SOLVED PAPERS

Chemistry
Complete Collection of all Questions asked
in ONLINE & OFFLINE JEE Main & AIEEE

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 Topicwise Solutions of Questions asked in
Last 20 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.
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 in Chemistry 1-11
2. States of Matter 12-25
3. Atomic Structure 26-37
4. Chemical Bonding and Molecular Structure 38-53
5. Chemical Thermodynamics 54-68
6. Solutions 69-86
7. Chemical Equilibrium 87-95
8. Ionic Equilibrium 96-107
9. Redox Reactions 108-112
10. Electrochemistry 113-129
11. Chemical Kinetics 130-147
12. Surface Chemistry 148-158
13. Classification of Elements and Periodicity in Properties 159-167
14. General Principles and Processes of Isolation of Metals 168-178
15. Hydrogen 179-185
16. s- Block Elements 186-194
17. p- Block Elements 195-211
18. d and f- Block Elements 212-223
19. Coordination Compounds 224-247
20. Environmental Chemistry 248-255
21. Purification and Characterisation of Organic Compounds 256-262
22. Some Basics Principles of Organic Chemistry 263-279
23. Hydrocarbons 280-294
24. Organic Compounds Containing Halogens 295-315
25. Organic Compounds Containing Oxygen 316-376
26. Organic Compounds Containing Nitrogen 377-409
27. Polymers 410-418
28. Biomolecules 419-435
29. Chemistry in Everyday Life 436-442
30. Principles Related to Practical Chemistry 443-452
SYLLABUS
SECTION- A (Physical Chemistry)
UNIT 1 Some Basic Concepts in hemistry
Matter and its nature, Dalton's atomic theory; Concept of atom, molecule, element and compound; Physical
quantities and their measurements in Chemistry, precision and accuracy, significant figures, S.I. Units,
dimensional analysis; Laws of chemical combination; Atomic and molecular masses, mole concept,
molar mass, percentage composition, empirical and molecular formulae; Chemical equations and
stoichiometry.

UNIT 2 States of Matter

Classification of matter into solid, liquid and gaseous states.
Gaseous State Measurable properties of gases; Gas laws - Boyle's law, Charle's law, Graham's law of
diffusion, Avogadro's law, Dalton's law of partial pressure; Concept of Absolute scale of temperature;
Ideal gas equation, Kinetic theory of gases (only postulates); Concept of average, root mean square and
most probable velocities; Real gases, deviation from Ideal behaviour, compressibility factor, van der Waals’
Equation, liquefaction of gases, critical constants.
Liquid State Properties of liquids - vapour pressure, viscosity and surface tension and effect of temperature
on them (qualitative treatment only).
Solid State Classification of solids: molecular, ionic, covalent and metallic solids, amorphous and crystalline
solids (elementary idea); Bragg's Law and its applications, Unit cell and lattices, packing in solids (fcc, bcc
and hcp lattices), voids, calculations involving unit cell parameters, imperfection in solids; electrical,
magnetic and dielectric properties.

UNIT 3 Atomic Structure

Discovery of sub-atomic particles (electron, proton and neutron); Thomson and Rutherford atomic models
and their limitations; Nature of electromagnetic radiation, photoelectric effect; spectrum of hydrogen atom,
Bohr model of hydrogen atom - its postulates, derivation of the relations for energy of the electron and radii
of the different orbits, limitations of Bohr's model; dual nature of matter, de-Broglie's relationship,
Heisenberg uncertainty principle.
Elementary ideas of quantum mechanics, quantum mechanical model of atom, its important features,ψ and
ψ2, concept of atomic orbitals as one electron wave functions; Variation of ψ and ψ2 with r for 1s and 2s
orbitals; various quantum numbers (principal, angular momentum and magnetic quantum numbers) and
their significance; shapes of s, p and d - orbitals, electron spin and spin quantum number; rules for filling
electrons in orbitals – aufbau principle, Pauli's exclusion principle and Hund's rule, electronic
configuration of elements, extra stability of half-filled and completely filled orbitals.

UNIT 4 Chemical Bonding and Molecular Structure

Kossel Lewis approach to chemical bond formation, concept of ionic and covalent bonds.
Ionic Bonding Formation of ionic bonds, factors affecting the formation of ionic bonds; calculation of
lattice enthalpy.
Covalent Bonding Concept of electronegativity, Fajan's rule, dipole moment; Valence Shell Electron Pair
Repulsion (VSEPR) theory and shapes of simple molecules.
Quantum mechanical approach to covalent bonding Valence bond theory - Its important features, concept
of hybridization involving s, p and d orbitals; Resonance.
Molecular Orbital Theory Its important features, LCAOs, types of molecular orbitals (bonding,
antibonding), sigma and pi-bonds, molecular orbital electronic configurations of homonuclear diatomic
molecules, concept of bond order, bond length and bond energy.
Elementary idea of metallic bonding. Hydrogen bonding and its applications.

UNIT 5 Chemical Thermodynamics

Fundamentals of thermodynamics System and surroundings, extensive and intensive properties, state
functions, types of processes.
First law of thermodynamics Concept of work, heat internal energy and enthalpy, heat capacity, molar
heat capacity, Hess's law of constant heat summation; Enthalpies of bond dissociation, combustion,
formation, atomization, sublimation, phase transition, hydration, ionization and solution.
Second law of thermodynamics Spontaneity of processes; ΔS of the universe and ΔG of the system as
criteria for spontaneity, ΔGo (Standard Gibb's energy change) and equilibrium constant.

UNIT 6 Solutions
Different methods for expressing concentration of solution - molality, molarity, mole fraction,
percentage (by volume and mass both), vapour pressure of solutions and Raoult's Law - Ideal and non-
ideal solutions, vapour pressure - composition plots for ideal and non-ideal solutions.
Colligative properties of dilute solutions - relative lowering of vapour pressure, depression of freezing
point, elevation of boiling point and osmotic pressure; Determination of molecular mass using colligative
properties; Abnormal value of molar mass, van’t Hoff factor and its significance.

UNIT 7 Equilibrium
Meaning of equilibrium, concept of dynamic equilibrium.
Equilibria involving physical processes Solid -liquid, liquid - gas and solid - gas equilibria, Henry’s law,
general characteristics of equilibrium involving physical processes.
Equilibria involving chemical processes Law of chemical equilibrium, equilibrium constants
(K and K) and their significance, significance of ΔG and ΔG o in chemical equilibria, factors affecting
equilibrium concentration, pressure, temperature, effect of catalyst; Le -Chatelier’s principle.
Ionic equilibrium Weak and strong electrolytes, ionization of electrolytes, various concepts of acids and
bases (Arrhenius, Bronsted - Lowry and Lewis) and their ionization, acid-base equilibria (including
multistage ionization) and ionization constants, ionization of water, pH scale, common ion effect,
hydrolysis of salts and pH of their solutions, solubility of sparingly soluble salts and solubility products,
buffer solutions.

UNIT 8 Redox Reactions and Electrochemistry

Electronic concepts of oxidation and reduction, redox reactions, oxidation number, rules for assigning
oxidation number, balancing of redox reactions.
Eectrolytic and metallic conduction,
conductance in electrolytic solutions, specific and molar conductivities and their variation with
concentration: Kohlrausch's law and its applications.
Electrochemical cells - Electrolytic and Galvanic cells, different types of electrodes, electrode potentials
including standard electrode potential, half - cell and cell reactions, emf of a Galvanic cell and its
measurement; Nernst equation and its applications; Relationship between cell potential and Gibbs’
energy change; Dry cell and lead accumulator; Fuel cells; Corrosion and its prevention.

UNIT 9 Chemical Kinetics

Rate of a chemical reaction, factors affecting the rate of reactions concentration, temperature, pressure
and catalyst; elementary and complex reactions, order and molecularity of reactions, rate law, rate
constant and its units, differential and integral forms of zero and first order reactions, their characteristics
and half - lives, effect of temperature on rate of reactions - Arrhenius theory, activation energy and its
calculation, collision theory of bimolecular gaseous reactions (no derivation).
UNIT 10 Surface Chemistry
Adsorption Physisorption and chemisorption and their characteristics, factors affecting adsorption of
gases on solids- Freundlich and Langmuir adsorption isotherms, adsorption from solutions.
Catalysis Homogeneous and heterogeneous, activity and selectivity of solid catalysts, enzyme catalysis
and its mechanism.
Colloidal state distinction among true solutions, colloids and suspensions, classification of colloids
- lyophilic, lyophobic; multi molecular, macromole-cular and associated colloids (micelles),
preparation and properties of colloids Tyndall effect, Brownian movement, electrophoresis, dialysis,
coagulation and flocculation; Emulsions and their characteristics.

SECTION- B (Inorganic Chemistry)

UNIT 11 Classification of Elements and Periodicity in Properties
Periodic Law and Present Form of the Periodic Table, s, p, d and f Block Elements, Periodic Trends in
Properties of Elementsatomic and Ionic Radii, Ionization Enthalpy, Electron Gain Enthalpy, Valence,
Oxidation States and Chemical Reactivity.

UNIT 12 General Principles and Processes of Isolation of Metals

Modes of occurrence of elements in nature, minerals, ores; steps involved in the extraction of metals -
concentration, reduction (chemical and electrolytic methods) and refining with special reference to the
extraction of Al, Cu, Zn and Fe; Thermodynamic and electrochemical principles involved in the extraction of
metals.

UNIT 13 Hydrogen
Position of hydrogen in periodic table, isotopes, preparation, properties and uses of hydrogen; physical and
chemical properties of water and heavy water; Structure, preparation, reactions and uses of hydrogen
peroxide; Classification of hydrides ionic, covalent and interstitial; Hydrogen as a fuel.

UNIT 14 s - Block Elements

(Alkali and Alkaline Earth Metals)
Group 1 and 2 Elements
General introduction, electronic configuration and general trends in physical and chemical properties of
elements, anomalous properties of the first element of each group, diagonal relationships.
Preparation and properties of some important compounds - sodium carbonate, sodium chloride, sodium
hydroxide and sodium hydrogen carbonate; Industrial uses of lime, limestone, Plaster of Paris and cement;
Biological significance of Na, K, Mg and Ca.

UNIT 15 p - Block Elements

Group 13 to Group 18 Elements, General Introduction Electronic configuration and general trends in
physical and chemical properties of elements across the periods and down the groups; unique behaviour
of the first element in each group.
Group wise study of the p – block elements
Group 13 Preparation, properties and uses of boron and aluminium; structure, properties and uses of
borax, boric acid, diborane, boron trifluoride, aluminium chloride and alums.
Group 14 Tendency for catenation; Structure, properties and uses of allotropes and oxides of carbon,
silicon tetrachloride, silicates, zeolites and silicones.
Group 15 Properties and uses of nitrogen and phosphorus; Allotrophic forms of phosphorus; Preparation,
properties, structure and uses of ammonia nitric acid, phosphine and phosphorus halides,(PCl3, PCl5);
Structures of oxides and oxoacids of nitrogen and phosphorus.
Group 16 Preparation, properties, structures and uses of dioxygen and ozone; Allotropic forms of sulphur;
Preparation, properties, structures and uses of sulphur dioxide, sulphuric acid (including its industrial
preparation); Structures of oxoacids of sulphur.
Group 17 Preparation, properties and uses of chlorine and hydrochloric acid; Trends in the acidic nature of
hydrogen halides; Structures of Interhalogen compounds and oxides and oxoacids of halogens.
Group 18 Occurrence and uses of noble gases; Structures of fluorides and oxides of xenon.

UNIT 16 d – and f – Block Elements

Transition Elements General introduction, electronic configuration, occurrence and characteristics,
general trends in properties of the first row transition elements - physical properties, ionization enthalpy,
oxidation states,
atomic radii, colour, catalytic behaviour, magnetic properties, complex formation, interstitial compounds,
alloy formation; Preparation, properties and uses of K2 Cr2 O7 and KMnO4.
Inner Transition Elements Lanthanoids Electronic configuration, oxidation states, chemical reactivity and
lanthanoid contraction. Actinoids Electronic configuration and oxidation states.

UNIT 17 Coordination Compounds

Introduction to coordination compounds, Werner's theory; ligands, coordination number, denticity,
chelation; IUPAC nomenclature of mononuclear coordination compounds, isomerism; Bonding Valence
bond approach and basic ideas of Crystal field theory, colour and magnetic properties; importance of
coordination compounds (in qualitative analysis, extraction of metals and in biological systems).

Unit 18 Environmental Chemistry

Environmental pollution Atmospheric, water and soil.
Atmospheric pollution Tropospheric and stratospheric.
Tropospheric pollutants : Gaseous pollutants Oxides of carbon, nitrogen and sulphur, hydrocarbons; their
sources, harmful effects and prevention; Green house effect and Global warming; Acid rain;
Particulate pollutants Smoke, dust, smog, fumes, mist; their sources, harmful effects and prevention.
Stratospheric pollution Formation and breakdown of ozone, depletion of ozone layer - its mechanism
and effects.
Water pollution Major pollutants such as, pathogens, organic wastes and chemical pollutants their harmful
effects and prevention. Soil pollution Major pollutants such as: Pesticides (insecticides, herbicides and
fungicides), their harmful effects and prevention. Strategies to control environmental pollution.

SECTION- C (Organic Chemistry)

UNIT 19 Purification & Characterisation of Organic Compounds
Purification Crystallization, sublimation, distillation, differential extraction and chromatography principles
and their applications.
Qualitative analysis Detection of nitrogen, sulphur, phosphorus and halogens.
Quantitative analysis (basic principles only) Estimation of carbon, hydrogen, nitrogen, halogens, sulphur,
phosphorus. Calculations of empirical formulae and molecular formulae; Numerical problems in organic
quantitative analysis.

UNIT 20 Some Basic Principles of Organic Chemistry

Tetravalency of carbon; Shapes of simple molecules hybridization (s and p); Classification of organic
compounds based on functional groups: —C=C—,—C=C— and those containing halogens, oxygen,
nitrogen and sulphur, Homologous series; Isomerism - structural and stereoisomerism.
Nomenclature (Trivial and IUPAC)
Covalent bond fission Homolytic and heterolytic free radicals, carbocations and carbanions; stability of
carbocations and free radicals, electrophiles and nucleophiles.
Electronic displacement in a covalent bond Inductive effect, electromeric effect, resonance and
hyperconjugation.
Common types of organic reactions Substitution, addition, elimination and rearrangement.

UNIT 21 Hydrocarbons
Classification, isomerism, IUPAC nomenclature, general methods of preparation, properties and reactions.
Alkanes Conformations: Sawhorse and Newman projections (of ethane); Mechanism of halogenation
of alkanes.
Alkenes Geometrical isomerism; Mechanism of electrophilic addition: addition of hydrogen, halogens,
water, hydrogen halides (Markownikoff's and peroxide effect); Ozonolysis, oxidation, and polymerization.
Alkynes acidic character; addition of hydrogen, halogens, water and hydrogen halides; polymerization.
Aromatic hydrocarbons Nomenclature, benzene structure and aromaticity; Mechanism of electrophilic
substitution: halogenation, nitration, Friedel – Craft's alkylation and acylation, directive influence of
functional group in mono-substituted benzene.

UNIT 22 Organic Compounds Containing Halogens

General methods of preparation, properties and reactions; Nature of C—X bond; Mechanisms of
substitution reactions. Uses/environmental effects of chloroform, iodoform

UNIT 23 Organic Compounds Containing Oxygen

General methods of preparation, properties, reactions and uses.
Alcohols, Phenols and Ethers
Alcohols Identification of primary, secondary and tertiary alcohols; mechanism of dehydration.
Phenols Acidic nature, electrophilic substitution reactions: halogenation, nitration and sulphonation,
Reimer - Tiemann reaction.
Ethers Structure.
Aldehyde and Ketones Nature of carbonyl group;
Nucleophilic addition to >C=O group, relative reactivities of aldehydes and ketones; Important reactions
such as - Nucleophilic addition reactions (addition of HCN, NH3 and its derivatives), Grignard reagent;
oxidation; reduction (Wolff Kishner and Clemmensen) acidity of α-hydrogen, aldol condensation,
Cannizzaro reaction, Haloform reaction; Chemical tests to distinguish between aldehydes and Ketones.
Carboxylic Acids Acidic strength and factors affecting it.

UNIT 24 Organic Compounds Containing Nitrogen

General methods of preparation, properties, reactions and uses.
Amines Nomenclature, classification, structure basic character and identification of primary, secondary and
tertiary amines and their basic character.
Diazonium Salts Importance in synthetic organic chemistry.

UNIT 25 Polymers
General introduction and classification of polymers, general methods of polymerization-addition and
condensation, copolymerization; Natural and synthetic rubber and vulcanization; some important polymers
with emphasis on their monomers and uses - polythene, nylon, polyester and bakelite.
UNIT 26 Biomolecules
General introduction and importance of biomolecules.
Carbohydrates Classification: aldoses and ketoses; monosaccharides (glucose and fructose), constituent
monosaccharides of oligosacchorides (sucrose, lactose, maltose) and polysaccharides (starch, cellulose,
glycogen).
Proteins Elementary Idea of α-amino acids, peptide bond, . polypeptides; proteins: primary, secondary,
tertiary and quaternary structure (qualitative idea only), denaturation of proteins, enzymes.
Vitamins Classification and functions.
Nucleic Acids Chemical constitution of DNA and RNA. Biological functions of Nucleic acids.

UNIT 27 Chemistry in Everyday Life

Chemicals in medicines Analgesics, tranquilizers, antiseptics, disinfectants, antimicrobials, antifertility
drugs, antibiotics, antacids, antihistamins - their meaning and common examples.
Chemicals in food Preservatives, artificial sweetening agents - common examples.
Cleansing agents Soaps and detergents, cleansing action.

UNIT 28 Principles Related to Practical Chemistry

— Detection of extra elements (N, S, halogens) in organic compounds; Detection of the following
functional groups: hydroxyl (alcoholic and phenolic), carbonyl (aldehyde and ketone), carboxyl and
amino groups in organic compounds.
— Chemistry involved in the preparation of the following
— Inorganic compounds Mohr's salt, potash alum.
— Organic compounds Acetanilide,
p-nitroacetan ilide, aniline yellow, iodoform.
— Chemistry involved in the titrimetric excercises - Acids bases and the use of indicators, oxali acid vs
KMnO4, Mohr's salt vs KMnO4.
— Chemical principles involved in the qualitative salt analysis
— Cations — Pb2+ , Cu2+, Al3+, Fe3+, Zn2+, Ni2+, Ca2+, Ba2+, Mg2+ NH4+. Anions – CO32-, S2-, SO42-, NO2, NO3,
Cl-, Br-, I- (Insoluble salts excluded).
— Chemical principles involved in the following experiments
1. Enthalpy of solution of CuSO4
2. Enthalpy of neutralization of strong acid and strong base.
3. Preparation of lyophilic and lyophobic sols.
4. Kinetic study of reaction of iodide ion with hydrogen peroxide at room temperature.
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01
Some Basic Concepts
in Chemistry
TOPIC 1 03 Among the following statements, (a) 10−6 m (b) 10−4 m
(c) 10−8 m (d) 10−2 m
Nature of Matter, that which was not proposed by
Dalton was Ans. (a)
Significant Figures and Laws [2020, 7 Jan Shift-I]
100 mL (cm3) of hexane contains 0.27 g
(a) chemical reactions involve
of Chemical Combinations reorganisation of atoms. These are of fatty acid.
neither created nor destroyed in a In 10 mL solution, mass of the fatty acid,
01 The number of significant figures in chemical reaction. 0.27
0.00340 is …… . m= × 10
(b) when gases combine or reproduced 100
[2021, 25 July Shift-II] in a chemical reaction they do so in a
Ans. (3) = 0.027 g
simple ratio by volume provided all
gases are at the same T and P. Density of fatty acid, d = 0.9 g cm−3
Number of significant figures = 0.00340
(c) all the atoms of a given element have ∴Volume of the fatty acid over the watch
= 3.40 × 10 − 3 glass,
identical properties including
So, total number of significant figure = 3. m 0.027
identical mass. Atoms of different V= =
Here, elements differ in mass. d 0.9
0.00 34 0 (d) matter consists of indivisible atoms. = 0.03 cm3
Trailing zero
Leading Non-zero Ans. (b) Let, height of the cylindrical monolayer
digits
zero
The postulates given in options (a), (c) = h cm
None-zero digits and trailing zero are and (d) are proposed by Dalton. Q Volume of the cylinder = Volume of
counted. fatty acid
Option (b) is defining the Gay-Lussac’s
(Note You can convert it into simplest law of combining volumes of gases.
form first.)
04 0.27 g of a long chain fatty acid
02 The number of significant figures in was dissolved in 100 cm 3 of h cm
50000.020 × 10 −3 is ………… . hexane. 10 mL of this solution was
[2021, 26 Feb Shift-I]
added dropwise to the surface of
Ans. (7)
water in a round watch glass. 10 cm
Non-zero digits are always significant.
Hexane evaporates and a
Any zeros between two significant digits ⇒ V = π r2 × h
are significant. monolayer is formed. The distance V
from edge to centre of the watch ⇒ h= 2
∴ Zero’s between 5 and 2 are all πr
significant. glass is 10 cm. What is the height of
0.03 cm3
50000.020 × 10 −3 the monolayer? =
3 × (10)2 cm2
↑ [Density of fatty acid = 0.9 g cm −3 ;
= 1 × 10 −4 cm
(Number of significant figures = 7) π = 3] [2019, 8 April Shift-II]
= 1 × 10 −6 m
2 JEE Main Chapterwise Topicwise Chemistry

TOPIC 2 35
Cl : 37 Cl On solving the equation, we obtain
3  3 3 1 MA = 5 × 10 −3 and MB = 10 × 10 −3
Atomic Mass, Molecular : 1 −  ⇒ :
4  4 4 4 So, the molar mass of A (MA ) is
Mass and Formulae of On simplify this ratio, we get 3 : 1. 5 × 10 −3 kgmol −1 and B (MB) is 10 × 10 −3 kg
Compounds mol −1.
07 The mass percentage of nitrogen in
05 A solution of phenol in chloroform histamine is ……… 09 The ratio of mass per cent of C and
when treated with aqueous NaOH [2020, 9 Jan Shift-I] H of an organic compound
gives compound P as a major Ans. (37.84) (C x Hy O z ) is 6 : 1. If one molecule of
product. The mass percentage of Histamine : the above compound (C x Hy O z )
carbon in P is ……… . N NH2 contains half as much oxygen as
(to the nearest integer) required to burn one molecule of
N compound C x Hy completely to CO 2
(Atomic mass: C =12; H= 1; O = 16)
[2020, 6 Sep Shift-II]
Molecular formula = C5H9N3. Molecular and H2O. The empirical formula of
mass = 111
Ans. (69) compound C x Hy O z is [JEE Main 2018]
Number of nitrogen atoms per molecule
A solution of phenol in chloroform react =3 (a) C 3H6O 3 (b) C2H4O
with aqueousNaOHgivescompoundP (c) C 3H4O2 (d) C2H4O 3
Mass due to N = 3 × 14 = 42
(salicylaldehyde). Ans. (d)
42
OH OH % of N = × 100 = 37.84%
111 We can calculate the simplest whole
CHO number ratio of C and H from the data
NaOH
The value have a range from 37.80 to
+ CHCl3 38.20. given, as

Simplest
(P)
(Salicylaldehyde)
08 5 moles of AB2 weight 125 × 10 −3 kg Element
Relative Molar Relative
whole
mass mass mole
and 10 moles of A 2B2 weight no. ratio
∴ Mass % of C in P (Compound)
Mass of C 300 × 10 −3 kg. The molar mass of C 6 12 6 0.5
= × 100 = 0.5 =1
Mass of Compound A(M A ) and molar mass of B (M B ) in kg 12 0.5
Here, mass of C = 12 × 7 mol −1 are [2019, 12 April Shift-I] H 1 1 1 1
=1 =2
mass of compound (P) = (a) M A = 10 × 10−3 and M B = 5 × 10−3 1 0.5
 (b) M A = 50 × 10−3 and M B = 25 × 10−3
 C H O Alternatively this ratio can also be
 (12 × 7 + 6 × 1 + 16 + 2) (c) M A = 25 × 10−3 and M B = 50 × 10−3 calculated directly in the terms of x and y
12 × 7 (d) M A = 5 × 10−3 and M B = 10 × 10−3 as
= × 100 = 68.85% = 69%
84 + 6 + 32 Ans. (d) 12x 6
=
06 The average molar mass of Key Idea To find the mass of A and B in y 1
chlorine is 35.5 g mol −1 . The ratio of the given question, mole concept is (given and molar mass of C = 12, H = 1)
35 used. Now, after calculating this ratio look for
Cl to 37 Cl in naturally occurring given mass (w ) condition 2 given in the question i.e.
chlorine is close to Number of moles (n) =
molecular mass (M) quantity of oxygen is half of the quantity
[2020, 6 Sep Shift-II] required to burn one molecule of
(a) 4 : 1 (b) 3 : 1 Compound Mass of A Mass of B compound Cx Hy completely to CO2 and
(c) 2 : 1 (d) 1 : 1 (g) (g) H2O. We can calculate number of oxygen
Ans. (b) AB2 MA 2M B atoms from this as consider the
equation.
Given, A2B2 2M A 2M B
Cx CHy +  x +  O2 → xCO2 + H2O
y y
Average molar mass of chlorine is
35.5 g mol − 1. We know that,  4  2
Naturally occurring chlorine are Number of moles Number of oxygen atoms required
given mass (w)
35
Cl 37
Cl (n) = = 2 ×  x +  = 2x + 
y y
Molar ratio x 1− x
molecular mass (M)
 4   2 
Total molar ratio = x + 1 − x = 1 n× M = w …(A)
Now given, z = 2x +  =  x + 
1 y y
Mass average =35 × x + 37 × (1 − x) Using equation (A), it can be concluded 2  2   4 
that
35.5 = 35x + 37 − 37 x Here we consider x and y as simplest
1. 5 3 5(MA + 2MB) = 125 × 10 −3 kg …(i) ratios for C and H so now putting the
2x = 37 − 35.5; x = = 0 .75 =
2 4 10 (2MA + 2MB) = 300 × 10 −3 kg …(ii) values of x and y in the above equation.
z =  x +  =  1 +  = 1.5
3 From equation (i) and (ii) y 2
35
For Cl, x=
4 1 (MA + 2MB)  125   4   4 
= 
37
For Cl; 1−
3 2 (2MA + 2MB)  300  Thus, the simplest ratio figures for x, y
4 and z are x = 1, y = 2 and z = 1.5
Some Basic Concepts in Chemistry 3

Now, put these values in the formula 12 A gaseous hydrocarbon gives upon (a) C 6H8N2 (b) C 7H10N
given i.e. (c) C 5H6N3 (d) C 4H18N3
combustion, 0.72 g of water and
Cx Hy Oz = C1H2O1.5 Ans. (a)
3.08 g of CO 2 . The empirical
So, empirical formula will be
formula of the hydrocarbon is Molar mass 108 g mol −1
[C1H2O1.5 ] × 2 = C2H4O3 [JEE Main 2013] Total part by weight = 9 + 1 + 3.5 = 13.5
(a) C2H4 (b) C 3H4 (c) C 6H5 (d) C 7H8 9
10 The most abundant elements by Weight of carbon = × 108 = 72 g
Ans. (d) 13.5
mass in the body of a healthy 18 g H2O contain 2g H. 72
human adult are Oxygen (61.4%); Number of carbon atoms = = 6
∴ 0.72 g H2O contain 0.08 g H 44 g CO2 12
Carbon (22.9%), Hydrogen (10.0 %); contain 12 g C. 1
and Nitrogen (2.6%). The weight Weight of hydrogen = × 108 = 8 g
∴3.08 g CO2 contain 0.84 g C. 13.5
which a 75 kg person would gain if ∴ C:H=
0.84 0.08
: = 0.07 :0.08 = 7 : 8 8
all 1 Hatoms are replaced by 2 H 12 1 Number of hydrogen atoms = = 8
1
atoms is [JEE Main 2017] ∴ Empirical formula = C7 H8
3.5
(a) 15 kg (b) 37.5 kg Weight of nitrogen = × 108 = 28 g
13 The mass of potassium dichromate 13.5
(c) 7.5 kg (d) 10 kg
Ans. (c) crystals required to oxidise 750 cm3 Number of nitrogen atom =
28
=2
Given, abundance of elements by mass of0.6 M Mohr’s salt solution is (molar 14
oxygen = 614
. %, carbon = 229
. %, mass = 392) [AIEEE 2011] Hence, molecular formula = C6H8N2 .
hydrogen = 10% and nitrogen = 26.% (a) 0.49 g (b) 0.45 g
Total weight of person = 75 kg (c) 22.05 g (d) 2.2 g 16 Experimentally, it was found that a
75 × 10 Ans. (c) metal oxide has formula M 0.98 O.
Mass due to 1H= = 7.5 kg Metal M, present as M 2+ and M 3+ in
100 Mohr’s salt is FeSO4 ⋅ (NH4 )2 SO4 ⋅6H2O .
1 2 Only oxidisable part Fe2 + is its oxide. Fraction of the metal
H atoms are replaced by H atoms,
[Fe2 + → Fe3+ +e − ] × 6 which exists as M 3+ would be
Mass due to 2 H = (7.5 × 2) kg [JEE Main 2013]
∴Mass gain by person = 7.5 kg Cr2O27− + 14H + 6 e − → 2Cr 3+ + 7H2O
+
(a) 7.01% (b) 4.08%
6Fe + Cr2O27− + 14H+ →
2+
(c) 6.05% (d) 5.08%
11 At 300 K and 1 atm, 15 mL of a 6Fe3+ + 2Cr 3+ + 7H2O Ans. (b)
gaseous hydrocarbon requires Millimoles of Fe = 750 × 0.6 = 450
2+
M0.98O
375 mL air containing 20% O 2 by 450
Moles of Fe2 + = = 0.450 mol Consider one mole of the oxide.
volume for complete combustion. 1000
2+ Moles of M = 0.98 mole of O2 −= 1
After combustion, the gases 6 mol Fe ≡ 1 mol Cr2O27−
Let moles of M3+ = x
occupy 330 mL. Assuming that the 2+ 0.450
∴ 0.450 mol Fe ≡ ⇒ Moles of M2 + = 0.98 − x
water formed is in liquid form and 6
⇒ On balancing charge,
the volumes were measured at the = 0.075 mol Cr2O27−
(0.98 − x) × 2 + 3x − 2 = 0
same temperature and pressure, = 0.075 × 294 g = 22.05 g
⇒ 1.96 − 2x + 3x − 2 = 0
the formula of the hydrocarbon is
[JEE Main 2016] 14 If we consider that 1/6, in place of ⇒ x = 0.04
0.04
(a) C3H8 (b) C 4H8 1/12, mass of carbon atom is taken ⇒ Percentage of M3+ = × 100
(c) C 4H10 (d) C 3H6 to be the relative atomic mass unit, 0.98
Ans. (None) the mass of one mole of a = 4.08%

Cx Hy (g) +  x +  O2 (g) → xCO2 (g)

y substance will [AIEEE 2005]
 4 (a) be a function of the molecular mass
y
75 mL
of the substance TOPIC 3
+ H2O (l )
2 30mL (b) remain unchanged Mole Concept and
(c) increase two fold
O2 used = 20% of 375 = 75 mL
(d) decrease twice
Concentration Terms
Inert part of air = 80% of 375 = 300 mL
Total volume of gases = CO2 + Inert part Ans. (b)
17 The number of atoms in 8 g of
of air The mass of one mole ofa substance will
= 30 + 300 = 330 mL
sodium is x × 10 23 . The value of x is
remain unchanged.
y ……… .
x+
x 30
= ⇒x =2 ⇒ 4 = 75 15 In an organic compound of molar (Nearest integer)
1 15 1 15 mass 108 g mol–1 C, H and N atoms [Given : N A = 6.02 × 10 23 mol −1
y
⇒ x+ =5 are present in 9 : 1 : 3.5 by weight. Atomic mass of Na = 23.0 u]
4 Molecular formula can be [2021, 1 Sep Shift-II]
⇒ x = 2, y = 12 ⇒ C2H12 [AIEEE 2002]
4 JEE Main Chapterwise Topicwise Chemistry

Ans. (2) Milliequivalent of Fe2 + (Round off to the nearest integer).

Given, mass of Na = 8g = Milliequivalent of K2 Cr2O7
[Given, atomic masses H : 1.0 u,
Molar mass of Na = 23 gmol −1 n1M1V1 = n2 M2V2
O : 16.0 u] [2021, 17 March Shift-I]
Weight of sodium atom M1 × 10 × 1 = 6 × 0.02 × 15
= 6 × 0.02 × 15 Ans. (64)
Molecular mass of sodium atom ⇒ M1 = = 0.18
Number of atoms 10 Given, molality = 100
= ⇒100 moles of solute in 1 kg of solvent
Avogadro’ s number M1 ~− 18 × 10 −2 M
8 g Number of atoms So, value of x is 18. Mole fraction of solute (χ Solute )
=
23 g 6.022 × 1023 =
Moles of solute
=
nSolute
8 × 6.022 20 If the concentration of glucose Total moles nSolute + nSolvent
Number of atoms = × 1023
23 (C 6H12O 6 ) in blood is 0.72 gL−1 , the
1000
molarity of glucose in blood is …… nSolvent = = 55.5
Number of atoms = 2.09 × 1023 18
x ≈2 ×10 −3 M. (Nearest integer) 100 100
χ Solute = = = 0.643
Hence, answer is 2. [Given : Atomic mass ofC = 12, 100 + 55.5 155.5
H = 1,O = 16 u] [2021, 22 July Shift-II] . × 10 − 2 = 64 × 10 −2
χ Solute = 643
18 10.0 mL of 0.05 M KMnO4 solution Ans. (4)
was consumed in a titration with Molar mass of glucose (C6H12O6 ) 23 The NaNO 3 weighed out to make
10.0 mL of given oxalic acid = 12 × 6 + 12 × 1 + 16 × 6 = 180 g mol −1 50 mL of an aqueous solution
dihydrate solution. The strength of Concentration of glucose containing 70.0 mg Na +
given oxalic acid solution is …… = 0.72 g L −1 (given) per mL is ……… g. (Rounded off to
× 10 −2 g/L. ∴Molarity (M) the nearest integer)
(Round off to the nearest integer) Concentration of glucose WB
[2021, 27 July Shift-II]
= = [Given : Atomic weight in g mol −1 ,
Molar mass of glucose MB
Ans. (1575) Na : 23 ; N : 14 ; O : 16].
0.72
M= = 0.004 [2021, 26 Feb Shift-II]
For titration of KMnO4 with oxalic acid, 180 Ans. (13)
neq (KMnO4 ) = neq (H2 C2O4 ⋅2H2O) = 4 × 10 −3 M. 70 mg Na + is present in 1 mL of NaNO 3
10 × 0.05 10 × M
or ×5= ×2 solution.
1000 1000 21 15 mL of aqueous solution of Fe 2+ ∴ 50 mL of NaNO 3 will contain
⇒ M = 0.125 M in acidic medium completely = 70 × 50 mg
Molar mass of H2 C2O4 ⋅2H2O reacted with 20 mL of 0.03 M 70 × 50
= = 3. 5 gm
= 2 × 1 + 2 × 12 + 4 × 16 + 2(18) aqueous Cr 2O 2−
7 . The molarity of 1000
= 126 g/mol the Fe 2+ solution is …… × 10 −2 M Moles of Na+ in solution = Moles of
Strength of oxalic acid = (126 × 0.125) g/L (Round off to the nearest integer). NaNO3 in solution
= 15.75 g/L [2021, 17 March Shift-I] [QNaNO3 → Na+ + NO−3 ]
= 1575 × 10 −2 g/L Ans. (24) 3.5
= mol
Cr2O27− + Fe2 + → Cr 3+ + Fe3+ 23
19 When 10 mL of an aqueous solution +6
+2 +3 +3
[QMolar mass of Na+ = 23g mol −1]
of Fe 2+ ions was titrated in the Dichromate (Cr2O27− ) oxidised Fe2 + to Fe3+ Mass of NaNO3 = mole × molar mass
presence of dil. H2SO 4 using and itself get reduced to Cr 3+ . [Qmolar mass of NaNO3 = 85 gmol −1]
diphenylamine indicator, Valency factor of Cr2O27− = 6 as Cr gets 3.5
= × 85 = 12934
. g−
~ 13 g
15 mL of 0.02 M solution of reduced from +6 to +3. 23
K 2Cr 2O 7 was required to get the Valency factor of Fe2 + = 1 as it gets
end point. The molarity of the oxidised from +2 to +3. 24 The mole fraction of glucose
solution containing Fe 2+ ions is From law of equivalence, (C 6H12O 6 ) in an aqueous binary
x × 10 −2 M. The value of x is …… . Milliequivalent of Cr2O27− = Milliequivalent solution is 0.1. The mass
of Fe2 +
(Nearest integer) percentage of water in it, to the
[2021, 25 July Shift-I] M1V1n1 = M2V2 n2
nearest integer, is ......... .
Ans. (18) (M1 × V1) × 6 = (M2 × V2 ) × 1
[2020, 3 Sep Shift-I]
(0.03 × 20) × 6 = (M2 × 15) 1
For the given reaction, Ans. (47.00)
⇒ M2 = 0.24 molar
Fe2 + + Cr2O27− → Fe3+ + Cr 3+ Let, for glucose :
= 24 × 10 − 2 molar
Volume of aqueous solution of Fe2 + ion Mass = w B g, mole = nB
(V1) = 10 mL. and mole fraction = χ B
Volume of K2 Cr2O7 solution (V2 ) = 15 mL
22 The mole fraction of a solute in a
(Molar mass, MB = 180 g mol −1)
Molarity of K2 Cr2O7 , M2 = 0.02 M
100 molal aqueous solution ………
For water : mass = w A g,
× 10 −2
Some Basic Concepts in Chemistry 5

mole = nA and mole fraction = χ A (a) 0.85 and 0.25 (b) 0.85 and 0.5 Ans. (4.97)
(Molar mass, MA = 18 g mol −1) (c) 1.7 and 0.5 (d) 1.7 and 0.25 Ferrous sulphate heptahydrate
Where, χ A + χ B = 1 Ans. (c) FeSO4 ⋅ 7H2O.
χB χB 0.1 1 Volume of hydrogen = 5.6 If the amount of the salt is ‘x’ gram.
⇒ = = =
χ A 1 − χ B 0.9 9 Volume strength = 11.2 × molarity Mass of iron contained in it
Volume strength x × atomic mass of Fe (= 55.85)
nB ⇒ Molarity = =
11.2 Molar mass of FeSO4 ⋅ 7H2O(= 277.85)
nA + nB 1
⇒ = 5.6 55.85 x
nA 9 = = 0.5 =
11.2 277.85
nA + nB
Suppose, that the solution taken is = 1 L 10 ppm of iron in 100 kg of wheat, can be
wB acheived as,
Mass of solution = 1000 mL × 1 g/mL
nB1 180 1 w B 18 1 mass of iron × 10 6
⇒ = ⇒ = ⇒ × = = 1000 g = = 10
nA 9 w A 9 180 w A 9 mass of wheat (= 100 kg = 10 5 g)
Mass of solute = Moles × Molar mass
18
= 0.5 × 34 55.85 x × 10 6 277.85
w B 10 w 10 = = 10 ⇒ x = = 497
. g
⇒ = ⇒ B + 1= +1 [Qmolar mass of H2O2 = 34] 277.85 × 10 5 55.85
wA 9 wA 9
= 17 g This value may vary from 4.95 to 4.99.
wA 9 17
⇒ = ⇒ Mass % = × 100 = 1.7%
wA + wB 19 1000 29 The molarity of HNO 3 in a sample
wA 9 which has density 1.4 g/mL and
⇒ % = × 100 = 47.368 −
~ 47.00
27 A 100 mL solution was made by
wA + wB 19 mass percentage of 63% is ………
adding 1.43 g of Na 2CO 3 ⋅ xH2O. The
So, mass percentage of water (A) in the (Molecular weight of HNO 3 = 63)
normality of the solution is 0.1 N.
solution is 47.00. [2020, 9 Jan Shift-I]
The value of x is ……… .
[2020, 4 Sep Shift-II]
Ans. (14.00)
25 6.023 × 10 22 molecules are present Ans. (10) For 100 g sample of the solution,
in 10 g of a substance ‘x’. The Molar mass of Na2 CO3 ⋅ xH2O. mass of HNO3 = 63 g,
molarity of a solution containing 5 g (Atomic mass of Na = 23, C = 12, O = 16) 63
∴ nHNO = = 1 mol
of substance ‘x’ in 2 L solution is = 23 × 2 + 12 + 48 + 18x 3
63
…… × 10 −3 . [2020, 3 Sep Shift-II]
=46 + 12 + 48 + 18x = Mass
Volume of solution =
Ans. (25) (106 + 18x) Density
× 1023 molecules are present Equivalent weight ofNa2 CO3 ⋅ xH2O 100 g
Given, 6023
. =
in 10 g substance. Molar mass M 14
. g /mL
= = = (53 + 9x)
Number of moles n factor 2 100 1
= mL = L
Number of molecules Mass (given) [Here, m = molar mass and n factor = 2] 14
. 14
= =
6 × 1023 Molar mass Weight n 1
Gram equivalent = Molarity = = = 14 M
10 × 6023
. × 1023 Equivalent weight V (L) (1 / 14)
Molar mass =
.
6023 × 1022 [Given, weight ofNa2 CO3 ⋅ xH2O = 143. g]
Hence, gram equivalent of
30 A 10 mg effervescent tablet
= 100 g/mol containing sodium bicarbonate and
1.43
We know that Na2 CO3 ⋅ xH2O =
53 + 9x oxalic acid releases 0.25 mL of CO 2
Moles of solute atT = 298.15 K and p = 1 bar. If molar
Molarity = G 143
.
Volume of solution (l ) Normality = meq ; 0.1 = volume of CO 2 is 25.0 L under such
Vlitre 53 + 9x
 Given, molarity of solution containing = 5 condition, what is the percentage
of subtance, Volume = 2L  0.1
  {As, volume = 100 mL = 0.1 L of sodium bicarbonate in each
(5 / 100) 5 tablet? [Molar mass of NaHCO 3
= = So, 10 −2 =
.
143
⇒ 53 + 9x = 143
2 100 × 2 53 + 9x = 84 g mol −1 ] [ 2019, 11 Jan Shift-I]
= 0.025 = 25 × 10 −3 9x = 90 ⇒ x = 10.00 (a) 8.4 (b) 0.84 (c) 16.8 (d) 33.6
Ans. (a)
26 The strengths of 5.6 volume 28 Ferrous sulphate heptahydrate is
2NaHCO3 + H2 C2O4 → 2CO2 + Na2 C4O4
hydrogen peroxide (of density used to fortify foods with iron. The
+ H2O
1 g/mL) in terms of mass amount (in grams) of the salt 2 mol 1 mol 2 mol
percentage and molarity (M), required to achieve 10 ppm of iron in ⇒In the reaction, number of mole of CO2
respectively, are 100 kg of wheat is ……… . produced.
pV 1 bar × 0.25 × 10 −3 L
(Take molar mass of hydrogen Atomic weight : Fe = 55.85; n= =
RT 0.082 L atm K−1mol −1 × 298.15 K
peroxide as 34 g/mol) S = 32.00; O = 16.00
[2020, 3 Sep Shift-II] [2020, 8 Jan Shift-I] = 1.02 × 10 −5 mol
6 JEE Main Chapterwise Topicwise Chemistry

Number of mole of NaHCO3 M1V1 + M2V2

M= 36 How many moles of magnesium
Weight of NaHCO3 V1 + V2 phosphate, Mg 3 (PO 4 ) 2 will contain
=
Molecular mass of NaHCO3 750 × 0.5 + 250 × 2 875 0.25 mole of oxygen atoms?
= =
∴ w NaHCO = 1.02 × 10 −5
× 84 × 10 mg
3 750 + 250 1000 [AIEEE 2006]
3
= 0.875 M (a) 0.02 (b) 3.125 × 10−2
= 0.856 mg (c) 1.25 × 10−2 (d) 2.5 × 10−2
0.856 34 The density of a solution prepared
⇒ NaHCO 3 % = × 100 = 8.56% Ans. (b)
10 by dissolving 120 g of urea (mol. 8 moles of O-atom are contained by 1 mole
mass = 60u) in 1000 g of water is Mg 3 (PO4 )2 .
31 The hardness of a water sample (in 1.15 g/mL. The molarity of this Hence, 0.25 moles of O-atom are
terms of equivalents of CaCO 3 ) contained by
solution is [AIEEE 2012]
containing 10 −3 M CaSO 4 is 1
= × 0.25 mol Mg 3( PO4 )2 = 3.125 × 10 −2
(a) 0.50 M (b) 1.78 M
(Molar mass of CaSO 4 = 136 g mol −1 ) (c) 1.02 M (d) 2.05 M
8
[2019, 12 Jan Shift-I]
Ans. (d) 37 Number of atoms in 560 g of Fe
(a) 100 ppm (b) 10 ppm
Total mass of solution = 1000 g (atomic mass = 56 g mol −1 ) is
(c) 50 ppm (d) 90 ppm
water + 120 g urea = 1120 g
Ans. (a) Density of solution = 1.15 g / mL
(a) twice that of 70 g N [AIEEE 2002]
Hardness of water sample can be mass (b) half that of 20 g H
Thus, volume of solution =
calculated in terms of ppm density (c) Both (a) and (b)
concentration of CaCO3. (d) None of the above
1120 g
Given, molarity = 10 −3 M =
1.15 g / mL Ans. (c)
i.e. 1000 mL of solution contains 10 −3
= 973.91 mL 560 g of Fe
mole of CaCO3. 560 g
∴ Hardness of water = ppm of CaCO3 = 0.974 L Number of moles = = 10 mol
56 g mol −1
10 −3 × 1000 Moles of solute =
120
= 2 mol
= × 10 6 For 70 g of N, 14 g N = 1 mol of N -atom
1000 60
moles of solute 70 g N = 5 mol of N -atom
= 100 ppm Molarity =
volume (L) of solution For 20 g of H, 1 g H = 1 mol of H -atom
32 The ratio of masses of oxygen and 2 mol 20 g H ≡ 20 mol of H -atom
= = 2.05 mol L−1
nitrogen in a particular gaseous 0.974 L
mixture is 1 : 4. The ratio of number
of their molecule is [ JEE Main 2014]
35 The molality of a urea solution in TOPIC 4
which 0.0100 g of urea,
(a) 1 :4 (b) 7 : 32
[( NH2 ) 2 CO] is added to
Stoichiometric and
(c) 1 :8 (d) 3 :16
0.3000 dm 3 of water at STP is Volumetric Calculations
Ans. (b) [AIEEE 2011]
The number of moles is given by (a) 5.55 × 10− 4 M (b) 33.3M
38 Sodium oxide reacts with water to
weight (w) produce sodium hydroxide. 20.0 g
n= (c) 3.33 × 10−2 M (d) 0.555 M
molecular weight (M) of sodium oxide is dissolved in
Ans. (a)
Thus, ratio of moles of O2 and N2 is given moles of the solute 500 mL of water. Neglecting the
by Molality = change in volume, the
mass of the solvent in kg
nO 2  WO / MO   WO   MN  concentration of the resulting
=  2 2 
= 2   2 
Moles of urea (nurea ) =
0.0100 g
n N2  W /M   W   M  60 g mol −1 NaOH solution is ....... × 10 − 1 M.
 N2 N2   N2   O 2 
(Nearest integer)
=   ×   =
1 28 7 Mass of 1000 mL of solution
 4   32  32 = volume × density [Atomic mass : Na = 23.0, O = 16.0,
Hence, ratio of nO 2 and n N 2 is 7 :32. 1g H = 1.0] [2021, 31 Aug Shift-II]
= 300 mL ×
mL Ans. (13)
33 The molarity of a solution obtained [Q 1 dm3 = 1000 mL] For the reaction,
by mixing 750 mL of 0.5 M HCl with = 300 g Na2O + H2O → 2NaOH
250 mL of 2M HCl will be Mass of solvent = 300 g − 0.0100 g 1 mol 2 mol
[JEE Main 2013] 20 x mol

(a) 0.875 M (b) 1.00 M = 299.9 g 62

mol

= 0.2999 kg 20
(c) 1.75 M (d) 0.0975 M Moles of NaOH formed ⇒x = ×2
0.0100 62
Ans. (a) Molality =
60 × 0.2999 Concentration of NaOH
The molarity of a resulting solution is −4 −1
= 5.55 × 10 Moles of NaOH
given by mol kg =
Volume of solution (in litre)
Some Basic Concepts in Chemistry 7
20 Ans. (3) Millimoles of HCl = 500 × 1 = 500
×2
= 62 = 1.29 M = 13 × 10 −1 M Given, 448 mL of A gives 1.53 g of Now, reaction is
500 vapours. NaOH + HCl → NaCl + H2O
1000 1.53 At t = 0, 125 500 0 0
∴ 22400 mL of A gives = × 22400
445 At t = t, 0 375 125 125
39 100 g of propane is completely
= 76.50 g of A 125 millimoles of NaOH reacts with 125
reacted with 1000 g of oxygen. The millimoles of HCl.
∴ Molecular mass is 76.5.
mole fraction of carbon dioxide in So, millimoles of HCl left = 375
∴ The possible compound is
the resulting mixture is x × 10 − 2 . Moles of HCl = 375 × 10 − 3
CH3  CH == CH  Cl
The value of x is ........ . (Nearest Number of HCl molecules
On ozonolysis followed by hydrolysis, it
integer) [Atomic weight : gives aldehyde as follows. = Avogadro’s constant (N A ) × moles of HCl
H = 1.008, C = 12.00, O =16.00] O3
[2021, 27 Aug Shift-II] H 3 CH C CH  Cl CH3  CH = 6.022 × 1023 × 375 × 10 −3
Zn/H2O
Ans. (19) = 225.8 × 1021 = 226 × 1021
O
For the reaction, Aldehyde Therefore, answer is 226.
CH3CH2 CH3 (g) + 5O2 (g) → + Cl  C O
1 : 5 43 10.0 mL of Na2CO3 solution is
3CO2 (g) + 4H2O(g) H
titrated against 0.2 M HCl solution.
3 : 4 The compound (A) CH3  CH == CH  Cl
(chloropropene) has 3 carbon atoms.
The following titre values were
1 mole of propane reacts completely with
5 moles
obtained in 5 readings. 4.8 mL,
of oxygen to form 3 moles of carbon 41 4g equimolar mixture of NaOH and 4.9 mL, 5.0 mL, 5.0 mL and 5.0 mL
dioxide and Na 2CO 3 contains x g of NaOH and based on these readings and
4 moles of steam. y g of Na 2CO 3 . The value of x is convention of titrimetric
44 g of propane = 1 mole of propane …… g. (Nearest integer) estimation of concentration of
1 Na2CO3 solution is ……… mM
100 g of propane = × 100 = 2.27 mol [2021, 20 July Shift-II]
44 (Round off to the nearest integer).
Ans. (1)
32 g of O2 = 1 mole of O2 [2021, 18 March Shift-II]
1 Total mass = 4 g (given)
1000 g of O2 = × 1000 = 31.25 moles Mass of NaOH = x g Ans. (50)
32
Mass of Na2 CO3 = y g 10.0 mL of Na2 CO3 solution is titrated
∴ 2.27 moles of propane requires
x + y =4 against 0.2 M HCl.
5 × 2.27 = 11.35 moles of O2
moles of CO2 formed Mass of NaOH Volume of Volume of 0.2 Mean volume
= 3 × 2.7 = 6.681 mol of CO2 Molar mass of NaOH Na 2CO 3 M HCl solution of HCl (mL)
Mass of Na2 CO3 solution (mL) (mL)
CH3CH2 CH3 + 5O2 → 3CO2 + 4H2O =
1 : 5 3 : 4 Molar mass of Na2 CO3 10 4.8
at t = 0 2.27 mol 31.25 mol 0 0
x y 10 4.9
at t = t 0 31.25 – (5 ×2.27) 3 × 2.27 4 ×2.27 = (Equimolar)
19.90 mol 6.81 mol 9.08 mol 40 106 10 5.0 5.0
y = 
When reaction is completed 19.90 moles 106  106
x ⇒ x+ x =4 10 5.0
of O2 ,  40  40
6.81 moles of CO2 and 9.08 moles of 10 5.0
x + 2065
. x = 4 ⇒ 3065
. x =4
steam are left in the flask.
x = 1.096 g ⇒ x ~− 1 Na2 CO3 + 2HCl → 2NaCl + H2O + CO2
Mole fraction of
Moles of CO2 (g) 10mL 0.2M HCl
CO2 = 42 250 mL of 0.5 M NaOH was added
Total number of moles M Na 2 co = ? 5 mL
3
6.81 to 500 mL of 1 M HCl. The number Meq of Na2 CO3 = Meq of HCl
= = 0.19
19.90 + 6.81 + 9.08 of unreacted HCl molecules in the MNa 2 CO × 10 × 2 = 0.2 × 5 × 1
x × 10 −2 = 0.19 ⇒ x = 19 solution after complete reaction is 3
MNa 2 CO = 5 × 10 −2 M = 50 × 10 − 3 M
……… × 10 21 . (Nearest integer) 3
= 50 mM
40 A chloro compound A, (N A = 6.022 ×10 23 )
[2021, 20 July Shift-I]
(i) Forms aldehydes on ozonolysis 44 Complete combustion of 750 g of
followed by the hydrolysis. Ans. (226)
an organic compound provides
(ii) When vaporised completely, We know that, number of moles 420 of CO 2 and 210 g of H2O. The
1.53 g of A gives 448 mL of = VL × molarity percentage composition of carbon
vapour at STP. and number of millimoles and hydrogen in organic compound
= VmL × molarity is 15.3 and …… respectively (Round
The number of carbon atoms in a
So, millimoles of off to the nearest integer).
molecule of compound A is ……… .
[2021, 26 Aug Shift-II] NaOH = 250 × 0.5 = 125 [2021, 16 March Shift-I]
8 JEE Main Chapterwise Topicwise Chemistry

Ans. (3) Suppose, volume of Cx Hy is V and volume To be saturated and alicyclic, n = 2, is,
of O2 is 6 times greater than Cx Hy = 6 V 24 6
Cx Hy +  x +  O2 → x CO2 + H2O
y y C% = × 100, H% = × 100 and
 4 2 then volume of xCO2 ⇒ Vx = 4 V M M
32
Any hydrocarbon, on combustion gives x =4 O% = × 100
M
CO2 and H2O. This is Liebig’s method for Since, VO 2 = 6 × VC xH y
⇒ C% : H% = 24 :6 = 4 : 1
estimation of ‘C’ and ‘H’ percentage.
V  x +  = 6 V
y C% : O% = 24 :32 = 3 :4
Mass of water formed = 210 g  4 So, X is C2H6O2 and its combination
18 g of H2O contains = 2 g of hydrogen x + y =6 equation is
  … (i)
210 g of H2O contains =  × 210 =  g
2 70  4 C2H6O2 +  2 + −  O2 →
6 1
 18 3  
Put value of x = 4 in Eq. (i) 4 2 6
of hydrogen. 2CO2 + H2O
y 2
Given, mass of organic compound = 750 g We get, 4+ =6 ⇒ y = 8
4 5
⇒ C2H6O2 + O2 → 2CO2 + 3H2O
Percentage of hydrogen 2
Mass of hydrogen 5
= × 100 47 1.86 g of aniline completely reacts 1 mol
2
mol
Mass of organic compound to form acetanilide. 10% of the 5
70 product is lost during purification. 2 mol × 2 = 5 mol of O2 will be required.
= × 100 = 3.11% 2
3 × 750 Amount of acetanilide obtained
Nearest integer = 3 after purification (in g) is ……… 49 The volume (in mL) of 0.1 N NaOH
× 10 − 2 . [2021, 24 Feb Shift-II] required to neutralise 10 mL of
45 Complete combustion of 1.80 g of Ans. (432) 0.1 N phosphonic acid is ............ .
an oxygen containing compound [2020, 3 Sep Shift-II]
Reaction O
(C x Hy O z ) gave 2.64 g of CO 2 and Ans. (10)
90% 
1.08 g of H2O. The percentage of C6H5NH2  → C6H5 N  C  CH3 Base + Acid → Salt + H2O
oxygen in the organic compound is Aniline
Efficiency

Mol. wt = 98 H NaOH + H3PO3
[2021, 25 Feb Shift-I]
Acetanilide Base Phosphonic acid
(a) 50.33 (b) 53.33 (mol. wt. = 135) → NaH2PO3 + H2O
(c) 63.53 (d) 51.63 Given, weight = 1.86 g Salt Water

Given 
Ans. (b) Here, 1 mole of aniline gives 1 mole of 0.1 N 0.1 N
CxHy Oz +O2 → CO2 + H2O acetanilide  = ? 10 mL
V
1.8 g 2.64 g 1.08 g ∴mole of aniline = mole of acetanilide On dilution (N 1V1)NaOH = (N2V2 )H2 PO 3
2.64 (Given mass) 1.86 WAcetanilide 0.1 × 10 mL
nC = nCO 2 = = 0.06 ⇒ = 0.1 V1 = 0.1 × 10 mL ⇒ V1 =
44 (Molecular mass) 93 135 0.1
(Moles)
1.86 × 135
1.08 WAcetanilide = g = 2.70 g V1 = 10 mL
nH = 2 × nH 2 O = × 2 = 0.12 93
18 Volume of NaOH = 10 mL
But efficiency of reaction is 90% only.
Weight of oxygen in Cx Hy Oz
Hence, mass of acetanilide produced 50 The mass of ammonia in grams
.
264 .
108
= 1.80 − 12 × − ×2 90 produced when 2.8 kg of dinitrogen
44 18 = 2.70 × g = 243
. g = 243 × 102 g
100 quantitatively reacts with 1 kg of
= 1.80 − 0.72 − 0.12 = 0.96 g x = 243 dihydrogen is ......... .
% of oxygen by weight [2020, 4 Sep Shift-I]
0.96 48 The ratio of the mass percentages Ans. (3400)
= × 100 = 5333. %
1.80 of ‘C’ and H’ and ‘C and O’ of a N2 + 3H2 → 2NH3
saturated acyclic organic 1 mol 3 mol 2 mol
46 The formula of a gaseous compound ‘X’ are 4 : 1 and 3 : 4 Molecular weight ofN2 (kg) = 0.028 kg/mol
hydrocarbon, which requires 6 respectively. Then, the moles of Mass of ‘N’ atom = 14 g
times of its own volume of O 2 for oxygen gas required for complete Then, mass ofN2 molecule = 28 g = 0.028
complete oxidation and produces combustion of two moles of kg/mol
4 times its own volume of CO 2 is organic compound ‘X’ is ……… . Molecular weight ofH2 = 2 g
C x Hy . The value of y is ……… . [2020, 2 Sep Shift-II] Here, 3H2 is = 3 × 2 = 6 g = 0.006 kg/mol
[2021, 24 Feb Shift II] Ans. (5) Molecular weight ofNH3 is = 17 g
Ans. (8) For the molecular formula, CnH2 n + 2O2 Molecular weight of2NH3 (kg) = 0.034
Combustion reaction : (M =Molar mass) kg/mol
2n + 2
Cx Hy (g) +  x +  O2 (g) →
y 12n 0.028 kg N2 require hydrogen = 0.006 kg
C% = × 100, H% = × 100,
 4 y M M 0.006
xCO2 (g) + H2O(l ) 32 1 kg N2 require =
z O% = × 100 0.028
M
Some Basic Concepts in Chemistry 9

2.8 kg N2 (limiting reagent) require (a) 100 mL of 0.2 N HCl 55 NaClO 3 is used, even in
0.006 (b) 200 mL of 0.4 N HCl spacecrafts, to produce O 2 . The
= × 2 . 8 = 0.6 kg H2 (Excess)
0.028 (c) 200 mL of 0.2 N HCl daily consumption of pure O 2 by a
Then 0.6 kgH2 is present in excess and (d) 100 mL of 0.1 N HCl
person is 492 L at 1 atm 300 K. How
N2 will be limiting reagent. Ans. (a) much amount of NaClO 3 , in grams,
Excess
0.028 kg N2 → 0.034 kg of NH3 NH2 CONH2 + 2 NaOH → is required to produce O 2 for the
0.034 (M = 60) 2 NH3 + Na2 CO3 daily consumption of a person at 1
1 kg N2 →
0.028 No. of moles of urea atm, 300 K .......... ?
0.034 = Given mass/molar mass NaClO 3 (s ) + Fe(s )→ O 2 (g )
2.8 kg N2 → × 2.8 0.6
0.028 = = 0.01 mol NH2 CONH2 + NaCl(s ) + FeO(s)
= 34
. kg or 3400 g 60
∴ It gives 0.02 molNH3 as per the R = 0.082 L atm mol − 1K − 1
Amount of NH3 = 3400 g
equation. [2020, 8 Jan Shift-II]

51 The minimum number of moles of To neutralise it, 0.02 equivalents of HCl Ans. (2130)
O 2 required for complete needed. Volume of O2 = 492 L
As we know, no. of equivalents of HCl pV
combustion of 1 mole of propane ∴ n=
= Normality × Volume RT
and 2 moles of butane is …… .
Therefore, 1 atm × 492 L
[2020, 5 Sep Shift-I] =
(a) 100 × 10 −3 × 0.2 = 0.02. 0.082 L atm K−1 mol −1 × 300 K
Ans. (18)
(b) 200 × 10 −3 × 0.4 = 0.08 492
Combustion of propane = mol
(c) 200 × 10 −3 × 0.2 = 0.04 8.2 × 3
C3H8 (g) + 5 O2 (g) → 3CO2 (g) + 4H2O(l )
(d) 100 × 10 −3 × 0.1 = 0.01 From the reaction,
Propane
Thus, option (a) is correct.
For 1 mole propane combustion 5 mole NaClO3 (s ) + Fe(s ) → O2 (g)
O2 is required. + NaCl(s ) + FeO(s )
Combustion of butane 54 The volume (in mL) of 0.125 M 492
13 nNaClO = nO 2 = = 20 mol
C4H10 (g) + O2 (g) → 4CO2 (g) AgNO 3 required to quantitatively 3
. ×3
82
Butane 2 precipitate chloride ions in 0.3 g of
2 mol + 5H2O(l ) mNaClO = n × molar mass of
3
For 2 moles of butane 13 moles of O2 is
[Co(NH3 ) 6]Cl 3 is ……… . NaClO3 (= 106.5)
required. M [Co(NH ) ]Cl = 267.46 g/mol = 20 × 106.5 = 2130 g
3 6 3
Hence, minimum number of moles ofO2 M AgNO = 169.87 g/mol The value in different situations may
required to oxidise 1 mole of propane and 3
[2020, 8 Jan Shift-I] range from 2120 to 2140.
13
2 moles of butane = 5 + 2 × = 18 Ans. (26.92)
2 56 The strength of 11.2 volume
Given, Mass of [Co(NH3) 6 ]Cl 3 = 0.3 g
solution of H2O 2 is [Given that
52 The volume, in mL, of 0.02 M Molar mass = 267.46 g mol −1
molar mass of
0.3
K 2Cr 2O 7 solution required to react ∴ n= mol H= 1 g mol −1 and O = 16 g mol −1 ]
with 0.288 g of ferrous oxalate in 267.46 [2019, 8 April Shift-II]
acidic medium is …… . From the formula, 1 mol complex will give (a) 1.7% (b) 34%
3 mol Cl − .
(Molar mass of Fe = 56 g mol −1 ) 0.3
(c) 13.6% (d) 3.4%
[2020, 5 Sep Shift-II] ∴ nCl– = ×3 Ans. (d)
267.46
Ans. (50) 11.2 volume of H2O2 means that 1 mL of
0.9
m eq. of K2 Cr2O7 = m eq. FeC2O4 = this H2O2 will give 11.2 mL of oxygen at
267.46 STP.
K2 Cr2O7 + 7H2SO4 + FeCrO4 → Fe2 (SO4 ) 3
The precipitation reaction is takes place
+ K2SO4 + Cr2 (SO4 ) 3 + 4CO2 + 7H2O 2H2O2 (l ) → O2 (g) + 2H2O(l )
as follows : 2 × 34 g 22.4 L at STP
FeC2O4 + Cr2O27− → Fe3+ + CO2 + Cr 3+
[Co(NH3) 6 ]Cl 3 + 3AgNO3 → 2AgCl 22.4 L ofO2 at STP is produced from
0. 288 × 3 × 1000
V × 0. 02 × 6 = (0.3g) (VmL,0.125g)
H2O2 = 68 g
144
0.3 × 3 ∴11.2 L of O 2 at STP is produced from
⇒ V = 50 mL ∴ = 0.125 × V × 10 –3
267.46 68
H2O2 = × 11.2
∴Volume of AgNO3 (in mL) 22.4
53 The ammonia (NH3 ) released on
0.9 × 1000 = 34 g
quantitative reaction of 0.6 g urea =
0.125 × 267.46 ∴34 g of H2O2 is present in 1000 g of
(NH2CONH2 ) with sodium solution
hydroxide (NAOH) can be = 2692
. mL.
34
This value may vary from 26.60 to 27.00. ∴ % w/w = × 100 = 34
. %.
neutralised by [2020, 7 Jan Shift-II] 1000
10 JEE Main Chapterwise Topicwise Chemistry

57 For a reaction, (a) C 4H7Cl (b) C 4H6 60 25 g of an unknown hydrocarbon

(c) C 4H10 (d) C 4H8
N 2 (g ) + 3H2 (g ) → 2NH3 (g ), upon burning produces 88 g of CO 2
Ans. (b) and 9 g of H2O. This unknown
identify dihydrogen (H2 ) as a
limiting reagent in the following In eudiometry, hydrocarbon contains
Cx Hy +  x +  O2 → x CO2 + H2O
y 300 K y [2019, 12 April Shift-II]
reaction mixtures. 
[2019, 9 April Shift-I]
4 1 atm 2 (a) 20 g of carbon and 5 g of hydrogen
 x + y  mol
(a) 56 g of N2 + 10 g of H2 1 mol   x mol (b) 22 g of carbon and 3 g of hydrogen
 4
(b) 35 g of N2 + 8 g of H2  x +  mL
y (c) 24 g of carbon and 1 g of hydrogen
1 mL   x mL
(c) 14 g of N2 + 4 g of H2  4 (d) 18 g of carbon and 7 g of hydrogen
(d) 28 g of N2 + 6 g of H2  x + y  × 10 mL Ans. (c)
10 mL   10x mL
 4
Ans. (a) Hydrocarbon containing C and H upon
Given, (i)VCO 2 = 10 x = 40 mL ⇒ x = 4 burning produces CO2 and water vapour
Key Idea The reactant which is present
(ii) VO 2 = 10  x +  mL = 55 mL
y respectively. The equation is
in the lesser amount, i.e. which limits the  4 represented as
amount of product formed is called
10  4 +  = 55 Cx Hy + (x + y /4)O2 → xCO2 + (y /2) H2O
y
limiting reagent. ⇒ [Qx = 4]
 4 12
When 56 g ofN2 + 10 g of H2 is taken as a Mass of carbon = × mass of CO2
y × 10
⇒ 40 + = 55 44
combination then dihydrogen (H2 ) act as 4 12
a limiting reagent in the reaction. = × 88 g = 24g
10 4
⇒ y × = 15 ⇒ y = 15 × = 6 44
N2 (g) + 3H2 (g) → 2NH3 (g) 4 10 2
…(i) Mass of hydrogen = × mass of H2O
2 × 14 g 3 ×2g 2 (14 + 3) So, the hydrocarbon (Cx Hy ) is C4H6 . 18
2
28 g 6g 34 g = × 9 = 1g
28 g N2 requires 6 gH2 gas. 59 The minimum amount of O 2 (g) 18
6g consumed per gram of reactant is So, the unknown hydrocarbon contains
56 g of N2 requires × 56 g = 12 g of H2 24 g of carbon and 1g of hydrogen.
28 g for the reaction (Given atomic mass
12 g of H2 gas is required for 56 g ofN2 : Fe = 56, O = 16, Mg = 24, P = 31, 61 For the following reaction, the
gas but C = 12, H= 1) [2019, 10 April Shift-II] mass of water produced from 445
only 10 g of H2 gas is present in option (a). (a) C 3H8 (g) + 5O2 (g) → g of C 57 H110 O 6 is :
Hence,H2 gas is the limiting reagent. 3CO2 ( g ) + 4H2O (l) 2C 57 H110 O 6 (s) + 163O 2 (g) →
In option (b), i.e. 35 g ofN2 + 8 g of H2 . 114CO 2 (g) + 110H2O ( l )
(b) P4 (s ) + 5O2 (g) → P4O 10 (s )
As 28 gN2 requires 6 g ofH2 .
(c) 4Fe (s ) + 3O2 (g) → 2Fe2O 3 (s ) [2019, 10 Jan Shift-II]
6g
35 g N2 requires × 35 g H2 (d) 2Mg (s ) + O2 (g) → 2MgO (s ) (a) 490 g (b) 495 g (c) 445 g (d) 890 g
28 g
Ans. (b) Ans. (b)
⇒ 7.5 g of H2 2 C57H110O6 (s ) + 163 O2 (g) →
(a) C3H8 (g) + 5O2 (g) →
Here, H2 gas does not act as limiting 44g 160g 3CO2 (g) + 4H2O(l ) 110 H2O(l ) + 114 CO2 (g)
reagent since 7.5 g ofH2 gas is required Molecular mass of C57H110O6
160
for 35 g of N2 and 8 g of H2 is present in ⇒1g of reactant = g of
44 = 2 × (12 × 57 + 1 × 110 + 16 × 6) g
reaction mixture. Mass ofH2 left
O2 consumed = 3.64 g = 1780 g
unreacted = 8 − 7.5 g of H2 . = 0.5 g of H2 .
(b) P4 (s ) + 5O2 (g) →P4O10 (s ) Molecular mass of 110H2O
Similarly, in option (c) and (d),H2 does not 124g 160g
160 = 110 (2 + 16) = 1980 g
act as limiting reagent.
⇒1g of reactant g of 1780 g of C57H110O6 produced
For 14g of N2 + 4 g of H2 . 124
O2 consumed = 129 . g = 1980 g of H2O.
As we know28g ofN2 reacts with 6 g ofH2 .
1980
6 (c) 4Fe(s ) +3O2 (g) →2Fe2O3 (s ) 445g of C57H110O6 produced = × 445
14 g of N2 reacts with × 14g of H2 244g 1780
28 96g
3 g of H2 ⇒ 1 g of reactant
96
g of g of H2O = 495 of H2O
For 28 g of N2 + 6 g of H2 , i.e. 28 g of 224
O2 consumed 62 A mixture of 100 mmol of Ca(OH) 2
N2 reacts with 6 g of H2 [by equation (i)]. = 0.43 g
(d) 2Mg(s ) +O2 (g) →2MgO(s ) and 2 g of sodium sulphate was
58 At 300 K and 1 atmospheric 48 g 32 g dissolved in water and the volume
pressure, 10 mL of a hydrocarbon 32 was made upto 100 mL.
required 55 mL of O 2 for complete ⇒1 g of reactant g of
48 The mass of calcium sulphate
combustion and 40 mL of CO 2 is O2 consumed = 0.67 g formed and the concentration of
formed. The formula of the So, minimum amount of O2 is OH− in resulting solution,
hydrocarbon is [2019, 10 April Shift-I] consumed per gram of reactant
(Fe) in reaction (c).
respectively, are :
Some Basic Concepts in Chemistry 11

(Molar mass of Ca(OH) 2 , Na 2SO 4 Ans. (d) carried out in the presence of HCl
and CaSO 4 are74, 143 and 136 g We know the molecular weight of because HCl [AIEEE 2008]
mol −1 , respectively; K sp of C8H7SO3Na (a) gets oxidised by oxalic acid to
Ca(OH) 2 is 5.5 × 10 −6 ) = 12 × 8 + 1 × 7 + 32 + 16 × 3 + 23 = 206 chlorine
[ 2019, 10 Jan Shift-I] We have to find, mole per gram of resin. (b) furnishes H + ions in addition to
(a) 13.6 g, 0.28 mol L −1 ∴ 1 g of C8H7SO3Na has number of mole those from oxalic acid
(b) 1.9 g, 0.28 mol L −1 (c) reduces permanganate toMn2 +
Weight of given resin 1
= = mol (d) oxidises oxalic acid to carbon dioxide
(c) 13.6 g, 0.14 mol L −1 Molecular weight of resin 206 and water
(d) 1.9 g, 0.14 mol L −1 Now, reaction looks like
Ans. (b) Ans. (c)
2C8H7SO3Na + Ca2 + →
The reaction involved is as follows : Titration of oxalic acid byKMnO4 in the
(C8H7SO3)2 Ca + 2Na+ presence of HCl gives unsatisfactory
Ca(OH)2 + Na2SO4 →
2 × 1000
Q 2 moles of C8H7SO3Na combines with 1 result because HCl is a better reducing
Millimoles 100 = 14 mol Ca2 + agent than oxalic acid and HCl reduces
142
att =0 Milimoles 86 0 ∴ 1 mole of C8H7SO3Na will combine with preferably MnO–4 to Mn2 + .
1
att = t [Limiting reagent] mol Ca2 +
CaSO4 + 2OH− + 2Na+
2 67 In the reaction,
1
0 0 0 ∴ mole of C8H7SO3Na will combine 2Al (s) + 6HCl (aq) → 2Al 3+ (aq)
14 28 206 + 6Cl − (aq ) + 3H2 (g )
Weight with
No. of moles = 1 1 1 [AIEEE 2007]
Molecular mass × mol Ca2 + = mol Ca2 +
2 206 412 (a) 6L HCl (aq) is consumed for every
14
∴ Mass of CaSO4 = × 136 = 1 .9 g 3L H2 (g) produced
1000 (b) 33.6 L H2 (g) is produced regardless of
Also,
65 3 g of activated charcoal was
temperature and pressure for every
No. of moles of solute added to 50 mL of acetic acid mole Al that reacts
Molarity =
Volume of solution (in L) solution (0.06 N) in a flask. After an (c) 67.2 L H2 (g) at STP is produced for
∴ Molarity of OH– , hour it was filtered and the every mole Al that reacts
28 1000 strength of the filtrate was found
[OH– ] = × (d) 11.2 L H2 (g) at STP is produced for
1000 100 to be 0.042 N. The amount of every moleHCl (aq) consumed
= 0.28mol L−1 = 0.28 M acetic acid adsorbed (per gram of Ans. (d)
charcoal) is [JEE Main 2015]
2Al(s ) + 6HCl(aq) → 2Al 3+ (aq)
63 1 g of a carbonate (M 2CO 3 ) on (a) 18 mg (b) 36 mg + 6Cl − (aq) + 3H2 (g)
treatment with excess HCl (c) 42 mg (d) 54 mg From the equation, it is clear that,
produces 0.01186 mole of CO 2 . The Ans. (a) 6 mol of HCl produces 3 mol ofH2
molar mass of M 2CO 3 in g mol − 1 is Given, initial strength of acetic acid 3 × 22.4
or 1 mole of HCl = L of H2
[ JEE Main 2017] = 0.06N 6
(a) 1186 (b) 84.3 (c) 118.6 (d) 11.86 Final strength = 0.042 N = 11.2 L of H2
Ans. (b) Volume given = 50 mL
M2 CO3 + 2HCl → 2M Cl + H2O + CO2 ∴Initial m moles of CH3COOH 68 What volume of hydrogen gas, at
1g 0.01186 mole = 0.06 × 50 = 3 273 K and 1 atm pressure will be
Number of moles of M2 CO3 reacted Final m moles of CH3COOH
consumed in obtaining 21.6 g of
= Number of moles of CO2 evolved = 0.042 × 50 = 2.1
elemental boron (atomic mass
1
= 0.01186 [M = molar mass of M2 CO3] ∴ m moles of CH3COOH adsorbed
= 3 − 2.1 = 0.9 m
= 10.8) from the reduction of boron
M
1 mol trichloride by hydrogen? [AIEEE 2003]
M= . g mol − 1
= 843 (a) 89.6 L (b) 67.2 L
0.01186 Hence, mass of CH3COOH absorbed per
gram of charcoal (c) 44.8 L (d) 22.4 L
64 The molecular formula of a 0.9 × 60 Ans. (b)
=
commercial resin used for 3 2BCl 3 + 3H2 → 2B + 6HCl
(Qmolar mass of CH3COOH = 60 gmol −1)
exchanging ions in water softening 2 mol 3 mol 2 mol
54
= = 18 mg. 21.6 g
is C 8H7 SO 3Na (mol. wt. = 206). 3
What would be the maximum 21.6 g B = 2 mol B ≡ 3 mol H2
uptake of Ca 2+ ions by the resin 66 Amount of oxalic acid present in a pV = nRT
when expressed in mole per gram solution can be determined by its nRT
⇒V = p
resin? [JEE Main 2015] titration with KMnO4 solution in the
1 1 2 1 presence of H2SO4 . The titration 3 × 0.0821 × 273
(a) (b) (c) (d) = = 67. 2 L
103 206 309 412 gives unsatisfactory result when 1
02
States of Matter
TOPIC 1 3.47 14.2
=
p 8.2
Gaseous State
3.47 × 41 pV
⇒ p= = 2.003 atm
01 An empty LPG cylinder weight 71
14.8 kg. When full, it weight 29.0 kg Hence, answer is 2.
p
and shows a pressure of 3.47 atm.
In the course of use at ambient 02 Which one of the following is the Hence, correct option is (a).
temperature, the mass of the correct pV vs p plot at constant
temperature for an ideal gas ? 03 Two flasks I and II shown below are
cylinder is reduced to 23.0 kg. The
(p and V stand for pressure and connected by a valve of negligible
final pressure inside of the cylinder
volume of the gas respectively) volume. [2021, 27 Aug Shift-II]
is ……… atm. (Nearest integer) [2021, 31 Aug Shift-I]
(Assume LPG of be an ideal gas) 2.8 g N2 0.2 g N2
[2021, 1 Sep Shift-II] 300 K 60 K
Ans. (2) pV 1L 2L
(a)
Weight of empty LPG cylinder = 14.8 kg
Weight of full LPG cylinder = 29 kg When the valve is opened, the
∴ Weight of gas = 29 − 14.8 = 14.2 kg p final pressure of the system in bar
If weight of full LPG cylinder = 23 kg is x × 10 − 2 . The value of x is
then weight of gas used = 29 − 23 = 6 kg .............. . (Integer answer)
at ambient temperature.
(b)
pV [Assume, Ideal gas, 1 bar = 10 5 Pa,
From ideal gas equaiton, pV = nRT molar mass of N 2 = 28.0 g mol − 1 ;
or pV =
Weight of solute
× RT R = 8.31 J mol − 1 K − 1 ]
Molecular mass of solute p
Ans. (84)
W
or pV = × RT
M nA=2.8 2.8g N2 0.2g N2 nB=0.2
28 28
Applying ideal gas to LPG cylinder when pV 300 K 60 K
gas is full, (c) T1=300 K 1L 2L T2=60 K

pV = nRT
14.2 kg T1=300K
3.47 atm × V = × RT …(i) p DUA
M DTA =(T1–T)
T
Applying ideal gas to LPG cylinder when
gas is reduced to 23 kg at ambient DUB DTB =(T–T2 )
pV
temperature, (d) T2=60K
pV = nRT On mixing the temperature of gas
8. 2 kg
p×V = × RT …(ii) p becomes T. Internal energy lost by gas A
M is the internal energy gained by gas B.
Ans. (a)
Divide Eq. (i) by (ii) ∆U A = ∆U B
14.2 kg RT From ideal gas equation, pV = nRT
f f
Given that, pV = constant, since nA R ∆TA = nBR∆TB (As both gases are
3.47 × V M
= temperature is constant.
2 2
p×V 8.2 kg × RT diatomic, f is same on both sides)
M Hence, graph for pV vs p will be
nA ∆TA = nB∆TB
States of Matter 13
2.8 0.2 p1 p2 8.8
× (T1 − T ) = (T − T2 ) Formula; = Moles of CO2 = = 0.2 mol
28 28 T1 T2 44
1
(300 − T ) =
1
(T − 60) 300 × 10 3 1.2 × 10 6 ntotal = 0.4 + 0.2 = 0.6 mol
10 140 = n RT
300 T2 ptotal = total
T = 284K V
1.2 × 10 6
On mixing the temperature becomes 284 10 3 = 0.6 × 8314
. × 300
K and volume becomes 3L and total T2 =
10
number of moles becomes
⇒ T2 = 1.2 × 10 3 = 149652
. = 150 kPa
(nA + nB) = 0.10 moles.
= 1200 K = 927 °C
According to gas equation,
08 A certain gas obeys p (Vm − b) = RT .
pV = (nA + nB) RT 06 A home owner uses 4.00 × 10 3 m 3
0.10 × 8.3 × 284 of methane (CH4 ) gas, (assume CH4  ∂Z  xb
= The value of   is . The
3 is an ideal gas) in a Year to heat his  ∂p  T RT
= 84.18 atm or 84.18 bar home. Under the pressure of 1.0 value of x is ………… .
This is final pressure of gas. atm and 300 K, mass of gas used is (Z = compressibility factor)
x × 10 5 g. The value of x is …… . [2021, 26 Feb Shift-I]
04 The unit of the van der Waals’ gas (Nearest integer) Ans. (1)
equation parameter ‘a ’in
(Given, R = 0.083 L atm K −1mol −1 ) For 1 mole of a real gas, the van der
 an 2  Waals’ equation is,
 p + 2  (V − nb) = nRT is [2021, 25 July Shift-I]
 V  Ans. (26)  a 
 p + 2  (Vm − b) = RT
[2021, 27 Aug Shift-I] Given, volume of CH4 gas V = 4 × 10 3m3  Vm 
−2 3 −1
(a) kg ms (b) dm mol Temperature = 300 K At very high pressure, the equation
(c) kg ms− 1 (d) atm dm6mol− 2 Pressure = 1 atm becomes,
Ans. (d) Using ideal gas equation, pV = nRT p(Vm − b) = RT
van der Waals’ gas equation, No. of moles of CH4 (n) =
pV ⇒ pVm = RT + pb
 RT pVm pb
an2  ⇒ = 1+
 p + 2  (V − nb) = nRT 4 × 10 3 × 1000 RT RT
 V  =
0.083 × 300 pb
⇒ Z = 1+
an2 RT
For dimensionally correct equation, 40 × 16 × 10 5
V Now, weight of CH4 = g pV
0.083 × 300 [Q Z = m = compressibility]
should have the same dimension of RT
pressure i.e. atm. = 25.7 × 10 5 g
 δZ  b b xb
Unit of parameter ‘a’ is as follows ∴   =0+ = = (Given)
= 26 × 10 5 g  δp  T RT RT RT
L2
= atm = atm L2 mol −2 So, value of x is 26. ⇒ x=1
mol2
= atm dm6 mol −2 . 07 The pressure exerted by a 09 A car tyre is filled with nitrogen gas
non-reactive gaseous mixture of at 35 psi at 27°C. It will burst if
05 An LPG cylinder contains gas at a 6.4 g of methane and pressure exceeds 40 psi. The
pressure of 300 kPa at 27°C. The 8.8 g of carbon dioxide in a 10L temperature in °C at which the car
cylinder can withstand the vessel at 27°C is …… kPa (Round off tyre will burst is ………
pressure of 12 × 10 6 Pa. The room in to the nearest integer) (Rounded-off to the nearest
which the cylinder is kept catches
(Assume gases are ideal,R = 8.314 integer). [2021, 25 Feb Shift-I]
fire. The minimum temperature at
J mol −1 K −1 Atomic mass, Ans. (70)
which the bursting of cylinder will
C : 12.0 u, H : 1.0 u, O : 16.0 u) p1 = 35 psi,T1 = 27 °C = 300 K
take place is ……… °C. (Nearest [2021, 17 March Shift-I]
integer) [2021, 25 July Shift-II] p2 = 40 psi,T2 = ?
Ans. (150)
Ans. (927) According to Charle’s law,
Given, mass of methane = 64. g
p ∝T
LPG cylinder contains gas at pressure, mass of CO2 = 8.8 g p2 T2 40 T2
p1 = 300 kPa = 300 × 10 3 Pa volume of container = 10 L = ⇒ =
p1 T1 35 300
T1 = 27 ° C temperature = 27 ° C
= 27 + 273 K = 300 K 300 × 40
To find, ptotal = Total pressure ⇒ T2 =
Cylinder can withstand the pressure, 35
Given mass
p2 = 1.2 × 10 6 Pa Moles of CH4 = = 342.85 K = 69.7 °C
Molar mass
Minimum temperature (T2 ) required for 6.4 T2 − 70 °C
~
bursting of cylinder is ; = = 0.4 mol
16 Hence, answer is 70.
14 JEE Main Chapterwise Topicwise Chemistry

10 The volume occupied by 4.75 g of T = temperature inK, (A) For 1 mole, U = internal energy and
R = molar gas constant, H = enthalpy.
acetylene gas at 50°C and 740 mm
w = mass of the gas in g, Heat capacity at constant volume.
Hg pressure is ……L (Rounded off
M = gram molar mass of the gas dU
to the nearest integer). and nC V =
dt
[Given, R = 0.0821 L atm w
d = = density of the gas. dU = nC V dT (n = 1 mol)
K − 1 mol − 1 ] [2021, 24 Feb Shift-II] V
1 dU = 1 × C V × dT
Ans. (5) (i) When, p = constant ⇒ d ∝
T (QC V = constant)
Given, mass of C2H2 (g) = 4.75 g
So, nature of the plot,d vsT is U = f (T ) (Function of temperature)
Molecular weight = 26 g/mol rectangular hyperbolic (I) but not U depends on temperature.
Temperature = 50 + 273 = 323 K linear (II). Heat capacity at constant volume,
Pressure = 740 torr/mm of Hg 1
Again, nature of the plot,d vs will dH
740 T nCp =
Pressure = atm dT
760 be linear as in (III).
(ii) When,T = constant ⇒ d ∝ p dH = nC pdT [n = 1 mol]
R = 0.0821 L atm mol −1 K −1
4.75 Here, nature of the plot,d vs p will dH = 1 × C p × dT
Hence, no. of mole n = mol
26 be linear as in (IV). In mathematically term,
Formula used, pV = nRT (ideal gas) H = f (T ) [QC p = constant]
nRT 12 A mixture of one mole each of H2 , Hence,H depends on function of
⇒ V= He and O 2 each are enclosed in a
p temperature
4.75 0.0821 × 323 cylinder of volume, V at (b) Compressibility factor (Z) describe
= × temperatureT. If the partial the deviation of real gas from ideal gas
26 (740 / 760)
pressure of H2 is 2 atm, the total behaviour.
96314078
.
= pV
19240 pressure of the gases in the Z= …(i)
RT
= 50059
. L = 5L cylinder is [2020, 3 Sep Shift-II]
For ideal gas, pV = nRT [n = 1 mol]
(a) 14 atm (b) 38 atm
(c) 22 atm (d) 6 atm pV = RT …(ii)
11 Which one of the following graphs
Ans. (d) Put in the value of pV from Eq. (ii) to Eq. (i)
is not correct for ideal gas?
RT
[2020, 2 Sep Shift-I] Volume of cylinder = V, Temperature =T, Z= =1
RT
Partial pressure of H2 = 2 atm
d d Compressibility factor is 1 for ideal gas
According to law of partial pressure
then option (b) is incorrect.
pi = χ i × pT
(c) For ideal gas,
pi = partial pressure of the ith
C p − C V = nR (n = 1 mol)
T T component,
(I) (II) χ i = mole fraction, pT = total pressure Cp − CV = R
 nH 2  It is correct statement.
⇒ 2 atm =   × pT
 nH 2 + nHe + nO 2 
dU
d d (d) ∆U = C V dT ⇒ nC V =
dT
3
Then, pT = 2 × = 6 atm dU = nC V dT (n = 1 mol)
1
1/T p dU = C V dT
(III) (IV) 13 For one mole of an ideal gas, which It is also correct.
d = density, p = pressure, of these statements must be true?
T = temperature (A) U and H each depends only on 14 A spherical balloon of radius 3 cm
(a) III (b) I temperature. containing helium gas has a
(c) IV (d) II (B) Compressibility factor Z is not pressure of 48 × 10 −3 bar. At the
Ans. (d) equal to 1. same temperature, the pressure,
Graph (II) is not correct for ideal gas. (C) C p,m − C V,m = R of a spherical balloon of radius
For n mole of an ideal gas, (D) dU = C V dT for any process. 12 cm containing the same amount
w
pV = nRT = RT [2020, 4 Sep Shift-I] of gas will be ……… × 10 −6 bar.
M [2020, 6 Sep Shift-I]
(a) (B), (C) and (D) (b) (A) and (C)
RT  w
Q = d
w RT Ans. (750)
⇒ p= × =d × (c) (A), (C) and (D) (d) (C) and (D)
V M M  M 
Ans. (c) Initial pressure (p1) = 48 × 10 −3 bar
p⋅ M
⇒ d= Statements (A), (C) and (D) are true Final pressure (p2 ) = …… × 10 −6 bar
RT 4
whereas (B) is false. Initial volume (V1) = π (3) 3
where, p = pressure,V = volume, 3
States of Matter 15
4 (c) A- v mp ; B - v av; C - v rms Ans. (a)
Final volume (V2 ) = π (12) 3
3 (d) A-v av; B -v rms ;C -v mp Noble gases such as Ne, Ar, Xe and Kr
According to Boyle’s law p1V1 = p2V2
Ans. (c) found to deviate from ideal gas
4
48 × 10 −3 × π (3) 3 behaviour.
p1V1 3 The increasing order of molecular
p2 = = Xe gas will exhibit steepest increase in
V2 4 velocities of gas molecules is as follows :
π (12) 3 plot of Z vs p. Equation of state is given
3 Most probable velocity (vmp ) < average as:
48 × 10 −3 × (3) 3 velocity (vav ) < rms velocity (vrms ). RT
= p=
(12) 3 Because, (V − b)
2RT 8RT
48 × 10 −3 × 27 vmp = , vav = ⇒ p (V − b) = RT
= = 0.0277 × 27 × 10 −3 M πM
1728 pV − pb = RT
3RT
= 750 × 10 −6 bar and vrms = ⇒ pV = RT + pb
M pV pb pV
Hence, the correct answer is 750. = 1+ . As, Z =
RT RT RT
15 The relative strength of interionic/ 17 Consider the van der Waals’ pb
so, Z = 1+ ⇒ y = c + mx
intermolecular forces in decreasing constants, RT
order is [2020, 7 Jan Shift-I]
a and b, for the following gases. The plot of Z vs p is found to be
(a) dipole-dipole > ion-dipole > ion-ion Gas Ar Ne Kr Xe
(b) ion-ion > ion-dipole > dipole-dipole 6
a/(atm dm mol ) 1.3 −2
0.2 5.1 4.1 slope = b
RT
(c) ion-dipole > ion-ion > dipole-dipole b/(10 −2 3
dm mol ) −1
3.2 1.7 1.0 5.0 Z
(d) ion-dipole > dipole-dipole > ion-ion
Ans. (b) Which gas is expected to have the
Interionic (ion-ion) forces are stronger
highest critical temperature ?
[2019, 9 April Shift-I] p
than ion-dipole, which in turn are
stronger than intermolecular forces like (a) Kr (b) Xe (c) Ar (d) Ne The gas with high value ofb will be
dipole-dipole interaction. Ans. (a) steepest as slope is directly proportional
This is because in case of ion-ion Critical temperature is the temperature to b. b is the van der Waals’ constant and
interactions there is complete transfer of of a gas above which it cannot be is equal to four times the actual volume
electrostatic charges from one atom to liquefied what ever high the pressure of the gas molecules. Xe gas possess the
another. Whereas in dipole-dipole may be. The kinetic energy of gas largest atomic volume among the given
interactions, there is involvement of only molecules above this temperature is noble gases (Ne, Kr, Ar). Hence, it gives
partial charges. sufficient enough to overcome the the steepest increase in the plot of Z
The strength of ion-dipole interactions attractive forces. It is represented asTc . (compression factor) vsp.
lies intermediate to that of ion-ion and 8a
Tc =
dipole-dipole interactions. 27 Rb 19 Consider the following table.
Thus, the correct decreasing order of 8 × 1.3 b/(dm3mol −1 )
For Ar, Tc = = 0.0144 Gas a/(k Pa
relative strength is : 27 × 8.314 × 3.2 dm6mol −1)
Ion-ion > ion-dipole > dipole-dipole. 8 × 0.2
For Ne, Tc = = 0.0041 A 642.32 0.05196
27 × 8.314 × 1.7
16 Identify the correct labels of A, B 8 × 5.1 B 155.21 0.04136
For Kr, Tc = = 0.18
and C in the following graph from 27 × 8314
. × 1.0 C 431.91 0.05196
the options given below : 8 × 4.1 D 155.21 0.4382
For Xe, Tc = = 0.02
A 27 × 8.314 × 5.0
B a and b are van der Waals’
C The value ofTc is highest for Kr (Krypton).
constants. The correct statement
no. of 18 At a given temperatureT, gases Ne, about the gases is
molecules [2019, 10 April Shift-I]
Ar, Xe and Kr are found to deviate (a) gas C will occupy lesser volume than
from ideal gas behaviour. Their gas A; gas B will be lesser
equation of state is given as, compressible than gas D
RT (b) gas C will occupy more volume than
Speed p= atT.
V −b gas A; gas B will be more
Root mean square speed (v rms ); compressible than gas D
Here, b is the van der Waals’
most probable speed (v mp ); (c) gas C will occupy more volume than
constant. Which gas will exhibit gas A; gas B will be lesser
Average speed (v av )
steepest increase in the plot of Z compressible than gas D
[2020, 7 Jan Shift-II]
(compression factor) vs p? (d) gas C will occupy more volume than
(a) A-v rms ;B -v mp ; C -v av [2019, 9 April Shift-II] gas A; gas B will be lesser
(b) A-v mp ; B -v rms ;C -v av (a) Xe (b) Ar (c) Kr (d) Ne compressible than gas D
16 JEE Main Chapterwise Topicwise Chemistry

Ans. (b) Ans. (c) 22 The volume of gas A is twice than

For 1 mole of a real gas, the van der Key Idea From kinetic gas equation, that of gas B. The compressibility
Waals’ equation is 2RT factor of gas A is thrice than that of
Most probable velocity (v mp ) =
 p + a  (V − b) = RT M gas B at same temperature. The
 
 V2  where, R = gas constant, pressures of the gases for equal
The constant ‘a’ measures the T = temperature, number of moles are
intermolecular force of attraction of gas M = molecular mass [2019, 12 Jan Shift-I]
molecules and the constant ‘b’ measures 2 RT T (a) pA = 2 pB (b) 2 pA = 3pB
the volume correction by gas molecules v mp = i.e. v mp ∝
M M (c) pA = 3pB (d) 3pA = 2 pB
after a perfectly inelastic binary collision
of gas molecules. Ans. (b)
Gas M T(K) T/M
For gas A and gas C given value of ‘b’ is Given, Z A =3Z B
0.05196 dm3 mol −1. Here, H2 2 300 300 /2 = 150 …III pV
Compressibility factor (Z) =
a ∝ intermolecular force of attraction (Highest) nRT
∝ compressibility ∝ real nature N2 28 300 300 /28 = 10.71 …I [for real gases]
1 (Lowest)
∝ On substituting in equation (i), we get
volume occupied pAVA 3p V
O2 32 400 400 /32 = 12.5 … II = B B …(ii)
Value of a/(kPa dm 6 mol −1) for gas A nA RTA nBRTB
(642.32) > gasC (431.91) So, gasC will So,
Also, it is given that
occupy more volume than gas A. I. corresponds to v mp of N2 (300 K)
VA =2VB, nA = nB andTA = TB
Similarly, for a given value ofa say II. corresponds to v mp of O2 (400 K)
155.21 kPa dm 6 mol −1 for gas B and gas D ∴ Eq. (ii) becomes
III. corresponds to v mp of H2 (300 K)
pA × 2VB 3pBVB
1
∝ intermolecular force of attraction = ⇒ 2pA =3pB
b 21 An open vessel at 27°C is heated nBRTB nBRTB
∝ compressibility ∝ real nature until two fifth of the air (assumed
1 23 Two closed bulbs of equal volume
∝ as an ideal gas) in it has escaped
volume accupied (V) containing an ideal gas initially
from the vessel. Assuming that the
b/(dm 3 mol −1) for gas B (0.04136) < Gas D volume of the vessel remains at pressure pi and temperatureT 1
(0.4382). constant, the temperature at which are connected through a narrow
So, gas B will be more compressible than the vessel has been heated is tube of negligible volume as shown
gas D. in the figure below. The
(a) 750 K (b) 500 K
(c) 750°C (d) 500°C temperature of one of the bulbs is
20 Points I, II and III in the following [2019, 12 Jan Shift-II] then raised to T 2 . The final
plot respectively correspond to Ans. (b) pressure pf is [JEE Main 2016]
(v mp : most probable velocity) Given, temperature (T1) = 27 ° C T1 T2
[2019, 10 April Shift-II]
= 273 + 27 = 300 K pi , V pi , V
Volume of vessel = constant
Distribution function f( v)

Pressure in vessel = constant

2
Volume of air reduced by so the
5 T1 T2
3 pf, V pf, V
remaining volume of air is .
5
Let atT1 the volume of air inside the
vessel is n so atT2 the volume of air will  T   T 
I II III (a) 2 pi  1  (b) 2 pi  2 
Speed, v 3
be n. T1 + T2  T1 +T2 
5
 TT   TT 
(a) v mp of H2 (300 K); v mp of N2 (300 K); v mp Now, as p and V are constant, so (c) 2 pi  1 2  (d) pi  1 2 
of O2 (400 K) T1 +T2  T1 +T2 
3
(b) v mp of O2 (400 K); v mp of N2 (300 K); v mp n ⋅T1 = nT2 ...(i)
5 Ans. (b)
of H2 (300 K) Putting the value ofT1 in equation (i) we Initially,
(c) v mp of N2 (300 K); v mp of O2 (400 K); v mp get, Number of moles of gases in each
of H2 (300 K) 3 pV
n × 300 = n ×T2 container = i
(d) v mp of N2 (300 K); v mp of H2 (300 K); v mp 5 RT1
5
of O2 (400 K) or T2 = 300 × = 500 K Total number of moles of gases in both
3 containers
States of Matter 17
piV
=2 25 If Z is a compressibility factor, van 27 The compressibility factor for a real
RT1
der Waals’ equation at low pressure gas at high pressure is [AIEEE 2012]
After mixing, number of moles in left
can be written as [ JEE Main 2014] RT
chamber (a) 1 + (b) 1
pV RT pb
= f (a) Z = 1 +
RT1 pb pb pb
a (c) 1 + (d) 1 −
Number of moles in right chamber =
pfV (b) Z = 1 − RT RT
RT2 VRT
pb Ans. (c)
Total number of moles (c) Z = 1 − van der Waals’ equation for one mole of
RT
pV pV real gas is
= f + f (d) Z = 1 +
pb
RT1 RT2 RT  p + a  ( V − b) = RT
 
pfV  1 1 Ans. (b)  V2 
=  + 
R  T1 T2  van der Waals’ equation is given by When pressure is high p >> 2
a
 p + a  (V − b) = RT V
As total number of moles remains   p + a  ≈ p
 V2 
constant. Such that  
a  V2 
2piV pfV pV At low pressure, V decreases. Thus,
Hence, = + f V2 Thus, p (V − b) = RT
RT1 RT1 RT2 increases. However, V is still large pV − pb = RT
 T  enough in comparison to ‘b’, hence, ‘b’ can
⇒ pf = 2pi  2  be neglected. Thus, van der Waals’ pV = RT + pb
 T1 + T2  equation becomes ∴ Compressibility factor,
 p + a  V = RT pV  pb 
  Z= = 1 + 
24 The intermolecular interaction that  V2  RT  RT 
is dependent on the inverse cube ⇒
a
pV + = RT
of distance between the molecules V 28 a and b are van der Waals’
a constants for gases. Chlorine is
is [ JEE Main 2015] ⇒ pV = RT −
V more easily liquefied than ethane
(a) ion-ion interaction pV a
⇒ = 1− because [AIEEE 2011]
(b) ion-dipole interaction RT RTV
(c) London force (a) a and b for Cl2 > a and b for C2H6
Z = 1−
a Q pV = Z 
(d) hydrogen bond RTV  RT  (b) a and b for Cl2 < a and b for C2H6
Ans. (b) (c) a for Cl2 > a for C2H6 but b for Cl2 > b
for C2H6
Ion-ion interaction is dependent on the 26 For gaseous state, if most probable (d) a for Cl2 > a for C2H6 but b for Cl2 < b
square of distance, i.e. ion-ion speed is denoted by C*, average
1 for C2H6
interaction ∝ 2 speed by C and mean square speed
r Ans. (d)
by C, then for a large number of
1 van der Waals’ constant a is due to force
Similarly, ion-dipole interaction ∝ 3 molecules, the ratios of these
r of attraction and b due to finite size of
1 speeds are [JEE Main 2013] molecules.
London forces ∝ 6
r (a) C* : C :C = 1.225 : 1. 128 : 1 Thus, greater the valuea and smaller the
1 (b) C* : C : C = 1.128 : 1.225 : 1 value of b, larger the liquefaction.
and dipole-dipole interactions ∝ 3
r (c) C * :C :C = 1 : 1.128 : 1.225 Thus, a (Cl2 ) > a (C2H6 )
Superficially it seems as both ion dipole (d) C * :C :C = 1 : 1.225 : 1.128 and b (Cl2 ) < b (C2H6 )
interaction and hydrogen bonding vary Ans. (c)
with the inverse cube of distance C* = most probable speed = 2RT / M
29 The molecular velocity of any gas is
between the molecules but when we look [AIEEE 2011]
C = average speed = 8 RT / πM
at the exact expressions of field (force) (a) inversely proportional to the square
created in two situations it comes as C = Mean square speed corrected as root of temperature
2| P| 3RT (b) inversely proportional to absolute
|E | or |F | = rms =
4 π ε0 r 3 M temperature
*
(In case of ion-dipole interaction) ∴ C< C< C (c) directly proportional to square of
* 4 3 temperature
2q2 r − 4q2a Hence, C: C : C = 1 : :
and F= (d) directly proportional to square root
4 πε0 r 3 π 2
of temperature
(In case of dipole-dipole interaction) = 1: 1.128 : 1.225 Ans. (d)
From the above it is very clear, the Note As no option correspond to mean
Molecular velocity can be
ion-dipole interaction is the better square speed, it is understood as
8RT
answer as compared to dipole-dipole misprint. It should be root mean square average velocity =
interaction i.e. hydrogen bonding. speed. πM
18 JEE Main Chapterwise Topicwise Chemistry

3RT (c) The fraction of the molecules with Ans. (c)

root mean square velocity =
M the most probable speed increases In between two successive collisions, no
2RT (d) The most probable speed increases force is acting on the gas molecules.
most probable velocity = Resultantly they travel with uniform
M Ans. (c)
velocity during this interval and hence,
In all cases, molecular velocity ∝ T Distribution of molecules (N ) with
moves along a straight line.
velocity (u) at two temperaturesT1 and
30 When r, p and M represent rate of T2 (T2 >T1) is shown below
At both temperatures, distribution of
36 Based on kinetic theory of gases
diffusion, pressure and molecular following laws can be proved
molecules with increase in velocity first
mass, respectively, then the ratio increases, reaches to a maximum value [AIEEE 2002]
of the rates of diffusion (rA / rB ) of and then decreases. (a) Boyle’s law
two gases A and B, is given as N (b) Charles’ law
[AIEEE 2011] T1 (c) Avogadro’s law
1/ 2
(a) (pA / pB) (M A / M B) (d) All of these
T2
(b) (pA / pB) (M B / M A) 1/2 Ans. (d)
(c) (pA / pB) 1/2 (M B / M A) On the basis of kinetic theory of gases
(d) (pA / pB) (M A /M B) 1/2 u 1
pV = Nmv 2
Ans. (b) 3
33 As the temperature is raised from 1 3
Rate of diffusion, r ∝ p and mv 2 = kT
1 p
20°C to 40°C, the average kinetic 2 2
r= ∴r ∝ energy of neon atoms changes by a
p =   mv 2
M M 1 N
pA factor of which of the following? 3 V 
For gas A, rA ∝ …(i) [AIEEE 2004]
p =   mv 2
MA 2 N 1
or
pB (a) 1/2 (b) 313 / 293 3 V  2
For gas B, rB ∝ …(ii) (c) 313/293 (d) 2 2  N   3
MB =     kT
Ans. (c) 3  V   2
Dividing Eq. (i) by Eq. (ii), we get
1/ 2
Average KE =
3 or pV = NkT
rA pA MB pA  MB  RT /N 0
= ⋅ or =   2
rB pB MA pB  MA  37 For an ideal gas, number of moles
⇒ (KE) ∝T
313 per litre in terms of its pressure p,
∴ (KE)313 /(KE)293 =
31 If 10 −4 dm 3 of water is introduced 293 temperatureT and gas constant R
into a 1.0 dm 3 flask at 300 K, then 34 In van der Waals’ equation of state is [AIEEE 2002]
how many moles of water are in the of the gas law, the constant ‘b’ is a
pT
(a) (b) pRT
vapour phase when equilibrium is measure of [AIEEE 2004]
R
established? p RT
(a) intermolecular repulsions (c) (d)
(Given, vapour pressure of H2O at RT p
(b) intermolecular attraction
300 K is 3170 Pa; (c) volume occupied by the molecules Ans. (c)
R = 8.314 JK −1 mol −1 ) [AIEEE 2010] (d) intermolecular collisions per unit According to ideal gas equation,
(a) 5.56 × 10−3 mol (b) 1.53 × 10−2 mol volume pV = nRT
(c) 4.46 × 10−2 mol (d) 1.27 × 10−3 mol Ans. (c) Number of moles, n =
pV p × 1 p
= =
Ans. (d) RT RT RT
van der Waals’ equation for one mole of a
Number of moles, gas is
pV 3170 × 10 −3  p + a  [ V − b] = RT TOPIC 2
n= =
RT 8.134 × 300  V 2 
= 1.27 × 10 −3 mol
Liquid State
where,b is volume correction. It arises
due to finite size of molecules.
32 Which one of the following 38 The predominant intermolecular
statements is not true about the 35 According to the kinetic theory of forces present in ethyl acetate, a
effect of an increase in gases, in an ideal gas, between two liquid, are :
[2020, 8 Jan Shift-I]
temperature on the distribution of successive collisions a gas
(a) London dispersion and dipole-dipole
molecular speeds in a gas? molecule travels [AIEEE 2003]
(b) London dispersion, dipole-dipole and
[AIEEE 2005] (a) in a circular path hydrogen bonding
(a) The area under the distribution curve (b) in a wavy path (c) Dipole-dipole and hydrogen bonding
remains the same as under the lower (c) in a straight line path (d) Hydrogen bonding and London
temperature
(d) with an accelerated velocity dispersion
(b) The distribution becomes broader
States of Matter 19

Ans. (a) B. Fe3O4 is ferrimagnetic because of 42 The parameters of the unit cell of a
O the presence of the unequal
substance are a = 2.5, b = 3.0, c = 4.0,
 alignment of magnetic moment in
Ethyl acetate (CH3  C O  CH2  CH3) opposite direction. α = 90° , β = 120° , γ = 90°. The crystal
molecules are polar. So, dipole-dipole C. O2 molecule has two unpaired system of the substance is
[2021, 27 July Shift-I]
interaction is present between its electrons. So, it is paramagnetic.
molecules. There are no such groups D. In MnO, the orientation of the (a) hexagonal (b) orthorhombic
such as hydroxyl ( OH) which are electrons of Mn and O is such that (c) monoclinic (d) triclinic
capable of forming hydrogen bond. they cancel their effects, hence it Ans. (c)
London dispersion forces are present in is antiferromagnetic. The parameters of unit cell of a
all substances involving ethyl acetate So, the correct match is A-3, B-4, substance are
also. C-2, D-1. a = 2.5, b = 3.0, c = 4.0
Thus in ethyl acetate, the predominant
that meansa ≠ b ≠ c
intermolecular forces are London 41 Select the correct statements.
dispersion and dipole-dipole forces. α = 90 °, β = 120 °, γ = 90 °
(A) Crystalline solids have long ∴ α = γ = 90 °
range order.
β = 120 °
TOPIC 3 (B) Crystalline solids are isotropic. (a) For hexagonal crystal, a = b ≠ c
Solid State (C) Amorphous solids are α = β = 90 °
sometimes called pseudo γ = 120 °
38 The empirical formula for a solids. (b) Orthorhombic crystal, a ≠ b ≠ c
compound with a cubic close (D) Amorphous solids soften over α = β = γ = 90 °
packed arrangement of anions and a range of temperatures. (c) Monoclinic crystal,a ≠ b ≠ c
with cations occupying all the (E) Amorphous solids have a α = γ = 90 °
octahedral sites in A x B. The value definite heat of fusion. β ≠ 90 °
of x is ........ (Integer answer) Choose the most appropriate (d) Triclinic crystal, a ≠ b ≠ c
[2021, 31 Aug Shift-II] answer from the options given α ≠ β ≠ γ ≠ 90 °
Ans. (1) below. [2021, 27 July Shift-II] Therefore, given parameters of unit cell
In Ax B, (a) (A), (B), (E) only is of monoclinic crystal.
Effective number of B atom = 4 (in ccp) (b) (B), (D) only
Effective number of A atom = 4 (c) (C), (D) only 43 Given below are two statements.
(octahedral void) (d) (A), (C), (D) only Statement I Frenkel defects are
So, formula of compound = A4 B 4 ⇒AB Ans. (d) vacancy as well as interstitial
∴ x=1 Statements (A), (C), (D) are correct defects.
whereas (B) and (E) are incorrect. Statement II Frenkel defect leads
40 Match List-I with List-II. (A) Crystalline solids have definate to colour in ionic solids due to
arrangement of constituent
List-I List-II presence of F-centres.
particles. Hence, they have long
(Property) (Example) range order. Choose the most appropriate
A. Diamagnetism 1. MnO (B) Crystalline solids are anisotropic, answer for the statements from
B. Ferrimagnetism 2. O2
i.e. some of its physical properties the options given below.
(like electrical resistance or [2021, 26 Aug Shift-I]
C. Paramagnetism 3. NaCl refractive index) show different (a) Statement I is false but Statement II
values when measured along is true.
D. Antiferromagnetism 4. Fe3O4
different directions in the same
(b) Both statement I and statement II
crystal.
Choose the most appropriate are true.
(C) Amorphous solids are highly
answer from the options given (c) Statement I is true but statement II
supercooled liquids of very high
below. [2021, 27 Aug Shift-I] viscosity thats why they are is false.
A B C D sometimes called pseudo solids. (d) Both Statement I and statement II
(a) 2 1 3 4 (D) Amorphous solids tend to soften are false.
(b) 1 3 4 2 slowly over a wide temperature Ans. (c)
(c) 3 4 2 1 range rather than having a well
Frenkel defect is vacancy as well as
defined melting point.
(d) 4 2 1 3 interstitial defect as atom leaves its
(E) Since, they melt over a range of place in lattice creating a vacancy and
Ans. (c) temperature and start to flow occupy interstitial site in a nearby
A. NaCl is diamagnetic because all without completely changing into location. Hence, statement I is true.
electrons are paired inNa+ and in liquid. Therefore, they do not have
Frenkel defect does not leads to colour
Cl − . So, it shows diamagnetism. definite heat of fusion.
in ionic solids due to absence of
20 JEE Main Chapterwise Topicwise Chemistry

F-centres. Ionic solids having anionic 46 In a binary compound, atoms of Number of tetrahedral void = 2Z = 12
vacancies because of metal excess
element A form a hcp structure and Number of octahedral void = Z = 6
defects. This leads to colour in ionic Total number of voids per unit cell = 18
solids due to presence of F-centres. those of element M occupy 2/3 of
the tetrahedral voids of the hcp Given mass 0.581
Hence, statement II is false. Moles of Ga = =
structure. The formula of the Molar mass 70
44 A copper complex crystallising in a binary compound is 0.581
No. of atoms = ×N A
ccp lattice with a cell edge of [2021, 18 Mar Shift-I] 70
0.4518 nm has been revealed by (a) M2 A3 (b) M 4 A3 (c) M 4 A (d) MA3 0.581 N A
No. of unit cells = ×
employing X-ray diffraction Ans. (b) 70 6
studies. The density of a copper For HCP unit cell, . × 1023 
 0.581 602
No. of voids =  ×  × 18
complex is found to be 7.62 g cm −3 . Number of atom per unit cell Z = 6, so  70 6 
A =6
The molar mass of copper = 1499
. × 1021.
Also, we know
complex is …… g mol −1 . (Nearest Nearest integer = 15 × 1021
If Z = 6, so the number of tetrahedral
integer) voids = 2 × 6 So, correct answer is 15.
[Given : N A = 6.022 × 10 23 mol −1 ] Now, if 2/3 of these voids are occupied
[2021, 22 July Shift-II] 2 49 The number of octahedral voids
by M the number of M = × 2 × 6 = 8
Ans. (106) 3 per lattice site in a lattice is ……… .
Edge length,a = 0.4518 nm ∴ Formula = M8 A6 = M4 A3 (Rounded off to the nearest
Density, d = 7.62 g/cm 3 integer) [2021, 26 Feb Shift-II]
Using formula of density, 47 KBr is doped with 10 −5 mole per
Ans. (1)
Z×M cent of SrBr 2 . The number of
d= Let us assume, the crystal has fcc or ccp
NA × V cationic vacancies in 1 g of KBr
lattice which has octahedral voids.
Here, Z = Number of atom per unit cell
crystal is ……… 10 14 (Round off to
Number of lattice sites occupied = 8
i.e. for ccp = 4 the nearest integer). corner + 6 face centres = 14
M = Molar mass of copper complex =? [Atomic mass : K = 39.1 u, Number of octahedral voids = 12 edge
N A = Avogadro number i.e. Br = 79.9 u, N A = 6.023 × 10 23] centres +1 body centre = 13
[2021, 17 March Shift-II]
6023
. × 1023 mol −1 Number of octahderal void (s) per lattice
V = Volume of unit cell.
Ans. (5) site
The number of cationic vacancies in 1 g 13
7.62 g / cm3 × 6022
. × 1023 mol −1 × = = 0.928 − ~1
of KBr crystal is 5 × 10 14 . 14
(0.4518 × 10 −7 cm) 3 For every Sr2 +   ion, 1 cationic vacancy is
⇒ M=
4 created. Hence, number ofSr2 +   ion = 50 The unit cell of copper corresponds
= 105.79 g/mol ~− 106 g mol −1 number of cationic vacancies to a face centered cube of edge
Since, the mole percentage of length 3.596 Å with one copper
45 Diamond has a three dimensional SrBr2   dopped is 10 −5   to that of total
atom at each lattice point. The
structure of C atoms formed by moles of KBr. calculated density of copper in
covalent bonds. The structure of Hence, number of cationic vacancy kg/m 3 is ……… . [Molar mass of Cu
diamond has face centred cubic 10 − 5 1 = 63.54 g ; Avogadro number =
= × × NA
lattice, where 50% of the 100 119 6.022 × 10 23 ] [2021, 25 Feb Shift-II]
tetrahedral voids are also occupied =
1
× 10 − 7 × 6022
. × 1023 Ans. (9077)
by carbon atoms. The number of 119
(Mass of KBr = 119) Z×M
carbon atoms present per unit cell Density of copper,d =
= 5 × 10 −2
× 10 −7
× 10 = 5 × 10
23 14 a3 × NA
of diamond is …… .
[2021, 20 July Shift-II] Given, Z = 4,for fcc lattice,
Ans. (8) 48 Ga (atomic mass 70 u) crystallises M = 63.54 g mol − 1
in a hexagonal close packed = 63.54 × 10 − 3 kg mol − 1,
Carbon atom in diamond occupy fcc
lattice points as well as half of the structure. The total number of a = 3.596 Å = 3.596 × 10 − 10 m,
tetrahedral voids. voids in 0.581 g of Ga is ……
N A = 6.022 × 1023 mol −1
Number of lattice point in fcc = 4 × 10 21 . (Round off to the nearest
On putting given values, we get
Number of tetrahedral voids = 2 × 4 = 8 integer). [2021, 16 March Shift-II]
4 × (63.54 × 10 −3)
Ans. (15) ⇒d=
∴ 50% of tetrahedral voids = 8 /4 × 2 (3.596 × 10 −10 ) 3 × (6.022 × 1023)
Effective number of atoms of carbon For HCP structure,
kg /m3
1 Effective number of atoms per unit cell
=4+ 8× = 8 (Z) = 6 = 9076.26 ~− 9077 kg /m3
2
States of Matter 21

51 The coordination number of an N A = 6 × 1023 mol − 1 Number of cation M2 occupies 12.5% of

2× M tetrahedral voids of oxide lattice,
atom in a body centered cubic ∴ 6 . 17 = −8 3
structure is ......... . (3 × 10 ) × 6 × 1023 12.5
×8=1
(For bcc, Z = 2) 100
[Assume that the lattice is made So, formula is (M1)2 (M2 ) O4 .
⇒ M = 50 g / mol
up of atoms.] [2021, 24 Feb Shift-I] This must be neutral. Both metals must
Hence, number of molecules present in
Ans. (8) 200 g of X2 is have + 8 charge on total.
Coordination number is the number of w 200 From given options :
N = × NA = × N A = 4N A
nearest neighbours of a central atom in M 50 Oxidaion number of M1 = + 2
the structure. 
Oxidaion number of M2 = + 4
bcc has a coordination number of 8 and 54 An element crystallises in a
contains 2 atoms per unit cell. ∴ (2 × + 2) + (1 × + 4) = + 8
face-centred cubic (fcc) unit
This is because each atom touches four Hence, correct option is (a).
cell with cell edge a. The distance
atoms in the layer above it, four in the
layer below it and none in its own layer.
between the centres of two 56 Which of the following compounds
nearest octahedral voids in is likely to show both Frenkel and
52 An element with molar mass the crystal lattice is Schottky defects in its crystalline
2.7 × 10 −2 kg mol −1 forms a cubic [2020, 5 Sep Shift-II]
form? [2020, 8 Jan Shift-II]
a
unit cell with edge length 405 pm. (a) (b) a (a) AgBr (b) CsCl
2
If its density is 2.7 × 10 3 kg m −3 , the a (c) KBr (d) ZnS
radius of the element is (c) 2a (d) Ans. (a)
2
approximately ............ × 10 −12 m AgBr shows both Schottky and Frenkel
Ans. (a)
(to the nearest integer). r
defects. Because the + (radius of cation
[2020, 3 Sep Shift-I] ov r−
Ans. (143.00) and radius of anion) ratio in AgBr is not
ov very large or not very small.
For the cubic (Z = 4) unit cell,
a/2 (AgCl shows only Schottky defect due to
Corner r
ov greater value of + , whereas AgI shows
a/2 r−
r
In fcc octahedral voids are present at the only Frenkel defect due to smaller value
2r r
Face edge centers at body center. of + ).
centre r−
r Minimum distance between centers of
a two octohedral voids.
2 2
57 Element ‘B ’ forms ccp structure
a2 a2
x =   +   =
a a a
r = Radius of the element + = and ‘A’ occupies half of the
 2  2 4 4 2
a = Edge length of the cubic unit cell octahedral voids, while oxygen
(fcc) = 405 pm atoms occupy all the tetrahedral
2 × 405
55 A crystal is made up of metal ions
4r = 2a ⇒ r = pm voids. The structure of bimetallic
4
M 1 and M 2 and oxide ions. Oxide
oxide is [2019, 8 April Shift-I]
= 143.189 pm ~− 143 pm = 143 × 10 −12 m
ions form a ccp lattice structure.
(a) A2BO 4 (b) AB2O 4 (c) A2B2O (d) A4B2O
The cation M 1 occupies 50% of
Ans. (b)
53 A diatomic molecule X 2 has a octahedral voids and the cation M 2
occupies 12.5% of tetrahedral voids The number of element ‘B ’ in the crystal
body-centred cubic (bcc) structure structure
with a cell edge of 300 pm. of oxide lattice. The oxidation =4N
The density of the molecule is numbers of M 1 and M 2 are, Number of tetrahedral voids = 2N
6.17 g cm −3 . The number of respectively [2020, 6 Sep Shift-II] Number of octahedral voids = N
molecules present in 200 g of X 2 is (a) +2, + 4 (b) +1, + 3 N 4
∴Number of ‘A’ in the crystal = = = 2
(c) +3, + 1 (d) +4, + 2 2 2
(Avogadro constant
(N A ) = 6 × 10 23 mol −1 ) Ans. (a) Number of oxygen (O) atoms
[2020, 5 Sep Shift-I] Number of O2 − ions in ccp = 4 = 2N = 2 × 4 = 8
(a) 40N A (b) 2N A (c) 8N A (d) 4N A Total charge on oxide = − 8 ∴The structure of bimetallic oxide
Ans. (d) Number of tetrahedral voids = 8 = A2 B 4 O8 = AB2 O4
Z×M Number of voids = 4
We know that, d = Number of cation M1 occupies 50% of 58 Consider the bcc unit cells of the
a3 × NA
octahedral voids, solids 1 and 2 with the position of
Given, densityd = 6 . 17 g, 50 atoms as shown below. The radius
×4=2
edge lengtha = 300 pm =3 × 10 − 8 cm, 100 of atom B is twice that of atom A.
22 JEE Main Chapterwise Topicwise Chemistry

The unit cell edge length is 50% Ans. (a) 61 The ratio of number of atoms
more is solid 2 than in 1. What is Given, volume present in a simple cubic, body
the approximate packing efficiency = 10 mL, Molarity = 1 mM = 10 −3 M centered cubic and face centered
in solid 2? ∴ Number of millimoles cubic structure are, respectively.
A A = 10 mL × 10 −3 M = 10 −2 [2019, 12 April Shift-II]
A A
A Number of moles = 10 −5 (a) 8 : 1 : 6 (b) 1 : 2 : 4
A A A (c) 4 : 2 : 1 (d) 4 : 2 : 3
B Now, number of molecules
A = Number of moles × Avogadro’s number Ans. (b)
A A A
A
= 10 −5 × 6 × 1023 = 6 × 10 18 The ratio of number of atoms present in
A A A A simple cubic, body centred cubic and
Solid 1 Solid 2 Surface area occupied by6 × 10 18
face centered cubic structure are 1 : 2 : 4
(a) 65% (b) 90% (c) 75% (d) 45% molecules = 0.24 cm2
respectively.
[2019, 8 April Shift-II] ∴Surface area occupied by 1 molecule
0.24
Ans. (b) = = 0.04 × 10 −18 cm2 62 At 100°C, copper (Cu) has FCC unit
6 × 10 18 cell structure with cell edge length
Key Idea Packing efficiency
Volume occupied by sphere As it is given that polar head is of x Å. What is the approximate
= × 100 approximated as cube. Thus, surface
Volume of cube
area of cube = a2 ,
density of Cu (in g cm −3 ) at this
Given, rB = 2rA ; a2 = a 1 +
50
a 1 = 1.5 a 1 where, a = edge length
temperature?
100
⇒ a2 = 4 × 10 −20 cm2
[Atomic mass of Cu = 63.55 u]
For bcc lattice [2019, 9 Jan Shift-II]
a = 2 × 10 −10 cm = 2 pm 211 205 105 422
4rA = 3 a 1 (a) 3 (b) 3 (c) (d)
x x x3 x3
⇒ rA =
3 a1 4r
⇒ a1 = A
60 An element has a face-centred
Ans. (d)
4 3 cubic (fcc) structure with a cell
 4rA  3  4rA  edge of a. The distance between For fcc, rank of the unit cell (Z) = 4
∴ a2 = 1.5  =   Mass of one Cu-atom, M = 63.55 u
 3 2  3 the centres of two nearest
tetrahedral voids in the lattice is Avogadro’s number,
a2 = 2 3 rA
[2019, 12 April Shift-I] N A = 6023
. × 1023 atom
Packing efficiency a 3 Edge length,a = x Å = x × 10 −8 cm
(a) 2a (b) a (c) (d) a
4 3 4
πrA × z A + πrB3 × z B 2 2 Z×M
density (d) =
= 3 3 Ans. (c) NA × a3
a23 In fcc unit cell, two tetrahedral voids are 4 × 63.55
formed on each of the four non-parallel =
[As the atoms A are present at the edges .
6023 × 1023 × (x × 10 −8 ) 3
1 body diagonals of the cube at a distance
only z A = × 8 = 1, atom B is present only 422048
.
8 of 3a /4 from every corner along the = g cm−3
at the body centre z B = 1] body diagonal. x3

 4 πr 3 × 1 +  4 πr 3 × 1 One of the body diagonal

    63 Which primitive unit cell has
 A
 3 B  of cubic unit cell
∴ PE 2 = 3 A unequal edge lengths (a ≠ b ≠ c) and
a23
1
— AB all axial angles different from 90°?
4 3 4 4 [2019, 10 Jan Shift-I]
πrA + π (2rA ) 3 √3 a
A′
Position of 2 TVs
3 3 — (a) Hexagonal (b) Monoclinic
= 4 1
—(AB)
on one of the
(2 3 rA ) 3 2 body diagonal (c) Tetragonal (d) Triclinic
of the unit cell
4 3 Ans. (d)
πrA × 9
= 3 B′ 1 Triclinic primitive unit cell has
8 × 3 3 rA3 —(AB)
4 dimensions as,a ≠ b ≠ c
B and α ≠ β ≠ γ ≠90 ° .
π
= = 90.72% ≈ 90% √3 a
—
2 3 4 Among the seven basic or primitive
crystalline systems, the triclinic system
59 10 mL of 1 mM surfactant solution is most unsymmetrical. In other cases,
The angle between body diagonal and an
edge length and axial angles are given as
forms a monolayer covering edge is cos−1 (1 / 3). So, the projection of
follows :
0.24 cm 2 on a polar substrate. If the line on an edge isa /4.
Hexagonal : a = b ≠ c
the polar head is approximated as a Similarly, other tetrahedral void also will
and α = β = 90 °, γ = 120 °
cube, what is its edge length? be a /4 away.
Monoclinic :a ≠ b ≠ c
So, the distance between these two is
[2019, 9 April Shift-II]
a − a  − a = a . and α = γ = 90 °, β ≠ 90 °
(a) 2.0 pm (b) 0.1 nm  Tetragonal : a ≠ b ≠ c and α = β = γ = 90 °
4  4 2
(c) 1.0 pm (d) 2.0 nm
States of Matter 23

64 A compound of formula A 2B3 has On substituting all the given values, we 68 Sodium metal crystallises in a body
get
the hcp lattice. Which atom forms 3 −3 23 −1
centred cubic lattice with a unit
(9 × 10 ) kg m × (6 × 10 ) mol cell edge of 4.29 Å. The radius of
the hcp lattice and what fraction of −12 3 3
tetrahedral voids is occupied by the × (200 2 × 10 ) m sodium atom is approximately
=
4 [ JEE Main 2015]
other atoms ? [2019, 10 Jan Shift-II] −1
2 = 0.0305 kg mol (a) 1.86 Å (b) 3.22 Å
(a) hcp lattice- A, tetrahedral voids-B (c) 5.72 Å (d) 0.93 Å
3
1 66 The radius of the largest sphere Ans. (a)
(b) hcp lattice-A, tetrahedral voids-B which fits properly at the centre of
3
1 the edge of a body centred cubic D
(c) hcp lattice-B, tetrahedral voids-A
3 unit cell is r
2 (Edge length is represented by ‘a’) a
(d) hcp lattice-B, tetrahedral voids-A
3 [2019, 11 Jan Shift-II]
2r
Ans. (c) (a) 0.134 a (b) 0.027 a C
(c) 0.047 a (d) 0.067 a r
Total effective number of atoms in hcp a
unit lattice Ans. (d) A B
= Number of octahedral voids in hcp = 6 For body centred cubic bcc structure, a
∴ Number of tetrahedral voids (TV) in hcp 3
radius (R) = a ...(i) From this figure ,
= 2 × Number of atoms in hcp lattice 4
(AC)2 = (AB)2 + (BC)2
= 2 × 6 = 12 Where,a = edge length
⇒ (AC)2 =a2 +a2 = 2 a2
As, formula of the lattice is A2 B3 . According to question, the structure of
Suppose, A B cubic unit cell can be shown as follows: Also, (AD)2 = (AC)2 + (DC)2
 1 × TV (hcp) ⇒ (4r)2 = 2a2 + a2
  R 2r R
3  16 r2 = 3 a2
1
⇒ × 12 6 3
3 ⇒ r= a
2 4
⇒ 1
3 Now, when Na metal crystallises in bcc
⇒ 2 3 unit cell with unit cell edge, a = 4.29 Å
1 a We have the formula for radius,
So, A = tetrahedral voids,
3 ∴ a = 2(R + r) 3
...(ii) i.e. r= × 4.29 Å = 1.86 Å
B = hcp lattice 4
On substituting the value of R from Eq. (i)
to Eq. (ii), we get
65 A solid having density of 69 CsCl crystallises in body centered
a 3
9 × 10 3 kg m −3 forms face centred = a+r cubic lattice. If ‘a’ its edge length,
2 4
cubic crystals of edge length then which of the following
a 3 2a − 3a
200 2 pm. What is the molar mass ⇒ r= − a= expressions is correct?
2 4 4
of the solid? [Avogadro constant (a) rCs + + rCl− = 3a [JEE Main 2014]
= 6 × 10 23 mol −1 , π = 3] a (2 − 3)
r= 3a
[2019, 11 Jan Shift-I] 4 (b) rCs + + rCl− =
2
(a) 0.03050 kgmol−1 ⇒ r = 0.067a
3
(b) 0.4320 kg mol−1 (c) rCs + + rCl− = a
(c) 0.0432 kg mol−1 67 A metal crystallises in a face 2
(d) 0.0216 kg mol−1 centred cubic structure. If the edge (d) rCs + + rCl− = 3a
Ans. (a) length of its unit cell is ‘a’, the Ans. (c)
closest approach between two atoms
Density of a crystal In CsCl, Cl − lie at the corners of simple
M×Z d × NA × a3
in metallic crystal will be cube and Cs + at the body centre.
d= ⇒ M= [ JEE Main 2017]
Therefore, along the body diagonal, Cs +
NA × a 3
Z
(a) 2 a (b) 2 2 a and Cl − touch each other.
Given, d = 9 × 10 3 kg m −3 (c) 2 a (d)
a
3
M = Molar mass of the solid 2 Hence, a = rCs + + rCl−
2
Z = 4 (for fcc crystal) Ans. (d)
70 Which of the following exists as
N A = Avogadro’s constant For fcc arrangement,4r = 2a
covalent crystals in the solid state?
= 6 × 1023 mol −1 where, r = radius anda = edge length [JEE Main 2013]
a = Edge length of the unit cell ∴ Closest distance = 2 r =
2a a
= (a) Iodine (b) Silicon
= 200 2 pm = 200 2 × 10 −12 m 2 2 (c) Sulphur (d) Phosphorus
24 JEE Main Chapterwise Topicwise Chemistry

Ans. (b) 74 The edge length of a face centered 78 Total volume of atoms present in a
Silicon exists as covalent crystal in solid cubic cell of an ionic substance is face-centred cubic unit cell of a
state. 508 pm. If the radius of the cation metal is (r is atomic radius)
(Network like structure, like diamond). [AIEEE 2006]
is 110 pm, the radius of the anion is
20 3 24 3
[AIEEE 2010] (a) πr (b) πr
71 Lithium forms body-centred cubic (a) 288 pm (b) 398 pm 3 3
structure. The length of the side of 12 3 16 3
(c) 618 pm (d) 144 pm (c) πr (d) πr
its unit cell is 351 pm. Atomic radius 3 3
Ans. (d)
of the lithium will be [AIEEE 2012] Ans. (d)
For fcc arrangement
(a) 75 pm (b) 300 pm Total number of atoms in face centred
2(r + + r − ) = edge length
(c) 240 pm (d) 152 pm cubic unit cell = 4
Ans. (d) 2 (110 + r − ) = 508 1
At corner = 8 × = 1
So, r − = 144 pm 8
In body-centred cubic structure,
Edge length = a = 351 pm, Radius = r = ? 1
75 Percentage of free space in cubic On faces = 6 × = 3
3a 2
Then, r = close packed structure and in body
4 Total = 4
centred packed structure are
3 × 351 4 πr 3 16 3
= = 152 pm respectively [AIEEE 2010] Total volume = 4 × = πr
4 3 3
(a) 30% and 26% (b) 26% and 32%
(c) 32% and 48% (d) 48% and 26% 79 An ionic compound has a unit cell
72 In a face-centred cubic lattice, atom Ans. (b)
A occupies the corner positions and consisting of A ions at the corners
π
atom B occupies the face centred Packing fraction of ccp = = 0.74 of a cube and B ions on the centres
3 2 of the faces of the cube. The
positions. If one atom of B is
⇒74% empirical formula for this
missing from one of the face
% free space in ccp = 26% compound would be [AIEEE 2005]
centred points, the formula of the
π 3 (a) A3B (b) AB 3
compound is [AIEEE 2011] Packing fraction of bcc = = 0.68
8 (c) A2 B (d) AB
(a) A2B (b) AB2
= 68% % free space in bcc = 32% Ans. (b)
(c) A2B2 (d) A2B2
Ans. (d) Unit cell consists of A ions at the
76 Copper crystallises in fcc with a corners.
Number of atoms (A) per unit cell unit cell length of 361 pm. What is
1 Thus, number of ions of the type
=8× =1 the radius of copper atom? 8
8 [AIEEE 2009] A= =1
8
Number of atoms (B) per unit cell (a) 108 pm (b) 127 pm
1 5 Unit cell consists of B ions at the centre
= (6 − 1) × = (one atom B is missing) (c) 157 pm (d) 181 pm
of the six faces.
2 2 Ans. (b) Thus, number of ions of the type
In fcc unit cell 2a = 4r 6
B= =3
2a 2 × 361 2
r= = = 127 pm
4 4 [Each corner is shared by 8 cubes
and each face is shared by 2 faces]
77 In a compound, atoms of element Y Thus, formula is AB 3.
form ccp lattice and those of
Thus, formula is A 1B 5 / 2 = A 2 B 5 element X occupy 2/3rd of 80 What type of crystal defect is
tetrahedral voids. The formula of indicated in the diagram shown
73 Copper crystallises in fcc lattice the compound will be [AIEEE 2008]
with a unit cell edge of 361 pm. The below? [AIEEE 2004]
(a) X 4Y3 (b) X2Y3
radius of copper atom is (c) X2Y (d) X 3Y4 Na+ Cl– Na+ Cl–
[AIEEE 2011]
Ans. (a)
(a) 181 pm (b) 108 pm Cl– Cl– Cl– Na+
(c) 128 pm (d) 157 pm Suppose atoms of elementY in ccp = 100
Number of tetrahedral voids = 2 × 100 Na+ Cl– Cl–
Ans. (c)
Number of atoms of element
Copper crystallises in fcc lattice. Cl– Na+ Cl– Na+
2 400
If, r = radius, a = edge length X = × 200 =
3 3 (a) Frenkel defect
a 361
then r = = pm ⇒
X 400
=
2 2 2 2 (b) Schottky defect
Y 300
(c) Interstitial defect
= 127.633 pm ≈ 128 pm Formula = X4Y3 (d) Frenkel and Schottky defects
States of Matter 25

Ans. (b) = a3 × d (a) 4, 4 (b) 4, 2

When equal number of cations and = a3 ×
MZ
=
MZ (c) 2, 4 (d) 1, 1
anions (such that charges are equal) are N 0a 3 N 0 Ans. (c)
missing (1Na+ , 1Cl − / 1 Fe2 + , 2Cl − ) then, it 58.5 × 4
m= g In Na unit cell (body centred cubic)
is a case of Schottky defect.
6.02 × 10 23 1
8 (corner atoms) × = 1
81 How many unit cells are present in 1 8
∴ Number of unit cells in 1g =
a cube shaped ideal crystal of NaCl m Atoms placed inside the unit cell = 1
of mass 1.00 g? 6.02 × 1023 Total atoms = 2
=
[Atomic mass : Na = 23, Cl = 35.5] 58.5 × 4 In Mg unit cell (face centred cubic)
[AIEEE 2003] = 2.57 × 10 21 1
8 (corner atoms) × = 1
(a) 2.57 × 10 21
(b) 5.14 × 10 21
8
(c) 1.28 × 10 21 (d) 1.71 × 10 21 82 Number of atoms in the unit cell of 1
6 (face atoms) × = 3
Ans. (a) Na (bcc type crystal) and Mg (fcc 2
Mass of one unit cell type crystal) are, respectively Total atoms = 4
(m) = volume × density [AIEEE 2002]
03
Atomic Structure
TOPIC 1 Number of neutrons in deuterium Statement II According to Bohr’s
(21 H or 21 D) is 1 (y)
Preliminary Models Number of neutrons in tritium
model of an atom, qualitatively the
magnitude of velocity of electron
(31 H or 31 T) is 2 (z)
01 If the Thomson model of the atom increases with decrease in
So, the sum of x , y and z is x + y + z =3
was correct, then the result of principal quantum number.
Rutherford's gold foil experiment In the light of the above
would have been TOPIC 2 statements, choose the most
(a) all of the α-particles pass through Bohr’s Model and appropriate answer from the
the gold foil without decrease in options given below.
speed. Hydrogen Spectrum [2021, 26 Aug Shift-I]
(b) α-particles are deflected over a wide (a) Both statement I and statement II
range of angles. 03 The kinetic energy of an electron in are false.
(c) all α-particles get bounced back by (b) Both statement I and statement II
the second Bohr orbit of a
180°. are true.
(d) α-particles pass through the gold foil h2
hydrogen atom is equal to . (c) Statement I is false but statement II
deflected by small angles and with xma 02 is true.
reduced speed. (d) Statement I is true but statement II
[2021, 27 July Shift-II]
The value of 10x is ……… .
is false.
Ans. (d) (a 0 is radius of Bohr’s orbit)
(Nearest integer) [Given, π = 3.14] Ans. (c)
According to Thomson model of atom, [2021, 27 Aug Shift-I] According to Bohr’s atom, velocity of
positive charge and mass of atom is electron is given by,
uniformely distributed and electrons are Ans. (3155)
Z
embedded in it like seeds in water melon. QAngular moment is given as, v∝ …(i)
n
Hence, if we strikeα-particles nh
(consisting of 2 positive charge protons mvr = where,v = velocity of electron
2π
and 2 neutral neutrons i.e. of heavier Z = atomic number of atom
n2h2 4h2 n = principal quantum number
mass than 1 proton) on a thin gold foil ∴Kinetic energy = =
then α-particles will pass through the 2
8π mr 2
8 π m(4a 0 )2
2
From Eq. (i), velocity of electron is
gold foil and will deflected by some angle directly proportional to atomic number
 4  h2 h2
(due to charge repulsion) with reduced = 2  = (Given) of atom, corresponding to positive
speed.  8 π × 16  ma 0 xma20
2
charge. So, as Z increases velocity also
This result is depicted in option (d) that 4 increases. Hence, statement I is false.
x=
α-particles pass through the gold foil 8 π2 × 16 Also, velocity of electron is inversely
deflected by small angle with reduced proportional to
speed. ⇒ x = 315.507
n i.e. as ‘n’ decreases velocity of electron
10x = 3155.07 increases. So, statement II is true.
02 Hydrogen has three isotopes (A), (B)
and (C). If the number of neutron(s) 04 Given below are two statements. 05 Given below are two statements.
in (A), (B) and (C) respectively, are Statement I According to Bohr’s Statement I Bohr’s theory
(x), (y) and (z), the sum of (x), (y) and model of an atom, qualitatively the accounts for the stability and line
(z) is [2020, 8 Jan Shift-II] magnitude of velocity of electron spectrum of Li + ion.
(a) 4 (b) 3 increases with decrease in Statement II Bohr’s theory was
(c) 2 (d) 1 positive charges on the nucleus as unable to explain the splitting of
Ans. (b)
there is no strong hold on the spectral lines in the presence of a
Number of neutrons in protium (11H) is
electron by the nucleus. magnetic field.
zero (x).
Atomic Structure 27

In the light of the above Choose the most appropriate T 2 >T 1

statements, choose the most answer from the options given Intensity
appropriate answer from the below. [2021, 24 Feb Shift-II] (d) of black body
radiation T1
options given below : (a) Only III (b) Only I
[2021, 18 March Shift-II] (c) I, III and IV (d) I and IV
Wavelength
(a) Both statements I and II are true. Ans. (d)
(b) Statement I is false but statement II Ans. (c)
is true. According to Bohr’s theory,
Quantum nature of atoms are associated
Z2 Z2 (eV)
(c) Both statements I and II are false. I. KE ∝ 2 or 136 . ∝ 2 , with following phenomena or processes
(d) Statement I is true but statement II n n (atom) (i) Absorption spectrum
is false. (∴ Correct) (ii) Emission spectrum
Z
Ans. (b) II. Speed of electron ∝ (iii) Black body radiation
n (iv) Photo-electricity
Statement I is false, because Bohr’s
(Here, Z = atomic number, Internal energy (U) of particles like atoms
theory accounts for the stability and
n = number of shells) depends upon the thermodynamic
spectrum of single electronic species
(e.g. He+ , Li2 + etc.) but Li+ has two ∴ v × n∝Z (∴ Incorrect) variables (p, V ,T ) of the system. Thus,
electrons. III. Frequency of revolution of electron U = f (pT
, )
v
Bohr’s theory fails to explain splitting of = or U = f1 (T ,V )
2πr
spectral lines in presence of magnetic or U = f2 (p,V )
field i.e. Zeeman effect . Z2  z n2 
Frequency ∝ 3 Qv ∝ , r ∝  So, quantum nature of atom is not
∴ Statement II is true. n  n z associated with its internal energy.
(∴Incorrect) Graph (c) is not a direct manifestation of
06 Electromagnetic radiation of kq 1q2 kZe2 the quantum nature of atoms.
wavelength IV. F = =
r2 r2
663 nm is just sufficient to ionise 09 The region in the electromagnetic
Z
the atom of metal A. The ionisation F= 2
spectrum where the Balmer series
energy of metal A in kJ mol −1 is  n2 
 
lines appear is [2020, 4 Sep Shift-I]
……… . (Rounded off to the nearest Z (a) infrared (b) ultraviolet
integer) (c) microwave (d) visible
Z3
[h = 6.63 × 10 −34 J-s, c = 3.00 × 10 8 F∝ (∴Correct) Ans. (d)
n4
ms −1 , N A = 6.02 × 10 23 mol −1] Hence, only I, and IV are correct.
Balmer series lies in the visible region of
[2021, 25 Feb Shift-II] the electromagnetic spectrum. Photons
Ans. (180) that correspond to these energies will
08 The figure that is not a direct not strongly absorb highly excited
Energy of EMR = IE of the metal (A) manifestation of the quantum hydrogen gas. So, there is the possibility
hc hc
= hν = atom−1 = − × N A mol −1 nature of atoms is for detecting absorption at Balmer line
λ λ [2020, 2 Sep Shift-I] wave length.
. × 10 −34 ) × (3 × 10 8 ) × (602
(663 . × 1023) Paschen, Brackett and Pfund series lies
= Increasing wavelength
(663 × 10 −9 ) in the infrared region whereas, only
J mol −1 Layman series lies in the ultraviolet
[Qλ = 663 nm = 663 × 10 − 9 m] (a) region of the electromagnetic spectrum.
= 180600 J mol −1 = 180.6 kJ mol −1
~− 180 kJ mol −1 Absorption spectrum 10 The shortest wavelength of H atom
in the Lyman series is λ 1 . The
longest wavelength in the Balmer
Kinetic energy of
photoelectrons

07 According to Bohr’s atomic theory, Rb K

2
Na
series of He + is [2020, 4 Sep Shift-II]
Z 36 λ 1 5λ 9λ 1 27λ 1
I. kinetic energy of electron is ∝ (b) (a) (b) 1 (c) (d)
n2 5 9 5 5
II. the product of velocity (v) of Ans. (c)
electron and principal quantum Frequency of incident hc
radiation As we know that,∆E =
number (n), ‘vn’ ∝ Z 2. λ
hc
III. frequency of revolution of Hence, λ will be, λ =
Z3 ∆E
Internal
electron in an orbit is ∝ 3 (c) energy of For, λ = minimum, i.e. shortest,
n Ar ∆E = maximum
IV. coulombic force of attraction 300 400 500 600 For Lyman series, n = 1 and for ∆E max
Z3 Temperature (K) transition must be form n = ∞ to n = 1 .
on the electron is ∝ 4
n
28 JEE Main Chapterwise Topicwise Chemistry

So,
1
= RH Z2
 1
 − 
1
(Qn 1 = 1 and
(III) The lines of longest wavelength frequencies in cm −1 . The ratio
λ  n2 n2  corresponds to n2 = 3 ∆ νLyman / ∆ ν Balmer is
 1 2
n2 = ∞) (IV) The ionisation energy of
[2019, 9 April Shift-I]
hydrogen can be calculated
= RH  2 − 2  × (1)2
1 1 1 (a) 27 :5 (b) 5 :4 (c) 9 :4 (d) 4 :1
λ  1 ∞  from wave number of these
Ans. (c)
1 lines [2020, 8 Jan Shift-I]
= RH (1 − 0) For any given series of spectral lines of
λ (a) I, II, IV (b) II, III, IV
1 (c) I, III, IV (d) I, II, III atomic hydrogen.
⇒ = R × (1)2
λ Let ∆ν = νmax − νmin be the difference in
Ans. (d)
1 maximum and minimum frequencies in
⇒ λ1 = Statements I, II and III are correct. The cm−1.
R
explanations of these statements are as For Lyman series,
For longest wavelength, ∆E = minimum follows :
for Balmer series, n = 3 to n = 2 will have ∆ν = νmax − νmin
(I) In each series of hydrogen spectrum,
∆E minimum.  1 1
For He+ , Z = 2
lines converge at the higher frequency or General formula: ν = 109677  2 − 2 
lower wavelength limit.  ni nf 
1  1 1
So, = RH × 22  2 − 2  Frequency For Lyman n1 = 1, n2 = 2, 3,K
λ2 n n 
 1 2
,  −  = 109677  1 − 0
1 1
1  1 1 1 5 νmax = 109677 ,  
= RH × 4 −  , = RH × 4 ×  1 ∞ 1 
λ2  4 9  λ2 36
1 5
Wavelength = 109677
,
= RH × ∴ This is correct. 1 1 
λ2 9 νmin = 109677
,  − 2
(II) For Balmer series, n1 = 2  1 (2) 
9
⇒ λ2 = λ 1 × ∴ This is correct.
5 ∆νLyman = νmax − νmin
(III) Longest wavelength represents the  109677
, × 3  109677
,
smallest wave number = 109677
, − =
11 The difference between the radii of  4  4
 1 1
3rd and 4th orbits of Li 2+ is ∆R 1 . ν = RH  2 − 2  . (n2 > n1) For Balmer series,
n n 
The difference between the radii of  1 2
3rd and 4th orbits of He + is ∆R 2 .  1 1 109677
When n1 = 2, smallest value of ν is for νmax = 109677
,  2−  ⇒
 (2) ∞  4
Ratio ∆R 1 : ∆R 2 is [2020, 5 Sep Shift-I] n2 = 3
(a) 3 : 2 (b) 8 : 3 ∴ This is a correct statement.  1 1 
(IV) This statement is not correct. It’s νmin = 109677
,  2 − 2
(c) 2 : 3 (d) 3 : 8  (2) (3) 
Ans. (c) corrected form is as follows: Ionisation
energy of hydrogen can be calculated 109677 × 5
n2 ⇒
We know that,r = 0.529 Å from Lyman series lines (n = 1) only by 36
Z using the following formula, ∆ν = νmax − νmin
For Li2 + (r ) − (r 2 + ) n = 3
Li 2 + n = 4 Li  1 1 
ν = RH  2 − 2 
− × 5
0.529 ,
109677 ,
109677
⇒ (16 − 9) = ∆R 1 …(i)  (1) ∞  ∆νBalmer =
3 4  36 
For He + (rHe + ) n = 4 − (rHe + ) n = 3  1
13 The radius of the second Bohr orbit = 109677
,  
0.529  9
⇒ (16 − 9) = ∆R2 …(ii) in terms of the Bohr radius, a 0 , in
∆ νLyman
3
0.529 Li 2 + is [2020, 8 Jan Shift-II] =
109677
, /4
(16 − 9) 2a0 4a0 4a0 2a0 ∆ νBalmer 109677
, /9
∆R 1 2
= 3 = (a) (b) (c) (d) ∆ νLyman
∆R2 0.529 3 3 9 9 9
(16 − 9)
3 ⇒ =
2 Ans. (b) ∆ νBalmer 4
Hence, the ratio of ∆R 1 : ∆R2 is 2 : 3. According to Bohr model, radius of orbit ∆ νLyman
∴ The ratio of is 9 : 4.
a × n2 ∆ νBalmer
12 For the Balmer series in the rn = 0 , wherea 0 = Bohr radius
Z
spectrum of H atom, (Radius of 1st orbit of H-atom) 15 The ratio of the shortest
 1 1  For, Li2 + , Z = 3 and n = 2 wavelength of two spectral series
ν = R H  2 − 2  , the correct 22 × a 0 4a 0 of hydrogen spectrum is found to
 n1 n2  ∴ r= =
3 3 be about 9. The spectral series are
statements among (I) to (IV) are : [2019, 10 April Shift-II]
(I) As wavelength decreases, the 14 For any given series of spectral (a) Lyman and Paschen
lines in the series converge lines of atomic hydrogen, let (b) Brackett and Pfund
(II) The integer n1 is equal to 2 ∆ν = ν max − ν min be the difference (c) Paschen and Pfund
in maximum and minimum (d) Balmer and Brackett
Atomic Structure 29

Ans. (a) On comparing with equation of straight Ans. (d)

According to Rydberg’s equation, line, y = mx + c, we get Bohr radius (rn ) = ∈0 n2h2
−RH
Slope = RH , intercept = .
1 RH  1 1 64 rn =
n2h2
⇒ k=
1
= − 2

λ hc  n1 n2  4 π ∈0
2 1 2 2
Thus, plot of wave number (ν) against 2 4π me kZ
n
1  1 1 ∴ rn =
n2h2 ∈0
= n2
a0
or ∝ 2 − 2  will be linear with slope (+ RH ).

λ  n1 n2  πme2 Z Z

For shortest wavelength, i.e. highest 17 The ground state energy of hydrogen where, m = mass of electron, e = charge of
energy spectral line, n2 will be (∞). atom is −13.6 eV. The energy of electron
For the given spectral series, ratio of the second excited state ofHe + ion in eV h = Planck’s constant,
shortest wavelength of two spectral is [ 2019, 10 Jan Shift-II] k = Coulomb constant
series can be calculated as follows : n2 × 0.53
1
(a) –54.4 (b) – 3.4 (c) – 6.04 (d) – 27.2 rn = Å
1 1
− −0 Ans. (c) Z
λL 32 ∞2 9 1 th
(a) = = = The ground state energy of H-atom is
Radius of n Bohr orbit for H-atom
λP 1
−
1 1−0 9 = 0.53 n2 Å [Z = 1 for H-atom]
+ 136
. eV.
12 ∞2 ∴Radius of 2nd Bohr orbit for H-atom
For second excited state, n = 2 + 1 = 3
1
−
1 = 0.53 × (2)2 = 2.12 Å
λ Bk 52 ∞2 Z2
(b) = =
1 16 16
× = ∴ E 3 (He+ ) = − 136
. × 2 eV
λ Pf 1 1 25 1 25 n
[Qfor He+ , Z = 2]
20 Which of the following is the
−
42 ∞2 22 energy of a possible excited state
. × 2 eV = − 604
= − 136 . eV of hydrogen?
1 1 3 [JEE Main 2015]
− 2
λ 2
∞ = 1 ×9= 9 (a) + 13.6 eV (b) − 6.8 eV
(c) P = 5 18 Heat treatment of muscular pain
λ Pf 1
−
1 25 1 25 (c) − 3.4 eV (d) + 6.8 eV
involves radiation of wavelength of
32 ∞2 Ans. (c)
about 900 nm. Which spectral line
1 1
− of H-atom is suitable for this
λ B 42 ∞2 1 4 1 n=4
(d) = = × = purpose? [R H = 1 × 10 5 cm–1 , n=3
λ Bk 1
−
1 16 1 4
n=2
22 ∞2 h = 6.6 × 10 −34 Js, c = 3 × 10 8 ms −1 ] n=1
Note Lyman = L (n1 = 1), Balmer = B (a) Paschen, 5 →3 (b) Paschen, ∞→ 3
(c) Lyman, ∞→ 1 (d) Balmer, ∞→ 2 Maximum population of e– of H-atom
(n1 = 2)
Paschen = P (n1 = 3), Brackett = Bk (n1 = 4) [2019, 11 Jan Shift-I] Since, at n = 1, the population of
Ans. (b) electrons is maximum i.e. at ground
Pfund = Pf (n1 = 5)
  1  state. So, maximum excitation will take
1 1 place from n = 1 to n = 2.
∆E = hc × = hc ×  RH  2 − 2  × Z2 
16 For emission line of atomic λ  
  n1 n2   Hence, n = 2 is the possible excited state.
hydrogen from ni =8 to nf = n, the 1 1 hc Now, we have the formula for energy of
⇒ 2 − 2 =
plot of wave number (ν) against n1 n2 RH × λ × Z2 × hc H-atom
 1  [for H, atom Z = 1] Z2
 2  will be (The Rydberg constant, 1 1 1 (E n )H = −13.6 2 eV
n  = = × n
RH × λ (1 × 10 7 m−1) (900 × 10 −9 m)
R H is in wave number unit) 1 1 1 where, Z = atomic number
(a) non linear ⇒ − = Z for H-atom = 1
n21 n22 9
(b) linear with slope −RH 1 1 1 1 ∴
1
(E n )H = −13.6 × 2 eV
(c) linear with slope RH So, in option (b) 2 − 2 = − 0 = 2
3 ∞ 9 9
(d) linear with intercept −RH ∴n1 = 3,  =−
13.6
eV = − 3.4 eV
[2019, 9 Jan Shift-I]  n = ∞ 4
Ans. (c)  2 

According to Rydberg’s formula, 19 The radius of the second Bohr orbit 21 Energy of an electron is given by
 1 1 Z2
wave number (ν) = RH Z2  2 − 2 
for hydrogen atom is (Planck’s E = − 2.178 × 10 −18 J  2  .
 ni nf  constant (h) = 6.6262 × 10 − 34 Js; n 
Given, ni = n, nf = 8
mass of electron = 9.1091 × 10 − 31 kg Wavelength of light required to
; charge of electron excite an electron in an hydrogen
[Q it is the case of emission] (e) = 1.60210 × 10 − 19 C; permitivity of atom from level n = 1 to n = 2 will be
 1 1
ν = RH × (1)2  2 − 2 
vacuum (∈0 ) = 8.854185 × 10 − 12 (h = 6.62 × 10 −34 J s and
n 8  kg − 1m − 3 A 2 ) [JEE Main 2017] c = 3.0 × 10 8 ms −1 ) [JEE Main 2013]
ν = RH  2 −  = 2H − H
1 1 R R (a) 1.65 Å (b) 4.76 Å (a) 1.214 × 10−7 m (b) 2.816 × 10−7 m
 n 64  n 64 (c) 0.529 Å (d) 2.12 Å (c) 6.500 × 10−7 m (d) 8.500 × 10−7 m
30 JEE Main Chapterwise Topicwise Chemistry

Ans. (a)  1 1 25 The number of photons emitted by

= constant ×  2 − 2 
Energy change  n1 n2  a monochromatic (single
 1 1  hc frequency) infrared range finder of
∆E = 2.178 × 10 −18  2 − 2  = (a) For n2 = 3 and n1 = 1,
1 2  λ power 1 mW and wavelength of
v ( H) = constant  − 
1 1
 1 1
=2.178 × 10 −18  2 − 2   1 9  1000 nm, in 0.1 second is x × 10 13 .
1 2  The value of x is ......... . (Nearest
8 3
6.62 × 10 −34 × 3.0 × 10 8 = × constant ≠ × constant integer)
= 9 4
λ (b) For n2 = 2 and n1 = 1, (h = 6.63 × 10 − 34 Js, c = 3.00 × 10 8
⇒λ ≈ 1.214 × 10 −7 m ms − 1 ) [2021, 27 Aug Shift-II]
v (H) = constant ×  − 
1 1
 1 4  Ans. (50)
22 A gas absorbs photon of 355 nm Power of the source = 1 mW = 10 −3 W
and emits at two wavelengths. If 3
= × constant = v( He+ ) hc
4 Energy of one photon, E = hν =
one of the emission is at 680 nm, λ
the other is at (c) For n = 3 and n 1 = 2
[AIEEE 2011] where, h = 6.6 × 10 −34 Js,
(a) 1035 nm (b) 325 nm 1 1
v (H) = constant ×  2 − 2  c = 3 × 10 8 m/ s and
(c) 743 nm (d) 518 nm 2 3  λ = 1000 nm
Ans. (c) 5 = 1000 × 10 −9 m (1 nm = 10 −9 m)
= × constant ≠v ( He+ )
Energy values are always additive. 36 = 10 −6 m
hc hc hc (d) For n2 = 4 and n1 = 3 6.6 × 10 −34 × 3 × 10 8
E total = E 1 + E2 ⇒ = + E=
λ λ 1 λ2 v (H) = constant ×  2 − 2 
1 1
 3 4  10 −6
−
~= 20 × 10 20 J
E1
E Power = number of photons emitted in
E2 TOPIC 3 one second × energy of 1 photon.
10 −3 = n × 20 × 10 −20
1 1 1 Wave Particle and 10 −3
∴ = + ⇒ n=
λ λ 1 λ2 Quality of Matter 20 × 10 −20
1 1 1 = 0.5 × 10 16
⇒ = +
355 680 λ2 24 A 50 watt bulb emits Number of photons emitted in 1 s
λ2 = 742 .77 nm monochromatic red light of = 0.5 × 10 16
≈ 743 nm wavelength of 795 nm. The number Number of photons emitted in 0.1 s
of photons emitted per second by = 0.5 × 10 16 × 0.1 = 50 × 10 13
23 The frequency of light emitted for the bulb is x × 10 20 . The value of x x × 10 13 = 50 × 10 13
the transition n = 4 to n = 2 of He + is is ……… . x = 50
equal to the transition in H atom
[Given, h = 6.63 × 10 −34 Js and 26 A metal surface is exposed to
corresponding to which of the
c = 3.0 × 10 8 ms −1 ] 500 nm radiation. The threshold
following? [AIEEE 2011]
[2021, 1 Sep Shift-II]
(a) n = 3 to n = 1 (b) n = 2 to n = 1 frequency of the metal for
Ans. (2)
(c) n = 3 to n = 2 (d) n = 4 to n = 3 photoelectric current is
Energy of photon is given as
Ans. (b) 4.3 × 10 14 Hz. The velocity of ejected
nhc
2 π2 mZ2 e 4 k2  1 1
E=
λ
…(i) electron is ……… × 10 5 ms − 1 .
∆E = hu =  2 − 2
h2  1
n n2
 where, E = energy of photon (50 W), (Nearest integer)
if electron falls from n2 -level to n1- level. n = number of photon [Use h = 6.63 × 10 − 34 Js,
∴ In He+, for n2 = 4 to n1 = 2 transition h = Planck’s constant (6.63 × 10 −34 J s) m e = 9.0 × 10 − 31 kg]
1 1 c = speed of light (3 × 10 8 m / s) [2021, 26 Aug Shift-II]
v + = constant (4)  2 − 2  λ = wavelength of light (795 × 10 −9 m) Ans. (5)
He
 2 4 
E = 50 W = 50 J = energy of photon According to photoelectric effect
[QZHe + = 2] hc 1
3 n × 6.63 × 10 −34 J s × 3 × 10 8 m / s = = hν0 + mv2
= constant × 4   50 J = λ 2
 16  795 × 10 −9 m
(where,h = Planck’s constant,
3 50 × 795 × 10 −9 λ = wavelength
= × constant ⇒ n=
4 6.63 × 10 −34 × 3 × 10 8 ν0 = threshold frequency,
 1 v = velocity of electron
1 = 1998.49 × 10 17 = 1.998 × 1020
v ( H) = constant (1)2  2 − 2  m = mass of electron,
 n1 n2  ⇒ ≈ 2 × 1020 ⇒ x = 2
c = speed of light)
∴ Answer is 2.
Atomic Structure 31

6.63 × 10 −34 × 3 × 10 8 28 An accelerated electron has a Speed of light, c = 3 × 10 8 m/s

⇒
speed of 5 × 10 6 ms −1 with an
−9
500 × 10 So, energy required to eject the
hc
1 uncertainty of 0.02%. The electrons E req =
= 6.63 × 10 −34 × 4.3 × 10 14 + mv2 λ
2 uncertainty in finding its location
.
6626 × 10 −34 Js × 3 × 10 8 ms−1
6.63 × 30 × 10 −19 while in motion is x × 10 −9 m. The =
= 6.63 × 4.3 × 10 −20 400 × 10 −9 m
50 1
value of x is ……… . (Nearest
+ mv2 100
integer) Number of ejected electrons =
2 E req
1 [Use mass of electron = 9.1 × 10 −31
11.271 × 10 −20 J = × 9 × 10 −31 × v2 kg, h = 6.63 × 10 −34 Js, π = 3.14] =
100
2
[2021, 25 July Shift-II] .
6626 × 10 −34 × 3 × 10 8
v = 5 × 10 5 m / s 400 × 10 −9
Ans. (58)
∴ x=5 400 × 10 −7 × 1026
Uncertainity in speed of electron =
0.02 6626
. ×3
27 Given below are two statements : = ∆v = × 5 × 10 6
100 40 × 10 −20
Statement I Rutherford’s gold foil =
= 10 3 m/s 6626
. ×3
experiment cannot explain the Uncertainity in position = x × 10 −9 m = 201
. × 1020
line spectrum of hydrogen atom. According to Heisenberg uncertainty ~ 2 × 2020
−
Statement II Bohr’s model of principle,
So, value is2 × 1020 and x is 2.
hydrogen atom contradicts h
∆x ⋅ ∆P =
Heisenberg’s uncertainty 4πm
here, ∆x = uncertainty in position 30 The wavelength of electrons
principle.
∆P = uncertainty of momentum accelerated from rest through a
In the light of the above potential difference of 40 kV is
h = Planck’s constant
statements, choose the most x × 10 −12 m. The value of x is ……
22
appropriate answer from the π = or 3.14
7 (Nearest integer)
options given below :
[2021, 27 July Shift-I]
m = mass of electron Given : Mass of electron
(a) Statement I is false but statement II x × 10 − 9 × 10 3 =
6.626 × 10 − 34 = 9.1 × 10 −31 kg
is true. 4 × 3.14 × 9.1 × 10 − 31 Charge on an electron = 1.6 × 10 −19 C
(b) Statement I is true but statement II x × 10 − 6 = 0.058 × 10 − 3 Planck’s constant = 6.63 × 10 −34 Js
is false. 0.058 × 10 − 3 [2021, 20 July Shift-II]
⇒ x= = 58
(c) Both statement I and statement II 10 − 6 Ans. (6)
are false.
De-broglie wavelength of electron :
(d) Both statement I and statement II 29 A source of monochromatic h
are true. λe =
radiation of wavelength 400 nm 2m(KE)
Ans. (d) provides 1000 J of energy in 10 where λ e = wavelength of electron
Both Statement I and Statement II are seconds. When this radiation falls KE = kinetic energy of electron
true.
on the surface of sodium, x × 10 20 also, kinetic energy = qV
Rutherford proposed the nuclear model q = charge of electron,
electrons are ejected per second.
of the atom by gold foil experiment
Assume that wavelength 400 nm is m = mass of electron,
which showed that the atom is mostly
sufficient for ejection of electron V = potential.
empty space with tiny, dense, positively
charged nucleus and electrons are from the surface of sodium metal. . × 10 −34
663
λe =
continuously moving around nucleus but The value of x is …… . . × 10 −19 × 9.1 × 10 −31 × 40 × 10 3
2 × 16
did not explain the line spectrum of
hydrogen atom. (Nearest integer) λ e = 6.14 × 10 −12 m
Definite line in H-spectrum are explained (h = 6.626 × 10 −34 Js) ∴ x = 6 (nearest)
by Bohr. [2021, 25 July Shift-I] or
Bohr’s model of an atom is contradicted Ans. (2) According to de-Broglie wavelength
by Heisenberg uncertainty principle. Total energy provided by source per equation for electron,
According to Bohr model, an electron in second 123.
λ= Å where,V = Voltage
an atom is located at definite distance 1000
= = 100 J V
from nucleus and is revolving with 10 123
.
= = 6.15 × 10 −12 m
definite velocity around it. While Wavelength, (λ) = 400 nm or 400 × 10 −9 m 200
uncertainty principle explain that it is Planck’s constant,
impossible to determine simultaneously x ≈6
h = 6626
. × 10 −34 Js
exact position and velocity of electron.
32 JEE Main Chapterwise Topicwise Chemistry

31 When light of wavelength 248 nm ∆x × m∆v ≥

h
(∴ m = 10 g (h = 6.63 × 10 −34 J s; c = 3 × 10 8 m/s)
4π ………… × 10 −21 J.
falls on a metal of threshold energy
= 10 × 10 −3 kg, v = 90ms−1) [2020, 2 Sep Shift-II]
3.0 eV, the de- Broglie wavelength
Uncertainty in position, Ans. (222)
of emitted electrons is …… Å.
h 1
[Round off to the nearest integer] ∆x = × For photoelectrons, its kinetic energy
4 π m × ∆v (with uncertainty) will be
[Use: 3 = 1.73, h = 6.63 × 10 −34 Js hc
. × 10 −34
663 1 KE = E − E a = − E0
= ×
m e = 9.1 × 10 −31 kg,
m λ
4 × 3.14 −3  5 
(10 × 10 ) ×  90 ×  6.63 × 10 −34 × 3 × 10 8
c = 3.0 × 10 8 ms −1 , 1 eV = 1.6 × 10 −19 J]  100  = . × 10 −19 J
− 441
300 × 10 −9
[2021, 16 March Shift-I] = 1.17 × 10 −33 m ~− 1 × 10 −33 m
= 222 × 10 −21 J
Ans. (9) λ = Wavelength of photon
Given wavelength, if incident light
33 A proton and a Li 3+ nucleus are = 300 nm = 300 × 10 −9 m
(λ) = 248 nm = 2480 Å accelerated by the same potential. E 0 = Threshold energy
Threshold energy = 30. eV If λ Li and λ P denote the de-Broglie = Work function of sodium metal
We know, for electron de-Broglie wavelengths of Li 3 + and proton . × 10 −19 J
= 441
wavelength is given by λ
λ=
h respectively, then the value of Li 35 The de Broglie wavelength of an
mv λP
electron in the 4th Bohr orbit is
λ=
h is x × 10 −1 . The value of x is ......... . [2020, 9 Jan Shift-I]
2m (KE)
(Rounded off to the nearest (a) 6 πa0 (b) 2 πa0 (c) 8 πa0 (d) 4 πa0
KE = q × V (where,q = charge of particle) Ans. (c)
integer)
V = voltage applied
h (Mass of Li 3 + = 8.3 mass of proton) The de-Broglie wavelength of an
λ= electron,
2m (qV ) [2021, 24 Feb Shift-I]
h h
Ans. (2) λ = , or
Putting mass of electron, p mv
me = 9.1 × 10 −31 kg Given, mass of Li 3+ = 83
. times of mass
But, from the Bohr’s postulate of
Charge of electron,q = 16 . × 10 −19 C of proton formula,
quantisation of angular momentum of
150 De-Broglie wavelength, nh
λ= Å …(i) electrons,l = mvr = ,
V h
λ= 2π
2mqV nh
We know, ∴ mv =
E applied = φ + KEmax …(ii) Here, h = Planck’s constant 2πr
h 2 πr
where, = 6.624 × 10 −34 J-s Upon substitution, λ = = ,
φ = threshold energy  nh  n
m = Mass of atom  
φ = 3 eV  2 πr 
q = Charge (or number of electrons)
12400 12400
E applied = = = 5 eV h where, r is the radius of orbits in Bohr
λÅ 2480 λ Li = …(i) n2a 0
2mLi (3 e) v model =
Putting value in Eq. (ii), Z
h
λP = …(ii) 2 π × n2 × a 0 2 πna 0
5 = 3 + KEmax 2mP (e) v ∴ λ= = = 8 πa 0
⇒ KEmax = 2 eV n× Z Z
Now, Eq. (i) divided by Eq. (ii), we get, Z = 1 for hydrogen
Voltage = 2
λ Li mP (e) v  
150 = n = 4 (given) 
λe = = 86
. Å [Eq. (i)] λP mLi (3e) v
2
We know that mLi = 83
. mp 36 What is the work function of the
Nearest integer = 9
λ Li mP × e × V metal, if the light of wavelength
=
32 A ball weighing 10 g is moving with λP . mP × 3e × V
83 4000 Å generates photoelectron of
a velocity of 90 ms −1 . If the 1 1 velocity6 × 10 5 ms −1 from it?
uncertainity in its velocity is 5%, = = = 0.2
. ×3 5
83 (Mass of electron = 9 × 10 −31 kg
then the uncertainty in its position
is ……… × 10 −33 m (Rounded off to
= 2 × 10 −1 Velocity of light = 3 × 10 8 ms −1
the nearest integer). [Given,
Hence, x × 10 −1, x = 2 Planck’s constant = 6.626 × 10 −34 Js
h = 6.63 × 10 −34 J -s] Charge of electron
[2021, 26 Feb Shift-II]
34 The work function of sodium metal = 1.6 × 10 −19 JeV −1 )
is 4.41 × 10 −19 J. If photons of (a) 4.0 eV (b) 2.1 eV (c) 0.9 eV (d) 3.1 eV
Ans. (1)
wavelength 300 nm are incident on [2019, 12 Jan Shift-I]
According to Heisenberg’s uncertainty
the metal, the kinetic energy of the
equation,
ejected electrons will be
Atomic Structure 33

Ans. (b) Ans. (d) 4 3

(a) λ (b) λ
Work function of metal (φ) = hν0 For photoelectric effect, 9 4
(i) KE = E − E 0 2 1
where, ν0 = threshold frequency (c) λ (d) λ
1 where,KE = Kinetic energy of ejected 3 2
Also, me v2 = hν − hν0
2 electrons. Ans. (a)
1 E = Energy of incident light = hν The expression of kinetic energy of
or me v2 = hν − φ …(i)
2 E 0 = Threshold energy = hν0 photo electrons,
1 hc ν = Frequency of incident light 1
me v2 = −φ …(ii) KE = mv2 = E − E 0
2 λ ν0 = Threshold frequency 2
Given : λ = 4000 Å = 4000 × 10 −10 m When,KE> > E 0 , the equation becomes,
KE
v = 6 × 10 5 ms −1, 1
KE = mv2 = E
0
me = 9 × 10 −31 kg, c = 3 × 10 8 ms −1 E0 E 2
h = 6626
. × 10 −34
Js 1 2 hc p2 hc
⇒ mv = ⇒ 2 =
2 λ 2m λ
Thus, on substituting all the given values Slope = ± 1, intercept = − E 0
1 1
in Eq. (i), we get So, option (a) is correct. ⇒λ = hc × 2m2 × 2 ⇒λ ∝ 2
1 p p
× 9 × 10 −31 kg × (6 × 10 5 ms −1 )2 (ii) KE of ejected electrons does not
hc
2 depend on the intensity of incident E= = energy of incident light.
light. λ
6.626 × 10 −34 J s × 3 × 10 8 ms−1 E 0 = threshold energy or work functions,
= −φ
4000 × 10 −10 m KE
1 2 1 (mv)2 1 p2
−21 2 −2 −19
mv = × = × 2
∴φ = 1.62 × 10 kgm s − 4.96 × 10 J 2 2 m2 2 m
= 3.36 × 10 −19 J [1 kg m2 s−2 = 1 J] Q p = momentum = mv
0
= 2.1 eV Intensity of light As per the given condition,
2
So, option (b) is correct. λ2 p 
37 Which of the graphs shown below =  1 
(iii) When, number of ejected electrons is λ 1  p2 
does not represent the relationship plotted with frequency of light, we get
2
between incident light and the λ2 p   2
2
4
⇒ =  =  =
electron ejected from metal λ  1.5 × p   3 9
Number
surface? [2019, 10 Jan Shift-I] of e–’s 4 Qλ 1 = λ 
⇒ λ2 = λ  p = p
K.E. of 9  1 
e ss
0
Frequency of light (n) 39 The de-Broglie wavelength (λ )
(a)
So, option (c) is also correct. associated with a photoelectron
0
Energy of light (iv) KE = hν − hν0 varies with the frequency (ν) of the
incident radiation as,
K.E. of KE
[ν 0 is threshold frequency]
ess 1 1
0 ν0 ν (a) λ ∝ 1
(b) λ ∝ 3
(b) (ν − ν 0 )4 (ν − ν 0 ) 2
1 1
0
Intensity of light (c) λ ∝ (d) λ ∝
Slope = + h, intercept = − hν0 (ν − ν 0 ) 1

So, option (d) is not correct. (ν − ν 0 ) 2

Number
of ess [2019, 11 Jan Shift-II]
38 If p is the momentum of the Ans. (d)
(c) fastest electron ejected from a de-Broglie wavelength (λ) for electron is
metal surface after the irradiation given by
0 h
Frequency of of light having wavelength λ, then λ= ...(i)
light 2 m K.E
for 1.5 p momentum of the
K.E. of photoelectron, the wavelength of Also, according to photoelectric effect
ess the light should be KE = hν − hν0
On substituting the value of KE in Eq (i),
(d) (Assume kinetic energy of ejected we get
photoelectron to be very high in h 1
0 λ= ⇒ λ∝
Frequency of comparison to work function) 2m × (hν − hν0 ) ( ν − ν0 ) 1 / 2
light [2019, 8 April Shift-II]
34 JEE Main Chapterwise Topicwise Chemistry

40 If the de-Broglie wavelength of the TOPIC 4 For 2p orbital, n = 2 and l = 1

electron in n th Bohr orbit in a Angular node (l ) = 1
Quantum
hydrogenic atom is equal to 1.5 πa 0 Therefore, number of radial nodes
(a 0 is Bohr radius), then the value
Mechanical Model =2− 1− 1=0
of n/ Z is It has one angular and zero radial node.
(a) 1.0 (b) 0.75 (c) 0.40 (d) 1.50
42 The value of magnetic quantum For 3p orbital, n = 3, l = 1
[2019, 12 Jan Shift-II] number of the outermost electron Angular node (l ) = 1
Ans. (b) of Zn + ion is [2021, 31 Aug Shift-II] It has one angular and one radial node.
Circumference Ans. (0) For 3s orbital, n = 3, l = 0
Number of waves =
Wavelength The configuration of No. of angular node (l ) = 0
2πr Zn+ = 1s 2 2s 2 2p6 3s 2 3p6 3d 10 4s 1 No. of radial node ⇒n − l − 1
n= ⇒ 2πr = nλ ...(i)
λ The outermost electron is in s-orbital. = 3 −0 − 1 = 2 = 2
Also, we know that radius (r) of an atom For s-orbital, azimuthal quantum Hence, for 3s-orbital has no angular
is given by number (l ) = 0 node and 2 radial nodes.
a n2 Magnetic quantum number, m = − l to + l
r= 0
Z For l = 0, m = 0 45 A certain orbital has n = 4 and
Thus, Eq. (i) becomes ml = − 3. The number of radial
n2
43 Ge (Z = 32) in its ground state
2 πa 0 = nλ ...(ii) nodes in this orbital is …… (Round
Z electronic configuration has x off to the nearest integer).
n2 completely filled orbitals with [2021, 17 March Shift-I]
∴ 2 πa 0 = n (1.5 πa 0 )
Z ml = 0. The value of x is Ans. (0)
[2021, 31 Aug Shift-I]
[Given, λ = 1 .5 πa 0 ] Given, n = 4, ml = − 3, so l = 3
n 1.5πa 0 1.5 Ans. (7)
= = = 0.75 Possible value of l = 0, 1, 2, 3
Z 2 πa 0 2 Ge (Z = 32) electronic configuration is As m = − 3 is possible only forl = 3
Ge (32) 1s2 2s2 2p6 3s2 For l = 3, ml = − 3, − 2, − 1 , 0, 1, 2, 3
41 A stream of electrons from a Orbital
So, this is4f-orbital.
heated filament was passed Number of radial nodes = n − l − 1
Value 0 0 –1 0 1 0
between two charged plates kept of ml = 4 − 3 − 1= 0
at a potential difference V esu. If (magnetic quantum
number) So, there is no radial node in4f orbital.
e and m are charge and mass of an 3p 6
4s2
3d10 4p2
electron, respectively, then the 46 The number of orbitals with n = 5,
value of h/λ (where, λ is wavelength ml = +2 is ……… . (Round off to the
associated with electron wave) is –1 0 1 0 –2 –1 0 1 2 –1 0 +1
nearest integer).
given by [JEE Main 2016] For s-orbitals (1s , 2s , 3s and 4s) [2021, 16 March Shift-II]
(a) 2 meV (b) meV ml = 0 {2 × 0 }
Ans. (3)
(c) 2 meV (d) meV For p-orbitals (2p, 3p) ml = 0
Given, n = 5, ml = + 2
Ans. (c) {(−1) × 2 + 0 × 2 + (+1) × 2 = 0 }
For n = 5, possible value ofl = 0, 1, 2,3, 4
As you can see in options, energy term is For d-orbitals (3d) ml = 0
For l = 0, ml = 0
mentioned hence, we have to find out (−2) × 2 + (−1) × 2 + 0 × 2
h   l = 1, ml = − 1, 0, 1
relation between and energy. For this, (+ 1) × 2 + (+2) × 2 = 0 
λ l = 2, ml = − 2, − 1, 0, 1, 2
we shall use de-Broglie wavelength and ∴ Completely filled orbitals with ml = 0
are seven (7). l = 3, ml = − 3, − 2, − 1, 0, 1, 2, 3
kinetic energy term in eV.
de-Broglie wavelength for an electron l = 4, ml = − 4, − 3, − 2, − 1, 0, 1, 2, 3, 4
h 44 A certain orbital has no angular Possible value of ml for a given value of l
(λ) =
p h
nodes and two radial nodes. The = 0, ± 1, ± 2, ± 3 .... ± l
⇒ p= …(i) orbital is [2021, 18 March Shift-I]
λ So, number of orbitals having n = 5 and
Kinetic energy of an electron = eV (a) 2s (b) 3s ml = ± 2 are 3.
p2 (c) 3p (d) 2p
As we know that, KE =
2m Ans. (b) 47 Given below are two statements:
p2 As, we know, one is labelled as Assertion (A) and
∴ eV = or p = 2meV …(ii)
2m For 2s orbital, n = 2, l = 0 the other is labelled as Reason (R).
From equations (i) and (ii), we get Angular node (l ) = 0 Assertion (A) In T lI 3 , isomorphous
h
= 2meV Radial nodes = n − l − 1 to CsI 3 , the metal is present in +1
λ ⇒ 2−0 − 1= 1 oxidation state.
Atomic Structure 35

Reason (R) Tl metal has fourteen Note l = 0 for s-orbital, l = 1 for p-orbital, Ans. (d)
f-electrons in the electronic l = 2 for d-orbital and l = 3 for f-orbital. The correct plot for3s-orbital is
2.0
configuration. 3rd peak

ak
4πr 2 R 2 n, l(r)
49 The spin only magnetic moment 1.5

ak

pe
In the light of the above

pe

d
of a divalent ion in aqueous

2n
Ist
statements, choose the most 1.0
appropriate answer from the solution
0.5
options given below. (atomic number = 29) is ……… BM.
[2021, 25 Feb Shift-II] 0
[2021, 26 Feb Shift-II] 5 10
(a) A is correct but R is not correct. Ans. (2) r(A)
(b) Both A and R are correct and R is the − For 3s,
correct explanation of A. Z = 29 [Cu] −→ Cu2 + = [Ar] 3d 9
2e
value of l = 0
(c) A is not correct but R is correct 3d 9 = , value of n = 3
(c) Both A and R are correct but R is not Number of peak = n − l = 3 − 0 = 3
correct explanation of A. Number of unpaired electron, n = 1
In graph D, three peaks are present, so
∴ Spin only magnetic moment, this is the correct plot for3s-orbital.
Ans. (b)
µ = n(n + 2)BM
Assertion (A) is correct. TlI3 and C sI3 are
51 The number of subshells
the triiodide, I−3 (polyhalide) compounds = 1(1 + 2) BM
of Tl + and Cs+ ions. Due to inert pair associated with n = 4 and m = −2
= 3 BM
effect of group -13 elements,Tl + is more quantum numbers is
stable thanTl 3+ . Cs and Tl belong to the = 1.73 BM −
~ 2 BM [2020, 2 Sep Shift-II]
same period (6th). (a) 8 (b) 2 (c) 16 (d) 4
Sizes of Cs+ and Tl + are nearly same. 50 The plots of radial distribution Ans. (b)
So, geometrical network and lattice functions for various orbitals of Principal quantum number (n) signifies
pattern of both CsI3 and TlI3 are same hydrogen atom against ‘r’ are given the shell or orbit number.
(bcc lattice). CsI3 and TlI3 are also able to
below. [2021, 25 Feb Shift-I] From the number of values of azimuthal
form mixed crystals when crystallisation
quantum number (l ), we can calculate
is carried out from a mixture of
number of subshells present in a shell as,
n, l(r)

saturated solutions of CsI3 and TlI3. 8

These properties enableTlI3 and CsI3 to l = 0 .... (n − 1)
4πr 2 R 2

be isomorphous crystals. (A) 4 So, when n = 4

Reason (R) is also correct. Electronic The permissible values ofl and subshells
configuration of Cs (Z = 55) and Tl (Z = 81) 0 are
5 10
as follows r(A) l = 0→ s-subshell
C s : [54 Xe] 6s 1 = 1 → p-subshell
55 3
n, l(r)

14 10 2 1 = 2 → d-subshell
81Tl : [54 Xe]4f 5d 6s 6p
2 = 3→f-subshell
4πr 2 R2

So, Tl has fourteenf-electrons in the

anti-penultimate (4th) shell. (B) 1 But, here values ofl are restricted by the
value of magnetic quantum number,
A and R are individually correct and R is 0
5 10 m = −2, where, m depends onl as
the correct explanation of A.
r(A) m = − l .... 0 .... + l
48 The orbital having two radial as well So, m = − 2 value is possible for two
as two angular nodes is 3 subshells, viz,l = 3 (f-subshell) and l = 2
n, l(r)

[2021, 26 Feb Shift-I]

(d-subshell) only.
2
l = 3 ⇒m = − 3, − 2 − 1, 0, + 1, + 2, + 3
4πr 2 R 2

(a) 3p (b) 4f (c) 4d (d) 5d (C)

1 l = 2 ⇒m = − 2, − 1, 0, + 1, + 2
Ans. (d)
0
Number of radial nodes = (n − l − 1) 5 10
r(A) 52 Consider the hypothetical situation
[n = principal quantum number,
where the azimuthal quantum
l = azimuthal quantum number]
2.0 number, l takes values 0, 1, 2, ……
Number of angular nodes = l
n, l(r)

1.5 n+ 1, where n is the principle

(n − l − 1) l
(D) quantum number. Then, the
4πr 2 R 2

(a) 3p(n = 3, l = 1) ⇒ 1 1 1.0

0.5 element with atomic number
(b) 4f (n = 4, l = 3) ⇒ 0 3 [2020, 3 Sep Shift-II]
0
(c) 4d (n = 4, l = 2) ⇒ 1 2 5 10 (a) 8 is the first noble gas
(d) 5d (n = 5, l = 2) ⇒ 2 2 r(A) (b) 13 has a half-filled valence subshell
So, 5d-orbital has two radial as well as The correct plot for 3s–orbital is (c) 9 is the first alkali metal
two angular nodes (option-d). (a) (A) (b) (B) (c) (C) (d) (D) (d) 6 has a 2p-valence subshell
36 JEE Main Chapterwise Topicwise Chemistry

Ans. (b) and each such combination is (d) The total energy of the electron is
Hypothetical situation : associated with an orbital. Each orbital maximum when it is at a distancea 0
can occupy a maximum of two electrons, from the nucleus.
Azimuthal quantum number
having a different value of spin quantum Ans. (d)
(l ) = 0 − (n − 1)
1 1
n = Principal quantum number number (ms ), which are + or − . Statement (d) is incorrect. For 1s-orbital
2 2
For, n = 1 l = 0, 1, 2 radial probability density (R2 ) against r is
∴ Number of orbitals associated with given as:
↓ ↓ ↓ n = 5 is n2 = 25. Each of those orbitals can
1s 1p 1d 1
be associated with ms = + as well as
1s 2 1p6 1d 10 2
Number of electrons in s-orbital = 2 1
ms = − .
Number of electrons in p-orbital = 6 2 R2
1s
Number of electrons ind-orbital = 10 ∴ Answer = 25
Z = 13 (Half-filled valence sub-shell) r
For n = 1, 1s 2 1p6 1d 5 (Z = 13)
55 The quantum number of four
electrons are given below: For 1s-orbital, probability density
Number of electrons in 1d-orbital are 5.
1 decreases sharply as we move away
(It is half-filled). I. n = 4, l = 2, ml = − 2, m s = − from the nucleus.
Element with atomic number 9 is not 2
first 1 The radial distribution curves obtained
alkali metal but a halogen 1s 2 2s 2 2p5 . II. n = 3, l = 2, ml = 1, m s = + by plotting radial probability functions
2
First noble gas has atomic number 2 1 vs r for 1s-orbital is
III. n = 4, l = 1, ml = 0, m s = +
not 8. 2
1
53 The correct statement about IV. n = 3, l = 1, ml = 1, m s = −
2

4πrR2
probability density (except at
The correct order of their
infinite distance from nucleus) is
[2020, 5 Sep Shift-II]
increasing energies will be
(a) it can be zero for 1s orbital [2019, 8 April Shift-I]
(b) it can be negative for 2p orbital (a) IV < III < II < I (b) I < II < III < IV r
(c) it can be zero for 3p orbital (c) IV < II < III < I (d) I < III < II < IV The graph initially increases and then
(d) it can never be zero for 2s orbital Ans. (c) decreases. It reaches a maximum at a
Ans. (c) Smaller the value of (n + l ), smaller the distance very close to the nucleus and
energy. If two or more sub-orbits have then decreases. The maximum in the
[R(r)]2 same values of (n + l ), sub-orbits with curve corresponds to the distance at
lower values of n has lower energy. The which the probability of finding the
3p (n + l ) values of the given options are as electron in maximum.
follows :
r
I. n = 4, l = 2 ; n + l = 6 57 The graph between | ψ | 2 and r
φ (Probability density) can be zero for 3p
2
II. n = 3, l = 2; n + l = 5 (radial distance) is shown below.
orbital other than infinite distance. III. n = 4, l = 1, n + l = 5 This represents [2019, 10 April Shift-I]
Since, n = 3, l = 1 for 3p orbital, the IV. n = 3, l = 1, n + l = 4
number of radial nodes = 3 − 1 − 1 = 1 Among II and III, n = 3 has lower value of
energy. Thus, the correct order of their
54 The number of orbitals associated increasing energies will be 2
|Ψ|
with quantum numbers n = 5, IV < II < III < I
1
m s = + is
2 [2020, 7 Jan Shift-I] 56 Which one of the following about
(a) 25 (b) 50 (c) 15 (d) 11 an electron occupying the
Ans. (a) 1s-orbital in a hydrogen atom is r
According to quantum mechanical atom incorrect? (The Bohr radius is (a) 1s-orbital
model, for each value of n (principal represented by a 0 ) (b) 2p-orbital
quantum number), there are ‘n’ different [2019, 9 April Shift-II] (c) 3s-orbital
values of l (azimuthal quantum number), (a) The electron can be found at a (d) 2s-orbital
i.e. l = 0, 1, 2, …, (n − 1). And, for each distance2a 0 from the nucleus.
value of l, there are2l + 1 different values Ans. (d)
(b) The magnitude of the potential
of ml (magnetic quantum number), i.e. energy is double that of its kinetic The graphs between | ψ|2 and r are radial
ml = 0, ±1, ±2 … ±l. energy on an average. density plots having (n − l − 1) number of
∴Total number of possible combinations (c) The probability density of finding the radial nodes. For 1s, 2s, 3s and 2
of n, l and ml , for a given value of n is n2 , electron is maximum at the nucleus. p-orbitals these are respectively.
Atomic Structure 37

a IV. The plot of ψ vs r for various

Y (x) azimuthal quantum numbers,
For 1s-orbital
|Ψ|2 number of radial node = 1–0–1=0 b +x → shows peak shifting towards
← –x higher r value.
[2019, 9 Jan Shift-II]
c (a) I, III (b) II, III
r
(c) I, II (d) I, IV
The graph between wavefunction (ψ) and
distance (r) from the nucleus helps in Ans. (d)
determining the shape of orbital. nh
|Ψ|2 For 2s-orbital (I) Angular momentum, mvr =
number of radial 2π
node = 2–0–1=1
59 Among the following, the energy of ⇒mvr ∝ n ∝ distance from the
2s-orbital is lowest in nucleus
r [2019, 12 April Shift-II]
(II) This statement is incorrect as size of
(a) K (b) H (c) Li (d) Na an orbit
Ans. (a) ∝ Azimuthal quantum number (l )
The energy of2s-orbital is lowest in (Qn = constant)
|Ψ|2 For 3s-orbital
number of radial K(potassium). An orbital gets larger as (III) This statement is incorrect as at
node = 3–0–1=2 the principal quantum number n ground state,
increases. n = 1, l = 0
r Correspondingly, the energy of the ⇒ Orbital angular momentum (wave
electron in such an orbital becomes less mechanics)
negative, meaning that the electron is h
less strongly bound and has less energy. = l (l + 1) = 0 [Ql = 0]
2π
|Ψ|2 For 2p-orbital The graph of principal quantum number
number of radial node with atomic number is (IV) The given plot is
= 2–1–1=0
l=0 (n=1)
Principal quantum

l=1 (n=2)
r 2
l=2 (n=3)
number

Thus, the given graph between | ψ|2 and r

represents 2s-orbital. ψ
l=3 (n=4)

58 The electrons are more likely to be 1 2s

found [2019, 12 April Shift-I] 1 25 50 75 100
Atomic number r

a Ψ (x) 60 Which of the following combination 61 The correct set of four quantum
of statements is true regarding the numbers for the valence electrons
b x interpretation of the atomic orbitals? of rubidium atom [Z = 37] is
–x [JEE Main 2014]
I. An electron in an orbital of high
1 1
angular momentum stays away (a) 5, 0, 0, + (b) 5, 1, 0, +
c 2 2
from the nucleus than an
1 1
electron in the orbital of lower (c) 5, 1, 1, + (d) 5, 0, 1, +
2 2
angular momentum.
(a) in the region a and c II. For a given value of the principal Ans. (a)
(b) in the region a and b quantum number, the size of The electronic configuration of rubidium
(c) only in the region a the orbit is inversely atom (Z = 37) is given by
(d) only in the region c Rb = [Kr] 5 s 1
proportional to the azimuthal
Ans. (a) quantum number. Hence, the quantum numbers for 5 s 1
The electrons are more likely to be found III. According to wave mechanics, electron is given by
in the regiona and c. At b, wave function the ground state angular n = 5, l = 0, m = 0,
becomes zero and is called radial nodal h 1 1
surface or simply node. momentum is equal to . s = + or −
2π 2 2
04
Chemical Bonding and
Molecular Structure
TOPIC 1 (B) O2 (b) B(OH) 3 is acidic and Al(OH)3 is
amphoteric in nature.
Type of Bonds, Bond O O
(c) Both NaOH and Ca(OH)2 are basic
Parameter and Resonance ∴O2 has 1π-bond and has 1
hydroxides.
structure.
(d) Both Be(OH)2 and Al(OH) 3 are
01 The interaction energy of London (C) SO2
amphoteric hydroxides.
forces between two particles is S S+ S+ Hence, onlyB(OH) 3 and Al(OH) 3
proportional to r x , where r is the O have different nature.
(I) (II)
distance between the particles.
The value of x is ∴SO2 has 1π-bond and has 2 04 Given below are two statements:
[2021, 26 Aug Shift-II] canonical forms. One is labelled as Assertion (A) and
(a) 3 (b) − 3 (c) − 6 (d) 6 (D) CO23− the other is labelled as Reason (R).
Ans. (c) O O Assertion (A) Dipole-dipole
In London forces, interaction energy in C C C interactions are the only
inversely proportional to the sixth power O non-covalent interactions,
of the distance between two interacting resulting in hydrogen bond
particles (1 / r 6 or r −6 ). ∴ CO23− has 1π-bond and has 3
canonical forms.
formation.
∴ x is –6. Reason (R) Fluorine is the most
Among SO3, O2 , SO2 and CO23 − , only
CO23 − has only one π-bond and electronegative element and
02 Identify the species having one
maximum number of canonical hydrogen bonds in HF are
π - bond and maximum number of forms. symmetrical.
canonical forms from the following
[2021, 25 July Shift-II]
In the light of the above
03 The set in which compounds have statements, choose the most
(a) SO 3 (b) O2 different nature is
(c) SO2 (d) CO2− appropriate answer from the
3 [2021, 20 July Shift-I]
Ans. (d) options given below.
(a) B(OH) 3 and H3 PO 3 [2021, 26 Feb Shift-I]
Canonical form of (b) B(OH) 3 and Al (OH) 3 (a) A is false but R is true.
O O (c) NaOH and Ca(OH)2 (b) Both A and R are true and R is the
(A) S S+ S+ (d) Be(OH)2 and Al (OH) 3 correct explanation of A.
O Ans. (b) (c) A is true R is false.
(I) (II) (a) Both are acidic in nature. (d) Both A and R are true but R is not the
O correct explanation of A.
B(OH) 3 is orthoboric acid. It can
accept a pair of electrons from Ans. (a)
S+
Lewis bases and hence, act as Lewis Assertion is false but Reason is true.
O acid. Corrected Assertion Diple-dipole
(III)
H3PO3 is (phosphorus acid) diprotic interactions are purely covalent
∴SO3 has 2π-bonds and has 3 acid as it readily ionises two interactions of dipolar covalent bonds.
number of canonical forms. protons.
Chemical Bonding and Molecular Structure 39
1
Ends of dipoles of a polar covalent bonds (I) ion-ion interaction energy ∝ 08 The potential energy curve for the
possess partial charges ( δ + and δ − ) [column -B(a)] r
H2 molecule as a function of
which are less than unit electronic (II) dipole-dipole interaction energy
charge, e = 1.6 × 10 −19 C. 1
internuclear distance is
∝ 3 [2020, 5 Sep Shift-I]
r
05 The dipole moments of CCl 4 , CHCl 3 [column-B (c)] (for stationary polar Energy

and CH4 are in the order molecules)

1 (a)
[2020, 7 Jan Shift-I] ∝ 6 [column-B (d)] (for rotating
(a) CCl4 < CH4 < CHCl3 r
polar molecules)
(b) CH4 < CCl4 < CHCl3 Internuclear
(c) CH4 == CCl4 < CHCl3 (III) London dispersion interaction distance
1
(d) CHCl3 < CH4 == CCl4 energy ∝ 6 [column-B (d)]
r Energy
Ans. (c) [dipole induced dipole
1
H Cl interaction energy ∝ 6 ] (b)
r
C C So, the matching is,
Internuclear
H H Cl Cl (I)–(a), (II)–(c), (III)–(d)] option (a).
distance
H Cl
CH4 (µ=0) CCl4 (µ=0)
07 The intermolecular potential Energy
energy for the molecules A, B, C
Individual bonds have some and D given below suggests that: (c)
dipole moment (µ), but
overall µ=0, due to mutual Interatomic distance (pm)
cancellation of dipole moments Internuclear
50 100 150
as the structures are symmetrical. 0 distance
Potential energy (kJ mol–1)

H –100 Energy

–200 (d)
C
Cl Cl –300
Cl A–D Internuclear
–400
CHCl3 (µ≠0) A–C distance
A–A
–500
The resultant of three A–B Ans. (c)
C  Cl bond dipoles is –600
not cancelled but When the distance of hydrogen nucleus
enhanced by C  H [2020, 4 Sep Shift-I] is decreasing at a particular point,
bond dipole. (a) A-B has the stiffest bond energy is minimum. At this point
(b) D is more electronegative than other potential energy will be least. It is the
atoms point when bond formation taken place.
06 Match the type of interaction in
column A with the distance (c) A-A has the largest bond enthalpy Minimum potential
energy
Energy

(d) A-D has the shortest bond length

dependence of their interaction
Ans. (a)
energy in column B :
(a) A - B has stiffest bond.
A B This is correct because the
(I) Ion-ion (a) 1 potential energy of A - B has
maximum negative value [between Internuclear distance
r
1 −500 to −600]. More negative is Hence, option (c) is correct.
(II) Dipole-dipole (b)
the potential energy means high
r2 energy is released. Higher the 09 Arrange the following bonds
(III) London (c) 1 released energy higher is the according to their average bond
dispersion r3 stability and hence the stiffness
bond. energies in descending order
(d) 1
(b) D is more electronegative than C Cl, C Br, C F, C I
r6 [2020, 8 Jan Shift-II]
other atoms, it is incorrect.
[2020, 2 Sep Shift-II] (c) A - A has the largest bond enthalpy, (a) C F > C Cl > C Br > C I
(a) (I)-(b), (II)-(d), (III)-(c) it is incorrect because value of (b) C Br > C I > C Cl > C F
(b) (I)-(a), (II)-(b), (III)-(d) potential energy is more negative (c) C I > C Br > C Cl > C F
(c) (I)-(a), (II)-(b), (III)-(c) in A - B. (d) C Cl > C Br > C I > C F
(d) (I)-(a), (II)-(c), (III)-(d) (d) A - D has shortest bond length, it is
incorrect because inter molecular Ans. (a)
Ans. (a) distance in between A - D more The correct descending order of bonds
When r is the inter-nuclear separation, than 150 (pm) which is height in all. according to their average bond
40 JEE Main Chapterwise Topicwise Chemistry

energies is as follows : OH OH (c) two sigma, one pi

C F > C  Cl > C Br > C I (d) two sigma, two pi
Bond length is inversely proportional to Ans. (a)
bond energy. So, bond length decreases (iii) (iv)
as bond energy increases. CaC2 º Ca2+
+ C22 −
Carbide ion
10 Which of the following compounds In carbide ion, two carbon atoms are
contain(s) no covalent bond(s)? OH SH joined by triple bond (It is isoelectronic
(a) Only (i) (b) (i) and (ii) with N2).
KCl, PH3 , O 2 , B 2H6 , H2SO 4
[JEE Main 2018] (c) Only (iii) (d) (iii) and (iv) — C≡≡ C —
(a) KCl, B2H6 , PH3 (b) KCl, H2 SO 4 Ans. (d) with two π and one σ-bonds.
(c) KCl (d) KCl, B2H6 OH SH
Ans. (c) 15 The charge/size ratio of a cation
KCl is the only ionic compound. The In quinol and thioquinol, determines its polarising power.
structure of PH3, O2 , B2H6 and H2SO4 are OHand Which one of the following
given below OH SH sequences represents the
increasing order of the polarising
Covalent SHgroups do not cancel their dipole power of the cationic species,
P bond moments and hence exists as different
H H
O O
conformations. K + , Ca 2+ , Mg 2+ , Be 2+ ? [AIEEE 2007]
H (O2)
(a) Mg2 + < Be2+ < K + < Ca2+
(PH3) Covalent H H
Bonds Cl Cl
(b) Be2+ <K + <Ca2+ <Mg2+
H H 1.33Å H O O
(c) K + <Ca2+ <Mg2+ <Be2+
1.19Å
120° B 97° B
(d) Ca2+ <Mg2+ < Be2+ <K +
H H H
Ans. (c)
H H H Higher the charge/size ratio, larger is the
H H H Cl CN O O polarising power.
B B µ=0 µ=0 H H
B B ∴ K+ < Ca2 + < Mg2 + < Be2 +
H H H 2 different conformers
[∴ µ ≠ 0]
H H (B2H6) H Banana bond
[same as thioquinol] 16 Lattice energy of an ionic
O compound depends upon
[AIEEE 2005]
S 13 Among the following, the maximum
(a) charge on the ion and size of the ion
HO OH O covalent character is shown by the (b) packing of ions only
compound [AIEEE 2011]
(c) size of the ion only
Sulphuric acid
(H2SO4) (a) FeCl2 (b) SnCl2 (d) charge on the ion only
(c) AlCl3 (d) MgCl2
Ans. (a)
All bond between S and O atom are Ans. (c)
covalent bonds. Greater the charge and smaller the
Covalent character is favoured by Fajan’s radius, larger the polarising power and
rule. thus, greater the covalent nature. This
11 The correct statement for the (i) Larger the charge on the ions, leads to increase in lattice energy.
molecule CsI 3 is [JEE Main 2014]
(ii) Smaller the size of cations,
(a) It is a covalent molecule (iii) Larger the size of anions, 17 Which one of the following pairs of
(b) It contains Cs+ and I−3 (iv) Cation with 18-electron structure molecules will have permanent
(c) It contains Cs3+ and I− ions (e. g., Cu+ ),
dipole moments for both
(d) It contains Cs+ , I− and latticeI2 then larger the polarising power and the
molecule covalent character is favoured. members? [AIEEE 2003]

Ans. (b) In all the given compounds, anion is (a) SiF4 and NO2
+ same (Cl − ), hence polarising power is (b) NO2 and CO2
CsI3 contains Cs and I−3 ions. decided by size and charge of cation. (c) NO2 and O 3
Al 3+ with maximum charge and smallest (d) SiF4 and CO2
12 For which of the following molecule size has maximum polarising power
significant µ ≠ 0 ? Ans. (c)
[JEE Main 2014] hence, AlCl 3 is maximum covalent.
Both NO2 and O3 have angular geometry,
Cl Cl
14 The number of types of bonds thus possess permanent dipole moment.
WhileSiF4 possesses regular tetrahedral
between two carbon atoms in
structure and CO2 possesses a linear
(i) (ii) calcium carbide is [AIEEE 2011] structure. In SiF4 and CO2 , the individual
(a) one sigma, two pi dipoles on theSi F and O bonds cancel
(b) one sigma, one pi and the molecules have no diple
Cl CN moment.
Chemical Bonding and Molecular Structure 41
µ1 µ2 µ1 µ2 O
N O Ans. (d)
O µ O O µ O Hybridisation = Number of sigma bonds
(iv) CO32– = C Trigonal planar
total total O O + number of lone pair of electrons +
(µ1 + µ2) (µ1 + µ2)
3 molecules/ions i.e. (i), (ii) and (iv) have number of coordinate bond.
Thus, µ total ≠ 0 Thus, µ ≠0
total non-pyramidal shape. For NO2− hybridisation = 2 sigma NO
bonds + 1 lone pair onN = 3; so NO2− is
µ1 µ2 F sp2 -hybridised.
µ4 20 Match List I and List II.
—
O— C — µ3 µ1
— O NO–2 N
Si List I List II
m total = 0 (µ1 = – µ2) F µ2 F O O–
(Species) (Hybrid
F µ resultant orbitals) For NO2+ hybridisation = 2 sigma NO
( µ 1 + µ2 + µ3 = – µ4 ) 3 2 bonds = 2;
(A) SF4 (i) sp d
\µ =0 so NO2+ sp-hybridised.
total (B) IF5 (ii) d2 sp 3 ⊕
NO+ O N O
(C) NO2+ (iii) sp 3d 2

+ For NO+4 Hybridisation = 4 sigma NH

18 Select the correct statement. (D) NH4 (iv) sp 3
[AIEEE 2002]
bonds = 4;so NH+4 is sp3-hybridised.
(v) sp +
(a) When a covalent bond is formed, H
transfer of electrons takes place [2021, 22 July Shift-II] NH+
4 N
(b) Pure H2O does not contain any ion A B C D H H
(c) A bond is formed when attractive (a) (i) (ii) (v) (iii) H
forces overcome repulsive forces
(b) (ii) (i) (iv) (v) Therefore, hybridisation of N in NO2− ,
(d) HF is less polar than HBr NO2+ , NH+4 are sp2 , sp, sp3 respectively.
(c) (iii) (i) (v) (iv)
Ans. (c)
(d) (iv) (iii) (ii) (v)
A bond is formed when attractive forces 22 The number of lone pairs of
Ans. (c)
[NA − e A and NB − e B or NA − e B and electron on the central I atom in I −3
NB − e A ] balances the force of repulsion A. The S atom in the SF 4   is bonded to
is …… . [2021, 20 July Shift-I]
[e A − e B or NA − NB]. Here,NA and NB are 4 fluorine atoms and has 1 lone
pair. All of them are in the Ans. (3)
the nucleus of two atoms, e A and e B are
the electrons of two atoms. hybridised orbitals and, there are 5 Shape of I−3 is :
such orbitals. Due to this, the I
hybridisation is sp3d.
B. Since, the central atom iodine has –
I
TOPIC 2 7 valence electrons out of which 5
electrons form 5 sigma bonds with
Hybridisation and F atoms and 2 electrons form 1
I

The number of lone pairs of electron on

VSEPR Theory lone pair making the steric number
the central atom is 3.
6 which implies the hybridisation
of the central atom is sp3d2 .
19 The number of species having 23 The number of species below that
C. NO2+ forms two bonds
non–pyramidal shape among the (double/triple bonds count only have two lone pairs of electrons in
following is once). Therefore,  hybridise the their central atom is ……… . (Round
(i) SO3 (ii) NO3− ones and one p-orbital to give sp3 off to the nearest integer)
(iii) PCl3 (iv) CO23 − hybridisation.
SF4 , BF4− , CIF3 , AsF3 , PCl 5 , BrF5,
D. The NH+4 ion has no pi bonds. As a
[2021, 27 Aug Shift-II]
result, all four electrons contained XeF4 , SF6
Ans. (3) in the atomic orbitals in the [2021, 18 March Shift-II]
The structure of the given compounds outermost shell of the nitrogen Ans. (2)
are as follows : atom can participate in Number of lone pairs on central atom in
hybridisation, making it  sp3. given compounds are as follows
O
(i) SO3 = The correct matches are :
Trigonal planar F F
S (A)-(iii), (B)-(i), (C)-( v) and (D)-(iv). F
O O SF4 = S , BF4 = B
F F F
O 21 The hybridisations of the atomic F F
–
⊕ orbitals of nitrogen in NO −2 , NO +2 (1 lp) (0 lp)
(ii) NO3 = N Trigonal planar
O O
and NH+4 respectively are F
[2021, 20 July Shift-II]
P CIF3= Cl—F , AsF3 = As
(a) sp 3, sp2 and sp (b) sp, sp2 and sp 3 F F
(iii) PCl3 = Cl Cl Pyramidal (c) sp 3, sp and sp2 (d) sp2 , sp and sp 3 F F
Cl (2 lp) (1 lp)
42 JEE Main Chapterwise Topicwise Chemistry

Cl F (c) T-shaped Ans. (d)

Cl F F (d) trigonal pyramidal Hybridisation of ‘O’ in H2O is sp3 as it is
PCI5 = Cl—P , BrF5= Br having two lone pair and two sigma bond.
Cl F F Ans. (c)
Cl Bond angle of sp3 hybridised compound
(0 lp) (1 lp) 2 lone pair + 3 bond pair should be 109.5°.
F Stearic number = 5 But in case of water, it is only 104.5° due
F F F F So, general formula is AB3L2. to repulsion between the lone pairs.
XeF4= Xe , SF6= S
F F F F (Here, L = number of lone pair.) Lone pair-lone pair repulsion is higher
(2 lp) than bond pair-bond pair repulsion.
F
Hybridisation = sp3d.
(0 lp) (VSEPR Theory)
Hence, two (lone pair) lp on central atom So, the shape is T- shape.
O
is CIF3 and XeF4 . B lp-lp > bp-bp
104.5º
H H Repulsion Repulsion
24 Amongst the following, the linear A B T-shape So, both A and R are true and R is the
species is correct explanation of A.
[2021, 17 March Shift-II]
(a) NO2 (b) Cl2O
B 27 The correct shape and I I I bond
(c) O 3 (d) N−3 Note Geometry of the compound having angles respectively in I −3 , ion are
Ans. (d) sp3d hybridisation should to tetragonal [2021, 24 Feb Shift-II]
bipyramidal (TBP) according to VSEPR
N3− is linear species. theory. But due to two lone pair,
(a) distorted trigonal planar, 135º and 90°
(b) T-shaped, 180° and 90°
geometry is distorted.
(c) Trigonal planar, 120°
– + – In TBP lone pair occupy equatorial
N O O N N N (d) Linear, 180°
position.
O O Cl Cl Linear Ans. (d)
B
Bent shape Bent shape Bent shape
B
Hybridisation of central I in I−3 is sp3d
l
Hybridisation = Number of sigma bond with 3 lone pair and 2 bond pair.
B A Equatorial −
+ number of lone pairs + number of  •• •• •• 
B
bond Shape Linear  •• I  I  I •• 
coordinate bonds. Axial bond
 •• •• •• 
l
Hybridisation of N in NO = 1 + 1 + 1 = 3. B
So, hybridisation is sp2 and structure Lone pair 3 lone pair
is bent or V-shape. 26 Given below are two statements : Bond angle 180° (for linear molecule)
l
Hybridisation of O inOCl2 = 2 + 2 = 4. one is labelled as Assertion (A)
So, hybridisation is sp3 and structure s
is bent or V-shape.
and the other is labelled as 180° or
l
Hybridisation of O inO3 = 1 + 1 + 1 = 3. Reason (R).
Linear
So, hybridisation is sp2 and structure Assertion (A) The HO H bond
is bent or V-shape. angle in water molecule is 104.5°.
l
Hybridisation of N inN−3 = 2.So,
hybridisation is sp and structure is
Reason (R) The lone pair - lone 28 Which of the following are
linear. pair repulsion of electrons is isostructural pairs ?
higher than the bond pair - bond A. SO 24 − and CrO 24 −
25 A central atom in a molecule has pair repulsion. [2021, 16 March Shift-I] B. SiCl 4 and TiCl 4
two lone pairs of electrons and (a) A is false but R is true.
(b) Both A and R are true, but R is not
C. NH3 and NO −3
forms three single bonds. The
shape of this molecule is the correct correct explanation of A. D. BCl 3 and BrCl 3
(c) A is true but R is false. [2021, 24 Feb Shift-I]
(a) see-saw [2021, 17 March Shift-I]
(d) Both A and R are true, and R is the (a) A and B only (b) A and C only
(b) planar triangular correct explanation of A. (c) B and C only (d) C and D only
Chemical Bonding and Molecular Structure 43

Ans. (a) Geometry : Octahedral

Shape : Square planar
H (Steric
Molecule Hybridisation B.P. L.P. Shape It has four equivalent Xe F bonds in the same plane.
number)
(b) SiF4 ⇒ F
SO2−
4 4 sp 3
4 0
S Si
O O–
F F
O–
Tetrahedral F
CrO2−
4 4 sp 3 4 0 Si ( sp3-hybridised)
Cr Geometry and shape : Tetrahedral
O O– It has four equivalentSi F bonds.
O– (c) •• SF4 ⇒
Tetrahedral
F
3 F
SiCl4 4 sp 4 0 Cl Axial
S bonds
Si F
Cl Cl Equatorial
Cl bonds F
Tetrahedral
S (sp3d-hybridised)
TiCl4 4 sp 3 4 0 Cl
Geometry : Trigonal bipyramidal
Ti Shape : see-saw
Cl Cl Axial S F bonds are longer than equatorial bonds.
Cl
Tetrahedral (d) BF4− ⇒ F

NH3 4 sp 3 3 1
B
N F F
H H F
H
Trigonal B (sp3-hybridised)
pyramidal
Geometry and shape : Tetrahedral
NO −3 4 sp2 3 0 It has four equivalentB F bonds.
N Hence, among given species onlySF4 has unequal bond lengths.
O O–
1 2 3 4
Trigonal planar 30 In CH2 == C == CHCH3 molecule,
BCl3 3 sp2 3 0 Cl the hybridisation of carbon 1, 2, 3 and 4 respectively are
B Cl [2021, 26 Feb Shift-II]
Cl
Trigonal planar
(a) sp 3, sp, sp 3, sp 3 (b) sp2 , sp2 , sp2 , sp 3
3
(c) sp2 , sp, sp2 , sp 3 (d) sp2 , sp 3, sp2 , sp 3
BrCl3 5 sp d 3 2 Cl
Ans. (c)
1 2 3 4
Cl Br
CH2 == C == CH  CH3
Cl It is buta -1, 2 - diene,
T - shape
H 1 2 3 H
If number of sigma bond (σ), co-ordinate bond and lone pair are H
same for given pairs, they are isostructural. Hence,SO24− , CrO24− , H C
4 H
SiCl 4 and TiCl 3 have tetrahedral shape and are isostructural. H
Here, C1 → sp , C2 → sp, C3 → sp and C4 → sp3 hybridised.
2 2

29 Which among the following species has unequal bond So, option (c) is the correct answer.
lengths ? [2021, 25 Feb Shift-II]
(a) XeF4 (b) SiF4 31 If AB4 molecule is a polar molecule, a possible geometry
(c) SF4 (d) BF4− of AB4 is [2020, 2 Sep Shift-I]
Ans. (c) (a) square pyramidal (b) square planar
•• (c) rectangular planar (d) tetrahedral
(a) • XeF ⇒
• 4 F F
Ans. (a)
Xe
F F If AB 4 molecule is a polar moelcule, a possible geometry of AB 4 is
square pyramidal.
Xe (sp3d2 -hybridised) All possible structure of AB 4 molecule are as follows :
44 JEE Main Chapterwise Topicwise Chemistry

(i) AB 4 ⇒ L =0 ⇒A is sp3 (tetrahedral) 33 The structure of PCl 5 in the solid [H2 O = Hybridisation is sp3 lone pair of
or A is dsp2 (square planar) electrons are two, so that bond angle is
⇒Dipole moment,µ = 0 state is [2020, 5 Sep Shift-I] 104°5′]
(Non-polar) (a) tetrahedral [PCl 4 ] + and octahedral
(ii) AB 4L2 ⇒ L =2 ⇒ A is sp3d2 [PCl 6 ] − C
(octahedral) (b) trigonal bipyramidal H H
⇒ µ = 0 (Non-polar), because (c) square planar [PCl 4 ] + and octahedral [No hybridisation as according to Draga's
[PCl 6 ] − rule, so that bond angle is 92°]
B B (d) square pyramidal According to VSEPR theory.
Ans. (a) Lone pair-Lone pair > Lone pair-Bond
A ⇒ µnet = 0 Phosphorus pentachloride (PCl 5 ) exist pair > Bond pair-Bond pair.
(Non-polar) as [PCl 4 ] + and [PCl 6 ] − .
B B Structure of [PCl 4 ] +
35 The ion that has sp 3d 2
Cl
hybridisation for the central atom,
(Assuming, B is more electronegative is [2019, 8 April Shift-II]
than A) P+ (a) [ICl2] − (b) [BrF2] −
(iii) AB 4L ⇒L = 1 ⇒A is sp3d (square
Cl Cl (c) [ICl4] − (d) [IF6] −
pyramidal or trigonal bipyramidal) Cl
Ans. (c)
Tetrahedral
⇒µ ≠ 0 (polar), because
(sp3-hybridisation) Key Idea The hybridisation for a central
B
− atom in a species can be calculated
B B B Structure of [PCl 6 ]
using formula
Cl 1
Cl Cl H = (V + M − C + A)
A A 2
P–
where,
B B Cl Cl
B Cl H = No. of hybridised orbitals used
B Octahedral by central atoms.
µplane = 0 µplane ≠ 0 (sp2d 2-hybridisation)
µaxis ≠ 0 V = No. of valence electrons of the
µaxis ≠ 0 central atom.
µnet ≠ 0 (polar) µnet ≠ 0 (polar)
In solid state PCl 5 prefer to exist as
oppositely charged ions like [PCl 4 ] + and M = No. of mono-valent atoms (bonded).
[Square pyramidal] [Trigonal pyramidal]
[PCl 6 ] − as the ionic bonding enhances C = No. of cationic (positive) charge.
So, it can be seen that when AB 4 molecule the crystalline nature. These structures A = No. of anionic (negative) charge.
is a polar molecule then possible geometry [PCl 4 ] + and [PCl 6 ] − .
The hybridisation of given species are as
of AB 4 is square pyramidal. Providing extra stability to solid. follows :
−
32 The molecular geometry of SF6 is ● For [ICl ]
2 and [BrF2 ] −
34 The compound that has the largest 1
octahedral. What is the geometry H = (7 + 2 − 0 + 1) = 5 (sp3d)
HM H bond angle (M = N, O, S, C) 2
of SF4 (including lone pair(s) of is [2020, 5 Sep Shift-II] ● For [ICl 4 ] − ,
electrons, if any)? [2020, 2 Sep Shift-II] (a) H2O (b) NH3 1
(a) Tetrahedral (b) Trigonal bipyramidal H = (7 + 4 − 0 + 1) = 6 (sp3d2 )
(c) H2 S (d) CH4 2
(c) Pyramidal (d) Square planar Ans. (d) ● For [IF6 ] − ,
Ans. (b) H 1
The geometry ofSF6 is octahedral and the H = (7 + 6 − 0 + 1) = 7 (sp3d 3)
C 2
geometry of SF4 is trigonal bipyramidal.
H H
SF6 F H 36 The correct statements among I to
F F [CH4 = hybridisation is sp3, lone pair of
S: sp3d2-hybridised III are :
S Geometry electrons is0, so that bond angle is
= shape maximum i.e., = 109°28' ]
I. Valence bond theory cannot
F F = octahedral explain the color exhibited by
F transition metal complexes.
SF4 F S: sp3d- C II. Valence bond theory can
F hybridised H H predict quantitatively the
Geometry H
S = trigonal magnetic properties of
F bipyramidal [NH3= Hybridisation is sp3, lone pair of transition metal complexes.
Shape electron is one, so that bond angle is
F = See-saw 107°]
III. Valence bond theory cannot
distinguish ligands as weak
and strong field ones.
N [2019, 9 April Shift-II]
H H
Chemical Bonding and Molecular Structure 45

(a) II and III only (b) I, II and III Ans. (d) bond pair and decreases the bond angle
(c) I and II only (d) I and III only IF7 Outer orbital diagram of I to 173°.
F
Ans. (d) I (53)
5s2 5p5 5d 0
Among the given statements, correct I(53) SiF4 Si
F F
statements are I and III only. Valence
(in ground state)
bond theory (VBT) cannot explain the
5s1 5p3 5d 3
colour exhibited by transition metal F
complexes. This theory cannot Regular tetrahedral
distinguish ligands as weak and strong
field ones. sp 3d 3 hybridisation (in excited state) F F

A B C D E F G XeF4 Xe
37 The molecule having smallest bond
angle is [AIEEE 2012] F F
(a) NCl3 (b) AsCl3 Square planar
Inclined at 72° at 90° with
(c) SbCl3 (d) PCl3 with one each other ABCDE plane F
Ans. (c) 3
Seven sp3 d hybrid orbitals
N  forming s-bonds with F-atoms,
Group = 15 B
P 
–
BF4 F F

As Valence  F
=5 F
Sb electrons F
F
3
MCl 3 has sp hybridized M-element with 90° Tetrahedral
F I 72°
one lone-pair.
Lone-pair and bond-pair repulsion F 42 The decreasing values of bond
F
decreases bond angle. However, the F angles from NH3 (107 ° ) to SbH3
bond-pairs of electrons are much farther Pentagonal-bipyramidal structure (91°) down group-15 of the periodic
away from the central atom than they
are in NCl 3. Thus, lone-pair causes even table is due to [AIEEE 2006]
40 Which of the following has (a) increasingbp -bp repulsion
greater distortion inPCl 3, AsCl 3 and SbCl 3.
Thus, bond angle decreases fromNCl 3 maximum number of lone pairs (b) increasing p -orbital character in sp3
(maximum) to SbCl 3 (minimum). associated with Xe? [AIEEE 2011] (c) decreasinglp -bp repulsion
(a) XeO 3 (b) XeF4 (d) decreasing electronegativity
38 In which of the following pairs, the (c) XeF6 (d) XeF2 Ans. (d)
two species are not isostructural? Ans. (d)
NH3 > PH3 > AsH3 > SbH3
[AIEEE 2012]
− Hybridi- Lone Bonding As the electronegativity of central atom
(a) CO 2−
3 and NO 3
Species sation pair on pairs increases, bonded electron polarise
(b) PCl +4 and SiCl 4 towards central atom more, so repulsion
of Xe Xe
(c) PF5 and BrF 5 increases and bond angle increases.
(a) XeO3 sp 3 1 3
(d) AlF 3−
6 and SF 6 (b) XeF4 sp 3d2 2 4 43 The molecular shapes of
Ans. (c)
(c) XeF6 sp 3d 3 1 6 SF4 ,CF4 and XeF4 are
(a) CO23− ,NO−3 Triangular planar
(d) XeF2 sp 3d 3 (max) 2 (a) different with 1, 0 and 2 lone pair of
(b) PCl +4 ,SiCl 4 Tetrahedral
electrons on the central atom,
(c) PF5 Trigonal bipyramidal respectively
41 In which of the following
BrF5 Square pyramidal (b) different with 0, 1 and 2 lone pair of
molecules/ions, all the bonds are
(d) AlF63− ,SF6 Octahedral electrons on the central atom,
not equal? [AIEEE 2006]
respectively
39 The structure of IF7 is (a) SF4 (b) SiF4 (c) the same with 1, 1 and 1 lone pair of
(d) BF4−
[AIEEE 2011]
(c) XeF4 electrons on the central atom,
(a) square pyramid respectively
Ans. (a)
(b) trigonal bipyramid (d) the same with 2, 0 and 1 lone pair of
SF4 has trigonal bipyramidal geometry,
(c) octahedral electrons on the central atom,
lone pair of electrons repels the axial
(d) pentagonal bipyramid respectively [AIEEE 2005]
46 JEE Main Chapterwise Topicwise Chemistry

Ans. (a) F

BF4– B Tetrahedral
Hybridisation
Molecule Structure of central Lone pair F F
atom F

46 The correct order of bond angles (smallest first) in

F H2S, NH3 , BF3 and SiH4 is [AIEEE 2004]
S sp 3d one
F (a) H2 S < SiH4 < NH3 < BF3 (b) NH3 < H2 S < SiH4 < BF3
SF4
F (c) H2 S < NH3 < SiH4 < BF3 (d) H2 S < NH3 < BF3 < SiH4
F
Ans. (c)
F
Species Structure lp bp VSEPR Bond angle
CF4 C sp 3 zero ••
2 2 lp-lp 90°
S
F F H2 S H •• H lp-bp
F
bp-bp
F ••
F 1 3 lp-bp 107°
N
XeF4 Xe sp d 3 2
two NH3 H  H bp →3bp
F F H
F 0 3 bp-bp 120°
BF3 F B
44 The maximum number of 90° angles between bond
pair-bond pair of electrons is observed in [AIEEE 2004] F
3
(a) dsp hybridisation 3
(b) sp d hybridisation H 0 4 bp-bp 109° 28′
(c) dsp2 hybridisation (d) sp 3d2 hybridisation SiH4 
Si H
Ans. (d) H H
3 2
sp d hybridisation has octahedral structure such that four hybrid
orbitals are at 90° wrt each other and others two at 90° with first Thus, the order of bond angles is
four. H 2 S < NH3 < SiH4 < BF3.

47 The states of hybridisation of boron and oxygen atoms in

boric acid (H3BO 3 ) are respectively [AIEEE 2004]
(a) sp2 and sp2 (b) sp2 and sp 3
(c) sp 3 and sp2 (d) sp 3 and sp 3
Ans. (b)
45 Which one of the following has the regular tetrahedral
structure ? [AIEEE 2004]
H3BO3 has structure sp3 sp2

(Atomic number : B = 5, S = 16, Ni = 28,Xe = 54) H— O—B—O—H

(a) XeF4 (b) SF4 (c) BF4− (d) [Ni(CN) 4] 2− |
O —H
Ans. (c)
Boron has three bonds, thus sp2 hybridised. Each oxygen has two
Tetrahedral structure is associated with sp3 hybridised central
atom without any lone pair. The structure of all the compounds bonds and two lone pairs, hence sp3 hybridised.
given are as follows
2
– 48 Which one of the following does not have sp 2 hybridised
2– CN CN carbon? [AIEEE 2004]
[Ni(CN)4] Ni Square (a) Acetone (b) Acetic acid
CN CN planar
(c) Acetonitrile (d) Acetamide
F
Ans. (c)
F
Distorted O O
XeF4 Xe octahedral  
(a) CH3  C CH3 (b) CH3  C OH
F F sp 3 sp 2 sp 3 sp 3 sp 2

O

F Distorted (c) CH3  C ≡≡N (d) CH3  C NH2
SF4
F S trigonal sp 3 sp sp 3 sp2
2
F bipyramidal Acetonitrile does not contain sp hybridised carbon.
F
Chemical Bonding and Molecular Structure 47

49 The pair of species having identical shapes for (c) NH3 NH+4 Change in shape
sp 3 sp 3 only, pyramidal to
molecules of both species, is [AIEEE 2003] tetrahedral
(a) CF4 , SF4 (b) XeF2 , CO2 (c) BF3, PCl3 (d) PF5 , IF5 (3 bp + 1 lp) (4 bp)
Ans. (b)
53 Underlined carbon is sp 3 hybridised in [AIEEE 2002]
XeF2 contains sp3d hybridised Xe atom with three lone pairs of
electrons. Fluorine atoms occupy axial positions while three lone (a) CH3C H == CH2 (b) CH3C H2NH2
pairs of elelctrons occupy equitorial positions in trigonal (c) CH3C ONH2 (d) CH3CH2 C N
bipyramid. Ans. (b)
Since, lone pair of electrons do not considered for the shape of H
the molecule, thus, shape of XeF2 comes out to be linear. While |
C−atom of CO2 is sp hybridised and thus, possesses a linear (a) CH3— C == CH2 (b) CH3— C —NH2
shape. | sp2 | sp3
F H H
O

Xe O C O (c) CH3— C — NH2 (d) CH3— CH2 — C N
sp2 sp
sp hybridised
F C-atom
sp3d hybridised 54 The number of lone pairs on Xe in XeF2 , XeF4 and XeF6
Xe-atom respectively, are [AIEEE 2002]
(a) 3, 2, 1 (b) 2, 4, 6 (c) 1, 2, 3 (d) 6, 4, 2
50 Which one of the following compounds has the smallest Ans. (a)
bond angle? [AIEEE 2003]
Number of lone pairs
(a) SO2 (b) OH2 (c) SH2 (d) NH3
= ( Total number of electron pairs) − (Number of shared pairs)
Ans. (c)
Number of electron pairs
1
Molecule Hybridisation Repulsion Bond angle = [Number of valence electrons of central atom
2
+ Number of atoms linked to central aom]
SO2 sp2 lp − bp, bp − bp 119.5° For XeF2
lp − lp, bp − lp 1
Number of e − pairs = [8 + 2] = 5
2
OH2 sp 3 bp − bp 104.5°
Number of lone pairs = 5 − 2 = 3
SH2 sp 3 —do— 90° 1
For XeF4 , Number of e − pairs = [8 + 4] = 6
2
NH3 sp 3 lp − bp, bp − bp 107°
Number of lone pairs = 6 − 4 = 2
For XeF6 ,
51 Bond angle of 109°28 ′ is found in [AIEEE 2002] 1
Number of e − pairs = [8 + 6] = 7
⊕ ⊕ 2
(a) NH3 (b) H2O (c) CH 5 (d) NH4
Number of lone pairs = 7 − 6 = 1
Ans. (d) Thus, number of lone pairs of electrons in XeF2 , XeF4 and XeF6 are
109° 28 ,′ it means pure regular tetrahedral geometry. 3, 2, 1 respectively.
(a) NH3, sp3, pyramidal (b) H2O, sp3, bent
+
(c) CH 5 , does not exist (d) NH +4 , sp3, tetrahedral
TOPIC 3
52 Hybridisation of the underline atom changes in Molecular Orbital Theory,
[AIEEE 2002]
(a)AlH3 changes to AlH4− (b) H2 O changes to H3O + Hydrogen and Metallic Bonding
(c)NH3 changes to NH4+ (d) In all cases
Ans. (a) 55 The spin-only magnetic moment value of B +2 species is
(a) AlH3 H Change in ……… × 10 −2 BM. (Nearest integer) [Given, 3 = 1.73]
2  hybridisation as well [2021, 1 Sep Shift-II]
sp H  −Al  H as in shape
sp 3 Ans. (173)
H
(b) H2O H3O + Change in shape Spin only mangnetic moment is given as
sp 3 sp 3 only, bent to µ S = n(n + 2) BM
(3bp + 1 lp) pyramidal where, n = number of unpaired electrons
(2 bp +2 lp)
Electronic configuration of B2+ is as follows
48 JEE Main Chapterwise Topicwise Chemistry

B2+ = σ 1s 2 , σ * 1s 2 , σ2s 2 , σ * 2s 2 , π2py1 ≈ π2pz0 (C)

∴B2+ has one unpaired electron,
OH O
µ = 1 (1 + 2) = 3 = 1.73 BM = 173 × 10 −2 BM
∴ x × 10 −2 = 173 × 10 −2 ∴ x = 173 H
Hence, answer is 173. Here, only one hydrogen atom bonded to electronegative oxygen
atom is present. So, intermolecular H-bonding is present but not
56 According to molecular orbital theory, the number of so extensive.
unpaired electron(s) in O 22 − is …… . [2021, 31 Aug Shift-II] So, option (a) is correct.
Ans. (0)
58 The total number of electrons in all bonding molecular
In O22 − , 18 electrons are present.
orbitals of O 2−
2 is ........… .
Configuration is given by
σ 1s 2 , σ * 1s 2 , σ2s 2 , σ * 2s 2 , σ2p2z , π2p2x = π2p2y
(Round off to the nearest integer) [2021, 27 July Shift-II]
π * 2p2x = π * 2p2y , σ *2pz0 Ans. (10)
2−
So, number of unpaired electrons inO2 = 0.
σ∗2pz
57 The compound/s which will show significant
intermolecular H–bonding is/are π∗2px π∗2 py
NO2 2px 2py 2pz 2pz 2py 2px
H
OH N CH3 π2px π2py

HO HO σ2pz
(A) (B)

Energy
(C)
[2021, 27 Aug Shift-II] 2s σ2s∗ 2s
(a) (B) only (b) (C) only
(c) (A) and (B) (d) (A), (B) and (C) σ2s
Ans. (a)
+
(A) – d
O– d O H (Hydrogen bonding) 1s σ1s∗ 1s
ÅN
O
σ1s
Atom Molecular Atom
configuration configuration configuration
In o-nitrophenol intramolecular hydrogen bonding takes place.
Configuration (O22 − ) = σ 1s 2 < σ ∗ 1s 2 < σ2s 2 < σ * 2s 2
(B) < σ2p2z < ( π2px = π2pz ) 4 ( π * 2px = π * 2py )2
OH
H Number of electrons in all bonding molecular orbitals = 10
Number of electrons in all anti-bonding molecular orbitals = 8
N
59 The difference between bond orders of CO and NO ⊕ is
O
H
x/2. where, x = ………… .
(Round off to the nearest integer). [2021, 27 July Shift-I]
N
Ans. (0)
H O Electronic configuration of CO (14 electrons).
O O (σ1s )2 (σ * 1s )2 (σ2s )2 (σ * 2s )2 ( π2px )2 ( π2py )2 , σ2p2z
[No. of bonding electron
HO N
− No. of antibonding electron]
Bond order =
H 2
10 − 4
= =3
Extensive H-bonding is observed in this case as two H-atoms 2
bonded to strongly electronegative atoms (nitrogen, oxygen) are Electronic configuration of NO+ (14 electrons)
present. H-bonding occurs when H-bonded to strongly (σ1s )2 (σ * 1s )2 (σ2s )2 (σ * 2s )2 ( π2px )2 ( π2py )2 (σ2pz )2
electronegative atoms exists in the vicinity of other 10 − 4
electronegative atoms possessing lone pairs of electron. BO = =3
2
Chemical Bonding and Molecular Structure 49

Bond order of both CO andNO⊕ = 3 ∴Correct order of bond order Ans. (c)
x
Difference = 0 = ; x = 0 = O2+ > O2 > O2− > O22 − According to Molecular Orbital Theory
2 (MOT), electronic configuration and their
62 Match List-I with List-II bond order of given options are as
60 The bond order and magnetic follows
List-I List-II
behaviour of O −2 ion are, ● O
2−
2 =
(Molecule) (Bond order) σ 1s 2 , σ * 1s 2 , σ2s 2 , σ * 2s 2 , σ2p2z , π2p2x ,
respectively [2021, 26 Aug Shift-II]
A. Ne2 (i) 1 π2p2y , π * 2p2x , π * 2p2y
(a) 1.5 and paramagnetic
B. N2 (ii) 2 Bond order
(b) 1.5 and diamagnetic
C. F2 (iii) 0 [No. of bonding electrons
(c) 2 and diamagnetic
D. O2 (iv) 3 − No. of antibonding electrons]
(d) 1 and paramagnetic =
2
Ans. (a)
Choose the correct answer from 10 − 8 2
O2− (Total electrons = 17) = = =1
the options given below. 2 2
= σ 1s 2 , σ * 1s 2 σ2s 2 σ * 2s 2 σ2p2z , π2p2x [2021, 26 Feb Shift-II] ● He2− = σ 1s 2 , σ * 1s 2 , σ2s 1
= π2p2y , π * 2p2x = π * 2py1 , σ *2pz0
A B C D A B C D 3−2 1
Number of unpaired electron = 1 Bond order = = = 0.5
(a) (iii) (iv) (i) (ii) (b) (i) (ii) (iii) (iv) 2 2
So, it is paramagnetic.
n − na
(c) (ii) (i) (iv) (iii) (d) (iv) (iii) (ii) (i) ● Be2 = σ 1s 2 , σ * 1s 2 , σ2s 2 , σ * 2s 2
Bond order = b Ans. (a) 4−4
2 Bond order = =0
(A) Ne2 (20e − ) 2
10 − 7
= = 1.5 He2+ = σ 1s 2 , σ * 1s 1
⇒σ 1s 2 σ * 1s 2 σ2s 2 σ * 2s 2 σ2p2z π2p2x
●
2
2− 1 1
π2p2y π * 2p2x π * 2p2y σ * 2p2z Bond order = = = 0.5
10 − 10 2 2
61 In the following the correct bond Bond order = =0
2 If bond order of chemical species is zero
order sequence is
then that chemical species does not
[2021, 25 July Shift-II] ⇒(iii) of List-II.
exist.
(a) O22 − > O2+ > O2− > O2 (B) N2 (14e − )
Therefore, Be2 does not exist.
(b) O2+ > O2− > O22 − > O2 ⇒ σ 1s 2 σ * 1s 2 σ2s 2 σ * 2s 2 π2px 2 ,
(c) O2+ > O2 > O2− > O22 − π2py 2 σ2pz2 64 A hard substance melts at high
(d) O2 > O2– > O22 − > O2+
10 − 4 temperature and is an insulator in
Ans. (c) Bond order = = 3 ⇒(iv) of List-II. both solid and in molten state.
2
Bond order
 No. of electrons in  (c) F2 (18 e − ) This solid is most likely to be a/an
 − ⇒σ 1s 2 σ * 1s 2 σ2s 2 σ * 2s 2 σ2pz2 π2px 2
[2021, 18 March Shift-II]
 bonding M.O.  (a) ionic solid (b) molecular solid
π2py 2 π * 2py 2 π * 2py 2
 No. of electrons in  (c) metallic solid (d) covalent solid
 
 anti -bonding M.O.  10 − 8 Ans. (d)
= Bond order = = 1 ⇒(i) of List-II.
2 2
Covalent or network solid have very high
Here, antibonding molecular orbital (d) O2 (16e − ) melting point and they are insulators in
electrons denoted by (*). ⇒σ 1s 2 σ * 1s 2 σ2s 2 σ * 2s 2 σ2pz2 π2px 2 their solid and molten form.
● O2+ = σ1s 2 σ ∗ 1s 2 σ2s 2 σ ∗2s 2 σ 2 p2z π2py 2 π * 2px 1 π * 2py 1 If a substance is an insulator in both
solid and molten phases, then it cannot
( π2p2x = π2 p2y ) ( π * 2px1 = π ∗2py ) 10 − 6
Bond order = = 2 ⇒(ii) of List-II. be ionic or metallic solid. If the melting
1
B.O. = (10 − 5) = 2.5 2 point is higher, then it cannot be a
2 molecular solid.
The correct matching is option (a).
● O2 = σ 1s 2 σ ∗ 1s 2 σ 2s 2 σ ∗2s 2 σ2p2z Note : Bond order ∴ It should be covalent network solid.
( π2p2z = π ∗2 p2y ) ( π * 2px1 = π * 2py1 ) No. of electrons in antibonding
1
B.O. = (10 − 6) = 2 MO (Molecular Orbital)
65 Of the species, NO, NO + , NO 2+ and
2 NO − , the one with minimum bond
− No. of electrons in bonding MO
● O2− = σ1s 2 σ ∗ 1s 2 σ2s 2 σ ∗2s 2 σ2 p2z = strength is [2020, 5 Sep Shift-I]
2
( π2p2x = π2 p2y ) ( π * 2p2x = π * 2py1 ) (a) NO + (b) NO (c) NO2+ (d) NO −
1 Ans. (d)
B.O. = (10 − 7) = 1.5 63 According to molecular orbital
2 Energy order of MOs
theory, the species among the N b −N a
● O22 − = σ1s 2 σ ∗ 1s 2 σ2s 2 σ ∗2s 2 σ2pz2 following that does not exist is B.O. =
( π2p2x = π2 p2y ) ( π * 2p2x = π * 2p2y ) [2021, 25 Feb Shift-I]
2
σ 1s σ 1*s σ2 s σ2* s π2 p x = π2 p y σ2 p z π2* p x = π2* p y
1
B.O. = (10 − 8) = 1 (a) O2−
2 (b) He2− (c) Be2 (d) He2+
2
50 JEE Main Chapterwise Topicwise Chemistry

10 − 5
NO(15e − ) : 2 2 2 2 2 2 2 1 0→ = 2.5 Its MO configuration must be similar to
2
N2 : σ 1s 2 σ * 1s 2 σ 2s 2 σ * 2s 2 π 2p2x π 2p2y σ2p2z
+ 10 − 4
NO(14e − ) : 2 2 2 2 2 2 2 0 0→ =3 10 − 4
2 ∴ Bond order = =3
2+ 9−4 2
N O (13e − ) : 2 2 2 2 2 2 1 0 0→ = 2.5
2 As there is no unpaired electron in CN− , thus it is diamagnetic.
− 10 − 6
NO(16e − ) : 2 2 2 2 2 2 2 1 1→ =2 68 If the magnetic moment of a dioxygen species is 1.73
2
We know, B.M, it may be. [2020, 9 Jan Shift-II]
1 (a) O2 ,O2− or O2+ (b) O2− or O2+ (c) O2 or O2− (d) O2 or O2+
Bond length ∝
BO (Bond order) Ans. (a)
1
∝ Species and Molecular orbital Number of unpaired
Bond strength
number of electronic electrons (n) and
So,the order of bond strength : electrons configuration magnetic moment
NO+ > NO = NO2 + > NO− 1. O2 -16 electrons ∗
σ1s σ1s
∗
σ2s σ2s σ2pz n = 2, µ = n (n + 2)
−
So, NO has minimum bond strength. µ = 2 × 4 BM
∗ ∗ ∗
π2pX = π2pY π2pX= π2pY σ2p
= 2.82 BM
66 If the boiling point of H2O is 373 K, the boiling point of Z

H2S will be [2020, 3 Sep Shift-I]

(a) less than 300 K 2. O2+ -15 electrons n = 1, µ = 1 × 3
(b) equal to 373 K = 1.73 BM
(c) more than 373 K
(d) greater than 300 K but less than 373 K 3. O −2 -17 electrons n = 1, µ = 1.73 BM
Ans. (a)
Two O H bonds of a H2O molecule make stronger and extensive
intermolecular hydrogen bonds which lead two association ofH2O
molecules into water orH2O(l ). OneH2O molecule can make four
H–bonds. 69 Among the following molecules/ions,
Association through C 2− 2− 2−
2 , N 2 , O2 , O2
nH2O intermolecular
(H2O)n or H2O(l)
Hbonds
Which one is diamagnetic and has the shortest bond
Water
length? [2019, 8 April Shift-II]
(a) C2−
2 (b) O2 (c) O2−
2 (d) N2−
2

H H H Ans. (a)
δ– δ+ δ– δ+ δ– n, no. of
H O H O H O Bond order Magnetic
Species MO energy order unpaired
(BO) character
e−
C2− −
2 (14e ) [8 e] π
6 −0 0
H-bonds 2 px2 =3 Diamagnetic
2
=π σ
But S H bonds of H2S cannot make H–bonds. So,H2S is a gas at 2 py2 2 pz2
room temperature butH2O is a liquid (water). So, boiling point of 6 −2
H2O is more 373 K thanH2S, because :
O2 (16e − ) [8 e] σ π =2 2 Paramagnetic
2 pz2 2 px2
2
Boiling point ∝ molecular association. = π 2 π*2 p 1 = π*2 p 1
2 py x y

67 The bond order and the magnetic characteristics of CN − O2− −

2 (18e ) [8 e] σ2 p 2 π 2 p 2
6 −4
=1 0 Diamagnetic
z x
are [2020, 7 Jan Shift-II] 2
= π 2 π* 2 p 2
1 2p y x
(a) 3, diamagnetic (b) 2 , paramagnetic
2 = π* 2 p 2
y
1
(c) 3, paramagnetic (d) 2 , diamagnetic N22 − (16 e − ) [8 e] π 2 p 2 6 −2 2
2 x *
=2 Paramagnetic

Ans. (a) = π2p 2 σ π 2p1 2

y 2 pz2 x

CN– has 14 electrons (6 from C, 7 from N and 1 for negative =π

*
2 py1
charge).
Chemical Bonding and Molecular Structure 51
1 (a) CO (b) B2
Bond length ∝ [8e– ] σ2p2z π2px2 [8e– ] σ2p2z π2p2x
BO (Bond order) (c) NO (d) O2
= π2py2 π* 2px1 = π* 2p1y = π2p2y π2p
* 2
So order of bond length Ans. (a) x
C22 < O2 = N22 − < O22 − = π* 2p1y
Key Idea Magnetic nature can be Half-filled
(BO = 3) (BO = 2) (BO = 1) anti-bonding
detected by molecular orbital theory.
π*-MOs
The diamagnetic species with shortest Presence of unpaired electrons means
bond length is C22 − (option-a). paramagnetic and absence of unpaired So, in the formation ofO2− from O2 , the
electrons means diamagnetic in nature.
70 Among the following, the molecule 17th electron goes to the π* 2px or π* 2py
Among the given options, CO is a
expected to be stabilised by anion diamagnetic molecule. It can be proved molecular orbital (anti-bonding) which is
formation is C 2 , O 2 , NO, F2 . by molecular orbital (MO) theory. The half-filled inO2 .
[2019, 9 April Shift-I] electronic configuration of given
(a) C2 (b) F2
diatomic molecules are given below. 73 According to molecular orbital
● CO (Number of electrons = 14) theory, which of the following is true
(c) NO (d) O2
Ans. (a) Electronic configuration with respect to Li +2 and Li −2 ?
= σ 1s 2 , σ * 1s 2 , σ2s 2 , σ * 2s 2 , [2019, 9 Jan Shift-I]
C2 will be stabilised after forming anion. (a) Both are unstable
σ2p2z , π2p2x ≈ π2p2y
The electronic configuration of carbon is
Since, there is no unpaired electron in (b) Li2+ is unstable and Li2− is stable
1s 2 2s 2 2p2 . There are twelve electrons in
C2 . After forming anion (i.e. C2– ), the the CO molecule, so it is diamagnetic. (c) Both are stable
electronic configuration is ● NO (Number of electrons = 15) (d) Li2+ is stable and Li2− is unstable
−
● C : ( σ 1s ) ( σ 1s )
2
2 * 2
( σ 2s ) 2 Electronic configuration Ans. (d)
(σ * 2s ) ( π2px = π2p2y ) (σ2pz1 ) or
2 2
= σ 1s 2 , σ * 1s 2 , σ2s 2 , Considering molecular orbital theory
KK (σ2s ) 2 (σ * 2s ) 2 ( π2p2x = π2p2y ). σ2pz1 σ * 2s 2 , σ2p2z , π2p2x ≈ π2p2y , (MOT) :
1 1
Bond order = (N b − N a ) = (9 − 4) = 2.5 π * 2px1 ≈ π * 2py0 The electronic configuration of
2 2
Since, NO has one unpaired electron Li2+ (Z = 5) = σ 1s 2 , σ * 1s 2 , σ2s 1
For other options such as F2− , O2− , NO− , in π * 2px1 orbital, so it is N − Na
the electronic configurations are as Bond order (BO) = b
paramagnetic. 2
follows : ● B (Number of electrons = 10)
− 2 3−2 1
2 : (σ 1s ) (σ 1s ) (σ2s )
2 * 2 2
● F
= =
Electronic configuration 2 2
(σ 2s ) (σ2pz )
* 2 2
= σ 1s 2 , σ * 1s 2 , σ2s 2 , σ * 2s 2 ,
( π2px2 = π2py2) ( π * 2p2x = π * 2p2y )(σ * 2pz1 ) The electronic configuration of
π2px1 ≈ πpy1
Bond order Li2− (Z = 7) = σ 1s 2 , σ * 1s 2 , σ2s 2 , σ ∗2s 1
Since, two unpaired electrons are
= 1 /2(N b − N a ) = 1 /2(10 − 9) = 0.5 present in π2px1 and π2py1 orbital. So, it N − Na
Bond order (BO) = b
● O2− : (σ 1s )2. (σ * 1s )2 (σ2s )2 is paramagnetic. 2
● O (Number of electrons = 16)
(σ * 2s )2 (σ2pz )2 2 4−3 1
= =
( π2p2x = π2p2y ) ( π * 2p2x = π * 2py1 ) Electronic configuration 2 2
1 1 = σ 1s 2 , σ * 1s 2 , σ2s 2 ,
Bond order = (N b − N a ) = (10 − 7) = 1.5 For the species having the same value of
2 2 σ * 2s 2 , σ 2pz2 , π2p2x ≈ π2p2y , BO, the specie having lesser number of
● NO− : (σ 1s )2 (σ * 1s )2 (σ 2s )2 π * 2px1 ≈ π * 2py1 antibonding electrons [N a ] will be more
(σ * 2s )2 (σ2pz )2 Since, two unpaired electrons are stable.
( π2p2x = π2p2y ) ( π * 2px1 = π * 2py1 ) present in π * 2px1 and π * 2py1 orbital. So, Here, N a of Li2+ (2) < N a of Li −2 (3) .
1 1 it is also paramagnetic.
Bond order = (N b − N a ) = (10 − 6) = 2 So, their order of stability will be
2 2 Li2+ > Li2− .
The value of bond order of C2− is highest 72 During the change of O 2 to O −2 , the
among the given options. Bond order incoming electron goes to the 74 In which of the following
between two atoms in a molecule may
be taken as an approximate measure of
orbital. [2019, 10 April Shift-I] processes, the bond order has
the bond length. (a) π2px (b) π * 2px increased and paramagnetic
The bond length decreases as bond (c) π2py (d) σ * 2pz character has changed to
order increases. As a result, stability of a Ans. (b) diamagnetic? [ 2019, 9 Jan Shift-II]
molecule increases. The change ofO2 to O2− can be as follows: (a) O2 → O2+
+e – – (b) N2 → N2+
71 Among the following species, the O2 (16 e –) O2 (17 e–)
[Dioxygen] [Super-oxide]
(c) O2 → O22 −
diamagnetic molecule is Energy Energy (d) NO → NO +
[2019, 9 April Shift-II]
52 JEE Main Chapterwise Topicwise Chemistry

Ans. (d)
N − Na 
Species Valence MOs Bond Order  b 
Magnetic Nature
 2 
NO(15e − ) [8 e −] π 2 p2x = π 2 p2y σ2 p2z 6 −1 Paramagnetic
= 2.5
2
π *2 px1 = π *2 py0σ * 2 pz 0
–e− − 6 −0
[8 e ] π 2 p2x = π 2 p2y σ2 p2z =3 Diamagnetic
NO + (14e − ) 2
π *2 px0 = π *2 py0σ *2 pz0
N2 (14e ) −
[8 e −] π 2 p2x = π 2 p2y σ2 p2z 6 −0 Diamagnetic
=3
2
–e− 5 −0
N2+ (13e −) π *2 px0 = π *2 py0, σ2 pz0 = 2.5 Paramagnetic
[8 e −] π 2 p2x = π 2 p2y σ 2 pz 1 2
π *2 px0 = π *2 py0σ *2 pz0
O2 (16 e − ) [8 e −] σ 2 p2z π 2 p2x = π 2 p2y 6 −2 Paramagnetic
=2
2
–e− π *2 px1 = π *2 py1 σ *2 pz0
−
[8 e ] σ 2 p2z π 2 p2x = π 2 p2y
O2+ (15e − )
6 −1
π *2 px1 = π *2 py0σ *2 pz0 = 2.5 Paramagnetic
+2e− 2
[8 e −] σ 2 p2z π 2 p2x = π 2 p2y
O22 − (18 e − ) 6 −4
π *2 p2x = π *2 p2y σ *2 pz0 =1
2 Diamagnetic

So, only in the conversion ofNO → NO+ , No unpaired electron is present.

the bond order has increased (2.5 → 3) Electronic Configu- Bond order Hence, it is diamagnetic.
and paramagnetic character has ration (c) O2 (8 + 8 = 16) − σ 1s 2 , σ * 1s 2 ,
changed to diamagnetic.
He +2 σ 1s 2 σ *1s 1 2 −1 σ2s 2 , σ * 2s 2 ,
= 05
.
75 Two pi and half sigma bonds are 2 σ2pz , π2px = π2p2x , π * 2px1 = π * 2py1
2 2

H −2 σ 1s 2 σ *1s 1 2 −1 Two unpaired electrons are present.

present in [2019, 10 Jan Shift-I] = 05
.
2 Hence, it is paramagnetic.
(a) O2+ (b) N2
H 2− σ 1s 2 σ *1s 2 2 −2 (d) B2 (5 + 5) − σ 1s 2 , σ * 1s 2 , σ2s 2 , σ * 2s 2 ,
(c) N2+ (d) O2 2 =0
2 π2px1 = π2py1
Ans. (c)
He 2+ σ 1s 2 2 −0 Two unpaired electrons are
The energy order of MOs of the given 2 =1 present.
species are as follows: 2
Hence, it is paramagnetic.
O2 (16 e − ’ s) The molecule having zero bond order will
= σ 1s 2 , σ * 1s 2 , σ2s 2 , σ * 2s 2 , σ2 p2z , not be viable hence,H22 − (option d) is the
correct answer. 78 Which one of the following
π2 p2x = π2 p2y , π * 2 p1x = π * 2 p1y ,
molecules is expected to exhibit
O2 (15e − ’ s) = σ1s 2 , σ * 1s 2 , σ2s 2 ,
+
77 Which of the following species is diamagnetic behaviour?
σ * 2s 2 , σ2 p2z ,
[JEE Main 2013]
π2 px = π2 py , π 2 px ≈ π * 2 py0
2 2 * 1 not paramagnetic? [JEE Main 2017]
(a) C2 (b) N2 (c) O2 (d) S2
N2 (14e − ’ s) = σ 1s 2 σ * 1s 2 , σ 2s 2 , σ * 2s 2 (a) NO (b) CO (c) O2 (d) B2
Ans. (a, b)
π2 p2x = π2 p2y , σ2 p2z Ans. (b)
* 1s 2 , σ2s 2 , σ
C2 (6 + 6 = 12) = σ1s 2 , σ * 2s 2 ,
N2 (13e − ’ s) = σ 1s 2 σ * 1s 2 σ2 s 2 σ * 2s 2
+
To identify the magnetic nature we need
π2 p2x = π2 p2z σ2 p1z to check the molecular orbital π2 p2x ≈π2 py2
Thus, in case of N+2 , two π-bonds and half configuration. If all orbitals are fully Since, all the electrons are paired, it is a
σ-bond are present in the bonding MOs. occupied, species is diamagnetic while diamagnetic specie.
when one or more molecular orbitals N2 (7 + 7 = 14) = σ 1s 2 , σ * 1s 2, σ2s 2 ,
is/are singly occupied, species is * 2s , π2p2 ≈ π2p2 , σ2p2
76 According to molecular orbital σ 2
x y z
paramagnetic.
theory, which of the following will It is also a diamagnetic specie because
(a) NO (7 + 8 = 15) − σ 1s 2 , σ * 1s 2 ,
not be a viable molecule? of the absence of unpaired electrons.
[JEE Main 2018]
σ2s 2 , σ * 2s 2 , O2 (8 + 8 = 16)
π2px = π2py , π2p2z , π * 2px1 = π * 2py0
2 2 ∗
(a) He2+
2 (b) He2+ (c) H2− (d) H2−
2
or S2 = σ 1s 2 , σ* 1s 2 , σ2s 2 , σ 2s 2 ,
One unpaired electron is present. *
Ans. (d) σ2p2z , π2p2x ≈ π2p2y , π* 2px1 ≈ π 2py1
Hence, it is paramagnetic.
Key Idea According to M.O.T, the Since,O2 or S2 contain 2 unpaired
viability of any molecule can be judged (b) CO (6 + 8 = 14) − σ 1s 2 , σ * 1s 2 , σ2s 2 ,
electrons, therefore they are
through the calculation of bond order. σ * 2s 2 , π2p2x = π2p2y , σ2p2z
paramagnetic.
Chemical Bonding and Molecular Structure 53

79 In which of the following pairs of (a) C 2– –

2 , O2 , CO, NO 86 Which of the following hydrogen
molecules/ions both the species (b) NO , C 2–
+ –
2 , CN , N2 bond is the strongest? [AIEEE 2007]
are not likely to exist? (c) CN , N2 , O 2 , CO 2–
– 2–
2 (a) O H LN (b) F H LF
(d) N2 ,O 2–, NO + , CO
[JEE Main 2013]
(c) O H LO (d) O H LF
(a) H 2+ , He2–
2 (b) H2–, He2–
2 Ans. (b) Ans. (b)
(c) H2+
2 , He2 (d) H2–, He2+
2 Isoelectronic species have same number Since,H−bond is the electrostatic force
Ans. (c) of electrons, NO+ , C22 – , CN – and N 2 all of attraction betweenH−atom and
have 14 electrons. electronegative element. Thus, fluorine
Species having zero or negative bond
order do not exist. being the most electronegative element
H22 + (1 + 1 − 2 = 0) = σ 1s 0
83 Which one of the following pairs of forms stronger H−bonds. On the other
species have the same bond order? hand, H − F possesses larger
Bond order = 0 electronegative difference thanO − H.
[AIEEE 2008]
* 1s 2
He2 (2 + 2 = 4) = σ 1s 2 , σ
(a) CN – and NO + (b) CN– and CN+ Therefore, H − F molecule is more
Nb − Na 2 − 2 polarised thanO − H, due to which
Bond order = = =0 (c) O2– and CN– (d) NO + and CN+
2 2 H−atom of H − F bears larger amount of
Ans. (a) partial charge than that ofO − H. This
So, both H22 + and He2 do not exist.
CN− and NO+ both have same number of suggests H−atom of H − F attracts more
80 Stability of the species Li 2 , Li 2− and electrons and same bond order (3). strongly F −atom than that of O − H.
Hence,H − F forms more stronger
Li +2 increases in the order of 84 Which of the following species H−bonds with fluorine than that ofO − H.
[JEE Main 2013]
exhibits diamagnetic behaviour?
(a) Li 2 < Li 2+ < Li 2– [AIEEE 2007] 87 Which of the following
(b) Li 2– < Li 2+ < Li 2 (a) O2− (b) O2+ (c) O2 (d) NO molecules/ions does not contain
2
(c) Li 2 < Li 2– < Li 2+ unpaired electrons? [AIEEE 2006]
(d) Li 2– < Li 2 < Li 2+ Ans. (a)
(a) O 2−
2 (b) B2 (c) N 2+ (d) O2
Ans. (b) The correct option isO22 − . This species Ans. (a)
has 18 electrons, which are filled in such
Li2 (3 + 3 = 6) = σ 1s 2 , σ* 1s 2 , σ2s 2 a way that all molecular orbitals are fully
Molecular orbital configuration of given
N − Na 4 − 2 molecules are
Bond order = b = =1 filled, so diamagnetic.
2 2 O22 − (Total number of electrons = 18)
σ 1s 2 , σ* 1s 2 , σ2s 2 , σ* 2s 2 , σ2p2z , π2p2x
Li + (3 + 3 − 1 = 5) = σ 1s 2 , σ* 1s 2 , σ2s 1 σ 1s 2 , σ* 1s 2 , σ2s 2 , σ* 2s 2 , σ2p2z , π2p2x
2
3−2 1 ≈ π2p2y , π* 2p2x ≈ π 2p2y
*
≈ π2p2y , π* 2p2x ≈ π* 2p2y
Bond order = = = 0.5
2 2 B2 ( Total number of electrons = 10)
Li2– (3 + 3 + 1 = 7) 85 In which of the following ionisation σ 1s 2 , σ * 1s 2 , σ2s 2 , σ * 2s 2 , π2px1 ≈ π2py1
processes, the bond order has N2+ ( Total number of electrons = 13)
= σ 1s 2 , σ* 1s 2 , σ2s 2 , σ* 2s 1
increased and the magnetic σ 1s 2 , σ * 1s 2 , σ2s 2 , σ * 2s 2 , π2p2x
4−3 1 behaviour has changed?
Bond order = = = 0.5 ≈ π2p2y , σ2pz1
2 2 [AIEEE 2007]
O2 ( Total number of electrons = 16)
Stability order isLi2 > Li2+ > Li2– (because (a) C2 → C2+ (b) NO → NO + σ 1s 2 , σ * 1s 2 , σ2s 2 , σ * 2s 2 , σ2p2z ,
Li 2– have more number of electrons in (c) O2 → O2+ (d) N2 → N2+ π2p2x ≈ π2py1 , π * 2px1
antibonding orbitals which destabilises 2−
the species). Ans. (b) Thus, O2 does not contain any unpaired
NO → NO+ + e − electron.
81 Using MO theory, predict which of (NO ) Total electrons = 14
+
88 Increasing order of bond strength
the following species has the σ 1s 2 , σ * 1s 2 , σ 2s 2 , σ * 2s 2 , π2p2z of O 2 , O −2 , O 22− and O +2 is [AIEEE 2002]
shortest bond length? [AIEEE 2009] ≈ π2p2x , σ2p2y (a) O2+ < O2 < O2− < O2−
(a) O 2+
2 (b) O2+ Diamagnetic, (b) O2 < O2+ < O2− < O22 −
(c) O2− (d) O2− 10 − 4 (c) O2− < O22 − < O2+ < O2
2
Bond order = =3
Ans. (a) 2 (d) O22 − < O2− < O2 < O2+
(NO) Total electrons = 15 Ans. (d)
Higher the bond order, shorter is the
bond lengthO22 + has the shortest bond σ 1s , σ* 1s 2 , σ2s 2 , σ* 2s 2 , σ2p2z , π 2px1 + 1
2 Higher the bond order, greater is the
length (BO = 3) bond strength.
Bond order of remaining species are ≈ π2py1 + 1, π* 2px1 ≈ π* 2py Species Bond order
O2+ (2.5), O2− (1.5) and O22 − (1) 10 − 5 O2−
Paramagnetic, Border = = 2.5 2 1
2
O2− 1.5
82 Which one of the following Electron is taken away from
constitutes a group of the O2 2.0
non-bonding molecular orbital, that’s
isoelectronic species? [AIEEE 2008] why bond order increases. O2+ 2.5
05
Chemical
Thermodynamics
TOPIC 1 According to first law of 04 Five moles of an ideal gas at 293 K
thermodynamics internal energy,
Generalised terms and First ∆U = q + W
is expanded isothermally from an
Law of Thermodynamics initial pressure of 2.1 MPa to 1.3
∆U = 150 + (− 200)
MPa against at constant external
{∆U = Change in internal energy}
01 For water ∆ vap H = 41kJ mol − 1 at = − 50 J
pressure 4.3 MPa. The heat
373 K and 1 bar pressure. Assuming transferred in this process is ………
Magnitude = | − 50 J | = | ∆ U |
that water vapour is an ideal gas kJ mol −1 . (Rounded off to the
= 50 J
that occupies a much larger nearest integer)
volume than liquid water, the 03 At 25°C, 50 g of iron reacts with [R = 8.314 J mol −1 K −1 ]
[2021, 25 Feb Shift-II]
internal energy change during HCl to form FeCl 2 . The evolved
Ans. (15)
evaporation of water is ……… kJ hydrogen gas expands against a
mol −1 . constant pressure of 1 bar. The The gas performs isothermal irreversible
work (W).
[Use R = 8.3 J mol − 1 K − 1 ] work done by the gas during this
where, ∆U = 0 (change in internal energy)
[2021, 26 Aug Shift-II] expansion is …… J. (Round off to
From, 1st law of thermodynamics,
Ans. (38) the nearest integer)
⇒ ∆U = ∆Q + W
H2O(l ) → H2O(g) [Given, R = 8.314 J mol–1 K –1 . ⇒ 0 = ∆Q + W
Q ∆H = ∆U + ∆ng RT Assume, hydrogen is an ideal gas] ⇒ ∆Q = − W
∆H = enthalpy of vaporisation [Atomic mass off Fe is 55.85 u] Now, W = − pext (V2 − V1)
∆U = change in internal energy [2021, 16 March Shift-II]
 nRT nRT 
∆ng = number of moles of water Ans. (2218) = − pext  − 
vapour  p2 p1 
R = 8.3 J mol –1 K–1 Fe(s ) + HCl(aq) → FeCl2 (aq) + H2 (g)
50 g  1 1
T = 373 K = − pext × nRT  − 
(Moles of Fe = Moles of H2 )  p2 p1 
∴41kJ = ∆U + RT 50
moles =
∆U = 41 − 8.3 × 373 × 10 −3 = 41 − 3.095 55.85
0.8952 mol 0.8952 mol Given, pext = 4.3 MPa, p1 = 2.1 MPa,
= 37.90 kJ mol −1 = 38 kJ mol −1 = 0.8952 mol p2 = 1.3 MPa,
Work done can be given by n = 5 mol,
02 A system does 200 J of work and W = − pext∆V = − ∆ng RT T = 293 K
at the same time absorbs 150 J of where, ∆ng = {gaseous moles on product and R = 8.314 J mol −1 K−1
heat. The magnitude of the change side } −  1 1
= − 43
. × 5 × 8314
. × 293  − 
in internal energy is ……… J. {gaseous mole on reactant side}  1.3 2.1 
(Nearest integer) = 0.8952 − 0 = − 15347.70 J mol −1
[2021, 25 July Shift-II]
W = − 0.8952 × 8314
. × 298 = − 15.347 kJ mol −1
Ans. (50) = −2217.92 J ~− − 15 kJ mol −1
Work done by the system, W = − 200 J Closest integer = 2218 ⇒ ∆Q = 15 kJ mol −1
Heat absorbed,q = + 150 J
Chemical Thermodynamics 55

05 The ionisation enthalpy of Na + ⇒ ∆ng = 5 QT = 373 K Ans. (b)

formation from Na(g) is 495.8 kJ We know that, From the 1st law of thermodynamics,
mol −1 , while the electron gain dH = dU + ∆ng RT ∆U = q + W
dU = Internal energy change where, ∆U = change in internal energy
enthalpy of Br is –325.0 kJ mol −1 .
Given, the lattice enthalpy of NaBr q = heat, W = work done
= dH − ∆ng RT
is –728.4 kJ mol −1 . The energy for = 41 × 1000 × 5
The above equation can be represented
for the given processes involving ideal
the formation of NaBr ionic solid is − 5 × 8314
. × 373 gas as follows:
(–) ………… × 10 −1 kJ mol −1 . = 18949439
. J ~− 18949400. J (a) Cyclic process For cyclic process,
[2021, 25 Feb Shift-I]
∆U = 0
Ans. (5576) 08 The magnitude of work done by a ∴ q = −W
IE 1
Na(g) → Na (g) + gas that undergoes a reversible Thus, option (a) is correct.
expansion along the path ABC (b) Adiabatic process For adiabatic
[IE1 = 495.8 kJ mol −1] process,
shown in the figure is ……… .
Electron
Br( g) → (EG) Br − ( g) [Gain [2020, 8 Jan Shift-I] q = 0 ⇒ ∆U = W
gain enthalpy Thus, option (b) is incorrect.
Pressure
enthalpy = − 325 kJ mol −1] (Pa)10 (c) Isochoric process For isochoric
Lattice
Na+ + Br − → (LE) NaBr (s ) 8 A B process,
energy ∆V = 0. Thus, W = 0 (QW = p∆V ).
[Lattice energy = − 7284 . kJ mol −1] 6 ∴ ∆V = q
∆HFormation = IE1 + Gain enthalpy 4 Thus, option (c) is correct.
+ Lattice energy C (d) Isothermal process For
∆H = 495.8 + (− 325) + (− 7284 .) (2, 2) 4 6 8 10 12 Volume isothermal process,
(m3) ∆U = 0
= − 557.6 kJ/mol
= − 5576 × 10 −1 kJ Ans. (48.00) ∴ q = −W
Thus, option (d) is correct.
Work done is equal to the area under
06 Five moles of an ideal gas at 1 bar pV-curve.
and 298 K is expanded into vacuum 1 11 5 moles of an ideal gas at 100 K are
∴Work done ( W ) = (6 + 10) × 6
to double the volume. The work 2 allowed to undergo reversible
done is [2020, 4 Sep Shift-II] = 4800
. Pa. m3 = 48.00 J. compression till its temperature
(a) −RT lnV2 / V1 (b) − RT (V2 − V1) becomes 200 K. If C V =28 JK −1
(c) C V (T2 − T1) (d) zero 09 At constant volume, 4 mol of an mol −1 , calculate ∆U and ∆pV for
Ans. (d) ideal gas when heated from 300 K this process. (R = 8.0 JK −1 mol −1 )
Expansion of a gas in vacuum (pext = 0) is to 500 K changes its internal [2019, 8 April Shift-II]
called free expansion. No work is done energy by 5000 J. The molar heat (a) ∆U = 2.8 kJ; ∆ (pV) = 0.8 kJ
during free expansion, since as the capacity at constant volume is (b) ∆U = 14 J; ∆ (pV) = 0.8 J
expansion is done in vacuum that is in ............ [2020, 8 Jan Shift-II] (c) ∆U = 14 kJ; ∆ (pV) = 4 kJ
absence of external pressure, hence w (d) ∆U = 14 kJ; ∆ (pV) = 18 kJ
will be
Ans. (6.25)
Given: n = 4 mol Ans. (c)
w = − pext∆V ⇒ w = 0
∆T = 500 K − 300 K = 200 K Given, n = 5 mol, T2 = 200 K, T1 = 100 K
(Here, pext = 0), because expansion takes
place in vacuum) ∆U = 5000 J C V = 28 JK−1 mol −1
∆U = nC V ∆T ∆U = nC V ∆T = nC V (T2 − T1)
07 The internal energy change (in J) ∆U 5000 50 = 5 mol × 28 JK−1 mol −1
CV = = = = 625
.
when 90 g of water undergoes n∆T 4 × 200 8 × (200 − 100) K
complete evaporation at 100°C is = 14000
, J = 14 kJ
………, (Given : ∆H vap for water 10 Which one of the following ∆pV = nR∆T = nR (T2 − T1)
at 373 equations does not correctly = 5 mol × 8 JK−1 mol −1 × (200 − 100) K
K = 41kJ/mol, R = 8.314 JK −1mol −1 ) represent the first law of = 4000 J = 4 kJ
[2020, 5 Sep Shift-I] thermodynamics for the given
Ans. (189494) processes involving an ideal gas? 12 Among the following the set of
Given, dH = 41 kJ/mol = 41 × 1000 × 5 J (Assume non- expansion work is zero) parameters that represents path
[For 90 g or 5 mol H2O(l )] [2019, 8 April Shift-I] functions, is [2019, 9 April Shift-I]
H2O(l ) → H2O(g) (a) Cyclic process : q = − W (A) q+W (B) q
t=0
90
mol — (b) Adiabatic process : ∆U = − W (C) W (D) H −TS
18
(c) Isochoric process : ∆U = q (a) (A) and (D) (b) (A), (B) and (C)
t=∝ 0 5 mol
(d) Isothermal process : q = − W (c) (B), (C) and (D) (d) (B) and (C)
56 JEE Main Chapterwise Topicwise Chemistry

Ans. (d) T2 If molar heat capacity of Al is 24 J

q (heat) and W (work) represents path mol −1 K −1 , the temperature of Al
functions. These variables are path |W| T1
increases by [2019, 10 Jan Shift-II]
dependent and their values depends (c) 3
upon the path followed by the system in (a) K (b) 1 K
attaining that state. They are inexact 2
2
differentials whose integration gives a O ln V (c) 2 K (d) K
3
total quantity depending upon the path.
T2 Ans. (d)
Option (a), i.e.q + W and option (d), i.e.
H–TS are state functions. The value of |W|
T1 It is an irreversible isothermal
state functions is independent to the compression of an ideal gas.
(d)
way in which the state is attained. All the (i) dE = dq + p (Vf − Vi )
state functions are exact differentials where,dE = Internal energy
and cyclic integration involving a state O change
ln V
functions is zero.
Ans. (c) dq = amount of heat released
13 0.5 moles of gas A and x moles of ⇒ 0 = dq + p (Vf − Vi )
For isothermal reversible expansion,
gas B exert a pressure of 200 Pa in V [QdE = 0 for an isothermal process]
| W | = nRT ln f
a container of volume 10 m 3 at 1000 Vi ⇒ dq = − 4 (1 − 5) = 16 J
K. Given R is the gas constant in V (ii) dq = n × C × ∆T (for Al)
= nRT ln
JK −1 mol −1 , x is [2019, 9 Jan Shift-I] Vi ⇒16 J = 1 mol × 24 J mol −1 K −1 × ∆T
2R 4 −R 4+R 2R 16
⇒ ∆T = K = K
2
(a) (b) (c) (d) where,V = final volume,Vi = initial final. 24 3
4−R 2R 2R 4+ R
or | W | = nRT lnV − nRT lnVi
Ans. (b) On comparing with equation of straight 16 For a diatomic ideal gas in a closed
From the ideal gas equation, line, y = mx + c, we get
system, which of the following
pV = ΣnRT ...(i) slope = m = + nRT
plots does not correctly describe
Given: p = 200 Pa, V = 10m3,T = 1000 K intercept = − nRT lnVi
the relation between various
nA = 0.5 moles, nB = x moles Thus, plot of | W | with lnV will give thermodynamic quantities?
On substituting the given values in straight line in which slope of2(T2 ) is
equation (i), we get greater than slope of 1 (T1) which is given
200 × 10 = (nA + nB) × R × 1000 in all options. Cp CV
(a) (b)
200 × 10 Now, if Vi < 1 then y intercept (− nRT Vi )
0.5 + x = becomes positive and if it is positive for
R × 1000 p T
one case then it is positive for other
1 2 2 1 4− R
+x= = − = case also. Thus, it is not possible that
2 R R 2 2R one y-intercept goes above and other
y-intercept goes below. Thus, option (b) (c) U (d) CV
14 Consider the reversible isothermal and (d) are incorrect.
expansion of an ideal gas in a closed If we extent plot given in option (a) it
T V
system at two different temp.T 1 seems to be merging which is not
[2019, 12 Jan Shift-I]
possible because if they are merging
andT 2 (T 1 < T 2 ). The correct graphical they give same +ve y-intercept. But they Ans. (a)
depiction of the dependence of cannot give same y-intercept because For diatomic ideal gases,
work done (W) on the final volume value ofT is different.
f f 
(V) is [2019, 9 Jan Shift-I] Now, if we extent the line ofT1 andT2 C V = R and C p =  + 1 R
2 2 
T2 given in option (c) it seems to be
touching the origin. If they touch the where,f = degree of freedom
T1
|W| origin then y-intercept becomes zero f = translational degree of freedom
which is not possible. Thus, it is not the + degree of freedom
(a) exactly correct answer but among the = 3 + 2 = 5 [at normal temperature]
given options it is the most appropriate
one. The explanation of various plots are as
O ln V follows.
T2 15 An ideal gas undergoes isothermal (a) We know that,C p is heat capacity
compression from 5 m 3 to 1 m 3 at constant pressure. Thus, it does
T1 not vary with the variation in
|W| against a constant external
pressure. Hence, plot given in
(b) pressure of 4 Nm −2 . Heat released option (a) is incorrect.
in this process is used to increase (b) In this plot,C V first increases
O
the temperature of 1 mole of Al. slightly with increase in
ln V
Chemical Thermodynamics 57

temperature and then increases Ans. (c) (a) − 900 J (b) − 900 kJ
sharply with temperature. The According to first law of (c) 270 kJ (d) 900 kJ
sharp increase is due to increase thermodynamics, Ans. (a)
in degree of freedom.
∆ U = q + W = q − p∆ V Work done due to change in volume
Thus, plot given in option (b) is In isochoric process (∆V = 0), ∆U = q against constant pressure is
correct.
In isobaric process (∆p = 0), ∆U = q W = − p (V2 − V1)
(c) For ideal gases, Internal energy In adiabatic process (q = 0), ∆U = W = − 1 × 10 5 Nm−2 (1 × 10 −2 − 1 × 10 −3) m3
(U) ∝T
In isothermal process (∆T = 0) and ∆U = 0 = − 900 Nm = − 900 J [1 Nm = 1 J]
Thus, as temperature increases
∴ ∆U is equal to adiabatic work.
internal energy also increases. As
temperature increases further 22 The internal energy change when a
degree of freedom also increases
19 A piston filled with 0.04 mole of an system goes from state A to B is
thus, there is slight variation in the ideal gas expands reversibly from 40 kJ/mol. If the system goes from
graph. First translational degree of 50.0 mL to 375 mL at a constant A to B by a reversible path and
freedom is present followed by temperature of 37.0°C. As it does returns to state A by an irreversible
rotational and vibrational degree so, it absorbs 208 J of heat. The path, what would be the net change
of freedom. Hence, plot given in values of q and W for the process
option (c) is also correct. in internal energy? [AIEEE 2003]
will be (R = 8.314 J / mol K, (a) 40 kJ (b) > 40 kJ
(d) C V is heat capacity at constant
ln 7.5 = 2.01) [JEE Main 2013] (c) < 40 kJ (d) zero
volume. Thus, it does not vary with
variation in volume. Hence, plot (a) q = + 208 J, W = − 208 J Ans. (d)
given in option (d) is correct. (b) q = − 208 J, W = − 208 J
∆E = 0, in a cyclic process.
(c) q = − 208 J, W = + 208 J
17 The combination of plots which (d) q = + 208 J, W = + 208 J 23 Heat required to raise the
does not represent isothermal Ans. (a) temperature of 1 mole of a
expansion of an ideal gas is As the process is carrying out at substance by 1° is called
[2019, 12 Jan Shift-II] constant temperature, therefore this (a) specific heat [AIEEE 2002]
type of expansion is called isothermal
reversible expansion, for which, ∆U = 0. (b) molar heat capacity
p p Hence,q = − W (c) water equivalent
i.e., heat absorbed by the system is equal (d) specific gravity
O 1/Vm O Vm to the work done by the system. Ans. (b)
(a) (b) Thus, q = + 208 J, W = − 208 J The amount of heat required to raise the
temperature of one mole of substance
pVm through 1°C is called molar heat capacity.
20 An ideal gas is allowed to expand
U q
both reversibly and irreversibly in C=
an isolated system. IfTi is the initial T2 − T1
O p O Vm
(c) (d) temperature andTf is the final
24 A heat engine absorbs heat q 1 from
Ans. (c) temperature, then which of the
a source at temperatureT 1 and
following statements is correct ?
In isothermal expansion, pVm = K [AIEEE 2006]
heat q 2 from a source at
(constant) temperatureT 2 . Work done is
(a) (Tf ) irrev > (Tf ) rev
This relation is plotted in graph ‘C’
(b) Tf > Ti for reversible process but found to be J (q 1 + q 2 ). This is in
K
Likewise, p = Tf = Ti for irreversible process accordance with [AIEEE 2002]
Vm
(c) (Tf ) rev = (Tf ) irrev (a) First law of thermodynamics
This relation is plotted in graph “A”. (b) Second law of thermodynamics
(d) Tf = Ti for both reversible and
Thus, graph B and D are incorrect. (c) Joules equivalent law
irreversible processes
For them the correct graphs are: (d) None of the above
Ans. (a)
Ans. (c)
In an ideal gas, there are no
p and U intermolecular forces of attraction. Joules law suggests
Mechanical work done
Hence,Tf = Ti for both reversible and
irreversible processes. by the system, W
Vm Vm J=
Net heat given to the system, Q
for graph B for graph D
21 An ideal gas expands in volume Hence, J=
W
from 1 × 10 −3 m 3 to1 × 10 −2 m 3 at q 1 + q2
18 ∆U is equal to [JEE Main 2017] 300 K against a constant pressure of Therefore, W = J (q 1 + q2 )
(a) isochoric work (b) isobaric work 1 × 10 5 Nm −2 . The work done is is constant with Joules law of
(c) adiabatic work (d) isothermal work [AIEEE 2004] equivalence.
58 JEE Main Chapterwise Topicwise Chemistry

400 × 0.2
TOPIC 2 nH + = × 2 = 0.16 moles Ans. (718)
1000 Born-Haber cycle for KCl is as follows
Reactions Related to and 1 mole of NaOH produces 1 mole of 1 KCl(s); DH°f
Enthalpies and Hess’s Law OH− . K(s)+ Cl
2 2 (g)
600 × 0.1
nOH − = = 0.06 DHsublimation DHdissociation
1000
25 200 mL of 0.2 M HCl is mixed with K(g) Cl (g)
nOH − is low.
300 mL of 0.1 M NaOH. The molar
IE1
heat of neutralisation of this EA
H2SO4 + 2NaOH → Na2SO4 + 2H2O
reaction is − 57.1 kJ. The increase K(+g) + Cl(–g) KCl(s), DH°lattice
Mol : 1 2 1 2
in temperature in °C of the system 1
∴ ∆Hf°
= ∆Hsublimation + ∆Hdissociation
on mixing is x × 10 − 2 . Now, 1 moleH2SO4 requires 2 moles
2
NaOH, then 0.06 mole of NaOH will
The value of x is ……… (Nearest require = 0.03 moles of H2SO4 + IE1 + EA+ ∆Hlattice
1 − 436.7 kJ / mol = 89.2 kJ / mol
integer) ∴ 0.06 mole of OH− reacts with 0.06 + × (243 kJ / mol) + 419 kJ/mol + (–348.6
[Given, specific heat of water = moleof H+ . 2
°
kJ/mol) + ∆Hlattice
4.18 J g − 1 K − 1 m = 1 × 1000
⇒ °
∆Hlattice = − 717.8 kJ / mol
Density of water = 1.00 gcm − 3 ] Now, heat liberated from reaction
= heat gained by solution. ∴ Magnitude of lattice enthalpy of KCl in
(Assume no volume change on
n × ∆H = m × C p × ∆T kJ/mol is 718 (nearest).
mixing) [2021, 27 Aug Shift-I]
0.06 × 57.1 × 10 3 = (1000 × 1) × 4.18 × ∆T
Ans. (82) 29 At 298 K, the enthalpy of fusion of a
⇒ ∆T = 0.8196 K
Millimoles of HCl = 200 × 0.2 = 40
= 82 × 10 −2 K
solid (X ) is 2.8 kJ mol −1 and the
Millimoles of NaOH = 300 × 0.1 = 30 enthalpy of vaporisation of the
Heat released (q) = n × molar heat 27 For water at 100°C and 1 bar, liquid (X ) is 98.2 kJ mol −1 . The
=
30
× 57.1 × 1000 = 1713 J ∆ vap H − ∆ vap U = …………… × 10 2 J enthalpy of sublimation of the
1000
mol −1 . substance (X ) in kJ mol −1 is …… .
Mass of solution = 500 × 1 = 500 g (Nearest integer)
We know that,
(Round off to the nearest integer) [2021, 25 July Shift-I]
q 1713 J [Use : R = 8.31 J mol −1 K −1 ] Ans. (101)
∆T = =
mc 500 g × 4.18 J /g -K [Assume volume of H2O(l) is much Given,
= 0.8196 K = 81.96 × 10 −2 K smaller than volume of H2O(g). Enthalpy of fusion,
x ≈ 82 Assume H2O(g) treated as an ideal ∆Hfus = 2. 8 kJ mol −1
gas] [2021, 27 July Shift-I] Enthalpy of vaporisation,
26 When 400 mL of 0.2 M H2SO4 Ans. (31) ∆Hvap = 98. 2 kJ mol −1
solution is mixed with 600 mL of H2O(l ) q H2O( g) ∆Hfus ∆Hvap
Solid Liquid Gas
0.1 M NaOH solution, the increase in Using formula, ∆H = ∆U + ∆ng RT
temperature of the final solution is For 1 mole water,
…………… × 10 −2 K. (Round off to ∆ng = 1
∆H sub

the nearest integer). ∴∆ng RT = 1 mol × 8.31 J/mol K × 373 K Using Hess’s law,
∆Hsub = ∆Hfus + ∆Hvap
[Use : H+ (aq) + OH+ (aq) → H2O; = 3099.63 J
= 2.8 + 98.2
∆ y H = − 57.1 kJ mol −1 ] ~− 31 × 102 J
= 101 kJ/mol
Specific heat of H2O = 0.18 J K −1 28 The Born-Haber cycle for KCl is
g −1 , density of H2O = 1.0 g cm −3 . evaluated with the following data : 30 At 298.2 K the relationship
Assume no change in volume of between enthalpy of bond
∆ f H° for KCl = − 436.7 kJ mol −1
solution on mixing. dissociation (in kJ mol −1 ) for
[2021, 27 July Shift-II] ∆ sub H° for K = 89.2 kJ mol −1 , hydrogen (E H ) and its isotope,
Ans. (82) ∆ ionisation H° for K = 419.0 kJ mol −1 ; deuterium (E D ), is best described
n × 1000 ∆ electron gain H° for Cl(g) = − 348.6 kJ by [2021, 25 July Shift-I]
Molarity =
V (mL) mol −1 , ∆ bond H° for 1
(a) EH = ED (b) EH = ED
where, n = number of moles
Cl 2 = 243.0 kJ mol −1 2
~ ED − 7.5
V = volume of solution in mL (c) EH − (d) EH = 2 ED
molarity × volume (mL) The magnitude of lattice enthalpy
Moles = Ans. (c)
1000 of KCl in kJ mol −1 is ………
Enthalpy of bond dissociation (kJ/mol) at
1 mole of H2SO4 produces 2 moles ofH+ (Nearest integer)
[2021, 26 Aug Shift-I]
298.2 K
Chemical Thermodynamics 59

For hydrogen = 435.88 kJ/mol This reaction involves the breaking of 275 + 6 × 80 + 1100
⇒ ES − F =
For deuterium = 443.35 kJ/ mol 2C—H bonds and formation, of 1 C == C 6
bond and 1H H bond. = 309.16 kJ mol −1 = 309kJ mol −1
Hence, difference in energy of
deuterium and hydrogen is approx. ∆rH =
7.50 kJ/mol [Sum of bond ethalpies ofreactants] 35 Lattice enthalpy and enthalpy of
Therefore, equation is [EH ~− E D − 7.5] − [Sum of bond enthalpies of products] solution of NaCl are 788 kJ mol −1
Here, deuterium is a heavy isotope of
= [1 ∆ C - C H + 6∆ C -H H] and 4 kJ mol −1 , respectively. The
hydrogen that’s why they required more − [1 ∆ C == C H + 4∆ C H H + 1∆H H H] hydration enthalpy of NaCl is
enthalpy of bond dissociation, i.e. = (357 + 6 × 414) − [611 + 4 × 414 + 436] [2020, 5 Sep Shift-II]
7.5 kJ/mol. = 2831 − 2703 (a) −780 kJ mol −1 (b) 780 kJ mol −1
= 128 kJ/mol. (c) −784 kJ mol −1 (d) 784 kJ mol −1
31 If the standard molar enthalpy Ans. (c)
change for combustion of graphite 33 The standard enthalpies of The enthalpy of solution of an ionic solid
powder is −2.48 × 10 2 kJ mol −1 , the formation of Al 2O 3 and CaO are is numericlly equal to the sum of its
amount of heat generated on −1675 kJ mol −1 and hydration and lat energies,
−625 kJ mol −1 respectively.
° ° °
combustion of 1 g of graphite i.e. ∆Hsol = ∆Hhydration + ∆Hlattice
For the reaction, ∆H = 4
powder is …… kJ. (Nearest integer) ∴ NaCl (s) NaCl (aq)
[2021, 22 July Shift-II] 3CaO + 2Al → 3Ca + Al 2O 3 the
∆H° =788 ∆H°
Ans. (21) standard reaction enthalpy ∆ r H ° hyd
Na+ (g) + Cl –(g)
Standard molar enthalpy change for ……… kJ.
combustion of graphite powder, i.e. ∆ solH ° = ∆ latticeH ° + ∆hyd H °
(Round off to the nearest integer).
. × 102 kJ mol −1.
carbon-12 is –248 [2021, 17 March Shift-I] 4 = 788 + ∆hyd H °
So, heat generated of 1g of graphite Ans. (230) ∆Hhyd H ° = − 784 kJ/mol
powder °
Given, ∆fHAl = − 1675 kJ/mol
. × 102
248 °
2 O3
36 The standard heat of formation
= ∆fHCaO = − 625 kJ/mol °
12
To find ∆ r H ° for the reaction
(∆ f H 298 ) of ethane (in kJ/mol), if
= 20.66 = 21 kJ. 3CaO + 2Al → 3Ca + Al2O3; ∆ r H º = ?
the heat of combustion of ethane,
Hence, amount of heat generated is ∆ r H ° = Σ∆fHProduct
°
− Σ∆fHReactant
° hydrogen and graphite are
21 kJ. °
= { ∆fHAl2 O + 3∆fHCa } ° −1560,−393.5 and −286 kJ / mol,
3
°
− {3∆fHCaO + 2∆fHAl°
}
respectively is ………
32 For the reaction, ° °
[2020, 7 Jan Shift-II]
= ∆Hf (Al2O3) − 3 × ∆Hf (CaO)
Ans. (192.50)
C 2H6 → C 2H4 + H2 We know, ∆fH ° for elemental state = 0
° ° ∆fH° of ethane is ∆H° of the reaction :
the reaction enthalpy ⇒ ∆fHCa = 0, ∆fHAl =0
2C(graphite) + 3 H2 (g) → C2H6 (g)
∆ r H = .......... kJ mol −1 Putting the value,
From ∆ cH° (heat of combustion) values,
(Round off to the nearest integer). ∆ r H ° = { − 1675 + 0 } − {3(− 625) + 0 }
= − 1675 + 1905 = 230 kJ ∆fH ° = (2 × ∆ cH ° of graphite)
[Given : Bond enthalpies in + (3 × ∆ cH ° of H2 ) − (∆ c H ° of C2H6 )
kJ mol −1 :
34 The average S—F bond energy in = (− 2 × 286) + (− 393.5 × 3)
C C = 347, C == C = 611; C H
kJ mol −1 of SF6 is ………… − (− 1560) kJ mol −1
= 414; HH = 436]
[2021, 18 March Shift-I]
(Rounded off to the nearest = − 192.50 kJ mol −1

Ans. (128)
integer) [Given, the values of
standard enthalpy of formation of 37 The heat of combustion of ethanol
The equation representing various
substances involved in chemical
SF6 (g), S(g) and F(g) are –1100, 275 into carbon dioxides and water is
reaction is and 80 kJ mol −1 respectively. ] − 327 kcal at constant pressure.
[2021, 26 Feb Shift-II] The heat evolved (in cal) at
H H
  Ans. (309) constant volume and 27°C (if all
H  C  C H → F gases behave ideally) is
 
(R =2 cal mol −1 K −1 ) ………
F F
H H H H S(g)+ 6F(g) SF6 (g) S
‚ ƒ F F [2020, 2 Sep Shift-II]
C == C + H H F
ƒ ‚ Ans. (326400)
H H So, ∆fH ° [S, g] + 6 × ∆fH ° [F, g]
The combustion equation of ethanol
Given bond enthalpies of various bonds = ∆fH ° [SF6 , g] + 6 × E S − F (C2H5OH or C2H6O) is
in kJ mol −1 i.e. C  C = 347, [∴E S − F = Average SF bond energy in  6 1 300 K
C == C = 611, C H = 414,H H = 436 SF6 ] C2H6O(l ) +  2 + −  O2 (g) →
 9 2
275 + 6 × 80 = − 1100 + 6 × E S − F
60 JEE Main Chapterwise Topicwise Chemistry

6 1000
Enthalpy (H1) of sublimation of iodine
2CO2 (g) + H2O(l )
2 =3 ∫ 23dT + 0.01T dT = 24 cal g –1
300
or C2H6O(l ) + 3O2 (g) → 2CO2 (g) + 3H2O(l ) 1000
If q is the amount of heat involved in a
 0.01T 2  system then at constant pressureq = q p
∆ng = (2 + 0) − (0 + 3) = − 1 = 3 23T + 
2  300 and
⇒dq p = duv + ∆ng RT 
∆H = C p ∆T
⇒duv = dq p − ∆ng RT
 0.01  H2 − H1 = C p (T2 −T1)
= − 327 − (− 1) × (2 × 10 −3) × 300 = 3 23 (1000 − 300) + (10002 − 3002 )
 2  H2 = H1 + ∆C p (T2 −T1)
= −326400
. kcal = −326400 cal
= 3 [16100 + 4550] = 61950 J ≈ 62 kJ H2 = 24 + (0.031 − 0.055) (250 − 200)
Q dq p = Heat at constant pressure or
H2 = 24 + (−0.024) (50)
enthapy change
dUv = Heat at constant volume or
40 The difference between ∆H and ∆U = 24 − 12. = 22. 8 cal/g
internal energy change (∆H − ∆U), when the combustion of Thus, the enthalpy of sublimation of
one mole of heptane (l) is carried out iodine at 250 is 22.8 cal/g.
38 If enthalpy of atomisation for Br 2 (l) at a temperature T, is equal to
[2019, 10 April Shift-II] 42 Given :
is x kJ/mol and bond enthalpy for (i) C(graphite) + O2 (g ) → CO2 (g );
(a) − 4 RT (b) 3 RT
Br 2 is y kJ/mol, the relation
(c) 4 RT (d) − 3 RT ∆ r H È = x kJ mol − 1
between them [2020, 9 Jan Shift-II]
Ans. (a) 1
(a) is x < y (b) does not exist (ii) C(graphite) + O2 (g ) → CO2 (g );
Key Idea The relation between ∆H and 2
(c) is x > y (d) is x = y
∆U is ∆ r H È = y kJ mol − 1
Ans. (c) ∆H = ∆U + ∆ng RT 1
Atomisation of Br2 (l ) where, ∆ng = Σnp − ΣnR (iii) CO (g ) + O2 (g ) → CO2 (g );
2
Br2 (l ) → 2Br (g); ∆H = x kJ mol −1 = number of moles of gaseous products ∆r H È = z kJ mol− 1
which can be considered as sum of − number of moles of gaseous reactants.
following : The general combustion reaction of a Based on the above
Br2 (l ) → Br2 (g) ; hydrocarbon is as follows : thermochemical equations, find
∆H = a positive value ...(i) Cx Hy +  x +  O2 → xCO2 + H2O
y y out which one of the following
(endothermic process)  4 2 algebraic relationships is correct?
Br2 (g) → 2Br (g); ∆H For heptane, x = 7, y = 16 (a) y = 2 z − x (b) x = y − z
(bond enthalpy ofBr2 ) = y ...(ii) ⇒ C7H16 (l ) + 11O2 (g) → 7CO2 (g) + 8H2O(l ) (c) z = x + y (d) x = y + z
∴ x = y + (Positive value), and x > y. ∴ ∆ng = 7 − 11 = − 4
[2019, 12 Jan Shift-II]

Now, from the principle of Ans. (d)

39 For silver, C p ( J K −1mol −1 ) thermochemistry, Second equation given in this question is
= 23 + 0.01 T. If the temperature (T ) ∆H = ∆U + ∆ng RT wrong. Hence, No answer in correct. If
⇒ ∆H − ∆U = ∆ng RT = −4RT corrected second equation is given, i.e.
of 3 moles of silver is raised from 1
300 K to 1000 K at 1 atm pressure, C(graphite) + O2 (g) → CO(g)
41 Enthalpy of sublimation of iodine is 2
the value of ∆H will be close to
[2019, 8 April Shift-I]
24 cal g −1 at 200°C. If specific heat and if we take the above reaction in
of I 2 ( s ) andI 2 (vap.) are 0.055 and consideration then x = y + z will be the
(a) 62 kJ (b) 16 kJ answer as :
(c) 21 kJ (d) 13 kJ 0.031 cal g −1 K −1 respectively, then 1
enthalpy of sublimation of iodine at (ii) C(graphite) + O2 (g) → CO(g),
Ans. (a) 2
According to Kirchoff’s relation,
250°C in cal g −1 is ∆ r H ° = y kJ/mol
T2 [2019, 12 April Shift-I]
1
∆H = n ∫ C pdT …(i) (a) 2.85 (b) 5.7 (iii) CO(g) + O2 (g) → CO2 (g),
2
(c) 22.8 (d) 11.4
T1
∆ r H ° = z kJ/mol
where, ∆H = Change in enthalpy. Ans. (c) Summing up both the equation you will
C p = Heat capacity at constant Key Idea When q is the amount of heat get equation (i)
pressure. involved in a system then at constant C(graphite) + O2 (g) → CO2 (g),
Given, n = 3 moles, pressure
∆ r H ° = x kJ/mol
T1 = 300 K, q = qp
Hence, x, y and z are related as:
T2 = 1000 K, and C p ∆T = ∆H
x =y + z
C p = 23 + 0.01 T Given reaction :
On substituting the given values in Eq. (i), I2 (s ) → I2 (g) 43 The combustion of benzene (l)
we get Specific heat ofI2 (s ) = 0.055 cal g −1 K −1.
1000 gives CO 2 (g) and H2O(l). Given that
Specific heat of
∆H = 3 ∫ (23 + 0.01T )dT I2 (vap) = 0.031 cal g –1 K–1.
heat of combustion of benzene at
300
constant volume is
Chemical Thermodynamics 61

−3263.9 kJ mol −1 at 25° C; heat of Ans. (c) ∆u = −136447. kJmol −1

combustion (in kJ mol −1 ) of Based on given ∆ r H ° Enthalpy of a combustion reaction is
benzene at constant pressure will ∆H = ∆u + ∆ng RT
∆fH ° = HCO
° = − 393.5 kJ mol − 1 …(i)
be (R = 8.314 JK −1 mol −1 ) 2 where, ∆u = internal energy
[JEE Main 2018] ∆fH ° = H °H 2 O = − 285.8 kJ mol − 1 …(ii) ∆ng = moles of gas
(a) 4152.6 (b) −452.46 (products − reactants)
(c) 3260 (d) −3267.6 ∆fH ° = H °O 2 = 0.00 (elements) …(iii) ∆R = Gas constant,
Ans. (d) Required thermal reaction is for ∆fH ° of T = Temperature inK
Key Idea Calculate the heat of CH4 As per equation,
combustion with the help of following Thus, from III ∆ng = 2 − 3 = −1
formula 890.3 = [∆fH ° (CH4 ) +2 ∆fH ° (O2 )] T = 25° C = 25 + 273 K ⇒ T = 298 K
∆Hp = ∆U + ∆ng RT  (−1) × 8314
. × 298 
− [∆fH ° (CO2 ) + 2 ∆fH ° (H2O)] Thus, ∆H = −136447 . +
where, ∆Hp = Heat of combustion at 
= ∆fH ° (CH4 ) + 0] − [− 393.5 − 2 × 285.5]  1000 
constant pressure
∆H = −136447
. − 2477
. = −1366947
. kJmol −1
∆U = Heat at constant volume (It is also ∴ ∆fH ° (CH4 ) = − 74.8 kJ / mol
called ∆E) Hence, the enthalpy of combustion, ∆ cH
for the given reaction will be
∆ng = Change in number of moles (In
45 The heats of combustion of carbon −1366.947 kJmol −1.
gaseous state).
and carbon monoxide are − 393.5
R = Gas constant;T = Temperature.
and − 283.5 kJ mol −1 , respectively.
47 The value of enthalpy change (∆H)
From the equation, for the reaction
15 The heat of formation (in kJ) of
C6H6 (l) + O2 (g) → 6CO2 (g) + 3H2O (l ) carbon monoxide per mole is C 2H5OH( l ) + 3O 2 (g )→ 2CO 2 (g )
2
[JEE Main 2016] + 3H2O(l )
Change in the number of gaseous moles
(a) 676.5 (b) −676.5 (c) −1105
. (d) 110.5 at 27°C is − 1366.5 kJ mol −1 . The
i.e.
15 3 Ans. (c) value of internal energy change
∆ng = 6 − = − or −1.5
2 2 C(s ) +O2 (g) → CO2 (g) ; for the above reaction at this
Now we have ∆ng and other values given ∆H = −393.5 kJ mol −1 …(i) temperature will be [AIEEE 2011]

in the question are 1 (a) − 1371.5 kJ (b) − 1369.0 kJ

CO + O2 → CO2 (g);
∆U = −32639 . kJ/mol 2 (c) − 1364.0 kJ (d) − 1361.5 kJ
T = 25° C = 273 + 25 = 298 K ∆H = − 283.5 kJ mol −1 …(ii) Ans. (c)
. JK−1 mol −1
R = 8314 On subtracting Eq. (ii) from Eq. (i), we get Relation between ∆H (enthalpy change)
So, ∆Hp = (−32639 . ) + (−1.5) × 8314
. 1
C(s ) + O2 (g) → CO(g); and ∆E (internal energy change) is
× 10 −3 × 298 2 ∆H = ∆E + ∆ng RT
= −3267.6 kJ mol −1 ∆H = (− 393.5 + 283.5) kJ mol − 1 where, ∆ng = (moles of gaseous
= − 110 kJ mol −1 products) – (moles of gaseous reactants)
(approx. )
44 Given, For the given reaction,
C (graphite) + O 2 (g) → CO 2 (g); 46 For the complete combustion of ∆ng = 2 − 3 = − 1
∆ r H° = − 393.5 kJ mol − 1 ethanol,
⇒ −1366.5 = ∆E − 1 × 8.314 × 10 −3 × 300
1 C 2H5OH(l) + 3O 2 (g) → 2CO 2 (g)
H2 (g) + O 2 (g) → H2O(l); . kJ mol −1
∴ ∆E = − 13640
2 +3H2O(l)
the amount of heat produced as 48 Consider the reaction,
∆ r H° = − 285.8 kJ mol − 1
measured in bomb calorimeter is 4NO 2 (g) + O 2 (g) → 2N 2O 5 (g),
CO 2 (g) + 2 H2O(l) → CH4 (g) ∆ r H = − 111 kJ.
1364.47 kJmol −1 at 25°C. Assuming
+2O 2 (g); ideality, the enthalpy of If N 2O 5 (s ) is formed instead of
−1
∆ r H° = + 890.3 kJ mol combustion, ∆ C H for the reaction N 2O 5 (g ) in the above reaction, the
Based on the above will be ∆ r H value will be
thermochemical equations, the [R = 8.314 JK −1mol −1 ] (Given, ∆H of sublimation for N 2O 5
value of ∆ r H° at 298 K for the [JEE Main 2014]
is 54 kJ mol −1 ) [AIEEE 2011]
reaction, [JEE Main 2017] (a) −1366.95 kJmol−1 (a) − 165 kJ (b) +54 kJ
. kJmol−1
(b) −136195
C (graphite) + 2 H2 (g) → CH4 (g) (c) +219 kJ (d) − 219 kJ
(c) −1460.50 kJmol−1 Ans. (a)
will be (d) −1350.50 kJmol−1 ∆H =− 111 KJ
(a) + 78.8 kJ mol− 1 Ans. (a) 4N2 (g) + O2 (g) → 2N2O5 (g),
(b) + 144.0 kJ mol− 1
144244 3
C2H5OH (l ) + 3O2 (g) → 2CO2 (g) + 3 H2O(l )
(c) − 74.8 kJ mol− 1 ∆H = ? + 54kJ
Amount of heat produced in bomb
(d) − 144.0 kJ mol− 1 2N2O5 (s )
calorimeter,
62 JEE Main Chapterwise Topicwise Chemistry

From Hess law, ∆Hr = ∆Hf (H2O, l ) − ∆Hf (H2 , g) Ans. (c)
∆Hf + ∆Hsub = ∆Hreaction ; 1 H2O (l ) → H2O (g)
− ∆Hf (O2 , g)
∆Hf = ∆Hreaction − ∆Hsub 2 ∆ng = 1 − 0 = 1
= −111 kJ − (54 kJ) = − 286.20 = ∆Hf (H2O, l ) − 0 − 0 ∆E = ∆H − ∆ng RT
= −111 − 54kJ = −165 kJ ∆Hf (H2O, l ) = − 286.20 = 41 − (1 × 8.3 × 373 × 10 −3)
Thus, the enthalpy of formation, ∆Hf for Now, consider the ionization ofH2O [R = 8.3 × 10 −3]
N2O5 (s ) is −165 kJ . H2O(l ) → H+ (aq) + OH− (aq) = 37.9 kJ mol −1

∆H = 57.32 kJ
49 The standard enthalpy of formation 53 (∆H − ∆E) for the formation of
of NH3 is −46.0 kJ mol −1 . If the ∆Hr = ∆Hf (H+ , aq) + ∆Hf (OH− , aq)
− ∆Hf (H2O, l ) carbon monoxide (CO) from its
enthalpy of formation of H2 from its
atoms is –436 kJ mol −1 and that of 57.32 = 0 + ∆Hf (OH− , aq) − (− 286.20) elements at 298 K is
N 2 is −712 kJ mol −1 , the average Thus, ∆Hf (OH− , aq) = 57.32 − 286.20 (R = 8.314 JK –1 mol–1 ) [AIEEE 2006]
bond enthalpy of N—H bond in NH3 = −228.80 kJ. (a) − 1238.78 J mol−1
is [AIEEE 2010]
(b) 1238.78 J mol−1
(a) – 964 kJ mol −1 (b) +352 kJ mol −1 51 Oxidising power of chlorine in (c) − 2477.57 J mol−1
(c) +1056 kJ mol −1 (d) –1102 kJ mol −1 aqueous solution can be (d) 2477.57 J mol−1
Ans. (b)
determined by the parameters Ans. (b)
1 3
indicated below Calculate ∆H − ∆E by using the formula,
N2 (g ) + H2 (g ) → NH3(g ), 1
∆ diss H ∆H − ∆E = ∆ng RT
s
2 2 1 ∆ EA H s
2
∆ r H = − 46 kJ mol −1 Cl 2 (g ) → Cl (g ) → 1
2 = × 8.314 × 298 = 1238.78 J mol −1
Bond enthalpy ofH2 = 436 kJ mol −1 s ∆ hyd H 2
[+ ve sign is taken because energy is Cl– (g ) → Cl– (aq )  C(s ) + 1 O (g ) → CO(g )
supplied  2
2 
The energy involved in the  
to break theH  H bond into its atoms] 1 1 1
 ∆ng = 1 − = 
Similarly, bond enthalpy of conversion of Cl 2 (g ) to Cl– (aq )  2 2 
2
N2 = +712 kJ mol −1
(using the data, ∆ diss H sC l = 240
1 3  54 The enthalpy changes for the
∆ r H =  BE (N2 ) + BE(H2 )  − 3 BE(N  H) kJ mol −1
2
2 2  following processes are listed below
∆ EA H Cl
s
= − 349 kJ mol −1 ,
1 3 
−46 =  × 712 + × 436 − 3 BE (N  H) Cl 2 (g ) = 2Cl(g ), 242.3 kJ mol −1
∆ hyd H Cl = − 381 kJ mol–1 ) will
s
2 2  I 2 (g ) = 2I (g ), 151.0 kJ mol −1
−46 = (356 + 654) − 3 BE (N  H)
be [AIEEE 2008]
(a) +152 kJ mol−1 ICl(g ) = I(g ) +Cl(g ),211.3 kJ mol −1
3 BE (N H) = (1010) + 46
(b) – 610 kJ mol−1 I 2 (s ) = I 2 (g ),62.76 kJ mol −1
3 BE (N  H) = 1056
(c) – 850 kJ mol−1 Given that the standard states for
BE (N  H) = 1056 /3 = 352 kJ mol −1
(d) + 120 kJ mol−1 iodine and chlorine are I 2 (s ) and
50 On the basis of the following Ans. (b) Cl 2 (g ), the standard enthalpy of
thermochemical data 1 formation of ICI is [AIEEE 2006]
Cl2 (g) → Cl – (aq)
[ ∆ f G° H+ (aq ) = 0] 2 (a) − 14.6 kJ mol−1
1 (b) − 16.8 kJ mol−1
H2O(l ) → H+ (aq ) + OH− (aq ); ∆H = ∆Hdiss (Cl2 ) + ∆HEA Cl + ∆Hhyd (Cl – )
2 (c) + 16.8 kJ mol−1
∆H = 57.32 kJ
=
240
− 349 − 381 = − 610 kJ mol –1 (d) + 244.8 kJ mol−1
1
H2 (g ) + O 2 (g ) → H2O(l ); 2 Ans. (c)
2
1 1
∆H = − 286.02 kJ 52 Assuming that water vapour is an I2 (s ) + Cl2 (g) → ICl(g)
2 2
The value of enthalpy of formation ideal gas, the internal energy 1 1
∆H = ∆Hs → g + ∆Hdiss (Cl2 )
of OH− ion at 25°C is [AIEEE 2009] change (∆E) when 1 mole of water  2 2
(a) –22.88 kJ (b) –228.88 kJ is vaporised at 1 bar pressure and 1 
+ ∆Hdiss (I2 ) − ∆H ICl
(c) +228.88 kJ (d) –343.52 kJ 100°C, (Given : molar enthalpy of 2 
Ans. (b) vaporisation of water at 1 bar 1 1 1 
and 373 K = 41 kJ mol −1 and =  × 62.76 + × 242.3 + × 151.0 
Consider the heat of formation ofH2O. 2 2 2 
1 R = 8.3 J mol −1 K −1 ) will be − 211.3
H2 (g) + O2 (g) → H2O(l ); [AIEEE 2007]
2 = 228.03 − 211.3
(a) 4.100 kJ mol−1 (b) 3.7904 kJ mol−1
∆H = − 286.20 kJ
(c) 37.904 kJ mol−1 (d) 41.00 kJ mol−1 ∆H = 16.73 kJ mol −1
Chemical Thermodynamics 63

55 The standard enthalpy of formation is − 200 kJ mol −1 . The bond Ans. (c)
(∆Hf° ) at 298 K for methane, CH4 (g) dissociation energy of X 2 will be Enthalpy change is state function and
is − 74.8 kJ mol −1 . The addition [AIEEE 2005] depends only on initial and final
−1 condition do not depend on path or
information required to determine (a) 400 kJ mol (b) 300 kJ mol−1 nature of its intermediates.
the average energy for C—H bond (c) 200 kJ mol−1 (d) None of these
formation would be [AIEEE 2006] Ans. (d) 60 If at 298 K, the bond energies of
(a) the dissociation energy ofH2 and Formation of XY is shown as C—H, C—C, C== C and H—H bonds
enthalpy of sublimation of carbon X2 + Y2 → 2XY are respectively 414, 347, 615 and
(b) latent heat of vaporisation of ∆H = [(BE) X  X + (BE) Y  Y ] − [ 2 (BE)X  Y ] 435 kJ mol −1 , the value of enthalpy
methane change for the reaction,
(c) the first four ionisation energies of If (BE) of X Y = a KJ /mol
H2C == CH2 (g ) + H2 (g) →
carbon and electron gain enthalpy of then, (BE) of (X  X) = a and (BE) of
hydrogen a  1 1  H3C CH3 (g ) at 298 K will be
(Y Y ) = Q X + Y → XY [AIEEE 2003]
(d) the dissociation energy of hydrogen 2  2 2 2 2 
molecule,H2 (a) + 250 kJ (b) − 250 kJ
∴ ∆Hf (X Y ) = − 200 kJ (c) + 125 kJ (d) − 125 kJ
Ans. (a)
 a 
Carbon is found in solid state. The state ∴ − 400 (for 2 mol XY ) =  a + − 2a  Ans. (d)
 2 
of substance affects the enthalpy CH2 == CH2 + H2 → CH3  CH3
a
change. − 400 = − ; a = + 800 kJ ∆H = (BE) reactants − (BE) products
2
C(s ) → C(g) sublimation, = 4 (BE) C —H + (BE) C == C + (BE) H  H
The bond dissociation energy of
and H2 (g) → 2H (g) dissociation are X2 = 800 kJ mol −1. − [6 (BE) C  H + (BE) C H ]
required for C—H bond. = − 125 kJ
58 The enthalpies of combustion of
56 Consider the reaction, carbon and carbon monoxide are
N 2 + 3H2 → 2NH3 carried out − 393.5 and − 283 kJ mol −1 ,
TOPIC 3
at constant temperature and respectively. The enthalpy of Entropy, Free Energy
pressure. If ∆H and ∆E are the formation of carbon monoxide per Change and Spontaneity
enthalpy and internal energy mole is [AIEEE 2004]
changes for the reaction, which of (a) 110.5 kJ (b) 676.5 kJ 61 For the reaction,
the following expressions is true ? (c) − 676.5 kJ (d) − 110.5 kJ 2NO 2 (g) s N 2O 4 (g), when
[AIEEE 2005]
(a) ∆H > ∆E (b) ∆H < ∆E
Ans. (d) ∆S = − 176.0 JK −1 and ∆H = − 57.8 kJ
(c) ∆H = ∆E (d) ∆H = 0 I C(s ) + O2 (g) → CO2 (g), mol −1 , the magnitude of ∆G at 298
∆H = − 393.5 kJ K for the reaction is ………
Ans. (b) 1
II CO(g) + O2 (g) → CO2 (g), kJ mol −1 . (Nearest integer)
According to relationship of ∆H and ∆E, 2 [2021, 1 Sep Shift-II]
∆H = ∆E + ∆ng RT ∆H = − 283.0 kJ
[I – II] gives Ans. (5)
∆H = enthalpy change 1
III C(s ) + O2 (g) → CO(g), Given, ∆H = − 57.8 kJ mol −1
(at constant pressure)
2 ∆S = − 176 JK −1 mol −1
∆E = internal energy change
[∆H = −393.5 + 2830. kJ] ∆H = − 110.5 kJ T = 298 K
(at constant volume)
(given reaction is exothermic) The equation III also represents Using Gibb’s free energy relation
( ∆ng = moles of gaseous products formation of one mole of CO and thus, ∆G = ∆H − T∆S
– moles of gaseous reactants) enthalpy change is the heat of formation
where, ∆G = change in Gibb’s free energy
For the reaction of CO (g).
∆H = change in enthalpy
N2 (g) + 3H2 (g) → 2NH3 (g) 59 The enthalpy change for a reaction T = temperature
∆ng = 2 − 4 = −2 does not depend upon the ∆S = change in entropy
Thus, ∆H = ∆E −2RT [AIEEE 2003]
∆G = 57.8 kJ / mol − [298 K
⇒ ∆H < ∆E (a) physical state of reactants and
× (−176 JK−1mol −1)]
Note Numerical value of ∆H < ∆E in products
−176 
exothermic reaction and when ∆ng < 0. (b) use of different reactants for the = 57.8 kJ / mol −  298 × kJ
 1000 
same product
(c) nature of intermediate reaction [∴1 kJ = 1000 J]
57 If the bond dissociation energies of
steps = − 5.352 kJ / mol
XY, X 2 and Y 2 (all diatomic
(d) difference in initial or final | ∆G | = 5.352
molecules) are in the ratio of 1 : 1 : temperatures of involved Hence, answer is 5.
0.5 and ∆Hf for the formation of XY substances
64 JEE Main Chapterwise Topicwise Chemistry

62 The incorrect expression among = 161 J K−1 mol −1 leads to a decrease in randomness. So,
According to Gibb’s equation, entropy decreases.
the following is [2021, 31 Aug Shift-II]
∆G System ∆G ° = ∆H ° − T∆S ° (A) Water 0°C→ ice; ∆S = − ve
(a) = − T (at constant p) (B) Water − 10 ° C
→ ice; ∆S = − ve
∆S Total The reaction becomes spontaneous
∆H ° − T∆S ° when ∆G ° is atleast zero or negative. (C) N2 (g) + 3H2 (g) → 2NH3 (g);
(b) ln k = ∆S = − ve
RT 0 = ∆H ° − T∆S °
−
∆G ° T∆S ° = ∆H ° Number of moles are decreasing
(c) k = e RT
∆H ° 156 kJ mol −1 n = 2 − (3 + 1)
⇒ T= =
(d) For isothermal process, ∆S ° 161 J K−1 mol −1 n= −2
V So, entropy decreases.
Wreversible = − nRT ln f 156000 mol −1
Vi = = 964 K (D) Adsorption; ∆S = − ve
161 J K−1 mol −1
Ans. (b) Adsorption will lead to a decrease
The temperature at which reaction in the randomness of gaseous
All the expression of thermodynamics becomes spontaneous is 964 K. particles.
are correct except
∆H ° − T∆S ° So, entropy decreases.
ln k = 64 For a given chemical reaction, (E) NaCl( s ) → Na+ (aq) + Cl − (aq);
RT
A → B at 300 K the free energy ∆S >0
As we know,
∆G = ∆H − T∆S ° …(i)
change is −49.4 kJ mol −1 and the The number of species on product
Also ∆G = − RT lnK …(ii)
enthalpy of reaction is 51.4 kJ side is more than the number of
∴ From (i) and (ii)
mol −1 . The entropy change of the species on reactant side. So,
− RT lnK = ∆H − T∆S ° reaction is …… JK −1mol −1 . entropy increases on dissolution
− ∆H ∆S ° [2021, 20 July Shift-II] of NaCl in water.
∴ ln K = +
RT R Ans. (360)
66 For a dimerisation reaction
The corect expression is 300K
For the reaction, A → B 2A(g ) → A 2 (g ),
− ∆H ° ∆S ° ∆H °−T∆S °
ln K = + = Gibb’s free energy change at 298 K, ∆U s = − 20kJ mol −1 ,
RT R RT
Given, ∆G = − 494 . kJ/mol ∆S È = − 30JK −1 mol −1 , then the
63 Data given for the following Change in enthalpy ∆Gs will be ……… J.
reaction is as follows. ∆Hreaction = 514
. kJ/mol [2020, 5 Sep Shift-II]

Change in entropy ∆S reaction = ? Ans. (13537.57)

FeO(s) + C (graphite) →
According to Gibbs free energy, ∆H = ∆U + ∆ng RT
Fe(s) + CO(g)
∆G = ∆H − T∆S ∆H = − 20 × 1000 − 1 × 8314
. J/mol.K × 298 K
∆H° ∆S° ∆H − ∆G = −22477.572 J
Substance ⇒∆S =
(kJ mol − 1) (J mol − 1 K − 1) T ∆G = ∆H − T∆S
. − (− 494
514 .) J ∆G = − 22477.572 + 298 × 30
FeO(s ) − 266.3 57.49 = × 1000
300 mol K ∆G = − 13537.57 Joule
C (graphite) 0 5.74 ∆S reaction = 336 J/mol K
Fe(s ) 0 27.28 67 For the reaction; A( l ) → 2B(g)
65 During which of the following ∆U = 2.1 kcal, ∆S = 20cal K −1 at
CO(g) − 110.5 197.6
processes, does entropy decrease ?
300 K.
A. Freezing of water to ice at 0°C.
The minimum temperature in K at Hence, ∆G in kcal is …… .
which the reaction becomes B. Freezing of water to ice at [2020, 8 Jan Shift-I]
spontaneous is ........... (Integer −10°C. Ans. (2.70)
answer) C. N 2(g) + 3H 2(g) → 2NH 3 (g)
[2021, 27 Aug Shift-II] Given: ∆U = 2.1 kcal
Ans. (964) D. Adsorption of CO(g) and lead 20
∆S = 20 cal K −1 = kcal K −1
surface. 1000
FeO(s ) + Cgraphite → Fe (s ) + CO(g)
E Dissolution of NaCl in water. A (l )
- 2B (g)
°
∆Hreaction = ∆Hf°(product) − ∆Hf°(reactants) [2021, 17 March Shift-II]
∴ ∆ng = 2 mol
= [∆Hf°(Fe) + ∆Hf°(CO) ] − [∆Hf°(FeO) − ∆Hf°(C) ] (a) A, B, C and D (b) B and C R = 2 cal K −1 mol −1
(c) A and E (d) A, C and E 2
= [0 + (−110.5)] − [−266.3 − 0] = kcal K −1 mol −1
Ans. (a) 1000
= 156 kJ −1 mol −1
Entropy will decrease in A,B,C and D As we know,
°
∆S reaction °
= ∆S product °
− ∆S reactant
processes. ∆G = ∆H − T∆S
= [∆S °(Fe) + ∆S °(CO) ] − [∆S °(FeO) − ∆S °(C) ] A, B → Freezing of water will decrease and ∆H = ∆U + ∆ng RT
entropy as particles will move closer and ∴ ∆G = ∆U + ∆ng RT − T∆S
= [27.28 + 197.6] − [57.49 + 5.79] forces of attraction will increase. This
Chemical Thermodynamics 65

2 × 2 × 300 300 × 20 ∆G ° = 42
. × 2303 (2.572 − 2.436)
∴ ∆G = 2.1 + − ∴ ln K = − and K = e − ∆G ° / RT .
1000 1000 RT . kJ K−1kg −1
= 131
= 2.1 + 12
. − 6 = −2 .70 The above equation is helpful in ∆Hvap. 2491 kJ kg −1
predicting the spontaneity of the ∆S 3 = =
68 The true statement amongst the reaction. e.g. ∆Tvap. 373 K
following is [2020, 9 Jan Shift-II] (i) If ∆G ° < 0, –∆G ° /RT = + ve . kJ kg −1K−1
= 667
(a) S is not a function of temperature and e − ∆G ° / RT > 1 and hence,K > 1. T  383 K 
but ∆S is a function of temperature. ∆S 4 = Cln 2 = 2 kJ K−1kg −1 ln  
It means that the reaction occur T1  373 K 
(b) Both ∆ S and S are functions of
spontaneously in the forward
temperature.
direction or products predominate = 2 × 2303
. (log 383 − log 373) kJ K−1 kg −1
(c) Both S and ∆ S are not functions of over reactants. = 2 × 2303
. (2.583 − 2.572) kJ K−1 kg −1
temperature.
(ii) If ∆G ° > 0 ; − ∆G ° /RT = − ve and = 0.05 kJ K−1 kg −1
(d) S is a function of temperature but ∆S
is not a function of temperature. e − ∆G ° / RT < 1 ∆S Total = ∆S 1 + ∆S2 + ∆S 3 + ∆S 4
Ans. (b) and hence,K < 1. It means that the = 1.22 + 1.31 + 6.67 + 0.05
Statement (b) is a true statement reaction is non-spontaneous in = 9.26kJ kg −1 K−1
whereas all other statements are forward direction (i.e. product
incorrect. side) but spontaneous in reverse 72 A process has ∆H = 200 J mol −1
By definition, direction (i.e. reactants
and ∆S = 40 JK −1 mol −1 . Out of the
predominate over products or the
and ∆S = ∫
dQ dQ values given below, choose the
dS = reaction occurs rarely).
T T (iii) When K = 1, then ∆G ° = 0. This minimum temperature above which
∴ ∆S is a function of temperature : situation generally occur at the process will be spontaneous
S is also a function of temperature. equilibrium. (a) 20 K (b) 4 K (c) 5 K (d) 12 K
[2019, 10 Jan Shift-II]
69 A process will be spontaneous at all 71 The entropy change associated Ans. (c)
temperature if [2019, 10 April Shift-I] with the conversion of 1 kg of ice at
∆G = ∆H − T∆S
(a) ∆H > 0 and ∆S < 0 273 K to water vapours at 383 K is The process will be spontaneous, when
(b) ∆H < 0 and ∆S > 0 (Specific heat of water liquid and ∆G = − ve, i.e. |T∆S | > | ∆ H |
(c) ∆H < 0 and ∆S < 0 water vapour are 4.2 kJK −1kg −1 and Given : ∆H = 200 J mol −1
(d) ∆H > 0 and ∆S > 0 2.0 kJK −1 kg −1 ; heat of liquid fusion and ∆S = 40 JK−1 mol −1
Ans. (b) and vapourisation of water are | ∆ H | 200
⇒ T> = = 5K
A process will be spontaneous when its
334kJ kg −1 and 2491kJkg −1 | ∆S | 40
free energy (Gibb’s energy) change will be
negative, i.e. ∆G < 0. respectively). So, the minimum temperature for
Spontaneity of a process is decided by (log 273 = 2.436, log373 = 2.572, spontaneity of the process is 5 K.
the value of ∆G, which can be predicted log383 = 2.583)
from the Gibb’s equation, ∆G = ∆H −T∆S (a) 9.26 kJ kg −1 K −1 (b) 8.49 kJ kg −1K −1 73 The process with negative entropy
for positive/negative signs of ∆H and ∆S (c) 7.90 kJ kg −1K −1 (d) 2.64 kJ kg −1K −1 change is
at any/higher/lower temperature as: (a) synthesis of ammonia from N2 and H2
[2019, 9 Jan Shift-II]
(b) dissociation of CaSO4 (s ) to CaO(s)
Comment on Comment on Ans. (a)
andSO3 (g)
∆H ∆S temperature ∆G the process The conversion of 1 kg of ice at 273 K into (c) dissolution of iodine in water
(T) water vapours at 383 K takes place as (d) sublimation of dry ice
< 0 > 0 at any temp. < 0 spontaneous follows: [2019, 10 Jan Shift-II]
> 0 < 0 at any temp. > 0 non- ∆S1 ∆S2 Ans. (a)
spontaneous H2O(s) H2O(l) H2O(l)
The explanation of all the options are as
< 0 < 0 at lower < 0 spontaneous 273K 273K 373K
follows :
temp. ∆S3
(a) N2 (g) + 3H2 (g) → 2NH3 (g),
> 0 > 0 at higher < 0 spontaneous H2O(g) H2O(g) ∆ng = 2 − (1 + 3) = − 2
temp. ∆S4
383K 373K So, ∆S is also negative (entropy
decreases)
70 The incorrect match in the ∆HFusion 334 kJ kg −1
∆S 1 = = ∆ CaO(s ) + SO (g),
following is [2019, 12 April Shift-II] ∆TFusion 273 K (b) CaSO4 (s ) → 3

(a) ∆G ° < 0,K > 1 (b) ∆G ° = 0,K = 1 = 1.22 kJ kg −1 K−1 ∆ng = (1 + 0) − 0 = + 1

(c) ∆G ° > 0,K < 1 (d) ∆G ° < 0,K < 1 T  373 K  So, ∆S = + ve
∆S2 = C ln 2 = 4.2 kJ K−1kg −1 ln   (c) In dissolution, ∆S = + ve because
Ans. (d) T1  273 K 
molecules/ions of the solid solute
The incorrect match is ∆G ° < 0, K < 1. = 42
. × 2303
. (log 373 − log273) kJ K−1kg −1 (here, iodine) become free to move
For an ideal gas ∆G ° = − RT lnK .
66 JEE Main Chapterwise Topicwise Chemistry

in solvated/dissolved state of the  1

77 The standard reaction Gibbs energy
solution, 2  (T1 + T2 ) 2  for a chemical reaction at an
(a) C p ln 
I2 (s ) Water
→ I2 (aq) TT  absolute temperatureT is given by,
(KI)  12 
(d) In sublimation process, molecules   ∆ r G° = A − BT
of solid becomes quite free when  T + T  Where A and B are non-zero
(b) 2 C p ln  1 2 
they become gas, constants.
 4TT 12 
CO2 (s ) → CO2 (g)  (T1 + T2 )2  Which of the following is true
Dry ice (c) C p ln   about this reaction?
So, ∆S will be positive.  4TT 12 
[2019, 11 Jan Shift-II]
T + T  (a) Endothermic if, A < 0 and B > 0
(d) 2 C p ln  1 2 
74 For the chemical reaction,  2TT 12  (b) Exothermic if, B < 0
X - Y , the standard reaction (c) Exothermic if, A > 0 and B < 0
Ans. (c)
Gibbs energy depends on (d) Endothermic if, A > 0
At the thermal equilibrium,
temperature T (in K) as T1 + T2 Ans. (d)
3 final temperature Tf =
∆ r G° (in kJ mol–1 ) =120 − T 2 According to Gibb’s Helmholtz equation,
8 Tf ∆ r G ° = ∆ r H ° − T∆ r S °
⇒for the 1st block, ∆SI = C p ln
The major component of the T1 Given, ∆ r G ° = A − BT
reaction mixture at T is T On comparing above two equations, we
[2019, 11 Jan Shift-I] ⇒for the 2nd block, ∆SII = C p ln f
T2 get,
(a) Y if T = 280 K A = ∆H ° and ∆S ° = B
(b) X if T = 350 K When brought in contact with each
We know that, if ∆H° is negative,
(c) X if T = 315 K other,
reaction is exothermic and when it is
(d) Y if T = 300 K T T
∆ S = ∆SI + ∆SII = C p ln f + C p ln f positive, reaction is endothermic.
Ans. (c) T1 T2
∴ If A > 0, i.e. positive, reaction is
For a given value ofT, T T   T2  endothermic.
= C p ln  f × f  = C p ln  f 
(i) If ∆ r G ° becomes < 0, the forward  T1 T2  TT
1 2

direction will be spontaneous and then 78 The following reaction is performed
the major and minor components will  T + T  2 
 1 2   at 298K
beY and X respectively.  2    (T + T )2 
= C p ln  = C p ln 1 2  2NO(g) + O 2 (g) 2NO 2 (g)
#
(ii) If∆ r G ° becomes > 0, the forward  TT 
 1 2
  4TT1 2  The standard free energy of
direction will be non-spontaneous
and then the major and minor   formation of NO (g) is 86.6 kJ/mol
components will be X andY at 298 K. What is the standard free
respectively. 76 The reaction, energy of formation of NO 2 (g) at
3 MgO(s) + C(s) → Mg(s) + CO(g), for
(a) ∆ r G ° = 120 − × 280 = 15 298 K? (K p = 1.6 × 10 12 )
8 which ∆ r Hº = + 491.1 kJ mol − 1 and [JEE Main 2015]
i.e. ∆ r G ° > O 0, major component
= X; ∆ r Sº = 198.0 JK − 1mol − 1 , is not (a) R (298) ln (1.6 × 1012 ) − 86600
3 feasible at 298 K. Temperature (b) 86600 + R (298) In (1.6 × 1012 )
(b) ∆ r G ° = 120 − × 350 = − 1125 .
8 above which reaction will be In (1.6 × 1012 )
(c) 86600 −
i.e. ∆ r G ° < 0, major component = Y feasible is [2019, 11 Jan Shift-II] R (298)
3
(c) ∆ r G ° = 120 − × 315 = 1.875 (a) 2040.5 K (b) 1890.0 K (d) 0.5 [2 × 86600 − R (298) In (1.6 × 1012 )]
8 Ans. (d)
(c) 2380.5 K (d) 2480.3 K
i.e. ∆ r G ° > 0, major component = X
Ans. (d) For the given reaction,
3
(d) ∆ r G ° = 120 − × 300 = 7.5 According to Gibbs-Helmholtz equation, 2NO(g) + O2 (g) #2NO (g)
8 2
∆ r G ° = ∆ r H ° − T∆ r S ° Given, ∆Gf° (NO) = 86.6 kJ / mol
i.e. ∆ r G ° > 0, major component = X
For a reaction to be feasible (spontaneous) ∆Gf° (NO2 ) = ? K p = 1.6 × 10 12
75 Two blocks of the same metal ∆rG° < 0 Now, we have,
having same mass and at ∆ r H °−T∆ r S ° <0
∆Gf° = 2∆Gf° (NO − [2∆Gf°(NO) + ∆Gf°(O 2 ) ]
temperatureT 1 andT 2 respectively, Given, ∆ r H° = + 491.1 kJ mol − 1, 2)

are brought in contact with each ∆ r S ° = 198 JK− 1 mol − 1 = − RT lnK p =2∆Gf°(NO 2 ) − [2 × 86600
, + 0]
1
other and allowed to attain thermal ∴ 491.1 × 10 − T × 198 < 0
3 ∆Gf°(NO 2 ) = [2 × 86600
,
2
equilibrium at constant pressure. 491.1 × 10 3
T> = 2480.3 K − R × 298 ln (1.6 × 10 12 )]
The change in entropy, ∆S, for this 198
∆Gf°(NO 2 ) = 0.5 [2 × 86600
,
process is [2019, 11 Jan Shift-I] ∴ Above 2480.3 K reaction will become
− R × (298)ln (1.6 × 10 12 )]
spontaneous.
Chemical Thermodynamics 67

89 The incorrect expression among ∆S = 2.303 nR log

V2 = − 394.4 + 2 (−237.2) − (−166.2) − 0
the following is V1 = − 394.4 − 474.4 + 166.2
∆G system Here, n = 2, V2 = 100 dm3, V1 = 10 dm3 . kJ mol −1
= −7026
(a) = −T 100 Percentage efficiency
∆G total [AIEEE 2012] = 2.303 × 2 × 83143
. log
10 7026.
(b) In isothermal process, = × 100 = 96.78% ≈ 97%
V = 38.296 J mol –1K–1 726
Wreversible = − nRT ln f
Vi
∆H ° − T∆S ° 81 For a particular reversible reaction, 83 Standard entropy of X 2 , Y 2 and XY 3
(c) lnK = at temperature T, ∆H and ∆S were
RT are 60, 40 and 50 JK −1 mol −1 ,
(d) K = e − ∆G ° / RT found to be both +ve. IfT e is the respectively. For the reaction,
temperature at equilibrium, the 1 3
Ans. (c) X 2 + Y 2 → XY 3 , ∆H = –30 kJ,
reaction would be spontaneous 2 2
According to Gibbs Helmholtz equation,
when [AIEEE 2010] to be at equilibrium, the
∆G = ∆H − T∆S
(a) T e > T (b) T > T e temperature will be [AIEEE 2008]
(a) For a system, total entropy change
= ∆S total
(c) T e is 5 times T (d) T = T e (a) 1250 K (b) 500 K
∆Htotal = 0 Ans. (b) (c) 750 K (d) 1000 K
∴ ∆G system = −T∆S total ∆G = ∆H − T∆S Ans. (c)
∆G system Here, ∆G = Gibb’s free energy 1 3
∴ = −T X2 + Y2 → XY3
∆S total ∆H = Enthalpy change 2 2
Thus, (a) is correct. ∆S = Entropy change ∆S reaction = S products − S reactants
T = Temperature 3 1 
(b) For isothermal reversible process, ∆S reaction = 50 −  × 40 + × 60 
∆E = 0 As equilibrium, ∆G = 0. Thus,T∆S = ∆H, 2 2 
as ∆H and ∆S are +ve, for a reaction to be
By first law of thermodynamics, = − 40 J mol −1
∆E = q + W feasible (spontaneous), ∆G should be
−ve. This can be possible only when ∆G = ∆H − T∆S
V
∴ Wreversible = − q = − ∫ f pdV T∆S > Te ∆H i.e.,T∆S > Te ∆S At equilibrium as ∆G = 0
Vi
or T > Te ∴ ∆H = T∆S
Vf
⇒ Wreversible = − nRT ln ∆ H 30 × 10 3
Vi [Te = temperature at equilibrium] ⇒ T= = = 750 K
∆S 40
Thus, (b) is correct.
82 In a fuel cell, methanol is used as
(c) ∆G ° = ∆H ° − T∆S ° …(i)
fuel and oxygen gas is used as an 84 Identify the correct statement
Also, ∆G ° = − RT In K
oxidiser. The reaction is regarding a spontaneous process.
− ∆G °
In K = 3 [AIEEE 2007]
RT CH3OH(l ) + O 2 (g ) → CO 2 (g ) (a) For a spontaneous process in an
(∆H °−T∆S ° ) 2
In K = [from Eq. (i)] + 2H2O(l ) isolated system, the change in
RT entropy is positive
At 298 K standard Gibb’s energies
Thus, (c) is incorrect. (b) Endothermic processes are never
of formation for CH3OH(l ),H2O(l )
(d) The standard free energy (∆G ° ) is spontaneous
related to equilibrium constantK
and CO 2 (g ) are –166.2, –237.2 and
(c) Exothermic processes are always
as −394.4 kJ mol −1 , respectively. If spontaneous
∆G ° = − RT In K standard enthalpy of combustion (d) Lowering of energy in the reaction
∴ InK = −
∆G °
⇒ K = e − ∆G ° / RT
of methanol is –726 kJ mol −1 , process is the only criteria for
RT efficiency of the fuel cell will be spontaneity
Thus, (d) is also correct. [AIEEE 2009]
Ans. (a)
(a) 80% (b) 87%
(c) 90% (d) 97% In an isolated system where either mass
80 The entropy change involved in the and energy are not exchanged with
isothermal reversible expansion of Ans. (d) surrounding for that spontaneous
2 moles of an ideal gas from a Percentage efficiency of the fuel cell process, the change in entropy is
volume of 10dm 3 to a volume ∆G positive.
= × 100
of 100 dm 3 at 27° C is [AIEEE 2011] ∆H
(a) 38.3 J mol−1 K −1 (b) 35.8 J mol−1 K −1 The concerned reaction is 85 In conversion of limestone to lime,
(c) 32.3 J mol−1 K −1 (d) 42.3 J mol−1 K −1 3
CH3OH(l ) + O2 (g) → CO2 (g) + 2H2O(l ) CaCO 3 (s ) → CaO(s) + CO 2 (g )
Ans. (a) 2 the values of ∆H° and ∆S° are
Entropy change for n moles of
∆G r = [ ∆Gf (CO2 , g) + 2∆Gf (H2O, l )] + 179.1 kJ mol −1 and 160.2 J /K,
3 respectively at 298 K and 1 bar.
isothermal expansion of an ideal gas [− ∆Gf (CH3OH, l ) − ∆Gf (O2 , g)]
from volume V1 to volume V2 is 2 Assuming that ∆H° and ∆S° do not
68 JEE Main Chapterwise Topicwise Chemistry

change with temperature, °

∆G ° = − nFE cell and the corresponding equilibrium
temperature above which If a cell reaction is spontaneous constant K c is [AIEEE 2003]
conversion of limestone to lime (proceeding in forward side), it means (a) ∆G = RT ln K c (b) − ∆G = RT ln K c
will be spontaneous is [AIEEE 2007] K eq > 1 (c) ∆G ° = RT ln K c (d) − ∆G ° = RT ln K c
(a) 1008 K (b) 1200 K and ° = + ve
E cell Ans. (d)
(c) 845 K (d) 1118 K Relationship between free energy and
Thus, ∆G ° = − ve
Ans. (d) equilibrium constant,
The entropy change can be given as − ∆G ° = RT ln K c
87 In an irreverible process taking
∆H place at constantT and p and in
∆S =
T 89 A reaction is non-spontaneous at
which only pressure-volume work
∆S = 160.2 J /K the freezing point of water but is
is being done, the change in Gibbs
∆H = 179.1 × 10 3 J /mol spontaneous at the boiling point of
free energy (dG) and change in
179.1 × 10 3 J /mol water, then [AIEEE 2002]
T= entropy (dS), satisfy the criteria
160.2 J /K [AIEEE 2003]
∆H ∆S
=1117.97 K ≈ 1118 K (a) (dS) V , E < 0, (dG)T ,p < 0 (a) + ve + ve
(b) – ve – ve
(b) (dS) V ,E > 0, (dG)T ,p < 0
86 For a spontaneous reaction, the ∆G, (c) (dS) V , E = 0, (dG)T ,p = 0
(c) – ve + ve
° (d) + ve − ve
equilibrium constant (K) and E cell (d) (dS) V , E = 0, (dG)T , p > 0
Ans. (a)
will be respectively [AIEEE 2005] Ans. (b)
For spontaneity, ∆G = − ve
(a) − ve, > 1, − ve An irreversible process
∆G = ∆H − T ∆S
(b) − ve, <1, − ve ⇒spontaneous process
∆H, for endothermic process + ve
(c) + ve, > 1, − ve ⇒(dS ) V ,E (change in entropy) = + ve > 0
At lower temperature, ∆S + ve
(d) − ve, > 1, + ve ⇒(dG) T ,p (change in Gibbs free energy)
Hence, ∆G = + ve
Ans. (d) − ve < 0 But at high temperature,T∆S will be
The standard free energy related to greater than ∆H.
equilibrium constantK as 88 The correct relationship between Hence, ∆G = −ve, spontaneous.
∆G ° = − 2303
. RT log K eq ; free energy change in a reaction
06
Solutions
[Atomic mass H = 1.0, C = 12.0, 04 100 mL of Na 3PO 4 solution
TOPIC 1 O = 16.0] [2021, 31 Aug Shift-I] contains 3.45 g of sodium. The
Expression of Concentration Ans. (20) molarity of the solution is ……
01 If 80 g of copper sulphate Molarity =
number of moles of solute × 10 − 2 mol L− 1 . (Nearest integer)
volume of solution (in litre)
CuSO 4 ⋅ 5H2O. is dissolved in [Atomic masses - Na = 23.0 u,
weight of solute/molecular mass
deionised water to make 5 L of O = 16.0 u, P = 31.0 u]
of solute
solution. The concentration of the = [2021, 26 Aug Shift-II]
volume of solution (in litre)
copper sulphate solution is x × 10 −3 Molecular mass of solute
Ans. (50)
mol L −1 . The value of x is ……… . Number of mole ofNa+ ions
[H2 C2O4 ⋅2H2O] = 126 g mass of sodium
[Atomic masses Cu = 63.54 u, 6.3 g / 126 g =
x × 10 −2 = × 1000 molar mass of sodium
S = 32 u,O = 16 u, H = 1 u] 250 mL 3.45
[2021, 1 Sep Shift-II] =
x × 10 −2 = 0.2 23
Ans. (64) x × 10 −2 = 20 × 10 −2 So, number of mole ofNa3PO4
Given, mass of CuSO 4 .5H2 O = 80 g ∴ x = 20 moles of sodium
The concentration of copper =
3
sulphate solution is x × 10 −3 mol/L. 03 The density of NaOH solution is {as 1 molecule ofNa3PO4 contains 3
Molarity =
Number of moles of solute
…(i) 1.2 g cm −3 . The molality of this atoms of Na}
Volume of solution (L)
solution is ………… m. =
3.45
= 0.05
Molar mass of 3 × 23
CuSO4 ⋅ 5H2O = 63.54 + 32 + 16 × 4
(Round off to the nearest integer)
Moles of Na3PO4
= 5 × 18 = 249.54 g / mol [Use : Atomic masses : Na = 23.0 Molarity =
Volume of solution (in L)
u, O = 16.0 u, H = 1.0 u, density of
Number of moles of solute 0.05
Weight of solute H2O : 1.0 g cm −3 ] = × 1000
= [2021, 27 July Shift-I]
100
Molecular mass of solute = 0.50
Ans. (5)
=
80 g
= 0.32 mol = 50 × 10 −2
Number of moles of solute
249.54 g / mol Molality = ∴ Answer is 50.
Weight of solution (kg)
Volume of solution = 5 L
Consider 1 litre solution, (1 litre = 1000 g) 05 The exact volumes of 1 M NaOH
From Eq. (i),
0.3205 Density of water is 1 g/mL solution required to neutralise
Molarity = = 64.11 × 10 −3 mol / L Mass of solution = Density × Volume
5 50 mL of 1 M H3PO 3 solution and
∴ x = 64.11 = 1.2 × 1000 g 100 mL of 2 M H3PO 2 solution,
or x ≈ 64 = 1200 g respectively, are
Hence, answer is 64. Neglecting volume of NaOH. [2021, 16 March Shift-II]
Mass of water = 1000 g (a) 100 mL and 100 mL
02 The molarity of the solution Mass of NaOH = (1200 − 1000) g (b) 100 mL and 50 mL
prepared by dissolving 6.3 g of = 200 g (c) 100 mL and 200 mL
oxalic acid (H2C 2O 4 ⋅ 2 H2O) in Moles of NaOH =
200
= 5 mol (d) 50 mL and 50 mL
250 mL of water in mol L − 1 is 40 Ans. (c)
x × 10 − 2 . The value of x is ......... Molarity =
5 mol
= 5 mol /kg H3PO3 +2NaOH → Na2HPO3 + 2H2O
1 kg 50 mL 1M
(Nearest integer) 1M V=?
70 JEE Main Chapterwise Topicwise Chemistry

Millimoles of H3PO3 = M × V = 1 × 50 = 50 4.5 1000d χ2

∴ C2 =
For 1 millimole of H3PO3, we require 2 = 90 = 0.2 or = 2 × 10 −1 M M1 + χ2 (M2 − M1)
millimoles of NaOH. 250
Hence, the correct option is (c).
For 50 millimole of H3PO3, we require 1000
(2 × 50) =` 100 millimoles of NaOH. Weight of solute (compound A)
∴ n= 09 The hardness of a water sample
Millimoles of NaOH = M × V = 100 Molecular weight of solute
containing 10 −3 M MgSO 4
1 × V = 100 (compound A) expressed as CaCO 3 equivalents
V = 100 mL −1
Hence, x × 10 µ (in ppm) is……
H3PO2 + NaOH → NaH2PO2 + H2O
100 mL
1M x =2 (molar mass of MgSO 4 is 120.37
V=?
2M
g/mol) [2020, 9 Jan Shift-II]
Millimoles of H3PO2 = M × V = 2 × 100 = 200
08 A solution of two components Ans. (100)
For 1 millimole of H3PO2 , we require 1
containing n 1 moles of the 1st Hardness in ppm
millimoles of NaOH.
component and n 2 moles of the Mass of CaCO3 equivalent to
For 200 millimole of H3PO2 , we require
200 millimoles of NaOH. 2nd component is prepared. M 1 and the total number of moles of
So, volume of NaOH = 200 mL M 2 are the molecular weights of
hardness causing substances × 10 6
component 1 and 2 respectively. If =
Mass of water sample
06 A 6.50 molal solution of KOH (aq) d is the density of the solution in g
Here, [Mg2 + ] = 10 −3 M
has a denisity of 1.89 g cm −3 . The mL −1 , C 2 is the molarity and χ 2 is
n 2 + = 10 −3 per 1 L water ≅ 1000 g
molarity of the solution is …… mol the mole-fraction of the 2nd Mg

dm −3 (Round off to the nearest component, then C 2 can be Mass of 10 −3 moles of CaCO3 = 10 −3 × 100 g
integer). expressed as [2020, 6 Sep Shift-I] = 0.1 g
1000 χ 2 0.1 × 10 6
[Atomic masses: K : 39.0 u, (a) C2 = ∴ ppm = = 100 ppm
O : 16.0u, H : 1.0 u] M 1 + χ 2 (M2 − M 1) 1000
[2021, 16 March Shift-I] dχ 2
(b) C2 = 10 10.30 mg of O 2 is dissolved into a
Ans. (9) M2 + χ 2 (M2 − M 1)
M × 1000 litre of sea water of density 1.03
Molality (m) = 1000 dχ 2
{(1000 d) − M × Msolute } (c) C2 = ] g/mL. The concentration of O 2 in
M 1 + χ 2 (M2 − M 1)
where, M = molarity ppm is [2020, 9 Jan Shift-II]
dχ 1 Ans. (10.00)
d = density of solution (d) C2 =
M2 + χ 2 (M2 − M 1) Mass of O2 = 10.30 mg (Given)
Msolute = molar mass of solute
Putting the values, Ans. (c) Mass of sea water solution
M × 1000 = volume × density
6.50 = In first component,
(1000 × 1.89) − (M × 56) Mass = number of moles × molecular = 1L × 1.03 g/mL
12285 weight = n1M1 = 1000mL × 1.03 g mL−1 = 1030 g
On solving, M =
1364 In second component, mass of O2
ppm = × 10 6
M = 9 molar Mass = n2 M2 mass of solution
Mass of solution = n1M1 + n2 M2 …(i) 10.30 × 10 −3 g × 10 6
07 4.5 g of compound A (MW = 90) was =
n2 1030 g
used to make 250 mL of its Mole-fraction (χ2 ) =
n1 + n2 = 10 ppm
aqueous solution. The molarity of
n2 (1 − χ2 )
the solution in M is x × 10 − 1 . The ∴ n1 = …(ii)
11 What would be the molality of 20%
χ2
value of x is ......... . (Rounded off to (mass/mass) aqueous solution of
Place the value of n1 in eq. (i)
the nearest integer). KI?
n2 (1 − χ2 ) M1
[2021, 24 Feb Shift-I] ∴ + n2 M2 Molar mass of KI = 166 g mol −1 )
Ans. (2) χ2 [2019, 9 April Shift-II]

Given, weight of compound A = 4.5 g n2 (a) 1.48 (b) 1.51 (c) 1.35 (d) 1.08
⇒ (M2 χ2 − M1χ2 + M1)
Molecular weight of compound A = 90 χ2 Ans. (b)
g/mol Volume of solution,
Volume of solution (in mL) = 250 mL n (M χ − M1χ2 + M1) Key Idea Molality is defined as number
= 2 2 2 L of moles of solute per kg of solvent.
Now, molarity is defined as number of 1000 × d × χ2
moles of solute or compound A divided w 1000
1000 × n2 × dχ2 m= 2 ×
by volume of solution (in L). C2 = Mw2 w1
Number of moles of solute (n) n2 (M2 χ2 − M1χ2 + M1)
M= w2 = mass of solute
Volume of solution
Solutions 71

Mw2 = molecular mass of solute 14 The amount of sugar (C 12H22O 11 ) w Solute

w 1 = mass of solvent. Mw Solute
required to prepare 2 L of its 0.1 M = × 1000
w Solvent (in g)
The molality of 20% (mass/mass) aqueous aqueous solution is
solution of KI can be calculated by 8
(a) 17.1 g (b) 68.4 g 0.2
following formula.
(c) 136.8 g (d) 34.2 g = 40 × 1000 = × 1000 = 11.11 mol kg − 1
w × 1000 18 18
m= 2 [2019, 10 Jan Shift-II]
Mw2 × w 1 Ans. (b)
Thus, mole fraction of NaOH in solution
and molality of the solution respectively
20% aqueous solution of KI means that Number of moles of solute (n) are 0.167 and 11.11 molkg − 1
Molarity =
20 gm of KI is present in 80 gm solvent. Volume of solution (in L)
20 1000
m= × = 1 . 506 ≈ 1 . 51 mol/kg w B (g) 16 A 5.2 molal aqueous solution of
166 80 Also, n =
MB (g mol −1) methyl alcohol, CH3OH, is supplied.
12 The mole fraction of a solvent in w B / MB What is the mole fraction of methyl
∴ Molarity =
aqueous solution of a solute is 0.8. V alcohol in the solution ? [AIEEE 2011]
The molality (in mol kg −1 ) of the Given,w B = mass of solute (B) in g (a) 0.100 (b) 0.190
MB = Gram molar mass of (c) 0.086 (d) 0.050
aqueous solution is
[2019, 12 April Shift-I] B (C12H22O11) Ans. (c)
(a) 13.88 × 10−2 (b) 13.88 × 10−1 = 342 g mol −1 5.2 molal aqueous solution of CH3OH
(c) 13.88 (d) 13.88 × 10−3 Molarity = 0.1 M, Volume (V ) = 2L
suggests that 5.2 moles of CH3OH are
dissolved in 1000 g of water.
Ans. (c) w /342
⇒ 0.1 = B n1 (CH3OH) = 5.2
Key Idea 2 1000
Mass of solute (w2 ) × 1000 ⇒ w B = 0.1 × 342 × 2 g = 684 n2 (H2O) = = 55.56
Molality ( m) = . g 18
Molar mass of solute (M2 ) ×
∴ n1 + n2 = 5.20 + 55.56
mass of solvent (w 1) 15 8 g of NaOH is dissolved in 18 g of
= 60.76 mol
w2 1000 H2O. Mole fraction of NaOH in
m= × ∴ X CH OH = Mole fraction of CH3OH
M2 w1 solution and molality (in mol kg − 1 ) 3
n1 5.2
1000 of the solution respectively are = = = 0.086
and also, m = n2 × n1 + n2 60.76
n1 × M1 (a) 0.2, 11.11 (b) 0.167, 22.20
Xsolvent = 0.8 (Given) (c) 0.2, 22.20 (d) 0.167, 11.11
17 The molality of a urea solution in
[2019, 12 Jan Shift-II]
It means that nsolvent (n1) = 0.8 which 0.0100 g of urea, [(NH2 ) 2 CO]
and nsolute (n2 ) = 0.2 Ans. (d)
is added to 0.3000 dm3 of water at
1000 Mole fraction of solute
Using formula m = n2 × STP is [AIEEE 2011]
n1 × M1 number of moles of solute+ number of
(a) 0.555 m (b) 5.55 × 10−4 m
1000 moles solvent
= 0.2 × = 13.88 mol kg −1 = (c) 33.3 m (d) 3.33 × 10−2 m
0.8 × 18 number of moles of solute
n Solute Ans. (b)
χ Solute = moles of solute
13 A solution of sodium sulphate n Solute + nSolvent Molality =
kg of water
contains 92 g of Na + ions per w Solute 0.010
kilogram of water. The molality of Moles of urea = mol
Mw Solute 60
=
Na + ions in that solution in mol kg −1 w Solute w
+ Solvent Water at STP ( d = 1g/cm 3 = 1 kg/dm 3)
is [2019, 9 Jan Shift-I] Mw Solute Mw Solvent
= 0.3 dm3 = 0.3 kg
(a) 16 (b) 4
Given, w Solute = w NaOH = 8 g 0.010
(c) 132 (d) 8 ∴ Molality = = 5.55 × 10 −4 m
Ans. (b) Mw Solute = Mw NaOH =40 g mol − 1 60 × 0.3
Number of moles of solute w Solvent = w H 2 O = 18 g
Molality (m) = 18 The density (in g mL−1 ) of a 3.60M
Mass of solvent (in g) Mw Solvent = 18 g mol − 1
8 sulphuric acid solution that is 29%
× 1000
∴χ Solute = χ NaOH = 40
8 18
H2SO 4 (molar mass = 98 g mol −1 ) by
Mass of solute (in g) × 1000 + mass will be
= 40 18
[AIEEE 2007]
Molecular weight of solute  0.2 0.2 (a) 1.64 (b) 1.88 (c) 1.22 (d) 1.45
 × mass of solvent (in g)  = = = 0.167
 0.2 + 1 1.2 Ans. (c)
w + × 1000 92 × 1000
= Na = = 4 mol kg − 1 Now, molality Molarity
MNa + × wH 2 O 23 × 1000 (m) =
Moles of solute 10 × density × % by wt. of solute
=
Mass of solvent (in kg) mol wt. of the solute
72 JEE Main Chapterwise Topicwise Chemistry

3.60 × 98 M1V1 + M2V2 25 Which of the following

Density = Total molarity =
10 × 29 V1 + V2 concentration factor is affected by
= 1.216 gML−1 = 1.22 gML−1 change in temperature? [AIEEE 2002]
1.5 × 480 + 1.2 × 520
= =1.34 M
480 + 520 (a) Molarity (b) Molality
19 Equal masses of methane and (c) Mole fraction (d) Weight fraction
oxygen are mixed in an empty
22 6.02 × 10 20 molecules of urea are Ans. (a)
container at 25°C. The fraction of
present in 100 mL of its solution. Molarity gets affected as it is the number
the total pressure exerted by
The concentration of urea solution of moles per unit volume (volume
oxygen is [AIEEE 2007] increases with increase in temperature).
2 1 273 is (Avogadro constant,
(a) (b) × N A = 6.02 × 1023 mol−1) [AIEEE 2004]
3 3 298
(c)
1
(d)
1 (a) 0.001 M (b) 0.01 M TOPIC 2
3 2 (c) 0.02 M (d) 0.1 M
Ans. (b)
Henry’s Law and
Ans. (c)
Suppose the equal mass of methane and Avogadro’s number,N A Raoult’s Law
oxygen = w = 1g = 6.02 × 1023 molecules = 1mol
w /32 ∴6.02 × 1020 molecules = 0.001 mol in 26 CO 2 gas is bubbled through water
Mole fraction of oxygen =
w /32 + w / 16 100 mL or (0.1 L) solution during a soft drink manufacturing
mol
1 /32 1 ∴Molar concentration = process at 298 K. If CO 2 exerts a
= = volume in litre
3 /32 3 partial pressure of 0.835 bar then
0.001
Let the total pressure = p = = 0.01 M x m mol of CO 2 would dissolve in
0.1
Pressure exerted by oxygen (partial 0.9 L of water. The value of x is
pressure) ……… . (Nearest integer)
1 23 To neutralise completely 20 mL of
= XO 2 × ptotal = p × 0.1 M aqueous solution of (Henry’s law constant for CO 2 at
3
phosphorous acid (H3PO 3 ), the 298 K is 1.67 × 10 3 bar)
Thus, the fraction of the total pressure [2021, 25 July Shift-I]
exerted by oxygen is 1/3. volume of 0.1 M aqueous KOH
solution required is [AIEEE 2004]
Ans. (25)
20 Density of a 2.05 M solution of (a) 10 mL (b) 20 mL According to Henry’s law,
acetic acid in water is 1.02 g /mL. (c) 40 mL (d) 60 mL pCO 2 = K H XCO 2
The molality of the solution is Ans. (c) pCO 2 , K H and XCO 2 are pressure of CO
[AIEEE 2006] gas. Henry’s constant and mole fraction
H 3 PO 3 is a dibasic acid (i. e., contains two of CO respectively.
(a) 1.14 mol kg −1 (b) 3.28 mol kg −1 ionisable protons attached directly to O). pCO 2
(c) 2.28 mol kg −1 (d) 0.44 mol kg −1 H3PO3 3 2H+ + HPO24− ⇒ XCO 2 = …(i)
KH
Ans. (c) ∴ 0.1 M H3PO3 = 0.2 N H3PO3
M Given, K H = 0.835 × 2 × 10 3 bar
Molality (m) = × 100 and 0.1 M KOH = 0.1 N KOH
1000 d − MM1 = 1.67 × 10 3 bar
N 1V1 = N2V2
M = Molarity; M1 = Molecular mass (KOH) (H 3 PO 3 )
pCO 2 =`0.835 bar
Put all values in equation (i), we get
d = density 0.1 V1 = 0.2 × 20; V1 = 40 mL
0.835
2.05 XCO 2 =
= × 1000 0.835 × 10 3 × 2
(1000 × 1.02) − (2.05 × 60) 24 25 mL of a solution of barium
−1 XCO 2 = 0.5 × 10 −3
= 2.28 mol kg hydroxide on titration with 0.1
molar solution of hydrochloric acid Volume of water = 0.9 L = 900 mL
21 Two solutions of a substance gave a titre value of 35 mL. The Density of water = 1 g/mL
(non-electrolyte) are mixed in the molarity of barium hydroxide Mass of water = density × volume = 900 g
following manner. 480 mL of 1.5 M solution was [AIEEE 2003]
So, number of mole of water
900
first solution + 520 mL of 1.2 M (a) 0.07 (b) 0.14 = = 50 moles
18
second solution. (c) 0.28 (d) 0.35
nCO 2
What is the molarity of the final Ans. (a) So, = 0.5 × 10 −3
nCO 2 + nH 2 O
mixture ? [AIEEE 2005] Let molarity of Ba(OH)2 = M1
(a) 2.70 M (b) 1.34 M ∴ Normality = 2 M1 nCO 2 << H2O = 50 moles
(c) 1.50 M (d) 1.20 M Molarity of HCl = 0.1 M = 0.1 N2 So, n
CO2 + nH 2 O = nH2O
Ans. (b) N 1V1 = N2V2 nCO 2 = 0.5 × 10 −3 × 50
The molarity of the resulting solution is 2M1 × 25 = 0.1 × 35 = 25 × 10 −3 mol
given by Millimoles of CO2 = 0.025 × 1000 = 25
M1 = 0.07 M
Solutions 73

27 The vapour pressures of A and B at pA° pB° pA° + pB° ° 0.20 + p ° 0.80
⇒ 560 = phex …(ii)
pT = + = hep
25°C are 90 mm Hg and 15 mm Hg 2 2 2 Eq. (i) multiplied by0.20
respectively. If A and B are mixed Putting in above equation (i), °
⇒ 550 × 0.20 = (0.25 × 0.20) phex
such that the mole-fraction of A in 70 °
+ (0.75 × 0.20) phep
2 70 °
⇒ 110 = 0.05phex + 0.15phep °
the mixture is 0.6, then the mole yA = = …(iii)
(70 + 20) 90
fraction of B in the vapour phase is Eq. (ii) multiplied by 0.25,
2
x × 10 −1 . The value of x is ……… . °
⇒ 560 × 0.25 = (0.20 × 0.25) phex
y A = 0.78 = 78 × 10 −2
(Nearest integer) °
+ (0.8 × 0.25) phep
[2021, 20 July Shift-II]
29 At 300 K, the vapour pressure of a 140 = 0.05phex° + 0.20 p ° …(iv)
Ans. (1) hep
solution containing 1 mole of Now, Eq. (iii) and Eq. (iv)
Partial pressure of A, pA° = 90 mm of Hg
n-hexane and 3 moles of n-heptane ° + 0.15p ° − 0.05p °
⇒0.05phex
Partial pressure of B, pB° = 15 mm of Hg hep hex
is 550 mm of Hg. At the same ° = 110 − 140
− 0.20 phep
Mole fraction of A, χ A = 0.6
temperature, if one more mole of ⇒0.15p ° − 0.20 p °
Mole fraction of B, χ B = 0.4 hep hep = − 30
n-heptane is added to this solution, ⇒ −0.05phep ° = − 30
Total pressure,
the vapour pressure of the solution
pT = χ A pA° + χ BpB° ⇒ ° = 30 = 600 mm of Hg
phep
increases by 10 mm of Hg. What is 0.05
= (0.6 × 90) + (0.4 × 15)
= 54 + 6 = 60 mm
the vapour pressure in mm Hg of Thus, vapour pressure of pure n-heptane
Now, mole fraction of B in vapour phase,
n-heptane in its pure state ........... ? ° ) is 600 mm of Hg.
(phep
[2020, 4 Sep Shift-I]
p χ p°
i.e. YB = B = B B = 0.1 = 1 × 10 −1 Ans. (600) 30 Henry’s constant (in kbar) for four
pT 60
Given, gases α, β, γ and δ in water at 298 K
x=1
Vapour pressure of solution = 550 mmHg is given below :
28 At 20°C, the vapour pressure of Mole of hexane (nhex) = 1 mol α β γ δ
Mole of heptane (nhep ) = 3 mol
benzene is 70 torr and that of KH 50 2 2 × 10−5 0.5
methyl benzene is 20 torr. The From Raoult’s law,
Vapour pressure in solution = vapour (density of water = 10 3 kg m −3 at
mole fraction of benzene in the
pressure of pure solvent × mole fraction 298 K). This table implies that
vapour phase at 20°C above an p = p° χ [2020, 3 Sep Shift-I]
equimolar mixture of benzene and Here, vapour pressure of solution = p, (a) α has the highest solubility in water
methyl benzene is…… × 10 −2 . vapour pressure of pure solvent = p° and at a given pressure
(Nearest integer) mole fraction = χ (b) solubility of γ at 308 K is lower than
[2021, 20 July Shift-I] Total vapour pressure of solution, at 298 K
Ans. (78) ptotal = p°hex χhex + p°hep χhep (c) The pressure of a 55.5 molal solution
of γ is 1 bar
Vapour pressure of pure benzene, Case I Mole fraction of hexane,
pA° = 70 Torr (d) The pressure of a 55.5 molal solution
1 of δ is 250 bar
χhex = = 0.25
Vapour pressure of pure methyl 1+ 3
benzene, pB° = 20 Torr Ans. (d)
Mole fraction of heptane, Henry’s equation for solubility (S ) of a gas
This mixture is equimolar, so, number of
3 (β) in a liquid is expressed in terms of
moles of benzene, nA = number of moles χhep = = 0.75
of methyl benzene, nB 1+ 3 mole- fraction of the gas (χ B) at a given
Mole fraction of benzene in vapour p = p°hex0.25 + p°hep × 0.75 temperature,
phase, 550 = p°hex0.25 + p°hep × 0.75 …(i) p = KH × χB = KH × S
p 1
yA = A …(i) Case II According to question, when 1 So, solubility of gas, S ∝ at T (K) and
pT KH
mole of heptane added and vapour
where pA is pressure of benzene in pressure increased by 10 mm of Hg. given pressure.
mixture. Mole fraction of hexane, Order of solubility of the gases (high the
pA = pA° χ A 1 value of K H , lower is the solubility) :
χhex = = 0.20
Mole fraction n 1+ 4 γ >δ>β>α
nA p° So, option (a) is not correct.
= pA° × = pA° × A = A Mole fraction of heptane,
nA + nB 2
n 2
4 Again,K H ∝temperature, i.e. solubility of
A χhep = = 0.80 the gas will decrease with increase in
1+ 4
pT is total pressure, temperature also.
p = p°hex χhex + p°hep χhep
pT = pA° χ A + pB° χ B = pA + pB But this conclusion cannot be drawn from
Vapour pressure increased by 10 mm of table.
(pressure of methyl benzene)
Hg then p = 560 So, option (b) is not correct.
74 JEE Main Chapterwise Topicwise Chemistry

We know, mole-fraction of a solute (B) in Option (c) is incorrect as for positive

X Y Z
a binary aqueous solution, deviation, ∆V > 0 because final volume of 800

Vapour pressure
18 m solution must be greater than the sum of
χB = 500

(mm Hg)
1000 + 18 m volumes of components taken.
400
[Qm = molality] Option (d) is correct. Since, in such
solution, ∆ mixH is positive because 200
For γ at m = 55.5 molal
energy is required to break A  A and
p = K Hγ × m = (2 × 10 −5 ) B  B bonds.
0 293 313 333 353
Temp
 18 × 55.5 
× 
 1000 + 18 × 55.5  32 Two open beakers one containing a The following inference are made :
−5
= 1 . 81 × 10 K bar = 1 . 8 × 10 bar−2 solvent and the other containing a A. X has higher intermolecular
So, option (c) is not correct.
mixture of that solvent with a interactions compared to Y.
For δ at m = 55.5 molal non-volatile solute are together B. X has lower intermolecular
 18 × 55.5  sealed in a container. Over time interactions compared to Y.
p = K Hδ = (0.5) ×   [2020, 7 Jan Shift-II]
 1000 + 18 × 55.5  C. Z has lower intermolecular
(a) the volume of the solution decreases interactions compared to Y.
= 0.2498 k bar ~− 250 bar and the volume of the solvent
So, option (d) is correct. increases The correct inference(s) is/are :
(b) the volume of the solution does not (a) (C) (b) (B)
31 At 35°C, the vapour pressure of change and the volume of the (c) (A) (d) (A) and (C)
CS 2 is 512 mm Hg and that of solvent decreases Ans. (b)
(c) the volume of the solution increases
acetone is 344 mm Hg. A solution From given graph it can be seen that , X
and the volume of the solvent has higher vapour pressure as compared
of CS 2 in acetone has a total decreases to Y at lower temperature (or to attain
vapour pressure of 600 mm Hg. (d) the volume of the solution and the same vapour pressure,Y need higher
The false statement amongst the solvent does not change temperature than X). It means that
following is [2020, 7 Jan Shift-I] Ans. (c) intermolecular interactions must be
(a) Raoult’s law is not obeyed by this weaker in X as compared toY, which
system Liquid Vapour further must be weaker than Z by the
(b) CS2 and acetone are less attracted to same reason also. Hence, option (b) is
each other than to themselves correct.
(c) a mixture of 100 mL CS2 and 100 mL
acetone has a volume < 200 mL 34 The vapour pressures of pure
(d) heat must be absorbed in order to liquids A andB are 400 and 600
produce the solution at 35°C mmHg, respectively at 298 K. On
Ans. (c) mixing the two liquids, the sum of
The incorrect statement among the Only solvent-It has Solvent + non- their initial volumes is equal to the
given statements is (c) and the more vapour volatile solut-It has
pressure
volume of the final mixture. The
explanation of all the statements is as less vapour pressure
mole fraction of liquid B is 0.5 in the
follows : If a non-volatile solute is added to a mixture. The vapour pressure of
According to Raoult’s law, vapour solvent to form a solution, the vapour
pressure of the solution pid (ideal vapour
the final solution, the mole
pressure gets decreased.
pressure) = pA ° + (pB ° − pA ° ) x B fractions of components A and B in
∴According to Raoult’s law, if vapour
(A = solvent : acetone, B = solute : CS2 ) vapour phase, respectively are
pressure of pure solvent is p°, vapour [2019, 8 April Shift-I]
Given; pA ° = 344 mm Hg. pressure of solvent in solution (p) is
(a) 450 mmHg, 0.4, 0.6
pB ° = 512 mm Hg. = p°⋅x A . (b) 500 mmHg, 0.5, 0.5
∴ pid = 344
. + (512 − 344) x B ∴ p < p°
(c) 450 mmHg, 0.5,0.5
or pid = 344 + 168 x B Since, vapour pressure of solution is
(d) 500 mmHg, 0.4,0.6
and so,0 < x B < 1. less, there will be net backward reaction
[i.e. vapour → liquid] in that beaker. Ans. (d)
Also, total vapour pressure (p)
Thus, its volume increases. According to Dalton’s law of partial
= 600 mmHg
In another beaker containing only net pressure ptotal = pA + pB
∴ For any value of x B, p > pid .
reaction is forward, = pA° χ A + pB° χ B …(i)
Since p ≠ pid , so, option (a) is correct. Thus, volume decreases. Given, pAº = 600 mm Hg
= 400 mm Hg, pBº
Option (b) is also correct. Since p > pid ,
(i.e. positive deviation) therefore 33 A graph of vapour pressure and χ B = 0.5, χ A + χ B = 1
attractive force between CS2 and temperature for three different ∴ χ A = 0.5
acetone is weaker than CS2 − CS2 or liquids X, Y, and Z is shown below : On substituting the given values in Eq. (i).
acetone-acetone attraction. [2020, 8 Jan Shift-I] We get,
ptotal = 400 × 0.5 + 600 × 0.5 = 500 mm Hg
Solutions 75

Mole fraction of A in vapour phase, χ gas = mole fraction of the gas (solute) in Liquid M and N form an ideal solution.
p pº χ 0.5 × 400 the solution. Vapour pressures of pure liquids M and N
YA = A = A A = = 0.4 are 450 and 700 mm Hg respectively.
ptotal ptotal 500 χH 2 O = mole fraction of water (solvent).
∴ pº N > pº M
Mole of B in vapour phase, So, by using Raoult’s law
YA + YB = 1 yN > xN …(i)
YB = 1 − 0. 4 = 0.6 pgas pgas
and xM > yM …(ii)
KH KH
Multiplying (i) and (ii) we get
35 For the solution of the gases w, x, y
yN xM > yM xN
and z in water at 298 K, the Henry’s xM yM
law constants (K H ) are 0.5, 2, 35 ∴ >
χH2O=0 χH2O=0 xN yN
and 40 K bar, respectively. The
χgas=1 χgas=0 Thus, correct relation is (a).
correct plot for the given data is
[2019, 8 April Shift-II]
[i.e. pgas = K H ] Higher the value ofK H , 37 Which one of the following
higher
statements regarding Henry’s law is
Partial pressure

will be the partial pressure of the gas

not correct?
(a) (pgas ), at a given temperature. The plot of
z pgas vs χH 2 O gives a (−ve) slope. (a) Different gases have differentK H
y (Henry’s law constant) values at the
pgas = K H − K H × χH 2 O
x w
same temperature
Comparing the above equation with the (b) Higher the value ofK H at a given
(0, 0) Mole fraction equation of straight line y = mx + c pressure, higher is the solubility of
of water Slope = − K H , intercept = K H the gas in the liquids
So, (i) Higher the value ofK H , more (−ve) (c) The value of K H increases with
Partial pressure

will be the slope and it is for increase of temperature andK H is

z
z (K H = 40 K bar) function of the nature of the gas
(b) y (ii) Higher the value ofK H , higher with the (d) The partial pressure of the gas in
x value of intercept, i.e. partial pressure vapour phase is proportional to the
and it is also for z. mole fraction of the gas in the
w
solution [2019, 9 Jan Shift-I]
(0, 0) Mole fraction 36 Liquid M and liquid N form an ideal Ans. (b)
of water
solution. The vapour pressures of At constant temperature, solubility of a
z pure liquids M and N are 450 and gas (S ) varies inversely with Henry’s law
Partial pressure

700 mmHg, respectively, at the constant (K H )

y Pressure P
(c) same temperature. Then correct KH = =
Solubility of a gas in a liquid S
x statement is [2019, 9 April Shift-I]
Thus, higher the value ofK H at a given
w x M = mole fraction of M in pressure, the lower is the solubility of
(0, 0) Mole fraction solution; the gas in the liquid.
of water
x N = mole fraction of N in solution;
z 38 Liquids A and B form an ideal
y y M = mole fraction of M in vapour solution in the entire composition
Partial pressure

phase; range. At 350 K, the vapour

xw
(d) y N = mole fraction of N in vapour pressures of pure A and pure B are
phase 7 × 10 3 Pa and 12 × 10 3 Pa,
xM y M respectively. The composition of
(a) >
(0, 0) Mole fraction
xN y N the vapour in equilibrium with a
of water xM y M solution containing 40 mole
(b) = percent of A at this temperature is
Ans. (a) xN y N
x y (a) xA = 0.76; xB = 024
.
According to Henry’s law (at constant (c) M < M (b) xA = 028
. ; xB = 0.72
temperature) xN y N
pgas = K H × χ gas (solute) (c) xA = 04
. ; xB = 0.6
(d) (xM − y M ) < (xN − y N )
= K H × [1 − χH 2 O (solvent) ] (d) xA = 0.37; xB = 0.63
Ans. (a)
[2019, 10 Jan Shift-I]
pgas = K H − K H χH 2 O Key Idea For a solution of volatile liquids
pgas = partial pressure of the gas above Ans. (b)
the partial vapour pressure of each
its solution with a liquid (solvent) component of the solution is directly For ideal solution,
say water. proportional to its mole fraction present p = x ′A p° A + x ′B p° B
in solution. This is known as Raoult’s law. Q x ′A = 0.4, x ′B = 0.6
76 JEE Main Chapterwise Topicwise Chemistry

p° A = 7 × 10 3 Pa, p° B = 12 × 10 3 Pa On subtracting Eq. (ii) by Eq. (i), we get Ans. (d)

On substituting the given values in Eq. (i), pB ° = 2800 − 2200 Mixture contains 78 g benzene = 1 mol
we get ⇒ pB ° = 600 benzene and 46 g toluene = 0.5 mol
p = 0.4 × 7 × 10 3 + 0.6 × 12 × 10 3 toluene
Putting the value of pB ° in Eq. (i)
= 10 × 10 3 Pa = 1 × 10 4 Pa Total moles of benzene and toluene
pA ° + 3 × 600 = 2200
In vapour phase, = 1.5 mol
pA ° = 2200 − 1800 = 400
p x ′ p° 0.4 × 7 × 10 3
xA = A = A A = = 0.28 Mole fraction of benzene in mixture
p p 1 × 10 4 41 A binary liquid solution is prepared 1 2
= =
∴ x B = 1 − 0.28 = 0.72 [Q x A + x B = 1] by mixing n-heptane and ethanol. 1.5 3
Which one of the following Vapour pressure of benzene
39 On mixing, heptane and octane pb° = 75 torr
statements is correct regarding the
form an ideal solution. At 373 K, the
behaviour of the solution? ∴Partial vapour pressure of benzene
vapour pressures of the two liquid [AIEEE 2009] = p° b Xb
components (heptane and octane) (a) The solution formed is an ideal
2
are 105 kPa and 45 kPa, solution = 75 × = 50 torr
3
respectively. Vapour pressure of (b) The solution is non-ideal, showing
the solution obtained by mixing positive deviation from Raoult’s law
(c) The solution is non-ideal, showing 44 Which of the following liquid pairs
25 g of heptane and 35 g of octane
negative deviation from Raoult’s law shows a positive deviation from
will be (molar mass of heptane
(d) n-heptane shows positive deviation Raoult’s law? [AIEEE 2004]
= 100 g mol −1 and of octane while ethanol show negative (a) Water — hydrochloric acid
= 114 g mol −1 ). [AIEEE 2010] deviation from Raoult’s law (b) Benzene — methanol
(a) 72.0 kPa (b) 36.1 kPa Ans. (b) (c) Water — nitric acid
(c) 96.2 kPa (d) 144.5 kPa n-heptane and ethanol forms non-ideal (d) Acetone — chloroform
Ans. (a) solution. As a result, n-heptane-ethanol Ans. (b)
pT = XH ⋅ p H° + X 0 ⋅ p°0 molecular interaction is very poor in Water and hydrochloric acid; and water
comparison to ethanol-ethanol or and nitric acid form miscible solutions.
25 / 100 n-heptane so the resulting gives positive
XH = = 0.45 They show negative deviation.
25 / 100 + 35 / 114 deviation from Raoult’s law. In case of CH3COCH3 and CHCl 3, there is
∴ X0 = 0.55 interaction between them, thus force of
pT = 0.45 × 105 + 0.55 × 45
42 A mixture of ethyl alcohol and attraction between CH3COCH3....CHCl 3 is
= 72 .0 kPa
propyl alcohol has a vapour larger than between
pressure of 290 mm at 300 K. The CHCl 3....CHCl 3 or CH3COCH3....CH3COCH3
vapour pressure of propyl alcohol is and thus, vapour pressure is less than
40 Two liquids X and Y form an ideal expected—a negative deviation.
solution at 300 K, vapour pressure 200 mm. If the mole fraction of
In case of CH3OH , there is association by
of the solution containing 1 mol of X ethyl alcohol is 0.6, its vapour intermolecular H-bonding. When
and 3 mol of Y is 550 mmHg. At the pressure (in mm) at the same benzene is added to CH3OH, H-bonding
same temperature, if 1 mol of Y is temperature will be [AIEEE 2007] breaks and thus, force of attraction
further added to this (a) 350 (b) 300 between CH3OH and benzene molecule is
(c) 700 (d) 360 smaller than between CH3OH or benzene
solution, vapour pressure of the molecules (in pure state). Vapour
solution increases by 10 mm Hg. Ans. (a)
pressure of mixture is greater than
Vapour pressure (in mmHg) of X According to Raoult’s law, expected—a positive deviation.
and Y in their pure states will be, p = p° A XA + p° B XB CH3 CH3 CH3
respectively [AIEEE 2009] 290 = 200 × 0.4 + p° B × 0.6  δ+  δ+ 
O  H ... O  H ... O  H ...
(a) 200 and 300 (b) 300 and 400 p° B = 350 mm δ− δ− δ− δ+

(c) 400 and 600 (d) 500 and 600

Ans. (c) 43 Benzene and toluene form nearly 45 If liquid A and B form an ideal
pT = pA ° XA + pB ° XB ideal solutions. At 20°C, the vapour solution, the [AIEEE 2003]
1 3 pressure of benzene is 75 torr and (a) enthalpy of mixing is zero
550 = pA ° × + pB ° ×
4 4 that of toluene is 22 torr. The (b) entropy of mixing is zero
Thus, pA ° + 3pB ° = 2200 …(i) partial vapour pressure of benzene (c) free energy of mixing is zero
When 1 mole of Y is further added to the (d) free energy as well as the entropy of
at 20°C for a solution containing
solution, vapour pressure of a solution mixing are each zero
becomes 560 mm Hg.
78 g of benzene and 46 g of toluene
Ans. (a)
1
Thus, 560 = pA ° × + pB ° ×
4 in torr is [AIEEE 2005]
For ideal solution, ∆H = 0, ∆V = 0;
5 5 (a) 535
. (b) 37.5
FA − A = FB− B = FA − B
Thus, pA ° + 4pB ° = 2800 …(ii) (c) 25 (d) 50
Solutions 77

46 In a mixture of A and B, components of ice (in g) that will be separated 50 When 3.00 g of a substance 'X' is
show negative deviation when out is ……… . (Nearest integer) dissolved in 100 g of CCl 4 , it raises
[AIEEE 2002] [Given, K f (H2O) = 1.86 K kg mol − 1 ] the boiling point by 0.60 K. The
(a) A  B interaction is stronger than [2021, 27 Aug Shift-I] molar mass of the substance 'X' is
A  A and B  B interaction ……… g mol −1 . (Nearest integer)
Ans. (518)
(b) A  B interaction is weaker than
A  A and B  B interaction Let mass of water (initially present) = x g [Given, K b for CCl 4 is 5.0 K kg
(c) ∆Vmix > 0, ∆S mix > 0 Mass of sucrose = (1000 − x) g mol −1 ] [2021, 25 July Shift-II]
(d) ∆Vmix =0, ∆S mix > 0 1000 − x Ans. (250)
Moles of sucrose =
Ans. (a) 342 Weight of substance ‘X’ = 3.00 g
moles of sucrose Elevation in boiling point, ∆Tb = 0.60
Negative deviation means lower vapour Molality =
pressure. It suggests high boiling point, mass of water (initially) K b (boiling constant) of CCl 4
thus resultant intermolecular force  1000 − x  = 5 K kg mol − 1
 
should be stronger than individual one.  342  Weight of compound
0.75 =
 x  Molar mass of compound
  Molality (m) =
 1000  Volume of solution (in L)
TOPIC 3 x 1000 − x 3
=
Colligative Properties 1000 342 × 0.75 = M ...(i)
100
256.5x = 10 6 − 1000 x
47 40 g of glucose (Molar mass = 180) ⇒ x = 795.86 g
1000
is mixed with 200 mL of water. The Formula, ∆Tb = K b × molality
Moles of sucrose = 0.5969
freezing point of solution is ............ New mass of H2O = a kg
Put value of (i) we get,
K. (Nearest integer) 3
Depression in freezing point 3 × 1000
[Given, K f = 1.86 K kg mol − 1 , ∆Tf = K f × m 0.60 = 5 × M ⇒ 0.60 = 5 ×
100 M × 100
density of water = 1.00 g cm − 3 , 0.5969
4= × 1.86 1000
freezing point of water = 273.15 K] a 150
[2021, 27 Aug Shift-II] 0.60 M = 5 × 30 ⇒ M = = 250
⇒ a = 0.2775 kg 0.60
Ans. (271) ∴ Molar mass of substance ‘X’ is 250 g
Ice separated = 795.86 − 277.5
40 g of glucose mixed with 200 mL of mol − 1.
= 518.3 g ≈ 518 g.
water
180 g of glucose =1 moles of glucose 51 Which one of the following 0.06 M
49 1.46 g of a biopolymer dissolved in a
40 g of glucose mol = 0.22 mol aqueous solutions has lowest
100 mL water at 300 K exerted an
1 mL of water = 1 g of water freezing point? [2021, 22 July Shift-II]
osmotic pressure of 2.42 × 10 −3 bar.
[d = 1g / cm2 , 1 mL = 1 cm 3] (a) Al2 (SO 4 ) 3 (b) C 6H12O 6
200 mL of water = 200 g of water
The molar mass of the biopolymer (c) Kl (d) K2 SO 4
∆Tf = K f m
is ……… × 10 4 g mol −1 . (Round off
Ans. (a)
where, ∆Tf = depression in freezing
to the nearest integer)
van’t Hoff factor of Al2 (SO4 ) 3 is 5
point, [Use : R = 0.083 L bar mol −1 K −1 ] (maximum), so this will have lowest
K f = molal elevation constant [2021, 27 July Shift-I]
freezing point.
= 1.86 K kg mol −1 and Ans. (15) Depression in freezing point, ∆Tf = iK f m
m = molality of solution Using formula; π =CRT where,i = van’t Hoff factor
1.86 × 0.22 π = osmotic pressure, K f = molal depression constant
∆Tf = × 1000 (Q1000 g = 1 kg)
200 C = molarity (concentration) m = molality
∆Tf = 2K T = temperature of solution For freezing point to be lowest,
∴ (Tf − Tf ′) = 2 Number of moles of solute ∆Tf should be highest and thei values are
Molarity, C =
Tf = freezing point of water (273 K)  Volume of solution (L) follows
 
Tf ′ = freezing point of solution Given mass 1.46 Solute i
 Moles = =
Molecular mass M C6H12O6 1
273 K − Tf ′ = 2K
. × 1000 Al2 (SO4 ) 3 5 →i highest,
Tf′ = (273 − 2)K Molarity =
146
=
1460
∆Tf maximum,
= 271K M × 100 (mL) 100 × M
Tf minimum
1460
∴ π= × 0.083 × 300 KI 2
48 1 kg of 0.75 molal aqueous solution 100 × M
K2SO4 3
of sucrose can be cooled up to Given, π = 2.42 × 10 −3 bar Hence, for Al 3 (SO4 ) 3 freezing point is
− 4°C before freezing. The amount Therefore, M = 15.02 × 10 4 g /mol lowest.
78 JEE Main Chapterwise Topicwise Chemistry

52 A solute a dimerises in water. The 54 A 1 molal K 4Fe(CN) 6 solution has a 5.12 × 5 × 10

5.5 − Tf1 =
boiling point of a 2 molar solution 58
degree of dissociation of 0.4. Its
of A is 100.52°C. ⇒ Tf1 = 1086
. °C
boiling point is equal to that of
or Tf1 ≈ 1°C
The percentage association of A is another solution which contains
……… . (Round off to the nearest 18.1 weight per cent of a non- 56 The size of a raw mango shrinks to
integer) electrolytic solute A. The molar a much smaller size when kept in a
[Use : K b for water mass of A is ....... u. (Round off to concentrated salt solution. Which
= 0.52 K kg mol −1 , the nearest integer). one of the following processes can
boiling point of water = 100°C] [Density of water = 1.0g cm −3 ] explain this? [2020, 2 Sep Shift-II]
[2021, 18 March Shift-II] [2021, 17 March Shift-II]
(a) Osmosis
Ans. (100) Ans. (85) (b) Dialysis
Given :Tb = 100.52° C K4Fe(CN) 6- 4K+ + [Fe(CN) 6 ] 4 − (c) Diffusion
Tb° = 100 ° C Initial conc. 1m 0 0 (d) Reverse osmosis
Final conc. (1 − 0.4) m 4 × 0.4 0.4 m Ans. (a)
⇒ K b = 0.52 K kg mol −1 = 0.6 m = 16
. m
Elevation in boiling point, When a raw mango is kept in a
Effective molality = 0.6 + 16. + 0.4 = 2.6 m concentrated salt solution, the mango
∆Tb = Tb − Tb° As elevation in boiling point is a will shrink because of exo-osmosis.
∆Tb = 100.52 − 100 colligative property which depends on Mango cell membrane acts as
∆Tb = 0.52º C the amount of solute. So, to have same semi-permeable membrane and its cell
boiling point, the molality of two cytoplasm is considered as a solution of
For dimerisation (van’t Hoff factor) solutions should be same. concentration,C 1M (say). Let, the
 α
i = 1 −  Molality of non-electrolyte solution concentration of salt solution isC2 M,
 2 where C 1 < C2 (mentioned).
Q ∆Tb = i × K b × m = molality of K4 [Fe(CN) 6 ] = 2.6 m
So, osmotic pressure developed at salt
 α Now, 18.1 weight per cent solution means
0.52 =  1 −  × 0.52 × 2 solution, π2 will be greater than that at
 2 18.1 g solute is present in 100 g solution
and hence, (100 − 18.1 =) 819. g water. cell cytoplasm, π 1 at a given
α=1 temperature.
Molality
So, percentage association = 100% (Mass of solute/Molar mass of solute ) π 1 =C 1RT
=
Mass of solvent (g) and π2 = C2 RT
53 2 molal solution of a weak acid HA × 1000 So, solvent molecules (water) will flow
has a freezing point of 3.885°C. The Now, 2.6 =
18.1/ M out from mango cells to salt solution
degree of dissociation of this acid 81.9/ 1000 resulting shrinking of mango. This state is
also known as plasmolysis.
is ……… × 10 −3 . (Round off to the where, M is the molar mass of
non-electrolyte solute
nearest integer). 57 A cylinder containing an ideal gas
Molar mass of solute, M = 85
[Given : Molal depression constant (0.1 mol of 1.0 dm 3 ) is in thermal
of water = 1.85K kg mol −1 , 55 C 6H6 freezes at 5.5°C. The equilibrium with a large volume of
freezing point of pure water = 0° C] 0.5 molal aqueous solution of
temperature at which a solution 10
[2021, 18 March Shift-I] ethylene glycol at its freezing point.
Ans. (50) g of C 4H10 in 200 g of C 6H6 freeze
If the stoppers S 1 and S 2 (as shown
is ………°C. (The molal freezing
Given, in the figure) are suddenly
point depression constant of C 6H6
Depression in freezing point, withdrawn, the volume of the gas in
is 5.12°C/m.) [2021, 24 Feb Shift-II]
K f = 1.85 K kg mol −1 litres after equilibrium is achieved
Ans. (1)
Tf° = 0 ° C will be ………
Pure solvent : C6H6 (l )
Tf = 3.885° C (Given, K f (water) = 2.0 K kg mol −1 ,
∆Tf = Tf − Tf° Given, Tf° = 5.5 ° C
R = 0.08dm 3 atm K −1mol −1 )
= 3.885 − C = 3.885° C K f = 5.12° [2020, 9 Jan Shift-II]
C/m ⇒ m = 200 g
∆Tf = 3.885°C
msolute = 10 g Frictionless
∆Tf = i × K f × m piston
Molar mass of solute
3.885 = i × 1.85 × 2
C4H10 = 12 × 4+ 10 = 58 S2
but, i = (1 + α) S1
Solute (C4H10 ) is non-dissociative;
3.885 = (1 + α) × 1.85 × 2
0.185 ∴ i=1
⇒ α= ∴ ∆Tf = iK f m Ideal gas
3.7
(10 / 58)
⇒ α = 0.05 ⇒ (Tf° − Tf1) = 1 × 5.12 × aq. ethylene glycol
(200 / 1000)
α = 50 × 10 −3
Solutions 79

Ans. (2.18) 59 A set of solutions is prepared using 60 1 g of a non-volatile,

K f = 2.0 (Given) m = 0 .5 m (Given) 180 g of water as a solvent and 10 g non-electrolyte solute is dissolved
∆Tf = K f × m = 2 × 0.5 = 1 of different non-volatile solutes A, B in 100 g of two different solvents A
∴ Tf = Actual freezing point of water is −1. and C. The relative lowering of and B, whose ebullisocopic
= 273 − 1 = 272 K. vapour pressure in the presence of constants are in the ratio of 1 : 5.
Pressure of gas after the stoppers are these solutes are in the order The ratio of the elevation in their
withdrawn = 1 atm (atmospheric ∆T (A)
pressure) [Given, molar mass of A =100g boiling points, b , is
∴ V=
nRT 0.1 × 0.08 × 272
= mol −1 ; B = 200g mol −1 ; ∆Tb (B)
p 1 atm C =10000
, g mol −1 ] [2019, 10 April Shift-II]
= 2.176 L ≈ 2.18 L [2020, 6 Sep Shift-II] (a) 5 : 1 (b) 10 : 1 (c) 1 : 5 (d) 1 : 0.2
(a) B > C > A (b) C > B > A Ans. (c)
58 The osmotic pressure of a solution (c) A > B > C (d) A > C > B
The expression of elevation of boiling
of NaCl is 0.10 atm and that of a Ans. (c) point,
glucose solution is 0.20 atm. The Relative lowering in vapour pressure w × 1000
osmotic pressure of a solution ∆Tb = K b × m × i = kb × 2 ×i
p ° − pS M2 × w 1
formed by mixing 1 L of the sodium (RLVP) = = χ solute or RLVP
p° where, m = molality
chloride solution with 2 L of the ∆p i = van’t Hoff factor = 1 (for
= = χ solute
glucose solution is x × 10 −3 atm. x is p° non-electrolyte/non-associable)
……… (nearest integer). w w2 = mass of solute in g = 1 g (present in
[2020, 4 Sep Shift-II] n→ moles of solute = ;
M both of the solutions)
Ans. (167) w M2 = molar mass of solute in g mol −1
N → moles of solvent =
Osmotic pressure, π = i × C × RT M (same solute in both of the solutions)
Given, weight of solvent (water) = 180 g w 1 = mass of solvent in g = 100 g (for both
Here, i = van’t Hoff factor,
of the solvents A and B)
T = temperature Weight of different non-volatile solute
w A , w B and w C = 10 K b = ebullioscopic constant
C = concentration and So, the expression becomes,
R = gas constant. Molar mass of MA = 100 g mol − 1
∆Tb ∝ K b
For NaCl, i = 2 MB = 200 g mol − 1
∆Tb (A) K b (A) 1
So, π NaCl = i × C NaCl × RT ⇒ MC = 10,000 g mol − 1 ⇒ = =
RLVP for A,
∆Tb (B) K b (B) 5
0.1 = 2 × C NaCl × RT 
10 K b (A) 1 
C NaCl =
0.05
 ∆p  Given K (B) = 5 
RT   = 100  b 
 p°  A 10
+
180
For glucose,i = 1because it cannot ionise 100 18 61 At room temperature, a dilute
So, π glucose = i × C glucose × RT 0. 1 solution of urea is prepared by
0.2 = 1 × C glucose × RT = = 0.091
1.1 dissolving 0.60 g of urea in 360 g of
0.2
Cglucose = RLVP for B, water. If the vapour pressure of
RT
10 pure water at this temperature is
(Q n NaCl = numbers of moles NaCl)  ∆p  200 0.05
  = = = 0.0049 35 mm Hg, lowering of vapour
nNaCl in 1 L = C NaCl × Vlitre  p°  B 10 180 10.05
+ pressure will be (Molar mass of
0.05
= (nglucose = number of moles of 200 18 urea = 60 g mol −1 )
RT RLVP for C, [2019, 10 April Shift-I]
glucose) 10
0.4 (a) 0.027 mmHg (b) 0.031 mmHg
nglucose in 2L = C glucose × Vlitre =  ∆p  10,000
RT   = (c) 0.017 mmHg (d) 0.028 mmHg
 p°  C 10
+
180
Vtotal = 1 + 2 = 3 L Ans. (c)
10,000 18
0.05 0.001 0.001 Key Idea For dilute solution, lowering of
So, final conc.NaCl = = =
3RT 0.001 + 10 10.001 vapour pressure (∆p) = p°− p and relative
0.4 ∆p
Final conc. glucose = = 0.000099 lowering of vapour pressure = which
3RT p°
From the above value the relative is a colligative property of solutions.
π total = π NaCl + π glucose lowering of vapour pressure in the ∆p
= [i × C NaCl + C glucose ] RT presence of there solute are in the = χ B × i ⇒ ∆p = χ B × i × p°
p°
 2 × 0.05 0.4  0.5 following order :
= +  × RT = atm
 3RT 3RT  3  ∆p   ∆p   ∆p  where, p° = vapour pressure of pure
  >  >  solvent
= 0.1666 atm = 1666 −3
. × 10 atm  p°  A  p°  B  p°  C
i = van’t Hoff factor
= 167.00 × 10 −3 atm Hence, option (c) is correct. χ B = mole fraction of solute
So, x = 167.00
80 JEE Main Chapterwise Topicwise Chemistry

Given, Ans. (d) Ans. (b)

p° = vapour pressure of pure water of25°C Elevation in boiling point Vapour pressure of water (p° ) = 760 torr
= 35 mm Hg (∆Tb ) = K b × m × i Number of moles of glucose
χ B = mole fraction of solute (urea) Depression is freezing point Mass (g)
0.60 =
(∆Tf ) = K f × m × i Molecular mass (g mol −1)
nB 60 0.01
= = = where, m = molality =
18 g
= 0.1 mol
nA + nB 360 + 0.60 20 + 0.01
For the glucose solution (van’t Hoff 180 gmol −1
18 60 factor,i = 1),
0.01 Molar mass of water = 18 g/mol
= = 0.0005 ∆Tb1m = ∆Tf2 m = 2K Mass of water (given) = 178.2g
20.01
So, K b × 1 × 1 = Kf × 2 × 1 Number of moles of water
i = van’t Hoff factor = 1 (for urea)
⇒ K b = 2K f Mass of water
Now, according to Raoult’s law, =
Molar mass of water
∆p = χ B × i × p° 178. 2g
64 Freezing point of a 4% aqueous = = 9.9 mol
On substituting the above given values, 18 g /mol
we get solution of X is equal to freezing
point of 12% aqueous solution of Y. Total number of moles = (0.1 + 99
. ) moles
∆p = 0.0005 × 1 × 35 = 0.0175 mm Hg
If molecular weight of X is A, then = 10 moles
molecular weight of Y is Now, mole fraction of glucose in solution
62 A solution is prepared by dissolving
= Change in pressure with respect to
0.6 g of urea (molar mass = 60 g (a) 4A (b) 2A
initial pressure
mol −1 ) and 1.8 g of glucose (molar (c) 3A (d) A
∆p 0.1
=
mass = 180 g mol −1 ) in 100 mL of [2019, 12 Jan Shift-I] i.e.
p° 10
water at 27°C. The osmotic Ans. (c)
or ∆p = 0.01p° = 0.01 × 760 = 7.6 torr
pressure of the solution is Given, Freezing point of 4% aqueous
∴ Vapour pressure of solution
(R = 0.08206 L atm K −1 mol −1 ) solution of X.
= (760 − 7.6) torr
[2019, 12 April Shift-II] = Freezing point of 12% aqueous solution
of Y = 7524
. torr
(a) 8.2 atm (b) 2.46 atm
(c) 4.92 atm (d) 1.64 atm or (∆Tf ) X = (∆Tf ) Y [Q∆Tf = Tf° − Tf ]
Ans. (c) K f × mX = K f mY
66 The vapour pressure of acetone at
where, mX and mY are molality of X and Y,
20°C is 185 torr. When 1.2 g of a
Key Idea Osmotic pressure is
proportional to the molarity (C) of the respectively. non-volatile substance was
solution at a given temperature (T). or mX = mY dissolved in 100 g of acetone at
Thus, π ∝C, π = CRT (for dilute solution) Now, 20°C, its vapour pressure
n
π = RT molality =
Number of moles of solute (n) was 183 torr. The molar mass
V Mass of solvent (in kg) (g mol–1 ) of the substance is
n Weight [JEE Main 2015]
For the relation, π = CRT = RT n=
V Molecular mass (a) 32 (b) 64
Given, mass of urea = 0.6 g wX wY (c) 128 (d) 488
=
Molar mass of urea = 60 g mol − 1 MX × (w solvent) 1 MY × (w solvent)2 Ans. (b)
Mass of glucose = 1.8 g Given, po = 185 torr at 20 ° C
Given, w X = 4 and w solvent) 1 =96
Molar mass of glucose = 180 g mol − 1 ps = 183 torr at 20 ° C
[n (urea) + n2 (glucose)] w Y = 12 and w (solvent) 2 =88
π= 2 RT MX = A Mass of non-volatile substance, m = 1.2 g
V Mass of acetone taken = 100 g
 0.6 1.8  4 × 1000 12 × 1000
 +  ∴ = M=?
  MX × 96 MY × 88
= 60 180 × 1000 × 0.0821 × 300 As , we have
100 12 × 1000 × MX × 96
Thus, MY = po − ps n
= (0.01 + 0.01) × 10 × 0.0821 × 300 4 × 1000 × 88 =
π = 4 .92 atm ps N
96 × 12
= ×A Putting the values, we get,
4 × 88
63 Elevation in the boiling point for 1.2
1 molal solution of glucose is 2 K . = 3.27A ≈ 3 A 185 − 183
= M
183 100
The depression in the freezing
65 18 g of glucose (C 6H12O 6 ) is added 58
point for 2 molal solution of
to 178.2 g water. The vapour 2 1.2 × 58
glucose in the same solvent is 2 K. ⇒ =
pressure of water (in torr) for this 183 100 × M
The relation between K b and K f is
aqueous solution is [JEE Main 2016] 183 × 12. × 58
(a) K b = 15
. Kf (b) K b = 05
. Kf ∴ M=
(a) 76.0 (b) 752.4 2 × 100
(c) K b = K f (d) K b = 2K f
[2019, 10 Jan Shift-II]
(c) 759.0 (d) 7.6 M = 63.684 ≈ 64 g / mol
Solutions 81
760 − ps
67 K f for water is 1.86 K kg mol −1 . If is a non-volatile solute. Thus, according =
0.1
your automobile radiator holds 1.0 to Raoult’s law, 760 10
kg of water, then how many grams p0 − p solute ⇒ ps = 760 − 7.6 = 752.40 torr
= X solute
of ethylene glycol (C 2H6O 2 ) must p0
18 72 Equimolar solutions in the same
you add to get the freezing point of Moles of glucose = = 0.1
180 solvent have [AIEEE 2005]
the solution lowered to –2.8°C?
178.2 (a) different boiling point and different
[AIEEE 2012] Moles of H2O = = 9.9
18 freezing point
(a) 72 g (b) 93 g
0.1 0.1 (b) same boiling point and same
(c) 39 g (d) 27 g Xglucose = = freezing point
. + 0.1 10
99
Ans. (b) (c) same freezing point but different
17.5 − ps 0.1
Coolant is glycol (C2H6O2 ) and it is Thus, = boiling point
non-electrolyte. 17.5 10 (d) same boiling point but different
1000K fw 1 So, ps = 17.325 mm Hg freezing point
∆Tf = 2.8° C ⇒ ∆Tf =
m1w2 Ans. (b)
1000 × 1.86 × w 1 70 A 5.25% solution of a substance is Boiling point and freezing point depend
2.8 = isotonic with a 1.5% solution of
62 × 1000 on K b (molal elevation constant) andK f
urea (molar mass = 60 g mol −1 ) in (molal depression constant) of the
⇒ w 1 = 93.33 g
the same solvent. If the densities solvent. Thus, equimolar solution (of the
of both the solutions are assumed non-electrolyte), will have same boiling
68 Ethylene glycol is used as an
antifreeze in a cold climate. to be equal to 1.0 g cm −3 , molar point and also same freezing point.
mass of the substance will be ∆Tf = K f × molality;
Mass of ethylene glycol ∆Tb = K b × molality
[AIEEE 2007]
which should be added to 4 kg
(a) 90.0 g mol−1 (b) 115.0 g mol−1 Note In this question, nature of solute
of water to prevent has not been mentioned. Hence, we
(c) 105.0 g mol−1 (d) 210.0 g mol−1
it from freezing at − 6° C will be have assumed that solute is
Ans. (d)
(K f for water = 1.86 K kg mol −1 and non-electrolyte.
molar mass of ethylene glycol Osmotic pressure of isotonic solutions
are equal.
= 62 g mol −1 ) [AIEEE 2011] 73 A pressure cooker reduces cooking
Therefore, π 1 = π2 time for food because [AIEEE 2003]
(a) 804.32 g (b) 204.30 g
⇒ C 1RT = C2 RT ⇒ C 1 = C2 (a) heat is more evenly distributed in the
(c) 400.00 g (d) 304.60 g
If densities of both the solutions are cooking space
Ans. (a) equal, then 5.25 g of a substance and 1. 5 g (b) boiling point of water involved in
∆Tf = Freezing point of H2O – freezing of urea are dissolved in the same volume cooking is increased
point of ethylene glycol solution of the solvent, thus, (c) the higher pressure inside the
= 0 − ( − 6° ) = 6° C1 =
5.25 /M cooker crushes the food material
K f = 1. 86 ° K kg mol −1 V (d) cooking involves chemical changes
w 1 = Mass of ethylene glycol in grams [QM = molecular weight of helped by a rise in temperature
unknown substance] Ans. (b)
w2 = Mass of solvent ( H2O) in grams 5.25 /60
C2 = Higher pressure inside the cooker
= 4000 g V
m1 = Molar mass of ethylene glycol increases boiling point, thus heat
5.25 /M 1. 5 /60
∴ = ⇒ M = 210.0 g mol −1 consistently given is used up by food
= 62 g mol −1 V V material instead in boiling and
1000 K f w 1 1000 × 1.86 × w 1
∆Tf = ⇒6= constant boiling evaporation.
m1 w2 62 × 4000 71 18 g of glucose (C 6H 12 O 6 ) is added
w 1 = 804.32g 74 For an aqueous solution, freezing
to 178.2 g of water. The vapour
point is – 0.186°C. Elevation of the
pressure of water for this aqueous
69 The vapour pressure of water at boiling point of the same solution is
solution at 100°C is
(K f = 1.86° mol −1 kg and
[AIEEE 2006]
20°C is 17.5 mmHg. If 18 g of glucose
(a) 759.00 torr (b) 7.60 torr
(C 6H12O 6 ) is added to 178.2 g of K b = 0.512° mol −1 kg) [AIEEE 2002]
(c) 76.00 torr (d) 752.40 torr
water at 20°C, the vapour pressure (a) 0.186° (b) 0.0512°
Ans. (d) (c) 1.86° (d) 5.12°
of the resulting solution will be
[AIEEE 2008] According to Raoult’s law, relative Ans. (b)
lowering of vapour pressure,
(a) 17.675 mmHg (b) 15.750 mmHg We know that, ∆Tb = mK b , ∆Tf = mK f
p° − ps n
(c) 16.500 mmHg (d) 17.325 mmHg = ∆Tb K b 0.512
p° N = =
Ans. (d) ∆Tf K f 1.86
760 − ps 18 / 180
This problem is related to the relative = 0.512
760 18 / 180 + 178.2/ 18 ∆Tb = × 0.186 = 0.0512 °
lowering of vapour pressure as glucose 1.86
82 JEE Main Chapterwise Topicwise Chemistry

Ans. (d) Freezing point of solution = Freezing

TOPIC 4 The van’t Hoff factor (i) is highest for point − ∆Tf of water
Abnormal Molecular Masses KHSO4 as it dissociate into its ions. van’t = 273 − 3.98 ~− 269.
and Distribution Law Hoff factor is the ratio of total number of
ions produced after complete 79 Of the following four aqueous
dissociation to before dissociation. solutions, total number of those
75 1.22 g of an organic acid is Hydrazine, glucose and glycine will not
separately dissolved in 100 g of solutions whose freezing point is
dissociate to produce ions.
benzene (K b = 2.6 K kg mol − 1 ) lower than that of 0.10 M C 2H5OH is
Whereas,KHSO4 dissociates into ions.
………… . (Integer answer)
and 100 g of acetone KHSO4 → K+ + HSO−4
(K b = 1.7 K kg mol − 1 ). The acid is Hence,i will highest forKHSO4 (i) 0.10 M Ba 3 (PO4) 2
∴ Colligative property i.e. freezing point (ii) 0.10 M Na 2SO4
known to dimerise in benzene but depression will be highest forKHSO4 as (iii) 0.10 M KCl
remain as a monomer in acetone. ∆Tf ∝ i [Qm is constant i.e. 0.1] (iv) 0.10 M Li3PO4
The boiling point of the solution in Hence, correct option is (d). [2021, 26 Aug Shift-I]
acetone increases by 0.17°C. The Ans. (4)
increase in boiling point of solution 77 In a solvent 50% of an acid HA As 0.10 M C2H5OH is non-dissociative in
in benzene in °C is x × 10 − 2 . The dimerises and the rest dissociates. nature and all salts [0.10 MBa3 (PO4 )2 ,
value of x is ........ (Nearest integer) 0.10 M Na2SO4 ,
The van’t Hoff factor of the acid is 0.10 M KCl, 0.10 MLi3PO4 ] are electrolyte
[Atomic mass : C = 12.0, H = 1.0, ………… × 10 −2 . and dissociative in nature.
O= 16.0] [2021, 31 Aug Shift-II]
(Round off to the nearest integer) ∆Tf = iK f m
Ans. (13) [2021, 27 July Shift-II] Wherei is van’t Hoff factor.
With benzene as solvent, RCOOH Ans. (125) i = 1 for C2H5OH (no dissociation)
dimerises. 1 mole of acid HA. i > 1 for all other electrolytes
2RCOOH a (RCOOH) Dimerisation 2HA q H2 A2 where dissociation takes place.
2
1 So, for all these electrolytes effective
∴ i= Initial 0.5 0
2 Final 0 0.25 molarity is more than 0.10. So, all the
elecrolytes given will have low freezing
∆Tb = i × K b × m Dissociation
point.
where, ∆Tb = boiling point elevation, HA q H+ + A −
K b = ebulliscopic constant Initial 0.5 0 0
Final 0 0.5 0.5 80 The water having more dissolved
m = molality Final moles O 2 is [2021, 22 July Shift-II]
van’t Hoff factor (i) =
i = van’t Hoff factor Initial moles (a) boiling water (b) water at 80°C
1 1.22 / Mw 0.25 + 0.5 + 0.5 (c) polluted water (d) water at 4° C
∆Tb = × 2.6 × …(i) =
2 100 / 1000 1 Ans. (d)
With acetone as solvent, no . = 125 × 10 −2
= 125 At 4°C, the water have more dissolved
dimerisation. O2 . Since, dissolution ofO2 gas in water is
∴ i=1 an exothermic process, and solubility of
78 83 g of ethylene glycol dissolved in oxygen in water is high, at lower
∆Tb = i × K b × m 625 g of water. The freezing point temperature. On increasing
1.22 / Mw
0.17 = 1 × 1.7 × …(ii) of the solution is ………K. (Nearest temperature, solubility of gas decreases
100 / 1000 and water pollution also decrease the
integer)
Eq. (i) divide by Eq. (ii), solubility. First, the solubility of oxygen
[Use, molal freezing point increases as temperature decreases i.e.
1 1.22 / Mw
× 2.6 × depression constant of water
∆Tb 2 100 / 1000 warmer surface water requires less
=
0.17 1 × 1.7 × 1.22/ Mw
= 1.86 K kg mol − 1 , dissolved oxygen to reach 100% air
100 / 1000 Freezing point of water = 273 K saturation than cooler water.
0.26 and Atomic masses : C = 12.0 u, O
⇒ ∆Tb = = 13 × 10 −2 81 When 12.2 g of benzoic acid is
2 = 16.0 u, H = 1.0 u]
[2021, 26 Aug Shift-II] dissolved in 100 g of water, the
x = 13
Ans. (269) freezing point of solution was
found to be – 0.93°C
76 Which one of the following 0.10 M ∆Tf = iK f × m
(K f (H2O) = 1.86 K kg mol −1 ). The
aqueous solutions will exhibit the For ethylene glycol,i = 1
Number of moles of solute number (n) of benzoic acid
largest freezing point depression ? Molality (m) =
[2021, 31 Aug Shift-I] Weight of solvent (kg) molecules associated
(a) Hydrazine (b) Glucose 83 × 1000 ~ (assuming 100% association) is
∆Tf = 1 × 1.86 × − 3.98 ……… . [2021, 26 Feb Shift-II]
(c) Glycine (d) KHSO 4 62 × 625
Solutions 83

Ans. (2) 60
α= = 0.6 86 The osmotic pressure of a dilute
Association 100
n PhCOOH → (PhCOOH) n solution of an ionic compound XY in
∆Tb = i ⋅K f ⋅ m
Benzoic acid water is four times that of a
Assuming 100% association (α = 1), = [(1 + (n − 1) α] × K f × m
solution of 0.01 M BaCl 2 in water.
∆Tb = [(1 + (5 − 1) 0.6] × 0.52 × 1
i = 1 − α  1 −  =
1 1 Assuming complete dissociation of
⇒ [Qα + 1]
 n n = (1 + 24 . ) × 0.52
the given ionic compounds in
Now, ∆Tf = K f × m × i ∆Tb = 1.768
water, the concentration of XY (in
w × 1000 1 Tb = 1.768 + 373.15
0 − (0.93) = 1. 86 × B × mol L−1 ) in solution is
w A × MB n = 37491 . = 375 K [2019, 9 April Shift-I]

[Qw B = mass of PhCOOH = 12.2 g (a) 4 × 10−2 (b) 16 × 10−4

84 The elevation of boiling point of (c) 4 × 10−4 (d) 6 × 10−2
w A = mass of H2O = 100 g 0.10 m aqueous CrCl 3 ⋅xNH3
MB = molar mass of PhCOOH] Ans. (d)
solution is two times that of 0.05 m
= 122g mol −1 aqueous CaCl 2 solution. The value Key Idea Osmotic pressure is
12.2 × 1000 1 proportional to the molarity (C) of the
= 1.86 × × of x is ....... . solution at a given temperature, π = CRT
100 × 122 n
[Assume 100% ionisation of the
1.86 × 122
. × 1000 Concentration of BaCl2 = 0.01 M (Given)
⇒ n= =2 complex and CaCl 2 , coordination
0.93 × 100 × 122 π XY = 4 π BaCl2 (Given)
number of Cr as 6, and that all
∴ Number of benzoic acid molecules i × CRT = 4 × i × CRT …(i)
NH3 molecules are present inside
associated, n = 2 For the calculation of i,
the coordination sphere]
[2020, 6 Sep Shift-I] XY → X + + Y − (Here, i = 2)
82 If a compound AB dissociates to
Ans. (5.00) BaCl2 → Ba2 + + 2Cl − (Here, i = 3)
the extent of 75% in an aqueous Putting the values ofi in (i)
∆Tb = i × m × K b
solution, the molality of the 2 × [XY ] = 4 × 3 × [BaCl2 ]
For CaCl2 , i = 3, m (CaCl2 ) = 0.05 m
solution which shows a 2.5 K rise in 2 × [XY ] = 12 × 0.01
∴ ∆Tb = 3 × 0.05 × K b =0.15K b 12 × 0.01
the boiling point of the solution is [XY ] =
Molality of CrCl 3 ⋅xNH3 = 0.1 m
……… molal. (Rounded off to the 2
∴ ∆Tb′ = i × m × K b = 0.1 iK b So, the concentration of XY
nearest integer)
Given that :0.1 iK b = 2 × 0.15 × K b = 0.06 mol L−1
[K b = 0.52 K kg mol −1 ]
∴i = 3 and coordination number is 6. = 6 × 10 −2 mol L−1
[2021, 25 Feb Shift-II]
Thus, complex will be [Cr(NH3) 5 Cl]Cl2
Ans. (3) 87 Molal depression constant for a
∴ x=5
As AB is a binary electrolyte,
Hence, the correct answer is 5. solvent is 4.0 K kg mol −1 . The
∴ AB q A + + B − , n = 2 depression in the freezing point of
i = 1 + α (n − 1) = 1 +
75
(2 − 1) = 1.75 85 How much amount of NaCl should the solvent for 0.03 mol kg −1
100 solution of K 2SO 4 is
be added to 600 g of water
Given, ∆Tb = 2.5 K
(ρ = 1.00 g/mL) to decrease the (Assume complete dissociation of
K b = 0.52 K kg mol −1 freezing point of water to −0.2°C? the electrolyte) [2019, 9 April Shift-II]
∴ ∆Tb = K b × m × i …… (The freezing point depression (a) 0.18 K (b) 0.36 K
⇒ m=
∆Tb
=
2.5 constant for water = 2 K kg mol −1 ) (c) 0.12 K (d) 0.24 K
K b × i 0.52 × 1.75 [2020, 9 Jan Shift-I] Ans. (b)
Ans. (1.76) Key Idea Depression in freezing point
= 2.74 ~− 3 mol /kg
i × K f × w NaCl × 1000 (∆Tf ) is given by ∆Tf = iK f m
∆Tf = i × m × K f =
MNaCl × wH 2 O i = vant Hoff factor
83 1 molal aqueous solution of an (= 58. 5 ) K f = molal depression constant
electrolyte A 2B3 is 60% ionised. w B × 1000 m = molality
The boiling point of the solution at (m = molality) =
MB × w A K f = 40. K kg mol −1 (Given)
1 atm is ………… K (Rounded off to m = 0.03 mol kg −1 (Given)
the nearest integer). [Given, K b for ∆Tf = 0.2 because freezing point
= − 0.2°C ∆Tf = ?
(H2O) = 0.52 K kg mol −1 ] For K2SO4 , i = 3
[2021, 25 Feb Shift-I] K f of water 2 K kg mol −1 (Given)
i = van’t Hoff factor, for NaCl = 2 It can be verified by the following
Ans. (375) equation :
Given, K b (H2O) = 0.52 K kg mol −1 ∆Tf × MNaCl × wH 2 O
∴w NaCl = K2SO4 - 2K+ + SO24−
A2 B 3 → 2A +3 + 3 B −2 i × K f × 1000 Using formula
No. of ions, n = 5, concentration, m = 1 0.2 × 58.5 × 600 ∆Tf = iK f × m
= = 1.755 g ≈ 1.76 g
molal (Given) 2 × 2 × 1000 = 3 × 4 × 0.03 = 0.36 K
84 JEE Main Chapterwise Topicwise Chemistry

88 A solution contain 62 g of ethylene For diluted milk Now, we know that depression in
∆Tf1 = K f × m1 × i freezing point (∆Tf ) is given by following
glycol in 250 g of water is cooled
⇒ 0 − (0.2) ⇒ 0.2 equation:
upto –10°C. If K f for water is 1.86 K
w milk × 1000 ∆Tf = i × K f × m
kg mol −1 , then amount of water = Kf × ×1 i × K f × w solute × 1000
Mmilk × w1 (H2O) = ...(i)
(in g) separated as ice is Mw solute × w solvent
[2019, 9 Jan Shift-II] For pure milk
(a) 32 (b) 48 (c) 64 (d) 16 ∆Tf2 = K f × m2 × i Given,w solute (benzoic acid) = w g
Ans. (c) ⇒ 0 − (−0.5) = 0.5 = K f w solvent (benzene) = 30 g
w milk × 1000
Considering the expression of the × ×1 Mw solute (benzoic acid) = 122 g mol − 1,
Mmilk × w2 (H2O) ∆Tf = 2 K
depression in freezing point of a solution,
∆Tf = K f × m × i 0.2 K f w milk × 1000 K f = 5 Kkg mol − 1, %α = 80 or α = 0.8
So, = ×
° w B × 1000 0.5 K f Mmilk × w 1 (H2O) 2(C6H5 COOH) (C6H5 COOH)2
-
Tf − Tf = K f × ×i …(i)
MB × w A (in g) Mmilk × w2 (H2O) Initial 1 0
× Final 1− α α /2
Here,Tf° = 0 ° C, Tf = − 10 °C w milk × 1000
= 1 − 0.8 = 0.2 0.8 / 2 = 0.4
w B = mass of ethylene glycol = 62 g w2 (H2O)
= Total number of moles at equilibrium
MB = molar mass of ethylene glycol w 1 (H2O)
= 0.2 + 0.4 = 0.6
  w 2 (H2O) (in pure milk)
CH2  CH2  2 Number of moles at equilibrium

 ⇒ = i=
 Number of moles present initially
    w1 (H2O) (in diluted milk) 5
 
OH OH 0.6



 i.e. 3 cups of water has to be added to 2 i= = 0.6
  1
cups of pure milk.
= 62 g mol −1 On substituting all the given values in Eq.
90 K 2HgI 4 is 40% ionised in aqueous (i), we get
w A = mass of water in g as liquid solvent, 0.6 × 5 × w × 1000
solution. The value of its van’t Hoff 2= , w = 244
. g
i = van’t-Hoff factor = 1 122 × 30
factor (i) is [2019, 11 Jan Shift-II]
(for ethylene glycol in water)
(a) 1.6 (b) 1.8 Thus, weight of acid (w) is 2.4
K f = 1.86 K kg mol −1
(c) 2.2 (d) 2.0 g.Molecules of benzoic acid dimerise in
On substituting in Eq. (i), we get benzene as:
62 × 1000 Ans. (b)
0 − (− 10) = 1.86 × ×1 2(C6H5 COOH) (C6H5 COOH)2
-
62 × w A The ionisation of K2HgI4 in aqueous
1.86 × 62 × 1000 solution is as follows:
⇒ wA = 92 For 1 molal aqueous solution of the
10 × 62 K2 [HgI4 ] - 2K+ + [HgI4 ]2 −
following compounds, which one
van’t Hoff factor (i) for ionisation reaction
= 186 g will show the highest freezing
is given as,i = 1 + α ( n − 1)
So, amount of water separated as point? [JEE Main 2018]
where, n = number of ions,
ice (solid solvent) (a) [Co(H2O) 6]Cl3
α = degree of ionisation or
= 250 − w A = (250 − 186) g = 64 g (b) [Co(H2O) 5 Cl]Cl2 ⋅H2O
dissociation
From above equation, it is clear that n = 3 (c) [Co(H2O) 4 Cl2]Cl⋅2H2O
89 The freezing point of a diluted milk (d) [Co(H2O) 3Cl3] ⋅ 3H2O
i = 1 + 0.4 (3 − 1)
sample is found to be −0.2° C, while
[Given, %α = 40% or α = 0.4] = 1.8 Ans. (a)
it should have been −0.5°C for pure
milk. How much water has been Key Idea ‘‘Addition of solute particles to
91 Molecules of benzoic acid a pure solvent results to depression in
added to pure milk to make the its freezing point.’’
(C 6H5COOH) dimerise in benzene. ‘
diluted sample? All the compounds given in question are
w’ g of the acid dissolved in 30 g of
(a) 2 cups of water to 3 cups of pure milk ionic in nature so, consider their van’t
benzene shows a depression in Hoff factor (i) to reach at final
(b) 1 cup of water to 3 cups of pure milk
(c) 3 cups of water to 2 cups of pure milk
freezing point equal to 2 K. If the conclusion.
(d) 1 cup of water to 2 cups of pure milk percentage association of the acid
The solution with maximum freezing
[2019, 11 Jan Shift-I] to form dimer in the solution is 80, point must have minimum number of
Ans. (c) then w is solute particles. This generalisation can
We know that, (Given that K f = 5K kg mol − 1 , molar be done with the help of van’t Hoff factor
Depression in freezing points (∆Tf ) mass of benzoic acid = 122 g mol − 1 ) (i) i.e.
[2019, 12 Jan Shift-II] Number of solute particles ∝ van’t Hoff
T °f − Tf = K f × m × i factor (i)
(a) 1.8 g (b) 1.0 g (c) 2.4 g (d) 1.5 g
where,K f = molal depression constant Thus, we can say directly
w solute × 1000 Ans. (c)
m = molality = Solution with maximum freezing point
Msolute × w solvent (in g) Molecules of benzoic acid dimerise in
will be the one in which soluste with
benzene as:
i = van’t Hoff factor minimum van’t Hoff factor is present
2(C6H5 COOH) - (C6H5 COOH)2
Solutions 85

Now, for α i −1
⇒ = 1 − 0.527 α=
Co(H2O) 6 ]Cl 3 - [Co(H2O) 6 ] 3+ + 3Cl − 2 n− 1
van’t Hoff factor (i) is 4. Similarly for, ∴ α = 0.946 Here, n are the moles of an electrolyte
Thus, percentage of association = 946
.% (A − B) dissolved in a solvent.
[Co(H2O) 5 Cl]Cl2 ⋅H2O
- For Ax B y , Ax B y 3 xA + y + yB − x
[Co(H2O) 5 Cl]2 + + 2Cl − ‘i’ is 3 i−1
94 Consider the separate solution of Therefore, α=
[Co(H O) Cl ]Cl ⋅2H O - (x + y − 1)
2 4 2 2
0.500 M C 2H5OH (aq ), 0.100 M
[Co(H2O) 4 Cl2 ] + + Cl − ‘i’ is 2
Mg 3 (PO 4 ) 2 (aq ), 0.250 M KBr (aq)
and for [Co(H2O) 3 Cl 3] ⋅ 3H2O, ‘i’ is 1 as it 96 If sodium sulphate is considered to
and 0.125 M Na 3PO 4 (aq ) at 25°C.
does not show ionisation. be completely dissociated into
Which statement is true about cations and anions in aqueous
Hence, [Co(H2O) 3 Cl 3] ⋅3H2O have
minimum number of particles in the
these solutions, assuming all salts solution, the change in freezing
solution. to be strong electrolytes? point of water (∆Tf ), when 0.01 mole
[JEE Main 2014]
So, freezing point of its solution will be of sodium sulphate is dissolved in
maximum. (a) They all have same osmotic pressure 1 kg of water, is
(b) 0.100 M Mg 3 (PO 4 )2 (aq) has the
highest osmotic pressure
(K f = 1.86 K kg mol −1 ) [AIEEE 2010]
93 The freezing point of benzene
(c) 0.125 M Na3PO4 (aq ) has the highest (a) 0.0372 K (b) 0.0558 K
decreases by 0.45°C when 0.2 g of (c) 0.0744 K (d) 0.0186 K
osmotic pressure
acetic acid is added to 20 g of
(d) 0.5000 M C2H5OH (aq ) has the Ans. (b)
benzene. If acetic acid associates highest osmotic pressure Na2SO4 → 2Na+ + SO24−
to form a dimer in benzene,
Ans. (a) van’t Hoff factor (i) for Na2SO4 = 3
percentage association of acetic
Osmotic pressure, π = i × MRT ∆Tf = i × K f × m = 3 × 1.86 × 0.01
acid in benzene will be (K f for
Where, i = van’t Hoff factor, M = Molarity  -1 
benzene = 5.12 K kg mol − 1 ) 0.01 mol
R = Gas constant, Qm = 1 kg = 0.01 mol kg 
[JEE Main 2017]  
(a) 64.6 % (b) 80.4 % T = Temperature = 0.0558 K
(c) 74.6 % (d) 94.6 % For 0. 500 M C2H5OH (aq ) , i = 1 , thus,
Ans. (d) π C 2H (aq) = 0. 5 RT 97 If α is the degree of dissociation of
5 OH
Let the degree of association of acetic Na 2SO 4 , the van’t Hoff factor (i )
For 0. 100 M Mg 3 (PO4 )2 (aq ),i = 5
acid (CH3COOH) in benzene isα, then used for calculating the molecular
[Q Mg 3 (PO4 )2 3 Mg2 + + 2 PO34− ]
2CH3COOH - (CH3COOH) 2 mass is [AIEEE 2005]
Thus, π Mg (aq ) = 5 × 0. 1 × RT (a) 1 − 2 α (b) 1 + 2 α
Initial moles 1 0 3 (PO 4 ) 2
α = 0. 5 RT (c) 1 − α (d) 1+ α
Moles at 1−α
equilibrium 2 For 0.250 M KBr (aq), Ans. (b)
α α i = 2 [Q KBr 3 K+ + Br - ]
∴ Total moles = 1 − α + = 1− Na2SO4 3 2Na +
+ SO24−
2 2 Thus, πKBr (aq ) = 2 × 0.250 × RT = 0. 5 RT
α van’t Hoff factor, i = [1 + ( y − 1) α]
or i = 1− For 0. 125 M Na3PO4 (aq ), i = 4
2 where y is the number of ions from one
[Q Na3PO4 3 3Na+ + PO43− ] mole solute, (in this case = 3), α is the
Now, depression in freezing point (∆Tf ) is
Thus, π Na PO 4 (aq ) = 4 × 0. 125 × RT = 0. 5 degree of dissociation, i = (1 + 2α)
given as 3
∆Tf = i K f m K(i) RT
98 Which one of the following
where,K f = molal depression constant or Hence, all solutions have same osmotic
aqueous solutions will exhibit
cryoscopic constant. pressure.
highest boiling point? [AIEEE 2004]
m = molality
number of moles of solute
95 The degree of dissociation (α) of a (a) 0.01 M Na2 SO 4 (b) 0.01 M KNO 3
Molality = weak electrolyte, A x By is related to (c) 0.015 M urea (d) 0.015 M glucose
weight of solvent (in kg)
van’t Hoff factor (i) by the Ans. (a)
0.2 1000
= × expression [AIEEE 2011] The colligative property will be given as
60 20
Putting the values in Eq. (i) i −1 i −1 ∆Tb = i × kb × m
(a) α = (b) α =
 α  0.2 1000  (x + y − 1) x+ y+1 Where, ∆Tb = Elevation in boiling point
∴ 0.45 = 1 − (5.12) × i = van’t Hoff factor
 2   60 20  x + y −1 x+ y+1
(c) α = (d) α = K b = molal elevation constant
α 0.45 × 60 × 20 i −1 i −1
1− = m = molality of the solution
2 5.12 × 0.2 × 1000 Ans. (a)
From the above equation, it is clear that,
α van’t Hoff factor (i) is related to degree of
⇒ 1 − = 0.527 ∆Tb α i
2 dissociation (α) as
86 JEE Main Chapterwise Topicwise Chemistry

This suggests that higher the value ofi, π = MRT, where M is the molarity of Thus,
larger is the boiling point of the solution. the solution i (for BaCl2 ) > KCl > CH3COOH >
For 100% dissociation, i = number of ions (c) The correct order of osmotic sucrose
produced by one mole of solute pressure for 0.01 M aqueous solution
Thus, (c) is also true.
of each compound is
Thus, for (d) ∆Tf = K f m.
BaCl2 > KCl > CH3COOH > sucrose
(a) Na2SO4 (d) Two sucrose solutions of same K f is dependent on solvent.
Na2SO4 3 2Na+ +SO24- molality prepared in different
[3 ions]
Thus, freezing points
∴ i =3 solvents will have the same freezing = [T (solvent) − ∆Tf ] are different.
point depression Thus, (d) is false.
(b) KNO3
Ans. (d)
KNO3 3 K+ + NO–
3 (a) pA = XA pA° true 100 In a 0.2 molal aqueous solution of a
[2 ions]
(b) π = iMRT = MRT weak acid HX, the degree of
∴ i =2
true ionisation is 0.3. Taking K f for
(c) Urea [(NH2 CONH2 ) and (d) glucose [If van’t Hoff factor, i = 1]
are poor electrolytes, therefore i water as 1.85, the freezing point of
for these two solutes are equal to (c) π ∝i the solution will be nearest to
zero. Greater the value of i, larger is the [AIEEE 2003]
Hence, 0.01 M Na2 SO 4 possess value of π. (a) − 0.480°C (b) − 0.360°C
highest boiling point. i, for BaCl2 (strong electrolyte) is 3. (c) − 0.260°C (d) + 0.480°C
[BaCl2 3 Ba2 + + Cl − (2 ions)] Ans. (a)
99 Which one of the following i for KCl is 2. [KCl
3 K + +Cl − ] HX 3H +
+ X −1
statements is false? [AIEEE 2004]
i for CH 3COOH is α = 0.3
(a) Raoult’s law states that the vapour
2 [CH 3 COOH 3 CH 3COO − +H + ] i = 1 + α = 1.3
pressure of a component over a
solution is proportional to its mole But CH 3COOH is weak electrolyte ∆Tf = molality × K f × i
fraction than KCl.
= 0.2 × 1.85 × 1.3 = 0.481°
(b) The osmotic pressure ( π) of a i for sucrose is 1 as it is a
∴ Freezing point = − 0.481° C
solution is given by the equation non-electrolyte.
07
Chemical Equilibrium
where, p = partial pressure − 1.844 + (1.844)2 + 4 × 5.532
TOPIC 1 At equilibrium, the partial pressure ofO2
=
2
Chemical Equilibrium, Basic is pO 2 = (4)2 = 16 atm.
∴ x = 1.603
Law of Mass Action and Moles of PCl 5 = 3 − 1.603
Equilibrium Constant 03 2 SO 2 (g) + O 2 (g) → 2SO 3 (g)
= 1.397 ≅ 1400 × 10 − 3
The above reaction is carried out
01 The number of moles of NH3 , that in a vessel starting with partial 05 The equilibrium constant K C at 298
must be added to 2 L of 0.80 M pressure p SO = 250m bar, K for the reaction A + B C + D is
-
2
AgNO 3 in order to reduce the pO = 750m bar and p SO = 0. 100. Starting with an equimolar
concentration of Ag + ions to
2 3
When the reaction is complete, solution with concentrations of
5.0 × 10 − 8 M (K formation for the total pressure in the reaction A, B, C and D all equal to 1M, the
[Ag(NH3 ) 2] + = 1.0 × 10 8 ) is ……… vessel is ………… m bar. (Round off equilibrium concentration of D is
(Nearest integer) of the nearest integer). ……… × 10 − 2 M. (Nearest integer)
[2021, 27 July Shift-II] [2021, 26 Aug Shift-II]
[Assume no volume change on
Ans. (875) Ans. (182)
adding NH3 ] [2021, 27 Aug Shift-I]
2SO2 (g) + O2 (g) → 2SO3 (g) A + B q C + D
Ans. (4)
Initial 250 m bar 750 m bar 0 Initially, 1 1 1 1
Let moles added = a  250 
Final 0  750 −  m bar 250 m bar At equilibrium, 1− x 1− x 1+ x 1+ x
Ag + + 2NH3 q Ag(NH3)2+  2  2
1+ x 
t=0
a
 
= 625 m bar ∴ K C =  
0.8
2  1− x 
Total final pressure = 625 + 250
t = ∞ 5 × 10 −8  a − 1.6 2
1+ x 
100 = 
0.8
 2  = 875 mbar

0.8  1− x 
= 10 8
2 04 PCl 5 =PCl + Cl 2 , K c = 1.844 1+ x
= 10
−8 a  3
5 × 10  − 1.6 1− x
2  3.0 moles of PCl 5 is introduced 9
a x=
− 1.6 = 0.4 ⇒ a = 4. in a 1 L closed reaction vessel at 11
2 380 K. The number of moles of 9 20
Moles of D = 1 + x = 1 + =
PCl 5 at equilibrium is ………… 11 11
02 The equilibrium constant for the × 10 −3 . (Round off to the nearest = 1.818 = 181.8 × 10 −2 = 181.8 × 10 −2
reaction integer) [2021, 27 July Shift-I] ~= 182 × 10 −2 M
1
A (s) M (s) + O 2 (g)
= Ans. (1400)
2 06 Value of K p for the equilibrium
PCl 5 (g) q PCl 3( g) + Cl2 (g)
is K p = 4. At equilibrium, the partial t=0 3 moles
reaction
pressure of O 2 is ……… atm. t=∞ (3 − x ) moles x x N 2O 4 (g) 2NO 2 (g)
-
(Round off to the nearest integer) [PCl 3] [Cl2 ] 2
x at 288 K is 47.9.
[2021, 27 July Shift-II] =
[PCl 5 ] 3−x The K C for this reaction at same
Ans. (16)
= 1.844 temperature is …… (Nearest
According to the equation,
1 x2 + 1.844 − 5.532 = 0 integer)
A (s ) → M(s ) + O2 (g) (R = 0.083 L bar K −1mol −1 )
2 − b ± b2 − 4ac
x= [2021, 22 July Shift-II]
Equilibrium constant,K p = pO1/22 = 4 2a
88 JEE Main Chapterwise Topicwise Chemistry

Ans. (2) [Use : R = 8.3 J mol −1 K −1 , In ∆ng = 1 (for given reaction)

Given reaction, 10 = 2.3] On putting given values, we will get
2 NO2 (g) - N2O4 ( g) log 10 2 = 0.30, 1 atm = 1bar] 600.1 = 20.4 (RT ) 1 ⇒ T ≈ 354 K
So, ∆ng = [molar of gaseous
[antilog (− 0.3) = 0.501] 10 For the reaction, A(g) B(g) at
-
products-moles of gaseous reactants]
[2021, 18 March Shift-II]
=2− 1= 1
Ans. (1.66) 495 K, ∆ r G° = − 9.478 kJ mol −1 .
∆n g
K p = K C (RT ) If we start the reaction in a closed
2A (g) 2 A2 (g)
where,K p = equilibrium constant in Given, ∆G = 252 . kJ mol −1 container at 495 K with 22
gaseous state = 47.9 = 25200 J mol −1 millimoles of A, the amount of B is
K C = equilibrium constant T = 400 K the equilibrium mixture is ………
R = gas constant According to standard free Gibb’s millimoles (Round off to the
T = temperature equation, nearest integer).
⇒ KC =
47.9 ∆G ° = − RT lnK p [R = 8.314 J mol −1 K −1 , ln10 = 2.303]
0.083 × 288 25200 = − 23 . × 83
. × 400 log(K p ) [2021, 16 March Shift-I]
= 20038 −25200 Ans. (20)
. log K p = = − 33
.
∴ Hence,K C at same temperature . × 83
23 . × 400
(288 K) is 2. K p = 10 − 3. 3 = 10 − 3 × 0.501
A ( g) c B ( g)
Given,T = 495 K, ∆ r G ° = − 9478
. kJ/mol
. × 10 −4 bar − 1
K p = 501 We know,
07 2SO 2 (g) + O 2 (g) 2SO 3 (g)
- . × 10 − 5 Pa− 1
K p = 501 ∆G ° = − 2303
. RT log K
In an equilibrium mixture, the [B]
We know that, Q K=
partial pressures are ∆n g [A]
K p = K c (RT )
p SO = 45kPa; p O2 = 530 Pa and where,K = equilibrium constant
3 K p = K c (RT ) −1 − ∆G °
p SO = 45kPa. The equilibrium Now, log K =
[∴∆ng = 1 − 2 = −1]
constant K p = ……… × 10 −2 .
2
2303
. RT
KC × 1000
(Nearest integer) Kp = log K =
9478
.
. × 400
83 2303
. × 8314
. × 495
[2021, 20 July Shift-I]
Ans. (172) . × 10 −5 × 83
K c = 501 . × 400 ∴ logK = 1
−5 ⇒ K = 10
On reaction, ⇒ K c = 166 × 10 3
m / mol
2SO2 (g) + O2 (g) → 2SO3 (g) [B] nB
. × 10 − 2 L/mol
= 166 ⇒ = = 10
Given values are : [A] nA
pSO = 45kPa, pO 2 = 530 Pa = 0.53 kPa 09 Consider the reaction, Now, A (g) c B ( g)
3
pSO 2 = 43 kPa N 2O 4 (g)= 2NO 2 (g). t =0 22 0
[pSO3 (g ) ]2 t =t 22 − x x
Now, Kp = The temperature at which
[B] x
[pSO2 (g ) ]2 × [pO2 ] K C = 20.4 and K p = 600.1, is ………… K= = = 10
[A] 22 − x
On putting given values, we get, K. (Round off to the nearest
integer). So, x = 20
(43)2
⇒ Kp = Milimoles of B = 20
(45)2 × 0.53 [Assume all gases are ideal and
=
1849
=
1849 R = 0.0831 L bar, K −1 mol −1 ]. 11 A homogeneous ideal gaseous
2025 × 0.53 1073.25 [2021, 17 March Shift-II]
reaction, AB2 (g) q A(g) + 2B(g) is
= 1.7228 Ans. (354)
carried out in a 25 L flask at 27°C.
1.7228 × 102 The temperature at whichK C = 20.4 and The initial amount of AB2 was 1
=
102 K p = 600.1, is 354 K.
mole and the equilibrium pressure
= 172.28 × 10 − 2 = 172 Given reaction is,
was 1.9 atm. The value of K p is
Hence, the equilibrium constant, N2O4 (g) - 2NO2 (g)
Given values are : K p = 600.1
x × 10 −2 . The value of x is ………… .
K p = 172. [2021, 26 Feb Shift-I]
K C = 20.4 Ans. (73)
08 The gas phase reaction ∆ng = number of moles of product AB2 (g) - A (g) + 2B (g)
2A(g) A 2 (g)
= − number of moles of reactant
t =0 1 0 0
at 400 K has ∆G° = + 25.2 kJ mol −1 . Using relation betweenK p
t = t eq (1 − x) x 2x
and K C = 2 − 1= 1
The equilibrium constant K C for ∆n g (Σ mole) t eq = 1 − x + x + 2x = (1 + 2x)
K p = K C (RT )
this reaction is ……… × 10 −2 . Partial
1−x x 2x
(Round off to the nearest integer). where R is the gas constant = 0.083 L pressure p p p
atm/K mol (atm) 1 + 2x 1 + 2x 1 + 2x
Chemical Equilibrium 89

[p = Total pressure at equilibrium 13 For the reaction, A (g) → B (g), the 15 For the equilibrium A r B , the
= 19
. atm]
Now, at equilibrium pV = (1 + 2x) RT value of the equilibrium constant at variation of the rate of the forward
pV . × 25
19 300 K and 1 atm is equal to 100.0. (a) and reverse (b) reaction with
⇒ 1 + 2x = = = 193
.
RT 0.082 × 300 The value of ∆ r G for the reaction at time is given by [2020, 4 Sep Shift-I]
[V = 25 L, R = 0.082 L atm mol −1K−1 300 K and 1 atm in J mol − 1 is − xR,

Rate of reaction
T = 300 K] where x is ......... . (Rounded off to a
. −1
193 the nearest integer) (a)
⇒ x= = 0.465 Equilibrium
2
(R = 8.31 J mol − 1 K − 1 and b
p × p2
⇒ Kp = A B ln10 = 2.3) [2021, 24 Feb Shift-I] Time
pAB
2 Ans. (1380)

Rate of reaction
2
 x   2x  For a reaction, A (g) → B (g) a
 p ×  p
 1 + 2x   1 + 2x  Given,K p (equilibrium constant) = 100 (b) Equilibrium
⇒
 1− x  Temperature = 300 K b
 p Pressure = 1 atm
 1 + 2x  Time
Formula used
4x 3 × p3 (1 + 2x)

Rate of reaction
= × ∆G ° = − RT ln K p …(i)
(1 + 2x) 3 (1 − x) × p
Here, ∆G ° = standard Gibb’s free energy a
4x 3 × p2 (c)
= R = gas constant Equilibrium
(1 + 2x)2 × (1 − x)
. J mol −1 K −1
= 831 b
4 × (0.465) 3 × (19
. )2 Put value in Eq (i), we get Time
=
(1 + 2 × 0.465)2 × (1 − 0.465) ∆G ° = − R (300) In 100

Rate of reaction
= 0.7285 atm ∆G ° = − R (300) (2) ln (10) a
= 72.85 × 10 −2 atm Qln (10) = 23
. (d) Equilibrium
~− 73 × 10 −2 = x × 10 −2 b
∆G ° = − R (300) (2) (23
.)
∴ x = 73 ∆G ° = − 1380 R Time
Hence, ∆G ° = − x R Ans. (a)
12 At 1990 K and 1 atm pressure, there
are equal number of Cl 2 molecules x = 1380 For the equilibrium, A r B
At equilibrium, ra = rb
and Cl atoms in the reaction 14 An open beaker of water in Equilibrium is the condition when a
mixture. The value of k p for the equilibrium with water vapour is in a forward chemical reaction and its
reaction Cl 2 (g) 2Cl(g ) under
- sealed container. When few grams reverse reaction proceed at equal rates.
the above conditions is x × 10 −1 . of glucose are added to the beaker It can be illustrated by following graph.

The value of x is ......... . of water, the rate at which water

(Rounded off to the nearest molecules [2020, 2 Sep Shift-I]
a
(a) leaves the solution decreases
integer) [2021, 24 Feb Shift-I] Rate of Equilibrium
(b) leaves the solution increases reaction b
Ans. (5) (c) leaves the vapour increases
Cl2 (g) 2Cl (g)
= (d) leaves the vapour decreases
Let, moles of both of Cl2 and Cl molecule Ans. (c) Time
be x.
Pure water is a volatile liquid (solvent)
x 1 16 If the equilibrium constant for
Partial pressure of Cl is, pCl = ×1= whereas glucose is a non-volatile solute.
2x 2 At a certain temperature, water A q B + C is K eq ( 1)
and that of
Partial pressure of Cl2 is maintains an equilibrium state with B + C = P is K eq , the equilibrium
( 2)
x 1 water vapour in a sealed container.
pCl2 = × 1= When glucose is added into water a constant for A q P is
2x 2 [2020, 4 Sep Shift-II]
completely miscible solution is formed in
(p ) 2 which glucose molecules occupy the
Now, K p = Cl (1)
(a) K eq (2)
/ K eq (1)
(b) K eq (2)
+ K eq
pCl2 inter-molecular space of solvent (H2O)
molecules.
(1) (2)
(c) K eq K eq (2)
(d) K eq − K eq
(1)

(1 /2)2 1
⇒ Kp = = = 0.5 In this solution, fraction of the surface Ans. (c)
1 /2 2 covered by water molecules get reduced. (1) [B][C]
or 5 × 10 −1 So, the number of solvent molecules - B + C; K
A eq =
[A]
… (i)
Hence, x × 10 −1 escaping from the surface of water as (2 ) [P]
water vapour also reduced. B + C - P; K = … (ii)
x=5 eq
[B][C]
90 JEE Main Chapterwise Topicwise Chemistry

Equilibrium constant for A → P The values of ∆H°, ∆G° atT 1 and

A - P; K eq =
[P]
∆G° atT 2 (in kJ mol −1 )
[A]
respectively, are close to [use
Multiplying equation (i) and (ii) R = 8.314 JK −1 mol −1 ]
[P]
K ((eq ) × K ( eq ) = = K eq
1) (2 ) [2020, 6 Sep Shift-I]
[A] (a) 28.4, − 7.14 and −5.71 (a) 4 (b) 2
(b) 0.64, − 7.14 and −5.71 (c) 8 (d) 1
17 For a reaction, X + Y = 2Z (c) 28.4, −5.71 and −14.29 Ans. (b)
(d) 0.64, −5.71 and −14.29 Assuming the reaction to be A - B,
1.0 mol of X, 1.5 mol of Y, and 0.5
mol of Z , were taken in a 1 L vessel Ans. (c) [B]
Equilibrium constant,K =
and allowed to react. At T1 = 298 K,T2 = 373 K, K 1 = 10, K 2 = 100 [A]
equilibrium, the concentration of K  ∆H °  1 1 Number of circles in the figure = 11
log  2  =  − 
Z was 1.0 mol L−1 . The equilibrium . R  T1 T2 
 K 1  2303 Number of squares in the figure = 6
constant of the reaction is ……… 11
∆H °  1 1  ∴ K = = 1. 8 ≈ 2
∴ log 
100 
x =  −  6
. The value of x is ……… .  10  2303
. .  298 373 
× 8314
15 ∴ ∆H ° = 284
. kJ/mol
[2020, 5 Sep Shift-II] 22 For the following reactions,
We know that, ∆G ° = − RT lnK equilibrium constants are given :
Ans. (16)
∴ ∆G ° at
x + y - 2z T1 = − 8314
. × 298 × 2.303 × log(10)
S(s) + O 2 (g)
- SO 2 (g); K 1 = 10 52
t = t eq. 1− a 1.5 − a 0.5 + 2α (a = 1 ⇒ − 5.71 kJ/mol 2S(s) + 3O (g) -2SO (g);
2 3
mol)
∆G ° atT2 = − 8314
. × 373 × 2.303 × log(100) K 2 = 10 129
x + y → 2z (a = 0.25) = − 14.29 kJ/mol
0.75 mol 1.25 mol 1 mol
The equilibrium constant for the
Hence, the correct option is (c).
[z]2 1 x reaction,
K eq = = =
[x][y] 0.75 × 125 . 15 20 The value of K C is 64 at 800 K for 2SO(g) + O 2 (g) 2SO 3 (g) is
-
⇒ x=
15
= 16
the reaction, [2019, 8 April Shift-II]
0.75 × 1 . 25 N 2 (g ) + 3H2 (g ) - 2NH3 (g ) (a) 1025 (b) 1077
(c) 10154 (d) 10181
The value of K C for the following
18 For the reaction, reaction is Ans. (a)
3
Fe 2N(s) + H2 (g) 2 1 3 S + O2 w SO2 , K 1
2 NH3 (g ) - N 2 (g ) + H2 (g ) ∴ SO2 w S + O2
Fe(s) + NH3 (g) 2 2 1
[2020, 6 Sep Shift-II] K 1′ =
[2020, 6 Sep Shift-I] K1
−1/ 2 (a) 1/64 (b) 8 (c) 1/4 (d) 1/8
(a) K C = K p (RT ) (b) K C = K p (RT )
Ans. (d) or, 2SO2 w 2S + 2O2 ,
(c) K C = K p (RT ) 1/2 (d) K C = K p (RT ) 3/2
1
Ans. (c) Equilibrium constant for equation, K 1 ′ ′ = (K 1 ′)2 = 2 … (i)
∆n g N2 (g) + 3H2 (g) r 2NH3 (g) K1
K p = K C (RT )
[NH3]2 ⇒ 2S + 3O2 w 2SO3, K 2 … (ii)
∆ng = number of gaseous product KC = = 64
[N2 ] [H2 ] 3 Now, [(i) + (ii)] gives
molecules − number of gaseous reactant
molecules and for 2SO2 + O2 w 2SO3, K 3
3 1 1 The value of equilibrium constant,
= 1− =− 2NH3 (g) r N2 (g) + 3H2 (g), K C′ =
2 2 KC 1
K 3 = K2 × K 1 ′ ′ = K2 × 2
Now, K p = K C (RT ) −1/ 2 and for equation, K1
Kp 1 3 1
∴ KC = ⇒K p (RT ) 1/ 2 NH3 (g) r N2 (g) + H2 (g) = 10 129 × = 10 129 − 104
(RT ) −1/ 2 2 2 52 2
(10 )
1 1 1 1 = 1025
Hence, the correct option is (c). K C′ = 1/ 2 = 1/ 2 = =
KC KC (64) 1/ 2 8
19 The variation of equilibrium 23 In which one of the following
constant with temperature is given 21 In the figure shown below, reactant equilibria, K p ≠ K c ?
below: A (represented by square) is in [2019, 12 April Shift-II]

Temperature Equilibrium constant equilibrium with product B (a) 2C(s ) + O2 (g) 2 2CO(g)
T 1 = 25°C K 1 = 10 (represented by circle). The (b) 2HI(g) 2 H2 (g) + I2 (g)
equilibrium constant is
T 2 = 100°C K 2 = 100 [2020, 9 Jan Shift-II]
(c) NO2 (g) + SO2 (g) 2 NO(g) + SO 3 (g)
(d) 2NO(g) 2 N2 (g) + O2 (g)
Chemical Equilibrium 91

Ans. (a) (a) 1, 24.62 dm 3 atm mol −1, KC =

[NH3] [H2S]
=
0.01 × 0.01
Key Idea The relationship betweenK p 606.0 dm 6 atm2 mol −2 [NH4HS(s)] 1
∆n
and K c is K p = K c (RT ) g (b) 1, 24.62 dm 3 atm mol −1,
= 10 −4 (mol L −1)2
1.65 × 10 −3 dm −6 atm −2 mol2
where, ∆ng = nproducts − nreactants ⇒ K p = K C (RT )
∆n g
(c) 24.62 dm 3 atm mol −1, 606.0 dm 6
If ∆ng = 0 then K p = K c atm −2 mol2 , 1.65 × 10 −3 dm−6 atm −2 [where, ∆ng = Σnproduct − Σnreactant]
If ∆ng = + ve then K p > K c mol2 = 2−0 = 2
If ∆ng = − ve then K p < K c (d) 1,4.1 × 10 −2 dm −3atm −1 mol, ∴ K p = K C (RT )2
Consider the following equilibria 606 dm 6 atm2 mol −2
= 10 − 4 × [0.082 × (273 + 327 )]2 atm2
reactions Ans. (b)
(a) 2C(s ) + O2 (g) 2 2CO(g) = 0.242 atm2
We know that, the relationship between
∆ng = nproduct − nreactant = 2 − (1) = 1 K p and K C of a chemical equilibrium 27 Consider the reaction,
∆ng ≠ 0 ⇒So, K p ≠ K c state (reaction) is
∆n g
N 2 (g) + 3H2 (g) 2NH3 (g) =
K p = K C (RT )
(b) 2HI(g) 2 H2 (g) + I2 (g) The equilibrium constant of the
∆ng = nproduct − nreactant = 2 − 2 = 0 Kp ∆n g above reaction is K p . If pure
⇒ = (RT )
∆ng = 0 ⇒So, K p = K c KC ammonia is left to dissociate, the
(c) NO2 (g) + SO2 (g) 2 NO(g) + SO3 (g) where, ∆ng = ΣnProducts − ΣnReactants partial pressure of ammonia at
∆ng = nproduct − nreactant = 2 − 2 = 0 c
(i) N2 (g) + O2 (g) 2NO(g) equilibrium is given by (Assume
∆ng = 0 ⇒So, K p = K c ⇒ (RT )2 − (1 + 1) = (RT ) 0 = 1
that pNH << p total at equilibrium)
3
[2019, 11 Jan Shift-I]
(d) 2NO(g) 2 N2 (g) + O2 (g) (ii) N2O4 (g) c 2NO2 (g) 3/2
3 K p1/2 p 2 33/2 K p1/2 p2
∆ng = nproduct − nreactant = 2 − 2 = 0 ⇒ (RT )2 − 1 = RT = 2462
. (a) (b)
∆ng = 0 ⇒So, K p = K c dm3 atm mol −1 4 16
(iii) N2 (g) + 3H2 (g ) c 2NH3 (g) K p 1/2 p2 K p 1/2 p2
24 Consider the following reversible (c) (d)
⇒(RT )2 − (3 + 1) = (RT ) − 2 16 4
chemical reactions, 1
K1 = Ans. (b)
A 2 (g) + B2 (g) -2AB (g) …(i) (24.62 dm3 atm mol −1)2 N2 (g) + 3H2 (g) 2NH3 (g) =
K2 = 1.649 × 10 −3 dm–6 atm− 2 mol2 At eq. pN 2 = P, pH 2 = 3P, pNH = 2P
(g) + 3B2 (g) …(ii)
3
6AB (g) - 3A 2 ⇒
26 5.1 g NH4SH is introduced in 3.0 L p(total) = pN 2 + pH 2 + pNH − pN 2 + pH 2
~
The relation between K 1 and K 2 is 3
evacuated flask at327°C. 30% of the [Qp (total) >> pNH ]
(a) K 2 = K 13 (b) K 1K 2 = 3
1 solidNH4 SH decomposed toNH3 = p + 3p = 4p
3

(c) K 2 = K 1− 3 (d) K 1 K 2 = andH2S as gases. The

3 p2 NH 3 p2NH
[2019, 9 Jan Shift-II] Kp of the reaction at327°C is Now, K p = = 3

(R = 0.082 atm mol −1 K −1 , molar mass pN 2 × pH3 2 p × (3p) 3

Ans. (c)
(i) A2 (g) + B 2 (g)
c 2AB (g) ofS = 32 g mol −1 , molar mass of p2NH p2NH
= = [QP = 4p]
N = 14 g mol −1 ) [ 2019, 10 Jan Shift-I]
3 3
[AB]2
K1 = 27 × p4 4
27 ×  
P
−4
[A2 ] [B2 ] (a) 0.242 × 10 atm 2
 4
(ii) 6AB(g ) c 3A2 (g ) + 3B2 (g); (b) 0.242 atm2 p2NH × 44
(c) 4 .9 × 10−3 atm2 Kp = 3
[A2 ] 3 [B2 ] 3 1 1 32 × 3 × P 4
K2 = = = , (d) 1 × 10−4 atm2
[AB] 6  [AB]2 
3
K 13 32 × 3 × P 4 × K p
  Ans. (b) ⇒ p2NH =
 [A ][B ] 
 2 2  Molar mass ofNH4SH = 18 + 33 = 51g mol −1
3
44
⇒ K 2 = K 1−3 Number of moles of NH4SH introduced 3 × 31/ 2 × P2 × K p1/ 2
⇒ pNH =
in the vessel 3
42
Kp Weight 5⋅ 1 3 3/ 2
× P × K p1/ 2
2
25 The values of for the following = = = 0.1 mol =
KC Molar mass 51 16
reactions at 300 K are, respectively NH4SH(s ) c NH3 (g) + H2S(g)
(At 300 K, 28 For the equilibrium,
Number of 0.1 0 0
T = 24.62 dm 3 atm mol −1 ) moles at 2H2O H3O + + OH− , the value
-
t =0 of ∆G° at 298 K is approximately
N 2 (g) + O 2 (g) 2NO(g)
= At t = t eq 0.1(1 − 0.03) 30% of 30% of 0.1 (a) − 80 kJ mol− 1 [2019, 11 Jan Shift-II]
N 2O 4 (g) 2NO 2 (g)
= 0.1 = 0.03 = 0.03
(b) 100 kJ mol− 1
0.03 0.03
N 2 (g) + 3H2 (g) 2NH3 (g)
= Active = 0.01 = 0.01 (c) 80kJ mol− 1
mass 3 3
− 100 kJ mol− 1
−1
[2019, 10 Jan Shift-I] (mol L ) (d)
92 JEE Main Chapterwise Topicwise Chemistry

Ans. (c) Ans. (d)

We know that, ∆G ° = − 2.303 RT log K For the given chemical reaction, ln K
A
Also, given equilibrium is A + 2B 2C + D
w
–
B
2H2O - H3O+ + OH At, t=0 a0 1.5a 0 0 0 1
t = teq a0 − x 1.5a 0 − 2x 2x x (0, 0) T(K)
[H+ ][OH− ] = 10 −14 or K = 10 − 14 [x = degree of dissociation]
∴∆G ° = − 2.303 × 8.314 JK–1 mol −1
Given, at equilibrium.
× 298K × log 10 −14
−1 [A] = [B] 32 The equilibrium constant at 298 K
= 79881.8 J mol
a 0 − x = 1.5a 0 − 2x for a reaction, A+B C+D is 100.
-
= 79.8 kJ ≈ 80 kJ mol − 1
x = 0.5a 0
If the initial concentrations of all
29 Two solids dissociate as follows: the four species were 1 M each,
∴ [A] = a 0 − x = a 0 − 0.5a 0 = 0.5a 0
A(s) B(g) + C (g); K p = x atm 2
- then equilibrium concentration of D
1 [B] = 1.5a 0 − 2x = 1.5a 0 − 2 × 0.5a 0 (in mol L−1 ) will be [JEE Main 2016]
D(s) C (g) + E (g); K p = y atm 2
- = 0.5a 0
2 (a) 0.818 (b) 1.818
The total pressure when both the [C] = 2x = 2 × 0.5a 0 = a 0 (c) 1.182 (d) 0.182
solids dissociate simultaneously is [D] = x = 0.5a 0 Ans. (b)
[ 2019, 12 Jan Shift-I]
[C]2 [D] A + B - C + D
(a) x + y atm (b) x + y atm
2 2 Now, K =
[A][B]2 Initially at t = 0 1 1 1 1
(c) (x + y) atm (d) 2( x + y ) atm
Ans. (d) Now, substituting the values in above At equilibrium 1− x 1− x 1+ x 1+ x
equation, we get [C] [D] (1 + x) (1 + x) (1 + x)2
The equilibrium reaction for the K eq = = =
(a )2 × (0.5a 0 ) [A] [B] (1 − x) (1 − x) (1 − x)2
dissociation of two solids is given as: K= 0 =4
A (s ) e B ( g) + C ( g) (0.5a 0 ) × (0.5a 0 ) 2
p1 + p2
 1+ x 1+ x
p1 or 100 =   or 10 =
31 Which of the following lines  1− x 1− x
At equilibrium
K p 1 = x = pB ⋅ pC = p1(p1 + p2 ) …(i) correctly show the temperature or 10 − 10 x = 1 + x
Similarly, dependence of equilibrium ⇒ 10 − 1 = x + 10 x
e
D(s ) C(g)+ E(g) constant, K, for an exothermic 9
9 = 11 x ⇒ x = = 0.818
At equilibrium p1 + p2 ⋅ p2 reaction? [JEE Main 2018] 11
K p 2 = y = pC ⋅ pE =(p1 + p2 )p2 …(ii) In K A ∴ [D] = 1 + x = 1 + 0.818 = 1.818
On adding Eq. (i) and (ii), we get. B 1
K p 1 + K p 2 = x + y = p1(p1 + p2 )+ p2 (p1 + p2 ) (0, 0) T(K) 33 The standard Gibbs energy change
××
××
at 300K for the reaction,
C
= (p1 + p2 )2 B + C is 2494. 2 J. At a
××
××
×× 2A #
××
or x + y = p1 + p2 …(iii) D given time, the composition of the
Now, total pressure is given as 1
(a) A and B (b) B and C reaction mixture is [A] = , [B] = 2
pT = pB + pC + pE (c) C and D (d) A and D 2
1
= p1 + (p1 + p2 ) + p2
Ans. (a) and [C] = . The reaction proceeds
=2 (p1 + p2 ) …(iv) 2
On substituting the value of p1 + p2 from From thermodynamics, in the[R = 8.314 JK / mol, e = 2.718]
Eq. (iii) to Eq. (iv), we get −∆H ° ∆S ° [JEE Main 2015]
lnk = + …(i)
pT =2 x + y RT R (a) forward direction because Q < K c
Mathematically, the equation of straight (b) reverse direction because Q < K c
30 In a chemical reaction, line is (c) forward direction because Q < K c
A + 2B
K
-2C + D, the initial y = c + mx …(ii) (d) reverse direction because Q < K c
After comparing Eq. (ii) with (i) we get, Ans. (b)
concentration of B was 1.5 times of
− ∆H ° ∆S ° Given, ∆G ° =2494.2J
the concentration of A, but the slope = and intercept =
R R [B][C] 2 × (1 /2)
equilibrium concentrations of A and Q= = =4
Now, we know for exothermic reaction [A]2  1
2
B were found to be equal. The ∆H is negative (−)ve. But here,  
 2
equilibrium constant (K) for the −∆H °
Slope = is positive ∴ We know,
aforesaid chemical reaction is R
[2019, 12 Jan Shift-I] ∆G = ∆G ° + RT ln Q
So, lines A and B in the graph represent = 24942. + 8314
. × 300 ln 4
1
(a) (b) 16 temperature dependence of equilibrium
4 constant K for an exothermic reaction as = 28747.27 J
(c) 1 (d) 4 shown below = positive value
Chemical Equilibrium 93

Also, we have 36 A vessel at 1000 K contains CO 2 III. CH4 (g) + 2H2O(g) a CO (g) 2

∆G = RT ln
Q
with a pressure of 0.5 atm. Some + 4H2 ( g); K 3
K
of the CO 2 is converted into CO on Which of the following relations is
if ∆G is positive, Q > K .
the addition of graphite. If the total correct?
Therefore, reaction shifts in reverse
pressure at equilibrium is 0.8 atm, (a) K 1 K 2 = K 3 (b) K 2 K 3 = K 1
direction.
the value of K p is [AIEEE 2011] (c) K 3 = K 1K 2 (d) K 3K 23 = K 21
34 For the reaction, (a) 1.8 atm (b) 3 atm Ans. (c)
1 (c) 0.3 atm (d) 0.18 atm As equation ‘III’ is obtained on adding
SO 2 (g ) + O 2 (g ) SO 3 (g ),
e
2 Ans. (a) equation ‘I’ and equation ‘II’, so
K 3 = K 1 ⋅K 2 .
if K P = K C (RT ) x where the CO2 (g) + C(s ) j2CO(g)
symbols have usual meanings Initial 0.5 atm —
At equilibrium (0.5 − p) 2p atm
39 The equilibrium constants K p 1 and
then, the value of x is
(assuming ideality). [JEE Main 2014] This is a case of heterogeneous K p2 for the reactions X 2Y and
a
1 1 equilibrium. Z a P + Q, respectively are in the
(a) − 1 (b) − (c) (d) 1 ratio of 1 : 9. If the degree of
2 2 C(s) being solid is not considered.
Ans. (b) Total pressure of CO2 and CO gases. dissociation of X and Z be equal,
By using this formula, Equilibrium p CO 2 + pCO = ptotal then the ratio of total pressure at
constant, these equilibria is [AIEEE 2008]
0.5 − (p + 2p) = 0.8, p = 0.3 atm
∆n g (a) 1 : 36 (b) 1 : 1
K P = K c (RT ) ∴ p CO 2 = 0.5 − 0.3 = 0.2 atm
(c) 1 : 3 (d) 1 : 9
where ∆ng = (no. of moles of products) p CO = 2p = 0.6 atm
− (no. of moles of reactants)
Ans. (a)
p2 0.6 × 0.6 Let the total pressure at equilibrium for
For the given reaction, K p = CO = = 1.8 atm
p CO 2 0 .2 the given two reactions are p1 and p2 ,
1
SO2 ( g ) + O2 (g) SO3 (g)
1 respectively.
2
37 In aqueous solution, the ionisation For first reaction,
1  3  1
∆ng = 1 − + 1 = 1 −   = − X 2Y
a
 2  2  2 constants for carbonic acid are
Initial 1 mol 0
K 1 = 4.2 × 10 −7 and
At equilibrium (1 − α) 2α
35 The equilibrium constant (K c ) for K 2 = 4.8 × 10 −11
Total moles = (1 − α) + 2α
the reaction Select the correct statement for a
[Here, α is the degree of dissociation]
N 2 (g ) + O 2 (g ) → 2NO(g ) at saturated 0.034 M solution of the
= (1 + α)
temperature T is 4 × 10 −4 . carbonic acid. [AIEEE 2010]
1−α
(a) The concentration of CO23− is 0.034 M px = p1
The value of K c for the reaction 1+ α
1 1 (b) The concentration of CO23− is greater
NO(g) → N 2 (g) + O 2 (g) at the [QPartial pressure = (Total no. of moles)
2 2 than that of HCO−3
× (Total pressure)]
(c) The concentration ofH+ and HCO−3
same temperature is [AIEEE 2012] 2α
are approximately equal py = p1
(a) 0.02 (b) 2.5 ×102 (d) The concentration ofH+ is double
1+ α
(c) 4 × 10−4 (d) 50.0 that of CO23− 2
 2α 
Ans. (d)  p1 
Ans. (c) 1+ α  4α2
N2 (g) + O2 (g) → 2NO(g) K p1 = = P1 = 4α2 P1
H2 CO3 r H+ + HCO−3 ; K 1 = 4.2 × 10 −7  1 − α  1 − α2
[NO]2 −  p1 
Kc = = 4 × 10 −4 HCO3 r H+ + CO23− ; K 2 = 4.8 × 10 −11 1+ α 
[N2 ][O2 ] K 1 >> K 2
[Qα 2 <<< 1]
For the reverse reaction, [H+ ] [CO23]
∴ [H+ ] = [HCO−3 ] ⇒ K 2 = For second reaction
2NO(g) → N2 (g) + O2 (g) [HCO−3 ]
1 [N ][O ] 1 10 4 So, [CO23− ] = K 2 = 4.8 × 10 −11
Z aP + Q
Kc′= = 2 22 = = Initial 1 mol 0 0
Kc [NO] 4 × 10 −4 4
At equilibrium 1−α α α
On dividing the reverse reaction by 2 38 For the following three reactions I, Total moles = 1 − α + α + α = (1 + α)
1
NO(g) → N2 (g) + O2 (g)
1 II and III, equilibrium constants are 1−α
pz = P2
2 2 given [AIEEE 2008] 1−α
[N ] 1/2 [O2 ] 1/2 I. CO ( g ) + H2O(g )a CO (g ) α
K c ′′ = 2 = Kc′ 2 pP = P2
[NO] + H ( g); K 1
1+ α
2
10 4 100 α
= = = 50
II. CH (g) + H O( g) a CO (g)
4 2 and pQ = P2
1+ α
4 2 + 3H2 ( g ); K 1
94 JEE Main Chapterwise Topicwise Chemistry

 α  α  Total number of moles at equilibrium ∴ K p = 1.8 × 10 −6 × 0.00831 × 457

 P2   P2 
1+ α  1+ α  = (1 − x) + x + x = 1 + x = 6.836 × 10 −6 > 1.8 × 10 −6
K P2 =
1+ α   x  Thus, K p > K c .
 P2  p PCl =  p
1+ α  1 + x
3

44 What is the equilibrium expression

α2 P2
= = α2 P2 [Qα2 <<< 1] 42 An amount of solid NH4HS is placed for the reaction
1 − α2 P4 (s) + 5O 2 (g) P4O 10 (s) ?
r
in a flask already containing
K P1 4α2 P1
= ammonia gas at a certain [AIEEE 2004]
K P2 α2 P2 [P4O 10] [P4O 10]
temperature and 0.50 atm (a) K c = (b) K c =
1 4P1 P 1 pressure. Ammonium hydrogen [P4] [O2] 5
5[P4] [O2] 5
⇒ = ⇒ 1 =
9 P2 P2 36 sulphide decomposes to yield NH3 1
(c) K c = [O2] 5 (d) K c =
and H2S gases in the flask. When [O2] 5
40 The equilibrium constant K c for the the decomposition reaction Ans. (d)
reaction reaches equilibrium, the total In the expression for equilibrium
1 pressure in the flask rises to constant (K p or K c ), species in solid state
SO 3 (g) r SO 2 (g ) + O 2 (g )
2 0.84 atm . The equilibrium constant are not written
(i.e., their molar concentrations are
is 4.9 × 10 −2 . The value of K c for for the decomposition of NH4HS at
taken as 1)
the reaction this temperature is [AIEEE 2005]
P4 (s ) + 5O2 (g) r P4O10 (s )
2SO 2 (g ) + O 2 (g ) 2SO 3 (g )
r (a) 0.11 (b) 0.17 1
(c) 0.18 (d) 0.30 Thus, Kc =
will be [AIEEE 2006] [O2 ] 5
Ans. (a)
(a) 416 (b) 2.40 × 10−3
(c) 9.8 × 10−2 (d) 4.9 × 10−2 NH4HS (s ) r NH3 (g) + H2S (g) 45 For the reaction,
Initially 1 0.5 0 CO(g) + Cl 2 (g) COCl 2 (g), the
Ans. (a) r
At equilibrium (1− x ) (0.5+ x ) x
K p / K c is equal to [AIEEE 2004]
Equilibrium constant for the reaction,
Total pressure at equilibrium
1 (a) 1/ RT (b) RT (c) RT (d) 1.0
SO2 (g) + O2 (g) SO3 (g)
r = p NH + p H 2 S
2 3
Ans. (a)
= 0.5 + x + x = 0.84
1
Kc = ∴ x = 0.17 atm K p = K c (RT )
∆n g
4.9 × 10 −2
∴ p NH = 0.50 + 0.17 = 0.67 atm ∆ng = (Sum of coefficients of gaseous
3
and for 2SO2 ( g) +O2 ( g) r 2SO ( g) p H 2 S = 0.17 atm
2
3
products) − (Sum of coefficients of
 1  10 4
∴ K p = p NH ⋅ pH 2 S gaseous reactants)
K c =   =
−2 
3
 4.9 × 10  (4.9)2 = 0.67 × 0.17 = 0.114 atm CO(g) + Cl2 (g) → COCl2 (g)
= 416.490 ≈ 416 ∴ ∆ng = 1 − 2 = − 1
43 For the reaction, ∴ K p = K c (RT ) −1
41 Phosphorus pentachloride 2NO 2 (g ) r 2NO(g ) + O 2 (g ) Kp 1
dissociates as follows, in a closed −6 ∴ = (RT ) −1 =
reaction vessel, [K c = 1.8 × 10 at 184° C, Kc (RT )
PCl 5 (g) PCl 3 (g) + Cl 2 (g)
r R = 0.00831kJ/(mol K)]
When K p and K c are compared at 46 For the reaction equilibrium,
If total pressure, at equilibrium, of
the reaction mixture is p and 184°C it is found that [AIEEE 2005] N 2O 4 (g) 2NO 2 (g)
r
(a) whether K p is greater than, less the concentrations of
degree of dissociation of PCl 5 is x,
than or equal to K c depends upon N 2O 4 and NO 2 at equilibrium are
the partial pressure of PCl 3 will be the total gas pressure
[AIEEE 2006] 4.8 × 10 −2 and 1.2 × 10 −2 mol L−1 ,
(b) K p = K c
 x   2x  respectively. The value of K c for
(a)  p (b)  p (c) K p is less than K c
 x + 1  1 − x the reaction is [AIEEE 2003]
(d) K p is greater than K c
 x   x  (a) 3.3 × 102 mol L−1
(c)  Ans. (d)
p (d)  p (b) 3 × 10−1 mol L−1
 x − 1  1 − x 2NO2 ( g) r 2NO(g) + O2 (g)
(c) 3 × 10−3 mol L−1
Ans. (a) K c = 1.8 × 10 −6 at 184° C (= 457 K)
(d) 3 × 103 mol L−1
PCl 5 (g ) r PCl (g) + R = 0.00831 kJ mol −1 K−1
3
∆n g Ans. (c)
Initially 1 0 K p = K c (RT )
At equilibrium ( 1 − x) x [NO2 ]2 (1.2 × 10 −2 )2
Cl2 (g) where, ∆ng = (gaseous products Kc = =
[N2O4 ] 4.8 × 10 −2
0 − gaseous reactants)
x =3−2= 1 = 3 × 10 mol L−1
−3
Chemical Equilibrium 95
0.1 × 0.2 0.1 × 0.2 (a) For the given equilibrium, ∆H is
47 For the following reaction in = × = 10 −4
2 2 negative, so the equilibrium
gaseous phase
1 ∴ K p = K C (RT ) ∆n constant will decrease with
CO + O 2 → CO 2 . K c /K p is [∆n = change in the number increase in temperature and the
2 of gaseous moles = 2] equilibrium will shift in the
[AIEEE 2002]
K p = 10 −4 × (0.08 × 300)2 backward direction.
(a) (RT ) 1/2 (b) (RT ) −1/2 K p = 10 −4 × (24)2 = 0.06 Thus, statement (a) is correct.
(c) (RT ) (d) (RT ) −1 x × 10 −2 = 0.06 (b) When inert gas is added at
Ans. (a) 0.06 constant volume and constant
⇒ x = −2 = 0.06 × 102 = 6 temperature, an equilibrium
According to the relationship ofK p andK c , 10 remains undisturbed.
∆n g
K p = K c (RT ) ⇒ ∆ng = 1 − 1.5 = − 0.5 x = 6 is the answer. Thus, statement (b) is correct.
Kc (c) For the equilibrium,
K p = K c (RT ) −1/ 2 = 49 Consider the following reaction :
(RT ) 1/ 2 ∆ng = 2 − (2 + 1) = − 1, i.e. (−ve)
Kc N 2O 4 (g) q 2NO 2 (g); ∆H° = + 58kJ So, increase in pressure will shift
⇒ = (RT ) 1/ 2
Kp For each of the following cases the equilibrium in the forward
(A, B),the direction in which the direction.
equilibrium shifts is Thus, statement (c) is correct.
TOPIC 2 (A) temperature is decreased. (d) The reaction takes place in the
presence of a catalyst which is
Le-Chatelier’s Principle (B) pressure is increased by V2O5 (s ) in contact process orNO(g)
adding N 2 at constantT. in chamber process.
48 When 5.1 g of solid NH4HS is [2020, 5 Sep Shift-I] Thus, statement (d) is incorrect.
(a) (A) towards product, (B) towards
introduced into a two litre 51 The exothermic formation of ClF3
reactant
evacuated flask at 27°C, 20% of the (b) (A) towards reactant, (B) no change
solid decomposes into gaseous is represented by the equation
(c) (A) towards reactant, (B) towards
ammonia and hydrogen sulphide. product Cl 2 (g ) + 3F2 (g )
r 2ClF3 (g );
The K p for the reaction at 27°C is (d) (A) towards product, (B) no change ∆H r = − 329 kJ
x × 10 − 2 . The value of x is ........... . Ans. (b) Which of the following will
(Integer answer) N2O4 (s ) r 2NO2 (s ); ∆H° = + 58 kJ increase the quantity of ClF3 in an
[Given, R = 0.082 L atm K − 1 mol − 1 ] Because in case of an endothermic equilibrium mixture of
[2021, 27 Aug Shift-II] reaction (∆H = + ve), the equilibrium Cl 2 , F2 and ClF3 ? [AIEEE 2005]
Ans. (6) constant increases with rise in (a) AddingF2
temperature and hence, the reaction (b) Increasing the volume of the container
51 g of NH4HS = 1 mol
moves in forward direction.On addingN2 , (c) Removing Cl2
1
5.1 g of NH4HS = × 5.1 = 0.1 mol pressure is increased at constant T, and (d) Increasing the temperature
51 volume would also be constant, so no
NH4HS (s ) q NH3 (g) + H2S (g) change is observed. Ans. (a)
At t = 0, 0.1 Reaction is exothermic. By Le-Chatelier
At t = t, 0.1 (1 − α) 0.1α 0.1α
50 For the reaction, principle, a reaction is spontaneous in
It is given that dissociation is 20% from 2SO 2 (g) + O 2 (g) → 2SO 3 (g), forward side (in the direction of
formation of more ClF3). If F2 is added,
100 moles. ∆H = − 57.2 kJ mol − 1 and temperature is lowered and ClF3 is
∴20 moles get dissociated. K c = 1.7 × 10 16 . Which of the removed.
20% dissociation from 1 mol 20/100 = 0.2 following statement is incorrect?
moles get dissociated. [2019, 10 April Shift-II] 52 One of the following equilibria is
α = 0.2 (a) The equilibrium constant decreases not affected by change in volume
[NH3][H2S] [NH3][H2S] as the temperature increases of the flask
Q KC = = [AIEEE 2002]
[NH4HS] 1 (b) The addition of inert gas at constant (a) PCl 5 (g)
r PCl3 (g) + Cl2 (g)
(Concentration of solid is volume will not affect the equilibrium (b) N2 (g) + 3H2 (g)
r 2NH3 (g)
constant
assumed as 1) (c) N2 (g) + O2 (g)
r 2NO (g)
Number of moles of NH3 (g) (c) The equilibrium will shift in forward
[NH3] = direction as the pressure increases (d) SO Cl (g) r SO (g) + Cl (g)
Volume (in L) 2 2 2 2
0.1α (d) The equilibrium constant is large Ans. (c)
= suggestive of reaction going to Change in volume affects number of
2
completion and so no catalyst is moles per unit volume and move in the
Number of moles of H2S 0.1α
[H2S] = = required direction which undo the change.
Volume (in L) 2
Ans. (d) N2 (g) + O2 (g) r 2NO(g)
0.1 α 0.1 α
KC = × The explanation of given statements are Number of moles of reactants and
2 2 as follows : products are equal
08
Ionic Equilibrium
Ans. (c) Ans. (2)
TOPIC 1 The overall dissociation constant of the Given, [HA] = 0.01
Ostwald’s Dilution Law acid is [HCl] = 0.1 M
K = K 1 × K2 When strong acid (HCl) is completely
01 The pH of a 0.1 molar solution of = 1.0 × 10 −5 × 5.0 × 10 −10 = 5 × 10 −15 dissociated,
the acid HQ is 3. The value of the HCl → H+ (aq) + Cl − (aq)
ionisation constant, K a of the acid 0.1 0.1 0.1

is [AIEEE 2012] TOPIC 2 For weak acid, dissociation is very less,

(a) 3 × 10−1 (b) 1 × 10−3 Acid Base Concepts HA ¾ H+ (aq) + A − (aq)
(c) 1 × 10−5 (d) 1 × 10−7 t=0 0.01 0.1 0
Ans. (c) 03 Assuming that Ba(OH) 2 is t = teq 0.01 − 0.01 α 0.1 + 0.01 α 0.01α

HQ = H+ + Q − completely ionised in aqueous [H+ ] [A − ]

Ka = = 2 × 10 − 6
[H+ ] = K a C by Ostwald’s solution under the given conditions [HA]
dilution law the concentration of H3O + ions in
[H+ ] = 10 − pH = 10 −3 M 0.005 M aqueous solution of (0.1 + 0.01α ) (0.01 α)
⇒ = 2 × 10 −6
C = 0.1 M Ba(OH) 2 at 298 K is …… (0.01 − 0.01α)
Thus, 10 −3 = K a × 0.1 ×10 −12 mol L−1 . (Nearest integer) As 0.01α << 0.1 [H+ ] = 0.1
10 −6 = K a × 0.1 ⇒ K a = 10 −5 [2021, 25 July Shift-II] and 0.01 α << 0.01 [HA] = 0.01
Ans. (1) (0.1) (0.01 α)
Alternate method ∴ 2 × 10 − 6 =
Ba(OH)2 is completely ionised in aqueous 0.01
HQ 1H +
+ Q− solution.
0 0 ⇒ α = 2 × 10 − 5
0.1 M
Ba(OH)2 → Ba2 + + 2OH−
Initial concentration ⇒ x =2
[Ba(OH)2 ] = 0.005M
Given, pH = 3, this suggests [H+ ] = 10 −3 M ⇒ 2 × 0.005 ⇒ 0.01
at equilibrium. 05 The decreasing order of electrical
[OH− ] = 10 − 2
Thus, [Q − ] at equilibrium = 10 −3 M conductivity of the following
At 298 K, in aqueous solution ;
Hence, [HQ ] = 0.1 M - 10 -3 M aqueous solution is
[H3O+ ] [OH− ] = 10 − 14
≈ 0.1 M [Q10 −3 M <<< 0.1 M] 0.1 M formic acid (A),
10 − 14
K a for the above reaction is given by [H3O+ ] = − 2 = 10 − 12 0.1 M acetic acid (B),
10
[H+ ] [Q − ] [10 −3] [10 −3]
Ka = = [H3O+ ] = 1 × 10 − 12 M 0.1 M benzoic acid (C).
[HQ ] [0.1] [2019, 12 April Shift-II]
⇒ K a = 1 × 10 −5 04 0.01 moles of a weak acid (a) A > C > B (b) C > B > A
HA (K a =2.0 × 10–6 ) is dissolved in (c) A > B > C (d) C > A > B
02 The first and second dissociation 1.0 L of 0.1 M HCl solution. The Ans. (a)
constants of an acid H2 A are degree of dissociation of HA Electrical conductivity of the given
1.0 × 10 −5 and 5.0 × 10 −10 , s …… × 10 −5 (Round off to the aqueous solutions depends on the
nearest integer). degree of ionisation. Degree of
respectively. The overall ionisation is directly proportional to the
dissociation constant of the acid [Neglect volume change on acidic strength. Electron withdrawing
will be [AIEEE 2007] adding HA. Assume degree of groups (EWGs) increases the stability of
(a) 5.0 × 10−5 (b) 5.0 × 1015 dissociation << 1] the carboxylate ion by dispersing the
negative charge through resonance
(c) 5.0 × 10−15
[2021, 17 March Shift-I]
(d) 0.2 × 105
Ionic Equilibrium 97

effect on the conjugate while electron SiCl 4 - Although this compound does not conjugate bases of the given acid is
donating groups (EDGs) decreases the have incomplete octet but it shows the opposite to their acidic strength.The
stability of the carboxylate ion by tendency to accept lone pair of basic strength of the conjugate bases of
intensifying the negative charge. electrons in its vacantd-orbital. This the given acids follows the order
O tendency of SiCl 4 is visible in following HSO3− < H2O < SO24− < CO23−
reaction. Hence, the acidic strength follows the
EWG C s
O Cl Cl order
Acidity of carboxylic H HSO3 F > H3O+ > HSO−4 > HCO−3
acids increases due Si + H2O Si O
H
Cl Cl
09 What is the conjugate base of OH− ?
to the presence of electron Cl Cl
withdrawing groups (EWGs) Cl Cl
Lone pair acceptance [AIEEE 2005]
O
in d-orbital (a) O2− (b) O −
EDG C s Cl
O
(c) H2O (d) O2
Acidity of carboxylic Si OH + HCl Ans. (a)
acids decreases due
Cl Conjugate base is formed by loss ofH+ .
to the presence of Cl
electron donating groups OH− → O2 − + H+
Conjugate
Thus option (b) and (d) both appear as
The correct order of acidic strength and base
correct but most suitable answer is (d) as
electrical conductivity is as follows: the condition of a proper Lewis acid is O2 − is the conjugate base ofOH− .
HCOOH > PhCOOH > CH3COOH more well defined inBCl 3 and AlCl 3 .
A C B
10 The conjugate base of H2PO–4 is
06 Which of the following are Lewis 07 Three reactions involving H2PO–4 [AIEEE 2004]
acids? [JEE Main 2018] are given below [AIEEE 2010] (a) PO 3−
4 (b) P2O 5
(a) PH3 and BCl3 (b) AlCl3 and SiCl4 (c) H3PO 4 (d) HPO 2−
I. H3PO 4 + H2O → H3O + 4

(c) PH3 and SiCl4 (d) BCl3 and AlCl3 Ans. (d)
+ H2PO–4
Ans. (d) H 3PO4 is a tribasic acid, thus ionises in
II. H2PO–4 + H2O → HPO 2–
4 three steps
Lewis acids are defined as,
‘‘Electron deficient compounds which + H 3O + I : H3PO4 r H+ + H2PO4−
have the ability to accept atleast one lone III. + OH → H3PO 4 + O
H2PO–4 – 2– II : H2PO4−r H+ + HPO24−
pair.’’ III : HPO24−
r H+ + PO34−
The compound given are
In which of the above doesH2PO–4
Conjugate base is formed when an acid
act as an acid?
PH3 Octet complete although P has loses its proton. Thus,HPO24− is the
(a) II only (b) I and II
vacant 3d-orbital but does not have the conjugate base ofH2PO−4 (which is an acid
tendency to accept lone pair in it. Hence, (c) III only (d) I only
in step II, but is the conjugate base of
it cannot be considered as Lewis acid. Ans. (a) H3PO4 in step I).
BCl 3 Incomplete octet with following Only in reaction (II),H2PO–4 , givesH+ to
orbital picture. H2O. Thus, behaves as an acid. 11 Which one of the following
1s 2s 2p Vacant substances has the highest proton
p- orbital 08 Four species are listed below affinity ? [AIEEE 2003]
B-
I. HCO–3 II. H3O + (a) H2O (b) H2 S
–
Used in bond III. HSO 4 IV. HSO 3F (c) NH3 (d) PH3
formation with Which one of the following is the Ans. (c)
Cl having one electron
each from B and Cl correct sequence of their acid The tendency to accept the proton by
strength? [AIEEE 2008] the donation of their lone pairs of
Hence, vacant p-orbital of B can accept electron is called proton affinity. This
one lone pair thus it can be considered (a) IV < II < III < I (b) II < III < I < IV
proton affinity is also called basicity.
as Lewis acid. (c) I < III < II < IV (d) III < I < IV < II
Therefore, the molecule which donates
AlCl 3 -Similar condition is visible in AlCl 3 Ans. (c) their lone pairs electron more readily, is
as well i.e. Al Conjugate bases of the given species are said to be more basic. Since, N can easily
( Valence orbital only) = donate their lone pairs of electrons than
Species Conjugate base
O, S and P due to their smaller size and
Vacant p-orbital HCO −3 CO2−
3 low electronegativity.
3s 3p 3d vacant +
H3O H2O Thus, NH3 possess the highest proton
HSO −4 SO2−
4
affinity. On the other hand, due to higher
Used in bond electronegativity of O, it cannot donate
formation with Cl HSO 3 F HSO −3
their electron pair easily while P possess
Hence this compound can also be Since, strong acid has a weak conjugate a larger size, becomes less basic in
considered as Lewis acid. base. Thus, the basic strength of the nature.
98 JEE Main Chapterwise Topicwise Chemistry

12 Which one of the following species K sp = (3S ) 3 (2S )2 = 108 S 5 Ans. (64)
acts as both Bronsted acid and x Given, solubility in water
Also, S=
base? [AIEEE 2002] m . × 10 −4 mol L−1
(S ) = 80
(a) H2PO –2 (b) HPO2–3 5 In pure water,
K sp = 108  
x
(c) HPO2− (d) All of these K sp = S 2 = (8 × 10 − 4 )2 = 64 × 10 − 8
4
 m
Ans. (c) In 0.01 M H2SO4
5
H2SO4 (aq) → 2H+ (aq) + SO24− (aq)
Given that,K sp = a  
According to Bronsted Lowry concept of x
0.02
acids and bases, an acid is a proton  m 0.01
donor whereas a base is a proton CdSO4 (s ) ¾ Cd2 + (aq) + SO24− (aq)
acceptor. ∴ a = 108 x x ( x + 0.01)
Thus, according to this concept,HPO24− − K sp = x (x + 0.01) = 64 × 10 − 8
can easily donate a proton and also 15 A solution is 0.1 M in Cl and
0.001 M in CrO 2− x + 0.01 ≅ 0.01 M
accepts a proton on reaction with water. 4 . Solid AgNO 3 is
HPO24− + H2O PO34− + H3O+
r gradually added to it. So, x (0.01) = 64 × 10 − 8 ⇒ x = 64 × 10 − 6 M
2−
HPO4 + H2O H2PO24− + OH−
r Assuming that the addition does
17 The oxygen dissolved in water
not change in volume and
exerts a partial pressure of 20 kPa
K sp (AgCl) = 1.7 × 10 −10 M 2 and
TOPIC 3 K sp (Ag 2CrO 4 ) = 1.9 × 10 −12 M 3
in the vapour above water. The
molar solubility of oxygen in water
Solubility Product and Select correct statement from the is …… × 10 −5 mol dm −3 .
Common Ion Effect following [2021, 20 July Shift-II]
(Round off to the nearest integer).
(a) AgCl precipitates first because its
13 The molar solubility of Zn(OH) 2 in K sp is high. [Given, Henry’s law constant (K H )
(b) Ag2 CrO4 precipitates first as itsK sp =8.0 × 10 4 kPa for O 2 , density of
0.1 M NaOH solution is x × 10 −18 M. is low. water with dissolved oxygen
The value of x is ……… (Nearest (c) Ag2 CrO4 precipitates first because
= 1.0 kg dm −3 ]. [2021, 17 March Shift-I]
integer) the amount of Ag + needed is low.
(d) AgCl will precipitate first as the Ans. (25)
(Given; The solubility product of
amount of Ag + needed to precipitate Given, partial pressure ofO2 = 20 kPa
Zn(OH) 2 is 2 × 10 −20 ). is low.
[2021, 1 Sep Shift-II] K H (Henry’s constant) = 8 × 10 4 kPa
Ans. (d) From Henry’s law,
Ans. (2)
K sp (AgCl ) = 1.7 × 10 −10 M2 p(g) = [K H ] χ O2
Zn(OH)2 q Zn2 + + 2OH−
S 2S K sp (Ag2 CrO4 ) = 19. × 10 −12 M 3 where, χ O 2 = solubility of oxygen
+
Due to common-ion effect (presence of (i) [Ag ] required to ppt. AgCl(s ) 20 × 10 3 = (8 × 10 4 × 10 3) χ O 2
NaOH) the concentration ofOH− will be +
K sp = [Ag ] [Cl ] −
⇒ χO 2 =
20
(2S + 0.1) ≈ 0.1 (Q0.1 > > 2 S) ⇒ 1.7 × 10 −10 = [Ag + ] [0.1] 8 × 10 4
∴Solubility of product, Solubility = 2.5 × 10 − 4 = 25 × 10 − 5
[Ag + ] = 1.7 × 10 −10
K sp = (0.1)2 × S +
(ii) [Ag ] required to ppt. Ag2 CrO4 (s )
2 × 10 −20 = 0.01 × S K sp = Ionic product = [Ag + ]2 [CrO24− ]
18 Two salts A 2 X and MX have the
2 × 10 −20 same value of solubility product of
⇒ S= = 2 × 10 −18 . × 10 −12 = [Ag + ]2 [0.001]
⇒ 19
0.01 4.0 × 10 −12 . The ratio of their molar
[Ag + ] = 19
. × 10 −9
∴ x =2 S (A 2 X )
Hence, answer is 2. = 19 × 10 −5 solubilities i.e = ……
S (MX )
. × 10 −5
= 43
14 A 3B2 is a sparingly soluble salt of +
(Round off to the nearest integer)
∴ [Ag ] required to precipitate AgCl is [2021, 16 March Shift-I]
molar mass M (g mol − 1 ) and low, so AgCl will precipitate first.
Ans. (50)
solubility x g L− 1 . The solubility
Let the solubility of A2 X be ‘S’.
x 5 16 The solubility of CdSO 4 in water is
product satisfies K sp = a   . The A2 X (s ) c 2A + (aq) + X2 – (aq);
M 8.0 × 10–4 mol L −1 . Its solubility in 2S S
K sp 1 = 4 × 10 −12
value of a is .......... (Integer answer) 0.01 M H2SO 4 solution is ………
K sp 1 = [A + ]2 [X2 – ]
[2021, 31 Aug Shift-I]
× 10–6 mol L −1 . (Round off to the
Ans. (108) nearest integer) 4 × 10 −12 = (2S )2 (S )
A3B2 q 3A2+
(aq) + 2B (aq) 3− 4 × 10 −12 = 4S 3 ⇒ S = 10 −3 M
(Assume that, solubility is much
3S 2S Let the solubility of MY be ‘S 1’.
less than 0.01 M)
K sp = [A2 + ] 3 [B 3− ]2 [2021, 18 March Shift-II] MY (s ) c M+ (aq) + Y − (aq),
S1 S1
Ionic Equilibrium 99

K sp 2 = 4 × 10 −12 0.1 × (2S )2 = 8 × 10 −9 Ans. (2)

K sp 2 = [M+ ] [Y − ] 4S 2 = 8 × 10 −8 AB 2 (s ) rA2 + (aq) + 2B − (aq)
K sp 2 = (S 1)2 ⇒ S = 141 × 10 −6
M If the molar solubility of the solid
4 × 10 −12 = (S 1)2 x = 141 substance is S mol L− 1 then
⇒ S 1 = 2 × 10 −6 M K sp = [A2 + ] 1 [B − ]2 ;
[A2Y ] S 10 −4 K sp = S 1 × (2S )2 = 4S 3
= = = 50 21 For the following Assertion and
[MY ] S 1 2 × 10 −6 Solubility product of AB2 = 320 . × 10 − 11 M3
Reason, the correct option is − 11
3.20 × 10 = 4 × S 3
Assertion (A) When Cu (II) and
3.20 × 10 − 11
19 The solubility of Ca(OH) 2 in water is sulphide ions are mixed, they ⇒ S3 = ;
4
[Given: The solubility product of react together extremely quickly 1/ 3
 320
. × 10 − 11 
Ca(OH) 2 in water = 5.5 × 10 −6 ] to give a solid. S =  
[2021, 25 Feb Shift-II]  4 
Reason (R) The equilibrium
(a) 1.11 × 10 −2 (b) 1.11 × 10 −6 constant of Cu 2+ (aq ) + S 2− (aq) ⇒ S = 2 × 10 − 4 mol L− 1
(c) 1.77 × 10 −2 (d) 1.77 × 10 −6
r CuS ( s ) is high because the
Ans. (a) solubility product is low. 23 The stoichiometry and solubility
Let, solubility of Ca(OH)2 in pure water [2020, 2 Sep Shift-I] product of a salt with the solubility
= S mol/L (a) Both (A) and (R) are false. curve given below is, respectively :
Ca(OH)2 q Ca2 + + 2OH− (b) Both (A) and (R) are true and (R) is the
[2020, 8 Jan Shift-I]
S mol/L 2 × S (mol/L)
explanation for (A).
K sp = [Ca2 + ] [OH ] = S × (2 S )
− 2 2 3

[Y ]/mM
(c) Both (A) and (R) are true but (R) is not
= 4 S 3 (mol/L) the explanation for (A). 2
The expression ofK sp can also be (d) (A) is false and (R) is true. 1
written as,
Ans. (c)
K sp = x x ⋅ y y ⋅ S x + y
Both (A) and (R) are correct, but (R) is not 1 2 3
= 11 ⋅22 ⋅ S 1 + 2 the correct explanation of (A). [ X ]/mM
= 4S 3 [A] Cu2 + (aq) and S2 − (aq) ions undergo
[QFor Ca(OH)2 : x = 1, y = 2]
(a) X2Y , 2 × 10−9 M3 (b) XY,2 × 10−6 M3
ionic reaction whose rate of reaction is
very fast. (c) XY2 , 1 × 10−9 M3 (d) XY2 , 4 × 10−9 M3
x and y are the coefficients of cations
Ans. (d)
and anions respectively Cu2 + (aq) + S2 − (aq) → CuS (s ) ↓
K 
1/ 3
 5.5 × 10 −6 
1/ 3
[R] For the reaction : Units given for all options is M3, or
S =  sp  =   (mol L−1 )3 , which implies that, the
 4   4  Cu2 + (aq) + S2 − (aq) c
CuS(s ) equilibrium has three ions. Therefore,
−2
= 1.11 × 10 mol/L The expression of equilibrium constant XY2 - X2 + (aq) + 2Y − (aq),
is, K sp = [X2 + ][Y − ]2
20 The solubility product of PbI 2 is [CuS] or X2Y - 2X (aq) + Y 2 − (aq),
+
K eq =
8.0 × 10 − 9 . The solubility of lead [Cu2 + ][S2 − ] K sp = [X + ]2 [Y 2 − ]
iodide in 0.1 molar solution of lead But, the expression of solubility product (i) K sp in case of XY2 ,
nitrate is x × 10 − 6 mol/L. The value (K sp ) of CuS(s ) will be K sp = (1 × 10 −3) (2 × 10 −3)2 = 4 × 10 −9 M3
of x is ……. (Rounded off to the CuS (s ) c Cu2 + (aq) + S2 − (aq) (ii) K sp in case of X2Y ,
nearest integer). K sp = (1 × 10 −3)2 (2 × 10 −3) = 2 × 10 −9 M
K sp = [Cu2 + ][S2 − ]
[Given, : 2 = 1.41] [CuS] 1
The only matching value ofK sp from
[2021, 24 Feb Shift-II] So, K eq = is, K eq ∝ options that satisfies the concentration
K sp K sp values from graph is
Ans. (141)
Because of high stability CuS, the value [X2 + ] = 1 mM = 1 × 10 −3 M
Given, [K sp ] PbI 2 = 8 × 10 −9
of K eq is high, i.e. the value ofK sp of CuS and [Y − ] = 2 × 10 −3 M
To calculate solubility ofPbI2 in 0.1 M will be low. Thus, salt is XY2 and
solution of Pb(NO3)2 .
K sp = (10 −3) (2 × 10 −3)2 = 4 × 10 −9 M3
(I) Pb(NO3)2 → Pb2 + (aq) + 2NO−3 (aq)
0.1 M 0.1 M 0.2 M
22 If the solubility product of AB2 is
24 The K sp for the following
Pb2 + (aq) + 2I− (aq) 3.20 × 10 −11 M 3 , then the solubility
(II) PbI2 (s ) c dissociation is 1.6 × 10 −5
2S of AB2 in pure water is ……… × 10 4
Pb 2+ (aq) + 2Cl − (aq)
S

∴ [Pb2 + ] = S + 0.1 ≈ 0.1 mol L−1 PbCl 2 (s) -

Q S < < 0.1 [Assuming that neither kind of ion Which of the following choices is
Now, K sp = 8 × 10 −9 reacts with water] correct for a mixture of 300 mL
[Pb2 ] [I− ]2 = 8 × 10 −9 [2020, 6 Sep Shift-II] 0.134 M Pb(NO 3 ) 2 and 100 mL 0.4
M NaCl ? [2020, 9 Jan Shift-I]
100 JEE Main Chapterwise Topicwise Chemistry

(a) Q < K sp  K sp 
1/ 6
 K sp 
1/ 7 Ans. (c)
(b) Q > K sp (a) S =   (b) S =  
 144   6912  Let the solubility of Ag2 CO3 is S. Now,
(c) Q = K sp 1/ 9 1/ 7 0.1 M of AgNO3 is added to this solution
(d) Not enough data provided  K sp   K sp  after which let the solubility of Ag2 CO3
(c) S =   (d) S =  
 929   216  becomes S ′.
Ans. (b)
∴ [Ag + ] = S + 0.1 and [CO23− ] = S ′
PbCl2 (s ) -Pb 2+
(aq) + 2Cl − (aq) ; Ans. (b) K sp = (S + 0.1)2 (S ′) ...(i)
K sp = 16. × 10 −5
Key Idea The concentration of a Given, K sp = 8 × 10 − 12
For mixture, 300 mL 0.134 M Pb(NO3)2 substance in a saturated solution is Q K sp is very small, we neglect S ′ against
and 100 mL 0.4 M NaCl defined as its solubility (S). S in Eq. (i)
After mixing, total volume = 400 mL For A x B y -xA y + + yB x −; ∴ K sp = (0.1)2 S ′
[Pb2 + ] after mixing (before any precipitate or 8 × 10 − 12 = 0.01 S ′
K sp = [A y + ] x [B x − ] y
forms)
or S ′ = 8 × 10 − 12 × 102
300 × 0.134 3 × 0.134 1
= = ≈ For, Zr3 (PO4 ) 4 , = 8 × 10 − 10 M
400 4 10
Zr3 (PO4 ) 4 (s) -3Zr 4 + (aq) + 4PO34− (aq) Thus, molar solubility of Ag2 CO3 in 0.1 M
[Cl − ] after mixing (before any precipitate 3S M
AgNO3 is 8 × 10 − 10 M.
4 SM
forms) K sp = [Zr 4 + ] 3 [PO34− ] 4
100 × 0.4 1
= = 0.1  K 7 29 An aqueous solution contains
7
400 K sp = (3S ) (4S ) = 6912 S or S =  sp 
3 4
 6912  0.10 M H2S and 0.20 M HCl. If the
As we know,
3 × 0.134 Thus, the relation between molar
equilibrium constants for the
Q = [Pb2 + ][Cl − ]2 = × 10 −2 ≈ 10 −3 formation of HS − from H2S is
4 solubility(S) and solubility product (K sp )
1/ 7 1.0 × 10 −7 and that of S 2− from HS −
K 
25 The solubility product of Cr(OH) 3 at will be S =  sp  ions is 1.2 × 10 −13 then the
 6912 
298 K is 6.0 × 10 −31 . The concentration of S 2− ions in
concentration of hydroxide ions in aqueous solution is : [JEE Main 2018]
27 What is the molar solubility of (a) 5 × 10−8 (b) 3 × 10−20
a saturated solution of Cr(OH) 3 will Al(OH) 3 in 0.2 M NaOH solution? (c) 6 × 10−21 (d) 5 × 10−19
be [2020, 9 Jan Shift-II] Given that, solubility product of Ans. (b)
(a) (2.22 × 10−31) 1/ 4 (b) (18 × 10−31) 1/ 4 Al(OH) 3 = 2.4 × 10 −24
(c) (4.86 × 10−29 ) 1/ 4 (d) (18 × 10−31) 1/2 [2019, 12 April Shift-I] Given,
Ans. (d) (a) 3 × 10 −19
(b) 12 × 10 −21 [H2S] = 0.10 M
−31 (c) 3 × 10−22 (d) 12 × 10−23 [HCl] = 0.20 M So, [H+ ] = 0.20 M
K sp of Cr(OH) 3 at 298 K is60. × 10 .
Ans. (c) H2S - H+ + HS − , K 1 = 1.0 × 10 −7
[OH− ] in saturated solution of Cr(OH) 3 = ? −
HS - H+ + S2 − , K 2 = 12
. × 10 −13
Cr(OH) 3 - Cr 3+ + 3OH− Key Idea Concentration of substance in
S S a saturated solution is defined as its It means for,
In a saturated solution, solubility (S). Its value depends upon the H2S - 2H+ + S2 −
nature of solvent and temperature. For K = K 1 × K2
K sp = [Cr 3+ ][OH− ] 3 reaction,
. × 10 −31
= S (3S ) 3 = 27 S 4 = 60 . × 10 −7 × 1.2 × 10 −13
= 10
AB - A+ + B − = 1.2 × 10 −20
. × 10 −31
60 +
K sp = [A ] [B ] −
∴ S = 4
K × [H2S]
27 3+ Now [S2 − ] =
1 Al(OH) - Al
3 + 3OH− [H+ ]2
 60
. × 10 −31  4 Initially 1 0 0
[according to the final equation]
⇒ S=  At equilibrium 1− S S 3 S + 0.2
 27  1.2 × 10 −20 × 0.1 M
=
1 NaOH → Na+ + OH− (0.2M)2
 60
. × 10 −31  4 0.2 0.2
[OH] – = 3S = 3   K sp of Al(OH) 3 = 2.4 × 10 −24 (Given) 1.2 × 10 −20 × 1 × 10 −1 M
 27  =
K sp = [Al 3+ ] [OH− ] 3 4 × 10 −2 M
1
 60
. × 34 4
1
2.4 × 10 −24 = [S ] [3 S + 0.2] 3 [Q0.2>> S ] = 3 × 10 −20 M
= × 10 −31  = (18 × 10 −31) 4
 3 3
 2.4 × 10 −24 = [S ] [0.008]
30 An aqueous solution contains an
[S ] = 3 × 10 −22
unknown concentration of Ba 2+ .
26 If solubility product of Zr 3 (PO 4 ) 4 is When 50 mL of a 1 M solution of
denoted by K sp and its molar 28 If K sp of Ag 2CO 3 is 8 × 10 − 12 , the
molar solubility of Ag 2CO 3 in 0.1 M Na 2SO 4 is added, BaSO 4 just
solubility is denoted by S, then
AgNO 3 is [2019, 12 Jan Shift-II]
begins to precipitate. The final
which of the following relation
volume is 500 mL. The solubility
between S and K sp is correct? (a) 8 × 10− 12 M (b) 8 × 10− 13 M
product of BaSO 4 is 1 × 10 −10 .
[2019, 8 April Shift-I] (c) 8 × 10− 10 M (d) 8 × 10− 11 M
Ionic Equilibrium 101

What is the original concentration 32 Solubility product of silver bromide the mass of AgIO 3 contained in
of Ba 2+ ? [JEE Main 2018] is 5.0 × 10 −13 . The quantity of 100 mL of its saturated solution?
(a) 5 × 10−9 M (b) 2 × 10−9 M potassium bromide (molar mass [AIEEE 2007]
(c) 1.1 × 10−9 M (d) 1.0 × 10−10 M taken as 120 g mol −1 ) to be added (a) 28.3 × 10−2 g (b) 2.83 × 10−3 g
Ans. (c) to 1 L of 0.05 M solution of silver (c) 1.0 × 10−7 g . × 10−4 g
(d) 10
Its given that the final volume is 500 mL nitrate to start the precipitation of Ans. (b)
−
and this final volume was arrived when
50 mL of 1 M Na2SO4 was added to
AgBr is
−10
[AIEEE 2010]
−9
AgIO3 (s ) r Ag (aq) + IO (aq)
+
3
. × 10 g
(a) 12 . × 10 g
(b) 12 Let the solubility of AgIO3 be S
unknown Ba2 + solution.
(c) 6.2 × 10−5 g (d) 5.0 × 10−8 g K sp = [Ag + ] [IO−3 ]
So, we can interpret the volume of
unknown Ba2 + solution as 450 mL i.e. Ans. (b) 1.0 × 10 −8 = S 2 or S = 1 × 10 − 4 mol /L
+
450mL + 50mL → 500mL [AgBr] = [Ag ] = 0.05 M
In 1000 mL moles of AgIO3 dissolved
Ba 2 +
solution
Na 2 SO 4
solution
BaSO 4
solution K sp [AgBr] = [Ag + ] [Br − ] = 1 × 10 − 4 moles
From this we can calculate the K sp (AgBr) In 100 mL moles of AgIO3 dissolved
⇒ [Br − ] =
concentration of SO24− ion in the solution [Ag + ] = 1 × 10 −5 moles
via
5.0 × 10 -13 Mass of AgIO3 in 100 mL
M1V1 = M2V2 = = 10 −11 M [mol L −1]
0.05 = 1 × 10 −5 mol × 283 g mol −1
1 × 50 = M2 × 500
Moles of KBr needed to precipitate AgBr = 2.83 × 10 −3 g
(as 1M Na2SO4 is taken into
= [Br − ] × V = 10 −11 mol L −1 × 1L = 10 −11 mol
consideration)
1 Therefore, amount of KBr needed to 35 The solubility product of a salt
M2 = = 0.1 M precipitate AgBr
10 having general formula MX 2 , in
= 10 −11 mol × 120 g mol −1 = 1.2 × 10 −9 g water is 4 × 10 − 12 . The
Now for just precipitation,
Ionic product = Solubility product (K sp ) concentration of M 2+ ions in the
33 Solid Ba(NO 3 ) 2 is gradually
i.e. [Ba2 + ][SO24− ] = K sp of BaSO4 aqueous solution of the salt is
Given K sp of BaSO4 = 1 × 10 −10 dissolved in a 1.0 × 10 −4 M Na 2CO 3 [AIEEE 2005]
So, [Ba2 + ][0.1] = 1 × 10 −10 solution. At what concentration of (a) 4.0 × 10−10 M (b) 1.6 × 10−4 M
or [Ba2 + ] = 1 × 10 −9 M Ba 2+ , will a precipitate begin to (c) 1.0 × 10−4 M (d) 2.0 × 10−6 M
Remember This is the concentration of form? Ans. (c)
Ba2 + ions in final solution. (K sp for BaCO 3 = 5.1 × 10 −9 ) 2+
[AIEEE 2009]
MX2 rM + 2X −
Hence, for calculating the [Ba2 + ] in S 2S
original solution we have to use (a) 4.1 × 10−5 M (b) 5.1 × 10−5 M
K sp = [M2 + ] [X − ] 2
M1V1 = M2V2 (c) 8.1 × 10−8 M (d) 8.1 × 10−7 M
If solubility be S, then
as M1 × 450 = 10 −9 × 500 Ans. (b) K sp = (S ) (2 S )2 = 4 S 3
so, M1 = 1.1 × 10 −9 M Na2 CO3 a 2Na+ + CO23 − 4 S 3 = 4 × 10 −12 ⇒ S = 1 × 10 −4 M
[Na2 CO3] = [CO23− ] = 1 × 10 −4 M ∴ [M2 + ] = S = 1 × 10 −4 M
31 The K sp for Cr(OH) 3 is 1.6 × 10 −30 . BaCO3 a Ba2 + CO23−
The molar solubility of this K sp (BaCO ) = [Ba2 + ] [CO23- ] 36 The molar solubility (in mol L−1 ) of a
3
compound in water is [AIEEE 2011] Ksp (BaCO3) sparingly soluble salt MX 4 is S. The
[Ba2 + ] = corresponding solubility product is
2
(a) 1.6 × 10 −30 [CO23− ]
K sp . S is given in terms of K sp by
5.1 × 10 -9
(b) 4 1.6 × 10−30 ⇒ [Ba2 + ] = the relation.
1 × 10 −4
−30 (a) S = (K sp / 128) 1/ 4 (b) S = (K sp / 128) 1/ 4
(c) 1.6 × 10
4
/27 [Ba ] = 5.1 × 10
2+ −5
M (c) S = (K sp / 256) 1/ 5 (d) S = (K sp / 256) 1/ 5
(d) 1.6 × 10−30 /27 Hence, at 5.1 × 10 −5 M concentration of [AIEEE 2004]
Ans. (c) Ba2 + , a precipitate will begin to form. Ans. (c)
Let molar solubility of Cr(OH) 3 = s mol L−1 MX4 r M4 + + 4X −
Cr 3+ (aq) + 3OH− (aq)
34 In a saturated solution of the
Cr(OH) 3 (s ) 1 K sp = [M ] [4X − ] 4
4+
3s sparingly soluble strong electrolyte
K sp = (S ) (4S) 4
s
K sp = 1.6 × 10 −30
AgIO 3 (molecular mass = 283) the
= [Cr 3+ ] [OH− ] 3 = (s )(3s ) 3 = 27 s 4 ⇒ K sp = 256 S 5
equilibrium which sets in is
1.6 × 10 −30 K sp
∴ s4 = AgIO 3 (s ) r Ag + (aq ) + IO 3− (aq ) S5 =
27 256
If the solubility product constant,
1.6 × 10 −30 K 
1/ 5
⇒ s =4 K sp of AgIO 3 at a given ⇒ S =  sp 
27
temperature is 1.0 × 10 −8 , what is  256 
102 JEE Main Chapterwise Topicwise Chemistry

37 The solubility in water of a sodium acetate in the buffer is pH = − log[H+ ] = − log(99

. × 10 −2 )
sparingly soluble salt AB2 is ………… M. (Round off to the . ≈ 1]
[Qlog 99
1.0 × 10 −5 mol L−1 . Its solubility nearest integer). = 2 − log 99
. = 2− 1
product will be [AIEEE 2003] [Given : pK a (acetic acid =4.74] pH = 1
(a) 4 × 10−15 (b) 4 × 10−10 [2021, 18 March Shift-I]
Ans. (10)
42 The pH of ammonium phosphate
(c) 1 × 10−15 (d) 1 × 10−10 solution, if pK a of phosphoric acid
Given : pH = 5.74
Ans. (a) and pK b of ammonium hydroxide
Concentration of acetic acid in buffer
AB2 rA 2+
+ 2B − = 10
. M are 5.23 and 4.75 respectively, is
S 2S Acetic acid and its conjugate base ……… . [2021, 26 Feb Shift-II]

K sp = [A2 + ] [B − ]2 = (S ) (2 S )2 = 4 S 3 sodium acetate makes acidic buffer. Ans. (7)

= 4 (1 × 10 −5 ) 3 = 4 × 10 −15 CH3COOH + CH3COONa → (Acidic Phosphoric acid is a weak tribasic acid
buffer) (H3PO4 ) and NH4OH is a weak monoacidic
base. So, hydrolysis of ammonium
38 Solubility of Ca(OH) 2 is S mol L−1 . Using formula,
phosphate (NH4 ) 3PO4 can be shown as,
[Salt]
The solubility product (K sp ) under pH = pK a + log (NH4 ) 3PO4 + 3H2O H3PO4 + 3NH4OH
-
[Acid] [3 : 1 type salt]
the same condition is [AIEEE 2002]
[CH3COONa] 12
(a) 4 S 3 (b) 3 S 4 (c) 4 S2 (d) S 3 pH = pK a + log  Kw 
[CH3COOH] So, [H+ ] =K a ×  
Ans. (a)  K a ×K b 
[CH3COONa]
Ca(OH)2 r Ca2 + + 2OH− 5.74 = 4.74 + log 1
− 2 [CH3COOH] pH = pK a + [pK w − pK a − pK b ]
K sp = [Ca ] [OH ] = (S ) ( 2 S )2 = 4 S 3
2+
2
[CH3COONa] 1
5.74 − 4.74 = log = 523
. + (14 − 523 . − 4.75)
[CH3COOH] 2
TOPIC 4 [CH3COONa]
[QpK w = 14H2O
pH, Buffer and Indicator 1 = log pK a = 523
. (H3PO4 )
[CH3COOH]
pK b = 4.75 (NH4OH)] = 7.24 − ~7
[CH3COONa]
39 The pH of a solution obtained by ⇒ = 10
[CH3COOH] 43 The solubility of AgCN in a buffer
mixing
[∴ [CH3COOH] = 1] solution of pH= 3 is x. The value of x
50 mL of 1 M HCl and 30 mL of 1 M
[CH3COONa] = [10 × 1] = 10 is…… .
NaOH is x × 10 − 4 . The value of x is
Thus, the concentration of sodium [Assume : No cyano complex is
......... (Nearest integer) acetate in buffer is 10 M. formed; K sp (AgCN) = 2.2 × 10 −16
[log 2.5 = 0.3979] and K a (HCN) = 6.2 × 10 −10 ]
[2021, 31 Aug Shift-II] 41 Sulphurous acid (H2SO 3 ) has [2021, 25 Feb Shift-I]
Ans. (6021)
K a = 1.7 × 10 −2 and K a = 6.4 × 10 −8 (a) 0.625 × 10−6 (b) 1.6 × 10−6
Milliequivalents of HCl 1 2
. The pH of 0.588 M is …… (c) 2.2 × 10−16 (d) 1.9 × 10−5
(N a Va ) = 50 × 1 = 50
Milliequivalents of NaOH
(Round off to the nearest integer) Ans. (d)
[2021, 16 March Shift-II]
(N bVb ) = 30 × 1 = 30 pH of AgCN buffer solution = 3
Ans. (1) [H+ ] = 10 −3
Since, N a Va > N bVb
and they neutralise each other
For H2SO3, K a 11 >>K a 2 K sp (AgCN) = 2.2 × 10 −16
N V − N bVb So, we mainly consider 1st ionisation K a [HCN] = 6.2 × 10 −10
[H+ ] = a a H+ + HSO−3 ; K a 1 = 1.7 × 10 −2
Va + Vb H2SO3 - AgCN q Ag + + CN− …… K sp
t =0 0.558 0 0 CN− + H+ q HCN ……
1
50 − 30
= = 0.25 = 2.5 × 10 −1 t = t eq 0.558 −0.558α 0.558α 0.558α Ka
80
pH = − log [H+ ] [H+ ][HSO−3 ] AgCN + H+ q HCN + Ag +
Ka 1 =
= − log (2.5 × 10 −1) [H2SO3] 1 [Ag + ][CN− ] [HCN]
K sp × =
= 1 − 0.3979 = 0.6021 (0.558α)(0.558α) 0.558α2 Ka [H+ ] [CN− ]
= =
pH × 10 4 = 0.6021 × 10 4 = 6021 0.558(1 − α) 1−α K sp [H+ ]
∴ x = 6021 [S ] =
α << 1 for weak acid Ka
(1 −α) ≈ 1
40 In order to prepare a buffer 2.2 × 10 −16 [S ] [S ]
⇒ =
solution of pH 5.74, sodium acetate Ka1 1.7 × 10 −2 6.2 × 10 −10 10 −3
α= =
is added to acetic acid. If the 0.558 0.558 2.2 × 10 −16
[S ]2 = × 10 −3
concentration of acetic acid in the α = 1.7 × 10 −1 = 0.17 6.2 × 10 −10
buffer is 1.0 M, the concentration of [H] + = 0.558α = 99
. × 10 −2 . × 10 −5
S = 19
Ionic Equilibrium 103

44 An acidic buffer is obtained on increases instantly but this

titration show pH increases slowly
mixing [2020, 3 Sep Shift-I]
(c) pH 7 because base (NaOH) is mix drop
(a) 100 mL of 0.1 M CH3COOH and 100 mL by drop.
of 0.1 M NaOH
(c) After equivalence point (pH = 7)
(b) 100 mL of 0.1 M HCl and 200 mL of
graph is constant. It is wrong
0.1 M NaCl vol. of NaOH
because graph increases and the
(c) 100 mL of 0.1 M CH3COOH and 200 mL solution becomes pure basic then
of 0.1 M NaOH graph show constant value.
(d) 100 mL of 0.1 M HCl and 200 mL of
(d) pH 7 (d) According to graph, equivalence
0.1 M CH3COONa
point (pH = 7) graph should increase
Ans. (d) but it decreases.
An acidic buffer is a mixture of weak acid vol. of NaOH
and its salt with strong base. Now, let us 46 A soft drink was bottled with a
study the composition of each mixture Ans. (a) partial pressure of CO 2 of 3 bar
obtained by mixing of two solutions. Given 100 mL of 0.1 M HCl is taken in over the liquid at room
–+
beaker and to it 100 mL of 0.1 M NaOH is
(a) CH3COOH + NaOH CH3COONa + H2O temperature. The partial pressure
t = 0 100 × 0.1 100 × 0.1
added.
millimol
0 0 of CO 2 over the solution
B
t=a 0 0 10 10 approaches a value of 30 bar when
So, it is not a buffer. 44 g of CO 2 is dissolved in 1 kg of
NaCl, a salt of strong acid (HCl) and pH 7
water at room temperature. The
strong base (NaOH) is not hydrolisable by approximate pH of the soft drink is
HCl also. So, it is not a buffer. A …… ×10 −1 .
–+
CH3COOH + NaOH CH3COONa + H2O Volume of NaOH (First dissociation constant of
millimol
t = 0 100 × 0.1
(Limiting)
200 × 0.1 0 0
This is acid (HCl) and base (NaOH) H2CO 3 = 4.0 × 10 −7 ) log2 = 0.3;
t=a 0 20 –10 = 10 10 10 titration. Here, phenolphthalein act as an density of the soft drink = 1g mL −1 )
After mixing, the solution contains indicator and colour change is pink. The [2020, 6 Sep Shift-I]
equimolar amounts by NaOH (a strong correct graph that depicts the change in Ans. (37)
−+ pH is as follows.
base) and CH3COON a (salt). At 30 bar pressure mass of CO2 in 1 kg
At first HCl (acid) is take in beaker and
So, it is also not a buffer. water = 44 g
base (NaOH) is taken in burette.
– + At 3 bar pressure mass of CO2 in 1 kg
CH3COONa + HCl CH3COOH + NaCl When base is added drop wise then
t = 0 200 × 0.1 100 × 0.1 0 0 water = 4 .4 g
acid-base reaction is occurs and
millimol (Limiting)
4.4
t = a 20 –10 = 10 0 10 10 following changes are observed. Moles of CO2 in 1 kg water = = 0 . 1 mol
44
Now, the resultant solution contains pH → 0 to 7 is acidic. pH → 7 is neutral.
pH → 7 to 14 is basic. In solution, H2O + CO2 r H2 CO3 (0.1 mol)
equimolar amount of CH3COOH (an weak
acid) and CH3COONa (a salt of CH3COOH Initially, the graph increases steeply but or H2 CO3 r H+ + HCO−3
with a strong base, NaOH). when concentration of acid becomes Initially 0.1 − −
So, it is an acid buffer. equal to base then no change is seen in At equil. 0 .1 (1 − α ) 0 .1 α 0 .1 α
graph. Here, α = degree of dissociation
45 100 mL of 0.1M HCl is taken is a This point is called neutral point or [H+ ][HCO−3 ]
Ka 1 =
beaker and to it 100 mL of 0.1 M equivalence point. Equivalence point, [H2 CO3]
NaOH is added in steps of 2 mL and where pH = 7.
[Here, K a 1 = first dissociation of
the pH continuously measured. After the equivalence point (pH = 7),
constant of H2 CO3]
base (NaOH) is continuously mixed drop
Which of the following graphs (0.1 α)2
by drop then pH increases by 7 and graph 4 × 10 − 7 = = 0.1 α2
correctly depicts the change in pH? also increases slowly. At the point B, 0.1(1 − α)
[2020, 3 Sep Shift-II]  Ka 
solution become basic, again base Q < 10 − 3,
(NaOH) is mixed drop by drop and the  C 
 
solution becomes basic at point B.  1 − α ≅ 1 
(a) pH 7 Following inference can be seen in the
graphs. . × 10 − 7 × 0.1 = 0.01 α2 ; α = 2 × 10 − 3
40
(a) According to this graph, pH = 7 is [H+ ] = 0 . 1 α = 0.1 × 2 × 10 − 3
equivalence point and use of NaOH = 2 × 10 − 4
vol. of NaOH
(base) drop by drop leads to basic pH = − log[H+ ]
solution as a result, value of pH = − log[2 × 10 − 4 ]
(b) pH 7 increases slowly. This is correct
= − [log 2 + log[10 − 4 ]]
option.
(b) According to graph, it shows = − [0.3 − 4]
vol. of NaOH straight line that mean graph = 3.7 = 37 × 10 − 1
104 JEE Main Chapterwise Topicwise Chemistry

47 3 g of acetic acid is added to 250 Ans. (b) 20 × 10 −3

= = 4 × 10 −4 M
mL of 0.1 M HCl and the solution (A) pOH of 0.01 M HCl : 50
made up to 500 mL. To 20 mL of HCl → H+ + OH− As we know,
(0.01M)
1 (0.01M) (0.01M)
pOH = –log[OH– ]
this solution mL of 5 M NaOH is [H+ ] = (0.01M); pH = − log [H+ ]
2 ∴ pOH = −log 4 × 10 −4 = 4 − log 4
added. The pH of the solution is ⇒ − log(10 −2 ) ⇒2 or pH = 14 − pOH
∴pOH = 14 − pH⇒14 − 2 = 12
………… = 14 − (4 − log 4)
(B) pOH of 0.01 M NaOH :
[Given : pK a of acetic acid = 4.75, = 10 + log 4 = 10.602
NaOH → Na+ + OH−
molar mass of acetic acid = 60 (0.01M) (0.01M) (0.01M)
50 The strength of an aqueous NaOH
g/mol, log 3 = 0.4771] [OH− ] = 10 −2
solution is most accurately
Neglect any changes in volume. ∴ pOH = − log [OH− ]
determined by titrating : (Note :
[2020, 7 Jan Shift-II] ⇒ − log(10 −2 ) = 2
Ans. (5.23) – +
consider that an appropriate
(C) pOH of 0.01 M CH3COON a : indicator is used) [2020, 8 Jan Shift-I]
3 1
3g CH3COOH (M = 60) = = mol (salt of weak acid + strong base) (a) Aq. NaOH in a volumetric flask and
60 20 1
250 pH = 7 + [pK a + log(10 −2 )] concentratedH2SO4 in a conical flask
250 mL of 0.1 M HCl = M × V = × 0.1 2 (b) Aq. NaOH in a pipette and aqueous
1000 ∴ pH > 7, thus pOH < 7 oxalic acid in a burette
−3
= 25 × 10 mol (c) Aq. NaOH in a burette and aqueous
(D) pOH of 0.01 M NaCl :
After mixing these two, solution is oxalic acid in a conical flask
diluted to 500 mL. (It is a salt of strong acid + strong base)
(d) Aq. NaOH in a burette and
Then from that solution, 20 mL is taken. ∴ pH = pOH ⇒ 7
concentratedH2SO4 in a conical flask
Number of moles of both CH3COOH and Thus, order of pOH value :
Ans. (c)
20 1 (A) > (D) > (C) > (B)
HCl will be now only = of original The strength of aqueous NaOH solution
500 25 Hence, the correct option is (b).
is most accurately determined by
solution.
titrating aqueous NaOH in burette and
1 1 1 49 Two solutions, A and B, each of 100
nCH COOH = × = = 2 × 10 −3 mol aqueous oxalic acid in conical flask with
3
20 25 500 L was made by dissolving 4 g of phenolphthalein as an indicator. (For
1
nHCl = 25 × 10 −3 × = 10 −3 mol NaOH and 9.8 g of H2SO 4 in water, weak acid-strong base titration, methyl
25 respectively. The pH of the orange cannot be used).
1
nNaOH added = M × V = × 5 × 10 −3 resultant solution obtained from Thus, solution turns colourless to pink at
2 the end point. (Phenolphthalein has pink
mixing 40 L of solution A and 10 L
= 2. 5 × 10 −3 of solution B is ……… .
colour when pH > 10 and it is colourless
when pH < 8 (approximately) which is
After mixing, all HCl and NaOH will be [2020, 7 Jan Shift-I]
easily to perceive.
neutralised. Remaining number of Ans. (10.60)
moles. If NaOH is taken in conical flask and
(A) 4 g NaOH in 100 L oxalic acid is added from burette, the
nNaCl = 10 −3
4 /40 end point will be the decolourisation of
nCH COONa = 1.5 × 10 −3 ⇒ M= = 10 −3 mol L −1. pink colour which is more difficult to
3
100
nCH COOH (unreacted) = 0.5 × 10 −3 percieve by human eye very quickly.
3
(B) 9.8 g H2SO4 in 100 L
∴Now the solution is a buffer solution. 9.8 /98 51 For the following Assertion and
[salt] ⇒ M= = 10 −3 mol L −1
pH = pK a = log 100 Reason, the correct option is
[acid] 40 L of solution A contains Assertion (A) The pH of water
(nCH COONa )
= pK a + log 3 = 40 × 10 −3 mol NaOH (Qn = M × V ) increases with increase in
(nCH COOH ) −3 − temperature.
3 = 40 × 10 mol OH
= 4.75 + log 3 = 4.75 + 0.4771 10 L of solution B contains Reason (R) The dissociation of
= 52271
. ≈ 5.23 = 10 × 10 −3 mol H2SO4 water into H+ and OH− is an
= 20 × 10 −3 mol H+ exothermic reaction.
48 Arrange the following solutions in When they are mixed, total volume = 50 L [2020, 8 Jan Shift-II]
the decreasing order of pOH. and all H+ is neutralised by OH− . (a) Assertion is not true, but Reason is
true.
(A) 0.01 M HCl (B) 0.01 M NaOH Number of moles (nOH − ) of excess OH− .
(C) 0.01 M CH3COONa (b) Both assertion and Reason are true
(D) 0.01 M NaCl [2020, 6 Sep Shift-I]
= (40 − 20) × 10 −3 = 20 × 10 −3 and the Reason is the correct
n − explanation for the Assertion.
(a) (A) > (C) > (D) > (B) [OH− ] = OH (in litre)
Vsolution (c) Both Assertion and Reason are false.
(b) (A) > (D) > (C) > (B)
nOH − (d) Both Assertion and Reason are true,
(c) (B) > (C) > (D) > (A)
Or [OH− ] = but the Reason is not the correct
(d) (B) > (D) > (C) > (A) Total volume explanation for the Assertion.
Ionic Equilibrium 105

Ans. (c) 53 Consider the following statements. 10 −5 × α

+
⇒ 10 −5 =
The dissociation of water intoH and I. The pH of a mixture containing 1 −α
OH− is an endothermic reaction. 400 mL of 0.1 M H2SO 4 and ⇒ α = 0.5 ⇒ α% = 50
∴ As temperature increases, its 400 mL of 0.1 M NaOH will be Hence, the option (c) is correct.
equilibrium constant also increases. In statement (IV), Le-Chatelier’s principle
approximately 1.3.
∴ [H+ ] and [OH− ] in water at equilibrium is applicable to common ion effect.
increases with increase in temperature. II. Ionic product of water is Because, in presence of common ion
∴ pH = − log [H+ ] decreases, as temperature dependent. −
(given) by strong electrolyte (say,Na+ A),
temperature increases. III. A monobasic acid with the product of the concentration terms
So, both Assertion and Reason are false. K a = 10 −5 has a pH = 5. The in RHS increases. For the weaker
degree of dissociation of this electrolyte, HA (say) the equilibrium
52 The molar solubility of Cd (OH) 2 is shifts to the LHS, HA H⊕ + A s.
-
acid is 50%.
1.84 × 10 −5 m in water. The expected As a result dissociation of HA gets
IV. The Le-Chatelier’s principle is suppressed. Hence, the option (d) is
solubility of Cd(OH) 2 in a buffer
not applicable to common-ion incorrect.
solution of pH= 12 is
[2019, 12 April Shift-I]
effect. The correct
statements are 54 20 mL of 0.1 M H2SO 4 solution is
. × 10−9 M
(a) 184 [2019, 10 April Shift-I]
2.49 added to 30 mL of 0.2 M NH4OH
(b) × 10−9 M (a) I, II and IV (b) II and III
184
. solution. The pH of the resultant
(c) I and II (d) I, II and III
(c) 6.23 × 10−11 M mixture is [pK b ofNH4OH = 4.7]
Ans. (d)
(d) 2.49 × 10−10 M (a) 9.3 (b) 5.0 (c) 9.0 (d) 5.2
The explanation of given statements are [2019, 9 Jan Shift-I]
Ans. (d)
as follows:
Ans. (a)
Key Idea The concentration of In statement (I), millimoles ofH+
substance in a saturated solution is = 400 × 0.1 × 2 = 80 The reaction takes place whenH2SO4 is
defined as its solubility (S). Its value Millimoles ofOH− = 400 × 0.1 = 40 added toNH4OH is as follows :
depends upon the nature of solvent and (Limiting reagent)
temperature. H2SO4 + 2NH4OH → (NH4 )2 SO4 + 2H2O
∴ Millimoles ofH+ left = 80 − 40 = 40 Strong Weak Salt of strong acid
Ax By - xA y + + yB x − 40 40 1 acid base + weak base
[H+ ] = = M= M
K sp = [A ] [B x − ] y
y+ x
400 + 400 800 20 Millimoles 20 × 0.1 = 2 30 × 0.2 = 6 0
at t = 0
pH = − log [H+ ] = − log  
1
Solubility of ⇒
 20  Millimoles 0 2 2
Cd(OH)2 (S) = 1.84 × 10 − 5 M at t = t
= − log 1 + log 2 + log 10
Given, pH = 12 [for Cd(OH)2 in buffer So, the resulting solution is a basic
= −0 + 0.301 + 1 ⇒1.30
solution] buffer [NH4OH + (NH4 )2 SO4 ] .
Hence, the option (a) is correct.
So, pOH = 2 (Q pH + pOH = pK w ) According to the Henderson’s equation,
In statement (II), ionic product ofH2O is
12 + pOH = 14 temperature dependent. [(NH4 )2 SO4 ]
pOH = pK b + log
pOH = 14 − 12 = 2 K w = [H+ ] [OH− ] ≈ 10 −14 (mol /L)2 at 25ºC [NH4OH]
∴ [OH− ] = 10 − 2 in buffer solution. With increase in temperature, 2
= 4.7 + log = 4.7
For reaction Cd(OH)2 → Cd2 + + 2OH− dissociation of H2O units into H+ and 2
S S2 OH− ions will also increase. As a result, ⇒ pH = 14 − pOH
K sp = [Cd2 + ] [OH− ]2 the value of ionic product, [H+ ] × [OH− ]
= 14 − 4.7 = 9.3
will be increased. e.g.
K sp = (S ) (2S )2 = 4S 3
= 4(1.84 × 10 − 5 ) 3 Temperature Kw L2 55 An alkali is titrated against an acid
5ºC . × 10
0186 −14 with methyl orange as indicator,
K sp = 24.9 × 10 − 15 which of the following is a correct
25ºC 1008
. × 10−14
2+ K sp combination? [JEE Main 2018]
[Cd ]= 45ºC 4.074 × 10−14
[OH− ]2
Base Acid End point
Hence, the option (b) is correct.
24.9 × 10 − 15 (a) Weak Strong Colourless to
[Cd2 + ] = In statement (III), for a weak monobasic
(10 − 2 )2 pink
acid HA
. × 10 − 15 × 10 +4
= 249 HA w H⊕ + A s
(b) Strong Strong Pinkish red to
− 11 (1− α ) C M αC M αC M
yellow
= 249
. × 10 M
⇒pH of the solution is 5, i.e. (c) Weak Strong Yellow to
[Cd2 + ] ⇒249. × 10 − 10 M pinkish red
The expected solubility of Cd(OH)2 in a [H+ ] = 10 −5 M = αC
(d) Strong Strong Pink to
buffer solution of pH = 12 is αC × αC 10 −5 × α colourless
2.49 × 10 − 10 M. ⇒ Ka = =
(1 − α)C 1 −α
106 JEE Main Chapterwise Topicwise Chemistry

Ans. (c) Ans. (a) Ans. (c)

Methyl orange show Pinkish colour pH of a solution = 5 When HA is 50% ionised, [HA] = [A − ]
towards more acidic medium and yellow ∴ [H+ ] = 10 − pH = 10 −5 Buffer solution of weak acidHA → acidic
orange colour towards basic or less buffer
acidic media. Its working pH range is HA (a weak acid) ionises as
[A − ]
Weak base have the pH range greater HA rH +
+ A− pH=pK a + log
[HA]
than 7. When methyl orange is added to 1.0 0 0
−5 −5 or pH = pK a = 4.5
this weak base solution it shows yellow (1 − 10 ) 10 10 −5
orange colour. pOH =pK w − pH
Now when this solution is titrated [H+ ] [A – ] 10 −5 × 10 −5 pOH = 14 − 4.5 =9.5
Ka = =
against strong acid the pH move towards [HA] (1 − 10 −5 )
more acidic range and reaches to end 62 Hydrogen ion concentration in
10 −10
point near 3.9 where yellow orange = [Q 1 >>> 10 −5 ] mol/L in a solution of pH= 5.4 will
colour of methyl orange changes to 1
Pinkish red resulting to similar change in = 1 × 10 −10 M
be [AIEEE 2005]
colour of solution as well. . × 10−6
(a) 398 (b) 3.68 × 10−6
59 At 25°C, the solubility product of . × 106
(c) 388 . × 108
(d) 398
56 pK a of a weak acid (HA) and pK b of Mg(OH) 2 is 1.0 × 10 −11 . At which pH, Ans. (a)
a weak base (BOH) are 3.2 and 3.4, will Mg 2+ ions start precipitating in pH = 5.4
respectively. The pH of their salt the form of Mg(OH) 2 from a ⇒ [H+ ] = 10 −5.4 = 10 −6 ⋅ 10 0.6
(AB) solution is [JEE Main 2017]
solution of 0.001 M Mg 2+ ions? Antilog of 0.6 is ≈ 3.98
(a) 7.2 (b) 6.9 [AIEEE 2010] ∴ [H+ ] ≈ 3.98 × 10 −6 M
(c) 7.0 (d) 1.0 (a) 9 (b) 10
Ans. (b) (c) 11 (d) 8 63 Which one of the following
For a salt of weak acid and weak base, Ans. (b) statements is not true?
1 1 Mg(OH)2 r Mg2 + + 2OH− [AIEEE 2003]
pH = 7 + pK a − pK b
2 2 K sp = [Mg ] [OH– ]2
2+
(a) The conjugate base of H2PO4− isHPO24−
K sp 1 × 10 −11 (b) pH + pOH = 14 for all aqueous
Given, pK a (HA) = 3.2, [OH− ] = = solutions
pK a (BOH) = 3.4 [Mg2 + ] 0.001
(c) The pH of 1 × 10 − 8 M HCl is 8
1 1 pOH = − log [OH−1] = − log [10 −4 ] (d) 96,500 C of electricity when passed
∴ pH = 7 + (3.2) − (3.4)
2 2 pOH = 4 and pH = 10 through a CuSO4 solution deposits 1g
= 7 + 1.6 − 1.7 = 6.9 ∴ pH = 14 − pOH = 14 − 4 = 10 equivalent of copper at the cathode
Ans. (c)
57 How many litres of water must be 60 The pK a of a weak acid, HA is 4.80. In 1 × 10 −8 M HCl solution, H2O is also
added to 1 L of an aqueous solution The pK b of a weak base, B OH, is present which also undergoes self
of HCl with a pH of 1 to create an 4.78. The pH of an aqueous ionisation.
aqueous solution with pH of 2? solution of the corresponding salt, H2O r H+ + OH−
[JEE Main 2014]
BA, will be [AIEEE 2008] 10 −7 M at 25°C[Concentration of water
(a) 0.1 L (b) 0.9 L (H2O)]
(a) 9.58 (b) 4.79
(c) 2.0 L (d) 9.0 L (c) 7.01 (d) 9.22 If it is taken simply even without
Ans. (d) common ion effect, higher
Ans. (c)
concentration must be considered which
pH = 1 ⇒ [H+ ] = 10 −1 = 0.1 M For salt of weak acid and weak base is 10 −7 M but H+ from HCl decreases self
pH = 2 ⇒ [H+ ] = 10 −2 = 0.01 M 1 ionisation of water and hence [H+ ] from
pH = − [log K a + log K w − log K b ]
For dilution of HCl, 2 H2O.
M1V1 = M2V2 1 1 1 Hence, net concentration must be
= pK a + pK w − pK b
0.1 × 1 = 0.01 × V2 2 2 2 smaller than 10 −7 M.
⇒ V2 = 10 L 1 1
= × 4. 80 + 7 − × 4. 78
Volume of water to be added = 10 − 1= 9L 2 2 64 An aqueous solution of 1M NaCl and
= 7.01 1M HCl is [AIEEE 2002]

58 An acid HA ionises as (a) not a buffer but pH < 7

HA j H+ + A − 61 The pK a of a weak acid (HA) is 4.5. (b) not a buffer but pH > 7
(c) a buffer with pH < 7
The pH of 1.0 M solution is 5. Its The pOH of an aqueous buffered
(d) a buffer with pH > 7
dissociation constant would be solution of HA in which 50% of the
[AIEEE 2011] Ans. (a)
acid ionised is [AIEEE 2007]
(a) 1 × 10−10 (b) 5 (a) 4.5 (b) 2.5 NaCl is salt of strong acid and strong
(c) 5 × 10−8 (d) 1 × 10−5 (c) 9.5 (d) 7.0 base. Its not the case of buffer.
Ionic Equilibrium 107

NaCl + H2O r NaOH + HCl Ans. (d) 68 Which of the following salts is the
Aqueous NaCl, itself exact neutral During boiling, solubleMg(HCO3)2 is most basic in aqueous solution?
solution. converted into insolubleMg(OH)2 and [JEE Main 2018]
HCl + H2O r H3O+ + Cl − Ca(HCO3)2 is converted into insoluble (a) Al(CN) 3
makes solution acidic. CaCO3. This is because of high solubility (b) CH3COOK
product of Mg(OH)2 as compared to
(c) FeCl3
65 On mixing ethyl acetate with MgCO3 hence,Mg(OH)2 is precipitated.
These precipitates can be removed by (d) Pb(CH3COO)2
aqueous sodium chloride, the
filtration. Thus, filtrate will be obtained Ans. (b)
composition of the resultant
in soft water. Among the given salts
solution is [AIEEE 2004]
Mg(HCO3)2 → Mg(OH)2 ↓ + 2CO2 FeCl 3 is acidic in nature i.e., have acidic
(a) CH3COOC2H5 + NaCl
Temporary hardness solution as it is the salt of weak base and
(b) CH3COONa + C2H5OH strong acid.
Ca(HCO3)2 → CaCO3 ↓ + CO2 + 2H2O
(c) CH3COCl + C2H5OH + NaOH Al(CN) 3 and Pb(CH3COO)2 are the salts of
K sp of Mg(OH)2 > K sp of MgCO3
(d) CH3Cl + C2H5COONa weak acid and weak base.
and hence,Mg(OH)2 precipitation first.
Ans. (a) CH3COOK is the salt of strong base and
weak acid.
Aqueous NaCl is neutral, hence there is 67 The pH of a 0.02 M NH4Cl solution
no reaction between ethyl acetate and Hence, the solution of CH3COOK will be
aqueous NaCl.
will be [Given K b (NH4OH) = 10 −5 and most basic because of the following
log2 = 0.301] [2019, 10 April Shift-II] reaction.
(a) 4.65 (b) 2.65 CH3COOK + H2O - CH COOH 3
TOPIC 5 (c) 5.35 (d) 4.35 (Weak acid)
+ KOH
Hydrolsis of Salts Ans. (c) (Strong base)

Key Idea NH4 Cl is a salt of weak base 69 pH of 0.005 M calcium acetate

66 Given below are two statements : (NH4OH) and strong acid (HCl). On (pK a of CH3COOH = 4.74) is
One is labelled as Assertion (A) and hydrolysis, NH4 Cl will produce an acidic [AIEEE 2002]
the other labelled as Reason (R). solution (pH < 7) and the expression of pH (a) 7.04 (b) 9.37
of the solution is (c) 9.26 (d) 8.37
Assertion (A) During the boiling of
water having temporary hardness, 1 Ans. (a)
pH = 7 − (pK b + log C)
Mg(HCO 3 ) 2 is converted to MgCO 3 . 2 Calcium acetate is a salt of weak acid
Given,K b (NH4OH) = 10 −5 and weak base.
Reason (R) The solubility product
∴ pK b = −log K b = − log(10 −5 ) = 5 0.005 M calcium acetate, (CH3COO)2 Ca
of Mg(OH) 2 is greater than that of
C = concentration of salt solution = 0.02 M (CH3COO)2 Ca → Ca2 + + 2CH3COO−
MgCO 3 . (2 × 0.005 = 0.01)
= 2 × 10 −2 M 0.005 M
In the light of the above 1 −
Now, pH = 7 − (pK b + log C) ∴ [CH3COO ] = 0.01 M
statements, choose the most 2
CH3COO− + H2O r CH3COOH
appropriate answer from the On substituting the given values in above
equation, we get + OH –
options given below pK a log C Alkaline
1 pH = 7 + +
(a) Both (A) and (R) are true but (R) is not = 7 − [5 + log(2 × 10 −2 )]
the correct explanation of (A). 2 2 2
1 log 0.01
(b) (A) is true but (R) is false. = 7 − [5 + log 2 − 2] = 7 + 2.37 +
(c) Both A and R are true and R is the 2 2
correct explanation of (A). 1 = 7 + 2.37 − 2.30
= 7 − [5 + 0.301 − 2]
(d) (A) is false but (R) is true. 2 = 7.04
[2021, 18 March Shift-I] = 7 − 165
. = 535
.
09
Redox Reactions
TOPIC 1 (d) C2O24 − → 2CO2 The maximum and minimum possible
Oxidation, Reduction and 2x − 8 − 2 = 0 x =4
oxidation state value for Br are + 7 and
x=5
Oxidation Number (∴1 e − change) − 1 respectively. So,BrO−4 cannot oxidise
Hence, in the process ofMnO−4 to Mn2 + further. Hence, it cannot show
the change in oxidation state is five. disproportionation reaction.
01 The sum of oxidation states of two
silver ions in [Ag(NH3 ) 2] [Ag(CN) 2] 05 In basic medium, H2O 2 exhibits
complex is …… . [2021, 1 Sep Shift-II] 03 Cu 2+ salt reacts with potassium
iodide to give [2021, 20 July Shift-II] which of the following reactions ?
Ans. (2)
(a) Cu2I2 (b) Cu2I3 A. Mn 2+ → Mn 4+ B. I 2 → I–
[Ag(NH3)2 ][Ag(CN)2 ] complex
dissociates into [Ag(NH3)2 ] + and (c) CuI (d) Cu(I3)2 C. PbS → PbSO 4
[Ag(CN)2 ]. Ans. (a) Choose the most appropriate
Oxidation of Ag in [Ag(NH3)2 ] + Cu2 + salt react with potassium iodide to answer from the options given
Ag + 0 × 2 = + 1 give Cu2I2 (white ppt.) below. [2021, 18 March Shift-II]
Ag = + 1 2Cu2 + (aq)+ 4I− (aq) → Cu2I2 ( s ) + I2 (a) A and C (b) Only A
Oxidation state of Ag in [Ag(CN)2 ] − (White ppt.) (c) Only B (d) A and B
Ag + (−1) × 2 = − 1 In this reaction, Cu2 + gets reduced to Ans. (d)
Ag − 2 = −1 Cu+ and I− gets oxidised to I2 . In basic medium, oxidising action of H2O2
⇒ Ag = + 1
Mn2 + + H2O2 → Mn4+ + 2OH−
∴ Sum of oxidation states of two silver 04 The species given below that does In basic medium, reducing action ofH2O2
ions in
[Ag(NH3)2 ][Ag(CN)2 ] complex is 2.
not show disproportionation I2 + H2O2 + 2OH− → 2I− + 2H2O + O2
reaction is [2021, 20 July Shift-I] In acidic medium, oxidising action of H2O2
02 Identify the process in which (a) BrO −4 (b) BrO − PbS (s ) + 4H2O2 (aq) →
change in the oxidation state is five (c) BrO2− (d) BrO −3 PbSO4 (s ) + 4H2O (l )
[2021, 25 July Shift-II] Ans. (a) Thus, in basic mediumH2O2 exhibits
(a) Cr2O27− → 2Cr 3+ BrO−4 will not undergo disproportionation reaction ‘A’ and ‘B’
(b) MnO −4 → Mn2 + because bromine is in its maximum Hence, correct option is (d).
(c) CrO24− → Cr 3+ oxidation state, i.e. + 7.
(d) C2O24− → 2CO2 For a species to undergo 06 Given below are two statements.
Ans. (b) disproportionation, the oxidation state Statement I Potassium
of the element undergoing
Change in oxidation state in different disproportionation should lie between its
permanganate on heating at 573 K
process is as follows : maximum and minimum possible forms potassium manganate.
(a) Cr2O27 − → 2Cr 3 + oxidation values. Statement II Both potassium
2x − 14 − 2 = 0 x =6
In option (a), we have the oxidation state permanganate and potassium
2x = 16
(∴ 2e − change) of Br = + 7 manganate are tetrahedral and
x=8
(b) MnO−4 → Mn 2+ In option (b), we have oxidation state of paramagnetic in nature.
x − 8+ 1=0 x =2 Br = + 1
x=7 (∴5 e − change) In option (c), we have oxidation state of
In the light of the above
(c) Cr O24 − → Cr 3+ Br = + 3 statements, choose the most
x − 8−2=0 x =3 In option (d), we have oxidation state of appropriate answer from the
x = 10 (∴7 e − change) Br = + 5 options given below
[2021, 17 March Shift-I]
Redox Reactions 109

(a) Statement I is true but statement II 08 Which of the following equation 11 On heating, lead (II) nitrate gives a
is false.
depicts the oxidising nature of brown gas (A). The gas (A) on
(b) Both statement I and statement II
are true.
H2O 2 ? [2021, 25 Feb Shift-I] cooling changes to a colourless
(c) Statement I is false but statement II (a) KIO 4 + H2O2 → KIO 3 + H2O + O2 solid/liquid (B). (B) on heating with
is true. (b) I2 + H2O2 + 2OH− → 2I− + 2H2O + O2 NO changes to a blue solid (C). The
(d) Both statement I and statement II (c) 2I− + H2O2 + 2H+ → I2 + 2H2O oxidation number of nitrogen in
are false. (d) Cl2 + H2O2 → 2HCl + O2 solid (C) is [2020, 4 Sep Shift-I]
Ans. (a) Ans. (c) (a) + 5 (b) + 4
Potassium permanganate on heating at Oxidation involves increase in oxidation (c) + 2 (d) + 3
573 K forms potassium manganate. number and reduction involves decrease Ans. (d)
+7 +6 in oxidation number. On heating lead (II) nitrate following
KMnO4 573
K→ K2 MnO4 + MnO2 + O2 1 −1 0 + 1 −2
Potassium Potassium 2I– + 2H+ +H2 O2 → I2 + 2H2 O reaction takes place.
permanganate manganate 1
In this reaction,H2O2 oxidises I− to I2 and Pb(NO3)2 → PbO + 2NO2 + O2 (g)
(Diamagnetic) (Paramagnetic) 2
(Lead nitrate) (A )
itself gets reduced toH2O, so the Brown gas
Both potassium permanganate and
reaction depicts oxidising nature of H2O2 .
potassium manganate are tetrahedral. Gas, NO2 (A) on cooling givesN2O4 (B).
While in other reactionsH2O2 does not
Manganese has four sigma bonds oxidise KIO4 , I2 and Cl2 . Cooling
forming tetrahedral structure. 2 NO2 (g) → N2O4
Brown gas (B)
09 The oxidation states of iron atoms Colourless solid/liq. N2O4 (B) on reaction
O – O 2–
in compounds (A), (B) and (C), with NO givesN2O3.
+ +
K Mn 2K Mn respectively, are x, y and z. The sum D
N2O4 + 2NO → N2O3
of x, y and z is (B) (C )
O O
Tetrahedral unit Tetrahedral unit Na 4 [Fe(CN) 5 (NOS)], Blue solid
Oxidation state of N inN2O3 (C).
KMnO4 ; + 1 + x − 8 = 0, ( A)
Na 4 [FeO 4], [Fe 2 (CO) 9 ] N2O3 ⇒ 2x + 3(−2) = 0
x=+ 7
6
K2MnO4 ; + 2 + x − 8 = 0 ( B) (C ) 2x = + 6 ⇒ x = = + 3
2
x=+6 [2020, 9 Sep Shift-I]
So, oxidation state is + 3.
So, Mn is present in + 7 oxidation state in Ans. (6)
KMnO4 and + 6 oxidation state inK2MnO4 . Na[Fe (CN) 5 NOS] ⇒4 × (+ 1) + x + 5 12 Oxidation number of potassium in
Mn = [Ar] 4s 2 3d 5 × (−1) + (+ 1) + (− 2) = 0
25 K 2O, K 2O 2 and KO 2 , respectively, is
Mn+ 7 = [Ar] 4s 0 3d 0 (Diamagnetic) ⇒x=+2 [2020, 7 Jan Shift-I]
Mn+6 = [Ar] 4s 1 CN – S 2–
(Paramagnetic) (a) +1, +4 and +2 (b) +1, + 2 and +4
So, potassium permanganate is NO + 1
y (c) +1, + 1 and +1 (d) +2, + 1 and +
diamagnetic and potassium manganate 2
Na4 [FeO4 ] ⇒4(+ 1) + y + 4 × (− 2) = 0
is paramagnetic.
⇒y=+4 Ans. (c)
Statement I is true but statement II is
false. [Fe2 (CO) 9 ] ⇒2 × z + 9 × 0 = 0 ⇒z = 0 Elements of group 1 (alkali metals) show
So, x + y + z = (+ 2) + (+ 4) + (0) = 6 only one non-zero oxidation number,
which is equal to + 1 .
07 Dichromate ion is treated with
10 The oxidation states of transition K2O consists of K+ and O2 − ions
base, the oxidation number of Cr in
metal atoms in K 2Cr 2O 7 , KMnO 4 K2O2 (potassium peroxide) consists ofK+
the product formed is ………… .
and K 2FeO 4 , respectively, are x, y and O22 − ions. KO2 (potassium superoxide)
[2021, 26 Feb Shift-I]
consists of K+ and O2− ions.
Ans. (6) and z. The sum of x, y and z is
Thus, in all the given compounds
In basic medium dichromate ion (Cr2O27− ) ……… . [2020, 2 Sep Shift-II]
potassium exhibits +1 oxidation state.
changes in chromate ion (CrO24− ). Ans. (19)
Oxidation state of Cr in CrO24− is +6. x
13 The redox reaction among the
K2 Cr2O7 ⇒2(+ 1) + 2x + 7 × (− 2) = 0
⇒ CrO24− = x + 4(−2) = − 2 following is [2020, 7 Jan Shift-II]
or x = + 6. ⇒ x=+6
y (a) reaction of H2SO4 with NaOH
Dichromate and chromate equilibrium KMnO4 ⇒1 × (+ 1) + x + 4 × (− 2) = 0 (b) reaction of [Co(H2O) 6 ]Cl 3 with AgNO3
depends on pH of the medium as ⇒ y=+ 7 (c) combination of dinitrogen with
+6 OH − (pH > 7) z dioxygen at 2000 K
Cr2 O27− 4 CrO24− K2 FeO4 ⇒2 × (+ 1) + z + 4 × (− 2) = 0
H + (pH < 7) (aq ) (d) formation of ozone from
(aq )
(Orange) (Yellow) ⇒ z=+6 atmospheric oxygen in the presence
So, (x + y + z) = 6 + 7 + 6 = 19 of sunlight
110 JEE Main Chapterwise Topicwise Chemistry

−2
Ans. (c) Here, CuBr get oxidised to CuBr2 and (A) H2O2−1 + 2H+ + 2e − → 2H2 O
(a) The given reactions are as follows: also it get reduced to Cu. Other given
reactions and their types are given In this reaction,H2O2 undergoes
H2SO4 +2NaOH → Na2SO4 + 2H2O below. reduction asO shows increase in
(+6) (+1) (+1) (+6) Reduction oxidation number.
(No change in oxidation state, so not +7 −1 0
a redox reaction). 2
–
MnO4 +10–I + 16 H
+ +2
2Mn + 5I2 + 8H2O (B) H2 O 2 − 2e − → O 2 + 2H+
(b) [Co(H2O) 6 ]Cl 3 + 3 AgNO3 → In this reaction,H2O2 undergoes
(+3) Oxidation
(+1)
oxidation as it shows decrease in
In the given reaction,MnO−4get oxidised
[ Co (H2O) 6 ](NO3) 3 + 3AgCl↓ 2+ − oxidation number. Thus,H2O2 acts
(+ 3) to Mn and I get reduced toI2 . It is an
(+ 1) as a reducing agent.
(No change in oxidation state, so not a example of redox reaction. The reaction −1 −2
redox reduction). takes place in acidic medium. (C) H2 O 2 + 2e − → 2 O H−
(c) N2 +O2 → 2N O
200 K 2KMnO4 → K2MnO4 + MnO2 + O2 In this reaction,H2O2 undergoes
(+2) (−2)
(0) (0) The given reaction is an example of reduction.
−1
(N2 oxidised from 0 to +2 oxidation state decomposition reaction. Here, one 0
(D) H2 O 2 + 2OH− − 2e − → O 2 + 2H2O
and O2 reduced from 0 to −2 oxidation compound split into two or more simpler
state). compounds, atleast one of which must In this reaction,H2O2 undergoes
∴ This is redox reaction. be in elemental form. reduction. Thus, acts as a reducing
agent.
hν 2NaBr + Cl2 → 2NaCl + Br2
(d) 3O2 s 2O3
The given reaction is an example of
(0 ) (0 )
displacement reaction. In this reaction,
18 The metal that cannot be obtained
(No change in oxidation states, so not a by the electrolysis of an aqueous
an atom (or ion) replaces the ion (or
redox reaction). solution of its salts is
atom) of another element from a
compound. [JEE Main 2014]
14 The compound that cannot act (a) Ag (b) Ca (c) Cu (d) Cr
both as oxidising and reducing 16 Which of the following reactions is Ans. (b)
agent is [2020, 9 Jan Shift-II] an example of a redox reaction? Higher the position of element in the
(a) H2 SO 3 (b) H3PO 4 [JEE Main 2017]
electrochemical series, more difficult is
(c) HNO2 (d) H2O2 (a) XeF4 + O2F2 → XeF6 + O2 the reduction of its cation. Thus, among
Ans. (b) (b) XeF2 + PF5 → [XeF] + PF6− all the given elements, only calcium on
In H3PO4 , P is in its highest oxidation electrolysis yieldsH2 gas at cathode
(c) XeF6 + H2O → XeOF4 + 2HF while other yields pure metals at
state (+5), it can only act as oxidising
agent but not as reducing agents, (d) XeF6 + 2H2O → XeO2F2 + 4HF cathode. In case of Ca2 + ion, water is
because it can be reduced but not Ans. (a) reduced in preference to calcium.
oxidised. For Cr At cathode, Cr 3+ + 3 e − → Cr
The reaction in which oxidation and
H2SO3 : S = + 4 can get oxidised or reduction occur simultaneously are For Ag At cathode, Ag + + e − → Ag
reduced. termed as redox reaction. For Cu At cathode, Cu2 + + 2e − → Cu
HNO2 : N = + 3 can get oxidised or +4 +1 +6 0
( X ) eF4 + O2 (F2 ) → X eF6 + O2
reduced. For Ca2 + At cathode,
H2O2 : O = − 1 can get oxidised or reduced. Since, Xe undergoes oxidation while O 1
undergoes reduction. So, it is an H2O + e − → H2 + OH−
2
15 An example of a disproportionation example of redox reaction.
reaction is [2019, 12 April Shift-I] 19 Which of the following chemical
17 In which of the following reactions
(a) 2MnO −4 + 10 I− + 16H+ → reactions depicts the oxidising
H2O 2 acts as a reducing agent?
2Mn2 + + 5I2 + 8H2O [JEE Main 2014] behaviour of H2SO 4 ? [AIEEE 2006]
(b) 2NaBr + Cl2 → 2NaCl + Br2 A. H2O2 + 2H+ + 2e − → 2H2O (a) 2HI + H2 SO 4 → I2 + SO2 + 2H2O
(c) 2KMnO 4 → K2MnO 4 + MnO2 + O2 B. H2O2 − 2e − → O2 + 2H+ (b) Ca(OH)2 + H2 SO 4 → CaSO 4 + 2H2O
(d) 2CuBr → CuBr2 + Cu C. H2O2 + 2e − → 2OH− (c) NaCl + H2 SO 4 → NaHSO 4 + HCl
Ans. (d) D. H2O2 + 2OH− − 2e − → O2 + 2H2O (d) 2PCl5 + H2 SO 4 → 2POCl3 + 2HCl
In disproportionation reactions, same (a) A, B (b) C, D
+ SO2Cl2
element undergoes oxidation as well as (c) A, C (d) B, D
Ans. (a)
reduction. Ans. (d) −1 +6 0 +4
e.g. Reduction
The reducing agent oxidises itself by 2HI +H2SO4 → I2 +SO2 + 2H2O
+1 +2 0
undergoing oxidation through the loss of
2CuBr CuBr2 +Cu H2SO4  Reduced to → SO2
electrons. Thus, reducing agent reduces
other molecules by supplying electrons Oxidising
Oxidation agent
to them.
Redox Reactions 111

20 The oxidation state of Cr in 24 MnO −4 is a good oxidising agent in Ans. (16)

[Cr(NH3 ) 4 Cl 2] + is [AIEEE 2005] different medium changing to Balancing by half-reaction method
(b) + 1 (c) + 2 (d) + 3 2MnO4− + bC2O24− + cH+ →
(a) 0 MnO −4 → Mn 2+ → MnO 24−
Ans. (d)
+7 +3 x Mn+2 + y CO2 + zH2O
→ MnO 2 → Mn 2O 3 +2
+4
[Cr(NH3) 4 Cl2 ] +
Changes in oxidation number Step 1 Separate two half-reactions
Let the oxidation state of Cr = x; NH3 = 0;
Cl = − 1
respectively, are [AIEEE 2002] Oxidation half (O.H.) C2O24− → CO2
Net charge = + 1 (a) 1, 3, 4, 5 (b) 5, 4, 3, 2 Reduction half (R.H.) MnO−4 → Mn2 +
(c) 5, 1, 3, 4 (d) 2, 6, 4, 3
∴ [Cr(NH3) 4 Cl2 ] + Step 2 Balance all the atoms except
Ans. (c) oxygen and ‘H’.
x + 4 × 0 + 2 (− 1) = + 1 ⇒ x = 3
+7
O.H. C2O24– → 2CO2
MnO4− → Mn2 + change 5
21 The oxidation state of chromium in +6 R.H. MnO−4 → Mn2 +
the final product formed by the → MnO24 − change 1 Step 3 Balance ‘O’ by addingH2O and ‘H’ by
reaction between KI and acidified +4 addingH+ .
→ MnO2 change 3
potassium dichromate solution is +3 O.H. C2O24– → 2CO2
[AIEEE 2005] → Mn2O3 change 4 R.H. 8H + MnO−4 → Mn2 + + 4H2O
+

(a) + 3 (b) + 2 Step 4 Balance charge by adding

(c) + 6 (d) + 4 25 Which of the following is a redox electron
Ans. (a) reaction ? [AIEEE 2002]
O.H C2O24– → 2CO2 + 2e −
Cr2O27− −
+ 14H + 6I → 2Cr
+ 3+ (a) NaCl + KNO 3 → NaNO 3 + KCl
(b) CaC2O 4 + 2HCl → CaCl2 + H2C2O 4 R.H. 5e − + 8H+ + MnO−4 → Mn2 + + 4H2O
+ 7H2O + 3I2
(c) Ca(OH)2 + 2NH4Cl → CaCl2 Step 5 Balance electron by multiplying
Cr2O27− is reduced to Cr 3+ .
O.H. by ‘5’ and R.H. by ‘2’.
Thus, final state of Cr is + 3. + 2NH3 + 2H2O
O.H. 5C2O24− → 10 CO2 + 10 e −
(d) 2K [Ag(CN)2] + Zn → 2Ag R.H. 10e − + 16H+ + 2MnO4− →
22 Among the properties (A) reducing,
+ K2 [Zn(CN) 4] 2Mn2 + + 8H2O
(B) oxidising and (C ) complexing,
Ans. (d) Step 6 Add both half-reaction
the set of properties shown by CN − +1 − 1 + 1 −1 +1 −1 + 1− 1 16H+ + 5C2O24– + 2MnO−4 →
ion towards metal species is (a) Na Cl + K NO3 → NaNO3 + K Cl
[AIEEE 2004] +2 −2 +1− 1 + 2 −1
10CO2 + 2Mn2 + + 8H2O
(a) A, B (b) B, C (b) Ca C2 O4 + 2 H Cl → Ca Cl2 So, c = 16
(c) C, A (d) A, B, C +1 −2
+H2 C2 O4 27 In basic medium CrO 2−
Ans. (c) 4 oxidises
+2 −1 − 3 +1 − 1 + 2 −1 2− 2−
CN− is a better complexing agent (C) as (c) Ca(OH)2 +2NH4 Cl → Ca Cl2 S 2O 3 to form SO 4 and itself
well as a reducing agent (A). −3 + 1 + 1 −2 changes into Cr(OH) −4 . The volume
+2NH3 + 2H2 O
Thus, properties (A) and (C) are shown of 0.154 M CrO 2−
4 required to react
Property (C) :
In all these cases during reaction, there with 40 mL of 0.25 M S 2O 2−3 is
is no change in oxidation state of ion or ………… mL
Ni2 + + 4CN− → [Ni(CN) 4 ]2 − molecule or constituent atom. These are
simply ionic reactions. (Rounded off to the nearest
Property (A) :
(d) 2K[Ag(CN)2 ] + Zn → 2Ag integer). [2021, 25 Feb Shift-I]
CuCl2 + 5KCN → K3 [Cu(CN) 4 ]
II I + K2 [Zn(CN) 4 ] Ans. (173)
1
+ (CN)2 + 2KCl Ag + → Ag gain of e − , reduction Given, Molarity of CrO24− (M1) = 0.154 M
2
Zn → Zn2 + loss of e − , oxidation Molarity of S2O23− (M2 ) = 0.25M
[CN reduces Cu2 + to Cu+ ]
Volume of S2O23− (V2 ) = 40 mL
23 Oxidation number of Cl in CaOCl 2 Volume of CrO24− (V1) = ?
TOPIC 2 +6 2 – +6 2 – +6 +3
(bleaching powder) is [AIEEE 2002] Balancing of CrO4 + S2 O3 → SO24− + Cr(OH) 4−
(a)zero, since it contains Cl2 Gram equivalent of CrO24− = Gram
(b)− 1, since it contains Cl− Chemical Equations equivalent of S2O23−
(c)+ 1, since it contains ClO − N 1V1 = N2V2
(d)+1 and − 1, since it contains ClO − 26 2MnO −4 + bC 2O 24− + cH+ →
Normality = Molarity × n factor
and Cl− x Mn 2+ + y CO 2 + zH2O n for Cr = 6 − 3 = 3
Ans. (d) If the above equation is balanced n for S ⇒S2O23– → 2 SO24– + 8e −
CaOCl2 is written basically as Ca(OCl)Cl. with integer coefficients, the 0.154 × 3 × V1 = 0.25 × 40 × 8
OCl − → Cl has + 1 oxidation state value of c is ……… .
Cl − → Cl has − 1 oxidation state [2021, 16 March Shift-I]
V1 = 173 mL
112 JEE Main Chapterwise Topicwise Chemistry

28 The reaction of sulphur in alkaline H2O2 + 2e − → 2HO− Ans. (c)

medium is given below 2Fe2 + + H2O2 → 2Fe3+ + 2HO− Reaction of oxalate with permanganate
( A) ( B)
in acidic medium.
S 8 (s) + aOH− (aq) → Hence, x = 2 and y = 2 .
bS 2 − (aq) + cS 2 O 23 − (aq) + dH2O (l) In acidic medium 5C2O24− + 2MnO4− → 10CO2 + 2Mn2 + + 8H2O
The value of ‘a’ is ....... . (Integer [8H+ + MnO−4 + 5e − → Mn2 + + 4H2O] × 2 n-factor : (4 − 3) × 2 = 2 (7 − 2) = 5
answer) [2021, 24 Feb Shift-I] [H2O2 → O2 (g) + 2H+ +2e − ] × 5 No. of 5 2 10
Ans. (12) 16H+ + 2MnO4− + 5H2O2 → 2Mn2 + mole
(C )
The two half reaction, one separately are ⇒ 5C2O24– ions transfer 10 e − to produce
+ 8H2O + 5O2 (g) 10 molecules of CO2 . So, number of
as follows (D ) (E )
S8 + 16 e − → 8 S2 − electrons involved in producing
(Reduction) So, x ′ = 2, y ′ = 8, z ′ = 5 10 molecules of CO2 is 10.
S 8 + 12H2O → 4S2O23− + 24 H+ + 16e− So, x + y + x′ + y′ + z′ Thus, number of electrons involved in
2S 8 + 12 H2O → 8S2 − + 4S2O23− + 24H+ ⇒ 2 + 2 + 2 + 8 + 5 ⇒19 producing 1 molecule of CO2 is 1.
(Oxidation)
30 In order to oxidise a mixture of one 32 Consider the following reaction,
For balancing in basic medium,
mole of each of FeC 2O 4 , x MnO −4 + y C 2O 24− + z H+ →
Add an equal number ofOH− that of H + ,
Fe 2 (C 2O 4 ) 3 , FeSO 4 and Fe 2 (SO 4 ) 3 z
we get
in acidic medium, the number of xMn 2+ + 2y CO 2 + H2O
2S 8 + 12H2O + 24OH− → 8S2 − + 4S2O23 − 2
moles of KMnO 4 required is
+24H2O [2019, 8 April Shift-I] The values of x, y and z in the
2S 8 + 24OH− → 8S2 − + 4S2O23− (a) 2 (b) 1 (c) 3 (d) 1.5 reaction are, respectively
+ 12H2O Ans. (a)
[AIEEE 2013]
or S 8 + 12OH− → 4S2 − + 2S2O23− (a) 5, 2 and 16
The oxidation of a mixture of one mole of (b) 2, 5 and 8
+ 6H2O …(i)
each of FeC2O4 , Fe2 (C2O4 ) 3 FeSO4 and
On comparing (i) with (c) 2, 5 and 16
Fe2 (SO4 ) 3 in acidic medium withKMnO4 is
S 8 + aOH− (aq) → bS2 − (aq) + c S2O23− (d) 5, 2 and 8
as follows
+ dH2O FeC2O4 + KMnO4 → Fe3+ + CO2 + Mn2 +
Ans. (c)
We get,a = 12; b = 4; c = 2; d = 6 …(i) The half equations of the reaction are
Fe2 (C2O4 ) 3 + KMnO4 → Fe3+ + CO2 MnO–4 → Mn2 +
29 Consider the following equations : + Mn2 + …(ii) C2O24– → CO2
2Fe 2+ + H2O 2 → xA + yB FeSO4 + KMnO4 → Fe + SO24− + Mn2 +
3+
The balanced half equations are
(in basic medium) …(iii) (MnO–4 + 8 H+ + 5 e −
2MnO −4 + 6H+ + 5H2O 2 → Change in oxidation number of Mn is 5. → Mn2 + + 4H2O) × 2
Change in oxidation number of Fe in (i),
x ′ C+ y ′ D + z ′ E (ii) and (iii) are +3, + 6, + 1, respectively. (C2O24– → 2CO2 + 2e − ) × 5
(in acidic medium) neqKMnO4 Equating number of electrons, we get
The sum of the stoichiometric = neq [FeC2O4 + Fe2 (C2O4 ) 3 + FeSO4 ] 2MnO–4 + 16 H+ + 10 e −
coefficients x, y, x ′ , y ′ and z′ for n× 5 = 1 × 3 + 1 × 6 + 1 × 1 ⇒ n = 2 → 2Mn2 + + 8H2O
products A, B, C, D and E, 5C2O24– → 10CO2 + 10 e −
respectively, is ……… . 31 In the reaction of oxalate with On adding both the equations, we get
[2020, 4 Sep Shift-II] permanganate in acidic medium,
2MnO–4 + 5C2O4– + 16 H+ → 2Mn2 +
Ans. (19) the number of electrons involved in 16
producing one molecule of CO 2 is + 2 × 5 CO2 + H2O
In basic medium 2
[Fe2 + → Fe3+ + e − ] × 2 (a) 2 (b) 5 (c) 1 (d) 10
Thus, x, y and z are 2, 5 and 16, respectively.
[2019, 10 Jan Shift-II]
10
Electrochemistry
Choose the most appropriate [where, Λm = molar conductivity]
TOPIC 1 answer from the options given 1.14 × 10 3
Electrolytic Conductance = = 760 S cm2 mol −1.
below [2021, 31 Aug Shift-II] 1500 × 0.001
Electrolysis and its A B C D A B C D
Quantitative Aspect (a) 3 1 4 2 (b) 3 1 2 4 04 The conductivity of a weak acid HA
(c) 1 4 3 2 (d) 2 1 3 4 of concentration 0.001 mol L −1 is
01 If the conductivity of mercury at
2.0 × 10 −5 S cm −1 . If Λ°m (HA) = 190 S
0°C is 1.07 × 10 6 S m −1 and the Ans. (a)
resistance of a cell containing (A) Cell constant =
l −1
m cm 2 mol −1 , the ionisation constant
mercury is 0.243 Ω, then the cell A (K a ) of HA is equal to
constant of the cell is x × 10 4 m −1 . (B) Molar conductivity ………… × 10 −6 . (Round off to the
κ × 1000
The value of x is ……… . (Nearest (λ m ) = Scm2 mol −1 nearest integer)
molarity [2021, 27 July Shift-I]
integer) [2021, 1 Sep Shift-II]
1 1 −1 −1
Ans. (26) (C) Conductivity (κ) = = Ω m Ans. (12)
ρ RA
Using formula for molar conductivity.
Conductance (G) is reciprocal of (D) Degree of dissociation of electrolyte Conductivity (κ)
resistance (R). = Number of moles dissociated out of Λm = 1000 ×
1 1 1 Concentration (M)
R= or G = = one mole.
G R 0.243 Ω 2 × 10 − 5
It is a ratio. Hence, it is dimensionless. = 1000 ×
−1
= 4.115 Ω Thus, the correct match is 0.001
Relation between conductance (G), A → 3, B→ 1, C → 4, D → 2. = 20 S cm2 mol − 1
⇒ Degree of dissociation,
conductivity (κ) and cell constant   is
l
03 The resistance of a conductivity Λ 20 2
 A α = ∞m = =
given as cell with cell constant 1.14 cm − 1 , Λm 190 19

κ=
Gl containing 0.001 M KCl at 298 K is where (use the symbol and meaning
A 1500 Ω. The molar conductivity of marked)
l κ 1.07 × 10 6 S m−1 0.001 M KCl solution at 298 K in S HA q H+ + A −
⇒ = = 0.001(1 − α) 0.001 α 0.001 α
A G 4.115 Ω −1 cm 2 mol − 1 is .......... . (Integer
answer)  α2 
= 26 × 10 4 m−1 ⇒ x = 26 [2021, 27 Aug Shift-II] ⇒ K a = 0.001  
∴ Answer is 26. Ans. (760)  1−α
Given,G * = 1.14 cm−1 = 1.14 × 10 3 m−1
2
2
0.001 ×  
02 Match List-I with List-II. R = 1500 Ω  19 
= = 12.3 × 10 − 6
C = 0.001 M 2
List-I List-II 1−  
(Parameter) (Unit) G*=R ×κ  19 
A. Cell constant 1. S cm2 mol − 1 [where, R = resistance
G * = cell constant 05 Given below are two statements.
B. Molar 2. Dimensionless
conductivity κ = conductivity Statement I The limiting molar
C. Conductivity 3. m − 1 C = concentration] conductivity of KCl (strong
G * 1.14 × 10 3 m−1 electrolyte) is higher compared to
D. Degree of 4. Ω − 1m − 1 ∴ κ= =
dissociation of R 1500 that of CH3COOH (weak
electrolyte κ electrolyte).
Λm =
C
114 JEE Main Chapterwise Topicwise Chemistry

Statement II Molar conductivity W=

E
×I ×t QQ = E  Cell constant
l
= 1.3 cm−1
 
F  F A
decreases with decrease in
where, W = weight of potassium chlorate κ
concentration of electrolyte. Λm =
E = Molar mass of potassium chlorate 1000 × C
In the light of the above F = Faraday’s constant where, Λm = molar conductivity
statements, choose the most I = Current κ = conductivity,C = molarity
appropriate answer from the t = Time for which current is passed l
Conductivity (κ) = G
options given below 10 =
.
1226
× x × 10 × 3600 A
[2021, 26 Aug Shift-I] 96500 × 6 = 0.55 × (1.3 × 100)
(a) Statement I is true but statement II 96500 × 6 × 10 = 55 × 1.3
x=
is false. 10 × 3600 × 122.6 55 × 1.3
Λm =
(b) Statement I is false but statement II
⇒ x = 1.311 1000 × 5 × 10 −3
is true. Λm = 14.3
(c) Both statement I and statement II 07 A KCl solution of conductivity Closest integer,
are true. 0.14 S m −1 shows a resistance of Λm = 14
(d) Both statement I and statement II
4.19 Ω in a conductivity cell. If the
are false. 09 Consider the following reaction,
same cell is filled with an HCl
Ans. (d) solution, the resistance drops to MnO −4 + 8H+ + 5e − →
Limiting molar conductivity of KCl 1.03 Ω. The conductivity of the HCl Mn 2+ +4H2O, E° = 1.51 V.
Λ°m KCl = Λ∞m (K+ ) + Λ∞m( Cl − ) solution is ……… × 10 −2 S m −1 The quantity of electricity
= 73.55 S cm2 /mol + 76.3 S cm2 /mol (Round off to the nearest integer) required in Faraday to reduce five
= 149.3 S cm2 /mol
moles of MnO −4 is ………… .
[2021, 17 March Shift-II]
Limiting molar conductivity of CH3COOH Ans. (57) [2021, 26 Feb Shift-I]
Λ°m (CH3COOH) = Λ∞m (CH3COO− ) + Λ∞m(H+ ) Given, Ans. (25)
= 349.8 S cm2 /mol + 40.9 S cm2 /mol Conductivity of KCl solution kKCl In the reduction half-cell,
= 390.7 S cm2 /mol = 0.14 Sm− 1
MnO4− + 8H+ + 5 e − → Mn2 + + 4H2O
∴ Limiting molar conductivity of RKCl = 4.19 ohm 1 mol 5F
CH3COOH is more than KCl. Hence, RHCl =1.03 ohm 5 mol 25 F
statement I is false. To find conductivity of HCl solution kHCl As one mole of MnO−4 required 5F of
Also, as the concentration decreases, We know that, charge,
dilution of the electrolyte increases k = 1/R ⋅ G * 5 moles of MnO−4 will require charge,
which will increase the degree of
where k is the conductivity, R is the Q = 5 × 5 Faraday = 25 Faraday
dissociation of weak electrolyte. Thus,
the number of ions in the solution resistance andG * is the cell constant.
increases and hence, the molar As k is constant. Therefore, k and G * 10 Amongst the following, the form of
conductance of electrolyte increases. constant water with the lowest ionic
Therefore, we can see that with ∴ kKCl ⋅ RKCl = kHCl ⋅ RHCl conductance at 298 K is
decrease in concentration of electrolyte, Therefore, 0.14 × 4.19 = k × 103
. [2020, 9 Jan Shift-II]
molar conductance increases. 0.14 × 4.19 (a) saline water used for intravenous
or, k of HCl solution =
Hence, statement II is also false. 103
. injection
= 0.5695 Sm− 1 = 5695. × 10 − 2 Sm− 1 (b) distilled water
06 Potassium chlorate is prepared by = 57 × 10 − 2 Sm− 1 (c) water from a well
electrolysis of KCl in basic solution (d) sea water
as shown by following equation 08 A 5.0 m mol dm −3 aqueous Ans. (b)
6OH− + Cl − → CIO −3 + 3H2O + 6e − solution of KCl has a conductance Among the given options, distilled water
A current of xA has to be passed of 0.55 mS when measured in a cell has the lowest ionic conductance at 298
for 10th to produce 10.0 g of constant 1.3 cm −1. K.
potassium chlorate. The value of x The molar conductivity of this Water from well or sea contains mineral
ions,
is …… . (Nearest integer) solution is …… mSm 2 mol −1 .
∴ they have ionic conductance.
(Molar mass of (Round off to the nearest integer) Saline water is an electrolyte and contain
KClO 3 = 122.6 g mol −1 , F = 96500 C ) [2021, 16 March Shift-II] ions.
[2021, 20 July Shift-II] Ans. (14) ∴ It also has ionic conductance.
Ans. (1) Given, concentration of KCl
Given, balanced equation is (C) = 5 m mol / L 11 Let CNaCl and C BaSO be the
4
6OH− + Cl − → ClO−3 + 3H2O + 6e − = 5 × 10 −3 mol/L conductances (in S) measured for
W = Q ×I ×t Conductance (G) = 0.55 mS saturated aqueous solutions of
Electrochemistry 115
2 8 × 60 × 2 1 (a) HCl (b) NaCl
NaCl and BaSO 4 , respectively, at a ⇒n produced = × =
Cr 3+ 6 96000 30 (c) KNO 3 (d) CH3COOH
temperature T. Which of the
Theoritically produced Ans. (d)
following is false? [2020, 3 Sep Shift-I]
Weight 3+ =  × 52 g
1
Molar and activity, λ m is defined as the
(a) Ionic mobilities of ions from both Cr  30 
salts increase with T. conducting power of all the ion produced
[QMass of Cr = 52] by dissolving one gram mole of on
(b) C BaSO 4 (T2 ) > C BaSO 4 (T1) forT2 > T1
Weight actual = 0.104 g electrolyte in solution. it is a function of
(c) C NaCl (T2 ) > C NaCl (T1) forT2 > T1 the ionic strength of a solution.
Weight (actual)
(d) C NaCl >> C BaSO 4 at a givenT Efficiency = × 100
Weight (theoritical) The molar conductivity of both weak and
Ans. (c) strong electrolytes increases with
NaCl is a strong electrolyte, whereas Efficiency of the process decrease in concentration.
BaSO4 is a sparingly soluble (weaker) 0.104 g Molar conductivity is the conductivity
= × 100 = 60%
electrolyte. So, even in saturated  1 × 52 affered by one mole of ions.
 
solution, NaCl will almost remain in  30  Increased dilution results in the
dissociated form to give freeNa+ and dissociation of more electrolytes into
Cl − . But availibility of Ba2 + and SO24− in 13 250 mL of a waste solution ions and effectively increasing the
water will be very poor. number of active ions in the solution.
obtained from the workshop of a
But degree of dissociation ofBaSO4 will These active ions impart more
increase with a temperature to give goldsmith contains 0.1 M AgNO 3 conductivity.
more ions. and 0.1 M AuCl. The solution was
BaSO4 (s ) c Ba2 + (aq) + SO24+ (aq) electrolysed at 2 V by passing a CH3COOH

Λ/(Scm–2mol–1)
Again, with increase in temperature ionic current of 1 A for 15 minutes. The
mobility also increases. So, options (a), metal /metals electrodeposited will
(b) and (d) are true but (c) is false. ° +
be (E Ag = 0.80 V,
/Ag
Solubility of NaCl in water remains
almost constant with increase in ° +
E Au = 1.69 V) KCl
/Au [2020, 4 Sep Shift-II]
temperature. So, option (c) is false.
(a) only silver
(b) silver and gold in equal mass c1/2/mol1/2L1/2
proportion
Solubility

(c) only gold

NaCl
(d) silver and gold in proportion to their 15 Potassium chlorate is prepared by
atomic weights the electrolysis of KCl in basic
Ans. (c) solution
Temperature (°C)
(Solubility curve) it 6 OH− + Cl − → ClO 3− + 3H2O + 6e − . If
Charge (q) = F
96500 only 60% of the current is utilised
12 An acidic solution of dichromate is 1 × 15 × 60 900 9 in the reaction, the time (rounded
= = = F = 0.0093 F
electrolysed for 8 minutes using 2A 96500 96500 965 to the nearest hour) required to
current. As per the following Number of moles of Au+ = 0.01 and produce 10 g of KClO 3 using a
equation number of moles of Ag + = 0.01 current of 2 A is ........ .
Cr 2O 72− + 14H+ + 6e − → Species with higher value of standard (Given : F = 96,500 C mol −1 ; molar
°
reduction potential, (E Au + = 1 .69 V) will mass of KClO 3 = 122 g mol −1 )
2Cr 3+ + 7H2O / Au
get deposited first at cathode. [2020, 6 Sep Shift-I]
The amount of Cr 3+ obtained was Au+ (aq) + e _ → Au(s ) Ans. (11.00)
0.01 0.0093 mol
0.104 g. The efficiency of the So, only Au will get deposited. For 1 mole of ClO−3 , 6 F charge required
process(in %) is but current efficiency is only 60%. So, to
(Take : F = 96000C, atomic mass 14 The variation of molar conductivity obtain 1 mol ClO−3 , charged required is
of chromium = 52) ........... . with concentration of an 10 F.
10 g
[2020, 3 Sep Shift-II]
electrolyte (X ) in aqueous solution Now, moles of KClO3 =
Ans. (60) 122
is shown in the given figure.
10
Given, ∴ Charge = × 10 F
122
Cr2O27− + 14H+ + 6e − → 2Cr 3+ + 7H2O
 8 × 60 × 2 
Molar ∴Current using = 2 A
Number of moles =   Conductivity
 96000  Apply, W = Z × I × t
100 2
[Q F = 96000 C] ∴ = × 2 × 3600
√c 122 96500
Using stoichiometry,
ne (used) nCr 3 + (Produced) The electrolyte X is ⇒ t = 11 hrs
= [2020, 5 Sep Shift-II] Hence, the correct answer is (11).
6 2
116 JEE Main Chapterwise Topicwise Chemistry

16 The equation that is incorrect is produced at 273 K and 1 bar (a) S 1 is correct and S2 is wrong
[2020, 7 Jan Shift-II] pressure from water by the same (b) S 1 is wrong and S2 is correct
(a) (Λ°m ) NaBr − (Λ°m ) NaCl quantity of electricity is ……… (c) Both S 1 and S2 are wrong
(d) Both S 1 and S2 are correct
= (Λ°m )KBr − (Λ°m )KCl
[2020, 9 Jan Shift-II]
Ans. (5.66) Ans. (b)
(b) (Λ°m )KCl − (Λ°m ) NaCl = (Λ°m )KBr
Equal quantity of electricity produces The explanation of statements (S 1 and S2 )
− (Λ°m ) NaBr same number of equivalents of products are as follows :
(c) (Λ°m ) NaBr − (Λ°m ) NaI in electrolysis. In conductivity cell, conductivity (κ) is
∴ No. of equivalent of O2 produced = No. equal to the sum of ionic conductances
= (Λ°m )KBr − (Λ°m ) NaBr of equivalents of Ag produced (c), of an electrolytic solution present is
(d) (Λ°m )H 2 O = (Λ°m )HCl No. of equivalent of Ag unit volume of the solution enclosed by
Mass 108 two electrodes of unit area (a ≠ 1)
+ (Λ°m ) NaOH − (Λ°m ) NaCl = = = 1. separated by a unit length (l = 1).
Equivalent mass 108
l
Ans. (c) κ=c×
∴No. of equivalents of O2 formed = 1. a
According to Kohlrausch’s law, For production of O2 from water ⇒ κ = c when l = 1, a = 1
Limiting molar conductivity of an 2H2O → O2 + 4H+ + 4e –
electrolyte is the sum of the individual So, with decrease in the concentration
n-factor = 4 of electrolyte, number of ions in the
contributions of the cation and the anion 1
of the electrolyte. Therefore, ∴1 equivalent = moles given unit volume also decreases, i.e. κ
4 [conductivity] also decreases.
for option (a).
Volume of gas at 273 K and 1 bar Thus, statement S 1 is wrong. S2 : Molar
λ ° m (Na+ ) + λ ° m (Br − ) − λ ° m (Na+ ) pressure conductivity (λ m ) is defined as the
− λ ° m (Cl − ) 1 conducting power of all the ions present
+ − + = 22.7 × n = 22.7 × = 5675
. L
= λ ° m (K ) + λ ° m (Br ) − λ ° m (K ) 4 in a solution containing 1 mole of an
− λ ° m (Cl − ) electrolyte.
or λ ° m (Br ) − λ ° m (Cl ) = λ ° m (Br − )
− −
18 A solution of Ni(NO 3 ) 2 is λ m = κ × VmL
− λ ° m (Cl − ) electrolysed between platinum = κ×
1000
∴ LHS = RHS electrodes using 0.1 Faraday M
∴ The LHS of option (a) electricity. How many mole of Ni where,VmL = volume in mL containing 1
= λ ° m (Br − ) − λ ° m (Cl − ) will be deposited at the cathode?
mole of electrolyte
and also RHS of that [2019, 9 April Shift-II] m = molar concentration (mol/L)
= λ ° m (Br − ) − λl° m (Cl − ) (a) 0.20 (b) 0.10 So, in a conductivity cell
LHS = RHS 1
(c) 0.15 (d) 0.05 λm ∝
For option (b), Ans. (d) M
λ ° m (K+ ) + λ ° m (Cl − ) − λ ° m (Na+ ) A solution of Ni(NO3)2 is electrolysed
i.e. molar conductivity increases with
decrease in the concentration (M) of
− λ ° m (Cl − ) between platinum electrodes using
electrolyte.
= λ ° m (K ) + λ ° m (Br ) − λ ° m (Na+ )
+ − 0.1 Faraday electricity. It means that
0.1 equivalent of Ni2 + will be discharged. Thus, statement S2 is correct.
− λ ° m (Br − )
or λ ° m (K ) − λ ° m (Na ) = λ ° m (K+ )
+ + Electrolysis of Ni(NO3)2 gives
20 Which one of the following graphs
− λ ° m (Na+ ) Ni2 + + 2e − → Ni
between molar conductivity (Λ m )
∴ LHS = RHS (Atomic mass of Ni = 58.7)
versus C is correct?
Similarly for option (c), Number of equivalents = Number of [2019, 10 April Shift-II]
moles × number of electrons.
LHS = λ ° m (Br − ) − λ ° m (I− )
0.1 = Number of moles × 2
Na

and RHS = λ ° m (K+ ) − λ ° m (Na+ )

Cl

0.1 KC
∴ LHS ≠ RHS ∴ Number of moles of Ni = = 0.05 l
2 (a) Λm
And for option (d), also
λ ° m (H+ ) + λ ° m (OH− ) = λ ° m (H+ ) 19 Consider the statements S 1 and S 2 :
+ λ ° m (OH− )
∴ LHS = RHS
S 1 : Conductivity always increases √C
with decrease in the
Thus, the correct answer is (c).
concentration of electrolyte.
17 108 g of silver (molar mass 108 g S 2 : Molar conductivity always
mol −1 ) is deposited at cathode increases with decrease in the (b) Λm
Na
KC

concentration of electrolyte.
Cl

from AgNO 3 (aq) solution by a

l

certain quantity of electricity. The The correct option among the

volume (in L) of oxygen gas following is [2019, 10 April Shift-I] √C
Electrochemistry 117

Ans. (d) from 1 mole of H2O at anode 4 moles

According to Kohlrausch’s law, the molar electrons are required.
(c) Λm conductivity of HA at infinite dilution is Likewise for the production of 3 moles of
given as, O2 12(3 × 4) moles of electrons will be
Λ°m (HA ) = [Λ°m (H+ ) + Λ°m (Cl − )] needed.
Na

KC
Cl

+ [Λ°m (Na+ ) + Λ°m (A − )] So, the total amount of charge required

to produce 3 moles of oxygen will be
√C − [Λ°m (Na+ ) + Λ°m (Cl − )]
12 × F or 12 × 96500
= 4259. + 100.5 − 1264 .
We know Q = it
= 400 S cm2 mol − 1
So, 12 × 96500 = 100 × t in seconds
(d) Λm Also, molar conductivity at given
12 × 96500
concentration is given as, or = t in hours = 32
. hours
1000 × κ 100 × 3600
Na

KC

Λm =
Cl

M
√C Given, κ = conductivity ⇒5 × 10 − 5 S cm − 1 23 Two Faraday of electricity is
Ans. (c) passed through a solution of
M = Molarity ⇒ 0.001 M
NaCl and KCl are strong electrolytes. So, CuSO 4 . The mass of copper
1000 × 5 × 10 − 5 S cm−1
the study of their molar conductances ∴ Λm = deposited at the cathode is (at.
(λ m) can be experimentally verified by 10 − 3 M
mass of Cu = 63.5 u) [JEE Main 2015]
Debye-Huckel Onsagar equation, = 50 S cm2 mol − 1
(a) 0g (b) 63.5g (c) 2g (d) 127g
Λcm = Λ∞m − B C Therefore, degree of dissociation (α), of
Ans. (b)
Λcm = molar conductance at HA is,
concentration. Λ 50 S cm2mol − 1 Given, Q = 2F
α = °m = = 0.125
Λ∞m = molar conductance at infinite Λm 400 S cm2mol − 1 Atomic mass of Cu = 63.5 u
dilution. Valency of the metal Z = 2
i.e. C→0
22 How long (approximate) should We have, CuSO4 → Cu2 + + SO24–
B = Debye-Huckel Onsagar constant.
water be electrolysed by passing Cu2 + + 2e− → Cu
For (both NaCl and KCl) a strong binary 2 mol 1mol = 63.5 g
through 100 amperes current so 1mol
electrolyte like AB, the nature of the plot 2F
of Λm vs C will be
that the oxygen released can E
completely burn 27.66 g of Alternatively, W = ZQ = ⋅ 2F = 2E
F
diborane? 2 ×63.5
= = 63.5
(Atomic weight of B = 10.8 µ) 2
[JEE Main 2018]
Λm
(a) 6.4 hours (b) 0.8 hours 24 Resistance of 0.2 M solution of an
√C (c) 3.2 hours (d) 1.6 hours electrolyte is 50 Ω. The specific
Ans. (c) conductance of the solution is
Size of Na⊕ is being smaller thanK⊕ and
Na⊕ will remain in more hydrated state, Given that,i = 100 amp. also, 27.66 g of 1.4Sm −1 . The resistance of 0.5 M
i.e. larger sized in aqueous solution. As a diborane (B2H6 ) solution of the same electrolyte is
result, ionic mobility as well as ionic Molecular mass of B2H6 280 Ω. The molar conductivity of
conductance of Na⊕ = 10.8 × 2 + 6 = 27.6 0.5 M solution of the electrolyte in
(or NaCl as Cl È is common to NaCl and
Number of moles of B2H6 in 27.66 g S mol −1 is [JEE Main 2014]
KCl) will be lower thanK⊕ (or KCl). Thus,
the plot of Λm vs C for NaCl and KCl is =
Given mass 27.66
= ≈1 (a) 5 × 10−4 (b) 5 × 10−3
as follows : Molar mass 27.6 (c) 5 × 103 (d) 5 × 102
Now consider the equation Ans. (a)
KC B2H6 + 3O2 → B2O3 + 3H2O For 0.2 M solution, R = 50 Ω
l
Na
Cl
From the equation we can interpret that . S m−1 = 14
κ = 14 . × 10 −2 Scm−1
Λm 3 moles of oxygen is required to burn 1 The resistivity of the solution is related
mole (i.e. 27.6 g)B2H6 completely. to specific conductance by
√C
Also consider the electrolysis reaction of 1 1
water i.e. ρ= = Ω cm
21 Λ° m for NaCl, HCl and NaA are κ 14 . × 10 −2
H2O s 2H+ + O−− l R l
126.4, 425.9 and It is known that, R = ρ ⇒ =
+2 e −
100.5 S cm 2 mol − 1 , respectively. If 2H+ → 2H → H2 ↑ a ρ a
Cathode
the conductivity of 0.001 M HA is l 1
Anode ⇒ = R × = 50 × 14. × 10 −2 cm
O−− →
2 such
O → O2 ↑
5 × 10 − 5 S cm − 1 , degree of −
−2e atoms
a ρ
dissociation of HA is From the above equation it can be easily For 0.5 M solution,
[2019, 12 Jan Shift-II] interpreted that in electrolysis of water R = 280 Ω; κ = ?
(a) 0.25 (b) 0.50 (c) 0.75 (d) 0.125 for the production of 1 mole of oxygen
118 JEE Main Chapterwise Topicwise Chemistry

l 1 l
. × 10 −2 cm
= 50 × 14 ⇒ κ= × = 13 . S m−1 (a) 124 × 10−4 S m2 mol−1
a 50 a (b) 1240 × 10−4 S m2 mol−1
l
The specific conductance of the solution ⇒ . × 50 m−1
= 13 (c) 1.24 × 10−4 S m2 mol−1
is given by a
(d) 12.4 × 10−4 S m2 mol−1
1 1 l l
κ= = × . × 50 × 10 −2 cm−1
= 13 Ans. (d)
ρ R a a
1 For 0.1 M solution
κ= . × 10 −2
× 50 × 14 For 0.4 M solution, R = 260 Ω
280 l 1 1 l R = 100 Ω
R =ρ ⇒ = κ = × 1 l
= 2.5 × 10 −3 S cm−1 a ρ R a ⇒ κ=  
1 R a 
Now, the molar conductivity of the κ= . × 50 × 10 −2 S cm−1
× 13 l
solution is given by 260 (cell constant) = 1.29 × 100 m−1
κ × 1000 2.5 × 10 −3 × 1000 Molar conductivity of the solution is a
Λm = =
M 0.5 given by For 0.2 M solution
= 5.5 cm2 mol −1 = 5 × 10 −4 S m2 mol −1 κ × 1000 Given, R = 520 Ω; C = 0.2 M
Λm =
Hence, the molar conductivity of0.5 M M µ (molar conductivity ) = ?
solution of the electrolyte is 1 . × 50 × 10 −2 × 1000
13
= × Molar conductivity,
5 × 10 −4 S m2 mol −1. 260 4 κ × 1000
Λm =
= 6.25 S cm2 mol −1 M
25 The equivalent conductance of = 6.25 × 10 −4 S m2 mol −1 1 l
[ κ can be calculated as κ =  ,
NaCl at concentrationC and at R a 
infinite dilution are λ c and λ ∞ , 27 The equivalent conductances of now cell constant is known]
respectively. The correct two strong electrolytes at infinite 1 1000
Hence, Λm = × 129 × × 10 −6 m3
relationship between λ c and λ ∞ is dilution in H2O (where ions move 520 0.2
given as [JEE Main 2014] freely through a solution) at 25°C = 12.4 × 10 −4 Sm2 mol −1
(a) λ c = λ ∞ + (B)C (b) λ c = λ ∞ − (B)C are given below
(c) λ c = λ ∞ − (B) C (d) λ c = λ ∞ + (B) C Λ° CH COONa = 91.0 S cm 2 /equiv 29 The molar conductivities Λ° NaOAc
3
Ans. (c) Λ° HCl = 426.2 S cm 2 /equiv and Λ° HCl at infinite dilution in
Debye-Huckel Onsager equation can be What additional information/ water at 25°C are 91.0 and
written as quantity one needs to calculate Λ° 426.2S cm 2 /mol, respectively. To
λ c = λ ∞ − (B) C of an aqueous solution of acetic calculate Λ° HOAc , the additional
Where, acid ? [AIEEE 2007] value required is [AIEEE 2006]
λ c = Molar conductivity of the solution at (a) Λ° of NaCl (a) Λ°H 2 O (b) Λ°KCl
certain concentration
(b) Λ° of CH3COOK (c) Λ°NaOH (d) Λ°NaCl
λ ∞ = Limiting molar conductivity (c) The limiting equivalent conductance
C = Concentration Ans. (d)
of H+ ( λ ° H + )
B = Constant that depends on (d) Λ° of chloroacetic acid (ClCH2 COOH)
According to Kohlrausch’s law
temperature, charges on the ions and O
dielectric constant as well as viscosity of Ans. (a) 
the solution Molar conductivity of aqueous CH3COOH [NaOAc == CH3 C O−Na+ ]
solution can be calculated from
26 Resistance of 0.2 M solution of an λ ° CH = λ ° CH – + λ °H + ...(i)
Kohlraush’s law as 3 COOH 3 COO
electrolyte is 50 Ω. The specific λ° CH COOH = λ ° CH COONa + λ °HCl − λ ° NaCl λ°HCl = λ °H + + λ ° Cl– ...(ii)
3 3
conductance of the solution is 1.3 S λ ° CH = λ ° CH COO – + λ ° Na + ...(iii)
Hence, for determining the molar 3 COONa
m −1 . If resistance of the 0.4M conductivity of CH3COOH solution, λ° NaCl
3
Thus, on adding Eqs. (ii) and (iii), if λ° Na +
solution of the same electrolyte is is required. and λ°Cl – are subtracted, we can
260 Ω, its molar conductivity is
[AIEEE 2011] 28 Resistance of a conductivity cell obtained the value of λ°HOAc . Thus,
2
(a) 6250 S m mol −1 additional value required is λ° NaCl.
filled with a solution of an
(b) 6.25 × 10−4 S m2 mol−1 electrolyte of concentration 0.1 M is
(c) 625 × 10−4 S m2 mol−1 30 The highest electrical conductivity
100 Ω. The conductivity of this
(d) 62.5 S m2 mol−1 from the following aqueous
solution is 1.29 S m −1 . Resistance of solutions is of [AIEEE 2005]
Ans. (b)
the same cell when filled with 0.2 M
For 0.2 M solution, (a) 0.1 M difluoroacetic acid
of the same solution is 520 Ω. The (b) 0.1 M fluoroacetic acid
Specific conductance (κ) molar conductivity of 0.2 M solution
 1 (c) 0.1 M chloroacetic acid
= Conductance   × Cell constant (l /a) of the electrolyte will be
R (d) 0.1 M acetic acid
[AIEEE 2006]
Electrochemistry 119

Ans. (a) 5.12 × 10 3 × 3 × 96500

Q= C TOPIC 2
Fluoro group causes negative inductive 27
effect increasing ionisation. Thus, 0.1 M =5.49 × 10 C 7 Electrochemical Series,
difluoroacetic acid has highest electrical Electrode Potential and EMF
conductivity. 33 The limiting molar conductivities
H O Λ° for NaCl, KBr and KCl are 126, 36 Consider the following cell
  152 and 150 S cm 2 mol −1 , reaction,
F ← C ← C ←O ←H respectively. The Λ° for NaBr is 9
↓ [AIEEE 2004]
Cd(s) + Hg 2SO 4 (s) + H2O(I) -
F 2 −1 2 −1
5
(a) 128 S cm mol (b) 176 S cm mol 9
(c) 278 S cm2mol−1 (d) 302 S cm2mol−1 CdSO 4⋅ H2O (s) + 2Hg(l)
5
31 Ans. (a) °
The value of E cell is 4.315 V at
Electrolyte KCl KNO 3 HCl NaOAc NaCl By Kohlrausch’s law.
25°C. If ∆H° = − 825.2 kJ mol − 1 ,
∞
Λ (S cm 2 Λ° NaBr = Λ° NaCl + Λ°KBr − Λ°KCl
mol −1)
149.9 145.0 426.2 91.0 126.5 the standard entropy change ∆S°
= 126 + 152 − 150
in J K − 1 is ....... (Nearest integer)
= 128 S cm2 mol −1
Calculate Λ∞HOAc using appropriate [Given, Faraday constant = 96487
molar conductances of the C mol − 1 ]
34 When during electrolysis of a [2021, 31 Aug Shift-I]
electrolytes listed above at
solution of AgNO 3 , 9650 C of Ans. (25)
infinite dilution in H2O at 25°C.
[AIEEE 2005]
charge pass through the ∆G ° = ∆H ° − T∆S ° …(i)
(a) 217.5 (b) 390.7 electroplating bath, the mass of where, ∆G ° = standard Gibb’s free
(c) 552.7 (d) 517.2 silver deposited on the cathode will energy change
be [AIEEE 2003] ∆H° = standard change in enthalpy
Ans. (b) ∆S ° = standard entropy change
(a) 1.08 g (b) 10.8 g
Λ∞AcOH = Λ∞AcONa + Λ∞HCl − Λ∞NaCl Also, ∆G ° = − nFE °
(c) 21.6 g (d) 108 g
= 91.0 + 426.2 − 126.5 = 390.7 where, n = number of electrons
Ans. (b)
F = Faraday constant
32 Aluminium oxide may be Ag + + e − → Ag
E ° = standard cell potential
electrolysed at 1000°C to furnish Number of moles of Ag =
9650 ∴ Equation (i) is,
aluminium metal (atomic mass 96500 − nFE ° = ∆H ° − T∆S °
= 27 u; 1 Faraday = 96,500 C). The 1 − nFE ° − ∆H ° = − T∆S °
=
moles
cathode reaction is 10 nFE ° + ∆H °
⇒ ∆S ° =
Al 3+ + 3e − → Al 0 Ag + + e − → Ag T
To prepare 5.12 kg of aluminium 1 (2 × 96487 C mol −1 × 4.315 V)
∴ Mass of Ag produced = × 108 = 10.8 g
metal by this method would 10 + (−825.2 kJ / mol)
=
require [AIEEE 2005] 298 K
35 Conductivity (Seimen’s S) is directly 832.682 × 10 3 J mol − 825.2 × 10 3 J / mol
(a) 5.49 × 101 C of electricity =
proportional to area of the vessel
(b) 5.49 × 104 C of electricity 298 K
(c) 1.83 × 107 C of electricity
and the concentration of the = 25.11 J / K mol
(d) 5.49 × 107 C of electricity solution in it and is inversely
Ans. (d)
proportional to the length of the 37 For the cell
− vessel, then constant of Cu (s)| Cu 2+ (aq) (0.1 ) M)||Ag + (aq)
+ 3 e → Al
Al 3+

w = zQ proportionality is expressed in (0.01M) | Ag(s)

[AIEEE 2002]
where, w = amount of metal the cell potential, E 1 = 0.3095 V
= 5.12 kg = 5.12 × 10 3 g (a) S m mol−1 (b) S2 m2 mol−2
z = electrochemical equivalent (c) S m2 mol−1 (d) S2 m2 mol For the cell,
equivalent weight Ans. (c) Cu (s)| Cu 2+ (aq) (0.01 M)||Ag + (aq)
=
96500 S ∝ area (m2 ) ∝ conc (mol /m3) (0.001M) | Ag (s)
atomic mass 1 the cell potential
= ∝ (m−1)
electrons × 96500 length =……………× 10 −2 V.
27 mol
= S = κm2 3 m−1 (Round off the nearest integer).
3 × 96500 m
 2.303 RT 
5.12 × 10 3 =
27
×Q ⇒ κ = S mol −1 m2 Use: = 0.059
3 × 96500  F 
[2021, 27 July Shift-II]
120 JEE Main Chapterwise Topicwise Chemistry

Ans. (28) 39 These are physical properties of an [Fe3+ ] 1

=
Cell reaction, element. [Fe2 + ] 10
Cu(s ) + 2Ag + (aq) → Cu2 + (aq) + 2Ag (s ) A. Sublimation enthalpy [Fe3+ ] 1 1
= =
° 0.0591 [Cu2 + ] [Fe ] + [Fe3+ ]
2+
1 + 10 4.16
E cell = E cell − log B. Ionisation enthalpy
2 [Ag2 + ]2 = 0.2402 = 24 × 10 − 2
C. Hydration enthalpy
° 0 .0591 (0.1) So, the value of x is 24.
E 1 = 0.3095 = E cell − log D. Electron gain enthalpy
2 (0.01)2
The total number of above
°
E cell = 0.3095 +
0 .0591
log(1000) properties that affect the
41 Assume a cell with the following
2
reduction potential is ……… reaction
= 0.3095 +
0.0591
log 10 3 (Integer answer) Cu(s) + 2Ag + (1 × 10 −3 M) →
2 [2021, 26 Aug Shift-I] Cu 2+ (0.250M) + 2Ag(s),
° 0.0591
E cell = 0.3095 + ×3 … (i) Ans. (3) E cell = 2.97 V
s
2
The physical properties of an element is
° 0.0591 (0.01) E cell for the above reaction is
E2 = E cell − log affected by sublimation enthalpy,
2 (0.001)2 ionisation enthalpy and hydration ……… V.
° 0.0591 enthalpy as these 3 enthalpies will affect (Nearest integer)
E2 = E cell − log 10000
2 the reduction potential.
[Given : log2.5 = 0.3979,T = 298 K]
° 0.0591
= E cell − log 10 4 [2021, 22 July Shift -II]
2 40 Consider the cell at 25° C
0.0591 Ans. (3)
°
E2 = E cell − ×4 Zn|Zn 2 + (aq), (1M)|
2 Given E ° cell = 297
. V
|Fe 3+ (aq), Fe 2 + (aq)| Pt(s)
From Eq. (i), Now, balanced the equation,
The fraction of total iron present
E2 = 0.3095 +
0.0591
×3−
0.0591
×4 Cu (s ) → Cu2 + (aq) + 2e − (oxidation)
as Fe 3+ ion at the cell potential of
2 2 2Ag + (aq) + 2e − → 2Ag (s ) (reduction)
0.0591 1.500 V is x × 10 −2 . The value of x is Overall:
= 0.3095 − = 0.3095 − 0.0295 ……… . (Nearest integer)
2 Cu (s ) + 2Ag + (aq) → Cu2 + (aq) + 2Ag (s )
= 0.28 = 28 × 10 −2 V (Given, E ° 3 + 2+ = 0.77 V, n = 2 (for 2 electrons)
Fe /Fe ° = 297
E cell . V
38 For the galvanic cell, E° = − 0.76 V) Using nernst equation,
Zn2+/ Zn
Zn (s) + Cu 2+ (0.02 M) → [2021, 25 July Shift-I]
° −
E cell = E cell
0.0591
log
[Cu2 + ]
Zn 2+ (0.04M) + Cu(s), Ans. (24) n [Ag + ]2
E Cell = ……… × 10 − 2 V. Reaction cell
= 2.97 −
0.0591 0.250
log −3 2
(Nearest integer) Zn|Zn2 (aq), (1M)||Fe3+ (aq)|, 2 (10 )
Fe2 + (aq),Pt( s ) = 2.81 ≈ 3 (approx.)
[Use E º = − 0.34 V,
Cu/Cu2 + (Anode) Zn → Zn + 2e −
2+
° of the reaction is 3V.
Hence, E cell
E º 2 + = + 0.76 V, (Cathode) 2Fe3+ + 2e − → 2Fe2 +
Zn/Zn
Overall Zn + 2Fe3+ → Zn2 + + 2Fe2 + 42 The molar conductivities at infinite
2.303 RT
= 0.059 V] Given values are : dilution of barium chloride,
F Reduction potential of Fe(III) = 0.77 V sulphuric acid and hydrochloric
[2021, 26 Aug Shift-II] Reduction potential of Zn(II) = −0.76 V acid are 280, 860 and 426 Scm 2
Ans. (109)
E °cell = E ° − E° mol −1 respectively. The molar
Fe 3+ / Fe 2 + Zn 2 + / Zn
Cell reaction,
= 0.77 − (−0.76) conductivity at infinite dilution of
Cu2 + (aq) + Zn(s ) q 2+
Cu (s ) + Zn (aq)
= 1.53 V barium sulphate is … S cm 2 mol −1
0.02 M 0.04 M
Using Nernst equation, (Round off to the nearest Integer).
° = E°
E cell − E° [2021, 18 March Shift-II]
Cu 2 + / Cu Zn 2 + / Zn 0.0591 [P]
E cell = E ° cell − log Ans. (288)
= 0.34 − (− 0.75) = 1.1 V n [R]
Molar conductivity of BaCl2 =280
0.059 [Zn2 + ] 2
° −
E cell = E cell log 0.0591  Fe2 +  Scm2 mol −1
2 [Cu2 + ] 1.50 = 1.53 − log  3+ 
2  Fe  Molar conductivity of H2SO4 = 860
= 1.1 −
0.059
log
[0.04] Scm2 mol −1
2 [0.02]  Fe2 +  0.03 1 Molar conductivity of HCl
log  3+  = =
= 1.1 − 0.03 log 2 = 1.1 − 0.03 × 0.30  Fe  0.06 2 = 426 Scm2 mol −1
= 1.09 V = 109 × 10 −2 V [Fe2 + ] Molar conductivity of BaSO4 = ?
∴ Answer is 109. = 10 1/ 2 = 10 From Kohlrausch’s law,
[Fe3+ ]
Electrochemistry 121

Λ∞m (BaSO4 ) = λ∞m (Ba2 + ) + λ∞m (SO24− ) Ans. (147) 0.17 =

0.059
[log Q 1 − 3log Q2 ]
Λ∞m (BaSO4 ) = Λ∞m (BaCl2 ) + Λ∞m (H2SO4 ) Zn|Zn2 + (0.1M) | | Ag + (0.01M) | Ag 6
0.059 Q
− 2Λ∞m (HCl) Cell reaction : = log 1
On putting given values we get, Zn( s )+ 2Ag + - Zn2 + + 2Ag ( s ) 6 Q2
0.01M 0.1M
= 280 + 860 − 2(426) 0.059 [Cu2 + ] 3 × (pNO )2
= log
= 288 Sc m2 mol − 1
2+
[Zn ] [Ag] 2
0.1 × 1 2
6 [NO−3 ]2 × [H+ ] 8
⇒ Q= = = 10 3
[Zn] [Ag + ]2 1 × (0.01)2
[NO−3 ] 6 × [H+ ] 12
43 For the reaction, ×
n=2 [Cu2 + ] 3 × (pNO ) 6
2Fe 3+ (aq ) + 2I − (aq ) → ° = EAg
and E cell ° + / Ag − E ° 2+
2
Zn / Zn
0.059 [H+ ] 4 × [NO−3 ] 4
2Fe 2+ (aq ) + I 2 ( s ) = log
= 0.8 − (−0.76) = 1.56 V 6 (pNO ) 4
The magnitude of the standard 2
⇒ ° − 0.059 log Q
E cell = E cell
molar Gibbs free energy change, n [QpNO = pNO 2 ]
°
∆ r Gm = − ........... kJ (Round off to 0.059 =
0.059 [HNO3] 4
= 1.56 − log 10 3 log
the nearest integer). 2 6 (pNO ) 4
2
E ° 2 + = − 0.440 V; = 14715
. V Now, pNO 2 ≡ [HNO3]
 Fe °/Fe( s ) = 147.15 × 10 −2 V
 E I /2I − = 0.539 V; So, 0.17 =
0.059
log [HNO3] 8
 2 = 147 × 10 −2 V 6
E ° 3+ = − 0.036 V = x × 10 −2 V 0.059
Fe /Fe( s )  = × 8 log [HNO3]
F = 96500 C  x = 147 6
log[HNO3] = 2.16
[2021, 18 March Shift-I] 45 Copper reduces NO −3 into NO and [HNO3] = 102.16 M = 10 xM
Ans. (45) NO 2 depending upon the ∴ x = 2.16
Given reaction is concentration of HNO 3 in solution. ⇒ 2x = 2 × 2.16 = 432
. ~− 4
2Fe3+ (aq) + 2I− (aq) → 2Fe2 + (aq) + I2 (s ) (Assuming fixed [Cu 2+ ] and
E 2° pNO = pNO2 ), the HNO 3 46 The magnitude of the change in
E 1°
Now, Fe3+ → Fe2 + → Fe concentration at which the oxidising power of the MnO −4 /Mn 2+
E 3°
thermodynamic tendency for couple is x × 10 − 4 V, if the H+
nE 1° + nE2° = nE 3° reduction of NO −3 into NO and NO 2 concentration is decreased from
[n = number of electron transferred] by copper is same is 10 x M. The 1 M to 10 − 4 M at 25°C. (Assume
concentration of MnO −4 and Mn 2+ to
1E 1° + 2E2° = 3E 3° value of 2x is ……… .
(Rounded off to the nearest be same on change in H+
E° + 2E ° = 3E ° concentration). The value of x is
Fe 3+ /Fe 2 + Fe 2 + /Fe (s ) Fe 3+ /Fe (s ) integer) [2021, 25 Feb Shift-II]
……… (Rounded off to the nearest
E° + (−0.440) × 2 = (−0.036) × 3 Ans. (4)
Fe 3+ /Fe 2 +  2.303 RT 
Cell-I (HNO3 → NO) integer). Given, = 0.059
E° = 0.772 V  F 
Fe 3+ /Fe 2 + 3Cu + 2NO−3 + 8H+ →
[2021, 24 Feb Shift-II]
E ° cell = E ° cathode − E ° anode 3Cu2 + + 2NO + 4H2O
2+ 3 Ans. (3776)
= 0.772 − 0.539 = 0.233 V [Cu ] × (pNO )2
Q1 = Reaction,
Using standard Gibb’s free energy, [NO−3 ]2 × [H+ ] 8 MnO−4 + H+ + 5e − → Mn2 + + 4H2O
°
∆G ° = nFE cell = + 2 × 96500 × 0.233
Q E 1º = 0.96 − (− 0.34) = 13
. V n= 5
∆G ° = 44969 J = 449 . kJ = 45 kJ 0.059
E 1 = 1.3 − log Q 1 Applying Nernst equation,
44 Emf of the following cell at 298 K in 6 ° 0.0591 [P]
E cell = E cell − log
V is x × 10 −2 , Zn | Zn 2+ (0.1 M) || Cell-II (HNO3 → NO2 ) n [R]
Ag + (0.01 M) | Ag Cu + 2NO−3 + 4H+ → 0.0591 [Mn2 + ]  1 
8
°
Cu2 + + 2NO2 + 2H2O or E cell = E cell − log
The value of x is ……… . 5 [MnO4− ]  H+ 
[Cu2 + ] × (pNO )2
(Rounded off to the nearest O2 = 2 (I) Given, [H+ ] = 1 M
integer). [NO3− ]2 + 4
× [H ] 0.0591 [Mn2 + ]
E1 = E ° − log
[Given, E ° 2+ = − 0.76 V, Q E2º= 0.79 − (− 0.34)V = 1.13V 5 [MnO4− ]
Zn /Zn
E2 = 1.13 −
0.059 (II) Now, [H+ ] = 10 −4 M
° +
E Ag = + 0.80 V, log Q2
/Ag 2 0.0591 [Mn2 + ] 1
E2 = E ° − log ×
2.303RT Now, E 1 = E2 5 [MnO−4 ] (10 −4 ) 8
= 0.059]
F 0.059 0.059
1.3 − log Q 1 = 1.13 − log Q2 ∴ | E 1 − E2 |
[2021, 26 Feb Shift-II] 6 2
122 JEE Main Chapterwise Topicwise Chemistry

0.0591
| E 1 − E2 | = × 32 = 0.3776 V The pH of aqueous HCl required to (b) If E ext = 1.1 V, no flow of electrons or
5 stop the photoelectric current current occurs.
= 3776 × 10 −4 (c) If E ext > 1.1 V, electrons flows from Cu
from K (w 0 = 2.25 eV), all other
x = 3776 to Zn.
conditions remaining the same, is (d) If E ext < 1.1 V, Zn dissolves at anode
........... × 10 −2 (to the nearest and Cu deposits at cathode.
47 The Gibbs energy change (inJ) for
integer). Ans. (a)
the given reaction at RT
[Cu 2+ ] = [Sn 2+ ] = 1M and 298 K is Given, 2.303 = 0.06 V; Given, E ° 2 +
Cu / Cu
= −0.34 V
F E° 2 + = −0.76 V
Cu (s) + Sn 2+ (aq) → Cu 2+ (aq) °
E AgCl|Ag|Cl − = 0.22 V Zn / Zn
°
+ Sn (s); E cell = E° − E°
[2020, 3 Sep Shift-I] Cu 2 + / Cu Zn 2 + / Zn
o
(E 2 + = − 0.16 0.16 V, Ans. (58.3) = 0.34 − (−0.76)
Sn /Sn
E o 2+ = 0.34 V, Pt(s )|H2 (g), 1 bar | HCl (aq) (pH = 1)| = 1.10 volt
Cu /Cu Statement (a) is incorrect whereas all
(Ag (s )| AgCl)
Reaction involved : other statements are correct.
Take, F = 96500 C mol −1 ) 1 If E ext > 1 . 1 V {act as electrolytic cell}
[2020, 2 Sep Shift-I] H2 + AgCl(s ) → Ag(s ) + H+ + Cl −
2 Cu → Anode
Ans. (96500)
E cell = E Ag = 0.22 − log [H+ ] [Cl − ] 
0.06 Zn → Cathode
Cu(s ) + Sn2 + (aq) → Cu2 + (aq) + Sn(s )  1  If, E ext = 1 . 10 V
(1 M) (1 M) 0.06 + − Zn → Anode
E cell = (E ° − E° ) E K = 0.22 − log [H ] [Cl ]
Sn 2 + / Sn Cu 2 + / Cu 1 Cu → Cathode
hc
0.0591 [Cu ] 2+ For Na, = 2.3 − E Na …(i) So, Zn dissolves at copper electrode and
−log λ
2 [Sn2 + ] hc Cu at Zn electrode.
0.0591 1 For K , = 2 . 25 − E K …(ii)
= (−0.16 − 0.34) − log = − 0.50 V λ
2 1 51 An oxidation-reduction reaction in
Equating (i) and (ii)
° = − 2 × 96500 × (− 0.50) J
∆G = − nF E cell which 3 electrons are transferred
2.3 E Na = 2 . 25 − E K
has a ∆G° of 17.37 kJ mol −1 at 25°
= 96500.00 J 0.05 − 0 . 22 + 0. 06log (10 −1) (10 −1) °
C. The value of E cell (in V) is ……
= − 0. 22 + 0.06log [H+ ] [Cl − ]
48 For the disproportionation reaction ×10 . (1 F = 96,500 C mol −1 )
−2
5 + 6log(10 −2 ) = 6log [H+ ]2
Cu(s) + Cu 2+ (aq) at
[2020, 5 Sep Shift-I]
2Cu + (aq ) c 7
− = log[H+ ] Ans. (6)
298 K, In K (where K is the 12
equilibrium constant) is ………× 10 −1 . 7 ∴ ∆G º = − nFE cell
º
pH = + = 0.5833
12 Here, ∆G = 17.37 kJ mol − 1
º
Given : (E ° 2 + + = 0.16 V,
Cu /Cu
pH = x × 10 −2 = 583
. × 10 −2 n = number of electrons
RT F = Faraday constant
° +
E Cu = 0.52 V and =0.025) So, value is 58.3.
/Cu F = 96500 C /mol
[2020, 2 Sep Shift-II] 50 = 17.37 × 1000 J mol − 1
º
Ans. (144) Eext 17.37 × 1000 = − 3 × 96500 × E cell
º 17. 37 × 1000
+
2Cu (aq) c Cu(s ) + Cu (aq) 2+
E cell =
For the cell reaction, 3 × 96500
°
E cell °
= E Cu + − E ° 2 + + = (0.52 − 0.16)
º
E cell = − 0.06 = − 6 × 10 − 2
/ Cu Cu / Cu

V = 0.36 V Zn rod Cu rod

52 For the given cell;
°
⇒ ∆G ° = − nF E cell –ve +ve Cu(s)|Cu 2+ (C 1M)||Cu 2+ (C 2M)|Cu(s)
°
⇒ − RT lnK = − nF E cell 1M Salt 1M change in Gibbs energy (∆G) is
E ° ZnSO4 Bridge CuSO4
⇒ lnK = n × × E cell solution solution negative, if [2020, 6 Sep Shift-II]
RT C1
1 ° (a) C 1 = C2 (b) C2 =
= 1× × 0.36 E = + 0.34 V 2
0.025 Cu2+ | Cu
(c) C 1 = 2C2 (d) C2 = 2 C 1
. = 144 × 10 −1
= 144 E ° 2+ = − 0.76 V
Zn | Zn Ans. (d)
Identify the incorrect statement Given, cell is
49 The photoelectric current from Na from the options below for the Cu(s )| Cu2 + (C 1M) | | Cu2 + (C2M)| Cu(s )
(work function, w 0 = 2.3 eV) is above cell. [2020, 4 Sep Shift-I] Gibbs free energy, ∆G = − nFE cell
stopped by the output voltage of (a) If E ext > 1.1 V, Zn dissolves at Zn ∆G is negative, if E cell is positive, two half
the cell Pt( s )|H2 (g, 1 bar) | electrode and Cu deposits at Cu reaction are as follows for given cell
HCl (aq.,pH =1) |AgCl( s ) | Ag( s ). electrode. reaction
Electrochemistry 123

At anode Cu(s ) → Cu2 + (C 1) + 2e − = − 123

. −
0.0591
log 1 × (10 −5 ) 4 Ans. (c)
At cathode Cu2 + (C2 ) + 2e− → Cu(s) 4 Higher the standard reduction potential
. − 0.0591  log 10 −20 
1
Total cell reaction = − 123 (E º M n + / M ), better is oxidising agent.
° =0
Cu2 + (C2 ) → Cu2 + (C 1); E cell 4 
Among the given, E °S 2 O 2 − / SO 2 − is highest,
° − 2303
. RT = − 1.23 − 0.0591 × 5log 10 henceS2O28− is the strongest oxidising
8 4

E cell = E cell log Q

nF = − 123
. − (0.0591 × −5) agent.
. RT
2303 C  = − 123
. + 0.295 The decreasing order of oxidising agent
E cell = 0 − log  1 
nF  C2  = −0.935 V ≈ –0.94 V among the given option is as follows:
C1 S2O28− > Au3+ > O2 > Br2
E cell > 0 ; if < 1 ⇒ C 1 < C2 55 For an electrochemical cell
C2
Sn(s)|Sn 2 + (aq, 1 M)||Pb 2 + 57 Calculate the standard cell
C2 = 2 C 1 is correct. [Sn 2 + ]
(aq, 1 M)|Pb(s) the ratio potential (in V) of the cell in which
53 Given that the standard potentials [Pb 2 + ] following reaction takes place
(E°) of Cu 2+ /Cu and Cu + /Cu are when this cell attains equilibrium is Fe 2+ (aq) + Ag + (aq) →
0.34 V and 0.522 V respectively, ……… .
Fe 3+ (aq) + Ag(s)
the E° of Cu 2+ /Cu + is Given : E ° 2 + = − 0.14 V, 
Given that, E ° Ag + /Ag = x V,
[2020, 7 Jan Shift-I]  Sn | Sn 
(a) − 0.158 V (b) +0.158 V
 ° 2.303 RT  E ° 2+ = y V
E Pb2 + | Pb = − 0.13 V,  Fe /Fe
E ° 3+ =z V
(c) − 0.182 V (d) 0.182 V  F  Fe / Fe [2019, 8 April Shift-II]
Ans. (b)  = 0.06 
  (a) x + 2 y − 3z (b) x − y
The half cell reactions are :
(1) Cu2 + + 2e − Cu ; E ° = 0.34 V
[2020, 8 Jan Shift-II] (c) x + y − z (d) x − z
- Ans. (2.15) Ans. (a)
(2) Cu+ + e − - Cu ; E ° = 0.522 V
(3) Cu2 + + e −- Cu+ ; E° = x (exact value –2.154) Fe2 + (aq) + Ag + (aq) → Fe3+ (aq) + Ag (s )
As we know, ∆G ° = − nFE Cell notation : °
∴ E cell °
= E Ag − E°
Fe 3+ /Fe 2 +
+
/ Ag
∴ To obtain the E ° of required equation, Sn(s ) |Sn2 + (aq ; 1 M)| |Pb2 + (aq; 1 M)) |Pb(s )
= x V − E ° 3+ 2 + …(i)
subtract ∆G ° of equation (2) from ∆G ° of Cell reaction : Fe /Fe
Now, for two half-cells
(1) as Sn(s ) + Pb2 + (aq ) - Pb(s ) + Sn2 + (aq )
∆G ° of (3) = ∆G ° of (1) − ∆G ° of (2) [Sn2 + ] (i) Fe2 + + 2e − → Fe;
°
or −1 × F × x = (−2 × F × 0.34) − (−1 × F
Equilibrium constant (K ) = EFe = E 1° = y V
[Pb2 + ]
2+
/Fe

× 0.522) ∆G2° = − 2FE 1°

⇒unknown
∴ x = 2 × 0.34 − 0.522 E ° Cell = E ° Cathode − E ° Anode (ii) Fe3+ + 3e − → Fe;
= 0.68 − 0.522 = 0.158 V = (−0.13 V) − (−0.14 V) = 0.01 V E ° 3+ = E2° = z V
Fe /Fe
From Nernst equation, ∆G2° = − 3FE2°
54 What would be the electrode So, Fe 3+
+ e → Fe2 + ;
–
2303
. RT 0.06
potential for the given half-cell E°= log K = log K
nF n E ° 3+ = E 3° = ?
reaction at pH= 5 ? …… . /Fe 2 +
Fe
nE °
∴ log K = ; (n = 2) ; ∆G 3° = − 1 × FE 3°
2H2O → O 2 + 4H⊕ +4e − ; 0.06
° 2 × 0.01 Again, ∆G 3° = ∆G2° − ∆G 1°
E red = 1.23 V = = 0.33 or
1
−1 −1 0.06 3 ⇒ − FE 3° = − 3FE2° − (− 2FE 1° )
(R = 8.314 J mol K ; Temp = 298
K; oxygen under std. atm. K = 10 0. 33 or ⇒ − E 3° = 2E 1° − 3E2°
pressure of 1 bar) = 3 10 = 2.154 ≈ 2.15 ⇒ E 3° = 3E2° − 2E 1°
The value may range from 2.13 to 2.17. °
[2020, 8 Jan Shift-I] ⇒ E = (3z − 2y) V
Fe 3+ /Fe 2 +
Ans. (0.94)
° 56 Given, that E Os2 /H2 O = +1.23V; So, from equation (i)
Given, E red = 123
. V °
E cell = xV − (3z − 2y) V
But as the given half cell reaction is an
oxidation reaction. Therefore,
E sS O2 − /SO2 − = 2.05V; = (x − 3z + 2y) V
2 8 4
°
E oxi °
= –E red = – 123
. V ⇒ n=4
s
E Br /Br s
= + 1.09V,
T = 298 K s
2 58 The standard Gibbs energy for the
E = +1.4V
⇒ pH = 5 Au3 + / Au given cell reaction in kJ mol −1 at
⇒ [H+ ] = 10 −5 The strongest oxidising agent is 298 K is
Zn(s) + Cu 2+ (aq) → Zn 2+ (aq)
[2019, 8 April Shift-I]
By Nernst equation, at 298 K :
(a) Au 3+ (b) O2
E = E° −
0.0591
log Q [QQ = pO 2 × [H+ ] 4 ] (c) S2O2− (d) Br2 + Cu(s), E° = 2 V at 298 K
8
n
124 JEE Main Chapterwise Topicwise Chemistry

(Faraday’s constant, F = 96000 C 60 If the standard electrode potential HClsolution is used. The standard
mol −1 ) [2019, 9 April Shift-I] for a cell is 2V at 300 K, the electrode potential of
(a) 384 (b) 192 equilibrium constant (K) for the (AgCl / Ag,Cl − ) electrode is
(c) −384 (d) −192 reaction,  2.303RT 
Given, = 0.06 V at 298 K
Ans. (c) Zn(s) + Cu 2+ (aq) Zn 2+ (aq)
-  F 
Key Idea Gibbs energy of the reaction is + Cu(s) at 300 K is approximately [ 2019, 10 Jan Shift-II]
related to E ° cell by the following formula (R = 8 JK −1mol −1 , F = 96000 C mol −1 ) (a) 0.40 V (b) 0.20 V
∆G º = − nFE ° cell (a) e −160 (b) e 160 (c) e −80 (d) e 320 (c) 0.94 V (d) 0.76 V
∆G º = Gibbs energy of cell [2019, 9 Jan Shift-II] Ans. (b)
nF = amount of charge passed Ans. (b) It is an electrochemical cell. The overall
E = EMF of a cell The relationship between standard cell reaction can be written, as
Given reaction is, electrode potential (E ° ) and equilibrium H2 (g) + 2AgCl(s ) → 2HCl(aq) + 2Ag(s )
Zn + Cu2 + → Zn2 + + Cu constant (K ) of the cell reaction, (1 bar) (10 −6 M)
Zn(s ) + Cu2 + (aq) 1 Zn2 + (aq) + Cu(s )
E º cell = 20
. V; F = 96000 C; n = 2 (i) According to Nernst equation,
can be expressed as,
To find the value of ∆G º (kJ mol), we use ° ° 2303
. × RT
E° =
RT
lnK ⇒K = e nFE ° / RT E cell = (E cathode − E anode )−
the formula nF n×F
∆G º = − nFE º cell Given, n = 2, F = 96000 C mol −1 [HCl]2 [Ag]2
log
∆G º = −2 × 96000 × 2 = −384000 J/mol E ° = 2 V, R = 8 JK−1 mol −1,T = 300 K pH 2 [AgCl]2
−384000 2 × 96000 × 2
In terms of kJ/mol, ∆G º =
1000 ∴ K =e 8 × 300
= e 160 Here, (i) E c° = E AgCl/
°
Ag, Cl−
°
= E cathode
= −384 kJ/mol ° °
(ii) E anode = E2H + = 0.00 V
59 Given, 61 Consider the following reduction /H 2

processes:
Co 3+ + e − → Co 2+ ; E ° = + 1.81 V (Standard hydrogen electrode)
Pb 4+ + 2e − → Pb 2+ ; E ° = + 1.67 V Zn 2+ + 2e − → Zn(s ); E ° = − 0.76 V ⇒ 0.92 = (E c° − 0) − 0.06 × log
(10 −6 )2 × 12

Ce 4+ + e − → Ce 3+ ; E ° = + 1.61 V Ca 2+ + 2e − → Ca(s); E ° = − 2.87 V 1 × 12

Bi 3+ + 3e − → Bi; E ° = + 0.20 V Mg 2+ + 2e − → Mg(s); E ° = − 2.36 V = E c° + 0.06 × 6 × 2

Ni 2+ + 2e − → Ni(s); E ° = − 0.25 V ⇒ E c°= 0.92 − 0.72
Oxidising power of the species will
= 0.20 V
increase in the order The reducing power of the metals
Note 10 −6 molal HCl is a very dilute
[2019, 12 April Shift-I] increases in the order
solution.
(a) Ce < Pb < Bi3+ < Co 3+
4+ 4+ (a) Zn < Mg < Ni < Ca
So, 10 −6 m ~− 10 −6 M
(b) Bi3+ < Ce 4 + < Pb 4 + < Co 3+ (b) Ni < Zn < Mg < Ca
(c) Co 3+ < Ce 4 + < Bi3+ < Pb 4 + (c) Ca < Zn < Mg < Ni
63 For the cell,
(d) Co 3+ < Pb 4 + < Ce 4 + < Bi3+ (d) Ca < Mg < Zn < Ni
[2019, 10 Jan Shift-I] Zn(s)|Zn 2+ (aq)||M x+ (aq)|M(s),
Ans. (b)
Ans. (b) different half cells and their
Key Idea Negative E ° means that redox standard electrode potentials are
couple is weaker oxidising agent than Reducing power of an element
H+ /H2 couple. Positive E° means that ∝
1 given below.
redox couple is a stronger oxidising agent Standard reduction potential
than H+ / H2 couple
Au 3+ Ag + Fe2+
Here, E ° 2 + values of the given metals x+ Fe 3+ (aq)/
M /M M (aq)/M(s) (aq)/ (aq)/ Fe2+ (aq) (aq)/
Given, are as, Au(s) Ag(s) Fe(s)
Co3+ + e − → Co2 + ; E ° = +1.81 V Metals Ni Zn Mg Ca
E °M x + / M /V 1.40 0.80 0.77 − 044
.
Pb4 + + 2e − → Pb2 + ; E ° = + 1.67 V E° (V) − 0.25 − 0.76 − 236
. − 2.87
Ce4 + + e− → Ce3+ ; E ° = + 1.61 V →
Reducing power
If E° 2 + = − 0.76 V, which
Bi3+ + 3e − → Bi; E ° = + 0.20 V Thus, the correct order of increasing Zn /Zn
Oxidising power of the species increases cathode will give a maximum value
reducing power of the given metal is,
in the order ofBi3+ < Ce4 + < Pb4 + < Co3+ . Ni < Zn < Mg < Ca. of E° cell per electron transferred?
Higher the emf value, stronger the [2019, 11 Jan Shift-I]
oxidising power. The maximum value of 62 In the cell, Ag + Fe2+
(a) (b)
emf is possessed by Co3+ . Hence, it has Ag Fe
maximum oxidising power. WhereasBi3+ Pt(s) H2 (g , 1 bar) HCl(aq )| AgCl(s)
Au 3+ Fe 3+
possess the lowest emf value. Hence, it Ag(s) Pt(s) the cell potential is (c) (d)
has minimum oxidising power. 0.92 V when a 10 −6 molal Au Fe2+
Electrochemistry 125

Ans. (a)
Cell E ° cell (SRP) = E ° C − E ° A E ° cell free electron Cell E ° cell (SRP) = E ° C − E ° A E ° cell free electron
Anode (A) Cathode (C) transfer Anode (A) Cathode (C) transfer
Zn 0.80 − (−0.76) 1.56 Zn 1.40 − (−0.76) 2.16
+ = + 0.78 V + = + 0.36 V
1. [Zn + 2Ag + → = + 1.56 V for 2e − 2 3. [3Zn + 2Au3 + → = + 24 . V for 6e − 6
Ag Au
Zn2 + + 2Ag] 3Zn2 + + 2Au]
Zn − 0.44 − (− 0.76) 0.32 Zn 0.77 − (−0.76) +
1.53
= + 0.765 V
2. [Zn + Fe 2 + → + = + 0.16 V
= + 0.32 V for 2e − 2 4. [3Zn + 2Fe 3 + → = + 1.53 V for 2e − 2
Fe Fe
Zn2 + + Fe] Zn2 + + 2Fe 2 + ]

64 The standard electrode potential 65 Given the equilibrium constant Ans. (a)
E° and its temperature coefficient (K C ) of the reaction : The substances which have lower
reduction potentials are stronger
 dE °  Cu(s) + 2Ag + (aq) → Cu 2 + (aq)
  for a cell are 2V and reducing agents. Therefore, Cr
 dT  + 2Ag(s) ° 3+
(E Cr = − 0.74 V) is the strongest
− 5 × 10 −4 VK −1 at 300 K
/ Cr
is 10 × 10 , calculate the E cell
15 ° of reducing agent among all the other given
respectively. The cell reaction is options.
this reaction at 298 K.
Zn(s) + Cu 2+ (aq) → Zn 2+ (aq) + Cu(s)
 RT 
The standard reaction enthalpy 2.303 F at 298 K = 0.059 V 67 Given below are the half-cell
(∆ r H s ) at 300 K in kJ mol −1 is, [2019, 11 Jan Shift-II]
reactions
[Use, R = 8 JK −1 mol −1 (a) 0.4736 V (b) 0.04736 mV Mn 2+ + 2e − → Mn, E ° = −1.18 V
and F = 96000 , C mol −1] (c) 0.4736 mV (d) 0.04736 V 2(Mn 3+ + e − → Mn 2+ ),
(a) − 412.8 (b) − 384.0
Ans. (a) E° = +1.51 V
(c) 206.4 (d) 192.0
[2019, 12 Jan Shift-I] According to Nernst equation, The E° for 3Mn 2+ → Mn + 2Mn 3+
Ans. (a) 2.303 RT will be [JEE Main 2014]
E cell = E ° cell − log Q
 dE °  nF (a) −2.69V, the reaction will not occur
Given, E ° = 2V,   2.303 RT (b) −2.69 V the reaction will occur
 dT  Given, = 0.059 V
F (c) −0.33V, the reaction will not occur
= − 5 × 10 −4 VK −1
0.059 (d) −0.33 V, the reaction will occur
T = 300 K ∴ E cell = E ° cell − log Q
n Ans. (a)
R = 8 JK −1mol −1,
At equilibrium, E cell = 0 Mn2 + + 2e − → Mn, E ° = −1.18 V …(i)
F = 96000 Cmol −1
0.059 2 (Mn3+ + e − → Mn2 + ), E ° = +1.51 V …(ii)
According to Gibbs-Helmholtz equation, E ° cell = log K C
n Subtracting Eq. (ii) from Eq. (i), we get
∆G = ∆H − T∆S …(i)
For the given reaction, 3 Mn2 + → Mn + 2Mn3+
Also, ∆G = − nFE ° cell …(ii)
n=2 E ° = −1.18 − (+1.51) = − 269
. V
On substituting the given values in
equation (ii), we get Also, K C = 10 × 10 15 [given] Since, the value of E ° is −ve, therefore
the reaction is non-spontaneous.
∆G = − 2 × 96000 C mol −1 × 2 V 0.059
∴ E ° cell = log (10 × 10 15 ) Alternate method
[Q n = 2 for the given reaction] 2
Mn2 + + 2e − → Mn, E ° = −1.18 V …(i)
= − 4 × 96000 J mol −1 = 0.472 V ≈ 0.473 V
= − 384000 J mol −1 ∆G ° = − nFE ° [here, n = number of e −

Now, ∆S = nF 
 dE °  66 Given, E °Cl − = 1.36 V, involved in the reaction]
 2 /Cl ∆G 1° = −2F (−1.18) = 236
 dT  . F
∆S = 2 × 96000 C mol −1 × (−5 × 10 −4 VK−1) E ° 3+ = − 0.74 V 2Mn 3+
+ 2e − → 2Mn2 + , E ° = +1.51 V …(ii)
Cr /Cr
= −96 JK −1 mol −1 ∆G2° = −2F [1.51] = −302
. F
E° = 1.33 V,
Thus, on substituting the values of ∆G Cr2O27 − /Cr3 + Subtracting Eq. (ii) from Eq. (i), we get
and ∆S in
E° = 1.51 V 3 Mn2 + → Mn + 2Mn3+ , [n = 2]
Eq. (i), we get − 384000 J mol −1 MnO−4 /Mn2 +
= ∆H − 300 K × (−96 JK−1mol −1) ∆G 3° = −2FE °
Among the following, the
∆H = − 384000 − 28800 J mol −1 ∆G 30 = ∆G 10 − ∆G20 = 538
. F
strongest reducing agent is
= − 412800 J mol −1 [JEE Main 2017] ⇒ −2FE ° = 538
. F
= − 412.800 kJ mol −1 (a) Cr (b) Mn2 + (c) Cr 3 + (d) Cl− ⇒ E ° = −269
. V
126 JEE Main Chapterwise Topicwise Chemistry

68 Given, E ° 3 + = − 0. 74 V; (c) X = Fe, Y = Zn

Ans. (c)
Cr /Cr
For hydrogen electrode,
Fe + Zn 2+
→ Fe 2+
+ Zn
E° = 1.51 V 1
MnO−4 /Mn2+ ° = E°
E cell + E° H+ (aq) + e − → H2 (g)
Fe /Fe 2 + Zn 2 + /Zn 2
E° = 1.33 V; = 0.44 − 0.76 = − 0.32 V (p H 2 ) 1 / 2
Cr2 O27− /Cr3 + 0.0591
E = E °− log
° − = 1.36 V
E Cl/Cl ° <0
E cell n [H+ ]
⇒Non-spontaneous reaction. Here, n = number of electrons involved in
Based on the data given above, the reaction
(d) X = Zn, Y = Ni
strongest oxidising agent will be (pH2 ) 1/ 2
Zn + Ni2 + → Zn2 + + Ni 0.0591
[JEE Main 2013] E = E °− log
(a) Cl (b) Cr 3+ 1 [H+ ]
° = E°
Ecell
Zn/ Zn 2+
+ E ° 2+
(c) Mn2+ (d) MnO −4 Ni /Ni
(p H 2 ) 1 / 2
Ans. (d) = 0.76 − 0.23 E = − 0.0591log
[H+ ]
Higher the SRP (Standard Reduction = 0.53 V
[QE ° = 0 for H− electrode]
Potential), stronger is the oxidising ° >0
E cell
agent Among the given, electrode (p H 2 ) 1 / 2
⇒Spontaneous reaction. ⇒ E will be −ve when is +ve.
potentials, E ° – 2 + is highest. Hence, [H+ ]
MnO 4 / Mn
MnO–4 is the strongest oxidising agent. 70 In view of the signs of ∆ r G° for the i.e., (pH 2 ) 1/ 2 > [H+ ]

69 The standard reduction potentials following reactions

pH2 [H+ ] (pH2 )1/ 2 Ered
for Zn 2+ /Zn, Ni 2+ /Ni and Fe 2+ / Fe PbO 2 + Pb → 2PbO, ∆ r G° < O
[H+ ]
are – 0.76, – 0.23 and – 0.44 V, SnO 2 + Sn → 2SnO, ∆ r G° > O
respectively. The reaction Which oxidation states are more (a) 1 atm 2.0 M 0.25 +ve
X + Y 2+ → X 2+ + Y will be characteristic for lead and tin? (b) 1 atm 1.0 M 1.0 0
spontaneous when [AIEEE 2012] [AIEEE 2011] (c) 2 atm 1.0 M 2.0 −ve
(a) X = Ni,Y = Fe (b) X = Ni, Y = Zn (a) For lead + 4, for tin + 2 (d) 2 atm 2.0 M 0.50 + ve
(c) X = Fe,Y = Zn (d) X = Zn,Y = Ni (b) For lead + 2 , for tin + 2
Ans. (d) (c) For lead + 4, for tin + 4 Hence, when p(H2 ) is 2 atm and [H+ ] is
(d) For lead + 2, for tin + 4 . M, E red is negative.
10
A cell reaction is spontaneous, if ∆G ° < 0.
Since, °
∆G ° = − nFE cell Ans. (d)
72 The Gibbs energy for the
PbO2 + Pb → 2PbO
Thus, ° > 0, E cell
E cell ° = E ox
° + E red
° decomposition of Al 2O 3 at 500°C is
Oxidation state +4 0 +2
as follows [AIEEE 2010]
Red Since, ∆G ° <0, i.e., it is negative. 2 4
X + Y 2 + → X2 + + Y Therefore, the reaction is spontaneous Al 2O 3 → Al + O 2 ,
Oxi in the forward direction. This suggest
3 3
−1
(a) X = Ni, Y = Fe that Pb2 + is more stable thanPb4+ . ∆ r G = +966 kJ mol
Ni + Fe2 + → Ni2 + + Fe SnO2 + Sn → 2SnO The potential difference needed
E ° 2 + = + 0. 23 V Oxidation state +4 0 +2 for electrolytic reduction of Al 2O 3
Ni/ Ni

E° 2 + = − 0.44 V Since, ∆ r G ° >0, i.e., it is positive, at 500°C is at least

Fe /Fe therefore, the reaction is (a) 4.5 V (b) 3.0 V
Thus, ° = E°
E cell
Ni/ Ni 2+ + E° 2 +
Fe /Fe
non-spontaneous in the forward (c) 2.5 V (d) 5.0 V
direction. But it will be spontaneous in
= − 0.21 V Ans. (c)
the backward direction. This suggests
° <0
E cell that Sn4+ will be more stable thanSn2 + . 2 4
Al2O3 → Al + O2
These facts are also supported by the 3 3
⇒Reaction is non-spontaneous. inert pair effect down the group. 2 2−
(b) X = Ni, Y = Zn Thus, × 3 (O )
3
Ni + Zn2 + → Ni2 + + Zn 71 The reduction potential of i.e., 2 O2 − → O2 + 4 e −1 [Qn = 4]
E° 2+ =0.23 V hydrogen half-cell will be negative ∆G = + 966 kJ mol −1
Ni /Ni
if [AIEEE 2011] = 966 × 10 3 J mol −1
E° = − 0.76 V
Zn 2 + / Zn (a) p(H2 ) = 1 atm and [H+ ] = 2.0 M ∆G = − nFE cell
° = 0.23 + (−0.76) = − 0.53 V
∴ E cell (b) p(H2 ) = 1 atm and [H+ ] = 1.0 M
966 × 10 3 = − 4 × 96500 × E cell
° <0
E cell (c) p(H2 ) = 2 atm and [H+ ] = 1.0 M
⇒ E cell = 2.5 V
⇒ Non-spontaneous reaction. (d) p(H2 ) = 2 atm and [H+ ] = 2.0 M
Electrochemistry 127

73 Given, E ° 3 + = − 0.036 V, ° 0.0591 [Cr 3+ ]2 0.059

Fe /Fe E cell = E cell − log E ° cell = log K sp
n [Fe2 + ] 3 n
E ° 2+ = − 0.439 V 0.059
Fe /Fe 0.0591 (0.1)2 − 0.952 = log K sp
= 0.30 − log 1
The value of standard electrode 6 (0.01) 3
− 0.952
potential for the charge, 0.0591 10 −2 log K sp = = − 16.135
= 0.30 − log −6 0.059
[AIEEE 2009] 6 10
Fe 3+ (aq ) + e − → Fe (aq ) 2+
0.0591 77 The E ° 3 + values for Cr, Mn, Fe
= 0.30 − log 10 4
will be 6 M /M 2 +
(a) – 0.072 V (b) 0.385 V Ecell = 0.2606 V and Co are − 0.41, + 1.57, + 0.77 and
(c) 0.770 V (d) – 0.270 V + 1.97 V, respectively. For which
Ans. (c) 75 The cell, Zn| Zn 2+ (1M) ||Cu 2+ (1M)|Cu one of these metals, the change in
It is given that, (E° cell = 1.10 V), was allowed to be oxidation state from + 2 to + 3 is
Fe3+ + 3 e − → Fe, completely discharged at 298 K. easiest ? [AIEEE 2004]

E 1 ° = − 0.036 V …(i) The relative concentration of Zn 2+ (a) Cr (b) Mn

Fe2 + + 2e − → Fe, (c) Fe (d) Co
 [Zn 2+] 
E2 ° = − 0.439 V …(ii) to Cu 2+   is Ans. (a)
 [Cu 2+]  [AIEEE 2007] E° = − 0.41 V
We need to calculate Cr 3+ / Cr 2 +
Fe3+ + e − → Fe2 + , E 3 ° = ? …(iii) (a) antilog (24.08) (b) 37.3 E° = + 1.57 V
Mn 3+ / Mn 2 +
Equation (iii) can be obtained by (c) 1037.3 (d) 9.65 × 104 E° = + 0.77 V
Fe 3+ /Fe 2 +
subtacting Eq. (ii) from (i) but E 0 being an Ans. (c) E° = + 1.97 V
intensive property, cannot be calculated Co 3+ / Co 2 +

by this way. In order to calculate E 3° ,

Cell is completely discharged. It means More negative value of E ° red indicates
equilibrium gets established, E cell = 0 better reducing agent. Thus, easily
concept of ∆G ° is used .
Zn|Zn2 + (1 M) | | Cu2 + (1 M) | Cu oxidised. Hence, oxidation of Cr2 + to
∆G 1° for Eq. (i) is given by
Cell reaction :Zn + Cu2 + r Zn2 + + Cu Cr 3+ is the easiest.
∆G 1° = −3 × F × (−0.036) 2+
[Zn ]
⇒ ∆G 1° = + 0.108 F K eq =
[Cu2 + ] 78 Consider the following E° values :
∆G2° for Eq. (ii) is given by
∆G2° = −2 × F × (−0.439) We know, E cell = E ° cell −
0.0591
log K eq
E° 3 + 2+ = + 0.77 V
Fe /Fe
⇒ ∆G2° = 0.878F
n E° 2+ = − 0.14 V
0.0591 Sn / Sn
∆G 3° for Eq. (iii) is given by E ° cell = log K eq Under standard conditions, the
n
∆G 3° = −1 × F × E 3° ⇒ ∆G 3° = ∆G 1° − ∆G2° potential for the reaction
0.0591
or 1.10 = log K eq Sn(s) + 2Fe 3+ (aq) → 2Fe 2+ (aq)
⇒ −1 × F × E 3° = 0.108 F − 0.878 F 2
⇒ E 3° = 0.770 V [Zn2 + ] + Sn 2+ (aq) is [AIEEE 2004]
K eq =
[Cu2 + ] (a) 1.68 V (b) 1.40 V
74 Given, E ° = 0.72 V,
= antilog
2.20
= antilog 37.3
(c) 0.91 V (d) 0.63 V
Cr3 + / Cr Ans. (c)
0.0591
E° = − 0.42 V. Sn (s ) + 2Fe3+ (aq) → 2Fe2 + (aq)
Fe2+ /Fe
76 Given the data at 25°C, + Sn2 + (aq)
The potential for the cell
Cr | Cr 3+ (0.1M) || Fe 2+ (0.01M) | Fe is Ag + I − → AgI + e − ; E° = 0.152 V E ° cell = E ° oxi + E ° red
[AIEEE 2008] Ag → Ag + + e − ; E° = − 0.8 V = E°
Sn/ Sn 2 +
+ E°
Fe 3+ /Fe 2 +
(a) 0.26 V (b) 0.399 V What is the value of log K sp for Given, E° = − 0.14 V
(c) – 0.339 V (d) – 0.26 V Sn 2 + / Sn
AgI ? ∴ E° = + 0.14 V
Ans. (a) Sn/ Sn 2 +
 RT 
3+ 2+ 2.303 = 0.059 V [AIEEE 2006] E° = 0.77 V
Cr | Cr (0.1 M) | | Fe (0.01 M) |Fe  F  Fe 3+ /Fe 2 +
Oxidation half cell ∴ E ° cell = 0.14 + 0.77= 0.91 V
3+
(a) − 8.12 (b) + 8.612
Cr → Cr + 3 e × 2 –
(c) −37.83 (d) −16.13
Reduction half cell
79 In a cell that utilises the reaction
Ans. (d)
Fe2 + + 2e – → Fe × 3 Zn (s) + 2H+ (aq) →
AgI(s ) + e − r Ag (s) + I ; −
Net cell reaction Zn 2+ (aq) + H2 (g)
E 1° = − 0.152
2Cr + 3Fe2 + → 2Cr 3+ +3Fe; n = 6 Ag (s ) → Ag + + e − ; E2° = − 0.8
addition of H2SO4 to cathode
E° = E° + E°
cell oxi red AgI(s ) → Ag + + I− ; E ° = − 0.952
compartment will [AIEEE 2004]
(a) lower the E and shift equilibrium to
= 0.72 − 0.42 = 0.30V [E ° = E 1° + E2° ]
the left
128 JEE Main Chapterwise Topicwise Chemistry

(b) lower the E and shift the equilibrium Ans. (a) 85 For a cell given below
to the right More negative value of E ° means higher
(c) increase the E and shift the reducing power.
Ag | Ag + || Cu 2+ | Cu
– +
equilibrium to the right 82 For the redox reaction Ag + + e − → Ag; E ° = x
(d) increase the E and shift the
equilibrium to the left Zn (s) + Cu 2+ (0.1 M) → Cu 2+ + 2e − → Cu; E ° = y
Ans. (c) Zn 2+ (1 M) + Cu (s ) E° cell is [AIEEE 2002]

Zn (s ) + 2H+ → Zn2 + (aq) + H2 (g) taking place in a cell, E°cell is 1.10 V. (a) x + 2 y
2+
[Zn ] E cell for the cell will be (b) 2x + y
Reaction quotient, Q = (c) y − x
[H+ ]2  RT 
 2.303 = 0.0591 (d) y − 2 x
Corresponding cell is  F  [AIEEE 2003]
Ans. (c)
Zn | Zn2 + (C1) || H+ (aq) | Pt(H2 ) (a) 2.14 V (b) 1.80 V
− (c) 1.07 V (d) 0.82 V At LHS (oxidation)
+
Anode Cathode 2 × (Ag → Ag + + e − );
0.0591 Ans. (c)
and E cell = E ° cell − log K E ° oxi = − x
2 By using Nernst equation,
0.0591 At RHS (reduction)
0.0591 [Zn2 + ] E cell = E ° cell − log Q
= E ° cell − log + 2 n Cu2 + + 2e − → Cu E ° red = + y
2 [H ]
Cu 2+
+ Zn → Zn 2+
+ Cu 2Ag + Cu 2+
→ Cu + 2Ag , +
0.0591 [H+ ]2
= E ° cell + log 0.1 M 1M
2 [Zn2 + ]
2+
[Zn ] 1 E ° red = ( y − x)
Q= = = 10
If H2SO4 is added to cathodic [Cu2 + ] 0.1
Note E ° values remain constant when
compartment, (towards reactant side), 0.0591 half-cell equation is multiplied/divided.
E cell = 1.10 − log 10
then Q decrease (due to increase inH+ ). 2
Hence, equilibrium is displaced towards = 1.10 − 0.0295 86 For the following cell with hydrogen
right and E cell increases. electrodes at two different
= 1.0705 V
pressures p 1 and p 2
80 The standard emf of a cell,
involving one electron change is 83 For a cell reaction involving a two Pt(H2 ) | H + (aq) |Pt(H2 )
found to be 0.591 V at 25° C. The electron change, the standard emf p
1
1M p2

equilibrium constant of the of the cell is found to be 0.295 V at emf is given by [AIEEE 2002]
reaction is (F = 96500 C mol −1 ) 25°C. The equilibrium constant of
the reaction at 25°C will be RT p RT p
[AIEEE 2004] (a) log e 1 (b) log e 1
[AIEEE 2003] F p2 2F p2
(a) 1.0 × 10 1
(b) 1.0 × 10 5
(a) 1 × 10−10 (b) 29.5 × 10−2
(c) 1.0 × 1010 (d) 1.0 × 1030 RT p RT p
(c) 10 (d) 1 × 1010 (c) log e 2 (d) log e 2
Ans. (c) F p1 2F p1
Ans. (d)
Relation betweenK eq and E °cell is The standard emf of the cell, Ans. (b)
2.303 RT 2303
. RT LHS half cell
E ° cell = log K eq E ° cell = log K eq
nF nF H2 (g) → 2H+ (1 M) + 2e −
0.0591 0.0591 p1
E ° cell = log K eq (at 298 K) ⇒ 0.295 = log K eq
n 2 RHS half cell
0.0591 ∴ log K eq = 10 ⇒ K eq = 1 × 10 10 2H+ (1 M) + 2e – → H2 (g)
0.591 = log K eq p2
1
H2 (g) → H2 (g)
∴ log K eq = 10 84 Which of the following reaction is p1 p2
⇒ K eq = 1 × 10 10 possible at anode ? [AIEEE 2002]
(a) Fe2 + 2 e − → 2F − E ° cell = 0.00 V,
81 Standard reduction electrode p
1 K = 2 ,n=2
potentials of three metals A, B and C (b) 2H+ + O2 + 2 e − → H2O p1
2
are + 0.5 V, − 3.0 V and − 1.2 V,
(c) 2Cr23+ + 7H2O → Cr2O27− + 14H+ + 6 e − RT
E cell = E ° cell − log e K
respectively. The reducing power
(d) None of the above nF
of these metals are [AIEEE 2003]
Ans. (c) RT p
(a) B >C > A =0 − log e 2
2F p1
(b) A >B >C Oxidation takes place at anode. Hence,
(c) C >B > A (a), (b) is not feasible as these are RT p
reduction reactions. But Cr 3+ is oxidised E cell = log e 1
(d) A >C >B 2F p2
to Cr 6 + (Cr2O27− ) under given condition.
Electrochemistry 129

TOPIC 3 (a) 11.4 (b) 7.6 Ans. (d)

(c) 15.2 (d) 22.8 Percentage efficiency of the fuel cell
Batteries, Fuel Cells Ans. (b) ∆G
and Corrosion = × 100
Key Idea This question is based upon ∆H
Faraday’s first law which states that The concerned reaction is
87 Compound A used as a strong “Mass of any substance deposited or 3
oxidising agent is amphoteric in liberated at any electrode is directly CH3OH(l ) + O2 (g ) → CO2 (g ) + 2H2O(l )
2
nature. It is the part of lead storage proportional to the quantity of electricity
passed.” ∆G r = [ ∆Gf (CO2 , g) + 2∆Gf (H2O, l )]
batteries. Compound A is 3
[2021, 26 Feb Shift-I] During charging : [− ∆Gf (CH3OH, l ) − ∆Gf (O2 , g)]
Pb + SO24 − → PbSO4 + 2e − 2
(a) PbO2 (b) PbO
(c) PbSO 4 (d) Pb 3O 4 ⇒ 1 F ≡ 1 g-equiv. of PbSO4 = − 394.4 + 2 (−237.2) − (−166.2) − 0
Ans. (a) 1
= mol of PbSO4 = − 394.4 − 474.4 + 166.2
2 . kJ mol −1
= −7026
In the set of four lead compounds Pb (II)
303 Percentage efficiency
compounds are PbO and PbSO4 . PbO2 is a ⇒ g PbSO4 7026.
Pb (IV) compound whereasPb3O4 is a 2 = × 100
mixed oxide of Pb (II) and Pb (IV) i.e. 303 726
∴ 0.05 F ≡ × 0.05 g of PbSO4
II (IV) 2 = 96.78% ≈ 97%
2PbO ⋅PbO2 .
= 7.575 g of PbSO4
Pb is a member of group 14 and it shows
+2 and +4 oxidation states. But due to 91 In a hydrogen-oxygen fuel cell,
inert pair effect,Pb2 + is more stable than 89 Galvanisation is applying a coating combustion of hydrogen occurs to
Pb4+ . So, Pb (IV) compounds are strong of [JEE Main 2016] [AIEEE 2004]
oxidising agents as Pb4+ gets easily (a) Cr (b) Cu (a) generate heat
reduced to more stablePb2 + . (c) Zn (d) Pb (b) create potential difference between
Pb+4 + 2 e − → Pb2 + , ∆G °<0 the two electrodes
Ans. (b)
(spontaneous) (c) produce high purity water
So, PbO2 or Pb3O4 can be the compound Zinc metal is the most stable metal to (d) remove adsorbed oxygen from
A. But out of these two compounds only cover iron surfaces. The process of electrode surfaces
PbO2 is used in lead storage batteries coating the iron surface by zinc is called
Ans. (b)
where a grid of lead packed withPbO2 galvanisation.
acts as cathode and also it is amphoteric Any cell (like fuel cell), works when
in nature. It reacts with both acids and potential difference is developed.
90 In a fuel cell, methanol is used as
alkali.
+4 −1 +2 0
fuel and oxygen gas is used as an
(i) PbO2 +2HCl → PbCl2 + Cl2 + H2O oxidiser. The reaction is 92 Several blocks of magnesium are
3 fixed to the bottom of a ship to
Here, PbO2 acts as a basic oxide as CH3OH(l ) + O 2 (g ) → CO 2 (g ) [AIEEE 2003]
well as an oxidising agent. 2 (a) keep away the sharks
(ii) PbO2 + 2NaOH → Na2PbO2 + H2O + 2H2O(l ) (b) make the ship lighter
Here, PbO2 acts as an acidic oxide. At 298 K standard Gibb’s energies (c) prevent action of water and salt
So, the compound A is PbO2 of formation for CH3OH(l ),H2O(l ) (d) prevent puncturing by under sea
(option-a). rocks
and CO 2 (g ) are –166.2, –237.2 and
88 The anodic half-cell of lead-acid −394.4 kJ mol −1 , respectively. If Ans. (c)
standard enthalpy of combustion Magnesium usually have a thin layer of
battery is recharged using
electricity of 0.05 Faraday. The of methanol is –726 kJ mol −1 , MgO over its surface which prevents the
underneath of metal from reacting with
amount of PbSO 4 electrolysed in g efficiency of the fuel cell will be moisture. Thus, several blocks of
[AIEEE 2009]
during the process is (Molar mass of magnesium are fixed to the bottom of
(a) 80% (b) 87%
PbSO 4 = 303g mol −1 ) (c) 90% (d) 97%
a ship to prevent action of water and
[2019, 9 Jan Shift-I] salt.
11
Chemical Kinetics
TOPIC 1 = 4.8 × 10 − 5 [(PtCl 4 ) 2− ] 04 PCl 5 (g) → PCl 3 (g) + Cl 2 (g)
Rate of Chemical Reaction = 2.4 × 10 −3 [{Pt(H2O)Cl 3 } − ][Cl − ] In the above first order reaction,
and Rate Expression where, square brackets are used the concentration of PCl 5 reduces
to denote molar concentrations. from initial concentration 50 mol
01 The reaction that occurs in a The equilibrium constant, L−1 to 10 mol L−1 in 120 minutes at
breath analyser, a device used to K C = .……… . (Nearest integer) 300 K. The rate constant for the
determine the alcohol level in a [2021, 26 Aug Shift-II] reaction at 300 K is x × 10 −2 min −1 .
person’s blood stream is Ans. (50) The value of x is …… . [Given,
2K 2Cr 2O 7 + 8 H2SO 4 + 3 C 2H6O → d [(PtCl 4 )2 − ] log 5 = 0.6989]
Consider, at equilibrium =0
[2021, 20 July Shift-II]
2Cr 2 (SO 4 ) 3 + 3 C 2H4O 2 + dt
−5 2− −3 Ans. (1)
2 K 2SO 4 + 11 H2O ∴ 4.8 × 10 [(PtCl 4 ) ] = 2.4 × 10
If the rate of appearance of [{Pt(H2O)Cl 3 } − ][Cl − ] 300K
PCl 5 (g) → PCl 3( g)+ Cl2 ( g)
Cr 2 (SO 4 ) 3 is 2.67 mol min − 1 at a Equilibrium constant,
It is of first order reaction.
particular time, the rate of [PtCl 4 ]2 –
KC = t = 050 M
disappearance of C 2H6O at the [Pt(H2O)Cl 3] – [Cl − ]
t = 120 min 10 M
same time is ……… mol min − 1 . 2.4 × 10 −3
= = 0.50 × 100 = 50 For first order reaction,
(Nearest integer) 4.8 × 10 −5 2.303 [A ]
[2021, 27 Aug Shift-I] k= log 0
t [At ]
Ans. (4) 03 For a chemical reaction A → B, it
Rate of appearence of 2 moles of [A0 ] = Initial concentration ofPCl 5
was found that concentration of B
Cr2 (SO4 ) 3, [At ] = Concentration of PCl 5 at
is increased by
d t = 120 min.
[Cr2 (SO4 ) 3] = 2.67 mol/min 0.2 mol L−1 in 30 min. The average
dt 2303
. 50
rate of the reaction is ……×10 −1 k= log
Rate of disappearence of 3 moles of 120 10
mol L−1 h −1 . (Nearest integer)
d [C2H6O] 2303
.
C2H6O, [2021, 25 July Shift-II] = × 0.6989
dt Ans. (4) 120
3 d [Cr2 (SO4 ) 3] 2.67 = 0.013413 min −1
= = ×3 Reaction, A → B
2 dt 2
At t = 0 0 = 13413
. × 10 −2 min −1
= 4.005
At t = 30 min 0.2 M 1.34 = Nearest integer = 1
= 4 mol/min
Here, initially at time zero, reaction is
02 The reaction rate for the reaction constant but after 30 minutes 05 The reaction 2A + B2 → 2AB is an
concentration of B is increased by
[PtCl 4] 2− + H2O elementary reaction. For a certain
- 0.2 mol L − 1 .
quantity of reactants, if the volume
[Pt(H2O)Cl 3] − + Cl − Average rate of reaction = −
∆ [A] ∆ [B]
= of the reaction vessel is reduced by
was measured as a function of ∆t ∆t
(0.2 − 0) a factor of 3, the rate of the
concentrations of different = reaction increases by a factor of
1
species. It was observed that ........... . (Round off to the nearest
2
− d [(PtCl 4 ) 2− ] = 0.4 mol L − 1 h − 1 integer). [2021, 17 March Shift-II]
dt = 4 × 10 − 1 mol L − 1 h − 1
Chemical Kinetics 131

Ans. (27) Rate of forward reaction is equal to rate 09 In the following reaction; xA → yB
Given, the reaction2A + B2 → 2AB is of reverse reaction at equilibrium and also,
K  d [A]  d [B] 
an elementary reaction. at equilibrium (K ) = f log 10 − = log 10  + 0.3010
So, rate of reaction = k [A]2 [B2 ] Kb  dt   dt 
Initial rate = k (a / V )2 (b / V ) 1 where,K (equilibrium constant) A and B respectively can be
where,a and b are the number of moles [N2 ] [H2O]2 Kf [N2 ] [H2O]2 [2019, 12 April Shift-I]
of A and B and V is the volume. = ⇒ = (a) n-butane and iso-butane
[H2 ]2 [NO]2 Kb [H2 ]2 [NO]2
On reducing the volume by a factor of 3, (b) C2H2 and C 6H6
the concentrations of A and B2 will Rearranging :
(c) C2H4 and C 4H8
become 3 times K f [H2 ] [NO]2 = K b [N2 ] [H2O]2 / [H2 ]
(d) N2O 4 and NO2
Final rate = k (3a / V)2 (3b / V ) 1 ∴ Rate of reverse reaction
Ans. (c)
2 1
= K b [N2 ] [H2O]2 / [H2 ]
32 × 3k     = 27 × initial rate
a b
In the given reaction; x A → y B
V  V 
08 NO 2 required for a reaction is  −d [A]   d [B] 
Hence, the rate becomes32 × 3 = 27 log 10   = log 10  dt  + 0.3010
 dt   
times of initial rate. produced by the decomposition of
Value of log 2 = 0.3010
3 N 2O 5 in CCl 4 as per the equation,
06 For the reaction 2A + 3B + C → 3P, Substituting0.3010 by log2
2 2N 2O 5 (g ) → 4NO 2 (g) + O 2 (g)
 d [A]   d [B] 
which statement is correct? he initial concentration of N 2O 5 is log 10  −  = log 10  dt  + log 2
 dt   
[2020, 3 Sep Shift-II] 3.00 mol L−1 and it is 2.75 mol L −1
dn 2 dnB 3 dnC Using logarithm rules,
(a) A = = after 30 minutes. The rate of
dt 3 dt 4 dt formation of NO 2 is  −d [A]   d [B] 
 dt  = 2 ×  dt 
dn 3 dnB 3 dnC [2019, 12 April Shift-II]    
(b) A = =
dt 2 dt 4 dt (a) 4.167 × 10−3 mol L −1 min −1 1  d [A]   d [B] 
(b) 1.667 × 10−2 mol L −1 min −1 ⇒−  = …(i)
2  dt   dt 
dn dn dn
(c) A = B = C
dt dt dt (c) 8.333 × 10−3 mol L −1 min −1
Using the rate equation (i) to determine
dnA 2 dnB 4 dnC (d) 2.083 × 10−3 mol L −1 min −1
(d) = = the reaction involved is
dt 3 dt 3 dt Ans. (b) 2A → B
Ans. (d) Key Idea The rate of a chemical reaction Option that fits correct in the above
For a reaction, means the speed with which the reaction is (c).
3 reaction takes place.
2A + 3B + C → 3P 2C2H4 → C4H8 .
2 For R → P
For a reaction, aA + bB = cC Rate of disappearance of R 10 A bacterial infection in an internal
Rate of reaction, Decrease in conc.of R ∆ [R] wound grows as N ′ (t) = N0 exp (t),
= =−
−1 d [A] −1 d [B] 1 d [C] Time taken ∆t where the time t is in hours. A dose
⇒ = =
a dt b dt c dt Rate of appearance of P of antibiotic, taken orally, needs
∴ For given reaction, Increase in conc. of P ∆[ P ]
= =+ 1 hour to reach the wound. Once it
−1 d [A] −1 d [B] −2 d [C] 1 d [P] Time taken ∆t
= = = reaches there, the bacterial
2 dt 3 dt 3 dt 3 dt Given, [N2O5 ] initial = 3.00 mol L− 1 population goes down as
d [A] 2 d [B] 4 d [C] 2 d [P]
= = = After 30 min, [N2O5 ] = 2 .75 mol L− 1 dN
= − 5N 2 . What will be the plot
dt 3 dt 3 dt 3 dt 2N2O5 (g) → 4NO2 (g) + O2 (g) dt
t= 0 3.0 M N
07 For the reaction t = 30 2.75 M of 0 vs t after 1 hour ?
N
2H2 (g) + 2NO(g) → N 2 (g) + 2H2O(g) From the equation, it can be concluded [2019, 10 April Shift-I]
that
the observed rate expression is,
1 − ∆ [N2O5 ] 1 ∆ [NO2 ] N0
rate =K f [NO] 2 [H2]. The rate × = × (a)
N0 (b)
expression for the reverse 2 ∆t 4 ∆t N N

reaction is [2020, 7 Jan Shift-II] − ∆ [N2O5 ] . ) mol L− 1

− (2.75 − 300
= = t(h) t(h)
2
(a) K b [N2][H2O] / [H2] ∆t 30
0.25
(b) K b [N2][H2O] ⇒ N0 N0
(c) K b [N2][H2O] 2 / [NO] 30 (c) (d)
N N
(d) K b [N2][H2O] 2 ∆ [NO2 ] ∆ (N2O5 )
and = −2
Ans. (a) ∆t ∆t t(h) t(h)
2H2 (g) + 2NO(g) = N2 (g) + 2H2O (g) ∆ [NO2 ] 0.25 Ans. (a)
⇒ = −2 ×
Rate law for forward reaction is given as: ∆t 30 The expression for bacterial growth is
rate = K f [NO]2 [H2 ] = − 1.667 × 10 − 2 mol L− 1 min− 1 N = N 0e t
132 JEE Main Chapterwise Topicwise Chemistry

⇒
N0
= e −t 12 For an elementary chemical 1
N k1
14 For a reaction A → 2B, rate of
2
From 0 to 1 hour N ′ (t) = N 0 e t reaction, A 2 =2A , the disappearance of ‘A’ is related to
k −1
From 1 hour onwards,
dN
= −5N 2 d [A] the rate of appearance of ‘B’ by the
dt expression for is expression [AIEEE 2008]
dt
On differentiating the above equation [2019, 10 Jan Shift-II] d [A] 1 d [B]
from N ′ to N we get. (a) − =
(a) 2k 1 [A2] − k −1 [A] 2
dt 2 dt
N t
−2 (b) k 1 [A2] − k −1 [A] 2 d [A] 1 d [B]
∫ N dN = −5∫ dt (b) − =
eN 0 1 (c) 2k 1 [A2] − 2k −1 [A] 2 dt 4 dt
[QAt 1 hour, N ′ = eN 0 ] (d) k 1 [A2] + k −1 [A] 2 d [A] d [B]
(c) − =
1 1  Ans. (c) dt dt
 −  = 5 (t − 1)
k1
 N eN 0  d [A] d [B]
The elementary reaction, A2 c 2A (d) − =4
Multiply both sides byN 0 , we get k −1 dt dt
N0 1 follows opposing or reversible kinetics, Ans. (b)
− = 5N 0 (t − 1) (i) Rate of the reaction,
N e 1
A → 2B
r = rforward − rbackward 2
N0 1
or, = 5N 0 (t − 1) + = k1 [A2 ] − k− 1 [A]2 … (i)
N e Remember for a A → bB
(ii) Again, rate of the reaction can be
= 5N 0t +  − 5N 0 
N0 1 1 d [A] 1 d [B]
 e  expressed as, − = = Rate of reaction
N d [A2 ] 1 d [A] a dt b dt
r=− =+
dt 2 dt For the given reaction
So, the rate of appearance of A, 2d [A] 1 d [B]
d [A] − =
N0 i.e. = 2r = 2k1 [A2 ] − 2 k− 1 [A]2 dt 2 dt
— dt
N
[From Eq. (i)] = Rate of reaction
d [A]
t(h) Rate of disappearance of A = −
13 Consider the reaction, dt
On comparing the above equation with
equation of straight line, y = mx + c
Cl 2 (aq ) + H2S(aq ) → =
1 d [B]

We get m = 5N 0 S(s ) + 2H+ (aq ) + 2Cl − (aq ) 2 × 2 dt

1 The rate equation for this reaction 1 d [B]
c = − 5N 0 =
e is, 4 dt
N
∴ Plot of 0 vs t is shown aside. rate = k[Cl 2] [H2S] 15 The rate equation for the reaction
N
Which of these mechanisms 2A + B → C is found to be rate
11 For a reaction scheme, is/are consistent with this rate = k [ A] [B]
k1 k2 equation? [AIEEE 2010] The correct statement in relation
A → B → C, if the rate of
(I) Cl 2 + H2S → H+ + Cl– to this reaction is that the
formation of B is set to be zero
+ Cl + + HS– (slow) [AIEEE 2004]
then the concentration of B is (a) unit of k must be s−1
given by [2019, 8 April Shift-II]
Cl + + HS– → H+ + Cl– + S (fast)
(b) t 1/ 2 is a constant
(II) H2S º H+ + HS − (fast)
k  (c) rate of formation of C is twice the
(a) k 1k2 [A] (b)  1  [A] Cl 2 + HS → 2 Cl − + H+ + S
−
rate of disappearance of A
 k2  (slow) (d) value of k is independent of the
(c) (k 1 − k2 )[A] (d) (k 1 + k2 )[A] (a) (II) only (b) Both (I) and (II) initial concentrations of A and B
Ans. (b) (c) Neither (I) nor (II) Ans. (d)
K1 K2
(d) (I) only 2A + B → C
A → B → C Ans. (d) Rate = k [A] [B]
Rate of formation of B is Slowest step is the rate determining It represents second order reaction.
d [B]
= k1 [A] − k2 [B] step. Thus, in case (I), rate law is given as Thus, unit of k is L mol −1 s −1.
dt rate = k[Cl2 ][H2S] Hence, (a) is false.
⇒ 0 = k1 [A] − k2 [B] While for the reaction given in case (II), t 1/ 2 is dependent of concentration but
 d [B]  rate law is given as rate
Q Given, dt = 0 
not constant. Hence, (b) is false.
  = k[H2S][Cl2 ][H+ ] –1. 1 d [A] d [C]
⇒ k2 [B] = k1 [A] And − =
k1 Hence, only mechanism (I) is consistent 2 dt dt
⇒Concentration of B, [B] = [A] with the given rate law.
k2 Thus, (c) is also false.
Chemical Kinetics 133

16 For the reaction, H2 + I 2 → 2HI, where,a = initial concentration of k1 Ea  1 1

log =  − 
the differential rate law is
reactant and k2 2.303R  T2 T1 
a − x = concentration of reactant after
[AIEEE 2002]
time t. At,T1 = 700 K, k1 = 6.36 × 10 −3 s−1,
(a) −
d [H2] d [I ]
= − 2 =2
d [HI]
For 50% completion, E a = 209 kJ mol −1, R = 8.314 J K−1 mol −1
dt dt dt 2.303 100 At,T2 = 600 K, k2 = x × 10 −6 s−1
d [H2] d [I2] d [HI] k= log …(i)
(b) − 2 = −2 = 100 − 50 6.36 × 10 −3 209
t 50% log −6
=
dt dt dt x × 10 2.303 × 8.314
d [H2] d [I2] d [HI] For 75% completion,
(c) − =− =  1 − 1 
k=
2.303 100  
dt dt dt log …(ii)  600 700 
t 75% 100 − 75
d [H2] d [I2] d [HI] 209  100 
(d) − =− = =  
2dt 2dt dt From Eqs. (i) and (ii), 2.303 × 8.314  420000 
Ans. (b) 2.303 100 2.303 100
log = log x = 16.
H2 + I2 → 2HI t 50% 50 t 75% 25
Rate of reaction 0.3010 0.6020 20 For the first order reaction,
=
=
− d [H2 ] − d [I2 ] 1 d [HI]
= = t 50% t 75% A → 2B, 1 mole of reactant A
dt dt 2 dt t 75% = 2t 50% gives 0.2 moles of B after
− 2d [H2 ] − 2d [I2 ] d [HI] t 75% 2 100 minutes. The half-life of the
or = = ∴ =
dt dt dt t 50% 1 reaction is …………… min. (Round
off to the nearest integer). [Use : In
17 Consider following two reactions,
19 The first order rate constant for 2 = 0.69, In 10 = 2.3; properties of
d [A] logarithms : ln x y = y ln x;
A → Product; − = k 1 [A] 0 the decomposition of CaCO 3 at
dt 700 K is 6.36 × 10 − 3 s − 1 and  x
ln   = In x − ln y]
B → Product; −
d [B]
= k 2 [B] activation energy is 209 kJ mol − 1 .  y
dt Its rate constant (in s − 1 ) at 600 K is (Round off to the nearest integer)
k 1 and k 2 are expressed in terms x × 10 − 6 . The value of x is .......... . [2021, 27 July Shift-II]
of molarity (mol L−1 ) and time (s −1 ) (Nearest integer) Ans. (656)
as [AIEEE 2002] [Given, R = 8.31 JK − 1 mol − 1 , log A → 2B
(a) s−1, M s −1 L−1 (b) M s−1, M s−1 6.36 × 10 − 3 Initial 1 mol 0
(c) s−1, M−1 s−1 (d) M s−1, s−1 = – 2.19, 10 − 4.79 = 1.62 × 10 − 5 ] Final 1− x 2x
Ans. (d) [2021, 27 Aug Shift-II] Given, 2x = 0.2 ⇒ x = 0.1
Unit of rate constant, Ans. (16) ∴Final 0.9 0.2
1 1 According to Arrhenius theory, Now, according to first order kinetics
k= . − E / RT
Time (conc) n − 1 k = Ae a 2303
. [A ]
t= log 10 0 … (i)
1 1 (k is the rate constant, A is Arrhenius k [At ]
For k1, n = 0, k= .
t (conc) 0 − 1 factor, E a = Activation energy, T is 0.691
t 1/ 2 = …(ii)
absolute temperature and R is gas
Hence, conc t −1 ≡ M⋅ s−1 k
constant.) Eq. (i) divided by Eq. (ii).
1 1 1
For k2 , n = 1, k = . = = s −1 E
t (conc) 1 − 1 t ln k = ln A − a t 2303
. ( 1)
RT = log 10
t 1/ 2 0.691 (0.9)
At temperatureT1,
1  10 
TOPIC 2 ln k1 = ln A −
Ea
…(i) = log 10  
9
RT1 0.3
Order and Molecularity =
1
[log 10 10 − log 10 9]
At temperatureT2 ,
Ea 0.3
18 For a first order reaction, the ratio ln k2 = ln A − …(ii) 1
RT2 = [1 − log 10 9]
of the time for 75% completion of a 0.3
reaction to the time for 50% Subtracting Eqs. (ii) from (i), 1
= [1 − log 10 32 ]
completion is ........... E  1 1 0.3
ln k1 − ln k2 = a  − 
(Integer answer) [2021, 31 Aug Shift-I] R  T2 T1  1
= [1 − 2log 10 3]
Ans. (2)  1 0.3
k1 E a 1
ln =  −  1
For a first order reaction, rate constant T T  = [1 − 2(0.477)]
k2 R  2 1
is given as, 0.3
2.303 a k1 E a  1 1 1
k= log 2.303 log =  −  = [1 − 0.954]
a−x T T 
t k2 R  2 1 0.3
134 JEE Main Chapterwise Topicwise Chemistry

t 0.0457 23 For the reaction, A + B -2C

=

Concentration
t 1/ 2 0.3
3 × t 3 × 100
The value of equilibrium constant
t 1/ 2 = = ≈ 656 (D)
is 100 at 298 K. If the initial
0.457 0.457
concentration of all the three
21 For a reaction of order n, the unit species is 1 M each, then the Time
of the rate constant is equilibrium concentration of C is
[2021, 27 July Shift-I] x × 10 −1 M. The value of x is …… .

Rate
(a) mol 1 − n L 1 − n s (b) mol 1 − n L2n s −1 (Nearest integer) (E)
(c) mol 1 − n L n − 1 s −1 (d) mol 1 − n L 1 − n s −1 [2021, 25 July Shift-I]

Ans. (c) Ans. (25)

According to given equilibrium Concentration
The unit of rate constant (k) for a
reaction of order n is reaction, Choose from the options given
Rate = k [A] n A + B q 2C below, the correct one regarding
or Rate = k [Reactant] n At t = 0 , 1 1 1 order of reaction is
Rate of reaction At t = t, 1− x 1− x 1 + 2x [2021, 25 July Shift-I]
⇒ k=
[Reactant] n [C]2 (a) (B) zero order (C) and (E) first order
So, equilibrium constant (k) =
(b) (A) and (B) zero order (E) first order
mol 1 L− 1s− 1 [A] [B]
= (c) (B) and (D) zero order (E) first order
[moln /Ln ] (1 + 2x)2
100 = (d) (A) and (B) zero order (C) and (E) first
= mol L s 1− n n−1 −1 (1 − x) (1 − x) order
Therefore, option (c) is correct. 1 + 2x
= 10 Ans. (b)
1−x
For zero order reaction, At = A0 − kt
22 The following data was obtained 3
1 + 2x = 10 − 10 x ⇒ x = Here, At = concentration at timet
for chemical reaction given below 4
A0 = initial concentration
at 975 K. Concentration of C at equilibrium, [C]
k = rate constant
2NO(g) + 2H2 (g)→ N 2 (g) + 2H2O(g) = 1 + 2x
Rate = k [A] 0
Put value of x, we get
[NO] [H2 ] [Rate] 3 Rate = k (constant)
mol L −1 mol L −1 mol L −1 [C] = 1 + 2 × compare with, y = mx + c
4
A. 8 × 10−5 8 × 10−5 7 × 10−9 3
= 1 + = 2.5 M = 25 × 10 −1 M
B. 24 × 10−5 8 × 10−5 2.1 × 10−8 2
Rate
So, concentration of C is 25 × 10 −1 M (A) Slope, k=constant
C. 24 × 10 −5
32 × 10 −5
8.4 × 10−8
Hence, x =`25.
The order of the reaction with Time
24 For the following graphs
respect to NO is ………… . [Integer For zero order reaction,
answer] [2021, 26 Aug Shift-I]
t 1/ 2 =
[A] 0
Rate

Ans. (1) 2k
(A)
Rate of the reaction = K [NO] x [H2 ] y Slope for graph betweent 1/ 2 and
where K is rate constant and x, y are [A] 0 = 1 /2k
order of reaction w.r.t. NO andH2 Time
t1/2
respectively.
(B) Slope = 1/2k
From observations A and B
7 × 10 −9 = K (8 × 10 −5 ) x (8 × 10 −5 ) y
t 1/2

…(i)
(B)
and 2.1 × 10 −8 = K (24 × 10 −5 ) x (8 × 10 −5 ) y [A]0
(Initial concentration)
…(ii)
Dividing Eqs. (i) by (ii) Initial For first order reaction,
concentration
7 × 10 −9 K (8 × 10 −5 ) x (8 × 10 −5 ) y Rate = k [concentration]
= Slope = k
Concentration

−8
2.1 × 10 K (24 × 10 −5 ) x (8 × 10 −5 ) y
x
1  1 (C)
= 
3  3 Slope = k
(E) Rate
x=1
Time
∴ Order of reaction w.r.t. NO is 1.
Concentration
Chemical Kinetics 135

1 Ans. (2) 29 For the reaction,

25 N 2O 5 (g) → 2NO 2 (g) + O 2 (g)
2 For first order reaction, aA + bB → cC + dD, the plot of
In the above first order reaction A
k × t = ln 0 …(i)
1
log k vs is given below
the initial concentration of N 2O 5 is At T
2.40 × 10 −2 mol L−1 at 318 K. The where, rate = rate constant
concentration of N 2O 5 after 1 hour t = time
was 1.60 × 10 −2 mol L−1. The rate Initial conc. of reactant, A0 = 100 Slope = –10000K

constant of the reaction at 318 K is Conc. of reactant after ‘t’ time, At = 32 log k
…… × 10 −3 min −1 . (Nearest integer) Put all values in equation (i)
[Given : log3 = 0.477, log 5 = 0.699] At = 32 1/T
[2021, 22 July Shift-II] 100
k × 570 = ln The temperature at which the rate
Ans. (7) 32
constant of the reaction is
k × 570 = 2303 (log 102 − log 25 )
For the reaction, .
10 −4 s −1 is ……… K
1 2303
.
N2O5 ( g) → 2NO(g) + O2 (g) ⇒ k= (2 − 5log 2) (Rounded off to the nearest
2 570
2303
.
integer).
For a first order reaction, rate constant = [2 − (5 × 0.3)]
will be 570 [Given : The rate constant of the
k=
2303
. C 2303
. reaction is 10 −5 s −1 at 500 K]
log 0 = × 0.5
t Ct 570 [2021, 25 Feb Shift-I]

.
2303 . × 10 −2
24 k = 2 × 10 − 3 s− 1 Ans. (526)
= log
60 . × 10 −2
16 According to Arrhenius equation,
−3
28 A and B decompose via first order Ea
= 6909
. × 10 log K = log A −
kinetics with half-lives 54.0 min .
2303 RT
k = 7 × 10 −3
and 18.0 min respectively. Starting Ea
∴Hence, k value at 318 K is 7 × 10 −3 min −1. Given, Slope = = 10,000
from an equimolar non-reactive 2303
. R
mixture of A and B, the time taken
26 A reaction has a half-life of 1 min. K 1 = 10 −5 , K 2 = 10 −4
The time required for 99.9% for the concentration of A to
become 16 times that of B is ……… T1 = 500 K
completion of the reaction is ………
min. K  Ea  1 1
min (Round off to the nearest log 10  1  =  − 
integer). (Round off to the nearest integer).  K 2  2.303R T1 T2 
[2021, 16 March Shift-II]
[Use : ln 2 = 0.69, ln 10 = 2.3]  10 −4   1 1
Ans. (108) log  = 10000  − 
−5 
[2021, 18 March Shift-II]
Given, (t 1/ 2 ) 1 = 54 min  10   500 T2 
Ans. (10)  1 1
(t 1/ 2 )2 = 18 min log 10 = 10000  − 
Using formula, 500 T
A B  2
1 C  t = 0, ‘ x ’ M t = 0, ‘ x ’ M
k = ln 0  T2 = 52631
. −
~ 526 K
t  Ct  To calculate, [At ] = 16 × [B t ] …(i)
As k =
ln2 time = ? 30 Sucrose hydrolyses in acid solution
t 1/ 2 A into glucose and fructose following
For Ist order reaction, [At ] = 0n
t 1/ 2 = 1min [Given] (2) first order rate law with a half-life
ln2 1  100  n = number of half-lives of 3.33 h at 25°C. After 9 h, the
∴ = ln 
1 t  0.1  From Eq. (i), fraction of sucrose remaining is f.
The value of log 10   is …… × 10 − 2
ln 1000 [At ] = 16 × [B t ] 1
⇒ t=
ln2 x
=
x
× 16 f 
3 × 23
. (2) n 1 (2) n 2
t= = 10 n2
(Rounded off to the nearest
0.69 (2) = (2) n 1 × (2) 4
integer).
⇒ n2 = n1 + 4 [Assume, ln 10 = 2.303,
27 For a certain first order reaction t t
= +4 ln 2 = 0.693] [2021, 24 Feb Shift-II]
32% of the reactant is left after (t 1/ 2 )2 (t 1/ 2 ) 1
570 s. The rate constant of this Ans. (81)
 1 1 
reaction is …… × 10 −3 s −1 . (Round ⇒ t  −  =4 Given,
 18 54 
off to the nearest integer). C12H22O11 + H2O 1  →
st order
4 × 18 × 54
⇒ t= Sucrose C6H12O6 + C6H12O6
[Given, log 10 2 = 0.301, In 10 = 2.303] 36 10 Glucose Fructose
[2021, 17 March Shift-I] = 108 min t 1/ 2 = h
3
136 JEE Main Chapterwise Topicwise Chemistry

t = 0, a = [A] 0 (initial conc.) Initial where,a 0 = initial concentration, k = rate

Experi- [B]/mol
At t = 9 h a − x = [A] t [A]/mol L−1 rate/mol L−1 constant
ment L−1 5 µg
[conc. at timet] min −1 t 1/ 2 =
For using 1st order equation, I 0.1 0.1 6.00 × 10−3 2 × 0.05 mg / year
2303
. [A] 0 = 50 years
K= log II 0.1 0.2 2.40 × 10−2
t [A] t −2 Thus, 50 years are required for the
III 0.2 0.1 . × 10
120 decomposition of 5 µg of X into 2.5 µg.
K ×t [A] 0
⇒ = log IV X 0.2 7.20 × 10−2
2303
. [A] t
V 0.3 Y 2.88 × 10−1 34 It is true that [2020, 3 Sep Shift-I]
ln2 × 9
= log  
1
(a) a second order reaction is always a
10 /3 × 2303
. F  X and Y in the given table are multistep reaction
 ln2  respectively
log   = 0.8124
1 [2020, 2 Sep Shift-II] (b) a zero order reaction is a multistep
⇒ Qk = 
F   t 1/ 2  (a) 0.4, 0.4 (b) 0.4, 0.3 reaction

(c) 0.3, 0.4 (d) 0.3, 0.3 (c) a first order reaction is always a
log   = 81.24 × 10 −2
1 single step reaction
F  Ans. (c)
(d) a zero order reaction is a single step
Let, the rate law is : r ∝ [A] a [B] b
x = 81.24 reaction
∴ a and b are the order of reaction w.r.t A
or x ≈ 81 Ans. (b)
and B respectively.
⇒Comparing first three (I, II, III) Only statement (b) is true whereas all
31 Gaseous cyclobutene isomerises to other statements are incorrect. A zero
experiments :
butadiene in a first order process a b order reaction is a multistep reaction
rII  0.1 
=   ×  
0.2
which has a ‘k’ value of 3.3 × 10 − 4 because in most of the zero order
rI  0.1   0.1 
s − 1 at 153°C. The time in minutes it reactions, free radical is the
. × 10 −2
24 intermediate which follow
takes for the isomerisation to ⇒ = 1 × 2b chain-initiation, chain-propagation and
proceed 40 % to completion at this 6 × 10 −3 chain-termination like steps, e.g., free
temperature is ....... . ⇒ 2 b = 4 ⇒b = 2 radical substitution reaction.
a 2 (a) A second order reaction is always a
rIII  0.2 
=   ×  
(Rounded off to the nearest 0.1
    single step reaction, e.g.,S N 2 and E2
integer) [2021, 24 Feb Shift-I] rI 0.1 0.1
reactions.
Ans. (26) . × 10 −2
12 (c) A first order reaction may be a
⇒ = 2a × 1
6 × 10 −3 multi-step reaction when intermediate
→ H2C == CHCH == CH2 ⇒ 2a × 2 ⇒a = 1
of the reaction, like carbocation (I 1) gets
1, 3-butadiene rearranged into its most stable form (I2 ).
Cyclobutene ⇒ rI = k × (0.1) 1 (0.1)2 Same is the case with (d).
It is a first order isomerisation reaction. ⇒ 6 × 10 = k × 10 −3
−3
So, options (a), (c) and (d) are not true.
Integrated rate law for 1st order reaction ⇒ k = 6 L2 mol −2 min −1
is
⇒ Expt. IV : rII = 6 × (X) 1 × (0.2)2 35 If 75% of a first order reaction was
[A]
kt = ln 0 …(i) ⇒ 7.2 × 10 −2 = 6 × (X) × (4 × 10 −2 )
[A] t completed in 90 minutes, 60% of
⇒ X = 0.3mol L −1 the same reaction would be
Here, k = rate constant ⇒ Ex pt. V : rV = 6 × (0.3) 1 × (Y )2 completed in approximately (in
[A] 0 = initial concentration ⇒ 2.88 × 10 −1 = 6 × 0.3 × (Y )2 minutes) ........... .
[A] t = concentration at time ‘t’ ⇒ Y = 0.4 mol L −1
Given, k = 33 . × 10 −4 s −1
(Take : log2 = 0.30; log2.5 = 0.40)
[2020, 4 Sep Shift-I]
[A] 0 = 100 33 Decomposition of X exhibits a rate Ans. (60)
⇒ [A] t = 100 − 40 = 60 constant of 0.05 µg/year. How Given, first order reaction,
Put values in Eq. (i), we get many years are required for the
100 t 75 = 90 minute
3.3 × 10 −4 s−1 × t = ln decomposition of 5 µg of X into ⇒ t 60 = ?
60 2.5 µg? [2019, 12 Jan Shift-I]
t = 1547.95 s = 25.79 min Consider the following reaction,
(a) 20 (b) 25 A → B
1
(1 min = 60 s or 1 s = min) (c) 40 (d) 50 (Reactant) (Product)
60 Time, t = 0 100
Ans. (d)
= 26 minutes t 15% = 90 min (100 − 75 ) = 25
Given, rate constant (k) = 0.05 µg/year t 60% = ? (100 − 60) = 40

32 The results given in the below table Thus, from the unit of k, it is clear that For first order reaction,
the reaction is zero order. Now, we know 2 . 303  a 0 
were obtained during kinetic t= log  
that k a 
studies of the following reaction : a
half-life (t 1/ 2 ) for zero order reaction = 0 a 0 = Initial concentration
2A+B → C+D 2k  a = Concentration 
 
Chemical Kinetics 137

For 75%, 37 Consider the following reactions where, t 1/ 2 = 693

. yr (given)
2 . 303  100 
t 75% = log   …(i) A→ P1; B→ P2; C→ P3; D→ P4, Also, we know 90% nuclei are decayed
k  25 
The order of the above reactions are N 0 100
 Initial conc.= 100 ∴ = = 10
 Conc. = 100 − 75 = 25 a, b, c and d, respectively. The following Nt 10
  graph is obtained when log[rate] vs N0
For 60%, log[conc.] are plotted : Put the values of λ and in Eq. (i), we get
Nt
2 . 303  100  [D]
t 60% = log   …(ii) [B] 693
.
k  40  [A] ∴t = × 2303
. × log 10 = 2303
. (yr)
0.693

log [rate]
 Initial conc.= 100 
 Conc. = 100 − 60 = 40  [C]
  39 For the reaction, 2A + B → C, the
On equating Eqs. (i) and (ii),
values of initial rate at different
2 . 303  100 
log   log [conc.] reactant concentrations are given
t 60%  40 
= k in the table below.
t 75% 2 . 303 log  100  Among the following, the correct
  The rate law for the reaction is
k  25 
sequence for the order of the [2019, 8 April Shift-I]
 0.3979  reactions is
t 60% = t 75% ×   [2020, 6 Sep Shift-I]
 0.602  [A] [B] Initial rate
(a) D > A > B > C (b) A > B > C > D
(mol L−1) (mol L−1) (mol L−1s −1)
0.3979 (c) C > A > B > D (d) D > B > A > C
⇒ t 60% = 90 × 0.05 0.05 0.045
0.602 Ans. (d)
t 60% = 5948
. minute 0.10 0.05 0.090
We know that,
≈ 60 min Rate = k (concentration) n 0.20 0.10 0.72
[n = order of reaction and k = rate (a) rate = k [A] [B] 2 (b) rate = k [A] 2 [B] 2
36 A flask contains a mixture of constant]
(c) rate = k [A] [B] (d) rate = k [A] 2 [B]
compounds A and B. Both Taking log both side,
log (Rate) = log k + nlog [concentration] Ans. (a)
compounds decompose by
Slope of graph is the order of reaction Let the rate equation be k [A] x [B] y
first-order kinetics. The half-life for
greater the slope, greater is the order of From Ist values,
A and B are 300 s and 180 s, reaction. 0.045 = k [0.05] x [0.05] y …(i)
respectively. If the concentrations ∴Correct sequence for the order of From 2nd values,
of A and B are equal initially, the reaction is D > B > A > C.
0.090 = k [0.10] x [0.05] y …(ii)
time required for the concentration Hence, the correct option is (d).
From 3rd values,
of A to be four times that of B (in s)
0.72 = k [0.20] x [0.10] y …(iii)
is (Use ln 2 = 0.693) 38 During the nuclear explosion, one
[2020, 5 Sep Shift-I] of the products is 90 Sr with On dividing equations (i) by (ii), we get
x
(a) 120 (b) 180 half-life of 6.93 years. If 1 µg of 0.045  0.05 
=
(c) 300 (d) 900 90
Sr was absorbed in the bones of 0.09  0.10 
Ans. (d) 1 x
a newly born baby in place of Ca,  0.05   0.05 
− Kt ⇒  0.10  =  0.10 
We know that,N = N 0 e how much time, in years, is    
K can be calculated as : required to reduce it by 90% if it is ∴ x=1
ln2
K= (Here, t 1/ 2 = half-life) not lost metabolically ……… . Similarly on dividing Eq. (ii) by (iii) we get
t 1/ 2 [2020, 7 Jan Shift-I] x y
0.09  0.1   0.05 
Q The time required for the Ans. (23.03) =
concentration of A to be four times that 0.72  0.2   0.10 
Radioactive decay follows first order y
of B. Hence, kinetics. 0.01 0.1  0.05 
⇒ =
A = 4B ∴ Time taken for decay fromN 0 to N t is 0.08 0.2  0.1 
− ln2 t − ln2 t (N = number of nuclei) y
 0.05 
N 0e 300 = 4⋅N 0 e 180
1 N 0.25 = 
t = ln 0 
 0.10 
ln2t ln2t λ Nt
⇒ − = ln4 − ⇒ 0.25 = [0.5] y
300 180 1 N
t = × 2303
. log 0 …(i) [0.5]2 = [0.5] y
 1 1  λ Nt
⇒ ln2t − = 2ln2; ⇒ y =2
 180 300 
Also, we know λ = (decay constant) Hence, the rate law for the reaction
2 × 180 × 300 0.693
t= = 900 s = Rate = k [A] [B]2
120 t 1/ 2
138 JEE Main Chapterwise Topicwise Chemistry

40 The given plots represent the 41 The following results were When concentration of only A is
variation of the concentration of a obtained during kinetic studies of doubled, the rate of reaction
reaction R with time for two the reaction; increases from
different reactions (i) and (ii). The 2A + B → Products 0.3 mol L −1 s −1 to 0.6 mol L −1 s −1 .
respective orders of the reactions Which of the following is true?
are Initial rate of
[2019, 9 April Shift-I] (a) The whole reaction is of 4th order
[A] [B] reaction
Experiment (b) The order of reaction w.r.t. B is one
(i) (ii) (molL−1) (molL−1 ) (in molL−1
min −1) (c) The order of reaction w.r.t. B is 2
In [R] [R] (d) The order of reaction w.r.t. A is 2
I. 0.10 0.20 6.93 × 10 −3
[2019, 9 Jan Shift-II]
II. 0.10 0.25 6.93 × 10 −3
Time Time Ans. (c)
III. 0.20 0.30 .
1386 × 10 −2
(a) 1, 1 (b) 0, 2 For the reaction,2A + B → products.
(c) 0, 1 (d) 1, 0 The time (in minutes) required to Let, the rate expression is r ∝ [A] a [B] b
a b
Expt 1 2 =    
Ans. (d) consume half of A is r 2A 2B
In first order reaction, the rate [2019, 9 Jan Shift-I] r1  A   B 
expression depends on the (a) 5 (b) 10 .
24
concentration of one species only having (c) 100 (d) 1 ⇒ = 2a × 2b ⇒ 23 = 2a + ` b
0.3
power equal to unity. Ans. (b) ⇒ 3=a + b … (i)
nr → products Let, the rate expression is r ∝ [A] a [B] b . r2  2A  a  B  b
−d [r] From experiment I, Expt 2 =   
= k [r] r1  A   B 
dt a b
 0.25 
=   × 
r2 0.1 0.6
On integration, − ln[r] = kt − ln[r0 ]  ⇒ = 2a × 1
r1  0.1   0.20  0.3
or ln(r) = ln(r0 ) − kt
6.93 × 10 − 3  5
b ⇒ 21 = 2a ⇒ a = 1 …(ii)
⇒ y = c + mx ⇒ =1×  
6.93 × 10 −3  4 ∴ From Eq. (i), 1 + b = 3 ⇒b = 2
m = slope = −k (negative);
⇒ Order of the reaction
c = intercept = ln (r0 )  5
b
 5
0
 5
b
⇒ 1=   ⇒   =  ⇒ b =0 (n) = a + b = 1 + 2 = 3
The graph for first order reactions is  4  4  4 ⇒ Order of the reaction wrt. A = 1
From experiment II, ⇒ Order of the reaction wrt. B = 2
a b
r3  0.2   0.30 
ln (r) =  ×  43 The reaction, 2 X → B is a zeroth
r1  0.1   0.20 
order reaction. If the initial
1.386 × 10 − 2
⇒ = (2) a × (1.5) 0 concentration of X is 0.2 M, the
t 0.693 × 10 − 2 half-life is 6 h. When the initial
In zero order reaction, ⇒ 2 = 2a × 1 ⇒ 21 = 2a ⇒ a = 1 concentration of X is 0.5 M, the
[r] → product ⇒So, r ∝ [A] 1 [B] 0 ⇒ r ∝ [A] time required to reach its final
−d [r] t Order of the reaction (n) = 1
∴ = k or −d [r] t = kdt concentration of 0.2 M will be
dt ⇒Now, let for the 1st experiment, [2019, 11 Jan Shift-II]
On integrating, − [r] t = kt + c r1 = k ⋅ [A] (a) 7.2 h (b) 18.0 h
r 6.93 × 10 − 3 (c) 12.0 h (d) 9.0 h
If t = 0, [r] t = [r] 0 ⇒ k= 1 =
[A] 0.1 Ans. (b)
∴ − [r] t = kt − [r] 0
= 6.93 × 10 − 2 s− 1 For zero order reaction,
⇒ [r] t = [r] 0 − kt
⇒ t 50 =
0.693 [A0 ] − [At ] = kt ...(i)
Thus, the graph plotted between [r] t and k where,
t gives a straight line with negative slope
=
0.693
= 10 s [A0 ] = initial concentration
(−k) and intercept equal to [r] 0 .
6.93 × 10 − 2 [At ] = final concentration at time ‘t’
The graph for zero order reaction is
k = rate constant
42 For the following reaction, [A0 ]
Also, for zero order reaction,t 1/ 2 =
2A + B → products 2k
Given,t 1/ 2 = 6 h and [A0 ] =0.2 M
[ r] When concentration of both 0.2 0.2 1
∴ 6= or k = =
(A and B) becomes double, then 2k 2 × 6 60
rate of reaction increases from Now, from Eq. (i)
0.3 mol L −1 s −1 to 2.4 mol L −1 s −1 . [A0 ] − [At ] = kt
t
Chemical Kinetics 139

[A0 ] = 0.5 M, [At ] = 0.2 M .

2303 0. 5 dc
Given, ∴ k=
log = 0.0277 min−1 ∴ for C at various concentrations are
1 Q k = 1  50 0.125 dt
∴ 0.5 − 0.2 = ×t
60  60  Now, as per reaction 1.2 × 10 −3 = k (0 . 1) x (0 . 1) y …(i)
1 2H2O2 → 2H2O + O2 1.2 × 10 −3 = k (0 . 1) x (0 .2) y …(ii)
0.3 = ×t
60 1 d [H2O2 ] 1 d [H2O] d [O2 ] 2.4 × 10 −3 = k (0 .2) x (0 . 1) y …(iii)
⇒ t = 0.3 × 60 = 18 h − = =
2 dt 2 dt dt Solving for x [divide Eq. (iii) by Eq. (i)]

d [H2O2 ] 2.4 × 10 −3 k (0 .2) x (0 . 1) y

44 At 518°C, the rate of decomposition Rate of reaction, − = k [H2O2 ] −3
=
dt 1.2 × 10 k (0 . 1) x (0 . 1) y
of a sample of gaseous
acetaldehyde, initially at a pressure d [O2 ]1 d [H2O2 ] 1 2 = (2) x ⇒ x = 1
∴ =− = k [H2O2 ] …(i)
of 363 Torr, was 1.00 Torr s −1 when dt 2 dt 2 Solving for y [divide Eq. (iii) by Eq. (i)]
5% had reacted and 0.5 Torr s −1 When the concentration of [H2O2 ] 2.4 × 10 −3 k (0 .2) x (0 . 1) y
−3
=
when 33% had reacted. The order reaches 0.05 M, 1.2 × 10 k (0 . 1) x (0 .2) y
of the reaction is : [JEE Main 2018] d [O2 ] 1
= × 0.0277 × 0.05 [from Eq. (i)]  0. 1 
y
(a) 2 (b) 3 dt 2 ⇒ 2 = (2) x  
(c) 1 (d) 0  0.2 
d [O2 ]
Ans. (a) or . × 10 −4 mol min−1
= 693 Put x = 1 in above Eq., we get
dt
y
For the reaction, Alternative Method  0. 1 
Decomposes
2 = (2) ′   ⇒ 1 = (0. 5) y
CH3CHO(g) → CH4 + CO In fifty minutes, the concentration ofH2O2  0.2 
decreases from 0.5 to 0.125 M or in one
Let order of reaction with respect to half-life, concentration of H2O2 (1) 0 = (0. 5) y ⇒ y = 0
decreases from 0.5 to 0.25 M. In two dc dc
CH3CHO is m. Thus, = k [A] 1 [B] 0 ⇒ = k [A] 1
Its given, r1 = 1 torr/sec. when CH3CHO is half-lives, concentration ofH2O2 dt dt
5% reacted i.e. 95% unreacted. decreases from 0.5 to 0.125 M or
Similarly, r2 = 0.5 torr/sec when CH3CHO 2t 1/ 2 = 50 min 47 For a first order reaction,
is 33% reacted i.e., 67% unreacted.  0.693  −1 (A) → products
t 1/ 2 = 25 min ⇒ k =   min
Use the formula,  25  the concentration of A changes
r ∝ (a − x) m d [O2 ] 1 d [H2O2 ] k [H2O2 ] from 0.1 M to 0.025 M in 40 min.
or =− =
where (a − x) = amount unreacted dt 2 dt 2 The rate of reaction when the
. × 10 −4 mol min−1
m
r (a − x 1) m r  a − x1  = 693 concentration of A is 0.01 M is
so, 1 = or 1 =  
r2 (a − x2 ) m r2  a − x2  (a) 1.73 × 10−5 M / min [AIEEE 2012]

Now putting the given values

46 For the non-stoichiometric (b) 3.47 × 10−4 M / min
m reaction, 2A + B → C + D, the (c) 3.47 × 10−5 M / min
1  0.95 
=  following kinetic data were (d) 1.73 × 10−4 M / min
0.5  0.67 
obtained in three separate Ans. (b)
⇒ 2 = (141
. ) m or m = 2 experiments, all at 298 K. Rate constant for the first order reaction
[JEE Main 2014] is given by
45 Decomposition of H2O 2 follows a
2.303  a 
first order reaction. In 50 min, the
Initial Initial Initial rate of k= log  
concentration concentration formation of C t a − x
concentration of H2O 2 decreases (A) (B) (mol L −1 s −1 )
a = 0.1 M
from 0.5 to 0.125 M in one such
0.1 M 0.1 M 1.2 × 10−3 (a − x) = 0.025 M ⇒ t = 40 min
decomposition. When the 2.303 0.1
concentration of H2O 2 reaches 0.05 0.1 M 0.2 M 1.2 × 10−3 ∴ k= log
−3
40 0.025 M
M, the rate of formation of O 2 will 0.2 M 0.1 M 2.4 × 10
= 0.0347 min−1
be [JEE Main 2016]
 dx 
The rate law for the formation of C Rate =   = k [A] 1
(a) 6.93 × 10−4 mol min−1  dt 
is
(b) 2.66 L min−1 at STP
dc dc = 0.0347 × 0.1
(c) 1.34 × 10−2 mol min−1 (a) = k [A] [B] (b) = k [A] 2 [B]
dt dt = 3.47 × 10 –4 M min–1
(d) 6.93 × 10−2 mol min−1 dc dc
Ans. (a) (c) = k [A] [B] 2 (d) = k [A]
dt dt 48 The time for half-life period of a
For first order reaction,
2303
. a Ans. (d) certain reaction, A → products is
k= log 1 h. When the initial concentration
t a−x Rate law equation is given by,
of the reactant ‘A’ is 2.0 mol L −1 ,
Given, t = 50 min,a = 0.5 M, dc
= k [A] x [B] y
a − x = 0.125 M dt how much time does it take for its
140 JEE Main Chapterwise Topicwise Chemistry

concentration to come from 0.50 Ans. (a) 52 A reaction was found to be second
to 0.25 mol L−1 , if it is a zero order 2A + B → Products order with respect to the
reaction? [AIEEE 2010] [B] is doubled, half-life didn’t change. concentration of carbon monoxide.
(a) 4 h (b) 0.5 h (c) 0.25 h (d) 1 h Half-life is independent of change in If the concentration of carbon
Ans. (c) concentration of reactant i.e., first order monoxide is doubled, with
First order wrt to B everything else kept the same, the
Half- life for a zero order reaction is
given by When [A] is doubled, rate increased by rate of reaction will
[A ] two times.
t 1/ 2 = 0 (a) remain unchanged [AIEEE 2006]
⇒ First order wrt A
2k [where [A0 ] = initial (b) triple
concentration of reactant] Hence, net order of reaction = 1 + 1 = 2
(c) increase by a factor of 4
[A] 0 2.0 mol L−1 Unit for the rate constant = conc (1− n ) t −1 (d) double
⇒ k0 = =
2 t 1/ 2 2× 1h = (mol L−1) −1 ⋅ s−1 = Lmol −1 s−1 Ans. (c)
= 1.0 mol L−1 h−1 r ∝ [CO]2 ; r ′ ∝ [2CO]2 ; r ′ ∝ 4 [CO]2
Rate constant for a zero order reaction 51 A radioactive element gets spilled r ′ 4 [CO]2
is given by over the floor of a room. Its half-life Hence, = or r ′ = 4 r
1 1
r [CO]2
k = [(A0 ) − (A)] ⇒ t = [(A0 ) − (A)] period is 30 days. If the initial
t k activity is ten times the permissible
(0.50) − (0 .25) mol L−1
53 The following mechanism has been
t= value, after how many days will it proposed for the reaction of NO
1 mol L−1 h−1 be safe to enter the room? with Br 2 to form NOBr
⇒ t = 0.25 h [AIEEE 2007]
(a) 1000 days (b) 300 days
NO(g ) + Br 2 (g ) r NOBr 2 (g )
49 The half-life period of a first order (c) 10 days (d) 100 days NOBr 2 (g ) + NO(g) → 2NOBr(g)
chemical reaction is 6.93 min. The Ans. (d) If the second step is the rate
time required for the completion of n determining step, the order of the
N  1
99% of the chemical reaction will Activity ∝N ⇒ =  reaction with respect to NO (g) is
N 0  2
be (log 2 = 0.301) [AIEEE 2009]
n
[AIEEE 2006]
1  1 (a) 1 (b) 0
(a) 230.3 min (b) 23.03 min or =   or 10 = 2n
(c) 46.06 min (d) 460.6 min 10  2  (c) 3 (d) 2
Ans. (c) Taking log on both sides Ans. (d)
1
Half-life = 6.93 min, k1 =
0.693
= 0.1 min −1 log 10 = n log 2 ⇒ n = = 3.32 Rate = k [NOBr2 ] [NO] ...(i)
6.93 0.301
But NOBr2 is in equilibrium.
Time = n × half-life [NOBr2 ]
Rate constant for the first order reaction ∴ K eq =
is given by = 3.32 × 30 [NO] [Br2 ]
2.303 [A ] =99.6 days≈ 100 days
k= log 0 [NOBr2 ] = K eq [NO] [Br2 ]
t [A] Alternate method
Putting the [NOBr2 ] in Eq. (i), we get
where, [A0 ] = initial concentration Let the activity of safe working is A.
Given, A 0 = 10 [A] Rate = k ⋅K eq [NO] [Br2 ] [NO]
[A] = final concentration Hence, Rate = k ⋅K eq [NO]2 [Br2 ]
Radioactivity decay is the first order
0.1 =
2.303
× log
100 reaction. Rate = k ′ [NO]2 [Br2 ]
t 1 Let the activity of safe working is A. where k ′ = k ⋅K eq
2.303 It is given that, A 0 = 10 [A]
0.1 = log 102
t Half-life of a first order reaction is given 54 A reaction involving two different
2.303 × 2 reactants can never be
t= × 2 log 10 = 46.06 min by
0.1 0.693 0. 693 0. 693 [AIEEE 2005]
t 1/ 2 = ⇒ k= =
k t 1/ 2 30 (a) bimolecular reaction
50 Consider the reaction, (b) second order reaction
Rate constant for a first order reaction is
2A + B → product. When given by, (c) first order reaction
concentration of B alone was 2. 303 A (d) unimolecular reaction
doubled, the half-life did not k= log 0
t A Ans. (d)
change. When the concentration of 2. 303 A0 2. 303 10 [A] There are two different reactants (say A
A alone was doubled, the rate t= log = log
k A (0. 693 /30) [A] and B).
increased by two times. The unit of 2. 303 A + B → product
rate constant for this reaction is = log 10 Thus, it is a bimolecular reaction.
(0. 693 /30)
[AIEEE 2007] dx
= 99. 69 days If = k [A] [B]
(a) L mol−1 s−1 (b) no unit dt
(c) mol L−1 s−1 (d) s−1 ≈ 100 days It is second order reaction.
Chemical Kinetics 141

 dx  2.303 log 2 2.303

=
0.1 59 Rate constant, k of the first order
If   = k [A] = k [B] log
 dt  15 t 0.025 reaction when initial concentration
It is first order reaction. 2.303
= log 4 (C 0 ) and concentration (C t ) at time
Molecularity is independent of rate but is t
t, is given by equation
the sum of the reacting substances. 2.303 log 2 2 × 2.303 log 2
∴ = kt = log C 0 − log C t
Thus, it cannot be unimolecular reaction. 15 t
⇒ t = 30 min
Graph is a straight line if we plot
[AIEEE 2002]
55 t 1/ 4 can be taken as the time taken
57 The rate law for a reaction between (a) t vs log C 0 (b) t vs log C t
for the concentration of a reactant
(c) t −1 vs log C t (d) log C 0 vs log C t
to drop to 3/4 of its initial value. If the substances A and B is given by
rate = k [A] n [B] m . On doubling the Ans. (b)
the rate constant for a first order
concentration of A and halving the kt = − log e C t + log e C 0
reaction is k, the t 1/ 4 can be written
1
as [AIEEE 2005] concentration of B, the ratio of the t = − log e C t + log e C 0
k
(a) 0.75 / k (b) 0.69 / k new rate to the earlier rate of the
y = mx + c, straight line, negative slope.
(c) 029
. /k (d) 010
. /k reaction will be as [AIEEE 2003]
Ans. (c) 1
(a) (b) (m + n) 60 H2 gas is adsorbed on the metal
A → Product 2m + n
(c) (n − m) (d) 2 (n − m )
surface like tungsten. This follows
Initially a 0
..... order reaction. [AIEEE 2002]
After time t (a − x) x Ans. (d)
a − a  a (a) third (b) second
After t 1 / 4   Rate, r = k [A] n [B] m (c) zero (d) first
 4 4
On doubling [A] and halving [B], the rate
Ans. (c)
For first order kinetics, becomes
2.303  a  r ′ = k [2A] n [1 /2 B] m Most of the reaction which takes place
k= log   on the surface of heterogeneous
t a − x r ′ k [2A] n [1 /2 B] m
⇒ = catalyst proceeds being independent of
2.303 a r k [A] n [B] m concentration.
⇒ k= log
t 1/ 4 3a (2) n
= = (2) n ⋅ (2) − m = (2) n − m
4 (2) m 61 For a reaction A + 2B → C, rate
4 d [C]
2.303 log is given by + = k [ A] [B], hence
t 1/ 4 = 3 = 0.29 58 For the reaction system, dt
k k
2NO( g ) + O 2 ( g ) → 2NO 2 ( g) the order of the reaction is
[AIEEE 2002]
56 In a first order reaction, the volume is suddenly reduced to
(a) 3 (b) 2
concentration of the reactant, half its value by increasing the (c) 1 (d) 0
decreases from 0.8 M to 0.4 M in pressure on it. If the reaction is of Ans. (b)
15 min. The time taken for the first order with respect to O 2 and
Rate of the reaction depend upon the
concentration to change from 0.1 M second order with respect to NO; concentration of A and B both, hence it is
to 0.025 M is [AIEEE 2004] the rate of reaction will a second order reaction.
[AIEEE 2003]
(a) 30 min (b) 15 min
(c) 7.5 min (d) 60 min (a) diminish to one-fourth of its initial
Ans. (a)
value TOPIC 3
(b) diminish to one-eighth of its initial Arrhenius Theory, Activation
Order = 1 value Energy and Collision Theory
Concentration changes from 0.8 M to 0.4 (c) increase to eight times of its initial
M in (50%).
of Bimolecular Gaseous
value
15 min, thus half-life = 15 min =T50 Reaction
(d) increase to four times of its initial
A change from 0.1 M to 0.025 is 75% and value
for first order reaction 62 Which one of the following given
Ans. (c)
T75 = 2 × T50 = 2 × 15 = 30 min graphs represents the variation of
 dx 
  = k [NO] [O2 ]
2
Alternate method rate constant (k ) with temperature
 dt 
2.303 log 2 (T ) for an endothermic reaction?
T50 = 15 min ⇒ k = 2
 nO 2 
= k  NO 
n [2021, 1 Sep Shift-II]
T50  
 V   V 
 
2.303 log2
=  dx  k
  = 3 (nNO ) (nO 2 ) (a) k
15 2

a = 0.1 M ⇒ (a − x) = 0.025 M  dt  V
2.303  a  k (nNO )2 (nO 2 )  dx 
For first order, k = log   = =8 
t a − x (V /2) 3  dt  T
142 JEE Main Chapterwise Topicwise Chemistry

10 −3 min −1 . (Nearest integer) 66 If the activation energy of a

[Use: In 10 = 2.303; log 10 3 = 0.477; reaction is 80.9 kJ mol −1 , the
(b) k property of logarithm : fraction of molecules at 700 K,
log x y = y log x] [2021, 20 July Shift-I] having enough energy to react to
Ans. (106) form products is e − x . The value of x
T
Unit of rate constant ismin− 1, so it must is ………
be a first order reaction. (Rounded off to the nearest
For first order reaction, integer)
(c) k
A
k × t = 2.303 log 0 [Use, R = 8.31 JK –1 mol–1 ].
At [2021, 26 Feb Shift-II]
T k is the rate constantt is the time Ans. (14)
A0 is the initial conc. According to Arrhenius equation, the
At is the conc. at time,t factor e − Ea / RT corresponds to the
(d) k Using formula, fraction of molecules that have kinetic
A0 = 100, At = 90 in 1 min energy greater than E a (activation
100 energy).
So, K × 1 = 2.303 × log
T 90 −80.9 × 1000
= e −13. 90
Ea / RT 8.31 × 700
Ans. (c) = 2.303 × (log 10 − 2 log 3) ⇒ e =e
According to Arrhenius equation, = 2.303 × (1 − 2 × 0.477) ~− e −14 = e − x
− E / RT
k = Ae a = 0.10593 = 105.93 × 10 −3
x = 14
As the temperature increases, rate ≈ 106
[QE a = 80.9kJ mol −1
constant k also increases which will Hence, the rate constant for viral = 80.9 × 1000 J mol −1, R = 831
. J mol −1 K−1]
generally speed up the process (increase inactivation is 106.
the rate). So, graph will exponentially
increases as in option (c). 65 The decomposition of formic acid 67 An exothermic reaction X → Y has
on gold surface follows first order an activation energy 30 kJ mol −1 . If
63 For the reaction A → B, the rate kinetics. If the rate constant at energy change ∆E during the
constant k 300K is 1.0 × 10 −3 s −1 and the reaction is –20 kJ mol −1 , then the
(in s − 1 ) is given by activation energy, activation energy for the reverse
(2.47 × 10 3 ) E a = 11.488 kJ mol −1 , the rate reaction in kJ is ………… .
log 10 k = 20.35 − ⋅ [2021, 26 Feb Shift-I]
T constant at 200 K is …… ×10 −5 s −1
Ans. (50)
The energy of activation in kJ mol (Round off to the nearest integer).
X → Y , it is an exothermic reaction
−1
is ......... (Nearest integer) [Given, R =8.314 J mol −1 K −1 ]
whose ∆E or ∆H = −20 kJ mol −1
[Given : R = 8.314 J K − 1 mol − 1 ]
[2021, 16 March Shift-I]

[2021, 31 Aug Shift-II] Ans. (10)

Ans. (47) Given,T1 = 200 K,T2 = 300 K Eaf
According to Arrhenius theory, E a = Activation energy = 11488
. kJ/mol Energy Eab
−Ea Rate constant (k2 ) at 300 K = 10 −3 s −1 (PE) Reactant (X)
log k = log A …(i) ∆H
2.303RT To find = rate constant (k1) at 200 K
2.47 × 10 3 We know,
log 10 k = 20.35 − …(ii)
T k E 1 1 Product (Y)
log 2 =  − 
− 2.47 × 10 3
=−
Ea k1 2303
. 
R  T1 T2  Time
T 2.303RT
10 −3 11488
. × 10 3 Given, activation energy of the forward
Comparing Eqs. (i) and (ii), log =
k1 2303
. × 8314
. reaction (X → Y ) ,
E a = 2.47 × 2.303 × 8.314
 1 1  Efa = 30 kJ mol −1
= 47.29 kJ / mol ~− 47 kJ / mol  − 
 200 300  Activation energy of the backward or
10 −3 reverse reaction (Y → X) ,
64 The inactivation rate of a viral log =1 E ab can be calculated as,
preparation is proportional to the k1
∆H = Efa − E ab
amount of virus. In the first minute 10 −3
log = log 10
after preparation, 10% of the virus k1 ⇒ E ab = Efa − ∆H
is inactivated. The rate constant ⇒ k1 = 10 −4 = 30 − (−20)
for viral inactivation is …… × = 10 × 10 −5 s −1 = 50 kJ mol −1
Chemical Kinetics 143
Ea 15 Ea  1 1 
68 The rate constant of a reaction ln 5 = × ln(3.555) = −
increases by five times on increase 8314
. 300 × 315 .  303 313 
8314
E 15 (ln3.555 = 1.268)
in temperature from 27°C to 52°C. 16094
. = a ×
8314
. 300 × 315 E  313 − 303 
The value of activation energy in kJ 1 . 268 = a  
mol −1 is ……… (Rounded off to the Ea =
16094
. × 8314
. × 300 × 315 8314
.  303 × 313 
15 1268
. × 8314
. × 303 × 313
nearest integer) Ea =
E a = 84297.47 50 J /mol 10
[R = 8.314 J K −1 mol −1 ] = 99980.7 = 9998. kJ /mol
[2021, 25 Feb Shift-II]
70 The rate constant (k ) of a reaction
Ans. (52) 72 The rate of a certain biochemical
is measured at different
T1 = (273 + 27) = 300 K, reaction at physiological
temperature (T ), and the data are
T2 = (273 + 52) = 325 K temperature (T ) occurs 10 6 times
plotted in the given figure. The
Given, temperature coefficient of the faster with enzyme than without.
activation energy of the reaction in
reaction, The change in the activation
K kJ mol −1 is (R is gas constant)
αT = 325 = 5 energy upon adding enzyme is :
K 300 10 [2020, 8 Jan Shift-I]
K T2 Ea T − T  (a) + 6 RT (b) − 6 (2.303) RT
log = ×  2 1  In k
(c) + 6 (2.303) RT (d) − 6 RT
K T1 2.303R  TT
1 2 
5
Ans. (b)
K 325 Ea 325 − 300 
log =   Let the activation energy with and
K 300 2303
. × 8314
.  300 × 325  0
1 2 3 4 5 without enzyme be E a* and E a .
Ea 25 103/T Rate constant of reaction without
log 5 = ×
2303
. × 8319
. 300 × 325 [2020, 5 Sep Shift-II] catalyst is given by Arrhenius equation.
2 1 − E a / RT
E a = 52194.78 J mol − (a) (b) (c) R (d) 2R k = Ae
= 52.194 kJ mol − 1 R R
Taking log on both sides, we get
~− 52kJ mol − 1 Ans. (d) Ea
log k = log A − ...(i)
−E a / RT RT (2.303)
∴ k = Ae
69 The number of molecules with Taking natural logarithm on both sides, With catalyst, rate constant is 10 6 times
energy greater than the threshold the Arrhenius equation becomes. more
−E a
energy for a reaction increases five E  1
⇒ ln k = ln A −  a  ∴ 10 6 k = Ae RT
fold by a rise of temperature from  R T
27 °C to 42 °C. Its energy of E a*
 E a  10 3 log k + log 10 6 = log A −
activation in J/mol is ……… . ⇒ ln k = ln A −  3
× RT (2303
. )
 R × 10  T E a*
(Take ln 5 = 1.6094; ∴ log k = log A − − 6 ...(ii)
−Ea −10
R = 8.314 J mol −1 K −1 ) Slope of a graph = = RT (2303
. )
[2020, 4 Sep Shift-II] R × 10 3 5 Comparing Eqs. (i) and (ii)
Ans. (84297.47) E a = 2R × 10 3 J mol −1 ⇒E a = 2R kJ Ea E a*
= +6
Given, temperature rise 27°C to 42°C RT (2303
. ) RT (2303
. )
Hence,T1 = 273 + 27 = 300 K
71 The rate of a reaction decreased by
∴ E a* − E a = −6 (2303
. ) RT
T2 = 273 + 42 = 315 K
3.555 times when the temperature
{ln 5 = 16094 . J mol −1K−1}
R = 8314
was changed from 40° C to 30° C.
. 73 Consider the following plots of rate
According to question kT2 = 5kT1 as
The activation energy (in kJ mol −1 ) 1
of the reaction is ……… . constant versus for four different
molecules activated are increased five T
times so k will increases 5 times. Now,
− E / RT
(Take; R = 8.314 J mol −1K −1 , ln reactions. Which of the following
k = Ae a (Arrhenius equation) 3.555 = 1.268) [2020, 6 Sep Shift-II] orders is correct for the activation
On apply log both sides Ans. (100.00) energies of these reactions?
 kT  E  1 1 The Arrhenius eqaution is
ln  2  = a  − 
 k  R T T   KT  E  1 1
 T1  1 2
ln  2  = a  − 
kT2  KT1  R T1 T2  a
Here, =5 log k
kT1 KT2 d c
Given, = 3.555
Ea  1 1  KT1
ln 5 =  −  b
R  300 315  . JK− 1 mol − 1
R = 8314
E  315 − 300  T1 = 30 + 273 = 303 K;T2 = 40 + 273 = 313 K
ln 5 = a   1/T
8314
.  300 × 315  Substituting the given values in the
[2020, 8 Jan Shift-II]
Arrhenius equation,
144 JEE Main Chapterwise Topicwise Chemistry

(a) Eb > Ea > Ed > Ec 75 A sample of milk splits after 60 D.’’ It can be easily explained by following
(b) Ea > Ec > Ed > Eb graph.
min. at 300 K and after 40 min. at
(c) Eb > Ed > Ec > Ea 400 K when the population of

Enthalpy (kJ mol–1)

(d) Ec > Ea > Ed > Eb lactobacillus acidophilus in it 20
Ans. (d) doubles. The activation energy (in 15
Activation
According to Arrhenius equation kJ/mol) for this process is closest 10 enthalpy
to (Given, R = 8.3 J mol −1K −1
− E / RT
D
k = Ae a 5
 2 A+B
⇒ log k = log A −
E act ln   = 0.4, e −3 = 4.0)
2303
. RT
 3 Reaction C
[2020, 9 Jan Shift-II]
coordinate
E act = activation energy
1 −E act Ans. (3.98) Activation enthalpy (or energy) is the
Slope of the graph of ‘log k’ vs is 1 extra energy required by the reactant
T 2303
. R Time taken for milk to split ∝ molecules that result into effective
k
Greater the value of E act, more will be the collision between them to form the
negative slope. where, k = rate constant of the process
products.
From the graph, and, k at 2 different temperatures and
activation energy are related.
most −ve slope = c, followed bya, d and b. 77 For the reaction of H2 with I 2 , the
k −Ea  1 1 t
∴ Order of activation energies must be ln 2 =  −  = ln 1 rate constant is
k1 
R  T1 T2  t2
Ec > Ea > Ed > Eb 2.5 × 10 − 4 dm 3mol − 1 s − 1 at 327°C
 60  − E a  1 1  and 1.0 dm 3 mol − 1 s − 1 at 527°C.
∴ ln   =  − 
74 For following reactions :  40  .  400 300 
83 The activation energy for the
700K E a = 0.4 × 83
. × 1200 reaction, in
A → Product; = 3984 J mol −1 = 3.984 kJ mol −1
500K
kJ mol − 1 is (R = 8.314 JK − 1 mol − 1 )
A → Product 2 3
Given, ln = 0.4 ⇒ ln = − 0.4 [2019, 10 April Shift-II]
Catalyst 3 2 (a) 59 (b) 72
It was found that the E a is 2 (c) 150 (d) 166
(These are wrong values, becauseln is
decreased by 30 kJ/mol in the 3 Ans. (d)
3
presence of catalyst. If the rate –ve and ln is +ve, but assume them to Key Idea The Arrhenius equation for
2
remains unchanged, the activation rate constants at two different
be correct).
energy for catalysed reaction is temperatures is
(Assume pre exponential factor is k E a T2 − T1 
76 Consider the given plot of enthalpy log 2 =   [where,T2 > T1]
same): [2020, 9 Jan Shift-I] of the following reaction between A k1 2.303R  TT 1 2 
(a) 198 kJ/mol (b) 105 kJ/mol and B. A + B → C + D where, k1 and k2 are rate constants at
(c) 75 kJ/mol (d) 135 kJ/mol temperaturesT1 andT2 , respectively.
Identify the incorrect statement.
Ans. (c) [2019, 9 April Shift-II] R = Gas constant, E a = Activation
For catalysed reaction, let E a be x. energy
20
Then, for uncatalysed reaction, For the reaction,H2 + I2 → 2HI
E a = x + 30 (given in question). Enthalpy 15
(kJ mol–1) Given k1 = 2.5 × 10 −4 dm3mol −1s−1
Also, rate of reaction at 700 K (without 10 D
catalyst) = rate of reaction at 500 K (with T1 = (273 + 327) K = 600 K
5 A +B
catalyst). C k2 = 1 dm 3mol −1 s −1
∴k at 700 K without catalyst = k at 500 K Reaction coordinate at T2 = (273 + 527) K = 800 K
with catalyst. (a) D is kinetically stable product.
k2 Ea  T2 − T1 
Using relation, (b) Formation of A and B from C has Now, log =  
− E / RT highest enthalpy of activation. k1 . R  TT
2303 1 2 

k = Ae a
(c) C is the thermodynamically stable 1 Ea
E a = Activation energy. product. ⇒log =
2.5 × 10 −4 2303
. × 8.314 × 10 −3
∴ Ae − (x + 30 ) / 700 R = Ae − x / 500 R (d) Activation enthalpy to formC is 5 kJ
mol −1 less than that to form D.  800 − 600 
x + 30 x  
∴ =  600 × 800 
700 500 Ans. (d)
⇒ 7 x = 5x + 150 Only statement (d) is incorrect. (10 × 10 3) E 200
⇒ log = a ×
Corrected statement is ‘‘Activation 2.5 0.019 48 × 10 4
2x = 150
enthalpy to form C is 15 kg mol −1 more
⇒ x = 75 kJ mol −1 than 5 kg mol −1 that is required to form ⇒ log 4 + 3log 10 −
~ E a × 0.022
Chemical Kinetics 145

2 × log 2 + 3 where, A = Arrhenius factor or frequency Ans. (c)

⇒ Ea =
0.022 factor or pre-exponential factor The temperature dependence of a
36. ~ R = Gas constant, chemical reaction is expressed by
= . kJ mol −1
– 1636
0.022 E a = Activation energy Arrhenius equation,
− E a$ / RT
Taking log on both sides of the Eq. (i), the k = Ae …(i)
78 Consider the given plots for a E
equation becomes ln k = lnA − a Taking natural logarithm on both sides,
reaction obeying Arrhenius RT the Arrhenius equation becomes,
equation (0°C < T < 300°C) : ( k and E
ln k = ln A − a
E a are rate constant and activation RT
energy, respectively) ln/k
E
where, − a is the slope of the plot and
R
lnA gives the intercept.
1/RT Eq. (i) at two different temperatures for a
k k
reaction becomes,
On comparing with equation of straight k E 1 1
line ln 2 = a  −  …(ii)
k1 R  T1 T2 
Ea T(°C) (y = mx + c), the nature of the plot of lnk
I II
vs
1
will be : ⇒In the given problem,
Choose the correct option. RT T1 = 400 K,T2 = 500 K,
[2019, 10 Jan Shift-I] (i) Intercept = C = ln A k1 = 10 − 5 s− 1, k2 = ?
(a) Both I and II are wrong (ii) Slope/gradient = m = − E a = − y Ea
(b) Both I and II are correct ⇒ Ea = y − (Slope) = − 4606
R
(c) I is wrong but II is right So, the energy required to activate the
On substituting all the given values in Eq.
(d) I is right but II is wrong reactant, (activation energy of the
(ii), we get
reaction, E a is = y )
ln 2 = 4606 
Ans. (b) k 1 1 
On comparing with equation of straight − 
The Arrhenius equation is, k = A. e a
− E / RT
10 −5  400 500 
line
where, k = rate constant, (y = mx + c), the nature of the plot of lnk k2
ln = 2303
.
1 10 − 5
A = Arrhenius constant, vs will be:
RT k2
E a = activation energy, = 10
and T = temperature in K (i) Intercept = C = ln A 10 −5
From the equation, it is clear that k (ii) Slope/gradient = m = − E a = − y ⇒ k2 = 10 − 4 s−1
decreases exponentially with E a . So, the ⇒ Ea = y
Therefore, rate constant for the reaction
plot-I is correct. So, the energy required to activate the at 500 K is 10 − 4 s− 1.
In the plot-II, k is plotted with reactant, (activation energy of the
reaction, E a is = y )
temperature (in °C but not in K). So, at 81 Two reactions R 1 and R 2 have
0°C, k ≠ 0 and k will increase identical preexponential factors.
exponentially with temperature upto 80 For a reaction, consider the plot of
Activation energy of R 1 exceeds
300°C. Therefore, the plot-II is also ln k versus 1 /T given in the figure. If
correct. that of R 2 by 10 kJ mol − 1 . If k 1 and
the rate constant of this reaction at
k 2 are rate constants for reactions
400 K is 10 − 5 s − 1 , then the rate
79 If a reaction follows the Arrhenius R 1 and R 2 ,
constant at 500 K is k 
equation, the plot lnk vs 1/(RT) gives respectively at 300 K, then ln  2 
− 1 −k1 1 
straight line with a gradient (−y) is equal to (R = 8.314 J mol K )
unit. [JEE Main 2017]
Slope = –4606 (a) 8 (b) 12
The energy required to activate the ln k (c) 6 (d) 4
reactant is [2019, 11 Jan Shift-I]
y Ans. (d)
(a) unit (b) −y unit
R According to Arrhenius equation,
1/ T − E / RT
(c) yR unit (d) y unit k = Ae a
Ans. (d) (a) 4 × 10− 4 s− 1 where, A = collision number or
The temperature dependence of rate of (b) 10− 6 s− 1 pre-exponential factor.
a chemical reaction is expressed by (c) 10− 4 s− 1 R = gas constant,
Arrhenius equation as, (d) 2 × 10− 4 s− 1 [2019, 12 Jan Shift-II] T = absolute temperature
k = Ae − E α / RT …(i) E a = energy of activation
146 JEE Main Chapterwise Topicwise Chemistry

− E a 1 / RT
For reaction R 1, k1 = Ae …(i) ⇒ log 2 =
− Ea  1 − 1 
  180 kJ mol −1 and 200 kJ mol −1 ,
− E a 2 / RT 2.303 × 8.314  310 300  respectively. The presence of a
For reaction R2 , k2 = Ae …(ii)
⇒ E a = 53603.93 J/mol = 53.6 kJ / mol catalyst lowers the activation
On dividing Eq. (ii) by Eq. (i), we get
(E a − Ea ) 84 The rate of a chemical reaction energy of both (forward and
reverse) reactions by 100 kJ mol −1 .
2 1
k2 −
=e RT …(iii) doubles for every 10°C rise of
k1 temperature. If the temperature is The enthalpy change of the
[Q Pre-exponential factor ‘A’ is same for raised by 50°C, the rate of the reaction (A 2 + B2 → 2 AB ) in the
both reactions] presence of catalyst will be (in
reaction increases by about
Taking ln on both the sides of Eq. (iii), we
[AIEEE 2011] kJ mol −1 ) [AIEEE 2007]
get
(a) 10 times (b) 24 times (a) 300 (b) 120
 k  E a 1− E a 2
ln  2  = (c) 32 times (d) 64 times (c) 280 (d) 20
 k1  RT
Ans. (c) Ans. (d)
Given, E a = E a + 10 kJ mol − 1 A 2 + B2
r 2AB
1 2 For every 10°C rise of temperature, rate
= E a 2 + 10,000 J mol − 1 is doubled. Thus, temperature E a (forward) = 180 kJ mol −1
k 10,000 J mol − 1 coefficient of the reaction = 2 E a (backward) = 200 kJ mol −1
∴ ln 2 = =4
k1 8.314 J mol − 1 K− 1 × 300 K When temperature is increased by 50°, In the presence of catalyst,
rate becomes E a (forward) = 180 − 100
82 Higher order (>3) reactions are rare = 2 (50 10 ) = 80 kJ mol −1
due to [JEE Main 2015]
= 25 times E a (backward) = 200 − 100
(a) low probability of simultaneous = 100 kJ mol −1
collision of all the reacting species = 32 times
∆H = E a (forward) − E a (backward)
(b) increase in entropy and activation
energy as more molecules are 85 A reactant (A) forms two products = 80 − 100
involved
k
A →
1 B , Activation energy E a 1 = − 20 kJ mol −1
(c) shifting of equilibrium towards k2 For the value of enthalpy change of the
reactants due to elastic collisions A
→ C , Activation energy E a2 reaction, negative sign can be
(d) loss of active species on collision neglected.
If E a2 = 2 E a 1 , then k 1 and k 2 are
Ans. (a) related as [AIEEE 2011] 87 Rate of a reaction can be
The main conditions for the occurrence of E a 2 / RT
(a) k 1 = 2k2 e expressed by Arrhenius equation as
a reaction is proper orientation and
effective collision of the reactants. E a 1 / RT k = Ae − E / RT
(b) k 1 = k2 e
Since the chances of simultaneous E a 2 / RT In this equation, E represents
collision with proper orientation (c) k2 = k 1 e [AIEEE 2006]
between more than 3 species is very E a 1 / RT (a) the energy above which all the
(d) k 1 = Ak2 e
rare, so reaction with order greater than colliding molecules will react
3 are rare. Ans. (b) (b) the energy below which colliding
k1 k2 molecules will not react
83 The rate of a reaction double A → B, A → C,
(c) the total energy of the reacting
when its temperature changes By Arrhenius equation, molecules at a temperature,T
from 300 K to 310 K. Activation − Ea 1 / RT (d) the fraction of molecules with
k1 = A ′ e
energy of such a reaction will be − Ea 2 / RT
energy greater than the activation
(R = 8.314 JK −1 mol −1 and and k2 = A ′ e .[A' is Arrhenius energy of the reaction
log 2 = 0.301) [JEE Main 2013] constant] Ans. (b)
(a) 53.6 kJ mol−1 (b) 48.6 kJ mol−1 Q Ea 2 = 2Ea1 According to Arrhenius equation
−2 E a 1 / RT
(c) 58.5 kJ mol−1 (d) 60.5 kJ mol−1 ⇒ k2 = A ′ e k = Ae − E / RT
Ans. (a) − Ea / RT where, E is the activation energy below
k1 A ′e 1 E / RT
From Arrhenius equation, = = e a1 which the colliding molecules will not
k2 A ′e −2 Ea 1 / RT react.
k − Ea  1 1
log 2 =  −  ∴ k1 = k2 e
Ea / RT

k1 2.303 R  T2 T1 
1
88 Consider an endothermic reaction
Given,
k2
= 2 ;T2 = 310 K ⇒ T1 = 300 K
X → Y with the activation energies
86 The energies of activation for
k1 E b and E f for the backward and
forward and reverse reactions for
forward reactions respectively. In
On putting values, A 2 + B2 r2AB are 180 kJ mol −1
general [AIEEE 2005]
Chemical Kinetics 147

(a) there is no definite relation between 89 A schematic plot of lnK eq versus Slope of the given line is positive
E b and Ef inverse of temperature for a indicating that term A is positive, thus
(b) E b = Ef ∆H° is negative.
reaction is shown below
(c) E b > Ef 6.0
Thus, reaction is exothermic.
(d) E b < Ef
Ans. (d) 90 In respect of the equation
k = Ae − E a /RT in chemical kinetics,
In Keq
X → Y is an endothermic reaction,
∆H = + ve which one of the following
2×10–3
2.0 –3 statements is correct ?
1.5×10 [AIEEE 2003]
Eb 1/T(K–1)
Energy

u (a) k is equilibrium constant

Ef The reaction must be [AIEEE 2005] (b) A is adsorption factor
∆H (a) highly spontaneous at ordinary (c) Ea is energy of activation
temperature (d) R is Rydberg constant
(b) one with negligible enthalpy change Ans. (c)
(c) endothermic By Arrhenius equation,
E b = energy of activation of backward (d) exothermic − E / RT
k = Ae a ,
reaction Ans. (d) k = Rate constant
Ef = energy of activation of forward Variation of K eq with temperatureT is A = Pre-exponential, frequency factor
reaction given by van’t Hoff equation. E a = Activation energy,
∆H = heat of reaction ∆H ° ∆S ° R = Gas constant
Thus, Ef = E b + ∆H, Ef > E b log K eq = − +
2.303 RT R T = Temperature
A B
12
Surface Chemistry
log   = log 3
v 1 Ans. (d)
TOPIC 1  10  n The graph that correctly describes the
Adsorption and log   = 0. 585 × 0.4771 = 0.2791
v absorption isotherms at two temperature
 10  T1 andT2 is given by option (d).
Various Isotherms v According to Freundlich’s adsorption
= 10 0 .2791
10 isotherm, the amount of the gas
01 CH4 is adsorbed on 1 g charcoal at adsorbed is directly proportional to
⇒ v = 10 × 10 0 .2791 1
0°C following the Freundlich = 10 1.279 = 10 x pressure applied raised to the power .
n
adsorption isotherm. 10.0 mL of x = 1.279 1
CH4 is adsorbed at x = 128 × 10 −2
x
∝ pn 0 < 1 < 1
m  n 
100 mm of Hg, whereas 15.0 mL is
adsorbed at 200 mm of Hg. The x
02 Select the graph that correctly So, on increasing temperature,
volume of CH4 adsorbed at 300 mm m
describes the adsorption isotherms
decreases.
of Hg is 10 x mL. The value of x is at two temperaturesT 1 andT 2
∴ Adsorption is basically exothermic in
....... × 10 − 2 . (Nearest integer) (T 1 >T 2 ) for a gas. nature. Hence, correct option is (d).
[Use log 10 2 = 0.3010, (x = mass of the gas adsorbed ;
m = mass of adsorbent ; 03 Given below are two statement :
log 10 3 = 0.4771] [2021, 31 Aug Shift-II]
p = pressure) [2021, 31 Aug Shift-I] one is labelled as Assertion (A) and
Ans. (128)
x the other is labelled as Reason (R).
According to Freundlich isotherm, m T2
1 Assertion (A) SO2 (g) is adsorbed
x to a large extent than H2 (g) on
= kp n (a) T1
m activated charcoal.
(Using, amount of adsorbate ∝ Volume of p Reason (R) SO2 (g) has a higher
absorbate)
1 x critical temperature than H2 (g).
10 m
= k × (100) n …(i) T1 In the light of the above
1
1 (b) T2
statements, choose the most
15 appropriate answer from the
= k × (200) n …(ii)
1 options given below.
1 p
v [2021, 27 July Shift-II]
= k × (300) n …(iii)
1 x (a) Both A and R are correct but R is
m T1 not the correct explanation of A
Divide Eq. (ii) by (i)
1 (b) Both A and R are correct and R is
15  3 1 (c)
= 2 x ⇒ log   = log 2 T2 the correct explanation of A.
10  2 n
(c) A is not correct but R is correct.
1 log 3 − log 2 0.4771 − 0.3010 p
= = (d) A is correct but R is not correct.
n log 2 0.3010
x Ans. (b)
1 m
= 0.585 T2 As intermolecular force of attraction
n increases, critical temperature
Divide Eq. (iii) by (i) (d) T1
increases. with increase in critical
1
v temperature, extent of adsorption also
= 3n p increases. AsSO2 has more critical
10
Surface Chemistry 149

temperature thanH2 , it is adsorbed to a 06 In Freundlich adsorption isotherm Given graph is Freundlich adsorption
larger extent on charcoal. isotherm.
at moderate pressure, the extent
∴Both Assertion and Reason are correct According to equation,
of adsorption   is directly
x
and Reason is the correct explanation 1
 m x
= kp n …(i)
for Assertion.
proportional to p x . The value of x is m
x
04 CO 2 gas adsorbs on charcoal [2021, 25 Feb Shift-I] where, = amount of gas
1 m
following Freundlich adsorption (a) 1 (b) zero (c) ∞ (d)
n k and n = constants depending upon
isotherm. For a given amount of Ans. (d) nature of adsorbate and absorbent.
charcoal, the mass of CO 2 According to Freundlich isotherm, at Now, taking log both side in Eq. (i), we get
adsorbed becomes 64 times when moderate pressure, extent of adsorption x 1
log = log k + log p
the pressure of CO 2 is doubled. 1 m n
x
The value of n in the Freundlich   ∝ ( p) n For straight line, comparing above
 m
isotherm equation is …… × 10 −2 . equation to y = mx + c
1
(Round off to the nearest integer) So, m = slope =
x/m x/m= kp1/n n
[2021, 27 July Shift-I] (Extent of 1
Ans. (17) adsorption) hence, 0≤ ≤ 1
n
According to Freundlich adsorption x/m=kp It value lies in between 0 to 1.
isotherm,
Hence, with  = 0 to 1 .
O Pressure p 1 1
x
= kp1/ n . At moderate pressure, n n 
m
x
where x, m, k, p and n are amount of = k (p) 1/ n
m 08 Amongst the following statements
adsorbate, amount of adsorbent,
x
pressure of gas and constant ∝ (p) 1/ n … (i) regarding adsorption, those that
respectively. m
are valid are: [2020, 2 Sep Shift-II]
For a given amount of charcoal, x ∝ p1/ n x
∝ px (Given inquestion) … (ii) (A) ∆H becomes less negative as
1/ n m
x2 p  adsorption proceeds.
= 2  Compare Eqs. (i) and (ii),
x 1  p1  (B) On a given adsorbent,
(p) 1/ n ∝ px
Therefore, 64 = (2) 1/ n 1 ammonia is adsorbed more
∴ x=
26 = 21/ n n than nitrogen gas.
1
6= (C) On adsorption, the residual
n 07 In Freundlich adsorption isotherm,
slope of AB line is force acting along the surface
⇒ n = 0.166 = 0.17
[2021, 24 Feb Shift-I] of the adsorbent increases.
n = 17 × 10 − 2
(D) With increase in temperature,
B the equilibrium concentration
05 Which one of the following is
correct for the adsorption of a gas A of adsorbate increases.
at a given temperature on a solid (a) (D) and (A) (b) (B) and (C)
m
log x

surface? [2021, 26 Aug Shift-I] (c) (A) and (B) (d) (C) and (D)
(a) ∆H > 0, ∆S > 0 (b) ∆H > 0, ∆S < 0 Ans. (c)
(c) ∆H < 0, ∆S < 0 (d) ∆H < 0, ∆S > 0 log p On adsorption (both physical and
Ans. (c) chemical), the residual force acting
(a) n with (n = 0.1 to 0.5) along the surface of absorbent
The ∆H (enthalpy change) and ∆S (b) logn with (n > 1) decreases. So, ∆H of the adsorption
(entropy change) will be less than zero becomes less negative as adsorption
1
for adsorption of gas on solid surface, (c) log with (n < 1) proceeds. So, statement (a) is correct
i.e. ∆H < 0, ∆S < 0. n
but statement (c) is incorrect. Ammonia
Entropy change (∆S) The randomness of 1 1 
(d) with  = 0 to 1 molecules (NH3) is larger in size and
the gas molecules decreases as they are n n  dipolar in nature. Nitrogen is smaller in
adsorb on solid surface due to Ans. (d) size and it is a non-polar molecule. So,
restriction in their motion. B degree of adsorption :NH3 > N2 . So,
∴ ∆S is negative. statement (b) is correct. With increase in
A
Enthalpy change (∆H) Adsorption of gas temperature, kinetic energy of
log x/m

on solid surface is an exothermic Slope=1/n adsorbate molecules will increase and

process, as there is force of attraction hence, its equilibrium concentration will
logk decrease.
between adsorbate and adsorbent.
∴∆H is negative. log p So, statement (d) is not correct.
150 JEE Main Chapterwise Topicwise Chemistry

200 K
09 The mass of gas adsorbed, x per line. The intercept and slope for
250 K
unit mass of adsorbate, m was the line is 0.4771 and 2,
x
(c) m 700 K
measured at various pressures, p. respectively. The mass of gas,
x adsorbed per gram of adsorbent if
A graph between log and log p
m p the initial pressure is 0.04 atm, is
gives a straight line with slope 270 K ……… × 10 −4 g. (log3 = 0.4771)
equal to 2 and the intercept equal [2020, 6 Sep Shift-II]
x x
(d) m 250 K Ans. (48)
to 0.4771. The value of at a
m 200 K According to Freundlich adsorption
pressure of 4 atm is isotherm
p x
(Given, log 3 = 0.4771) = Kp1/ n … (i)
[2020, 2 Sep Shift-I] Ans. (a) m
Ans. (6) Freundlich adsorption gives the variation Taking logarithm of Eq. (i)
in the quantity of gas adsorbed by a unit x 1
From Freundlich adsorption isotherm log = log K + log p … (ii)
mass of solid adsorbent with the change m n
equation,
in pressure of the system for a given 1
x 1
log = log K + log p temperature. Here, given slope = = 2,
m n n
pressure (p) = 0.04 atmand intercept
= log K = 0.4771 (∴ K = 3)
log x/m mass of gas adsorbed per gram of
Slop=1/n
x
log m θ adsorbent
Intercept=log k x
= = K . p1 / n
log p m
x
The expression for the Freundlich = 3. p2
log p m
isotherm can be represented by the
x
When we plotlog x / m vs log p, we get a
following equation. ⇒ = 3 × (0.04)2 = 48 × 10 − 4 .
x m
straight line of = kp1/ n
1 1 m
(i) slope = = 2 ⇒n = 12 A mixture of gases O 2 , H2 and CO
n 2 where, n> 1
(ii) intercept = log K = 0.4771
where, x is the mass of gas adsorbed, x is are taken in a closed vessel
the mass of adsorbent. p is pressure and containing charcoal. The graph that
⇒log K = log 3
n is a constant, which depends upon the represents the correct behaviour
⇒ K =3 nature of adsorbent and the gas at a
So,
x
= Kp1/ n = 3 × 42 given temperature. of pressure with time is
m [2020, 9 Jan Shift-II]
Taking the logarithm on both side of the
= 48.00 (Qp = 4 atm) equation,
Pressure

x 1
log = log k + log p (a)
10 Adsorption of a gas follows m n
x
Freundlich adsorption isotherm. If x ∝p (At low pressure)
m
is the mass of the gas adsorbed on Time
x
mass m of the adsorbent, the ∝ p° (At high pressure)
Pressure

x m
correct plot of versus p is On increasing temperature physical
m (b)
adsorption decreases
[2020, 5 Sep Shift-II]

Time
200 K
(x/m)
Pressure

x
(a) m 250 K
270 K (c)
p Temperature
Hence, option (a) is correct. Time
270 K
Pressure

250 K 11 For Freundlich adsorption

x
(b) m
isotherm, a plot of log  (y-axis)
200 K
x (d)
 m
p
and logp (x-axis) gives a straight Time
Surface Chemistry 151

Ans. (c) 14 A gas undergoes physical Ans. (c)

Option (c) is the graph that represents adsorption on a surface and follows According to Freundlich adsorption
correct behaviour of pressure with time. the given Freundlich adsorption isotherm,
With passage of time, the pressure of x 1

the gases decreases and finally reach a isotherm equation = Kp 0. 5 x

∝ pn ⇒
x
= Kp1/ n
constant value. m m m
It is due to adsorption of gases by Adsorption of the gas increases On taking log on both sides, we get
charcoal. The decrease in pressure is with x 1
[2019, 10 April Shift-I] log   = log K + log p
faster in the beginning, but as the  m n
(a) increase in p and increase inT
adsorbent charcoal gets saturated, On comparing with equation of straight
(b) increase in p and decrease inT
pressure attains constancy. x
(c) decrease in p and decrease inT line, y = mx + c,plot oflog vs log pgives,
m
13 Adsorption of a gas follows (d) decrease in p and increase inT
(y2 − y 1) 1 2 1
Ans. (b) Slope = ⇒ =
Freundlich adsorption isotherm. x (x2 − x 1) n 4 2
is the mass of the gas adsorbed on For physisorption or physical adsorption,
x
mass m of the adsorbent. The plot Adsorption isotherm (Temperature, ⇒ ∝ p1 / 2
T = constant) is shown below: m
x
of log versus log p is shown in the
m 16 The correct match between item-I
x
given graph. is proportional to x
— x and Item-II is
m m Moderate pressure zone, — ∝ p1/n
m A. Benzaldehyde
[2019, 8 April Shift-I]
P. Dynamic phase
p
B. Alumina
where, x = amount of adsorbate, Q. Adsorbent
x
log — 2 m = amount of adsorbent, C. Acetonitrile
m
x
3 = degree of adsorption R. Adsorbate [2019, 9 Jan Shift-II]
m
(a) (A) → (R) ; (B) → (Q); (C) → (P)
1 1
log p = order of the reaction, where,0 < < 1 (b) (A) → (P); (B) → (R); (C) → (Q)
n n
(c) (A) → (Q); (B) → (P); (C) → (R)
2 /3
(a) p (b) p 3/2 and so, 1< n < ∞
1 1 (d) (A) → (Q); (B) → (R); (C) → (P)
(c) p 3 (d) p2 x x
Here, = Kp2 , i.e. ∝ p2 Ans. (a)
Ans. (a) m m
Using the principle of adsorption
Adsorption isobar (Pressure, p = constant) chromatography, qualitative and
Key Idea According to Freundlich,
x quantitative analysis of benzaldehyde
= kp1/ n [n> 1] can be done from its mixture with
m x acetonitrile. Here, a mobile phase moves
—
where, m = mass of adsorbent, x = mass m
over a stationary phase (adsorbent).
of Adsorbents used are alumina (Al2O3) and
x silica gel. The sample solution of
the gas adsorbed, = amount of gas T
m benzaldehyde and acetonitrile when
So, the rate of physical adsorption of the comes in contact with the adsorbent,
adsorbed per unit mass of solid gas, increases with p (when,T is
adsorbent, benzaldehyde gets adsorbed on the
constant) and decreases withT (when p
p = pressure, K and n = constants. is constant).
surface of the adsorbent. So,
benzaldehyde acts as absorbate whereas
The logarithm equation of Freundlich acetonitrile starts moving as mobile
adsorption isotherm is 15 Adsorption of a gas follows phase over the stationary phase of the
x 1 Freundlich adsorption isotherm. In adsorbate. Hence, act as dynamic phase.
log = log K + log p
m n the given plot,x is the mass of the
On comparing the above equation with gas adsorbed on mass m of 17 Given,
straight line equation, (y = mx + c) the adsorbent at pressure p ⋅ (x / m) Gas : H2 , CH4 , CO 2 , SO 2
1
we get m = slope = and c = log K is proportional to Critical 33 190 304 630
n
From the given plot, temp./K
y −y 2 unit
m= 2 1 log x On the basis of data given above,
m 4 unit
x2 − x 1 predict which of the following
=
1 2
=
gases shows least adsorption on a
log p
n 3 definite amount of charcoal?
2 1/ 4
⇒
x
= Kp2 / 3 (a) p (b) p (c) p 1/2 (d) p (a) CH4 (b) SO2 (c) CO2 (d) H2
m [2019, 9 Jan Shift-I] [2019, 12 Jan Shift-I]
152 JEE Main Chapterwise Topicwise Chemistry

Ans. (d) 19 According to Freundlich adsorption 21 In Langmuir’s model of adsorption

Same adsorbant (charcoal in this case) at isotherm which of the following is of a gas on a solid surface
same temperature will adsorb different correct? [AIEEE 2012] [AIEEE 2006]
gases to different extent. The extent to x (a) the rate of dissociation of
which gases are adsorbed is (a) ∝ p 0 adsorbed molecules from the
proportional to the critical temperature m
x surface does not depend on the
of gas. (b) ∝ p 1 surface covered
8a m
Q Tc = x (b) the adsorption at a single site on
27 Rb (c) ∝ p 1/ n the surface may involve multiple
where,a is the magnitude of m
molecules at the same time
intermolecular forces between gaseous (d) All of the above are correct for
different range of pressure (c) the mass of gas striking a given
molecules.
area of surface is proportional to
Thus, higher the cirtical temperature Ans. (d) the pressure of the gas
more is the gas adsorbed. Among the By Freundlich adsorption isotherm
given gases,H2 has the minimum critical (d) the mass of gas striking a given
x
temperature, i.e. 33K thus, it shows least = kp1/ n area of surface is independent of
m the pressure of the gas
adsorption on a definite amount of
charcoal. [In between low and high Ans. (c)
pressure range]
The adsorption of a gas is directly
18 For a linear plot of log (x / m) versus When n = 1,
proportional to the pressure of the gas.
x
log p in a Freundlich adsorption ∝ p1
m
isotherm, which of the following 22 Which one of the following
[In low pressure range]
statements is correct? (k and n are x characteristics is not correct for
constants) When n is large, =k
[JEE Main 2016] m physical adsorption? [AIEEE 2003]
(a) 1/n appears as the intercept [Independent of pressure] (a) Adsorption on solids is reversible
(b) Only 1/n appears as the slope (b) Adsorption increases with
 1
(c) log   appears as the intercept
( mx ∝ p) increase in temperature
 n (c) Adsorption is spontaneous

(d) Both k and 1/n appear in the slope

x ( mx ∝ p )
0
(d) Both enthalpy and entropy of
m adsorption are negative
term Ans. (b)
Ans. (b)
According to Freundlich adsorption
( mx ∝ p )
1/n
As temperature increases desorption
increases. Adsorbent + Adsorbate
isotherm, pressure (p) Adsorbed state + ∆E
a
x
= kp1/ n x
Adsorption is exothermic process
m Thus, ∝ p0 (forward direction), desorption is
On taking logarithm of both sides, we get m endothermic process (backward
[At high pressure range when direction).
x saturation point is reached] According to Le-Chatelier’s principle,
log = log k + log p1/ n
m increase in temperature favours
20 Which of the following statements endothermic process.
x 1
or log = log k + log p
m n is incorrect regarding
y = c + mx physisorptions? [AIEEE 2009]
(a) It occurs because of van der Waals’
TOPIC 2
forces Catalyst
Slope= 1 (b) More easily liquefiable gases are
θ n
log x/m

adsorbed readily 23 Which one of the following

(c) Under high pressure, it results into statements is not true about
multi molecular layer on adsorbent enzymes ? [2021, 20 July Shift-II]
log k
surface (a) Enzymes are non-specific for a
(d) Enthalpy of adsorption (∆H adsorption ) reaction and substrate.
log p is slow and positive (b) Almost all enzymes are proteins.
x Ans. (d) (c) Enzymes work as catalysts by
y = log , c = intercept = log k,
m Adsorption is an exothermic processi. e., lowering the activation energy of a
1 energy is released against van der Waals’ biochemical reaction.
m = slope =
n force of attraction (physisorptions). (d) The action of enzymes is
and x = log p Hence, ∆H is always negative. temperature and pH specific.
Surface Chemistry 153

Ans. (a) increases from It is the key step in the

Statement (a) is not true whereas all Group 5 to Group 11 metals with manufacture of H2SO4 .
other statements are true. maximum activity shown by Group (iii) Fe (Iron) is used as catalyst in
An enzyme is a substance that acts as a Haber’s process for the
7-9 elements. manufacture of ammonia.
catalyst in living organism, regulating
rate at which chemical reaction proceed Reason The reactants are most Fe(s)
N2 (g ) + 3H2 (g ) → 2NH3 (g)
without itself being altered in the strongly adsorbed on group 7-9
process. elements. [2020, 8 Jan Shift-II] (iv) Pd (Palladium) is used to prepare
The biological processes that occur (a) The Assertion is true, but the ethanal. Reaction involved is
within all living organisms are chemical Reason is false. PdCl2 / CuCl2
H2 C == CH2 + O2 → CH3CHO
reaction and most are regulated by (b) Both Assertion and Reason are H2 O
enzymes. Enzymes are highly specific in true, but the Reason is not the This reaction is also known as
nature. correct explanation for the Wacker’s process.
Assertion.
24 Match List-I with List-II. (c) Both Assertion and Reason are 27 Which of the following is not an
List-I List-II true and the Reason is the correct
example of heterogeneous
(Process) (Catalyst) explanation for the Assertion.
catalytic reaction?
(A) Deacon’s (i) ZSM-5
(d) Both Assertion and Reason are
false. (a) Haber’s process
process
(b) Combustion of coal
(B) Contact (ii) CuCl2 Ans. (a)
(c) Hydrogenation of vegetable oils
process Assertion is correct but Reason is
(d) Ostwald’s process
(C) Cracking of (iii) Particles ‘Ni’ incorrect. Correct reason is as follows:
[2019, 10 Jan Shift-I]
hydrocarbons To show maximum catalytic activity,
reactants must be adsorbed on to the Ans. (b)
(D) Hydrogenation (iv) V2O5
of vegetable oils surface of catalysis reasonably strong In heterogeneous catalytic reactions,
but not too strong to become physical state of reactants and that of
Choose the most appropriate immobilised. So, most catalytic activity catalyst(s) used are different.
answer from the options given corresponds to a moderately strong Haber’s process, hydrogenation of
adsorption, not extremely strong vegetable oils and Ostwald’s process all
below [2021, 18 March Shift-I]
adsorption. are heterogeneous process. Combustion
A B C D A B C D
of coal is not a heterogeneous catalytic
(a) (ii) (iv) (i) (iii) (b) (i) (iii) (ii) (iv) 26 Match the catalysts Column I with reaction.
(c) (iii) (i) (iv) (ii) (d) (iv) (ii) (i) (iii) products Column II. In Haber’s process
Ans. (a) Fe(s ), Mo(s )
Column I Column II N2 (g) + 3H2 (g) → 2NH3 (g)
A. Deacon’s process is used for (Catalyst) (Product)
industrial preparation of chlorine Hydrogenation of vegetable oils,
gas. (A) V2O5 (i) Polyethlyene
[(Ph P) Rh] Cl
CuCl2 (B) TiCl 4 / Al(Me) 3 (ii) Ethanal Vegetable oil(l) 
3 3
→
HCl + [O2 ] → H2O + Cl2 (Unsaturated) or Ni ( s )
723 K Vanaspat (s)
(C) PbCl2 (iii) H2SO4
B. Contact process is used for Ostwald’s process,
industrial preparation of sulphuric (D) Iron oxide (iv) NH3
Pt(s )
acid where V2O5 as a catalyst 4NH3 (g) + 5O2 (g) →
[2019, 9 April Shift-I] V2 O5 (s )
involved in the process. (a) (A)-(ii), (B)-(iii), (C)-(i), (D)-(iv) 4NO(g) + 6H2O(g)
C. ZSM-5 used as catalyst in cracking (b) (A)-(iv), (B)-(iii), (C)-(ii), (D)-(i) No catalyst is used in combustion of
of hydrocarbons.
(c) (A)-(iii), (B)-(i), (C)-(ii), (D)-(iv) coal. The reaction is highly spontaneous
D. Ni catalysts enables the in nature.
hydrogenation of fats. (d) (A)-(iii), (B)-(iv), (C)-(i), (D)-(ii)
Ans. (c) C + O2 → CO2
(Coal)
Ni
C== C + H2 C C Correct match is
28 Match the catalysts to the correct
(A) → (iii); (B) → (i); (C) → (ii); (D) → (iv)
Vegetable oil H H processes. [JEE Main 2015]
Alkane (i) TiCl 4 + AlCl 3 (Ziegler- Natta catalyst)
is used to prepare polyethylene Catalyst Process
∴ Correct match is (A-ii), (B-iv), (C-i),
from ethene. (A) TiCl 3 (i) Wacker process
(D-iii).
(ii) V2O5 (Vanadium pentoxide) is used
(B) PdCl2 (ii) Ziegler- Natta
as catalyst to prepareH2SO4 from
25 For the following Assertion and contact process. Reaction
polymerisation
Reason the correct option is involved is (C) CuCl2 (iii) Contact process
Assertion For hydrogenation V2 O 5
(D) V2O5 (iv) Deacon's process
2SO2 (g ) + O2 (g ) → 2SO3 (g)
reactions, the catalytic activity
154 JEE Main Chapterwise Topicwise Chemistry

(a) (A)- (iii), (B) - (ii), (C) - (iv), (D) - (i) Choose the most appropriate (C) The diameter of the colloidal
(b) (A)- (ii), (B) - (i), (C) - (iv), (D) - (iii) answer from the options given particles is much larger than
(c) (A)- (ii), (B) - (iii), (C) - (iv), (D) - (i) below. [2021, 1 Sep Shift-II] the wavelength of light used.
(d) (A)- (iii), (B) - (i), (C) - (ii), (D) - (iv) A B C D A B C D (D) The refractive indices of the
Ans. (b) dispersed phase and the
(a) 1 3 2 4 (b) 4 1 3 2
(a) TiCl 3 is used as Ziegler-Natta (c) 4 2 3 1 (d) 1 2 4 3 dispersion medium are
catalyst for the polymerisation of comparable.
ethene. Ans. (b)
According to type of reaction for colloid (E) The dispersed phase has a
(b) PdCl2 is used in Wacker process, in
which alkene changed into preparation, colloids have been very different refractive index
aldehyde via catalytic cyclic classified. from the dispersion medium.
process initiated byPdCl2 . A. Hydrolysis — Choose the most appropriate
(c) CuCl2 is used in Deacon's process. FeCl 3 + 3H2O → Fe (OH) 3 (sol) + 3HCl conditions from the options given
(for Cl2 ) B. Reduction— below. [2021, 20 July Shift-I]
(d) V2O5 is used in contact process of 2AuCl 3 + 3HCHO + 3H2O → (a) (A) and (E) only
manufacturing sulphuric acid. 2Au(sol) + 3HCOOH + 6HCl (b) (C) and (D) only
Time Saving Technique This type of C. Oxidation—SO2 + 2H2S (c) (A) and (D) only
questions can also be solved through → 3S (sol) + 2H2O
elimination technique. There is no need
(d) (B) and (E) only
to know all the four matches to select D. Double decomposition— Ans. (a)
the correct response. Even if you know As2O3 + 3H2S → As2S 3 (sol) + 3H2O Option (A) and (E) are the conditions for
(b) matches then also you can solve the Hence, the correct match is showing Tyndall effect in colloidal
problem. e.g. suppose you know the A → 4, B→ 1, C → 3, D→ 2. solution.
usage of V2O5 in contact process (i.e. D The phenomenon of scattering of light
matches with (iii) andTiCl 3 is connected 30 Lyophilic sols are more stable than by colloidal particles as a result of which
to Ziegler-Natta catalyst (i.e. A matches the path of the beam becomes visible is
with ii). lyophobic sols because
[2021, 27 Aug Shift-II] called a Tyndall effect. Smaller the
These two combinations are present diameter and similar the magnitude of
only in option number (b). Likewise, for (a) there is a strong electrostatic
refractive indices, lesser is the
this question particularly if you know repulsion between the negatively
scattering and hence the Tyndall effect.
that V2O5 is used in contact process then charged colloidal particles.
The diameter of the dispersed phase
this combination is present in option (b) (b) the colloidal particles have particle should not be smaller than the
only out of all the four option given. In positive charge. wavelength of light used because they
this way you can eliminate wrong options (c) the colloidal particles have no won’t be able to scatter the light so,
to get the correct response. charge. therefore, the diameter of the dispersed
(d) the colloidal particles are solvated. particles should be equal or not much
Ans. (d) smaller than the wavelength of the light
TOPIC 3 used.
Lyophilic sols are more stable than
Colloids, Micelles In option (D), the refractive index (i.e. the
lyophobic sols. Lyophilic sols are solvent
ratio of the velocity of light in vacuum to
loving, whereas lyophobic sols are
and Emulsions solvent hating. The dispersed phase in
the velocity of light in any medium) of the
dispersed phase and the dispersion
lyophobic sols has no attraction for the
29 Match List-I with List-II. medium should differ greatly in
solvent. The dispersed phase in lyophilic
magnitude then only the particles will be
sols has attraction for the solvent. The
List-I able to scatter the light and Tyndall
List-II colloidal particles are solvated in the
(Colloid effect will be observed.
(Chemical dispersed medium and therefore
preparation stabilised through solvation process. Hence, option (a) is correct.
reaction)
method) Therefore, the option (d) is correct.
A. Hydrolysis 1. 2AuCl 3 + 3HCHO
32 Tyndall effect is more effectively
+ 3H2O → 2Au(sol) 31 The conditions given below are in shown by [2021, 27 Aug Shift-I]

+ 3HCOOH + 6HCl the context of observing Tyndall (a) true solution

effect in colloidal solutions (b) lyophilic colloid
B. Reduction 2. As2O3 + 3H2S →
(A) The diameter of the colloidal (c) lyophobic colloid
As2S 3(sol) + 3H2O
particles is comparable to the (d) suspension
C. Oxidation 3. SO2 + 2H2S → Ans. (c)
wavelength of light used.
3S (sol) + 2H2O
(B) The diameter of the colloidal Tyndall effect is more effectively shown
D. Double 4. FeCl 3 + 3H2O → particles is much smaller than by lyophobic colloid because in lyophobic
Decomposition Fe(OH) 3 (sol) + 3HCl colloids, the particles are not as highly
the wavelength of light used. solvated as in lyophilic sols. So, the
Surface Chemistry 155

difference in refractive index between be in the same or different state of 38 A colloidal system consisting of a
the particles and the medium is quite matter.
gas dispersed in a solid is called
large in lyophobic colloids. Therefore, Cheese→ Dispersion of liquid in solid.
the tyndall effect is more pronounced in a/an [2021 , 17 March Shift-I]
Pumice stone→ Dispersion of gas in
lyophobic sols or colloids. (a) solid sol (b) gel
solid.
(c) aerosol (d) foam
Hair cream→ Dispersion of liquid in
33 The sol given below with negatively liquid. Ans. (a)
charged colloidal particles is Cloud → Dispersion of liquid in gas. A colloidal system consisting of a gas
[2021, 26 Aug Shift-II] (dispersed phase) dispersed in a solid
(a) FeCl3 added to hot water 35 100 mL of 0.0018% (w/v) solution of (dispersed medium) is called a solid sol.
(b) KI added to AgNO 3 solution
Cl − ion was the minimum DP DM Type of colloid
(c) AgNO 3 added to KI solution
concentration of Cl − required to
(d) Al2O 3 ⋅xH2O in water (a) Gas Solid Solid sol
precipitate a negative sol in
Ans. (c) (b) Liquid Solid Gel
one h. The coagulating value of
When AgNO3 is added to KI, (c) Solid Gas Aerosol
Cl − ion is ……… (Nearest integer)
●

AgNO 3 − (d) Gas Liquid Foam

KI → AgI ↓ →
KI AgI I [2021, 20 July Shift-II]
Negatively charged Ans. (1)
Iodide ion gets adsorbed on the surface Coagulation value The minimum 39 The nature of charge on resulting
of AgI. This will result in formation of concentration of electrolyte in colloidal particles when FeCl 3 is
negatively charged colloids. millimoles required to cause coagulation added to excess of hot water is
● When KI is added to AgNO3 following of 1 L of colloidal solution. [2021, 26 Feb Shift-II]
reaction takes place.
Given, 0.0018 g Cl − present in 100 mL (a) Positive
AgNO solution
AgNO3 →
KI
AgI ↓ →
3
AgI Ag + (b) Sometimes positive and
Positively charged Coagulation value of Cl − is sometimes negative
Silver cation gets adsorbed on surface of 0.0018 (c) Neutral
× 10 3
AgI, resulting in formation of positively = 35.5 = 0.5070 ~− 1 (d) Negative
charged colloids. 0.1
Ans. (a)
● Option (a) and (d) will form positively
charged colloids. 36 The charges on the colloidal CdS When FeCl 3 is added to excess of hot
water,
sol and TiO2 sol are, respectively a positively charged hydrated ferric
34 Match List I with List II. [2021, 18 March Shift-II]
oxide [Fe2O3 ⋅xH2O/Fe3+ ] is formed due to
(a) positive and positive adsorption Fe3+ ion (adsorbate) on the
List I List II
(b) positive and negative surface of hydrated ferric oxide
(A) Cheese I. Dispersion of (c) negative and negative (adsorbent).
liquid in liquid (d) negative and positive H 2 O (Excess)
FeCl 3 →
∆
(B) Pumice II. Dispersion of Ans. (d)
stone liquid in gas [Fe2O3 ⋅ xH2O] ⋅Fe3+ + 3Cl − (aq)
Oxides and hydroxide sol are positively (Positively charged sol
charged. or positive colloid)
(C) Hair cream III. Dispersion of gas
in solid So, TiO2 is positive sol. Sulphide sol are
negatively charge hence, CdS is 40 Which one of the following
(D) Cloud IV. Dispersion of negatively charge sol. statements is false for hydrophilic
liquid in solid sols ? [2021, 25 Feb Shift-II]
37 For the coagulation of a negative (a) They do not require electrolytes
Choose the most appropriate sol, the species below, that has the for stability.
answer from the options given highest flocculating power is (b) These sols are reversible in nature.
below. [2021, 25 July Shift-II] [2021, 17 March Shift-II] (c) Their viscosity is of the order of
A B C D (a) SO 2−
4 (b) Ba2+ that of H2O.
+
(a) IV III II I (c) Na (d) PO 3−
4 (d) The sols cannot be easily
Ans. (b) coagulated.
(b) IV I III II
(c) III IV I II To coagulate negative sol,Ba2 + cation Ans. (c)
(d) IV III I II has highest coagulation value. Statement (c) is false whereas other
For a negative sol, a positive ion is statements are true. Corrected
Ans. (d) statement is as follows :
required for flocculation.
Dispersion of various system in which Viscosity of hydrophilic sols is higher
According to Hardy-Schulze law, greater
distributed particles of one material are than that of the dispersion medium, i.e.
the valence of the flocculating ion
dispersed in a continuous phase of H2O, because there is a high
added, the greater is its power to cause
another material. The two phases may concentration of dispersed phase in
precipitation.
water.
156 JEE Main Chapterwise Topicwise Chemistry

41 Most suitable salt which can be (I) Foam – Froth Mond process is associated with
Foam forms gas particles trapped refining of nickel.
used for efficient clotting of blood
in solid or liquid. 80 ° C
Ni + 4 O →
will be [2021, 24 Feb Shift-II] [Ni(CO) 4 ]
(II) Gel – Jellies Crude
(a) NaHCO 3 (b) FeSO 4 200 ° C
Gel is a colloid, where dispersed → Ni
(c) Mg(HCO 3)2 (d) FeCl3 −4 CO Pure
phase is liquid and dispersion
Ans. (d) medium is solid. van Arkel method, ultra pure Zr, Hf,
Ti metals get refined.
According to Hardy-Schulze rule, for (III) Aerosol – Smoke
°C
600
negatively charged sol, most (+ve) Aerosol is a colloid, where Zr + 4I2 → ZrI4 (g)
charged ion is needed for efficient Crude
solid/liquid particles dispersed in 1800 ° C
coagulation. → Zr
gas. −2 I 2 Pure
Blood is a negatively charged sol. Hence (IV) Emulsion– Milk
FeCl 3 can be used for blood clotting and
it from Fe3+ ion.
Emulsion is formed by mixing two 46 Identify the correct molecular
liquids. (Milk is combination of 2 picture showing what happens at
liquid) the critical micellar concentration
42 Tyndall effect is observed when
[2020, 3 Sep Shift-I] (CMC) of an aqueous solution of a
44 A sample of red ink (a colloidal
(a) the diameter of dispersed surfactant (• polar head; ~~
suspension) is prepared by mixing
particles is much larger than the non-polar tail; • water).
wavelength of light used eosin dye, egg white, HCHO and [2020, 5 Sep Shift-I]
(b) the diameter of dispersed water. The component which
particles is much smaller than the ensures stability of the ink sample
(A) (B)
wavelength of light used is [2020, 4 Sep Shift-II]
(c) the refractive index of dispersed (a) egg white (b) eosin dye
phase is greater than that of the (c) HCHO (d) water
dispersion medium (C) (D)
Ans. (a)
(d) the diameter of dispersed
Egg white is a lyophilic colloid and for its
particles is similar to the (a) (C) (b) (B)
stability lyophobic colloid is mixed in it.
wavelength of light used Because, egg white is a lyophilic colloid (c) (D ) (d) (A)
Ans. (d) it is mixed with red ink sample for its Ans. (d)
Tyndall effect, an optical property, is stability. Hence, option (a) is correct.
CMC (critical micelle concentration) is
observed by colloids, preferably the concentration of a surfactant in a
lyophobic colloidal sols. 45 Which of the following is used for bulk phase, above which aggregates of
Here, visible light of wavelength range the preparation of colloids? surfactant molecules, so called micelles,
more than 400 nm scattered when they [2020, 2 Sep Shift-I] start to form.
are incident on colloidal particles of (a) Bredig’s Arc method A micelle is an aggregate of monomer
sizes (diameter, 10 −7 - 10 −5 cm) (b) Ostwald process surfactant molecules dispersed in a liquid
commensurate with their wavelengths. (c) Mond process colloid.
In lyophobic colloids, refractive index of
the dispersed phase is smaller than that (d) van Arkel method Hydrophilic ‘Head’ regions in contact
of dispersion medium. Ans. (a) with surrounding solvent, sequestering
the hydrophobic ‘ Tail’ regions in the micelle
So, option (c) is also not correct. Using Bredig’s arc method, colloids centre.
(metal sols which are lyophobic) can be
43 Match the following: prepared.
I. Foam (A) Smoke In this method, two electrodes of metal
II. Gel (B) Cell fluid (whose sol is to be prepared) are dipped
in concentrated alkali. The electrodes
III. Aerosol (C) Jellies Hence, option (d) is correct.
act as arc for high voltage transmission
IV. Emulsion (D) Rubber of current. The metal particles get
(E) Froth dispersed in the medium to produce 47 Kraft temperature is the
(F) Milk metal sols like Au-sol, Ag-sol, Pt-sol etc. temperature [2020, 6 Sep Shift-II]
[2020, 4 Sep Shift-I]
Ostwald process is an industrial process (a) below which the aqueous solution
(a) (I)-(D), (II)-(B), (III)-(A), (IV)-(E) for manufacturing HNO3. Reactions are of detergents starts freezing
(b) (I)-(B), (II)-(C), (III)-(E), (IV)-(D) as follows : (b) below which the formation of
(c) (I)-(E), (II)-(C), (III)-(A), (IV)-(F) Pt gauge micelles takes place
(i) 4NH3 + 5O2 →
(d) (I)-(D), (II)-(B), (III)-(E), (IV)-(F) 500 K, 9 atm (c) above which the aqueous solution
3NO + 6H2O
Ans. (c) of detergents starts boiling
(ii) 2NO + O2 → 2NO2
Correct match is (I)→ E, (II) → C, (III) → A, (d) above which the formation of
(iii) 3NO2 + H2O → 2HNO3 + NO
(IV) → F micelles takes place
Surface Chemistry 157

Ans. (d) As flocculation power increases, (c) process of converting a colloidal

Micelles formation take place only above flocculation value decreases. Therefore, solution into precipitate
a particular temperature called Kraft order of flocculation values is (d) process of converting soluble
temperature (TK ). K3 [Fe(CN) 6 ] < K2 CrO4 < KBr particles to form colloidal solution
Hence, the correct option is (d). = KNO3 = AlCl 3 Ans. (b)
Peptisation is a process of converting
48 The flocculation value of HCl for 50 The aerosol is a kind of colloid in precipitate into colloidal solution. This
arsenic sulphide sol. is 30 m mol which [2019, 9 April Shift-I] process involves the shaking of
L −1 . If H2SO 4 is used for the (a) gas is dispersed in liquid precipitate with the dispersion medium
flocculation of arsenic sulphide, (b) gas is dispersed in solid in the presence of small amount of
(c) liquid is dispersed in water electrolyte. The electrolyte added is
the amount in grams of H2SO 4 is called peptising agent.
250 mL required for the above (d) solid is dispersed in gas
During peptisation, the precipitate
purpose is …… (molecular mass of Ans. (d)
adsorbs one of the ions of the
H2SO 4 =98 g /mol) The aerosol is a kind of colloid in which electrolyte on its surface. This causes
[2020, 7 Jan Shift-II] solid is dispersed in gas. e.g. smoke, dust. the development of positive or negative
Ans. (0.37) charge on precipitates, which ultimately
(exact value : 0.3675 g)
51 The correct option among the breakup into smaller particles of the size
following is [2019, 10 April Shift-II] of a colloid.
Flocculation value = number of m mol of
electrolyte needed per litre. (a) colloidal medicines are more
effective, because they have small 53 Among the following, the incorrect
Since, As2S 3 is negatively charged
surface area. statement about colloids is
colloid, H+ causes its flocculation.
[2019, 12 April Shift-II]
Here, 30 m mol of HCl is needed per 1 L (b) brownian motion in colloidal
solution is faster if the viscosity of (a) They can scatter light
per 250 mL, HCl required would be (b) They are larger than small
the solution is very high.
30 × 250 molecules and have high molar
= = 7 .5 m mol (c) addition of alum to water makes it
1000 unfit for drinking. mass
∴ nH + required = 7.5 m mol (d) colloidal particles in lyophobic sols (c) The osmotic pressure of a colloidal
7.5 m mol can be precipitated by solution is of higher order than the
So, mol of H2SO4 required =
2 electrophoresis. true solution at the same
= 3.75 m mol Ans. (d) concentration
3.75 × 98 (d) The range of diameters of colloidal
Mass of H2SO4 = = 0.3675 g. The explanation of the given statements particles is between 1 and 1000 nm
1000 are as follows :
The value may range from 0.36 to 0.38. (a) Colloidal medicines are more
Ans. (c)
effective because they (dispersed Statement (c) is incorrect about colloids.
49 As per Hardy-Schulze formulation, phase) have larger surface area. Colligative properties such as relative
Thus, option (a) is incorrect. lowering of vapour pressure, elevation in
the flocculation values of the
boiling point, depression in freezing
following for ferric hydroxide sol (b) Brownian motion of dispersed
point and osmotic pressure of a colloidal
are in the order : [2020, 8 Jan Shift-I] phase particles in colloidal solution
solution is of low order than the true
is faster if the viscosity of the
(a) K 3 [Fe(CN) 6] < K2CrO 4 < AlCl3 < KBr solution is very low. Thus, option (b)
solution at the same concentration.
< KNO 3 is incorrect.
(b) AlCl3 > K 3 [Fe(CN6] > K2CrO 4 > 54 Which of the salt-solution is most
(c) Addition of alum effective for coagulation of
KBr = KNO 3 (K2SO4 ⋅ Al2 (SO4 ) 3 ⋅24H2O), an
(c) K 3 [Fe(CN) 6] < K2CrO 4 < KBr = electrolyte to water makes it fit for arsenious sulphide?
KNO 3 = AlCl3 drinking purposes because alum (a) BaCl2 (b) AlCl3 (c) Na3PO 4 (d) NaCl
(d) K 3 [Fe(CN) 6] > AlCl3 > K2CrO 4 > KBr coagulates mud particles from [2019, 9 Jan Shift-II]
> KNO 3 water. Ans. (b)
Ans. (c) Thus, option (c) is incorrect. Arsenious sulphide sol is a negative
(d) Precipitation of lyophobic solution colloid, As2S 3.(S2 − ). So, it will be
Ferric hydroxide sol (and other metal
particles by electrophoresis is coagulated by the cation of an electrolyte.
oxide and hydroxide sols) is generally
positively charged. So, as per called cottrell precipitation. According to the Hardy-Schulze rule, the
Hardy-Schulze rule, the flocculation Thus, option (d) is correct. higher the charge of the ion, the more
power is greatest for electrolyte having effective it is in bringing about
most highly negatively charged anion. 52 Peptisation is a [2019, 12 April Shift-I] coagulation. Here, the cations available
are Al 3+ (from AlCl 3), Ba2 + (from BaCl2 )
∴Flocculation power follow the order (a) process of bringing colloidal
molecule into solution and Na+ (from Na3PO4 and NaCl). So,
K3 [Fe (CN) 6 ] > K2 CrO4 >KBr their power to coagulate As2S 3. (S2 − ) will
Anionic charge : (–3) (–2) (–1) (b) process of converting precipitate follow the order as
= KNO3 = AlCl 3 into colloidal solution
Al 3+ > Ba2 + > Na+
158 JEE Main Chapterwise Topicwise Chemistry

55 Haemoglobin and gold sol are 58 Among the following, the false (i) The diameter of the colloids should
not be much smaller than the
examples of statement is
wavelength of light used.
(a) negatively and positively charged (a) Tyndall effect can be used to
(ii) The refractive indices of the
sols, respectively distinguish between a colloidal
dispersed phase and dispersion
(b) negatively charged sols solution and a true solution medium should differ greatly in
(c) positively charged sols (b) It is possible to cause artificial rain magnitude.
(d) positively and negatively charged by throwing electrified sand
sols, respectively carrying charge opposite to the
60 The coagulating power of
[2019, 10 Jan Shift-II] one on clouds from an aeroplane
electrolytes having ions Na + , Al 3+
Ans. (d) (c) Lyophilic sol can be coagulated by
adding an electrolyte and Ba 2+ for arsenic sulphide sol
Haemoglobin and gold sol both are increases in the order
colloids and always carry an electric (d) Latex is a colloidal solution of
[JEE Main 2013]
charge. Haemoglobin is a positively rubber particles which are
positively charged (a) Al3+ < Ba2+ < Na+
charged sol, because in haemoglobin,
(b) Na+ < Ba2+ < Al3+
Fe2 + ion is the central metal ion of the [2019, 12 Jan Shift-II]
octahedral complex. Ans. (d) (c) Ba2+ < Na2+ < Al3+
All metal sols like, Au-sol, Ag-sol etc; are (d) Al3+ < Na+ < Ba2+
Statement given as statement (d) is
negatively charged sols. incorrect. Latex is a stable dispersion, Ans. (b)
i.e. emulsion of polymer microparticles According to Hardy Schulze rule, greater
56 An example of solid sol is in an aqueous medium. the charge on oppositely charged ion,
[2019, 11 Jan Shift-I] These microparticles belong to rubber greater is its coagulating power. Since
(a) gem stones (b) hair cream and are negatively charged in nature. arsenic sulphide is a negatively charged
(c) butter (d) paint Natural latex contains some amount of sol, thus, the order of coagulating power
sugar, resin, protein and ash as well. is Na+ < Ba2 + < Al 3+ .
Ans. (a)
The closest synthetic latex that can be
Solid sol consists of solid as both
dispersed phase and dispersion medium.
associated with the properties of natural 61 Gold numbers of protective colloids
latex is SBR, i.e. Styro Butane Rubber. A, B, C and D are 0.50, 0.01, 0.10
In gemstones, metal crystals (salt and
oxides of metals) are dispersed in solid Rest of all the statements are correct. and 0.005, respectively. The
(stone) medium. Hair cream is an emulsion correct order of their protective
(liquid in liquid). Butter is a colloidal 59 The Tyndall effect is observed only powers is [AIEEE 2008]
solution of liquid in solid. Paint is also sol when following conditions are
(solid in liquid).
(a) D < A < C < B
satisfied [JEE Main 2017]
(b) C < B < D < A
57 Among the colloids cheese (C), milk I. The diameter of the dispersed (c) A < C < B < D
particles is much smaller than (d) B < D < A < C
(M) and smoke (S), the correct
the wavelength of the light Ans. (c)
combination of the dispersed
used. Higher the gold number, lesser will be
phase and dispersion medium,
respectively is [2019, 11 Jan Shift-II] II. The diameter of the dispersed the protective power of colloid.
particle is not much smaller
(a) C : liquid in solid; M : liquid in liquid;
S : solid in gas than the wavelength of the 62 The disperse phase in colloidal iron
(b) C : solid in liquid; M : liquid in liquid; light used. (III) hydroxide and colloidal gold is
S : gas in solid III. The refractive indices of the positively and negatively charged,
(c) C : liquid in solid; M : liquid in solid; dispersed phase and respectively. Which of the following
S : solid in gas dispersion medium are almost statement is not correct?
(d) C : solid in liquid; M : solid in liquid; similar in magnitude. (a) Coagulation in both sols can be
S : solid in gas IV. The refractive indices of the brought about by electrophoresis
Ans. (a) dispersed phase and (b) Mixing the sols has no effect
dispersion medium differ (c) Sodium sulphate solution causes
Dispersed Dispersion Type of Examples coagulation in both sols
phase medium colloid
greatly in magnitude.
(d) Magnesium chloride solution
(a) I and IV (b) II and IV
Liquid Solid Gel Cheese (C), coagulates the gold sol more
butter, jellies (c) I and III (d) II and III
readily than the iron (III) hydroxide
Liquid Liquid Emulsion Milk (M), hair Ans. (b) sol [AIEEE 2005]
cream
Colloidal solutions show Tyndall effect Ans. (b)
Solid Gas Aerosol Smoke (S), due to scattering of light by colloidal
dust Mixing the sols together can cause
particles in all directions in space. It is
observed only under the following coagulation, since the charges are
Thus, C : liquid in solid, M : liquid in liquid neutralised.
and S : solid in gas. conditions.
13
Classification of Elements
and Periodicity in Properties
TOPIC 1 03 The atomic number of the element 05 The correct electronic
Periodic Table and unnilennium is [2020, 3 Sep Shift-I] configuration and spin-only
Classification of Elements (a) 109 (b) 102 magnetic moment (BM) of Gd 3+
(c) 108 (d) 119 (Z = 64), respectively, are
Ans. (a) [2020, 5 Sep Shift-I]
01 Identify the element for which
The atomic number of the element (a) [Xe] 4 f 7 and 7.9 (b) [Xe] 5 f 7 and 7.9
electronic configuration in +3
unnilennium is 109. (c) [Xe] 5 f 7 and 8.9 (d) [Xe] 4 f 7 and 8.9
oxidation state is [Ar] 3d 5 .
1 {
(a) Z = { 0 { 9 Ans. (a)
[2021, 1 Sep Shift-II] un nil enn − ium ⇒ unnilennium Electronic configuration of Gd 3 + is
(a) Ru (b) Mn 3+
1 {
(b) Z = { 0 {
2 64 Gd = [Xe]4f 7
(c) Co (d) Fe un nil bi − ium ⇒ unnilbiium
Ans. (d) = [Xe]
1 {
(c) Z = { 1 {
8
Iron (Fe) has electronic configuration un nil oct − ium ⇒ unniloctium Gd 3 + having 7 unpaired electrons.
[Ar] 3d 5 in +3 oxidation state. Magnetic moment (µ ) = n(n + 2) BM
1 {
(d) Z = { 1 9
{
Electronic configuration of Fe enn − ium ⇒ ununennium
un nil ⇒ µ = 7 (7 + 2) BM = 7.9 BM
= [Ar] 3d 6 , 4s 2 Hence, option (a) is correct. where, n = number of unpaired electrons.
Electronic configuration of
Fe3+ = [Ar] 3d 5 . 04 The process that is not 06 In the sixth period, the orbitals that
endothermic in nature is are filled are [2020, 5 Sep Shift-I]
[2020, 4 Sep Shift-II]
02 Outermost electronic configuration (a) 6 s ,5 f, 6d, 6 p (b) 6 s ,4 f,5d, 6 p
(a) O (g) + e → O2 − (g)
− −
of a group-13 element E is 4s 2 4p 1 . (b) Na(g) → Na+ (g) + e −
(c) 6 s ,5d,5 f, 6 p (d) 6 s , 6 p, 6d, 6 f
The electronic configuration of an Ans. (b)
(c) H(g) + e − → H− (g)
element of p-block period-five Filling of electrons in orbitals in any
(d) Ar (g) + e − → Ar − (g)
placed diagonally to element, E is period takes place as :
[2021, 20 July Shift-II]
Ans. (c) s → ns (n − 2)f (n − l )d np
(a) [Kr] 3d 104 s 2 4 p2 (a) O– (g) + e − → O2 − (g) (endothermic) if possible if possible

(b) Na(g) → Na+ (g) + e − (endothermic) ∴ A per (n + l ) rule for sixth period n = 6,
(b) [Ar] 3d 104 s 2 4 p2 orbitals that are filled are
(c) H(g) + e − → H− (g) (exothermic)
(c) [Xe] 5d 10 6 s 2 6 p2 (d) Ar (g) + e − → Ar − (g) (endothermic) 6s, 4f, 5d and 6p
(d) [Kr] 4 d 105 s 2 5 p2 Reaction (c) is not endothermic. It is
Ans. (d) exotherrnic. Electron gain ethalpy of
07 The atomic number of unnilunium
H(g) is negative, due to ‘s ’ configuration is …… . [2020, 6 Sep Shift-II]
13th 14th 15th
while that of Ar(g) is positive due to Ans. (101)
2nd period 2s 2 2p1 B C N
ns 2 np6 configuration. Unnilunium
3rd period 3s 2 3p1 Al Si P
Second election gain enthalpy is always IUPAC symbol = Unu
4th period 4s 2 4p1 Ga Ge As positive for an atom. Atomic number (Z) = 101
5th period 5s 2 5p1 In Sn Sb Ionisation potential of an atom is Because, the roots are strung together
That element is 50 Sn ⇒[Kr] 4d 10 5s 2 5p2 positive. in the order of digits which makes up the
160 JEE Main Chapterwise Topicwise Chemistry

atomic numbers and ‘ium’ is added at the 11 The isoelectronic set of ions is Ans. (c)
end. [2019, 10 April Shift-I] The element with Z = 120 will be an
Digit Name Abbreviation (a) F − , Li+ , Na+ and Mg2+ alkaline earth metal. Recently,
(b) N3− , Li+ , Mg2+ and O2 − oganesson (Og) with atomic number 118
1 un` u is named by IUPAC is a noble gas and
(c) Li+ , Na+ , O2 − and F −
0 nil n placed just two place before 120. So, the
(d) N3− , O2 −, F − and Na+ general electronic configuration is
1 un u Ans. (d) represented as [noble gas] ns 2 and
element with Z = 120 exist as an alkaline
08 The electronic configuration of Key Idea Isoelectronic species contains earth metal.
same number of electrons.
bivalent europium and trivalent
cerium are The species with its atomic number and 14 The group having isoelectronic
(atomic number : Xe = 54, Ce = 58 number of electrons are as follows : species is [JEE Main 2017]

Eu=63) [2020, 9 Jan Shift-I] Species At. no. No. of (a) O2 − , F − , Na+ , Mg2 +
7
(a) [Xe] 4 f and [Xe] 4 f 1 (ions) (Z) electrons (b) O − , F − , Na, Mg +
(c) O2 − , F − , Na, Mg2 +
(b) [Xe] 4 f 7 6 s 2 and [Xe] 4 f2 6 s 2 N3− 7 7 + 3 = 10
(d) O − , F − , Na+ , Mg2 +
(c) [Xe] 4 f2 and [Xe] 4 f 7
O2− 8 8 + 2 = 10 Ans. (a)
(d) [Xe] 4 f 4 and [Xe] 4 f 9
F− 9 9 + 1 = 10 Isoelectronic species are those which
Ans. (a)
Na +
11 11 − 1 = 10 contains same number of electrons.
The electronic configuration of bivalent
+ Atomic Number of
europium and trivalent cerium are as Li 3 3 −1 = 2 Species
follows: number electrons
Mg 2+
12 12 − 2 = 10
63Eu = [Xe]4f 5d 6s ⇒Eu
7 0 2 2+
= [Xe] 4f 7 O2 − 8 10
58
Ce = [Xe]4f 5d 6s ⇒Ce = [Xe] 4f 1
1 1 2 3+
Thus, option (d) contains isoelectronic F− 9 10
set of ions. +
Na 11 10
09 The size of the iso-electronic
species Cl − , Ar and Ca 2+ is affected 12 The group number, number of Mg2 + 12 10
by [2019, 8 April Shift-I] valence electrons and valency of an O− 8 9
(a) azimuthal quantum number of element with atomic number 15, Na 11 11
valence shell respectively, are Mg + 12 11
(b) electron-electron interaction in [2019, 12 April Shift-I]
the outer orbitals (a) 16, 5 and 2 (b) 15, 5 and 3 ∴ Option (a) is correct which contains
(c) principal quantum number of (c) 16, 6 and 3 (d) 15, 6 and 2 isoelectronic speciesO2 − , F − , Na+ , Mg2 + .
valence shell Ans. (b)
(d) nuclear charge 15 Which one of the following sets of
The group number, number of valence
Ans. (d) electrons and valency of an element with ions represents a collection of
atomic number 15 are 15, 5 and 3 isoelectronic species ? [AIEEE 2006]
The radius of isoelectronic species is
inversely proportional to their nuclear respectively. Modern periodic table is (a) K + , Cl − , Ca 2 + , Sc 3+
charge or atomic number (Z). Thus, based on the atomic number. Number of (b) Ba2+ , Sr2+ , K + , S2−
greater the value of Z, lesser the radii of valence electrons present in an atom (c) N 3 – , O 2 − , F − , S 2 –
decides the group number.
isoelectronic species. (d) Li+ ,Na+ ,Mg2+ ,Ca2+
Electronic configuration of element
having atomic number Ans. (a)
10 The IUPAC symbol for the element
15 = 1s 2 2s 2 2p6 3s 2 3p3 Isoelectronic means having same
with atomic number 119 would be Valence electrons number of electrons,
[2019, 8 April Shift-II]
As five electrons are present in valence K+ , Cl − , Ca2 + , Sc3+ (all are having
(a) unh (b) uue shell, its group number is 15. Valency of 18 electrons).
(c) uun (d) une element having atomic number 15 is +3
Ans. (b) (8 − 5 = 3). 16 According to the periodic law of
Atomic number (119) = 1 1 9 elements, the variation in
un un en 13 The element with Z = 120 (not yet properties of elements is related to
So, symbol of the element = uue discovered) will be an/a their [AIEEE 2003]
Name of the element = ununennium [2019, 12 Jan Shift-I]
(a) atomic masses
It is expected to be s-block element an (a) transition metal (b) nuclear masses
alkali metal and the first element in (b) inner-transition metal (c) atomic numbers
eighth period. It is the lightest element (c) alkaline earth metal (d) nuclear neutron-proton number
that has not yet been synthesised. (d) alkali metal
ratios
Classification of Elements and Periodicity in Properties 161

Ans. (c) Ans. (b) 21 AX is a covalent diatomic molecule,

All physical and chemical properties of On moving from left to right in periodic where A and X are second row
elements are periodic function of their table, metallic character decreases elements of periodic table. Based
atomic number— Modern Periodic Law. while non-metallic character increases.
This is due to decrease in ionisation
on molecular orbital theory, the
enthalpy and increase in electron gain bond order of AX is 2.5. The total
TOPIC 2 enthalpy when we move from left to right number of electrons in AX is ……… .
in periodic table. Hence, (A) is true while (Round off to the nearest integer).
Periodic Properties (R) is false. [2021, 18 March Shift-I]
Hence, correct option is (b). Ans. (15)
17 The correct order of ionic radii for
AX is a covalent diatomic molecule. The
the ions, P 3 − , S 2 − , Ca 2 + , K + , Cl − is 19 The correct order of first ionisation
molecule is NO (Nitric oxide). Its bond
[2021, 27 Aug Shift-II] enthalpy is [2021, 27 July Shift-II]
order is 2.5 and it has a total of 15
(a) P 3− > S2 − > Cl − > K + > Ca2 + (a) Mg < S < Al < P electrons (7 + 8 = 15).
(b) Cl − > S2 − > P 3− > Ca2 + > K + (b) Mg < Al < S < P Here ‘A’ denotes nitrogen (N) and ‘X’
(c) P 3− > S2 − > Cl − > Ca2 + > K + (c) Al < Mg < S < P denotes oxygen (O). NO is colourless and
(d) K + > Ca2 + > P 3− > S2 − > Cl − (d) Mg < Al < P < S toxic gas.
Ans. (a) Ans. (c) Note : Total number of electrons equal
to 13 will also have the 2.5 bond order,
The electronic configuration of given The correct order of first ionisation
but in this case neutral diatomic
ions are as follows : enthalpy is Al < Mg < S < P.
molecule will not be possible.
K19 = 2, 8, 8, 1 K+ = 2, 8, 8 Generally, it increases on moving from
Ca20 = 2, 8, 8, 2 Ca2 + = 2, 8, 8 left to right in a period. But due to the
22 The set of elements that differ in
presence of half-filled (3s 2 3p3) orbital in
P15 = 2, 8, 5 P3− = 2, 8, 8 mutual relationship from those of
P and fully filled (3s 2 ) in Mg, results in the
S 16 = 2, 8, 6 S2 − = 2, 8, 8 high ionisation energy. the other sets is
Cl 17 = 2, 8, 7 Cl − = 2, 8, 8 [2021, 17 March Shift-II]
As the effective nuclear charge 20 The ionic radii of F − and O 2− (a) Li-Mg (b) B-Si
increases from P to Ca, the atomic size respectively are 1.33 Å and 1.4 Å (c) Be-Al (d) Li-Na
decreases in the same order. while the covalent radius of N is Ans. (d)
Order of ionic radii 0.74Å. The correct statement for Li-Na pair is different from remaining
P3− > S2 − > Cl − > K+ > Ca2 + the ionic radius of N 3− from the three options as it do not shows diagonal
15 16 17 19 20
Therefore, option (a) is correct. following is [2021, 25 July Shift-II] relationship. Both Li-Na belongs to same
(a) it is smaller than F − and N group and are not placed diagonally.
18 Given below are two statements : (b) it is bigger than O2− and F − Li - Mg, B - Si and Be - Al show diagonal
relationship.
one is labelled as Assertion (A) and (c) it is bigger than F − and N, but
the other is labelled as Reason (R). smaller than of O2− Li Be B (Diagonal
relationship)
Na Mg Al Si
Assertion (A) Metallic character (d) it is smaller than O2− and F − , but
decreases and non-metallic bigger than of N
23 Identify the elements X and Y using
character increases on moving Ans. (b)
the ionisation energy values given
from left to right in a period. The electronic configuration of F − , O2−
below.
and N3− are given below.
Reason (R) It is due to increase in
ionisation enthalpy and decrease F − = 1s 2 2s 2 2p6  Ionisation energy (Ist) kJ/mol (IInd)

in electron gain enthalpy, when O = [He] 2s 2 2p6 10 e −
2−
X 495 4563

3−
one moves from left to right in a N = [He] 2s 2p  2 6
731 1450
 Y
period. (isoelectronic species) [2021, 16 March Shift-II]
In the light of the above Among all these,N3 − have least number (a) X = Na, Y = Mg
statements, choose the most of protons due to which its size
(b) X = Mg, Y = F
appropriate answer from the increases as least nuclear attractions
experienced by outer shell electrons. (c) X = Mg, Y = Na
options given below. (d) X = F, Y = Mg
[2021, 31 Aug Shift-I]
From top to bottom of periodic table
ions will increase in radii. However, now Ans. (a)
(a) (A) is false but (R) is true. left to right, the radius is more of a Given data,
(b) (A) is true but (R) is false function of the number of proton or IE1 IE2
(c) Both (A) and (R) are correct and (R) nuclear charge. Similarly,O2 − will be
is the correct explanation of (A). larger thanF − as both have 10 electrons X 495 4563 kJ/mol
(d) Both (A) and (R) are correct but (R) but Z = 8 for oxygen and Z = 9 for Y 731 1450 kJ/mol
is not the correct explanation of fluorine. X is Na (3s 1) as it has very high second
(A). ∴Option (b) is correct. ionisation energy due to removal of
162 JEE Main Chapterwise Topicwise Chemistry

electron from highly stable noble gas (c) N2O → oxide of nitrogen B Be O N
configuration. (non-metal) : neutral (d) (a) (b) (c)
IE BaO → oxide of barium (metal) :
Na → 1
Na+ + e − ; IE 1 = 495 kJ/mol (i) (ii) (iii) (iv)
basic
1s 2 2s 2 2p6 3s 1 1s 2 2s 2 2p6 or [Ne] [801] [899] [1319] [1902]
IE2 (d) CaO → oxide of calcium (metal):
Na+ → Na2 + + e − ; IE2 = 4563 kJ/mol basic The correct matching is (A)-(ii), (B)-(iii),
(C)-(iv), (D)-(i)
1s 2s 2p6
2 2
1s 2 2s 2 2p5 SiO2 → oxide of silicon
(non-metal): acidic Note The order of IE, or ∆ iH1 of 2nd
(Stable noble gas configuration).
period elements is
In case of Mg, noble gas configuration is So, option (b) is the correct answer.B2O3
and SiO2 are being acidic oxide they react Li < B < Be < C < O < N < F < Ne
achieved after removal of second
electron. So,IE2 is comparatively less. with base to give salt and water.
B2O3 + 2NaOH → 2NaBO2 + H2O
27 In general, the property
Mg → Mg + + e − ;
[Ne]3 s 2 [Ne]3 s 1 Sodium (magnitudes only) that shows an
IE1 = 731 kJ/mol metaborate
opposite trend in comparison to
Mg + → Mg2 + + e − SiO2 + 2NaOH → Na2SiO3 + H2O
Sodium other properties across a period is
[Ne] 3 s 1 [Ne]
; IE2 = 1450 kJ/mol silicate [2020, 2 Sep Shift-I]
(a) electronegativity
26 Match List-I with List-II.
24 The first ionisation energy of (b) electron gain enthalpy
magnesium is smaller as compared List-I List-II (c) ionisation enthalpy
to that of elements X and Y, but (Electronic (∆i in kJ mol −1) (d) atomic radius
higher than that of Z. The elements configuration of Ans. (d)
X, Y and Z, respectively, are elements)
With increase in atomic number (Z) along
[2021, 18 March Shift-II] A. 1s 2 2 s 2 (i) 801 a period, effective nuclear charge (Z *) of
(a) chlorine, lithium and sodium the elements also increases. We know,
B. 1s 2 2 s 2 2 p 4 (ii) 899
(b) argon, lithium and sodium Z ∝ Electronegativity (χ)
2 2 3
(c) argon, chlorine and sodium C. 1s 2 s 2 p (iii) 1314 ∝ Electron gain enthalpy or | ∆ e g H |
(d) neon, sodium and chlorine D. 2
1s 2 s 2 p 2 1
(iv) 1402 ∝ Ionisation enthalpy
Ans. (c) 1
or ∆ iH ∝
The order of first ionisation energy of 3 rd Choose the most appropriate Atomic radius (r)
period is as follows answer from the options given So, with increase in atomic number
Na < AI < Mg < Si < S < P < CI<Ar below. [2021, 26 Feb Shift-I]
across a period. Electronegativity,
electron gain enthalpy and ionisation
On moving along a period from left to A B C D enthalpy increases whereas atomic
right, nuclear charge increases that
(a) (ii) (iii) (iv) (i) radius decreases.
outweighs the shielding effect. As a
result, outermost electrons are held (b) (i) (iv) (iii) (ii) Note Z* = Z − σ
more tightly. Hence, ionisation enthalpy (c) (i) (iii) (iv) (ii) Where, σ = shielding constant which can
increases. (d) (iv) (i) (ii) (iii) be calculated using SLATER’s rule.
Ionisation enthalpy of group 2 is greater Ans. (a)
than group 13 and that of group 15 is 28 Three elements X , Y and Z are in
Here, (B), (C) and (D) are p-block
greater than group 16. This is due to fully
elements of the 2nd period.
the 3rd period of the periodic table.
filled and half-filled orbital. The oxides of X, Y and Z,
(D) → p1 configuration → B of group 13
∴X, Y and Z are argon, chlorine and respectively, are basic, amphoteric
sodium respectively. (C) → p3 configuration → N of group 15
(B) → p4 configuration → O of group 16
and acidic. The correct order of the
25 Which pair of oxides is acidic in Stability order : p3 > p4 >> p1
atomic number of X , Y and Z is
[2020, 2 Sep Shift-II]
nature? [2021, 26 Feb Shift-II] Half- filled Partially filled
(a) Z < Y < X (b) X < Y < Z
(a) B2O 3, CaO (b) B2O 3, SiO2 We know, ionisation enthalpy (∆ iH) ∝ (c) X < Z < Y (d) Y < X < Z
(c) N2O, BaO (d) CaO, SiO2 stability of the subshell concerned. Ans. (b)
Ans. (b) Therefore, half-filled subshell is more
While moving across a period, metallic
(a) B2O3 → oxide of boron stable than partially filled.
property of elements changes first into
(non-metal) :acidic ∴ ∆ iH order is c > b >> d metalloids than into non-metallic nature
CaO → oxide of calcium (metal) : (A) is a s-block element (group 2) of 2nd therefore.
basic period with s 2 -configuration → Be of ⇒Metal gives basic oxides.
(b) B2O3 → oxide of boron group2 [fully-filled; stable] Metalloid produces amphoteric oxides.
(non-metal) : acidic So, the correct order of IE, or ∆ iH1 Non-metal gives acidic oxides.
SiO2 → oxide of silicon (in kJ mol −1) of the 2nd period elements So, X→ metal,Y → metalloid and
(non-metal) : acidic will be Z → non-metal
Classification of Elements and Periodicity in Properties 163

⇒Order of atomic number : X< Y < Z electrons. All halogens have negative increase in nuclear charge and decrease
⇒As, X, Y and Z belongs to 3rd period, ∆ e g H (exothermic) values. Generally, in radii.
X can be Na or Mg ∆ e g H becomes less negative when Therefore, the expected order of first
Y can be Al or Si comparing elements of the same group ionisation enthalpies of given elements
from top to bottom. should be
Z can be P or S or Cl
But among fluorine and chlorine there is Na < Mg < Al < Si
29 The ionic radii of O 2− ,F − ,Na + and an anomaly because inter-electron But first ionisation energies of Mg and Al
Mg 2+ are in the order repulsion is stronger in fluorine due to its show anomalous order because Mg has
[2020, 4 Sep Shift-I] extra small size. stable [Ne] 3s 2 configuration and,
(a) O2 − > F − > Mg2 + > Na+ ∴ ∆ e g H is less exothermic than expected therefore higher ionisation energy than
for F-atom. expected, whereas Al has [Ne]3s 2 3p1
(b) Mg2 + > Na+ > F − > O2 −
Thus, the correct values of electron gain configuration, which on ionisation
(c) O2 − > F − > Na+ > Mg2 +
enthalpies becomes stable [Ne]3s 2 .
(d) F − > O2 − > Na+ > Mg2 +
F < Cl > Br > I ∴ Its ionisation energy is less than
Ans. (c) (−333) (−349) (−325) (−296) expected.
O2 − , F − , Na+ and Mg2 + are isoelectronic kJ mol −1
species. 34 The third ionisation enthalpy is
2− − + 2+
32 Within each pair of elements F and minimum for : [2020, 8 Jan Shift-I]
Ionic O F Na Mg
Cl, S and Se, and Li and Na,
− 10 10 10 10 (a) Mn (b) Ni
Number of e respectively, the elements that (c) Co (d) Fe
For isoelectrons species, release more energy upon an Ans. (d)
−ve charge electron gain are
Radius ∝ Fe has minimum value of third ionisation
+ ve charge [2020, 7 Jan Shift-II]
enthalpy. Ground state electronic
So, correct order of ionic radius is (a) F, Se and Na (b) F, S and Li configuration of Fe is [Ar]3d 6 4s 2 .
O2 − > F − > Na+ > Mg2 + . (c) Cl, S and Li (d) Cl, Se and Na
Fe2 + has [Ar]3d 6 configuration, whereas
Ans. (c) Fe3+ has [Ar]3d 5 .
30 The correct order of the ionic radii
The first electron gain enthalpy is
of O 2− , N 3− , F − , Mg 2+ , Na + and Al 3+ exothermic (or negative).
The latter is a stable configuration and
easier to ioniseFe2 + toFe3+ than
is [2020, 5 Sep Shift-II] Generally, electron gain enthalpy expected.
(a) N3− < O2 − < F − < Na+ < Mg2+ < Al3+ becomes less exothermic (or less Hence possess least value.
(b) Al3+ < Na+ < Mg2+ < O2 − < F − < N3− negative) when comparing elements of a
Ni has highest value of third ionisation
(c) Al3+ < Mg2+ < Na+ < F − < O2 − < N3− group from top to bottom.
enthalpy due to its greater nuclear
(d) N3− < F − < O2 − < Mg2+ < Na+ < Al3+ Therefore, electron gain enthalpy of charge and smaller size.
S > Se and Li > Na.
Ans. (c) Due to the same reason, Co > Fe > Mn
1 But there are some exceptions to this. should be the order for the remaining
Size of species ∝
Nuclear charge One of them is the case of a group 17 elements, but the anomalous order is due
Iso-electronic species are those atoms
elements where electron gain is most to greater stability ofMn2 + having
negative for Cl instead of F, due to extra [Ar]3d 5 configuration than Mn3+ with
or ions which has the same number of
small size of fluorine.
electrons. [Ar]3d 4 .
∴ Upon an electron gain, energy releases Whereas for Co+ , the electronic
Size of species decreases with
in the order :
increasing protons. configuration is [Ar] 3d 7 , Thus,
Cl > F, S > Se and Li > Na ionisation enthalpy needed to remove
More is effective nuclear charge (Zeff)
lesser will be ionic size. third electron is less as compared to that
33 The first ionisation energy (in of Mn2 + .
Correct order of ionic radii
kJ/mol) of Na, Mg, Al and Si
Al 3+ < Mg2 + < Na+ < F − < O2 − < N3−
respectively, are : 35 The increasing order of the atomic
[2020, 8 Jan Shift-I] radii of the following elements is
31 The electron gain enthalpy (in
(a) 496, 577, 737, 786 (A) C (B) O (C) F
kJ/mol) of fluorine, chlorine, (b) 786, 737, 577, 496
bromine and iodine, respectively, (D) Cl (E) Br [2020, 8 Jan Shift-II]
(c) 496, 577, 786, 737
are [2020, 7 Jan Shift-I] (d) 496, 737, 577, 786 (a) (A) < (B) < (C) < (D) < (E)
(a) −333, −325, −349 and −296 Ans. (d)
(b) (C) < (B) < (A) < (D) < (E)
(b) −296, −325, −333 and −349 (c) (D) < (C) < (B) < (A) < (E)
The first ionisation energy (in kJ/mol) of
(c) −333, −349, −325 and −296 Na, Mg, Al and Si respectively are
(d) (B) < (C) < (D) < (A) < (E)
(d) −349, −333, −325 and −296 Ans. (b)
496, 737, 577, 786
Ans. (c) Atomic radius generally decreases as we
All four elements belong to the same compare elements in a period from left
Electron gain enthalpy (∆ e g H) is the period (3rd period) and the general trend to right,
enthalpy change for converting 1 mol of in a period from left to right is increase in
∴ C> O >F
isolated atoms to anions by adding first ionisation energy, because of
164 JEE Main Chapterwise Topicwise Chemistry

but elements present in next period are ∴ For 1 mol of that base, 1 mol of HCl (a 40 In comparison to boron, beryllium
larger in size, monoacidic acid) and 0.5 mol ofH2SO4 (a
has [2019, 12 April Shift-II]
∴ Br > Cl > C > O > F; dibasic acid ) will be needed for complete
reaction. (a) lesser nuclear charge and lesser
CNO F first ionisation enthalpy
size decreases
Cl 38 The process that is not (b) greater nuclear charge and lesser
Br endothermic in nature is first ionisation enthalpy
[2020, 4 Sep Shift-II] (c) greater nuclear charge and greater
size increases
So, the correct increasing order of the (a) O − (g) + e − → O2 − (g) first ionisation enthalpy
atomic radii (b) Na(g) → Na+ (g) + e − (d) lesser nuclear charge and greater
(c) H(g) + e − → H− (g) first ionisation enthalpy
C < B < A< D < E
(d) Ar (g) + e − → Ar − (g) Ans. (d)
36 B has a smaller first ionisation Ans. (c) In comparison to boron, beryllium has
− 2− lesser nuclear charge and greater first
enthalpy than Be. Consider the (a) O (g) + e → O (g)
–
ionisation enthalpy.
following statements : (endothermic)
Electronic configuration of
(I) It is easier to remove 2p (b) Na(g) → Na+ (g) + e −
Be(4) = 1s 2 , 2s 2 .
(endothermic)
electron than 2s electron It possess completely filled s-orbitals.
(c) H(g) + e − → H− (g) (exothermic)
(II) 2p electron of B is more Hence, high amount of energy is
(d) Ar (g) + e − → Ar − (g) required to pull the electron from the
shielded from the nucleus by (endothermic) gaseous atom. Beryllium (4) lies left to
the inner core of electrons than Reaction (c) is not endothermic. It is the boron (5) and on moving from left to
the 2s electrons of Be exotherrnic. Electron gain ethalpy of right an electron is added due to which
(III) 2s electron has more H(g) is negative, due to ‘s ’ configuration nuclear charge increases from Be to B.
penetration power than 2p while that of Ar(g) is positive due to
ns 2 np6 configuration. 41 In general, the properties that
electron
Second election gain enthalpy is always decrease and increase down a
(IV) atomic radius of B is more than positive for an atom. group in the periodic table,
Be
Ionisation potential of an atom is respectively are [2019, 9 Jan Shift-I]
(atomic number B = 5, Be = 4) positive. (a) electronegativity and atomic
The correct statements are radius
[2020, 9 Jan Shift-II] 39 The element having greatest (b) electronegativity and electron gain
(a) (I), (II) and (III) difference between its first and enthalpy
(b) (II), (III) and (IV) second ionisation energy, is (c) electron gain enthalpy and
(c) (I), (III) and (IV) [2019, 9 April Shift-I] electronegativity
(d) (I), (II) and (IV) (a) Ca (b) Sc (d) atomic radius and electronegativity
Ans. (a) (c) Ba (d) K Ans. (a)
Ans. (d)
Statements I, II and III are correct, The summary of variation of periodic
whereas statement IV is incorrect. It’s The electronic configuration of given properties is given in table below:
correct form is that, atomic radius of B is elements are as follows :
less than Be. K(19) = 1s 2 2s 2 2p6 3s 2 3p6 4s 1 Variation
Mg(12) = 1s 2 2s 2 2p6 3s 2 S. Periodic
No. property Along a Along a
37 The first and second ionisation Sr(38) = 1s 2 2s 2 2p6 3s 2 3p6 4s 2 period group
enthalpies of a metal are 496 and 3d 10 4p6 5s 2 1. Atomic Decreases Increases
4560 kJ mol −1 , respectively. How Sc(21) = 1s 2s 2p 3s 3p 4s 2 3d 1
2 2 6 2 6
radius
many moles of HCl and H2SO 4 , First ionisation enthalpy (I.E.) of K is lowest 2. Electron gain Increases Decreases
respectively, will be needed to among the given options. Here, the enthalpy
energy required to remove an electron
react completely with 1 mole of the from 4s 1 is least as only one electron is 3. Electronegat Increases Decreases
metal hydroxide? [2020, 9 Jan Shift-II] present in the outermost shell. I.E. (I) is
ivity
(a) 1 and 2 (b) 1 and 1 comparatively high for Mg and Sr and two Thus, electronegativity decreases and
(c) 2 and 0.5 (d) 1 and 0.5 electrons (fully-filled) are placed in atomic radius increases down a group in
s-orbital. the periodic table.
Ans. (d)
Second ionisation enthalpy of K is
A small first ionisation enthalpy highest among the given options. 42 The correct option with respect to
(496 kJ mol –1) and a great difference Now, removal of an electron occur from
between first and second ionisation the Pauling electronegativity values
p6 (fully-filled). So, high energy is
enthalpies (4064 kJ mol –1) characterise required to remove the electron. From
of the elements is
an alkali metal (group-1) element. [2019, 11 Jan Shift-II]
the above discussion, it can be concluded
It’s hydroxide is a monoacidic base that (I.E 2 − I.E 1) value is maximum for K (a) P > S (b) Si < Al
(MOH). (potassium). (c) Te > Se (d) Ga < Ge
Classification of Elements and Periodicity in Properties 165

Ans. (d) increases. It is because of the successive 47 The first ionisation potential of Na
addition of one extra shell of electrons.
The electronegativity values of given is 5.1 eV. The value of electron gain
elements on the Pauling scale can be So, the order of the atomic radii of the
given elements will be: enthalpy of Na+ will be
shown as follows : [JEE Main 2013]
C < S < Al < Cs
Period Group Group Group Group (a) – 2.55 eV (b) – 5.1 eV
No. 13 14 15 16
45 The ionic radii (in Å) ofN 3− , O 2– and (c) –10.2 eV (d) + 2.55 eV
3 Al (1.5) Si (1.8) P (2.1) S (2.5) F − respectively are [JEE Main 2015] Ans. (b)
4 Ga (1.6) Ge (1.8) Se (2.4) (a) 1.36, 1.40 and 1.71 Na → Na+ + e − First IE
5 Te (b) 1.36, 1.71 and 1.40 Na + e − → Na
+

(2.01) (c) 1.71, 1.40 and 1.36 Electron gain enthalpy ofNa+
(d) 1.71, 1.36 and 1.40 Because reaction is reverse so
On moving from left to right across a ∆Heg = − 5.1 eV
period, i.e. from Ga to Se, the effective Ans. (c)
nuclear charge increases and size Number of electrons inN3– = 7 + 3 = 10
decreases. Number of electrons in O2 – = 8 + 2 = 10
48 The increasing order of the ionic
As a result, the value of electronegativity Number of electrons in F − = 9 + 1 = 10 radii of the given isoelectronic
increases due to increase in the Since, all the three species have each 10 species is [AIEEE 2012]
attraction between the outer electrons electrons hence they are isoelectronic (a) Cl− ,Ca2+ , K + , S2
and the nucleus. Whereas on moving species. (b) S2− ,Cl− ,Ca2+ ,K +
down the group, (i.e. from Se to Te), the
atomic size increases.
It is considered that, in case of (c) Ca2+ ,K + ,Cl− , S2−
isoelectronic species as the negative (d) K + , S2− ,Ca2+ ,Cl−
As a result, the force of attraction charge increases, ionic radii
between the outer electron and the Ans. (c)
increases and therefore the value of
nucleus decreases. Hence, the 1
ionic radii are For isoelectronic species, rn ∝
electronegativity decreases. Z
N3− = 1.71
(highest among the three) Here, Z is atomic number
43 Which of the following atoms has
O2 − = 1.40 Species Z Electrons
the highest first ionisation energy?
[JEE Main 2016]
F − = 1.36 Cl− 17 18
(a) Na (b) K (c) Sc (d) Rb
(lowest among the three) Ca2+ 20 18
Ans. (c)
Time Saving Technique There is no need K+ 19 18
to mug up the radius values for different
Order of first ionisation energy is Sc > Na > S2− 16 18
ions. This particular question can be
K > Rb. solved through following time saving. Thus, ionic size is in order
Due to poor shielding effect, removal of Trick The charges on the ions indicate Ca2 + < K+ < Cl − < S2 −
one electron from4s orbital is difficult as the size asN3− > O2 − > F − . Thus, you have
compared to 3s-orbital. to look for the option in which the above 49 Which one of the following orders
trend is followed. Option (c) is the only
44 The correct order of the atomic one in which this trend is followed.
presents the correct sequence of
radii of Hence, it is the correct answer. the increasing basic nature of the
C, Cs, Al and S is given oxides? [AIEEE 2011]

(a) C < S < Al < Cs

46 Which of the following represents (a) Al2O 3 < MgO < Na2O < K2O
(b) C < S < Cs < Al
the correct order of increasing first (b) MgO < K2O < Al2O 3 <Na2O
(c) S < C < Cs < Al ionisation enthalpy for Ca, Ba, S, Se (c) Na2O <K2O <MgO < Al2O 3
(d) S < C < Al < Cs and Ar ? [JEE Main 2013]
(d) K2O <Na2O < Al2O 3 <MgO
[2019, 11 Jan Shift-I] (a) Ca < S < Ba < Se < Ar Ans. (a)
Ans. (a) (b) S < Se < Ca < Ba < Ar
In a period, the nature of oxides varies
(c) Ba < Ca < Se < S < Ar
from basic to acidic while in a group,
Element Period No. Group No. (d) Ca < Ba < S < Se < Ar basic nature of oxides increases.
C 2nd 14 Ans. (c) Thus
Ionisation energy increases along a Decreases
Al 3rd 13 Along the Oxides In a period, basic nature
period atomic period from left to right and decreases
S 3rd 16 down a group. The position of given changes to acidic nature
radius Basic nature
decreases, so, elements in the periodic table is as
Increases in a group
radii : 2 16 18
Al > S. Ca S Ar Group 1 2 1 3
Cs 6th 1 Ba Se Period 3 → Na2O MgO Al2O3
Thus, the order of increasing ∆HIE1 is (Amphoteric oxide)
With the addition of a new shell, period Ba < Ca < Se < S < Ar Period 4 → K2O (Strongly basic)
number as well as atomic radius
166 JEE Main Chapterwise Topicwise Chemistry

Hence, basic nature of oxides are as 53 The ionic mobility of alkali metal Ans. (d)
follows
ions in aqueous soluton is maximum The chemical reactivity of alkali metals is
Al2O3 < MgO < Na2O < K2O due to their ability to loose electron more
for [AIEEE 2006]
readily than other elements. Since, the
(a) K + (b) Rb +
50 The correct order of electron gain tendency to loose electron by alkali
(c) Li+ (d) Na+ metals increases down the group,
enthalpy with negative sign of F, Cl,
Ans. (b) therefore, their chemical reactivity
Br and I, having atomic number 9,
Li+ is having largest hydrated ionic size increases down the group.
17, 35 and 53 respectively, is
[AIEEE 2011]
while Rb+ is having smallest. On the other hand, chemical reactivity of
Smaller the size, greater is the mobility. halogens is due to their ability to gain
(a) I > Br > Cl > F (b) F > Cl > Br > I extra electron more readily than other
(c) Cl > F > Br > I (d) Br > Cl > I > F elements. Since the tendency to gain
54 The increasing order of the first
Ans. (c) electron by halogens decreases down
ionisation enthalpies of the the group, hence their chemical
As we go down the group in periodic elements B, P, S and F (lowest first) reactivity decreases down the group.
table, atomic size increases, force of
attraction for the added electron
is [AIEEE 2006]

decreases. Thus, the added electron (a) F < S < P < B 56 In which of the following
becomes loosely bound. Hence, electron (b) P < S < B < F arrangements the order is not
gain enthalpy decreases down a group. (c) B < P < S < F according to the property indicated
X (g) + e − → X − (g) (d) B < S < P < F against it ? [AIEEE 2005]
Actual order is Cl > F > Br > I Ans. (d) (a) Li < Na < K < Rb Increasing metallic
The fact that fluorine has a less electron Examine the positions in periodic table. radius
gain enthalpy than chlorine seems to be Group 13 14 15 16 17 (b) I < Br < F < Cl Increasing electron
due to the relatively greater B C N O F gain enthalpy (with negative sign)
effectiveness of 2p-electron in the small P S
F-atom to repel the additional electron (c) B < C < N < O Increasing first
Ionisation enthalpy increases along a
entering the atom than 3p-electrons in ionisation enthalpy
period due to increased nuclear charge
the larger Cl-atom.
and decreased atomic radii. While in a (d) Al3+ <Mg2+ <Na+ < F − Increasing
group, it decreases from top to bottom. ionic size
51 The correct sequence which shows Along with this trend ionisation enthalpy Ans. (c)
decreasing order of the ionic radii of is highest for the elements possessing
(a) Metallic radii increase in a group
the elements is [AIEEE 2010] half filled and sable electronic
from top to bottom.
(a) Al 3+ > Mg2+ > Na+ > F – > O2– configuration.
Thus, Li < Na < K < Rb —True
Since, phosphorus is having stable
(b) Na+ > Mg2+ > Al 3+ > O2– > F – (b) Electron gain enthalpy of Cl > F and
half-filled configuration. Hence, order is
(c) Na+ > F – > Mg2+ > O2– > Al 3+ B < S < P < F. decreases along a group.
(d) O2– > F – > Na+ > Mg2+ > Al3+ Thus, I < Br < F < Cl is true.
Ans. (d) 55 Following statements regarding the (c) Ionisation enthalpy increases
2− − +
O ,F ,Na ,Mg and Al are 2+ 3+ periodic trends of chemical along a period from left to right but
isoelectronic species. reactivity of the alkali metals and due to presence of half filled
For isoelectronic species, r ∝ 1/ z the halogens are given. Which of orbitals in N, ionisation enthalpy of
Thus, larger the atomic number these statements give the correct N > O.
(effective nuclear charge) smaller is the picture? [AIEEE 2006] Thus, B < C < N < O is incorrect.
ionic radii. (a) The reactivity decreases in the (d) Higher the negative charges,
alkali metals but increases in the larger is their ionic radii
52 The set representing the correct halogens with increase in atomic Al +3 < Mg2 + < Na+ < F − is also true.
order of ionic radius is [AIEEE 2009] number down the group
(a) Li+ > Be2+ > Na+ > Mg2+ (b) In both the alkali metals and the 57 Based on lattice energy and other
(b) Na+ > Li+ > Mg2+ > Be2+ halogens the chemical reactivity considerations which one of the
decreases with increase in atomic following alkali metal chlorides is
(c) Li2+ > Na+ > Mg2+ > Be2+
number down the group expected to have the highest
(d) Mg2+ > Be2+ > Li+ > Na+ (c) Chemical reactivity increases with melting point ? [AIEEE 2005]
Ans. (b) increase in atomic number down
(a) RbCl (b) KCl (c) NaCl (d) LiCl
The ionic radius in general increases the group in both the alkali metals
and halogens Ans. (c)
moving top to bottom and further
decreases moving left to right. So the (d) In alkali metals, the reactivity As we go down in the group, ionic
correct order is increases but in the halogens it character increases, hence melting
Na+ > Li+ >Mg2 + > Be2 + decreases with increase in atomic point of halides should increase but NaCl
0.98 Å 0.68 Å 0.65 Å number down the group has the highest melting point (800°C)
due to its high lattice energy.
Classification of Elements and Periodicity in Properties 167

58 Which one of the following ions has electron-electron repulsion overweighs 62 The atomic numbers of vanadium
the highest value of ionic radius ? the stability gained by achieving the noble
gas configuration.
(V), chromium (Cr), manganese (Mn)
[AIEEE 2004]
and iron (Fe) are, respectively 23,
(a) Li+ (b) B 3+ (c) O2− (d) F −
60 Which among the following factors 24, 25 and 26. Which one of these
Ans. (c) may be expected to have the
is the most important in making
All the ions belong to same period, thus fluorine the strongest oxidising highest second ionisation
for them cations will be smaller than
anions. Now, O2 − and F − are isoelectronic
agent ? [AIEEE 2004] enthalpy? [AIEEE 2003]

1 (a) Electron affinity (a) V

and rn ∝ (b) Ionisation enthalpy
Z (b) Cr
Thus, ionic radius of (c) Hydration enthalpy (c) Mn
(d) Bond dissociation energy (d) Fe
O2 − (Z = 8) > F − (Z = 9)
Ans. (c) Ans. (b)
59 The formation of the oxide ion F2 has the most negative ∆G ° value which Fe+ (26) = [Ar] 3d 6 ,4s 1
O 2− (g ) requires first an exothermic is dependent on hydration enthalpy. Mn+ (25) = [Ar] 3 d 5 ,4s 1
and then an endothermic step as V + (23) = [Ar] 3d2 ,4s 2
shown below 61 Among Al2 O 3 , SiO 2 , P2O 3 and SO 2 Cr + (24) = [Ar] 3d 5 ,4s 0 [By first IP]
O(g) + e − = O − (g); the correct order of acid strength The electronic configuration of Cr + is
∆H° = − 142kJ mol −1 is [AIEEE 2004] most stable, hence formation of Cr2 +
(a) SO2 < P2O 3 < SiO2 < Al2O 3 by second IP requires maximum
O − (g) + e − = O 2− (g); enthalpy.
(b) SiO2 < SO2 < Al2O 3 < P2O 3
∆H° = 844kJ mol −1 (c) Al2O 3 < SiO2 < SO2 < P2O 3
This is because [AIEEE 2004] (d) Al2O 3 < SiO2 < P2O 3 < SO2 63 Ce 3+ , La 3+ , Pm 3+ and Yb 3+ have
(a) oxygen is more electronegative Ans. (d) ionic radii in the increasing order as
(b) oxygen has high electron affinity [AIEEE 2002]
While moving along a group from top to
(c) O − ion will tend to resist the bottom, acidic nature of oxides (a) La3+ < Ce 3+ < Pm3+ < Yb 3+
addition of another electron decreases and along a period from left to (b) Yb 3+ < Pm3+ < Ce 3+ < La3+
(d) O − ion has comparatively larger right, acidic nature increases. (c) La3+ < Ce 3+ < Pm3+ < Yb 3+
size than oxygen atom Al Si P S (d) Yb 3+ < Pm3+ < La3+ < Ce 3+
Ans. (c) Z 13 14 15 16 Ans. (b)
O− (g) + e − → O2 − ( g); Al2O3 SiO2 P2O3 SO2 rn (radius) ∝
1
∆H° = 844kJ mol −1 → Z
This process is unfavourable in the gas
amphoteric acidic max. acidic
Thus, Yb3+ < Pm3+ < Ce3+ < La3+ .
Thus, Al2O3 < SiO2 < P2O3 < SO2
phase because the resulting increase in
14
General Principles and
Processes of Isolation
of Metals
TOPIC 1 Ans. (a) In the light of the above
Ore and their chemical formula are given
Occurrence, Thermodynamic below
statements, choose the most
and Electrochemical appropriate answer from the
(A) Calamine (3) ZnCO3
Principles of Metallurgy (B) Malachite (4) CuCO3 ⋅ Cu(OH)2 options given below.
[2021, 26 Aug Shift-I]
(C) Siderite (2) FeCO3
(a) Both statement I and statement II
01 Calamine and malachite, (D) Sphalerite (1) ZnS
are true.
respectively, are the ores of Therefore, the correct match is A→ 3, B
→ 4, C→2, D → 1. (b) Statement I is false but statement
[2021, 1 Sep Shift-II] II is true.
(a) nickel and aluminium 03 The statement that is incorrect (c) Both statement I and statement II
(b) zinc and copper about Ellingham diagram is are false.
(c) copper and iron [2021, 27 July Shift-I] (d) Statement I is true but statement
(d) aluminium and zinc (a) provides idea about the reaction II is false.
Ans. (b) rate. Ans. (d)
Calamine is the ore of Zn and is found as (b) provides idea about free energy The Ellingham diagram, a plot of ∆G vs
zinc carbonate (ZnCO3), where malachite change. temperature is used to choose reducing
is the ore of copper and is found as (c) provides idea about changes in the agents for metal extraction. Any element
copper hydroxide [Cu(OH)2 ] and copper phases during the reaction. will reduce the oxide of other metal if it
carbonate [CuCO3]. (d) provides idea about reduction of lie above that element in Ellingham
metal oxide. diagram because the free energy change
02 Match List-I with List-II. Ans. (a) will become more negative. Hence,
Ellingham diagram is a plot between ∆G ° statement I is true.
List-I List-I and temperature (T ). It compares thermal In Ellingham diagram the value of
(Name of (Chemical stability of metal oxide as well as entropy change (∆S ) decreases from left
ore/mineral) formula) reducing power of metals. to right.
A. Calamine 1. ZnS It does not give any information Hence, statement II is false.
regarding rate of reaction.
B. Malachite 2. FeCO 3
05 Sulphide ion is soft base and its
C. Siderite 3. ZnCO 3 04 Given below are two statements.
ores are common for metals
D. Sphalerite 4. CuCO 3 ⋅ Cu(OH)2 Statement I The choice of
(A) Pb (B) Al (C) Ag (D) Mg
reducing agent for metals
Choose the most appropriate extraction can be made by using Choose the correct answer from
answer from the options given Ellingham diagram, a plot of ∆Gvs the options given below
[2021, 22 July Shift-II]
below [2021, 27 Aug Shift-II] temperature. (a) (A) and (C) only
A B C D A B C D Statement II The value of ∆S (b) (A) and (D) only
(a) 3 4 2 1 (b) 3 4 1 2 increases from left to right in (c) (A) and (B) only
(c) 4 3 1 2 (d) 3 2 4 1 Ellingham diagram. (d) (C) and (D) only
General Principles and Processes of Isolation of Metals 169

Ans. (a) 08 The point of intersection and sudden increase in the

Pb and Ag are found as sulphide ore as these ores are frequently slope, in the diagram given below, respectively,
associated with a range of important metals, most indicates.
commonly  copper, lead, nickel, zinc, silver, and gold. 0
Metal Common ore 100
Pb PbS (Galena) Cu 2O
200 O →2
Al Al2O 3 ⋅2H2O (Bauxite) 4Cu+ 2 FeO
300 O →2
2Fe+ 2
Ag Ag2 S (Argentite) C+O2→CO2
400
Mg KCl⋅MgCl2 ⋅ 6H2O (Carnallite) 2C
+O
2CO 2
O 2→ 2 →2
500

∆G°/kJmol–1 of O2
+ CO
CO O
06 Given below are two statements. One is labelled as 600 2 2Zn
+O 2→
Assertion (A) and the other is labelled as Reason (R). Zn
700 2
Assertion (A) Sharp glass edge becomes smooth on 800
heating it upto its melting point. /3Al 2
O3 A
900
O →2
Reason (R) The viscosity of glass decreases on l+ 2
1000 4/3A
melting. 2MgO
O 2→
1100 2Mg+
Choose the most appropriate answer from the options
given below. [2021, 20 July Shift-I] 1200
(a) A is true but R is false
(b) Both A and R are true but R is not the correct explanation 0°C 400°C 800°C 1200°C 1600°C 2000°C
of A. 273K 673K 1073K 1473K 1873K 2273K
(c) A is false but R is true. Temperature
(d) Both A and R are true and R is the correct explanation of A. [2021, 17 March Shift-I]
Ans. (b) (a) ∆G = 0 and melting or boiling point of the metal oxide
On heating the glass, it melts and takes up rounded shape at the (b) ∆G > 0 and decomposition of the metal oxide
edges, which has minimum surface area. This is due to the (c) ∆G < 0 and decomposition of the metal oxide
property of surface tension of liquids and not due to decrease in (d) ∆G = 0 and reduction of the metal oxide
viscosity. Ans. (a)
Viscosity generally decreases as the temperature increases.
At intersection point ∆G = 0, which represents the equilibrium
Hence, both A and R are true but R is not the correct explanation of point and sudden increase in slope is due to melting or boiling
A. point of the metal oxide.
According to Gibb’s free rule,
07 Match List-I and List-II. ∆G = ∆H − T∆S
List-I List-II where, ∆H = change in enthalpy
∆G = change in Gibb’s free energy
A. Haematite 1. Al2O 3 ⋅ x H2O
∆S = change in entropy
B. Bauxite 2. Fe2O 3 We can see that ∆G is dependent on ∆S.
C. Magnetite 3. CuCO 3 ⋅ Cu(OH)2 So, when the phase changes (s → l or l → g) the entropy increases
and hence, slope increases.
D. Malachite 4. Fe 3O 4

Choose the correct answer from the options given 09 Match List-I with List-II.
below. [2021, 17 March Shift-II] List-I List-II
A B C D A B C D A. Siderite (i) Cu
(a) 2 3 1 4 (b) 4 1 2 3
B. Calamine (ii) Ca
(c) 1 3 2 4 (d) 2 1 4 3
C. Malachite (iii) Fe
Ans. (d)
D. Cryolite (iv) Al
Correct matches are A-2, B-1, C-4, D-3.
(v) Zn
Ore Formula
Chose the correct answer from the options given
Haematite Fe2O 3 below. [2021, 26 Feb Shift-II]
Bauxite Al2O 3 ⋅ xH2O A B C D A B C D
Magnetite Fe 3O 4 (a) (iii) (i) (v) (ii) (b) (i) (ii) (v) (iii)
Malachite CuCO 3 ⋅Cu(OH)2 (c) (iii) (v) (i) (iv) (d) (i) (ii) (iii) (iv)
170 JEE Main Chapterwise Topicwise Chemistry

Ans. (c) diagrams can also be constructed for standard Gibbs energies of formation of
(A) Siderite (FeCO3) is the ore of sulphides and halides. Such diagrams some metal oxides.
Fe ⇒(iii) of List-II. can help us in pridicting the feasibility of It predicts the feasibility of thermal
thermal reduction of an ore. reduction of the ore. The criterion of
(B) Calamine (ZnCO3) is the ore of
Zn ⇒(v) of List - II. feasibility is that at given temperature,
12 Match List-I with List-II. Gibbs energy of the reaction must be
(C) Malachite [CuCO3 ⋅ Cu(OH)2 ] is the
negative.
ore of Cu ⇒(i) of List II. List I List II
(D) Cryolite (Na3AlF6 ) is the ore of (Metal) (Ores) 14 For a reaction,
Al ⇒(iv) of List II. (as well as F2 )
A. Aluminium 1. Siderite 4M (s) + nO 2 (g) → 2M 2O n (s)
So, option -(c) is the correct matching.
Note Siderite and calamine are B. Iron 2. Calamine
The free energy change is plotted
carbonate ores whereas malachite is C. Copper 3. Kaolinite as a function of temperature. The
basic carbonate ore. Cryolite is the
D. Zinc 4. Malachite temperature below which the
thioxide ore.
oxide is stable could be inferred
Choose the correct answer from from the plot as the point at which
10 Match List-I with List-II.
the options given below. [2020, 6 Sep Shift-II]
List-I List-II [2021, 24 Feb Shift-II]
(a) the slope changes from negative
(Ore) (Element A B C D
to positive
present) (a) 4 3 2 1
(b) the free energy change shows a
A. Kernite (i) Tin (b) 2 4 1 3 change from negative to positive
B. Cassiterite (ii) Boron (c) 1 2 3 4 value
C. Calamine (iii) Fluorine (d) 3 1 4 2 (c) the slope changes from positive to
D. Cryolite (iv) Zinc Ans. (d) negative
(A) Siderite→FeCO3 (d) the slope changes from positive to
Choose the most appropriate
zero
answer from the options given Siderite is a mineral composed of
iron (II) carbonate (FeCO3). Ans. (b)
below. [2021, 26 Feb Shift-I]
(B) Calamine→ZnCO3 Ellingham diagram usually consists of
A B C D A B C D
Calamine is used to treat mild plots of ∆fG È vsT for the formation of
(a) (i) (iii) (iv) (ii) (b) (ii) (i) (iv) (iii)
itchiness and contain zinc in its oxide of various elements.
(c) (ii) (iv) (i) (iii) (d) (iii) (i) (ii) (iv) formula. For the reaction,
Ans. (b) (C) Kaolinite → Al2 (OH) 4 ⋅Si2O5 4M(s ) + nO2 (g) → 2M2On (s )
(A) Kernite (Na2B4O7 ⋅4H2O) is sodium Kaolinite is a type of clay found in
tetraborate tetrahydrate. It is also free energy change plot as a function of
nature. It is a dioctahedral temperature is as follows :
called rasovite. Kernite is also pyrosilicate clay containingSi2O5 .
written asNa2B4O6 (OH)2 ⋅3H2O
(D) Malachite→ Cu(OH)2 ⋅ CuCO3 Less –ve
(s)
It is an ore of boron (ii). On
Malachite is a copper carbonate 2
(B) Cassiterite (SnO2 ) is the oxide. 2M
hydroxide mineral, with the O ) →
It is an ore of tin (i). (g
formula Cu2 CO3 (OH)2 . 2
(C) Calamine (ZnCO3) is zinc nO
+
carbonate. It is also called smith (s)
13 An Ellingham diagram provides 4M
∆fG
s
sonite.
It is an ore of zinc (iv). information about More –ve
[2020, 5 Sep Shift-I] T
(D) Cryolite (Na3AlF6 ) is sodium
hexafluoroaluminate. (a) the kinetics of the reduction
In this reaction,O2 (a gas) is used up and
process.
It is an ore of fluorine (iii). M2On (s ), a solid is formed. Since, gases
(b) the pressure dependence of the have higher entropy than solids, ∆S
So, correct match is (A)-(ii), (B)-(i),
standard electrode potentials of becomes negative. Thus, on increasing
(C)-(iv), (D)-(iii).
reduction reactions involved in the the temperature,T∆f S È becomes more
extraction of metals. negative, hence ∆fG È becomes less
11 Ellingham diagram is a graphical (c) the temperature dependence of
representation of the standard Gibbs energies of negative which is shown in figure.
[2021, 25 Feb Shift-I] The slope of the curves for the formation
formation of some metal oxides.
(a) ∆G vs T (b) ∆H vs T (d) the conditions of pH and potential of metal oxides is positive as ∆fG È
(c) ∆G vs p (d) (∆G – T∆S) vs T under which a species is becomes less negative.
Ans. (a) thermodynamically stable. Any metal oxide having lower value of
Ellingham diagram is the graphical Ans. (c) ∆fG È is more stable as compared to
representation of ∆G vsT. For the Ellingham diagram provides information metal oxide with higher value of ∆ G È. f
formation of oxides of elements similar about temperature dependence of the
General Principles and Processes of Isolation of Metals 171

From the graph it is evident, that the ∴ B can reduce AO2 at these conditions. Ans. (d)
temperature below which the oxide is But above 1400°C, AO2 formation has Cryolite ore (Na3AlF6 , sodium
stable, is the point at which free energy more negative ∆G ° than BO2 , hexafluoroaluminate) contain fluorine
change shows a change from negative to ∴ A can reduce BO2 . while other given options such as
positive. malachite (Cu2 (CO) 3 (OH)2 ), sphalerite
17 With respect to an ore, Ellingham ((Zn,Fe)S) and bauxite (Al2O3) does not
15 The incorrect statement is diagram helps to predict the contain fluorine.
[2020, 6 Sep Shift-I]
feasibility of its [2019, 9 April Shift-I]
(a) bronze is an alloy of copper and 19 The one that is not a carbonate ore
tin. (a) electrolysis
(b) zone refining
is [2019, 9 April Shift-II]
(b) cast iron is used to manufacture
(c) vapour phase refining (a) siderite (b) calamine
wrought iron.
(d) thermal reduction (c) malachite (d) bauxite
(c) german silver is an alloy of zinc,
copper and nickel. Ans. (d) Ans. (d)
(d) brass is an alloy of copper and With respect to an ore, Ellingham Bauxite is not a carbonate ore. Its
nickel. diagram helps to predict the feasibility of chemical formula is Al2O3 or AlOx
Ans. (d) its thermal reduction. It is a graph (OH) 3 − 2 x , where 0 < x < I. Chemical
representation of Gibbs energy change formula of other ores given in options
Statements (d) is incorrect whereas all are as follows:
other statements are correct. versus absolute temperature.
Generally, the diagram consists of plots Siderite-FeCO3
(a) Bronze is an alloy of Cu (96%) and
Sn (4%). of ∆G ° versusT for the formation of Calamine-ZnCO3
oxides of elements Malachite-CuCO3 ⋅ Cu(OH)2
(b) Cast iron is used to manufacture
wrought iron. 2xM(s ) + O2 (g) → 2Mx O(s )
(c) German silver is an alloy of 50% Thermal reduction 20 The alloy used in the construction
Cu, 30% Zn and 20% Ni.
product of aircrafts is [2019, 10 April Shift-II]
(d) Brass is an alloy of 70% Cu and In this reaction, amount of gas (a) Mg-Zn (b) Mg-Mn
30% Zn. decreases thus, randomness decreases. (c) Mg-Sn (d) Mg-Al
Hence, the incorrect option is (d). Hence, ∆S becomes negative. Ans. (d)
Therefore, the value of free energy
increases with increase in temperature. Names of magnesium alloys are given by
16 According to the following diagram, There is a point in a curve below which two letters followed by two numbers.
A reduces BO 2 when the ∆G is negative. So, Mx O is stable. Above The common alloying elements are A
temperature is [2020, 9 Jan Shift-I] this point, Mx O will decompose on its (Aluminium), Z (zinc),T (tin), M
own. (manganese) etc. Numbers indicate
0
respective nominal compositions of
–600 –100
main alloying elements, e.g.
2Cu 2O
∆Gº/kJ mol–1

–200 4Cu+O 2 ‘AZ 91’ implies the composition of the

–800 2FeO
–300 2Fe+O 2 C+O2 CO2 alloy as : Al = 9%, Zn = 1% and Mg = 100 – (9
–1000 A+O2 AO2 –400 + 1) = 90%
2C+O
2CO2
∆Gº/kJ mol–1 of O2

2
–500 +O2 O 2CO
2CO 2Zn Among the alloys given, Mg – Al
–1200 B+O2 BO2 –600 +O2
2Zn (Magnalium ; Mg = 5%, Al =95%) is being
–700
0 200 400 600 800 10001200 1400 1600 –800
light, tough and strong, hence it is used
l +O3
T (ºC) –900 2/3 A 2 in aircrafts.
l+ O2
A O
–1000 4/3 2 Mg
(a) > 1200°C but < 1400°C 2 Mg
+O 2
(b) >1400° C
–1100 21 The ore that contains both iron and
–1200
(c) <1200°C copper is [ 2019, 9 Jan Shift-I]
0°C 400°C 800°C 1200°C 1600°C 2000°C (a) malachite
(d) <1400°C 273 K 673 K 1073 K 1473 K 1873 K 2273 K
Ans. (b) Temperature (b) azurite
Gibbs energy (∆Gº) versus T plots (schematic)
(c) dolomite
A metal with more negative value of ∆G ° for the formation of some oxides (Ellingham diagram)

of oxide formation reduces oxide of (d) copper pyrites

another metal which has less negative 18 The ore that contains the metal in Ans. (d)
value of ∆G °. Value of ∆G ° of oxide the form of fluoride is The formulae of the given ores are as
formation plotted against temperature [2019, 9 April Shift-I] follows:
(as given in question) is called (a) magnetite Malachite : CuCO3 ⋅ Cu(OH)2
Ellingham’s diagram.
(b) sphalerite Copper pyrites : CuFeS2
From the graph given, ∆G ° of BO2
(c) malachite Dolomite : CaMg(CO3)2
formation is more negative than AO2
upto 1400°C. (d) cryolite Azurite : Cu3 (CO) 3 (OH)2
172 JEE Main Chapterwise Topicwise Chemistry

22 The correct statement regarding (C) Malachite is an ore of copper with Based on these, select correct
molecular formula CuCO3 ⋅ Cu(OH)2 alternative.
the given Ellingham diagram is [AIEEE 2002]
(Q).
2Cu 2
O (a) zinc can be oxidised by CO
→ (D) Calamine is an ore of zinc with
+O 2 (b) zinc oxide can be reduced by
4Cu molecular formula ZnCO3 (P).
carbon
–300
24 The hottest region of Bunsen flame (c) Both (a) and (b)
(d) None of the above
∆Gº (kJ/mol)

2C
+O shown in the figure given below is
nO 2 →2 [JEE Main 2016] Ans. (b)
–600 O2 → 2Z CO
2Zn+ Region 4 ZnO + C → Zn + CO,
Region 3
Al 2O 3 ∆G ° = − ve
2 /3 Region 2
l+ O2 → Hence, this is spontaneous.
4/3 A Region 1
–1050
500ºC 800ºC
Temperature (ºC)
2000ºC
TOPIC 2
[2019, 10 Jan Shift-II] (a) region 2 (b) region 3 Extraction and
(a) At 800°C, Cu can be used for the (c) region 4 (d) region 1 Isolation of Metals
extraction of Zn from ZnO Ans. (a)
(b) At 1400°C, Al can be used for the 27 Given below are two statements.
Region 1 (Pre-heating zone)
extraction of Zn from ZnO One is labelled as Assertion (A) and
Region 2 (Primary combustion zone,
(c) At 500°C, coke can be used for the the other is labelled as Reason (R).
hottest zone)
extraction of Zn from ZnO Assertion (A) Aluminium is
(d) Coke cannot be used for the Region 3 (Internal zone)
Region 4 (Secondary reaction zone) extracted from bauxite by the
extraction of Cu from Cu2O
electrolysis of molten mixture of
Ans. (b)
25 Which of the following factors is of Al 2O 3 with cryolite.
From the Ellingham diagram, we can say
that any oxide with lower value of ∆G ° is no significance for roasting Reason (R) The oxidation state of
more stable than a oxide with higher sulphide ores to the oxides and not Al in cryolite is +3 .
value of ∆G °. subjecting the sulphide ores to In the light of the above
We can also predict that the oxide carbon reduction directly? statements, choose the most
placed higher in the diagram can be [AIEEE 2008]
reduced by the element involved in the appropriate answer from the
(a) Metal sulphides are
formation of its oxide placed lower at that thermodynamically more stable
options given below.
temperature in the diagram. It is [2021, 31 Aug Shift-I]
than CS2
happening in case of ZnO for its reduction (a) (A) is true but (R) is false
(b) CO2 is thermodynamically more
by Al at 1400°C. (b) (A) is false but (R) is true.
stable than CS2
(c) Metal sulphides are less stable (c) Both (A) and (R) are true and (R) is
23 Match the ores ( Column A ) with the correct explanation of (A).
than the corresponding oxides
the metals (Column B). (d) Both (A) and (R) are true but (R) is
(d) CO2 is more volatile than CS2
not the correct explanation of (A).
Column A Column B Ans. (c)
(Ores) (Metals) Ans. (d)
2 MS + C → 2M + CS2 ; ∆G 1 = +ve
Aluminium is reactive metal. So,
A. Siderite P. Zinc 2MO + C →2M + CO2 ; ∆G2 = –ve
aluminium is extracted by electrolysis of
B. Kaolinite Q. Copper The value of ∆G for the formation of CO2 alumina with molten mixture of cryolite.
C. Malachite R. Iron is negative, i,e., it is thermodynamically Hence, Assertion is true.
D. Calamine S. Aluminium more stable than CS2 . Also, metal Cryolite has molecular formulaNa3AlF6 .
sulphides are thermodynamically more
(a) A - P; B- Q; C - R; D- S Oxidation state of Al inNa3AlF6
stable than CS2 .
(b) A - R; B- S; C - P; D- Q 3 × (+1) + Al + 6 × (−1) = 0
Metal sulphides are more stable than the
(c) A - Q; B- R; C - S; D- P corresponding oxides, so they are 3 + Al − 6 = 0 ⇒ Al = + 3
(d) A - R; B- S; C - Q; D- P roasted to convert into less stable Hence, Reason is true.
[2019, 11 Jan Shift-I] oxides. Oxidation state cannot explain that Al is
Ans. (d) extracted from bauxite by electrolysis.
The correct match is: A→ R; B → S; 26 Consider the following reactions at ∴ The correct option is (d).
C → Q; D → P. 1100°C
(A) Siderite is an ore of iron with 28 Given below are two statements.
molecular formula FeCO3 (R). (I) 2C + O 2 → 2CO,
(B) Kaolinite is an ore of aluminium ∆G° = − 460 kJ mol −1 Statement I Sphalerite is a
with molecular formula (II) 2Zn + O 2 → 2ZnO, sulphide ore of zinc and copper
Al2Si2 (OH)2 O5 (S). ∆G° = − 360 kJ mol −1 glance is a sulphide ore of copper.
General Principles and Processes of Isolation of Metals 173

Statement II It is possible to Choose the correct answer from Ans. (a)

separate two sulphide ores by the options given below. (A) Heating of carbonate ores in
adjusting proportion of oil to [2021, 25 July Shift-II] absence or limited supply of air or
A B C D oxygen is called calcination.
water or by using ‘depressants’ in
a froth flotation method. (a) III II I IV ∆
ZnCO3 (s ) → ZnO(s ) + CO2 (g)
Choose the most appropriate (b) III IV I II (B) Roasting includes heating of
answer from the options given (c) IV I III II sulphide ore in the presence of
below. [2021, 26 Aug Shift-II] (d) IV III II I oxygen or air.
(a) Statement I is true but statement Ans. (a) ∆
2ZnS( s ) + 3O2 ( g) → 2ZnO( s )+ 2SO2 ( g)
II is false. A. Concentration of Ag ore is
Therefore, (A) is calcination process
(b) Both statement I and statement II performed by leaching with dilute
while (B) is roasting.
are true. NaCN solution.
(c) Statement I is false but statement B. Pig iron is formed in blast furnace.
II is true. 33 Match List-I with List-II.
C. Blister copper is produced in
(d) Both statement I and statement II bessemer converter. List-I List-II
are false. D. Froth floatation method is used for
A. Mercury 1. Vapour phase
Ans. (b) sulphide ores. It is selectively refining
Both statements I and II are true. separating hydrophobic materials
from hydrophilic. B. Copper 2. Distillation refining
Sphalerite –ZnS (Sulphide ore of zinc).
Note During extraction of Cu C. Silicon 3. Electrolytic refining
Copper glance – Cu2S (Sulphide ore of
reverberatory furnace is involved. D. Nickel 4. Zone refining
copper).
It is possible to separate two sulphide
ores by adjusting the proportion of oil to 31 In the leaching of alumina from Choose the most appropriate
water or by using depressants. bauxite, the ore expected to leach answer the option given below
out in the process by reacting with [2021, 18 March Shift-II]
29 The addition of silica during the NaOH is [2021, 25 July Shift-I] A B C D A B C D
extraction of copper from its (a) TiO2 (b) Fe2O 3 (a) 1 4 2 3 (b) 2 3 1 4
sulphide ore [2021, 27 July Shift-II] (c) ZnO (d) SiO2 (c) 2 3 4 1 (d) 2 4 3 1
(a) converts copper sulphide into Ans. (d) Ans. (c)
copper silicate
In bauxite impurities of Fe2O3, TiO2 and (A) The pyrometallurgical extraction
(b) converts iron oxide into iron
SiO2 are present,Fe2O3 and TiO2 are basic of mercury from its ore is
silicate essentially a distillation process.
oxides, it does not reacts with or
(c) reduces copper sulphide into dissolve in NaOH whereas SiO2 is acidic (B) The purification of metals by
metallic copper oxide it dissolve in NaOH, hence leach electrolysis is commonly applied to
(d) reduces the melting point of the outeasily. copper. A large piece of impure
reaction mixture
SiO2 +2NaOH → Na2SiO(aq) + H2O copper is used as the anode with a
Ans. (b) Silica Sodium thin strip of pure copper as the
hydroxide
Silica is used to remove FeO impurity cathode.
from the ore of copper. The impurities of (C) Zone refining is a very useful
iron oxide combine with silica and form
32 Consider two chemical reactions method to get metals with very
insoluble slag. (A) and (B) that take place during high purity such as silicon and
Fuse
FeO + SiO2 → Fe SiO3
metallurgical process : germanium. It is also referred as
Basic ∆ zone melting.
impurity
Acidic
flux
Iron silicate
(slag) (A) ZnCO 3 (s) → ZnO (s) +CO 2 (g ) (D) Mond’s process for extraction of
∆ nickel and van-Arkel method for
(B) 2ZnS (s) + 3O 2 (g) → 2ZnO (s) preparing ultra-pure titanium are
30 Match List I with List II : (Both
having metallurgical terms) +2SO 2 (g) based on the principle of vapour
phase refining.
The correct option of names given Hence, correct match is (A-2), (B-3),
List I List II
to them respectively is (C-4), (D-1).
(A) Concentration I. Reverberatory [2021, 20 July Shift-II]
of Ag ore furnace
(a) (A) is calcination and (B) is roasting 34 The chemical that is added to
(B) Blast furnace II. Pig iron (b) Both (A) and (B) are producing
(C) Blister copper III. Leaching with
reduce the melting point of the
same product so both are roasting
dilute NaCN solution (c) Both (A) and (B) are producing
reaction mixture during the
(D) Froth IV. Sulphide ores same product so both are extraction of aluminium is
floatation [2021, 18 March Shift-I]
calcination
method (d) (A) is roasting and (B) is calcination (a) cryolite (b) bauxite
(c) calamine (d) kaolite
174 JEE Main Chapterwise Topicwise Chemistry

Ans. (a) Ans. (d)

In the extraction of aluminium by electrolytic process, cryolite is Consider the following flow sheet :
added to reduce the melting point of the mixture. The use of
Pig iron Scrap iron/coke Cast iron In
cryolite reduces some of the energy cost involved in extracting
aluminium. C% = 5-6 hot air C% = 3-3.5 Reverberatory
furnance
Reactions involved in the electrolysis are given below In
– CO2 O2 (air)
Al2O3 « 2Al +3 + 3O–2 Bessemer – P2O5
– SO2
Na3AlF6 « 3Na+ + Al +3 + 6F − convertor – CO2
– MnO
– P2O5
CaF2 « Ca+2 + 2F − Spiegeleisen – SiO2
– SiO2
At cathode : Al 3+ + 3e − → Al (reduction) (an alloy of – SO2
Fe, Mn and C)
At anode : C + O2 − → CO + 2e − (oxidation)
C + 2O2− → CO2 + 4e −
Steel Wrought iron
35 Which of the following reduction reaction cannot be C% =0.5-1.5 C% =0.2-0.5
carried out with coke? [2021, 16 March Shift-II]
So, it is clear from the flow chart that cast iron is used in the
(a) Al2O 3 → Al (b) ZnO → Zn
manufacture of wrought iron and steel.
(c) Fe2O 3 → Fe (d) Cu2O → Cu
Ans. (a)
39 Among statements (A)-(D), the correct ones are :
Reduction of alumina (Al2O3) to Al cannot be achieved by carbon
reduction. As aluminium has greater reactivity with oxygen than (A) Limestone is decomposed to CaO during the
carbon and hence cannot be reduced by carbon. So, extraction of iron from its oxides.
electrometallurgy (Hall-Heroult process) is used to get Al. (B) In the extraction of silver, silver is extracted as an
2Al2O3 (l ) + 3C → 4Al + 3CO2 anionic complex.
Rest oxides can be reduced by coke as follows (C) Nickel is purified by Mond’s process.
Fe2O3 + 3C → 2Fe +3CO (D) Zr and Ti are purified by van-Arkel method.
Cu2O + C → 2Cu + CO [2020, 4 Sep Shift-I]
Coke, 1673 K (a) (A), (B), (C) and (D) (b) (A), (C) and (D) only
ZnO + C → Zn + CO
(c) (C) and (D) only (d) (B), (C) and (D) only
36 The process that involves the removal of sulphur from Ans. (a)
the ores is [2021, 16 March Shift-I] Statements (A), (B), (C) and (D) are correct.
∆
(a) smelting (b) roasting (c) leaching (d) refining (A) CaCO3 → CaO + CO2
Ans. (b) Limestone Gas

The process that involves the removal of sulphur from the ores is (B) Ag with CN È form cyanide complex [Ag(CN)2 ] È .
called roasting. Ag + CNÈ → [Ag(CN)2 ] È
In roasting, the ore is heated in a regular supply of air in a furnace (C) Mond’s process is used to purification of Ni.
at a temperature below the melting point of the metal. (D) van-Arkel method is used to purification of Zr and Ti.
Some of the reactions involving sulphide ores are
2ZnS + 3O2 → 2ZnO + 2SO2 40 The processes of calcination and roasting in
2PbS + 3O2 → 2PbO + 2SO2 metallurgical industries, respectively, can lead to
2Cu2S + 3O2 → 2Cu2O + 2SO2 [2020, 4 Sep Shift-II]
(a) global warming and acid rain
37 Which of the following ore is concentrated using group 1 (b) global warming and photochemical smog
cyanide salt ? [2021, 24 Feb Shift-I] (c) photochemical smog and ozone layer depletion
(a) Calamine (b) Malachite (c) Siderite (d) Sphalerite (d) photochemical smog and global warming
Ans. (d) Ans. (a)
The chemical formulas of given ore in options are as follows (a) Due to industrial process, CO2 release from calcination andSO2
Sphalerite ore : ZnS ; Calamine ore : ZnCO 3 release from roasting respectively which is responsible for global
Siderite ore : FeCO 3; Malachite ore : Cu(OH)2 ⋅ CuCO3 warming and acid rain.
Sphalerite ore containing ZnS is concentrated using group is Calcination It involves heating where the volatile matter escapes
cyanide salt (NaCN) as a depressant by froth flotation method. leaving behind the metal oxide. In this process, the ore is heated
below its melting point in the absence of air or in the limited
38 Cast iron is used for the manufacture of supply of air.
∆
(a) wrought iron and pig iron [2020, 2 Sep Shift-II] e.g. CaCO3 (s ) → CaO(s ) + CO2 ↑
(b) pig iron, scarp iron and steel (Carbon dioxide)
Responsible for
(c) wrought iron, pig iron and steel
global warming
(d) wrought iron and steel
General Principles and Processes of Isolation of Metals 175

Roasting In this process the ore is (c) Both the assertion and reason are Ans. (b)
heated in a regular supply of air in a correct and the reason is the The idea of froth floatation method
furnace at a temperature below the correct explanation for the came from a person ‘washer woman’ (X)
melting point of the metal. assertion. and this method is related to the process
e.g. (d) Only the assertion is correct. concentration (Y ) of ores.
2ZnS + 3O2 → 2ZnO + 2SO2 ↑ Ans. (d) This method is based upon the
(Sulphur dioxide) preferential wetting properties with the
Responsible for
Only assertion is correct and reason is
incorrect. Haematite is not a carbonate frothing agent (collector) and water.
acid rain
ore. It is an oxide ore, i.e. Fe2O3. Cast iron
41 The purest form of commercial iron is extracted chiefly from its oxide ore 46 The correct statement is
(haematite) by heating in the presence of (a) leaching of bauxite using
is [2020, 7 Jan Shift-I]
coke and limestone in a blast furnace. concentrated NaOH solution gives
(a) cast iron
sodium aluminate and sodium
(b) scrap iron and pig iron 44 The correct statement is silicate.
(c) wrought iron (a) zone refining process is used for (b) the hall-heroult process is used for
(d) pig iron the refining of titanium. the production of aluminium and
Ans. (c) (b) zincite is a carbonate ore. iron.
Wrought iron is the purest form of (c) sodium cyanide cannot be used in (c) pig iron is obtained from cast iron.
commercial iron. the metallurgy of silver. (d) the blistered appearance of
(d) aniline is a froth stabiliser. copper during the metallurgical
42 Among the reactions (A) - (D), the [2019, 10 April Shift-II] process is due to the evolution of
reaction(s) that does/do not occur Ans. (d) CO2 . [2019, 12 April Shift-II]
in the blast furnace during the The explanation of given statements are Ans. (a)
extraction of iron is/are as follows : The correct statement is ‘‘leaching of
(A) CaO + SiO2 → CaSiO 3 (a) Zone refining process is used for bauxite using concentrated NaOH
the refining of B, Ga, In, Si and Ge. solution gives sodium aluminate and
(B) 3Fe2O 3 + CO → 2Fe 3O 4 + CO2
Ti is refined by van Arkel method. sodium silicate’’. Bauxite usually
(C) FeO + SiO2 → FeSiO 3 contains SiO2 , iron oxides and titanium
Thus, statement (a) is incorrect.
1 oxide (TiO2 ) as impurities.
(D) FeO → Fe + O2 (b) Zincite (ZnO) is an oxide ore of Zn.
2 Concentration is carried out by digesting
[2020, 8 Jan Shift-II] Thus, statement (b) is incorrect. the powdered ore with a concentrated
(a) (C) and (D) (b) (A) (c) NaCN is used in the solution of NaOH at 473-523 K and 35-36
(c) (A) and (D) (d) (D) hydrometallurgy of silver. It is bar pressure. Al2O3 is leached out as
known as Mc. Arthur Forrest sodium aluminate (andSiO2 too as
Ans. (a) process. sodium silicate) leaving the impurities
Reaction (C) and (D) do not occur in the The reactions occuring during the behind.
blast furnace during the extraction of iron. process are as follows : Al2O3 (s ) + 2NaOH(aq) + 3H2O(l ) →
(C) FeO + SiO2 → FeSiO3 Ag2S + 4NaCN → 2Na[Ag(CN)2 ] 2Na[Al(OH) 4 ] (aq)
⇒ (occur in Cu metallurgy) + Na2S The aluminate in solution is neutralised
1
(D) FeO → Fe + O2 4Na2S + 2H2O + 5O2 → 2Na2SO4 by passing CO2 gas and hydrated Al2O3 is
2 precipitated. Here, the solution is
+ 4NaOH + 2S
(not possible without reducing agent like seeded with freshly prepared samples of
2Na[Ag(CN)2 ] + Zn →
CO) whereas, both (A) and (B) reactions hydrated Al2O3 which induces
occur during extraction of Fe. Na2 [Zn(CN) 4 ] + 2Ag precipitation.
(A) CaO + SiO2 → CaSiO3 Thus, statement (c) is incorrect.
(d) Aniline and cresol help in 2Na[Al(OH) 4 ] (aq) + CO2 (g) →
(slag formation in blast furnace)
stabilising the froth in froth Al2O3 ⋅ xH2O(s ) + 2NaHCO3 (aq)
(B) 2Fe2O3 + CO → 2Fe3O4 + CO2
floatation process. The sodium silicate remains in the
⇒ (reduction of Fe3+ to Fe3O4 ) solution and hydrated alumina is filtered,
Thus, statement (d) is correct.
dried and heated to give back pure Al2O3.
43 Assertion For the extraction of 45 The idea of froth floatation method Al2O3 ⋅xH2O(s ) 1470
K→ Al2O3 (s ) + xH2O(g)
iron, haematite ore is used. came from a person X and this
[2019, 9 April Shift-II]
method is related to the process Y 47 Hall-Heroult’s process is given by
Reason Heamatite is a carbonate of ores. X and Y, respectively, are Coke, 1673 K
(a) ZnO + C → Zn + CO
ore of iron. [2019, 12 April Shift-I]
(b) Cr2O 3 + 2Al → Al2O 3 + 2Cr
(a) Only the reason is correct. (a) fisher woman and concentration
(b) Both the assertion and reason are (b) washer woman and concentration (c) 2Al2O 3 + 3C → 4Al + 3CO2
correct explanation for the (c) fisher man and reduction (d) Cu2+ (aq ) + H2 ( g ) → Cu( s ) + 2H+ (aq )
assertion. (d) washer man and reduction
[ 2019, 10 Jan Shift-I]
176 JEE Main Chapterwise Topicwise Chemistry

∆
Ans. (c) At anode Fe2 (SO4 ) 3 → Fe2O3 (s ) + 3 SO3 ↑
Hall-Heroult’s process is an C(s) + O2 − (melt) → CO(g) +2e −
electro-reduction process by which pure C(s) + 2O2 − (melt) → CO2 (g) + 4e − O 2 ,heat dil. H 2 SO 4
alumina (Al2O3) is reduced to crude Al. In (b) Fe → FeO → FeSO4
this process, electrolysis of a fused
50 The pair that does not require → Fe
Heat
mixture of Al2O3, Na3 [AlF6 ] (cryolite) and
CaF2 (fluorspar) is carried out at carbon calcination is [2019, 12 Jan Shift-II]
This reaction series is also
cathode and graphite anode. The overall (a) ZnO and MgO incorrect.
reaction is represented as: (b) ZnO and Fe2O 3 ⋅xH2O The correct reaction series is
2Al2O3 + 3C → 4Al + 3CO2 (c) ZnCO 3 and CaO O2
F → FeO [It could also be Fe2O3
(d) Fe2O 3 and CaCO 3 ⋅MgCO 3 ∆
48 The reaction that does not define or Fe3O4 ]
calcination is Ans. (a)
FeO + H2SO4 → FeSO4 + H2O
∆ The hydroxide, hydrated oxides and
(a) Fe2O 3 ⋅ XH2O → Fe2O 3 + XH2O carbonate ores, after concentration, are
∆
2FeSO4 → Fe2O3 + SO2 + SO3
∆ subjected to calcination. In the process,
(b) ZnCO 3 → ZnO + CO2 Cl2 ,heat
the ore is heated below its melting point Heat, air
∆ (c) Fe → FeCl 3 → FeCl2
(c) CaCO 3 ⋅MgCO 3 → CaO in the limited supply or absence of air. As
Zn
+ MgO + 2CO2 the result, these are converted into their → Fe
∆ oxides.
(d) 2Cu2 S + 3O2 → 2Cu2O + 2SO2 The reaction ofFeCl 3 is not
So, among the given options, the options possible. Thus, the above reaction
[2019, 11 Jan Shift-II] having either carbonates (e.g.ZnCO3 and series is incorrect.
Ans. (d) CaCO3 ⋅ MgCO3) or hydrated oxide (e.g.
∆ CO , 600 ° C
Calcination is one of the pyrometallurgical Fe2O3 ⋅ xH2O), require calcination while (d) Fe → Fe3O4 → FeO
process, like roasting by which a pair of option (a), i.e. ZnO and MgO does O2
CO , 700 ° C
concentrated ore gets converted into its not require calcination. → Fe
oxide. This reaction series is correct.
In calcination, a hydrated carbonate or
51 Which series of reactions correctly
bicarbonate ore or a hydrated ore is represent chemical relations 52 Which one of the following ores is
heated at lower temperature (compared related to iron and its compound? best concentrated by froth-floatation
to roasting) in absence of air to give its [JEE Main 2014]
method ? [AIEEE 2004]
oxide as in options (a), (b) and (c). Here, Dil. H2 SO 4 H2 SO 4 , O2
(a) Fe → FeSO 4 → (a) Magnetite
volatile non-metallic oxides likeH2O, CO2 , Heat
are also produced. Fe2 (SO 4 ) 3 → Fe (b) Cassiterite
Roasting is valid mainly for sulphide ores dil. H 2 SO 4
(c) Galena
O 2 , heat
like option (d), whereSO2 gets liberated. (b) Fe → FeO → FeSO 4 (d) Malachite
In this reaction, calcination cannot be Heat
Ans. (c)
used. → Fe
Cl2 ,heat Heat, air Froth-floatation is used to concentrate
(c) Fe → FeCl3 → FeCl2 sulphide ores [Galena (PbS)].
49 In the Hall-Heroult process, Zn
aluminium is formed at the → Fe
53 Aluminium is extracted by the
cathode. The cathode is made out O 2 ,heat CO , 600° C
(d) Fe → Fe 3O 4 → FeO electrolysis of [AIEEE 2002]
of [2019, 12 Jan Shift-I]
(a) alumina
CO ,700° C
(a) platinum → Fe (b) bauxite
(b) carbon (c) molten cryolite
Ans. (d)
(c) pure aluminium (d) alumina mixed with molten cryolite
(d) copper This problem involves the concept of
Ellingham diagram as this diagram Ans. (d)
Ans. (b) predicts the basis of oxidation state and Aluminium is extracted by electrolysis of
In the Hall-Heroult’s process, aluminium stability of iron compounds. a fused mixture of alumina (2-8%),
in formed at the cathode. The cathode is dil. H 2 SO 4 H 2 SO 4 , O 2 synthetic cryolite Na3AlF6 (80-85%), AlF3
made out of carbon. In this method, Al2O3 (a) Fe → FeSO4 → and fluorspar.
is melted with cryolite, Na3 [AlF6 ] and Heat This makes alumina good conductor and
electrolysed in a graphite lined steel Fe2 (SO4 ) 3 → Fe
lowers the fusion temperature also.
tank, which serves as the cathode. The The above given reaction series is
anode is also made of graphite. 54 Cyanide process is used for the
incorrect. The correct reactions series is
The cell runs continuously and at as follows
extraction of [AIEEE 2002]
intervals molten aluminium is drained (a) barium
Fe + H2SO4 → FeSO4 + H2
from the bottom of the cell and more 1 (b) silver
bauxite is added. The electrolytic H2SO4 + 2FeSO4 + O2 → Fe2 (SO4 ) 3 (c) boron
reactions are as follows: 2
+H2O (d) zinc
At cathode Al 3+ + 3 e − → Al
General Principles and Processes of Isolation of Metals 177
Ans. (b) (Hg), zinc (Zn), cadmium (Cd) etc. In this
58 Using the provided information in
CyanideprocessorMacArthur-Forest method pure metal is heated and its
the following paper chromatogram.
cyanideprocess vapours are separately condensed in a
2Ag2S + 8NaCN + O2 + 2H2O → receiver, while the pure metal distils
out, impurities (non-volatile) are left
4Na [Ag(CN)2 ] + 4NaOH + 2S Solvent front behind.
Soluble silver complex is filtered and
treated with zinc dust and silver gets 5cm 2cm 61 The refining method used when the
precipitated. metal and the impurities have low
2Na [Ag(CN)2 ] + Zn →Na2 [Zn(CN) 4 ] 2cm and high melting temperatures,
+ 2Ag ↓ respectively, is [2020, 7 Jan Shift-II]
(a) distillation
TOPIC 3 (b) zone refining
Spot Base line (c) liquation
Refining of Metals Paper chromatography (d) vapour phase refining
for compounds A and B Ans. (c)
55 In the electrolytic refining of blister
Liquation is used when melting points of
copper, the total number of main The calculated R f value of A ………
metal and impurity are quite different.
impurities from the following, × 10 −1 . [2021, 25 Feb Shift-I]
Metal melts at a lower temperature and
removed as anode mud is …… Ans. (4) flows down a slope while the impurity
Pb, Sb, Se, Te, Ru, Ag, Au and Pt The retention factor (Rf ) value can be stays as solid.
[2021, 31 Aug Shift-II] used to identify the components of a
Ans. (6) mixture (solutes). 62 The Mond process is used for the
Distance travelled by solute [2019, 8 April Shift-II]
Impurities from blister copper deposited Rf =
as anode mud contain antimony, Distance travelled by solvent front (a) purification of Ni
selenium, tellurium, silver, gold and On chromatogram, distance travelled by (b) extraction of Mo
platinum. compound is 2 cm. (c) purification of Zr & Ti
These are basically less active metals Distance travelled by solvent = 5 cm (d) extraction of Zn
which cannot be oxidised at anode. 2
∴ Rf = = 4 × 10 −1 Ans. (a)
5 Mond process is used in the purification
56 Which refining process is generally of Ni. It is a vapour phase refining
used in the purification of low 59 Boron and silicon of very high process.
melting metals? [2021, 27 Aug Shift-I] purity can be obtained through It is based on the principle that Ni is
(a) Chromatographic method (a) liquation [2020, 5 Sep Shift-II] heated in the presence of carbon
(b) Liquation (b) zone refining monoxide to form nickel tetracarbonyl,
which is a volatile complex. This
(c) Electrolysis (c) vapour phase refining
complex is then decomposed by
(d) Zone refining (d) electrolytic refining subjecting it to a higher temperature
Ans. (b) Ans. (b) (450-470 K) to obtain pure nickel metal.
Liquation is used for separating metals In zone refining the impure metal rod is Crude nickel (s) + 4 CO (g)
which have lower melting points than the electrically heated till life metal in the (Impure) Recycled
impurities. The process is done by heated zone melts. There metal is
keeping the metal to be refined in a 330-350 K
collected at one end of the rod.
sloping surface of a furnace. The Repeating the metal with the product Ni (s)
temperature will be maintained above obtained each time highly pure metal is [Ni (CO)4] (g) 450-470 K Pure + 4 CO (g)
the melting point of metals. Thus, pure (Volatile compound)
obtained. This method is very useful for
metal melts and moves down. producing semiconductor and other
metals with high purity. 63 Match the refining methods
57 The method used for the e.g. Germanium, silicon, boron, gallium Column I with metals Column II.
purification of indium is and indium etc.
[2021, 25 Feb Shift-II]
Column I Column
(a) van-Arkel method 60 The element that can be refined by (Refining Methods) II
(b) liquation (Metals)
distillation is [2020, 6 Sep Shift-II]
(c) zone refining
(a) nickel (b) zinc I. Liquation (A) Zr
(d) vapour phase refining
(c) tin (d) gallium II. Zone refining (B) Ni
Ans. (c) Ans. (b)
Zone refining method is very helpful for III. Mond process (C) Sn
Zinc is refined by distillation.
producing semiconductor and other IV. van Arkel method (D) Ga
metals of high purity, It is used for purification of low boiling
e.g., Si, Ge, B, Ga, In etc. point or volatile metals, such as mercury [2019, 10 April Shift-I]
178 JEE Main Chapterwise Topicwise Chemistry

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

(b) I- (B) ; II-(C); III-(D) ; IV-(A) Electroplating is a process of coating one metal or metal object
(c) I- (C) ; II-(A); III-(B) ; IV-(D) with a very thin layer of another metal typically applying a direct
(d) I- (B) ; II-(D); III-(A) ; IV-(C) electric current.
Ans. (a) Electrolytes used in the electroplating of gold and silver are given
Refining of crude metals results pure metals and its impurities in the table below :
get separated out. Pure metal block
I. Liquation In this method low melting metals like Sn, Pb, Bi acts an anode
and Hg can be made to flow down through a sloping by which
surface leaving behind the higher melting impurities on the electroplating will
hearth. be done
II. Zone refining The basic principle of the method is, (a) Gold Article Ai(S) Na[Au(CN)2]
impurities are more soluble in the molten metal than in the plating (Sodium
solid state of the metal. This method is useful to produce auro-cyanide)
semiconductors and ultra-pure metals like B, Ga, In, Si and (b) Silver Article Ag(S) Na[Ag(CN)2]
Ge. plating (Sodium argento
III. Mond process cyanide)
330-350 K
Crude nickel (s) + 4CO(g) Ni(CO)4(g)
(Impure) (Volatile compound) 65 Which method of purification is represented by the
following equation? [AIEEE 2012]
Recycled
450-470 K
523 K 1700 K
Ti (s ) + 2I 2 (g ) → TiI 4 (g) → Ti (g ) + 2 I 2 (g )
Ni(s) (a) Zone refining (b) Cupellation
4CO(g) +
(Pure) (c) Polling (d) van-Arkel
Ans. (d)
IV. van Arkel method
van-Arkel method is used for refining Titanium and Zirconium.
330-350 K 450-470 K
Crude nickel (s) + 4CO(g) Ni(CO)4(g) This method is useful for removing volatile impurities likeO2 , N2 , I2
(Impure) (Volatile compound)
present in the metals of Zr
Recycled Ni(s) and Ti.
4CO(g) +
(Pure) In this method, metal iodide is formed by direct combination of
metal and iodine.
Here, M = Zr, Hf, Ti
The metal iodide undergo decomposition on a tungsten filament
Hence, the correct matching is
and thus, pure metal is deposited on the filament.
I → (C), II → (D), III → (B), IV → (A).
66 During the process of electrolytic refining of copper,
64 The electrolytes usually used in the electroplating of
some metals present as impurity settle as ‘anode mud’.
gold and silver, respectively, are [2019, 10 Jan Shift-II]
These are [AIEEE 2005]
(a) [Au(OH) 4] − and [Ag(OH)2] −
(a) Fe and Ni (b) Ag and Au (c) Pb and Zn (d) Se and Ag
(b) [Au(NH3)2] + and [Ag(CN)2] −
Ans. (b)
(c) [Au(CN)2] − and [Ag(CN)2] −
During electrolysis, noble metals (inert metals) like Ag, Au and Pt are
(d) [Au(CN)2] − and [AgCl2] − not affected and separate as anode mud from the impure anode.
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15
Hydrogen
TOPIC 1 Atomic mass 3
T
Nitrogen dioxide reacts with water to
Atomic number 1 form nitric acid and nitrous oxide.
Preparation and Properties We know that, for neutral element 3NO2 + H2O → 2HNO3 + NO
of Hydrogen Atomic number (Z) = Number of protons The single largest industrial application
(np ) = Number of electrons (ne ) = 1 of dihydrogen in the synthesis of
01 Which one of the following Atomic mass (A) = Number of neutrons + ammonia (Haber’s process).
statements is incorrect ? Number ofprotons N2 ( g)+ 3H2 ( g) q 2NH3( g)
[2021, 31 Aug Shift-II] 3 = nn + np
(a) Atomic hydrogen is produced 3 = nn + 1 05 Dihydrogen of high purity
when H2 molecules at a high 3 − 1 = nn ⇒ nn = 2 (> 99.95%) is obtained through
temperature are irradiated with [2020, 6 Sep Shift-II]
UV radiation. (a) the reaction of Zn with dilute HCl
(b) At around 2000 K, the dissociation
03 Isotope(s) of hydrogen which emits
(b) the electrolysis of acidified water
of dihydrogen into its atoms is low energy β − particles with t 1/ 2 using Pt electrodes
nearly 8.1%. value > 12 years is/are (c) the electrolysis of brine solution
[2021, 22 July Shift-II]
(c) Bond dissociation enthalpy of H2 is (d) the electrolysis of warm Ba(OH)2
highest among diatomic gaseous (a) protium
solution using Ni electrodes.
molecules which contain a single (b) tritium
Ans. (d)
bond . (c) deuterium
(d) deuterium and tritium Electrolysis of warm aqueous Ba(OH)2
(d) Dihydrogen is produced on
solution between nickel electrodes is a
reacting zinc with HCl as well as Ans. (b) commercial method to obtain highly
NaOH(aq). Tritium is the only isotope of hydrogen pure (> 99.95%) dihydrogen.
Ans. (b) which is radioactive. In the presence ofBa(OH)2 , water
Tritium has a half-life of 12.3 yr and it dissociates into ions easily and quickly
Statement (b) is incorrect. The corrected
emits low energyβ-particles (β − ). and H+ ions are produced, which go on
statement is :
cathode, gets discharged there and
At around 2000 K, the dissociation of liberate hydrogen gas.
dihydrogen into its atoms is only ~0.081%. 04 The single largest industrial
Bond dissociation enthalpy ofH2 application of dihydrogen is
[2021, 20 July Shift-II]
06 The equation that represents the
molecule is highest due to very strong
attraction between the atoms. (a) manufacture of metal hydrides water-gas shift reaction is
[2020, 5 Sep Shift-I]
Zn + 2HCl → H2 + ZnCl2 (b) rocket fuel in space research
1270 K
Zn + NaOH → Na2ZnO2 + H2 (c) in the synthesis of ammonia (a) C (s ) + H2O (g) ———→ CO (g) + H2 (g)
H—H bond dissociate by increasing (d) In the synthesis of nitric acid 1273 K
temperature and shining UV light. (b) 2C( s ) + O2 ( g ) + 4N2 ( g ) ———→
Ans. (c)
2 CO( g ) + 4N2 ( g )
02 The number of neutrons and Dihydrogen is used as rocket fuel in
673 K
space research. Metal react with (c) CO( g ) + H2O (g ) ———→ CO2 + H2 (g)
electrons, respectively, present in Catalyst
hydrogen gas to form metal hydrides.
the radioactive isotope of hydrogen
Metal + H2 → Metal hydrides 1270 K
(d) CH4 (g) + H2O(g) ———→
is [2021, 27 July Shift-II] Ni CO(g) + 3H2 (g)
H2 also used for synthesis of nitric acid
(a) 1 and 1 (b) 3 and 1 (HNO3). Ans. (c)
(c) 2 and 1 (d) 2 and 2 Hydrogen gas react with nitrogen dioxide In water gas shift reaction, hydrogen gas
Ans. (c) to form water and nitrous oxide. is produced economically by the reaction
Radioactive isotope of hydrogen is H2 (g) + NO2 (g) → H2O(g) + NO(g) of carbon monoxide with water vapour at
tritium. It is represented as follows
180 JEE Main Chapterwise Topicwise Chemistry

673 K in presence of iron, cromium and The second isotope of hydrogen is called (c) H2 is removed through occlusion
copper zinc catalyst. heavy hydrogen or deuterium. It consists with Pd
CO + H2O(g) Catalyst
→ CO2 (g) + H2 (g) of one proton and one neutron in the (d) CO is oxidised to CO2 with steam in
∆ nucleus and an electron revolving around the presence of a catalyst
07 5 g of zinc is treated separately it. The third isotope of hydrogen is called followed by absorption of CO2 in
tritium. It consists of one proton and two
with an excess of alkali.
neutrons in the nucleus and an electron
(1) dilute hydrochloric acid and revolving around it. Ans. (d)
(2) aqueous sodium hydroxide. CO is oxidised to CO2 with steam in the
10 The total number of isotopes of presence of a catalyst followed by the
The ratio of the volume of H2 absorption of CO2 in alkali
hydrogen and number of radioactive
evolved in these two reactions is
[2020, 9 Jan Shift-II]
isotopes among them, respectively, Steam
CO + H2 → CO2 + 2H2
are [2019, 10 Jan Shift-I] catalyst
(a) 2 : 1 (b) 1 : 1
(a) 2 and 1  KOH
(c) 1 : 4 (d) 1 : 2 ↓
Ans. (b) (b) 3 and 2
K2 CO3
(c) 2 and 0
Treatment of zinc with an excess of dil.
HCl and aqueous sodium hydroxide are (d) 3 and 1 13 Which of the following could act as
as follows : Ans. (d) a propellant for rockets ?
Zn + 2HCl → ZnCl2 + H2 ↑ Hydrogen has three isotopes: [AIEEE 2003]

Zn + 2NaOH → Na2ZnO2 + H2 ↑ 1 2 3 (a) Liquid hydrogen + liquid nitrogen

1H 1H 1H (b) Liquid oxygen + liquid argon
In both cases, 1 mol Zn gives 1 molH2 , Protium (P) Deuterium (D) Tritium (T)
ratio is 1 : 1. (c) Liquid hydrogen + liquid oxygen
p 1 1 1
(d) Liquid nitrogen + liquid oxygen
08 The metal that gives hydrogen gas n 0 1 2
Ans. (c)
upon treatment with both acid as n/p 0 1 2
Liquid hydrogen and liquid oxygen are
well as base is Only tritium (T) is radioactive, because of good fuels.
[2019, 12 April Shift-I]
n n 
(a) magnesium (b) mercury its very high value,  = 2 .
p p 
(c) zinc (d) iron TOPIC 2
Ans. (c) 11 Very pure hydrogen (99.9) can be Hydrides and Water
Metal that gives hydrogen gas upon made by which of the following
treatment with both acid as well as base 14 Which one of the following
processes? [AIEEE 2012]
is zinc.
(a) Reaction of methane with steam methods is most suitable for
Hence, it is amphoteric in nature.
Reactions involved are as follows: (b) Mixing natural hydrocarbons of preparing deionised water?
high molecular weight [2021, 26 Aug Shift-I]
Zn + Dil. NaOH → Na2ZnO2 + H2 ↑
(c) Electrolysis of water (a) Synthetic resin method
Zn + 2HCl(dil.) → ZnCl2 + H2 ↑
(d) Reaction of salts like hydrides with (b) Clark’s method
water (c) Calgon’s method
09 The isotopes of hydrogen are
Ans. (d) (d) Permutit method
(a) deuterium and tritium only
(b) protium and deuterium only Hydrides are instant source of hydrogen Ans. (a)
of higher purity. They react withH2O Synthetic resin method is most suitable
(c) protium, deuterium and tritium
forming H2 gas. for preparing deionised water. Deionised
(d) tritium and protium only
CaH2 + 2H2O → Ca(OH)2 + 2H2 water is obtained by passing water
[2019, 9 Jan Shift-I]
through cation exchange and an anion
Ans. (c)
12 In context with the industrial exchange resin.
There are three known isotopes of
hydrogen, each possessing an atomic
preparation of hydrogen from
water gas (CO + H2 ) , which of the 15 The functional groups that are
number 1 and atomic masses 1, 2 and 3
following is the correct statement ? responsible for the ion-exchange
respectively. These are named as
protium (1H), deuterium [AIEEE 2008] property of cation and anion
(2 Hor D) and tritium (3Hor T) (a) CO and H2 are fractionally exchange resins, respectively, are
separated using differences in [2021, 17 March Shift-II]
The most common isotope is the
ordinary hydrogen usually called their densities (a)  SO 3H and NH2
protium. It consists of one proton in the (b) CO is removed by absorption in (b) SO 3H and COOH
nucleus and an electron revolving aqueous Cu2Cl2 solution (c)  NH2 and COOH
around it. (d) NH2 and SO 3H
Hydrogen 181

Ans. (a) can be removed by filteration. While Ether

2. 3LiAlH4 + 4BF3 → 2B2H6
The functional group responsible for the permanent hardners of water is removed (Diborane)
ion-exchange property of cation is by treatment with sodium carbonate (
+3LiF + 3AlF3
SO3H and that of anion is NH2 . Na2 CO3), Calogon method and ion
Thus, statement (2) is correct.
exchange method.
Cation resins  attract positively charged 3. PH3 and CH4 are covalent hydrides
ions and contain acidic group like SO3H and in both of the hydrides, octet
or COOHgroups. While anion 18 In comparison to the zeolite
of P and C have been satisfied. But
resins  attract negatively charged ions process for the removal of
P in PH3 has one lone pair of
and contains basic groups like NH2 . permanent hardness, the synthetic electrons and C in CH4 does not
resins method is have so PH3 (group 15) and CH4
16 Calgon is used for water treatment. [2020, 7 Jan Shift-I]
(group 14) are electron rich and
Which of the following statement is (a) more efficient as it can exchange electron precise hydrides,
not true about Calgon? only cations respectively.
[2021, 26 Feb Shift-II] (b) less efficient as it exchanges only Thus, statement (3) is correct.
(a) Calgon contains the 2nd most anions 4. HF and CH4 are called as molecular
abundant element by weight in the (c) less efficient as the resins cannot hydrides because of their discrete
Earth’s crust. be regenerated and sterically symmetrical
(b) It is polymeric compound and is (d) more efficient as it can exchange structure.
water soluble. both cations as well as anions Thus, statement (4) is also correct.
(c) It is also known as Graham’s salt. Ans. (d)
(d) It does not remove Ca2+ ion by Zeolites exchange theirNa+ ions with 20 The temporary hardness of a water
precipitation. Ca2 + or Mg2 + in hard water. But, they sample is due to compound X.
Ans. (a) can’t exchange anions. Boiling this sample converts X to
Calgon is used to remove permanent 2NaZ(s ) +Mg2 + (or Ca2 + ) (aq) compound Y. X and Y, respectively,
hardness of water by removing cation From hard water
are [2019, 12 April Shift-II]
Mg2 + . → MgZ2 (s ) (or CaZ2 ) (s ) + 2Na+ (aq) (a) Mg(HCO 3)2 and Mg(OH)2
Calgon is not an element, it is a In synthetic resin method, all types
compound. The 2nd most abundant cations (Na + , Ca2 + , Mg2 + etc.) and (b) Ca(HCO 3)2 and Ca(OH)2
element by weight in the Earth’s crust is anions (c) Mg(HCO 3)2 and MgCO 3
silicon (Si). So, the statement in option (Cl – , SO24– etc.) can be removed.
(a) is not true.
(d) Ca(HCO 3)2 and CaO
Thus, this method is more efficient than Ans. (a)
Calgon is sodium hexametaphosphate zeolite process.
(NaPO3) 6 or Na2 [Na4 (PO3) 6 ]. It is a The temporary hardness of a water
polymeric water soluble compound. It is sample is due to compound X [i.e.
19 The correct statements among (a) to
also named as Graham’s salt. Mg(HCO3)2 ]. Boiling of this sample
(d) are : [2019, 10 April Shift-II]
Mg2 + of hard water is removed as converts X [i.e. Mg(HCO3)2 ] to compound
Na2 [Na4 (PO4 ) 3] + 2Mg2 + (aq) → 1. Saline hydrides produce H2 Y[i.e. Mg(OH)2 ]. Generally, temporary
Calgon Na [Mg (PO ) ] (s) + 4Na + (aq) gas when reacted with H2O. hardness is due to presence of
2+
2 2 3 6 magnesium and calcium hydrogen
Ca ion cannot be removed by calgon as 2. Reaction of LiAlH4 with BF3 carbonates. It can be removed by boiling.
Ca2 + is larger in size than Mg2 + . leads to B 2H6 . During boiling, the solubleMg(HCO3)2 is
So, the statement of option (b), (c) and (d) 3. PH3 and CH4 are electron rich converted into insolubleMg(OH)2 and
are true. Ca(HCO3)2 changed to insoluble CaCO3.
and electron precise hydrides, These precipitates can be removed by
17 The one that is not suitable for the respectively. filteration.
removal of permanent hardness of 4. HF and CH4 are called as Mg(HCO3)2 Heating
→ Mg(OH)2 ↓ + 2CO2 ↑
water is [2020, 5 Sep Shift-II] molecular hydrides. Heating
Ca(HCO3)2 → CaCO3 ↓
(a) Clark’s method (a) (1), (2), (3) and (4)
(b) (1), (2) and (3) only + H2O + CO2 ↑
(b) Ion-exchange method
(c) Calgon’s method (c) (3) and (4) only
(d) (1), (3) and (4) only 21 What is reason of temporary
(d) Treatment with sodium carbonate
Ans. (a) hardness of water?
Ans. (b) [2019, 9 Jan Shift-II]
Temporary hardness of water is The explanation of given statements are
(a) Na2 SO 4 (b) CaCl2
removed by Clark’s method and boiling. as follows :
(c) NaCl (d) Ca(HCO 3)2
In method a calculated quality of milk of 1. Saline or ionic hydrides produceH2
Ans. (d)
lime [Ca(OH)2 ] is added to the temporary with H2O.
hard water. This treatment converses ⊕È Temporary hardness of water is due to
MH + H2O → H2 ↑ + MOH presence of soluble Ca(HCO3)2 or
the soluble bicarbonates into insoluble
carbonates which get precipitated and Thus, statement (1) is correct. Mg(HCO3)2
182 JEE Main Chapterwise Topicwise Chemistry

Permanent hardness of water is due to (iv) Portland cement constitutes, TOPIC 3

the presence of CaCl2 or CaSO4 or MgCl2 tricalcium aluminosilicate,
or MgSO4 . 3CaO ⋅Al2O3. SiO2 , i.e. Heavy Water and H2O2
Temporary hardness of water is also Ca3Al2O6 ⋅ SiO2 .
called carbonate hardness which can be 26 Hydrogen peroxide reacts with
easily removed by boiling or by treatment 23 The recommended concentration of iodine in basic medium to give
with Ca(OH)2 (Clark’s method). fluoride ion in drinking water is up to [2021, 1 Sep Shift-II]
1 ppm as fluoride ion is required to (a) IO −4 (b) IO − (c) I− (d) IO −3
22 Match the following items in Column make teeth enamel harder by Ans. (c)
I with the corresponding items in converting [3Ca 3 (PO 4 ) 2 ⋅ Ca(OH) 2]
Column II. Hydrogen peroxide reacts with iodine in
to : [JEE Main 2018] basic medium to giveI− (Iodide ion).
Column I Column II (a) [CaF2] I2 + H2O2 + 2OH− → 2I− + 2H2O + O2
(b) [3(CaF2 ) ⋅Ca(OH)2]
(i) Na2 CO3 ⋅ 10H2O A. Portland cement
ingredient (c) [3Ca3 (PO 4 )2 ⋅CaF2] 27 The oxide that gives H2O 2 most
(d) [3{Ca3 (PO 4 )2 } ⋅CaF2]
(ii) Mg(HCO3)2 B. Castner-Kellner readily on treatment with H2O is
process Ans. (c) [2021, 27 Aug Shift-II]
(iii) NaOH C. Solvay process Fluoride ions help in making teeth (a) PbO2 (b) Na2O2
enamel harder by converting (c) SnO2 (d) BaO2 ⋅ 8 H2O
(iv) Ca3Al2O6 D. Temporary [3Ca3 (PO4 )2 ⋅ Ca(OH)2 ] i.e. Hydroxy
hardness Ans. (b)
apatite to [3Ca3 (PO4 )2 ⋅ CaF2 ] i.e.,
Fluorapatite (Harder teeth enamel) via When sodium peroxide reacts with
[2019, 11 Jan Shift-II]
following reaction: water,
(a) (i) - (D); (ii) - (A); (iii) - (B); (iv) - (C) it is hydrolysed and forms sodium
(b) (i) - (B); (ii) - (C); (iii) - (A); (iv) - (D) [3Ca3 (PO4 )2 ⋅ Ca(OH)2 ] + 2F − hydroxide and hydrogen peroxide.
From
(c) (i) - (C); (ii) - (B); (iii) - (D); (iv) - (A) drinking water Na2O2 + 2H2O → 2NaOH + H2O2
(d) (i) - (C); (ii) - (D); (iii) - (B); (iv) - (A) → [3Ca3 (PO4 )2 ⋅ CaF2 ] + 2OH− The reaction is highly exothermic.
Ans. (d) Therefore, the option (b) is correct.
24 Which one of the following
(i) Washing soda (Na2 CO3 ⋅ 10H2O) is statements about water is false?
manufactured in Solvay process. In [JEE Main 2016]
28 Given below are two statements :
this method, CO2 gas is passed (a) Water can act both as an acid and
One is labelled as Assertion A and
through a conc. solution of NaCl
as a base other is labelled as Reason R.
saturated withNH3. It gives
(b) There is extensive intramolecular Assertion (A) The dihedral angles
ammonium carbonate followed by
ammonium hydrogen carbonate. hydrogen bonding in the in H2O 2 in gaseous phase is 90.2°
condensed phase and in solid phase is 111.5°.
The obtainedNH4HCO3 is treated
with solution of NaCl which result (c) Ice formed by heavy water sinks in Reason (R) The change in dihedral
in the formation of NaHCO3. The normal water
angle in solid and gaseous phase
crystal obtained are heated to (d) Water is oxidised to oxygen during
photosynthesis
is due to the difference in the
obtain Na2 CO3.
Ans. (b) intermolecular forces.
NaCl + NH3 + CO2 + H2O →
NaHCO3 + NH4 Cl There is extensive intermolecular Choose the most appropriate
∆
H-bonding in the condensed phase. answer from the options given
2NaHCO3 → Na2 CO3 below for A and R.
−H2O, CO2 25 Which one of the following [2021, 20 July Shift-I]
Crystallisation processes will produce hard water? (a) A is correct but R is not correct.
→ Na2 CO3 ⋅ 10H2O [AIEEE 2003]
(b) Both A and R are correct but R is
(ii) Mg(HCO3)2 and Ca(HCO3)2 cause (a) Saturation of water with CaCO 3 not the correct explanation of A.
temporary hardness to water that (b) Saturation of water with MgCO 3 (c) Both A and R are correct and R is
can be easily removed by boiling. (c) Saturation of water with CaSO 4 the correct explanation of A.
(iii) NaOH is manufactured by (d) Addition of Na2 SO4 to water (d) A is not correct but R is correct.
Castner-Kellner process.
Ans. (c) Ans. (d)
In this reaction, Na amalgam flows Alkaline earth metal salts causes
out and treated with water to give On the basis of structure,
hardness of water. Temporary hardness
NaOH and H2 gas. During is caused by soluble Ca and Mg hydrogen (a) H2O2 structure in gas phase,
electrolysis, hydrogen is evolved at carbonates. Whereas calcium and dihedral angle is 111.5°.
cathode and chlorine is evolved at magnesium soluble sulphates and (b) H2O2 structure in solid phase at 110
anode, which are the by product of chlorides cause permanent hardness of K, dihedral angle is 90.2°.
this process. water.
Hydrogen 183

H (D) has a higher dielectric Due to open book like structure both
95.0 pm 94.8° OH groups are not in same plane and
111.5° constant than water.
hence,H2O2 is non-planar.
147.4 pm H Choose the correct answer from
Gas the options given below :
[2021, 17 March Shift-I] H
H (a) (B) only 95.0 pm
98.8 pm 101.9°
90.2° (b) (C) only 147.5 pm
O O 111.5º
145.8 pm H (c) (D) only 94.8° H
Solid (crystal)
(d) (C) and (D) only
Ans. (c) (a) Gas phase
Whereas, the change in dihedral angle in
solid and gaseous phase is due to the Dielectric constant of water is greater
difference in the intermolecular forces. than heavy water (D2O).
Hence, A is not correct but R is correct. A. It is widely used as moderator in H
nuclear reactors. 98.08 pm
145.8 pm
29 Given below are two statements. B. It can be prepared as a by-product O O 90.2º
One is labelled as Assertion (A) and in some fertiliser industries. 101.9°
H
the other is labelled as Reason (R). C. It is used in exchange reactions
for the study of the reaction (b) Solid phase
Assertion (A) Heavy water is used mechanism.
(a) H2O2 structure in gas phase,
for the study of reaction D. Species Dielectric constant dihedral angle is 111.5°.
mechanism. (C2 / Nm2 )
(b) H2O2 structure in solid phase at 110
Reason (R) The rate of reaction D2O 78.06 K, dihedral angle is 90.2°.
for the cleavage of O H bond is H2O 78.39 H2O2 used in treatment of
slower than that of O D bond. effluents.
31 The correct statements about
Choose the most appropriate
H2O 2 are 32 Given below are two statements.
answer from the options given
below. (A) used in the treatment of
Statement I H2O 2 can act as both
[2021, 26 Aug Shift-II] effluents.
oxidising and reducing agent in
(a) Both (A) and (R) are true but (R) (B) used as both oxidising and
basic medium.
is not the correnct explanation reducing agents.
of (A). (C) the two hydroxyl groups lie in Statement II In the hydrogen
(b) Both (A) and (R) are true and (R) is the same plane. economy, the energy is
the correct explanation of (A). (D) miscible with water. transmitted in the form of
(c) (A) is false but (R) is true. dihydrogen. In the light of the
Choose the correct answer from
(d) (A) is true but (R) is false. above statements, choose the
the options given below.
Ans. (d) [2021, 16 March Shift-II]
correct answer from the options
Assertion is true but Reason is false. (a) (A), (B), (C) and (D) given below : [2021, 16 March Shift-I]
Heavy water (D2O) is used as a moderator (b) (A), (B) and (D) (a) Both statement I and statement II
in nuclear reactor and in exchange (c) (B), (C) and (D) are false.
reaction for study of reaction (d) (A), (C) and (D) (b) Both statement I and statement II
mechanisms. are true.
Ans. (b)
As bond energy of O—H < Bond energy of (c) Statement I is true but statement
O—D. Reaction rate for cleavage of O—H H2O2 act as both oxidising and reducing II is false.
bond is faster than O—D bond. agent. (d) Statement I is false but statement
Oxygen is present in −1 oxidation state, II is true.
30 The incorrect statement(s) about so it can be oxidised to O2 as well as
Ans. (b)
reduced to water.
heavy water is (are) −1 −2 H2O2 can act as both oxidising and
(A) used as a moderator in nuclear H2 O2 → H2O (Reduction) reducing agent in basic medium as in
Oxidising agent hydrogen peroxide oxygen is present in
reactor.
−1 0 intermediate-1 oxidation state. So, it can
(B) obtained as a by-product in H2 O2 → O2 (Oxidation)
get oxidised to O2 and reduced to water.
fertiliser industry. Reducing agent
H2O2 → H2O (reduction)
(C) used for the study of reaction H2O2 is miscible with water due to −1 −2
mechanism. intermolecular H-bonding. Oxidising
agent
184 JEE Main Chapterwise Topicwise Chemistry

H2O2 → O2 (oxidation) (c) H2O2 act as oxidising and reducing (C) 2-ethylanthraquinone is useful
−1 0 agent respectively in equations (A)
Reducing for the industrial preparation
agent and (B). of hydrogen peroxide.
In the hydrogen economy, the energy is (d) H2O2 acts as reducing and oxidising (D) hydrogen peroxide is used for
transmitted in the form of dihydrogen agent respectively in equations (A) the manufacture of sodium
and not as electric power. and (B). perborate. [2020, 7 Jan Shift-II]
So, both statement I and statement II are Ans. (b)
true. (a) (A), (B) and (C) only
In equation (A), HOCl undergoes (b) (A), (B), (C) and (D)
reduction in presence ofH2O2 . (c) (A), (C) and (D) only
33 Statements about heavy water are
given below. Reduction (d) (A) and (C) only
Ans. (b)
A. Heavy water is used in (+1) (–1)
exchange reactions for the HOCl + H2O2 → H3O+ + Cl– + O2 The complete chemical equations for
the given reactions are as follows :
study of reaction Here, oxidation state of Cl changes from ∆ 1
mechanisms. +1 to –1 (A) H2O2 → H2O + O2
2
B. Heavy water is prepared by (i.e. reduces)
Thus, statement (A) is correct
exhaustive electrolysis of ∴H2O2 act as reducing agentI2 reduces to 3
∆
water. I− in presence ofH2O2 . (B) KClO3 → KCl + O2
2
In equation (B),
C. Heavy water has higher boiling ∆
Pb(NO3)2 → PbO + 2NO2 + O2
1
point than ordinary water. Reduction 2
D. Viscosity of H2O is greater than ∆ 1
0 +1 –1 +2 NaNO3 → NaNO2 + O2
D 2O. I2 + H2O2 + 2OH– → 2I– + 2H2O + O2 2
Thus, statement (B) is correct.
Which of the given statements are Here oxidation state of iodine decreases
correct? [2021, 26 Feb Shift-I] (from 0 to –1)
C2H5
(a) A, B and C (b) Only A and B ∴ H2O2 act as reducing agent in both the
(C) + H2
(c) Only A and D (d) Only A and C equations.
Ans. (a)
35 Hydrogen peroxide, in the pure
Statement A is true. Heavy water (D2O) is 2-ethyl anthraquinone
state, is [2020, 5 Sep Shift-II]
used in OH
exchange reactions as a tracer (a) non-planar and almost colourless
C2H5
compound for the study of reaction (b) linear and blue in colour
+ O2
mechanisms. (c) linear and almost colourless
e.g. NaOH + D2O → NaOD + HDO (d) planar and blue in colour
Statement B is true. Heavy water is Ans. (a) OH
prepared by prolonged exhaustive 2-ethyl anthraquinol
(multi-stage ) electrolysis of ordinary
H C2H5
water (H2O) containing NaOH.
O
Statement C is true. Heavy water has + H2O2
higher boiling point (374.4K) than O
ordinary water (373K). H
Statement D is false. Because viscosity 2-ethyl anthraquinone regenerated
(in centipoise) of D2O is greater (1.107)
Hydrogen peroxide is a colour less Thus, statement (C) is also correct.
than H2O (0.8903).
viscous liquid but in large quantity it (D) 2NaBO2 + 2H2O2 → Na2B2O4 (OH) 4
So, statements A, B and C are correct appears pale blue liquid. or Na2H4B2O8 (sodium perborate)
(option-a).
Hydrogen peroxide is a mild antiseptic Statement (D) is also correct.
used on the skin to prevent infections.
34 (A) 37 The chemical nature of hydrogen
HOCl + H2O 2 → H3O + + Cl − + O 2 36 Among statements (A) - (D), the peroxide is [2019, 10 Jan Shift-I]
(B) I 2 + H2O 2 + 2OH− → 2I − correct ones are
(a) oxidising and reducing agent in
+ 2H2O + O 2 (A) decomposition of hydrogen both acidic and basic medium
Choose the correct option. peroxide gives dioxygen. (b) oxidising and reducing agent in
[2021, 24 Feb Shift-I] (B) like hydrogen peroxide, acidic medium, but not in basic
compounds, such as medium
(a) H2O2 acts as oxidising agent in
(c) reducing agent in basic medium,
equations (A) and (B). KClO 3 , Pb(NO 3 ) 2 and NaNO 3
but not in acidic medium
(b) H2O2 acts as reducing agent in when heated liberate
(d) oxidising agent in acidic medium,
equations (A) and (B). dioxygen. but not in basic medium
Hydrogen 185

Ans. (a) (III) NaNi5 , Ti -TiH2 etc. are used for 41 Hydrogen peroxide oxidises
storage of H2 in small quantities.
H2O2 can act as both oxidising and [Fe(CN) 6] 4− to [Fe(CN) 6] 3− in
reducing agents in both acidic and basic Thus, option (c) is correct.
acidic medium but reduces
medium. (IV) On combustion values of energy
H2O2 as oxidising agent released per gram of liquid [Fe(CN) 6] 3− to [Fe(CN) 6] 4− in
In acidic medium : dihydrogen (H2 ) : 142 kJ g −1, and for alkaline medium. The other
LPG : 50 kJ g −1. So, option (d) is products formed are, respectively.
H2O2 + 2H+ + 2e − → 2H2O incorrect. (a) (H2O + O2 ) and H2O [JEE Main 2018]
In basic medium :
− (b) (H2O + O2 ) and (H2O + OH− )
H2O2 + 2O H+ 2e − → 2H2O+ 2O2 − 39 A metal on combustion in excess
air forms X. X upon hydrolysis with (c) H2O and (H2O + O2 )
H2O2 as reducing agent (d) H2O and (H2O + OH− )
In acidic medium :
water yields H2O 2 and O 2 along
with another product. The metal is Ans. (c)
H2O2 → O2 + 2H+ + 2e −
(a) Li (b) Mg Both reactions in their complete format
In basic medium :
(c) Rb (d) Na are written below
H2O2 + 2OH− → O2 + 2H2O + 2e − [2019, 12 Jan Shift-I] (i) In acidic medium,
Ans. (c) −1
38 The correct statements among (I) [Fe2 + (CN) 6 ] 4 − + H2 O2 + 2H+
to (IV) regarding H2 as a fuel are : Metal (A) is rubidium (Rb). In excess of air, −2
it forms RbO2 (X). X is a superoxide that → [Fe3+ (CN) 6 ] 3− + 2H2 O
I. It produces less pollutants have O2− ion. It is due to the stabilisation
than petrol. of large anion by large cations through (ii) In alkaline medium,
−1
II. A cylinder of compressed lattice energy effects. RbO2 (X) gets [Fe3+ (CN) 6 ] 3− + H2 O2 + 2OH− →
easily hydrolysed by water to form the
dihydrogen weights ~30times
hydroxide, H2O2 and O2 . [Fe2 + (CN) 6 ] 4 − + O2 + 2H2O
more than a petrol tank
The reaction involved are as follows: Hence,H2O (for reaction (i)) and O2 + H2O
producing the same amount of
Rb + O2 → RbO2 (superoxide) (for reaction (ii)) are produced as by
energy. (X ) product.
III. Dihydrogen is stored in tanks 2RbO2 +2H2O → 2RbOH+ H2O2 + O2
of metal alloys like NaNi 5 . (X ) 42 From the following statements
IV. On combustion, values of regarding H2O 2 , choose the
energy released per gram of 40 The volume strength of 1 M H2O 2 is incorrect statement. [JEE Main 2015]
liquid dihydrogen and LPG are (Molar mass of H2O 2 = 34 g mol − 1 ) (a) It can act only as an oxidising
50 and 142 kJ, respectively. (a) 16.8 (b) 22.4 agent
[2019, 11 Jan Shift-I] (c) 11.35 (d) 5.6 (b) It decomposed on exposure to
(a) I, II and III only [2019, 12 Jan Shift-II] light
(b) II, III and IV only Ans. (c) (c) It has to be stored in plastic or wax
(c) II and IV only lined glass bottles in dark
Concentration of H2O2 is expressed in
(d) I and III only terms of volume strength, i.e. “volume of (d) It has to be kept away from dust
O2 liberated byH2O2 at NTP”. Molarity is Ans. (a)
Ans. (a)
connected to volume strength as : H2O2 acts as an oxidising as well as
(I) H2 is a 100% pollution free fuel. So, x
Molarity (M) = or x = Molarity × 11.2 reducing agent, because oxidation
option (I) is correct. 112
. number of oxygen in H2O2 is –1. So, it
1
(II) Molecular weight ofH2 (2u) = × where, x = volume strength can be oxidised to oxidation state 0 or
29 reduced to oxidation state −2.
molecular weight of butane, C4H10 H2O2 decomposes on exposure to light.
(LPG) [58u]. So, for 1 M H2O2
So, it has to be stored in plastic or wax
So, compressedH2 weighs ~30 x = 1 × 11.2 = 11.2
lined glass bottles in dark for the
times more than a petrol tank and Among the given options, 11.35 is nearest prevention of exposure. It also has to be
option (b) is correct. to 11.2. kept away from dust.
16
s-Block Elements
TOPIC 1 less negative on descending the oppositely charged ions even stronger,
group. thus increasing the strength of bond.
Group 1 Elements (b) The low solubility of Csl in water is Increase in strength is more than the
(Alkali Metals) due to its high lattice enthalpy. weakness produced due to lengthening
(c) Among the alkali metal halides, LiF is of bond because of increase in size of
least soluble in water. metal ions down the group. This makes
01 Given below are two statements : ∆Hf more negative on moving down the
(d) LiF has least negative standard
One is labelled as Assertion (A) and group.
enthalpy of formation among alkali
the other is labelled as Reason (R). metal fluorides. Option (a) is incorrect, due to reason
Assertion (A) Lithium salts are Ans. (c) produced in (B).
hydrated. Option (b) is incorrect. As CsI has Cs⊕
The ∆Hf of alkali metal halides is shown
and Is an constituent ions and both the
Reason (R) Lithium has higher through this graph.
ions are larger in size. The lattice
polarising power than other alkali enthalpy is not so high as shown in
metal group members. F graph. But it has low solubility due to
Cl
less hydration energy released when
In the light of the above Br
–DHf hydration of larger ions takes place.
statements, choose the most I Option (c) is correct. As LiF has highest
appropriate answer from the lattice enthalpy as shown in graph. This
options given below is due to the size of ions that is smallest
[2021, 31 Aug Shift-II] T
Li Na K Rb Cs in their respective groups. Smaller is the
(a) Both (A) and (R) are true but (R) is not This graph shows that formation of size, shorter is the bond length and
the correct explanation of (A). metal halide is negative, i.e. energy is stronger is the bond. The energy
(b) (A) is true but (R) is not true released during the formation of metal required is break the bond and release
(c) (A) is false but (R) is ture. halides. the constituents ions is more than the
(d) Both (A) and (R) are true (R) is the (A) energy released in the hydration of ions.
M—F So, LiF is least soluble in water.
correct explanation of (A).
Option (d) is incorrect. LiF has most
Ans. (a) M—Cl
negative enthalpy in all metal fluorides
Both Assertion and Reason are true but M—Br as shown in graph.
Reason is not the correct explanation of M—I
Assertion. 03 The ratio of number of water
On moving down the group, the size of
Lithium ions have smaller size as halogens increase which results in the molecules in Mohr’s salt and potash
compared to other ions of the group. lengthening of bond, making the bond alum is ………… × 10 −1 .
Hence, it has greater value of charge to weaker. Therefore, ∆Hf is less negative
radius ratio and polarising power. on moving down the group as the (Integer answer)
[2021, 26 Aug Shift-I]
Among alkali metals ions, Li has smallest stability of metal halide decreases down
size due to which it can easily polarise the group. Ans. (2.5)
water molecule. LiCl contains 2 water (B) Formula for Mohr’s salt is
molecules per mole. However, due to Li—X (NH4 )2 Fe(SO4 )2 ⋅6H2O.
bigger size of other alkali metals, they
cannot easily polarise water molecules. Na—X ∴ Number of water molecule in Mohr’ salt
K—X = 6.
02 Choose the correct statement from Formula for potash alum is
Rb —X
K2SO4 Al2 (SO4 ) 3 ⋅24H2O.
the following. [2021, 27 Aug Shift-II] On moving down the group, the ∴ Number of water molecules in potash
(a) The standard enthalpy of formation electropositivity of metal increases alum is 12.
for alkali metal bromide becomes making the attraction between the
s-Block Elements 187

∴ Ratio of water molecules in Mohr’s salt Ans. (b) Choose the correct answer from
and potash alum is s-block elements form metal hydroxide the options given below.
6 1
= = 2.5 × 10 −1 that are basic in nature exceptBe(OH)2 . [2021, 25 July Shift-II]
24 4 Be and Al are diagonally related, their A B C D
hydroxide are amphoteric in nature. (a) IV III II I
04 Match List I with List II. Boron (non-metal) forms oxide [B(OH) 3]
(b) I III II IV
which is acidic in nature.
List I List II (c) IV II III I
A. NaOH → Basic
A. Li I. Photoelectric cell B. Be(OH)2 → Amphoteric (d) I II III IV
B. Na II. Absorbent of CO2 C. Ca(OH)2 → Basic Ans. (a)
C. K III. Coolant in fast D. B(OH) 3 → Acidic (A) Li2 CO3 decomposes easily on
breeder nuclear E. Al(OH) 3 → Amphoteric heating due to high covalent
reactor character caused by small size Li+
Hence, correct match is
cation.
D. Cs IV. Treatment of A → II, B → III, C → II, D → I, E → III.
cancer (B) NaHCO3 is used in fire
extinguisher. NaHCO 3 reacts with
V. Bearings for motor 06 Given below are two statements. acid to produce carbon dioxide.
engines One is labelled as Asseriton A and (C) K is most abundant element in cell
Choose the correct answer from the other labelled as Reason R. fluid.
the options given below. Assertion A Lithium halides are (D) Csl salt has poor water solubility
[2021, 27 July Shift-II] some what covalent in nature. due to its low hydration energy. As
A B C D hydration energy is inversely
Reason R Lithium possess high proportional to the size of ion.
(a) V I II IV polarisation capability. Both Cs and I are larger in size.
(b) V II IV I Hence, correct match is
According the above statements,
(c) IV III I II A → IV, B→ III, C→ II, D→ I.
choose the most appropriate
(d) V III II I
answer from the options given
Ans. (d) below [2021, 27 July Shift-I]
08 A s-block element (M) reacts with
(A) Li makes alloy with lead which is (a) A is true but R is false oxygen to form an oxide of the
used to make metal bearings for (b) A is false but R is true formula MO 2 . The oxide is pale
motor engines. yellow in colour and paramagnetic.
(c) Both A and R are true but R is not the
(B) Liquid Na is used as coolant in fast correct explanation of A The element (M) is
breeder nuclear reactor. (d) Both A and R are true and R is the [2021, 20 July Shift-I]
(C) K is used as absorbent of CO2 . correct explanation of A (a) Mg (b) Na (c) Ca (d) K
(D) Cs is used in making photoelectric Ans. (d) Ans. (d)
cell.
Both Assertion and Reason are true and The element (M) is potassium (K). It
Hence, the correct match is Reason is the correct explanation of reacts withO2 to form KO2 , which is
A → V; B → III; C → II; D → I Assertion. paramagnetic in nature. All other
Lithium ion due to its smaller size than elements form oxides or peroxides
05 Match List-I with List-II. other alkali metal cation has very high which are diamagnetic in nature.
polarisation power and least Chemical reaction is as follows
List-I List-II
electropositive character. Which results K + O2 (excess) → KO2
A. NaOH I. Acidic into increase in covalent nature in the (Paramagnetic) Superoxide
molecule [Fajan’s rule].
B. Be(OH)2 II. Basic whereas,
(a) 2Mg + O2 → 2MgO (Diamagnetic)
C. Ca(OH)2 III. Amphoteric 07 Match List I with List II.
(b) 2Na + O2 → Na2O (Diamagnetic)
D. B(OH) 3 List I List II 2Na + O2 (excess) → Na2O2
E. Al(OH) 3 (Elements) (Properties) (Diamagnetic)
(A) Li I. Poor water (c) 2Ca + O2 → 2CaO (Diamagnetic)
Choose the most appropriate solubility of I − salt Ca + O2 → CaO2 (Diamagnetic)
answer from the options given
(B) Na II. Most abundant
below [2021, 27 July Shift-I] element in cell fluid 09 The ionic radius of Na + ions is
A B C D E
(C) K III. Bicarbonate salt used 1.02 Å. The ionic radii (in Å) of Mg 2+
(a) II II III II III in fire extinguisher and Al 3+ , respectively, are
(b) II III II I III (D) Cs IV. Carbonate salt [2021, 18 March Shift-I]
(c) II II III I III decomposes easily on (a) 1.05 and 0.99 (b) 0.72 and 0.54
(d) II I II III III heating (c) 0.85 and 0.99 (d) 0.68 and 0.72
188 JEE Main Chapterwise Topicwise Chemistry

Ans. (b) Choose the correct answer form 13 Number of amphoteric compounds
For iso-electronic system, radius is the options given below. among the following is ......... .
inversely proportional to the Z eff. . The [2021, 26 Feb Shift-II] [2021, 24 Feb Shift-I]
effective nuclear charge (Z eff) is net A B C D (a) BeO (b) BaO
positive charge, experienced by an
(a) (iv) (iii) (i) (ii) (c) Be(OH)2 (d) Sr(OH)2
electron in a multi-electron atom.
(b) (i) (iii) (iv) (ii) Ans. (Two)
Na+ Mg2+ Al3+ (c) (iv) (i) (ii) (iii) An amphoteric compound is a molecule
Z=11 Z=12 Z=13 (d) (iii) (ii) (i) (iv) or ion that can react with both as an acid
(10 electrons in each) Ans. (a) or as a base.
BeO = Amphoteric
(Z = atomic number) (A) Sodium carbonate is manufactured
by Solvay process ⇒(iv) of List-II. BaO = Basic
We know that, more is the positive
Solvay process’s reactions are as follows Be(OH)2 = Amphoteric
charge on an ion, smaller will be its ionic
radii. Whereas more is the negative In Solvay’s process, first ammonia (NH3) Sr(OH)2 = Basic
charge on an ion more will be its ionic reacts with CO2 and H2O to give Both beryllium compound BeO and
radii. ammonium bicarbonate (NH4HCO3). Be(OH)2 are amphoteric in nature while
So, order of ionic size This bicarbonate react with NaCl to give compound BaO and Sr(OH)2 are basic in
sodium bicarbonate (NaHCO3) along with nature, they form alkaline solution inH2O.
Na+ > Mg2 + > Al 3+
ammonium chloride (NH4 Cl).
Ionic radii of Na+ (1.02 Å)>Mg2 + (0.72 Å)
14 The metal mainly used in devising
> Al 3+ (0.54 Å). At last, NaHCO3 is heated to form sodium
carbonate as major product. photoelectric cells is
NH3 + CO2 + H2O → NH4HCO3 [2020, 2 Sep Shift-I]
10 The correct order of conductivity
NH4HCO3 + NaCl → NaHCO3 ↓ + NH4 Cl (a) Na (b) Li
of ions in water is (Brine) (c) Cs (d) Rb
[2021, 17 March Shift-I]
∆ Ans. (c)
(a) Na+ > K + > Rb + > Cs+ 2NaHCO3 Na2CO3 +CO2 +H2O
(b) Cs+ > Rb + > K + > Na+ Sodium The expression of kinetic energy (KE) of
carbonate photoelectrons is : KE = E − E 0
(c) K + > Na+ > Cs+ > Rb +
where, E = Energy of incident light
(d) Rb + > Na+ > K + > Li+
12 Match List-I with List-II. E 0 = Threshold energy of the metal used
Ans. (b)
in photoelectric cells
Correct order of conductivity of ions in List-I List-II
A metal with lower ionisation energy (IE)
water is (Salt) (Flame colour will have lower value of E 0 , also which
Cs+ > Rb+ > K+ > Na+ wavelength) will increase the value of KE of
+
Cs (aq) has lower hydrated radius so its A. LiCl 1. 455.5 nm photoelectrons.
electrical conductivity is higher. B. NaCl 2. 670.8 nm Group-1 metals have lower IE, values and
Extent of hydration depends on charge C. RbCl 3. 780.0 nm we know the order of IE, of group-I
density on the ion. metals will be
D. CsCl 4. 589.2 nm
As the size of gaseous ion decreases, it IE 1 : Li > Na > K > Rb > Cs
get more hydrated in water and hence, So, the order is E 0 : Li > Na > K > Rb > Cs
the size of aqueous ion increases. When
Choose the correct answer from
the options given below. KE : Li < Na < K < Rb < Cs
this bulky ion move in solution, it
[2021, 24 Feb Shift-II] That is why, Cs metal is the best choice
experience greater resistance and
A B C D A B C D in devising photoelectric cells.
hence lower conductivity.
Size of gaseous ion : (a) 4 2 3 1 (b) 2 1 4 3
15 On combustion of Li, Na and K in
Cs+ > Rb+ > K+ > Na+ (c) 1 4 2 3 (d) 2 4 3 1
excess of air, the major oxides
Size of aqueous ion : Ans. (d) formed, respectively, are
Cs+ < Rb+ < K+ < Na+ Alkali metal Colour (Flame) λ (nm) [2020, 4 Sep Shift-I]
Conductivity: Li Crimson red 670.8 (a) Li2 O, Na2 O and K2 O2
Cs+ > Rb+ > K+ > Na+ Na Yellow 589.2 (b) Li2 O, Na2 O2 and K2 O
Rb Red, violet 780.0 (c) Li2 O, Na2 O2 and KO2
11 Match List-I with List-II Cs Blue 455.5 (d) Li2 O2 , Na2 O2 and K2 O2
List-I List-II Alkali metals have very low value of Ans. (c)
ionisation energy as compared to other On combustion of Li, Na and K in excess
A. Sodium carbonate (i) Deacon
metals. So, alkali metals easily get of air, the major oxides formed
B. Titanium (ii) Castner-Kell excited and impart colour to flame.
ner respectively areLi2O, Na2O2 and KO2 .
Hence, Rb is most excited and having Reactions are as follows:
C. Chlorine (iii) van-Arkel high value of wavelength in all alkali Li + O2 → Li2O
D. Sodium hydroxide (iv) Solvay metals. Excess Oxide
s-Block Elements 189

Na + O2 → Na2O2 (c) Na+ > Li+ > K + > Cs+ > Rb + This deep blue solution also shows the
Excess Peroxide (d) Li+ > Na+ > K + > Rb + > Cs+ following properties due to the presence
K + O2 → KO2 Ans. (d)
of ammoniated electrons.
Excess Super oxide (i) It is strongly reducing in nature.
Key Idea The amount of energy released
(ii) It is paramagnetic.
16 Reaction of an inorganic sulphite X when one mole of gaseous ions combine
with water to form hydrated ions is (iii) It is a good conductor of
with dilute H2SO 4 generates electricity.
called hydration enthalpy.
compound Y. Reaction of Y with
The correct order of hydration
NaOH gives X. Further, the reaction enthalpies of alkali metal ions is 21 NaH is an example of
of X with Y and water affords Li+ > Na+ > K+ > Rb+ > Cs+ (a) metallic hydride
compound Z. Y and Z respectively, +
Li possesses the maximum degree of (b) electron-rich hydride
are [2020, 6 Sep Shift-II] hydration due to its small size. As a (c) saline hydride
(a) SO2 and Na2 SO 3 consequence of hydration enthalpy, (d) molecular hydride
(b) SO 3 and NaHSO 3 their mobility also get affected. Cs+ has [2019, 11 Jan Shift-I]
highest andLi+ has lowest mobility in Ans. (c)
(c) SO2 and NaHSO 3
aqueous solution.
(d) S and Na2 SO 3 r s
NaH is an example of ionic or saline
Ans. (c) hydride. These hydrides are formed
19 The incorrect statement is
Dil.H 2 SO 4 NaOH when hydrogen combines with metals
Na2SO3 → SO2 → Na2SO3 [2019, 12 April Shift-II]
having less electronegativity and more
(X ) (Y ) (X ) (a) lithium is the strongest reducing electropositive character with respect
SO 2 +H 2 O agent among the alkali metals. to hydrogen. Except Be and Mg, all
→ NaHSO3
(Z )
(b) lithium is least reactive with water s-block metals form saline hydrides.
among the alkali metals. Hydrides of p-block elements are
Here, X, Y , Z are
(c) LiNO 3 decomposes on heating to covalent in nature,viz, electron deficient
X = Na2SO3, Y = SO2 , Z = NaHSO3 give LiNO2 and O2 . hydrides (by group-13 elements),
Na2SO3 react withdil.H2SO4 form sulphur electron-precise hydrides (by group-14
(d) LiCl crystallise from aqueous
dioxide (SO2 ) gas. SO2 on reaction with
solution as LiCl⋅2H2O. elements), and electron-rich hydrides (by
NaOH again form Na2SO3. By the reaction group 15-17 elements). Hydrides of
of SO2 and H2O, Na2SO3 form NaHSO3. Ans. (c)
d, f-block metals are called interstitial or
Here, X, Y , Z are Na2SO3, SO2 , NaHSO3 Statement (c) is incorrect.LiNO3 (Lithium metallic hydrides.
respectively. nitrate) on heating gives a mixture of
Li2O, NO2 and O2 . 22 The correct statement(s) among I
17 Among the statements (A)-(D), the ∆
4LiNO3 → 2Li2O + 4NO2 ↑ + O2 ↑ to III with respect to potassium
correct ones are [2020, 9 Jan Shift-II] ions that are abundant within the
Among the alkali metals, lithium is the
(A) lithium has the highest strongest reducing agent. cell fluids is/are
hydration enthalpy among I. They activate many enzymes.
alkali metals. 20 Sodium metal on dissolution in II. They participate in the
(B) lithium chloride is insoluble in liquid ammonia gives a deep blue oxidation of glucose to
pyridine. solution due to the formation of produce ATP.
(C) lithium cannot form ethynide [2019, 10 Jan Shift-II]
III. Along with sodium ions, they
upon its reaction with ethyne. (a) sodium ammonia complex
are responsible for the
(D) Both lithium and magnesium (b) sodium ion-ammonia complex
transmission of nerve signals.
react slowly with H2O. (c) sodamide
(a) I, and III only
(a) (A) and (D) only (d) ammoniated electrons
(b) I, II and III
(b) (B) and (C) only Ans. (d)
(c) I and II only
(c) (A), (C) and (D) only Sodium metal on dissolution in liquid (d) III only [2019, 12 Jan Shift-II]
(d) (A), (B) and (D) only ammonia gives a deep blue solution due
Ans. (b)
Ans. (c) to the formation of ammoniated
electrons. The reaction is represented All the statements are correct.K+ being
Statement (A), (C) and (D) are correct as follows : metallic unipositive ions work as enzyme
whereas statement (B) is incorrect. It’s activators.
corrected form is that lithium chloride is Na(s ) + (x + y ) NH3 (l ) →
These also participate in many reactions
soluble in pyridine. [Na(NH) x ] + + [e (NH ] of glycolysis and Kreb’s cycle to produce
3)y
[Ammoniated Na + [Ammoniated
or expanded Na] electrons]
ATP from glucose.
18 The correct order of hydration Being unipositive these are also equally
enthalpies of alkali metal ions is Ammoniated (solvated) electrons show responsible for nerve signal
[2019, 8 April Shift-I] electronic transition in visible region and transmission along withNa+ .
(a) Li+ > Na+ > K + > Cs+ > Rb + the solution becomes deep blue (Na+ ion-pump theory)
(b) Na+ > Li+ > K + > Rb + > Cs+ coloured.
190 JEE Main Chapterwise Topicwise Chemistry

23 Sodium salt of an organic acid ‘X’ 26 What is the best description of the Ans. (d)
produces effervescence with conc. change that occurs when Na 2O(s) is The chemical formula of
dissolved in water? [AIEEE 2011] gypsum – CaSO4 ⋅2H2O, dead burnt
H2SO 4 . ‘X’ reacts with the acidified
(a) Oxidation number of sodium plaster – CaSO4 and plaster of Paris –
aqueous CaCl 2 solution to give a 1
decreases CaSO4 ⋅ H2O.
white precipitate which (b) Oxide ion accepts a shared pair of 2
decolourises acidic solution of electrons So, number of water molecules in
KMnO 4 . ‘X’ is [JEE Main 2017] (c) Oxide ion donates a pair of electrons gypsum, dead burnt plaster and plaster
(d) Oxidation number of oxygen of Paris are 2, 0 and 0.5 respectively.
(a) C 6H5COONa (b) HCOONa
increases
(c) CH3COONa (d) Na2C2O 4
Ans. (c) 30 Given below are two statements :
Ans. (d) One is labelled as Assertion (A) and
Na2O+ H2O → 2NaOH
The reaction takes place as follows the other is labelled as Reason (R).
Oxidation number +1 −2 −2 +1 +2
Na2 C2O4 + H2SO4 → Na2 SO4 + H2O
(X ) (conc. )
of Na and Oxygen Assertion (A) Barium carbonate is
+ CO ↑ + CO2 ↑ No change in oxidation number, so (a) insoluble in water and is highly
Effervescence
and (d) are not true. stable.
Na2 C2O4 + CaCl2 → CaC2O4 + 2NaCl (b) is also not true.
(X ) White ppt.
Reason (R) The thermal stability
Oxide ion donates a pair of electrons,
5CaC2O4 + 2KMnO4 + 8H2SO4 → K2SO4 of the carbonates increases with
thus changes toOH− .
Purple increasing cationic size.
+ 5CaSO4 + 2MnSO4 + 10CO2 + 8H2O [2021, 26 Aug Shift-II]
27 KO 2 is used in space and
Colourless (a) Both (A) and (R) are true and (R) is the
Hence, X is Na2 C2O4 .
submarines because it correct explanation of (A).
(a) absorbs CO2 and increasesO2 (b) (A) is true but (R) is false.
24 The main oxides formed on concentration (c) Both (A) and (R) are true and (R) is not
(b) absorbs moisture the true explanation of (A).
combustion of Li, Na and K in
(c) absorbs CO2 (d) (A) is false but (R) is true.
excess of air respectively are
[JEE Main 2016] (d) produces ozone [AIEEE 2002] Ans. (a)
(a) LiO2 , Na2O2 and K2O Ans. (a) Both Assertion and Reason are true and
Reason is the correct explanation of
(b) Li2O2 , Na2O2 and KO2 4KO2 + 2CO2 → 2K2 CO3 + 3O2
Assertion.
(c) Li2O, Na2O2 and KO2
(d) Li2O , Na2O and KO2 Stability of group-2 metal carbonates
Ans. (c) TOPIC 2 increases as we move down the group
because large cations are stabilised by
1
2Li + O2 (g) → Li2O Group 2 Elements large anion and vice-versa. Carbonates
2 (Alkaline Metals) being a large anion is stabilised by larger
(Excess) cations.
2Na + O2 (g) → Na2O2 BeCO3 MgCO3 CaCO3 SrCO3 BaCO3
( Excess) 28 The major component/ingredient →
of Portland cement is Stability increases
K + O2 (g) → KO2
(Excess) [2021, 31 Aug Shift-I] Solubility in water decreases as we move
(a) tricalcium aluminate down the group because of decrease in
(b) tricalcium silicate hydration energy of cations.
25 The products obtained on heating
(c) dicalcium aluminate
LiNO 3 will be [AIEEE 2011]
31 What are the products formed in
(d) dicalcium silicate
(a) LiNO2 + O2 (b) Li2O + NO2 + O2 sequence when excess of CO 2 is
Ans. (b)
(c) Li3N + O2 (d) Li2O + OH + O2 passed in slaked lime?
The major component of Portland
Ans. (b) [2021, 26 Aug Shift-I]
cement is tricalcium silicate (51%,
LiNO 3 behave differently from other 3CaO⋅SiO2 ). Hence, correct option is (b). (a) Ca(HCO 3)2 ,CaCO 3
alkali metal nitrates. (b) CaCO 3,Ca(HCO 3)2
Lithium nitrates decompose on heating 29 The number of water molecules in (c) CaO, Ca(HCO 3)2
producingNO2 . Whereas other alkali gypsum, dead burnt plaster and (d) CaO, CaCO 3
nitrates likeNaNO3 produces nitrite and Ans. (b)
oxygen on decomposition.
plaster of Paris, respectively are
(a) 2, 0 and 1 [2021, 27 Aug Shift-I] When excess of CO2 passes through
∆ 1
2Li NO3 → Li 2O+ 2NO2 + O2 (b) 0.5, 0 and 2 slaked lime [Ca(OH)2 ], the calcium
2 carbonate (CaCO3) and calcium hydrogen
(c) 5, 0 and 0.5
∆ 1 carbonate Ca(HCO3)2 will be formed as
NaNO3 → NaNO2 + O2 (d) 2, 0 and 0.5 follows
2
s-Block Elements 191

Ca(OH)2 + CO2 → CaCO3 ↓ (C) Li → Being small in size, the Statement II BeO is amphoteric,
Slaked lime Calcium carbonate compounds of lithium are covalent whereas the oxides of other
+ H2O in nature, so its compounds are
soluble in organic solvent. elements in the same group are
(Milky)
e.g. LiCl is soluble in pyridine i.e (i). acidic.
CaCO3 + CO2 + H2O → Ca(HCO3)2 (D) Na → NaOH, strong monoacidic In the light of the above
Calcium base i.e. (iv). statements, choose the correct
hydrogen carbonate
The correct match is : answer from the options given
32 The conversion of hydroxyapatite (A)-(ii), (B)-(iii), (C)-(i) and D-(iv). below. [2021, 16 March Shift-I]

occurs due to presence of F − ions (a) Statement I is false but statement II

in water. The correct formula of 34 Match List-I with List-II. is true
(b) Both statement I and statement II
hydroxyapatite is List-I List-II are false
[2021, 26 Aug Shift-I]
(c) Both statement I and statement II
(a) [3Ca3 (PO4 )2 Ca(OH)2 ] (A) Ca(OCl)2 (i) Antacid
are true
(b) [3Ca(OH)2 CaF2 ] (B) CaSO ⋅ 1 H O (ii) Cement (d) Statement I is true but statement II
4 2
(c) [Ca3 (PO4 )2 CaF2 ] 2 is false
(d) [3Ca3 (PO4 )2 CaF2 ] (C) CaO (iii) Bleach Ans. (b)
Ans. (a) The dehydration of hydrated chlorides,
(D) CaCO 3 (iv) Plaster of
The correct formula for hydroxyapatite Paris bromides and iodides of Ca, Sr, Ba is
is 3 [Ca3 (PO4 )2 Ca(OH)2 ]. The presence of possible but hydrated halides of Be and
F − ions on enamel make the enamel Choose the most appropriate answer Mg on heating suffer hydrolysis due to
much harder as hydroxyapatite from the options given below. their small size or high charge density.
[3Ca3 (PO4 )2 Ca(OH)2 ] converts into [2021, 18 March Shift-I] ∆
fluoroapatite [3Ca3 (PO4 )2 CaF2 ]. CaCl2 ⋅6H2O → CaCl2 + 6H2O
A B C D A B C D Anhydrous
(a) (i) (iv) (iii) (ii) (b) (iii) (ii) (iv) (i)
33 Match List I with List II. ∆
(c) (iii) (iv) (ii) (i) (d) (iii) (ii) (i) (iv) MgCl2 ⋅ 8H2O → MgO + 7H2O + 2HCl
List-I List-II Ans. (c) MgCl2 can be made anhydrous by heating
(Elements) (Properties) A. Ca(OCl)2 → Bleaching powder in presence of dry HCl.
∆ ( Calcination )
A. Ba (i) Organic solvent B. CaSO4 ⋅ 1/2H2O → Plaster of Paris MgCl2 ⋅6H2O  → MgCl2 + 8H2O
soluble Dry HCl(g )
compounds C. CaO → is major component of cement
D. CaCO3 → used as an antacid Hence, on heating CaCl2 ⋅6H2O undergoes
B. Ca (ii) Outer electronic dehydration butMgCl2 ⋅ 8H2O does not.
configuration 6 s 2 Correct match is (A-iii), (B-iv), (C-ii), (D-i).
Metal oxides are generally basic. In
C. Li (iii) Oxalate insoluble in alkaline earth metal BeO is amphoteric
water 35 One of the by-products formed
and shows anomalous behaviour while
D. Na (iv) Formation of very during the recovery of NH 3 from other oxides are basic.
strong monoacidic solvay process is So, both statement I and statement II are
base [2021, 17 March Shift-II]
false.
(a) Ca(OH)2 (b) NaHCO 3
Choose the correct answer from (c) CaCl2 (d) NH 4 Cl
the options given below 37 The correct set from the following in
Ans. (c)
[2021, 22 July Shift-II] which both pairs are in correct order
CaCl2 is one of the by-products formed
A B C D of melting point is
during the recovery ofNH3  from Solvay
(a) (ii) (iii) (i) (iv) [2021, 24 Feb Shift-II]
process.
(b) (iv) (i) (ii) (iii) (a) LiF > LiCl, MgO > NaCl
Ammonia required for the process can
(c) (iii) (ii) (iv) (i) be prepared by heating ammonium (b) LiCl > LiF, NaCl > MgO
(d) (i) (iv) (ii) (iii) chloride with calcium hydroxide. (c) LiF > LiCl, NaCl > MgO
Ans. (a) 2NH4 Cl + Ca(OH)2 → (d) LiCl > LiF, MgO > NaCl
Outer electronic configuration of given 2NH3 + CaCl2 + H2O Ans. (a)
elements are Hence, the only by-product of the Correct option is (a) i.e. LiF > LiCl; MgO >
Li →2s 1; Na →3s 1 reaction is calcium chloride. NaCl. Melting point is directly
Ca →4s ;2
Ba →6s 2 proportional to lattice energy. Lattice
36 Given below are two statements. energy is the energy required to
(A) Ba → Outer electronic
separate a mole of an ionic solid into
configuration →6s 2 . i.e. (ii). Statement I Both CaCl 2 ⋅ 6H2O and gaseous ions.
(B) Ca → Calcium oxalate MgCl 2 ⋅ 8H2O undergo dehydration It depends upon charge of ions and size
(CaC2O4 ) → insoluble in water i.e. on heating. of ions.
(iii).
192 JEE Main Chapterwise Topicwise Chemistry

Charge 2NH3 + H2O + CO2 → (NH4 )2 CO3

M.P ∝ L.E ∝ (III) Charge/radius ratio of Be is
Size (NH4 )2 CO3 + H2O + CO2 → 2NH4HCO3
greater than that of Al.
Li → + 1 Li → + 1 (IV) Both Be and Al form mainly NH4HCO3 + NaCl → NH4 Cl + NaHCO3 (s )
F =−1 Cl → − 1 2NaHCO3 →∆ Na2 CO3 + CO2 + H2O
covalent compounds.
Both LiF and LiCl having same charge, so 1
[2020, 3 Sep Shift-II] (III) CaSO4 ⋅ H2O (plaster of Paris) is
melting point will depend on size. (a) (II), (III) and (IV) (b) (I), (II) and (IV) 2
Larger the size of anion, lesser the (c) (I), (III) and (IV) (d) (I), (II) and (III) used for making casts of statues.
lattice energy and hence, melting point (IV) CaCO3 is used as an antacid.
order is LiF > LiCl. Ans. (b)
Similarly, MgO NaCl Statements (I), (II) and (IV) are correct 42 Among the sulphates of alkaline
Mg → 2 + Na → 1 + whereas statement (III) is incorrect.
earth metals, the solubilities of
Corrected statement is
O→ 2 − Cl → 1 − BeSO 4 and MgSO 4 in water,
(Charge/Radius) of Be and Al is same
MgO having + 2 charge which is greater respectively, are [2020, 6 Sep Shift-I]
because of diagonal relationship.
than NaCl (+ 1) charge. So, greater the
(a) poor and poor (b) high and poor
charge on the ions greater will be lattice
energy and hence, melting point order is 40 An alkaline earth metal ‘M’ readily (c) high and high (d) poor and high
MgO > NaCl. forms water soluble sulphate and Ans. (c)
water insoluble hydroxide. Its oxide Hydration enthalpies of BeSO4 and
38 Two elements A and B have similar MO is very stable to heat and does MgSO4 are quite high because of small
chemical properties. They don’t not have rock-salt structure. M is size of Mg2 + and Be2 + ions. These
form solid hydrogencarbonates, [2020, 4 Sep Shift-II] hydration enthalpy values are higher
than their corresponding lattice
but react with nitrogen to form (a) Sr (b) Ca
enthalpies and therefore,BaSO4 and
nitrides. A and B, respectively, are (c) Be (d) Mg
MgSO4 are highly soluble in water.
[2020, 2 Sep Shift-II] Ans. (c) Hence, the correct option is (c).
(a) Na and Rb (b) Na and Ca Solubility of BeSO4 is highest among the
(c) Cs and Ba (d) Li and Mg given options and order is as follows : 43 In the following reactions, products
Ans. (d) BeSO4 > MgSO4 > CaSO4 > SrSO4 (A) and (B), respectively, are
Group-2 metals (Be, Mg, Ca, Sr, Ba) form > BaSO4
II NaOH + Cl 2 → ( A) + side products
nitrides (M3 N2 ) and their hydrogen- or BeSO4 is water soluble sulphate and
(hot and conc.)
II Be(OH)2 is insoluble.
bicarbonates [M(HCO3)2 ] are known only BeO is stable to heat and does not form Ca(OH) 2 + Cl 2 → (B) + side
in solution phase (in situ). rock salt like structure. products (dry) [2020, 7 Jan Shift-II]
∆ II (a) NaClO 3 and Ca(OCl)2
M +N2 → M3 N2 41 Match the following compounds (b) NaClO 3 and Ca(ClO 3)2
II 25 ° C (Column -I) with their uses (c) NaOCl and Ca(OCl)2
M CO3 (s ) + CO2 (g) + H2O(l ) →
(Columns -II). (d) NaOCl and Ca(ClO 3)2
II
M(HCO3)2 (aq) Ans. (a)
Column -I Column - II
The above two properties are not given 6 NaOH+ 3Cl2 → NaClO3 + 5NaCl + 3H2O
(I) Ca(OH)2 (A) Casts of (Hot and conc.) (A )
by group-I metals (Li, Na, K, Rb Cs) statues
except Li. Li resembles with group-II (II) NaCl (B) White wash 2Ca(OH)2 + 2Cl2 → Ca(OCl)2
metals in comparison of their chemical (Dry) (B)
properties. (III) CaSO ⋅ 1 H O (C) Antacid
4
2
2 + CaCl2 + 2H2O
Specifically, Li (A) and Mg (B) have similar
chemical properties as they show (IV) CaCO 3 (D) Washing soda Thus, A : NaClO3; B : Ca(OCl)2
“diagonal relationship” in the periodic preparation
table.
[2020, 6 Sep Shift-II] 44 When gypsum is heated to 393 K, it
2nd period : Li Be B C N O F
(a) (I)-(D), (II)-(A), (III)-(C), (IV)-(B) forms : [2020, 8 Jan Shift-I]

3rd period : Na Mg Al Si P S Cl (b) (I)-(B), (II)-(D), (III)-(A), (IV)-(C) (a) Dead burnt plaster
(c) (I)-(B), (II)-(C), (III)-(D), (IV)-(A) (b) CaSO 4 ⋅0.5H2O
39 Among the statements (I-IV), the (d) (I)-(C), (II)-(D), (III)-(B), (IV)-(A) (c) CaSO 4 ⋅5H2O
correct ones are : Ans. (b) (d) Anhydrous CaSO 4
(I) Be has smaller atomic radius Correct match is I→ (B), II → (D), III → (A), Ans. (b)
IV → (C) When gypsum is heated to 393 K, it
compared to Mg.
(I) Ca(OH)2 used in white wash. forms, plaster of Paris CaSO4 . 0.5H2O.
(II) Be has higher ionisation
(II) NaCl is used in the preparation of The reaction is as follows :
enthalpy than Al. washing soda. ∆
CaSO4 . 2H2O → CaSO4 . 0.5H2O
393 K
s-Block Elements 193

45 A metal (A) on heating in nitrogen Ans. (a) < 373K

Na2 CO3 ⋅ 10H2O → Na2 CO3 ⋅H2O
−9H 2 O
gas gives compound B. B on Magnesium powder burns in air to give Washing soda Monohydrate
treatment with H2O gives a MgO and Mg 3N2 . MgO does not combine (X ) (Y )
with excess oxygen to give any
colourless gas, which when passed superoxide. Mg reacts with nitrogen to →
> 373K
Na2 CO3
−H 2 O
through CuSO 4 solution gives a form magnesium nitride (Mg 3N2 ). Anhydrous white powder
dark blue-violet coloured solution. (soda ash) (Z )
Mg + O2 → MgO
A and B respectively, are 3Mg + N2 → Mg 3 N2 50 The correct sequence of thermal
[2020, 8 Jan Shift-II]
(a) Na and Na3N
stability of the following carbonates
(b) Mg and Mg 3N2
48 The structures of beryllium is [2019, 12 April Shift-I]

(c) Mg and Mg(NO 3)2 chloride in (a) BaCO 3 < CaCO 3 < SrCO 3 < MgCO 3
(d) Na and NaNO 3 the solid state and vapour phase, (b) MgCO 3 < CaCO 3 < SrCO 3 < BaCO 3
Ans. (b) respectively are [2019, 9 April Shift-II] (c) MgCO 3 < SrCO 3 < CaCO 3 < BaCO 3
(a) dimeric and dimeric (d) BaCO 3 < SrCO 3 < CaCO 3 < MgCO 3
According to the question,
(b) chain and chain Ans. (b)
A =Mg and B =Mg 3N2
(c) dimeric and chain The correct sequence of thermal
Complete reactions are as follows : (d) chain and dimeric stability of carbonates is
6Mg + 2N2 → 2Mg 3N2 Ans. (d) MgCO3 < CaCO3 < SrCO3 < BaCO3
Mg 3N2 + 6H2O → 3Mg(OH)2 + 2NH3 The structures of beryllium chloride in On moving down the group, i.e. from Mg
Cu2 + + 4NH3 → [Cu(NH3) 4 ]2 + the solid state and vapour phase, to Ba, atomic radius generally increases.
(dark blue violet colour) respectively are dimeric and chain. In It is due to the addition of shell. As a
vapour phase at above 900°C,BeCl2 is result, the atomic size increases. CO23− is
46 The covalent alkaline earth metal monomeric having a linear structure Cl a large anion. Hence, more stabilised by
halide (X =Cl, Br, I) is BeCl. The bonding inBeCl2 is Ba2 + (large cation) and less stabilised by
[2019, 8 April Shift-II] covalent and Be atom accommodates Mg2 + . Therefore,BaCO3 has highest
2 + 2 = 4 electrons in the two sp-hybrid thermal stability followed bySrCO3,
(a) SrX2 (b) CaX2 orbitals. Below 900°C, beryllium chloride
(c) MgX2 (d) BeX2 CaCO3 and MgCO3.
in vapour phase exists as a mixture of
Ans. (d) monomerBeCl2 and dimerBe2 Cl 4 .
51 The alkaline earth metal nitrate that
Key Idea According to Fajan’s rule, does not crystallise with water
degree of covalency (ionic potential), φ 49 A hydrated solid X on heating
∝-polarisation power of the cation ∝
molecules, is
initially gives a monohydrated (a) Ca(NO 3)2 (b) Sr(NO 3)2
charge on the cation
1 compound Y. (c) Ba(NO 3)2 (d) Mg(NO 3)2
∝ . Y upon heating above 373 K leads [ 2019, 9 Jan Shift-I]
size of the cation
to an anhydrous white powder Z. X Ans. (c)
Alkaline earth metals contains bipositive I
(H2 + ) ions in their compounds. So, here and Z, respectively, are A saturated aqueous solution of M (NO3)2
[2019, 10 April Shift-II]
(i) Charge on cation, i.e. + 2 is on crystallisation will produce hydrated
constant. (a) baking soda and soda ash II
crystal, M (NO3)2 ⋅ nH2O only when
(ii) Halide present (X − ) is also (b) washing soda and soda ash
(c) baking soda and dead burnt plaster hydration enthalpy (∆H°hyd ) of M2 + ion
constant. will be appreciably more negative.
So, the covalent character depends on (d) washing soda and dead burnt
plaster Hydration of an ion depends on its size.
the size of alkaline earth metal. As we
Smaller the size of an ion, higher will be
move down the group, size of metal ion Ans. (b) its charge density and as a result it will
increases.
Baking soda (NaHCO3) is not a hydrated remain more solvated (hydrated) through
Be2 + < Mg2 + < Ca2 + < Sr2 + < Ba2 + solid. Thus, (X) is not baking soda. Thus, ion dipole interaction.
So, Be2 + readily forms covalent option (a) and (c) are incorrect. Dead Size of group-2 metal ions increases on
compounds likeBeX2 , because of very burnt plaster (CaSO4 ) is obtained from going down the group. So, their ability to
high positive charge density over its gypsum via the formation of plaster of form hydrated crystals follows the order:
small size, so that it readily polarises Paris. Be2 + >> Mg2 + >> Ca2 + >> Sr2 + >> Ba2 +
anionic spherical electron cloud.
380- 393 K 1 Thus, Ba(NO3)2 is slightly or almost
CaSO4 ⋅2H2O → CaSO4 ⋅ H2O
−1/2 H 2 O 2 insoluble in water.
47 Magnesium powder burns in air to Gypsum
Plaster of Paris
give [2019, 9 April Shift-I] > 393K
→ CaSO4 52 The metal used for making X-ray
(a) MgO and Mg 3N2 1
− H 2 O Dead burnt
2 tube window is
(b) Mg(NO 3)2 and Mg 3N2 plaster
[2019, 10 Jan Shift-I]
(anhydrous)
(c) MgO only Therefore, the reaction takes place as (a) Na (b) Be
(d) MgO and Mg(NO 3)2 follows : (c) Mg (d) Ca
194 JEE Main Chapterwise Topicwise Chemistry

Ans. (b) 55 Which one of the following alkaline Ans. (c)

Among the four elements given, Na, Be, earth metal sulphates has its Mg 3N2 (s ) + 6H2O(l ) → 3Mg(OH)2
Mg and Ca, Be has highest IE value hydration enthalpy greater than its 1 mol +2NH3 (g)
because of its smallest size and2s 2 2 mol
valence shell configuration. lattice enthalpy? [JEE Main 2015]
(a) CaSO 4 (b) BeSO 4 58 The solubilities of carbonates
So, X-ray cannot cause ionisation from
(c) BaSO 4 (d) SrSO 4 decrease down the magnesium
the material used, i.e. Be in the tube
window, which may cause interference Ans. (b) group due to a decrease in
[AIEEE 2003]
in the study. As we move down the group, size of
metal increases. Be has lower size while (a) lattice energies of solids
53 The amphoteric hydroxide is SO24− has bigger size, that's why BeSO4 (b) hydration energies of cations
breaks easily and lattice energy (c) inter ionic attraction
(a) Be(OH)2 (b) Ca(OH)2
becomes smaller but due to lower size of (d) entropy of solution formation
(c) Sr(OH)2 (d) Mg(OH)2 Be, water molecules are gathered Ans. (b)
[2019, 11 Jan Shift-I] around and hence hydration energy
Ans. (a) increases. The solubilities of carbonates of the
alkaline earth metals decrease down the
For group-2 metal hydroxides, basicity On the other hand, rest metals i.e. Ca,
group mainly due to decreasing
increases down the group, as: Ba, Sr have bigger size and that's why
hydration ethalpies of the cartions from
lattice energy is greater than hydration
Be(OH)2 < Mg(OH)2 < Ca(OH)2 Be2 + to Ba2 + .
energy.
< Sr(OH)2 < Ba(OH)2
Time Saving Technique In the question 59 The substance not likely to contain
This is because as the size of metal atom of finding hydration energy only check
increases, M—OH bond length increases CaCO 3 , is [AIEEE 2003]
the size of atom. Smaller sized atom has
or M—OH bond become weaker thus more hydration energy. (a) a marble statue
readily breaks to release OH − ions which (b) calcined gypsum
Thus, in this question Be is placed upper
are responsible for the basicity of these (c) sea shells (d) dolomite
most in the group has lesser size and not
solutions.
comparable with the size of sulphates. Ans. (b)
But Be(OH)2 shows amphoteric (basic as Hence,BeSO4 is the right response.
well as acidic) character as it reacts with Calcined gypsum does not contain CaCO3
acid and alkali both which is shown in the as gypsum is CaSO4 ⋅2H2O.
following reactions. Be(OH)2 as a base :
56 Which of the following on thermal i.e., it is sulphate.
decomposition yields a basic as
Be(OH)2 + 2HCl → BeCl2 + 2H2O
well as acidic oxide? [AIEEE 2012] 60 The substance used in Holmes
Be(OH)2 as an acid :
(a) NaNO 3 (b) KCIO 3 signals of the ship is a mixture of
Be(OH)2 + 2NaOH → Na2 [Be(OH) 4 ] (c) CaCO 3 (d) NH4NO 3 [AIEEE 2003]
Ans. (c) (a) CaC2 + Ca3P2 (b) Ca3 (PO 4 )2 + Pb 3O 4
54 Both lithium and magnesium ∆ (c) H3PO 4 + CaCl2 (d) NH3 + HOCl
display several similar properties (a) 2NaNO3 → 2NaNO2 + O2
Ans. (a)
due to the diagonal relationship; ∆
(b) 2KClO3 → 2KCl + 3O2 In Holmes signals of the ship, mixture of
however, the one which is ∆ CaC2 and Ca3P2 is used.
incorrect is [JEE Main 2017] (c) CaCO3 → CaO + CO2
Basic Acidic
(a) Both form basic carbonates 61 A metal M forms water soluble
∆
(b) Both form soluble bicarbonates (d) NH4NO3 → N2O + H2O MSO 4 and inert MO ⋅ MO in aqueous
(c) Both form nitrides solution forms insoluble M(OH) 2 ,
(d) nitrates of both Li and Mg yield NO2 57 One mole of magnesium nitride on soluble in NaOH. Metal M is
and O2 on heating reaction with an excess of water [AIEEE 2002]
Ans. (a) gives [AIEEE 2004] (a) Be (b) Mg (c) Ca (d) Sr
Mg can form basic carbonate while Li (a) one mole of ammonia Ans. (a), (b)
can not. (b) one mole of nitric acid Both Be(OH)2 and Mg (OH)2 being insoluble
5 Mg2 + + 6 CO23– + 7H2O → (c) two moles of ammonia are obtained fromNaOHsolution through
4MgCO3 ⋅Mg(OH)2 ⋅ 5H2O + 2 HCO−3 (d) two moles of nitric acid precipitation.
17
p-Block Elements
TOPIC 1 (B) H H H Ans. (a)
B B
Group 13 Elements H H H Diborane (B2H6 ) reacts independently
with O2 and H2O to produce B2O3 and H3BO3
3 3
sp sp respectively. Diborane is a colourless,
01 In which one of the following Hybridisation of boron in B2H6 is sp3.
highly toxic gas, having boiling point 180
molecules strongest back donation K. Because of its inflammable nature, it
(C) B2H6 has two bridged, catches fire spontaneously when
of an electron pair from halide to 3-centre-2-electron bond. exposed to air and burns in oxygen
boron is expected? (D) B2H6 is a non-planar molecule. releasing an enormous amount of energy
[2021, 27 Aug Shift-I]
as :
(a) BCl3 (b) BF3 (c) BBr3 (d) BI3 03 The correct statement about B 2H6 B2H6 + 3O2 → B2O3 + 3H2O
Ans. (b) + 1976 kJ/mol
is [2021, 25 Feb Shift-I]
Smaller the halide atom, more effective It gets hydrolysed readily to give boric
(a) all B—H—B angles are of 120°
is back donation of an electron pair from acid.
halide atom. (b) the two B—H—B bonds are not of
same length B2H6 + 6H2O → 2H3BO3
So, correct answer isBF3. Borane Orthoboric acid
(c) terminal B—H bonds have less
p-character when compared to + 6H2 ↑
02 Given below are the statements bridging bonds
Dihydrogen

about diborane. (d) Its fragment, BH3, behaves as a Lewis 05 The correct statements among I to
(A) Diborane is prepared by the base III regarding group 13 element
oxidation of NaBH4 and I2 . Ans. (c) oxides are: [2019, 9 April Shift-II]

(B) Each boron atom is in Statement (c) is correct, whereas all I. Boron trioxide is acidic.
sp 2 -hybridised state. other statements are incorrect. II. Oxides of aluminium and
(C) Diborane has one bridged 3 H H H gallium are amphoteric.
θ2 B θ1 B III. Oxides of indium and thallium
centre -2 - electron bond.
H H H
(D) Diborane is a planar molecule. θ2 < θ1
are basic.
(a) I, II and III (b) I and III only
The option with correct
Correct statements are as follows (c) I and II only (d) II and III only
statement(s) is [2021, 22 July Shift-II] ● Both B  H B bridge bond having
Ans. (a)
(a) (C) and (D) only same bond length.
(b) (A) only All the given statements are correct. For
● B  H B bond angle is90°.
group 13 elements, the acidic nature of
(c) (C) only BH3 is electron deficient species and oxides decreases and the basic nature of
(d) (A) and (B) only therefore act as Lewis acid. oxides increases on moving from B to Tl.
Ans. (b) This is because as we move down the
Statement (A) is correct whereas all 04 Diborane (B 2H6 ) reacts group, the atomic size of elements goes
other options are incorrect. Diborane is on increasing, whereas the ionisation
independently with O 2 and H2O to energy decreases, due to which the
prepared by the oxidation of NaBH 4
with I2 .
produce, respectively. strength of metal oxide (MO) bond goes
[2019, 8 April Shift-I] on decreasing.
Chemical reaction is as follows:
(a) B2O 3 and H3BO 3 Thus, boron trioxide or boron oxide is
(A) The oxidation of sodium borohydride
with iodine in diglyme gives (b) B2O 3 and [BH4] − acidic and reacts with basic oxides to
give metal borates. Aluminium and
diborane. (c) H3BO 3 and B2O 3 gallium oxides are amphoteric while
Diglyme
I2 + 2NaBH4 → 2NaI+ B2H6 + H2 (d) HBO2 and H3BO 3 oxides of indium and thallium are basic in
nature.
196 JEE Main Chapterwise Topicwise Chemistry

06 Aluminium is usually found in +3 In B2H6 , four 2-centre-2-electron can have the required number of
(2c − 2e) bonds are present in the same electrons to write their conventional
oxidation state. In contrast,
plane and two 3-centre-2-electron Lewis structures.
thallium exists in +1 and +3 (3 c − 2e) bonds are present in another H
oxidation states. This is due to plane. 8e– around Si
[2019, 9 Jan Shift-I] Si (Octet gets satisfied)
H
(a) lattice effect 09 The relative stability of + 1 oxidation H H
(b) lanthanoid contraction state of group 13 elements follows
(c) inert pair effect the order [2019, 11 Jan Shift-II] 11 When metal ‘M’ is treated with
(d) diagonal relationship (a) Al < Ga < Tl < In (b) Al < Ga < In < Tl NaOH, a white gelatinous
Ans. (c) (c) Tl < In < Ga < Al (d) Ga < Al < In < Tl precipitate ‘X’ is obtained, which is
Due to inert pair effect, group-13 Ans. (b) soluble in excess of NaOH.
elements (ns 2 np1) show + 3 and + 1 Compound ‘X’ when heated strongly
oxidation states in their compounds. The stability order of + 3 and + 1
oxidation states of group 13 elements gives an oxide which is used in
Stability order of these oxidation states
will be as, + 3 oxidation states will be: chromatography as an adsorbent.
B3+ > Al 3+ > Ga3+ > In3+ > Tl 3+ B3 + > Al 3 + > Ga3 + > In3 + >>Tl 3+ The metal ‘M’ is [JEE Main 2018]
3+
B does not exist in free states. All B(III) (order of + 3 oxidation state) (a) Zn (b) Ca (c) Al (d) Fe
compounds are covalent. B+ <<Al + < Ga+ < In+ < Tl + Ans. (c)
+ 1 oxidation states (order of + 1 oxidation state) Among the given metals Al forms white
B+ < Al + < Ga+ < In+ < Tl + The presence of two oxidation states in gelatinous ppt. with NaOH. Hence, the
+ p-block elements is due to the inert pair probable metal can be Al.
B does not exist in ionic as well covalent effect.
compounds. This ppt. is dissolved in excess of NaOH
Because of the presence of poor due to the formation of sodium metal
shieldingd and f-orbitals, as we move Aluminate. Both the reactions are shown
07 The electronegativity of aluminium from Ga to Tl, effective nuclear charge of below.
is similar to [2019, 10 Jan Shift-I] these elements increases so as to hold Al 3+ NaOH
→ Al(OH) 3 ↓
(a) lithium (b) carbon the valence ns 2 electrons tightly. It White gelatinous
(c) beryllium (d) boron causes difficulty to the ionisation of ppt. (X ) of
Ans. (c) ns 2 -electrons and it remains inert, only aluminium
hydroxide
np1-electron ionises to give + 1 oxidation
Let, us consider the electronegativity 
state. Excess of NaOH
values of the given elements,
↓
Group-1 Group-2 Group-13 Group-19
10 The hydride that is not electron NaAlO2
Period 2 ⇒ Li Be B C (Sodium
(1 .0) (1 .5) (2 .0) (2 .5) deficient is [2019, 11 Jan Shift-II] metaaluminate)
(a) AlH3 (b) B2H6 soluble
Period 3 ⇒ Al
(1.5) (c) SiH4 (d) GaH3 Aluminium hydroxide on strong heating
Ans. (c) gives alumina (Al2O3) which is used as an
Be and Al show diagonal relationship adsorbent in chromatography. This
Z∗ GaH3, AlH3 and B2H6 are the hydrides of
which is based on their same value reaction can be seen as :
r group-13 (ns 2 np1), whereasSiH4 is an ∆
2Al(OH) 3 → Al2O3 + 3H2O
(Z * is effective nuclear charge, r = atomic hydride of group 14.
radius). So, they have similar Thus, metal M is Al.
electronegativity. H H Ca, being below sodium in
sp2 sp2 electrochemical reactivity series, cannot
Ga Al
08 The number of 2-centre-2-electron H H H H displaces Na from its aqueous solution.
and 3-centre-2-electron bonds in 6e – around 6e – around Zn reacts with NaOH to form sodium
B 2H6 , respectively, are Ga 3+ <8e – (octet) Al 3+ <8e – (octet) zincate which is a soluble compound.
(GaH3) (AlH3) Fe reacts with sodium hydroxide to form
[2019, 10 Jan Shift-II]
3c–2e – bridge bond tetrahydroferrate (II) sodium which is
(a) 4 and 2 (b) 2 and 4 H
H sp3 H again a soluble complex.
(c) 2 and 2 (d) 2 and 1
B B
Ans. (a) H H 12 Boron can’t form which one of the
H
The structure of B2 H6 can be shown as : B is sp3, but cannot satisfy octet due following anions? [AIEEE 2011]

H H H
to the attachment of two 3c-2e – (a) BF63− (b) BH−4
H bridge bonds (B–H–B) (c) B(OH) −4 (d) BO2−
H e H
–2
3c–3e 2c3 So, B2H6 , AlH3 and GaH3 are electron Ans. (a)
B B ⇒ B B sp
deficient hydrides. B5
H H 1s 2 2s 2 2p 1
H H But, SiH4 is an electron precise hydride
H H
of group-14 (ns 2 np2 ), i.e. these hydrides Ground state
p-Block Elements 197

2s 1 2p 2 Ans. (c) (c) forming covalent halides

Excited state Chlorides of both beryllium and (d) exhibiting amphoteric nature in their
aluminium have bridged structures in oxides
Fourth lone pair is accommodated solid phase. Ans. (a)
in this empty orbital Be (Z = 4) has maximum covalency of
Maximum covalency = 4 16 The type of hybridisation of boron 4 while Al (Z = 13) has maximum
Due to absence of2d-orbital, maximum in diborane is [AIEEE 2007] covalency of 6.
covalency is four. Thus, BF63− is not (a) sp hybridisation 20 Aluminium chloride exists as dimer,
formed. (b) sp2 hybridisation Al 2Cl 6 in solid state as well as in
Therefore, (a) is not formed while (c) sp 3 hybridisation solution of non-polar solvents such
BH−4 (BH3 + H− ), B(OH) –4 , (B[OH) 3 + OH– ] (d) sp 3d2 hybridisation as benzene. When dissolved in
and BO2– are formed. Ans. (c) water, it gives [AIEEE 2004]
Boron atom in B2H6 (diborane) is sp3 (a) Al3+ + 3Cl−
13 Which one of the following order hybridised.
represents the correct sequence of (b) [Al[H2O) 6] 3+ + 3Cl−
the increasing basic nature of the (c) [Al(OH) 6] 3 – + 3HCl
17 The structure of diborane (B 2H6 )
given oxides? [AIEEE 2011] (d) Al2O 3 + 6HCl
contains [AIEEE 2005]
(a) MgO < K2O < Al2O3 < Na2O Ans. (b)
(a) four 2c − 2e − bonds and four
(b) Na2O < K2O < MgO < Al2O3
3 c − 2e − bonds AlCl 3 is covalent but in water, it become
(c) K2O < Na2O < Al2O3 < MgO (b) two 2c − 2e − bonds and two3 c − 3e − ionic due to large hydration energy of
(d) Al2O3 < MgO < Na2O < K2O bonds Al 3+ .
Ans. (d) (c) two2c − 2e − bonds and four3 c − 2e − AlCl 3 + 6H2O
r [Al(H2O) 6 ] 3+ + 3Cl −
bonds
Metallic character decreases on moving
(d) four 2 c − 2e − bonds and two 21 Alum is widely used to purify water
along a period in the sequence as
3 c − 2 e − bonds since
Na > Mg > Al and increases down the
group. Ans. (d) (a) it forms complex with clay particles
As metallic character of the element Structure of B2H6 (b) it coagulates the mud particles
attached to oxygen atom increases, the Electrons of H Electrons of B (c) it exchanges Ca2 + and Mg2 + ions
basic character of oxides increases. 3c-2e– bonds
present in hard water
Hence, the increasing correct order of (d) its sulphate ion is water purifier
basic nature is Al2O3 < MgO < Na2O < K2O. [AIEEE 2002]
–
2c-2e bonds B Ans. (b)
14 Among the following, the maximum B 2c-2e– bonds
Mud is colloidal charged solution which
covalent character is shown by the on treatment with alum (Al 3+ ) gets
compound. [AIEEE 2011] neutralised or coagulated.
(a) SnCl2 (b) AlCl3 3c-2e– bonds
(c) MgCl2 (d) FeCl2
Ans. (b) 18 Heating of an aqueous solution of TOPIC 2
aluminium chloride to dryness will
Greater the charge and smaller the size
give [AIEEE 2005]
Group 14 Elements
of the cation, larger the charge density.
Thus, greater is the polarization of M − Cl (a) Al(OH)Cl2 (b) Al2O 3
bond and hence, maximum covalent (c) Al2Cl6 (d) AlCl3 22 Which one of the following
character is possessed by the Ans. (b) compounds of group-14 elements
compound. is not known? [2021, 25 July Shift-I]
Aqueous solution of AlCl 3 is acidic, as it
Among the given species, only AlCl 3 gives HCl on hydrolysis. (a) [GeCl6] 2−
possesses maximum covalent charge (b) [Sn(OH) 6] 2−
AlCl 3 + 3H2O r Al(OH) 3 + 3HCl
due to the presence of large charge
density on Al 3+ ion. On strongly heating, Al(OH) 3 is converted (c) [SiCl6] 2−
into Al2O3. (d) [SiF6] 2−
15 Which one of the following is the ∆ Ans. (c)
2Al(OH) 3 → Al2O3 + 3H2O
correct statement ? [AIEEE 2007] In group 14, [SiCl 6 ]2 − does not exist due
(a) Boric acid is a protonic acid to steric crowding of surrounding atoms.
19 Beryllium and aluminium exhibit
(b) Beryllium exhibits coordination The main reasons are:
number of six many properties which are similar.
(i) Six large chloride ions cannot be
(c) Chlorides of both beryllium and But the two elements differ in
[AIEEE 2004]
accommodated around Si4+ .
aluminium have bridged chloride
(a) exhibiting maximum covalency in (ii) Interaction between lone pair of
structures in solid phase
compounds chloride ion andSi4+ is not very
(d) B2H6 ⋅2NH3 is known as ‘inorganic strong.
benzene’ (b) forming polymeric hydrides
198 JEE Main Chapterwise Topicwise Chemistry

23 The incorrect statement regarding (c) mercury 29 The number of pentagons in C 60

the structure of C 60 is (d) zinc sulphide and trigons (triangles) in white
[2021, 16 March Shift-II] Ans. (a) phosphorus, respectively, are
(a) the six-membered rings are fused to ‘X’ is carbon tetrachloride. It is a [2019, 10 April Shift-II]
both six and five-membered rings molecular solid. It melts at low (a) 20 and 3 (b) 12 and 4
(b) each carbon atom forms three sigma temperature and is a bad conductor of (c) 20 and 4 (d) 12 and 3
bonds electricity in both liquid and solid state. Ans. (b)
(c) the five-membered rings are fused Other options are explained as follows :
only to six-membered rings In C60 (Buckminster fullerene) twenty
(d) it contains 12 six-membered rings (1) Silicon Network (or covalent) hexagons and twelve pentagons are
and 24 five-membered rings carbide solid. Very high melting present which are interlocked resulting a
point. Not electric shape of soccer ball. Every ring in this
Ans. (d) conductor as solid or structure is aromatic.
liquid.
(2) Mercury Metallic solid with an
exceptionally low melting
point, conduct electricity
in both solid and molten
forms.
(3) Zinc Ionic crystal. High melting
sulphide point and conduct
electricity in molten state
but not as solid.

C60 molecule has a shape like soccer ball

and called Buckminster fullerene. It is an 26 C 60 an allotrope of carbon contains Structure of C 60 Buckminster fullerene
allotrope of carbon. It contains [2019, 9 April Shift-I]
twenty-six membered rings and (a) 16 hexagons and 16 pentagons Phosphorus has large atomic size and
twelve-five membered rings. A six less electronegativity, so it forms single
(b) 20 hexagons and 12 pentagons
membered ring is fused with six or five bond instead of pπ-pπ multiple bond. So,
(c) 12 hexagons and 20 pentagons it consists of discrete tetrahedralP4
membered rings but a five membered
(d) 18 hexagons and 14 pentagons molecule as shown below :
ring can only fuse with six membered
rings. Ans. (b)
P
All the carbon atoms are equal and they C60 is aromatic allotrope of carbon
P P
undergo sp2 -hybridisation . Each carbon containing 12 pentagons and 20
atom forms three sigma bonds with hexagons. It is a fullerene having a shape P
other three carbon atoms. like soccer ball and called Buckminster
fullerene. ∴ Number of trigons (triangles) = 4
So, statement (d) is wrong.

27 The amorphous form of silica is 30 The basic structural unit of feldspar,

24 Water does not produce CO on
[2019, 9 April Shift-II] zeolites, mica and asbestos is
reacting with [2021, 25 Feb Shift-II] [2019, 12 April Shift-I]
(a) tridymite (b) kieselguhr
(a) CH 4 (b) C (c) CO2 (d) C 3H8 (a) (SiO 3)2−
(c) cristobalite (d) quartz
Ans. (c) (b) SiO2
Ans. (b)
Water (steam) can produce CO on (c) (SiO 4 ) 4−
Silica occurs in nature in several
reacting with CH4 , C and C3H8 as, R
amorphous and crystalline forms.
1270 K
CH4 + H2O → CO + 3H2 Kieselguhr is the amorphous form of 
Ni
silica. Quartz, tridymite and cristobalite (d) ( Si O ) n (R = Me)
1270 K
C + H2O → CO + H2 are crystalline forms of silica. 
R
1270 K
C3H8 + 3H2O → 3CO + 7H2 28 The correct order of catenation is Ans. (c)
Ni
[2019, 10 April Shift-I]
But, water on reaction with CO2 The basic structural unit of feldspar,
(a) C > Sn > Si ≈ Ge (b) Si > Sn > C > Ge zeolites, mica and asbestos is (SiO4 ) 4− .
produces carbonic acid (H2 CO3), not CO.
(c) C > Si > Ge ≈ Sn (d) Ge > Sn > Si > C These all are silicates. All silicates
CO2 + H2O → H2 CO3
Ans. (c) involve two types of Si  O bonds.
25 ‘X’ melts at low temperature and is Catenation property is an unique (i) Terminal Si O bonds in which
property of group 14 elements. Down the oxygen is bonded to a silicon and
a bad conductor of electricity in not other atom.
group 14, catenation power decreases
both liquid and solid state. X is (ii) BridgingSi O Si bonds in which
[2020, 9 Jan Shift-II]
as :
C > Si > Ge ≈ Sn oxygen is bonded to two silicon
(a) carbon tetrachloride atoms.
(b) silicon carbide Pb does not show catenation.
p-Block Elements 199
O– s
Ans. (d) of catenation among all elements of
Silicones are polysiloxanes with general family due to higher bond energy. The
Si O– decreasing tendency of catenation
chemical formula, [R2SiO] n , where R is
O– O– s s an organic group such as:  CH3, among group 14 elements is as follows:
Tetrahedral structure of SiO24 − anion  C2H5 ,  C6H5 etc. C >> Si > Ge ≈ Sn
In SiO4− Silicones have many useful properties: However, Pb does not show catenation.
4 ion, each Si atom is bonded to
four oxygen atoms tetrahedrally. (i) They repel water and form
watertight seals. 36 Which of the following exists as
31 The C  C bond length is maximum (ii) They are heat resistant because of covalent crystals in the solid state?
constancy of properties over a [JEE Main 2013]
in [2019, 12 April Shift-II]
wide range of temperature (a) Iodine (b) Silicon
(a) graphite (b) C 70 (− 100 ° to 250° C). (c) Sulphur (d) Phosphorus
(c) C 60 (d) diamond (iii) Silicones are non-toxic.
Ans. (b)
Ans. (d) (iv) Silicones are biocompatible
because these do not support Silicon exists as covalent crystal in solid
The C  C bond length is maximum in state. It exhibits a network structure like
diamond having value 154 pm. Here, each microbiological growth and these
have high gas permeability at room diamond.
carbon atom undergoes
sp3-hybridisation and linked to four other temperature.
carbon atoms by using hybridised (v) They are resistant to O2 , O3 and 37 Among the following substituted
orbitals in tetrahedral fashion. It has a UV-radiation. silanes the one which will give rise
rigid three-dimensional network of (vi) Silicones are formulated to be to cross linked silicone polymer on
carbon atoms. electrically insulative. hydrolysis is [AIEEE 2007]
C  C bond length within the layers of (vii) Silicone grease is typically used as (a) R4 Si (b) R SiCl3
graphite is 141.5 pm. In C60 , C  C a lubricant for brake components (c) R2 SiCl2 (d) R3SiCl
distances between single and double in automobiles, since it is stable at
bonds are 143.5 pm and 138.3 pm high temperature, is not water Ans. (b)
respectively. soluble and is a odourless viscous R SiCl 3 give cross linked silicone polymer
liquid. on hydrolysis.
32 The one that is extensively used as
a piezoelectric material is 34 The element that shows greater 38 The stability of dihalides of Si, Ge,
[2019, 9 Jan Shift-I] ability to form pπ-pπ multiple Sn and Pb increases steadily in the
(a) quartz bonds, is [2019, 12 Jan Shift-II] sequence [AIEEE 2007]
(b) tridymite (a) Ge (b) Si (a) GeX2 < SiX2 < SnX2 < PbX2
(c) amorphous silica (c) Sn (d) C (b) SiX2 < GeX2 < PbX2 < SnX2
(d) mica Ans. (d) (c) SiX2 < GeX2 < SnX2 < PbX2
Ans. (a) Carbon (C) has greatest ability to form (d) PbX2 < SnX2 < GeX2 < SiX2
Piezoelectric materials are those stable pπ-pπ multiple bonds.2p-orbitals Ans. (c)
materials that produce an electric of this element participate in the
current when they are placed under process. The stability of multiple bonds Inert pair effect becomes predominant
mechanical stress. Crystalline solids can of C is attributed to their closeness with due to which +2 oxidation state becomes
be used as piezoelectric material hence, C-nucleus. Thus, the smaller size of C more stable down the group and hence,
quartz is a correct answer. plays a significant role in the process. the stability of dihalides increases down
the group.
33 Correct statements among (I) to (IV) 35 The element that does not show SiX2 < GeX2 < SnX2 < PbX2
regarding silicones are: catenation is [2019, 12 Jan Shift-II]

I. They are polymers with (a) Ge (b) Sn 39 Which of the following oxides is
(c) Si (d) Pb amphoteric in character?
hydrophobic character. [AIEEE 2005]
Ans. (d)
II. They are biocompatible. (a) SnO2 (b) SiO2
The property of self-linking of atoms of
III. In general, they have high an element through covalent bonds to (c) CO2 (d) CaO
thermal stability and low form straight or branched chains and Ans. (a)
dielectric strength. rings of different sizes is called A species is amphoteric, if it is soluble in
catenation. Down the group, catenation acid (behave as a base) as well as in base
IV. Usually, they are resistant to tendency decreases due to decrease in (behave as an acid).
oxidation and used as greases. element bond strength. Carbon (C),
(a) I and II only SnO2 +4HCl → SnCl 4 + 2H2O
[2019, 9 Jan Shift-I] silicon (Si), germanium (Ge), tin (Sn), lead
(b) I, II, III only (Pb) are group-14 elements. Base Acid
(c) I, II, III and IV Catenation tendency is highest in carbon SnO2 +2NaOH → Na2SnO3 + H2O
(d) I, II and IV only while silicon has second highest tendency Acid Base
200 JEE Main Chapterwise Topicwise Chemistry

40 In silicon dioxide [AIEEE 2005] 43 Graphite is a soft solid lubricant 46 The oxidation states of ‘P’ in
(a) there are double bonds between extremely difficult to melt. The H4P2O 7 , H4P2O 5 and H4P2O 6 ,
silicon and oxygen atoms reason for this anomalous respectively are [2021, 27 July Shift-I]
(b) silicon atom is bonded to two oxygen behaviour is that graphite (a) 7, 5 and 6 (b) 5, 4 and 3
atoms
(a) is a non-crystalline substance (c) 5, 3 and 4 (d) 6, 4 and 5
(c) each silicon atom is surrounded by
(b) is an allotropic form of diamond Ans. (c)
two oxygen atoms and each oxygen
atom is bonded to two silicon atoms (c) has molecules of variable molecular
H 4 P2 O 7
masses like polymers
(d) each silicon atom is surrounded by
four oxygen atoms and each oxygen (d) has carbon atoms arranged in large
plates of rings of strongly bound HO—P—O—P—OH
atom is bonded to two silicon atoms | |
carbon atoms with weak interplate OH OH
Ans. (d) bonds [AIEEE 2003]
Oxidation state of ‘P’ in H4P2O7
In SiO2 , each silicon atom is bonded to Ans. (d)
four oxygen atoms, that are arranged →4(+ 1) + 2x + 7 (− 2) = 0
C-atoms of graphite form covalently 2x − 10 = 0
tetrahedrally around it and eachO− atom
bonded plates (layers). These layers are
is attached to two silicon atoms by
held together by weak forces of x=+ 5
covalent bonds. H 4 P2 O 5
attraction.
O O
i.e., one layer can slide over other to
O O
cause lubricacy. It cannot be melted HO — P — O — P — OH
Si Si easily as large number of atoms being | |
bonded strongly in the layer to form big H H
O O O O O
entity. Oxidation state of P inH4P2O5
→4(+ 1) + 2x + 5 (− 2) = 0

41 The soldiers of Napolean army TOPIC 3 2x − 6 = 0

x=+3
while at Alps during freezing winter Group 15 Elements H 4 P2 O 6
suffered a serious problem as O O
regards to the tin buttons of their 44 The oxide without nitrogen-
nitrogen bond is HO — P —— P — OH
uniforms. White metallic tin | |
[2021, 1 Sep Shift-II]
buttons got converted to grey OH OH
powder. This transformation is (a) N2O (b) N2O 4 (c) N2O 3 (d) N2O 5 Oxidation state of P in H4P2O6
related to [AIEEE 2004] Ans. (d) →4(+ 1) + 2x + 6(− 2) = 0
⊕
(a) a change in the crystalline (a) Structure of N2O N N––O 2x − 8 = 0
structure of tin O ⊕ ⊕ O x=+4
(b) an interaction with nitrogen of the air (b) Structure of N2O4 N––N
O Hence, oxidation state of P in and are 5,
at very low temperature O
3 and 4 respectively.
(c) a change in the partial pressure of O ⊕ O
oxygen in the air (c) Structure of N2O3 N––N
(d) an interaction with water vapour O 47 Which one of the following
contained in the humid air O O
group-15 hydride is the strongest
⊕ ⊕
Ans. (a) (d) Structure of N2O5 N—O—N reducing agent ?
[2021, 22 July Shift-II]
As temperature decreases, white tin O O
(a) AsH3 (b) BiH3
(β -form changes to grey tin (α-form). The oxide without nitrogen-nitrogen
bond is N2O5 .
(c) PH3 (d) SbH3
13.2° C
α - Sn r β - Sn Ans. (b)
α-Sn has a much lower density. 45 Which one of the following is BiH 3 is a strongest reducing agent
formed (mainly) when red among group-15, as we move down the
42 Glass is a [AIEEE 2003] phosphorus is heated in a sealed group reducing strength of hydride
increases.
(a) microcrystalline solid tube at 803 K ? [2021, 27 Aug Shift-II]
(b) super cooled liquid Reason As we move down the group, the
(a) White phosphorus
M—H bond can break more easily to
(c) gel (b) Yellow phosphorus evolve H2 gas which acts as the reducing
(d) polymeric mixture (c) β-black phosphorus agent. Thus,  BiH3 is least stable  among
Ans. (b) (d) α-black phosphorus the hydrides of group 15 and hence is the
Glass is a supercooled liquid, which Ans. (d) strongest reducing agent.
forms a non-crystalline solid. The When red phosphorus is heated in a Reducing nature of hydride
common lime-soda glass used for sealed tube at 803 K,α-black 1
bottles and jars is a supercooled mixture ∝
phosphorus is formed. Therefore , Thermal stability (or) bond strength
of sodium and calcium silicates. option (d) is correct.
p-Block Elements 201

Order of thermal stability bond strength : Phosphorus trichloride + Phosphonic P4 + 3NaOH + 3H2O →
NH3 > PH3 > AsH3 > SbH3 > BiH3 acid → Pyrophosphoric acid PH3 + 3NaH2PO2
Order of reducing nature + Hydrochloric acid (A )
Sodium
NH3 < PH3 < AsH3 < SbH3 < BiH3 Product is pyrophosphoric acid, i.e. hypophosphite
H4P2O5 .
48 Chemical nature of the nitrogen The structure of pyrophosphoric acid
1 mole of NaH2PO2 reacts with excess of
oxide compound obtained from a shows that it has two acidic or ionisable
AgNO3 in aqueous medium to give 4
hydrogen, i.e. *H.
reaction of concentrated nitric acid moles of Ag.
O O NaH2PO2 + 4AgNO3 +2H2O →
and P4O 10 (in 4 : 1 ratio) is
[2021, 20 July Shift-I] P P 4Ag + H3PO4 + NaNO3 + 3HNO3
(a) acidic (b) basic *HO O OH* Hence, 1 mole produce 4 moles of Ag.
H H
(c) amphoteric (d) neutral (Two ionisable H)
Ans. (a) 54 Statement I Sodium hydride can be
Chemical nature of the nitrogen 51 The set that represents the pair of used as an oxidising agent.
pentaoxide compound obtained from a neutral oxides of nitrogen is Statement II The lone pair of
reaction of concentrated nitric acid and [2021, 17 March Shift-II] electrons on nitrogen in pyridine
P4O10 (in 4 : 1 ratio) is acidic. (a) NO and N2O (b) N2O and N2O 3 makes it basic.
Chemical reaction is as follows (c) N2O and NO2 (d) NO and NO2 Choose the correct answer from
P4O10 + 4HNO3 →
Phosphorus Nitric acid
Ans. (a) the options given below.
pentaoxide N2O and NO are neutral oxides of [2021, 16 March Shift-II]
4HPO3 + 2N2O5 nitrogen, whereasNO2 and N2O3 are (a) Both statement I and statement II
Meta-phosphoric Nitrogen
acid pentaoxide acidic oxides. are true
(Acidic) Neutral oxides are neither acidic nor (b) Both statement I and statement II
∴ N2O5 is an acidic oxide. basic. These oxides neither react with are false
acids nor with bases. (c) Statement I is true but statement II
49 The oxidation states of nitrogen in is false
NO, NO2, N2O and NO –3 are in the 52 Which of the following compound (d) Statement I is false but statement II
cannot act as a Lewis base? is true
order of [2021, 18 March Shift-II]
Ans. (c)
(a) NO −3 > NO2 > NO > N2O
[2021, 17 March Shift-I]
(a) NF3 (b) PCl5 (c) SF4 (d) ClF3 NaH is not an oxidising agent as Na+ and
(b) NO2 > NO −3 > NO > N2O H− ions are formed. Na exists only in + 1
Ans. (b)
(c) N2O > NO2 > NO > NO −3 PCl 5 has no lone-pair on the central atom
and hydrogen is present in minimum −1
state so, cannot be reduced further. NaH
(d) NO > NO2 > N2O > NO −3 but has emptyd-orbital in valence shell,
is used as reducing agent.
so that it can accept a pair of electrons
Ans. (a) (from a Lewis base). So,PCl 5 act as a Lone pair on nitrogen in pyridine is
Oxidation states of ‘N’ in the given Lewis acid. localised and does not take part in
compounds are as follows resonance. So, it can acceptH+ acting as
Lewis acid Species which accepts a pair
a base.
NO → x +1(− 2) = 0 of electron in their vacant orbital e.g.
x=+2 BF3, AlCl 3, PCl 5 .
NO2 → x + 2 × (− 2) = 0 Lewis base Species which can donate a N
x=+4 pair of electron, e.g. Pyridine
N2O → 2x + (− 2) = 0 •• •• •• •• ••
x=+ 1 PCl 3 , NH3, NF3, •• ClF3, S F4 . So, statement I is true but statement II is
NO−3 → x + 3(− 2) = − 1 false.
⇒ x=+ 5 53 The reaction of white phosphorus
Decreasing order of oxidation state of ‘N’ on boiling with alkali in inert 55 A group 15 element, which is a
is as follows
atmosphere resulted in the metal and forms a hydride with
NO−3 > NO2 > NO > N2O. strongest reducing power among
formation of product A. The
reaction of 1 mol of A with excess group 15 hydrides. The element is
50 The number of ionisable hydrogens [2021, 16 March Shift-I]
of AgNO 3 in aqueous medium gives
present in the product obtained (a) Sb (b) P
…… mol(es) of Ag (Round off to the (c) As (d) Bi
from a reaction of phosphorus
nearest integer). Ans. (d)
trichloride and phosphonic acid is [2021, 17 March Shift-I]
[2021, 18 March Shift-I] BiH3 is the strongest reducing agent and
Ans. (4)
(a) 3 (b) 0 (c) 2 (d) 1 have strongest reducing power. The
Reaction of white phosphorus with alkali reducing character of the group 15
Ans. (c)
in inert atmosphere forms sodium element hydrides increases down the
PCl 3 + H3PO3 + H2O → H4P2O5 + HCl hypophosphite (NaH2PO2 ). group. Ammonia is only a mild reducing
202 JEE Main Chapterwise Topicwise Chemistry

agent whileBiH3 is the strongest Ans. (d) Ans. (c)

reducing agent amongst all the hydrides. The structure of pyrophosphoric acid Nitrogen monoxide react with dinitrogen
This is due to the decrease in bond (H4P2O7 ) molecule is tetraoxide at 250 K temperature forms
energy down the group. blue solid.
HO OH
Property NH3 PH3 AsH3 SbH3 BiH3 2NO + N2O4 250
K→ 2N2O3
HO P O P OH N2O3 is acidic in nature. InN2O3, N has + 3
∆ diss .H 389 322 297 255
kJ/mol −1 O O
oxidation state. Generally, oxides with
higher oxidation states are more acidic
NH3 than oxides having lower oxidation state.
Number of P OH moieties = 4, P == O
PH3 bonds = 2 and P O  P bond = 1. It is a blue solid because it strongly
AsH3 (Increase in reducing power) absorbs in the visible region to appear
bright blue in colour.
SbH3 58 Reaction of ammonia with excess
BiH3
Cl 2 gives [2020, 5 Sep Shift-II] 61 White phosphorus on reaction with
(a) NH4Cl and N2 concentrated NaOH solution in an
So, correct answer is Bi (bismuth).
(b) NH4Cl and HCl inert atmosphere of CO 2 gives
(c) NCl3 and NH4Cl phosphine and compound (X). (X)
56 Find A, B and C in the following
(d) NCl3 and HCl on acidification with HCl gives
reactions:
Ans. (d) compound (Y). The basicity of
NH3 + A + CO 2 → (NH4 ) 2 CO 3
A yellow explsive liquid n drogen compound (Y) is [2020, 8 Jan Shift-II]
(NH4 ) 2 CO 3 + H2O +B → NH4HCO 3 trichloride is formed (a) 4 (b) 3 (c) 2 (d) 1
NH4HCO 3 + NaCl → NH4Cl + C N + 3Cl2 → 3HCl + NCl 3 Ans. (d)
[2021, 26 Feb Shift-I] Nitrogen
(Excess)
trichloride P4 + 3NaOH + 3H2O → PH3 + 3NaH2PO2
(a) A – O2 , B – CO2 , C – Na2CO 3 It here ammonia is taken in excess then (X )
(b) A – H2O , B – O2 , C – Na2CO 3 ammonium chloride is formed. +3HCl
(c) A – H2O, B – O2 , C – NaHCO 3
7NH3 + 3Cl2 → NH4 Cl + N2 3H3PO2+3NaCl
(d) A – H2O, B – CO2 , C – NaHCO 3 (Excess)
(Y)
Ans. (d) H3PO2 (Y) is a monobasic acid. Here, the
The given reaction take place as follows 59 The correct statement with H-atom of OH group is ionisable and cause
the basicity.
(i) Ammonia (NH3) reacts withH2O and respect to dinitrogen is O
CO2 to give ammonium carbonate [2020, 6 Sep Shift-I] ||
[(NH4 )2 CO3]. (a) N2 is paramagnetic in nature. H P  O H
|
2NH3 + H2O + CO2 → (NH4 )2 CO3 (b) it can combine with dioxygen at H
(A ) 25°C.
(ii) Ammonium carbonate react with (c) liquid dinitrogen is not used in 62 The correct order of the oxidation
water (H2O) and CO2 to give cryosurgery. states of nitrogen in NO, NO 2 , NO 2
ammonium hydrogen carbonate (d) it can be used as an inert diluent for
and N 2O 3 is [2019, 9 April Shift-I]
(NH4HCO3). reactive chemicals.
(a) NO2 < NO < N2O 3 < N2O
(NH4 )2 CO3 + H2O + CO2 → 2NH4HCO3 Ans. (d)
(b) N2O < NO < N2O 3 < NO2
(B) (a) All electrons inN2 are paired, thus (c) O2 < N2O 3 < NO < N2O
(iii) Ammonium hydrogen carbonate it is diamagnetic, not
(d) N2O < N2O 3 < NO < NO2
reacts with sodium chloride (NaCl) paramagnetic.
to give ammonium chloride Above Ans. (b)
2000 ° C
(NH4 Cl ) along with sodium The correct increasing order of oxidation
bicarbonate (NaHCO3).
(b) N2 + O2 - 2NO(g),
state of nitrogen for nitrogen oxides is
+1 +2 +3 +4
NH4HCO3 + NaCl → NH4 Cl +NaHCO3 (c) Liquid N2 gas is used to create
N 2 O< N O < N2 O3 < N O2
(C ) extremely cold temperature to
distroy diseased tissues located Oxidation state of N inN2O is
So, A - H2O, B - CO2 ; C - NaHCO3. 2
outside the body. 2(x) − 2 = 0; x = + = +1
(d) N2 gas used as a diluent due to it’s 2
57 In a molecule of pyrophosphoric inert nature. Oxidation state of N in NO is
acid, the number of P OH, P == O Hence, the correct option is (d). x − 2 = 0; x = +2
and P O P bonds/moiety(ies) Oxidation state of N inN2O3 is
6
respectively are [2020, 3 Sep Shift-I] 60 The reaction of NO with N 2O 4 at 2x + 3(−2) = 0; x = = 3
2
(a) 2, 4 and 1 (b) 3, 3, and 3 250 K gives [2020, 6 Sep Shift-II]
Oxidation state of N inNO2 is
(c) 4, 2, and 0 (d) 4, 2, and 1 (a) N2O (b) NO2 (c) N2O 3 (d) N2O 5 x + 2(−2) = 0; x − 4 = 0; x = +4
p-Block Elements 203

63 The correct statement among the Na3PO4 in presence of HNO3 form H3PO4 Ans. (d)
and NaNO3.
following is [2019, 12 April Shift-I] Let us consider the structure of the
Na3PO4 + 3HNO3 → H3PO4 + 3NaNO3 phosphorus oxyacids,
(a) (SiH3) 3N is planar and less basic than
(CH3) 3N. Upon cooling, a few drops of ammonium O O
(b) (SiH3) 3N is pyramidal and more basic molybdate solution are added. A yellow
ppt. confirms the presence of P P
than (CH3) 3N. H OH HO H
phosphorus in the organic compound. H OH
(c) (SiH3) 3N is pyramidal and less basic
than (CH3) 3N. H3PO4 +12 (NH4 )2 MoO4 + 21HNO3 → H3PO2 H3PO3
Hypophosphorus Orthophosphorus
(d) (SiH3) 3N is planar and more basic (NH4 ) 3PO4 .12MoO3 ↓ +21NH4NO3 +12H2O acid acid
than (CH3) 3N. Yellow ppt (P  H bonds=2) (P  H bond=1)
Ans. (d) 65 Good reducing nature of H3PO 2 is O O O O

The correct statement is that (SiH3) 3N is attributed to the presence of P P P P

[2019, 9 Jan Shift-II] H O H O OH
planar and less basic than (CH3) 3N. The HO OH OH OH
compounds trimethylamine (CH3) 3N and (a) two P H bonds H4P2O5 H4P2O6
trisilylamine (SiH3) 3N have similar (b) one P H bond Pyrophosphorus Hypophousphoric
formulae, but have totally different (c) two P OH bonds acid acid
structures. (P  H bonds=2) (P  H bond=0)
(d) one P  OH bond
In trimethylamine the arrangement of Ans. (a)
electrons is as follows : 68 The compound that does not
1s 2s 2p The structure of H3PO2 produce nitrogen gas by the
Electronic structure (hypophosphorous) acid is
of nitrogen atom thermal decomposition is
O [JEE Main 2018]
(ground state)
Three unpaired electrons
(a) Ba(N3)2 (b) (NH4 )2 Cr2O 7
form bonds with CH3 groups P
tetrahedral arrangements of H (c) NH4NO2 (d) (NH4 )2 SO 4
three bond pairs and one HO H
lone pair
Ans. (d)
Due to the presence of twoP  H bonds, The thermal decomposition of given
In trisilylamine, three sp2 orbitals are H3PO2 acts a strong reducing agent. e.g., compounds is shown below
used for σ -bonding, giving a plane +1 +1
triangular structure. 4AgNO3 + H3PO2 + 2H2O → ∆
(NH4 )2 Cr2O7 → N2 + 4H2O + Cr2O3
0 +5
H3Si SiH3
4Ag ↓ + H3 PO4 + 4HNO3 ∆
NH4NO2 → N2 + 2H2O
N N
∆
H 3C CH3 66 The metal that forms nitride by (NH4 )2 SO4 → 2NH3 +H2SO4
CH3 SiH3 reacting directly with N 2 of air, is Ba(N3)2 → Ba + 3N2
N(CH3)3 N(SiH3)3 [2019, 9 Jan Shift-II]
molecule molecule (a) Rb (b) K Thus, only (NH4 )2 SO4 does not givesN2
(c) Cs (d) Li on heating (It giveNH3). While rest of the
64 An organic compound A is oxidised given compounds givesN2 on their
Ans. (d) thermal decomposition.
with Na 2O 2 followed by boiling with Among the group-1 metals, only Li is able
HNO 3 . The resultant solution is then to form its nitride,Li3N. [All alkaline earth 69 The species in which the N-atom is
treated with ammonium molybdate metals of group-2 form their nitride,
in a state of sp hybridisation is
to yield a yellow precipitate. M3N2 ] [JEE Main 2016]
Based on above observation, the 6Li + N2 → 2Li3N (Ruby red solid) (a) NO2− (b) NO −3
element present in the given (Air) (c) NO2 (d) NO2+
I II
compound is [2019, 12 April Shift-I] [3M + N2 → M3N2 ] Ans. (d)
(a) nitrogen Li⊕ is the smallest metal ion of group-1. Species Hybridisation
(b) phosphorus Smaller size ofLi⊕ and larger size of
(c) fluorine nitride ion,N3− , enableLi⊕ to polarise the
spherical electron cloud ofN3− and it N sp2
(d) sulphur –O
gives higher stability toLi3N. O
Ans. (b) O

Organic compound ‘A’ contain 67 The pair that contains two PH N sp2
phosphorus as it gives positive test with –O
bonds in each of the oxoacids is O
ammonium molybdate. Phosphorus
present in organic compound ‘A’ get
(a) H4P2O 5 and H4P2O 6
oxidised withNa2O2 and form Na3PO4 . (b) H3PO 3 and H3PO2 N sp2
(c) H4P2O 5 and H3PO 3 O O
2P + 5Na2O2 → 2Na3PO4 + 2Na2O +
Compound Sodium phosphate
(d) H3PO2 and H4P2O 5 O N O sp
[2019, 10 Jan Shift-II]
204 JEE Main Chapterwise Topicwise Chemistry

70 The pair in which phosphorus (c) Single N—N bond is weaker than the This is due to the absence of empty
single P—P bond 2p− orbital and hence, back donation
atoms have a formal oxidation
(d) N2O4 has two resonance structure does not occur.
state of +3 is [JEE Main 2016]
[AIEEE 2011]
(a) pyrophosphorous and Ans. (a) 74 In which of the following
hypophosphoric acids arrangements, the sequence is not
(b) orthophosphorous and hypophosphoric (a) Thermal stability of the hydrides
decrease as we go down the group strictly according to the property
acids
(c) pyrophosphorous and
in periodic table for group 15 written against it? [AIEEE 2009]
(N-family) (a) CO2 < SiO2 < SnO2 < PbO2
pyrophosphoric acids
(d) orthophosphorous and BiH 3 < SbH 3 < AsH 3 < PH 3 < NH 3 increasing oxidising power
pyrophosphorous acids Least stable Most stable (b) HF < HCl < HBr < HI
Ans. (d) M-H — 255 247 322 391 increasing acid strength
Bond-energy (kJ mol −1) (c) NH3 > PH3 < AsH3 < SbH3
Orthophosphorous acid,H3PO3 :
O (b) Due to absence ofd-orbital, increasing basic strength
 nitrogen can’t form dπ − pπ bond, (d) B < C < O < N
HO P  OH thus it is correct. increasing first ionisation enthalpy
 (c) The N–N bond (BE 160 kJ mol −1) is Ans. (c)
x H weaker than P–P bond (BE 209 kJ
H3 PO3 =3 + x + 3(−2) = 0 or x = + 3 mol −1). Thus, it is correct.
The correct increasing basic strength
SbH3 < AsH3 < PH3 < NH3
Pyrophosphorous acid, (d) N2 O 4 can form two resonance
O O structures NH3 is most basic because of its small
size, the electron density of electron pair
  r r
H4P2O5 : HO P O P OH is concentrated over small region.
O N N O
  As the size increases, the electron
H H – r r density gets diffused over a large
x sO sO O N N O surface area and hence the ability to
H4 P2 O5 = 4 + 2x + 5 (− 2) = 0
donate the electron pair (basicity)
4 + 2x − 10 = 0 ⇒ x = + 3 O O decreases. Hence, basic strength
s
decreases down the group.
Thus, it is correct.
71 Which one of the following
properties is not shown by NO? 75 Regular use of which of the
[JEE Main 2014]
73 The bond dissociation energy of following fertilizers increases the
(a) It is diamagnetic in gaseous state
B—F in BF3 is 646 kJ mol −1 whereas acidity of soil ? [AIEEE 2007]
(b) It is a neutral oxide that of C—F in CF4 is 515 kJ mol −1 . (a) Potassium nitrate
(c) It combines with oxygen to form The correct reason for higher B—F (b) Urea
nitrogen dioxide bond dissociation energy as (c) Superphosphate of lime
(d) Its bond order is2.5 compared to that of C—F is (d) Ammonium sulphate
Ans. (a) [AIEEE 2009]
Ans. (d)
(a) smaller size of B-atom as compared
The electronic configuration of
to that of C-atom (NH4 )2 SO4 → 2NH +4 + SO24−
NO[15 e − ] is given by Acidic
σ 1s 2 , σ * 1s 2 , σ2s 2 , σ * 2s 2 , σ2p2z , π2p2x (b) stronger σ-bond between B and F in
BF3 as compared to that between C 76 Which of the following statements
= π 2p 2y , π * 2p1z and F in CF4
is true ? [AIEEE 2006]
Thus, NO possess one unpaired electron, (c) significant pπ - pπ interaction
hence, it is paramagnetic in nature. between B and F inBF3 whereas (a) H3PO3 is a stronger acid thanH2SO3
However, it dimerises at low there is no possibility of such (b) In aqueous medium, HF is a stronger
temperature to become diamagnetic. interaction between C and F in CF4 acid than HCl
2NO s N2O2 (d) lower degree of pπ - pπ interaction (c) HClO4 is weaker acid thanHClO3
1 between B and F in BF3 than that (d) HNO3 is a stronger acid thanHNO2
Bond order of NO = [10 − 5] = 2.5 between C and F in CF4
2 Ans. (d)
Thus, bond order ofNO is 2.5 and it Ans. (c) Conjugate base of HNO3 is resonance
combines withO2 to give NO2 . Due to identical sizes of2p−orbitals on B stablised than that of HNO2 . Hence,HNO3
Hence, the correct option is (a). and F, back donation of a lone pair of is stronger acid thanHNO2 .
electrons from the filled2p− orbital of F -
to the empty2p -orbital of B occurs to a O O
72 Which of the following statements
considerable extent. HON HN
is wrong?
As a result, B  F bond has some double -
(a) The stability of hydrides increases O O
bond character and hence, bond
from NH3 to BiH3 in group 15 of the
dissociation energy ofB  F bond inBF3 O
periodic table
is much higher that of C  F bond in CF4 . HON No resonance
(b) Nitrogen can’t form dπ-pπ bond
p-Block Elements 205

77 The number of hydrogen atom(s) (a) solvated electron e − (NH3) x Electronic configuration of O2 − is :
(b) solvated atomic sodium, Na(NH3) y 1s 2 , 2s 2 , 2p6
attached to phosphorus atom in
(c) (Na+ + Na− ) Hence,O2 − is also diamagnetic.
hypophosphorous acid is
[AIEEE 2005] (d) NaNH2 + H2 Electronic configuration of O2− is :
(a) three (b) one (c) two (d) zero Ans. (a) σ 1s 2 , σ * 1s 2 , σ2s 2 , σ * 2s 2 , σ2p2x ,
Ans. (c) All alkali metals dissolve in liquid π2p2y ≈ π2p2z , π * 2p2y ≈ π * 2pz1
Hypophosphorous acid (H3PO2 ) is a ammonia and gives solvated Since, unpaired electron is present in
monobasic acid and has only one ammoniated electrons. π *2pz orbital.
ionisable H because two H-atoms are M + (x + y) NH3 → M+ (NH3) x + e − (NH3) y Therefore, O2− is paramagnetic in nature.
directly attached to phosphorus. Thus, These electrons are excited to higher ∴ Only KO2 is paramagnetic oxide.
the correct statement is (c). energy levels and the absorption of
The structure of H3PO2 is photons occurs in the red region of the 83 The depositions of X and Y on
H spectrum. Thus, solution appears blue.
| ground surfaces is referred to as
H P  O  H . Ionisable as directly wet and dry depositions,
|| 81 PCl 3 and PCl 5 both exist; NCl 3
O respectively. X and Y are
exists but NCl 5 does not exist. It is [2021, 31 Aug Shift-II]
attached to O. due to [AIEEE 2002]
(a) X = Ammonium salts, Y = CO2
(a) lower electronegativity of P than N (b) X = SO2 , Y = Ammonium salts
78 Ammonia forms the complex ion (b) lower tendency of N to form covalent
[Cu(NH3 ) 4] 2+ with copper ions in bond
(c) X = Ammonium salts, Y = SO2
the alkaline solutions but not in (c) availability of vacantd-orbital in P but
(d) X = CO2 , Y = SO2
acidic solutions. What is the reason not in N Ans. (c)
for it? [AIEEE 2003] (d) statement is itself incorrect Oxides of nitrogen and sulphur are acidic
(a) In acidic solutions, hydration Ans. (c) and settle down on ground as dry
protects copper ions deposition.
Phosphorus (3rd period element) can
(b) In acidic solutions, protons raise covalency facilitating vacant Ammonium salts in rain drops result in
coordinate with ammonia molecules d-orbitals wet deposition.
forming NH+4 ions and NH3 molecules P (ground) [Ne] 3s 2 3p3 3d 0 ∴ X = Ammonium salts
are not available Y = SO2
P (excited) [Ne] 3s 1 3p3 3d 1
(c) In alkaline solutions, insoluble
Cu(OH)2 is precipitated which is 84 Consider the sulphides HgS, PbS,
soluble in excess of any alkali TOPIC 4 CuS, Sb 2S 3 , As 2S 3 and CdS.
(d) Copper hydroxide is an amphoteric
substance Group 16 Elements Number of these sulphides soluble
Ans. (b)
in 50% HNO 3 is [2021, 31 Aug Shift-I]
82 Number of paramagnetic oxides Ans. (4)
In acidic solutions, N atoms of NH 3
donates their lone pair electrons to among the following given oxides is PbS, CuS, As2S 3, CdS, are soluble in 50%
protons forming NH +4 ions. Therefore, Li 2O, Na 2O 2 , KO 2 , HgO and K 2O HNO3 while HgS,Sb2S 3 are insoluble in
lone pair electrons ofNH3 are not 50% HNO3.
[2021, 1 Sep Shift-II]
available for forming the complex with
copper ions. (a) 1 (b) 2 85 In polythionic acid, H2S x O 6 (x = 3 to
(c) 3 (d) 0
5) the oxidation state(s) of sulphur
79 What would happen when a Ans. (a)
is/are [2021, 27 Aug Shift-I]
solution of potassium chromate is For the oxides Li2O, CaO, Na2O2 ,KO2 , MgO
(a) only + 5 (b) only + 6
treated with an excess of dilute and K2O,
(c) + 3 and + 5 (d) 0 and + 5
nitric acid? [AIEEE 2003] Li2O ⇒ O2 −
Ans. (d)
(a) Cr 3+ and Cr2O2−
7 are formed CaO ⇒ O2 −
(b) Cr2O27− and H2O are formed Na2O2 ⇒ O22 –
Polythionic acid with a small number of
(c) CrO2− sulphur atoms (3 to 5) are most stable.
4 is reduced to +3 state of Cr KO2 ⇒ O2−
(d) None of the above The oxidation state of sulphur in
MgO ⇒ O2 − polythionic acid are 0 and +5 only. They
Ans. (b) have straight chain of sulphur.
K2O ⇒ O2 −
2CrO24− + 2H+ → Cr2O27− + H2O
∴ Electronic configuration of O22 − O O
molecule is 0
80 The metallic sodium dissolves in HO S
+5
Sx S—OH
+5

liquid ammonia to form a deep blue σ 1s 2 , σ * 1s 2 , σ2s 2 , σ * 2s 2 , σ2p2z ,

coloured solution. The deep blue π2p2x ≈ π2p2y , π * 2p2x ≈ π * 2p2y O O
2−
colour is due to the formation of Hence,O2 is diamagnetic in nature as no where x = 3 to 5.
[AIEEE 2002] unpaired electron is present.
206 JEE Main Chapterwise Topicwise Chemistry

86 The product obtained from the H2S2O7 (l ) + H2O(l ) → 2H2SO4 (aq) reversibly between themselves with slow
D. Hall-Heroult process- Aluminium heating (above 369 K) or cooling.
electrolytic oxidation of acidified > 369 K
extraction
sulphate solutions, is Sα - Sβ
[2021, 27 July Shift-I] 2Al2O3 + 3C → 4Al + 3CO2 (Rhombic) Cooling (Monoclinic)

(a) HSO −4 (b) HO 3SOOSO 3H Correct match is, So, statement I is true.
(c) HO2 SOSO2H (d) HO 3SOSO 3H A → (iii), B→ (i), C → (iv), D → (ii)
At room temperature or at standard
Ans. (b) conditions of pressure and temperature,
89 The correct order of electron gain rhombic sulphur is the
Electrolysis of concentrated solution of
enthalpy is [2021, 26 Feb Shift-II] thermodynamically most stable
acidified sulphate solution yields
peroxydisulphuric acid (H2S2O8 ). (a) S > Se > Te > O (b) Te > Se > S > O crystalline allotrope of sulphur (∆fH º = 0).
During electrolysis, (b) O > S > Se > Te (d) S > O > Se > Te So, statement II is false.
At cathode Ans. (a)
2 H2O + 2e − → 2OH− + H2 ↑ Oxygen is the second most 91 Among the following allotropic
At anode electronegative element in comparison forms of sulphur, the number of
to fluorine. In group -16 family (O, S, Se, allotropic forms, which will show
2H2SO4 → H2S2O8 + 2H+ + 2e − Te), O-atom is smallest in size. So,
2H2O → 4H+ + O2 + 2e −
paramagnetism is ……… .
electron density on O-atom is very high [2021, 24 Feb Shift-II]
in group -16 .
87 Chalcogen group elements are (a) α-sulphur (b) β-sulphur
During addition of a free electron to
[2021, 26 Aug Shift-II] (c) S2 -form
gaseous O-atom,
Ans. (1)
(a) Se, Tb and Pu (b) Se, Te and Po O( g) + e − → O− ( g)
(c) S, Te and Pm (d) O, Ti and Po We have to supply a significant amount Only S2 -form of sulphur is paramagnetic
Ans. (b) of energy (endothermic) to overcome the in nature. Because S2 is likeO2 i.e.
electrostatic repulsion between the paramagnetic as per molecular orbital
Oxygen family is also known as theory. It contains unpaired electron.
chalcogen family. approaching electron and O-atom of very
high electron density. So, the net value Whileα-sulphur andβ-sulphur are
O, Se, S, Te and Po are chalcogen family diamagnetic as they do not have
of electron affinity (EA) or (negative)
member. unpaired electron.
electron gain enthalpy
[∆ egH or | ∆ egH | ] of oxygen decreases to
88 Match List -I with List II. a higher extent in comparison to other 92 The number of bonds between
List-I List-II
elements of group -16 who have larger sulphur and oxygen atoms in S 2O 2−
8
size and lower electronegativity. and the number of bonds between
(Industrial (Application)
process) So, the correct order of EA or ∆ egH of sulphur and sulphur atoms in
group -16 elements will be rhombic sulphur, respectively, are
A. Haber’s process (i) HNO3 synthesis
S > Se > Te > O. [2020, 8 Jan Shift-I]
B. Ostwald’s (ii) Aluminium
(a) 4 and 6 (b) 8 and 8
process extraction 90 Given below are two statements. (c) 4 and 8 (d) 8 and 6
C. Contact process (iii) NH3 synthesis Statement I α and β-forms of Ans. (b)
D. Hall-Heroult (iv) H2SO4 synthesis sulphur can change reversibly S2O28− is
process between themselves with slow
Choose the correct answer from heating or slow cooling.
O—S—O—O—S—O
the options given below : Statement II At room
[2021, 16 March Shift-I] temperature, the stable
(a) A-(ii), B-(iii), C-(iv), D-(i) crystalline form of sulphur is Total number of S O or S == O bond = 8
(b) A-(iii), B-(iv), C-(i), D-(ii) monoclinic sulphur. Rhombic sulphur is
(c) A-(iii), B-(i), C-(iv), D-(ii) S S S
In the light of the above S S
(d) A-(iv), B-(i), C-(ii), D-(iii)
statements, choose the correct S
Ans. (c) S S
answer from the options given
A. Haber’s process - NH3 synthesis below. [2021, 25 Feb Shift-II] Total number of S S bond = 8
N2 ( g)+ 3H2 ( g) → 2NH3( g) (a) Both statements I and II are true. Thus, the correct answer is (b).
B. Ostwald’s process - HNO3 synthesis (b) Both statements I and II are false.
4NH3 (g) + 5O2 (g) → 4NO(g) + 6H2O(g) (c) Statement I is true but statement II 93 The acidic, basic and amphoteric
2NO( g) + O2 ( g) → 2NO2 ( g) is false. oxides, respectively, are
(d) Statement I is false but statement II [2020, 9 Jan Shift-I]
4NO2 (g) + 2H2O(l ) + O2 (g) → 4HNO3 (aq)
is true. (a) Cl2O,CaO,P4O 10
C. Contact process - H2SO4 synthesis Ans. (c) (b) N2O 3,Li2O,Al2O 3
2SO2 ( g) + O2 ( g) → 2SO3( g)
Two crystalline allotropic forms of (c) Na2O,SO 3,Al2O 3
SO3( g) + H2SO4 (aq) → H2S2O7 (l ) sulphur (S α and S β ) can change (d) MgO, Cl2O,Al2O 3
Oleum
p-Block Elements 207

Ans. (b) The expression of second electron gain +2 in S2O23−

The acidic, basic and amphoteric oxides, enthalpy of oxygen will be, +4 in SO2
respectively areN2O3, Li2O and Al2O3. The O− (g) + e − → O2 − (g), ∆e gH2 = + ve +6 in SO3
normal oxides of the elements present ∆e gH2 of oxygen is positive, i.e. Thus, incorrect. (Valency can be less
on extreme left of periodic table are endothermic, because a strong than 4)
most acidic (Li2O) as they form strong electrostatic repulsion will be observed Hence, correct option is (d).
base when dissolved in water and oxides between highy negativeO − and the
of the elements present in extreme right incoming electron (e − ). A very high
are acidic (N2O3). The amphoteric oxides amount of energy will be consumed 98 Which one of the following is an
show both the acidic and basic character (endothermic) by the system to amphoteric oxide? [AIEEE 2003]
(Al2O3) . overcome the electrostatic repulsion. (a) ZnO (b) Na2O
(c) SO2 (d) B2O 3
94 The oxoacid of sulphur that does 96 Which of the following is wrong Ans. (a)
not contain bond between sulphur statement? ZnO can react with both acid as well as
atoms is [2019, 10 April Shift-I] (a) ONCl and ONO − are not isoelectronic base to form salt and water.
(a) H2 S2O 3 (b) H2 S2O 4 (b) O3 molecule is bent ZnO + 2HCl → ZnCl 2 + H2O
(c) H2 S2O 7 (d) H2 S4O 6 (c) Ozone is violet-black in solid sate ZnO + 2NaOH → Na2ZnO2 + H2O
Ans. (c) (d) Ozone is diamagnetic gas
[JEE Main 2013]
S  S bond is not present inH2S2O7
(pyrosulphuric acid or oleum). Ans. (*) TOPIC 5
O O (a) Number of electrons in Group 17 Elements
ONCl = 3.2 e − ; ONO− = 24 e −
H2S2O7 ⇒ HO—S—O—S—OH Thus, ONCl and ONO− are not
99 Which one of the following
isoelectronic.
O O
(b) O3 has bent shape structure.
correctly represents the order of
While the other given oxoacids of Central atom O is sp2 hybridised
stability of oxides, X 2O
sulphur, i.e. with 1 lone pair of electrons. (X = halogen) ? [2021, 31 Aug Shift-II]
H2S2O3 (thiosulphuric acid),H2S2O4 (a) Br > Cl > I (b) Br > I > Cl
(hyposulphurous or dithionous acid) and O
(c) Cl > I > Br (d) I > Cl > Br
H2S 4O6 (tetrathionic acid) contains SS O O Ans. (d)
bonds.
O (c) Ozone is violet-black in solid state. Iodine oxygen bond is stable due to
(d) O3 has no unpaired electrons, thus greater polarity of bond. Stability of
H2S2O3 ⇒ HO—S—OH it is diamagnetic. chlorine oxygen bond is due to multiple
bond formation of oxygen withd-orbital
Hence, all the given statements
S of chlorine atom.
are correct.
O OH Bromine lacks both these
H2S2O4 ⇒ S——S characteristics. So, the stability order of
HO
97 Which of the following statements oxide is I > Cl > Br.
O
regarding sulphur is incorrect?
O O [AIEEE 2011]
100 The number of halogen (s) forming
H2S4O6 ⇒ HO—S—S—S—S—OH (a) S2 molecule is paramagnetic
halic (V) acid is [2021, 31 Aug Shift-I]
(b) The vapour at 200°C consists mostly
O O of S 8 rings Ans. (3)
(c) At 600°C, the gas mainly consists of The halic (V) acids formed by chlorine
S2 molecules (Cl), bromine (Br) and iodine (I) areHClO3,
95 When the first electron gain
(d) The oxidation state of sulphur is HBrO3 and HIO3 respectively.
enthalpy (∆ e g H) of oxygen is never less than +4 in its compounds
− 141kJ /mol, its second electron 101 Which one of the following is used
Ans. (d)
gain enthalpy is to remove most of plutonium from
(a) S2 molecule is paramagnetic due
(a) a positive value to unpaired electrons in MO and is spent nuclear fuel?
(b) a more negative value than the first blue coloured compound, thus [2021, 27 Aug Shift-II]
(c) almost the same as that of the first true. (a) ClF3 (b) O2F2 (c) I2O 5 (d) BrO 3
(d) negative, but less negative than the (b) The vapour at 200°C consists Ans. (b)
first [2019, 9 Jan Shift-II] mostly of S 8 rings, thus correct.
Ans. (a) (c) At 600°C, the gas mainly consists Dioxygen difluoride is used to remove
of S2 molecules, thus correct. the plutonium from spent nuclear fuel.
As given, the first electron gain enthalpy
(d) Oxidation states of sulphur are 3F  O O F + Pu →
of oxygen can be shown as, (From nuclear
O(g) + e − → O− (g), −2 in H2S fuel)
PuF6 + 3O2 ↑
∆e gH1 = − 141 kJ/mol 0 in S8
Therefore, the option (b) is correct.
208 JEE Main Chapterwise Topicwise Chemistry

102 Number of Cl==O bonds in chlorous But magnitude of electron gain enthalpy O
of second period element F is slightly
acid, chloric acid and perchloric less than third period element ‘Cl’ owing Cl —OH
acid respectively are to its small size. Due to small size of ‘F’ O O
[2021, 27 July Shift-II] there is high electronic repulsion
Thus, Cl== O bond is 3.
(a) 3, 1 and 1 (b) 4, 1 and 0 between the existing and approaching
electron. Hence, the correct answer is 3.
(c) 1, 1 and 3 (d) 1, 2 and 3
Ans. (d) Hence, magnitude of electron gain
enthalpy decreases. 108 Chlorine reacts with hot and
Structure of chlorous acid, chloric acid concentrated NaOH and produces
and perchloric acid are shown below compounds (X ) and (Y ). Compound
105 The correct order of bond
dissociation enthalpy of halogens is (X ) gives white precipitate with
Cl H Cl H Cl H [2021, 25 Feb Shift-II] silver nitrate solution. The average
O O O
(a) F2 > Cl2 > Br2 > I2 bond order between Cl and O atoms
Chlorous
(b) I2 > Br2 > Cl2 > F2 in (Y ) is …… . [2020, 7 Jan Shift-I]
acid Chloric acid Perchloric acid (c) Cl2 > Br2 > F2 > I2 Ans. (1.67)
Formula HClO 3 HClO 4
(d) Cl2 > F2 > Br2 > I2
HClO2 The reaction is,
No. of 1 2 3
Ans. (c)
3Cl2 + 6 NaOH 5 NaCl + NaClO3 + 3H2O
Cl == O Among halogens ( F2 , Cl2 , Br2 and I2 ), bond (X) (Y)
dissociation enthalpy (∆ dissH°) of I2 , is
+ AgNO3
103 Choose the incorrect statement. minimum because of larger size of
I-atom there is a steric repulsion AgCl
[2021, 26 Aug Shift-I]
between bonded I-atoms, which makes (white ppt.)
(a) Cl2 is more reactive than CIF.
I  I bond weakest. +
Y = NaClO3 (Na and ClO3 )
–
(b) F2 is more reactive than CIF.
Whereas, smaller size and highest –
The structure of ClO3 (chlorate ion) is,
(c) On hydrolysis CIF froms HOCl and HF.
electronegativity of F-atom cause
(d) F2 is a stronger oxidising agent than highest electron density on F-atom ofF2 Cl Cl == Cl
Cl
Cl2 in aqueous solution. molecule. O O O O
O O O O O O O
O
Ans. (a) As a result, F F bond becomes weaker
‘ClO’ bond order in the hybrid
The Cl2 is more reactive than ClF is due to electrostatic repulsion between
Number of bonds between Cl and O
incorrect statement as reactivity order bonded =
can be written as follows F-atoms. Total number of O (surrounding atoms)
F2 > ClF (interhalogen compounds) > Cl2 . Thus, the order of ∆ dissH° (in kJ mol −1) is 5
= = 166
. or 1.67
Interhalogen compounds are more Cl  Cl > Br Br > F  F > I I 3
reactive than pure halogen compounds (242.6) (192.3) (158.8) (151.1)
as the bonds are polar and weaker than Electrostatic
repulsion
Steric
repulsion
109 Among the following reactions of
pure halogen compounds. hydrogen with halogens, the one
∴ statement (a) is incorrect. 106 Among the following, the number that requires a catalyst is
F2 is highly reactive among all of halide(s) which is/are inert to (a) H2 + Cl2 → 2HCl
interhalogens or pure halogen
hydrolysis is …………… . (b) H2 + I2 → 2HI
compounds due to strong (c) H2 + F2 → 2HF
[2021, 25 Feb Shift-I]
interelectronic repulsion between
(i) BF3 (ii) SiCl 4 (d) H2 + Br2 → 2HBr
F-atoms.
[2019, 10 Jan Shift-II]
(iii) PCl 5 (iv) SF6 Ans. (b)
104 The absolute value of the electron Ans. (1)
gain enthalpy of halogens satisfies Chemical reactivity of halogens
[2021, 17 March Shift-I]
BF3, SiCl 4 and PCl 5 are easily hydrolysed decreases down the group.
whileSF6 is inert to hydrolysis due to the The chemical reactivity follows the
(a) I > Br > Cl > F (b) Cl > Br > F > I presence of sterically protected sulphur
(c) Cl > F > Br > I (d) F > Cl > Br > I order.
atom by six F atoms, which does not
Ans. (c) permit the reactions like hydrolysis to ∴ F2 > Cl2 > Br2 > I2 .
take place. The highest reactivity of fluorine is
Order of electron gain enthalpy
Thus, only 1 halide is inert to hydrolysis. attributed to two factors :
(absolute value)
(i) The low dissociation energy of
Cl > F > Br > I
107 The number of Cl == O bonds in F—F bond (which results in low
Element F Cl Br I attraction energy for the reaction).
perchloric acid is ‘‘..........’’.
[2020, 6 Sep Shift-I] (ii) Very strong bonds which are
∆He g (kJ/mol) − 328 − 349 − 325 − 295 formed.
Ans. (3.00)
Both properties arise from, small
Absolute value of electron gain enthalpy Perchloric acid isHClO4 . Structure of size of fluorine.I2 is being the least
decreases down the group in a periodic HClO4 is
table due to increase in size.
p-Block Elements 209

reactive halogen, it requires a hydrogen bond exists between hydrogen 115 Chlorine on reaction with hot and
catalyst for the reaction. of one molecule and fluorine atom of
oncentrated sodium hydroxide
H2 + I2 → 2HI another molecule as shown below.
δ+ δ− δ+ δ− δ+ δ−
gives [2019, 12 Jan Shift-II]
… H F … H F … H F (a) Cl− and ClO − (b) Cl− and ClO −3
110 What products are expected from
In this molecule, hydrogen bond behaves (c) ClO −3 and ClO2− (d) Cl− and ClO2−
the disproportionation reaction of
like a bridge between two atoms that Ans. (b)
hypochlorous acid ? [AIEEE 2006]
holds one atom by covalent bond and the Halogens form halates and halides with
(a) HClO 3 and Cl2O other by hydrogen bond. hot and concentrated solution of NaOH
(b) HClO2 and HClO 4 as :
(c) HCl and Cl2O 113 The chloride that cannot get 3X2 + 6NaOH → 5NaX + NaXO3 + 3H2O
(d) HCl and HClO 3 hydrolysed is [2019, 11 Jan Shift-I]
So, Cl2 will also give Cl − (as NaCl) and
Ans. (d) (a) SnCl4 (b) CCl4 ClO−3
3HOCl → 2HCl + HClO3 (c) PbCl4 (d) SiCl4 (as NaClO3) in the above reaction.
Ans. (b) Thus, option (b) is correct.
111 The correct statement aboutICl 5 and The compounds given are the Note When halogens react with cold and
tetrahalides dilute solution of NaOH, hypohalites and
ICl −4 is [2019, 8 April Shift II]
(MCl 4 ) of group 14 elements. For the halides are produced as:
(a) ICl 5 is square pyramidal andICl −4 is hydrolysis, (nucleophilic substitution) of X2 + 2NaOH → NaX + NaXO + H2O
tetrahedral MCl 4 the nature of the M—Cl bond should
(b) ICl 5 is square pyramidal andICl −4 is be as: 116 Total number of lone pair of
square planar
δ+
δ – electron in I −3 ion is [JEE Main 2018]
(c) Both are isostructural
M——Cl (a) 3 (b) 6 (c) 9 (d) 12
(d) ICl 5 is trigonal bipyramidal and ICl −4 is
tetrahedral It must expand its covalency beyond 4 by the use Ans. (c)
Ans. (b) of its vacant d-orbital which will accommodate the The structure of I−3 ion is
lone pair of electrons of H2O (the–nucleophile).
• • –
For I Cl 5
1 sp3d I
H= (7 + 5 − 0 + 0) = 6 (sp3d2 ) sp3
2 Cl3 M—— Cl Cl3 M——Cl
[refer the solution of Q. No. 4] d + d – OH2
d0 O
Cl
sp3d2 -hybridised H H I
–HCl
Cl Cl Transition state
Geometry : Octahedral
I Shape / Structure : sp3
3H2O I
Square pyramidal M(OH)4 Cl3 M—(OH)
Cl Cl –3HCl

For &&I Cl −4 Here, M can be Si, Sn and Pb because they Hence, 9 is the correct answer.
1 have vacant nd-orbital. But, carbon is a
H = (7 + 4 − 0 + 1) = 6 (sp3d2 ) member of second period (n = 2,l = 0, 1), it 117 The products obtained when
2
does not haved-orbital (l = 2). So, CCl 4 will chlorine gas reacts with cold and
Cl Cl sp3d2 -hybridised not be hydrolysed and correct option is
s dilute aqueous NaOH are
(b). [JEE Main 2017]
I Geometry : Octahedral
Shape/Structure : Square (a) ClO − and ClO −3 (b) ClO2− and ClO −3
Cl Cl planar 114 Iodine reacts with concentrated
(c) Cl− and ClO − (d) Cl− and ClO2−
HNO 3 to yield Y along with other
So, ICl 5 and ICl −4 are isolobal but not products. The oxidation state of
Ans. (c)
isostructural. Cl2 , Br2 and I2 form a mixture of halide
iodine in Y, is [2019, 12 Jan Shift-I]
and hypohalites when react with cold
(a) 1 (b) 3
112 HF has highest boiling point among dilute alkalies while a mixture of halides
(c) 7 (d) 5 and haloate when react with concentrated
hydrogen halides, because it has
[2019, 10 April Shift-I]
Ans. (d) cold alkalies.
(a) lowest ionic character Iodine reacts with concentratedHNO3to Cl2 + 2NaOH → NaCl + NaClO + H2O
(b) strongest van der Waals’ yield HIO3 along with NO2 and H2O. The Cold and dilute
reaction involved in as follows :
interactions ∴ Cl − and ClO− are obtained as products
(c) strongest hydrogen bonding I2 + 10HNO3 → 2HIO3 + 10NO2 + 4H2O when chlorine gas reacts with cold and
(d) lowest dissociation enthalpy The oxidation state of ‘I’ in HIO3 is + 5 as dilute aqueous NaOH.
Ans. (c) calculated below :
1 + x + 3(−2) = 0 118 Which among the following is the
HF has highest boiling point among
x − 5=0 most reactive? [JEE Main 2015]
hydrogen halides because it has
strongest hydrogen bonding. Here, the x=+5 (a) Cl2 (b) Br2 (c) I2 (d) ICl
210 JEE Main Chapterwise Topicwise Chemistry

Ans. (d) – Ans. (c)

O O
Cl2 , Br2 and I2 are homonuclear diatomic In a group, ∆G °f (HX) changes from
molecule in which electronegativity of ClO2– Cl Cl negative to positive downwards.
the combining atoms is same, so they – HF (g), ∆G = − 273.20 kJ mol −1
O O
are more stable and less reactive, HI(g), ∆G = + 1.72 kJ mol −1
whereas, I and Cl have different
Thus, HF is thermally stable and HI not.
electronegativities and bond between ClO− does not show resonance. Thus, the
them are polarised and hence, reactive. stability order of conjugate base due to Thus, HF > HCl > HBr > HI
Therefore, interhalogen compounds are resonance is
more reactive. ClO−4 > ClO−3 > ClO2− > ClO−
123 Concentrated hydrochloric acid
Time Saving Technique In this type of Hence, the acidic strength of given when kept in open air sometimes
question of halogen, only go through the oxoacids is as follows produces a cloud of white fumes.
polarity of the molecule. As we know, HClO4 > HClO3 > HClO2 > HClO The explanation for it is that
diatomic molecule does not have polarity
(a) concentrated hydrochloric acid
but molecules with dissimilar sizes have
polarity resulting in more reactivity.
120 Identify the incorrect statement emits strongly smelling HCl gas all
among the following [AIEEE 2007] the time
(a) Ozone reacts withSO2 to give SO3 (b) oxygen in air reacts with the emitted
119 Among the following oxoacids, the HCl gas to form a cloud of chlorine
correct decreasing order of acid (b) Silicon reacts with NaOH (aq) in the
presence of air to giveNa2SiO3 and gas
strength is H2O (c) strong affinity of HCl gas for
(a) HOCl >HClO2 >HClO3 >HClO4 (c) Cl2 reacts with excess ofNH3 to give moisture in air results in forming of
(b) HClO4 > HOCl >HClO2 >HClO3 N2 and HCl droplets of liquid solution which
(c) HClO4>HClO3 >HClO2 > HOCl appears like a cloudy smoke
(d) Br2 reacts with hot and strong NaOH
(d) HClO2 >HClO4>HClO3 > HOCl solution to give NaBr, NaBrO4 and H2O (d) due to strong affinity for water,
[JEE Main 2014] concentrated hydrochloric acid pulls
Ans. (d) moisture of air towards itself. This
Ans. (c) Br2 reacts with hot and strong NaOH to moisture forms droplets of water and
Acidic strength of oxoacids depends give NaBr, NaBrO3 and H2O. hence, the cloud [AIEEE 2003]
upon the stability of conjugate base. Ans. (b)
More stable the conjugate base of an 121 A metal, M forms chlorides in its +2 1
acid, stronger is the acid. 2HCl + O2 → H2O + Cl2
and +4 oxidation states. Which of 2
HClO4 S ClO−4 + H+ the following statements about
HClO3 S ClO−3 + H+ these chlorides is correct?
HClO2 S ClO2− + H+ [AIEEE 2006] TOPIC 6
HOCl S ClO− + H+ (a) MCl2 is more volatile than MCl 4
Group 18 Elements
Conjugate bases stabilizes by (b) MCl2 is more soluble in anhydrous
resonance. ethanol than MCl 4
O
-
(c) MCl2 is more ionic than MCl 4 124 Match List-I with List-II.
O
(d) MCl2 is more easily hydrolysed than List-II
MCl 4 List-I (Number of lone
ClO4– Cl Cl
Ans. (c) (Species) pair of electrons on
–
O O O the central atom)
O In MCl2 , oxidation state of M = + 2
O O
In MCl 4 , oxidation state of M = + 4 A. XeF2 1. 0
Higher the oxidation state, smaller is the
O B. XeO2F2 2. 1
O size.
Greater the polarising power, greater is C. XeO3F2 3. 2
Cl the covalent characteristic.
Cl D. XeF4 4. 3
–
O O Hence, MCl 4 is more covalent and MCl2 is
O O more ionic
O
- O Choose the most appropriate
answer from the options given
ClO3– 122 The correct order of the thermal
below : [2021, 27 Aug Shift-I]
stability of hydrogen halides (H — X)
– O A B C D
O O is [AIEEE 2005]
(a) 4 1 2 3
(a) HI > HCl > HF > HBr
(b) 3 4 2 1
Cl Cl Cl (b) HCl < HF > HBr < HI
(c) 3 2 4 1
O –
O O (c) HF > HCl > HBr > HI
–
(d) HI > HBr > HCl > HF (d) 4 2 1 3
O O O
p-Block Elements 211

Ans. (d) Ans. (a) Ans. (a)

The geometries of [XeF5 ] – In XeOF4 , Xe is sp3d2 -hybridised.
F Geometry of the molecule is octahedral,
F but shape of the molecule is square
Three lone F Xe : sp3d3-hybridised
A. XeF2 Xe pyramidal.
pairs s Geometry = Pentagonal
Xe F bipyramidal According to VSEPR, theory it has one π
F bond. Remaining six electron pairs form an
F Shape/Structure
F = Pentagonal planar octahedron with one position occupied
F
O by a lone pair.
B. XeO2F2 Xe O
One lone XeO 3F2 F F
O
F pair
Number of bp = 5
F Xe: sp3d-hybridised Xe
F O Number of lp = 1
Zero lone Geometry = Shape/ structure
O pair Xe O
C. XeO3F2 O Xe = Trigonal bipyramidal F F
O [because, Xe in XeO3F2 does not
O F Here, Xe contains one lone pair of
F have pair of electrons] electrons.

F F 127 The reaction in which the 129 The noble gas that does not occur
Two lone
D. XeF4 Xe pairs hybridisation of the underlined in the atmosphere is
F F [2019, 10 April Shift-II]
atom is affected is
[2020, 4 Sep Shift-II] (a) Ra (b) Kr (c) He (d) Ne
So, the correct match is A-4, B-2, C-1, (a) XeF4 + SbF5 → Ans. (a)
D-3. 420 K Radium (Ra) is a radioactive element. Ra
(b) H2 SO 4 + NaCl →
belongs to group 2 (alkaline earth
125 A xenon compound ‘A’ upon partial Disproportionation metals), it is not a noble gas.
(c) H3PO2 →
hydrolysis gives XeO2F2. The Note In question noble gas which does
number of lone pair of electrons H+ not exist in the atmosphere is asked and
(d) NH3 →
present in compound A is ……… answer is Ra. But Ra (radium) is an
Ans. (a) alkaline earth metal and not noble gas. It
(Round off to the nearest integer).
[2021, 18 March Shift-II] Complete reaction with change in can be Rn (radon) and is misprint in JEE
hybridisation is as follows : Main Paper.
Ans. (19)
(a) XeF4 + SbF5 → [XeF3] + [SbF6 ] −
Xenon hexa fluoride (A) on partial 130 Which one has the highest boiling
hydrolysis gives XeO2F2 as a product. sp3d 2 sp3d
Change in hybridisation point? [JEE Main 2015]
XeF6 + 2H2O → XeO2F2 + 4HF (a) He (b) Ne (c) Kr (d) Xe
(A ) Partially
Xenon (b)H2 SO4 + 2NaCl → Na2SO4 + 2HCl
Ans. (d)
hexa fluoride
sp3
As we move down the group of noble
Structure of XeF6 sp3
No change in hybridisation gases, molecular mass increases by
which dipole produced for a moment and
F Disproportionation
(c) H3PO2 → H3PO4 + PH3 hence London forces increases from He
∆
F F to Xe. Therefore more amount of energy
sp3 sp3
Xe No change in hybridisation is required to break these forces, thus
F F + boiling point also increases from He to Xe.
•• +
(d) N H3 N→ NH4
F sp3 sp3 131 Which one of the following reaction
No change in hybridisation
∴Total no. of lone pair = lone pair on of xenon compounds is not
Xe + 6 × lone pair on F = 1 + 6 × 3 = 19 In the reaction (a), hybridisation of Xe in feasible? [AIEEE 2009]
XeF4 is sp3d2 converted into [XeF3] + and (a) XeO 3 + 6HF → XeF6 + 3H2O
126 The shape/structure of [XeF5] − hybridisation of Xe in [XeF3] + is sp3d. (b) 3XeF4 + 6H2O → 2Xe + XeO 3
In this reaction, sp3d2 -hybridisation +12HF + 1.5O2
and XeO 3F2 , respectively, are change into sp3d.
[2020, 2 Sep Shift-II] (c) 2XeF2 + 2H2O → 2Xe + 4HF + O2
(a) pentagonal planar and trigonal (d) XeF6 + RbF → Rb[XeF7]
128 The type of hybridisation and
bipyramidal Ans. (a)
number of lone pair(s) of electrons
(b) octahedral and square pyramidal XeF6 has much tendency to hydrolyse.
of Xe in XeOF 4 , respectively, are
(c) trigonal bipyramidal and pentagonal The reverse reaction is more
[2019, 10 Jan Shift-I]
planar spontaneous.
(a) sp 3d2 and 1 (b) sp 3d and 2
(d) trigonal bipyramidal and trigonal XeF6 + 3H2O → XeO3 + 6HF
bipyramidal (c) sp 3d and 1 (d) sp 3d2 and 2
18
d and f-Block Elements
TOPIC 1 (a) 3.87, 1.73, 0 (b) 1.73, 3.87, 0 04 In the ground state of atomic
Characteristics of (c) 1.73, 0, 3.87 (d) 0, 3.87, 1.73 Fe(Z = 26), the spin-only magnetic
d-block Elements Ans. (b) moment is ………… × 10 −1 BM.
Spin magnetic moment is a magnetic (Round off to the nearest integer).
moment caused due to the spin of [Given : 3 = 1.73, 2 = 1.41]
01 The nature of oxides V2O 3 and CrO
particles. [2021, 17 March Shift-II]
is indexed as ‘X’ and ‘Y ’ type The formula to find the spin only
Ans. (49)
respectively. The correct set of X magnetic moment is,
and Y is [2021, 27 Aug Shift-I] µ = n(n + 2) Electronic configuration of Fe :
1s 2 2s 2 2p6 3s 2
(a) X = basic, Y = amphoteric where, n = number of unpaired electrons
In 3d 6 , number of unpaired electrons
(b) X = amphoteric, Y = basic Ti3+ (22) → [Ar] 3d 1 (n) = 4
(c) X = acidic, Y = acidic
Spin only magnetic moment
(d) X = basic, Y = basic
= n(n + 2) BM
Ans. (d) 3d 4s
= 4(4 + 2)
V2O3 is a basic oxide as on dissolving in = 24 = 49 .
acids, give solution of vanadium (III) 4p = 49 × 10 − 1
complexes. In case of transition metal
oxide, the metal with lower oxidation Only 1 unpaired electron. Nearest integer value will be 49.
states are basic. So, CrO is also basic as ∴ n= 1
oxidation state of Cr is +2. µ = 1 (1 + 2)
05 The common positive oxidation
= 3 = 1.73 BM
states for an element with atomic
02 Which one of the following when number 24, are
dissolved in water gives coloured V2 + (23) → [Ar] 3d3 [2021, 17 March Shift-II]
solution in nitrogen atmosphere? (a) + 2 to + 6
[2021, 26 Aug Shift-I] (b) + 1 and + 3 to + 6
3d 4s
(a) CuCl2 (b) AgCl (c) ZnCl2 (d) Cu2Cl2 (c) + 1 and + 3
Ans. (a) (d) + 1 to + 6
CuCl2 will dissolve in water to give blue 4p Ans. (a)
colour Cu2 + ions. The colour is due to the 3 unpaired electrons. Common positive oxidation states for an
presence of unpaired e − in Cu2 + ions. ∴ n=3 element with atomic number 24, are + 2
CuCl2 + nH2O → Cu2 + (aq) µ = 3(3 + 2) = 15 to + 6.
(Blue colour)
Chromium (Z = 24)
= 3.87 BM
AgCl and Cu2 Cl2 are insoluble in water Electronic configuration: [Ar] 4s 1 3d 5
Sc3 + (21) → [Ar] 3d 0 4s 0
whileZnCl2 on dissolving in water forms
It has five electrons in 3d-subshell and
colourless solution due to formation of
one electron in4s -subshell. Thus,
Zn2 + ions, which has no unpaired e − . chromium metal has six valence
3d 4s
electrons. Chromium can lose some or
03 The spin only magnetic moments all of its valence electrons to form ions
(in BM) for free Ti 3+ , V 2+ , and Sc 3+ 4p
with different oxidation states. Thus,
ions respectively are chromium shows the oxidation states of
No electron, n=0 + 1, + 2, + 3, + 4, + 5 and + 6 respectively.
(Atomic number: Sc = 21, Ti = 22, V ∴ µ = 0 (0 + 2) The most common oxidation states of
= 23) [2021, 25 July Shift-II]
=0 chromium are + 2, + 3 and + 6.
d and f-Block Elements 213

06 The major components of German density increase across the period from (c) Cu, Ni and Fe
left to right. (d) Al, Cu, Mg and Mn
silver are [2021, 25 Feb Shift-II]
(a) Cu, Zn and Ag Metal Density (g/cm3 ) Ans. (a)
(b) Cu, Zn and Ni Zn 7.13 ‘Gun metal’ also called as red brass (in
(c) Ge, Cu and Ag Cr 7.19 USA). It is greyish in colour and originally
(d) Zn, Ni and Ag Fe 7.8 used for making guns. The major
Co 8.7 components of ‘Gun metal’ are
Ans. (b)
Cu 8.9 Cu = 87%
The major components of German silver
are Cu : 25-30%, Zn : 25-30% and Ni : Correct order is Zn = 3%
40-30%. Cu > Co > Fe > Cr > Zn. Sn = 10%
It is also used in manufacturing of gears
07 In which of the following pairs, the 10 Given below are two statements. and bearing that are to be subjected to
outer most electronic Statement I Colourless cupric heavy loads and low speeds.
configuration will be the same? metaborate is reduced to cuprous
[2021, 25 Feb Shift-I] 12 The electrode potential of M 2 + / M
metaborate in a luminous flame.
(a) V2+ and Cr + (b) Cr + and Mn2+ of 3d-series elements shows
Statement II Cuprous metaborate
(c) Ni2+ and Cu + (d) Fe2+ and Co + positive value for
is obtained by heating boric
Ans. (b) [2021, 24 Feb Shift-I]
anhydride and copper sulphate in
(a) V 2+ 3
- [Ar] 3d ; +
Cr - [Ar] 3d 5 (a) Fe (b) Co
a non-luminous flame. (c) Zn (d) Cu
+ 5 2+ 5
(b) Cr - [Ar] 3d ; Mn - [Ar] 3d In the light of the above Ans. (d)
(c) Ni2 + - [Ar] 3d 8 ; Cu+ - [Ar] 3d 10 statements, choose the most In the electrode potential series, only
(d) Fe2 + - [Ar] 3d 6 ; Co+ - [Ar] 3d 7 4s 1 appropriate answer from the copper have positive value for electrode
Thus, in option (b), both ions have same options given below. potential because copper has lower
outer most electronic configuration. [2021, 24 Feb Shift-I] tendency than hydrogen to form ions.
(a) Both statement I and statement II So, if standard hydrogen electrode
08 The incorrect statement among are true. (E Cell = 0) is connected to copper
the following is [2021, 24 Feb Shift-II] (b) Both statement I and statement II half-cell, the copper with be relatively
are false. less negative or less number of
(a) VOSO4 is a reducing agent.
(c) Statement I is true but statement II electrons.
(b) Cr2O3 is an amphoteric oxide.
is false. E° = + 0.34 V;
(c) RuO4 is an oxidising agent. (Cu2 + / Cu)
(d) Red colour of ruby is due to the (d) Statement I is false but statement II E ° 2+ = − 0.41 V
presence of Co3+ . is true. (Fe /Fe )

Ans. (b) E ° +2 = − 0.28 V ;

Ans. (d) Co / Co
(i) In presence of luminous flame, blue °
Red colour of ruby is due to presence of E = −0.76 V
cupric metaborate is reduced to (Zn2 + / Zn)
Cr 3+ ions in Al2O3. Chromium is the trace
colourless cuprous metaborate. ∴ Electrode potential of Cu E °
element that causes ruby’s red colour, Cu +2 / Cu
which ranges from an orange red to a 2Cu(BO2 )2 + 2NaBO2 + C
Luminous
→ show positive value.
flame
publish re(d) The strength of ruby’s red
depends on how much chromium is 2CuBO2 + Na2B4O7 + CO 13 The set that contains atomic
present. If non-luminous flame is present in numbers of only transition
reaction, cupric metaborate is obtained
elements, is [2020, 6 Sep Shift-I]
09 What is the correct order of the by heating boric anhydride with copper
sulphate. (a) 37, 42, 50, 64
following elements with respect to
Non- luminous (b) 21, 25, 42, 72
their density ? [2021, 24 Feb Shift-II] CuSO4 + B2O3 → Cu(BO)2 (c) 9, 17, 34, 38
f lame
(a) Cr < Zn < Co < Cu < Fe Cupric metaborate
(d) 21, 32, 53, 64
(b) Zn < Cu < Co < Fe < Cr + SO3
Ans. (b)
(c) Zn < Cr < Fe < Co < Cu
11 The major components in Gun d-block elements in the periodic table
(d) Cr < Fe < Co < Cu < Zn
are called transition elements. The set
Ans. (c) metal are [2021, 24 Feb Shift-I]
that contains atomic number of only
Generally, due to decrease in metallic (a) Cu, Sn and Zn transitive elements is 21, 25, 42, 72.
radius and increase in atomic mass (b) Cu, Zn and Ni
214 JEE Main Chapterwise Topicwise Chemistry

d-block
21 22 23 24 25 26 27 28 29 30 Sc (atomic no.) 21
Sc Ti V Cr Mn Fe Co Ni Cu Zn
39 40 41 42 43 44 45 46 47 48 Mn (atomic no.) 25
Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
57 72 73 74 75 76 77 78 79 80 Mo (atomic no.) 42
La Hf Ta W Re Os Ir Pt Au Hg
89 104 105 106 107 108 109 110 111 112 Hf (atomic no.) 72
Ac Rf Db Sg Bh Hs Mt Ds Rg Uun
Hence, the correct option is (b).

14 Consider the hydrated ions of n=3 n=4 n=0 n=0

Ti 2+ , V 2+ , Ti 3+ and Sc 3+ . The [Qn = no. of unpaired electrons] Fe2 + 3d 4s 4p
correct order of their spin-only ∆°HAtomisation (kJ mol −1)
magnetic moment is 4d
[2019, 10 April Shift-I] = 515 418 339 130
(a) Sc 3+ < Ti3+ < Ti2+ < V2+ So, absence of unpairedd-electrons and n1=4
(b) Sc 3+ < Ti3+ < V2+ < Ti2+ larger size of Zn atoms, make the crystal
2+
lattice of Zn less closely packed. Ni 3d 4s 4p
(c) Ti3+ < Ti2 + < Sc 3+ < V2 +
(d) V2 + < Ti2 + < Ti3+ < Sc 3+
16 The highest value of the calculated 4d
Ans. (a)
spin only magnetic moment (in BM)
The spin only magnetic moment (µ ) of among all the transition metal n1=2
each ion can be calculated as :
complexes is [2019, 9 Jan Shift-I]
Ni2+
does not form low spin
µ = n (n + 2) BM
(a) 5.92 (b) 3.87 (c) 6.93 (d) 4.90 octahedral complexes.
[Qn = No. of unpaired electron(s)]
⇒ µ ∝ n, i.e. higher the number of Ans. (a) Co2 + 3d 4s 4p
unpaired electron, higher will be the The spin only magnetic moment (µ) (in
value of µ. BM) is given by 4d
n (for metal ion) M (BM) Nature
µ (in BM) = n(n + 2)
Metal ion Z
where, n = number of unpaired electrons ∴ n1=3
Ti2 + 22 2 (3d2 ) 8 Parama
gnetic The highest value of n in transition metal
V2 + 3 (3d 3) complex is 5 in itsd 5 -configuration. Number of e − in low spin complex (n2 )
23 15 Parama n2 − n1
gnetic ∴ µ = 5(5 + 2) BM = 5.916 BM
Ti3+ 22 1 (3d 1) 3 Parama 3d 4s 4p 5− 1 = 4
= 5.92 BM
gnetic
Sc 3+ 21 0 (3d 0 ) 0 Diamag 17 The difference in the number of 4d
netic
unpaired electrons of a metal ion in
Thus, the correct order of spin only n2=1
its high-spin and low-spin
magnetic moments of given hydrated
ions will be
octahedral complexes is two. The 3d 4s 4p 4−0 = 4
Sc3+ < Ti3+ < Ti2 + < V2 +
metal ion is [2019, 10 Jan Shift-II]
(a) Mn2+ (b) Fe2+ 4d
15 The transition element having least (c) Ni2+ (d) Co2+
enthalpy of atomisation is Ans. (d) n2=0
(a) Zn (b) V The difference in the number of
(c) Fe (d) Cu unpaired electrons of different metal 3d 4s 4p 3− 1 = 2
[2019, 9 Jan Shift-II] ions in their high spin and low spin
Ans. (a) octahedral complexes are given in the 4d
table below :
For transition metals,
° Metal ion Number of e − in high spin complex ∴ n1=1
∆HAtomisation ∝ Strength of metallic
(n1 )
bonding
Mn2 + 3d 4s 4p
∝ Number of unpaired electrons 18 The element that usually does not
in the metal atom show variable oxidation states is
4d
For the given3d-transition metals, [2019, 1 Jan Shift-I]
V Fe Cu Zn (a) Sc (b) Cu
n1=5
3d 34s 2 3d 64s 2 3d 104s 1 3d 104s 0 (c) Ti (d) V
d and f-Block Elements 215

Ans. (a) (host lattice). Examples of small atoms belong to beryl lattice
The most stable oxidation states in the (guest atom) are H, B, C and N. (Be3Al2Si6O18 ).
compounds of the given transition Interstitial compounds are Thus, statement (a) is incorrect.
metals of 3d-series are, non-stoichiometric (Birtholide) in (b) [Co(Cl)(NH3) 5 ]2 + is a low spin
Sc : + 3; Ti : + 3, + 4; V : +2, + 3, + 4, + 5; composition. They are very hard with octahedral complex of Co3+ . It
Cu : + 1, + 2 very high melting points. The electrical absorbs low energy yellow light
conductivity of interstitial compounds
The electronic configuration of Sc (Z = and high energy complementary
are comparable to that of the pure
21) is [Ar] 3d 1, 4s 2 . violet light will be shown off. Thus,
metal. These are chemically unreactive
Due to the presence of only one statement (b) is correct.
in nature.
3d-electron
It is a hexadentate ligand. (c) [Fe(H2O) 6 ]2 + and [Cr(H2O) 6 ]2 + are
(no pairing energy) and two 4s-electrons, the high-spin octahedral
they easily ionise to achieve most stable complexes of Fe2 + (3d 6 , n = 4) and
+3 oxidation state. 21 The correct order of the first
Cr2 + (3d 5 , n = 5) ions and weak field
ionisation enthalpies is
[2019, 10 April Shift-II] ligand,H2O respectively. So,
19 The pair of metal ions that can spin-only magnetic moment
given a spin-only magnetic (a) Mn < Ti < Zn < Ni
= n(n + 2) of the complexes.
moment of 3.9 BM for the complex (b) Ti < Mn < Zn < Ni
[Fe(H2O) 6 ]2 + , µ 1 = 4(4 + 2)
[M(H2O) 6]Cl 2 , is (c) Zn < Ni < Mn < Ti
(d) Ti < Mn < Ni < Zn (n = 4), = 24 = 4.89BM
(a) Co2+ and Fe2+ (b) Cr2+ and Mn2+ [Cr(H2O) 6 ]2 + , µ 2 = 5(5 + 2)
Ans. (d)
(c) V2+ and Co2+ (d) V2+ and Fe2+
The 3d-transition series is (n = 5), = 35 = 5.92 BM
[2019, 12 Jan Shift-I]
Sc Ti V Cr Mn Fe Co Ni Cu Zn
So, µ 1 ≈ µ 2 .Thus, statement (c) is
Ans. (c) correct.
Atomic 21 22 23 24 25 26 27 28 29 30
As H2O is a weak field ligan(d) It readily number (d) [Ni(NH3) 4 (H2O)2 ]2 + is also a
⇒

forms high spin complexes. In Outermost 3d24s2 3d54s2 ⇒

3d84s2 3d104s2 high-spin octahedral complex of
[M(H2O) 6 ]Cl2 , M exist in +2 oxidation Electronic
Ni2 + (3d 8 , n = 2)
Configurection
state. The arrangement of electrons in µ = 2(2 + 2) = 8 = 2.83 BM
the given metal ions are as follows: In 1st ionisation, one electron will be
removed from 4s 2 subshell/orbital. Thus, statement (d) is correct.
Spin only With increase in atomic number (Z), i.e.
Number of Magnetic with increase in number of protons in the
23 The pair that has similar atomic
Metal radii is
Configuration unpaired moment nucleus, effective nuclear charge (Z * ) [2019, 12 April Shift-II]
ions (in BM)
electrons also increases from Sc to Zn. (a) Mn and Re (b) Ti and Hf
= n(n + 2) IE ∝ Z * (c) Sc and Ni (d) Mo and W
Co2 + (d 7 ) = t25g e2g 3 3.9 So, IE order of the given elements will Ans. (d)
be, The pair that has similar atomic radii is
Fe2 + (d 6 ) = t2 4g e2g 4 4.9 Ti < Mn < Ni < Zn Mo and W. It is due to lanthanoid
contraction. The factor responsible for
Cr2 + (d 4 ) = t23g e g1 4 4.9 22 The incorrect statement is lanthanoid contraction is the imperfect
2+
[2019, 10 April Shift-II] shielding of one electron by another in
Mn (d 5 ) = t23g e2g 5 5.9
(a) the gemstone, ruby, has Cr 3 + ions the same set of orbitals. Shielding of4f is
occupying the octahedral sites of very less due to its diffused shape. As a
V2 + (d 3) = t23g e g0 3 3.9 result, nuclear charge increases. Hence,
beryl
Mo and W have similar atomic radii.
Therefore, Co2 + and V2 + contains same (b) the color of [CoCl(NH3) 5] 2 + is violet
value of magnetic moment (3.9 BM). as it absorbs the yellow light 24 In the following reactions, ZnO is
(c) the spin only magnetic moments respectively acting as a/an
20 The statement that is incorrect of Fe(H2O) 6] 2 + and [Cr(H2O) 6] 2 + are [JEE Main 2017]
about the interstitial compounds is nearly similar (i) ZnO + Na 2O → Na 2ZnO 2
[2019, 8 April Shift-II] (d) the spin only magnetic moment of (ii) ZnO + CO 2 → ZnCO 3
(a) they are very hard [Ni(NH3) 4 (H2O)2] 2 + is 2.83 BM
(a) base and acid (b) base and base
(b) they have metallic conductivity Ans. (a) (c) acid and acid (d) acid and base
(c) they have high melting points The explanation of given statements are Ans. (d)
(d) they are chemically reactive as follows :
Zinc oxide (ZnO) when react withNa2O it
Ans. (d) (a) Ruby, a pink or blood-red coloured act as acid while with CO2 it act as base.
gemstone belongs to corundum Therefore, it is an amphoteric oxide.
Interstitial compounds are formed when
(Al2O3, alumina) system which has
a neutral atom with a small radius ZnO +Na2O → Na2ZnO2
trigonal crystalline lattice
occupies in an interstitial hole Acid Base Salt
containing the repeating unit of
(tetrahedral or octahedral voids) in a ZnO + CO2 → ZnCO3
transition metal’s hcp or ccp lattices Al2O3 – Cr 3+ . So, ruby does not Base Acid Salt
216 JEE Main Chapterwise Topicwise Chemistry

25 Which of the following compounds 28 Four successive members of the Ans. (b)
is metallic and ferromagnetic? first row transition elements listed As oxidation state increases,
[JEE Main 2016] below with atomic numbers. Which electronegativity increases thus acidic
(a) CrO2 (b) VO2 characteristic increases not basic
one of them is expected to have the
(c) MnO2 (d) TiO2 highest E ° 3 + 2 + value? 31 On heating, mixture of Cu 2O and
Ans. (a) M /M [JEE Main 2013]
Only three elements iron (Fe), cobalt (Co) (a) Cr (Z = 24) (b) Mn (Z = 25) Cu 2S will give [AIEEE 2005]
and nickel (Ni) show ferromagnetism at (c) Fe (Z = 26) (d) Co (Z = 27) (a) Cu2 SO 3 (b) CuO + CuS
room temperature. CrO2 is also a metallic (c) Cu + SO 3 (d) Cu + SO2
and ferromagnetic compound which is Ans. (d)
used to make magnetic tapes for SRP value normally increases from left Ans. (d)
cassette recorders. to right in the period ofd-block Following reaction takes place during
elements. Some SRP value are bessemerisation.
26 The reaction of zinc with dilute and exceptionally higher due to stability of 2Cu2O + Cu2S → 6Cu + SO2
concentrated nitric acid, product ion. e.g.,
respectively, produce E° = + 1.57 V; 32 Calomel (Hg 2Cl 2 ) on reaction with
Mn 3 + / Mn 2 +
ammonium hydroxide gives
E°
[JEE Main 2016]
= +1.97 V
(a) NO2 and NO (b) NO and N2O Co 3 + / Co 2 + [AIEEE 2005]

(c) NO2 and N2O (d) N2O and NO2 Thus, E ° 3 + 2 + is highest for Co. (a) HgO
M /M
Ans. (d) (b) Hg2O
Zn +4HNO3 → Zn(NO3)2 + 2H2O + 2NO2 29 The correct order of E °2+ values (c) NH2 Hg HgCl
M /M
(Conc.) (d) HgNH2Cl
with negative sign for the four
4Zn + 10HNO3 → 4Zn(NO3)2 Ans. (d)
successive elements Cr, Mn, Fe and
(Dil. ) + N2O + 5H2O Co is [AIEEE 2010]
Hg2 Cl2 + 2NH4OH → Hg (NH2 ) Cl
white
(a) Mn > Cr > Fe > Co
27 Which of the following (b) Cr > Fe > Mn > Co + Hg ↓ + NH4 Cl + 2H2O
arrangements does not represent (c) Fe > Mn > Cr > Co
black
the correct order of the property (d) Cr > Mn > Fe > Co 33 Of the following outer electronic
stated against it? [JEE Main 2013]
Ans. (a) configurations of atoms, the
(a) V2+ < Cr2+ < Mn2+ < Fe2+ : highest oxidation state is achieved
paramagnetic behaviour Usually across the first transition series,
the negative values for standard by which one of them ? [AIEEE 2004]
(b) Ni2+ < Co2+ < Fe2+ < Mn2+ : ionic size
electrode potential decrease except for (a) (n − 1) d 8ns 2 (b) (n − 1) d 5ns 1
(c) Co 3+ < Fe 3+ < Cr 3+ < Sc 3+ : stability
in aqueous solution Mn due to stabled 5 -configuration. (c) (n − 1) d ns
3 2
(d) (n − 1) d 5ns 2
(d) Sc < Ti < Cr < Mn : number of So, correct order :Mn > Cr > Fe > Co Ans. (d)
oxidation states
Ans. (a) 30 In context with the transition (n–1)d8ns2 4(as in Ni)
2+
(a) V = 3 unpaired electrons elements, which of the following (n–1)d 8
ns2

Cr2 + = 4 unpaired electrons statements is incorrect?

Mn2 + = 5 unpaired electrons (a) In addition to the normal oxidation (n–1)d5ns1 6(as in Cr)
Fe2 + = 4 unpaired electrons state, the zero oxidation state is (n–1)d5 ns1
Hence, the order of paramagnetic also shown by these elements in
behaviour should be complexes [AIEEE 2009] (n–1)d3ns2 5(as in V)
V2 + < Cr2 + = Fe2 + < Mn2 + (b) In the highest oxidation states, the
(n–1)d3 ns2
(b) Ionic size decreases from left to transition metal shows basic
right in the same period. character and form cationic (n–1)d5ns2 7(as in Mn)
(c) (As per data from NCERT) complexes
5
Co3+ / Co2 + = 1.97; (c) In the highest oxidation states of (n–1)d ns2
Fe3+ / Fe2 + = 0.77; the first five transition elements
Cr 3+ / Cr2 + = – 0.41 (Sc to Mn), all the 4s and 3d 34 Which of the following groups of
Sc3+ is highly stable (It does not electrons are used for bonding transition metals is called coinage
show + 2). (d) Once the d 5 configuration is metals? [AIEEE 2003]
(d) The oxidation states increases as exceeded, the tendency to involve (a) Cu, Ag, Au (b) Ru, Rh, Pd
we go from group 3 to group 7 in all the 3d electrons in bonding (c) Fe, Co, Ni (d) Os, Ir, Pt
the same period. decreases
d and f-Block Elements 217

Ans. (a) 38 A red solid is insoluble in water. Cr2 + = [Ar] 3 d 4 ,4s 0

Cu, Ag, Au are called coinage metals However, it becomes soluble if
because in the early times, they were some KI is added to water. Heating
used in making coins. 3d4
the red solid in a test tube results
Number of unpaired electrons = 4
in liberation of some violet
35 Which one of the following nitrates Hence,Mn2 + : [Ar] 3 d 5 with five unpaired
coloured fumes and droplets of a
will leave behind a metal on strong electrons have maximum magnetic
metal appear on the cooler parts of
heating? [AIEEE 2003] moment.
the test tube. The red solid is
(a) Ferric nitrate [AIEEE 2003]
(b) Copper nitrate
(c) Manganese nitrate
(a) (NH4 )2 Cr2O 7 (b) HgI2 TOPIC 2
(c) HgO (d) Pb 3O 4
(d) Silver nitrate Ans. (b)
Important Compounds of
Ans. (d)
HgI2 becomes soluble in water, when KI d-block Elements
Metal oxides lying below Hg in is added to it due to the formation of
electrochemical series decompose to K2Hg I4 complex which is soluble in 40 In the given chemical reaction,
form metal. water. colours of the Fe 2+ and Fe 3+ ions,
∆ HgI2 + 2KI → K2Hg I4
ZnO, MgO, CuO → no effect are respectively
∆ (soluble) 5Fe 2+ + MnO −4 + 8H+ →
Ag2O → Ag + O2
But when HgI2 is heated,Hg I2 Mn 2+ + 4H2O + 5Fe 3+
∆ decomposes to give violet coloured
AgNO3 → Ag2O → Ag + O2 [2021, 1 Sep Shift-II]
fumes of I2 that deposits on the cooler
(a) yellow, orange (b) yellow, green
parts of the test tube.
(c) green, orange (d) green, yellow
36 For making good quality mirrors, ∆
HgI2 → Hg + I2 ↑ Ans. (d)
plates of float glass are use(d)
These are obtained by floating The Fe2 + ion has green colour whileFe3+
molten glass over a liquid metal 39 Which of the following ions has the is yellow in colour.
which does not solidify before maximum magnetic moment?
[AIEEE 2002] 41 In which one of the following sets
glass. The metal used can be
(a) Mn2+ (b) Fe2 + all species show disproportionation
(a) mercury [AIEEE 2003] (c) Ti2+ (d) Cr2+ reaction [2021, 31 Aug Shift-II]
(b) tin Ans. (a)
(c) sodium (a) ClO2− , F2 , MnO2− 2−
4 and Cr2O 7
Larger the number of unpaired
(d) magnesium (b) Cr2O27 − , MnO −4 , ClO2− and Cl2
electrons, greater the magnetic
Ans. (a)
moment,µ = n (n + 2) (c) ClO2− , Cl2 and Mn3 +
Mercury (Hg) solidifies after glass, so where, n = Number of unpaired electrons (d) ClO −4 , MnO2− −
4 , ClO2 and F2
used mercury for making good quality
Mn25 = [Ar] 4s 2 ,3 d 5 Ans. (c)
mirrors.
Disproportionation reactions are redox
Mn2 + = [Ar] 3d 5 4s 0
reaction in which a compound
37 Which one of the following undergoes oxidation as well as
statements is correct? [AIEEE 2003] reduction.The element of reacting
(a) Manganese salts give a violet borax 3d5 species is in an intermediate oxidation
bead test in the reducing flame state and simultaneously gets oxidised
Number of unpaired electrons = 5
(b) From a mixed precipitate of AgCl and reduced
Fe26 = [Ar] 4s 2 , 3 d 6 +3 −1 +5
and AgI, ammonia solution
Fe2 + = [Ar] 3 d 6 , 4s 0 3 Cl O2− → Cl − + 2 Cl O3−
dissolves only AgCl 0 −1 +5
(c) Ferric ions give a deep green Cl2 + OH− → Cl − + Cl O3− + H2O
+4
precipitate on adding potassium 2Mn3+ + 2H2O → Mn2 + +Mn O2 + 4H+
ferrocyanide solution 3d6
(d) On boiling a solution having Number of unpaired electrons =4 But MnO−4 does not get disproportonated.
K + , Ca2+ and HCO −3 ions, we get a Ti22 = [Ar] 4s 2 3d2 Hence, option (c) is the correct answer.
precipitate of K2Ca(CO 3)2 Ti2 + = [Ar] 3d2 4s 0
Ans. (b) 42 Potassium permanganate on
heating at 513 K gives a product
Ammonia can dissolve precipitate of
AgCl due to the formation of complex as 3d2 which is [2021, 27 Aug Shift-II]
given below Number of unpaired electrons = 2 (a) paramagnetic and colourless
AgCl + 2NH3 → [Ag (NH3)2 Cl] Cr24 = [Ar] 3 d 5 ,4s 1
(b) diamagnetic and green
218 JEE Main Chapterwise Topicwise Chemistry

(c) diamagnetic and colourless Ans. (c) Ans. (b)

(d) paramagnetic and green Oxidation number of3d-metal oxides are Generally,d-block elements shows
Ans. (d) A. CrO3 → Cr ⇒+6 magnetic property due to presence of
When KMnO4 is heated at 513 K, it forms B. Fe2O3 → Fe ⇒+3 unpaired electrons in itsd-block. Mn i.e.
C. MnO2 → Mn ⇒+4 manganese shows + 2 and +3 oxidation
K2 MnO4 and MnO2 and O2 .
+7 +6 +4 D. V2O5 → V ⇒+5 state.
D
2KMnO4 →
513 K
K2 MnO4 + MnO2 + O2 E. Cu2O → Cu ⇒+1 Both having unpaired electrons as
(Green) (Black residue) shown below
So, oxidation state order is
Mn25 = 1s , 2s , 2p , 3s 2 , 3p6 , 4s 2 , 3d 5
2 2 6
Mn = [Ar]3d 5 4s 2
CrO3 > V2O5 > MnO2 > Fe2O3 > Cu2O 25
Mn+6 = 1s 2 , 2s 2 , 2p6 , 3s 2 , 3p6 , 4s 1; or A > D > C > B > E. Mn2 + (3d 5 4s 0 ) having 5 unpaired
1 unpaired electron, so paramagnetic electrons in3d orbital.
So, option (d) is correct. 46 The set having ions which are Mn+3, (3d 4 4s 0 ) having 4 unpaired
coloured and paramagnetic both is electrons in 3d orbital.
43 The addition of dilute NaOH to [2021, 22 July Shift-II] SiO2 , p-block element compound is
Cr 3 + salt solution will give (a) Cu2 + , Cr 3 + , Sc + commonly believed to be a typical
[2021, 27 Aug Shift-II] (b) Cu2 + , Zn2 + , Mn4+ diamagnetic as no unpaired electrons
(a) a solution of [Cr(OH) 4] − (c) Sc 3 + , V 5 + , Ti4 + are present.
(b) precipitate of Cr2O 3 (H2O) n MgO and Na2O also have unpaired
(d) Ni2 + , Mn7 + , Hg2+
(c) precipitate of [Cr(OH) 6] 3 − electrons and hence are diamagnetic.
Ans. (a)
(d) precipitate of Cr(OH) 3 Hence,Mn3O4 show magnetic property.
Cu2 + , Cr 3+ and Sc+ are paramagnetic and
Ans. (b) coloured due to presence of unpaired 49 Fex 2 and Fey 3 are known when x
The addition of dil. NaOH to Cr 3+ solution electrons.
will produce ppt. of Cr2O3 (H2O)n .
and y are [2021, 16 March Shift-II]
(i) Electronic configuration of
(a) x = F, Cl, Br, I and y = F, Cl and Br
Cr 3+ + NaOH → Cr2O3 (H2O) n 29 Cu = [Ar] 4s , 3d
1 10

(Precipitate)
2+
whereas for Cu = [Ar], 3d 9 (b) x = F, Cl, Br and y = F, Cl, Br and I
So, n =1. (c) x = Cl, Br, I and y = F, Cl, Br and I
Therefore, the option (b) is correct.
(ii) Electronic configuration of (d) x = F, Cl, Br, I and y = F, Cl, Br and I
24 Cr = [Ar] 4s , 3d
1 5
44 Which one of the following metals Ans. (a)
forms interstitial hydride easily ? whereas for Cr 3+ = [Ar], 3d 3 Fel 3 does not exist because ofI− . Being a
[2021, 25 July Shift-II] So, n = 3. very good reducing agent,I− reduces
(a) Cr (b) Fe (iii) Electronic configuration of Fe3+ to Fe2 + .
21Sc = [Ar] 4s , 3d 2Fe3+ + 2I− → 2Fe2 + + I2
2 1
(c) Mn (d) Co
Ans. (a) whereas for Sc+ = [Ar] 4s 1, 3d 1 Reducing nature order I > Br > Cl > F
So, n = 2.
The metal like chromium (Cr) absorb Fe3+ + e − → Fe2 + E ° = 0.77 V
Due to presence of unpaired electron(s)
dihydrogen in almost all stoichiometric I2 + 2e − → 2I− E ° = – 0.54 V
in Cu2 + , Cr 3+ and Sc + they are
quantities. This phenomenon is known paramagnetic and coloured. As standard reduction potential value of
as occlusion and compound formed are Fe3+ is more thanI2 , so it is reduced to
Whereas
called as interstitial hydride or metallic Fe2 + . Hence, exceptFeI3, all other
hydride. Mn7 + (d 0 ), Hg2 + (d 10 ), Zn2 + (d 10 ), Cu+ (d 10 )
halogens can form iron halide
Elements of group 7, 8, 9 do not form Sc3+ (d 0 ) and Ti4 + (d 0 ) do not have compounds.
hydrides. Only Cr will form hydride unpaired electrons. So, they are
among the given elements (Fe, Mn, Co) colourless and diamagnetic in nature. 50 In mild alkaline medium,
(Mainly d and f-block elements form thiosulphate ion is oxidised by
47 Number of electrons that vanadium
interstitial hydrides).
MnO −4 to “ A”. The oxidation state of
(Z = 23) has in p-orbitals is equal to
sulphur in “ A” is ……… .
45 The correct order of following ……… . [2021, 22 July Shift-II]
[2021, 26 Feb Shift-II]
3d-metal oxides, according to their Ans. (12) Ans. (6)
oxidation numbers is Vanadium (Z = 23) Mild
S2O23− + MnO4− →
(A) CrO 3 (B) Fe 2O 3 Electronic configuration Thiosulphate ion Permanganate ion
Alkaline
medium
(C) MnO 2 (D) V2O 5 = 1s 2 2s 2 2p6 3s 2 3p6 4s 2 3d 3 [Reducing agent] [ Oxidising agent]

Total number of electrons in p-orbital is SO24− + MnO24−

(E) Cu 2O [2021, 25 July Shift-I]
6 + 6 = 12. Sulphate ion Manganate ion
(a) (D) > (A) > (B) > (C) > (E) (A)

(b) (A) > (C) > (D) > (B) > (E) Oxidation number of sulphur inSO24− (A) is
48 The oxide that shows magnetic + 6.
(c) (A) > (D) > (C) > (B) > (E) property is [2021, 18 March Shift-II] Q x + 4(−2) = − 2
(d) (C) > (A) > (D) > (E) > (B)  
(a) SiO2 (b) Mn3O 4 (c) Na2O (d) MgO  ⇒x = + 6 
d and f-Block Elements 219

51 On treating a compound with warm Ans. (b) 2. in the presence of HCl,

dil. H2SO 4 , gas X is evolved, which Statement (b) is incorrect whereas all permanganate titrations
turns K 2Cr 2O 7 paper acidified with other statements are correct. provide satisfactory results.
dil. H2SO 4 to a green compound Y. Corrected statement is : 3. some lanthanoid oxides can be
X and Y respectively are (b) Manganate ions contain 1 unpaired
used as phosphors.
[2021, 26 Feb Shift-I]
electron that it shows
[2020, 4 Sep Shift-II]
paramagnetic nature but
(a) X = SO2 ,Y = Cr2O 3 permanganate ion, has no (a) 2 and 3 only (b) 2 only
(b) X = SO 3,Y = Cr2O 3 unpaired electron so, it shows (c) 1 only (d) 1 and 2 only
(c) X = SO2 ,Y = Cr2 (SO 4 ) 3 diamagnetic nature. Ans. (b)
(d) X = SO 3,Y = Cr2 (SO 4 ) 3 Manganate Permanganate Only statement 2 is incorrect, whereas 1
Ans. (c) +6 2– +7 s and 3 are correct.
MnO4 MnO4
Gas, X turns acidified dichromate O O KMnO4 will not give satisfactory result
(K2 Cr2O7 ) green that means it is a when it is titrated by HCl, because same
reducing agent. Mn Mn amount of KMnO4 is consumed to oxidise
+6 HCl into Cl2 .
Cr (VI) from compound K2 Cr2 O7 on O O– O– O O O–
reduction changes its colour from Hybridisation-p3s Hybridisation-p3s 54 Consider the following reactions :
orange to green which is the colour of Cr
(III) compound Y .
Colour - Green Colour - Purple NaCl + K 2Cr 2O 7 + H2SO 4 → (A) +
Unpair e– = 1 e– Unpair e– = No unpair e–
+4
Magnetic nature Magnetic nature side products (conc)
SO2 can show both reducing and
+6
= Paramagnetic = Diamagnetic
(A) + NaOH→ (B) + side products
oxidising properties whereasSO3 cannot Other statements are discussed as
show reducing property because of follows :
(B) + H2SO 4 + H2O 2 → (C) + side
highest group number 16, oxidation state (a) Manganate ions contain 1 unpair
products (dilute)
(+6) of sulphur inSO3. electron that it show paramagnetic The sum of the total number of
So, X is SO2 . nature but in paramagnetic ion has atoms in one molecule each of (A),
As, X reacts withK2 Cr2O7 in dil.H2SO4 no unpair electron, so it shows
(B) and (C) is …………
medium, the green coloured Cr (III) diamagnetic nature. [2020, 7 Jan Shift-II]
compound, Y must be Cr (III) sulphate or (c) Mn → 3d 5 4s 2 Ans. (18.00)
Cr2 (SO4 ) 3.
So, Y is Cr2 (SO4 ) 3. G.S. Reactions : 4NaCl + K2 Cr2O7 + 6 H2SO4
The overall reactions can be shown as : 3d 4s 4p → 2 CrO2 Cl2 + 4 NaHSO4 + 2KHSO4
Dil. (A ) + 3H2O
(Compound) → E.S.
Water soluble SO −3 salt H 2 SO 4
CrO2 Cl2 + 4 NaOH → Na2 CrO4 + 2NaCl
3d 4s 4p + 2H2O (B)
K 2 Cr2 O 7
Dil.
→ SO2 (g) → Cr2 (SO4 ) 3 O → 2s 2 2p 4 O
H 2 SO 4 dil. H 2 SO 4 pπ–dπ Na2 CrO4 + 2 H2SO4 + 2 H2O2 → CrO5
(X ) (Y )
(C )
(Green) Mn
2s 2p pπ–dπ + 2NaHSO4 + 3H2O
(i) SO23− +H2SO4 → SO2 ↑ + H2O + SO24− O
s
Hybridisation is-d3s O O Number of atoms : (A) CrO2 Cl2 = 5
(X )
+6 +4 pπ–dπ
(ii) K2 Cr2 O7 + SO2 + H2SO4 → Shape-tetrahedral (B) Na2 CrO4 = 7
(Orange) (X ) O
(C) CrO5 = 6
+3 +6
2–
It is same as MnO4–
Cr2 (SO4 ) 3 +K2SO4 + H2O MnO4 Mn d3s-hybridisation and ∴ A + B + C = 18
(Y ) – tetrahedral shape.
(Green) O O– O 55 The sum of the total number of
−
In MnO4 and MnO24− , the π-bonding bonds between chromium and
52 The incorrect statement is :
[2020, 3 Sep Shift-II] take place by overlap of p-orbital of oxygen atoms in chromate and
(a) Manganate ion is green in colour oxygen and d-orbital of Mn. This dichromate ions is .........
option is also correct. [2020, 9 Jan Shift-II]
and permanganate ion is purple in
colour. (d) We have seen in option (c) Ans. (12.00)
manganate and permanganate ions
(b) Manganate and permanganate 2–
Chromate (CrO4 ) Dichromate (Cr2 O7 )
2–
are tetrahedral.
ions are paramagnetic. O O O
This option is also correct.
(c) In manganate and permanganate
ions, the π-bonding takes place by 53 The incorrect statement(s) among
Cr Cr Cr
O– –
O–
O O
overlap of p-orbitals of oxygen and – O
d-orbitals of manganese.
(1)-(3) is (are) O O O
4 CrO or 8CrO
(d) Manganate and permanganate 1. W(VI) is more stable than
ions are tetrahedral. Cr(VI).
220 JEE Main Chapterwise Topicwise Chemistry

Total number of bonds between (a) K 3MnO 4 , K2MnO 4 and Cl2 Ans. (d)
chromium and oxygen atoms in (b) K2MnO 4 , KMnO 4 and SO2 (a) FeO > Fe2O3 (basic). Thus, it is
chromate and dichromate ions (c) KMnO 4 , K2MnO 4 and Cl2 correct statement.
= 4 + 8 = 12. (b) FeCl2 > FeCl 3 (ionic), larger the
(d) K2MnO 4 , KMnO 4 and Cl2
charge greater the polarizing
4 KOH, O Ans. (c)
56 A   
→ 2B + 2H2O
2
Thermal decomposition of Mn
power. Thus, greater the covalent
(Green) nature. Thus, the given statement
compound (X), i.e. KMnO4 at 513 K results is correct
3B 4 
HCl
→ 2C + MnO 2 + 2H2O in compound Y(i.e. K2MnO4 ), MnO2 and a (c) Fe2 + salts are more ionic thus less
(Purple) gaseous product. MnO2 reacts with NaCl volatile thanFe3+ salts. Thus, given
H2 O, KI and concentratedH2SO4 to give a statement is correct.
2C  
→ 2A + 2KOH + D pungent gas Z(i.e. Cl2 ). The reactions (d) Greater the covalent nature, more
involved are as follows :
In the above sequence of easily they are hydrolyze(d) Thus,
reactions, A and D, respectively, 2KMnO4 513K→ K2MnO4 + MnO2 + O2 (g) FeCl 3 is more hydrolyzed than
(X ) ∆
(Y ) FeCl2 .
are [2019, 11 Jan Shift-II]
MnO2 + 4NaCl + 4 H2SO4 → Thus, statement (d) is incorrect.
(a) KI and KMnO 4
MnCl2 + 4NaHSO4 + 2H2O + Cl2 (g)
(b) MnO2 and KIO 3 (Z) pungent gas. 60 Excess of KI reacts with CuSO 4
(c) KI and K2MnO 4 solution and then Na 2S 2O 3 solution
(d) KIO 3 and MnO2 58 The colour of KMnO 4 is due to is added to it. Which of the
Ans. (b) [JEE Main 2015]
following statements is incorrect
When MnO2 (A) is fused with alkali in (a) M → L charge transfer transition for this reaction? [AIEEE 2004]
presence of air then potassium (b) d − d transition
(a) Cu2I2 is formed
manganate (B) is forme(d) Potassium (c) L → M charge transfer transition
(b) CuI2 is formed
manganate (B) is of green colour which (d) σ − σ* transition
disproportionate in a neutral or acidic (c) Na2 S2O 3 is oxidised
Ans. (c)
solution to produce potassium (d) Evolved l2 is reduced
permanganate (C). Potassium KMnO4 → K+ + MnO−4 Ans. (b)
permanganate (C) in presence of acidic ∴ In MnO−4 , Mn has +7 oxidation state
CuSO4 + 2KI → CuI2 + K2SO4
medium oxidises iodide to iodate. having no electron in d-orbitals.
It is considered that higher the oxidation Unstable
The reaction can be shown as :
0 state of metal, greater is the tendency to 2CuI2 → Cu2I2 + I 2
+4 +6 −2
4 KOH, O2 occurL→ M charge transfer, because Thus, CuI2 is not formed.
(i) 2Mn O2 → 2K2 Mn O 4
( A) ∆ (B)
ligand is able to donate the electrons
Potassium manganate into the vacant d- orbital of metal.
(Green)
−2
Since, charge transfer is Laporte as well TOPIC 3
+ 2H2 O as spin allowed, therefore, it shows
+6
colour. Inner Transition Elements
(ii) 3K2 MnO4 4HCl
→ Time Saving Technique There is no need
( B) to check all the four options. Just find out 61 The Eu 2 + ion is a strong reducing
+7 +4 the oxidation state of metal ion. If
2KMnO4 + MnO2 + 2H2O + 4KCl agent in spite of its ground state
oxidation state is highest and ligand
(C ) electronic configuration
Potassium permanganate present there is of electron donating
(Purple)
nature, gives LMCT, which shows more (outermost) : [Atomic number of
−1
intense colour. Eu = 63] [2021, 31 Aug Shift-II]
+7 K I , H2O +4
(iii) 2KMnO4 → 2Mn O2 (a) 4 f 7 6 s 2 (b) 4 f 6
(C ) ( A) 59 Iron exhibits +2 and +3 oxidation (c) 4 f 7 (d) 4 f 6 6 s 2
+5
2KOH + K I O3 states. Which of the following Ans. (c)
(D ) statements about iron is incorrect? The electronic configuration of Eu and
Thus, A and D areMnO2 andKIO3 [AIEEE 2012] Eu2 + ion is as follows :
respectively. (a) Ferrous oxide is more basic in Eu (Z = 63) = [Xe] 4f 7 6s 2
nature than the ferric oxide Eu2 + (Z = 63) = [Xe] 4f 7
(b) Ferrous compounds are relatively
57 Thermal decomposition of a Mn
more ionic than the corresponding 62 Which one of the following
compound (X) at 513 K results in ferric compounds
compound (Y), MnO 2 and a gaseous lanthanides exhibits + 2 oxidation
(c) Ferrous compounds are less
product. MnO 2 reacts with NaCl state with diamagnetic nature ?
volatile than the corresponding
and concentrated H2SO 4 to give a ferric compounds (Given, Z for Nd = 60, Yb = 70,
pungent gas Z. X, Y and Z, (d) Ferrous compounds are more La= 57, Ce = 58) [2021, 31 Aug Shift-I]
respectively, are easily hydrolysed than the (a) Nd (b) Yb
[2019, 12 April Shift-II] corresponding ferric compounds (c) La (d) Ce
d and f-Block Elements 221

Ans. (b) In the light of the above Ans. (d)

Ytterbium shows +2 oxidation state and it statements, choose the most In oxides, MO2 (M is lanthanoid metal)
is diamagnetic in nature. only four lanthanoids exhibit + 4
appropriate answer from the
Yb = [Xe], 4f 14 , 6s 2 oxidation state. These lanthanoids are
options given below. praseodymium (Pr, Z = 59), neodymium
Yb2 + = [Xe], 4f 14 [2021, 16 March Shift-I]
(Nd, Z = 60) terbium (Tb, Z = 65)
Yb2 + = [Xe], (a) Both statement I and statement II dysprosium (Dy, Z = 66).
are correct. So, Yb (ytterbium) option (d) does not
123 (b) Statement I is incorrect but form MO2 type of oxide.
Diamagnetic statement II is correct. Note The common and predominant
Since, there is no unpaired electron, it is (c) Both statement I and statement II are oxidation state of lanthanoids is +3.
diamagnetic in nature. incorrect. Consequently M4+ compounds are
(d) Statement I is correct but statement strong oxidising agents which changes
63 The number of f-electrons in the II is incorrect. to the common +3 state. Similarly,
ground state electronic Ans. (d) lanthanoid compounds of +2 state have a
E° = 1.74 (data given) tendency to show reducing property as
configuration of Np (Z = 93) is …… . Ce 4 + / Ce +3 they get changed to +3 state easily.
(Nearest integer) [2021, 27 Aug Shift-I Ce can be reduced to Ce3+ and can
4+

Ans. (18) oxidise water. 69 Given below are two statements:

The electronic configuration ofNp = 93 is Ce4+ + e − → Ce3+ Statement I CeO 2 can be used for
4+
1s 2 2s 2 2p6 3s 2 3p6 3d 10 4s 2 4p6 4d 10 5s 2 5p6 Ce is having noble gas configuration oxidation of aldehydes and
4f 14 5d 10 6s 2 6p6 5f 4 6d 1 7 s 2 [Xe]4f 0 but it is strong oxidant and gets ketones.
converted to Ce3+ .
In ground state, total number of f Statement II Aqueous solution of
electrons = 14 + 4 = 18 Statement I is correct but statement II is
incorrect. EuSO 4 is a strong reducing agent.
64 The number of 4f electrons in the In the light of the above
67 Given below are two statements. statements, choose the correct
ground state electronic One is labelled as Assertion (A) and
configuration of Gd 2+ is answer from the options given
the other is labelled as Reason (R).
below. [2021, 25 Feb Shift-I]
[Atomic number of Gd is 64.] Assertion (A) Size of Bk 3+ ion is
[2021, 26 Aug Shift-I]
(a) Both statement I and statement II
less than Np 3+ ion. are true.
Ans. (7) (b) Both statement I and statement II
Reason (R) The above is a
The electronic configuration of Gd is as are false.
follows
consequence of the lanthanoid (c) Statement I is true but statement II
Gd = [Xe] 4f 7 , 5d 1, 6s 2
contraction. In the light of the is false.
So, electronic configuration of Gd2 + will
above statements, choose the (d) Statement I is false but statement II
be correct answer from the options is true.
Gd2 + = [Xe], 4f 7 , 5d 1, 6s 0 given below [2021, 16 March Shift-I] Ans. (a)
∴ The number of4f electrons in ground (a) A is false but R is true. Both statement I and statement II are
state configuration of Gd2 + is 7. (b) Both A and R are true but R is not the true. The
correct explanation of (a) + 3 oxidation state of lanthanide is most
65 Number of electrons present in 4f (c) Both A and R are true and R is the stable and therefore lanthanide in + 4
correct explanation of (a) oxidation state has strong tendency to
orbital of Ho 3+ ion is …… . (Given, gain electrons and converted into + 3 and
(d) A is true but R is false.
atomic number of Ho = 67) therefore act as strong oxidising agent,
Ans. (d)
[2021, 25 July Shift-II] e.g. Ce4+ .
Ans. (10) 97 Bk (Berkelium) and 93Np(Neptunium) ∴ CeO2 is used to oxidised alcohol,
are present in actinide series. Due to aldehyde and ketones.
Holmium isf-block element (actinide)
actinoid contraction, there is gradual
having atomic number 67.
decrease in size of M3+ ions across the Lanthanides in + 2 oxidation state has
Ho(Holmium) = [Xe] 4f 116s 2 period due to poor shielding of strong tendency to loss electron and
Electronic configuration of 5f-electrons. converted into + 3 oxidation state e.g.
Ho3 + = [Xe] 4f 10 6s 0 Eu+2 .
So, Bk 3+ is smaller than that ofNp3+ due
So, number of electrons present in4f is to actinoid contraction. ∴ EuSO4 acts as strong reducing agent.
10. So, A is true and R is false. 70 The elements with atomic numbers
66 Given below are two statements. 101 and 104 belong to, respectively,
68 Which one of the following [2020, 4 Sep Shift-I]
Statement I The E° value of lanthanoids does not form MO 2? (a) actinoids and group 4
Ce 4+ /Ce 3+ is +1.74 V. [M is lanthanoid metal] (b) actinoids and group 6
[2021, 26 Feb Shift-I]
Statement II Ce is more stable in (c) group 6 and actinoids
Ce 4+ state than Ce 3+ state. (a) Pr (b) Dy (c) Nd (d) Yb (d) group 11 and group 4
222 JEE Main Chapterwise Topicwise Chemistry

Ans. (a) 74 The effect of lanthanoid increasing atomic number in the

Actinoid series have atomic number contraction in the lanthanoid series series.
from 90 to 103 (f-block element). of elements by and large means (b) All the member exhibit +3
So, element with atomic number (Z) 101 [2019, 10 Jan Shift-I] oxidation state.
belongs to actinoid series and elements (a) increase in atomic radii and (c) Because of similar properties the
with atomic number (Z) 104 belongs to decrease in ionic radii separation of lanthanoids is not
4th group. (b) decrease in both atomic and ionic easy.
radii (d) Availability of 4f electrons results
71 The lanthanoid that does not show (c) increase in both atomic and ionic in the formation of compounds in
+ 4 oxidation state is radii +4 state for all the members of the
[2020, 6 Sep Shift-I] (d) decrease in atomic radii and series. [AIEEE 2011]
(a) Dy (b) Ce (c) Eu (d) Tb increase in ionic radii Ans. (d)
Ans. (c) Ans. (b) (a) There is a gradual decrease in the
Europium (Eu = atomic number 63) Lanthanoid contraction in the lanthanoid radii of the lanthanoids with
Electronic configuration of Eu = series takes place due to the presence increasing atomic number — a
[Xe]4f 7 , 6s 2 of electron(s) in the4f-orbitals. f-orbitals case of lanthanide contraction,
have poor shielding effect. As a result, thus true.
It can show +2 and +3 oxidation state
the effective nucleur charge will be more (b) Ionisation potential for the
in +2 oxidation: Eu2 + = [Xe]4f 7 , 6s 0
experienced by the 5d and 6s- electrons formation of Lu3+ is comparatively
in +3 oxidation : Eu3+ = [Xe]4f 6 , 6s 0 and it will cause contraction or decrease low, hence +3 state is favourable,
Being a typical member of the in both atomic and ionic radii. thus true.
lanthanide, Eu usually assumes the (c) Due to lanthanoide contraction–Zr
oxidation state +3 and +2 but it doesn’t 75 The correct order of atomic radii is and Hf; Nb and Ta, Mo and W have
show +4 oxidation state due to very high [2019, 12 Jan Shift-II] the same size and thus similar
ionisation energy (4140 kJ/mol). (a) Ho > N > Eu > Ce properties and thus separation is
Hence, the correct option is (c). (b) N > Ce > Eu > Ho not easy, thus true.
(c) Eu > Ce > Ho > N (d) Formation of +4 state requires
72 Mischmetal is an alloy consisting (d) Ce > Eu > Ho > N very high energy, thus incorrect.
mainly of [2020, 6 Sep Shift-II]
Ans. (c)
(a) lanthanoid metals
The correct order of atomic radii is 78 The outer electron configuration of
(b) actinoid and transition metals
(c) lanthanoid and actinoid metals Europium (Eu) > Cerium (Ce) Gd (At. no. 64) is [AIEEE 2011]

(d) actinoid metals 199 pm 183 pm (a) 4 f 3, 5d 5 , 6 s 2 (b) 4 f 8 , d 0, 6 s 2

Ans. (a) > Holmium (Ho) > Nitrogen (N) (c) 4 f 4 , 5d 4 , 6 s 2 (d) 4 f 7 , 5d 1, 6 s 2
Lanthanoids are used in the production 176 pm 65 pm Ans. (d)
of alloy steels to improve the strength Note Gd (64)
and work ability of steel. A well known 7
(i) N being the member of p-block and 4f
alloy is mischmetal which has the following
second period, have the smallest [Xe]54
composition.
radii.
Mischmetal − lanthanoid metals = 95%
(ii) Rest of all the 3 members are 5d 1 6s 2
(About 40% La, 50% Ce and the rest lanthanides withEu having stable
other lanthanoids) with traces of iron half-filled configuration thus with
= 5% bigger size than rest two. All the electrons in4f-orbital are
S, C, Ca and Al. (iii) Among Ce and Ho, Ce has larger unpaired, hence stable. Thus, Gd (64) has
size which can be explained on the EC as [Xe] 54 4f 7 , 5 d 1, 6s 2
73 The highest possible oxidation basis of “Lanthanoid contraction”. Instead of [Xe] 54 4f 8 , 6s 2 .
states of uranium and plutonium,
respectively, are 76 The atomic radius of Ag is closest 79 Knowing that the chemistry of
[2019, 10 April Shift-II] to [2020, 7 Jan Shift-I] lanthanoids (Ln) is dominated by its
(a) 7 and 6 (b) 6 and 7 (a) Hg (b) Au (c) Ni (d) Cu +3 oxidation state, which of the
(c) 6 and 4 (d) 4 and 6 Ans. (b) following statements is incorrect?
Ans. (b) The atomic radii of Ag is almost equal to [AIEEE 2009]
Actinoids show a variety of oxidation Au due to lanthanide contraction. (a) Because of the large size of the Ln
states due to comparable energies of 5f, (III) ions the bonding in its its
6d and 7s energy levels. 77 In context of the lanthanoids, compounds is predominantly ionic
In the actinoids family (5f-block), which of the following statements in character
uranium (U) neptunium (Np), plutonium is not correct? (b) The ionic sizes of Ln (III) decrease
(Pu) and americium (Am) have highest
(a) There is a gradual decrease in the in general with increasing atomic
possible oxidation states of +6, + 7, + 7
and +6 respectively. radii of the members with number
d and f-Block Elements 223

(c) Ln (III) compounds are generally 82 The actinoids exhibit more number (b) Poorer shielding of 5d electron by
colourless of oxidation states in general than 4f electrons
(d) Ln (III) hydroxide are mainly basic the lanthanoids. This is because (c) Effective shielding of one of 4f
in character [AIEEE 2007] electron by another in the subshell
(a) the 5f orbitals are more buried (d) Poor shielding of one of 4f electron
Ans. (c)
by another in the subshell
The most common oxidation state of than the 4f orbitals
(b) there is a similarity between 4f and Ans. (d)
lanthanoid is +3. Lanthanoids in +3
oxidation state usually have unpaired 5f orbitals in their angular part of Lanthanide contraction is due to poor
electron in f-subshell and impart the wave function shielding of one of4f electron by another
characteristic colour in solid as well as in (c) the actinoids are more reactive in the sub-shell.
solution state due to f-f transition. than the lanthanoids
(Except lanthanum and lutetium) (d) the 5f orbitals extend farther from 85 Cerium (Z = 58) is an important
the nucleus than the 4f orbitals member of the lanthanides. Which
80 Larger number of oxidation states Ans. (d) of the following statements about
are exhibited by the actinoides The actinoids (5f-element) exhibit more cerium is incorrect?
than those by the lanthanoides, the number of oxidation states in general (a) The common oxidation states of
main reason being [AIEEE 2008] than the lanthanoids because 5f orbitals cerium are +3 and +4 [AIEEE 2004]
(a) 4f orbitals more diffused than the extend farther from the nucleus than the (b) The +3 oxidation state of cerium is
5f orbitals 4f-orbitals. more stable than the +4 oxidation
(b) lesser energy difference between Thus, the attraction on the 5f electrons state
5f and 6d than between 4f and 5d in actinoid series decreases. Hence, (c) The +4 oxidation state of cerium is
orbitals they can easily participate in bonding
not known in solutions
and therefore, exhibits more number of
(c) more energy difference between (d) Cerium (IV) acts as an oxidising
oxidation states.
5f and 6d than between 4f and 5d agent
orbitals
83 Lanthanoid contraction is caused Ans. (c)
(d) more reactive nature of the
actinoides than the lanthanoides due to +3 and +4 states are shown by Ce in
(a) the appreciable shielding on outer aqueous solution. Thus, statement (c) is
Ans. (b) incorrect.
electrons by 4f electrons from the
Lanthanoides : [Xe] 4f 1− 14 5 d 0 − 16s 2 nuclear charge
Actinoides : [Rn] 5f 1− 14 6 d 0 − 1 7 s 2 (b) the appreciable shielding on outer 86 The radius of La 3+ (atomic number
Lanthanoides and actinoides use core d electrons by 5d electrons from the : La = 57) is 1.06 Å. Which one of the
and f orbitals also to show higher nuclear charge following given values will be
oxidation state. As actinoides have (c) the same effective nuclear charge closest to the radius of Lu 3+
comparatively low energy difference from Ce to Lu
between f and d orbitals, thus, they show (atomic number : Lu = 71) ?
(d) the imperfect shielding on outer [AIEEE 2003]
more number of oxidation states.
electrons by 4f electrons from the (a) 1.60Å (b) 1.40 Å
nuclear charge [AIEEE 2006] (c) 1.06 Å (d) 0.85 Å
81 Identify the incorrect statement
Ans. (d) Ans. (d)
among the following. [AIEEE 2007]
Imperfect shielding on outer electrons Due to lanthanide contraction, there
(a) d-block elements show irregular
by 4f electrons from the nuclear charge occurs net decrease in size. Only, 0.85 Å
and erratic chemical properties is due to the diffused large shape of is smaller one.
among themselves 4f-orbitals.
(b) La and Lu have partially filled d This imperfect shielding is unable to 87 Most common oxidation states of
orbitals and no other partially filled counterbalance the effect of the
orbitals Ce (Cerium) are [AIEEE 2002]
increased nuclear charge. Hence, the
(c) The chemistry of various net result shows contraction in size.
(a) + 3, + 4
lanthanoids is very similar (b) + 2, + 3
(d) 4f and 5f orbitals are equally 84 Which of the following factors may (c) + 2, + 1
shielded be regarded as the main cause of (d) + 3, + 5
Ans. (d) lanthanide contraction? Ans. (a)
4f orbital is nearer to nucleus as [AIEEE 2005] Cerium, Ce58 = [Xe] 4f 1 5d 16s 2 . Its most
compared to 5f orbital. Therefore, (a) Greater shielding of 5d electron by stable oxidation state is +3 but +4 is also
shielding of4f is more than 5f orbital. 4f electrons existing.
19
Coordination
Compounds
TOPIC 1 03 The number of optical isomers 05 3 moles of metal complex with
Nomenclature, Isomerism possible for [Cr(C 2O 4 ) 3] 3 − is ... formula Co(en)2Cl3 gives 3 moles of
and Werner’s Theory [2021, 27 Aug Shift-II] silver chloride on treatment with
Ans. (2) excess of silver nitrate. The
The structure of [Cr(C2O4 ) 3] 3− is secondary valency of Co in the
01 Spin only magnetic moment in BM ox ox complex is ………… .
of [Fe(CO) 4 (C 2O 4 )] + is
(Round off to the nearest integer)
[2021, 31 Aug Shift-II] ox Cr Cr ox [2021, 27 July Shift-II]
(a) 5.92 (b) 0 Ans. (6)
(c) 1 (d) 1.73 ox ox
2–
Cr2 O4 =ox 1 mole of [Co(en)2 Cl 3] produces 1 mole
Ans. (d) Mirror image optical isomers of AgCl.
In [Fe(CO) 4 (C2O4 )] + , oxidation number of Oxalate is bidentate symmetrical ligand. 3 moles of [Co(en)2 Cl 3] produces 3
Fe = + 3 The complex does not possess any moles of AgCl.
{ x + 4 × 0 + (−2) = 1 element of symmetry and are optically ∴ Given compound is [Co(en)2 Cl2 ]Cl.
∴ x =3 active. The two optical isomers are [Co(en)2 Cl2 ]Cl (aq) + AgNO3 (aq) →
shown above.
Fe3+ = [Ar] 3d 5 4s 0 (excess)
∴ Answer is two (2). [Co(en)2 Cl2 ] NO3 (aq) + AgCl (s ) ↓
CO is a strong field ligand, so pairing is
(white)
favoured 04 1 mol of an octahedral metal
Fe3+ = t22 ,g2 , 1, e g0 , 0 complex with formula MCl 3 ⋅2L on en
Cl
Number of unpaired electron (n) = 1 reaction with excess of AgNO 3 en
µ = n(n + 2) BM gives 1 mol of AgCl. The denticity of Co Cl
en
= 1 (1 + 2) ligand L is ……… . (Integer answer) Cl
en
= 3 = 1.73 BM [2021, 27 Aug Shift-I]
Ans. (2) Dotted line represents primary valency
02 The denticity of an organic ligand, Since, the compound is octahedral, the = 3.
biuret is [2021, 31 Aug Shift-I] central metal M will form 6 bonds. On Solid line represents secondary valency
(a) 2 (b) 4 reaction with excess of AgNO 3, only 1 (coordinated ions) of Co = 6.
(c) 3 (d) 6 mol of AgCl is precipitated that means
only 1 Cl − is present as counter ion and 06 Given below are two statements.
Ans. (a)
2Cl − ions are present in coordinate
Biuret is bidentate ligand and denticity sphere. Statement I [Mn(CN) 6] 3– ,
of this organic ligand is 2. So ‘ L ’ should by bidentate to form an [Fe(CN) 6] 3– and [Co(C 2O 4 ) 3] 3– are
O O octahedral complex alongwith2Cl − ions. d 2 sp 3 hybridised.
Cl
C—NH—C Statement II [MnCl 6] 3– and
H2 N
NH2 L M L [FeF6] 3– are paramagnetic and
M have 4 and 5 unpaired electrons,
Cl respectively.
Hence, correct option is (a). [MCl2L2 ] Cl
Coordination Compounds 225

In the light of the above 07 The number of geometrical 09 The number of geometrical
statements, choose the correct isomers possible in isomers found in the metal
answer from the options given triamminetrinitrocobalt (III) is X and complexes [PtCl 2 (NH3 ) 2],
below [2021, 27 July Shift-II] in trioxalatochromate (III) is Y. [Ni(CO) 4], [Ru(H2O) 3 Cl 3] and
(a) Statement I is true but statement Then, the value of X + Y is …………… [CoCl 2 (NH3 ) 4] + respectively, are
II is false . [2021, 27 July Shift-I] [2021, 27 July Shift-I]
(b) Both statement I and statement II Ans. (2) (a) 1, 1, 1, 1 (b) 2, 1, 2, 2
are false (c) 2, 0, 2, 2 (d) 2, 1, 2, 1
(c) Statement I is false but statement Formula of triamminetrinitrocobalt (III) is
Ans. (c)
II is true [Co(NO2 ) 3 (NH3) 3]. Its geometrical
(d) Both statement I and statement II isomers are as follows Number of geometrical isomers of
are true NO2 NO2 [PtCl2 (NH3)2 ] two geometrical isomers.
H3N NO2 H3N NH3 H3N Cl H3N Cl
Ans. (d) Co3+ and Co3+ Pt and Pt
Hybridisation of all the given complexes H3N NO2 H3N NO2 H3 N Cl Cl NH3
NH3 NO2
are given in following table. In [Ni(CO) 4 ] complex all ligands are
[Mn(CN) 6 ] 3− ⇒Mn3+ The formula of trioxalatochromate (III) same. Therefore, it does not show
CN − is a strong field ligand. ion is geometrical isomers.
∴Pairing of electron takes place. [Cr(C2O4 ) 3] 3 − . It has no geometrical [Ru(H2O) 3 Cl 3] two geometrical isomers.
isomers.
3d 4s 4p Cl Cl
× × × × × × H2O Cl H 2O Cl
3+
144424443 C Ru and Ru3+
d2sp3 O C H2O OH2 H 2O Cl
Cl H 2O
[Fe(CN) 6 ] 3− ⇒Fe3+
C—O O
CN − is a strong ligand. Cr3+ [CoCl2 (NH3) 4 ] + two geometrical
∴Pairing of electron takes place. C—O O isomers.
3d 4s 4p O Cl Cl
C O
× × × × × × C H3N NH3 H 3N 3+
Cl
3+
144424443 Co and Co
H3N NH3 H 3N NH3
d2sp3 NH3
Zero geometrical isomer Cl
[Co(C2O4 ) 3] 3− ⇒ Co3+
C2O24− acts as strong field ligand with Thus, the value of X + Y = 2 + 0 = 2 10 The type of hybridisation and
Co3+ . magnetic property of the complex
∴Pairing of electrons takes place. 08 An organic compound is subjected
[MnCl 6] 3− , respectively, are
3d 4s 4p to chlorination to get compound A [2021, 27 July Shift-I]
× × × × × × using 5.0 g of chlorine. When 0.5 g (a) sp 3d2 and diamagnetic
144424443
of compound A is reacted with (b) d2 sp 3 and diamagnetic
d2sp3
3− 3+
AgNO 3 [Carius method], the (c) d2 sp 3 and paramagnetic
[Fe F6 ] ⇒ Fe percentage of chlorine in (d) sp 3d2 and paramagnetic
F is a weak field ligand. compound A is ………… when it Ans. (d)
∴Pairing of electron does not occurs. forms 0.3849 g of AgCl. (Round off The type of hybridisation and magnetic
to the nearest integer) property of [MnCl 6 ] 3 − are sp3d2 and
4s 4p 4d (Atomic masses of Ag and CI are paramagnetic respectively.
× × × × × × 107.87 and 35.5 respectively) In [MnCl 6 ] 3 − , oxidation state of Mn is
x + 6(− 1) = − 3
144424443
[2021, 27 July Shift-I]
sp3d2
Ans. (19) x = −3+ 6 ⇒ x = + 3
[MnCl 6 ] 3− ⇒ Mn3+
Cl − is a weak field ligand. Mass of organic compound = 0.5 g Electronic configuration of Mn is
Mass of AgCl formed = 0.3849 g [Ar]3d 5 4s 2 .
∴Pairing of electron does not occurs.
% of Cl Electronic configurationMn3 + = [Ar] 3d 4
 Atomic mass of Cl 
  Mn3+ =
4s 4d4p  × Mass of AgCl formed 
= 3d
× × × × × ×  Molecular mass of AgCl 
 
× Mass of organic compound 
144424443

sp3d2 4s 4p 4d
3−
[FeF6 ] have 5 unpaired electrons and × 100 sp3d 2
[MnCl 6 ] 3− have 4 unpaired electrons. 35.5 × 0.3849
= × 100
So, both statement I and statement II are 143.37 × 0.5 As Cl is a weak field ligand, so no pairing
of electrons occurs.
true. = 19.06 ~− 19
226 JEE Main Chapterwise Topicwise Chemistry

Thus, hybridisation is sp3d2 . CrCl 3 ⋅ 3NH3 ⋅ 3H2O reacts with (c) [Co(CN)6 ]3− ; Electronic
Magnetic behaviour is paramagnetic excess of silver nitrate. The configuration of Co3+ = [Ar] 3d 6 4s 0
(having 4 unpaired electrons). number of chloride ions satisfying CN− is a strong field ligand so, pairing of
the secondary valency of the metal electrons occur.
11 Indicate the complex/complex ion 3d 4s 4p
ion is ……… . [2021, 25 July Shift-I]
which did not show any
Ans. (0)
geometrical isomerism.
[2021, 26 Aug Shift-II] No. of mole of AgCl precipitated is equal d2sp3
(a) [CoCl2 (en)2] to the mole of Cl − present in ionisation 4d
sphere.
(b) [Co(CN) 5 (NC)] 3−
(c) [Co(NH3) 3 (NO2 ) 3] Now, reaction is
Hybridisation = d2 sp3 (Octahedral)
(d) [Co(NH3) 4 Cl2] + [Cr(H2O) 3 (NH3) 3]Cl 3 →
1 mol
Unpaired electrons = 0 (all paired)
Ans. (b) Magnetic nature = Diamagnetic
[Cr(H2O) 3 (NH3) 3] 3+ +3Cl −
AgNO 3
(a) [CoCl2 (en)2 ] shows cis-trans →
excess
AgCl (d) [Ni(CO)4] Electronic configuration
isomerism. 1 mol 3 mol 3 mol
of Ni = [Ar] 3d 8 4s 2
(b) [Co(CN) 5 (NC)] 3– is of MA5 B type Since, there is no Cl − present in the
CO is a strong field ligand so, pairing of
complex, which will not show any coordination sphere. Therefore, zero
electrons occur.
isomerism. chloride ions satisfy the secondary 4p
3d 4s
(c) [Co(NH3) 3 (NO2 ) 3] shows facial and valency of the metal ion.
meridonial isomerism.
(d) [Co(NH3) 4 Cl2 ] + shows geometrical 14 Which one of the following species
sp3
(cis-trans) isomerism. In cis responds to an external magnetic
Hybridisation = sp3 (tetrahedral)
isomer, two Cl ligands are adjacent field [2021, 25 July Shift-I]
to each other. In trans isomer two Unpaired electron = 0
(a) [Fe(H2O) 6] 3+ (b) [Ni(CN) 4] 2−
Cl ligands are opposite to each Magnetic nature = Diamagnetic
(b) [Co(CN) 6] 3− (d) [Ni(CO) 4]
other.
Ans. (a)
∴ Option (b) is correct. 15 The total number of unpaired
Only paramagnetic substance or electrons present in [Co(NH3 ) 6]Cl 2
12 Which one of the following metal complex response to external magnetic
and [Co(NH3 ) 6]Cl 3 is …… .
field.
complexes is most stable? [2021, 22 July Shift-II]
[2021, 25 July Shift-II] (a) [Fe(H2O)6 ]3+ ; Electronic Ans. (1)
(a) [Co(en)(NH3) 4]Cl2 configuration of Fe3+ = [Ar] 3d 5 4s 0 (i) [Co(NH3) 6 ] Cl2 ⇒Oxidation state of
(b) [Co(en) 3]Cl2 All electrons are unpaired (No pairing as cobalt Co2 + is +2.
(c) [Co(en)2 (NH3)2]Cl2 H2O is Electronic configuration 27 Co
(d) [Co(NH3) 6]Cl2 (a weak field ligand) = [Ar]4s 2 3d 7
Ans. (b) Co2 + = [Ar] 4s 0 3d 7 i.e.
Stability of a complex depends on the 3d
chelating effect. Complex [Co(en) 3]Cl2 is NH3 acts as SFL (strong field
most stable complex among the given ligand) due to small size of cobalt
4s 4p 4d
complex compounds because more with +2 charge, so pairing will took
3 2
number of chelate rings are present in sp d place.
this complex as compare to others.
(a) [Co(en) (NH3) 4 ] Cl2 1 chelate ring Hybridisation = sp3d2 (octahedral), Co2+ =

(b) [Co(en) 3]Cl2 3 chelate ring Unpaired electrons = 5

(c) [Co(en)2 (NH3)2 ]Cl2 2 chelate ring Magnetic nature = Paramagnetic (so this =
complex response to external magnetic
(d) [Co(NH3) 6 ]Cl2 0 chelate ring One
field) unpaired electron
The structure of [Co (en) 3] Cl2 is (b) [Ni(CN)4]2− Electronic configuration
Co2 + have one unpaired electron.
2+ of Ni2 + = [Ar] 3d 8 4s 0
en
CN− is a strong field ligand therefore, (ii) [Co(NH3) 6 ] Cl 3 ⇒Oxidation state
Co 2Cl
– pairing of electrons occur. of cobalt (CO2 + ) is +3.
en So, NH3 acts as strong field ligand.
en
Hence, Co3+ → 4s 0 3d 6
3d 4s 4p
2 4s0 3d6
dsp
13 Three moles of AgCl get
precipitated when one mole of an Hybridisation = dsp2 (square planar)
octahedral co-ordination Unpaired electron = 0 (all paired)
compound with empirical formula Magnetic nature = Diamagnetic Zero unpaired electron
Coordination Compounds 227

Co3+ have zero unpaired electron. Cl – is a weak field ligand. So, no 18 The correct structures of trans-
[Co(NH3) 6 ]Cl2 ⇒ Co2 + → 3d 7 pairing of electrons occurs.
[NiBr 2 (PPh 3 ) 2] and meridonial-
(S.F.L) n = 1 For C.N.= 6
[Co(NH3 ) 3 (NO 2 ) 3], respectively are
[Co(NH3) 6 ] Cl 3 ⇒ Co3+ → 3d 6 3d
[2021, 18 March Shift-I]
(S.F.L) n = 0

q
q
So, total (1 + 0) = 1 unpaired No pairing Ph3P Br
(a) Ni
electron. 4s 4p 4d Br PPh3
NO2
16 The correct order of intensity of H3N NO2
colors of the compound is Hybridisation sp3d2 and Co
[2021, 20 July Shift-I] (Octahedral) H3N NO2
(a) [Ni(CN) 4] 2− > [NiCl4] 2− > (b) K 2 [Ni(CN)4 ] NH3
[Ni(H2O) 6] 2+ K2 [Ni(CN) 4 ] → 2K+ + [Ni(CN) 4 ]2 –
Ph3P Br
Ni
(b) [Ni(H2O) 6] 2+ > [NiCl4] 2− > (b) Ph3P Br
x + 4(−1) − (−2) = 0; where x, 4,−1
[Ni(CN) 4] 2− and −2 are the oxidation number of NO3
(c) [NiCl4] 2− > [Ni(H2O) 6] 2+ > Ni, number of CN ligands, charge O2N NH3
[Ni(CN) 4] 2− on one CN and charge on complex. and Co
(d) [NiCl4] 2− > [Ni(CN) 4] 2− > O2N NH3
[Ni(CN) 4 ]2 – ⇒x − 4 + 2 = 0 ⇒ x = +2
[Ni(H2O) 6] 2+ Electronic configuration of Ni2 + ⇒
NH3
Ans. (c) [Ar]3d 8 4s 0 Ph3P Br
(c) Ni
Correct order of intensity of colours of CN– is a strong field ligand. So, Ph3P Br
the compounds is pairing of electrons occur. NH3
[NiCl 4 ]2 − > [Ni(H2O) 6 ]2 + > [Ni(CN) 4 ]2 − For C.N. = 4 O 2N NH3
and Co
Ni is in +2 oxidation state in all 3d 4s 4p O 2N NO2
complexes. The intensity of colour
NH3
q

q
q

depends on the strength of the ligand

Ph3P Br
attached with the central metal atom Hybridisation dsp2 (d) Ni
because more strong ligand more (Square planar) Br PPh3
splitting energy, less is intensity of (c) Ni(CO)4 NH3
colour. Strength of ligand is in the order H3N NO2
CO is neutral and strong field ligand.
CN− > H2O > Cl − . So, pairing of electrons occur.
and Co
O2N NO2
Splitting energy order [NiCl 4 ]2 − < Oxidation number of Ni is zero NH3
[Ni(H2O) 6 ]2 + < [Ni(CN) 4 ]2 −
Electronic configuration of
∴Intensity of colour of compound Ni = [Ar]3d 10 4s 0
Ans. (d)
[NiCl 4 ]2 − > [Ni(H2O) 6 ]2 + > [Ni(CN) 4 ]2 – For C.N. = 4 Trans [Ni Br2 (PPh3)2 ]
3d 4s 4p PPh3 Br
17 According to the valence bond Ni
theory the hybridisation of central
q

Br
q

PPh3
Square planar shape
metal atom is dsp 2 for which one
Hybridisation sp3
of the following compounds? (Tetrahedral) and meridional [Co(NH3) 3 (NO2 ) 3]
[2021, 20 July Shift-I] NH3
(d) Na 2 [NiCl4 ]
(a) NiCl2 ⋅6H2O (b) K2 [Ni(CN) 4]
Na2 [NiCl 4 ] → 2Na + [NiCl 4 ]2 − H3N NO2
(c) [Ni(CO) 4] (d) Na2 [NiCl4]
x + 4(−1) − (−2) = 0;where x, 4,−1 Co
Ans. (b) and −2 are the oxidation number of O 2N NO2
According to VBT i.e. valence bond Ni, number of CN ligands, charge
NH3
theory, on one CN and charge on complex.
Meridional (mer)
Electronic configuration of [NiCl 4 ]2 − ⇒x − 4 + 2 = 0 ⇒ x = +2 [trans]
Ni = [Ar] 3d 8 4s 2 . Electronic configuration of
(a) NiCl 2 ⋅ 6H 2O Ni2 + = [Ar]3d 8 4s 0 19 Match List-I and List-II.
NiCl2 ⋅6H2O → NiCl2 + 6H2O For C.N.= 4
List-I List-II
Oxidation number of 3d 4s 4p
Ni(x) = x + 2(−1) = 0; where x,−1 and 2 A. [Co(NH3) 6] [Cr(CN) 6] 1. Linkage isomerism
q
q

are the oxidation number of Ni,

oxidation number of Cl and number Hybridisation sp3 B. [Co(NH3) 3 (NO 2 ) 3] 2. Solvate isomerism
of Cl atoms respectively. (Tetrahedral)
C. [Cr(H2O) 6] Cl 3 3. Co-ordination
NiCl2 ⇒x + (−2) = 0 ⇒ x = 2 isomerism
Hence, onlyK2 [Ni(CN) 4 ] has dsp2
Electronic configuration of hybridisation. D. cis-[CrCl 2 (ox) 2 ] 3− 4. Optical isomerism
Ni2 + = [Ar]3d 8 4s 0
228 JEE Main Chapterwise Topicwise Chemistry

Choose the correct answer from Structure are as follows: 23 Given below are two statements.
−
the options given below. CN can bind through C and N atoms.
Statement I The identification of
[2021, 17 March Shift-II]
C N C N Ni 2+ is carried out by dimethyl
A B C D A B C D NO2− can bind through N and O. glyoxime in the presence of
(a) 3 1 2 4 (b) 4 2 3 1 NH4OH.
N N
(c) 2 1 3 4 (d) 1 2 3 4 –
O O O O Statement II The dimethyl
Ans. (a)
glyoxime is a bidentate neutral
(A)-3, (B)-1, (C)-2, (D)-4 21 The equivalents of ethylene ligand.
A. Coordination isomerisms occurs in diamine required to replace the
coordination salts in which there is
In the light of the above
neutral ligands from the statements, choose the correct
an interchange of ligands between
the metal in the cationic coordination sphere of the answer from the options given
coordination spheres and the trans-complex of COCl 3 ⋅ 4NH3 is below. [2021, 25 Feb Shift-II]
metal in the anionic coordination …… (Round off to the nearest (a) Both statements I and II are true.
sphere. integer). [2021, 16 March Shift-I] (b) Both statements I and II are false.
[Co(NH3) 6 ] [Cr(CN) 6 ] ⇔ Ans. (2) (c) Statement I is true but statement
[Co(CN) 6 ] [Cr(NH3) 6 ] (Coordinate
isomerism) [Co(NH3) 4 Cl2 ] Cl + 2en → II is false.
[Co(en)2 Cl2 ] + 4NH3 (d) Statement I is false but statement
B. Linkage isomerism occurs in
coordination compounds that have NH3 is the neutral monodentate ligand. II is true.
the same composition but differ in Ethylene diamine is a neutral didentate Ans. (a)
the connectivity of the ligand to ligand. Both statements are true. Dimethyl
the metal. •• ••
H2 N  CH2  CH2 NH2 (en ) glyoxime (DMG) is a neutral bidentate
[Co(NH3) 3 (NO2 ) 3] shows linkage ligand (DMG − ).
isomerism. NO2 can connect So, two ethylene diamine are equivalent Ni2 + ion is identified with DMG in
through N and O donor sites. to four ‘NH3’ ligand. presence ofNH4OH to give a red ppt. Its
C. Solvate isomerism is also known reaction is as follows.
as ‘hydrate isomerism’ where water 22 The number of stereoisomers OH
behaves as a ligand and water of possible for [Co(ox) 2 (Br)(NH3 )] 2– is
crystallisation. CH3—C N
……… [ox = oxalate]. 2. + Ni2+
e.g., The [2021, 26 Feb Shift-II] CH3—C N
complex  [Cr(H2O) 6 ]Cl 3  (violet) NH4OH
Ans. (3)
contains water as a ligand and its (DMG–) O—H
solvate The coordination compound O– H—O
III
isomer  [Cr(H2O) 5 Cl] Cl2H2O  (grey- [Co (ox)2 (Br) (NH3)]2 − of general formula [
green) contain water as a water of CH3—C N N C—CH3
crystallisation. [M(A  A)2 BC] can show both Ni2+
geometrical and optical isomerism CH3—C N N C—CH3
D. Optical isomerism occurs mainly in
(stereoisomerism). O—H O –
compounds that are mirror images 2–
of each other. ox or [Ni(DMG)2] (Red ppt.)
Br
cis [CrCl2 (ox)2 ] 3+   is chiral
Co
compound, hence shows optical
H 3N
24 The one that is not expected to
isomerism. ox show isomerism is
2– [2020, 2 Sep Shift-II]
20 The correct pair(s) of the ambident ox
Br (a) [Ni(NH3) 4 (H2O)2] 2+
nucleophiles is(are) Co cis-form (±) (b) [Ni(en) 3] 2+
A. AgCN/KCN H 3N (c) [Ni(NH3)2 Cl2]
ox
B. RCOOAg/RCOOK (d) [Pt(NH3)2 Cl2]
C. AgNO2/KNO2 The cis-form produces Ans. (c)
D. AgI/KI [2021, 17 March Shift-II] non-superimposable mirror images, i.e. [Ni(NH3) 4 (H2O)]2 + of formula Ma 4b2
(a) B and C (b) Only A enantiomeric pairs (optically active) shows geometrical isomerism.
Br 2–
(c) A and C (d) Only B b a
Ans. (c) a a a b
ox Co ox trans-form
The correct pair(s) of ambident M M
nucleophile are (A) KCN and AgCN and (C) a a a b
AgNO2 and KNO2 . NH3
b a
Ambident nucleophiles have the ability The trans-form is optically inactive. cis ( +
trans –) [also shows
to bind the central atom via the two So, total number of stereoisomers optical isomerism]
different atoms. possible = cis (± ) + trans = 3
Coordination Compounds 229

[Ni(en) 3]2 + of formula, M(a − a) 3 shows ox 3– ONO

optical isomerism. en Pt [Pt(en) (NO2) (ONO)]-III
Cl
a a NO2
(d) Cr
a a a a
M M Cl 28 The total number of coordination
a a a a ox sites in
a a ⇒ cis- [CrCl2(ox)2]3– ethylenediaminetetraacetate
Enantiomeric (+
–) Meso form will give non-supper imposable [EDTA 4− ] is … . [2020, 5 Sep Shift-I]
mirror image.
In [Ni(NH3)2 Cl2 ], Ni(II) is sp3-hybridised. Ans. (6)
So, the complex has tetrahedral So, it is optically active.
EDTA4 − is ethylenediaminetetraacetate
geometry. So, stereoisomers So, option (d) is correct. anion. It is a polyprotic acid containing
(geometrical and optical) as well as
four carboxylic acid groups and two
structural isomerism will not be shown 26 Complex (A) has a composition of amine groups with lone-pair electrons
by the complex. In [Pt(NH3)2 Cl2 ] , Pt(II) is
H12O 6Cl 3Cr. If the complex on that chelate calcium and several other
dsp2 -hybridised and the complex has metal ions, it has six coordination sites.
square planar geometry of general treatment with conc. H2SO 4 loses
O O
formula, Ma2b2 which shown geometrical 13.5% of its original mass, the
–
isomerism. correct molecular formula of (A) O C CH2 CH2 C –
O
•• ••
a b a b is[Given : atomic mass of Cr = 52 –
N CH2CH2 N
–
M M amu and Cl = 35 amu] O C CH2 CH2 C O
[2020, 3 Sep Shift-II] O O
a b b a
cis trans (a) [Cr(H2O) 4 Cl2]Cl⋅2H2O It is a hexadentate ligand.
(b) [Cr(H2O) 6]Cl3
25 The complex that can show optical (c) [Cr(H2O) 5 Cl]Cl2 ⋅H2O 29 Consider the complex ions, trans-
activity is [2020, 3 Sep Shift-I] (d) [Cr(H2O) 3Cl3] ⋅ 3H2O [Co(en) 2 Cl 2] + (A) and cis-
(a) trans-[Cr(Cl2 )(ox)2] 3− Ans. (a) [Co(en) 2 Cl 2] + (B). The correct
(b) trans-[Fe(NH3)2 (CN) 4] − Complex (A) = [Cr(H2O) 4 Cl2 ]Cl ⋅2H2O statement regarding them is
(c) cis-[Fe(NH3)2 (CN) 4] − Generally, conc.H2SO4 can act as [2020, 5 Sep Shift-II]
(d) cis-[CrCl2 (ox)2] 3− (ox = oxalate) oxidising agent as well as dehydrating (a) both (A) and (B) cannot be optically
Ans. (d) agent. Here,H2SO4 act as dehydrating active
Cl 3– agent. (b) (A) can be optically active, but (B)
Molar mass of complex = 266.5 g/mol cannot be optically active
On reaction with conc.H2SO4 the mass (c) both (A) and (B) can be optically
(a) ox Cr ox 13.5
by complex = × 266.5 = 359775
. ≈ 36 g active
100 (d) (A) cannot be optically active, but
It means that 2 moles of H2O are present (B) can be optically active
Cl
in complex.
⇒ trans-[Cr(Cl2) (ox)2]3– Ans. (d)
[QMolar mass of H2O = 18 g/mol]
will give super-imposable (A) trans-[Co(en)2 Cl2 ] +
mirror image. (Optically inactive) Then, formula of complex is
[Cr(H2O) 4 Cl2 ]Cl ⋅2H2O Cl
NH 3 –

NC CN 27 The number of isomers possible for en Co en

(b) Fe [Pt(en) (NO 2 ) 2 ] is [2020, 4 Sep Shift-I]
(a) 3 (b) 2 (c) 4 (d) 1 Cl
NC CN trans-form (A)
Ans. (a)
NH 3 (A) is a trans-form and shows plane of
Total number of possible isomers for
⇒ trans-[Fe(NH3)2(CN)4]– symmetry which makes it optically
[Pt(en)(NO2 )2 ] are 3. inactive (not optically active).
will also give super-impoable
mirror image. (Optically inactive) NO2  ambidentate ligand, en (B) cis-[Co(en)2 Cl2 ] +
– bidentate ligand and coordination Cl
CN number is 4.
NC Cl
NH3 Structures are as follows : en Co
(c) Fe NO2
en Pt [Pt(en) (NO2)2]-I
NH3
en

NC
NO2 cis-form
CN (B)
⇒ cis- [Fe(NH3)2(CN)4]– ONO
cis-form does not contain any plane of
has also plane of symmetry en Pt [Pt(en) (ONO)2]-II symmetry. So that, the compound (B) is
and it is also optically inactive. ONO optically active.
230 JEE Main Chapterwise Topicwise Chemistry

30 The theory that can completely/ monoanionic ligands, 34 Among (A) - (D), the complexes that
properly explain the nature of bonding respectively. [2020, 7 Jan Shift-II] can display geometrical isomerism
in [Ni(CO) 4] is : [2020, 7 Jan Shift-I] (a) 0 and 0 (b) 0 and 1 are
(a) Werner’s theory (c) 2 and 2 (d) 0 and 2 (A) [Pt(NH3 ) 3 Cl] +
Ans. (a)
(b) Crystal field theory (B) [Pt(NH3 )Cl 5] −
(c) Valence bond theory Optical isomerism is possible only in
(d) Molecular orbital theory chiral molecules. A structure is chiral, if (C) [Pt(NH3 ) 2 Cl(NO 2 )]
Ans. (d)
its mirror image is non-superimposable (D) [Pt(NH3 ) 4 ClBr] 2+
and therefore, it should not have a [2020, 8 Jan Shift-II]
Bonding in metal carbonyls like [Ni(CO) 4 ] centre of symmetry or plane of (a) (D) and (A) (b) (C) and (D)
can’t be properly explained by Werner’s symmetry.
theory, valence bond theory or crystal (c) (A) and (B) (d) (B) and (C)
An MA2 B2 complex of sp3-hybridised
field theory. The concept of synergic metal (M) has tetrahedral geometry. Ans. (b)
bonding based on molecular orbital (A) [Pt(NH3) 3 Cl] + : No geometrical
theory is used to explain their bonding. In A
isomerism
Ni(CO) 4 , backbonding involving filled
M (B) [Pt(NH3)Cl 5 ] − : No geometrical
d-orbitals of Ni and antibonding
B B isomerism
π * orbitals of carbon monoxide is part of
synergic bonding. A (C) [Pt(NH3)2 Cl (NO2 )] : Has 2
geometrical isomers
Thus, the nature of bonding inNi(CO) 4 is There are clearly many planes of
completely explained by molecular symmetry in the structure and the (D) [Pt(NH3) 4 ClBr]2 + : exhibit
orbital theory. structure is geometrical isomerism.
superimposable on its mirror image. All Pt2 + complexes with coordination
31 The IUPAC name of the complex number equals to4 are square planar.
∴ It has no optical isomers.
[Pt(NH3 ) 2 Cl(NH2CH3 )]Cl is ∴ The two NH3 ligands could arrange in
An MA2 B2 complex of dsp2 -hybridised
[2020, 7 Jan Shift-I] cis or trans positions.
metal (M) has square planar geometry.
(a) diammine (methanamine) chlorido ∴ There are two geometrical isomers.
platinum (II) chloride A A A B
NH3 NH3 NH3 NO2
M or M
(b) diamminechlorido (methanamine) Pt Pt
platinum (II) chloride B B B A
cis trans
Cl NO2 Cl NH3
(c) diamminechlorido (aminomethane) cis trans
platinum (II) chloride There are two geometrical isomers cis
(d) bisammine (methanamine) and trans. (D) ) [Pt(NH3) 4 ClBr] : Two geometrical
chlorido platinum (II) chloride But, since they are planar and therefore isomers Coordination number = 6
Ans. (b) they always have a plane of symmetry. ∴ Octahedral geometry
∴ No optical isomerism also. Cl and Br can be cis or trans
The given compound has a cationic part
[Pt(NH3)2 Cl(NH2 CH3)] + and anionic part ∴ 2 geometrical isomers
Cl − . Cationic part is a complex, so its 33 The complex that can show fac-
Cl Cl
name starts with ligands in alphabetical and mer-isomers is :
order followed by metal (with oxidation [2020, 8 Jan Shift-I] H3N NH3 Br NH3
Pt Pt
number in bracket). Ligands are NH3 (a) [Pt(NH3)2 Cl2] H3N NH3 NH3 NH3
(ammine), Cl − (chloride) and CH3NH2 (b) [Co(NH3) 3 (NO2 ) 3] NH3
Br
(methanamine). For two NH3, diammine
is used. (c) [Co(NH3) 4 Cl2] + trans

‘Methanamine’ is written inside (d) [CoCl2 (en)2]

paranthesis or bracket because it is Ans. (b) 35 Complex X of composition
itself a composite name. (For such Octahedral coordination entities of the Cr(H2O) 6 Cl n has a spin only
ligands, when two of them are present, type [Ma3 b3 ] shows geometical isomers: magnetic moment of 3.83BM. It
‘bis’ is used instead of ‘di’). Oxidation fac and mer isomers. Among the given reacts with AgNO 3 and shows
number of Pt in the complex is +2. complexes, the complex with general geometrical isomerism. The IUPAC
∴ The correct IUPAC name is diammine- formula [Ma3 b3 ] is [Co(NH3) 3 (NO2 ) 3] .
nomenclature of X is
chlorido (methanamine) platinum (II) Thus, it can show fac and mer isomers as [2020, 9 Jan Shift-II]
chloride. follows:
(a) tetraaquadichlorido chromium (IV)
NH3 NH3 chloride dihydrate
32 The number of possible optical
NH3 H N (b) hexaaqua chromium (III) chloride
isomers for the complexes MA 2B2 O2N 3 NO2
Co Co (c) dichloridotetraaqua - chromium
with sp 3 and dsp 2 hybridised metal NH3 O N (IV) chloride dihydrate
2 NO2
atom, respectively, is O2N
NO2 (d) tetraaquadichlorido - chromium
NH3
Note : A and B are unidentate (fac) (mer) (III) chloride dihydrate
neutral and unidentate
Coordination Compounds 231

Ans. (d) Ans. (b) Ans. (d)

Cr(H2O) 6 Cl n (X) Key Idea Denticity of ligand is defined as Key Idea The total number of ligands to
Spin only magnetic moment = 3.83 BM donor sites or number of ligating groups. which the metal is directly attached is
∴ n(n + 2) = 3.83 The given ligand is tetradentate. It called coordination number.
⇒ n (number of unpaired electrons) = 3 contains four donor atoms. It can bind The coordination numbers of Co and Al
through two nitrogen and two oxygen in [Co(Cl)(en)2 ]Cl and K3 [Al(C2O4 ) 3] are 5
(Note : the ‘n’ used in the formula atom to the central metal ion. and 6 respectively.
Cr(H2O) 6 Cl n is not this ‘n’).
Ligand bound to the central atom or ion In first complex, ‘en’ is a didentate ligand
To have 3 unpaired electrons, Cr must be through coordinate bond in the and ‘Cl’ is a unidentate ligand.
in +3 oxidation state. Cr 3+ = d 3, coordination entity. It act as a Lewis [Co(Cl)(en)2 ]Cl, coordination number
∴3 unpaired electrons are present. base. The attacking site of the given = 1 + 2 × 2 = 1 + 4 ⇒5
∴Chemical formula = Cr(H2O) 6 Cl 3 ligand is given in bold.
So, the coordination number is 5.
(n in the formula Cr (H2O) 6 Cl n is also = 3, NEt2
because Cr is +3, 3Cl − must be there). For K3 [Al(C2O4 ) 3], ‘C2O24 − ’ is a didentate
N ligand.
To show geometrical isomerism, at least
two different types of ligands must be Coordination number = 3 × 2 = 6.
O- -O
Hence, coordination number is 6.
there and at least two ligand of each
type should be present.
∴ It must be [Cr(H2O) 4 Cl2 ]Cl.2H2O or 40 The total number of isomers for a
[Cr(H2O) 3 Cl 3] ⋅3H2O square planar complex
But it is also given that, the complex 38 The species that can have a [M(F) (Cl) (SCN) (NO 2 )] is
reacts with AgNO3. trans-isomer is (en = ethane -1, (a) 12 (b) 16
∴ At least one Cl − ion must be outside 2-diamine, ox = oxalate) (c) 4 (d) 8
coordination sphere. [2019, 10 April Shift-I] [2019, 10 Jan Shift-I]
O
∴It must be [Cr(H2O) 4 Cl2 ]Cl.2H2O O
Ans. (a)
–
IUPAC name : O C CH2 CH2 C O
–
•• ••
A square planar complex of general
Tetraaquadichloridochromium (III) N CH2CH2 N formula, Mabcd gives three geometrical
– –
chloride dihydrate. O C CH2 CH2 C O isomers only.
36 The isomer (s) of [Co(NH3 ) 4 Cl 2] O O Let, a = F − , b = Cl − , c = S CN− , d = NO2−
+
(a) [Pt(en)Cl2] (b) [Cr(en)2 (ox)] SCN− and NO2− are ambidentate ligands
that has/have a Cl Co Cl angle
(c) [Pt(en)2 Cl2] 2+ (d) [Zn(en)Cl2] and they also show linkage isomerism
of 90°, is/are [2020, 9 Jan Shift-II]
Ans. (c) (structural). Considering both linkage
(a) cis and trans and geometrical isomerism.
(b) meridional and trans Key Idea Square planar complexes of
general formulae : [M(a − a)b2 ] and Total number of possible isomers given
(c) cis only by the complex, = 3 × (2 + 2) = 12
[M(a − a) (b − b)] do not show geometrical
(d) trans only
isomerism. Whereas, an octahedral
Ans. (c) complex of general formula [M(a − a)2 b2 ] 41 A reaction of cobalt (III) chloride
The isomers of [Co(NH3) 4 Cl2 ] that have a can show geometrical (cis-trans) and ethylene diamine in a 1 : 2 mole
Cl  Co  Cl angle of 90° is cis only. isomerism. ratio generates two isomeric
[Pt(en)2 (Cl2 )]2 + with formula [M(a − a)2 b2 ] products A (violet coloured) and B
Cl
will show geometrical isomerism as
90° (green coloured). A can show
Cl NH3 follows:
Co optical activity, but B is optically
H3N NH3 Cl 2+
2+
NH3
inactive. What type of isomers
en
Cl does A and B represent ?
trans isomer has Cl  Co  Cl angle of en Pt en [ 2019, 10 Jan Shift-II]
180°. Pt
(a) Ionisation isomers
Cl (b) Coordination isomers
37 The following ligand is en (c) Geometrical isomers
Cl
NEt2 cis- trans- (d) Linkage isomers
(optically active) (optically inactive)
N (I) Ans. (c)
According to the situation given in
39 The coordination numbers of Co question, reactions are as follows:
O– –
O and Al in [CoCl(en) 2]Cl and III III
CoCl 3 + 2en → [Co(en)2 Cl2 ]Cl
K 3 [Al(C 2O 4 ) 3], respectively, are (en •• 
= ethane-1, 2-diamine) CH2  N H2 
[2019, 8 April Shift-I] [2019, 12 April Shift-II] en = ethylene-1, 2-diamine,  
(a) hexadentate (b) tetradentate (a) 5 and 3 (b) 3 and 3 CH2  N H2 
••
(c) bidentate (d) tridentate 
(c) 6 and 6 (d) 5 and 6
232 JEE Main Chapterwise Topicwise Chemistry

Cl 44 Consider the following reaction and

en 45 A solution containing 2.675 g of
Cl statements : [JEE Main 2018] CoCl 3 ⋅ 6NH3 (molar mass = 267.5 g
[Co(NH3 ) 4 Br 2] + + Br − →
III
Co Cl en Co en Cl mol −1 ) is passed through a cation
[Co(NH3 ) 3 Br 3] + NH3 exchanger. The chloride ions
Cl
en I. Two isomers are produces if obtained in solution were treated
Cl with excess of AgNO 3 to give 4.78
‘A’ Optically active ‘B’ Optically inactive
the reactant complex ion is a
(cis-form) (trans-form) cis-isomer. g of AgCl (molar mass
(Violet) (Green) II. Two isomers are produced if = 143.5 g mol −1 ). The formula of the
the reactant complex ion is a complex is (Atomic mass of
42 The coordination number of Th in trans-isomer. Ag = 108 u) [AIEEE 2010]
K 4 [Th(C 2O 4 ) 4 (OH2 ) 2] is III. Only one isomer is produced if (a) [Co(NH3) 6]Cl3
(C 2O 24 − = Oxalato) the reactant complex ion is a (b) [CoCl2 (NH3) 4]Cl
(a) 14 (b) 10 trans-isomer. (c) [CoCl3 (NH3) 3]
(c) 8 (d) 6 IV. Only one isomer is produced if (d) [CoCl(NH3) 5]Cl2
[2019, 11 Jan Shift-II]
the reactant complex ion is a Ans. (a)
Ans. (b) cis-isomer. 2.675
Mole of CoCl 3 ⋅6NH3 = = 0.01 mol
Coordination number is defined as the 267.5
The correct statements are
total number of ligands to which the
(a) (I) and (II) AgNO3 (aq) + Cl − (aq) → AgCl ↓ (white)
metal is directly attached. + NO−3 (aq)
(b) (I) and (III)
Here, C2O24 − is a bidentate ligand, 4.78
(c) (III) and (IV) Moles of AgCl = = 0.03 mol

O 143.5
CO (d) (II) and (IV)
0.01 mol CoCl 3 ⋅6NH3 gives = 0.03 mol



M (Metal) Ans. (b)

CO  AgCl
O
 If the reactant is cis isomer than ∴1 mol CoCl 3 ⋅6NH3 ionises to give = 3 mol
following reaction takes place. Cl −
and H2O is a monodentate ligand,
H2O M Br Br Hence, the formula of compound is
NH3 Br NH3 Br [Co(NH3) 6 ]Cl 3.
So, total number of sites offered by
C2O24 − and H2O ligands around Br–
Th(IV) = Coordination number of Th (IV) 46 On treatment of 100 mL of 0.1 M
= 4 × 2 (by C2O24 − ) + 2 × 1 (by H2O) = 10 NH3 NH3 NH3 Br solution of CoCl 3 . 6H2O with excess
NH3 NH3 of AgNO 3 ; 1.2 × 10 22 ions are
43 The oxidation states of Cr, in Cis-isomer Facial precipitated. The complex is
[Cr(H2O) 6]Cl 3 , [Cr(C 6H6 ) 2], and Br [JEE Main 2017]
K 2 [Cr(CN) 2 (O) 2 (O 2 ) (NH3 )] NH3 Br (a) [Co(H2O) 4 Cl2 ] Cl ⋅ 2H2O
respectively are [JEE Main 2018] (b) [Co(H2O) 3Cl3] ⋅3H2O
+
(a) +3, +4 and +6 (b) +3, +2 and +4 (c) [Co(H2O) 6 ]Cl 3
(c) +3, 0 and +6 (d) +3, 0 and +4 NH3 NH3 (d) [Co(H2O) 5 Cl] Cl2 ⋅H2O
Ans. (b) Ans. (d)
Br
Let the oxidation state of Cr in all cases Meridonial Number of moles of solute
is ‘ x ’ Molarity (M) =
i.e. two isomers are produced. Volume of solution (in L)
(i) Oxidation state of Cr in [Cr(H2O) 6 ]Cl 3 ∴Number of moles of complex
If the reactant is trans isomer than
x + (0 × 6) + (−1 × 3) = 0 Molarity × volume (in mL)
following reaction takes place. =
or x + 0 − 3 = 0 or x = + 3 1000
(ii) Oxidation state of Cr in [Cr(C6H6 )2 ] Br Br
NH3 NH3 NH3 NH3 0.1 × 100
= = 0.01 mole
x + (2 × 0) = 0 or x = 0 1000
Br–
(iii) Oxidation state of Cr in Number of moles of ions precipitate
K2 [Cr(CN)2 (O)2 (O2 )(NH3)] . × 1022
12
NH3 NH3 NH3 Br = = 0.02 moles
1 × 2 + x + (−1 × 2 ) + (−2 × 2 ) + (−2) + 0 = 0
. × 1023
602
Br Br
or 2 + x − 2 − 4 − 2 = 0
Trans Meridonial ∴Number of Cl − present in ionisation
or x −6=0 sphere
hence x = + 6 i.e. only 1 isomer is produced. Thus,
Number of moles of ions precipitated
Thus, +3, 0 and +6 is the answer.
statement (I) and (III) are correct resulting =
to option (b) as the correct answer. Number of moles of complex
Coordination Compounds 233
0.02 [Co(NH3) 3 Cl 3] exists in fac and Ans. (c)
= =2
0.01 mer-isomeric forms and both are Optical isomerism is exhibited by only
∴ 2 Cl − are present outside the square optically inactive. those complexes which lacks elements
brackets, i.e. in ionisation sphere. Thus, NH3 NH3 of symmetry.
the formula of complex is Cl NH3 Cl NH3 [Co(NH3) 3 Cl 3] shows facial as well as
[Co(H 2 O) 5 Cl] Cl2 ⋅H 2 O. meridional isomerism. But both the forms
Co Co contain plane of symmetry. Thus, this
47 The pair having the same magnetic complex does not exhibit optical isomerism.
Cl NH3 Cl Cl
moment is Cl NH3
[at. no. Cr = 24, Mn = 25, Fe = 26 fac-isomer mer-isomer
51 Which among the following will be
and Co = 27] [JEE Main 2016] (optically inactive) (optically inactive) named as dibromidobis-
(a) [Cr(H2O) 6] 2+ and [Fe(H2O) 6] 2+ (ethylenediamine) chromium (III)
(b) [Mn(H2O) 6] 2+ and [Cr(H2O) 6] 2+ 49 The equation which is balanced bromide? [AIEEE 2012]

(c) [CoCl4] 2−
and [Fe(H2O) 6] 2+ and represents the correct (a) [Cr (en) 3]Br3 (b) [Cr (en)2 Br2]Br
product(s) is [JEE Main 2013] (c) [Cr (en)Br4] – (d) [Cr (en)Br2]Br
(d) [Cr(H2O) 6] 2+ and [CoCl4] 2−
(a) Li2O + 2KCl → 2LiCl + K2O Ans. (b)
Ans. (a)
(b) [CoCl (NH3) 5] + + 5H+ → CO2+ Two Br, two (en) and one Cr are parts of
Electronic Number of + 5NH+4 + Cl− complex.
Complex ion configuration unpaired (c) [Mg (H2O) 6] + (EDTA) 4 −
2+ Charge on the complex is
of metal ion electrons (n) excessNaOH 2(Br) = −2
→ [Mg (EDTA)] 2 + + 6H2O 
2(en) = 0  = +1
[Cr(H2O) 6] 2 + Cr 2 + ; [Ar] 3 d 4 ; 4
(d) CuSO 4 + 4KCN → 1(Cr) = +3 
[Fe(H2O) 6] 2+
Fe 2+
; [Ar] 3 d 6
;5 K2 [Cu (CN) 4] + K2 SO 4
Thus, complex ion is [Cr(en)2 Br2 ] + .
Ans. (b)
Since, anion is bromide thus, complex is
[Mn(H2O) 6] 2 + Mn2 + ; [Ar] 3 d 5 ;3
(a) Li2O + 2KCl → 2LiCl + K2O [Cr(en)2 Br2 ]Br.
2− 2+ 7 The above equation is incorrect
[CoCl 4] Co ; [Ar] 3 d
52 Among the ligands NH3 , en, CN −
;4
because K2O, a stronger base
cannot be generated by a weaker
base, Li2O. and CO, the correct order of their
48 Which one of the following increasing field strength, is
(b) [CoCl (NH3) 5 ] + + 5H+ → CO2 + [AIEEE 2011]
complexes shows optical + 5NH+4 + Cl −
isomerism? [JEE Main 2016] (a) CO < NH3 < en < CN−
The above equation is correct (b) NH3 < en < CN− < CO
(a) cis [Co(en)2 Cl2]Cl
(b) trans [Co(en)2 Cl2]Cl
because amine complexes (c) CN− < NH3 < CO < en
decomposes under acidic medium. (d) en < CN− < NH3 < CO
(c) [Co(NH3) 4 Cl2]Cl Thus, the complex [CoCl (NH3) 5 ]
decomposes under acidic Ans. (b)
(d) [Co(NH3) 3Cl3]
conditions to give ammonium ions. Based on spectrochemical series,
Ans. (a)
(c) [Mg (H2O) 6 ]2 + + (EDTA) 4 − ligands arranged in increasing order of
Cl Cl crystal field strength are as
excess NaOH
Cl → [Mg (EDTA)]2 + + 6H2O NH3 < en < CN− < CO
en Co en Co en The above equation is incorrect
because the product formed would 53 Which one of the following
en
Cl be [Mg (EDTA)]2 − . complex ions has geometrical
cis-[Co(en)2Cl2]Cl trans-[Co(en)2Cl2]Cl (d) CuSO4 + 4KCN → K2 [Cu (CN) 4 ] isomers? [AIEEE 2011]
(optically active) (optically inactive due
+K2SO4 (a) [Co (en) 3] 3+
to plane of symmetry)
The above equation is incorrect. (b) [Ni (NH3) 5 Br] +
[Co(NH3) 4 Cl2 ]Cl can exist in both cis and Thus, the correct equation is (c) [Co(NH3)2 (en)2] 3+
trans forms that are given below: 2KCN + CuSO4 → K2SO4 (d) [Cr(NH3) 4 (en)] 3+
+ + + Cu + (CN)2 Ans. (c)
Cl NH3
(Cyanogen gas)
H 3N NH3 H3N Cl
Complex Isomerism shown
Co Co 50 Which of the following complex (a) | Co(en) 3 | 3+ Optical only
H 3N NH3 H3N Cl species is not expected to exhibit (b) |Ni(NH3) 5 Br| +
No geometrical isomer
Cl NH3 optical isomerism? [JEE Main 2013] (c) | Co(NH3) 2 (en) 2 | 3+ Cis and trans
trans-[Co(NH3)4Cl2]Cl cis-[Co(NH3)4Cl2]Cl (a) [Co(en) 3] 3+ (b) [Co(en)2 Cl2] +
(optically inactive) (optically inactive) (c) [Co(NH3) 3Cl3] (d) [Co(en) (NH3)Cl2] + (d) | Cr(NH3) 4 (en)| 3+ No geometrical isomer
234 JEE Main Chapterwise Topicwise Chemistry

54 Which one of the following has an 57 The coordination number and the 60 The IUPAC name of the
optical isomer? oxidation state of the element ‘E’ in coordination compound
(en = ethylenediamine) the complex [E (en) 2 (C 2O 4 )] NO 2 K 3 [Fe(CN) 6] is [AIEEE 2005]
[AIEEE 2010] (where (en) is ethylene diamine) (a) tripotassium hexacyanoiron (II)
(a) [Zn(en)(NH3) 2] 2+ are, respectively [AIEEE 2008] (b) potassium hexacyanoiron (II)
(b) [Co(en) 3] 3+ (a) 6 and 2 (b) 4 and 2 (c) potassium hexacyanoferrate (III)
(c) [Co(H2O) 4 (en)] 3+ (c) 4 and 3 (d) 6 and 3 (d) potassium hexacyanoferrate (II)
(d) [Zn(en) 2] 2+ Ans. (d) Ans. (c)
Ans. (b) en, CH2 NH2 is bidentate ligand K3 [Fe(CN) 6 ]
Complex [Co(en) 3] 3+ has no plane of  Cation Anion
CH2 NH2
symmetry and centre of symmetry. Oxidation state of Fe in anion = + 3
That’s why, it is optically active. C2O24– is also bidentate ligand. Thus, it is potassium hexacyanoferrate
en en Hence, coordination number of the (III).
element E in the given complete comes
en en out to be 6. 61 Which of the following compounds
Co3+ Co 3+
The complex can be ionised as shows optical isomerism ?
[AIEEE 2005]
[E (en)2 (C2O4 )] NO2 →
en en [E (en)2 (C2O4 )] + NO2− (a) [Co(CN) 6] 3− (b) [Cr(C2O 4 ) 3] 3−
(c) [ZnCl4] 2− (d) [Cu(NH3) 4] 2+
Oxidation number x + 0 + (−2) = + 1
55 Which of the following has an ⇒Oxidation number, x = 3 Ans. (b)
optical isomer? [AIEEE 2009] C2O4
3–

(a) [Co(NH3) 3Cl] + 58 How many EDTA (ethylenediamine

(b) [Co(en)(NH3)2] 2+ tetraacetic acid) molecules are C2O4 Cr
(c) [Co(H2O) 4 (en)] 3+ required to make an octahedral
(d) [Co(en)2 (NH3)2] 3+ complex with a Ca 2+ ion?
C2O4
Ans. (d) [AIEEE 2006]
(a) Six (b) Three Mirror image is not superimposable,
NH3 3+ H3N 3+
(c) One (d) Two hence optical isomerism is possible.
H2N NH3 H3N NH2 Ans. (c)
Co Co EDTA (Ethylenediamine tetraacetic acid)
62 Which one of the following has
−
largest number of isomers?
H2N NH2 H2N NH2 OOCCH2 CH2 COO−
(R = alkyl group, en =
NH2 NH2 N CH2  CH2 N
•• •• ethylenediamine) [AIEEE 2004]
−
OOCCH2 CH2 COO− (a) [Ru(NH3) 4 Cl2] +
56 Which of the following pairs It is hexadentate (6 electron pairs). (b) [Co(NH3) 5 Cl] 2+
represents linkage isomers? That’s why for octahedral complex, only (c) [Ir(PR 3)2 H(CO)] 2+
[AIEEE 2009]
one EDTA is required. (d) [Co(en)2 Cl2] +
(a) [Cu(NH3) 4][PtCl4] Ans. (d)
and [Pt(NH3) 4][CuCl4] 59 The IUPAC name for the complex All the given compounds, exhibits
(b) [Pd(PPh3)2 (NCS)2] [Co(NO 2 ) (NH3 ) 5]Cl 2 is [AIEEE 2006] geometrical (cis and trans isomers) but
and [Pd(PPh3)2 (SCN)2] only cis isomer of [CO (en)2 Cl2 ] +
(a) nitrito-N-pentamminecobalt (III)
(c) [Co(NH3) 5]NO 3SO 4 chloride possess optical isomers (d and l) due to
and [Co(NH3) 5 SO 4]NO 3 (b) nitrito-N-pentamminecobalt (II) the presence of symmetrical didentate,
(d) [PtCl2 (NH3) 4]Br2 en [ethylediamine].
chloride
and [PtBr2 (NH3) 4]Cl2 (c) pentammine nitrito-N-cobalt (II) 63 One mole of the complex
Ans. (b) chloride compound Co(NH3 ) 5 Cl 3 , gives 3
Linkage isomers are caused due to the (d) pentammine nitrito-N-cobalt (III) moles of ions on dissolution in
presence of ambidentate ligands chloride water. One mole of the same
[Pd(PPh3)2 (NCS)2 ] and Ans. (d)
[Pd(PPh3)2 (SCN)2 ] are linkage isomers complex reacts with two moles of
due to SCN, an ambidentate ligand. The IUPAC name for the complex AgNO 3 solution to yield two moles
Thus, SCN can linked to Pd by both N as [Co(NO2 ) (NH3) 5 ]Cl2 of AgCl(s). The structure of the
well as S through their lone pairs. Pentammine nitrito-N-cobalt (III) chloride complex is [AIEEE 2003]
Coordination Compounds 235

(a) [Co(NH3) 5 Cl] Cl2 (FeCl 3) due to formation of iron 70 In the structure of the dichromate
(b) [Co(NH3) 3Cl3] ⋅2NH3 (III)hexacyanoferrate (II).
ion, there is a [2021, 31 Aug Shift-I]
(c) [Co(NH3) 4 Cl2]Cl⋅NH3 FeCl 3 + K4 [Fe(CN) 6 ] →
(a) linear symmetrical Cr O Cr
(d) [Co(NH3) 4 Cl] Cl2 ⋅NH3 Fe4 [Fe(CN) 6 ] 3 bond.
Iron (III) hexacyanido-ferrate (II)
Ans. (a) (Prussian blue colour) (b) non-linear symmetrical Cr O Cr
bond.
The oxidation state of nickel is 68 The crystal field stabilisation (c) linear unsymmetrical Cr O Cr
[Co(NH3) 5 Cl] Cl2 energy (CFSE) and magnetic
r [Co(NH3) 5 Cl]2 + + 2Cl −
bond.
1444 424444 3 moment (spin-only) of an (d) non-linear unsymmetrical
three ions octahedral aqua complex of a Cr O Cr bond.
64 In the coordination compound, metal ion (M + ) are − 0.8 ∆ o and 3.87 Ans. (b)
K 4 [Ni(CN) 4] the oxidation state of BM, respectively. The structure of dichromate ion (Cr2O27– )
nickel is [AIEEE 2003]
Identify (M 2+ ). [2021, 1 Sep Shift-II] contains a non-linear symmetrical
(a) − 1 (b) 0 (c) + 1 (d) + 2 (a) V 3+ (b) Cr 3+ Cr—O—Cr bond.
Ans. (b) (c) Mn4+ (d) Co2+ O O
The oxidation state of nickel is Ans. (d)
K4 [Ni(CN) 4 ] → 4K+ + [Ni(CN) 4 ] 4 − The crystal field stabilisation energy
Cr Cr
O O O
[Ni(CN) 4 ] 4– → x + (4 × − 1) = − 4 (CFSE) and magnetic moment (spin-only) O
O
x − 4 = − 4 or x = 0 of Co2 + octahedral aqua complex are −
0.8∆ o and 3.87 BM respectively. Hence, correct option is (b).
65 Type of isomerism shown by
[Cr(NH3 ) 5 NO 2] Cl 2 is [AIEEE 2002] Co2+
71 Acidic ferric chloride solution on
(a) optical (b) ionisation d-orbital treatment with excess of
(c) geometrical (d) linkage eg potassium ferrocyanide gives a
Ans. (d) +0.6Do prussian blue coloured colloidal
[Cr(NH3) 5 NO2 ] Cl2 (Pentamminenitrito –0.4Do species. It is [2021. 27 Aug Shift-I]
chromium (III) chloride) exhibits linkage t2 g (a) Fe 4 [Fe(CN) 6] 3
isomerism as −NO2 is ambidentate (b) K 5Fe[Fe(CN) 6] 2
ligand. Isomer is [Cr(NH3) 5 ONO] Cl2 . CFSE= [(e − in t2 g ) × (− 0.4) (c) HFe[Fe(CN) 6]
+ (e − in e g ) × 0.6] ∆ o
66 A square planar complex is formed (d) KFe[Fe(CN) 6]
= [5 × − 0.4 + 2 × 0.6] ∆ o
by the hybridisation of the following Ans. (a)
= − 0.8 ∆ o
atomic orbitals [AIEEE 2002]
Magnetic moment (spin only) can be
When a solution of ferric chloride is
(a) s, px, py, pz calculated as : treated with potassium ferrocyanide
(b) s, px, py, pz, d solution, a prussian blue precipitate of
µ = n(n + 2)
ferric ferrocyanide is obtained.
(c) d, s, px, py (where,µ = spin only magnetic moment
(d) s, px, py, pz, d, d and 4FeCl 3 + 3K4 [Fe(CN) 6 ] →
Ferric chloride Potassium ferrocyanide
Ans. (c) n = number of unpaired electrons = 3
A square planar geometry is the result of = 3(3 + 2) = 15 = 3.87 BM Fe4 [Fe(CN) 6 ] 3 + 12KCl
Ferric ferrocyanide
dsp2 hybridisation where innerd
sub-shell (d 2 2 orbital) participates. 69 The number of hydrogen bonded
x −y
water molecule(s) associated with 72 The overall stability constant of the
TOPIC 2 stoichiometry CuSO 4 ⋅ 5H2O is/are. complex ion [Cu(NH3 ) 4] 2+ is
2.1 × 10 13 . The overall dissociations
Bonding in Coordination [2021, 31 Aug Shift-I]
constant is y × 10 − 14 . Then, y is
Ans. (1)
Compounds ……… . (Nearest integer)
The number of hydrogen bonded water
[2021, 26 Aug Shift-II]
molecule associated with stoichiometry
67 The potassium ferrocyanide CuSO4 ⋅ 5H2O is 1. Ans. (5)
solution gives a prussian blue H H Given, K f = 2.1 × 10 13
colour, when added to | | + δ
+
O—H δ H O O Dissociation constant
[2021, 1 Sep Shift-II] H—O
1
(a) CoCl3 (b) FeCl2 (c) CoCl2 (d) FeCl3 δ
– (K d ) =
Cu2+ O S Kf
Ans. (d) δ
+
O—H = 4.7 × 10 −14
Potassium ferrocyanide solution H—O H O O
{K4 [Fe(CN) 6 ]} will give prussian blue
| | δ
+
∴ y = 4.7 −
~ 5.
H H
colour when added to ferric chloride
236 JEE Main Chapterwise Topicwise Chemistry

73 Arrange the following cobalt Ni+4 → 3d 6 = t26g , e g0 (a) 6 and 4 (b) 4 and 1
complexes in the order of (Presence of strong field) (c) 6 and 5 (d) 5 and 1
increasing crystal field stabilisation Unpaired electron = 0 Ans. (b)
energy (CFSE) value. Similarly, NiCl2 → Ni2 + CuSO4 ⋅ 5H2O is blue vitriol, which is
3− 3+ 8 represented as [Cu(H2O) 4 ] ⋅H2O⋅SO4 .
[CoF6] , [Co(H2O) 6] , d =
( A) ( B)
Here, secondary valencies are4H2O and
(Two unpaired electrons) 1H2O molecule outside coordination
[Co(NH3 ) 6] 3+ and [Co(en) 3] 3+ Number of unpaired electron inNiCl2 and sphere is involved in hydrogen bonding.
(C ) ( D) [Ni(CN) 6 ]2 − are two and zero
δ+ δ-
respectively. O–
Choose the correct option. H 2O
2+
OH2 H
[2021 26 Aug Shift-II] Change in number of unpaired electrons Cu O δ+ S
δ-
⇒2 to 0. H 2O OH2 H O O–
(a) A < B < C < D (b) B < A < C < D
Change = 2
(c) B < C < D < A (d) C < D < B < A Hydrogen bonded
Ans. (a) water molecule=1
76 The spin only magnetic moment secondary valency=4
For the same central metal ion, the CFSE value for the complex [Co(CN) 6] 4− Hence, option (b) is correct.
increases with increase in strength of
is …… BM.
the ligand. The order of strength of
ligand is given by the spectrochemical [Atomic number of Co = 27] 78 The total number of unpaired
series : [2021, 20 July Shift-I] electrons present in the complex
Ans. (2)
I− < Br − < SCN− < Cl − < S2 − < F − < OH− K 3 [Cr(oxalate) 3 ] is ........... .
< C2O24– < H2O < NCS − < EDTA4 − < NH3 < en [Co(CN) 6 ] 4 − [2021, 18 March Shift-I]

< CN− < CO x + 6 × (− 1) = − 4 Ans. (3)

Thus, the order of CFSE of given where x, 6, − 1 and −4 are the oxidation K3 [Cr(ox) 3]
complexes will be : number of Co, number of CN ligands,
Let, x be the oxidation state of Cr in
charge on one CN and charge on
[CoF6 ] 3− < [Co(H2O) 6 ] 3+ < [Co(NH3) 6 ] 3+ K3 [Cr(C2O4 ) 3]. Since, the overall charge
complex.
(A ) (B) (C ) on the complex is 0, the sum of oxidation
x = + 2, i.e. Co2 + states of all elements in it should be
< [Co(en) 3] 3+ .
(D )
Electronic configuration of Co2 + : equal to 0. Therefore,
[Ar] 3d 7 and CN− is a strong field ligand + 3 + x + 3(− 2) = 0 (oxalate is bidentate
74 Which one of the following which can pair electron of central atom. ligand and having −2 charge)
complexes is violet in colour?
[2021, 26 Aug Shift-I]
Transference or, x = + 3.
of electrons
(a) [Fe(CN) 6] 4− Hence, chromium is in + 3oxidation state.
3d
(b) [Fe(SCN) 6] 4− Cr → 3d 5 4s 1 (ground state electronic
Co2+ : [Ar]
(c) Fe 4 [Fe(CN6 )] 3.H2O configuration)
(d) [Fe(CN) 5 NOS] 4−
4s 4p 4d Cr 3+ → 3d 34s 0 (Excited state)
Ans. (d) 3d 4s 4p
4− 3d 4s 4p
The complex [Fe(CN) 5 NOS] is violet in
colour. It is formed when sodium Co2+ : [Ar]
nitroprusside reacts with sulphide ion to d2sp3
give violet colour as follows d2sp3 hybridisation
4d CN = 6
S2 − + [Fe(CN) 5 NO]2 − → [Fe(CN) 5 NOS] 4 − ∴ oxalate is weak field ligand
(Violet colour)
It has one unpaired electron (n) in ∴ 3 unpaired electron ind-orbital. The
75 An aqueous solution of NiCl 2 was 4d-subshell. hybridisation of chromium in the
heated with excess sodium cyanide So, spin only magnetic moment complex isd2 sp3.
in presence of strong oxidising (µ) = n(n + 2) BM
agent to form [Ni(CN) 6] 2− . The = 1(1 + 2) BM = 3 BM 79 On complete reaction of FeCl3 with
total change in number of unpaired oxalic acid in aqueous solution
where, n = number of unpaired electrons
electrons on metal centre is …… . containing KOH, resulted in the
µ = 3 BM = 1.73 BM
[2021, 20 July Shift-II] formation of product A. The
Nearest integer = 2 secondary valency of Fe in the
Ans. (2)
[Ni(CN) 6 ]2 − product A is ........ . (Round off to
77 The secondary valency and the
Oxidation state of Ni in [Ni(CN) 6 ]2 − the nearest integer).
number of hydrogen bonded water [2021, 17 March Shift-II]
⇒ x + 6 (− 1) = − 2 molecules in CuSO 4 ⋅ 5H2O, Ans. (6)
x −6=−2 respectively, are
⇒ x=+4 [2021, 18 March Shift-II]
Secondary valency is equal to
coordination number of central metal
Coordination Compounds 237

ion. In this reaction, central metal atom (C) 63Eu → [Xe]4f 9 5d 0 6s 0 84 In which of the following order the
iron is attached with 3-oxalato ligand, In complex given complex ions are arranged
63Eu → [Xe]4f 5d 6s
and oxlaic acid it is a bidentate ligand i.e. +3 6 0 0
have two donor sites. So, coordination correctly with respect to their
contain six unpaired electrons.
number or secondary valency = 3 × 2 = 6 decreasing spin only magnetic
So, µ m = 6(6 + 2)
FeCl 3 + 3H2 C2O4 + 6KOH → moment?
= 48 BM
K3 [Fe(C2O4 ) 3] + 3KCl + 6H2O (i) [FeF6] 3− (ii) [Co(NH3 ) 6] 3+
= 6.93 BM
(A ) (iii) [NiCl 4] 2− (iv) [Cu(NH3 ) 4] 2+
Hence, order of spin only magnetic
Hence, product A have iron with [2021, 25 Feb Shift-II]
moment B > C > A.
secondary valency = 6 (a) (i) > (iii) > (iv) > (ii)
82 [Ti(H2O) 6] 3+ absorbs light of (b) (ii) > (iii) > (i) > (iv)
80 What is the spin-only magnetic (c) (iii) > (iv) > (ii) > (i)
moment value (BM) of a divalent wavelength (d) (ii) > (i) > (iii) > (iv)
metal ion with atomic number 25, 498 nm during a d-d transition. The Ans. (a)
in it's aqueous solution? octahedral splitting energy for the
Spin only magnetic moment,
[2021, 17 March Shift-I] above complex is ……… × 10 −9 J
µ = n(n + 2) BM
(a) 5.92 (b) 5.0 (Round off to the nearest intger). [h
where, n = number of unpaired electrons
(c) zero (d) 5.26 = 6.626 × 10 −34 Js, c = 3 × 10 8 ms −1 ] and µ ∝ n.
Ans. (a) [2021, 16 March Shift-II]
(i) [FeF6 ] 3−
Atomic number 25 is for manganese Ans. (4)
⇒Fe3+ = (3d 5 ) + 6 × F −
(Mn). [Ti(H2O) 6 ] 3+ is an octahedral complex.
(weak field ligand).
Configuration of Mn = [Ar] 4s 2 3d 5
eg Thus, pairing of electron does not
In aqueous medium,Mn2 + = [Ar] 3d 5 take place.
∆o
3d
d-orbital
3d t2g

Total number of unpaired electrons = 5 4s 4p 4d

For transition of electron from t2 g to e g
µ (magnetic moment) = n (n + 2) BM orbital, ∆ o amount of energy is required.
where, n = number of unpaired electron Given, λ = 498 nm = 498 × 10 −9 m sp3d2 (Fe), n=5
∴ µ = 5 (5 + 2) = 35 BM = 592
. BM ∆ o = hc / λ
where,h = Planck’s constant (ii) [Co(NH3) 6 ] 3+ ⇒
81 Arrange the following metal c = speed of light Co3+ = (3d 6 ) + 6 × NH3 (strong field
complex/compounds in the ligand). Thus, pairing of electron
λ = wavelength of radiation
takes place.
increasing order of spin only 66. × 10 −34 × 3 × 10 8
So, ∆ o = 3d 4s 4p
magnetic moment. Presume all the 498 × 10 −9
three, high spin system. . × 10 −19 J
= 398
(Atomic numbers Ce = 58, Gd = 64 = 4 × 10 −19 d2sp3 (Co), n=0
and Eu = 63.)
(iii) [NiCl 4 ]2 − ⇒Ni2 + = (3d 8 ) + 4 × Cl −
A. (NH4 ) 2 [Ce(NO 3 ) 6] 83 Number of bridging CO ligands in
(weak field ligand). Thus, pairing of
[Mn 2 (CO) 10 ] is ………… .
B. Gd(NO 3 ) 3 and [2021, 26 Feb Shift-I]
electron takes place.
C. Eu(NO 3 ) 3 [2021, 16 March Shift-II] 3d 4s 4p
Ans. (0)
(a) (B) < (A) < (C) (b) (C) < (A) < (B) [Mn2 (CO) 10 ] is a polynuclear metal
(c) (A) < (B) < (C) (d) (A) < (C) < (B) carbonyl compound. It is sp3 (Ni), n=2
Ans. (d) decarboxyldimanganese (0) which is
(A) Ce → [Xe]4f2 5d 0 6s 2 made up of two square pyramidal (iv) [Cu(NH3) 4 ]2 + ⇒
58
Mn(CO) 5 units joined by a MnMn bond. Cu2 + (3d 9 ) + 4 × NH3(strong field
In complex
The structure of [Mn2 (CO) 10 ] is
Ce+4 → [Xe]4f 0 5d 0 6s 0 ligand). Thus, pairing of electron
There is no unpaired electron, so CO CO CO takes place.
CO
µ m = 0 BM 3d 4s 4p
(B) 64 Gd → [Xe]4f 7 5d 16s 2 OC Mn Mn CO
In complex, sp3 (Cu), n=1
OC CO
64 Gd → [Xe]4f 5d
2+ 7 1 OC CO
There are 8 unpaired electrons. So, the decreasing order ofµ is
Here, no CO ligand is a bridging ligand.
∴ µ m = 8(8 + 2) So, number of bridging CO ligands in µ i > µ iii > µ iv > µ ii
(n = 5 ) (n = 2 ) (n = 1) (n = 0 )
= 80 = 8.94 BM [Mn2 (CO) 10 ] is 0 (zero).
238 JEE Main Chapterwise Topicwise Chemistry

85 The hybridisation and magnetic eg k = k1 × k2 × k3 × k4

nature of [Mn(CN) 6] 4− and k = 10 4 × 1.58 × 10 3 × 5 × 102 × 102
[Fe(CN) 6] 3− , respectively are ∆o < P k = 7.9 × 10 11
[2021, 25 Feb Shift-I] d6 t2g where, k = equilibrium constant for
(a) d2 sp 3 and paramagnetic formation of [Cu(NH3) 4 ]2 +
(b) sp 3d2 and diamagnetic All electrons are paired, n = 0 So, equilibrium constant k′ for
1
(c) d2 sp 3 and diamagnetic hence,µ = 0 dissociation of [Cu(NH3) 4 ]2 + is .
k
(d) sp 3d2 and paramagnetic (iii) MnO24− → Mn+6 → [Ar]3d 1 1 1 −12
k′ = = = 126
. × 10
Ans. (a) n= 1 k 7.9 × 10 11
[Mn(CN)6 ] 4– In this complex, oxidation = n(n + 2) BM = 1 (1 + 2) BM
Hence, k ′ = x × 10 −12 ⇒ x = 126
.
state of Mn is + 2. = 3 BM = 1.73 BM
Mn2+= [Ar] 3d5 88 Simplified absorption spectra of
87 The stepwise formation of
three complexes [(i), (ii) and (iii)] of
eg [Cu(NH3 ) 4] 2 + is given below
Strong M n+ ion are provided below; their
∆o > P K1
field ligand Cu 2 + + NH3
-[Cu(NH )] 2+ λ max values are marked as A, B and
– 3
(CN ) C respectively. The correct match
K2
t2g 2+
[Cu(NH )] + NH -
3 3
between the complexes and their
Hybridisation- d2 sp3 2+ λ max values is
[Cu(NH ) ] 3 2
Magnetic nature-Paramagnetic K3
[Fe(CN)6 ]−3 [Cu(NH ) ] + NH -2+
3 2 3
3+ 5 2+
Fe = [Ar] 3d [Cu(NH )] 3 C
K4 A
2+

Absorption
Strong
eg [Cu(NH ) ] + NH -
3 3 3
B

Do > P 2+
field ligand [Cu(NH3 ) 4]
–
(CN )
The value of stability constants K 1 ,
t2g
2 3
K 2 , K 3 and K 4 are 10 4 , 1.58 × 10 3 ,
Hybridisation- d sp
Magnetic nature-Paramagnetic
5 × 10 2 and 10 2 respectively. The
λmax λmax λmax
overall equilibrium constants for Wavelength (nm)
86 The calculated magnetic moments dissociation of [Cu(NH3 )] 2 + ] is
x × 10 − 12 . The value of x is ........ .
[2020, 2 Sep Shift-II]
(spin only value) for species ( − 6 + n)
[FeCl 4] 2− , [Co(C 2O 4 ) 3] 3− and (Rounded off to the nearest (i) [M (NCS) 6]
MnO 2−
4 respectively are integer) [2021, 24 Feb Shift-I] (ii) [MF6] ( − 6 + n)
[2021, 24 Feb Shift-II]
Ans. (1.26) (iii) [M (NH3 ) 6] n+
(a) 5.82, 0 and 0 BM (a) A-(iii), B-(i), C-(ii)
Given, stability constant value, k1 = 10 4
(b) 4.90, 0 and 1.73 BM (b) A-(ii), B-(i), C-(iii)
k2 = 1.58 × 10 3
(c) 5.92, 4.90 and 0 BM (c) A-(ii), B-(iii), C-(i)
k3 = 5 × 102
(d) 4.90, 0 and 2.83 BM (d) A-(i), B-(ii), C-(iii)
k4 = 102
Ans. (b) k 1 Ans. (a)
(i) [FeCl 4 ]2 − → Fe2 + → [Ar] 3d 6 Cu2 + + NH3 q [Cu(NH3)]2 + …(i) Here, same metal ion, Mn + form three
∴Cl is weak field ligand so does not k2 homoleptic octahedral complexes (i), (ii)
pairing occur [Cu(NH3)]2 + + NH3 q [Cu(NH3)2 ]2 + and (iii) on separate combination with
…(ii) È È
t2g three mono-dentate ligands–N CS,F and
k3
[Cu(NH3)2 ]2 + + NH3 q [Cu(NH3) 3]2 + NH3 respectively.
∆o < P …(iii) So, we have to compare their CFSE (∆ 0 )
d6 k4 as well as wavelength (λ) values, where
eg
[Cu(NH3) 3]2 + + NH3 q [Cu(NH3) 4 ]2 + ∆E(CFSE) =
hc
or, ∆ 0 ∝
1
…(iv) λ λ
So, magnetic moment (µ ) = n(n + 2) BM
M M M Again, ∆ 0 value will depend on power of
= 4(4 + 2) BM
On adding Eqs. (i), (ii), (iii) and (iv), we get ligand as placed in spectrochemical
(n = Number of total unpaired e − = 4) k series.
= 24 BM = 490 . BM Cu2 + + 4NH3 = [Cu(NH3) 4 ]2 + 1
Power of ligand ∝ ∆ 0 ∝ ,
(ii) [Co(C2O4 ) 3] 3− → Co3+ → [Ar] 3d 6 ∴ The overall reaction constant (k) or λ
C2O4 is strong field ligand so pairing equilibrium constant for formation of − −
F − < NCS − < NH3, F > NCS > NH3
occur. [Cu(NH3) 4 ]2 + is
Coordination Compounds 239

→ Power of Ligand ← λ III. With strong field ligands like —CN− ,

→ ∆ o Mn(II) octahedral complexes can be Number of Number of
low spin, electrons in e set. electrons in t2 set.
So, for the given complexes, it is
evidented from the plot II
(Absorption vs. λ) [Mn(CN)6] 4– ⇒ Mn 2+: So, the geometry and the crystal field
stabilisation energy of the complex is
λ (ii)
max > λ max > λ max
(i) (iii)
tetrahedral and −0.6 ∆ t respectively.
(C ) (B) (A )
[F − ] [NCS − ] [NH 3 ]
91 The electronic spectrum of
d2sp3 (octahedral complex) [Ti(H2O) 6] 3+ shows a single
89 For octahedral Mn (II) and [Inner orbital, low spin]
broad peak with a maximum at
tetrahedral Ni (II) complexes,
IV. Aqueous solution of Mn(II) ion is 20,300 cm −1 . The crystal field
consider the following statements :
pale pink in colour. stabilisation energy (CFSE) of the
(I) Both the complexes can be Hence, statement I, II and III are complex ion, in kJ mol −1 , is
high spin. correct whereas statement IV is (1 kJ mol −1 = 83.7 cm −1 )
(II) Ni(II) complex can very rarely incorrect. [2020, 3 Sep Shift-I]
be low spin. 6 2+ (a) 145.5 (b) 242.5
(III) With strong field ligands, Mn(II) 90 Consider that a d metal ion (M ) (c) 83.7 (d) 97
complexes can be low spin. forms a complex with aqua ligands Ans. (d)
(IV) Aqueous solution of Mn(II) ions and the spin only magnetic In [Ti(H2O)] 3+ , Ti3+ ion of d 1 configuration
is yellow in colour. moment of the complex is 4.90 BM. is present in the octahedral complex.
The correct statements is The geometry and the crystal field Under octahedral crystal field, the
(a) (I) and (II) only [2020, 2 Sep Shift-I] stabilisation energy of the complex configuration of Ti3+ will be,t21 g e g0 .
(b) (II), (III) and (IV) only is [2020, 2 Sep Shift-I] So, CFSE = [(− 0.4) × 1 + (+ 0.6) × 0] ∆ 0
(c) (I), (II) and (III) only (a) tetrahedral and −1.6∆ t + 1 P = − 0.4 × ∆ 0 = − 0.4 × 20,300 cm−1
(d) (I), (III) and (IV) only (b) octahedral and −2.4 ∆ 0 + 2 P [Q∆ 0 = 20,300 cm−1]
20,300
Ans. (c) (c) octahedral and −1.6 ∆ 0 = − 0.4 × kJ mol −1
(d) tetrahedral and −0.6 ∆ t 83.7
I. In presence of weak field ligand like
Cl − , both octahedral Mn(II) and [Q1 kJ mol −1 = 83.7 cm −1]
Ans. (d)
tetrahedral Ni(II) complexes can be high = − 97.103 kJ mol −1
spin, like M2 + + mH2O → [M (H2O) m ]2 + ⇒ CFSE =97 kJ mol −1
(d 6 )
3d
II 2+
[MnCl4] 2– ⇒ Mn : Here, H2O is a weak field ligand and it 92 The d-electron configuration of
(d5) should give a high spin paramagnetic
[Ru(en) 3]Cl 2 and [Fe(H2O) 6]Cl 2 ,
4s 4p 4d (µ = 490
. BM) complex ion.
respectively are [2020, 3 Sep Shift-II]
We know,µ = n(n + 2) BM
= 490
. BM (n = 4) (a) t26g e g0 and t26g e g0

sp3d2 (octahedral complex) [∴n = Number of unpaired (b) t26g e g0 and t24g e2g
[outer orbital, high spin] electrons in the complex] (c) t24g e2g and t26g e g0
3d (n–1)d6 ns0 np0
II (d) t24g e2g and t24g e2g
[NiCl4] 2– ⇒ 2+ : M 2+=
Ni (d6) Ans. (b)
(d8) H2O H2O H2O H2O
4s 4p n=4 The d-electron configuration
M2+ is sp3 hybridised, i.e. it [Ru(en) 3]Cl2 and [Fe(H2O) 6 ] Cl2
is a tetrahedral complex ion
respectively aret26g e g0 and t24g e2g .
[M(H2O)4]2+ [∴ M = 4]
sp3 (Tetrahedral complex) [Ru(en) 3]Cl2
So, the complex will experience splitting
[outer orbital, high spin] Ru = 4d series
of (n − 1) d -orbitals in tetrahedral field.
II. In presence of strong field ligand en = bidentate ligand (strong field ligand)
like CN− , Ni2 + can form low spin t2
C.N. = 6
square planar complex.
+0.4 ∆ t Oxidation number + 2
II
[NiCl4] 2– ⇒ Ni 2+ : Ru2 + = [Kr] 4d 6 5s 0

–0.6 ∆ t Ru2+ =
e 4d 5s 5p
dsp2 (Square planar complex)
CFSE = [(− 0.6) × 3 + (0.4) × 3] ∆ t = − 0.6 ∆ t In presence of en, pairing should be done
[Inner orbital, low spin]
240 JEE Main Chapterwise Topicwise Chemistry

[Fe(H2O)6 ] 2+ Ans. (d)

[Ru(en) 3 ]Cl2 = eg
Electronic configuration,Fe = 3d 6 4s 2 Complex Electronic Number Magnetic
0.6∆0
or Fe2 + = 3d 6 configuration of behaviour
∆0 t 6 , e 0
(n–1)d 2g g Here, coordination number = 6 unpaired
electron
(4d) 0.4∆0 Oxidation number = +2
Weak field ligand =H2O (a) [Pd(gly) 2] Pd 2 + = 4d 8 0 Diamagn
6 etic
t2g
Fe2+ (b) [Fe(en)(bipy) Fe 2 + = 3d 6 0 Diamagn
For [Fe(H2O) 6 ]Cl2 ⇒H2O (weak field (NH 3) 2] 2 + → t 2 g 6 ,e 0g etic
ligand) 3d
Oxidation number = + 2 ; C.N. = 6 Hence, unpaired electrons are4. (c) [Co(ox) 2 Co 3+ = 3d 6 0 Diamagn
(NH 3) 2] − etic
Fe2 + = 3d 6 [Co(OH)4 ] 2− ( ∆ 0 > P) → t 2 g 6° e 0g

Fe2+ = Electronic configuration, Co = 3d 7 4s 2

(d) [Ti(NH 3) 6] 3 + Ti 3+ = 3d 1 1 Paramag
or Co2+ = 3d 7 netic
→ t 2 g 1 ,e 0g
[Fe(H 2O) 6 ]Cl2 = Here, coordination number = 4
eg
0.6∆0 Oxidation number = +2 The paramagnetism of a complex is
Weak field ligand =OH expressed in terms of magnetic moment
∆0 t 4 , e 2
(n–1)d 2g g (µ). Greater is the number of unpaired
(3d) 0.4∆0 Co2+ electrons in the central atom/ion of
given compound, greater is its
3d
t2g paramagnetic character among the given
Hence, unpaired electrons are 3. option [Ti(NH3) 6 ] 3+ have unpaired
[Fe(NH) 3] 6 electron so, it exhibit highest
93 The pair in which both the species paramagnetic behaviour.
have the same magnetic moment Electronic configuration,Fe = 3d 6 4s 2
or Fe 2+ = 3d 6
(spin only) is [2020, 4 Sep Shift-I] 95 The molecule in which hybrid MOs
Here, coordination number = 6
(a) [Mn(H2O) 6] 2+ and [Cr(H2O)] 2+ involve only one d-orbital of the
Oxidation number = 2
(b) [Cr(H2O) 6] 2+ and [Fe(H2O) 6] 2+ central atom is [2020, 4 Sep Shift-II]
Weak field ligand =NH3
(c) [Co(OH) 4] 2− and [Fe(NH3) 6] 2+ (a) XeF4 (b) [CrF6] 3−
NH3 is SFL (strong field ligand) but act as
(d) [Cr(H2O) 6] 2+ and [CoCl4] 2− (c) BrF5 (d) [Ni(CN) 4] 2−
a weak field ligand withFe 2+ .
Ans. (b) Ans. (d)
The pairs in which both the species have
same magnetic moment is [Cr(H2O) 6 ]2 + 3d
Molecule Hybridisation
and [Fe(H2O) 6 ]2 + . (a) XeF4 sp 3d 2
Hence, unpaired electrons are 4.
All the given options is described as
[CoCl 4 ] 2− (b) [CrF6] 3− d 2 sp 3
follows :
[Mn(H2O)6 ] 2+ Electronic configuration, Co = 3d 7 4s 2 (c) BrF5 sp 3d 2
or Co2+ = 3d 7 2−
Electronic configuration, (d) [Ni(CN) 4] dsp 2
Here, coordination number = 4
Mn = 3d 5 4s 2 or Mn2 + = 3d 5
Oxidation number = +2 In [Ni(CN) 4 ]2 − molecule hybrid MOs
Here, coordination number = 6 involve only oned-orbital of the central
Weak field ligand = Cl
Oxidation number = +2 atom.
Weak field ligand = H2O
96 The crystal field stabilisation
Mn2+ 3d
Hence, unpaired electrons = 3
energy (CFSE) of [CoF3 (H2O) 3]
3d5
(∆ 0 < P) is [2020, 4 Sep Shift-II]
Hence, unpaired electrons are 5.
(a) −08
. ∆0 (b) −08
. ∆0 + 2P
[Cr(H2O)6 ] 2+ 94 The one that can exhibit highest
(c) −04
. ∆0 (d) −04
. ∆0 + P
Electronic configuration, Cr = 2d 5 4s 1 paramagnetic behaviour among the
Ans. (c)
or Cr2 + = 3d 4 following is [2020, 4 Sep Shift-II]
[CoF3 (H2O) 3] is an octahedral complex.
Here, coordination number = 6 gly = glycinato;
In this complex (compound) all ligands
Oxidation number = +2 bpy = 2, 2′-bipyridine are weak field ligand.
Weak field ligand = H2O (a) [Pd(gly)2] With weak field ligands ∆ 0 < P (pairing
(b) [Fe(en) (bpy)(NH3)2] 2+ energy), so the electronic configuration
Cr2+
(c) [Co(OX)2 (OH)2] − (∆ 0 > P) of Co (III) will be t24g e2g , i.e. it has four
3d unpaired electrons.
(d) [Ti(NH3) 6] 3+
Hence, unpaired electrons are 4.
Coordination Compounds 241

Ans. (0) Ans. (a)

eg
Magnetic moment (in BM) of [Ru(H2O) 6 ]2 In octahedral complexes:
+0.6∆ would be; while considering that ∆ 0 > P, (i) If ∆ 0 < P (weak field, high spin
Ru (44 ) ;[Kr]4d 7 5s 1 (in ground state) situation).
∆0
Degenerate ⇒ In Ru2 + ⇒ 4d 6 ⇒ (t2 g) 6 (e g ) 0 The fourth electron enters one of
d-orbital of +0.4∆ the e g orbitals giving the
Co3+ ion t2g (eg )0 configuration t23g e g 1.

Here, CFSE can be calculated as : (ii) If ∆ 0 > P (strong field, low spin
∆0 > P
CFSE = [−04. x + 0.6y] ∆ 0 situation), pairing will occur in the
t2 g level with e g level remaining
Where, ∆ 0 = CFSE in octahedral complex 4d 6 (t2g )
6
unoccupied giving configuration
x = Number of electrons int2 g orbitals t2g t24g e g 0 .
y = Number of unpaired electrons in e g
⇒ Here, number of unpaired electrons Hence, for d 4 metal ion in an octahedral
orbitals
in field, the correct, electronic
= [−0.4 × 4 + 0.6 × 2] ∆ 0 + 0
Ru2 + = (t2 g ) 6 (e g ) 0 = 0 and hence configuration is t23g e g 1, when ∆ 0 < P.
= [−16
. + 12
. ] ∆ 0 = [−0.4 ∆ 0 ]
µ = n(n + 2)BM = 0 BM
Hence, the crystal field stabilisation
energy (CFSE) of [CoF3 (H2O) 3] will be 101 Among the statements (A)-(D), the
−0.4 ∆ 0 . 99 The species that has a spin-only incorrect ones are
magnetic moment of 5.9 BM, is (A) octahedral Co(III) complexes
97 The values of the crystal field (T d = tetrahedral) with strong, field ligands have
stabilisation energies for a high [2020, 6 Sep Shift-I]
very high magnetic moments
spin d 6 metal ion in octahedral and (a) [Ni(CN) 4] 2− (square planar)
(B) When ∆ 0 < P, the d-electron
tetrahedral fields respectively, are (b) [NiCl4] 2− (Td ) configuration of Co(III) in an
4
[2020, 5 Sep Shift-I] (c) [Ni(CO) 4] (Td ) octahedral complex is t eg , eg2
(a) −0.4 ∆ 0 and −0.27 ∆ t (d) [MnBr4] 2− (Td ) (C) Wavelength of light absorbed
(b) −1.6 ∆ 0 and −0.4 ∆ t
Ans. (d) by [Co(en) 3] 3+ is lower than
(c) −2.4 ∆ 0 and −0.6 ∆ t that of [CoF6] 3−
Given that n(n + 2) = 591
. BM.
(d) −0.4 ∆ 0 and −0.6 ∆ t ∴ n= 5 (D) If the ∆ 0 for an octahedral
Ans. (d)
Electronic Unpaired
complex of Co(III) is 18,000 cm −1 ,
Crystal field stabilisation energy (CFSE) Complex Ligand the ∆ t for its tetrahedral
configuration electron
for high spind 6 metal ion.
complex with the same ligand
(b) [NiCl 4] 2 − Ni 2 + = [Ar] 3d 8 2 (Cl − )
Crystal field splitting in octahedral field.
Weak will be 16,000 cm −1
neg = 2 [2020, 7 Jan Shift-II]
(a) [Ni(CN) 4] 2 − Ni 2 + = [Ar] 3d 8 0 (CN) −
eg Strong (a) B and C only (b) A and B only
(c) C and D only (d) A and D only
d6 (c) [Ni(CO) 4] Ni = [Ar] 3d 8 2 (CO) Ans. (d)
Strong
nt = 4 (A) Co3+ has d 6 configuration with
2g (d) [MnBr4] 2 − Mn 2 + = [Ar] 3d 5 5 (Br − )
t2g strong field ligands, the
Weak
configuration becomest26g e g 0 .
CFSE = [− 0.4nt 2 g + 0.6ne g ] ∆ 0 Only [MnBr4 ]2 − have 5 unpaired As no unpaired electron is present
= [− 0.4 × 4 + 0.6 × 2] ∆ 0 = − 0.4 ∆ 0 electrons, it is high spin complex due to in Co3+ , so it has zero magnetic
Crystal field splitting in tetrahedral field weak ligand.
moment.
∴Magnetic moment (γ) = n(n + 2)
nt = 3 ∴ Statement is incorrect.
2g BM ⇒ n = 5
(B) When ∆ o < P, pairing of
∴ (γ) = 5(5 + 2) = 35, γ = 59
. BM d-electrons takes place only after
d6
Hence, the correct option is (d). filling every orbital with single
neg = 3 electron.
CFSE = (− 0.6 ne g + 0.4nt 2 g ) ∆ t 100 For a d 4 metal ion in an octahedral ∴ Configuration of d 6 = t24g e g2
= (− 0 . 6 × 3 + 0.4 × 3) ∆ t field, the correct electronic Statement is correct.
= (− 1 . 8 + 1 . 2) ∆ t = − 0.6 ∆ t configuration is [2020, 6 Sep Shift-II] (C) ‘en’ or ethan-1, 2-diamine has
(a) t23g e g1 when ∆ 0 < P greater field strength than F − .
98 Considering that ∆ 0 > P, the (b) t23g e g1 when ∆ 0 > P
∴ Frequency of light absorbed in
[Co(en) 3] 3+ is greater and
magnetic moment (in BM) of [ (c) t24g e g0 when ∆ 0 < P wavelength is lower than [CoF6 ] 3− .
Ru(H2O) 6] 2+ would be ……… . Thus, this statement is correct.
[2020, 5 Sep Shift-II] (d) t2g e22g when ∆ 0 < P
242 JEE Main Chapterwise Topicwise Chemistry

4 (C) : Na2 [Ni(CN) 4 ]

(D) ∆ t ≈ ∆ o for complexes with same 105 The correct order of the spin only
9 Ni2 + has (d 8 ) configuration and square magnetic moments of the following
metal and ligand. planar (strong field ligand).
4 complexes is [2020, 9 Jan Shift-II]
∴∆ t must be × 18000 ∴ dsp2 hybridisation and no unpaired
9 electron (I) [Cr(H2O) 6]Br 2
= 8000cm −1. (II) Na 4 [Fe(CN) 6]
∴ µ = 0 BM
This statement is incorrect.
(D) : PdCl2 (PPh3)2 (III) Na 3 [Fe(C 2O 4 ) 3](∆ 0 > P)
Hence, among the given options, (IV) (Et 4N) 2 [CoCl 4]
Pd2 + has (d 8 ) configuration. All
option (d) is correct. (a) (II) ≈ (I) > (IV) > (III)
coordination number = 4
Complexes of Pd2 + are square planar. (b) (I) > (IV) > (III) > (II)
102 Complexes (ML 5 ) of metals Ni and (c) (III) > (I) > (IV) > (II)
∴ dsp2 hybridised.
Fe have ideal square pyramidal and (d) (III) > (I) > (II) > (IV)
No unpaired electron,µ = 0 BM
trigonal bipyramidal geometries, Ans. (d)
The correct order of the calculated spin
respectively. The sum of the 90°, I. In [Cr(H2O) 6 ]Br2 , chromium is in
only magnetic moments of complexes is
120° and 180° L-M-L angles in the Cr2 + having electronic configuration
µ (B) > µ (A) = µ (C) = µ (D).
two complexes is ............... . [Ar]3d 4 .
[2020, 8 Jan Shift-II]
104 [Pd (F) (Cl) (Br) (I)] 2− has n number H2O is a weak field ligand.
Ans. (20) It has octahedral geometry
of geometrical isomers. Then, the
Nickel : ML 5 complex is square ∴ 3d 4 = t 23g e g1
pyramidal, spin-only magnetic moment and
Unpaired electrons = 4
crystal field stabilisation energy
L µ s = 4 × 6 = 24 BM.
180° angles = 2
[CFSE] of [Fe(CN) 6] n− 6
L L 90° angles = 8 II. Na4 [Fe(CN) 6 ] → Fe2 + = [Ar]3d 6
M (4 in square plane respectively, are [2020, 9 Jan Shift-II]
L L 4 = perpendicular to plane) CN− is a strong field ligand
[Note Ignore the pairing energy]
Octahedral geometry
(a) 1.73 BM and −2.0∆ o
Fe :ML 5 complex is trigonal bipyramidal ∴ 3d 6 = t26g e 0g
(b) 2.84 BM and −1.6 ∆ o
L (c) 0 BM and −2.4 ∆ o Unpaired electrons = 0
180° angle =1
L 90° angle = 6 (d) 5.92 BM and 0 µ s =0
L M
Ans. (a) III. Na3 [Fe(C2O4 ) 3] → Fe3+ = [Ar] 3d 5
L 120° angle = 3
L Pd2 + complexes with coordination ∆ o > p (Given)
number = 4 are of square planar Octahedral geometry
Sum of all L-M-L angles in two
geometry, irrespective of the field ∴ 3d 5 = t25g e g0
complexes is = 2 + 8 + 1 + 6 + 3 = 20
strength of ligands.
Unpaired electrons = 1;
For square planar complex with four
103 The correct order of the calculated different ligands, three, geometrical µ s = 3 = 1.73 BM
spin only magnetic moments of isomers are possible. IV. (Et4N)2 [CoCl 4 ] [CoCl 4 ]2 − :
complexes (A) to (D) is These are as follows : Co2 + = [Ar] 3d 7
(A) Ni(CO) 4 [2020, 8 Jan Shift-II] F Cl F Cl F l Cl − is a weak field ligand.
Pd , Pd and Pd
(B) [Ni(H2O) 6]Cl 2 In this complex, coordination number is 4
Br I I Br Br Cl
(C) Na 2 [Ni(CN) 4] Tetrahedral geometry
∴ n=3 Splitting of d - orbitals in tetrahedral
(D) PdCl 2 (PPh 3 ) 2
[Fe(CN) 6 ]n −6 = [Fe(CN) 6 ] −3. So, oxidation field is
(a) (A) ≈ (C) < (B) ≈ (D)
state of iron in [Fe(CN) 6 ] –3 is +3.
(b) (C) ≈ (D) < (B) < (A) t23
Fe3+ = d 5 .
(c) (C) < (D) < (B) < (A)
(d) (A) ≈ (C) ≈ (D) < (B) It forms a low spin complex (CN− is a
Ans. (d)
strong field ligand). d7 e4
0
eg
(A) : Ni(CO) 4 Unpaired electrons = 3
Ni has 3d 8 4s 2 configuration and ∆o µ s = 15 BM
tetrahedral (strong field ligand). d5 5 ∴ Spin only magnetic moment order is :
t2g
∴ Unpaired electrons = 0, µ = 0 BM I > IV > III > II
∴Number of unpaired electrons (n) = 1
(B) : [Ni(H2O) 6 ]Cl2
Ni2 + has (d 8 ) configuration and has Spin only magnetic moment = 3 = 1.73 106 The correct order of the spin only
unpaired electrons. BM magnetic moment of metal ions in
µ s = n(n + 2) BM the following low spin complexes,
[Ni(H2O)6]2+= CFSE = (Number of electrons in [V(CN) 6] 4− , [Fe(CN) 6] 4− ,
t2 g × − 0.4∆ o ) + (Number of electrons in [Ru(NH3 ) 6] 3+ , and [Cr(NH3 ) 6] 2+ , is
µ = n(n + 2) = 2 × 4 = 8 B.M = 2.82 BM
e g × 0.6∆ o ). = 5 × − 0.4∆ o = − 20
. ∆o. [2019, 8 April Shift-I]
Coordination Compounds 243

(a) Cr2+ > Ru 3+ > Fe2+ > V2+ In [Fe(H2O) 6 ]Cl2 , H2O is a weak field eg
(b) V2+ > Cr2+ > Ru 3+ > Fe2+ ligand, so it is a high spin (outer orbital)
(c) V2+ > Ru 3+ > Cr2+ > Fe2+ octahedral complex ofFe2 + . +0.6 ∆o
(d) Cr2+ > V2+ > Ru 3+ > Fe2+ eg Fe3+
Ans. (b) Fe2+(3d6) = –0.4 ∆o
t2g
Key Idea In presence of strong field t2g
ligands, ∆ o > P,for fourth electron it is ∴ CFSE = (−0.4x + 0.6y) ∆ o CFSE = 5 × −0.4 ∆ o = −2.0 ∆ o
more energetically favourable to occupy = [−0.4 × 4 + 0.6 × 2] ∆ o = − 0.4∆o Fe2 + upon oxidation of its metal to +3
t2 g orbital with configurationt24g e g0 and In K2 [NiCl 4 ], Cl − is a weak field ligand, so state lose its CFSE from −2.4 ∆ o to
form low spin complexes. it is a high spin tetrahedral complex of −2.0 ∆ o .
The correct order of the spin only Ni2 + .
magnetic moment of metal ions in the t 109 Complete removal of both the axial
given low-spin complexes is Ni2+(3d6) = ligands (along the z-axis) from an
V2 + > Cr2 + > Ru3+ > Fe2 + . e octahedral complex leads to which
All the given complexes possess strong of the following splitting patterns?
field ligands (CN, NH3). Hence, readily ∴ CFSE = (−0.6 × 4 + 0.4 × 4) ∆ t = − 0.8∆ t
(relative orbital energies not on
form low spin complexes.
108 The complex ion that will lose its scale). [2019, 12 April Shift-I]
Oxidation

crystal field stabilisation energy dx2 – y2 dz2

state

No. of
Orbital
Complex Configuration
splitting
unpaired
electrons
upon oxidation of its metal to +3 dxy dx2 – y2
eg state is [2019, 12 April Shift-I] (a) E (b) E
[V(CN)6]4– V
2+ 3
t2g eg
0
3
dz2 dxz, dyz
t2g
dxz, dyz dxy
eg (Phen =
[Cr(NH3)6]2+ Cr2+ 4 dx2 – y2 dx2 – y2
t2g eg0 2 N N
t2g
Ignore pairing energy dz2 dz2
(c) E (d) E
eg dyz, dxz
[Ru(NH3)6]3+ Ru3+ t25g eg0 1 (a) [Co(phen) 3] 2+ dxy
t2g (b) [Ni(phen) 3] 2+ dxz, dyz dxy
eg
(c) [Zn(phen) 3] 2+ Ans. (a)
[Fe(CN)6]4– Fe2+ t26g eg0 0 (d) [Fe(phen) 3] 2+
Complete removal of both the axial
t2g
Ans. (d) ligands (along the z-axis) from an
Key Idea Crystal field splitting occurs octahedral complex leads to the
due to the presence of ligands in a following splitting pattern.
107 The crystal field stabilisation definite geometry. In octahedral dx2–y 2
energy (CFSE) of [Fe(H2O) 6]Cl 2 and complexes the energy of two, e g orbitals
K 2 [NiCl 4], respectively, are will increase by (0.6) ∆ o and that of three
[2019, 10 April Shift-II] t2 g will decrease by (0.4) ∆ o . dxy
Energy

(a) − 04
. ∆ o and − 12. ∆t The complex ion that will lose its crystal eg

(b) − 04
. ∆ o and − 08 . ∆t field stabilisation energy upon oxidation
of its metal to +3 state is [Fe(phen) 3]2 + .
dz2
(c) − 2.4 ∆ o and − 12
. ∆t t2g
−e −
(d) − 0.6 ∆ o and − 08. ∆t [Fe(phen) 3]2 + → [Fe(phen) 3] 3+
Ans. (b) In [Fe(phen) 3]2 + , electronic dxzdyz
Key Idea Crystal field stabilisation configuration of Fe2 + is 3d 6 4s 0 .
energy (CFSE) for octahedral complexes Phenanthrene is a strong field The single electron in thed 2 2 orbital is
x −y
symmetrical bidentate ligand. The being repelled by four ligands, while the
= (−0.4x + 0.6y) ∆ o
splitting of orbital inFe2 + is as follows: electron in thed 2 orbital is only being
where, x = number of electrons repelled
z

occupying t2 g orbital. eg
by two ligands. Thus, the energy of the
y = number of electrons occupying e g d 2 2 increases relative to that ofd 2 .
orbital. +0.6 ∆o x −y z

Fe2+
A more stable arrangement arises when
CFSE for tetrahedral complexes
both the e g electrons pair up and occupy
= (−0.6x + 0.4y) ∆ t –0.4 ∆o
the lower energyd 2 orbital. This leaves
where, x = number of electrons t2g z
the d 2 2 orbital empty.
occupying e orbital. x −y
CFSE = 6 × −0.4∆ o = −2.4 ∆ o . Thus, four ligands can now approach
y = number of electrons occupying along + x, − x, + y and −y directions
t orbital. The splitting of orbital and arrangement
of electrons inFe3+ is as follows : without any difficulty asd 2 2 orbital is
x −y
244 JEE Main Chapterwise Topicwise Chemistry

empty. However, ligands approaching So, the octahedral complexes (a, b, c) 114 Mn 2 (CO) 10 is an organometallic
along + z and −z directions meet very have higher ∆ o values than that of compound due to the presence of
strong repulsive forces from filledd 2 tetrahedral,K2 [CoCl 4 ].
z
orbitals. Thus, only four ligands succeed (a) Mn C bond (b) Mn O bond
Now, for the complexes, a, b and c,
in bonding to the metal. A square planar (c) C O bond (d) Mn Mn
the magnitude of ∆O ∝ ligand strength,
complex is formed, the attempt to form which is based on their positions in the [2019, 12 Jan Shift-I]
an octahedral complex being spectrochemical series. Ans. (a)
unsuccessful.
Cl − < H2O < NH3 < CN− Mn2 (CO) 10 is an organometallic
Hence,K3 [Co(CN) 6 ] will have the highest compound due to the presence of
110 Two complexes [Cr(H2O) 6]Cl 3 (A)
∆ value. MnC bond. The metal-carbon bond in
and [Cr(NH3 ) 6]Cl 3 (B) are violet and organometallic compounds possess
yellow coloured, respectively. The 112 Homoleptic octahedral complexes both σ and π-character. The MC
σ-bond is formed by the donation of lone
incorrect statement regarding of a metal ion ‘M 3+ ’ with three pair of electrons from the carbonyl
them is monodentate ligands L 1 , L 2 and L 3 carbon into a vacant orbital of the metal.
(a) ∆ o value for (A) is less than that of absorb wavelengths in the region The MC π-bond is formed by the
(B) of green, blue and red respectively. donation of pair of electrons from a filled
(b) both absorb energies The increasing order of the ligand d-orbital of metal into vacant
corresponding to their antibonding π * orbital of CO. The M L
strength is [2019, 9 Jan Shift-II]
bonding creates a synergic effect which
complementary colours
(a) L1 < L2 < L3 (b) L2 < L1 < L3 strengthens the bond between CO and
(c) ∆ o values of (A) and (B) are
(c) L3 < L1 < L2 (d) L3 < L2 < L1 the metal.
calculated from the energies of
violet and yellow light, respectively Ans. (c) The structure of Mn2 (CO) 10 is shown
In homoleptic complexes, the metal below :
(d) both are paramagnetic with three CO CO
unpaired electrons atom/ion is linked to only one type of CO CO
[2019, 9 Jan Shift-I] ligand. Assuming, ligands are neutral, CO Mn Mn CO
the octahedral complexes of M3+ can be,
Ans. (c) CO
[M(L1) 6 ] 3+ ,[M(L2 ) 6 ] 3+ and [M(L3) 6 ] 3+ CO CO CO
‘A’ absorbs yellow light of less energy and (I) (II) (III)
emits violet light of high energy λ Absorption Green
(complementary colour) becauseH2O is a
Blue Red (wavelength) 115 The metal d-orbitals that are
L L
weak field ligand. But in case of ‘B’, due So, λIII3 > λLI 1 > λII2 directly facing the ligands in
to presence of strong field ligand (NH3), K 3 [Co(CN) 6] are
∴∆°absorption : ∆II2 > ∆LI 1 > ∆III3
L L
it absorbs high energy violet light and (a) dxz , dyz and dz 2 (b) dx 2 − y 2 and dz 2
emits low energy complementary yellow 1
[QEnergy (∆, CFSE) ∝ ] (c) dxy , dxz and dyz (d) dxz and dx 2 − y 2
colour. l
∆(CFSE) is measured with help of We know, ligand strength ∝ ∆°absorption [2019, 12 Jan Shift-I]
wavelength of the colour absorbed by So, the increasing order of the ligand Ans. (b)
the given coordination compound, as strength will be, L3 < L1 < L2 In K3 [Co(CN) 6 ], Co have +3 oxidation
c
∆O = h ν = h × state and electronic configuration of
λ 113 The number of bridging CO ligand(s) Co3+ is [Ar] 18 3d 6 .
Both the complexes contain three and Co Co bond(s) in Co 2 (CO) 8 , 3d6 4s0 4p0
unpaired electrons. Therefore, both are respectively are [2019, 11 Jan Shift-II] Co3+=
paramagnetic.
(a) 2 and 0 (b) 0 and 2
(c) 4 and 0 (d) 2 and 1 As, CN − is a strong field ligands so it
111 The complex that has highest pairs up thede − s
Ans. (d)
crystal field splitting energy (∆), is
The structure of Co2 (CO) 8 (a polynuclear 3d6
[2019, 9 Jan Shift-II]
(a) [Co(NH3) 5 Cl] Cl2 metal carbonyl) can be written as : ∴ [Co(CN)6]3–= XX XX XX XX XX XX

Inner orbital
O d2sp3 -hybridised
(b) [Co(NH3) 5 (H2O)]Cl3 complex
(6e− pairs donated
(c) K 3 [Co(CN) 6] by 6 CN− ligands)
OC C CO
(d) K2 [CoCl4] In an octahedral complex, the metal is at
OC——Co——–Co——CO the centre of the octahedron and the
Ans. (c)
OC CO
ligands are at the six corners. The lobes
All of the complex given are the C
of the eg orbitals (d 2 2 and d 2 ) point
octahedral complexes of Co (III) except x −y z
O along the axes x, y and z under the
K2 [CoCl 4 ], which is a tetrahedral
complex of Co (II) (sp3-hybridised). Total number of bridging CO ligands = 2 influence of an octahedral field, the d-
and the Co  Co bond = 1 orbitals split as follow.
 4 
We know, ∆ t < ∆O Q∆ = ∆
 t 9 O 
Coordination Compounds 245

dx2-y2, dz 2 Py Py NH3 order of wavelength or decreasing order

NH3
Pt Pt of energy [QE∝ 1 / λ]. Therefore,
NH2OH Cl E Red < E yellow < E green < E blue
Cl HOH2N ( L4 )
Average dxy, dyz, dxz ( L1 ) ( L2 ) ( L3 )
d-orbitals energy of Py Cl
in free ion the d-orbitals Splitting of d-orbitals Py This suggests thatL4 will absorbs higher
in a spherical in an octahedral Pt energy wavelength followed byL2 , L3 and
crystal field crystal field HOH2N NH3 L1. Since, higher absorbed energy
corresponds to greater extent of crystal
Hence, this complex shows three field splitting and thus, higher field
As the d-orbitals, i.e. d and d are geometrical isomers.
x2 −y2 z2
strength of the ligand.
vacant.
Hence, the increasing order of ligand
Hence, these both orbitals are directly 118 Which of the following compounds strength of the four ligands is
facing the ligands in K3 [Co(CN) 6 ]. is not coloured yellow? L1 < L3 < L2 < L4
(a) Zn2 [Fe(CN) 6] [JEE Main 2015]
116 The magnetic moment of an (b) K 3 [Co(NO2 ) 6] 120 Which of the following facts about
octahedral homoleptic Mn(II) (c) (NH4 ) 3 [As(Mo 3O 10) 4] the complex [Cr(NH3 ) 6]Cl 3 is
complex is 5.9 BM. The suitable (d) BaCrO 4 wrong? [AIEEE 2011]
ligand for this complex is Ans. (a) (a) The complex involves d2 sp 3
−
(a) CN hybridization and is octahedral in
Zn2 [Fe (CN) 6 ], K3 [Co (NO2 ) 6 ] and
(b) ethylenediamine shape
[(NH4 ) 3 As (Mo3O10 ) 4 ] show colour due to
(c) NCS− d-d transition whileBaCrO4 is coloured (b) The complex is paramagnetic
(d) CO [2019, 12 Jan Shift-II] due to charge transfer phenomenon. (c) The complex is an outer orbital
Ans. (c) Further, according to spectrochemical complex
The magnetic moment of the magnitude series the strong ligand possessing (d) The complex gives white precipitate
5.9 BM suggest the presence of 5 complex has higher energy and hence with silver nitrate solution
unpaired electrons in Mn(II). This can be lower wavelength. Therefore, complexes Ans. (c)
cross verified by putting the value (5) of containingNO2 , NH4+ , O2 − etc ligands
unpaired electrons in the formula, show yellow colour while CN− forces the [Cr(NH3) 6 ]
14243
Cl
{3 j
complex to impart white colour. Coordinate sphere Ionisable
µ = n(n + 2) BM
Spectrochemical Series [Cr(NH3) 6 ] 3+ + 3Cl –
Thus, the valence electronic AgNO 3
configuration of Mn(II) in the complex is I− < Br − < S2 – < SCN− < Cl − < NO3− < N3− → AgCl ↓
White precipitate
< F − < OH−
Mn2+= In [Cr (NH3) 6 ] 3+ , Cr exists as Cr 3+ ion. The
< C2O24− ≈ H2O < NCS − < CH3CN < py < NH3
3d 4s 4p 4d outer orbital electronic configuration of
< en < bipy
− Cr is 3d 3 4s 0 . The orbital diagram is
The octahedral homoleptic complex < Phen < NO2 < PPh3 < CN− ≈ CO represented by
suggests sp3d2 -hybridisation in the
3d 3 4s0 4p0
complex, i.e. 119 The octahedral complex of a metal 3+
[Cr] =
sp3d2-hybridisation ion M 3+ with four monodentate
Mn2+= ligands L 1 , L 2 , L 3 and L 4 absorb [Cr(NH3)6 ]3+ =
3d 4s 4p 4d wavelengths in the region of red,
green, yellow and blue, d 2sp3
Thus, 5 unpaired electrons are present in hybridisation
respectively. The increasing order
the complex which suggest the presence Here, indicates lone-pair ofNH3
of a weak ligand like NCS.
of ligand strength of the four
ligands is [JEE Main 2014] donated to Cr.
117 The number of geometric isomers (a) L 4 < L 3 < L 2 < L 1
Hence,
that can exist for square planar (b) L 1 < L 3 < L 2 < L 4 (a) d2 sp3-hybridization, octahedral.
[Pt(Cl) (py) (NH3 ) (NH2OH)] + is (c) L 3 < L 2 < L 4 < L 1 Thus, correct.
(d) L 1 < L 2 < L 4 < L 3 (b) There are three unpaired
(py = pyridine) [JEE Main 2015]
electrons, hence paramagnetic
Ans. (b)
(a) 2 (b) 3 Thus, correct.
(c) 4 (d) 6 Ligand L1 L2 L3 L4 (c) d2 sp3-inner orbital complex, thus
Ans. (b) incorrect.
Coloured region of
[Pt(Cl) (py) (NH3) (NH2OH)] + is square Red Green Yellow Blue (d) Due to ionizable Cl − ions, white
absorbed wavelength
planar complex. The structures are precipitate with AgNO3, thus
formed by fixing a group and then Coloured regions of visible light correct.
arranging all the groups. (VIBGYOR) are arranged in the increasing Therefore, (c) is wrong.
246 JEE Main Chapterwise Topicwise Chemistry

121 The magnetic moment (spin only) 124 In Fe (CO) 5 , the Fe—C bond (c) d 4 (in weak ligand field)
of [NiCl 4] 2 – is [AIEEE 2011] possesses [AIEEE 2006] (d) d 4 (in strong ligand field)
(a) 1.82 BM (b) 5.46 BM (a) π-character only Ans. (d)
(c) 2.82 BM (d) 1.41 BM (b) both σ and π-characters (a) d 5 in strong field
Ans. (c) (c) ionic character n = unpaired electron = 1
[NiCl 4 ]2 – ; oxidation number of Ni (d) σ-character only
,x − 4 = − 2 Ans. (b) eg
∴ x = + 2, Ni (28) [Ar] 3d 8 , 4s 2 Fe (CO) 5 is an organometallic
sp 3 coordinated compound in which t2g
3d 8 electrons from d-orbital of Fe are
Ni 2+[Ar] partially transferred to anti-bonding Magnetic moment = n (n + 2) BM
∗
4s 0 4p molecular oritals ( π ) of CO. This type of
bonding is called π-backbonding. = 3 BM = 1.73 BM
[NiCl4]2– (b) d 3 in strong/weak field
Fe C=O
sp 3 sp 3 sp 3 sp 3
σ-bond eg
Four sp 3 hybrid orbitals electron donation
sp3-hybrid orbitals, tetrahedral from CO to Fe
Since, Cl − is a weak ligand, thus unpaired t2g
electrons are not paired. Lone pairs from
4 Cl − are accommodated in four sp3 n=3
Fe C ≡≡ O
hybrid orbitats. Magnetic moment = 15 = 3.87 BM
n = unpaired electron = 2, paramagnetic (c) d 4 in weak field
Magnetic moment (spin only) electron donation
through π -backbonding eg
= n (n + 2) BM = 8 = 2.828 BM
Thus,Fe (CO) 5 possesess both σ and
122 In which of the following octahedral π-character. t2g
complexes of Co (At no. 27), will the
magnitude of ∆ o be the highest? 125 Nickel (Z = 28) combines with a n=4
[AIEEE 2008] uninegative monodentate ligand Magnetic moment = 24 = 4.90 BM
(a) [Co (CN) 6] 3– X − to form a paramagnetic (d) d 4 in strong field
(b) [Co (C2O 4 ) 3] 3– complex [NiX 4] 2− . The number of
eg
(c) [Co (H2O) 6] 3+ unpaired electron (s) in the nickel
(d) [Co (NH3) 6] 3+ and geometry of this complex ion
Ans. (a) are, respectively [AIEEE 2006] t2g
(a) one, tetrahedral
CFSE (crystal field splitting energy) for
(b) two, tetrahedral n=2
octahedral complex, ∆ o depends on the
strength of negative ligand. (c) one, square planar Magnetic moment = 8 = 2.83 BM
Spectrochemically, it has been found (d) two, square planar
that the strength of splitting is as follows Ans. (b) 127 Which one of the following cyano
CO > CN– > NO2– > en >NH3 > py > 2 8 complexes would exhibit the
28 Ni = [Ar]4s ,3 d
NCS – > H2O > O2 − > OX2 – > OH– > F – > Ni2 + = [Ar] 3 d 8 lowest value of paramagnetic
behaviour ?
Cl – > SCN− > S2– > Br − > I –
[AIEEE 2005]

3d 4s 4p (At. no. of Cr = 24, Mn =25, Fe = 26,

123 Which one of the following has a sp3 Co = 27)
square planar geometry? Nickel has two unpaired electrons and (a) [Co(CN) 6] 3− (b) [Fe(CN) 6] 3−
geometry is tetrahedral due to sp3 (c) [Mn(CN) 6] 3− (d) [Cr(CN) 6] 3−
(At. no.
hybridisation. Ans. (a)
Co = 27, Ni = 28, Fe = 26, Pt = 78)
[AIEEE 2007] Hybridisation Unpaired Magnetic
2− 2− 126 The value of the ‘spin only’ electrons moment
(a) [CoCl4] (b) [FeCl4]
magnetic moment for one of the (a) [Co(CN) 6 ] 3− d2 sp3(0) 0
(c) [NiCl4] 2− (d) [PtCl4] 2−
Ans. (d)
following configurations is (b) [Fe(CN) 6 ] 3− d2 sp3(1) 3 BM
2.84 BM. The correct one is (c) [Mn(CN) 6 ] 3− d2 sp3(2)
Cl − is a weak ligand but Cl − cause the [AIEEE 2005]
8 BM
pairing of electrons with largePt2 + and 5 (d) [Cr(CN) 6 ] 3− d2 sp3(3) 15 BM
consequently givedsp2 hybridisation and (a) d (in strong ligand field)
(b) d 3 (in weak as well as in strong fields) Thus, least paramagnetism is (a).
square planar geometry.
Coordination Compounds 247

128 The correct order of magnetic [Co(NH3)6]3 += [Ar] 132 The compound used in the
moments (spin only values in BM) treatment of lead poisoning is
among the following is × × × × × × [2019, 12 April Shift-II]

(At. no of Mn = 25, Fe = 26, Co = 27) NH 3 is a (a) D-penicillamine

[AIEEE 2004]
d2 sp3 (inner (b) desferrioxime-B
strong ligand
d orbital complex)
(a) [MnCl4] 2 − > [CoCl4] 2 − > [Fe(CN) 6] 4 − (c) cis-platin
(d) Ni 2+= [Ar]
(b) [MnCl4] 2 − > [Fe(CN) 6] 4 − > [CoCl4] 2 − (d) EDTA
(c) [Fe(CN) 6] 4 − > [MnCl4] 2 − > [CoCl4] 2 − Ans. (d)
(d) [Fe(CN) 6] 4 − > [CoCl4] 2 − > [MnCl4] 2 − 3d8 4s 4p The compound used in the treatment of
Ans. (a) lead poisoning is EDTA. Medication
In this case also,NH3 is a strong ligand
occurs through chelation therapy.
Number of unpaired electrons in but electrons remain unpaired, since
only one orbital is left vacant in3d. Thus, Calcium disodium ethylenediamine
[Fe(CN) 6 ] 4− is zero. tetraacetic acid chelates divalent metal
[Ni(NH3) 6 ] 2 +
Thus, magnetic moment ion such as Pb2 + from plasma and
= n (n + 2) = 0 BM [Ar] interstitial body fluids.
(n = unpaired electrons) 3d8 The metal displaces Ca and is chelated,
n in [MnCl 4 ]2 − = 5, 35 BM mobilised and usually excreted. Less
× × × × × × then 5% CaNa2 EDTA is absorbed in the
n in [CoCl 4 ]2 − = 3, 15 BM
gastrointestinal tract and it possibly
4s 4p 4d
increases the absorption of Pb present
129 Which one of the following sp3d2
in the tract. Therefore, it is not
(outer d-orbital complex)
complexes is an outer orbital recommended for oral use. It is usually
complex? [AIEEE 2004] given intravenously.
130 The most stable ion is [AIEEE 2002]
(At. no. of Mn = 25,Fe = 26, (a) [Fe(OH) 5] 3− (b) [FeCl6] 3−
Co = 27, Ni = 28) 3− 133 Wilkinson catalyst is
4− 4−
(c) [Fe(CN) 6] (d) [Fe(H2O) 6] 3+ [2019, 10 Jan Shift-I]
(a) [Fe(CN) 6] (b) [Mn(CN) 6]
Ans. (c) (a) [(Et 3P) 3RhCl]
(c) [Co(NH3) 6] 3+ (d) [Ni(NH3) 6] 2+
Stability of complex increases with (b) [(Et 3P) 3IrCl] (Et = C2H5 )
Ans. (d)
increase in charge on the central metal
(a) Fe2+ = [Ar] ion and with increase in basic strength (c) [(Ph3P) 3RhCl]
of ligand. (d) [(Ph3P) 3IrCl]
In [Fe(CN) 6 ] 3− , oxidation state of Fe is +3 Ans. (c)
3d6 4s 4p and basicity of CN− is higher than
2+ – OH– , Cl − and H2O. Wilkinson’s catalyst is a σ-bonded
Fe in strong ligand CN = [Ar]
organometallic compound [(Ph3P) 3 RhCl]
. It is commercially used for
3d6 4s 4p TOPIC 3 hydrogenation of alkenes and vegetable
oils (unsaturated).
4–
[Fe(CN)6 ] [Ar]
Importance of IUPAC name Chloridotris
× × × × × × Coordination Compounds (triphenylphosphene) rhodium (I).

d2 sp3 (inner 131 Aqua-regia is used for dissolving 134 Coordination compounds have
d orbital complex)
noble metals (Au, Pt, etc.). The gas great importance in biological
(b) Mn2+= [Ar] evolved in this process is systems. In this context, which of
[2020, 3 Sep Shift-I]
the following statements is
(a) NO (b) N2O 5 incorrect ? [AIEEE 2004]
3d5 4s 4p (c) N2 (d) N2O 3
(a) Chlorophyll is green pigment in
[Mn(CN)6 4 – ] = [Ar] Ans. (a) plant and contain calcium
Aqua-regia is a mixture of conc. HCl and
(b) Haemoglobin is the red pigment of
× × × × × × conc. HNO3 (3 : 1,V /V )
blood and contains iron
(i) HNO3 + 3HCl → NOCl + Cl2 ↑ + 2H2O
(ii) NOCl → NO ↑ + [Cl] (c) Cyanocobalamin is vitamin B 12 and
d2 sp3 (inner
⇒Pt(s) + 4 [Cl] + 2HCl → H2 [PtCl 6 ](aq) contains cobalt
d orbital complex)
(d) Carboxypeptidase-A is an enzyme
⇒Au(s) + 3[Cl] + HCl → H[AuCl 4 ](aq)
(c) Co3+= [Ar] and contains zinc
Soluble form
Ans. (a)
Hence, the gas evolved in this process is
Chlorophyll contains Mg, hence (a) is
3d6 4s 4p NO.
incorrect statement.
20
Environmental
Chemistry
TOPIC 1 (iv) ClO + O → Cl + O2 04 Given below are two statements.
Atmospheric Pollution So, the intermediate in first step are One is labelled as Assertion (A) and
• •
Cl + CClF2 . the other is labelled as Reason (R).
01 In stratosphere most of the ozone Assertion (A) Photochemical
formation is assisted by 03 Match List I with List II. smog causes cracking of rubber.
[2021, 27 Aug Shift-II] List I List II Reason (R) Presence of ozone,
(a) cosmic rays (Compound) (Effect/affecte
nitric oxide, acrolein,
(b) γ–rays d species)
formaldehyde and peroxyacetyl
(c) ultraviolet radiations A. Carbon I. Carcinogenic
(d) visible radiations monoxide nitrate in photochemical smog
B. Sulphur dioxide II. Metabolised by
makes it oxidising.
Ans. (c)
pyrus plants Choose the most appropriate
In the stratosphere, the UV-light causes
the splitting ofO2 molecule into oxygen C. Polychlorinated III. Haemoglobin answer from the options given
atoms. These atoms react with oxygen biphenyls below. [2021, 26 Aug Shift-II]
present in the air to form ozone. D. Oxides of IV. Stiffness of (a) Both (A) and (R) are true but (R)
UV radiation nitrogen flower buds is not the correct explanation
O2 (g) → O(g) + O(g)
of (A).
O 2 (g ) + UV radiation Choose the correct answer from (b) Both (A) and (R) are true and (R) is
→ O3 (g)
Ozone
the options given below : the correct explanation of (A).
[2021, 27 July Shift-II] (c) (A) is false but (R) is true.
Therefore, the option (c) is correct.
A B C D A B C D (d) (A) is true but (R) is false.
02 The gas ‘A’ is having very low (a) III IV I II (b) IV I III II Ans. (b)
(c) I II III IV (d) III IV II I
reactivity reaches to stratosphere. Both Assertion and Reason are true and
It is non-toxic and non-flammable Ans. (a) Reason is the correct explanation of
but dissociated by UV-radiations in A. If haemoglobin binds CO, it Assertion. Smog is a type of intense air
prevents the binding ofO2 to pollution.
stratosphere. The intermediates
haemoglobin due to the It is composed of nitrogen oxides,
formed initially from the gas ‘A’ are competition for same binding sulphur oxides, ozone, smoke and other
[2021, 27 Aug Shift-I]
• • • •
sites. particulates. Rubber is an organic
(a) ClO + CF2Cl (b) ClO + CH3 B. Higher conc.SO2 in air can cause compound and it is sensitive to number
• • • • stiffness of flower buds. of chemical influences-oxidation,
(c) CH3 + CF2 Cl (d) Cl + CF2 Cl reduction etc. Excessive cracking of
C. Polychlorinated biphenyls are
Ans. (d) carcinogenic (cancer causing) in rubber products can be one of the
humans as well as animals. indicators of the presence of
The gas is chlorofluoro carbon. Its atmospheric photochemical oxidants.
reaction in stratosphere is as follows : D. Certain plants, e.g. pinus,
• •
Juniparus, quercus, pyrus and vitis Excessive cracking of rubber is
(i) CCl2 F2 + UV light → CClF2 + Cl caused by atmospheric ozone formed in
can metabolise nitrogen oxides.
(ii) CCl 3 F + UV light → CCl2 F + Cl Hence, the correct match is the photochemical smog formation
A → (III), B → (IV), C → (I), D → (II). process.
(iii) Cl + O3 → ClO + O2
Environmental Chemistry 249

05 Given below are two statements : (C) Methane is a stronger global Choose the most appropriate
Statement I Chlorofluoro carbons warming gas than CO 2 . answer from the options given
break down by radiation in the (D) Methane is a part of reducing below. [2021, 16 March Shift-II]

visible energy region and release smog. (a) Only (A) and (C) (b) Only (A)
chlorine gas in the atmosphere Choose the most appropriate (c) (A), (C) and (D) (d) Only (A) and (B)
which then reacts with answer from the options given Ans. (c)
stratospheric ozone. below [2021, 18 March Shift-I] Greenhouse gases are carbon dioxide,
(a) (A), (B), (C) only (b) (A) and (B) only methane, water vapours, nitrous oxide,
Statement II Atmospheric ozone
(c) (B), (C), (D) only (d) (A), (B), (D) only CFCs and ozone. The greenhouse effect
reacts with nitric oxide to give is a natural process that warms the
nitrogen and oxygen gases, which Ans. (a) Earth’s surface. When the Sun’s energy
add to the atmosphere. Methane leads to both global warming reaches the Earth’s atmosphere, some
and photochemical smog. of it is reflected back to space and the
For the above statements choose
Order of contribution of global warming rest is absorbed and re-radiated by
the correct answer from the greenhouse gases. The absorbed energy
gas
options given below : warms the atmosphere and the surface
[2021, 25 July Shift-II]
CO2 > CH4 > CFC > O3 > N2O > H2O
● Methane is generated in large
of the Earth.
(a) Statement I is incorrect but
statement II is true amounts from paddy fields. CH4 is 40
times stronger greenhouse gas than
10 The type of pollution that gets
(b) Both statement I and II are false increased during the day time and
CO2 .
(c) Statement I is correct but in the presence of O 3 is
statement II is false
●
CO2 can be absorbed by
[2021, 16 March Shift-I]
(d) Both statement I and II are correct photosynthesis or by formation of
acid rain etc., while no such activities (a) reducing smog (b) oxidising smog
Ans. (b) are there for methane. (c) global warming (d) acid rain
Chlorofluoro carbons are broken down by ● It has more heating effects. Hence,
Ans. (b)
powerful UV radiation and releases methane is stronger global warming
chlorine free radical which reacts with Oxidising smog (photochemical smog)
gas than CO2 . gets increased during the day time and in
ozone and start chain reaction.
• •
●
Methane is not a part of reducing smog. the presence ofO3.
CF2 Cl2 (g) 
UV
→ Cl (g) + CF2 Cl(g) Hence, statements (A), (B) and (C) are It occurs in warm, dry and sunny climate.
• • true. When fossil fuels are burnt,
CI (g) + O3 (g) → CIO(g) + O2 (g)
hydrocarbons (unburnt fuels) and nitric
• •
CIO (g) + O(g) → CI (g) + O2 (g) 08 Reducing smog is a mixture of oxide (NO) are produced. Ozone reacts
[2021, 17 March Shift-I] rapidly with the NO to generateNO2 .
∴Statement (I) is incorrect. (a) smoke, fog and O 3 NO( g) + O3( g) → NO2 ( g) + O2 ( g)
Atmosphere ozone reacts with nitric (b) smoke, fog and SO2
oxide to produce nitrogen dioxide and Ozone is a toxic gas and bothNO2 and O3
(c) smoke, fog and CH2 == CH CHO
oxygen. are strong oxidising agents and can
(d) smoke, fog and N2O 3
NO (g) + O3 (g) → NO2 (g) + O2 (g) react with the unburnt hydrocarbons in
Ans. (b) the polluted air to produce chemicals
∴Statement (II) is also incorrect.
Classical smog (reducing smog) occurs such as formaldehyde, acrolein and
06 Which one of the following gases is in cool humid climate, it is a mixture of peroxyacetyl nitrate (PAN).
smoke, fog and SO2 .
reported to retard photosynthesis ?
[2021, 20 July Shift-II] It is a reducing mixture/smog. 11 Given below are two statements.
(a) CO (b) CFCs (c) CO2 (d) NO2 Reducing smog = smoke + fog + SO2 Statement I The pH of rain water is
Ans. (d) Note Photochemical smog occurs in normally ~ 5.6.
warm, dry and sunny climate. The main Statement II If the pH of rain
From the given gases,NO2 is the gas components of the photochemical smog
which damage the leaves of plants and result from the action of sunlight on water drops below 5.6, it is called
retard the photosynthesis. Higher unsaturated hydrocarbons and nitrogen acid rain.
concentration of NO2 damage the leaves oxides produced by automobiles and In the light of the above
of plants and retard the rate of factories. Photochemical smog has high
photosynthesis. statements, choose the correct
concentration of oxidising agents and is
therefore, called as oxidising smog. answer from the options given
07 The statements that are true. below. [2021, 25 Feb Shift-II]

(A) Methane leads to both global 09 The greenhouse gas/es is (are) (a) Both statements I and II are true.
(b) Both statements I and II are false.
warming and photochemical (A) carbon dioxide
(d) Statement I is true but statement
smog. (B) oxygen II is false.
(B) Methane is generated from (C) water vapour (d) Statement I is false but statement
paddy fields. (D) methane II is true.
250 JEE Main Chapterwise Topicwise Chemistry

Ans. (a) reacts with O 3 to give chlorine Ans. (c)

The pH of rain water is normally 5.6. If it dioxide radicals Statements (A), (B) and (D) are correct
pH drop below 5.6, it is called acid rain. (b) in the atmosphere, it is depleted whereas (C) is incorrect. Corrected
∴ Both statements are correct. by CFCs statement is as follows : Acid rain can
(c) in the stratosphere, it forms a cause health problems in people. It
protective shield against UV causes respiratory aliments in human
12 Given below are two statements: radiation. being and animals.
Statement I An allotrope of (d) it is a toxic gas and its reaction
oxygen is an important with NO gives NO2 17 Among the gases (A)-(E), the gases
intermediate in the formation of Ans. (a) that cause greenhouse effect are :
reducing smog. Statement (a) is not true whereas all the [2020, 8 Jan Shift-I]

Statement II Gases such as oxides given statements are true. (A) CO 2 (B) H2O
of nitrogen and sulphur present in In the stratosphere, CFCs release (C) CFCs (D) O 2
troposphere contribute to the chlorine free radicals (Cl • ) which reacts
(E) O 3
with O3 to give chlorine monoxide (ClO • )
formation of photochemical radicals but not chlorine dioxide radicals. (a) (A), (B), (C) and (D)
smog. (b) (A) and (D)
In the light of the above 15 Thermal power plants can lead to (c) (A), (B), (C) and (E)
statements, choose the correct (a) acid rain [2020, 3 Sep Shift-I] (d) (A), (C), (D) and (E)
answer from the options given (b) blue baby syndrome Ans. (c)
below. [2021, 25 Feb Shift-I] (c) ozone layer depletion CO2 , H2O, CFCs and O3 are green house
(a) Both statement I and statement II (d) eutrophication gases. These gases trap the
are true. UV-radiations coming from the sun and
Ans. (a)
(b) Both statement I and statement II heat up the earth. Thus, heating up of
Thermal power plants emit oxides of earth is called green house effect.
are false.
nitrogen (NO2 ) and sulphur (SO2 ) in the
(c) Statement I is true but statement atmosphere which are converted into
II is false. 18 Assertion (A) Ozone is destroyed
HNO3 and H2SO4 respectively in the
(d) Statement I is false but statement pressure of rain water (H2O).
by CFCs in the upper stratosphere.
II is true. Reason (R) Ozone holes increase
4NO2 + O2 + 2H2O → 4HNO3
Ans. (d) 1 the amount of UV radiation
SO2 + O2 + H2O → H2SO4
Reducing smog is a mixture of smoke, 2 reaching the earth.
fog and sulphur dioxide. Therefore, Their presence in rain water becomes [2019, 8 April Shift-I]
statement I is false. acidic (pH< 56. ) and it is called acid rain. (a) Assertion and Reason are
Tropospheric pollutants such as ‘Blue baby syndrome’ is the condition due incorrect.
nitrogen oxide and sulphur oxide to poor oxygen transportation in the (b) Assertion and Reason are both
contribute to the formation of blood, resulting in blueness of the skin in correct and the Reason is the
photochemical smog. So, statement II is babies. correct explanation for the
true. Assertion.
Ozone layer depletion takes place due to
the attack of chlorofluorocarbon (CFCs) (c) Assertion and Reason are correct,
13 The gas released during anaerobic to ozone molecules. but the Reason is not the
degradation of vegetation may lead explanation for the Assertion.
‘Eutrophication’ is associated with water
to (d) Assertion is false, but the Reason
[2021, 24 Feb Shift-I] pollution when huge quantities of
is correct.
(a) acid rain phosphates and nitrates are released into
aquatic ecosystem. Ans. (c)
(b) global warming and cancer
(c) corrosion of metals Ozone is destroyed by CFCs in the upper
(d) ozone hole 16 The incorrect statement(s) among stratosphere.

Ans. (b)
(A) – (D) regarding acid rain is (are) : These compounds ultimately reach the
(A) It can corrode water pipes. stratosphere where they get broken
Methane (CH4 ) gas is evolved due to down by powerful UV radiations and
anaerobic degradation of vegetation (B) It can damage structures made release chlorine free radical. The
which causes global warming and up of stone. chlorine free radicals react with ozone
cancer. It is a heat trapping gas that (C) It cannot cause respiratory and cause its depletion by converting it
forces the planet to warm drastically ailments in animals. into chlorine monoxide radical and
and quickly. (D) It is not harmful for trees. molecular oxygen.
hν •
[2020, 3 Sep Shift-II] CF2 Cl2 (g) → Cl(g) + CF2 Cl(g)
14 The statement that is not true (a) (C) and (D) hν •
about ozone is [2020, 2 Sep Shift-I] (b) (A), (C) and (D) CFCl 3 (g) → CFCl2 (g) + Cl(g)
(a) in the stratosphere, CFCs release (c) (C) only • •
chlorine free radicals (Cl), which (d) (A), (B) and (D) Cl(g) + O3 (g) → ClO(g) + O2 (g)
Environmental Chemistry 251

Ozone holes increase the amount of UV colour. It occurs in warm, dry and sunny When the concentration of these
radiation reaching the earth. These climate. In presence of sunlight,NOx pollutants is sufficiently high, a chain
radiations can cause skin cancer, (N-oxides), O2 and unburnt hydrocarbons reaction initiate because of the
sunburns, ageing of skin. of air combine to produce interaction of sunlight with oxides of
photochemical smog which mainly nitrogen.
19 Excessive release of CO 2 into the contains peroxyacetyl nitrate (PAN). Sunlight
O 2NO(g) + O2 (g)  
→ 2NO2 (g)
atmosphere results in || hν
[2019, 9 April Shift-I] CH3  C O O NO2 (PAN) NO2 (g) → NO(g) + [O]
(a) formation of smog Nascent
oxygen
(b) depletion of ozone 23 The correct set of species O3 (g) + NO(g) → NO2 (g) + O2 (g)
(c) polar vortex responsible for the photochemical Brown gas
(d) global warming smog is [2019, 12 April Shift-I]
Ans. (d) (a) N2 , NO2 and hydrocarbons 25 The pH of rain water, is
The effect of release of CO2 gas into (b) CO2 , NO2 , SO2 and hydrocarbons approximately
atmosphere is global warming. (c) NO, NO2 , O 3 and hydrocarbons (a) 7.5 (b) 6.5
(d) N2 , O2 , O 3 and hydrocarbons (c) 5.6 (d) 7.0
20 The layer of atmosphere between [2019, 9 Jan Shift-II]
Ans. (c)
10 km to 50 km above the sea level Ans. (c)
is called as The correct set of species responsible
[2019, 9 April, Shift-II] In clean air, rain water picks up some
for the photochemical smog is NO,NO2 ,
(a) stratosphere (b) mesosphere acidic oxides like CO2 and SO2 (obtained
O3 and hydrocarbons. Photochemical
(c) thermosphere (d) troposphere from volcanic eruptions). These
smog appears in warm, dry and sunny
Ans. (a) substance make the rain slightly acidic
climate which are obtained by the action
(pH = 5.6 − 6). But, when rain falls
The atmosphere between the heights 10 of sunlight on unsaturated hydrocarbons
through polluted air, it consumes oxides
to 50 km above the sea level is and nitrogen oxides. Following reactions
of sulphur (SOx ) and oxides of nitrogen
stratosphere. Atmosphere is not of the are involved during the formation of
(NOx ), mists of HCl etc. They make the
same thickness at heights. photochemical smog.
rain more acidic (called acid rain) of pH
(i) N2 (g) + O2 (g) → 2NO(g) range 3.5 to 5.6.
21 The regions of the atmosphere, (Originates from burning of fossil fuels)
where clouds form and where we Sunlight
(ii) 2NO(g) + O2 (g) → 2NO2 (g) 26 The reaction that is not involved in
live, respectively, are hν the ozone layer depletion
[2019, 10 April, Shift-I] NO2 (g) → NO(g) + [O]
Nascent oxygen
mechanism in the stratosphere is
(a) stratosphere and stratosphere
(iii) O (g) + O2 (g) - O ( g) (a) CH4 + 2O 3 → 3CH2 == O + 3H2O
(b) troposphere and troposphere 3 • •
(c) troposphere and stratosphere Reacts rapidly with NO (b) ClO(g) + O(g) → Cl(g) + O2 (g)
(d) stratosphere and troposphere O3 (g) + NO(g) → NO (g) + O (g)
2 • •
(c) HOCl(g) → OH(g) + Cl(g)
2 hn
Brown gas (in high
Ans. (b) hn • •
The lowest region of atmosphere is
concentration form haze) (d) CF2Cl2 (g) → Cl(g) + CF2Cl(g)
troposphere which extends upto the 3CH4 (g) + 2O3 (g) → 3CH2 == O(g) [2019, 10 Jan Shift-II]
height of 10 km (approx) from sea level. Formaldehyde
Ans. (a)
We live in the tropospheric region. It (Unburnt hydrocarbon)
CH4 is not present in the stratosphere
contains air, water vapour and dust
+ CH2 == CHCH == O+ H2O and also it cannot diffuse or escape into
which can form clouds with the help of
Acrolein the stratosphere like freon-12 (CF2 Cl2 )
strong air movement.
from the atmosphere.
Above the troposphere, stratospheric 24 The primary pollutant that leads to
In the stratosphere, ozone layer
region extends upto 50 km from sea photochemical smog is depletion take place mainly by
level. It contains mainlyN2 , O2 , O3 and [2019, 12 April Shift-II]
chlorofluorocarbons (CFCs) like CF2 Cl2
little water vapour.O3 in the stratosphere (a) acrolein (b) nitrogen oxides and the mechanism of ozone layer
absorbs 99.5% of the sun’s harmful UV (c) ozone (d) sulphur dioxide depletion can be shown as:
raditions and thus protects the lives on • •
the earth.
Ans. (b) (i)
hν
CF2 Cl2 (g) → Cl (g) + CF2 Cl(g)
The primary pollutant that leads to [Option, (d)]
photochemical smog is nitrogen oxides. •
22 Air pollution that occurs in sunlight (ii) Cl (g) + O3 (g) → ClO (g) + O2 •
Burning of fossil fuels such as petrol and
is [2019, 10 April, Shift-II]
(a) acid rain (b) oxidising smog
diesel in automobiles, reaction between (iii) ClO• (g) + O(g) → Cl • (g) + O2 (g)
nitrogen and oxygen and other such [Option (b)]
(c) fog (d) reducing smog reactions result in a variety of pollutants, •
Ans. (b) two main of which are hydrocarbons (iv) Cl (g) + H2O(g)
(unburnt fuel) and nitric oxide (NO). [Present in the
In sunlight oxidising smog or stratosphere]
photochemical smog or Los-Angeles In petrol and
N2 (g) + O2 (g)  → 2NO(g) → HOCl(g ) + H•(g )
smog is formed. This smog is brown in diesel engines
252 JEE Main Chapterwise Topicwise Chemistry

•
(v) HOCl(g) → hν
OH(g) + Cl • (g) 29 The compound that is not a (c) The Assertion is incorrect but the
common component of Reason is correct.
[Option (c)]
(d) Both the Assertion and Reason are
⇒One Cl • can destroy or deplete 10 5 O3 photochemical smog is incorrect.
molecules. (a) CF2Cl2 (b) H3C C OONO2
 Ans. (a)
As (i) reaction is involved in the formation
O Nitrogen is an inert gas because of the
of photochemical smog, not in ozone
layer depletion. So, option (a) is correct. (c) CH2 == CHCHO (d) O 3 presence of strong bond. That's why
although there is 78%N2 in the
[2019, 12 Jan Shift-II]
atmosphere but nitrogen oxide in not
27 Taj Mahal is being slowly disfigured Ans. (a) formed under ordinary conditions.
and discoloured. This is primarily Freons or CFCs or chlorofluoro carbons, But when temperature is high enough
due to [2019, 11 Jan Shift-II] i.e. CF2Cl 2 is not the common i.e. ≈ 2000 K, it reacts with oxygen to
(a) water pollution component of photochemical smog. form nitrogen oxide.
(b) soil pollution This smog is produced as the result of ≈ 2000 K
tropospheric pollution while freons are N2 + O2 → 2NO
(c) global warming
the components of stratospheric Thus, Assertion and Reason are true and
(d) acid rain
pollution. These are infact considered as Reason is the correct explanation of the
Ans. (d)
the major cause of ozone layer depletion. Assertion.
Acid rain (pH = 3.5 − 5.6) constitutes
strong acids likeHNO3, H2SO4 and H2SO3 30 The upper stratosphere consisting
which slowly react with marble (CaCO3)
32 The gas leaked from a storage tank
of the ozone layer protects us from of the Union Carbide plant in
of Taj Mahal and make it disfigured and
discoloured. the sun’s radiation that falls in the Bhopal gas tragedy was
Here, CaCO3 (marble) gets dissolved in wavelength region of (a) Methylisocyanate [JEE Main 2013]
acids. [2019, 12 Jan Shift-II]
(b) Methylamine
(a) 600- 750 nm (b) 400-550 nm
2 H⊕ (aq) (c) Ammonia
CaCO3 (s ) → Ca2 + (aq) (c) 08
. -15
. nm (d) 200- 315 nm
(Acid rain) (d) Phosgene
Ans. (d)
+ H2O(l ) + CO2 (g) ↑ Ans. (a)
Sun emits UV-radiations, which according
Methylisocyanate CH3 N == C == O (MIC
28 The molecule that has minimum/no to following EM categorisation have the
gas) gas was leaked from the storage
wavelength range from 1 nm to 400 nm.
role in the formation of tank of the union carbide plant in Bhopal
photochemical smog, is gas tragedy.
Type Wavelength range
[2019, 12 Jan Shift-I]
Radio wave > 0.1 m 33 Identify the incorrect statement
(a) N2 (b) CH2 == O
Microwave 0.1 m to 1 mm from the following [AIEEE 2011]
(c) NO (d) O 3
Infrared wave 1 mm to 700 nm (a) Oxides of nitrogen in the
Ans. (a)
Visible rays 700 nm to 400 nm atmosphere can cause the
N2 molecule has minimum role in the Ultraviolet rays 400 nm to 1 nm depletion of ozone layer
formation of photochemical smog. While
X-rays 1 nm to 10 − 3 nm (b) Ozone absorbs the intense
CH2 == O, O3 and NO has major role. When
Gamma rays < 10 − 3 nm ultraviolet radiations of the sun
fossil fuels are burnt, a variety of
pollutants are emitted.
(c) Depletion of ozone layer is
Thus, option (d) with 200-315 nm range is because of its chemical reactions
Two of them are hydrocarbons (unburnt) the correct option. with chlorofluoro alkanes
and NO. When these pollutants build
(d) Ozone absorbs infrared radiations
upto high levels, a chain reaction
31 Assertion (A) Nitrogen and oxygen Ans. (d)
occurs from their interaction with
sunlight. The reactions involved in the are the main components in the NO + O3 → NO2 + O2
formation of photochemical smog are as atmosphere but these do not react O3 + hv → O2 + O
follows: to form oxides of nitrogen. NO2 + O → NO + O2
NO2 (g) 
hν
→ NO(g) + O(g) Reason (R) The reaction between (a) Net reaction 2O3 + hν → 3O2
O(g) + O2 (g) 1 O3 (g) nitrogen and oxygen requires high Thus, ozone layer is depleted by
NO(g) + O3 (g) → NO2 (g) + O2 (g) temperature. [JEE Main 2015] oxides of nitrogen.
O3 reats with unburnt hydrocarbons to (a) Both Assertion and Reason are Thus, (a) is correct statement.
produce chemicals such as correct and the reason is the (b) Ozone layer is a protective layer
formaldehyde, acrolein and PAN. correct explanation for the and absorbs harmful UV rays from
Assertion. the sun.
3CH4 + 2O3 → 3CH2 == O + 3H2O (b) Both Assertion and Reason are Thus, (b) is also correct statement.
+ CH2 == CCH == O+ CH3 COONO2 correct but the reason is not the •
 correct explanation for the (c) Cl +O3 → ClO + O2
O Assertion. •
(PAN) O3 +hv → O + O2
Environmental Chemistry 253
• •
ClO +O → Cl +O2 (c) uninfluenced by occurrence of Ans. (c)
thunderstorm Statement (c) is not correct as
Net reaction
(d) which depends on the amount of eutrophication leads to decrease in
2O3 + hv → 3 O2
dust in air oxygen level. Eutrophication means well
Thus, ozone layer is also depleted
Ans. (a) nourished. It occur in following four
by reaction with freons.
simple steps:
Thus, (c) is also correct statement. During thunderstorm, there is formation
● Lakes in many parts of the Earth have
of NO which changes toNO and
(d) It is a incorrect statement as ozone been severly eutrophied by sewage,
ultimately to HNO3 (acidrain).
2
layer is permeable for UV rays. agricultural industrial wastes.
O2
Thus, correct answer is (d). N2 + O2 → NO → NO2 ● The contaminents are rich in nitrate

4NO2 + O2 + 2H2O → 4HNO3 and phosphate, spark the over growth

34 Identify the wrong statements in of algae in water bodies.
[pH< 7]
the following [AIEEE 2008] ● When algae forms, it blocks sunlight

(a) Chlorofluorocarbons are from entering water and user up

responsible for ozone layer
depletion
TOPIC 2 oxygen. Eventually, water becomes
oxygen depleted.
(b) Green house effect is responsible Water and Soil Pollution ● Finally, this oxygen depleted water

for global warming becomes a dead zone and can no

(c) Ozone layer does not permit 37 Water sample is called cleanest on longer support life.
infrared radiation from the sun to the basis of which one of the BOD
reach the earth values given below 40 Given below are two statements
(d) Acid rain is mostly because of
oxides of nitrogen and sulphur
[2021, 1 Sep Shift-II] Statement I Non-biodegradable
Ans. (c) (a) 11 ppm (b) 15 ppm wastes are generated by the
Ozone layer permits the infrared (c) 3 ppm (d) 21 ppm thermal power plants.
radiation to pass through but doesn’t Ans. (c) Statement II Bio-degradable
permit the higher range of ultraviolet BOD is the biological oxygen demand. detergents leads to
radiation to pass through. Cleanest water sample will have BOD eutrophication.
value equal to (SO2 ) 3 ppm as clean
35 The smog is essentially caused by water could have BOD value of less than In the light of the above
the presence of [AIEEE 2004] 5 ppm. statements, choose the most
(a) O2 and O 3 appropriate answer from the
(b) O2 and N2 38 BOD values (in ppm) for clean water option given below.
(c) oxides of sulphur and nitrogen (A) and polluted water (B) are [2021, 18 March Shift-II]

(d) O 3 and N2 expected respectively (a) Both statements I and II are false.
[2021, 31 Aug Shift-I] (b) Statement I is true but statement
Ans. (a) II is false.
(a) A > 50, B < 27 (b) A > 25, B < 17
Smog is formed by the action of sunlight (c) Statement I is false but statement
(c) A < 5, B > 17 (d) A > 15, B > 47
on unsaturated hydrocarbons and II is true.
nitrogen oxides. Ans. (c)
(d) Both statements I and II are true.
Smog mainly contains higher BOD value of clean water is less than 5
Ans. (d)
concentration of Peroxyacetyl nitrate ppm.
(PAN) formed by the reaction ofNO2 , O3 So, A < 5 Non-biodegradable wastes are
and unsaturated hydrocarbons. generated by the thermal power plants
BOD value of polluted water is greater which produces fly ash. Detergents
NO → hv NO + O than 17 ppm.
2 which are biodegradable causes problem
So, B > 17 called eutrophication, which kills aquatic
O + O2 1 O3
NO + O3 → NO2 + O2 Thus, correct option is (c). life by deprieving it of oxygen.
NO + O3 + unsaturated hydrocarbons Hence, both statements are true.
→ PAN 39 Which one of the following
statements is not correct ? 41 Which of the following statement(s)
[2021, 27 July Shift-I] is (are) incorrect reason for
36 When rain is accompanied by a
(a) Eutrophication indicates that eutrophication ?
thunderstorm, the collected rain
water body is polluted.
water will have a pH value (b) The dissolved oxygen A. Excess usage of fertilisers.
[AIEEE 2003]
concentration below 6 ppm B. Excess usage of detergents.
(a) slightly lower than that of rain inhibits fish growth. C. Dense plant population in
water without thunderstorm (c) Eutrophication leads to increase in water bodies.
(b) slightly higher than that when the the oxygen level in water. D. Lack of nutrients in water
thunderstorm is not there (d) Eutrophication leads to anaerobic bodies that prevent plant
conditions. growth.
254 JEE Main Chapterwise Topicwise Chemistry

Choose the most appropriate into water. It enables rapid growth of Ans. (d)
answer from the options given bacteria and algae in water and then According to W.H.O. and US
microorganism use so much oxygen, environmental protection agency
below. [2021, 17 March Shift-II]
enough oxygen in not left for other guidelines, maximum allowable
(a) Only A (b) Only C animals living in the water. concentration of metals in drinking
(c) B and D (d) Only D In eutrophication nutrient enriched water are as follows :
Ans. (d) water bodies support a dense plant
population, which kills animal life by Metal Maximum concentration
Statement (D) is incorrect. (ppm or mg dm−3)
depriving it of oxygen and results in
As eutrophication is the  gradual increase subsequent loss of biodiversity. It Cd 0.005
in the concentration of phosphorus, indicates polluted environment.
nitrogen, and other plant nutrients  in an Mn 0.05 (option-c)
aging aquatic ecosystem such as a lake. 44 Biochemical oxygen demand (BOD) Al 0.2
The productivity or fertility of such an
is the amount of oxygen required Fe 0.2
ecosystem naturally increases as the
amount of organic material that can be (in ppm) [2020 Jan Shift-II] Cu 3.0 (option-d)
broken down into nutrients increases. (a) for the photochemical breakdown Zn 5.0 (option-a)
of waste present in 1 m3 volume of
42 Given below are two statements. a water body.
(b) for sustaining life in a water body. 47 The concentration of dissolved
Statement I The value of the oxygen (DO) in cold water can go
(c) by anaerobic bacteria to
parameter “Biochemical Oxygen breakdown inorganic waste upto
Demand (BOD)” is important for present in a water body. (a) 14 ppm (b) 10 ppm
survival of aquatic life. (d) by bacteria to breakdown organic (c) 8 ppm (d) 16 ppm
Statement II The optimum value waste in a certain volume of a [2019, 11 Jan Shift-I]
water sample. Ans. (b)
of BOD is 6.5 ppm.
Ans. (d)
In the light of the above Dissolved oxygen (DO) is the oxygen
B.O.D is defined as the amount of oxygen dissolved in water either from
statements, choose the most (ppm) required by bacteria to breakdown atmosphere or by photosynthesis. The
appropriate answer from the organic waste in certain volume of a lower the concentration of DO in a water
options given below. water sample. sample, the more polluted is the water
[2021, 24 Feb Shift-II] sample.
(a) Statement I is false but statement 45 Which is wrong with respect to our
The concentration range of dissolved
II is true. responsibility as a human being to oxygen (DO) in cold water reaches upto
(b) Both statements are true. protect our environment? 10 ppm, but that in normal water (at room
(c) Statement I is true but statement [2019, 8 April Shift-I] temperature) is within 5 ppm.
II is false. (a) Restricting the use of vehicles
(d) Both statements are false. (b) Avoiding the use of floodlighted 48 A water sample has ppm level
Ans. (c) facilities concentration of the following
(c) Setting up compost tin in gardens metals: Fe = 0.2; Mn = 5.0; Cu = 3.0;
Statement I is true but statement II is
(d) Using plastic bags
false. Zn = 5.0. The metal that makes the
Ans. (d)
Clean water would have BOD value of water sample unsuitable for drinking
less than Using plastic bags is wrong with respect
is [2019, 9 Jan Shift-I]
5 ppm whereas highly polluted water to responsibility as a human being to
could have a BOD value of 17 ppm or protect our environment. Plastic bags are (a) Cu (b) Fe
more. non-biodegradable in nature. It remains in (c) Mn (d) Zn
Hence, the value of parameter ‘BOD’ is the environment as such and does not Ans. (c)
important for survival of aquatic life but degraded by bacteria. If it is not For drinking water, the maximum
optimum value of BOD is 17 ppm or more. disposed properly then it may lead recommended levels of some metals,
So, statement II is incorrect. serious threat to the environment. The set by European Environment
activities that can be used to protect our Commission (EEC) is
43 The condition that indicates a environment are as follows:
●
Restricting the use of vehicles. Metal Max. concentration in ppm
polluted environment is
[2020, 5 Jan Shift-I]
●
Avoiding the use of flood lighted Zn 5
(a) pH of rain water to be 5.6 facilities. Mn 0.05
●
Setting up compost tin in gardens.
(b) eutrophication Fe 0.2
(c) BOD value of 5 ppm 46 The maximum prescribed Cu 3
(d) 0.03% of CO2 in the atmosphere concentration of copper in drinking As the concentration of Mn in the given
Ans. (b) water is [2019, 8 April Shift-II] water sample is more than the
In this process large quantities of (a) 5 ppm (b) 0.5 ppm recommended concentration. Thus, it
phosphates and nitrates are released (c) 0.05 ppm (d) 3 ppm makes water unsuitable for drinking.
Environmental Chemistry 255

49 The condition for is a secondary pollutant. It is present in methemoglobinemia (blue baby

photochemical smog (oxidising or Los syndrome.)
methemoglobinemia by drinking
Angeles smog). PAN is a powerful SO24 − The maximum limit of sulphate
water is [2019, 9 Jan Shift-II]
lachrymator or tear producer and it also
(a) > 50 ppm nitrate causes breathing troubles. (SO24 − ) according to WHO is 500 pm
(b) > 50 ppm chloride and its sources are acid rain,
(c) > 50 ppm lead 52 Water samples with BOD values of industries. Excess SO24 − has laxative
effect.
(d) > 100 ppm sulphate 4 ppm and 18 ppm, respectively,
F − The maximum limit of fluoride (F − ) is
Ans. (a) are [2019, 12 Jan Shift-I]
about 1.5 ppm. Its higher concentration
According to EEC (European (a) clean and clean converts enamel to more harder
Environment Commission), excess of (b) highly polluted and clean fluorapatite. Concentration (>2ppm)
NO−3 (> 50 ppm) in drinking water may (c) highly polluted and highly polluted causes brown mottling of teeth and high
lead to methemoglobinemia (‘Blue baby (d) clean and highly polluted concentration (>10 ppm) are harmful for
syndrome’). It also may cause bones and teeth.
Ans. (d)
stomach-cancer.
The amount of oxygen required by ∴ SO24 − (100 ppm) andNO−3 (50 ppm) in
bacteria to break down the organic water is suitable for drinking but the
50 Water filled in two glasses A and B concentration of F − (10 ppm) makes
matter present in a certain value of a
have BOD values of 10 and 20, sample of water is called biochemical water unsuitable for drinking.
respectively. The correct oxygen demand (BOD). The amount of
statement regarding them, is BOD in the water is a measure of the 54 The concentration of fluoride, lead,
[2019, 10 Jan Shift-I] amount of organic material in the water,
nitrate and iron in a water sample
(a) A is more polluted than B in terms of how much oxygen will be
(b) A is suitable for drinking, wherease required to break it down biologically. from an underground lake was
B is not Clean water would have BOD value of found to be 1000 ppb, 40 ppb, 100
(c) Both A and B are suitable for less than 5ppm whereas highly polluted ppm and 0.2 ppm, respectively.
drinking water would have BOD value of 17 ppm or This water is unsuitable for drinking
(d) B is more polluted than A more.
due to high concentration of
BOD value of clean water = 4 ppm [JEE Main 2016]
Ans. (d)
BOD value of highly polluted water = 18 (a) lead (b) nitrate
BOD is defined as the amount of oxygen ppm.
required by bacteria to break down the (c) iron (d) fluoride
organic matter present in a certain Ans. (b)
volume of a sample of water. Clean 53 A water sample has ppm level
concentration of following anions : This water is unsuitable for drinking due
water or drinking water has a BOD value
[JEE Main 2017] to high concentration of nitrate. In
< 5 ppm.
− drinking water, maximum permissible
So, water filled with A, BOD = 10 ppm is F = 10 concentration of
polluted and water filled with B, SO 24 − = 100 Lead ~− 50 ppb
BOD = 20 ppm, is also polluted.
NO −3 = 50 − 50 ppb
Nitrate ~
But, B is more polluted than A.
The anion/anions that − 0.2 ppm
Iron ~
51 Peroxyacetyl nitrate (PAN), an eye make/makes the water sample Fluoride ~− 1 ppm
irritant is produced by unsuitable for drinking is/are
[2019, 11 Jan Shift-I] (a) Only NO −3 55 What is DDT among the following?
(a) organic waste (b) Both SO24 − and NO −3 (a) Green house gas [AIEEE 2012]
(b) acid rain (c) Only F − (b) A fertilizer
(c) classical smog
(d) Only SO24 − (c) Biodegradable pollutant
(d) photochemical smog (d) Non-biodegradable pollutant
Ans. (c)
Ans. (d) Ans. (d)
NO−3 The maximum limit of nitrate (NO−3 )
Molecular formula of peroxyacetyl DDT is a non-biodegradable pollutant. It
O in drinking water is 50 ppm and its
source is fertilisers. If the maximum limit is the first chlorinated organic

nitrate (PAN) is CH3  C O O NO2 . It is increased in water it will cause insecticide.
21
Purification and
Characterisation of
Organic Compounds
TOPIC 1 Boiling point of propanone = 56°C 03 Given below are two statements.
Methods of Purification Difference in boiling points
= 41° C > 20 ° C
Statement I Retardation factor
(R f ) can be measured in
01 Given below are two statements. Hence, option (d) is correct.
metre/centimetre.
One is labelled as Assertion (A) and Statement II R f value of a
02 Which purification technique is
the other is labelled as Reason (R). compound remains constant in all
used for high boiling organic
Assertion (A) A simple distillation liquid compound (decomposes solvents.
can be used to separate a mixture near its boiling point)? Choose the most appropriate
of propanol and propanone. [2021, 22 July Shift-II] answer from the options given
Reason (R) Two liquids with a (a) Simple distillation below [2021, 17 March Shift-I]
difference of more than 20°C in (b) Steam distillation (a) Statement I is true but statement
their boiling points can be (c) Fractional distillation II is false.
separated by simple distillations. (d) Reduced pressure distillation (b) Both statement I and statement II
In the light of the above Ans. (d) are true.
Distillation under reduced pressure is (c) Both statement I and statement II
statements, choose the most
used to purify liquids having very high are false.
appropriate answer from the (d) Statement I is false but statement
boiling points and those, which
options given below. decompose at or below their boiling II is true.
[2021, 31 Aug Shift-I]
points. Ans. (c)
(a) (A) is false but (R) is true.
Because the boiling point of liquids
(b) Both (A) and (R) are correct but (R) is are decreased at reduced pressure. Solvent
not the correct explanation of (A). Organic compounds can be distilled at front
(c) (A) is true but (R) is false lower temperatures. Spot
(d) Both (A) and (R) are correct and (R) is Such liquids are made to boil at a
the correct explanation of (A). temperature lower than their normal
Ans. (d) y
boiling points by reducing the x Base line
Propanol and propanone can be pressure on their surface.
separated by simple distillation technique By reducing pressure, it can be
as difference in boiling point of propanol distilled at low boiling point to avoid
and propanone is more than 20°C. Developed
their decomposition. chromatogram
Boiling point of propanol = 97°C.
Purification and Characterisation of Organic Compounds 257

Distance moved by the substance Ans. (d) acetophenone. When the column
from base line (x) Statement I is true, i.e. a mixture of is eluted with a mixture of
Rf =
Distance moved by the solvent chloroform and aniline can be separated
solvents, hexane : ethyl acetate
by simple distillation. Boiling points of
from base line (y) (20 : 80), the sequence of obtained
chloroform (334 K) and aniline
Rf (Retardation factor is dimensionless) (457 K) differ largely. So, on boiling the compounds is [2020, 7 Jan Shift-II]
Different compounds are differently mixture, vapours of CHCl 3 are formed (a) (C), (A) and (B) (b) (A), (B) and (C)
adsorbed in various. first which is then condensed to pure (c) (B), (C) and (A) (d) (B), (A) and (C)
So, Rf value of a compound varies with liquid CHCl 3. Whereas, the vapours of
aniline will form later and liquid aniline
Ans. (a)
solvent and it is not constant.
can be collected separately. In column chromatography, individual
Both statements I and II are false.
Statement II is also true, i.e. aniline and components of a mixture are separated
water can be separated by steam by elution (washing with solvents). The
04 In chromatography technique, the distillation technique. Aniline is steam component with relatively stronger rate
purification of compound is volatile but immiscible with water. So, a of adsorption attached with mobile
independent of mixture of aniline and water will boil
phase (solvents) move faster down the
[2021, 16 March Shift-I] close to but below 373 K. After
column (greater Rf value), and gets
(a)
mobility or flow of solvent system distillation, the mixture of aniline
(bottom layer) and water (top layer) can eluted first, followed by other
(b)
solubility of the compound components in the decreasing order of
(c)
length of the column or TLC plate be separated by separating funnel.
So, both statements I and II are true Rf values.
(d)
physical state of the pure
compound (option-d). In the given separation, the solvent
used has greater polarity due to greater
Ans. (d) 06 Glycerol is separated in soap composition of polar solvent ethyl
In chromatography technique, the industries by [2020, 3 Sep Shift-I] acetate (80%), and therefore, more
purification of compound is (a) fractional distillation polar component (having greater dipole
independent of physical state of the
(b) differential extraction moment) of mixture will have more Rf
pure compound (stationary phase).
Chromatography is based on the (c) steam distillation value and will get eluted faster. Dipole
principle of adsorbtion. Different (d) distillation under reduced pressure moment of components in mixture is in
substances are differently adsorbed. Ans. (d) the order :
The technique of chromatography uses In soap industries, glycerol is separated O
the difference in the rates at which the from spent lye using distillation under
C
components of a mixture move through reduced pressure.
(C) acetophenone CH3 >
a porous medium (stationary phase) So, option (d) is correct.
under the influence of some solvent or
(a) Fractional distillation is used to
gas (moving phase).
separate two liquids when NH
difference in their boiling points is C
05 Given below are two statements : (A) benzanilide
not much.
Statement I A mixture of e.g. Separation of different NH2
chloroform and aniline can be fractions of crude oil in petroleum
separated by simple distillation. refinery. > (B) aniline
Statement II When separating (b) Differential extraction is based on
different solubilities of an organic
aniline from a mixture of aniline ∴ The sequence of obtained
compound in different solvents. In
and water by steam distillation this process same solvent is compounds is (C) > (A) > (B)
aniline boils below its boiling repeatedly used (continuous
point. extraction) for extraction of the 08 A flask contains a mixture of
compound. isohexane and 3-methylpentane.
In the light of the above
(c) Steam distillation method is used One of the liquids boils at 63°C
statements, choose the most to separation substances which while the other boils at 60°C. What
appropriate answer from the are steam volatile and are is the best way to separate the
options given below. immiscible with water.
[2021, 26 Feb Shift-I] two liquids and which one will be
e.g. Separation of aniline water
(a) Statement I is false but statement mixture. distilled out first?
[2020, 8 Jan Shift-I]
II is true
(b) Both statement I and statement II 07 A chromatography column, packed (a) Fractional distillation
are false with silica gel as stationary phase, 3-methylpentane
(c) Statement I is true but statement was used to separate a mixture of (b) Fractional distillation, isohexane
II is false (c) Simple distillation,
compounds consisting of (A)
(d) Both statement I and statement II 3-methylpentane
benzanilide (B) aniline and (C) (d) Simple distillation, isohexane
are true
258 JEE Main Chapterwise Topicwise Chemistry

Ans. (b) Ans. (b) (a) (A) → (Q); (B) → (R); (C) → (S)
The boiling points of the given In chromatography, the expression of (b) (A) → (Q); (B) → (R); (C) → (P)
compounds are very close. retention factor (Rf ) is (c) (A) → (S); (B) → (R); (C) → (P)
(d) (A) → (R); (B) → (P); (C) → (S)
∴ Simple distillation can’t be used. Distance travelled by the
compound from origin Ans. (a)
Fractional distillation is only suitable to Rf = <1
separate the two liquids. Distance travelled by the The correct option is :
(A) → (Q); (B) → (R); (C) → (S)
Further, the liquid with lower boiling solvent from origin
(A) H2O and sugar mixture They do not
point distills out first. Since, 3-methyl The value of Rf signifies the relative react chemically. On heating,
pentane has a more symmetrical ratio of migration of each component of solubility of sugar inH2O increases
structure as compared to isohexane. the mixture with respect to the and on rapid cooling of saturated
Therefore, it has a greater area of developing solvent used. Rf value solution, sugar recrystallises (Q).
contact and better interaction between depends on the type of adsorption (B) H2O and aniline mixture Aniline is
molecules. This accounts for the chromatography like TLC (Thin-Layer steam volatile but insoluble inH2O.
greater boiling point of 3-methyl Chromatography), paper So, steam distillation (R) is
pentane as compared to isohexane. employed for their separation.
chromatography etc. The Rf value is
also the characteristic of a compound (C) H2O and toluene mixture Toluene is
steam non-volatile and also
(sample) for a given developing solvent at
insoluble inH2O. So, differential
Isohexane 3-methyl pentane a given temperature. extraction method (S) can be used
60°C 63°C
When the compound in the sample to separate them.
(usually less polar) is weakly adsorbed
09 The principle of column the spot will travel a shorter distance 13 The distillation technique most
chromatography is
[2019, 10 April Shift-I]
from the origin and hence the Rf value suited for separating glycerol from
will be decreased. spent lye in the soap industry is
(a) differential absorption of the
[JEE Main 2016]
substances on the solid phase
11 If dichloromethane (DCM) and (a) fractional distillation
(b) differential adsorption of the
substances on the solid phase water (H2O) are used for (b) steam distillation
(c) gravitational force differential extraction, which one (c) distillation under reduced pressure
(d) capillary action of the following statements is (d) simple distillation
Ans. (b) correct? Ans. (c)
(a) DCM and H2O would stay as lower and
In column chromatography, separation Glycerol with high boiling point (290°C)
upper layer respectively in the S.F.
of mixture of compounds (adsorbate) can be separated from spent lye by
(b) DCM and H2O would stay as upper
takes place over a column of solid and lower layer respectively in the distillation under reduced pressure.
adsorbent (silica gel and Al2O3) packed in separating funnel (SF) This process is used to purify liquids
a glass tube. (c) DCM and H2O will be miscible clearly having very high boiling points. By this
(d) DCM and H2O will make process, liquid is made to boil at lower
When an appropriate eluant (liquid) is
turbid/colloidal mixture temperature than its boiling point by
allowed to flow down the column, the
[2019, 10 Jan Shift-I] lowering the pressure on its surface.
compounds present in the mixture get
adsorbed to different extent on the Ans. (a)
adsorbent column and thus complete
separation takes place.
Dichloromethane, DCM (CH2 Cl2 ) is
heavier (density = 1.3266 g cm−3) than
TOPIC 2
water (density = 1g cm−3). So, DCM and Qualitative Analysis
Thus, column chromatography is based H2O will stay as lower and upper layer
on the differential adsorption of the respectively in the separating funnel
substance on the solid phase. (SF). 14 The metal that can be purified
economically by fractional
10 In chromatography, which of the 12 The correct match between items distillation method is
following statements is incorrect I and II is [2019, 11 Jan Shift-I]
[2021, 20 July Shift-I]
for R f ? [2019, 10 April Shift-II] (a) Fe (b) Zn (c) Cu (d) Ni
Item I Item II
(a) Rf value depends on the type of Ans. (b)
(Mixture) (Separation method)
chromatography Zinc can be purified economically by
(b) Higher Rf value means higher A. H2O : Sugar P. Sublimation
fractional distillation.
adsorption B. H2O : Aniline Q. Recrystallisation Fractional distillation process utilises
(c) Rf value is dependent on the mobile C. H2O : Toluene R. Steam distillation the boiling point difference between
phase metal and that of impurity. Using this
(d) The value of Rf can not be more than S. Differential process, crude zinc containing Cd, Fe
one extraction and Pb as impurities can be refined.
Purification and Characterisation of Organic Compounds 259

15 In the sulphur estimation, 0.471 g 17 Nitrogen can be estimated by (II) Duma’s method → CuO/ CO2
of an organic compound gave Kjeldahl's method for which of the This method is based upon the
fact that nitrogenous compound
1.44 g of barium sulphate. The following compound ?
when heated with cupric oxide in
percentage of sulphur in the [2021, 17 March Shift-II]
an atmosphere of CO2 , yield free
compound is ……… %. nitrogen. Traces of oxide of
(Nearest integer) (a) (b) nitrogen, which may be formed in
some cases, are reduced to
(Atomic mass of Ba = 137 u) elemental nitrogen by passing
[2021, 26 Aug Shift-II] +
N≡≡ NCl– CH2NH2 over heated copper spiral.
Ans. (42) (III) Kjeldahl’s method →H2SO4
Atomic mass of sulphur is 32 g. This method is used for the
Molecular weight ofBaSO4 is 233 g. quantitative determination of
(c) (d)
So, weight of sulphur in BaSO 4 nitrogen containing organic
Atomic mass of sulphur N substances. In this method,
= NO2 consists of heating a sample at
Molecular weight of BaSO4
Ans. (b) 360-410°C with concentrated
× Weight of BaSO4 sulphuric acid (H2SO4 ), which
32 Nitrogen can be estimated by Kjeldahl's decomposes the organic sample
= × 1.44 method for the benzyl amine as in this
233 by oxidation to liberate the
compound nitrogen is not the part of reduced nitrogen as ammonium
Percentage of sulphur
ring and is free to react. sulphate.
Weight of sulphur
= × 100 Because this method can be readily
Weight of organic compound (IV) Hinsberg test →
applied to the compound in which C6H5SO2 Cl /aq. KOH
32 1. 44 nitrogen is free to react with the
= × × 100 = 41.98 −
~ 42% Hinsberg reagent is an alternative
233 0.471 reagent. The compounds which have name for benzene sulphonyl
nitrogen in the ring (like pyridine), an azo chloride.
16 Reagent, 1-naphthylamine and compound, or in nitro compounds are This name is given for its use in
sulphanilic acid in acetic acid is not readily converted into the the Hinsberg test for the detection
ammonium sulphate by the action of and distinction of primary, secondary
used for the detection of sulphuric acid.
[2021, 18 March Shift-I] and tertiary amine in a given
(a) N2O (b) NO −3 (c) NO (d) NO2− sample.
18 Match the following : So, correct match is option (c).
Ans. (d)
When a solution is acidified with acetic Test / Method Reagent
19 Which of the following compounds
acid, sulphanilic acid and then I. Lucas test (A) C 6H5SO 2 Cl / KOH will be suitable for Kjeldahl’s
1-naphthylamine is added, the red
coloured precipitate obtain indicates II. Dumas method (B) HNO 3 / AgNO 3 method for nitrogen estimation?
presence ofNO2− anions. For detection III. Kjeldahl’s method (C) CuO /CO 2
[JEE Main 2018]

of NO2− following test is used. NH2

+
– IV. Hinsberg test (D) Conc. HCl and
NH3CH3COO N==N—OCOCH3 ZnCl 2 (a) (b)

+ – (E) H2SO 4 N
+ HNO2 + 2H2O
NO2 N+2Cl–
[2020, 6 Sep Shift-II]
SO3H (a) (I)-(D), (II)-(C), (III)-(B), (IV)-(E) (c) (d)
SO3H
Sulphanilic (b) (I)-(B), (II)-(D), (III)-(E), (IV)-(A)
acid solution
(c) (I)-(D), (II)-(C), (III)-(E), (IV)-(A) Ans. (b)
Above reagent is used to detectNO2– ion. (d) (I)-(B), (II)-(A), (III)-(C), (IV)-(D)
N== NOCOCH3 Estimation of nitrogen through
Ans. (c)
Kjeldahl’s method is not suitable for
Correct match is organic compounds containing nitrogen
+ I → (D), II → (C), III → (E), IV → (A) in ring or nitrogen in nitro or azo groups.
(I) Lucas test → Conc.HCl + ZnCl2 It is because of the fact that nitrogen of
SO3H NH3 It is a solution of anhydrous zinc these compounds does not show
Diazotised 1-naphthylamine
acid
chloride in concentrated conversion to Ammonium sulphate
hydrochloric acid. This solution is ((NH4 )2 SO4 ) during the process. Hence,
used to classify alcohols of low among the given compounds only
molecular weight. Primary,
HO3S 
aniline can be used suitably for
 N== N —NH2 secondary and tertiary alcohols
estimation of nitrogen by Kjeldahl’s
are classified based on their
(Red azo dye) reactivity with the Lucas reagent. method.
+ CH3COOH
260 JEE Main Chapterwise Topicwise Chemistry

1.2
TOPIC 3 22 In carius method for estimation of VH 2 SO 4 =
100
L {1 L = 1000 mL}
halogens, 0.2 g of an organic
Quantitative Analysis compound gave 0.188 g of AgBr. VH 2 SO 4 = 12 mL
The percentage of bromine in the
20 The transformation occurring in 24 KMnO4 'A'
compound is ……… (Nearest H2SO4, ∆
Duma’s method is given below integer)
(Major product)

C 2H7 N + 2x +  CuO → x CO 2

y
[Atomic mass; Ag = 108, Br = 80] KMnO4
 2 [2021, 27 Aug Shift-I] H2O, 273K
'B'
(Major product)
+ H2O + N 2 + 2x +  Cu
y z y Ans. (40)
2 2  2 Mass of bromine = 80 u
For above chemical reactions,
identify the correct statement
The value of y is ......... . (Integer Mass of silver = 108 u
from the following
answer) [2021, 31 Aug Shift-II] Mass of AgBr = 108 + 80 = 188 u [2021, 20 July Shift-I]
Ans. (7) Weight of organic compound = 0.2 g (a) Both compound 'A' and compound
Molar mass of Br
For the reaction % of Br = × 'B' are dicarboxylic acids.
Molar mass of AgBr (b) Both compound 'A' and compound
C2H7N+  2x +  CuO →
y
 Weight of AgBr 'B' are diols.
2 × 100
Weight of organic compound (c) Compound 'A' is diol and
H2O + N2 +  2x +  Cu
y z y
x CO2 + 80 0.188 compound 'B' is dicarboxylic acid.
2 2  2 = × × 100 = 40%.
188 0.2 (d) Compound 'A' is dicarboxylic acid
On reactant side number of H-atom = 7 and compound 'B' is diol.
On product side number of H-atom 23 0.8 g of an organic compound was Ans. (d)
y
= ×2 analysed by Kjeldahl's method for Compound ‘A’ is dicarboxylic acid and
2
y the estimation of nitrogen. If the compound ‘B’ is ‘diol’. Alkenes forms
7 = ×2 dicarboxylic acid on treating with hot
2 percentage of nitrogen in the
acidicKMnO4 .
∴ y=7 compound was found to be 42%,
Chemical reactions are as follows
then ……… mL of 1 M H2SO 4 would 2
1
21 The number of moles of CuO, that have been neutralised by the KMnO4 3 COOH
will be utilised in Dumas method ammonia evolved during the H2SO4,∆ 4 6
COOH
for estimation nitrogen in a sample analysis. [2021, 25 July Shift-II] 5
Cyclohex-1-ene 1,6-hexa-dioic acid
of 57.5 g of Ans. (12) (Dicarboxylic acid)
(A)
N, N-dimethylaminopentane is Organic compound analysed by
……… × 10 − 2 . (Nearest integer) Kjeldahl’s method = 0.8 g Alkenes on treating withKMnO4 in water
at room temperature gives diol.
Weight of nitrogen =  × 0.8 g
[2021, 27 Aug Shift-I] 42
Ans. (1125)  100  2
1 OH
KMnO4 3
weight of N
In Dumas method, Mole of N = H2SO4,273K 4 6
molar mass of N
Cx Hy Nz +  2x +  CuO → xCO2
y OH
5
 2 42 × 0.8 2.4 Cyclohexene
Mole of N = = mol Diol (Cyclo-1,6-hexanol)
100 × 14 100 (B)
H2O + +  2x +  Cu
y z y
+ 2.4
2 2  2 Mole of NH3 = mol
N,N-dimethylaminopentane has formula
100 25 Methylation of 10 g of benzene
C7H17N. Reaction, gave 9.2 g of toluene. Calculate
2NH3 + H2SO4 → (NH4 )2 SO4 the percentage yield of toluene
So, relating with Cx Hy Nz
2.4 1.2
x = 7; y = 17; z = 1 mol mol ……… . (Nearest integer)
100 100 [2021, 22 July Shift-II]
Molar mass of C7H17N = 115 g
∴2 moles of NH3 will neutralise 1 mole of Ans. (78)
1 mole C7H17N requires =  2x +  CuO
y
H2SO4 .
 2 For the reaction,
Given 1 M H2SO4 is neutralised byNH3
= 22.5 moles of CuO C6H6 (10g) + CH3Cl + Anhyd. AlCl 3
∴Molarity of
 57.5  Moles of H2SO4 → C6H5 CH3 (9.2 g)
57.5 g i.e.   C7H17N will utilise H2SO4 =
 115  Volume of solution (L) 1 mole of benzene produced 1 mole of
22.5 toluene, if reaction yield is 100%.
= × 57.5 moles of CuO 12
. 1
1M = × 78 g of benzene produced 92 g of
115 100 VH 2 SO 4 (L)
toluene, if reaction yield is 100%.
= 11.25 g mol 1⋅ 2 Actual yield
≈ 1125 × 10 −2 mol. ∴ Number of mole ofH2SO4 = % yield = × 100
100 100% yield
Purification and Characterisation of Organic Compounds 261
9.2
% yield = × 100 = 78% Consider the above reaction of moles of bromomethane
92
× 10 where 6.1 g of benzoic acid is consumed in this reaction are
78
used to get 7.8 g of m-bromo n × 10 −1 , when n = ......... (Round off
Hence, % yield of toluene is 78.
benzoic acid. The percentage to the nearest integer).
26 When 0.15 g of an organic yield of the product is ……… . (Given : Atomic masses : C = 12.0
compound was analysed using (Round off to the nearest u, H = 1.0 u, N = 14.0 u, Br = 80.0 u]
Carius method for estimation of integer). [2021, 18 March Shift-I]

bromine, 0.2397 g of AgBr was [Given : Atomic masses : Ans. (3)

obtained. The percentage of C = 12.0 u, H = 1.0 u, O = 16.0u, Benzylamine reacts with bromoethane
bromine in the organic compound Br = 80.0 u] [2021, 18 March Shift-II] to produce benzyltrimethyl ammonium
bromide.
is …… . (Nearest integer) Ans. (78) The reaction is as follows :
[Atomic mass : Silver = 108, Moles of benzoic acid (i) CH3Br
bromine = 80] [2021, 20 July Shift-II] 6.1 (weight) PhCH2 NH2
= –HBr
Ans. (68) 122 (molecular weight) Benzyl amine
(0.1 mol)
Carius halogen method is generally used = moles of m-bromobenzoic acid PhCH2NH¾CH3
to determine the quantity of halogens in So, weight of m-bromobenzoic acid –HBr
(ii) CH3Br
a chemical compound. In this method, 6.1
= × 201 g
heat known mass of an organic 122 CH3
compound with fumingHNO3 in = 10.05 g  (iii) CH3Br
presence of AgNO3 in a hard glass tube. Actual weight PhCH2 N CH3 Br– –HBr
% yield = × 100 +
Moles of Br = Moles of AgBr obtained Theoretical weight 
Mass of AgBr 7.8 CH3
Mass of Br = = × 100 = 77.61% ~− 78% Benzyl trimethyl ammonium
Molecular weight of AgBr 10.05 bromide (23 g)
CH
× Molecular weight of Br Ph CH2N  3
0.2397 29 ......... grams of 3-hydroxy propanal CH3
= × 80 g
188 (MW = 74) must be dehydrated to Ph  CH2NH2 + 3CH3Br →
+
w produce 7.8 g of acrolein (MW= 56) 0.1 mol
PhCH2 N(Me) 3Br –
% of Br = Br × 100
w Total (C 3H4O), if the percentage yield is w 23g
= = 0 .1 mol
m 230
0.2397 × 80 64 (Round off to the nearest
= × 100 = 0.85 × 80 = 68 ⇒ 0.1 × 3 = 0.3
188 × 0.15 integer).
Total moles of CH3Br = 0.3
[Given : Atomic masses : C = 12.0 = 3 × 10 −1 mol.
27 In Carius method, halogen u, H = 1.0 u, O = 16.0 u]
containing organic compound is [2021, 18 March Shift-I]
31 In Carius method of estimation of
heated with fuming nitric acid in Ans. (16) halogen 0.172 g of an organic
the presence of [2021, 20 July Shift-II On reaction compound showed presence of
(a) HNO 3 (b) AgNO 3 ∆ 0.08 g of bromine. Which of these
HO  CH2  CH2  CHO →
(c) CuSO 4 (d) BaSO 4 64%
3-hydroxy propanal is the correct structure of the
Ans. (b) (mol. wt = 74) C3H4O + H2O compound? [2020, 2 Sep Shift-I]
Acrolein
Organic compound is heated with (mol. wt=56) (a) H3C Br (b) H3C CH2Br
fuming nitric acid in the presence of Let’s assume required man of NH2 NH2
silver nitrate in Carius method. 3-hydroxypropanal be x to produce 0.64
Br
This method used for quantitative g acrolein.
(c) (d)
determination of halogens in chemical ∴Number of moles = x /74
substance. Method is based on the fact x
So, mol gives 0.64 g yield.
that when organic compound 74 Br Br
containing halogen (Cl, Br, I) is heated in Now, 7.8 g of acrolein gives,
sealed tube with fumingHNO3 in
Ans. (c)
x 7.8
presence of excess of AgNO3, silver × 0.64 = In the organic compound
74 56
halide is formed. 0.08
⇒ x = 16.10 or x ~= 1600
. Br% = × 100 = 46.51
0.172
28 COOH COOH
30 A reaction of 0.1 mole of Now, let us calculate Br % in the given
compounds.
FeBr3 benzylamine with bromomethane
+ Br2 + HBr (a) CH3Br (M = 95)
gave 23 g of benzyl trimethyl
80
Br ammonium bromide. The number ⇒Br % = × 100 = 8421
.
95
262 JEE Main Chapterwise Topicwise Chemistry

(b) C2H5Br (M = 109) combustion tube in the atmosphere of 35 For the estimation of nitrogen,
80 CO2 . Upon heating, C and H present are
⇒Br% = × 100 = 7339
. 1.4 g of an organic compound was
oxidised to CO2 and water vapours while
109 digested by Kjeldahl’s method and
N2 is set free.
(c) C6H6NBr (M = 172) Let, the molecular formula of the the evolved ammonia was
80 organic compound (1 mol) be Cx Hy Nz . In absorbed in 60 mL of M/10
⇒ Br% = × 100 = 46.51
172 Dumas method, sulphuric acid. The unreacted acid
Cx Hy Nz +  2x +  CuO → xCO2
y required 20 mL of M/10 sodium
(d) C6H5NBr2 (M = 251)
1 mol
 2  hydroxide for the complete
160
⇒ Br% = × 100 = 63.74 y z neutralization. The percentage of
251 x mol mol mol
2 2 nitrogen in the compound is
So, correct structure of compound is
+ H2O + N2 +  2x +  Cu
y z y [JEE Main 2014]
(c).
2 2  2 (a) 6% (b) 10%
32 In an estimation of bromine by y z (c) 3% (d) 5%
Now, x = 6, = 4 ⇒ y = 8 and = 1
Carius method, 1.6 g of an organic 2 2 Ans. (b)
compound gave 1.88 g of AgBr. ⇒ z =2 Mass of an organic compound (OC) = 1.4 g
The mass percentage of bromine ∴ Molecular formula of the compound is Suppose x m mole of N-atom is present
in the compound is ....... . (Atomic C6H8N2 . in organic compound. Thus,
mass, Ag = 108, Br = 80 g mol −1 ) Kjeldahl’ s
Organic compound → NH 3
[2020, 6 Sep Shift-I] method x m mole
34 In Carius method of estimation of
Ans. (50) M
halogens, 250 mg of an organic Initial m mol ofH2SO4 = 60 × = 6 mmol
Molar mass of AgBr = 108 + 80 ⇒188g/mol compound gave 141 mg of AgBr. 10
Weight of organic compound = 16 The percentage of bromine in the mmoles of NaOH required by
. g
M
Weight of AgBr = 1.88 g compound is (at. mass Ag = 108, Br H2SO4 = 20 × = 2 mmol
10
% of Br
= 80) [JEE Main 2015]
Involved reactions are
Weight of AgBr × 80 (a) 24 (b) 36
= 2NH3 + H2SO4 → (NH4 )2 SO4
Weight of organic compound × 188 (c) 48 (d) 60
 6 mmol 
 Initially taken 
× 100 Ans. (a)
1.88 × 80 H2SO4 + 2NaOH → Na2SO4 + 2H2O
= × 100 = 50% Given, Weight of organic compound
2 mmol reacted
1.6 × 188 = 250 mg
Weight of AgBr = 141 mg Hence, 1 mmole ofH2SO4 reacted with
Hence, the correct answer is 50.
NaOH.
∴According to formula of % of bromine
33 An organic compound is estimated ⇒mmoles of H2SO4 reacted from first
by Carius method equation = 6 − 1 = 5 mmoles
through Dumas method and was Atomic weight of Br
% of Br = ⇒mmoles of NH3 in first equation = 2 × 5
found to evolved 6 moles of CO 2 , Molecular weight of Ag Br = 10 mmoles
4 moles of H2O and 1 mole of
Weight of AgBr ⇒mmoles of N atoms in the organic
nitrogen gas. The formula of the × × 100
Weight of organic bromide compound = 10 m moles
compound is [2019, 11 Jan Shift-I]
80 141 ⇒ mass of N = 10 × 10 −3 × 14
(a) C 6H8N (b) C 12H8N ∴ % of Br = × × 100
188 250 = 0.14g % of N in
(c) C 12H8N2 (d) C 6H8N2
Mass of N in OC
Ans. (d) =
1128000 OC = × 100
47000 Total mass of OC
In Dumas method, organic compound is 0.14
heated with dry cupric oxide in a = 24% ∴ % of N = × 100 = 10%
1.4
22
Some Basic Principles
of Organic Chemistry
TOPIC 1 03 The total number of CC sigma Ans. (b)
Nomenclature bond/s in mesityl oxide (C 6H10 O) is 6
........ . (Round off to the nearest CHO
3 CH3
01 The number of sigma bonds in integer). [2021, 17 March Shift-II] 5 2
H 3C
H3C  C == CHC ≡≡ C His …… . Ans. (5) 4
Principal
 [2021, 25 July Shift-I]
The structural formula with C  C sigma
1 COOH chain
H bond(s) in mesityl oxide is as follows:
IUPAC name is 2,
Ans. (10) σ
H3C— σ
C==CH— σ
C—
σ
CH3
σ
5-dimetyl-6-oxo-3-enoic acid.
According to given structure,
H CH3 O
06 The IUPAC name of the following
σ σ σ σ σ σ Therefore, number of C  C sigma
H  C  C == C  C ≡≡ C  H bonds in mesityl oxide = 5. compound is
σ σ σ
σ  
H H H
04 Mesityl oxide is a common name of CH3 O
Total number of σ bonds = 10 C—OH
[2021, 17 March Shift-I]
Note Double bond or triple bond
(a) 2,4-dimethyl pentan-3-one
contains one Br
(b) 3-methyl cyclohexane carbaldehyde
σ-bond and 2pi-bonds, respectively.
(c) 2-methyl cyclohexanone [2020, 4 Sep Shift-I]
02 In the following molecules, (d) 4-methyl pent-3-en-2-one (a) 3-bromo-5-methylcyclopentane
a Ans. (d) carboxylic acid
H3C b c
C C O Mesityl oxide is a common name of (b) 3-bromo-5-methylcyclopentanoic
H
H 4-methyl pent-3-en-2-one. acid
hybridisation of carbon a, b and c (c) 5-bromo-3-methylcyclopentanoic
5 acid
respectively are
[2021, 18 March Shift-II] 4 2 (4-methyl pent-3-en-2-one) (d) 4-bromo-2-methylcyclopentane
3 1
3
(a) sp , sp, sp 3
(b) sp , sp , sp2 carboxylic acid
(c) sp 3, sp2 , sp2 (d) sp 3, sp, sp2 05 The IUPAC name for the following Ans. (d)
Ans. (c) compound is The IUPAC name of the given
Hybridisation of carbon a, b and c compound.
CHO
respectively are sp3, sp2 and sp2 .
CH3 CH3 O
Here, a = carbon is sp3 hybridised with 3 H3C 2
H atoms, C OH
b = carbon is sp2 hybridised with C == C, COOH 3 1

c = carbon is sp2 hybridised within [2020, 2 Sep Shift-I]

4 5
benzene ring as C == C. (a) 6-formyl-2-methyl-hex-3-enoic acid Br
Structure is as follows (b) 2, 5-diamethyl-6-oxo-hex-3-enoic
a(sp3) acid 4-bromo-2-methylcyclopentane
c(sp2)
H3 C b(sp2) (c) 2, 5-dimethyl-6-carboxy-hex-3-enal carboxylic acid.
C C—O— (d) 2, 5-dimethyl-5-carboxy-hex-3-enal
H H
264 JEE Main Chapterwise Topicwise Chemistry

07 The IUPAC name of the following 09 The correct IUPAC name of the CH3
compounds is following compound is H 3C 7 CH
5
4 6
OH [2019, 9 April Shift-I]
2 3 Longest possible
NH2 NO2 CH3 chain containing
1
CH2 double and
O2N triple bond

CHO Cl If both double and triple bonds are

[2020, 6 Sep Shift-II] CH3 present in the compound, the endings
(a) 2-nitro-4-hydroxymethyl-5-amino like-en-yne, a (numeral)
benzaldehyde (a) 2-methyl-5-nitro-1 dien-(numeral)-yne etc., are used.
(b) 3-amino-4-hydroxymethyl-1-5- -chlorobenzene Numbers as low as possible are given to
nitrobenzaldehyde (b) 3-chloro-1-methyl-1-nitrobenzene double and triple bonds as a set.
(c) 5-amino-4-hydroxymethyl (c) 2-chloro-1-methyl
1-2-nitrobenzaldehyde 1-4-nitrobenzene 11 What is the IUPAC name of the
(d) 4-amino-2-formyl -5- (d) 5-chloro-4-methyl following compound ?
hydroxymethyl -nitrobenzene 1-1-nitrobenzene
CH3 CH3
Ans. (c) Ans. (c)
OH The IUPAC name of the given compound H
Substituent H
4
is Br
NH2
3 5 CH3
NO2
2 6
O2N 4 [2019, 10 Jan Shift-II]
Incorrect

1
Correct
3 (a) 3-bromo-3-methyl-1,
way

way
CHO Main functional
Substituent 2-dimethylprop-1-ene
group 2
Cl (b) 3-bromo-1,2-dimethylbut-1-ene
5-amino-4-hydroxymethyl-1-2-nitrobenzal 1
dehyde (c) 2-bromo-3-methylpent-3-ene
CH3
(d) 4-bromo-3-methylpent-2-ene
2- chloro-1-methy l-4-nitrobenzene Ans. (d)
08 The IUPAC name of the following
compound is Here, the given compound contains two While naming the compound, alkene
CH3 OH or more functional groups. So, the gets priority over functional group
  numbering is done in such a way that ( Br) and numbering starts from
H3C  CH CHCH2 COOH the sum of the locants is the lowest. alkene side. Hence, IUPAC name:
[2019, 8 April Shift-I]
4-bromo-3-methylpent-2-ene
10 The IUPAC name for the following
(a) 4,4 - dimethyl -3-hydroxybutanoic 1
CH3
compound is [2019, 12 April Shift-II] CH3
acid
(b) 2-methyl-3-hydroxypentan-5-oic CH3 2 H
acid 3
H3C CH H
4
(c) 3- hydroxy -4- methylpentanoic acid
(d) 4-methyl-3-hydroxypentanoic acid CH3 Br
5
Ans. (c) CH3
The IUPAC name of the given compound CH2 12 The IUPAC name of neopentane is
is 3-hydroxy-4-methylpentanoic acid. (a) 2-methylbutane [AIEEE 2009]
(a) 3-methyl-4-(3-methylprop-
CH3 OH 1-enyl)-1-heptyne (b) 2,2-dimethylpropane
5
4 3 2 1 (b) 3, 5-dimethyl-4-propylhept- (c) 2-methylpropane
H3 C  CH  CH  CH2  COOH 6-en-1-yne (d) 2,2-dimethylbutane
Principal chain Ans. (b)
(c) 3-methyl-4-(1-methylprop-
While naming the compound, the The neopentane
2-ynyl)-1-heptene
longest chain that have principal (d) 3, 5-dimethyl-4-propylhept- CH3
functional group —COOH is choosen and 1-en-6-yne 3  1 2
numbered in such a manner that the CH3  C  CH3
Ans. (d)
principal functional group gets the 
lowest possible number. —OH act as The IUPAC name for the given CH3
substituent and used as prefix in compound is 3, IUPAC name : 2,2-dimethylpropane
nomenclature. 5-dimethyl-4-propylhept-1-en-6-yne.
Some Basic Principles of Organic Chemistry 265

13 The correct decreasing order of 16 The number and type of bonds (b) CH3 CHCH2CHO
priority for the functional groups 
between two carbon atoms in CH3
of organic compounds in the calcium carbide are [AIEEE 2005]
IUPAC system of nomenclature is 3-methyl butanal
[AIEEE 2008] (a) two sigma, two pi O
(b) two sigma, one pi 
(a)  COOH,  SO 3H, CONH2 , (c) CH3 CHC CH2CH3
 CHO (c) one sigma, two pi
(d) one sigma, one pi 
(b)  SO3H, COOH, CONH2 , CH3
 CHO Ans. (c) 2-methyl-3-pentanone
(c)  CHO,  COOH,  SO 3H, CaC 2 (calcium carbide) is ionic. (d) CH3 C H CH CH3
 CONH2 
CaC2 → Ca2 + + C22 − 
(d)  CONH2 ,  CHO,  SO 3H, − OH
 COOH C ≡≡ C− H3C
2−
C2 has one σ and two π-bonds. 2-methyl-3-butanol
Ans. (a)
Ans. (d)
The correct decreasing order of priority 17 The IUPAC name of the compound is 4 3 2 1
for the functional groups of organic incorrect
CH3CHCHCH3
compounds in the IUPAC system is numbering 1 2| 3| 4
 COOH > SO3H >  COOR > COCl CH3 OH
>  CONH2 >  CN >  CH == O HO Correct name 3-methyl butan-2-ol
[AIEEE 2004] or 3-methyl-2-butanol
14 The IUPAC name of [AIEEE 2007] (a) 3, 3-dimethyl-1-hydroxy cyclohexane Correct numbering
(b) 1, 1-dimethyl-3-hydroxy cyclohexane functional group
(c) 3, 3-dimethyl-1-cyclohexanol should be given
is priority
(d) 1, 1-dimethyl-3-cyclohexanol
Ans. (c)
(a) 1, 1-diethyl-2, 2-dimethylpentane
(b) 4, 4-dimethyl-5, 5-diethylpentane
5 TOPIC 2
6 4
(c) 5, 5-diethyl-4, 4-dimethylpentane
1 3
Isomerism
(d) 3-ethyl-4, 4-dimethylheptane
HO 20 The number of stereoisomers
Ans. (d) 2
6 2 Carbon with —OH group is givenC1, thus possible for 1,2-
it is 3, 3-dimethyl-1-cyclohexanol. dimethylcyclopropane is
7 4 1
5 3 [2021, 26 Aug Shift-II]

18 The IUPAC name of (a) one (b) four

CH3COCH(CH3 ) 2 is [AIEEE 2003] (c) two (d) three
3-ethyl-4, 4-dimethylheptane
(a) isopropylmethyl ketone Ans. (d)
(b) 2-methyl-3-butanone 1,2-dimethylcyclopropane is
15 The IUPAC name of the compound (c) 4-methylisopropyl ketone
shown below is [AIEEE 2006]
(d) 3-methyl-2-butanone
Cl Ans. (d) CH3 CH3
O Hence, stereoisomers are as follows

CH3  C  CH  CH3 (i)
Br 1 2
3 4
CH3 meso
(a) 2-bromo-6-chlorocyclohex-1-ene
3 -methyl butan-2-one
(b) 6-bromo-2-chlorocyclohexene (ii) (iii)
or 3 -methyl-2-butanone
(c) 3-bromo-1-chlorocyclohexene
O
(d) 1-bromo-3-chlorocyclohexene
 Enantiomers
Ans. (c) keto ( C  ) functional group is given
meso form in optically inactive, whereas
Unsaturation (double bond) is given priority. enantiomeric pairs are optically active.
priority over halogen. So, the correct Therefore, total number of stereo
IUPAC name is 19 Which of the following compounds isomers are three (3).
3-bromo-1-chlorocyclohexene. has incorrect IUPAC
Cl nomenclature? [AIEEE 2002] 21 Arrange the following
O conformational isomers of
6 2  n-butane in order of their
(a) CH3CH2CH2 C OC2H5
5 increasing potential energy
3 Br ethyl butanoate
4 [2021, 31 Aug Shift-II]
266 JEE Main Chapterwise Topicwise Chemistry

CH3 (  CH3) methyl group at front and rear Since, h.p. groups are in opposite
H H carbon atom. direction. So, E configuration will be
I. ∴ It has maximum potential energy. assigned to double bond at second
While the repulsion in anti form is position.
H H Hence, full IUPAC name of given
minimum.
compound is
CH3 ∴ It has minimum potential energy.
2E-2-bromohex-2-en-4-yne.
CH3
CH3 22 The number of acyclic structural Hence, correct option is (c).
isomers (including geometrical
II. isomers) for pentene are ……… . 24 Which of the following molecules
H H [2021, 22 July Shift-II] does not show stereoisomerism ?
H H Ans. (6) [2021, 22 July Shift-II]

CH3 (i) CH2 == CH  CH2 CH2 CH3 (1-pentene) (a) 3, 4 - dimethyl hex-3ene
(b) 3- methyl hex-1-ene
H CH3 (c) 3 - ethyl hex-3-ene
III. (ii) CH3  CH == CH  CH2 CH3 (d) 4- methyl hex-1-ene
H H (2-pentene, it shows geometrical Ans. (c)
isomerism, i.e. cis and trans)
H 3-ethylhex-3-ene does not show
H stereoisomerism as it optically inactive
H
due to absence of chiral carbon centre.
IV. (a) 3, 4-dimethylhex-3-ene
H (iii) CH2 == C(CH3)  CH2 CH3 (2-methyl
but-1-ene)
H3C H CH3  CH2  C* == C  CH2  CH3
CH3  
(a) II < III < IV < I (b) I < IV < III < II CH3 CH3
(c) II < IV < III < I (d) I < III < IV < II (iv) (CH3)2 C == CHCH3 (2-methyl but-2-ene) It shows geometrical isomerism
Ans. (d) i.e cis/trans.
The order of potential energy of above (b) 3-methylhex-1-ene
conformations is (cis) *
CH2 == CH  CH  CH2  CH2  CH3
CH3 (v) (CH3)2 CH  CH == CH2 (3-methyl 
CH3 but-1-ene) CH3
Total number of acyclic structural
isomers (including geometrical isomers) It shows optical isomerism.
(II)
for pentene is 6. (c) 3-ethylhex-3-ene
H H
CH3  CH2  C == CH  CH2  CH3
H H
CH3
23 Choose the correct name for 
Fully eclipsed compound given below CH2 CH3
H
Br It cannot show stereoisomerism.
> (IV) i.e. no chiral center.
H
H [2021, 31 Aug Shift-I] (d) 4-methylhex-1-ene
H3C
CH3 (a) (4E)-5-bromohex-4-en-2-yne *
Partially eclipsed (b) (2E)-2-bromohex-4-yn-2-ene CH2 == CH  CH2  CH  CH2  CH3
(c) (2E)-2-bromohex-2-en-4-yne 
CH3 CH3
(d) (4E)-5-bromohex-2-en-4-yne
H CH3 It shows optical isomerism.
Ans. (c)
(III) 1 Note *C shows chiral carbon.
Hence, 3-ethylhex-3-ene does not
H H Br
5 2 show stereo isomerism.
H CH3 6 4 3

Gauche H H The IUPAC name of above compound is 25 Which one of the following pairs of
(I) 2-bromohex-2-en-4-yne.
> isomers is an example of
Now, to assign E/Z first assign priority
metamerism ? [2021, 20 July Shift-II]
H H to groups along the double bond.
(l.p) (a) CH3CH2CH2CH2CH3
CH3 CH
Anti Br(h.p.) h.p.=high priority
l.p.=low priority and H3CCCH3
The fully eclipsed form is least stable
(h.p.) N(l.p.)
due to repulsion between bulky (  CH3) CH3
Some Basic Principles of Organic Chemistry 267

No change in chirality or optical activity

(b) N
due to hydrogenation of (a), (b) and (c)
C6H5
but in (d) the substrate (alkene) on
and H5C6 H H O
hydrogenation becomes optically
inactive as the product obtained does
C CH3
OH H3C not have any chiral atom.
(c) H5C6 HO
OH
N 29 The number of chiral centres
and H5C6 present in [B] is ............. .
Ans. (5)
O [2020, 4 Sep Shift-I]
*
(d) *
N (i) C2H5MgBr
 CH C≡≡N
O (ii) H3O+
H * O CH3
and *
(i) CH3MgBr
Ans. (d) C* [A]
(ii) H2O
[B]
H3C CH3
Metamers are compounds which have HO
different alkyl groups present along
Ans. (2)
both side of polyvalent functional group. Complete reaction is as follows :
No polyvalent functional group in option The molecule contains five chiral
carbon (C*) atoms. (i) C2H5MgBr attacks in the form of
(a).
−δ +δ
The two functional groups are different R Mg  X
in option (b). 28 Which of the following compounds
produces an optically inactive Step I
Alcohol is not a polyvalent functional
group. compound on hydrogenation? –δ +δ
[2020, 3 Sep Shift-I] C2H5MgBr
Alkyl groups are different along both CH C N
sides of polyvalent functional group. H CH3 H CH3
CH3
O O (a) (b)
and s δ+
CH3 CH C N + MgBr
H H CH3
3-heptanone 4-heptanone
(c) (d)
(Metamers) CH3 C2H5

Ans. (d) C2H5 contain (−δ) charge attack on

26 Compound with molecular formula carbon.
C 3H6O can show Reaction of all options are as follows :
Step II On hydrolysis following
[2021, 18 March Shift-I]
H CH3 intermediate is formed.
(a) positional isomerism H2
(a)
(b) both positional isomerism and * Catalyst
metamerism CH C N H
H CH3
(c) metamerism
(d) functional group isomerism CH3 C2H5
*
Ans. (d) H CH3
30 The number of chiral centres
Functional isomers are those which H2
have same molecular formula but (b) * present in threonine is ……… .
Catalyst
[2020, 4 Sep Shift-II]
different functional groups. C3H6O
molecule can exists as aldehyde as well H CH3 Ans. (2)
as ketone as follows Structure of threonine is
*
CH3  CH2  CH == O
(Aldehyde) COOH
H CH3
and CH3  C  CH3 * H
H2 NH2
 (c) *
Catalyst
O
(Ketone)
H CH3 *
So, they are functional isomers of each CH OH
other.
*
CH3
27 The number of chiral carbons H CH3 H CH3
present in the molecule given (d) H2 Threonine have 2 chiral carbon atoms.
below is …… . [2020, 2 Sep Shift-I] * Catalyst
268 JEE Main Chapterwise Topicwise Chemistry

31 Among the following compounds, 32 Which of the following compounds Ans. (a)
geometrical isomerism is exhibited shows geometrical isomerism? Alkene in which different groups are
by [2020, 5 Sep Shift-II] [2020, 6 Sep Shift-I] attached with the double bonded
(a) 2-methylpent-2-ene carbon atoms, exhibit geometrical
CH2 CHCl isomerism.
(b) 4-methylpent-2-ene
(c) 4-methylpent-1-ene 1-phenyl -2-butene =
(a) (b) (d) 2-methylpent-1-ene H H
CH3 Ph
Ans. (b) H
Ph
Cl Only 4-methylpent-2-ene shows
CHCl CHCl geometrical isomerism. H
trans cis
H H
(c) (d) C==C It will show geometrical isomerism.
H 3C
H3C CH3 C CH3 3-phenyl-1-butene
H 3C
Ans. (b) H Same group, does not show
(cis-4-methylpent-2-ene) geometrical isomerism. H
Geometric isomers are molecule that
(CH3)2CH H
are locked into their saptial positions H
C==C
with respect to one another due to H CH3 H Ph
double bond or a ring structure. The
(trans-4-methylpent-2-ene)
presence of restricted rotation is due to
double bond or a ring structure. Hence, the correct option is (b). 2-phenyl-1-butene
Same group, does not show
Two different groups must be attached geometrical isomerism.
33 The absolute configuration Ph
to any two carton atoms of restricted
rotation. H
H
C
H CO2H H
H OH
not show geometrical
of H Cl is 1,1-diphenyl-1-propane being an alkane
(a) isormerism (saturated compound) does not show
CH3 [JEE Main 2016] geometrical isomerism.
Cl (a) (2S, 3R) (b) (2S, 3S) Time Saving Technique We do not need
(c) (2R, 3R) (d) (2R, 3S) the check all options, but it should
H Cl remind that double bonded compounds
C Ans. (a)
show geometrical isomerism.
1
COOH Thus, (d) is eliminated, (i.e. propane).
2
(b) H OH Now, eliminate the terminal alkene and
3
CH 3 H Cl get the correct response.
4
show geometrical (possible CH3
cis and trans isomer) 35 Out of the following, the alkene
For C-2, order of priority of substituents
Cl H is OH > CH(Cl) (CH3) > COOH
that exhibits optical isomerism is
C [AIEEE 2010]
For C-3, order of priority of substituents (a) 3-methyl-2-pentene
and is (b) 4-methyl-1-pentene
Cl > CH(OH)COOH > CH3
CH 3 (c) 3-methyl-1-pentene
Hence, according to CIP rules, (d) 2-methyl-2-pentene
H Cl 3 Ans. (c)
C COOH
1 Optical isomerism is shown by the
H OH 2S
2 1 carbon compounds which possess
H Cl 3R
(c) atleast one chiral carbon.
3 CH
H 3C CH 3 3 Thus, 3 −methyl−1 −pentane possess a
chiral carbon, hence it shows optical
not show geometrical 34 Which of the following compound isomerism.
isomerism will exhibit geometrical H
H Cl isomerism? [JEE Main 2015] *
C CH3  CH2  C  CH == CH2
(a) 1-phenyl-2-butene 
(b) 3-phenyl-1-butene CH3
(d) (c) 2-phenyl-1-butene 3-methyl-1-pentene

not shows geometrical isomerism (d) 1, 1-diphenyl-1-propane (It has one chiral centre)
Some Basic Principles of Organic Chemistry 269

36 The alkene that exhibits 38 The absolute configuration of One chiral centre ⇒optically active
geometrical isomerism is HO2C CO2H H2N NH2
[AIEEE 2009]
H H
(a) propene
HO H H OH Ph Ph
(b) 2-methyl propene
(c) 2-butene [AIEEE 2008] Two chiral centres, but plane of
(d) 2-methyl-2-butene (a) S, S (b) R, R (c) R, S (d) S, R symmetry within molecule ⇒optically
Ans. (c) inactive.
Ans. (b)
Geometrical isomerism is shown by
those alkenes only in which atoms or 2 2 41 Increasing order of stability among
HOOC COOH
groups attached to each carbon atom 3 3 the three main conformations (i.e.,
are different. Thus, H OH Eclipse, Anti, Gauche) of
HO R H1 COOH
CH3 1 2-fluoroethanol is [AIEEE 2006]
H
C or H OH R (a) Eclipse, Gauche, Anti
C
HO H R (b) Gauche, Eclipse, Anti
H H
Propene COOH (c) Eclipse, Anti, Gauche
[three atoms (H) linked
(d) Anti, Gauche, Eclipse
to doubly bonded
C-atoms are same, thus
39 Which one of the following Ans. (b)
no geometrical isomerism] conformations of cyclohexane is
HO  CH2  CH2 F H
CH3 H
chiral ? [AIEEE 2007]
(a) Twist boat (b) Rigid H H
C C
H (c) Chair (d) Boat
H3C
2-methyl propene
Ans. (c)
(no geometrical isomerism)
H Fδ–
H3C CH3
C C O Hδ+
H H Chair form is unsymmetrical and has Gauche conformation is comparatively
cis 2-butene absence of any element of symmetry. more stable due to hydrogen linkage in
(methyl group and H-atom
linked to doubly bonded 40 Which of the following molecules between F and H (at O-atom), hence
C-atom lie on same side, is expected to rotate the plane of order is eclipse, anti (staggered),
hence cis isomer) polarised light ? [AIEEE 2007] gauche.
H3 C H CHO
C C 42 Which type of isomerism is shown
H CH3 (a) HO H by 2, 3-dichlorobutane? [AIEEE 2005]
trans-2-butene (a) Structural (b) Geometric
(methyl groups and CH2OH
(c) Optical (d) Diastereo
H-atom lie on opposite
side to one another, Ans. (c)
hence trans isomer) (b) * *
SH CH3  CH  CH  CH3
H3C CH3 H2N NH2  
C C Cl Cl
(c) H H
H3C H There are two chiral C-atoms (*).
Ph Ph
2-methyl-2-butene Thus, it shows optical isomerism.
(no geometrical isomerism) COOH

(d) H2N H 43 For which of the following

37 The number of stereoisomers parameters, the structural isomers
possible for a compound of the H
C 2H5OH and CH3OCH3 would be
molecular formula Ans. (a) expected to have the same
CH3 —CH== CH—CH(OH) —Me is The molecule, which is optically active, values? (Assume ideal behaviour)
[AIEEE 2009] has chiral centre, is expected to rotate [AIEEE 2004]
(a) 3 (b) 2 the plane of polarised light. (a) Heat of vaporisation
(c) 4 (d) 6 (b) Vapour pressure at the same
CHO
Ans. (c) temperature
There are four stereoisomers. HO * H (c) Boiling points
cis —R, cis—S (d) Gaseous densities at the same
trans—R trans—S CH2OH temperature and pressure
270 JEE Main Chapterwise Topicwise Chemistry

Ans. (d) Ans. (c) (a) all four are chiral compounds
* (b) only I and II are chiral compounds
In CH3CH2OH, there is intermolecular CH3— CH—
H-bonding while it is absent in isomeric | (c) only III is a chiral compound
ether CH3OCH3. CH2CH3 (d) only II and IV are chiral compounds
Larger heat is required to vaporise contains asymmetric carbon atom, thus Ans. (b)
CH3CH2OH, as compared to CH3OCH3 optically active.
thus (a) is incorrect. Chiral compounds are those which have
46 Which of the following will have a one chiral centre i.e., all four atoms or
CH3CH2OH, is less volatile than CH3OCH3,
thus vapour pressures are different, meso-isomer also? [AIEEE 2004] groups attached to same carbon are
thus (b) is incorrect. (a) 2-chlorobutane different. Here, I and II are chiral but III
Bp of CH3CH2OH > CH3OCH3, thus (c) is (b) 2, 3-dichlorobutane and IV are achiral compounds.
incorrect. (c) 2, 3-dichloropentane
mass (d) 2-hydroxypropanoic acid 48 Following types of compounds
Density = , due to ideal behaviour
volume (as I, II)
Ans. (b)
at a given temperature and pressure, * (I) CH3CH == CHCH3
volume and molar mass are same. (a) CH3  CH  CH2 CH3
 (II) CH3  CH OH
Hence, they have same vapour density.
Cl 
44 Which of the following compounds One asymmetric carbon atom, forms CH2CH3
is not chiral ? [AIEEE 2004]
d-and l-optical isomers. are studied in terms of isomerism
CH3 in [AIEEE 2002]
(a) 1-chloropentane |
(b) 2-chloropentane *
H—C—Cl (a) chain isomerism
(b) Plane of |
(c) 1-chloro-2-methyl pentane symmetry (b) position isomerism
H—*C—Cl (c) conformers
(d) 3-chloro-2-methyl pentane |
Ans. (a) CH3 (d) stereoisomerism
meso due to Ans. (d)
Chiral carbon has all the four different internal compensation
groups attached to it. H3C CH3
Two asymmetric carbon atoms,
(a) CH3CH2 CH2 CH2 CH2 Cl C C
forms d-, l- and meso forms.
(no chiral carbon atom) * * H H
(c) CH3  CH  CH  CH2 CH3 (cis)
(b) CH3 CH CH2 CH2 CH3  
 Cl Cl H3C H
Cl and C C
(one chiral carbon atom) Two asymmetric carbon atoms
but does not have symmetry. H CH3
*
(c) CH3CH2 CH2 CHCH2 Cl Hence, meso form is not formed. (trans)
 * geometrical isomers
CH3 (d) CH3  CH  COOH (cis-trans)

(one chiral carbon atom) OH H H
* * One asymmetric carbon atom,
(d) CH3  CH  CHC H2 CH3
  meso form is not formed.
CH3 C C CH3
CH3 Cl
OH HO
47 Among the following four
(two chiral carbon atoms) CH2CH3 CH3CH2
structures I to IV
CH3 molecule is optically
45 Amongst the following active enantiomers
compounds, the optically active 
C 2H5 CH  C 3H7 Geometrical isomers and enantiomers
alkane having lowest molecular
(I) O CH3 both are stereoisomers.
mass is [AIEEE 2004]
 
(a) CH3 CH2 CH2 CH3 CH3 C CH  C 2H5 49 Racemic mixture is formed by
CH3 (II)
mixing two [AIEEE 2002]

(b) CH3  CH2  CH  CH3 H CH3 (a) isomeric compounds
 (b) chiral compounds
H 
| H C ⊕ C 2H5 CH  C 2H5 (c) meso compounds
(c) CH3 C   (d) enantiomers with chiral carbon
|
C2H5 H Ans. (d)
(III) (IV)
Racemic mixture is an equimolar
(d) CH3 CH2 C ≡≡ CH mixture of enantiomers.
It is true that [AIEEE 2003]
Some Basic Principles of Organic Chemistry 271

50 Geometrical isomerism is not (c) CH3CH2CH2CONH2 (b) H3C—C ≡≡ C—H

shown by [AIEEE 2002] (d) CH3CH2CH ==CHCH2NH2 O
(c)
(a) 1, 1-dichloro-1-pentene Ans. (d)
(b) 1, 2-dichloro-1-pentene CH3CH2 CH == CHCH2NH2 will not show H3C CH3
(c) 1, 3-dichloro-2-pentene resonance as it does not have
(d) 1, 4-dichloro-2-pentene conjugated system, whereas; O O
Compounds a, b and c have conjugated
Ans. (a) system. So, they exhibit resonance. (d)
MeO OMe
Cl CH2 CH2 CH3 H
C== C (a) CH3—CH2—O—CH==CH2
O OMe
Cl H Ans. (d)
CH2OH
At least two groups or atoms attached
(b) Acidity of H-atom ∝ Attachment with
to doubly bonded carbon atoms should
O more and stronger electron withdrawing
be different.
(c) CH3—CH2—CH2—C— NH2
groups.
–I
(d) CH3CH2 CH == CH  CH2 NH2 (This δ+
TOPIC 3 molecule does not have
NC H
δ–
Bond Fission and conjugation). (a) C
Electronic Displacement 53 Arrange the following labelled NC H
hydrogens in decreasing order of –I
51 Which one among the following It experiences two –I
acidity [2020, 2 Sep Shift-II]
resonating structures is not effects, so can show acidity
NO2 C == C— H a
correct ? [2021, 25 July Shift-I] δ +
δ–
O (b) H3C C C H
(a) N sp
d H —O COO H b It is also removable hydrogen
O
O— H c O
O δ– δ+
(b) N (a) b > a > c > d (b) c > b > d > a (c) CH3 C CH2 H
O (c) b > c > d > a (d) c > b > a > d –I
Ans. (c) It also shows acidity because
O
(c) N of the –I effect
Carboxylic acids (  COOH) [b] are
O stronger to phenolic OHgroups O
Stronger
O –I effect
(c and d). (d)
O δ–
(d) N Phenolic OH(c) experiences stronger MeO OMe
−R effect of NO2 group being placed +
O Stronger H δ
at para position to (c), whereas phenolic –I effect O
Ans. (a) OMe
OH(d) enjoys comparatively weaker
Stability of a resonating structure electron withdrawing, −I effect of the Stronger
depends on : NO2 group from meta-position. –I effect
(i) Charge separation between It is most acidic, because the
So, acid strength : c > d or b > c > d.
opposite charges should be carbon atom bearing this H-atom
minimum. The H-atom (a) attacked with sp-carbon enjoys three stronger –I effects
(ii) Charge separation between same (s % = 50) is also acidic but lesser acidic of enter groups
charges should be maximum. than H-atoms (b, c and d) who are O
Here, two cationic charges in attacked with more electronegative C OMe.
option (a) are very close to each O-atoms.
other. So, these charge repel ∴Electronegativity : O(sp3) > C (sp) Compound (d) possess the most acidic
each other. Therefore, structure hydrogen because of three stronger
(a) is unstable. Hence, the order of acidity :b > c > d > a. −I-effects.

52 Which of the following compounds 54 Which one of the following 55 Which of the following has the
does not exhibit resonance ? compounds possesses the most shortest C Cl bond?
[2021, 22 July Shift-II] acidic hydrogen? [2020, 3 Sep Shift-I] [2020, 8 Jan Shift-II]
(a) CH3CH2OCH ==CH2 (a) Cl CH == CH CH3
N ≡≡ C C ≡≡ N
CH2OH (b) Cl CH == CH NO2
(a) (c) Cl CH == CH OCH3
(b)
H H (d) Cl CH == CH2
272 JEE Main Chapterwise Topicwise Chemistry

Ans. (b) Ans. (c) such rapid interconversion that can’t be

Due to −R (or −M) effect of ‘NO2 ’, there is Ethene (H2 C == CH2 ) is sp2 -hybridised independently isolated.
stronger double bond character for the and ethyne (HC ≡≡ CH) is sp-hybridised. O H OH
In ethyne, the sp-hybridised carbon
‘C  Cl’ bond in Cl  CH == CH NO2 . atom possesses maximum s-character C C C CH
(option-b) and hence, maximum electronegativity.
Due to which, it attracts the shared Keto H Enol
O
electron pair of CH bond to a greater
Cl—CH==CH—N extent and makes the removal of proton
O O O
easier. Hence, alkyne is much more
O
acidic than alkene.
Cl == CH—CH==N Keto Enol in phenol
O Presence of electron donating group in
alkyne (H3C  C ≡≡ CH) decreases the Thus, (c) 2-pentanone and (d) phenol
∴ The bond length is shortest in (b). acidic strength of compound. Hence, exhibit tautomerism.
the correct order of acidic strength is:
60 Consider thiol anion (R S s ) and
56 Which amongst the following is HC ≡≡ CH > H3C  C == CH > CH2 == CH2
alkoxy anion
the strongest acid?
[2019, 9 Jan Shift-I] 58 Which of the following molecules (RO s ) . Which of the following
(a) CHBr3 (b) CHI3 is least resonance stabilised? statements is correct? [AIEEE 2011]
(c) CHCl3 (d) CH(CN) 3 [JEE Main 2017] (a) R Ss is less basic and less
nucleophilic than RO s
Ans. (d)
(a) (b) (b) R Ss is less basic but more
We know, a stronger acid produces its O nucleophilic than RO s
stable or weaker conjugate base. Here, (c) R Ss is more basic and more
CH(CN) 3 produces the most stable (c) (d) nucleophilic than RO s
conjugate base (NC) 3 C− . Stronger −R N (d) R Ss is more basic but less
and −I effects of the CN − group, make O
nucleophilic than R Ss
the carbanion (conjugate base) very Ans. (b)
stable. The resonance hybrid structure Ans. (d) Nucleophilic strength depends on the
of [(NC) 3 C] − is as follows :
Aromatic compounds are stable due to electronegativity of the atom. Lower
CN the electronegativity of an atom, larger
δ– δ+ resonance while non-aromatics are not.
(NC)3C H NC C s
+H ⊕ According to Huckel’s rule (or 4n + 2 the nucleophilic strength of an atom
(–I) and more readily it will donate electrons
rule), “For a planar, cyclic compound to
C N (–R) to the electrophilic (e − deficient)
be aromatic, its π cloud must contain
species.
– (4n + 2) π electrons, where, n is any
(NC)2C C N Since, electronegativity decreases
whole number.” Thus,
down the group, thus nucleophilic
s and
strength increases down the group.
N , Hence, RS − is more nucleophilic than
C
O N RO− due to less electronegativity of S
(6πe– system) (4πe– + 2e– system) (6πe– system) than O.
N C C
are aromatic and stabilised by resonance. On the other hand, basic strength of an
C
They follow Huckel’s rule. atom depends upon the tendency to
N
accept a proton more readily. Since,
Resonance hybrid structure of [NC)3C]– is non-aromatic, hence, O  H bond is longer thanS  H bond,
least stabilised by resonance. thus RO− has a greater tendency to
accept a proton than RS − . Hence, RO− is
57 The correct order for acid strength O a stronger base than RS − .
of compounds Thus, basic strength of the central atom
CH ≡≡ CH, CH3  C ≡≡ CH and 59 Identify the compound that decreases down the group.
CH2 == CH2 is as follows : exhibits tautomerism [AIEEE 2011] Hence, RS − is more nucleophilic but
(a) CH3  C ≡≡ CH > CH2 == CH2 (a) 2-butene (b) lactic acid less basic than RO− .
> HC ≡≡ CH (c) 2-pentanone (d) phenol
61 The correct order of increasing
(b) CH3 C ≡≡ CH > CH ≡≡ CH Ans. (c), (d)
acid strength of the compounds is
> CH2 == CH2 Tautomerism is due to spontaneous [AIEEE 2006]
(c) HC ≡≡CH > CH3 −− C ≡≡ CH interconversion of two isomeric forms (A) CH3CO 2H (B) MeOCH2CO 2H
> CH2 == CH2 with different functional groups into Me
(d) CH ≡≡ CH > CH2 == CH2 one another. The term tautomer means
> CH3 C ≡≡ CH (C) CF3CO 2H (D)  CO 2H
constitutional isomers that undergo
[2019, 12 Jan Shift-I] Me
Some Basic Principles of Organic Chemistry 273

(a) B < D < A < C (b) D < A < C < B Ans. (c) H
(c) D < A < B < C (d) A < D < C < B  ⊕ H+
O O– H  C  CH2 ←→H  C == CH2


Ans. (c) H—C H—C  
O–


Acidic strength of the compound
O H H
depends on the ease of release of O– Ethyl cation
+


proton. I effect exerting groups HC Ethyl cation (CH3  CH2 ) involves
[e − withdrawing] increases the acidic O


overlapping of Csp3 H1s bond with
strength while + I effect exerting group Resonating (canonical)
empty 2p-orbital.
decreases the strength of an acid. structures of formate ion
∴ Statement I is true and statement II is
Thus, O Due to resonance, C O bonds are false.
Me found to be of equal length.
CH C OH < CH2
Me 64 In the following benzyl/allyl system
[ 2+I effect exerting
groups, increases e– density 66 CH2==CH
on O-atom, thus the release R  CH == CH2 or R (B)
of ease of proton becomes (A)
difficult (least acidic)] O CH3—CH2 H2C ≡≡C
(R is alkyl group) (C) (D)
CH3 C OH < decreasing order of inductive The correct order of stability of
effect is [AIEEE 2002]
given carbocation is
[+I effect group of
(a) (CH3) 3 C  > (CH3)2 CH  > CH3CH2  [2021, 27 July Shift-I]
 CH3 group]
(b) CH3CH2  > (CH3)2 CH  > (CH3) 3 C  (a) A > C > B > D (b) D > B > C > A
O
(c) (CH3)2 CH  > CH3CH2  > (CH3) 3 C  (c) D > B > A > C (d) C > A > D > B
(d) (CH3)2 C  > CH3CH2  > (CH3) 3 CH  Ans. (a)
MeO CH2 C OH
O Ans. (a) Correct order of stability of
F Both where R is attached to vinylic carbocations will be
< F C C OH (≈ arylic) system, positive inductive
CH2
F effect occurs in the following order
[CF3 exerts more O− >  COO− > (CH3) 3 C  >
–I effect than Meo (A) Benzyl carbocation get
(most acidic)]
(CH3)2 CH  > CH3CH2  > CH3 

stabilise by resonance. It’s resonating

62 Among the following acids which TOPIC 4 structures are as follows
has the lowest pK a value?
[AIEEE 2005] Reaction Intermediates CH2 CH2 CH2 CH2
(a) CH3CH2COOH
(b) (CH3)2 CH COOH 65 Given below are two statements.
(c) HCOOH Statement I Hyperconjugation is
a permanent effect. ⊕
(d) CH3COOH (C) CH3  CH2 gets stabilised due to
Ans. (c) Statement II Hyperconjugation in hyperconjugation.
+
Stronger the acid, lower is their pK a ethyl cation (CH3 CH2 ) involves H H+ H
value. Thus, out of the given acids,
strongest acid is HCOOH.
the overlapping of C sp2  H1s H—C—CH2 H—C CH2 H C CH2
Hence,HCOOHpossess lowest pK a
bond with empty 2p orbital of
H H H
value. other carbon. H
Choose the correct option :
63 In the anion, HCOO − the two [2021, 27 July Shift-II] H—C CH2
carbon-oxygen bonds are found to (a) Both statement I and statement II H
be of equal length. What is the are false. + +
(b) Statement I is incorrect but CH2 == CH (B) and H2 C ≡≡ C (D) are not
reason for it ? [AIEEE 2003]
statement II is true. stabilised by resonance or
(a) Electronic orbits of carbon atom hyperconjugation, thus, they are
(c) Statement I is true but statement II
are hybridised unstable also positive charge is not
is false.
(b) The C == O bond is weaker than stabilised by more electronegative
(d) Both Statement I and statement II
the C—O bond C-atom. Electronegativity of carbon
are true.
(c) The anion, HCOO − has two increases with increase in
resonating structures Ans. (c) %s-character.
(d) The anion is obtained by removal Hyperconjugation is a permanent For sp-hybridised carbon, %s-character
of a proton from the acid molecule effect. is 33%.
274 JEE Main Chapterwise Topicwise Chemistry

For sp-hybridised carbon, %s-character O δ+

is 50%. So, positive charge is less stable R → C → Cl >
on sp-hybridised carbon. (c)
CH3 
O
So, the correct order of stability of (Chlorine in electron
carbocation is withdrawing group)
OH O
A > C > B > D. R → C→O  C ←
R >
 
CH2 (d) O O

> CH3—CH2 > CH2 CH > CH C O

The charge is not Ans. (a) δ + •• ••
stable on more R → C  O R > R C ← N H2
Resonance Hyperconjugation electronegative O CH3  
elements will provide a O O
O (NH 2 is electron
67 Which among the following is the donating group hence
reduce positive charge)
tertiary alcohol on reaction with excess
strongest acid ? of CH3MgBr followed by hydrolysis.
[2021, 25 July Shift-II] 70
Chemical reaction is as follows; CH2 CH2
(a) CH3CH2CH2CH3 (b)
H CH2
O CH3
CH3MgBr
(c) (d) O (1, 2 addition) H
– + O (A) (B) (C)
Ans. (d) OMgBr CH2
+ CH3— C —CH3
The acid whose conjugate base is most
CH3MgBr
stable will be strongest acid. (D)
−H +
(a) CH3  CH2  CH2  CH3 → OH OMgBr Among the given species the
Butane NH4Cl resonance stabilised
s CH3—C —CH3 CH3— C —CH3
CH3  CH2  CH2  CH2 carbocations are
CH3 CH3 [2021, 20 July Shift-I]
CH3 CH2 (3° alcohol)
–H+ (a) (C) and (D) only
(b)
(b) (A), (B) and (D) only
Toluene Benzylic carbanion 69 (A) R Cl (c) (A) and (B) only
+ (d) (A), (B) and (C) only
–H
(c) Ans. (c)
Cyclopropene Anti-aromatic (B) R O R Resonance is shown by compound (A)
–H+ and (B) only, hence they form stable
(d) carbocations.
(C) R R
Cyclopenta-
Aromatic
O Compound (A) is aromatic and these
1,3-diene
compounds is stable due to resonance.
Conjugate base of molecule (d) is most Whereas in compound (B), double bond
(D) R H
stable as an aromatic compound is N and positive charge are in conjugation,
formed after donating a proton. H hence form stable carbocation due to
The correct order of their resonance.
68 Which of the following compounds reactivity towards hydrolysis at Compound (C) and compound (D) does
will provide a tertiary alcohol on not shows resonance because double
room temperature is bond and positive charge are not in
reaction with excess of CH3MgBr [2021, 20 July Shift-II]
followed by hydrolysis ? conjugation.
(a) (A) > (B) > (C) > (D)
[2021, 22 July Shift-II] Only compounds (A) and (B) show
(b) (D) > (A) > (B) > (C) resonance as follows
O CH3 (c) (D) > (B) > (A) > (C) ⊕
(a) (d) (A) > (C) > (B) > (D) CH2 CH2
O (A)
Ans. (a) ⊕
OCH2CH3 Rate of hydrolysis is directly
(b)
proportional to positive charged ⊕
NC present on carbon of C == O group. CH2 ⊕
CH2 CH2
C
Therefore,
CH Rate of hydrolysis → Acid chloride> Acid ⊕
anhydride> Ester > Amide.
Some Basic Principles of Organic Chemistry 275
–
H O + HBr + Br
⊕
H +
H ,O But-1-ene 2°carbocation
(B)
⊕ (d) (B) –
H OH + Br
+
1°carbocation
71 Given below are two statements. (A)
Statement I C 2H5OH and AgCN Ans. (c) Carbocation B is more stable as it is
both can generate nucleophile. secondary carbocation having more
The given reaction is aldol condensation
number of  α-hydrogens, having a
Statement II KCN and AgCN both reaction. Here, enolate ion reacts with a
greater + I effect and formed with
will generate nitrile nucleophile carbonyl compound in the presence of
faster rate due to low activation energy.
dil. NaOH to form aβ-hydroxy ketone,
with all reaction conditions. followed by dehydration to give a
Choose the most appropriate conjugated enone. It take place as 74 The increasing order of basicity for
option. [2021, 18 March Shift-II] follows the following intermediates is
(a) Statement I is true but statement II –
(from weak to strong)
O O [2020, 8 Jan Shift-II]
is false.
CH3
(b) Both statements I and II are true.
(c) Statement I is false but statement II
+ OH–  s
is true. Enolate ion H3C  C s H2C == CH CH2
(d) Both statements I and II are false. O
–
O  (ii)
Ans. (a) CH3
dil.
Both C2H5OH and AgCN can generate + (i)
NaOH s s s
nucleophile. KCN generates nitriles on
O O– HC ≡≡ C C H3 CN
substitution reactions with haloalkanes, (v)
where AgCN generates isonitriles on
(iii) (iv)
substitution reactions with haloalkanes. (a) (v) < (iii) < (ii) < (iv) < (i)
Because KCN is ionic and has ‘C’ (b) (iii) < (i) < (ii) < (iv) < (v)
H2O (Aldol reaction) (c) (v) < (i) < (iv) < (ii) < (iii)
nucleophilic centre whereas AgCN is
covalent and has ‘N’ nucleophilic centre. O OH (d) (iii) < (iv) < (ii) < (i) < (v)
Hence, statement I is true but Ans. (a)
statement II is false. Basicity order for the following in
(X)
intermediates is
72 O O OH O
È È
H
+
CN− < CH==CÈ < H2 C == CH CH2 < CH2 <
dil. NaOH H+, Heat (v) (iii) (ii) (iv)
‘‘X’’ ‘‘Y’’ C1
Mechanism (Y) CH3
(X) –H2O 
Consider the above reaction, the CH3  CÈ
product ‘X’ and ‘Y ’ respectively are 73 Choose the correct statement 
[2021, 18 March Shift-II] regarding the formation of CH3
OH carbocations A and B. (i)

[2021, 17 March Shift-II] which is also the opposite of the order

,
(a) CH3CH2CH CH2+HBr of stability of carbanions.
O + –
CH3––CH2––CH2––CH2+Br
O C N > CH C > CH2 CH—CH2 >
(A)
+
(sp-carbon) (resonance)
CH3––CH2––CH––CH3+Br – stabilised
O (B) CH3
(a) Carbocation B is more stable and CH3 > C CH3
,O formed relatively at faster rate. CH3
(b) (less stable due to +I
OH (b) Carbocation A is more stable and effect of CH3 groups)
formed relatively at slow rate.
(c) Carbocation B is more stable and 75 The increasing order of
formed relatively at slow rate.
O nucleophilicity of the following
(d) Carbocation A is more stable and
formed relatively at faster rate. nucleophiles is
,O
(c) Ans. (a) (1) CH3CO 2È (2) H2O
OH È
Carbocation B is more stable due to (3) CH3SO 3È (4) OH
more hyperconjugation and formed
[2019, 10 April Shift-II]
relatively at faster rate compared to A.
276 JEE Main Chapterwise Topicwise Chemistry

– – – –
(a) (1) < (4) < (3) < (2) (a) R– COO <HC–== C < R– < NH2 Thus,
–
(b) (2) < (3) < (1) < (4) (b) R < HC ≡≡ C < RCOO <– NH–2 Cl
– –
(c) (4) < (1) < (3) < (2)
(c) RCOO– <NH2 <HC ≡≡ C < R– Cl C
s
>
s
—–CH2
(d) (2) < (3) < (4) < (1) – –
(d) RCOO <HC ≡≡ C <N H2 < R
Ans. (b)
Ans. (d) Cl (–I effect of phenyl
Higher the basicity of a base, stronger − (3-I effect exerting group as well as
O O group of Cl)
will be its nucleophilic power. delocalisation of electrons)
 
Again we know, a weaker acid produces R — C O ←→ R — C == O CH3
a stronger base (conjugate), i.e. a CH3 s
In carboxylate ion, the negative charge > > CH3 C
stronger nucleophile. is present on oxygen, a most
s
CH3 CH
−H ⊕ electronegative element here, thus it is
Acid → Conjugate base (+ I effect of CH3
resonance stabilised. 2-CH3 group) (+ I effect of
+
H3O H2O HC ≡≡ C− : Carbon is sp hybridised so its 3 - CH3 groups)
CH3SO3H CH3SO3È electronegativity is increased higher
CH3CO2H CH3CO2È relative to nitrogen. 79 The increasing order of stability of
È –
H2O OH N H2 : Nitrogen is more electronegative the following free radicals is
Acid Base strength
than sp3 hybridised C-atom. From the • •
[AIEEE 2006]
•
strength ≡ Nucleophilicity
above discussion, it is clear that the (a) (CH3) 2 C H < (CH3) 3 C < (C 6H5 ) 2 C H
Thus, the correct order of order of the stability of conjugated •
nucleophilicity of given nucleophiles are bases is as < (C 6H5 ) 3 C
as follows : • • •
–
H2O(2) < CH3SO3− (3) < CH3CO2− (1) <OH(4)
− RCOO− > HC ≡≡ C− > N H2 > R − (b) (C 6H5 ) 3 C < (C 6H5 ) 2 C H < (CH3) 3 C
•
and higher is the stability of conjugated < (CH3) 2 C H
• • •
76 The order of stability of the bases, lower will be basic character. (c) (C 6H5 ) 2 C H < (C 6H5 ) 3 C < (CH3) 3 C
following carbocations Hence, the order of basic character is •
as < (CH3) 2 C H
+
CH2 CH  CH2 ; RCOO− < HC ≡≡ C− < N H2 < R −
– • •
(d) (CH3) 2 C H < (CH3) 3 C < (C 6H5 ) 3 C
•

(I) •
+ – < (C 6H5 ) 2 CH
CH3 CH2 CH2; 78 Arrange the carbanions, (CH3 ) 3 C, Ans. (a)
(II) + – – –
CH2 CCl 3 , (CH3 ) 2 CH, C 6H5 CH2 , in Free radicals stability
• •
order of their decreasing stability C6H5  C  C6H5 > C6H5  CH
is [AIEEE 2009]  
– – – C6H5 C6H5
(III) (a) C 6H5 CH2 >CCl3 > (CH3)2 C
– (highly stable by delocalisation
[JEE Main 2013] > (CH3)2 CH
– – –
of 3 phenyl groups)
(a) III > II > I (b) II > III > I • •
(b) (CH3)2 CH > CCl3 > C 6H5 CH2 > CH3  C  CH3 > H3C  C  H
(c) I > II > III (d) III > I > II –
 
> (CH3) 3 C CH3 CH3
Ans. (d) – – –
(c) CCl3 > C 6H5 CH2 > (CH3)2 CH (9-hyperconjugative
The order of stability of carbocation will –
> (CH3) 3 C hydrogens and + I effect
be
– – – – of 3 alkyl group)
CH2 (d) (CH3) 3 C > (CH3)2 CH> CH2 > CCl3
Ans. (c) 80 Due to the presence of an
> CH2 CH CH3 > CH3 unpaired electron, free radicals
− I effect [e − withdrawing] exerting are [AIEEE 2005]
Benzyl carbocation Allylcarbocation groups stablises carbanion by the
(more resonance (resonance (a) cations
dispersal of their −ve charge while
stabilised) stabilised) (b) anions
+ I effect exerting [e − releasing] groups
(c) chemically inactive
CH2 CH2 destablises the carbanion by increasing
(d) chemically reactive
Propylcarbocation electron density on them.
(stabilised by Ans. (d)
On the other hand, resonance stablised
+I effect)
carbanion are stable due to the Free radicals have unpaired electrons,
involvement of their lone pair of so are neutral and reactive.
77 The correct order of increasing • •
electron with the delocalisation of CH3 + CH3 → CH3  CH3
basicity of the given conjugate π −electrons of attached phenyl group.
bases (R = CH3 ) is [AIEEE 2010]
Some Basic Principles of Organic Chemistry 277
O
81 The decreasing order of – Cl Cl
CH3MgBr
nucleophilicity among the CH3—C—OC2H5
nucleophiles [AIEEE 2005]
Ethyl acetate
(A) CH3 C  O − (B) CH3O − (C) CN − O OH
 –
CH3MgBr
O CH3—C—CH3 CH3—C—CH3 NO2
O H2O
(i) (ii)
CH3
– Acetone Cl Cl
(D) H3C S O 2-methyl-2-propanol
NO2 O2N NO2

O 83 (1) Zn/HCl
(2) Cr2O3 773K
(a) (C), (B), (A), (D) (b) (B), (C), (A), (D)
10-20 atm
(c) (D), (C), (B), (A) (d) (A), (B), (C), (D) O NO2 NO2
Ans. (b)
considering the above reaction, (iii) (iv)
Weaker the acid, more stable is their the major product among the
conjugate base and greater is their
(a) (iv) < (iii) < (ii) < (i)
nucleophilicity. Thus, nucleophilicity
following is [2021, 26 Feb Shift-II] (b) (iv) < (i) < (ii) < (iii)
order of the conjugate bases is opposite CH2CH3 CH2CH2CH3 (c) (iv) < (i) < (iii) < (ii)
to their acidic strength. (d) (i) < (ii) < (iii) < (iv)
Conjugate bases Acids Ans. (d)
(a) (b)
CH3  C  O − CH3  C  OH Rate of nucleophilic substitution in
  aromatic halide are as follows
O O CH3 COCH2CH3
CH3O − CH3OH Cl Cl
− CH3
CN HCN
O (c) (d) <
O <
CH3   C  O–
CH3   C OH chloro benzene
O Ans. (a) (Minimum rate) NO2
O (i)
In this reaction, an open chain ketone 4-nitro
Since, alcohols and cyanides are weaker (4-ethyl hexan -2- one) undergoes chlorobenzene
Clemmensen reduction first to give (ii)
acid than sulphonic and carboxylic
3-ethylhexane which on aromatisation Cl Cl
acids. Thus, the order of acidic strength produces an aromatic hydrocarbon,
of the given species are NO2 O2N NO2
ethyl benzene [option -(a)] as the major
Hence, the decreasing order of product. <
nucleophicity of the given nucleophiles
is as follows 2 Zn–Hg/CHCl
NO2 NO2
6 4
O 3 1
4 [H], –H2O
2,4-dinitro 2,4, 6-trinitro
5 chlorobenzene chlorobenzene
[Clemmensen
– O reduction] (iii) (Maximum rate)
H3C— —S—O 4-ethylhexan-2-one
Greater the number of nitro ( NO2 )
O 5
group in chlorobenzene, greater the
1 3
–
4 6 rate of nucleophilic substitution
< CH3 C O – < CN < CH3O 2
reaction in aromatic halides.
When a nitro group is present at ortho and
O 3-ethylhexane para position, it can withdraw electrons
from the benzene ring. This facilitates,
TOPIC 5 CH2CH3 Cr2O3
773K, the attack of nucleophiles on
10-20 atm haloarenes.
Types of Organic Reactions – 4H2
[Aromatisation]
85 The major product of the following
82 To synthesis 1.0 mole of Ethyl benzene reaction is
(Major)
2-methylpropan -2-ol from CH3
ethylethanoate …… equivalents of
CH3MgBr reagent will be required. 84 The correct order of the following 2HBr
(Integer value) [2021, 20 July Shift-I] compounds showing increasing
tendency towards nucleophilic
Ans. (2)
substitution reaction is NO2
2 moles of CH3MgBr reagent will be [2021, 24 Feb Shift-II]
used. Chemical reaction is as follows [2020, 6 Sep Shift-I]
278 JEE Main Chapterwise Topicwise Chemistry

CH3 Ans. (d) Ans. (b)

H3 C Br
The potential energy (PE) diagram for
Br Ozonolysis
S N 1 reaction is
(a) (b) O
Br Br (A) Carbocation
O
+ intermediate
NO2 NO2
(B)
CH3 (C)
Br CH3
Br Alkene (A) undergoes ozonolysis and PE R++X–
(c) (d) gives an aldehyde and ketone. –
+Nu
Br Br O R X
I2+NaOH – + R  Nu
NO2 NO2 (B) H—C—ONa + CHI3
∆
(Yellow ppt.) Progress of reaction
Ans. (d)
Ag2O S N 1 reaction has two steps. In the first
Addition of HBr to unsymmetrical ∆
CH3COO– + Ag (¯)
step, the carbon halogen bond breaks
alkene take place according to (Silver mirror)
heterolytically, with the halogen
Markownikoff’s rule. I2+NaOH
( C) No yellow ppt. retaining the previously shared pair of
∆
OH electron. In the second step, the
CH3 CH3 nucleophile reacts rapidly with the
LiAIH4
C2H5—CH—C2H5 carbocation formed in the first step.
+ Br–
H Br ∆
( D) In the above graph, the alkyl halide is the
Anhydrous Conc. only species that participates in the rate
ZnCl2 HCl limiting step. Here, the rate of reaction
NO2 NO2
depends on the concentration of the
C2H5—CH—C2H5 alkyl halide and does not depend on the
CH3 CH3
Br Br Cl concentration of nucleophile.
+ – (White turbidity)
H Br
Methyl ketones react withI2 + NaOH , so 88 Which of the following is the
Br correct order of decreasing SN 2
option (a) and (c) are incorrect, while
NO2 NO2 option (b) only gives aldehydes, thus (b) reactivity? (X = a halogen)
(Major product) also incorrect. [AIEEE 2007]

Hence, the correct option is (d). Hence, the correct option is (d). (a) R CH2 X > R3C X > R2CH X
(b) R CH2 X > R2CHX > R3 CX
86 Consider the following reactions: 87 Which of the following potential (c) R3CX > R2CHX > R CH2 X
(A) Ozonolysis
→ (B) + (C) energy (PE) diagrams represents (d) R2CH2 X > R3C X > R CH2 X
(C 7H14 )
the SN 1 reaction? Ans. (b)
[2019, 9 April Shift-II]
(I2 + NaOH) S N 2 reactions are greatly controlled by
‘B’ yellow ppt.
∆ steric factor.
Ag2O (a) PE
R  CH2  X, R2 CH  X, R 3 C  X
Silver mirror 2° 3°
∆ 1°
S N 2 reactivity decreases as bulkyness of
(I2 + NaOH)
no yellow ppt. Progress of reaction alkyl group increases.
∆
(C)
LiAlH4
(D)
Anhydrous ZnCl2 89 Tertiary alkyl halides are
∆ and conc. HCl (b) PE practically inert to substitution by
Gives white turbidity within SN 2 mechanism because of
5 minutes (a) steric hindrance [AIEEE 2005]
Progress of reaction
(A) is [2020, 6 Sep Shift-I] (b) inductive effect
(c) instability
(c) PE (d) insolubility
(a) Ans. (a)
(b) In S N 2 reaction, attack of nucleophile
Progress of reaction
and breaking of C Br bond takes place
in one step.
(c) R R R
(d) PE 
−
R  C Br + Nu → Nu.. ..... C..... .Br
(d)  
Progress of reaction R R
Some Basic Principles of Organic Chemistry 279

Since, tertiary carbon is sterically

hindered, thus the attack of nucleophile (c) r 1° carbocation
91 SN 1 reaction is feasible in
becomes difficult. Hence, tertiary alkyl [AIEEE 2002]
halides undergoS N 2 reaction very
r
rarely. (a) Cl + KOH (d) CH2 CH2
unstable
90 The reaction Cl
1° carbocation
O O (b) + KOH
(due to the presence of - I
  effect exerting phenyl group)
R C  X + Nu s → R C Nu + X s
(c) Cl + KOH
is fastest when X is 92 Following reaction,
[AIEEE 2005, 2004]
(CH3 ) 3 CBr + H2O → (CH3 ) 3 COH
(a) OCOR (b) OC2H5
(c) NH2 (d) Cl + HBr is an example of [AIEEE 2002]
(d) CH2CH2Cl + KOH
(a) elimination reaction
Ans. (d)
(b) free radical substitution
Poor the nucleophile, better is the
(c) nucleophilic substitution
leaving group ability. Among the given Ans. (a)
species, Cl − is a poor nucleophile, thus (d) electrophilic substitution
S N 1 (unimolecular nucleophilic Ans. (c)
it will act as a better leaving group.
Thus, X will be Cl and hence, the given substitution) reaction is favoured with
stability of carbocation. (CH3) 3 C Br + H2O →
reaction will be fast in the presence of
(CH3) 3 C OH + HBr
Cl.
(a) r 3° carbocation Here, Br is substituted by  OH−
O O
(nucleophile)
 
R  C  Cl + Nu− → R  C  Nu + Cl − (b) 1° carbocation → S N 1 reaction (unimolecular
(X ) (X − ) r substitution reaction)
23
Hydrocarbons
TOPIC 1 (c) Statement I is correct but 05 Which of these factors does not
statement II is incorrect.
Alkanes (d) Statement I is incorrect but
govern the stability of a
statement II is correct.
conformation in acyclic
01 Experimentally reducing a compounds? [2019, 10 April, Shift-II]
Ans. (c)
functional group cannot be done (a) Electrostatic forces of interaction
by which one of the following Statement I is correct, whereas (b) Torsional strain
statement II is incorrect. Corrected
reagents ? [2021, 1 Sep Shift-II]
statement is as follows:
(c) Angle strain
(a) Pt-C/H2 (b) Na / H2 (d) Steric interactions
Tertiary alkanes can be oxidised to
(c) Pd-C/H2 (d) Zn / H2O alcohol by treating withKMnO4 . Ans. (c)
Ans. (b) n-alkane are very less reactive and have The four types of strains viz (a)
A functional group cannot be reduced no reaction withKMnO4 . electrostatic force of attraction, (b)
KMnO torsional strain, (c) angle strain, (d)
by Na/H2 as it is not a reducing agent. n-alkanes  4→ No reaction
steric stain, are responsible for the
stability or energy barriers of
02 The dihedral angle in staggered 04 Identify A in the given chemical
conformers. In cyclic compounds, all
form of Newman projection of 1, 1, reaction. [2021, 25 Feb Shift-I] types of strains may be present.
1-trichloro ethane is .........… CH3
Compound Type of strains/forces
degree. (Round off to the nearest CH2
integer) [2021, 27 July Shift-II] a+c
CH2 CH3 Mo2O3
Ans. (60) CH
CH2 CH3 773 K, 10-20 atm a+b+ c
Newman staggered form of ‘A’
1,1,1-trichloro ethane (CCl 3  CH3). (Major product) OH F a+b+ c+d
Cl CH3
(a) (b)
H H
In a cyclic or open-chain compounds,
CH3 angle strain (c) is absent. e.g.
Cl Cl
φ (c) (d) Compound Types of
H strains/forces
Dihedral angles (φ) = 60 ° Ans. (b) H a
H
CH3
03 Given below are two statements. CH2 Mo2O3 H
773 K, 10-20 atm
Statement-I 2-methylbutane on CH2 CH3 H H
CH H
oxidation with KMnO 4 gives CH2 CH3
2-methylbutan-2-ol. + 4H2
CH3 a+b
2-methyl hexane
H CH3
Statement-II n-alkanes can be
Toluene
easily oxidised to corresponding H H
Oxides of molybdenum, vanadium and
alcohols with KMnO 4 . chromium, i.e. Mo2O3, V2O5 and Cr2O3 H
Choose the correct option. work as catalyst. When they are OH a+b+d
[2021, 17 March Shift-II] operated under certain temperature
H OH
(a) Both statements I and II are correct. and pressure with n-heptane then they
(b) Both statements I and II are form toluene which is aromatic
H H
incorrect. compound. Mo2O3 behave as
H
aromatising agent.
Hydrocarbons 281

06 In the following skew 09 Of the five isomeric hexanes , the Ans. (d)
conformation of ethane, isomer which can give two In neopentane, all H are equivalents.
H′ C C H′ ′ dihedral angle is monochlorinated compounds, is CH3 CH3
H [AIEEE 2005]
H′ 29°  
H (a) 2-methylpentane H3C  C  CH3 →
hv
H3C  C  CH2 Cl
H Cl2
(b) 2,2-dimethylbutane  
(c) 2,3-dimethylbutane CH3 CH3
H′′ H (d) n-hexane
[2019, 12 April Shift-II] Ans. (c)
13 Butene-1 may be converted to
(a) 58° (b) 149° Cl2 butane by reaction with
(c) 151° (d) 120° (a) 2-methylpentane → five
[AIEEE 2003]
Ans. (b) types of monochlorinated
compounds (a) Zn-HCl (b) Sn-HCl
A dihedral angle is the angle between (c) Zn-Hg (d) Pd/H2
Cl2
two C—H bonds projected on a plane (b) 2, 2-dimethylbutane → three Ans. (d)
orthogonal to the C—C bond. In the types
Pd /H
given skew conformation, having Cl2 CH2 == CHCH2 CH3 → 2
∆ , pressure
Newman’s projection the dihedral angle (c) 2, 3-dimethylbutane → two Butene-1
is types CH3CH2 CH2 CH3
H′ C  C H′′ Cl2 Butane
(d) n-hexane → three types
= (H ′  C  C H a ) + (H a  C  C H ′′) Other reagents are successful with
= 29 °+120° = 149 ° polar double bonds.
10 Which one of the following is
H reduced with zinc and hydrochloric
H H′
Ha
29° (ethane, C2H6) acid to give the corresponding TOPIC 2
hydrocarbon? [AIEEE 2004]
120° (a) Ethyl acetate (b) Acetic acid
Alkenes
H′′ H
b (c) Acetamide (d) Butan-2-one H3C H
Ans. (d) 14 + Br2
07 Alkyl halides react with dialkyl Carbonyl compounds are reduced to H3C H
copper reagents to give corresponding alkanes with (Zn + conc.
CCl4
(a) alkenyl halides [AIEEE 2005] HCl). It is called Clemmensen reduction. Product (P)
(b) alkanes O
|| Consider the above chemical
(c) alkyl copper halides Zn(Hg) + HCl
CH3CH2 ⋅ C  CH3 → reaction. The total number of
(d) alkenes
CH3CH2 CH2 CH3 stereoisomers possible for
Ans. (b)
product P is ……
R2 CuLi + R ′ X → R  R ′+ R  Cu + LiX 11 Which one of the following has the [2021, 25 July Shift-II]
(dialkyl copper minimum boiling point? Ans. (2)
lithium) [AIEEE 2004] Br2 / CCl 4 gives anti-addition of bromine
(a) n-butane (b) 1-butyne with alkene but product formed in the
08 2-methyl butane on reacting with (c) 1-butene (d) Isobutene reaction depends upon the stereo of
bromine in the presence of Ans. (d) alkene (E or Z alkene).
sunlight gives mainly [AIEEE 2005] H3C Here, cis alkene /Z-alkene is given, so
(a) 1-bromo-3-methylbutane Isobutene C == CH2 has we get racemic mixture of two isomers.
H3C
(b) 2-bromo-3-methylbutane CH3
minimum force of attraction (due to H3C H
(c) 2-bromo-2-methylbutane Br2 H Br
(d) 1-bromo-2-methylbutane steric hindrance). Thus, minimum CCl4 Br H
boiling point. H3C H (anti-addition) CH3
Ans. (c)
cis/Z
H H CH3
| | Br2
12 On mixing a certain alkane with
H3C  C C CH3 → Br H
chlorine and irradiating it with +
H Br
| | ultraviolet light, it forms only one
H CH3 CH3
monochloroalkane. This alkane
Br
| could be [AIEEE 2003] The total number of products possible = 2
CH3  CH2  C  CH3 (a) propane Mechanism First cis-alkene reacts with
| (b) pentane Br2 to form bromonium ion and then ring
CH3 opening takes place by nucleophileBr −
2-bromo- 2- methyl butane (c) isopentane
to form two racemic products.
(d) neopentane
282 JEE Main Chapterwise Topicwise Chemistry

+
CH3 CH3 H3C Br CH3 16 For the given reaction CH3 CH3
[2021, 26 Feb Shift-I]
+ Br  Br (c) A : B:
(i) NaNH2
H H H H HC CHBr OH O
(ii) Red hot iron tube iron,
– CH3 873 K
Br Br O
(A)
Major product (c) A : OHC CH2CH2CH2 C CH3
H3C Br CH3 H3C Br –
(a) CH3CH2CH2NH2 (b) CH CH NH2 O
CH3
CH2 B : HOOC CH2CH2CH2 C CH3
H Br H H Br – H
H 3C CH3 Ans. (d)
CH3 CH3 (c) (d) In first step, KMnO 4 (dil.) help to break
Br H H Br alkene in ketone and aldehyde and in
H Br Br H second step, CrO3 is used for selective
CH3 over oxidation of aldehyde only. CrO 3
CH3 CH3 will form aldehyde to acid in product (B).
Racemic mixture
Ans. (d)
When 1-bromo-prop-1-ene reacts with CH3 + –
KMnO4/273K
NaNH2 (a strong base), β-elimination or
15
dehydrobromination, (–HBr) takes place
Br 1-methyl
to give propyne in next step. When O O–
cyclopentene
(i) (C6H5CO)2O2, HBr P propyne is passed through red hot iron Mn
(ii) CoF2 (Major tube, cyclic trimerisation (aromatisation
product) also) occurs to produce mesitylene (A) O O

Major product P of above reaction as major product.

O O–
is [2021, 20 July Shift-II] Step I
Mn
F Br
NaNH2 O O
CH3—C C CH3—C H
H –HBr
(a) Propyne CH3
H
Br 1-bromo-propene
F OO
(b) Step II (5-oxohexanal)
Br Red hot
3CH3—C H H
iron tube
873 K (A)
(c)
F CrO3 (over oxidation)
Br HC
CH3 CH3 H3C CH3
F C C CH3
(d)
CH
Br CH OO
C
Ans. (d) (5-oxohexanoic acid)
CH3
CH3 OH
Addition of HBr in presence of peroxide (A) ( B)
follows anti-Markownikoff rule. i.e. (Major)
Mesitylene or
hydrogen atoms are attached to carbon
atom with least hydrogen substituents.
1, 3, 5-trimethyl 18 The major product in the following
benzene
reaction is
(C6H5CO)2O2 H3C CH == CH2
17 Identify products A and B.
Br HBr H3O+
CH3
Heat
Br Dil. KMnO4 CrO3
A B [2020, 2 Sep Shift-I]
273 K
Br
3-(4' bromophenyl) bromopropane [2021, 24 Feb Shift-I] H3C CH3
CH3
On reaction with CoF2 , bromine is CH3 CH3
(a) (b)
replaced by fluorine in haloalkanes. This CH3
reaction is known as Swarts reaction. (a) A : OH B:
CoF2 OH
OH
O H3C
Br CH3
CH3
CH3 CH3 (c) (d)
Br
F CH3
(b) A : OH B: OH
Br
3-(4' bromophenyl) fluoropropane OH O
Hydrocarbons 283

Ans. (d) Br F(–I) charge means it is unstable. ThenH2O

β′ β will remove from here.
Complete mechanism is as follows: α
CH3 CH CH 2C CH3
5 4 3 1 CH3
CH CH2 Hr H H More r –H2O
acidic H3C C CH2 OH2
(H3O+) Hofmann Saytzeff
Electrophilic addition centre for centre for CH3
CH3 E2 α, β-elimination (1° carbocation)
r E2 CH3
CH CH2 (E 2)
3 r
4 –HBr
2 H3C C CH2
5 F
6
CH3
(3° carbocation) CH3
CH3 CH2 CH C CH3
5 4 3 2 1
Stability of carbocation
(2-fluoro-pent-2-ene)
(Rearrangement is 3° > 1°.
Ring expansion (Major)
intermediate)
of carbonation −I-effect of F atom makes the CH3
β-hydrogen more acidic for its
CH3 H3C C CH2 CH3
4
3
H2 O elimination by a strong base used inE2 .
1 r
r 3° carbocation
5 2 (H3O+)
6
CH3 20 When neopentyl alcohol is heated
–Hr On heating 3° carbocation, 2 possible
with an acid, it slowly converted
5 membered 6 membered ring products are possible.
into an 85 : 15 mixture of alkenes A
(Thermodynamically and B, respectively. What are these These are as follows :
more stable)
alkenes? α
Saytzeff centre [2020, 4 Sep Shift-I] CH3
H α
CH3 CH3 α
–H2O CH3 H3C C CH2 CH3
∆
H3C r
H (a) H3C
OH and Left Right
CH3 H3C (–H+)
Hofmann CH2 (–H+)
centre H CH3
H3C CH2 H3C CH3 CH3
(b) CH3
and H2C C CH2 CH3 C CH2 CH3
CH3 H3C H2C CH3
2- substituted 3- substituted
(Major) (Minor product)
CH3 CH2 (Major product)
H3C H3C (B) (15%) (A) 85%
The major product obtained in the given (c)
and
reaction is 1, 2-dimethyl cyclohexene. So, correct option is (a).
H3C H3C
19 The major product obtained from CH3 CH2
H3C 21 The major product [B] in the
E 2 -elimination of 3-bromo- (d) H3C
and following reactions is
2-fluoropentane is H3C
[2020, 2 Sep Shift-II] CH2 CH3
Br Ans. (a)

 CH3 CH2 CH CH2
(a) CH3CH2 CH  CH2 == CH2 Reaction is as follows :
OCH2CH3
CH3 HI H2SO4
(b) CH3CH2CH == C  F H2SO4 (acid) → [A] alcohol → [B]
 Heat ∆
H3C C CH2 OH
CH3 CH3
[2020, 4 Sep Shift-II]
F CH3 CH3
 H3 C C CH2 OH2
r
(c) CH3 CH == CH C H CH3 
(a) CH3 CH == C  CH3
Br CH3
 H2SO4 is sulphuric acid, that containH⊕ (b) CH2 == CH2
(d) CH3 CH2  C ==CH CH3
and alcohol of contain lone pair. CH3
Ans. (b) Lone pair of oxygen acceptH⊕ ion and 
Br atom is larger than F atom. So, C Br ⊕ (c) CH3 CH2 C == CH2
form OH2 but oxygen is electronegative
is weaker than C F bond. In elimination (d) CH3 CH2 CH ==CH CH3
element and here O contain positive
(E2 ), C Br bond will be cleared.
284 JEE Main Chapterwise Topicwise Chemistry

Ans. (a) OH
CH3
CH3
H
Tautomerism CH C CH2
H3C CH
CH3 CH2 CH CH2 O CH2 CH3
via I H3C
(Iodine attached
HI (SN2)
to less hindered O
reaction
alkyl group) CH3
CH3
CH C CH3
H3C CH
CH3 CH2 CH CH2 OH + CH3 CH2 I
[A] H2SO4/∆ CH3
E1 reaction) OH
CH3 CH3
NaBH4 CH CH CH3
r
CH3 CH2 CH CH2 Reduction CH3 CH (Q)
CH3
O
Rearrangement CH3
CH3 CH2
CH3 C ∆ conc . H2SO4
1, 2-H-shift r of C group
For more stable According to
carbonation Markownikoff‘s rule
∆ H
(more subtituted CH3
alkene formed) r
C CH CH3
CH3 CH3 H3C CH
CH3 CH3 C + CH3 CH C (1, 2 shift)
CH3 CH3 H3C Rearrangement
(Minor product) (Major product)
undergoes for more
(B)
stable carbocation
CH3 r
22 The major product [R] in the following sequence of C CH2 CH3
CH3 CH
reactions is H3C
(According to Markownikoff rule)
(i) LiNH2 /ether
Hydrogen aliminate from highly
HC ≡≡ CH → [P] substituted carbon
(ii) H3 C CH3
CH  Br C CH2 CH3
(CH3 ) 2 CH CH3 C
(R)
CH3
Major product
(i) HgSO4 /H2 SO4 Conc. H SO
→ [Q] →
2 4
[R] So, correct option is (c).
(ii) NaBH4 ∆

[2020, 4 Sep Shift-II] 23 The major product [B] in the following sequence of
reactions is
H3C H 3C
(a) C== CH  CH3 (b) CH—CH==CH2 (i) B H Dil. H2 SO4
CH2 C == CH CH2CH3   →È [A] → [B]
2 6
∆
(CH3)2CH (CH3)2CH  (ii) H 2 2 , OH
O

H2C CH(CH3 ) 2 [2020, 8 Jan Shift-II]

H3C
(c) C==C(CH3)2 (d) C  CH2  CH3
(a) CH3 C CH == CH CH3 (b) CH3 C == CH  CH2CH3
(CH3)2CH  
H3CCH2
CH(CH3)2 CH(CH3)2
Ans. (c)
r (c) CH3—C—CH2CH2CH3 (d) CH2 == C CH2CH2 CH3
LiNH2/ether s 
H C CH H C CLi+ C
It abstract H+ CH(CH3)2
(P )
Acetylene from alkine and H3C CH3
act as a base
Ans. (c)
H C
s
C Li+ + CH3 CH Br OH
(i) B2H6
CH3—C == CH—CH2CH3 – CH3—CH—CH—CH2CH3
CH(CH3)2 (ii) H2O2/OH
CH Anti-Markownikoff CH
CH3 hydration
CH C C H CH3 CH3 CH3 CH3
H3C HC Hg2+ (HgSO4) (A)
HO H
H3C Hydration
Hydrocarbons 285

CHO and OHC  CHO molecule that contains both OH group

(+H+)/∆ (a) OHC
(A) + dil. H2SO4 and a halogen. In a vicinal halohydrin,
–H2O
(b) OHC the OH and halogen are bonded to
(Protonation of OH
CHO adjacent carbons.
group and removal of H2O)
(c) OHC CHO Cl2 /H 2 O
+
CH3—CH—CH—CH2—CH3 H 3C  CH == CH2 →
OtBu H3C  CH  CH2 +
(2° carbocation)
CH (d) OHC  
CH3 CH3 CHO OH Cl
Ans. (a) A chlorohydrin (major product)
Carbocation
rearrangement 3 Step II CH3  CH  CH2 + HBr
2° to 3° Step I O3/Me2S  
–
by H shift KOtBu
2
Ozonolysis Cl Cl
1 (Minor product)
Br Cyclohex-1,
3-diene The reaction proceeds through
CH3—C—CH2—CH2—CH3
–H+ CHO following mechanism :
C From b-position with OHC Slow
least number of CH3—CH=
=CH2 + Cl—Cl
CH3 CH3 and OHC CHO
H-atoms forms major +
[B] product (Saytzeff's rule) In step-1 dehydrohalogenation reaction Cl
H2O
takes place. Here, hydrogen is CH3—CH—CH2 Fast
β β eliminated fromβ-carbon and the
+ Chloronium –
CH3—C——CH2—CH2—CH3 ion + Cl
halogen is lost fromα-carbon atom. As
CH (3° carbocation)
a result diene is formed. H2O
CH3—CHCH2—Cl Fast
CH3 CH3
H +| +
– OH
OtBu CH3CH—CH2—Cl + H3O
| |
24 The correct order of heat of Br Cyclohex-1,3-diene H OH
combustion for following Chlorohydrin
Cyclohex -1, 3-diene on ozonolysis gives
alkadienes is [2020, 9 Jan Shift-I]
butane-1, 4- dial and ethane- 1, 2- dial. 27 But-2-ene on reaction with alkaline
(A) (B) CHO KMnO 4 at elevated temperature
CHO |
O3
| + (CH2)2 followed by acidification will give
Me2S [2019, 12 April Shift-I]
(C) CHO |
CHO (a) CH3  CH  CH— CH3
(a) (B) < (C) < (A) (b) (A) < (B) < (C)  
(c) (A) < (C) < (B) (d) (C) < (B) < (A) 26 The major product of the following OH OH
Ans. (b) addition reaction is (b) one molecule of CH3CHO and one
Cl2 /H2 O molecule of CH3COOH
All given three alkadienes are isomers. H3C CH == CH2 → (c) 2 molecules of CH3COOH
Upon combustion, all of them gives [2019, 12 April Shift-I] (d) 2 molecules of CH3CHO
same product. (a) CH3 CH CH2 Ans. (c)
The most stable isomer will have least   But-2-ene on reaction with alkaline
heat of combustion. Between two Cl OH KMnO4 at elevated temperature
geometrical isomers of an acyclic
(b) CH3  CH CH2 followed by acidification will give acetic
alkene, trans is more stable than cis. In   acid (CH3COOH). Hot alkaline solution of
the given options, (a) have both double OH Cl potassium permanganate followed by
bonds that are trans, O acidification oxidatively cleaved
(b) have one cis and other one trans and (c) H3C alkenes. The reaction proceed as
(c) have both cis. So, the correct follows :
Alk. KMnO4 , heat
stability order of heat of combustion is
O CH3  CH ==CH  CH3 →
H3O+
A < B < C. 2CH3COOH
(d) H3C CH3
Acetic acid
25 The major product(s) obtained in Ans. (b) 28 The major product of the following
the following reaction is/are The major product of the given addition reaction is [2019, 11 Jan Shift-I]
[2019, 12 April Shift-I] reaction is H3C  CH  CH2 . In this
reaction,   Cl
OH Cl (i) HBr
(i) KOtBu
(ii) O3/Me2S H2O is used as a solvent and the major (ii) alc. KOH
product of the reaction will be a vicinal
Br O
halohydrin. A halohydrin is an organic
286 JEE Main Chapterwise Topicwise Chemistry

OH Cl CH3O 31 Ozonolysis of an organic

(c)
(a) (b) compound gives formaldehyde as
Cl one of the products. This confirms
O O Cl the presence of [AIEEE 2011]
Cl (a) two ethylenic double bonds
(c) (d) (d) CH3O (b) a vinyl group
(c) an iso propyl group
O (d) an acetylenic triple bond
OH
Ans. (c) Ans. (b)
Ans. (c)
The given reactant in presence of Cl2 /
Alkenes give carbonyl compounds on
In presence of HBr, reactant containing CCl 4 , given vicinal dihalide. Chlorine
ozonolysis.
C==C undergoes electrophilic adds up to alkene via electrophilic
addition reaction involving cyclic 3O /Zn/H O
2 → HCHO
addition reaction and give substituted Alkene  

chlorinium ion formation. (A )
alkyl halide. On further reaction with alc.
H3CO + other carbonyl compound
KOH, α,β-elimination takes place that Cl2/CCl4
give corresponding diene. The diene  R1 
Cl  
undergoes enolisation to give stable  C == O
product (phenol). H3CO R (B) 
 2 
Cl –I effect at a-position to C==C
Cl In order to determine alkene, place
HBr carbonyl compounds with their O-atom
The vicinal dihalide in presence of
face to face. Replace O-atom by a
O Carbocation formation in the
anhyd. AlCl 3 results in the formation of
double bond.
electrophilic addition of HBr carbocation that rearranges itself to
R1
–I-effect at b-position to C==C form a cyclic compound.
C==O + O == CH2
Cl (B) (A )
Cl H R2
H3CO + AlCl3
—Br Acidic (Anhyd.) o- atoms face to face
β–H Cl
Replace
O H
Cl  →
O-atom by ( ==) bond R1
H3CO
+ –
r + AlCl C == CH2
–HCl Alc. KOH 4
–HBr (α, β–elimination) R2

H CH3O
Conjugated 32 In the following sequence of
H diene, stable
reactions, the alkene affords the
Cl
CH3O H compound ‘B’
2 O HO
Enolisation to –H+ CH3CH == CHCH3 →
3
A → B
attain aromaticity Cl Zn
OH The compound B is [AIEEE 2008]
[Very stable, phenol] 30 The reaction of propene with HOCl
(a) CH3CH2CHO
(Cl 2 + H2O) proceeds through the
29 The major product of the following (b) CH3COCH3
intermediate [JEE Main 2016]
+ + (c) CH3CH2COCH3
reaction is (a) CH3 CHCH2Cl (b) CH3CH(OH)CH2
+ + (d) CH3CHO
CH3O (c) CH3CHClCH2 (d) CH3 CHCH2OH
(i) Cl2/CCl4
Ans. (d)
(ii) AlCl3 (anhyd.)
Ans. (a) O3
CH3CH ==CHCH3
[ 2019, 12 Jan Shift-I] δ– δ+
HO—Cl O
CH3—CH— CH2
Cl (Electrophilic
addition) CH3 CH CH CH3
+
CH3—CH—CH2—Cl
CH3O O O
(a) (Intermediate)
– Zn , H2O
OH
Reductive
CH3O CH3—CH—CH2—Cl ozonolysis
(b) 2CH3 CH ==O
Cl OH
‘B’
Hydrocarbons 287

Me OH
33 35 Reaction of one molecule of HBr
∆ with one molecule of 1,
r Me (c)
s N 3-butadiene at 40°C gives
Et predominantly [AIEEE 2005] O
OH O2N
n -Bu (a) 1-bromo-2-butene under OCH3
kinetically controlled conditions O
The alkene formed as a major (d)
(b) 3-bromobutene under
product in the above elimination thermodynamically controlled
reaction is [AIEEE 2006] conditions O2N
Ans. (b) (c) 1-bromo-2-butene under Ans. (a)
Compounds bearing a quaternary thermodynamically controlled
nitrogen atom bonded to four alkyl conditions Alkynes undergo hydration in presence
groups when heated in the presence of of HgSO4 and ether are least reactive
(d) 3-bromobutene under kinetically
base like OH− undergo E2 elimination with and their cleavage take place only under
controlled conditions drastic conditions.
the formation of less substituted alkene
as a major product with the loss of β −H Ans. (c)
atom. CH2 ==CHCH == CH2 + HBr → O2N— —C C— OCH3
This type of elimination is called Hofmann CH3 CH CH == CH2 + CH3CH ==CHCH2Br Hg2+/H+
elimination.  H2O
Br 1, 4-addition product
B 4(H)
1, 2-addition product OH
H
CH 3
+ CH 3 β1(H) Addition is through the formation of O2N— —CH== C— —OCH3
N
H H CH 2 — CH 3 allylic carbocation.
⊕ ⊕ Tautomerisation
CH2== CH C HCH3 ←→ CH3CH == CH CH2
CH 2 — CH 2 — CH 2 — CH 3
β3(H) β2(H) O
(2 ° allylic) (1° allylic)
s (more stable) O2N— —CH2C — —OCH3
∆ OH (less stable)

Under mild conditions (temperature Hence, the correct option is (a).

CH 3 ≈ − 80 ° C ) kinetic product is the 1,
+CH 2 CH 2 2-addition product and under vigorous 37 The major product (Y ) in the
conditions, (temp. ≈ 40 ° C )
CH 3
following reaction is
N
thermodynamic product is the [2020, 9 Jan Shift-I]
CH 2 — CH 2 — CH 2 — CH 3
1, 4-addition product.
(Major product) CH3
Thus, 1-bromo-2-butene is the major

CH 3
product under given condition.
+CH 2 CH 2CH 2CH 3
N
CH 3
(Minor product) CH3  CH  C ≡≡ CH
HgSO4 , H2 SO4 (i) C2H5MgBr, H2 O
CH 2 — CH 3
TOPIC 3 → X → Y
H2 O (ii) Conc. H2 SO4 / ∆
Hence, CH == CH2 will be a major
product. Alkynes CH3

24 Elimination of bromine from (a) CH 3 C == C CH3
36 The major product obtained from 
2-bromobutane results in the the following reaction is CH2CH3
formation of [AIEEE 2005] [2020, 6 Sep Shift-I]
CH3
(a)
predominantly 2-butyne
O2N— —C C— —OCH3 
(b)
predominantly 1-butene (b) CH3  CH C == CH CH3
(c)
predominantly 2-butene Hg2+/H+ 
(d)
equimolar mixture of 1 and H2O CH3
2-butene CH2
OCH3
Ans. (c) 
(c) H3C  C  CH  CH3
CH3CH2 CH CH3 → CH3CH2 CHCH3 → (a)
⊕ −H+ 

(2 ° carbocation) O C2H5
Br O2N
OH CH3
CH3CH2 CH == CH2 + CH3CH == CHCH3 O

Less substituted More substituted (b) (d) CH3  CH C == CH2
II I 
Stability of I > II, hence I is predominant. O2N CH2CH3
288 JEE Main Chapterwise Topicwise Chemistry

Ans. (a) Conc. HCl

+
NaBH4 ZnCl2
CH3 CH3 O CH3 CH CH3 CH3 CH CH3
Hg SO4 , H2 SO4
CH3— CH— C≡≡CH CH3—CH—C—CH3 OH Cl
H2O
(X) (2° alcohol) Turbidity within 5 minutes
(Hydration of alkynes) (Ketone) (Insoluble in Lucas reagent)
C2H5 MgBr ,H2O CH3 OH In step-1, prop-1-yne reacts with Ag2O to form CH3  C ≡≡ C  Ag,
CH3—CH—C—CH3 that forms white precipitates.
Conc. H2SO4 In step 2, prop-1-yne in presence of mercuric sulphate and
∆ C2H5
CH3 CH3 (3° alcohol) dil ⋅H2SO4 produces carbonyl compound (CH3)2 C == O which
C==C produces (CH3)2 CH OH in presence ofNaBH4 . 2ºalcohol on
CH3 CH2 — CH3 (acid catalysed
dehydration of alcohol reaction with Lucas reagent produces turbidity in about 5 min.
2, 3-dimethyl pent-2-ene give alkene,
(Y) major product
is Saytzeff's) 40 The major product of the following reaction is
(i) KOH alc.
CH3CH2 CH CH2  →
38 The major product of the following reaction is   (ii) NaNH2
CH3C ≡≡ CH (i)
DCl (1 equiv.)
→ Br Br
in liq. NH3
(ii) DI [2019, 9 April Shift-I]
(a) CH3CH2 C H CH2
(a) CH3CD(Cl)CHD(I) (b) CH3CD2CH(Cl) (I)  
(c) CH3CD(I)CHD(Cl) (d) CH3C (I) (Cl)CHD2 NH2 NH2
Ans. (d) (b) CH3CH == CHCH2NH2
The major product obtained in the given reaction is (c) CH3CH == C == CH2
CH3C (I) (Cl) CHD2 . (d) CH3CH2C ≡≡ CH [2019, 12 Jan Shift-II]
1. DCl (1 equiv. ) Ans. (d)
CH3C ≡≡ CH → CH3C(I) (Cl) CHD2
2. DI
The reaction proceeds as :
Addition in unsymmetrical alkynes takes place according to Alc. KOH
Markovnikov’s rule. CH3 CH2 CH CH2 CH3 CH2 CH CH2

Reaction proceed as follows : Br Br Br

NaNH2/liquid NH3
Cl Cl –
DCl
(1 equiv.)  DI
 CH3 CH2 C CH
H+
CH3CH2C CNa+
CH3 C ≡≡ CH → CH3 C == CHD → CH3  C  CHD2
Prop -1-yne  Thus, option (d) is the correct answer.
I
Product
41 The trans-alkenes are formed by the reduction of
39 Consider the following reactions, alkynes with [JEE Main 2018]

Ag2O
(a) H2 -Pd/C, BaSO 4 (b) NaBH4
ppt (c) Na/liq. NH3 (d) Sn-HCl
∆
A Turbidity Ans. (c)
Hg2+/H+ NaBH4 ZnCl2
B C Conc. HCl
within
5 minutes Sodium metal in liquid ammonia reduces alkynes with anti
stereochemistry to give trans alkenes. The reduction is
A is [2019, 12 April Shift-II] selectively anti since the vinyl radical formed during reduction is
(a) CH ≡≡ CH (b) CH3 C ≡≡ C CH3 more stable in trans configuration.
(c) CH3 C ≡≡ CH (d) CH2 == CH2 R R H
H–NH2
Ans. (c) RC C R′ C C C C
–NH2
According to the given conditions, the compound should be Na Na+ R′ R′
Vinylic
alkyne with triple bond present at the terminal. The chemical
radical
reactions involved are as follows : Sodium atom donates an electron to alkyne
Ag2O which after H-abstraction fromNH3 forms
Step 1 CH3 C CH CH3 C C Ag vinylic radical. Transfer of another electron
Prop-1-yne (Precipitates) gives a vinylic anion, which is more stable in
trans form. This in turn gives trans-alkene Na Na+
Step 2 after H-abstraction fromNH3 .
Hg2+
CH3 C CH dil. H SO
2 4 R H R H
H–NH2
OH Tauto-
O C C –NH2 – C C
merisation H R′ R′
CH3 C CH2 CH3 C CH3 Vinylic anion
Hydrocarbons 289

42 The major organic compound H H

| |
TOPIC 4
formed by the reaction of (c) CH3 C == C  CH3 Aromatic Hydrocarbons
1, 1, 1 −trichloroethane with silver (d) CH4
powder is [JEE Main 2014]
Ans. (d) 48 Which one of the following
(a) acetylene (b) ethene
Terminal alkyne has acidic hydrogen compound(s) is/are aromatic in
(c) 2 −butyne (d) 2 −butene
which is enough to protonate the nature ? [2021, 1 Sep Shift-II]
Ans. (c) Grignard reagent.
Cl CH3MgX + CH3C ≡≡ CH → (a) (b)
 Ag
2Cl  C  CH3 → CH4 + CH3C ≡≡ CMgX
 CH3
Cl 46 Acetylene does not react with
(1, 1, 1 − trichloroethane) [AIEEE 2002] +
CH3  C ≡≡ C  CH3 + 6AgCl (a) Na (c) (d)
(2 -butyne) (b) ammoniacal AgNO 3 Ans. (a,d)
43 2-hexyne gives trans-2-hexene on (c) HCl Aromatic compounds are conjugated
treatment with (d) NaOH planar ring system having delocalised
[AIEEE 2012] π-electron clouds and follows
Ans. (d)
(a) Pt / H2 (b) Li / NH3 (4n + 2) π-electron rule, i.e. Huckel’s rule.
1
(c) Pd / BaSO 4 (d) LiAlH4 CH ≡≡ CH + Na → CH ≡≡ C−Na+ + H2 { n = 0, 1, 2, K }
2
Ans. (b)
CH ≡≡ CH + AgNO3 →
(b) Li/NH3 (ammonical) (a)
CH3CH2 CH2  C ≡≡ C  CH3 → CH ≡≡ C− Ag +
2-hexyne [Birch reduction] White ppt.

CH ≡≡ CH + HCl → CH2 == CH  Cl. 10pe– in cyclic conjugation place.

H CH3 Usually occurs in the presence ofHg2 + . It is aromatic.
C ==C CH == CH + NaOH → no reaction
CH3CH2 CH2 H (b) 4pe– in cyclic conjugation
Because of hard acid, hard base and It is anti-aromatic.
Trans -2- hexene soft acid, soft base (HASB) theory. But
is reacts withNaNH2 . Å
2
(a) Pt/H (c) CH3
2-hexyne → n -hexane CH ≡≡ CH + NaNH2 →
CH ≡≡ C−Na+ feasible. 4pe– in cyclic conjugation.
(c) Pd /BaSO It is anti-aromatic.
→
4
cis -2-hexene
[Lindlar’s catalyst] 6pe– in cyclic conjugation.
47 Acetylene reacts with (d) It is aromatic.
(d) LiAlH
→
4
no reaction hypochlorous acid to form
[AIEEE 2002]
(a) Cl2CHCHO
49 For the following
44 The hydrocarbon which can react
(b) ClCH2COOH 1. Br2/Fe/∆
with sodium in liquid ammonia is 2. Mg/dry ether
[AIEEE 2008] (c) CH3COCl 3. CH3OH
Product
(a) CH3CH2CH2C ≡≡ CCH2CH2CH3 (d) ClCH2CHO
[2021, 31 Aug Shift-II]
(b) CH3CH2C ≡≡ CH Ans. (a)
OCH3
(c) CH3CH == CHCH3 HC ≡≡ CH + Cl OH (a) + HMgBr
(d) CH3CH2C ≡≡ CCH2CH3 (Acetylene) (hypochlorous acid)
Ans. (b) Cl H
−H2O OCH3
Only terminal alkynes undergo reduction CH  CH == ← (b) + Mg
with sodium (Na) in liquid ammonia (NH3). Cl Br
Hence, CH3CH2 C ≡ CH reacts withNa in (2, 2 dichloroethanol) Tautomerises CH3
OH
liq. NH3. [Cl  CH == CH OH] (c) + Mg
2 − chloroeth -1en -1-ol Br
Na /liq. NH 3
CH3CH2 C ≡ CH →  Cl  CH  CH OH Br
∆
CH3CH2 C ≡ C−Na+     OH
(d) + Mg
 Cl OH  OCH3
45 The treatment of CH3MgX with
Ans. (b)
CH3C ≡≡ C H produces Benzene on reaction with Br2 /Fe give 5
[AIEEE 2008]
bromo benzene as follows
(a) CH3 CH == CH2
(b) CH3C ≡≡ C  CH3
290 JEE Main Chapterwise Topicwise Chemistry

Br Cl Br Here, H2SO4 acts as acid to give proton

(H+ ). This H+ react withHNO3 to give
1. Br2/ ⊕
H2 N O3 which provideNO2+ (electrophile)
Fe/D
Cl Cl
Benzene (Halogenation) Bromobenzene (C) (D) to benzene to form nitrobenzene.
Bromobenzene on reaction with Mg / dry (a) (D) > (C) > (B) > (A)
ether and CH3OH gives benzene as (b) (C) > (D) > (A) > (B) 53 Which of the following is an
follows (c) (C) > (B) > (A) > (D) aromatic compound?
[2021, 17 March Shift-I]
Br (d) (A) > (B) > (C) > (D)
MgBr Ans. (a)
2. Mg/ (a)
At constant volume, density depends on (b) ⊕
Dry ether
the mass of the compound. So, density
MgBr 3. CH OH is directly proportional to mass. On
3 moving down the group, mass ⊕
(c) (d)
increases.
H OCH3
Order of decreasing density in benzene
+ Mg
ring is Ans. (a)
Br I > Br > Cl > F.
Benzene
Density order is is an aromatic compound (6πe– ).
Br Cl
50 Which one of the following
compounds is not aromatic ? Aromatic compound possess following
[2021, 26 Aug Shift-II] > characteristics :
Cl Cl
(i) Planarity
(a) (b) 3-chlorobromobenzene 3-chloro-chlorobenzene
(D) or (ii) Complete delocalisation of the
+ 1, 3 dichlorobenzene π-electrons in the ring.
O (C) (iii) Presence of (4n + 2) π-electrons in
H Cl
(c) (d) the ring, where n is an integer
(n = 0, 1, 2 …).
Ans. (c) > > That compound follow all aromatic
characteristics.
The compound which follows Huckel‘s
Chlorobenzene Benzene
rule has planar structure is aromatic in (B)
nature.
(A) 54 Among the following, the aromatic
(c) compounds are
[2021, 16 March Shift-I]
52 Benzene on nitration gives
It exist in a non-planar tube shape, so it nitrobenzene in presence of HNO 3 (A) CH2 (B)
is non-aromatic. and H2SO 4 mixutre, where
[2021, 20 July Shift-II]
(a) It is aromatic in nature. (a) both H2SO4 and HNO3 act as a bases (C) (D)
(b) HNO3 acts as an acid andH2SO4 acts
Number of πe − = 4n + 2 (n = 2) = 6πe − as a base ⊕
(c) both H2SO4 and NHO3 act as an acids
Choose the correct answer from
(b) It is also aromatic in nature (d) HNO3 acts as a base andH2SO4 acts
as an acid
the following options.
(a) Only (A) and (B) (b) Only (B) and (C)
as the lone pair is in Ans. (d)
conjugation with πe − .
(c) (B), (C) and (D) (d) (A), (B) and (C)
Benzene on nitration gives
OH
Ans. (b)
nitrobenzene in presence ofHNO3 and
H2SO4 . For aromatic compounds following
(d)
⊕ conditions should be satisfied
H SO + HNO q HSOÈ + H N O
2 4 3 4 2 3
It is aromatic in nature as it (i) planarity
(Acid) (Base)
containsenzene ring. ⊕ ⊕ (ii) complete delocalisation of
H2 N O3 q H2O + N O2 π-electrons in the ring.
51 The correct decreasing order of (iii) presence of (4n + 2) π-electrons in
NO2
densities of the following the ring, where n =0, 1, 2, … . This
compounds is [2021, 25 July Shift-II] is called Huckel rule.
Cl + NO2+ e.g. n = 0, 2π e −
n = 1, 6πe −
(Electrophile)
Benzene Nitrobenzene n = 2, 10 π e −
(A) (B)
Hydrocarbons 291
CH2CH3 CH2CH3 NO2
(C) 1
2 NO2 NO2
6 HNO3/H2SO4
– 3 (Nitration) +
6pe (Huckel¢s rule 5
4
planar followed, i.e. (Major product)
aromatic) Br Br
4-bromo-2-nitro 4-bromo-ethyl
ethyl benzene benzene
(Major) 57 Consider the following chemical
[−I-effect of Br directs at its NO2− reaction.
meta-position] (1) Red hot Fe tube, 873 K
(B) (C) CH ≡≡ CH →
So, option (b) is the correct sequence of (2) CO, HCl, AlCl3
– reagents used.
(Planar) 6pe Product
4pe–
(Huckel's rule
(Not 56 The major product of the following The number of sp 2 hybridised
followed, i.e.
aromatic) aromatic) carbon atom(s) present in the
reaction is [2021, 25 Feb Shift-II]
NO2
product is … . [2021, 25 Feb Shift-I]
(A) CH 2 Ans. (7)
No complete delocalisation The reaction take place as follows
of p-electrons in the ring H2SO4 Red hot
(Not aromatic)
Fe-tube, 873 K
CH CH
NO2
55 The correct sequence of reagents Acetylene
Benzene
used in the preparation of (a) O
4-bromo-2-nitroethyl benzene
from benzene is NO2 C—H
[2021, 25 Feb Shift-II]
(b) CO +HCl
(a) CH3COCl / AlCl 3,Br2 / AlBr3,
AlCl3
HNO3 / H2SO4 , Zn/HCl
NO2 Benzaldehyde
(b) CH3COCl / AlCl 3, Zn-Hg/HCl,
Br2 / AlBr3,HNO3 / H2SO4 Every carbon atom found in
(c) Br2 / AlBr3, CH3COCl / AlCl 3, (c) benzaldehyde (6 carbon in benzene ring
HNO3 / H2SO4 , Zn/HCl +1 in aldehyde group), forms three bonds
NO2 with neighbouring atoms-(one double
(d) HNO3 / H2SO4 ,Br2 / AlCl 3,
bond + two single bond). Therefore, in
CH3COCl / AlCl 3, Zn-Hg/HCl
benzaldehyde total number of sp2 ‘C’
Ans. (b) (d) are 7.
Benzene on reaction with
CH3COCl / AlCl 3 gives acetophenone Ans. (b) 58 Which one of the following
which on reduction with Zn-Hg/HCl compounds is non-aromatic ?
gives ethyl benzene. Bromination of The reaction take place as follows :
[2021, 24 Feb Shift-II]
ethyl benzene give NO2
+
4-bromo-ethylbenzene which upon H
Step I
nitration gives 4-bromo-2-nitroethyl (a) (b)
benzene. NO2 O
+
CH3 C==O CH3  CH  CH  CH3 + CH3 +
(More stable intermediate) (c) (d)
CH 3COCl/AlCl 3 2° carbocation +
(Friedel-Craft NO2
acylation) +
Benzene Acetophenone  CH  CH2  CH2 Ans. (a)
(Less stable intermediate)
CH2CH3 Compound, which obey Huckel rule,
1° carbocation
(4n + 2) π is called aromatic compound.
Zn-Hg/HCl NO2
⊕
Compound, which obey4nπ rule, is called
(Clemmensen CH3 CHCH  CH3 anti-aromatic compound.
reduction) Step II
Ethyl benzene +
CH3 CHCH2  CH2 Compound which contain one or more
sp3 carbon in its structure is called
Bromination Br2/AlCl3 NO2 non-aromatic compound.
(For major product) The nature of following
(For minor product) ions/compounds are as follows :
292 JEE Main Chapterwise Topicwise Chemistry

Ans. (c)
(a) sp3 Aromatic electrophilic substitution
Carbon
reactions are fast in those compounds
Non-aromatic Each sp2 -hybridised atom has three sp2 in which the attacking site possess high
hybrid orbitals. electron density. Electron withdrawing
(b) (6e–) ∴ Total number of sp2 hybrid orbitals in groups (EWGs) reduces the electron
O
a molecule of benzene is = 6 × 3 = 18 density in the benzene ring due to its
Aromatic (follow Huckel's rule) strong –I effect and makes further
61 Polysubstitutiion is a major substitution difficult. Hence, called as
(c) (2e–) deactivating groups. While electron
drawback in [2019, 8 April Shift-II]
releasing groups (ERGs) increases the
Aromatic (follow Huckel's rule) (a) Friedel-Craft’s alkylation electron density in the benzene due to
(b) Reimer-Tiemann reaction resonance. Therefore, activates the
(d) (c) Friedel-Craft’s acylation benzene ring for the attack by an
(d) Acetylation of aniline electrophile.
(14e–)
Ans. (a) Hence, called as activating groups.
Anthracene Aromatic
Through aromatic electrophilic In given options,
Only (a) is non-aromatic and rest all are
substitution mechanism (ArSE2) when Activating groups are
aromatic.
••
mono-alkylation (Friedel- Craft’s — CH3 < — O CH3
reaction) is performed, we get ••
59 The reaction of H3N 3B 3Cl 3 (A) with (+ I , + R ) Strong + R - effect
mono-alkylated benzene. As, the alkyl
LiBH4 in tetrahydrofuran gives group is ring activating (towards ArSE2) Deactivating groups are
inorganic benzene (B). Further, the in nature, again o- and p-substituted — CN > — Cl
reaction of (A) with (C) leads to Strong – I - effect (− I > − R )
alkyl benzene will be obtained and so on.
H3N 3B 3 (Me) 3 . Compounds (B) and e.g.
CH2CH3 So, the correct order is
(C) respectively, are
CN Cl
[2020, 9 Jan Shift-II]
C2H5Cl (1 eqv.)
(a) diborane and MeMgBr
AlCl3 (anhyd.)
(b) boron nitride and MeBr —HCl < <
(c) borazine and MeBr C2H5
(d) borazine and MeMgBr D A
C2H5Cl (excess)
Ans. (d) Me OCH3
AlCl3 (anhyd.)

Road map of the given reactions is as C 2H 5

C2H5
follows : <
+LiBH4 C 2H 5
C2H5Cl
H3N3B3Cl3 (THF)
(B), + C B
(A) Inorganic AlCl3
benzene
C2H5 63 Increasing order of reactivity of
+ (C)
C 2H 5 C2H5 the following compounds for SN 1
C 2H
H3N3B3(Me)3 5
H5C2 C2H5 C2H5Cl
substitution is [2019, 9 April Shift-II]
Complete reactions are as follows : + AlCl3
CH3
H CH2 Cl
H3C Cl
H (Minor) CH3
B B– C2H5 (A) (B)
H H H + + (Major)
N N N N
Cl Cl
B B –
B B
+ 62 The increasing order of reactivity H3CO
H H H H
N N+ of the following compounds (C) (D)
(B3N3H6) towards aromatic electrophilic
H H (a) (A) < (B) < (D) < (C)
(Borazine) substitution reaction is
[2019, 9 April Shift-I]
(b) (B) < (C) < (D) < (A)
60 The number of sp 2 -hybrid orbitals Cl OMe Me CN (c) (B) < (A) < (D) < (C)
(d) (B) < (C) < (A) < (D)
in a molecule of benzene is
[2020, 9 Jan Shift-II] Ans. (c)
(a) 24 (b) 12 (c) 18 (d) 6 Reactivity of substitution nucleophilic
Ans. (c) B
unimolecular (S N 1) reaction depends on
A C D
the formation of carbocation. Greater
In benzene, every carbon atom is (a) A < B < C < D (b) B < C < A < D the stability of carbocation, greater will
sp2 -hybridised. (c) D < A < C < B (d) D < B < A < C be its ease of formation of alkyl halide
Hydrocarbons 293

and faster will be the rate of reaction. Electron-donating groups (EDG) will OCH3
(c) CH3
So, the correct order of (S N 1) reactivity increase electron density in benzene
is nucleus by any or both of their +R/+M
CH2Cl CH2—Cl and hyperconjugative (HPC) effects.
Now, let us consider the given substrte. (d) CH3O
> >
Cl –I-effect
dominates
[ 2019, 10 Jan Shift-I]
the +R-effect
OCH3 Ans. (d)
(+R)
(C) (D) (I)
CH3 + HPC In the given reaction, AlCl 3 act as Lewis
acid and helps in generation of
> CH3 CH2Cl carbocation. The resulting carbocation
(II)
Cl (1°) rearranges itself to stable
( A) (B) As –R effect is more powerful than carbocation (3°).
–I effect, the order of their reactivity,
In compound C, the carbocation formed MeO
towards an electrophile will be Cl AlCl3(anhy.)
is stabilised by activating group
III I II
( OCH3). Compound D forms benzyl (–R) < (–I>+R) < (+ HPC)
carbocation (C6H5  CH2+ ) that is
stabilised by resonance. Compound A r s
65 Which of the following compounds MeO Cl AlCl3
produces a primary carbocation that
is not aromatic? [2019, 9 Jan Shift-II]
further rearranges itself to secondary s
–AlCl4
carbocation. (a) (b) MeO
Nus N ⊕ H r (1°)
r H s
a-H shift
Cl (c) (d) (H2O)
1° carbocation
N
Rearrangement
r MeO
Ans. (b) r
2° carbocation Aromaticity of a compound can be
Compound B produces primary decided by Huckel’s rule. In 3° carbocation, more stable
carbocation which is least stable among cyclopentadienyl cation (b), resonance Protic medium, H2O supports the
takes place as follows: rearrangement of carbcation
all the given options. Intramolecular
ArSE2 pathway
64 The increasing order of the r
reactivity of the following Hence, is anti-aromatic does not Me O
compounds towards electrophilic follow Huckel’s rule as it has conjugated
aromatic substitution reaction is 4π-electron (4n π, n = 1) system. Rest of
[2019, 10 April Shift-I] H
the species are aromatic as each of MeO
Cl CH3 COCH3 them belongs to6π-electron –Hr
[(4n + 2) π, n = 1] system.

66 The major product of the following 67 The major product of the following
(I) (II) (III) reaction is reaction is
Br
(a) III < I < II (b) II < I < III CH3O KOH alc. (excess)
(c) III < II < I (d) I < III < II CH2Cl ∆
(i) AlCl3 (anhyd.)
Ph
Ans. (a) (ii) H2O
Br
Key Idea In electrophilic aromatic
substitution (Ar S E 2) reaction, the (a) CH3O
aromatic (benzene nucleus here)
compound (substrate) acts as a CH3 (a) Ph (b) Ph
nucleophile which gets attacked by an
electrophile in the rate determining (b) CH3O
step (rds). (c) Ph (d) Ph
Higher electron density on the [2019, 10 Jan Shift-I]
nucleophile, i.e. benzene nucleus will
fasten the rate of the reaction.
294 JEE Main Chapterwise Topicwise Chemistry

Ans. (d) Hence, melting point is lowest for

(B) ⇒4π-e − system
The reaction follows α,β-elimination naphthalene (−
~ 80 ° C), i.e. compound (b).
mechanism to give a more
substituted stable alkene as a major [4nπ, n = 1]⇒Anti-aromatic 70 The electrophile, E + attacks the
product. As the substrate is a α, γ (C) benzene ring to generate the
-dibromo (1, 3-) compound it gives a intermediate σ-complex. Which of
conjugated diene.
⇒8π-e − system [4nπ, n = 2] the following σ-complex is of
Br ⇒Anti-aromatic lowest energy? [AIEEE 2008]
HOs H Alc. KOH
∆
–2HBr NO2 NO2
Ph H (D)
Br sOH
sp3 (a) + H (b) +
⇒The sp -carbon does not
3 E
H E
support conjugation and also
devoids planarity. NO2
H H
(It is very stable because ⇒ Non-aromatic
(c) + E (d) + E
the conjugated diene
system present. It is 69 Among the following four aromatic
further conjugated with
the benzene ring.) compounds, which one will have Ans. (c)
the lowest melting point? NO2 being an electron withdrawing
[2019, 12 Jan Shift-II] group destabilises the carbocation by
68 Which compound (s) out of the
O decreasing electron density form σ −
following is/are not aromatic? complex. Thus, the presence ofNO2
[2019, 11 Jan Shift-I]
(a) OH
(b) group on a benzene ring of σ − complex
OH decreases their stability. However, the
carbocation (c) does not contain any
O
r NO2 group.
r CH3
(A) (B) Thus, it would be highly stable than
OH
O other σ -complexes. Hence, σ -complex
(c) O (d) (c) is of lowest energy.

s CH3 71 Presence of a nitro group in a

(C) ( D) Ans. (b) benzene ring
(a) (B), (C) and (D) (b) (C) and (D) Melting point of a compound depends (a) activates the ring towards
(c) (B) (d) (A) and (C) on size and force of attraction between electrophilic substitution
the molecules. Compound (c) has (b) renders the ring basic
Ans. (a) largest size and also possess weak (c) deactivates the ring towards
A compound is considered to be intermolecular association due to nucleophilic substitution
aromatic, if it follows three rules: dipole-dipole interactions.
(d) deactivates the ring towards
• Must be cyclic and planar. Compound (a) is a dicarboxylic acid and electrophilic substitution
• Must have conjugated system in it. possess high melting point due to [AIEEE 2007]
• It must follow Huckel rule which intermolecular hydrogen bonding.
Ans. (d)
states that number of π-electrons As a result, it exist as associated
 NO2 group withdraw electron from
= (4n + 2) molecule. Compound (d) is an alcohol
the ring, thus shows −M effect and
and possess intermolecular H-bonding.
(A) ⇒2π-e − system makes ring more electron deficient.
No interactions are present in
hydrocarbon (naphthalene) Hence,  NO2 deactivates the ring for
[(4n + 2) π, n = 0] compound (b). electrophilic substitution.
⇒Aromatic
24
Organic Compounds
Containing Halogens
TOPIC 1 CH3 Cl CH2Cl
(c) > >
Haloalkane (a) (b)
CH3
OH
01 In the following sequence of HO CH3 CH3
reactions, [2021, 01 Sep Shift-II] CH3 Cl CH Cl
+ OH CH3 >
H /H O
C 3H6  
2 KIO
→ A  →B+C (c) (d)
dil. KOH CH3
The compounds B and C Ans. (d) Cl Cl
respectively are In the given reaction E2 elimination (d) > >
(a) CI3COOK, HCOOH reaction takes place in which two
substituents are removed from a
(b) CI3COOK,CH3I CH3
molecule to form double bond (alkene).
(c) CH3I,HCOOK CH3 CH2Cl CI CH3
(d) CHI3, CH3COOK Cl CH3 >
Ans. (d) NaOH
C2H5OH
Propene (C3H6 ) undergoes acidic Ans. (a)
1-methyl cyclopent
hydrolysis to give A which is 2° alcohol. -1-3-diene The correct order of reactivity of
This alcohol undergoes iodoform (Major product) chlorides with acetate in acetic acid is
reaction in presence of KIO and dil. KOH CH3
to give iodoform alongwith potassium Cl Cl
03 The correct order of reactivity of
salt of carboxylic acid.
the given chlorides with acetate in > >
This reaction is known as iodoform test.
acetic acid is [2021, 31 Aug Shift-I]
H + /H 2 O
CH3  CH == CH2 → CH3 CH3
Acidic hydrolysis
Propene CH3 CH2Cl
(C 3H6 ) Cl Cl Cl
CH3  CH  CH3
(a) > > >

OH
(A ) The given chlorides undergoesS N 1
Propan -2 -ol CH3
KIO/Dil. KOH reaction. So, as the stability of
→ CH3  C O K + CHI3 s + Cl CH3 CH2Cl
carbocation formed increases, rate of
Iodoform
 Iodoform > reaction increases.
(B )
O
Potassium salt of Stability of carbocation is as follows
ethanoic acid CH3
(Postassium acetate) CH3
(C ) CH2Cl Cl
(b) >
> >
02 The major product of the following
reaction is [2021, 31 Aug Shift-II] Cl Cl CH3
> > CH3
CH3
Cl NaOH Allylic carbocation Allylic carbocation
Major product CH3 + 2α-H +1α-H
C2H5OH
296 JEE Main Chapterwise Topicwise Chemistry

CH3 CH2 s Br
● The O CH3 when acts as nucleophile (c)
> undergoes nucleophilic substitution
and replaces Brs to form ether, Br
which is a minor product. (d) Br
4α-H 1α-H OCH3 Ans. (a)
Hence, correct option is (a). Br HBr
SN 2
+ OCH3
04 The major product (A) formed in 2-methylbut-1,3-diene

the reaction given below is (Minor product)

[2021, 27 Aug Shift-II] Br
CH3—CH2—CH—CH2Br So, option (b) is correct. 1-bromo 3-methylbut-2-ene
This addition is known as 1, 4-addition.
CH3OH 05 In the following sequence of Mechanism This reaction can undergoes
+ CH3O A
Major reactions the P is two pathways
product [2021, 27 Aug Shift-I]
(a) CH3CH2CHCH2Br Path A
Cl Dry Ethanol
+ Mg (A) H—Br
ether
(P) H
Major product
OCH3
2° carbocation
(b) CH3—CH2—C==CH2
(a)
O—CH2CH3 Path B H—Br
(b)
(c) CH3—CH2—CH—CH2—OH CH2CH3
(c)
3° carbocation
(d) Out of the two intermediates formed in
two paths, the path B intermediate is
(d) CH3—CH2—CH—CH2—OCH3 more stable as it has more stable
Ans. (a)
carbocation. So, major product will be
In the first step, Grignard reagent is formed because of path B.
obtained. In the second step, acid-base
reaction occurs. Due to presence of an
Ans. (b) acidic hydrogen in alcohol,
On reaction of haloalkane with neutralisation reaction takes place that
methoxide ion, alkene is formed. produces alkane and water. 1, 2-addition Br
The reaction is
CH3O
CH3—CH2—CH—CH2—Br
CH3OH — Cl Mg MgCl Br
H3C—CH2—C==CH2 Dry ether
Br
Chloro- (A) (1, 4-addition)
cyclopentane
C2H5OH

(A) ( P) Br
Mechanism Cyclopentane
(Major product) 1, 2-addition product is formed at low
temperature and will be less stable as
H double bond is less substituted. 1,
06 The major product formed in the
Br 4-addition is thermodynamically stable
following reaction is product as double bond is more
OCH3 [2021, 26 Aug Shift-I]
substituted. As diene is in excess and
HBr HBr is limited in reaction, so diene
Major product
(More favoured cannot be formed. So option (b) is
product) (excess) incorrect.
s
● O CH3 will act as a base due to its small
(a) 07 Excess of isobutane on reaction
size and high electron density and Br
therefore, abstracts proton to form with Br 2 in presence of light at
double bond which is in conjugation Br 125°C gives which one of the
with aromatic ring. (b)
following, as the major product?
Br [2021, 26 Aug Shift-I]
Organic Compounds Containing Halogens 297

Br CH3 CH3 Complete reaction is as follows

   O
(a) CH3 C  CH2 Br H3C  C • + H3C  C • →
  
CH3 CH3 CH3 C2H5MgBr CH3
CH3 H+
CH3 CH3 OH
(b) CH3 CH  CH2Br   Acetophenone CH3
 H3C  C —— C  CH3
CH2Br  
(3-phenyl 3-butanol)
CH3 CH3
(c) CH3  CH CH2Br CH3
 Reactivity order of abstraction of H Cl
CH3 towards bromination of alkane as more HCl + Znl2 CH3
CH3 stable alkyl free radical is formed as Lucas reagent
 follows
(3-phenyl 3-chloro
(d) CH3 C  Br 3° H > 2° H > 1° H butane)
 Since, isobutane is in excess, so (Instant turbidity)
CH3 dibromination of single isobutane is not
favourable reaction. This make (a) and 09
Ans. (d) Br A
(b) incorrect options. CCI4 (Major product)
Excess of isobutane reacts withBr2 in CH3
presence of light at 125°C gives [2021, 17 March Shift-I]
08 Reaction of Grignard reagent,
2-bromo-2-methyl propane as major Product A is
product. C 2H5MgBr with C 8H8O followed by
Br
CH3 hydrolysis gives compound ‘A’
 Br2 which reacts instantly with Lucas
(a)
CH3  CH  CH3 → reagent to give compound B, CH3
hν / 125 ° C
Isobutane
(excess) CH3 C 10 H13Cl. Br CH
3
 The compound B is
H3C  C  CH3 [2021, 18 March Shift-I]
(b) CH3

Br Cl Br
2- bromo -2 - methyl propane

Mechanism The above reaction is CH3

(c)
halogenation of alkane via free radical
substitution reaction. CH3
(a) CH3
Initiation step
Br
CH3 CH3
Br2 →
hν
Br • + Br • (d)
Propagation step CH3
CH3
 (b) Ans. (d)
H3C  C  H + Br • → Cl
Alkene undergoes electrophilic addition
 CH3 with HBr to give a major product by
CH3 CH3 Cl Markownikoff rule by S N 1 mechanism.
 Step 1. Addition of electrophile to form
H3C  C • + HBr CH3
 (c) carbocation.
CH3
CH3 Cl CH3 HBr
 CCl4
H3C  C • + Br2 → Alkene 2° carbocation
 CH3
CH3 (d) 2° carbocation undergoes methyl shift
CH3
to form more stable 3° carbocation.

H3C  C  Br + Br • Ans. (c)
 Rearrangement
CH3 Reaction of Grignard reagent, C2H5MgBr
Termination step with C8H8O followed by hydrolysis gives (1, 2-methyl
Br • + Br • → Br2 compound A, which reacts instantly with shifting)

CH3 CH3 Lucas reagent to give compound B,

•
  C10H13Cl. It will show instant turbidity.
Br + H3C  C • → H3C  C  Br
  Step (i) C H O C 2 H 5 MgBr
→ (A) 3° carbocation
8 8
H+ Step 2. Attack of nucleophile on
CH3 CH3 Lucas reagent
(Major product)
Step (ii) (A)  → ( B) C10H13Cl carbocation.
298 JEE Main Chapterwise Topicwise Chemistry

Br CH3 H3C Cl
12 Identify A and B in the chemical
Br– CH3 (CH3)3CO K
– + 'B' reaction. [2021, 25 Feb Shift-I]
(Major product)
OCH3
Product (A)

Cl
The product A and B formed in HCl
[A]
Nal
[B]
10 Dry acetone
above reactions are (Major) (Major)
[2021, 16 March Shift-I]
′A′ CH2 CH2 NO2
OCH3 I
(a) A- B- Cl Cl
Cl
Identify the reagent(s) ‘A’ and (a) A= B=
condition(s) for the reaction: CH3 CH3
[2021, 16 March Shift-II]
NO2 NO2
(a) A = HCl, anhydrous AlCl3 (b) A- B-
(b) A = HCl, ZnCl2 OCH3 OCH3
(c) A = Cl2 , UV light Cl l
CH3 CH2
(d) A = Cl2 , dark, anhydrous AlCl3 (b) A= B=
Ans. (c)
The reaction can be achieved by Cl2 /UV (c) A- B-
NO2 NO2
light (A). Given, reaction follows free
radical substitution mechanism. OCH3 I
CH2 CH3
Cl
(c) A= B=
Cl2 (d) A- B-
UV light Cl Cl
Cyclohexene NO2 NO2
Cl Ans. (c)
1, 4-dichloro cyclohexene OCH3 OCH3
Alcohols undergo dehydration (removal
Mechanism of water molecule) in the presence of Cl
(I) Initiation : This involves formation protic acids (conc.H2SO4 ,H3PO4 ) at high
of radicals. (d) A= B=
temperature to give Saytzeff alkene
Cl2 light
UV
2Cl (more alkylated) as major product. Cl

CH3 NO2 NO2

(II) Propagation : Reactive free radicals H3C OH
react with stable molecules to form H Ans. (b)
new free radicals. 20% H3PO4/∆
E1 reaction OCH3 OCH3
Cl + + HCl Cl
1-methyl HCl
cyclohexanol
(More stable allylic Markownikoff's
free radical is formed) + addition
Cl
NO2 NO2
Major Saytzeff (B)
alkene (A) 4-methoxy- 3-chloro-4-
+ Cl— Cl + Cl (More alkylated) nitro-hex-2-ene methoxy nitrohexane
(A)
Bulky bases like tert-butoxide, due to OCH3
Similarly second Cl atom is also steric hindrance, a bulky base abstracts l
attached at allylic position. a less hindered proton, that leads to NaI
Cl Cl formation of the less substituted Dry acetone
product as, the major one, called the
Hofmann product. NO2
+ Cl2
Cl 3-iodo-4-methoxy nitro
hexane
(CH3)3CO– K+ (B)
Cl +
D Ist reaction is Markownikoff’s addition
11 H3C OH 1-chloro- Major Hofmann of HCl on double bond while 2nd
1-methyl cyclo alkene reaction is halide substitution by
20% H3PO4 'A' hexane Finkelstein reaction in which chlorine
(Major product)
358 K get displaced by iodine.
Organic Compounds Containing Halogens 299
CH3
13 The product formed in the first N Br
step of the reaction of (c) CH3 C CH CH3
Br (d)
CH3 I
CH3 CH2 CH CH2
(d) CH3 CH CH CH2 CH3 Ans. (b)
CH CH3 with excess
All given species in the question are
Br CH3 I
alkyl halide. They react with aqueous
Mg/Et2O (Et = C2H5) is Ans. (b) AgNO3 solution with different rate.
[2021, 24 Feb Shift-I] The major product formed is 2-iodo-2, Reaction undergoes as follows:
(a) CH3 CH2 CH CH2 CH CH3 3-dimethylbutane. Steps involved in the
reaction are as follows : → R + +
R  X + AgNO3 (aq) RDS AgX
Precipitate
CH3 CH CH2 CH Step 1 It is electrophilic addition
CH2 CH3 Hence, rate precipitate formation of
reaction, π-bond of alkene attack H+ ion
CH3 AgX depends on stability of carbocation
of HI and form more stable carbocation.
(b) CH3 CH (R + ) .
Step 2 Formation of more stable 3°
CH CH3 carbocation take place by 1, 2 shifting of In the given question all formed
(c) CH3 CH2 CH CH2 CH CH3 Me group. carbocation will be
Step 3 Direct addition of Is ion . r N
CH3 CH2 CH CH2 CH CH3 r
Mechanism
MgBr N
CH3
H I
(d) CH3 CH2 CH CH2 CH CH3 Electrophilic
CH3 CH3
addition
MgBr 3, 3-dimethylbut-1-ene OCH3
Ans. (d) CH3 (a) (b)
r
Here, in first step only one mole of CH3 CH3 N
Mg/ Et2O attacks on bromine and form 1° carbocation
two 2MgBr in the first step.
–
1,2-shifting of CH3 r
Br Br
O
CH3—CH2—CH —CH2—CH—CH3 CH3
(c) (d)
2, 4 dibromo hexane CH3
MgBr +I Among the above given option(s)
Mg (excess) CH3 CH3 carbocation (a) is most stable due to
(dry ether)
CH3— CH2—CH
CH3 3° carbocation r
CH2 CH3 (More stable)
CH3 I (Carbocation stable
by 6α-H)
N
BrMg—CH (Product)
2-iodo-2,3-dimethylbutane
stronger + M effect, so give
CH3
(Product)
On further moving in the reaction, two 15 Which of the following compounds precipitate with aqueous AgNO3
MgBr are eliminated to form alkene in will form the precipitate with solution most readily.
respective positions. aq. AgNO 3 solution most readily?
[2020, 4 Sep Shift-II] 16 Which of the following compounds
14 What is the major product formed Br
will show retention in
by HI on reaction with configuration on nucleophilic
CH3 CH N substitution by OH− ion?
C CH2 ? (a) [2020, 2 Sep Shift-I]
CH3 (a) CH3  CH  Br
CH3 [2021, 24 Feb Shift-I] 
Br
CH3 N C 6H5

(a) CH3 C CH CH2I (b) CH3 — CH — CH2Br

(b)

CH3 H C2H5
CH3 OCH3 (c) CH3  CH  Br
(b) CH3 (c) O Br

C CH CH3
CH3
I CH3
300 JEE Main Chapterwise Topicwise Chemistry

Br s A student writes general

RDS
 r OH
3° Br
OH
(d) CH3  C  H –Br fast characteristics based on the
 (t-BuBr) Carbocation given mechanism as :
C 6H13 intermediate (A) The reaction is favoured by
Ans. (b) Reaction (2) weak nucleophiles.
In (a) and (d), carbon atoms bearing the Rate = k [t-ByBr] [OH− ] , it is a second
(B) R ⊕ would be easily formed if
leaving group (Br atom) are chiral. So, (base) the substituents are bulky.
their configurational change will take order α, β-elimination reaction (E2 ), (C) The reaction is accompanied
because t-BuBr undergoes
place withOH− ion by S N 2 or S N 1 by recemisation.
dehydrohalogenation ( HBr) with a
pathway.
strong base (alcoholic or ethanolic OH− ) (D) The reaction is favoured by
Me Me to give an alkene. So, rate of the non-polar solvents.
* Br * Br reaction depends on concentrations of
Ph
Which observations are correct?
C6H13 substrate (t-ByBr) and base (OH/alc.). [2020, 3 Sep Shift-I]
So, option (a) is not correct.
In (c), (CH3)2 CH Br does not have any (a) (A) and (B) (b) (A) and (C)
È È
chiral centre. So, no comment on O R is a stronger base thanOH. So, use of (c) (A), (B) and (C) (d) (B) and (D)
configuration will arise with (c). È
Ans. (c)
OR will make theE2 reaction faster.
In option (b), theα-carbon (with respect ⊕ ⊕ YÈ
Hence, option (a) is also not correct. R  X → R X È → R||X È →
to CH2Br with whichS N 2 reaction will
take place) is only chiral. This α-carbon R Y + X È
18 The total number of
remains unaffected inS N 2 pathway. So, It indicates R ⊕ (carbocation) formation
monohalogenated organic
it will show retention in configuration. takes place and R ⊕ got stabilised by
products in the following (including electronic factors and polar solvent
17 Consider the reaction sequence stereoisomers) reaction is ...... molecules because solvent separation
given below : (i) H2 /Ni/∆ of R ⊕ is possible.
A   →
OH
(Simplest optically (ii) X 2 /∆ So, statement (D) is not correct.
Br OH + Br (1) active alkene)
H2 O Here, X È (leaving group) of R  X is
rate = k [t-BuBr] [2020, 3 Sep Shift-I]
substituted byY È, (nucleophile) via the
Ans. (8.00)
CH3 formation of carbocation (R ⊕)
(i) H 2 / Ni/ ∆ intermediate. So, it is anS N 1 reaction.
OH
+ HOH + Br CH3CH2  CH  CH == CH2 →
 ( ii) X 2 / ∆ S N 1 mechanism supports weaker
C2H5OH H 2C CH3 (2)
CH3 nucleophiles. So, statement (A) is
rate = k [t-BuBr] [OH] (A ) correct.
Which of the following (Simplest optically active alkene) S N 1 reaction is accompanied by
statements is true? inversion and retention in configuration,
X
[2020, 2 Sep Shift-II] i.e. racemisation provided ‘R’ of R  X is
X chiral. So, statement (C) is correct.
(a) Changing the base from OHÈ to * + * * +
È
OR will have no effect on Attachment of bulkier substituents or
reaction (2) (+ (+ 3°-nature of the carbon atom of CX
–) P –) ( +– ) Q
bond of R  X will favour formation of
(b) Changing the concentration of
base will have no effect on X R ⊕ (carbocation). So, statement (B) is
reaction (1) + also correct.
(c) Doubling the concentration of
base will double the rate of both X 20 The major product in the following
the reactions R S reaction is
(d) Changing the concentration of In the reaction, total number of I
base will have no effect on t-BuOH
monohalogenated products (including Heat
reaction (2)
stereoisomers)
Ans. (b)
P = 2, Q = 4, R = 1, S = 1, i.e. Total = 8 [2020, 3 Sep Shift-II]
Reaction (1)
Rate = k [t-BuBr], it is a first order 19 The mechanism of SN 1 reaction is O t-Bu
nucleophilic substitution reaction (S N 1),
given as : (a) (b)
so, rate of this reaction will depend only
on the concentration of the substrate, R  X → R ⊕ X È → R ⊕||X È
Ion pair Solvent
i.e. t-BuBr. Separated ion
pair (c) (d)
So, option (b) is correct, but option (c) is È
not correct. →
Y R Y +XÈ
Organic Compounds Containing Halogens 301

Ans. (b) Cl (a) CH3CH(Br)CH2CH(CH3)2

–Cl– (b) CH3CH2CH(Br)CH(CH3)2
Complete reaction is as follows :
AgNO3
(Polar protic (b) (c) Br(CH2 ) 3CH(CH3)2
I bond) OCH3 (d) CH3CH2CH2C(Br) (CH3)2
t-BuOH ⊕ 1, 2H (B) r
Ans. (d)
∆ Shift
H HBr
CH3  CH ==CH  CH  CH3 →
∆ ⊕ 
1, 2 H Shift OCH3
⊕ CH3
Aromatic and +M effect
H H
(ii)
⊕ 
(c) CH3  CH2  CH  C  CH3
− Cl− ⊕ 
More substituted CH3  CH  CH3 → CH3  CH  CH3 CH3
AgNO 3 (2°)
Alkene (major) |
Cl (iii)

The alkene formed is stable according (C)  1, 2 − H shift (for more stable carbon cation)
− − Cl ↓
to Saytzeff’s rule. It states that alkenes
(d) CH3  CH  CH2NO2 → ⊕
with less number of hydrogen on the  AgNO 3
CH3  CH2  CH2  C  CH3
double bonded carbon atoms are Cl 
⊕  Br s
preffered product. ( D) CH3  CH  CH2 NO2 ↓ CH3
(iv)
Br
21 The decreasing order of reactivity NO2 shows −M effect 
of the following organic molecules Stability of carbocation is (ii) > (i) > (iii) > CH3  CH2  CH2  C  CH3
towards AgNO 3 solution is 
(iv). CH3
[2020, 4 Sep Shift-I]
So, the reactivity order towards AgNO3 Major
Cl Cl solution is (B) > (A) > (C) > (D).
24 The increasing order of the boiling
(A) (B) 22 Among the following compounds, points of the major products A, B
OMe which one has the shortest C—Cl and C of the following reactions
(C) CH3 CHCH3 bond? [2020, 4 Sep Shift-II] will be [2020, 6 Sep Shift-II]

 Cl O

Cl (a) H3C—Cl (b) CH + HBr

(C6H5CO)2
I. A
(D) CH3 CHCH2 NO 2 CH2
 H3C II. + HBr B
HC Cl
Cl (c) H3C——Cl (d)
(a) (A) > (B) > (C) > (D) CH3 CH2 III. + HBr C
(b) (C) > (D) > (A) > (B)
(c) (B) > (A) > (C) > (D) Ans. (b) (a) II < III < I (b) III < I < II
(d) (A) > (B) > (D) > (C) In option (c) vinyl chloride, CCl bond is (c) I < II < III (d) I < III < II
Ans. (c) shortest due to resonance of lone pair Ans. (a)
General reaction : of  Cl (chlorine atom).
Complete reaction of I, II and III are as
AgNO3 + X (Halogen) → AgX + NO23– Due to resonance C  Cl bond aquire follow:
partial double bond character. O
It follows S N 1 reaction.
In S N 1 reaction, Hence, vinyl chloride have least C  Cl + HBr
(C6H5CO)2
(A )
Rate of reaction ∝ stability of bond length. Br
carbocation
Cl lone pair involved
+ HBr Br (B )
Cl in resonance
CH
Br
–Cl–
(a) CH2 + HBr (C )
AgNO3
(A) r
s 23 The major product formed in the RX are polar, therefore intermolecular
NO3 + AgCl forces of attraction (e.g., dipole-dipole
following reaction is
Aromatic and van der Waals’) are stronger in RX.
HBr
(i) CH3CH== CHCH(CH3 ) 2 → Hence, the boiling point of RX is greater
[2020, 5 Sep Shift-II] than those of hydrocarbons of
comparable molecular masses.
302 JEE Main Chapterwise Topicwise Chemistry

Branching decreases the surface area as in Ans. (d) Ans. (c)

alkane because the branched C chains are E 1 reaction proceeds via carbocation
CH3 CH2  CH2  Br
more spherical -like, which results in formation,therefore greater the
lower boiling point. CH3CH2CH2OCH2CH3 stability of carbocation faster is the
1 ks (Rate constant reaction. Carbocation formed by D,
B.P ∝ + CH3CH2O–
Branching Z –= (A) of substitution) (2°, resonance stabilised
–Br– ke (Rate constant the product is diene) is most stable
Hence, the boiling point of isomeric RX of elimination) followed by B, (1° and the
decreases with increase in branching, product formed is diene). Further
hence the order will be B < C < A. CH3CH=== CH2+CH3CH2OH
among C and A, the carbocation formed
25 1-methyl ethylene oxide when CH3
by C is more stable (2°) than A,
treated with an excess of HBr CH3
+ CH3CO– (1°). Thus, the reactivity
produces : [2020, 7 Jan Shift-I]
CH3 ks CH3CH2CH2OCCH3
towards dehydrohalogenation follows
Br the order :
Br CH3
(a) Br (b) Z – = (B)
–
D>B>C>A
Br – Br ke
CH3
CH3
Br 28 Which of the following reactions
(c)
Br
(d) CH3CH== CH2 + will not produce a racemic
CH3 CH3 product? [2020, 9 Jan Shift-II]
Ans. (a) CH3COH H3C
HCl
The given reaction is completed as (a)
CH3
follows :
H+ When alkyl halides react with CH3
CH3—CH—CH2
(From HBr) nucleophiles (Z − ), both substitution and
O
O elimination reactions can be expected.
1-methylethyleneoxide
CH3—CH—CH2
+
 HCN
1° alkyl halides generally favour (b) CH3 C CH2CH3 →
O
substitution, but stronger bases favour HBr
H elimination. So, in the above reactions (c) CH3CH2CH == CH2 →
Br in which (CH3  CH2  CH2 Br is 1° alkyl CH3
HBr Br– halide, CH3CH2 O− is a strong base), 
CH3—CH—CH2 HCl
reasonable amounts of substitution and (d) CH3  C CH == CH2 →
Br OH
elimination products can form between 
CH3—CH—CH2Br A = CH3CH2O− and alkyl halide. H
(Product) Ans. (d)
(A) is an unhindered nucleophile, so it
can give substitution better than (B) Reaction (d) will not produce a racemic
26 For the following reactions : which is hindered (more crowded or product whereas other reactions will
CH3CH2 sterically hindered). But (B) tends to give form racemic mixture.
ks
i t ut ion CH2Z+Br elimination better than (A) due to the CH3
S ubst same reason also.
CH3CH2CH2Br+Z
Elim k k CH3—C—CH==CH2
ina e ∴ µ = s is in the order A > B
tion ke
CH3CH==CH2 H
+HZ+Br CH3
and ke is in the order B > A.
where, H Cl
CH3 CH3—C—CH—CH3
27 The decreasing order of reactivity
Carbocation
rearrangement

Z =CH3CH2O (A) or H3C—C—O (B) H

towards dehydrohalogenation (E 1 )
CH3 reaction of the following CH3
k s and k e , are respectively the compounds is : [2020, 8 Jan Shift-I] Cl
CH3—C—CH2 —CH3
rate constants for substitution (A) Cl (B) Cl
k CH3
and elimination, and µ = s , the
ke (C) (D) CH3—C—CH2—CH3
correct option is ……… . Cl Cl
Cl
[2020, 7 Jan Shift-II]
(a) B > A > D > C There is no chiral carbon atom present
(a) µ B > µ A and k e (B) > k e (A) (b) B > D > A > C in the product.
(b) µ B > µ A and k e (A) > k e (B) (c) D > B > C > A ∴ Product would not be a racemic
(c) µ A > µ B and k e (A) > k e (B) (d) B > D > C > A mixture.
(d) µ A > µ B and k e (B) > k e (A)
Organic Compounds Containing Halogens 303

H3C H3C Similarly, The intermediate, I can be rearranged

HCl δ+ δ–
(a)
+
into the more stable form I′ (3°) by
·· H—Cl
H2N —CH —
— CH2 NH2—CH—CH3 α-hydride shift.
Cl
CH3 CH3
(+R) Cl I ′ will give the major product.
–
Product has a chiral carbon atom Cl
NH2 — CH — CH3 Me r s
α-H shift
(marked by a circle). Both enantiomers Fast C CHMe
are formed in the reaction equally. δ+ δ– Me
∴ It is a racemic mixture. H—Cl
CH3O —CH —
— CH2 CH3O H
O (+R)
– I
HCN + Cl
(b) CH3—C—CH2—CH3 —CH— CH3 CH3O — CH—CH3 (2° carbocation) Me r
Fast
C—CH2—Me
OH Cl Me
δ– δ+ I′ CH3OH –H
r
CH3—C—CH2—CH3 Cl — H (3° carbocation)

HCl Me
CN < CH —
F 3C — — CH2 Slow
F3C — CH2 C—CH2Me
Product has a chiral carbon atom (– I) – Cls
Me
(marked by the circle). Both s OCH3
r Cl
enantiomers are formed in the — CH2 Slow F3C — CH2CH2Cl (Major)
reaction equally.
∴ It is a racemic mixture.

(c) CH3— CH2— CH==CH2

HBr 30 The major product of the following 31 The major product Y in the
CH3—CH2—CH—CH3
reaction is following reaction is
CH3
Br  CH3 OH Cl
Product has a chiral carbon
atom (marked by the circle). CH3 C  CHCH3   → EtONa
X
HBr
Y
Heat
Both enantiomers are formed  
in equal amount.
∴ It is also a racemic mixture. H Br [2019, 10 April Shift-I] [2019, 10 April Shift-II]
CH3
29 Which one of the following alkenes  (a) Br (b) Br
(a) CH3 C == CHCH3
when treated with HCl yields
CH3
majorly an anti Markownikoff  (c) (d) HO
product? [2019, 8 April Shift-II] (b) CH3 C  CH == CH2 Br
(a) Cl CH == CH2  Ans. (b)
(b) H2N CH == CH2 H
CH3 The given reaction takes place as
(c) CH3O CH == CH2
(d) F3C CH == CH2  follows :
(c) CH3 C  CHCH3
Ans. (d)  Cl
Attachment of electron donating group ( OCH3 H β-H for EtONa/∆
+ R or + I) with sp2 -carbon of an CH3 Saytzeff β-elimination
unsymmetrical alkene supports elimination –HCl
 CH2
Markownikov’s addition rule through (d) CH3 C  CHCH3 H β-H for
electrophilic-addition-pathway. Hoffmann
  elimination
But, attachment of H OCH3
electron-withdrawing group Ans. (c) Markownikov’s
(− R or − I) for the same will follow centre for Brs
anti-Markownikov’s pathway (even in In the given question, the substrate is a +
absence of organic peroxide which 2°-halide (bromide) and the medium, 3-methyl but-2-ene 3-methyl-but-1-ene
favours free radical addition) through CH3OH (as well as a poor nucleophile) is major (X) minor
electrophilic addition pathway. protic in nature, So, the reaction will (Saytzeff product) (Hoffmann product)
follow mainly S N 1 pathways via the
The product formed by given alkenes
formation of a carbocation intermediate Electrophilic addition
when treated with HCl. HBr
(I). (Markownikov’s rule)
+R δ+ δ– Me Me r
H—Cl
–B r
Cl — CH — CH2 Br
Slow Me H
rds

Br +
H Br
r Cl – Me Me
Cl — CH — CH3 Me r CH 3OH 2-bromo-3-methyl 2-bromo-2-methyl
fast C CH r CH—CHMe butane (minor) butane (major) (Y)
Cl Me (2°) –H Fast Me
H (I) OCH3
(Minor)
Cl — CH — CH3
304 JEE Main Chapterwise Topicwise Chemistry

OH
32 The major product obtained in the Assertion (A) Vinyl halides do not
given reaction is undergo nucleophilic substitution
(a) Ph (b) Ph
CH3 O CH2 CH3 easily.
CH2 CH OH
Reason (R) Even though the
OH
Cl intermediate carbocation is
AlCl3
Product (c) Ph (d) Ph
stabilised by loosely held
[2019, 10 April Shift II]
π-electrons, the cleavage is
Ans. (c)
difficult because of strong
CH3 Heating of 2-chloro-1-phenylbutane bonding.
with EtOK/EtOH gives 1-phenyl
(a) CH3 O but-1-ene(X). Reaction of X with (a) Both (A) and (R) are wrong
Hg(OAc)2 /H2O followed by NaBH4 gives statements.
1-phenyl butan-1-ol (Y). Reaction (b) Both (A) and (R) are correct
involved is as follows : statements and (R) is correct
explanation of (A).
(b) H3C O CH Cl
CH2 –+
EtOK
(c) Both (A) and (R) are correct
CH statements but (R) is not the
Ph EtOH Ph
CH3 OH correct explanation of (A).
1. Hg (OAc)2,H2O (d) (A) is a correct statement but (R) is
(c) H3C O 2. NaBH4 a wrong statement.
Ph
(Y) Ans. (c)
Mechanism Vinyl halide (CH2 == CH  Cl) do not
CH3 Cl undergo nucleophilic substitution
s
OEt reactions. This is because it forms
(d) H3C O CH2
Ph dehydro- highly unstable carbocation
CH2 halogenation ⊕
CH CH2 H OAc (CH2 == CH). It cannot delocalise its
π-electron. In vinyl halide C—Cl bond
Ans. (c) + Hg OAc
Ph possess double bond character also.
The given reaction takes place as Oxymercuration s r
follows : CH2 CH Cl CH2 CH Cl
OAc
CH3 O
AlCl3 35 The major product of the following
Hg+
Cl – AlCl4s Ph reaction is
H
C H H3C
CH3 O
H H CH2 HCl
C2H5
r H2 O H
It will stabilise the
Intramolecular Ph CH CH Hg OAc
ArSE 2-reaction CH2 Cl
carbocation by
(+ve) hyperconjugation OH C2 H5 CH3
(a)
CH3 H H
O CH3
–HCl r s
–AlCl3 OAc
CH2 Cl
H Ph CH CH HgOAc (b)
CH3 O – H
AlCl4
OH C2H5 CH3
Demercuration NaBH4 CH3
(c)
CH3 Ph CH CH2 + AcO
s
H
Cl
33 Heating of 2-chloro-1-phenyl OH C2H5 (Y)
CH3
butane with EtOK/EtOH gives X as
34 An Assertion and a Reason are CH3
the major product. Reaction of X (d)
with Hg(OAc) 2 /H2O followed by given below. Choose the correct Cl
H
NaBH4 gives Y as the major answer from the following options. [ 2019, 12 Jan Shift-II]
[2019, 12 April Shift-II]
product. Y is [2019, 12 April Shift-II]
Organic Compounds Containing Halogens 305

Ans. (d) produced. As per the position of Cl in Ans. (b)

substrate, following 2 alkenes are Complete reaction can be represented
It is a simple case of Markownikoff
formed as product: as
addition. The reaction proceeds as :
(i) CH3CH2 C == CH2
CH3 Br
 + –
CH2 NaOMe
H+ COOCH2 CH3
MeOH
CH3
H (ii) CH3 CH ==C  CH3 H
+ CH3
+ NaBr + MeOH

COOCH2 CH3 Thus, the given reaction is
H dehydrohalogenation which is a
3° stable In accordance with Saytzeff rule
carbocation
β-elimination proceeding through E2
CH3 CH == C  CH3 mechanism.
Cl– 
COOCH2 CH3 Mechanism The reaction proceeds
CH3 through the formation of following
CH3 will be the major product.
transition state with simultaneous
Cl removal of Br and H atoms.
37 Which hydrogen in compound (E) is
H Na+ Na+Br–
easily replaceable during
The structure of options given may (Product)
bromination reaction in presence
BF
confuse an aspirant with ring expansion Br
of light?
BB
but that is seen as the minor product
Here, B B =
CH3 CH2 CH == CH2
B ond breakage
only [Due to the formation of a 3° stable BF
δ γ β α
BF =
carbocation in the process] the major BB B ond
– formation
(E)
(Product) H
product is (T ransition BF OMe
(a) β-hydrogen (b) δ-hydrogen
S tate)
CH3 MeOH (Product)
CH3 (c) γ-hydrogen (d) α-hydrogen
Cl [2019, 10 Jan Shift-I] 39 The increasing order of reactivity
H Ans. (c) of the following halides for the SN 1
The compound (E) has two reaction is
36 The major product of the following allyl-hydrogen atoms (γ). When E reacts I. CH3CH(Cl)CH2CH3
reaction is [2019, 12 Jan Shift-II] with Br2 /hν, it readily undergoes allylic
free radical substitution and forms 3, II. CH3CH2CH2Cl
CH2CH3 3-dibromobut-1-ene III. p -H3CO  C 6H4  CH2Cl
NaOEt δ γ β α Br2 / hν
H3C C Cl ∆ CH3  CH2  CH == CH2  →
[JEE Main 2017]

But-1-ene
–HBr (a) (III) < (II) < (I) (b) (II) < (I) < (III)
COOCH2CH3 Br (c) (I) < (III) < (II) (d) (II) < (III) < (I)
|
(a) CH3CH2C == CH2 C H3  CH  CH == CH2 Ans. (d)
δ γ β α
 3-bromo -but -1-ene (i) The rate of S N 1 reaction depends
CO2CH2CH3 only upon the concentration of
Br the alkyl halide.
(b) CO2CH2CH3 Br2 / hν|
  → CH3  Cγ  CH == C H2 (ii) S N 1 reaction proceeds through
–HBr δ | β α the formation of carbocation.
CH3C == CHCH3
Br The reactivity is decided by ease of
CH2CH3
3,3- dibromobut-1-ene dissociation of alkyl halide.
(c) H3C C OCH2CH3 R X - R ⊕ + XÈ
38 The major product of the following
reaction is [JEE Main 2018]
Higher the stability of R + (carbocation),
COOCH2CH3 higher would be the reactivity towards
OCH2CH3 Br
S N 1 reaction.
NaOMe
(d) H3C H2C C CO2CH2CH3 MeOH p -H3CO  C6H4  CH2 ⊕ is the most
stable carbocation due to resonance
CH3 OMe
and then CH3 CHCH2 CH3 (2° carbocation)
(a) (b) ⊕
Ans. (b) ⊕
Presence of strong base (EtO− ) and heat while CH3CH2 CH2 (1°) is least stable.
indicates elimination. OMe Thus, the correct increasing order of
Thus, the compound undergo (c) (d) the reactivity of the given halides
dehydrohalogenation and alkene is towards the SN 1 reaction is
306 JEE Main Chapterwise Topicwise Chemistry

CH3CH2 CH2 Cl < CH3 CHCH2 CH3 Ans. (d) III. C 2H5CH == C  CH3
|
Cl
The number of stereoisomers in 
(II) (I) molecules which are not divisible into CH3
two equal halves and have n number of
< p - CH3CO  C6H4  CH2 Cl asymmetric C-atoms = 2n . (a) Both I and III
(III)
3-methyl-pent-2-ene on reaction with
(b) Only III
40 Which of the following, upon HBr in presence of peroxide forms an (c) Both I and II
treatment with tert-BuONa addition product i.e. (d) All of the above
followed by addition of bromine 2-bromo-3-methyl pentane. It has two Ans. (d)
water, fails to decolourise the chiral centres. Therefore, 4 Strong nucleophile (OMe) in polar
colour of bromine ? [JEE Main 2017] stereoisomers are possible solvent (MeOH) gives elimination products
O C6H5 2 4 over substitution products but all
1 3 5 HBr products are possible in different yields.
(a) (b)
Peroxide Cl
Br Br 3-methylpent-2-ene
O Br – +
2 4 MeONa
O CH3—C—CH2CH2CH3
1 3 5
MeOH
(c) (d) OCH3
CH3
Br Br Anti-Markownikoff's addition
Ans. (a) Four stereoisomers are possible CH3—C—CH2—CH2—CH3 +
(As molecule has two chiral
To show decolourisation, compound centres and asymmetric). CH3
must be unsaturated. (Less yield)
42 The major product obtained in the CH3—C==CH—CH2CH3+CH2 ==C—CH2—CH2CH3
O
tert-BuONa
– +
following reaction is [JEE Main 2017]
O Br CH3 CH3
Br H tBuOK
C6H5 (More yield)
D
C6H5
O—tBu
(Saturated) (a) (± ) C6 H5CH(O tBu)CH2C6 H5 44 The synthesis of alkyl fluorides is
(cannot decolourise Br2 water)
(b) C6 H5CH == CHC6 H5 best accomplished by
C6H5 – + [JEE Main 2015]
tert–BuONa (c) (+ ) C 6H5CH(O tBu)CH2C6 H5
(a) free radical fluorination
Br C6H5 (d) (−)C6 H5CH(O tBu)CH2C6 H5
(b) Sandmeyer’s reaction
Ans. (b) (c) Finkelstein reaction
An alkyl halide in presence of a bulkier (d) Swarts reaction
(Unsaturated)
(decolourise Br2 water) base removes a proton from a carbon Ans. (d)
adjacent to the carbon bonded to the Alkyl fluorides can be prepared by
O – +
tert–BuONa halogen. This reaction is called E2 action of mercurous fluoride or
O ( β-elimination reaction). antimony trifluorides (inorganic
Br
Br fluorides) on corresponding alkyl halide.
H This reaction is known as Swarts
C6H5 t-BuO–K+
(Unsaturated) reaction.
O C6H5
(decolourise Br2 water)
H C6H5 H CH3Br + AgF → CH3F + AgBr
– + H C==C
tert–BuONa H C6H5 Methyl fluoride
O + tert-BuOH + Br– But, when action of NaI/acetone takes
Br
place on alkyl chloride or bromide, alkyl
43 2-chloro-2-methylpentane on iodide forms. This reaction is called
‘Finkelstein reaction’.
(Unsaturated)
reaction with sodium methoxide in
(decolourise Br2 water) methanol yields [JEE Main 2016] C2H5 Cl →
NaI
acetone
C2H5I + NaCl
CH3 Free radical fluorination is highly
41 3-methyl-pent-2-ene on reaction  explosive reaction. so not preferred for
with HBr in presence of peroxide I. C 2H5CH2 C  OC H3 the preparation of fluoride.
forms an addition product. The 
number of possible stereoisomers CH3 45 How many chiral compounds are
for the product is [JEE Main 2017]
II. C 2H5CH2 C == CH2 possible on monochlorination of
(a) six (b) zero  2-methyl butane? [AIEEE 2012]
(c) two (d) four CH3 (a) 8 (b) 2 (c) 4 (d) 6
Organic Compounds Containing Halogens 307

Ans. (b) The correct order of SN 1 reactivity 49 Which of the following reactions
2−methylbutane an monochlorination is will yield 2, 2-dibromopropane?
gives 4 isomers, among which I and III (a) (B) > (C) > (A) (b) (B) > (A) > (C) [AIEEE 2007]
are chiral in nature. (c) (C) > (B) > (A) (d) (A) > (B) > (C) (a) CH3  C ≡≡ CH + 2HBr →
*
CH3  CH2  CH  CH3 → 2 Cl Ans. (a) (b) CH3CH == CHBr + HBr →
 The reactivity ofS N 1 reaction depends (c) CH ≡≡ CH + 2HBr →
CH3 Cl upon the stability of the intermediate, (d) CH3  CH == CH2 + HBr →
 carbocation formed during these
*
CH3CH2 — CH— CH2 Cl + CH3CH2  C  CH3 Ans. (d)
 reactions. The stabiliIty order of the (a) CH3  C ≡≡ CH + HBr

CH3 CH 3 carbocation formed from the given → CH3  C == CH2
(I) (II) species is |
Br
Cl Me Me
 > H +
+ Me + ↓
+ CH3 — CH —CH —CH3 + CH2 CH2  CH  CH3
*    Allylic carbocation 2°carbocation Rearrangement +
CH3 Cl CH3 (stabilises through (stabilises by ← H3C  CH  CH2
(III) (IV) resonance due to hyperconjugation
(Hydride transfer)

conjugution) due to 6 α-H atoms) Br
+ Br
Hence, 2 chiral compounds are formed CH2  Br − +
in the above reaction. > CH3  C  CH3 ← CH3  C  CH3
Me +
 
1°carbocation Br Br
46 Which branched chain isomer of (stablises by hyperconjugation 2, 2-dibromopropane More stable
the hydrocarbon with molecular due to 2 α-H-atoms) carbocation
mass 72 u gives only one isomer of Hence, the reactivity order of the given (b) CH3CH == CHBr →HBr

mono substituted alkyl halide? bromide towardsS N 1 reaction is CH3CH2 CHBr2

[AIEEE 2012] 2 HBr
Me Me (c) CH ≡≡ CH → CH3CHBr2
(a) Tertiary butyl chloride >
Me
(b) Neopentane (d) CH3  CH == CH2 →
HBr
CH3
(c) Isohexane Br Br CHBrCH3
(B) (C)
(d) Neohexane
Ans. (b) > Me Br 50 HBr reacts with CH2 ==CHOCH3
Molar mass = 72 = CnH2 n + 2 (A)
under anhydrous conditions at
= 12 n + (2 n + 2) room temperature to give
n= 5 48 The organic chloro compound,
(a) CH3CHO and CH3Br [AIEEE 2006]
Thus, hydrocarbon is C5H12 . which shows complete
stereochemical inversion during (b) BrCH2CHO and CH3OH
Since, it gives only single C5H11Cl, This
an SN 2 reaction is (c) BrCH2 CH2 OCH3
suggests that C5H12 is symmetrical.
Hence, it is containing all 12 equivalent [AIEEE 2008] (d) H3C CHBr OCH3
H-atoms. (a) (C2H5 )2 CHCl (b) (CH3) 3 CCl Ans. (d)
CH3 (c) (CH3)2 CHCl (d) CH3Cl HBr
 Cl2 CH2 == CH OCH3 →
H3C  C  CH3 → Ans. (d)
 ∆ CH3  CH OCH3
CH3 Nucleophilic substitution bimolecular 
CH3 Br
(S N 2) prefers less sterically hindered
 First protonation occurs, two possible
H3C  C  CH2 Cl + HCl site to attack. Lesser the steric
intermediates are
 hindrance faster theS N 2 reaction. So
C H3 → CH → OCH3
CH3 ease of reaction is 1° > 2° > 3°. +

H H H (I)
47 Consider the following bromides,
Nu (−I effect destabilises carbocation)
(A) Me Br H Nu +
Cl H and CH3  CH  O CH3
H H • •
Me (II)
(C) Me (+ M effect stabilises carbocation)
S N 2 involves inversion of configuration
Br stereo, chemically. II, is more favourable. Hence,Brs
attacks and product is
Me Since, 1° alkyl halides are prone toS N 2 CH3  CH O  CH3
(B) reactions, therefore CH3Cl undergoes 
complete strerochemical inversion. Br
Br [AIEEE 2010]
308 JEE Main Chapterwise Topicwise Chemistry

O Br Ans. (b)
51 trans-2-phenyl-1-bromocyclopentane
on reaction with alcoholic KOH Cl (i) NaOH
(ii) dil. HNO3
produces [AIEEE 2006] (a)
(iii) AgNO3
CH2I
(a) 4-phenylcyclopentene IV
O Cl
(b) 2-phenylcyclopentene + AgI
(c) 1-phenylcyclopentene (yellow
(b) CHO ppt.)
(d) 3-phenylcyclopentene
Ans. (b) Br O Cl Cl
NaOH
H CH2I CH2 OH+NaI
HO (c)
Alc.KOH
H Ph Ph This compound halide will only give
E2
Br yellow ppt. as benzyl carbocation
H anti-elimination O
formed shown below is highly stable by
Br H H conjugation.
3-phenylcyclopentene (d) Cl
Br
Anti-elimination, means —H and the —Br
both departing group must be present Ans. (c) CH2
at dihedral angle of 180° (anti). In presence of Lewis acid, electrophilic Benzyl carbocation
halogenation reaction Other compounds halide cannot be
takes place at meta position to give removed because their corresponding
carbocation is highly unstable.
52 CH3Br + Nu − → CH3 Nu + Br − O
OH OH
The decreasing order of the rate
of the above reaction with
55
nucleophile (Nu – ) A and D is Br
[Nu = (A) PhO– ,(B)AcO − , (C)HO − , as follows
O Br
(D)CH3O– ] [AIEEE 2006] (Major product)
(a) D > C > A > B (b) D > C > B > A Br2
(c) A > B > C > D (d) B > D > C > A
The given reaction can occur in
AIBr3/(C2H5)2O
the presence of
Ans. (a) O
(A) bromine water
Nucleophilicity order is
s s (B) Br 2 in CS 2, 273 K
CH3 O>H O>
(D) (C)
(C) Br 2 /FeBr 3
+ I effect s O Br (D) Br 2 in CHCl 3 , 273 K
O
s (A) Choose the correct answer from
> CH3 C O (Major product)
(B)
the options given below
[2021, 22 July Shift-I]
(A) Negative charge
comparatively 54 Among the following compounds (a) (B) and (D) only
Negative charge
stabilised by
stable than I-IV, which one forms a yellow (b) (A) and (C) only
phenoxide ion
resonance precipitate on reacting (c) (B), (C) and (D) only
sequentially with (d) (A), (B) and (D) only
(i) NaOH (ii) dil. HNO 3 Ans. (c)
TOPIC 2
(iii) AgNO 3 ? [2021, 26 Aug Shift-I] Only bromine water gives tribromo
Haloarenes products, while all other gives
Cl Cl monobromo products in which para
O bromo is major product.
53
H3C OH OH
Br2 I II
CH3 Br Br
AIBr3/(C2H5)2O
'A' Br Cl + Br2/water
(Major product)
CH3 CH2I Phenol
Consider the given reaction, the III IV Br
product A is [2021, 26 Aug Shift-II] (a) II (b) IV (c) I (d) III 2,4,6-tribromophenol
(Major product)
Organic Compounds Containing Halogens 309

When phenol reacts with bromine in the H Cl

presence ofCS2 , FeBr3, CHCl 30, it results
in the formation of two products. The O—CH3
623 K
products is ortho bromophenol and + NaOH
300 atm
para bromophenol. The major product I
of this reaction is p-bromophenol SN2 Chlorobenzene ONa+
because no steric hindrance is present OH
at para position. (Dow process)
OH
+ CH3—I Sodium phenoxide

273K Methyl
+ Br2 in CS2 1-naphthanol iodide Nucleophilic substitution is not
or Br2 / FeBr3 preferred in aromatic compounds. So,
Phenol to do such reactions high temperature
or Br2/CHCl3
57 Which of the following reaction is and pressure are required.
OH OH
an example of ammonolysis?
Br [2021, 17 March Shift-I]
59 Match List-I with List-II.
+
(a) C 6H5COCl + C 6H5NH2 → List-I
C 6H5CONHC 6H5 Cl
(Minor
Br +
product) [H] N2Cl–
(Major product)
o-bromophenol p-bromophenol
(b) C 6H5CH2CN → C 6H5CH2CH2NH2 Cu2Cl2
+ A. + N2
HCl −
(c) C 6H5NH2 → C 6H5 NH3Cl
56 Main products formed during a
(d) C 6H5CH2Cl + NH3 → C 6H5CH2NH2 Cl
reaction of 1-methoxy naphthalene
Ans. (d) +
N2Cl–
with hydroiodic acid are
[2021, 18 March Shift-II] Reaction of alkyl halide with ammonia is Cu,HCl
B. + N2
I called ammonolysis reaction.
NH
C6H5 CH2 Cl  3→ C6H5 CH2NH2
C. 2CH3CH2Cl + 2Na →
and CH3OH Ether
(a) Carbon-halogen bond in alkyl or benzyl
halides can be easily cleaved by a
OH nucleophile. Hence, an alkyl or benzyl C 2H5 C 2H5 + 2NaCl
halide on reaction with an ethanolic Ether
solution of ammonia undergoes
D. 2C 6H5Cl + 2Na →
and CH3I nucleophilic substitution reaction in
(b) C 6H5 C 6H5 + 2NaCl
which the halogen atom is replaced by
an amino (NH2 ) group. List-II
OH
This process of cleavage of the CX (i) Wurtz reaction
bond by ammonia molecule is known as (ii) Sandmeyer reaction
(c) and CH3OH ammonolysis.
(iii) Fittig reaction
I 58 Cl O–Na+ (iv) Gattermann reaction
Choose the correct answer from
(d) and CH3I + NaOH the options given below.
[2021, 26 Feb Shift-II]
A B C D
Ans. (b) The above reaction requires
(a) (iii) (i) (iv) (ii)
Given reaction is completed via SN2 which of the following reaction
(b) (ii) (i) (iv) (iii)
mechanism. Methyl of methoxy group conditions? [2021, 17 March Shift-I]
will be substituted by (c) (ii) (iv) (i) (iii)
(a) 573 K, Cu, 300 atm
H + ion to give OH(hydroxy group) as (b) 623 K, Cu, 300 atm
(d) (iii) (iv) (i) (ii)
follows Ans. (c)
(c) 573 K, 300 atm
Mechanism Benzene diazonium chloride undergoes
(d) 623 K, 300 atm
Ans. (d) Sandmeyer reaction in presence of
O—CH3 Cu2 Cl2 while undergoes Gattermann
When chlorobenzene is treated with reaction in presence of Cu/HCl to give
H+I– NaOH at 623 K and 300 atm sodium chlorobenzene along with nitrogen gas
phenoxide is formed by nucleophilic (N2 ).
1-methoxy substitution.
naphthalene
310 JEE Main Chapterwise Topicwise Chemistry

N2Cl Br CH3 61 The decreasing order of reactivity

CH CH2CH3
of the following compounds
towards nucleophilic substitution
Benzene (SN 2) is
diazonium Cu2Cl2 (c) (d)
chloride CH2Cl CH2Cl
–N2 CN Br CN
Cl NO2
(Sandmeyer reaction) (I) (II)
+ N2
Ans. (c)
When 3-ethyl benzonitrile undergoes NO2
Chlorobenzene photochemical reaction (UV) with
bromine (1 equivalent), we get a CH2Cl CH2Cl
Cu, HCl
monobrominated product 1 bromo -1 (3 -
(Gattermann reaction)
cyanophenyl) ethane (A) as the major
So, (A) - (ii) Sandmeyer reaction product. (III) (IV)
(B) - (iv) Gattermann reaction NO2 O2N NO2
CH2—CH3
(C) Ethyl chloride reacts with sodium in NO2
presence of dry ether to give n-butane. Br2 (1 eqi.)
This reaction is known as Wurtz UV light [2020, 3 Sep Shift-II]
reaction. CN –HBr
(a) (II) > (III) > (IV) > (I)
Ether 3-ethyl benzonitrile (b) (IV) > (II) > (III) > (I)
2CH3CH2 Cl + 2Na →
Ethyl chloride Br (c) (III) > (II) > (IV) > (I)
[Aliphatic 1° -halide] CH—CH3
(d) (II) > (III) > (I) > (IV)
CH3CH2  CH2 CH3 + 2NaCl Ans. (a)
n - butane
CN Rate of S N 2 reaction
It is Wurtz reaction in which an aliphatic 1
1° or 2° halides produces a symmetrical (A) ∝
1-bromo-1 (3-cyanophenyl) Stability of carbocation
alkane like n-butane. ethane (Major)
1
(D) Chlorobenzene reacts with sodium in Stability of carbocation ∝
presence of dry ether to give biphenyl. The reaction follows benzylic free −I / − M
This is known as Fittig reaction. radical substitution mechanism which (effective group)
has a 2° benzylic free radical
Cl
intermediate (stable due to resonance δ+ δ+
2 + 2Na Ether CH2 Cl CH2Cl
with the benzene ring).
(i) Initiation step In this step radicals NO2
Chlorobenzene + 2NaCl are generated via homolytic
fission of covalent bond.
[Biphenyl]
UV NO2
It is Fittig reaction in which a Br—Br Br + Br –I-effect –M-effect
halobenzene (ii) Propagation step 3-methyl (I) –I-effect
produces biphenyl. benzonitrile reacts with bromine (II)
radical to give (Distance dominating)
So, C - (i) Wurtz reaction
1-bromo-1-(3-cyanophenyl) ethane
D - (iii) Fittig reaction
along withH• . δ+ δ+
So, correct match is A-(ii), B-(iv), C-(i)
CH2Cl CH2Cl
and D-(iii). —CH—CH3 + Br

60 For the given reaction, H

Benzylic carbon
CH2CH3 CN
A —CH—CH3 + H NO2 NO2 NO2
Br2
(Major product) NO2
UV light Br –I-effect
monobrominated (IV)
–M-effect
• •
(iii) Termination stepH and Br –I-effect
CN reacts to form HBr. (III)
What is A? [2021, 26 Feb Shift-I] H • + Br • → HBr
So, the decreasing order of reactivity of
CH2CH3 CH2CH3
—CH—CH3 the given compounds towardS N 2
Br Intermediate :
2° benzylic
reaction is
(a) (b) free radical (II) > (III) > (IV) > (I).
CN CN CN

Br
Organic Compounds Containing Halogens 311

62 In the following reaction Anhyd. AlCl3 Ans. (b)

(B) + Cl2 (excess)
sequence, [C] is dark Friedel-Crafts reaction is an
Cl Cl electrophilic substitution reaction. In
NH2
general, the rate of these reactions
Cl Cl is highest when benzene have
(i) NaNO2 + HCl, 0-5°C Cl
[A] 2 [B] some electron releasing groups, (i.e.
(ii) Cu2Cl2 + HCl hν
Cl Cl NH2 , OH) attached to the
Na+dry ether nucleus.
CH3 [ C] Anhyd. AlCl3
(C) + CH2== CH—Cl NH2 OH
(Major
product)
—CH==CH2
••
[2020, 4 Sep Shift-II] But in and , NH2 and
(D) + CH2 == CH—CH2Cl ••
(a) Cl CH2CH2 —Cl  OH groups are deactivated because the
••
Anhyd. AlCl3
—CH2—CH==CH2 Lewis acid (anhydrous AlCl 3)
used in these reactions form an adduct
(b) CH3  CH3 Which of these reactions are with the ‘NH2 ’ or OH’ groups and
possible? [2020, 7 Jan Shift-II] becomes ineffective.
(a) (B) and (D) (b) (A) and (D) O
(c) Cl CH2 CH2Cl (c) (B), (C) and (D) (d) (A) and (B) ||
‘ C NH2 ’ is a electron withdrawing
Ans. (a)
(deactivating) group.
(A) and (C) are not possible : Aryl halides
(d) CH2   CH2 and vinyl halides in the presence of CONH2

Cl Cl anhyd. AlCl 3 do not act as electrophiles

to give Friedel-Crafts reaction with ∴ is not highly reactive. ‘Cl’
Ans. (a) benzene. Therefore, these reactions are
not possible. Cl
N2Cl–
r
NH2
Anhyd. AlCl3
(B) +Cl2 (excess) in is weakly electron
NaNO2 + HCl, 0-5°C Dark
Cl
Cu2Cl2, (Diazotisation
reaction) Cl Cl withdrawing (deactivating) group, but
among the given options, it is most
CH3 CH3 reactive towards Friedel-Crafts
(A) Cl Cl
reaction.
Cl
Cl Cl (This reaction is possible)
65 The major product of the following
Cu2Cl2 (D) + CH2==CH—CH2—Cl reaction is
(Allyl halide : easily form CH3
electrophile with AlCl3 and
CH2Cl CH3 can react with benzene to give (1) Cl2/hν
,
(B) Friedel-Craft s reaction) (2) H2O, ∆
Cl 2 Anhyd. AlCl3
(Wurtz reaction) CH2—CH==CH2 Cl
hν
Na/ether (This is also possible) [2019, 8 April Shift-II]

CHCl2 CO2H
Cl 64 Which of these will produce the
CH2 CH2 Cl
highest yield in Friedel-Crafts (a) (b)
(C)
(Final product) reaction? [2020, 9 Jan Shift-I]

NH2 Cl
Cl Cl
63 Consider the following reactions :
(a) (b) CH2 OH CHO
Anhyd. AlCl3
(A) + —Cl
CONH2 (c) (d)
OH
—
(c) (d) Cl Cl
312 JEE Main Chapterwise Topicwise Chemistry

CH3
(c)
Ans. (d) (d)
CH3 n
n

OH
Cl OH
hν/benzylic free radical
Ans. (b)
substitution with Cl2 In presence of alc. KOH, the given halide undergoes
Cl2(1 eqv.) Cl2(2 eqv.) Cl2(excess) elimination reaction.
–HCl –2HCl –3HCl
Alc. KOH

CH2Cl CHCl2 CCl3 Cl

Cl Cl
The alkene produced undergoes polymerisation via free
Cl Cl Cl radical mechanism. This process involve three steps, i.e.
s s
s s
–Cl OH(Cl) –2HCl 2H2O/∆
–3H –3OH(aq) initiation, propagation and termination.

OH
Polymerisation n
OH
CH2OH CH C OH
O—H
Cl Cl
OH Polymer
Cl Cl Cl
(Option-c) Gem-diol
(unstable)
–H2O
OH 67 Increasing rate of SN 1 reaction in the following
compounds is [2019, 10 April Shift-I]
–H2O C O
I
I
CH O MeO
Cl
– (B)
COO (A)
Cl as
(Option-d) I
Cl I
in basic medium (D)
(C)
H3O r
H3CO
H3C
COOH
(a) (A) < (B) < (C) < (D) (b) (B) < (A) < (C) < (D)
(c) (A) < (B) < (D) < (C) (d) (B) < (A) < (D) < (C)
Cl Ans. (b)
(Option-b)
More stable the carbocation intermediate, higher will be the rate
So, considering the second reaction condition, Cl − , H2O, ∆ in the of S N 1 reaction.
statement of the question, the correct answer is option (d). The reaction involving carbocation intermediate formation
for the given compounds are as follows:
66 The major product of the following reaction is CH3 Three positive
I hyperconjugation
1. KOH (alc.)
r
2°-benzyl carbocation
–I s Þ Stable
Cl 2. Free radical rds
polymerisation
Cl
[2019, 9 April Shift-I] (A)
+R
CH3 (AN)

(a) (b) I
CH3
MeO
n n –I
s
rds
MeO r ⇒ Less
stable
(B)
Cl –I effect
from m-position
Cl (BN)
Organic Compounds Containing Halogens 313
I OEt Ans. (c)
* Br
–I
s * The mechanism of the given reaction is
rds as follows:
H3C Racemised ± as well as
(C) CH3 inverted (+ and –) it is electrophilic
r ⇒ More stable ⊕ y
substitution (Ar SE2):
[CH2==OH]Cl , Haloformylation
69 The major product of the following
–HCl
H3C reaction is [CH2==O + H Cl]
CH2 OH
Additional
three hyperconjugation
(C ′) (i) KOH (aq.)
Br
(ii) CrO3/H+ HCl
I –H2O
(iii) H2SO4/∆ (SN1)
Br SN2
s Ag CN
CH2Cl
–I
(D )
O O
rds More covalent
CH3O (Ag—C≡≡N )
CH3 (a) (b) –AgCl ( A)
(Benzyl chloride)
r ⇒ Highly Br
stable HO CH2CN CH2NC
O +
O
CH3O
(c) (d) (Minor) B (Major)
Additional +R effect from (Benzyl
p-position (DN) isocyanide)
HO
Stability of intermediates will follow the Br Thus, both benzyl cyanide and benzyl
order [2019, 9 Jan Shift-I]
isocyanide are the products of reaction
B′ > A′ > C′ > D′ Ans. (a) but benzyl isocyanide being the major
(–I) (–HPC=3) (+HPC=6)
( +HPC=3
+R=1 ( Key Idea The reaction involves product gives the correct option as (c).
hydrolysis or nucleophilic substitution in
So, the rate of S N 1 reaction with the
first step followed by oxidation and 71 Which of the following compounds
given compounds will be, B < A < C < D
dehydration in last step. The most
will produce a precipitate with
68 The major product of the following important fact is that, the Br group
attached directly to aromatic ring will AgNO 3 ? [2019, 11 Jan Shift-II]
reaction is not undergo substitution in step (i) Br
(i) Br2 Br
The road map of the given reaction is as
(ii) EtOH follows: (a) (b)
Br OEt
N
OEt aq. KOH CrO3/H+ Br Br
Br OH
(a) (b) SN2

Br Br (c) (d)
OEt OEt
It is aryl halide, remains unaffected
OEt Br under ordinary SN2 reaction conditions
(c) (d) Ans. (a)
O
Only ionic halides (X − ) give precipitate of
[2019, 9 Jan Shift-I] O
H OH H2SO4/∆ AgX with AgNO3 solution. So, an organic
Ans. (d) –H2O bromide able to produce R ⊕ (stable
The road map of the given reaction is : Br
(Intramolecular carbocation) and Br − in aqueous
dehydration) Br
Isolated C=C solution will give precipitate of AgBr
Br2 /CCl4 with AgNO3.
Anti-addition (electrophilic)
of Br2 with the isolated
70 The compounds A and B in the (+ R-effect)
(non-aromatic) C==C following reaction are, respectively (a) —Br + Br
Br HCHO+HCl AgCN
Br
*
A B (Bond energy Unstable
also increases) (Aryl carbocation)
*
(a) A = Benzyl alcohol,
EtOH (Polar protic
B = Benzyl isocyanide (b) —Br + Br
medium as well
–
SN1,–Br as nucleophile) (b) A = Benzyl alcohol, Stable carbocation
B = Benzyl cyanide (Aromatic, 6π system)
2°-benzyl (c) A = Benzyl chloride,
carbocation
(Stable) B = Benzyl isocyanide (c) —Br + Br
⊕
EtOH Br (d) A = Benzyl chloride, (Unstable carbocation)
–H
⊕
* B = Benzyl cyanide
[2019, 9 Jan Shift-I]
314 JEE Main Chapterwise Topicwise Chemistry

(+R-effect) SN2 Reaction

(d) —Br + Br 74 A solution of
(Zeisel’s Method)
N N (–l )-chloro-1-phenylethane in
Unstable CH3Br + HO CH CH2 CH3 toluene racemises slowly in the
(Aryl carbocation)
Br presence of a small amount of
Br Product SbCl 5 , due to the formation of
Here, BB = Bond breakage [JEE Main 2013]
So, only produces a BF = Bond formation (a) carbanion (b) carbene
(c) carbocation (d) free radical
precipitate of AgBr with AgNO3 solution. 73 Compound (A),C 8H9 Br gives a white Ans. (c)
precipitate when warmed with The given compound, (−l )−
72 The major product in the following alcoholic AgNO 3 . Oxidation of (A) chloro-1-phenylethane in the presence
conversion is [2019, 12 Jan Shift-II] gives an acid (B),C 8H6O 4 . (B) easily of SbCl 5 forms a carbocation.
SbCl
forms anyhydride on heating. Cl  CH  CH3 → 5
CH3O CH CH CH3 Toluene
Identify the compound (A). 
HBr (excess)
? [JEE Main 2013] Ph
Heat
+
CH2Br C2H5 [Ph  CH  CH3] SbCl −6
(a) CH3O CH CH2 CH3 (a) (b)
Since, the carbocation is a planar
Br
Br species, therefore it can be attacked by
CH3 SbCl −6 either from the front or back side
(b) HO CH2 CH CH3 CH2Br of the carbocation with equal ease. As a
CHB2r result, 50 : 50 mixture of two
Br (c) (d) enantiomers of
CH3 1−chloro−1 −pheynylethane undergoes
(c) CH3O CH2 CH CH3 racemization due to the formation of a
CH3
carbocation intermediate.
Br +
[Ph  CH  CH3] SbCl 6− →
(d) HO CH CH2 CH3 Ans. (d)
Ph  CH  CH3 + SbCl 5
Br
Compound A gives a precipitate with 
alcoholic AgNO3 (here white is Cl
Ans. (d) misprinting because the colour of ppt is [ d and l forms]
Key Idea The excess of HBr and high light yellow), so it must contains Br in
temperature in given reaction serves side chain. On oxidation, it gives C8H6O4 , 75 The structure of the major product
for dual purpose : which shows the presence of two alkyl formed in the following reaction is
(i) Hydrolysis of ether via SN2 chains attached directly with the
mechanism, benzene nucleus.
i.e. Zeisel’s method. Since, compound B gives anhydride on NaCN
(ii) Markownikoff addition at double heating, the two alkyl substituent must DMF
bond of the branch. occupy adjacent (1, 2) position. [AIEEE 2006]
Thus, A must be
The road map of complete reaction is as CN
CH2Br (a)
follows:
CH3
CH3 O CH CH CH3
and the reactions are as follows CN
H+ HBr excess/Heat CH2Br
Alcoholic Cl
+
(b)
AgNO3
CH3 O CH CH2 CH3 CH3 NC
Br– CH2 OR
+ AgBr Cl
CH3 O CH CH2 CH3 CH3 (c)

Br (A)
Oxidation
Br– H+ O CN
H COOH
∆
d– BF d+ BB d–
O CN
Br C O CH CH2 CH3 -H2O (d)
BF
COOH
H H H d+ Br (B) O
Transition state Phthalic anhydride
I
Organic Compounds Containing Halogens 315

Ans. (d) presence of concentrated B gave a yellow precipitate. Which

sulphuric acid is [AIEEE 2004] one of the following statements is
Cl NaCN
(a) gammexane true for this experiment?
DMF
(b) DDT [AIEEE 2003]
(c) freon (a) A was C 6H5I
CN
I (d) hexachloroethane (b) A was C 6H5CH2I
Ans. (b) (c) B was C 6H5 I
(d) Addition of HNO 3 was unnecessary
I
CCl3CHO + 2 Cl Ans. (a)
Chloride present on 1° aliphatic carbon Chloral In tube A
can be substituted easier than iodide Chlorobenzene
NaOH
because I is attached to benzene ring. C6H5I → No reaction (QpH –I
Conc×H2SO4 boil
Lone pair of e − of I is involved in DDT does not break)
delocalisation with π − e − of benzene. (i) Dil. HNO 3
→ No
Cl
77 Bottles containing C 6H5I and (ii) AgNO 3 yellow ppt. of AgI
C 6H5CH2I lost their original labels. In tube B
They were labelled A and B for NaOH , boil (i) Dil. HNO 3

testing . A and B were separately C6H5 CH2I → NaI →

− C 6H 5 CH 2 OH (ii) AgNO 3
– I taken in test tubes and boiled with
AgI
Hence,I is difficult to substitue. NaOH solution. The end solution in yellow ppt.

each tube was made acidic with ↓
76 The compound formed on heating dilute HNO 3 and then some AgNO 3 (PhCH 2I bonds breaks)
chlorobenzene with chloral in the solution was added. Substance B Thus, A was C6H5I.
25
Organic Compounds
Containing Oxygen
TOPIC 1 02 The major product formed in the following reaction is
Alcohols and Phenols CH3
Conc.H2SO4
CH3—C—CH—CH3 Major product
a few drops
01 Given below are two statements.
One is labelled as Assertion (A) and the other is labelled CH3 OH
[2021, 31 Aug Shift-I]
as Reason (R). CH3 CH3
Assertion (A) Treatment of bromine water with (a) CH3C CHCH2CH3 (b)
propene yields 1-bromopropan-2-ol. CH3 H3C CH3
Reason (R) Attack of water on bromonium ion follows CH3
Markownikoff rule and results in 1-bromopropan-2-ol. CH3
(c) C CH—CH3 (d) CH3CCH CH2
In the light of the above statements, choose the most CH3
CH3
appropriate answer from the options given below.
[2021, 31 Aug Shift-I] Ans. (b)
(a) Both (A) and (R) are true but (R) is not the correct explanation 3,3-dimethylbutan-2-ol reacts with concentratedH2SO4 to form
of (A). but-2,3-diene.
(b) (A) is false but (R) is true. CH3 CH3
(c) Both (A) and (R) are true and (R) is the correct explanation of (A).
Conc. H2SO4 –H2O
(d) (A) is true but (R) is false H3C—C——CH—CH3 H3C—C——CH—CH3
Ans. (c) CH3 OH H+ CH3 OH2
Propene reacts with bromine water to yield 1-bromopropan-2-ol. CH3
–H
+ ⊕ Rearrangement ⊕
Br—Br H3C—C——CH—CH3 H3C—C—CH—CH3
CH3—CH==CH2 CH3—CH—CH2 of carbocation
Propene CH3 CH3 [1,2-methyl shift] CH3
Br
H 3C CH3
Markownikoff¢s O CH3
H 3C
addition
H H H Buta-2,3-diene
+ (Major product)
–H
CH3—C — CH2 CH3—CH—CH2
Hence, correct option is (b).
OH Br O Br
1-bromo propan-2-ol
H H 03 The major product of the following reaction, if it occurs
Markownikoff’s rule states that in an unsymmetrical alkene the by SN 2 mechanism is [2021, 27 Aug Shift-II]
electron rich nucleophile adds to the C-atom with lesser number OH
of hydrogen.
Hence, both A and R are true and R is the correct explanation of A. +  K2CO3
Br Acetone
Hence, correct option is (c).
Organic Compounds Containing Oxygen 317
O Mechanism
O
O
(a) (b) H
Å
+ CH3MgBr
O (1)
(c) O (d) O
Å
MgBr + CH4
Å
O
Ans. (d) CH3MgBr (2)
In S N 2 reaction, no formation of carbocation takes place. The Å
nucleophile here which is phenoxide attacks from the back side O MgBr Å Å
to the carbon bearing the leaving group (bromide ion). MgBr MgBr
O
OH CH3
Å
O OMgBr Å CH3MgBr
Å

+ Br SN 2 MgBr
K2CO3 / (3)
Acetone
CH3
Phenol +
H2O/H
In S N 2 mechanism
d – d+ d–
Nu.....R+.....X Nu —R + X– OH
—
—

Nu R—X
Bond formation and bond CH3
breaking takes place at the CH3
same time (intermediate) (3°-alcohol)
Here, in the question
Å 3 molecules of CH3MgBr is used for this conversion.
OH O K
∴ Statement II is false.
K2CO3
05 OH
Phenol
Conc. H2SO4 +
O K
Å ∆
O A B
SN 2
+ Consider the above reaction, and choose the correct
Br
statement. [2021, 27 July Shift-II]
So, here option (d) is correct. (a) The reaction is not possible in acidic medium.
(b) Both compounds A and B are formed equally.
04 Given below are two statements. (c) Compound A will be the major product.
Statement I Ethyl pent–4–yn–oate on reaction with (d) Compound B will be the major product.
CH3MgBr gives a 3° alcohol. Ans. (c)
Statement II In this reaction, one mole of ethyl (i) Complete mechanism of given reaction is as follows:
pent–4–yn–oate utilizes two moles of CH3MgBr . Hydrolysis process Acid catalysed hydration of alcohol
group.
In the light of the above statements, choose the most H
appropriate answer from the options given below.
[2021, 27 Aug Shift-II] OH O—H
(a) Both statement I and statement II are false.
H+
(b) Statement I is false but statement II is true.
(From H2SO4)
(c) Statement I is true but statement II is false.
1-phenyl-1-propanol
(d) Both statement I and statement II are true.
Ans. (c) (ii) Removal of water molecule/formation of carbocation.
Ethyl pent-4-yn-oate on reaction with CH3MgBr gives 3° alcohol. H
2 4 Å
1 O—H
CH3MgBr MgBr
3 5
OÅ MgBr
OH
Ethyl pent-4-yn-oate
+
H2O/H
CH 3
CH 3 (iii) Removal of corresponding hydrogen ion by HSO−4 and
3° alcohol formation of cis and trans 1-phenyl-1-propene.
∴ Statement I is true.
318 JEE Main Chapterwise Topicwise Chemistry

OH
–H2SO4
HSO4– +
H
A B H3PO4 (BH3)2
07 A P
(major product) cis-propenylbenzene 120ºC (Major H2O2/OH–, H2O (Major
trans-propenylbenzene product) product)

trans alkenes are more stable than cis alkene, so product A Consider the above reaction and identify the product
is major product formed in the reaction. (P). [2021, 27 July Shift-I]

06 OH
OH CH3 OH
Conc.HBr
C—OCH3 P
H 3C (Major product)
(a) (b)
Consider the above reaction, the major product P
OH CH3
formed is [2021, 27 July Shift-II]
OH OH
Br
(c) (d)
(a) C––OCH3 (b) C––OCH3
CH3 CH3
Br
Ans. (d)
OBr Br OH OH2
⊕
(c) C––OCH3 (d) CBr
CH3 CH3
H3PO4
Ans. (b) ∆

Complete reaction with mechanism is as follows

(i) Hydrolysis process Attack of H+ on OH− ion. OH
(BH3)2
H
–
H2O2/OH , H2O
OH O—H Major (P) Major (A)
H+
C—O—CH3 C—O—CH3
Formation of compound (A) takes place by dehydration of alcohol
H 3C by E ′ reaction.
CH2 CH2
Methyl 3-hydroxy-2- Conversion of compound A to compound P in undergoes through
methylene butanoate hydroboration-oxidation reaction that converts an alkene into an
(ii) Removal of water molecule/formation of carbocation. alcohol. In this process, H-attached at more hindered site while
H
OH attached at less hindered site.

O—H
H+
08 Which one of the following phenols does not give colour
C—O—CH3 C—O—CH3 when condensed with phthalic anhydride in presence of
H3C H3C conc. H2SO 4 ? [2021, 26 Aug Shift-II]
CH2 CH2
OH
Carbocation
(iii) Resonance Movement of double bond/shifting of OH
carbocation. (a) (b)

H+ CH3
C—O—CH3 C—O—CH3
OH OH
H 2C H 3C
CH2 CH2 OH
(c) (d)
(iv) Addition of bromide ion.
OH
Ans. (b)
–Br–
C—O—CH3 C—O—CH3 In the electrophilic substitution reaction, phenol gives ortho and
H3C H 3C para substituted product in which para is the major product. The
CH2 H2 C electrophilic substitution reaction of phthalic anhydride with
Br phenol is taking place at para position of the phenol. All the given
(P) molecules have free para position except in p-cresol. Hence, it
Major product does not give colour of phthalic anhydride.
Organic Compounds Containing Oxygen 319

The reaction is as follows : (i) C2H5MgBr, dry ether

(ii) H2O, HCl
10 P
OH (Major product)
H2SO4
O + O Consider the above reaction, the major product P is
NaOH
[2021, 25 July Shift-I]
OH
OH
HO OH (a) (b)
(Pink colour)
OH
OH
09 The correct options for the products A and B of the (c) (d) Cl
following reactions are [2021, 26 Aug Shift-I]
Cl
OH
Ans. (c)
Br2 (excess) Br2 In the given reaction, Grignard reagent is used for 1, 2-addition in
A B
H 2O CS2, <5ºC the carbonyl carbon and form alcohol as a major product.
O s
OH OH OMg⊕ OH
–
CH3—CH2 MgBr H2O
Br Br Br
(Grignard reagent)
(a) A= , B= But-3-en-2-one
(1,2-addition)
HCl

Br Br OH OH
OH OH
Cl + H
Br Br
(b) A= , B= H Cl
(Minor product) (P)
1-chloro-3-methyl pentan-3-ol (Major product)
Br Br 1-chloro-3-methyl pentan-3-ol

OH OH Addition of HCl at the alkene gives 2-chloro-3-methylpentan-3-ol

Br Br Br as major product.
(c) A= , B=
11 In the given reaction, 3-bromo-2, 2-dimethyl butane
Br C2H5 OH
Br → (A) .
Major product
OH OH
Product A is [2021, 20 July Shift-I]
(a) 2-ethoxy-3, 3-dimethyl butane
(d) A= , B=
(b) 1-ethoxy-3, 3-dimethyl butane
(c) 2-ethoxy-2, 3-dimethyl butane
Br Br (d) 2-hydroxy-3, 3-dimethyl butane
Ans. (b) Ans. (c)
Bromination of phenol with excess of bromine and water will The given reaction proceeds viaS N 2 reaction mechanism as follows
result in multiple substitution around ring as water ionises
phenol to phenoxide ion, which activities the ring for CH3 Br CH3
trisubstitution, while less polar solvent, i.e. CS2 will give C2H5OH +
CH3—C—CH—CH3 – Br– CH3—C—CH—CH3
mono-substituted compound.
OH OH CH3 CH3
Br Br 3-bromo-2,2-dimethyl butane 1,2, methyl
shift
+ Br2 (excess) H
+ C2H5OH +
Phenol O—CH2—CH3 CH3—C—CH—CH3
Br
(A) H3C—C—CH—CH3 CH3CH3
2,4,5 tribromophenol
OH OH CH3CH3 O—CH2—CH3
H+
1 2 3 4
Br2 CH3—C— CH—CH3
CS2 < 5°C
CH3 CH3
Phenol (A) (Major product)
Br
2-ethoxy-2,3–dimethyl butane
(B)
mono-substituted product ∴Therefore, product A is 2-ethoxy-2, 3-dimethyl butane.
320 JEE Main Chapterwise Topicwise Chemistry

12 Identify A in the given reaction. (ii) Pyridine reacts with HCl to give pyridinium chloride.
OH
+ HCl Cl
SOCl3 N N Acts as Na in
A (Major product)
(Pyridine) SN2 reaction
H
Pyridinium ion
HO CH2OH
[2021, 26 Feb Shift-II] (iii) Chlorosulphite reacts with chloride ion via. bimolecular
nucleophilic substitution reaction to give alkyl chloride.
OH OH

O Cl Cl/SN 2
(a) (b) R S –SO2,
R— Cl

O –Cl

HO CH2Cl Cl CH2Cl
13 Ceric ammonium nitrate and CHCl 3 /alc. KOH are used
Cl
Cl for the identification of functional groups present in
……… and ……… respectively. [2021, 26 Feb Shift-II]

(c) (d) (a) alcohol, phenol (b) amine, alcohol

(c) alcohol, amine (d) amine, phenol
OH CH2OH Ans. (c)
Cl CH2Cl
Ceric ammonium nitrate and CHCl 3 / alc. KOH are used for the
Ans. (b) identification of functional groups present in alcohol and amine
The given reaction is an application of Darzen’s reaction in which respectively.
an aliphatic alcohol (preferably 1° Ceric ammonium nitrate (CAN) test When an alcohol reacts with
or 2°) gets converted into the respective alkyl chloride (in pure few drops of CAN, a red complex ammonium nitrate is developed
form) through SN2 pathway when it uses which confirms presence of alcoholic OH group.
− NH 4 NO 3
3ROH + (NH4 )2 [Ce(NO3) 6 ] → [Ce(NO3) 4 (ROH) 3]
Red colour
pyridine or as organic base. Alcohol Ceric ammonium Red complex
nitrate
N
Test with CHCl 3 and alcoholic KOH
OH Phenolic — OH group OH [Carbylamine test or Saytzeff’s isocyanide test]
When a primary amine (aliphatic or aromatic) is heated with
SOCl2/Pyridine
alcoholic KOH and chloroform (CHCl 3), the isocyanide
–2HCl (carbylamine) is formed as indicated by a foul order.
–2SO2
∆
HO CH2—OH Cl CH2—Cl R  NH2 + CHCl 3 + 3KOH → R NC
(alc. ) −3KCl
2° 1° (Major) 1°-amine −3H 2 O Carbylamine

[Aliphatic — OH [Option-b]
group] 14 Identify the major products A and B respectively in the
Note Phenolic  OH group does not respond to this reaction as
following reactions of phenol. [2021, 26 Feb Shift-I]

+ R-effect of phenolic OHgroup gives double bond character OH

to the C O bond.
(i) CHCl3, NaOH Br2 in CS2
(B) (A)
(ii) H3O+ 273K
OH O—H
OH OH
Br
Machanism
(i) Alcohol react with thionyl chloride to give chlorosulphite (a) and
and HCl.
CHO
Cl
OH OH
–HCl O Cl
R—OH + S—Cl R S CHO
O O (b) and
(SOCl2) Chlorosulphite
Thionyl chloride
Br
Organic Compounds Containing Oxygen 321
OH OH So, o-nitrophenol exists in monomeric state and becomes steam
Br CHO volatile. Statement II is false, because, due to the presence of
(c) intramolecular hydrogen bonding, boiling point and melting point
and
of o-nitrophenol will be lower.
Note p-nitrophenol is the positional isomer ofo-nitrophenol.
OH OH p-nitrophenol shows intermolecular hydrogen bonding and so, it
has higher boiling point, melting point and water solubility.
Intramolecular
(d) and H-bonding O
HO— N
O HO— N
Br CHO
p-nitrophenol
Ans. (b)
Phenol on reaction withBr2 in CS2 / 273 K undergoes an 16 What is ‘X’ in the given reaction?
electrophilic substitution reaction byBr + (electrophile) in aprotic CH2OH
solvent CS2 to give 4-bromophenol as the major product. 210°C
 + Oxalic acid → X
OH OH OH CH2OH (Major product)
Br
Br2 in CS2/273K [2021, 25 Feb Shift-II]
+ CHO CH2OH CH2 CH—OH
Phenol (a)  (b)  (c) (d) 
Br CHO CHO CH2 CH2
4-bromophenol 2-bromophenol
(major) (A) (minor) Ans. (c)
Phenol on reaction with CHCl 3, NaOH followed by hydrolysis gives When ethylene glycol is heated with oxalic acid at 210ºC, first we
salicylaldehyde as a major product. get an unstable cyclic-diester (ethylene oxalate) which readily
It is Reimer-Tiemann reaction. It is also an electrophilic decarboxylate to give ethylene as the major product.
substitution reaction of phenol by dichlorocarbene CCl2 O O
(electrophilic). CH2O H OH CH2 O
C 210ºC C –2CO2 CH2
OH OH OH +
–2H2O CH2
CHO CH2O H OH C CH2 O C
O O
(i) CHCl3, NaOH Ethylene
+ Ethylene Oxalic Ethylene (Major)
(ii) H3O+ oxalate
glycol acid
Phenol 2-hydroxybenzaldehyde
or CHO
Salicylaldehyde 4-hydroxybenzaldehyde 17 Which of the following compound gives pink colour on
(major) (B) (minor) reaction with phthalic anhydride in conc. H2SO 4
followed by treatment with NaOH? [2021, 24 Feb Shift-I]
15 Given below are two statements: CH3
Statement I o-nitrophenol is steam volatile due to
intramolecular hydrogen bonding. (a)
Statement II o-nitrophenol has high melting due to HO
hydrogen bonding. CH3
In the light of the above statements, choose the most (b)
appropriate answer from the options given below.
[2021, 26 Feb Shift-I] OH
(a) Statement I is false but statement II is true H3C CH3
(b)Both statement I and statement II are true
(c)
(c) Both statement I and statement II are false
(d) Statement I is true but statement II is false HO OH

Ans. (d) HO CH3

Statement I is true. Because of closer proximity (d)
(1, 2-positions) of OH and NO2 groups, o-nitrophenol shows
intramolecular hydrogen bonding. HO CH3

δ+ Ans. (b)
H Intramolecular
O Oδ− H-bonding Correct answer is
CH3
N

OH
o-nitrophenol 2-propylphenol
322 JEE Main Chapterwise Topicwise Chemistry

Firstly phthalic anhydride in presence of conc.H2SO4 undergoes CH3

protonation to give an intermediate carbocation. This
CH3 Rearrangement CH3
carbocation reacts with 2-propylphenol in presence of NaOH to H
give pink colour compound. 1,2-hydride shift H
CH3
Mechanism Carbocation
stable by 4α-H
OH
Carbocation
CH3 stable by 5α-H
Conc. H2SO4 (more stable)
O O+
H+
C Step 2 Elimination reaction always give minor product than
Phthalic (Intermediate
anhydride substitution reaction.
carbocation) HO NaOH
OH CH3 H CH3
H
+ CH3 Cl– CH3
–H2O –HCl
O H+
O+ (Elimination
C C Cl reaction) (Minor)
1-ethylidene
HO CH3 -2-methylcyclohexane
OH Cl
O CH3
CH3
OH
CH3 (Major)
OH 1-chloro-1-ethyl-2-
methylcyclohexane
CH3 CH3
OH (Pink colour)
19 Two compounds A and B with same molecular formula
2-propylphenol gives pink colour on reaction with phthalic (C 3H6O) undergo Grignard’s reaction with
anhydride in conc. followed by treatment with NaOH. methylmagnesium bromide to give products C and D.
Products C and D show following chemical tests.
18 What is the final product (major) ‘A’ in the given
reaction? [2021, 24 Feb Shift-I] Test C D
CH3 OH
Ceric ammonium Positive Positive
CH nitrate test
‘A’
CH3 HCl Lucas test Turbidity obtained Turbidity obtained
Major product
after five minutes immediately
Iodoform test Positive Negative
CH3 Cl CH3
CH C and D respectively are [2020, 2 Sep Shift-II]
CH
(a) CH3 (b) CH3 OH CH3
 
(a) C=H3C CH2 CH CH3 ; D =H3C C  OH
CH3 CH3 
CH3
CH CH2 Cl
(c) (d) CH2 CH3
(b) C =H3C CH2 CH2 CH2 OH;

Ans. (d) D =H3C CH2 CH  CH3


Steps involved in this reaction are as follows
OH
Step 1 HCl → H+ + Cl − CH3
⊕ ⊕
+
H attacks on —OH (lone pair) and formedOH2 ion. Here,OH2 is 
the good leaving group. (c) C =H3C CH2 CH2 CH2 OH; D = H3C C  OH

CH3
CH3 OH CH3 OH2 CH3
CH3 H+Cl– CH3 –OH2 
H H (d) C=H3C C  OH; D =H3 CCH2 CH  CH3
 
1-(2-methyl cyclohexyl) CH3 OH
ethan-1-ol
Organic Compounds Containing Oxygen 323

Ans. (a)
α Slow
Br + Brs + H2O
OH (alc.)
H CH2 Isobutylene
β

(t-BuBr)
C3H6O
O

(Aldehyde) CH3 CH2 CH O CH3 C CH3 (Ketone)

(i) CH3MgBr (i) CH3MgBr

(ii) H2O (ii) H2O
CH3
2° alcohol CH3 CH2 CH CH3
C CH3 C CH3
OH
OH D 3° alcohol

Positive Ceric ammonium Positive

Colour change: nitrate Colour change:
yellow → red test (CAN) yellow → red

Lucas test
White turbidity Immediate
ZnCl2 (anhyd.)/
after 5 min white turbidity
conc. HCl/20°C

Iodoform Negative,
Positive
test I2/OH– because D is
CH3 CH2 CH CH3 a 3°-alcohol
which is not
OH oxidisable
by halogen
s s
[O] I2 /OH or OI

CH3 CH2 C CH3 I2 /OH– –

CH3CH2COO + CHI3
O Iodoform
(Yellow
keto methyl ppt.)
group
OH OH
20 The major product of the following reaction is
OH H3C H3C NO2
(c) (d)
CH3
Conc. HNO3 + conc. H2SO4 NO2 NO2
NO2 NO2
NO2
[2020, 2 Sep Shift-II]
OH Ans. (c)
H3C The substrate undergoes nitration reaction (ArSE2 ). The
(a) electrophile (NO2+ ) will prefer to attack benzene nucleus which is
O2N NO2 rich with electron density (by + R or +I-effect of substituent,
where + R > + I) as wall as sterically less crowded.
OH
Out of three substituents, the —OH group will dominate the rate
H3C NO2
(b) of initiation reaction, because —OH has strong ring activating
property by its + R or + M effect.
NO2
324 JEE Main Chapterwise Topicwise Chemistry

The ring activating order is CH2CH3 CH2CH3

—OH > —CH3 > —NO2
(+ R effect) (+ ve hyper (– R effect) (a) (b)
conjugation)

+R O O
H
OH r CH==CH2 CHCH3
H C NO2 will suffer steric repulsion
δ– of OH and NO2 groups
(c) (d)
H
+ve N O O O
δ– –R
hyper Ans. (a)
conjugation O
H
Electronically and sterically
favorable to NO2 + HO CH2CH3 H—O CH2CH3
OH H2SO4
+
CH3 (H from H2SO4)
HNO3+ H2SO4 O O
(major) –H2O
(NO+) 2
NO2
CH2CH3 CH2—CH3
NO2
– H
HSO4

21 Consider the following reaction : –H2SO4

O O
OHc
dHO CH3 23 The increasing order of boiling points of the following
OHb compounds is
OHa OH OH OH OH

Chromic
→ ‘P’ The product ‘P’ gives positive ceric
anhydride
ammonium nitrate test. This is because of the
presence of which of these OHgroup(s)? CH3 NO2 NH2 OCH3
[2020, 3 Sep Shift-II] (I) (II) (III) (IV)
[2020, 5 Sep Shift-II]
(a) (b) and (d) (b) (d) only
(c) (b) only (d) (c) and (d) (a) I < III < IV < II (b) I < IV < III < II
(c) IV < I < II < III (d) III < I < II < IV
Ans. (c)
Ans. (b)
Only 3° alcohol give positive ceric ammonium nitrate test.
OH
OH
HO shows strongest hydrogen bonding
Chromic
anhydride
from  O H group.
OH
OH
N
O O
HO (II)
OH
OH
COOH
shows stronger hydrogen bonding
Product ‘P ’ from both side of  OH group as
(3° alcohol gives red colour well as  NH2 group.
with ceric ammonium nitrate)
NH2
(III)
22 The major product of the following reaction is
HO CH2CH3 OH
shows stronger hydrogen bonding
H2SO4 from one side  OH group and
another side of  OCH3 group
O shows only dipole-dipole interaction.
[2020, 5 Sep Shift-II]
OCH3
(IV)
Organic Compounds Containing Oxygen 325

OH 26 Arrange the following compounds in increasing order of

Boiling point µ dipole moment (µ). C OH bond length : methanol, phenol, p-ethoxyphenol
shows hydrogen bonding from [2020, 8 Jan Shift-I]
 OH group only. (a) phenol < methanol < p-ethoxyphenol
(b) phenol < p-ethoxyphenol < methanol
CH3
(c) methanol < p-ethoxyphenol < phenol
(I)
(d) methanol < phenol < p-ethoxyphenol
Ans. (b)
24 The number of chiral carbons in chloramphenicol is …… .
[2020, 7 Jan Shift-I] The increasing order of C OH bond length in the given
Ans. (2.00) compounds is : phenol < p-ethoxy phenol < methanol. It is
explained as follows:
Structure of chloramphenicol is
Methanol has no resonance and no partial double bond character
OH OH in C OH bond.
∴It has maximum C OH bond length.
Cl
In both phenol and p-ethoxyphenol, resonance is involved.
NH
O2N Cl ∴ C OH bond has partial double bond character and hence
C OH bond length is less than methanol.

The two carbon atoms shown by black circles are chiral. H H H H

O O O O

25 The major product of the following reaction is :

H3C OH
Dil, H2SO4

H3C H3C
H
[2020, 8 Jan Shift-I] O
OH
H3C H3C OH
OH
(a) (b)
H3C OH H3C
OH CH3 HO CH3
(p-ethoxyphenol also exhibits similar resonating structures).
CH3
CH3 But in p-ethoxyphenol, there is + R-effect of
‘OC2H5 ’ group also.
(c) (d) OH

OH OH
H3C CH3 H 3C CH3
Ans. (c)
OC2H5
The reaction proceeds as follows:
So the ‘C OH’ bond has less double bond character and slightly
H 3C H+ (from more bond length than C OH’ bond length in phenol.
OH H2SO4)

+
27 An organic compound neither reacts with neutral ferric
H 3C H3C 5 4 1
H 3C
7
OH2 chloride solution nor with Fehling solution. It however,
6 3 2 reacts with Grignard reagent and gives positive
H 3C CH3 iodoform test. The compound is [2019, 8 April Shift-I]

CH3 CH3 O
3
CH3 O
4 2 +H2O CH3
(a) (b)
5 –H
1 H
6 OH OH
r
H 3C CH3 H3C CH3 O
(Torpineol)
326 JEE Main Chapterwise Topicwise Chemistry

O OH Step I In presence ofPBr3, alcohols undergo substitution

reactions to give halides. ReagentPBr3 is usually generated
C2H5 CH3
(c) (d) insitu by the reaction of red phosphorus with bromine.
CH3 C2H5
O
PBr3
O OH Br
Ans. (d)
O O
According to the given conditions, compound (d) neither reacts 3-bromohexanone
with neutral ferric chloride solution nor with Fehling solution. It
however reacts with Grignard reagent and gives positive Step II 3-bromohexanone in presence of alc. KOH undergoes
iodoform test. elimination reaction and gives cyclohex-2-en-1-one.
● As the compound does not contain any phenolic —OH group.
Hence, it gives negative neutralFeCl 3 test. Alc. KOH
Br
OH
|
CH3 Neutral O O
no reaction Cyclohex-2-en-1-one
FeCl3
(FeCl3 test for phenolic
C—Et
group)
O 29 The major product of the following reaction is
LiAlH4
● Compound gives reaction with CH3CH == CHCO 2CH3   → [2019, 9 April Shift-I]

RMgX as it contains  C  E t. (a) CH3CH == CHCH2OH (b) CH3CH2CH2CH2OH

 (c) CH3CH2CH2CO2CH3 (d) CH3CH2CH2CHO
O Ans. (a)
OH OH
| | Key Idea LiAlH4 reagent is used for the reduction of CHO,
CH3 CH3
RMgX O

Grignard R
reagent C2H5
C—Et
— C OCH3. It does not reduce double bonds.
O OH
The reaction of an ester withLiAlH4 produces two alcohols, one
Compound with CH3 CH  group undergoes iodoform test in corresponding to the acyl portion of the ester and one
 corresponding to the alkyl portion.
OH
O
presence of NaOH andI2 .  LiAlH 4
CH3CH == CHC—OCH3 → CH3 CH == CHCH2OH + CH3OH
OH O Methanol
But-2- en-1- ol
|
CH3 NaOH+I2
O–Na+ Thus, the major product of the given reactant CH3CH == CH
CH3I ↓ + O
Iodoform
Et
C—Et test Yellow 
ppts. C OCH3 in presence ofLiAlH4 is CH3CH == CH CH2OH and CH3OH.
O
O The reaction proceeds through following mechanism.
Mechanism
28 The major product of the following reaction is
1. PBr3
O Nucleophilic acyl
OH 2. KOH (alc.) – substitution reaction
CH3CH CH C OCH3 + H AlH3
O [2019, 9 April Shift-I] s
O

(a) (b) OH CH3CH CH C OCH3

O H
HO O
–
CH3CH CH C + CH3O
(c) (d) An aldehyde
H Nu H– –
cle
op A lH
O O h
rea ilic a 3 s
cti dd O
on itio
Ans. (c) n
H+
Key Idea PBr3 reagent is used for the substitution of —Br group CH3 CH CH CH2OH H2O
CH3CH CH C H
while alc. KOH reagent is used to carry out elimination reaction. Primary alcohol
H
The given reaction proceed in following manner:
Organic Compounds Containing Oxygen 327

30 The major product of the following reaction is 31 The major products of the following reaction are
OH

(i) CrO3 (1) CHCl3/aq. NaOH

HO (ii) SOCl2/∆ (2) HCHO, NaOH (conc.)
(3) H3O+
(iii) D
HO Cl [2019, 12 April Shift-I]
[2019, 12 April Shift-I]
OH OH
O
COOH COOH
O (a) and methanol (b) and methanol

(a) (b)
HO Cl OH
HO OH OH

O OH OH
(c) (d)
and formic acid and formic
O acid
(c) (d) OH Cl
Ans. (d)
Cl
Cl The major products of the given reaction are as follows:
OH OH
Ans. (b)
The major product formed in the reaction is as follows: (1) CHCl3/aq. NaOH OH
(2) HCHO, conc. NaOH and HCOOH
(3) H3O+

HO ==O Cl Cl
(1) CrO3
(2) SOCl2/∆ In step-I, substituted phenol undergoes Reimer- Tiemann
(3)∆ reaction in presence of CHCl 3 / aq. NaOH
HO HO
OH OH
Primary alcohol readily oxidised to corresponding carboxylic acid CHO
with oxidising agent, chromium trioxide (CrO3) in acidic medium. (1) CHCl3/aq. NaOH

COOH
HO Cl Cl
CrO3
The aldehyde obtained in above equation does not possess
HO HO α-hydrogen. In presence of formaldehyde and conc. NaOH it
undergoes Cannizaro reaction. In this reaction, one molecule of
OHgroup of carboxylic acid get substituted by Cl in aldehyde is reduced to alcohol while another molecule is
presence ofSOCl2 (Thionyl chloride). oxidised to salt of carboxylic acid.
OH O–Na+
COOH COCl CHO
SOCl2/∆ Conc.
+ HCHO OH
NaOH + HCOO–Na+
+ SO2↑ + HCl↑
HO HO
Cl Cl
Further, heating of product leads to intramolecular cyclisation. Upon hydrolysis, following reaction takes place
O–Na+ OH
COCl
C==O H3O+ OH
∆
OH + HCOOH
+ HCOO–Na+
HO HO
Cl Cl
328 JEE Main Chapterwise Topicwise Chemistry

32 What will be the major product when m-cresol is Carbonyl

group O O
reacted with propargyl bromide (HC ≡≡ C CH2Br) in O OH
presence of K 2CO 3 in acetone? [2019, 12 April Shift-II] CH2 C OCH3 CH2 C OCH3
NaBH4
O OH MeOH
Ester
(a) (b) group
Isolated
C C
CH3 CH3
OH OH 34 The increasing order of the pK a values of the following
(c) (d) compounds is [2019, 10 Jan Shift-I]

OH OH OH OH
CH3 CH3

Ans. (a) NO2

The major product when m-cresol reacts with propargyl bromide NO2 OMe
(HC ≡≡ C  CH2Br) in presence ofK2 CO3 in acetone is given in the A B C D
following reaction: (a) D < A < C < B (b) B < C < A < D
OH O– (c) C < B < A < D (d) B < C < D < A
Step 2 Ans. (b)
Step 1
1. K2CO3 Br CH2 C CH
Acidic strength is inversely proportional to pK a value. The acidity
–Brs of phenols is due to greater resonance stabilisation of phenoxide
O CH2 C CH ion relative to phenol.
Therefore, any substituent which stabilises the phenoxide ion
more by dispersal of negative charge will tend to increase the
acidity of phenol.
Electron withdrawing groups ( NO2 ) increases the acidic
Major product strength of phenol whereas electron donating group ( OCH3)
decreases the acidic strength of phenol. In case of NO2 group
In step 1 K2 CO3 act as a base and abstract H-atom from OH attached to phenol, the dispersal of negative charge is more
group. pronounced at o- and p-position than at m-position.
This leads to the formation of substituted phenoxide ion (highly Thus, order of acidic strength of nitrophenol is:
stable). p-nitrophenol > o-nitrophenol and the correct order of the pK a
In step 2 substituted phenoxide ion on reaction with values of give option is
Br  CH2  C ≡≡ CH gives the required product.
OH OH OH OH

33 The major product ‘X’ formed in the following reaction is

< < <
O
O NO2
CH2 C OCH3
NaBH4 NO2 OMe
X
MeOH (B) (C) (A ) (D)
O
OH OH 35 The major product of the following reaction is
CH2 C OCH3
CH2 CH2 OH OH
(a) (b)
Br2 (excess)
O OH
O
CH2 C H CH2 CH2 OH
(c) (d) SO3H [2019, 11 Jan Shift-I]
[2019, 10 Jan Shift-I] OH OH
Ans. (b) Br
NaBH4 is a selective reducing agent. It reduces carbonyl (a) (b)
C Br Br
O group into an alcohol but cannot reduce an isolated
Br SO3H
C == C and an ester group too.
Organic Compounds Containing Oxygen 329

OH OH OCH3 Br
Br Br Br Br H
(c) (d) OCH3 Br2/H2O
H
(excess) Br

Br SO3H (b) EtMgBr

No reaction
Ans. (c) OH Br
OH Acidic 'H' H
Br2/H2O
H
(excess)
Br
In , ipso-substitution takes place with the carbon bearing OH
SO3H group. After the attack of the electrophilic O Mg Br
+
SO3H
Br in the rate determining step (rds) of the ArS E2 (c)
Et MgBr
pathway desulphonation ( SO3) takes place with a + C2H6
faster rate. [Et acts as a base]
δ+ δ– δ–
N≡C
(+R) O—H O—H OH
(rds) (fast) δ+
Br2/H2O –SO3 (d)
(Br ) –H
Br—Br Br Et group can react but (Br2/H2O) does not react
SO3H S Br
—Br
OH
H
OH 
Br Br
(i) 2 moles of Br2 37 CH3CH2 C  CH3 cannot be prepared by
(ii) Attack at ortho- 1 
and ortho-2 by Br+
(iii) –2HBr
Ph [2019, 12 Jan Shift-I]
Br (a) CH3CH2COCH3 + PhMgX (b) PhCOCH3 + CH3CH2MgX
A white ppt. of
2,4,6-tribromophenol
(c) PhCOCH2CH3 + CH3MgX (d) HCHO + PhCH(CH3) CH2MgX
Ans. (d)
OH

36 Which of the following compounds reacts with ethyl CH 3 CH2  C  CH 3 cannot be prepared by HCHO and
magnesium bromide and also decolourises bromine 
water solution [2019, 11 Jan Shift-II] Ph
CN OCH3 PhCH(CH3)CH2MgX. This can be easily illustrated by following
CH2—CO2CH3 reaction.
CH
(a) (b) CH2 O
d– d+ d – d+
H C H + PhCH CH2 MgX Ph CHCH2 CH2 O MgX
OH CN O
CH3 CH3
(c) (d) H3O+

Ph CH (CH2)2 OH
Ans. (c)
CH3
Ethyl magnesium bromide is a Grignard reagent (GR), it
⊕ The obtained product is not the required substance. While
constitutes C2H–5 [C2H–5 MgBr in ether/aprotic medium] which can
option (a), (b) and (c) can readily prepare the required substance.
act as nucleophile as well as strong base. Bromine water (Br2 /H2O, The reactions are as follows :
red) gets decolourised with phenol derivatives (option, c), anisole
d – d+
derivatives (option, b) etc., as C==C is present outside the O O MgX
ring (aliphatic, not aromatic). d– d+
δ+ δ–
Ph C CH2 CH3 + CH3MgX Ph C CH2CH3
C≡N Et group can react
CH3
δ+ δ– OH
(a) CH2—C—OMe
H3O+
δ–
Ph C CH2CH3
(Br2/H2O does not react) CH3
330 JEE Main Chapterwise Topicwise Chemistry

d – d+ (ii) SN AE
O O MgX
d– d+
O
Ph C CH3 + CH3CH2MgX Ph C CH3 O
–
O O C OCH3
Cl C OCH3
CH2CH3
OH
H3O+ In the product ofS N AE the attached group is ortho and
Ph C CH3 para-directing due to following cross conjugation

CH2CH3 O
δ–
d – d+ 6 O1 C O 2 CH3
5 1
O O MgX
4 2
d – d+ δ– 3 δ–
CH3CH2 C CH3 + PhMgX CH3CH2 C CH3
Cross conjugation due to which lone pair of oxygen 1 will be easily
Ph available to ring resulting to higher electron density at 2, 4, 6
OH position with respect to group. However from the stability point
H3O+ of view ortho positions are not preferred by substituents as
CH3CH2 C CH3
group O  C O  CH3 is bulky.
||
Ph O
Hence, on further bromination ofS N AE product para bromo
38 Phenol reacts with methyl chloroformate in the derivative will be the preferred product i.e.
presence of NaOH to form product A. A reacts with Br 2
O C O CH3 O C O CH3
to form product B. A and B are respectively [JEE Main 2018]
OH Br OH O O
+ Br2 + HBr
(a) and
OCH3 OCH3
Br
O O
O O O O 39 The product of the reaction given below is
[JEE Main 2016]
(b) and
O O (i) NBS/hν
X
(ii) H2O/K2CO3
Br
O O O O
OH O
(c) and
O O (a) (b)
Br
OH OH CO2H
(d) and (c)
OCH3 OCH3 (d)

O Br O
Ans. (c) Ans. (a)

Given NBS Br
OH hν
NaOH
+ Methyl chloroformate A
Br2
Br HO OH
B H2O/K2CO3
+ +
In the above road map, first reaction appears as acid base
reaction followed byS N AE (Nucleophilic substitution through
Addition and Elimination). Both the steps are shown below
(i) Acid base reaction 40 The most suitable reagent for the conversion of
R  CH2 OH→ R  CHO is [JEE Main 2014]
(a) KMnO 4 (b) K2Cr2O 7
(c) CrO 3
(d) PCC [Pyridinium chlorochromate]
Organic Compounds Containing Oxygen 331

Ans. (d) O δ+
H
Mild oxidising agents like PCC [Pyridinium chlorochromate] are δ– intramolecular H-bonding
particularly used for the conversion of R  CH2OH→ R  CHO. δ+ O
N
41 Arrange the following compounds in the order of O
decreasing acidity [JEE Main 2013]
OH OH OH OH 44 Iodoform can be prepared from all except
(a) ethyl methyl ketone [AIEEE 2012]

; ; ; (b) isopropyl alcohol

(c) 3-methyl-2-butanone
(d) isobutyl alcohol
Cl CH3 NO2 OCH3
Ans. (d)
I II III IV
Iodoform reaction is given by alcohols and ketones containing
(a) II > IV > I > III (b) I > II > III > IV O
(c) III > I > II > IV (d) IV > III > I > II 
Ans. (c) CH3  CH  and CH3  C  group, respectively. Thus, among

OH OH OH OH OH
the given compounds, isobutyl alcohol does not contain
> > >
CH3  CH  group.

NO2 Cl CH3 OCH3 OH
(strong (–I (+I,hyper (strong
–M,–I conjugation) +M Hence, it does not give iodoform reaction on treatment with
effect)
effect) effect) I2 /NaOH.
O
Electron releasing group decreases while electron withdrawing 
group increases acidic strength by destabilising and stabilising CH3  CH  CH3 CH3  C  CH2 CH3
the phenoxide ion formed respectively.  Ethyl methyl ketone
OH
42 An unknown alcohol is treated with the ‘Lucas reagent’ Isopropyl alcohol
to determine whether the alcohol is primary, secondary
O CH3
or tertiary. Which alcohol reacts fastest and by what
 
mechanism? [JEE Main 2013]
CH3  C  CH  CH3 CH3  CH  CH2OH
(a) Secondary alcohol by SN1  Isobutylalcohol
(b) Tertiary alcohol by SN1 CH3
(c) Secondary alcohol by SN2 3-methyl-2 -butanone
(d) Tertiary alcohol by SN2 Hence, compounds (a), (b) and (c) will give iodoform while compound
Ans. (b) (d) (isobutyl alcohol) does not give any iodoform reaction.
The reaction of alcohol with Lucas reagent is mostlySN 1 reaction
and the rate of reaction is directly proportional to the stability of 45 Phenol is heated with a solution of mixture of KBr and
carbocation formed in the reaction. KBrO 3 . The major product obtained in the above
Since 3° R OHforms 3° carbocation (most stable) hence it will reaction is [AIEEE 2011]
react fastest by S N 1 reaction. (a) 2-bromophenol (b) 3-bromophenol
(c) 4-bromophenol (d) 2, 4, 6-tribromophenol
43 Ortho-nitrophenol is less soluble in water than p- and Ans. (d)
m-nitrophenols because Br2 is formed by a redox reaction.
(a) o-nitrophenol is more volatile steam than those of 5Br – + BrO–3 + 6H+ → 3Br2 + 3H2O
m- and p-isomers.
—OH group is the activating group and thus activates the
(b) o-nitrophenol shows intramolecular H-bonding benzene towards electrophilic substitution reaction ato-and
(c) o-nitrophenol shows intermolecular H-bonding p-positions giving yellowish white precipitate of
(d) melting point of o-nitrophenol is lower than those of 2,4,6-tribromophenol.
m- and p-isomers [AIEEE 2012] OH OH
Ans. (b) Br Br
There is intramolecular H-bonding in o-nitrophenol and thus + 3Br2 + 3HBr
solubility in water is decreased.

Br
332 JEE Main Chapterwise Topicwise Chemistry

46 The correct order of acid strength of the following 48 From amongst the following alcohols the one that would
compounds is [AIEEE 2011] react fastest with conc. HCl and anhydrous ZnCl 2 is
I. Phenol II. p-cresol (a) 2-butanol (b) 2-methylpropan-2-l
III. m-nitrophenol IV. p-nitrophenol (c) 2-methylpropanol (d) 1-butanol [AIEEE 2010]
(a) III > II > I > IV (b) IV > III > I > II (c) II > IV > I > III (d) I > II > IV > III Ans. (b)
Ans. (b) The reaction of alcohol with conc. HCl and anhydrousZnCl2 follows
OH OÈ S N 1 pathway, so greater the stability of carbocation formed, faster
is the reaction.2-methylpropan-2-ol gives 3° carbocation.

I. + H
+ Hence, it reacts rapidly with conc. HCl and anhydrous ZnCl2
l (Lucas reagent).
phenoxide
49 Phenol, when it first reacts with concentrated sulphuric
(a), (b), (d) may be formed but (c) is never formed. acid and then with concentrated nitric acid gives
47 The main product of the following reaction is (a) 2, 4, 6-trinitrobenzene [AIEEE 2008]

Conc. H SO (b) o-nitrophenol

C 6H5CH2CH(OH)CH(CH3 ) 2 →
2 4
? [AIEEE 2010]
(c) p-nitrophenol
H5C 6 H (d) nitrobenzene
(a) C == C Ans. (b)
H CH(CH3) 2 OH OH
C 6H5CH2 CH3 SO3H
Conc. H2SO4
(b) C == C
sulphonation
H CH3
H5C 6 CH(CH3) 2
(c) C == C SO3H
H H OH OH
H5C 6CH2CH2 O2N SO3H O2N
Conc. HNO3 H3O+
(d) C ==CH2
Boil
H3C
Ans. (a)
o-nitrophenol
− SO3H
First sulphonation is the means to block para and ortho position
OH
and to reduce the reactivity of phenolic ring against strong
+
 CH3 H
C6H5  CH2  CH  CH 
oxidising agent HNO3. (The use of conc.HNO3 over phenol cause
CH3 the oxidation of ring mainly).  SO3H groups are knocked out on
boiling withH2O.
H
+
O 50 In the following sequence of reactions,


 CH3
C6H5  CH2  CH  CH  P+I Mg HCHO HO
CH3 CH3CH2OH →
2
A → B → C →
2
D
ether

C6H5  CH  CH  C CH3 the compound ‘D’ is [AIEEE 2007]

CH3 (a) butanal (b) n-butyl alcohol
H H (c) n-propyl alcohol (d) propanal
[β1] [β2] Ans. (c)
By the loss of β1 -H P + I2 Mg, ether
CH3CH2OH → CH3CH2  I →
 CH3  H PO
C6H5 — CH == CH — CH  3 3 A O
CH3 OMgI
Extension of conjugation By the loss of 
β2 - H

H  C H CH CH  CH
(More stable) CH3CH2MgI → 3 2 2
(Major product) B C
CH3
C6H5 — CH2 — CH == C OH
CH3 H2O 
(Less stable) → CH3 CH2 CH2 + Mg(OH)
(Minor product)
D
n -propyl alcohol
Organic Compounds Containing Oxygen 333

51 Among the following the one that gives positive CH3 CH3
Br
iodoform test upon reaction with I 2 and NaOH is OH Br2, H2O
[AIEEE 2006]
(a) CH3CH2CH(OH)CH2CH3 (b) C 6H5CH2CH2OH OH
CH3 Br
(c) H3C Dibromo derivative
OH (d) PhCHOHCH3 CH3 CH3
Ans. (d) Br
Br2/H2O Br
For positive iodoform test, alcohol molecule must have
CH3  CH  group.

OH
OH OH
Thus, iodoform test is given by only (d)Ph  CH  CH3 while
others will not give this test. 
OH CH2OH CH2Br
I2 +NaOH
Ph  CH  CH3 → CHI3 + Ph  COO−
 Br2/H2O
OH + HBr
52 Phenyl magnesium bromide reacts with methanol to
give [AIEEE 2006] m-cresol due to phenoxide ion in H2O solvent, gives
(a) a mixture of anisol and Mg(OH)Br tribromoderivative at all ortho and para positions.
(b) a mixture of benzene and Mg(OMe)Br OH OH
(c) a mixture of toluene and Mg(OH)Br
(d) a mixture of phenol and Mg(Me)Br Br
(d) and
Ans. (b) CH2Br
PhMgBr can be protonated by any of the protic solvent e.g.,
CH3OH. – +
54 OH O Na
Br
+ CHCl + NaOH
Ph MgBr + CH3O H → Ph  H + Mg CHO
Benzene OCH3
The electrophile involved in the above reaction is
Methoxy ⊕
magnesium (a) dichloromethyl cation (CHCl2 ) [AIEEE 2006]
bromide
(b) dichlorocarbene (: CCl2 )
53 The structure of the compound that gives a tribromo (c) trichloromethyl anion (CCl3)
⊕
derivative on treatment with bromine water is (d) formyl cation (CHO)
[AIEEE 2006] Ans. (b)
CH3 CH2OH
OH- + CHCl3 w H O + CCl2
-
: CCl2 + Cl
-
3
[from Na+OH-] Dichloro
(a) (b) carbene
+
OH ( E)
O− O
CH3 CH3
H
−
OH + : CCl2 CCl2
(c) (d)
s −
O O

CHCl2
s OH
CH 
OH 2NaOH OH
Ans. (a) − 2NaCl
(unstable)
CH3 CH3
Br − OH
O
Br2, H2O
CHO CHO
− H2O H
OH OH
Br
(2-hydroxybenzaldehyde)
Tribromo derivative
334 JEE Main Chapterwise Topicwise Chemistry

55 Acid catalysed hydration of alkenes except ethene leads O H3C H3C

  aq. NH4 Cl |
to the formation of [AIEEE 2005] H3C  C H3C + H3CMgI→ H3C  C  OMgI → H3C  C OH
(a) mixture of secondary and tertiary alcohols  |
(b) mixture of primary and secondary alcohols H3C H3C
(c) secondary or tertiary alcohol 2-methyl-2-
propanol
(d) primary alcohol
Ans. (c) 58 During dehydration of alcohols to alkenes by heating
Hydration of ethene gives 1° alcohol (ethanol) while all other with concentrated H2SO 4 the initiation step is
alkenes give either 2° or 3° alcohols. (a) protonation of alcohol molecule [AIEEE 2003]
H2O/H+ (b) formation of carbocation
CH2 == CH2 → CH3CH2OH
(c) elimination of water
Ethene (d) formation of an ester
H2O/H+
CH3  CH == CH2 → CH3 CH CH3 Ans. (a)

OH Protonation of OH is first step. It involves conversion of poor
+
⊕ leaving group (—OH) into good leaving group ( OH2 ) .
[(2°alcohol) through 2° carbocation CH3 CHCH3 ]
H O/H+
2
CH3  C == CH2 → (CH3) 3 COH 59 Maximum dehydration takes place in that of [AIEEE 2002]
 OH CH3
O O
CH3 ⊕
[(3° alcohol) through 3° carbocation (CH3) 3 C] OH
(a) (b) (c) (d)

OH OH
OH
CH3 CH3 Ans. (b)
| H2O/H+ |
CH3 —CH—CH==CH 2 CH3CH—CH—CH3 Dehydration takes place with the formation of more stable
⊕
2° carbocation carbocation. Among the given compounds, only compound (b)
1, 2 H– H2 O
shift forms conjugated carbocation. Thus, maximum amount of
CH3 2° alcohol dehydration takes place in compound (b).
|
H2O
CH3 — C — CH2—CH3 3° alcohol O O
⊕
3° carbocation
H
H2SO4 (conc.)
56 Among the following compounds which can be H
– H2O
dehydrated very easily ? [AIEEE 2004] OH
OH

(a) CH3CH2CH2CH2CH2OH (b) CH3CH2CH2 CHCH3
CH3
TOPIC 2
| Ethers
(c) CH3CH2C CH2CH3 (d) CH3CH2 CHCH2CH2OH
|  60 Given below are two statements : one is labelled as
OH CH3
Assertion (A) and the other is labelled as Reason (R).
Ans. (c)
Assertion (A) Synthesis of ethyl phenyl ether may be
Dehydration of alcohol is in the order 1°< 2° < 3° achieved by Williamson synthesis.
Thus (c), a 3° alcohol is dehydrated very easily. Reason (R) Reaction of bromobenzene with sodium
ethoxide yields ethyl phenyl ether.
57 Acetyl bromide reacts with excess of CH3MgI followed
In the light of the above statements, choose the most
by treatment with a saturated solution of NH4Cl gives appropriate answer from the options given below
[AIEEE 2004]
[2021, 27 Aug Shift-I]
(a) acetone (b) acetamide (a) Both (A) and (R) are correct and (R) is the correct explanation
(c) 2-methyl-2-propanol (d) acetyl iodide of (A)
Ans. (c) (b) (A) is correct but (R) is incorrect
O O (c) (A) is incorrect but (R) is correct
  (d) Both (A) and (R) are correct but (R) is not the correct
H3C  C Br + H3CMgI → H3C  C  CH3 explanation of (A)
Organic Compounds Containing Oxygen 335

Ans. (b)
Ph
Williamson’s synthesis is used to prepare mixed ethers as well as δ+ δ– –+
simple ether. To prepare ethyl phenyl ether following reaction take C N C NMgBr
place. PhMgBr
–+
Dry ether
ONa OEt
+
OCH3 OCH3 H 3O
+ EtBr Ph Ph
Ethyl
Sodium phenoxide bromide Ethylphenyl ether C O C NH
H3O+ Br
Br +Mg
– NH3 OH
–+
+ EtONa No reaction.
OCH3 OCH3
Sodium
ethoxide
Bromo benzene
This reaction is not possible as bromine has partial double bond 62 In the following reaction sequence, structures of A and
character with benzene ring, so it cannot be dissociated. So, B, respectively will be [2020, 7 Jan Shift-II]
Assertion is correct but Reason is not correct.
O
61 CN HBr Na
(i)C6H5MgBr ∆ A Ether (Intramolecular product) B
(1.0 equivalent), Dry ether
X
(ii)H3O+ CH2Br
(Major product)

OCH3 Br CH2Br
[2021, 16 March Shift-II]
OH
NH2 NH2 (a) and
(a) (b)
CH2Br O

OH OH
C6H5 OCH3
Br
O O (b) and
CH2Br
C6H5 C6H5
(c) (d) Br Br
C6H5
OH
(c) and
O
OCH3 CH2Br
Ans. (d)
OH OH
Cyanide undergoes nucleophilic addition with Grignard followed
by hydrolysis to give carbonyl compound. Br
(d) and
Ph
– +
CH2Br
CN C6H5MgBr C NMgBr
(1.0 equivalent)/dry ether Ans. (d)
The given reaction can be completed as follows :
OCH3 OCH3
O OH
Br
O HBr
H3O+/Hydrolysis Ph
CH2Br CH2Br
(ether + HBr reaction) (A) OH
OCH3
Na/ether
Mechanism Carbon of cyanide is electrophilic and is attacked by (intramolecular
nucleophilic phenyl anion. Wurtz reaction)
(B)
336 JEE Main Chapterwise Topicwise Chemistry

63 The correct order of stability for the following alkoxides (c) A = H3CO OCH3
is [2020, 7 Jan Shift-II]
O– O– O–
O2N OCH3
NO2 NO2
(A) (B) (C)
B = HO OH
(a) (C) > (B) > (A) (b) (B) > (C) > (A)
(c) (B) > (A) > (C) (d) (C) > (A) > (B)
Ans. (a) HO
(C) is most stable due to strong –I effect as well as –R (or −M)
effect of ‘NO2 ’ group. The negative charge is delocalised as
(d) A = HO OH
represented by the following resonance structure :

O CH O O CH O
N CH N CH HO
O O B = H3CO OCH3
In (A), there is no resonance delocalisation of negative
charge, and hence it is least stable. In (B), negative charge is
delocalised by resonance as shown :
OCH3
CH2 O CH2 O Ans. (d)
C C
Alcohols have higher boiling point than ethers of same molecular
N N mass due to possibility of intermolecular hydrogen bonds in
O O O O
alcohols and not in ethers. So, A is alcohol derivative and B is
But the contribution of structure on RHS is relatively less, so ether derivative.
stability of (B) is more than (A) but less than (C).
A=HO OH
B=H3CO OCH3
64 Among the compounds A and B with molecular formula
C 9 H18O 3 , A is having higher boiling point the B. The
possible structures of A and B are [2020, 8 Jan Shift-II] OH
OCH3
(a) A = HO OH
65 The major product of the following reaction is
OCH3
Conc. HBr (excess)
HO
Heat
B = HO
OH CH=== CH2
[2019, 8 April Shift-I]

Br OH
OH (a) (b)
(b) A = H3CO OCH3
BrCHCH3 BrCHCH3
Br OH
(c) (d)
OCH3
B = HO CH2CH2Br CH2CH2Br
OH
Ans. (b)
Key Idea Ethers are least reactive functional groups. The
OH cleavage of C—O bond in ethers take place under drastic
conditions with excess of HX.
Organic Compounds Containing Oxygen 337

The major product obtained in the reaction is as follows: Ans. (d)

OCH3 OH The given reaction takes place as follows :
Conc. HBr (excess)
Heat Cleavage-I
| H+ |
+
O O
CH=
=CH2 Br—CH— CH3 HI (excess) H
Cleavage-II
As conc. HBr is in excess. So, reaction will take place at both the Cleavage-I
substituents. + H
NC O H+ NC O
Cleavage-II
Mechanism
Step 1 Protonation of ether to form oxonium ion. II
va ge-
H lea
via c SN1 pathway
|r
s [via cleavage I]
O—CH3 O—CH3 + Br
H—Br
I OH
+ CH3OH + s
I
+ CH3 CH3I
+
CH=
=CH2 CH=
=CH2 + CH (CH3)2CHI
Oxonium ion + (CH3)2CHOH

Step 2 Attack of nucleophile at the protonated ether. NC OH CH3 CH3 NC I

Product-1 Product-2
H Hs
|r |+ Product-2 is formed because
O—CH3 O CH3
|

SN2
(i) Cleavage-I will give more stable aryl carbocation.
Br-+ Slow
Br (ii) Cleavage- I will give intermediate which is in conjugation
with ring.
CH=
=CH2 CH=
=CH2
67 The major product of the following reaction is
OH
CH3
CH3—Br +
OH
(i) aq. NaOH
CH=
=CH2 (ii) CH3I
[2019, 10 Jan Shift-II]
Step 3 As HBr is in excess, so, reaction will also take place at CH3 CH3
alkene. OH OH
(a) (b)
OH OH
Markownikov’s rule, HBr CH3 CH3
Addition reaction
CH3 CH3
CH=
=CH2 Br CH3 OCH3 OH
(c) (d)
66 The major product of the following reaction is
CH3
O
HI (excess) Ans. (c)
∆
Substituted phenols react withaq.NaOHto form sodium
phenoxides which on reaction with CH3I undergoes S N 2 reaction
NC O to give 2-methoxy-1-methyl benzene.
[2019, 10 April Shift-I]
CH3
OH I OH
(a) (b) NaOH (aq)
Acid-base reaction
–H2O
NC
NC OH OH CH3 CH3
s r
I OH O Na d+ d– OCH3
CH3 I
(c) (d) SN2 reaction
–NaI 2-methoxy-1-
methyl benzene
NC I NC I
338 JEE Main Chapterwise Topicwise Chemistry

68 The major product of the following reaction is 70 The major product formed in the following reaction is
[JEE Main 2018]
COCH3
(i) KMnO4/KOH,D
(ii) H2SO4 (dil.) O HI
CH3 [2019, 11 Jan Shift-I]
Heat
COOH COCH3 O
(a) (b)
HOOC HOOC OH I
(a) (b)
COOH COCOOH
OH I
(c) (d)
OHC HOOC
OH I
(c) (d)
Ans. (a)
I OH
In presence of alkalineKMnO4 , vigorous oxidation of alkyl or acyl
benzene takes place. During oxidation, aromatic nucleus
Ans. (d)
remains intact but the entire chain is oxidised to —COOH group The reaction given is a nucleophilic substitution reaction in which
irrespective of the length of carbon chain. cleavage at CO bond is visible. The product formation can be
visualised with the help of following analysis.
Oxidative cleavage
O==C—CH3 in strong
– – –
O ==C—O K These two atoms are directly
(MnO4 /OH /D) attached to benzene ring.
KMnO4/KOH/∆ a O Hence, development of
any charge on these atoms is
Strong oxidation, [O] stabilised by the ring itself due
O b to conjugation (Resonance)
CH3 COOK
(also H3O+(dil. H2SO4)
oxidisable)
If any one properly visualise the fact written with figure above,
COOH than a conclusion can be made that C O bonds marked (a) and (b)
in the figure will undergo heterolysis during the reaction.
The reaction can be represented as

COOH
O HI I
Heat + I + CH3OH
69 The major product obtained in the following conversion O
is OH
Mechanism
CH3
Step I The reaction begins with the attack ofH+ of HI on oxygen
O to form oxonium ion as
Br2 (1 eqv.) MeOH +
O O
HI
∆ H
[2019, 11 Jan Shift-II] O O
Oxonium ion
Ans. (b)
Step II This oxonium ion undergoes lysis and addition ofI − to
In presence ofBr2 /EtOH, the reactant containing double bond
form two products as
undergoes electrophilic addition reaction via the formation of
•• +
bromonium ion. On further attack of  OMe on bromonium ion O
••
I– I + CH OH
gives the addition product. H 3

H3C COMe O O
O
Br2(1 eqiv) O MeOH Step III Similar pathway is followed at the other oxygen atom,
O in MeOH
Br which can be visualised as
(Protic solvent)

O I HI I I– I
O ∆ + CH3CH2I
+
O
O O O
OMe H H
Br
Note Mechanism of a reaction is always a logical sequencing of
(Major) events which may occur simultaneously as well.
Organic Compounds Containing Oxygen 339

71 Consider the following reaction, TOPIC 3

C 2H5OH + H2SO 4 → Product Aldehydes and Ketones
Among the following, which one cannot be formed as
a product under any conditions? [AIEEE 2011]
74 Given below are two statements.
(a) Ethyl hydrogen sulphate (b) Ethylene
Statement I The nucleophilic addition of sodium
(c) Acetylene (d) Diethyl ether
hydrogen sulphite to an aldehyde or a ketone involves
Ans. (c)
proton transfer to form a stable ion.
(a), (b), (d) may be formed but (c) is never formed.
Statement II The nucleophilic addition of hydrogen
Room temp. cyanide to an aldehyde or a ketone yields amine as
C2H5OH + H2SO4
final product.
C2H5HSO4 In the light of the above statements, choose the most
Ethylhydrogen sulphate
appropriate answer from the options given below.
[2021, 1 Sep Shift-II]
0°

17
–H
14

0°

(a) Both statement I and statement II are true.

5O

2
SO
2H

(b) Statement I is false but statement II is true.

4
C

(c) Statement I is true but statement II is false.

C2H5OC2H5 CH2==CH2 (d) Both statement I and statement II are false.
Diethyl ether Ethylene
Ans. (c)
Nucleophilic addition of sodium hydrogen sulphite (NaHSO3) to
72 Sodium ethoxide has reacted with ethanoyl chloride. carbonyl compound (aldehyde or ketone) involves proton
The compound that is produced in the above reaction is transfer to form a stable ion.
[AIEEE 2011] OH
(a) diethyl ether (b) 2-butanone O O
NaHSO3 Transfer of proton C
C==O C O
(c) ethyl chloride (d) ethyl ethanoate
Carbonyl S S s
Ans. (d) compound O—H O
O
− O
C2H5O Na+ s C2H5O—+ Na+ Stable ion
s (due to conjugation)
O O Hence, statement I is true.
Nucleophilic addition of HCN (hydrogen cyanide) to an
CH3 — C — Cl e CH — C — Cl 3 r C2H5O– aldehyde/ketone yield cyanohydrin as final product.
(ethanoyl chloride)
OH
HCN
s ==O
O O CN
Carbonyl Cyanohydrin
compound
CH3 — C — Cl CH3 — C — OC2H5 + Cl–
Hence, statement II is false.
O — C2H5
75 Which one of the following is the major product of the
Na+ + Cl — → NaCl
given reaction? [2021, 27 Aug Shift-II]
This is byS N reaction. Cl − is a better leaving group than C2H5O−
CH3
and the ethyl ethanoate is formed.
NC
(i) 2CH3MgBr
Major product
73 An ether is more volatile than an alcohol having the (ii) H3O+
same molecular formula. This is due to [AIEEE 2003] CH3 (iii) H2SO4, heat

(a) dipolar character of ethers CH3

(b) alcohols having resonance structures CH3
(c) intermolecular hydrogen bonding in ethers (a) CH3
(d) intermolecular hydrogen bonding in alcohols CH3
Ans. (d) CH3
Alcohol has polar H which makes intermolecular H-bonding NC CH3
possible. Ether is non-polar, hence has no H-bonding. Lack of (b)
H-bonding in ether makes it more volatile than alcohol.
CH3
340 JEE Main Chapterwise Topicwise Chemistry

CH3
76 In the following sequence of reactions, the final product
NC CH3 D is [2021, 27 Aug Shift-I]
(c) OH
CH3
Br CH3
CH3 CH3 C==C H + NaNH2 A B
H2/Pd–C CrO3
CH3 C D
(d) CH3
O
CH3 
(a) H3C CH2 CH2 CH2 CH2 C H
Ans. (a)
(b) CH3 CH == CH CH2 CH2 CH2 COOH
The reaction of keto and cyanide group with Grignard reagent
and further hydrolysis gives alcohol and keto group respectively. (c) H3C CH == CH CH(OH) CH2 CH2 CH3
On further heating withH2SO4 at — OH group is eliminated O
resulting in formation of alkene. 
(d) CH3 CH2 CH2 CH2 CH2 C CH3
Å
NC O NººC O MgBr Ans. (d)
(i)CH3MgBr
NaNH2 is a strong base that causes deprotonation of propyne
and forms acetylide ion (A) which further combines with the
carbon chain and forms hept-5-yn-2-ol (B) that undergoes
CH3MgBr reduction in presence ofH2 /Pd-C and forms heptan-2-ol (C).
CH3 Being a secondary alcohol (C), oxidises in presence of CrO3 to
Å give corresponding ketone i.e. heptan-2-one (D).
Å C O MgBr
BrMg N The complete reaction take place as follows.

CH3—CººCH + NaNH 2 CH3—CººC Na+ + NH 3

Å Propyne (A)
(ii)H3O
Acetylide ion
OH OH OH
H 2 O H 2N Å −HÅ HN
Br CH3

CH3—CººC—CH 2—CH 2—CH—CH 3

OH
H 2N (B) OH
O Hept-5-yn-2-ol
H Å H  H2 / Pd - C
↓
OH OH OH
Å Å
−HÅ 
H 3N O HO CH3  CH2  CH2  CH2  CH2  CH  CH3
H (C )
Heptan-2 -ol
O
OH  CrO 3
↓
Å
OH2
(iii) H2SO4/D O CH3  (CH2 ) 4  C  CH3

O
(D )
O O Heptan-2 -one
H
Å
a a (i) DIBAL–H
b
–HÅ
77 R  CN → R Y
(ii) H2 O
H (More favoured)
The double bond is Consider the above reaction and identify Y.
b –HÅ in conjugation with [2021, 27 July Shift-II]
O aromatic ring.
(a) CH2NH2 (b) CONH2 (c)  CHO (d)  COOH
Ans. (c)
DIBAL-H, i.e. di-isobutyl aluminium hydride causes partial
(Less forward) reduction of cyanide group and further hydrolysis forms
corresponding aldehyde.
Therefore, option (a) is correct.
Organic Compounds Containing Oxygen 341
O
List-I List-II
(ii) H 2 O


(i) DIBAL-H
R  CN  → R  CH → R  C H (Chemical reaction) (Reagent used)
H +
(R  Y )
Cyanide  C. CH3C ≡≡ N → CH3CHO 3. DIBAL -H/H2O
Aldehyde
NH
Imine D. CH3C ≡≡ N → 4. SnCl 2 , HCl /H2O
O
Hence,Y is CHO group.

78 Which one of the following compounds will give orange CH3 CH3
precipitate when treated with 2, 4 dinitrophenyl Choose the most appropriate option given below.
hydrazine? [2021, 27 July Shift-I] [2021, 26 Aug Shift-II]

O A B C D A B C D
OH (a) 2 4 3 1 (b) 4 2 3 1
(a) (b) OCH2CH3 (c) 2 3 4 1 (d) 3 2 1 4
OCH2CH3
Ans. (c)
O (A) This reaction is reverse of esterification. As it takes place in
O presence of acid and the ester molecule gets hydrolysed,
O the reaction is called as acidic hydrolysis of ester (hydrolysis
C—OH is breaking of molecule in presence of water). Acidic
(c) (d) CH3 hydrolysis is reversible reacton, hence does not go to
completion.
OH
H 2 SO 4
Ans. (d) CH3COOC2H5 → C2H5OH
H2 O
2, 4-dinitrophenylhydrazine can be used for qualitative Ester Alcohol
identification of ketone or aldehyde functional group. (B) Diisobutylaluminium hydride (DIBAL-H) is a reducing agent,
A successful test is indicated by formation of yellow, orange or which reduces ester to aldehyde.
red colour precipitate which is known as
DIBAL-H
dinitrophenylhydrazone. CH3COOCH3 → CH3CHO
H2 O
Ester Aldehyde
OH
(a) – Presence of alcohol and ester (C) This reaction is called Stephen aldehyde synthesis which
OC2H5 involves preparation of aldehyde from nitrile using SnCl2 ,
HCl and quenching of resulting iminium salt
([R —CH == NH2 ] + Cl − ) with H2O.
SnCl
CH3C ≡≡ N →
2
CH3CHO
HCl/H 2 O
Nitrile Aldehyde
(b) OC2H5 – Presence of ester group
(D) Grignard reagent (CH3MgBr) attack electrophilic carbon in
the nitrile to form imine salt, this salt then gets hydrolysed
to form a ketone.
C—OH
– Presence of alcoholic and CH MgBr
(c) CH3  C ≡≡ N →
3
CH3 CH3
carboxylic acid group H O+ 3
Nitrile
OH Ketone
Thus, the correct match is (c) A → 2, B → 3, C → 4, D → 1.
Above compounds will not give 2, 4-DNP test due to absence of
carbonyl group.
80 The major products formed in the following reaction
sequence A and B are [2021, 26 Aug Shift-I]
C—CH3 – Presence of ketone group,
(d) so it will give orange ppt.
when treated with 2, 4-DNP. CH3 Br2
KOH A+B

79 Match List-I with List-II. O

List-I List-II (a) A= C , B=CHBr3
(Chemical reaction) (Reagent used) OK

A. CH3COOC 2H5 → 1. CH3MgBr /H3O + (1.equivalent) O O

C 2H5OH
(b) A= CCH2Br , B= CCH2OH
B. CH3COOCH3 → 2. H2SO 4 /H2O
CH3CHO Br Br
342 JEE Main Chapterwise Topicwise Chemistry

O OEt H2C OEt

(c) A= CCBr3 , B= CHO (c) EtO
,
OEt OEt
Br OEt OEt
t
(d) Br BuO
Br O HO O ,
OEt OEt
(d) A= CCH3 , B= CCH3 Ans. (a)
In reaction t -BuOsH+ is used as a base to remove HBr and form
Br HO alkene as a major product (B) via E2 elimination mechanism.
Ans. (a) Machanism Firstly, 1-bromoacetaldehyde undergoes protonation
Acetophenone is a methyl ketone which on reaction withBr2 and which is then react witht -BuOsH+ . (t - BuOs act as nucleophile
KOH will give conjugate base of an acid and methyl group will and attack on carbonyl carbon). In next step,t -BuOsH+ act as
turn into haloform. This reaction is haloform reaction. base and accepts proton and at last alkene is formed as major
product.
OH O—H
C C H+ EtOH
CH3 Br2 O K + CHBr3 Br C Br C Br
H H +
KOH H O—H
1-bromo acetaldehyde
Acetophenone (A) (B) Et
Haloform H
Conjugate base of
Mechanism acid (Bromoform)
O—H OEt
Br Br
H OEt EtOH H O—Et
C –
C
CH3 OH CH2
H
OEt t OEt
–H+ BuO– K+
Br H2C== C
C C ==CH2 –HBr OEt
CH2 Br—Br H OEt (E2-mechanism)
1, 1-diethoxy ethene
–Br
(2-bromo-
Br 1,1-diethoxy ethane)

–2Br +2OH 82 A reaction of benzonitrile with one equivalent CH3MgBr

+2Br2
followed by hydrolysis produces a yellow liquid P. The
compound P will give positive [2021 25 July Shift-II]
C (a) iodoform test (b) Schiff’s test
C OH CBr3
CBr3 (c) ninhydrin’s test (d) Tollen’s test
OH
Ans. (a)
Treatment of benzonitrile with Grignard reagent followed by acid
+ C hydrolysis gives acetophenone product.
C H transfer OH
OK
+ CBr3 C N CH3
+ CHBr3 +–
Stabilised by 3
electron
– +
CH3MgBr
C NMgBr
withdrawing groups Grignard
reagent Intermediate O
– + Bromonitrile
EtOH (excess) BuO K in ionic form
81 Br CHO Dry HCl gas A B C CH3
(Major (Major
product) product)
+
H 3O
+ NH3
[where, Et = C 2H5 , t Bu = (CH3 ) 3 C—]
Consider the above reaction sequence, product A and Acetophenone
(Its gives positive
product B formed respectively are [2021, 25 July Shift-II] iodoform test)

OEt H2C OEt Iodoform test is used to check the presence of carbonyl
(a) compound with the structure R  CO  CH3 or alcohols with the
Br
OEt
,
OEt structure R  CH(OH)  CH3 in a given unknown substance. The
reaction of iodine, a base and a methyl ketone gives a yellow
OtBu precipitate along with an “antiseptic” smell.
(b) EtO CHO EtO
, C6H5  CO  CH3 + I2 + NaOH → C6H5 COONa + CHl 3 ↓
OEt
This conclude that acetophenone give iodof form test.
Organic Compounds Containing Oxygen 343
O O
O
CH3CHO (i) I2/NaOH, filter +
H C
83 NaOH
‘P’
(ii) Filtrate + HCl
‘X’ (a) + KMnO4 +
(Major product) H H
2-methylpropene (C3H6O)
Consider the given reaction, the product X is B
[2021, 22 July Shift-I] O O
O OH O O Zn/H2O2
+ O3 +
(C3H6O) H H
(a) (b) B
O
O O H+
(c) + KMnO4 2 H
OH
(C2H4O)
(c) CHO (d) OH
O
Zn/H2O2
+ O3 2 H
Ans. (d)
In first step, aldol reaction is involved in reaction mechanism and So, only 2-methylpropene gives compound B with molecular
in second step, (I2 , NaOH) is used for iodoform test, which gives formula, C3H6O.
CHI3 ( yellow precipitate) as by product. Therefore, compound A is 2-methylpropene.
Reaction Mechanism
85 An organic compound A (C 6H6O) gives dark green
O O
colouration with ferric chloride. On treatment with
H OH CHCl 3 and KOH, followed by acidification gives
–H2O Enolate compound B. Compound B can also be obtained from
2,2-dimethylcyclopentan
s
compound C on reaction with pyridinium
-1-one O
O O O– chlorochromate (PCC). Identify A, B and C.
[2021, 22 July Shift-II]
CH CH3—C—H
H—O—H OH OH
CH3 Rate
determining OH CHO CH2OH
step
(a) A= B= C=

O OH
O O CH2OH
OH OH
(i) I2, NaOH
CH3 C—ONa OH CHO
(Iodoform test) Carboxylate (b) A= B= C=
+ CHI3
( P) ion (Yellow
(Major product) (Filtrate)
ppt.)
[5-(1-hydroxyethyl)-2,2-
dimethyl CH2OH OH OH
(ii) HCl
cyclopentan-1-one] OH CHO
(c) A= B= C=
O O

OH OH CH2OH OH
CHO OH
(X)
(3,3-dimethyl-2-oxycyclopentane- (d) A= B= C=
1-carboxylic acid)

Ans. (a)
84 An organic compound ‘A’ C 4H8 on treatment with
Compound A is phenol, compound B is salicylaldehyde and
KMnO 4 /H+ yield’s compound ‘B’ C 3H6O. compound C is 2-hydroxy methyl phenol.
Compound ‘A’ also yields compound ‘B’ an ozonolysis. When phenols react with ferric chloride solution to give blue,
Compound ‘A’ is [2021, 25 July Shift-I] violet or green colouration  due to the formation of ferric
(a) 2-methylpropene phenoxide which gives different coloured water soluble complex
compounds.
(b) 1-methylcyclopropane
(c) but-2-ene Phenol reacts with chloroform and alcoholic KOH to
give  salicylaldehyde. This reaction is called Reimer-Tiemann
(c) cyclobutane
reaction.
Ans. (a) Salicylaldehyde also obtained on reaction of 2-hydroxy methyl
Alkenes react withKMnO4 / H+ andO3 to give carbonyl compound. phenol with pyridinium chlorochromate (PCC).
344 JEE Main Chapterwise Topicwise Chemistry

Chemical reactions are as follows : Step IIIβ-hydroxy ketone undergoes dehydrate to form a
conjugated enone.
OH OH
OH
CHO
Reimer-Tiemann
+ CHCl3 + KOH
reaction O −H2O O

(A) (B)
Phenol OH Salicylaldehyde O O
Conjugated enone
CH2OH Pyridinium
chlorochromate
87 OH
Oxidation reaction O
OH
(C) CHO OH
2-hydroxy methyl phenol (I) (II) (III) (IV)
Which among the above compound/s does/do not
86 The major product P in the following reaction is
form silver mirror when treated with Tollen's reagent?
[2021, 20 July Shift-I]
CHO
(i) KOH (alc.) (a) (I), (III) and (IV) only (b) Only (IV)
P
(ii) H+, ∆ (Major product) (c) Only (II) (d) (III) and (IV) only
[2021, 20 July Shift-II] Ans. (c)
O O Only compound (II) which has ketonic group does not form silver
OHC
mirror when treated with Tollen’s reagent.
(a) (b) Because Tollen’s reagent oxidises an aldehyde into the
corresponding carboxylic acid. Ketones are not oxidised by
O Tollen’s reagent, so the treatment of a ketone with Tollen’s
O
reagent in a glass test tube does not result in a silver mirror.
CHO
Aldehydes give positive Tollen’s test (silver mirror test).
(c) (d)
(I) Positive
O O CHO
Ans. (b) OH O
Tauto Negative
Given reaction is aldol condensation. (II)
Ketone
H3C O
CH==O C==O Tauto
(III) Positive
CH2—CH2 KOH (alc.) O OH H
+
H, ∆ –
O O O +
[Ag(NH3)2] OH– O O
(IV) Positive
H2O H
In this reaction, substrate undergoes intramolecular aldol OH O– O
condensation in which condensation reaction of two aldehyde Hemiacetal

groups or ketone groups occur in same molecule.

Mechanism 88 An unsaturated hydrocarbon X on ozonolysis gives A.
Step I Abstraction of proton by base KOH to form enolate. Compound A when warmed with ammonical silver
nitrate forms a bright silver mirror along the sides of the
H 3C ÈCH
2 test tube. The unsaturated hydrocarbon X is
CH==O C==O CH==O C==O [2021, 17 March Shift-II]
CH2—CH2 CH2—CH2 CH3
KOH
|
O O (a) CH3 C === C  CH3 (b) CH3  C ==
Enolate  
CH3 CH3
Step II Reaction of enolate and aldehyde group on substrate to
form β-hydroxy ketone. (c) HC ≡≡ C  CH2  CH3 (d) CH3  C ≡≡ C  CH3
OH Ans. (c)
È –
O
CH2 On ozonolysis, unsaturated hydrocarbon X will form carbonyl
CH==O C==O β α
H + O compound, which gives positive Tollen’s test. So, it should be
CH2—CH2 O aldehyde.
O (a) 2, 3-dimethylbut-2-ene undergoes ozonolysis reaction to
O O β-hydroxy ketone give 2 molecules of acetone.
Organic Compounds Containing Oxygen 345

H3C—C==C—CH3
(i) O3
2 CH3 — C==O
90 Assertion (A) Enol form of acetone
(ii) Zn/H2O
[CH3COCH3] exists in < 0.1% quantity. However, the
CH3 CH3 CH3
Ketone (acetone)
enol form of acetyl acetone [CH3COCH2OCCH3] exists
2-3-dimethylbut-2-ene
in approximately 15% quantity.
(b) Isopropylidiene undergoes ozonolysis reaction to give Reason (R) Enol form of acetyl acetone is stabilised by
acetone along with cyclopropanone.
intramolecular hydrogen bonding, which is not
CH3 CH3 possible in enol form of acetone.
(i) O3
—
CH3—C — —O + O—
H3C—C — — Choose the correct statement. [2021, 16 March Shift-I]
(ii) Zn/H2O
Acetone Cyclopropanone (a) A is false but R is true.
Isopropylidiene
(b) Both A and R are true and R is the correct explanation of A.
(c) Butyne reacts with O3 and Zn/H2O to give
(c) Both A and R are true but R is not the correct explanation
2-oxobutyraldehyde. The aldehyde will give Tollen’s test to
give silver mirror. of A.
Note Tollen’s reagent contain silver nitrate (AgNO3),
(d) A is true but R is false.
ammonia and sodium hydroxide (NaOH) which react with Ans. (b)
aldehydes to give Ag (silver mirror). Enol form of acetone [CH3COCH3] exists in
< 0.1% quantity as monocarbonyl are more stable in keto form
due to high bond energy.
O3
CH C—CH2 —CH3 HC—C—CH2 —CH3 O OH
Zn/H2O
Butyne 2-oxobutyraldehyde  Tautomerisation 
Tollen's CH3  C  CH3 → CH3  C == CH2
Silver mirror Keto Enol
reagent
The enol form of acetyl acetone [CH3COCH2OCCH3] exists in
(d) But-2-yne undergoes ozonolysis to give butan-2, 3-dione. approximately 15% quantity as it is stabilised by intramolecular
hydrogen bonding, which is not possible in enol form of acetone.
O3 CH
CH3—C C—CH3 H3C—C—C—CH3 CH3—C C—OC2H5
Zn/H2O
But-2-yne Butan-2, 3-dione
CH3—C—CH2—C—O—C2H5
O O
Only product of option (c) contains aldehyde group. δ−
H
δ+
89 O O (More stable enol
form due to H-bonding)
Ethylene glycol
OC2H5 A So, both A and R are true and R is the correct explanation of A.
H+ (Major product)
91 O
The product in the above reaction is O
[2021, 16 March Shift-I]

OH (i) DIBAL-H,Toluene,–78°C
'P'
O O (ii) H3O+
(a) OH (b) O (Major product)
O O
OC2H5 The product P in the above reaction is
OC2H5 [2021, 16 March Shift-I]
O
OH
(c) OC2H5 (d) O
O O COOH CHO
OH OH (a) (b)

Ans. (b) O
Nucleophilic addition of ethylene glycol in ketone to give ketal. OCH

O O (c) (d) CHO

Ethylene glycol

H 3C H+
OC2H5 OC2H5
Cyclic-ketal
Ethyl-3-oxobutanoate Ans. (b)
(Product A)
DIBAlL is added to produce aldehyde from ester by keeping the
Addition of one molecule of alcohol on ketone give hemiketal and temperature low while at higher temperature it can perform
addition of two molecules give ketal. different conversions.
346 JEE Main Chapterwise Topicwise Chemistry

Complete reaction is as follows:

CH2O—H CH2ONa
OH CH3CH2–Br
Na H (in DMF)
–78°C CHO –H2 –NaBr [SN2
O
(Acid-base reaction]
O i) DIBAL-H,
(P) reaction)
Toluene OCH3 OCH3
+ OH CH2OCH2CH3
ii) H3O
25°C CH2OH

Diisobutyl aluminium hydride (DIBAL-H) is parallel to LAH OCH3

(Lithium aluminium hydride) as a reducing agent but it is more
(iii) In last step, 1-ethoxymethyl-4-methoxybenzene undergoes
selective.
solvolysis reaction followed by S N 2 attack of two iodide ion
It forms different product at different temperature. (I− ) to give 4-iodomethyl phenol, iodoform and iodoethane.
Role of DIBAL-H is shown below Less
–
H—I I active
Reagent DIBAL-H (− 78°C) DIBAL-H (25° C) DIBAL-H (–78°C) 1° 1°
CH2—O—CH2CH3 CH2—O—CH2CH3
Reactant Ester Ester Cyanide
2HI/∆ H
Product Aldehyde Alcohol Aldehyde
[Complete
Note : DIBAL-H does not reduce double bond. solvolysis
with HI]
I
O—CH3 –2I H—O—CH3
92 Identify A in the following chemical reaction. H—I Benzylic Aromatic
[2021, 26 Feb Shift-II] 1º-carbon sp2-carbon
CHO Diether more active (Aryl centre)
(i) HCHO, NaOH in SN1
A CH2I
(ii) CH3CH2Br, NaH, DMF
SN2 attack of
CH3O (iii) HI, ∆
two I– (nucleophile
O CH3I + CH3CH2OH + to protonated
CH2OH HI –H2O Diether
C OCH2CH3
(a) (b) OH
CH3CH2I
4-iodomethyl phenol
CH3O
HO
93 Identify A in the given chemical reaction,
CH2I CH2OH
CH2CH2CHO
NaOH
(c) (d) A (Major product)
C2H5OH, H2O
HO HO
CH2CH2CHO
Ans. (c) [2021, 26 Feb Shift-II]

Here, 4-methoxybenzaldehyde in series of reaction finally forms CHO CH2CH2COOH

4-(iodomethyl) phenol (A). Let us compute the reaction step by (a) (b)
step with mechanism as follows
CH2CH2CH2OH
(i) In first step, oxidising agent (p-methoxybenzaldehyde) O
reacts with formaldehyde in presence of strong base NaOH
to give p-methoxybenzyl alcohol along with sodium salt of C H
methanoic acid. It is known as Cannizzaro’s reaction. O
CH2OH (c) (d)
+1
CHO O
NaOH
+ HCHO + HCOONa Ans. (c)
Cannizzaro
CH3O Reducing reaction
Oxidising agent CH2 C—CHO CH2 CHO
agent (Formaldehyde) OCH3 NaOH,
(p-methoxy H HO C2H5OH, H2O
C
benzaldehyde) CH CH
CH2 CH2 CH2 CH2
(ii) In second step, deprotonation of p-methoxybenzyl alcohol or
CHO
in presence of sodium hydride (NaH) to form alkoxide which
further react with bromoethane in presence of DMF to give
1-ethoxymethyl-4-methoxybenzene.
Organic Compounds Containing Oxygen 347

It is an example of intramolecular aldol condensation. Compound A (C4H8 Cl2 ) is a dihalide which undergoes hot
α - hydrogen atom of one  CHO group gets abstracted by NaOH hydrolysis (H2O/373 K) to give B, a ketone. So, A is a non-terminal
form enolate ion which then attacks of another  CHO group to geminal or gem dichloride and A is
form aldol or β - hydroxy aldehyde. The aldol on heating Cl
C2H5OH/H2O forms the final product (α, β-unsaturated aldehyde) 
CH3  C  CH2 CH3 (C4H8 Cl2 )
as the major product.  2,2-dichlorobutane
Mechanism Cl
2 2 The reaction can be computed as,
3 1 3 1
O OH O Cl O—H O
H H H
O –H2O O 2H2O/373K –H2O
4 6 4 6 CH3—C—CH2CH3 CH3—C—CH2CH3 CH3—C—CH2CH3
5 7 5 7 –2HCl
Enolate ion (B)
Cl OH 2-butanone
H2 O
(A ) Butane-2, 2-diol (unstable)
–OH 2, 2-dichlorobutane [Non-terminal gem-diol]
2 2
3 1 3 1
α O C2H5OH/H2O α O 96 The major product of the following reaction is
β H β
4 7 ∆ H 2 / CO
CH3CH2CH== CH2 →
4 7
5 6 –H2O 5 6 OH
α,β-unsaturated aldehyde More acidic β-H Aldol Rh catalyst [2021, 25 Feb Shift-II]
(Major aldol [β-elimination] [β-hydroxy aldehyde]
condensation product) (a) CH3CH2CH2CH2CHO (b) CH3CH2CH2CHO
(c) CH3CH2CH== CH—CHO (d) CH3 CH2 C == CH2

94 2,4-DNP test can be used to identify [2021, 26 Feb Shift-II] CHO
(a) amine (b) aldehyde
Ans. (a)
(c) ether (d) halogens
The major product of the reaction is CH3CH2 CH2 CH2 CHO. Here,
Ans. (b) +
electrophilic addition ofH— C == O (formylation) take place to the
2, 4 - DNP test is used to detect the presence of carbonyl group
(aldehyde or ketone) in organic compound.The test is carried out alkene through Markownikoff addition.
••• ⊕
→ [H — C == O] H s
with 2, 4- dinitro phenyl hydrazine or 2, 4 - DNP (Brady’s reagent) Rh
(i) H2 + •• C == O •
to give a reddish orange precipitate. Water gas (Catalyst)

NO2 ⊕
H— C == O
(ii) CH3CH2 — CH == CH2 →
H+ Slow
C O + H2 N—NH— — NO2 But-1-ene
–H2O
NO2 ⊕ Hs
Aldehyde or ketone 2, 4-DNP CH3CH2  CH  CH2  CHO → CH3CH2 CH2 CH2 CHO (major)
Fast
Pentanal
C N —NH— —NO2
(Reddish orange ppt.) 97 Which one of the following reactions will not form
2, 4-dinitrophenyl hydrazone
compound acetaldehyde? [2021, 25 Feb Shift-I]
Pd (II) / Cu (II)
(a) CH2 == CH2 + O2 →
Hydrolysis H2 O
95 A → B CrO 3 -H 2 SO 4
373 K
(C 4H 8 Cl2 ) (C 4H 8 O)
(b) CH3CH2OH →
B reacts with hydroxyl amine but does not give Tollen's (i) DIBAL -H
(c) CH3CN →
test. Identify A and B. [2021, 26 Feb Shift-I] (ii) H 2 O

(a) 1,1-dichlorobutane and 2-butanone Cu

(d) CH3CH2OH →
(b) 2,2-dichlorobutane and butanal 573 K
(c) 1,1-dichlorobutane and butanal Ans. (b)
(d) 2,2-dichlorobutane and 2-butan-one Pd(II)/Cu(II)
CH2 == CH2 + O2  
→ CH3CHO
Ans. (d) Ethene
H2 O
Ethanal
Compound B (C4H8O) reacts with hydroxylamine (NH2OH) . So, O
compound B is an aldehyde or a ketone. Again, B does not give  CrO3 ⋅H2 SO4
Tollen’s test which indicates that B is a ketone but not an CH3CH2OH  → CH3  C OH
aldehyde. So, B is Ethanol Ethanoic acid
O O
 
CH3  C  CH2 CH3 (C4H8O ) CH3CN DIBAL-
 H→ CH3  C H CH3CH2OH 
Cu
→ CH3CHO
Acetonitrile H2 O 573 K
2- butan- one Ethanal Ethanol Ethanal
348 JEE Main Chapterwise Topicwise Chemistry

Since, CrO3 ⋅H2SO4 behave as strong oxidising agent and it Ans. (c)
converts alcohol directly to carboxylic acid. Thus, reaction (b) will Reaction of HgSO4 /dil. H2SO4 with alkyne result in addition of
not form acetaldehyde. water as per Markownikoff’s rule.
98 The major product of the following chemical reaction is O
+ HgSO4
(i) H3 O , ∆ (a) HC CH CH2 CH CH3—CH
H2SO4
(ii) SOCl2 Acetylene Acetaldehyde
CH3CH2CN → ? OH
(iii) Pd /BaSO4 , H2
[2021, 25 Feb Shift-I]
HgSO4
(a) CH3CH2CH2OH (b) (CH3CH2CO)2 O (b) —C CH H SO —C CH
2 4
(c) CH3CH2CH3 (d) CH3CH2CHO
Cyclohexyl ethyne OH
Ans. (d) O
The complete reaction take place as follows
—C—CH3

(i) H3O+ 1-cyclo hexylethan-1-one

CH3 CH2 C — N D
CH3—CH2 — C — OH
Ethyl cyanide Propanoic acid HgSO4
(c) CH3—C CH H SO CH3—C CH2
2 4
(ii) SOCl2 Prop-1-yne
CH3 — CH2 — C — Cl OH O
Propanoyl chloride
Rosenmund's (iii) Pd/BaSO4, H2 CH3—C—CH3
reaction
Acetone

CH3 — CH2 — C — H Hence CH3  CO  CH3 cannot be form.

Propanaldehyde HgSO
(d) CH3C ≡≡ C  CH3 → 4
CH3  C == CH  CH3
Final product of reaction is propanaldehyde. But -2 - yne
H 2 SO 4

OH
99 O

? c CH3  C  CH2  CH3
But -2 - one
O
101 Match List-I with List-II.
Which of the following reagent is suitable for the
preparation of the product in the above reaction? List-I List-II
[2021, 24 Feb Shift-II]
È⊕ A. O 1. Br2 /NaOH
(a) NaBH4 (b) NH2 NH2 /C2H5 ONa 
R  C  Cl → R  CHO
(c) Ni/H2 (d) Red P + Cl2
B. R  CH2  COOH 2. H2 /Pd -BaSO 4
Ans. (b)
→ R  CH  COOH
To reduce the carbonyl groups into alkane, wolff-Kishner reduction

is used, without affecting the double bond. Cl
Wolff-Kishner reagent It utilises hydrazine (NH2 NH2 ) as the
C. O 3. Zn(Hg) / Conc.HCl
reducing agent in the presence of strong base KOH or
− + 
C2H5 ONa in a high boiling protic solvent. The driving force for R  C NH2 → R NH2
the reaction is the conversion of hydrazine to nitrogen gas. O
D. 4. Cl 2 / Red P, H2O

R  C  CH3 → R  CH2  CH3
(i) NH2–NH2
(ii) C2 H5 O– Na+ /∆
Choose the correct answer from the options given
below. [2021, 24 Feb Shift-II]
100 Which one of the following carbonyl compounds cannot A B C D
be prepared by addition of water on an alkyne in the (a) 2 1 4 3
presence of HgSO 4 and H2SO 4 ? [2021, 24 Feb Shift-II] (b) 3 4 1 2
O O (c) 2 4 1 3
(a) CH3 C H (b) (d) 3 1 4 2
C CH3
Ans. (c)
O O
(A) Alkyl chloride reacts withH2 /Pd-BaSO 4 and reduced to alkyl
(c) CH3 CH2 C H (d) CH3 C CH2CH3 aldehyde. This is known as Rosenmund reduction.
Organic Compounds Containing Oxygen 349
O O Ans. (d)
 H2 
R  C  Cl  → R  C H Addition of HCN to C O group of a carbonyl compound
Pd -BaSO4 Alkylal dehyde follows nucleophilic addition mechanism.
Alkyl chloride
(Rosenmund reduction) δ+ δ–
Rate of nucleophilic addition ∝ Polarity of the C O
(B) Carboxylic acid reacts with Cl2 /P in aqueous medium to
form 2-chlorocarboxylic acid. This reaction is known as HVZ group ∝ Attachment of electron withdrawing group (EWG), i.e.,
reaction. −R and −I groups, where − R > − I
Cl 2 /P 1
∝
R  CH2  COOH  → R  CH  COOH Attachment of electron donating group (EDG)
H2 O
Alkyl carboxylic acid 
Cl i.e., + R and + I groups
2-chlorocarboxylic acid In substituted benzaldehyde, NO2 (EWG) shows −R effect from
[Hell-Volhard-Zelinsky (HVZ) reaction] ortho-and para-positions and −I effect (only) from
(C) Alkyl amide reacts withBr2 in presence of NaOH to give alkyl meta-positions. The group OCH3 (EDG) shows + R effect from
amine. This reaction is known as Hofmann bromide ortho-and para-position but −I effect from meta-positions.
reaction, EWG (−R > −I) increases ‘δ +’ character of sp2 carbon of the
O C O group and hence attack of the nucleophile (CN− ) will be
 Br2
R  C NH2   → R  NH2 easier.
NaOH (–I)
Alkyl amide Alkyl amine
CH3O CHO CHO
(Hofmann bromide reaction)
(D) Ketone reacts with Zn-Hg in presence of conc.HCl to give (i) (ii)
alkane. This reaction is known as clemmensen reduction. NO2
O (–R)
 Zn(Hg)
(–I )
R  C  CH3   → R  CH2  CH3 CHO O2N CHO
Conc. HCl
Ketone Alkane
(Clemmenson reduction) (iii) (iv)
Hence, correct match is (A)–2, (B)–4, (C)–1, (D)–3. OCH3
(+R )
102 Which of the following reagent is used for the following So, the increasing order of HCN addition is :
reaction ?
CH3CH2CH3 → ?
CH3CH2CHO (iii) < (i) < (iv) < (ii)
+R –I –I –R
[2021, 24 Feb Shift-I]
(a) Copper at high temperature and pressure – I effect : NO2 > OCH3
(b) Molybdenum oxide
(c) Manganese acetate
(d) Potassium permanganate
104 The increasing order of the reactivity of the following
compounds in nucleophilic addition reaction is :
Ans. (b)
Propanal, Benzaldehyde, Propanone, Butanone
Molybdenum oxide (Mo2O3) is used for oxidising alkanes to
[2020, 3 Sep Shift-II]
aldehyde. It used to manufacture molybdenum metal, which
serves as an additive to steel and corrosive resistant alloys. (a) Benzaldehyde < Butanone < Propanone < Propanal
Mo 2 O 3
(b) Butanone < Propanone < Benzaldehyde < Propanal
CH3  CH2  CH3 → CH3  CH2  CHO (c) Propanal < Propanone < Butanone < Benzaldehyde
Oxidising agent
Propane Propanal
(d) Benzaldehyde < Propanal < Propanone < Butanone
Ans. (b)
103 The increasing order of the following compounds
towards HCN addition is [2020, 2 Sep Shift-I]
Reactivity order toward nucleophilic addition reaction is
aldehydes > ketones. Due to the following reasons aldehydes are
H3CO CHO CHO more reactive than ketones.
(i) (ii) (i) Inductive effect An alkyl group has electron donating (+I)
NO2 inductive effect. Hence, greater the number of alkyle group
CHO O2N CHO attached to carbonyl group, greater the electron density on
(iii) (iv) carbonyl carbon. Thus, it lowers the attack of nucleophile
OCH3 and hence, reactivity decreases.
(ii) Steric effect Increase in the number of alkyl group attached
(a) (i) < (iii) < (iv) < (ii) to carbon results in the attack of nucleophile on carbonyl
(b) (iii) < (iv) < (i) < (ii) group becomes more and more difficult due to steric
(c) (iii) < (iv) < (ii) < (i) hinderance. Therefore, due to two bulky R groups, ketones
(d) (iii) < (i) < (iv) < (ii) are less reactive than aldehydes.
350 JEE Main Chapterwise Topicwise Chemistry

So, the correct reactivity order is

(a) Br D
O O O (b)
O
D Br
C H > Ph C H > >
Br Br
105 The compound, A in the following :
(i) CH MgBr/H O (i) O
A  
3

2
→ B  3→ C + D (c) D (d)
(ii) Conc. H2 SO4 / ∆ (ii) Zn/H2 O
D
(i) Conc. KOH +
C —COO K + —CH2OH Ans. (c)
(ii) ∆

O
CH3 O
(i) NaBH4
Ba(OH) 2   CH2 CH C H CH2 CH CH2Cl
D → H3C C == CHC CH3 (ii) SOCl2
(A)
∆ [2020, 3 Sep Shift-II]
O
O O
  (i) NaBH4 reduce C group in —OH and then
(a) C 6H5 CH2 C CH3 (b) C 6H5 C CH3 (ii) SOCl2 react with it
O
O
 CH3
(c) C 6H5 C CH2CH3 (d) C6H5—C—CH + Anhy. AlCl3
CH3
Ans. (a) (Friedel-Crafts reaction)

Complete reaction is as follows : Br D

CH2 CH CH2
O OH CH CH2 CH2 r s
DBr
CH2 C CH3 CH2 C CH3
(i) CH3MgBr
+ CH3
H3O Br
(A)

CH3 D
Hence (C) will be
CH C
(ii) Conc. H2SO4 CH3 Step I
D, H2O
In the above reaction,
(B) O
(i) O3 
(ii) Zn/H2O Step I NaBH4 reduce  C H group into alcohol.
O CHO
Step II SOCl2 react with this alcohol and form R —X.
CH3 C CH3 +
Step III This R —X react with benzene in the presence of
(D) anhydrous AlCl 3 via Friedel-Crafts reaction and form product.
(C)
Step IV DBr react with this product and form rearranged
Ba(OH)2/∆ product.
CH3 C CH C CH3

CH3 O 107 In the following reaction sequence the major products A

– +
and B are
(i) Conc. KOH
Ph COO K + Ph CH2 OH O
(ii) ∆
Anhydrous (1) Zn–Hg/HCl
+ O A B
106 The major product [C] of the following reaction AlCl3 (2) H3PO4
sequence will be O [2020, 5 Sep Shift-I]
(i) NaBH4
CH2 == CHCHO → [A] O
(ii) SOCl2

(a) A = ;B=
DBr
[ B] [C]
Anhy. AlCl3 CO2H
O
[2020, 4 Sep Shift-II]
Organic Compounds Containing Oxygen 351

O O O O

(b) A = ;B= Ph Ph
(A) (B)
CO2H O O
O
OMe NMe2
(C) (D)
(c) A = ;B=
CO2H (a) (D ) < (C) < (A) < (B) (b) (C) < (A) < (B) < (D )
O (c) (A) < (C) < (D ) < (B) (d) (B) < (C) < (A) < (D )
O
Ans. (a)
(d) A = ;B= O O O O
> > >
CO2H Ph OMe
O Ph
(B) (A) (C)
Ans. (d) Active methylene O
(highly acidic)
O Addition of O (In this case most
anhydrous stable anion is formed) NMe2
(D)
AlCl3 r s
O OAlCl3 Lower-M (mesomeric)
effect as compaired
Ring
opening to C group
O O
H O O O
r Compound (B) is a active methylene compound is highly
+ s resonance stabilised. This compound possessing a methylene
+ OAlCl3 bridge located between two strong electron withdrawing groups
sO (such as carbonyl group). So, it is highly acidic in nature.
AlCl3
O O Compounds (C) and (D) having electron donating group. Which
decreases the acidity and compound (A) is more acidic than (C) and
Hr
(D) because it does not contain any electron releasing group.
O Hence option (a) is correct.
(D) < (C) < (A) < (B)
Zn-Hg/HCl
(Clemmension H 109 The correct match between Item-I (starting material)
HO reduction) HO
and Item-II (reagent) for the preparation of
O O benzaldehyde is [2020, 6 Sep Shift-II]
(A ) 2H3PO4
Major
Hr Item - I Item - II
O I Benzene (P) HCl and SnCl 2 , H3O +
+ II Benzonitrile (Q) H2 , Pd-BaSO 4, S and quinoline
III Benzoyl chloride (R) CO, HCl and AlCl 3
+
H (a) (I) - (Q), (II) - (R) and (III) - (P) (b) (I) - (P), (II) - (Q) and (III) - (R)
O O (c) (I) - (R), (II) - (P) and (III) - (Q) (d) (I) - (R), (II) - (Q) and (III) - (P)
–H+
Ans. (c)
(I) Given, reaction is Gattermann -Koch reaction involves the
formation of an aryl aldehyde using CO and HCl as reactants.
O The reaction catalysed by AlCl 3.
(B)
Major
C—H
108 The increasing order of the acidity of the α-hydrogen of CO, HCl
the following compounds is [2020, 5 Sep Shift-I] AlCl3
Benzene
352 JEE Main Chapterwise Topicwise Chemistry

(II) Given, reaction is Stephen reduction reaction involves the The major product is called Hofmann product.
preparation of aldehydes from nitriles using tin (II) chloride,
The rest of the given reactions produce Saytzeff products as
hydrochloric acid and quenching the resulting minimum salt
with water. follows :
O (a) CH3
Conc. H2SO4
CN CH==NH C—H CH3—C — CH—CH3 CH3—C == C—CH3

SnCl2, HCl +
H3O CH3 OH CH3 CH3

AA
AA
H 3O + β α β
Alc. KOH
Cyanobenzene Imine
(b) CH3  CH  CH  CH3 → CH3  C == CH  CH3
(Benzonitrile) | | |
CH3 Br CH3
(III) Given, reaction is Rosenmund reduction is a hydrogenation
β
process in which an acyl chloride is selectively reduced to an CH3
aldehyde. CH3 H
β | β | |
O α ∆
O Cl (d) CH3  C  CH2  CHO → CH3  C == C  CHO
C C—H |
OH
H2, Pd-BaSO4
S and Quinoline 111 The most suitable reagent for the given conversion is
Benzoyl chloride
CH3
Correct match of Item-I and Item-II will be CONH2 CONH2
C==O COCH3
(I) - (R), (II) - (P) and (III) - (Q).
?

110 Consider the following reactions : HO2C HOH2C

Conc. H2 SO4 CN CN
(A) (CH3 ) 3 CCH(OH)CH3 → [2020, 8 Jan Shift-I]

KOH Alc. (a) B2H6 (b) LiAlH4 (c) NaBH4 (d) H2 /Pd
(B) (CH3 ) 2 CHCH(Br)CH3 →
Ans. (a)
(CH ) OÈK ⊕ The most suitable reagent for the given conversion isB2H6 .
(C) (CH3 ) 2 CHCH(Br)CH3 →
3 3
CH3 CH3
∆ CONH2 CONH2
(D) (CH3 ) 2 C  CH2 CHO → C C
| B 2H 6
OH
HO2C HOH2C
Which of these reaction(s) will not produce Saytzeff CN CN
LiAlH4 or
product? [2020, 7 Jan Shift-I] NaBH4 H2/Pd (Given product)
(a) (A), (C) and (D) (b) (B) and (D) CH3 CH3
(c) Only (C) (d) Only (D) CONH2 CH3NH2
CH CH
Ans. (c)
OH OH
In a β-elimination reaction, a leaving group (like Cl − ) leaves along
with a hydrogen (asH+ ) from a β-position. Among available HO2C HOH2C
β-positions, H+ removal is preferred to take place from the CN CH2NH2
β-position having least H atoms according to Saytzeff’s rule.
But in reaction (c),
112 The major product in the following reaction is
O
the major product is not Saytzeff ’s product
CH 3 + H3O
|
because the given base, CH3  C  O− is bulky and∴due to steric CH3
| [2020, 8 Jan Shift-II]
CH 3
OH OH O
hinderance removes H+ from CH3 group.
In this case reaction occurs as : (a) (b) OH
CH 3
|
CH3 CH3
CH 3  C  O È K ⊕ OH
| O
β α β CH 3
CH3  CH  CH  CH3 → CH3  CH  CH == CH2 (c) (d)
  
CH3 Br CH3 CH3
HO CH3
Organic Compounds Containing Oxygen 353
Ans. (c)
So, the structure of B is
Option (c) is the major product formed. CH3
OH 
CH3  C  CH2  CH3

+H3O+ OH
CH3 CH3 To get B (alcohol) CH3MgBr must react with a ketone.
Aromatic product O
||
CH3  C  CH2  CH3 = (A)
113 Identify (A) in the following reaction sequence :
Complete reaction is as follows :
C O OH
(i) CH MgBr O3 /Zn, H2 O H (i) CH3MgBr Cu, 573 K
(A) → (B) →
3
+
Gives positive (i) H , H2 O CH3 (ii) H3O+
iodoform test (i) Conc. H SO / ∆ (A) (B)
2 4
H3C C==O % C by mass
mass of C (= 4 × 12) × 100
CH3 =
total molar mass [= 4 × 12 + (16) + (8 × 1)]
[2020, 9 Jan Shift-I]
48 × 100
CH3 = = 6667
. %
72
CH3
(a) (b)
CH3 O CH3 115 In the following reaction A is [2020, 9 Jan Shift-II]
O O
H
CH3 (i) Br2, hn
CH3 (ii) KOH (alc.)
A
(d) (iii) O3
(c) (iv) (CH3)2S
CH3 O CH3 (v) NaOH (aq) + D
O
Ans. (d)
(d)
Conc. H2SO4/∆

CH3 CH3 (a) (b) (c)

(H+ ) (–H2O)

(i) CH3 MgBr

(ii) H+ /H2O
O
CH3 HO CH3 Ans. (c)
1442443 CH3
O Br
 ’ 1
has ‘CH3  C  CH3 CH3 KOH (alcoholic) 2 6
Br2/hν
group ∴ positive
–H+ (Free radical
3 5
iodoform CH3 C—CH3
test. halogenation) (β-elimination) 4
CH3 Cyclohexane 1-bromo Cyclohex
CH3 cyclohexane -1-ene
O3/Zn-H2O (A )
CHO
O3/(CH3)2S O
CH3 (Reductive H
ozonolysis) H
COCH3
CH3
OH–
O (NaOH) O
α
H –H2O H
114 Consider the following reactions : H H H H
(i) CH MgBr Cu (Intramolecular aldol condensation)
A →
3
+
B → 2-methyl- 2- butene H H
(ii) H3 O 573 K
5
HO
The mass percentage of carbon in A is ...... ∆ 1
4
[2020, 9 Jan Shift-II] –H2O
2 3
Ans. (66.67)
On reversing the given reaction we can get the A and B. 116 The major product of the following reaction is
CH3 O
Cu | Br
B → CH3  C == CH  CH3 NaBH4
573 K 2 methyl-2 -butene MeOH, 25°C

∴ B must be a 3° alcohol that, on oxidation produces alkene. [2019, 8 April Shift-I]

354 JEE Main Chapterwise Topicwise Chemistry

OH OH Ans. (d)
Br OMe –I
O O
(a) (b) H β-elimination
Cl s r /∆
tBuOK
–HCl
Acidic hydrogen H
This benzylic –H activates r
H (Conc. H2SO4)
p-position by +ve Electrophilic addition
OMe O for ArSO2

(c) (d) H H
O O

2°
r
Ans. (d) r 1°
1°, but more stable 2°, but less stable carbocation
Major product obtained in the given reaction is carbocation because of –I effect of O
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 addition of a ∆ –Hr (more stable) ∆ –Hr
H
hydride ion and a proton. Carbon-oxygen double bonds are easily O O
reduced by sodium borohydride. The actual reducing agent in
these reductions is hydride ion (H− ). Hydride ion adds to the
carbonyl carbon and the alkoxide ion that is formed is Major product 5- membered ring Minor product
subsequently protonated by water. In other words, the carbonyl (option-d) (lon stable) (option-c)
group is reduced by adding anH− followed by an H+ . The
mechanism of the given reaction is as follows :
O O– 118 In the following reaction,
HCl
C – C—CH2Br Carbonyl compound + MeOH -acetalRate of the
CH2Br H from NaBH4 H2O
reaction is the highest for:
H (a) Acetone as substrate and methanol in excess
OH (b) Propanal as substrate and methanol in stoichiometric
amount
EtOH, 25°C
C—CH2 — Br (c) Acetone as substrate and methanol in stoichiometric
O amount
Intramolecular
cyclisation H
(d) Propanal as substrate and methanol in excess
[2019, 9 April Shift-II]
117 The major product of the following reaction is Ans. (d)
O (1) t-BuOK
Key Idea Aldehydes are more reactive than ketones in
nucleophilic addition reactions.
(2) Conc. H2 SO4 /∆
Cl
For the reaction,
[2019, 8 April, Shift-II] HCl
Carbonyl compound + MeOH -Acetal
O
(a) Rate of reaction is the highest for propanal as substrate and
methanol in excess. Propanal is an aldehyde and more reactive
than ketones. When MeOH is taken in excess then reaction
moves in the forward direction that results in the formation of
O
acetal. Reaction involved is as follows :
(b)
Et H+/MeOH Et OH MeOH Et OMe
C O C C
Excess
H H OMe H OMe
Acetal
O
(c) 119 The major product obtained in the following reaction is
[2019, 8 April Shift-II]
CH3 O
O
NaOH
(d) OHC ∆
Organic Compounds Containing Oxygen 355

H3 C H3 C density at o and p-positions. —OH group also exhibit –I group that

(a) H (b) H reduces the electron density to some extent ato and p-positions.
But overall electron density increases at these positions of the
O CH3 O CH2 ring due to resonance. Hence, attack of —Br occur at ortho-
position.
CH3 CH3
Resonating structures are as follows:
OH +OH +OH +OH OH

(c) (d) σ σ

O O σ
Ans. (c)
It is in intermolecular aldol condensation reaction. 121 Major products of the following reaction are
O CHO
(i) 50% NaOH
+ HCHO
OHC CH 2 (ii) H3O+

H H [2019, 10 April Shift-I]

H
Acidic H-atom (a) CH3OH and HCO2H

s O O COOH
4
(b) CH3OH and
OH 6 1 T his attack will result
HC 2 CH 2 7-membering. S o, it
–H 2O 5 3
7 s will not proceed.
CH2OH
O (c) HCOOH and
OH – 4 2
5 1
– H 2O O==CH s
3
CH2OH COOH
(d) and
L ess acidic
H s
∆ HO H 2O
O 4
Ans. (c)
5 3
–H 2O –OHs 1 2

The given reaction is a crossed Cannizzaro reaction which is a

(option-c)
O Major O H More acidic
β-H for
O redox reaction too. Oxidation number of carbon atom of the
β-elimination CHO groups of PhCHO and HCHO are +1 and zero
respectively. So, HCHO is the stronger reducing agent than
120 p-hydroxybenzophenone upon reaction with bromine in PhCHO. As a result, HCHO is oxidised to HCOONa (by donation of
carbon tetrachloride gives [2019, 9 April Shift-II]
hydride,H− ) and PhCHO (H− acceptor) is reduced to PhCH2 OH.
+1 0 50% NaOH −1 +2 −+
O O Ph  CHO + HCHO → Ph  CH2OH + H COON a
Br  +
Br ↓ H3O
(a) (b)
HO HO PhCH2OH + HCOOH
O Br O (Major products)
Br
The reaction proceed via following mechanism.
(c) (d) OH
HO HO – | s
OH Slowest
Ans. (b) H2C=
=O Slower H—C—O
δ+ δ– | Ph—CH=
=O
p-hydroxy benzophenone upon reaction with bromine in carbon H
More polar and less
tetrachloride gives 3-bromo-4-hydroxy benzophenone. crowding for –
H shift
O nucleophilic addition
O OH
|
Br H—C==O + Ph—CH2—Os
Br2
CCl4 Fast
Os
Ö

HO
HO |
H—C==O + PhCH2OH
—OH group attached on the benzene ring direct the incoming
group at ortho and para-positions due to increase in electron Thus, the correct option is (c).
356 JEE Main Chapterwise Topicwise Chemistry

122 The major product Y in the following reaction is Ans. (c)

Ph CH3 (i) C9H10O shows positive iodoform test thus,  C  CH3 group
NaOCl (i) SOCl2 ||
X Y
(ii) Aniline O
O [2019, 10 April Shift-II] is present.
O (ii) C9H10O on strong oxidation (KMnO4 /KOH), gives acid
Ph (C8H6O4 ), indicating it can be a dicarboxylic acid. So, ‘A’
N HN Ph contains COCH3 and one CH3 group which get oxidised
O into COOHand COOHrespectively.
(a) (b)
(iii) In the preparation of phenolphthalein from phenol, phthalic
anhydride is used. So, ‘B’ can be phthalic acid (benzene-1,2-
NH2 NH2 dicarboxylic acid) which readily forms anhydride.
O
Thus, the reaction sequence is as follows :
(c) (d)
Ph CH3
I2/NaOH
+ CHI3
CH3 (Iodoform test) – +
O Ph COONa Yellow ppts.
CH3
Ans. (b) C O
NaOCl (sodium hypochlorite) is the reagent of haloform C
O
(chloroform formation) reaction. A(C9H10O) (i) [O] OH
+ CO2
2NaOH + Cl2 → NaOCl + NaCl + H2O KMnO4/KOH OH
(ii) H3O
r C
The given reaction takes place as follows :
O
O O Phthalic acid
B(C8H6O4)
NaOCl s r
H
Ph—C—CH3 Ph—C—ONa + CHCl3 O ∆ –H2O
r
H3O (It is missing in the (2 mol)/
O
Keto-methyl statement of the question) O Conc. H2SO4
group
O C
OH
O
Ph—C—OH –H2O C
Benzoic acid
(X)
O
O O Phthalic anhydride
OH OH
2 SOCl (Phenolphthalein
Ph—C—OH Ph—C—Cl an indicator)
– SO2 [Acyl SN2
(X) Benzoyl
– HCl H N—
chloride 2 pathway]
Aniline –HCl 124 Major product of the following reaction is
O
Cl
—NH—C—Ph Cl NH2
Benzanilide + H2N (i) Et3N
(Y) O O (ii) Free radical
polymerisation

123 Compound A(C 9 H10 O) shows positive iodoform test.

Oxidation of A with KMnO 4 /KOH gives acid B (C 8H6O 4 ). Cl O Cl O
(a) n (b)
Anhydride of B is used for the preparation of NH2
O N n
phenolphthalein. Compound A is [2019, 10 April Shift-II]
H
O
O HN NH2

CH2 C H CH3 O Cl Cl
(a) (b)
(c) (d)
CH3 n n

HN O
O CH3 NH2 NH2
N
CH3 CH3 O H
O
(c) (d) [2019, 9 Jan Shift-I]
CH3
O

O
Organic Compounds Containing Oxygen 357

Ans. (d) + H
—O—O—H —O—O
The analysis of both the substrates : H
O2 hν H+ Ph-group
Vinylic centre 5 atm migration
Cl
Cumene
(+R) ⊕

OH O O

O Cl OH
Acyl SN2 centre Hydrolysis H 2O
+
Acts as
H2N nucleophile
(1°-amine) 126 The tests performed on compound X and their
This N-atom can
O inferences are :
not act as nucleophile
NH2 + R
Test Inference
Amide group
(a) 2, 4- DNP test Coloured precipitate

So, the reaction can take place as follows : (b) Iodoform test Yellow precipitate
Decrease in the delocalisation of π-bonds (c) Azo-dye test No dye formation
because of which it undergoes free radical
addition (chain growth) polymerisation Compound ‘X’ is

H3C CH3 H3C CH3

Cl Cl Cl N
Free
radical
N
–Cl – polymerisation COCH3
n CHO
absorbed –H O (a)
by Et3N O C (b)
NH
O Cl NH2 NH2 OH NH2
NH2 O
CH3 CHO
NH2 (c) (d)
O
O
NH2
[2019, 9 Jan Shift-II]
NH2
Ans. (b)
125 The products formed in the reaction of cumene with O 2 Let us study the chemical nature of the functional groups
followed by treatment with dil. HCl are present in the following compound (b).
O CH3 It is a 3°-amino group (—NMe2)
though aromatic which will not
respond to diazotisation (NaNO2 +
(a) and CH3—OH dil. HCl/5°C). So, formation of
CH3 diazonium ion and its further reaction
OH O N with alkaline phenol or β-napthol at 5-
CH3
10°C to produce a precipitate of azo-
dye will not take place.
(b) H3C CH3
and
It is a keto group C==O and so it
responds to 2, 4-DNP test with
O (b) Brady’s reagent (2, 4-dinitrophenyl
hydrazine) to give a reddish orange
(c) H3C CH3 precipitate.
and CH3 —— C==O O

OH OH It is a keto-methyl group —C—CH3

and hence, it responds to iodoform
H3C CH3 test to give a yellow precipitate of
(d) and iodoform (CHI3).
[2019, 9 Jan Shift-I]

Ans. (b) Compound (c) is an alcohol and does not give positive 2,4-DNP
test. Hence, eliminated.
The given process is cumene process (Hock process) to
synthesise phenol and acetone industrially. In Hock p rocess, (a) and (d) does not have —CH3CO group and does not give
iodoform test. Hence, eliminated.
Ph— group migrate and releaseH2O.
358 JEE Main Chapterwise Topicwise Chemistry

127 The major product of the following reaction is 128 The major product formed in the following reaction is
HO CH3
CH3
O AlCl3, ∆ H3C H Dil. NaOH
+ +

O OH OH O
OH OH
H3C (b) H3C
CH3 (a) H3C
(a) O
(b)
O OH
OH O
O (d) H
(c) H3C H H3C
OH
OH [2019, 9 Jan Shift-II]
CH3
CH3
Ans. (c)
(c) (d) In aldol condensation, generally aldehydes react at a faster rate
than ketones towards base. In the given case CH3CHO will lose
O O
[2019, 9 Jan Shift-II]
C
Ans. (c) CH3
α-hydrogen faster than
It is an aromatic electrophilic substitution reaction (Ar SE2).
The reaction follows Ar SE2 (Aromatic electrophlic substitution
pathway) as shown below : to one more reason, i.e. conjugation between benzene ring and
‚ C == O group. Along with sterically less hindered nucleophile of
it makes ring activating ƒ
It becomes ring activating
and p-directing
and m-directing CH3CHO will also add to the major product formation.

H—O HO—AlCl3 Following four products are possible in the reaction:

H
AlCl3
(i) CH3—C—CH2—CHO (Self Aldol condensation
Friedel-Craft's of CH3CHO)
acetylation OH
O reaction
H (Cross Aldol condensation of
CH3CHO and CH3COC6H5
O (ii) CH3—C—CH2—C—C6H5 in which >C=O group of
CH3CHO is carbanion
OH acceptor).
HO—AlCl3 O—AlCl3
OH (Cross Aldol condensation of
H 3C CH3CHO and CH3COC6H5
–H /+H (iii) CH3—C—C6H5 in which >C=O group of
O O C6H5COCH3 is carbanion
H CH2 acceptor).
H—C
O HO
Stabilises the complex by −AlCl3
hyperconjugation OH
(Self Aldol condensation
(iv) C6H5—C—CH2—C—C6H5
O O product of C6H5COCH3)
CH3
–
O –H2O O OH of base will prefer to attack on CH3 group of CH3CHO for the
formation of carbanion and as among the> C == O groups
available, the> C == O group of CH3CHO is the best carbanion
CH3 H 2O acceptor. Hence, self condensation product of CH3CHO will be
OH O the major product.

129 The major product obtained in the following reaction is

O O
CO2Et
H NaOEt/∆

[2019, 10 Jan Shift-II]

Organic Compounds Containing Oxygen 359

H
(a) (b) HO –HCl O
CO2Et
–AlCl3
AlCls4
CO2Et
It does not show SN reaction H
with HCl because of double bond
(c) (d)
CO2Et nature of the O—C bond, (due
to +R-effect of the —OH group.)
CO2Et
Ans. (b) 131 The major product of the following reaction is
In presence of strong base, acidic H can easily be removed that CN
result in formation of anion. The resulting anion undergoes (i) DIBAL-H

intramolecular nucleophilic addition which on hydrolysis O (ii) H3O+

followed by heating gives the required product. O

More acidic CHO CHO
H H (a) (b)
CO2Et O O O
s r
EtONa
O –EtOH s CO2Et O
O O CH NH CHO
(Nucleophilic (c) (d)
addition) OH
OH
O OH
H2O CHO
s
–OH
CO2Et
[2019, 12 Jan Shift-I]
s
O
s Ans. (d)
EtO
–H
O cidic b
H
more a DIBAL-H (Diisobutylaluminium hydride) is a reducing agent with
CO2Et formula [λ-Bu2 AlH]. At ordinary temperatures, nitriles give imines
a, b-eliminatioin –EtOH OH which are readily converted in aldehydes by hydrolysis whereas
–OHs
lactones are reduced directly to aldehydes.
O H
CO2Et Al
Al Al
+ (DIBAL–H) + H (DIBAL–H)
N N
130 The major product of the following reaction is CN
C C H
HO
(i) HCI O
(ii) AlCl3 (Anhyd.) O O
O
HO O O
Cl
H 2O
(a) (b)
CHO CHO CHO
+H+ DIBAL–H
(Hs)
OH O O
HO Cl H
(c) (d) O –O
H O

[2019, 11 Jan Shift-II] 132 In the following reaction,

Ans. (a) Aldehyde + Alcohol HCl
→ Acetal
In the given reaction, AlCl 3 helps in the generation of electrophile Aldehyde Alcohol Aldehyde Alcohol
that further undergoes ArSE2 reaction to give the required HCHO t
BuOH CH3CHO MeOH
product.
AlCl3
The best combination is [2019, 12 Jan Shift-I]
HO H—Cl (a) CH3CHO and MeOH (b) CH3CHO and t BuOH
–AlCl s
4 (c) HCHO and MeOH (d) HCHO and t BuOH
HO
Ans. (c)
Acetal formation is nucleophilic addition reaction due to the
addition of alcohols on aldehydes. The reactivity of nucleophilic
Intramolecular addition depends on following two factors.
ArSE2 reaction
360 JEE Main Chapterwise Topicwise Chemistry

● Inductive effect Greater the number of alkyl group attached 134 The aldehydes which will not form Grignard product with
to carbonyl group, greater is the electron density on carbonyl
one equivalent Grignard reagents are
carbon. Thus, lowers the attack of nucleophile. Hence,
reactivity decreases. CHO CHO
● Steric effect As the number of alkyl group attached to
(A) (B)
carbonyl carbon increases, the attack of nucleophile on HO2C
carbonyl group becomes more difficult due to steric CHO
CHO
hinderance.
(C) ( D)
Thus, the best combination is HCHO and MeOH. The reaction is
HO3CO HOH2C
as follows:
O OH OMe (a) (C), (D ) (b) (B), (D )
HCl MeOH (c) (B), (C), (D ) (d) (B), (C)
H CH + MeOH H C H H C H [2019, 12 Jan Shift-II]

OMe
Ans. (b)
OMe
Acetal
Key Idea Grignard reagent usually attacks on> C ==O group as
133 In the following reactions, products A andB are C2 O
O O ( C == O + RMgX→ ( C 'OMgX →
Hydration ( C ' OH
Dil. NaOH ' ' (R − Mg (OH) X ' (R
H 3C H [A]
H 3C CH3 (Ionic salt)

H3O+ The question is related to above reaction only with the condition
[A] ∆
[B]
that the consumption of RMgX will be more than 1 equivalent in
some of the given cases.
O O
CH3 CH3 Among the given compounds B, i.e.
(a) A= CH3 ; B= CH3 CHO CHO
HO
O O
CH3 CH3 HO2C and D, i.e. HOH2C
(b) A= CH3 ; B= CH3
HO contain additional groups which can give active hydrogens.
Grignard reagents produce alkanes whenever come in contact
O with any group or compound which can give active hydrogen as:
O
OH CH3 OR
C
H H ROH + R ′MgX Dry
→ R ′H + Mg '
(
HC ether X
(c) A = 3 ;B=
These reactions are equivalent to acid-base reactions. So, in
H3C H3C
CH3 CH3 both of these compounds more than one equivalent will be
O required to form Grignard products. Remember these
O
OH
C H2C compounds will give 2 type of products as:
H H
A = H3C ;B= (i) from the > C ==O group
(d) (ii) from the group which release active hydrogen
H3C H3C
CH3 CH3 The additional reactions involved are:
[2019, 12 Jan Shift-I]
CHO CHO
Ans. (b) Dry
(i) + RMg X RH +
The reactant in presence of Dil. NaOH undergoes intramolecular ether
aldol condensation reaction. HO2C δ+ δ– C
X MgO
As a result of this,β-hydroxyketone (A) is obtained which on O
hydrolysis followed by heating producesα, β-unsaturated CHO CHO
ketone (B) Dry
(ii) + RMg X + RH
O O O O ether
dil. HOH2C XMgOH2C
H 3C H NaOH s H
H3 C CH3
135 The major product of the following reaction is
O O [2019, 12 Jan Shift-II]
O

H2 O O
D
s
–H2O HO O NaBH4
(B) H (A) H EtOH
Organic Compounds Containing Oxygen 361

O
OH OH OH 137 The major product obtained in the following reaction is
O
(a) (b) (c) (d)
O
OEt DIBAL-H
Ans. (a)
Reducing agents likeLiAlH4 , NaBH4 , i.e. complex hydrides usually
does not affect olifenic or π-bonds. Thus, ifNaBH4 is applied to a COOH [JEE Main 2017]
O
OH OH

compound like then its ( C == O bond will be reduced (a) CHO (b) CHO
'
OH
COOH CHO

only and we get as the final product. (c) CHO (d) CHO

136 The correct sequence of reagents for the following COOH CHO
conversion will be [JEE Main 2017] Ans. (a)
– +
COOH COONa DIBAL-H (Di-isobutyl aluminium hydride) is a reducing agent with
CO2 formula. This is generally used for the preparation of aldehydes.
+ NaHCO3 + H2CO3 Using DIBAL −H, Lactones are reduced directly to aldehydes.
H2O O
Benzoic acid Sodium Sodium (Weak acid)
OH
(Strong acid) bicarbonate benzoate O
(B)
DIBAL–H
CHO
O HO CH3
COOH
COOH

138 Which compound would give 5-keto-2-methyl hexanal

CHO H3C OH
CH3 upon ozonolysis? [JEE Main 2015]

+ − + CH3 CH3
(a) [Ag(NH3)2] OH , H / CH3OH, CH3MgBr
CH3
(b) CH3MgBr, H+ / CH3OH, [Ag(NH3)2] + OH−
(c) CH3MgBr, [Ag(NH3)2] + OH− , H+ / CH3OH (a) (b)
(d) [Ag(NH3)2] + OH− , CH3MgBr, H+ / CH3OH
CH3
Ans. (a)
CH3 CH3
O O O
H3C
[Ag (NH3)2]OH (c) (d)
Esterification
Tollen’s reagent CH3OH, H+
CH3
CHO COOH COOCH3
Ans. (b)
CH3MgBr CH3
(Excess)
CH3
HO CH3 O3
∇ O O
|| ||
Zn,H2O2 CH3  C  CH2  CH2  CH2  C  CH3
Heptan-2,6-dione
CH3
OH

Before final product is formed, intermediate is (b) O3

∇
HO CH3 Zn,H2O2
CH3 O
6 || 5 4 3 1
CH3  C  CH 2  CH 2  CH  CHO

CH3
CH3
O
5-keto-2-methyl hexanal
362 JEE Main Chapterwise Topicwise Chemistry

CH3
140 Trichloroacetaldehyde was subjected to Cannizzaro’s
reaction by using NaOH. The mixture of the products
(c) O3
∇ contains sodium trichloroacetate ion and another
Zn,H2O2 compound. The other compound is [AIEEE 2011]
H3C O CH3 (a) 2, 2, 2-trichlorethanol (b) trichloromethanol
|| |
CH3 —C —CH2 — CH—CH2 —CHO (c) 2, 2, 2-trichloropropanol (d) chloroform
5-keto-3-methyl hexanal Ans. (a)
CH3 Cannizzaro’s reaction is given by aldehydes (RCHO) lacking H at
α-carbon or lacking α-carbon (as in HCHO). With NaOH, there is
H3 C
(d)
O3
∇ formation of acid salt (RCOO– ) by oxidation and alcohol (RCH2OH)
by reduction.
Zn,H2O2 Cl
O CH3
|| | 
2Cl  C  CHO + NaOH →
CH3 —C —CH —CH2 —CH2 —CHO

5-keto-4-methyl hexanal Cl
a-carbon without H
139 In the given transformation, which the following is the Cl O Cl
| || |
most appropriate reagent? [AIEEE 2012] Cl  C  C ONa + Cl  C  CH2OH
| |
CH CHCOCH3 Cl Cl
Reagent (By oxidation) (By reduction 2, 2, 2,
trichloroethanol)
HO
CH CHCH2CH3 141 Silver mirror test is given by which one of the following
compounds? [AIEEE 2011]
(a) Acetaldehyde (b) Acetone
HO
(c) Formaldehyde (d) Benzophenone
s Ans. (a, c)
(a) NH2NH2 ,OH (b) Zn -Hg / HCl
(c) Na, Liq. NH3 (d) NaBH4 All aldehydes including reducing sugar (as glucose, fructose)
gives Silver-mirror test (with Tollen’s reagent)
Ans. (a)
RCHO+ 2[Ag(NH3)2 ] + + 3OH– →∆ RCOO– + 2Ag ↓ + 4NH3 + 2H2O
CH CHCOCH3 Silver mirror (R=H, CH3)
(a)
Thus, acetaldehyde and formaldehyde give silver-mirror test.
HO
142 Ozonolysis of an organic compound A produces acetone
NH2NH2, OH – glycol and propionaldehyde in equimolar mixture. Identify A from
the following compounds. [AIEEE 2011]
CH CHCH2CH3 (a) 2-methyl-1-pentene
(b) 1-pentene
(c) 2-pentene
HO
(Wolff-Kishner)
(d) 2-methyl-2-pentene
Ans. (d)
Cl O /H 2 O / Zn
H3C
Alkene  
3
→ C == O + CH3CH2 CHO
CHCH2COCH3 H3C
Zn(Hg)/HCl
(b) Acetone Propionaldehyde
Cl To identify alkene (from ozonolysis products) place these
products with O-atoms face to face.
HCl attacks 2° alcohol as well as (C==C) bond. Replace O-atoms by == (double) bond.
CH CHCOCH3 H3C Replace
Na/NH3 C == O + O == CHCH2 CH3 → O-atom face to face
(c) O −atoms by
H3C double bond
NaO
H3C 2 3 4 5
C == CH CH2 CH3
NaBH4
(d) Low yield H3C
2-methyl-2-pentene
Organic Compounds Containing Oxygen 363
Ans. (b)
143 One mole of a symmetrical alkene on ozonolysis gives
two moles of an aldehyde having a molecular mass of In Cannizaro reaction, the transfer ofH− to a carbonyl group is a
44 u. The alkene is [AIEEE 2010] slowest step of the reaction and hence, it is a rate determining
(a) propene (b) 1-butene (c) 2-butene (d) ethene step of the reaction.
–
Ans. (c) O O
The general molecular formula for carbonyl compound is CnH2 nO. OH– Ph  CH==O
Ph  C  H Ph  C  H
⇒ CnH2 nO = 44 u (fast) Hydride transfer
(Nucleophilic attack) (slow)
⇒ CnH2 n = 44 − 16 OH
⇒ CnH2 n = 28 u ⇒ n = 2 O
Thus, the aldehyde comes out to be C2H4O or CH3CHO. In order to
identify an alkene, place 2 molecules of CH3CHO with O−atom Ph  C  OH + Ph  CH2  O–
face to face. +
H
transfer H  OH
Then, replaceO atom by doube bond.
H Ph  CH2  OH

CH3 C == O + O == CHCH3 → CH3CH == CHCH3 146 The increasing order of the rate of HCN addition to
but- 2- ene compounds A-D is [AIEEE 2006]
(symmetrical alkene)
Hence, O (A) HCHO (B) CH3COCH3
O3
(C) PhCOCH3 (D) PhCOPh
CH3CH ==CHCH3 CH3 CH CH CH3 (a) A < B < C < D (b) D < B < C < A
2-butene (c) D < C < B < A (d) C < D < B < A
O O Ans. (c)
Zn/H2O Addition of HCN is a nucleophilic reaction. Greater the electron
deficiency of C atom of carbonyl group, higher the rate of
2CH3 CHO
reaction.
Hence,
O O O O
144 Which of the following on heating with aqueous KOH,    
produces acetaldehyde? [AIEEE 2009] Ph  C Ph < Ph  C  CH3 < CH3  C  CH3 < H  C  H
(a) CH3COCl (b) CH3CH2Cl (c) CH2ClCH2Cl (d) CH3CHCl2
Ans. (d) 147 The best reagent to convert pent-3-en-2-ol into
O O pent-3-en-2-one is [AIEEE 2005]
 KOH ( aq )  (a) pyridinium chloro-chromate
CH3 C  Cl → CH3  C  OH+KCl [SN reaction] (b) chromic anhydride in glacial acetic acid
KOH ( aq ) (c) acidic dichromate
CH3  CH2  Cl → CH3  CH2  OH [S N 2 reaction]
(d) acidic permanganate
KOH ( aq ) Ans. (b)
Cl  CH2  CH2  Cl → CH2  CH2 [S N 2 reaction]
2°
  CH3  CH  CH ==CH  CH3 → CH3  C  CH ==CH  CH3
OH OH 

KOH ( aq ) OH O
CH3  CH  Cl → CH3  CH  OH
  Only suitable reagent is chromic anhydride in glacial acetic acid.
Cl OH Other will also effect(C == C) bond.
(unstable)
O

148 Which one of the following undergoes reaction with
− H 2O
→ CH3  C  H 50% sodium hydroxide solution to give the
(acetaldehyde ) corresponding alcohol and acid? [AIEEE 2004]
(a) Phenol (b) Benzaldehyde
145 In Cannizzaro reaction given below (c) Butanal (d) Benzoic acid
OHs Ans. (b)
2PhCHO → PhCH2OH+ PhCO s2
A + NaOH → alcohol + acid
the slowest step is [AIEEE 2009] Thus, it is Cannizzaro reaction.
(a) the attack of : : OHs at the carboxyl group A is thus aldehyde without H atα-carbon.
(b) the transfer of hydride to the carbonyl group (as C6H5 CHO, HCHO)
(c) the abstraction of proton from the carboxylic group 2C6H5 CHO + NaOH → C6H5 CH2OH + C6H5 COONa
(d) the deprotonation of PhCH2OH
364 JEE Main Chapterwise Topicwise Chemistry

149 On vigorous oxidation by permangnate solution (a) compound with both alcohol and acid functional groups
(CH3 ) 2 C == CHCH2CHO gives [AIEEE 2002]
(b) monocarboxylic acid
(c) dicarboxylic acid
(a) (CH3)2 CO and OHCCH2CHO
(d) diol
(b) (CH3)2 C  CHCH2CHO
  Ans. (c)
OH OH In this reaction, one compound having alcohol and acid
(c) (CH3)2 CO and OHCCH2COOH functional group and another one having two alcohol groups are
formed.
(d) (CH3)2 CO and CH2 (COOH)2
Ans. (d) CHO CH2OH COOH
C == C bond is cleaved and oxidised to COOH, CHO group is
1. NaOH
also oxidised to COOH. +
2. H3O+
(CH3 )2 C == CHCH2CHO →(CH3 )2 C == O
+ HOOC CH2 COOH
CH2OH CH2OH CH2OH

∴ Dicarboxylic acid not formed as a product.

TOPIC 4
Carboxylic Acids 152 The structure of product C, formed by the following
sequence of reactions is
150 In the following sequence of reactions a compound A, CH3COOH + SOCl 2 → A Benzene
→ B KCN → C
(molecular formula C 6H12O 2 ) with a straight chain AlCl3 − OH

structure gives a C 4 carboxylic acid. A is [2021, 31 Aug Shift-I]

LiAIH4 Oxidation
A →
+
B → C 4 carboxylic acid NC OH
H O
3 [2021, 01 Sep Shift-II]
(a) CH3 CH2 COO CH2 CH2 CH3 (a) CH3 (b) CH3
OH
CN

(b) CH3 CH2 CH CH2 O  CH == CH2 H COOH
CH2—CH2CN
C
(c) CH3 CH2 CH2 COO  CH2 CH3 (c) CH3 (d)
(d) CH3 CH2 CH2 O CH == CH CH2 OH
Ans. (c)
Ans. (a)
Ethylbutanoate on reduction withLiAlH4 and hydrolysis gives
butanol and ethanol. Butanol on further oxidation gives butanoic Acetic acid on reaction withSOCl2 gives acetyl chloride (A).
acid which has four carbon atoms. The complete reaction is as O
follows SOCl2

CH3  CH2  CH2  C  O  CH2  CH3 H3C  COOH → CH3  C  Cl
Acetic acid Acetyl chloride (A)

O Acetyl chloride undergoes Friedel-Craft acylation in presence of
Ethylbutanoate (A)
 LiAlH 4 , H 3O
+ anhyd. AlCl 3 and benzene to form acetophenone (B).
↓
CH3  CH2  CH2  CH2  OH + CH3  CH2  OH Benzene
Butanol (B ) Ethanol CH3 CCl C
Anhy. AlCl3 CH3
 Oxidation Acetyl chloride
↓
Acetophenone (B)
CH3  CH2  CH2  C  OH
 Acetophenone reacts with KCN to give (C) the final product, i.e.
O 2-hydroxy-2-phenolpropionitrile.
151 For the reaction given below. OH
CHO C
C C
CH3 CH3 H
+ CH3
1. NaOH, ∆ CN
Product CN
2. H3O+
K+C≡≡N (C)
Acetophenone 2-hydroxy-2-phenolpropionitrile
CH2OH

The compound which is not formed as a product in the Hence, correct option is (a).
reaction is a [2021, 31 Aug Shift-II]
Organic Compounds Containing Oxygen 365

153 The structure of the starting compound P used in the 155 The major product formed in the following reaction is
reaction given below is [2021, 27 Aug Shift-I] [2021, 26 Aug Shift-I]

COOH
OH SOCl2, CH3OH Major
(i) NaOCl
P product
(ii) H3O+ N NH2
H
CO2CH3
H
(a) (b) (a)
O O N NH2HCl
H.HCl
O
O CO2M
(c) Cl
(d)
(b)
N NH2
Ans. (a) H
Sodium hypochlorite (NaOCl) is a strong oxidising agent that will CO2CH3
convert ketone to carboxylic acid.
(c)
Since, product is carboxylic acid, therefore reactant (P) would be
N NH2HCl
ketone.
H
(i) NaOCl OH COCl
(ii) H3O+ (d)
O O N NH2
(P) But-2-enoic
acid H
Pent-3-en-2-one
Ans. (c)
154 The correct sequential addition of reagents in the Esterification of carboxylic group (COOH) take place in
preparation of 3-nitrobenzoic acid from benzene is presence ofSOCl2 and CH3OH as follows
[2021, 26 Aug Shift-I]
COOH
(a) Br2 /AlBr3, HNO 3 /H2 SO 4 , Mg /ether, CO2 ,H3O + COOCH3
(b) Br2 / AlBr3, NaCN, H3O + ,HNO 3 / H2 SO 4 NH2
SOCl2
N CH3OH
(c) Br2 /AlBr3, HNO 3 /H2 SO 4 , NaCN, H3O + H N NH2HCl
(d) HNO 3 /H2 SO 4 ,Br2 / AlBr3 , Mg/ether,CO2 , H3O + H
Ans. (d) Mechanism
O O
The preparation of 3-nitrobenzoic acid from benzene is as
follows C S
● Nitration of benzene OH + Cl Cl
NO2 N NH2
H
+HNO3 Nucleophilic attack on SOCl2
+H2SO4
Benzene Nitrobenzene
OH O
● Electrophilic substitution of nitrobenzene
C S
NO2 NO2 O Cl
Cl
Br2 N NH2
H –
+ AlBr3 Removal of Cl as
Br leaving group
Nitrobenzene m-bromo nitrobenzene
OH O
● m-bromo nitrobenzene is converted to 3-nitrobenzoic acid.
C S
NO2 O Cl
NO2 NO2
CO2, H3O+ N NH2
Mg/ether
H
Cl–
Br MgBr COOH Nucleophilic attack
on carbonyl
3-nitrobenzoic
acid
366 JEE Main Chapterwise Topicwise Chemistry

Ans. (b)
OH O
Maleic acid is an organic compound that is a dicarboxylic acid.
C S It mainly used as a precursor to fumaric acid, and relative to its parent
O Cl maleic anhydride. Maleic anhydride can be prepared by heating
Cl cis-but-2-enedioic acid.
N NH2 O
H H COOH
Leaving group C –H2O HC O
removal
∆ HC
C
H COOH O
OH
cis-but-2-enoic acid Maleic anlydride
C (Maleic acid)
H COOH
Cl H 2O C
+ SO2 +Cl – ∆ or
N NH2 isomerisation C
H HOOC H
Deprotonation O trans-but-2-enoic acid
(Fumaric acid)
C
Cl + SO2 +HCl 157 Which one of the following compounds will liberate CO 2 ,
N NH2 when treated with NaHCO 3 ? [2021, 25 July Shift-I]
H r s rs
CH3OH (a) (CH3) 3 NHCl (b) (CH3) 3 NOH
O O

C (c) CH3 C  NH2 (d) CH3NH2
Cl Ans. (a)
O
N NH2 CH3 Compound (A), reacts with sodium bicarbonate to form carbonic
H H acid which further dissociate to liberate CO2 effervescence.
Bicarbonate test
⊕
(CH3) 3 NHCl − + NaHCO3 → H2 CO3 + (CH3) 3N + NaCl
O Sodium Carbonic Trimethyl-
bicarbonate acid amine
C
O H2 CO3 → CO2 + H2O
Carbon dioxide
CH3 (effervescence)
N NH2 H
H
158 CH3
–
Cl
O Alkaline KMnO4
'X'
H+
C
OCH3
OCH3
N NH2HCl
H Considering the above chemical reaction, identify the
(Final product)
product ‘X’. [2021, 18 March Shift-I]
O CHO CH2OH

156 O
(a) X- (c) X-

O
(Maleic anhydride) OCH3 OCH3
Maleic anhydride can be prepared by COOH CH3
[2021, 25 July Shift-II]
(a) heating trans-but-2-enedioic acid
(b) heating cis-but-2-enedioic acid (c) X- (d) X-
(c) treating cis-but-2-enedioic acid with alcohol and acid
(d) treating trans-but-2-enedioic acid with alcohol and acid
OCH3 OH
Organic Compounds Containing Oxygen 367

Ans. (c) CH3 COO–K+ COOH

4-methoxy toluene in the presence of alkalineKMnO4 to give
4-methoxy benzoic acid. Alkaline H+
KMnO4
Chemical reaction is as follows :

CH3 COOH OCH3 OCH3 OCH3

4-methoxy 4-methoxy 4-methoxy
Alkaline KMnO4 toluene benzoate benzoic acid
H+
161 The number of compound(s) given below which
OCH3 OCH3
4-methoxy toluene (X)
contain(s) — COOH group is ……… .
4-methoxy benzoic acid (i) Sulphanilic acid
(ii) Picric acid
159 C≡≡ N
(iii) Aspirin
COOH
H 2O
''A'' H2O (iv) Ascorbic acid [2021, 25 Feb Shift-II]
+ +
H (Major product) H , ∆ Ans. (1)
Structure of given compounds are as follows
Consider the above chemical reaction and identify
SO3H
product “A” [2021, 18 March Shift-I]
CH2NH2 CH2NO2
(i) (Sulphanilic acid) ⇒
(a) (b)
H NH2
CONH2 C==N—OH OH
(c) (d) O2N NO2
(ii) (Picric acid) ⇒
Ans. (c)
1-cyano cyclo hexane on complete hydrolysis gives 1-cyclo NO2
hexanoic acid. Intermediate 1- methanamide cyclohexane (A) is
formed by partial hydrolysis. COOH
Complete reaction is as follows OCOCH3
(iii) (Aspirin) ⇒

Cºº N C—NH2 C—OH

OH–
H 3O H3O HO CH—CH2OH
D
1-methanamide 1-cyclohexanoic acid (iv) (Ascorbic acid) ⇒ O
1-cyano
cyclohexane cyclohexane (Complete
'A' hydrolysis)
HO
Major product
(Partial hydrolysis) Only one compound (iii) contains COOHgroup.

160 CH3 COOH 162 The correct order of acid character of the following
′A′ compounds is [2021, 25 Feb Shift-II]
OH COOH COOH COOH

OCH3 OCH3

In the above reaction, the reagent ‘A’ is

[2021, 16 March Shift-II]
(a) NaBH4 , H3O + (b) LiAIH4 NO2 CH3
(c) Alkaline KMNO 4 ,H+ (d) HCl, Zn - Hg I II III IV
Ans. (c) Options
In the given reaction, A is alkalineKMnO4 , H+ . (a) I > II > III > IV
Alkaline KMnO4 /H+ is a strong oxidising agent and oxidises alkyl (b) III > II > I > IV
benzene to benzoic acid. WhileNaBH4 ,LiAlH4 and Zn-Hg/HCl are (c) II > III > IV > I
reducing agent. (d) IV > III > II > I
368 JEE Main Chapterwise Topicwise Chemistry

Ans. (c) ∴ CO2 gas is liberated

OH COOH COOH COOH NH2 NH2

+ NaHCO3 H2CO3 +
H2 N NH2 (Strong H2 N NH2
(–R) acid)
NO2(–I) CH3(+I) OH ONa
(I) (II) (III) (IV) (Weak acid)
(A)
Acidity of phenol (I) is weaker than any carboxylic acid. Equilibrium favours backward direction and CO2 is not liberated.
Electron withdrawing nature (− R, − I), of NO2 group at para Thus, only B and C will liberate carbon dioxide with sodium
position increases acidic strength of (II), whereas + I effect of bicarbonate solution.
CH3 group at para position decreases acidic strength of (IV).
So, the order of acid character is II > III > IV > I. 164 An organic compound [A], molecular formula C 10 H20 O 2
163 Compound(s) which will liberate carbon dioxide with was hydrolysed with dilute sulphuric acid to give a
sodium bicarbonate solution is/are [2021, 25 Feb Shift-I] carboxylic acid [B] and an alcohol [C]. Oxidation of [C]
with CrO 3 H2SO 4 produced [B]. Which of the following
NH2 COOH
structures are not possible for [A]? [2020, 3 Sep Shift-I]
CH3
A= B= 
(a) CH3CH2  C H OCOCH2 CH  CH2CH3
NH2 NH2 
OH CH3
CH3
OH 
NO2 NO2 (b) CH3CH2  C H COOCH2 CH  CH2CH3

C= CH3
(c) CH3CH2CH2COOCH2CH2CH2CH3
NO2 (d) (CH3) 3 C COOCH2C(CH3) 3
(a) A and B (b) C only Ans. (a, c)
(c) B and C (d) B only A can be written as : (CH3) 3 C  COOCH2 C(CH3) 3]
Ans. (c) H 2O
C10H20O2 H2SO4
Carboxylic acid + Alcohol
The reactions of given compound with sodium bicarbonate (B) (C)
(A )
solution are as follows [O]
– +
COOH COONa CrO3/H2SO4

CO2 From the informations given, it is clear that A is an ester which

+ NaHCO3 + H2CO3 contain 10 carbon atoms. Again,C on oxidation gives B. It
H2O indicates B and C contains equal number of carbon atom, i.e.
Benzoic acid Sodium Sodium (Weak acid)
(Strong acid) bicarbonate benzoate
each of B and C contains 5 carbon atom.
(B) O
H 2O
As H2 CO3 is weak acid it dissociate to liberate CO2 gas and H2O. R C OR′ R COOH + R′ OH
H+
– +
10C 5C (R+C) 5C (R′)
OH ONa
NO2 NO2 NO2 NO2 CH3 O CH3
+ NaHCO3
(a) CH3CH2 CH O C CH2 CH CH2CH3
4C(R′) 6C(R+C)
OH NO2
(Strong acid) CO2 CH3 O CH3
(C) + H2CO3
CH3CH2 CH C O CH2 CH CH2CH3
H 2O (b)
(Weak acid) 5C (R+C) 5C (R′)
O
Equilibrium favours forward direction and CO2 is liberated. In the
above two reactions,H2 CO3 is comparatively weak acid. (c) CH3CH2CH2 C O CH2 CH2CH2CH3
4C (R+C) 4C (R′)
Organic Compounds Containing Oxygen 369

Note It is not having the molecular formula of Ans. (b)

A(C 10H 20O 2 ). Its molecular formula (C 8H 16O 2 ). ZnCl2 + HCl → Lucas reagent
O (C) give precipitate with Lucas reagent (immediately ppt.). It
mean C will be 3° alcohol So, according to the given hints option
(d) (CH3)3C C O CH2 C (CH3)3 (b) fits the category.
5C (R+C) 5C (R′) (b) O O
Dil. H2SO4
+
H3Or Hydrolysis
(CH3)3C COOH + HO CH2 C (CH3)3 O OH HO (3°OH)
(B) [O] (C) (B) (C)

is 3°OH. In 3°OH, it gives immediate ppt. then this is correct option.

165 Consider the following molecules and statements Explanation of other options are as follows :
related to them
(a) O Dil. H2SO4
O 1
H O 2°OH
O H Hydrolysis +
(A) H (B ) O O OH HO
(B) 2
O C Ester (C)
C H
C is 2° alcohol, we want 3° alcohol then that this is incorrect
O
option.
(I) (B) is more likely to be crystalline than (A). (c) O O
Dil. H2SO4
(II) (B) has higher boiling point than (A). +
HO
Hydrolysis
(III) (B) dissolves more readily than (A) in water. O OH (C)
(B)
Identify the correct option from below : 1°OH
[2020, 3 Sep Shift-II]
C is 1°OH, it does not give ppt. immediately then that this is
(a) (I) and (III) are true (b) Only (I) is true
incorrect option.
(c) (II) and (III) are true (d) (I) and (II) are true
(d) O O
Ans. (c) Dil. H2SO4
+
Hydrolysis HO
Given, molecules (A) and (B) undergoes intramolecular H-bonding O OH (C)
and intermolecular H-bonding respectively. It is shown as (B)
1°OH
follows :
C is 1°OH that does not give test immdiately.
δ+ δ–
δ+ H O According to the question, compound
H O
C (A) gives carboxylic acid and alcohol on hydrolysis. So, A must be
O O δ– O H
an ester.
C
O H 167 [P] on treatment with Br 2 /FeBr 3 in CCl 4 produced a
single isomer C 8H7 O 2 Br while heating [P] with sodalime
(A ) C δ– O gave toluene. The compound [P] is [2020, 4 Sep Shift-I]
δ+
o- salicyclic acid
H O O COOH COOH
intramolecular (B) H
H-bonding p-salicyclic acid
intermolecular H-bonding
(a) (b)
Among the given statements, II and III are true whereas I is false. CH3
Corrected statement I, (A) is more likely to crystalline than (B). CH3
COOH CH2COOH
166 An organic compound (A) (molecular formula C 6H12O 2 ) CH3
was hydrolysed with dil. H2SO 4 to give a carboxylic acid (c) (d)
(B) and an alcohol (C). ‘C’ gives white turbidity immediately
when treated with anhydrous ZnCl 2 and conc. HCl. The Ans. (b)
organic compound (A) is [2020, 4 Sep Shift-I]
The compound [P] is 4-methyl benzoic acid.
O O Option (b) COOH
(a) O (b) O
O O
(c) O (d) O
CH3
370 JEE Main Chapterwise Topicwise Chemistry

Here, CH3 group is o-and p-directing but p-position is already 169 The major products of the following reaction are
acquired by  COOH group. So, only one single product is formed.
On treatment option (b) with sodalime, CO2 gas is released COOH.
CH3
 t
(i) KO Bu / ∆
COOH
CH3  CH CHCH3  →
 (ii) O 3 / H 2O 2
+ CO2 OSO 2CH3
[2020, 6 Sep Shift-I]

CH3 CH3
CH3 CH3
Toluene (a) + CH3CHO (b) + CH3COOH
CH3 O CH3 O
Other given options does not satisfy the condition.
COOH CH3 CH3
Option (a)
(c) + HCHO (d) + HCOOH
CH3 CHO CH3 COOH

CH3 Ans. (d)

On promination 2 possible isomers will form. Tertiary butoxide is a bulky base, which favour elimination to
Option (c) COOH form less substituted alkenes (Hofmann-product).
CH3 CH3 CH3
 (i) KO t Bu/ ∆ 
CH3  CH  CH  CH → CH3  CH  C == CH2
3
 
In respect of COOH, bromination occurs at ortho but in ortho is OSO2 CH3 H
blocked by CH3 and in respect of CH3 bromination not possible. Now, alkene in presence ofO3/H2O2 undergoes oxidative
Option (d) ozonloysis to produce 2-methyl propionic acid and formic acid.
CH2COOH CH3 CH3
(ii) O3/H2O2
CH3—CH—C== CH2 CH3—CH—COOH + HCOOH
2-methyl Formic
H propionic acid acid

In respect of CH2 COOH bromination is done at ortho and para,

then single isomer not possible. 170 A solution of m-chloroaniline, m-chlorophenol and
m-chlorobenzoic acid in ethyl acetate was extracted
initially with a saturated solution of NaHCO 3 to give
168 Which of the following derivative of alcohols is unstable fraction A.
in an aqueous base? [2020, 5 Sep Shift-I] The left over organic phase was extracted with dilute
NaOH solution to give fraction B. The final organic layer
(a) (b) RO was labelled as fraction C. Fractions A, B and C contain
RO O respectively [2020, 7 Jan Shift-I]
(a) m-chlorobenzoic acid, m-chloroaniline and
O
(c) (d) RO—CMe3 m-chlorophenol
RO Me (b) m-chlorophenol, m-chlorobenzoic acid and
m-chloroaniline
Ans. (c) (c) m-chlorobenzoic acid, m-chlorophenol and
Derivative of alcohols is unstable in an aqueous basic solution m-chloroaniline,
and undergoes hydrolysis to give alcohol and carboxylate. (d) m-chlorobenzoic acid and m-chlorophenol
OH Ans. (c)
s
OH/H2O m-chloroaniline,
R O C CH3 R O C CH3
NH2
O Os
doesn’t dissolve inNaHCO3 or
s
CH3 C O– +R OH CH3 C OH + OR Cl
Base
O O NaOH solutions because it has no considerable acidity and
Acid
therefore can’t form salt with bases.
(It is a hydrolysis of ester in basic medium).
Organic Compounds Containing Oxygen 371

In m-chlorophenol; O Cl O
OH
(c) (d)
COOH Cl
Cl O
which is substituted phenol is very weakly acidic which is Ans. (d)
sufficient to form their salt with NaOH. Therefore, these dissolve The major product of the given reaction is (d).
in dil. NaOH solution. But not acidic enough to form a salt with
saturated NaHCO3 solution. This reaction proceed via Friedel-Craft acylation. Here, —Cl
group present on chlorobenzene is ortho and para-directing. It can
Carboxylic acids such as be easily understood by resonating structures of chlorobenzene.
COOH O

Cl COOH Cl
(d)
are strongly acidic. Their acidity is sufficient to form salt with
r r r
aq.NaOHor aq.NaHCO3. Cl Cl Cl Cl Cl
Therefore, m-chlorobenzoic acid (layer A) can be extracted by aq. s s
NaHCO3, then from the left over, m-chlorophenol (layer B) can be
extracted byaq. NaOH. While the final organic layer (C) is of
s
m-chloroaniline.
The given reaction proceed as follows :
171 What is the product of following reaction? O
(i) NaBH4 O +
Hex -3 -ynal → ? C
(ii) PBr3
O + AlCl3 –
(iii) Mg /ether O----Al + Cl3
(iv) CO2 /H3 O+ [2020, 7 Jan Shift-I]
O
O
(a) COOH (b) Cl
COOH

(c) COOH (d) COOH

Ans. (d) O
O
NaBH4 C
H2O
CHO CH2OH
Hex-3-ynal Cl C—O – + Cl
PBr3 COOH —AlC
Mg/Ether l3
CH2MgBr CH2Br O

CO2/H3O+
CH2  COOH 173 The major product of the following reaction is
(Product) CH2CH3

(i) Alkaline KMnO4

172 The major product of the following reaction is
(ii) H3 O+
O Cl
[2019, 9 April Shift-I]
(i) AlCl3, heat
O + COOH CH2CHO
(ii) H2O

O [2019, 8 April Shift-I] (a) (b)

O
CO2H Cl COCH3 CH2COOH
(a) (b)
Cl (c) (d)
O O
372 JEE Main Chapterwise Topicwise Chemistry

Ans. (a) I groups/atoms. More powerful the − I group, stronger will be the
acid. −I power of different groups is as follows :
The major product of the given reaction is benzoic acid
(C6H5 COOH). On vigorous oxidation of alkyl benzene with acidic or NO2 > CN > F >  Cl.
Thus, the correct decreasing order for acid strength is:
alkaline KMnO4 , aromatic acids are obtained. During oxidation of
alkyl benzene, the aromatic nucleus remains intact and the NO2 CH2 COOH > NCCH2 COOH > FCH2 COOH > ClCH2 COOH.
entire chain is oxidised to COOHgroup irrespective of the
length of carbon chain. 176 The decreasing order of ease of alkaline hydrolysis for
the following esters is [2019, 10 Jan Shift-I]
–+
CH2CH3 COOK COOH
COOC2H5 Cl COOC2H5
(i) Alk. KMnO4 (ii) H3O+ I II

O 2N COOC2H5 CH3O COOC2H5

Ethyl Potassium Benzoic acid III IV
benzene benzoate

(a) III > II > IV > I (b) III > II > I > IV
174 The major product of the following reaction is (c) II > III > I > IV (d) IV > II > III > I
OH Ans. (b)
Alkaline hydrolysis of an ester (carboxylic acid derivative) follows
CH2OH H2SO4(cat.)
acyl S N 2 mechanism.
CO2Et CHCl3
O s O O
[2019, 9 April Shift-II] OH
C C + ROs C + ROH
O O OR OH Os
(a) (b)
Rate of S N 2 mechanism depends on the polarity of group of
CO2Et COOH COOR group. Electron withdrawing group (− R > − I) increases
OH OH the rate of S N 2 reaction whereas electron donating group
(+ R > + I) decreases the rate ofSN2 reaction.
(c) (d) Here, the nature of functional groups attached para to the
OEt O
benzene ring are: NO2 >  Cl >  OCH3
O O (− R ) (−I) (+ R )

Ans. (d) So, the order of hydrolysis will be, III > II > I > IV
(− R ) (−I ) (+ R )
Given reaction involves acidic hydrolysis of esters followed by
177 Which dicarboxylic acid in presence of a dehydrating
the intramolecular cyclisation. The chemical equation is as
agent is least reactive to give an anhydride?
follows: [2019, 10 Jan Shift-I]
OH OH
CH2
CH2OH H2SO4(cat.) CH2OH
+C2H5OH CO2H CH2 COOH
CHCl3
(a) (b)
COEt C OH COOH
CH2
CO2H
O O CH2
OH OH
O
CH2 OH –H2O COOH C
O CH2 OH
(c) (d)
C OH CH2 OH
O COOH C
O
O
175 The correct decreasing order for acid strength is
Ans. (b)
(a) FCH2COOH> NCCH2COOH > NO2CH2COOH> ClCH2COOH COOH
(b) CNCH2COOH> O2NCH2COOH > FCH2COOH> ClCH2COOH Heating of (CH2)4 (adipic acid) with
COOH
(c) NO2CH2COOH> NCCH2COOH > FCH2COOH> ClCH2COOH
a dehydrating agent, decarboxylates (  CO2 ) to give a ketone
(d) NO2CH2COOH> FCH2COOH > CNCH2COOH> ClCH2COOH
[2019, 9 Jan Shift-I] (cyclopentanone), not an anhydride.
Ans. (c)
COOH D
All the given compounds areα-monosubstituted acetic acid O
COOH –CO2
derivatives and theα-substitutions have been made by strong–I –H2O
Organic Compounds Containing Oxygen 373

178 The major product of the following reaction is Here, the haloform reaction will give following reaction:
O CH3 2 4 6 s s
(i) Dil. HCl/∆ 1 5 I2/OH I2/OH
(ii) (COOH)2/ 3 [O]
CH3O OH Polymerisation OH O

O O CI3 s 2 4 OH + CHI3
OH 5
O— 1 3 (G)
(a) —O O (b) —O O (Yellow ppt.)
n O
n
O (i) Tollen’s reagent (AgNO3 + NH4OH) is a mild oxidising agent. It
does not react with  CH  CH3 group (2°-alcohol).
OH OH

O OH
O (ii) Alkaline KMnO4 cannot perform the oxidative cleavage,
(c) O O— rather it will hydroxylate the C == C.
—O n (d) —O
O n OH
O  KMnO
OCOCH3 CH3  CH == CH  CH2  CH  CH3  4→
OCH3 6 5 4 3 2 1 OH −
[ 2019, 10 Jan Shift-II]
OH OH OH
Ans. (c)
  
In the given reaction, ester get cleaved in presence of dil. HCl CH3  CH  CH  CH2  CH  CH3
and readily forms alcohol. This alcohol on reaction with oxalic 6 5 4 3 2 1
acid undergoes polymerisation reaction. (iv) CrO2 Cl2 / CS2 will not react here.
Hydrolysis of the ester group
H CH3 180 The major product obtained in the following reaction is
O OH
Dil. HCl/D O O OH
Me – CH3COOH
O LiAlH4
O OH OH OH C C OH
{

Ether group (excess)

remains unaffected CH3
by dil. HCl (hot) Me
O O H OH C C OH
NO2 [2019, 11 Jan Shift-II]
(COOH)2/
Polymerisation O O
–H2O OH OH
O
O
O (a) (b)
CH3 CH3
O n
NO2 OH NH2 OH
OCH3
O OH OH

179 Which is the most suitable reagent for the following

transformation ? (c) (d)
CH3
OH CH3
 NO2 OH NH2 OH
CH3  CH == CH CH2  CH CH3 → Ans. (b)
CH3 CH == CHCH2CO 2H LiAlH4 acts as a nucleophilic reducing agent that can reduce
[2019, 10 Jan Shift-II] COOHto CH2OH,  C == O
(a) Tollen’s reagent (b) I2 /NaOH 
(c) Alkaline KMnO 4 (d) CrO2Cl2 / CS2 into  CH OHand NO2 into NH2 , but it
Ans. (b) 
The most suitable reagent to carry out given transformation is cannot reduce isolated C==C
I2 /NaOH
O OH isolated C==C OH
OH

CH3  CH == CH  CH2  CH  CH3 Strong
oxidation, [O]
→ LiAlH4 (excess)
6 5 4 3 2 1 (Oxidative cleavage)
CH3
O
 NO2 NH2 OH
CH3  CH == CHCH2  C  OH +CHI3 ↓ + CO2 ↑
6 5 4 3 2 Compound
(b)
374 JEE Main Chapterwise Topicwise Chemistry

181 The increasing order of the reactivity of the following O

with LiAlH4 is [2019, 12 Jan Shift-II] O
O CH3
O O
O CH3
(A) (B)
(a) (b)
C2H5 NH2 C2H5 OCH3
CO2H
O O O CO2H
(C) (D)
C2H5 C 2H 5 O CO2H
C2H5 Cl O O CH3
C
(a) (A) < (B) < (D ) < (C) (b) (A) < (B) < (C) < (D ) O
(c) (B) < (A) < (D ) < (C) (d) (B) < (A) < (C) < (D ) (c) OH (d)
Ans. (a)
CO2H
All the given compounds are acid derivatives, thus contain O CH3
carbonyl group
in them.LiAlH4 reduces these compounds through nucleophilic O
substitution via addition elimination (S NA E) reaction. The rate of
reaction depends upon the following factors : Ans. (a)
(i) Size of alkyl group.
OH
(ii) Steric hinderance around the> C == O group. + CO2+NaOH
Followed by
acidification
X
(iii) (+ ) ve charge on the C-atom of> C == O group. (CH3CO)2O
The alkyl groups are more or less same in the given compounds. conc. H2SO4
(Catalytic amount)
Thus, the reactivity order of given compounds depends upon 2nd
and 3rd factor written above. The cumulative effect of these ?
two factors results to leaving group ability (LGA) of the The very first reaction in the above road map looks like Kolbe’s
substituents in the following order : reaction which results to salicylic acid as
O
− −
 − OH OH
Cl > O  C  CH3 > O  CH3 > NH2 (i) CO2, NaOH
Good leaving Poor leaving (ii) Acidification
group group
COOH
This leaving group ability (weak conjugate Salicylic acid
base) corresponds directly to the reactivity order. (X)

The salicylic acid with acetic anhydride [(CH3CO)2 O] in the

presence of catalytic amount of conc. H2SO4 undergoes
Hence, the correct reactivity order is: acylation to produce aspirin as
O O O
 O
C2H5  C  Cl > C2H5 O C2H5
CH3 C O
Most reactive (D) O
O O OH + CH3 C
O—C—CH3
  Conc.
> C2H5  C OCH3 > CH3 C NH2 O
H2SO4 + CH3COOH
(B) Least reactive COOH
COOH
(A) Acetyl salicylic acid (Aspirin)
Note The −I-effect of —Cl and + m-effects of
O Aspirin is a non-narcotic analgesic (Pain killer).
•• 
 N H2 O  C  C2H5 and  OCH3 groups while attached to 183 In the following sequence of reaction,
 C  group to be reduced KMnO SOCl H /Pd
 Toluene →
4
A →
2
B →
2
BaSO
C
4
O
The product C is [JEE Main 2015]
Also, add to the group leaving ability.
(a) C 6H5 COOH (b) C 6H5CH3 (c) C 6H5CH2OH (d) C 6H5CHO
182 Phenol on treatment with CO 2 in the presence of NaOH Ans. (d)
Toluene undergoes oxidation withKMnO4 , forms benzoic acid. In
followed by acidification produces compound X as the this conversion, alkyl part of toluene converts into carboxylic
major product. X on treatment with (CH3CO) 2 O in the group. Further, benzoic acid reacts with thionyl chloride (SOCl2 )
presence of catalytic amount of H2SO 4 produces: to give benzoyl chloride which upon reduction withH2 /Pd or
[JEE Main 2018] BaSO4 forms benzaldehyde (Rosenmund Reduction).
Organic Compounds Containing Oxygen 375

The conversion look like, (a) acetaldehyde (b) acetylene

O Cl (c) ethylene (d) acetylchloride
CH3 COOH C Ans. (c)

KMnO4 SOCl2
The complete series of reaction can be represented as
+ SO2 + HCl LiAlH4 PCl5
CH3COOH CH3CH2OH
(A )
(A) (B)
Toluene Benzoic Benzoyl chloride CH3CH2Cl + POCl3 + HCl
acid H2 / Pd (Rosenmund elimination alc.KOH
BaSO4 reaction) reaction

O
CH2=CH2
H
C (C)

186 Aspirin is known as [AIEEE 2012]

+ HCl
(a) acetyl salicylic acid (b) phenyl salicylate
(c) acetyl salicylate (d) methyl salicylic acid
(C)
Benzaldehyde Ans. (a)
Aspirin is acetyl derivative of salicylic acid.
184 Sodium phenoxide when heated with CO 2 under
OH O—COCH3
pressure at 125°C yields a product which on acetylation
produces C. [JEE Main 2014] COOH COOH
ONa + + CH3COCl
125°C H
+ CO2 B C
5 atm Ac2O
Acetyl salicylic acid
The major productC would be
OCOCH3 OH 187 Which of the following reagents may be used
COOH COCH3 to distinguish between phenol and benzoic acid ?
(a) (b) [AIEEE 2011]
(a) Aqueous NaOH (b) Tollen’s reagent
(c) Molisch reagent (d) Neutral FeCl3
COCH3
OH OCOCH3 Ans. (d)
COOCH3
Reagent Phenol Benzoic acid Conclusion
(c) (d)
(a) Aqueous Salt formation Salt formation No specific
COOH NaOH colour change
(b) Tollen’s No effect No effect
Ans. (a) reagent
s r (c) Molisch No effect No effect
ONa Os
+ reagent
e + Na
(d) Neutral Violet colour Buff- Thus, FeCl 3 can
FeCl 3 coloured be used to make
− + + precipitate distinction
O O O
H O−
- O= C= O C 188 The strongest acid amongst the following compounds is
O [AIEEE 2011]
(a) CH3COOH (b) HCOOH
OCOCH3 (c) CH3CH2CH(Cl)CO2H (d) ClCH2CH2CH2COOH
OH OH
− Ans. (c)
COOH (CH CO) O COOH COO
3 2 H+ − I effect exerting (electron withdrawing) groups increases the
acidic strength of an acid by withdrawing electron density
(C) (B) towards itself, they weakning OH bond and thus, the release
of H+ ion by an acid becomes easier.
185 In the reaction, Whereas +I effect excerting (e − releasing) groups decreases the
LiAlH 4 PCl 5 acidic strength by donating electron density to O-atom. Further,
alc ⋅ KOH
CH3COOH → A → B → C − I effect decreases with distance. Thus, the acidic strength of
the given acids would be
the product C is [JEE Main 2014]
376 JEE Main Chapterwise Topicwise Chemistry

O 191 The compound formed as a result of oxidation of ethyl

CH3 CH2 CH C
benzene by KMnO 4 is [AIEEE 2007]
OH
O
(a) benzophenone
Cl (b) acetophenone
CI  CH2  CH2  CH2 C  OH > (c) benzoic acid
O O (d) benzyl alcohol
Ans. (c)
CH3 C  OH > H  C  OH Any aliphatic carbon with hydrogen attached to it, in
O combination with benzene ring, will be oxidised to benzoic acid
 by KMnO4 / H+ .
Hence, CH3 CH2 CH  C OH is most acidic and strongest acid
 192 p-cresol reacts with chloroform in alkaline medium to
Cl
give the compound A which adds hydrogen cyanide to
than other given compounds.
form the compound B. The latter, on acidic hydrolysis
189 A liquid was mixed with ethanol and a drop of gives chiral carboxylic acid. The structure of the
concentrated H2SO 4 was added. A compound with a carboxylic acid is [AIEEE 2005]

fruity smell was formed. The liquid was [AIEEE 2009] CH3
(a) CH3OH (b) HCHO (c) CH3COCH3 (d) CH3COOH CH2COOH
Ans. (d) (a) (b)
Conc. H2SO 4
A liquid + C2H5OH → Compound CH2COOH
(Fruity smell)
OH OH
Fruity smell is the characteristic property of ester, thus the
above reaction leads to the formation of ester. CH3 CH3
O
Conc. H2SO 4  CH(OH)COOH
CH3COOH + C2H5OH → CH3 C— OC2H5 + H2O (d)
(c)
Ethyl acetate
(Fruity smell) CH(OH)COOH
This reaction is called esterification.
OH OH
190 The major product obtained on interaction of phenol Ans. (c)
with sodium hydroxide and carbon dioxide is
[AIEEE 2009] CH3 CH3 CH3
(a) benzoic acid (b) salicylaldehyde
(c) salicylic acid (d) phthalic acid CHCl3 H  CN OH
Ans. (c) KOH (aq) (nucleophilic
CHO CHCN
(Riemer addition
OH OH OH OH reaction) OH (B)
OH Tieman
(p-cresol) reaction) (o-hydroxy
NaOH —COONa H+ p-methyl +
—COOH benzaldehyde) CH3
H2O/H
CO2
OH
Salicylic acid
CHCOOH
The above reaction is called Kolbe’s reaction.
OH
26
Organic Compounds
Containing Nitrogen
TOPIC 1 Mechanism
Aliphatic Amines (i) Hydride nucleophile attacks the electrophilic carbon in
nitrile to form imine anion.
OH OH OH
01 The major products A and B in the following set of
reactions are [2021, 31 Aug Shift-I]
CººN C==N CH2—N

—
OH

—
H AlH2
H
—

—
LiAIH4 H3O+ AlH2 Amine derivative
A B H—Li—Al—H
H3O + H2SO4
—

CN
H
OH OH
(ii) Hydrolysis of amine derivative.
(a) A =
, B= OH OH
—OH CHO H—OH

OH OH CH2—N CH2—NH—AlH2
—

(b) A = AlH2 H—OH

, B=
—CHO CO2H
OH
OH
— NH2
(c) A = ——COOH (A)
, B=
—NH2 2-hydroxy-2-methyl propionitrile on acidic hydrolysis
gives 2-hydroxy-2-methylpropionic acid.
OH OH
OH OH
(d) A = H3O+ H2SO4
, B= COOH
—NH2 CHO CN COOH
(B)
2-hydroxy-2-methyl 2-hydroxy-2-methyl
Ans. (c) propionitrile propionic acid
Nitriles can be converted to 1° amines by reaction withLiAlH4 . Mechanism
OH OH OH OH OH
LiAlH4 H
+ OH2
H3O+ — NH2 N—H
CN CººN CººN — H
H
2-hydroxy-2-methyl propionitrile 1-amino-2-methylpropan-2-ol OH2
(A )
378 JEE Main Chapterwise Topicwise Chemistry

OH OH (iii) NaNO 2 , HCl

(iv) H 2 O
Tautomerism NH2 NH2 CH3 —CH— CH2 —CH2 —NH2 →CH3 —CH—CH2 —CH2OH
+H2O
 
OH OH CH3 CH3
H 2O
OH 3-methyl -butanamine 3-methyl -butanol
OH OH (Major product)
+
H transfer NH3 –NH3 OH –H+ OH
OH 03 Which of the following is not a correct statement for
OH O OH
primary aliphatic amines? [2021, 27 Aug Shift-I]

The last step of dehydration takes place in presence ofH2SO4 to (a) The intermolecular association in primary amines is less
form 2-methylacrylic acid. than the intermolecular association in secondary amines.
2-methylacrylic acid is the product (B). (b) Primary amines on treating with nitrous acid solution
form corresponding alcohols except methyl amine.
H OH
H2SO4 (c) Primary amines are less basic than the secondary amines.
COOH (d) Primary amines can be prepared by the gabriel
COOH (B) phthalimide synthesis.
2-methylacrylic acid
Ans. (a)
02 The major product of the following reaction is The intermolecular association is more in primary amines than in
CH3 O secondary amines as there is only one hydrogen atom available for
formation of hydrogen bond in secondary amines, while primary
 
amines has two hydrogen atoms. So, statement (a) is not correct.
CH3  CH CH2 CH2 C Cl
(i) Alcoholic NH3 04 What is A in the following reaction?
(ii) NaOH, Br2
 
→ Major product CH2Br (i) N K
(iii) NaNO2 , HCl A
(iv) H2 O (Major
(ii) OH/H2O
[2021, 27 Aug Shift-I] product)
Br [2021, 27 July Shift-II]

(a) CH3  CH CH CH2OH
 NHCH2
(a)
CH3
(b) CH3  CH CH2 CH2 CH2OH CH2OH
 (b)
CH3
(c) CH3  CH CH2 CH2OH

CH3 (c) NH
(d) CH3  CH CH2 CH2 Cl

CH3 CH2NH2
Ans. (c) (d)
In first step, ammonia reacts with ethanoyl chloride to give
ethanamide and HCl. In the second step degradation of amide Ans. (d)
takes place that is known as Hoffmann’s bromamide degradation Complete reaction is as follows :
reaction. (i) Removal of Br − and formation of C N bond via SN2
The third step is diazotisation, where an unstable diazonium salt mechanism.
is obtained, which further gives alcohol as a major product and
alkene and alkyl halides. K+
CH2—Br
The complete reaction is SN2
CH3 + N
O
  (i) Alcoholic NH 3
Benzyl bromide
CH3 —CH—CH2 — CH2 —C— Cl →
4-methylpentanoyl chloride O
 (ii) NaOH, Br2
CH3 —CH— CH2 —CH2 —C—NH2 →
 CH2—N
CH3
4-methyl pentanamide
Organic Compounds Containing Nitrogen 379

(ii) Hydrolysis process in basic medium Addition of OH− ions OH Cl

for formation of phthalic acid and addition ofH+ ions for
formation of benzyl amine. O== S==O O== S==O

H—OH
NaOH
PCl5
OH–/H2O
CH2—N (Benzene sulphonic
acid) Benzene sulphonyl
chloride
(Hinsberg reagent)
H—OH

CH2—NH2 06 The number of nitrogen atoms in a semicarbazone

HO
+ molecule of acetone is …… . [2021, 20 July Shift-I]
HO
Ans. (3)
Benzyl amine
(A) Three nitrogen atoms are present as per structure below
(Major product) Phthalic acid
H H

05 Which one of the products of the following reactions N N

does not react with Hinsberg reagent to form N
sulphonamide? [2021, 25 July Shift-I] O
Semicarbazone molecule of acetone
CN

C2H5OH 07 Compound A is converted to B on reaction with CHCl 3

(a) + Na/Hg
and KOH. The compound B is toxic and can be
decomposed by C. A, B and C respectively are
NO2
[2021, 20 July Shift-I]
CN (a) primary amine, nitrile compound, conc. HCl
(b) secondary amine, isonitrile compound,
(b) + SnCl2 + HCl conc. NaOH
(c) primary amine, isonitrile compound, conc. HCl
CN (d) secondary amine, nitrile compound, conc. NaOH
H3O+ Ans. (c)
(c) + LiAIH4
Primary amine reacts in presence of chloroform gives isonitrile
which is toxic in nature which further reacts in presence of
CHO HCl /H3O+ to give primary amine and acid.
CN Chemical reaction is as follows
CHCl3 H3O+
(d) + H2/Ni RNH2 R—N ≡≡C RNH2+ HCOOH
HCl
1° amine Isonitrile
CH3 (C)
(A) (B)

Ans. (b)
Toxic
Hinsberg reaction is a test for the detection of primary,
secondary and tertiary amines. In this test, Hence, A-primary amine, B-isonitrile compound and C-conc. HCl.
the amine is shaken well with Hinsberg reagent in the presence
of aqueous alkali. 08 In the reaction of hypobromite with amide, the carbonyl
A reagent containing an aqueous sodium hydroxide solution and carbon is lost as [2021, 18 March Shift-II]
benzene sulphonyl chloride is added to a substrate. In reaction
(b), imino group formed does not react with Hinsberg reagent. (a) CO2−
3 (b) HCO −3
(c) CO2 (d) CO
(Imino group)
Ans. (a)
CN CH==NH
Hypobromite transforms the primary amide to carbonic acid
which further loses carbonyl carbon as CO23− , yielding the amine
SnCl2 + HCl
product.
Chemical reaction is as follows
Cyanobenzene (Imino group does not react
with Hinsberg reagent
R—C—NH2 + Br2 + 4NaOH

Product formed in all other reactions is a primary amine so, it O

gives Hinsberg reagent. R—NH2 + Na2CO3 + 2NaBr + 2H2O
380 JEE Main Chapterwise Topicwise Chemistry

Mechanism Reaction involved are as follows:

H OH
Primary (1°) amine Primary amines react with para toluene
R—C—N –H2O
R—C—NH + Br—Br sulphonyl chloride to form a precipitate that is soluble in NaOH.
H
Me— —SO2Cl
–H2O
R—C—N—Br R—C—N—Br R—NH2 RNHSO2 — —Me (ppt.)
OH –HCl
H Soluble in
NaOH (Base)
–Br
H2O
R—N — C — O R—NH2 + Na2CO3 Secondary (2°) amine Secondary amines reacts with para toluene
H—OH (2NaOH)
or sulphonyl chloride to give a precipitate that is insoluble in NaOH.
H—OH 2–
CO 3
(Carboxylate ion) Me— —SO2Cl
Thus, the carbonyl carbon is lost as CO23− in the given reaction. R2—NH
–HCl
RNSO2 — —Me (ppt.)
The complete reaction in ionic form looks like. Not soluble in base
O
Tertiary (3°) amine Tertiary amines do not react with para
 − toluene.
R CNH2 + 4BrO− + 2H+ → RNH2 + CO23− + 4Br − + OH
(Amine)
Me— —SO2Cl
R3N No reaction
09 An organic compound “A” on treatment with benzene
sulphonyl chloride gives compound B. B is soluble in dil.
NaOH solution. Compound A is [2021, 18 March Shift-II]
11 Which of the following is least basic?
[2021, 16 March Shift-II]
(a) C 6H5  N  (CH3)2 (b) C 6H5 NHCH2CH3 •• ••
(a) (CH3CO) NHC2H5 (b) (C2H5 ) 3 N
(c) C 6H5 CH2NHCH3 (d) C 6H5  CH NH2
•• ••
 (c) (CH3CO)2 NH (d) (C2H5 )2 NH
CH3
Ans. (d)
Ans. (c)
Hinsberg reagent (benzene sulphonyl chloride) with 1º amine
Basic nature is directly proportional to electron releasing
gives sulphonamide product i.e. N-ethylbenzene sulphonamide
tendency. If lone pair is delocalised, electron density decreases
and it is soluble in dil. NaOH.
and basic strength decreases.

R—NH2 + Cl—S—
(a) CH3—C—NH—C2H5 CH3—C==NH—C2H5
(A)
1º amine Benzene sulphonyl
chloride
(c) CH3—C—NH—C—C2H5 Delocalised with both
dil. NaOH
carbonyl group
R—NH—S—
(B) So, there is delocalisation of electron in both options (a) and (c).
Sulphonamide But it option (c) there is delocalisation of electron with both
carbonyl group. Hence, it is weakest base.
R—N—S— There is a subtle interplay of the inductive effect, solvation
effect and steric hinderance of the alkyl group, which decides
the basic strength of alkyl amines in the aqueous state. The
order of basic strength in case of ethyl substituted amines in
Hence, A is 1° amine i.e. C6H5  CH NH2 aqueous solution is as follows
|
CH3 (C2H5 )2 NH > (C2H5 ) 3N > C2H5NH2 > NH3
••
10 Primary, secondary and tertiary amines can be ∴ (C2H5 )2 NH is strong base.
separated using [2021, 17 March Shift-II]
(a) para-toluene sulphonyl chloride 12 Ammonolysis of alkyl halides followed by the treatment
(b) chloroform and KOH with NaOH solution can be used to prepare primary,
(c) benzene sulphonic acid secondary and tertiary amines. The purpose of NaOH in
(d) acetyl amide the reaction is [2021, 16 March Shift-II]
Ans. (a) (a) to remove basic impurities
Primary, secondary and tertiary amines can be separated using (b) to activate NH 3 used in the reaction
para-toluene sulphonyl chloride. This test is known as Hinsberg (c) to remove acidic impurities
test. (d) to increase the reactivity of alkyl halide
Organic Compounds Containing Nitrogen 381

Ans. (c)
Ammonolysis of alkyl halides CN C—NH2 NH2
NH3 R—X R—X RX ⊕s (i) KOH, H2O
R–X R—NH2 R2NH R3N R4NX
–HX –HX –HX (ii) Br2/NaOH
Cyanobenzene
During the reaction HX (acid) is formed. Hence, we use NaOH to Aniline
remove this acidic impurities.
(d) Acid chloride undergoes nucleophilic substitution withNH3
to form acid amide. Acid amide undergoes Hoffmann
13 Which of the following reaction does not involve bromamide degradation.
Hoffmann bromamide degradation? [2021, 16 March Shift-I]
O

CH2CNH2 C—Cl C—NH2

(a) (i) NH3,NaOH NH2

CH2NH2 (ii) Br2/NaOH
Benzoyl
Br2,NaOH chloride
Aniline

CN NH2
(i) KOH,H2O
14 An amine on reaction with benzene sulphonyl chloride
(b)
(ii) Br2,NaOH
produces a compound insoluble in alkaline solution. This
O amine can be prepared by ammonolysis of ethyl
chloride. The correct structure of amine is
CH2—C—CH3 [2021, 26 Feb Shift-I]
CH2NH2 NH CH2CH2CH3
(c) (i) Br2,NaOH/H+
(ii) NH3/D (a) (b) CH3CH2NH2
(iii) LiAlH4/H2O
H
O (d) CH3CH2CH2N CH2CH3
(c) CH3CH2CH2NHCH3
NH2
Cl (i) NH2,NaOH Ans. (d)
(d)
(ii) Br2,NaOH The amine on reaction with benzene sulphonyl chloride
(Heisenberg reagent) produces a compound insoluble in alkali. It
Ans. (c) indicates the amine is a 2° amine. i.e. all options are possible
Methyl ketone gives haloform reaction to form carboxylic acid except option (b) which is a 1° amine (CH3CH2NH2 ).
salt which on heating withNH3 forms amide. Amide is reduced to As this 2° amine can be prepared by ammonolysis of ethyl
amine byLiAlH4 . chloride, the 2°-amine should have at least one ethyl (C2H5 )
group.
– + (a) Ph NH  CH2 CH2 CH3 does not have ethyl group.
CH2—C—CH3 CH2—C—ONa
(i) NaOH/H+ (ii) NH3 (c) CH3CH2 CH2 NH  CH3 does not have ethyl group.
Br2 D (d) CH3CH2 CH2 NH  CH2 CH3 has one ethyl group.
1-phenyl So, option (d) is the correct answer.
propan-2-one
Preparation CH3CH2 CH2 NH  CH2 CH3 by ammonolysis of
C—NH2 CH2—NH2 CH3CH2 Cl
(iii) LiAlH4/H2O NH 3 CH 3 CH 2 Cl
CH3CH2 Cl → CH3CH2 NH2 →
−HCl (n - propyl chloride )
Ethyl Ethanamine
Benzamide Benzylamine chloride (1° )
CH3CH2 NH  CH2 CH2 CH3
(a) Benzamide undergoes Hofmann bromamide degradation 1-(N-ethyl) -propanamine
when treated with bromine and aqueous sodium (2 ° )
hydroxide, to produces benzylamine. Heisenberg test of CH3CH2 NH  CH2 CH2 CH3 or EtNHnPr

CH2—C—NH2 CH2—NH2 Cl —S—Ph

Br2/NaOH Et—N H Et—N—S—Ph + HCl

(Heisenberg
Benzamide Benzylamine reagent)
nPr nPr
(b) Benzene nitrile undergoes alkaline hydrolysis to form No acidic H-atom attached
acidamide which further give Hofmann bromamide with the nitrogen atom,
degradation. hence, it is insoluble in alkali.
382 JEE Main Chapterwise Topicwise Chemistry

15 The most appropriate reagent for conversion of C 2H5CN 17 The increasing order of pK b for the following
into CH3CH2CH2NH2 is [2020, 5 Sep Shift-I]
compounds will be :
(a) Na(CN)BH3 (b) LiAlH4 (c) NaBH4 (d) CaH2
N
Ans. (b) NH2  CH  NH,
(A) N NH, CH3  NH  CH3
For the conversion of C2H5 CN into CH3CH2 CH2NH2 , strong
reducing agent is required among the given reducing agent. ( C)
Strong reducing agent isLiAlH4 . It is the most appropriate (B) [2020, 7 Jan Shift-I]
reagent for this reduction. (a) (B) < (C) < (A) (b) (C) < (A) < (B)
LiAlH
C2H5 CN  4→ CH3CH2 CH2NH2 (c) (A) < (B) < (C) (d) (B) < (A) < (C)
Ans. (d)
16 Which of the following compounds can be prepared in
(B) is most basic because of high resonance stabilisation of its
good yield by Gabriel phthalimide synthesis?
[2020, 6 Sep Shift-II] conjugate acid.
CH2NH2 + H H H
N N N
(a) (b) CH3 CH2 NHCH3
N NH N NH N NH
O
NH2
CH2CNH2 Among rest two compounds,NH2  CH == N H (A) has higher
⋅⋅
(c) (d)
basicity than CH3 NH  CH3 (C) because conjugate acid of (B) is
resonance stabilised but conjugate acid of (C) is not resonance
Ans. (a) stabilised at all.

Gabriel phthalimide synthesis is used for the preparation of 1° NH2—CH==NH2 NH2—CH==NH2

aliphatic amine and 1° aromatic amine.
Hence, the correct order of basicity of the given compounds is,
Phthalimide on treatment with ethanolic KOH forms potassium
B > A > C. Stronger is the base, smaller will be its pK b value.
salt of phthalimide which on heating with RX followed by either
Thus, the increasing order of pK b values is B < A < C.
alkaline hydrolysis or hydrazinolysis with hydrazine (H2N⋅NH2 )
produces the corresponding 1° amine. 1° aromatic amine (except
18 The number of sp 2 -hybridised carbons present in
those containing EWG at o-and p-positions, e.g., NO2 group
cannot be synthesised by this method because ArX does not “aspartame” is ………… [2020, 7 Jan Shift-II]

urdergo SN reaction with anion formed by phthalimide. Ans. (9)

O H Structure of aspartame :
N—H
COOH H
∆
O
–H2O –H2O
COOH O OCH3
Phthalic acid O N
O Phthalic O H
anhydride OH NH2
RX Alc. The 9 carbon atoms highlighted by the dark circle are
NK NH
–KX KOH
sp2 -hybridised.
O O
Potassium Phthalimide 19 The major products A and B in the following reactions
phthalimide are : [2020, 8 Jan Shift-I]
O O CN Peroxide
[A]
Heat
H2N—NH2 NH
N—R + RNH2 [A] + B
Hydrazinolysis NH 1° amine

O O · CN
N-alkyl 1º amine (a) A= and B =
H CN
phthalic acid
s · CN CN
H /H2O or OH /H2O H—C— (b) A= and B =
COOH

COOH
+ RNH2
1º amine
(
— Here, R = ) (c) A= ·
CN
and B =
CN
Organic Compounds Containing Nitrogen 383

CN CN In second case, substituted ammonium cation is also stabilised

(d) A= · and B =
by solvation with water molecules. Greater the size of ion, lesser
will be the solvation and less stabilised is the ion.
Ans. (c)
OH2
The reaction is given as follows :
H
CN Peroxide CN | C2H5 H----OH2
+
heat C2H2—N+—H----OH2 > N
| C2H5 H----OH2
(A) H
2° amine

CN OH2
1° amine
(B)
Considering both steric and solvation effect, it can be concluded
It can be proceed as : that greater the number of H-atoms on the N-atom, greater will
Peroxide on heating give radicals which abstract hydrogen from be the H-bonding and hence more stable is the ammonium
cation. But in case of C2H5 group, + I-effect predominates over
C N
to give (A) H-bonding. Therefore, order is 2° amine > 1° amine > ammonia,
i.e. (C2H5 )2 NH > C2H5NH2 > NH3.
C N C N,
21 Which of the following amines can be prepared by
(A) Gabriel phthalimide reaction? [2019, 8 April Shift-I]
(a) n - butylamine (b) triethylamine
‘A’which on addition to
(c) t-butylamine (d) neo -pentylamine
(Anti-Markownikoff ’s)
Ans. (a)
CN
(Free radical) n- butylamine (CH3CH2 CH2 CH2NH2 ) can be prepared by Gabriel
phthalimide reaction. This method produces only primary
+ CN
amines without the traces of secondary or tertiary amines.
In this method, phthalimide is treated with ethanolic KOH, it
Abstract
hydrogen Termination forms potassium salt of phthalimide which on heating with alkyl
free radical halide followed by alkaline hydrolysis forms corresponding
primary amines.
CO CO
CN
NH+ Alc. KOH –H O N–K+
2
CO CO
nBu—X
20 In the following compounds, the decreasing order of
COO–Na+ CO
basic strength will be [2019, 8 April Shift-I]
+ n Bu—NH2
NaOH(aq.)
N—R
(a) C2H5NH2 > NH3 > (C2H5 )2 NH (b) (C2H5 )2 NH> NH3 > C2H5NH2 COO–Na+ CO
1° amine
(c) (C2H5 )2 NH> C2H5NH2 > NH3 (d) NH3 > C2H5NH2 > (C2H5 )2 NH N-alkyl phthalimide
Ans. (c) Triethylamine,t-butylamine and neo-pentylamine cannot be
Basic strength can be compared by the reaction of an prepared by Gabriel phthalimide reaction.
alkanamine and ammonia with proton.
H H 22 The major products A and B for the following reactions
| |
R—N + H+ R—N+—H are, respectively [2019, 9 April Shift-II]
| |
H H O
H H I H2/Pd
| | KCN
[A] [B]
H—N + H+ H—N+—H DMSO
| |
H H O OH

Basicity of an amine in aqueous solution depends upon the CN CH2NH2

(a) ;
solubility of ammonium cation formed by accepting proton from
water. The stability of ammonium cation depends upon the HO CN HO CH2 NH2
following factors. I H
(a) + I-effect (b) Steric effect (c) Solvation effect (b) ;

In first case, on increasing the size of alkyl group +I effect O O

increases and the positive charge of ammonium cation gets
CN CH2NH2
dispersed more easily, Therefore, order of basicity is 2º amine > (c) ;
1º amine > ammonia.
384 JEE Main Chapterwise Topicwise Chemistry

HO CN HO CH2 NH2
25 Ethylamine (C 2H5NH2 ) can be obtained from
I I
(d) ; N-ethylphthalimide on treatment with
[2019, 10 April Shift-I]
Ans. (c) (a) NaBH4 (b) NH2NH2
O O (c) H2O (d) CaH2
I CN
Step I Ans. (b)
KCN
DMSO The reaction for the production of ethylamine from
N-ethylphthalimide can be takes place as follows:
[A ] Step II H2/Pd

O O H HN O
CH2NH2
Hydrazinolysis
NH
N—C2H5 | + C2H5—NH2
NH2—NH2
(Hydrazine)
NH Ethylamine
H HN (An aliphatic
O O
[B] 1°-amine)
(N-ethylphthalimide)
Step I involves the nucleophilic substitution reaction in which I
(Iodine) is substituted by CN group. This reaction is the second step of Gabriel phthalimide synthesis
In step II, H2 /Pd reagent is used for reduction process. Here, for the preparation of aliphatic 1°-amines and amino acid. In this
CN group reduces itself to CH2 NH2 . step concentrated alkali can also be used in place of hydrazine.

23 Hinsberg’s reagent is [2019, 9 April Shift-II] 26 Which of the following is not a correct method of the
(a) SOCl2 (b) C 6H5COCl (c) C 6H5 SO2Cl (d) (COCl)2 preparation of benzylamine from cyanobenzene?
[2019, 10 April Shift-II]
Ans. (c)
(a) H2 / Ni
Hinsberg’s reagent is C6 H5SO2 Cl (benzene sulphonyl chloride). (b) (i) HCl /H2O (ii) NaBH4
This reagent is used to distinguish between primary, secondary
(c) (i) LiAlH4 (ii) H3O +
and tertiary amines.
(d) (i) SnCl2 + HCl (gas) (ii) NaBH4
24 The major product of the following reaction is Ans. (b)
OH The preparation of benzylamine from cyanobenzene using given
 Ethyl formate (1 equiv.) reagents are as follows :
CH3 C H CH2CH2NH2 →
Triethylamine [2019, 10 April Shift-I]
H2/Ni
OH Ph  C= N ∆ Ph  CH2  NH2
(Cyanobenzene)
 Benzylamine
(a) CH3 CHCH2CH2NHCHO (b) CH3CH == CH CH2NH2
OH O
(i) LiAlH4 (ii) NaBH4
 (ii) H Or
(c) CH3 CH CH == CH2 (d) 3
O H r
(i) SnCl2
[Ph  CH==NH2[2 SnCl 62-
CH3CHCH2CH2NH2 (ii) HCl (g) bis (benzaldiminium )
Ans. (a) hexachlorostannate (IV)
The mechanism of the given reaction is as follows :
HCl , H O NaBH
OH
O
PhCN →
2
PhCOOH →
4
PhCH2OH
–NH 4 Cl Benzoic acid
H—C—OEt Benzyl alcohol
CH3—CH—CH2CH2—NH2
[–NH2 is stronger
Et3N Thus, option (b) is incorrect.
—EtOs
nucleophile than
—OH] OH 27 The major product of following reaction is
r
(i) AIH(i - Bu)
CH3—CH—CH2CH2—NH—CH=
=O R  C ≡≡ N →
2
?
(ii) H2 O [2019, 9 Jan Shift-I]
H
EtOs
(a) RCHO (b) RCONH2
OH
(c) RCOOH (d) RCH2NH2
CH3—CH—CH2CH2—NH—CHO Ans. (a)
The basic mechanism of the reaction is acyl Key Idea DIBAL-H is diisobutyl aluminium hydride,
S N 2 because the nucleophile, [(CH3)2 CHCH2 ]2 AlH. It is a selective reducing agent. It reduces
CH3 (OH)CH2 CH2 NH2 attacks the sp2 carbon of the ester carboxylic acids, carboxylic acid derivatives and nitriles into
(H  CO2Et) and gets substituted. aldehydes. It is an electrophilic reducing agent.
Organic Compounds Containing Nitrogen 385

The mechanism of the reaction is as follows: COCH3

OH OH
H
(sp2) s (a) (b)
Al (DIBAL-H) Al NH2 NHCOCH3
(An electrophilie)
r OCOCH3
R C N H
R C N Hydride donor
(Reducing agent) (c) (d)
(A nucleophile) NHCOCH3 NH2
[Nitrile]
Al
Ans. (b)
N Rate of acetylation NH2 > OH because N-bases are stronger
H 2O than O-bases. Size of N-atom is larger than O-atom and at the
R CH O CH (An imine) same time, N atom is less electronegative than O-atom.
–NH3
[Aldehyde] ••
–DIBAL-H
R So, N-atom of the  N H2 group can donate its lone pair of
electrons (Lewis basicity) more easily than that of O atom of the
••
So, R  CH is the correct answer.  O Hgroup.
 OH OH
O s
CH3 CH3COO
28 The increasing basicity order of the following H 2N C HN—COCH3
compounds is H
O—COCH3
CH2CH3 s
O—C—CH3
 OH
(A) CH3CH2NH2 (B) CH3CH2NH
CH3COOH +
CH3 CH3 Absorbed NHCOCH3
  by pyridine
(C) H3C N CH3 (D) Ph N  H [2019, 9 Jan Shift-II]
N

(a) (D) < (C) < (B) < (A) (b) (A) < (B) < (C) < (D)
(c) (A) < (B) < (D) < (C) (d) (D) < (C) < (A) < (B)
30 The correct structure of product ‘P’ in the following
NEt
Ans. (d) reaction is Asn − Ser + (CH3CO) 2 O →
3
P
(Excess) [2019, 10 Jan Shift-I]
If we consider Lewis basicity (basicity in aprotic solvents or in O
vapour phase), the order of basicity will be.
O NH2 O
D A B C H
N
2° 1° 2° 3° (a) H3C N OH
H
But, this order does not match with the options given. So, it has O OCOCH3
been asked on basicity of the amines in aqueous solution. When OCOCH3
no phase is given, then basicity of amine is considered in O O
aqueous solution as they are liquids. N
(b) H3C N H OH
In aqueous solution, basicity of 2°-amines (aliphatic) is maximum H
O NHCOCH3
because, of the thermodynamic stability of its conjugate acid.
⊕ È O
Et2NH + H2O 1 Et2 N H2 + OH
OCOCH3
(B) Conjugate acid O O
⊕ H
Et2 NH2 is a sterically symmetric tetrahedral ion as it contains N
(c) H3C N OH
equal number (two) of bulkier Et-group and small size H-atoms. H
O NH2
Here, two H-atoms give additional stability through hydrogen
bonding withH2O (solvent) molecules. O
O
29 The major product obtained in the following reaction is NHCOCH3
O
OH O
(d) H3C N NH
(CH3CO)2O/pyridine (1 eqv.) H OH
O OCOCH3
NH2 room temperature
[2019, 9 Jan Shift-II]
386 JEE Main Chapterwise Topicwise Chemistry

32 The major product of the following reaction is

Ans. (a)
Acetylation by Ac2O / Et3N is possible with NH2 (1°-amine) and CH3N NaBH4
OH(alcohol) groups only, but not with ‘ NH ’ part of
2 OH
O (a) CH3N

 C NH2 (amide) groups, because thelp of nitrogen in amide
group is involved in resonance with C O part. (b) CH3NH
s
O O OH
r (c) CH3NH
C NH2 C NH2
OH
O (d) CH3N
[2019, 10 Jan Shift-II]
H2N CH C NH CH COOH Ans. (c)
CH2 C NH2 CH2 OH NaBH4 is a selective reducing agent. It can reduce C==O
group into alcohol, N-methyl imine group, Me N = = CH  into
O
2°-amine but cannot reduce an isolatedC == C.
Asp Ser
(Asparagine) (Serine) O OH
NaBH4
Ac2O or (CH3CO)2O (2 moles) N NH
Et3N H3 C H3C
–2 AcOH N-methyl isolated Keto
O O imine C C group

CH3 C NH CH C NH CH COOH
33 A compound ‘X’ on treatment with Br 2 /NaOH, provided
CH2 CONH2 CH2O C CH3
C 3H9 N, which gives positive carbylamine test.
O Compound ‘X’ is [2019, 11 Jan Shift-II]
(a) CH3COCH2NHCH3 (b) CH3CH2CH2CONH2
31 The major product formed in the reaction given below (c) CH3CON(CH3)2 (d) CH3CH2COCH2NH2
will be Ans. (b)
NH2 The molecular formula, C3H9N refers to four structural isomers of
NaNO2 amines
Aq. HCI, 0-5°C (a) CH3CH2CH2NH2 (b) CH3–CH–CH3
[2019, 10 Jan Shift-I]
NH2

(a) (b) OH Primary amine

NO2
NO2 OH CH3

(c) (d) (c) CH3–NH–CH2CH3 (d) CH3–N–CH3

Secondary amine Tertiary amine
Ans. (*)
Here, onlya and b (primary amines) can be prepared from their
No option is the correct answer. Amines in presence ofNaNO2 + respective amides by Hoffmann bromamide (Br2 /NaOH) method
dil. HCl undergoes diazotisation. The diazotised product readily and can give positive carbylamine test.
loses nitrogen gas with the formation of carbocation. The
resulting carbocation rearranges itself to give the expanded ring.
Br2
r s ⇒ CH3CH2CH2—C—NH2 CH3CH2CH2—NH2
NaNO2+dil. HCl NaOH
NH2 N2Cl –Na2CO3
0-5°C
(Diazotisation) H2N—C NH2
(1°-amine) Aliphatic diazonium –N2
salt (unstable) Br2/NaOH
⇒ CH3—CH—CH3 CH3—CH—CH3
–Na2CO3

OH 4
–Hr 3
4
5
r So, ‘X’ can be CH3CH2 CH2  CONH2 (a) or CH3CH(CONH2 )CH3 (b).
3 5
6 Ring expansion 6 Carbylamine test given by (a) and (b)
H2O 2 1 2
r
(Major)
leads to give 1
CH3CH2 CH2NH2 + CHCl 3 + 3KOH 
∆→ CH (CH ) NC + 3KCl + 3H
thermodynamically 3 2 2 2
more stable
carbocation
Organic Compounds Containing Nitrogen 387
NH2
35 The increasing order of basicity of the following

CH3  CH  CH3 + CHCl 3 + 3KOH 
∆→ compounds is [JEE Main 2018]
NC
 NH2
NH
CH3  CH  CH3 + 3KCl +3H2 I. II.
As (b) is not among the given options So, it is ruled out and NH2
compound (X) is CH3CH2 CH2 CONH2 . III. IV.
NHCH3
NH
34 The major product of the following reaction is
(a) (I) < (II) < (III) < (IV) (b) (II) < (I) < (III) < (IV)
H3C O (i) NaNO2/H+
(c) (II) < (I) < (IV) < (III) (d) (IV) < (II) < (I) < (III)
NH2
O (ii) CrO3/H+ Ans. (d)
(iii) H2SO4 (conc.), ∆ Among the given compounds the basic nature depends upon their
[JEE Main 2018] tendency to donate electron pair.
O O NH
Among the given compounds in Nitrogen is
2
(a) CH3 O (b) HO sp -hybridised.
This marginally increases the electronegativity of nitrogen which
O in turn decreases the electron donation tendency of nitrogen.

O Thus making compound least basic.

HO CH3
(c) (d) NH2
Among the rest is totally different from others as in
O O O NH
this compound lone pair of one nitrogen are in conjugation with
Ans. (c)
π bond i.e.
Key Idea The reaction involves:
A. Deamination in step (i) 1
B. Oxidation in step (ii) NH2
HN
C. Hydroysis in step (iii) In conjugation
The complete pathway of reactions is as follows: As a result of this conjugation the cation formed after
H 3C O protonation becomes resonance stabilised
(i) NH2
O Protonation

+ +
H 3C O HN NH2 NH2 NH2
NaNO2/H+ H 2N H2 N
OH
Deamination Equivalent resonance
O

H 3C O
(ii) OH This equivalent resonance in cation makes HN NH2 most
O basic among all.
O
H3C NH2
CrO3/H+ O Categorisation is very simple between rest two as
Oxidation OH
O N CH3
(primary amine) is less basic than (secondary
amine) H
HO O
H Hence, the correct order is
H3C O Intramolecular
(iii) dehydration (II) < (I) < (IV) < (III)
O i.e. option (c) is correct.
H OH
Hydrolysis
Conc. H2SO4/D 36 In the Hofmann-bromamide degradation reaction, the
Cyclisation
HO
number of moles of NaOH and Br 2 used per mole of
amine produced are [JEE Main 2016]
(a) four moles of NaOH and two moles of Br2
(b) two moles of NaOH and two moles of Br2
O
Final product (c) four moles of NaOH and one mole of Br2
(d) one mole of NaOH and one mole of Br2
Thus, option (c) is the correct answer.
388 JEE Main Chapterwise Topicwise Chemistry

Ans. (c) amide with three carbon atoms. Hence, the compound C is
O
Hofmann-bromamide degradation reaction is given as:

RCONH2 + 4NaOH + Br2 → RNH2 CH3  CH2  C NH2 .
(1° amine)
Since, all the options shows that A is an acid and it forms acid
+ Na2 CO3 + 2NaBr + 2H2O
amide on reaction withNH3. Thus, acid must contain three
Hence, four moles of NaOH and one mole of Br2 are used. carbon atoms. Hence, the compound A is CH3CH2 COOH. The
complete series of reaction can be represented as
37 On heating an aliphatic primary amine with chloroform
NH3 –
and ethanolic potassium hydroxide, the organic CH3CH2COOH CH3CH2COO NH4+
compound formed is [JEE Main 2014] ( A) (B)
(a) an alkanol O
∆ ||
(b) an alkanediol CH3CH2 — C — NH2
(c) an alkyl cyanide Hofmann (C)
(d) an alkyl isocyanide bromamide KOH/Br2
Ans. (d) reaction

Reaction of aliphatic primary amine with chloroform and ethanolic CH3CH2NH2

potassium hydroxide, leads to the formation of
isocyanides/carbylamines. Thus, this reaction is called 40 A compound with molecular mass 180 µ is acylated with
carbylamine reaction.
CH3COCl, to get a compound with molecular mass 390 µ.
∆
R  NH2 + CHCl 3 + KOH → R  NC + 3KCl + 3H2O The number of amino groups present per molecule of
Alkyl isocyanide the former compound is [JEE Main 2013]
(a) 6 (b) 2 (c) 5 (d) 4
38 Considering the basic strength of amines in aqueous Ans. (c)
solution, which one has the smallest pK b value?
During acetylation, one H atom with atomic mass 1 amu of
[JEE Main 2014]
 NH2 group is replaced by an acetyl group CH3 CO [molecular
(a) (CH3)2 NH (b) CH3NH2 mass = 434µ]. Thus,
(c) (CH3) 3N (d) C 6H5NH2  NH2 + CH3COCl →  NHCOCH3 + HCl
Ans. (a) The above equation suggests that, the acylation of each  NH2
It is known that, pK b = − log kb group increases the mass by 42µ [43 − 1]. If the molecular mass
Thus, larger the value of kb , smaller is the value of pK b and of the organic compound is 180µ while that of the acylated
hence, stronger is the base. product is 390µ, then the increase in the mass due to acylation
is given by
The order of basic strength of amines is as follows
•• •• •• •• 390 − 180 = 210 µ
(CH3)2 NH > CH3 NH2 (CH3) 3 N > C6H5 NH2 210 µ
Hence, the number of  NH2 groups = =5
The basic strength of amines depends on the inductive effect as 42 µ
••
will as steric hinderance of alkyl groups. Hence, (CH3)2 NH
[secondary amine] possess the smallest value of pK b . 41 Which one of the following is the strongest base in
aqueous solution ? [AIEEE 2007]
39 An organic compound A on reacting with NH3 gives B. (a) Trimethylamine (b) Aniline
(c) Dimethylamine (d) Methylamine
On heating B gives C. C in the presence of KOH reacts
with Br 2 to give CH3CH2NH2 . A is [JEE Main 2013] Ans. (c)
(a) CH3  CH  COOH (b) CH3CH2CH2CH2COOH In aqueous solution, basicity order is
 Dimethylamine >methylamine > trimethylamine > aniline
CH3 2° 1° 3°
This order depends upon the inductive effect and steric
(c) CH3CH2COOH (d) CH3COOH
hinderance of alkyl groups.
Ans. (c)
NH ∆ KOH/ Br2 42 In the chemical reaction,
A →
3
B → C → CH3 CH2 NH2
CH3CH2NH2 + CHCl 3 + 3KOH → (A) + (B) + 3H2O,
The reaction of C with KOH/Br2 to give amine is called Hofmann
bromamide reaction. This reaction is give by acid amides only in
the compounds (A) and (B) are respectively [AIEEE 2007]
which (a) C2 H5CN and 3KCl
O (b) CH3CH2CONH2 and 3KCl
 (c) C2 H5 NC and 3KCl
R  CH2  C NH2 group undergoes rearrangement along with
(d) C2 H5 NC and 3KCl
the loss of CO2 molecule. Thus, the compound C must be acid
Organic Compounds Containing Nitrogen 389

Ans. (c) Mole formula weight 60

∴ n= = =1
Emp formula weight 60
CH3 CH2 NH2 + CHCl 3 + 3kOH → CH3 CH2  N →
== C + 3KCl + 3H2O
∴ Molecular formula = CH4N2O
(alc) (A) (B)
Given compound gives biuret test, thus given compound is urea
The above reaction is called carbylamine reaction in which (NH2 )2 CO.
isocyanides or carbylamines are produced. ∆
NH2 CONH2 + HNHCONH2 → NH2 CONHCONH2 + NH3
Biuret
43 Which one of the following methods is neither meant for  as CuSO 4
the synthesis nor for separation of amines ? [AIEEE 2005] ↓
(a) Curtius reaction (b) Wurtz reaction Violet colour
(c) Hofmann method (d) Hinsberg method
Ans. (b) 46 The correct order of increasing basic nature for the
Wurtz reaction is used to prepare alkanes from alkyl halides.
bases NH3 ,CH3NH2 and (CH3 ) 2 NH is [AIEEE 2003]
(a) CH3NH2 < NH3 < (CH3)2 NH (b) (CH3)2 NH < NH3 < CH3NH2
Dry ether
2R  X + 2Na → R  R + 2NaX (c) NH3 < CH3NH2 < (CH3)2 NH (d) CH3NH2 < (CH3)2 NH < NH3
Ans. (c)
44 Reaction of cyclohexanone with dimethylamine in the The basicity of an amine in aqueous solution primarily depends
presence of catalytic amount of an acid forms a upon the stability of the ammonium cation or the conjugate acid
compound. Water during the reaction is continuously formed by accepting the proton from water.
+
removed. The compound formed is generally known as R NH2 + H2O 1 R NH3 + OH −
(a) an amine (b) an imine [AIEEE 2005]
[ammonium cation]
(c) an enamine (d) a Schiff ’s base The stability of the ammonium cation depends upon
Ans. (c) (i) + I effect of alkyl groups
CH3 CH3 (ii) Extent of H-bonding with water molecules
O + HN — HN (iii) Steric effects of the alkyl groups
CH3 CH3 On the basis of above factors, the basic strength of amine
Enamine is as follows
CH3 (CH3)2 NH > CH3 NH2 > NH3
— OH + H N (+ I effect of  CH3
CH3 group predominates)
Enol

45 An organic compound having molecular mass 60 is TOPIC 2

found to contain C = 20%,H=6.67% and N = 46.67% Aromatic Amines
while rest is oxygen. On heating, it gives NH3 alongwith
a solid residue. The solid residue gives violet colour with 47 Which one of the following gives the most stable
alkaline copper sulphate solution. The compound is diazonium salt ? [2021, 01 Sep Shift-II]
(a) CH3CH2CONH2 (b) (NH2 )2 CO [AIEEE 2005] NH2
(c) CH3CONH2 (d) CH3NCO (a) CH3—CH2—CH2—NH2 (b)
Ans. (b) CH3
CH3
Element Percentage Percentage Simple Ratio NHCH3
at. wt. (c) CH3—C—NH2 (d)

C 20.0 20.0 1.66 H

= 1.66 =1
12 1.66 Ans. (b)
H 6.67 6.67 6.67 Primary amines react withNaNO2 and HCl to give diazonium
= 6.67 =4
1 1.66 salts.

N 46.67 46.67 3.33 Å

= 3.33 =2 NH2
NaNO2+HCl
NººNCl
14 1.66 (a)
Cl
26.66 1.66 Propylamine Diazonium salt
O 26.66 = 1.66 =1
16 1.66
NaNO2+HCl Å
(b) H3C NH2 H 3C NººNCl
Empirical formula=CH4N2O
Empirical formula weight = 12 + (4 × 1) + (2 × 14) + 16 = 60 p-methylaniline Most stable diazonium
salt due to +H effect
390 JEE Main Chapterwise Topicwise Chemistry

NaNO + HCl ⊕ NO2

(c) CH3  CH  NH2 →
2
H3C  CH  N ≡≡ N Conc. HNO3
  Conc. H2SO4
CH3 CH3 (A )
Benzene
2-methylethanamine Nitrobenzene
NaNO2+HCl
N—CH3
Nitrobenzene on reaction with Cl2 / anhyd. AlCl 3 undergoes
(d) NH—CH3
electrophilic substitution reaction to give 1-chloro-3-nitro
N-methylaniline N==O
benzene, which on reaction with Fe/HCl gives chloroaniline.
N-alkyl nitroso amine
NO2 NO2 Cl
Cl2
Diazonium salt is not formed rather N-alkylnitroso amine is
formed as product. Anhyd. AlCl3
∴ In option (b) the most stable diazonium salt is formed. (B)
1-chloro-3-nitro benzene

48 Identify A in the following reaction. NO2 Cl NH2 Cl

Fe/HCl
NH2
(C)
K2Cr2O7
A Chloroaniline
[2021, 01 Sep Shift-II]
Ans. (a) 50 The major products A and B formed in the following
Aniline reacts with potassium dichromate (K2 Cr2O7 ) to form reaction sequence are [2021, 31 Aug Shift-II]
1,4-benzoquinone as the product. The nascent oxygen produced
NH2
from K2 Cr2O7 reacts with aniline to form 1,4-benzoquinone with
the removal of NH+4 ion. O Br2, CH3COOH
This reaction involves oxidation of aniline. A B
Room temperature
NH2 O

K2Cr2O7
+ NH+
4
NH CH3 NH CH3
Aniline
O
(A ) (a) A = , B=
1,4-benzoquinone Br

49 Identify correct A, B and C in the reaction sequence given

below. [2021, 31 Aug Shift-II] NH CH3 NH CH3
Conc. HNO3
+
Conc. H2SO4 Cl2 Fe/HCl (b) A = , B=
A B C
∆ Anhyd . AlCl3

NO2 NO2 Cl Cl NH2 Br

(a) A = B= C=
, , NH2 NH2
Cl Br
NO2 NO2
C= (c) A = , B=
(b) A = B= ,
,
OH COCH3 COCH3
Cl
NO2 NO2 NH2 NH2 NH2
(c) A = B= C=
, , Br Br
Cl Cl (d) A = , B=
NO2 NO2 NH2
(d) A = B= C= COCH3
, , COCH3

Cl OH Ans. (b)
Ans. (a) Aniline reacts with acetic anhydride to give acetanilide.
Benzene undergoes nitration on reaction with conc.HNO3 and The acetic acid part is removed and N-acylation takes place by
conc. H2SO4 . nucleophilic substitution reaction.
Organic Compounds Containing Nitrogen 391

NH2 s
O O O O
r OH O
+CH3—C—O—C—CH3 Ph—NH2—C—O—C—CH3 CH3
Acetic anhydride
Aniline (c) A= , B=
O

NH—C—CH3 NHCOCH3 NH2 NH2

Br2 OH OH
+ CH3COOH
CH3COOH
Room temperature
(A) (d) A= , B=
Br Acetanilide
(B)
p-bromoacetanilide NH2 NH CH3

Acetanilide is brominated with bromine/acetic acid. As

NHCOCH3 is ortho/para directing group (since lone pair on Ans. (d)
N activates the ring). Since, only one equivalent of acetic anhydride is present and
Bromine attached to para position is the major product losse. — NH2 group is more nucleophilic than —OH group due to lower
electronegativity of nitrogen. So, it attacks at the carbonyl
51 The total number of reagents from those given below, center of acetic anhydride forming the product B.
that can convert nitrobenzene into aniline is ........
OH OH O O OH
(Integer answer) [2021, 31 Aug Shift-I]

I. Sn − HCl II. Sn − NH4OH H2/Pd CH3 O CH3

III. Fe − HCl IV. Zn − HCl

C2H5OH 1 eq.

V. H2 − Pd VI. H2-Raney nickel NO2 NH2 HN CH3

p-nitrophenol (A )
Ans. (5) p-aminophenol O
(B)
The nitrobenzene can be reduced to aniline via following (Major product)
reagents.
(I) Sn-HCl (V) H2 -Pd (III) Fe-HCl (VI) H2 (Raney Ni) Mechanism
(IV) Zn-HCl OH OH OH OH

H2/Pd
52 The correct structures of A and B formed in the + CH3COOH
C2H5OH
following reactions are [2021, 27 Aug Shift-II] O
Å O Å
OH N==O2 NH2 HN O HN
O
O H O CH3
H2/Pd O B (A) O
C2H5OH A 1 eq. (Major product)
Therefore, the option (d) is correct.
NO2
53 Given below are two statements.
OH OH Statement I Aniline is less basic than acetamide.
Statement II In aniline, the lone pair of electrons on
(a) A= , B= CH3
nitrogen atom is delocalised over benzene ring due to
resonance and hence less available to a proton.
NH2 NH2 Choose the most appropriate option : [2021, 27 July Shift-I]
(a) Statement I is true but statement II is false.
(b) Statement I is false but statement II is true.
O CH3 O CH3 (c) Both statement I and statement II are true.
(d) Both statement I and statement II are false.
(b) A= , B= Ans. (b)
Statement I is false but Statement II is true.
NH2 NH CH3 Aniline (C6H5NH2 ) is more basic than acetamide (C2H5NO) because
in acetamide lone pair of electron present on nitrogen is
delocalised to more electronegative element, i.e. oxygen.
392 JEE Main Chapterwise Topicwise Chemistry

As lone pair of N in acetamide is in conjugation with C == O that is Ans. (c)

strong electron withdrawing than phenyl group, so lone pair of N Both (A) and (R) are true and (R) is correct explanation of (A).
is unavailable for proton, so it is less basic than aniline. Aromatic halide does not giveSN2 reaction.
In aniline, lone pair of electrons on the N atom is delocalised over Gabriel pthalimide synthesis is used to form primary aliphatic
benzene ring. amine, because aryl halides do not undergo nucleophilic
substitution reaction.
NH2 NH2 NH2 NH2 NH2 Gabriel phthalimide reaction
O O
s
C C
s KOH
NK R—X
N—H
–H2O
Ph  NH2 > RCONH2 (Basic strength). C C SN 2
(This step not
given by aryl halide)
54 NH2 O O
O
Phthalimide
(CH3CO)2O P
(Major product) C
NH2
N—R
C
The major product in the above reaction is
[2021, 26 Aug Shift-II] O
N-alkyl-phthalimide

NHCOCH3 NH2 O O

C C
(a) (b) RNH2
NHCOCH3 NHCOCH3 N—H+ KOH N—K (Primary
C C aliphatic
+ amine)
–
NH3CH3COO NHCOCH3 O O O
Phthalimide
(c) (d) C
NHCOCH3 NH2 N—R
C
Ans. (d)
O
Since — CH2 — NH2 is more basic, the resulting amide will fail to N-alkyl-phthalimide
react further. Therefore, imide formation takes place at only one
site (i.e. primary amine). The complete reaction is as follows :
56 Which one of the following reactions does not occur?
NH2 NH [2021, 22 July Shift-II]

O NH2 NHCOCH3
+
NH2 NH2
OH (a) + (CH3CO)2O/Pyridine

NH2 NH2
55 Given below are two statements, one is labelled as :
Assertion (A) and other is labelled as Reason (R). (b) + H2SO4
Assertion (A) Gabriel phthalimide synthesis cannot be
used to prepare aromatic primary amines. SO3H
Reason (R) Aryl halides do not undergo nucleophilic NH2 NH3
substitution reaction.
(c) + AlCl3 + CH3Cl
In the light of the above statements, choose the
correct answer from the options given below
[2021, 22 July Shift-I] CH3
(a) Both (A) and (R) true but (R) is not the correct explanation NH2 NH2
of (A).
(b) (A) is false but (R) is true. (d) + HNO3/H2SO4
(c) Both (A) and (R) true and (R) is correct explanation of (A).
(d) (A) is true but (R) is false. NO2
Organic Compounds Containing Nitrogen 393

Ans. (c) O
Friedel-Craft reaction is not possible in highly activated ring, i.e.
NH2 LiAlH4 NH2
aniline because NH2 group forms complex with Lewis acid and
deactivate the ring. Reduction
Chemical reaction is as follows :
Br Br
NH2 NH3 AlCl3 LiAlH4 reduces amide to primary amine with same number of
carbon atom.
CH3Cl
+ AlCl3 No reaction 58 The correct structure of Rhumann's Purple, the
compound formed in the reaction of ninhydrin with
(Unstable)
proteins is [2021, 20 July Shift-I]
Due to lone pair of electrons on N, aniline is a strong Lewis base. O– O–
So, an acid base reaction occur between aniline and AlCl 3 leading
to anilinium salt formation. (a) N
+
Since,NH3 is a deactivating group and hence electrophilic
substitution via Friedel-Craft alkylation does take place. O O
O– O–
57
(b) N
NH2 KOBr A
(Major product)
O O
–
O O
Br
+
(c) N N N
NH2 LiAIH
+
4 B
H3O (Major product)
O O
Br O O

In the above reactions, products A and B respectively

(d) N
are [2021, 20 July Shift-II]
NH2
NH2 O O
(a)
, Ans. (d)
Br Rhumann’s purple is confirmatory test for the presence of
NH2 protein. The correct structure of Rhumann’s Purple, the
NH2 compound formed in the reaction of ninhydrin with proteins is an
(b) follows
,
R O O
Br   OH
NH2 H2 NCHCΟH + 2
OH
NH2
(c) O–
, Amino acid O O
Ninhydrin
NH2 N
NH2
(d)
, O O
(Purple-blue)
Br Br
Ans. (d) 59 Hofmann bromamide degradation of benzamide gives
Hofmann reagent reduces amide to amine with one carbon less. product A, which upon heating with CHCl 3 and NaOH
This reaction is known as Hofmann bromamide reaction. gives product B. The structures of A and B are
O [2021, 17 March Shift-I]
NH2 NH2
NH2
NH2 (KOH+Br ) CHO
2
(a) A= B=
(Hofmann bromamide reaction)
Br Br
(A) Br Br
394 JEE Main Chapterwise Topicwise Chemistry

NH2 NC Ans. (d)

During nitration of aniline, meta-nitroaniline is also formed as
(b) A = product due to formation of NH3+ group which is meta directing
B=
group under strongly acidic medium. The percentage of p, m and
o product is 51%, 47% and 2%, respectively.
NH2 NH2 Reaction is as follows
CHO
NH2 NH2 NH2 NH2
(c) A = (Nitration) NO2
B=
HNO3 + H2SO4
288 K + +
O O NO2
NH2 NH2 Aniline (A ) (B)
CHO (2%) (47%) NO2
(C)
(d) A = B= (51%)
% yield order isC > B > A.

Br Br 61 A. phenyl methanamine B. N,N-dimethylaniline

Ans. (b)
C. N-methyl aniline D. Benzenamine
Hofmann bromamide degradation of benzamide gives product
aniline (A), which upon heating with CHCl 3 and NaOH gives
Choose the correct order of basic nature of the above
product benzene isocyanide (B), by carbylamine reaction. amines. [2021, 26 Feb Shift-II]

Hofmann bromamide degradation method is for preparation of (a) A > C > B > D (b) D > C > B > A
primary amines by treating an amide with bromine in an aqueous (c) D > B > C > A (d) A > B > C > D
or ethanolic solution of sodium hydroxide. Ans. (d)
The amine formed contains one carbon less than that present in In phenyl methanamine, the lone pair on nitrogen of NH2 group
the amide. is localised and does not undergoes resonance as attached to
O sp3-hybridised C-atom.
Phenyl methanamine or benzyl amine
C—NH2 NH2
+I
Donation
Br2 /NaOH CH2—NH2

Benzamide Aniline
(A) Benzyl group (Aliphatic)
Hofmann bromamide reaction
(B), (C) and (D) are aromatic amines in which lone pair of electrons
Aliphatic and aromatic primary amines on heating with of N-atoms goes in resonance
chloroform and ethanolic potassium hydroxide form isocyanides (+ R effect) with the benzene ring. So, Lewis basicity or donation
or carbylamines which are foul smelling substances. of lone of electrons of these amines will be decreased in
comparison to (A).
NH2 NC
+R (+I)
CH3
CHCl3/NaOH (B) N (+I)
CH3
Aniline Benzene isocyanide –R
(B) N, N-dimethyl aniline (3°-amine)
Carbylamine reaction
+ I effects of two CH3 groups are in compensation with
Note Secondary and tertiary amines do not show this reaction. −R-effect of the ring.
This reaction is known as carbylamine reaction or isocyanide
test and is used as a test for primary amines. +R
(+I)
(C) NH CH3
60 NH2 NH2 NH2 NH2
–R
NO2
HNO3, H2SO4 N-methyl aniline (2°-amine)
+ +
288 K + I effect of one CH3 group is trying to compensate − R effect
NO2 of the ring.
(A) (B)
NO2 +R
(C) (D) NH2
Consider the given reaction, percentage yield of
[2021, 18 March Shift-II] –R
(a) (C) > (A) > (B) (b) (B) > (C) > (A) Benzenamine or aniline (1° amine)

(c) (A) > (C) > (B) (d) (C) > (B) > (A) It has no + I-effect on N-atom to outweigh −R-effect of the ring.
Organic Compounds Containing Nitrogen 395

So, A is purely aliphatic 1 °-amine. B is aromatic During nitration, in strongly acidic medium, aniline gets
⊕
3°-amine with more aliphatic nature (for two CH3 groups). C is protonated to form the anilinium ion i.e, (C6H5 NH3) which is
aromatic 2°-amine with less aliphatic nature (for one CH3 ⊕
group). D is purely aromatic 1°-amine. meta-directing as NH3 is an electron withdrawing (−I) group.
Hence basicity order is A > B > C > D. As a result, we get meta-nitro aniline (B) as the major product.

62 Carbylamine test is used to detect the presence of 64 Which of the following reaction(s) will not give
primary amino group in an organic compound. Which of p-aminoazobenzene? [2021, 25 Feb Shift-I]
the following compound is formed when this test is
NO2 NO2
performed with aniline? [2021, 25 Feb Shift-II]
NHCH3 CN
(i) Sn/HCl (i) NaBH4
(a) (b) A= B=
(ii) HNO2 (ii) NaOH
(iii) Aniline (iii) Aniline
NC CONH2
(c) (d) NH2

Ans. (c) (i) HNO2

C=
(ii) Aniline, HCl
Aniline on carbylamine reaction produces a foul smelling gas,
phenyl isocyanide (C6H5NC).
NH2 NC (a) A only (b) C only
∆ (c) B only (d) A and B
+ CHCl3 + 3KOH – 3 KCl
Ethanolic – 3 H2O Ans. (c)
Aniline Phenyl
[1º amine] isocyanide Nitrobenzene in presence ofNaBH4 , NaOH and aniline will not
give p-amino azobenzene.
Carbylamine test is used to detect aliphatic and aromatic
primary amines. NO2 NO2

NH2 NH2 NH2 NaBH4 NaOH

63 NH2 No reaction
No reaction
NO2
HNO3, H2SO4 Nitrobenzene Nitrobenzene Aniline
+ + (B)
288 K Product not
NO2 formed
NO2
In case of (A) and (C), coupling reaction takes place as the
(A) (B ) (C )
medium is quite acidic follows
Correct statement about the given chemical reaction +
is [2021, 25 Feb Shift-II] NO2 NH2 N2
••
(a)  N H2 group is ortho and para directing, (i) Sn+HCl (ii) HNO2 (iii) Aniline

so product (B) is not possible.

(b) reaction is possible and compound (B) will be the major Nitrobenzene Phenylamine Diazonium
(A)
product.
(c) the reaction will form sulphonated product instead of —N==N—
NH2
nitration.
(d) reaction is possible and compound (A) will be major p-aminoazo benzene
product.
+
Ans. (d)
NH2 N2
NH2 NH2 NH2 NH2
HNO3, NO2 HNO2 Aniline
H2SO4
+ + HCl
288K Nitrobenzene Benzene
NO2
Aniline (B) (C) (C) diazonium
NO2 —N== N—
(A )
[47%] [2%] NH2
[51%] m-nitroaniline o-nitroaniline
p-aminoazo benzene
p-nitroaniline
396 JEE Main Chapterwise Topicwise Chemistry

65 The total number of amines among the following which 67 The increasing order of basicity of the following
can be synthesised by Gabriel synthesis is ……… . compounds is [2020, 5 Sep Shift-I]
[2021, 24 Feb Shift-II]
N
CH3
(a) CH CH2 NH2 (b) CH3CH2NH2 N N N N
CH3
H H H
CH2 NH2 NH2 (A) (B) (C) (D)
(c) (d) (a) (A) < (B) < (C) < (D) (b) (D) < (A) < (B) < (C)
(c) (B) < (A) < (D) < (C) (d) (B) < (A) < (C) < (D)
Ans. (3) Ans. (c)
Gabriel phthalimide synthesis is used to prepare
1° aliphatic or alicyclic amine. Hence, amine which can be
synthesised by Gabriel phthalimide synthesis method contains N
N sp3-hybridised
α-carbon.
sp2-hybridised H
Aniline (C6H5NH2 ) does not contain α -C cannot be prepared by
(localised lone pair) (B)
Gabriel reaction.
(A) Lone pair involved
Rest amines all containα-C in its respective position, hence they in aromaticity
can easily give Gabriel phthalimide reaction.
α Weakest base
CH3 α α CH2 —NH2 (least basic)
CH–CH2—NH2 , CH–CH2—NH2 ;
CH3
N
(Shows
∴ Three amins out of given four anions can be prepared by reasonating
Gabriel synthesis. N N structure
sp3 -hybridised after accepting H+)
H H
66 In the following reaction the reason why meta-nitro
(C) (D)
product also formed is [2021, 24 Feb Shift-I]
More free lone pair of electron for donation, hence most basic.
NH2 NH2 NH2 NH2
N
NO2
Conc. HNO3 > > >
+ + N N N
Conc. H2SO4, 288K N
NO2 (A )
H H H
NO2 [B] [C]
(B) (D) (C)
[A] 47% 2% Most basic
Least basic
51%
Hence, correct increasing order of basicity is
(a) NH2 group is highly meta-directive (B) < (A) < (D) < (C)
(b) NO2 substitution always takes place at meta-position
(c) Formation of anilinium ion 68 The final major product of the following reaction is
(d) Low temperature [2020, 5 Sep Shift-II]
Ans. (c) Me
(i) Ac2O/Pyridine
Aniline on protonation forms anilinium ion, which is
meta-directing. So, a considerable amount of meta product is (ii) Br2, FeCl3
(iii) OH–/∆
formed alongwitho-nitroaniline and p-nitroaniline.
NH2
NH2 NH3 (–I) very high effect Me Me Br

conc.H2SO4 (a) (b)

Br
conc.HNO3
Aniline
(Nitration)
Anilinium ion
NH2 NH2
Br
Nitrating mixture is mixture of conc.HNO3 and a conc.H2SO4 . Me Me
When aniline is reacted with nitrating mixture ortho, meta and
para nitroanilines are obtained. (c) (d)
Br
Aniline being basic in nature, reacts with acids to form anilinium
ion which is meta directing. NH2 NH2
Organic Compounds Containing Nitrogen 397

Ans. (d) pK a value decreases. Electron density within the ring is

CH3 CH3 maximum in (I) thus it has least pK b value. So, option (a), (c) and
Acetylation
(d) are incorrect.
CH3—C—O—C—CH3
In (III) structure, —CN group attached at meta-position, thus
NH2 O O H—N—C—OCH3 electron density is less affected, so pK b value is more than
Bromination
structure (IV).
m-toluidine O
Br2/FeCl3 Thus decreasing order forK b is (I) > (II) > (IV) > (III)
∴ Order of pK b : (III) > (IV) > (II) > (I).
Br Br
CH3 CH3 Hence, the correct option is (b).
+HOH
CH3COOH 70 Consider the following reaction :
NH2 H—N—C—OCH3 CH3 ⊕ s ⊕ s OH–
N + Na SO3 — —N2 Cl X
O CH3

The basic nature of m-toluidine is not greatly affected by the

The product ‘X’ is used [2020, 7 Jan Shift-I]
CH3 group.
(a) in acid base titration as an indicator
NH  C OCH3 is moderately activating

(b) in protein estimation as an alternative to ninhydrin
O (c) as food grade colourant
(d) in laboratory test for phenols
group, its activating nature overcome weak activating CH3
group. Ans. (a)
Due to bulky nature of NHC  CH3 attack CH3 ⊕ ⊕
 —N
s
+Na SO3 — —N2Cl
s
O CH3
happen para to NHCO–CH 3.
CH3 s ⊕
Here, NH2 group has been protected by forming its aceyl OH–
N— —N==N — —SO3 Na
Diazo CH3
derivative and as such if does not interfere in the bromination. coupling
Methyl orange
69 The increasing order of pK b values of the following
Methyl orange is used as an indicator in acid-base titration.
compounds is [2020, 6 Sep Shift-I]

N(CH3)2 N(CH3)2 NHCH3 NHCH3 71 In the following reaction sequence,

NH2

CN OH Ac2O Br2
OCH3 A B
AcOH
(I) (II) (III) (IV)
CH3
(a) II < IV < III < I (b) I < II < IV < III
(c) II < I < III < IV (d) I < II < III < IV
the major product B is: [2020, 7 Jan Shift-II]
Ans. (b)
NHCOCH3 NHCOCH3
N(CH3)2 N(CH3)2 NHCH3 NHCH3
Br
(a) (b)
Br
CN OH
CH3 CH3
OCH3
(I) (II) (III) (IV)
NHCOCH3 NHCOCH3

( )
+M effect of (– I effect of (–I effect of
+R OCH3 CN group) OH group) COCH3 Br
group (c) (d)
–I

pK b is inversely proportional to basic strength and as the CH3 CH2Br

electron density increases in the ring,K b will increases and pK a
398 JEE Main Chapterwise Topicwise Chemistry

Ans. (b) N
The first step of the reaction is acylation. II. : No resonance or delocalisation of lone pair of
O
 electrons on nitrogen.
••
In the second step of reaction,  NH  C  CH3 has +R (or + M) The ring contains sp2 carbon atoms that have −I-effect,
effect, so it acts as ortho/para-directing group. But, since para compared to sp3 C-atoms.
position has CH3 group, substitution at ortho takes place. CH3
∴ Less basic than compound III.
has weak ortho-/para- directing effect due to hyperconjugation,
but it is suppressed due to more predominant effect of NH2
O
•• 
NH  C  CH3. I. : Resonance or delocalisation of lone pair of electrons

Thus, the complete reaction is given as follows : on benzene ring occur that decreases basicity.
O O

NH2 NH—C—CH3 NH—C—CH3 IV. N : Strong resonance or delocalisation of

Ac2O or
(CH3CO)2O Br2
Br H
lone pair of electron on nitrogen.The electron pair is a part of
AcOH
aromatic 6 electron system.
CH3 CH3 CH3 ∴ Least basic among given options.
(A) (B) So, the correct order of basicity is III > II > I > IV

72 Kjeldahl’s method cannot be used to estimate nitrogen 74 The major product obtained in the following reaction is
for which of the following compounds? NH2
(i) CHCl3/KOH
[2020, 8 Jan Shift-II]
(ii) Pd/C/H2
O

(a) C 6H5NO2 (b) NH2 C NH2 CN O [2019, 8 April Shift-II]

(c) CH3CH2 C ≡≡ N (d) C 6H5NH2 H H

NCH3 NCH3
Ans. (a) (a) (b)
Kjeldahl’s method cannot be used for nitro compounds, diazo
compounds and compounds with nitrogen in a ring, because CN O CN OH
these on reaction withH2SO4 do not give ammonium ion. H H
NCHCl2 NCH3
73 The decreasing order of basicity of the following amines (c) (d)
is [2020, 9 Jan Shift-II]

NH2 CN OH H2N OH
N NH2 N Ans. (d)
1° NH2 responds
H
NH2 N≡≡C
(I) (II) (III) (IV) CHCl3/KOH
(Carbylamine reaction)
(a) (III) > (I) > (II) > (IV)
(b) (III) > (II) > (I) > (IV) CN O N≡≡C O
(c) (I) > (III) > (IV) > (II) Pd/C/H2
(d) (II) > (III) > (IV) > (I) NH—CH3
Ans. (b)
Among the given options, compound (III) has maximum basicity.
NH2 H2N OH

In step (i), 1° amine is converted into isocyanide, when reacts

III. : No resonance or delocalisation of lone pair of with CHCl 3 /KOH. This reaction is known as carbylamine reaction.
This reaction is used to detect primary amine in a compound.
electron on nitrogen.
In step (ii), isocyanide is reduced to secondary amine and cyanide
The ring contains sp3 carbon atoms that cause +I-effect. is reduced to primary amine, and carbonyl group to alcoholic
∴ More basic among options. group when treated with Pd/C/H2 .
Organic Compounds Containing Nitrogen 399

75 The increasing order of the pK b of the following Ans. (d)

compound is [2019, 12 April Shift-I] Key Idea Basicity ∝ Ease of donation of lone pair of electrons
1 1
F ∝ ∝
S % of s- character of N Electronegativity of N
(A) The % of s-character in the given amines are as follows:
N N

H H
N N N
sp2-hybridised sp3-hybridised
CH3O [s-character=33.3%]
H [s-character=25%]
S sp2-hybridised H
(B) [s-character=33.3%]
Pyridine Pyrrole Piperidine
N N (I) (II) (III)

H H Therefore, piperidine (III) having minimum

O2N % s-character is most basic. Among the rest, pyridine (I) and
S pyrrole (II) the lone pair of electrons of N in pyrrole (II) is involved
(C)
in delocalisation and follows (4n + 2) π aromatic (n = 1) system.
N N So, the N-atom of pyrrole (II) will show least basicity.
H H Thus, the order of basicity is as follows:
H3C
S
(D) > >
N N N N N
H H H H
(a) (A) < (C) < (D) < (B) (b) (C) < (A) < (D) < (B) (III) (I) (II)
(c) (B) < (D) < (A) < (C) (d) (B) < (D) < (C) < (A)
Ans. (c) 77 The major product of the following reaction is
O
Key Idea pK b value is defined as the minus logarithm ofK b .
Smaller the value of pK b , stronger is the base and vice-versa. C
In the given options, +R effect is shown by —CH3 and —OCH3 group NH2 (i) Br2/hν
( OCH3 >  CH3). These group increases the electron density at (ii) KOH (dil.)
CH2 CH3
o and p-positions. Groups such as F and —NO2 shows –R-effect
( NO2 > F). These group decreases the electron density at o [2019, 9 Jan Shift-II]
and p- positions.
Increase in electron density at p-position makes the unshared NH
(a) (b) NH
electron pair of ‘N ’ more available and decrease in electron
CH3
density at p-position makes the unshared electron pair of ‘N ’ less
available. Compound containing —OCH3 group act as strongest CH3
base and hence possess lowest value of pK b . So, the correct
increasing order of pK b in the given compound is NH NH
F (c) (d)
O2N S S
> >
N N N N Ans. (a)
H H H H
In the given reaction,
(C) (A)
H 3C H3CO Responds to Hoffmann's
S S
> bromamide degradation and
gets converted into
N
H N
H N
H N
H [NH2 +K2CO3] by Br2/KOH
C
NH2
(D) (B)
CH2 Undergo benzylic free
(i) Br2/hν radical substitution with
76 Arrange the following amines in the decreasing order of CH3 Br2/hν to give [CHCH3]
(ii) KOH (dil.)
basicity : [2019, 9 Jan Shift-I]
H Br
N + H
H –Br N
N N N H
Br
(I) –H+
CH3
H H Formation of
(II) (III) 2° carbocation NH
s
by removing Br
(a) I > II > III (b) III > II > I (c) I > III > II (d) III > I > II CH3
400 JEE Main Chapterwise Topicwise Chemistry

78 An aromatic compound ‘A’ having molecular formula

O –R
C 7 H6O 2 on treating with aqueous ammonia and heating A +R
forms compound ‘B’. The compound ‘B’ on reaction with N
B
molecular bromine and potassium hydroxide provides
H
compound ‘C’ having molecular formula C 6H7 N. The
structure of ‘A’ is Ring-(A) is activated, i.e. becomes more nucleophilic by the + R
••
OHC CHO effect of the  N H  group and it becomeso / p-directing
(a) (b) towards the electrophile, NO2+ in the ArSE2 reaction. For
OH OH ⊕
mononitration, NO2 will preferably come at p-position, whereas
COOH
(c) (d) O
O CH==CHCHO 
the ring-(B) gets deactivated by −R- effect of the  C  group,
[2019, 10 Jan Shift-II] r
O2N O
Ans. (c) r
NO2
Using retro-synthesis, to get the required compounds, A, B and C rds of ArSE2
C. NH
Br NH / D
C6H7N ←2 B ←
3
A
(C ) KOH [An amide] [Carboxylic acid
[1° -amine]
Hoffmann (No.of C = 7) C 7H 6 O2 ] H
bromamide O O2N O
(No. of C = 6 reaction
1 carbon less) (step down) O2N
r C C
So, the reactions can be shown as: NH Fast,–Hr
NH
COOH CONH2 NH2
NH3/D Br2/KOH
–H2O –K2CO3
–KBr 80 The major product of the following reaction is
(A ) (B) (C)
[C7H6O2] Benzenamide [C6H7N] O
Benzoic Aniline
acid OEt (i) Ni/H2

CN (ii) DIBAL- H
79 What will be the major product in the following
mononitration reaction ? NH N
(a) (b)
O
H
N HNO3
H Conc.H2SO4 O OH
(c) CHO (d)
NH2
O
O NO2 [2019, 11 Jan Shift-I]
(a)
(c) O2N N Ans. (b)
N
H Ni/H2 can reduce —C ≡≡ N into  CH2 NH2 (1°-amine) but
H
cannot reduce an ester group (  CO2Et) whereas DIBAL-H,
O2N di-isobutylaluminium hydride, [(CH3)2 CH]2 AlH reduces the ester
O
O group (  CO2Et) into —CHO (an aldehyde) and C2H5OH.
(b) (d)
N
H N O O
H
NO2 OEt Ni/H2/D OEt
C≡N DIBAL–H
[2019, 10 Jan Shift-II] NH2 –EtOH
Ans. (b)
1 CH
2
Here, in mononitration the electrophile produced from mixed N –H2O NH2
+ (Nucleophilic addition
3
acid (HNO3 + conc.H2SO4 ) is NO2 . elimination reaction)
4
Organic Compounds Containing Nitrogen 401

81 The increasing order of reactivity of the following

NH2 NH3HSO4
compounds towards reaction with alkyl halides
directly is [2019, 12 Jan Shift-I] Conc.H2SO4
O O CN +Conc.HNO3
NO2
NH2 NH2
NH2
NH
83 Amongst the following the most basic compound is
O [AIEEE 2005]
(A) (B) (C) (D) (a) p -nitroaniline (b) acetanilide
(a) (A) < (C) < (D) < (B) (b) (B) < (A) < (C) < (D) (c) aniline (d) benzylamine
(c) (B) < (A) < (D) < (C) (d) (A) < (B) < (C) < (D)
Ans. (d)
Ans. (b)
Basic nature of the compound is related to their tendency to
The reaction of alkyl halide with amine or amides is a
donate their lone pair of electrons more readily. − I effect [e −
nucleophilic substitution reaction.
withdrawing] exerting group decreases the basic strength while
More nucleophilic nitrogen is more + I effect [e − donating] exerting group increases the basic
reactive with alkyl halide. Compound (A) is benzamide and lone strength of the compound.
pair of ‘N’ of it, is not available in this compound.
s NH2
O O
+
C NH2 C NH2 (a) NO2 group
(electron withdrawing)
(A) decreases basic nature of aniline
NO2
In compound (D), lone pair of ‘N’ are available but in compound (C),
the lone pair of ‘N’ are not readily available due to the presence of O O
electron withdrawing group (  CN) attach to benzene ring.
In compound (B), i.e. pthalimide, ‘N’ is not nucleophilic due to the (b) CH3C NH2 where, CH3C group is also
electron withdrawing
presence of two polar groups attached to it that pulls lone pair
towards them.
:

(c) NH2 phenyl group is

Hence, the correct order is : (B) < (A) < (C) < (D).
also electron withdrawing.

82 Which of the following compounds will give significant (d) Benzylamine (C6H5 CH2NH2 ) contains alkyl group linked to
amount of meta-product during mononitration reaction? amine,  NH2 group. This alkyl group is + I effect [e−
[JEE Main 2017] donating] exerting group which increases the basicity of
OH OCOCH3 benzylamine.
Thus, most basic compound is benzylamine.
(a) (b)
84 Which of the following is the strongest base?
[AIEEE 2004]
NH2 NHCOCH3

(a) NH2 (b) NH3

(c) (d)
CH3
Ans. (c)
(c) NHCH3 (d) CH2NH2
Aniline in presence of nitrating mixture
(conc. HNO3 +conc. H2 SO4 ) gives significance amount (≈ 47%) of
Ans. (d)
meta-product because in presence ofH2SO4 its protonation
takes place and anilinium ion is formed. CH3  [an electron releasing (+ I) group] increases electron
density at N-atom, hence basic nature is increased.
NH2 NH3HSO4
I–
(a) NH2 (b) NH CH3
H2SO4
I+
I–
Aniline Anilinium ion I–
(c) NH2 (d) CH2 NH2
Here, anilinium ion is strongly deactivating group and
meta-directing in nature. So, it gives meta-nitration product. I+
CH3
402 JEE Main Chapterwise Topicwise Chemistry

+
C6H5 decreases electron density at N-atom due to delocalisation Sn + HCl C 6H5N2 Cl –
of e − of NH2 with π e − of benzene. Thus, basic nature is 87 C 6H5NO 2 → A → P
+ (Yellow coloured
decreased. H
compound)
Hence, (d) is the strongest base.
Consider the above reaction, the product P is
[2021, 25 July Shift-II]
85 The reaction of chloroform with alcoholic KOH and
p -toluidine form [AIEEE 2003] N==N — N== N— —NH2
(a) (b)
NH2
(a) H3C CN (b) H3C N2Cl H
N
N— N == N—N—
(c) H3C NHCHCl2 (d) H3C CN (c) (d)

Ans. (b)
Ans. (c)
Sn  HCl is used for reduction of  NO2 group into NH2
NH2 NC group. On next step,PhN2+ Cl − is used to form yellow coloured azo
dye with aniline. This is a coupling reaction.
∆ NO2 NH2 NH2
+ CHCl3 + alc. KOH
+
Sn-HCl Ph – N2 Cl –
Reduction (para-attack)
CH2 CH3
p-toluidine Nitrobenzene Aniline
N==N —
(A)
This is carbylamine reaction.
p-aminoazobenzene
(Y-aminoazobenzene)

TOPIC 3 Due to its various resonating structures, there’s an excess of

electron or negative charge over ortho and para positions of the
Diazonium Salts benzene ring than the meta-position. Thus, anilines areo and
p-directing towards electrophilic substitution reactions.
86 What is the major product P of the following reaction ? + –
88 N2Cl
CH3 B. Anhyd. CH2CH3
(i) NaNO2, HCl, 278K
P AlCl3
(ii) H2O (Major + A + H2O
NH2 product)
(Major product)
[2021, 25 July Shift-II]

CH3 CH3
In the chemical reactions given above A and B
(a) (b)
respectively are [2021, 22 July Shift-II]
CH3 Cl (a) H3PO2 and CH3CH2Cl (b) CH3CH2OH and H3PO2
OH CH3 (c) H3PO2 and CH3CH2OH (d) CH3CH2Cl and H3PO2
(c) (d) Ans. (a)
N2 Cl OH H3PO2 is compound A and CH3CH2 Cl is compound B.
When benzene diazonium chloride reacts withH3PO2
Ans. (d)
(hypophosphorus acid) and water gives benzene (major product)
In first step,NaNO2 , HCl is used for diazotisation reaction at which on reaction with ethyl chloride in presence of anhydrous
0-5°C. In last step,H2O is used as a nucleophilic substitution of N2 AlCl 3 gives ethyl benzene.
(leaving group). Chemical reaction is as follows ;
N2 is best leaving group to form (1-methylcyclohexyl) methanol as + –
major product. N2Cl H
CH3 CH3
(i) NaNO2+HCl,
0-5°C or 273-278 K + – + H3PO2 + H2O
NH2 (Diazotisation reaction) CH2 N2 Cl
(A )
+ – Benzene Hypophosphorus Benzene
(ii) H OH acid
diazonium (Major product)
CH3 chloride
(Friedel-Craft reaction) CH2CH3
CH2 OH (B) CH3CH2Cl
(1-methylcyclohexyl) methanol Anhyd. AlCl3
(P)
(Major product) Ethyl benzene
Organic Compounds Containing Nitrogen 403

NH2 CH3
N
CH3
90 H3C CH3
N
NaNO2, HCl NH2
89 273-278 K
A
273 K
B
(Major (Major
product) product) NaNO2, HCl
'X' 'Y'
SO3H 273 K- 278 K (Major product) (Major product)

Consider the above reaction, compound B is [2021, 18 March Shift-I]

[2021, 20 July Shift-II] –
+
CH3 N2Cl
N
CH3 N
N
(a) HO3S— —N==N— (a) and
N—CH3
CH3 CH3
(b) —N==N — —N
CH3
+ –
N2Cl
CH3 CH3
(c) HO3S— —N==N — —N N
N N
CH3 (b) and CH3

CH3 Cl
(d) HO3S— — —N
CH3
N== CH3
Ans. (c) N N
(c) and CH3
Diazonium salt is formed on treating an amine withNaNO2 / HCl at
low temperature.
+ Cl
NH2 N2
N==
N
NaNO2 + HCl
(d) and
0-5°C
N
H 3C CH3
SO3H SO3H
A (Major product)

Diazonium salt on treating with a N,N-dimethylaniline gives an Ans. (b)

azo compound. N, N-dimethyl aniline forms bond with N at Aniline reacts with sodium nitrite and HCl in cold condition to
para-position as amine group is a o, p-directing group. form benzene diazonium chloride (X) and on further reaction, it
+ form azo dye (Y ).
N2 NMe2 NMe2
Chemical reactions are as follows
H 3C CH3
+ +
N
NH2 N2Cl–

SO3H N==N SO3H NaNO2+HCl

273 K-278 K
B (Major product) (Aniline) X (Major product)
(Azo compound) (Benzene diazonium
⊕ chloride)
N2 CH3
—N==N— —N
CH3
Therefore, A is para-diazosulphonic Y (Major product)
acid (Azo dye)
NMe2
SO3H
91 OCH3
B is
C7H7N2OCl + C2H5OH + N2 + X + Y
N==N SO3H
(A )
In the above reaction, the structural formula of (A), X
para (N,N-dimethylaminophenyl
Benzene sulphonic acid
and Y respectively are [2021, 17 March Shift-II]
404 JEE Main Chapterwise Topicwise Chemistry

N2+Cl– Ans. (c)

O Aniline reacts withNaNO2 , HCl at 273-278 K to give benzene
+ −
(a) , CH3––C––H, HCl diazonium salt (C6H5 N2 Cl = X) which on hydrolysis (H2O/ ∆) gives
phenol. Complete reaction is as follows
+ –
NH2 N2Cl OH
OCH3
+–
N2 OCH3 NaNO2, HCl H2O/D (A)
273-278 K
H H
Aniline Benzene Phenol
(b)
, H
O
H
, HCl diazonium
chloride
(X)
+ –
Cl N2Cl
–
N2+OCH3
So, X = and A = H2O/∆
O

(c) , CH3––C––H , H2O 93 The diazonium salt of which of the following compounds
will form a coloured dye on reaction with β-naphthol in
NaOH ? [2021, 24 Feb Shift-II]
Cl
N2+Cl– CH3

H H CH2NH2 N CH3
(d) , (a) (b)
, H
O
H
H2 O

NH2 NH2 CH3

OCH3 (c) (d)
Ans. (a)
The structural formula of (A), X and Y are p-methoxy benzene Ans. (c)
diazonium chloride, acetaldehyde and hydrochloric acid Initially aniline reacts with diazotisation reagent to form
respectively. Reaction involved are as follows diazonium salt. Thenβ-naphthol react with salt and orange-red
+ – dye is obtained. So, diazonium salt of aniline is used to prepare
N2Cl OCH3 orange-red dye.
C2H5OH N+
2 Cl
– OH
+ N2 + CH3CHO + HCl
NH2 OH–
Nitrogen Acetaldehyde Hydrochloric NaNH2 + HCl
Methoxy (X) acid (β-naphthol)
OCH3 benzene (Y) 0-5ºC
(A) Aniline Diazonium
p-methoxy benzene salt
diazonium chloride N N
OH
92 NH2 OH

2-naphthol aniline
NaNO2,HCI 'A'
'X' Orange-red dye
273–278 K

(Major product) 94 What is the correct sequence of reagents used for

In the above chemical reaction, intermediate X and converting nitrobenzene into m-dibromobenzene?
reagent / condition A are [2021, 16 March Shift-I] NO2 Br
N2+ Cl – NO2

(a) X- ; A -H2O/NaOH ; A -H2O/∆

(b) X- Br [2021, 24 Feb Shift-II]
NaNO 2 HCl KBr H+
(a)  → /  → / → / →
N2+ Cl– NO2 Br2 /Fe NaNO 2 /HCl
(b)   → / Sn/HC
→ l
/  → / CuBr
/HBr
→
Br +
; A -H2O/∆ ; A -H2O/NaOH (c) Sn/HCl
→ / KBr H
→ / 2→ /  →
(c) X- (d) X- Br2 NaNO 2
Sn/HCl
(d)  → / → /  → / NaBr
→
Organic Compounds Containing Nitrogen 405

Ans. (b) 96 Three isomers A,B and C (molecular formula C 8H11N) give
In first step,NO2 group is electron withdrawing group, it
the following results :
decreases the electron density in meta position and bromination
Diazotisation
occur in meta position. In second step, Sn/HCl used for A and C →
reduction to convert NO2 to NH2 and form aniline. In next
step, diazonium salt is formed and at last bromine replaceN2+ Cl − (i) Hydrolysis
R (product of A)
P + Q → +
group to form 1, 3-dibromobenzene. (ii) Oxidation S (product of C)
Complete reaction is as follows (KMnO 4 +H + )
NO2 NO2 NH2 R has lower boiling point than S.
C 6H 5 SO2Cl
Br2/Fe Sn
B → alkali-insoluble product.
∆ +HCl
(Bromination) Br
(Reduction) A, B and C, respectively are [2020, 3 Sep Shift-II]
3-bromo Aniline
Nitrobenzene
nitrobenzene NH2 CH2NHCH3 CH2CH3
–
N+
2 Cl Sandmeyer
Br (a) ; ;
reaction H2N
NaNO2/HCl
CH2CH3
HBr
0-5ºC CuBr
Br Br NH2 CH2NH2 NH2
(Diazotisation
reaction)
Diazonium 1, 3-dibromo (b) ; ;
salt benzene
(m-dibromobenzene) CH2CH3
CH3 CH2CH3
95 ‘A’ and ‘B’ in the following reaction are
CH2CH3 NHCH2CH3 NH2
NH2
(c) ; ;
H2N CH2CH3
NaNO2/HCl SnCl2/HCl/H3O+
(A) (B )
KCN
CH2CH3 CH2NHCH3 NH2
[2021, 24 Feb Shift-I]
+ + (d) ; ;
– –
N2Cl Cl N2Cl CHO
CH2CH3
NH2
(a) (A) (B) (b) (A) (B)
Ans. (a)
CN Cl CN CHO A, B and C respectively are
NH2 CH2NHCH3
(c) (A) (B) (d) (A) (B)
,
CH2CH3
Ans. (d)
CH2CH3
Step 1 In step 1,NaNO2 + HCl , 0-5°C used for diazotisation
and
reaction. It will form diazonium salt. Further, it will react with
KCN to form cyanobenzene. H 2N
NH2 N2+Cl– CN
According to the question, A and C undergoes diazotisation to
(i) NaNO2+HCl (ii) KCN give P and Q. So, amine must be primary aromatic amine.
0-5ºC +–
Aniline Diazotisation Cyanobenzene NH2 N ≡ NCl
salt (A )
diazotisation

Step 2 In step 2, SnCl2 and HCl is a Stephen’s reduction reagent.

CH2CH3 CH2CH3
Cyanobenzene reduced to benzaldehyde by SnCl2 /HCl. (P )
(A )
H CH2CH3 CH2CH3
C N C NH.HCl C—H
– +
H 2N
(C ) ClN ≡ N
SnCl2/HCl H2O (Q )
+2[H] + NH4Cl

Cyanobenzene Intermediate (B) Which on hydrolysis followed by oxidation gives alcohol

Benzaldehyde derivative.
406 JEE Main Chapterwise Topicwise Chemistry

H Br Br
O+ H Hydrolysis is done and X –
O2N
(c) (d)
Ortho attack the hydrogen and
bond shift to oxygen Br Br
NO2
(Para) OH
OH Ans. (c)
+ –
CH2CH3 NH2 N2Cl Br
+ Cu2Br2
NaNO2/HCl
CH2CH3 273-278K (Sandmeyer
(Ortho) Br Br reaction) Br
(Diazotisation)
(Para) (X) (Y)
Br
OH OH
COOH HNO3
H2SO4
+ Br
NO2
Intramolecular
(Nitration of
H-bonding COOH benzene)
(R) Intermolecular H-bonding
(S ) Br is o, p-directing group.
∴ NO2 is attached at the ortho position of one of the Br atoms
Given, R has low boiling point than S. Intramolecular H-bond is
which is also para position with respect to the other Br atom.
weaker than intermolecular H-bond.
It means intramolecular H-bonding show low boiling point and 98 Consider the following reactions :
here, R is ortho product and S is para product.
C 6H SO2 Cl (i) NaNO2/HCl, 0-5ºC
Given, (B) →
5
alkali-insoluble product (ii) β-naphthol/NaOH
Coloured solid
C6H5SO2 Cl act as electrophile then B must be amine.
[P]
Secondary amine act as a nucleophile.
Br2/H2O
The C6H5SO2 Cl act as electrophile and displace Cl. C7H6NBr3
In the given option (b), secondary amine is present in the The compound [P] is [2020, 9 Jan Shift-II]
reaction takes place as follows :
NH2 NH2 NHCH3 NH2
CH2 —NHCH3
+ s –HCl CH3
+ Ph SO2Cl (b) (c)
(a) (d)
CH3
Ph CH2 N CH3 CH3
SO2Ph CH3

Alkali insoluble amine Ans. (a)

Primary and secondary amine forms poorly soluble ppt. on Compound [P] is 3-methylaniline.
reaction withPhSO2 Cl. Complete reaction is as follows :
OH
97 The major product Z obtained in the following reaction NH2 N2Cl
scheme is [2020, 9 Jan Shift-I]
NaNO2/HCl (β-naphthol)
NH2 0-5ºC NaOH
CH3 CH3
3-methyl aniline
NaNO2/HCl Cu2Br2 HNO3 (P)
X Y Z
273-278 K H2SO4
Br OH
NO2
—N==N—
NO2
(a) (b)
Br Br CH3 (Coloured azo dye)
Br Br
NO2
Organic Compounds Containing Nitrogen 407

NH2 NH2 s NaOH

[Ar  N ≡≡ N] + OH - Ar  N == N  OH
Br Br H+ Does not couple
Br2/H2O
NaOH − +
CH3 - Ar N == N ONa
CH3 H+ Does not couple
(P) Br
C7H6NBr3 Following conditions are very useful for coupling reaction to take
place.
On comparing the formula C7H6NBr3 with the formula of (a) The solution must be so alkaline that the concentration of
m-methylaniline (C7H9N), it is noticed that, three H atoms are diazonium ion is too low.
substituted with three Br atoms (tribromination). To get a (b) It must not be so acidic that the concentration of free
tribrominated product, all three activated positions of aniline phenoxide ion is too low.
(2 ortho and one para) must be free, where Br can come.
Then, it can be concluded that the methyl group must be at 100 Aniline dissolved in dil. HCl is reacted with sodium nitrite
meta-position only. at 0°C. This solution was added dropwise to a solution
NH2 containing equimolar mixture of aniline and phenol in dil.
HCl. The structure of the major product is
[2019, 9 April Shift-I]

CH3 (a) N N NH2

99 Coupling of benzene diazonium chloride with 1-naphthol

(b) N N O
in alkaline medium will give [2019, 8 April Shift-I]
OH
(c) N N OH
(a) (b)

(d) N N NH
N N

N OH N Ans. (a)
Major product of the reaction is

N N NH2

It is obtained by coupling reaction.

Reaction of aniline with dil. HCl and sodium nitrite at 0°C is
OH
shown below :
(c) N +–
(d) NH2 N≡≡NCl
N N
N
+ NaNO2 + Dil. HCl 0°C

Diazonium salt

Diazonium salt formed when added to equimolar mixture of

OH aniline and phenol in dil. HCl then aniline couples with diazonium
Ans. (c) salt. Reaction is as follows :
Coupling of benzene diazonium chloride with 1-naphthol in
+ +
alkaline medium will give the following coupling reaction. N≡≡NCl + H2N
OH OH
In acidic
H+ medium
PhN2+
OH – N=
=N —NH2 + HCl

N==N
For an effective coupling, the solution must be so alkaline that
− + the concentration of diazonium ion is too low. It must not be so
In the presence ofOH ion, ArN 2 exists in equilibrium with an acidic that the concentration of free amine or phenoxide ion is
unionised compound (Ar  N == N  OH) and salts [ArN == N+ ] – too low. That is why amines couple fastest in mild acidic solution
s
OH derived from it, which do not couple. and phenols couple fastest in mild alkaline solution.
408 JEE Main Chapterwise Topicwise Chemistry

101 Benzene diazonium chloride on reaction with aniline in Ans. (c)

the presence of dilute hydrochloric acid gives +
[2019, 12 April Shift-II] NH2 N2Cl – CN

(a) —NH2 NaNO2 / HCl CuCN / KCN + CuCl

0 – 5°C ∇
diazotisation

CH3 CH3 CH3

(b) —N ===N — ( E)
4- methyl aniline (D)
4- methyl 4- methyl benzocyanide
H2N diazonium
chloride

(c) —N ===N — —NH2

103 In the chemical reaction,
NH2
(d) —N ===N—NH—
NaNO2 CuCN
A ∆ B,
HCl 278K
Ans. (c)
Benzene diazonium chloride on reaction with aniline in the
compounds A and B respectively are
presence of dilute hydrochloric acid undergoes coupling
(a) fluorobenzene and phenol [AIEEE 2011]
reaction and produces p-amino azobenzene. In this reaction,
benzene diazonium chloride reacts with aniline in which aniline (b) benzene diazonium chloride and benzonitrile
molecule at its para-position is coupled with diazonium salt to (c) nitrobenzene and chlorobenzene
give p-amino azobenzene (yellow dye). (d) phenol and bromobenzene
Ans. (b)
+ –
N NCl + H NH2 Formation of A is by diazotisation and formation of B from A is by
Benzene Aniline S N reaction. Thus, the complete series of reaction is given by
diazonium + –
salt NH2 N2Cl CN

H+
N N NH2+Cl–+H2O NaNO2 CuCN
p-amino azobenzene HCl, 0-4°C ∆
(yellow dye) (Diazotization) SN reaction
(A ) (B)
+ N2 + CuCl
102 In the reaction,
NH2
104 In the chemical reaction, [AIEEE 2010]

NaNO2 / HCl CuCN / KCN NH2

D ∇ E + N2
0.5°C
NaNO2 HBF4
A B
CH3 HCl, 278 K
The product E is [JEE Main 2015]
the compounds ‘A’ and ‘B’ respectively are
COOH
(a) nitrobenzene and fluorobenzene
(b) phenol and benzene
(a) (b) H3C CH3 (c) benzene diazonium chloride and fluorobenzene
(d) nitrobenzene and chlorobenzene
CH3 Ans. (c)
CH3 NH2 N2Cl
CN

NaNO2 HBF4
(c) (d)
HCl, 278 K
(Diazotization)
CH3 (A)
Organic Compounds Containing Nitrogen 409
+ –
N2BF4 F CH3 CH3
+
–
N NCl
∆ + N2 +BF3
+ HCl +
Diazonium Aryl fluoride
fluoroborate (B) +
N NCl–
The reaction of diazonium chloride with fluoroboric acid (HBF4 ) is
called Balz-Schiemann reaction.
CuBr, Heat
Sandmeyer’s reaction
105 Toluene is nitrated and the resulting product is reduced
with tin and hydrochloric acid. The product so obtained
CH3 CH3
is diazotised and then heated with cuprous bromide.
The reaction mixture so formed contains [AIEEE 2008] Br
(a) mixture of o-and p-bromotoluenes +
(b) mixture of o-and p-dibromobenzenes
(c) mixture of o-and p-bromoanilines (o-bromotoluene)
(d) mixture of o-and m-bromotoluenes Br
Ans. (a) (p-bromotoluene)
CH3 CH3 CH3
Conc HNO3 NO2 106 Fluorobenzene (C 6H5F) can be synthesized in the
+ H2SO4
+ laboratory [AIEEE 2006]
(a) by heating phenol with HF and KF
o-,p-directing (b) from aniline by diazotisation followed by heating the
NO2 diazonium salt with HBF4
Sn/HCl
(c) by direct fluorination of benzene with F2 gas
(Reduction of NO2) (d) by reacting bromobenzene with NaF solution
CH3 CH3 Ans. (b)
NH2
N2Cl –
+
NH2
+ NaNO2, HCl
diazotisation

NH2 F
HBF4
NaNO2, HCl
diazotisation
27
Polymers
TOPIC 1 Ans. (a)
Classification of Polymers The structure of the given polymers are as follows
OH OH OH
(a)
01 The polymer formed on heating novolac with —CH2 —CH2 —CH2 —CH2 Novolac
formaldehyde is [2021, 26 Aug Shift-I]
(a) bakelite
(b) polyester (b)  O  CH  CH 2  C O  CH  CH2 C  PHBV
(c) melamine    
CH3 O CH2 CH3 O n
(d) nylon 6,6
Ans. (a) O O
∆ (c) —C —C —O —CH2 —CH2 —O— Dacron
Novolac + Formaldehyde → Bakelite
Novolac when heated with formaldehyde will undergoes cross n

linking to form an infusible solid mass called bakelite. (

(d) —OCH 2—CH2—OOC CO—
(n Glyptal

OH OH OH

HCHO + Q Novolac does not contain any ester group.

Formaldehyde ∴ It is not a polyester.
Phenol Novolac
(Phenol-formaldehyde
resin)
03 Monomer of novolac is [2021, 31 Aug Shift-I]
(a) 3-hydroxybutanoic acid (b) phenol and melamine
+HCHO +∆
(c) o-hydroxymethylphenol (d) 1,3-butadiene and styrene
Ans. (c)
OH OH OH The monomer of novolac iso-hydroxymethylphenol.
OH
CH2OH

CH2 CH2 CH2

o-hydroxymethylphenol
Hence, correct option is (c).

04 Staggered and eclipsed conformers of ethane are

OH OH OH
[2021, 27 July Shift-I]
Bakelite
(a) polymers (b) rotamers
(c) enantiomers (d) mirror images
02 Which among the following is not a polyester ?
[2021, 31 Aug Shift-II]
Ans. (b)
(a) Novolac (b) PHBV Rotamers are isomers of a molecule which can be
(c) Dacron (d) Glyptal interconverted by rotation of a part of molecule about a
particular bond.
Polymers 411

Conformational isomerism is a form of stereo isomerism in 07 Match List-I with List-II.

which isomers can be inter converted just by rotation about
formally single bonds. List-I List-II
H (Chemicals) (Use / Preparation / Constituent)
H H
(A) Alcoholic (i) Electrodes in batteries
H H
potassium
H hydroxide
H H H H
H (B) Pd/BaSO 4 (ii) Obtained by addition reaction
H (C) BHC (Benzene (iii) Used for β-elimination reaction
Staggered Eclipsed hexachloride)
(θ=60º) (θ=0º)
(More stable) (Less stable) (D) Polyacetylene (iv) Lindlar catalyst

05 Match List I with List II. Choose the most appropriate match
[2021, 18 March Shift-I]
List I List II A B C D A B C D
(A) Chloroprene (i) (a) (ii) (i) (iv) (iii) (b) (iii) (iv) (ii) (i)
(c) (iii) (i) (iv) (ii) (d) (ii) (iv) (i) (iii)
(B) Neoprene (ii) Cl
Ans. (b)
(A) Alcoholic KOH is used for β - elimination reaction. It will
(C) Acryonitrile (iii) Cl form alkane as a major product.
( ) (B) Pd/ BaSO 4 (Lindlar’s catalyst) is used for convert alkyne
n to alkane.
(D) Isoprene (iv) CH2 == CH  CN (C) BHC (Benzene hexachloride) is used to obtained
addition product of benzene and chlorine.
Choose the correct answer from the options given (D) Polyacetylene is used as electrodes in batteries.
below. [2021, 22 July Shift-II]
∴ Correct match is (A-iii), (B-iv), (C-ii), (D-i).
A B C D A B C D
(a) (iii) (iv) (ii) (i) (b) (ii) (iii) (iv) (i) 08 Which of the following polymer is used in the
(c) (ii) (i) (iv) (iii) (d) (iii) (i) (iv) (ii) manufacture of wood laminates? [2021, 16 March Shift-II]
Ans. (b) (a) cis-polyisoprene
Correct matches are as follows : (b) Melamine formaldehyde resin
Cl (c) Urea formaldehyde resin
(A) Chloroprene (d) Phenol and formaldehyde resin
Cl Ans. (c)
( Urea-formaldehyde is used to manufacture unbreakable cups
(B) Neoprene
( n and laminated sheets.
(C) Acrylonitrile CH2 == CH  CN It is an example of condensation polymer in which water
molecule is removed from urea and formaldehyde forming an
amide linkage.
(D) Isoprene
(a) cis-poly isoprene is natural rubber.
(Neoprene is produced by free radical polymerisation of
(b) Melamine - formaldehyde polymer used in the
chloroprene)
manufacture of unbreakable crockery.
Hence, (A)-(ii), (B)-(iii), (C)-(iv), (D)-(i).
(d) Phenol-formaldehyde resin used as good wood
adhesives for plywood and particle board.
06 Orlon fibres are made up of [2021, 20 July Shift-I]
(a) polyacrylonitrile (b) polyester 09 The structure of neoprene is [2021, 26 Feb Shift-I]
(c) polyamide (d) cellulose
Ans. (a) (a) CH2CH CH CH2 CH2 CH
Orlon is the commercial name for polyacrylonitrile. N
n

Therefore, it is the polymer of acrylonitrile.

(b) CH2 CH
H
CN CN CN n
H C C CN
C N HC C CH C CH C Cl
Orlon
H
(c) CH2 C CH CH2
Acrylonitrile
n
412 JEE Main Chapterwise Topicwise Chemistry

Styrene butadiene rubber is also called buna-S, in which ‘Bu’

(d) NH N NHCN2 stands for butadiene, ‘na’ stands for sodium and ‘S’ stands for
n styrene.
N N Since, butadiene and styrene is one of the constituent monomer
of given polymer.
NH
12 Match List-I with List-II.
Ans. (c)
List-I List-II
Neoprene is an addition homopolymer of chloroprene. (Monomer Unit) (Polymer)
Cl Cl A. Caprolactum 1. Natural rubber
----+CH2 C—CH CH2 + CH2 C—CH CH2 + ---- B. 2-chloro buta-1,3-diene 2. Buna-N
Chloroprene C. Isoprene 3. Nylon-6
Polymerisation
D. Acrylonitrile 4. Neoprene
Cl
Choose the correct answer from the options given
—CH2—C CH—CH2—
Neoprene
n below [2021, 24 Feb Shift-I]
A B C D A B C D
10 Which statement is correct? [2021, 25 Feb Shift-I]
(a) 1 2 3 4 (b) 4 3 2 1
(c) 2 1 4 3 (d) 3 4 1 2
(a) Buna-N is a natural polymer.
(b) Buna-S is a synthetic and linear thermosetting polymer. Ans. (d)
(c) Neoprene is an addition copolymer used in plastic bucket (a)
manufacturing.
N—H
(d) Synthesis of buna-S needs nascent oxygen.
Ans. (d)
Only statement (d) is correct whereas other statements are
incorrect. The correct statements are as follows Caprolactum is the monomeric unit of
Buna-N is a synthetic polymer. polymer nylon-6
O
Buna-S is an elastomer. Buna-S is polymerised by addition
polymerisation method, which needs radical initiator for chain ––HN––(CH2 )5 ––C––
n
propagation step. Nascent oxygen can be used as an radical
initiator. (b) 2-chlorobuta -1, 3-diene is the monomeric unit of
polymer neoprene.
+ Nascent
(
—CH 2 )
CH2—CH2—CH— Cl Cl
oxygen
Ph Buna-S TiCl4, AIX3
Ph
Neoprene is a synthetic rubber not an addition copolymer. n n
2-chlorobuta-1,3-diene Neoprene
11 In polymer buna-S: ‘S’ stands for [2021, 24 Feb Shift-II]
(a) sulphonation (b) strength (c) 2-methylbuta-1, 3-diene (isoprene) is the monomeric
(c) sulphur (d) styrene unit of polymer natural rubber.
Ans. (d) H CH3H H H CH3 H H

Buna-S is the co-polymer of but 1, 3-diene and styrene as nC C—C C —C—C C—C—
follows.
H H H H n
H 2-methyl buta-1,3-diene Natural rubber
C CH2 (Isoprene)

Value of n is about 10,000.

n H2C CH—CH CH2 + n (d) CH2 ==CH CN (acrylonitrile) is one of the monomeric
Butadiene
Styrene
unit of polymer buna-N.
CN
( H2—CH— CH2—CH
—C CH––CH2––
(n n CH2==CH—CH==CH 2 + n CH2== CH
1, 3-butadiene Acrylonitrile
CN
Polymerisation
Buna-S —CH2—CH CH—CH2—CH—CH2—
n
Buna–N
Polymers 413

13 The correct match between Item - I and Item - II is : Ans. (a)

PHBV, (Poly 3- hydroxybutyrate -co-3- hydroxyvalerate) is a
Item - I Item - II
copolymer of
(A) Natural rubber (I) 1,3- butadiene + styrene
OH OH
(B) Neoprene (II) 1,3- butadiene + acrylonitrile Chiral Chiral
carbon COOH carbon COOH
(C) Buna -N (III) Chloroprene and
3-hydroxy butanoic acid 3-hydroxy pentanoic acid
(D) Buna -S (IV) Isoprene (or β-hydroxybutyric acid) (β-hydroxyvaleric acid)
[2020, 6 Sep Shift-II]
(a) (A)-(III), (B)-(IV), (C)-(I), (D)-(II) In both monomers, there is one chiral centre (shown by dark
(b) (A)-(III), (B)-(IV), (C)-(II), (D)-(I) spot).
(c) (A)-(IV), (B)-(III), (C)-(II), (D)-(I) ∴ Polymer contains chiral monomers.
(d) (A)-(IV), (B)-(III), (C)-(I), (D)-(II)
Ans. (c) 15 The structure of nylon-6 is [2019, 8 April Shift-II]
O H O H
Correct match is (A)→ (IV), (B) → (III), (C) → (II), (D) → (I) || | || |
(a) nCH2 == C  CH== CH2 → Polycis-isoprene (a) 
[ (CH2 ) 6 C N]
n (b) 
[ C  (CH2 ) 5 N]
n
 Natural rubber
O H O H
CH3 || | || |
Isoprene
(c) 
[ (CH2 ) 4 C N]
n (d) 
[ C(CH2 ) 6 N]
n
CH3 H
 Ans. (b)

C ==C 
 O
 CH2 CH2 
Polymerisation
n NH
(b) nCH2 == C  CH == CH2 →

Caprolactum
Cl  CH2  C == CH  CH2 
Chloroprene


O O
Cl
Neoprene
n —C—NH—(CH2)5 —C—NH—(CH3)5—
or
(c) nCH2 == CH  CH == CH2 + nCH2 == CH
1, 3 butadiene  O
CN
Acrylonitrile —NH—(CH2)5—C—
n
CN  Nylon-6

  

 CH2 CH == CH  CH2  CH2  CH  Nylon-6 is prepared by ring opening polymerisation of
→ 
  caprolactum. It is heated about 533 K in an inert atmospheric
 Buna-N  nitrogen about 4-5 hrs. Nylon-6 fibres are tough, possessing high
 n
tensile strength, as well as elasticity and lustre. They are wrinkle
(d) proof and highly resistant to abrasion and chemicals such as
nCH2 ==CH  CH== CH2 + nCH2  CH → acids and alkalis.

1, 3-butadiene 16 Which of the following compounds is a constituent of

Styrene the polymer
O
 CH2  CH == CH  CH2  CH2  CH  
—[ HN — C — NH — CH2— ]n ? [2019, 9 April Shift-II]
(a) N-methyl urea (b) Methylamine
Buna-S n (c) Ammonia (d) Formaldehyde
Hence, option (c) is correct match. Ans. (d)
O
14 Which polymer has ‘chiral’ monomer? ||
Monomer of 
[ NH  C NH  CH2
]n is formaldehyde. The
[2020, 9 Jan Shift-II]
(a) PHBV (b) Buna-N polymer is also known as urea-formaldehyde resin. It is made
(c) Nylon 6, 6 (d) Neoprene from urea (NH2 CONH2 ) and formaldehyde (HCHO).
414 JEE Main Chapterwise Topicwise Chemistry

Polymerisation 20 The homopolymer formed from 4-hydroxybutanoic acid

NH2 CONH2 + HCHO →
Urea Formaldehyde O is [2019, 11 Jan Shift-II]
||
( NH  C NH  CH2 
)n
Urea-formaldehyde resin
(a) —OC(CH2)3—O— (b) —C(CH2)2C—
It is used for making unbreakable cups and laminated sheets. n n

17 Which of the following is a thermosetting polymer?

[2019, 12 April Shift-I] (c) —C(CH2)3—O— (d) —C(CH2)2C—O—
n n
(a) Bakelite (b) Buna-N (c) Nylon-6 (d) PVC
Ans. (c)
Ans. (a)
On polymerisation, 4-hydroxy butanoic acid will produce a
Bakelite is a thermosetting polymer. These polymers are
condensation homopolymer by loss of H2O molecules.
cross-linked or heavily branched molecules which on heating
undergo extensive cross linking in moulds and become infusible.
Once they get set, they cannot be reshaped and reused. HO—C—CH2CH2CH2—O H + HO —C—(CH2)3—O H
4-hydroxy butanoic acid
18 Glucose and galactose are having identical configuration –H2O

in all the positions except position.

(a) C-3 (b) C-4 (c) C-2 (d) C-5 -----—C—(CH2)2CH2—O—C—(CH2)2CH2—O----
Ans. (b)
Ester linkage
Glucose and galactose are having identical configuration at all
The homopolymer obtained can also be represented as
the positions except at C-4 position. Both of them are
O
diastereomers that differ in configuration at only one chirality 
center. Hence, these are called epimers. Structures of glucose —[ C— (CH2 ) 3O —
]n
and galactose are as follows:
1 1 21 Poly-β-hydroxybutyrate-Co-β-
H—C==O H—C==O
2 2 hydroxyvalerate (PHBV) is a copolymer of ……
H OH H OH
3 3 (a) 3-hydroxybutanoic acid and 2-hydroxypentanoic acid
HO H HO H
4 4 (b) 2-hydroxybutanoic acid and 3-hydroxypentanoic acid
H OH C–4 HO H
(c) 3-hydroxybutanoic acid and 4-hydroxypentanoic acid
H OH H OH
(d) 3-hydroxybutanoic acid and 3-hydroxypentanoic acid
CH2OH CH2OH
[2019, 12 Jan Shift-I]
D-glucose D-galactose
Ans. (d)
19 The correct name of the following polymer is Poly-β-hydroxy butyrate Co-β-hydroxyvalerate (PHBV) is a
copolymer of 3-hydroxybutanoic acid and 3-hydroxypentanoic
CH3 CH3 acid. It is used in speciality packaging, orthopaedic devices and in
controlled release of drugs. PHBV undergoes bacterial
degradation in the environment. The reaction involved is as
n
[2019, 12 April Shift-I] follows :
(a) polyisobutane (b) polytert-butylene OH OH
(c) polyisoprene (d) polyisobutylene  
CH3  CH  CH2 COOH+ CH3CH2 CHCH2 COOH →
Ans. (d)
3-hydroxybutanoic acid 3-hydroxypentanoic acid
The correct name of the given polymer is
 O CH2 CH 3 
polyisobutylene. It’s monomer unit is isobutylene.    
Reaction involved is as follows :

 O  CH  CH2 C  O  CH  CH2  C
 
  
CH3  CH O n
 3 
CH3
Polymerisation
nCH2 C CH2 C
CH3 22 Which of the following statements about low density
CH3 n polythene is false? [JEE Main 2016]
Isobutylene
Polyisobutylene (a) It is a poor conductor of electricity
(b) Its synthesis required dioxygen or a peroxide initiator as a
The above reaction proceed via addition polymerisation. Polymer is catalyst
formed by the repeated addition of monomer molecules (c) It is used in the manufacture of buckets, dustbins etc.
possessing double bond. (d) Its synthesis requires high pressure
Polymers 415

Ans. (c) 27 Which of the following is a polyamide?

High density polythene is used in the manufacture of buckets, (a) Bakelite (b) Terylene
dustbins etc. (c) Nylon-6 6 (d) Teflon [AIEEE 2005]
Ans. (c)
23 Which polymer is used in the manufacture of paints and
Nylon-6 6 is a polyamide of hexamethylene diamine (CH2 ) 6 (NH2 )2
lacquers? [JEE Main 2015]
and adipic acid (CH2 ) 4 (COOH)2 .
(a) Bakelite (b) Glyptal
(Each reactant has six-carbon chain, hence trade code 6, 6 is
(c) Polypropene (d) Polyvinyl chloride
used.)
Ans. (b)
(a) Bakelite is used for making gears, protective coating 28 Nylon threads are made up of [AIEEE 2003]
and electrical fittings. (a) polyvinyl polymer (b) polyester polymer
(b) Glyptal is used in the manufacture of paints and (c) polyamide polymer (d) polyethylene polymer
lacquers. Ans. (c)
(c) PP is used in the manufacture of textile, packaging
Nylon threads are made up of polyamide, some common are
materials etc.
O
(d) Polyvinyl chloride (PVC) is used in the manufacture of 
rain coats, hand bags, leather clothes etc. Nylon 6 : H2N ( CH2 
) 5 C OH ; Monomer Polymer
O O
24 The polymer containing strong intermolecular forces  
e.g., hydrogen bonding, is [AIEEE 2010] HN 
( CH2 )5  C NH ( CH2 )5  C NH 
(a) teflon (b) nylon 6 6 O
(c) polystyrene (d) natural rubber 
Nylon 6 6 :HO  C ( CH2 )
4 COOH
Ans. (b)
and H2N 
( CH2 )6 NH2 ; Copolymer
Nylon-6 6 contains strong intermolecular forces like hydrogen
O O O 
   
bonds that are formed between  C  NHgroup of successive  C ( CH2 ) 4 C NH ( CH2 ) 6  NH 

 
chains.

25 Buna-N synthetic rubber is a copolymer of [AIEEE 2009] TOPIC 2

Cl
 Methods of Polymerisation
(a) H2C == CH —C == CH2 and H2C ==CH — CH == CH2
(b) H2C ==CH — CH == CH2 and H5C 6 — CH ==CH2 29 Monomer units of dacron polymer are
(c) H2C == CH — CN and H2C == CH — CH == CH2 [2021, 01 Sep Shift-II]

(a) ethylene glycol and phthalic acid

(d) H2C == CH — CN and H2C — C == CH2
 (b) ethylene glycol and terephthalic acid
CH3 (c) glycerol and terephthalic acid
Ans. (c) (d) glycerol and phthalic acid
Buna-N is actually abbreviated form, where Bu represents Ans. (b)
1,3-butadiene, na represents Na, sodium and N represents nitrile Monomer units of dacron are ethylene glycol and terephthalic acid.
(acrylonitrile).
CH2 OH
Thus, buna-N is a copolymer of 1,3-butadiene and acrylonitrile HO C C OH +
usually polymerise in the presence of sodium. CH2 OH
O O
26 Which of the following is fully fluorinated polymer? Terephthalic acid Ethylene glycol
[AIEEE 2005]
(a) PVC (b) Thiokol
(c) Teflon (d) Neoprene
 C C O CH2 CH2 O
Ans. (c)
Teflon is 
[ CF2 CF2 ]n . O O n
Dacron
416 JEE Main Chapterwise Topicwise Chemistry

30 A biodegradable polyamide can be made from Ans. (c)

[2021, 25 July Shift-II] Bakelite is a cross-linked polymer of formaldehyde and novolac.
(a) glycine and isoprene
OH OH OH
(b) hexamethylene diamine and adipic acid
(c) glycine and aminocaproic acid – CH2OH
(d) styrene and caproic acid + CH2==O OH +
Ans. (c) Methanal
o-hydroxy
A biodegradable polyamide nylon-2-nylon-6 is made from glycine Phenol
benzyl alcohol CH2OH
and amino caproic acid.
p-hydroxy
O O benzyl alcohol
 
nH2N  CH2  C OH + mH2N  ( CH2 ) C OH
5 OH OH
Glycine (Amino caproic acid)
(Amino acid)
O H O H Polymerisation
–H2O
— C — CH2 — N — C — (CH2)5 — N —
5
Nylon-2-nylon-6
(Polyamide) CH2 CH2
H O
 
Here; N  C  is amide linkage.

OH OH
OH OH
—CH2 CH2 CH2— Bakelite
31
Condensation reaction between phenol and formaldehyde with
excess of phenol form novolac.
Novolac on further heating with formaldehyde undergoes
is a repeating unit for [2021, 25 July Shift-I]
cross-linking to form bakelite.
(a) novolac (b) buna-N
(c) acrilan (d) neoprene 33 Which one of the following polymers is not obtained by
Ans. (a) condensation polymerisation? [2020, 5 Sep Shift-II]
OH OH (a) Nylon 6, 6 (b) Buna-N
CH2 CH2 CH2 (c) Bakelite (d) Nylon 6
Ans. (b)
Buna-N is an addition polymer. It is obtained by copolymerisation
is a repeating unit for novolac. of 1, 3-butadiene and acrylonitrile in the presence of a peroxide
catalyst.
OH OH
CH2 == CH CH == CH2 + CH2 == CH C ≡≡ N
H – CH2 OH Buta -1, 3 - diene Acrylonitrile
OH
n + n C==O 2n  Na
H ↓
Phenol Formaldehyde Intermediate
 
Polymerise  
CH2 CH == CH2 CH CH2 
OH OH   
 CN 
CH2 Nitrile rubber (Buna-N)

Linear polymer n 34 Preparation of bakelite proceeds via reactions

(Novolac) [2020, 8 Jan Shift-II]
(a) Electrophilic addition and dehydration
Novolac is low molecular weight polymer derived from phenol (b) Condensation and elimination
and formaldehyde. They are related to bakelite, which is more
highly cross-linked.
(c) Nucleophilic addition and dehydration
(d) Electrophilic substitution and dehydration
32 Bakelite is a cross-linked polymer of formaldehyde and Ans. (d)
[2021, 20 July Shift-II] Preparation of bakelite proceeds via electrophilic substitution
(a) PHBV (b) buna-S (c) novolac (d) dacron and dehydration reactions. It is shown below :
Polymers 417

OH OH CN CN
CH2OH
+
| O 2 − /O 2 
H
+ (H , polymerisation) (B) nCH2 ==CH → 
2
[ CH2 CH ]
n
+ HCHO (Catalyst) Polyacrylonitrile
Acrylonitrile (I) (PAN)
Phenol (electrophilic
substitution)
OH OH OH OH
H2C CH2 CH2
∆ (–H2O) CH2OH
sOH
(dehydration) (C) + HCHO Polymerisation/
Acid or H3Or
Formaldehyde
Novolac base catalyst
Phenol (IV)
OH OH OH
H 2C CH2 CH2 CH2 OH OH
CH2

CH2 CH2 CH2 n

Novolac
H 2C CH2 CH2 CH2

O
NH
550 K
OH (D) O 20 atm
—C—NH—(CH2)5—
3D-cross linked polymer (bakelite) –H2O Nylon-6 n
Caprolactum (II)

35 Which of the following is a condensation polymer? Thus, the correct match is as follows :
[2019, 10 April Shift-I]
(A) → (III), (B) → (I), (C) → (IV), (D) → (II)
(a) Nylon-6, 6 (b) Neoprene (c) Teflon (d) Buna - S
Ans. (a) 37 The polymer obtained from the following reaction is:
Nylon-6, 6 (an amide) is a condensation copolymer because it is (i) NaNO2 /H3O
+

obtained by condensation between adipic acid and NH2

HOOC (ii) Polymerisation
hexamethylenediamine.

O O O O
H H
(a) —C—(CH2)4—N— (b) —O—(CH2)4—C—
nHO—C—(CH2)4—C—OH + nN—(CH2)6—NH H n n

H Hexamethylene –n H 2 O
Adipic acid
diamine
O O H
(c) —OC(CH2)4O— (d) —HNC(CH2)4—C—N—
n n
——C—(CH2)4—C—NH—(CH2)6—NH——
1 mol n
[2019, 11 Jan Shift-I]
nylon-6,6
Ans. (c)
Neoprene, teflon and buna-S are addition polymers. Given amino acid on reaction withNaNO2 /H3O+ gives
diazotisation reaction which further evolves N2 gas along with
36 The correct match between Item-I and Item-II is formation of carbocation. On further reaction with water, it form
[2019, 10 April Shift-II] HOOC  (CH2 )  OH that undergoes polymerisation to give
polymer.
Item-I Item-II
NaNO2/H3O+
A. High density polythene I. Peroxide catalyst HOOC—(CH2)4—NH2 HOOC—(CH2)4—N2
(Diazotisation)
B. Polyacrylonitrile II. Condensation at high Aliphatic diazonium ion
(Unstable)
temperature and pressure –N2
+
C. Novolac III. Ziegler-Natta catalyst HOOC—(CH2)3—CH2
D. Nylon-6 IV. Acid or base catalyst –H –H2O
Polymerisation
Codes C—(CH2)4—O H HOOC—(CH2)4—OH
A B C D A B C D OH OH
(a) III I IV II (b) IV II I III –H2O
(c) III V I III (d) III I II IV H O—(CH2)4—C == O

Ans. (a)
-----O—(CH2)4—C—O—(CH2)4—C--- or —O—(CH2)4—C—
[TiCl +(C H ) Al] n
(A) nCH2 ==CH2 →
4 2 5 3

[ CH2 
]n (An ester group) (Polymer)
Ziegler -Natta catalyst
Ethylene High density
(III)
polythene (HDPE)
418 JEE Main Chapterwise Topicwise Chemistry

38 The two monomers for the synthesis of 40 The species which can best serve as an initiator for the
nylon 6, 6 are [2019, 12 Jan Shift-II] cationic polymerization is [AIEEE 2012]
(a) HOOC(CH2 ) 4 COOH, H2N(CH2 ) 4 NH2 (a) LiAlH4 (b) HNO 3
(b) HOOC(CH2 ) 6 COOH, H2N(CH2 ) 4 NH2 (c) AlCl3 (d) BaLi
(c) HOOC(CH2 ) 4 COOH, H2N(CH2 ) 6 NH2 Ans. (c)
(d) HOOC(CH2 ) 6 COOH, H2N(CH2 ) 6 NH2 Electron-deficient specie (Lewis acid) is used as an initiator for
Ans. (c) cationic polymerization.
Nylon 6, 6 has following structure:
 O O  41 Thermosetting polymer, bakelite is formed by the
    reaction of phenol with [AIEEE 2011]
 N (CH2 )6 N C (CH2 )4 C 
    (a) CH3CH2CHO (b) CH3CHO
 H H  (c) HCHO (d) HCOOH
n

6 C-atoms 6 C-atoms Ans. (c)

As it is a condensation polymer hence, each of its monomeric Bakelite is a thermosetting polymer formed by the condensation
unit must contain 6 carbon atoms in them. Hence, a combination reaction of phenol with HCHO in the presence of conc.H2SO4 .
of adipic acid and hexamethylene diamine is the correct answer. It is thus, a cross-linked polymer in which condensation takes
Both of these units react as follows to form nylon-6, 6. place at o- and p−positions.
O
Thus, HCHO is the correct option.
nH N (CH2)6 N H + OH C (CH2)4 C OH

Adipic acid
42 Bakelite is obtained from phenol by reacting with
H H –nH2O H
[AIEEE 2008]
Hexamethylene O
diamine (a) (CH2OH)2 (b) CH3CHO
N (CH2)6 N C (CH2)4 C (c) CH3COCH3 (d) HCHO
Ans. (d)
H H O
n
Nylon-6, 6 Bakelite is obtained from phenol by reacting with HCHO in the
acidic or alkaline medium.
39 The formation of which of the following polymers
involves hydrolysis reaction? [JEE Main 2017] 43 Monomers are converted to polymer by
(a) Nylon-6 (b) Bakelite (c) Nylon-6, 6 (d) Terylene (a) hydrolysis of monomers [AIEEE 2002]
Ans. (a) (b) condensation reaction between monomers
Nylon-6 or perlon is prepared by polymerisation of amino caproic (c) protonation of monomers
acid at high temperature. Caprolactam is first hydrolysed with
(d) None of the above
water to form amino acid which on heating undergoes
polymerisation to give nylon-6. Ans. (b)
O Condensation is the process of aggregation of more than one
O molecule without loosing any atom or group (sometimes smaller
NH Hydrolysis + – group or atoms H2O, R OH etc are released).
H3N—(CH2)5—C—O O
nCH2 == CH2 →  CH2  (CH2  CH2 )  CH2 
Polymerisation
Caprolactam ∆
[ HN— (CH2)5—C —
]n (Monomer) Polymer
Nylon-6
28
Biomolecules
TOPIC 1 1
CHO Ans. (d)
Carbohydrates H—C—OH
2 Lactose is a disaccharide of
3 β-D-galactose and β-D-glucose with C 1
CH2OH HO—C—H of galactose and C4 of glucose linkage.
01 Which one of the following 4
Complete reactions are as follows
O H—C—OH
compounds contain β-C 1 C 4 OH H+
H—C—OH
5
(a) Amylose + H2O → D-glucose
glycosidic linkage ? OH OH 6
[2021, 31 Aug Shift-I] H+
OH CH2OH (b) Sucrose + H2O → D-glucose +
(a) Lactose 1444442444443
a-D-(+)-glucose
D-fructose
(b) Sucrose
H+
(c) Maltose 1
CH2OH (c) Maltose + H2O → D-glucose
2
(d) Amylose H+
C O (d) Lactose + H2O → D-glucose +
Ans. (a) 3
CH2OH HO—C—H D-galactose
Lactose contains β -C 1 C 4 glycosidic OH 4
O
linkage. H—C—OH
HO 5
04 Given below are two statements :
The linkage is between C-1 of galactose
and C-4 of glucose. It’s structure is as CH2OH H—C—OH One is labelled as
6
follows : CH2OH Assertion (A) and other is labelled
HO
144444424444443 as Reason (R).
CH2OH b-D-(–)-fructose
Assertion (A) Sucrose is a
OH O H Therefore, option (d) is correct answer. disaccharide and a non-reducing
H ‘D’ represents the orientation of sugar.
CH2OH
4 α hydroxyl group at the chiral carbon that
OH H Reason (R) Sucrose involves
OH is farthest from the highest oxidised
OH O O
carbon (aldehyde group in case of glycosidic linkage between C 1 of
H β 1
H OH
glucose and keto group in fructose) β-glucose and C 2 of α-fructose.
OH H when the — OH group is on the right
H H β -D-glucose
side, ‘ L ’ is used when — OH group is on
Choose the most appropriate
the left side. (+) and (–) represents the answer from the options given
H OH direction of rotation of plane polarised below. [2021, 26 Aug Shift-II]
β -D-galactose light (+) is clockwise rotation and (–) (a) Both (A) and (R) are true but (R) is not
is anticlockwise rotation. the correct explanation of (A).
Hence, correct option is (a). α-is used when —OH group at anomeric (b) (A) is false but (R) is true.
carbon is below the ring in Haworth (c) (A) is true but (R) is false.
02 Hydrolysis of sucrose gives projection,β is used when — OH group at (d) Both (A) and (R) are true and (R) is
[2021, 27 Aug Shift-II] anomeric carbon is above the rings in the correct explanation of (A).
(a) α-D-(−)-glucose andβ-D(−)-fructose Haworth projection.
Ans. (c)
(b) α-D-(+)-glucose andβ-D-(+)-fructose Assertion is true but Reason is false.
(c) α-D-(−)-glucose andβ-D-(+)-fructose
03 Compound A gives D-galactose
Sucrose is formed by linkage of C1 of
(d) α-D-(+)-glucose andβ-D-(−)-fructose
and D-glucose on hydrolysis. The α-D glucose and C2 of β-D fructose. The
compound A is [2021, 27 July Shift-II] glycosidic bond in sucrose is formed
Ans. (d)
(a) amylose between reducing ends of both glucose
Hydrolysis of sucrose gives, (b) sucrose and fructose.
Sucrose + H2O q α - D- (+) -glucose (c) maltose Sucrose is a disaccharide and a
+ β -D- (−) -fructose (d) lactose non-reducing sugar as it contains no
free —CHO group (Anomeric carbon of
420 JEE Main Chapterwise Topicwise Chemistry

both monosaccharides are involved in formation of glycosidic Barfoed’s reagent in cupric acetate in 1% acetic acid. Brick
bond). red colour is obtained in this test due to formation of
The structure is as follows cuprous oxide.
6 (a) Seliwanoff’s test is used to distinguish between functional
CH2OH group (ketone or aldehyde) present on sugar.
5 O H (b) Iodine test is used for detection of starch and help to
H distinguish starch from monosaccharide, disaccharides and
4 H 1 polysaccharides.
OH H
α-link (d) While Tollen’s test is used to determine the presence of an
OH
3 2 aldehyde or ketone group in unknown solution.
H OH
O
(Glucose unit) 07 A non-reducing sugar “A” hydrolyses to give two
6
O β-link
reducing monosaccharides. Sugar A is
HOH2C [2021, 18 March Shift-I]
5 2 (a) fructose (b) galactose
H HO
(c) glucose (d) sucrose
H CH2OH
4 3 1 Ans. (d)
OH H A non-reducing sugar is one kind of carbohydrate that is not
(Fructose unit)
oxidised by a weak oxidising agent (an oxidising agent that
oxidises aldehydes but not alcohols, such as the Tollen’s reagent)
05 Identify the incorrect statement from the following. in a basic aqueous solution.
[2021, 20 July Shift-I] C12H22O11 + H2O → C6H12O6 + C6H12O6
(a) Amylose is a branched chain polymer of glucose. Sucrose D-glucose D-fructose
(b) Starch is a polymer of α-D-glucose . (A )
(Non-reducing
(c) β-glycosidic linkage makes cellulose polymer. sugar)
(d) Glycogen is called as animal starch.
While all others, i.e. glucose, fructose and galactose are
Ans. (a) reducing sugar.
Amylose consists of linear, helical chains of roughly 500 to CH2OH
20,000 D-glucose monomers linked together through
α -1,4 glycosidic bonds. In contrast to amylose, amylopectin is H O H HOCH2 O
H
branched. H
Linear structure of amylose is as follows OH H O H HO
HO
CH2OH CH2OH CH2OH CH2OH
O O O
OH OH OH H OH OH H
O O O O Sucrose
OH OH OH
α-1,4-glycosidic bonds Hydrolysis
CH2OH

CH2OH CH2OH H O H HOCH2 O OH

O O H
OH OH
HO OH H H HO
O O OH CH2OH
H
OH OH
Therefore, option (a) is incorrect statement. H OH OH H
Glucose Fructose
06 Which one among the following chemical tests is used Thus, sugar (A) is sucrose.
to distinguish monosaccharide from disaccharide ?
Enzyme A
[2021, 27 July Shift-I] 08 C 12H22O 11 + H2O → C 6H12O 6 + C 6H12O 6
(a) Seliwanoff's test (b) Iodine test Sucrose Glucose Fructose
(c) Barfoed test (d) Tollen’s test Enzyme B
C 6H12O 6 → 2C 2H5OH + 2CO 2
Ans. (c)
Glucose Ethanol
A monosaccharide is a single sugar molecule like glucose,
fructose, galactose while disaccharides are double sugars, e.g. In the above reactions, the enzyme A and enzyme B
sucrose. respectively are [2021, 17 March Shift-II]
(c) Barfoed’s test is used for distinguishing monosaccharides (a) amylase and invertase
from reducing disaccharides. Monosaccharides usually (b) invertase and amylase
react in about 1-2 minutes while disaccharide take 7-12 (d) invertase and zymase
minutes to react with reagent. (d) zymase and invertase
Biomolecules 421

Ans. (c) (C) In maltose, C1 of α - D-glucose is linked to C4 of another α -

Invertase and zymase are enzyme A and enzyme B respectively. D - glucose unit (iii).
Invertase  is the enzyme that catalyses the hydrolysis of sucrose 6
CH2OH
with a resulting mixture of fructose and glucose, which is called
1
inverted sugar. It cleaves theO  C bond. OH
5 O H HOH2C O H
Invertase
C12H22O11 + H2O  
→ C6H12O6 + C6H12O6 (A) 4
H 1 2 5
Sucrose Glucose Fructose OH H H OH
H O
CH2OH
Zymase  is an enzyme that catalyses the fermentation of sugar 3 2 3 4
into ethanol and carbon dioxide. H OH OH H
Zymase
C6H12O6  → 2C2H5OH + 2CO2 α-D-glucose β-D-fructose
Glucose Ethanol
Sucrose
09 Fructose is an example of [2021, 17 March Shift-II] 6 6
(a) pyranose (b) ketohexose CH2OH CH2OH
(c) aldohexose (d) heptose 5 O 5 O OH
OH H
Ans. (b) H H
(B) 4 1 O 4 1
Fructose is an example of ketohexose is a class of sugars that OH H OH H
contains six-carbon atoms and a ketonic group. Fructose has a H H H
3 2 3 2
ketonic group with six carbon atoms.
It contains five hydroxyl group and one ketonic group. H OH H OH
β-D-galactose β-D-glucose
The structure of fructose is
Lactose
1
CH2OH 6 6
CH2OH CH2OH
2
C==O Ketonic group 5 O H 5 O H
H H
3
HO H H H
4 (C) 4 1 4 1
H OH OH H OH H
HO O
H
5
OH OH
3 2 3 2
6
CH2OH H OH H OH
α-D-glucose α-D-glucose

Maltose
10 Match List-I with List-II.
So, option (c) is the correct answer.
List-I List-II
11 Which of the following is correct structure of α-anomer
A. Sucrose (i) β-D-galactose and
β-D-glucose
of maltose? [2021, 25 Feb Shift-II]
CH2OH CH2OH
B. Lactose (ii) α-D-glucose and
β-D-fructose H O H H O HO
H H
C. Maltose (iii) α-D-glucose and (a)
H H H H
α-D-glucose HO O H

Choose the correct answer from the options given OH OH HO OH

below. [2021, 26 Feb Shift-II] CH2OH CH2OH
(a) A → (i), B → (iii), C → (ii) O O
H H H OH
(b) A → (iii), B → (i), C → (iii) H
(c) H
(c) A → (ii), B → (i), C → (iii) OH H OH H
O
(d) A → (iii), B → (ii), C → (i) HO H
Ans. (c) H OH H OH
Sucrose (cane sugar), lactose (milk sugar) and maltose are CH2OH CH2OH
disaccharides in which two monosaccharides are hold together
by a glycosidic linkage. H O H H O
(c) H
(A) In sucrose, C1 of α - D - glucose and C2 of H H
HO H HO H
β-D-fructose are linked together (ii). HO O OH
(B) In lactose, C1 of β - D-galactose and C4 of
β-D-glucose are linked together (i). H OH H OH
422 JEE Main Chapterwise Topicwise Chemistry

CH2OH CH2OH
x’, ‘y’ and ‘z’ in these reactions are respectively
H O H H O [2020, 2 Sep Shift-I]
HO
(d)
H H (a) 5, 4 and 5 (b) 4, 5 and 5
H H H H
O (c) 5, 6 and 5 (d) 4, 6 and 5
HO H
Ans. (d)
HO OH HO OH
Glucose is a polyhydroxy aldohexose. Its number of free —OH
Ans. (c)
groups can be calculated by acetylation process which is done by
Maltose is a disaccharide which is made of twoα-D-glucose using (CH3CO)2 O/Py or CH3COCl /Py as :
units in which C1 (anomeric carbon) of one glucose (I) is linked to
C4 of another glucose unit (II). O O
6 6
CH2OH CH2OH – CH3COOH
R—O H + CH3 — C — O — C — CH3
5 O H 5 O H Py
H H
H H
O
4 1 4 1
OH H OH H
O R — O — C — CH3
OH OH
3 2 3 2 Acetyl derivative
H OH H OH
(I) C1-C4 (II) Free anomeric – nCH COOH
Glycosidic carbon (C1) to Or R(OH)n + n(CH3CO)2 O →
3
R (OCOCH3 ) n
Py
linkage show reducing
property H OR H OR
C C
Maltose
(i) ROH (CH3CO)2O
(CHOH)3 O (CHOCOCH3)3 O
12 Which of the glycosidic linkage between galactose and HCl(g) 4 eq
glucose is present in lactose? [2021, 25 Feb Shift-I] CH (x = 4) CH
(a) C-1 of galactose and C-4 of glucose CH== O
(b) C-1 of galactose and C-6 of glucose CH2OH CH2OCOCH3
(c) C-1 of glucose and C-4 of galactose (CH—OH)3 [Four — OH groups]

(d) C-1 of glucose and C-6 of galactose CH—OH CH2OH CH2OCOCH3

Ans. (a) (ii) Ni (CH3CO)2O
CH2OH (CHOH)4 (CHOCOCH3)4
Glycosidic linkage is a type of covalent bond that joins H2 6 eq.
carbohydrate molecules to another group. [Five—OH] (y = 6)
CH2 OH CH2OCOCH3
6
Glucose
HO [Six—OH groups]
6
HO 5 O OH CHO
HO 5 O
(iii) (CH3CO)2O
O 4 OH 1 (CHOCOCH3)4
4 (z = 5)
OH 1
3 2 CH2 OCOCH3
3 2
OH
So, x, y and z in these reactions are 4, 6 and 5 respectively.
OH
b-D-galactose b-D-glucose
14 The correct observation in the following reactions, is
Lactose
Glycosidic bond
In lactose, glycosidic linkage is formed between C-1 of galactose Sucrose   → A + B Se
liwanoff's
→
Cleavage reagent
and C-4, glycosidic of glucose. (Hydrolysis)
[2020, 2 Sep Shift-II]
13 Consider the following reactions : (a) Formation of blue colour
(i) Glucose + ROH → Acetal
Dry HCl (b) Gives no colour
(c) Formation of red colour
x eq. of
→ Acetyl derivative (d) Formation of violet colour
(CH3 CO)2 O
Ans. (c)
(ii) Glucose Glycosidic bond
Ni/H2 C12H22O11 + H2O → C6H12O6 + C6H12O6
y eq.of Cleavage (Mutarotation)
→ A → Acetyl derivative Sucrose Glucose Fructose
(CH3CO) 2O A (Say) B
z eq.of
(iii) Glucose  → Acetyl derivative Soliwanoffs reagent
→ Red colouration
(CH3CO) 2O Dilute resorsinol + Dilute HCl
Biomolecules 423

Soliwanoff’s reagent test is given by ketohexoses (here, B) and 6 6

CH2OH CH2OH
sucrose only but not by any aldohexose (here, A), lactose and β
5 5
maltose. OH O H O OH
1
H H
15 What are the functional groups present in the structure 4
OH H β-l O 4 OH H
1
ink
age
of maltose? [2020, 4 Sep Shift-I] H H H
3 2 3 2
(a) One ketal and one hemiketal
H OH H OH
(b) One acetal and one ketal
β-D-glucose β-D-glucose
(c) One acetal and one hemiacetal
Lactose
(d) Two acetals
Hence, option (a) is not true.
Ans. (c)
The functional groups present in the structure of maltose is one 18 Which of the following statements is correct?
acetal and one hemiacetal. It is illustrated in following structure. [2020, 7 Jan Shift-II]
(a) Gluconic acid is obtained by oxidation of glucose with
CH2OH Acetal CH2OH HNO 3
O H H O (b) Gluconic acid is a dicarboxylic acid
H H
H H (c) Gluconic acid can form cyclic (acetal/hemiacetal)
structure
OH H OH H
HO O OH (d) Gluconic acid is a partial oxidation product of glucose
Ans. (d)
H OH H OH Hemiacetal
The correct chemical equations are given as follows :
Maltose
CHO COOH
COOH
16 The number of chiral carbons present in sucrose is HNO3 (greater
extent of oxidation) (CHOH)4 Br2 -H2O (CHOH)4
……… . [2020, 5 Sep Shift-II] (CHOH)4
(partial oxidation)
Ans. (9.00) CH2OH CH2OH
COOH
Saccharic acid (glucose) Gluconic acid
CH2OH (dicarboxylic acid) (monocarboxylic
acid)
* O OH O
H OHCH2 H Therefore,
H O
* OH H * * H OH * (i) Saccharic acid not gluconic acid is obtained by the
Gycosidic
OH linkage oxidation of glucose withHNO3. Thus, it is incorrect
CH2OH
* * * * statement.
H OH OH H (ii) Gluconic acid is a monocarboxylic acid and not a
dicarboxylic acid. Thus, it is incorrect statement.
Total number of chiral carbon in sucrose = 9 (iii) Glucose exists predominantly in the cyclic structure than
the open chain structure :
17 Which one of the following statements is not true?
[2020, 6 Sep Shift-II] CH2OH
CHO
(a) Lactose contains α-glycosidic linkage between C 1 of O
galactose and C 4 of glucose. (CHOH)4 HO OH
(b) Lactose is a reducing sugar and it gives Fehling’s test.
(c) Lactose (C 11H22O 11) is a disaccharide and it contains 8 CH2OH
OH OH
hydroxyl groups.
(d) On acid hydrolysis, lactose gives one molecule of D(+ ) - But gluconic acid can not exist in cyclic structure.
glucose and one molecule of D (+ ) - galactose (Stereochemical configurations are not specified in the
structures given above, for simplicity). Thus, (iii) is
Ans. (a)
incorrect.
Lactose contains β-glycosidic linkage between C1 of galactose (iv) Gluconic acid is a partial oxidation product of glucose.
and C4 of glucose. It is found in milk and is also known as milk Hence, it is correct statement.
sugar. On hydrolysis with dilute acid, it yield an equimolar mixture
of D-glucose and D-galactose. It is a reducing sugar and gets 19 Which of the following statement is not true for
hydrolysed by emulsion, which is an enzyme that specifically glucose? [2020, 8 Jan Shift-I]
hydrolysisβ-glycosidic linkages. Lactose contain anomeric OH. (a) The pentaacetate of glucose does not react with
So, it give Fehling test. hydroxylamine to give oxime
Now, in ∆SPT, (b) Glucose exists in two crystalline forms α and β
PT 3 (c) Glucose gives Schiff’s test for aldehyde
= sin60 ° ⇒ PT = km
SP 2 (d) Glucose reacts with hydroxylamine to form oxime
424 JEE Main Chapterwise Topicwise Chemistry

Ans. (c) 22 Fructose and glucose can be distinguished by

The incorrect statement is (c). It can be corrected as follows : [2019, 8 April Shift-II]
Glucose does not give Schiff’s test due to absence of free —CHO (a) Fehling’s test (b) Barfoed’s test
in cyclic form. (c) Benedict’s test (d) Seliwanoff’s test
The correct statements can be explained as follows : Ans. (d)
(a) Pentaacetate of glucose does not react with Both fructose and glucose give following test positive.
hydroxylamine to give oxime. Because, the cyclic form
(pyranose) of glucose after pentaacetate formation does (i) Fehling’s test (red ppt. of Cu2O is obtained).
not have free —CHO or ‚ƒ C ==O group.
(ii) Barfoed’s test (red ppt. of Cu2O is obtained)
(b) Cyclic form of glucose has two diastereomeric forms (iii) Benedict’s test (red ppt. of Cu2O is obtained)
which are named asα and β form. Each form its own Fehling’s solution : CuSO4 + Na, K-tartrate
crystal. (Rochelle salt)
(d) Glucose reacts with hydroxylamine to form oxime.
Barfoed’s reagent (CH3COO)2 Cu + CH3COOH + H2O
(7%) (1%) (92%)
20 Two monomers in maltose are [2020, 8 Jan Shift-II]
(a) α-D-glucose and α-D-glucose Benedict’s solution : CuSO4 + Na-citrate + Na2 CO3
(b) α-D-glucose and α-D-galactose Seliwanoff’s test is used to differentiate between ketose and
(c) α-D-glucose and β-D-glucose aldose. The reagent is a solution of resorcinol in concentrated
(d) α-D-glucose and α-D-fructose HCl. The reagent when heated along with a sugar will produce
Ans. (a) furfural or hydroxy-methylfurfural, which further reacts to give
red color. Ketose (fructose) reacts more quickly than aldose
Maltose is a disaccharide formed from monosaccharidesα-D- (glucose).
glucose andα-D glucose via C1 C 4 glycosidic linkage.
It is shown in following structure: 23 Which of the following statement is not true about
sucrose? [2019, 9 April Shift-I]
CH2OH CH2OH
(a) It is also named as invert sugar.
H O H H O H (b) The glycosidic linkage is present between C 1 of
H 1 4 H α-glucose and C2 of β-fructose
OH H O OH H (c) It is a non-reducing sugar
HO H OH (d) On hydrolysis, it produces glucose and fructose
Ans. (b)
H OH H OH
Statement-(b) is not true for sucrose. It is linked through a
glycosidic linkage between C-1 ofα-glucose and C-2 of
21 Maltose on treatment with dilute HCl gives β-fructose. Since, the reducing groups of glucose and fructose
[2019, 8 April Shift-I]
are involved in glycosidic bond formation, sucrose is a
(a) D-glucose and D-fructose (b) D-fructose
non-reducing sugar.
(c) D-galactose (d) D-glucose
Ans. (d) CH2OH
O
Maltose on treatment with dil. HCl gives D-glucose. Hydrolysis of H H HOH2C O
H H
maltose yields two moles of α β
α- D-glucose. Thus, it is composed of twoα-D-glucose units in OH H
HO Glycosidic
which C-1 of one glucose unit (I) is linked to C-4 of another linkage H HO CH2OH
glucose unit (II). The free aldehyde group can be produced at C-1 H OH
of second glucose in solution and it shows reducing properties. α-D-glucose OH H
So, it is a reducing sugar. β-D-fructose
CH2OH CH2OH
O O On hydrolysis with acids or enzyme, sucrose gives equimolar
H H H H H mixture of D-(+)-glucose and D-(–)-fructose.
H
O HCl
OH
OH H OH H
OH C12H22O11 + H2O → C6H12O6 + C6H12O6
D -(+) - glucose D-(–) -fructose
H OH H OH CH2OH
H
O 24 Amylopectin is composed of [2019, 10 April Shift-I]
OH
Dil. HCl
2
H (a) β-D-glucose, C 1-C 4 and C2 -C 6 linkages
OH
OH H H (b) α-D-glucose, C 1-C 4 and C2 -C 6 linkages
(c) β-D-glucose, C 1-C 4 and C 1-C 6 linkages
H OH
α-D-glucose (d) α-D-glucose, C 1-C 4 and C 1 -C 6 linkages
Biomolecules 425

Ans. (d) Ans. (a)

Amylopectin is the water-soluble component of starch. It is a Statement (a) is incorrect. Glycogen is not a straight chain
branched-chain polymer ofα-D-glucose. The main chain polymer similar to amylose. It is highly branched structure
consists of an α − 1, 4′- glycosidic linkages betweenα-D- glucose similar to amylopectin. It is known to be the storage material of
units and the branches are connected to the main chain byα - 16 , ′- animals. It is found in liver, muscles and brain. It breaks down to
glycosidic linkages. Its structure can be represented as: glucose by the action of enzymes when body needs a glucose. It
6
is also found in yeast and fungi.
4 CH2OH O
O
5 2
H
27 Glucose on prolonged heating with HI gives
HO
3 OH
1
α-1, 6′-glycosidic linkage (Branch)
(a) n-hexane (b) 1-hexene [JEE Main 2018]
O
6 6 (c) Hexanoic acid (d) 6-iodohexanal
4 CH2 O 4 CH2OH
O Ans. (a)
5 2 5 2 H
H
HO HO 1 HI is a strong reducing agent. It reduces both primary and
3 OH 3 OH O
O secondary alcoholic groups of glucose along with the carbonyl
α-1, 4′-glycosidic linkage (Chain) group to produce n-hexane as
Structure of amylopectin
CHO Carbonyl group CH3
Secondary HI
25 Number of stereo-centers present in linear and cyclic (CHOH)4 alcoholic
∆ (CH2)4
group
structures of glucose are respectively (Prolonged)
[2019, 10 April Shift-II] CH2OH Primary CH3
alcoholic
(a) 4 and 5 (b) 4 and 4 Glucose group n-hexane
(c) 5 and 4 (d) 5 and 5
Ans. (a) 28 Which of the following compounds will behave as a
Key Idea Chiral centre is also called stereo-centre or reducing sugar in an aqueous KOH solution?
stereogenic center. [JEE Main 2017]

Linear structure of glucose is as follows : HOH2C O CH2OH HOH2C O CH2OH

CHO (a) HO (b) HO
H OH
OCOCH3
HO H
OH OH
H OH
HOH2C
H OH
CH2OH HOH2C O CH2OH O CH2OCH3
(c) HO (d) OH
Fischer formula
Number of stereo-centre (C* ) = 4. OCH3 OH
Cyclic structure of glucose are as follows : OH OH
CH2OH CH2OH Ans. (a)
O O
H H H H H OH Sugars that have an aldehyde, a ketone, a hemiacetal or a
hemiketal group is able to reduce an oxidising agent. These
HO OH H OH HO OH H H sugars are classified as reducing sugars.
HOH2C O CH2OH HOH2C O CH2OH
H OH H OH aq·KOH
α-D-glucose β-D-glucose HO –+ OH
OCOCH3 –CH3COOK O–
*
Haworth formula Number of stereo-centre (C ) in each anomer
OH OH
= 5. Hemiacetal

26 Which of the given statements is incorrect about

glycogen? [2019, 12 April Shift-II] O
HOH2C CH2OH
(a) It is straight chain polymer similar to amylose
HO
(b) Only α-linkages are present in the molecule
(c) It is present in animal cells
(d) It is present in some yeast and fungi OH
(α-hydroxyketone)
426 JEE Main Chapterwise Topicwise Chemistry

Hemiacetal can be easily reduced by oxidising agent such as Ans. (c)

Tollen’s reagent. α-D(+) glucose and β-D(+) glucose are anomers of glucose.
CH2OH CH2OH
O
HOH2C CH2OH O O
Tollen’s H H H H H OH
O positive silver
OH reagent
mirror test.
HO OH H OH HO OH H H
OH
(Reducing sugar) H OH H OH
α-D-glucose β-D-glucose
29 Synthesis of each molecule of glucose in
photosynthesis involves [JEE Main 2013] 34 The term anomers of glucose refers to
(a) 18 molecules of ATP (a) isomers of glucose that differ in configurations at
(b) 10 molecules of ATP carbons one and four (C-1 and C-4
(c) 8 molecules of ATP (b) a mixture of (D)-glucose and (L)-glucose
(c) enantiomers of glucose
(d) 6 molecules of ATP
(d) isomers of glucose that differ in configuration at carbon
Ans. (a) one (C – 1) [AIEEE 2006]
6CO2 + 12NADPH + 18ATP → C6H12O6 + 12NADP + 18 ADP Ans. (d)
Anomers of glucose are cyclic diastereomers (epimers) differing
30 Which of the following compounds can be detected by in configuration of the hydroxyl group at C-1, existing in two formsα
Molisch’s test? [AIEEE 2012] andβ, respectively.
(a) Nitro compounds (b) Sugars
(c) Amines (d) Primary alcohols 35 Complete hydrolysis of cellulose gives [AIEEE 2003]

Ans. (b) (a) D-fructose (b) D-ribose (c) D-glucose (d) L-glucose
Molisch’s test is used for the detection of carbohydrates. Add Ans. (c)
two drops of alcoholic solution ofα-naphthol to the carbohydrate Partial hydrolysis of cellulose gives the disaccharide cellobiose
solution under study. Add conc.H2SO4 slowly by the side of the (C12H22O11). Cellobiose resembles maltose (which on acid
test tube. A violet ring is formed at the junction of the two catalysed hydrolysis yields two molar equivalents of D-Glucose)
liquids, if carbohydrate is present. in every respect except one : the configuration of its glycosidic
linkage.
31 The change in the optical rotation of freshly prepared
solution of glucose is known as [AIEEE 2011]
(a) tautomerism (b) racemization
TOPIC 2
(c) specific rotation (d) mutarotation Proteins and Enzymes
Ans. (d)
A spontaneous change in the specific rotation of a solution of an 36 A peptide synthesised by the reactions of one molecule
optically active compound is called mutarotation. each of glycine, leucine, aspartic acid and histidine will
Hemiacetal forms of α- and β-D- glucose are stable in solid state have ……… peptide linkages. [2021, 01 Sep Shift-II]
but in aqueous solution, there is opening of the cyclic structure Ans. (3)
which gives solution of constant specific rotation. Peptide synthesised by reaction of glycine, leucine, aspartic acid
and histidine is as follows.
32 The two functional groups present in a typical O O
carbohydrate are [AIEEE 2009]
H2N—CH2—C—OH + H2N—CH—C—OH—H2N—CH—C—OH
(a) —OH and —COOH (b) —CHO and —COOH
(c) C == O and —OH (d) —OH and —CHO O CH2 CH2
Ans. (c, d) Glycine CH—CH2 COOH
Carbohydrates are optically active polyhydroxy aldehyde or Aspartic Acid
polyhydroxy ketones. CH3 +
Leucine H2N—CH—COOH
C == O, OH are the functional groups of typical ketose
while —CH ==O, OH are the functional groups of typical aldose. CH2

N
33 α-D(+)-glucose and β-D-(+)-glucose are [AIEEE 2008]
NH
(a) conformers (b) epimers Histidine
(c) anomers (d) enantiomers
Biomolecules 427

Ans. (b)
O O O
Albumin, a globular protein is soluble in water. It is half saturated
H2N—CH2—C—NH—CH—C—NH—CH—C—NH—CH—COOH with a salt such as ammonium sulphate. Serum albumin is a
component of blood serum.
CH2 CH2 CH2 Rest all others are fibrin, collagen and myosin are insoluble in
water and all are fibrous proteins.
CH COOH N
H3C CH3 NH 40 Which of the following is correct structure of tyrosine?
[2021, 17 March Shift-I]
O
 COOH
3 peptide linkage 
( C NH 
) are present. (a) H2 N H
Hence, answer is 3.
OH
37 Which of the following is not an example of fibrous
protein ? [2021, 31 Aug Shift-II] COOH
(a) Keratin (b) Albumin H2 N OH
H
(c) Collagen (d) Myosin (b)
Ans. (b)
Insulin and albumin are globular protein. Fibrous proteins are
generally composed of long and narrow strands and have COOH
H2N OH
structural role while globular proteins generally have more (c) H
compact and rounded shape and involved in metabolic functions.

38 The total number of negative charge in the tetrapeptide,

Gly-Glu-Asp-Tyr, at pH 12.5 will be ……… . (Integer COOH
answer) [2021, 26 Aug Shift-I] H 3N H
Ans. (4) (d)

The structures of tetrapeptide Gly-Glu-Asp-Tyr is as follows OH

Ans. (d)
H2N—CH2—C —NH—CH—C —NH The structure of tyrosine amino acid is
CH2—CH2—COOH COOH
tetrapeptide H2N——H
CH2— —OH
CH2 OH
CH C —NH—
It is an example of non-essential amino acid which contains
COOH
CH2—COOH aromatic (phenolic) ring.
pH=12.5
(highly basic)
41 The secondary structure of protein is stabilised by
[2021, 16 March Shift-II]
(a) peptide bond (b) glycosidic bond
H2N—CH2— C — NH—CH — C — NH — (c) hydrogen bonding (d) van der Waals’ forces
CH2—CH2—COO
Ans. (c)
In secondary structure of protein, hydrogen bond is formed
CH2 O O
CH—C —NH— 
COO between  C  and NH  groups of the peptide bond.
CH2—COO Peptide linkage is an amide formed between COOHgroup and
+
(All protons (H ) from carboxylic group and phenol are lost NH2 group while connecting two amino acids.
neutralised in basic medium) The two monosaccharides are joined together by an oxide
Total negative charge = 4. linkage formed by the loss of a water molecule is called
glycosidic linkage.
39 The water soluble protein is [2021, 22 July Shift-I]
42 Out of the following, which type of interaction is
(a) fibrin responsible for the stabilisation of α-helix structure of
(b) albumin
proteins ? [2021, 24 Feb Shift-I]
(c) myosin
(a) van der Waals’ forces (b) Covalent bonding
(d) collagen
(c) Ionic bonding (d) Hydrogen bonding
428 JEE Main Chapterwise Topicwise Chemistry

Ans. (d) *
HN C NH (CH2)3 CH COOH
α-helix structure of proteins is stabilised by H-bonds
between hydrogen of —NH and oxygen of C == O group is NH2 (Arg) NH2
amino acids.
Number of chiral carbons present in the given tripeptide is 4.
H
C 45 Which of the following is not an essential amino acid?
C N [2020, 5 Sep Shift-I]
H O C (a) Leucine (b) Valine
H
N C (c) Lysine (d) Tyrosine
C
N
C O
Ans. (d)
Hydrogen
C
HO bond Tyrosine is not an essential amino acid and remaining all are
H
C C essential amino acid.
N C N
O Amino acids which are synthesised by the body, are called
HO C non-essential. On the otherhand, those amino acids which
H C cannot be synthesised in the human body and are supplied in the
C N
form of diet are called essential amino acids the ten essential
N C O amino acids.
C
HO Valine, leucine, isoleucine, arginine lysine, threonine,
C
N methionine, phenylalanine, trpropham, histidine are essential
O amino acid.
α-helix
Secondary structure 46 Consider the Assertion and Reason given below.
Assertion (A) Ethene polymerised in the presence of
Ziegler-Natta catalyst at high temperature and
43 The number of C == O groups present in a tripeptide
pressure is used to make buckets and dustbins.
Asp-Glu-Lys is ........... . [2020, 3 Sep Shift-II] Reason (R) High density polymers are closely packed
Ans. (5) and are chemically inert.
Number of C O groups is 5 in tripeptide Choose the correct answer from the following:
Asp - Glu - Lys. [2020, 6 Sep Shift-I]

O O O
(a) (A) is correct but (R) is wrong.
(b) Both (A) and (R) are correct but (R) is not the correct
H2N—CH—C—NH—CH—C—NH—CH—C—OH explanation of (A).
(c) Both (A) and (R) are correct and (R) is the correct
CH2 CH2 (CH2)4 explanation of (A).
(d) (A) and (R) both are wrong.
O C CH2 CH2
Ans. (c)
OH C O NH2 Both (A) and (R) are correct and (R) is the correct explanation of
OH (A). High density polymers are formed by polymerisation of
ethene in presence of catalyst like (C2H5 ) 3 Al + TiCl 4 called
44 The number of chiral carbon(s) present in peptide, Ziegler- Natta catalyst at 333 K to 343 K and under 6-7
atmospheric pressure.
Ile-Arg-Pro, is …… . [2020, 5 Sep Shift-I]
High density polythene (HDP) thus produced, consists of linear
Ans. (4) molecules and has high density due to closed packing. It is used
The amino acids present in the given tripeptide Ile-Arg-pro are for making buckets, dustbins, bottles, pipe, etc.
isolucine, arginine and proline. Hence, the correct option is (c).
Chiral carbon
47 A, B and C are three biomolecules. The results of the
* * tests performed on them are given below:
CH3 CH2 CH CH COOH
[2020 Jan Shift-II]
CH3 NH2
(Ile) Molisch’s test Barfoed test Biuret test
A Positive Negative Negative
*
HN CH COOH B Positive Positive Negative
C Negative Negative Positive
(Pro)
Biomolecules 429

A, B and C are respectively: Acetamidine group present in arginine is

(a) A = Lactose, B = Glucose, C = Alanine NH2
(b) A = Glucose, B = Fructose, C = Albumin C
NH
(c) A = Lactose, B = Glucose, C = Albumin
its self-protonation/deprotonation makes its conjugate acid very
(d) A = Lactose, B = Fructose, C = Alanine
stable.
Ans. (c)
NH2
Molisch’s test is for all carbohydrates (except trioses and So, C is a strongly basic in nature.
tetroses). NH
∴ Lactose, fructose and glucose give positive test. The resonating structure of acetamidine group is
Barfoed test is positive only for monosaccharides. H –
N H NH NH
∴ It is given by glucose and fructose, not by lactose (because it is C C C
+
disaccharide). NH NH2 NH2
Biuret test is for compounds with peptide linkages.
The basicity order of given amino acids in aqueous solution is as
∴ Albumin (a protein) gives positive test. Alanine is an amino acid
follows:
but have no peptide linkage.
∴ It does not give biuret test. Asp < Gly < Lys < Arg
So, A = lactose, B = glucose andC = albumin. Thus, order of pK a values is also,
Asp < Gly < Lys < Arg
48 The peptide that gives positive ceric ammonium nitrate pK a value : (3) (6) (9.8) (10.8)
and carbylamine tests is [2019, 9 April Shift-II]
(a) Lys-Asp (b) Ser-Lys (c) Gln-Asp (d) Asp-Gln 50 The correct sequence of amino acids present in the
Ans. (b) tripeptide given below is [2019, 9 Jan Shift-II]
The peptide that gives positive cerric ammonium nitrate and Me Me Me OH
carbylamine tests is ser-lys. The structures of serine and lysine are, H
N OH
HO  CH2  CH  COOH; H2 N  (CH2 ) 4  CH  COOH H 2N N C
| | H
OH
NH2 NH2
Serine Lysine (a) Thr - Ser - Leu (b) Leu - Ser - Thr
(c) Val - Ser - Thr (d) Thr - Ser - Val
49 The increasing order of pK a of the following amino Ans. (c)
acids in aqueous solution is Gly, Asp, Lys, Arg Formation of the tripeptide (Val-Ser-Thr) can be shown as:
(a) Asp < Gly < Arg < Lys (b) Arg < Lys < Gly < Asp Me Me Me OH
CH CH
(c) Gly < Asp < Arg < Lys (d) Asp < Gly < Lys < Arg
[2019, 9 Jan Shift-II] CH OH H HN C CH OH
C CH OH H HN C
Ans. (d) H2 N
CH2
Amino acid molecules can be represented as, OH

Valine (Val) Serine (Ser) Threonine (Thr)

COOH
R CH –2H2O
NH2
Nature of the ‘R’ group will determine the basicity (hence, pK a ) of Me Me Me OH
CH CH
an amino acid.
CH NH C CH OH
‘R’ in the amino group Nature of R Nature of the H 2N C CH NH C
amino acids CH2
+ OH
NH2 More basic (due
 (CH2)3 NH  C to the presence Val Ser Thr
1. Basic of acetamidine
NH2
group)
(Arginine : Arg) 51 Which of the following tests cannot be used for
O Acidic Acidic identifying amino acids ? [2019, 10 Jan Shift-II]
2. CH2 C (a) Barfoed test (b) Ninhydrin test
O–
(Aspartic acid: Asp)
(c) Xanthoproteic test (d) Biuret test
Ans. (a)
3. H (Glycine) : Gly Neutral Neutral
4.  (CH ) NH +
Basic Basic (i) Barfoed test is used for detecting the presence of
2 4 3 monosaccharides like glucose, fructose etc. Barfoed reagents is
(Lysine : Lys) Cu (II) acetate solution.
430 JEE Main Chapterwise Topicwise Chemistry

CHO COOH At highly acidic pH, i.e. 2 both the nitrogens with lone pairs will
H OH H OH accept oneH+ each and  C OHwill not loose itsH+ .
HO H HO 
+ Cu2+ + 2H2O H
H OH O
H OH
H OH (Cu (II) Thus, the final structure of histidine at
H OH
acetale) pH = 2 will be
CH2OH CH2OH
(D-glucose) (D-gluconic acid) +
H3 N CH C OH
+ Cu2O + 4H+
(Red ppt.) CH2 O
(ii) (Ninhydrin Test)
Violet +
Ninhydrin/ D H N
colouration
NH
Amino acid (Xanthoprotic Test) Yellow
(Protein) Conc. HNO3 colouration
(Biuret Test) 54 The correct match between Item I and Item II is
Violet
CuSO4 (aq)+NaOH
colouration Item I Item II
A. Allosteric effect P. Molecule binding to the active
52 Among the following compounds, most basic amino acid site of enzyme.
is [2019, 12 Jan Shift-I]
B. Competitive inhibitor Q. Molecule crucial for
(a) serine (b) asparagine (c) lysine (d) histidine communication in the body.
Ans. (c) C. Receptor R. Molecule binding to a site other
The most basic amino acid is lysine. There are only two basic than the active site of enzyme.
amino acids (amino acids with two basic nitrogen containing D. Poison S. Molecule binding to the enzyme
groups). These are lysine and arginine. Lysine have an ε-amino covalently.
group. At physiological pH, the groups are protonated as follows:
+ (a) A → P; B → R; C → S; D → Q
NH3 O
δ γ β (b) A → P, B → R; C → Q; D → S
+ ý α
H 3N CH2CH2CH2CH2 CH C O
s
(c) A → R; B → P; C → S; D → Q
an ε-amino group (d) A → R; B → P; C → Q; D → S [2019, 11 Jan Shift-II]
Ans. (d)
Asparagine is an acidic amino acid. It is the amide of aspartate.
Histidine is an imidazole substituted alanine. (A) Molecule binding to a site other than the active site of
enzyme is called allosteric effect.
Serine contain alcohol group and is an HO-substituted alanine.
(B) Molecule binding to the active site of enzyme is called
competitive inhibitor.
53 The correct structure of histidine in a strongly acidic (C) Molecule crucial for communication in the body is called
solution (pH= 2) is [2019, 12 Jan Shift-II] receptor.
r s r (D) Molecule binding to the enzyme covalently is called poison.
(a) H3N CH COO (b) H3N CH COOH Thus, the correct match is :
r r A → R, B → P, C → Q, D → S
NH2 NH2

N N 55 The predominant form of histamine present in human

(c) H3N
r
CH
s
COO (d) H3N
r
CH COOH blood is (pK a , Histidine = 6.0) [JEE Main 2018]

NH + H H
NH N N r
NH NH2 NH3
Nr (a) (b)
r
H N N
Ans. (d) H
H H
Histidine has following structure in N N r
NH2 NH3
(c) (d)
H2N CH C OH r
N N
CH2 O H
Lone pairs of
These lone pairs are Ans. (d)
both of these N
nitrogen are not free for donation as Our blood is slightly basic in nature with pH range from 7.35-7.4.
freely available N H these are delocalised
with-π bonds. The structure of histamine is given below :
for donation
Biomolecules 431

Aliphatic
amino group
58 Biuret test is not given by [AIEEE 2010]
H (a) carbohydrates (b) polypeptides
Imidazole N
NH2 (c) urea (d) proteins
ring
Ans. (a)
N
Biuret test is characteristically given by the compound having
Basic nitrogen of imidazole ring O

It is produced by decarboxylation of histidine having following —C — NH — functional group.
structure.
It is clearly visible from the above structure that histamine has 59 The secondary structure of a protein refers to
two basic centres namely aliphatic amino group and basic [AIEEE 2007]
nitrogen of imidazole ring. (a) α-helical backbone
The aliphatic amino group has pK a around 9.4. (b) hydrophobic interactions
In blood with pH around 7.4 the aliphatic amino group of (c) sequence of α-amino acids
histamine become protonated to give a single charged cation as (d) fixed configuration of the polypeptide backbone
shown below
Ans. (a)
H
N + Primary structure involves sequence ofα-amino acids in a
NH3 polypeptide chain.
N Secondary structure involvesα-helical andβ-pleated sheet like
structures.
56 Thiol group is present in [JEE Main 2016]
(a) cystine (b) cysteine 60 Identify the correct statement regarding enzymes.
[AIEEE 2004]
(c) methionine (d) cytosine
Ans. (b) (a) Enzymes are specific biological catalysts that can
normally function at very high temperatures (T~ 1000 K)
NH2
(b) Enzymes are normally heterogeneous catalysts that are
Cystine HO S COOH very specific in their action
C S
(c) Enzymes are specific biological catalysts that cannot be
O NH2 poisoned
COOH
Cysteine (d) Enzymes are specific biological catalysts that possess
HS well defined active sites
NH2
Ans. (d)
O
Normal optimum temperature of enzymes is between 25°C to
S C 40°C. Hence (a) is false. Enzymes are normally homogeneous
Methionine catalysts that can be poisoned.
H3C OH
Thus, (b) and (c) are also false. Enzymes have well defined active sites
NH2
and their actions are specific in nature.
NH2
61 Insulin production and its action in human body are
N
Cytosine responsible for the level of diabetes. This compound
belongs to which of the following categories ?
O N [AIEEE 2004]
H
(a) A coenzyme (b) A hormone
(c) An enzyme (d) An antibiotic
57 Which one of the following statements is correct?
[AIEEE 2012] Ans. (b)
(a) All amino acids except lysine are optically active. Insulin is a hormone built up of two polypeptide chains.
(b) All amino acids are optically active.
(c) All amino acids except glycine are optically active. 62 A substance forms Zwitter ion. It can have functional
(d) All amino acids except glutamic acids are optically active. groups [AIEEE 2002]
Ans. (c) (a) NH2 , COOH (b) NH2 ,  SO 3H
NH2 (c) Both (a) and (b) (d) None of these
Glycine CH2 is α-amino acetic acid with no chiral carbon, Ans. (c)
COOH For the formation of Zwitter ion, basic part and acidic part both
thus optically inactive. should be present in a molecule.
432 JEE Main Chapterwise Topicwise Chemistry

TOPIC 3 65 Thiamine and pyridoxine are also known respectively as

[2021, 22 July Shift-II]
Vitamins and Nucleic Acids (a) vitamin B2 and vitamin E
(b) vitamin E and vitamin B2
H3C H (c) vitamin B 6 and vitamin B2
N
63 (d) vitamin B 1 and vitamin B 6
H N Ans. (d)
Thiamine is also called vitamin B 1 and pyridoxine is also known
H
(A) as vitamin B 6 .
Some common name of vitamins are as follows
The compound ‘A’ is a complementary base of
Vitamin B 1 → Thiamine,
…………… in DNA stands. [2021, 27 July Shift-I]
Vitamin B 6 → Pyridoxine
(a) uracil (b) guanine
Vitamin B2 → Riboflavin
(c) adenine (d) cytosine
Vitamin E → Tocopherol
Ans. (c)
Given structure of compound A is thymine, so its complementary 66 Deficiency of vitamin K causes [2021, 18 March Shift-II]
base will be adenine.
(a) increase in blood clotting time
Adenine form hydrogen bonds with thymine and cytosine will (b) increase in fragility of RBC’s
form hydrogen bond with guanine.
(c) cheilosis
NH2
(d) decrease in blood clotting time
H3C N
N H N Ans. (a)
Vitamin K deficiency causes increase in blood clotting time
N NH N
| because their blood does not have enough vitamin K to form a
H Adenine
clot. The bleeding can occur anywhere i.e. inside or outside the
Thymine (Pyrimidine) (Purine base) body.
Note : Vitamin K related to blood factor.
64 Which one of the following is correct structure for
cytosine? [2021, 25 July Shift-II]
67 Which among the following pair of vitamins is stored in
our body relatively for longer duration ?
[2021, 16 March Shift-I]
H3C
N N—H (a) Thiamine and vitamin A (b) Vitamin A and vitamin D
(a) (b)
(c) Thiamine and ascorbic acid (d) Ascorbic acid and vitamin D
H3C N N
| | Ans. (b)
H H Vitamin A and vitamin D are stored in our body relatively for
NH2 longer duration. These are water insoluble and soluble in fats and
H2N oils. Hence, these are called fat soluble vitamins.
N N Thiamine (vitamin B) and ascorbic acid (vitamin C) are water
(c) (d)
soluble vitamins and must be supplied regularly in diet. These
N N vitamins are not stored in our body.
| |
H H
68 Which of the following vitamin is helpful in delaying the
Ans. (c)
blood clotting ? [2021, 26 Feb Shift-I]
Cytosine is one of four chemical bases in DNA and RNA. (a) Vitamin C (b) Vitamin B (c) Vitamin E (d) Vitamin K
It is a pyrimidine derivative, with a heterocylic aromatic ring and
two substituents attached. The nucleoside of cytosine is Ans. (d)
cytidine. Deficiency of vitamin K increases blood clotting time. So, vitamin
Hence, correct structure of cytosine is, K is helpful in blood clotting. It is a fat-soluble vitamin.
Vitamin C is used to prevent and treat scurvy. It is a water soluble
NH2 vitamin.
4 Vitamin B are also water soluble and play significant roles in cell
5 N
2 metabolism and synthesis of RBC.
6 1
Vitamin E is a fat-soluble vitamin. Deficiency of it may cause
N
| increased fragility of RBCs, nerve problems and mascular
H weakness. Vitamin E is a fat-soluble
Cytosine anti-oxidant which protects cell membranes.
Biomolecules 433

69 Match List-I and List-II. (a) Adenine

1°
List-I List-II NH2
A. Valium 1. Antifertility drug N
N
B. Morphine 2. Pernicious
anaemia N N
C. Norethindrone 3. Analgesic
D. Vitamin B12 4. Tranquiliser H
In this structure, primary amine is present. Thus, it shows
Choose the correct answer from the option given carbylamine reaction.
below. [2021, 24 Feb Shift-II] Lysine
1°
A B C D NH2
(a) 4 3 2 1 1 3 5
2
(b) 4 3 1 2 1°
NH2 4 COOH
(c) 2 4 3 1
(d) 1 3 4 2 Here, 2 primary amine are present, thus it show
carbylamine reaction.
Ans. (b)
(b) Thymine O
(A) Valium – (4) Tranquilizer CH3
2°
A tranquilizer drug became a standard drug for the N H
treatment of anxiety and one of most commonly
prescribed drugs of all time.
N O
(B) Morphine – (3) Analgesic
Morphine is effective for both acute and chronic pain and H
often used before and after surgery.
Here, secondary amine (2°) are present, thus it doesn’t
(C) Norethindrone – (1) Antifertility drug show carbylamine reaction.
It is a form of progesterone, a female hormone Proline Cyclic amino acid
important for regulating ovulation and menstruation.
COOH
(D) Vitamin B 12 –(2) Pernicious anaemia 1
2°
It is a nutrient that helps to keep our body blood cells and 2 NH
nerve cells healthy and help in making DNA.
3 4

70 Which of the following will react with CHCl 3 + alc. KOH? Here, secondary amine (2°) are present, thus it doesn’t
[2020, 4 Sep Shift-I] show carbylamine reaction.
(a) Adenine and lysine (b) Thymine and proline (c) Adenine show this reaction but thymine does not show this
reaction with carbylamine reaction.
(c) Adenine and thymine (d) Adenine and proline
(d) Adenine It show the reaction with carbylamine reaction but
Ans. (a)
proline does not show reaction.
Adenine and lysine react with CHCl 3 and alc. KOH. This type of
reagent show carbylamine reaction. Carbylamine reaction is 71 Match the following :
given by only primary amine.
(i) Riboflavin (A) Beriberi
CH2OH (ii) Thiamine (B) Scurvy
Cl O O (iii) Pyridoxine (C) Cheilosis
OH HO (iv) Ascorbic acid (D) Convulsions
O
CH2Cl [2020, 7 Jan Shift-I]

OH OH (a) (i)-(C), (ii)-(D), (iii)-(A), (iv)-(B)

(b) (i)-(C), (ii)-(A), (iii)-(D), (iv)-(B)
NH2 (c) (i)-(D), (ii)-(B), (iii)-(A), (iv)-(C)
—NH
NH (d) (i)-(A), (ii)-(D), (iii)-(C), (iv)-(B)
S OH
Ans. (b)
(i) Riboflavin - (C) Cheilosis
General reaction is as follows : (ii) Thiammine - (A) Beri-beri
R NH2 + CHCl 3 + 3KOH → R N ≡≡ C + 3KCl + 3H2O (iii) Pyridoxine - (D) Convulsions
1° amine Isocyanide (iv) Ascorbic acid - (B) Scurvy
Thus, the correct option is (b).
Adenine and lysine both have primary amine.
434 JEE Main Chapterwise Topicwise Chemistry

72 Which of the following statement is not true about RNA? 74 Which of the vitamins given below is water soluble?
[2019, 12 April Shift-I] [JEE Main 2015]
(a) It controls the synthesis of protein (a) Vitamin C (b) Vitamin D
(b) It has always double stranded α-helix structure (c) Vitamin E (d) Vitamin K
(c) It usually does not replicate Ans. (a)
(d) It is present in the nucleus of the cell
Vitamin B and C are water soluble while vitamin A,D,E and K are
Ans. (b)
fat soluble or water insoluble.
RNA does not have double strandedα-helix structure. Helixes
present in RNA are single-stranded but sometimes they fold 75 Which one of the following bases is not present in DNA?
back on themselves to form a double helix structure. RNA usually [JEE Main 2014]
does not replicate.
(a) Quinoline
It is present in the nucleus of the cell. It controls the synthesis of (b) Adenine
protein. RNA molecules are of three types, i.e. messenger’s RNA (c) Cytosine
(m-RNA), ribosomal RNA (rRNA), transfer RNA (t-RNA). (d) Thymine
Ans. (a)
73 Among the following compounds, which one is found in
RNA? [2019, 11 Jan Shift-I] DNA contains four nitrogenous pyramidine bases, adenine,
guanine, cytosine, thymine. While quinoline is an alkaloid, hence,
O O it is not present in DNA.
CH3
NH NH
(a) (b) 76 The presence or absence of hydroxy group on which
N O N carbon atom of sugar differentiates RNA and DNA?
O
H [AIEEE 2011]
H
(a) 1st (b) 2nd
NH2 O (c) 3rd (d) 4th
N N Me
(c) (d) Ans. (b)
N O N O
In RNA molecule, sugar moeity is β-D-ribose in which —OHgroup
H Me is present at 2nd carbon. Whereas in DNA, it is
Ans. (a) β-D-2-deoxyribose in which OH group is absent at 2nd carbon.
RNA contains, adenine (A), guanine (G), cytosine (C) and uracil (U). 5 5 4
HOH2C O HOH2C O
OH OH
In the given options, 4 1 4 1
H H H H
H H
3 2 H 3 2 H
OH OH OH H
NH β-D-2-deoxyribose
(a) is uracil (present in RNA only) β-D-ribose

77 The pyrimidine bases present in DNA are [AIEEE 2006]

(a) cytosine and adenine
H 3C (b) cytosine and guanine
NH (c) cytosine and thymine
(b) is thymine (present in DNA only)
(d) cytosine and uracil
Ans. (c)
NH2
In DNA, cytosine and thymine are pyrimidine bases.
H
N
(c) is cytosine (present in both DNA and RNA)
C
N N

HC CH
N¾Me
CH
(d) is not a pyrimidine base but a derivative of uracil.
Pyrimidine base
Me
Biomolecules 435

78 In both DNA and RNA, heterocylic base and phosphate 79 Which base is present in RNA but not in DNA?
ester linkages are at [AIEEE 2005] [AIEEE 2004]

(a) C′5 and C′1 respectively of the sugar molecule (a) Uracil (b) Cytosine (c) Guanine (d) Thymine
(b) C′1 and C′5 respectively of the sugar molecule Ans. (a) Uracil is present in RNA but not in DNA.
(c) C′2 and C′5 respectively of the sugar molecule
(d) C′5 and C′2 respectively of the sugar molecule 80 The reason for double helical structure of DNA is
Ans. (a)
operation of [AIEEE 2003]

Synthesis of RNA/DNA from phosphoric acid, ribose and (a) van der Waals’ forces (b) dipole-dipole interaction
cytosine is given below. Thus, ester linkages are at C′5 and C1′ of (c) hydrogen bonding (d) electrostatic attractions
sugar molecule. Ans. (c)
Dehydration Hydrogen bonding is involved as a molecular force in the DNA
OH molecule.
5′ NH2
HOCH2
O OH Watson and Crick observed the purine- pyrimidine type of
O P OH
+ 4 H H 1′ 5 4 N hydrogen bonding (instead of purine-purine and
OH + 3 pyrimidine-pyrimidine type).
3 2 6 12
H H N O
OH OH H
81 RNA contains [AIEEE 2002]
(a) ribose sugar and thymine
NH2 (b) ribose sugar and uracil
OH 5 4
(c) deoxyribose sugar and uracil
3N
5' 1 2
(d) deoxyribose sugar and thymine
6
O P O CH2 N O
–2H2O O Ans. (b)
OH 4' H H 1' RNA, Ribonucleic acid.
3' 2' Sugar present in RNA is D (–) ribose. It consists of cytosine and
H H
uracil as pyrimidine and guanine and adenine as purine bases.
OH OH
29
Chemistry in
Everyday Life
TOPIC 1 02 Consider the following structures : (b) (B), (C) and (D) are tranquillizers
Chemicals in Medicines CH3 (c) (A) and (D) are tranquillizers
(d) (B) and (C) are tranquillizers
N
01 Which one of the following Ans. (d)
chemicals is responsible for the The structures A and D are narcotic
production of HCl in the stomach A.
analgesics, where A is morphine and D
is codeine.
leading to irritation and pain?
[2021, 27 Aug Shift-II]
HO O OH The structures B and C are tranquillizers
viz. diazepam and serotonin
CO CH3 respectively.
(a) NH N
SO2 03 Given below are two statements.
B. HO N Statement I Penicillin is a
HN
(b) bacteriostatic type antibiotic.
N NH2
Statement II The general
HO NH2 structure of penicillin is
(c) CH2CH2NH2
N C. HO
H R N S CH3
H N H CH3
NNH2 H
(d) CH3 N
COOH
H
N
Ans. (b)
Choose the correct option.
H [2021, 27 July Shift-II]
N D.
(a) Both statement I and statement II
The compound is
H3CO are false
N NH2 O OH
(b) Statement I is false but statement
responsible for the production II is true
The correct statement about (A),
(B), (C) and (D) is (c) Both statement I and statement II
of HCl in the stomach leading to are true
[2021, 27 Aug Shift-I]
irritation and pain.
(a) (A), (B) and (C) are narcotic (d) Statement I is true but statement
So, the option (b) is correct. II is false
analgesics
Chemistry in Everyday Life 437

Ans. (b) Choose the most appropriate (D) Artificial sweetener→ Alitame
Penicillin kills the bacteria, therefore it answer the option given below. Alitame is an artificial sweetener
is a bactericidal type antibiotic. [2021, 18 March Shift-II] containing aspartic acid.
The structure of penicillin is A B C D A B C D Hence, correct match is (A-3),
(a) 4 3 1 2 (b) 4 3 2 1 (B-4), (C-1), (D-2).

R N S CH3 (c) 3 4 5 2 (d) 3 4 2 5

07 Match the list-I with list- II
H CH3 Ans. (b)
List-I List-II
(A) Metallic beryllium is used for
N making windows of X-ray tubes. (A) Chlorophyll (i) Ruthenium
COOH
H (B) When Mg combined with water (B) Vitamin-B 12 (ii) Platinum
∴ Statement I is false and statement II while burning it releases gas and (C) Anticancer drug (iii) Cobalt
is true. oxygen. Magnesium is used in
(D) Grubbs catalyst (iv) Magnesium
either powdered or solid form as
04 Match List-I with List-II. an incendiary agent for both Choose the most appropriate
List-I List-II illumination and antipersonnel answer from the options given
(Drug) (Class of drug) purposes.
below [2021, 18 March Shift-I]
(C) Pure calcium metal is used as a
A. Furacin I. Antibiotic A B C D
reducing agent in the extraction
B. Arsphenamine II. Tranquilisers (a) (iii) (ii) (iv) (i)
of other types of metal, such as
C. Dimetone III. Antiseptic thorium, uranium and zirconium. (b) (iv) (iii) (ii) (i)
D. Valium IV. Synthetic (D) Due to its radioactive nature Ra is (c) (iv) (iii) (i) (ii)
antihistamines used in the treatment of cancer. (d) (iv) (ii) (iii) (i)
Choose the most appropriate Hence, correct match is (A-4), (B-3), Ans. (b)
match : [2021, 27 July Shift-I]
(C-2), (D-1).
A. Chlorophyll is coordination
A B C D A B C D complex of Mg.
06 Match List-I with List-II.
(a) I III IV II (b) III IV II I B. VitaminB12 , cyanocobalamine is a
(c) II I III IV (d) III I IV II List-I coordination compound of cobalt.
List-II
Ans. (d) (Class of C. cis-platin [Pt(NH3)2 Cl2 ] used in the
(Example)
chemicals) treatment of cancer and is a
A. Furacin acts as antiseptic which is coordination compound of
applied to wounds, cuts, ulcers etc. A. Antifertility 1. Meprobamate
drug
platinum.
to prevent the growth of
D. Grubbs catalyst is a series of
micro-organisms. B. Antibiotic 2. Alitame catalysts containing ruthenium.
B. Arsphenamine also known as
salvarsan acts as antibiotic, a drug
C. Tranquilizer 3. Norethindrone ∴ Correct match is (A-iv), (B-iii),
effective against syphilis was D. Artificial 4. Salvarsan (C-ii), (D-i)
introduced at beginning of 1910 but sweetener
have now been supplanted by [2021, 18 March Shift-II] 08 Match the List-I with List- II.
modern antibiotics. A B C D A B C D List-I List-II
C. Dimetone is synthetic (a) 2 3 4 1 (b) 4 3 2 1 (Class of drug) (Example)
antihistamines. They interfere with
natural action of histamines by (c) 3 4 1 2 (d) 2 4 1 3 (A) Antacid (i) Novestrol
competing with histamine for Ans. (c) (B) Artificial (ii) Cimetidine
binding sites of receptor where sweetener
(A) Antifertility drug → Norethindrone
histamine exerts its effect. (C) Antifertility (iii) Valium
Norethindrone is a synthetic
D. Valium is tranquilisers (D) Tranquilizers (iv) Alitame
progesterone which is amongst
(neurologically active drug).
the most commonly used [2021, 18 March Shift-I]
Hence, correct match is A→ III, antifertility drugs.
B → I, C → IV, D → II. A B C D
(B) Antibiotic → Salvarsan
(a) (ii) (iv) (i) (iii)
05 Match List-I with List-II. Arsphenamine, also known as
(b) (iv) (i) (ii) (iii)
salvarsan used as antibiotic.
List-I List-II (c) (iv) (iii) (i) (ii)
(C) Tranquilizer→ Meprobamate
A. Be 1. Treatment of cancer (d) (ii) (iv) (iii) (i)
Meprobamate is used to treat
B. Mg 2. Extraction of metals anxiety disorders or for Ans. (a)
C. Ca 3. Incendiary bombs and short-term relief of the symptoms A. Antacid – Cimetidine
signals of anxiety in adults and children 6 Cimetidine is a stomach acid
D. Ra 4. Windows of X-ray tubes years of age and older. reducer that is used to treat and
5. Bearings for motor Meprobamate is in a class of prevent certain types of stomach
engines. medications called tranquilizers. ulcer.
438 JEE Main Chapterwise Topicwise Chemistry

B. Artificial sweetener – Alitame 10 The number of chiral centres in penicillin is ……… .

Alitame is an aspartic acid containing dipeptide [2020, 8 Jan Shift-I]
sweetener. Ans. (3.00)
C. Antifertility – Novestrol H H
Penicillin
Antifertility drugs is a chemical substances which R N CH3
* S
suppress the action of hormones that promote pregnancy. *
An antifertility drug is novestrol (ethynylestradiol). Another N *
example of antifertility drugs is norethindrone. CH3
D. Tranquilizers – Valium
OH
Valium, trade name of a tranquiliser drug introduced by the
pharmaceutical company Hofmann-La-Roche in 1963. There are three chiral centres shown by asterisk sign.
∴ Correct match is A-(ii), B-(iv), C-(i), D-(iii)
11 The antifertility drug “Novestrol” can react with
09 With respect to drug-enzyme interaction, (a) ZnCl2 /HCl; FeCl3; alcoholic HCN [2020, 3 Sep Shift-I]
identify the wrong statement [2021, 17 March Shift-I] (b) Br2 /water; ZnCl2 /HCl;FeCl3
(a) Non-competitive inhibitor binds to the allosteric site. (c) alcoholic HCN; NaOCl; ZnCl2 /HCl
(b) Allosteric inhibitor changes the enzyme's active site. (d) Br2 /water; ZnCl2 /HCl;NaOCl
(c) Allosteric inhibitor competes with the enzyme's active site. Ans. (b)
(d) Competitive inhibitor binds to the enzyme's active site.
The antifertility drug “novestrol” or ethinylestradiol has the
Ans. (c)
following structure :
Allosteric inhibitor combines at allosteric site and not the active
site. OH
Drugs inhibit the attachment of substrate on active site of CH3 C CH
enzymes in two different ways;
(i) Drugs compete with the natural substrate for their H
attachment on the active sites of enzymes. Such drugs are
called competitive inhibitors.
H H 3°OH group responds
Active Drug
Drug to Lucas test
site HO
(anhydrate ZnCl2 /CHCl)
to and immediately
Substrate
Phenolic  OH group responds turbidity will be observed.
Enzyme Enzyme Substrate to Br2/H2O to give white ppt.
Drug and substrate Drug blocks the active and phenolic  OH group gives
competing for active site of enzyme violet coloration with
site of enzyme neutral FeCl3 .
Drug and substrate competing for active site
So, the correct combination of reagents is in option (b).
(ii) Some drugs do not bind to the enzyme's active site. These
bind to a different site of enzyme which is called allosteric i.e. Br2 /water, ZnCl2 /HCl and FeCl 3.
site. This binding of inhibitor at allosteric site changes the
shape of the active site in such a way that substrate 12 Match the following drugs with their therapeutic actions :
cannot recognise it.This is also called non-competitive
inhibitor. (i) Ranitidine (a) Antidepressant

Active site with (ii) Nardil (Phenelzine) (b) Antibiotic

Active changed shape
site (iii) Chloramphenicol (c) Antihistamine
(iv) Dimetane (Brompheniramine) (d) Antacid
(e) Analgesic
[2020, 3 Sep Shift-II]
Enzyme Allosteric site
Inhibitor
Inhibitor occupying (a) (i)-(a); (ii)-(c); (iii)-(b); (iv)-(e)
allosteric site
(b) (i)-(e); (ii)-(a); (iii)-(c); (iv)-(d)
Non-competitive inhibitor changes the active site of (c) (i)-(d); (ii)-(a); (iii)-(b); (iv)-(c)
enzyme after binding at allosteric site. (d) (i)-(d); (ii)-(c); (iii)-(a); (iv)-(e)
Chemistry in Everyday Life 439

Ans. (c) Ans. (d)

Correct match is Synthetic Brompheniramine is an antihistamine that is used to
(i) → (d), (ii) → (a), (iii) → (b) and (iv) → (c) treat sneezing, runny nose and itchy or watery eyes caused by
(i) Ranitidine→ Antacid allergies, hay fever and the common cold.
[Ranitidine, in which backward flow of acid occur from
stomach.] 16 The presence of soluble fluoride ion upto 1 ppm
(ii) Nardil (Phenelzine) → Antidepressant. concentration in drinking water, is [2020, 6 Sep Shift-I]
[It is used as an antidepressant and anxiotytic] (a) harmful for teeth
(iii) Chloramphenicol→ Antibiotic (b) harmful to skin
[It is an antibiotic used for treatment (c) harmful to bones
of bacterial infections] (d) safe for teeth
(iv) Dimetane (Brompheniramine) → Antihistamine
Ans. (d)
[It is used for treatment of the symptoms
of common cold and allergic such as According to WHO, optimal fluoride ion concentration is 0.5 to 1
runny nose, itchy eyes etc.] ppm in drinking water is safe and good for enamel of teeth and it
makes teeth much harder.
13 The mechanism of action of ‘‘Terfenadine’’ (Seldane) is Hence, the correct option is (d).
(a) Inhibits the secretion of histamine [2020, 4 Sep Shift-II]
(b) Inhibits the action of histamine receptor 17 Noradrenaline is a/an [2019, 9 April Shift-II]
(c) Helps in the secretion of histamine (a) antidepressant
(d) Activates the histamine receptor (b) antihistamine
Ans. (b) (c) neurotransmitter
Seldane (Terfenadine) is also an antihistamines drug. which (d) antacid
interfere with the natural action of histamine by competing with Ans. (c)
histamine for binding sites of receptors, where histamine acts.
Noradrenaline is one of the example of neurotransmitters. It
Thus, it do not affect the secretion of acid in stomach but
plays a major role in mood changes. If the level of noradrenaline
compete with histamine where histamine exterts its effect.
is low for some reason, then signal-sending activity becomes low
and the person suffers from depression.
14 If a person is suffering from the deficiency of
nor-adrenaline, what kind of drug can be suggested? 18 The correct match between item (I) and item (II) is
[2020, 5 Sep Shift-I]
(a) Antihistamine (b) Analgesic Item - I Item - II
(c) Antidepressant (d) Anti-inflammatory (A) Norethindrone (P) Antibiotic
Ans. (c)
(B) Ofloxacin (Q) Antifertility
Nor-adrenaline is one of the neurotransmitter that plays an
(C) Equanil (R) Hypertension
important role in mood changes. If the level of nor-adrenaline in
the body is low for some reason, then the signal-sending activity (S) Analgesics
becomes low and the person suffers from depression. In such [2019, 11 Jan Shift-I]
cases, antidepressant drugs are needed. These drugs inhibit the (a) (A) → (Q); (B) → (R); (C) → (S)
enzymes which catalyse the degradation of nor-adrenaline. If the (b) (A) → (Q); (B) → (P); (C) → (R)
enzyme is inhibited, this important neurotransmitter is slowly
(c) (A) → (R); (B) → (P); (C) → (S)
metabolised and can activate its receptor for longer period of
(d) (A) → (R); (B) → (P); (C) → (R)
time, thus counteracting the effect of depression. Iproniazid and
phenelzine are two such antidepressant drugs.
Ans. (b)
The correct match is :
15 The following molecule acts as an A → (Q), B → (P), C → (R)
N (A) Norethindrone It is an antifertility drug(Q ) containing
(CH2)2 synthetic progesterone derivative. [Other similar drug, is
N ethinylestradiol (novestrol)].
(Brompheniramine) (B) Ofloxacin It is an antibiotic (P), i.e produced wholly or partly
by chemical synthesis with low concentration of
microorganism.[Some other similar drugs : Penicillin,
chloramphenicol, salvarsan etc.]
Br
(C) Equanil (meprobamate) It is a mild tranquilizer for relieving
[2020, 5 Sep Shift-II]
hypertension. It relieve anxiety, stress, excitement by
(a) antiseptic (b) anti-depressant inducing a sense of well being.
(c) anti-bacterial (d) anti-histamine (Other similar drug is chlordiazepoxide.)
440 JEE Main Chapterwise Topicwise Chemistry

19 Which of the following compounds is not an antacid? Ans. (c)

[JEE Main 2015] O
(a) Aluminium hydroxide
(b) Cimetidine O  C  CH3
(c) Phenelzine
(d) Ranitidine COOH
Ans. (c)
Aluminium hydroxide Al (OH) 3, cimetidine and ranitidine are A
antacids while phenelzine is not. o-acetyl salicylic acid
aspirin (Analgesic)
H
N CH3
N

N S C TOPIC 2
N NHCN
H
Chemicals in Food
Cimetidine
22 Match List-I and List-II.
List-I
Me2N S List-II
O (Chemical (Used as)
CH (NO2) compound)
C A. Sucralose 1. Synthetic detergent
N NHMe B. Glyceryl ester of stearic 2. Artificial sweetener
H
Ranitidine acid
C. Sodium benzoate 3. Antiseptic
Phenelzine is a tranquilizer, not an antacid. D. Bithionol 4. Food preservative
H Choose the correct match. [2021, 17 March Shift-II]
N NH2
A B C D A B C D
(a) 4 3 2 1 (b) 2 1 4 3
(c) 3 2 4 1 (d) 1 2 4 3
Ans. (b)
20 Which one of the following types of drugs reduces The correct matches are A-2, B-1, C-4, D-3.
fever ? [AIEEE 2005] A. Sucralose → Artificial sweetener
(a) Tranquiliser (b) Antibiotic Artificial sweetener is the sugar that is sweet like sugar but
(c) Antipyretic (d) Analgesic has zero or low calories. Artificial sweeteners can be plant
extract or chemical synthesised. Saccharin, aspartame,
Ans. (c) sodium cyclamate and sucralose are the examples of
Antipyretic drugs reduce fever. Analgesic relieve in pain, artificial sweeteners.
antibiotics act against bacterial infections while tranquilisers are B. Glyceryl ester of stearic acid→ Synthetic detergent Esters
used against mental disorders. of stearic acid are used in synthesis of soaps and
detergents.
C. Sodium benzoate→ Food preservative
21 Compound A given below is [AIEEE 2002]
The food is oxidised or hydrolysed by several factors such
OCOCH3 as air that is known as aerial oxidation, or by moisture,
bacteria and light.
COOH
Sodium benzoate has an aromatic ring that can stabilise
the free radical which causes the oxidation of food.
Sodium benzoate is a food preservative.
A D. Bithionol → Antiseptic
Bithionol is added to soap to impart antiseptic property. It
(a) antiseptic (b) antibiotic
reduces odour produced by bacterial decomposition of
(c) analgesic (d) pesticide
organic matter on the skin.
Chemistry in Everyday Life 441

23 A chemist has 4 samples of artificial sweetener A, B, C TOPIC 3

and D. To identify these samples, he performed Cleaning Agents
certain experiments and noted the following
observations :
24 Which one of the following chemical agent is not being
(i) A and D both form blue-violet colour with used for dry cleaning of clothes ?
ninhydrin. [2021, 25 July Shift-I]
(ii) Lassaigne extract of C gives positive AgNO 3 test (a) H2O2 (b) CCl4 (c) Liquid CO2 (d) Cl2C == CCl2
and negative Fe 4 [Fe(CN) 6] 3 test. Ans. (b)
(iii) Lassaigne extract of B and D gives positive sodium CCl 4 (carbon tetrachloride) was commonly blended with other
nitroprusside test. solvents for use as a dry cleaning solvent. Due to its high toxicity
Based on these observations which option is correct? and tendency to corrode equipment. Carbon tetrachloride is no
[2020, 8 Jan Shift-I]
longer used as a dry cleaning solvent.
(a) A : Alitame; B : Saccharin ; Other solvents are,
C : Aspartame; D : Sucralose H2O2 - Bleaching agent in laundry.
(b) A : Saccharin; B : Alitame; CO2 - Dry cleaning agent for clothes.
C : Sucralose; D : Aspartame CCl2 == CCl2 → Dry cleaning agent for clothes.
(c) A : Aspartame; B : Alitame;
25 Sodium stearate CH3 (CH2 ) 16 COO − Na + is an anionic
Ans. (d)
surfactant which forms micelles in oil.
Based on the observations, given in question, A : Aspartame, B :
Choose the correct statement for it from the
Saccharin, C : Sucralose, D : Alitame.
following. [2021, 22 July Shift-I]
(A) Aspartame Gives −
(a) It forms spherical micelles with CH3 (CH2 ) 16 group pointing
ninhydrin test
towards the centre of sphere.
(has amino
group). (b) It forms non-spherical micelles with COO − group
HO OMe pointing outwards on the surface.
NH −
(c) It forms spherical micelles with CH3 (CH2 ) 16 group pointing
NH2 outwards on the surface of sphere
(d) It forms non–spherical micelles with CH3 (CH2 ) −16 group
(B) Saccharin Positive test pointing towards the centre.
for S (sodium
nitroprusside
Ans. (a)
NH test) Micelles formed are spherical with hydrocarbon part towards the
S centre of sphere.

(C) Sucralose CH2OH Positive

AgNO 3 test Stearate
Cl O O due to Cl and ion
OH HO no nitrogen
Water
O ∴negative
CH2Cl Fe 4 [Fe(CN) 6] 3
OH OH test.

(D) Alitame NH2 O Gives Ionic

ninhydrin test micelle
NH (has amino
S —NH OH
group) and
sodium
nitroprusside
test (has
sulphur). Carbon chain (Hydrocarbon)
442 JEE Main Chapterwise Topicwise Chemistry

The formation of a micelle is a response to the amphipathic Ans. (a)

nature of fatty acids, meaning that they contain both hydrophilic
An ionic micelle is formed due to presence of hydrophobic chain.
regions (polar head groups) as well as hydrophobic regions (the
long hydrophobic chain). It can easily be formed by the addition of
Å
26 Green chemistry in day–to–day life is in the use of N N
[2021, 20 July Shift-I]
H3C CH3
(a) chlorine for bleaching of paper.
(b) large amount of water alone for washing clothes. s
SO4
(c) Tetrachloroethene for laundry.
(d) Liquified CO2 for dry cleaning of clothes.
Ans. (d)
28 Which of the following is an anionic detergent?
[JEE Main 2016]
Liquified CO2 for dry cleaning of clothes is in the use of green
(a) Sodium lauryl sulphate
chemistry in day to day life.
(b) Cetyltrimethyl ammonium bromide
Chlorine gas was used earlier for bleaching paper. Now a days,
hydrogen peroxide (H2O2 ) with suitable catalyst are used. (c) Glyceryl oleate
Earlier solvents like tetrachloroethylene were used in dry (d) Sodium stearate
cleaning of clothes but they pollute the ground water and are Ans. (a)
carcinogenic.
Sodium lauryl sulphate [(CH3 (CH2 ) 10 CH2OSO3−Na+ )]

27 An ionic micelle is formed on the addition of = Anionic detergent

[2020, 3 Sep Shift-II] Cetyltrimethyl ammonium bromide
+
(a)  CH3 
N N
  
H3C CH3  CH3 (CH2 ) 15 N  CH3  Br −
  
 CH3 
SO4–  
(b) liquid diethyl ether to aqueous NaCl solution = Cationic detergent
(c) sodium stearate to pure toluene excess water to liquid Glyceryl oleate [(C17 H32 COO) 3 C3H5 ]

PF6 = Non-ionic detergent

N N
(c) H3C CH3 Sodium stearate [C17H35 COO−Na+ ]
= Anionic soap
30
Principles Related to
Practical Chemistry
TOPIC 1 02 NO2
Detection of Extra Elements
HNO3
and Functional Groups H2SO4

01 Which one of the following tests used for the In the above reaction 3.9 g of benzene on nitration gives 4.92 g of
identification of functional groups in organic nitrobenzene. The percentage yield of nitrobenzene in the above
reaction is ……… % (Round off to the nearest integer).
compounds does not use copper reagent ?
[2021, 27 Aug Shift-II] (Given, atomic mass C : 12.0 u, H : 1.0 u, O : 16.0 u, N : 14.0 u)
[2021, 17 March Shift-I]
(a) Barfoed’s test
(b) Seliwanoff’s test Ans. (80)
HNO
(c) Benedict’s test C6H6  3→ C6H5NO2 (Molar mass = 123)
H2 SO4
(d) Biuret test for peptide bond
 39
. 
Ans. (b) Moles of C6H6 =   = 0.05
 78 
Barfoed’s test is used to detect monosaccharides.
39
.
In this test, the aldehyde group of monosaccharides reduces So, moles of C6H5NO2 formed should be .
Cu(II) acetate to Cu(I) oxide which result in the formation of brick 78
red ppt. Mass of C6H5NO2 = Moles × Molar mass
RCHO + 2 Cu2 + + H2O → RCOOH + Cu2O ↓ + 4H+ 39
.
= × 123 = 6.15 g
(ppt. ) 78
Benedict’s test is used to test the presence of reducing sugar.
Copper (II) sulphate is used in Barfoed’s test. By conserving moles of carbon, mole or C6H5NO2 .
Weight actually formed
Biuret test is used to test the presence of peptide bond. The % yield = × 100
biuret reagent contains hydrated copper sulphate, sodium Weight theoretical
hydroxide and Rochelle salt (sodium-potassium tartarate). When .
492
= × 100 = 80%
the aqueous, solution of protein is treated with this reagent, the 6.15
solution turns purple confirming the presence of amide bond.
144444424444443

O 03 In Duma's method of estimation of nitrogen, 0.1840 g of

—
—
—

—
—
O —
an organic compound gave 30 mL of nitrogen collected
HN NH
at 287 K and 758 mm of Hg pressure. The percentage
—

Peptide
R—C Cu 2+ C—R chain composition of nitrogen in the compound is ……… .
—
—

—
——

(Round off to the nearest integer).

—
O —
O
HN NH
[Given: Aqueous tension at 287 K = 14 mm of Hg]
—
—

[2021, 16 March Shift-II]

Chelated complex of Cu2 + ions formed gives purple colour to the Ans. (19)
solution.
Given, mass of organic compound 0.1840 g
So, correct answer is option (b) Seliwanoff’s test which is used to
distinguish between ketoses and aldoses. The Seliwanoff’s Total pressure = 758 mm of Hg
reagent contains resorcinol and HCl. Aqueous tension = 14 mm of Hg
444 JEE Main Chapterwise Topicwise Chemistry

Partial pressure of dry N2 = 758 − 14 = 744 mm of Hg NH2

For N2 , NaNO2
(IV)
V = 30 mL =0.03 L HCl
T = 287 K Diazotisation
744
p = 744 mm of Hg = atm reaction
760 r s
N N Cl
pV 744 0.03
So, moles of N2 (n) = = ×
RT 760 0.0821 × 287
Kjeldahl method
. × 10 −3 moles of N2
n = 125 Benzene is not applicable
Weight of N2 = Moles × Molar mass diazonium
for N N
chloride
= 1.25 × 10 −3 × 28 = 35 × 10 −3 g N or azo group
% composition of N2
Mass of N2 35 × 10 −3 So, products of reactions (c) and (d) (option-a) fail to give
= × 100 = × 100 = 19% Kjeldahl’s method. So, option (a) is correct.
Mass of organic compound 0.1840

04 The Kjeldahl method of nitrogen estimation fails for 05 The correct match between Item I and Item II is
which of the following reaction products? Item I Item II
[2020, 3 Sep Shift-I]
NO2 CN A. Ester test P. Tyr
B. Carbylamine test Q. Asp
Sn/HCl LiAlH4
I. II. C. Phthalein dye test R. Ser
S. Lys
CH2CN
NH2 [2019, 11 Jan Shift-II]
NaNO2
(i) SnCl2+HCl IV.
III. HCl (a) A → Q; B → S; C → R
(ii) H2O
(b) A → R, B → Q; C → P
(a) III and IV (b) I and IV (c) I, III and IV (d) II and III (c) A → R; B → S; C → Q
Ans. (a) (d) A → Q; B → S; C → P
Complete reactions I, II, III, IV are as follows : Ans. (d)
NO2 The correct match is :
Sn/HCl
(I) [H] A → (Q); (B) → (S) (C) → (P)
Nitrobenzene R ⇒ CH2—COOH C2H5OH/H2SO4/∆
Asp [Aspartic acid]
NH2 [Ester test] (A)
‘N’ of NH2 can be (Q)
Sweet smell
estimated by of ester
Kjeldahl method
R ⇒ (CH2)4—NH2 CHCl3/alc.KOH
Aniline Lys [Lysine]
[Carbylamine test] (B)
CN OOC (S)
LiAlH4 CH— R Foul smell
(II) of isocyanide
[H] H 3N
General
CH2 NH2 formula of
O, Conc. H2SO4/∆
amino acid

R ⇒ ¾CH2 OH
Benzylamine
Tyr [Tyrosine]
(P) [Phthalein dye test] (C)
CH2CN
(i) SnCl2 + HCl Resultant colourless
(III) solution turns pink
(ii) H2O
(Stephen reduction)
(A) Ester test confirms the presence of
CH2 CH O COOHgroup.
(B) Carbylamine test confirms the presence of
NH2 group (1°).
(2-phenyl ethanal) (C) Phthalein dye test confirms the presence of phenolic OH
This compound does not contain group.
‘N’. So, Kjeldahl method is not applicable.
Principles Related to Practical Chemistry 445

TOPIC 2 Ans. (c)

(A) Lassaigne test is used to detect N, S, P, X elements.
Chemistry Involved in Organic The elements present in the compound are converted from
and Inorganic Compounds covalent form into the ionic form by fusing the compound
with sodium metal. Following reactions take place.
∆
Na + C + N → NaCN
06 An inorganic compound 'X' on treatment with ∆
concentrated H2SO 4 produces brown fumes and gives 2Na + S → Na2S
dark brown ring with FeSO 4 in presence of Na + X →∆
NaX (X = Cl, Br or I )
concentrated H2SO 4 . Also compound 'X' gives (B) Carbon and hydrogen are detected by heating the
precipitate 'Y ', when its solution in dilute HCl is treated compound with copper (II) oxide.
with H2S gas. The precipitate 'Y ' on treatment with C + 2CuO → 2Cu + CO2
concentrated HNO 3 followed by excess of NH4OH 2H + CuO → Cu + H2O
further gives deep blue coloured solution, compound 'X' (C) Halides are detected by silver nitrate.
is [2021, 20 July Shift-I] They form precipitate of AgXexcept fluorine.
(a) Co(NO 3)2 (b) P(NO2 )2 Ag + (aq) +X − (aq) → AgX (s )
(c) Cu(NO 3)2 (d) Pb(NO 3)2 (D) Sodium fusion extract gives black precipitate of PbS with
Ans. (c) acetic acid and lead acetate to confirm the presence of
sulphur.
Compound ‘X’ is copper nitrate, i.e. Cu(NO3)2 is an inorganic
compound. On treatment with concentratedH2SO4 produces Na2S + (CH3COO)2 Pb → PbS + 2CH3 COONa
Black ppt.
brown fumes and gives dark brown ring withFeSO4 in presence
of concentrated H2SO4 . Chemical reaction is as follows
NO−3 + H2SO4 → NO2 ↑ + H2O
08 Seliwanoff test and xanthoproteic test are used for the
X (Conc.) (Brown fumes) identification of ……… and ……… respectively.
(Anion) [2021, 26 Feb Shift-II]
FeSO4 + H2SO4 + NO3− → [Fe(H2O) 5 (NO)]
(Sol) (Conc. ) X (a) aldoses, ketoses (b) proteins, ketoses
(Dark brown )
(c) ketoses, proteins (d) ketoses, aldoses
Cu2 + is a group II cation with group II reagents
(HCl/H2S), it gives black coloured precipitates. These precipitates Ans. (c)
gives blue colour solution on treatment withHNO3 followed by Seliwanoff and xanthoproteic tests are used for the
excess of NH4OH. identification of ketoses and proteins respectively.
Cu2 + + (Dil HCl + H2S) → CuS ↓ Seliwanoff test It is a chemical test which distingusihes between
X (Group-II, reagent) (Black ppt.) aldose sugars (e.g. glucose and maltose) and ketose sugars (e.g.,
(Cation) Y
Conc. HNO3 fructose and sucrose). The test is based on the principle that,
CuS → Cu(NO3)2 + NO2 + H2SO4 + H2O when heated with acid, ketoses are more readily dehydrated
Y X than aldoses. The reagents used in the test consist of
(Soluble) conc. HCl and resorcinol.
Excess NH OH sol. For ketoses, a deep cherry red colour is formed rapidly indicating
4
→ [Cu(NH3)2 ]2 +
(Deep blue a positive test.
colour) Xanthoproteic test It is qualitative test to detect the presence of
∴ X → Cu(NO3)2
protein soluble in a solution usingHNO3.
Copper nitrate
In this test, solution of protein is first heated with
conc. HNO3 and then the mixture is neutralised by 40% NaOH
07 Match List-I with List-II. solution. If the colour changes from yellow to orange, this
confirms presence of a protein.
List-I List-II
(i) Conc . HNO / ∆
(Test / Reagents / (Species detected) Protein solution →
3
Yellow colouration which
(ii) 40%NaOH
Observation(s))
finally changes into orange colour.
A. Lassaigne’s test (i) Carbon
B. Cu(II) oxide (ii) Sulphur 09 Which of the following is a false statement?
C. Silver nitrate (iii) N, S, P, and halogen (a) Carius tube is used in the estimation of sulphur in an organic
D. The sodium fusion extract (iv) Halogen specifically compound [2021, 26 Feb Shift-I]
gives black precipitate with
acetic acid and lead acetate (b) Carius method is used for the estimation of nitrogen in an
organic compound
The correct match is [2021, 16 March Shift-II] (c) Phosphoric acid produced on oxidation of phosphorus
(a) A-(iii), B-(i), C-(ii), D-(iv) present in an organic compound is precipitated asMg2P2O7
(b) A-(i), B-(iv), C-(iii), D-(ii) by adding magnesia mixture
(c) A-(iii), B-(i), C-(iv), D-(ii) (d) Kjeldahl's method is used for the estimation of nitrogen in an
(d) A-(i), B-(ii), C-(iv), D-(iii) organic compound
446 JEE Main Chapterwise Topicwise Chemistry

Ans. (b) The first aid for removal of HCl should be basic in nature. But
Statement (b) is false whereas all other statements are true. NaOH is a hard base whereasNH4OH is a very soft base. So, the
There are two methods for estimation of nitrogen in an organic best substance to remove the spill (HCl) is NaHCO3.
compound which are Duma’s method and Kjeldahl’s method. HCl + NaHCO3 → NaCl + CO2 ↑ + H2O
So, the statement in option (b) is false.
13 An organic compound X showing the following solubility
10 Which of the following compound is added to the profile is [2019, 8 April Shift-I]
sodium extract before addition of silver nitrate for Water
Insoluble
testing of halogens? [2021, 25 Feb Shift-II]
X
5% HCl
(a) Hydrochloric acid (b) Sodium hydroxide Insoluble
(c) Nitric acid (d) Ammonia
10% NaOH
Ans. (c) Soluble
Nitric acid is added to sodium extract before addition of silver 10% NaHCO3
Insoluble
nitrate for testing halogens. Because it decomposes NaCN and
Na2S or else they interfere in the test. (a) o -toluidine (b) oleic acid
The reaction are as follows : (c) m-cresol (d) benzamide
NaCN + HNO3 → NaNO3 + HCN ↑ Ans. (c)
Na2S + HNO3 →NaNO3 + H2S ↑ m-cresol is the organic compound that shows the following
Sodium extract Nitric acid solubility profile.
Water
CH3 Insoluble
11 On heating compound (A) gives a gas (B) which is a 5% HCl
Insoluble
constituent of air. This gas when treated with H2 in the 10% NaOH
presence of a catalyst gives another gas (C) which is Soluble
OH
basic in nature. m-cresol 10% NaHCO3
Insoluble
(A) should not be [2020, 2 Sep Shift-I]
m-cresol on reaction with 10% NaOH forms 3-methyl
(a) NH4 NO2 (b) (NH4)2 Cr2O 7
sodiumphenoxide ion.
(c) NaN3 (d) Pb (NO 3)2
Ans. (d) OH O–Na+

(A) can beNH4NO2 or (NH4 )2 Cr2O7 or NaN3 but not Pb(NO3)2 10% NaOH
because each option a, b, c on heating liberatesN2 gas (B).
CH3 CH3
∆ N + 2H O
NH4NO2 → 2 2
It does not react withH2O, 5% HCl and 10%NaHCO3.
∆ N + Cr O + 4H O
(NH4 )2 Cr2O7 → Oleic acid (C18H34O2 ) is soluble in 10% NaOH and 10%NaHCO3 due
2 2 3 2
to the presence of COOH group.
∆ 3N + 2Na
2NaN3 → O
2

But, Pb(NO3)2 on heating liberatesNO2 and O2 . Benzamide (C6H5 C NH2) is insoluble in 5% HCl, 10% NaOH and

∆ 2PbO + 4NO + O 10% NaHCO3 due to the presence CONH2 group. o-toluidine is
2Pb(NO3)2 → 2 2 soluble in 5%. HCl due to presence of basic group ( NH2 )
N2 is a constituent of air (N2 = 78%, O2 = 21% by volume). It reacts attached to ring.
with H2 in presence of a catalyst to give ammoniaNH3 (C) gas
which is basic in nature. 14 The organic compound that gives following qualitative
200 atm, 773 K analysis is [2019, 9 April Shift-I]
N2 + 3H2 → 2NH3
Fe (catalyst) Test Inference
(i) Dil. HCl Insoluble
(ii) NaOH solution Soluble
12 If you spill a chemical toilet cleaning liquid on your hand,
(iii) Br2 /water Decolourisation
your first aid would be [2020, 2 Sep Shift-II]
(a) vinegar (b) aqueous NaOH NH2 OH
(c) aqueous NaHCO 3 (d) aqueous NH3 (a) (b)
Ans. (c)
NH2 OH
Toilet cleaning liquid contains mainly HCl and surfactants like
classical ATX. HCl is corrosive to our skin. So, it should be (c) (d)
removed immediately.
Principles Related to Practical Chemistry 447

Ans. (b) Ans. (b)

Phenol (ArOH) is insoluble in dil. HCl and readily soluble in NaOH Phenolic
solution. It reacts withBr2 /water to give 2, 4, 6-tribromophenol. OH –OH group
FeCl3
It readily decolourises the yellow colour ofBr2 water. Reactions (Ferric chloride)
involved are as follows : (A) Violet colouration
(R)
OH H 3C CH3
Cl
Chloroxylenol (Dettol)
Dil. HCl no reaction
· OH
H 3C C≡≡CH
Phenol
H Dil. KMnO4/5°C/OH –
H Pink colour of
(Acidic in nature) (Baeyer’s test)
(B) (S)
KMnO4 gets
– + H H
OH ONa discharged
O
Norethindrone

· NaOH C C
(Double bond)

Phenol Sodium O
(Acidic in nature) phenoxide
(C) H2N S N
OH OH H N
Br Br O
Primary Sulphapyridine
Br2 Water amine (–NH2) CHCl3 + KOH (alc.)
· Foul smell
(Carbylamine
Phenol test) (P) of isocyanide
Br O
White ppts. H H CH3
(2, 4, 6-tribromophenol)
S
(D) R C NH
CH3
N COOH
15 Which one of the following is likely to give a precipitate O
H
with AgNO 3 solution? [2019, 9 April Shift-II] Penicillin
NaHCO3(aq)
(a) CH2 == CH  Cl (b) CCl4 Becomes soluble
(Sodium
(c) CHCl3 (d) (CH3) 3CCl hydrogen with effervescence
carbonate) of CO2 gas
Ans. (d) (Q)

(CH3) 3 CCl gives a precipitate with AgNO3 solution because it Thus, the correct match is :
forms stable carbocation. (i.e. tertiary) that readily combines
A → R; B → S; C → P; D → Q
with AgNO3 to give precipitates of AgCl.
CH3 17 The correct match between item ‘I’ and item ‘II’ is
 + Item ‘I’ Item ‘II’
CH3  C  Cl + AgNO3 → (CH3 )3 C + AgCl
(Compound) (Reagent)
 (White
ppts. )
CH3 (A) Lysine (P) 1-naphthol
(B) Furfural (Q) Ninhydrin
CH2 == CH  Cl forms unstable carbocation.
(C) Benzyl alcohol (R) KMnO 4
Hence, it does not readily react with AgNO3.
(D) Styrene (S) Ceric ammonium
nitrate
16 The correct match between Item-I and Item-II is [2019, 10 Jan Shift-II]

Item-I (Drug) Item- II (Test) Codes

A B C D A B C D
A. Chloroxylenol P. Carbylamine test
(a) Q R S P (b) R P Q S
B. Norethindrone Q. Sodium hydrogen carbonate test (c) Q P S R (d) Q P R S
C. Sulphapyridine R. Ferric chloride test Ans. (c)
D. Penicillin S. Bayer’s test (A) → Q; B → (P) ; C → (S), D → (R)

[2019, 9 Jan Shift-I] (A) Lysine (R=–(CH2)4–NH2)

NH2
(a) A→ R ; B→ P ; C→ S ; D→ Q Ninhydrin test (B)
R CH Violet
(b) A→ R ; B→ S ; C→ P ; D→ Q COOH O
colouration
(c) A→ Q ; B→ P ; C→ S ; D→ R OH
(Ninhydrin),
(d) A→ Q ; B→ S ; C→ P ; D→ R OH boil
O
448 JEE Main Chapterwise Topicwise Chemistry

OH x = 0.02 M
Molar mass of KMnO4 = 158 g / mol
(B)
CHO + Strength = x × 158 = 0.02 × 158 = 3.16 g / L
O
(Furfural) = 316 × 10 −2 g /L
CH2SO4
∆ Violet colouration ∴ x ≈ 316.
Molisch Test(P)
(Molisch reagent) 20 The OH− concentration in a mixture of 5.0 mL of 0.0504
CH2OH Ceric ammonium M NH4Cl and 2 mL of 0.0210 M NH3 solution is x × 10 −6 M.
(C)
nitrate (s) [CAN] The value of x is ……… . (Nearest integer)
50% CH3COOH CHO [Given, K w = 1 × 10 −14 and K b = 1.8 × 10 −5 ]
(Benzyl alcohol)
[2021, 26 Aug Shift-I]
Ans. (3)
(Benzaldehydel)
– Number of moles of NH4 Cl = concentration of NH4 Cl × volume of
dil. KMnO4/OH /Cold (R) NH4 Cl
(D)
(Pink) OH = 0.0504 M × 5 mL = 0.2520 millimoles
OH
(Styrene) Total volume of solution in mixture
= Volume of NH 4 Cl solution + volume of NH 3 solution
H H
H = 5 + 2 = 7 mL.
+Mn2+(Colourless)
Concentration of NH4 Cl in mixture
Number of moles of NH4 Cl
=
Total volume
18 The compound formed in the positive test for nitrogen 0.2520 millimole
with the Lassaigne solution of an organic compound is = = 0.036 M
7 mL
[AIEEE 2004]
Number of moles of NH3 = concentration of NH3 × volume of NH3
(a) Fe 4 [Fe(CN) 6] 3 (b) Na3 [Fe(CN) 6]
= 0.0210 × 2 = 0.042 millimole
(c) Fe(CN) 3 (d) Na4 [Fe(CN) 5 NOS] Number of moles of NH3
Ans. (a) Concentration of NH3 in mixture =
Total volume
If nitrogen is present in organic compound, then sodium extract 0.042
= = 0.006 M
contains NaCN. 7
Fuse
Na + C + N → NaCN According to Handerson’s equation
FeSO4 + 6NaCN → Na4 [Fe(CN) 6 ] + Na2SO4 [Salt]
pOH = pK b + log
(A ) [Base]
A changes to Prussian blueFe4 [Fe(CN) 6 ] 3 on reaction withFeCl 3. [Salt] = [NH4 Cl]
4FeCl 3 + 3Na4 [Fe(CN) 6 ] → Fe4 [Fe(CN) 6 ] 3 + 12NaCl [Base] = [NH 3]
0.036
pOH = − log K b + log
0.006
TOPIC 3 pOH = − log(1.8 × 10 −5 ) + 0.7782
pOH = 5.523
Chemistry Involved in Titrimetric Exercise
Q pOH = − log [OH− ]
So, [OH− ] = 2.9 × 10 −6 ≈ 3 × 10 −6
19 When 10 mL of an aqueous solution of KMnO 4 was
∴ x =3
titrated in acidic medium, equal volume of 0.1 M of an
aqueous solution of ferrous sulphate was required for 21 Given below are two statements.
complete discharge of colour. Statement I In the titration between strong acid and
The strength of KMnO 4 in g/L is weak base methyl orange is suitable as an indicator.
……… × 10 − 2 . (Nearest integer) Statement II For titration of acetic acid with NaOH
[Atomic mass of K = 39, Mn = 55, O = 16] phenolphthalein is not a suitable indicator.
[2021, 27 Aug Shift-I]
In the light of the above statements, choose the most
Ans. (316)
appropriate answer from the options given below.
Let molarity of KMnO4 = x [2021, 26 Aug Shift-I]
KMnO4 + FeSO4 → Fe(SO4 ) 3 + Mn2 + (a) Statement I is false but statement II is true.
n= 5 n= 1 (b) Statement I is true but statement II is false.
(Equivalent of KMnO4 reacted) = (Equivalent of FeSO4 reacted) (c) Both statement I and statement II are true.
⇒ 5x × 10 = 1 × 0.1 × 10 (d) Both statement I and statement II are false.
Principles Related to Practical Chemistry 449

Ans. (b) 17.5

= 0.1 ×
In the titration of strong acid with the weak base methyl orange 1000
is an suitable indicator. Initially, pH of weak base is high, as acid Equivalent of HCl = 1.75 × 10 −3
is added pH falls slowly and equivalence point is attained. Equivalents of NaOH = 1.75 × 10 −3
(Equivalence point is point when chemical equivalent quantities Weight of NaOH = Equivalent of NaOH × equivalent weight of
of acid and base are mixed). After equivalence point pH falls NaOH
sharply. So, methyl orange having pH range 3.2 - 4.4 will work as
= 40 × 1.75 × 10 −3 = 0.07 g
suitable indicator. Methyl orange shows red colour in acidic
medium and yellow colour in basic medium. Now, weight % of NaOH
0.07 70
Hence, statement I is true. = × 100 = = 17.5%
0.4 4
In titration of weak acid and strong base initially pH of weak acid
is below 7. As strong base is added pH increases slowly and Similarly for Na2 CO3,
equivalence point is attained. After equivalence point pH Equivalent of HCl = Equivalent of Na2 CO3
abruptly increases. So, phenolphthalein having pH range 1.5
Equivalent of Na2 CO3 = 0.1 × = 0.15 × 10 −3
8.2–10.0 will work as suitable indicator. Phenolphthalein is 1000
colourless in acidic solution whereas pink in basic solution. Weight of Na2 CO3 = Equivalent of Na2 CO3
Hence, statement II is false.
× equivalent weight ofNa2 CO3
22 Consider titration of NaOH solution versus = 0.15 × 10 −3 × 106 = 159. × 10 −3 g
−3
1.25 M oxalic acid solution. At the end point following 15.9 × 10
Weight % ofNa2 CO3 = × 100
burette readings were obtained. 0.4
= 0.039 × 100 = 39 . %− ~ 4%
(i) 4.5 mL (ii) 4.5 mL (iii) 4.4 mL
(iv) 4.4 mL (v) 4.4 mL 24 While titrating dilute HCl solution with aqueous NaOH,
If the volume of oxalic acid taken was 10.0 mL, then which of the following will not be required?
the molarity of the NaOH solution is ……… M. (Rounded (a) Pipette and distilled water [2020, 2 Sep Shift-I]
off to the nearest integer) [2021, 25 Feb Shift-II] (b) Burette and porcelain tile
Ans. (6) (c) Bunsen burner and measuring cylinder
Average burette reading = Volume of NaOH solution (V1) (d) Clamp and phenolphthalein
4.5 + 4.5 + 44
. + 44
. + 44
. Ans. (c)
=
5 Titration (neutralisation) of dil. HCl solution with aqueous NaOH
= 444
. mL will require the following steps and apparatus. NaOH solution
Strength of NaOH solution = S 1(M) (say) = S 1 (N) made with distilled water and solid NaOH is taken in a burette
Volume of oxalic acid solution (V2 ) = 10 mL and then it is fitted with a clamp.
Strength of oxalic acid solution (S2 ) = 125
. M 3= 125. × 2N A given volume of standard HCl solution (dilute) is then pipetted
So, V1S 1 = V2 S2 (QLaw of equivalence) out and taken in a conical flask for titration. Then, few drops of
VS 10 × (1.25 × 2) phenolphthalein indicator is added in this HCl solution. So, we do
⇒ S1 = 2 2 = = 5.63 N
V1 4.44 not require measuring cylinder and bunsen burner as the
~− 6 M = 6 M titration takes place at room temperature.
Note n-factor of NaOH = 1
25 The volume strength of 8.9 M H2O 2 solution calculated
n-factor of H2 C2O4 = 2 (oxalic acid)
N =M×n at 273 K and 1 atm is .......... . (R = 0.0821 L atm K −1
mol −1 ) (rounded off to the nearest integer).
23 0.4 g mixture of NaOH, Na 2CO 3 and some inert [2020, 3 Sep Shift-I]

N Ans. (100.00)
impurities was first titrated with HCl using
10 x
“x vol” H2O2 = M H2O2
phenolphthalein as an indicator, 17.5 mL of HCl was 112
.
required at the end point. After this methyl orange was x
So, = 89
.
added and titrated. 1.5 mL of same HCl was required for 112
.
the next end point. The weight percentage of Na 2CO 3 in ⇒ x = 112
. × 89
. = 9968
. −~ 100
the mixture is …………. (Rounded off to the nearest So, at NTP volume strength of 8.9 MH2O2 solution is 100 vol.
integer). [2021, 25 Feb Shift-I]
Ans. (4) 26 A 20.0 mL solution containing 0.2g impure H2O 2 reacts
As given, NaOH and Na2 CO3 is titrated with N/10 HCl. completely with 0.316 g of KMnO 4 in acid solution. The
For NaOH, purity of H2O 2 (in%) is ............. (molecular weight of
Equivalents of NaOH = Equivalents of HCl H2O 2 = 34; molecular weight of KMnO 4 = 158).
Equivalents of HCl = Normality × Volume (L) [2020, 4 Sep Shift-I]
450 JEE Main Chapterwise Topicwise Chemistry

Ans. (85)
Given, volume of solution = 20.0 mL
Impure sample ofH2O2 = 0.2 g
pH
Mass of KMnO4 = 0.316 g
Impure H2O2 react withKMnO4 (acidic)
+7 −1 +2 0 V(mL)
KMnO4 + H2O2 → Mn + O2

KMnO4 acts as an oxidising agent, In this case, both the titrants are completely ionised.
+ −
+7 +2
− HCl + NaOH -Na Cl + H O
Mn + 5e → Mn 2

(valency factor = 5) ⊕
−1 0
As H is added to a basic solution, [OHÈ] decreases and [H+ ]
−
O2 → O2 + 2e increases. Therefore, pH goes on decreasing. As the equivalence
(valency factor = 2) point is reached, [OHÈ] is rapidly reduced. After this point [OH È]
We have to compare bothKMnO4 and H2O2 . decreases rapidly and pH of the solution remains fairly constant.
Thus, there is an inflexion point at the equivalence point.
(Mass equivalent)H O2 = (Mass equivalent)KMnO 4
2
The difference in the volume of NaOH solution between the end
Weight point and the equivalence point is not significant for most of the
× 1000
molecular weight/valence factor commonly used indicators as there is a large change in the pH
weight value around the equivalence point. Most of them change their
= × 1000
molecular weight/valence factor colour across this pH change.
(weight)H 2 O 2 0.316
× 1000 = × 1000 28 25 mL of the given HCl solution requires 30 mL of 0.1 M
34 /2 158 / 5 sodium carbonate solution. What is the volume of this
0.316 34 26.86 HCl solution required to titrate 30 mL of 0.2 M aqueous
(weight)H = ×5× =
2 O2 158 2 158 NaOH solution? [2019, 11 Jan Shift-II]

(weight)H = 0.17 g (a) 75 mL (b) 25 mL

2 O2
(c) 12.5 mL (d) 50 mL
(Pure)H 0.17
(Purify)H = 2 O2
× 100 = × 100 = 85% Ans. (b)
2 O2 (Impure)H 0.2
2 O2 The reaction of HCl withNa2 CO3 is as follows:
2HCl + Na2 CO3 → 2NaCl + H2O + CO2
27 In an acid-base titration, 0.1 M HCl solution was added to We know that, Meq of HCl = Meq of Na2 CO3
the NaOH solution of unknown strength. Which of the 25
× 1 × MHCl =
30
× 0.1 × 2
following correctly shows the change of pH of the 1000 1000
titration mixture in this experiment? 30 × 0.2 6
MHCl = = M
[2019, 9 April Shift-II] 25 25
The reaction of HCl with NaOH is as follows:
NaOH + HCl → NaCl + H2O
pH pH
Also, M eq of HCl = M eq of NaOH
6 V 30
× 1× = × 0.2 × 1
V(mL) V(mL) 25 1000 1000
(A ) (B)
V = 25 mL

29 50 mL of 0.5 M oxalic acid is needed to neutralise 25 mL

pH pH of sodium hydroxide solution. The amount of NaOH in 50
mL of the given sodium hydroxide solution is
[ 2019, 12 Jan Shift-I]
V(mL) V(mL) (a) 40 g (b) 80 g (c) 20 g (d) 10 g
(C) (D) Ans. (*)
(a) (D) (b) (A) (c) (B) (d) (C) The reaction takes place as follows,
Ans. (b) H2 C2O4 + 2NaOH → Na2 C2O4 + 2H2O
The graph that shows the correct change of pH of the titration Now, 50 mL of 0.5 M H2 C2O4 is needed to neutralize 25 mL of
mixture in the experiment is NaOH.
Principles Related to Practical Chemistry 451

∴ Meq of H2 C2O4 =Meq of NaOH 32 Which one of the following set of elements can be
50 × 0.5 × 2 = 25 × MNaOH × 1 detected using sodium fusion extract ?
MNaOH = 2M [2021, 27 July Shift-II]
Number of moles (a) Sulphur, nitrogen, phosphorus, halogens
Now, molarity =
Volume of solution (in L) (b) Phosphorus, oxygen, nitrogen, halogens
Weight/molecular mass (c) Nitrogen, phosphorus, carbon, sulphur
=
Volume of solution (in L) (d) Halogens, nitrogen, oxygen, sulphur
w NaOH 1000 Ans. (a)
2= ×
40 50
By sodium fusion extract we can detect sulphur, nitrogen,
2 × 40 × 50
w NaOH = = 4g phosphorus and halogens. The elements present in the
1000 compound are converted from covalent into ionic form by fusing
Thus, (*) none option is correct. the compound with sodium metal. Following reactions take
place :
30 29.5 mg of an organic compound containing nitrogen ∆
was digested according to Kjeldahl’s method and the Na + C + N → NaCN
evolved ammonia was absorbed in 20 mL of 0.1M HCl ∆
2Na + S → Na2S
solution. The excess of the acid required 15 ML of 0.1 M
∆
NaOH solution for complete neutralization. The Na + X → NaX (X = Cl, Br or I)
percentage of nitrogen in the compound is [AIEEE 2010] ∆
3Na + PO34− → Na3PO4
(a) 59.0 (b) 47.4 (c) 23.7 (d) 29.5
Ans. (c) 33 In Tollen’s test for aldehyde, the overall number of
Mass of organic compound = 29.5 mg electron(s) transferred to the Tollen’s reagent formula
mmoles of HCl = 20 × 0.1 = 2 mmoles
[Ag(NH3 ) 2] + per aldehyde group to form silver mirror is
mmoles of NaOH = 15 × 0.1 = 1.5 mmole
Involved reactions are
……… (Round off to the nearest integer).
[2021, 18 March Shift-II]
NH3 + HCl → NH4 Cl
Ans. (2)
(2 mmoles
initially taken) When an aldehyde is heated with freshly prepared Tollen’s
reagent i.e. [Ag(NH3)2 ] + , a bright silver mirror of Ag is formed.
HCl + NaOH →NaCl + H2O
AgNO3 + NaOH → AgOH + NaNO3
(Lewis acid) (1.5 mmoles
initially taken) 2AgOH → Ag2O + H2O
From the above equation, it is clear that Ag2O + 4NH3 + H2O →2Ag(NH3)2+ + 2OH−
mmoles of HCl reacted with NaOH = 2 − 1.5 = 0.5 mmol Tollen’s reagent
m moles of NH3 reacted in first equation with HCl = 0.5 × 17 mg Reaction of aldehyde with Tollen’s reagent take place as follows
Mass of NH3 = 0.5 × 17 mg = 8.5 mg O
14 O
Mass of N contained inNH3 = 8.5 mg × = 7 mg –e– OH
17 R H +
Ag Ag0 R H
7
Thus, % of N present in OC = × 100 = 23.7%
29.5 HO O OH
R H
R OH
TOPIC 4
OH
Qualitative Salt Analysis
O O O
OH –e–
31 To an aqueous solution containing ions such as R O R OH Ag
0
Ag+ R OH
Al 3+, Zn 2+, Ca 2+, Fe 3+, Ni 2+, Ba 2+ and Cu 2+ conc. HCl, −
Total 2e transfer to Tollen’s reagent.
was added followed by H2S. The total number of cations
precipitated during this reaction is/are
[2021, 27 July Shift-II]
34. If Fe 3+ and Cr 3+ both are present in group III of
(a) 1 (b) 3 (b) 4 (d) 2 qualitative analysis, then distinction can be made by
[AIEEE 2002]
Ans. (a)
2+ (a) addition of NH4OH in the presence of NH4Cl when only
Only Cu get precipitated when HCl followed by H2S was added.
Fe(OH) 3 is precipitated
Al 3+ and Fe3+ sulphides hydrolyse in water.Ni2 + and Zn2 + require
basic medium withH2S to form ppt. Ca2 + and Ba2 + sulphides are (b) addition of NH4OH in presence of NH4Cl when Cr(OH) 3 and
soluble. Fe(OH) 3 both are precipitated and on adding Br2 water and
Hence, we will recieve ppt. of only CuS. NaOH, Cr(OH) 3 dissolves
452 JEE Main Chapterwise Topicwise Chemistry

(c) precipitate of Cr(OH) 3 and Fe(OH) 3 as obtained in (b) are As we know that, colloids can be prepared from precipitate by
treated with conc. HCl when only Fe(OH) 3 dissolves using suitable electrolytes. Colloids may be positively or
negatively charged depend on electrolyte we adding.
(d) both (b) and (c) If we add AgNO 3 and KI, it gives Agl andKNO3.
Ans. (b) AgNO3 + KI → AgI + KNO3
If Fe3+ and Cr 3+ both are present, then very first solid ammonium and thus AgI adsorb I − ion as KI is in excess.
chloride and ammonium hydroxide is added slowly till the If KNO3 added, then AgNO3 will be in excess, so
solution smells of ammonia.Fe3+ and Cr 3+ precipitates in the
AgI adsorb Ag + ion.
hydroxide form.
Hence, Agl produce theI– ion.
For identification, precipitate is treated with NaOH and Br2
water, yellow colouration confirms Cr 3+ ion.
2NaOH + Br2 → NaBrO + NaBr + H2O
36 The reaction of cyanamide, NH2CN (s) with oxygen was
NaBrO → NaBr + [O] run in a bomb calorimeter and ∆U was found to be
2Cr(OH) 3 + 4NaOH + 3[O] → 2Na2 CrO4 + 5H2O –742.24 kJ mol −1 . The magnitude of ∆H 298 for the
Solution is acidified and treated with lead acetate solution. reaction
Na2 CrO4 + Pb(CH3COO)2 → PbCrO4 + 2CH3COONa 3
NH2CN(s) + O 2 (g) → N 2 (g) + O 2 (g) + H2O(l)
(Yellow ppt) 2
is ……… kJ (Rounded off to the nearest integer).
TOPIC 5 [Assume ideal gases and R = 8.314 J mol −1 K −1 ]
[2021, 25 Feb Shift-I]
Experiments Ans. (741)
Involving Enthalpy . kJ mol −1
∆U = − 74224
∆ng = [Number of gaseous molecules of products − Number of
35 When silver nitrate solution is added to potassium gaseous molecules of reactants]
iodide solution then the sol produced is 3
NH2 CN(s ) + O2 (g) → N2 (g) + O2 (g) + H2O(l )
[2021, 22 July Shift-II] 2
(a) AgI/I− (b) AgI/ Ag + 3 1
∆ng = 2 − =
(c) Kl / NO −3 (d) AgNO 3 / NO 3− 2 2
Ans. (a) ∆H = ∆U + ∆ng RT
Since, AgNO3 solution was passed to KI solution, the AgI/I − sol = − 74224
. + ×
.
1 8314
× 298 = − 741 kJ/mol
was produced. (Here, the KI solution through which AgNO 3 2 1000
passed, was considered to be in excess). Hence, answer is 741.
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