Chapterwise Topicwise

Solved Papers
2021-1979

IITJEE
JEE Main & Advanced

Chemistry
Ranjeet Shahi

Arihant Prakashan (Series), Meerut

Arihant Prakashan (Series), Meerut
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CONTENTS
1. Some Basic Concepts of Chemistry 1-22 19. Extraction of Metals 282-293

2. Atomic Structure 23-40 20. Qualitative Analysis 294-306

3. Periodic Classification and 21. Organic Chemistry Basics 307-331

Periodic Properties 41-47
22. Hydrocarbons 332-349
4. Chemical Bonding 48-66
23. Alkyl Halides 350-363
5. States of Matter 67-83
24. Alcohols and Ethers 364-377
6. Chemical and Ionic Equilibrium 84-108
25. Aldehydes and Ketones 378-396
7. Thermodynamics and
Thermochemistry 109-129 26. Carboxylic Acids and
their Derivatives 397-412
8. Solid State 130-139
27. Aliphatic Compounds
9. Solutions and Colligative Properties 140-155 Containing Nitrogen 413-422

10. Electrochemistry 156-177 28. Benzene and Alkyl Benzene 423-440

11. Chemical Kinetics 178-195 29. Aromatic Compounds

Containing Nitrogen 441-457
12. Nuclear Chemistry 196-199
30. Aryl Halides and Phenols 458-470
13. Surface Chemistry 200-206
31. Aromatic Aldehydes, Ketones
14. s-Block Elements 207-217 and Acids 471-484
15. p-Block Elements-I 218-227 32. Biomolecules and Chemistry
16. p-Block Elements-II 228-248 in Everyday Life 485-501

17. Transition and 33. Environmental Chemistry 502-504

Inner-Transition Elements 249-258
JEE Advanced Solved Paper 2021 1-16
18. Coordination Compounds 259-281
SYLLABUS
JEE MAIN
Section A : PHYSICAL CHEMISTRY
UNIT I Some Basic Concepts in Chemistry Quantum mechanical approach to covalent bonding Valence bond
Matter and its nature, Dalton's atomic theory; Concept of atom, theory - Its important features, concept of hybridization involving s, p
molecule, element and compound; Physical quantities and their and d orbitals; Resonance.
measurements in Chemistry, precision and accuracy, significant Molecular Orbital Theory Its important features, LCAOs, types of
figures, S.I. Units, dimensional analysis; Laws of chemical molecular orbitals (bonding, antibonding), sigma and pi-bonds,
combination; Atomic and molecular masses, mole concept, molar molecular orbital electronic configurations of homonuclear diatomic
mass, percentage composition, empirical and molecular formulae; molecules, concept of bond order, bond length and bond energy.
Chemical equations and stoichiometry.
Elementary idea of metallic bonding. Hydrogen bonding and its
UNIT II States of Matter applications.
Classification of matter into solid, liquid and gaseous states. UNIT V Chemical Thermodynamics
Gaseous State Measurable properties of gases; Gas laws - Boyle's law, Fundamentals of thermodynamics System and surroundings, extensive
Charle's law, Graham's law of diffusion, Avogadro's law, Dalton's law of and intensive properties, state functions, types of processes.
partial pressure; Concept of Absolute scale of temperature; Ideal gas
First law of thermodynamics Concept of work, heat internal energy and
equation, Kinetic theory of gases (only postulates); Concept of average,
enthalpy, heat capacity, molar heat capacity, Hess's law of constant heat
root mean square and most probable velocities; Real gases, deviation
summation; Enthalpies of bond dissociation, combustion, formation,
from Ideal behaviour, compressibility factor, van der Waals' equation,
atomization, sublimation, phase transition, hydration, ionization and
liquefaction of gases, critical constants.
solution.
Liquid State Properties of liquids - vapour pressure, viscosity and
Second law of thermodynamics Spontaneity of processes; ΔS of the
surface tension and effect of temperature on them (qualitative
universe and ΔG of the system as criteria for spontaneity, ΔGo
treatment only).
(Standard Gibb's energy change) and equilibrium constant.
Solid State Classification of solids: molecular, ionic, covalent and
metallic solids, amorphous and crystalline solids (elementary idea); UNIT VI Solutions
Bragg's Law and its applications, Unit cell and lattices, packing in solids Different methods for expressing concentration of solution - molality,
(fcc, bcc and hcp lattices), voids, calculations involving unit cell molarity, mole fraction, percentage (by volume and mass both), vapour
parameters, imperfection in solids; electrical, magnetic and dielectric pressure of solutions and Raoult's Law - Ideal and non-ideal solutions,
properties. vapour pressure - composition plots for ideal and non-ideal solutions.
UNIT III Atomic Structure Colligative properties of dilute solutions - relative lowering of vapour
pressure, depression of freezing point, elevation of boiling point and
Discovery of sub-atomic particles (electron, proton and neutron);
osmotic pressure; Determination of molecular mass using colligative
Thomson and Rutherford atomic models and their limitations; Nature of
properties; Abnormal value of molar mass, van't Hoff factor and its
electromagnetic radiation, photoelectric effect; spectrum of hydrogen
significance.
atom, Bohr model of hydrogen atom - its postulates, derivation of the
relations for energy of the electron and radii of the different orbits, UNIT VII Equilibrium
limitations of Bohr's model; dual nature of matter, de-Broglie's Meaning of equilibrium, concept of dynamic equilibrium.
relationship, Heisenberg uncertainty principle.
Equilibria involving physical processes Solid -liquid, liquid - gas and
Elementary ideas of quantum mechanics, quantum mechanical model solid - gas equilibria, Henry's law, general characteristics of equilibrium
of atom, its important features, involving physical processes.
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 Equilibria involving chemical processes Law of chemical equilibrium,
numbers (principal, angular momentum and magnetic quantum equilibrium constants (K and K) and their significance, significance of
numbers) and their significance; shapes of s, p and d - orbitals, electron ΔG and ΔGo in chemical equilibria, factors affecting equilibrium
spin and spin quantum number; rules for filling electrons in orbitals – concentration, pressure, temperature, effect of catalyst; Le -Chatelier's
aufbau principle, Pauli's exclusion principle and Hund's rule, principle.
electronic configuration of elements, extra stability of half-filled and Ionic equilibrium Weak and strong electrolytes, ionization of
completely filled orbitals. electrolytes, various concepts of acids and bases (Arrhenius, Bronsted -
Lowry and Lewis) and their ionization, acid-base equilibria (including
UNIT IV Chemical Bonding and Molecular Structure
multistage ionization) and ionization constants, ionization of water, pH
Kossel Lewis approach to chemical bond formation, concept of ionic scale, common ion effect, hydrolysis of salts and pH of their solutions,
and covalent bonds. solubility of sparingly soluble salts and solubility products, buffer
Ionic Bonding Formation of ionic bonds, factors affecting the formation solutions.
of ionic bonds; calculation of lattice enthalpy.
UNIT VIII Redox Reactions and Electrochemistry
Covalent Bonding Concept of electronegativity, Fajan's rule, dipole Electronic concepts of oxidation and reduction, redox reactions,
moment; Valence Shell Electron Pair Repulsion (VSEPR) theory and oxidation number, rules for assigning oxidation number, balancing of
shapes of simple molecules. redox reactions.
Eectrolytic and metallic conduction, conductance in electrolytic temperature on rate of reactions - Arrhenius theory, activation energy
solutions, specific and molar conductivities and their variation with and its calculation, collision theory of bimolecular gaseous reactions
concentration: Kohlrausch's law and its applications. (no derivation).
Electrochemical cells - Electrolytic and Galvanic cells, different types of UNIT X Surface Chemistry
electrodes, electrode potentials including standard electrode Adsorption - Physisorption and chemisorption and their
potential, half - cell and cell reactions, emf of a Galvanic cell and its characteristics, factors affecting adsorption of gases on solids-
measurement; Nernst equation and its applications; Relationship Freundlich and Langmuir adsorption isotherms, adsorption from
between cell potential and Gibbs' energy change; Dry cell and lead solutions.
accumulator; Fuel cells; Corrosion and its prevention.
Catalysis Homogeneous and heterogeneous, activity and selectivity of
UNIT IX Chemical Kinetics solid catalysts, enzyme catalysis and its mechanism.
Rate of a chemical reaction, factors affecting the rate of reactions Colloidal state distinction among true solutions, colloids and
concentration, temperature, pressure and catalyst; elementary and suspensions, classification of colloids - lyophilic, lyophobic; multi
complex reactions, order and molecularity of reactions, rate law, rate molecular, macromole-cular and associated colloids (micelles),
constant and its units, differential and integral forms of zero and first preparation and properties of colloids Tyndall effect, Brownian
order reactions, their characteristics and half - lives, effect of movement, electrophoresis, dialysis, coagulation and
flocculation; Emulsions and their characteristics.

Section B : INORGANIC CHEMISTRY

UNIT XI Classification of Elements and Group 16 Preparation, properties, structures and uses of dioxygen
Periodicity in Properties and ozone; Allotropic forms of sulphur; Preparation, properties,
Periodic Law and Present Form of the Periodic Table, s, p, d and f Block structures and uses of sulphur dioxide, sulphuric acid (including
Elements, Periodic Trends in Properties of Elementsatomic and Ionic Radii, its industrial preparation); Structures of oxoacids of sulphur.
Ionization Enthalpy, Electron Gain Enthalpy, Valence, Oxidation States and Group 17 Preparation, properties and uses of chlorine and
Chemical Reactivity. hydrochloric acid; Trends in the acidic nature of hydrogen halides;
Structures of Interhalogen compounds and oxides and oxoacids of
UNIT XII General Principles and Processes of Isolation of Metals halogens.
Modes of occurrence of elements in nature, minerals, ores; steps involved Group 18 Occurrence and uses of noble gases; Structures of
in the extraction of metals - concentration, reduction (chemical and fluorides and oxides of xenon.
electrolytic methods) and refining with special reference to the extraction
of Al, Cu, Zn and Fe; Thermodynamic and electrochemical principles UNIT XVI d–and f–Block Elements
involved in the extraction of metals. Transition Elements General introduction, electronic
configuration, occurrence and characteristics, general trends in
UNIT XIII Hydrogen properties of the first row transition elements - physical properties,
Position of hydrogen in periodic table, isotopes, preparation, properties ionization enthalpy, oxidation states, atomic radii, colour, catalytic
and uses of hydrogen; physical and chemical properties of water and behaviour, magnetic properties, complex formation, interstitial
heavy water; Structure, preparation, reactions and uses of hydrogen compounds, alloy formation; Preparation, properties and uses of
peroxide; Classification of hydrides ionic, covalent and interstitial; K2 Cr2 O7 and KMnO4.
Hydrogen as a fuel. Inner Transition Elements
UNIT XIV s - Block Elements (Alkali and Alkaline Earth Metals) Lanthanoids - Electronic configuration, oxidation states, chemical
reactivity and lanthanoid contraction. Actinoids - Electronic
Group 1 and 2 Elements configuration and oxidation states.
General introduction, electronic configuration and general trends in
UNIT XVII Coordination Compounds
physical and chemical properties of elements, anomalous properties of the
first element of each group, diagonal relationships. Introduction to coordination compounds, Werner's theory; ligands,
coordination number, denticity, chelation; IUPAC nomenclature of
Preparation and properties of some important compounds - sodium mononuclear coordination compounds, isomerism; Bonding
carbonate, sodium chloride, sodium hydroxide and sodium hydrogen Valence bond approach and basic ideas of Crystal field theory,
carbonate; Industrial uses of lime, limestone, Plaster of Paris and cement; colour and magnetic properties; importance of coordination
Biological significance of Na, K, Mg and Ca. compounds (in qualitative analysis, extraction of metals and in
biological systems).
UNIT XV p - Block Elements
Group 13 to Group 18 Elements UNIT XVIII Environmental Chemistry
General Introduction Electronic configuration and general trends in Environmental pollution Atmospheric, water and soil.
physical and chemical properties of elements across the periods and Atmospheric pollution - Tropospheric and stratospheric.
down the groups; unique behaviour of the first element in each Tropospheric pollutants Gaseous pollutants Oxides of carbon,
group.Group wise study of the p – block elements nitrogen and sulphur, hydrocarbons; their sources, harmful effects
Group 13 Preparation, properties and uses of boron and aluminium; and prevention; Green house effect and Global warming; Acid rain;
structure, properties and uses of borax, boric acid, diborane, boron Particulate pollutants Smoke, dust, smog, fumes, mist; their
trifluoride, aluminium chloride and alums. sources, harmful effects and prevention.
Group 14 Tendency for catenation; Structure, properties and uses of Stratospheric pollution Formation and breakdown of ozone,
allotropes and oxides of carbon, silicon tetrachloride, silicates, zeolites and depletion of ozone layer - its mechanism and effects.
silicones. Water pollution Major pollutants such as, pathogens, organic
wastes and chemical pollutants their harmful effects and
Group 15 Properties and uses of nitrogen and phosphorus; Allotrophic
prevention.
forms of phosphorus; Preparation, properties, structure and uses of
ammonia nitric acid, phosphine and phosphorus halides,(PCl3, PCl5); Soil pollution Major pollutants such as: Pesticides (insecticides,
Structures of oxides and oxoacids of nitrogen and phosphorus. herbicides and fungicides), their harmful effects and prevention.
Strategies to control environmental pollution.
Section C : ORGANIC CHEMISTRY
UNIT XIX Purification & Characterisation of Organic Compounds UNIT XXIV Organic Compounds Containing Nitrogen
Purification Crystallisation, sublimation, distillation, differential General methods of preparation, properties, reactions and uses.
extraction and chromatography principles and their applications. Amines Nomenclature, classification, structure basic character and
Qualitative analysis Detection of nitrogen, sulphur, phosphorus and identification of primary, secondary and tertiary amines and their basic
halogens. character.
Quantitative analysis (basic principles only) Estimation of carbon, Diazonium Salts Importance in synthetic organic chemistry.
hydrogen, nitrogen, halogens, sulphur, phosphorus.
UNIT XXV Polymers
Calculations of empirical formulae and molecular formulae;
Numerical problems in organic quantitative analysis. General introduction and classification of polymers, general methods
of polymerization-addition and condensation, copolymerization;
UNIT XX Some Basic Principles of Organic Chemistry Natural and synthetic rubber and vulcanization; some important
Tetravalency of carbon; Shapes of simple molecules hybridization polymers with emphasis on their monomers and uses - polythene,
(s and p); Classification of organic compounds based on functional nylon, polyester and bakelite.
groups: —C=C—,—C=C— and those containing halogens, oxygen,
nitrogen and sulphur, Homologous series; Isomerism - structural and UNIT XXVI Biomolecules
stereoisomerism. General introduction and importance of biomolecules.
Nomenclature (Trivial and IUPAC) Carbohydrates Classification aldoses and ketoses; monosaccharides
Covalent bond fission Homolytic and heterolytic free radicals, (glucose and fructose), constituent monosaccharides of
carbocations and carbanions; stability of carbocations and free radicals, oligosacchorides (sucrose, lactose, maltose) and polysaccharides
electrophiles and nucleophiles. (starch, cellulose, glycogen).
Electronic displacement in a covalent bond Inductive effect, Proteins Elementary Idea of α-amino acids, peptide bond, .
electromeric effect, resonance and hyperconjugation. polypeptides; proteins: primary, secondary, tertiary and quaternary
Common types of organic reactions Substitution, addition, structure (qualitative idea only), denaturation of proteins, enzymes.
elimination and rearrangement. Vitamins Classification and functions.
UNIT XXI Hydrocarbons Nucleic Acids Chemical constitution of DNA and RNA. Biological
Classification, isomerism, IUPAC nomenclature, general methods of functions of Nucleic acids.
preparation, properties and reactions. UNIT XXVII Chemistry in Everyday Life
Alkanes Conformations: Sawhorse and Newman projections (of Chemicals in medicines Analgesics, tranquilizers, antiseptics,
ethane); Mechanism of halogenation of alkanes. disinfectants, antimicrobials, antifertility drugs, antibiotics, antacids,
Alkenes Geometrical isomerism; Mechanism of electrophilic addition: antihistamins - their meaning and common examples.
addition of hydrogen, halogens, water, hydrogen halides Chemicals in food Preservatives, artificial sweetening agents - common
(Markownikoff's and peroxide effect); Ozonolysis, oxidation, and examples.
polymerization.
Cleansing agents Soaps and detergents, cleansing action.
Alkenes acidic character; addition of hydrogen, halogens, water and
hydrogen halides; polymerization. Unit XXVIII Principles Related to
Aromatic hydrocarbons Nomenclature, benzene structure and Practical Chemistry
aromaticity; Mechanism of electrophilic substitution: halogenation, — Detection of extra elements (N, S, halogens) in organic
nitration, Friedel – Craft's alkylation and acylation, directive influence of compounds; Detection of the following functional groups:
functional group in mono-substituted benzene. hydroxyl (alcoholic and phenolic), carbonyl (aldehyde and ketone),
UNIT XXII Organic Compounds Containing Halogens carboxyl and amino groups in organic compounds.
General methods of preparation, properties and reactions; Nature of Chemistry involved in the preparation of the following
C—X bond; Mechanisms of substitution reactions. — Inorganic compounds Mohr's salt, potash alum.
Uses/environmental effects of chloroform, iodoform, freons and DDT. — Organic compounds Acetanilide,
p-nitroacetan ilide, aniline yellow, iodoform.
UNIT XXIII Organic Compounds Containing Oxygen
General methods of preparation, properties, reactions and uses. — Chemistry involved in the titrimetric excercises - Acids bases and
Alcohols, Phenols and Ethers the use of indicators, oxali acid vs KMnO4, Mohr's salt vs KMnO4.
Alcohols Identification of primary, secondary and tertiary alcohols; — Chemical principles involved in the qualitative salt analysis
mechanism of dehydration. — Cations — Pb2+ , Cu2+, Al3+, Fe3+, Zn2+, Ni2+, Ca2+, Ba2+ , Mg2+ NH4+.
Phenols Acidic nature, electrophilic substitution reactions: Anions – CO32-, S2-, SO42-, NO2, NO3, Cl -, Br-, I- (Insoluble salts
halogenation, nitration and sulphonation, Reimer - Tiemann reaction. excluded).
Ethers: Structure — Chemical principles involved in the following experiments
Aldehyde and Ketones Nature of carbonyl group; 1. Enthalpy of solution of CuSO4
Nucleophilic addition to >C=O group, relative reactivities of aldehydes 2. Enthalpy of neutralization of strong acid and strong base.
and ketones; Important reactions such as - Nucleophilic addition 3. Preparation of lyophilic and lyophobic sols.
reactions (addition of HCN, NH3 and its derivatives), Grignard reagent;
4. Kinetic study of reaction of iodide ion with hydrogen peroxide
oxidation; reduction (Wolff Kishner and Clemmensen); acidity of α -
at room temperature.
hydrogen, aldol condensation, Cannizzaro reaction, Haloform reaction;
Chemical tests to distinguish between aldehydes and Ketones.
Carboxylic Acids Acidic strength & factors affecting it.
JEE ADVANCED
PHYSICAL CHEMISTRY Chemical Kinetics Rates of chemical reactions, Order of
reactions, Rate constant, First order reactions,
General Topics Concept of atoms and molecules,
Temperature dependence of rate constant (Arrhenius
Dalton's atomic theory, Mole concept, Chemical formulae,
equation).
Balanced chemical equations, Calculations (based on
mole concept) involving common oxidation-reduction, Solid State Classification of solids, crystalline state, seven
neutralisation, and displacement reactions, Concentration crystal systems (cell parameters a, b, c), close packed
in terms of mole fraction, molarity, molality and normality. structure of solids (cubic), packing in fcc, bcc and hcp
lattices, Nearest neighbours, ionic radii, simple ionic
Gaseous and Liquid States Absolute scale of
compounds, point defects.
temperature, ideal gas equation, Deviation from ideality,
van der Waals' equation, Kinetic theory of gases, average, Solutions Raoult's law, Molecular weight determination
root mean square and most probable velocities and their from lowering of vapour pressure, elevation of boiling
relation with temperature, Law of partial pressures, point and depression of freezing point.
Vapour pressure, Diffusion of gases.
Surface Chemistry Elementary concepts of adsorption
Atomic Structure and Chemical Bonding Bohr model, (excluding adsorption isotherms), Colloids, types,
spectrum of hydrogen atom, quantum numbers, methods of preparation and general properties,
Wave-particle duality, de-Broglie hypothesis, Uncertainty Elementary ideas of emulsions, surfactants and micelles
principle, Qualitative quantum mechanical picture of (only definitions and examples).
hydrogen atom, shapes of s, p and d orbitals, Electronic
Nuclear Chemistry Radioactivity, isotopes and isobars,
configurations of elements (up to atomic number 36),
Properties of rays, Kinetics of radioactive decay (decay
Aufbau principle, Pauli's exclusion principle and Hund's
series excluded), carbon dating, Stability of nuclei with
rule, Orbital overlap and covalent bond; Hybridisation
respect to proton-neutron ratio, Brief discussion on fission
involving s, p and d orbitals only, Orbital energy diagrams
and fusion reactions.
for homonuclear diatomic species, Hydrogen bond,
Polarity in molecules, dipole moment (qualitative aspects
only), VSEPR model and shapes of molecules (linear, INORGANIC CHEMISTRY
angular, triangular, square planar, pyramidal, square Isolation/Preparation and Properties of the following
pyramidal, trigonal bipyramidal, tetrahedral and Non-metals Boron, silicon, nitrogen, phosphorus, oxygen,
octahedral). sulphur and halogens, Properties of allotropes of carbon
(only diamond and graphite), phosphorus and sulphur.
Energetics First law of thermodynamics, Internal energy,
work and heat, pressure-volume work, Enthalpy, Hess's Preparation and Properties of the following
law, Heat of reaction, fusion and vaporization, Second law Compounds Oxides, peroxides, hydroxides, carbonates,
of thermodynamics, Entropy, Free energy, Criterion of bicarbonates, chlorides and sulphates of sodium,
spontaneity. potassium, magnesium and calcium, Boron, diborane,
boric acid and borax, Aluminium, alumina, aluminium
Chemical Equilibrium Law of mass action, Equilibrium chloride and alums, Carbon, oxides and oxyacid (carbonic
constant, Le-Chatelier's principle (effect of concentration, acid), Silicon, silicones, silicates and silicon carbide,
temperature and pressure), Significance of DG and DGo in Nitrogen, oxides, oxyacids and ammonia, Phosphorus,
chemical equilibrium, Solubility product, common ion oxides, oxyacids (phosphorus acid, phosphoric acid) and
effect, pH and buffer solutions, Acids and bases (Bronsted phosphine, Oxygen, ozone and hydrogen peroxide,
and Lewis concepts), Hydrolysis of salts. Sulphur, hydrogen sulphide, oxides, sulphurous acid,
Electrochemistry Electrochemical cells and cell reactions, sulphuric acid and sodium thiosulphate, Halogens,
Standard electrode potentials, Nernst equation and its hydrohalic acids, oxides and oxyacids of chlorine,
relation to DG, Electrochemical series, emf of galvanic bleaching powder, Xenon fluorides.
cells, Faraday's laws of electrolysis, Electrolytic Transition Elements (3d series) Definition, general
conductance, specific, equivalent and molar conductivity, characteristics, oxidation states and their stabilities,
Kohlrausch's law, Concentration cells. colour (excluding the details of electronic transitions) and
calculation of spin-only magnetic moment; Coordination (boiling points, density and dipole moments), Acidity of
compounds: nomenclature of mononuclear coordination alkynes, Acid catalysed hydration of alkenes and alkynes
compounds, cis-trans and ionisation isomerisms, (excluding the stereochemistry of addition and
hybridization and geometries of mononuclear elimination), Reactions of alkenes with KMnO4 and ozone,
coordination compounds (linear, tetrahedral, square Reduction of alkenes and alkynes, Preparation of alkenes
planar and octahedral). and alkynes by elimination reactions, Electrophilic
Preparation and Properties of the following addition reactions of alkenes with X2, HX, HOX and H2O
Compounds Oxides and chlorides of tin and lead, Oxides, (X=halogen), Addition reactions of alkynes, Metal
chlorides and sulphates of Fe2+, Cu2+ and Zn2+, Potassium acetylides.
permanganate, potassium dichromate, silver oxide, silver Reactions of Benzene Structure and aromaticity,
nitrate, silver thiosulphate. Electrophilic substitution reactions, halogenation,
Ores and Minerals Commonly occurring ores and nitration, sulphonation, Friedel-Crafts alkylation and
minerals of iron, copper, tin, lead, magnesium, aluminium, acylation Effect of o-, m- and p-directing groups in
zinc and silver. monosubstituted benzenes.
Extractive Metallurgy Chemical principles and reactions Phenols Acidity, electrophilic substitution reactions
only (industrial details excluded), Carbon reduction (halogenation, nitration and sulphonation), Reimer-
method (iron and tin), Self reduction method (copper and Tiemann reaction, Kolbe reaction.
lead), Electrolytic reduction method (magnesium and Characteristic Reactions of the following (including
aluminium), Cyanide process (silver and gold). those mentioned above) Alkyl halides, rearrangement
Principles of Qualitative Analysis Groups I to V (only reactions of alkyl carbocation, Grignard reactions,
Ag+, Hg2+, Cu2+, Pb2+, Bi3+, Fe3+, Cr3+, Al3+, Ca2+, Ba2+, Zn2+, Mn2+ nucleophilic substitution reactions, Alcohols,
and Mg2+), Nitrate, halides (excluding fluoride), sulphate esterification, dehydration and oxidation, reaction with
and sulphide. sodium, phosphorus halides, ZnCl2/concentrated HCl,
conversion of alcohols into aldehydes and ketones, Ethers,
Preparation by Williamson's Synthesis, Aldehydes and
ORGANIC CHEMISTRY Ketones, oxidation, reduction, oxime and hydrazone
Concepts Hybridisation of carbon, Sigma and pi-bonds, formation, aldol condensation, Perkin reaction, Cannizzaro
Shapes of simple organic molecules, Structural and reaction, haloform reaction and nucleophilic addition
geometrical isomerism, Optical isomerism of compounds reactions (Grignard addition), Carboxylic acids, formation
containing up to two asymmetric centres, (R,S and E,Z of esters, acid chlorides and amides, ester hydrolysis.
nomenclature excluded), IUPAC nomenclature of simple Amines, basicity of substituted anilines and aliphatic
organic compounds (only hydrocarbons, mono-functional amines, preparation from nitro compounds, reaction with
and bi-functional compounds), Conformations of ethane nitrous acid, azo coupling reaction of diazonium salts of
and butane (Newman projections), Resonance and aromatic amines, Sandmeyer and related reactions of
hyperconjugation, Keto-enol tautomerism, Determination diazonium salts, carbylamine reaction, Haloarenes,
of empirical and molecular formulae of simple nucleophilic aromatic substitution in haloarenes and
compounds (only combustion method), Hydrogen bonds, substituted haloarenes (excluding Benzyne mechanism
definition and their effects on physical properties of and Cine substitution).
alcohols and carboxylic acids, Inductive and resonance Carbohydrates Classification, mono and disaccharides
effects on acidity and basicity of organic acids and bases, (glucose and sucrose), Oxidation, reduction, glycoside
Polarity and inductive effects in alkyl halides, Reactive formation and hydrolysis of sucrose.
intermediates produced during homolytic and heterolytic
bond cleavage, Formation, structure and stability of Amino Acids and Peptides General structure (only
carbocations, carbanions and free radicals. primary structure for peptides) and physical properties.

Preparation, Properties and Reactions of Alkanes Properties and Uses of Some Important Polymers
Homologous series, physical properties of alkanes Natural rubber, cellulose, nylon, teflon and PVC.
(melting points, boiling points and density), Combustion Practical Organic Chemistry Detection of elements (N, S,
and halogenation of alkanes, Preparation of alkanes by halogens), Detection and identification of the following
Wurtz reaction and decarboxylation reactions. functional groups, hydroxyl (alcoholic and phenolic),
Preparation, Properties and Reactions of Alkenes and carbonyl (aldehyde and ketone), carboxyl, amino and
Alkynes Physical properties of alkenes and alkynes nitro, Chemical methods of separation of mono-functional
organic compounds from binary mixtures.
1
Some Basic Concepts
of Chemistry
6. The percentage composition of carbon by mole in methane is
Topic 1 Mole Concept (2019 Main, 8 April II)
(a) 75% (b) 20% (c) 25% (d) 80%
Objective Questions I (Only one correct option)
7. 8 g of NaOH is dissolved in 18 g of H2 O. Mole fraction of
1. 5 moles of AB2 weight 125 × 10−3 kg and 10 moles of A2 B2
NaOH in solution and molality (in mol kg− 1 ) of the solution
weight 300 × 10−3 kg. The molar mass of A ( M A ) and molar
respectively are (2019 Main, 12 Jan II)
mass of B ( M B ) in kg mol −1 are (2019 Main, 12 April I) (a) 0.2, 11.11 (b) 0.167, 22.20
(a) M A = 10 × 10−3 and M B = 5 × 10−3 (c) 0.2, 22.20 (d) 0.167, 11.11
(b) M A = 50 × 10−3 and M B = 25 × 10−3 8. The volume strength of 1 M H2 O2 is
(c) M A = 25 × 10−3 and M B = 50 × 10−3 (Molar mass of H2 O2 = 34 g mol −1 ) (2019 Main, 12 Jan II)
−3 −3
(d) M A = 5 × 10 and M B = 10 × 10 (a) 16.8 (b) 22.4 (c) 11.35 (d) 5.6
2. The minimum amount of O2 ( g ) consumed per gram of 9. The amount of sugar (C12 H22 O11 ) required to prepare 2 L of
reactant is for the reaction (Given atomic mass : Fe = 56, its 0.1 M aqueous solution is (2019 Main, 10 Jan II)
O = 16, Mg = 24, P = 31, C = 12, H = 1) (2019 Main, 10 April II) (a) 17.1 g (b) 68.4 g (c) 136.8 g (d) 34.2 g
(a) C3 H8 ( g ) + 5O2 ( g ) → 3CO2 ( g ) + 4H2 O( l ) 10. For the following reaction, the mass of water produced from
(b) P4 ( s ) + 5O2 ( g ) → P4 O10 ( s ) 445 g of C57 H110 O6 is :
(c) 4Fe( s ) + 3O2 ( g ) → 2Fe2 O3 ( s ) 2C57 H110 O6 ( s ) + 163O2 ( g ) → 114CO2 ( g ) + 110 H2 O ( l )
(d) 2Mg ( s ) + O2 ( g ) → 2MgO( s ) (2019 Main, 9 Jan II)

3. At 300 K and 1 atmospheric pressure, (a) 490 g (b) 495 g (c) 445 g (d) 890 g
10 mL of a hydrocarbon required 55 mL of O2 for complete 11. A solution of sodium sulphate contains 92 g of Na + ions per
combustion and 40 mL of CO2 is formed. The formula of the kilogram of water. The molality of Na + ions in that solution
hydrocarbon is (2019 Main, 10 April I) in mol kg−1 is (2019 Main, 9 Jan I)
(a) C4H7Cl (b) C4H 6 (c) C4H10 (d) C4H 8
(a) 16 (b) 4 (c) 132 (d) 8
4. 10 mL of 1 mM surfactant solution forms a monolayer
12. The most abundant elements by mass in the body of a healthy
covering 0.24 cm 2 on a polar substrate. If the polar head is human adult are oxygen (61.4%), carbon (22.9%), hydrogen
approximated as a cube, what is its edge length? (10.0 %), and nitrogen (2.6%). The weight which a 75 kg
(2019 Main, 9 April II)
person would gain if all 1 Hatoms are replaced by 2 Hatoms is
(a) 2.0 pm (b) 0.1 nm (c) 1.0 pm (d) 2.0 nm (2017 JEE Main)
5. For a reaction, (a) 15 kg (b) 37.5 kg
N 2 ( g ) + 3H 2 ( g ) → 2NH 3 ( g ), identify dihydrogen (H 2 ) (c) 7.5 kg (d) 10 kg
as a limiting reagent in the following reaction mixtures. 13. 1 g of a carbonate (M 2 CO3 ) on treatment with excess HCl
(2019 Main, 9 April I)
produces 0.01186 mole of CO2 . The molar mass of M 2 CO3
(a) 56 g of N 2 + 10 g of H 2 (b) 35 g of N 2 + 8 g of H 2 in g mol −1 is (2017 JEE Main)
(c) 14 g of N 2 + 4 g of H 2 (d) 28 g of N 2 + 6 g of H 2 (a) 1186 (b) 84.3 (c) 118.6 (d) 11.86
2 Some Basic Concepts of Chemistry

14. At 300 K and 1 atm, 15 mL of a gaseous hydrocarbon 24. The normality of 0.3 M phosphorus acid (H3PO3) is
requires 375 mL air containing 20% O2 by volume for (1999, 2M)
complete combustion. After combustion, the gases occupy (a) 0.1 (b) 0.9 (c) 0.3 (d) 0.6
330 mL. Assuming that the water formed is in liquid form 25. In which mode of expression, the concentration of a solution
and the volumes were measured at the same temperature and remains independent of temperature? (1988, 1M)
pressure, the formula of the hydrocarbon is (2016 Main) (a) Molarity (b) Normality (c) Formality (d) Molality
(a) C3 H8 (b) C4 H8 (c) C4 H10 (d) C3 H6 26. A molal solution is one that contains one mole of solute in
15. The molecular formula of a commercial resin used for (1986, 1M)
exchanging ions in water softening is C8 H7 SO3 Na (a) 1000 g of solvent (b) 1.0 L of solvent
(molecular weight = 206). What would be the maximum (c) 1.0 L of solution (d) 22.4 L of solution
uptake of Ca 2+ ions by the resin when expressed in mole per 27. If 0.50 mole of BaCl 2 is mixed with 0.20 mole of Na 3 PO4 ,
gram resin? (2015 Main) the maximum number of moles of Ba 3 (PO4 )2 that can be
1 1 2 1 formed is (1981, 1M)
(a) (b) (c) (d)
103 206 309 412 (a) 0.70 (b) 0.50 (c) 0.20 (d) 0.10
16. 3 g of activated charcoal was added to 50 mL of acetic acid 28. 2.76 g of silver carbonate on being strongly heated yields a
solution (0.06 N) in a flask. After an hour it was filtered and residue weighing (1979, 1M)
the strength of the filtrate was found to be 0.042 N. The (a) 2.16 g (b) 2.48 g (c) 2.32 g (d) 2.64 g
amount of acetic acid adsorbed (per gram of charcoal) is 29. When the same amount of zinc is treated separately with
(2015 Main) excess of sulphuric acid and excess of sodium hydroxide, the
(a) 18 mg (b) 36 mg (c) 42 mg (d) 54 mg ratio of volumes of hydrogen evolved is (1979, 1M)
17. The ratio mass of oxygen and nitrogen of a particular gaseous (a) 1 : 1 (b) 1 : 2 (c) 2 : 1 (d) 9 : 4
mixture is 1 : 4. The ratio of number of their molecule is 30. The largest number of molecules is in (1979, 1M)
(2014 Main)
(a) 1 : 4 (b) 7 : 32 (c) 1 : 8 (d) 3 : 16 (a) 36 g of water
(b) 28 g of CO
18. The molarity of a solution obtained by mixing 750 mL of
(c) 46 g of ethyl alcohol
0.5 M HCl with 250 mL of 2 M HCl will be (2013 Main)
(d) 54 g of nitrogen pentaoxide (N2 O5 )
(a) 0.875 M (b) 1.00 M (c) 1.75 M (d) 0.0975M
31. The total number of electrons in one molecule of carbon
19. Dissolving 120 g of urea (mol. wt. 60) in 1000 g of water dioxide is (1979, 1M)
gave a solution of density 1.15 g/mL. The molarity of the (a) 22 (b) 44 (c) 66 (d) 88
solution is (2011)
32. A gaseous mixture contains oxygen and nitrogen in the ratio
(a) 1.78 M (b) 2.00 M (c) 2.05 M (d) 2.22 M
of 1:4 by weight. Therefore, the ratio of their number of
20. Given that the abundances of isotopes 54 Fe, 56 Fe and 57 Fe molecules is (1979, 1M)
are 5%, 90% and 5%, respectively, the atomic mass of Fe is (a) 1 : 4 (b) 1 : 8 (c) 7 : 32 (d) 3 : 16
(2009)
(a) 55.85 (b) 55.95 Numerical Answer Type Questions
(c) 55.75 (d) 56.05 33. A 100 mL solution was made by adding 1.43 g of
21. Mixture X = 0.02 mole of [Co(NH3 )5 SO4 ]Br and 0.02 mole Na 2CO3 ⋅ xH 2O. The normality of the solution is 0.1 N. The
of [Co(NH3 )5 Br]SO4 was prepared in 2 L solution. value of x is ……… .
1 L of mixture X + excess of AgNO3 solution → Y (The atomic mass of Na is 23 g/mol) (2020 Main, 4 Sep II)
1 L of mixture X + excess of BaCl 2 solution → Z 34. Galena (an ore) is partially oxidised by passing air through it
Number of moles of Y and Z are (2003, 1M) at high temperature. After some time, the passage of air is
(a) 0.01, 0.01 (b) 0.02, 0.01 stopped, but the heating is continued in a closed furnace such
(c) 0.01, 0.02 (d) 0.02, 0.02 that the content undergo self-reduction. The weight (in kg) of
Pb produced per kg of O 2 consumed is ……… .
22. Which has maximum number of atoms? (2003, 1M)
(Atomic weights in g mol −1 : O = 16, S = 32, Pb = 207)
(a) 24 g of C (12) (b) 56 g of Fe (56)
(2018 Adv.)
(c) 27 g of Al (27) (d) 108 g of Ag (108) 35. To measure the quantity of MnCl 2 dissolved in an aqueous
23. How many moles of electron weighs 1 kg? solution, it was completely converted to KMnO4 using the
23 1 reaction,
(a) 6.023 × 10 (b) × 1031 (2002, 3M)
9.108 MnCl 2 + K 2 S2 O8 + H2 O → KMnO4 + H2 SO4 + HCl
6.023 1 (equation not balanced).
(c) × 1054 (d) × 108
9.108 9.108 × 6.023
 Some Basic Concepts of Chemistry 3

Few drops of concentrated HCl were added to this solution K in a container of volume is 2.46 cm 3 . Density of surface sites
and gently warmed. Further, oxalic acid (225 mg) was is 6.023 × 1014 /cm 2 and surface area is 1000 cm 2 , find out the
added in portions till the colour of the permanganate ion
number of surface sites occupied per molecule of N2 . (2005, 3M)
disappeared. The quantity of MnCl 2 (in mg) present in the
initial solution is ……… . 45. In a solution of 100 mL 0.5 M acetic acid, one gram of active
(Atomic weights in g mol −1 : Mn = 55, Cl = 35.5) charcoal is added, which adsorbs acetic acid. It is found that the
concentration of acetic acid becomes 0.49 M. If surface area of
(2018 Adv.)
charcoal is 3.01 × 102 m2 , calculate the area occupied by single
36. In the following reaction sequence, the amount of D (in acetic acid molecule on surface of charcoal. (2003)
gram) formed from 10 moles of acetophenone is …….
46. Find the molarity of water. Given: ρ = 1000 kg/m3 (2003)
−1
(Atomic weights in g mol : H = 1, C = 12, N = 14,
47. A plant virus is found to consist of uniform cylindrical particles
O = 16, Br = 80. The yield (%) corresponding to the
of 150 Å in diameter and 5000 Å long. The specific volume of
product in each step is given in the parenthesis)
the virus is 0.75 cm 3 /g. If the virus is considered to be a single
O particle, find its molar mass. (1999, 3M)

NaOBr NH3, ∆ Br2/KOH

48. 8.0575 × 10−2 kg of Glauber’s salt is dissolved in water to
H3O+
A B C
obtain 1 dm 3 of solution of density 1077.2 kg m −3 . Calculate
(60%) (50%) (50%)
the molality, molarity and mole fraction of Na 2 SO4 in solution.
Br2(3 equivalent ) (1994, 3M)
D
AcOH
(100%)
(2018 Adv.) 49. A is a binary compound of a univalent metal. 1.422 g of A reacts
completely with 0.321 g of sulphur in an evacuated and sealed
tube to give 1.743 g of a white crystalline solid B, that forms a
Fill in the Blanks hydrated double salt, C with Al 2 (SO4 )3 . Identify A, B and C.
37. The weight of 1 × 1022 molecules of CuSO4 ⋅ 5H2 O is (1994, 2M)

…………. . (1991, 1M) 50. Upon mixing 45.0 mL 0.25 M lead nitrate solution with
25.0 mL of a 0.10 M chromic sulphate solution, precipitation of
38. 3.0 g of a salt of molecular weight 30 is dissolved in 250 g
lead sulphate takes place. How many moles of lead sulphate are
water. The molarity of the solution is ………. (1983, 1M)
formed? Also calculate the molar concentrations of species left
39. The total number of electrons present in 18 mL of water is behind in the final solution. Assume that lead sulphate is
…………. . (1980, 1M) completely insoluble. (1993, 3M)
40. The modern atomic mass unit is based on the mass of 51. Calculate the molality of 1.0 L solution of 93% H2 SO4 ,
…………. . (1980, 1M)
(weight/volume). The density of the solution is 1.84 g/mL.
(1990, 1M)
Integer Answer Type Questions 52. A solid mixture (5.0 g) consisting of lead nitrate and sodium
41. The mole fraction of a solute in a solution is 0.1. At 298 K, nitrate was heated below 600°C until the weight of the residue
molarity of this solution is the same as its molality. Density was constant. If the loss in weight is 28.0 per cent, find the
of this solution at 298 K is 2.0 g cm−3 . The ratio of the amount of lead nitrate and sodium nitrate in the mixture.
(1990, 4M)
m 
molecular weights of the solute and solvent,  solute  is ... 53. n-butane is produced by monobromination of ethane followed
 msolvent 
by Wurtz’s reaction.Calculate volume of ethane at NTP
. (2016 Adv.) required to produce 55 g n-butane, if the bromination takes
42. A compound H2 X with molar weight of 80 g is dissolved place with 90% yield and the Wurtz’s reaction with 85% yield.
in a solvent having density of 0.4 g mL−1 . Assuming no (1989, 3M)

change in volume upon dissolution, the molality of a 3.2 54. A sugar syrup of weight 214.2 g contains 34.2 g of sugar
molar solution is (2014 Adv.) (C12 H22 O11 ). Calculate (i) molal concentration and (ii) mole
fraction of sugar in syrup. (1988, 2M)
43. 29.2% (w/W ) HCl stock solution has density of 1.25g mL
−1
. The molecular weight of HCl is 36.5 g mol − 1 . The 55. An unknown compound of carbon, hydrogen and oxygen
volume (mL) of stock solution required to prepare a 200 contains 69.77% C and 11.63% H and has a molecular weight
of 86. It does not reduces Fehling’s solution but forms a
mL solution 0.4 M HCl is (2012)
bisulphate addition compound and gives a positive iodoform
test. What is the possible structure(s) of unknown compound?
Subjective Questions (1987, 3M)
44. 20% surface sites have adsorbed N2 . On heating N2 gas 56. The density of a 3 M sodium thiosulphate solution ( Na 2 S2 O3 )
evolved from sites and were collected at 0.001 atm and 298 is 1.25 g per mL. Calculate (i) the percentage by weight of
4 Some Basic Concepts of Chemistry

sodium thiosulphate (ii) the mole fraction of sodium oxygen. All volumes have been reduced to NTP. Calculate
thiosulphate and (iii) the molalities of Na + and S2 O2−
3 ions. the molecular formula of the hydrocarbon gas. (1979, 3M)
(1983, 5M) 59. In the analysis of 0.5 g sample of feldspar, a mixture of
57. (a) 1.0 L of a mixture of CO and CO2 is taken. This mixture chlorides of sodium and potassium is obtained, which weighs
is passed through a tube containing red hot charcoal. The 0.1180 g. Subsequent treatment of the mixed chlorides with
volume now becomes 1.6 L. The volumes are measured silver nitrate gives 0.2451 g of silver chloride. What is the
under the same conditions. Find the composition of percentage of sodium oxide and potassium oxide in the
mixture by volume. sample? (1979, 5M)
(b) A compound contains 28 per cent of nitrogen and 60. The vapour density (hydrogen = 1) of a mixture consisting of
72 per cent of a metal by weight. 3 atoms of metal NO2 and N2 O4 is 38.3 at 26.7°C. Calculate the number of
combine with 2 atoms of nitrogen. Find the atomic moles of NO2 in 100 g of the mixture. (1979, 5M)
weight of metal. (1980, 5M)
61. Accounts for the following. Limit your answer to two
58. 5.00 mL of a gas containing only carbon and hydrogen were sentences, “Atomic weights of most of the elements are
mixed with an excess of oxygen (30 mL) and the mixture fractional”. (1979, 1M)
exploded by means of electric spark. After explosion, the
62. Naturally occurring boron consists of two isotopes whose
volume of the mixed gases remaining was 25 mL.
atomic weights are 10.01 and 11.01. The atomic weight of
On adding a concentrated solution of KOH, the volume natural boron is 10.81. Calculate the percentage of each
further diminished to 15 mL, the residual gas being pure isotope in natural boron. (1978, 2M)

Topic 2 Equivalent Concept, Neutralisation and Redox Titration

Objective Questions I (Only one correct option) surface of water in a round watch glass. Hexane evaporates
1. An example of a disproportionation reaction is and a monolayer is formed. The distance from edge to centre
(2019 Main, 12 April I) of the watch glass is 10 cm. What is the height of the
(a) 2MnO−4 + 10I + 16H → 2Mn2 + +5I2 + 8H 2O
− + monolayer? [Density of fatty acid = 0.9 g cm −3 ; π = 3]
(2019 Main, 8 April II)
(b) 2NaBr + Cl2 → 2NaCl + Br2
(a) 10−6 m (b) 10−4 m
(c) 2KMnO4 → K 2MnO4 + MnO2 + O2
(c) 10−8 m (d) 10−2 m
(d) 2CuBr → CuBr2 + Cu
4. In order to oxidise a mixture of one mole of each of FeC2 O4 ,
2. In an acid-base titration, 0.1 M HCl solution was added to
Fe2 (C2 O4 )3 , FeSO4 and Fe2 (SO4 )3 in acidic medium, the
the NaOH solution of unknown strength. Which of the
number of moles of KMnO4 required is (2019 Main, 8 April I)
following correctly shows the change of pH of the titration
(a) 2 (b) 1 (c) 3 (d) 1.5
mixture in this experiment? (2019 Main, 9 April II)
5. 100 mL of a water sample contains 0.81 g of calcium
bicarbonate and 0.73 g of magnesium bicarbonate. The
hardness of this water sample expressed in terms of
pH pH equivalents of CaCO3 is (molar mass of calcium bicarbonate
is 162 g mol−1 and magnesium bicarbonate is 146 g mol−1 )
(2019 Main, 8 April I)
V(mL) V(mL)
(a) 5,000 ppm (b) 1,000 ppm
(A) (B)
(c) 100 ppm (d) 10,000 ppm
6. 50 mL of 0.5 M oxalic acid is needed to neutralise 25 mL of
sodium hydroxide solution. The amount of NaOH in 50 mL
pH pH
of the given sodium hydroxide solution is
(2019 Main, 12 Jan I)
(a) 40 g (b) 80 g (c) 20 g (d) 10 g
V(mL) V(mL)
(C) (D) 7. 25 mL of the given HCl solution requires 30 mL of 0.1 M
(2019 Main, 9 April II)
sodium carbonate solution. What is the volume of this HCl
(a) (D) (b) (A)
solution required to titrate 30 mL of 0.2 M aqueous NaOH
(c) (B) (d) (C) solution? (2019 Main, 11 Jan II)
3. 0.27 g of a long chain fatty acid was dissolved in 100 cm 3 of (a) 75 mL (b) 25 mL
hexane. 10 mL of this solution was added dropwise to the (c) 12.5 mL (d) 50 mL
 Some Basic Concepts of Chemistry 5

8. In the reaction of oxalate with permanganate in acidic 17. The oxidation number of sulphur in S 8 , S 2 F 2 , H 2 S
medium, the number of electrons involved in producing one respectively, are (1999)
molecule of CO2 is (2019 Main, 10 Jan II) (a) 0, +1 and –2 (b) +2, +1 and –2
(a) 2 (b) 5 (c) 1 (d) 10 (c) 0, +1 and +2 (d) –2, +1 and –2
9. The ratio of mass per cent of C and H of an organic 18. The number of moles of KMnO 4 that will be needed to react
compound (Cx H y O z ) is 6 : 1. If one molecule of the above
completely with one mole of ferrous oxalate in acidic
compound (Cx H y O z ) contains half as much oxygen as
medium is (1997)
required to burn one molecule of compound Cx H y
2 3 4
completely to CO2 and H2 O. The empirical formula of (a) (b) (c) (d) 1
compound Cx H y O z is (2018 Main)
5 5 5
(a) C3 H6 O3 (b) C2 H4 O (c) C3 H4 O2 (d) C2 H4 O3 19. The number of moles of KMnO 4 that will be needed to react
10. An alkali is titrated against an acid with methyl orange as with one mole of sulphite ion in acidic solution is
(1997)
indicator, which of the following is a correct combination?
(2018 Main) 2 3 4
(a) (b) (c) (d) 1
5 5 5
Base Acid End point
(a) Weak Strong Colourless to pink 20. For the redox reaction
(b) Strong Strong Pinkish red to yellow MnO4− + C2 O24 − + H+ → Mn 2+ + CO2 + H2 O
(c) Weak Strong Yellow to pinkish red The correct coefficients of the reactants for the balanced
(d) Strong Strong Pink to colourless reaction are
11. From the following statements regarding H2 O2 choose the MnO−4 C2 O42 − H+ (1992)
incorrect statement. (2015 Main) (a) 2 5 16
(a) It can act only as an oxidising agent (b) 16 5 2
(b) It decomposed on exposure to light (c) 5 16 2
(c) It has to be stored in plastic or wax lined glass bottles in (d) 2 16 5
dark 21. The volume strength of 1.5 N H2 O2 is (1990, 1M)
(d) It has to be kept away from dust (a) 4.8 (b) 8.4 (c) 3.0 (d) 8.0
12. Consider a titration of potassium dichromate solution with 22. The oxidation number of phosphorus in Ba(H2 PO2 )2 is
acidified Mohr’s salt solution using diphenylamine as
(a) +3 (b) +2 (1988)
indicator. The number of moles of Mohr's salt required per
(c) +1 (d) –1
mole of dichromate is (2007, 3M)
(a) 3 (b) 4 (c) 5 (d) 6 23. The equivalent weight of MnSO 4 is half of its molecular
13. In the standardisation of Na 2 S2 O3 using K 2 Cr2 O7 by weight, when it converts to (1988, 1M)
iodometry, the equivalent weight of K 2 Cr2 O7 is (2001, 1M) (a) Mn 2 O3 (b) MnO2
(a) (molecular weight)/2 (b) (molecular weight)/6 (c) MnO−4 (d) MnO2−
4
(c) (molecular weight)/3 (d) same as molecular weight
14. The reaction, 3ClO − (aq) → ClO3– (aq) + 2Cl − (aq) is an Objective Question II (More than one correct option)
example of (2001) 24. For the reaction, I− + ClO3− + H2 SO4 → Cl − + HSO4− + I2
(a) oxidation reaction the correct statement(s) in the balanced equation is/are
(b) reduction reaction (a) stoichiometric coefficient of HSO−4 is 6 (2014 Adv.)
(c) disproportionation reaction (b) iodide is oxidised
(d) decomposition reaction (c) sulphur is reduced
15. An aqueous solution of 6.3 g oxalic acid dihydrate is made up (d) H2 O is one of the products
to 250 mL. The volume of 0.1 N NaOH required to
completely neutralise 10 mL of this solution is (2001, 1M) Numerical Answer Type Questions
(a) 40 mL (b) 20 mL (c) 10 mL (d) 4 mL 25. 5.00 mL of 0.10 M oxalic acid solution taken in a conical
16. Among the following, the species in which the oxidation flask is titrated against NaOH from a burette using
number of an element is + 6 (2000) phenolphthalein indicator. The volume of NaOH required for
(a) MnO−4 (b) Cr(CN)3−
6
the appearance of permanent faint pink color is tabulated
below for five experiments. What is the concentration, in
(c) NiF62− (d) CrO2 Cl 2
molarity, of the NaOH solution?
6 Some Basic Concepts of Chemistry

Exp. No. Vol. of NaOH (mL) Integer Answer Type Questions

1 12.5
31. The difference in the oxidation numbers of the two types of
2 10.5
sulphur atoms in Na 2 S4 O6 is (2011)
3 9.0
4 9.0
32. Among the following, the number of elements showing only
one non-zero oxidation state is O, Cl, F, N, P, Sn, Tl, Na, Ti
5 9.0 (2010)
(2020 Adv.)
33. A student performs a titration with different burettes and
26. Aluminium reacts with sulphuric acid to form aluminium finds titrate values of 25.2 mL, 25.25 mL, and 25.0 mL. The
sulphate and hydrogen. What is the volume of hydrogen gas number of significant figures in the average titrate value is
in litre (L) produced at 300 K and 1.0 atm pressure, when (2010)
5.4 g of aluminium and 50.0 mL of 5.0 M sulphuric acid are
combined for the reaction? Subjective Questions
(Use molar mass of aluminium as 27.0 g mol −1 , R = 0.082
34. Calculate the amount of calcium oxide required when it
reacts with 852 g of P4 O10 . (2005, 2M)
atm L mol −1 K −1 ) (2020 Adv.)
35. Hydrogen peroxide solution (20 mL) reacts quantitatively
27. A 20.0 mL solution containing 0.2 g impure H 2O2 reacts with a solution of KMnO4 (20 mL) acidified with dilute
completely with 0.316 g of KMnO4 in acid solution. The H2 SO4 . The same volume of the KMnO4 solution is just
purity of H 2O2 (in%) is ............. (molecular weight of decolourised by 10 mL of MnSO4 in neutral medium
H 2O2 = 34; molecular weight of KMnO4 = 158 ). simultaneously forming a dark brown precipitate of hydrated
(2020 Main, 4 Sep I) MnO2 . The brown precipitate is dissolved in 10 mL of 0.2 M
28. The ammonia prepared by treating ammonium sulphate with sodium oxalate under boiling condition in the presence of
calcium hydroxide is completely used by NiCl 2 ⋅ 6H2 O to dilute H2 SO4 . Write the balanced equations involved in the
form a stable coordination compound. Assume that both the reactions and calculate the molarity of H2 O2 . (2001)
reactions are 100% complete. If 1584 g of ammonium 36. How many millilitres of 0.5 M H2 SO4 are needed to dissolve
sulphate and 952 g of NiCl 2 ⋅ 6H2 O are used in the 0.5 g of copper (II) carbonate? (1999, 3M)
preparation, the combined weight (in grams) of gypsum
and the nickel-ammonia coordination compound thus 37. An aqueous solution containing 0.10 g KIO3
produced is____ (formula weight = 214.0) was treated with an excess of KI
solution. The solution was acidified with HCl. The liberated
(Atomic weights in g mol −1 : H = 1, N = 14, O = 16, S = 32, I2 consumed 45.0 mL of thiosulphate solution decolourise
Cl = 35.5, Ca = 40, Ni = 59) (2018 Adv.) the blue starch-iodine complex. Calculate the molarity of the
sodium thiosulphate solution. (1998, 5M)
Assertion and Reason 38. To a 25 mL H2 O2 solution, excess of acidified solution of
Read the following questions and answer as per the direction potassium iodide was added. The iodine liberated required
given below :
20 mL of 0.3 N sodium thiosulphate solution. Calculate the
(a) Statement I is true; Statement II is true; Statement II is the
volume strength of H2 O2 solution. (1997, 5M)
correct explanation of Statement I.
(b) Statement I is true; Statement II is true; Statement II is not 39. A 3.00 g sample containing Fe3 O4 , Fe2 O3 and an inert
the correct explanation of Statement I. impure substance, is treated with excess of KI solution in
(c) Statement I is true; Statement II is false. presence of dilute H2 SO4 . The entire iron is converted into
(d) Statement I is false; Statement II is true. Fe2+ along with the liberation of iodine. The resulting
solution is diluted to 100 mL . A 20 mL of the diluted
29. Statement I In the titration of Na 2 CO3 with HCl using solution requires 11.0 mL of 0.5 M Na 2 S2 O3 solution to
methyl orange indicator, the volume required at the reduce the iodine present. A 50 mL of the dilute solution,
equivalence point is twice that of the acid required using after complete extraction of the iodine required 12.80 mL of
phenolphthalein indicator. 0.25 M KMnO4 solution in dilute H2 SO4 medium for the
Statement II Two moles of HCl are required for the oxidation of Fe2+ . Calculate the percentage of Fe2 O3 and
complete neutralisation of one mole of Na 2 CO3 . (1991, 2M) Fe3 O4 in the original sample. (1996, 5M)
40. A 20.0 cm 3 mixture of CO, CH4 and He gases is exploded by
Fill in the Blanks an electric discharge at room temperature with excess of
30. The compound YBa 2 Cu 3 O7 , which shows super oxygen. The volume contraction is found to be 13.0 cm 3 .
conductivity, has copper in oxidation state ………. Assume A further contraction of 14.0 cm 3 occurs when the residual
that the rare earth element yttrium is in its usual + 3 oxidation gas is treated with KOH solution. Find out the composition
state. (1994, 1M)
of the gaseous mixture in terms of volume percentage.
(1995, 4M)
 Some Basic Concepts of Chemistry 7

41. A 5.0 cm 3 solution of H2 O2 liberates 0.508 g of iodine from Calculate the amount of H2 C2 O4 and NaHC2 O4 in the
an acidified KI solution. Calculate the strength of H2 O2 mixture. (1990, 5M)
solution in terms of volume strength at STP. (1995, 3M) 47. An organic compound X on analysis gives 24.24 per cent
42. One gram of commercial AgNO3 is dissolved in 50 mL of carbon and 4.04 per cent hydrogen. Further, sodium extract
of 1.0 g of X gives 2.90 g of silver chloride with acidified
water. It is treated with 50 mL of a KI solution. The silver
silver nitrate solution. The compound X may be represented
iodide thus precipitated is filtered off. Excess of KI in the
by two isomeric structures Y and Z. Y on treatment with
filtrate is titrated with (M/10) KIO 3 solution in presence of
aqueous potassium hydroxide solution gives a dihydroxy
6 M HCl till all I− ions are converted into ICl. It requires compound while Z on similar treatment gives ethanal. Find
50 mL of (M/10) KIO 3 solution, 20 mL of the same stock out the molecular formula of X and gives the structure
solution of KI requires 30 mL of (M/10) KIO3 under similar of Y and Z. (1989, 5M)
conditions. Calculate the percentage of AgNO3 in the
sample. 48. An equal volume of a reducing agent is titrated separately
Reaction KIO3 + 2KI + 6HCl → 3ICl + 3KCl + 3H2 O with 1 M KMnO4 in acid, neutral and alkaline medium. The
(1992, 4M)
volumes of KMnO4 required are 20 mL in acid, 33.3 mL in
neutral and 100 mL in alkaline media. Find out the oxidation
43. A 2.0 g sample of a mixture containing sodium carbonate, state of manganese in each reduction product. Give the
sodium bicarbonate and sodium sulphate is gently heated till balanced equations for all the three half reaction. Find out the
the evolution of CO2 ceases. The volume of CO2 at 750 mm volume of 1M K 2 Cr2 O7 consumed, if the same volume of the
Hg pressure and at 298 K is measured to be 123.9 mL. A 1.5 g reducing agent is titrated in acid medium. (1989, 5M)
of the same sample requires 150 mL of (M/10) HCl for
49. A sample of hydrazine sulphate ( N2 H 6 SO4 ) was dissolved in
complete neutralisation. Calculate the percentage
composition of the components of the mixture. (1992, 5M) 100 mL of water, 10 mL of this solution was reacted with
excess of ferric chloride solution and warmed to complete
44. A 1.0 g sample of Fe2 O3 solid of 55.2% purity is dissolved in the reaction. Ferrous ion formed was estimated and it,
acid and reduced by heating the solution with zinc dust. The required 20 mL of M/50 potassium permanganate solution.
resultant solution is cooled and made up to 100.0 mL. An Estimate the amount of hydrazine sulphate in one litre of the
aliquot of 25.0 mL of this solution requires for titration. solution.
Calculate the number of electrons taken up by the oxidant in Reaction 4Fe3+ + N2 H4 → N2 + 4Fe2+ + 4H+
the reaction of the above titration. (1991, 4M)
MnO−4 + 5Fe2+ + 8H+ → Mn 2+ + 5Fe3+ + 4H2 O
45. A solution of 0.2 g of a compound containing Cu 2+ and
(1988, 3M)
C2 O2−
4 ions on titration with 0.02 M KMnO4 in presence of
50. 5 mL of 8 N nitric acid, 4.8 mL of 5 N hydrochloric acid and
H2 SO4 consumes 22.6 mL of the oxidant. The resultant a certain volume of 17 M sulphuric acid are mixed together
solution is neutralised with Na 2 CO3 , acidified with dilute and made up to 2 L. 30 mL of this acid mixture exactly
acetic acid and treated with excess KI. The liberated iodine neutralise 42.9 mL of sodium carbonate solution containing
requires 11.3 mL of 0.05 M Na 2 S2 O3 solution for complete one gram of Na 2 CO3 ⋅ 10H2 O in 100 mL of water. Calculate
reduction. Find out the mole ratio of Cu 2+ to C2 O2−4 in the the amount in gram of the sulphate ions in solution.
compound. Write down the balanced redox reactions (1985, 4M)
involved in the above titrations. (1991, 5M) 51. 2.68 × 10−3 moles of a solution containing an ion A n+ require
46. A mixture of H2 C2 O4 (oxalic acid) and NaHC2 O4 weighing 1.61 × 10−3 moles of MnO−4 for the oxidation of A n+ to A O−3
2.02 g was dissolved in water and the solution made up to one in acidic medium. What is the value of n ? (1984, 2M)
litre. Ten millilitres of the solution required 3.0 mL of 0.1 N 52. 4.08 g of a mixture of BaO and unknown carbonate MCO3
sodium hydroxide solution for complete neutralisation. In
was heated strongly. The residue weighed 3.64 g. This was
another experiment, 10.0 mL of the same solution, in hot
dissolved in 100 mL of 1 N HCl. The excess acid required
dilute sulphuric acid medium, required 4.0 mL of 0.1 N
16 mL of 2.5 N NaOH solution for complete neutralisation.
potassium permanganate solution for complete reaction.
Identify the metal M. (1983, 4M)

Answers
Topic 1 13. (b) 14. (*) 15. (d) 16. (d)
1. (d) 2. (c) 3. (b) 4. (a) 17. (b) 18. (a) 19. (c) 20. (b)
5. (d) 6. (b) 7. (d) 8. (c) 21. (a) 22. (a) 23. (d) 24. (d)
9. (b) 10. (b) 11. (b) 12. (c) 25. (d) 26. (a) 27. (d) 28. (a)
29. (a) 30. (a) 31. (a) 32. (c)
8 Some Basic Concepts of Chemistry

33. (10.00) 34. (6.47kg) 35. (126 mg) 36. (495 g) 5. (d) 6. (*) 7. (b) 8. (c)
37. (4.14 g) 38. (0.4) 39. (6.023×10 24 ) 40. C-12 9. (d) 10. (c) 11. (a) 12. (d)
isotope 13. (b) 14. (c) 15. (a) 16. (d)
41. (9) 42. (8) 43. (8 mL) 44. (2) 17. (a) 18. (b) 19. (a) 20. (a)
45. (5 × 10 −19 m 2 ) 46. (55.56 mol 21. (b) 22. (c) 23. (b) 24. (a,b,d)
L −1) 47. (70.91 × 10 6g) 48. (4.3 × 10 −3) 25. (0.11) 26. (6.15) 27. (85)
51. (10.42) 52. (1.7 g) 53. (55.55 L) 54. (9.9 × 10 −3) 28. (2992) 29. (b) 30. 7/3 31. (5)
56. (i) (37.92), (ii) (0.065), (iii) (7.73m) 57. (a) (0.6), (b) (24) 32. (2) 33. (3) 34. (1008 g) 36. (8.096 mL)
59. (i) (0.0179 g), (ii) (10.6 %) 60. (0.437) 62. (20 %) 37. (0.062 M) 38. (1.334 V) 42. (85%) 44. (1.04)
Topic 2 45. (1:2) 48. (16.67 mL) 49. (6.5gL −1) 50. (6.5376 g)
1. (d) 2. (b) 3. (a) 4. (a) 51. (2) 52. (Ca)

Hints & Solutions

Topic 1 Mole Concept (c) 4Fe(s) + 3O2(g ) → 2Fe2O3 (s)
244g 96g 96
Key Idea To find the mass of A and B in the given question, ⇒ 1 g of reactant = g of O2 consumed = 0.43 g
1. 224
mole concept is used.
given mass (w) (d) 2Mg(s) + O2(g ) → 2MgO(s)
Number of moles( n) = 48 g 32 g
molecular mass (M )
32
⇒ 1 g of reactant = g of O2 consumed = 0.67 g
48
Compound Mass of A (g) Mass of B (g)
So, minimum amount of O2 is consumed per gram of reactant
AB2 MA 2 MB (Fe) in reaction (c).
A 2B 2 2 MA 2 MB 3. In eudiometry,
300 K
 y y
We know that, CxH y +  x +  O2 → x CO2 + H2O
 4 1 atm 2
given mass (w)
Number of moles (n) =  y
molecular mass (M ) 1 mol  x +  mol x mol
 4
n×M = w …(A) 1 mL
 y
 x +  mL x mL
 4
Using equation (A), it can be concluded that
 y
10 mL  x +  × 10 mL 10x mL
5(M A + 2M B ) = 125 × 10−3 kg …(i)  4

10(2M A + 2M B ) = 300 × 10−3 kg …(ii) Given, (i) VCO2 = 10x = 40 mL ⇒ x = 4

 y
From equation (i) and (ii) (ii) VO2 = 10  x +  mL = 55 mL
 4
1 (M A + 2M B )  125 
=   y
2 (2M A + 2M B )  300 ⇒ 10  4 +  = 55 [Qx = 4]
 4
On solving the equation, we obtain
y × 10
M A = 5 × 10−3 ⇒ 40 + = 55
4
and M B = 10 × 10−3 10 4
⇒ y× = 15 ⇒ y = 15 × =6
So, the molar mass of A (M A ) is 4 10
5 × 10−3 kg mol −1 and B (M B ) is 10 × 10−3 kg mol −1. So, the hydrocarbon (CxH y ) is C4H6.

2. (a) C3H8 (g ) + 5O2 (g ) → 3CO2 (g ) + 4H2O(l ) 4. Given, volume = 10 mL

44g 160g Molarity = 1mM = 10−3 M
160 ∴Number of millimoles = 10 mL × 10−3 M = 10−2
⇒ 1g of reactant = g of O2 consumed = 3.64 g
44 Number of moles = 10−5
(b) P4 (s) + 5O2(g ) → P4O10 (s) Now, number of molecules
124g 160g
= Number of moles × Avogadro’s number
160
⇒1 g of reactant = g of O2 consumed = 129
. g = 10−5 × 6 × 1023 = 6 × 1018
124
 Some Basic Concepts of Chemistry 9

Surface area occupied by 6 × 1018 molecules = 0.24 cm2 w Solute

∴Surface area occupied by 1 molecule n Solute Mw Solute
χ Solute = =
0.24 n Solute + nSolvent w Solute w
+ Solvent
= = 0.04 × 10−18 cm2 Mw Solute MwSolvent
6 × 1018
As it is given that polar head is approximated as cube. Thus, Given, wSolute = wNaOH = 8 g
surface area of cube = a2, where Mw Solute = MwNaOH = 40g mol − 1
a =edge length w Solvent = w H2 O = 18g
∴ a = 4 × 10−20 cm2
2
Mw Solvent = 18 g mol− 1
a = 2 × 10−10 cm = 2 pm 8 / 40 0.2 0.2
∴ χ Solute = χ NaOH = = = = 0167
.
8 18 0.2 + 1 12
.
5. Key Idea The reactant which is present in the lesser amount, +
i.e. which limits the amount of product formed is called 40 18
limiting reagent. Moles of solute
Now, molality (m) =
Mass of solvent (in kg)
When 56 g of N2 + 10 g of H2 is taken as a combination then w Solute 8
dihydrogen (H2 ) act as a limiting reagent in the reaction.
Mw Solute 40
N2 (g ) + 3H2 (g ) → 2NH3 (g ) …(I) = × 1000 = × 1000
wSolvent (in g ) 18
2 × 14 g 3 × 2g 2(14 + 3) g
0.2
28g 6g 34g = × 1000 = 11.11mol kg − 1
18
28g N2 requires 6g H2 gas.
Thus, mole fraction of NaOH in solution and molality of the
6g
56g of N2 requires × 56 g = 12g of H2 solution respectively are 0.167 and 11.11 mol kg − 1 .
28 g
8. Concentration of H2O2 is expressed in terms of volume strength,
12g of H2 gas is required for 56g of N2 gas but
i.e. “volume of O2 liberated by H2O2 at NTP”. Molarity is
only 10 g of H2 gas is present in option (a).
connected to volume strength as:
Hence, H2 gas is the limiting reagent. x
In option (b), i.e. 35g of N2 + 8 g of H2. Molarity (M) = or x = Molarity × 11.2
112
.
As 28 g N2 requires 6g of H2. where, x = volume strength
6g So, for 1 M H2O2, x = 1 × 112. = 112.
35g N2 requires × 35 g H2 ⇒ 7.5 g of H2.
28 g Among the given options, 11.35 is nearest to 11.2.
Here, H2 gas does not act as limiting reagent since 7.5 g of H2 Number of moles of solute (n)
gas is required for 35g of N2 and 8g of H2 is present in reaction 9. Molarity =
Volume of solution (in L)
mixture. Mass of H2 left unreacted = 8 − 7.5 g of H2.
wB (g)
= 0.5 gof H2. Also, n =
M B (gmol−1 )
Similarly, in option (c) and (d), H2 does not act as limiting
reagent. w / MB
∴ Molarity = B
For 14 g of N2 + 4 g of H2. V
As we know 28g of N2 reacts with 6g of H2. Given, wB = mass of solute ( B ) in g
6 M B = Gram molar mass of B (C12H22O11 ) = 342 g mol −1
14 g of N2 reacts with × 14 g of H2 ⇒ 3g of H2.
28 Molarity = 01. M
For 28g of N2 + 6 g of H2, i.e. 28g of N2 reacts with 6g of H2 Volume (V ) = 2 L
(by equation I). w / 342
⇒ . = B
01 ⇒ wB = 01
. × 342 × 2 g = 68.4 g
2
6. Key Idea The percentage composition of a compound is given 10. 2 C57 H110O6 (s) + 163 O2 (g ) → 110H2O(l ) + 114 CO2 (g )
by the formula.
% composition = [Composition of a substance in a compound / Molecular mass of C57H110O6
Total composition total of compound] ×100 = 2 × (12 × 57 + 1 × 110 + 16 × 6) g = 1780 g
Molecular mass of 110 H2O = 110 (2 + 16) = 1980 g
In CH4 , 1780 g of C57H110O6 produced = 1980 g of H2O.
mole of carbon = 1 1980
mole of hydrogen = 4 445g of C57H110O6 produced = × 445 g of H2O
1780
1 = 495 of H2O
∴ % of carbon by mole in CH4 = × 100 = 20%
1+ 4
Number of moles of solute
11. Molality (m) = × 1000
7. Mole fraction of solute Mass of solvent (in g)
number of moles of solute + number of moles solvent
=
number of moles of solute
10 Some Basic Concepts of Chemistry

Mass of solute (in g) × 1000 16. Given, initial strength of acetic acid = 0.06 N
=
Molecular weight of solute 
 × mass of solvent (in g) Final strength = 0.042 N; Volume = 50 mL
wNa + × 1000 92 × 1000 ∴Initial millimoles of CH3COOH = 0.06 × 50 = 3
= = = 4 mol kg − 1
M Na + × wH 2 O 23 × 1000 Final millimoles of CH3COOH = 0.042 × 50 = 2.1
∴ Millimoles of CH3COOH adsorbed = 3 − 2.1= 0.9 mmol
12. Given, abundance of elements by mass
= 0.9 × 60 mg = 54 mg
oxygen = 614. %, carbon = 22.9%, hydrogen = 10% and (mO 2 )
nitrogen = 2.6% nO 2 (M O 2 )
Total weight of person = 75 kg 17. =
nN 2 (mN 2 )
75 × 10
Mass due to 1 H = = 7.5 kg (M N 2 )
100
1 2
H atoms are replaced by H atoms, where, mO 2 = given mass of O2 , mN 2 = given mass of N2 ,
Mass due to 2 H = (7.5 × 2) kg M O 2 = molecular mass of O2 , M N 2 = molecular mass of N2 , nO 2 =
number of moles of O2 , nN 2 = number of moles of N2
∴ Mass gain by person = 7.5 kg
 mO  28 1 28 7
13. M 2CO3 + 2HCl → 2M Cl + H2O + CO2 = 2 = × =
1g 0.01186  mN 2  32 4 32 32
mole
M 1V1 + M 2V2
Number of moles of M 2CO3 reacted = Number of moles of 18. From the formula, M f =
CO2 evolved V1 + V2
1 Given, V1 = 750 mL, M 1 = 0.5 M
= 0.01186 [M = molar mass of M 2CO3]
M V2 = 250 mL, M 2 = 2 M
1
M = = 84.3 g mol − 1 750 × 0.5 + 250 × 2 875
0.01186 = = = 0.875 M
750 + 250 1000
14. CxH y (g ) +  x +  O2 (g ) → xCO2 (g ) + H2O(l )
y y
Moles of solute
 4 30 mL
2 19. Molarity =
75 mL Volume of solution (L)
O 2 used = 20% of 375 = 75 mL 120
Moles of urea = =2
Inert part of air = 80% of 375 = 300 mL 60
Total volume of gases = CO2 + Inert part of air Weight of solution = Weight of solvent + Weight of solute
= 30 + 300 = 330 mL = 1000 + 120 = 1120 g
x 30 1120 g 1
= ⇒x=2 ⇒ Volume = × = 0.973 L
1 15 1.15 g / mL 1000 mL / L
y 2.000
x+ ⇒ Molarity = = 2.05M
4 = 75 ⇒ x + y = 5 0.973
1 15 4
⇒ x = 2, y = 12 ⇒ C2 H12 20. From the given relative abundance, the average weight of Fe can be
calculated as
15. We know the molecular weight of C8 H7 SO3Na 54 × 5 + 56 × 90 + 57 × 5
A= = 55.95
= 12 × 8 + 1 × 7 + 32 + 16 × 3 + 23 = 206 100
we have to find, mole per gram of resin. 21. 1.0 L of mixture X contain 0.01 mole of each [Co(NH3 )5 SO4 ]Br
∴ 1g of C8 H7 SO3Na has number of mole and [Co(NH3 )5 Br]SO4. Also, with AgNO3, only
weight of given resin 1 [Co(NH3 )5 SO4 ]Br reacts to give AgBr precipitate as
= = mol
Molecular, weight of resin 206 [Co(NH3 )5 SO4 ]Br + AgNO3 → [Co(NH3 )5 SO4 ]NO3 + AgBr
1.0 mol Excess 1.0 mol
Now, reaction looks like With BaCl 2, only [Co(NH3 )5 Br]SO4 reacts giving BaSO4
2C8 H7 SO3Na + Ca 2+ → (C8 H7 SO3 )2 Ca + 2Na precipitate as
Q 2 moles of C8 H7 SO3Na combines with 1 mol Ca 2+ [Co(NH3 )5 Br]SO4 + BaCl 2 → [Co(NH3 )5 Br]Cl 2 + BaSO4
1.0 mol Excess 1 mol
1 Hence, moles of Y and Z are 0.01 each.
∴1 mole of C8 H7 SO3Na will combine with mol Ca 2+
2
22. Number of atoms = Number of moles
1
∴ mole of C8 H7 SO3 Na will combine with × Avogadro’s number (N A)
206 24
1 1 1 Number of atoms in 24 g C = × NA = 2NA
× mol Ca 2+ = mol Ca 2+ 12
2 206 412
 Some Basic Concepts of Chemistry 11

56 30. Number of molecules present in 36 g of water

Number of atoms in 56 g of Fe = NA = NA
56 36
27 = × N A = 2N A
Number of atoms in 27 g of Al = NA = NA 18
27
108 28
Number of atoms in 108 g of Ag = NA = NA Number of molecules present in 28 g of CO = × NA = NA
108 28
46
Hence, 24 g of carbon has the maximum number of atoms. Number of molecules present in 46 g of C2H5OH = × NA = NA
46
23. Mass of an electron = 9.108 × 10−31 kg 54
Number of molecules present in 54 g of N2O5 = × N A = 0.5 N A
Q 9.108 × 10−31 kg = 1.0 electron 108
1 1031 1 Here, NA is Avogadro’s number. Hence, 36 g of water contain
∴ 1 kg = −31
electrons = × the largest (2NA ) number of molecules.
9.108 × 10 9.108 6.023 × 1023
1 31. In a neutral atom, atomic number represents the number of
= × 108 mole of electrons protons inside the nucleus and equal number of electrons around
9.108 × 6.023
it. Therefore, the number of total electrons in molecule of CO2
24. Phosphorus acid is a dibasic acid as : = electrons present in one carbon atom
O
+ 2 × electrons present in one oxygen atom

H—P — OH only two replaceable hydrogens = 6 + 2 × 8 = 22.

Weight of a compound in gram (w)
OH 32. = Number of moles (n)
Molar mass (M )
Therefore, normality = molarity × basicity = 0.3 × 2 = 0.60
Number of molecules (N )
25. Molality is defined in terms of weight, hence independent of =
Avogadro number (NA )
temperature. Remaining three concentration units are defined in
terms of volume of solution, they depends on temperature. w (O2 ) N (O2 )
⇒ = …(i)
26. Molality of a solution is defined as number of moles of solute 32 NA
present in 1.0 kg (1000 g) of solvent. w (N2 ) N (N2 )
And = …(ii)
27. The balanced chemical reaction is 28 NA
3BaCl 2 + 2Na 3PO4 → Ba 3 (PO4 )2 + 6NaCl Dividing Eq. (i) by Eq. (ii) gives
In this reaction, 3 moles of BaCl 2 combines with 2 moles of N (O2 ) w (O2 ) 28 1 28 7
Na 3PO4. Hence, 0.5 mole of of BaCl 2 require = × = × =
N (N2 ) w (N2 ) 32 4 32 32
2
× 0.5 = 0.33 mole of Na 3PO4. 33. Molar mass of Na 2CO3⋅ xH2O .
3
Since, available Na 3PO4 (0.2 mole) is less than required mole (Atomic mass of Na = 23, C = 12, O = 16)
(0.33), it is the limiting reactant and would determine the = 23 × 2 + 12 + 48 + 18x
amount of product Ba 3 (PO4 )2. = 46 + 12 + 48 + 18x
Q 2 moles of Na 3PO4 gives 1 mole Ba 3 (PO4 )2 = (106 + 18x )
1
∴0.2 mole of Na 3PO4 would give × 0.2 = 0.1 mole Ba 3 (PO4 )2 Equivalent weight of Na 2CO3⋅ xH2O
2
Molar mass M
28. Unlike other metal carbonates that usually decomposes into = = = (53 + 9x )
n factor 2
metal oxides liberating carbon dioxide, silver carbonate on
heating decomposes into elemental silver liberating mixture of [ Here, m = molar mass and n factor = 2]
carbon dioxide and oxygen gas as : Weight
Gram equivalent =
Heat 1 Equivalent weight
Ag2CO3 (s) → 2Ag (s) + CO2 (g ) + O (g )
2 2
[Given, weight of Na 2CO3 ⋅ xH2O = 143
. g]
MW = 276 g 2 × 108 = 216 g
Hence, 2.76 g of Ag2CO3 on heating will give Hence, gram equivalent of
216 1.43
× 2.76 = 2.16g Ag as residue. Na 2CO3 ⋅ xH2O =
276 53 + 9x
Gmeq
29. The balanced chemical reaction of zinc with sulphuric acid and Normality =
NaOH are Vlitre
Zn + H2SO4 → ZnSO4 + H2 (g ) ↑ 143
.
01. =
Zn + 2NaOH + 2H2O → Na 2[ Zn(OH)4 ] + H2 (g ) ↑ 53 + 9x
Since, one mole of H2 (g ) is produced per mole of zinc with both 01.
sulphuric acid and NaOH respectively, hydrogen gas is As, volume = 100 mL = 0.1 L
produced in the molar ratio of 1:1 in the above reactions.
12 Some Basic Concepts of Chemistry

143
.
So, 10−2 = 36. Given,
53 + 9x O
53 + 9x = 143
9x = 90 NaOBr NH3/∆ Br2/KOH Br2(3-eqiv.)
A B C D
x = 10.00 H3O+ (60%) (50%) (50%)
AcOH
(100%)
34. The equations of chemical reactions occurring during the process
The products formed are
are
In the presence of oxygen O HO O H2N O
2PbS + 3O2 → 2PbO + 2SO2 …(i)
NaOBr NH3/∆
By self reduction
H3O+
2PbO + PbS → 3Pb + SO2
Acetophenone Benzoic acid Benzamide
Thus 3 moles of O2 produces 3 moles of Pb (60%) (50%)
Br2/KOH
10 mol
i.e. 32 × 3 = 96 g of O 2 produces 3 × 207 = 621 g of Pb i.e., i.e.,
6 mol 3 mol
So 1000 g (1kg) of oxygen will produce (A) (B)
621 NH2 NH2
× 1000 = 6468.75 g
96 Br Br
= 6.4687 kg ≈ 6.47 kg Br2(3-eqiv.)
AcOH
Alternative Method
From the direct equation, Aniline
Br (50%)
PbS + O2 → Pb + SO2 2,4,6-tribromo aniline i.e.,
32 g 207 g 1.5 mol
(100%)
i.e., (C)
So, 32 g of O 2 gives 207 g of Pb 1.5 mol
207 (D)
1 g of O 2 will give g of Pb
32 NH2
207 Br Br
1000g of O 2 will give × 1000 = 6468.75 g
32
= 6.46875 kg ≈ 6.47kg So, 1.5 mol of are produced from

35. The balanced equations are

Br
(1) 2MnCl 2 + 5K 2S2O 8 + 8H2O →
2KMnO 4 + 4 K 2SO 4 + 6H2SO 4 + 4HCl 10 moles of acetophenone.
NH2
(2) 2KMnO 4 + 5H2C 2O 4 + 3H2SO 4 → Br Br
K 2SO 4 + 2MnSO 4 + 8H2O +10CO 2
Molar mass of = 240 + 14 + 4 + 72 = 330
Given, mass of oxalic acid added = 225mg
225
So, millimoles of oxalic acid added = = 2.5 Br
90
NH2
Now from equation 2
Br Br
Millimoles of KMnO 4 used to react with oxalic acid=1 and
Millimoles of MnCl 2 required initially=1 Hence, amount of produced is 330 × 1.5 = 495 g
∴ Mass of MnCl 2 required initially = 1 × (55 + 71) = 126mg
Alternative Method Br
m moles of MnCl 2 = m moles of KMnO 4 = x (let) 37. Molar mass of CuSO4 ⋅ 5H2O
and M eq of KMnO 4 = M eq of oxalic acid
= 63.5 + 32 + 4 × 16 + 5 × 18
225
So, x×5= ×2 = 249.5 g
90
Also, molar mass represents mass of Avogadro number of
Hence, x = 1 molecules in gram unit, therefore
∴ m moles of MnCl 2 = 1 Q 6.023 × 1023 molecules of CuSO4 ⋅ 5H2O weigh 249.5 g
Hence mass of MnCl 2 = (55 + 71) × 1 = 126 mg. 249.5
∴ 1022 molecules will weigh × 1022 = 4.14 g
6.023 × 1023
 Some Basic Concepts of Chemistry 13

Number of moles of solute Mass of HCl required for 200 mL 0.4 M HCl
38. Molarity =
Volume of solution in litre 200
= × 0.4 × 36.5 = 0.08 × 36.5 g
Weight of solute 1000 1000
= ×
Molar mass Volume in mL ∴ 0.365 g of HCl is present in 1.0 mL stock solution.
3 1000 0.08 × 36.5
= × = 0.4 M 0.08 × 36.5 g HCl will be present in = 8.0 mL
30 250 0.365
39. Considering density of water to be 1.0 g/mL, 18 mL of water is 44. Partial pressure of N2 = 0.001 atm,
18 g (1.0 mol) of water and it contain Avogadro number of T = 298 K, V = 2.46 dm 3.
molecules. Also one molecule of water contain
2 × (one from each H-atom) + 8 × (from oxygen atom) From ideal gas law : pV = nRT
pV 0.001 × 2.46
= 10 electrons. n(N2 ) = = = 10−7
RT 0.082 × 298
⇒ 1.0 mole of H2O contain = 10 × 6.023 × 1023
⇒ Number of molecules of N2 = 6.023 × 1023 × 10−7
= 6.023 × 1024 electrons.
= 6.023 × 1016
40. Carbon-12 isotope. According to modern atomic mass unit, one Now, total surface sites available
atomic mass unit (amu) is defined as one-twelfth of mass of an
atom of C-12 isotope, i.e. = 6.023 × 1014 × 1000 = 6.023 × 1017
1 20
1 amu (u) = × weight of an atom of C-12 isotope. Surface sites used in adsorption = × 6.023 × 1017
12 100
w w = 2 × 6.023 × 1016
41. Moles of solute, n1 = 1 ; Moles of solvent, n2 = 2
m1 m2 ⇒ Sites occupied per molecules
χ 1 (solute) = 0.1and χ 2 (solvent) = 0.9 Number of sites 2 × 6.023 × 1016
= = = 2
χ 1 n1 w1 m2 1 Number of molecules 6.023 × 1016
∴ = = ⋅ =
χ 2 n2 m1 w2 9 45. Initial millimol of CH3COOH = 100 × 0.5 = 50
Solute (moles) w1 × 1000 × 2
Molarity = = millimol of CH3COOH remaining after adsorption
Volume (L) m1 (w1 + w2 )
= 100 × 0.49 = 49
Total mass of solution  w1 + w2 
Note Volume = =  mL ⇒ millimol of CH3COOH adsorbed = 50 – 49 = 1
Density  2 
⇒ number of molecules of CH3COOH adsorbed
Solute (moles) w1 × 1000 1
Molality = = = × 6.023 × 1023 = 6.023 × 1020
Solvent (kg) m1 × w2 1000
Given, molarity = molality 3.01 × 102
⇒ Area covered up by one molecule =
2000 w1 1000 w1 6.02 × 1020
hence, =
m1 (w1 + w2 ) m1 w2 = 5 × 10−19 m 2
w2 1
∴ = ⇒ w1 = w2 = 1 46. Mass of 1.0 L water = 1000 g
w1+ w2 2
1000
⇒ Molarity = = 55.56 mol L−1
w1 m2 1 m (solute) 18
∴ = ⇒ 1 =9
m1 w2 9 m2 (solvent)
47. Volume of one cylinderical plant virus = πr2l
42. PLAN This problem can be solved by using concept of conversion of = 3.14 (75 × 10−8 )2 × 5000 × 10−8 cm 3 = 8.83 × 10−17 cm 3
molarity into molality.
Volume of a virus
Molarity = 3.2 M ⇒ Mass of one virus =
Specific volume
Let volume of solution = 1000 mL = Volume of solvent
8.83 × 10−17 cm 3
Mass of solvent = 1000 × 0.4 = 400 g = = 1.1773 × 10−16 g
Since, molarity of solution is 3.2 molar 0.75 cm 3 g−1
∴ n solute = 3.2 mol ⇒ Molar mass of virus
3.2 = Mass of one virus × Avogadro’s number
Molality (m) = =8
400 / 1000 = 1.1773 × 10−16 × 6.023 × 1023 g
Hence, correct integer is (8).
= 70.91 × 106 g
43. Mass of HCl in 1.0 mL stock solution
48. Molar mass of Glauber’s salt (Na 2SO4 ⋅ 10H2O)
29.2
= 1.25 × = 0.365 g = 23 × 2 + 32 + 64 + 10 × 18 = 322g
100
14 Some Basic Concepts of Chemistry

80.575 If we consider 100 mL solution, weight of solution = 184 g

⇒ Mole of Na 2SO4 ⋅ 10H2O in 1.0 L solution = = 0.25
322 Weight of H2O in 100 mL solution = 184 – 93 = 91 g
⇒ Molarity of solution = 0.25 M Moles of solute
⇒ Molality = × 1000
Also, weight of 1.0 L solution = 1077.2 g Weight of solvent (g)
weight of Na 2SO4 in 1.0 L solution = 0.25 × 142 = 35.5 g 93 1000
⇒ Weight of water in 1.0 L solution = 1077.2 – 35.5 = 1041.7 g = × = 10.42
98 91
0.25
⇒ Molality = × 1000 = 0.24 m 52. Heating below 600°C converts Pb(NO3 )2 into PbO but to
1041.7
Mole of Na 2SO4 NaNO3 into NaNO2 as
Mole fraction of Na 2SO4 = ∆ 1
Mole of Na 2SO4 + Mole of water Pb(NO3 )2 → PbO(s) + 2NO2 ↑ + O ↑
2 2
0.25 MW : 330 222
= = 4.3 × 10−3. ∆ 1
1041.7 NaNO3 → NaNO2 (s) + O ↑
0.25 + 2 2
18 MW : 85 69
28
49. Compound B forms hydrated crystals with Al 2 (SO4 )3. Also, B is Weight loss = 5 × = 1.4 g
100
formed with univalent metal on heating with sulphur. Hence,
compound B must has the molecular formula M 2SO4 and ⇒ Weight of residue left = 5 – 1.4 = 3.6 g
compound A must be an oxide of M which reacts with sulphur to Now, let the original mixture contain x g of Pb(NO3 )2.
give metal sulphate as Q 330 g Pb(NO3 )2 gives 222 g PbO
A + S → M 2SO4 222 x
B
∴ x g Pb(NO3 )2 will give g PbO
330
Q 0.321 g sulphur gives 1.743 g of M 2SO4
Similarly, 85 g NaNO3 gives 69 g NaNO2
∴ 32.1 g S (one mole) will give 174.3 g M 2SO4
69 (5 − x )
Therefore, molar mass of M 2SO4 = 174.3 g ⇒ (5 – x) g NaNO3 will give g NaNO2
85
⇒ 174.3 = 2 × Atomic weight of M + 32.1 + 64
222 x 69 (5 − x )
⇒ Atomic weight of M = 39, metal is potassium (K) ⇒ Residue : + = 3.6 g
330 85
K2SO4 on treatment with aqueous Al 2 (SO4 )3 gives potash-alum.
Solving for x gives, x = 3.3 g Pb(NO3 )2 ⇒ NaNO3 = 1.7 g.
K2SO4 + Al 2 (SO4)3 + 24H2O → K2SO4Al 2 (SO4)3 ⋅ 24H2O
B C 53. Reactions involved are
If the metal oxide A has molecular formula MOx, two moles of it C2H6 + Br2 → C2H5Br + HBr
combine with one mole of sulphur to give one mole of metal 2C2H5Br + 2Na → C4H10 + 2NaBr
sulphate as Actual yield of C4H10 = 55 g which is 85% of theoretical yield.
2KOx + S → K2SO4
55 × 100
⇒ x = 2, i.e. A is KO2. ⇒ Theoretical yield of C4H10 = = 64.70 g
85
50. The reaction involved is Also, 2 moles (218 g) C2H5Br gives 58 g of butane.
3Pb(NO3 )2 + Cr2 (SO4 )3 → 3PbSO4 (s) ↓ + 2Cr(NO3 )3 ⇒ 64.70 g of butane would be obtained from
millimol of Pb(NO3 )2 taken = 45 × 0.25 = 11.25 2
× 64.70 = 2.23 moles C2H5Br
millimol of Cr2 (SO4 )3 taken = 2.5 58
Here, chromic sulphate is the limiting reagent, it will determine Also yield of bromination reaction is only 90%, in order to have
the amount of product. 2.23 moles of C2H5Br, theoretically
Q 1 mole Cr2 (SO4 )3 produces 3 moles PbSO4. 2.23 × 100
= 2.48 moles of C2H5Br required.
∴ 2.5 millimol Cr2 (SO4 )3 will produce 7.5 millimol PbSO4. 90
Hence, mole of PbSO4 precipitate formed = 7.5 × 10−3 Therefore, moles of C2H6 required = 2.48
⇒ Volume of C2H6 (NTP) required = 2.48 × 22.4 = 55.55 L.
Also, millimol of Pb(NO3 )2 remaining unreacted
34.2
11.25 – 7.50 = 3.75 54. Moles of sugar = = 0.1
342
⇒ Molarity of Pb(NO3 )2 in final solution
Moles of water in syrup = 214.2 – 34.2 = 180 g
millimol of Pb(NO3 )2 3.75 Moles of solute
= = = 0.054 M Therefore, (i) Molality = × 1000
Total volume 70 Weight of Solvent (g)
Also, millimol of Cr(NO3 )2 formed 0.1
= × 1000 = 0.55
= 2 × millimol of Cr2 (SO4 )3 reacted 180
5 Mole of sugar
⇒ Molarity of Cr(NO3 )2 = = 0.071 M (ii) Mole fraction of sugar =
70 Mole of sugar + Mole of water
51. 93% H2SO4 solution weight by volume indicates that there is 0.1
= = 9.9 × 10−3
93 g H2SO4 in 100 mL of solution. 0.1 + 10
 Some Basic Concepts of Chemistry 15

55. From the given elemental composition, empirical formula can 58. In the present case, V ∝ n (Q all the volumes are measured
be derived as : under identical conditions of temperature and pressure) Hence,
Element C H O the reaction stoichiometry can be solved using volumes as :
Weight % 69.77 11.63 18.60  y y
CxH y (g ) +  x +  O2 (g ) → x CO2 (g ) + H2O (l )
Mole % 5.81 11.63 1.1625 (obtained by  4 2
dividing from M ) volume of CO2 (g ) + O2 (g ) (remaining unreacted) = 25
Simple ratio 5 10 1 ⇒ Volume of CO2 (g ) produced
Hence, empirical formula is C5H10O and empirical formula = 10 mL (15 mL O2 remaining)
weight is 86. Q 1 mL CxH y produces x mL of CO2
Since, empirical formula weight and molecular weight both are ∴ 5 mL CxH y will produce 5x mL of CO2 = 10 mL ⇒ x = 2
(86), empirical formula is the molecular formula also.  y
Also, 1 mL CxH y combines with  x +  mL of O2
Also, the compound does not reduce Fehling’s solution,  4
therefore it is not an aldehyde, but it forms bisulphite, it must be
 y
a ketone. 5 mL CxH y will combine with 5  x +  mL of O2
 4
Also, it gives positive iodoform test, it must be a methyl ketone.
 y
O ⇒ 5  x +  = 15 (15 mL of O2 out of 30 mL)
 4
 (remaining unreacted)
C3H7 — C — CH3
⇒ y = 4, hence hydrocarbon is C2H4.
Based on the above information, the compound may be one of
the following : 59. Oxides of sodium and potassium are converted into chlorides
according to following reactions :
O CH3 O
   Na 2O + 2HCl → 2NaCl + H2O
CH3CH2CH2— C — CH3 or CH3 — CH— C — CH3 K2O + 2HCl → 2KCl + H2O
2-pentanone 3-methyl -2-butanone
Finally all the chlorides of NaCl and KCl are converted into
56. (a) Let us consider 1.0 L solution for all the calculation. AgCl, hence
(i) Weight of 1 L solution = 1250 g moles of (NaCl + KCl) = moles of AgCl
Weight of Na 2S2O3 = 3 × 158 = 474 g (one mole of either NaCl or KCl gives one mole of AgCl)
474 Now, let the chloride mixture contain x g NaCl.
⇒ Weight percentage of Na 2S2O3= × 100 = 37.92
1250 x 0.118 − x 0.2451
⇒ + =
(ii) Weight of H2O in 1 L solution = 1250 − 474 = 776 g 58.5 74.5 143.5
3 Solving for x gives x = 0.0338 g (mass of NaCl)
Mole fraction of Na 2S2O3 = = 0.065
776 ⇒ Mass of KCl = 0.118 – 0.0338 = 0.0842 g
3+
18 1
3×2 Also, moles of Na 2O = × moles of NaCl
(iii) Molality of Na + = × 100 = 7.73 m 2
776 1 0.0338
57. (a) After passing through red-hot charcoal, following reaction ⇒ Mass of Na 2O = × × 62 = 0.0179 g
2 58.5
occurs
1 0.0842
C(s) + CO2 (g ) → 2CO(g ) Similarly, mass of K2O = × × 94 = 0.053 g
2 74.5
If the 1.0 L original mixture contain x litre of CO2, after
0.0179
passing from tube containing red-hot charcoal, the new ⇒ Mass % of Na 2O = × 100 = 3.58 %
volumes would be : 0.5
2x (volume of CO obtained from CO2) + 1 0.053
Mass % of K2O = × 100 = 10.6 %
– x(original CO) = 1 + x =1.6 (given) 0.5
⇒ x = 0.6 60. From the vapour density information
Hence, original 1.0 L mixture has 0.4 L CO and 0.6 L of CO2 , Molar mass = Vapour density × 2 (Q Molar mass of H2 = 2)
i.e. 40% CO and 60% CO2 by volume. = 38.3 × 2 = 76.6
(b) According to the given information, molecular formula of Now, let us consider 1.0 mole of mixture and it contains
the compound is M 3N2. Also, 1.0 mole of compound has 28 g x mole of NO2.
of nitrogen. If X is the molar mass of compound, then :
⇒ 46 x + 92 (1 − x ) = 76.6 ⇒ x = 0.3348
28
X × = 28 100
100 Also, in 100 g mixture, number of moles =
76.6
⇒ X = 100 = 3 × Atomic weight of M + 28 100
72 ⇒ Moles of NO2 in mixture = × 0.3348 = 0.437
⇒ Atomic weight of M = = 24 76.6
3
16 Some Basic Concepts of Chemistry

61. Most of the elements found in nature exist as a mixture of The difference in the volume of NaOH solution between the end
isotopes whose atomic weights are different. The atomic weight point and the equivalence point is not significant for most of the
of an element is the average of atomic weights of all its naturally commonly used indicators as there is a large change in the pH
occurring isotopes. value around the equivalence point. Most of them change their
colour across this pH change.
62. Average atomic weight
Σ Percentage of an isotope × Atomic weight 3. 100 mL (cm3) of hexane contains 0.27 g of fatty acid.
= In 10 mL solution, mass of the fatty acid,
100
10.01x + 11.01 (100 − x) 0.27
⇒ 10.81 = ⇒ x = 20% m= × 10 = 0.027 g
100 100
Density of fatty acid, d = 0.9 g cm−3
Therefore, natural boron contains 20% (10.01) isotope and 80%
other isotope. ∴Volume of the fatty acid over the watch glass,
m 0.027
V = = = 0.03 cm3
Topic 2 Equivalent Concept, Neutralisation d 0.9
and Redox Titration Let, height of the cylindrical monolayer = h cm
Q Volume of the cylinder = Volume of fatty acid
1. In disproportionation reactions, same element undergoes
oxidation as well as reduction.
Reduction
e.g.
+1 +2 0 h cm
2CuBr CuBr2 +Cu

Oxidation
10 cm
Here, CuBr get oxidised to CuBr2 and also it get reduced to Cu.
Other given reactions and their types are given below. ⇒ V = πr 2 × h
Reduction
V 0.03 cm3
+7 ⇒ h= =
2 MnO4
– –
+10I + 16 H
+ +2
2Mn + 5I2 + 8H2O πr2 3 × (10)2 cm2
Oxidation = 1 × 10−4cm = 1 × 10−6 m
In the given reaction, MnO−4 get oxidised to Mn 2+ and I− get 4. The oxidation of a mixture of one mole of each of
reduced to I2. It is an example of redox reaction. The reaction FeC2O4 , Fe2 (C2O4 )3 FeSO4 and
takes place in acidic medium. Fe2 (SO4 )3 in acidic medium with KMnO4 is as follows :
2KMnO4 → K 2MnO4 + MnO2 + O2 FeC2O4 + KMnO4 → Fe3 + + CO2 + Mn 2+ …(i)
The given reaction is an example of decomposition reaction. Fe2(C2O4 )3 + KMnO4 → Fe3 + + CO2 + Mn 2+ …(ii)
Here, one compound split into two or more simpler compounds,
atleast one of which must be in elemental form. FeSO4 + KMnO4 → Fe 3+
+ SO24− + Mn 2+
…(iii)
2NaBr + Cl2 → 2NaCl + Br2 Change in oxidation number of Mn is 5. Change in oxidation
The given reaction is an example of displacement reaction. In number of Fe in (i), (ii) and (iii) are +3, + 6, + 1, respectively.
this reaction, an atom (or ion) replaces the ion (or atom) of neq KMnO 4 = neq [ FeC 2O 4 + Fe 2 ( C 2O 4 ) 3 + FeSO 4 ]
another element from a compound. n × 5 = 1× 3 + 1× 6 + 1× 1
2. The graph that shows the correct change of pH of the titration ∴ n=2
mixture in the experiment is 5. Given, W Ca (HCO 3) 2 = 0.81 g
W Mg (HCO ) = 0.73 g
3 2
M Ca (HCO ) = 162 g mol −1,
pH 3 2

M Mg(HCO 3 ) 2 = 146 mol −1

V H 2 O = 100mL
V(mL)
Now, neq (CaCO3) = neq [Ca(HCO3 )2 ]+ neq [Mg(HCO3 )2 ]
In this case, both the titrants are completely ionised.
+ − W 0.81 0.73
×2= ×2+ ×2
HCl + NaOH - N a Cl + H O 2 100 162 146
⊕ W
As H is added to a basic solution, [ OHÈ ] decreases and [ H+ ] ∴ = 0.005 + 0.005
increases. Therefore, pH goes on decreasing. As the equivalence 100
point is reached,[OHÈ ] is rapidly reduced. After this point [OH È] W = 0.01 × 100 = 1
1
decreases rapidly and pH of the solution remains fairly constant. Thus, hardness of water sample = × 106 = 10,000 ppm
Thus, there is an inflexion point at the equivalence point. 100
 Some Basic Concepts of Chemistry 17

6. The reaction takes place as follows, 12x 6

= (given and molar mass of C = 12, H = 1)
H2C2O4 + 2NaOH → Na 2C2O4 + 2H2O y 1

Now, 50 mL of 0.5 M H2C2O4 is needed to neutralize 25 mL of Now, after calculating this ratio look for condition 2 given in the
NaOH. question i.e. quantity of oxygen is half of the quantity required
to burn one molecule of compoundC xH y completely to CO2 and
∴ Meq of H2C2O4 = Meq of NaOH H2O. We can calculate number of oxygen atoms from this as
50 × 0.5 × 2 = 25 × M NaOH× 1 consider the equation.
M NaOH = 2M  y y
CxH y + x + O2 → xCO2 + H2O
Number of moles  4  2
Now, molarity =
Volume of solution (in L)  y  y
Number of oxygen atoms required = 2 × x + = 2x +
Weight / molecular mass  4   2 
=
Volume of solution (in L) 1 y  y
Now given, z = 2x + = x+
w 1000 2  2   4 
2 = NaOH ×
40 50 Here we consider x and y as simplest ratios for C and H so now
2 × 40 × 50 putting the values of x and y in the above equation.
wNaOH = = 4g
1000  y  2
z= x+ = 1+ = 1.5
Thus, (*) none option is correct.  4   4 
7. The reaction of HCl with Na 2CO3 is as follows: Thus, the simplest ratio figures for x , y and z are x = 1, y = 2 and
z = 15
.
2HCl + Na 2CO3 → 2NaCl + H2O + CO2 Now, put these values in the formula given i.e.
We know that, M eq of HCl = M eq of Na 2CO3 CxH yOz = C1H2O1.5
25 30 So, empirical formula will be [C1H2O1.5 ] × 2 = C2H4O3
× 1 × M HCl = × 0.1 × 2
1000 1000 10. Methyl orange show Pinkish colour towards more acidic
30 × 0.2 6 medium and yellow orange colour towards basic or less acidic
M HCl = = M media. Its working pH range is
25 25
The reaction of HCl with NaOH is as follows: 3.9 –4.5
Pinkish Yellow
NaOH + HCl → NaCl + H2O Red orange
Also, M eq of HCl = M eq of NaOH
Weak base have the pH range greater than 7. When methyl
6 V 30 orange is added to this weak base solution it shows yellow
×1× = × 0.2 × 1
25 1000 1000 orange colour.
V = 25mL Now when this solution is titrated against
strong acid the pH move towards more acidic 1
8. Reaction of oxalate with permanganate in acidic medium. range and reaches to end point near 3.9 where
NH2
5C2O24− + 2MnO−4 → 10CO2 + 2Mn 2+ + 8H2O yellow orange colour of methyl orange HN
changes to Pinkish red resulting to similar In conjugation
n-factor : (4 − 3 ) × 2 = 2 (7 − 2 ) = 5 change in colour of solution as well.
Number of mole 5 2 10
−
11. H2O2 acts as an oxidising as well as reducing agent, because
⇒ 5C2O42– ions transfer 10e to produce 10 molecules of CO2.
oxidation number of oxygen in H2O2 is −1. So, it can be oxidised
So, number of electrons involved in producing 10 molecules of to oxidation state 0 or reduced to oxidation state –2.
CO2 is 10. Thus, number of electrons involved in producing 1 H2O2 decomposes on exposure to light. So, it has to be stored in
molecule of CO2 is 1. plastic or wax lined glass bottles in dark for the prevention of
9. We can calculate the simplest whole number ratio of C and H exposure. It also has to be kept away from dust.
from the data given, as 12. n-factor of dichromate is 6.
Element Relative Molar Relative Simplest whole Also, n-factor of Mohr’s salt is 1 as :
mass mass mole number ratio O. A
6 0.5 FeSO4 (NH4 )2 SO4⋅ 6H2O → Fe3+
C 6 12 = 0.5 =1 Mohr’s salt
12 0.5
H 1 1 1 1 Q 1 mole of dichromate = 6 equivalent of dichromate.
=1 =2
1 0.5 ∴ 6 equivalent of Mohr’s salt would be required.
Since, n-factor of Mohr’s salt is 1, 6 equivalent of it would also
Alternatively this ratio can also be calculated directly in the
be equal to 6 moles.
terms of x and y as
Hence, 1 mole of dichromate will oxidise 6 moles of Mohr’s salt.
18 Some Basic Concepts of Chemistry

13. The following reaction occur between S2O32− and Cr2O2−

7 :
Here n-factor is the net change in oxidation number per formula
unit of oxidising or reducing agent. In the present case, n-factor
26H ++
3S2O32−+ 4Cr2O72−
→ 6SO24− + 8Cr 3+ + 13H2O is 2 because equivalent weight is half of molecular weight. Also,
Change in oxidation number of Cr2O72− per formula unit is 6 (it is 1
n-factor MnSO4 → Mn 2O3 1 (+ 2 → + 3)
always fixed for Cr2O2−
7 ).
2
Molecular weight MnSO4 → MnO2 2 (+ 2 → + 4)
Hence, equivalent weight of K2Cr2O7 = −
6 MnSO4 → MnO4 5 (+ 2 → + 7)
14. It is an example of disproportionation reaction because the same MnSO4 → MnO42− 4 (+ 2 → + 6)
species (ClO− ) is being oxidised to ClO−3 as well as reduced to Cl − . Therefore, MnSO4 converts to MnO2.
15. Oxalic acid dihydrate H2C2O4 ⋅ 2H2O : mw = 126 24. PLAN This problem includes concept of redox reaction. A redox
It is a dibasic acid, hence equivalent weight = 63 reaction consists of oxidation half-cell reaction and reduction
6.3 1000 half-cell reaction. Write both half-cell reactions, i.e. oxidation
⇒ Normality = × = 0.4 N half-cell reaction and reduction half-cell reaction.Then balance
63 250 both the equations.
⇒ N 1V1 = N 2V2 Now determine the correct value of stoichiometry of H2SO4.
⇒ 0.1 × V1 = 0.4 × 10 Oxidation half-reaction, 2 I − → I2 + 2 e − …(i)
Hence, V1 = 40 mL Here, I − is converted into I2. Oxidation number of I is increasing
16. In MnO−4 , oxidation state of Mn is +7 from –1 to 0 hence, this is a type of oxidation reaction.
Reduction half-reaction
In Cr(CN)63− , oxidation state of Cr is +3
6H+ + ClO3− + 6e− → Cl − + 3H2O …(ii)
In NiF62− , Ni is in + 4 oxidation state. l
Here, H2 O releases as a product. Hence, option (d) is
In CrO2Cl 2, oxidation state of Cr is +6. correct.
17. In S8 , oxidation number of S is 0, elemental state. Multiplying equation (i) by 3 and adding in equation (ii)
In S2F2, F is in – 1 oxidation state, hence S is in + 1 oxidation 6I− + ClO3− + 6H+ → Cl − + 3I2 + 3H2O
state.
In H2S, H is in +1 oxidation state, hence S is in – 2 oxidation 6I− + ClO−3 + 6H2SO4 → Cl − + 3I2 + 3H2O + 6HSO−4
state. l
Stoichiometric coefficient of HSO−4 is 6.
18. The balanced redox reaction is : Hence, option (a), (b) and (d) are correct.
3MnO−4 + 5FeC2O4 + 24H+ → 3Mn 2+ + 5Fe3+ 25. Oxalic acid solution titrated with NaOH solution using
+ 10CO2 + 12H2O phenolphthalein as an indicator.
Q 5 moles of FeC2O4 require 3 moles of KMnO4
H2 C2 O4 + 2NaOH → Na 2 C2 O4 + 2H2 O
3
∴ 1 mole of FeC2O4 will require mole of KMnO4. Equivalent of H2C2O4 reacted = Equivalent of NaOH reacted
5
5 × 2 × 01
. 9 × M(NaOH) × 1
19. The balanced chemical reaction is : = =
1000 1000
2MnO−4 + 5SO23− + 6H+ → 2Mn 2+ + 5SO24− + 3H2O 1
M (NaOH) = = 0.11
Q 5 moles SO2−
3 reacts with 2 moles of KMnO 4 9
2
∴ 1 mole of SO2−
3 will react with mole KMnO4. 26. Aluminium reacts with sulphuric acid to form aluminium
5 sulphate and hydrogen.
20. The balanced redox reaction is :
2Al + 3H2 SO4 → Al 2 (SO4 )3 + 3H2
2MnO4− + 5C2O24− + 16H + → 2Mn 2+ + 10CO2 + 16H2O  5. 4


= 0. 2 mol   50 × 5 
 27   = 0. 25 mol 
 1000 
Hence, the coefficients of reactants in balanced reaction are 2, 5
and 16 respectively. H2SO 4 is limiting reagent and moles of H2 (g ) produced
= 0.25 mol
21. Volume strength of H2O2 = Normality × 5.6 = 1.5 × 5.6 = 8.4 V
Using ideal gas equation,
22. In Ba(H2PO2 )2, oxidation number of Ba is +2. Therefore, pV = nRT
H2PO2− : 2 × (+1) + x + 2 × (−2) = − 1 0.25 × 0.082 × 300
⇒ V = ⇒ 6.15 L
⇒ x=+1 1 atm
23. Equivalent weight in redox system is defined as : 27. Given, volume of solution = 20.0 mL
Molar mass
E= Impure sample of H2O2 = 0.2 g
n-factor
Mass of KMnO4 = 0.316 g
 Some Basic Concepts of Chemistry 19

Impure H2O2 react with KMnO4 (acidic) 30. If x is the oxidation state of Cu then :
+7 −1 +2 0
3 + 2 × 2 + 3x + 7 × (− 2) = 0 ⇒ x = 7/ 3
KMnO4 + H2O2 → Mn + O2
KMnO 4 acts as an oxidising agent, 31. Na2S4O6 is a salt of H2S4O6 which has the following structure
+7 +2 O O
Mn + 5e− → Mn (valency factor = 5) (0) (v)
−1 0
−
HO S S S S OH
O2 → O2 + 2e (valency factor = 2)
We have to compare both KMnO4 and H2O2. O O
(Mass equivalent) H O2 = (Mass equivalent) KMnO4 ⇒ Difference in oxidation number of two types of sulphur = 5
2

Weight 32. Only F and Na show only one non-zero oxidation state.
× 1000
molecular weight / valence factor O = O− , O2− , O2+ ;
weight Cl = − 1 to + 7
= × 1000
molecular weight / valence factor N = − 3 to + 5
(weight)H 2 O 2 0.316 P = − 3 to + 5
× 1000 = × 1000
34 / 2 158 / 5 Sn = + 2, + 4
0.316 34 Tl = + 1, + 3 (rare but does exist)
(weight)H2 O2 = ×5×
158 2 Ti = + 2, + 3, + 4
26.86
= 33. Average titrate value is 25.15, but the number of significant
158 figure cannot be greater than the same in either of them being
(weight)H2 O2 = 017
. g manipulated.

(Pure)H2 O2 34. The balanced reaction is

(Purify) H
2O2
= × 100 6CaO + P4O10 → 2Ca 3 (PO4 )2
(Impure)H2 O2
852
017
. Moles of P4O10 = =3
= × 100 = 85% 284
0.2 Moles of CaO required = 3 × 6 = 18
28. Balanced equations of reactions used in the problem are as follows Mass of CaO required = 18 × 56 = 1008 g
(i) ( NH4)2SO 4 + Ca(OH)2 → CaSO 4 ⋅ 2H2O + 2NH3 35. Meq of oxalate = 10 × 0.2 × 2 = 4
1 mol 1 mol 2 mol
132 g 172 g (2 × 17) = 34 g Meq of MnO2 formed = Meq of oxalate = 4
(ii) NiCl 2 ⋅ 6H2O + 6NH3 → [Ni(NH3)6] Cl 2 + 6H2O Meq of KMnO4 in 20 mL = 4
1 mol
238 g
6 mol
102 g
1 mol
232 g
⇒ Normality of H2O2 × 20 = 4
⇒ Normality of H2O2 = 0.20 N
Now, in Eq. (i)
0.20
if, 1584 g of ammonium sulphate is used. ⇒ Molarity of H2O2 = = 0.10 M
2
1584
i.e., 1584 g (NH4 )2 SO4 = = 12 mol The balanced reactions are
132
2KMnO4 + 5H2O2 + 3H2SO4 → 2MnSO4 + 5O2
So, according to the Eq. (i) given above 12 moles of (NH4 )2 SO4
+ K2SO4 + 8H2O
produces
MnO2 + Na 2C2O4 + 2H2SO4 → MnSO4 + Na 2SO4
(a) 12 moles of gypsum
+ 2CO2 + 2H2O
(b) 24 moles of ammonia
36. The balanced chemical reaction is
Here, 12 moles of gypsum = 12 × 172 = 2064 g
CuCO3 + H2SO4 → CuSO4 + H2O + CO2
and 24 moles of NH3 = 24 × 17 = 408g
0.5 × 1000
Further, as given in question, millimol of CuCO3 = = 4.048
123.5
24 moles of NH3 produced in reaction (i) is completly utilised
⇒ Millimol of H2SO4 required = 4.048
by 952g or 4 moles of NiCl 2 ⋅ 6H2O to produce 4 moles of
[Ni(NH3 )6 ] Cl 2. Q Millimol = Molarity × Volume (in mL)
So, 4 moles of [Ni(NH3 )6 ] Cl 2 = 4 × 232 = 928gms 4.048
⇒ Volume = = 8.096 mL
Hence, total mass of gypsum and nickel ammonia coordination 0.50
compound [Ni(NH3 )6 ] Cl 2 = 2064 + 928 = 2992 37. The redox reaction involved are
29. Both assertion and reason are factually true but the reason does IO−3 + 5I− + 6H+ → 3I2 + 3H2O
not exactly explain the assertion. The correct explanation is, I2 + 2S2O32− → 2I− + S4O62−
methyl orange and phenolphthalein changes their colour at
different pH.
20 Some Basic Concepts of Chemistry

0.1 4
millimol of KIO3 used = × 1000 = 0.467 Vol % of CH4 = × 100= 20%
214 20
⇒ millimol of I2 formed = 3 × 0.467 = 1.4 Vol % of He = 30%
⇒ millimol of Na 2S2O3 consumed = 2 × 1.4 = 2.8
2.8 41. The redox reaction involved is :
⇒ Molarity of Na 2S2O3 = = 0.062 M H2O2 + 2I− + 2H+ → 2H2O + I2
45
If M is molarity of H2O2 solution, then
38. Meq of H2O2 = Meq of I2 = Meq of Na 2S2O3
0.508 × 1000
If N is normality of H2O2, then 5M = (Q 1 mole H2O2 ≡≡ 1 mole I2)
254
N × 25 = 0.3 × 20 ⇒ N = 0.24 ⇒ M = 0.4
⇒ Volume strength = N × 5.6 = 1.334 V Also, n-factor of H2O2 is 2, therefore normality of H2O2 solution
39. Let the original sample contains x millimol of Fe3O4 and is 0.8 N.
y millimol of Fe2O3. In the first phase of reaction, ⇒ Volume strength = Normality × 5.6 = 0.8 × 5.6 = 4.48 V
Fe3O4 + I− → 3Fe2+ + I2 (n-factor of Fe3O4 = 2) 42. The reaction is
−
Fe2O3 + I → 2Fe 2+
+ I2 (n-factor of Fe2O3 = 2) KIO3 + 2KI + 6HCl → 3ICl + 3KCl + 3H2O
⇒ Meq of I2 formed = Meq (Fe3O4 + Fe2O3 ) KIO3 required for 20 mL original KI solution = 3 millimol.
= Meq of hypo required ⇒ 7.5 millimol KIO3 would be required for original 50 mL KI.
⇒ 2x + 2 y = 11 × 0.5 × 5 = 27.5 …(i) ⇒ Original 50 mL KI solution contain 15 millimol of KI.
Now, total millimol of Fe2+ formed = 3x + 2 y. In the reaction
After AgNO3 treatment 5 millimol of KIO3 is required, i.e. 10
Fe2+ + MnO−4 + H+ → Fe3+ + Mn 2+ millimol KI is remaining.
n-factor of Fe2+ = 1 ⇒ 5 millimol KI reacted with 5 millimol of AgNO3.
⇒ Meq of MnO−4 = Meq of Fe 2+ 5
⇒ Mass of AgNO3 = × 170 = 0.85 g
1000
⇒ 3x + 2 y = 12.8 × 0.25 × 5 × 2 = 32 …(ii)
Solving Eqs. (i) and (ii), we get ⇒ Mass percentage of AgNO3 = 85%
x = 4.5 43. CO2 is evolved due to following reaction :
and y = 9.25 2NaHCO3 → Na 2CO3 + H2O + CO2
4.5
⇒ Mass of Fe3O4 = × 232 = 1.044 g pV 750 123.9 1
1000 Moles of CO2 produced = = × ×
RT 760 1000 0.082 × 298
1.044
% mass of Fe3O4 = × 100 = 34.80%
3 = 5 × 10−3

Mass of Fe2O3 =
9.25
× 160 = 1.48 g ⇒ Moles of NaHCO3 in 2 g sample = 2 × 5 × 10−3 = 0.01
1000 ⇒ millimol of NaHCO3 in 1.5 g sample
1.48
% mass of Fe2O3 = × 100 = 49.33% 0.01
3 = × 1.5 × 1000= 7.5
2
40. The reaction involved in the explosion process is Let the 1.5 g sample contain x millimol Na 2CO3, then
1
CO(g ) + O (g ) → CO2 (g ) 2x + 7.5 = millimol of HCl = 15
2 x2
x mL x mL
mL ⇒ x = 3.75
2
CH4 (g ) + 2O2 (g ) → CO2 (g ) + 2H2O(l ) 7.5 × 84
⇒ Mass of NaHCO3 = = 0.63 g
y mL 2 y mL y mL 1000
The first step volume contraction can be calculated as : 3.75 × 106
Mass of Na 2CO3 = = 0.3975 g
 x  1000
 x + + y + 2 y − (x + y) = 13 0.63
 2  ⇒ % mass of NaHCO3 = × 100 = 42 %
⇒ x + 4 y = 26 …(i) 1.50
0.3975
The second volume contraction is due to absorption of CO2. % mass of Na 2CO3 = × 100 = 26.5%
1.5
Hence, x + y = 14 …(ii)
44. Mass of Fe2O3 = 0.552 g
Now, solving equations (i) and (ii), 0.552
millimol of Fe2O3 = × 1000 = 3.45
x = 10 mL, y = 4 mL and volume of He = 20 – 14 = 6 mL 160
⇒ Vol % of CO =
10
× 100 = 50% During treatment with Zn-dust, all Fe3+ is reduced to Fe2 + ,
20 hence
 Some Basic Concepts of Chemistry 21

millimol of Fe2 + (in 100 mL) = 3.45 × 2 = 6.90 Because X can be represented by two formula of which one
6.90 gives a dihydroxy compound with KOH indicates that X has two
⇒ In 25 mL aliquot, = 1.725 millimol Fe2+ ion. chlorine atoms per molecule.
4
Finally Fe2+ is oxidised to Fe3+ , liberating one electron per Fe2+ ⇒ X = C2H4Cl 2 with two of its structural isomers.
ion. Therefore, total electrons taken up by oxidant. Cl— CH2— CH2 — Cl and CH3— CHCl 2
= 1.725 × 10−3 × 6.023 × 1023 I II
20 On treatment with KOH, I will give ethane-1, 2-diol, hence it is
= 1.04 × 10
Y. Z on treatment with KOH will give ethanal as
45. With KMnO4, oxalate ion is oxidised only as : ClCH2CH2Cl + OH− → CH2 — CH2
5C2O42− + 2MnO−4 + 16H+ → 2Mn 2+ + 10CO2 + 8H2O  
OH OH
Let, in the given mass of compound, x millimol of C2O2−
4 ion is (Y )
present, then –H2 O
CH3CHCl 2 + KOH → CH3CH(OH)2 → CH3CHO
Meq of C2O42− = Meq of MnO−4 Unstable (Z )
⇒ 2x = 0.02 × 5 × 22.6 ⇒ x = 1.13
48. Let the n-factor of KMnO4 in acid, neutral and alkaline media
At the later stage, with I − , Cu 2+ is reduced as :
are N 1, N 2 and N 3 respectively. Also, same volumes of reducing
2Cu 2+ + 4I − → 2CuI + I2 agent is used everytime, same number of equivalents of KMnO4
would be required every time.
and I2 + 2S2O32− → 2I− + S4O62−
100 5
Let there be x millimol of Cu 2+ . ⇒ 20N 1 = N 2 = 100N 3 ⇒ N 1 = N 2 = 5N 3
3 3
⇒ Meq of Cu 2+ = Meq of I2 = meq of hypo Also, n-factors are all integer and greater than or equal to one but
less than six, N 3 must be 1.
⇒ x = 11.3 × 0.05 = 0.565
2+ ⇒ N 1 = 5, N 2 = 3
⇒ Moles of Cu : moles of C2O42− = 0.565 : 1.13 = 1 : 2
∴ In acid medium MnO−4 → Mn 2+
46. Let us consider 10 mL of the stock solution contain x millimol In neutral medium MnO−4 → Mn 4+
oxalic acid H2C2O4 and y millimol of NaHC2O4. In alkaline medium MnO−4 → Mn6+
When titrated against NaOH, basicity of oxalic acid is 2 while ⇒ meq of K2Cr2O7 required = 100
that of NaHC2O4 is 1.
⇒ 100 = 1 × 6 × V (n-factor = 6)
⇒ 2x + y = 3 × 0.1 = 0.3 … (i)
⇒ V = 100/ 6 = 16.67 mL
When titrated against acidic KMnO4, n-factors of both oxalic 1
acid and NaHC2O4 would be 2. 49. Meq of MnO−4 required = 20 × ×5=2
50
⇒ 2x + 2 y = 4 × 0.1 = 0.4 … (ii) ⇒ Meq of Fe2+ present in solution = 2
Solving equations (i) and (ii) gives
⇒ millimol of Fe2+ present in solution = 2 (n-factor = 1)
y = 0.1, x = 0.1 Also,
0.1 Q 4 millimol of Fe2+ are formed from 1 millimol N2H4
⇒ In 1.0 L solution, mole of H2C2O4 = × 100 = 0.01
1000 1 1
∴ 2 millimol Fe2+ from × 2 = millimol N2H4
0.1 4 2
Mole of NaHC2O4 = × 100 = 0.01
1000 Therefore, molarity of hydrazine sulphate solution
⇒ Mass of H2C2O4 = 90 × 0.01 = 0.9 g 1 1 1
= × =
Mass of NaHC2O4 = 112 × 0.01= 1.12 g 2 10 20
35.5 1
47. Mass of chlorine in 1.0 g X = × 2.9 = 0.717 g ⇒ In 1 L solution mol N2H6SO4 is present.
143.5 20
1
Now, the empirical formula can be derived as : ⇒ Amount of N2H6SO4 = × 130 = 6.5 gL−1
20
C H Cl
50. Molecular weight of Na 2CO3 ⋅10H2O = 286
% wt : 24.24 4.04 71.72
1 1000
Mole : 2 4 2 ⇒ Molarity of carbonate solution = × = 0.035
286 100
Simple ratio : 1 2 1 ⇒ Normality of carbonate solution = 2 × 0.035 = 0.07 N
⇒ Empirical formula = CH2Cl.
22 Some Basic Concepts of Chemistry

8×5 BaO(s) BaO(s)

In acid solution : Normality of HNO3 = = 0.02
2000 4.08 g 3.64 g
5 × 4.8 From the decomposition information, it can be deduced that the
Normality of HCl = = 0.012
2000 original mixture contained 0.01 mole of MCO3 and the solid
Let normality of H2SO4 in final solution be N. residue, obtained after heating, contain 0.01 mole (10 millimol)
of MO.
⇒ (N + 0.02 + 0.012) × 30 = 0.07 × 42.9
Also, millimol of HCl taken initially = 100
⇒ N = 0.0681 millimol of NaOH used in back-titration = 16 × 2.5 = 40
⇒ Gram equivalent of SO2−
4 in 2 L solution = 2 × 0.0681 ⇒ millimol of HCl reacted with oxide residue = 60
= 0.1362 HCl reacts with oxides as :
96 MO + 2HCl → MCl 2 + H2O
⇒ Mass of SO2−
4 in solution = 0.1362 × = 6.5376 g 10 millimol 20 millimol
2
BaO + 2HCl → BaCl 2 + H2O
51. For the oxidation of A n+ as :
60 – 20 = 40 millimol
A n+ → AO−3 n-factor = 5 – n Therefore, the residue contain 20 millimol of BaO.
⇒ Gram equivalent of A n+ = 2.68 × 10−3 (5 − n) Also, molar mass of BaO = 138 + 16
Now equating the above gram equivalent with gram equivalent = 154
of KMnO4 : 154 × 20
2.68 × 10−3 (5 − n) = 1.61 × 10−3 × 5 ⇒ Mass of BaO = = 3.08 g
1000
⇒ n=+2 ⇒ Mass of MCO3 = 4.08 – 3.08 = 1.0 g
52. During heating MCO3 is converted into MO liberating CO2 Q 0.01 mole of MCO3 weight 1.0 g
while BaO is remaining unreacted : ∴ 1 mole of MCO3 = 100 g
Heat
MCO3 (s) → MO(s) + CO2 (g ) ↑ 0.44 g = 0.01 mol ⇒ 100 = (Atomic weight of metal) + (12 + 3 × 16)
⇒ Atomic weight of metal = 40, i.e. Ca
2
Atomic Structure
Topic 1 Preliminary Developments and Bohr’s Model
Objective Questions I (Only one correct option) 5. Which of the graphs shown below does not represent the
1. Which one of the following about an electron occupying relationship between incident light and the electron ejected from
the 1s-orbital in a hydrogen atom is incorrect? (The metal surface? (2019 Main, 10 Jan I)

Bohr radius is represented by a0 ) (2019 Main, 9 April II)

K.E. of K.E. of
(a) The electron can be found at a distance 2a0 from es s e ss
the nucleus.
(b) The magnitude of the potential energy is double
that of its kinetic energy on an average. (a) (b)
(c) The probability density of finding the electron is 0 0
maximum at the nucleus. Energy of light Intensity of light
(d) The total energy of the electron is maximum when
it is at a distance a0 from the nucleus. Number K.E. of
of ess ess
2. If p is the momentum of the fastest electron ejected
from a metal surface after the irradiation of light having
wavelength λ, then for 1.5 p momentum of the (c) (d)
photoelectron, the wavelength of the light should be 0 0
(Assume kinetic energy of ejected photoelectron to be Frequency of light Frequency of light
very high in comparison to work function)
(2019 Main, 8 April II)
6. A stream of electrons from a heated filament was passed between
4 3 two charged plates kept at a potential difference V esu. If e and m
(a) λ (b) λ are charge and mass of an electron, respectively, then the value of
9 4
h/ λ (where, λ is wavelength associated with electron wave) is
2 1
(c) λ (d) λ given by (2016 Main)
3 2
(a) 2 meV (b) meV (c) 2meV (d) meV
3. What is the work function of the metal, if the light of
wavelength 4000 Å generates photoelectron of velocity 7. Rutherford’s experiment, which established the nuclear model of
6 × 105 ms −1 from it? the atom, used a beam of (2002, 3M)

(Mass of electron = 9 × 10 −31

kg (a) β -particles, which impinged on a metal foil and got absorbed
Velocity of light = 3 × 10 ms −1
8 (b) γ-rays, which impinged on a metal foil and got scattered
(c) helium atoms, which impinged on a metal foil and got
Planck’s constant = 6.626 × 10−34 Js
scattered
Charge of electron = 1.6 × 10−19 JeV−1 ) (d) helium nuclei, which impinged on a metal foil and got
(2019 Main, 12 Jan I)
scattered
(a) 4.0 eV (b) 2.1 eV
8. Rutherford’s alpha particle scattering experiment eventually led
(c) 0.9 eV (d) 3.1 eV
to the conclusion that (1986, 1M)
4. The ground state energy of hydrogen atom is −13.6 eV. (a) mass and energy are related
The energy of second excited state of He+ ion in eV is (b) electrons occupy space around the nucleus
(2019 Main, 10 Jan II)
(c) neutrons are burried deep in the nucleus
(a) −54.4 (b) −3.4 (c) −6.04 (d) −27.2
(d) the point of impact with matter can be precisely determined
24 Atomic Structure

9. The radius of an atomic nucleus is of the order of (1985, 1M) List-I List-II
−10 −13 −15 −8
(a) 10 cm (b) 10 cm (c) 10 cm (d) 10 cm (I) Radius of the n th orbit (P) ∝ n −2

10. Bohr’s model can explain (1985, 1M) (II) Angular momentum of the electron (Q) ∝ n −1
in the nth orbit
(a) the spectrum of hydrogen atom only
(b) spectrum of an atom or ion containing one electron only (III) Kinetic energy of the electron in the (R) ∝ n0
nth orbit
(c) the spectrum of hydrogen molecule
(d) the solar spectrum
(IV) Potential energy of the electron in (S) ∝ n1
the nth orbit
11. The increasing order (lowest first) for the values of e/m (T) ∝ n2
(charge/mass) for electron ( e ), proton (p), neutron (n) and
(U) ∝ n 1/ 2
alpha particle (α) is (1984, 1M)
(a) e, p, n, α (b) n, p, e, α Which of the following options has the correct combination
(c) n , p , α , e (d) n , α, p , e considering List-I and List-II? (2019 Adv.)
12. Rutherford’s scattering experiment is related to the size of (a) (III), (P) (b) (III), (S)
the (1983, 1M) (c) (IV), (U) (d) (IV), (Q)
(a) nucleus (b) atom (c) electron (d) neutron 20. Consider the Bohr’s model of a one-electron atom where the
13. Rutherford’s experiment on scattering of α-particles showed electron moves around the nucleus. In the following List-I
for the first time that the atom has (1981, 1M) contains some quantities for the nth orbit of the atom and
(a) electrons (b) protons List-II contains options showing how they depend on n.
(c) nucleus (d) neutrons
List-I List-II

Objective Questions II (I) Radius of the nth orbit (P) ∝ n −2

(One or more than one correct option) (II) Angular momentum of the electron in (Q) ∝ n −1
the nth orbit
14. The energy of an electron in the first Bohr orbit of H-atom is
(III) Kinetic energy of the electron in the (R) ∝ n0
–13.6 eV. The possible energy value(s) of the excited state(s) nth orbit
for electrons in Bohr orbits of hydrogen is (are) (1988) (IV) Potential energy of the electron in the (S) ∝ n1
(a) − 3.4 eV (b) − 4.2 eV (c) − 6.8 eV (d) + 6.8 eV nth orbit
15. The atomic nucleus contains (1988, 1M) (T) ∝ n2
(a) protons (b) neutrons (c) electrons (d) photons (U) ∝ n 1/ 2
16. The sum of the number of neutrons and proton in the isotope
Which of the following options has the correct combination
of hydrogen is (1986, 1M)
considering List-I and List-II? (2019 Adv.)
(a) 6 (b) 5 (c) 4 (d) 3
(a) (II), (R) (b) (I), (P)
17. When alpha particles are sent through a thin metal foil, most (c) (I), (T) (d) (II), (Q)
of them go straight through the foil, because (1984, 1M)
21. According to Bohr’s theory,
(a) alpha particles are much heavier than electrons
En = Total energy K n = Kinetic energy
(b) alpha particles are positively charged
Vn = Potential energy rn = Radius of nth orbit
(c) most part of the atom is empty space
Match the following : (2006, 6M)
(d) alpha particles move with high velocity
18. Many elements have non-integral atomic masses, because Column I Column II
(a) they have isotopes (1984, 1M) A. V / K = ?
n n
p. 0
(b) their isotopes have non-integral masses B. q.
If radius of nth orbit ∝ E xn ,x= ? –1
(c) their isotopes have different masses
(d) the constituents, neutrons, protons and electrons, C. Angular momentum in lowest r. –2
combine to give fractional masses orbital
D. 1 s. 1
Match the Columns n
∝ Zy, y = ?
r
19. Consider the Bohr’s model of a one-electron atom where the
electron moves around the nucleus. In the following List-I
contains some quantities for the nth orbit of the atom and Fill in the Blanks
List-II contains options showing how they depend on n. 22. The light radiations with discrete quantities of energy are
called ................ . (1993, 1M)
 Atomic Structure 25

23. The mass of a hydrogen is …… kg. (1982, 1M) Use Avogardo constant as 6.023 × 1023 mol −1 . (2020 Adv.)
24. Isotopes of an element differ in the number of …… in their
nuclei.
d

Potential energy
(1982, 1M) H H

(kJ mol–1)
25. Elements of the same mass number but of different atomic
numbers are known as …… . (1983, 1M) E0

Numerical Answer Type Questions

26. The figure below is the plot of potential energy versus d0
internuclear distance ( d ) of H2 molecule in the electronic Internuclear distance (d)
ground state. What is the value of the net potential energy
E0 (as indicated in the figure) in kJ mol −1 , for d = d 0 at Subjective Questions
which the electron-electron repulsion and the 27. With what velocity should an α-particle travel towards the
nucleus-nucleus repulsion energies are absent? As nucleus of a copper atom so as to arrive at a distance 10−13 m
reference, the potential energy of H atom is taken as zero from the nucleus of the copper atom ? (1997 (C), 3M)
when its electron and the nucleus are infinitely far apart.

Topic 2 Advanced Concept (Quantum Mechanical Theory)

Electronic Configuration and Quantum Number
Objective Questions I (Only one correct option) 3. Among the following, the energy of 2s-orbital is lowest in
(2019 Main, 12 April II)
1. The figure that is not a direct manifestation of the quantum
(a) K (b) H (c) Li (d) Na
nature of atoms is (2020 Main, 2 Sep I)
Increasing wavelength 4. The electrons are more likely to be found
a Ψ (x)
(a)
b x
–x
Absorption spectrum

c
Rb K
Na
(2019 Main, 12 April I)
Kinetic energy of
(b) photoelectrons (a) in the region a and c (b) in the region a and b
(c) only in the region a (d) only in the region c
Frequency of incident radiation 5. The ratio of the shortest wavelength of two spectral series of
hydrogen spectrum is found to be about 9. The spectral series
are (2019 Main, 10 April II)
Internal (a) Lyman and Paschen (b) Brackett and Pfund
(c) energy of (c) Paschen and Pfund (d) Balmer and Brackett
Ar
300 400 500 600 6. The graph between | ψ |2 and r (radial distance) is shown below.
Temperature (K) This represents (2019 Main, 10 April I)

T 2 >T 1
Intensity
2
(d) of black body |Ψ|
radiation T1

Wavelength

2. The number of orbitals associated with quantum numbers r

1
n = 5, ms = + is (a) 1s-orbital (b) 2 p-orbital
2 (2020 Main, 7 Jan I)
(c) 3s-orbital (d) 2s-orbital
(a) 25 (b) 50 (c) 15 (d) 11
26 Atomic Structure

7. For any given series of spectral lines of atomic hydrogen, 13. For emission line of atomic hydrogen from ni = 8 to n f = n,
let ∆ν = ν max − ν min be the difference in maximum and  1
minimum frequencies in cm −1 . The ratio the plot of wave number ( ν ) against  2  will be (The
n 
∆ νLyman / ∆ νBalmer is (2019 Main, 9 April I) Rydberg constant, RH is in wave number unit)
(a) 27 : 5 (b) 5 : 4 (c) 9 : 4 (d) 4 : 1 (2019 Main, 9 Jan I)
(a) non linear (b) linear with slope −RH
8. The quantum number of four electrons are given below:
1 (c) linear with slope RH (d) linear with intercept −RH
I. n = 4 , l = 2, ml = − 2, ms = −
2 14. The radius of the second Bohr orbit for hydrogen atom is
II. n = 3, l = 2, ml = 1, ms = +
1 (Planck’s constant ( h ) = 6.6262 × 10− 34 Js; mass of electron
2 = 91091
. × 10− 31 kg ; charge of electron
1 − 19
III. n = 4 , l = 1, ml = 0, ms = + ( e ) = 160210
. × 10 C; permitivity of vacuum
2
1 (∈0 ) = 8.854185 × 10− 12kg − 1 m − 3A 2 ) (2017 Main)
IV. n = 3, l = 1, ml = 1, ms = −
2 (a) 1.65 Å (b) 4.76 Å
The correct order of their increasing energies will be
(2019 Main, 8 April I)
(c) 0.529 Å (d) 2.12 Å
(a) IV < III < II < I (b) I < II < III < IV 15. P is the probability of finding the 1s electron of hydrogen
(c) IV < II < III < I (d) I < III < II < IV atom in a spherical shell of infinitesimal thickness, dr,
th at a distance r from the nucleus. The volume of this shell is
9. If the de-Broglie wavelength of the electron in n Bohr orbit
. πa0 (a0 is Bohr radius),
in a hydrogenic atom is equal to 15 4 πr2 dr. The qualitative sketch of the dependence of P on r is
(2016 Adv.)
then the value of n / Z is (2019 Main, 12 Jan II)
(a) 1.0 (b) 0.75 (c) 0.40 (d) 1.50 P P

10. The de-Broglie wavelength ( λ ) associated with a photoelectron

varies with the frequency ( ν ) of the incident radiation as, [ν 0 is (a) (b)
threshold frequency] (2019 Main, 11 Jan II)
1 1 0 0
(a) λ ∝ 1
(b) λ ∝ 3
r r

( ν − ν0 )4 ( ν − ν0 )2 P P
1 1
(c) λ ∝ (d) λ ∝
( ν − ν0 ) 1
(c) (d)
( ν − ν0 )2
11. Which of the following combination of statements is true
regarding the interpretation of the atomic orbitals? 0 r 0 r
(2019 Main, 9 Jan II)
16. Which of the following is the energy of a possible excited
I. An electron in an orbital of high angular momentum state of hydrogen? (2015 Main)
stays away from the nucleus than an electron in the (a) + 13.6 eV (b) – 6.8 eV
orbital of lower angular momentum. (c) –3.4 eV (d) + 6.8 eV
II. For a given value of the principal quantum number, the
size of the orbit is inversely proportional to the azimuthal 17. The correct set of four quantum numbers for the valence
quantum number. electrons of rubidium atom ( Z = 37 ) is (2013 Main)
1 1
III. According to wave mechanics, the ground state angular (a) 5, 0, 0, + (b) 5, 1, 0, +
h 2 2
momentum is equal to . 1 1
2π (c) 5, 1, ,1, + (d) 5, 0, 1, +
IV. The plot of ψ vs r for various azimuthal quantum 2 2
numbers, shows peak shifting towards higher r value. 18. Energy of an electron is given by
(a) I, III (b) II, III (c) I, II (d) I, IV  Z2 
E = − 2.178 × 10−18 J  2 
12. Heat treatment of muscular pain involves radiation of n  (2013 Main)
wavelength of about 900 nm. Which spectral line of H-atom
Wavelength of light required to excite an electron in an
is suitable for this purpose? [RH = 1 × 105 cm–1 , hydrogen atom from level n = 1to n = 2 will be
h = 6.6 × 10−34 Js, c = 3 × 108 ms −1 ] (2019 Main, 11 Jan I) (h = 6.62 × 10−34 Js and c = 3.0 × 108 ms −1 )
(a) Paschen, 5 →3 (b) Paschen, ∞ → 3 (a) 1.214 × 10−7 m (b) 2.816 × 10−7 m
(c) Lyman, ∞ → 1 (d) Balmer, ∞ → 2 (c) 6.500 × 10 −7
m (d) 8.500 × 10−7 m
 Atomic Structure 27

19. The kinetic energy of an electron in the second Bohr orbit of a 29. For a d-electron, the orbital angular momentum is(1997, 1M)
hydrogen atom is [a0 is Bohr radius] (2012)  h  h  h  h
(a) 6   (b) 2   (c)   (d) 2  
h2 h2 h2 h2  2π   2π   2π   2π 
(a) (b) (c) (d)
4π 2 ma02 16π 2 ma02 32π 2 ma02 64π 2 ma02 30. The first use of quantum theory to explain the structure of
20. The number of radial nodes in 3s and 2p respectively are atom was made by (1997, 1M)

(a) 2 and 0 (b) 0 and 2 (2005, 1M)

(a) Heisenberg (b) Bohr
(c) 1 and 2 (d) 2 and 1 (c) Planck (d) Einstein
21. Which hydrogen like species will have same radius as that of 31. Which of the following has the maximum number of
Bohr orbit of hydrogen atom? (2004, 1M) unpaired electrons ? (1996, 1M)
(a) n = 2, Li 2+
(b) n = 2, Be 3+ (a) Mg2+ (b) Ti 3+ (c) V3+ (d) Fe2+
(c) n = 2, He+ (d) n = 3, Li 2+ 32. The orbital angular momentum of an electron in 2s-orbital is
7 (1996, 1M)
22. If the nitrogen atom had electronic configuration 1s , it 1 h h h
would have energy lower than that of the normal ground (a) + ⋅ (b) zero (c) (d) 2 ⋅
2 2π 2π 2π
state configuration 1s2 2s2 2 p 3 , because the electrons would
33. Which of the following relates to photons both as wave
be closer to the nucleus, yet 1s7 is not observed, because it
motion and as a stream of particles ?
violates (2002, 3M)
(1992, 1M)
(a) Heisenberg uncertainty principle
(b) Hund’s rule (a) Interference (b) E = mc2
(c) Pauli exclusion principle (c) Diffraction (d) E = hν
(d) Bohr postulate of stationary orbits 34. Which of the following does not characterise X-rays ?
1 1 (a) The radiation can ionise gases (1992, 1M)
23. The quantum numbers + and − for the electron spin
2 2 (b) It causes ZnS to fluoresce
represent (2001, 1M) (c) Deflected by electric and magnetic fields
(a) rotation of the electron in clockwise and anti-clockwise (d) Have wavelengths shorter than ultraviolet rays
direction respectively
35. The correct set of quantum numbers for the unpaired
(b) rotation of the electron in anti-clockwise and clockwise
direction respectively
electron of chlorine atom is (1989, 1M)

(c) magnetic moment of the electron pointing up and down n l m n l m

respectively (a) 2 1 0 (b) 2 1 1
(d) two quantum mechanical spin states which have no classical (c) 3 1 1 (d) 3 0 0
analogue 36. The correct ground state electronic configuration of
24. The wavelength associated with a golf ball weighing 200 g chromium atom is (1989, 1M)
and moving at a speed of 5 m/h is of the order (2001, 1M) (a) [ Ar ] 3d 5 4 s1 (b) [ Ar ] 3d 4 4 s2
(a) 10−10 m (b) 10−20 m (c) [ Ar ] 3d 6 4 s0 (d) [ Ar ] 4 d 5 4 s1
(c) 10−30 m (d) 10−40 m 37. The outermost electronic configuration of the most
25. The number of nodal planes in a px orbital is electronegative element is (1988, 90, 1M)
(2001, 1M)
(a) one (b) two (c) three (d) zero (a) ns2 np3 (b) ns2 np4
(c) ns2 np5 (d) ns2 np6
26. The electronic configuration of an element is
1s , 2s 2 p 6 , 3s2 3 p 6 3d 5 , 4 s1 . This represents its (2000, 1M)
2 2
38. The orbital diagram in which the Aufbau principle is
(a) excited state (b) ground state violated (1988, 1M)
(c) cationic form (d) anionic form (a) (b)
27. The electrons, identified by quantum numbers n and l,
(i) n = 4, l = 1, (ii) n = 4, l = 0, (iii) n = 3, l = 2, (iv) n = 3, l = 1 (c) (d)
can be placed in order of increasing energy, from the lowest to
highest, as (1999, 2M) 39. The wavelength of a spectral line for an electronic transition
(a) (iv) < (ii) < (iii) < (i) (b) (ii) < (iv) < (i) < (iii) is inversely related to (1988, 1M)
(c) (i) < (iii) < (ii) < (iv) (d) (iii) < (i) < (iv) < (ii) (a) the number of electrons undergoing the transition
(b) the nuclear charge of the atom
28. The energy of an electron in the first Bohr orbit of H-atom is
–13.6 eV. The possible energy value(s) of the excited state(s) (c) the difference in the energy of the energy levels involved in
the transition
for electrons in Bohr orbits of hydrogen is (are) (1998, 2M)
(d) the velocity of the electron undergoing the transition
(a) –3.4 eV (b) – 4.2 eV
(c) – 6.8 eV (d) + 6.8 eV
28 Atomic Structure

40. The ratio of the energy of a photon of 200 Å wavelength 48. The ground state electronic configuration of nitrogen atom
radiation to that of 4000 Å radiation is (1986, 1M) can be represented by (1999, 3M)
1 1
(a) (b) 4 (c) (d) 2. (a)
4 2
41. Which one of the following sets of quantum numbers (b)
represents an impossible arrangement? (1986, 1M)
n l m s (c)
1
(a) 3 2 –2
2 (d)
1
(b) 4 0 0
2 49. Which of the following statement (s) is (are) correct ?
1 (1998, 2M)
(c) 3 2 –3 (a) The electronic configuration of Cr is [Ar] 3d 5 4 s1 (atomic
2
1 number of Cr = 24)
(d) 5 3 0 −
2 (b) The magnetic quantum number may have a negative value
42. Electromagnetic radiation with maximum wavelength is (c) In silver atom, 23 electrons have a spin of one type and 24 of
(a) ultraviolet (b) radio wave (1985, 1M)
the opposite type. (atomic number of Ag = 47)
(c) X-ray (d) infrared (d) The oxidation state of nitrogen in HN3 is – 3
76
43. Which electronic level would allow the hydrogen atom to 50. An isotone of 32 Ge is (1984, 1M)
absorb a photon but not to emit a photon? (1984, 1M) (a) 77
(b) 77
32 Ge 33 As
(a) 3s (b) 2p (c) 2s (d) 1s 77 78
(c) 34 Se (d) 34 Se
44. Correct set of four quantum numbers for the valence
(outermost) electron of rubidium ( Z = 37 ) is (1984, 1M)
Assertion and Reason
1 1
(a) 5, 0, 0, + (b) 5, 1, 0 , + Read the following questions and answer as per the direction
2 2
1 1 given below :
(c) 5, 1, 1, + (d) 6, 0, 0, +
2 2 (a) Both Statement I and Statement II are correct; Statement
II is the correct explanation of Statement I
45. The principal quantum number of an atom is related to the
(a) size of the orbital (1983, 1M)
(b) Both Statement I and Statement II are correct; Statement
(b) spin angular momentum II is not the correct explanation of Statement I
(c) orientation of the orbital in space (c) Statement I is correct; Statement II is incorrect
(d) orbital angular momentum (d) Statement I is incorrect; Statement II is correct
46. Any p-orbital can accommodate upto (1983, 1M) 51. Statement I The first ionisation energy of Be is greater than
(a) four electrons that of B.
(b) six electrons
Statement II 2p-orbital is lower in energy than 2s. (2000)
(c) two electrons with parallel spins
(d) two electrons with opposite spins
Passage Based Questions
Objective Questions II The hydrogen-like species Li2+ is in a spherically symmetric
state S 1 with one radial node. Upon absorbing light the ion
(One or more than one correct option)
undergoes transition to a state S 2 . The state S 2 has one radial
47. The ground state energy of hydrogen atom is node and its energy is equal to the ground state energy of the
−13.6 eV. Consider an electronic state Ψ of He+ whose hydrogen atom.
energy, azimuthal quantum number and magnetic quantum
52. The state S 1 is
number are −3.4 eV, 2 and 0, respectively. (2010)
(a) 1s (b) 2s (c) 2p (d) 3s
Which of the following statement(s) is(are) true for the
state Ψ? (2019 Adv.) 53. Energy of the state S 1 in units of the hydrogen atom ground
(a) It is a 4 d state state energy is (2010)
(b) The nuclear charge experienced by the electron in this state (a) 0.75 (b) 1.50 (c) 2.25 (d) 4.50
is less than 2e, where e is the magnitude of the electronic 54. The orbital angular momentum quantum number of the state
charge
S 2 is (2010)
(c) It has 2 angular nodes (a) 0 (b) 1 (c) 2 (d) 3
(d) It has 3 radial nodes
 Atomic Structure 29

Match the Columns

Answer Q. 55, Q. 55 and Q. 56 by appropriately matching the information given in the three columns of the following table.
The wave function, ψ n , l , ml is a mathematical function whose value depends upon spherical polar coordinates ( r, θ , φ ) of the electron
and characterised by the quantum number n , l and ml . Here r is distance from nucleus, θ is colatitude and φ is azimuth. In the
mathematical functions given in the Table, Z is atomic number and a0 is Bohr radius. (2017 Adv.)

Column 1 Column 2 Column 3

3  Zr 
(I) 1s-orbital (i) (P)
Z  2 −  a 0 
ψn, l , ml ∝   e
 a0 
ψn, I, ml (r)

0
r/a0

(II) 2s-orbital (ii) One radial node (Q) 1

Probability density at nucleus ∝
a03
5  Zr 
(III) 2 pz-orbital (iii) (R) Probability density is maximum at nucleus
 Z  2 − a 
ψn, l ml ∝   re  0  cosθ
 a0 

(IV) 3 dz2-orbital (iv) xy-plane is a nodal plane (S) Energy needed to excite electron from n = 2 state to n = 4 state
27
is times the energy needed to excite electron from n = 2
32
state to n = 6 state

55. For He+ ion, the only INCORRECT combination is

(a) (I) (i) (S) (b) (II) (ii) (Q) Fill in the Blanks
(c) (I) (iii) (R) (d) (I) (i) (R) 59. The outermost electronic configuration of Cr is
56. For the given orbital in Column 1, the Only CORRECT .......................... . (1994, 1M)
combination for any hydrogen-like species is 60. 8 g each of oxygen and hydrogen at 27°C will have the total
(a) (II) (ii) (P) (b) (I) (ii) (S) kinetic energy in the ratio of .......... . (1989, 1M)

(c) (IV) (iv) (R) (d) (III) (iii) (P) 61. The uncertainty principle and the concept of wave nature of
matter were proposed by ............ and .............respectively.
57. For hydrogen atom, the only CORRECT combination is (1988, 1M)
(a) (I) (i) (P) (b) (I) (iv) (R) 62. Wave functions of electrons in atoms and molecules are
(c) (II) (i) (Q) (d) (I) (i) (S) called .............. . (1993, 1M)
58. Match the entries in Column I with the correctly related 63. The 2 px, 2 p y and 2 p z orbitals of atom have identical shapes
quantum number(s) in Column II. (2008, 6M)
but differ in their ........... . (1993, 1M)
Column I Column II 64. When there are two electrons in the same orbital, they have
p. …… spins. (1983, 1M)
A. Orbital angular momentum Principal
of the electron in a quantum
True/False
hydrogen-like atomic orbital. number
q.
65. In a given electric field, β -particles are deflected more than
B. A hydrogen-like one-electron Azimuthal
wave function obeying quantum α-particles in spite of α-particles having larger charge.
(1993, 1M)
Pauli’s principle. number
66. The electron density in the XY-plane in 3d x 2 − y
orbital is
2
C. Shape, size and orientation r. Magnetic zero. (1986, 1M)
of hydrogen-like atomic quantum 67. The energy of the electron in the 3d-orbital is less than that in
orbitals. number the 4s-orbital in the hydrogen atom. (1983, 1M)
D. Probability density of s. Electron spin 68. Gamma rays are electromagnetic radiations of wavelengths
electron at the nucleus in quantum of 10−6 to 10−5 cm. (1983, 1M)
hydrogen-like atom. number 69. The outer electronic configuration of the ground state
chromium atom is 3d 4 4 s2 . (1982, 1M)
30 Atomic Structure

Integer Answer Type Questions work done in the above neutralisation process. Also, if the
magnitude of the average kinetic energy is half the
70. Not considering the electronic spin, the degeneracy of the magnitude of the average potential energy, find the average
second excited state ( n = 3 ) of H-atom is 9, while the potential energy. (1996, 2M)
degeneracy of the second excited state of H− is (2015 Adv.)
81. Calculate the wave number for the shortest wavelength
71. In an atom, the total number of electrons having quantum transition in the Balmer series of atomic hydrogen.(1996, 1M)
numbers (2014 Adv.)
82. Iodine molecule dissociates into atoms after absorbing light
1
n = 4, | ml | = 1 and ms = − is to 4500Å. If one quantum of radiation is absorbed by each
2 molecule, calculate the kinetic energy of iodine atoms.
72. The atomic masses of He and Ne are 4 and 20 amu,
(Bond energy of I2 = 240 kJ mol –1 ) (1995, 2M)
respectively. The value of the de-Broglie wavelength of He
gas at −73°C is ‘M’ times that of the de-Broglie wavelength 83. Find out the number of waves made by a Bohr’s electron in
of Ne at 727°C. M is (2013 Adv.) one complete revolution in its 3rd orbit. (1994, 3M)
73. The work function (φ) of some metals is listed below. The 84. What transition in the hydrogen spectrum would have the
number of metals which will show photoelectric effect when same wavelength as the Balmer transition n = 4 to n = 2 of
light of 300 nm wavelength falls on the metal is (2011) He+ spectrum? (1993, 3M)
Metal Li Na K Mg Cu Ag Fe Pt W 85. Estimate the difference in energy between 1st and 2nd
Φ (eV) 2.4 2.3 2.2 3.7 4.8 4.3 4.7 6.3 4.75 Bohr’s orbit for a hydrogen atom. At what minimum atomic
number, a transition from n = 2 to n = 1 energy level would
74. The maximum number of electrons that can have principal result in the emission of X-rays with l = 3.0 × 10–8 m ?
quantum number, n = 3 and spin quantum number,
Which hydrogen atom-like species does this atomic number
ms = − 1 / 2 , is (2011)
correspond to? (1993, 5M)

Subjective Questions 86. According to Bohr’s theory, the electronic energy of

hydrogen atom in the nth Bohr’s orbit is given by :
75. (a) Calculate velocity of electron in first Bohr orbit of hydrogen
atom (Given, r = a0 ). −21.7 × 10−19
En = J
(b) Find de-Broglie wavelength of the electron in first Bohr n2
orbit. Calculate the longest wavelength of electron from the third
(c) Find the orbital angular momentum of 2p-orbital in terms of Bohr’s orbit of the He+ ion. (1990, 3M)
h / 2π units. (2005, 2M)
87. What is the maximum number of electrons that may be
76. (a) The Schrodinger wave equation for hydrogen atom is present in all the atomic orbitals with principal quantum
3/ 2 number 3 and azimuthal quantum number 2 ?
1  1  r  − r / 2a 0 (1985, 2M)
ψ 2s =   2 −  e
4 (2π )1/ 2  a0   a0  88. Give reason why the ground state outermost electronic
configuration of silicon is (1985, 2M)
where, a0 is Bohr’s radius. Let the radial node in 2s be at r0.
3s 3p 3s 3p
Then, find r in terms of a0.
(b) A base ball having mass 100 g moves with velocity and not
100 m/s. Find out the value of wavelength of base ball.
(2004, 2M) 89. The electron energy in hydrogen atom is given by
21.7 × 10−12
77. The wavelength corresponding to maximum energy for En = − erg. Calculate the energy required to
hydrogen is 91.2 nm. Find the corresponding wavelength for n2
He+ ion. (2003, 2M) remove an electron completely from the n = 2 orbit. What is
the longest wavelength (in cm) of light that can be used to
78. Calculate the energy required to excite 1 L of hydrogen gas
cause this transition? (1984, 3M)
at 1 atm and 298 K to the first excited state of atomic
hydrogen. The energy for the dissociation of H—H bond is 90. Calculate the wavelength in Angstroms of the photon that is
436 kJ mol −1 . (2000) emitted when an electron in the Bohr’s orbit, n = 2 returns to
the orbit, n = 1in the hydrogen atom. The ionisation potential
79. An electron beam can undergo diffraction by crystals.
Through what potential should a beam of electrons be of the ground state hydrogen atom is 2.17 × 10−11 erg per
accelerated so that its wavelength becomes equal to 1.54 Å. atom. (1982, 4M)
(1997 (C), 2M) 91. The energy of the electron in the second and third Bohr’s
80. Consider the hydrogen atom to be proton embedded in a orbits of the hydrogen atom is − 5.42 × 10−12 erg and
cavity of radius a0 (Bohr’s radius) whose charge is − 2.41 × 10−12 erg respectively. Calculate the wavelength of
neutralised by the addition of an electron to the cavity in
vacuum, infinitely slowly. Estimate the average total energy the emitted light when the electron drops from the third to the
of an electron in its ground state in a hydrogen atom as the second orbit. (1981, 3M)
 Answers
Topic 1 33. (a) 34. (c) 35. (c) 36. (a)
1. (d) 2. (a) 3. (b) 4. (c) 37. (c) 38. (b) 39. (c) 40. (d)
5. (d) 6. (c) 7. (d) 8. (b) 41. (c) 42. (b) 43. (d) 44. (a)
9. (b) 10. (b) 11. (d) 12. (a) 45. (a) 46. (d) 47. (a,c)
13. (c) 14. (a) 15. (a,b) 16. (d) 48. (a,d) 49. (a,b,c) 50. (b,d) 51. (c)
17. (a,c) 18. (a,c) 19. (a) 20. (c)
52. (b) 53. (c) 54. (b) 55. (c)
21. A → r; B → q; C → p, D → s
56. (a) 57. (d)
22. (photons) 23. (1 . 66 × 10 –27 kg) 24. (neutrons)
58. A → q; B → p, q, r, s C → p, q, r D → p, q, r
25. (isobars) 26. (–5242.41) 27. 6.3 × 10 6
5 1
59. Cr = [Ar] 3d , 4s 60. 1 : 16
Topic 2
61. Heisenberg, de-Broglie. 62. orbital
1. (c) 2. (a) 3. (a) 4. (a)
63. Orientation in space 64. opposite
5. (a) 6. (d) 7. (c) 8. (c)
65. True 66. False 67. True 68. False
9. (b) 10. (d) 11. (d) 12. (b)
69. False 70. (3) 71. (6) 72. (5)
13. (c) 14. (d) 15. (c) 16. (c) 73. (4.14 eV) 74. (9) 77. (22.8 nm) 78. (98.44 kJ)
17. (a) 18. (a) 19. (c) 20. (a)
79. (63.56 V) 81. (2.725× 10 6 M −1)
21. (b) 22. (c) 23. (d) 24. (c)
82. (2.16 × 10 20 J/atom) 86. (471 nm) 87. (10)
25. (a) 26. (b) 27. (a) 28. (a)
−5
29. (a) 30. (b) 31. (d) 32. (b) 89. (3.66 × 10 cm) 90. (1220 Å) 91. (660 nm)

Hints & Solutions

Topic 1 Preliminary Developments decreases. The maximum in the curve corresponds to the
and Bohr’s Model distance at which the probability of finding the electron in
maximum.
1. Statement (d) is incorrect. For 1s-orbital radial probability
density (R 2 ) against r is given as: 2. The expression of kinetic energy of photo electrons,
1
mv 2 = E − E0
KE =
2
When, KE > > E0, the equation becomes,
1
KE = mv 2 = E
R2 2
1s
1 2 hc p2 hc
⇒ mv = ⇒ =
2 λ 2m 2
λ
r 2 1 1
⇒ λ = hc × 2m × 2 ⇒ λ ∝ 2
For 1s-orbital, probability density decreases sharply as we move p p
away from the nucleus. hc
E= = energy of incident light.
The radial distribution curves obtained by plotting radial λ
probability functions vs r for 1s-orbital is E0 = threshold energy or work functions,
1 2 1 (mv )2 1 p2
mv = × = × 2
2 2 m2 2 m
Q p = momentum = mv
4πrR2

As per the given condition,

2
λ 2  p1 
= 
λ 1  p2 
2 2
λ2  p   2 4
r ⇒ =  =  =
λ  15
. × p  3 9
The graph initially increases and then decreases. It reaches a
maximum at a distance very close to the nucleus and then
32 Atomic Structure

4 Q λ 1 = λ  So, option (a) is correct.

⇒ λ2 = λ
9  p1 = p  (ii) KE of ejected electrons does not depend on the intensity of
3. Work function of metal (φ ) = hν 0 incident light.
where, ν 0 = threshold frequency
KE
1
Also, mev 2 = hν − hν 0
2
1
or mev 2 = hν − φ …(i)
2 0
Intensity of light
1 hc
mev 2 = −φ …(ii)
2 λ So, option (b) is correct.
Given : λ = 4000 Å = 4000 × 10−10m (iii) When, number of ejected electrons is plotted with frequency
v = 6 × 105 ms −1, of light, we get

me = 9 × 10−31 kg, c = 3 × 108 ms −1

Number
h = 6.626 × 10−34 Js of e–’s
Thus, on substituting all the given values in Eq. (i), we get
1
× 9 × 10−31 kg × (6 × 105 ms −1 )2
2 0
Frequency of light (n)
6.626 × 10−34 J s × 3 × 108 ms −1
= −φ So, option (c) is also correct.
4000 × 10−10 m
(iv) KE = hν − hν 0
∴ . × 10−21 kgm 2s −2 − 4.96 × 10−19 J
φ = 162
= 3.36 × 10−19 J [1 kgm2s −2 = 1J]
KE
= 21
. eV
0 n0 n
4. The ground state energy of H-atom is + 13.6 eV.
For second excited state, n = 2 + 1 = 3
Z2
∴ E3 (He+ ) = − 13.6 × 2 eV [Qfor He+ , Z = 2] Slope = + h, intercept = − hν 0. So, option (d) is not correct.
n
22
6. Plan As you can see in options, energy term is mentioned hence, we
= − 13.6 × 2 eV = − 6.04 eV have to find out relation between h / λ and energy. For this, we
3 shall use de-Broglie wavelength and kinetic energy term in eV.
h
5. For photoelectric effect, de-Broglie wavelength for an electron (λ ) =
(i) KE = E − E0 p
h
⇒ p= …(i)
λ
Kinetic energy of an electron = eV
|Ψ|2 For 1s-orbital
number of radial node = 1–0–1=0 p2
As we know that, KE =
2m
r p2
∴ eV = or p = 2 meV …(ii)
where, 2m
KE = Kinetic energy of ejected electrons. h
From equations (i) and (ii), we get = 2 meV
E = Energy of incident light = hν λ
E0 = Threshold energy = hν0
7. Rutherford used α-particle (He2+ nuclei) in his experiment.
ν = Frequency of incident light
ν0 = Threshold frequency 8. According to Rutherford’s model, there is a heavily positively
charged nucleus and negatively charged electrons occupies space
around it in order to maintain electro-neutrality.
KE 9. Radius of a nucleus is in the order of 10−13 cm, a fact.
0
E0 E
10. Bohr’s model is applicable to one-electron system only.
11. Neutron has no charge, hence e/ m is zero for neutron. Next,
α-particle (He2+ ) has very high mass compared to proton and
electron, therefore very small e/ m ratio. Proton and electron
Slope = ± 1, intercept = − E0
 Atomic Structure 33

have same charge (magnitude) but former is heavier, hence has 1  Ze2 
smaller value of e/ m.
21. A. Vn = −  
4 πε 0  r 
e
: n<α < p< e 1  Ze2 
m Kn =  
8πε 0  r 
12. The negligibly small size of nucleus compared to the size of
atom was first established in Rutherford’s experiment. Vn
⇒ = − 2  (r )
13. The most important findings of Rutherford’s experiment is Kn
discovery of nucleus.
Ze2
14. Energy of electron in H-atom is determined by the expression: B. En = − ∝ r −1
8πε 0r
13.6
En = − eV where, n =1, 2, 3, .... ⇒ x = − 1  (q )
n2
13.6 h
In excited states, E2 = − = − 3.4 eV C. Angular momentum = l (l + 1) = 0 in 1s-orbital — (p)
4 2π
a0n2 1
13.6 D. rn = ⇒ ∝ Z  (s)
E3 = − = − 1.51 eV etc. Z rn
9
15. Nucleus is composed of neutrons and protons. 22. Photons have quantised energy.
16. The isotopes of hydrogen are 1 H2 and 1H3. 10−3
23. Mass of one H-atom = kg = 1.66 × 10−27 kg
6.023 × 1023
17. Alpha particles passes mostly undeflected when sent through
thin metal foil mainly, because 24. Isotopes have different number of neutrons.
(i) it is much heavier than electrons. 25. Isobars have same mass number but different atomic numbers.
(ii) most part of atom is empty space.
26. Given that, electrons and nucleus are at infinite distance, so
18. Many elements have several isotopes. For such elements, potential energy of H-atom is taken as zero.
atomic mass is average of the atomic masses of different
Therefore, according to Bohr’s model, potential energy of a
isotopes, which is usually non-integral.
H-atom with electron in its ground state = − 27.2 eV
19. (III) Kinetic energy of the electron in nth orbit, At d = d0, nucleus-nucleus and electron-electron repulsion is
Z2 absent.
K.E. = + 13.6 × Hence, potential energy will be calculated for 2H atoms
n2
= − 2 × 27.2 eV= − 54.4 eV
1
or K.E. ∝ or K.E. ∝ n−2 Potential enery of 1 mol H atoms in kJ
n2
. × 10−19
54.4 × 6.02 × 1023 × 16
From list-II, correct match is (III P). = = − 5242. 4192 kJ/mol
1000
(IV) Potential energy of the electron in the nth orbit,
Z2 27. When α-particle stop at 10−13m from nucleus, kinetic energy is
P.E. = − 2 × 13.6 × 2 zero, i.e. whole of its kinetic energy at the starting point is now
n
converted into potential energy.
1
P.E. ∝ 2 Potential energy of this α-particle can be determined as
n
P.E. ∝ n−2 Z1 × Z2e2
PE = −
From List II, correct match is (IV P). (4 πε 0 ) r
Hence, correct matching from list-I and list-II on the basis of
given option is (III, P). (Z1 = + 2, Z2 = + 29, ε 0 = 8.85 × 10−12 J−1 C2 m −1,
r = 10−13 m)
20. (I) Radius of the nth orbit, −19 2
2 × 29 × (1.6 × 10 )
n2 ⇒ | PE | = J
r = 0.529 × 4 × 3.14 × 8.85 × 10−12 × 10−13
Z
= 1.33 × 10−13 J
Here, r ∝ n2
From list-II, correct match is (I, T ) = kinetic energy of α-particle at t = 0
1
(II) Angular momentum of the electron, ⇒ KE = mv 2 = 1.33 × 10−13
nh 2
mvr = or mvr ∝ n
2π 2 × 1.33 × 10−13
⇒ v= = 6.3 × 106 ms−1
From list-II, correct match (II, S) 4 × 1.66 × 10−27
Hence, correct matching from list-I and list-II on the basis of
given option is (I, T ).
34 Atomic Structure

The graph between wavefunction (ψ ) and distance (r) from the

Topic 2 Advanced Concept (Quantum Mechanical nucleus helps in determining the shape of orbital.
Theory) Electronic Configuration and
Quantum Number 5. According to Rydberg’s equation,
1. Quantum nature of atoms are associated with following 1 RH  1 1 1  1 1
=  −  or ∝ − 
phenomena or processes : λ hc  n12 n22  λ  n12 n22 
(i) Absorption spectrum (ii) Emission spectrum For shortest wavelength, i.e. highest energy spectral line, n2 will
(iii) Black body radiation (iv) Photo-electricity
be (∞ ).
Internal energy (U ) of particles like atoms depends upon the
For the given spectral series, ratio of the shortest wavelength of
thermodynamic variables ( p, V , T ) of the system. Thus,
two spectral series can be calculated as follows :
U = f ( p,T ) or U = f1 (T ,V ) orU = f2 ( p,V )
1 1 1
So, quantum nature of atom is not associated with its internal − −0
λ L 32 ∞ 2 9 1
energy. (a) = = =
λP 1
−
1 1 − 0 9
Graph (c) is not a direct manifestation of the quantum nature of
atoms. 12 ∞ 2
1 1
2. According to quantum mechanical atom model, for each value − 2
λ Bk 5 2
∞ 1 16 16
of n (principal quantum number), there are ‘n’ different values of (b) = = × =
l (azimuthal quantum number), i.e. l = 0, 1, 2, …, (n − 1). And, λ Pf 1
−
1 25 1 25
for each value of l, there are 2l + 1 different values of ml 4 2 ∞2
(magnetic quantum number), i.e. ml = 0, ±1, ±2 … ± l. 1 1
− 2
∴Total number of possible combinations of n, l and ml , for a λP 5 2
∞ 1 9 9
(c) = = × =
given value of n is n2, and each such combination is associated λ Pf 1
−
1 25 1 25
with an orbital. Each orbital can occupy a maximum of two 32 ∞ 2
electrons, having a different value of spin quantum number (ms ), 1 1
1 1 − 2
which are + or − . λB 4 2
∞ 1 4 1
2 2 (d) = = × =
λ Bk 1
−
1 16 1 4
∴ Number of orbitals associated with n = 5 is n2 = 25. Each of 22 ∞ 2
1
those orbitals can be associated with ms = + as well as Note Lyman = L (n1 = 1), Balmer = B (n1 = 2)
2
1 Paschen = P (n1 = 3), Brackett = Bk (n1 = 4 )
ms = − .
2 Pfund = Pf (n1 = 5)
∴ Answer = 25 6. The graphs between | ψ |2 and r are radial density plots having
3. The energy of 2s-orbital is lowest in K(potassium). An orbital (n − l − 1) number of radial nodes. For 1s, 2s, 3s and 2 p-orbitals
gets larger as the principal quantum number n increases. these are respectively.
Correspondingly, the energy of the electron in such an orbital
becomes less negative, meaning that the electron is less strongly
bound and has less energy. The graph of principal quantum
number with atomic number is |Ψ|2 For 2s-orbital
number of radial node = 2–0–1=1
Principal quantum

2
r
number

1 2s |Ψ|2 For 3s-orbital

number of radial node = 3–0–1=2
1 25 50 75 100
Atomic number
r
4. The electrons are more likely to be found in the region aand c. At
b, wave function becomes zero and is called radial nodal surface
or simply node.
a |Ψ|2 For 2p-orbital
Y (x) number of radial node = 2–1–1=0

b +x →
← –x r

c Thus, the given graph between | ψ |2 and r represents 2s-orbital.

 Atomic Structure 35

7. For any given series of spectral lines of atomic hydrogen. Thus, Eq. (i) becomes
Let ∆ν = ν max − ν min be the difference in maximum and n2
2πa0 = nλ ...(ii)
minimum frequencies in cm−1. Z
For Lyman series, n2
∴ 2πa0 = n (1.5 πa0) [Given, λ = 1 .5 πa0]
∆ν = ν max − ν min Z
General formula: n 15 . πa0 1.5
= = = 0.75
1 1 Z 2πa0 2
ν = 109677  2 − 2 
 ni nf  10. de-Broglie wavelength (λ) for electron is given by
For Lyman n1 = 1, n2 = 2, 3, K λ=
h
...(i)
1 1 1  2 m K.E
ν max = 109,677 −  = 109,677  − 0
 1 ∞ 1  Also, according to photoelectric effect
= 109,677 KE = hν − hν 0
1 1  On substituting the value of KE in Eq (i), we get
ν min = 109,677 − 2  h
 1 (2)  λ=
2m × (hν − hν 0 )
∆ν Lyman = ν max − ν min
109,677 × 3  109,677 1
= 109,677 −  ∴ λ∝
 4  = 4 (ν − ν 0 )1/ 2
For Balmer series, nh
11. (I) Angular momentum, mvr =
 1 1 109677 2π
ν max = 109,677 2 −  ⇒
 (2) ∞  4 ⇒ mvr ∝ n
∝ distance from the nucleus
 1 1  109677 × 5
ν min = 109,677 2 − 2  ⇒ (II) This statement is incorrect as size of an orbit
 (2) (3)  36
∝ Azimuthal quantum number (l )
∆ν = ν max − ν min
(Q n = constant)
109,677 109,677   1
∆ν Balmer = − × 5 = 109,677   (III) This statement is incorrect as at ground state,
4  36   9 n = 1, l = 0
∆ν Lyman 109,677 / 4 ⇒ Orbital angular momentum (wave mechanics)
=
∆ν Balmer 109,677 / 9 h
= l (l + 1) =0 [Q l = 0 ]
∆ν Lyman 9 2π
= (IV) The given plot is
∆ν Balmer 4
∆ν Lyman
∴The ratio of is 9 : 4. l=0 (n=1)
∆ν Balmer l=1 (n=2)

8. Smaller the value of (n + l ), smaller the energy. If two or more l=2 (n=3)
sub-orbits have same values of (n + l ), sub-orbits with lower ψ
values of n has lower energy. The (n + l ) values of the given l=3 (n=4)
options are as follows :
I. n = 4, l = 2 ; n + l = 6
II. n = 3, l = 2; n + l = 5
r
III. n = 4 , l = 1, n + l = 5
IV. n = 3, l = 1, n + l = 4 1   1 1 
12. ∆E = hc × = hc × RH  2 − 2  × Z 2 
Among II and III, n = 3 has lower value of energy. Thus, the λ   n1 n2  
correct order of their increasing energies will be
1 1 hc
IV < II < III < I ⇒ − 2= [for H, atom Z = 1]
n1 n2 RH × λ × Z 2 × hc
2
Circumference 2πr
9. Number of waves = ⇒ n= 1 1 1
Wavelength λ = = ×
RH × λ (1 × 10 7 m−1 ) (900 × 10−9 m)
∴ 2πr = nλ ...(i)
1 1 1
Also, we know that radius (r) of an atom is given by ⇒ − =
n12 n22 9
a n2
r= 0 1 1 1 1 ∴ n1 = 3,
Z So, in option (b) − = −0=
32 ∞ 2 9 9  n2 = ∞ 
36 Atomic Structure

13. According to Rydberg’s formula, 17. Given, atomic number of Rb, Z = 37

1 2 1 Thus, its electronic configuration is [ Kr ]5s1. Since, the last
wave number (ν) = RH Z  2 − 2 
 ni nf  electron or valence electron enter in 5s subshell.
Given, ni = n, nf = 8 [Q it is the case of emission] So, the quantum numbers are n = 5, l = 0, (for s-orbital) m = 0
(Q m = + l to −l), s = + 1 / 2 or − 1 / 2.
1 1
ν = RH × (1)2  2 − 2  Z2 
n 8  18. Given, in the question E = − 2.178 × 10−18 J  2 
n 
1 1 R R For hydrogen Z = 1,
ν = RH  2 −  = H2 − H
 n 64  n 64 1
So, E1 = − 2.178 × 10−18 J  2 
On comparing with equation of straight line, y = mx + c, we get 1 
−RH 1
Slope = RH , intercept = . −18
E2 = − 2.178 × 10 J  2 
64 2 
1 Now, E1 − E2
Thus, plot of wave number (ν) against 2 will be linear with
n 1 1  hc
i.e. ∆E = 2.178 × 10−18  2 − 2  =
slope (+ RH ). 1 2  λ
14. Bohr radius (rn ) = ∈0 n2h2 1 1 6.62 × 10−34 × 3.0 × 108
2.178 × 10−18  2 − 2  =
n2h2 1 2  λ
rn =
4π 2me2kZ ∴ λ ≈ 1.21 × 10−7 m
1 19. According to Bohr’s model,
k=
4 π ∈0 nh n2h2
mvr = ⇒ (mv )2 =
2 2
n h ∈0 a 2π 4 π 2r2
∴ rn = = n2 0
πme2Z Z 1 n2h2
⇒ KE = mv 2 = …(i)
where, m = mass of electron 2 8π 2r2m
e = charge of electron Also, Bohr’s radius for H-atom is, r = n2a0
h = Planck’s constant Substituting ‘r’ in Eq. (i) gives
k = Coulomb constant h2 h2
KE = when n = 2 , KE =
n2 × 0.53 8π 2n2a02m 32π 2 a02 m
rn = Å
Z 20. The number of radial nodes is given by expression (n − l − 1).
Radius of n th
Bohr orbit for H-atom For 3s, number of nodes = 3 − 0 − 1 = 2
= 0.53 n Å2
[Z = 1for H-atom] For 2p, number of nodes = 2 − 1 −1 = 0
a0n2
∴Radius of 2nd Bohr orbit for H-atom 21. Expression for Bohr’s orbit is, rn = = a0
Z
= 0.53 × (2)2 = 212
. Å when n = 2, Z = 4.
15. This graph shows the probability of finding the electron within 22. 1s7 violate Pauli exclusion principle, according to which an
shell at various distances from the nucleus (radial probability). orbital cannot have more than two electrons.
The curve shows the maximum, which means that the radial 1 1
probability is greatest for a given distance from the nucleus.
23. + and − just represents two quantum mechanical spin states
2 2
This distance is equal to Bohr’s radius = a0 which have no classical analogue.
24. Using the de-Broglie’s relationship :
P h 6.625 × 10−34
1s
λ= = = 2.3 × 10−30 m
mv 0.2 × 5
r 60 × 60

(a) It is for 2s-orbital. 25. Nodal plane is an imaginary plane on which probability of
(b) It is radial wave function for 1s. finding an electron is minimum. Every p-orbital has one nodal
plane :
(c) Correct
(d) Probability cannot be zero at a certain distance from nucleus.
13.6 px
16. ∴ En = − eV where, n = 1, 2, 3 ...
n2
−13.6 YZ-plane, a nodal plane
In excited states, E2 = = −3.4 eV
4
 Atomic Structure 37

26. 1s2 2 s2 2 p6 3s2 3 p6 3d 5 4 s1 is ground state electronic configuration 38. Option (b) is wrong representation according to aufbau
of Cr. principle. A high energy atomic orbital (2p) cannot be filled
unless the low energy orbital (2s) is completely occupied.
27. (i) n = 4, l = 1 ⇒ 4 p-orbital
(ii) n = 4, l = 0 ⇒ 4s-orbital  1 1  hc
39. Transition energy (∆E ) = kZ 2  − 2 =
n = 3, l = 2 ⇒  n1 n2  λ
2
(iii) 3d-orbital
(iv) n = 3, l = 1 ⇒ 3d-orbital
1
According to Aufbau principle, energies of above mentioned i.e. ∆E ∝
λ
orbitals are in the order of
hc E λ
(iv) 3p < (ii) 4s < (iii) 3d < (i) 4 p 40. E = ⇒ 1 = 2 =2
λ E2 λ 1
28. The energy of an electron in a Bohr atom is expressed as
41. n l m s
where, k = Constant,
kZ 2 1
En = − 2 Z = Atomic number, 3 2 −3
n 2
n = Orbit number
This is the wrong set of quantum number because | m | cannot be
= − 13.6 eV for H (n = 1) greater than l.
− 13.6
when n = 2 , E2 = eV = − 3.40 eV 42. The wavelength order is
22
X-ray < ultraviolet < infrared < radio wave
(n can have only integral value 1, 2, 3,…… ∞)
43. When electron jumps to lower orbit photons are emitted while
h
29. The orbital angular momentum (L) = l (l + 1) photons are absorbed when electron jumps to higher orbit.
2π 1s-orbital is the lower most, electron in this orbital can absorb
h photons but cannot emit.
= 6 (l = 2 for d - orbital )
2π
44. The valence shell configuration of Rubidium (Rb) is
30. Bohr first made use of quantum theory to explain the structure of 1 1
[ Kr ] 5s1 n = 5, l = 0, m = 0, s = + or −
atom and proposed that energy of electron in an atom is 2 2
quantised.
45. The principal quantum number ‘n’ represents orbit number
31. Mg2+ = 1s2 2s2 2 p6 no unpaired electron hence, determine the size of orbitals.
3+ 2 2 6 2 6 1
Ti = 1s 2 s 2 p 3s 3 p 3d one unpaired electron 46. According to Pauli exclusion principle, an atomic orbital can
3+ 2 2 6 2 6 2 accommodate at the most, two electrons, with opposite spins.
V = 1s 2 s 2 p 3s 3 p 3d two unpaired electrons
47. Given, ground state energy of hydrogen atom = − 13.6 eV
Fe2+ = 1s2 2 s2 2 p6 3s2 3 p6 3d6 four unpaired electrons
Energy of He + = − 3.4 eV, Z = 2
32. Expression for orbital angular momentum (L) is 13.6 × Z 2
h Energy of He + , E = − eV
L = l (l + 1) = 0 for 2s-electrons n2
2π
− 13.6 × (2 )2 13.6 × 4
Q For s-orbital, l = 0. − 3.4 eV = ⇒ n= ⇒ n=4
n2 3.4
33. Diffraction is property of wave, E = mc2 determine energy of Given, azimuthal quantum number (l ) = 2 (d – subshell
particle and E = hν determine energy of photon. Interference Magnetic quantum number (m) = 0
phenomena is exhibited by both matter and waves.
∴ Angular nodes (l ) = 2
34. X-rays is electrically neutral, not deflected in electric or Radial node = n − l − 1= 4 − 2 − 1= 1
magnetic fields.
nl = 4 d state
35. Cl (17) = 1s2 2 s2 2 p6 3s2 3 p5 Hence, options (a), (c) are correct.
48. Both (a) and (d) are correct. The three electrons in the
2p-orbitals must have same spin, no matter up spin or down spin.
The last, unpaired electron has, n = 3, l = 1( p) and m can have 49. (a) Cr = [Ar] 3d 5 4 s1 , an exception to aufbau principle.
any of the three value (− 1, 0, + 1).
(b) For a given value of l, m can have any value from
36. Cr (24) = 1s2 2 s2 2 p6 3s2 3 p6 3d 5 4 s1 (−l to + l), so can have negative value.
1442443
Ar (c) Ag is in copper group with d 10s1 configuration,
i.e. 46 electrons are spin paired.
The above configuration is exception to Aufbau’s principle.
37. Fluorine, a halogen, is the most electronegative atom, has the 50. Isotones have same number of neutrons.
76 77
2 5
electronic configuration 2s 2 p (valence shell). 32 Ge , 33As and 34Se78 have same number (44) of neutrons,
hence they are isotones.
38 Atomic Structure

51. Assertion is correct Be(1s2 , 2s2 ) has stable electronic 66. 3dx2 − y2 orbital lies in XY-plane.
configuration, removing an electron require more energy than 67. Aufbau principle.
the same for B(2 p1 ). Reason is incorrect
(Aufbau principle). 68. This is the wavelength of infrared radiation.
52. S 1 is spherically symmetrical state, i.e. it correspond to a 69. Cr = 3d 5 4 s1.
s-orbital. Also, it has one radial node. 70. In an one electron (hydrogenic) system, all orbitals of a shell
Number of radial nodes = n − l − l remains degenerate, hence in second excited state, the
⇒ n − 0 − 1 = 1 ⇒ n = 2 i.e. S 1 = 2s-orbital. degeneracy of H-atom is nine
3s 3p 3d
53. Ground state energy of electron in H-atom (EH ) H(1s1) Second excited
Ground state state of H-atom
kZ 2
EH = = k (Z = 1, n = 1) All are degenerate
n2 degeneracy = 9
For S 1 state of Li 2+ , In case of many electrons system, different orbitals of a shell are
k (3)2 9 non-degenerate. Hence,
E = 2 = k = 2.25 k
2 4 1s 1s 2s 2p 1s 2s 2p
–
2+ H
54. In S 2 state, E (Li ) = K (given)
Second excited
Ground state First excited state
qk state only three p-orbitals
K = 2 ⇒ n=3 (2px, 2py, 2pz) are
n
degenerate.
Since, S 2 has one radial node.
3 − l −1 = 1 ⇒ l = 1 71. PLAN This problem is based on concept of quantum number. Follow
+ the following steps to solve this problem.
55. In the wave function (ψ ) expression for 1s-orbital of He , there Write all possible orbitals having combination of same principal,
should be no angular part. Hence (iii) can’t be true for ψ 1s of azimuthal, magnetic and spin quantum number.
He+ . Then count the all possible electrons having given set of
56. Correct : 2s orbital has one radial node. quantum numbers.
No of radial node = n − l − 1 = 2 − 0 − 1 = 1 For n = 4, the total number of possible orbitals are
Also, when radial part of wave function (ψ ) is plotted against 4s 4p 4d 4f
‘‘r’’, wave function changes its sign at node. 0 –1 0 +1 –2 –1 0 +1 +2 –3 –2 –1 0 +1 +2 +3

57. i is the correct expression of wave function for 1s-orbital of According to question | m l | = 1, i.e. there are two possible
hydrogenic system.
values of m l , i.e. +1 and –1 and one orbital can contain
58. A. Orbital angular momentum 1
maximum two electrons one having s = + and other having
h 2
(L) = l (l + 1)
2π s = − 1/ 2 .
i.e. L depends on azimuthal quantum number only. So, total number of orbitals having {| m l | = 1} = 6
B. To describe a one electron wave function, three quantum Total number of electrons having
numbers n, l and m are needed. Further to abide by Pauli 1
{| m l | = 1and ms = − } = 6
exclusion principle, spin quantum number(s) is also needed. 2
1 3
C. For shape, size and orientation, only n, l and m are needed. 72. PLAN KE = mv 2 = RT
2 2
D. Probability density (ψ 2 ) can be determined if n, l and m are ∴ m2v 2 = 2mKE ∴ mv = 2mKE
known.
h h h
λ (wavelength) = = ∝
59. Cr = [Ar] 3d 5 4 s1 mv 2mKE 2m(T )
60. 1 : 16 where, T = Temperature in Kelvin
h
61. Heisenberg proposed uncertainty principle and de-Broglie λ (He at −73° C = 200 K) =
proposed wave nature of electron. 2 × 4 × 200

62. orbital h
λ (Ne at 727°C = 1000 K) =
2 × 20 × 1000
63. 2 px ,2 py and 2pz have different orientation in space.
λ (He) 2 × 20 × 1000
64. Two electrons in same orbital must have opposite spin. ∴ =M = =5
λ (Ne) 2 × 4 × 200
65. Very large mass of alpha particles than beta particles is
responsible for less deflection in former case. Thus, M =5
 Atomic Structure 39

73. Energy of photon pV 1×1

78. Moles of H2 = = = 0.0409
–34 8 RT 0.082 × 298
hc hc 6.625 × 10 × 3 × 10
= J= eV = = 4 . 14 eV ⇒ Bond energy = 0.0409 × 436 = 17.84 kJ
λ eλ 300 × 10–9 × 1.602 × 10–19
Number of H-atoms produced after dissociation
For photoelectric effect to occur, energy of incident photons = 2 × 0.0409 × 6.023 × 1023 = 4.93 × 1022
must be greater than work function of metal. Hence, only Li, Na,
K and Mg have work functions less than 4.14 V.  1
Transition energy/atom = 2.18 × 10−18 1 −  J
 4
74. When n = 3, l = 0, 1, 2 i.e. there are 3s, 3p and 3d-orbitals. If all
3
these orbitals are completely occupied as = × 2.18 × 10−18 J
4
⇒ Total transition energy
1
Total 18 electrons, 9 electrons with s = + and 9 with 3
2 = × 2.18 × 10−18 × 4.93 × 1022 J
4
1
s=– . = 80.60 × 103 J = 80.60 kJ
2
Therefore, total energy required
Alternatively In any nth orbit, there can be a maximum of 2n2
electrons. Hence, when n = 3, number of maximum electrons = = dissociation energy + transition energy
1 = (17.84 + 80.60) kJ = 98.44 kJ
18. Out of these 18 electrons, 9 can have spin –
1 2 79. If accelerated by potential difference of V volt, then
and remaining nine with spin + .
2 1
nh mv 2 = eV
75. (a) mvr = 2
2π
p2
nh 6.625 × 10−34 ⇒ = eV , here p = momentum (mv )
⇒ v= = 2m
2πmr 2 × 3.14 × 9.1 × 10−31 × 0.529 × 10−10 h h
Using de-Broglie equation, λ = =
= 2.18 × 106 ms − 1 p 2meV
h 6.625 × 10−34 6.625 × 10−34
(b) λ = = = 0.33 × 10−9 m ⇒ 1.54 × 10−10 =
mv 9.1 × 10−31 × 2.18 × 106 (2 × 9.1 × 10−31 × 1.6 × 10−19 V )1/ 2
(c) Orbital angular momentum Solving for V gives : V = 63.56 V.
h  h
(L) = l (l + 1) = 2  80. The work done in the given neutralisation process is
2π  2π 
∞ e2
[Q For p-orbital, l = 1] W =−∫ F dr and F =
a0 4πε 0r2
2
76. (a) At radial node, ψ must vanishes, i.e. ∞
e2  1  e2
⇒ W = = − = Total energy (E )
4 πε 0  r  a 0
2 2 r0
 1   r0  − a 0 4 πε 0r
ψ 22s = 0 =   2 −  e
 4 2π   a0 
Now, if ‘V’ is magnitude of potential energy, then according to
r0 given information, kinetic energy (Ek ) is V / 2. Therefore,
⇒ 2− = 0 ⇒ r0 = 2a0 V
a0 E = −V + (PE is always negative)
2
h 6.625 × 10−34
(b) λ= = = 6.625 × 10−35 m V
mv 100 × 10−3 × 100 =−
2
= 6.625 × 10−25 Å (negligibly small) − e2
⇒ V = − 2E =
77. The general Rydberg’s equation is 2πε 0r
1  1 1 81. The Rydberg’s equation for H-atom is
ν= = R (Z )2  2 − 2
λ  1
n n2  1
1 1
1 = ν (wave number) = RH  2 − 2 
⇒ ∝ Z2 λ  n1 n2 
λ
For Balmer series, n1 = 2 and n2 = 3, 4 , 5, ..., ∞
λ (He+ ) Z (H)2 1
⇒ = = For shortest λ , n2 has to be maximum, i.e. infinity. Then
λ (H) Z (He+ )2 4
 1 1 R 1.09 × 107
λ (H) 91.2 ν = RH  −  = H = = 2.725 × 106 m −1
⇒ λ (He+ ) = = nm = 22.8 nm  4 ∞ 4 4
4 4
40 Atomic Structure

82. After breaking of the bond of I2 molecule, the remaining energy For longest wavelength transition from 3rd orbit, electron must
would be distributed uniformly to iodine atoms as their kinetic jump to 4th orbit and the transition energy can be determined as
energy, i.e. 1 1
∆E = + 4 × 21.7 × 10−19  −  J = 4.22 × 10−19 J
E (energy of photon) = Bond energy + 2 × kinetic energy  9 16

6.625 × 10−34 × 3 × 108 240 × 103 Also, Q ∆E =

hc
⇒ = + 2 × Ek λ
4500 × 10−10 6.023 × 1023
hc 6.625 × 10−34 × 3 × 108
⇒ Ek = 2.16 × 1020 J/atom ∴ λ= = m
∆E 4.22 × 10−19
83. The Bohr de-Broglie relationship is
= 471 × 10−9 m = 471 nm
2πr = nλ = circumference of Bohr’s orbit.
i.e. number of complete waves formed in one complete 87. Ten, the given value of n and l correspond to 3d-orbital which
revolution of electron in any Bohr orbit is equal to orbit number, has five fold degeneracy level.
hence three. 88. The 2nd configuration is against Hund’s rule of maximum
84. The expression for transition wavelength is given by Rydberg’s multiplicity which states that the singly occupied degenerate
equation : atomic orbitals must have electrons of like spins.
1  1 1 89. The required transition is n1 = 2 to n2 = ∞ and corresponding
= RH Z 2  2 − 2 
λ  n1 n2  transition energy is
Equating the transition wavelengths of H-atom and He ion, +  1 1
∆E = 21.7 × 10−12  2 − 2  erg
 1 1 4 4  n1 n2 
RH  2 − 2  = RH  2 − 2 
 n1 n2  2 4  21.7
= × 10−12 erg = 5.425 × 10−12 erg
4
Equating termwise on left to right of the above equation gives
n1 = 1 and n2 = 2 The longest wavelength that can cause above transition can be
determined as :
85. For H-atom, the energy of a stationary orbit is determined as
hc 6.625 × 10−34 × 3 × 108
k −18 λ= =
En = − 2 where, k = constant (2.18 × 10 J) ∆E 5.425 × 10−12 × 10−7
n
 1 3 = 3.66 × 10−7 m = 3.66 × 10−5 cm
⇒ ∆E (n = 2 to n = 1) = k 1 −  = k
 4 4
90. Ionisation potential of H-like species
= 1.635 × 10−18 J = E1 = 2.17 × 10−11 erg
For a H-like species, energy of stationary orbit is determined as
kZ 2  1
En = − 2 ⇒ ∆E = 2.17 × 10−11 1 − 2  × 10−7 J
 2 
n
where, Z = atomic number hc
= 1.6275 × 10−18 J ⇒ λ =
 1 1 ∆E
⇒ ∆E = kZ 2  2 − 2 
 n1 n2  6.625 × 10−34 × 3 × 108
= m
1.6275 × 10−18
1 ∆E k 2  1 1 2 3
⇒ = = Z  −  = RH Z × = 122 × 10−9 m = 1220 Å
λ hc hc 1 4  4
4 4 91. Transition energy = [ − 2.41 − (− 5.42)] × 10−12 erg
⇒ Z2 = = = 4.05
3RH λ 3 × 1.097 × 107 × 3 × 10−8 = 3.01 × 10−12 erg
= 3.01 × 10−19 J [Q 1 erg = 10−7 J ]
⇒ Z = 2 (He+ )
hc
Also, ∆E =
86. For H-like species, the energy of stationary orbit is expressed as λ
E ( X ) = Z 2 × E (H ) 6.625 × 10−34 × 3 × 108
+
⇒ For He (Z = 2) ⇒ λ= m
3.01 × 10−19
4 × 21.7 × 10−19
E=− J = 660 × 10−9 m = 660 nm
n2
3
Periodic Classification
and Periodic Properties

Topic 1 History and Periodic Classification

Objective Questions I (Only one correct option) (c) the first ionisation energies of elements along a period do not
vary in a regular manner with increase in atomic number
1. The IUPAC symbol for the element with atomic number 119
(d) for transition elements the d-subshells are filled with electrons
would be (2019 Main, 8 April II)
monotonically with increase in atomic number
(a) unh (b) uue
(c) uun (d) une Objective Question II
2. The element with Z = 120 (not yet discovered) will be an/a (One or more than one correct option)
(2019 Main, 12 Jan I)
(a) transition metal (b) inner-transition metal 4. The statements that is/are true for the long form of the
(c) alkaline earth metal (d) alkali metal periodic table is/are (1988, 1M)
(a) it reflects the sequence of filling the electrons in the order of
3. The statement that is not correct for the periodic sub-energy level s, p, d and f
classification of elements, is (1992, 1M)
(b) it helps to predict the stable valency states of the elements
(a) the properties of elements are the periodic functions of their
(c) it reflects tends in physical and chemical properties of the
atomic numbers
elements
(b) non-metallic elements are lesser in number than metallic
(d) it helps to predict the relative ionicity of the bond between any
elements
two elements

Topic 2 Periodic Properties

Objective Questions I (Only one correct option) 3. The group number, number of valence electrons and valency
2−
1. The correct order of the ionic radii of O , N , F , Mg ,3− − 2+ of an element with atomic number 15, respectively, are
(2019 Main, 12 April I)
+ 3+
Na and Al is (2020 Main, 5 Sep II) (a) 16, 5 and 2 (b) 15, 5 and 3
(a) N3 − < O2 − < F− < Na + < Mg 2+ < Al 3+ (c) 16, 6 and 3 (d) 15, 6 and 2
(b) Al 3+ < Na + < Mg 2+ < O2 − < F− < N3 − 4. The element having greatest difference between its first and
(c) Al 3+ < Mg 2+ < Na + < F− < O2 − < N3 − second ionisation energy, is (2019 Main, 9 April I)
3− − 2− 2+ + 3+ (a) Ca (b) Sc
(d) N <F <O < Mg < Na < Al
(c) Ba (d) K
2. Within each pair of elements F and Cl, S and Se, and Li and
5. The correct option with respect to the Pauling
Na, respectively, the elements that release more energy upon
electronegativity values of the elements is
an electron gain are (2020 Main, 7 Jan II) (2019 Main, 11 Jan II)
(a) F, Se and Na (b) F, S and Li (a) P > S (b) Si < Al
(c) Cl, S and Li (d) Cl, Se and Na (c) Te > Se (d) Ga < Ge
42 Periodic Classification and Periodic Properties

6. The correct order of the atomic radii of C, Cs, Al and S is 18. Which of the following has the maximum number of
(2019 Main, 11 Jan I) unpaired electrons ? (1996, 1M)
(a) C < S < Al < Cs (b) C < S < Cs < Al (a) Mg2+ (b) Ti 3+
(c) S < C < Cs < Al (d) S < C < Al < Cs (c) V 3+ (d) Fe2+
7. In general, the properties that decrease and increase down a 19. Amongst the following elements (whose electronic
group in the periodic table, respectively are configurations are given below), the one having the highest
(2019 Main, 9 Jan I)
ionisation energy is (1990, 1M)
(a) electronegativity and atomic radius
(a) [Ne] 3s2 3 p1 (b) [Ne] 3s2 3 p3
(b) electronegativity and electron gain enthalpy 2 2
(c) electron gain enthalpy and electronegativity (c) [Ne] 3s 3 p (d) [Ar] 3d 10 4s2 4 p3
(d) atomic radius and electronegativity 20. Which one of the following is the smallest in size?
3− 2− − (1989, 1M)
8. The ionic radii (in Å) of N ,O and F respectively are
(2015 Main) (a) N3− (b) O2−
(a) 1.36, 1.40 and 1.71 (b) 1.36, 1.71 and 1.40 (c) F − (d) Na +
(c) 1.71, 1.40 and 1.36 (d) 1.71, 1.36 and 1.40 21. The first ionisation potential of Na, Mg, Al and Si are in the
9. Which one of the following alkaline earth metal sulphates order (1988, 1M)
has its hydration enthalpy greater than its lattice enthalpy? (a) Na < Mg >Al < Si (b) Na > Mg > Al > Si
(a) CaSO4 (b) BeSO4 (2015 Main) (c) Na < Mg <Al >Si (d) Na > Mg > Al <Si
(c) BaSO4 (d) SrSO4
22. The electronegativity of the following elements increases in
10. Which among the following is the most reactive? the order (1987, 1M)
(a) Cl 2 (b) Br2 (2015 Main) (a) C, N, Si, P (b) N, Si, C, P
(c) I2 (d) ICl (c) Si, P, C, N (d) P, Si, N, C
11. Which one has the highest boiling point? 23. Atomic radii of fluorine and neon in Angstrom units are
(a) He (b) Ne (c) Kr (d) Xe respectively given by (1987, 1M)
12. The first ionisation potential of Na is 5.1 eV. The value of (a) 0.72, 1.60 (b) 1.60, 1.60
electron gain enthalpy of Na + will be (2013 Main) (c) 0.72, 0.72 (d) None of these
(a) − 2.55 eV (b) − 5.1 eV 24. The first ionisation potential in electron volts of nitrogen and
(c) − 10.2 eV (d) + 2.55 eV oxygen atoms are respectively given by (1987, 1M)
13. Which of the following represents the correct order of (a) 14.6, 13.6 (b) 13.6, 14.6
increasing first ionisation enthalpy for Ca, Ba, S, Se and Ar? (c) 13.6, 13.6 (d) 14.6, 14.6
(2013 Main)
(a) Ca < S < Ba < Se < Ar (b) S < Se < Ca < Ba < Ar
25. The hydration energy of Mg 2+ is larger than that of
(c) Ba < Ca < Se < S < Ar (d) Ca < Ba < S < Se < Ar (1984, 1M)
(a) Al 3+ (b) Na +
14. Identify the least stable ion amongst the following. (c) Be2+ (d) Mg3+
(a) Li + (b) Be− (2002, 3M)
(c) B− (d) C − 26. The element with the highest first ionisation potential is
(1982, 1M)
15. The set representing the correct order of first ionisation (a) boron (b) carbon
potential is (2001, 1M) (c) nitrogen (d) oxygen
(a) K > Na > Li (b) Be > Mg > Ca 27. The correct order of second ionisation potential of carbon,
(c) B > C > N (d) Ge > Si > C nitrogen, oxygen and fluorine is (1981, 1M)
(a) C > N > O > F (b) O > N > F > C
16. The correct order of radii is (2000, 1M) (c) O > F > N > C (d) F > O > N > C
(a) N < Be < B (b) F − < O2− < N3−
(c) Na < Li < K (d) Fe3+ < Fe 2+ < Fe4+ Objective Questions II
17. The incorrect statement among the following. (1997(C), 1M)
(One or more than one correct option)
(a) The first ionisation potential of Al is less than the first 28. The option(s) with only amphoteric oxides is(are)
ionisation potential of Mg (2017 Adv.)
(b) The second ionisation potential of Mg is greater than the (a) NO, B2O3 , PbO, SnO2 (b) Cr2O3 , CrO, SnO, PbO
second ionisation potential of Na (c) Cr2O3 , BeO, SnO, SnO2 (d) ZnO, Al 2O3 , PbO, PbO2
(c) The first ionisation potential of Na is less than the first 29. Ionic radii of (1999, 3M)
ionisation potential of Mg (a) Ti 4+ < Mn 7 + (b) 35
Cl − < 37
Cl −
(d) The third ionisation potential of Mg is greater than third
(c) K + > Cl − (d) P 3+ > P 5+
ionisation potential of Na
 Periodic Classification and Periodic Properties 43

30. The first ionisation potential of nitrogen and oxygen atoms Atomic Ionisation enthalpy (kJ/mol)
are related as follows. (1989, 1M) number I1 I2 I3
(a) The ionisation potential of oxygen is less than the ionisation n 1681 3374 6050
potential of nitrogen n+1 2081 3952 6122
(b) The ionisation potential of nitrogen is greater than the
n+ 2 496 4562 6910
ionisation potential of oxygen
(c) The two ionisation potential values are comparable n+ 3 738 1451 7733
(d) The difference between the two ionisation potential is too large
31. Sodium sulphate is soluble in water whereas barium sulphate
Fill in the Blanks
is sparingly soluble because (1989, 1M) 38. Compounds that formally contain Pb 4+ are easily reduced to
(a) the hydration energy of sodium sulphate is more than its lattice Pb 2+ . The stability of the lower oxidation state is due to
energy …… . (1997, 1M)
(b) the lattice energy of barium sulphate is more than its hydration 39. Ca 2+ has a smaller ionic radius than K + because it has
energy
............ (1993, 1M
(c) the lattice energy has no role to play in solubility
(d) the hydration energy of sodium sulphate is less than its lattice 40. On Mulliken scale, the average of ionisation potential and
energy electron affinity is known as ................ (1985, 1M)

41. The energy released when an electron is added to a neutral

Assertion and Reason gaseous atom is called …… . (1982, 1M)
Read the following questions and answer as per the direction
given below : True/False
(a) Statement I is true; Statement II is true; Statement II is
42. The basic nature of the hydroxides of group 13 (III B)
the correct explanation of Statement I.
decreases progressively down the group. (1993, 1M)
(b) Statement I is true; Statement II is true; Statement II is
not the correct explanation of Statement I. 43. The decreasing order of electron affinity of F, Cl, Br is
(c) Statement I is true; Statement II is false. F > Cl > Br. (1993, 1M)
(d) Statement I is false; Statement II is true. 44. In group IA of alkali metals, the ionisation potential
32. Statement I Nitrogen and oxygen are the main components decreases down the group. Therefore, lithium is a poor
in the atmosphere but these do not react to form oxides of reducing agent. (1987, 1M)
nitrogen. 45. The softness of group IA metals increases down the group
Statement II The reaction between nitrogen and oxygen with increasing atomic number. (1986, 1M)
requires high temperature. (2015 Main)

33. Statement I Pb 4+ compounds are stronger oxidising agents Subjective Questions

4+
than Sn compounds. 46. Arrange the following ions in order of their increasing radii
Statement II The higher oxidation states for the group 14 Li + , Mg 2+ , K + , Al 3+. (1997, 1M)
elements are more stable for the heavier members of the
group due to ‘inert pair effect’. (2008, 3M) 47. Compare qualitatively the first and second ionisation
potentials of copper and zinc. Explain the observation.
34. Statement I Band gap in germanium is small. (1996, 2M
Statement II The energy spread of each germanium atomic
48. Arrange the following as stated :
energy level is infinitesimally small. (2007, 3M)
“Increasing order of ionic size’’ N3– ,Na + , F− , O2 − , Mg 2+
35. Statement I The first ionisation energy of Be is greater than
(1991, 1M)
that of B.
Statement II 2p-orbital is lower in energy than 2s. 49. Explain the following :
(2000, (S), 1M) “The first ionisation energy of carbon atom is greater than
36. Statement I F-atom has a less negative electron affinity than that of boron atom whereas, the reverse is true for the second
Cl-atom. ionisation energy.’’ (1989, 2M)
Statement II Additional electrons are repelled more 50. Arrange the following in the order of their increasing size:
effectively by 3 p-electrons in Cl-atom than by 2 p-electrons in Cl − , S2 − , Ca 2+ , Ar (1986, 1M)
F-atom. (1998, 2M)
51. Arrange the following in order of their
Numerical Answer Type Questions (i) decreasing ionic size Mg 2+ , O2 − , Na + ,F−
37. The 1st, 2nd and 3rd ionisation enthalpies, I1 , I 2 , and I 3 , of (ii) increasing first ionisation energy Mg, Al, Si, Na
four atoms with atomic numbers n , n + 1, n + 2, and n + 3, (iii) increasing bond length F2 , N2 , Cl 2 , O2 (1985, 3M)
where n < 10, are tabulated below. What is the value of n ?
(2020 Adv.)
44 Periodic Classification and Periodic Properties

Answers
Topic 1 21. (a) 22. (c) 23. (a) 24. (a)
1. (b) 2. (c) 3. (d) 4. (b,c,d) 25. (b) 26. (c) 27. (c) 28. (a,b)
29. (d) 30. (a,b,c) 31. (a,b) 32. (a)
Topic 2
33. (c) 34. (c) 35. (c) 36. (c)
1. (c) 2. (c) 3. (b) 4. (d)
37. (9) 38. (inert pair effect)
5. (d) 6. (a) 7. (a) 8. (c)
39. (higher effective nuclear charge)
9. (b) 10. (d) 11. (d) 12. (b)
40. (electronegativity) 41. (electron affinity)
13. (c) 14. (b) 15. (b) 16. (b)
42. F 43. F 44. F 45. T
17. (b) 18. (d) 19. (b) 20. (d)

Hints & Solutions

Topic 1 History and Periodic Classification Topic 2 Periodic Properties
1. Atomic number (119) = 1 1 9 1
un un en 1. Size of species ∝
Nuclear charge
So, symbol of the element = uue
Name of the element = ununennium Iso-electronic species are those atoms or ions which has the
It is expected to be s-block element an alkali metal and the first same number of electrons.
element in eighth period. It is the lightest element that has not Size of species decreases with increasing protons.
yet been synthesised. More is effective nuclear charge (Zeff) lesser will be ionic size.
2. The element with Z = 120 will be an alkaline earth metal. Correct order of ionic radii
Recently, oganesson (Og) with atomic number 118 is named by Al 3+ < Mg2+ < Na + < F− < O2− < N3−
IUPAC is a noble gas and placed just two place before 120. So,
the general electronic configuration is represented as [noble gas] 2. The first electron gain enthalpy is exothermic (or negative).
ns2 and element with Z = 120 exist as an alkaline earth metal.
Generally, electron gain enthalpy becomes less exothermic (or
3. (a) Correct statement According to Moseley’s law, the less negative) when comparing elements of a group from top to
properties of elements are the periodic function of their bottom.
atomic numbers. Therefore, electron gain enthalpy of S > Se and Li > Na.
(b) Correct statement The whole s-block, d-block, f -block But there are some exceptions to this.
and heavier p-block elements are metal. One of them is the case of a group 17 elements where electron
(c) Correct statement Trend is not regular, Be has higher first gain is most negative for Cl instead of F, due to extra small size
ionisation energy than B, nitrogen has higher first ionisation of fluorine.
energy than oxygen. ∴ Upon an electron gain, energy releases in the order :
(d) Inccorrect statement d-subshells are not filled Cl > F, S > Se and Li > Na
monotonically, regularity break at chromium and copper. 3. The group number, number of valence electrons and valency of
4. (a) Incorrect Electrons are not filled in sub-energy levels an element with atomic number 15 are 15, 5 and 3 respectively.
s, p, d and f in the same sequence. Modern periodic table is based on the atomic number. Number
(b) Correct Number of valence shell electrons usually of valence electrons present in an atom decides the group
determine the stable valency state of an element. number. Electronic configuration of element having atomic
number 15 = 1s2 2s2 2 p6 3s2 3 p3
(c) Correct Physical and chemical properties of elements are
periodic function of atomic number which is the basis of Valence electrons
modern, long form of periodic table. As five electrons are present in valence shell, its group number
(d) Correct Relative ionicity of the bond between any two is 15. Valency of element having atomic number 15 is +3
(8 − 5 = 3).
elements is function of electronegativity difference of the
bonded atoms which in turn has periodic trend in long form 4. The electronic configuration of given elements are as follows :
of periodic table. K(19) = 1s2 2s2 2 p6 3s2 3 p6 4 s1
 Periodic Classification and Periodic Properties 45

Mg(12) = 1s2 2s2 2 p6 3s2 It is considered that, in case of isoelectronic species as the
Sr(38) = 1s2 2s2 2 p6 3s2 3 p6 4 s2 3d 10 4 p6 5s2 negative charge increases, ionic radii increases and therefore the
value of ionic radii are
Sc(21) = 1s2 2s2 2 p6 3s2 3 p6 4 s2 3d 1
N3− = 1.71 (highest among the three)
First ionisation enthalpy (IE) of K is lowest among the given O2− = 1.40 F− = 136. (lowest among the three)
options. Here, the energy required to remove an electron from
Time Saving Technique There is no need to mug up the radius
4 s1 is least as only one electron is present in the outermost shell.
values for different ions. This particular question can be solved
IE (I) is comparatively high for Mg and Sr and two electrons
through following time saving.
(fully-filled) are placed in s-orbital. Second ionisation enthalpy
of K is highest among the given options. Trick The charges on the ions indicate the size as
N3− > O2− > F− . Thus, you have to look for the option in which
Now, removal of an electron occur from p6 (fully-filled). So,
the above trend is followed. Option(c) is the only one in which
high energy is required to remove the electron. From the above this trend is followed. Hence, it is the correct answer.
discussion, it can be concluded that (IE 2 − IE 1 ) value is
maximum for K (potassium). 9. As we move down the group, size of metal increases. Be has
lower size while SO2− 4 has bigger size, that’s why BeSO 4 breaks
5. The electronegativity values of given elements on the Pauling
scale can be shown as follows: easily and lattice energy becomes smaller but due to lower size
of Be, water molecules are gathered around and hence hydration
Period No. Group 13 Group 14 Group 15 Group 16 energy increases.
3 Al (1.5) Si (1.8) P (2.1) S (2.5) On the other hand, rest of the metals, i.e Ca, Ba, Sr have bigger
4 Ga (1.6) Ge (1.8) Se (2.4) size and that’s why lattice energy is greater than hydration energy.
5 Te (2.01) Time Saving Technique In the question of finding hydration
energy only check the size of atom. Smaller sized atom has more
On moving from left to right across a period, i.e. from Ga to Se,
hydration energy. Thus, in this question Be is placed upper most
the effective nuclear charge increases and size decreases. in the group has lesser size and not comparable with the size of
As a result, the value of electronegativity increases due to sulphates. Hence, BeSO4 is the right response.
increase in the attraction between the outer electrons and the
10. Cl 2, Br2 and I2 are homonuclear diatomic molecule in which
nucleus. Whereas on moving down the group, (i.e. from Se to
Te), the atomic size increases. electronegativity of the combining atoms is same, so they are
more stable and less reactive, whereas, I and Cl have different
As a result, the force of attraction between the outer electron and electronegativities and bond between them are polarised and
the nucleus decreases. Hence, the electronegativity decreases. reactive. Therefore, interhalogen compounds are more reactive.
Time Saving Technique In this type of question of halogen,
6. Element Period Group No.
only go through the polarity of the molecules. As we know,
No.
diatomic molecule does not have polarity but molecules with
C 2nd 14
dissimilar sizes have polarity resulting in more reactivity.
Al 3rd 13 Along the period atomic radius
S 3rd 16 decreases, so, radii : Al > S. 11. As we move down the group of noble gases, molecular mass
increases by which dipole produced for a moment and hence
Cs 6th 1
London forces increases from He to Xe.
With the addition of a new shell, period number as well as atomic Therefore, more amount of energy is required to break these
radius increases. It is because of the successive addition of one forces, thus boiling point also increases from He and Xe.
extra shell of electrons. So, the order of the atomic radii of the
12. Na → Na + + e− First IE
given elements will be: C < S < Al < Cs
Na + e− → Na
+
7. The summary of variation of periodic properties is given in table
below: Electron gain enthalpy of Na + is reverse of (IE)
Because reaction is reverse so ∆H (eq) = − 5.1 eV
S.No. Periodic property Variation 13. Ionisation energy increases along a period from left to right and
Along a period Along a group decreases down a group. The position of given elements in the
1. Atomic radius Decreases Increases periodic table is as
2. Electron gain Increases Decreases Group No. 2 16 18
enthalpy Ca S Ar
3. Electronegativity Increases Decreases Ba Se
Thus, electronegativity decreases and atomic radius increases Thus, the order of increasing ∆H IE1 is Ba < Ca < Se < S < Ar
down a group in the periodic table.
14. Be− is the least stable ion, Be (1s2 2s2 ) has stable electronic
8. Number of electrons in N3−, = 7 + 3 = 10 configuration, addition of electron decreases stability.
Number of electrons in O2− = 8 + 2 = 10
15. In a group, ionisation energy decreases down the group
Number of electrons in F− = 9 + 1 = 10 Be > Mg > Ca
Since, all the three species have each 10 electrons, hence they
16. Among isoelectronic species, greater the negative charge,
are isoelectronic species.
greater the ionic size, hence F− < O2− < N3− .
46 Periodic Classification and Periodic Properties

17. (a) Correct statement In a period, element of 2nd group has In general, ionisation energy increases from left to right in a
higher first ionisation potential than element of group 13. period. However, exception occur between adjacent atoms in a
(b) Incorrect statement Mg+ require less energy for further period, greater amount energy is required for removal of
electron from completely half-filled or completely filled orbital
ionisation than Na + because of noble gas configuration of Na + .
than the same for adjacent atom with either less than completely
(c) Correct statement Ionisation energy increases from left half-filled or less than completely filled orbital. Therefore,
to right in a period. ionisation potential of O+ is greater than that of F+ . Also ionisation
18. Mg2+ = 1s2 2 s2 2 p6 = no unpaired electron potential of N+ is greater than C+ but less than both O+ and F+
(periodic trend). Hence, overall order is 2nd IP : O > F > N > C.
Ti 3+ = 1s2 2 s2 2 p6 3s2 3 p6 3d 1 = one unpaired electron
V3+ = 1s2 2 s2 2 p6 3s2 3 p6 3d 2 = two unpaired electrons 28. (c) is incorrect because NO is neutral oxide.
2+ 2 2 6 2 6 6 (d) is incorrect because CrO is basic oxide.
Fe = 1s 2 s 2 p 3s 3 p 3d = four unpaired electrons
29. (a) Ti 4+ > Mn 7+ is the correct order of size due to lower positive
19. [Ne] 3s2 3 p3 has highest ionisation energy, periodic trend.
charge on Ti 4+ .
20. Among isoelectronic species, the relation in size is (b) Cl − = 37 Cl − : Isotopes with same charge have same size
37
cation < neutral < anion
because isotopes differ in compositions of nuclei which do
Hence, Na + has smallest size. not affect the atomic/ionic radius.
21. Ionisation energy increases from left to right in a period. (c) K+ < Cl − is the correct order. Among isoelectronic species,
However, exception occur between group 2 and group 13 anion has greater size than cation.
elements on account of stability of electronic configuration of
valence shell. (d) P3+ > P5+ is the correct order. For the same elements, lower
IE the positive charge, larger the ions.
Group 2 = > Group 13 = 30. (a) and (b) are infact the same statements and both are correct. N
ns2 ns2 np1 has slightly greater ionisation energy than oxygen which is
⇒ The desired order is Na < Mg > Al < Si against periodic trend. This exception is due to completely
half-filled (2 p3 ) orbital in nitrogen that makes ionisation
22. Electronegativity increases from left to right in a period and slightly difficult than oxygen.
decreases from top to bottom in a group. Variation is more rapid (c) Also correct : Although N has greater first ionisation
in group than in a period, hence the desired order is
potential than oxygen, two values of ionisation potentials are
Electronegativity : Si < P < C < N
comparable since they are adjacent in a period, i.e. electrons
23. Atomic radius of noble gases are greater than halogens of same are removed from same orbit during ionisation.
period, hence (a) is the correct answer.
(d) Incorrect – opposite to (c). of the bonded atoms which in
24. First ionisation energy of oxygen is less than that of nitrogen on turn has periodic trend in long form of periodic table.
the ground of stability of valence shell configuration, hence (a)
31. (a) Correct For greater solubility, hydration energy must be
is the correct answer.
greater than lattice energy.
25. Hydration energy depends on charge of ion and ionic radius. (b) Correct Greater lattice energy discourage dissolution of a salt.
Higher the charge, greater the hydration energy. On the other (c) Incorrect When a salt dissolve, energy is required to break
hand, smaller the size, greater the hydration energy. Charge is the lattice, which comes from hydration process.
considered first for comparison. Hence, Mg2+ has higher
(d) Incorrect Explained in (A).
hydration energy than Na + .
32. Statement I and II are true and Statement II is the correct
26. Nitrogen has highest ionisation potential due to exceptional explanation of statement I.
stability of its valence shell configuration mentioned in
question 21. 33. Statement I is true. Stronger oxidising agent is one which itself
27. For second ionisation potential, electron will have to be can easily be reduced. Pb4+ is unstable, due to inert pair effect,
removed from valence shell of the following ions: can easily be reduced to stable Pb2+ , hence a stronger oxidising
agent than Sn 4+ .
C+ (5e–) = 1s2 2s2 Statement II is false. Due to inert pair effect, the higher
2p oxidation states of group 14 elements becomes less stable for
+ –
N (6e ) = heavier member.
1s2 2s2
2p 34. Both statements I and II are true and Statement II is the correct
explanation of statement I.
O+ (7e–) = 1s2 2s2
2p 35. Statement I is true Be has higher first ionisation energy than B
which is against periodic trend.
F+ (8e–) = 1s2 2s2 Statement II is false 2s-orbital is lower in energy than 2p,
2p Aufbau’s principle.
 Periodic Classification and Periodic Properties 47

36. Statement I is true; Statement II is false. 47. Zn = 3d 10 4 s2 , Cu = 3d 10 4 s1

F atom has slightly lower affinity for the electron than chlorine. The first ionisation energy is greater for Zn but reverse is true for
It is due to the reason that additional electrons are repelled more 2nd ionisation energy.
effectively by 2p-electrons in F than by 3p-electrons in Cl-atom.
48. Ionic size Mg2+ < Na + < F− < O2− < N3−
37. By observing the values of different ionisation energies, I 1 , I 2
and I 3 for atomic number (n + 2 ), it is observed that there is very 49. The first ionisation energy of carbon is greater than the same of
large difference between the second ionisation energy and first boron as predicted from periodic trend. However, for 2nd
ionisation energy (I 2 >> I 1 ).
B+ = 1s2 ; more stable than C+ =1s2 2s2
This indicates that number of valence shell electrons is 1 and
2s2 2p1
atomic number (n + 2 ) should be an alkali metal.
Also for atomic number (n + 3 ), I 3 >> I 2. ionisation trend is reversed due to stability of completely filled
This indicates that it will be an alkaline earth metal which 2s-orbital of B+ :
suggests that atomic number (n + 1) should be a noble gas and
atomic number (n) should belong to halogen family. Since,
50. Size Ca 2+ < Ar < Cl − < S2− .
n < 10; hence, n = 9 (F atom) 51. (i) Mg2+ , O2− , Na + and F − are all isoelectronic, has
38. Inert pair effect-favours lower oxidation state. 10 electrons each. Among isoelectronic species, the order of
size is cation < neutral < anion.
39. Higher effective nuclear charge due to greater p/e ratio. Also, between cations, higher the charge, smaller the size
IP + EA and between anions, greater the negative charge, larger the
40. Electronegativity = (Mulliken formula)
2 size. Therefore, the decreasing order of ionic radii :
O2− > F− > Na + > Mg2+
41. Electron affinity–definition.
42. Basic nature of hydroxides increases down a group. (ii) First ionisation energy increases from left to right in a period.
However, exception occur between group 2 and 13 and group 15
43. Cl has maximum electron affinity, hence the correct order is and 16 where trend is reversed on the grounds of stability of
Cl > F > Br completely filled and completely half-filled orbitals. Therefore,
44. Ionisation potential decreases down the group but this is not the Ionisation energy (1st) : Na < Al < Mg < Si
only criteria of reducing power. (iii) If the atoms are from same period, bond length is inversely
45. In a group, size increases from top to bottom. proportional to bond order. In a group, bond length is related
directly to atomic radius.
46. Li + < Al 3+ < Mg2+ < K+ . Size decreases from left to right in a Therefore,
period and it increases from top to bottom in a group. Variation bond length N2 < O2 < F2 < Cl 2
is more pronounced in group than in period.
4
Chemical Bonding

Topic 1 Preliminary Concepts of Electrovalent

and Covalent Bonding
Objective Questions I (Only one correct option) 7. The number and type of bonds between two carbon atoms in
1. The isoelectronic set of ions is (2019 Main, 10 April I) CaC2 are (1996, 1M)
− + +
(a) F , Li , Na and Mg 2+ (a) one sigma (σ ) and one pi ( π ) bonds
(b) one sigma (σ ) and two pi ( π ) bonds
(b) N3 − , Li + , Mg 2+ and O2 − (c) one sigma (σ ) and one half pi ( π ) bonds
(c) Li + , Na + , O2 − and F− (d) one sigma (σ ) bond
(d) N3 − , O2 − , F− and Na +
8. The molecule which has zero dipole moment is (1989, 1M)
(a) CH2 Cl 2 (b) BF3 (c) NF3 (d) ClO2
2. Which of the following compounds contain(s) no covalent
bond(s)? 9. Element X is strongly electropositive and element Y is
KCl, PH3 , O2 , B2 H6 , H2 SO4 (2018 Main) strongly electronegative. Both are univalent. The compound
formed would be (1980, 1M)
(a) KCl, B2 H6 , PH3 (b) KCl, H2 SO4
(a) X +Y − (b) X −Y + (c) X −− Y (d) X → Y
(c) KCl (d) KCl, B2 H6
3. The intermolecular interaction that is dependent on the 10. Which of the following compound is covalent? (1980, 1M)

inverse cube of distance between the molecules is (2015 Main) (a) H2 (b) CaO
(a) ion-ion interaction (b) ion-dipole interaction (c) KCl (d) Na 2 S
(c) London force (d) hydrogen bond 11. The total number of electrons that take part in forming the
4. The nodal plane in the π-bond of ethene is located in bonds in N2 is (1980, 1M)
(a) 2 (b) 4 (c) 6 (d) 10
(a) the molecular plane (2002, 3M)
(b) a plane parallel to the molecular plane 12. The compound which contains both ionic and covalent bonds
(c) a plane perpendicular to the molecular plane which is (1979, 1M)
bisects the carbon-carbon σ-bond at right angle (a) CH4 (b) H2 (c) KCN (d) KCl
(d) a plane perpendicular to the molecular plane which
contains the carbon-carbon σ-bond Objective Questions II
5. Amongst H2 O, H2 S, H2 Se and H2 Te, the one with the highest (One or more than one correct option)
boiling point is (2000, 1M)
13. Each of the following options contains a set of four
(a) H2 O because of hydrogen bonding molecules. Identify the option(s) where all four molecules
(b) H2 Te because of higher molecular weight posses permanent dipole moment at room temperature.
(c) H2 S because of hydrogen bonding (a) SO2 , C6 H5 Cl, H2 Se, BrF5 (2019 Adv.)
(d) H2 Se because of lower molecular weight (b) BeCl 2 , CO2 , BCl 3 , CHCl 3
6. Arrange the following compounds in order of increasing (c) NO2 , NH3 , POCl 3 , CH3 Cl
dipole moment, toluene (I), m-dichlorobenzene (II), (d) BF3 , O3 , SF6 , XeF6
o-dichlorobenzene (III), p-dichlorobenzene (IV) (1996, 1M) 14. Dipole moment is shown by (1986, 1M)
(a) I < IV < II < III (b) IV < I < II < III (a) 1, 4-dichlorobenzene (b) cis-1, 2-dichloroethene
(c) IV < I < III < II (d) IV < II < I < III (c) trans-1, 2-dichloroethene (d) trans-1, 2-dichloro-2- pentene
 Chemical Bonding 49

Numerical Answer Type Questions 17. Statement I LiCl is predominantly a covalent compound.
15. Consider the following compounds in the liquid form : Statement II Electronegativity difference between Li and Cl
O 2 ,HF,H 2O,NH 3 ,H 2O 2 ,CCl 4 ,CHCl 3 , C6H 6 ,C6H 5Cl is too small. (1998, 2M)

When a charged comb is brought near their flowing stream, Fill in the Blank
how many of them show deflection as per the following
figure? (2020 Adv.) 18. There are …… π -bonds in a nitrogen molecule. (1982, 1M)

True/False
19. All molecules with polar bonds have dipole moment.
(1985, 1/2 M)
20. Linear overlapping of two atomic p-orbitals leads to a sigma
bond. (1983, 1M)

Subjective Questions
21. Arrange the following ions in order of their increasing radii:
Li + , Mg 2+ , K + , Al 3+ . (1997, 1M)
+ +
22. Between Na and Ag , which is stronger Lewis acid and
why? (1997, 3M)
−
23. In the reaction, I + I2 → I3− , which is the Lewis acid?
(1997, 1M)
16. Among the species given below, the total number of 24. Explain the difference in the nature of bonding in LiF and LiI.
diamagnetic species is____ (1996, 2M)
H atom, NO2 monomer, O−2 (superoxide), dimeric sulphur in 25. The dipole moment of KCl is 3.336 × 10−29 C-m which
vapour phase, Mn 3 O4 ,( NH4 )2 [ FeCl 4 ], ( NH4 )2 [ NiCl 4 ], indicates that it is a highly polar molecule. The interatomic
K 2 MnO4 , K 2 CrO4 (2018 Adv.) distance between K + and Cl − in this molecule is
2.6 × 10−10 m. Calculate the dipole moment of KCl molecule
Assertion and Reason if there were opposite charges of one fundamental unit
Read the following questions and answer as per the direction located at each nucleus. Calculate the percentage ionic
given below: character of KCl. (1993, 2M)

(a) Statement I is true; Statement II is true; Statement II is the 26. Give reasons in two or three sentences only for the following :
correct explanation of Statement I “Hydrogen peroxide acts as an oxidising as well as a reducing
(b) Statement I is true; Statement II is true; Statement II is not agent.’’ (1992, 1M)
the correct explanation of Statement I 27. State four major physical properties that can be used to
(c) Statement I is correct; Statement II is incorrect distinguish between covalent and ionic compounds. Mention
(d) Statement I is incorrect; Statement II is correct the distinguishing features in each case. (1978, 2M)

Topic 2 VBT, Hybridisation and VSEPR Theory

Objective Questions I (Only one correct option) 2. The correct statement about ICl 5 and ICl −4 is
1. The correct statements among I to III are : (2019 Main, 8 April II)

I. Valence bond theory cannot explain the color exhibited (a) ICl 5 is square pyramidal and ICl −4 is tetrahedral
by transition metal complexes. (b) ICl 5 is square pyramidal and ICl −4 is square planar
II. Valence bond theory can predict quantitatively the (c) Both are isostructural
magnetic properties of transition metal complexes. (d) ICl 5 is trigonal bipyramidal and ICl −4 is tetrahedral
III. Valence bond theory cannot distinguish ligands as weak
and strong field ones. (2019 Main, 9 April II) 3. The ion that has sp 3 d 2 -hybridisation for the central atom, is
(a) II and III only (b) I, II and III (2019 Main, 8 April II)

(c) I and II only (d) I and III only (a) [ICl 2 ]− (b) [BrF2 ]− (c) [ICl 4 ]− (d) [IF6 ]−
50 Chemical Bonding

4. The size of the iso-electronic species Cl − , Ar and Ca 2+ is 17. Which of the following molecular species has unpaired
affected by (2019 Main, 8 April I) electron (s)? (2002, 3M)
(a) azimuthal quantum number of valence shell (a) N2 (b) F2 (c) O–2 (d) O2–
2
(b) electron-electron interaction in the outer orbitals
18. Specify the coordination geometry around and hybridisation
(c) principal quantum number of valence shell of N and B atoms in a 1 : 1 complex of BF3 and NH3 .
(d) nuclear charge (a) N : tetrahedral, sp 3 ; B: tetrahedral, sp 3 (2002, 3M)
5. In which of the following processes, the bond order has (b) N : pyramidal, sp 3 ; B: pyramidal, sp 3
increased and paramagnetic character has changed to (c) N: pyramidal, sp 3 ; B: planar, sp 2
diamagnetic? (2019 Main, 9 Jan II) (d) N: pyramidal, sp 3 ; B: tetrahedral, sp 3
(a) O2 → O2+ (b) N2 → N+2 19. The correct order of hybridisation of the central atom in the
(c) O2 → O22 − (d) NO → NO+ following species NH3 , [PtCl 4 ]2 − , PCl 5 and BCl 3 is
6. Total number of lone pair of electron in I−3 ion is (2018 Main)
(2001, 1M)
(a) dsp 2 , dsp 3 , sp 2 and sp 3 (b) sp 3 , dsp 2 , sp 3 d and sp 2
(a) 3 (b) 6
(c) dsp 2 , sp 2 , sp 3 and dsp 3 (d) dsp 2 , sp 3 , sp 2 and dsp 3
(c) 9 (d) 12
20. The common features among the species CN – , CO
7. The group having isoelectronic species is (2017 Main)
and NO+ are (2001, 1M)
(a) O2 − , F− , Na + , Mg 2 + (b) O− , F− , Na, Mg + (a) bond order three and isoelectronic
(c) O2 − , F− , Na, Mg 2 + (d) O− , F− , Na + , Mg 2 + (b) bond order three and weak field ligands
(c) bond order two and acceptors
8. The correct statement for the molecule, CsI3 is (2014 Main)
(d) isoelectronic and weak field ligands
(a) it is a covalent molecule
(b) it contains Cs + and I−3 ions 21. The hybridisation of atomic orbitals of nitrogen in NO+2 , NO−3
(c) it contains Cs 3+ and I− ions and NH+4 are (2000, 1M)
(d) it contains Cs + , I− and lattice I2 molecule (a) sp, sp 3 and sp 2 respectively
9. The species having pyramidal shape is (2010) (b) sp, sp 2 and sp 3 respectively
(a) SO3 (b) BrF3 (c) SiO2−
3 (d) OSF2 (c) sp 2 , sp and sp 3 respectively
(d) sp 2 , sp 3 and sp respectively
10. Assuming that Hund’s rule is violated, the bond order and
magnetic nature of the diatomic molecule B2 is (2010)
22. In the compound CH2 == CH  CH2  CH2  C ≡≡ CH, the
C2  C3 bonds is of (1999, 2M)
(a) 1 and diamagnetic (b) 0 and diamagnetic
(a) sp - sp 2 (b) sp 3 - sp 3
(c) 1 and paramagnetic (d) 0 and paramagnetic
(c) sp - sp 3 (d) sp 2 - sp 3
11. The species having bond order different from that in CO is
23. The geometry of H2 S and its dipole moment are (1999, 2M)
(a) NO− (b) NO+ (2007, 3M)
(a) angular and non-zero (b) angular and zero
(c) CN− (d) N2 (c) linear and non-zero (d) linear and zero
12. Among the following, the paramagnetic compound is 24. The geometry and the type of hybrid orbital present about the
(2007, 3M) central atom in BF3 is (1998, 2M)
(a) Na 2 O2 (b) O3 (c) N2 O (d) KO2 (a) linear, sp (b) trigonal planar, sp 2
13. Which of the following contains maximum number of lone (c) tetrahedral, sp 3 (d) pyramidal, sp 3
pairs on the central atom? (2005, 1M) 25. Which one of the following compounds has
(a) ClO −3 (b) XeF 4 (c) SF 4 (d) I −3 sp 2 - hybridisation? (1997, 1M)

14. Number of lone pair(s) in XeOF4 is/are (a) CO2 (b) SO2 (c) N2 O (d) CO
(2004, 1M)
(a) 0 (b) 1 (c) 2 (d) 3 26. Among KO2 , AlO−2 , BaO2 and NO+2 , unpaired electron is
present in (1997 C, 1M)
15. Which of the following are isoelectronic and isostructural ?
(a) NO+2 and BaO2 (b) KO2 and AlO−2
NO–3 , CO2– –
3 , ClO3 , SO3 (2003, 1M)
(c) Only KO2 (d) Only BaO2
(a) NO3 , CO2−
–
3 (b) SO3 , NO–3
27. The cyanide ion CN− and N2 are isoelectronic, but in contrast
(c) ClO–3 , CO2– (d) CO2–
3 , SO3
3
to CN− , N2 is chemically inert because of (1997 C, 1M)
16. Among the following, the molecule with the highest dipole (a) low bond energy
moment is (2003, 1M) (b) absence of bond polarity
(a) CH 3 Cl (b) CH 2 Cl 2 (c) unsymmetrical electron distribution
(c) CHCl 3 (d) CCl 4 (d) presence of more number of electron in bonding orbitals
 Chemical Bonding 51

28. Among the following species, identify the isostructural 40. On hybridisation of one s and one p-orbital we get
pairs. (a) two mutually perpendicular orbitals (1984, 1M)
NF3 , NO3− , +
BF3 , H3 O , N3 H (b) two orbitals at 180°
(1996, 1M) (c) four orbitals directed tetrahedrally
(d) three orbitals in a plane
(a) [NF3 ,NO−3 ] and [BF3 ,H3 O+ ]
41. Carbon tetrachloride has no net dipole moment because of
(b) [NF3 , N3 H] and [NO−3 ,BF3 ]
(a) its planar structure (1983, 1M)
(c) [ NF3 , H3 O+ ] and [NO–3 , BF3 ] (b) its regular tetrahedral structure
(d) [NF3 , H3 O+ ] and [N3 H, BF3 ] (c) similar sizes of carbon and chlorine atoms
29. Which one of the following molecules is planar? (1996, 1M) (d) similar electron affinities of carbon and chlorine
(a) NF3 (b) NCl 3 (c) PH3 (d) BF3 42. The ion that is isoelectronic with CO is (1982, 1M)
(a) CN− (b) O+2 (c) O−2 (d) N+2
30. The maximum possible number of hydrogen bonds a water
molecule can form is (1992, 1M) 43. Among the following, the linear molecule is (1982, 1M)
(a) 2 (b) 4 (c) 3 (d) 1 (a) CO2 (b) NO2 (c) SO2 (d) ClO2
31. The type of hybrid orbitals used by the chlorine atom in 44. If a molecule MX 3 has zero dipole moment, the sigma
ClO−2 is (1992, 1M) bonding orbitals used by M (atomic number < 21) are
(a) sp 3
(b) sp 2 (a) pure p (b) sp-hybridised (1981, 1M)

(c) sp (d) None of these (c) sp 2 -hybridised (d) sp 3 -hybridised

32. The molecule which has pyramidal shape is (1989, 1M) Objective Questions II
(a) PCl 3 (b) SO3 (c) CO2– (d) NO–3
3 (One or more than one correct option)
33. Which of the following is paramagnetic? (1989, 1M) 45. The molecules that will have dipole moment are (1992, 1M)
(a) O–2 (b) CN– (c) CO (d) NO+ (a) 2, 2-dimethyl propane (b) trans-2-pentene
34. The Cl—C—Cl angle in 1, 1, 2, 2-tetrachloroethene and (c) cis-3-hexene (d) 2,2,3,3-tetramethyl butane
tetrachloromethane respectively will be about (1988, 1M)
46. Which of the following have identical bond order?
(a) 120° and 109.5° (b) 90° and 109.5° (a) CN– (b) O–2 (1992, 1M)
(c) 109° and 90° (d) 109.5° and 120° (c) NO+ (d) CN+
35. The molecule that has linear structure is 47. The linear structure assumed by (1991, 1M)
(1988, 1M)
(a) CO2 (b) NO2 (c) SO2 (d) SiO2 (a) SnCl 2 (b) CS2 (c) NO+2 (d) NCO–

36. The species in which the central atom uses sp 2 -hybrid 48. CO2 is isostructural with (1986, 1M)
orbitals in its bonding is (1988, 1M) (a) HgCl 2 (b) C2 H2 (c) SnCl 2 (d) NO2
(a) PH3 (b) NH3 (c) CH+3 (d) SbH3
37. Of the following compounds, which will have a zero dipole Match the Columns
moment ? (1987, 1M) 49. Match the orbital overlap figures shown in Column I with the
(a) 1, 1-dichloroethylene description given in Column II and select the correct answer
(b) cis-1, 2-dichloroethylene using the codes given below the Columns. (2014 Adv.)

(c) trans-1, 2-dichloroethylene Column I Column II

(d) None of the above A. 1. p-d π antibonding
38. The hybridisation of sulphur in sulphur dioxide is (1986, 1M)
(a) sp (b) sp 3
B. 2. d-d σ bonding
(c) sp 2 (d) dsp 2
39. The bond between two identical non-metal atoms has a pair
of electrons (1986, 1M) C. 3. p-dπ bonding
(a) unequally shared between the two
(b) transferred fully from one atom to another
D. 4. d-d σ antibonding
(c) with identical spins
(d) equally shared between them
52 Chemical Bonding

Codes 64. In benzene, carbon uses all the three p-orbitals for
A B C D A B C D hybridisation. (1987, 1M)
(a) 4 3 2 1 (b) 1 2 3 4
(c) 2 3 1 4 (d) 4 1 2 3 65. SnCl 2 is a non-linear molecule. 1
(1985, M)
2
50. Match each of the diatomic molecules in Column I with its
property/properties in Column II. (2009) Integer Answer Type Questions
Column I ColumnII 66. The sum of the number of lone pairs of electrons on each
A. B2 p. Paramagnetic central atom in the following species is
B. N2 q. Undergoes oxidation [TeBr6 ]2 − , [BrF2 ]+ , SNF3 and [XeF3 ]−
C. O−2 r. Undergoes reduction (Atomic numbers : N = 7, F = 9, S = 16, Br = 35,
Te = 52, Xe = 54) (2017 Adv.)
D. O2 s. Bond order ≥ 2
67. Among the triatomic molecules/ions BeCl 2 , N−3 , N2 O, NO+2 ,
t. Mixing of ‘s’ and ‘p’ orbitals
O3 , SCl 2 , ICl −2 , I−3 and XeF2 , the total number of linear
Codes
molecules(s)/ion(s) where the hybridisation of the central
A B C D
atom does not have contribution from the d-orbital(s) is
(a) q, r, s p, r, t, s q, r, t p, q, t
[atomic number of S = 16 , Cl = 17 , I = 53 and Xe = 54]
(b) p, q, r, t q, r, s, t p, q, r, t p, r, s, t (2015 adv.)
(c) q, r, s, t p, q, r r, s, t p, q, r, t
(d) p, q, s, t p, q, s p, t q, r, t 68. A list of species having the formula XZ4 is given below
(2014 Adv.)

Fill in the Blanks XeF4 , SF4 , SiF4 , BF4− , BrF4− , [Cu(NH3 )4 ] 2+ , [FeCl 4 ] 2− ,

51. Among N2 O, SO2 , I+3 and I–3 , the linear species are …… and [CoCl 4 ] 2− and [PtCl 4 ] 2−
…… (1997 C, 1M)
Defining shape on the basis of the location of X and Z atoms,
the total number of species having a square planar shape is
52. When N2 goes to N+2 , the N  N bond distance … , and when
69. The total number of lone-pair of electrons in melamine is
O2 goes to O+2 the O  O bond distance …… (1996, 1M) (2013 Adv.)

53. The two types of bonds present in B2 H6 are covalent and …… 70. Based on VSEPR theory, the number of 90° F—Br—F angles
(1994, 1M) in BrF5 is (2010)

54. The kind of delocalisation involving sigma bond orbitals is

called................. (1994, 1M)
Subjective Questions
55. The valence atomic orbitals on C in silver acetylide is 71. Predict whether the following molecules are isostructural or
.............hybridised. (1990, 1M) not. Justify your answer.
(i) NMe3 (ii) N(SiMe3 )3 (2005, 2M)
56. The shape of CH3 + is …… . (1990, 1M)
72. On the basis of ground state electronic configuration, arrange
57. …… hybrid orbitals of nitrogen atom are involved in the the following molecules in increasing O—O bond length
formation of ammonium ion. (1982, 1M) order. KO2 , O2 , O2 [AsF6 ] (2004, 2M)
58. Pair of molecules which forms strongest intermolecular 73. Draw the shape of XeF4 and OSF4 according to VSEPR
hydrogen bonds is ……… . (SiH4 and SiF4 , acetone and
theory. Show the lone pair of electrons on the central atom.
CHCl 3 , formic acid and acetic acid) (1981, 1M)
(2004, Main, 2M)
59. The angle between two covalent bonds is maximum in …… . 74. Using VSEPR theory, draw the shape of PCl 5 and BrF5 .
(CH4 , H2 O, CO2 ) (1981, 1M)
(2003, 2M)

True/False 75. Draw the molecular structures of XeF 2 , XeF 4 and XeO2 F2 ,
indicating the location of lone pair(s) of electrons. (2000, 3M)
60. The dipole moment of CH3 F is greater than that of CH3 Cl.
(1993, 1M) 76. Interpret the non-linear shape of H2 S molecule and
non-planar shape of PCl 3 using valence shell electron pair
61. H2 O molecule is linear. (1993, 1M) repulsion (VSEPR) theory. (Atomic number : H = 1, P = 15,
62. The presence of polar bonds in a polyatomic molecule S = 16, Cl = 17) (1998, 4M)
suggests that the molecule has non-zero dipole moment. 77. Using the VSEPR theory, identify the type of hybridisation
(1990, 1M) and draw the structure of OF2 . What are the oxidation states of
63. sp 3 hybrid orbitals have equal s and p character. (1987, 1M) O and F ? (1997, 3M)
 Chemical Bonding 53

+
78. Write the Lewis dot structural formula for each of  H   H 
the following. Give also, the formula of a neutral molecule,  ••••   •••• 
which has the same geometry and the same arrangement of H • •O• • H H • •N• • H
the bonding electrons as in each of the following. An    
   
example is given below in the case of H3 O+ and NH3 .
Lewis dot. structure Neutral .molecule (1983, 4M)
−
(i) O2−
2 (ii) CO2−
3 (iii) CN (iv) NCS−

Topic 3 Resonance, LCAO, MOT, Other Bonding Types

Objective Questions I (Only one correct option) 7. Two pi and half sigma bonds are present in
(2019 Main, 10 Jan I)
1. The intermolecular potential energy for the molecules A, B, C
and D given below suggests that: (2020 Main, 4 Sep I) (a) O+2 (b) N2 (c) N+2 (d) O2
Interatomic distance (pm) 8. According to molecular orbital theory, which of the following
50 100 150 is true with respect to Li +2 and Li −2 ? (2019 Main, 9Jan I)
0
(a) Both are unstable
–100
(b) Li+2 is unstable and Li−2 is stable
–200 (c) Both are stable
Potential
Energy –300 (d) Li+2 is stable and Li−2 is unstable
(kJ mol–1) A–D
–400 9. According to molecular orbital theory, which of the
A–A A–C
–500 following will not be a viable molecule? (2018 Main)

–600
A–B (a) He2+
2 (b) He+2
(c) H−2 (d) H2−
2
(a) A-B has the stiffest bond 10. Which of the following species is not paramagnetic?
(b) D is more electronegative than other atoms (2017 Main)
(c) A-A has the largest bond enthalpy (a) NO (b) CO
(d) A-D has the shortest bond length (c) O2 (d) B2
2. During the change of O2 to O−2 , the incoming electron goes to 11. Assuming 2s-2p mixing is not operative, the paramagnetic
the orbital. (2019 Main, 10 April I) species among the following is (2014 Adv.)

(a) π2 px *
(b) π 2 px (c) π2 p y *
(d) σ 2 p z (a) Be2 (b) B2
(c) C2 (d) N2
3. HF has highest boiling point among hydrogen halides, 12. Stability of the species Li 2 , Li −2 and Li +2 increases in the order
because it has (2019 Main, 9 April II) of (2013 Main)
(a) lowest ionic character (a) Li 2 < Li 2+ < Li 2− (b) Li –2 < Li +2 < Li 2
(b) strongest van der Waals’ interactions (c) Li 2 < Li 2− < Li 2+ (d) Li −2 < Li 2 < Li +2
(c) strongest hydrogen bonding
13. In which of the following pairs of molecules/ions both the
(d) lowest dissociation enthalpy
species are not likely to exist? (2013 Main)
4. Among the following species, the diamagnetic molecule is (a) H+2 , He2− (b) H −2 , He22 −
2
(2019 Main, 9 April II)
(a) CO (b) B2 (c) NO (d) O2 (c) H22 + , He2 (d) H−2 , He2+
2

5. Among the following, the molecule expected to be stabilised 14. Hyperconjugation involves overlap of which of the following
by anion formation is C2 , O2 , NO, F2 . (2019 Main, 9 April I) orbitals? (2008, 3M)
(a) C2 (b) F2 (a) σ - σ (b) σ - p
(c) NO (d) O2 (c) p - p (d) π - π

6. Among the following molecules/ions, C2− 2− 2− 15. According to MO theory, (2004, 1M)
2 , N2 , O2 , O2
(a) O+2 is paramagnetic and bond order greater than O2
Which one is diamagnetic and has the shortest bond length?
(2019 Main, 8 April II)
(b) O+2 is paramagnetic and bond order less than O2
(a) C2−
2 (b) O2 (c) O2−
2 (d) N 2−
2
(c) O+2 is diamagnetic and bond order is less than O2
(d) O+2 is diamagnetic and bond order is more than O2
54 Chemical Bonding

16. Molecular shape of SF4 , CF4 and XeF4 are 24. Statement I The electronic structure of O 3 is
(2000, 1M)
(a) the same, with 2, 0 and 1 lone pair of electrons respectively +
O
(b) the same, with 1, 1 and 1 lone pair of electrons respectively •• −
• •
(c) different, with 0, 1 and 2 lone pair of electrons respectively • O • O •• .
•• ••
(d) different, with 1, 0 and 2 lone pair of electrons respectively
O
17. In compounds of type ECl 3 , where E = B, P, As or Bi, the ••
•
angles Cl—E—Cl is in order (1999, 2M) Statement II • O O •• structure is not allowed
•• ••
(a) B > P = As = Bi (b) B > P > As > Bi because octet around O cannot be expanded. (1998, 2M)
(c) B < P = As = Bi (d) B < P < As < Bi
Match the Columns
18. The correct order of increasing CO bond length of
CO, CO23 − , CO2 is (1999, 2M) 25. Match the reactions in Column I with nature of the
reactions/type of the products in Column II. (2007, 6M)
(a) CO23 − < CO2 < CO (b) CO2 < CO2–
3 < CO
Column I Column II
(c) CO < CO2– 3 < CO2 (d) CO < CO2 < CO2–
3
A. O−2 → O2 + O22 − 1. Redox reaction
19. Which contains both polar and non-polar bonds? (1997, 1M)
(a) NH4 Cl (b) HCN B. CrO24 − + H+ → 2. One of the products has
(c) H2 O2 (d) CH4 trigonal planar structure
20. Which one among the following does not have the hydrogen C. MnO−4 + NO−2 3. Dimeric bridged
bond? (1983, 1M) + tetrahedral metal ion
+ H →
(a) Phenol (b) Liquid NH3
(c) Water (d) HCl D. NO−3 + H2 SO4 4. Disproportionation
2+
Objective Questions II + Fe →

(One or more than one correct option)

Codes
21. According to molecular orbital theory, which of the
A B C D A B C D
following statements is(are) correct? (2016 adv.)
(a) 2 1, 4 3 4 (b) 1, 4 3 1, 2 1
(a) C2−
2 is expected to be diamagnetic (c) 2 3 1 4 (d) 3 4 2, 3 1
(b) O2+
2 is expected to have a longer bond length than O2
(c) N+2 and N−2 have the same bond order Integer Answer Type Questions
(d) He+2 has the same energy as two isolated He atoms 26. Chlorine reacts with hot and concentrated NaOH and produces
22. Hydrogen bonding plays a central role in which of the compounds ( X ) and (Y ). Compound ( X ) gives white
following phenomena? (2014 Adv.)
precipitate with silver nitrate solution. The average bond
order between Cl and O atoms in (Y ) is …… .
(a) Ice floats in water
(2020 Main, 7 Jan I)
(b) Higher Lewis basicity of primary amines than tertiary
amines in aqueous solutions 27. Among H2 ,He+2 , Li 2 , Be2 , B2 , C2 , N2 , O−2 and F2 , the
(c) Formic acid is more acidic than acetic acid number of diamagnetic species is
(d) Dimerisation of acetic acid in benzene
(Atomic numbers : H = 1, He = 2, Li = 3, Be = 4, B = 5, C = 6,
23. Which one of the following molecules is expected to exhibit N = 7, O = 8, F = 9) (2017 Adv.)
diamagnetic behaviour? (2013 Main)
(a) C 2 (b) N 2 (c) O 2 (d) S 2 Subjective Questions
28. Write the MO electron distribution of O2 . Specify its bond
Assertion and Reason
order and magnetic property. (2000, 3M)
Read the following questions and answer as per the direction given
below: 29. Arrange the following as stated.
(a) Statement I is correct; Statement II is correct; Statement II is “Increasing strength of hydrogen bonding ( X  H  X ).”
the correct explanation of Statement I. O, S, F, Cl, N (1991, 1M)
(b) Statement I is correct; Statement II is correct; Statement II is 30. What effect should the following resonance of vinyl chloride
not the correct explanation of Statement I.
have on its dipole moment? (1987, 1M)
(c) Statement I is correct; Statement II is incorrect. +
(d) Statement I is incorrect; Statement II is correct. CH2 ==CH  Cl ←→ CH2–  C HCl
 Answers
Topic 1
1. (d) 2. (c) 3. (b) 4. (a) 49. (c) A → 2; B → 3; C →1; D →4
5. (a) 6. (b) 7. (b) 8. (b) 50. (b) A → p, q, r, t; B → q, r, s, t; C → p, q, r, t; D → p, r, s, t
9. (a) 10. (a) 11. (c) 12. (c) 51. N 2O, I 3− 52. increases, decreases
13. (a, c) 14. (a) 15. (6) 16. (1) 53. three centre bond-two electrons
17. (c) 18. (2) 19. F 20. T 54. hyperconjugation
25. (80.2%) 55. sp 56. Triangular planar 57. sp 3
Topic 2 58. HCOOH and CH3COOH 59. CO2 60. F
1. (d) 2. (b) 3. (c) 4. (d) 61. F 62. F 63. F 64. F
5. (d) 6. (c) 7. (a) 8. (d) 65. T 66. (6) 68. (4) 69. (6)
9. (d) 10. (a) 11. (a) 12. (d)
Topic 3
13. (d) 14. (b) 15. (a) 16. (a)
1. (a) 2. (b) 3. (c) 4. (a)
17. (c) 18. (a) 19. (b) 20. (a)
5. (a) 6. (a) 7. (c) 8. (d)
21. (b) 22. (d) 23. (a) 24. (b)
9. (d) 10. (b) 11. (c) 12. (b)
25. (b) 26. (c) 27. (b) 28. (c)
13. (c) 14. (b) 15. (a) 16. (d)
29. (d) 30. (b) 31. (a) 32. (a)
17. (b) 18. (a) 19. (c) 20. (d)
33. (a) 34. (a) 35. (a) 36. (c)
21. (a, c) 22. (a, b, d) 23. (a,b) 24. (a)
37. (c) 38. (c) 39. (d) 40. (b)
25. (b) A → 1, 4; B → 3; C →1, 2; D →1 26. (1.67)
41. (b) 42. (a) 43. (a) 44. (c)
27. (6) 28. (2)
45. (b, c) 46. (a, c) 47. (b, c, d) 48. (a, b)

Hints & Solutions

Topic 1 Preliminary Concepts of Electrovalent
Covalent
and Covalent Bonding P bond
O O
1. Key Idea Isoelectronic species contains same number of H H (O2)
H
electrons. (PH3) Covalent
H H 1.33Å Bonds
Å H
The species with its atomic number and number of electrons are 1.19
as follows : 120° B 97° B
H H H
Species (ions) At. no. ( Z ) No. of electrons
H H H
N3− 7 7 + 3 = 10 H
H H
O2− 8 8 + 2 = 10 B B B B
H H H
F− 9 9 + 1 = 10 H H (B2H6) H Banana bond
Na + 11 11 − 1 = 10 O
+
Li 3 3 −1 = 2 S
Mg 2+
12 12 − 2 = 10 HO OH O
Sulphuric acid
Thus, option (d) contains isoelectronic set of ions. (H2SO4)
2. KCl is the only ionic compound. The structure of PH3, O2, B2H6 All bond between S and O atom are covalent bonds.
and H2SO4 are given below
56 Chemical Bonding

3. Ion-ion interaction is dependent on the square of distance, i.e. 8. BF3 has triangular planar arrangement.
1
ion-ion interaction ∝ F
r2 120°
1 F—B
Similarly, ion-dipole interaction ∝ F
r3
1 1 sp2
London force ∝ and dipole-dipole interaction ∝
r6 r3 Three identical vectors acting in outward direction at equal
Superficially it seems as both ion-dipole interaction and angles in a plane cancel each other giving zero resultant, hence
hydrogen bonding vary with the inverse cube of distance between non-polar.
the molecules but when we look at the exact expressions of field 9. Strongly electropositive, univalent X will form an 1 : 1 ionic
(force) created in two situations, compound with strongly electronegative, univalent Y.
it comes as X + Y → X +Y −
2| P |
| E | or | F | = (In case of ion-dipole interaction) 10. H2 is a covalent, diatomic molecule with a sigma covalent bond
4 π ∈ r3
between two hydrogen atoms.
2q2r – 4 q2a 11. N2 has triple bond and each covalent bond is associated with
and F = (In case of dipole-dipole interaction)
4 π ∈0 r3 one pair of electrons, therefore, six electrons are involved in
forming bonds in N2.
From the above, it is clear that the ion-dipole interaction is the
better answer as compared to dipole-dipole interaction, i.e. 12. In KCN, the bonding between potassium ion and cyanide ion is
hydrogen bonding. ionic while carbon and nitrogen are covalently bonded in
cyanide ion as:
Covalent bonds
H H + –
4. [K] [ C ≡≡N]
C—–C
H H Ionic bond

Pi bond is formed by the p-orbitals whose lobes have minima in 13. Key Idea Dipole moment of a bond depends on the
the plane of molecule, hence molecular plane is the nodal plane of difference in the electronegativities of bonded atoms.
pi-bond. More is the difference in the electronegativities, greater
will be the dipole moment. Also,
5. H-bond is the strongest intermolecular force. For symmetrical molecule, µ = 0
All are different with 1, 0 and 2 lone pairs of electrons at central
For unsymmetrical molecule, µ ≠ 0
atom.
The molecules which gives permanent dipole moment are
6. p-dichlorobenzene is non-polar.
polar in nature.
Cl— —Cl Cl
S Se
p-dichlorobenzene , ,
The two dipole vectors cancelling each other giving zero O O H H
resultant dipole moment. o-dichlorobenzene has greater m¹0 m¹0 m¹0
(polar) (polar) (polar)
dipole moment than meta-isomer.
F
Cl F F
m1 m2
Cl µ1 > µ2 Br
Cl Be Cl
µ1
,
µ2 F m¹0 F mnet» 0
(non-polar)
Cl Cl (polar)

(o-dichlorobenzene) (m-dichlorobenzene) Cl
dipole vectors are at 60° angle dipole vectors are at 120° angle m1 m2
,
O C O B Cl
Toluene is less polar than both ortho and para
mnet 0 m 0
dichlorobenzene. Therefore, the increasing order of dipole Cl
(non-polar) (non-polar)
moment is
p-dichlorobenzene (IV) < toluene (I) < m-dichlorobenzene (II) Cl
N N Cl
< o-dichlorobenzene (III)
H C Cl , , , O P Cl ,
7. The carbide (C2−
2 ) ion has the following bonding pattern:
O O H H H
Cl Cl
– – m¹0 m¹0 m¹0 m¹0
: C ≡≡ C : one sigma and two pi-bonds. (polar) (polar) (polar) (polar)
 Chemical Bonding 57

F F
(vi) (NH4)2FeCl 4 has Fe as central metal atom with +2 oxidation
H F F state. The electronic configuration of Fe 2+ in the complex is
B O
H C Cl , , , Xe 4s 4p
3d
F F O O
H m¹0 m=0 sp3
(polar) (non-polar) m¹0 F F
Cl– Cl– Cl– Cl– hybridisation
(polar) F 4 unpaired
m»0
(non-polar)
electrons

Thus, options (a, c) are correct. (vii) (NH4)2NiCl 4 has Ni as central metal atom with +2 oxidation
state. The electronic configuration of Ni 2+ in the complex is
14. 1,4-dichlorobenzene is non-polar, individual dipole vectors
4s 4p
cancel each other. 3d
µ≠0 sp3
Cl Cl H Cl ClCH2 H Cl– Cl– Cl– Cl– hybridisation
2 unpaired
C==C C==C C==C electrons
H H Cl H Cl C2 H 5 (viii) In K2MnO4 central metal atom Mn has +6 oxidation state
µ=0
Polar Non-polar Polar with following structure
O–
15. Only polar liquid will be attracted towards charged comb due to
the formation of electrically charged droplets in the polar liquid 2K+ Mn
stream, induced by a nearby charged object. Hence, liquid –
O
showing deflection are HF,H2O,NH3 ,H2O2 ,CHCl 3 , C6H5Cl. O O
16. Among the given species only K2CrO4 is diamagnetic as central Electronic configuration of Mn6+ is
0
metal atom Cr in it has [ Ar ]3d electronic configuration i.e., all
3d 4s
paired electrons. The structure and oxidation state of central
metal atom of this compound are as follows
O one unpaired
electron
Structure K+ Cr , Oxidation state Cr6+
O – 17. Statement I is correct but Statement II is incorrect. The
O– O covalency in LiCl is due to small size of Li + ion which brings
Rest all the compounds are paramagnetic. Reasons for their about large amount of polarisation in bond.
paramagnetism are given below 18. These are 2π-bonds in a nitrogen molecule.
(i) H-atom have 1s1 electronic configuration, i.e. 1 unpaired 19. The resultant of individual bond dipoles may or may not be
electron. non-zero.
20. Linear overlapping of p-orbitals form sigma bond while sidewise
N
(ii) NO2 , i.e. in itself is an odd electron species. overlapping of two p-orbitals forms a pi bond.
O O
(iii) O−2 (Superoxide) has one unpaired electron in π * molecular 21. Li + < Al 3+ < Mg2+ < K+
orbital. 22. Ag+ is stronger Lewis acid because it can easily accommodate
(iv) S2 in vapour phase has O2 like electronic configuration i.e., lone pair of electrons from Lewis base. On the other hand, Na +
have 2 unpaired electrons in π * molecular orbitals. has noble gas configuration, cannot accept lone pair of electron,
not at all a Lewis acid.
(v) Mn 3O4 has following structure
23. I2 is Lewis acid because I − coordinate its one lone pair to I2.
+2 O +4
O +2
Mn Mn Mn 24. Both LiF and LiI are expected to be ionic compounds. However ,
O O LiI is predominantly covalent because of small size of Li + and
large size of iodide ion. A smaller cation and a larger anion
Thus, Mn is showing +2 and +4 oxidation states. The outermost introduces covalency in ionic compound.
electronic configuration of elemental Mn is 3d 5 4 s2. Hence, in
both the above oxidation states it has unpaired electrons as 25. Dipole moment is calculated theoretically as
3d 4s µ = q⋅d
Mn2+ Here, q = 1.6 × 10−19 C and d = 2.6 × 10−10 m
5 unpaired electrons µ Theo = 1.6 × 10−19 × 2.6 × 10−10 = 4.16 × 10−29 cm
3d 4s µ obs 3.336 × 10−29
Mn4+ % ionic character = × 100 = × 100
µ Theo 4.16 × 10−29
3 unpaired electrons = 80.2%
58 Chemical Bonding

26. In hydrogen peroxide (H2O2 ), oxygen is in –1 oxidation state, The hybridisation of given species are as follows :
can be oxidised to O2 (zero oxidation state) or can be reduced to l
For [ ICl2 ]− and [ BrF2 ]−
H2O (–2 oxidation state of oxygen).
1
H = (7 + 2 − 0 + 1) = 5 (sp3d )
Hence, H2O2 can act as both oxidising agent and reducing agent. 2
With strong oxidising agent like KMnO4, H2O2 acts as a l
For [ ICl4 ]− ,
reducing agent while with strong reducing agent like H2C2O4 , it
1
acts as an oxidising agent. H = (7 + 4 − 0 + 1) = 6 (sp3d 2 )
2
27. (i) Melting points Ionic compounds have higher melting points l
For [ IF6 ]− ,
than covalent compounds.
(ii) Boiling points Ionic compounds have higher boiling points 1
(7 + 6 − 0 + 1) = 7 (sp3d 3 )
H =
than covalent compounds. 2
(iii) Solubility Ionic compounds have greater solubility in water 4. The radius of isoelectronic species is inversely proportional to
than a covalent compound. their nuclear charge or atomic number (Z). Thus, greater the
value of Z, lesser the radii of isoelectronic species.
(iv) Conductivity in aqueous solution Ionic compounds have
greater electrical conductivity in aqueous solution while 5.
covalent compounds are usually non-conducting. Species Valence MOs Bond Order Paramagnetic/
 N b − N a  Diamagnetic
  Nature
 2 
Topic 2 VBT, Hybridisation and 6−1
NO(15e− ) [ 8 e− ] π 2 px2 = π 2 py2σ 2 pz2 = 2.5 Paramagnetic
VSEPR Theory 2
1. Among the given statements, correct statements are I and III –e− π * 2 p1x = π * 2 py0σ * 2 pz 0
only. Valence bond theory (VBT) cannot explain the colour
exhibited by transition metal complexes. This theory cannot [ 8 e− ] π 2 px2 = π 2 py2σ 2 pz2 6−0 Diamagnetic
=3
distinguish ligands as weak and strong field ones. NO + (14e− ) 2
•• π * 2 px0 = π * 2 py0σ * 2 pz0
2. For ICl5
1 N 2 (14 e− ) [ 8 e− ] π 2 px2 = π 2 py2σ2 pz2 6−0 Diamagnetic
H= (7 + 5 − 0 + 0) = 6 (sp3d 2 ) −
=3
2 –e 2
N 2+ (13 e− ) π * 2 px0 = π * 2 py0 , σ 2 pz0 5−0 Paramagnetic
Cl = 2.5
2
[ 8e− ] π 2 px2 = π 2 p2y σ 2 pz 1
3 2
Cl Cl sp d hybridised
Geometry : Octahedral
I Shape / Structure : Square pyramidal
π * 2 px0 = π * 2 p0y σ * 2 pz0

Cl Cl
O2 (16 e− ) [ 8 e− ] σ 2 pz2 π 2 px2 = π 2 py2 6−2 Paramagnetic
=2
For &&ICl−4 π * 2 p1x = π * 2 p1y σ * 2 pz0
2
1 –e− [ 8 e− ] σ 2 pz2 π 2 px2 = π 2 py2
H = (7 + 4 − 0 + 1) = 6 (sp3d 2 ) O2+ (15 e− )
2 6−1
π * 2 p1x = π * 2 py0σ * 2 pz0 = 2.5 Paramagnetic
Cl Cl sp 3 d 2 hybridised +2e− 2
s Geometry : Octahedral [ 8 e− ] σ 2 pz2 π 2 px2 = π 2 py2
I Shape/Structure : Square planar O22− (18 e− )
Cl Cl π * 2 px2 = π * 2 py2σ * 2 pz0 6 − 4 = 1 Diamagnetic
2
So, ICl5 and ICl−4 are isolobal but not isostructural.
So, only in the conversion of NO → NO+, the bond order has
3. Key Idea The hybridisation for a central atom in a species increased (2.5 → 3) and paramagnetic character has changed to
can be calculated using formula diamagnetic.
1
H = (V + M − C + A ) 6. The structure of I−3 ion is
2 –
where, H = No. of hybridised orbitals used by central atoms. I
V = No. of valence electrons of the central atom.
M = No. of mono-valent atoms (bonded).
C = No. of cationic (positive) charge. I
A = No. of anionic (negative) charge.
I

Hence, 9 is the correct answer.

 Chemical Bonding 59

7. Isoelectronic species are those which contains same number of SF4 : F one lone pair at S.
electrons. F
S
Species Atomic number Number of electrons F
F
O2 − 8 10
•• •• −
F− 9 10 I3− : I I •
• ← •
• I •• three lone pairs at central iodine.
•• ••
+
Na 11 10 O
2+ F  F
Mg 12 10
14. Xe At central atom (Xe), there is one lone pair.
• •
O− 8 9 F F
Na 11 11
15. NO−3 and CO2−
3 both have 32 electrons, central atom
+
Mg 12 11 sp2 hybridised, triangular planar.
∴ Option (a) is correct which contains isoelectronic species 16. CH3Cl has the highest dipole moment.
O2 − , F − , Na + , Mg 2 + . 17. O−2 has odd number(17) of electrons, therefore it must contain
8. I −3 is an ion made up of I 2 and I − which has linear shape. at least one unpaired electron.
While Cs + is an alkali metal cation.  F H 
   
9. 18. F  B− ← N+  H Both ‘B’ and ‘N’ sp3 tetrahedral.
F—S==O S    
 F H 
—

F O  
F F
S is sp3 hybridised Pyramidal 19. NH3 = sp3 ,[ PtCl 4 ]2− = dsp2 , PCl 5 = sp3d , BCl 3 = sp2
SO3 is planar (S is sp2 hybridised), BrF3 is T-shaped and SiO2−
3 is
20. All three have 14 electrons (iso electronic) with bond order of
planar (Si is sp2 hybridised). three.
O H
10. For molecules lighter than O2, the increasing order of energies of
+ +
molecular orbitals is –
N H
O==N==O, O—N==O,
* 21.
π 2 p y  π 2 p y ..... H
σ1s σ* 1sσ 2s σ* 2s  σ 2 p σ
*
2 p sp sp2 sp3 H
 π 2 p z
x x
*
π 2 p z 1 2 3 4 5 6
22. CH2 == CH  CH2  CH2  C ≡≡ CH
where, π2 p y and π2 p z are degenerate molecular orbitals, first
Hybridisation at C2 = sp2 and at C3 = sp3.
singly occupied and then pairing starts if Hund’s rule is obeyed.
If Hund’s rule is violated in B2 , electronic arrangement would 23. H2S has sp3 hybridised sulphur, therefore, angular in shape
be with non-zero dipole moment.
π 2 p 2y H
σ1 s2 σ* 1s2 σ 2s2 σ* 2s2  ...
π 2 p z
S
No unpaired electron-diamagnetic.
H
bonding electrons − antibonding electrons
Bond order =
2
6− 4 (Non-linear, polar molecule)
= =1 F
2
+ −
11. The bond order of CO = 3. NO , CN and N2 are isoelectronic 24. F—B
with CO, have the same bond order as CO. NO− (16e− ) has bond F
order of 2. sp2
12. O−2 in KO2 has 17 electrons, species with odd electrons are always (Trigonal planar)
paramagnetic. 25. Sulphur in SO2 is sp2-hybridised.
••
13. ClO−3 : − O  Cl == O one lone pair at Cl. S
 O O
O Electron pair = 2 (σ-bonds) + 1 (lone pair) = 3
XeF4 : F Xe two lone pairs at Xe. Hybridisation = sp 2
Carbon in CO2 is sp-hybridised, N in N2 O is sp-hybridised,
F F carbon in CO is sp-hybridised.
F
60 Chemical Bonding

26. Molecular orbital electronic configuration are 32. PCl 3 has sp3-hybridised phosphorus, with one lone pair. Therefore,
molecule has pyramidal shape like ammonia.
π 2 p 2y π* 2 p 2y
KO2 (O−2 ) : σ1s2 σ* 1s2 σ 2s2 σ* 2s2 σ 2 px2 σ* 2 px0 33. O−2 has odd number of electrons, hence it is paramagnetic.
π 2 p 2z *
π 2 p1z Cl
Cl Cl 109°
Has one unpaired electron in π* 2 p orbital.
C==C 120° C Cl
AlO−2 has both oxygen in O2− state, therefore, no unpaired 34.
Cl Cl Cl
electron is present. BaO2 (O2− Cl
2 ) sp2-hybridised
* sp3-hybridised
π 2 p 2y π 2 p 2y *
σ1s2 σ* 1s2 σ 2s2 σ* 2s2 σ 2 px2 σ 2 px0
π 2 p 2z 35. CO2 is linear because carbon is sp-hybridised.
π* 2 p 2z
Has no unpaired electron. 36. In CH+3 , there are only three electron pairs around carbon atom
+
NO+2 has [O== N==O] bonding, hence no unpaired giving sp2-hybridisation state.
electron.
+
H
27. N2 is a neutral, non-polar, inert molecule while CN − is a H—C
highly polar, highly active ion. H
28. sp2-hybridised
F
NF3 : N F BF3 : F—B
F 37. Dipole vectors in trans-1, 2-dichloroethylene are at 180° and
F directed in opposite direction, cancelling each other.
F Triangular planar
Pyramidal (B-sp2) H Cl
(N-sp3)
C==C dipole moment = 0
– +
– O + O H
NO3 : H 3O : H Cl
O==N H
O H 38. In SO2, the Lewis-dot structure is
Triangular planar Pyramidal
• •
(N-sp2) (O-sp3)
O == S == O
•• + •• Electron pairs at S = 2 (σ-bonds) + 1 (lone-pair) = 3
N3H •• • N == N == N  H
•
Central nitrogen is sp -hybridised sp2 hybridised.
NOTE
Therefore, NF3 , H3O+ and BF3 , NO3− pairs have same shape.
π-bonded electrons are not present in hybrid orbitals, therefore not
counted in electron pairs. Rather π bonds are formed by lateral
29. BF3 has triangular planar arrangement. overlapping of pure p-orbitals.
F
39. Bonds between identical non-metal is purely covalent due to same
F—B 120° electronegativities of the bonded atoms. Hence, the bonded atoms
F have equal holds on the shared pair of electrons.
sp2-hybridised
40. Hybridisation of one ‘s’ and one ‘p’ orbitals gives two
There identical vectors acting in outward direction, at sp hybrid orbitals oriented linearly at 180°.
equal angles in a plane, cancel each other giving zero s + p → 2 sp hybrid orbitals
resultant, hence non-polar.
41. CCl 4 has a regular tetrahedral shape.
30. A water molecule can form at the most four H-bonds.
Cl
H µ
C µ Cl Net dipole = 0
O
Cl
H Cl
Four sites of H-bonding 42. CO has a total of 14 electrons and CN− also has 14 electrons.
• • C (6e− ) + N (7e− ) + e− → CN− (14 e− )
−
31. O  Cl == O
• • 43. CO2 is a linear molecule because of sp-hybridisation around
electron pairs at Cl = 2 (σ-bonds) + 2 (lone-pairs) = 4 carbon atom.
3 44. For non-polar MX 3, it must have triangular planar arrangement,
Hybridisation at Cl = sp
i.e. there should be sp2-hybridisation around M.
 Chemical Bonding 61

CH3
H3C H C. p-d π antibonding

45. H3C  C  CH3 C == C
 H CH2CH3
CH3 Polar
Symmetric, non-polar

CH3 CH3
CH3H2C CH2CH3   D. d-d σ antibonding
C == C H3C  C  C  CH3
H H  
CH3 CH3
Polar Symmetric, non-polar ∴ A → 2, B → 3, C → 1, D → 4
Hence, (c) is the correct option.
46. CN− and NO+ are isoelectronic, have the same bond order of 3.
+
π 2 p1y
47. S== C == S O== N == O −
O  C ≡≡ N
50. (A) B2 : σ1s2 σ* 1s2 σ 2 s2 σ* 2s2 paramagnetic.
Linear Linear Linear π 2 pz1
•• •• 6− 4
Sn S Bond order = =1
2
Cl Cl O O
Bent Bent Bond is formed by mixing of s and p orbitals.
B2 undergoes both oxidation and reduction as
48. CO2 , HgCl 2 , C2H2 are all linear. Heat
B2 + O2 → B2 O3 (Oxidation)
49. PLAN This problem includes basic concept of bonding. It B2 + H2 → B2 H6 (Reduction)
can be solved by using the concept of molecular orbital theory.
π 2 p 2y
+ ve phase (B) N2 : σ1s2 σ* 1s2 σ 2 s2 σ* 2 s2σ 2 px2 diamagnetic.
10 − 4 π 2 p 2z
Bond order = = 3> 2
2
– ve phase N2 undergoes both oxidation and reduction as
∆
Any orbital has two phase +ve and –ve. In the following N2 + O2 → NO
diagram, +ve phase is shown by darkening the lobes and –ve by Catalyst
without darkening the lobes. N2 + 3H2 → NH3
In N2 , bonds are formed by mixing of s and p orbitals.
π 2 p2y π* 2 p2
(C) O2− : σ1s2 σ
*
1s 2 σ 2 s 2 σ
*
2 s2 σ 2 px2 y σ
*
2 px0
π 2 pz2 π* 2 pz1
Bonding MO Antibonding MO −
Paramagnetic with bond order = 1.5. O2 undergoes both
When two same phase overlap with each other, it forms bonding
oxidation and reduction and bond involves mixing of s and
molecular orbital otherwise antibonding.
p-orbitals.
σ-bond
π 2 p2y π* 2 p1y
(D) O2 : σ1s2 σ
*
1s2 σ 2 s2 σ
*
2 s2 σ 2 px2 σ
*
2 px0
π 2 pz2 π* 2 p1
z
π-bond Paramagnetic with bond order = 2.
O2 undergoes reduction and the bond involves mixing of
s and p-orbitals.
On the basis of above two concepts, correct matching can be 51. N2O and I−3 are linear species.
done as shown below:
52. Bond order in N2 is 3 while same in N+2 is 2.5, hence bond
distance increases as N2 goes to N+2 .
A. d-d σ bonding Bond order in O2 is 2 while same in O+2 is 2.5, hence bond
distance decreases as O2 goes to O+2 .
53. Three centred-2 electrons.
54. Hyperconjugation involves delocalisation of σ-electrons.
B. p-d π bonding
55. sp-hybridised.
56. Triangular planar. Carbon in CH+3 is sp2 hybridised.
62 Chemical Bonding

57. sp3-hybrid orbital holding the lone pair is involved in formation 2+ 2–

of ammonium ion. H3N NH3 Cl Cl
O O Cu Pt
  H3N NH3 Cl Cl
58. H  C  OH and CH3  C  OH . Both are capable of forming
H-bonds. SF4 (See-saw) as shown below:
59. CO2, it is 180°. F
F
60. Dipole moment (µ ) = q.d S
F
Since electronegativity of F and Cl are very close, it is the
F
internuclear distance (d) that decides dipole moment here.
Hence, C  Cl bond has greater dipole moment the C-F bond. SiF4 , BF4− , [FeCl 4 ]2− , [CoCl 4 ]2− are tetrahedral as shown below:
61. H2O is V-shaped molecule.
O
H H
V-shaped
62. False
63. In sp3-hybrid orbital, there is 25 % s-character and 75 % p-character.
64. Carbon in benzene is sp2-hybridised, i.e. uses only two of its
p-orbitals in hybridisation.
65. Sn in SnCl 2 has sp2-hybridisation.
66. S.N. Species No. of σ-bonds No. of L.P at
with central atom central atom
Hence, correct integer is 4.
(i) In [ TeBr6 ]2− 6 1
(ii) In [ BrF2 ]+ 2 2 69. PLAN Melamine is a heterocyclic compound.

(iii) In SNF3 4 0 H2N N NH2

(iv) In [ XeF3 ]− 3 3
••
N N
–
67. Cl  Be  Cl N ≡≡ N → N ••
↑ ↑ •• NH2
sp sp
•• + Each nitrogen atom has one pair of lone pair. Thus, in all six
N≡≡ N → O•• O == N == O lone pairs.
↑ •• ↑
sp sp 70. F
F F
All the above mentioned molecules/ions have sp-hybridised
central atom and no one pair at central atom, hence linear also. Br
Others are :
O S [Cl  I  Cl] F F
O O Cl Cl Lone pair would push the Br—F bond pairs in upward direction
sp2-bent sp3-V-shaped sp3d-linear and all Br—F bond angles will contract.
[I  I  I]– F  Xe  F
71. No, (i) NMe3 is pyramidal while (ii) N(SiMe3 )3 is planar. In the
sp3d-linear sp3d-linear latter case, pπ - dπ back bonding between N and Si makes N
–
[Although ICl 2 , I–3 and XeF2 all also are linear but in them sp2-hybridised.
d-orbital contribute in hybridisation.] 72. Bond order : O2− = 1.5, O2 = 2, O2+ = 2.5
68. PLAN This problem includes concept of hybridisation using VBT, Bond length : O+2 < O2 < O−2
VSEPR theory, etc.,
73.
XeF4 , BrF4− , [Cu(NH3 )4 ]2+ , [PtCl 4 ]2− are square planar as shown F F
below: F F

s Xe O S
F F F F
Xe Br F
F
F F F F
F F
Square planar Trigonal bipyramidal
 Chemical Bonding 63

74. F (d) A - D has shortest bond length, it is incorrect because inter

Cl Cl
F F molecular distance in between A - D more than 150 (pm)
which is height in all.
Cl P Br 2. The change of O2 to O−2 can be as follows:
+e – –
F F O2 (16 e –) O2 (17 e–)
Cl Cl [Dioxygen] [Super-oxide]
Energy Energy
Trigonal bipyramidal Square pyramidal
(P is sp3d-hybridised) (Br is sp3d 2 -hybridised) [8e– ] σ2p2z π2px2 [8e– ] σ2p2z π2p2x = π2p2y π* 2px2
75. = π2py2 π* 2px1 = π* 2p1y = π* 2p1y
F F
F F O Half-filled
anti-bonding
π*-MOs
Xe Xe Xe
So, in the formation of O−2 from O2, the 17th electron goes to the
F F * *
O π 2px or π 2py molecular orbital (anti-bonding) which is
F F
Linear Square planar See-saw shaped half-filled in O2.
3 3. HF has highest boiling point among hydrogen halides because it
76. In H2S, S is sp -hybridised with two lone pairs of electrons on it
has strongest hydrogen bonding. Here, the hydrogen bond exists
giving V-shaped (water like) shape. In PCl 3 , P is sp3-hybridised between hydrogen of one molecule and fluorine atom of another
with one lone pair of electrons on it. Therefore, PCl 3 is molecule as shown below.
pyramidal in shape. δ+ δ− δ+ δ− δ+ δ−
+2
…H F…H F…H F
×× •• ×× O In this molecule, hydrogen bond behaves like a bridge between
× × −1
77. × F ו O •× F × F F −1 two atoms that holds one atom by covalent bond and the other by
×× •• ×× V-shaped hydrogen bond.

Electron pair = P = 2 + 2 = 4 4. Key Idea Magnetic nature can be detected by molecular orbital
Hybridisation = sp3 theory. Presence of unpaired electrons means paramagnetic and
absence of unpaired electrons means diamagnetic in nature.
•• •• 2− •• ••
•  •  • • Among the given options, CO is a diamagnetic molecule. It can
78. (i) O2−
2 :  • O •• O •  and • Cl •• Cl • (Cl 2 )
•• ••
  •• •• be proved by molecular orbital (MO) theory. The electronic
configuration of given diatomic molecules are given below.
2−
 • •  CO (Number of electrons = 14)
•O•
l

 •• 
 ••  Electronic configuration = σ1s2 , σ* 1s2 , σ 2s2 , σ* 2s2,
2−
(ii) CO3 :  C  and F • • B • • F (BF3 ) σ2 pz2 , π 2 px2 ≈ π 2 p2y
 • • • •  •
•
• O • • O • F Since, there is no unpaired electron in the CO molecule, so it
 • • • • • • • •  is diamagnetic.
 ••
• • − •• •• l
NO (Number of electrons = 15)
(iii) CN − :  •• C • • N  and C •• •• O •• (CO) Electronic configuration = σ1s2 , σ* 1s2 , σ 2s2,
••
 
−
σ* 2s2 , σ 2 pz2 , π 2 px2 ≈ π 2 p2y, π * 2 px1 ≈ π * 2 p0y
 ••  ••
•• ••
(iv) NCS− :  •• S ••C •• N and •• Cl • • C • • N (ClCN) Since, NO has one unpaired electron in π * 2 px1 orbital, so it is
•• ••
 ••  • •
paramagnetic.
l
B2 (Number of electrons = 10)
Topic 3 Resonance, LCAO, MOT, Electronic configuration = σ1s2 , σ* 1s2 , σ2s2, σ* 2s2,
Other Bonding Types π 2 px1 ≈ πp1y
1. (a) A - B has stiffest bond.
Since, two unpaired electrons are present in π 2 px1 and π 2 p1y
This is correct because the potential energy of A - B has
maximum negative value [between −500 to −600]. More orbital. So, it is paramagnetic.
negative is the potential energy means high energy is l
O2 (Number of electrons = 16)
released. Higher the released energy higher is the stability
Electronic configuration = σ1s2 , σ* 1s2 , σ 2s2 , σ* 2s2,
and hence the stiffness bond.
(b) D is more electronegative than other atoms, it is incorrect. σ 2 pz2 , π 2 px2 ≈ π 2 p2y, π * 2 px1 ≈ π * 2 p1y
(c) A - A has the largest bond enthalpy, it is incorrect because Since, two unpaired electrons are present in π * 2 px1 and π * 2 p1y
value of potential energy is more negative in A - B.
orbital. So, it is also paramagnetic.
64 Chemical Bonding

5. C2 will be stabilised after forming anion. The electronic configuration of carbon is1s2 2s2 2 p2. There are twelve electrons inC2. After forming
anion (i.e. C–2 ), the electronic configuration is
l
C−2 : (σ1s) 2 (σ *1s) 2 (σ 2 s) 2 (σ * 2 s) 2 ( π 2 px2 = π 2 p 2y ) (σ2 pz1 ) or KK (σ 2 s) 2 (σ * 2 s) 2 ( π 2 px2 = π 2 p 2y ). σ 2 pz1
1 1
Bond order = (N b − N a ) = (9 − 4 ) = 2.5
2 2
For other options such as F2− , O2− , NO− , the electronic configurations are as follows :
l
F2− : (σ1s)2 (σ* 1s)2 (σ 2s)2 (σ* 2s)2 (σ 2 pz )2 (π 2 px2 = π 2 py2 ) (π * 2 px2 = π * 2 p2y )(σ* 2 pz1 )
Bond order = 1 / 2(N b − N a ) = 1 / 2(10 − 9) = 0.5
l
O−2 : (σ1s)2. (σ* 1s)2 (σ 2s)2 (σ* 2s)2 (σ 2 pz )2(π 2 px2 = π 2 p2y ) (π * 2 px2 = π * 2 p1y )
1 1
Bond order = (N b − N a ) = (10 − 7) = 15 .
2 2
−
l
NO : (σ1s) (σ 1s) (σ 2s) (σ * 2s) (σ 2 pz )2 (π 2 px2 = π 2 p2y ) (π * 2 px1 = π * 2 p1y )
2 * 2 2 2

1 1
Bond order = (N b − N a ) = (10 − 6) = 2
2 2
The value of bond order of C−2 is highest among the given options. Bond order between two atoms in a molecule may be taken as an
approximate measure of the bond length.
The bond length decreases as bond order increases. As a result, stability of a molecule increases.

6. Species MO energy order Bond order (BO) n, number of unpaired e− Magnetic character
C22− (14e− ) [ 8e ] π = π σ 6−0 0 Diamagnetic
2p x2 2p y2 2p z2 =3
2
O2 (16e− ) [ 8 e ]σ π = π π* = π* 6−2 2 Paramagnetic
2p z2 2p x2 2p y2 2p1x 2p1y =2
2
O22− (18e− ) [ 8 e ]σ π = π π* *
= π 6−4 0 Diamagnetic
2p z2 2p x2 2p y2 2p x2 2p y2 =1
2
N22− (16e− ) 6−2 2 Paramagnetic
[ 8e ] π = π σ *
π = *π 2p1y =2
2p x2 2p y2 2p z2 2p1x 2

1 Nb − Na 3 − 2 1
Bond length ∝ . So order of bond length Bond order (BO) = = =
BO (Bond order) 2 2 2
C22− < O2 = N22− < O22− The electronic configuration of
(BO = 3) (BO = 2) (BO = 1) Li−2 (Z = 7) = σ1s2 , σ* 1s2 , σ2 s2 , σ ∗ 2 s1
The diamagnetic species with shortest bond length is C2−
2 N − Na 4 − 3 1
Bond order (BO) = b = =
(option-a). 2 2 2
7. The energy order of MOs of the given species are as follows: For the species having the same value of BO, the specie having
lesser number of antibonding electrons[ N a ] will be more stable.
O2 (16 e− ’s) = σ1s2 , σ* 1s2 , σ 2s2 , σ* 2s2 , σ 2 p2z ,
Here, N a of Li+2 (2) < N a of Li −2 (3) . So, their order of stability
π 2 p2x = π 2 p2y , π * 2 px1 = π * 2 p1y , will be Li+2 > Li2− .
O+2 (15e− ’s ) = σ1s2, σ* 1s2 , σ2s2, σ* 2s2 , σ2 p2z , 9. Key Idea According to M.O.T, the viability of any molecule can
be judged through the calculation of bond order.
π 2 p2x = π 2 p2y , π * 2 px1 ≈π *
2 p0y
Electronic Bond order
N2 (14 e− ’s ) = σ 1s2 σ* 1s2 , σ 2s2 , σ* 2s2 Configuration
π 2 p2x = π 2 p2y, σ 2 pz2 He+2 σ 2 σ* 1 2−1
1s 1s = 0.5
2
N+2 (13e− ’s) = σ1s σ 1s σ2 s σ* 2s2
2 * 2 2

H−2 σ σ* 2−1
π 2 p2x = π 2 pz2 σ 2 pz1 1s 2 1s1 = 0.5
2
Thus, in case of N+2 , two π-bonds and half σ-bond are present in 2−2
H2− σ σ* =0
2 1s 2 1s 2
the bonding MOs. 2
8. Considering molecular orbital theory (MOT) : He2+ σ 2−0
2 1s 2 =1
The electronic configuration of Li+2 (Z = 5) = σ1s , σ 1s , σ 2s 2 * 2 1
2
 Chemical Bonding 65

The molecule having zero bond order will not be viable hence, Stability order is Li −2 < Li 2+ < Li 2 (because Li −2 has more number
H2−
2 (option d) is the correct answer. of electrons in antibonding orbitals which destabilises the
10. To identify the magnetic nature we need to check the molecular species).
orbital configuration. If all orbitals are fully occupied, species is 13. Species having zero or negative bond order do not exist.
diamagnetic while when one or more molecular orbitals is/are
H2+
2 (1 + 1 − 2 = 0) = σ1s
0
singly occupied, species is paramagnetic.
(a) NO (7 + 8 = 15) − σ1s2 , σ* 1s2 , σ 2s2 , σ* 2s2 , Bond order = 0
He2 (2 + 2 = 4 ) = σ1s2 , σ* 1s2
π 2 px2 = π 2 p2y , π 2 pz2 , π * 2 px1 = π * 2 p0y
N − Na 2 − 2
One unpaired electron is present. Hence, it is paramagnetic. Bond order = b = =0
2 2
(b) CO (6 + 8 = 14 ) − σ1s2 , σ* 1s2 , σ 2s2 , σ* 2s2 ,
So, both H2+
2 and He2 do not exist.
π 2 px2 = π 2 p2y, σ 2 pz2
H H
No unpaired electron is present. Hence, it is diamagnetic.   −
(c) O2 (8 + 8 = 16) − σ1s2 , σ* 1s2 , σ 2s2 , σ* 2s2 , σ 2 pz2 , 14. H  C  CH == CH2 ←→ H  C == CH  CH2
 +
π 2 px2 = π 2 px2 , π * 2 px1 = π * 2 p1y H H
Two unpaired electrons are present. (I) (II)
Hence, it is paramagnetic. I and II are hyperconjugation structures of propene and involves
(d) B2(5 + 5) − σ1s2 , σ* 1s2 , σ 2s2 , σ* 2s2 , π 2 px1 = π 2 p1y σ-electrons of C—H bond and p-orbitals of pi bond in
delocalisation.
Two unpaired electrons are present.
Hence, it is paramagnetic. π 2 p2y π* 2 p1y
15. O+2 (15e− ) : σ1s2 σ* 1s2 σ 2s2 σ* 2s2 σ 2 px2 σ
*
2 px0
11. PLAN This problem can be solved by using the concept involved in π 2 pz2 π* 2 p0
molecular orbital theory. Write the molecular orbital electronic 10 − 5 z
configuration keeping in mind that there is no 2s-2p mixing, Bond order = = 2.5; paramagnetic.
then if highest occupied molecular orbital contain unpaired 2
electron then molecule is paramagnetic otherwise diamagnetic. −
π 2 p2y π* 2 p1y *
O2 (16e ) : σ1s σ 1s2 σ 2s2 σ
2* *
2s2 σ 2 px2 σ 2 px
Assuming that no 2s-2p mixing takes place the molecular orbital π 2 pz2 π* 2 p1
electronic configuration can be written in the following sequence z
10 − 6
of energy levels of molecular orbitals Bond order = =2
* 1s, σ 2s, σ
* 2s, σ 2 p , π 2 p ≡ π 2 p , π* 2 p ≡ π* 2 p , σ
* 2p 2
σ1s, σ z x y x y z Hence, (a) is the correct answer.
* 1s2 , σ 2s2 , σ
(a) Be2 → σ1s , σ 2 * 2s2 (diamagnetic)
F F F F F
* 1s2 , σ 2s2 , σ
2 * 2s2 , σ 2 p2 , π 2 px0
(b) B2 → σ1s , σ z (diamagnetic)
π 2 py0 S Xe
16. C
F
* 2s2 , σ 2 p2 , π 2 px ,
1

(c) C2 → σ1s2 , σ * 1s2 , σ 2s2 , σ F F F F

π 2 p1y
z
F F
π* 2 px0 * 0 See-saw shape Tetrahedral Square planar
, σ 2 p (paramagnetic)
z molecule
π* 2 py0
17. When E = Bin BCl 3 , bond angle is 120°. When E = P, As or Bi in
* 2s2 , σ 2 p2 , π 2 px ,
2
(d) N2 → σ1s2 , σ * 1s2 , σ 2s2 , σ
z
π 2 py2 ECl 3 , hybridisation at E will be sp3. Also, if central atoms are
from same group, bond angle decreases down the group provided
π* 2 px0
, σ * 2 pz0 (diamagnetic) all other things are similar. Hence, the order of bond angles is
*
π 2p 0 BCl 3 > PCl 3 > AsCl 3 > BiCl 3
y

Hence, (c) is the correct choice. 1

18. Bond length ∝
Bond order
12. Li 2 (3 + 3 = 6) = σ1s2 , σ* 1s2 , σ 2s2
1 4
Nb − Na 4 − 2 Bond order : CO2 = 2, CO = 3 , CO23− = 1 + =
Bond order = = =1 3 3
2 2
+ 2 * 2 Therefore, order of bond length is CO23− < CO2 < CO
Li 2 (3 + 3 − 1 = 5) = σ1s , σ 1s , σ 2s1
3−2 1 19. H2O2 H
Bond order = = = 0.5
2 2
O—O
Li −2 (3 + 3 + 1 = 7) = σ1s2 , σ*1s2 , σ 2s2 σ* 2s1 polar bond
H
4−3 1 Non-polar bond
Bond order = = = 0.5
2 2
66 Chemical Bonding

20. HCl does not form hydrogen bond. For formation of hydrogen state, i.e. reduced. Hence, in the above reaction, oxygen
bond, atleast one hydrogen atom must be bonded to one of the ( O−1 / 2 ) is simultaneously oxidised and reduced
three most electronegative atom O , N and F. disproportionated.
21. (B) In acidic medium, CrO2− 2−
4 is converted into Cr2 O7 which
Species Electrons MOEC N B N A BO Magnetic is a dimeric, bridged tetrahedral.
character O– O–
C2−
2
14 σ1s2 , σ * 1s2 , 10 4 3 Diamagnetic
Cr Cr
O O
σ 2s2 , σ * 2s2 , O
O O
π 2 px2 ≈ − π 2 p2y ,
(C) MnO−4 + NO−2 + H+ → Mn 2+ + NO−3
σ 2 pz2
The above is a redox reaction and a product NO−3 has
O2+ 14 As above 10 4 3 Diamagnetic
2 trigonal planar structure.
according to
O2 16 number of 10 6 2 Paramagnetic (D) NO−3 + H2SO4 + Fe2+ → Fe+ + NO
N+2 13 electrons 9 4 2.5 Paramagnetic The above is a redox reaction.
N −2 15 10 5 2.5 Paramagnetic 26. The reaction is,
He+2 3 2 1 0.5 Paramagnetic 3Cl2 + 6 NaOH 5 NaCl + NaClO3 + 3H2O
(X) (Y)
Thus, (a) is correct.
+ AgNO3
(b) Bond order O2+ 2 > O 2 thus,
Bond length of O2+
2 < O 2 thus, incorrect. AgCl
(c) N+2 and N−2 have same bond order thus correct. (white ppt.)
+ –
(d) He+2 with bond order = 0.5 is more stable thus, less energy than Y = NaClO3 (Na and ClO3 )
isolated He atoms. Thus, (d) is incorrect. –
The structure of ClO3 (chlorate ion) is,
22. PLAN This problem can be solved by using concept of H-bonding and
applications of H-bonding. Cl Cl Cl == Cl
O O O O O O O O
23. C2 (6 + 6 = 12) = σ1s , σ* 1s , σ 2s , σ* 2s ,
2 2 2 2
π 2 px2 ≈ π 2 p2y O O O O
Since, all the electrons are paired, it is a diamagnetic species. ‘ClO’ bond order in the hybrid
N2 ( 7 + 7 = 14 ) = σ1s , σ* 1s2, σ 2s2 ,
2
=
Number of bonds between Cl and O
Total number of O (surrounding atoms)
σ* 2s2 , π 2 px2 ≈ π 2 p 2y , σ 2 p 2z
5
It is also a diamagnetic species because of the absence of = = 166
. or 1.67
3
unpaired electrons.
O2 (8 + 8 = 16) or S2 = σ1s2 , σ* 1s2 , σ 2s2 , σ∗ 2s2 , 27. H2 , Li 2 , Be2 , C2 , N2 and F2 are diamagnetic according to
molecular orbital theory.
σ 2 p 2 , π 2 p 2 ≈ π 2 p 2 π* 2 p1 ≈ π* 2 p1
z x y x y
Due to the presence of two unpaired electrons, O2 and S2 both are π 2 p2y π* 2 p1y
28. O2 : σ1s2 σ* 1s2 σ 2s2 σ* 2s2 σ 2 px2
paramagnetic molecules.
π 2 pz2 π* 2 p1
24. Statement I is correct, given structure is one of the resonance z

structure of ozone. 10 − 6
Bond order = = 2, paramagnetic.
+ + 2
O ←→ O
29. Strength of hydrogen bonding in X—H—X depends on
O O− −O O electronegativity as well as size of X . X with higher
Statement II is also correct because oxygen cannot expand its electronegativity and smaller size forms stronger H-bond.
octet. It is also the explanation for the given structure of ozone. Hence, increasing order of strength of H-bond is
25. (A) In the reaction : O−2 → O2 + O22− S < Cl < N < O < F
Oxygen on reactant side is in − 1/ 2 oxidation state. In 30. Resonance in vinyl chloride increases polar character of the
product side, one of the oxygen is in zero oxidation state, molecule.
i.e. oxidised while the other oxygen is in –1 oxidation
5
States of Matter
Topic 1 Gaseous State (a) vmp of H 2 ( 300 K ); vmp of N 2(300 K); vmp of
O2(400 K)
Objective Questions I (Only one correct option) (b) vmp of O2 ( 400 K ); vmp of N 2(300 K); vmp of
1. If the distribution of molecular speeds of a gas is as per the H 2(300 K)
figure shown below, then the ratio of the most probable, the (c) vmp of N 2(300 K); vmp of O2 ( 400 K ); vmp of
average, and the root mean square speeds, respectively, is H 2(300 K)
(2020 Adv.)
(d) vmp of N 2(300 K); vmp of H 2(300 K); vmp of
O2(400 K)
4. Consider the following table.
Fraction of
molecules

Gas a/(k Pa dm6mol −1) b/(dm 3mol −1 )

A 642.32 0.05196
B 155.21 0.04136
C 431.91 0.05196
D 155.21 0.4382
Speed
a and b are van der Waals’ constants. The correct
(a) 1 : 1 : 1 (b) 1 : 1 : 1.224
statement about the gases is (2019 Main, 10 April I)
(c) 1 : 1.128 : 1.224 (d) 1 : 1.128 : 1
(a) gas C will occupy lesser volume than gas A; gas B
2. For one mole of an ideal gas, which of these statements must be will be lesser compressible than gas D
true? (2020 Main, 4 Sep I) (b) gas C will occupy more volume than gas A; gas B
(A) U and H each depends only on temperature. will be more compressible than gas D
(B) Compressibility factor Z is not equal to 1. (c) gas C will occupy more volume than gas A; gas B
(C) C p,m − CV,m = R will be lesser compressible than gas D
(D) dU = CV dT for any process. (d) gas C will occupy more volume than gas A; gas B
(a) (B), (C) and (D) (b) (A) and (C) will be lesser compressible than gas D
(c) (A), (C) and (D) (d) (C) and (D) 5. At a given temperature T, gases Ne, Ar, Xe and Kr are
3. Points I, II and III in the following plot respectively correspond found to deviate from ideal gas behaviour. Their equation
to (vmp : most probable velocity) RT
(2019 Main, 10 April II) of state is given as, p = at T.
V −b
Here, b is the van der Waals’ constant. Which gas will
Distribution function f( v)

exhibit steepest increase in the plot of Z (compression

factor) vs p? (2019 Main, 9 April II)
(a) Xe (b) Ar (c) Kr (d) Ne
6. Consider the van der Waals’ constants, a and b, for the
following gases.
Gas Ar Ne Kr Xe
6 −2
a/(atm dm mol ) 1.3 0.2 5.1 4.1
I II III
−2 3 −1
Speed, v b/(10 dm mol ) 3.2 1.7 1.0 5.0
68 States of Matter

Which gas is expected to have the highest critical figure below. The temperature of one of the bulbs is then
temperature ? (2019 Main, 9 April I) raised to T2 . The final pressure p f is (2016 Main)
(a) Kr (b) Xe (c) Ar (d) Ne
 T1   T 
7. The combination of plots which does not represent isothermal (a) 2 pi   (b) 2 pi  2 
 T1 + T2   T1 +T2 
expansion of an ideal gas is
(2019 Main, 12 Jan II)  TT   TT 
(c) 2 pi  1 2  (d) pi  1 2 
 T1 +T2   T1 +T2 

p p
13. If Z is a compressibility factor, van der Waals’ equation at
low pressure can be written as (2014 Main)
RT a
(a) Z = 1 + (b) Z = 1 −
O 1/Vm O Vm pb VRT
(A ) (B) pb pb
(c) Z = 1 − (d) Z = 1 +
RT RT
pVm 14. For gaseous state, if most probable speed is denoted by C *,
U average speed by C and root square speed by C, then for a
large number of molecules, the ratios of these speeds are
O O (a) C * : C : C = 1.225 : 1.128 : 1 (2013 Main)
p Vm
(C) (D) (b) C * : C : C = 1.128 : 1.225 : 1
(c) C * : C : C = 1 : 1.128 : 1.225
(a) ( A ) and (C ) (b) ( B ) and (C )
(c) ( B ) and ( D ) (d) ( A ) and ( D ) (d) C * : C : C = 1 : 1.225 : 1.128

8. An open vessel at 27ºC is heated until two fifth of the air 15. For one mole of a van der Waals’ gas when b = 0 and
(assumed as an ideal gas) in it has escaped from the vessel. T = 300 K, the pV vs 1/V plot is shown below. The value of
Assuming that the volume of the vessel remains constant, the the van der Waals’ constant a (atm L mol − 2 ) (2012)
temperature at which the vessel has been heated is
(2019 Main, 12 Jan II) 24.6
(a) 750 K (b) 500 K
pV (L atm mol–1)

23.1
(c) 750ºC (d) 500ºC
21.6
9. The volume of gas A is twice than that of gas B. The
20.1
compressibility factor of gas A is thrice than that of gas B at
same temperature. The pressures of the gases for equal
number of moles are (2019 Main, 12 Jan I)
(a) p A = 2 pB (b) 2 p A = 3 pB
(c) p A = 3 pB (d) 3 p A = 2 pB 0 2.0 3.0
1/ V (mol L–1)
10. A 10 mg effervescent tablet containing sodium bicarbonate
and oxalic acid releases 0.25 mL of CO2 at T = 29815
. K and (a) 1.0 (b) 4.5 (c) 1.5 (d) 3.0
p = 1 bar. If molar volume of CO2 is 25.0 L under such 16. The term that corrects for the attractive forces present in a
condition, what is the percentage of sodium bicarbonate in real gas in the van der Waals’ equation is (2009)
each tablet? (a) nb (b) n 2 a / V 2
[Molar mass of NaHCO 3 = 84 g mol −1 ] (2019 Main, 11 Jan I) 2 2
(c) − ( n a / V ) (d) − nb
(a) 8.4 (b) 0.84 (c) 16.8 (d) 33.6 17. The given graph represent the variations of Z
11. 0.5 moles of gas A and x moles of gas B exert a pressure of 200 (compressibility factor ( Z ) = pV / nRT ) ) versus p, for three
3
Pa in a container of volume 10m at 1000 K. Given R is the real gases A, B and C. Identify the only incorrect statement.
(2006, 5M)
gas constant in JK −1 mol−1 , x is (2019 Main, 9 Jan I) C A
2R 4 −R 4 +R 2R A Ideal gas
(a) (b) (c) (d) B
4−R 2R 2R 4+R C
1
12. Two closed bulbs of equal volume (V) containing an ideal gas B
Z
initially at pressure pi and temperature T1 are connected
through a narrow tube of negligible volume as shown in the 0 p (atm)
 States of Matter 69

(a) For the gas A, a = 0 and its dependence on p is linear at all 25. A gas will approach ideal behaviour at (1999, 2M)
pressure (a) low temperature and low pressure
(b) For the gas B, b = 0 and its dependence on p is linear at all (b) low temperature and high pressure
pressure (c) high temperature and low pressure
(c) For the gas C, which is typical real gas for which neither a (d) high temperature and high pressure
nor b = 0 . By knowing the minima and the point of
intersection, with Z = 1, a and b can be calculated
26. According to Graham’s law, at a given temperature the ratio
rA
(d) At high pressure, the slope is positive for all real gases of the rates of diffusion of gases A and B is given by
rB
18. If helium and methane are allowed to diffuse out of the
(where, p and M are pressures and molecular weights of gases
container under the similar conditions of temperature and
A and B respectively)
pressure, then the ratio of rate of diffusion of helium to 1 1
(1998, 2M)
methane is (2005)  p   M 2  M   p 2
(a)  A   A  (b)  A   A 
(a) 2.0 (b) 1.0  pB   M B   M B   pB 
(c) 0.5 (d) 4.0 1 1
 p   M 2  M   p 2
19. For a monatomic gas kinetic energy = E. The relation with (c)  A   B  (d)  A   B 
 pB   M A   M B   pA 
rms velocity is (2004, 1M)

 2E 
1/ 2
 3E 
1/ 2 27. The compressibility factor for an ideal gas is (1997, 1M)
(a) u =   (b) u =   (a) 1.5 (b) 1.0 (c) 2.0 (d) ∞
 m  2m
1/ 2 1/ 2 28. The ratio between the root mean square speed of H2 at 50 K
 E  E
(c) u =   (d) u =   and that of O2 at 800 K is (1996, 1M)
 2m  3m 1
(a) 4 (b) 2 (c) 1 (d)
20. Positive deviation from ideal behaviour takes place because 4
of (2003, 1M) 29. Equal weights of ethane and hydrogen are mixed in an empty
(a) molecular interaction between atom and pV / nRT > 1 container at 25° C. The fraction of the total pressure exerted
(b) molecular interaction between atom and pV / nRT < 1 by hydrogen is (1993, 1M)
(c) finite size of atoms and pV / nRT > 1 (a) 1 : 2 (b) 1 : 1 (c) 1 : 16 (d) 15 : 16
(d) finite size of atoms and pV / nRT < 1 30. At constant volume, for a fixed number of moles of a gas the
21. Which of the following volume (V ) temperature (T ) plots pressure of the gas increases with rise of temperature due to
represents the behaviour of one mole of an ideal gas at the (a) increase in average molecular speed (1992, 1M)
atmospheric pressure? (2002, 3M) (b) increase rate of collisions amongst molecules
(a) V(L) (38.8 L, (b) V(L) (c) increase in molecular attraction
373 K) (28.6 L, (d) decrease in mean free path
373 K)
(22.4 L, (20.4 L,
273 K) 273 K) 31. According to kinetic theory of gases, for a diatomic molecule
(1991, 1M)
T(K) T(K) (a) the pressure exerted by the gas is proportional to mean
(c) V(L) (d) V(L) velocity of the molecule
(30.6 L,
373 K) (b) the pressure exerted by the gas is proportional to the root
(22.4 L, (22.4 L,
273 K) (14.2 L,
mean velocity of the molecule
273 K)
373 K) (c) the root mean square velocity of the molecule is inversely
proportional to the temperature
T(K) T(K)
(d) the mean translational kinetic energy of the molecule is
22. The root mean square velocity of an ideal gas at constant proportional to the absolute temperature
pressure varies with density (d ) as (2001, S, 1M) 32. The rate of diffusion of methane at a given temperature is
(a) d 2 (b) d (c) d (d) 1 / d twice that of a gas X. The molecular weight of X is
(1990, 1M)
23. The compressibility of a gas is less than unity at STP.
Therefore, (a) 64.0 (b) 32.0 (c) 4.0 (d) 8.0
(a) Vm > 22.4 L (b) Vm < 22.4 L (2000, 1M) 33. The density of neon will be highest at (1990, 1M)
(c) Vm = 22.4 L (d) Vm = 44.8 L (a) STP (b) 0° C, 2 atm
24. The rms velocity of hydrogen is 7 times the rms velocity of (c) 273° C, 1 atm (d) 273° C, 2 atm
nitrogen. If T is the temperature of the gas (2000, 1M) 34. The value of van der Waals’ constant a for the gases O2 , N2 ,
(a) T (H2 ) = T (N2 ) (b) T (H2 ) > T (N2 ) NH3 and CH4 are 1.360, 1.390, 4.170 and 2.253L2 atm mol −2
(c) T (H2 ) < T (N2 ) (d) T (H2 ) = 7 T (N2 ) respectively. The gas which can most easily be liquefied is
(a) O2 (b) N2 (c) NH3 (d) CH4
70 States of Matter

35. A bottle of dry ammonia and a bottle of dry hydrogen Objective Questions II
chloride connected through a long tube are opened
simultaneously at both ends the white ammonium chloride
(One or more than one correct option)
ring first formed will be (1988, 1M) 45. Which of the following statement(s) is(are) correct regarding
(a) at the centre of the tube the root mean square speed (U rms ) and average translational
(b) near the hydrogen chloride bottle kinetic energy ( Eav ) of a molecule in a gas at equilibrium?
(2019 Adv.)
(c) near the ammonia bottle
(a) Urms is inversely proportional to the square root of its
(d) throughout the length of the tube molecular mass
36. In van der Waals’ equation of state for a non-ideal gas, the (b) Urms is doubled when its temperature is increased four times
term that accounts for intermolecular forces is (1988, 1M) (c) Eav is doubled when its temperature is increased four times
 a
(a) (V − b ) (b) RT (c)  p + 2  (d) ( RT )−1 (d) Eav at a given temperature does not depend on its
 V  molecular mass
37. The average velocity of an ideal gas molecule at 27° C is 46. One mole of a monoatomic real gas satisfies the equation
0.3 m/s. The average velocity at 927° C will be (1986, 1M) p(V − b)= RT where, b is a constant. The relationship of
(a) 0.6 m/s (b) 0.3 m/s (c) 0.9 m/s (d) 3.0 m/s interatomic potential V(r) and interatomic distance r for gas is
given by (2015 Adv.)
38. Rate of diffusion of a gas is (1985, 1M)
(a) directly proportional to its density V(r) V(r)
(b) directly proportional to its molecular weight (a) 0 (b) 0
r r
(c) directly proportional to the square root of its molecular weight
(d) inversely proportional to the square root of its
molecular weight V(r) V(r)
39. Equal weights of methane and hydrogen are mixed in an (c) 0 (d) 0
empty container at 25° C. The fraction of the total pressure r r
exerted by hydrogen is (1984, 1M)
1 8 1 16 47. According to kinetic theory of gases
(a) (b) (c) (d) (2011)
2 9 9 17 (a) collisions are always elastic
40. When an ideal gas undergoes unrestrained expansion, no (b) heavier molecules transfer more momentum to the wall
cooling occurs because the molecules (1984, 1M) of the container
(a) are above the inversion temperature (c) only a small number of molecules have very high velocity
(b) exert no attractive forces on each other (d) between collisions, the molecules move in straight lines
(c) do work equal to loss in kinetic energy with constant velocities
(d) collide without loss of energy 48. A gas described by van der Waals’ equation (2008, 4M)
41. Helium atom is two times heavier than a hydrogen molecule. (a) behaves similar to an ideal gas in the limit of large molar
At 298 K, the average kinetic energy of a helium atom is volumes
(a) two times that of a hydrogen molecule (1982, 1M) (b) behaves similar to an ideal gas in the limit of large pressures
(b) same as that of a hydrogen molecule (c) is characterised by van der Waals’ coefficients that are
(c) four times that of a hydrogen molecule dependent on the identity of the gas but are independent
(d) half that of a hydrogen molecule of the temperature
(d) has the pressure that is lower than the pressure exerted
42. Equal weights of methane and oxygen are mixed in an empty by the same gas behaving ideally
container at 25°C. The fraction of the total pressure exerted
49. If a gas is expanded at constant temperature (1986, 1M)
by oxygen is (1981, 1M)
1 1 2 1 273 (a) the pressure decreases
(a) (b) (c) (d) × (b) the kinetic energy of the molecules remains the same
3 2 3 3 298 (c) the kinetic energy of the molecules decreases
43. The temperature at which a real gas obeys the ideal gas laws (d) the number of molecules of the gas increases
over a wide range of pressure is (1981, 1M)
(a) critical temperature (b) Boyle temperature Numerical Answer Type Questions
(c) inversion temperature (d) reduced temperature 50. A spherical balloon of radius 3 cm containing helium gas has a
44. The ratio of root mean square velocity to average velocity of pressure of 48 × 10−3 bar. At the same temperature, the
a gas molecule at a particular temperature is (1981, 1M) pressure, of a spherical balloon of radius 12 cm containing the
(a) 1.085 : 1 (b) 1 : 1.086 (c) 2 : 1.086 (d) 1.086 : 2 same amount of gas will be ............ × 10−6 bar.
(2020 Main, 6 Sep I)
 States of Matter 71

51. A closed tank has two compartments A and B, both filled with 54. The experimental value of d is found to be smaller than the
oxygen (assumed to be ideal gas). The partition separating the estimate obtained using Graham’s law. This is due to
two compartments is fixed and is a perfect heat insulator (Fig. (a) larger mean free path for X as a compared of that of Y
1). If the old partition is replaced by a new partition which can (b) larger mean free path for Y as compared to that of X
slide and conduct heat but does not allow the gas to leak (c) increased collision frequency of Y with the inert gas as
across (Fig. 2), the volume (in m3 ) of the compartment A after compared to that of X with the inert gas
the system attains equilibrium is ____. (d) increased collision frequency of X with the inert gas as
compared to that of Y with the inert gas
1 m3, 5 bar
3 m3, 1 bar, 300 K
55. The value of d in cm (shown in the figure), as estimated from
400 K
B Graham’s law, is
A
(a) 8 (b) 12 (c) 16 (d) 20
Fig. 1 Match the Column
56. Match the gases under specified conditions listed in
A B Column I with their properties/laws in Column II.
Column I Column II
Fig. 2 (2018 Adv.) A. Hydrogen gas ( p = 200 atm, p. compressibility
T = 273 K) factor ≠ 1
Assertion and Reason
B. Hydrogen gas ( p ~ 0, T = 273 K) q. attractive forces
Read the following questions and answer as per the direction given are dominant
below : C. CO2 ( p = 1 atm, T = 273 K) r. pV = nRT
(a) Statement I is correct; Statement II is correct; Statement
II is the correct explanation of Statement I D. Real gas with very large molar s. p (V − nb ) = nRT
volume
(b) Statement I is correct; Statement II is correct; Statement
II is not the correct explanation of Statement I (2007, 6M)

(c) Statement I is correct; Statement II is incorrect Fill in the Blanks

(d) Statement I is incorrect; Statement II is correct 57. The absolute temperature of an ideal gas is …… to/than the
52. Statement I The pressure of a fixed amount of an ideal gas is average kinetic energy of the gas molecules. (1997, 1M)
proportional to its temperature. 58. 8 g each of oxygen and hydrogen at 27°C will have the total
Statement II Frequency of collisions and their impact both kinetic energy in the ratio of …… . (1989, 1M)

increase in proportion to the square root of temperature. 59. The value of pV for 5.6 L of an ideal gas is ......... RT, at NTP.
(2000) (1987, 1M)

53. Statement I The value of van der Waals’ constant ‘a’ is 60. The rate of diffusion of a gas is .......... proportional to both
larger for ammonia than for nitrogen. .......... and square root of molecular mass. (1986, 1M)
61. C p − CV for an ideal gas is ……
Statement II Hydrogen bonding is present in ammonia. (1984, 1M)
(1998) 62. The total energy of one mole of an ideal monoatomic gas at
27°C is …… cal. (1984, 1M)
Passage Based Questions
X and Y are two L = 24 cm
True / False
volatile liquids with 63. A mixture of ideal gases is cooled up to liquid helium
molar weights of temperature (4.22 K) to form an ideal solution. (1996, 1M)
10 g mol −1 and 40 g  n2a
64. In the van der Waals’ equation,  p + 2  (V − nb ) = nRT
mol −1 respectively. Cotton wool d Initial formation Cotton wool  V 
of the product soaked in Y
Two cotton plugs, one soaked in X the constant ‘a’ reflects the actual volume of the gas
soaked in X and the molecules. (1993, 1M)
other soaked in Y, are simultaneously placed at the ends of a tube of 65. A gas in a closed container will exert much higher pressure
length L = 24 cm, as shown in the figure. due to gravity at the bottom than at the top. (1985, 1/2 M)
The tube is filled with an inert gas at 1 atm pressure and a 66. Kinetic energy of a molecule is zero at 0°C. (1985, 1/2 M)
temperature of 300 K. Vapours of X and Y react to form a product
which is first observed at a distance d cm from the plug soaked in X. Integer Answer Type Questions
Take X and Y to have equal molecular diameters and assume ideal
behaviour for the inert gas and the two vapours. (2014 Adv.)
67. The diffusion coefficient of an ideal gas is proportional to its
mean free path and mean speed. The absolute temperature of
72 States of Matter

an ideal gas is increased 4 times and its pressure is increased 2 77. Using van der Waals’ equation, calculate the constant a when
times. As a result, the diffusion coefficient of this gas two moles of a gas confined in a four litre flask exert a
increases x times. The value of x is ... (2016 Adv.) pressure of 11.0 atm at a temperature of 300 K. The value of b
68. A closed vessel with rigid walls contains 1 mole of 238
92 Uand 1
is 0.05 L mol –1 . (1998, 4M)

mole of air at 298 K. Considering complete decay of 238 92 U to

78. An evacuated glass vessel weighs 50.0 g when empty 148.0 g
206
Pb, the ratio of the final pressure to the initial pressure of when filled with a liquid of density 0.98 g mL–1 and 50.5 g
82
the system at 298 K is (2015 Adv.)
when filled with an ideal gas at 760 mm Hg at 300 K.
Determine the molar mass of the gas. (1998, 3M)
69. If the value of Avogadro number is 6.023 × 10 mol −1 and
23
79. A mixture of ideal gases is cooled up to liquid helium
the value of Boltzmann constant is 1.380 × 10−23 JK −1 , then
temperature (4.22 K) to form an ideal solution. Is this
the number of significant digits in the calculated value of the
universal gas constant is (2014 Adv.)
statement true or false ? Justify your answer in not more than
two lines. (1996, 1M)
70. To an evacuated vessel with movable piston under external
pressure of 1 atm, 0.1 mole of He and 1.0 mole of an unknown 80. The composition of the equilibrium mixture (Cl 2 s 2Cl)
compound (vapour pressure 0.68 atm at 0° C ) are introduced. which is attained at 1200° C, is determined by measuring the
Considering the ideal gas behaviour, the total volume (in rate of effusion through a pin-hole. It is observed that at
litre) of the gases at 0° C is close to (2011) 1.80 mm Hg pressure, the mixture effuses 1.16 times as fast
as krypton effuses under the same conditions. Calculate the
Subjective Questions fraction of chlorine molecules dissociated into atoms (atomic
weight of Kr = 84) (1995, 4M)
71. At 400 K, the root mean square (rms) speed of a gas X
(molecular weight = 40) is equal to the most probable speed of 81. A mixture of ethane (C2 H6 ) and ethene (C2 H4 ) occupies 40 L
gas Y at 60 K. The molecular weight of the gas Y is (2009) at 1.00 atm and at 400 K. The mixture reacts completely with
72. The average velocity of gas molecules is 400 m s − 1 , find the 130 g of O2 to produce CO2 and H2 O. Assuming ideal gas
rms velocity of the gas. (2003, 2M) behaviour, calculate the mole fractions of C2 H4 and C2 H6 in
73. The density of the vapour of a substance at 1 atm pressure and the mixture. (1995, 4M)

500 K is 0.36 kg m–3 . The vapour effuses through a small hole 82. An LPG (liquefied petroleum gas) cylinder weighs 14.8 kg
at a rate of 1.33 times faster than oxygen under the same when empty. When full it weighs 29.0 kg and shows a pressure
condition. of 2.5 atm. In the course of use at 27° C, the weight of the full
(i) Determine, (a) molecular weight (b) molar volume cylinder reduces to 23.2 kg. Find out the volume of the gas in
(c) compression factor (Z) of the vapour and (d) which cubic metres used up at the normal usage conditions, and the
forces among the gas molecules are dominating, the final pressure inside the cylinder. Assume LPG to the n-butane
attractive or the repulsive? with normal boiling point of 0° C. (1994, 3M)
(ii) If the vapour behaves ideally at 1000 K, determine the 83. A 4 : 1 molar mixture of He and CH4 is contained in a vessel
average translational kinetic energy of a molecule.
(2002, 5M) at 20 bar pressure. Due to a hole in the vessel, the gas mixture
leaks out. What is the composition of the mixture effusing out
74. The compression factor (compressibility factor) for one mole initially? (1994, 2M)
of a van der Waals’ gas at 0° C and 100 atm pressure is found to
be 0.5. Assuming that the volume of a gas molecule is negligible, 84. A gas bulb of 1 L capacity contains 2.0 × 1021 molecules of
calculate the van der Waals’ constant ‘a’. (2001, 5M) nitrogen exerting a pressure of 7.57 × 103 Nm–2 . Calculate
75. Calculate the pressure exerted by one mole of CO2 gas at the root mean square (rms) speed and the temperature of the
273 K if the van der Waals’ constant a = 3.592 dm 6 atm gas molecules. If the ratio of the most probable speed to root
mol −2 . Assume that the volume occupied by CO2 molecules is mean square speed is 0.82, calculate the most probable speed
negligible. (2000) for these molecules at this temperature. (1993, 4M)

76. (i) One mole of nitrogen gas at 0.8 atm takes 38 s to diffuse 85. At room temperature, the following reaction proceed nearly
through a pin-hole, whereas one mole of an unknown to completion. 2NO + O2 → 2NO2 → N2 O4
compound of xenon with fluorine at 1.6 atm takes 57 s to The dimer, N2 O4 , solidifies at 262 K. A 250 mL flask and a
diffuse through the same hole. Calculate the molecular 100 mL flask are separated by a stopcock. At 300 K, the nitric
formula of the compound. oxide in the larger flask exerts a pressure of 1.053 atm and the
(ii) The pressure exerted by 12 g of an ideal gas at smaller one contains oxygen at 0.789 atm.
temperature t ° C in a vessel of volume V litre is one atm. The gases are mixed by opening the stopcock and after the
When the temperature is increased by 10°C at the same end of the reaction the flasks are cooled to 220 K. Neglecting
volume, the pressure increases by 10%. Calculate the the vapour pressure of the dimer, find out the pressure and
temperature t and volume V. composition of the gas remaining at 220 K. (Assume the
(Molecular weight of the gas = 120) (1999, 5M) gases to behave ideally). (1992, 4M)
 States of Matter 73

86. At 27° C, hydrogen is leaked through a tiny hole into a vessel pressure becomes 1.5 atm. Assuming ideal gas behaviour,
for 20 min. Another unknown gas at the same temperature calculate the ratio of the molecular weights M A : M B .
and pressure as that of hydrogen is leaked through same hole (1983, 2M)
for 20 min. After the effusion of the gases the mixture exerts a 94. At room temperature, ammonia gas at 1 atm pressure and
pressure of 6 atm. The hydrogen content of the mixture is 0.7 hydrogen chloride gas at p atm pressure are allowed to effuse
mole. If the volume of the container is 3 L. What is the through identical pin holes from opposite ends of a glass tube
molecular weight of the unknown gas? (1992, 3M) of one metre length and of uniform cross-section.
87. Calculate the volume occupied by 5.0 g of acetylene gas at Ammonium chloride is first formed at a distance of 60 cm
50° C and 740 mm pressure. (1991, 2M) from the end through which HCl gas is sent in. What is the
value of p ? (1982, 4M)
88. The average velocity at T1 K and the most probable at T2 K of
95. Calculate the average kinetic energy, in joule per molecule in
CO2 gas is 9.0 × 104 cm s –1 . Calculate the value of T1 and T2
8.0 g of methane at 27°C. (1982, 2M)
(1990, 4M)
96. The pressure in a bulb dropped from 2000 to 1500 mm of
89. A spherical balloon of 21 cm diameter is to be filled up with mercury in 47 min when the contained oxygen leaked through
hydrogen at NTP from a cylinder containing the gas at 20 atm a small hole. The bulb was then evacuated. A mixture of
at 27° C. If the cylinder can hold 2.82 L of water, calculate the oxygen and another gas of molecular weight 79 in the molar
number of balloons that can be filled up. (1987, 5M) ratio of 1 : 1 at a total pressure of 4000 mm of mercury was
90. Calculate the root mean square velocity of ozone kept in a closed introduced. Find the molar ratio of the two gases remaining in
vessel at 20° C and 82 cm mercury pressure. (1985, 2M) the bulb after a period of 74 min. (1981, 3M)

91. Give reasons for the following in one or two sentences. 97. A hydrocarbon contains 10.5 g of carbon per gram of
(i) Equal volumes of gases contain equal number of moles. hydrogen. 1 L of the vapour of the hydrocarbon at 127°C and
(1984, 1M) 1 atm pressure weighs 2.8 g. Find the molecular formula of
(ii) A bottle of liquor ammonia should be cooled before the hydrocarbon. (1980, 3M)
opening the stopper. (1983, 1M) 98. 3.7 g of a gas at 25°C occupied the same volume as 0.184 g of
92. Oxygen is present in one litre flask at a pressure of 7.6 × 10−10 hydrogen at 17°C and at the same pressure. What is the
molecular weight of the gas ? (1979, 2M)
mm Hg. Calculate the number of oxygen molecules in the
flask at 0° C. (1983, 2M)
99. 4.215 g of a metallic carbonate was heated in a hard glass
tube, the CO2 evolved was found to measure 1336 mL at
93. When 2 g of a gas A is introduced into an evacuated flask kept 27°C and 700 mm of Hg pressure. What is the equivalent
at 25° C, the pressure is found to be one atmosphere. If 3 g of weight of the metal ? (1979, 3M)
another gas B is then added to the same flask, the total
100. Calculate the density of NH3 at 30°C and 5 atm pressure.
(1978, 2M)

Topic 2 Liquid State

Objective Questions I (Only one correct option) 2. At 100°C and 1 atm if the density of the liquid water is
1. The qualitative sketches I, II and III given below show the 1.0 g cm–3 and that of water vapour is 0.0006 g cm−3 , then the
variation of surface tension with molar concentration of three volume occupied by water molecules in 1 L of steam at this
different aqueous solutions of KCl, CH3 OH and temperature is (2000, 1M)
− +
CH3 (CH2 )11 OSO3 Na at room temperature. (2016 Adv.) (a) 6 cm 3 (b) 60 cm 3
(c) 0.6 cm 3 (d) 0.06 cm 3
Surface tension

Surface tension

Surface tension

I II III
3. The critical temperature of water is higher than that of O2
because the H2O molecule has (1997)
(a) fewer electrons than O2
(b) two covalent bonds
Concentration Concentration Concentration (c) V-shape
(d) dipole moment
The correct assignment of the sketches is
I II III 4. A liquid is in equilibrium with its vapour at it’s boiling point.
(a) KCl CH3OH CH3 (CH2 )11 OSO−3 Na + On the average, the molecules in the two phases have equal
(a) inter-molecular forces
(b) CH3 (CH2 )11 OSO3− +
Na CH3OH KCl
(b) potential energy
(c) KCl CH3 (CH2 )11 OSO−3 Na + CH3OH (c) kinetic energy
(d) CH3OH KCl CH3 (CH2 )11 OSO3− Na + (d) total energy
 Answers
Topic 1
1. (b) 2. (c) 3. (c) 4. (b) 56. (A → p,s; B → r; C→ p, q; D → r)
5. (a) 6. (a) 7. (c) 8. (b) 57. (less) 58. (1 : 16) 59. (0.25)
9. (b) 10. (a) 11. (b) 12. (b) 60. (inversely, time) 61. (R) 62. (900)
13. (b) 14. (c) 15. (c) 16. (b) 63. (F) 64. (F) 65. (F) 66. (F)
17. (b) 18. (a) 19. (a) 20. (a) 67. (4) 68. (9) 69. (4) 70. (7 L)
21. (c) 22. (d) 23. (b) 24. (c) 71. (4) 72. 435 ms −1 74. (1.25) 75. (0.99 atm)
25. (c) 26. (c) 27. (b) 28. (c) 77. (6.46) 78. (123 g mol −1) 80. (0.14)
29. (d) 30. (a) 31. (d) 32. (a) 82. (2.46 m 3) 83. (8:1) 84. (407 ms −1) 85. (0.221 atm)
86. (1020 g mol −1) 87. (5.23 L) 89. (10)
33. (b) 34. (c) 35. (b) 36. (c)
90. (390.2 ms −1) 92. (2.7 × 1010 g mol −1)
37. (a) 38. (d) 39. (b) 40. (b)
93. (1 : 3) 94. (2.20 atm) 95. (6.2 × 10 −21 J/molecule)
41. (b) 42. (a) 43. (b) 44. (a)
98. (41.32 g) 99. (12.15) 100. (3.42 gL −1)
45. (a, b, d) 46. (c) 47. (a) 48. (a,c)
49. (a,b) 50. (750) 51. (2.22) 52. (d) Topic 2
53. (a) 54. (d) 55. (c) 1. (d) 2. (c) 3. (d) 4. (c)

Hints & Solutions

Topic 1 Gaseous State Heat capacity at constant volume,
1. Fraction of molecules vs velocity graph is Maxwell distribution dH
nCp =
curve. dT
This curve is slightly unsymmetrical as shown below. dH = nC p dT [n = 1mol]
Most probable speed (vp) dH = 1 × C p × dT
In mathematically term,
Average speed (vavg)
Fraction of molecules

H = f (T ) [QC p = constant]
Root-mean-square speed (vrms) Hence, H depends on function of temperature
(b) Compressibility factor (Z ) describe the deviation of real gas
from ideal gas behaviour.
pV
Z= …(i)
RT
For ideal gas,
vp vavg vrms pV = nRT [n = 1mol]
Speed v
pV = RT …(ii)
The ratio of most probable, the average and the root mean square Put in the value of pV from Eq. (ii) to Eq. (i)
speeds for this graph is 1 : 1.128 : 1.224 RT
Z= =1
But the graph in question is completly symmetrical. Therefore, RT
the most probable and the average speed will be same here but Compressibility factor is 1 for ideal gas then option (b) is
root mean square speed will be greater than average speed. So, incorrect.
the correct ratio is 1 : 1: 1224
. .
(c) For ideal gas,
2. Statements (A), (C) and (D) are true whereas (B) is false. C p − CV = nR (n = 1mol)
(A) For 1 mole, U = internal energy and H = enthalpy. C p − CV = R
Heat capacity at constant volume. It is correct statement.
dU
nCV = (d) ∆U = CV dT
dt dU
nCV =
dU = nCV dT (n = 1 mol) dT
dU = 1 × CV × dT (QCV = constant) dU = nCV dT (n = 1mol)
U = f (T ) (Function of temperature) dU = CV dT
U depends on temperature. It is also correct.
 States of Matter 75

3. pV
Key Idea From kinetic gas equation, As, Z=
RT
2RT
Most probable velocity (vmp ) = so, Z =1+
pb
⇒ y = c + mx
M RT
where, R = gas constant, T = temperature, The plot of z vs p is found to be
M = molecular mass
b
2RT T slope =
vmp = , i.e. vmp ∝ RT
M M Z

Gas M T ( K) T/M
H2 2 300 300 / 2 = 150 …III (Highest)
p
N2 28 300 300 / 28 = 10.71 …I (Lowest)
The gas with high value of b will be steepest as slope is directly
proportional to b. b is the van der Waals’ constant and is equal to
O2 32 400 400 / 32 = 12.5 … II
four times the actual volume of the gas molecules. Xe gas
So, possess the largest atomic volume among the given noble gases
(Ne, Kr, Ar). Hence, it gives the steepest increase in the plot of Z
I. corresponds to vmp of N2 (300 K)
(compression factor) vsp.
II. corresponds to vmp of O2 (400 K)
III. corresponds to vmp of H2 (300 K) 6. Critical temperature is the temperature of a gas above which it
cannot be liquefied what ever high the pressure may be. The
4. For 1 mole of a real gas, the van der Waals’ equation is kinetic energy of gas molecules above this temperature is
sufficient enough to overcome the attractive forces. It is
 a
 p + 2  (V − b) = RT represented as Tc.
 V  8a
Tc =
The constant ‘a’ measures the intermolecular force of attraction 27Rb
of gas molecules and the constant ‘b’ measures the volume 8 × 13
.
correction by gas molecules after a perfectly inelastic binary For Ar, Tc = = 0.0144
27 × 8.314 × 3.2
collision of gas molecules.
8 × 0.2
For gas A and gas C given value of ‘b’ is For Ne, Tc = = 0.0041
0.05196 dm3 mol −1. Here, 27 × 8.314 × 17
.
8 × 51
.
a ∝ intermolecular force of attraction For Kr, Tc = = 018
.
∝ compressibility ∝ real nature 27 × 8.314 × 1.0
8 × 4.1
∝
1 For Xe, Tc = = 0.02
volume occupied 27 × 8.314 × 5.0
The value of Tc is highest for Kr (Krypton).
Value of a/(kPa dm6 mol −1) for gas A (642.32) > gas C (431.91)
So, gas C will occupy more volume than gas A. Similarly, for a 7. In isothermal expansion, pVm = K (constant)
given value of a say 155.21 kPa dm6 mol −1 for gas B and gas D This relation is plotted in graph ‘C’
1 K
∝ intermolecular force of attraction Likewise, p=
b Vm
∝ compressibility ∝ real nature This relation is plotted in graph “ A”.
1
∝ Thus, graph B and D are incorrect.
volume accupied For them the correct graphs are:
b/(dm 3 mol −1) for gas B (0.04136) < Gas D (0.4382)
So, gas B will be more compressible than gas D.
p for graph B and U for graph D
5. Noble gases such as Ne, Ar, Xe and Kr found to deviate from
ideal gas behaviour.
Xe gas will exhibit steepest increase in plot of Z vs p. Vm Vm
Equation of state is given as:
RT 8. Given, temperature (T1 ) = 27° C = 273 + 27 = 300 K
p= ⇒ p(V − b) = RT
(V − b) Volume of vessel = constant
pV − pb = RT ⇒ pV = RT + pb Pressure in vessel = constant
pV pb 2 3
=1+ Volume of air reduced by so the remaining volume of air is .
RT RT 5 5
76 States of Matter

Let at T1 the volume of air inside the vessel is n so at T2 the pf V

3 After mixing, number of moles in left chamber =
volume of air will be n. RT1
5 pf V
Now, as p and V are constant, so Number of moles in right chamber =
RT2
3
n ⋅T1 = n T2 ...(i) pf V pf V pf V  1 1
5 Total number of moles = + =  + 
Putting the value of T1 in equation (i) we get, RT1 RT2 R  T1 T2 
3 As total number of moles remains constant.
n × 300 = n × T2
5 2 piV pf V pf V  T2 
Hence, = + ⇒ pf = 2 pi  
5 RT1 RT1 RT2  T1 + T2 
or T2 = 300 × = 500 K
3
13. PLAN To solve this problem, the stepwise approach required, i.e.
9. Given, ZA = 3ZB (i) Write the van der Waals’ equation, then apply the condition that
pV at low pressure, volume become high,
Compressibility factor (Z) = [for real gases]
nRT i.e. V − b~−V
On substituting in equation (i), we get (ii) Now calculate the value of compressibility factor (Z ).
pAVA 3p V [ Z = pV / RT ]
= B B …(ii) According to van der Waals’ equation,
nARTA nB RTB
 a
Also, it is given that  p + 2  (V − b) = RT
 V 
VA = 2VB , nA = nB and TA = TB
∴ Eq. (ii) becomes  a
At low pressure,  p + 2  V = RT
pA × 2VB 3 pBVB  V 
= a a
nB RTB nB RTB ⇒ pV + = RT or pV = RT −
V V
⇒ 2 pA = 3 pB
pV a
10. 2NaHCO3 + H2C2O4 → 2CO2 + Na 2C4O4 + H2O Divide both side by RT, =1−
RT RTV
2 mol 1 mol 2 mol
⇒ In the reaction, number of mole of CO2 produced. 2RT
14. C * = Most probable speed =
pV 1 bar × 0.25 × 10−3 L M
n= =
RT 0.082 L atm K−1mol −1 × 298.15 K 8RT
C = Average speed =
−5
= 1.02 × 10 mol πM
Weight of NaHCO3 C = Root square speed corrected as root means square speed, i.e.
Number of mole of NaHCO3 =
Molecular mass of NaHCO3 3RT
rms = and as we know C* < C < C
∴ . × 10−5 × 84 × 103 mg
wNaHCO3 = 102 M
= 0.856 mg * 4 3
C : C : C =1 : : = 1 : 1.128 : 1.225
0.856 p 2
⇒ NaHCO 3 % = × 100 = 8.56%
10 NOTE
11. From the ideal gas equation, As no option correspond to root square speed, it is understood as
misprint. It should be root mean square speed.
pV = ΣnRT ...(i)
Given: p = 200 Pa, V = 10m3 , T = 1000 K 15. The van der Waals’ equation of state is
nA = 0.5 moles, nB = x moles  n2a
 p + 2  (V − nb) = nRT
On substituting the given values in equation (i), we get  V 
200 × 10 = (nA + nB ) × R × 1000
For one mole and when b = 0, the above equation condenses to
200 × 10
0.5 + x =  a
R × 1000  p + 2  V = RT
 V 
1 2 2 1 4−R
+x= = − = a
2 R R 2 2R ⇒ pV = RT − …(i)
V
12. Initially, 1
pV Eq. (i) is a straight equation between pV and whose slope is ‘
Number of moles of gases in each container = i V
RT1 − a’. Equating with slope of the straight line given in the graph.
piV 20.1 − 21.6
Total number of moles of gases in both containers = 2 −a= = − 1.5 ⇒ a = 1.5
RT1 3− 2
 States of Matter 77

16. In the van der Waals’ equation V

27. Compressibility factor (Z ) = =1
Videal
 n a
2
 p + 2  (V − nb) = nRT Q For ideal gas V = Videal
 V 
3RT
n2a 28. Expression of rms is, urms =
The additional factor in pressure, i.e. corrects for M
V2
intermolecular force while b corrects for molecular volume. 3R × 50
urms (H2 at 50 K) 2
17. Option (b) is incorrect statement because at high pressure slope ⇒ =
urms (O2 at 800 K) 3R × 800
of the line will change from negative to positive.
32
r(He) 16
18. = =2 :1 50 32
r(CH4 ) 4 = × =1
2 800
3
19. Kinetic energy (E ) = kT 29. Let x g of each gas is mixed.
2 x
Mole of ethane =
3kT 2E 30
RMS speed (u) = ⇒ u=
m m x
Mole of hydrogen =
2
20. Positive deviation corresponds to Z > 1 x
pV pV 15
Q Z= , for positive deviation, > 1. Mole fraction of hydrogen = 2 =
nRT nRT x x 16
+
21. Option (b) and (d) are ruled out on the basis that at the initial 2 30
point of 273 K, 1 atm, for 1.0 mole volume must be 22.4 L, and it Partial pressure of H2
⇒ = Mole fraction of hydrogen
should increase with rise in temperature. Total pressure
Option (a) is ruled out on the basis that initial and final points are = 15 : 16
not connected by the ideal gas equation V ∝ T , i.e. V /T do not 8RT
have the same value at the two points. 30. Average speed =
In option (c), at the initial point, the volume is 22.4 L as required πM
by ideal gas equation and (V /T ) have the same value at both i.e. at constant volume, for a fixed mass, increasing temperature
initial and final points. increases average speeds and molecules collide more frequently
3RT to the wall of container leading to increase in gas pressure.
22. Root mean square velocity (urms ) =
M 31. The mean translational kinetic energy (∈) of an ideal gas is
3
Also, p ⋅ M = dRT ∈= k BT ; T = Absolute temperature, i.e. ∈ ∝ T
2
Substituting for RT / M in urms expression gives,
rCH 4 MX
urms =
3p
⇒ urms ∝
1 32. =2= ⇒ M X = 64
d rX 16
d
w
V 33. The ideal gas equation, pV = nRT = RT
23. Compressibility factor (Z ) = < 1(given) M
Vid  w
⇒ V < 22.4 L ⇒ pM =   RT = dRT (d = density)
V 
Q Vid (1 mol ) = 22.4 L at STP pM
⇒ d=
3RT RT
24. Root mean square speed urms =
M i.e. density will be greater at low temperature and high pressure.
urms (H2 ) T (H2 ) 28 14T (H2 ) 34. The ease of liquefication of a gas depends on their intermolecular
⇒ = 7= × ⇒ 7=
urms (N2 ) 2 T (N2 ) T (N2 ) force of attraction which in turn is measured in terms of van der
⇒ T (N2 ) = 2T (H2 ) i.e. T (H2 ) < T (N2 ) Waals’ constant a. Hence, higher the value of a, greater the
intermolecular force of attraction, easier the liquefication.
25. At high temperature and low pressure, the gas volume is
In the present case, NH3 has highest a, can most easily be
infinitely large and both intermolecular force as well as
liquefied.
molecular volume can be ignored. Under this condition
postulates of kinetic theory applies appropriately and gas 35. HCl will diffuse at slower rate than ammonia because rate of
approaches ideal behaviour. 1
effusion ∝ .
26. Rate of effusion ∝ pi ; pi = Partial pressure of ith component M
1 Therefore, ammonia will travel more distance than HCl in the
∝ same time interval and the two gas will first meet nearer to HCl
M
end.
78 States of Matter

36. In van der Waals’ equation of state 44. The two types of speeds are defined as;
 a 3RT
 p + 2  (V − b) = RT (For 1 mole) Root mean square speed (urms ) =
 V  M
The first factor ( p + a/V 2 ) correct for intermolecular force while 8RT
Average speed (uav ) =
the second term (V − b) correct for molecular volume. πM
8RT For the same gas, at a given temperature, M and T are same,
37. Expression for average velocity is uav = therefore
πM
urms 3RT 8RT
For the same gas but at different temperature = :
uav M πM
uavg (T1 ) T1 300 1
= = = 8
uavg (T2 ) T2 1200 2 = 3: = 3 : 2.54 = 1.085 : 1
π
⇒ uav (927° C) = 2 × uav (27° C) = 0.6 ms−1 45. The explanation of given statements are as follows:
1 (a) Urms is inversely proportional to the square root of its
38. Rate of effusion ∝ ,
M molecular mass.
3RT
39. Let x grams of each hydrogen and methane are mixed, Urms =
x M
Moles of H2 = Hence, option (a) is correct.
2
x (b) When temperature is increased four times then Urms become
Moles of CH4 = doubled.
16
x 3R
Urms = × 4T
2 8 M
⇒ Mole fraction of H2 = =
x x 9 3RT
+ Urms = 2 ×
2 16 M
Partial pressure of H2 8
⇒ = Mole fraction of H2 = Hence, option (b) is correct.
Total pressure 9
(c) and (d) Eav is directly proportional to temperature but
40. According to postulates of kinetic theory, there is no does not depends on its molecular mass at a given
intermolecular attractions or repulsions between the molecules 3
temperature as Eav = KT . If temperature raised four times
of ideal gases. 2
3 than Eav becomes four time multiple.
41. According to kinetic theory, average kinetic energy (E ) = k BT Thus, option (c) is incorrect and option (d) is correct.
2
where, k B is Boltzmann’s constant. Since, it is independent of 46. Equation of state p(V − b) = RT indicates absence of
molar mass, it will be same for He and H2 at a given temperature. intermolecular attraction or repulsion, hence interatomic
potential remains constant on increasing ‘π’ in the beginning. As
42. If x g of both oxygen and methane are mixed then :
the molecules come very close, their electronic and nuclear
x
Mole of oxygen = repulsion increases abruptly.
32
x 47. (a) According to a postulate of kinetic theory of gases, collision
Mole of methane = between the molecules as well as with the wall of container is
16
perfectly elastic in nature.
x
32 1 (b) If a gas molecule of mass m moving with speed u collide to
⇒ Mole fraction of oxygen = = the wall of container, the change in momentum is
x x 3
+ ∆p = – 2mu. Therefore, heavier molecule will transfer more
32 16
momentum to the wall as there will be greater change in
According to law of partial pressure
momentum of the colliding gas molecule. However, this is
Partial pressure of oxygen ( pO 2 ) = Mole fraction × Total pressure not postulated in kinetic theory.
pO 2 1 (c) According to Maxwell-Boltzmann distribution of molecular
⇒ =
p 3 speed, very few molecules have either very high or very low
43. It is the Boyle temperature TB . At Boyle temperature, the first speeds. Most of the molecules moves in a specific,
virial coefficient ( B ) vanishes and real gas approaches ideal intermediate speed range.
behaviour. (d) According to kinetic theory of gases, a gas molecule moves
a in straight line unless it collide with another molecule or to
TB =
Rb the wall of container and change in momentum is observed
only after collision.
Here, a and b are van der Waals’ constants.
 States of Matter 79

48. Option (a) is correct because in the limit of large volume, both 11
or 4 (1+ x ) = 15 − 5x or 4 + 4 x = 15 − 5x or x =
intermolecular force and molecular volume becomes negligible 9
in comparison to volume of gas. 11 20
Hence, new volume of A i.e., (1+ x ) will comes as 1 + = or
Option (b) is wrong statement because in the limit of large 9 9
pressure Z > 1. 2.22.
Option (c) is correct statement. For a van der Waals’ gas, 52. Assertion is incorrect because besides amount, pressure also
van der Waals’ constants a and b are characteristic of a gas, depends on volume. However, reason is correct because both
independent of temperature. frequency of collisions and impact are directly proportional to
Option (d) is wrong statement because Z can be either less or root mean square speed which is proportional to square root of
greater than unity, hence real pressure can be less or greater than absolute temperature
ideal pressure. 53. a is the measure of intermolecular force of attraction. Greater the
intermolecular force of attraction (H-bond in the present case)
49. Pressure is inversely proportional to volume at constant higher the value of a.
temperature, hence (a) is correct.
Average kinetic energy of a gas is directly proportional to 54. X is a lighter gas than Y, hence X has greater molecular speed. Due
absolute temperature, hence (b) is correct. to greater molecular speed of X, it will have smaller mean free path
and greater collision frequency with the incrt gas molecules. As a
Expansion at constant temperature cannot change the number of
result X will take more time to travel a given distance along a
molecules, hence (d) is incorrect.
straight line. Hence X and Y will meet at a distance smaller than one
50. Initial pressure ( p1 ) = 48 × 10−3 bar calculated from Graham’s law.
Final pressure ( p2 ) = …… × 10−6 bar Hence, (d) is the correct choice.
4 55. PLAN This problem can be solved by using the concept of Graham’s law
Initial volume (V1 ) = π (3)3 of diffusion according to which rate of diffusion of non-reactive
3
gases under similar conditions of temperature and pressure are
4
Final volume (V2 ) = π (12)3 inversely proportional to square root of their density.
3 1
Rate of diffusion ∝
According to Boyle’s law p1V1 = p2V2 molar weight of gas
pV
p2 = 1 1 Let distance covered by X is d, then distance covered by Y is
V2 24 – d.
4 If rX and rY are the rate of diffusion of gases X and Y,
48 × 10−3 × π (3)3
3 48 × 10−3 × (3)3 40
p2 = = rX
=
d
= =2
4 (12)3
π (12)3 rY 24 − d 10
3
[Q Rate of diffusion ∝ distance travelled]
48 × 10−3 × 27
= = 0.0277 × 27 × 10−3 = 750 × 10−6 bar d = 48 − 2d
1728
⇒ 3d = 48 ⇒ d = 16 cm
Hence, the correct answer is 750.
Hence, (c) is the correct choice.
51. Given p1 = 5 bar, V1 = 1 m 3, T1 = 400 K
56. A. At p = 200 atm, very high pressure, Z > 1. Also, at such a high
5  n2a
So, n1 = (from pV = nRT )
400 R pressure, the pressure correction factor  2  can be ignored
V 
3
Similarly, p2 = 1 bar, V2 = 3 m 3, T2 = 300 K, n2 = in comparison to p.
300 R
B. At p ~ 0, gas will behave like an ideal gas, pV = nRT .
Let at equilibrium the new volume of A will be (1+ x )
C. CO2 (p = 1atm, T = 273 K), Z < 1.
So, the new volume of B will be (3− x )
D. At very large molar volume, real gas behaves like an
Now, from the ideal gas equation. ideal gas.
p1V1 pV
= 2 2 3
n1RT1 n2RT2 57. Less; E = RT
2
and at equilibrium (due to conduction of heat) 3
p1 p2 58. 1 : 16, KE = nRT . At same temperature, KE (total) ∝ n.
= 2
T1 T2 1
59. 0.25 RT because at NTP, 5.6 L = mole.
V1 V2 4
So, = or V1n2 = V2n1
n1 n2 60. Inversely, time.
After putting the values 61. For an ideal gas, Cp − CV = R
3 5 (3 − x ) 5 3 3
(1+ x ) × = (3 − x ) × or (1+ x ) = 62. At 27°C, E = RT = × 2 × 300 = 900 cal
300 R 400 R 4 2 2
80 States of Matter

63. An ideal gas cannot be liquefied because there exist no 71. Given, urms = umps
intermolecular attraction between the molecules of ideal gas.
3RT 2RT
64. a is the measure of intermolecular force. ⇒ =
M (X ) M (Y )
65. In a close container, gas exert uniform pressure everywhere in 3R × 400 2R × 60
the container. ⇒ = ⇒ M (Y ) = 4
40 M (Y )
3
66. KE = RT where, T is absolute temperature (in Kelvin). uav 8RT 3RT 8
2 72. = : =
urms πM M 3π
67. (DC) Diffusion coefficient ∝ λ (mean free path) ∝ U mean
3π 3 × 3.14
Thus (DC) ∝ λ Umean ⇒ urms = uav = × 400 = 434 ms−1
8 8
RT T
But, λ= ⇒ λ∝ rgas
2 N0 σp p 32
73. = 1.33 =
rO 2 Mgas
8RT
and U mean =
πM (i) (a) Mgas = 18 g mol −1
U mean ∝ T 18
(b) Vm = = 50 L mol −1
0.36
(T )3/ 2
∴ DC ∝ pV 1 × 50
p (c) Z = = = 1.22
RT 0.082 × 500
3/ 2 3/ 2
(DC)2 p  T2   p   4T  (d) Q Z > 1, repulsive force is dominating.
(x ) =  1    =  1   1
(DC)1  p2   T1   2 p1   T1 
3 3
(ii) Ek = k BT = × 1.38 × 10−23 × 1000 J = 2.07 × 10−20 J
 1 2 2
=   (8) = 4
 2
74. In case of negligible molecular volume, b = 0. For 1 mole of gas
68. 92 U
238
→ 82Pb
206
+ 8 2He4 (g ) + 6− 1β 0  a a
 p + 2  V = RT ⇒ pV + = RT
n(gas)[Initial] = 1 (air)  V  V
n(gas)[Final] = 8 (He) + 1(air) = 9 pV a  pV 
⇒ + =1 =Z
 RT 
Q
⇒ At constant temperature and volume; RT VRT
p ∝ n. a ap
⇒ Z+ =1 ⇒ Z+ =1
So,
pf nf 9
= = =9  ZRT  ZR 2T 2
ni 1   RT
pi  p 
69. PLAN This problem can be solved by using the concept involved in ZR 2T 2 (1 − Z ) 0.5 (0.082 × 273)2 (1− 0.5)
calculation of significant figure. ⇒ a= =
p 100
Universal gas constant, R = kN A
a = 1.25 atm L2 mol −2
where, k = Boltzmann constant
and N A = Avogadro’s number 75. In case of negligible molecular volume, b = 0 and
∴ −23
R = 1.380 × 10 × 6.023 × 10 J/Kmol 23 van der Waals’ equation reduces to
= 8.31174 =~ 8.312  n2a
 p + 2  V = nRT
Since, k and N A both have four significant figures, so the value of  V 
R is also rounded off upto 4 significant figures. RT a
⇒ p= − 2 (n =1 mole)
[When number is rounded off, the number of significant figure is V V
reduced, the last digit is increased by 1 if following digits ≥ 5 and 0.082 × 273 3.592
is left as such if following digits is ≤ 4.] = − = 0.99 atm
22.4 (22.4)2
Hence, correct integer is (4).
76. (i) For the same amount of gas being effused
70. Since, the external pressure is 1.0 atm, the gas pressure is also
1.0 atm as piston is movable. Out of this 1.0 atm partial pressure r1 t2 p1 M2 57 0.8 M2
= = ⇒ =
due to unknown compound is 0.68 atm. r2 t1 p2 M1 38 1.6 28
Therefore, partial pressure of He ⇒ M 2 = 252 g mol −1
= 1.00 – 0.68 = 0.32 atm.
Also, one molecule of unknown xenon-fluoride contain only
n(He)RT 0.1 × 0.082 × 273
⇒ Volume = = =7L one Xe atom [M (Xe) = 131], formula of the unknown gas can
p(He) 0.32 be considered to be XeFn.
⇒ Volume of container = Volume of He. ⇒ 131 + 19n = 252; n = 6.3, hence the unknown gas is XeF6.
 States of Matter 81

(ii) For a fixed amount and volume, p ∝ T 82. Weight of butane gas in filled cylinder = 29 − 14.8 kg = 14.2 kg
1 T ⇒ During the course of use, weight of cylinder reduces to 23.2 kg
⇒ = where, T = Kelvin temperature
1.1 T + 10
⇒ Weight of butane gas remaining now = 23.2 − 14.8 = 8.4 kg
⇒ T = 100 K = t + 273 Also, during use, V (cylinder) and T remains same.
⇒ t = − 173° C p1 n1
Therefore, =
nRT  12  0.082 × 100 p2 n2
Volume = =  × = 0.82 L
p  120 1 n   8.4   n w 
⇒ p2 =  2  p1 =   × 2.5 Here, 2 = 2 
 n1   14.2  n1 w1 
77. The van der Waals’ equation is
 n2a = 1.48 atm
 p + 2  (V − nb) = nRT Also, pressure of gas outside the cylinder is 1.0 atm.
 V 
⇒ pV = nRT
V 2  nRT  (4 )2  2 × 0.082 × 300  nRT (14.2 − 8.4 ) × 103 0.082 × 30
⇒ a= 2 
− p = 2 
− 11 ⇒ V = = × L
n V − nb  (2)  4 − 2 (0.05)  p 58 1
= 6.46 atm L2 mol −2 = 2460 L = 2.46 m 3
78. Mass of liquid = 148 − 50 = 98 g rHe nHe M CH 4 4 16
98 83. = = =8
⇒ Volume of liquid = = 100 mL = volume of flask rCH4 n CH4 M He 1 4
0.98 Initial ratio of rates of effusion gives the initial composition of
mass of gas = 50.5 − 50 = 0.50 g mixture effusing out. Therefore, n (He) : n (CH4 ) = 8 : 1
 w
Now applying ideal gas equation : pV =   RT 2 × 1021
M 84. Number of moles = = 0.33 × 10−2
wRT 0.5 × 0.082 × 300 6 × 1023
⇒ M = = = 123 g mol −1 p = 7.57 × 103 Nm −2
pV 1 × 0.1
Now, pV = nRT
79. False, ideal gas cannot be liquefied as there is no intermolecular
pV 7.57 × 103 × 10−3
attraction between the molecules of ideal gas. Hence, there is no ⇒ T = = = 276 K
point of forming ideal solution by cooling ideal gas mixture. nR 0.33 × 10−2 × 8.314
80. If ‘α’ is the degree of dissociation, then at equilibrium 3RT 3 × 8.314 × 276
⇒ urms = = m s−1 = 496 ms−1
Cl 2 r 2Cl M 28 × 10−3
Moles 1 −α 2α Total = 1 + α umps
Also, = 0.82
From diffusion information urms
r(mix) 84 ⇒ umps = 0.82 × urms = 0.82 × 496 ms−1 = 407 ms−1
= 1.16 =
r(Kr) M (mix)
85. First we calculate partial pressure of NO and O2 in the combined
⇒ M (mix) = 62.4 system when no reaction taken place.
71 pV = constant ⇒ p1V1 = p2V2
⇒ M (mix) = = 62.4
1+ α 1.053 × 250
⇒ p2 (NO) = = 0.752 atm
⇒ α = 0.14 350
0.789 × 100
pV 1 × 40 p2 (O2 ) = = 0.225 atm
81. The total moles of gaseous mixture = = 350
RT 0.082 × 400
= 1.22 Now the reaction stoichiometry can be worked out using partial
pressure because in a mixture.
Let the mixture contain x mole of ethane. Therefore, pi ∝ ni
7
C2H6 + O2 → 2CO2 + 3H2O 2NO + O2 → 2NO2 → N2O4
x 2 Initial 0.752 atm 0.225 atm 0 0
C2H4 + 3O2 → 2CO2 + 2H2O Final 0.302 0 0 0.225 atm
1.22− x
7 x Now, on cooling to 220 K, N2O4 will solidify and only unreacted
Total moles of O2 required = x + 3 (1.22 − x ) = + 3.66 NO will be remaining in the flask.
2 2
130 x Q p∝T
⇒ = + 3.66 p1 T1
32 2 ∴ =
p2 T2
⇒ x = 0.805 mole ethane and 0.415 mole ethene.
0.805 0.302 300
⇒ Mole fraction of ethane = = 0.66 ⇒ =
1.22 p2 220
Mole fraction of ethene = 1 − 0.66 = 0.34 ⇒ p2 (NO) = 0.221 atm
82 States of Matter

pV 6×3 pressure inside the bottle. When the bottle is opened, there is
86. Total moles of gas in final mixture = = = 0.731
RT 0.082 × 300 chances of bumping of stopper. To avoid bumping, bottle
should be cooled that lowers the pressure inside.
Q Mole of H2 in the mixture = 0.70
(ii) According to Avogadro’s hypothesis, “Under identical
∴ Mole of unknown gas ( X ) = 0.031 conditions of pressure and temperature, equal volume of ideal
Because both gases have been diffused for same time gases contain equal number of molecules.”
r (H2 ) 0.70 M pV
= = ⇒ M = 1020 g mol −1 92. Number of moles (n) =
r ( X ) 0.031 2 RT
N (Number of molecules)
nRT and n=
87. V = N A (Avogadro number)
p
 pV 
5 ⇒ N = nNA =   N
For acetylene gas, 5 g = mol  RT  A
26
 7.6 × 10−10 1 
740 = ×  × 6.023 × 1023
p = 740 mm = atm  760 0.082 × 273
760
T = 50° C = 323 K = 2.7 × 1010 molecules

Substituting in ideal gas equation 93. From the given information, it can be easily deduced that in the
5 0.082 × 323 final mixture,
V = × × 76 = 5.23 L partial pressure of A = 1.0 atm
26 74
partial pressure of B = 0.5 atm
8RT1
88. uav (average velocity ) = Also
pV
nA = A =
V
πM RT RT
4
9 × 10 8 × 8.314 T1 pBV 0.5 V
⇒ ms−1 = ⇒ nB = =
100 3.14 × 44 × 10−3 RT RT
T1 = 1682.5 K nB 1 wB M 3 M 
⇒ = = × A = ×  A
Also, for the same gas nA 2 M B wA 2  M B 
uav 8RT1 2RT2 8T1 1 4T1 ⇒ M A :M B = 1 : 3
= : = × =
umps πM M π 2T2 πT2 p
94. Rate of effusion (r) ∝
4T1 M
⇒ 1=
πT2 r (NH3 ) 1 36.5 40 1 36.5
⇒ = × ⇒ =
4T 4 × 1682.5 r (HCl ) 17 p 60 p 17
⇒ T2 = 1 = = 2142 K
π 3.14 3 36.5
⇒ p= = 2.20 atm
Hence, T1 = 1682.5 K, T2 = 2142 K 2 17
3
4 3 4  21 3
89. Volume of balloon = πr = × 3.14 ×   cm 3 95. KE = k BT : k B = Boltzmann’s constant
3 3  2 2
= 4847 cm 3 ≈ 4.85 L 3
= × 1.38 × 10−23 × 300 J = 6.21 × 10−21 J/molecule
2
Now, when volume of H2 (g ) in cylinder is converted into NTP dp kp
volume, then 96. Rate of effusion is expressed as − =
dt M
p1V1 p2V2 20 × 2.82 1 × V2 k = constant, p = instantaneous pressure
= ⇒ =
T1 T2 300 273 dp k dt
⇒ − =
V2 = NTP volume ⇒ V2 = 51.324 L p M
Also, the cylinder will not empty completely, it will hold 2.82 L p kt
Integration of above equation gives ln  0  =
of H2 (g ) when equilibrium with balloon will be established.  p M
Hence, available volume of H2 (g ) for filling into balloon is  2000  k 47
51.324 − 2.82 = 48.504 L
Using first information : ln   =
 1500  32
48.504
⇒ Number of balloons that can be filled = = 10 32  4
4.85 ⇒ k= ln   …(i)
47  3
3RT 3 × 8.314 × 293 Now in mixture, initially gases are taken in equal mole ratio, hence
90. urms = = = 390.2 ms−1
M 48 × 10−3 they have same initial partial pressure of 2000 mm of Hg each.
After 74 min :
91. (i) NH3 (l ) is highly volatile, a closed bottle of NH3 (l ) contains
large number of molecules in vapour phase maintaining high
 States of Matter 83

 2000 74 k Also, the decomposition reaction is :

For O2 ln   =
MCO3 → MO + CO2
 pO 2  32
0.05 mol 0.05 mol
Substituting k from Eq. (i) gives Q 0.05 mole MCO3 = 4.21 5 g
 2000 4.215
74 32  4 ∴ 1.0 mole MCO3 = = 84.3 g (molar mass)
ln   = × ln   0.05
 O2 
p 32 47  3
⇒ 84.3 = MW of M + 12 + 48
 2000 74  4 ⇒ Molecular weight of metal = 24.3
ln   = ln  
 O2 
p 47  3 Q Metal is bivalent, equivalent weight
Molecular weight
Solving gives p (O2 ) at 74 min = 1271.5 mm = = 12.15
2
 2000 74 k
For unknown gas : ln   = 100. The ideal gas equation :
 pg  79 w
pV = nRT = RT
Substituting k from (i) gives M
 2000 74 32  4 w
ln   = × ln   ⇒ pM = RT = d RT where, ‘d’ is density.
 g 
p 79 47  3 V
pM 5 × 17
Solving gives : pg = 1500 mm ⇒ d= = = 3.42 g L−1.
RT 0.082 × 303
⇒ After 74 min, p (O2 ) : p (g ) = 1271.5 : 1500
Also, in a mixture, partial pressure ∝ number of moles Topic 2 Liquid State
⇒ n (O2 ) : n (g ) = 1 : 1.18
1. I (CH3OH) : Surface tension decreases as concentration increases.
97. First we determine empirical formula as II (KCl) : Surface tension increases with concentration for ionic
C H salt.
III [CH3 (CH2 )11 OSO−3 Na + ] : It is an anionic detergent.
Weight 10.5 1
There is decrease in surface tension before micelle formation,
10.5 and after CMC (Critical Micelle Concentration) is attained, no
Mole = 0.875 1
12 change in surface tension.
Simple ratio 1 1/0.875 = 1.14
KCl (II)
Surface tension

Whole no. 7 8

⇒ Empirical formula = C7H8 CH3OH (I)

−
 w CH3(CH2)11OSO3 Na + (III)
From gas equation : pV =   RT
M
wRT 2.8 × 0.082 × 400 Concentration
M = = = 91.84 ≈ 92
pV 1× 1
2. Let us consider, 1.0 L of liquid water is converted into steam .
Q Molar mass (M ) is same as empirical formula weight. Volume of H2O (l) = 1L, mass = 1000 g
Molecular formula = Empirical formula = C7 H8 1000
1 ⇒ Volume of 1000 g steam = cm 3
98. For same p and V , n ∝ 0.0006
T 1000
Q Volume of molecules in cm 3 steam = 1000 cm 3
n (gas) T (H2 ) 0.0006
⇒ =
n (H2 ) T (gas) ∴ Volume of molecules in
0.184 1000
n(H2 ) = = 0.092 1000 cm 3 steam = × 0.0006 × 1000 = 0.60 cm 3
2 1000
290 3. Critical temperature is directly proportional to intermolecular
⇒ n(gas) = × 0.092 = 0.0895
298 force of attraction. H2O is a polar molecule, has greater
Q 0.0895 mole of gas weigh 3.7 g intermolecular force of attraction than O2, hence higher critical
3.7 temperature.
∴ 1 mole of gas will weigh = 41.32 g
0.0895 4. At liquid-vapour equilibrium at boiling point, molecules in two
phase posses the same kinetic energy.
99. Moles of CO2 can be calculated using ideal gas equation as :
pV  700  1336 1
n= =    × = 0.05
RT  760  1000 0.082 × 300
6
Chemical and Ionic Equilibrium

Topic 1 Chemical Equilibrium

Objective Questions I (Only one correct option) The equilibrium constant for the reaction,
1. Consider the following reaction: 2SO2 ( g ) + O2 ( g ) 2SO3 ( g ) is
-
(2019 Main, 8 April II)
N 2O4 ( g ) q 2NO2 ( g ); ∆H ° = + 58 kJ 25 77 154
(a) 10 (b) 10 (c) 10 (d) 10181
For each of the following cases (A , B ), the direction in which the K
equilibrium shifts is (2020 Main, 5 Sep I) 6. In a chemical reaction, A + 2B - 2C + D,
the
(A) temperature is decreased. initial concentration of B was 1.5 times of the
(B) pressure is increased by adding N 2 at constant T. concentration of A, but the equilibrium concentrations of
(a) (A) towards product, (B) towards reactant A and B were found to be equal. The equilibrium
(b) (A) towards reactant, (B) no change
constant (K ) for the aforesaid chemical reaction is
(2019 Main, 12 Jan I)
(c) (A) towards reactant, (B) towards product
1
(d) (A) towards product, (B) no change (a) (b) 16
4
2. The incorrect match in the following is (2019 Main, 12 April II)
(c) 1 (d) 4
(a) ∆G ° < 0, K > 1 (b) ∆G ° = 0, K = 1
(c) ∆G ° > 0, K < 1 (d) ∆G ° < 0, K < 1
7. Two solids dissociate as follows:
- B (g ) + C(g ); K
A (s ) p1 = x atm2
3. In which one of the following equilibria, K p ≠ K c ?
(2019 Main, 12 April II) D ( s ) - C( g ) + E ( g ); K p2
= y atm2
(a) 2C(s) + O2 (g )
c 2CO(g )
The total pressure when both the solids dissociate
(b) 2HI(g ) c H2 (g ) + I2 (g ) simultaneously is (2019 Main, 12 Jan I)
(c) NO2 (g ) + SO2 (g )
c NO(g ) + SO3 (g ) (a) x + y atm (b) x 2 + y2 atm
(d) 2NO(g ) c N2 (g ) + O2 (g )
(c) (x + y) atm (d) 2( x + y ) atm
4. For the reaction,
8. Consider the reaction,
2SO2 ( g ) + O2 ( g ) → 2SO3 ( g ), ∆H = − 57.2 kJ mol −1 and
N 2 ( g ) + 3H 2 ( g ) =2NH (g ) 3
K c = 1.7 × 1016 . Which of the following statement is incorrect?
The equilibrium constant of the above reaction is K p . If
(2019 Main, 10 April II)
pure ammonia is left to dissociate, the partial pressure
(a) The equilibrium constant decreases as the temperature increases of ammonia at equilibrium is given by (Assume that
(b) The addition of inert gas at constant volume will not affect the pNH 3 < < p total at equilibrium) (2019 Main, 11 Jan I)
equilibrium constant
33/ 2 K p1/ 2P 2 33/ 2 K p1/ 2P 2
(c) The equilibrium will shift in forward direction as the pressure (a) (b)
increases 4 16
1/ 2 2 1/ 2 2
(d) The equilibrium constant is large suggestive of reaction going to Kp P Kp P
(c) (d)
completion and so no catalyst is required 16 4
5. For the following reactions, equilibrium constants are given : 9. 5.1 g NH4 SH is introduced in 3.0 L evacuated flask at
52
- SO (g ); K = 10
S( s ) + O2 ( g ) 2 1 327°C. 30% of the solid NH4 SH decomposed to NH3
2S( s ) + 3O ( g ) - 2SO ( g ); K = 10 129 and H2 S as gases. The K p of the reaction at 327° C is
2 3 2
 Chemical and Ionic Equilibrium 85

(R = 0.082 atm mol −1 K −1 , molar mass of S = 32 g mol −1 , 1

15. For the reaction, SO2 ( g ) + O2 ( g ) q SO3 ( g )
molar mass of N = 14 g mol ) −1 2
(2019 Main, 10 Jan II)
if K p = K C ( RT )x where, the symbols have usual meaning,
(a) 0. 242 × 10−4 atm 2 (b) 0. 242 atm 2
then the value of x is (assuming ideality) (2014 Main)
(c) 4 . 9 × 10−3 atm 2 (d) 1 × 10−4 atm 2 1 1
(a) − 1 (b) − (c) (d) 1
Kp 2 2
10. The values of for the following reactions at 300 K are,
KC 16. The species present in solution when CO2 is dissolved in
respectively (At 300 K, RT = 24.62 dm atm mol ) 3 −1 water are (2006 Main)
(a) CO2 , H2CO3 , HCO3− , CO32−
N 2 ( g ) + O2 ( g )=2NO(g ) (b) H2CO3 , CO2−
3
N 2O4 ( g ) =2NO (g ) 2
(c) HCO−3 , CO23−
N (g ) + 3H (g ) =2NH (g )
2 2 3
(d) CO2 , H2CO3
(2019 Main, 10 Jan I)
17. N2 + 3H2 r 2NH3
(a) 1, 24.62 dm 3 atm mol −1 , 606.0 dm 6 atm 2 mol −2 Which is correct statement if N2 is added at equilibrium
(b) 1, 24.62 dm 3 atm mol −1, 1.65 × 10−3 dm −6 atm −2 mol 2 condition? (2006, 3M)
(c) 24.62 dm 3 atm mol −1, 606.0 dm6 atm −2 mol 2, (a) The equilibrium will shift to forward direction because
1.65 × 10−3 dm −6 atm −2 mol 2 according to IInd law of thermodynamics, the entropy must
(d) 1, 4.1 × 10−2 dm −3atm −1 mol, 606 dm6 atm 2 mol −2 increases in the direction of spontaneous reaction
(b) The condition for equilibrium is G(N2) + 3G(H2)
11. Consider the following reversible chemical reactions, = 2G(NH3) where, G is Gibbs free energy per mole of the
K1
A2 ( g ) + B2 ( g ) -2 AB (g ) …(i) gaseous species measured at that partial pressure. The
K2 condition of equilibrium is unaffected by the use of
6 AB ( g ) - 3 A ( g ) + 3B ( g )
2 2 …(ii) catalyst, which increases the rate of both the forward and
backward reactions to the same extent
The relation between K 1 and K 2 is (2019 Main, 9 Jan II)
(c) The catalyst will increase the rate of forward reaction by α
(a) K 2 = K13 (b) K 1K 2 = 3
and that of backward reaction by β
1
(c) K 2 = K1− 3 (d) K 1K 2 = (d) Catalyst will not alter the rate of either of the reaction
3
18. Ag + + NH3 s [Ag(NH3 )]+ ; K 1 = 3. 5 × 10−3
12. An aqueous solution contains 0.10 M H2S and 0.20 M HCl. If
the equilibrium constants for the formation of HS− from H2S [Ag (NH3 )]+ + NH3 s [Ag (NH3 )2 ]+ ; K 2 = 1.7 ×10−3
. × 10−7 and that of S2− from HS− ions is 12
is 10 . × 10−13 then then the formation constant of [Ag(NH3 )2 ]+ is (2006, 3M)
the concentration of S2− ions in aqueous solution is : (a) 6.08 × 10 −6
(b) 6.08 × 106
(2018 Main) −9
(a) 5 × 10−8 M (b) 3 × 10−20 M (c) 6.08 × 10 (d) None of these
−21 −19
(c) 6 × 10 M (d) 5 × 10 M 19. Consider the following equilibrium in a closed container
13. The equilibrium constant at 298 K for a reaction, N2 O4 ( g ) r 2NO2 ( g )
A + B q C + D is 100. If the initial concentrations of all At a fixed temperature, the volume of the reaction container is
the four species were 1 M each, then equilibrium halved. For this change, which of the following statements
concentration of D (in mol L−1 ) will be (2016 Main) hold true regarding the equilibrium constant ( K p ) and degree
(a) 0.818 (b) 1.818 of dissociation (α ) ? (2002, 3M)
(c) 1.182 (d) 0.182 (a) Neither K p nor α changes
14. The standard Gibbs energy change at 300 K for the reaction, (b) Both K p and α change
2A a B + C is 2494. 2 J. At a given time, the composition
1 1 (c) K p changes but α does not change
of the reaction mixture is [A]= , [ B ] = 2 and [C ] = . The
2 2 (d) K p does not change but α changes
reaction proceeds in the
20. At constant temperature, the equilibrium constant ( K p ) for
(R = 8.314JK / mol, e = 2.718) (2015, Main)