Arihant NEET 34 Years Chapterwise Solutions Chemistry 2022

34
YEARS’ (1988-2021)
Chapterwise Topicwise
NEET
Solved Papers
CHEMISTRY
34
YEARS’ (1988-2021)
Chapterwise Topicwise
NEET
Solved Papers
CHEMISTRY
Complete Collection of all Questions
asked in last 34 years’ in NEET & CBSE AIPMT
Arihant Prakashan (Series), Meerut

Arihant Prakashan
(Series), Meerut
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PREFACE
Whenever a student decides to prepare for any examination his/her

first and foremost curiosity is to know about the type of questions that
are expected in the exam. This becomes more important in the context
of competitive entrance examinations where there is neck-to-neck
competition.
We feel great pleasure in presenting before you this book containing

Error Free Chapterwise Topicwise Solutions of CBSE AIPMT/NEET
Chemistry Questions from the years 1988 to 2021.
It has been our efforts to provide correct solutions to the best of our
knowledge and opinion. Detailed explanatory discussions follow the
answers. Discussions are not just sketchy–rather, have been drafted in a
manner that the students will surely be able to answer some other
related questions too ! Going through this book, the students would be
able to have the complete idea of the questions being asked in the test.
We hope this chapterwise solved papers would be highly beneficial to

the students. We would be grateful if any discrepancies or mistakes in
the questions or answers are brought to our notice so that these could
be rectified in subsequent editions.
Publisher
CONTENTS
1. Some Basic Concepts in Chemistry 1-8
2. Atomic Structure 9-16
3. Chemical Bonding and Molecular Structure 17-32
4. Chemical Thermodynamics 33-43
5. States of Matter 44-49
6. Solid State 50-55
7. Solutions 56-64
8. Chemical Equilibrium 65-69
9. Ionic Equilibrium 70-79
10. Redox Reactions and Electrochemistry 80-89
11. Chemical Kinetics 90-99
12. Surface Chemistry 100-103
13. Classification of Elements and Periodicity in Properties 104-108
14. General Principles and Processes of Isolation of Metals 109-112
15. Hydrogen 113-114
16. s-Block Elements 115-118
17. p- Block Elements 119-134
18. d and f-Block Elements 135-144

19. Co-ordination Compounds 145-156
20. Purification and Characterisation of Organic Compounds 157-159
21. Some Basics Principles of Organic Chemistry 160-174
22. Hydrocarbons 175-184
23. Organic Compounds Containing Halogens 185-190
24. Organic Compounds Containing Oxygen 191-216
25. Organic Compounds Containing Nitrogen 217-226
26. Polymers 227-231
27. Biomolecules , Chemistry in Everyday Life and Environmental Chemistry 232-242

SYLLABUS
CLASS 11th
UNIT I Some Basic Concepts of Chemistry
General Introduction Important and scope of chemistry. Laws of chemical combination, Dalton's atomic theory
concept of elements, atoms and molecules. Atomic and molecular masses. Mole concept and molar mass,
percentage composition and empirical and molecular formula, chemical reactions, stoichiometry and
calculations based on stoichiometry.
UNIT II Structure of Atom

Atomic number, isotopes and isobars. Concept of shells and subshells, dual nature of matter and light, de-
Broglie's relationship, Heisenberg’s uncertainty principle, concept of orbital, quantum numbers, shapes of s,p
and d orbitals, rules for filling electrons in orbitals- Aufbau principle, Pauli exclusion principles and Hund's rule,
electronic configuration of atoms, stability of half-filled and completely filled orbitals.
UNIT III Classification of Elements and Periodicity in Properties

Modern periodic law and long form of periodic table, periodic trends in properties of elements- atomic radii,
ionic radii, ionisation enthalpy, electron gain enthalpy, electronegativity, valence.
UNIT IV Chemical Bonding and Molecular Structure

Valence electrons, ionic bond, covalent bond, bond parameters, Lewis structure, polar character of covalent
bond, valence bond theory, resonance, geometry of molecules, VSEPR theory, concept of hybridization
involving s, p and d orbitals and shapes of some simple molecules, molecular orbital theory of homonuclear
diatomic molecules (qualitative idea only). Hydrogen bond.
UNIT V States of Matter: Gases and Liquids

Three states of matter, intermolecular interactions, types of bonding, melting and boiling points, role of gas
laws of elucidating the concept of the molecule, Boyle's law, Charles’ law, Gay Lussac's law, Avogadro's law, ideal
behaviour of gases, empirical derivation of gas equation. Avogadro number, ideal gas equation. Kinetic energy
and molecular speeds (elementary idea), deviation from ideal behaviour, liquefaction of gases, critical
temperature. Liquid State- Vapour pressure, viscosity and surface tension (qualitative idea only, no
mathematical derivations).
UNIT VI Thermodynamics
First law of thermodynamics internal energy and enthalpy, heat capacity and specific heat, measurement of U
and H, Hess's law of constant heat summation, enthalpy of : bond dissociation, combustion, formation,
atomization, sublimation, phase transition, ionization, solution and dilution. Introduction of entropy as state
function, Second law of thermodynamics Gibbs’ energy change for spontaneous and non-spontaneous process,
criteria for equilibrium and spontaneity. Third law of thermodynamics Brief introduction.
UNIT VII Equilibrium

Equilibrium in physical and chemical processes, dynamic nature of equilibrium, law of chemical equilibrium,
equilibrium constant, factors affecting equilibrium-Le Chatelier's principle, ionic equilibrium- ionization of acids
and bases, strong and weak electrolytes, degree of ionization, ionization of polybasic acids, acid strength,
concept of pH, Hydrolysis of salts (elementary idea), buffer solutions, Henderson equation, solubility product,
common ion effect (with illustrative examples).
UNIT VIII Redox Reactions
Concept of oxidation and reduction, redox reactions oxidation number, balancing redox reactions in terms of
loss and gain of electron and change in oxidation numbers.
UNIT IX Hydrogen
Occurrence, isotopes, preparation, properties and uses of hydrogen, hydrides-ionic, covalent and interstitial,
physical and chemical properties of water, heavy water, hydrogen peroxide-preparation, reactions, uses and
structure.
UNIT X s-Block Elements (Alkali and Alkaline Earth Metals)

Group 1 and group 2 elements General introduction, electronic configuration, occurrence, anomalous
properties of the first element of each group, diagonal relationship, trends in the variation of properties (such
as ionization enthalpy, atomic and ionic radii), trends in chemical reactivity with oxygen, water, hydrogen and
halogens, uses. Preparation and Properties of Some important Compounds. Sodium carbonate, sodium
chloride, sodium hydroxide and sodium hydrogencarbonate, biological importance of sodium and potassium.
Industrial use of lime and limestone, biological importance of Mg and Ca.
UNIT XI Some p-Block Elements

General Introduction to p-Block Elements.
Group 13 elements General introduction, electronic configuration, occurrence, variation of properties,
oxidation states, trends in chemical reactivity, anomalous properties of first element of the group; Boron, some
important compounds borax, boric acids, boron hydrides. Aluminium, uses, reactions with acids and alkalies.
General 14 elements General introduction, electronic configuration, occurrence, variation of properties,
oxidation states, trends in chemical reactivity, anomalous behaviour of first element. Carbon, allotropic forms,
physical and chemical properties, uses of some important compounds, oxides.
Important compounds of silicon and a few uses, silicon tetrachloride, silicones, silicates and zeolites, their uses.
UNIT XII Organic Chemistry- Some Basic Principles and Techniques

General introduction, methods of purification qualitative and quantitative analysis, classification and IUPAC
nomenclature of organic compounds. Electronic displacements in a covalent bond: inductive effect,
electromeric effect, resonance and hyper conjugation. Homolytic and heterolytic fission of a covalent bond free
radials, carbocations, carbanions, electrophiles and nucleophiles, types of organic reactions.
UNIT XIII Hydrocarbons

Alkanes Nomenclature, isomerism, conformations (ethane only), physical properties, chemical reactions
including free radical mechanism of halogenation, combustion and pyrolysis. Alkenes Nomenclature, structure
of double bond (ethene), geometrical isomerism, physical properties, methods of preparation, chemical
reactions, addition of hydrogen, halogen, water, hydrogen halides (Markovnikov's addition and peroxide
effect), ozonolysis, oxidation, mechanism of electrophilic addition.
Alkynes Nomenclature, structure of triple bond (ethyne), physical properties, methods of preparation, chemical
reactions, acidic character of alkynes, addition reaction of- hydrogen, halogens, hydrogen halides and water.
Aromatic hydrocarbons Introduction, IUPAC nomenclature, Benzene, resonance, aromaticity, chemical
properties, mechanism of electrophilic substitution- Nitration sulphonation, halogenation, Friedel Craft's
alkylation and acylation, directive influence of functional group in mono-substituted benzene, carcinogenicity
and toxicity.
UNIT XIV Environmental Chemistry

Environmental pollution Air, water and soil pollution, chemical reactions in atmosphere, smogs, major
atmospheric pollutants, acid rain ozone and its reactions, effects of depletion of ozone layer, greenhouse effect
and global warming-pollution due to industrial wastes, green chemistry as an alternative tool for reducing
pollution, strategy for control of environmental pollution.
CLASS 12th
UNIT I Solid State
Classification of solids based on different binding forces, molecular, ionic covalent and metallic solids,
amorphous and crystalline solids (elementary idea), unit cell in two dimensional and three dimensional lattices,
calculation of density of unit cell, packing in solids, packing efficiency, voids, number of atoms per unit cell in a
cubic unit cell, point defects, electrical and magnetic properties, Band theory of metals, conductors,
semiconductors and insulators.
UNIT II Solutions
Types of solutions, expression of concentration of solutions of solids in liquids, solubility of gases in liquids,
solid solutions, colligative properties- relative lowering of vapour pressure, Raoult's law, elevation of boiling
point, depression of freezing point, osmotic pressure, determination of molecular masses using colligative
properties abnormal molecular mass. Van Hoff factor.
UNIT III Electrochemistry

Redox reactions, conductance in electrolytic solutions, specific and molar conductivity variation of conductivity
with concentration, kohlrausch's Law, electrolysis and Laws of electrolysis (elementary idea), dry cell-
electrolytic cells and Galvanic cells; lead accumulator, EMF of a cell, standard electrode potential, Relation
between Gibbs’ energy change and EMF of a cell, fuel cells, corrosion.
UNIT IV Chemical Kinetics

Rate of a reaction (average and instantaneous), factors affecting rates of reaction, concentration, temperature,
catalyst, order and molecularity of a reaction, rate law and specific rate constant, integrated rate equations and
half-life (only for zero and first order reactions), concept of collision theory ( elementary idea, no mathematical
treatment). Activation energy, Arrhenious equation.
UNIT V Surface Chemistry

Adsorption physisorption and chemisorption, factors affecting adsorption of gases on solids, catalysis
homogeneous and heterogeneous, activity and selectivity, enzyme catalysis, colloidal state, distinction
between true solutions, colloids and suspensions, lyophillic, lyophobic multimolecular and macromolecular
colloids, properties of colloids, Tyndall effect, Brownian movement, electrophoresis, coagulation, emulsions-
types of emulsions.
UNIT VI General Principles and Processes of Isolation of Elements

Principles and methods of extraction concentration, oxidation, reduction electrolytic method and refining,
occurrence and principles of extraction of aluminium, copper, zinc and iron.
UNIT VII p- Block Elements

Group 15 elements General introduction, electronic configuration, occurrence, oxidation states, trends in
physical and chemical properties, preparation and properties of ammonia and nitric acid, oxides of nitrogen
(structure only), Phosphorous allotropic forms, compounds of phosphorous, preparation and properties of
phosphine, halides (PCI3, PCI5) and oxoacids (elementary idea only).
Group 16 elements General introduction, electronic configuration, oxidation states, occurrence, trends in
physical and chemical properties, dioxygen, preparation, properties and uses, classification of oxides, ozone.
Sulphur allotropic forms, compounds of sulphur, preparation, preparation, properties and uses of sulphur
dioxide, sulphuric acid, industrial process of manufacture, properties and uses, oxoacids of sulphur
(structures only).
Group 17 elements General introduction, electronic configuration, oxidation states, occurrence, trends in
physical and chemical properties, compounds of halogens, preparation, properties and uses of chlorine and
hydrochloric acid, interhalogen compounds oxoacids of halogens (structures only).
Group 18 elements General introduction, electronic configuration, occurrence, trends in physical and chemical
properties, uses.
UNIT VIII d-and f-Block Elements
General introduction, electronic configuration, characteristics of transition metals, general trends in properties
of the first row transition metals metallic character, ionization enthalpy, oxidation states, ionic
radii, colour, catalytic property, magnetic properties, interstitial compounds, alloy formation. Preparation and
properties of K2Cr2O7 and KMnO4. Lanthanoids electronic configuration, oxidation states, chemical reactivity
and lanthanoid contraction and its consequences. Actinoids Electronic configuration, oxidation states and
comparison with lanthanoids.
UNIT XI Coordination Compounds

Coordination compounds Introduction, ligands, coordination number, colour, magnetic properties and
shapes, IUPAC nomenclature of mononuclear coordination compounds, isomerism (structural and stereo)
bonding, Werner's theory VBT,CFT, importance of coordination compounds (in qualitative analysis, biological
systems).
UNIT X Haloalkanes and Haloarenes

Haloalkanes Nomenclature, nature of C –X bond, physical and chemical properties, mechanism of substitution
reactions. Optical rotation. Haloarenes Nature of C-X bond, substitution reactions (directive influence of
halogen for monosubstituted compounds only). Uses and environment effects of – dichloromethane,
trichloromethane, tetrachloromethane, iodoform, freons, DDT.
UNIT XI Alcohols, Phenols and Ethers

Alcohols Nomenclature, methods of preparation, physical and chemical properties (of primary alcohols only),
identification of primary, secondary and tertiary alcohols, mechanism of dehydration, uses with special
reference to methanol and ethanol. Phenols, Nomenclature, methods of preparation, physical and chemical
properties, acidic nature of phenol, electrophillic substitution reactions, uses of phenols. Ethers, Nomenclature,
methods of preparation, physical and chemical properties uses.
UNIT XII Aldehydes, Ketones and Carboxylic Acids

Aldehydes and Ketones Nomenclature, nature of carbonyl group, methods of preparation, physical and
chemical properties, and mechanism of nucleophilic addition, reactivity of alpha hydrogen in aldehydes, uses.
Carboxylic Acids Nomenclature, acidic nature, methods of preparation, physical and chemical properties, uses.
UNIT XIII Organic Compounds Containing Nitrogen

Amines Nomenclature, classification, structure, methods of preparation, physical and chemical properties, uses,
identification of primary secondary and tertiary amines. Cyanides and Isocyanides will be mentioned at
relevant places. Diazonium salts Preparation, chemical reactions and importance in synthetic
organic chemistry.
UNIT XIV Biomolecules

Carbohydrates Classification (aldoses and ketoses), monosaccharide (glucose and fructose), D.L. configuration,
oligosaccharides (sucrose, lactose, maltose), polysaccharides (starch, cellulose, glycogen): importance. Proteins
Elementary idea of – amino acids, peptide bond, polypeptides, proteins, primary structure, secondary structure,
tertiary structure and quaternary structure (qualitative idea only), denaturation of proteins, enzymes. Hormones
-Elementary idea (excluding structure). Vitamins Classification and function. Nucleic Acids DNA and RNA
UNIT XV Polymers
Classification Natural and synthetic, methods of polymerisation (addition and condensation),
copolymerization. Some important polymers natural and synthetic like polyesters, bakelite, rubber,
Biodegradable and non-biodegradable polymers.
UNIT XVI Chemistry in Everyday Life

Chemicals in medicines analgesics, tranquilizers, antiseptics, disinfectants, antimicrobials, antifertility drugs,
antibiotics, antacids, antihistamines. Chemicals in food preservatives, artificial sweetening agents, elementary
idea of antioxidants. Cleansing agents soaps and detergents, cleansing action.
1
Some Basic
Concepts in Chemistry
Weight of 45 mL ofH2 = V × d
TOPIC 1 = 0.045 × 0.089
Ans. (c)
According to Avogadro’s law “equal
Nature of Matter, Significant = 4.005 × 10 −3 g volumes of all gases contain equal
Figures and Laws of Chemical Therefore, vapour density number of molecules under similar
Combinations =
Weight of certain volume of substance conditions of temperature and
Weight of same volume of hydrogen pressure.” Thus, if 1 L of one gas
01 The number of significant figures 0.24 contains N molecules, 2 L of any gas
= = 59.93 under similar conditions will contain
for the three numbers 161 cm, 0.161 4005
. × 10 – 3
2 N molecules.
cm, 0.0161 cm are
[CBSE AIPMT 1998] 03 In the final answer of the
(a) 3,4 and 5 respectively expression TOPIC 2
(b) 3,4 and 4 respectively
(29.2 − 20.2) (1.79 × 10 5 ) Atomic Mass, Molecular
(c) 3,3 and 4 respectively
(d) 3,3 and 3 respectively 1.37 Mass and Formulae of
Ans. (d) the number of significant figures Compounds
(i) All non-zero digits are significant. is [CBSE AIPMT 1994]
(ii) Non-zero digits to the right of the (a) 1 (b) 2 05 An organic compound contains
decimal point are significant. (c) 3 (d) 4 78% (by wt.) carbon and remaining
(iii) Zeroes to the left of the first Ans. (c) percentage of hydrogen. The right
non-zero digit in a number are not
significant.
On calculation we find option for the empirical formula of
(29.2 − 20.2) (1.79 × 10 5 ) this compound is [At. wt. of C is 12,
So, the number of significant figures = 1.17 × 10 6
for the numbers 161 cm, 0.161 cm and 1.37 H is 1] [NEET 2021]
0.0161 cm are same, i.e. 3. As the least precise number contains (a) CH (b) CH2
3 significant figures, therefore answer (c) CH 3 (d) CH 4
02 0.24 g of a volatile gas, upon should also contains 3 significant
figures. Ans. (c)
vaporisation, gives 45 mL vapour at
Simplest
NTP. What will be the vapour 04 The molecular weight of O 2 and Atomic
Relative Simple
whole
density of the substance? Element % number ratio of
SO 2 are 32 and 64 respectively. At mass number
of moles moles
(Density of H2 = 0.089) 15°C and 150 mmHg pressure, 1 L of
ratio
[CBSE AIPMT 1996] 78 6.5
O 2 contains ‘N ’ molecules. The C 78 12 = 6.5 =1 1
(a) 95.93 (b) 59.93 number of molecules in 2L of SO 2 12 6.5
(c) 95.39 (d) 5.993
under the same conditions of H 22 1 22
= 22
22
= 3
Ans. (b)
temperature and pressure will be 1 6.5
Weight of gas = 0.24 g [CBSE AIPMT 1990] 3.3
Volume of gas (V ) = 45 mL = 0.045 L (a) N/2 (b) N The empirical formula of the organic
Density of H2 (d ) = 0.089 (c) 2 N (d) 4 N compound is CH3.
2 NEET Chapterwise Topicwise Chemistry
06 The number of protons, neutrons Thus, the empirical formula of the 12 An organic compound contains
and electrons in 175 compound is CH3O.
71 Lu, C = 40%,O = 53.34% and
respectively, are [NEET (Sep.) 2020] H =6.60%. The empirical formula
09 An element, X has the following
(a) 104, 71 and 71 (b) 71, 71 and 104 of the compound is
isotopic composition: [CBSE AIPMT 1994]
(c) 175, 104 and 71 (d) 71, 104 and 71 200
Ans. (d)
X : 90%, 199 X : 8.0%, (a) CH2O (b) CHO
202
175
X :2.0% (c) CH4O2 (d) C2H2O
In 71 Lu,
The weighted average atomic Ans. (a)
Mass number (A) = 175 = n + p
mass of the naturally occurring
Atomic number (Z) = 71 = p = e −
Element
element X is closest to
∴ Number of protons = 71 % At. wt. Molar ratio
Simple
[CBSE AIPMT 2007] ratio
Number of neutrons
(a) 201 u (b) 202 u
= A − Z = 175 − 71 = 104
(c) 199 u (d) 200 u C 40 12 40 3.33
Number of electrons = 71 = 3.33 = 1
Ans. (d) 12 3.33
07 Suppose the elements X and Y Weight of 200 X = 0.90 × 200 = 180.00 u H 6.60 1 6.60 6.60
= 6.60 =2
combine to form two compounds Weight of 199 X = 0.08 × 199 = 15.92u 1 3.33
XY 2 and X 3Y 2 . When 0.1 mole of XY Weight of 202 X = 0.02 × 202 = 4.04u 3.33
O 53.3 16 53.34 =1
Total weight = 199.96 ≈ 200 u = 3.33
2 weighs 10 g and 0.05 mole of 4 16 3.33
X 3Y 2 weighs 9 g, the atomic
weights of X and Y are 10 Which of the following is Hence, empirical formula is
isoelectronic? [CBSE AIPMT 2002]
[NEET Phase II 2016] C : H : O = 1 : 2 : 1 = CH2O
(a) 40, 30(b) 60, 40(c) 20, 30(d) 30, 20 (a) CO2 , NO2
Ans. (a) (b) NO2–, CO2 13 Boron has two stable isotopes, 10 B
(c) CN–, CO (19%) and 11 B (81%). Calculate
Let atomic masses of X and Y be AX and
AY , respectively (d) SO2 , CO2 average atomic weight of boron in
10 Ans. (c) the periodic table.
For XY2 , nXY2 = 0.1 =
AX + 2AY CN− and CO are isoelectronic because [CBSE AIPMT 1990]
or AX + 2AY = 100 …(i) they have equal number of electrons. (a) 10.8 (b) 10.2
For X3Y2 , nX Y2 = 0.05 =
9 InCN− the number of electrons (c) 11.2 (d) 10.0
3
3AX + 2AY = 6 + 7 + 1 = 14 Ans. (a)
or 3AX + 2AY = 180 …(ii) In CO the number of electrons Average of atomic weight
On solving Eqs. (i) and (ii), we get, = 6 + 8 = 14
% of 10
B × atomic mass of 10 B + % of 11B
−1 −1
A X = 40 g mol ⇒ A Y = 30 g mol × atomic mass of 11B
11 An organic compound containing C, =
H and N gave the following results % of 10 B + % of 11B
08 An organic compound contains
on analysis C = 40%, 19 × 10 + 81 × 11
carbon, hydrogen and oxygen. Its =
H = 13.33%, N = 46.67%. Its 19 + 81
elemental analysis gave C, 38.71%
empirical formula would be 190 + 891
and H, 9.67%. The empirical [CBSE AIPMT 2002, 1999, 98] = = 10.81
formula of the compound would be 100
(a) C2 H7 N2 (b) CH5 N
[CBSE AIPMT 2008]
(c) CH4 N (d) C2 H7 N 14 While extracting an element from
(a) CH3O (b) CH2O (c) CHO (d) CH4O
Ans. (c) its ore, the ore is grind and leached
Ans. (a)
Table for empirical formula with dil. KCN solution to form the
Element
% At. Molar Simple soluble product potassium

Element
abundance wt. ratio ratio

%
At.
Molar ratio
Simple argento- cyanide. The element is
wt. ratio [CBSE AIPMT 1989]
C 38.71 12 38.71 = 3.23 3.23 = 1 (a) lead
12 3.23 C 40.00 12 40 3.33
= 3.33 =1 (b) chromium
12 3.33 (c) manganese
H 9.67 1 9.67 9.67 (d) silver
= 9.67 =3 H 13.33 1 13.33 13.33
1 3.23 = 13.33 =4
1 3.33 Ans. (d)
46.67 3.33 Silver metal is extracted from the
O [100 – (38.71 16 51.62 = 3.23 3.23 = 1 N 46.67 14 = 3.33 =1
14 3.33 argentite ore Ag2S by cyanide process. In
+ 9.67)] 16 3.23
this method, the concentrated ore is
= 51.62 treated with dilute solution of potassium
Hence, empirical formula is CH4N.
Some Basic Concepts in Chemistry 3
cyanide, then a soluble complex 17 Which one of the followings has Number of molecules of water
potassium dicyanoargentate (I) is formed = 0.01 × N A
maximum number of atoms?
which when reacted with zinc, silver is (iii) 0.00224 L of water vapours at 1 atm
[NEET (Sep.) 2020]
extracted as a ppt. and 273 K. At STP [1 atm and 273 K],
(a) 1 g of Mg(s ) [Atomic mass of Mg = 24]
Ag2S + 4KCN → 2K[Ag(CN) 2 ] + Na2S Number of moles [with reference to
(b) 1 g of O2 (g) [Atomic mass of O = 16]
2K[Ag(CN)2 ] + Zn → K2 [Zn(CN) 4 ] volume]
(c) 1 g of Li(s ) [Atomic mass of Li = 7] Volume of gas in litres
+ 2Ag ↓ (d) 1 g of Ag(s ) [Atomic mass of Ag = 108] =
22.4
Ans. (c) 0.00224
15 A metal oxide has the formula = = 0.0001
Z 2O 3. It can be reduced by Number of atoms (n) 22.4
Mass in g (1 g) × Atomicity of Number of molecules of water
hydrogen to give free metal and
the molecule = 0.0001 × NA
water. 0.1596 g of the metal oxide = × NA
Gram molar mass (M) (iv) 10 −3 mol of water
requires 6 mg of hydrogen for Number of molecules of water
[QN A = Avogadro’s number]
complete reduction. The atomic Atomicity = 10 −3 × N A
weight of the metal is ⇒ n∝
M ∴ Among the given options, option (i)
[CBSE AIPMT 1989] contains the maximum number of water
1
(a) 27.9 (b) 159.6 (a) nMg = molecules.
24
(c) 79.8 (d) 55.8 2 1
Ans. (d) (b) nO = = 19 If Avogadro number N A , is changed
32 16
Z2O3 + 3H2 → 2 Z + 3H2O 1 from 6.022 × 10 23 mol −1 to
(c) nLi =
Q 6 × 10 −3 g H2 reduces = 0.1596 g of Z2O3 7 6.022 × 10 20 mol −1 this would
0.1596 (d) nAg =
1 change [CBSE AIPMT 2015]
∴ 1 g H2 reduces = g Z2O 3
6 × 10 –3 108 (a) the definition of mass in units of
= 26.6 g of Z2O 3 So, nLi > nO > nMg > nAg grams
(b) the mass of one mole of carbon
∴ Equivalent weight of Z2O 3 =26.6
18 In which case is the number of (c) the ratio of chemical species to each
Equivalent weight of Z + Equivalent molecules of water maximum? other in a balanced equation
weight of O = 26.6 (d) the ratio of elements to each other in
[NEET 2018]
Equivalent weight of Z + 8 = 26.6 (a) 0.00224 L of water vapours at 1 atm
a compound
Equivalent weight of Z = (26.6 – 8) = 18.6 and 273 K Ans. (b)
Valency of metal inZ2O3 =3 (b) 0.18 g of water If Avogadro numberN A , is changed from
Equivalent weigh (c) 18 mL of water 6.022 × 1023 mol − 1 to 6.022 × 1020 mol − 1,
Atomic weight (d) 10 −3 mol of water this would change the mass of one mole
= of carbon.
Valency Ans. (c)
Q 1 mole of carbon has mass = 12 g
Atomic weight Number of molecules = Mole ×
Avogadro’s number (N A ) or 6.022 × 1023 atoms of carbon have
= 18.6 × 3 = 55.8 mass = 12 g
The number of molecules of water in
each of the given options is calculated ∴6.022 × 1020 atoms of carbon have
TOPIC 3 as mass
12
Mole Concept and (i) 18 mL of water = × 6.022 × 1020 = 0.012 g
Number of moles (nH 2 O ) 6.022 × 1023
Concentration Terms Mass of substance in g (wH 2 O )
= 20 How many grams of concentrated
16 One mole of carbon atom weighs 12 Molar mass in g mol −1 (MH 2 O ) nitric acid solution should be used
g, the number of atoms in it is wH 2 O = 18g to prepare 250 mL of 2.0 M HNO 3 ?
equal to, (Mass of carbon -12 is [QDensity of water (dH 2 O ) = 1 g L−1] The concentrated acid is 70%
1.9926 × 10 −23 g) [NEET (Oct.) 2020] 18 HNO 3 .
∴ nH 2 O = = 1 [NEET 2013]
(a) 1.2 × 1023 (b) 6.022 × 1022 18 (a) 45.0 g conc. HNO 3
(c) 12 × 1022 (d) 6.022 × 1023 Number of molecules of water (b) 90.0 g conc. HNO 3
Ans. (d) = 1 × NA (c) 70.0 g conc. HNO 3
(ii) 0.18 g of water (d) 54.0 g conc. HNO 3
1 mole of carbon atoms weight 12 g, its
wH O 0.18
contains Avogadro number of carbon nH 2 O = 2 = = 0.01 Ans. (a)
atoms, i.e. 6022
. × 1023 number of carbon MH 2 O 18 Given, molarity of solution = 2
atoms.
Volume of solution = 250mL
250 1 23 Volume occupied by one molecule 25 Percentage of Se in peroxidase

= = L
1000 4 of water (density = 1 g cm −3 ) is anhydrase enzyme is 0.5% by weight
Molar mass of [CBSE AIPMT 2008] (at. weight = 78.4), then minimum
HNO3 = 1 + 14 + 3 × 16 = 63 g mol −1 (a) 9.0 × 10−23 cm3 molecular weight of peroxidase
Q Molarity (b) 6.023 × 10−23 cm3 anhydrase enzyme is
=
Weight of HNO3 (c) 3.0 × 10−23 cm3 [CBSE AIPMT 2001]
Molecular mass of HNO3 (d) 5.5 × 10−23 cm3 (a) 1.568 × 103 (b) 15.68
× volume of solution (L) Ans. (c) (c) 2.168 × 104 (d) 1.568 × 104
∴Weight of 1 mole = 6.023 × 1023 molecule Ans. (d)
HNO3 = molarity × molecular mass 18 g = 6.02 × 1023 molecule Suppose the molecular weight of
× volume (L) 18 g = mass of 6.02 × 1023 enzyme = x
1
= 2 × 63 × g water molecules 0.5% by weight means in 100 g of
4 enzyme weight of Se = 0.5 g
Mass of one water molecule
= 31.5 g 0.5
18 ∴ In x g of enzyme weight ofSe = ×x
It is the weight of 100%HNO3 = g
6.023 × 1023 100
But the given acid is 70%HNO3 0.5 × x
100 Density = 1g cm–3 Hence, . =
784
∴ Its weight = 31. 5 × g Mass of one water molecule 100
70 Volume =
Density ∴ x = 15680
= 45 g
18 = 1.568 × 10 4
= cm3
21 6.02 × 10 20 molecules of urea are 6.023 × 1023 × 1
≈ 3.0 × 10 −23 cm3
26 The number of atoms in 4.25 g of
present in 100 mL of its solution.
NH3 is approximately
The concentration of solution is [CBSE AIPMT 1999]
[NEET 2013] 24 The maximum number of
molecules are present in (a) 4 × 1023 (b) 2 × 1023
(a) 0.02 M (b) 0.01 M
[CBSE AIPMT 2004] (c) 1 × 1023 (d) 6 × 1023
(c) 0.001 M (d) 0.1 M
(a) 15 L of H2 gas at STP Ans. (d)
Ans. (b)
(b) 5 L of N2 gas at STP Weight of NH3 = 4.25 g
Given, number of molecules of urea
= 602
. × 1020 (c) 0.5 g of H2 gas Number of moles of
(d) 10 g of O2 gas Weight
. × 1020
602 NH3 =
∴ Number of moles = Ans. (a) Molecular weight
NA
4.25
. × 1020
602
In 15 L of H2 gas at STP, = = 0.25 mol
= the number of molecules 17
6023
. × 1023
Number of molecules in 0.25 mole ofNH3
6.023 × 1023
= 0.999 × 10 −3 = × 15 = 0.25 × 6.023 × 1023
~− 1 × 10 −3 mol 22.4
So, number of atoms
Volume of the solution = 4.033 × 1023 = 4 × 0.25 × 6.023 × 1023
100 In 5 L of N2 gas at STP,
= 100 mL = L = 0.1 L = 60
. × 1023
1000 the number of molecules
Concentration of urea solution (in molL−1) 6.023 × 1023 × 5 27 Haemoglobin contains 0.33% of iron
=
1 × 10 −3 by weight. The molecular weight of
= mol L−1 22.4
0.1 haemoglobin is approximately
= 1.344 × 1023
= 1 × 10 −2 mol L−1 67200 g. The number of iron atoms
In 0.5 g of H2 gas,
= 0.01 mol L−1 (at. weight of Fe is 56) present in one
the number of molecules
molecule of haemoglobin are
22 The number of atoms in 0.1 mole of 6.023 × 1023 × 0.5
= [CBSE AIPMT 1998]
a triatomic gas is 2
(a) 1 (b) 6 (c) 4 (d) 2
(N A = 6.023 × 10 23 mol −1 ) = 1.505 × 1023 Ans. (c)
[CBSE AIPMT 2010] In 10 g of O2 gas,
Q 0.33 % of iron by weight means 100 g
(a) 6.026 × 1022 (b) 1.806 × 1023 the number of molecules of haemoglobin has 0.33 g of iron
(c) 3.600 × 1023 (d) 1.800 × 1022 6.023 × 1023 × 10
= 100 g of haemoglobin contains iron
Ans. (b) 32 = 0.33 g
Number of atoms = number of moles ∴ 67200 g of haemoglobin contains iron
= 1.882 × 1023
× NA × atomicity 0.33 × 67200
Hence, maximum number of molecules = g
= 0.1 × 6.023 × 1023 × 3 100
are present in 15 L ofH2 at STP.
= 1.806 × 1023 atoms = 221.76 g of Fe
221.76 Ans. (b) Ans. (d)
Number of Fe-atoms =
56 6.023 × 1023 molecules of CO At NTP 22400 cc ofN2O contains
= 3.96 ≈ 4 = 1 mole of CO = 6.02 × 1023 molecules
6.02 × 1024 molecules of CO ∴1 cc N2O will contain
28 The number of moles of oxygen in 1 = 10 moles of CO 6.02 × 1023
L of air containing 21% oxygen by = 10 g atoms of O = 5 g molecules of O2 = molecules
22400
volume, under standard conditions,
In N2O molecule, number of atoms
is [CBSE AIPMT 1995] 32 The number of oxygen atoms in
=2+ 1=3
(a) 0.0093 mole (b) 2.10 moles 4.4 g of CO 2 is [CBSE AIPMT 1990]
Thus, number of atoms
(c) 0.186 mole (d) 0.21 mole (a) 1.2 × 10 23 (b) 6 × 10 22
(c) 6 × 10 23 (d) 12 × 10 23 3 × 6.02 × 1023
Ans. (a) = atoms
22400
Volume of oxygen in 1 L of air Ans. (a)
1.8 × 1022
=
21
× 1000 = 210 mL 1 mole of CO2 = 44 g of CO2 = atoms
224
100 = 6.023 × 1023 molecules
Q 22400 mL volume at STP is occupied ∴ 4.4 g of CO2 = 0.1 mole of CO2 In N2O molecule, number of electrons
by oxygen = 1 mole = 6.023 × 0.1 × 1023 molecules = 7 + 7 + 8 = 22
Therefore, number of moles occupied = 6.023 × 1022 molecules Hence, number of electrons
by 210 mL = 6.023 × 1022 molecules of O2 6.02 × 1023
210 = 2 × 6.023 × 1022 atoms of O = × 22 electrons
= = 0.0093 mol 22400
22400 ≈ 1.2 × 1023 atoms of O
1.32 × 1023
= electrons
33 Ratio of C p and C V of a gas ‘ X ’ is 224
29 The percentage weight of Zn in
white vitriol [ZnSO4 ⋅ 7H2O] is 1:4. The number of atoms of the 35 At STP, the density of CCl 4 vapour
approximately equal to gas ‘ X ’ present in 11.2 L of it at NTP
(at. mass of Zn = 65, S = 32,O = 16 in g/L will be nearest to
will be [CBSE AIPMT 1989]
[CBSE AIPMT 1988]
and H= 1) [CBSE AIPMT 1995] (a) 6.02 × 1023 (b) 1.2 × 1023 (a) 6.87 (b) 3.42 (c) 10.26 (d) 4.57
(a) 33.65% (b) 32.56% (c) 3.01 × 1023 (d) 2.01 × 1023
(c) 23.65% (d) 22.65% Ans. (a)
Ans. (a)
Ans. (d)
For the gas X ratio of C p /C V = 1 : 4 1 mole CCl 4 vapours
Molecular weight of
So, the gas X is diatomic. = 12 + 4 × 35.5 = 154 g
ZnSO4 ⋅ 7H2O= 65 + 32+ (4 × 16) + 7 (18)
At NTP, volume of 1 mole of a gas At STP, volume of 1 mole of a gas
= 287
= 22.4 L = 22.4 L
65
∴ Percentage weight ofZn = × 100 1 mole of a gas = 6.023 × 1023 molecules
287 Thus, 154 g = 22.4 L
Thus, at NTP 22.4 L contains 154
= 22.65% ∴ Density of CCl 4 vapours = g L–1
= 6.023 × 1023 molecules 22.4
30 The total number of valence So, at NTP 11.2 L contains = 6.87 g L–1
electrons in 4.2 g of N −3 ion is (NA is 6.023 × 1023 × 11.2
= molecules
the Avogadro’s number) 22.4 TOPIC 4
[CBSE AIPMT 1994]
= 301
. × 1023 molecules
(a) 2.1 N A (b) 4.2 N A (c) 1.6 N A (d) 3.2 N A Stoichiometric and
Hence, number of atoms of gas ‘X ’
Ans. (c) (diatomic) Volumetric Calculations
4.2
Moles of N−3 ion = = 0.1 = 3.01 × 1023 × 2 atoms
42 36 The number of moles of hydrogen
= 6.02 × 1023 atoms molecules required to produce 20
Each nitrogen atom has 5 valence
electrons. Therefore, total number of moles of ammonia through Haber’s
electrons inN−3 ion = 16 34 1 cc N 2O at NTP contains process is [NEET (National) 2019]
Total number of electrons in 0.1 mole or [CBSE AIPMT 1988] (a) 20 (b) 30 (c) 40 (d) 10
4.2 g of N−3 ion = 0.1 × 16 × N A = 1.6 N A 1.8
(a) × 1022 atoms Ans. (b)
224
According to Haber’s process,
31 The number of gram molecules of 6.02
(b) × 1023 molecules N2 (g) + 3H2 (g) - 2NH3 (g)
oxygen in 6.02 × 10 24 CO molecules 22400
Now, according to above equations
is [CBSE AIPMT 1990] 1.32
(c) × 1023 electrons 2 moles of ammonia (NH3) require = 3
(a) 10 g molecules (b) 5 g molecules 224 moles of H2
(c) 1 g molecule (d) 0.5 g molecule (d) All of the above ∴ 1 mole of NH3 require = 3 /2 moles of H2
3 NaCl in equal volume with the help of

or, 20 moles of NH3 require = × 20 40 1.0 g of magnesium is burnt with
2 mole concept.
0.56 g of oxygen in a closed vessel.
moles of H2 = 30 moles of H2 . 16.9% solution of AgNO3 means 16.9 g
AgNO3 is present in 100 mL solution. Which reactant is left in excess and
Note Involvement of any limiting
∴8.45 g AgNO3 will be present in 50 mL how much? [CBSE AIPMT 2014]
reagent is not mentioned in question.
solution. (At. weight of Mg = 24, O = 16)
37 20.0 g of a magnesium carbonate Similarly, (a) Mg, 0.16 g
sample decomposes on heating to 5.8 g NaCl is present in 100 mL solution (b) O2 , 0.16 g
give carbon dioxide and 8.0 g ∴2.9 g NaCl is present in 50 mL solution (c) Mg, 0.44 g
magnesium oxide. What will be the AgNO3 + NaCl → AgCl + NaNO3 (d) O2 , 0.28 g
percentage purity of magnesium Initial mole Ans. (a)
8.45 2.9 The balanced chemical equation is
carbonate in the sample? 0 0
(Atomic weight of Mg = 24) 169.8 58.5 1
Mg + O2 → MgO
[CBSE AIPMT 2015] =0.049 = 0.049 2
(a) 75 (b) 96 (c) 60 (d) 84 After reaction 24 g 16 g 40 g
Ans. (d) 0 0 0.049 0.049 From the above equation, it is clear that,
∴Mass of AgCl precipitated 24 g of Mg reacts with 16 g ofO2 .
Key Concept In the given problem we
have provided practical yield of MgO. For = 0.049 × 143.5 = 7 g Thus, 1.0 g of Mg reacts with
calculation of percentage yield of MgO, 16
g of O2 = 0.67 g of O2 .
we need theoretical yield of MgO. For 39 When 22.4 L of H2 (g) is mixed with 24
this we shall use mole concept.
11.2 L of Cl 2 (g), each at STP, the But only 0.56 g ofO2 is available which is
MgCO3( s ) → MgO( s ) + CO2 ( g ) …(i) less than 0.67 g. Thus,O2 is the limiting
moles of HCl(g) formed is equal to
Weight in gram reagent.
Moles of MgCO3 = [CBSE AIPMT 2014]
Molecular weight (a) 1 mole of HCl (g) Further, 16 g ofO2 reacts with 24 g of Mg.
20 ∴ 0.56 g of O2 will react with Mg
= = 0.238 mol (b) 2 moles of HCl (g)
84 24
(c) 0.5 mole of HCl (g) = × 0 . 56
From Eq. (i) (d) 1.5 moles of HCl (g) 16
1 mole of MgCO3 gives = 1 mol MgO Ans. (a) = 0 . 84 g
∴0.238 moleMgCO3 will give The given problem is related to the ∴ Amount of Mg left unreacted
= 0.238 mol MgO concept of stoichiometry of chemical = (1.0 − 0.84) g Mg
equations. Thus, we have to convert the = 0.16 g Mg
= 0.238 × 40 g
given volumes into their moles and then,
= 9.52 g MgO identify the limiting reagent [possessing 41 10 g of hydrogen and 64 g of
Now, practical yield ofMgO = 8 g minimum number of moles and gets oxygen were filled in a steel vessel
8 completely used up in the reaction]. The and exploded. Amount of water
∴ % purity = × 100 = 84%
9.52 limiting reagent gives the moles of
product formed in the reaction.
produced in this reaction will be
Alternate Method [CBSE AIPMT 2009]
MgCO3 → MgO + CO2 H2 ( g ) + Cl2 ( g ) → 2HCl ( g )
(a) 2 moles (b) 3 moles
84 g 40 g Initial vol. 22.4 L 11.2 L 2 mol (c) 4 moles (d) 1 mole
84
∴8 g MgO will be form from g Q 22.4 L volume at STP is occupied by
5 Ans. (c)
84 100 Cl2 = 1 mole 1
∴ % purity = × = 84% H2 + O2 → H2O
5 20 ∴ 11.2 L volume will be occupied by 2
1 × 11.2 1 mol
1
mol 1 mol
Cl2 = mol = 0.5 mol 2
38 What is the mass of precipitate 22.4 10 64
mol mol ?
formed when 50 mL of 16.9% 22.4 L volume at STP is occupied byH2 2 32
= 1 mol 5 mol 2mol
solution of AgNO 3 is mixed with 50
mL of 5.8% NaCl solution? Thus, H2 (g) + Cl2 (g) → 2HCl (g) 1
Q mole of O2 gives = 1 mole of H2O
1 mol 0.5 mol 2
(Ag = 107.8,N = 14, O = 16,
Since, Cl2 possesses minimum number ∴ 2 moles of O2 will give = 1 × 2 × 2
Na = 23,Cl = 35.5) of moles, thus it is the limiting reagent.
= 4 moles of water
[CBSE AIPMT 2015] As per equation,
(a) 28 g (b) 3.5 g 1 mole of Cl2 = 2 moles of HCl 42 How many moles of lead (II)
(c) 7 g (d) 14 g ∴ 0.5 mole of Cl2 = 2 × 0.5 mole of HCl chloride will be formed from a
Ans. (c) = 1.0 mole of HCl reaction between 6.5 g of PbO and
Plan For the calculation of mass of AgCl Hence, 1.0 mole ofHCl (g) is produced by 3.2 g of HCl? [CBSE AIPMT 2008]
precipitated, we find mass of AgNO3 and 0.5 mole of Cl2 [or 11.2 L]. (a) 0.044 (b) 0.333 (c) 0.011 (d) 0.029
Ans. (d) 45 The number of moles of KMnO 4 Q For 108 g of Al, 36 g of C is required in
PbO + 2HCl → PbCl2 + H2O that will be needed to react with above reaction.
207 + 16 2 × 36.5 one mole of sulphite ion in acidic ∴For270 × 10 3 g of Al required amount of C
(1 mol)
= 223 = 73 solution is 36
(1 mol) (2 mol) [CBSE AIPMT 2007] = × 270 × 10 3
(a) 4/5 (b) 2/5 108
6.5
Mole of PbO = = 0.029 (c) 1 (d) 3/5 = 90 × 10 3 g = 90 kg
223
Ans. (b)
3.2
Mole of HCl = = 0.087
2KMnO4 + 3H2SO4 → K2SO4 + 2MnSO4
48 In Haber process 30L of dihydrogen
36.5
+ 3H2O + 5[O]
and 30L of dinitrogen were taken
Since, 1 mole of PbO reacts with 2 moles
of HCl, thus in this reaction PbO is the [MnO–4 + 8H+ + 5e – → Mn2 + + 4H2O] × 2
for reaction which yielded only 50%
of the expected product. What will
limiting reagent. [SO23– + H2O → SO24– + 2H+ + 2 e − ] × 5
Hence, 1 mole of PbO forms be the composition of gaseous
2 MnO–4 + 6H+ + 5SO23– → 2Mn2 + + 5 SO24–
= 1 mole of PbCl2 mixture under the aforesaid
0.029 mole of PbO will form = 0.029 mole + 3H2O condition in the end?
of PbCl2 5 moles of sulphite ions react with [CBSE AIPMT 2003]
= 2 moles of MnO–4 (a) 20 L ammonia, 10 L nitrogen, 30 L
43 What volume of oxygen gas (O 2 ) So, 1 mole of sulphite ions react with hydrogen
2 (b) 20 L ammonia, 25 L nitrogen, 15 L
measured at 0°C and 1 atm, is = moles of MnO−4 .
5 hydrogen
needed to burn completely 1L of (c) 20 L ammonia, 20 L nitrogen, 20 L
propane gas (C 3H8 ) measured hydrogen
46 The number of moles of KMnO 4
under the same conditions? (d) 10 L ammonia, 25 L nitrogen,
[CBSE AIPMT 2008]
reduced by one mole of KI in 15 L hydrogen
(a) 7 L (b) 6 L alkaline medium is Ans. (d)
[CBSE AIPMT 2005]
(c) 5 L (d) 10 L N2 + 3H2 → 2NH3
(a) one fifth (b) five
Ans. (c) 1V 3V 2V
(c) one (d) two 10 L 30 L 20 L
C3H8 + 5O2 → 3CO2 + 4H2O Ans. (c)
As only 50% of the expected product is
22.4 L 5 × 22.4 L In alkaline medium,KMnO4 is reduced to formed, hence only 10 L ofNH3 is formed.
For the combustion of 22.4 L propane, K2MnO4
Thus, for the production of 10 L ofNH3, 5
oxygen required = 5 × 22.4 L KI + H2O → KOH + HI L of N2 and 15 L of H2 are used and
For the combustion of 1 L of propane +7 +6
composition of gaseous mixture under
2KMnO4 + 2KOH → 2K2 MnO4
oxygen required the aforesaid condition in the end is
5 × 22.4 + H2O + [O]
= L = 5L H2 = 30 − 15 = 15 L
22.4 Hence, one mole ofKMnO4 is reduced by
one mole of KI. N2 = 30 − 5 = 25 L
NH3 = 10 L
44 Number of moles of MnO–4 required
47 The mass of carbon anode
to oxidise one mole of ferrous consumed (giving only carbon 49 Which has maximum number of
oxalate completely in acidic dioxide) in the production of 270 kg molecules? [CBSE AIPMT 2002]
medium will be [CBSE AIPMT 2008] of aluminium metal from bauxite by (a) 7 g N2 (b) 2 g H2
(a) 0.6 mole (b) 0.4 mole the Hall process is (c) 16 g NO2 (d) 16 g O2
(c) 7.5 moles (d) 0.2 mole (at. mass of Al = 27) Ans. (b)
Ans. (b) [CBSE AIPMT 2005] In 7 g nitrogen, number of molecules
In acidic mediumMnO−4 oxidises ferrous (a) 180 kg (b) 270 kg (c) 540 kg(d) 90 kg 7.0
= mol
oxalate as follows: Ans. (d) 28
2MnO–4 + 5C2O24– + 16H+ → 2Mn2 +
In Hall and Heroult process, = 0.25 × NA molecules
+ 10CO2 + 8H2O
2 Al2O3 + 4C → 4 Al + 2CO2 + 2CO where, N A = Avogadro numbe
Q 5 moles of oxalate ions are oxidised by
2 moles of MnO−4 . but for the removal of only CO2 , following = 6.023 × 1023
equation is possible. 2.0
∴ 1 mole of oxalate ion is oxidised by In 2 g of H2 = mol
2 2 Al2O3 + 3C → 4Al + 3CO2 2
= mole of MnO−4 = 0.4 mole of MnO–4
3 × 12 4 × 27
5
= 108 = 1 × N A molecules
= 36
16.0 Ans. (c)

In 16 g of NO2 = mol 53 What is the weight of oxygen
46 4NH3 (g) + 5O2 (g) → 4NO(g) +6H2O(l ) required for the complete
= 0.348 × NA molecules 4 mol 5 mol 4 mol 6 mol combustion of 2.8 kg of ethylene?
In 16 g of According to equation, [CBSE AIPMT 1989]
16
O2 = mol = 0.5 × NA molecules 5 moles of O2 required = 4 moles of NH3 (a) 2.8 kg (b) 6.4 kg
32 1 mole of O2 requires (c) 9.6 kg (d) 96 kg
Hence, maximum number of molecules 4 Ans. (c)
= = 0.8 mole of NH3
are present in 2 g ofH2 . 5
C2H4 + 3O2 → 2CO2
5
While 1 mole ofNH3 requires = 12 × 2 + 4 × 1 16 × 6
50 Assuming fully decomposed, the 4 =28 g = 96 g + 2H2O
volume of CO 2 released at STP on = 1.25 moles of O2
heating 9.85 g of BaCO 3 (at. mass As there is 1 mole ofNH3 and 1 mole ofO2 ,
Q For the combustion of 28 × 10 −3 kg of
of Ba = 137) will be so all the oxygen will be consumed.
ethylene oxygen required = 96 × 10 −3 kg
[CBSE AIPMT 2000]
∴ For the combustion of 2.8 kg of
(a) 1.12 L (b) 0.84 L 52 Liquid benzene (C 6H6 ) burns in
ethylene oxygen required
(c) 2.24 L (d) 4.96 L oxygen according to the equation, 96 × 10 −3 × 2. 8
Ans. (a) =
2C 6H6 (l) + 15O 2 (g) → 28 × 10 −3
On decomposition,BaCO3 liberates CO2 as 12CO 2 (g) + 6H2O(g)
= 9.6 kg
BaCO3 → BaO + CO2 ↑ How many litres of O 2 at STP are
197 g 22.4 L at STP
needed to complete the 54 One litre hard water contains 12.00
Q 197 g of BaCO3 gives combustion of 39 g of liquid mg Mg 2+ . Milliequivalents of
= 22.4 L of CO2 at STP benzene? (Mol. weight of O 2 = 32, washing soda required to remove
∴ 9.85 g of BaCO3 will give C 6H6 = 78) [CBSE AIPMT 1996]
its hardness is [CBSE AIPMT 1988]
22.4 × 9.85 (a) 74 L (b) 11.2 L (c) 22.4 L (d) 84 L
= = 1.12 L (a) 1
197 Ans. (d) (b) 12.16
2C6H6 + 15O2 (g) → 12CO2 (g) (c) 1 × 10−3
51 In the reaction, 2 × 78 15 × 32 + 6H2O( g ) (d) 12.16 × 10−3
4NH3 (g) + 5O 2 (g) → = 156 = 330
Ans. (a)
Q 156 g of benzene required oxygen
4NO(g) + 6H2O(l) Mg2 + +Na2 CO3 → MgCO3 + 2Na+
= 15 × 22.4 L
When 1 mole of ammonia and 1 1 g -eq 1 g -eq
∴ 1 g of benzene required oxygen
mole of O 2 are made to react to 1 g-equivalent of Mg2 + = 12 g of Mg2 +
15 × 22.4
completion, then = L
156 = 12000 mg of Mg2 +
[CBSE AIPMT 1998]
∴ 39 g of benzene required oxygen Now, 12000 mg ofMg2 + ≡ 1000
(a) 1.0 mole of H2O is produced
15 × 22.4 × 39 milliequivalent ofNa2 CO3
(b) 1.0 mole of NO will be produced =
156 12 mg of Mg2 + ≡ 1 milliequivalent of
(c) all the oxygen will be consumed Na2 CO3
(d) all the ammonia will be consumed = 84.0 L
2
Atomic Structure
TOPIC 1 03 The energy absorbed by each 05 The frequency of radiation emitted
Preliminary Models molecule (A 2 ) of a substance is when the electron falls from n = 4
4.4 × 10 −19 J and bond energy per to n = 1 in a hydrogen atom will be
01 Which of the following is never true molecule is 4.0 × 10 −19 J. The (Given ionisation energy of
for cathode rays? kinetic energy of the molecule per H = 2.18 ×10–18 J atom–1 and
[CBSE AIPMT 1994] atom will be [CBSE AIPMT 2009] h = 6.625 × 10–34 Js)
(a) They possess kinetic energy (a) 2.0 × 10−20 J (b) 2.2 × 10−19 J [CBSE AIPMT 2004]
(b) They are electromagnetic waves (c) 2.0 × 10−19 J (d) 4.0 × 10−20 J (a) 1.54 × 1015 s–1 (b) 1.03 × 1015 s–1
(c) They produce heat Ans. (a) (c) 3.08 × 1015 s–1 (d) 2.00 × 1015 s–1
(d) They produce mechanical pressure Kinetic energy (KE) of molecule Ans. (c)
Ans. (b) = energy absorbed by molecule Ionisation energy of H
Cathode rays are not electromagnetic − bond energy per molecule = 2.18 × 10 − 18 J atom–1
wave because they do not have electric . × 10 −19 ) − (40
= (44 . × 10 −19 ) J ∴ E 1 ( Energy of Ist orbit of H-atom)
and magnetic components = 0.4 × 10 −19 J
perpendicular to each other. = − 2.18 × 10 −18 J atom–1
KE per atom
− 2 .18 × 10 −18
0.4 × 10 –19 ∴ En = J atom–1
= J n2
2
TOPIC 2 = 2.0 × 10 −20 J
Z = 1 for H-atom
∆E = E 4 − E 1
Bohr’s Model and
− 2 .18 × 10 −18 − 2 .18 × 10 −18
Hydrogen Spectrum 04 The energy of second Bohr orbit of = −
the hydrogen atom is 42 12
= − 2 .18 × 10 −18 ×  2 − 2 
1 1
02 The energies E 1 and E 2 of two –328 kJ mol–1 , hence the energy of  4 1 
fourth Bohr orbit would be
radiations are 25 eV and 50 eV [CBSE AIPMT 2005] ∆E = − 2 .18 × 10 −18 × −
15
respectively. The relation between (a) – 41 kJ mol–1 16
their wavelengths, i.e. λ 1 and λ 2 (b) –1312 kJ mol–1 = + 2 .0437 × 10 −18 J atom–1
will be [CBSE AIPMT 2011] ∆E
(c) –164 kJ mol–1 ∴ ν=
(a) λ 1 = 2 λ 2 (b) λ 1 = 4 λ 2 h
(d) – 82 kJ mol–1
1
(c) λ 1 = λ 2 (d) λ 1 = λ 2 2 .0437 × 10 −18 J atom–1
Ans. (d) =
2 6 .625 × 10 −34 J s
Ans. (a) The energy of second Bohr orbit of
hydrogen atom (E2 ) is – 328 kJ mol –1 = 3 .084 × 10 15 s− 1 atom–1
E 1 = 25 eV, E2 = 50 eV 1312
hc hc E n = – 2 kJ mol –1
E1 = and E2 = n 06 In hydrogen atom, energy of first
λ1 λ2
1312 excited state is –3.4 eV. Then, KE
E1 λ2 ∴ E2 = − 2 kJ mol –1
or = 2 of same orbit of hydrogen atom is
E2 λ 1 [CBSE AIPMT 2002]
If n = 4
25 λ 2 1312 (a) + 3.4 eV (b) + 6.8 eV
or = ∴ E4 = – kJ mol –1
50 λ 1 42 (c) – 13.6 eV (d) + 13.6 eV
or λ 1 = 2 λ2 = − 82 kJ mol –1 Ans. (a)
Q Total energy ( E n ) =KE + PE 10 When an electron of charge e and (a) Energy of the electrons in the orbits
1  Ze2  mass m moves with a velocity v are quantised
In first excited state = mv2 + –  (b) The electron in the orbit nearest the
2  r  about the nuclear charge Ze in nucleus has the lowest energy
1 Ze2 Ze2 circular orbit of radius r, the (c) Electrons revolve in different orbits
=+ –
2 r r potential energy of the electrons is around the nucleus
Energy of first excited state is 3.4 eV given by [CBSE AIPMT 1994] (d) The position and velocity of
1 Ze2 Z2 e2 Ze2 Ze2 mv 2 electrons in the orbit cannot be
– 3 .4 eV = – (a) (b) − (c) (d) determined simultaneously
2 r r r r r
Ans. (d)
1 Ze2 Ans. (b)
∴ KE = = + 3 .4 eV The main postulates of Bohr model of
2 r Potential energy = work done
atom are
r Ze2 dr Ze2
=∫ − =− (i) The electrons in an atom revolve
07 Who modified Bohr’s theory by ∞ r 2
r around the nucleus only in certain
introducing elliptical orbits for selected circular paths, called orbits.
electron path? [CBSE AIPMT 1999] 11 If ionisation potential for hydrogen (ii) The energy is emitted or absorbed
(a) Hund (b) Thomson atom is 13.6 eV, then ionisation only when the electrons jump from
(c) Rutherford (d) Sommerfeld potential for He + will be one energy level to another.
Ans. (d) [CBSE AIPMT 1993] (iii) Only those orbits are permitted in
(a) 54.4 eV (b) 6.8 eV which the angular momentum of the
Sommerfeld modified Bohr’s theory.
(c) 13.6 eV (d) 24.5 eV electron is a whole number multiple
According to him electrons move in h
elliptical orbits in addition to circular Ans. (a) of (where, h is Planck’s constant)
orbits. 2π
For hydrogen atom Z = 1 that's why only certain fixed orbits
2 π2 me 4 are allowed, i.e. the momentum of an
08 Bohr radius for the hydrogen atom ∴ Ionisation energy, EH = …(i)
n2h2 electron is quantised.
(n = 1) is approximately 0.530Å. The
For He+ ion, (He+ = 1s 1 )
radius for the first excited state 14 If r is the radius of the first orbit,
so, (He+ = H) ionisation energy,
(n = 2) is (in Å) [CBSE AIPMT 1998]
2 π2 me 4 Z2 the radius of nth orbit of H-atom is
(a) 0.13 (b) 1.06 (c) 4.77 (d) 2.12 EHe + = …(ii)
n2h2 given by [CBSE AIPMT 1988]
Ans. (d) Eq (i)/Eq (ii), we get (a) rn2 (b) rn
r ∝ n /Z 2
EHe + = EH × Z2 = 136 . × 4 = 54.4 eV (c)
r
(d) r2n2
where, n = number of orbit n
Z = atomic number 12 The energy of an electron in the nth Ans. (a)
Q r1 ∝ n21 Bohr orbit of hydrogen atom is Radius of an orbit,
r2 ∝ n22 (Z = 1 for H-atom) [CBSE AIPMT 1992]
n2h2
r1 n21 13.6 13.6 rn =
So, = (a) − 4 eV (b) − 3 eV 4π2 me2 Z
r2 n22 n n
13.6 13.6 0.529n2
0 . 530 12 (c) − 2 eV (d) − eV = Å
= 2 n n Z
r2 2 For H-atom, Z = 1
Ans. (c)
∴ r2 = 0 .530 × 4 = 2 .120 Å Energy of an electron in an orbit, If r1 = r
2 π2 me 4 Z2 1311.8 Z2 (according to question r1 = r)
09 The radius of hydrogen atom in the En = − = − kJ mol –1
n2h2 n2 r × n2
ground state is 0.53 Å. The radius ∴ rn = = rn2
21. 8 × 10 −12 Z2 1
of Li 2+ ion (at. no. = 3) in a similar En = − erg atom–1
n2
state is [CBSE AIPMT 1995] 15 The spectrum of helium is
21. 8 × 10 −19 Z2
(a) 0.17 Å (b) 0.53 Å En = − J atom–1 expected to be similar to that of
(c) 0.265 Å (d) 1.06 Å n2 [CBSE AIPMT 1988]
13.6 Z2 −13.6
Ans. (a) En = − eV atom−1 = 2 eV atom (a) H (b) Na
n2 n (c) Li+ (d) He +
We know that rn (H-like)
(Q Z = 1 atomic number Ans. (c)
r (H- atom) × n2
= n for hydrogen atom)
Z The spectrum of an atom depends on
For ground state, n = 1 the number of electrons present in it.
13 Which of the following statements Here, helium has two electrons, so the
0.53 Å × (1)2 do not form a part of Bohr’s model
∴ rn (Li2 + ) = spectrum of Li+ (Z = 3) is similar to that of
3 of hydrogen atom? helium because both He andLi+ have
(Li,Z = 3) = 0.17 Å [CBSE AIPMT 1989] two electrons.
Atomic Structure 11
TOPIC 3 18 Which one is the wrong statement? According to Hund’s rule of maximum
multiplicity, An orbital can accommodate
[NEET 2017]
Wave Particle and a maximum number of 2 electrons of
(a) de-Broglie’s wavelength is given by
Quality of Matter h
exactly opposite spin. Hence, option (a)
λ= , where is correct.
mv Caution Remember, maximum number
16 A particular station of All India m = mass of the particle, of electrons in an orbital do not depend
Radio, New Delhi, broadcasts on a v = group velocity of the particle upon the quantum numbers as given in
frequency of 1,368 kHz (kilohertz). (b) The uncertainty principle is the question.
The wavelength of the ∆E × ∆t ≥ h /4π
electromagnetic radiation emitted (c) Half-filled and fully filled orbitals 20 The number of d-electrons in
by the transmitter is have greater stability due to greater Fe 2+ (Z=26) is not equal to the
exchange energy, greater symmetry number of electrons in which one
[Speed of light, c = 3.0 × 10 3 ms −1 ] and more balanced arrangement
[NEET 2021] of the following? [CBSE AIPMT 2015]
(d) The energy of2s-orbital is less than
(a) 219.3 m (b) 219.2 m the energy of2p-orbital in case of (a) s-electrons in Mg (Z = 12)
(c) 2192 m (d) 21.92 cm hydrogen like atoms (b) p-electrons in CI (Z = 17)
Ans. (a) Ans. (d) (c) d-electrons in Fe (Z = 26)
(d) p-electrons in Ne (Z = 10)
Frequency of electromagnetic radiation (a) According to de-Broglie’s equation,
ν = 1368 kHz h Ans. (b)
Wavelength (λ) =
= 1368 × 10 3 s−1 mv Electronic configuration of Fe2 + is
Speed of light, c = 3 × 10 8 ms −1 where,h = Planck’s constant. [Ar]3d 6 4s 0 .
Wavelength of electromagnetic Thus, statement (a) is correct. ∴Number of electrons = 6
radiation, λ =
c (b) According to Heisenberg uncertainty Mg – 1s 2 2s 2 2p6 3s 2 (6s electrons)
ν principle, the uncertainties of It matches with the6d electrons of Fe2 +
3 × 10 8 ms−1 position (∆x) and momentum
λ= = 219.3 m Cl – 1s 2 2s 2 2p6 3s 2 3p5 (11p electrons)
(p = m∆v) are related as
1368 × 10 3 s−1 It does not match with the6d electrons
h
∆x . ∆p ≥
4π of Fe2 + .
17 In hydrogen atom, the de-Broglie h Fe – [Ar]3d 6 4s 2 (6d electrons)
wavelength of an electron in the or, ∆x . m∆v ≥
4π It matches with the6d electrons of Fe2 + .
second Bohr orbit is h Ne – 1s 2 2s 2 2p6 (6p electrons)
∆x . m. ∆a . ∆t ≥
[Given that, Bohr radius, 4π It matches with the6d electrons of Fe2 + .
a 0 = 52.9 pm] [NEET (Odisha) 2019]  ∆v = ∆a, a = acceleration Hence, Cl has 11p electrons which does
(a) 211.6 pm (b) 211.6 π pm  ∆t  not matches in number with6d electrons
of Fe2 + .
(c) 52.9 π pm (d) 105.8 pm h
or, ∆x ⋅ F ⋅ ∆t ≥ [QF = m⋅ ∆a]
Ans. (b) 4π
h 21 The angular momentum of
According to Bohr, or, ∆E ⋅ ∆t ≥ electrons in d orbital is equal to
nh 4π
mvr = [Q∆E = F ⋅ ∆x, E = energy]
[CBSE AIPMT 2015]
2π (a) 6 h (b) 2 h (c) 2 3 h (d) 0 h
nh  h  Thus, statement (b) is correct.
2πr = = nλ …(i) Qλ = Ans. (a)
mv  mv  (c) The half and fully filled orbitals have
greater stability due to greater Angular momentum of electron in
where, r = radius, exchange energy, greater symmetry d-orbital is
λ = wavelength and more balanced arrangement. h
= l (l + 1) ;for d-orbital, l = 2
n = number of orbit Thus statement (c) is correct. 2π
a n2 (d) For a single electronic species like H,  h 
Also, r= 0 …(ii) energy depends on value of n and = 2(2 + 1 Q h = 
Z  2π 
does not depend onl. Hence energy
where,a 0 = Bohr radius = 52.9 pm of 2s-orbital. and 2p-orbital is equal in h= 6h
Z = atomic number case of hydrogen like species.
On substituting the value of ‘r ’ from Eq. Therefore, statement (d) is incorrect. 22 Calculate the energy in joule
(ii) to Eq. (i), we get corresponding to light of
2 πn2a 0 19 How many electrons can fit in the wavelength 45 nm (Planck’s
nλ =
Z orbital for which n = 3 and l = 1? constant, h = 6.63 × 10 −34 Js; speed
λ=
2 πna 0 [NEET (Phase II) 2016] of light, c = 3 × 10 8 ms −1 ).
Z (a) 2 (b) 6 [CBSE AIPMT 2014]
λ = 2 π × 2 × 52.9 [Q n = 2, Z = 1] (c) 10 (d) 14 (a) 6.67 × 1015 (b) 6 . 67 × 1011
= 211.6π pm Ans. (a) (c) 4 .42 × 10−15 (d) 4 .42 × 10− 18
Ans. (d) 25 If uncertainty in position and 27 The value of Planck’s constant is

The wavelength of light is related to its momentum are equal, then 6.63 × 10 −34 Js. The velocity of light
hc
energy by the equation, E = . (E = hv) uncertainty in velocity is is 3 .0 × 10 8 ms −1 . Which value is
λ [CBSE AIPMT 2008] closest to the wavelength in
Given, λ = 45 nm = 45 × 10 −9 m 1
(a)
h
(b)
h nanometers of a quantum of light
[Q1 nm = 10 −9 m] 2m π 2π with frequency of 8 × 10 15 s −1 ?
6.63 × 10 −34 Js × 3 × 10 8 m s−1
Hence, E = 1 h h [CBSE AIPMT 2003]
45 × 10 −9 m (c) (d)
m π π (a) 4 × 101 (b) 3 × 107
−18
= 4.42 × 10 J Ans. (a) (c) 2 × 10−25 (d) 5 × 10−18
Hence, the energy corresponds to light
According to Heisenberg’s uncertainty
of wavelength 45 nm is 4.42 × 10 −18 J. Ans. (a)
principle
c 3 × 10 8 m s–1
h Frequency (ν) = =
23 The value of Planck’s constant is ∆x ⋅ ∆p = λ 8 × 1015 s–1
4π
6.63 × 10 −34 Js. The speed of light is =0.375 × 10 –7 m
Given, ∆x = ∆p (∆x = uncertainty in
3 × 10 17 nm s −1 . Which value is position) = 3.75 × 10 1 nm ≈ 4 × 10 1 nm
closest to the wavelength in h
(∆p)2 = (∆p = m × ∆v)
nanometer of a quantum of light 4π 28 The energy of photon is given as :
with frequency of 6 × 10 15 s −1 ? m2 ∆v2 =
h
m = mass ∆e/atom= 3.03 × 10 −19 J atom–1 ,
[NEET 2013] 4π then the wavelength (λ) of the
(a) 10 (b) 25 h 1 h photon is [CBSE AIPMT 2000]
∆v2 = 2 ⇒ ∆v =
(c) 50 (d) 75 m 4π 2m π (Given,h(Planck’s constant)
Ans. (c) (∆v = uncertainty in velocity) = 6.63 × 10 −34 Js, c (velocity of light)
Given, Planck’s constant, = 3.00 × 10 8 ms −1 )
h = 6.63 × 10 −34 Js 26 Given, the mass of electron is (a) 6.56 nm (b) 65.6 nm
Speed of light, c = 3 × 10 17 nm s−1 9.11 × 10–31 kg, Planck’s constant is (c) 656 nm (d) 0.656 nm
Frequency of quantam light 6.626 × 10–34 Js, the uncertainty Ans. (c)
ν = 6 × 10 15 s−1 involved in the measurement of hc  c
According to formula, E = ν = 
velocity within a distance of 0.1 Å is λ  λ
Wavelength, λ = ?
[CBSE AIPMT 2006]
c
We know that, ν = or λ =
c Energy E = hν
λ ν
(a) 5.79 × 106 ms–1 (b) 5.79 × 107 ms–1 hc
. × 10 – 19 =
303
3 × 10 17
(c) 5.79 × 108 ms–1 (d) 5.79 × 105 ms–1 λ
=
6 × 10 15
Ans. (a) 6.63 × 10 –34 × 3 .0 × 10 8
λ=
By Heisenberg’s uncertainty principle 3 .03 × 10 –19
= 0.5 × 102 nm = 50 nm
h h
∆x × ∆px ≥ or ∆x × ∆ (mvx ) ≥ = 6 .56 × 10 –7 m
4π 4π
24 The measurement of the electron = 6.56 ×10 –7 × 10 9 nm
h
position is associated with an ∆x × ∆vx ≥ = 6.56 × 102 nm
4πm
uncertainty in momentum, which is = 656 nm
∆p = uncertainty in momentum
equal to 1 × 10 −18 g cm s −1 . The
∆x = uncertainty in position 29 The de-Broglie wavelength of a
uncertainty in electron velocity is
∆v = uncertainty in velocity
(mass of an electron is 9 × 10 −28 g) particle with mass 1 g and velocity
m= mass of particle 100 m/s is [CBSE AIPMT 1999]
[CBSE AIPMT 2008]
Given that,
(a) 1 × 109 cm s−1 (a) 6 . 63 × 10–33 m (b) 6 . 63 × 10–34 m
∆x = 0.1 Å = 0.1 × 10 −10 m
(b) 1 × 106 cm s−1 (c) 6 . 63 × 10–35 m (d) 6 . 65 × 10–36 m
m = 9.11 × 10 −31 kg
(c) 1 × 105 cm s−1 Ans. (a)
h = Planck’s constant = 6626 . × 10 −34 Js
(d) 1 × 1011 cm s−1 π = 3 .14 p=
h
(de-Broglie equation)
Ans. (a) λ
Thus,
h
Given, ∆p = 1 × 10 −18 g cm s–1 (uncertainty 6.626 × 10 −34 λ= (Qp = mv)
∆v × 0.1 × 10 −10 = mv
in momentum) 4 × 3.14 × 9.11 × 10 −31
h = 6625
. × 10 −34
Mass = 9 × 10 −28 g 6.626 × 10 −34
∆v = . × 10 −34 kg/s
≈ 663
∆p = m∆v 4 × 3.14 × 9.11 × 10 −31 × 0.1 × 10 −10 . × 10 –34 kg m2 / s
663
1 × 10 −18
= 9 × 10 −28 × ∆v λ=
ms–1 10 –3 kg × 100 m/ s
(uncertainty in velocity) = 5.785 × 10 ms6 –1
= 663
. × 10 –33 m
∆v = 1 × 10 9 cm s−1 = 5.79 × 10 6 ms–1
Atomic Structure 13
30 The uncertainty in momentum of Ans. (c) increase the kinetic energy of ejected
electron.
an electron is 1 × 10– 5 kg m/s. The According to de-Broglie relation,
h h
uncertainty in its position will be λ= = 35 The electron was shown
mv p
(Given, h = 6.62 × 10–34 kg m 2 /s) where, λ = wavelength experimentally to have wave
[CBSE AIPMT 1999]
h = Planck’s constant properties by [CBSE AIPMT 1994]
(a) 1.05 × 10–28 m (b) 1.05 × 10–26 m (a) de-Broglie
p = momentum
(c) 5 . 27 × 10–30 m (d) 5 . 25 × 10–28 m
Here, h = 6.625 × 10 −34 J s (b) N Bohr
Ans. (c) (c) Davisson and Germer
λ = 10 −17 m
According to Heisenberg’s uncertainty h 6.625 × 10 –34 (d) Schrodinger
&&
principle ∴ p= =
λ 10 −17 Ans. (c)
h
∆p × ∆ x ≥ = 6.625 × 10 −34 × 10 17 The wave nature of an electron is proved
4π
= 6.625 × 10 −17 kg m s–1 by Davisson and Germer experiment. In
Uncertainty in momentum this experiment the scattering pattern of
∆p = 1 × 10 −5 kg m/s 33 Uncertainty in position of an an electron is similar to that of X-rays.
6.62 × 10 –34 electron (mass of an
1 × 10 –5 × ∆ x = (Given)
4×
22 electron is = 9.1 × 10 −28 g) moving TOPIC 4
7 with a velocity of 3 × 10 4 cm/ s Quantum Mechanical,
6.62 × 10 –34 × 7 accurate upto 0.001% will be (use
∆x = Model and Electronic
1 × 10 –5 × 4 × 22 h
in uncertainty expression where
= 5 .265 × 10 –30 m 4π Configuration
≈ 5 .27 × 10 –30 m h = 6.626 × 10 −27 erg s)
[CBSE AIPMT 1995] 36 The number of angular nodes and
31 The position of both, an electron (a) 1.93 cm (b) 3.84 cm radial nodes in 3s orbital are
and a helium atom is known within (c) 5.76 cm (d) 7.68 cm [NEET (Oct.) 2020]
1.0 mm. Further the momentum of Ans. (a) (a) 0 and 2, respectively
the electron is known within According to Heisenberg’s uncertainty (b) 1 and 0, respectively
(c) 3 and 0, respectively
5.0 × 10 −26 kg ms–1 . The minimum principle
h (d) 0 and 1, respectively
uncertainty in the measurement of ∆ x × ∆v =
4π m Ans. (a)
the momentum of the helium atom
is [CBSE AIPMT 1998] Here, ∆ x = uncertainty in position For 3 s-orbital, n = 3, l = 0
(a) 50 kg ms–1 ∆v = uncertainty in velocity Number of radial nodes
(b) 80 kg ms–1 h = Planck’s constant (6.626 × 10 −27 Js) = (n − l − 1) = 3 − 0 − 1 = 2
(c) 80 × 10–26 kg ms–1 m = mass of electron (9.1 × 10 −28 kg) Number of angular nodes = l = 0.
Here, ∆v = 0.001% of 3 × 10 4 Hence, option (a) is correct.
(d) 5.0 × 10–26 kg ms–1
0.001
Ans. (d) = × 3 × 10 4 =0.3 cm / s
100 37 4d, 5p, 5f and 6p-orbitals are
By Heisenberg’s uncertainty principle h
h ∴ ∆x = arranged in the order of decreasing
∆ x × ∆p ≥ 4πm ∆v
4π energy. The correct option is
6.626 × 10 −27 [NEET (National) 2019]
when the position of electron and helium = = 1.93 cm
atom is same and momentum of 4 × 3.14 × 9.1 × 10 −28 × 0.3 (a) 6 p > 5 f > 5 p > 4 d
electron is known within a range, (b) 5 p > 5 f > 4 d > 5 p
therefore the momentum of helium 34 In the photoelectron emission, the (c) 5 f > 6 p > 4 d > 5 p
atom is also equal to the momentum of energy of the emitted electron is (d) 5 f > 6 p > 5 p > 4 d
electron, i.e. [CBSE AIPMT 1994] Ans. (d)
5 × 10 −26 kg m s–1 (a) greater than the incident photon
The order of energy of orbitals can be
(b) same as that of the incident photon calculated from (n + l ) rule. The lower the
32 The momentum of a particle having (c) smaller than the incident photon value of (n + l ) for an orbital, lower is its
a de-Broglie wavelength of 10 −17 m (d) proportional to the intensity of energy. If two orbitals have same (n + l )
is [CBSE AIPMT 1996] incident photon value, the orbital with lower value of n
(Given, h = 6.625 × 10 −34 m) Ans. (c) has the lower energy.
(a) 3.3125 × 10−7 kg m s–1 In the photoelectric effect, the energy of (i) 6p = 6 + 1 = 7 (ii) 5f = 5 + 3 = 8
(b) 26.5 × 10−7 kg m s–1 the emitted electron is smaller than that (iii) 4d = 4 + 2 = 6 (iv) 5p = 5 + 1 = 6
(c) 6.625 × 10–17 kg m s–1 of the incident photon because some ∴ The order of decreasing energy will be
(d) 13.25 × 10−17 kg m s−1 energy of photon is used to eject the 5f > 6p > 5p > 4d.
electron and remaining energy is used to
38 Orbital having 3 angular nodes and 41 Which is the correct order of 45 If n = 6, the correct sequence for
3 total nodes is [NEET (Odisha) 2019] increasing energy of the listed filling of electrons will be
(a) 5 p (b) 3 d orbitals in the atom of titanium? [CBSE AIPMT 2011]
(c) 4 f (d) 6 d [CBSE AIPMT 2015] (a) ns → (n − 1) d → (n − 2) f → np
Ans. (c) (a) 3s 4s 3p 3d (b) 4s 3s 3p 3d (b) ns → (n − 2) f → np → (n − 1) d
Angular node (l ) = 3 (c) 3s 3p 3d 4s (d) 3s 3p 4s 3d
(c) ns → np → (n − 1) d → (n − 2) f
Total node = radial node + angular node Ans. (c) (d) ns → (n − 2) f → (n − 1) d → np
3 = (n − l − 1) + l According to Aufbau rule Ans. (d)
3s < 3p < 3d < 4s
3 = n− 1 6s → 4f → 5d → 6p for n = 6
⇒ n=4 42 What is the maximum numbers of
∴Orbital having 3 angular nodes and 3 electrons that can be associated 46 Which of the following is not
total nodes is = nl = 4f [Ql = 3 for f- with the following set of quantum permissible arrangement of
orbital]
numbers? electrons in an atom?
[CBSE AIPMT 2009]
n = 3, l = 1 and m = − 1
39 Which one is a wrong statement? (a) n = 4,l = 0, m = 0, s = −1/2
[NEET 2013]
[NEET 2018]
(a) 10 (b) 6 (b) n = 5,l = 3, m = 0, s = + 1/2
(a) The electronic configuration of (c) n = 3,l = 2, m = − 3, s = −1/2
N-atom is (c) 4 (d) 2
Ans. (d) (d) n = 3,l = 2, m = −2, s = −1/2
2p1x 2p1y 2p1z Ans. (c)
1s2 2s2 The orbital of the electron having n = 3,
l = 1 and m = − 1 is 3pz (as nl m ) and an If n = 3,
orbital can have a maximum number of l = 0 to (3 − 1) = 0, 1, 2
(b) An orbital is designated by three
two electrons with opposite spins.
quantum numbers while an electron m = − l to + l = − 2, − 1, 0, + 1, + 2
in an atom is designated by four ∴ 3pz orbital contains only two electrons 1
or only 2 electrons are associated with s =±
quantum numbers 2
(c) Total orbital angular momentum of n = 3 , l = 1, m = − 1.
Therefore, option (c) is not a permissible
electron in ‘s’ orbital is equal to zero set of quantum numbers.
(d) The value of m for d 2 is zero
43 Maximum number of electrons in a
z subshell with l = 3 and n = 4 is
Ans. (a) 47 Maximum number of electrons in a
[CBSE AIPMT 2012]
According to Hund’s rule “the pairing of (a) 14 (b) 16 (c) 10 (d) 12 subshell of an atom is determined
electrons in the orbitals of a particular by the following [CBSE AIPMT 2009]
subshell does not takes place until all the Ans. (a)
(a) 4 l + 2 (b) 2 l + 1
orbitals of a subshell are singly occupied. n represents the main energy level and
Moreover, the singly orbitals must have l represents the subshell. (c) 4 l − 2 (d) 2 n2
the electrons with parallel spin. i.e. If n = 4 and l = 3, the subshell is 4f. Ans. (a)
1s2 2s2 2p 1x 2p1y 2p1z In f-subshell, there are 7 orbitals and Total number of subshells = (2l + 1)
each orbital can accommodate a ∴ Maximum number of electrons in the
maximum number of two electrons, so subshell
or maximum number of electrons in
1s2 2s2 2p 1x 2p1y 2p1z = 2 (2l + 1) = 4l + 2
4f subshell = 7 × 2 = 14 .
44 The correct set of four quantum 48 Consider the following sets of

∴ Option (a) is the incorrect option. numbers for the valence electron quantum numbers.
of rubidium atom (at. no. = 37) is n l m s
40 Two electrons occupying the same [CBSE AIPMT 2012]
(i) 3 0 0 +1 / 2
orbital are distinguished by (a) 5, 1, 1, +
1
(b) 6, 0, 0, +
1
[NEET (Phase I) 2016] 2 2 (ii) 2 2 1 +1 / 2
(a) Magnetic quantum number 1 1 −1 / 2
(c) 5, 0, 0, + (d) 5, 1, 0, + (iii) 4 3 –2
(b) Azimuthal quantum number 2 2
(iv) 1 0 –1 −1 / 2
(c) Spin quantum number Ans. (c)
(d) Principal quantum number (v) 3 2 3 +1 / 2
37 Rb = 36[Kr] 5 s 1
Ans. (c) Its valence electron is 5 s 1. Which of the following sets of
Two electrons occupying the same n= 5
quantum number is not possible?
orbital has equal spin but the directions l =0 (For s-orbital) [CBSE AIPMT 2007]
of their spin are opposite. Hence, spin m = 0 (As m = − l to + l)
quantum number, s, (represented +1 /2 (a) (ii), (iii) and (iv) (b) (i), (ii), (iii) and (iv)
1
and − 1 /2) distinguishes them. s =+ (c) (ii), (iv) and (v) (d) (i) and (iii)
2
Atomic Structure 15
Ans. (d) 52 The electronic configuration of Ans. (b)

The value of l varies from 0 to (n − 1) and gadolinium (at. no. = 64) is For n = 3,l = 2 the subshell is 3d (n + l = 5)
the value of m varies from − l to + l [CBSE AIPMT 1997] n = 4, l = 2 the subshell is 4d (n + l = 6)
through zero. (a) [Xe] 4f 8 , 5 d 9 , 6 s 2 n = 4, l = 1 the subshell is 4p (n + l = 5)
1 (b) [Xe] 4 f 7 , 5 d 1, 6 s 2
The value of ‘ s ’ ± which signifies the n = 5, l = 0, the subshell is 5s (n + l = 5)
2 (c) [Xe] 4 f 6 , 5 d2 , 6 s 2
According to (n + l ) rule greater the (n + l )
spin of electron. The correct sets of (d) [Xe] 4 f 3, 5 d 5 , 6 s 2
quantum number are following value, greater the energy that is 6.
n l m s
Ans. (b)
(ii) 2 1 1 −
1 Gd 64 = 1s 2 , 2s 2 2p6 , 3s 2 3p6 3d 10, 56 Electronic configuration of calcium
2 4s 2 4p6 4d 10 4f 7, 5s 2 5p6 5d 1, 6s 2 atom can be written as
1 = [Xe] 4f 7 , 5d 1, 6s 2 [CBSE AIPMT 1992]
(iv) 1 0 0 −
2 (a) [Ne] 4p2
1 53 The orbitals are called degenerate (b) [Ar] 4s 2
(v) 3 2 2 +
2 when [CBSE AIPMT 1996] (c) [Ne] 4s 2
(a) they have the same wave functions (d) [Kr] 4p2
(b) they have the same wave functions
49 The orientation of an atomic orbital Ans. (b)
but different energies
is governed by [CBSE AIPMT 2006] (c) they have different wave functions To write the electronic configuration of
(a) azimuthal quantum number but same energy an atom, it is better if we remember the
(b) spin quantum number atomic number of noble gases and the
(d) they have the same energy
orbitals follow the noble gas. The atomic
(c) magnetic quantum number Ans. (d) number of Ca is 20 and its nearest noble
(d) principal quantum number gas is argon (Ar = 18).
The orbitals having the same energy
Ans. (c) energy but different in orientation, are Hence, the electronic configuration of
The orientation of an atomic orbital is called degenerate orbitals. e.g.3d-orbital, Ca = [Ar] 4s 2 .
governed by magnetic quantum number. l = 2, m = −2, –1, 0, +1, +2, i.e. there are five
different orientations represented byd xy , 57 The electronic configuration of
d yz ,d zx ,d 2 2 and d 2 .
50 The following quantum numbers x −y z Cu (at.no. = 29) is [CBSE AIPMT 1991]
are possible for how many orbital(s) (a) 1s 2 , 2 s 2 2 p 6 , 3 s 2 3p 6 , 4 s 2 , 3d 9
54 If an electron has spin quantum
n = 3, l = 2 and m = + 2? 1 (b) 1s 2 , 2 s 2 2 p 6 , 3 s 2 3p 6 3d 10, 4 s 1
[CBSE AIPMT 2001]
number + and magnetic quantum (c) 1s 2 , 2 s 2 2 p 6 , 3 s 2 3p 6 , 4 s 2 4 p 6 ,
2
(a) 1 (b) 2 5 s2 5 p 1
number –1, it cannot be present in
(c) 3 (d) 4 [CBSE AIPMT 1994]
(d) 1s , 2 s 2 p , 3 s 3p , 4 s 4 p , 3d 3
2 2 6 2 6 2 6
Ans. (a) (a) d-orbital (b) f-orbital Ans. (b)

n = 3,l = 2, m = + 2, s = ± 1 /2 (c) p-orbital (d) s-orbital The electronic configuration of Cu (29) is
These values of quantum numbers are Ans. (d) an exceptional case due to exchange of
possible for only one of the five energy and symmetrical distribution of
Spatial orientation of the orbital with electrons in orbital to acquire more
3d-orbitals as +2 value of m is possible
respect to standard set of cordinate stability.
only for one orbital.
axis. Magnetic quantum number –1 is
m = +2 +1 0 –1 –2 possible only when the azimuthal
quantum number have valuel = 1, which
Cu(29)= ½¾ ½¾ ½¾ ½¾ ½¾ ½¾
1s 2s 2p 3s
is possible for p, d and f-subshells but
not for s-subshell because the value of l ½¾ ½¾ ½¾ ½¾ ½¾ ½¾ ½¾ ½¾ ½
51 Which of the following for s-subshell is zero. 3p 3d 4s
configuration is correct for iron? = 1s 2 , 2 s 2 2p6 , 3 s 2 3p6 3d 10 , 4s 1
[CBSE AIPMT 1999] 55 For which one of the following sets
(a) 1s 2 , 2 s 2 2 p 6 , 3s 2 3p 6 3d 5 of four quantum numbers, an
electron will have the highest
58 The order of filling of electrons in
(b) 1s 2 , 2 s 2 2 p 6 , 3s 2 3p 6 , 4 s 2 , 3d 5 energy? [CBSE AIPMT 1994]
the orbitals of an atom will be
[CBSE AIPMT 1991]
(c) 1s 2 , 2 s 2 2 p 6 , 3s 2 3p 6 , 4 s 2 , 3d 7 n l m s
1 (a) 3d, 4 s , 4 p, 4 d, 5 s
(d) 1s 2 , 2 s 2 2 p 6 , 3s 2 3p 6 3d 6 , 4 s 2 (a) 3 2 1 (b) 4 s , 3d, 4 p, 5 s , 4 d
Ans. (d) 2
1 (c) 5 s , 4 p, 3d, 4 d, 5 s
Firstly the electrons are filled in (b) 4 2 –1 (d) 3d, 4 p, 4 s , 4 d, 5 s
increasing order of energy and then 2
1 Ans. (b)
rearrange the subshells in increasing (c) 4 1 0 −
order as 2 The sequence of energy level can be
1 remembered by the systematic diagram
26 Fe = 1s , 2s 2p , 3s 3p 3d , 4s
2 2 6 2 6 6 2
(d) 5 0 0 − as shown below
2
(a) Hund’s rule (a) 4l − 2 (b) 4l + 2

1s (b) Aufbau principle (c) 2 l + 2 (d) 2 n2
2s 2p
(c) Uncertainty principle Ans. (b)
(d) Pauli’s exclusion principle The number of orbitals in a subshell
3s 3p 3d Ans. (d) = (2l + 1)
4s 4p 4d According, to Pauli’s exclusion principle where,l = azimuthal quantum number
4f
“no two electrons in an atom can have Since, each orbital contains maximum
5s 5p 5d 5f the same values of all the four quantum two electrons, the number of electrons
numbers.” in any subshell
6s 6p 6d In 1s 2 = 2 × number of orbitals
1 = 2 (2l + 1)
7s 7p for I electron n = 1, l = 0, m = 0, s = +
2 = 4l + 2
for II electron n = 1,
1 63 Number of unpaired electrons in
l = 0, m = 0, s = −
Hence, the correct order is 2 N 2+ is/are [CBSE AIPMT 1989]
1s , 2 s , 2p, 3s , 3p, 4s , 3d, 4p, 5s , 4d, 5p, 4f, It means if the values of n, l, and m are (a) 2 (b) 0
5d, 6p, 7s…… same, then the value of spin quantum (c) 1 (d) 3
number must be different, i.e. +1/2 and
Ans. (c)
−1/2.
59 For azimuthal quantum number The electronic configuration of
l = 3,the maximum number of
61 The total number of electrons that
electrons will be [CBSE AIPMT 1991]
can be accommodated in all the
7N = ½¾ ½¾ ½½ ½
(a) 2 (b) 6 (c) 0 (d) 14 1s 2s 2p
orbitals having principal quantum
Ans. (d) ∴ 7N
2+
When azimuthal quantum number is 3

number 2 and azimuthal quantum = ½¾ ½¾ ½
number 1 are [CBSE AIPMT 1990] Hence, the number of unpaired
m = (2l + 1) (a) 2 (b) 4 electron in N2+ is 1.
l =3 (c) 6 (d) 8
m = (2 × 3 + 1) Ans. (c) 64 The number of spherical nodes in
= 7 orbitals 3p-orbital is/are [CBSE AIPMT 1988]
When n = 2 and l = 1, then subshell is 2p.
then total values of m = (2 × 3 + 1) = 7 The number of orbitals in p-subshell (a) one
orbitals. We know that, one orbital
= (2l + 1) = (2 × 1 + 1) (b) three
contains two electrons. Hence, total
number of electrons = 7 × 2 = 14. =3 (c) two
Total (maximum) number of electrons (d) None of the above
Alternative
Total number of electrons = 4l + 2 = 2 × number of orbitals Ans. (a)
= 4 × 3 + 2 = 12 + 2 = 14electrons =2×3=6 The number of spherical nodes in any
(as each orbital contains 2 electrons) orbital ( = n − l − 1)
60 In a given atom no two electrons For 3p-orbital, n = 3 and l = 1
can have the same values of all the 62 The maximum number of electrons ∴ Number of spherical nodes = n − l − 1
four quantum numbers. This is in a subshell is given by the =3− 1− 1
called [CBSE AIPMT 1991] expression [CBSE AIPMT 1989] = 3 − 2 = 1 node
3
Chemical Bonding
and Molecular Structure
TOPIC 1 (b) CH 2O Hybridisation =
1
(6) = 3 (sp2 ) (d) Ammonia, beryllium difluoride,
Type of Bonds, Bond 2 water, 1,4-dichlorobenzene
Shape = Trigonal planar. Ans. (c)
Parameter and Resonance
In option (c), for all molecules,
01 The correct sequence of bond C [i, vi, iii, viii]µ =0.
H H
enthalpy of ‘CX’ bond is The structure of all compounds are as
[NEET 2021] Dipole moment,µ ≠ 0
follows :
(a) CH3 F < CH3  Cl < CH3 Br< CH3 I CH2O is polar in nature.
1 (i) Boron trifluoride (BF3)
(b) CH3 F> CH3  Cl > CH3 Br > CH3 I (c) SbCl 5 Hybridisation =× 10 = 5 (sp3d)
(c) CH3 F < CH3  Cl > CH3 Br > 2 F
CH3 I Shape = Trigonal bipyramidal ⇒ F B ; µ=0
(d) CH3  Cl > CH3 F > CH3 Br > Cl
CH3 I F
Ans. (b) Cl (ii) Hydrogen fluoride (HF)
Cl Sb
On moving down the group from F to I, ⇒ H F; µ ≠ 0
Cl
the size of atom increases. Order of the (iii) Carbon dioxide (CO2)
Cl
size of halogen atoms is I > Br > Cl > F.
Dipole moment, µ = 0 ⇒ O C O ; µ=0
So, the bond length of C—X bond also
increases from F to I and hence, the SbCl 5 is non-polar in nature.
(iv) 1,3-dichloro benzene
bond enthalpy decreases from F to I. (d) NO2 Hybridisation (m-C6H4Cl2) ⇒ Cl
Correct order of bond length of C—X 1 1
= × (4 + 2) = × 6 = 3 (sp2 ).
bond is 2 2
; µ≠0
H3C  I > H3C Br > H3C  Cl > H3C F.
Correct order of bond enthalpy is Cl
N
H3C  F > H3C  Cl > CH3 Br > H3C I. (v) Nitrogen trifluoride (NF3)
02 Which of the following molecules is Shape = Trigonal planar

Dipole moment,µ ≠ 0 ⇒ N ;µ ≠ 0
non-polar in nature? [NEET 2021]
(a) POCl3 (b) CH2O NO2 is polar in nature. F F
F
(c) SbCl5 (d) NO2
03 Which of the following set of (vi) Beryllium difluoride (BeF2)
Ans. (c) molecules will have zero dipole ⇒ FBeF ;µ=0
1 moment ?
(a) POCl 3 Hybridisation = × 8 = 4 (sp3) [NEET (Sept.) 2020]
2 (a) Boron trifluoride, hydrogen fluoride, (vii) Water (H2O)
carbon dioxide, 1,3-dichlorobenzene
P (b) Nitrogen trifluoride, beryllium
⇒ O ; µ≠0
Cl Cl difluoride, water,
Cl 1,3-dichlorobenzene H H
Shape = Tetrahedral (c) Boron trifluoride, beryllium
Dipole moment, µ ≠ 0 difluoride, carbon dioxide, 1,
POCl3 is polar in nature. 4-dichlorobenzene
(viii) 1,4-dichloro benzene Key concept The species that have same µ4
(p=C6H4Cl2) ⇒ Cl number of electrons have same bond µ4
N µ1 µ3 N µ1
order. µ3
H µ2H F µ2 F
Species Number of electrons H F
; µ=0
CO 6 + 8 = 14 Resultant of Resultant of
3N  H 3N  F
Cl NO 7 + 8 = 15 bond lie in the same bond lie opposite to µ4
direction as µ4
(ix) Ammonia (NH3) O2 8 + 8 = 16
Hence, µnet = µres + µ4
+
NO 7 + 8 − 1 = 14 This is because in case ofNH3, the net
−
6 + 7 + 1 = 14
N H bond dipole is in the same direction
⇒ N ; µ≠0 CN
as the direction of dipole of lone pair but
H H O −2 8 + 8 + 1 = 17 in case of NF3, the direction of net bond
H dipole of three N F bonds is opposite
[Q µ = Dipole moment] Thus, both CN− and CO have equal than that of the dipole of the then lone
number of electrons. So, their bond pair.
order will be same.
04 Which of the following is the
correct order of dipole moment? 08 Which one of the following
06 Predict the correct order among molecules contain no π-bond?
[NEET (Odisha) 2019]
the following. [NEET 2016, Phase I] [NEET 2013]
(a) NH3 < BF3 < NF3 < H2O
(a) lone pair-lone pair > bond pair-bond (a) CO2 (b) H2O
(b) BF3 < NF3 < NH3 < H2O pair > lone pair-bond pair (c) SO2 (d) NO2
(c) BF3 < NH3 < NF3 < H2O (b) bond pair-bond pair > lone pair-bond
(d) H2O < NF3 < NH3 < BF3 Ans. (b)
pair > lone pair-lone pair
Ans. (b) (c) lone pair-bond pair > bond pair-bond All the molecules have O-atom with lone
pair > lone pair-lone pair pairs, but inH2O the H-atom has no
BF3 has zero dipole moment as it is vacant orbital for π-bonding. That’s why
symmetrical in nature.H2O has maximum (d) lone pair-lone pair > lone pair-bond
it does not have any π-bond.
dipole moment as it possess two lone pair > bond pair-bond pair
In all other given molecules, the central
pair of electrons. BetweenNH3 and NF3, Ans. (d)
atom because of the presence of vacant
NH3 has greater dipole moment though According to the postulate of VSEPR orbitals is capable to form π-bonds.
in NH3 and NF3, both N possesses one theory, a lone pair occupies more space
lone pair of electrons. than a bonding pair, since it lies closer to
This is beacuse in case ofNF3, the net
09 Which of the following is least likely
the central atom. This means that the
N—H bond dipole is in the same direction to behave as Lewis base?
repulsion between the different electron
as the direction of dipole of lone pair. [CBSE AIPMT 2011]
pairs follow the order.
But in case ofNF3, the direction of net (a) NH3 (b) BF3
lp − lp > lp − bp > bp − bp
dipole moment of three —N—F bonds is (c) OH− (d) H2O
opposite to that of the dipole moment of Ans. (b)
the lone pair. Thus, the correct of dipole 07 Which of the following molecules
moment is has the maximum dipole moment? BF3 is an electron deficient species, thus
[CBSE AIPMT 2014] behaves like a Lewis acid.
N − Na
O > N >
(a) CO2 (b) CH 4 Q Bond order = b
(c) NH 3 (d) NF 3 2
H H H H
H Ans. (d)
(H2O) (NH3) 10 The electronegativity difference
CO2 and CH4 have zero dipole moment as
these are symmetrical in nature. between N and F is greater than
F
N > F BetweenNH3 and NF3,NF3 has greater that between N and H yet the
B
F F F
dipole moment though inNH3 and NF3 dipole moment of NH3 (1.5 D) is
F both, N possesses one lone pair of larger than that of NF3 (0.2 D). This
(NF3) (BF3) electrons. is because [CBSE AIPMT 2006]
H
µ1 (a) in NH3 as well as inNF3 , the atomic
05 Which one of the following pairs of µres
O C O C µ4 dipole and bond dipole are in the
species have the same bond order? µ1 same direction
net = 0
[NEET 2017] H µH
H 3 (b) in NH3 , the atomic dipole and bond
(a) CO, NO ∴ µ = µ + µ + µ = –µ dipole are in the same direction
res 1 2 3 4
(b) O2 , NO + and µnet = µres + µ4 whereas inNF3 these are in opposite
(c) CN− , CO ∴ µnet = µ1 + µ2 + µ3 + µ4 directions
(d) N2 , O2− = – µ4 + µ4 = 0 (c) in NH3 as well asNF3 , the atomic
dipole and bond dipole are in
Ans. (c) net = 0
opposite directions
Chemical Bonding and Molecular Structure 19
(d) in NH3 the atomic dipole and bond F F Ans. (b)

dipole are in the opposite directions In NH+4 bond angle is maximum (nearer
whereas inNF3 these are in the same B Si 109°) due to its tetrahedral geometry.
directions F F F F
Ans. (b)
µ=0
F 16 In PO 3−
4 ion, the formal charge on
µ=0
each oxygen atom and P—O
N N F F F F bond order respectively are
[CBSE AIPMT 1998]
F F H H S Xe
F H
(a) – 0.75, 0.6 (b) – 0.75, 1.0
F F F F (c) – 0.75, 1.25 (d) – 3, 1.25
µ = 0.24 D µ = 1.47 D
F is more electronegative than N, µ = 0.632 D µ=0 Ans. (c)
therefore direction of bond is from N to (Permanent dipole moment) P—O bond order
F whereas N is more electronegative
Q SF 4 have µ > 0 Total Number of bonds in all possible
than H, the direction of the bond is from
H to N. Thus whereas resultant moment ∴ It has permanent dipole moment. =
direction between two atoms
of N-H bonds adds up to the bond Total number of resonating structures
moment of lone pair, that of 3N-F bonds 13 In BrF3 molecule, the lone pairs 2+ 1+ 1+ 1 5
= = = 1.25
partly cancel the resultant moment of occupy equatorial positions to 4 4
lone pair. Hence, the net dipole moment ∴ Bond order = 1.25
of NF3 is less than that ofNH3.
minimise [CBSE AIPMT 2004]
(a) lone pair-bond pair repulsion Resonating structures are
(b) bond pair-bond pair repulsion –
11 In which of the following molecules O O
(c) lone pair-lone pair repulsion and lone |
| |
are all the bonds not equal? –O—
P—O– O== P—O
–
pair-bond pair repulsion
[CBSE AIPMT 2006] | |
(a) ClF3 (b) BF3
(d) lone pair-lone pair repulsion O– O–
(c) AlF3 (d) NF3 Ans. (d)
In BrF3 molecule, Br is sp 3d hybridised, O– O–
Ans. (a)
but its geometry is T-shaped due to |
O–— P==O –O— |
In ClF3 all bonds are not equal due to its P—O–
distortion of geometry from trigonal | ||
trigonal-bipyramidal (sp3d hybridisation)
bipyramidal to T-shaped by the O– O
geometry
involvement of lone pair-lone pair
Total charge onPO3–4 ion is –3
F repulsion.
Total charge
F Cl F =
F Total entity of O- atom
Trigonal bipyramidal geometry
Br—
So, the average formal charge on each
BF3 and AlF3 show trigonal symmetric F 3
F O-atom is = − = − 0.75
structure due to sp2 hybridisation. Here, lp – lp repulsion = 0 4
F lp – bprepulsion = 4
F B bp – bprepulsion = 2 17 Which one is not paramagnetic
F among the following? [at. no. of
14 In NO −3 ion number of bond pair and Be = 4,Ne = 10, As = 33, Cl = 17]
F
lone pair of electrons on nitrogen [CBSE AIPMT 1998]
and F Al
atom are [CBSE AIPMT 2002] (a) Cl− (b) Be
F
(a) 2, 2 (b) 3, 1 (c) 1, 3 (d) 4, 0 (c) Ne2+ (d) As+
NF3 shows pyramidal geometry due to
Ans. (a)
sp3 hybridisation. Ans. (d)
In NO3− ion Paramagnetic character is based upon
N O presence of unpaired electron.
17 Cl = 1s , 2 s 2p , 3 s 3px 3py 3pz
– – 2 2 6 2 2 2 2
F F O–—N O N O
F O O
3bp + 1lp In Cl − no unpaired electron, so it is in
Nitrogen has four bond pair and zero nature diamagnetic.
lone pair of electrons, due to the
4 Be = 1s , 2 s 2px
2 1 1
12 Which of the following would have presence of one coordination bond.
10 Ne
2+
= 1s , 2 s 2px 2py1 2pz1
2 2 2
a permanent dipole moment?
[CBSE AIPMT 2005] 15 In which of the following, bond = 1s 2 , 2 s 2 2p6 , 3 s 2 3p6 3d 10 ,
+
33 As
(a) BF3 (b) SiF4 angle is maximum? 4s 2 4px1 4py1 4pz0
(c) SF4 (d) XeF4 [CBSE AIPMT 2001]
While all others have unpaired electron,
Ans. (c) (a) NH3 (b) NH+4 (c) PCl3 (d) SCl2 so they are paramagnetic in nature.
18 The molecule which does not Ans. (d) Ans. (b)

exhibit dipole moment is H-bond is weakest bond because its NaF has high lattice energy because Na +
[CBSE AIPMT 1997] bond dissociation energy is very low as is smallest in size and lattice energy
(a) NH3 (b) CHCl3 compared to other given bonds (10 kJ increases as the size of cation
mol −1). decreases. (In the given question anion
(c) H2O (d) CCl4
is common in all compound)
Ans. (d) 23 Which of the following pairs will
CCl 4 does not show dipole moment form the most stable ionic bond? 27 Strongest hydrogen bonding is
because it has tetrahedral symmetrical [CBSE AIPMT 1994] shown by [CBSE AIPMT 1992]
structure.
(a) Na and Cl (b) Mg and F (a) H2O (b) NH3
(c) Li and F (d) Na and F (c) HF (d) H2 S
19 For two ionic solids CaO and KI,
Ans. (b) Ans. (c)
identify the wrong statement among
The ionic bond between Mg and F is most HF have strongest hydrogen bond
the following. [CBSE AIPMT 1997]
stable because in these the electrostatic because the electronegativity of F-atom
(a) Lattice energy of CaO is much larger is high and produce strong electrostatic
force of attraction is maximum. As Mg
than that of KI force of attraction.
has high electropositive character and F
(b) KI is soluble in benzene has high electronegative character
(c) KI has lower melting point among all other options that are given in 28 Which one of the following
(d) CaO has higher melting point question. formulae does not correctly
Ans. (b) represent the bonding capacities
KI is ionic compound, so it is not soluble 24 Which of the following statements of the atoms involved?
in non-polar solvent (i.e. dipole moment is not correct? [CBSE AIPMT 1991]
(µ) for benzene = 0). [CBSE AIPMT 1993, 1990] +
 H 
(a) Double bond is shorter than a single 
 
20 Which one of the following has the bond (a) H — P —H 
highest dipole moment? (b) Sigma bond is weaker than a π-bond   
[CBSE AIPMT 1997] (c) Double bond is stronger than a single  H 
(a) AsH3 (b) SbH3 bond F F
(d) Covalent bond is stronger than (b)
(c) PH3 (d) NH3 O
hydrogen bond
Ans. (d) O
Ans. (b)
In the given molecules nitrogen has (c) O ← N
greater electronegativity. So, it has Sigma bond is always stronger than
π-bond because the extent of O —H
greater dipole moment and correct order
of dipole moment is overlapping is maximum in sigma bond O
formation. (d) H —C ==C
NH3 > PH3 > AsH3 > SbH3
O —H
21 The BCl 3 is a planar molecule 25 Which one of the following is the
correct order of interactions? Ans. (d)
whereas NCl 3 is pyramidal because [CBSE AIPMT 1993] O
1 2
[CBSE AIPMT 1995] In H— C==C carbon number 2
(a) Covalent < hydrogen bonding < van
(a) B — Cl bond is more polar than N — Cl der Waals’ < dipole-dipole O —H
bond (b) van der Waals’ < hydrogen bonding have five valency which is not possible,
(b) N — Cl bond is more covalent than < dipole-dipole < covalent so it does not correctly represent the
B — Cl bond (c) van der Waals’ < dipole-dipole < bonding capacities of C atom.
(c) nitrogen atom is smaller than boron hydrogen bonding < covalent
atom (d) Dipole-dipole < van der Waals’ <
(d) BCl 3 has no lone pair butNCl 3 has a
29 Among LiCl, BeCl 2 , BCl 3 and CCl 4 ,
hydrogen bonding < covalent
lone pair of electrons the covalent bond character
Ans. (b)
Ans. (d) follows the order
The van der Waals’ forces are weakest [CBSE AIPMT 1990]
BCl 3 have sp2 hybridisation and no lone forces and covalent bond is strongest,
pair of electron on central atom butNCl 3 so the order of interactions is van der (a) LiCl <BeCl2 > BCl3 > CCl4
have sp3 hybridisation and also contains Waals’ < H-bonding < dipole-dipole < (b) LiCl <BeCl2 <BCl3 > CCl4
one lone pair of electron on nitrogen, so covalent. (c) LiCl <BeCl2 <BCl3 <CCl4
BCl 3 is planar. (d) LiCl > BeCl2 > BCl3 > CCl4
26 Among the following which Ans. (c)
22 The weakest among the following compound will show the highest The electronegativity increases from left
types of bond is [CBSE AIPMT 1994] lattice energy? [CBSE AIPMT 1993] to right in any period, so the
(a) ionic (b) covalent electronegativity follows the order
(a) KF (b) NaF
(c) metallic (d) H-bond (c) CsF (d) RbF Li < Be < B < C
and hence, the covalent character of Cl Ans. (c)

chlorides of these elements increase Cl Hybridisation of a central atom can be
from Li to C because size of cation left to Cl P calculate by using the formula :
right decreases and according to Fajans’ Cl 1
rule covalent character increases. Hybridisation = [number of valence
Cl 2
Hybridisation of P → sp3d electrons + Number of side atoms –
30 H2O has a net dipole moment while Positive charge + Negative charge]
Structure of PCl 5 → Trigonal bipyramidal
BeF2 has zero dipole moment Electronic configuration of B
(B) SF6
because [CBSE AIPMT 1989] = 1s 2 , 2s 2 , 2p1
S (Ground state) = 3 s 2 3 p4
(a) H2O molecule is linear whileBeF2 is Number of valence electrons in B = 3
S* (excited state)
bent electrons in last shell, n = 2
3s 3p 3d
(b) BeF2 molecule is linear whileH2O is Number of side atoms in
bent BF3 = 3F-atoms.
(c) fluorine has more electronegativity 1 1
So, hybridisation = (3 + 3) = × 6 = 3.
than oxygen F F F F F F F 2 2
(d) beryllium has more electronegativity
F F Hybridisation of B in BF3 is sp2 .
than oxygen
S Number of electrons around central
Ans. (b) F F atom, B inBF3 is equal to the number of
H2O have bent structure in which the two electrons in three sigma bonds (B—F) i.e.
F
O—H bonds are oriented at an angle of = 3 B—F bonds × 2 electrons in one
104.5°, so water have a net dipole Hybridisation of S→ sp3d2
σ-bond.
moment whereasBeF2 have linear Structure of SF6 → Octahedral
= 6 electrons
geometry, so the dipole moment of one (C) BrF5
bond is cancelled by another bond, so it Br (Ground state) = 3 s 2 3 p5
have zero dipole moment. 33 Match the coordination number
Br* (excited state) and type of hybridisation with
3s 3p 3d
TOPIC 2 distribution of hybrid orbitals in
space based on valence bond theory.
Hybridisation and Lone [NEET (Oct.) 2020]
VSEPR Theory pair F F F F F
Coordination
F number and Distribution of
hybrid orbitals
31 Match List-I with List-II. F F
type of
in space
hybridisation
Br
List-I List-II F F
4, sp 3 trigonal
Square A. I.
A. PCl5 I. bipyramidal
pyramidal Hybridisation of Br → sp d 3 2
Structure of BrF5 → Square pyramidal B. 4, dsp2 II. octahedral

B. SF6 II. Trigonal planar
(D) BF3
C. BrF5 III. Octahedral B (Ground state) = 2 s 2 2 p1 C. 5, sp 3d III. tetrahedral
Trigonal B* (excited state) D. 6, d2 sp 3 IV. square planar

D. BF3 IV. 2p F
bipyramidal 2s
Select the correct option.
Choose the correct answer from B A B C D A B C D
the options given below [NEET 2021] F F F F F
(a) II III IV I (b) III IV I II
A B C D A B C D
Hybridisation of B→ sp2 (c) IV I II III (d) III I IV II
(a) IV III I II (b) II III IV I
Structure of BF3 → Trigonal planar Ans. (b)
(c) III I IV II (d) IV III II I ∴ Correct match is
Ans. (a) (A)-(IV); (B)-(III); (C)-(I); (D)-(II)
(A) PCl 5 (A) CN==4, sp3
P (Ground state) = 3 s 2 3 p3 32 BF 3 is planar and electron deficient
P* (excited state) compound. Hybridisation and or tetrahedral ⇒ (III)
3s 3p 3d number of electrons around the
central atom, respectively are (B) CN==4, dsp2
[NEET 2021]
Cl Cl Cl Cl Cl (a) sp 3 and 4 (b) sp 3 and 6

or square planar ⇒ (IV)
(c) sp2 and 6 (d) sp2 and 8
Column I Column II (a) The H—O—H bond angle in H2 O is

(C) CN==5, sp3d larger than the H—C—H bond angle in
Distorted CH 4
C. XeOF4 (iii)
or trigonal bipyramidal ⇒ (I) octahedral (b) The H—O—H bond angle in H2 O is
smaller than the H—N—H bond angle
XeO 3 Square in NH 3
D. (iv)
(D) CN ==6, d2sp3 pyramidal (c) The H—C—H bond angle in CH 4 is
larger than the H—N—H bond angle in
Codes NH 3
or octahedral ⇒ (II) A B C D A B C D (d) The H—C—H bond angle in CH 4 , the
Hence, option (b) is correct. (a) (ii) (iii) (iv) (i) (b) (iii) (iii) (i) (iv) H—N—H bond angle in NH 3 and the
(c) (iii) (iv) (i) (ii) (d) (i) (ii) (iii) (iv) H—O—H bond angle in H2 O are all
34 Identify the wrongly matched pair. greater than 90°
Ans. (a)
[NEET (Oct.) 2020] Ans. (a)
The given xenon compounds with its
Molecule Shape of geometry of As the number of lone pair of electrons
structures are as follows:
molecule on central element increases, repulsion
F F between those lone pair of electrons
(a) PCl5 Trigonal planar
(A) XeF4 Xe (Square planar) increases and therefore, bond angle
(b) SF6 Octahedral F F decreases.
Molecules Bond angle
(c) BeCl2 Linear
F CH 4 (no lone pair of electrons) 109.5°
(d) NH3 Trigonal pyramidal F F NH 3 (one lone pair of electrons) 107.5°
Ans. (a) (B) XeF6 Xe (Distorted octahedral)
H2 O (two lone pair of electrons) 104.45°
F F
Cl F 38 The hybridisations of atomic
orbitals of nitrogen in NO +2 , NO −3
Cl
O
(A) PCl5 ⇒ Cl P F F and NH+4 respectively are
Cl (C) XeOF4 Xe (Square pyramidal)
sp3dCl
[NEET 2016, Phase II]
F F (a) sp, sp 3 and sp2 (b) sp2 , sp 3 and sp
⇒ Geometry=shape=trigonal
bipyramidal (c) sp, sp2 and sp 3 (d) sp2 , sp and sp 3
[Nottrigonalplanar] Ans. (c)
F (D) XeO3 Xe (Pyramidal)
Ion Structure Hybridisation
F F O O
O NO 2+ sp
(B) SF6 ⇒ S O==N==O
Hence, the correct match is NO −3 sp 2
F F O
(A) → (ii), (B) → (iii), (C)→ (iv), (D) → (i) N→O
sp3d2 F O
⇒ Geometry = shape = octahedral 36 Predict the correct order among NH 4+ H sp 3
sp the following. [NEET 2016, Phase I]
(C) BeCl2 ⇒ Cl Be Cl
+
N
⇒ Geometry = shape = linear (a) lone pair-lone pair > bond pair-bond H H
pair > lone pair-bond pair H
(b) bond pair-bond pair > lone pair-bond Thus, option (c) is correct.
pair > lone pair-lone pair
(D) NH3 ⇒ H N H
(c) lone pair-bond pair > bond pair-bond 39 Which of the following species
3 pair > lone pair-lone pair contains equal number of σ and
sp H (d) lone pair-lone pair > lone pair-bond π-bonds? [CBSE AIPMT 2015]
⇒electrongeometry = tetrahedral pair > bond pair-bond pair (a) HCO–3 (b) XeO4
⇒ Shape = trigonal pyramidal
Ans. (d) (c) (CN)2 (d) CH2 (CN)2
Hence, option (a) is wrongly matched
According to the postulate of VSEPR Ans. (b)
pair.
theory, a lone pair occupies more space
than a bonding pair, since it lies closer to Structure σ and π bonds
35 Match the xenon compounds in
the central atom. This means that the (a) O
Column I with its structure in
repulsion between the different electron  σ bond-4
Column II and assign the correct pairs follow the order. C
π bond-1
code : [NEET (National) 2019] lp − lp > lp − bp > bp − bp O O H
Column I Column II (b) O
37 Consider the molecules CH4 , NH3

A. XeF4 (i) Pyramidal and H2O. Which of the given Xe
statements is false?  σ bond-4
B. XeF6 (ii) Square planar [NEET 2016, Phase I]
O O O π bond-4
Structure σ and π bonds Ans. (b) Ans. (d)

(c) N ≡≡ C C ≡≡ N σ bond-3 Symmetrical molecules are generally NO2− → sp2
π bond-4
non-polar although they have polar NO−3 → sp2
bonds. This is because bond dipole of NH2+ → sp3
H one bond is cancelled by that of the
NH−4 → sp3
 σ bond-6 other. BF3, SiF4 and XeF4 being
π bond-4 SCN+ → sp
(d) N ≡≡ C C C ≡≡ N symmetrical as non-polar. SF4 is
 unsymmetrical because of the NO2 and NO−3 both have the same
−
H presence of a lone pair of electrons. hybridisation, i.e. sp2 .

Due to which it is a polar molecule.
46 In which of the following pairs of
40 Which of the following pairs of ions 43 Which of the following species molecules/ions, the central atoms
are isoelectronic and isostructural? contains three bond pairs and one have sp 2 hybridisation?
[CBSE AIPMT 2015] [CBSE AIPMT 2010]
lone pair around the central atom?
(a) CO23– , SO23– (b) CIO–3, CO23– [NEET 2013] (a) NO2− and NH3
(c) SO2– –
3 , NO 3 (d) ClO –3, SO2–
3 (a) H2O (b) BF3 (c) NH2− (d) PCl3 (b) BF3 and NO2−
Ans. (d) Ans. (d) (c) NH2− and H2O
ClO−3 , == SO23− (a) H2O ⇒ O (d) BF3 and NH2−
Cl H H Ans. (b)
S
(2 bp + 2 lp)
O –
O
–
O O – Key Idea For sp2 hybridisation, there
O O [bp = bond pair and lp = lone pair] must be 3 σ-bonds or 2σ-bonds along
F with a lone pair of electrons.
O– O  (i) NO2− ⇒2 σ + 1 lp = 3, i.e. sp2
O C N – (b) BF3 ⇒ B hybridisation
O F
– F
O O (3 bp + 0 lp) (ii) NH3 ⇒3 σ + 1 lp = 4, i.e. sp3
Number of electrons – hybridisation
(c) NH2 ⇒
–
CO23− = 6 + 2 + 24 = 32 N iii) BF3 ⇒3 σ + 0 lp = 3, i.e. sp2
H H
SO23− = 16 + 2 + 24 = 42 hybridisation
(iv) NH2− ⇒2 σ + 2 lp = 4, i.e. sp3
(2bp + 2lp)
ClO−3 = 4 + 24 + 1 = 42
CO23− = 6 + 24 + 2 = 32
Cl hybridisation
(d) PCl3 ⇒ P
NO−3 = 7 + 2 + 24 = 33 Cl Cl (v) H2O ⇒2 σ + 2 lp = 4, i.e. sp3
hybridisation
Hence, ClO−3 and SO23− are isoelectronic (3 bp + 1 lp)
and are pyramidal in shape. Thus, in PCl3 , the central P-atom is Thus, among the given pairs, only BF3
surrounded by three bond pairs and one and NO2− have sp2 hybridisation.
41 Which one of the following species lone pair.
has plane triangular shape? 47 In which one of the following
44 Considering the state of species the central atom has the
[CBSE AIPMT 2014]
hybridisation of carbon atoms, find type of hybridisation which is not
(a) N3 (b) NO −3
(c) NO2− (d) CO2 out the molecule among the the same as that present in the
Ans. (b)
following which is linear? other three? [CBSE AIPMT 2010]
(b) I−3
[CBSE AIPMT 2011]
Species with sp2 hybridisation are planar (a) SF4
(a) CH3 —C ≡≡ C—CH3 (c) SbCl2− (d) PCl5
triangular in shape. Among the given 5
speciesNO−3 is sp2 hybridised with no
(b) CH2 == CH—CH2 — C ≡≡ CH Ans. (c)
lone pair of electrons on central atom, N. (c) CH3 — CH2 — CH2 — CH3
Key Idea Molecules having same
Whereas,N3, NO2− and CO2 are (d) CH3 — CH == CH— CH3
hybridisation have same number of hybrid
sp hybridised with a linear shape. Ans. (a) orbitals,
– 4 3 2 1 1
O H3 C  C ≡≡ C  CH3 is linear because C2 H = [V + X − C + A]
+ 2
N N N N
– and C3 are sp hybridised carbon atom.
where,
O O 45 Which of the two ions from the list V = number of valence electrons of
–
given below, have the geometry central atom
O N– O O C O that is explained by the same X = number of monovalent atoms
hybridisation of orbitals, C = charge on cation
NO–2 , NO–3 , NH–2 , NH+4 , SCN– ? A = charge on anion
42 Which of the following is a polar [CBSE AIPMT 2011] SbCl25− = sp 3d2 , PCl 5 = sp 3d
molecule? [NEET 2013]
(a) NH+4 and NO –3 −
(b) SCN and NH2– SF 4 = sp 3d , I −3 = sp 3d
(a) BF3 (b) SF4 (c) SiF4 (d) XeF4 (c) NO2– and NH2– (d) NO2– and NO –3
48 In which of the following Ans. (d) Ans. (a)

molecules/ions BF3 , NO −2 , NH−2 and (a) SF4 = irregular tetrahedral (sp3d,one SCl 4 is not isostructural with SiCl 4
H2O, the central atom is lone pair) because it shows square planar
XeF4 = square planar (sp3d2 , two lone structure due to involvement of
sp 2 hybridised? [CBSE AIPMT 2009] pairs) repulsion between lone pair and bond
(a) NO2− and NH2− (b) NH2− and H2O (b) SO23− = pyramidal (sp3, one lone pair) pair of electrons.
(c) NO2− and H2O (d) BF3 and NO2− NO−3 = trigonal planar (sp2 ) SO24− shows tetrahedral structure due to
Ans. (d) (c) BF3 = trigonal planar (sp2 ) sp3 hybridisation.
NF3 = pyramidal (sp3) PO3−
BF3 4 shows tetrahedral structure due
F (d) BrO−3 = pyramidal (sp3, one lone pair) to sp3 hybridisation.
σ XeO3 = pyramidal (sp3, one lone pair)
B— σ
F ⇒3 σ-bonds, i.e. sp2 hybridisation NH+4 shows tetrahedral structure due to
σ sp3 hybridisation.
F 51 Which of the following species has
Planar structure a linear shape? [CBSE AIPMT 2006] 54 Which of the following molecules
NO2− (a) NO2– (b) SO2 has trigonal planar geometry?
•• s (c) NO2+ (d) O 3 [CBSE AIPMT 2005]
O==•• N •• ==O ⇒2σ-bonds +1 lone pair of Ans. (c) (a) IF3 (b) PCl3
electrons, i.e. sp2 hybridisation + (c) NH3 (d) BF3
NO2 has linear shape due to sp
NH2– +
Ans. (d)
••
H σ—N σ—H ⇒2σ-bonds +2 lone pairs, i.e.
hybridisation of N in NO2 IF3 has bent-T geometry
•× + F
sp3 hybridisation O==N == O
••
•O WhileSO2 , NO2– and O3 have angular I F
•
H2O =σ σ
shape
F
H H S N
2lp + 3 bp = sp3d hybridisation
⇒ 2σ-bonds +2 lone pairs, i.e. sp3 –
O O O O PCl3 has pyramidal geometry
hybridisation, Thus, inBF3 and NO2− , V-shape V-shape
central atom is sp2 hybridised, while +
NH2 , NH 3 and H2 O are sp 3 hybridised. O
P
49 The angular shape of ozone O O– Cl Cl
V-shape Cl
molecule (O 3 ) consists of 1lp + 3 bp = sp3 hybridisation
[CBSE AIPMT 2008] Angular shape (due to sp 2 hybridisation
of central atom or ion) NH3 has trigonal pyramidal geometry
(a) 1 sigma and 2 pi-bonds
(b) 2 sigma and 2 pi-bonds
(c) 1 sigma and 1 pi-bonds 52 Which of the following is not a
N
(d) 2 sigma and 1 pi-bonds correct statement? H H
[CBSE AIPMT 2006] H
Ans. (d)
(a) The electron deficient molecules can 1lp + 3bp = sp3 hybridisation
In case of single bond, there is only one act as Lewis acids
σ-bond, in case of double bond, there is BF3 has trigonal planar geometry
(b) The canonical structures have no
one σ and one π-bonds while in case of real existence F
triple bond, there is one σ and two (c) Every AB 5 molecule does infact have F B
π-bonds. Thus, angular shape of ozone F
square pyramid structure (µ = 0)
(O3) contains 2σ and 1 π-bonds as shown
(d) Multiple bonds are always shorter 3bp only = sp2 (hydridisation)
below
than corresponding single bond
Ans. (c) 55 H2O is dipolar, whereas BeF2 is not.
Generally, AB 5 molecules have trigonal
It is because [CBSE AIPMT 2004]
2 sigma and one π-bonds. bipyramidal structure due to sp3d
hybridisation but in some cases due to (a) the electronegativity of F is greater
presence of lone pair of electrons, its than that of O
50 In which of the following pairs, the (b) H2O involves hydrogen bonding
geometry becomes distorted.
two species are isostructural? whereas BeF2 is a discrete molecule
[CBSE AIPMT 2007] (c) H2O is linear andBeF2 is angular
53 Which of the following is not
(a) SF4 and XeF4 (d) H2O is angular andBeF2 is linear
− isostructural with SiCl 4 ?
(b) SO2−
3 and NO 3 [CBSE AIPMT 2006] Ans. (d)
(c) BF3 and NF3
(a) SCl4 (b) SO2– The structure of H2O is angular or
(d) BrO −3 and XeO 3 (c) PO 3–
4
(d) NH4+ V-shape and has sp3-hybridisation and
4
104.5° bond angle. Thus, its dipole 14 Si = 1s 2 , 2 s 2 , 2p6 , 3s 2 3p2 (in ground 59 Which of the following has pπ - dπ
moment is positive or more than zero. state)
bonding? [CBSE AIPMT 2002]
14 Si = 1s , 2 s 2p , 3s 3p (in excited
2 2 6 1 3
O
state) (a) NO –3 (b) SO2–
3
3–
H
104.5°
H 3s 3p (c) BO 3 (d) CO2–
3
But in BeF2 , structure is linear due to Ans. (b)

3
sp hybridisation (µ = 0) In SO2–
3 , S is sp hybridised, so
180° sp3 hybridisation O–
π σ
3
F Be F
Hence, four equivalent sp hybrid O σ S
orbitals are obtained and they are σ
Thus, due toµ > 0, H2O is dipolar and due O–
overlapped by four p-orbitals of four
to µ = 0, BeF2 is non-polar. 16 S= 1s , 2 s 2p , 3 s
2 2 6 2
3px1
3py1 3pz1
fluorine atoms on their axis. Thus, it 1 442 443
(Sulphur atom in
shows following structure : excited state) sp 3hybridisation
56 In an octahedral structure, the pair F
of d orbitals involved in 1
3d xy
d 2 sp 3 -hybridisation is Unhybridised
[CBSE AIPMT 2004] Si In ‘S’ the three p-orbitals forms σ-bonds
(a) dx 2 − y 2 , dz 2 (b) dxz , dx 2 − y 2 with three oxygen atoms and
F F unhybridised d-orbital is involved in
(c) dz 2 , dxz (d) dxy , dyz π-bond formation.
Ans. (a)
F O8 = 1s 2 , 2 s 2 2p2x 2py1 2pz1
F
In the formation of d2 sp3 hybrid orbitals, In oxygen two unpaired p-orbitals are
two (n − 1) d-orbitals of e g set, i.e. σ present, one is involved in σ-bond
(n– 1) dz 2 and (n– 1) d x 2 –y 2 orbitals, one n s formation while other is used in π-bond
or Si
and three np (npx , npy and npz .) orbitals σ σ formation.
combine together. F σ F
Thus inSO23– , p and d-orbitals are involved
for pπ- dπ bonding.
57 In a regular octahedral molecule, F
MX 6 the number of X M  X WhileSF4 is not tetrahedral but it is 60 Which of the following two are
bonds at 180° is [CBSE AIPMT 2004] arranged in trigonal bipyramidal isostructural? [CBSE AIPMT 2001]
geometry (has see saw shape) because (a) XeF2 , and IF2– (b) NH3, and BF3
(a) 3 (b) 2 in itS is sp3d hybrid.
(c) 6 (d) 4 (c) CO2–
3 , and SO 3
2–
(d) PCl5 , and ICl5
16 S = 1 s , 2 s 2p , 3s 3px 3py 3pz
2 2 6 2 2 1 1
Ans. (a) Ans. (a)

(in ground state)
In octahedral structure M X6 , the six Compounds having same structure and
hybrid orbitals (sp3d2 ) are directed same hybridisation are known as
= 1s 2 , 2 s 2 2p6 , 3 s 2 3px1 3py1 3pz1, 3d xy
1
towards the cornes of a regular 144424443 isostructural species. e.g.

octahedral with an angle of90°. sp 3d hybridisation XeF2 and IF2– are sp3d hybridised and
According to following structure of M X6 , (in first excitation state) both have linear shape.
the number of X — M — X bonds at 180° F F — I– — F F — Xe — F
must be three.
X 61 Which one of the following is
X X F S planar? [CBSE AIPMT 2000]
(a) XeF4 (b) XeO4
M (c) XeO3F (d) XeO3F2
F F
Ans. (a)
X X F σ F
σ Structure of XeF4 is as follows
X or S
σ σ F F
58 Among the following, the pair in F F
which the two species are not Hence, five sp3d hybrid orbitals are
Xe
isostructural, is [CBSE AIPMT 2004] obtained. One orbital is already paired
F F
(a) SiF4 and SF4 (b) IO –3 and XeO 3 and rest four are overlapped with four
(c) BH−4 and NH+4 (d) PF6− and SF6 p-orbitals of four fluorine atoms on their
axis in trigonal bipyramidal form. It involves sp3d2 hybridisation in
Ans. (a) Xe-atom. The molecules has square
This structure is distorted from trigonal
SiF4 and SF4 are not isostructural bipyramidal to tetrahedral due to planar structure. Xe and four F-atoms
because SiF4 is tetrahedral due to sp3 involvement of repulsion between lone are coplanar. The lone pairs are present
hybridisation of Si. pair and bond pair. on axial positions, minimise electron pair
repulsion.
62 The type of hybridisation of boron (c) H — O — H in water Ans. (b)

in diborane is [CBSE AIPMT 1999] (d) sp bonds BeF2 — sp hybridisation
(a) sp hybridisation Ans. (b) BF3 — sp2 hybridisation
(b) sp2 hybridisation When px and py form bond, then the C2H2 — sp hybridisation
(c) sp 3 hybridisation bond angle is minimum and it is only 90°. NH3 — sp3 hybridisation
(d) sp 3d2 hybridisation NOTE
Ans. (c) Bond angle in sp3 bonds, H − O − H in 70 Which of the following molecule
water and in sp bonds are 109°28, 180 ° does not have a linear arrangement
Each boron atom in diborane (B2H6 ) is
and 180° respectively. of atoms?
sp3 hybridised. In the structure of [CBSE AIPMT 1989]
diborane four H-atoms, two on the left 66 When the hybridisation state of (a) H2 S (b) C2H2
and two on the right, known as terminal (c) BeH2 (d) CO2
hydrogens, are in different environments
carbon atom changes from sp 3 to
from the other two hydrogen atoms sp 2 and finally to sp, the angle Ans. (a)
which are known as bridging atoms. The between the hybridised orbitals H2S have sp3 hybridisation while
two boron atoms and the four terminal [CBSE AIPMT 1993] remaining all have sp hybridisation, so
hydrogen atoms lie in the same plane (a) decreases gradually H2S have bent structure and other have
while the two boron atoms and the two linear geometry.
(b) decreases considerably
bridging hydrogen atoms, one above and
(c) is not affected
the other below, lie in a plane 71 Equilateral shape has
perpendicular to this plane. (d) increases progressively [CBSE AIPMT 1988]
H H H Ans. (d) (a) sp hybridisation
B B In sp3 hybridisation bond angle is 109°28′. (b) sp2 hybridisation
H H H In sp2 hybridisation bond angle is 120°. (c) sp 3 hybridisation
Structure of diborane molecule In sp hybridisation bond angle is 180°. (d) dsp2 hybridisation
Ans. (a)
63 AsF5 molecule is trigonal 67 Which structure is linear? Equilateral or triangular planar geometry
bipyramidal. The hybrid orbitals [CBSE AIPMT 1992]
is formed by sp2 hybridisation.
used by As-atoms for bonding are (a) SO2 (b) CO2
[CBSE AIPMT 1997] (c) CO2−
3 (d) SO2−
4
(a) dx 2 − y 2 , dz 2 , s , px , py Ans. (b) + +
(b) dxy , s , px , py , pz Out of SO2 , CO23− ,SO24−
and CO2 , CO2 have s-orbital p-orbital
(c) s , px , py , pz , dxy sp hybridisation, thus have linear p-orbital
(d) dx 2 − y 2 , s , px , py , pz geometry.
Ans. (c)
68 An sp 3 hybrid orbital contains 120°
As = 1s 2 , 2 s 2 , 2p6 , 3s 13px1 3py1 3pz1 3d 1 [CBSE AIPMT 1991] 120°
14442444 3
1
sp3d hybridisation (a) s-character 120°
Due to this hybridisation, geometry of 4 sp2 hybrid
the AsF5 molecule is trigonal bipyramidal 1 orbital
(b) s-character
and the hybrid orbitals used by As-atom 2
are s , px , py , pz and d xy . 1
(c) s-character
72 The angle between the overlapping
3 of one s-orbital and one p-orbital is
64 Which of the following does not 2 [CBSE AIPMT 1988]
(d) s-character
have a tetrahedral structure? 3 (a) 180° (b) 120°
[CBSE AIPMT 1994]
Ans. (a) (c) 109 °28′ (d) 120° 60′
(a) BH−4 (b) BH3 (c) NH+4 (d) H2O Ans. (a)
In sp3 hybrid orbital one part, out of four
Ans. (b) 1 When s-orbital and p-orbital overlap
orbital is s-orbital, so it have 25% or
BH3 have sp2 hybridisation, so it have 4 each other, then the bond angle formed
trigonal planar structure, not tetrahedral s-character. is 180° as given below
structure.
69 In which one of the following +
65 Among the following orbital bonds, molecules, the central atom said to s-orbital p-orbital
the angle is minimum between adopt sp 2 hybridisation?
(a) sp 3 bonds (a) BeF2 (b) BF3 180°
(b) px and py -orbitals (c) C2H2 (d) NH3
TOPIC 3 From the information mentioned in the 77 Consider the following species
above curve, bond energy (BE) of H2
Molecular Orbital Theory, molecule is (b − a) or | b − a |. CN + , CN − , NO and CN
Hydrogen and Metallic Which one of these will have the
Bonding 75 Which of the following diatomic highest bond order? [NEET 2018]
molecular species has only (a) CN+ (b) CN−
π-bonds according to molecular (c) NO (d) CN
73 Identify a molecule which does not
exist. [NEET (Sep.) 2020] orbital theory? [NEET (National) 2019] Ans. (b)
(a) Li2 (b) C2 (c) O2 (d) He2 (a) N2 (b) C2 The formula of bond order is given as
Ans. (d) (c) Be2 (d) O2 B.O.
No. of electrons  No. of electrons 
If bond order of a molecules becomes
Ans. (b) in bonding  − in antibonding 
zero, the molecule will not exist. The molecular orbital configuration of C2 =   
is 2
Bond order
Number of bonding electrons − C2 (Z = 12 ) = σ1s 2 , σ * 1s 2 , σ2s 2 , σ * 2s 2 , Energy level pattern for molecular
orbitals of different molecules depends
Number of antibonding electrons π2p2x = π2p2y . upon their central atom.
=
2 Double bond in C2 consists of both NO : Central atom is N
N b −N a π-bonds because of the presence of last (Total number of electrons = 15)
= (valence) four electrons in two
2 ∴ σ 1s 2 , σ * 1s 2 , σ2s 2 , σ * 2s 2 ,
4−2 π-molecular orbitals.
Li2 (6e − ) ⇒σ21s σ *1s2 σ22 s ; BO = =1 ( π2p2x ~− π2p2y ), σ2p2z ,( π2*px1 ≈ π2*py0 )
The configuration of N2 , Be2 and O2 are as
2 10 − 5
C2 (12e − ) ⇒σ21s σ *1s2 σ2 s σ2 s π2 p x = π22 py ;
2 *2 follows: B.O. = = 2.5
2
8−4 N2 (Z = 14) − σ1s 2 , σ * 1s 2 , σ2s 2 , σ * 2s 2 ,
BO = =2 CN − : Central atom is C
2 π2p2x = π2p2y , σ2p2z (1 σ and 2π-bonds)
[Total number of electrons= 14]
O2 (16e − ) ⇒σ21s σ 1*s2 σ22 s σ2*2s σ22 p z π 22 p x Be2 (Z = 8) − σ1s 2 , σ * 1s 2 , σ2s 2 , σ * 2s 2 (σ
= π22 p y π2*1p x = π2*1p y ; σ 1 s 2 , σ * 1 s 2 , σ2s 2 , σ * 2s 2 , ( π2px2
bonds only) ≈ π2py2 σ2p2z )
10 − 6
BO = =2
O2 (Z = 16) − σ1s 2 , σ * 1s 2 , σ2 s 2 , σ * 2 s 2 , 10 − 4
2 B.O. = =3
2−2 σ * 2p2z , π2p2x = π2p2y , π * 2px1 = π * 2pz1 (σ, π 2
He2 (4e − ) = σ21s σ *1s2 ; BO = =0
2 and 1π* bond) CN : Central atom is C
So, He2 does not exist. Hence, option (b) is correct. [Total number of electrons = 13]
σ 1s 2 , σ * 1s 2 , σ2s 2 , σ * 2s 2 ,( π2p2x
74 The potential energy (y) curve for 76 Which of the following is ≈ π2p2y ), σ2pz1
paramagnetic? [NEET (Odisha) 2019] 9−4
H2 formation as a function of B.O = = 2.5
(a) N2 (b) H2 2
internuclear distance (x) of the
H-atoms is shown below. (c) Li2 (d) O2 CN + : Central atom is C
[NEET (Oct.) 2020] Ans. (d) [Total number of electrons = 12]
Key Idea If all the electron in a molecule σ 1s 2 , σ * 1s 2 , σ2s 2 , σ * 2s 2 , ( π2p2x ≈ π2p2y )
are paired, the molecule is diamagnetic 8−4
a B.O = =2
and if there are unpaired electrons in a 2
molecule, it is paramagnetic. Therefore, option (b) is correct.
y
b Molecular orbital configuration of given
c molecules are as follows: 78 Which one of the following
x
(a) N2 (Z = 14) − σ 1s 2 , σ * 1s 2 , σ2s 2 , compounds shows the presence of
The bond energy of H2 is σ * 2s 2 , π2p2x = π2p2y , σ2p2z intramolecular hydrogen bond?
(c − a)
(a) (b − a) (b) It is a diamagnetic molecule due to [NEET 2016, Phase II]
2 absence of unpaired electron.
(b − a) (a) H2O2
(c) (d) (c − a) (b) H2 (Z = 2) − 1σ2 (b) HCN
2 It is a diamagnetic molecule. (c) Cellulose
Ans. (a) (c) Li2 (Z = 6) − σ 1s 2 , σ * 1s 2 , σ2s 2 (d) Concentrated acetic acid
[Repulsion between two H-atoms]
+ve
H H
It is a diamagnetic molecule. Ans. (c)
(0.00) a
H H
(d) O2 (Z = 16) − σ 1s 2 , σ * 1s 2 , σ2s 2 , σ * 2s 2 , Intermolecular hydrogen bonding is
y
–ve BE Infinite separation of two σ2p2z , π2p2x = π2p2y , π * 2px1 = π * 2py1 present in concentrated acetic acid,H2O2
H-atom (No attraction)
(PE)
(No repulsion) It is a paramagnetic molecule due to and HCN while cellulose has intra-
(–ve) b H H
Ovarlapping of two H-atom to
presence of unpaired electrons in molecular hydrogen bonding as shown
C form a covalent bond (σ) each orbital of degenerate levels. below :
x (Internuclear distance) Thus, option (d) is correct.
δ– δ+ Ans. (b) Molecular orbital configuration of

O H O
Bond order of O2− O2+ ( 8 + 8 − 1 = 15)
H3 C C δ+ δ–
C CH3
O H O O2− = σ 1s 2 , σ* 1s 2 ,σ 2s 2 ,σ* 2s 2 = σ 1 s 2 , σ* 1s 2 , σ2 s 2 , σ* 2 s 2 , σ2p2z ,
Concentrated Acetic Acid σ 2p2z ( π2p2x = π2p2y ) ( π *2px1 = π *2py1 ) π2p2x ≈ π2p2y , π* 2px1 ≈ π* 2py0
Bond order Nb − Na
H δ+ number of electrons in BMO − number Bond order (BO) =
O O 2
δ–
=
of elections ABMO (where,N b = number of electrons in
H δ+ H δ+ bonding molecular orbital,
2
δ– 10 − 7 3 N a = number of electrons in antibonding
O O δ– = = = 1.5
H δ+ 2 2 molecular orbital)
10 − 5
H2O 2 O2+ = σ 1s 2 , σ* 1s 2 , σ 2s 2 , σ* 2s 2 σ 2p2z ∴ BO = = 2.5
2
δ– δ+ δ– ( π2p2x = π 2p2y ) ( π *2px1 = π *2py0 ) Similarly,
H C N H C N
10 − 5 5 (b) O2− (8 + 8 + 1 = 17)
BO = = = 2. 5
HCN 2 2 N − N a 10 − 7
so, BO = b = = 1.5
HO δ+ 3
OH
1 O2 = σ 1s 2 σ* 1s 2 , σ 2s 2 , σ* 2s 2 σ 2p2z 2 2
δ– 2
(c) O22 − (8 + 8 + 2 = 18)
6 HO
4 O O
( π2p2x = π 2p2y ) ( π* 2px1 = π* 2py1 )
5 N − N a 10 − 8
O 2 O 10 − 6 4 BO = b = =1
δ+ 3 1 4 5 O BO = = =2 2 2
δ–
HO OH HO 6 n 2 2
(d) O2 (8 + 8 = 16)
Cellulose So, the correct sequence is 10 − 6
O2− < O2 < O2+ BO = =2
In above molecules, dotted lines 2
represent hydrogen bonding.
Thus, O2− shows the bond order 1.5.
81 Which of the following is
79 Which of the following pairs of ions paramagnetic? [NEET 2013]
83 The pair of species with the same
is isoelectronic and isostructural? (a) CO (b) O2−
bond order is [NEET 2013]
[NEET 2016, Phase II] (c) CN− (d) NO +
(a) O22 − , B2 (b) O2+ , NO +
(a) CO23− , NO −3 (b) CIO −3 , CO23− Ans. (b) (c) NO, CO (d) N2 , O2
(c) SO23− , NO −3 (d) CIO −3 , SO23− Paramagnetic species contains unpaired Ans. (a)
Ans. (a) and (d) electrons in their molecular orbital
electronic configuration. According to molecular orbital theory,
Total
Molecular orbital configuration of the O22 − (8 + 8 + 2 = 18)
Species number of Structure Shape
electrons given species is as = σ 1 s 2 , σ* 1 s 2 , σ2 s 2 , σ* 2 s 2 , σ2p2z , π2p2x
CO (6 + 8 = 14)
ClO –3 42 Cl Pyramidal ≈ π2p2y , π* 2p2x ≈ π* 2p2y
–
O = σ 1s , σ* 1s 2 , σ2 s 2 , σ* 2 s 2 , π2p2x
2
Nb − Na 10 − 8
O O Bond order (BO) = = =1
≈ π2p2y , σ2p2z 2 2
SO 2–
3 42 S Pyramidal
– (All the electrons are paired so, it is
–
O
diamagnetic). B2 (5 + 5 = 10) = σ 1s , σ 1s 2 , σ2 s 2 , σ* 2 s 2 ,
2 *
O O
O2− (8 + 8 + 1 = 17) π2px1 ≈ π2py1
CO 2– 32 O Trigonal 6−4
3 BO = =1
C
planar = σ 1s 2 , σ* 1 s 2 , σ2 s 2 , σ* 2s 2 , σ2p2z , π2p2x 2
–
* 2p2 ≈ π Thus, O22 − and B2 have the same bond
≈ π2p2y , π * 2py1
O –
O x order.
NO –3 32 O Trigonal (It contains one unpaired electron so, it NOTE
planar
N is paramagnetic.) BO of O2+ = 2.5 , NO + = 3 , NO = 2 .5 , CO = 3 ,
– CN− (6 + 7 + 1 = 14) = same as CO N2 = 3 and O2 = 2
O O
NO+ ( 7 + 8 − 1 = 14) = same as CO
Hence both options (a) and (d) are Thus, among the given species onlyO2− is 84 Which of the following has the
correct. paramagnetic. minimum bond length?
[CBSE AIPMT 2011]
80 Which of the following options 82 Bond order of 1.5 is shown by (a) O2− (b) O2–
2
represents the correct bond order? [NEET 2013] (c) O2 (d) O2+
[CBSE AIPMT 2015] (a) O2+ (b) O2− Ans. (d)
(a) O2– > O2 > O2+ (b) O2– < O2 < O2+ (c) O2− (d) O2 10 − 5
2 Bond order of O2+ = = 2.5
(c) O2– > O2 < O2+ (d) O2– < O2 > O2+ Ans. (b) 2
10 − 7 Hence, it is the intermolecular 10 − 5
Bond order of O2– = = 1.5 BO = = 2.5
2 H-bonding that must be overcome in 2
10 − 8 converting liquid CH3OH to gas. C22 − (6 + 6 + 2 = 14) = σ 1s 2 , σ* 1s 2 ,
Bond order of O22 – = =1
2 σ2 s 2 , σ* 2 s 2 , π2p2y ≈ π2p2z , σ2p2x
10 − 6 87 According to molecular orbital 10 − 4
Bond order of O2 = =2 BO = =3
2 theory which of the following lists 2
Q Maximum bond order = minimum bond rank the nitrogen species in terms He2+ (2 + 2 − 1 = 3) = σ 1s 2 , σ* 1s 1
length. of increasing bond order? 2− 1 1
BO = = = 0.5
∴ Bond length is minimum forO2+ [CBSE AIPMT 2009] 2 2
(a) N2− < N2 < N22 − (b) N22 − < N2− < N2 Hence, order of increasing bond order is
85 Which one of the following species (c) N2 < N22 − < N2− (d) N2− < N22 − < N2
He2+ < O2– < NO < C22 –
does not exist under normal Ans. (b)
conditions? [CBSE AIPMT 2010] According to the molecular orbital 89 The correct order of C—O bond
(a) Be +2 (b) Be 2 theory (MOT), length among CO, CO 2−
3 , CO 2 is
(c) B2 (d) Li 2 [CBSE AIPMT 2007]
N2 ( 7 + 7 = 14) = σ 1s 2 , σ* 1s 2 , σ 2 s 2 ,
Ans. (b) (a) CO2 <CO2–
3 <CO
σ* 2 s 2 , π2p2x ≈ 2p2y , σ2p2z
Key Idea Molecules with zero bond order, (b) CO <CO2–
3 <CO2
do not exist. 10 − 4 (c) CO2– <CO
Bond order = =3 3 2 <CO
According to molecular orbital theory, 2 (d) CO <CO2 <CO2–3
(a) Be 2+ (4 + 4 − 1 = 7) N2− ( 7 + 7 + 1 = 15) Ans. (d)
= σ 1s 2 , σ* 1s 2 , σ 2 s 2 , σ* 2 s 2 , A bond length is the average distance
= σ 1s 2 , σ* 1 s 2 , σ2 s 2 , σ* 2 s 1 between the centres of nuclei of two
σ2p2z , π2p2x ≈ 2p2y , π* 2px1 bonded atoms. A multiple bond (double
4− 3
Bond order (BO) = = 0.5 10 − 5 or triple bonds) is always shorter than
2 BO = = 2.5
2 the corresponding single bond.
(b) Be 2 (4 + 4 = 8)
N22 − ( 7 + 7 + 2 = 16) The C-atom inCO23 – is sp2 hybridised as
= σ 1 s 2 , σ* 1s 2 , σ2 s 2 , σ* 2 s 2 shown:
4−4 = σ 1s 2 , σ* 1s 2 , σ2 s 2 , σ* 2 s 2 ,
BO = =0 O– O
2 σ2p2z , π2p2x ≈ π2p2y , π* 2px1 ≈ π* 2py1 O= =C ←→ O – —C ←→
(c) B2 (5 + 5 = 10) 10 − 6 O
–
O
–
BO = =2
= σ 1s 2 , σ* 1s 2 , σ2 s 2 , σ* 2 s 2 , π2px1 ≈ π2py1 2 O–
6−4 Hence, the increasing order of bond
Bond order (BO) = =1 O– —C
2 order is,
O
N22 − < N2− < N2
(d) Li2 (3 + 3 = 6) = σ 1s 2 , σ* 1s 2 , σ2s 2 The C-atom inCO2 is sp hybridised with
4−2 bond distance carbon-oxygen is 122 pm.
BO = =1 88 Four diatomic species are listed –
2 +
below in different sequences. O== C==O ←→ O ≡≡ C —O ←→
Thus, Be2 does not exist under normal Which of these presents the – +
conditions. O— C ≡≡ O
correct order of their increasing
The C-atom in CO is sp hybridised with
86 What is the dominant bond order? [CBSE AIPMT 2008]
C—O bond distance is 110 pm.
intermolecular force on bond that (a) O2– <NO <C2–
2 <He2
+
• ≡≡ + •
2– – + •C O •
must be overcome in converting (b) NO <C 2 <O2 <He2 So, the correct order is
liquid CH3OH to a gas? (c) C2– +
2 <He2 <NO <O2
–
CO < CO2 < CO23–
+ – 2–
[CBSE AIPMT 2009] (d) He2 <O2 <NO <C2
(a) Hydrogen bonding Ans. (d) 90 The number of unpaired electrons
(b) Dipole-dipole interaction The molecular orbital configuration of in a paramagnetic diatomic
(c) Covalent bonds O2− (8 + 8 + 1 = 17) = σ 1s 2 , σ* 1s 2 , molecule of an element with
(d) London or dispersion force σ2 s 2 , σ* 2 s 2 , atomic number 16 is
Ans. (a) σ2px , π2py ≈ π2pz , π 2py ≈ π 2pz1
2 2 2 * 2 * [CBSE AIPMT 2006]
In betweenCH3OH molecules N − N a 10 − 7 (a) 2 (b) 3
Bond order (BO) = b = = 1.5 (c) 4 (d) 1
intermolecular H-bonding exist. 2 2
δ+ δ− δ+ δ− δ+ δ− Ans. (a)
- - - H — O- - - H — O- - - H — O- - - NO (7 + 8 = 15) = σ 1s 2 , σ* 1s 2 , σ2s 2 ,
   σ* 2 s 2 , σ2p2x Suppose the diatomic molecule is X.
CH3 CH3 CH3 π2py ≈ π2pz , π 2py1 ≈ π* 2pz0
2 2 * Then, molecular orbital electronic
configuration of
Intermolecular H-bond
16 X = σ 1s 2 , σ* 1s 2 , σ2 s 2 , σ* 2 s 2 , σ2p2z , π2p2x 94 Among the following group which So, bond order of
represents the collection of N − N a 10 − 4
N2 = b = =3
≈ π2p2y , π* 2px1 ≈ π* 2py1 2 2
isoelectronic species?
9−4
Due to presence of two unpaired [CBSE AIPMT 2000] and bond order ofN2 + = =2.5
electrons, it shows paramagnetic (a) NO, CN–, N2 , O2– 2
character. (b) NO + , C2– – As the bond order ofN2 is greater than
2 , O2 , CO
2–
(c) N2 , C2 , CO, NO N2 + so, the dissociation energy ofN2 will
91 Main axis of a diatomic molecule is be greater thanN2 + .
(d) CO, NO + , CN–, C2– 2
z molecular orbital, p x and p y
Ans. (d) 97 Which one of the following
overlaps to form which of
Species having equal number of molecules will form a linear
the following orbitals? electrons are known as isoelectronic
[CBSE AIPMT 2001] polymeric structure due to
species.
(a) π-molecular orbital hydrogen bonding?
Number of electrons,
(b) σ-molecular orbital [CBSE AIPMT 2000]
In CO = 6 + 8 = 14
(c) δ-molecular orbital (a) NH3 (b) H2 O
In NO+ = 7 + 8 − 1 = 14 (c) HCl (d) HF
(d) No bond will form
In CN– = 6 + 7 + 1 = 14 Ans. (d)
Ans. (a)
In C22 − =12 + 2 = 14
For π-overlap the lobes of the atomic HF molecules have linear polymeric
Hence, all have 14 electrons, so they are structure due to hydrogen bonding.
orbitals are perpendicular to the line
isoelectronic species.
joining the nuclei. H — F --- H — F --- H — F --- H — F
↑
+ + + 95 Which one of the following is not H- bond
π-overlapping paramagnetic? [CBSE AIPMT 2000]
+ 98 The number of antibonding
(a) NO (b) N2+
– – – electron pairs in O 2−
2 molecular ion
(c) CO (d) O2−
on the basis of molecular orbital
Ans. (c)
92 In X — H− − − Y , X and Y both are theory is (at. no. of O is 8)
Paramagnetic character is shown by [CBSE AIPMT 1998]
electronegative elements, then those atoms or molecules which have
[CBSE AIPMT 2001] (a) 5 (b) 2 (c) 4 (d) 6
unpaired electrons.
(a) electron density on X will increase Ans. (c)
In the given compounds CO is not
and on H will decrease paramagnetic since, it does not have Total number of electrons in
(b) in both electron density will increase unpaired electrons. The configuration of O 22 – = 19 + 2 = 18
(c) in both electron density will decrease CO molecule is According to MOT, the configuration of
(d) on X electron density will decrease O 22 − is
CO(14)= σ 1s 2 , σ
*
1s 2 , σ2 s 2 , σ
*
2 s 2 , σ2p2x ,
and on H increase
π2p2y ≈ π2p2z σ 1s 2 , σ* 1s 2 , σ2 s 2 , σ* 2 s 2 , σ2p2x , π2p2y ≈
Ans. (a)
In X — H ----- Y, X and Y both are π 2p2z , π* 2p2y ≈ π* 2p2z
96 The relationship between the
electronegative elements, then electron
density on X will increase and on H will dissociation energy of N 2 and N 2+ is So, the number of antibonding electron
[CBSE AIPMT 2000] pairs = 4
decrease.
(a) dissociation energy ofN2+ >
dissociation energy ofN2 99 The high density of water
93 A compound contains atoms of
(b) dissociation energy ofN2 = compared to ice is due to
three elements A, B and C. If the
dissociation energy ofN2+ [CBSE AIPMT 1997]
oxidation number of A is +2, B is +5 (c) dissociation energy of (a) hydrogen bonding interactions
and that of C is –2, the possible N2 > dissociation energy ofN2+ (b) dipole-dipole interactions
formula of the compound is (d) dissociation energy ofN2 can either (c) dipole-induced dipole interactions
[CBSE AIPMT 2000] be lower or higher than the (d) induced dipole-induced dipole
(a) A2 (BC 3)2 (b) A3 (BC 4 )2 dissociation energy ofN2+ interactions
(c) A3 (B4C)2 (d) ABC2 Ans. (c) Ans. (a)
Ans. (b) The dissociation energy will be more Due to polar nature, water molecules
In A3 (BC 4 )2 when the bond order will be greater and show intermolecular hydrogen bonding
bond order ∝ dissociation energy as
3 × oxidation number of A
Molecular orbital configuration of - - - H —O- - - H —O - - - H —O
+ 2 [oxidation number ofB + 4 × oxidatio
oxidation number ofC ] = 0 N2 (14) = σ 1s 2 , σ
*
1s 2 , σ 1 s 2 , σ
*
2 s 2 , π 2py 2   
H H H
3 × (+2) + 2 [5 + 4 × (–2)] = 0
≈ π2pz2 , σ2px 2 Hydrogen bonding
6 + 2 [–3] = 0
whereas the ice has open structure with

103 The ground state electronic (d) p-nitrophenol has a higher molecular
large number of vacant spaces. So, weight than o-nitrophenol
configuration of valence shell
density of ice is lower than water. Ans. (c)
electrons in nitrogen molecule (N 2 )
is written as The boiling point of p-nitrophenol is
100 N 2 and O 2 are converted into higher than that of o-nitrophenol
−
monoanions N 2 and O 2 − KK , σ2 s 2 , σ * 2s 2 , σ2p x2 , π2p y2 ≈ π2p z2 because p-nitrophenol have
respectively. Which of the following Bond order in nitrogen molecule is intermolecular hydrogen bonding
[CBSE AIPMT 1995] whereas o-nitrophenol have
statements is wrong?
(a) 0 (b) 1 intramolecular H-bonding as given below
[CBSE AIPMT 1997]
(c) 0 (d) 3 H
(a) In N2 , the N—N bond weakens O O
Ans. (d)
(b) In O2− , O—O bond length increases N
(c) In O2–, bond order decreases The MO configuration of N2 is O
(d) N2− , becomes diamagnetic KK , σ2 s 2 , * σ2 s 2 , σ2p2x , π2p2y ≈ π2p2z
Ans. (d) Bond order of
o-nitrophenol
1
In N2− total electrons = 14 + 1 = 15 N2 = [N b − N a ]
2 O
Electronic configuration of N2− is 1 ---HO— —N O
= [8 − 2] O---HO— —N
σ 1s , σ 1s
2 * 2
, σ2 s , σ 2 s , σ2p2x ,
2 * 2
2 O
p-nitrophenol
π2p2y ≈ π2p2z , π* 2py1 6
= =3
2 107 Linus Pauling received the Nobel
Due to presence of one unpaired
electron, it shows paramagnetic Prize for his work on
character.
104 The correct order of the O — O [CBSE AIPMT 1994]
bond length in O 2 , H2O 2 and O 3 is (a) atomic structure
[CBSE AIPMT 1995] (b) photosynthesis
101 The ion that is isoelectronic with
CO is [CBSE AIPMT 1997]
(a) O2 > O 3 > H2O2 (b) O 3 > H2O2 > O2 (c) chemical bonds
(c) O2 > H2O2 > O 3 (d) H2O2 > O 3 > O2
(a) O2− (b) N2+ (d) thermodynamics
(c) O2+ (d) CN− Ans. (d) Ans. (c)
Ans. (d) The bond length of O—O inH2O2 is 147.5 Linus Pauling contributed to chemical
pm, inO3 is 128 pm and inO2 it is 121 pm, bonding, so, he received the Nobel Prize
Isoelectronic species are having same
so the correct order isO2 < O3 < H2O2 . for his work in chemical bonding.
number of electrons.
Number of electrons in CO = 6 + 8 = 14 108 Mark the incorrect statement in the
105 Which of the following species is
Number of electrons inO2− = 16 + 1 = 17 following.
paramagnetic? [CBSE AIPMT 1995] [CBSE AIPMT 1994]
Number of electrons inN2+ = 14 − 1 = 13 (a) The bond order in the speciesO2 ,O2+
(a) O2− (b) NO
Number of electrons inO2+ = 16 − 1 = 15
2
(c) CO (d) CN− and O2− decreases asO2+ > O2 > O2–
Number of electrons in (b) The bond energy in a diatomic
Ans. (b)
CN− = 6 + 7 + 1 = 14 molecule always increases when an
Hence, CO isoelectronic withCN− ion. The molecular orbital configuration of electron is lost
NO is (c) Electrons in antibonding MO
102 The correct order of N — O bond KK (σ 2s ) 2 (σ* 2s ) 2 (σ 2px ) 2 ( π2py ) 2 contribute to repulsion between two
lengths in NO, NO −2 , NO −3 and N 2O 4 ( π2pz )2 ( π* 2py ) 1
atoms
(d) With increase in bond order, bond
is [CBSE AIPMT 1996]
length decreases and bond strength
So, NO is paramagnetic because it
(a) N2O 4 > NO2– > NO –3 > NO contains one unpaired electron. increases
(b) NO > NO –3 > N2O 4 > NO2– Ans. (b)
(c) NO –3 > NO2– > N2O 4 > NO 106 The boiling point of p-nitrophenol is When a diatomic molecule lost electron,
(d) NO > N2O 4 > NO2– > NO –3 higher than that of o-nitrophenol then its bond order may increase or
Ans. (c) because [CBSE AIPMT 1994] decrease, so its bond energy may
(a) NO2 group at p-position behave in a decrease or increase.
As the bond order increases, bond length
decreases and bond order is highest for different way from that at o-position
109 The dielectric constant of H2O is
NO, i.e. 2.5 and least forNO−3 , i.e. 1.33. So, (b) intramolecular hydrogen bonding
the order of bond length is exists in p-nitrophenol 80. The electrostatic force of
NO–3 > NO2– > N2O4 > NO (c) there is intermolecular hydrogen attraction between Na + and Cl −
2.5 bonding in p-nitrophenol
1.33 1.5 1.5 will be [CBSE AIPMT 1994]
1 (a) sigma bond Since, F is most electronegative and

(a) reduced to in water than in air
40 (b) double bond has smaller size, HF shows maximum
1 strength of hydrogen bond.
(b) reduced to in water than in air (c) coordinate bond
80
(d) pi-bond
(c) will be increased to 80 in water than 112 Which of the following does not
Ans. (a)
in air
When two hybridised orbitals of two atoms
apply to metallic bond?
(d) will remain unchanged [CBSE AIPMT 1989]
undergoes linear combination, they form
Ans. (b) (a) Overlapping valence orbitals
sigma bond.
Water is a polar solvent and have (b) Mobile valence electrons
dielectric constant 80. As NaCl is a polar 111 Which one shows maximum hydrogen (c) Delocalised electrons
compound and like dissolves like so, (d) Highly directed bonds
forces of attraction betweenNa+ and
bonding?
1 [CBSE AIPMT 1990] Ans. (d)
Cl − ion will reduce to in water.
80 (a) H2O (b) H2 Se Metallic bond have force of attraction
(c) H2 S (d) HF on all sides between the mobile
110 Linear combination of two Ans. (d) electrons and the positive kernels.
hybridised orbitals belonging to the Metals having free electrons as a
Hydrogen bonding ∝ electronegativity
1 mobile electrons. So, the metallic
two atoms, each having one ∝ bond does not have directional
electron leads to a Size of atom to which property.
[CBSE AIPMT 1990] H is covalently bonded
4
Chemical
Thermodynamics
TOPIC 1 03 Under isothermal condition, a gas W = −10 5 Nm−2 (10 −2 m3 − 10 −3m3)
Generalised Terms and First at 300 K expands from 0.1 L to 0.25 = −10 5 Nm−2 × 10 −3 (10 − 1) m3
Law of Thermodynamics L against a constant external = −900 Nm = −900 J
pressure of 2 bar. The work done
01 Which one among the following is by the gas is 05 A gas is allowed to expand in a well
the correct option for right (Given that 1 L bar = 100 J) insulated container against a
relationship between C p and C V for [NEET (National) 2019] constant external pressure of 2.5
(a) 5 kJ (b) 25 J (c) 30 J (d) −30 J atm from an initial volume of 2.50 L
one mole of ideal gas? [NEET 2021]
(a) C p + C V = R (b) C p − C V = R Ans. (d) to a final volume of 4.50 L. The
(c) C p = RC V (d) C V = RC p Key Idea For an isothermal irreversible change in internal energy ∆U of the
expansion, Wirrev = − pext (V2 − V1) gas in joules will be [NEET 2017]
Ans. (b)
Given,V1 = 0.1 L, V2 = 0.25 L, pext = 2 bar (a) 1136.25 J (b) − 500 J
For an ideal gas,
We know that, (c) − 505 J (d) + 505 J
C p − C V = nR
Wirrev = − pext (V2 − V1) Ans. (c)
(where, n = number of moles of gas,
On substituting the given values in the Key concept According to first law of
C p , C V = specific heat at constant above equation, we get
pressure and volume, R = universal gas thermodynamics,
Wirrev = − 2 bar (0.25 − 0.1) L ∆U = q + w
constant)
= − 2 × 0.15 L bar = − 0.3 L bar where, ∆U = internal energy
As n = 1, so C p − C V = R
= − 0.3 × 100 J [Q1 L bar = 100 J] q = heat absorbed or evolved,w = work
02 The correct option for free = − 30 J done.
expansion of an ideal gas under the Also, work done against constant
adiabatic condition is 04 An ideal gas expands isothermally external pressure (irreversible process).
[NEET (Sept.) 2020] from10 −3 m 3 to10 −2 m 3 at 300 K w = − pext ∆V .
(a) q = 0, ∆T < 0 and w > 0 against a constant pressure of 10 5 Work done in irreversible process,
(b) q < 0, ∆T < 0 and w = 0 Nm −2 . The work done on the gas is w = − pext ∆V = − pext (V2 − V1)
(c) q > 0, ∆T < 0 and w > 0 [NEET (Odisha) 2019] = − 2.5 atm (4.5 L − 2.5 L)
(d) q = 0, ∆T = 0 and w = 0 (a) + 270 kJ (b) − 900 J = − 5 L atm = − 5 × 1013. J
(c) + 900 kJ (d) − 900 kJ
Ans. (d) = − 505 J
Ans. (b) Since, the system is well insulated,q = 0
For adiabatic process,q = 0
For adiabatic free expansion of an ideal For an isothermal irreversible expansion, ∴ ∆U = w = − 505 J
gas, no work will be done, because, Work done (W) = − pext (V2 − V1) Hence, change in internal energy, ∆U of
dV = 0. where,V1 = initial volume the gas is − 505 J.
∴ w = pdV = 0 V2 = final volume
For adiabatic free expansion of an ideal Given, pext = 10 5 Nm −2 , 06 Which one of the following is
gas, no change in internal energy. −3
V1 = 10 m , V2 = 10 m
3 −2 3 correct option for free expansion
So, dU = 0 and dT =0 [QdU = nC V dT ] of an ideal gas under adiabatic
On substituting the given values in Eq, (i),
So, option (d) is correct.
We get,
condition? [CBSE AIPMT 2011]
(a) q ≠ 0, ∆T = 0, W = 0 Given that, c = 75 JK–1 mol –1 Ans. (b)

(b) q = 0, ∆T = 0, W = 0 q = 1.0 kJ = 1000 J For endothermic reactions standard
(c) q = 0, ∆T < 0, W ≠ 0 Mass = 100 g water heat of reaction (∆H) is positive because
(d) q = 0, ∆T ≠ 0, W = 0 Molar mass of water = 18 g
in these reactions total energy of
reactants is lower than that of products,
Ans. (b) 1000
75 = i.e. E R < E P
In adiabatic process, heat exchange is 5.55 × ∆T So, ∆H = E P − E R = + ve
constant, so q = 0 and for free expanion,  100 
W = 0,∴∆T = 0.  Number of moles = = 5 .55
 18  13 One mole of an ideal gas at 300 K is
1000 expanded isothermally from an
07 Which of the following are not ∴ ∆T = = 2 .4 K
5.55 × 75 initial volume of 1 L to 10 L. The ∆E
state functions?
[CBSE AIPMT 2008] for this process is
I. q + W II. q 10 In a closed insulated container a (R = 2cal mol–1K –1 )
[CBSE AIPMT 1998]
liquid is stirred with a paddle to
III. W IV. H − TS (a) 163.7 cal (b) zero
increase the temperature, which of
(a) I and IV (c) 1381.1 cal (d) 9 L atm
the following is true?
(b) II, III and IV
[CBSE AIPMT 2002] Ans. (b)
(c) I, II and III
(a) ∆ E = W ≠ 0, q = 0 Isothermal process means temperature
(d) II and III
(b) ∆ E = W = 0, q ≠ 0 remains constant. At constant
Ans. (d) temperature, internal energy (∆E) also
(c) ∆ E = 0, W = q ≠ 0
The thermodynamic parameters which remains constant. So, ∆E = 0
depend only upon the initial and final
(d) W = 0, ∆ E = q ≠ 0
states of system, are called state Ans. (a) 14 During isothermal expansion of an
functions, such as enthalpy (H = q + W), In closed insulated container a liquid is ideal gas, its [CBSE AIPMT 1991, 94]
Gibbs free energy (G = H − TS ), etc. While stirred with a paddle to increase the
those parameters which depend on the (a) internal energy increases
temperature, therefore it behaves as
path by which the process is performed adiabatic process, so for it q = 0. (b) enthalpy decreases
rather than on the initial and final states, Hence, from first law of thermodynamics
(c) enthalpy remains unaffected
are called path functions, such as work (d) enthalpy reduces to zero
done, heat, etc. ∆E =q + W
if, q = 0 Ans. (c)
∴ ∆ E = W but not equal to zero. We know that,
08 The work done during the
H=E+ W
expansion of a gas from a volume
11 When 1 mole gas is heated at Enthalpy = internal energy + pressure ×
of 4 dm 3 to 6dm 3 against a
volume
constant external pressure of 3 constant volume, temperature is
raised from 298 to 308 K. Heat H = E + pV
atm, is [CBSE AIPMT 2004]
supplied to the gas is 500 J. Then, ∆H = ∆E + ∆ (pV )
(a) − 6 J (b) – 608 J
which statement is correct? ∆H = ∆E + ∆ (ng RT ) (Q pV = nRT )
(c) + 304 J (d) – 304 J
[CBSE AIPMT 2001] For isothermal expansion of ideal gas,
Ans. (b) ∆T = 0
(a) q = W = 500 J, ∆ E = 0
Work done ( W) = − pext (V2 − V1) ∴ ∆H = ∆E
(b) q = ∆ E = 500 J, W = 0
= − 3 × (6 − 4) = − 6 L atm
(c) q = − W = 500 J, ∆ E = 0
= − 6 × 101.32 J (Q 1 L atm = 101.32 J)
(d) ∆ E = 0, q = W = − 500 J
TOPIC 2
= − 607.92 ≈ –608 J
Ans. (b) Reactions Related to
09 The molar heat capacity C of water We know that, ∆ H = ∆ E + p∆V Enthalpies and Hess’s Law
at constant pressure is 75 JK −1 mol When, ∆V = 0
−1 15 At standard conditions, if the
, when 1.0 kJ of heat is supplied ∴ ∆H = ∆ E
to 100 g of water which is free to From first law of thermodynamics change in the enthalpy for the
expand, the increase in ∆E =q –W following reaction is
temperature of water is In given problem ∆H = 500 J −109 kJ mol −1 .
[CBSE AIPMT 2003] –W = – p∆V , ∆V = 0 H2 (g) + Br 2 (g) → 2HBr(g)
(a) 4.8 K (b) 6.6 K So, ∆E = q = 500 J Given that, bond energy of H2 and
(c) 1.2 K (d) 2.4 K
Br 2 is 435 kJ mol −1 and 192 kJ mol
Ans. (d) 12 In an endothermic reaction, the −1
respectively, what is the bond
According to heat capacity rule, value of ∆H is [CBSE AIPMT 1999] energy (in kJ mol −1 ) of HBr?
q
q = mc∆T , c = (a) zero (b) positive [NEET (Oct.) 2020]
m(T2 − T1) (c) negative (d) constant (a) 368 (b) 736 (c) 518 (d) 259
Chemical Thermodynamics 35
Ans. (a) Ans. (c) 20 Standard enthalpy of vaporisation

H2 (g) + Br2 (g) → 2HBr(g) The given phase equilibria is ∆ vap H ° for water at 100°C is 40.66
[H  Br]
[H H] [Br  Br] Liquid r Vapour kJ mol −1 . The internal energy of
⇒ ∆ r H = (ΣBE)Reactants − (ΣBE) Products This equilibrium states that, when liquid vaporisation of water at 100°C
[QBE = bond energy] is heated, it converts into vapour but on (in kJ mol −1 ) is (assume water
⇒− 109 = [(BE)H 2 + (BE) Br2 ] − (BE) HBr × 2 cooling, it further converts into liquid,
which is derived by Clausius Clapeyron
vapour to behave like an ideal gas).
= (435 + 192) − (BE)HBr × 2 and the relationship is written as,
[CBSE AIPMT 2012]
⇒ (BE)HBr = 368 kJ mol − 1 d ln p ∆H (a) + 37.56 (b) − 43.76
= − v2 (c) + 43.76 (d) + 40.66
dT RT
16 The bond dissociation energies Ans. (a)
where, ∆Hv = Heat of vaporisation
of X 2 , Y 2 and XY are in the ratio of 100 ° C
H2O(l ) → H2O(g)
1 : 0.5 : 1 . ∆H for the formation of 18 The heat of combustion of carbon ∆ vapH ° = ∆ vap E ° + ∆ng RT
XY is −200 kJ mol −1 . The bond to CO 2 is −393.5kJ / mol. The heat ∆ vapH ° = enthalpy of vaporisation
dissociation energy of X 2 will be released upon the formation of 35.2 = 40.66 kJ mol − 1
[NEET 2018]
g of CO 2 from carbon and oxygen For the above reaction,
(a) 800 kJ mol−1 (b) 100 kJ mol−1
gas is [CBSE AIPMT 2015] ∆ng = np − nr = 1 − 0 = 1
(c) 200 kJ mol−1 (d) 400 kJ mol−1
(a) −315 kJ (b) +315 kJ R = 8314
.
Ans. (a) (c) −630 kJ (d) −315
. kJ T = 100 ° C = 273 + 100 = 373 K
Key Concept Relation between heat of
reaction (∆ r H) and bond energies (BE) of
Ans. (a) ∴ 40.66 kJ mol −1 = ∆ vap E ° + 1 × 8.314
reactants and products is given by Given, C( s ) + O2 ( g ) → CO2 ( g ) ; × 10 −3 × 373
∆ r H = Σ BEReactants − Σ BE Products ∆fH = − 393.5 kJ mol − 1 ∆ vap E° = 40.66 kJ mol − 3.1 kJ mol −1
−1
The reaction of formation for XY is Q Heat released on formation of 44 g or 1 = + 37.56 kJ mol −1

1 1 mole
X2 (g) + Y2 (g) → XY (g);
2 2 CO2 = −395.5kJ mol 21 Enthalpy change for the reaction,
∆H = − 200kJ mol −1 Q Heat released on formation of 35.2 g 4H(g) → 2H2 (g) is – 869.6 kJ
Given, the bond dissociation energies of of CO2
X2 , Y2 and XY are in the ratio 1 : 0.5 : 1. Let − 393.5 kJ mol − 1 The dissociation energy of H—H
the bond dissociation energies of X2 , Y2 = × 35.2 g bond is [CBSE AIPMT 2011]
44g
and XY are a kJ mol −1, 0.5a kJ mol −1 and (a) – 869.6 kJ (b) + 434.8 kJ
a kJ mol −1, respectively. = − 315 kJ mol −1
(c) + 217.4 kJ (d) – 434.8 kJ
∴ ∆ r H = ΣBEReactants − ∆ BEProducts
19 A reaction having equal energies of Ans. (b)
1 1 
= × a + × 0.5a − [1 × a] 4H(g) → 2 H2 (g) , ∆H = − 869.6 kJ
 2 2  activation for forward and reverse
a a reactions has [NEET 2013] 2H2 (g) → 4H(g) , ∆H = 869.6 kJ
−200 = + − a H2 (g) → 2 H(g) ,
2 4 (a) ∆S = 0
2a + a − 4a −a (b) ∆G = 0 Dissociation energy of H—H bond
−200 = = 869.6
4 4 (c) ∆ H = 0 = = 434.8 kJ
a = 800 kJ mol −1 (d) ∆ H = ∆G = ∆S = 0 2
∴ The bond dissociation energy of Ans. (c)
22 From the following bond energies
X2 = a kJ mol −1 = 800 kJ mol −1 Energy profile diagram for a reaction is
as H—H bond energy : 431.37 kJ mol −1
17 Consider the following C==C bond energy:606.10 kJ mol −1
liquid-vapour equilibrium C—C bond energy : 336.49 kJ mol −1
[NEET 2016, Phase I]
C—H bond energy : 410.50 kJ mol −1
Energy
(Ea)f
(Ea)b
Liquid Vapour
!
∆H Enthalpy for the reaction,
Which of the following relations is H H H H
correct? Progress of the reaction    
dlnP − ∆Hv C == C + H — H → H —C—C— H
(a) =
dT RT From the figure, it is clear that    
dlnP − ∆Hv (E a ) b = (E a ) f + ∆H H H H H
(b) =
dT 2 T2 [Here (E a ) b = activation energy of will be [CBSE AIPMT 2009]
dlnP − ∆Hv backward reaction and (E a )f = activation
(c) = (a) 1523.6 kJ mol −1
dT RT 2 energy of forward reaction].
(b) –243.6 kJ mol −1
dln G − ∆Hv If (E a ) b = (E a ) f
(d) = (c) –120.0 kJ mol −1
dT 2 RT 2 then ∆H = 0 (d) 553.0 kJ mol −1
Ans. (c) 25 Consider the following reactions, Ans. (a)

For reaction, (i) H+ (aq) + OH− (aq) →H 2O(l), As we know that,
H H H H
− x 1kJmol −1 ∆ H = ∆ E + p∆ V
   
C == C + H — H → H — C— C— H 1 or ∆ H = ∆ E + ∆ ng RT
(ii) H 2 (g) + O 2 (g) → H 2O(l), where, ∆ng → number of gaseous moles
    2
H H H H of product – number of gaseous moles of
x 2 kJ mol–1
∆Hreaction reactant
(iii) CO 2 (g) + H 2 (g) → CO(g) + H 2O(l) If ∆ng = 0 (for reactions in which the total
= ∑ BE (reactant) − ∑ BE (product) ,
− x 3 kJ mol −1 number of moles of gaseous products
[BE = bond energy]
5 are equal to total number of moles of
∆Hr = [4 × BE (C—H) + 1 × BE (C= =C) + 1 (iv) C 2H2 (g) + O 2 (g) → 2 CO 2 (g) gaseous reactants), therefore ∆ H = ∆ E
2
× BE (H—H) ] − [6 × BE (C —H) + 1 × BE (C  C) ] So, for reaction (a) ∆ n = 2 − 2 = 0
+ H 2O(l), + x 4 kJ mol −1 Hence, for reaction (a), ∆ H = ∆E
= (4 × 410.50 + 1 × 606.10 + 1 × 431.37)
Enthalpy of formation of H2O(l) is
− [(6 × 410.50) + (1 × 336.49)] kJmol −1
[CBSE AIPMT 2007] 28 The absolute enthalpy of
= [1642 + 606.1 + 43137
. ]
(a) − x2 kJ mol−1 (b) + x3 kJ mol−1 neutralisation of the reaction
. ] kJmol −1
− [2463 + 33649 (c) − x4 kJ mol−1 (d) + x1 kJ mol−1 [CBSE AIPMT 2005]
= [267947
. ] − [279949. ] kJmol −1
−1
Ans. (a) MgO(s) +2HCl(aq) → MgCl 2 (aq)
= − 120.0 kJ mol
Enthalpy of formation The amount of + H2O( l ) will be
23 Bond dissociation enthalpy of H2 ,
heat evolved or absorbed during the (a) less than – 57.33 kJ mol–1
formation of 1 mole of a compound from (b) – 57.33 kJ mol–1
Cl 2 and HCl are 434, 242 and 431 kJ its constituent elements is known as
(c) greater than –57.33 kJ mol–1
mol −1 respectively. Enthalpy of heat of formation. So, the correct
(d) 57.33 kJ mol–1
answer is
formation of HCl is 1 Ans. (a)
[CBSE AIPMT 2008] H2 ( g) + O2 ( g) → H2O(l ),
2 Heat of neutralisation of strong acid and
(a) 93 kJ mol −1 (b) –245 kJ mol −1 ∆H = − x2 kJ mol −1 strong base is − 57.33 kJ. MgO is weak
(c) –93 kJ mol −1 (d) 245 kJ mol −1 base while HCl is strong acid, so the heat
Ans. (c) 26 The enthalpy of combustion of H2 , of neutralisation of MgO and HCl is lower
Given, ∆HH H = 434 kJ / mol cyclohexene (C 6H10 ) and than –57.33 kJ because MgO requires
some heat for ionisation, therefore the
∆HCl  Cl = 242 kJ / mol cyclohexane (C 6H12 ) are –241,
net released amount of heat is
∆HH  Cl = 431 kJ / mol –3800 and –3920 kJ per mol decreased.
1 1 respectively. Heat of hydrogenation
H2 + Cl2 → HCl , ∆Hr = ?
2 2 of cyclohexene is 29 If the bond energies of
1 1 [CBSE AIPMT 2006] H — H, Br — Br and H — Br are 433,
∆Hr = × ∆HH H +
2 2 (a) –121 kJ per mol (b) + 121 kJ per mol 192 and 364 kJ mol −1 respectively,
× ∆HCl  Cl − ∆HH  Cl (c) + 242 kJ per mol(d) –242 kJ per mol then ∆ H° for the reaction
=
1 1
× 434 + × 242 − 431
Ans. (a) H2 (g) + Br 2 (g) → 2HBr (g) is
2 2 [CBSE AIPMT 2004]
= 217 + 121 − 431 = − 93 kJ / mol + H2 (a) − 261kJ (b) +103kJ
(c) +261kJ (d) −103kJ
24 Given that bond energies of H—H Cyclohexene Cyclohexane Ans. (d)
and Cl—Cl are 430 kJ mol −1 and 240 ∆H = [∆H of combustion of cyclohexane For reaction,
kJ mol −1 respectively and ∆Hf for – (∆H of combustion of cyclohexene H2 ( g) + Br2 ( g) → 2HBr( g) ∆H ° = ?
HCl is –90 kJ mol −1 . Bond enthalpy + ∆H of combustion of H2 )] ∆H° = − [(2 × bond energy of HBr) – (bond
of HCl is [CBSE AIPMT 2007] = − [− 3920 − (−3800 − 241)] kJ energy of H2 + bond energy of Cl2 )]
(a) 290 kJ mol−1 = − [−3920 + 4041] kJ ∆H° = − [2 × (364) − (433 + 192)] kJ
(b) 380 kJ mol−1 = − [121] kJ = − 121kJ = − [728 − (625)] kJ = − 103 kJ
(c) 425 kJ mol−1
(d) 245 kJ mol−1 27 Assume each reaction is carried 30 For the reaction,
Ans. (b) out in an open container. For which C 3H8 ( g) + 5O 2 ( g) → 3CO 2 ( g)
∆Hreaction = ∆H—H + ∆HCl — Cl − 2∆HHCl reaction will ∆ H = ∆ E? + 4H2O(l)
[CBSE AIPMT 2006]
∆HH— Cl =
430 + 240 − (–90) at constant temperature, ∆H − ∆E
or (a) H2 (g ) + Br2 (g ) → 2HBr (g )
2
(b) C ( s ) + 2 H2O ( g) → 2 H2 ( g) + CO2 ( g)
is [CBSE AIPMT 2003]
760 (b) −RT
= = 380 kJ mol −1 (c) PCl5 (g) → PCl3 (g) + Cl2 ( g) (a) +3RT
2 (c) + RT (d) −3RT
(d) 2 CO ( g) + O2 ( g) → 2 CO2 ( g)
Ans. (d) Ans. (b) On addition Eqs. (i) and (ii)

For the reaction, 1 S(s ) + O2 ( g) → SO2 ( g) + (2 x − y) kcal
CH4 ( g) + O2 ( g ) → CH3OH(l )
C3H8 (g) + 5O2 (g) → 3CO2 (g) + 4H2O(l ) 2 Hence, heat of formation ofSO2 is (2x − y)
∆ng = number of gaseous moles of ∴ ∆H = –[(∆Hc of CH3OH) – (∆Hc of CH4 )] kcal.
products – number of gaseous moles of = –[(–y) – (–x)] = – [–y + x] = y – x
reactants = 3 − 6 = − 3 37 Given that,
∴ x< y
∴ ∆ H = ∆ E + ∆nRT C (s) +O 2 (g) → CO 2 (g) ,
or ∆ H − ∆ E = ∆nRT 34 Change in enthalpy for reaction, ∆H ° = − x kJ
∴ ∆ H − ∆ E = − 3 RT
2H2O 2 (l) → 2H2O(l) + O 2 (g) 2CO(g) +O 2 (g) → 2CO 2 (g) ,
31 For which one of the following if heat of formation ofH2O 2 (l) and ∆H ° = − y kJ
equations ∆H °r equal to ∆Hf° for H2O(l) are –188 and –286 kJ/mol The enthalpy of formation of
the product? [CBSE AIPMT 2003] respectively is [CBSE AIPMT 2001] carbon monoxide will be
(a) – 196 kJ/mol (b) + 196 kJ/mol
(a) Xe( g) + 2F2 ( g) → XeF4 ( g) [CBSE AIPMT 1997]
(b) 2CO (g) + O2 (g) → 2CO2 ( g)
(c) + 948 kJ/mol (d) – 948 kJ/mol y − 2x 2x − y
(a) y − 2 x (b) 2x − y (c) (d)
(c) N2 ( g) + O 3 ( g) → N2O 3 ( g) Ans. (a) 2 2
(d) CH4 ( g) + 2Cl2 (g) → 2H2O2 (l ) → 2H2O(l ) + O2 ( g) ∆H = ? Ans. (c)
CH2Cl2 (l ) + 2HCl ( g) ∆H = [(2 × ∆Hf of H2O(l )) + (∆ Hf of O2 (g)] C+ O2 → CO2 , ∆H ° = − x kJ ...(i)
Ans. (a) –(2 × ∆Hf of H2O2 (l ))] On reversing given second equation we
When one mole of a substance is directly = [(2 × –286) + (0) –(2 × – 188)] get,
formed from its constituent elements, = [–572 + 376] = –196 kJ / mol 2CO2 → 2CO + O2 , ∆H ° = + y kJ
then the enthalpy change is called heat
or CO2 → CO+ 1 / 2O2 ,
of formation. 35 If ∆E is the heat of reaction for ∆H ° = + y /2kJ ...(ii)
For the reaction,
Xe( g) +2F2 ( g) → XeF4 ( g)
C 2H5OH(l) + 3O2 (g) → 2CO2 (g) From Eqs. (i) and (ii) (by addition)
+ 3H2O(l) at constant volume, the 1
1mol C+ O2 → CO,
∆H ° react = ∆Hf° ∆H (heat of reaction at constant 2
y y − 2x
pressure), then the correct ∆H ° = − x = kJ
2 2
32 Heat of combustion ∆H° for C(s), relation is [CBSE AIPMT 2000]
H2 (g) and CH4 (g) are –94, –68 and (a) ∆H = ∆ E + RT
38 If enthalpies of formation of
–213 kcal/mol. Then, ∆H° for (b) ∆H = ∆ E − RT
C 2H4 (g), CO 2 (g) and H2O(l) at 25°C
C(s) +2H2 (g) → CH4 (g) is (c) ∆H = ∆ E − 2 RT
(d) ∆H = ∆ E + 2 RT
and 1 atm pressure are 52, –394
[CBSE AIPMT 2002]
and –286 kJ/mol, the enthalpy of
(a) – 17 kcal/mol (b) – 111 kcal/mol Ans. (b)
combustion of ethene is equal to
(c) – 170 kcal/mol (d) – 85 kcal/mol We know that, ∆H = ∆E + ∆ng RT [CBSE AIPMT 1995]
Ans. (a) where, ∆ng = total number of moles of (a) –141.2 kJ/mol (b) –1412 kJ/mol
For reaction, gaseous product – total number of moles
(c) +14.2 kJ/mol (d) +1412 kJ/mol
of gaseous reactant
C(s ) + 2H2 ( g) → CH4 ( g), ∆H ° = ? Ans. (b)
= 2 – 3 = –1
C + O2 → CO2 , ∆H = −94kcal ...(i)
So, ∆ H = ∆ E – RT Combustion of hydrocarbon,
2H2 + O2 → 2H2O,
C2H4 (g) + 3O2 (g) → 2CO2 (g) + 2H2O(l )
∆H = − 68 × 2kcal ...(ii)
36 From the given reactions, ∆ r H = Σ∆fHp − Σ∆fHr
CH4 + 2O2 → CO2 + 2H2O,
3 = {2 × ∆fH (CO2 ) + 2 × ∆fH (H2O)}
∆H = −213 kcal ...(iii) S(s) + O 2 (g) → SO 3 (g) + 2x kcal
2 − { ∆fH (C2H4 ) + 3∆fH(O2 )}
On adding Eqs. (i) and (ii) and then
1 = (2 × − 394 + 2 × − 286) − (52 + 3 × 0)
subtracting Eq. (iii) SO 2 (g) + O 2 (g) → SO 3 (g) + y kcal,t
= (−94) + (−2 × 68) − (−213) 2 = − 788 − 572 − 52 = − 1412kJ mol −1
= −230 + 213 = −17 k cal / mol he heat of formation ofSO 2 is
[CBSE AIPMT 1999] 39 For the reaction, [CBSE AIPMT 1991]
33 Enthalpy of the reaction, (a) (x + y) (b) (x − y) N 2 + 3H2 2NH3 , ∆H = ?
3
1 (c) (2x + y) (d) (2x − y) (a) ∆E + 2 RT (b) ∆E − 2 RT
CH4 + O 2 → CH3OH, is
2 Ans. (d) (c) ∆H = RT (d) ∆E − RT
negative. If enthalpy of combustion 3
S(s ) + O2 ( g) → SO3 ( g) +2x kcal …(i) Ans. (b)
of CH4 and CH3 OH are x and y 2
According to enthalpy equation
respectively, then which relation is By inverting second equation we get, ∆H = ∆E + ∆ng RT
correct? 1 Enthalpy
[CBSE AIPMT 2001] SO3 (g) → SO2 ( g) + O2 ( g) – y kcal …(ii) change
Internal
energy
(a) x > y (b) x < y (c) x = y (d) x ≥ y 2
∆n = 2 − (1 + 3) 44 Hydrolysis of sucrose is given by

[∆n = nP − nR ] TOPIC 3 the following reaction.
Product Reactant
mole mole
Entropy, Free Energy Sucrose + H2O c Glucose +
= 2 − 4 = −2
Fructose
∴ ∆H = ∆E + (− 2) RT Change and Spontaneity
If the equilibrium constant (K C ) is
∆H = ∆E − 2 RT
42 For irreversible expansion of an 2 × 10 13 at 300 K, the value of ∆ r G È
40 Equal volumes of molar ideal gas under isothermal at the same temperature will be
hydrochloric acid and sulphuric condition the correct option is [NEET (Sept.) 2020]
acid are neutralised by dilute NaOH [NEET 2021] (a) 8.314 J mol −1 K −1 × 300 K ×ln(2 × 10 13)
solution and x kcal and y kcal of (a) ∆U = 0, ∆S total = 0 (b) 8.314 J mol −1 K −1 × 300 K ×ln(3 × 10 13)
heat are liberated respectively. (b) ∆U ≠ 0, ∆S total ≠ 0 (c) − 8.314 J mol −1 K −1 × 300 K ×ln(4 × 10 13)
Which of the following is true? (d) − 8.314 J mol −1 K −1 × 300 K ×ln(2 × 10 13)
(c) ∆U = 0, ∆S total ≠ 0
(a) x = y Ans. (d)
[CBSE AIPMT 1991] (d) ∆U ≠ 0, ∆S total = 0
1 Sucrose + H2O r Glucose + Fructose
(b) x = y Ans. (c)
2 For this equilibrium,
(c) x = 2 y The change in internal energy depends ∆ r G s = − RT ln K C
on the temperature. For isothermal
(d) None of the above Given,K C = 2 × 10 13 andT = 300 K
process, ∆T = 0.
Ans. (b) ⇒∆ r G s = − (8.314 J mol − 1K− 1) × (300 K) ×
So, ∆U = 0.
HCl + NaOH → NaCl + H2O + x kcal ln (2 × 10 13)
With an expansion of an ideal gas, more
H2SO4 + 2NaOH → Na2SO4 + 2H2O space is available for the gaseous
+ y kcal particles. 45 For the reaction, 2Cl(g) → Cl 2 (g),
1 molar HCl = 1 g - equivalent of HCl ∴Entropy of gas increases so, entropy of the correct option is
1 molar H2SO4 = 2 g - equivalent of H2SO4 system is not zero. [NEET (Sep.) 2020]
1 i.e. ∆S ≠ 0 (a) ∆ r H > 0 and ∆ r S < 0
so, y =2x ⇒ x = y
2 (b) ∆ r H < 0 and ∆ r S > 0
43 If for a certain reaction ∆ r H is 30 (c) ∆ r H < 0 and ∆ r S < 0
41 If ∆H is the change in enthalpy and kJ mol −1 at 450 K, the value of ∆ r S (d) ∆ r H > 0 and ∆ r S > 0
∆E, the change in internal energy (in JK −1 mol −1 ) for which the same Ans. (c)
accompaning a gaseous reaction, reaction will be spontaneous at the In this reaction, combination of two Cl
then [CBSE AIPMT 1990] same temperature is atoms takes place to give more stable
(a) ∆ H is always greater than ∆ E [NEET (Oct.) 2020] Cl2 molecule. So, the reaction is
(b) ∆ H < ∆ E only if the number of moles exothermic, i.e, ∆ r H < 0.
(a) 70 (b) −33
of products is greater than the Here, ∆ng = 1 − 2 = − 1
(c) 33 (d) −70
number of moles of the reactants So, entropy change of the reaction will
(c) ∆H is always less than ∆ E
Ans. (a) be, ∆ r S < 0.
(d) ∆ H < ∆ E only if the number of moles ∆G = ∆H − T∆S (Gibbs equation)
of products is less than the number For a spontaneous reaction, 46 Reversible expansion of an ideal
of moles of the reactants ∆G < 0, i.e.T∆S > ∆H gas under isothermal and adiabatic
Ans. (d) ∆H 30 × 1000 J mol − 1 conditions are as shown in the
⇒ T> =
Reactions in which there is a decrease in ∆S ∆S figure. [NEET (Odisha) 2019]
the number of moles of the gaseous [Given,T = 450 K] A ( pA, VA, TA)
components,
30 × 1000 J mol − 1
i.e. ∆ng is negative, the enthalpy change ⇒∆S >
450 K B ( pB, VB, TB)
(∆H) is lesser than the internal energy p
change (∆E). −1 −1
= 6667
. J mol K
Reaction in which there is a increase in When ∆S > 6667 . J mol − 1 K− 1, the C ( pC, VC, TC)
the number of moles of gaseous reaction will be spontaneous.
components i.e. ∆ng is positive, the So, from the options, V
enthalpy change is greater than the ∆ r S = 70 J mol − 1K− 1 indicates AB → Isothermal expansion
internal energy change. spontaneity of the reaction.
∆H = ∆E + ∆ng RT
AC → Adiabatic expansion
Which of the following option is (c) Entropy is negative in case of 51 For a sample of perfect gas when
not correct? 2H(g) → H2 (g) as the number of
its pressure is changed
moles of gaseous reactants are more
(a) ∆S isothermal > ∆S adiabatic than that of gaseous products. isothermally from pi to pf , the
(b)TA = TB (d) Entropy is positive in case of entropy change is given by
evaporation of water as gas is much [NEET 2016, Phase II]
(c) Wisothermal > Wadiabatic
disordered than a liquid. p 
(d) Tc > TA (a) ∆S = nR ln  f 
Hence, option (c) is correct.  pi 
Ans. (d)
49 For a given reaction, ∆H = 35.5 kJ p 
From first law of thermodynamics, (b) ∆S = nR ln  i 
∆U = q + W mol −1 and ∆S = 83.6 JK −1 mol −1 . The  pf 
In adiabatic expansion,q = 0 reaction is spontaneous at : p 
∴ ∆U = W (c) ∆S = nRT ln  f 
(Assume that ∆H and ∆S do not  pi 
During expansion of a gasw is negative vary with temperature) [NEET 2017]  pi 
i.e w < 0 or ∆U < 0. (d) ∆S = RT ln  
(a)T < 425 K
We know that, ∆U = nC V ∆T  pf 
(b)T > 425 K
∴ nC V ∆T < 0 (c) all temperatures Ans. (b)
or ∆T < 0 (d)T > 298 K Entropy change is given as,
∴ TC −TA < 0 Ans. (b) T p
∆S = nC p ln f + nR ln i K(i)
or TC < TA According to Gibbs-Helmholtz equation, Ti pf
Thus, option (d) is incorrect while the Gibbs energy (∆G) = ∆H − T∆S For isothermal process,Ti = Tf
remaining options are correct.
Where, ∆H = Enthalpy change T T
∴ nC p ln f = nC p ln i = 0 [ln 1 = 0]
∆S = Entropy change Ti Ti
47 For an ideal solution, the correct
T = Temperature
option is [NEET (National) 2019] From Eq. (i)
For a reaction to be spontaneous pi
(a) ∆ mix V ≠ 0 at constantT and p ∆S = nR ln
∆G < 0.
(b) ∆ mix H = 0 at constantT and p pf
∴ Gibbs -Helmholtz equation becomes,
(c) ∆ mix G = 0 at constantT and p
(d) ∆ mix S = 0 at constantT and p ∆G = ∆H − T∆S < 0 52 Which of the following statements
or, ∆H < T∆S is correct for a reversible process
Ans. (b)
∆H 35.5 kJ mol −1 in a state of equilibrium?
Ideal solutions are those which obey or, T> =
Raoult’s law over all concentration ∆S 83.6 JK−1mol −1 [CBSE AIPMT 2015]
ranges at a given temperature, e.g. 35.5 × 1000 (a) ∆G = – 2.30 RT log K
= = 425 K
benzene-toluene, n-hexane-n-heptane, 836
. (b) ∆G = 2.30 RT log K
etc. T > 425 K (c) ∆G ° = – 2.30 RT log K
For an ideal solution,
(d) ∆G ° = 2.30 RT log K
∆Vmix = 0, ∆Hmix = 0, 50 The correct thermodynamic
Ans. (a)
∆G mix < 0, ∆S mix > 0. conditions for the spontaneous
Mathematical expression of the
Hence, option (b) is correct. reaction at all temperatures is
thermodynamic equilibrium is
∆G = ∆G ° + 2 .303RT log Q
48 In which case change in entropy is (a) ∆H > 0 and ∆S < 0
At equilibrium when ∆G = 0 and Q = K
negative? [NEET (National) 2019] (b) ∆H < 0 and ∆S > 0
then ∆G = ∆G ° + 2.303 RT log K = 0
(a) Expansion of a gas at constant (c) ∆H < 0 and ∆S < 0
∆G ° = − 2.303 RT log K
temperature (d) ∆H < 0 and ∆S = 0
(b) Sublimation of solid to gas Ans. (b,d)
(c) 2H(g )→ H2 (g ) 53 Which of the following statements
We have the Gibbs Helmholtz reaction is correct for the spontaneous
(d) Evaporation of water for spontaneity as
Ans. (c) absorption of a gas?
∆G = ∆H − T∆S [CBSE AIPMT 2014]
The explanation of given statements are : For reaction to be spontaneous, ∆G must (a) ∆S is negative and therefore, ∆H
(a) Entropy is positive in case of be negative. should be highly positive
expansion of a gas at constant For this, ∆H should be negative and ∆S (b) ∆S is negative and therefore, ∆H
temperature. It is because during should be positive. should be highly negative
expansion of gas volume increases
∴ ∆H < 0 (c) ∆S is positive and therefore, ∆H
and hence randomness increases.
(b) Entropy is positive in case of and ∆S > 0. should be negative
and also ∆S = 0 shows ∆G a negative (d) ∆S is positive and therefore, ∆H
sublimation of solid to gas as gas is
quantity. should also be highly positive
much disordered than a solid.
Ans. (b) 1 58 The values of ∆ H and ∆S for the

(a) C (graphite) + O2 ( g) → CO ( g)
∆S [change in entropy] and ∆H [change 2
1 reaction,
in enthalpy] are related by the equation (b) CO ( g) + O2 ( g) → CO2 ( g)
∆G = ∆H − T ∆S 2 C (graphite) + CO 2 (g) → 2CO(g) are
[Here, ∆G = change in Gibbs free energy] 1
(c) Mg (s ) + O2 ( g) → MgO (s ) 170 kJ and 170 JK −1 , respectively.
For adsorption of a gas, ∆S is negative 2 This reaction will be spontaneous
because randomness decreases. Thus, 1 1
(d) C (graphite) + O2 ( g) → at [CBSE AIPMT 2009]
in order to make ∆G negative [for 2 2 1 (a) 710 K (b) 910 K
spontaneous reaction], ∆H must be CO2 ( g)
highly negative. Hence for the 2 (c) 1110 K (d) 510 K
adsorption of a gas, if ∆S is negative, Ans. (a) Ans. (c)
therefore, ∆H should be highly negative. Among the given reactions only in the Given, ∆H = 170 kJ = 170 × 10 3 J
case of ∆S = 170 JK−1 ; T = ?
54 For the reaction, 1 ∆G = ∆H –T∆S
C (graphite) + O2 ( g) → CO ( g)
X 2 O 4 (l) → 2XO 2 (g), 2 For spontaneous reaction,
∆U = 2.1kcal, entropy increases because randomness ∆G < 0
∆S = 20cal K −1 at 300 K. (disorder) increases. Thus, standard
⇒ 0 < 170 × 10 3 − T × 170 ; T > 1000
entropy change (∆S ° ) is positive.
Hence, ∆G is [CBSE AIPMT 2014] Moreover, it is a combustion reaction ∴ T = 1110 K
(a) 2.7 kcal (b) − 2.7 kcal and all the combustion reactions are
(c) 9.3 kcal (d) − 9.3 kcal generally exothermic, i.e. ∆H° = −ve 59 For the gas phase reaction,
Ans. (b) We know that, PCl 5 (g) º PCl 3 (g) + Cl 2 (g)
The change in Gibbs free energy is given ∆G ° = ∆H ° − T∆S ° which of the following conditions
by ∆G ° = − ve − T (+ ve) are correct? [CBSE AIPMT 2008]
∆G = ∆H − T∆S Thus, as the temperature increases, the (a) ∆H = 0 and ∆S < 0
value of ∆G ° decreases. (b) ∆H > 0 and ∆S > 0
where, ∆H = change enthalpy of the
reaction 56 The enthalpy of fusion of water is (c) ∆H < 0 and ∆S < 0
∆S = change entropy of the reaction (d) ∆H > 0 and ∆S < 0
1.435 kcal/mol. The molar entropy
Thus, in order to determine ∆G, the values change for the melting of ice at 0°C Ans. (b)
of ∆H must be known. The value of ∆H can is [CBSE AIPMT 2012] From enthalpy equation,
be calculated by using equation ∆H = ∆E + ng RT
(a) 10.52 cal/mol K (b) 21.04 cal/mol K
∆H = ∆U + ∆ng RT K(i) For the reaction,
(c) 5.260 cal/mol K (d) 0.526 cal/mol K
where, ∆U = change in internal PCl 5 ( g)3 PCl 3 ( g) + Cl2 ( g)
energy using Ans. (c)
∆ng = product mole − reactant mole
∆ng = number of moles of gaseous Molar entropy change for the melting of
∆n = 2 − 1 = 1
products − number of moles of gaseous ice,
∆Hfusion 1435
. kcal / mol Thus, the value of ∆H is positive or > 0.
reactants ∆S melt = =
(0 + 273) K ∆G = ∆H − T∆S
= 2−0 = 2 T
For a spontaneous reaction, ∆G must be
R = gas constant = 2 cal . × 10 −3 kcal/mol K
= 526 negative. Since in this reaction ∆H is
given, ∆U = 2.1 kcal = 526
. cal/mol K positive, so for the negative value of ∆G,
= 2.1 × 10 3 cal ∆S must be positive or > 0.
[Q1 kcal = 10 3 cal] 57 If the enthalpy change for the Hence, ∆H > 0, ∆S > 0
By putting the values in eq. (i) we get, transition of liquid water to steam
∴ ∆H = (2.1 × 10 3) + (2 × 2 × 300) is 30 kJ mol −1 at 27°C, the entropy 60 The enthalpy and entropy change
= 3300 cal change for the process would be for the reaction,
Hence, ∆G = ∆H − T∆S [CBSE AIPMT 2011]
Br 2 (l) + Cl 2 (g) → 2BrCl (g)
⇒ ∆G = (3300) − (300 × 20) (a) 1.0 J mol −1K −1 (b) 0.1 J mol −1K −1
are 30 k J mol–1 and 105 JK –1 mol–1
(c) 100 J mol −1K −1 (d) 10 J mol −1K −1
∆G = −2700 cal respectively. The temperature at
∴ ∆G = − 2.7 kcal
Ans. (c)
which the reaction will be in
∆G ° = ∆H ° − T∆S ° equilibrium is [CBSE AIPMT 2006]
55 In which of the following reactions, Given, ∆Hvap. = 30kJ mol −1 (a) 285.7 K (b) 273 K
standard reaction entropy changes T = 27 + 273 = 300k (c) 450 K (d) 300 K
(∆S° ) is positive and standard Gibbs ∆G ° = 0 at equilibrium,
energy change (∆G° ) decreases Ans. (a)
∆Hvap 30 × 10 3 J mol –1
sharply with increasing ∆S vap = = At equilibrium Gibbs free energy change (
T 300 K ∆G) is equal to zero.
temperature? [CBSE AIPMT 2012]
= 100 J mol –1 K–1 ∆G = ∆H − T∆S
0 = 30 × 10 3 (J mol –1) following equation (Gibbs-Helmholtz (a) 2.198 JK−1mol −1 (b) 21.98 JK−1mol −1
− T × 105 (J K–1 mol –1) equation) (c) 20.13 JK−1mol −1 (d) 2.013 JK−1mol −1
30 × 10 3 ∆G = ∆ H − T∆ S Ans. (b)
∴ T= K = 285.71 K If the magnitude of ∆ H − T∆ S is negative,
105 Given, ∆Hf = 60. kJ mol −1
then the reaction is spontaneous.
T = 0 + 273 = 273 K
61 Identify the correct statement for whenT∆ S > ∆ H or we can say that ∆H
∆Hf 60 .
and ∆ S are positive, then ∆G is ∆S = = = 0.02198 kJ K–1 mol –1
change of Gibbs free energy for a negative. T 273
system (∆G system ) at constant (T = 0 ° C + 273 = 273 K)
temperature and pressure. 64 Considering entropy (S) as a
= 0.02198 × 1000 JK–1 mol –1
[CBSE AIPMT 2006] thermodynamic parameter, the
(a) If ∆G system > 0, the process is = 21.98 JK–1 mol –1
criterion for the spontaneity of any
spontaneous process is [CBSE AIPMT 2004]
(b) If ∆G system = 0, the system has 67 The densities of graphite and
(a) ∆S system + ∆S surrounding >0
attained equilibrium diamond at 298 K are 2.25 and 3.31
(b) ∆S system – ∆S surrounding >0
(c) If ∆G system = 0, the system is still g cm −3 , respectively. If the
(c) ∆S system >0
moving in a particular direction standard free energy difference
(d) ∆S surrounding >0
(d) If ∆G system < 0, the process is not (∆G° ) is equal to 1895 J mol −1 , the
spontaneous Ans. (a)
pressure at which graphite will be
Ans. (b) For spontaneous process, ∆S must be transformed into diamond at 298 K
positive. In reversible process
If the Gibbs free energy for a system ( is [CBSE AIPMT 2003]
∆G system ) is equal to zero, then system is ∆ S system + ∆ S surrounding = 0
(a) 9.92 × 106 pa
present in equilibrium at a constant Hence, system is present in equilibrium.
(i.e. it is not spontaneous process) (b) 9.92 × 105 pa
temperature and pressure.
∆G = ∆ r G o + RT ln K ; ∆G = 0 While in irreversible process (c) 9.92 × 108 pa
∆S system + ∆S surrounding > 0 (d) 9.92 × 107 Pa
∆ r G o = − RT ln K
Hence, in the process ∆ S is positive. Ans. (c)
K = equilibrium constant
Mass 12
If ∆G system < 0, then the process is 65 Standard enthalpy and standard Volume of graphite = =
Density 2.25
spontaneous entropy changes for the oxidation 12
of ammonia at 298 K are Volume of diamond =
62 Which of the following pairs of a 3.31
−382.64 kJ mol −1 and Change in volume,
chemical reaction is certain to
−145.6 JK –1mol–1 , respectively.  12 12  −3
result in a spontaneous reaction? ∆V =  −  × 10 L
[CBSE AIPMT 2005]
Standard Gibbs energy change for  331
. . 
225
(a) Exothermic and decreasing disorder
the same reaction at 298 K is = − 1.91 × 10 −3 L
[CBSE AIPMT 2004]
(b) Endothermic and increasing disorder ∆G ° = work done= − p∆V
(c) Exothermic and increasing disorder (a) − 221.1 kJmol–1 (b) − 339.3 kJ mol–1 ∆G °
(c) − 439.3 kJ mol–1 (d) − 523.2 kJ mol–1 p= −
(d) Endothermic and decreasing disorder ∆V
Ans. (c) Ans. (b) 1895 J mol –1
=
If reaction is exothermic, therefore ∆H is ∆G ° = ∆H ° − T∆S ° K(i) 1.91 × 10 −3 × 101.3
negative and on increasing disorder, ∆S Given that, ∆H ° = − 382 .64 kJ mol –1 = 9794 atm
is positive thus, at these condition, ∆G is ∆S ° = − 1456
. J K–1 mol –1 [Q 1 atm = 10 5 × 1.013 Pa]
negative according to following
= − 145.6 × 10 −3 kJ K–1 = 992
. × 10 8 Pa
equation.
T = 298 K
∆G = ∆H − T∆S
∆G = negative, and for spontaneous On putting the given values in eq. (i) 68 2 moles of an ideal gas at 27°C
reaction ∆G must be negative. we get, temperature is expanded reversibly
or ∆G ° = − 382 .64 from 2 L to 20 L. Find entropy
63 A reaction occurs spontaneously if − [298 × (− 145.6 × 10 −3)] change (R = 2 cal/mol K).
= − 339.3 kJ mol –1
(a)T∆S < ∆H and both ∆H and ∆S are +ve (a) 92.1 (b) 0 (c) 4 (d) 9.2
(b)T∆S > ∆H and both ∆H and ∆S are +ve 66 What is the entropy change (in Ans. (d)
(c)T∆S = ∆H and both ∆H and ∆S are +ve J K −1 mol −1 ) when one mole of ice V2
(d)T∆S > ∆H and ∆H is +ve and ∆S is –ve ∆S (entropy change) = 2 .303 nR log 10
is converted into water at 0°C? V1
Ans. (b) (The enthalpy change for the 20
= 2 .303 × 2 × 2 × log 10
The spontaneity of a reaction is based conversion of ice to liquid water is 2
upon the negative value of ∆G and ∆G is
6.0 kJ mol −1 at 0°C) = 2 .303 × 2 × 2 × 1 = 9.212 cal
based upon T, ∆S and ∆H according to
[CBSE AIPMT 2003]
69 Unit of entropy is Ans. (b) 74 Given the following entropy values

[CBSE AIPMT 2002] ∆G of formation of different substances (in JK −1 mol −1 ) at 298 K and 1 atm :
(a) JK −1 mol −1 are as H2 (g) : 130.6, Cl 2 (g ) : 223.0, HCl(g) :
(b) J mol −1 2 SO2 = –544 kJ 186.7. The entropy change (in
(c) J −1 K −1 mol −1 2 ZnS = –293 kJ JK −1 mol −1 ) for the reaction
(d) JK mol −1 2ZnO = –480 kJ H2 (g) + Cl 2 (g) → 2HCl(g), is
Ans. (a) For the reaction, [CBSE AIPMT 1996]
Entropy change equal to change in heat 2ZnS + 3 O2 ( g) → 2ZnO(s ) + 2 SO2 ( g) (a) +540.3 (b) +727.0
q
per degree. ∆S = ∆G = [(∆G (products) —∆G (reactants) ]
(c) –166.9 (d) +19.8
T
Ans. (d)
q = required heat per mol = [(− 480) + (− 544) − ( − 293)]
H2 ( g) + Cl2 ( g) → 2HCl( g)
T = constant absolute temperature = − 1024 + 293
∆ r S = Σ S m ° (P) − Σ S m ° (R)
Thus, unit of entropy is JK–1mol –1 = − 731kJ ∆ r S ° = 2 × S m ° (HCl) − [S m ° (Cl2 )
70 PbO 2 → PbO, ∆G 298 < 0 + S m ° (H2 )]
72 The entropy change in the fusion of
= (2 × 186.7) − (223 + 130.6)
SnO 2 → SnO, ∆G 298 > 0 one mole of a solid melting at
= 373.4 − 353.6
27°C (latent heat of fusion is
Most probable oxidation state of = + 19.8 JK−1 mol −1
2930 J mol −1 ) is
Pb and Sn will be [CBSE AIPMT 2000]
(a) Pb 4+ , Sn4+ [CBSE AIPMT 2001] 75 According to the third law of
(a) 9.77J K –1 mol–1
(b) Pb 4+ , Sn2+ thermodynamics which one of the
(b) 10.73 J K –1 mol–1
(c) Pb2+ , Sn2+ following quantities for a perfectly
(c) 2930 J K –1 mol–1 crystalline solid is zero at absolute
(d) Pb2+ , Sn4+
(d) 108.5 J K –1 mol–1 zero? [CBSE AIPMT 1996]
Ans. (d)
+4 +2
Ans. (a) (a) Free energy
Pb O2 → Pb O, ∆G298 < 0 ∆ Hf (b) Entropy
Entropy, ∆Sf =
For this reaction ∆G is negative, hence Tf (c) Enthalpy
Pb2 + is more stable thanPb4+ . Fusion enthalpy (d) Internal energy
+4 +2 =
Sn O2 → Sn O, ∆G298 > 0 Temperature Ans. (b)
2930 J mol –1 Entropy is the degree of randomness or
For this reaction ∆G is positive, hence ∆Sf =
Sn4+ is more stable thanSn2 + because 300 K disorder of the system. When the
for spontaneous change ∆G must be temperature of the system is zero kelvin,
= 9.77 J K–1 mol –1
negative. then all the motion of molecules ceases.
According to third law of
73 Identify the correct statement thermodynamics “At absolute zero the
71 The factor of ∆G values is regarding entropy. entropy of a perfectly crystalline
important in metallurgy. The ∆G [CBSE AIPMT 1998] substance is taken as zero.”
values for the following reactions (a) At absolute zero temperature, entropy
at 800°C are given as of a perfectly crystalline substance is 76 The correct relationship between
taken to be zero
S 2 (s) +2O 2 (g) → 2SO 2 (g), free energy and equilibrium
(b) At absolute zero temperature, the
∆G = − 544 kJ entropy of a perfectly crystalline constant K of a reaction is
[CBSE AIPMT 1996]
2Zn(s) +S 2 (s) → 2ZnS(s), substance is positive
(c) At absolute zero temperature, the (a) ∆G ° = − RT ln K
∆G = − 293 kJ
2Zn(s) + O 2 (g) → 2ZnO(s),
entropy of all crystalline substances (b) ∆G = RT ln K
is to be zero (c) ∆G ° = RT ln K
∆G = − 480 kJ (d) At 0°C, the entropy of a perfectly
(d) ∆G = − RT ln K
The ∆G for the reaction, crystalline substance is taken to be
zero Ans. (a)
2ZnS(s) + 3O 2 ( g) → 2ZnO(s) Ans. (a) The Gibbs free energy of a reaction, ∆ r G
+ 2SO 2 (g) “At absolute zero temperature, entropy
is related to the composition of the
reaction mixture and the standard
will be [CBSE AIPMT 2000] of a perfectly crystalline substance is
reaction Gibbs free energy ∆ r G ° as
(a) –357 kJ (b) –731 kJ taken to be zero.” It is called third law of
thermodynamics. ∆ r G = ∆ r G ° + RT ln Q
(c) –773 kJ (d) –229 kJ
where, Q = reaction quotient
At equilibrium Q = K and ∆ r G = 0. According to Le-Chatelier’s principle, the number of moles of gaseous

Therefore, the above reaction becomes when we increase the concentration of products, so entropy also increases and
0 = ∆ r G ° + RT ln K trans-2-pentene, then the reaction hence, ∆S = positive.
shifts in backward direction and hence, Thus,
∆ r G ° = − RT ln K
the concentration of cis-2-pentene ∆G = ∆H − T∆S = − ve − T (+ ve)
or ∆ r G ° = − 2.303 RT log K increase to maintain the equilibrium
K = equilibrium constant constant K constant at given = − ve at any temperature
temperature.
77 Standard Gibb's free energy change 79 A chemical reaction will be
for the isomerisation reaction 78 Consider the following reaction spontaneous if it is accompanied
occurring in an automobile by a decrease in [CBSE AIPMT 1994]
cis-2-pentene 3trans-2-pent
ene is –3.67 kJ/mol at 400 K. If 2C 8H18 (g) + 25O 2 (g) → (a) entropy of the system
more trans-2-pentene is added to 16CO 2 (g) + 18H2O(g) (b) enthalpy of the system
(c) internal energy of the system
the reaction vessel, then The sign of ∆H, ∆S and ∆G would
(d) free energy of the system
[CBSE AIPMT 1995] be [CBSE AIPMT 1994]
(a) more cis-2-pentene is formed Ans. (d)
(a) +, –, + (b) –, +, – (c) –, +, + (d) +, +, –
(b) equilibrium remains unaffected Gibbs free energy of a system will decide
Ans. (b)
(c) additional trans-2-pentene is formed the spontaneity of a process.
The given reaction is combustion If ∆G is negative, then the process is
(d) equilibrium is shifted in forward
reaction, so it takes place by evolution of spontaneous.
direction
heat and hence, the sign of
Ans. (a) ∆H = negative and there is a increase in
5
States of Matter
TOPIC 1 1
p∝ nH 2 =
Mass of H2
V Molar mass of H2
Gaseous State λ
p = , (λ is a constant) 2
V = = 1 mol
01 Choose the correct option for 2
pV = λ
graphical representation of Boyle’s Total number of moles of mixture,
law, which shows a graph of nT = nO 2 + nH2
pressure vs volume of a gas at p 1
nT = + 1 = mol
9
different temperatures [NEET 2021] 8 8
Ideal gas equation;
pV = nRT
Pressure (p)
 Given, R = 0.082 L atm mol –1 K–1 

(bar)
200
V  
K  
400 As temperature increases, gas expands T = 0 ° C = 273 K, V = 1 L 
K
600 K i.e. volume of gas increases. 9
(a) p× 1= × 0.082 × 273
So, the product pV increases and the p 8
Volume (V) vs V curve of Boyle’s law shifts upwards. ⇒ p = 25.18 atm
(dm3)
03 The minimum pressure required to

Pressure (p)
compress 600 dm 3 of a gas at 1 bar

(bar)
(200 K, 400 K, 600 K) p

(bar)
to 150 dm 3 at 40°C is
600 K [NEET (Oct.) 2020]
(b) 400 K (a) 4.0 bar (b) 0.2 bar
200 K
Volume (V) (c) 1.0 bar (d) 2.5 bar
V
(dm3) Ans. (a)
(dm3)
p1 = 1 bar, p2 = ?
V1 = 600 dm3
40 K
Pressure (p)
02 Choose the correct option for the

K
0
K
0
20
V2 = 150 dm3
(bar)
0 total pressure (in atm) in a mixture

60
of 4g O 2 and 2 g H2 confined in a ⇒From Boyle’s law (Temperature, 40ºC
is constant)
(c) total volume of one litre at 0°C is
p1V1 = p2V2
[Given, R = 0.082 L atm mol − 1 K − 1 , p V 1 × 600
Volume (V)
T = 273K] [NEET 2021] ⇒ p2 (min) = 1 1 = = 4 bar
(dm3) V2 150
(a) 2.518 (b) 2.602
(c) 25.18 (d) 26.02
Pressure (p)
04 A gas at 350 K and 15 bar has molar

Ans. (c)
(bar)
600 volume 20 percent smaller than

K
400 Given, mass of O2 = 4 g that for an ideal gas under the
200 K Molar mass of O2 = 32 g mol −1
(d) K same conditions. The correct
Number of moles of O2 , option about the gas and its
Volume (V) Mass of O2 4 1
nO 2 = = = mol compressibility factor (Z) is
(dm3) Molar mass of O2 32 8 [NEET (National) 2019]
Ans. (d) Given, mass of H2 = 2 g (a) Z > 1 and repulsive forces are
Boyle’s law states, that at constant Molar mass of H2 = 2 g mol −1 dominant
temperature, pressure of a gas of fixed (b) Z < 1 and attractive forces are
Number of moles of H2 ,
amount varies inversely with volume. dominant
States of Matter 45
(c) Z < 1 and repulsive forces are  an2  nO 2 2

 p + 2  (V − nb) = nRT ⇒ =
dominant nH 2 32
 V 
(d) Z > 1 and attractive forces are
dominant ‘a’ and ‘b’ are known as van der Waals’ nO 2 1
constant. ⇒ =
Ans. (b) nH 2 16
‘a’ is the measure of force of attraction
Compressibility factor (Z) is the factor between gas molecules. Greater the nO 2 1
which decides the extent of deviation of ⇒ =
value of a, easier the liquefaction of the 0.5 4
real gases from ideal gases. gas. 0.5 1
V ⇒ nO 2 = =
Z = real Thus, amongNH3 (4.17),H2 (0.244),O2 (1.36) 4 8
Videal and CO2 (3.59), the value ofa is greatest
Real gases deviate from ideal gas in NH3, hence it is most easily liquefied. 09 A mixture of gases contains H2 and
behaviour because for ideal gas it is
considered that there is no force of 07 The correction factor ‘a’ to the ideal O 2 gases in the ratio of 1 : 4 (w/w).
attraction between gas molecules. gas equation corresponds to What is the molar ratio of the two
Also, for ideal gas, volume of gas [NEET 2018] gases in the mixture?
molecules is negligible as compared to [CBSE AIPMT 2015]
(a) electric field present between the
volume of gas container.
gas molecules (a) 1 : 4 (b) 4 : 1 (c) 16 : 1 (d) 2 : 1
Given, Vreal < Videal (b) volume of the gas molecules Ans. (b)
∴ Z< 1 (c) density of the gas molecules Let the mass of H2 gas be xg and mass of
If Z < 1, the gas is more compressible (d) forces of attraction between the gas O2 gas 4xg
than expected from ideal behaviour. As a molecules
result, attractive forces are present
Ans. (d) Molar H2 : O2
between molecules and are dominant.
According to van der Waals’ equation, mass 2 : 32
05 The volume occupied by 1.8 g of  an2  i.e. 1 : 16
 P + 2  (V − nb) = nRT
water vapour at 374°C and 1 bar  V  nH
∴ Molar ratio = 2
pressure will be where,a and b are called van der Waals’ nO 2
[Use R = 0.083 bar L K −1 mol −1 ] constant. x /2
[NEET (Odisha) 2019] an2 =
is called internal pressure of the gas 4x /32
(a) 96.66 L (b) 55.87 L V2 x × 32 4
(c) 3.10 L (d) 5.37 L where, ‘a’ is a measure of force of = = = 4: 1
2 × 4x 1
Ans. (d) attraction between gas molecules.
‘b’ is also called co-volume or excluded
According to ideal gas equation,
volume. 10 Equal masses of H2 , O 2 and
pV = nRT methane have been taken in a
The constants ‘a’ and ‘b’ are expressed in
…(i) Qn =
nRT w RT w 
or V = = atm L2 mol −2 and L mol −1, respectively. container of volume V at
p M.wt p 
 M.wt 
temperature 27°C in identical
Given, w = 1.8 g,T = 374º C 08 Equal moles of hydrogen and conditions. The ratio of the
= (374 + 273) K = 647 K oxygen gases are placed in volumes of gases H2 : O 2 : CH4
p = 1 bar, R = 0.083 bar LK −1 mol −1 container with a pin-hole through would be [CBSE AIPMT 2014]
On substituting the given values in Eq. (i), which both can escape. What (a) 8 : 16 : 1 (b) 16 : 8 : 1
we get fraction of the oxygen escapes in
1.8 g (c) 16 : 1 : 2 (d) 8 : 1 : 2
V= the time required for one-half of
18 g mol -1 Ans. (c)
0.083 bar LK–1 mol –1 × 647 K the hydrogen to escape?
× According to Avogadro’s hypothesis,
1 bar [NEET 2016, Phase I]
Volume of a gas (V ) ∝number of moles (n)
(a) 1/4 (b) 3/8
= 537
. L Therefore, the ratio of the volumes of
(c) 1/2 (d) 1/8
gases can be determined in terms of
06 Given van der Waals’ constant of Ans. (d) their moles.
NH3 , H2 , O 2 and CO 2 are Given, number of moles of hydrogen ∴ The ratio of volumes of H2 : O2 :
respectively 4.17, 0.244, 1.36 and (nH 2 ) and that of oxygen (nO 2 ) are equal. methane (CH4 ) is given by
3.59, which one of the following ∴ We have, the relation between ratio of VH 2 :VO 2 :VCH 4 = nH 2 : nO 2 : nCH 4
number of moles escaped and ratio of mH 2 mO 2 mCH
gases is most easily liquefied? molecular mass. ⇒ VH 2 :VO 2 :VCH 4 : = : : 4
[NEET 2018] MH 2 MO 2 MCH 4
nO 2 MH 2
(a) O2 (b) H2 =
nH 2 MO 2 Given, mH 2 = mO 2 = mCH 4 = m
(c) NH3 (d) CO2
 mass 
Ans. (c) where, M = Molecular mass of the Qn =
 molar mass
In the van der Waals’ equation, molecule.
m m m then, according to ideal gas equation, Ans. (a)

Thus, VH 2 :VO 2 :VCH 4 = : :
2 32 16 pressure of both gases CO andN2 At higher temperature and low pressure
= 16 : 1 :2 becomes equal real gas acts as an ideal gas and obey pV
∴ pCO = pN 2 = nRT relation.
11 Maximum deviation from ideal gas Given, pCO + pN 2 = Total pressure of
is expected from [NEET 2013] mixture. 17 The beans are cooked earlier in
(a) H2 (g) (b) N2 (g) (c) CH4 (g) (d) NH3 (g) or 2pN 2 = 1 atm or pN 2 = 0.5 atm pressure cooker, because
Ans. (d) [CBSE AIPMT 2001]
The extent to which a real gas deviates 14 Two gases A and B having the (a) boiling point increases with
from ideal behaviour can be understood same volume diffuse through a increasing pressure
by a quantity ‘Z’ called the porous partition in 20 and 10s (b) boiling point decreases with
compressibility factor. Easily liquifiable respectively. The molecular mass increasing pressure
gases likeNH3, SO2 etc. exhibit maximum (c) extra pressure of pressure cooker,
of A is 49 u. Molecular mass of B
deviation from ideal gas as for them softens the beans
Z < < < 1. will be [CBSE AIPMT 2011]
(d) internal energy is not lost while
CH4 also exhibits deviation but it is less (a) 12.25 u (b) 6.50 u cooking in pressure cooker
as compared to NH3. (c) 25.00 u (d) 50.00 u
Ans. (b)
Ans. (a)
12 50 mL of each gas A and of gas B The beans are cooked earlier in pressure
According to Graham’s law of diffusion, cooker because boiling point decreases
takes 150 and 200 s respectively rate of diffusion with increasing pressure.
for effusing through a pin hole 1 V
r∝ ,r ∝
under the similar conditions. If M t 18 Which of the following expressions
molecular mass of gas B is 36, the where, V is the volume of the gas diffused correctly represents the
molecular mass of gas A will be in time t.
relationship between the average
[CBSE AIPMT 2012] rA MB V t MB
= or A × B = molar kinetic energy, KE of CO and
(a) 96 (b) 128 (c) 32 (d) 64 rB MA t A VB MA N 2 molecules at the same
Ans. (*)
Given, VA = VB temperature?
Given, VA = VB = 50 mL 10 MB 1 M (a) KECO < KE N 2 [CBSE AIPMT 2000]
TA = 150 s ∴ = ⇒ = B
20 49 4 49 (b) KECO > KE N 2
TB = 200 s
49 (c) KECO = KE N 2
MB = 36 MB = = 12.25 u
4
MA = ? (d) Cannot be predicted unless volumes
From Graham’s law of effusion of the gases are given
15 If a gas expands at constant Ans. (c)
rB MA VBTA MA VA × 150 temperature, it indicates that
= = ⇒ = 3
rA MB TBVA 36 200 × VA [CBSE AIPMT 2008] KE= RT (for one mole of a gas)
2
MA 15 3 M 9 (a) kinetic energy of molecules
or = = ⇒ A= decreases The temperature is constant and kinetic
36 20 4 36 16 energy is independent on molecular
(b) pressure of the gas increases
9 × 36 9 × 9 81 weights. So,
MA = = = = 20.2 (c) kinetic energy of molecules remains
16 4 4 the same KECO =KEN 2
* According to question, no option is (d) number of the molecules of gas
correct in this condition, answer any increases 19 Which one of the following
option. statements is wrong for gases?
Ans. (c)
NOTE [CBSE AIPMT 1999]
3
IfTA = 200 s andTB = 150 s then MA = 64 KE = RT (for one mole of a gas) (a) Gases do not have a definite shape
2
and volume
13 A gaseous mixture was prepared by As, the kinetic energy of a gaseous (b) Volume of the gas is equal to volume
molecule depends only on temperature, of container confining the gas
taking equal moles of CO and N 2 . If thus at constant temperature, the
the total pressure of the mixture (c) Confined gas exerts uniform
kinetic energy of the molecules remains pressure on the walls of its container
was found 1 atom, the partial the same. in all directions
pressure of the nitrogen (N 2 ) in the (d) Mass of gas cannot be determined by
mixture is [CBSE AIPMT 2011] 16 van der Waals’ real gas, act as an weighing a container in which it is
(a) 0.8 atm (b) 0.9 atm ideal gas, at which condition? enclosed
[CBSE AIPMT 2002]
(c) 1 atm (d) 0.5 atm Ans. (d)
(a) High temperature, low pressure
Ans. (d) Mass of gas can be determined by
(b) Low temperature, high pressure
Equal moles of CO andN2 weighing a container in which it is
(c) High temperature, high pressure enclosed as follows:
nCO = nN 2 (d) Low temperature, low pressure
States of Matter 47
Mass of the gas = mass of the cylinder p2V = n2 RT …(ii) Ans. (d)
including gas – mass of empty cylinder From Eqs. (i) and (ii) Root mean square velocity atT1
So, it is a wrong statement. p1V n1RT p n temperature,
= ⇒ 1 = 1
p2V n2 RT p2 n2 3RT1 3R (27 + 273)
20 At 25°C and 730 mm pressure, 380 U1 = = …(i)
n1 p1 170 M M
mL of dry oxygen was collected. If = = = 0.30
n2 p2 570 Root mean square velocity atT2
the temperature is constant, what temperature,
volume will the oxygen occupy at 23 600 cc of a gas at a pressure of 750 3RT2 3R (927 + 273)
760 mm pressure? U2 = = …(ii)
mm is compressed to 500 cc. M M
[CBSE AIPMT 1999]
Taking the temperature to remain Eq. (i) divided by Eq. (ii)
(a) 365 mL (b) 2 mL
constant,the increase in pressure U1 27 + 273
(c) 10 mL (d) 20 mL =
is [CBSE AIPMT 1995] U2 927 + 273
Ans. (a)
(a) 150 mm (b) 250 mm 300 1
As the temperature is constant, Boyle’s (c) 350 mm (d) 450 mm = =
law is applicable. 1200 2
Ans. (a)
p 1V1 = p2V2 U2 = 2 U 1
V1 = 380 mL, p1 = 730 mm ,V2 = ?, According to Boyle’s law,
p2 = 760 mm p 1V1 = p2V2 26 When is the deviation more in the
730 × 380 = 760 × V2 750 × 600 = p2 × 500 behaviour of a gas from the ideal gas
730 × 380 750 × 600 equation pV = nRT ?
V2 = = 365 mL p2 =
760 500 [CBSE AIPMT 1993]
= 900 mm (a) At high temperature and low
21 At which one of the following So, the increase in pressure pressure
temperature pressure conditions, = 900 − 750 = 150 mm (b) At low temperature and high
the deviation of a gas from ideal pressure
behaviour is expected to be 24 500 mL of nitrogen at 27°C is (c) At high temperature and high
pressure
minimum? [CBSE AIPMT 1996] cooled to –5°C at the same
(d) At low temperature and low pressure
(a) 350 K and 3 atm pressure. The new volume
Ans. (b)
(b) 550 K and 1 atm becomes [CBSE AIPMT 1995]
(a) 326.32 mL Gases show deviation from ideal gas
(c) 250 K and 4 atm
behaviour when the temperature is low
(d) 450 K and 2 atm (b) 446.66 mL
and pressure is high. At low
Ans. (b) (c) 546.32 mL temperature, the volume of one
A real gas behave as an ideal gas at low (d) 771.56 mL molecule is not negligible in comparison
pressure and high temperature. Among Ans. (b) to total volume and intermolecular force
the given option 550K temperature is the of attraction is maximum at low
Initial volume,V1 = 500 mL
highest and 1atm pressure is the lowest temperature and high pressure.
Initial temperature,
pressure.
T1 = 27 ° C = 27 + 273 = 300 K 27 The ratio among most probable
22 Cyclopropane and oxygen at partial Final temperature, velocity, mean velocity and root
pressures 170 torr and 570 torr are T2 = − 5 + 273 = 268 K mean square velocity is given by
mixed in a gas cylinder. What is the V2 = ? [CBSE AIPMT 1993]
V1 V2 (a) 1 :2 : 3 (b) 1 : 2 : 3
ratio of the number of moles of =
cyclopropane to the number of T1 T2 8 8
(c) 2 : 3 : (d) 2 : : 3
moles of oxygen? VT 500 × 268 π π
V2 = 1 2
=
[CBSE AIPMT 1996] T1 300 Ans. (d)
170 × 42 = 446.66 mL
(a) = 0.39 Most probable velocity, U mp =
2 RT
570 × 32 M
170  170 570 25 The temperature of the gas is
(b)  +  ≈0.19 Mean velocity, U av =
8RT
42  42 32  raised from 27°C to 927°C the root πM
170 mean square velocity is
(c) = 0.23 Root mean square velocity, U rms =
3RT
740 [CBSE AIPMT 1994]
M
170 927
(d) = 0.30 (a) times of the earlier value so,
570 27 2RT 8RT 3RT
U mp : U av : U rms = : :
Ans. (d) (b) same as before M πM M
According to ideal gas equation, (c) halved 8
= 2: : 3
p1V = n1RT …(i) (d) doubled π
28 Internal energy and pressure of a 31 An ideal gas cannot be liquefied 34 The root mean square speeds at
gas per unit volume are related as because [CBSE AIPMT 1992] STP for the gases H2 , N 2 ,O 2 and
[CBSE AIPMT 1993] (a) its critical temperature is always HBr are in the order
2 3 above 0°C [CBSE AIPMT 1991]
(a) p = E (b) p = E
3 2 (b) its molecules are relatively smaller in (a) H2 < N2 < O2 < HBr
1 size
(c) p = E (d) p = 2 E (b) HBr < O2 <N2 <H2
2 (c) it solidifies before becoming a liquid (c) H2 <N2 == O2 <HBr
Ans. (a) (d) forces operating between its (d) HBr <O2 <H2 <N2
molecules are negligible
The average translational kinetic energy Ans. (b)
1 Ans. (d)
of a gas molecule is mu− 2 at a The root mean square velocity of gas
2 Gases can be liquefied by lowering the molecule at STP is given by
temperature, T. The total energy of the temperature and increasing the
3RT
whole of the gas containingN molecules pressure. An ideal gas have no U rms =
is intermolecular force of attraction, so it M
1 cannot be liquefied by applying high ∴ As the molar mass of gas increases,
E k = mN u− 2 …(i) pressure and decreasing temperature.
2 then U rms will decrease, so the order of
U rms of these gases is
The kinetic gas equation is
1 32 The correct value of the gas HBr < O2 < N2 < H2
pV = mN u− 2 …(ii)
3 constant ‘ R ’ is close to
[CBSE AIPMT 1992]
35 At constant temperature, in a given
2 1
pV = × mN u− 2 mass of an ideal gas
3 2 (a) 0.082 L atm K
[CBSE AIPMT 1991]
2 (b) 0.082 L atm K −1 mol −1
pV = E k …(iii) (a) the ratio of pressure and volume
3 (c) 0.082 L atm −1 K mol −1 always remains constant
2
so, p = E k per unit volume. (d) 0.082 L −1 atm −1 K mol (b) volume always remains constant
3 Ans. (b) (c) pressure always remains constant
The numerical value of R depends upon (d) the product of pressure and volume
29 Under what conditions will a pure the units in which pressure and volume always remains constant
sample of an ideal gas not only are expressed. When pressure is Ans. (d)
exhibit a pressure of 1 atm but also expressed in atmosphere and volume in According to ideal gas equation,
a concentration of 1 mol L−1 ? litres, then the value of R at STP for pV = nRT
1 mole of gas is
(R=0.082 L atm mol–1 deg–1 ) If T is constant and mass is constant, so
1 atm × 22.414 L
(a) At STP [CBSE AIPMT 1993] R= number of moles (n) also constant
1 mole × 273.15 K  mass 
(b) When V = 22.4 L n= ,
= 0.082 L atm K–1 mol –1  molar mass
(c) WhenT = 12 K
(d) Impossible under any conditions therefore
Ans. (c) 33 Which is not true in case of an ideal pV = constant
gas? [CBSE AIPMT 1992]
According to ideal gas equation,
(a) It cannot be converted into a liquid 36 In a closed flask of 5 L, 1.0 g of H2 is
pV = nRT
n (b) There is no interaction between the heated from 300 to 600 K. Which
p = RT molecules
V statement is not correct?
(c) All molecules of the gas move with
1atm = 1mol L–1 × 0.082 × T [CBSE AIPMT 1991]
1 same speed
T= =12 K (d) At a given temperature, pV is
(a) Pressure of the gas increases
0.082 (b) The rate of collision increases
proportional to the amount of the
gas (c) The number of moles of gas
30 Select the correct statement. In increases
Ans. (c)
the gas equation pV = nRT (d) The energy of gaseous molecules
[CBSE AIPMT 1992] A gas is a collection of tiny particles increases
separated from one another by large
(a) n is the number of molecules of a gas Ans. (c)
empty space and moving rapidly at
(b) V denotes volume of one mole of the
random in all the directions. In the Here, volume is constant and mass of
gas
course of their motion, they collide with hydrogen gas is also fixed, therefore the
(c) n moles of the gas have a volume V one another and also with the walls of number of moles remains same. Now as
(d) p is the pressure of the gas when the container. Due to frequent collisions, the temperature increases, then
only one mole of the gas is present speeds and direction of motion of pressure also increases. This will lead to
Ans. (c) molecules keeps on changing. Thus, all more collisions among the gaseous
The ideal gas equation is pV = nRT the molecules in a sample of a gas do not molecules and hence, the energy of
have same speeds. molecules increases.
where, V is the volume of n moles of a gas.
States of Matter 49
37 A gas is said to behave like an ideal (c) at which ether boils pM =

w
RT Q w = d 
(d) All of the above V  V 
gas when the relation
pV Ans. (a) pM = dRT
= constant. When do you pM
T At absolute zero temperature, the ⇒ d=
entropy of substance becomes zero, it RT
expect a real gas to behave like an
means that all the molecular motions are
ideal gas? [CBSE AIPMT 1991]
stopped or ceased.
(a) When the temperature is low TOPIC 2
(b) When both the temperature and
pressure are low
40 Root mean square velocity of a gas Liquid State
(c) When both the temperature and molecule is proportional to
pressure are high [CBSE AIPMT 1990] 43 The surface tension of which of the
(d) When the temperature is high and (a) m 1/2 (b) m 0 following liquids is maximum?
pressure is low (c) m −1/2 (d) m [CBSE AIPMT 2005]
Ans. (d) Ans. (c) (a) H2O (b) C 6H6
As we know that the van der Waals’ Root mean square speed is given by the (c) CH3OH (d) C2H5OH
equation is expression Ans. (a)
 p + a  (V − b) = RT 3RT
  U rms = [Q M = mN ] Surface tension of H2O is maximum due
 V2  M to maximum hydrogen bonding in
The real gases show ideal behaviour 1 comparison to C6H6 , CH3OH, C2H5OH . The
∴ U rms ∝
when pressure approaches zero and m order of H-bonding is
temperature is high. At this condition H2O > CH3OH > C2H5OH
there is no force of attraction and ⇒ U rms ∝ (m) −1/ 2
(Benzene does not form H-bond).
repulsion between the molecules of gas.
a 41 Pressure remaining the same, the
Thus, the effect of 2 and b is negligible, 44 A liquid can exist only
V volume of a given mass of an ideal [CBSE AIPMT 1994]
i.e. gas increases for every degree (a) between triple point and critical
pV = RT centigrade rise in temperature by temperature
pV definite fraction of its volume at
=1 (b) at any temperature above the
RT [CBSE AIPMT 1989] melting point
pV
We also know = Z (for ideal gas Z = 1) (a) 0°C (c) between melting point and critical
RT temperature
(b) absolute zero
(Z is compressibility factor) (c) its critical temperature (d) between boiling and melting
Therefore an real gas behaves like ideal temperature
(d) its Boyle’s temperature
gas when the temperature is high and Ans. (d)
pressure is low. Ans. (a)
According to Charle’s law “the volume of A liquid below its melting point, is
present in solid state and above its
38 In van der Waals’ equation of state a fixed mass of a gas increases or
1 melting point, is present in vapour
for a non-ideal gas, the term that decreases by of its volume at 0°C (gaseous) state, so a liquid can exist
273.15
accounts for inter molecular forces between melting point and boiling point.
for each degree rise or fall of
is [CBSE AIPMT 1990] temperature, if pressure is kept
(a) (V − b ) (b) (RT ) −1 constant”. 45 A closed flask contains water in all
 a its three states solid, liquid and
(c)  p + 2  (d) RT
 V  42 If p, V, M, T and R are pressure, vapour at 0°C. In this situation, the
Ans. (c) volume, molar mass, temperature average kinetic energy of water
The van der Waals’ equation is and gas constant respectively, then molecules will be
 p + a  (V − b) = RT for an ideal gas, the density is given [CBSE AIPMT 1992]
 
 V2  by [CBSE AIPMT 1989] (a) the greatest in all the three states
(b) the greatest in vapour state
The term  p + 2  is used for pressure
a RT p
(a) (b)
 V  pM RT (c) the greatest in the liquid state
correction, it measures the M pM (d) the greatest in the solid state
(c) (d)
intermolecular forces between the V RT Ans. (b)
molecules of gas.
Ans. (d) In the three states of matter, the
We know that ideal gas equation is maximum kinetic energy is possessed by
39 Absolute zero is defined as the the gaseous molecules, so water vapour
temperature [CBSE AIPMT 1990] pV = nRT state has maximum kinetic energy in this
w
(a) at which all molecular motion ceases pV = RT situation.
M
(b) at which liquid helium boils
6
Solid State
TOPIC 1 06 The correct option for the number
Classification of Solid of body centred unit cells in all 14
types of Bravais lattice unit cell is
01 A pure crystalline substance on [NEET 2021]
being heated gradually first forms a (a) 7 (b) 5 (c) 2 (d) 3
turbid liquid at constant Ans. (d)
temperature and still at higher Crystal system Bravais lattice
So, axial distancesa ≠ b ≠ c and axial
temperature turbidity completely angles α = β = γ = 90 °. Cubic Primitive, body centred,
disappears. The behaviour is a face centred, end
characteristic of substance forming centred
04 The ability of a substance to
[CBSE AIPMT 1993] Orthorhombic Primitive, body centred,
assume in two or more crystalline
(a) allotropic crystals face centred, end
structure is called centred
(b) liquid crystals [CBSE AIPMT 1990]
(c) isomeric crystals Tetragonal Primitive, body centred
(a) isomerism (b) polymorphism
(d) isomorphous crystals Monoclinic Primitive, end centred
(c) isomorphism (d) amorphism
Ans. (b) Triclinic Primitive
Ans. (b)
Such type of phenomenon is only Rhombohedral Primitive
Some substances adopt different
exhibited by liquid crystals. Hexagonal Primitive
structural arrangement under different
conditions. Such arrangements are Body centred unit cell exists in three
02 Most crystals show good cleavage called polymorphs and this phenomenon systems, i.e. cubic, orthorhombic and
because their atoms, ions or is called polymorphism. tetragonal.
molecules are [CBSE AIPMT 1991]
07 An element has a body centered
(a) weakly bonded together TOPIC 2 cubic (bcc) structure with a cell
(b) strongly bonded together
(c) spherically symmetrical Unit Cell and edge of 288 pm. The atomic radius
(d) arranged in planes Packaging and Solid is [NEET (Sep.) 2020]
Ans. (d) 2 4
(a) × 288 pm (b) × 288 pm
In crystals the constituents (atoms, ions 05 Right option for the number of 4 3
or molecules) are arranged in definite tetrahedral and octahedral voids in 4 3
orderly arrangement. When these (c) × 288 pm (d) × 288 pm
hexagonal primitive unit cell are 2 4
crystals are cleaved they cut into regular [NEET 2021]
patterns. Ans. (d)
(a) 8, 4 (b) 6, 12 In bcc crystal,
03 For orthorhombic system axial (c) 2, 1 (d) 12, 6 3a 3 × 288
Q 4r = 3a; r = = pm
ratios are a ≠ b ≠ c and the axial Ans. (d) 4 4
angles are [CBSE AIPMT 1991] Number of octahedral and tetrahedral
(a) α = β = γ ≠ 90° voids are equal to N and 2N respectively,
where N is the number of atoms in unit r Corner
(b) α = β = γ = 90°
cell.
(c) α = γ = 90°,β ≠ 90°
Number of atoms per unit cell in 2r
(d) α ≠ β ≠ γ ≠ 90° hexagonal primitive unit cell = 6. a
Ans. (b) Number of tetrahedral voids r
Orthorhombic crystal has three unequal = 2N = 2 × 6 = 12.
axis which are at right angle to each Number of octahedral voids = N = 6. Body centre
other a ≠ b ≠ c, all angles = 90 °
Solid State 51
where, r = radius of atoms, On substituting the given values, we get 12 The vacant space in bcc lattice cell
a = edge length of the unit cell. d room temp. 2× M 4× M is
= [CBSE AIPMT 2015]
d 900 ° C  4r 
3
N A × (2 2r) 3 (a) 26% (b) 48%
08 A compound is formed by cation C NA ×  
 3 (c) 23% (d) 32%
and anion A. The anions form
[QGiven, M and r of iron remains Ans. (d)
hexagonal close packed (hcp) constant with temperature]
lattice and the cations occupy 75% Q Packing efficiency in bcc lattice = 68%.
2 × 3 3 16 2 r 3 ∴ Vacant space in bcc lattice
of octahedral voids.The formula of = ×
64 r 3 4 = 100 − 68 = 32%
the compound is
d bcc 3 3
[NEET (National) 2019] =
(a) C 3A2 (b) C 3A4 (c) C 4 A3 (d) C2 A3 d fcc 4 2 13 A given metal crystallises out with
Ans. (b)
a cubic structure having edge
Anions (A) form hexagonal close packed
10 The ionic radii of A + and B − ions length of 361 pm. If there are four
(hcp) lattice, so are 0.98 × 10 −10 m and 1.81 × 10 −10 m. metal atoms in one unit cell, what
Number of anions (A) = 6 The coordination number of each is the radius of one atom?
ion in AB is [CBSE AIPMT 2015]
Number of octahedral voids = Number of [NEET 2016, Phase I]
atoms in the close packed structure = 6. (a) 4 (b) 8 (a) 40 pm (b) 127 pm
(c) 2 (d) 6 (c) 80 pm (d) 108 pm
Cations (C ) occupy 75% of octahedral
75 Ans. (b)
voids, so number of cations (C ) = 6 × Ans. (d)
100
Given, ionic radius of cation (A + ) = 0.98 Given, edge length = 361 pm
= 6 × 3 /4 = 9 /2
× 10 −10 m Four metal atoms in one unit cell
∴The formula of compound = C 9 / 2 A6 i.e. effective number in unit cell (z) = 4
Ionic radius of anion (B − ) = 1.81 × 10 −10 m
= C 9 A12 = C 3A4 (given)
∴ Coordination number of each ion in AB
Thus, option (b) is correct.
=? ∴ It is a FCC structure
Now, we have ∴ Face diagonal = 4r
09 Iron exhibits bcc structure at room Radius of cation 2 a = 4r
temperature. Above 900°C , it Radius ratio =
2 × 361
Radius of anion r=
transforms to fcc structure. The 4
0.98 × 10 −10 m
ratio of density of iron at room = = 127 pm
1.81 × 10 −10 m
temperature to that at 900°C
(assuming molar mass and atomic = 0.541 14 Lithium metal crystallises in a body
radii of iron remains constant with If radius ratio range is in between 0.441 – centred cubic (bcc) crystal. If the
0.732, ion would have octahedral
temperature) is [NEET 2018] length of the side of the unit cell of
structure with coordination number ‘six’.
3 3 4 3 3 1 lithium is 351 pm, the atomic radius
(a) (b) (c) (d)
4 2 3 2 2 2 11 In calcium fluoride, having the of the lithium will be
[CBSE AIPMT 2009]
Ans. (a) fluorite structure, the coordination
Z×M numbers for calcium ion (Ca 2+ ) and (a) 240.8 pm (b) 151.8 pm
Density of unit celld =
NA × a 3 fluoride ion (F − ) are (c) 75.5 pm (d) 300.5 pm
[NEET 2016, Phase II] Ans. (b)
where, Z = Number of atoms per unit cell
(a) 4 and 2 (b) 6 and 6 In case of body centred cubic (bcc)
M = Molar mass crystal,
(c) 8 and 4 (d) 4 and 8
a 3 = Volume of unit cell [a = edge length] a 3 = 4r
Ans. (c)
NA = Avogadro’s number = 6.022 × 1023
In CaF2 (Fluorite structure), Ca2 + ions Given, edge length,a = 351 pm
3a
For bcc, Z = 2, radius (r) = are arranged in ccp arrangement (Ca2 + Hence, atomic radius of lithium,
4 ions are present at all corners and at the a 3 351 × 1.732
a=
4r centre of each face of the cube) whileF − r= =
4 4
3 ions occupy all the tetrahedral sites.
= 151.98 pm
a
For fcc, Z = 4, r = ⇒ a =2 2r
2 2
15 Copper crystallises in a face
According to question Ca2+ centred cubic (fcc) lattice with a
 ZM  F– unit cell length of 361 pm. What is
 
d room temp.  N Aa 3  bcc the radius of copper atom in pm?
= [CBSE AIPMT 2009]
d 900 ° C  ZM  From the above figure, you can clearly
  (a) 128 pm (b) 157 pm
N a3  see that coordination number ofF − is 4
 A  fcc (c) 181 pm (d) 108 pm
while that of Ca2 + is 8.
Ans. (a) a Ans. (d)

=
In case of face centred cubic (fcc) 2 2 In a face centred cubic (fcc) lattice, a
lattice, Hence, the ratio of radii unit cell is shared equally by six unit
2a 1 3 1 cells.
radius = = a: a: a
4 2 4 2 2
∴ Radius of copper atom (fcc lattice) 21 A compound formed by elements X
2 × 361 18 Which one of the following and Y crystallises in a cubic
= = 128 pm
4 statements is an incorrect? structure in which the X-atoms are
[CBSE AIPMT 2008] at the corners of a cube and the
16 Percentage of free space in body (a) The fraction of the total volume Y-atoms are at the face centres.
centred cubic (bcc) unit cell is occupied by the atoms in a primitive
[CBSE AIPMT 2008]
The formula of the compound is
cell is 0.48 [CBSE AIPMT 2004]
(a) 30% (b) 32% (c) 34% (d) 28% (b) Molecular solids are generally volatile
(a) X Y3 (b) X 3Y
Ans. (b) (c) The number of carbon atoms in an
(c) X Y (d) X Y2
unit cell of diamond is 4
In bcc unit cell, the number of atoms = 2 Ans. (a)
(d) The number of Bravais lattices in
Thus, volume of atoms in unit cell which a crystal can be categorised is In unit cell, X-atoms at the corners
4
(v) = 2 × πr 3 14 1
3 = ×8=1
Ans. (a) 8
3
For bcc structure (r) = a 4 3 1
4 Volume of atoms in a unit cell (V ) = πr Y-atoms at the face centres = × 6 = 3
3 3 2
4  3  3 a Ratio of X and Y = 1 :3.
(V ) = 2 × π a = π a3 For primitive cell, r =
3  4  8 2 Hence, formula is XY3.
3
Volume of unit cell (V ) = a 3 4 a  πa 3
V= π  =
Percentage of volume occupied by unit 3  2 6 22 Zn converts from its melted state
cell to its solid state, it has hcp
Volume of the unit cell (V ) = a 3
=
Volume of the atoms in unit cell structure, then find out the number
Thus, total volume occupied by the
Volume of unit cell
atoms
of nearest atoms.
3 [CBSE AIPMT 2001]
π a3 Volume of the atoms in unit cell
8 3 = (a) 6 (b) 8
= × 100 = π × 100 = 68% Volume of unit cell
a 3
8 (c) 12 (d) 4
πa 3 1 π Ans. (c)
Hence, the free space in bcc unit cell = × 3 = = 0.52 = 100 -0.52 = 0.48
= 100 − 68 = 32% 6 a 6
HCP is a closed packed arrangement, in
which the unit cell is hexagonal and
17 If ‘ a ’ stands for the edge length of 19 The fraction of total volume coordination number is 12.
the cubic systems : simple cubic, occupied by the atoms present in a
body centred cubic and face simple cube is [CBSE AIPMT 2007] 23 A compound formed by elements A
centred cubic, then the ratio of π π and B crystallises in the cubic
(a) (b)
radii of the spheres in these 6 3 2 structure, where A atoms are
systems will be respectively, π π present at the corners of a cube
(c) (d)
[CBSE AIPMT 2008] 4 2 4 and B atoms are present at the
1 3 1 Ans. (a) face centres. The formula of the
(a) a : a: a
2 4 2 2 For simple cube, compound is [CBSE AIPMT 2000]
1 1 a (a) A2B2 (b) AB3
(b) a : 3 a : a Radius (r) = [a = edge length]
2 2 2 (c) AB (d) A3B
3
1 3 2 4 a  Ans. (b)
(c) a : a: a Volume of the atom = π 
2 2 2 3  2 A-atoms are present at the corners of a
(d) 1a : 3 a : 2 a 4 a 
3 cube. So, the number of A-atoms per
π  1
Ans. (a)   π unit cell = 8 × = 1
∴ Packing fraction = 3 32 = 8
If a = edge length of cubic systems a 6
a Similarly, B-atoms are present at face
For simple cubic structure, radius = centres of a cube.
2 20 In a face centred cubic (fcc) lattice, So, the number of B-atoms per unit cell
For body centred cubic structure, radius a unit cell is shared equally by how 1
3 =6× =3
= a many unit cells? [CBSE AIPMT 2005] 2
4 (a) 8 (b) 4 Hence, the formula of compound is A B 3.
For face centred cubic structure, radius (c) 2 (d) 6
Solid State 53
24 The edge length of face centred Ans. (c) Ans. (a)

unit cubic cell is 508 pm. If the In fluorite structure each Ca2 + ion is Let, in the given crystalNi0.98O
radius of the cation is 110 pm, the surrounded by eightF − ions. Thus, the Ni2 + = x and Ni3+ = 0.98 − x
radius of the anion is coordination number of Ca2 + is eight. Total charge on M2 + and M3+
[CBSE AIPMT 1998] = (+2 ) x + (+3) (0.98 − x)
(a) 288 pm (b) 398 pm 28 The number of atoms contained in = 2x + 2.94 − 3x = 2.94 − x
(c) 144 pm (d) 618 pm a fcc unit cell of a monoatomic As metal oxide is neutral. Therefore,
Ans. (c) substance is [CBSE AIPMT 1993] total charge on cations = total charge on
Edge length (a) = 2 r + + 2 r −
(a) 1 (b) 2 anions.
(c) 4 (d) 6 2.94 − x = 2
a = 2(r + + r − )
Ans. (c) [Q Charge of oxygen atom = −2]
a = 508 pm
Face centred cubic is also called cubic x = 2.94 − 2 = 0.94
r + = 110 pm
508 close packed arrangement. It has So, the fraction of Ni2 + ions in the crystal
= r+ + r− points at all the corners as well as at the 0.94
2 = = 0 .96
centre of each of the six faces. 0.98
254 = 110 + r − The number of atoms present at corners
r − = 254 − 110 = 144 pm 1
per unit cell = 8 × = 1. 31 Which is the incorrect statement?
8 [NEET 2017]
25 The intermetallic compound LiAg
The number of atoms present at faces (a) FeO0.98 has non-stoichiometric metal
crystallises in cubic lattice in which 1
per unit cell = 6 × = 3 deficiency defect
both lithium and silver have 2 (b) Density decreases in case of crystals
coordination number of eight. The ∴ Total number of atoms in ccp or with Schottky’s defect
crystal class is [CBSE AIPMT 1997] fcc arrangement = 1 + 3 = 4 (c) NaCl(s) is insulator, silicon is
(a) simple cube semiconductor, silver is conductor,
(b) body centred cube quartz is piezoelectric crystal
(c) face centred cube TOPIC 3 (d) Frenkel defect is favoured in those
(d) None of the above ionic compounds in which sizes of
Density and Imperfection cation and anions are almost equal
Ans. (b) in Solid Ans. (a,d)
In body centered cubic, each atom/ion
(a) FeO0.98 has non-stoichiometric metal
has a coordination number of 8. 29 Which one of the following excess defect. It occurs due to
26 The edge length of a centred unit compounds show both, Frenkel as missing of a negative ion from its
cubic cell is 508 pm. If the radius of well as Schottky defects? lattice site, thus leaving a hole which
[NEET (Oct.) 2020] is occupied by an electron.
the cation is 100 pm, the radius of Non-stoichiometric ferrous oxide is
(a) AgBr (b) Agl
the anion is [CBSE AIPMT 1996] FeO0.93 − 0.96 and it is due to metal
(c) NaCl (d) ZnS
(a) 288 pm (b) 398 pm deficiency defect. Thus, statement
Ans. (a) (a) is incorrect.
(c) 154 pm (d) 618 pm
Ans. (c) Frenkel defect is shown by ionic (b) In an ionic crystal of A + B − type, if
substances in which there is a large equal number of cations and anions
For centred unit cell, difference in size of ions. are missing from their lattice sites,
2(r + + r − ) = a e.g., AgBr, AgI, ZnS the defect is called Schottky defect.
+
r = radii of cation Schottky defect is shown by ionic Due to such defect, density of solid
r − = radii of anion substances in which the cation and decreases. Thus, statement (b) is
correct.
2 (100 + r − ) = 508 anion are of almost similar sizes.
(c) NaCl-insulator; Silicon (Si) -
508 e.g. : AgBr, NaCl, KCl, CsCl
100 + r − = semiconductor, Silver (Ag) -
2 So, AgBr shows both, Frenkel as well as conductor; Quartz - piezoelectric
− 508 Schottky defects. crystal.
r = − 100
2 Thus, statement (c) is correct.
= 254 − 100 30 Formula of nickel oxide with metal (d) In an ionic crystal when an ion is
= 154 pm deficiency defect in its crystal is missing from its lattice site and
Ni 0.98O. The crystal contains Ni 2+ occupies interstitial site, the defect
27 In the fluorite structure, the and Ni 3+ ions. The fraction of nickel is called Frenkel’ defect. This type of
coordination number of Ca 2+ ion is existing as Ni 2+ ions in the crystal defect is seen in those crystals
[CBSE AIPMT 1993]
where the difference in the size of
is [NEET (Odisha) 2019] cations and anions is very large and
(a) 4 (b) 6 (a) 0.96 (b) 0.04 their coordination number is low.
(c) 8 (d) 3 (c) 0.50 (d) 0.31 Thus, statement (d) is incorrect.
32 Lithium has a bcc structure. Its Ans. (c) 37 The pyknometric density of sodium
density is 530 kg m − 3 and its Doping of NaCl with 10 −4 mol% of SrCl2 chloride crystal is 2.165
atomic mass is 6.94 g means, 100 moles of NaCl are doped with × 10 3 kg m–3 while its X-ray density
10 −4 mol of SrCl2 .
mol − 1 . Calculate the edge length of is 2.178 × 10 3 kg m–3 . The fraction
∴ 1 mol of NaCl is doped with
a unit cell of lithium metal. of unoccupied sites in sodium
(N A = 6.02 × 10 23 mol − 1 ) 10 −4
SrCl2 = = 10 −6 mole chloride crystal is
[NEET 2016, Phase I] 100 [CBSE AIPMT 2003]
(a) 352 pm (b) 527 pm As each Sr2 + ion introduces one cation (a) 5.96 × 10−1
(c) 264 pm (d) 154 pm vacancy. (b) 5.96 × 10−3
∴ Concentration of cation vacancies (c) 5.96
Ans. (a)
= 10 −6 mol/mol of NaCl (d) 5.96 × 10−2
Given, Li has a bcc structure.
= 10 −6 × 6023
. × 1023 mol −1
Density (ρ) = 530 kg-m −3 Ans. (b)
Atomic mass (M) = 6.94 g mol −1 = 6023
. × 10 17 mol −1 The fraction of unoccupied site in
Avogadro’s number (N A ) sodium chloride crystal
35 The appearance of colour in solid X - ray density – pyknometric density
= 6.02 × 1023 mol −1 =
alkali metal halides is generally due X - ray density
We know that, number of atoms per unit
cell in bcc (Z) = 2. to [CBSE AIPMT 2006] 2.178 × 10 3 − 2.165 × 10 3
=
∴ We have the formula for density, (a) F-centres 2.178 × 10 3
ZM (b) Schottky defect 0.013 × 10 3
ρ= =
N Aa 3 (c) Frenkel defect
2.178 × 10 3
(d) Interstitial positions
where a = edge-length of a unit cell. =
13
Ans. (a)
ZM 2178
or a = 3 F-centres are the sites where anions are
ρN A = 5 .96 × 10 −3.
missing and instead electrons are
. g mol −1
2 × 694 present and the appearance of colour in
38 The second order Bragg diffraction
=3 solid alkali metal halides is generally due
0.53 g cm−3 × 602
. × 1023 mol −1 of X-rays with λ = 1.0 Å from a set
to F-centres.
. × 10 −23 cm−3
= 3 435 of parallel planes in a metal occurs
= 3.52 × 10 −8 cm
36 CsBr crystallises in a body centred at an angle 60°. The distance
a = 352 pm
cubic lattice. The unit cell length is between the scattering planes in
436.6 pm. Given that the atomic the crystals is [CBSE AIPMT 1998]
33 The correct statement regarding mass of Cs = 133 u and that of Br = (a) 0.575 Å (b) 1.00 Å
defects in the crystalline solid is 80 u and Avogadro number being (c) 2.00 Å (d) 1.17 Å
[CBSE AIPMT 2015] 6.023 × 10 23 mol–1 , the density of Ans. (d)
(a) Schottky defects have no effect on CsBr is [CBSE AIPMT 2006] According to Bragg’s equation,
the density of crystalline solids (a) 42.5 g /cm 3 nλ = 2 d sinθ
(b) Frenkel defects decreases the (b) 0.425 g /cm 3 n=2
density of
crystalline solids (c) 8.25 g /cm 3 λ=1
(c) Frenkel defect is a dislocation defect (d) 4.25 g /cm 3 deflected angleθ = 60 °
(d) Frenkel defect is found in halides of Ans. (d) d=?
alkaline metals Z×M Distance between two plane of crystal.
Density of CsBr =
Ans. (c) a3 × N0 2 × 1 = 2 × d × sin 60 °
In Frenkel defect, ions in solids dislocate 3
Z → number of atoms in the bcc unit cell 2× 1=2×d ×
from their positions. Hence, Frenkel =2 2
defect is a dislocation defect. 2
M → molar mass of CsBr = 133 + 80 = 213 d=
a → edge length of unit cell = 436.6 pm 3
34 If NaCl is doped with 10 −4 mol % of 2
= 436.6 × 10 −10 cm = = 1.17 Å
SrCl 2 , the concentration of cation 1.7
2 × 213
vacancies will be ∴ Density =
(436.6 × 10 −10 ) 3 × 6.023 × 1023
(NA = 6.023 × 10 23 mol −1 ) 39 Schottky defect in a crystal is
[CBSE AIPMT 2007] = 8.49 × 10 −7 × 10 7 g / cm3 observed when [CBSE AIPMT 1998]
(a) 6.023 × 1015 mol−1 = 8.50 g / cm 3 (a) an ion leaves its normal site and
(b) 6.023 × 1016 mol−1 For a unit cell =
8 .50 occupies an interstitial site
(c) 6.023 × 1017 mol−1 2 (b) unequal number of cations and
(d) 6.023 × 1014 mol−1 = 4 .25 g /cm3 anions are missing from the lattice
Solid State 55
(c) density of the crystal is increased Ans. (b)

(d) equal number of cations and anions
TOPIC 4 In lithium crystal free electrons are
are missing from the lattice Electrical and Magnetic present so, Li have high thermal and
Ans. (d) Properties of Solids electrical conductivity.
Schottky defect in crystals is observed
when equal number of cations and 43 On doping Ge metal with a little
41 With which one of the following
anions are missing from the lattice. So, of In or Ga, one gets
elements silicon should be doped so
the crystal remains neutral, e.g. NaCl. [CBSE AIPMT 1993]
as to give p-type of semiconductor?
(a) p-type semiconductor
[CBSE AIPMT 2008]
40 When electrons are trapped into (b) insulator
the crystalline anion vacancy, the (a) Germanium (b) Arsenic
(c) n-type semiconductor
(c) Selenium (d) Boron (d) rectifier
defect is known as
[CBSE AIPMT 1994] Ans. (d) Ans. (a)
(a) Schottky defect p-type of semiconductor are obtained by When we add some of In or Ga (group
(b) Stoichiometric defect doping silicon or germanium with elements 13 element) into Ge (group number 14
(c) Frenkel defect of group 13 like B, Al, Ga or In so silicon is element), then electron vacancy is
doped with boron. created which is called holes. In this
(d) F-centres
type of semiconductor the charge
Ans. (d) 42 A solid with high electrical and carrier are holes (positive), so it is
When the electrons are trapped in anion thermal conductivity from the called p-type semiconductor.
vacancy, then the defect is called following is [CBSE AIPMT 1994]
F-centres. This defect is observed in
LiCl, NaCl, KCl, etc. (a) Si (b) Li (c) NaCl (d) ice
7
Solutions
TOPIC 1 Alternate Method N =
1000
= 55.5 mol Ans. (d)
18
Expression of Normality
n= 1 Weight percentage × density × 10
Concentration =
[Q 1 m solution implies that 1 mole of Equivalent weight
solute is present in 1 kg or 1000 g water] 98 × 1.8 × 10
01 Which of the following is ∴Mole fraction of solute = = 36 N
49
dependent on temperature? n 1
[NEET 2017] = = = 0.0177 N2 = 2 × 0.1 N = 0.2 N
n + N 1 + 55.5
(a) Molality N 1V1 = N2V2
(b) Molarity 03 25.3 g of sodium carbonate, 36 × V = 0.2 × 1000
(c) Mole fraction Na 2CO 3 is dissolved in enough 0.2 × 1000
(d) Weight percentage water to make 250 mL of solution. V=
36
Ans. (b) If sodium carbonate dissociates = 5.55 mL (dissociation of acid)
Molarity and normality are temperature completely, molar concentration of
dependent because they involve volume sodium ion, Na + and carbonate ion, 05 The mole fraction of the solute in
of solutions. Volume is dependent on CO 2−
temperature. 3 are respectively (Molar mass one molal aqueous solution is
of Na 2CO 3 = 106 g mol −1 ) [CBSE AIPMT 2005]
Moles of solute [CBSE AIPMT 2010]
Molarity (M) = (a) 0.027 (b) 0.036
Volume of solution (in L) (a) 0.955 M and 1.910 M (c) 0.018 (d) 0.009
(b) 1.910 M and 0.955 M Ans. (c)
Molality, mole fraction and weight
percentage does not depend on (c) 1.90 M and 1.910 M
Molality of solution = mole of solute per
temperature because they involve (d) 0.477 M and 0.477 M
kg of solvent
masses of solute and solvent. Ans. (b) So, 1 m = 1 mole of solute per 1000 g of
Molarity solvent
02 What is the mole fraction of the =
Number of moles of solute
× 1000 Hence,
solute in a 1.00 m aqueous Volume of solution (in mL) moles of solute in 1 m aqueous solution = 1
solution? 25. 3 × 1000
[CBSE AIPMT 2015] = = 0.9547 ≈ 0.955 M moles of solvent in 1 m aqueous solution
(a) 0.177 (b) 1.770 106 × 250 1000
= = 55 .55
(c) 0.0354 (d) 0.0177 Na2 CO3 in aqueous solution remains 18
Ans. (d) dissociated as Mole fraction of solute in 1 m solution
1000 × n Na2 CO3 a 2 Na+ + CO23− 1 1
Molality (m) = x 2x x = =
N×M 1 + 55.55 56.55
Since, the molarity ofNa2 CO3 is 0.955 M,
where, n = number of moles of solute = 0.0176 ≈ 0.018
the molarity of CO23− is also 0.955 M and
N = number of moles of solvent that of Na+ is 2 × 0.955 = 1.910 M
06 1 M and 2.5 L NaOH solution is
M = molar mass of solvent
04 Concentrated aqueous sulphuric mixed with another 0.5 M and 3 L
Given, m = 1
acid is 98% H2SO 4 by mass and has NaOH solution. Then, find out the
1000 × n
∴ 1= a density of 1.80 g mL−1 . Volume of molarity of resultant solution.
N × 18
acid required to make one litre of [CBSE AIPMT 2002]
n 18 0.1 M H2 SO4 solution is
⇒ = (a) 0.80 M (b) 1.0 M
N 1000 [CBSE AIPMT 2007] (c) 0.73 M (d) 0.50 M
n 18
or = = 0.0177 (a) 11.10 mL (b) 16.65 mL Ans. (c)
n + N 1018 (c) 22.20 mL (d) 5.55 mL
Moles of 2.5 L of 1M NaOH = 2 .5 × 1 = 2 .5
Solutions 57
Moles of 3.0 L of 0.5 M NaOH Q 68 g of H2O2 produce O2 at NTP = 22 .4 L =

3 2
× 280 + × 420
= 3.0 × 0.5 = 1.5 ∴ 25.5 g of H2O2 will produce 5 5
Total moles of NaOH in solution =
22.4
× 25.5 = 3 × 56 + 2 × 84
= 2 .5 + 1.5 = 40
. 68 = 168 + 168
(Total volume of solution = 8.4 L of O2 = 336 mm of Hg
= 2 .5 + 3.0 = 5 .5 L)
Thus, M1 × V1 = M2 × V2 10 Which one of the following modes 12 A mixture of N 2 and Ar gases in a
4 = M2 × 5 .5 of expressing concentration is cylinder contains 7 g of N 2 and 8 g
∴Molarity of resultant solution, independent of temperature? of Ar. If the total pressure of the
4 [CBSE AIPMT 1995, 92]
mixture of the gases in the cylinder
M2 = M
5.5 (a) Molarity (b) Molality is 27 bar, the partial pressure of N 2
≈0.73 M (c) Formality (d) Normality
is
Ans. (b) [Use atomic masses (in g mol −1 ) :
07 Molarity of liquid HCl, if density of Molality is the best method of expressing N = 14, Ar =40] [NEET (Sep.) 2020]
solution is 1.17 g/cc is concentration of solution because in
[CBSE AIPMT 2001]
(a) 12 bar (b) 15 bar
molality we take mass of solvent which is
independent of temperature, so molality (c) 18 bar (d) 9 bar
(a) 36.5 (b) 18.25
(c) 32.05 (d) 42.10 of solution is independent of Ans. (b)
temperature. From Dalton’s law of partial pressure of
Ans. (c)
gases. We know,
Density = 1.17 g /cc = 1170 g/L
pi = χ i × p
Molarity of solution =
Strength in g / L TOPIC 2 where,
Molecular weight
1170
Henry’s Law and pi = partial pressure ofith component
= M
Raoult’s Law χ i = mole-fraction of ith component
36.5
p = total pressure = 27 bar
= 32.05 M
11 The correct option for the value of (partial pressure) N 2
08 How many gram of a dibasic acid vapour pressure of a solution at = (mole-fraction) N 2 × p
nN 2
(mol. wt. 200) should be present in 45°C with benzene to octane in = ×p
100 mL of the aqueous solution to molar ratio 3 : 2 is nN 2 + nAr
give 0.1 N? [CBSE AIPMT 1999] [At 45°C vapour pressure of 7
(a) 1 g (b) 2 g benzene is 280 mm Hg and that of = 28 × 27 bar = 15 bar
(c) 10 g (d) 20 g octane is 420 mm Hg. Assume 7 8
+
Ans. (a) ideal gas]. [NEET 2021]
28 40
(a) 160 mm of Hg (b) 168 mm of Hg ∴ Partial pressure of N2 in the mixture is
Equivalent weight of dibasic acid
Molecular weight 15 bar.
= (c) 336 mm of Hg (d) 350 mm of Hg
2 Ans. (c)
200
13 The mixture which shows positive
E= = 100 n 3 deviation from Raoult’s law is
2 Molar ratio of benzene to octane, B =
nO 2 [NEET (Sep.) 2020]
Strength = 0.1 N, m = ?V = 100 mL
Mass 1000 Let nB = 3x mol, nO = 2x mol (a) Benzene + toluene
Normality (N ) = × Total number of moles (b) Acetone + chloroform
E V (L)
E NV 100 × 100 × 0.1 = nB + nO = 3x + 2x = 5x mol (c) Chlorethane + bromoethane
w= = = 1g (d) Ethanol + acetone
1000 1000 Mole fraction of benzene,
nB 3x 3 Ans. (d)
χB = = = .
09 The volume strength of 1.5 N H2O 2 nB + nO 5x 5 Let us study the nature of binary
Mole fraction of octane, solutions made of two volatile liquids:
solution is [CBSE AIPMT 1997]
nO 2x 2 (a) (Benzene + Toluene) Ideal solution,
(a) 4.8 (b) 5.2 χO = = = obeys Raoult’s law.
(c) 8.4 (d) 8.8 nB + nO 5x 5
(b) (Acetone + Chloroform) Non-ideal
Ans. (c) Vapour pressure of benzene, solution, shows negative deviation
Normality = 1.5 N pB° = 280 mm Hg from Raoult’s law.
Equivalent weight ofH2O2 = 17 (c) (Chloroethane + Bromoethane) Ideal
Vapour pressure of octane,
solution, obeys Raoult’s law.
So,, strength of the solutions, S = E × N pO° = 420 mm Hg (d) (Ethanol + Acetone) Non-ideal
=17 × 1.5 = 25.5 Total vapour pressure of solution, solution, shows positive deviation
2H2O2 → 2H2O + O2 pS = χ BpB° + χ O pO° from Raoult’s law.
= 2 × 34 = 68 g
14 The mixture that forms maximum 17 Which of the following statements 20 Which one is not equal to zero for
boiling azeotrope is about the composition of the an ideal solution?
[NEET (National) 2019] vapour over an ideal 1 : 1 molar [CBSE AIPMT 2015]
(a) ethanol + water mixture of benzene and toluene is (a) ∆H mix
(b) acetone + carbon disulphide correct? Assume that the (b) ∆S mix
(c) heptane + octane temperature is constant at 25°C. (c) ∆Vmix
(d) water + nitric acid [NEET 2016, Phase I] (d) ∆P = Pobserved − PRaoult
Ans. (d) (Given, vapour pressure data at Ans. (b)
Key Idea The binary liquid mixtures 25°C, benzene = 12.8 kPa, toluene For an ideal solution
having the same composition in liquid and = 3.85 kPa) (i) There will be no change in volume on
vapour phase and boil at constant (a) The vapour will contain a higher mixing the two components i.e.
temperature are called azeotropic percentage of toluene ∆Vmixing = 0
mixtures or azeotropes. (ii) There will be no change in enthalpy
(b) The vapour will contain equal
The solutions that show large negative amounts of benzene and toluene so ∆Hmixing = 0
deviation from Raoult’s law forms (c) Not enough information is given to So, ∆S mix ≠ 0 for an ideal solution.
maximum boiling azeotrope. For, e.g. make a prediction
nitric acid and water. 21 p A and p B are the vapour pressure
(d) The vapour will contain a higher
The remaining option containing percentage of benzene
different mixtures forms minimum of pure liquid components A and B,
boiling azeotrope.
Ans. (d) respectively of an ideal binary
Since, component having higher vapour solution. If χ A represents the mole
15 Which of the following statements pressure will have higher percentage in
fraction of component A, the total
vapour phase. Benzene has vapour
is correct regarding a solution of pressure of the solution will be
pressure 12.8 kPa which is greater than
two compounds A and B exhibiting toluene 3.85 kPa. [CBSE AIPMT 2012]
positive deviation from ideal Therefore, the vapour will contain a (a) pA + χ A (pB − pA) (b) pA + χ A (pA − pB)
behaviour? [NEET (Odisha) 2019] higher percentage of benzene. (c) pB + χ A (pB − pA) (d) pB + χ A (pA − pB)
(a) Intermolecular attractive forces Ans. (d)
between A—A and B—B are stronger 18 Which one of the following is
According to Raoult’s law, if volatile
than those between A—B. incorrect for ideal solution?
liquid added in pure solvent, then total
(b) ∆mix H = 0 at constant T and p [NEET 2016, Phase II]
pressure equal to sum of the partial
(c) ∆mix V = 0 at constant T and p (a) ∆H mix = 0 pressure of volatile liquid and solvent.
(d) Intermolecular attractive forces (b) ∆Umix = 0 Total pressure, pT = pA′ + pB′ …(i)
between A—A and B—B are equal to (c) ∆P = Pobs. − Pcalculated by Raoult’ s law = 0
those between A—B. We know that, pA′ = pA χ A
(d) ∆G mix = 0 pB′ = pBχ B
Ans. (a)
Ans. (d) Substituting the values of pA′ and pB′ in
Solution exhibits positive deviation from
Key Idea For this problem, the following Eq. (i)
ideal behaviour if the intermolecular
expression can be used. pT = pA χ A + pBχ B
interactions, i.e., A  B interactions are
more stronger than in pure components, ∆G mix = ∆Hmix −T∆S mix Mole fraction, χ A + χ B = 1 ⇒ χ B = 1 − χ A
i.e. between A  B or B  B. Thus. For an ideal gas On substituing in above equation,
option (a) is correct. The remaining ∆Hmix = 0; ∆U mix = 0; ∆S mix ≠ 0 pT = pA χ A + pB (1 − χ A )
options are valid only for ideal solutions. Putting all these values in the
= pA χ A + pB − pBχ A
expression,
16 In water saturated air the mole ∴ pT = pB + χ A (pA − pB)
∆G mix = ∆Hmix −T∆S mix
fraction of water vapour is 0.02. If
⇒ ∆G mix = 0 −T∆S mix
the total pressure of the saturated 22 A solution of acetone in ethanol
∴ ∆G mix ≠ 0 [CBSE AIPMT 2006]
air is 1.2 atm, the partial pressure
Thus, option (d) is incorrect. (a) shows a negative deviation from
of dry air is [NEET (Odisha) 2019]
Raoult’s law
(a) 1.18 atm (b) 1.76 atm 19 A gas such as carbon monoxide (b) shows a positive deviation from
(c) 1.176 atm (d) 0.98 atm would be most likely to obey the Raoult’s law
Ans. (c) ideal gas law at [CBSE AIPMT 2015] (c) behaves like a near ideal solution
Partial pressure of dry air = total (a) high temperatures and low pressures (d) obeys Raoult’s law
pressure × mole fraction of dry air (b) low temperatures and high pressures Ans. (b)
⇒ pdry air = ptotal × λ dry air (c) high temperatures and high pressures A solution of acetone in ethanol shows a
Given, λ saturated air = 0.02 (d) low temperatures and low pressures positive deviation from Raoult’s law due
λ dry air = 1 − 0.02 = 0.98 Ans. (a) to miscibility of these two liquids with
ptotal = 12. atm Real gases show ideal gas behaviour at difference of polarity and length of
∴ pdry air = 12 . atm × 0.98 = 1. 176 atm high temperatures and low pressures. hydrocarbon chain.
Solutions 59
23 A solution has 1 : 4 mole ratio of 3 2  (c) mole fraction of solute

=  × 80 + × 60  = 48 + 24 = 72 torr
pentane to hexane. The vapour 5 5  (d) mole fraction of solvent
pressure of the pure hydrocarbons Ans. (c)
at 20°C are 440 mm of Hg for 25 Formation of a solution from two According to Raoult’s law, the relative
pentane and 120 mm of Hg for components can be considered as lowering of vapour pressure is equal to
[CBSE AIPMT 2003] the mole fraction of solute, i.e.
hexane. The mole fraction of
I. pure solvent → separated p° − p
pentane in the vapour phase would = χB
solvent molecules, ∆H 1 p°
be [CBSE AIPMT 2005]
(a) 0.549 (b) 0.200 II. pure solute → separated solute χ B = mole fraction of solute
(c) 0.786 (d) 0.478 molecules, ∆H 2
Ans. (d) III. separated solvent and solute 28 The relative lowering of vapour
Total vapour pressure of mixture molecules → solution, ∆H 3 pressure is equal to the ratio
= Vapour pressure of Solution so formed will be ideal, if between the number of
pentane in mixture [CBSE AIPMT 1991]
(a) ∆H sol. = ∆H 1 − ∆H2 − ∆H 3
+ vapour pressure of hexane (a) solute molecules to the solvent
(b) ∆H sol. = ∆H 3 − ∆H 1 − ∆H2 molecules
in mixture (c) ∆H sol. = ∆H 1 + ∆H2 + ∆H 3
Since, the ratio of pentane to hexane (b) solute molecules to the total
(d) ∆H sol. = ∆H 1 + ∆H2 − ∆H 3 molecules in solution
= 1 :4
1 Ans. (c) (c) solvent molecules to the total
∴ Mole fraction of pentane = molecules in the solution
5 For an ideal solution,
4 ∆Hsol = ∆H1 + ∆H2 + ∆H3 (d) solvent molecules to the total
Mole fraction of hexane = number of ions of the solute
5
26 A solution containing components Ans. (b)
= (mole fraction of pentane × vapour
pressure of pentane) + (mole fraction of A and B follows Raoult’s law, when According to Raoult’s law the relative
hexane × vapour pressure of hexane) [CBSE AIPMT 2002] lowering of vapour pressure is equal to
mole fraction of solute, i.e. the ratio of
=  × 440 + × 120  = 184 mm
1 4 (a) A - B attraction force is greater than
5 5  A - A and B - B number of moles of solute to total
number of moles of all component in
Q Vapour pressure of pentane in mixture (b) A - B attraction force is less than A - A
solution.
and B - B
= Vapour pressure of mixture × mole
fraction of pentane in vapour phase (c) A - B attraction force remains same
as A - A and B - B 29 All form ideal solution except
88 = 184 × mole fraction of pentane in [CBSE AIPMT 1988]
(d) volume of solution is different from
vapour phase (a) C 6H6 and C 6H5CH3
sum of volumes of solute and
∴Mole fraction of pentane in vapour phase solvent (b) C2H5Cl and C2H5I
88
= = 0.478 Ans. (c) (c) C 6H5Cl and C 6H5Br
184
Raoult’s law is valid for ideal solution (d) C2H5I and C2H5OH
only. The two components A and B Ans. (d)
24 The vapour pressure of two liquids
follows the condition of Raoult’s law only
P and Q are 80 and 60 torr, when the force of attraction between A
When we mix C2H5I and C2H5OH, there is
respectively. The total vapour change in enthalpy and volume, so it is
and B is equal to the force of attraction
an example of non-ideal solution.
pressure of solution obtained by between A – A and B – B.
mixing 3 moles of P and 2 moles of While non-ideal solutions exhibit either
30 An ideal solution is formed when its
Q would be [CBSE AIPMT 2005] positive or negative deviations from
Raoult’s law. When A – B attraction force components [CBSE AIPMT 1988]
(a) 140 torr (b) 20 torr (a) have no volume change on mixing
is greater than A – A and B – B, then
(c) 68 torr (d) 72 torr
solution shows negative deviation and (b) have no enthalpy change on mixing
Ans. (d) when A–B attraction force is less than (c) have both the above characteristics
3 3 A–A and B–B, the solution shows positive (d) have high solubility
Mole fraction of P = =
3+2 5 deviation.
Ans. (c)
2 2
Mole fraction of Q = = 27 According to Raoult’s law, relative In ideal solution there is no change in
3+2 5 enthalpy and volume after mixing, i.e.
lowering of vapour pressure of a
Hence, total vapour pressure ∆Vmixing = 0,
solution is equal to [CBSE AIPMT 1995]
= Mole fraction of ∆Hmixing = 0
(a) moles of solute
P × vapour pressure of P + mole fraction and Tmix = 0
(b) moles of solvent
of Q × vapour pressure of Q
TOPIC 3 33 If 8 g of a non-electrolyte solute is Ans. (d)
Colligative Properties dissolved in 114 g of n-octane to From Raoult’s law of partial pressure,
reduce its vapour pressure to 80%, pA° − pS nB
=
the molar mass (in g mol −1 ) of the pS nA
31 The following solutions were
solute is [Given that, molar mass of 760 − 732 WB × MA
prepared by dissolving 10 g of ⇒ =
n-octane is 114 g mol −1 ] 732 MB × WA
glucose (C 6H12O 6 ) in [NEET (Oct.) 2020]
250 mL of water (p 1 ), 10 g of urea 28 6.5 × 18
(a) 40 (b) 60 (c) 80 (d) 20 ⇒ =
(CH4N 2O) in 250 mL of water (p 2 ) 732 MB × 100
Ans. (*)
and 10 g of sucrose ⇒ MB = 30.6
Does not match with the options.
(C 12H22O 11 ) in 250 mL of water (p 3 ). 6.5 × 1000
Here, relative lowering of given vapour ∴ ∆Tb = 0.52 × = 1.10
The right option for the decreasing 30.6 × 100
pressure,
order of osmotic pressure of these ∆p p° − p° × 0.8 ∴ Boiling point = 100 + 1.10 = 101.1°C
solutions is = = 0.2
[NEET 2021] p° p° ≈ 101° C
(a) p2 > p1> p3 (b) p1 > p2 > p3 wB
(c) p2 > p3 > p1 (d) p3 > p1 > p2 ∆p nB MB 36 An aqueous solution is 1.00 molal in
Now, = xB = = KI. Which change will cause the
Ans. (a) p° nB + nA w B + w A
MB MA vapour pressure of the solution to
van’t Hoff factor for glucose, urea and
sucrose is one as all are non-ionic.
increase? [CBSE AIPMT 2010]
p° = vapour pressure of pure solvent
Mass of glucose = 10 g (a) Addition of NaCl
(octane)
(b) Addition of Na2 SO 4
Molar mass of glucose = 180 g mol −1 Mass of solute (w B) = 8 g
(c) Addition of 1.00 molal KI
Number of moles of glucose Mass of solvent (w A ) = 114g
10 1 (d) Addition of water
= = mol = 0.056 mol Molar mass of solute (MB) = ?
180 18 Ans. (d)
Molar mass of solvent (octane) (MA )
Mass of urea = 10 g Key Idea Vapour pressure depends upon
= 114g mol − 1.
Molar mass of urea = 60 g mol −1 8 / MB
the surface area of the solution. Larger
10 1 ⇒ 0.2 = ⇒ MB = 32g mol − 1 the surface area, higher is the vapour
Number of moles of urea = = mol 8
+
114 pressure.
60 6 MB 114
= 0.167 mol Addition of solute decreases the vapour
pressure as some sites of the surface
Mass of sucrose = 10 g
34 If molality of the dilute solution is are occupied by solute particles,
Molar mass of sucrose = 342 g mol −1 resulting in decreased surface area.
doubled, the value of molal
Number of moles of sucrose However, addition of solvent, i.e.
10 depression constant (K f ) will be dilution, increases the surface area of
= = 0.029 mol [NEET 2017]
342 the liquid surface, thus results in
(a) doubled (b) halved increased vapour pressure.
Osmotic pressure is a colligative
property which depends on the amount (c) tripled (d) unchanged Hence, addition of water to the aqueous
of solute present in the solution. As the Ans. (d) solution of (1 molal) KI, results in
amount of urea is more than that of increased vapour pressure.
For a dilute solution, the depression in
glucose and sucrose. freezing point (∆Tf ) is directly
Amount of solute : Urea > Glucose > proportional to molality (m) of the 37 A solution of sucrose (molar mass
Sucrose solution. = 342 g mol −1 ) has been prepared
∴Osmotic pressure, p2 > p1 > p3 ∆Tf ∝ m or ∆Tf = K f m by dissolving 68.5 g of sucrose in
Where,K f is called molal depression 1000 g of water. The freezing point
32 Isotonic solutions have same constant or freezing point depression of the solution obtained will be
[NEET (Oct.) 2020] constant or cryoscopic constant. The (k f for water = 1.86 K kg mol −1 )
(a) vapour pressure value of K f depends only on nature of the [CBSE AIPMT 2010]
(b) freezing temperature solvent and independent of composition
of solute particles, i.e. does not depend (a) − 0.372 °C (b) − 0.520°C
(c) osmotic pressure
on the concentration of solution. (c) + 0.372 °C (d) − 0.570°C
(d) boiling temperature Ans. (a)
Ans. (c) 35 At 100°C the vapour pressure of a Depression in freezing point,
Isotonic solutions have same osmotic solution of 6.5 g of a solute in 100 g ∆Tf = kf × m
pressure ( π) at a given temperature. water is 732 mm. If K b = 0.52, the W × 1000
where, m = molality = B
π = CRT boiling point of this solution will be MB ⋅ WA
When, two solution have same molar [NEET 2016, Phase I]
68.5 × 1000 68. 5
concentration (C) their osmotic pressure (a) 100°C (b) 102°C = =
will be equal. 342 × 1000 342
(c) 103°C (d) 101°C
Solutions 61
68.5 40 1.00 g of a non-electrolyte solute 42 A solution contains non-volatile

∆Tf = 1.86 × = 0.372 °C
342 (molar mass 250 g mol–1 ) was solute of molecular mass, M 2 .
Tf = TF − ∆TF
0
dissolved in 51.2 g of benzene. If Which of the following can be used
= 0 − 0.372° C
the freezing point depression to calculate the molecular mass of
= − 0.372° C
constant, k f of benzene is 5.12 K kg solute in terms of osmotic
38 A solution containing 10 g per dm 3 mol–1 , the freezing point of pressure? [CBSE AIPMT 2002]
benzene will be lowered by m   m  RT
of urea (molecular mass = 60 g (a) M2 =  2  VRT (b) M2 =  2 
mol–1 ) is isotonic with a 5% solution
[CBSE AIPMT 2006]
π  V  π
(a) 0.4 K (b) 0.3 K  m2  m  π
of a non-volatile solute. The (c) 0.5 K (d) 0.2 K (c) M2 =   πRT (d) M2 =  2 
molecular mass of this non-volatile  
V  V  RT
Ans. (a)
solute is [CBSE AIPMT 2006] Ans. (b)
Molality of non-electrolyte solute
(a) 250 g mol–1 (b) 300 g mol–1 Weight of solute in (g) For dilute solution,
(c) 350 g mol–1 (d) 200 g mol–1 molecular weight of solute pV = nRT (p = π, osmotic pressure)
= n
Ans. (b) Weight of solvent in (kg) or πV = nRT or π = RT
10 g per dm 3 of urea is isotonic with 5% 1 V
solution of a non-volatile solute. Hence, m m RT
= 250 ⇒ πV = 2 RT ⇒ M2 = 2
between these solutions osmosis is not 0.0512 M2 πV
possible, so their molar concentrations
=
1
= 0.0781 m where, π =osmotic pressure
are equal to each other.
250 × 0.0512 V = volume of solution
Thus, molar concentration of urea
solution ∆Tf = kf × molality of solution n = number of moles of solute
10 g / dm3 = 5.12 × 0.0781 ≈ 0.4 K m2 =mass of solute
= M2 = molecular mass of solute
Molecular weight of urea
10 1 41 A solution of urea (mol. mass 56 g
= M= M mol–1 ) boils at 100.18°C at the 43 Pure water can be obtained from
60 6
Molar concentration of 5% non-volatile atmospheric pressure. If k f and k b sea water by [CBSE AIPMT 2001]
solute for water are 1.86 and 0.512 K kg (a) centrifugation (b) plasmolysis
50 g / dm3 mol–1 respectively, the above (c) reverse osmosis (d) sedimentation
=
Molecular weight of non − solution will freeze at Ans. (c)
[CBSE AIPMT 2005] Reverse osmosis The minimum
volatile solute
(a) –6.54°C (b) 6.54°C external pressure applied to a solution
50
= M (c) 0.654°C (d) –0.654°C separated from a solvent by
m semipermeable membrane to prevent
Ans. (d)
Both solutions are isotonic to each osmosis, is called osmotic pressure.
other, therefore According to depression of freezing When the pressure applied to solution is
1 50 point, more than osmotic pressure, solute will
= ∆Tf = kf × molality of solution
6 m pass from the solution into solvent
According to elevation of boiling point, through the semipermeable membrane.
or m = 50 × 6 = 300 g mol −1
∆Tb = kb × molality of solution This phenomenon is known as reverse
osmosis.
39 During osmosis, flow of water ∆Tf k
or = f The osmotic pressure of sea water is 25
through a semipermeable ∆Tb kb
atm at 15°C. When pressure greater than
membrane is [CBSE AIPMT 2006] Given that 26 atm is applied on sea water separated
(a) from solution having higher ∆Tb = T2 − T1 = 100.18 − 100 = 0.18 by a rigid semipermeable membrane,
concentration only kb for water = 1.86 K kg mol –1 pure water is obtained. This is also called
(b) from both sides of semipermeable desalination of sea water.
kb for water = 0.512 K kg mol –1
membrane with equal flow rates
∆Tf 1.86
(c) from both sides of semipermeable ∴ = 44 Which of the following colligative
membrane with unequal flow rates 0.18 0.512
property can provide molar mass of
1.86 × 0.18
(d) from solution having lower ∆Tf = = 0.6539 ≈ 0.654 proteins (or polymers or colloids)
concentration only 0.512
with greatest precision?
Ans. (d) ∆Tf = T1 − T2 [CBSE AIPMT 2000]
During osmosis, flow of water through a 0.654 = 0 ° C − T2 (a) Osmotic pressure
semipermeable membrane is from ∴ T2 = − 0.654° C (b) Elevation in boiling point
solution having lower concentration (T2 → freezing point of aqueous urea (c) Depression in freezing point
only. solution) (d) Relative lowering of vapour pressure
Ans. (a) Ans. (c) Ans. (c)

Osmotic pressure is a colligative Isotonic solutions are the solutions We know that, according to Raoult’s law
property which is used to find the having same osmotic pressure. p° − p
= χB
molecular weight of polymer because Osmotic pressure of 5% cane sugar p°
other colligative properties give so low solution p° − 60 nB 0.2
value of molecular weight that it cannot 50 g / L = =
be measured accurately. ( π 1) = C × R × T = × 0.0821 × T p° nA + nB 0.2 + 0.8
342
0.2 2 1
Osmotic pressure of 1% solution of = = =
45 The vapour pressure of benzene at 1.0 10 5
substance p°
a certain temperature is 640 10 g / L p° − 60 =
X ( π2 ) = × 0.0821 × T 5
mmHg. A non-volatile and M p°
non-electrolyte solid, weighing Both are isotonic ⇒ p° − = 60
5
2.175 g is added to 39.08 g of So, π 1 = π2 5p° − p°
50 10 = 60
benzene. If the vapour pressure of or × 0.0821 × T = × 0.0821 × T 5
the solution is 600 mm Hg, what is 342 M
4p° = 60 × 5
342
the molecular weight of solid ∴ M (molecular weight of X) = = 68.4 60 × 5 300
5 p° = = = 75 mm of Hg
substance? [CBSE AIPMT 1999] 4 4
(a) 49.50 (b) 59.60 (c) 69.40 (d) 79.82
48 The vapour pressure of a solvent
Ans. (c) decreased by 10 mm in two 50 Vapour pressure of benzene at
According to Raoult’s law, columns of mercury when a 30°C is 121.8 mm. When 15 g of a
p° − p w × M non-volatile solute was added to non-volatile solute is dissolved in
=
p° m× W the solvent. The mole fraction of 250 g of benzene its vapour
640 − 600 2 .175 × 78 the solute in the solution is 0.2. pressure decreased to 120.2 mm.
=
640 m × 3908
. What should be the mole fraction The molecular weight of the solute
(M for C6H6 = 78) of the solvent if the decrease in the is (mol. weight of solvent = 78)
[CBSE AIPMT 1995]
2 .175 × 78 × 640 vapour pressure is to be 20 mm of
m= (a) 356.2 (b) 456.8 (c) 530.1 (d) 656.7
40 × 3908
. mercury [CBSE AIPMT 1998]
(a) 0.8 (b) 0.6 (c) 0.4 (d) 0.2 Ans. (a)
= 6945
. ≈ 694
.
Ans. (b) Given, vapour pressure of pure benzene
( p° ) = 121.8 mm
46 If 0.15 g of solute, dissolved in 15 g According to Raoult’s law, the relative
Vapour pressure of solution
of solvent, is boiled at a lowering of vapour pressure is equal to
(p) = 120.2 mm
the mole fraction of solute, i.e.
temperature higher by 0.216°C, p° − p n ∆p n Mass of solute (w B) = 15 g
than that of the pure solvent, the = or =
p° n+ N p° n + N Mass of benzene (w A ) = 250g
molecular weight of the substance 10 Molar mass of solvent (mA ) = 78
is (molal elevation constant for the = 0.2 ⇒ p° = 50 mm
p° Molecular weight of solute (mB) = ?
solvent is 2.16°C) Hence, according to Raoult’s law,
For other solution of same solvent
[CBSE AIPMT 1999] p° − p w B × mA
20 n 20 n =
(a) 1.01 (b) 10 = or = p° mB × w A
p° n + N 50 n + N
(c) 10.1 (d) 100
n p° = vapour pressure of solvent
Ans. (d) 0.4 = (mole fraction of solute)
n+ N p = vapour pressure of the solution
w = 0.15 g, W = 15 g,
Q Mole fraction of solvent + mole fraction 121.8 − 120.2 15 × 78
∆Tb = 0.216° C kb = 2 .16, m = ? =
of solute = 1 121.8 mB × 250
1000 × kb w
m= × So, mole fraction of solvent = 1 − 0.4 = 0.6 121.8 × 15 × 78
∆Tb W mB =
250 × (121.8 − 120.2)
1000 × 2 .16 × 0.15 49 The vapour pressure, at a given
= = 100 142506 142506
0.216 × 15 temperature, of an ideal solution = = = 356.26 g mol −1
250 × 1.6 400
containing 0.2 mole of a
47 A 5% solution of cane sugar (mol. non-volatile solute and 0.8 mole of
wt. = 342) is isotonic with 1% 51 Which one is a colligative property?
solvent is 60 mm of Hg. The vapour [CBSE AIPMT 1992]
solution of a substance X. The pressure of the pure solvent at the
(a) Boiling point
molecular weight of X is same temperature is
[CBSE AIPMT 1998] (b) Vapour pressure
[CBSE AIPMT 1996]
(a) 34.2 (b) 171.2 (c) Osmotic pressure
(a) 150 mm of Hg (b) 60 mm of Hg
(c) 68.4 (d) 136.8 (d) Freezing point
(c) 75 mm of Hg (d) 120 mm of Hg
Solutions 63
Ans. (c) to the molal concentration of the (b) C6H12O6 s no ions [i = 0]

Osmotic pressure is an example of solution i.e. because glucose does not gives ions.
colligative property because its value ∆Tb ∝ m or ∆Tb = K b m (c) Al2 (SO4 ) 3 (aq)
s 2Al 3+ + 3SO24−
depends only on the number of moles of where, m is the molality of the solution [Total ions = 5, thus,i = 5 ]
solute, not on their chemical nature. and K b is molal boiling point constant or (d) K2SO4 (aq) s 2K+ + SO24−
ebullioscopic constant.
52 Blood cells retain their normal [Total ions = 3, thus, i = 3 ]
∴ By elevation in boiling point relation
shape in solutions which are Hence, Al2 (SO4 ) 3 will exhibit largest
∆Tb = iK b m or ∆Tb ∝ i freezing point depression due to the
[CBSE AIPMT 1991]
where,i is van’t Hoff factor highest value ofi.
(a) hypotonic to blood
Since, ∆Tb of solution X is greater than
(b) isotonic to blood
∆Tb of solution Y. 57 The van’t Hoff factor, i for a
(c) hypertonic to blood
(Observed colligative property is greater compound which undergoes
(d) equinormal to blood than normal colligative property). dissociation in one solvent and
Ans. (b) ∴ i of solution X > i of solution Y association in other solvent is
When blood cells are placed in a solution ∴ Solution X undergoing dissociation respectively. [CBSE AIPMT 2011]
of similar concentration as that of blood,
(a) less than one and less than one
then they neither swell nor shrink it
55 Which one of the following (b) greater than one and less than one
means the concentration of solution is
same as that of inside the blood cells, electrolytes has the same value of (c) greater than one and greater than one
i.e. they are isotonic to each other. van't Hoff's factor (i) as that of (d) less than one and greater than one
Al 2 (SO 4 ) 3 (if all are 100% ionised)? Ans. (b)
[CBSE AIPMT 2015]
TOPIC 4 (a) K2 SO 4 (b) K 3 [Fe(CN) 6]
Abnormality present due to dissociation
and association of the solution.
Abnormal Molecular Masses (c) AI (NO 3) 3 (d) K 4 [Fe(CN) 6] For dissociation, van’t Hoff factor is
and Distribution Law Ans. (d) greater than one and for association,
Al2 (SO4 ) 3a 2 Al 3+ + 3 SO24− van’t Hoff factor is less than one.
53 The van’t Hoff factor (i) for a dilute Value of van’t Hoff’s factor (i) = 5 For dissociation, i > 1
aqueous solution of the strong (a) K2SO4 a 2K+ + SO24− (i = 3) For association, i < 1
electrolyte barium hydroxide is (b) K3 [Fe(CN) 6 ]
a 3 K+ + [Fe(CN) 6 ] 3−
(i = 4)
58 The freezing point depression
(a) 0 (b) 1 (c) 2 (d) 3 (c) Al(NO3) 3 a Al 3+ + 3 NO−3
constant for water is – 1.86°C m −1 .
Ans. (d) (i = 4) If 5.00 g Na 2 SO4 is dissolved in
Key Idea Strong electrolytes dissociate (d) K4 [Fe(CN) 6 ]
a 4 K+ + [Fe(CN) 6 ] 3− 45.0 g H2O, the freezing point
completely in their solutions. (i = 5) is changed by – 3.82°C. Calculate
van’t Hoff factor = total number of ions Therefore, K4 [Fe(CN) 6 ] has same value the van’t Hoff factor for Na 2 SO4 .
after dissociation of i that ofAl2 (SO4 ) 3 i.e. i = 5. [CBSE AIPMT 2011]
So for Ba(OH)2 q Ba2 + (aq ) + 2OH− (aq) (a) 2.63 (b) 3.11 (c) 0.381 (d) 2.05
Number of ions 1 2 56 Of the following 0.10 m aqueous Ans. (a)
van’t Hoff factor, i = 1 + 2 = 3 solutions, which one will exhibit the According to depression in freezing point,
largest freezing point depression? ∆Tf = i × kf ⋅ m
−1
54 The boiling point of 0.2 mol kg [CBSE AIPMT 2014]
where, kf = cryoscopic constant
solution of X in water is greater (a) KCl (b) C 6 H 12O 6
∆Tf × Wsolvent
than equimolal solution of Y in (c) Al2 (SO 4 ) 3 (d) K2 SO 4 or i =
kf × nsolute × 1000
water. Which one of the following Ans. (c)
3.82 × 45
statements is true in this case? ∆Tf (freezing point depression) is a = = 2.63
 5 
[CBSE AIPMT 2015] colligative property and depends upon 1.86 ×   × 1000
(a) X is undergoing dissociation in water. the van’t Hoff factor (i), i.e. number of  142 
(b) Molecular mass of X is greater than ions given by the electrolyte in aqueous
the molecular mass ofY. solution. 59 A 0.0020 m aqueous solution of an
(c) Molecular mass of X is less than the ∆Tf = i × kf × m ionic compound Co(NH3 ) 5 (NO 2 )Cl
molecular mass of Y. where, kf = molal freezing point
(d) Y is undergoing dissociation in water depression constant freezes at – 0.00732°C. Number of
while X undergoes no change. m = molality of the solution moles of ions which 1 mole of ionic
Ans. (a) ∴ kf and m are constant, compound produces on being
∴ ∆Tf ∝ i dissolved in water will be
Molality of solution X = molality of
solution Y = 0 .2 mol/kg van’t Hoff factor for ionic solution. (k f = − 1.86° C / m)
We know that, elevation in the boiling (a) KCl (aq) s K+ (aq) + Cl − (aq), [CBSE AIPMT 2009]
point (∆Tb ) of a solution is proportional (Total ions =2 thus, i = 2) (a) 2 (b) 3 (c) 4 (d) 1
Ans. (a) 61 Which of the following 0.10 M (a) Al2 (SO 4 ) 3

Given, molality, m = 0.0020 m aqueous solution will have the (b) NaCl
∆Tf = 0 ° C − 0.00732° C lowest freezing point? (c) Al(NO 3) 3
= − 0.00732° C [CBSE AIPMT 1997] (d) Na2 SO 4
kf = − 1.86° C / m (a) Al2 (SO 4 ) 3 (b) C 5H10O 5 Ans. (a)
∆Tf = i ⋅ kf × m (c) KI (d) C 12H22O 11 Both K4 [Fe(CN) 6 ] and Al2 (SO4 ) 3 gives 5
∆Tf Ans. (a) ions after dissociation, so they have
i= same value of van’t Hoff factor (i).
kf × m Depression in freezing point ∝ number of
K4 [Fe(CN) 6 ] → 4K+ + [Fe(CN) 6 ] 4–
0.00732 particles.
= Al2 (SO4 ) 3 → 2Al 3+ + 3SO24–
1.86 × 0.0020 In colligative properties ions behave like
= 1.96 ≈ 2 particles.
Al2 (SO4 ) 3 provides five ions on ionisation 64 In a pair of immiscible liquids, a
Since, the compound is ionic, so number
as common solute dissolves in both
of moles produced is equal to van’t Hoff
factor, i. Al2 (SO4 ) 3 → 2 Al 3+ + 3SO24– and the equilibrium is reached.
Hence, 2 moles of ions are produced. KI º K + + I– Then, the concentration of the
[Co(NH3) 5 NO2 ]Cl → while KI provides two ions and C5 H10O5 solute in upper layer is
1 mol and C12H22O11 are not ionised, so they [CBSE AIPMT 1994]
[Co(NH3) 5 NO2 ] + + Cl – have single particle (a) in fixed ratio with that in the lower
1444 424444 3
2 ions Hence, lowest freezing point is possible layer
for Al2 (SO4 ) 3. (b) same as the lower layer
60 0.5 molal aqueous solution of a
(c) lower than the lower layer
weak acid (HX) is 20% ionised. If k f 62 At 25°C, the highest osmotic (c) higher than the lower layer
for water is 1.86K kg mol −1 , the pressure is exhibited by 0.1 M Ans. (a)
lowering in freezing point of the solution of [CBSE AIPMT 1994] According to Nernst distribution law
when we mixed a common solute in a
(a) CaCl2 (b) KCl
(a) –1.12 K (b) 0.56 K (c) glucose (d) urea pair of immiscible liquids, then the ratio
(c) 1.12 K (d) – 0.56 K of amount of solute in both liquids is
Ans. (a)
Ans. (c) fixed at a fixed temperature.
+
CaCl2 is an electrolyte and dissociates to
HX ºH + X− give three ions as
Weak acid 65 Which of the following aqueous
CaCl2 → Ca2 + + 2Cl −
1 0 0 (initially) solutions has minimum freezing
While KCl gives two ions and glucose and
1−α α α (at equilibrium) point? [CBSE AIPMT 1991]
urea are non-electrolytes, so remains
Total = 1 − α + α + α = 1 + α undissociated. (a) 0.01 m NaCl
1+ α (b) 0.005 m MgI2
i= As osmotic pressure is a colligative
1 property (i.e. depend only on number of (c) 0.005 m C2H5OH
α = 20%dissociation particles), so highest for CaCl2 . (d) 0.005 m MgSO 4
i.e. α = 0.2 Ans. (a)
i = 1 + α = 1 + 0.2 = 1.2 63 Which one of the following salts 0.01 molal NaCl solution have minimum
∆Tf = i × K f × m will have the same value of van’t freezing point because its molality is
= 1.2 × 1.86 K kg mol –1 × 0.5 Hoff factor (i) as that of more and it gives two ions after
= 1.12 K K 4 [Fe(CN) 6] ? [CBSE AIPMT 1994] dissociation of one molecule.
8
Chemical Equilibrium
TOPIC 1 Ans. (a) Ans. (a)
The Chemical Equilibrium, The equilibrium constant at two Plan As we can see the reaction for
different temperatures for a which we have to find out equilibrium
Basic Law of Mass Action thermodynamic process is given by constant is different only in
and Equilibrium Constant K ∆H °  1 1 stoichiometric coefficient as compared
log 2 =  −  to the given reaction. Hence, we can
K 1 2.303R T1 T2 
find equilibrium constant for the
01 A 20 litre container at 400 K
Here,K 1 and K 2 are replaced byK p andK ′p . required reaction with the help of
contains CO 2 (g) at pressure 0.4 atm mentioned equilibrium constant in the
K′ ∆H °  1 1
and an excess of SrO (neglect the Therefore, log p =  −  problem.
K p 2.303R T1 T2 
volume of solid SrO). The volume of Given, equilibrium constant for the
the container is now decreased by For exothermic reaction, reaction,
moving the movable piston fitted in T2 > T1 and H = −ve N22 ( g ) + O2 (g ) - 2NO(g ) is K
the container. The maximum ⇒ K p > K ′p [NO]2
i.e. K= …(i)
volume of the container, when [N2 ][O2 ]
pressure of CO 2 attains its 03 If the value of an equilibrium
Let equilibrium constant for the
maximum value, will be [NEET 2017] constant for a particular reaction is reaction,
(Given that : 1.6 × 10 12 , then at equilibrium the 1 1
system will contain N2 (g ) + O2 (g ) - NO(g ) is K ′
SrCO 3 (s) q SrO(s) + CO 2 (g), 2 2
(a) all reactants [CBSE AIPMT 2015] [NO]
K p = 1.6 atm) (b) mostly reactants
i.e. K ′ =
[N2 ] 1/2 [O2 ] 1/2
(a) 5 L (b) 10 L (c) 4 L (d) 2 L (c) mostly products
Ans. (a) (d) similar amounts of reactants and On squaring both sides
For the reaction, products [NO]2
K ′2 = …(ii)
SrCO3 (s ) q S rO(s ) + CO2 (q), Ans. (c) [N2 ][O2 ]
K p = 16
. atm = pCO 2 = maximum For a reaction, On comparing Eqs. (i) and (ii), we get
pressure of CO2
A eB K = K ′2
Given, p1 = 0.4 atm, V1 = 20 L,T1 = 400 K Reactant Product or K′= K
p2 = 16. atm, V2 = ?,T2 = 400 K [B] eq
K=
At constant temperature, p1V1 = p2V2 [A] eq 05 Using the Gibbs energy change,
0.4 × 20 = 16
. × V2 ∆G° = + 63.3 kJ for the following
[B] eq
0.4 × 20 1.6 × 10 12 =
V2 = = 5L [A] eq reaction,
.
16
∴ [B] eq >> [A] eq
Ag 2 CO 3 (s) 2Ag + (aq )
r
02 For a given exothermic reaction, So, mostly the product will be present in + CO 23− (aq)
K p and Kp′ are the equilibrium the equilibrium mixture. the K sp of Ag 2 CO 3 (s) in water at
constants at temperaturesT 1 and 25°C is
T 2 , respectively. Assuming that 04 If the equilibrium constant for
(R = 8.314 JK −1mol −1 )
heat of reaction is constant in N 2 (g ) + O 2 (g )a 2NO(g ) is K, the [CBSE AIPMT 2014]
temperature range betweenT 1 and equilibrium constant for (a) 3.2 × 10−26 (b) 8.0 × 10−12
T 2 , it is readily observed that 1 1
N 2 (g )+ O 2 (g )a NO(g ) will be, (c) 2.9 × 10−3 (d) 7.9 × 10−2
[CBSE AIPMT 2014] 2 2 Ans. (b)
[CBSE AIPMT 2015]
(a) K p > K ′p (b) K p < K ′p
1 1 ∆G ° is related toK sp by the equation,
(c) K p = K ′p (d) K p = (a) K 1/2 (b) K (c) K (d) K 2
K′p 2 ∆G ° = −2.303RT log K sp
Given, ∆G ° = + 63.3 kJ where, [∆ng gaseous = np − nR ] By dividing eq. (ii) by (i) we get
= 63.3 × 10 3 J (a) nP = nR = 2, thus, K p = K C 1
×x=1
Thus, substitute ∆G ° = 63.3 × 10 3 J, (b) nP = nR = 2, thus, K p = K C 64
R = 8.314 JK−1 mol −1 andT = 298K [25 + ⇒ x = 64 times
(c) nP = nR = 2, thus, K p = K C
273 K] from the above equation we get,
(d) nP = 2, nR = 1, thus, K p ≠ K C 10 The value of equilibrium constant
63.3 × 10 3 = − 2.303 × 8.314 × 298 log K sp
∴ log K sp = − 11.09 of the reaction,
08 The dissociation constants for
⇒ K sp = antilog (− 11.09) 1 1
acetic acid and HCN at 25°C are HI(g) r H2 (g) + I 2 (g) is 8.0.
K sp = 8.0 × 10 −12 1. 5 × 10 −5 and 4.5 × 10 −10 , 2 2
respectively. The equilibrium The equilibrium constant of the
06 For the reaction, reaction,
constant for the equilibrium,
N 2 (g) + O 2 (g) r 2NO(g), the H2 ( g ) + I 2 (g ) r2HI(g) will be
CN– + CH3COOH HCNr
equilibrium constant is K 1 . The [CBSE AIPMT 2008]
equilibrium constant is + CH3COO– would be 1 1 1
[CBSE AIPMT 2009] (a) (b) (c) 16 (d)
K 2 for the reaction, 16 64 8
(a) 3.0 × 105 (b) 3.0 × 10−5
2NO(g) + O 2 (g) r 2 NO 2 (g). What is (c) 3.0 × 10−4 (d) 3.0 × 104
Ans. (b)
K for the reaction,
1
Ans. (d) HI( g) s 12 H (g) + 21 I (g)
2 2
NO 2 (g) r N 2 (g) + O 2 (g)? Given, CH3COOH s CH COO + H , 3

– +
2 −5 [I2 ] 1/2 [H2 ] 1/2

[CBSE AIPMT 2011] K = 1.5 × 10a …(i) K= …(i)
+ –
[HI]
(a) 1/(4 K 1K 2 ) (b) [1/K 1K 2] 1/2 HCN sH + CN ,
K a 1 = 4.5 × 10 −10 …(ii) H2 ( g) + I2 ( g) s2HI( g)
(c) 1/(K 1K 2 ) (d) 1/(2 K 1K 2 )
[HI]2
Ans. (b) For K′= …(ii)
CN− + CH3COOH sHCN + CH COO – [H2 ][I2 ]
N2 ( g) + O2 ( g) s 2NO( g);K 1 …(i) 3
K =? From Eqs. (i) and (ii)
2NO( g) + O2 ( g) s 2NO2 ( g);K 2 …(ii)
On adding Eqs. (i) and (ii)
On subtracting Eq. (ii) from Eq. (i), we get K × K′ =1
N2 (g) + 2O2 ( g) 2NO2 (g); K = K 1 × K 2 CH3COOH + CN –
HCN + CH3COO – 1 1 1
s s K′= = =
…(iii) Ka 1.5 × 10 −5 K2 (8)2 64
K= =
1
On dividing (iii) by and on reversing we K a 1 4.5 × 10 −10
2 11 The equilibrium constants of the
10 5 following are
get, = = 3.33 × 10 4 ≈ 3 × 10 4
1 3 [NEET 2017, CBSE AIPMT 2007]
NO2 ( g) s N2 ( g) + O2 ( g);
2
09 If the concentration of OH− ions in N 2 + 3H2 q 2NH3 ; K1
(N ) 1/2 (O2 )
So, K= 2 the reaction, N 2 + O 2 q 2NO; K2
(NO2 )
1/ 2
Fe(OH) 3 (s) Fe 3+ (aq)
r 1
H2 + O 2 → H2O; K3
 1 
∴ K = 
+ 3OH− (aq) 2
 K 1K 2  is decreased by 1/4 times, then The equilibrium constant (K) of the
equilibrium concentration of Fe 3+ reaction
07 In which of the following will increase by [CBSE AIPMT 2008] 5 K
equilibrium K c and K p are not 2NH3 + O 2 q 2NO + 3H2O, will
(a) 8 times (b) 16 times 2
equal? [CBSE AIPMT 2010] (c) 64 times (d) 4 times be
(a) 2NO( g) r N ( g) + O ( g)
2 2 Ans. (c) (a) K 1K 33 / K 2 (b) K 2K 33 / K 1
(b) SO2 ( g) + NO2 ( g)
rSO ( g) + NO( g) (d) K 23K 3 / K 1
3 Fe(OH) 3 (s ) sFe (aq) + 3OH− (aq)
3+ (c) K 2K 3 / K 1
(c) H ( g) + I ( g) r2HI ( g)
2 2 [Fe ][OH– ] 3
3+
Ans. (b)
K= …(i)
(d) 2C(s ) + O ( g) r2CO ( g)
2 2 [Fe(OH) 3] Given,N2 + 3H2 q 2NH3, K 1 …(i)
Ans. (d) To maintain equilibrium constant, let the N2 + O2 q 2NO, K 2 …(ii)
Key Idea The reaction for which the concentration of Fe3+ is increased x 1
H2 + O2 → H2O, K 3 …(iii)
number of moles of gaseous products (np ) times, on decreasing the concentration 2
1
is not equal to the number of moles of of OH− by times To calculate,
gaseous reactants (nR ), has different 4 K
1 5
value of K C and K p . [x Fe3+ ][ × OH− ] 3 2NH3 + O2 q 2NO + 3H2O,
∆n g 4 2
From the equation,K p = K C × (RT ) K= …(ii)
[Fe(OH) 3] K =? …(iv)
Chemical Equilibrium 67
On reversing the equation (i) and the concentration of CO2 will increased Ans. (c)
multiplying the equation (iii) by 3, we get in same order. Hence, on addition of CH4 r1
2NH2 q N2 + 3H2 ,
1
…(v)
or O2 equilibrium will cause to the right. BaO2 (s ) sBaO(s) +O (g), ∆H = + ve
r2 2
K1 Combustion reaction is an example of

According to law of mass action,
exothermic reaction.
3
3H2 + O2 → 3H2O, K 33 …(vi) the rate of forward reaction=r1
2 r1 ∝ [BaO2 ]
13 In the two gaseous reactions (i) and
Now, add equation. (ii), (v) and (vi), we get (ii) at 250°C or r1 = k1 [BaO2 ]
the resultant equation. (iv).
1 BaO2 is solid substance in pure state
5 K
2NH3 + O2 q 2NO + 3H2O
(i) NO(g) + O 2 (g) NO 2 (g),K 1
r concentration = 1m
2 2
then, r1 = k1
K K3 (ii) 2NO 2 (g) 2NO(g) + O 2 (g),K 2
r Similarly the rate of backward reaction
∴ K= 2 3
K1 the equilibrium constants K 1 and =r2
K 2 are related as r2 ∝ [BaO] [O2 ]
[CBSE AIPMT 2005, 1994] or r2 = k2 [BaO][O2 ]
12 For the reaction, 1
(a) K 2 = (b) K 2 = K 11/2 Q Concentration of solid [BaO] = 1 [O2 (g)]
CH4 (g) + 2 O 2 (g) rCO (g) K1
2 ∴ r2 = k2 [O2 ]
+ 2H2O(l), 1
(c) K 2 = 2 (d) K 2 = K 21 At equilibrium,
∆ r H = –170.8kJ mol–1 K1 r1 = r2
Which of the following statement is Ans. (c) K 1 =K 2 [O2 ]
not true ? [CBSE AIPMT 2006] For equation (i), or K 1 =K 2 ⋅ pO 2
(a) At equilibrium, the concentrations of 1 where, pO 2 = partial pressure ofO2
NO ( g) + O2 ( g) s NO2 ( g)
CO2 ( g) and H2O(l ) are not equal 2 K1
or = pO 2 (equilibrium
(b) The equilibrium constant for the [NO2 ] K2
[CO2 ] K1 = …(i)
reaction is given byK p = [NO][O2 ] 1/2 constant)
[CH4 ] [O2 ] K1
For equation (ii), Q =K
(c) Addition of CH4 ( g) or O2 ( g) at K2
2NO2 (g) s 2NO(g) + O2 (g)
equilibrium will cause a shift to the
[NO]2 [O2 ] or K = pO 2
right K2 = …(ii)
[NO2 ]2 So, from the above it is clear that
(d) The reaction is exothermic
pressure of O2 does not depend upon the
Ans. (b) Now, on reversing equation (i), we get, concentration of reactants. The given
1 1
For the reaction, = equation is an endothermic reaction. If
K1 [NO2 ] the temperature of such reaction is
CH4 ( g) + 2O2 ( g)
s CO (g) +2H O(l)
2 2
[NO][O2 ] 1/2 increased, then dissociation ofBaO2
∆Hr = − 170.8 k J mol −1 would increase and moreO2 is produced.
This equilibrium is an example of [NO][O2 ] 1/2
=
heterogeneous chemical equilibrium. [NO2 ] 15 For the equilibrium,
Hence, for it 2 2
[CO2 ]  1   [NO][O2 ] 1/2  ∆
Kc = ...(i)   =  MgCO 3 (s) rMgO(s) + CO (g) 2
[CH4 ][O2 ]2 K 1   [NO2 ] 
which of the following expressions
(equilibrium constant on the [NO]2 [O2 ] is correct? [CBSE AIPMT 2000]
= = K2
basis of concentration) [NO2 ]2 (a) K p = pCO 2
pCO 2
and Kp = ...(ii) 1 [MgO][CO2]
= K2 (b) K p =
pCH 4 × p 2 K 21 [MgCO 3]
O
2
p MgO ⋅ p CO 2
(equilibrium constant according (c) K p =
to partial pressure) 14 Reaction, p MgCO 3
Thus, in this concentration of CO2 ( g) and BaO 2 (s) BaO(s) +O 2 (g),
r p MgO + pCO 2
H2O (l ) are not equal at equilibrium. ∆H = +ve (d) K p =
p MgCO 3
The equilibrium constant In equilibrium condition, pressure
[CO2 ] Ans. (a)
(K p ) = is not correct of O 2 depends on
[CH4 ] [O2 ] [CBSE AIPMT 2002] In heterogeneous system,K C and K p are
expression. (a) increased mass ofBaO2 not depend upon the concentration or
On adding CH4 ( g) or O2 ( g) at equilibrium, (b) increased mass of BaO pressure of solid substance. Hence, at
K C will be decreased according to (c) increased temperature of equilibrium their concentration or
expression (i) but K C remains constant at equilibrium pressure are assumed as one.
constant temperature for a reaction, so (d) increased mass ofBaO2 and BaO MgCO3 ( s ) s MgO (s ) + CO2 ( g)
for maintaining the constant value ofK C , both ∴ K p = p CO 2
16 If K 1 and K 2 are the respective total number of moles of reactants 1 1 [NO]

= =
and products at equilibrium are K 2 [N2 ] 1/2 [O2 ] 1/2 [N2 ] 1/2 [O2 ] 1/2
equilibrium constants for the two
[CBSE AIPMT 1996] [NO]
reactions,
(a) 2 + 2 α (b) 2  1 
2
 
2
XeF6 (g ) + H2O(g) XeOF4 (g )   = 
r [NO]
(c) 1 + α (d) 2 − α K  1/2 1/2 
+2HF (g)  2  [N2 ] [O2 ] 
Ans. (b)
XeO 4 (g) + XeF6 (g) XeOF4 (g)
r 2HI(g) s H2 (g) + I2 (g) [NO]2
= =K1
+XeO 3 F2 (g) In initial 2 mol 0 mol 0 mol [N2 ] [O2 ]
At equilibrium (2 − 2α) α mol α mol
The equilibrium constant of the mol
reaction,
So, at equilibrium total moles
TOPIC 2
XeO 4 (g ) + 2HF (g) XeO 3F2 (g )
r = 2 − 2α + α + α Factors Affecting
+ H2O(g) = 2 − 2α + 2α = 2 Equilibrium and
will be [CBSE AIPMT 1998] Le-Chatelier’s Principles
(a) K 1 / (K 2 )2 (b) K 1 ⋅ K 2 19 The rate constants for forward and
(c) K 1 /K 2 (d) K 2 /K 1 backward reaction of hydrolysis of
ester are 1.1 × 10 −2 and 1.5 × 10 −3 per 21 Which one of the following conditions
Ans. (d)
minute. Equilibrium constant for the will favour maximum formation of the
XeF6 ( g) + H2O( g) s XeOF4 ( g) + 2HF ( g)
reaction, product in the reaction, [NEET 2018]
[XeOF4 ][HF]2 [CBSE AIPMT 1995]
K1 = ...(i) A 2 (g) + B2 (g) r X 2 (g);
[XeF6 ][H2O] CH3COOC 2H5 + H+ r
XeO4 ( g) + XeF6 ( g) sXeOF ( g) CH3COOH + C 2H5OH is ∆ r H = − X kJ?
4
(a) 4.33 (b) 5.33 (a) High temperature and high pressure
+ XeO3F2 ( g)
(c) 6.33 (d) 7.33 (b) Low temperature and low pressure
[XeOF4 ] [XeO3F2 ]
K2 = ...(ii) (c) Low temperature and high pressure
[XeO4 ] [XeF6 ] Ans. (d)
(d) High temperature and low pressure
kf
For the reaction, Equilibrium constant,K = Ans. (c)
kb
XeO4 ( g) +2HF ( g) s XeO F ( g) 3 2 Key Concept The given question is based
Forward rate constant
+ H2O ( g) = upon Le-Chatelier’s principle. According
[XeO3F2 ][H2O] Backward rate constant to this principle, if a stress is applied to a
K= …(iii)
[XeO4 ][HF]2 1.1 × 10 −2 1.1 × 10 11 reaction mixture at equilibrium, reaction
K= = = = 7.33 proceeds in such a direction that relieves
1.5 × 10 −3 1.5 1.5
By dividing eq. (ii) by (i) we get, the stress.
K The given reaction is
K= 2 20 K 1 and K 2 are equilibrium constant
K1 A2 (g) + B2 (g) r X2 (g); ∆ r H = − X kJ
for reactions (i) and (ii) According to Le-Chatelier’s principle,
17 The equilibrium constants for the N 2 (g) + O 2 (g) r 2NO(g) …(i) with increase in temperature the
reaction, A 2 2 A at 500 K and
r 1 1 equilibrium shifts in the direction of
NO(g) r N 2 (g) + O 2 (g) …(ii)
700 K are 1 × 10 −10 and 1 × 10 −5 . The 2 2
endothermic reaction (i.e., heat is
absorbed).
given reaction is [CBSE AIPMT 1996] Then, [CBSE AIPMT 1989] Alternatively, the decrease in
2
(a) exothermic (b) slow  1  temperature shifts the equilibrium
(c) endothermic (d) fast (a) K 1 =   (b) K 1 = K 22 towards the direction of exothermic
K2  reaction (i.e. heat is produced).
Ans. (b)
1 Endothermic
For the reaction, (c) K 1 = (d) K 1 = (K 2 ) 0 ∴ A2 (g) + B2 (g) r X2 (g)
K2 Exothermic
A2 s2 A Ans. (a) Similarly, an increase in pressure will
[A]2
K= shifts the equilibrium to that direction
[A2 ] Consider reaction (i), which leads to decrease in total number
The value of equilibrium constant is very N2 ( g) + O2 ( g) s2NO( g) K(i) of gaseous moles. Whereas, a decrease
less and hence, the product 2 in the pressure will shift the equilibrium
[NO]
K1 = to that direction which leads to an
concentration is also very less. So, the [N2 ] [O2 ]
reaction is slow. increase in total number of gaseous
Now, consider reaction (ii), moles.
18 If α is the fraction of HI dissociated 1 1 For, A2 (g) + B2 (g) r X2 (g)
NO(g) s N2 (g) + O2 (g) K(ii)
at equilibrium in the reaction, 2 2 ∆ng = 1 − 2 = − 1
2HI(g) H2 (g) + I 2 (g) starting Thus, low temperature and high
r [N2 ] 1/2 [O2 ] 1/2
K2 = pressure will favour maximum formation
with the 2 moles of HI, then the [NO] of the product in the given reaction.
Chemical Equilibrium 69
22 For the reversible reaction, Ans. (c) 26 For a reversible reaction, if the
N 2 (g) + 3H2 (g) r 2NH 3 (g) + heat Since,OH− are generated from weak acid concentrations of the reactants are
(H2O), and a weak acid (like CO2 ) should be doubled, the equilibrium constant
the equilibrium shifts in forward used to remove it. Because if we add
direction [CBSE AIPMT 2014] strong acid like (HCl) it reverse the
will be [CBSE AIPMT 2000]
(a) by increasing the concentration of reaction. KOH increases the (a) one-fourth (b) halved
NH3 ( g) concentration of OH− , thus again shifts (c) doubled (d) the same
(b) by decreasing the pressure the reaction in backward side. Ans. (d)
(c) by decreasing the concentrations of CO2 combines withOH− to give carbonate Consider a hypothetical change,
N2 ( g) and H2 ( g) which is easily removed.
A+B s C +D
(d) by increasing pressure and SO2 reacts with water to give strong acid, [C] [D]
decreasing temperature so it cannot be used. For this reaction,K eq =
[A] [B]
Ans. (d)
Any change in the concentration,
24 The value of ∆H for the reaction, For the above reaction if concentration
of reactants are doubled then the rate of
pressure and temperature of the X 2 (g) + 4Y 2 (g) 2 XY 4 (g)
r forward reaction increases for a short
reaction results in change in the time but after sometime equilibrium will
direction of equilibrium. This change in is less than zero. Formation of
established. So, concentration has no
the direction of equilibrium is governed XY 4 (g) will be favoured at effect on equilibrium constant. It
by Le-Chatelier’s principle. According to [CBSE AIPMT 2011]
remains unchanged after increasing the
this equilibrium shifts in the opposite (a) low pressure and low temperature concentration of reactants.
direction to undo the change. (b) high temperature and low pressure
N2 ( g) + 3H2 ( g)
s 2NH3 ( g) + Heat (c) high pressure and low temperature 27 According to Le-Chatelier’s
(a) Increasing the concentration of (d) high temperature and high pressure principle, adding heat to a solid
NH 3 (g) On increasing the Ans. (c) r liquid equilibrium will cause
concentration of NH3 ( g), the the
equilibrium shifts in the backward X2 (g) + 4Y2 s2 XY (g); where
4
[CBSE AIPMT 1993]
∆H < 0 (a) temperature to increase

direction where concentration of
(b) temperature to decrease
NH3 ( g) decreases. and ∆n< 0 [∆n = nP − nR ]
(c) amount of liquid to decrease
(b) Decreasing the pressure Since, p ∝ n ∴ The forward reaction is favoured at
(number of moles), therefore, high pressure and low temperature. (d) amount of solid to decrease
equilibrium shifts in the backward (According to Le-Chatelier’s principle) Ans. (d)
direction where number of moles are When we add heat to the equilibrium
increasing. 25 The reaction quotient (Q) for the between solid and liquid, then the
(c) Decreasing the concentration of reaction, equilibrium shifts towards liquid and
N 2 (g) and H2 (g) Equilibrium shifts in hence, the amount of solid decrease and
the backward direction when
N 2 (g) +3H2 (g) 2NH3 (g) is
r amount of liquid increase.
concentration of N2 ( g) and H2 ( g) given by
decreases. [NH3] 2 28 Which one of the following
(d) Increasing pressure and decreasing
Q= . information can be obtained on the
[N 2] [H2] 3
temperature On increasing pressure, basis of Le-Chatelier’s principle?
equilibrium shifts in the forward The reaction will proceed towards [CBSE AIPMT 1992]
direction where number of moles right side, if [CBSE AIPMT 2003] (a) Dissociation constant of a weak acid
decreases. It is an example of (b) Entropy change in a reaction
exothermic reaction therefore (a) Q > K c (b) Q = 0
(c) Q = K c (d) Q < K c (c) Equilibrium constant of a chemical
decreasing temperature favours the reaction
forward direction. where, K c is the equilibrium (d) Shift in equilibrium position on
constant. changing value of a constant
23 KMnO 4 can be prepared from Ans. (a) Ans. (d)
K 2MnO 4 as per reaction, For the reaction, Le-Chatelier’s and Braun French
3MnO 24− + 2H2O N2 ( g) +3H2 ( g) s2NH (g) chemists made certain generalisations
r 3
to explain the effect of changes in
2MnO −4 + MnO 2 + 4OH− [NH3]2
Q (Quotient) = , concentrations, temperature or
The reaction can go to completion [N2 ][H2 ] 3 pressure on the state of system in
by removing OH− ions by adding ∆ ng = 2 − 4 = − 2
equilibrium. When a system is subjected
to a change in one of these factors, the
[NEET 2013] At equilibrium Q is equal toK c but for the equilibrium gets disturbed and the
(a) HCl (b) KOH progress of reaction towards right side, system re-adjusts itself until it return to
(c) CO2 (d) SO2 Q >Kc equilibrium.
9
Ionic Equilibrium
TOPIC 1 Ans. (c) Eq. (i) divide by Eq. (ii)
Y + Z Kp α2 × p
Ostwald’s Dilution Law In equation, X 3 1
= 2 1
Initial moles 1 0 0 Kp 4α × p2
2
01 The percentage of pyridine (C 5H5N) At equil. ( 1 − α) α α
9 p1
where,α = degree of dissociation =
that forms pyridinium ion 1 4p2
Total number of moles
(C 5H5N + H) in a 0.10M aqueous p1 36
= 1 − α + α + α = (1 + α) = = 36 : 1
pyridine solution (K b for p2 1
 1−α
C 5H5N = 1.7 × 10 −9 ) is pX =   p1
[NEET 2016, Phase II]  1+ α
 α 
03 The dissociation equilibrium of a
(a) 0.0060% (b) 0.013% pY =   p1 gas AB2 can be represented as
(c) 0.77% (d) 1.6%  1+ α
Ans. (b) α 2 AB2 (g) 2 AB(g) + B2 (g)
3
pZ = p1
The percentage of pyridine can be equal (1 − α) The degree of dissociation is x and
to the percentage of dissociation of  α   α  is small compared to 1. The
pyridinium ion and pyridine solution as   p1 ×   p1 expression relating the degree of
[pY ][pZ ]  1 + α   1 + α
shown below: K p1 = = dissociation (x) with equilibrium
[pX ]  1−α
  p1 constantK p and total pressure p is
+ H2O +OH
–  1 + α [CBSE AIPMT 2008]
r
N N  α 
2
(a) (2K p / p) (b) (2 K p / p) 1/ 3
H   p1 (c) (2 K p / p) 1/2 (d) (K p / p)
 1 + α
As pyridinium is a weak base, so degree = …(i) Ans. (b)
of dissociation is given as  1−α
 
Kb 1. 7 × 10 −9  1 + α 2 AB2 (g) 3 2 AB (g) + B2 (g)
α= =
C 0 . 10 For equation, A 2B 3 Initial 1 0 0
= 1. 7 × 10 −8
= 1.3 × 10 −4 Initial moles 1 0 moles
At equil. (1 − α) 2α At equil. 2 ( 1 − x) 2x x
or, percentage of dissociation Total number of moles at equilibrium
= (α × 100)% where, x = degree of dissociation
= (1 + α)
= (1.3 × 10 −4 ) × 100 = 0 .013% Total moles at equilibrium
 2α 
pB =   p2 = 2 − 2x + 2 x + x = (2 + x)
 1 + α 2 (1 − x) p 2x p
02 The values of Kp and K p for the So, pAB = , pAB =
1 2  1−α 2
(2 + x) (2 + x)
reactions pA =   p2
 1 + α xp
pB =
X3 Y +Z …(i) 2 2
(2 + x)
  2α  
and A3 2B …(ii)   p2  2
[p ] 2
 1 + α   2x p    x  
= B =    p
are in ratio of 9 : 1. If degree of (pAB) (pB )  2 + x    2 + x  
Kp 2
2 [pA ]  1−α  
dissociation of X and A be equal,   p2 Kp = 2
=
 1 + α (pAB )2   2 (1 − x)  
2
then total pressure at equilibrium
  p
2
2
(i) and (ii) are in the ratio  2α 
  p2   (2 + x)  
[CBSE AIPMT 2008]  1 + α 4x 3p3 (2 + x)2 x 3p
K p2 = …(ii) = × =
(a) 3 :1 (b) 1 :9  1−α
  (2 + x) 3
p 4(1 − x)
2 2
(2 + x)(1 − x)2
(c) 36 :1 (d) 1 :1
 1 + α
Ionic Equilibrium 71
x 3p 06 Ionisation constant of CH3COOH is Ans. (b)

= [Q x <<< 1
2
1/ 3 1. 7 × 10 −5 and concentration of H+ An acid on losing a proton produces a
 2K p  so, (1 − x) ≈ 1 species which has the tendency to
and 2 x=  ions is 3.4 × 10 −4 . Then, find out accept H+ .
 p  (2 + x) ≈ 2
initial concentration of CH3COOH It is called conjugate base of that acid.
molecules. [CBSE AIPMT 2001] −
04 A weak acid, HA, has a K a of H2O - OH + H+ ,
(a) 3 .4 × 10−4 (b) 3 .4 × 10−3 Conjugate
1.00 × 10 −5 . If 0.100 mole of this acid
Acid
(c) 6 .8 × 10−4 (d) 6 .8 × 10−3
base
is dissolved in one litre of water, Ans. (a) HF - F − + H+

Acid Conjugate
the percentage of acid dissociated CH3COOH 3 CH3COO– + H+ base
at equilibrium is closest to [CH3COO– ] [H+ ] Water (H2O) is amphoteric in nature and
[CBSE AIPMT 2007] Ka =
[CH3COOH] thus act both as an acid and base. e.g.
(a) 99.0% (b) 1.00% HF + H2O - F− + H3O+
Given that, [CH3COO– ] = [H+ ] = 3.4 × 10 –4 M
(c) 99.9% (d) 0.100% Acid
Base
Conjugate Conjugate
K a for CH3COOH = 1.7 × 10 –5 base acid
Ans. (b)
HA 3 H+ + A − CH3COOH is weak acid, so in it
[CH3COOH] is equal to initial 09 Which of the following
At equilibrium [H+ = A − ] fluoro-compounds is most likely to
concentration. Hence,
[H+][ A – ] [H+]2
Ka = = (3.4 × 10 −4 ) (3.4 × 10 −4 ) behave as a Lewis base?
[HA] [HA] 1.7 × 10 −5 = [NEET 2016, Phase II]
[CH3COOH]
[H+ ] = K a [HA] = 1 × 10 −5 × 0.1 3.4 × 10 × 3.4 × 10
–4 –4 (a) BF3 (b) PF3
[CH3COOH] = (c) CF4 (d) SiF4
= 1 × 10 −6 = 1 × 10 −3 1.7 × 10 –5
Ans. (b)
Actual ionisation = 6.8 × 10 −3M
α= Key Idea The molecule with lone pair at
Molar concentration centre atom, will behave as Lewis base.
10 −3 TOPIC 2
= = 10 −2 In the given molecules, onlyPF3 has lone
0.1 pair at P as shown below:
% of acid dissociated = 10 −2 × 1.00
Acid Base Concepts
= 1% = 100%
07 Which of the following cannot act
05 At 25°C, the dissociation constant both as Bronsted acid and as
of a base, BOH is 1.0 × 10 −12 . The Bronsted base?
[NEET (Odisha) 2019] Thus, PF3 acts as a Lewis base
concentration of hydroxyl ions in (electron-pair donor) due to presence of
(a) HCO −3 (b) NH3 (c) HCl (d) HSO −4
0.01 M aqueous solution of the base lone pair on P-atom.
Ans. (c)
would be [CBSE AIPMT 2005]
Key Idea Bronsted acid is a substance 10 Which is the strongest acid in the
(a) 2.0 × 10–6 mol L–1
which has a tendency to donate proton. following?
(b) 1.0 × 10–5 mol L–1 Bronsted base is a substance which has
[NEET 2013]
(c) 1.0 × 10–6 mol L–1 a tendency to accept proton. (a) H2 SO 4 (b) HClO 3
(d) 1.0 × 10–7 mol L–1 (c) HClO 4 (d) H2 SO 3
HCl can act as Bronsted acid becuase it
Ans. (d) can only donate proton. Ans. (c)
Base, BOH is dissociated as follows HCl + H2O - H3O+ + Cl − The strength of oxyacids can also be
Acid Base decided with the help of the oxidation
BOH 3 B + + OH–
The remaining options contains number of central atom. Higher the
So, the dissociation constant of BOH oxidation number of central atom, more
substances which act both as Bronsted
base acidic is the oxyacid.
acid and Bronsted base.
[B + ] [OH– ] +6 +5 +7 +4
Kb = …(i) HCO–3 + HCO–3 - H2 CO3 + CO23– H2SO4 , HClO3, HClO4 , H2SO3
[OH]
NH3 + NH3 - NH+4 + NH2−
At equilibrium [B + ] = [OH– ] – –
Order of acidic nature
HSO4 + HSO4 - H2SO4 + SO24–
[OH– ] 2 HClO4 > H2SO4 > HClO3 > H2SO3
∴ Kb = Thus, option (c) is correct.
Since, inHClO4 , oxidation number of Cl is
[BOH]
08 Conjugate base for Bronsted acids highest, so,HClO4 is the strongest acid
Given that K b = 1.0 × 10 −12 among the given acids.
and [BOH] = 0.01 M H2O and HF are
[NEET (National) 2019]
[OH– ] 2 11 Which of these is least likely to act
Thus, 1.0 × 10 –12 = (a) H3O + and F − , respectively
0.01 as a Lewis base? [NEET 2013]
(b) OH− and F − , respectively
[OH– ]2 = 1 × 10 –14
(c) H3O + and H2F + , respectively (a) CO (b) F −
[OH– ] = 1.0 × 10 –7 mol L–1 (c) BF3 (d) PF3
(d) OH− and H2F + , respectively
72 NEET Chapterwise Topiewise Chemistry
Ans. (c) CH3COOH is weak acid while NaOH is Ans. (a)

Electron rich species are called Lewis strong base, so one equivalent of NaOH On hydrolysis sodium borate form
base. Among the given,BF3 is an cannot be neutralised with one sodium hydroxide and boric acid, so the
electron deficient species, so have a equivalent of CH3COOH. Hence, one solution will show basic character
capacity of electron accepting instead of equivalent of each does not have pH because sodium hydroxide is strong
donating. That’s why it is least likely to value 7. As the NaOH is a strong base, base and boric acid is weak acid. While
act as a Lewis base. It is a Lewis acid. the solution will be basic having a pH solution of sodium sulphate is neutral
more than 7. and that of NH4 Cl and calcium nitrate is
12 Which of the following is electron acidic.
deficient? [NEET 2013]
15 The conjugate acid of NH2− is
(a) (CH3)2 (b) (SiH3)2 [CBSE AIPMT 2000] 19 Aqueous solution of acetic acid
(c) (BH3)2 (d) PH3 (a) N2H4 (b) NH4+ contains [CBSE AIPMT 1991]
Ans. (c)
(c) NH2OH (d) NH3 (a) CH3COO – and H+
Ans. (d) (b) CH3COO –,H3O + and CH3COOH
Boron is an element of 13 group and
The species formed after adding a (c) CH3COO –, H3O + and H+
contains three electrons in its valence
shell. When its compoundBH3 dimerises, proton to the base is known as (d) CH3COOH,CH3COO – and H+
each boron atom carry only 6 electrons conjugate acid of the base and the Ans. (b)
that is their octet is incomplete. Hence, species formed after losing a proton is
known as conjugate base of acid. So, The aqueous solution of acetic acid
(BH3)2 is an electron deficient ionise as follows:
compound. NH2– + H+ → NH3
Conjugate acid H2O+ CH3COOH ! CH3COO– +H3O+
In all other given molecules octet of Base
Base Acid
central atom is complete. 16 The strongest conjugate base is
[CBSE AIPMT 1999] So, the aqueous solution of acetic acid
contains CH3COO– , H3O+ and CH3COOH.
13 Which of the following molecules (a) NO –3 (b) Cl–
acts as a Lewis acid? (c) SO2–
4 (d) CH3COO –
[CBSE AIPMT 2009] Ans. (d) TOPIC 3
(a) (CH3) 3B (b) (CH3)2 O Weak acid forms strong conjugate base. Solubility Product and
(c) (CH3) 3P (d) (CH3) 3N In HNO3 , HCl, H2SO4 and CH3COOH ,
CH3COOH is weakest acid, so its Common Ion Effect
Ans. (a)
conjugate base is strongest.
CH3
CH3COOH 3 CH3COO– + H+ 20 Find out the solubility of Ni(OH) 2 in
×• ••×
CH3 ×• B CH3 ×• O • CH3 0.1 M NaOH. Given, that the ionic
••
×•
CH3 Complete octet and 17 The hydride ion H− is stronger base product of Ni(OH) 2 is 2 × 10 −15 .
presence of lp of e – than its hydroxide ion OH− . Which [NEET (Sep.) 2020]
Incomplete (Lewis base)
octet of the following reactions will occur (a) 2 × 10−8 M (b) 1 × 10−13 M
(Lewis acid) if sodium hydride (NaH) is dissolved (c) 1 × 108 M (d) 2 × 10−13 M
CH3 CH3 in water?
•× ×• Ans. (d)
CH3 ×• P •• CH3 •× N •• [CBSE AIPMT 1997]
×• NaOH(aq) → Na+ (aq) + OH− (aq)
CH3
•×
CH3 (a) 2H– (aq) + H2O(l ) → H2O + H2 + 2 e – (0. 1 M ) (0. 1 M)
(b) H– (aq) + H2O (l ) → OH– + H2
complete octet complete octet
(c) H– + H2O (l ) → No reaction Ni(OH)2 (s ) w Ni (aq) + 2OH− (aq)
2+
and presence and presence S′ 0.1 + 2S ′
of lp of e – of lp of e – (d) None of the above
(Lewis base) (Lewis base)
Ans. (b) Ionic product = (S ′) (0.1 + 2S ′)2 (Q2S ′ is
very small)
Sodium hydride dissolved in water as
14 Which of the following statements 2 × 10 −15 = S ′ (0.1)2
NaH +H2O → NaOH + H2
about pH and H + ion concentration S ′ = 2 × 10 −13 M
or H− (aq) +H2O(l ) → OH– + H2 ↑
is incorrect? [CBSE AIPMT 2000]
In the above reaction hydride ion take
(a) Addition of one drop of
proton from water molecule and
21 The molar solubility of CaF2 (
concentrated HCl in NH4 OH solution
decreases pH of the solution
hydrogen gas is evolved. K sp = 5.3 × 10 −11 ) in 0.1 M solution of
(b) A solution of the mixture of one NaF will be [NEET (Odisha) 2019]
equivalent of each of CH3COOH and 18 0.1M solution of which one of these (a) 5.3 × 1011 mol L −1
NaOH has a pH of 7 substances will be basic? (b) 5.3 × 10−8 mol L −1
(c) pH of pure neutral water is not zero [CBSE AIPMT 1992]
(c) 5.3 × 10−9 mol L −1
(d) A cold and concentratedH2SO4 has (a) Sodium borate . × 10 −10 mol L −1
(d) 53
lowerH+ ion concentration than a (b) Calcium nitrate
dilute solution ofH2SO4
Ans. (c)
(c) NH4Cl
Ans. (b) Let the solubility of CaF2 in 0.1 M NaF is
(d) Sodium sulphate
‘S’ mol L −1
CaF2 (s ) - Ca2 + (aq) + 2F − (aq) Solubility product (K sp ) = [A y + ] x [B x − ] y NaCl(aq ) → Na+ (aq ) + Cl – (aq )
S 2S For BaSO4 (binary solute giving two ions) 0.1 M 0 0
0 0.1M 0.1+s
NaF (aq) - Na+ + F − (aq) BaSO4 (s ) r Ba2 + (aq) + SO24− (aq)
AgCl(s ) q Ag + (aq ) + Cl – (aq )
[F ] = 2 S + 0.1 1 M 0. 1 M
− 0. S S s s+0.1
K sp of CaF2 = [Ca2 + ] [F − ]2 ∴ K sp = [Ba2 + ] [SO24− ] = (S ) (S ) = S 2 …(i)
Given, K sp = 1.6 × 10 −10 = [Ag + ][Cl − ]
= [S ] [2S + 0.1]2 [where, S =
Solubility] or 1.6 × 10 −10 = s (0 . 1 + s ) = 0.1 s + s 2
= 53 . × 10 −11 = [S ] [2 S + 0. 1]2
−11 Given, S = 2.42 × 10 −3 gL−1 Q K sp is small, so s is very less in
⇒ . × 10 = [S ] [0. 1]2 [Q2S << 0.1 ]
53 comparison with 0.1. Hence, s 2 can be
Molar mass of BaSO4 = 233 g mol −1
. × 10 −11
53
[S ] = = 5.3 × 10 −9 mol L−1 ∴Solubility of BaSO4
neglected.
(0. 1)2 Thus, 1.6 × 10 −10 = 0 . 1 s
2.42 × 10 −3
(S ) = mol L−1 or s = 1.6 × 10 −9 M
22 pH of a saturated solution of 233
Ca(OH) 2 is 9. The solubility product = 1.04 × 10 −5 mol L−1 26 MY and NY 3 , two nearly insoluble
(K sp ) of Ca(OH) 2 is On substituting the value of S in Eq. (i), salts, have the same K sp values of
[NEET (National) 2019] we get 6.2 × 10 −13 at room temperature.
. × 10−10
(a) 025 (b) 0125
. × 10−15 K sp = (1.04 × 10 −5 mol L−1)2 Which statement would be true in
. × 10−10
(c) 05 . × 10−15
(d) 05 = 1.08 × 10 −10 mol2 L−2 regard to MY and NY 3 ?
Ans. (d) +
24 Concentration of the Ag ions in a (a) The molar solubility of MY in water is
For the reaction, less than that of NY 3.
− saturated solution of Ag 2C 2O 4 is
Ca(OH)2 (s ) - Ca2 + (aq) + 2OH(aq) (b) The salts MY and NY 3 are more
S 2S 2.2 × 10 −4 mol −1 solubility product soluble in 0.5M KY than in pure water
[where, S = solubility] of Ag 2C 2O 4 is [NEET 2017] (c) The addition of the salt of KY to
K sp = [Ca2 + ] [OH− ]2 = S (2 S )2 … (i) (a) 2.42 × 10−8 (b) 2.66 × 10−12 solution of MY and NY 3 will have no
Given, pH = 9 effect on their solubilities
(c) 4.5 × 10−11 (d) 5.3 × 10−12
(d) The molar solubilities of MY and NY 3
We know that, pH + pOH = 14 Ans. (d) in water are identical.
∴ pOH = 14 − 9 = 5 Key concept For a sparingly soluble salt,
− Ans. (a)
pOH = − log[OH] if S is the molar solubility,
For MY, MY r M+ + Y −
− Ax B y (s ) + H2O q xA y + + yB x − 0 S S
5 = − log [OH] where, s = solubility andK sp = solubility
At saturation,
or, [OH− ] = 10 − 5 K [Ax B y ] = [A y + ] x × [B x − ] y = [xS ] x [yS ] y
product.
∴ K sp = [M+ ] [Y − ] = S 2
From above equation, or K sp = x y . y y S x + y
− S = K sp = 6.2 × 10 −13 = 7.874 × 10 −7
[OH] = 2 S = 10 − 5 Where, the constantK sp is called
solubility product. Similarly, for NY3,
10 −5 Ag2 C2O4 ( s ) q 2Ag + + C2O24−
∴ S= NY3 r N + + 3Y −
2 2S S 0 S 3S
On substituting the value of ‘S’ in eqn. (i), K sp = [Ag + ]2 [C2O24− ] = [2S ]2 [S ] ∴ K sp = [N + ] [Y − ] 3 = s × (3s ) 3
we get Given, 2S = 22 . × 10 −4 or S = 1.1 × 10 −4 M K sp = 27 S 4
3
 10 −5  ∴ . × 10 −4 ]2 [1.1 × 10 −4 ]
K sp = [22 K sp 6.2 × 10 −13
K sp = 4S = 4 
3
 = 0.5 × 10 − 15 ∴ s =4 =4 = 3.89 × 10 −4
 2  . × 10 −12
= 53 27 27
 
Therefore, molar solubility of MY in water
23 The solubility of BaSO 4 in water is 25 The solubility of AgCl(s) with is less than that ofNY3.
solubility product 1.6 × 10 −10 in 0.1 M
2.42 × 10 −3 g L−1 at 298 K. The 27 The K sp of Ag 2CrO 4, AgCl, AgBr
NaCl solution would be
value of its solubility product (K sp ) [NEET 2016, Phase II]
will be and AgI are respectively,
(a) 1.26 × 10−5 M (b) 1. 6 × 10−9 M 1.1 × 10–12 , 1.8 × 10 −10 , 5.0 × 10 −13 ,
(Given molar mass of BaSO 4 = 233 (c) 1. 6 × 10−11 M (d) zero 8.3 × 10 −17 . Which one of the
g mol −1 ) [NEET 2018]
Ans. (b) following salts will precipitate last
(a) 1.08 × 10−14 mol2L−2
(b) 1.08 × 10−12 mol2L−2 Key Idea As solubility of AgCl(s) is asked if AgNO 3 solution is added to the
(c) 1.08 × 10−10 mol2L−2
in 0.1 M NaCl solution, so in the solution containing equal moles of
calculation, solubility of Cl – (from NaCl)
(d) 1.08 × 10−8 mol2L−2 must be added to the solubility of
NaCl,NaBr,NaI and Na 2CrO 4 ?
Ans. (c) Cl – (from AgCl). [CBSE AIPMT 2015]
For a general reaction, Let s be the solubility of Ag + and Cl – in (a) AgI (b) AgCI
y+ x− AgCl before the addition of NaCl. (c) AgBr (d) Ag2CrO 4
Ax B y r xA + yB
Ans. (d) Ans. (c) 32 Solubility of a M 2 S type salt is

Ag2 CrO4 s 2Ag + + CrO24− AX2 is ionised as follows 3. 5 × 10 −6 , then find out its
Solubility product A X2 3 A2 + + 2 X – solubility product.
K sp = (2s )2 × S = 4s 3 S mol L–1 S 2S [CBSE AIPMT 2001]
K sp = (1.1 × 10 −12 ) (given) Solubility product of A X2 , (a) 1. 7 × 10−6 (b) 1. 7 × 10−16
2+ − 2
K
S = 3 sp = 0 .65 × 10 − 4
K sp = [A ] [X ] (c) 1. 7 × 10−18 (d) 1. 7 × 10−12
4 = S × (2 S )2 = 4S 3 Ans. (b)
−
AgCl s Ag + Cl
+
Q K sp of A X2 = 3.2 × 10 − 11 Solubility of M2 S salt is 3.5 × 10 – 6 M
K sp = S × S (K sp = 1. 8 × 10 −10 ) ∴ 3 .2 × 10 − 11 = 4S 3 M2 S 3 2 M+ + S 2–
S = K sp = 1.34 × 10 −5 S 3 = 0.8 × 10 −11 3.5 × 10 –6 M 2 × 3. 5 × 10– 6 M 3.5 × 10 –6 M
−12
AgBr s Ag + + Br − = 8 × 10 (on 100% ionisation)
K sp = S × S (K sp = 5 × 10 −13) Solubility = 2 × 10 − 4 mol/L ∴ K sp (solubility product of M2 S )
S = K sp = 0.71 × 10 −6 = [M+] 2 [S 2– ]
30 The solubility product of AgI at =(7.0 × 10 –6 )2 (3.5 × 10 –6 )
AgI s Ag + + I−
K sp = S × S (K sp = 83 . × 10 −17 )
25°C is 1.0 × 10 −16 mol 2 L−2 . The = 171. 5 × 10 –18
S = K sp = 0.9 × 10 −8 solubility of AgI in 10 −4 N solution = 1. 71 × 10 –16 [M] 3
Q Solubility of Ag2 CrO4 is highest.
of KI at 25°C is approximately
So, it will precipitate last.
(in mol L−1 ) [CBSE AIPMT 2003] 33 The solubility of a saturated
(a) 1 .0 × 10 −10 solution of calcium fluoride is
28 H2S gas when passed through a (b) 1 .0 × 10−8 2 × 10–4 mol/L. Its solubility
solution of cations containing HCl (c) 1 .0 × 10−16 product is [CBSE AIPMT 1999]
(d) 1 .0 × 10−12 (a) 12 × 10–2 (b) 14 × 10–4
precipitates the cations of second
Ans. (d) (c) 22 × 10–11 (d) 32 × 10–12
group in qualitative analysis but not
AgI → Ag + + I– Ans. (d)
those belonging to the fourth 2+
group. It is because For binary electrolyte CaF2 3 Ca + 2F –
2 2 × 10 –4 M 2 × 10 –4 M 2 × 2 × 10 –4 M
[CBSE AIPMT 2005] K sp = S
(a) presence of HCl decreases the where, S = solubility in mol/L K sp of CaF2 = [Ca2 + ] [F – ]2
sulphide ion concentration 1.0 × 10 –16
=S 2 = [2 × 10 –4 ] [4 × 10 –4 ]2
(b) presence of HCl increases the = 32 × 10 –12 (mol/L)2
or S =1 × 10 −8 mol/L
sulphide ion concentration
(c) solubility product of group II Normality of KI solutiuon = 10 −4 N
34 Which of the following is most
sulphides is more than that of group Here change is one
soluble? [CBSE AIPMT 1994]
IV sulphides ∴ M = 10 −4 M [n = 1]
(a) Bi2 S3 (K sp = 1 × 10−70)
(d) sulphides of group IV cations are or S for KI solution = 10 −4 M
unstable in HCl (b) MnS (K sp = 7 × 10−16 )
Solubility of AgI in K I solution
Ans. (a) (c) CuS (K sp = 8 × 10−37 )
= 1 × 10 –8 × 10 – 4 (d) Ag2 S (K sp = 6 × 10−51)
In qualitative analysis of cations of = 1 × 10 –12 mol /L
second group H2S gas is passed in Ans. (b)
presence of HCl, therefore due to 31 Solubility of MX 2 type electrolytes Higher the value of solubility product,
common ion effect, lower concentration
of sulphide ions is obtained which is is 0.5 × 10 −4 mol/L, then find out higher is its solubility. In all these
compounds the MnS is most soluble
sufficient for the precipitation of second K sp of electrolytes. because its solubility product is
group cations in the form of their [CBSE AIPMT 2002] maximum.
−12
sulphides due to lower value of their (a) 5 × 10 (b) 25 × 10−10
solubility product (K sp ). Here, fourth (c) 1 × 10−13 (d) 5 × 10−13
group cations are not precipitated
35 In which of the following the
because it require more sulphide ions for Ans. (d) solubility of AgCl will be minimum?
exceeding their ionic product to their MX2 → M2 + [CBSE AIPMT 1993]
solubility products which is not obtained Solubility 0.5 × 10 – 4M 0.5 × 10 – 4M (a) 0.1 M NaNO 3
here due to common ion effect. (b) Water
+ 2X –
2 × 0.5 × 10 –4M (c) 0.1 M NaCl
29 The solubility product of a sparingly (d) 0.1 M NaBr
soluble salt AX 2 is 3.2 × 10 − 11 . Its (on 100% ionisation)
∴ K sp of MX2 = [M2 + ] [X – ]2 Ans. (c)
solubility (in mol/L) is
[CBSE AIPMT 2004] = (0.5 × 10 – 4 ) (1.0 × 10 – 4 )2 In 0.1 M NaCl, the solubility of AgCl is
minimum due to the phenomenon of
(a) 5.6 × 10−6 (b) 3.1 × 10− 4 =0.5 × 10 –12
common ion effect.
(c) 2 × 10− 4 (d) 4 × 10− 4 = 5 × 10 –13 [M] 3
TOPIC 4 Let us consider all the options, pH of which one of them will be
(a) 100 mL of 0.1 M CH3COOH + 100 mL equal to 1? [NEET 2018]
pH, Buffer and Indicator of 0.1M NaOH (a) IV (b) I (c) II (d) III
CH3COOH + NaOH → CH3COONa + H2O
Ans.
36 The pK b of dimethyl amine and pK a Initial 100 mL × 100 mL × 0 mmol
M M
of acetic acid are 3.27 and 4.77 conc. 0.1 M 0.1 M 75 mL HCl + 25 mL NaOH
5 5
respectively atT(K). The correct =10mmol =10mmol
Milliequivalent of HCl
option for the pH of dimethyl Final conc. 0 0 10 mmol M 1
It is not basic buffer because hydrolysis = 75 mL of HCl = × 75 = 15
ammonium acetate solution is 5 5
[NEET 2021] of salt takes place and final solution Milliequivalent of NaOH
contains salt of weak acid with strong M
(a) 8.50 (b) 5.50 (c) 7.75 (d) 6.25
base only. = 25 mL of NaOH
Ans. (c) 5
Hence, option (a) is incorrect. 1
= × 25 = 5
Dimethyl ammonium acetate (b) 100 mL of 0.1 M HCl + 200 mL of 0.1 M 5
[CH3COONH2 (CH3)2 ] is a salt of weak acid NH4OH ∴ Milliequivalent of HCl left unused
(CH3COOH) and weak base [(CH3)2 NH].
HCl + NH4OH → NH4 Cl + H2O = 15 − 5 = 10
pH of dimethyl ammonium acetate salt
solution can be calculated using Initial conc. 100 mL× 200 mL × 0 mmol Volume of solution = 100 mL
formula : 0.1 M HCl 0.1 M ∴ Molarity of [H+ ] in the resulting mixture
1 =10 mmol =20mmol 10 1
pH = 7 + (pK a − pK b ) = =
2 Final conc. 0 10 mmol 10 mmol 100 10
pK a of acetic acid = 4.77 1
It is basic buffer because final solution ∴ pH = log + = log(10) = 1
pK b of dimethyl amine = 3.27 contains weak base and its salt with [H ]
1 strong acid. Hence, option (b) is correct.
pH = 7 + (4.77 − 3.27)
2 (c) 100 mL of 0.1 M HCl + 100 mL of 0.1 M 40 What is the pH of the resulting
1 NaOH solution when equal volumes of 0.1
pH = 7 + × 1.50
2 HCl + NaOH → NaCl + H2O M NaOH and 0.01 M HCl are mixed?
⇒ pH = 7 + 0.75 Initial conc. 100 mL 100 mL × 0 mmol [CBSE AIPMT 2015]
pH = 7.75 ×01
.M 0.1 M (a) 12.65 (b) 2.0 (c) 7.0 (d) 1.04
=10 mmol =10 mmol Ans. (a)
37 The pH of 0.01 M NaOH (aq) solution Final conc. 0 0 10 mmol Key Concept When equal volumes of
will be [NEET (Odisha) 2019] It is a neutral solution. Hence, option (c) acid and base are mixed, then resulting
(a) 7.01 (b) 2 is incorrect. solution become alkaline if concentration
(c) 12 (d) 9 (d) 50 mL of 0.1 M NaOH + 25mL of 0.1 M of base is taken high.
CH3COOH Let normality of the solution after mixing
Ans. (c)
0.1 M NaOH and 0.01 M HCl is N.
NaOH is a strong base, thus CH3COOH + NaOH → CH3COONa + H2O ∴ N 1V1 − N2V2 = NV
[OH− ] = 0.01M = 10 −2 M Initial 25mL 50mL or 0.1 × 1 − 0.01 × 1 = N × 2
0 mmol
pOH = − log [OH− ] conc. × 0.1 M × 0.1 M Since, normality of NaOH is more than
= − log(10 −2 ) = 2 =2 .5 mmol = 5mmol that of HCl.
We know that, pH + pOH = 14 Final conc. 0 2.5 mol 2.5 mmol Hence, the resulting solution is alkaline.
∴ pH = 14 − 2 = 12 It is basic solution. Hence, option (d) is or [OH] = N =
0.09
= 0.045 N
Thus, option (c) is correct. incorrect. 2
or pOH = − log (0.045) = 1.35
38 Which will make basic buffer? 39 Following solutions were prepared ∴ pH = 14 − pOH = 14 − 1.35 = 12.65
[NEET (National) 2019] by mixing different volumes of
(a) 100 mL of 0.1 M CH3COOH + 100 mL NaOH and HCl of different 41 Which one of the following pairs of
of 0.1 M NaOH
concentrations : solution is not an acidic buffer?
(b) 100 mL of 0.1 M HCl + 200 mL of 0.1 M [CBSE AIPMT 2015]
NH4OH
M M
I. 60 mL HCl + 40 mL NaOH (a) HClO 4 and NaClO 4
(c) 100 mL of 0.1 M HCl + 100 mL of 0.1 M 10 10
NaOH M M (b) CH3COOH and CH3COONa
(d) 50 mL of 0.1 M NaOH + 25 mL of 0.1 M II. 55 mL HCl + 45 mL NaOH (c) H2CO 3 and Na2CO 3
10 10
CH3COOH (d) H3 PO 4 and Na3 PO 4
M M
Ans. III. 75 mL HCl + 25mL NaOH Ans. (a)
Key idea A buffer solution having pH
5 5
Strong acid with its salt cannot form
more than 7 is known as basic buffer. It is M M
IV. 100 mL HCl + 100mL NaOH buffer solution. Hence,HClO4 and NaClO4
obtained by mixing weak base and its salt 10 10 is not an acidic buffer.
with strong acid in a fixed proportion.
42 pH of a saturated solution of 44 A buffer solution is prepared in K w = (H+ ) (OH− )

Ba(OH) 2 is 12. The value of which the concentration of NH3 is K w = 1 × 10 −14
K
solubility product K sp of Ba(OH) 2 is 0.30 M and the concentration of OH− = +ω
[CBSE AIPMT 2012] NH+4 is 0.20 M. If the equilibrium H
(a) 3.3 × 10−7 (b) 5.0 × 10−7 − 1 × 10 −14
constant, K b for NH3 equals and [OH ] =
(c) 4.0 × 10−6 (d) 5.0 × 10−6 1.8 × 10 −5 , what is the pH of this 1 × 10 −12
Ans. (b) [Q[H+ ] [OH− ] = 1 × 10 −14 ]
solution? (log 2.7 = 0.43)
Given, pH ofBa(OH)2 = 12 [CBSE AIPMT 2011] = 1 × 10 −2 mol/L
∴ pOH = 14 − pH (a) 9.43 (b) 11.72 (c) 8.73 (d) 9.08 Ba(OH)2 → Ba2 + + 2 OH−
= 14 − 12 = 2
S 2S
Ans. (a) 2+ − 2
We know that, [salt] K sp = [Ba ] [OH ] = [S ] [2 S ]2
pOH = −log[OH− ] pOH = pK b + log  1 × 10 −2 
[base] −2 2
=  (1 × 10 )
2 = − log[OH− ]
− =− log K b + log
[salt]  2 
[OH ] = antilog (−2) [base] = 0.5 × 10 −6 = 5.0 × 10 −6 M3
[OH− ] = 1 × 10 −2 0.20
= − log 1.8 × 10 −5 + log
Ba(OH)2 dissolves in water as 0.30 47 In a buffer solution containing
Ba2 + + 2OH− = 5 − 0.25 + (− 0.176)
Ba(OH)2 (s ) a S 2S
equal concentration of B − and H B,
S mol L−1 = 4. 75 − 0.176 = 4. 57 the K b for B − is 10 −10 . The pH of
− −2
∴ [OH ] = 2 S = 1 × 10 ∴ pH = 14 − 4.57 = 9.43 buffer solution is
[OH− ]
S= [Ba2 + = S ] [CBSE AIPMT 2010]
2 45 What is [H+ ] in mol/L of a solution (a) 10 (b) 7
[OH− ] 1 × 10 −2 that is 0.20 M in CH3COONa and (c) 6 (d) 4
[Ba2 + ] = =
2 2 0.10 M in CH3COOH ? Ans. (d)
K sp = [Ba2 + ] [OH− ]2 (K a for CH3COOH = 1.8 × 10 −5 ) Key Idea (i) For basic buffer,
 1 × 10 −2  [CBSE AIPMT 2010] [salt]
=   (1 × 10 −2 )2 pOH = pKb + log
 2  (a) 3.5 × 10−4 (b) 1.1 × 10−5 [base]
= 0.5 × 10 −6 (c) 1.8 × 10−5 (d) 9.0 × 10−6 (ii) pH + pOH = 14
= 5 × 10 −7 Ans. (d) Given, K b = 1 × 10 −10 , [salt] = [base]
[salt]
Key Idea CH3COOH (weak acid) and pOH = − log K b + log
43 Buffer solutions have constant CH3COONa (conjugated salt) form acidic [base]
acidity and alkalinity because buffer and for acidic buffer, ∴ pOH = − log (1 × 10 −10 ) + log 1 = 10
[CBSE AIPMT 2012] [salt]
pH = pK a + log pH + pOH = 14
(a) these give unionised acid or base on [acid]
[Qconcentration of [B − ] = [HB]
reaction with added acid or alkali and [H+ ] = − antilog pH pH = 14 − 10 = 4
(b) acids and alkalies in these solutions [salt]
are shielded from attack by other pH = − log Ka + log
ions
[acid] 48 What is the [OH− ] in the final
(c) they have large excess ofH+ or OH− [QpK a = − log K a ] solution prepared by mixing 20.0
(0.20)
ions = − log (1.8 × 10 −5 ) + log mL of 0.050 M HCl with 30.0 mL of
(d) they have fixed value of pH (0.10)
0.10 M Ba(OH) 2 ?
Ans. (a) = 4.74 + log2 [CBSE AIPMT 2009]
If small amount of an acid or alkali is = 4.74 + 0.3010 = 5.041 (a) 0.10 M (b) 0.40 M
added to a buffer solution, it converts Now, [H+ ] = antilog (− 5.045) (c) 0.0050 M (d) 0.12 M
them into unionised acid or base. Thus, = 9.0 × 10 −6 mol/L Ans. (a)
its pH remains unaffected or in other
Number of milliequivalents of HCl
words its acidity/alkalinity remains 46 If pH of a saturated solution of
constant. e.g. = 20 × 0.050 × 1 = 1
Ba (OH) 2 is 12, the value of its K sp is Number of milliequivalents of Ba(OH)2
H3O+ + A − a H2O + HA [CBSE AIPMT 2010]
− = 2 × 30 × 0.10 = 6
OH + H A → H2O + A − (a) 4.00 × 10−6 M3 (b) 4.00 × 10−7 M3
If acid is added, it reacts with A − to form (c) 5.00 × 10−7 M3 (d) 5.00 × 10−6 M3 [OH− ] of final solution
undissociated H A. Similarly, if Milliequivalents of Ba(OH)2
Ans. (d)
base/alkali is added,OH− combines with – milliequivalents of HCl 6−1
H A to give H2O and A − and thus, Given, pH ofBa(OH)2 = 12 = =
Total volume 50
maintains the acidity/ alkalinity of buffer So, pOH = 2
solution. ∴ [H+ ] = [1 × 10 −12 ] = 0.1 M
49 Equal volumes of three acid So, in aqueous solution of 10 –8 M HCl, neutralisation of NaOH with H2O,H2S,
solutions of pH 3, 4 and 5 are mixed [H+ ] = [H+ ] of HCl + [H+ ] of water H2Se and H2Te.
in a vessel. What will be the H+ ion = 10 –8 + 10 –7 Na2O > Na2S > Na2Se > Na2Te
concentration in the mixture? = 11 × 10 –8 M ≈ 1.10 × 10 –7 M (Q pH of basic solution is higher than
acidic or least basic solution)
[CBSE AIPMT 2008]
(a) 1.11 × 10−4 M (b) 3.7 × 10−4 M 52 Which of the following pairs
54 The rapid change of pH near the
(c) 3.7 × 10−3 M (d) 1.11 × 10−3 M constitutes a buffer?
[CBSE AIPMT 2006] stoichiometric point of an acid
Ans. (b)
(a) HNO2 and NaNO2 base titration is the basis of
Let the volume of each acid = V indicator detection. pH of the
(b) NaOH and NaCl
pH of first, second and third acids = 3, 4 solution is related to ratio of the
(c) HNO 3 and NH4NO 3
and 5 respectively
(d) HCl and KCl concentrations of the conjugate
[H+ ] of first acid (M1) = 1 × 10 −3
Ans. (a) acid (HIn) and base (In − ) forms of
[Q H+ = 1 × 10 − pH ]
A pair constituent withHNO2 and NaNO2 the indicator given by the
[H ] of second acid (M2 ) = 1 × 10 −4
+
because HNO2 is weak acid andNaNO2 is expression [CBSE AIPMT 2004]
[H+ ] of third acid(M3) = 1 × 10 −5 a salt of weak acid (HNO2 ) with strong [In–]
Total [H+ ] concentrated of mixture base (NaOH). Hence, it is an example of (a) log = pK In – pH
[HIn]
M V + M2V2 + M3V3 acidic buffer solution.
(M) = 1 1 [HIn]
V1 + V2 + V3 (b) log = pK In – pH
53 What is the correct relationship [In–]
1 × 10 −3 × V + 1 × 10 −4 × V + 1 × 10 −5 × V between the pH of isomolar [HIn]
= (c) log = pH –pK In
V +V +V solutions of sodium oxide (pH1 ), [In–]
1 × 10 −3 × V (1 + 0.1 + 0.01) sodium sulphide (pH2 ) , sodium [In–]
= (d) log = pH – pK In
3V selenide (pH3 ) and sodium telluride [HIn]
1.11 × 10−3 (pH4 ) ? Ans. (d)
= = 3.7 × 10−4 M [CBSE AIPMT 2005]
3 (a) pH1 > pH2 ≈ pH3 > pH4 Acid indicators are generally weak acid.
(b) pH1 < pH2 < pH3 < pH4 The dissociation of indicator HIn takes
50 Calculate the pOH of a solution at (c) pH1 < pH2 < pH3 ≈ pH4 place as follows
25°C that contains 1 × 10 −10 M of (d) pH1 > pH2 > pH3 > pH4 HIn 3 H+ + In–
hydronium ion. [CBSE AIPMT 2007] Ans. (d) [H ] [In– ]
+
∴ K In =
(a) 7.00 (b) 4.00 The correct order of pH of isomolar [HIn]
(c) 9.00 (d) 1.00 solution of sodium oxide (pH1), sodium [HIn]
or [H ] =K In ⋅
+
K(i)
Ans. (b) sulphide (pH2 ),sodium selenide (pH3) and [In– ]
[H3O+ ] = [H+ ] =10 −10 sodium telluride (pH4 ) is
Q pH = – log [H+ ] K(ii)
pH1 > pH2 > pH3 > pH4 because in
pH + pOH = 14 K(i) aqueous solution, they are hydrolysed as From eq. (i) and (ii) we get,
and pH = − log [H+ ] follows.  [HIn] 
∴ pH = − log  KIn ⋅ 
pH = − log [10 −10 ] K(ii) Na2O + 2H2O → 2NaOH + H2O  [In− ] 
pH = 10 Base
[In– ]
from eq. (i) and (ii), we get Na2S + 2H2O → 2NaOH + H2 S = − log KIn + log
[HIn]
pOH + 10 = 14 Strong base Weak acid
[In– ]
pOH = 14 − 10 = 4 Na2Se + 2H2O → 2NaOH = pK In + log
Strong base [HIn]
51 The hydrogen ion concentration of [In– ]

+ H2 Se or log = pH − pK ln
a 10–8 M HCl aqueous solution at [HIn]
Weak acid
298 K (K w = 10–14 ) is Na2Te + 2H2O → 2NaOH
[CBSE AIPMT 2006] Strong base 55 Solution of 0.1 N NH4 OH and 0.1 N
(a) 1.0 × 10 M
–6
(b) 1.0525 × 10 M–7
+ H2Te NH4 Cl has pH 9.25, then find out
(c) 9 .525 × 10–8 M (d) 1.0 × 10–8 M Weak acid pK b of NH4 OH. [CBSE AIPMT 2002]
Ans. (b) On moving down the group acidic (a) 9.25 (b) 4.75
−8 + character of oxides increases. (c) 3.75 (d) 8.25
In aqueous solution of 10 M HCl, [H ]
ion concentration is based upon the Order of acidic strength Ans. (b)
concentration of H+ ion of 10 −8 M HCl H2Te > H2Se > H2S > H2O Solution of NH4OH and NH4 Cl acts as a
and concentration ofH+ ion of water. Order of neutralisation of NaOH basic buffer solution. For basic buffer
K w of H2O = 10 –14 = [H+ ][OH− ] H2Te > H2Se > H2S > H2O solution
or [H+ ] = 10 –7 M [salt]
Hence, their aqueous solutions have the pOH = pK b + log
(due to its neutral behaviour) following order of basic character due to [base]
pOH = 14 – pH 58 The pH value of blood does not [Where ⇒WB= Weak base,SB =
= 14 – 925
. = 4.75 Strong base WA = Weak acid,SA =
change appreciably by a small
0.1 Strong acid.]
4.75 = pK b + log addition of an acid or base,
0.1 Hence, option (d) is the correct.
because the blood
pK b = 4.75 [CBSE AIPMT 1995]
61 Which of the following salts will
(a) is a body fluid
give highest pH in water?
56 The concentration of [H+ ] and (b) can be easily coagulated [CBSE AIPMT 2014]
concentration of [OH– ] of a 0.1 M (c) contains iron as a part of the
(a) KCl (b) NaCl
aqueous solution of 2% ionised molecule
(c) Na2CO 3 (d) CuSO4
(d) contains serum protein that acts as
weak monobasic acid is Ans. (c)
buffer
[CBSE AIPMT 1999]
Ans. (d) The highest pH refers to the basic
[ionic product of water = 1 × 10–14 ] solution containingOH− ions. Therefore,
Blood is an example of buffer solution,
. × 10–3 Mand 5 × 10–11 M
(a) 002 the basic salt releasing moreOH− ions on
which contains serum protein, so its pH
(b) 1 × 10–3 M and 3 × 10–11 M does not change appreciably by adding
hydrolysis will give highest pH in water.
(c) 2 × 10–3 M and 5 × 10–12 M small amount of an acid or a base to it. Only the salt of strong base and weak
(d) 3 × 10–2 M and 4 × 10–13 M acid would release moreOH− ion on
hydrolysis. Among the given salts,
Ans. (c) 59 The pH value of a 10 M solution of Na2 CO3 corresponds to the basic salt as
[H + ] in monobasic acid HCl is [CBSE AIPMT 1995] it is formed by the neutralisation of
= molarity × degree of ionisation (a) less than 0 (b) equal to 0 NaOH [strong base] and H2 CO3 [weak
2 (c) equal to 1 (d) equal to 2 acid].
= 0.1 ×
100 Ans. (a) CO23− + H2O s HCO3− + OH−
= 2 × 10 –3 M +
HCl(aq) → H (aq) + Cl (aq) −
ionisation constant of water 62 Equimolar solutions of the

[S = K sp ]
K w = (H+ ) (OH− ) following substances were
[HCl] = 10 M
1 × 10 –14 prepared separately. Which one of
K
[OH– ] = w+ = ⇒ [H+ ] = 10 mol / L
[H ] 2 × 10 –3 these will record the highest pH
pH = − log [H+ ] = − log 10
value? [CBSE AIPMT 2012]
= 5 × 10 –12 M = − 1, so the pH is less than zero.
(a) BaCl2 (b) AlCl3 (c) LiCl (d) BeCl2
57 A physician wishes to prepare a Ans. (a)
buffer solution at pH= 3.58 that
TOPIC 5 BaCl2 is a salt of strong acid HCl and
efficiently resist changes in pH yet Hydrolysis of Salts strong base Ba(OH)2 . So, its aqueous
solution is neutral with pH 7. All other
contains only small concentration
salts give acidic solution due to cationic
of the buffering agents. Which one 60 Which among the following salt hydrolysis, so their pH is less than 7.
of the following weak acid together solutions is basic in nature? Thus, pH value is highest for the solution
with its sodium salt would be best [NEET (Oct.) 2020]
of BaCl2
to use? [CBSE AIPMT 1997] (a) Ammonium chloride
(a) m-chlorobenzoic acid
(b) Ammonium sulphate 63 The ionisation constant of
(c) Ammonium nitrate
(pK a = 3 .98) ammonium hydroxide is 1.77 × 10 −5
(b) p-chlorocinnamic acid (d) Sodium acetate
(pK a = 441
. ) Ans. (d) at 298 K. Hydrolysis constant of
(c) 2, 5-dihydroxy benzoic acid ammonium chloride is
Nature of a salt solution depends on the
(pK a = 2 .97) nature of constituent acid and base
[CBSE AIPMT 2009]
(d) Acetoacetic acid (pK a = 3 .58) whether they are strong or weak. (a) 5.65 × 10−10 (b) 6.50 × 10−12
Ans. (d) (a) NH4 Cl is made of (c) 5.65 × 10−13 (d) 5.65 × 10−12
By the use of Henderson’s equation [NH4OH(WB) + HCl(SA)] → Acidic Ans. (a)
[salt] solution. Given,K a (NH4OH) = 1.77 × 10 −5
pH = pKa + log 10 (b) (NH4 )2 SO4 is made of
[acid] NH+4 + OH–
[NH4OH(WB) + H2SO4 (SA)] → Acidic NH4OH 3
When, [salt] = [acid] solution. [NH4 ][OH– ]
+
Ka = = 1.77 × 10 −5 …(i)
∴ pH = pK a (c) NH4NO3 is made of [NH4OH]
Q pK a = 3.58, thus at this state [NH4OH(WB) + CH3COOH(WA)] →
Hydrolysis of NH4 Cl takes place as,
pH = 3.58 Basic solution.
(d) CH3COONa is made of NH4 Cl + H2O → NH4OH + HCl
So, acetoacetic acid (pK a = 3.58) is best NH+4 + H2O → NH4OH + H+
[NaOH(SB) + CH3COOH(WA)] → Basic or
to use.
solution Hydrolysis constant,
[NH4OH][H+ ] Ammonium chloride (NH4 Cl) is a salt of Sodium carbonate (Na2 CO3) is a salt of
Kh = …(ii)
[NH+4 ] weak base and strong acid. So, its strong base and weak acid. Its aqueous
aqueous solution will be acidic as solution is also basic and its pH value will
[NH4OH][H+ ][OH– ]
or K h = …(iii) NH4 Cl + H2O → NH4OH + HCl be more than 10,
[NH+4 ][OH– ] i.e. highest among them.
Weak base Strong acid
From Eqs. (i), (ii) and (iii)
So, pH of NH4 Cl is less than 7. Na2 CO3 + H2O → 2NaOH
K
Kh = w [Q [H+ ][OH− ] = K w ] Sodium nitrate (NaNO3 ) is the salt of
Strong base
Ka
strong acid and strong base. So, its + H2 CO3
10 −14 Weak acid
= aqueous solution is neutral as
1.77 × 10 −5 NaNO3 + H2O → NaOH 65 The compound whose aqueous
= 5.65 × 10 −10 Strong base solution has the highest pH is
[CBSE AIPMT 1988]
+ HNO3
64 Which has highest pH? Strong acid (a) NaCl (b) NaHCO3
[CBSE AIPMT 2002] (c) Na2CO3 (d) NH4Cl
So, pH of NaNO3 is 7.
(a) CH3CO −OK + (b) Na2CO3 Ans. (c)
Potassium acetate (CH3COOK) is a salt of
(c) NH4 Cl (d) NaNO3 strong base and weak acid. Its aqueous The hydrolysis of NaCl gives neutral
Ans. (b) solution will be basic and pH value will be solution because it is salt of strong acid
pH=log
1 greater than 7 ≈ 8.8 and strong base and hence, its pH is 7.
[H+ ] CH3COO−K+ + H2O → CH3COOH NH4 Cl is salt of weak base and strong
acid, so its pH is less than 7.NaHCO3 is
pH is inversely proportional to hydrogen Weak acid
also acidic whereasNa2 CO3 is salt of
ion concentration. As concentration of + KOH strong base and weak acid, so its pH is
H+ decreases pH increases and Strong base
more than 7.
vice-versa.
10
Redox Reactions and
Electrochemistry
TOPIC 1 O
TOPIC 2
Redox Reactions O 115° O Electrolytic Conductance,
Cr Electrolysis and Its
O O
01 The oxidation state of Cr in CrO 5 is Quantitative Aspect
Oxidation state of Cr in CrO5 is +6 due to
[NEET (Odisha) 2019]
the presence of two peroxide linkages
(a) − 6 (b) + 12 which can be calculated as 05 The molar conductance of NaCl,
(c) + 6 (d) + 4 x + (−1) × 4 + 1 × (−2) HCl and CH3COONa at infinite
[For Cr]
Ans. (c) [For 0 − 0] [For 0] dilution are 126.45, 426.16 and 91.0
The structure of CrO5 is x − 6 = 0; x = +6 S cm 2 mol − 1 respectively. The
O molar conductance of CH3COOH at
O O 03 Oxidation state of Fe in Fe 3 O 4 is infinite dilution is
Cr Choose the right option for your
O O [CBSE AIPMT 1999]
3 4 5 8 answer. [NEET 2021]
Oxidation state of Cr is +6 due to the (a) (b) (c) (d)
presence of two peroxide linkages, 2 5 4 3 (a) 201.28 S cm2 mol − 1
which can be calculated as. Ans. (d) (b) 390.71 S cm2 mol − 1
In CrO(O2 )2 , let the oxidation state of Cr (c) 698.28 S cm2 mol − 1
Oxidation state of Fe inFe3O4 is
be x calculated as (d) 540.48 S cm2 mol − 1
x + (−1) 4 + (−2) = 0 x –2
Ans. (b)
Fe3 O4
x − 6 = 0 ⇒ x = +6
Molar conductance of NaCl,
3x + (–2 × 4) = 0
λ°NaCl = 126.45 S cm2 mol −1
02 In acidic medium, H2O 2 changes 3x = + 8
8 Molar conductance of HCl,
Cr 2O 2−
7 to CrO 5 which has two
x=+
λ°HCl = 426.16 S cm2 mol −1
3
(—O—O—) bonds. Oxidation state of − +
Cr in CrO 5 is Molar conductance of CH3COONa,
[CBSE AIPMT 2014] 04 The oxidation state of Cr in
λ°CH COONa = 91.0 S cm2 mol −1
(a) +5 (b) +3 (c) +6 (d) −10 K 2Cr 2O 7 is [CBSE AIPMT 1988] 3
According to Kohlrausch’s law;
Ans. (c) (a) +5 (b) +3 (c) +6 (d) +7
λ°HCl = λ°H + + λ°Cl− …(i)
When H2O2 is added to an acidified Ans. (c)
solution of a dichromate Cr2O27− , a deep λ°NaCl = λ°Na + + λ°Cl− …(ii)
Let the oxidation state of Cr is x
blue coloured complex, chromic
K2 Cr2O7 λ°CH + = λ°Na + + λ°CH − …(iii)
3 COONa 3 COO
peroxide CrO5 [or CrO(O2 )2 ] is formed.
∴ 2 (+1) + 2x + 7 (−2) = 0 λ°CH = λ°CH + λ°H +
Cr2O27− + 2 H+ + 4H2O → 2 CrO(O2 )2 3 COOH 3 COO
−
14243 2 + 2x − 14 = 0
Chromic peroxide λ°CH = (λ°CH + λ°Na + )
2x − 12 = 0 3 COOH 3 COO
−
[blue coloured complex] + 5H2O

2x = 12 + (λ°H + + λ°Cl− ) − (λ°Na + + λ°Cl− )
This deep blue coloured complex has the 12
following structure x = = +6 λ°CH = λ° − + λ°HCl − λ°NaCl
2 3 COOH CH 3 CO O Na +
Redox Reactions and Electrochemistry 81
λ°CH = 91.0 + 426.16 − 126.45 H2SO4 → 2H+ + SO24 − The above reaction is a
3 COOH
Strong electrolyte disproportionation reaction as Cu(+1)
λ°CH = 390.71 S cm2 mol −1 as it is dilute is oxidised to Cu(+2 ) and reduced to
3 COOH
H2O r H+ + OH− Cu(0).
+6 +7 +4
06 The molar conductivity of 0.007 M Reaction at cathode (Pt) (ii) 3MnO24 − + 4H+ → 2MnO4− + MnO2
acetic acid is 20 S cm 2 mol − 1 . 2H+ + 2e − → H2 ↑ + 2H2O
The above reaction is a
What is the dissociation constant Reaction at anode (Pt)
− disproportionation reaction as Mn
of acetic acid ? Choose the correct 4OH − 4e − → O2 ↑ + 2H2O (+ 6) is oxidised to MnO−4 (Mn+ 7 ) and
option. +4
We get,O2 gas at anode. reduced toMnO2 (Mn).
[λ °H = 350S cm 2 mol − 1 , +7 +6 +4
λ °CH COO− = 50 S cm 2 mol − 1 ] 08 The number of Faradays (F ) ∆ K2 MnO4 + MnO2 + O2
(iii) 2KMnO4 →
3 [NEET 2021] required to produce 20 g of The above reaction is not a
−4 −1 −1 disproportionation reaction as Mn
(a) 1.75 ×10 mol L calcium from molten CaCl 2 (Atomic
(+7) is only reduced toK2MnO4 (Mn+ 6 )
(b) 2.50 ×10− 4 mol − 1 L − 1 mass of Ca = 40 g mol −1 ) is and MnO2 (Mn+ 4 ).
(c) 1.75 ×10− 5 mol − 1 L − 1 [NEET (Sep.) 2020] +7
(iv) 2MnO−4 + 3Mn2 + + 2H2O + 4
(d) 2.50 ×10− 5 mol − 1 L − 1 (a) 2 (b) 3 (c) 4 (d) 1
→ 5MnO2 + 4H+
Ans. (c) Ans. (d)
The above reaction is not a
λ CH COOH = 20 S cm2 mol −1 CaCl2 r Ca2 + + 2Cl − disproportionation reaction as Mn(+7 ) is
3 Molten
Concentration of CH3COOH , C = 0.007 M only reduced toMnO2 (+ 4).
2+
λ°H + = 350 S cm2 mol −1 At cathode Ca + 2e − → Ca Hence, option (d) is correct.
(Reduction)
λ°CH − = 50 S cm2 mol −1 According to Faraday’s first law,
10 Following limiting molar
3 COO
Charge passed in Faraday = Gram
According to Kohlrausch’s law, equivalent of product
conductivities are given as
λ°CH COOH = λ°H + + λ°CH COO −
3 =
Given mass
× no. of e − released
λ °m (H SO ) = x S cm 2mol −1
3 2 4
Atomic mass
λ°CH
3 COOH
= 350 + 50
20 λ °m (K = y S cm 2mol −1
2 SO4 )
= × 2= 1 F
= 400 S cm2 mol −1 40 λ °m (CH COOK) = z S cm 2mol −1
2
Degree of dissociation, So, one Faraday (F) is required for the
λ CH COOH process. λ °m (in S cm 2mol −1 ) for CH3COOH
α= 3
λ°CH COOH will be [NEET (Odisha) 2019]

3 09 Which of the following reactions
20 1 (a) x − y + 2 z (b) x + y − z
α= = = 0.05 = 5 × 10 −2 are disproportionation reaction? (x − y)
400 20
(i) 2Cu + → Cu 2+ + Cu 0 (c) x − y + z (d) +z
2
CH3COO– + H+
t=0
CH3COOH q
C – –
(ii) 3MnO 24− + 4H+ → 2MnO 4− Ans. (d)
t = teq C − Cα Cα Cα + MnO 2 + 2H2O Key Idea According to Kohlrausch’s law,
∆
Equilibrium constant, (iii) 2KMnO 4 → K 2MnO 4 λºm for Ax B y = xλº y + + yλº(B) x −
(A )
C2α2 Cα2 where, λºm = limiting molar conductivity
k= = + MnO 2 + O 2
C (1 − α) 1 − α of electrolyte and λº y + and λº(B) x − are
As α < < 1;1 − α ≈ 1
(iv) 2MnO −4 + 3Mn 2+ + 2H2O → (A )
the limiting molar conductivities of
k = Cα2 = 0.007 × (0.05)2 5MnO 2 + 4H⊕ cation (A ) and anion (B x − ),
y+
= 0.007 × 25 × 10 −4 Select the correct option from the respectively.
= 1.75 × 10 −5 mol L−1 following. [NEET (National) 2019] Given

(a) (i), (ii) and (iii) λºm = 2λ°H + + λº 2 − = x S c2mol −1
(H 2 SO 4 ) SO
4 …(i)
07 On electrolysis of dilute sulphuric (b) (i), (iii) and (iv)
λºm = 2λºK + + λº
acid using platinum (Pt) electrode, (c) (i) and (iv) only (K 2 SO 4 ) SO 2 −
4
(d) (i) and (ii) only
the product obtained at anode will = y S cm2mol −1 …(ii)
be [NEET (Sep.) 2020] Ans. (d)
λºm (CH3COOK) = λºCH − + λºK +
(a) oxygen gas (b) H2 S gas The reaction in which the same species 3 COO
is simultaneously oxidised and reduced = z S cm2mol −1 …(iii)
(c) SO2 gas (d) hydrogen gas are called disporportionation reactions. To find : = λºCH COO − + λºH +
λºm(CH COOH)
Ans. (a) Let us, consider the given reaction one
3 3
The above equation can be obtained by
Dilute H2SO4 contains H2SO4 and H2O and by one: Eq. (i) Eq. (ii)
Eq. (iii) + −
they show electrolytic dissociation as, (i) 2Cu+ → Cu2 + + Cu0 2 2
λºm(H 2 SO 4 ) where, E = gram-equivalent mass of Cl − 15 When 0.1 mole of MnO 2−

∴ λºm(CH = λºm (CH + 4 is
3 COOH) 3 COOK) 2 i = current,t = time, it = q
oxidised, the quantity of electricity
λºm(K 2 SO 4 ) Given,w = 0.10 mol = (0 . 10 × 71) g,
required to completely oxidise
− i = 3 A, E = 35.5 −
2 MnO 2−
4 to MnO 4 is
 x y The following reactions occured, [CBSE AIPMT 2014]
=  z + −  S cm mol −1
2
 2 2 At cathode : (a) 96500 C (b) 2 × 96500 C
 x−y  +2e–
= + z  S cm2 mol −1 2H2O → H2 + 2OH−
(c) 9650 C (d) 96.50 C
 2  Ans. (c)
At anode :
[1 mole e − = 1F]
−2e–
11 The molar conductivity of a 0.5 2Cl − → Cl2 MnO24− Ç MnO−4
(+6) (+7)
mol/dm 3 solution of AgNO 3 with 35.5g 71 g
electrolytic conductivity of Putting all values in expression (i) we get As per the equation, for 1 mole ofMnO24− , 1
F of electricity is required. Thus, for 0.1
5.76 × 10 −3 S cm −1 at 298 K is (0.10 × 71) =
35.5
×3 ×t mole of MnO24− , 0.1 F of electricity is
[CBSE AIPMT 2016, Phase II] 96500
required.
(a) 2.88 S cm2 /mol or t = 6433 s
Since, 1 F = 96500 C
(b) 11.52 S cm2 /mol or t = 107 .22 min
∴ 0.1 F = 0.1 × 96500 C = 9650 C
(c) 0.086 S cm2 /mol ~− 110 min  1 s = 1 min
Hence, 9650 C of electricity is required
(d) 28.8 S cm2 /mol  60  to completely oxidise MnO24− to MnO−4 .
Ans. (b)
Key Idea The relation between molar
13 The number of electrons delivered 16 The weight of silver (at. wt. = 108)
conductivity (λm) and electrolytic at the cathode during electrolysis
displaced by a quantity of
conductivity (κ) is given as by a current of 1 ampere in 60
κ × 1000 electricity which displaces
λm = seconds is (charge on electron =
5600 mL of O 2 at STP will be
M 1.60 × 10 −19 C) [CBSE AIPMT 2014]
where, M is molarity of solution. [CBSE AIPMT 2016, Phase II]
(a) 5.4 g (b) 10.8 g
Given, concentration of solution, (a) 6 × 1023
(b) 6 × 10 20
(c) 54.0 g (d) 108.0 g
M = 0 . 5 mol / dm3 (c) 3.75 × 1020 (d) 7.48 × 1023
Ans. (d)
Electrolytic conductivity, Ans. (c)
Since, 22400 mL volume is occupied by 1
κ = 5. 76 × 10 −3 S cm–1 From Faraday’s first law of electrolysis, mole of O2 at STP.
Temperature,T = 298 K w it
= …(i) Thus, 5600 mL O2 means
∴ Molar conductivity, E 96500 5600 1
κ × 1000 Given,i = 1 A;t = 60 s = mol O2 = mol O2
λm = 22400 4
M Putting these values in Eq. (i), we get 1
5. 76 × 10 −3 × 1000 w 1 × 60 ∴ Weight of O2 = × 32 = 8 g
= = 4
0. 5 E 96500 According to problem,
= 11. 52 S cm2 /mol or
w
=
6
Equivalents of Ag = Equivalents of O2
E 9650 Weight of Ag
12 During the electrolysis of molten =
= Number of mole of electrons Equivalent weight of Ag
sodium chloride, the time required ∴ Number of electrons WO2
to produce 0.10 mol of chlorine gas 6 =
= × 6.022 × 1023 Equivalent weight of O2
using a current of 3 amperes is 9650
WAg WO 2
[CBSE AIPMT 2016, Phase II] = 3.75 × 1020 =
(a) 55 minutes (b) 110 minutes MAg MO 2
(c) 220 minutes (d) 330 minutes 14 Aqueous solution of which of the 1 4
Ans. (b) following compounds is the best ∴
WAg
×1=
8
×4
Key Idea This problem is based on conductor of electric current? 108 32
Faraday’s first law of electrolysis which [CBSE AIPMT 2015] [Q2H2O → O1 + 4H+ + 4e − ]
states that when an electric current is (a) Acetic acid, C2 H4O2 ⇒ WAg = 108 g
passed through an electrolytic solution, (b) Hydrochloric acid, HCl
the amount of substance (w), deposited at (c) Ammonia, NH3
the electrode, is proportional to the 17 At 25° C molar conductance of
(d) Fructose, C 6 H12O 6
electric charge (q) passed through the 0.1 molar aqueous solution of
electrolytic solution. Ans. (b)
ammonium hydroxide is
The formula used in the problem is Since, HCl is strong acid and dissociates 9.54 Ω −1 cm 2 mol −1 and at infinite
Eit completely. Hence, it conducts
w= …(i) dilution its molar conductance is
96500 electricity best in its aqueous solution.
238 Ω −1 cm 2 mol −1 . The degree of 20 The equivalent conductance of

M 22 Kohlrausch’s law states that at
ionisation of ammonium hydroxide 32 [CBSE AIPMT 2008]
at the same concentration and solution of a weak monobasic acid (a) infinite dilution, each ion makes definite
temperature is [NEET 2013] is 8.0 mho cm 2 and at infinite contribution to equivalent conductance
of an electrolyte, whatever be the
(a) 2.080 % (b) 20.800 % dilution is 400 mho cm 2 . The
nature of the other ion of the
(c) 4.008 % (d) 40.800 % dissociation constant of this acid is electrolyte
Ans. (c) [CBSE AIPMT 2009]
(b) infinite dilution, each ion makes
Given, molar conductance at 0.1 M . × 10−5
(a) 125 . × 10−6
(b) 125 definite contribution to equivalent
concentration, (c) 6.25 × 10−4 . × 10−4
(d) 125 conductance of an electrolyte
depending on the nature of the other
λ c = 9.54 Ω −1 cm2 mol −1 Ans. (a)
ion of the electrolyte
Molar conductance at infinite dilution, Λc (c) infinite dilution, each ion makes
Degree of dissociation,α =
λ∞c = 238 Ω −1 cm2 mol −1 Λ∞ definite contribution to conductance
We know that, degree of ionisation, ∞ of an electrolyte, whatever be the
where, Λ and Λ are equivalent
c
λ conductances at a given concentration nature of the other ion of the
α = ∞c × 100
λc and at infinite dilution respectively. electrolyte
8.0 (d) infinite dilution, each ion makes
=
9.54
× 100 = 4.008% ⇒ α= = 2 × 10 −2 definite contribution to equivalent
238 400
conductance of an electrolyte,
From Ostwald’s dilution law (for weak whatever be the nature of the other
18 Limiting molar conductivity of monobasic acid), ion of the electrolyte
NH4OH Cα2 Ans. (d)
Kc =
(1 − α)
° m (NH OH) ) is equal to
(i.e. Λ
Kohlrausch’s law states that “the
4
or = Cα2 (Q 1>>> α) equivalent conductance of an electrolyte
[CBSE AIPMT 2012] at infinite dilution is equal to the sum of
1 −2 2
= (2 × 10 ) the equivalent conductances of the
(a) Λ°m(NH 4Cl) + Λ°m(NaCl) − Λ°m(NaOH) 32
component ions.”
(b) Λ °m (NaOH) + Λ°m(NaCl) − Λ °m (NH 4Cl) = 1.25 × 10 −5 λ∞ = λa + λc
where, λ a = equivalent conductance of
(c) Λ °m(NH 4OH) + Λ °m(NH 4Cl) − Λ °m(HCl) 21 Al 2O 3 is reduced by electrolysis at the anion
(d) Λ °m(NH 4Cl) + Λ °m(NaOH) − Λ°m(NaCl) low potentials and high currents. If λ c = equivalent conductance of the
cation
Ans. (d) 4.0 × 10 4 A of current is passed
Each ion has the same constant ionic
According to Kohlrausch’s law, through molten Al 2O 3 for 6 h, what conductance at a fixed temperature, no
limiting molar conductivity ofNH4OH mass of aluminium is produced? matter of which electrolyte it forms a
(Assume 100% current efficiency, part.
Λ°m (NH OH) = Λ°m (NH Cl) + Λ°m (NaOH)
4 4 atomic mass of Al = 27 g mol −1 )
− Λ°m (NaCl) [CBSE AIPMT 2009] 23 4.5 g of aluminium (atomic mass
(a) 9.0 × 103 g (b) 8.1 × 104 g 27u) is deposited at cathode from
19 An increase in equivalent (c) 2.4 × 105 g (d) 1.3 × 104 g Al 3+ solution by a certain quantity
conductance of a strong Ans. (b) of electric charge. The volume of
electrolyte with dilution is mainly
Al2O3 ionises as,
hydrogen produced at STP from H+
due to [CBSE AIPMT 2010] ions in solution by the same
Al2O3 º Al 3+ + AlO3–
3
(a) increase in ionic mobility of ions Cathode Anode quantity of electric charge will be
(b) 100% ionisation of electrolyte at [CBSE AIPMT 2005]
normal dilution At cathode
(a) 44.8 L (b) 22.4 L (c) 11.2 L (d) 5.6 L
(c) increase in both, i.e. number of ions Al 3+ +3 e − → Al
3F 27g Ans. (d)
and ionic mobility of ions
(d) increase in number of ions Q Mass of aluminium deposited by 3 F of From second law of Faraday
mAl E Al
Ans. (a) electricity = 27 g =
mH EH
k × 1000 ∴ Mass of aluminium deposited by
Key Idea λ eq = κ × V = . 4.5 27 /3
Normality 4.0 × 10 4 × 6 × 3600 C of electricity =
mH 1
On dilution, the number of current 27 × 4.0 × 10 4 × 6 × 3600
carrying particles per cm3 decreases but = g or mH = 0.5 g
3F
the volume of solution increases. Q Volume of 2 gH2 at STP = 22.4 L
Consequently, the ionic mobility 27 × 4.0 × 10 4 × 6 × 3600 ∴ Volume of 0.5 gH2 at STP
increases, which in turn increases the = g
3 × 96500 22.4 × 0.5
equivalent conductance of strong = L = 5.6 L
= 8.1 × 10 4 g 2
electrolyte.
24 In electrolysis of NaCl when Pt Ans. (a) 29 A 5A current is passed through a

electrode is taken then H2 is The equivalent conductance ofBaCl2 at solution of zinc sulphate for 40
liberated at cathode while with Hg infinite dilution, min. The amount of zinc deposited
cathode it forms sodium amalgam 1 at the cathode is
λ ∞ of BaCl2 = λ ∞ of Ba2 + + λ ∞ of Cl –
because [CBSE AIPMT 2002] 2 [CBSE AIPMT 1996]
127 (a) 40.65 g (b) 0.4065 g
(a) Hg is more inert than Pt = + 76 = 139.5
(b) more voltage is required to reduce 2 (c) 4.065 g (d) 65.04 g
H+ at Hg than at Pt Ans. (c)
(c) Na is dissolved in Hg while it does not 27 The specific conductance of a 0.1 N Current, I = 5 A
dissolved in Pt KCl solution at 23°C is 0.012 time,t = 40 min = 40 × 60 = 2400 s
(d) concentration of H+ ions is larger Ω −1 cm −1 . The resistance of cell
when Pt electrode is taken Amount of electricity passed
containing the solution at the same Q = It
Ans. (b) temperature was found to be 55 Ω. Q = 5 × 2400
Sodium chloride in water dissociates as The cell constant will be Q = 12000 C.
NaCl º Na+ + Cl – [CBSE AIPMT 1999]
Zn2 + + 2e – → Zn
H2O ºH +
+ OH– (a) 0.142 cm−1
n = 2e −
When electric current is passed through (b) 0.66 cm−1 From Faraday first law
this solution using platinum electrodes, (c) 0.918 cm−1 W = ZI t
Na+ and H+ move towards cathode
(d) 1.12 cm−1 Z = equivalent mass
whereas Cl – and OH– ions move towards
anode. Ans. (b) [65.39 = mass of zinc]
Mass 65.39
At cathode Specific conductivity, = − = g of zinc
H+ + e – → H k = 0.012 Ω −1 cm−1 ; e × F 2 × 96500
H + H → H2 Resistance = 55 Ω therefore, 12000 C charge will deposite
1 l  1 65.39 × 12000
At anode k= × G= =
Cl – → Cl + e − resistance a  R  2 × 96500
Cl + Cl → Cl2 l
= cell constant = 4.065 g of zinc
If mercury is used as cathode,H+ ions a
l
are not discharged at mercury cathode = 55 × 0.012 = 0.66 cm−1
because mercury has a high hydrogen a TOPIC 3
over voltage. Na+ ions are discharged at Electronium Series,
cathode in preference ofH+ ions yielding 28 Equivalent conductance of NaCl,
sodium, which dissolves in mercury to Electrode Potential and Emf
HCl and C 2H5COONa at infinete
form sodium amalgam.
dilution are 126.45, 426.16 and 30 Identify the reaction from following
25 Cell reaction is spontaneous when 91 Ω −1 cm 2 , respectively. The having top position in EMF series
[CBSE AIPMT 2000] equivalent conductance of (Standard reduction potential)
° is negative (b) Ered
(a) Ered ° is positive C 2H5COOH is [CBSE AIPMT 1997] according to their electrode
(a) 201.28 Ω −1 cm2 potential at 298 K.
(c) ∆G° is negative (d) ∆G° is positive
Ans. (c) (b) 390.71 Ω −1 cm2 [NEET (Oct.) 2020]
−1
(c) 698.28 Ω cm 2 (a) Mg2+ + 2 e − → Mg(s )
When the value of ∆G ° is negative, the (b) Fe2+ + 2 e − → Fe(s )
cell reaction is spontaneous. (d) 540.48 Ω −1 cm2
(c) Au 3+ + 2 e − → Au(s )
∆G ° = − nFE ° Ans. (b)
(d) K + +1 e − → K(s )
where, n = number of electrons take part By Kohlrausch’s law Ans. (c)
F = Faraday constant λ ∞ for NaCl =λ Na + + λ Cl− …(i) Let us consider the segment of EMF
E ° = EMF of the cell
λ ∞ for HCl =λH + + λ Cl− …(ii) series (standard reduction potential) of
Thus, for a spontaneous reaction, the the given reduction half-call reactions:
EMF of the cell must be positive. λ ∞ for C2H5 COONa =λ Na + + λ C –
2 H 5 COO
…(iii) Reduction half reaction E/V at 298K
26 The equivalent conductances of So, λ ∞ for C2H5 COOH can be obtained by
(a) Mg 2 + + 2e → Mg – 2.36
Ba 2+ and Cl − are 127 and adding Eqs. (ii) and (iii) and then
2+
76 Ω −1 cm −1 eq −1 respectively at subtracting Eq. (i) (b) Fe + 2e → Fe – 0.44
infinite dilution. The equivalent = λ ∞ of C2H5 COONa + λ ∞ of HCl (c) Au3 + + 3 e → Au + 140
.
conductance of BaCl 2 at infinite − λ ∞ for NaCl
(d) K + + e → K – 2.93
dilution will be [CBSE AIPMT 2000] = (91 + 426.16 − 126.45) Ω −1 cm2
(a) 139.52 (b) 203 (c) 279 (d) 101.5 = 390.71 Ω –1 cm2 Hence, option (c) is correct.
31 The standard electrode potential 33 In the electrochemical cell ∴ For potential of H2 electrode to be
zero, pH 2 should be equal to [H+ ]2 , i.e.
(E − ) values of Zn||ZnSO 4 (0.01 M)|| CuSO 4 (1.0M) 10 −14 atm.
(Al 3+ / Al, Ag + / Ag, K + /K and Cu, the emf of this Daniel cell is 10 −14
∴ log =0
Cr 3+ /Cr are − 1.66 V, 0.80V, 2.93 V E 1 . When the concentration (10 −7 )2
and − 0.74 V, respectively. The ZnSO 4 is changed to 1.0 M and
°
correct decreasing order of that of CuSO 4 changed to 0.01 M, 35 If the E cell for a given reaction has
reducing power of the metal is the emf changes to E 2 . From the a negative value, which of the
[NEET (Odisha) 2019] followings, which one is the following gives correct
(a) Ag > Cr > Al > K relationship between E 1 and E 2 ? relationships for the values of ∆G°
(b) K > Al > Cr > Ag RT
( Given, = 0.059) and K eq ?
(c) K > Al > Ag > Cr F [CBSE AIPMT 2016, Phase II, 2011]
[NEET 2017, 2003]
(d) Al > K > Ag > Cr (a) E1 = E2 (b) E1 < E2 (a) ∆G ° > 0; K eq < 1 (b) ∆G ° > 0; K eq > 1
Ans. (b) (c) E1 > E2 (d) E2 = 0 ≠ E1 (c) ∆G ° < 0; K eq > 1 (d) ∆G ° < 0; K eq < 1
More negative the value of standard Ans. (c) Ans. (a)
reduction potential, higher is the Given, ° = −ve
E cell
Thinking process Calculate the value of
reduction power.
E cell i.e. E 1 and E2 by substituting the ° is
i.e. Reducing power The relation between ∆G ° and E cell
respective given values in the Nernst
1 given as
∝ equation,
standard reduction potential 0.059 [Zn2 + ] ∆G ° = − nF E ° ... (i)
E cell = E ° − log cell
Thus, the correct decreasing order of n [Cu2 + ] ° is negative , so ∆G ° comes out to
If E cell
reducing power of the metal is
Compare the calculated values of E 1 and be positive. Again, relation between ∆G °
K > Al > E2 and find the correct relation. and K eq is given as
(EKº + /K = −2.93V) (E º 3 + = −166 . V)
Al / Al For the electrochemical cells, ∆G ° = −2 . 303 nRT log K eq ... (ii)
Cr >Ag Zn|ZnSO4 (0.01M)| | CuSO4 (1M)| Cu From Eq. (i) we get that ∆G ° is positive.
(E º 3 + = −0.74 V) (E Ag º
+ / Ag = 0.80 V) Cell reaction : Now, if ∆G ° is positive thenK eq comes
Cr / Cr
Zn + Cu2 + → Zn2 + + Cu; n = 2 out to be negative from eq (ii).
32 For the cell reaction, i.e. ∆G ° >1 and K eq < 1
0.059 Zn2 +
2Fe 3+ (aq) + 2I − (aq) → 2Fe 2+ (aq) E1 = E ° − log 2 +
2 Cu Short trick As E ° is negative so
cell
+I 2 (aq) 0.059 0.01 reaction is non-spontaneous or you can
= E° − log
E cell = 0. 24 V at 298 K. The
È
2 1 say reaction is moving in backward
direction. For non-spontaneous
standard Gibbs energy (∆ r G È ) of E1 = E ° −
0.059
log
1
= (E ° + 0.059) reaction, ∆G ° is always positive andK eq
the cell reaction is 2 100
is always less than 1.
[Given that Faraday constant For cell, Zn|ZnSO4 (1M)| | CuSO4 (0.01M)| Cu
0.059 1
F = 96500 C mol −1 ] E2 = E ° − log 36 A hydrogen gas electrode is made
2 0.01
0.059 by dipping platinum wire in a
(a) −23.16 kJ mol −1 (b) 46.32 kJ mol −1 E2 = E ° − log 100
2 solution of HCl of pH=10 and by
(c) 23.16 kJ mol −1 (d) −46.32 kJ mol −1 ∴ = (E °− 0.059) ⇒ E 1 > E2 passing hydrogen gas around the
Ans. (d) platinum wire at 1 atm pressure.
The relation between E cell
º
and ∆ r G º is as 34 The pressure of H2 required to The oxidation potential of
follows: make the potential of H2 -electrode electrode would be [NEET 2013]
∆ r G º = − nFE cell
º
zero in pure water at 298 K is (a) 0.059 V (b) 0.59 V
For the cell reaction, [CBSE AIPMT 2016, Phase I] (c) 0.118 V (d) 1.18 V
2Fe3 + (aq) + 2 I− (aq) → 2Fe2 + (aq) + I2 (aq) (a) 10−12 atm (b) 10−10 atm Ans. (b)
n=2 (c) 10−4 atm (d) 10−14 atm For hydrogen electrode, oxidation half
Given, F = 96500 C mol −1
= 0.24 V
, E cell
º Ans. (d) reaction is
Now, we know that ∆ r G º = − nFE cell
º
From the question, we have an equation H2 → 2H+ + 2e−
(1 atm) (At pH 10)
On substituting the given values in above 2H+ + 2e − → H2 (g)
equation we get According to Nernst equation, If pH = 10
∆ r G º = − 2 mol × 96500 C mol − 1 0.0591 pH H+ = 1 × 10 − pH = 1 × 10 −10
E = E° − log + 2 2
× 0.24 J mol − 1 2 [H ] From Nernst equation,
= − 46320 J mol −1
0.0591 pH 2 0.0591 [H+ ]2
=0 − log E cell = E ° cell − log
. KJ mol − 1
= − 4632 2 (10 −7 )2 2 pH 2
Hence, option (d) is correct. [Q [H+ ] = 10 −7 ] For hydrogen electrode, E ° cell = 0
0.0591 ( 10 −10 )2 39 Standard electrode potential for Ans. (a)

E cell = − log
2 1 Sn 4+ / Sn 2+ couple is +0.15 V and ∆G ° = − nFE °
0.0591 × 2 1 that for the Cr 3+ /Cr couple is –0.74. For reaction,
=+ log −10
2 10 These two couples in their Cu2 + + 2e − → Cu, K(i)
= 0 .0591 log 10 10 standard state are connected to ∆G ° = − 2 × F × 0.337
= 0 .0591 × 10 make a cell. The cell potential will For reaction, Cu+ → Cu2 + + e − , K(ii)
= 0.591 V be [CBSE AIPMT 2011] ∆G ° = − 1 × F × (−0.153)
(a) + 0.89 V (b) + 0.18 V = + 0.153 F
37 Standard electrode potential of (c) + 1.83 V (d) + 1.199 V Adding Eqs. (i) and (ii), we get
three metals X, Y and Z are –1.2V, + Cu+ + e − → Cu, ∆G ° = −0.521 F
Ans. (a)
0.5V and –3.0V respectively. The ∆G ° = − nFE °
reducing power of these metals will E° = + 0.15 V
Sn 4+ / Sn 2 +
∴ − 0.521 F = − nFE °
be [CBSE AIPMT 2011] E ° 3+ = −0.74 V ∴ E ° = 0.52 V
Cr / Cr
(a) Y > X > Z (b) Z > X > Y
(c) X > Y > Z (d) Y > Z > X ° = E cathode
E cell ° °
(RP) − E anode(RP) 42 Standard free energies of
Ans. (b) = 0.15 − ( − 0.74) formation (in kJ/mol) at 298 K are
E X° = − 12
. V, = + 0.89 V –237.2, –394.4 and –8.2 for H2O(l),
CO 2 (g) and pentane (g),
E Y° = + 0.5 V, 40 For the reduction of silver ions with ° for
respectively. The value of E cell
E Z° = − 3.0 V, copper metal, the standard cell
potential was found to be + 0.46 V the pentane-oxygen fuel cell is
∴ Z> X>Y [CBSE AIPMT 2008]
at 25°C. The value of standard
[Q higher the reduction potential, (a) 1.968 V (b) 2.0968 V
lesser the reducing power.] Gibbs energy, ∆G° will be
(c) 1.0968 V (d) 0.0968 V
(F = 96500C mol −1 ) Ans. (c)
38 The electrode potentials for [CBSE AIPMT 2010]
∆G of H2O(l ) = − 237.2kJ / mol
Cu 2+ (aq ) + e – → Cu + (aq ) (a) − 89.0 kJ (b) − 89.0 J
(c) − 44.5 kJ (d) − 98.0 kJ ∆G of CO2 ( g) = − 394.4kJ / mol
and Cu + (aq ) + e – → Cu( s ) ∆G of pentane ( g) = − 8.2kJ / mol
Ans. (a)
are +0.15 V and +0.50 V In pentane-oxygen fuel cell following
We know that, standard Gibbs energy,
respectively. The value of reaction takes place
°
∆G ° = − nFE cell C5H12 + 10H2O(l ) → 5CO2 + 32 H+ + 32 e −
E ° 2+ will be
Cu /Cu [CBSE AIPMT 2011] For the cell reaction, 8O2 + 32H+ + 32 e − → 16 H2O(l )
(a) 0.325 V (b) 0.650 V 2 Ag + + Cu → Cu2 + + 2 Ag C5H12 + 8O2 → 5CO2 + 6H2O(l ), E ° = ?
(c) 0.150 V (d) 0.500 V ° = + 0.46 V
∆E cell ∆G reaction = Σ∆G product − Σ ∆G reactant
Ans. (a) °
∆G ° = − nF E cell = 5 × ∆G (CO 2 ) + 6∆G (H 2 O) − [∆G (C H 12 )
Cu2+
+ e → Cu ,
– +
n=2
5
+8 × ∆GO 2 ]
E 1° = 0.15 V, ∆G 1° = − n1E 1°F ∆G ° = − 2 × 96500 × 0.46
= 5 × (−394.4) + 6 × (−237.2) − (−8.2 + 0)
Cu+ + e – → Cu, E2° = 0.50 V, = − 88780 J
= − 1972 − 1423.2 + 8.2
∆G2° = − n2 E2°F = − 88.7 kJ ≈ − 89.0 kJ
= − 3387 kJ / mol
Cu2 + + 2e – → Cu, E ° = ?, 41 Given, = −3387 × 10 3 J / mol
∆G ° = − nE °F °
∆G = − nFE cell
(i) Cu 2+ + 2 e − → Cu,
∆G ° = ∆G 1° + ∆G2° E° = 0.337 V °
−3387 × 10 3 = − 32 × 96500 × E cell
(ii) Cu 2+ + e − → Cu + , ° =
−3387 × 10 3
= 1.0968 V
− nE ° F = − n1E 1°F − n2 E2°F E cell
E° = 0.153 V –32 × 96500
or − 2 E ° F = − 1 F × 0.15 + (− 1 F × 0.50)
Electrode potential, E° for the
or − 2 E ° F = − 0.15 F − 0.50 F reaction, 43 On the basis of the following E°
or − 2 FE ° = − F(0.15 + 0.50) Cu + + e − → Cu, will be values, the strongest oxidising
0.65 [CBSE AIPMT 2009] agent is [CBSE AIPMT 2008]
∴ E° = = 0.325 V
2 (a) 0.52 V (b) 0.90 V [Fe(CN) 6] 4– → [Fe(CN) 6] 3– + e − ;
(c) 0.30 V (d) 0.38 V E° = − 0.35 V
Fe 2+ → Fe 3+ + e − ; Cell reaction At equilibrium, E cell = 0

E° = − 0.77 V (i) Fe → Fe2 + + 2e − , Given that,
(a) [Fe(CN) 6] 4– (b) Fe2+ E ° = 0.441 V R = 8.314 JK– 1 mol – 1
(c) Fe 3+ (d) [Fe(CN) 6] 3− (ii) 2Fe3+ + 2 e − → 2Fe2 + , E ° = + 0.771 V T = 25° C + 273 = 298 K
Ans. (c) F = 96500 C and n = 2
° = 1.212 V
Fe + 2Fe3+ → 3Fe2 + , E cell 2 .303 × 8314
. × 298
Substance which have higher reduction ∴ E ° cell = log 10 K
2 × 96500
potential are stronger oxidising agent. Alternative On the basis of cell reaction
[Fe(CN) 6 ] 4– → [Fe(CN) 6 ] 3– + e − , 0.0591
following half-cell reactions are written = log 10 K
E ° = − 0.35 V At anode 2
Fe2 + → Fe3+ + e − , E ° = − 0.77 V Fe → Fe2 + + 2e − (oxidation) Given that E ° cell = 0.295 V
0.0591
Q ° = − E red
E oxi ° At cathode ∴ 0.295 = log 10 K
2
2Fe3+ + 2e − → 2Fe2 + (reduction)
∴ [Fe(CN) 6 ] 3− + e − → [Fe(CN) 6 ] 4 − , 0.295 × 2
° = E cathode
So, E cell ° °
− E anode log 10 K = = 10
E ° = 0.35 V 0.0591
Fe3+ + e − → Fe2 + , E ° = 0.77 V = (+ 0.771) − (− 0.441) = + 1.212 V. antilog log 10 K = antilog 10
Hence,Fe3+ has maximum tendency to K = 1 × 10 10
reduced, so it is the strongest oxidising 46 A hypothetical electrochemical cell
agent. is shown below 48 On the basis of the information
A | A + (xM ) || B + (yM) | B available from the reaction.
44 The equilibrium constant of the 4 2
The EMF measured is + 0.20V. Al + O 2 → Al 2O 3 ,
reaction,
The cell reaction is 3 3
Cu(s) + 2 Ag + (aq) → Cu 2+ (aq) [CBSE AIPMT 2006] ∆G = −827kJ mol–1 of O 2 , the
+ 2Ag( s ), E° = 0.46 V at 298 K (a) A + B + → A+ + B minimum EMF required to carry
is [CBSE AIPMT 2007] (b) A+ + B → A + B +
out the electrolysis of Al 2O 3 is
(a) 2.0 × 10 10
(b) 4.0 × 10 10 (F = 96500 C mol −1 ) [CBSE AIPMT
(c) A+ + e – → A, B + + e – → B 2003]
(c) 4.0 × 1015 (d) 2.4 × 1010 (d) the cell reaction cannot be predicted
(a) 2.14 V (b) 4.28 V
Ans. (c) Ans. (a) (c) 6.42 V (d) 8.56 V
2+ 2+
Cu(s ) + 2 Ag (aq) → Cu (aq) Electrochemical cell, Ans. (a)
+ 2 Ag(s ) A | A + (xM) | | B + ( yM) | B 4 2
Al + O2 → Al2O3 ,
E ° = 0.46 V at 298 K 3 3
The EMF of cell is + 0.20 V. So, cell
RT ln K = nFE ° reaction is possible. The half-cell ∆G =–827 kJ mol –1
− 2−
nFE ° reactions are given as follows 12e + 6O → 3 O2
lnK =
RT (i) At negative pole 4 Al 3+ → Al + 12e −
2 × 0.46 A → A + + e – 4 3+ 4
lnK = (oxidation) or Al → Al + 4e −
0.0591 (ii) At positive pole 3 3
K = 3.68 × 10 15 ~− 4 × 10 15 B + + e – → B 4e − + 2O−2 → O2
(reduction) ∆G = − nEF ° (n = 4)
45 E ° 2+ = − 0.441 V and Hence, cell reaction is −827 × 10 3 J = − 4 × E ° × 96500
Fe /Fe
A + B + → A + + B, ° = + 0.20 V
E cell 827 × 10 3
E ° 3+ = 0.771V E=
Fe /Fe2+ 4 × 96500
47 The standard EMF of a galvanic cell E° = 2.14 V
the standard emf of the reaction
involving cell reaction with n = 2 is
Fe + 2Fe 3 + → 3Fe 2 + will be
[CBSE AIPMT 2006]
found to be 0.295 V at 25° C. The 49 The most convenient method to
(a) 0.111 V (b) 0.330 V
equilibrium constant of the protect the bottom of the ship
(c) 1.653 V (d) 1.212 V reaction would be made of iron is [CBSE AIPMT 2001]
Ans. (d) (Given F = 96500 C mol–1 , (a) coating it with red lead oxide
R = 8.314 JK –1 mol–1 ) (b) white tin plating
Given that E ° = − 0.441 V [CBSE AIPMT 2004]
Fe 2 + /Fe (c) connecting it with Mg block
So, Fe → Fe + 2e , 2+ − (a) 2.0 × 1011 (b) 4.0 × 1012
(d) connecting it with Pb block
E ° = + 0.441 V …(i) . × 102
(c) 10 . × 1010
(d) 10
Ans. (b)
and E° = 0.771 V Ans. (d)
Fe 3+ /Fe 2 + The most convenient method to protect
By Nernst equation, the bottom of ship made of iron is white
So, 2Fe3+ + 2 e − → 2 Fe2 + , 2 .303 RT
E ° = 0.771 V …(ii) E cell = E ° cell − log 10 K tin plating which prevents the build up of
nF barnacles.
°
50 Standard electrode potentials are On adding above equation we get, E cell = 0.00 V
2Cu+ Cu2+ + Cu ; ∆G − RT C2
Fe 2+ / Fe, E° = − 0.44 V º E= ln
∆G = ∆G 1 + ∆G2
Fe 3+ / Fe 2+ , E° = 0.77 V
nF C 1
− nFE ° = 0.15F + (−0.53F ) RT C2
Fe 2+ , Fe 3+ and Fe block are kept E= ln
−FE ° = = 0.38F nF C 1
together, then [CBSE AIPMT 2001]
E ° = 0.38V C2 > C 1
(a) Fe 3+ increases
Thus, for the result reaction E ° value is RT C2
(b) Fe2+ decreases 0.38 V. E= ln
nF C 1
Fe2 +
(c) 3+ remains unchanged (R, T, n and F are constant)
Fe 52 Which one of the following pairs of
C
(d) Fe2+ decreases substances on reaction will not therefore, E ° is based upon ln 2
C1
Ans. (b) evolve H2 gas? [CBSE AIPMT 1998]
(a) Iron and H2 SO 4 (aq) ∆G = − nFE °
The metals have higher negative values RT C2
of their electrode potential can displace (b) Iron and steam = − nF × ln
(c) Copper and HCl (aq) nF C 1
metals having lower values from their
salt solution. (d) Sodium and ethyl alcohol C2
= − RT ln
So, Fe3+ decreases. Ans. (c) C1
Since copper is placed below hydrogen Hence, at constant temperature Gibbs
51 Cu + (aq ) is unstable in solution and in the electrochemical series, thus C
free energy ∆G depends uponln 2 .
undergoes simultaneous oxidation copper does not give hydrogen with C1
and reduction according to the dilute acids. While all other pairs give
hydrogen on reaction. 55 E° for the cell,
reaction [CBSE AIPMT 2000]
Fe + dil. H2SO4 → FeSO4 + H2 ↑ Zn|Zn 2+ (aq )||Cu 2+ (aq )|Cu is 1.10 V
2Cu + (aq ) º Cu 2+ (aq ) + Cu( s ) 3Fe + 4H2O → Fe3O4 + 4H2 ↑ at 25°C. The equilibrium constant
Choose the correct E° for above Steam
for the reaction,
reaction if 2Na + C2H5OH → 2C2H5ONa + H2 ↑
Zn( s ) + Cu 2+ (aq ) Cu( s )
E ° 2+ = 0.34 V Cu + dil. HCl → No reaction º
Cu /Cu + Zn 2+ (aq ) is of the order
and E° = 0.15 V 53 Without losing its concentration [CBSE AIPMT 1997]
Cu2+ /Cu+
ZnCl 2 solution cannot be kept in (a) 10−37 (b) 10−28 (c) 1018 (d) 1017
(a) – 0.38 V (b) + 0.49 V (c) + Ans. (a)
0.38 V (d) – 0.19 V contact with [CBSE AIPMT 1998]
(a) Au (b) Al (c) Pb (d) Ag Zn(s ) + Cu2 + (aq) º Cu(s) + Zn 2+
(aq),
Ans. (c)
Ans. (b) E ° = + 1.10 V
∆G ° = − nFE ° 0.0591
From given data, In electrochemical series, Al is placed ∴ E° = log 10 K eq
above Zn and all other are present below n
(i) Cu(s ) → Cu2 + (aq) + 2e − , because at equilibrium, E cell = 0
Zn. So, aluminium displaces zinc from
∆G 1° = − 2 (− 0.34) × F ZnCl2 solution. Hence, it cannot keep in (n = number of electrons exchanged = 2)
(ii) Cu2 + (aq) + e − → Cu + (aq), contact with Al.
1.10 =
0.0591
log 10 K eq
∆G2° = − 1 (0.15) × F 2
54 For the cell reaction, 2.20
= log 10 K eq
On addition, Cu 2+ (C 1 , aq ) + Zn( s ) º 0.0591
Cu(s ) → Cu+ (aq) + e − ,
Zn 2+ (C 2 , aq ) + Cu(s) K eq = antilog 37.225 = 1.66 × 10 −37
∆G 3° = − 1 × E ° × F
of an electrochemical cell, the
and ∆G 3° = ∆G 1° + ∆G2° change in free energy (∆G) at a 56 Reduction potential for the
− n3FE ° = − n 1FE 1° − n2FE2 given temperature is a function of following half-cell reactions are
− E ° = − 2(−0.34) − 1(0.15)
[CBSE AIPMT 1998] Zn → Zn 2+ + 2 e − ,
= (−2 × − 0.34) + ( − 1 × 0.15)
(a) ln (C 1) (b) ln (C2 /C 1) (E ° 2+ = − 0.76 V)
(Zn /Zn)
(c) ln (C2 ) (d) ln (C 1 + C2 )
− E ° = + 0.68 − 0.15 = 0.53
Ans. (b) Fe → Fe 2+
+ 2 e− ,
or E ° = − 0.53 V
∆G = − nFE ° (E ° 2+ = − 0.44 V)
Cu+ (aq) º Cu2 + (aq) + e − ; Fe /Fe
For concentration cell, from Nernst
∆G 1 = − 1 × (−0.15) × F The EMF for the cell reaction,
equation,
Cu+ (aq) + e −
º Cu(s ) ;
°
E = E cell −
RT C 1
ln Fe 2+ + Zn → Zn 2+ + Fe will be
∆G2 = − 1 × (−0.53) × F nF C2 [CBSE AIPMT 1996]
(a) + 0.32 V TOPIC 4 (a) fuel cell

(b) – 0.32 V (b) electrolytic cell
(c) +1.20 V
Arrhenius Theory, Activation (c) dynamo
(d) – 1.20 V Energy and Collision Theory (d) Ni-Cd cell
Ans. (a)
of Biomolecular Gaseous Ans. (a)
Reaction
E° = − 0.76 V Fuel cell is a device that converts energy
Zn 2 + / Zn
of combustion of fuels like hydrogen and
59 In a typical fuel cell, the reactants
E° = − 0.44 V methane, directly into electrical energy.
Fe 2 + /Fe (R) and product (P) are
Electrolytic cell converts electrical
Cell reaction, [NEET (Oct.) 2020]
energy into chemical energy.
Fe2+
+ Zn → Zn 2+
+ Fe (a) R = H2 (g), O2 (g); P = H2O2 (l)
Dynamo is an electrical generator that
(b) R = H2 (g), O2 (g); P = H2O(l) produces direct current with the use of a
° = E °(cathode) − E °(anode)
E cell
(c) R = H2 (g), O2 (g), Cl2 (g) ; P = HClO 4 (aq) commutator.
= − 0.44 – (–0.76) (d) R = H2 (g), N2 (g);P = NH3 (aq) Ni-Cd cell is a type of rechargeable
= + 0.32 V Ans. (b) battery which consists of a cadmium
The reaction takes place in a fuel cell is anode and a metal grid containingNiO2
57 An electrochemical cell is shown +1 –2
acting as a cathode.
0 0
2H2 (g) + O2 (g) 2H2O(l) +
below Pt, H2 (1atm) | HCl (0.1 M) | [at anode] [at cathode] 62 A button cell used in watches
Product (P)
CH3COOH (0.1 M) | H2 (1 atm), Pt Reactants R functions as following [NEET 2013]
The EMF of the cell will not be Heat energy [gets converted Zn(s) + Ag 2O (s) + H2O (l)
zero, because [CBSE AIPMT 1995]
º
into electrical energy] 2Ag (s) + Zn 2+ (aq) + 2OH− (aq)
(a) EMF depends on molarities of acids
Hence, option (b) is the correct. If half-cell potentials are
used
(b) pH of 0.1 M HCl and 0.1 M CH3COOH is
60 Zinc can be coated on iron to Zn 2+ (aq) + 2e − → Zn (s),
not same
produce galvanised iron but the E° = − 0.76 V
(c) the temperature is constant
(d) acids used in two compartments are reverse is not possible. It is because Ag 2O (s) + H2O (l) + 2e −
[CBSE AIPMT 2016, Phase II]
different → 2Ag (s) + 2OH− (aq),E° = 0.34 V
Ans. (b) (a) zinc is lighter than iron
(b) zinc has lower melting point than iron
The cell potential will be
The EMF of the cell will not be zero (c) zinc has lower negative electrode (a) 1.10 V (b) 0.42 V
because concentration ofH+ ions in two potential than iron (c) 0.84 V (d) 1.34 V
electrolytic solutions is different. Mean (d) zinc has higher negative electrode Ans. (a)
HCl is strong acid where, acetic acid is potential than iron Anode is always the site of oxidation
weak acid and gives different pH.
Ans. (d) thus, anode half-cell is
The metal with higher negative standard Zn2 + (aq) + 2e − → Zn(s ), E ° = − 0.76 V
58 Standard reduction potentials at
reduction potential, have higher Cathode half-cell is
25°C of Li + / Li, Ba 2+ / Ba, Na + / Na tendency to get reduced. Ag2O( s ) + H2O(l ) + 2e − →
and Mg 2+ / Mg are –3.05, –2.90, Zn2 + + 2e – → Zn; E ° = −0 . 76 V 2Ag( s ) + 2OH− (aq ) ,
–2.71 and –2.37 V respectively. Fe2 + + 2e – → Fe; E ° = −0 .44 V E ° = 0.34 V
Which one of the following is the Here, in galvanised iron, Zn has higher E ° cell = E ° cathode − E ° anode
strongest oxidising agent? negative reduction potential means Zn = 0.34 − (− 0.76) = + 1.10 V
[CBSE AIPMT 1994] takes electrons given by iron and itself
(a) Mg2+ gets reduced. 63 The efficiency of a fuel cell is given
(b) Ba2+ Thus, Zn works as anode and protects by [CBSE AIPMT 2007]
iron from rusting by making iron as
(c) Na+ (a) ∆G / ∆ S (b) ∆G / ∆ H
cathode.
(d) Li+ (c) ∆ S / ∆G (d) ∆ H / ∆G
Ans. (a) 61 A device that converts energy of Ans. (b)
∆G
A cation having maximum (positive) value combustion of fuels like hydrogen Efficiency of a fuel cell (φ) = × 100
of standard reduction potential is the ∆H
and methane, directly into
strongest oxidising agent. Hence,Mg2 + electrical energy is known as Fuel cells are expected to have an
is the strongest oxidising agent. efficiency of 100%.
[CBSE AIPMT 2015]
11
Chemical Kinetics
TOPIC 1 Ans. (d) (c) 6.25 × 10 −3molL−1s−1
and 3.125 × 10 −3mol L−1s−1
Rate of Chemical Reaction, Let the order of reaction with respect to
A and B is x and y respectively. So, the (d) 1.25 × 10 −2 mol L−1s−1
Rate Expression rate law can be given as and 6.25 × 10 −3mol L−1s−1
R = k [A] x [B] y …(i) Ans. (b)
01 Mechanism of a hypothetical When the concentration of only B is Key Idea Rate of disappearance of
reaction X 2 + Y 2 → 2XY is given doubled, reactant = rate of appearance of product
below [NEET 2017] the rate is doubled, so or
(i) X 2 q X + X(fast) R 1 = k [A] x [2B] y = 2R …(ii) −
1 d [reactant]
Stoichiometric coefficient dt
(ii) X + Y 2 → XY + Y (slow) If concentrations of both the reactants A
and B are doubled, the rate increases by of reactant
(iii) X + Y → XY (fast) a factor of 8, so 1
=+
The overall order of the reaction R ′ ′ = k [2A] x [2B] y = 8R …(iii) Stoichiometric coefficient
will be ⇒ k2x 2y [A] x [B] y = 8R …(iv) of product d [product]
(a) 1 (b) 2 From Eqs. (i) and (ii), we get
dt
(c) 0 (d) 1.5 2R [A] x [2B] y
⇒ = For the reaction,
Ans. (d) R [A] x [B] y 1
N2O5 (g) → 2NO2 (g) + O2 (g)
We know that, slowest step is the rate 2 = 2y ⇒ y = 1 2
determining step. rom Eqs. (i) and (iv), we get − d [N2O5 ] 1 d [NO2 ] 2 d [O2 ]
∴ Rater (r) = K 1 [X] [Y2 ] … (i) 8R 2x 2y [A] x [B] y =+ =+
⇒ = or 8 = 2x 2y dt 2 dt dt
Now, from equation. (i), i.e. R [A] x [B] y d [NO2 ] d [N2O5 ]
X2 → 2X [fast] ∴ = −2
Substitution of the value of y gives, dt dt
[X]2 8 = 2x 21
K eq = = 2 × 6.25 × 10 −3 mol L−1 s−1
[X2 ] 4 = 2x = 12.5 × 10 −3 mol L−1 s−1
[X] = {K eq [X2 ]} 1/ 2 … (ii) (2)2 = (2) x = 1.25 × 10 −2 mol L−1 s−1
Now, substitute the value of [X] from ∴ x =2 d [O2 ] d [N2O5 ] 1
equation. (ii) in equation. (i), we get Substitution of the value of x and y in Eq. =− ×
dt dt 2
Rate (r) = K 1 (K eq ) 1/ 2 [X2 ] 1/2 [Y2 ] (i) gives,
6.25 × 10 −3 mol L−1s−1
= K [X2 ] 1/ 2 [Y2 ] R = k [A]2 [B] =
2
1 3
∴ Order of reaction = + 1 = = 1.5 = 3.125 × 10 −3 mol L−1s−1
2 2 03 For the reaction,
1
N 2O 5 (g) → 2NO 2 (g) + O 2 (g) 04 During the kinetic study of the
02 In a reaction, A + B → Product, rate 2
reaction, 2A + B → C + D,
is doubled when the concentration The value of rate of disappearance
following results were obtained
of B is doubled and rate increases of N 2O 5 is given as 6.25 × 10 −3 mol
by a factor of 8 when the L−1 s −1 . The rate of formation of NO 2 Initial rate of
and O 2 is given respectively as Run A/mol L−1 B/mol L−1 formation of
concentrations of both the D/mol L−1 min−1
[CBSE AIPMT 2010]
reactants (A and B) are doubled.
(a) 6.25 × 10 −3mol L−1s−1 I 0.1 0.1 6.0 × 10 −3
Rate law for the reaction can be
and 6.25 × 10 −3mol L−1s−1 II 0.3 0.2 7.2 × 10 −2
written as [CBSE AIPMT 2012] −2 −1 −1
(b) 1.25 × 10 mol L s III 0.3 0.4 2.88 × 10 −1
(a) rate = k [A][B] 2 (b) rate = k [A] 2 [B] 2 and 3.125 ×10 −3mol L−1s−1 IV 0.4 0.1 2.40 × 10 −2
(c) rate = k [A][B] (d) rate = k [A] 2 [B]
Chemical Kinetics 91
Based on the above data which one Ans. (a) The rate of this reaction is, given
of the following is correct? Rate of appearance/disappearance by
1
[CBSE AIPMT 2010] =± × (a) rate =k [A] 2 [B]
(a) Rate = k [A] 2 [B] stoichiometric coefficient
(b) rate =k [A][B] 2
[reactant or product]
(b) Rate = k [A] [B] (c) rate = k [A] 2 [B] 2
time taken
(c) Rate = k [A] 2 [B] 2 (d) rate = k [A][B]
For the reaction,
(d) Rate = k [A] [B] 2 Ans. (b)
BrO−3 (aq) + 5Br − (aq) + 6H+ → 3Br2 (l )
Ans. (d) For the reaction,
+ 3H2O(l )
Let the order of reaction with respect to A + B → Products
Rate of appearance of bromine (Br2 )
A is x and with respect to B is y.Thus, On doubling the initial concentration of A
1 d [Br2 ]
rate = k [A] x [B] y =+ only, the rate of the reaction is also
3 dt doubled, therefore
(x and y are stoichiometric coefficient )
For the given cases,
Rate of disappearance of bromide ion Rate ∝ [A] 1 …(i)
(Br − ) Let initial rate law is
I. rate = k (0.1) x (0.1) y = 6.0 × 10 −3 1 d [Br − ]
=− Rate = k [A][B] y …(ii)
II. rate = k (0.3) x (0.2) y = 7.2 × 10 −2 5 dt If concentration of A and B both are
III. rate = k (0.3) x (0.40) y = 2.88 × 10 −1 d [Br2 ] 3 d [Br − ] doubled, the rate gets changed by a
or =−
IV. rate = k (0.4) x (0.1) y = 2.40 × 10 −2 dt 5 dt factor of 8.
Dividing Eq. (I) by Eq. (IV), we get 8 × rate = k [2 A] [2 B] y …(iii)
x y −3 06 For the reaction, [Q Rate ∝ [A] 1]
 0.1   0.1  = 6.0 × 10
    N 2 + 3H2 → 2NH3 , if
 0.4   0.1  −
2.4 × 10 2 Dividing Eq. (iii) by Eq. (ii), we get
x 1 d [NH3] 8 = 2 × 2y
or  1 =  1
    = 2 × 10 −4 mol L−1 s −1 , the 4 = 2y
 4  4 dt (2)2 = (2) y
∴ x=1 −d [H2]
value of would be ∴ y =2
On dividing Eq. (II) by Eq. (III), we get dt [CBSE AIPMT 2009] Hence, rate law is,rate = k [A][B]2
7.2 × 10 −2
x y
 0.3   0.2 
    = (a) 3 × 10−4 mol L−1 s−1 08 The bromination of acetone that
 0.3   0.4  2.88 × 10 −1
(b) 4 × 10−4 mol L−1 s−1 occurs in acid solution is
y
 1
or   =
1 (c) 6 × 10−4 mol L−1 s−1 represented by this equation
 2 4 (d) 1 × 10−4 mol L−1 s−1
y 2 Ans. (a)
CH3COCH3 (aq) + Br 2 (aq) →
 1  1 CH3COCH2Br(aq) + H+ (aq) + Br − (aq)
or   = 
 2  2 For the reaction,
These kinetic data were obtained
∴ y =2 N2 + 3H2 → 2NH3
for given reaction concentrations.
Thus, rate law is, d [N2 ] 1 d [H2 ] 1 d [NH3] Initial concentrations, M
rate = k [A] 1 [B]2 Rate = − =− =+
dt 3 dt 2 dt [CH3COCH3] [Br2 ] [H + ]
= k [A] [B]2
1 d [H2 ] 1 d [NH3]
or − =+ 0.30 0.05 0.05
3 dt 2 dt
05 In the reaction, 0.30 0.10 0.05
d [H2 ] 3
BrO −3 (aq) + 5Br − (aq) + 6H+ → − = × 2 × 10 −4 mol L−1s−1 0.30 0.10 0.10
dt 2
3Br 2 (l) + 3H2O(l) −4 −1 −1 0.40 0.05 0.20
= 3 × 10 mol L s
the rate of appearance of bromine
Initial rate, disappearance of Br 2 ,
(Br 2 ) is related to rate of 07 For the reaction,
Ms–1
disappearance of bromide ions as A + B → products, it is observed 5.7 × 10−5
following. that
[CBSE AIPMT 2009, 2000] 5.7 × 10−5
I. On doubling the initial 1.2 × 10−4
d [Br2] 3 d [Br −]
(a) =− concentration of A only, the 3.1 × 10−4
dt 5 dt rate of reaction is also doubled
d [Br2] 5 d [Br −] Based on these data, the rate
(b) =− and equation is [CBSE AIPMT 2008]
dt 3 dt
II. On doubling the initial (a) rate = k [CH3COCH3][H+]
d [Br2] 5 d [Br −]
(c) = concentrations of both A and
dt 3 dt (b) rate = k [CH 2 == COCH3][Br2]
B, there is a change by a factor
d [Br2] 3 d [Br −] of 8 in the rate of the reaction. (c) rate = k [CH3COCH3][Br2][H+] 2
(d) =
dt 5 dt [CBSE AIPMT 2009] (d) rate = k [CH3COCH3][Br2][H+]
Ans. (a)
−
d [N2 ]
=−
1 d [H2 ]
=+
1 d [NH3] y = −2
Let the order of reaction wrt CH3COCH3, dt 3 dt 2 dt Hence, order of reaction with respect to
Br2 and H+ are x, y and z respectively. d [NH3] 2 d [H2 ] B is –2.
or + =−
Thus, dt 3 dt d [B]
Rate (r) = [CH3COCH3] x [Br2 ] y [H+ ] z d [NH3] 2d [N2 ] 12 3A → 2B, rate of reaction +
or + =− dt
5.7 × 10 −5 = (0.30) x (0.05) y (0.05) z …(i) dt dt
is equal to [CBSE AIPMT 2002]
5.7 × 10 −5 = (0.30) x (0.10) y (0.05) z …(ii) 3 d [A] 2 d [A]
10 For the reaction, (a) − (b) −
1.2 × 10 −4 = (0.30) x (0.10) y (0.10) z …(iii) 2 dt 3 dt
2A + B → 3 C + D 1 d [A] d [A]
(c) − (d) + 2
3.1 × 10 −4 = (0.40 )x (0.05)y (0.20 )z …(iv) which of the following does not 3 dt dt
From Eqs. (i) and (ii) express the reaction rate? Ans. (b)
y y
 1 or 1° =  
1 [CBSE AIPMT 2006]
1=   For reaction,
 2  2 d [C] d [B]
(a) – (b) – 3A → 2 B
y =0 3 dt dt
1 d [A]
d [D] d [A] Rate = −
From Eqs. (ii) and (iii) (c) (d) – 3 dt
z=1 dt 2 dt
[Rate of disappearance]
From Eqs. (i) and (iv) Ans. (a) 1 d [B]
=+
x=1 For the reaction, 2 dt
Thus, rate law ∝ [CH3COCH3] 1 [Br2 ] 0 [H+ ] 1 2A + B → 3 C + D [Rate of appearance]
= k [CH3COCH3][H+ ] The reaction rate is written as follows: d [B] 2 d [A]
∴ + =−
The reaction rate with respect to dt 3 dt
09 Consider the reaction, 1 d [A]
A=−
N 2 (g) + 3H2 (g) → 2NH3 (g) 2 dt 13 3A → B + C It would be a zero
The equality relationship between The reaction rate with respect to order reaction, when
d [NH3] d [H2] B=−
d [B] [CBSE AIPMT 2002]
and – is
dt dt dt (a) the rate of reaction is proportional to
[CBSE AIPMT 2006] The reaction rate with respect to square of concentration of A
d [NH3] 1 d [H2 ] 1 d [C] (b) the rate of reaction remains same at
(a) =– C=+ any concentration of A
dt 3 dt 3 dt
(c) the rate remains unchanged at any
d [NH3] 2 d [H2 ] The reaction rate with respect to
(b) + =– concentration of B and C
3 dt d [D]
dt D= (d) the rate of reaction doubles if
d [NH3] 3 d [H2 ] dt concentration of B is increased to
(c) + =–
dt 2 dt Hence, the answer (a) is not correct double
d [NH3] d [H2 ] expression to represent the rate of the Ans. (b)
(d) =– reaction.
dt dt For reaction,
Ans. (b) 11 The rate of reaction between two 3A → B + C
For the reaction, reactants A and B decreases by a If it is zero order reaction, then the rate
remains same at any concentration of A
N2 ( g) + 3H2 ( g) → 2NH3 ( g) factor of 4, if the concentration of dx
or = k [A 0 ] [A 0 = 1].
The rate of reaction wrt reactant B is doubled. The order of dt
d [N2 ] this reaction with respect to
N2 = − It means that for zero order reaction,
dt reactant B is [CBSE AIPMT 2005] rate is independent of concentration of
[Rate of disappearance] (a) −1 (b) −2 reactants.
The rate of reaction with respect to (c) 1 (d) 2
1 d [H2 ] Ans. (b) 14 For the reaction,
H2 = −
3 dt A + B → Product 2N 2O 5 → 4NO 2 + O 2 , rate and
[Rate of disappearance] Rate, r ∝ [A] x [B] y …(i) rate constant are 1.02 × 10 −4 and
The rate of reaction with respect to The rate decreases by a factor 4 if the 3 .4 × 10 −5 s −1 respectively, then
1 d [NH3] concentration of reactant B is doubled concentration of N 2O 5 at that time
NH3 = +
2 dt r
∝ [A] x [2 B] y …(ii) will be [CBSE AIPMT 2001]
[Rate of appearance] 4
(a) 1.732 (b) 3
From Eqs. (i) and (ii)
y . × 10−4
(c) 102 (d) 3 .4 × 105
Hence, at a fixed time  1
4=   Ans. (b)
 2
2N2O5 → 4NO2 + O2 Rate constant (k) = 4.606 × 10 − 3 s− 1 19 If the rate constant for a first order
–d [N2O5 ] Initial amount (a 0 ) = 2g reaction is k, the time (t) required
= k ⋅ [N2O5 ]
Final amount (a) = 0.2 g
dt for the completion of 99% of the
So, time required,
. × 10 –4 = 3 .4 × 10 –5 s–1 × [N2O5 ]
102 reaction is given by
2.303 a
t= log 0 [NEET (National) 2019]
1.02 × 10 –4 k a
∴ [N2O5 ] = =3 (a) t = 6.909/k (b) t = 4.606/k
3.4 × 10 –5 2.303 2
= × log = 500 s (c) t = 2.303/k (d) t = 0.693/k
4.606 × 10 − 3 0.2
15 The experimental data for the Ans. (b)
reaction 2 A+B2 → 2 AB is 17 The half-life for a zero order Key Idea For first order reaction,
reaction having 0.02 M initial 2 .303 a
Exp. [A] [B2] Rate (M s −1)
t= log
concentration of reactant is 100 s. K a−x
. × 10 −4
1. 0.50 0.50 16
The rate constant (in mol L −1 s −1 ) where,a = initial concentration,a − x =
2. 0.50 1.00 3. 2 × 10 −4 for the reaction is [NEET (Oct.) 2020] final concentration.
3. 1.00 1.00 3. 2 × 10 −4 (a) 1.0 × 10−4 (b) 2.0 × 10−4 Let the initial concentration (a) = 100
After timet, final concentration
(c) 2.0 × 10−3 (d) 1.0 × 10−2
The rate equation for the above (a − x) = 100 − 99 = 1
Ans. (a) 2 .303 a
data is [CBSE AIPMT 1997] We know that, t = log
1 a−x
(a) rate = k [B2] (b) rate = k [B2] 2 For a zero order reaction,t = (a 0 − a) K
k
(c) rate = k [A] [B] (d) rate = k [A] 2 [B]
2 2
1 a0
On substituting the given values in above
⇒ t 50 = × [Qat t 50 , a = a 0 /2] eqn. we get
Ans. (a) k 2 2.303 100 2 .303
Consider the following rate law equation, a0 0.02 M t= log = log 102
⇒ k= = K 1 K
dx
= k [A] m [B2 ] n 2 × t 50 2 × 100 s 2.303 4606
.
dt = × 2log 10 =
= 1 × 10 − 4 Ms− 1 = 1 × 10 − 4 mol L− 1 s− 1 K K
1 .6 × 10 −4 = k [0.50] m [0.50] n ...(i)
Thus, option (b) is correct.
3 .2 × 10 −4 = k [0.50] m [10 . ]n ...(ii) 18 A first order reaction has a rate
−4
3 . 2 × 10 = k [100 constant of2.303 × 10 −3 s −1 . The
m
. ] [10 . ]n ...(iii) 20 The correct difference between
By dividing Eq. (iii) by (ii) we get, time required for 40 g of this first-and second- order reactions is
3 .2 × 10 −4 k [1.00] m [1.0] n reactant to reduce to 10 g will be that
= [NEET 2018]
3 .2 × 10 −4 k [0.50] m [1.0] n [Given that log 10 2 = 0.3010] (a) a first-order reaction can be
1 = 2m or 20 = 2m [NEET (Odisha) 2019] catalysed; a second-order reaction
cannot be catalysed
∴ m=0 (a) 230.3 s (b) 301 s
(b) the half-life of a first-order reaction
By dividing Eq. (ii) by (i) (c) 2000 s (d) 602 s
does not depend on [A] 0 ; the
3 .2 × 10 −4 [0.50] m [1.0] n Ans. (d) half-life of a second-order reaction
=
1.6 × 10 −4 [0.50] m [0.50] n For first order reaction, does depend on [A] 0
2 = 2n or 21 = 2n 2.303 a (c) the rate of a first-order reaction does
t= log …(i)
k a−x not depend on reactant
∴ n= 1
concentrations; the rate of a
Hence rate, Given : k = 2.303 × 10 −3 s−1,
second-order reaction does depend
 dx  a = 40 g, a − x = 10 g on reactant concentrations
  = k [A] [B2 ] = k [B2 ]
0 1
 dt  On substituting the given values in Eq. (i), (d) the rate of a first-order reaction does
we get depend on reactant concentrations;
2.303 40 the rate of a second-order reaction
t= log
TOPIC 2 2.303 × 10 −3 10 does not depend on reactant
concentrations
Order and Molecularity = 10 3 log 22 = 2 × 10 3 × log 2
= 2 × 10 3 × 0.3010 = 602 s Ans. (b)
Alternative method For first order reactions, the rate of
16 The rate constant for a first order reaction is proportional to the first
For first order reaction,
reaction is 4.606 × 10 −3 s −1 . The power of the concentration of the
0.693
time required to reduce 2.0 g of t 1/ 2 = reactant .
k For, A → B
the reactant to 0.2 g is
0.693 d [A]
[NEET (Sep.) 2020] t 1/ 2 (t 50%) = = 301s Rate = − = k [A]
(a) 200 s (b) 500 s 2.303 × 10 −3 dt
(c) 1000 s (d) 100 s Also, t 75% = 2t 50% [where, k = constant]
Ans. (b) 0.693
∴ t 75% = 2 × 301 = 602 s Half-life (t 1/ 2 ) =
For a first order reaction, k
∴ Rate of first order reaction depends Alternatively, (a) rate is proportional to the surface
upon reactant concentrations and half Half-life for the first order reaction, coverage
life does not depend upon initial t 1/ 2 0.693 0.693 (b) rate is inversely proportional to the
concentration of reactant, [A] 0 . = = −2 = 69.3 s surface coverage
2 k 10
For second order reactions, the rate of (c) rate is independent of the surface
reaction is proportional to the second Two half-lives are required for the coverage
power of the concentration of the reduction of 20 g of reactant into 5 g. (d) rate of decomposition is very slow
t1/2 t1/2
reactant. 20 g → 10 g → 5 g. Ans. (a)
For, 2A → B ∴ Total time = 2t 1/ 2 W 3
Rate = k [A]2 PH3 → P + H2
= 2 × 693 . = 1386
. s 2
1
Half-life (t 1/ 2 ) = This is an example of surface catalysed
k [A] 0 23 The rate constant of the reaction unimolecular decomposition.
∴ Rate of second order reaction A → B is 0.6 × 10 −3 mole per second. For the above reaction, rate is given as
depends upon reactant concentration If the concentration of A is 5 M then kαp
and half life also does depend on [A] 0 . Rate =
concentration of B after 20 min is 1 + αp
[CBSE AIPMT 2015]
21 When initial concentration of the where, p = partial pressure of absorbing
(a) 1.08 M (b) 3.60 M substrate.
reactant is doubled, the half-life (c) 0.36 M (d) 0.72 M At low pressure, αp<< 1 or Rate = kαp
period of a zero order reaction
[NEET 2018]
Ans. (d) So, (αp + 1) can be neglected.
(a) is tripled Key Concept For a zero order reaction hus, the decomposition is predicted to
unit of rate constant is mole per second. be first order.
(b) is doubled
Hence, we can easily calculate
(c) is halved concentration of B after 20 min by the 26 When initial concentration of a
(d) remains unchanged following formula, reactant is doubled in a reaction,
Ans. (b) x = Kt its half-life period is not affected.
For zero order reaction, x = Kt = 0.6 × 10 −3 × 20 × 60 = 0.72 M The order of the reaction is
[R] 0
t 1/ 2 = [CBSE AIPMT 2015]
2k 24 The rate of a first-order reaction is (a) zero
where, [R] 0 = Initial concentration of the 0.04 mol L−1 s −1 at 10 sec and 0.03 (b) first
reactant. mol L−1 s −1 at 20 sec after initiation (c) second
k = Rate constant. of the reaction. The half-life period (d) more than zero but less than first
Thus, t 1/ 2 for zero order reaction is of the reaction is Ans. (b)
directly proportional to the initial [NEET 2016, Phase I]
concentration of the reactant. For a zero order reactiont 1/ 2 is directly
(a) 34.1 s (b) 44.1 s (c) 54.1 s (d) 24.1 s
proportional to the initial concentration
t 1/ 2 ∝ [R] 0 Ans. (d) of the reactant [R]0
∴ For zero order reaction, when the
Given, order of reaction = 1 t 1/ 2 ∝ [R]0
concentration of reactant is doubled, the
half-life (t 1/ 2 ) will also get doubled. Rate of reaction at 10 s = 0.04 mol L −1 s −1 For a first order reaction
Rate of reaction at 20 s = 0.03 mol L −1 s −1 k=
2303
. [R]
log 0
22 A first order reaction has a specific ∴ Half-life period (t 1/ 2 ) = ? t [R]
reaction rate of 10 −2 s −1 . How much We have the equation for rate-constant ‘ at t 1/ 2 , [R] =
[R] 0
time will it take for 20 g of the k’ in first order reaction. 2
2303
. A 2.303 0.04
reactant to reduce to 5 g? k= log t = log So, the above equation becomes
[NEET 2017] t A0 105 0.03 2303
. [R] 0
2.303 K= log
(a) 238.6 s (b) 138.6 s = × 0.124 t 1/ 2 [R]0 /2
(c) 346.5 s (d) 693.0 s 105
2303
. 2303
.
k = 0.028 s−1 t 1/ 2 = = log 2= × .3010
Ans. (b) K K
We know that, .693
For a first order reaction, t 1/ 2 =
0.693 0.693
Rate constant (k) =
.
2303 a t 1/ 2 = = K
log k 0.028773391 s−1
t a−x i.e., half life period is independent of
where,a = initial concentration = 24.14 s ≈ 24.1 s initial concentration of a reactant.
a − x = concentration after time ‘t’
25 The decomposition of phosphine 27 Which one of the following
t = time in sec.
(PH 3 ) on tungsten at low pressure is statements for the order of a
Given, a = 20 g, a − x = 5 g, k = 10 −2
2303
. 20
a first-order reaction. It is because reaction is incorrect?
∴ t = −2 log = 1386. s the [NEET 2016, Phase II] [CBSE AIPMT 2011]
10 5
(a) Order is not influenced by is first order reaction with respect toH2 Ans. (d)
stoichiometric coefficient of the and ICI. Thus, the mechanism B will be For first order reaction,
reactants more consistent with the given 2.303 a
(b) Order of reaction is sum of power to information. Rate constant, k = log
t (a − x)
the concentration terms of
reactants to express the rate of 30 If 60% of a first order reaction was 2.303 a  a
t 1/ 2 = log x = 
reaction completed in 60 min, 50% of the k a−
a  2
(c) Order of reaction is always whole 2
same reaction would be completed
number 2.303 ln2
in approximately (log 4 = 0.60, = log 2 or =
(d) Order can be determined only k k
experimentally log 5 = 0.69) [CBSE AIPMT 2007]
Ans. (c) (a) 50 min (b) 45 min 32 For a first order reaction, A → B,
(c) 60 min (d) 40 min
Order of reaction may be zero, whole the reaction rate at reactant
number or fraction number. Ans. (b)
concentration of 0.01 M is found to
From first order reaction,
be 2.0 × 10–5 mol L–1 s–1 . The half-life
28 Half-life period of a first order Rate constant,
reaction is 1386s. The specific rate 2.303 a period of the reaction is
k= log 10 [CBSE AIPMT 2005]
constant of the reaction is t (a − x)
(a) 220 s (b) 30 s
[CBSE AIPMT 2009] 2.303 a1
−3 −1 −2 −1 k1 = log …(i) (c) 300 s (d) 347 s
(a) 5.0 × 10 s (b) 0.5 × 10 s t1 a1 − x1
Ans. (d)
(c) 0.5 × 10−3 s−1 (d) 5.0 × 10−3 s−1 2.303 a2
k2 = log …(ii) For first order reaction,
Ans. (c) t2 a2 − x2
A → B
Specific rate constant, 60
x1 = a 1,t 1 = 60 rate = k × [A]
0.693 0.693 100
k= = Rate = 2.0 × 10 –5 mol L–1s–1
t 1/ 2 1386 50
x2 = a2 ,t2 = ? [A] = 0.01 M
100
= 0.5 × 10 −3 s−1 So, 2 .0 × 10 −5 = k × 0.01
From Eqs. (i) and (ii)
2.303 a1 2.303 a2 2.0 × 10 –5 –1
29 The reaction of hydrogen and log = log k= s
t1 a1 − x1 t2 a2 − x2 0.01
iodine monochloride is given as −3 −1
= 2 .0 × 10 s
2.303 a1 2.303
H2 (g) + 2ICl(g) → 2HCl(g) + I 2 (g) log = log For first order reaction,
60  a − 60 a  t2
This reaction is of first order with  1 1
t 1/ 2 =
0.693
 100  a2
respect to H2 (g) and ICl(g), k
 50 
following mechanisms were  a2 − a2 
=
0.693
 100 
proposed 2 .0 × 10 −3
2.303 100a 1 2.303 100a2
Mechanism A log = log =346.5 ≈ 347 s
60 40a 1 t2 50a2
H2 (g) + 2ICl(g) → 2HCl(g) + I 2 (g) 1 100 1 100
log = log 33 The rate of first order reaction is
Mechanism B 60 40 t2 50 1.5 × 10 −2 mol L–1 min–1 at 0.5 M
H2 (g) + ICl(g) → HCl(g) + HI(g), 60 log
100
concentration of the reactant. The
slow t2 = 50
100 half-life of the reaction is
HI(g) + ICl(g) → HCl(g) + I 2 (g), fast log [CBSE AIPMT 2004]
40
Which of the above mechanism(s) 60 (log 10 − log 5) (a) 0.383 min (b) 23.1 min
=
can be consistent with the given (log 10 − log 4) (c) 8.73 min (d) 7.53 min
information about the reaction? 60(1 − 0.69) 60 × 0.31 Ans. (b)
[CBSE AIPMT 2007] = =
(1 − 0.60) 0.40 For the first order reaction,
(a) Only B = 1.5 × 31 = 46.5 ≈ 45 min  dx 
Rate   = k [A]
(b) Both A and B  dt 
(c) Neither A nor B 31 In a first order reaction, A → B, [A] = concentration of reactant
(d) Only A if k is rate constant and initial k = rate constant
Ans. (a) concentration of the reactant A is Given that,
In the reactions which take place in a 0.5 M, then the half-life is dx
[CBSE AIPMT 2007] = 1.5 × 10 − 2 mol L–1 min–1
number of steps, the slowest step is dt
known as the rate determining step. 0.693 log 2
(a) (b) k=?
Hence, rate of reaction always depends 0.5k k
on slow step. and [A] = 0.5 M
log 2 ln2
H2 (g) + ICl(g) → HCl(g) + HI (g) (c) (d) ∴ 1.5 × 10 − 2 = k × 0.5
k 0.5 k
1.5 × 10 − 2 (c) first power of final concentration For first order reaction
∴ k=
0.5 (d) square root of final concentration A0 = Initial concentration
= 3 × 10 − 2 min−1 Ans. (a) A = Final concentration
For first order reaction, 1 2.303 [A] 0
t 1/ 2 of nth order reaction ∝ Rate constant, k = log
0.693 0.693 a n –1 t [A]
half-life period,t 1/ 2 = =
k 3 × 10 −2 where,a = initial concentration of =
2.303
log
2.0
= 23.1 min reactant 200 0.15
n= order of reaction 2.303
= (log 200 − log 15)
34 If the rate of a reaction is equal to ∴t 1/ 2 for first order reaction (n = 1) 200
the rate constant, the order of the 1
t 1/ 2 ∝ 1– 1 =
2.303
× (2.3010 − 1.1761)
reaction is [CBSE AIPMT 2003] a 200
1
(a) 2 (b) 3 (c) 0 (d) 1 or t 1/ 2 ∝ 0 (a 0 = 1) 2.303 × 1.1249
a =
Ans. (c) 200
So, for a first order reaction half-life is
Rate of reaction is equal to the rate
independent on initial concentration of = 0.01295 min−1
constant for zero order reaction. 0.6932
reactants. Now, half life,t 1/ 2 =
Let us consider the following k
hypothetical change. 37 The plot of concentration of the 0.6932
=
A → B + C reactant versus time for a reaction 0.01295
Suppose this reaction is zero order, then is a straight line with a negative = 53.50 min
rate ∝ [A] 0 slope. This reaction follows
∴ rate = k [A] 0 = k [CBSE AIPMT 1996]
(a) zero order rate equation
TOPIC 3
35 The reaction, A→ B follows first (b) first order rate equation Activation Energy, Arrhenius
order kinetics. The time taken for (c) second order rate equation and Collision Theory, Factors
0.8 mole of A to produce 0.6 mole (d) third order rate equation Affecting Rate of Reaction
of B is 1h. What is the time taken Ans. (b)
for the conversion of 0.9 mole of A For first order reaction, we know that 39 For a reaction, A → B, enthalpy of
to 0.675 mole of B ? log [A] = −
kt
+ log [A] 0 reaction is − 4.2 kJ mol −1 and
[CBSE AIPMT 2003] 2.303 enthalpy of activation is 9.6 kJ mol
(a) 0.25 h (b) 2 h (c) 1 h (d) 0.5 h −1
On comparing it with the equation of . The correct potential energy
Ans. (c) straight line, profile for the reaction is shown in
Rate constant of first order reaction i.e. y = mx + c option. [NEET 2021]
2 .303 (A) Plot of log [A] versus time
k= log 10 0
t (A) t → straight line
−k
2 .303 0.8 slope = (negative)
or k= × log 10 ...(i) 2.303
1 0.2 PE B
(a)
(because 0.6 mole of B is formed) A
Suppose t 1 hour are required for log [A]
changing the concentration of A from Reaction progress
0.9 mole to 0.675 mole of B. slope (m) = –k
log [A]0 2.303
Remaining mole of A = 0.9 − 0.675 = 0.225
2 .303 0.9
∴ k= log 10 ...(ii)
t1 0.225
t
From Eqs. (i) and (ii) PE A
(b)
2 .303 0.8 2 .303 0.9 B
log 10 = log 10 38 A substance A decomposes by a
1 0.2 t1 0.225 Reaction progress
first order reaction starting initially
2 .303
2 .303 log 10 4 = log 10 4 ⇒ t 1 = 1 h with [A] = 2.00 m and after 200 min,
t1
[A] becomes 0.15 m. For this
reaction t 1/ 2 is [CBSE AIPMT 1995]
36 For a first-order reaction, the
(a) 53.49 min (b) 50.49 min
half-life period is independent of (c)
PE
[CBSE AIPMT 1999]
(c) 48.45 min (d) 46.45 min A B
(a) initial concentration Ans. (a)

Reaction progress
(b) cube root of initial concentration [A] 0 = 2.0 m, [A] = 0.15 m, t = 200 min
Ans. (b) (c) Enzymes catalyse mainly

From collision theory of chemical biochemical reaction
reaction, Arrhenius equation. (d) Coenzymes increase the catalytic
B − E / RT activity of enzyme
PE A We get, k = A × e a
(d) Ans. (b)
where, k = rate constant,
− E / RT For a reversible reaction, it accelerates
e a = fraction of molecules with
Reaction progress the speed of forward as well as
energy greater than E a atT K. (option-(a)) backward reaction to the same extent.
Ans. (b) A = Arrhenius factor or frequency factor Hence, it does not disturb the
The enthalpy of reaction is negative, = P × Z AB equilibrium, i.e. does not change the
– 4.2 kJ mol −1. The reaction is an when, P = steric factor (option-(c)) equilibrium constant of the reaction but
exothermic reaction i.e. the energy of Z AB = collision frequency of reactants, A helps to attain the equilibrium faster.
product B, is less than the energy of and B
reactant A. So, the potential energy 44 The addition of a catalyst during a
= number of effective binary collisions
profile for the reaction is chemical reaction alters which of
between A and B in one second in unit
volume (option-(b)). the following quantities?
9.6 kJ mol –1 Hence, option (b) is the correct. [NEET 2016, Phase I]
PE
A (a) Internal energy
–4.2 kJ mol –1 42 For a reaction, activation energy (b) Enthalpy
B E a = 0 and the rate constant at (c) Activation energy
200K is 1.6 × 10 6 s −1 . The rate (d) Entropy
Reaction process
constant at 400 K will be Ans. (c)
40 The slope of Arrhenius plot [Given that gas constant
A catalyst is a substance which alters
 1 R = 8.314 JK −1 mol −1 ] the reaction rate but itself remains
ln k vs  of first order reaction is
 T
[NEET (Odisha) 2019] unchanged in amount and chemical
(a) 3.2 × 104 s−1 (b) 1.6 × 106 s−1 composition at the end of the reaction. It
− 5 × 10 3 K. The value of E a of the (c) 1.6 × 103 s−1 (d) 3.2 × 106 s−1 provides a new reaction path with a
reaction is Ans. (b) lower energy barrier (lowering activation
[Given, R = 8.314 JK − 1 mol − 1 ] Key Idea Rate constants at two
energy).
[NEET 2021] Activated complex
−1 −1
different temperatures is given by B without catalyst
(a) 41.5 kJ mol (b) 83.0 kJ mol Arrhenius equation as follows : Activated complex with catalyst
(c) 166 kJ mol − 1 (d) − 83 kJ mol − 1 k Ea  1 1  Lowest energy
log 2 =  − ,T2 > T1 of activation
Ans. (a) k1 2303. R T1 T2  Ea provided by the
Energy
catalyst through new

Arrhenius equation,
. × 10 6 s−1
ER
− E / RT
Given, E a = 0, T1 = 200 K, k1 = 16 reaction pathway
k = Ae a T2 = 400 K,
Reactants
ln k = ln A − a  
E 1 . JK −1 mol −1
R = 8314 EP
R T  According to Arrhenius equation,
Products
−E a Progress of reaction
is the slope of Arrhenius plot k Ea  1 1
R log 2 =  − 
 ln k vs 1  k1 2.303R T1 T2 
 
 T 45 The activation energy of a reaction
On substituting the given values in above
ln A is the intercept equation, we get can be determined from the slope
Slope = − 5 × 10 3 K k2 0  1 1  of which of the following graphs?
log = −
R = 8.314 J K–1 mol –1 . × 10 6 2.303 × 8314
16 .  200 400  [CBSE AIPMT 2015]
Ea In K
So, − = − 5 × 10 3 K  k2  (a) In K vs T (b) vs T
R log   =0 T
 16
. × 10 6 
⇒ E a = 5 × 10 3 × R = 5 × 10 3 × 8.314 I T I
k2 (c) In K vs (d) vs
= 41.57 × 10 3 J mol −1 = 41.5 kJ mol −1 = 10 0 = 1 T In K T
. × 10 6
16
41 In collision theory of chemical . × 10 6 s−1 at 400K
k2 = 16 Ans. (c)
reaction, Z AB represents Thus, option (b) is correct. By Arrhenius equation
[NEET (Oct.) 2020] K = Ae − Ea / RT
(a) the fraction of molecules with
43 Which one of the following
statements is not correct? where, E a = energy of activation
energies greater than E a
[NEET 2017] Applyinglog on both the side,
(b) the collision frequency of reactants, E
(a) Catalyst does not initiate any ln k = ln A − a …(i)
A and B
reaction RT
(c) steric factor
(b) The value of equilibrium constant is Ea
(d) the fraction of molecules with
changed in the presence of a or log k = − + log A …(ii)
energies equal to E a 2303
. RT
catalyst in the reaction equilibrium
Compare the above equation w.r.t. 47 In a zero order reaction for every 49 The rate constants k 1 and k 2 for
straight line equation of y = mx + c. 10°C rise of temperature, the rate is
1 two different reactions are
Thus, if a plote oflnk vs is a straight doubled. If the temperature is
T 10 16 ⋅ e −2000 /T and 10 15 ⋅ e −1000 /T ,
line, the validity of the equation is increased from 10°C to 100°C, the
respectively. The temperature at
confirmed. rate of the reaction will become
E [CBSE AIPMT 2012] which k 1 = k 2 is [CBSE AIPMT 2008]
Slope of the line = − a 2000
R (a) 256 times (b) 512 times (a) 1000 K (b) K
(c) 64 times (d) 128 times 2.303
Thus, measuring the slope of the line, 1000
the value of Ans. (b) (c) 2000 K (d) K
2.303
E a can be calculated. For 10° rise in temperature, n = 1
Ans. (d)
so rate = 2n = 21 = 2
Given, k1 = 10 16 ⋅ e −2000 / T
When temperature is increased from
Ea 10°C to 100°C, change in temperature k2 = 10 15 ⋅ e −1000 / T
lnk
slope = –
R = 100 − 10 = 90 ° C On taking log of both the equations we
i.e. n=9 get
2000
So, rate = 29 = 512 times log k1 = 16 −
2.303T
1/T Alternate method with every 10° rise in
1000
temperature, rate becomes double, log k2 = 15 −
2.303T
 100 − 10 
46 What is the activation energy for a r′  
At k1 = k2
so =2 10 
= 29 = 512 times.
reaction if its rate doubles when r 2000 1000
the temperature is raised from 16 − = 15 −
2.303T 2.303T
20°C to 35°C? 48 For an endothermic reaction, 1000
T= K
(R = 8.314J mol −1 K −1 ) [ NEET 2013] energy of activation is E a and 2.303
(a) 342 kJ mol−1 enthalpy of reaction is ∆H (both of
(b) 269 kJ mol−1 these in kJ/mol). Minimum value of 50 The activation energy for a simple
(c) 34.7 kJ mol−1 E a will be [CBSE AIPMT 2010] chemical reaction, A → B is E a in
(d) 15.1 kJ mol−1 (a) less than ∆H forward direction. The activation
Ans. (c) (b) equal to ∆H energy for reverse reaction
Given, initial temperature, (c) more than ∆H [CBSE AIPMT 2003]
T1 = 20 + 273 = 293 K
(d) equal to zero (a) can be less than or more than Ea
Final temperature, Ans. (c) (b) is always double of Ea
T2 = 35 + 273 = 308 K Key Idea In endothermic reactions, (c) is negative of Ea
. J mol −1 K−1
R = 8314 energy of reactants is less than that of (d) is always less than Ea
the products. Ans. (a)
Since, rate becomes double on raising
temperature, Potential energy diagram for endothermic
The energy of activation of reverse
r reactions is
reaction is less than or more than energy
∴ r2 = 2r1 or 2 = 2
r1 of activation (E a ) of forward reaction.
As rate constant, k ∝ r ∴ ∆H = (E a ) F − (E a ) R
k2 Ea' Because it depends upon the nature of
∴ =2 Ea reaction.
k1
Potential P
If (E a ) F > (E a ) R , reaction is endothermic
From Arrhenius equation, we know that Energy
∆H or (E a ) F < (E a ) R , reaction is exothermic
k E a T1 − T2 
log 2 = −  
R
k1 2.303 R  TT1 2  Progress of the reaction 51 The temperature dependence of rate
Ea  293 − 308  constant (k ) of a chemical reaction is
log 2 = − where,
.  293 × 308 
2.303 × 8314 written in terms of Arrhenius equation,
E a = activation energy of forward
Ea  −15  reaction k = Ae −E */ RT . Activation energy (E*) of
0.3010 = −
.  293 × 308 
2.303 × 8314 activation energy of backward reaction the reaction can be calculated by
∴ ∆H = enthalpy of the reaction. plotting [CBSE AIPMT 2003]
0.3010 × 2.303 × 8.314 × 293 × 308 From the above diagram, 1 1
Ea = (a) log k vs (b) log k vs
15 E a = E a′ + ∆H T log T
= 34673.48 J mol −1 1
Thus, E a > ∆H (c) k vs T (d) k vs
= 34.7 kJ mol −1 log T
Ans. (a) 53 Activation energy of a chemical 55 A chemical reaction is catalysed by

Arrhenius equation k = Ae − E * / RT reaction can be determined by a catalyst X. Hence, X
E*
ln k = ln A − [CBSE AIPMT 1998] [CBSE AIPMT 1995]
RT (a) evaluating rate constant at standard (a) reduces enthalpy of the reaction
(E * = energy of activation) temperature (b) decreases rate constant of the
E* (b) evaluating velocities of reaction at reaction
or log k = log A −
2 .303 RT two different temperatures (c) increases activation energy of the
(c) evaluating rate constants at two reaction
Compare this equation with the straight
different temperatures (d) does not affect equilibrium constant
line equation,
(d) changing concentration of reactants of the reaction
i.e. y = mx + c
Ans. (c) Ans. (d)
where ‘m’ is slope and ‘c’ is intercept
Activation energy can be calculated by Although a catalyst speeds up the
Hence, E * can be calculated with the using Arrhenius equation. The Arrhenius reaction but it does not shift the position
help of following slope equation is of equilibrium. This is due to the fact
k E a T2 − T1  that the presence of catalyst reduces
log A log 2 =   the height of barrier by providing an
E* k1 2 .303 R  TT1 2 
Slope () = m alternative path for the reaction and
2.303 R
log k where, k1 and k2 = rate constants at two lowers the activation energy. However,
different temperatures, i.e.T1 andT2 the lowering in activation energy is to
respectively. the same extent for the forward as well
E a = Activation energy as the backward reaction.
1
T R = Gas constant
So, activation energy of a chemical
56 For exothermic reaction, the
52 When a biochemical reaction is reaction can be determined by energy of activation of the
carried out in laboratory from evaluating rate constants at two reactants is [CBSE AIPMT 1994]
outside of human body in the different temperatures. (a) equal to the energy of activation of
products
absence of enzyme, the rate of
54 In a reversible reaction, the energy (b) less than the energy of activation of
reaction obtained is 10 −6 times, products
of activation of the forward
then activation energy of the (c) greater than the energy of activation
reaction is 50 kcal. The energy of
reaction in the presence of enzyme of products
activation for the reverse reaction
is [CBSE AIPMT 2001] (d) sometimes greater and sometimes
6 will be [CBSE AIPMT 1996]
less than that of the products
(a) (a) < 50 kcal
RT Ans. (b)
(b) P is required (b) 50 kcal
The plot of activation energy versus
(c) different from E a obtained in (c) either greater than or less than 50 kcal reaction coordinates is given below for
laboratory (d) > 50 kcal exothermic reaction.
(d) cannot say any things Ans. (c)
Ans. (c) The activation energy of a reverse Activation
(Ea )R
When a biochemical reaction is carried reaction decide whether the given energy
out in laboratory from outside of human reaction is exothermic or endothermic, (Ea )P
body in the absence of enzyme, then rate so, the energy of activation of reverse
of reaction obtained is 10 –6 times than reaction is either greater or less than Reactant
∆ rH
activation energy of reaction in the 50 kcal. In case of exothermic reaction, Product
presence of enzyme. It is different from the activation energy for reverse
E a obtained in laboratory because for a reaction is more than activation energy Reaction coordinates
given chemical reaction. of the forward reaction and in case of
− E / RT
k = Ae a (Arrhenius equation) endothermic reaction, the activation It is clear from the above plot that the
energy for reverse reaction is less than activation energy of reactant is less than
Also activation energy have different activation energy of the forward the activation energy of products.
value in absence or presence of reaction.
enzyme.
12
Surface Chemistry
TOPIC 1 As the process is exothermic and The value of n is always greater than 1.
randomness of molecule (entropy) So, the value of 1/n lies between 0 and 1
Adsorption and decreases hence, both ∆H and ∆S will be in all cases.
Various Isotherms negative as well.
05 If x is amount of adsorbate and m is
01 The correct option representing a 03 Which of the following statements amount of adsorbent, which of the
Freundlich adsorption isotherm is is correct for the spontaneous following relations is not related to
[NEET (Odisha) 2019] adsorption of a gas? adsorption process?
x x [CBSE AIPMT 2014]
(a) = kp 0. 3 (b) = kp2. 5 (a) ∆S is negative and therefore, ∆H
[CBSE AIPMT 2011]
m m x
should be highly positive (a) = f (T ) at constant p
x x m
(c) = kp −0. 5 (d) = kp −1 (b) ∆S is negative and therefore, ∆H
m m  x
should be highly negative (b) p = f (T ) at constant  
Ans. (a) (c) ∆S is positive and therefore, ∆H  m
should be negative x
According to Freundlich adsorption (c) = p × T
isotherm, (d) ∆S is positive and therefore, ∆H m
x should also be highly positive x
= kp1/ n (d) = f (p) at constant T
m Ans. (b) m
x
where, = amount of the gas adsorbed ∆S [change in entropy] and ∆H [change Ans. (c)
m in enthalpy] are related by the equation x
= p × T is the incorrect relation. The
per unit mass of adsorbent ∆G = ∆ H − T ∆S m
p = pressure k and n = constants. [Here, ∆G = change in Gibbs free energy] correct relation is amount of adsorption
x p
The value of n lies in between 0 to 1. For adsorption of a gas, ∆S is negative ∝
x because randomness decreases. Thus, m T
Thus, = kp0. 3 and option (a) is correct.
m in order to make ∆G negative [for
spontaneous reaction], ∆H must be 06 The Langmuir adsorption isotherm
highly negative because reaction is is deduced by using the
02 Which one of the following exothermic. Hence, for the adsorption of
characteristics is associated with assumption that
a gas, if ∆S is negative, therefore, ∆H
[CBSE AIPMT 2007]
adsorption? [NEET 2016, Phase I] should be highly negative.
(a) the adsorption takes place in
(a) ∆G, ∆H and ∆S all are negative
multilayers
(b) ∆G and ∆H are negative but ∆S is 04 In Freundlich adsorption isotherm,
(b) the adsorption sites are equivalent in
positive the value of 1/n is their ability to adsorb the particles
(c) ∆G and ∆S are negative but ∆H is [CBSE AIPMT 2012]
(c) the heat of adsorption varies with
positive (a) between 0 and 1 in all cases coverage
(d) ∆G is negative but ∆H and ∆S are (b) between 2 and 4 in all cases (d) the adsorbed molecules interact
positive
(c) 1 in case of physical adsorption with each other
Ans. (a) (d) 1 in case of chemisorption Ans. (b)
Adsorption is a spontaneous process Ans. (a) The main points of Langmuir’s theory of
that occurs with release in energy and
In Freundlich adsorption isotherm, adsorption are as
decrease in the randomness (i.e.
x (i) Adsorption takes place on the
entropy) of the adsorbed substance. = kp1/ n
m surface of the solid only till the whole
For a spontaneous process, ∆G must be
Where, x = amount of adsorbent of the surface is completely covered
negative.
with a unimolecular layer of the
∆G = ∆H −T∆S m = amount of adsorbate
adsorbed gas.
Surface Chemistry 101
(ii) Adsorption consist of two opposing Ans. (a) TOPIC 3

processes (a) condensation and (b) Adsorption is the ability of a substance
evaporation. to concentrate or hold gases, liquids
Colloids, Micelles and
(iii) The rate of condensation depend upon its surface. Emulsions
upon the uncovered surface of the Solids adsorb greater amounts of
adsorbent available for substances at lower temperature. In 11 The right option for the statement
condensation. general adsorption decreases with “Tyndall effect is exhibited by”, is
increasing temperature. [NEET 2021]
07 For adsorption of a gas on a solid, (a) NaCl solution (b) glucose solution
x
the plot of log vs log p is linear (c) starch solution (d) urea solution
m TOPIC 2 Ans. (c)
with slope equal to (n being a whole
number) [CBSE AIPMT 2006, 1994]
Catalyst Tyndall effect is shown by colloidal
solution in which particles having larger
(a) k (b) log k size scatters the light.
1 09 Which one of the following
(c) n (d) NaCl, glucose and urea do not form a
n statements is incorrect about colloidal solution. Only starch solution is
Ans. (d) enzyme catalysis? colloidal solution. So, Tyndall effect is
If we plot a graph betweenlog   and
x [CBSE AIPMT 2012] exhibited by starch solution.
 m (a) Enzymes are mostly proteinous in
log p, a straight line will be obtained. The nature 12 In which of the sols, the colloidal
1 (b) Enzyme action is specific particles are with negative charge?
slope of the line is equal to and the
n (c) Enzymes are denaturated by UV-rays [NEET (Oct.) 2020]
intercept is equal tolog k. and at high temperature (a) TiO2 (b) Haemoglobin
(d) Enzymes are least reactive at
(c) Starch (d) Hydrated Al2O 3
optimum temperature
Ans. (c)
1 Ans. (d)
Slope = (a) In TiO2 sol, TiO2 particles are
log
x n Most of the enzymes have proteinous positively charged.
m nature. They are highly specific and get
(b) In blood, haemoglobin is positively
denaturated by high temperature or
charged.
Intercept log k UV-rays. At optimum temperature,
(c) In starch sol, starch is negatively
which is generally in between 25°-35°C,
charged.
log p enzyme activity is maximum.
(d) In hydrated Al2O3, Al2O3 ⋅ xH2O is
x
where, = amount of adsorption positively charged.
m 10 According to the adsorption theory Hence, option (c) is the correct.
According to Freundlich adsorption of catalysis, the speed of the
isotherm reaction increases because
x
13 Measuring zeta potential is useful
= kp1/ n [CBSE AIPMT 2003] in determining which property of
m (a) adsorption produces heat which colloidal solution? [NEET (Sep.) 2020]
Taking log of both sides, increases the speed of the reaction
x 1 (b) adsorption lowers the activation
(a) Solubility
log = log k + log p
m n energy of the reaction (b) Stability of the colloidal particles
from y = zx + c (c) the concentration of reactant (c) Size of the colloidal particles
1 molecules at the active centres of (d) Viscosity
z = (slope) the catalyst becomes high due to
n Ans. (b)
adsorption
Stability of a colloidal solution is
(d) in the process of adsorption, the
08 Which is not correct regarding the explained by zeta potential.
activation energy of the molecules
adsorption of a gas on surface of becomes large
The particles of colloid carry an electric
solid? [CBSE AIPMT 2001] charge, i.e. acquire positive or negative
Ans. (b) charge by preferential adsorption of
(a) On increasing temperature
According to adsorption theory of positive or negative ions from dispersion
adsorption increases continuously
catalysis, the speed (rate) of the reaction medium. The combination of two layer of
(b) Enthalpy and entropy change is positive and negative charges around
increases because adsorption lowers
negative the colloid is called Helmholtz electrical
the activation energy of the reaction.
(c) Adsorption is more for some specific
 1  double layer and the potential difference
substance ∴ Rate of reaction ∝  of this double layer is called zeta
 activation energy 
(d) Reversible potential.
14 Which mixture of the solutions will I− < SO24− < PO34− < [Fe(CN) 6 ] 4 − . 19 Which property of colloidal solution
lead to the formation of negatively Similarly, to coagulate a negatively is independent of charge on the
charged colloidal [AgI]I − sol ? charged sol, the order of coagulating colloidal particles?
[NEET (National) 2019] power of positive ions is [CBSE AIPMT 2015, 2014]
(a) 50 mL of 1 M AgNO3 + 50 mL of 2 M KI Ag + < Pb2 + < Fe3+ < Si4+ (a) Coagulation
(b) 50 mL of 2 M AgNO3 + 50 mL of 1.5 M KI (b) Electrophoresis
(c) 50 mL of 1 M AgNO3 + 50 mL of 0.1 M KI 16 Fog is a colloidal solution of (c) Electroosmosis
(d) 50 mL of 1 M AgNO3 + 50 mL of 1.5 M KI (d) Tyndall effect
Ans. (d) (a) Gas in liquid (b) Solid in gas
Ans. (d)
(c) Gas in gas (d) Liquid in gas
Key Idea The colloidal particles acquire Coagulation is generally brought about
positive or negative charge by Ans. (d)
by the addition of electrolytes. When an
preferential adsorption of positive ions Fog is a colloidal solution of liquid in a electrolyte is added to a colloidal
on negative ions. gas, in which liquid is the dispersed solution, the particles of the sol take up
When silver nitrate (AgNO3) solution is phase whereas gas is the dispersion the ions which are oppositely charged.
added to potassium iodide (KI) solution, medium. Examples of other options are As a result their charge gets neutralised.
the precipitated silver iodide (AgI) as follows: Electrophoresis The movement of
adsorbs iodide ions (I− ) from the Gas in liquid : Shaving cream, soda colloidal particles under an applied
dispersion medium and negatively water, froth electric potential is called
charged colloidal solution results. Solid in gas : Dust in air electrophoresis.
Among the given options, in option (a) Gas in gas : Atmospheric air. Electroosmosis may be defined as a
and option (b) millimole of KI is higher phenomenon in which the molecules of
than AgNO3. Hence, both the mixture will 17 The coagulation values in the dispersion medium are allowed to
lead to the formation of negatively more under the influence of an electric
charged colloidal [AgI]I− sol. millimoles per litre of the
electrolytes used for the field whereas colloidal particles are not
Note The most appropriate option is (a) allowed to more.
because millimole of KI coagulation of As 2 S 3 are given
Tyndall effect is the scattering of light
(50 mL × 2 M = 100 mmol)is maximum in below by sol particles, which cannot be
this option. I. (NaCl) = 52, affected by charge on them.
II. (BaCl 2 ) = 0.69
15 On which of the following 20 The protecting power of lyophilic
properties does the coagulating III. (MgSO 4 ) = 0.22
colloidal sol is expressed in terms
power of an ion depend? The correct order of their of [CBSE AIPMT 2012]
[NEET 2018] coagulating power is (a) coagulation value
(a) Both magnitude and sign of the [NEET 2016, Phase II]
(b) gold number
charge on the ion (a) I > II > III (b) II > I > III
(c) critical micelle concentration
(b) Size of the ion alone (c) III > II > I (d) III > I > II
(d) oxidation number
(c) The magnitude of the charge on the Ans. (c)
ion alone Ans. (b)
Lower the coagulating power, higher is
(d) The sign of charge on the ion alone Lyophobic sols are unstable, so they are
the coagulation value in millimoles per
Ans. (a) stabilised by adding some lyophilic
litre, i.e. coagulating power is inversely
colloids which protect them from
The process of settling of colloidal proportional to coagulation values. Thus,
precipitation. Thus, lyophilic colloids are
particles due to the neutralisation of correct order of coagulating power is
called protecting colloids. Their
their charge by any means is called MgSO4 > BaCl2 > NaCl or III > II > I protecting power is expressed in terms
coagulation. of gold number. In other words, gold
Coagulation power of an ion depends 18 The suspension of slaked lime in number can be defined as the minimum
both on magnitude and sign of the water is known as amount of lyophilic colloid in milligrams,
charge (positive or negative) on the ion. [NEET 2016, Phase II] which prevent the flocculation of 10 mL
This fact can be explained by Hardy gold sol by the addition of 1 mL of 10%
Schulze rule.
(a) limewater
NaCl solution.
(b) quicklime
According to this rule “greater the NOTE Lesser the gold number, higher is
valency of the coagulating (c) milk of lime
the protecting power.
ion/flocculating ion (oppositely charged (d) aqueous solution of slaked lime
ion) added, the greater is its power to Ans. (c) 21 Which one of the following forms
cause coagulation.
Aqueous solution of slaked lime is called micelles in aqueous solution above
To coagulate a positively charged sol, lime water whereas suspension solution
the order of coagulating power of certain concentration?
of slaked lime is called milk of lime. [CBSE AIPMT 2005]
negative ion is
Surface Chemistry 103
(a) Urea Ans. (a) Ans. (d)

(b) Dodecyl trimethyl ammonium Micelles are the clusters formed by the According to Hardy-Schulze law,
chloride association of colloids. They are formed coagulation ∝ charge of ion
(c) Pyridinium chloride by lyophilic and lyophobic groups. As the So, coagulation is affected by both
(d) Glucose concentration increases, the lyophobic magnitude of charge and nature of
Ans. (b) parts receding away from the solvent charge. For coagulation of a positive sol,
approach each (non-polar part) other and negative ions are required and for
Surfactants like detergents, form form a cluster, the lyophobic ends are in
micelles in aqueous solution above to coagulation of negative sol, positive ions
the interior, lyophilic groups (polar part) are required.
their critical micelle concentration projecting outward in contact with the
(CMC). Dodecyl trimethyl ammonium solvent. Greater the magnitude of charge,
chloride is an example of surfactant quicker will be the coagulation.
(cationic surfactant), 24 The method usually employed for The ions having opposite charge to sol
CH3 the precipitation of a colloidal particle causes coagulation.
+
CH3  (CH2 ) 11  N  CH3 solution is Coagulating power of an electrolyte is
14 4244 3 – directly proportional to the fourth power
Non- polar part Cl CH3 (a) dialysis [CBSE AIPMT 2000]
14 4244
3 of the valence of the ions causing the
Polar part (b) addition of electrolytes coagulation.
(c) diffusion through animal
22 Which of the following forms membrane 27 During dialysis [CBSE AIPMT 1996]
cationic micelles above certain (d) condensation (a) only solvent molecules can diffuse
concentration? [CBSE AIPMT 2004] Ans. (b) (b) solvent molecules, ions and colloidal
(a) Sodium ethyl sulphate On addition of electrolyte charge of particles can diffuse
colloidal particles will neutralise and (c) all kinds of particles can diffuse
(b) Sodium acetate
hence, coagulation or precipitation of through the semipermeable
(c) Urea membrane
colloidal solution will occur.
(d) Cetyl trimethyl ammonium bromide (d) solvent molecules and ions can
Ans. (d) 25 At the critical micelle diffuse
Cetyltrimethylammonium bromide forms concentration (CMC) the surfactant Ans. (d)
cationic micelles above a certain molecules [CBSE AIPMT 1998] The principle of dialysis is based upon
concentration. In the molecule of (a) decompose the fact that colloidal particles cannot
detergents and soap, the negative ions pass through a parchment or cellophane
(b) dissociate
aggregate to form a micelle of colloidal membrane while the ions of the
size. In polar medium (like water), the (c) associate
(d) become completely soluble electrolyte can pass through it.
negative ion has a long hydrocarbon
chain and a polar group (—COO− ) at one Ans. (c)
end and on other end, it hasN+ ion, thus
28 If a beam of light is passed through
The soap concentration at which true solution, then it is
cationic micelle is formed. micelles first appear is called critical
micelle concentration (CMC). At this (a) visible [CBSE AIPMT 1995]
23 Position of non-polar and polar condition the surfactant molecules (b) scatter
parts in micelle is associate with each other. (c) not visible
[CBSE AIPMT 2002] (d) None of the above
(a) polar at outer surface but non-polar 26 The ability of anion to bring about Ans. (c)
at inner surface coagulation of a given colloid
When a beam of light is passed through
(b) polar at inner surface but non-polar depends upon true solution, then the path of light is
at outer surface (a) its charge [CBSE AIPMT 1997] invisible due to fact that the size of
(c) distributed all over the surface (b) the sign of the charge alone particles in true solution is below 1 nm,
(d) present in the surface only (c) the magnitude of its charge so they cannot scatter the light that
(d) both magnitude and sign of its charge means cannot show Tyndall effect.
13
Classification of Elements
and Periodicity in Properties
TOPIC 1 Ans. (c) 04 Which one of the elements with the
Periodic Table and Atomic following outer orbital
IUPAC official
Classification of Elements Name number configurations may exhibit the
name
(Z) largest number of oxidation states?
01 From the following pairs of ion [CBSE AIPMT 2009]
(A) Unnilunium 101 (i) Mendelevium
which one is not an iso-electronic (Md) (a) 3 d 3, 4 s 2 (b) 3d 5 , 4 s 1
pair? [NEET 2021] (B) Unniltrium 103 (ii) Lawrencium (c) 3d 5 , 4 s 2 (d) 3d2 , 4 s 2
2− − + 2+
(a) O , F (b) Na , Mg (Lr) Ans. (c)
(c) Mn2+ , Fe 3+ (d) Fe2 + , Mn2+
(C) Unnilhexium 106 (iii) Seaborgium The sum of number of electrons
Ans. (d) (Sg) (unpaired) in d-orbitals and number of
electrons in s-orbital gives the number
Ion Number of electrons (D) Unununnium 111 (iv) Roentgenium
of oxidation states (os) exhibited by a
2− (Rg) [but (iv)
O 10 d-block element. Therefore,
Darmstadtium
F− 10 (Ds), Given] [Z (a) 3d 3, 4s 2 ⇒OS = 3 + 2 = 5
Na +
10 = 110] (b) 3d 5 , 4 s 1 ⇒OS = 5 + 1 = 6
Mg 2 + 10 (c) 3d 5 , 4 s 2 ⇒OS = 5 + 2 = 7
So, D-(iv) is the incorrect match.
2+
Mn 23 (d) 3d2 , 4 s 2 ⇒OS = 2 + 2 = 4
Fe 3 + 23 03 The element Z = 114 has been Hence, element with3d 5 ,4s 2
Fe 2 + 24 discovered recently. It will belong
configuration exhibits largest number of
oxidation states.
Mn2 + 23 to which of the following
O2 − and F − are iso-electronic pair.
family/group and electronic 05 An atom has electronic
Na+ and Mg2 + are iso-electronic pair.
configuration? [NEET 2017] configuration
Mn2 + and Fe3+ are iso-electronic pair. (a) Halogen family, [Rn] 5f 14 6d 10 7 s 2 7 p5 1s 2 , 2s 2 2p 6 , 3s 2 3p 6 3d 3 , 4s 2 , you
Fe2 + and Mn2 + are not iso-electronic pair. (b) Carbon family, [Rn] 5f 14 6d 10 7 s 2 7 p2 will place it in [CBSE AIPMT 2002]
(c) Oxygen family, [Rn] 5f 14 6d 10 7 s 2 7 p4 (a) fifth group (b) fifteenth group
02 Identify the incorrect match. (d) Nitrogen family, [Rn] 5f 6d14 10 2
7s 7p 6 (c) second group (d) third group
IUPAC official Ans. (b) Ans. (a)
Name
name The amount of energy required to
The element with atomic number, Z = 114
(A) Unnilunium (i) Mendelevium is flerovium (F1). It is a super heavy remove an electron from the outermost
artificial chemical element. In the orbit of a gaseous atom is known as
(B) Unniltrium (ii) Lawrencium ionisation potential. Elements having
periodic table of the elements, it is a
transactinide element in the p-block. It is half-filled or completely filled orbitals
(C) Unnihexium (iii) Seaborgium
a member of the 7th period and is the are more stable than partially filled
(D) Unununnium (iv) Darmstadtium
heaviest known member of the carbon orbitals.
[NEET (Sep.) 2020] family. In a period from left to right ionisation
Electronic configuration for Z = 114 is potential decreases as the atomic
(a) (B), (ii) (b) (C), (iii) number increases. The given elements
(c) (D), (iv) (d) (A), (i) [Rn] 86 5f 14 , 6d 10 , 7 s 2 , 7 p2 (Be, B, C, N, O) are present in II period as
Classification of Elements and Periodicity in Properties 105
Be B C N O Ans. (c) 11 In which of the following options

Ionisation potential increases The electronic configuration of element the order of arrangement does not
→
But in case of Be and B, Be has higher with atomic number 33 is agree with the variation of property
ionisation potential due to stable 1s 2 , 2 s 2 2p6 , 3 s 2 3p6 ,4s 2 , 3d 10 , 4p3. As, its indicated against it?
configuration. last shell have five electrons and hence, [NEET 2016, Phase I]
2
4 Be = 1s , 2s
2 its group is 10 + 5 = 15th or V A. (a) B < C < N < O (increasing first
ionisation enthalpy)
2 s2 Stable configuration
09 The electronic configuration of (b) I < Br < Cl < F (increasing electron
5
B = 1s 2, 2s 2 2p1 four elements are given below. gain enthalpy)
Unstable Which element does not belong to (c) Li < Na < K < Rb (increasing metallic
2p1 configuration radius)
the same family as others?
In the same way in case of N and O, N has [CBSE AIPMT 1989] (d) Al 3+ < Mg2 + < Na + <F − (increasing
ionic size)
higher ionisation potential than O due to (a) [Xe] 4 f 14 , 5 d 10, 6 s 2
stable configuration Ans. (a,b)
2 2 3
(b) [Kr] 4 d 10, 5 s 2
7 N = 1s , 2s 2p (c) [Ne] 3 s 2 , 3p 5 For option (a)
2p3 Stable configuration First ionisation energy is the energy
(half-filled) (d) [Ar] 3 d 10, 4 s 2 required to remove an electron from
2
Ans. (c) outermost shell.
8 O = 1s , 2s 2 2p4
In a family, all elements have same Hence, correct order is B < C < O < N.
Unstable outermost electronic configuration. For option (b)
2p 4
configuration Since [Ne] 3s 2 3p5 , chlorine belongs to Electron gain enthalpy is the energy
So, the correct order of increasing halogen family while the remaining three required to gain an electron in the
ionisation potential will be are in same group i.e. group 12. outermost shell.
B < Be < C < O < N = [Xe]4f 14 5d 10 6s 2 Hence, the correct order is I < Br < F < Cl.
80 Hg
For option (c)
48 Cd = [Kr]4d 10 5s 2
06 The element with the atomic As we move down the group in alkali
number 118, will be 30 Zn = [Ar] 3d 10 4s 2 metal, metallic radius increases Li < Na <
(a) alkali [CBSE AIPMT 1996] K < Rb.
(b) noble gas For option (d)
(c) lanthanide
TOPIC 2 In case of isoelectronic species, as
positive charge decreases or negative
(d) transition element Periodic Properties charge increases the ionic size of the
Ans. (b) species increases and vice-versa
The outermost electronic configuration 10 The correct order of atomic radii in Al 3+ < Mg2 + < Na+ < F − .
of element with atomic number 118 is group 13 elements is [NEET 2018]
7 s 2 7 p6 , so it will be a noble gas. 12 The species Ar, K + and Ca 2+
(a) B < Ga < Al < Tl < In
(b) B < Al < Ga < In < Tl contain the same number of
07 The electronic configuration of an electrons. In which order do their
element is 1s 2 , 2 s 2 2p 6 , 3s 2 3p 3 . (c) B < Al < In < Ga < Tl
(d) B < Ga < Al < In < Tl radii increase? [CBSE AIPMT 2015]
What is the atomic number of the
Ans. (d) (a) Ar < K+ < Ca2 + (b) Ca2 + < Ar < K+
element, which is present just +
(c) Ca < K < Ar
2+
(d) K + < Ar < Ca2+
below the above element in the The atomic radii as well as ionic radii
increases on moving down the group 13 Ans. (c)
periodic table? [CBSE AIPMT 1995]
elements because of the successive Ca2 + < K+ < Ar
(a) 33 (b) 34 (c) 36 (d) 49 addition of one extra shell of electrons. + 2+
Ar, K and Ca are isoelectronic i.e. with
Ans. (a) However, there is an anomaly at gallium same number of electrons, 18. For
The element which present just below in case of atomic radii. Atomic radii of Ga isoelectronic species ionic radii decreases
the given element will have outermost is lesser as compared to Al. with increase in effective (relative) positive
electronic configuration as4 s 2 4p3, so Gallium (Ga) with electronic charge. Also Ar, K and Ca belong to the
its full electronic configuration is configuration, [Ar] 18 3d 10 4s 2 4p1 has an same period (3rd period).
1s 2 , 2 s 2 2p6 , 3s 2 3p6 , 4 s 2 , 3d 10 , 4p3 and extra d-electrons which do not screen
hence, its atomic number is 33. the nucleus effectively. Consequently, 13 Which of the following orders of
electrons of Ga are more attracted by ionic radii is correctly represented?
08 If the atomic number of an element nucleus. [CBSE AIPMT 2014]
is 33, it will be placed in the Thus, the increasing order of atomic (a) H− > H+ > H
periodic table in the radii of the group 13 elements is B (85
pm) < Ga (135 pm) < Al (143 pm) < In (167
(b) Na+ > F − > O2 −
[CBSE AIPMT 1993]
pm) < Tl (170 pm). (c) F − > O2 − > Na+
(a) first group (b) third group (d) Al3+ > Mg2 + > N3−
(c) fifth group (d) seventh group
Ans. (*) (a) Ca2 + > K + > S2 − > Cl− 17 Amongst the elements with
(No option is correct.) (b) Cl− > S2 − > Ca2 + > K + following electronic configurations,
(a) H− > H+ > H (c) S2 − > Cl− > K + > Ca2 + which one may have the highest
It is known that radius of a cation is (d) K + > Ca2 + > Cl− > S2 − ionisation energy?
always smaller than that of a neutral Ans. (c) [CBSE AIPMT 2009]
atom due to decrease in the number of (a) [Ne] 3 s 2 3p 3
Key Idea Ionic radii ∝ charge on anion
orbits. Whereas, the radius of anion is
∝
1 (b) [Ne] 3 s 2 3p2
always greater than a cation due to
decrease in effective nuclear charge. charge on cation (c) [Ar] 3d 10, 4 s 2 4 p 3
Hence, the correct order is During the formation of a cation, the (d) [Ne] 3 s 2 3p 1
H− > H > H+ electrons are lost from the outer shell Ans. (a)
and the remaining electrons experience
(b) Na+ > F − > O2 − Key Idea Across a period, increasing
a great force of attraction by the
The given species are isoelectronic as nuclear charge outweighs the
nucleus, i.e. attracted more towards the
they contain same number of electrons. shielding, hence the outermost
nucleus. In other words, nucleus hold the
For isoelectronic species, remaining electrons more tightly and electrons are held more and more
1 tightly and ionisation energy. increases
Ionic radii ∝ this results in decreased radii.
atomic number across a period while as we move down
However, in case of anion formation, the
Ion: Na+ F − O2 − a group increase in shielding outweighs
addition of electron(s) takes place in the
same outer shell, thus the hold of
the increasing nuclear charge and the
Atomic number : 11 9 8
nucleus on the electrons of outer shell removal of the outermost electron
Hence, the correct order of ionic radii is required less energy down a group.
decreases and this results in increased
O2 − > F − > Na+ Electronic configuration Group
ionic radii.
(c) Similarly, the correct option is [Ne] 3 s 2 3p3 V
Thus, the correct order of ionic radii is
O2 − > F − > Na+ [Ne] 3 s 2 3p2
S2 − > Cl − > K+ > Ca2 + IV
(d) Ions : Al 3+ Mg2 + N3− [Ar] 3d 10 , 4 s 2 4p3 V
Atomic number : 13 12 7 16 Which of the following represents [Ne] 3 s 2 3p1 III
Hence, the correct order is, the correct order of increasing Since, ionisation energy increases in a
N3− > Mg2 + > Al 3+ electron gain enthalpy with period and decreases in a group,
negative sign for the elements [Ne] 3 s 2 3p3 configuration has the
14 Identify the wrong statement in the O, S, F and Cl? [CBSE AIPMT 2010]
highest ionisation energy among the
following. [CBSE AIPMT 2012] given elements.
(a) Cl < F < O < S
(a) Amongst isoelectronic species,
(b) O < S < F < Cl 18 Which of the following oxides is not
smaller the positive charge on the
cation, smaller is the ionic radius (c) F < S < O < Cl expected to react with sodium
(b) Amongst isoelectronic species, (d) S < O < Cl < F hydroxide? [CBSE AIPMT 2009]
greater the negative charge on the Ans. (b) (a) B2O 3 (b) CaO (c) SiO2 (d) BaO
anion, larger is the ionic radius Key Idea Electron gain enthalpy, Ans. (b)
(c) Atomic radius of the elements generally, increases in a period from left
increases as one moves down the to right and decreases in a group on Sodium hydroxide, NaOH, being a strong
first group of the periodic table moving downwards. However, members alkali never react with a basic oxide
(d) Atomic radius of the elements of III period have somewhat higher (compound). Among the given options,
decreases as one moves across electron gain enthalpy as compared to B2O3 and BeO are amphoteric oxides,SiO2
from left to right in the 2nd period of the corresponding members of second is an acidic oxide and CaO is a basic
the periodic table period, because of their small size. oxide. Therefore, NaOH does not react
with CaO.
Ans. (a) O and S belong to VI A (16) group and Cl
Atomic radius of the elements and F belong to VII A (17) group. Thus, the
electron gain enthalpy of Cl and F is 19 The correct order of decreasing
decreases across a period from left to
higher as compared to O and S. second ionisation enthalpy of
right due to increase in effective nuclear
charge. On moving down a group, since, Cl and F > O and S Ti(22), V(23), Cr(24) and Mn(25) is
number of shells increases, so atomic [CBSE AIPMT 2008]
Between Cl and F, Cl has higher electron
radius increases. gain enthalpy then the F, since the (a) Cr > Mn > V > Ti
Amongst isoelectronic species, ionic incoming electron experiences a greater (b) V > Mn > Cr > Ti
radius increases with increase in force of repulsion because of small size (c) Mn > Cr > Ti > V
negative charge or decrease in positive of F-atom. Similar is true in case of (d) Ti > V > Cr > Mn
charge. O and S, i.e. the electron gain enthalpy
of S is higher as compared to O due to
Ans. (a)
15 The correct order of the its small size. Thus, the correct order The amount of energy required to
of electron gain enthalpy of given remove an electron from unipositive ion
decreasing ionic radii among the is referred as second ionisation
elements is
following isoelectronic species is potential.
O < S < F < Cl
[CBSE AIPMT 2010]
Classification of Elements and Periodicity in Properties 107
In Ti, V, Cr and Mn, generally second Ans. (a) Unstable

ionisation energy increases with configuration
1
Ionic radii ∝ 2 p1
increase in atomic number but second Z eff
ionisation potential of Cr is greater than So, the correct order of ionisation
that of Mn due to the presence of exactly Z eff → effective nuclear charge potential of given elements is
half-filled d-subshell in Cr. This Z eff is calculated as follows : Li < B < Be < C
Thus, the order of second ionisation Z eff = Z − screening constant (σ)
enthalpy is This value of screening constant is 25 Correct order of Ist ionisation
Cr > Mn > V > Ti based upon the number of electrons in potential (IP) among following
valence shell as well as in penultimate
shells.
elements Be, B, C, N, O is
20 Which of the following electronic [CBSE AIPMT 2001]
configuration of an atom has the 23 The ions (a) B < Be < C < O < N
lowest ionisation enthalpy? O 2– , F – , Na + , Mg 2+ and Al 3+ are (b) B < Be < C < N < O
[CBSE AIPMT 2007] (c) Be < B < C < N < O
isoelectronic. Their ionic radii show
(a) 1s 2 , 2 s 2 2 p 5 (b) 1s 2 , 2 s 2 2 p 3 [CBSE AIPMT 2003] (d) Be < B < C < O < N
(c) 1s , 2 s 2 p , 3 s (d) 1s 2 , 2 s 2 2 p 6
2 2 5 1
(a) an increase fromO2 − to F − and then Ans. (a)
decrease fromNa+ to Al 3+ An atom has electronic configuration
Ans. (c)
(b) a decrease fromO2 – to F − and then
1s 2 , 2s 2 , 2p6 , 3s 2 3p6 3d 3, 4s 2
The electronic configuration increase fromNa+ to Al 3+
1s 2 , 2 s 2 2p5 , 3 s 1 shows lowest ionisation (c) a significant increase fromO2 – to Al 3+ It is a member ofd- block element
energy because this configuration is because the last electron is filled in
(d) a significant decrease fromO2– to
d- subshell as3d 3 and the following
unstable due to the presence of one Al 3+
electron in s-orbital. Hence, less energy electronic configuration is possible for
Ans. (d) d- subshell as (n − 1)d (1 to 10 )
is required to remove the electron.
On increasing atomic number of
isoelectronic species ionic radii Group number IIIB IVB VB VIB VIIB
21 Identify the correct order of the decreases due to increasing effective
size of the following. 3 4 5 6 7
nuclear charge (Z eff).
[CBSE AIPMT 2007] 1 1 ns 2 (n − 1) s 2 p6 d 1 d2 d 3 d 4 d 5
Radius ∝ ∝
(a) Ca2+ < K + < Ar < S2– < Cl– Atomic number Z eff VIII VIII VIII IB IIB
(b) Ca2+ < K + < Ar < Cl– < S2– So, as the negative charge increases 8 9 10 11 12
(c) Ar < Ca2+ < K + < Cl– < S2– ionic radii increases while on increasing d 6 d 7 d 8 d 9 d 10
(d) Ca2+ < Ar < K + < Cl– < S2– positive charge ionic radii decreases. Hence, it is member of third group.
Anions having higher ionic radii than the
Ans. (b)
cation. 26 The first ionisation potential (in eV)
A cation has always the lesser ionic size Hence, order of radii
than a metal atom due to loss of of Be and B, respectively are
electrons and an anion has always the O2 – > F – > Na+ > Mg2 + > Al 3+ [CBSE AIPMT 1998]
greater size than metal atom due to gain (a) 8.29, 9.32 (b) 9.32, 9.32
of electrons. The given species are
24 Which of the following order is (c) 8.29, 8.29 (d) 9.32, 8.29
isoelectronic species as they contain wrong? [CBSE AIPMT 2002]
Ans. (d)
same number of electrons. For (a) NH3 < PH3 < AsH3 – Acidic
isoelectronic species ionic radii (b) Li < Be < B < C–1st Ionisation potential First ionisation potential of beryllium
1 (Be) is greater than boron (B) due to
∝ . (c) Al2O3 < MgO < Na2O < K2O – Basic
stable configuration
atomic number (d) Li+ < Na+ < K+ < Cs+ – Ionic radius
4 Be = 1s , 2 s
2 2
Ion : Ca2 + K+ Ar S2 Cl Ans. (b)
Atomic number : 20 19 18 16 17 5
B = 1s , 2 s 2p1
2 2
Li, Be, B and C are present in IInd period. Order of attraction of electrons towards
So, the correct order of size is as In a period from left to right ionisation nucleus is2 s > 2 p, so more amount of
Ca2 + < K+ < Ar < Cl – < S2 – potential increases. energy is required to remove the
Ionisation potention increases electron from 2 s orbital in comparison
22 Ionic radii are [CBSE AIPMT 2004]  → to 2p orbital. So, ionisation potential of
Li Be B C
(a) inversely proportional to effective Be is 9.32 eV and B is 8.29 eV.
* But in case of Be and B, Be has higher
nuclear charge
ionisation potential than B due to stable
(b) inversely proportional to square of configuration of Be.
27 In crystals of which of the following
effective nuclear charge ionic compounds would you expect
4 Be = 1s , 2s
2 2
(c) directly proportional to effective maximum distance between
nuclear charge Stable configuration
(due to fully-filled orbital) centres of cations and anions?
(d) directly proportional to square of [CBSE AIPMT 1998]
effective nuclear charge 2 s2
2 2 1 (a) LiF (b) CsF
5B = 1s , 2 s 2p
(c) CsI (d) LiI
Ans. (c) the atomic volume first decreases and Ans. (c)
On moving from top to bottom in a group then increases because atomic size in N, O, F are more electronegative
of periodic table distance between ions last of any period increases. element, so they accept electrons more
in ionic compounds increases. Hence, it easily and form negative ions (anions).
is maximum in CsI. 32 One of the characteristic
properties of non-metals is that 36 The ionisation of hydrogen atom
28 Which one of the following ions will they [CBSE AIPMT 1993] would give rise to
be smallest in size? (a) are reducing agents [CBSE AIPMT 1990]
[CBSE AIPMT 1996] (b) form basic oxides (a) hydride ion (b) hydronium ion
(a) Na+ (b) Mg2+ (c) F − (d) O2− (c) form cations by electron gain (c) proton (d) hydroxyl ion
Ans. (b) (d) are electronegative Ans. (c)
Na+ ,Mg2 + , O2 − and F − all are isoelectronic Ans. (d) Hydrogen have one proton and one
but Mg2 + have 12 protons in his nucleus, Non-metals easily gain electrons and electron, when it ionise, i.e. it lose one
so the attraction force on last shell is hence, they form negative ions, so they electron, then only proton is left in the
maximum and hence, it have smallest are electronegative in nature. nucleus, soH+ ion is formed during
size. ionisation which is also called proton.
33 Na + , Mg 2+ , Al 3+ and Si 4+ are H → H+ + e −
 e − = 1
29 Among the following, the one   Proton
isoelectronic. The order of their  p= 1 
which is most basic is
[CBSE AIPMT 1994] ionic size is [CBSE AIPMT 1993]
37 In the periodic table, with the
(a) ZnO (b) MgO (a) Na+ > Mg2+ < Al3+ < Si4+
increase in atomic number, the
(c) Al2O 3 (d) N2O 5 (b) Na+ < Mg2+ > Al3+ > Si4+
metallic character of an element
Ans. (b) (c) Na+ > Mg2+ > Al3+ > Si4+
[CBSE AIPMT 1989]
(d) Na+ < Mg2+ > Al3+ < Si4+
ZnO and Al2O3 are amphoteric oxide,N2O5 (a) decrease in a period and increases in
is oxide of non-metal, so it is acidic and Ans. (c) a group
hence, MgO is most basic among In isoelectronic species the number of (b) ncreases in a period and decreases
Al2O3, ZnO, N2O5 and MgO. electrons are same but nuclear charge in a group
is different. As the nuclear charge (c) increases in a period as well as in the
30 Which electronic configuration of increase, the attraction force on last group
an element has abnormally high electron increases, so the size (d) decreases in a period and also in the
difference between second and decreases or in other words group
1
third ionisation energy? Ionic size ∝ and Ans. (a)
[CBSE AIPMT 1993] Charge on cation
In periodic table, the metallic character
(a) 1s 2 , 2 s 2 2 p 6 , 3 s 1 hence, order is increases down the group because the
(b) 1s 2 , 2 s 2 2 p 6 , 3 s 2 3p 1 Na+ > Mg2 + > Al 3+ > Si4+ ionisation enthalpy decreases down the
→ group and metallic character decreases
(c) 1s 2 , 2 s 2 2 p 6 , 3 s 2 3p2
from left to right because the ionisation
(d) 1s 2 , 2 s 2 2 p 6 , 3 s 2 Nuclear charge increase
→ enthalpy increases from left to right.
Ans. (d) Size decrease
When the element having 38 Pauling’s electronegativity values
1s 2 , 2 s 2 2p6 , 3 s 2 configuration, loss two 34 One would expect proton to have for elements are useful in
electrons, then it acquire the electronic very large [CBSE AIPMT 1993] predicting [CBSE AIPMT 1989]
configuration of noble gas (Ne), so to (a) charge (a) polarity of the molecules
remove third electron a large amount of (b) ionisation potential (b) position in the emf series
energy is required and hence, its second (c) hydration energy (c) coordination numbers
and third ionisation energy have large (d) radius (d) dipole moments
difference. Ans. (c) Ans. (a)
Proton have very small size, so have Pauling’s electronegativity values are
31 In the periodic table from left to
large hydration energy. The degree of useful in determination of polarity of the
right in a period, the atomic volume hydration depends upon the size of the bond in molecules. If electronegativity
[CBSE AIPMT 1993] cation. Smaller the size of a cation difference is zero, then the molecule is
(a) decreases greater the hydration energy. non-polar otherwise it is polar.
(b) increases x A − x B = 0.028 ∆ E
(c) remains same 35 Which of the following sets has
x A and x B are electronegativities of the
(d) first decrease then increases strongest tendency to form
atoms A and B respectively. While,
Ans. (d) anions? [CBSE AIPMT 1993]
∆ E = actual bond energy
In the periodic table the atomic size first (a) Ga, In, TI (b) Na, Mg, Al
− EA − A × EB − B
decreases from left to right in period, so (c) N, O, F (d) V, Cr, Mn
14
General Principles and
Processes of Isolation
of Metals
TOPIC 1 03 Considering Ellingham diagram, 04 Roasting of sulphides gives the gas
Occurrence, Thermodynamic which of the following metals can X as a by-product. This is a
and Electrochemical be used to reduce alumina? colourless gas with choking smell
Principles of Metallurgy [NEET 2018] of burnt sulphur and causes great
(a) Mg (b) Zn damage to respiratory organs as a
(c) Fe (d) Cu result of acid rain. Its aqueous
01 Identify the incorrect statement.
[NEET (Odisha) 2019] Ans. (a) solution is acidic acts as a reducing
(a) The scientific and technological Key concept Ellingham diagrams help us agent and its acid has never been
process used for isolation of the in predicting the feasibility of thermal insolated. The gas X is [NEET 2013]
metal from its ore is known as reduction of an ore. The criterion of
(a) H2 S (b) SO2 (c) CO2 (d) SO 3
metallurgy feasibility is that at a given temperature,
(b) Minerals are naturally occurring Gibbs energy of the reaction must be Ans. (b)
chemical substances in the earth’s negative. SO2 gas is obtained when any sulphide
crust Gibbs energy ∆G °vsT plots (schematic) ore is roasted.
(c) Ores are minerals that may contain a for formation of some oxides (Ellingham ∆ 2 M2O + 2 SO2
2 M2S + 3 O2 →
metal diagram). This gas exhibits all the characteristics
(d) Gangue is an ore contaminated with According to Ellingham diagram, the that are given in the question.
undesired materials temperature at which two lines intersect
Ans. (d) shows that the metal will reduce the 05 Which one of the following is a
oxide of other metals which lie above it
The earthly impurities like sand, clay, in Ellingham diagram.
mineral of iron? [CBSE AIPMT 2012]
mica, etc., associated with ores are (a) Malachite (b) Cassiterite
0
called gangue or matrix. In other words, –100 (c) Pyrolusite (d) Magnetite
2Cu 2O
contaminated undesired materials –200
4Cu+O 2
present in an ore is called gangue. Thus, 2FeO Ans. (d)
DG°/kJ mol–1of O2
–300 2Fe+O 2 C+O2 CO2

statement (d) is incorrect while other –400 Mineral Chemical composition
2CO 2 2C+O
options contain correct statements. –500 +O 2
2 2CO Malachite CuCO3.Cu(OH)2
2CO 2ZnO
–600 O2
2Zn+ Cassiterite SnO2
02 Which one is malachite from the –700
I O3
A Pyrolusite MnO2
–800 2/3A 2
following? [NEET (National) 2019]
–900 AI+O 2 Magnetite FeO4
4/3
2MgO
(a) Cu(OH)2 –1000 2Mg+
O2 Thus, magnetite is a mineral of iron.
(b) Fe 3O 4 –1100
(c) CuCO 3 ⋅Cu(OH)2 –1200
06 Sulphide ores of metals are usually
(d) CuFeS2 0°C 400°C 800°C 1200°C 1600°C 2000°C
concentrated by froth floatation
273K 673K 1073K 1473K 1873K 2273K
Ans. (c) Temperature process. Which one of the
Malachite is an ore of copper and its In other words, the metal oxide having following sulphide ores offers an
composition is CuCO3 ⋅ Cu(OH)2 . more negative value of ∆Gf° can reduce exception and is concentrated by
Azurite (Cu(OH)2 ) and copper pyrites the oxide having less negative ∆Gf° . As, chemical leaching?
(CuFeS2 ) are also the ores of copper (Cu). Mg has more − ∆G ° value than alumina,
[CBSE AIPMT 2007]
Mgnetite (Fe3O4 ) is an ore of iron (Fe). so it will be in lower part of Ellingham
diagram. Hence, Mg will be used to (a) Argentite (b) Galena
Hence, option (c) is correct. (c) Copper pyrite (d) Sphalerite
reduce alumina.
Ans. (d) TOPIC 2 (a) iron (II) sulphide

Galena (PbS), copper pyrites (CuFeS2 ) (b) carbon monoxide
and argentite (Ag2S) are concentrated by
Extraction and (c) copper (I) sulphide
froth floatation process but sphalerite Isolation of Metals (d) sulphur dioxide
(ZnS) is concentrated by chemical
Ans. (c)
leaching. 11 The maximum temperature that
Cu2S + 2Cu2O → 6Cu + SO2 ↑
can be achieved in blast furnace is
07 Cassiterite is an ore of [NEET 2021] 14 Aluminium is extracted from
[CBSE AIPMT 1999] (a) upto 1200 K alumina (Al 2O 3 ) by electrolysis of a
(a) Mn (b) Ni (b) upto 2200 K molten mixture of
(c) Sb (d) Sn (c) upto 1900 K [CBSE AIPMT 2012]
Ans. (d) (d) upto 5000 K (a) Al2O 3 + HF + NaAlF4
Cassiterite is an ore of Sn, its chemical Ans. (b) (b) Al2O 3 + CaF2 + NaAlF4
composition is SnO2 . It is also known as (c) Al2O 3 + Na3AlF6 + CaF2
A blast furnace is generally used for
tin stone. (d) Al2O 3 + KF + Na3AlF6
reduction of iron oxides but it can be
used for extraction of other metals like Ans. (c)
08 Calcium is obtained by the Pb from PbO, etc.
Alumina, Al2O3 is a bad conductor of
[CBSE AIPMT 1997] In a blast furnace, hot air is blown from electricity and has very high melting
(a) roasting of limestone the bottom of furnace. This bottom point, so before subjecting to
(b) electrolysis of solution of calcium surface has the maximum temperature electrolysis, it is mixed with fluorspar
chloride inH2O of upto 2200 K. (CaF2 ) and cryolite (Na3AlF6 ), which lower
(c) electrolysis of molten anhydrous its melting point and make it more
calcium chloride
12 Extraction of gold and silver conducting. Mainly CaF2 and Na3AlF6 are
involves leaching with CN − ion. mixed with Al2O3 for converting Al2O3 in
(d) reduction of calcium chloride with
carbon Silver is later recovered by molten state.
Ans. (c) (a) liquation [NEET 2017]
(b) distillation 15 In the extraction of copper from its
Calcium is obtained by electrolysis of
molten anhydrous calcium chloride. (c) zone refining sulphide ore, the metal is finally
(d) displacement with Zn obtained by the reduction of
Ans. (d) cuprous oxide with
09 Cinnabar is an ore of [CBSE AIPMT 2012]
[CBSE AIPMT 1991] Extraction of gold and silver involves
leaching with CN− ion. Silver is later (a) copper (I) sulphide (Cu2 S)
(a) Hg (b) Cu
recovered by distillation of Zn. (b) sulphur dioxide (SO2 )
(c) Pb (d) Zn
In the metallurgy of silver or gold, the (c) iron sulphide (FeS)
Ans. (a) respective metal is leached with a dilute (d) carbon monoxide (CO)
Cinnabar is an ore of mercury which have solution of NaCN or KCN in the presence
Ans. (a)
formula HgS. of air to obtain the metal in solution as
complex. From the complex, metal is In the extraction of copper from its
obtained later by replacement. sulphide ore, when ore is subjected to
10 Calgon used as a water softner, is roasting, some of it is oxidised to Cu2O
[CBSE AIPMT1989] In general,
which reacts with the remaining Cu2S
(a) Na2 [Na4 (PO 3) 6] 4M( s ) + 8CN − (aq ) + 2H2O(aq ) (sulphide ore) to give copper metal.
+ O2 (g) → 4[ M( CN)2 ] − (aq ) + 4OH− (aq )
(b) Na4 [Na2 (PO 3) 6] 2Cu2S + 3O2 → 2Cu2O + 2SO2 ↑
2[ M( CN)2 ] − (aq ) + Zn( s ) →
(c) Na4 [Na4 (PO 4 ) 5] 2Cu2O + Cu2S → 6Cu + SO2 ↑
[Zn(CN) 4 ]2 − (aq ) + 2M(s)
(d) Na4 [Na2 (PO 4 ) 6] In this process Cu2S behaves as reducing
M = Ag or Au
Ans. (a) agent.
This method is known as Mac-Arthur
Sodium polymetaphosphate is used to Forest cyanide process.
remove the permanent hardness of 16 Which of the following elements is
water. The commercial name of sodium 13 In the extraction of copper from its present as the impurity to the
polymetaphosphate is calgon meaning sulphide ore, the metal finally maximum extent in the pig iron?
calcium gone. obtained by the reduction of [CBSE AIPMT 2011]
The molecular formula of calgon is cuprous oxide with (a) Carbon (b) Silicon
Na2 [Na4 (PO3) 6 ]. [CBSE AIPMT 2015] (c) Phosphorus (d) Manganese
General Principles and Processes of Isolation of Metals 111
Ans. (a) Ans. (c) 23 Match items of Column I with the

Pig iron contains about 4% carbon Mercury is the only metal which is liquid items of Column II and assign the
(major impurity) and other impurities (S, at room temperature. Impure mercury correct code. [NEET 2016, Phase I]
P, Si, Mn) in trace amounts. metal is evaporated to obtain highly pure
mercury metal as distillate. This method Column I Column II
17 Which of the following statements, is known as distillation.
A. Cyanide process 1. Ultrapure Ge
about the advantage of roasting of
sulphide ore before reduction is 21 Match the elements in Column I B. Froth floatation 2. Dressing of ZnS
not true? [CBSE AIPMT 2007]
with methods of purification in process
(a) Carbon and hydrogen are suitable Column II. [NEET (Oct.) 2020]
C. Electrolytic 3. Extraction of Al
reducing agents for metal Column I Column II reduction
sulphides
A. Boron I. van-Arkel method D. Zone refining 4. Extraction of Au
(b) The ∆f G ° of the sulphide is greater
than those for CS2 and H2S B. Tin II. Mond’s process 5. Purification of Ni
(c) The ∆f G ° is negative for roasting of C. Zirconium III. Liquation
sulphide ore to oxide Codes
D. Nickel IV. Zone refining
(d) Roasting of the sulphide to the oxide A B C D A B C D
is thermodynamically feasible A B C D A B C D (a) 2 3 1 5 (b) 1 2 3 4
Ans. (a) (a) IV III I II (b) IV III II I (c) 3 4 5 1 (d) 4 2 3 1
Carbon and hydrogen are not suitable (c) II I IV III (d) III IV I II Ans. (d)
reducing agents for metal sulphides. Ans. (a) A – 4, B – 2, C – 3, D – 1
(A) Boron (and Ge, Si, Ga, In) get purified • Cyanide process It is a metallurgical
18 Which one of the following by zone refining (IV). technique for extracting Au (gold)
elements constitutes a major (B) Tin (and Bi, Pb) get purified by from low grade ore by converting the
impurity in pig iron? Liquation (III). Au to a water-soluble coordination
[CBSE AIPMT 1998] (C) Zirconium (and Ti, Hf) get purified by complex.
(a) Silicon (b) Oxygen van Arkel method (I). • Froth floatation process This
(c) Sulphur (d) Graphite (D) Nickel is purified by Mond’s process process is used for dressing of
(II). sulphide ore, i.e. ZnS.
Ans. (d)
Hence, option (a) is correctly match. • Electrolytic reduction This process
Graphite produces impurity in pig iron.
Pig iron contains 2.5 to 5.0% of carbon. is used for extraction of Al which is
22 Identify the correct statement from carried out in a steel tank lined inside
the following: [NEET (Sep.) 2020] with graphite. Here, graphite serves
19 The reaction of H2O 2 with hydrogen
(a) Blister copper has blistered as cathode. The electrolyte consists
sulphide is an example of ………… appearance due to evolution of CO2 . of alumina dissolved in fused cryolite
reaction. [CBSE AIPMT 1988] (b) Vapour phase refining is carried out (Na3 AlF6 ) and fluorspar (CaF2 ).
(a) addition (b) oxidation for nickel by van Arkel method. • Zone refining This process is used
(c) reduction (d) acidic (c) Pig iron can be moulded into a variety for ultra pure Ge element. An ingot of
Ans. (b) of shapes. Ge is first purified by zone refining.
(d) Wrought iron is impure iron with 4% Then a small amount of antimony is
When H2O2 is reacted with hydrogen
carbon. placed in the molten zone which is
sulphide (H2S), it form S and water. In this
reaction H2S is oxidised to sulphur. H2O2 Ans. (c) passed through the pure Ge with the
act as oxidising agent. (a) Matte on auto-reduction produces proper choice of rate of heating and
H2O2 + H2S → S + 2 H2O blister copper, which has blistered other variables.
appearance due to evolution ofSO2
(not CO2 ). 24 Which of the following pairs of
TOPIC 3 Cu2S + 2Cu2O → 6 Cu + SO2 ↑
Blister copper
metals is purified by van-Arkel
Refining of Metals
Matte method? [CBSE AIPMT 2011]
(b) Vapour phase refining is carried out (a) Zr and Ti
for Ni by Mond’s process (not by van (b) Ag and Au
20 Which one of the following Arkel method).
°C
(c) Ni and Fe
methods can be used to obtain Ni 4CO→ Ni(CO) 4 200 → Ni
Impure 80 °C − 4CO Pure (d) Ga and In
highly pure metal which is liquid at
(c) Pig iron can be moulded into variety Ans. (a)
room temperature? [NEET 2021]
of shapes. Zr and Ti are purified by van-Arkel
(a) Electrolysis (d) Wrought iron the purest form of iron method.
(b) Chromatography which contains 0.2-0.5% carbon (not
600 °C 1800 °C
(c) Distillation 4%). Zr + 2 I2 → Zr I4 → Zr + 2 I2
Impure Pure
(d) Zone refining So, option (c) is correct.
This method is useful for removing all of the impurity in the molten state than in this process 99.9% pure aluminium
the oxygen and nitrogen present in the the solid. metal is obtained.
form of impurity in certain metals like Zr Elements which are used as The cell used for this process consist of
and Ti. semiconductors like Si, Ge, Ga etc, are three layers. In this cell pure Al acts as
refined by this method. Gallium arsenide cathode and anode is made up of impure
25 The method of zone refining of and indium antimonide (also used as Al.
metals is based on the principle of semiconductor) are also refined by this
[CBSE AIPMT 2003] method. 27 Elemental silicon to be used as a
(a) greater noble character of the solid semiconductor is purified by
metal than that of the impurity 26 Purification of aluminium by [CBSE AIPMT 1996]
(b) greater solubility of the impurity in electrolytic refining is known as (a) heating under vacuum
the molten state than in the solid [CBSE AIPMT 1999]
(b) floatation
(c) greater mobility of the pure metal (a) Hall’s process (c) zone refining
than that of impurity (b) Baeyer's process (d) electrolysis
(d) higher melting point of the impurity (c) Hoope's process
than that of the pure metal
Ans. (c)
(d) Serpeck's process
Ans. (b) Zone refining is used for metals which
Ans. (c) are required in very high purity.
The method of zone refining of metals is Purification of aluminium by electrolytic Semiconductor grade silicon is purified
based on the principle of greater solubility refining is known as Hoope’s process. By by this method (Si, Ge).
15
Hydrogen
TOPIC 1 Protium is the most common isotopes of
TOPIC 2
hydrogen with an abundance of 99.98%.
Preparation and
Properties of Hydrogen
Hydrides and Water
03 ‘‘Metals are usually not found as
nitrates in their ores’’. 04 Match the following and identify the
01 Tritium, a radioactive isotope of [CBSE AIPMT 2015]
correct option. [NEET (Sep.) 2020]
hydrogen, emits which of the Out of the following two (I and II)
following particles? [NEET 2021] reasons which is/are true for the A. CO(g ) + H2 (g ) (i) Mg(HCO 3) 2 +
(a) Beta (β − ) (b) Alpha (α) above observation? Ca(HCO 3) 2
(c) Gamma (γ) (d) Neutron (n) I. Metal nitrates are highly B. Temporary (ii) An electron
Ans. (a) hardness of deficient
unstable. water hydride
Tritium ( 31 H) is an isotope of hydrogen. It II. Metal nitrates are highly soluble
is a radioactive isotope and decays by C. B2H6 (iii) Synthesis gas
emitting beta-particle ( β − ) to form 23He+ . in water.
D. H2O 2 (iv) Non-planar
3
→ 23He+ + e− (a) I and II are true structure
1H
Tritium β-particle (β – ) (b) I and II are false
+ 18.6 keV (c) I is false but II is true A B C D A B C D
(d) I is true but II is false (a) (iii) (ii) (i) (iv) (b) (iii) (iv) (ii) (i)
02 Which of the following statements
Ans. (c) (c) (i) (ii) (ii) (iv) (d) (iii) (i) (ii) (iv)
about hydrogen is incorrect?
[NEET 2016, Phase I] Metals are usually not found as nitrates Ans. (d)
in their ores, because metal nitrates are So, correct combinations are:
(a) Hydrogen never acts as cation in
highly soluble in water.
ionic salts (a)—(iii), (b)—(i), (c)—(ii), (d)—(iv)
(b) Hydronium ion, H 3O + exists freely in For example,KNO3 (salt peter) would be (a) Water gas (CO + H2 ) is also known as
solution classified as completely soluble. synthesis gas (iii).
(c) Dihydrogen does not act as a Thus, KNO3 could be expected to (b) Temporary hardness of water is due
reducing agent dissociate completely in aqueous to the presence ofHCO−3 radicals of
(d) Hydrogen has three isotopes of solution to give K+ and NO−3 ions. Mg2 + and/or Ca2 + ion(s) (i).
+ −
which tritium is the most common KNO3 eK (aq) + NO (aq) 3 (c) Boron atoms of B2H6 are
Ans. (c,d) The nitrate anion has three equivalent sp3-hybridised but due to the
oxygen surrounding a central nitrogen presence of twoB H B bonds
• For ionic salts, hydrogen never
behaves as cation, but behaves as atom. (3C2e − ), B2H6 becomes as an
electron deficient hydride (ii).
anion (H− ). This tends to spread the single negative
(d) H2O2 has a book-shaped non-planar
• H3 O + exists freely in solution. charge and make it easier for water
structure (iv).
• Dihydrogen acts as a reducing agent. (using hydrogen bonds) to separate the
ions in solution. H
• Hydrogen has three isotopes. – – O
O O O
• Protium (11H)
• Deuterium (21 H) N N N O
• Tritium (31 H) – – – – H
O O O O O O
Non-planar structure
TOPIC 3 method calculated amount of lime is (c) spherical

added to hard water. It precipitates out (d) linear
Heavy Water and H2O2 calcium carbonate and magnesium Ans. (b)
hydroxide which can be filtered off.
H2O2 shows non-planar structure. It has a
05 The method used to remove Ca(HCO3)2 + Ca(OH)2 →
half opened book like structure in which
temporary hardness of water is 2CaCO3 ↓ + 2H2O the two O—H groups lie on the two pages
[NEET (National) 2019] Mg(HCO3)2 + 2Ca(OH)2 → of the book.
(a) Clark’s method 2CaCO3 ↓ + Mg(OH)2 ↓ + 2H2O
(b) ion-exchange method Besides this, temporary hardness can 0.97Å
(c) synthetic resins method also be removed by boiling. All the other O H
(d) Calgon’s method. given methods are used to remove 97°
permanent hardness of water. 101.5° 1.48 Å
Ans. (a)
H O
Temporary hardness in water is due to 06 The structure of H2O 2 is
presence of magnesium and calcium 94°
[CBSE AIPMT 1999]
hydrogen carbonates.
(a) planar O—O single bond distance is 1.48 Å.
Temporary hardness in water can be
removed by Clark’s method. In this (b) non-planar
16
s-Block Elements
TOPIC 1 decreases in which of the following Ans. (d)
Group 1 Elements orders? [CBSE AIPMT 2008] The correct order of the mobility of the
(a) CsH > RbH > KH > NaH > LiH alkali metal ions in aqueous solution is
(Alkali Metals) Rb+ > K+ > Na+ > Li+ due to following
(b) KH > NaH > LiH > CsH > RbH
order of hydration energy of these ions
01 The following metal ion activates (c) NaH > LiH > KH > RbH > CsH Li+ > Na+ > K+ > Rb+ and as the hydration
many enzymes, participates in the (d) LiH > NaH > KH > RbH > CsH of ion increases, mobility decreases.
oxidation of glucose to produce Ans. (d) Hydration enthalpy
ATP and with Na, is responsible for As the size of the alkali metal cation 1
∝
the transmission of nerve signals increases, thermal stability of their Size of cation
[NEET (Sep.) 2020]
hydrides decreases.
(a) copper (b) calcium Hence, the correct order of thermal 06 Sodium is made by the electrolysis
stability of alkali metal hydrides is
(c) potassium (d) iron of a molten mixture of about 40%
LiH > NaH > KH > RbH > CsH
Ans. (c) NaCl and 60% CaCl 2 because
[CBSE AIPMT 1995]
The ionic-gradients between two sides 04 The sequence of ionic mobility in
(a) Ca2 + can reduce NaCl to Na
of a cell membrane, is operated by aqueous solution is
Na K pump and consumes one-third of (b) Ca2 + can displace Na from NaCl
[CBSE AIPMT 2008]
the ATP used by a resting animal. (c) CaCl2 helps in conduction of
(a) K + > Na+ > Rb + > Cs+ electricity
Potassium ion (K+ ) present in synapse (b) Cs+ > Rb + > K + > Na+
helps transmission of nerve signals from (d) this mixture has a lower melting
one neuron to another.
(c) Rb + > K + > Cs+ > Na+ point than NaCl
(d) Na+ > K + > Rb + > Cs+ Ans. (d)
02 Ionic mobility of which of the Ans. (b) The melting point of sodium chloride is
following alkali metal ions is lowest The smaller the size of the ion, the high, so to reduce the melting point of
when aqueous solution of their greater is the degree of hydration, thus NaCl some CaCl2 is added to the
degree of hydration is highest forLi+ and electrolytic mixture.
salts are put under an electric
lowest for Cs+ . Thus, Li+ holds more
field? [NEET 2017] water molecules in its hydration sphere
(a) Na (b) K
07 A certain compound X when
and becomes largest in size among alkali
(c) Rb (d) Li metals and Cs+ . ion hold least number of treated with copper sulphate
Ans. (d) water molecules. solution yields a brown precipitate.
Hence, ionic mobility is highest for Cs+ . On adding hypo solution, the
Key concept More the extent of
hydration, lesser is the ionic mobility . (due to its smallest size in aqueous precipitate turns white. The
solution) and lowest for Li+ Here the compound X is [CBSE AIPMT 1994]
In all the alkali metals,Li+ ion is smallest.
lowest is for Na+ . Thus, the order of ionic
Thus, extent of hydration is maximum in (a) K2CO 3 (b) KI
mobility in aqueous solution is
Li+ ion. (c) KBr (d) K 3PO 4
Cs+ > Rb+ > K+ > Na+
i.e. the dissolution ofLi+ in water occurs Ans. (b)
and get hydrated. Smaller the size of a
cation, greater is the extent of hydration 05 The correct order of the mobility of When potassium iodide is reacted with
the alkali metal ions in aqueous CuSO4 , it gives iodine gas which is brown
and lesser is the ionic mobility.
colour. This iodine reacted with sodium
thiosulphate and form white precipitate
03 The alkali metals form salt like (a) Li+ > Na+ > K + > Rb + of sodium tetrathionate.
hydrides by the direct synthesis at (b) Na+ > K + > Rb + > Li+ 2CuSO4 + 4 KI → K2SO4 + I2 ↑ + 2CuI
elevated temperature. The thermal (c) K + > Rb + > Na+ > Li+ 2Na2S2O3 + I2 → Na2S 4O6 ↓ + 2NaI
stability of these hydrides (d) Rb + > K + > Na+ > Li+
08 Which of the following is known as Ans. (a) 15 HCl was passed through a solution
fusion mixture? [CBSE AIPMT 1994] The ionic radii of alkali metal increases of CaCl 2 , MgCl 2 and NaCl. Which of
(a) Mixture of Na2CO 3 + NaHCO 3 as the atomic number increases when the following compound(s)
we move from top to bottom because on
(b) Na2CO 3 ⋅10H2O crystallise(s)? [NEET (Sep.) 2020]
moving down the group, there is a
(c) Mixture of K2CO 3 + Na2CO 3 increase in the number of shells and (a) Only NaCl (b) Only MgCl2
(d) NaHCO 3 therefore, ionic radii increases. (c) NaCl, MgCl2 and CaCl2
Ans. (c) (d) Both MgCl2 and CaCl2
A mixture of Na2 CO3 and K2 CO3 is used as Ans. (a)
a fusion mixture. TOPIC 2 Let us explain the crystallisation process
by a flow-sheet diagram.
09 Which of the following elements is Group 2 Elements
Aqueous solution : Filtration
extracted commercially by the (Alkaline Earth Metals) CaCl2+MgCl2+NaCl Insoluble
Filtrate
electrolysis of an aqueous solution impurities Excess of
of its compound? get removed HCl(g) is
13 Among the following alkaline earth passed
[CBSE AIPMT 1993]
metal halides, one which is
(a) Cl (b) Br (c) Al (d) Na covalent and soluble in organic Aqueous solution
Crystals of
Ans. (d) solvents is [NEET 2021] pure NaCl(s) of CaCl2 and MgCl2
Sodium is prepared by electrolysis of as these are more
(a) calcium chloride soluble than NaCl
molten NaCl as (b) strontium chloride
Electrolysis
2NaCl → 2Na + Cl2 (c) magnesium chloride
16 What is the role of gypsum,
At cathode : 2Cl – + 2 e − → Cl2 (d) beryllium chloride
CaSO 4 ⋅ 2H2O is setting of cement?
At anode : 2Na → 2Na+ + 2e − Ans. (d)
Identify the correct option from the
On moving down the group, the ionic size following. [NEET (Oct.) 2020]
10 Which of the following has largest of alkaline earth metals increases. So,
(a) to fasten the setting process
size? [CBSE AIPMT1993] due to small size ofBe2 + ion, Be has
highest polarising power [ability to attract (b) to provide water molecules for
(a) Na the electron cloud of anion (Cl − )]. hydration process
(b) Na+ (c) to help to remove water molecules
∴ BeCl2 is more covalent than other
(c) Na– alkaline earth metal halides. (d) to slow down the setting process
(d) Can’t be predicted Organic molecules are covalent in Ans. (d)
Ans. (c) nature. Rule for solubility is “Like Gypsum (CaSO4 ⋅2H2O) is present in
Na− has largest size because anion is dissolves like”. So,BeCl2 is soluble in cement (Portland cement) by a mass of
always larger than neutral atom and organic solvents as both are covalent in 2-3%.
cation is smaller than neutral atom. So nature. Gypsum slow down the process of
the order is given as setting of cement so that it gets
Na− > Na > Na+ 14 The structures of beryllium sufficiently hardened.
Anion > Parental atom > Cation chloride in solid state and vapour
phase, are [NEET 2021] 17 Which of the following is an
11 Washing soda has formula (a) chain and dimer, respectively amphoteric hydroxide?
[CBSE AIPMT 1990] (b) linear in both [NEET (National) 2019]
(a) Na2CO 3 ⋅ 7H2O (b) Na2CO 3 ⋅10H2O (c) dimer and linear, respectively (a) Ca(OH)2 (b) Mg(OH)2
(c) Na2CO 3 ⋅ 3H2O (d) Na2CO 3 (d) chain in both (c) Be(OH)2 (d) Sr(OH)2
Ans. (b) Ans. (a) Ans. (c)
Washing soda is chemicaly named as Beryllium chloride (BeCl2 ) is an electron Be(OH)2 is amphoteric in nature as it
sodium carbonate decahydrate, so its deficient compound. So, it does not exist reacts with acid and alkali both as :
formula is Na2 CO3 ⋅ 10H2O. in its monomer form. Be(OH)2 + 2HCl → BeCl2 + 2H2O
In solid state and vapour phase,BeCl2 Be(OH)2 + 2NaOH → Na2 [Be(OH) 4 ]
12 Which one of the following exists in chain and dimer forms This amphoteric nature of Be is due to
properties of alkali metals respectively. small size of Be. The other hydroxides of
increases in magnitude as the Cl Cl Cl alkaline earth metals are basic in nature.
Be Be Be
atomic number rises?
[CBSE AIPMT 1989] Cl Cl Cl 18 The product obtained as a result of
(a) Ionic radius
Chain form a reaction of nitrogen with CaC 2 is
Cl [NEET 2016, Phase I]
(b) Melting point Cl Be Be Cl
(c) Electronegativity (a) CaCN (b) CaCN 3
Cl (c) Ca2 CN (d) Ca(CN)2
(d) First ionisation energy Dimer form
s-Block Elements 117
Ans. (*) Mg > Ca > Sr > Ba 25 In which of the following the

When calcium carbide (CaC2 ) reacts with The magnitude of the lattice energy hydration energy is higher than the
nitrogen (N2 ) under high temperature, it remains almost constant as the size of
lattice energy? [CBSE AIPMT 2007]
forms calcium cyanamide which is also the sulphate ion is so big that small
called nitrolim. increase in the size of the cation from Be (a) BaSO 4 (b) MgSO 4
High to Ba does not make any difference. (c) RaSO 4 (d) SrSO 4
CaC2 + N2 → CaCN2 However, the hydration energy Ans. (b)
temperature
Calcium cyanamide
decreases fromBe2 + to Ba2 + appreciably
Hydration energy of sulphate decreases
+ C as the size of the cation increases down
from top to bottom in II group.Mg2 + is
Hence, option (d) should be CaCN2 the group. The significantly high
smaller than other given ions of II group,
solubility of MgSO4 is due to high
instead of Ca(CN)2 . Thus no option is so Mg2 + is readily hydrated.MgSO4 has
correct. enthalpy of solvation of the smallerMg2 +
higher hydration energy than lattice
ions.
energy.
is false? [NEET 2016, Phase I]
22 On heating which of the following 26 The correct order of increasing
2+
(a) Ca ions are important in blood releases CO 2 most easily? thermal stability of K 2CO 3 , MgCO 3 ,
[CBSE AIPMT 2015]
clotting CaCO 3 and BeCO 3 is
(b) Ca2 + ions are not important in (a) K2CO 3 (b) Na2CO 3 [CBSE AIPMT 2007]
maintaining the regular beating of (c) MgCO 3 (d) CaCO 3
(a) BeCO 3 < MgCO 3 < K2CO 3 < CaCO 3
the heart Ans. (c)
(c) Mg2 + ions are important in the green
(b) BeCO 3 < MgCO 3 < CaCO 3 < K2CO 3
Order of thermal stability is (c) MgCO 3 < BeCO 3 < CaCO 3 < K2CO 3
parts of plants
K2 CO3 > Na2 CO3 > CaCO3 > MgCO3
(d) Mg2 + ions form a complex with ATP (d) K2CO 3 < MgCO 3 < CaCO 3 < BeCO 3
Hence,MgCO3 releases CO2 most easily
Ans. (b) Ans. (b)
MgCO3 →∆ MgO + CO2
• Ca2 + ions are very important factor in Thermal stability of carbonates
blood clotting. increases in a group as we move from
23 Which one of the following is
• Ca2 + ions are very important for top to bottom and decreases in a period
present as an active ingredient in as we move from left to right, so the
maintaining the regular heart beating.
bleaching powder for bleaching correct order of thermal stability of
• Mg2 + ions is present in the green
parts of plants i.e., chlorophyll. action? [CBSE AIPMT 2011] given carbonates is
BeCO3 < MgCO3 < CaCO3 < K2 CO3
• Mg2 + can form a complex with ATP. (a) Ca(OCl)2 (b) CaO2Cl2
(c) CaCl2 (d) CaOCl2 Be, Mg and Ca are present in second
20 In context with beryllium, which Ans. (a) group and K is present in first group.
one of the following statements is Ca(OCl)2 , calcium hypochlorite is the
27 Which one is the correct statement
incorrect? [NEET 2016, Phase II] active ingredient in bleaching powder
which releases chlorine. with reference to the solubility of
(a) It is rendered passive by nitric acid
MgSO 4 in water? [CBSE AIPMT 1996]
(b) It forms Be2 C
24 Equimolar solutions of the (a) SO24− ions mainly contributes towards
(c) Its salts rarely hydrolyse
following were prepared in water hydration energy
(d) Its hydride is electron-deficient and
polymeric separately. Which one of the (b) Sizes of Mg2 + and SO24− are similar
Ans. (c) solutions will record the highest (c) Hydration energy of MgSO4 is higher
in comparison to its lattice energy
Beryllium salts are covalent in nature pH? [CBSE AIPMT 2008]
(d) Ionic potential (charge/radius ratio)
because of very small size ofBe2 + ion (a) SrCl2 (b) BaCl2 of Mg2 + is very low
and its high polarising power, so it is (c) MgCl2 (d) CaCl2
easily hydrolysed. Ans. (c)
Ans. (b)
e.g. BeCl2 + 2H2O → Be(OH) 2 + 2HCl MgSO4 is soluble in water because it
All salts are soluble in water and give have hydration energy more than lattice
strong acid and weak base energy.
21 Solubility of the alkaline earth's
SrCl2 + 2H2O → Sr(OH) 2 + 2HCl Mg2 + ions mainly contributes towards
metal sulphates in water decreases
BaCl2 + 2H2O → Ba(OH) 2 + 2HCl hydration energy
in the sequence [CBSE AIPMT 2015]
MgCl2 + 2H2O → Mg(OH) 2 + 2HCl size of SO24− ion is greation thanMg2 +
(a) Mg > Ca > Sr > Ba
CaCl2 + 2H2O → Ca(OH) 2 + 2HCl ions.
(b) Ca > Sr > Ba > Mg
The basic nature of alkaline earth metals
(c) Sr > Ca > Mg > Ba
generally increases from Be to Ra. Thus, 28 Identify the correct statement.
(d) Ba > Mg > Sr > Ca the order of basic nature of these [CBSE AIPMT 1995]
Ans. (a) hydroxides is (a) Gypsum is obtained by heating
Solubility of the sulphates. The Mg(OH)2 < Ca(OH)2 < Sr(OH) 2 < Ba(OH) 2 plaster of Paris
sulphates becomes less soluble as you Hence, pH is highest forBaCl2 . (As pH (b) Plaster of Paris can be obtained by
go down the group i.e. increases with basic nature) hydration of gypsum
(c) Plaster of Paris is obtained by partial (c) Ca and CaH2 36 Which of the following metal
oxidation of gypsum (d) Ba and BaO2 evolves hydrogen on reacting with
(d) Gypsum contains a lower percentage Ans. (c)
of calcium than plaster of Paris
cold dilute HNO 3 ?
Ca and CaH2 gives H2 and calcium [CBSE AIPMT 1989]
Ans. (d) hydroxide when reacted with water. (a) Mg (b) Al
The formula of gypsum is CaSO4 ⋅2H2O Ca + H2O → Ca(OH)2 + H2 ↑ (c) Fe (d) Cu
and that of plaster of Paris is CaH2 + 2H2O → Ca(OH) 2 + 2H2 ↑ Ans. (a)
(CaSO4 )2 ⋅2H2O, so the percentage of Ca
in plaster of Paris is more than gypsum. Magnesium react with cold and dilute
33 Which one of the following has nitric acid to form hydrogen.
29 Which of the following statement is minimum value of size of Mg + 2HNO3 → Mg(NO3)2 + H2
false? [CBSE AIPMT 1994] cation/anion ratio?
(a) Strontium decomposes water readily [CBSE AIPMT 1993] 37 Which one of the following atoms
than beryllium (a) NaCl (b) KCl will have the smallest size?
(b) BaCO3 melts at a higher temperature (c) MgCl2 (d) CaF2 [CBSE AIPMT 1989]
than CaCO3 Ans. (c) (a) Mg (b) Na
(c) Barium hydroxide is more soluble in
water than Mg(OH)2 The size of Mg2 + is minimum amongNa+ , (c) Be (d) Li
Ca2 + , K+ and Mg2 + and size of Cl − is more Ans. (c)
(d) Beryllium hydroxide is more basic
than F − , so the ratio of size of cation and
than barium hydroxide Atomic size increases down the group
anion are minimum inMgCl2 .
Ans. (d) and decreases in period from left to
right. So, Be is smallest in size in these
The size of beryllium is very small and 34 When chlorine is passed over dry elements.
the hydroxide formed by it, are
amphoteric in nature, so its hydroxide is slaked lime at room temperature,
Alkali Alkaline earth
less basic than barium hydroxide. the main reaction product is metal metal
[CBSE AIPMT 1992] Group 1 Group 2
30 Which of the following metal ions (a) Ca(ClO2 )2 (b) CaCl2
play an important role in muscle (c) CaOCl2 (d) Ca(OCl)2 Li Be
contraction? [CBSE AIPMT 1994] Ans. (c) Size increases
Na Mg
(a) K + (b) Na+ (c) Mg2+ (d) Ca2+ When chlorine gas is passed over dry
Ans. (d) slaked lime, it form bleaching powder i.e.
CaOCl2 . Size decreases
Calcium ion (Ca2 + ) play an important role
in muscle contraction. Ca(OH)2 + Cl2 → CaOCl2 + H2O
38 Bleaching powder is obtained by
31 The formula for calcium chlorite is 35 Compared with the alkaline earth the action of chlorine gas and
metals, the alkali metals exhibit
(a) Ca(ClO 4 )2 (b) Ca(ClO 3)2 [CBSE AIPMT 1990] (a) dilute solution of Ca(OH)2
(c) CaClO2 (d) Ca(ClO2 )2 (a) smaller ionic radii (b) concentrated solution of Ca(OH)2
Ans. (d) (b) higher boiling points (c) dry CaO
The formula of calcium chlorite is (c) greater hardness (d) dry slaked lime
Ca(ClO2 )2 . (d) lower ionisation energies Ans. (d)
Ans. (d) Bleaching powder is prepared by passing
32 All the following substances react chlorine gas over dry slaked lime Ca(OH)2
with water. The pair that gives the Alkali metals have the lowest ionisation
enthalpy in each period because alkali by Hesenclaver method or by Bachmann
same gaseous product is metals are largest in their respective method.
[CBSE AIPMT 1994] periods and therefore, the valency Ca(OH)2 + Cl2 → CaOCl2 + H2O
(a) K and CO2 electrons are loosely held by the
(b) Na and Na2O2 nucleus.
17
p-Block Elements
TOPIC 1 03 AlF 3 is soluble in HF only in 06 Which one of the following
Group 13 Elements molecular hydrides acts as a Lewis
presence of KF. It is due to the
acid? [CBSE AIPMT 2010]
formation of [NEET 2016, Phase II]
01 Which one of the following (a) K 3 [AIF3H3] (b) K 3 [AIF6]
(a) NH3 (b) H2O
elements is unable to form MF63− (c) AIH 3 (d) K [AIF3H]
(c) B2H6 (d) CH4
ion? [NEET 2018] Ans. (c)
Ans. (b)
(a) B (b) Al Key Idea Electron deficient molecules
(c) Ga (d) In Key Idea Al 3+ shows maximum behave as Lewis acid.
coordination number 6, thus it will form
Ans. (a) Among the given molecules, only
AlF63− .
diborane is electron deficient, i.e. does
Boron belongs to 2nd period of the AlF3 forms K3 [AlF6 ] when dissolved in HF not have complete octet. Thus, it acts as
periodic table with electronic in the presence of KF as shown below: a Lewis acid.
configuration 1s 2 , 2s 2 2p1. It does not HF
have vacant d-orbitals, thus cannot AlF3 + 3KF → K3 [AlF6 ] NH3 and H2O being electron rich
increase its covalency above four. molecules behave as Lewis base.
Therefore, boron (B) cannot form MF63− 04 The stability of +1 oxidation state
ion. In contrast, aluminium (Al), gallium among Al, Ga, In and Tl increases 07 The tendency of BF3 , BCl 3 and
(Ga), indium (In) have the vacant in the sequence [CBSE AIPMT 2015] BBr 3 behave as Lewis acid
3d-orbitals, thus can increase their decreases in the sequence
covalence above four and form MF63− ion. (a) Ga < ln < Al < Tl (b) Al < Ga < ln < Tl
(c) Tl< ln < Ga < Al (d) ln < Tl < Ga < Al [CBSE AIPMT 2009]
Ans. (b) (a) BCl3 > BF3 > BBr3

02 Boric acid is an acid because its
molecule [NEET 2016, Phase II] Al < Ga < In < Tl (b) BBr3 > BCl3 > BF3
+
(a) contains replaceableH ion This is due to inert pair effect or (c) BBr3 > BF3 > BCl3
(b) gives up a proton tendency of ns 2 electrons do not (d) BF3 > BCl 3 > BBr3
(c) accepts OH − from water releasing participate in bond formation. This
Ans. (b)
proton tendency decreases on moving down the
group. As the size of halogen atom increases,
(d) combines with proton from water the acidic strength of boron halides
molecule
05 Which of the following structure is increases. Thus,BF3 is the weakest
Ans. (c) similar to graphite? [NEET 2013] Lewis acid. This is because of the
Boric acid can be considered as an acid pπ − pπ back bonding between the fully
(a) BN (b) B (c) B 4C (d) B2H6
because its molecule acceptsOH− from filled unutilised2p-orbitals of F and
water, releasing proton. Ans. (a) vacant 2p-orbitals of boron which makes
BF3 less electron deficient. Such back
H3BO3 + H2O q B(OH) –4 + H+ Boron nitride (BN)x resembles with
Conjugate Conjugate graphite in structure as shown below donation is not possible in case ofBCl 3 or
Acid Base base acid BBr3 due to larger energy difference
B B C C between their orbitals. Thus, these are
Remember In the given options to the N N N C C C more electron deficient. Since on
question, (a), (b) and (c) are correct as all moving down the group the energy
of these sentences have more or less B B B C C C difference increases, the Lewis acid
similar meaning but here (c) option is the N N C C character also increases. Thus, the
most appropriate one as it gives B B C C tendency to behave as Lewis acid
complete explanation of the fact that N N C follows the order
how boric acid can be combined with an BBr3 > BCl 3 > BF3
acid. Boron nitride Graphite
08 The stability of +1 oxidation state 11 Which one of the following Ans. (a)
increases in the sequence statements about the zeolites is In diborane 3 centred 2 electron bond is
[CBSE AIPMT 2009] false? [CBSE AIPMT 2004] present.
(a) Al < Ga < In < Tl (b) Tl < In < Ga < Al H H H
(a) They are used as cation exchangers
(c) In < Tl < Ga < Al (d) Ga < In < Al < Tl (b) They have open structure which B B
Ans. (a) enables them to take up small H H H
molecules Diborane
The given elements belong to third (3c -2 e bond present)
(c) Zeolites are aluminosilicates having
group. These elements mainly exhibit +3
three dimensional network
and +1 oxidation states. As we know, the
(d) Some of the SiO4–
stability of lower oxidation state, 4 units are replaced
by AlO54 – and AlO96 – ions in zeolites about H3BO 3 is not correct?
increases on moving down a group due [CBSE AIPMT 1994]
to inert pair effect. Thus, the sequence Ans. (d) (a) It is a strong tribasic acid
of stability of +1 state is
Zeolites are aluminosilicates having (b) It is prepared by acidifying an
Al < Ga < In < Tl three dimensional open structure in aqueous solution of borax
which four or six membered rings (c) It has a layer structure in which
09 Al 2O3 can be converted into predominates. Thus, due to open chain planar BO3 units are joined by
anhydrous AlCl 3 by heating structure, they have cavities and can hydrogen bonds
[CBSE AIPMT 2006] take up water and other small molecules.
(d) It does not act as proton donor but
(a) Al2O3 with HCl gas acts as a Lewis acid by accepting
(b) Al2O3 with NaCl in solid state 12 In borax bead test which hydroxyl ion
(c) a mixture of Al2O3 and carbon in dry compound is formed? Ans. (a)
Cl2 gas [CBSE AIPMT 2002]
Boric acid (H3BO3) is a weak monobasic
(d) Al2O3 with Cl2 gas (a) Ortho borate (b) Meta borate acid withK a = 1.0 × 10 −9 .It may be noted
Ans. (c) (c) Double oxide (d) Tetra borate that boric acid does not act as a protonic
Al2O3 may be converted into anhyd. AlCl 3 Ans. (b) acid (i.e. proton donor) but behaves as a
by heating a mixture of Al2O3 and carbon In borax bead test the coloured meta Lewis acid by accepting a pair of
in dry chlorine. borates are formed by transition metal electrons from OH− ion.
salts. B(OH) 3 + 2H — O — H →
Al2O3 + 3C + 3Cl2 → Al2 Cl 6
∆ [B(OH) 4 ] – + H3O+
Hot and dry AnhyAlCl3 Na2B4O7 ⋅ 10H2O → Na2B4O7
–10H2O
NOTE Anhydrous AlCl 3 exists in the form
of dimer as Al2 Cl 6 ∆ 2NaBO2 + B2O3
→ TOPIC 2
B2O3 + CuO → Cu(BO2 ) 2
10 Which of the following is the Cupric metaborate Group 14 Elements
(Blue bead)
electron deficient molecule?
[CBSE AIPMT 2005] 16 Which of the following oxide is
(a) B2H6 (b) C2H6 13 Among the following the electron
amphoteric in nature?
(c) PH3 (d) SiH4 deficient compound is [NEET (Oct.) 2020]
[CBSE AIPMT 2000]
Ans. (a) (a) SnO2 (b) SiO2
(a) BCl3 (b) CCl4 (c) PCl5 (d) BeCl2 (c) GeO2 (d) CO2
B2H6 is electron deficient molecule
Ans. (a) Ans. (a)
because boron atom has three half-filled
orbitals in excited state. The structure of  Cl
In BCl 3  Cl —B  boron contains six Nature of dioxides (MO2 ) of group 14
B2H6 is represented as follows:   elements can be represented as.
 Cl
H CO2 SiO2 GeO2 SnO2 PbO2
electrons in its valence shell so, it is
H 97° H capable to accommodate one pair of Acidic oxides Amphoteric oxides
electrons. Hence, it acts as Lewis acid or Hence, option (a) is correct.
122° B B 122° electron deficient (incomplete octate)
compound. As we know that Lewis acids
H Å 97° H are the substances having a tendency to
17 Identify the correct statements
1.19 3Å
1.3 accept a pair of electron. from the following:
H
1. CO 2 (g) is used as refrigerant
1.77Å
14 Which of the following compound for ice-cream and frozen
has a 3-centre bond? food.
In it two electrons of aB H bond are [CBSE AIPMT 1996]
involved in formation of three centre 2. The structure of C 60 contains
(a) Diborane (b) CO2 twelve six carbon rings and
bond, these bonds are represented as
dotted lines. (c) Boron trifluoride twenty five carbon rings.
(d) Ammonia
p-Block Elements 121
3. ZSM-5, a type of zeolite, is 20 Which of these is not a monomer  CH3  CH3

   
used to convert alcohols into for a high molecular mass silicon  Si  O
O  Si  O—
—
gasoline. polymer? [NEET 2013]    
 CH3  CH3
4. CO is colourless and odourless (a) MeSiCl3 (b) Me2 SiCl2   n −1
Straight chain polymer
gas. [NEET (Sep.) 2020] (c) Me 3SiCl (d) PhSiCl3
(silicon)
(a) (1) and (3) only Ans. (c)
Straight chain silanes are silicon oils.
(b) (2) and (3) only Me3SiCl is not a monomer for a high These are more stable at high
(c) (3) and (4) only molecular mass silicon polymer because temperature than mineral oils and have
(d) (1), (2) and (3) only it generatesMe3SiOH when subjected to less tendency to thicken at low
hydrolysis which contains only one temperature.
Ans. (c)
reacting site. Hence, the polymerisation
3 and 4 are correct statements, whereas reaction stops just after first step.
1 and 2 are incorrect.
23 Which one of the following anions
1. Dry ice or CO2 (s ) [not CO2 (g)] is used is present in the chain structure
21 Name the type of the structure of
as refrigerant for ice-cream and silicates? [CBSE AIPMT 2007]
silicate in which one oxygen atom
frozen food. (a) Si2O 76– (b) (Si2O2–
5 )n
2. C60 contains 20 hexagones (not 12) of [SiO 4] 4– is shared? (c) (SiO2– (d) SiO 4–
3 )n 4
and 12 pentagones (not 20). [CBSE AIPMT 2011]
Ans. (c)
3. ZSM-5, a type of zeolite, is used to (a) Sheet silicate
convert alcohols directly into [SiO23– ] n and [Si4O11] 6 − have chain
(b) Pyrosilicate
gasoline. It is true. structure of silicates.
(c) Three dimensional silicate
4. CO is a colourless and odourless gas. (d) Linear chain silicate
It is true. 24 Which of the following oxidation
Ans. (b) states are the most characteristics
In pyrosilicate, only one oxygen atom is for lead and tin respectively?
18 Which of the following is incorrect shared. [CBSE AIPMT 2007]
– –
statement? [NEET (National) 2019] (a) +4, +2 (b) +2, +4
(a) SiCl 4 is easily hydrolysed (c) +4, +4 (d) +2, +2
(b) GeX4 (X =, F, Cl, Br, I) is more stable – – O=O Ans. (b)
= Si
than GeX2 The tendency to form +2 ionic state
(c) SnF4 is ionic in nature increase on moving down the group due
– –
(d) PbF4 is covalent in nature Pyrosilicate to inert pair effect.
Ans. (d) Most characteristic oxidation state for
All the tetrahalides of group 14 elements 22 The straight chain polymer is lead and tin are +2, +4 respectively.
are covalent in nature and sp3-hybridised formed by [CBSE AIPMT 2009]
with tetrahedral geometry. Exceptions (a) hydrolysis of (CH3) 3SiCl followed by
are SnF4 and PbF4 which are ionic in condensation polymerisation 25 Percentage of lead in lead pencil is
nature. Thus, statement (d) is incorrect (b) hydrolysis of CH3SiCl 3 followed by [CBSE AIPMT 1999]
while the remaining statements are condensation polymerisation (a) zero (b) 20 (c) 80 (d) 70
correct. (c) hydrolysis of (CH3) 4 Si by addition Ans. (a)
polymerisation
19 The basic structural unit of In lead pencil graphite and clay is
(d) hydrolysis of (CH3)2 SiCl2 followed by
[NEET 2013] present, so the percentage of lead is
silicates is condensation polymerisation
zero.
(a) SiO − (b) SiO 4−
4 Ans. (d)
2−
(c) SiO 3 (d) SiO2−4 CH3 CH3 26 Which of the following does not
Ans. (b)  Hydrolysis  show electrical conduction?
Cl  Si  Cl → HO  Si  OH
The basic building unit of all silicates  –HCl
 [CBSE AIPMT 1999]
is the tetrahedral SiO 4−
4 . It is CH3 CH3 (a) Potassium (b) Graphite
represented as Dimethyl (c) Diamond (d) Sodium
– dichlorosilane
O Ans. (c)
CH3
Si
=O  Diamond does not show electrical
–
= Si nHO  Si  OH → conductivity due to the absence of free
– –H2O
O –
O  electrons. Sodium and potassium are
O CH3 (Condensation
polymerisation) metallic conductors while graphite is a
Structure of SiO4–
4 unit non-metallic conductor.
27 A one litre flask is full of brown Ans. (a) Ans. (a)

bromine vapours. The intensity of Water gas is produced when steam is The given road map problem is
brown colour of vapours will not passed over red hot coke beds.
‘X’ + H2O ‘Y’ (colourless)
decrease appreciably on adding to C(s ) + H2O( g ) → CO( g ) + H2 ( g ) Rotten fish smell
14 4244 3
the flask some [CBSE AIPMT 1998] Water gas
CuSO4
(a) pieces of marble
(b) animal charcoal powder 31 Which of the following types of Cu3P2 + Product
(c) carbon tetrachloride forces bind together the carbon
(d) carbon disulphide atoms in diamond? As compound ‘X’ produces a colorless
gas ‘Y ’ with rotten fish smell, it can be
Ans. (a) [CBSE AIPMT 1992]
Ca3P2 (calcium phosphide). The reaction
Bromine is soluble in CCl 4 and CS2 . (a) Ionic takes palce as follows :
Animal charcoal also adsorbs on bromine (b) Covalent
Ca3P2 + H2O → Ca(OH) 2 + PH3
water. But marble has no action withBr2 . (c) Dipolar
So, after adding marble piece to the Colorless gas with rotten fish smell. ‘Y ’
(d) van der Waals’
flask, there will be no change in the CuSO4 +PH3 → Cu3P2 + H2SO4
Ans. (b)
intensity of brown colour. 'Y'
In diamond, each carbon atom
undergoes sp3 hybridisation and is 35 Which of the following oxoacids of
28 The structure and hybridisation of phosphorus has strongest reducing
covalently bonded to three other carbon
Si(CH3 ) 4 is [CBSE AIPMT 1996]
atoms by single bonds. property? [NEET (National) 2019]
(a) octahedral, sp 3d
(a) H4P2O 7 (b) H3PO 3
(b) tetrahedral, sp 3 32 Glass is a [CBSE AIPMT 1991]
(c) bent, sp (c) H3PO2 (d) H3PO 4
(a) liquid
(d) trigonal, sp2 (b) solid
Ans. (c)
Ans. (b) (c) supercooled liquid P H bonds found in phosphorus
In tetramethyl silicane, i.e.Si(CH3) 4 , Si is acids have reducing properties. Thus,
(d) transparent-organic polymer
sp3 hybridised. Hence it has tetrahedral reducing property is directly
Ans. (c) proportional to number of P H
structure.
Glass is an example of amorphous solid. bonds. The structures of given
It is also known as supercooled liquid. oxoacids of phosphorus are as
29 In graphite, electrons are
Glass have short range order of follows :
[CBSE AIPMT 1993, 97]
constituents.
(a) localised on each C-atom
O O O
(b) localised on every third C-atom 33 The substance used as a smoke
(c) spread out between the structure P P P
screen in warfare is HO O OH H OH
(d) Both (b) and (c) [CBSE AIPMT 1989] HO OH OH
Ans. (d) (a) SiCl4 (b) PH3 (H4P2O7) (H3PO3)
Structure of graphite consist of a two (c) PCl5 (d) acetylene O O

dimensional sheet like network joined Ans. (a) P P
together in hexagonal rings. These H OH HO OH
Silicon chloride is easily hydrolysed to
layers are held together by weak van der H
give white fumes, so it is used as a HO
Waals’ forces. In graphite each carbon (H3PO2)
smoke screen in warfare. (H3PO4)
atom is bonded to three others, forming
sp2 hybrid bonds. The fourth electron SiCl 4 + 4H2O → Si(OH) 4 + 4HCl
H3PO2 contains 2P H bonds which is
forms a π-bond. maximum among given options. Thus,
Graphite is a conductor of electricity H3PO2 has strongest reducing
which is due to the fact that all the TOPIC 3 property.
carbon bonds being not satisfied. Thus,
some of the electrons are free to move
Group 15 Elements
through the crystal. 36 Identify the incorrect statement
34 A compound ‘X’ upon reaction with related to PCl 5 from the following:
30 Water gas is produced by H2O produced a colourless gas ‘Y’ [NEET (National) 2019]
[CBSE AIPMT 1992] with rotten fish smell. Gas ‘Y ’ is (a) Two axial P Cl bonds make an
(a) passing steam through a red hot absorbed in a solution of CuSO 4 to angle of 180° with each other
coke bed give Cu 3P2 as one of the products. (b) Axial P Cl bonds are longer than
(b) saturating hydrogen with moisture equatorial
Predict the compound ‘X’ P Cl bonds
(c) mixing oxygen and hydrogen in the [NEET (Odisha) 2019]
ratio of 1 :2 (c) PCl 5 molecule is non-reactive
(a) Ca3P2 (b) NH4Cl (d) Three equatorial PCl bonds make
(d) heating a mixture of CO2 and CH4 in (c) As2O 3 (d) Ca3 (PO 4 )2
petroleum refineries an angle of 120° with each other
Ans. (c) exhaust fumes and when fossil fuels are Due to the presence of one replaceable
In gaseous and liquid phases,PCl 5 has a burnt as well as produced during proton in phosphinic acid, it is
trigonal bipyramidal structure with thunderstorms. In each case NO is monoprotic acid. And due to presence of
sp3d-hybridisation. formed first and thenNO2 . two replaceable proton in phosphonic
acid, it is diprotic acid.
Axial
Cl 39 The species, having bond angles of
Cl bond
202
120° is [NEET 2017] 41 Among the following, which one is
90°
a wrong statement?
120°
Cl—— P pm
(a) PH3 (b) ClF3 (c) NCl3 (d) BCl3
Equatorial 240 Cl Ans. (d)
bond
pm
Cl (a) PH5 and BiCl5 do not exist
The species having bond angles of 120°
(b) pπ-dπ bonds are present in SO2
Due to presence of longer and weaker is BCl 3. It is sp2 -hybridised and central
axial bonds PCl 5 is a reactive molecule. atom does not have any lone pair of (c) SeF4 and CH4 have same shape
Hence, statement in option (c) is electrons. (d) I+3 has bent geometry
incorrect while the remaining options Ans. (c)
Chemical
contain correct statements. Species Bond angle
formula PH5 does not exist due to very less
electronegativity difference between P
PH 3 93.5°
37 The correct order of N-compounds and H. Hydrogen is slightly more
in its decreasing order of oxidation P electronegative than phosphorus, thus
states is [NEET 2018] could not hold significantly the sharing
H H H electrons.
(a) HNO 3, NH4Cl, NO, N2 (Pyramidal) On the other hand,BiCl 5 does not exist
(b) HNO 3, NO, NH4Cl, N2 due to inert pair effect.
(c) HNO 3, NO, N2 , NH4Cl ClF3 F 90°
On moving down the group, +5 oxidation
(d) NH4Cl, N2 , NO, HNO 3 Cl F state becomes less stable while +3
Ans. (c) oxidation state becomes more stable.
F In SO2 , pπ-dπ and pπ-pπ both types of
Let the oxidation state of nitrogen in (T-shaped)
each of the given N-compounds be x. bonds are present
(i) HNO3 : + 1 + x + 3 (−2) = 0 NCl 3 N 107.8°
x=+5 Cl Cl Cl
∴Oxidation state of N inHNO3 is +5. (Pyramidal)
(ii) NO : x + 1(−2) = 0
x = +2 BCl 3 Cl 120°
∴Oxidation state of N in NO is +2. B
(iii) NH4 Cl : x + 4(+1) + 1(−1) = 0 Cl
Cl Thus, SeF4 and CH4 do not have same
x = −3 (Trigonal planar) shape.
∴ Oxidation state of N inNH4 Cl is −3.
(iv) N2 : x = 0 [QN2 is present in elemental r
state] 40 Which is the correct statement for
∴Oxidation state of N inN2 is 0. the given acids? I
Thus, the correct decreasing order of [NEET 2016, Phase I]
I I
oxidation states of given N- (a) Phosphinic acid is a monoprotic acid
Geometry-Bent
compounds will be while phosphonic acid is a diprotic
+5 +2 0 −3 acid
HN O3 > NO >N2 > NH4 Cl Thus, option (c) is incorrect statement.
(b) Phosphinic acid is a diprotic acid
while phosphonic acid is a
42 Maximum bond angle at nitrogen is
38 Which oxide of nitrogen is not a monoprotic acid
(c) Both are triprotic acids
present in which of the following?
common pollutant introduced into [CBSE AIPMT 2015]
the atmosphere both due to natural (d) Both are diprotic acids
(a) NO2 (b) NO2–
and human activity? Ans. (a)
[NEET 2018] (c) NO2+ (d) NO –3
(a) N2O (b) NO2 Phosphinic acid Ans. (c)
(c) N2O 5 (d) NO O
Ans. (c) Species Hybridisation Bond angle
P
H OH NO 2 sp less than 120°
Nitrous oxide (N2O) , nitrogen dioxide
(NO2 ) and nitric oxide (NO) are the H
NO −2 sp 2
115.4°
common pollutant introduced into the Phosphonic acid
atmosphere. O NO 2+ sp ( linear) 180°
N2O occurs naturally in environment. NO NO −3 sp 2 120°
P
and NO2 causes considerable amount of HO H
air pollution. They are given off in car HO So, NO2+ has maximum bond angle.
43 Strong reducing behaviour of 4 + 2x − 10 = 0 48 Nitrogen forms N 2 , but phosphorus

H3PO 2 is due to [CBSE AIPMT 2015] 2x = 6
when form P2 readily converted
(a) presence of one  OHgroup and two ∴ x=+3
into P4 , reason is
P  H bonds [CBSE AIPMT 2001]
(b) high electron gain enthalpy of In H4P2O6 (a) triple bond present between
phosphorus (+ 1) × 4 + 2 × x + (− 2) × 6 = 0 phosphorus atom
(c) high oxidation state of phosphorus 4 + 2x − 12 = 0 (b) pπ – pπ bonding is weak
(d) presence of two —OH groups and one (c) pπ – pπ bonding is strong
2x = 8
P  H bond
∴ x=+4 (d) multiple bond form easily
Ans. (a)
In H4P2O7 Ans. (b)
The oxy acid of phosphorus which
(+ 1) × 4 + 2 × x + (− 2) × 7 = 0 Nitrogen form N2 (i.e. N ≡≡ N) but
contain P—H bond act as a reducing
agent or reductant. 4 + 2x − 14 = 0 phosphorus form P2 , it is at a time
2x = 10 convert inP4 , because inP2 , pπ - pπ
O bonding is present which is a weaker
∴ x=+ 5
P bonding due to larger size.
Thus, the oxidation states of P inH4P2O5 ,
H H OH H4P2O6 and H4P2O7 are +3, + 4 and + 5
49 Among the following ions the pπ-
respectively.
In H3PO2 one —OH group and two P—H dπ overlap could be present in
bonds are present. 46 Which of the following is the most [CBSE AIPMT 2000]
basic oxide? [CBSE AIPMT 2006] (a) NO2− (b) NO −3 (c) PO 3−

4 (d) CO2−
3
44 Which of the following statements Ans. (c)
(a) Al2O 3 (b) Sb2O3
is not valid for oxoacids of (c) Bi2O3 (d) SeO2 In P—O bond, π-bond is formed by the
phosphorus? [CBSE AIPMT 2012] sidewise overlapping of d-orbital of P
Ans. (c)
(a) Orthophosphoric acid is used in the and p-orbital of oxygen. Hence, it is
manufacture of triple In Al2O3, Sb2O3, Bi2O3 and SeO2 ,Bi2O3 is formed by pπ and dπ-overlapping.
superphosphate most basic oxide. As across the period
basic nature of oxide decreases and on O
(b) Hypophosphorous acid is a diprotic σ π
moving down the group it increases.
acid P
Bi2O3 + 6HCl → 2BiCl3 + 3H2O O
– O
–
(c) All oxoacids contain tetrahedral four –
coordinated phosphorus O
(d) All oxoacids contain at least one 47 Zn gives H2 gas with H2 SO 4 and
In nitrogen and carbon, no vacant
P ==O unit and oneP OHgroup HCl but not with HNO 3 because d-orbital is present. So, they do not form
Ans. (b) [CBSE AIPMT 2002] pπ-dπ bond.
Hypophosphorous acid, H3PO2 , has the (a) Zn act as oxidising agent when react
following structure. with HNO3 50 Which of the following phosphorus
O (b) HNO3 is weaker acid thanH2SO4 and is the most reactive?
HCl [CBSE AIPMT 1999]
H P OH (c) In electrochemical series Zn is (a) Red phosphorus
H placed above hydrogen
(b) White phosphorus
As it contains only one replaceable (d) NO−3 is reduced in preference to
hydronium ion (c) Scarlet phosphorus
H-atom (that is attached with O, not with
(d) Violet phosphorus
P directly) so it is a monoprotic acid. Ans. (d)
All other given statements are true. ° Ans. (b)
Zn have lower value of E cell and easily
gives oxidation. Zn is present aboveH2 in White phosphorus has low ignition
45 Oxidation states of P in H4P2O 5 , electrochemical series. So, it liberates temperature. So, it is most reactive.
hydrogen gas from dilu. HCl/H2SO4 . But
H4P2O 6 and H4 P2O 7 , respectively HNO3 is an oxidising agent. The hydrogen 51 Which of the following is most
are [CBSE AIPMT 2010] obtained in this reaction is converted acidic? [CBSE AIPMT 1999]
(a) +3, + 5 and + 4 (b) +5, + 3 and + 4 into H2O. In HNO3,NO–3 ion is reduced and (a) N2O5 (b) P2O5 (c) As2O5 (d) Sb2O5
(c) +5, + 4 and + 3 (d) +3, + 4 and + 5 give NH4NO3,N2O, NO andNO2 (based
Ans. (a)
upon the concentration ofHNO3)
Ans. (d)
[Zn + 2HNO3 → Zn (NO3)2 + 2H] × 4 Acidic nature of oxides decreases down
Oxidation state of H is +1 and that of O is a group. So, N2O5 is most acidic.
(Nearly 6%)
–2. Another reason of acidic strength of
HNO3 + 8H → NH3 + 3H2O
Let the oxidation state of P in the given N2O5 is that the electronegativity of N is
compounds is x. NH3 + HNO3 → NH4NO3
maximum in the given Vth group
In H4P2O5 4Zn + 10HNO3 → 4 Zn(NO3)2 + NH4NO3 elements. As we know that on increasing
(+1) × 4 + 2 × x + (− 2) × 5 = 0 + 3H2O the electronegative character, acidic
nature increases.
52 Repeated use of which one of the 55 An aqueous solution of sodium 59 Cane sugar on reaction with nitric
following fertilizers would increase carbonate absorbs NO and NO 2 to acid gives [CBSE AIPMT 1992]
the acidity of the soil? give [CBSE AIPMT 1996] (a) CO2 and SO2 (b) 2HCOOH
(a) Urea [CBSE AIPMT 1998] (a) CO2 + NaNO 3 (c) (COOH)2 (d) no reaction
(b) Superphosphate of lime (b) CO2 + NaNO2 Ans. (c)
(c) Ammonium sulphate (c) NaNO2 + CO When nitric acid reacts with cane sugar,
(d) Potassium nitrate (d) NaNO 3 + CO it forms oxalic acid.
Ans. (c) Ans. (c) COOH
C12H22O11 + 18[O] → 6  + 5H2O
The fertilizer ammonium sulphate is a 2Na2 CO3 + NO + 3NO2 → 4NaNO2 + CO COOH
Cane sugar From
salt of weak base and strong acid, thus nitric acid Oxalic acid
its aqueous solution is acidic, so it 56 Which of the following fluorides
produces acidity. does not exist? [CBSE AIPMT 1993] 60 Number of electrons shared in the
(a) NF5 (b) PF5 formation of nitrogen molecule is
53 The structural formula of (c) AsF5 (d) SbF5 [CBSE AIPMT 1992]
hypophosphorous acid is (a) 6 (b) 10
Ans. (a)
[CBSE AIPMT 1997]
Nitrogen does not form pentahalide (c) 2 (d) 8
O
|| because it does not have vacant Ans. (a)
(a) P d-orbital. Nitrogen molecule is formed by sharing
|
H OH of three electrons by each nitrogen, so
H
57 H3PO 2 is the molecular formula of total number of electrons shared are six.
O
|| an acid of phosphorous. Its name
(b) P and basicity respectively are N N ⇒ N N ⇒N N
|
OH [CBSE AIPMT 1992]
H OH
(a) phosphorous acid and 2
O
|| (b) hypophosphorous acid and 2 61 Which is used in the laboratory for
(c) P (c) hypophosphorous acid and one fast drying of neutral gases?
| (d) hypophosphoric acid and two [CBSE AIPMT 1992]
HO H OH
Ans. (c) (a) P2O 5
O The name ofH3PO2 is hypophosphorous (b) Anhyd. CaCl2
|| acid when dissolve in water, it gives only (c) Activated charcoal
(d) P one H+ , so its basicity is one. (d) Na3PO 4
|
OH O O Ans. (a)
HO OH
 
Ans. (a) P → H+ + P P2O5 absorb moisture, so it is used as a
Hypophosphorous acid (H3PO2 ) is H  OH H  O– drying agent for neutral gases.
H H
monobasic acid, so its structure is
O 62 Pure nitrogen is prepared in the
 58 Nitrogen is relatively inactive laboratory by heating a mixture of
P element because [CBSE AIPMT 1991]
H  OH [CBSE AIPMT 1992]
H (a) NH4OH + NaCl (b) NH4NO 3 + NaCl
(a) its atom has a stable electronic (c) NH4Cl + NaOH (d) NH4Cl + NaNO2
configuration
54 Which of the following oxides will (b) it has low atomic radius
Ans. (d)
be the least acidic? (c) its electronegativity is fairly high In the laboratory dinitrogen is prepared
[CBSE AIPMT 1996]
(d) dissociation energy of its molecule is by heating an aqueous solution
(a) As4O 6 (b) As4O 10 fairly high containing an equivalent amount of
(c) P4O 10 (d) P4O 6 ammonium chloride and sodium nitrite.
Ans. (d)
Ans. (a) NH4 Cl(aq) + NaNO2 (aq) →
Heat
N2 (g)
Dinitrogen (N2 ) is chemically unreactive
As the oxidation state of central atom at ordinary temperature. The N—N bond + 2 H2O(l ) + NaCl
increases the acidic character in nitrogen molecule is a triple bond
increases, so the correct order of acidic (N ≡≡ N) with a bond distance of 109.8 pm 63 PH4I + NaOH forms
character is and bond dissociation energy of 946 kJ
[CBSE AIPMT 1991]
+5 +3 +5 +3 mol −1. The low reactivity of nitrogen is
P4 O10 >P4 O6 > A s4 O10 > A s4 O6 due to fairly high bond dissociation (a) PH3 (b) NH3
and hence, As4O6 is least acidic. energy of the molecule. (c) P4O 6 (d) P4O 10
Ans. (a) 68 Which of the following statements 72 Which of the following compound
When PH4I and NaOH react, phosphine is not correct for nitrogen? does not exist? [CBSE AIPMT 1989]
gas is obtained. [CBSE AIPMT 1990] (a) NCl5 (b) AsF5
PH4I + NaOH → PH3 + NaI + H2O (a) Its electronegativity is very high (c) SbCl5 (d) PF5
(b) d-orbitals are available for bonding Ans. (a)
64 PCl 3 reacts with water to form (c) It is a typical non-metal
Nitrogen does not formNCl 5 (nitrogen
[CBSE AIPMT 1991] (d) Its molecular size is small
pentachloride) because nitrogen does
(a) PH3 (b) H3PO 3, HCl Ans. (b) not have vacant d-orbital, so it can form
(c) POCl3 (d) H3PO 4 Nitrogen does not have vacant d-orbital only NCl 3.
Ans. (b) in its outermost shell.
PCl 3 is easily hydrolysed by water to give N(7) = 1s 2 , 2 s 2 2p3 73 Which of the following is a nitric
POCl 3 and finally it givesH3PO3 and HCl. acid anhydride? [CBSE AIPMT 1988]
=
PCl 3 + H2O → POCl 3 + 2HCl (a) NO (b) NO2
POCl 3 + 3H2O → H3PO3 + 3HCl 1s 2s 2p (c) N2O 5 (d) N2O 3
Ans. (c)
65 Basicity of orthophosphoric acid is 69 Which one has the lowest boiling Dinitrogen pentaoxide (N2O5 ) is prepared
[CBSE AIPMT 1991] point? [CBSE AIPMT 1989] by dehydrating the concentrated nitric
(a) 2 (b) 3 (a) NH3 (b) PH3 acid with phosphorus pentoxide.
(c) 4 (d) 5 (c) AsCl3 (d) SbH3 4HNO 3 + P4O 10 → 2N2O 5 + HPO 3
Ans. (b) Ans. (b) So, N2O5 is regarded as anhydride of
Orthophosphoric acid (H3PO4 ) have the In the hydrides of group 15, the boiling HNO3.
following structure points changes as
O NH3 > PH3 < AsH3 < SbH3 < BiH3
 TOPIC 4
P 238.5 K 185.5 K 210.6 K 254.6 K 290 K
HO  OH
OH
∴Generally mass increases then boiling Group 16 Elements
point increases.
It is clear from the structure that it The higher boiling point ofNH3 is due to
contains three replaceable hydrogen excessive hydrogen bonding, soPH3
74 In which one of the following
atoms, so it gives threeH+ ions on have lowest boiling point among arrangements the given sequence
dissolution in water. So, the basicity of hydrides of group number 15, i.e. is not strictly according to the
H3PO4 is three. nitrogen family. properties indicated against it?
H3PO4 → 3H+ + PO34− [NEET 2021]
70 When orthophosphoric acid is (a) HF< HCI < HBr < HI : Increasing
66 P2O 5 is heated with water to give heated to 600°C, the product acidic strength
[CBSE AIPMT 1991] formed is [CBSE AIPMT 1989] (b) H2O < H2S < H2Se < H2Te : Increasing
(a) PH3 (b) P2O 5 (c) H3PO 3 (d) HPO 3 pK a values
(a) hypophosphorous acid
(c) NH3 < PH3 < AsH3 < SbH3 : Increasing
(b) phosphorous acid Ans. (d) acidic character
(c) hypophosphoric acid When orthophosphoric acid (H3PO4 ) is (d) CO2 < SiO2 < SnO2 < PbP2 : Increasing
(d) orthophosphoric acid heated and dehydration takes place. It oxidising power
Ans. (d) form metaphosphoric acid (HPO3).
Ans. (b)
∆
When P2O5 (or P4O10 ) is heated with water, H3PO4 → HPO3 + H2O HF < HCl < HBr < HI; Down the group,
600 ° C
it form orthophosphoric acid (H3PO4 ). size of atom increases, bond length
P4O10 + 6H2O → 4H3PO4 decreases and bond enthalpy decreases.
71 Each of the following is true for So, acidic strength increases.
67 Aqueous solution of ammonia white and red phosphorus except ∴ The given sequence is correct
consists of [CBSE AIPMT 1991] that they [CBSE AIPMT 1989] H2O > H2S > H2Se > H2Te, pK a is inversely
(a) H+ (a) both are soluble in CS2 proportional to acidic strength. So, pK a
decreases.
(b) OH− (b) can be oxidised by heating in air
∴ The given sequence is incorrect.
(c) NH+4 (c) consist of the same kind of atoms
(d) NH+4 and OH− (d) can be converted into one another NH3 < PH3 < AsH3 < SbH3; Acidic
Ans. (a) character increases down the group,
Ans. (d)
∴ The given sequence is correct.
When ammonia dissolve in water, it form White and red phosphorus are the main
allotropes of phosphorus. White CO2 < SiO2 < SnO2 < PbP2 ; on moving
ammonium hydroxide which is ionise as down the group oxidising power
given below phosphorus is soluble in carbon
disulphide whereas red phosphorus is increases.
NH3 + H2O → NH4OH ºNH+4 + OH– ∴ The given sequence is correct.
insoluble in carbon disulphide.
75 Which of the following oxoacid of Al2O3 + 6HCl → 2AlCl 3 + 3H2O Ans. (b)
sulphur has O O  linkage? Al2O3 + 2NaOH → 2NaAlO2 + H2O For group 16 elements, the hydrides with
[NEET (Sep.) 2020] (D) Cl2O7 It is an acidic oxide and high molar mass (e.g.H2 Po) are less
(a) H2 SO 4 , sulphuric acid produces a very strong acid, thermally stable than hydride with lower
(b) H2 S2O 8 , peroxodisulphuric acid perchloric acid inH2O. molar mass (e.g.H2O). This is due to the
(c) H2 S2O 7 , pyrosulphuric acid Cl2O7 + H2O → 2HClO4 increase in size of central atom which
results to the weakening of MHbond
(d) H2SO3, sulphurous acid due to increased bond length.
77 Identify the correct formula of
Ans. (b) Thus, the correct order of thermal
oleum from the following
The structure of given sulphur oxyacids [NEET (Odisha) 2019] stability for
are : H2 E(E = O, S, Se, Te and Po) is as follows:
(a) H2 S2O 7 (b) H2 SO 3
l H2SO4 (Sulphuric acid) ⇒ (c) H2 SO 4 (d) H2 S2O 8 H2Po < H2Te < H2Se < H2S < H2O
O Ans. (a)
HOSOH The correct formula of oleum isH2 S2O7 80 In which pair of ions both the
which is also known as pyrosulphuric
O acid.
species contain S S bond?
l H2S2O8 (Peroxodisulphuric acid) ⇒ [NEET 2017]
O O
Peroxy linkage (a) S2O27− , S2O23−
O O HO—S—O—S—OH (b) S4O26− , S2O23−
HOSO OSOH
O O
(c) S2O27− , S2O28−
O O (d) S4O26− , S2O27−
l
H2S2O7 (Pyrosulphuric acid) ⇒ 78 Match the oxide given in column A Ans. (b)
l
H2S2O7 (Pyrosulphuric acid) ⇒ with its property given in column B. S 4O26− and S2O23− have S—S bond
O O Which of the following options has O 2–
O– S–
HOSO SOH all correct pairs? S S O
[NEET (Odisha) 2019] O S S S
O O O– O O
l
H2SO3 (Sulphurous acid) ⇒ Column-A Column-B O O
O 1. Na 2O i. Neutral 1
(S4O62–) Thiosulphate ion
HOSOH 2. Al 2O 3 ii. Basic (tetrathionate) (S2O32–)
3. N 2O iii. Acidic
76 Match the following. 4. Cl 2O 7 iv. Amphoteric 81 Hot concentrated sulphuric acid is
Oxide Nature
a moderately strong oxidising
1 2 3 4 1 2 3 4 agent. Which of the following
A. CO (i) Basic (a) (ii), (i), (iv), (iii) (b)(iii), (ii), (i), (iv) reaction does not show oxidising
B. BaO (ii) Neutral (c) (i), (ii), (ii), (iii) (d)(ii), (iv), (i), (iii) behaviour? [NEET 2016, Phase II]
Ans. (d) (a) Cu + 2H2SO4 → CuSO4 + SO2 + 2H2O
C. Al 2O 3 (iii) Acidic
Key Idea Metal oxides are basic, (b) 3S + 2H2SO4 → 3SO2 + 2H2O
D. Cl 2O 7 (iv) Amphoteric non-metal oxides are acidic while (c) C + 2H2SO4 → CO2 + 2SO2 + 2H2O
semi-metal oxides are amphoteric in
Which of the following is correct nature. Thus, the basic character of (d) CaF2 + H2SO4 → CaSO4 + 2HF
option? [NEET (Sep.) 2020] oxides decreases across the period and Ans. (d)
increases down the group. Key Idea An oxidising agent is a species,
A B C D A B C D
The correct match of oxide with its which oxidises the other species and
(a) (ii) (i) (iv) (iii) (b) (iii) (iv) (i) (ii) property are as follows: itself gets reduced.
(c) (iv) (iii) (ii) (i) (d) (i) (ii) (iii) (iv) Na2O- Basic Al2O3- Amphoteric 0 +2
(i) Cu+ 2H2SO4 → CuSO4 + SO2 + 2H2O
Ans. (a) N2O- Neutral Cl2O7 - Acidic
0 +4
The correct matching is : Thus, option (d) is correct. (ii) 3S+ 2H2SO4 → 3 S O2 + 2H2O
(A)-(ii), (B)-(i), (C)-(iv), (D)-(iii) 0 +4
(A) CO It is a neutral oxide and almost 79 Which is the correct thermal (iii) C+ H2SO4 → CO2 + 2SO2 + 2H2O
insoluble in water. stability order for H2E (E = O, S, Se, +2 –1 +2 –1
(iv) C aF2 + H2SO4 → C aSO4 + 2HF
(B) BaO It is basic oxide. Te and Po)? [NEET (National) 2019]
BaO + H2O → Ba(OH)2 (a) H2O < H2 S < H2 Se < H2Te < H2Po In reaction (iv), oxidation number of
(C) Al2O 3 It is an amphoteric oxide, (b) H2Po < H2Te < H2 Se < H2 S < H2O elements remains unchanged. Thus, in
because it reacts with both acids and this reaction,H2SO4 does not act as an
(c) H2 Se < H2Te < H2Po < H2O < H2 S
alkalis. oxidising agent.
(d) H2 S < H2O < H2 Se < H2Te < H2Po
82 Nitrogen dioxide and sulphur (c) Number of electrons in ONF = 24 S to Te size increases, bond dissociation
dioxide have some properties in Number of electrons inNO2 = 24 enthalpy decreases and acidic nature
∴ ONF and NO2 both are increases.
common. Which property is shown
isoelectronic.
by one of these compounds, but (d) OF2 is a fluoride of oxygen because 87 Sulphur trioxide can be obtained by
not by the other? [CBSE AIPMT 2015] electronegativity of fluorine is more which of the following reaction?
(a) Forms’ acid-rain than that of oxygen. [CBSE AIPMT 2012]
(b) Is a reducing agent OF2 = Oxygen difluoride ∆
(c) Is soluble in water (a) CaSO 4 + C →
(d) Is used as a food-preservative 85 The formation of the oxide ion ∆
(b) Fe2 (SO 4 ) 3 →
Ans. (a) O 2− (g), from oxygen atom requires
first an exothermic and then an ∆
Nitrogen dioxide and sulphur dioxide (c) S + H2 SO 4 →
forms acid rain. ‘Acid rain’ is the rain endothermic step as shown below, ∆
water containing sulphuric acid and [CBSE AIPMT 2015] (d) H2 SO 4 + PCl5 →
nitric acid. O(g )+ e − → O−(g ); Ans. (b)
HNO2 + 2H2O + O2 → 4HNO3 ∆f H° = −141 kJmol−1 ∆
(a) CaSO4 + C → CaO + SO2 + CO
2SO2 + 2H2O + O2 → 2H2SO4
∆
(b) NO2 and SO2 act as a good reducing
O−(g ) + e − → O2−(g ); (b) Fe2 (SO4 ) 3 → Fe2O3 + 3 SO3
agent
∆
e.g. SO2 reduces halogens to halogen ∆f H° = +780 kJ mol−1 (c) S + 2H2SO4 → 3SO2 + 2H2O
acid Thus, process of formation ofO 2− ∆
(d) H2SO4 + PCl 5 → SO3HCl
Cl2 + 2H2O + SO2 → 2HCl + H2SO4 in gas phase is unfavourable even Chloro sulphonic acid
(c) NO2 and SO2 both are soluble in water.
though O 2− is isoelectronic with + POCl 3 + HCl
(d) SO2 is used in the manufacture of
neon. It is due to the fact that Thus, SO3 is obtained by heating
sodium bisulphite (NaHSO3) which is
(a) electron repulsion outweighs the Fe2 (SO4 ) 3.
used as a preservative for jams,
jellies and squashes. stability gained by achieving noble
gas configuration 88 Which one of the following oxides
83 Decreasing order of stability of (b) O− ion has comparatively smaller is expected to exhibit
size than paramagnetic behaviour?
O 2 ,O −2 ,O +2 and O 2−
2 is oxygen atom
(c) Oxygen is more electronegative (a) CO2 (b) SO2
(a) O2+ > O2 > O2− > O22 − (d) addition of electron in oxygen result (c) ClO2 (d) SiO2
(b) O22 − > O2− > O2 > O2+ in large size of the ion
(c) O2 > O2+ > O22 − > O2− Ans. (a)
Ans. (c)
(d) O2− > O22 − > O2+ > O2 ClO2 shows paramagnetic character due
Since, electron repulsion predominate to presence of unpaired electron in its
Ans. (a) over the stability gained by achieving structure.
Order of stability ∝ bond order noble gas configuration. Hence,
formation of O2 − in gas phase is Cl
∴Order of the stability of given species, unfavourable.
+
O2+ > O2 > O2− > O22 − O O
Bond order 2.5 2 1.5 1 86 Acidity of diprotic acids in aqueous
solutions increases in the order 89 The oxidation states of sulphur in
84 Which of the statements given [CBSE AIPMT 2014] the anions SO 2– 2– 2−
3 , S 2O 4 and S 2O 6
below is incorrect? (a) H2 S < H2 Se < H2Te follows the order
[CBSE AIPMT 2015] (b) H2 Se < H2 S < H2Te [CBSE AIPMT 2003]
(a) Cl2O7 is an anhydride of perchloric acid (c) H2Te < H2 S < H2 Se (a) S2O2– 2– 2–
4 < S2O 6 < SO 3
(b) O3 molecule is bent (d) H2 Se < H2Te < H2 S (b) S2O 6 < S2O 4 < SO2–
2– 2–
3
(c) ONF is isoelectronic withNO2
Ans. (a) (c) S2O2– 2– 2–
4 < SO 3 < S2O 6
(d) OF2 is an oxide of fluorine (d) SO2– 2– 2–
3 < S2O 4 < S2O 6
Acidic strength of hydrides increases as
Ans. (d) Ans. (c)
the size of central atom increases which
(a) Cl2O7 is an anhydride of perchloric acid weakens the MH bond. Since, the size Oxidation state of S inSO23−
∆ Cl2O7
2HClO4 → increases from S to Te thus acidic x + (− 2 × 3) = − 2.
−H2 O strength follows the order. x = + 6−2= + 4
(b) Shape of O3 molecule is bent. H2S < H2Se < H2Te Oxidation state of S inS2O24−
Acidic nature 2 x + (–2 × 4) = –2
1
∝ 2x = + 8 − 2 = + 6
O Bond dissociation enthalpy +6
O x= =+3
O 2
Oxidation state of S inS2O26− O Ans. (b)

2 x + (–2 × 6) = – 2 S—O—O—H Pyrogallol absorb the oxygen gas and oil
2x = +12 − 2 = 10 of cinnamon absorb the ozone (O3).
10 O OH
x= =+5
2 98 Oxygen will directly react with each
93 Polyanion formation is maximum in of the following elements except?
Hence, increasing order of oxidation [CBSE AIPMT 1994]
states of S is [CBSE AIPMT 1989]
(a) nitrogen (b) oxygen
S2O24− < SO23− < S2O26− (c) sulphur (d) boron
(a) P (b) Cl
(c) Na (d) S
Ans. (c)
90 Oxidation of thiosulphate by iodine Ans. (b)
gives [CBSE AIPMT 1996] Sulphur has more tendency to form
Out of P, Na, S and Cl, chlorine does not
polyanion such as S2– 2− 2−
3 , S4 and S5
(a) tetrathionate ion react directly but Na, P and S react with
because sulphur has more tendency
(b) sulphide ion oxygen directly.
for catenation among the given
(c) sulphate ion P4 + 5O2 → P4O10
elements.
(d) sulphite ion S + O2 → SO2
Ans. (a) 94 Oleum is [CBSE AIPMT 1991] 4Na + O2 → 2Na2O
2S2O23– + I2 → S 4O26– + 2I – (a) castor oil (b) oil of vitriol
Thiosulphate Tetrathionate (c) fuming H2 SO 4 (d) None of these 99 Hypo is used in photography to
ion ion [CBSE AIPMT 1988]
Ans. (c)
(a) reduce AgBr grains to metallic silver
91 About 20 km above the earth, there Disulphuric acid (H2S2O7 ) is called oleum
(b) convert metallic silver to silver salt
is an ozone layer. Which one of the or fuming sulphuric acid. It is strongest
oxidising agent and more powerful (c) remove undecomposed silver
following statements about ozone bromide as a soluble complex
dehydrating agent.
and ozone layer is true? (d) remove reduced silver
[CBSE AIPMT 1995]
95 Which would quickly absorb Ans. (c)
(a) Ozone is a triatomic linear molecule oxygen? [CBSE AIPMT 1991]
(b) It is harmful as it stops useful After the developing, the sensitive
radiation
(a) Alkaline solution of pyrogallol emulsion of silver bromide is still present
(c) It is beneficial to us as it stops (b) Conc ⋅H2 SO 4 on the plate in the parts unaffected by
(c) Lime water light. Therefore, it is necessary to
UV-radiation
(d) Alkaline solution of CuSO 4 remove it in order to get the permanent
(d) Conversion of O3 to O2 is an image. This process is called fixing of
endothermic reaction Ans. (a) image. The negative plate after washing
Ans. (c) Alkaline solution of pyrogallol is used to is dipped in a fixing solution of sodium
Ozone is an allotropic form of oxygen. It absorb dioxygen gas (O2 ). thiosulphate (hypo). It dissolves
is present in the upper atmosphere unaffected silver bromide but leaves
(about 20 km above the surface of the 96 It is possible to obtain oxygen from metallic silver unaffected.
earth). It is believed to be formed in the air by fractional distillation because 2Na2S2O3 + AgBr → Na3 [Ag(S2O3) 2 ]
upper atmosphere by the action of [CBSE AIPMT 1989] + NaBr
UV-rays on oxygen as (a) oxygen is in a different group of the
3O2 + UV - rays → 2O3, periodic table from nitrogen
∆ H = 142.7 kJ mol −1 (b) oxygen is more reactive than TOPIC 5
nitrogen
Therefore, UV-rays, which are harmful to
human beings are absorbed by oxygen to (c) oxygen has higher boiling point than Group 17 Elements
form ozone. The layer of ozone, thus nitrogen
formed also prevents the remaining (d) oxygen has a lower density than 100 Statement I Acid strength
UV-rays to reach the earth’s surface. nitrogen increases in the order given as
Ans. (c) HF << HCl << HBr << HI.
92 The acid which has a peroxy Oxygen gas is prepared by fractional
linkage is Statement II As the size of the
[CBSE AIPMT 1994] distillation of air. During this process,
dinitrogen with less boiling point (78 K) elements F, Cl, Br and HI
(a) sulphurous acid
(b) pyrosulphuric acid distills as vapours while dioxygen with increases down the group. the
(c) dithionic acid
higher boiling point (90 K) remains in the bond strength of HF, HCl, HBr and
liquid state and can be separated. HI decreases and so the acid
(d) Caro’s acid
Ans. (d) 97 The gases respectively absorbed strength increases.
Peroxomonosulphuric acid,H2SO5 is also by alkaline pyrogallol and oil of In the light of the above
known as Caro’s acid. It has peroxy cinnamon are [CBSE AIPMT 1989] statements, choose the correct
linkage —O—O— which is confirmed by (a) O 3,CH4 (b) O2 ,O 3 answer from the options given
X-ray studies. (c) SO2 ,CH4 (d) N2O,O 3 below. [NEET 2021]
(a) Both Statement I and Statement II Time Saver If someone know correct to accept an electron. Thus, option
are true. match of B, i.e. (iii) then according to the (b) is correct.
(b) Both Statement I and Statement II options (c) is the only correct answer as (c) All halogens form monobasic
are false. this match is given in this option only. oxyacids. Thus, option (c) is also
(c) Statement I is true but Statement II correct.
is false. 102 The correct structure of (d) Electron gain enthalpy of halogens
(d) Statement I is false but Statement II tribromooctaoxide is become less negative down the
is true. [NEET (National) 2019]
group. However, the negative
O electron gain enthalpy of fluorine is
Ans. (a) O O less than chlorine due to small size of
–
The order of acidic strength is (a) O == BrBrBrO fluorine atom.
HF << HCl << HBr << HI O– Thus, option (d) is also correct.
O O–
As we move down the group, the size of O
atom increases. Thus, the bond length O O– 104 In the structure of ClF3 , the number
–
also increases and bond enthalpy (b) O Br  Br  Br == O–
decreases. So, it becomes easier to
of lone pairs of electrons on central
break H—X bond on moving down the
–
O O– O– atom ‘Cl’ is [NEET 2018]
group. This results the increase in the O O– O (a) four (b) two
acidic strength. (c) one (d) three
(c) O == BrBrBrO –
So, both statements I and II are true. Ans. (b)
O O– O–
The central atom Cl has seven electrons
101 Match the following : O O O in the valence shell. Three of these will
A. Pure nitrogen (i) Chlorine (d) O == BrBrBr==O form electron pair bonds with three
fluorine atoms leaving behind four
B. Haber process (ii) Sulphuric acid O O O electrons.
C. Contact (iii) Ammonia Ans. (d) F
process
The correct structure of F Cl
D. Deacon’s (iv) Sodium azide tribromooctaoxide is
process or barium O F
O O
azide
Thus, there are three bond pairs and two
O=
=Br—Br—Br=
=O
Which of the following is the lone pairs of electrons.
correct option? O O O
[NEET (National) 2019] In this compound, Br exhibits variable 105 Match the interhalogen compounds
A B C D oxidation state. The oxidation state of Br of Column I with the geometry in
(a) (ii) (iv) (i) (iii) from left to right are + 6, + 4 and + 6, Column II and assign the correct
respectively. code. [NEET 2017]
(b) (iii (iv) (ii) (i)
(c) (iv) (iii) (ii) (i) 103 Which of the following statements Column I Column II
(d) (i) (ii) (iii) (iv) is not true for halogens? A. XX′ (i) T- shape
Ans. (c) [NEET 2018]
B. XX′ 3 (ii) Pentagonal
The correct match is as follows : (a) All but fluorine show positive bipyramidal
oxidation states
(A) Pure nitrogen Pure nitrogen can be C. XX′ 5 (iii) Linear
obtained by thermal decomposition (b) All are oxidising agents
of sodium or barium azide. (c) All form monobasic oxyacids D. XX′ 7 (iv) Square-pyramidal
∆ Ba + 3N2
Ba(N3)2 → (d) Chlorine has the highest (v) Tetrahedral
electron-gain enthalpy
2NaN3 → ∆ 2Na + 3N2
(B) Haber’s process On large scale, Ans. (a) Code
ammonia is manufactured by Haber’s Fluorine is the most electronegative A B C D
process. element and cannot exhibit any positive
oxidation state. Other halogens have
(a) (iii) (iv) (i) (ii)
N2 (g) + 3H2 (g) -
2NH3 (g)
d-orbitals and therefore, can expand (b) (iii) (i) (iv) (ii)
(C) Contact process Sulphuric acid is
manufactured by the contact their octets and show +1, +3, +5 and +7 (c) (v) (iv) (iii) (ii)
process. oxidation states. Thus, option (a) is
(d) (iv) (iii) (ii) (i)
incorrect.
(D) Deacon’s process Chlorine is Ans. (b)
prepared by Deacon’s process. Note Fluorine can form an oxoacid, HOF
CuCl in which oxidation state ofF is +1. But Two different halogens may react to
4HCl + O2  2→ 2Cl2 + 2H2O. form interhalogen compounds as
HOF is highly unstable compound.
Hence, the correct match is (b) All halogens are strong oxidising XX′ (ClF, BrF, BrCl, IF, ICl) Linear
(A) → (iv), (B) → (iii), (C)→ (ii), (D) → (i) agents as they have strong tendency
XX′ 3 (ClF3, BrF3, IF3, ICl 3) Bent T-shaped
XX′ 5 (ClF5 , BrCl 5 , IF5 ) Square- Ans. (b) Ans. (c)

pyramidal Since, there is a strong hydrogen Generally as the size of the atom
XX′ 7 (IF7 ) Pentagonal bonding between HF molecules. Hence, increases, bond dissociation energy
bipyramidal boiling point is highest for HF. decreases, so in halogensI2 have lowest
HF > HI > HBr > HI bond dissociation energy, but the bond
dissociation energy of chlorine is higher
106 Among the following, the correct than that of fluorine because in fluorine
order of acidity is 109 When Cl 2 gas reacts with hot and
there is a greater repulsion between
[NEET 2016, Phase I, CBSE AIPMT 2005] concentrated sodium hydroxide non-bonding electrons (2p). Hence, the
(a) HClO < HClO2 < HClO3 < HClO4 solution, the oxidation number of order of bond dissociation energy is
(b) HClO2 < HClO < HClO3 < HClO4 chlorine changes from Cl2 > F2 > Br2 > I2
(c) HClO4 < HClO2 < HClO < HClO3 [CBSE AIPMT 2012] Bond dissociation 243 159 193 151
(d) HClO3 < HClO4 < HClO2 < HClO (a) zero to +1 and zero to −5 energy (kJ/mol)
Ans. (a) (b) zero to −1 and zero to +5
As the oxidation state of halogen i.e. —Cl (c) zero to −1 and zero to +3 112 Which one of the following ionic
in this case increases, acidity of oxyacid (d) zero to +1 and zero to −3 species has the greatest proton
increases.
Ans. (b) affinity to form stable compound?
HClO : Oxidation state of Cl = +1 [CBSE AIPMT 2007]
HClO2 : Oxidation state of Cl = + 3 When chlorine gas reacts with hot and
concentrated NaOH solution, it (a) HS− (b) NH2−
HClO 3 : Oxidation state of Cl = + 5 (c) F − (d) I−
disproportionates into chloride (Cl − ) and
HClO 4 : Oxidation state of Cl = + 7 chlorate (ClO−3 ) ions. Ans. (c)
Therefore, the correct order of acidity Oxidation
would be Fluorine is the most electronegative
0 −1 +5 element in the periodic table. So, it has
HClO < HClO2 < HClO 3 < HClO 3 Cl2 + 6NaOH → 5Na Cl+ Na ClO3 + 3H2O the greatest proton affinity to form
stable compounds.
107 Which one of the following orders Hot and
concentrated
is correct for the bond dissociation reduction 113 Which one of the following orders
enthalpy of halogen molecules? is not in accordance with the
110 Among the following which is the property stated against it?
(a) Cl2 > Br2 > F2 > I2
(b) Br2 > I2 > F2 > Cl2
strongest oxidising agent? [CBSE AIPMT 2006]
(c) F2 > Cl2 > Br2 > I2

[CBSE AIPMT 2009] (a) F2 > Cl2 > Br2 > I2 Oxidising power
(d) l2 > Br2 > Cl2 > F2 (a) F2 (b) Br2 (b) Hl > HBr > HCl > HF acidic property in
(c) I2 (d) Cl2 water
Ans. (a)
Ans. (a) (c) F2 > Cl2 > Br2 > I2 Electronegativity
As the size increases, bond dissociation (d) F2 > Cl2 > Br2 > I2 Bond dissociation
enthalpy becomes lower. Also, as the Fluorine is the most electronegative
energy
size of atoms get smaller, ion pairs on element because electronegativity
decreases on moving down the group. Ans. (d)
the two atoms get close enough
together to experience repulsion. In Hence, it gets reduced readily intoF − ion Incorrect order of bond dissociation
case of F2 , this repulsion is bigger and and is the strongest oxidising agent. energy F2 > Cl2 > Br2 > I2 due to following
bond becomes weaker. NOTE The electron gain enthalpy of order of size I > Br > Cl > F.
Hence, the correct order is fluorine is less negative than that of
Cl2 > Br2 > F2 > I2 chlorine inspite of that flourine is the 114 Which one of the following
strongest oxidising agent. This is due to arrangements represents the
108 The variation of the boiling point of its low bond dissociation energy and high
heat of hydration as compared to those
correct order of electron gain
the hydrogen halides is in the order of chlorine. enthalpy (with negative sign) of the
HF > HI > HBr > HCl. What explains given atomic species?
the higher boiling point of hydrogen 111 Which one of the following [CBSE AIPMT 2005]
fluoride? [CBSE AIPMT 2015] arrangements does not give the (a) Cl < F < S < O
(a) The electronegativity of fluorine is correct picture of the trends (b) O < S < F < Cl
much higher than for other elements indicated against it? (c) S < O < Cl < F
in the group
[CBSE AIPMT 2008] (d) F < Cl < O < S
(b) There is strong hydrogen bonding
(a) F2 > Cl2 > Br2 > I2 Oxidising power Ans. (b)
between HF molecules
(c) The bond energy of HF molecules is (b) F2 > Cl2 > Br2 > I2 Electron gain The correct order of electron gain
greater than in other hydrogen enthalpy enthalpy or (electron affinity) is
halides (c) F2 > Cl2 > Br2 > I2 Bond dissociation O < S < F < Cl
(d) The effect of nuclear shielding is energy Values of electron affinity are (in eV) 1.48,
much reduced in fluorine which (d) F2 > Cl2 > Br2 > I2 Electronegativity 2.07, 3.45 and 3.61.
polarises the HF molecule
115 Among K, Ca, Fe and Zn, the (c) Mn(III) oxidation state is more stable (c) Both MnO2 and KMnO 4
than Mn(II) in aqueous state (d) Either MnO2 and KMnO 4
element which can form more than
(d) Elements of 15th group shows only Ans. (c)
one binary compound with chlorine +3 and +5 oxidation states
is [CBSE AIPMT 2004] MnO2 + 4HCl → MnCl2 + 2H2O + Cl2
Ans. (b)
(a) Fe (b) Zn (c) K (d) Ca 2KMnO4 + 16HCl → 2KCl + 2MnCl2
Bond energy ofF2 is less than Cl2
Ans. (a) + 8H2O + 5Cl2
because inF2 molecule electron-electron
A binary compound is that compound repulsion of 2p-orbital of two fluorine
which is formed by two different atom is maximum in comparison to the 122 Which of the following elements
elements. Metals or elements which repulsion of 3p-orbitals of two chlorine has maximum electron affinity?
shows variable oxidation states can form atom. So, less amount of energy is [CBSE AIPMT 1999]
more than one binary compound. In the required to break the bond ofF2 in (a) Cl (b) Br
given elements only Fe shows +2 and +3 comparison to Cl2 . (c) I (d) F
oxidation states. So, it can form two
Ans. (a)
binary compounds with chlorine asFeCl2 119 Which reaction is not feasible?
and FeCl 3. [CBSE AIPMT 2002]
The electron affinity decreases from
Cl → Br → I, i.e. on moving down the
(a) 2KI + Br2 → 3KBr + I2 group. However, electron affinity of
116 Which is the best description of
(b) 2KBr + I2 → 2KI + Br2 fluorine is unexpected low. It cannot be
behaviour of bromine in the
(c) 2KBr + Cl2 → 2KCl + Br2 explained by any simple mechanism. It is
reaction given below? probably due to small size of the atom.
(d) 2H2O + 2F2 → 4HF + O2
H2O + Br 2 → HBr + HOBr Ans. (b)
The addition of an extra electron
[CBSE AIPMT 2004] produces high electron charge density in
(a) Only oxidised 2KBr + I2 → 2KI + Br2 a relatively compact 2p subshell
(b) Only reduced Reaction is not possible becauseBr − ion resulting in strong electron-electron
is not oxidised in Br2 with I2 due to higher repulsion. The repulsive forces between
(c) Both oxidised and reduced electrons imply low electron affinity. So,
electrode potential ofI2 than bromine.
(d) Only proton accepted the correct order of electron affinity for
In halogens, fluorine can displace chlorine
Ans. (c) bromine and iodine, chlorine can displace halogens is
In the reaction, bromine and iodine and bromide can I < Br < F < Cl
0 +1 –1 displace iodine from their salts.
H2O + Br2 → HOBr + HBr 123 Regarding F − and Cl − which of the
The oxidation number of bromine 120 Which one of the following following statement (s) is/are
increases from 0 to + 1 and decreases arrangements does not truly correct?
from 0 to − 1, due to this reason bromine
is both oxidised as well as reduced in the
represent the property indicated I. Cl − can give up an electron
above reaction.
against it? [CBSE AIPMT 2000] more easily than F − .
(a) Br2 < Cl2 < F2 Oxidising power II. Cl − is a better reducing agent
117 Which of the following statement is (b) Br2 < Cl2 < F2 Electronegativity than F − .
not true? [CBSE AIPMT 2003] (c) Br2 < F2 < Cl2 Electron affinity III. Cl − is smaller in size than F − .
(a) HOCl is a stronger acid than HOBr (d) Br2 < Cl2 < F2 Bond energy IV. F − can be oxidised more
(b) HF is a stronger acid than HCl Ans. (d) readily than Cl − .
(c) Among halide ions, iodide is the most sbond dissociation enthalpy of halogens [CBSE AIPMT 1996]
powerful reducing agent follows the sequency as : (a) I and II (b) I, II and IV
(d) Fluorine is the only halogen that does
not show a variable oxidation state Cl2 > Br > F2 > I2 (c) III and IV (d) Only I
Enthalpy of dissociation decreass as the Ans. (d)
Ans. (b)
bond distance increases fromF2 to I2 due
Due to strong H—F bond,H+ ions are not The electronegativity of F − ion is high, so
to a corresponding increase in size of
easily removed due to higher it accept an electron and Cl − ion can give
the atom as one move down the group
electronegativity (EN) of F. Hence more an electron more easily. Also the size of
from F to I. However, the F-F bond
bond dissociation energy required. F − is smaller than chloride ion (Cl − ).
dissociation enthalpy is smaller than that
1 of Cl-Cl (even than that of Br-Br) because
Acidic nature ∝ 124 HI can be prepared by all the
Bond dissociation energy F-atom is very small and hence
So, HF is not a stronger acid than HCl. electron-electron repulsion between the following methods except
lone pairs of electrons are very large. [CBSE AIPMT 1994]
118 Which of the following statements (a) PI3 + H2O (b) KI + H2 SO 4

121 Which of the following is used in Pt
is true? [CBSE AIPMT 2002] (c) H2 + I2 → (d) I2 + H2 S
the preparation of chlorine?
(a) Silicon exhibits 4 coordination Ans. (b)
[CBSE AIPMT 1999]
number in its compounds
(b) Bond energy ofF2 is less than Cl2 (a) Only MnO2 8KI+ 5H2SO4 → 4K2SO4
(b) Only KMnO 4 +4I2 + H2S + 4H2O
125 Which one of the following oxides Bromide ion when treated with Cl2 gas Ans. (a)
then form chloride ion and Br2 gas
of chlorine is obtained by passing When bleaching powder reacts with HCl,
liberated. it form chlorine gas.
dry chlorine over silver chlorate at
90°C? [CBSE AIPMT 1994] 130 Strongest hydrogen bonding is CaOCl2 + 2HCl → CaCl2 + H2O + Cl2
(a) Cl2O (b) ClO 3 shown by [CBSE AIPMT 1992]
(c) ClO2 (d) ClO 4
Ans. (c)
(a) water (b) ammonia TOPIC 6
(c) HF
2 AgClO3 + Cl2 (dry) →
Heat
2AgCl (d) hydrogen sulphide Group 18 Elements
+ 2ClO2 + O2
Ans. (c)
HF has strongest hydrogen bonding due 135 Noble gases are named because of
126 Which among the following is to the fact that it have small size and their inertness towards reactivity.
paramagnetic? [CBSE AIPMT 1994] high electronegativity. Identify an incorrect statement
(a) Cl2O (b) ClO2 (c) Cl2O 7 (d) Cl2O 6
about them. [NEET 2021]
131 Elements of which of the following (a) Noble gases are sparingly soluble in
Ans. (b) groups will form anions most water.
ClO2 contains total valence electrons 19, readily? [CBSE AIPMT 1992] (b) Noble gases have very high melting
7 valence electrons of Cl (a) Oxygen family (b) Nitrogen family and boiling points.
6 valence electrons of one oxygen atom (c) Halogens (d) Alkali metals (c) Noble gases have weak dispersion
So there must be unpaired electron, thus forces.
Ans. (c)
it is paramagnetic in nature. (d) Noble gases have large positive
Halogens have maximum electron gain values of electron gain enthalpy.
enthalpy due to the fact that the atoms Ans. (b)
127 A solution of KBr is treated with of these elements have only one
each of the following. Which one electron less than the stable noble gas (a) Noble gases or inert gases are
would liberate bromine? (ns 2 np6 ) configuration. Therefore, they sparingly soluble in water as they are
[CBSE AIPMT 1993] have maximum tendency to accept the non-polar in nature. For solubility the
electron to form negative ion (anion). thumb rule is “Like dissolves like”.
(a) Hydrogen iodide
∴ Statement (a) is correct.
(b) Sulphur dioxide
132 Which of the following bonds will (b) Nobles gases have weak interatomic
(c) Chlorine forces (van der Waals’ forces). So,
(d) Iodine be most polar? [CBSE AIPMT 1992) they have low melting and boiling
Ans. (c) (a) N—Cl (b) O—F (c) N—F (d) N—N points.
Chlorine is good oxidising agent than Ans. (c) ∴ Statement (b) is incorrect.
bromine, so, Cl2 oxidise Br − to bromine. The polar character arises due to the (c) Noble gases have weak London
2KBr + Cl2 → 2KCl + Br2 difference in electronegativity. The dispersion forces which is weaker
electronegativity difference of N—F than all other intermolecular forces.
128 Which of the following species has bond is maximum, so it is more polar ∴ Statement (c) is correct.
bond. (d) The last shell of noble gas have 8
four lone pairs of electrons?
electrons. They have stable
[CBSE AIPMT 1993]
133 The bleaching action of chlorine is electronic configuration. So, addition
(a) I (b) O − of an electron is difficult. Hence, they
(c) Cl− (d) He
due to [CBSE AIPMT 1992]
have large positive values of electron
(a) reduction (b) hydrogenation gain enthalpy.
Ans. (c)
(c) chloronation (d) oxidation ∴ Statement (d) is correct.
Cl − has eight electrons in it valence shell,
•• – Ans. (d)
so its Lewis dot structure is •• Cl •• thus, it
•• When chlorine react with water it gives 136 Match the compounds of Xe in
has four lone pairs of electrons. nascent oxygen which bleaches the column I with the molecular
coloured substances. structure in column II.
129 In the manufacture of bromine H2O + Cl2 → 2HCl + [O] [NEET (Oct.) 2020]
from sea water the mother liquor Coloured substance +
Column I Column II
containing bromide is treated with [O] → Colourless substance
[CBSE AIPMT 1992] A. XeF2 I. Square planar
(a) carbon dioxide
134 Bleaching powder reacts with a B. XeF4 II. Linear
(b) chlorine few drops of conc. HCl to give C. XeO 3 III. Square pyramidal
[CBSE AIPMT 1989]
(c) iodine D. XeOF4 IV. Pyramidal
(d) sulphur dioxide (a) chlorine
(b) hypochlorous acid A B C D A B C D
Ans. (b)
(c) calcium oxide (a) II I III IV (b) II IV III I
Cl2 + 2Br – → Br2 + 2Cl – (d) oxygen
(c) II III I IV (d) II I IV III
Ans. (d) Codes Species lp + bp Structure

(A) XeF2 (B) XeF4 A B C D XeF 2 4lp + 2bp Linear
F (a) 1 2 4 3
sp3d F F
(b) 4 3 1 2 F Xe F
Xe Xe sp3d2
F F (c) 4 1 2 3
F (d) 1 3 4 2 TeF 2 2lp + 2bp Angular or
Linear (II) Square planar (I) V-shape
Ans. (d)
(C) XeO3 (D) XeOF4 Te
A – 1, B – 3, C – 4, D – 2
O The structure of the xenon compounds F F
F F are represented below: ICl –2 4lp + 2bp Linear
sp3
Xe Xe sp3d2
O O F
F F
O F F Cl I– Cl
Pyramidal (IV) Square pyramidal (III) Xe
F F Xe
Hence, option (d) is correct match. BaCl 2 0lp + 2bp Cl—Ba—Cl (linear)
F O O
Distorted O
137 Which of the following pairs of Thus, XeF2 is isostructural with ICl2− .
octahedral XeF6 Pyramidal XeO3
compounds is isoelectronic and
isostructural ? [NEET 2017]
O
F F 141 Which of the following statements
(a) BeCl2 , XeF2
F F is false? [CBSE AIPMT 1994]
Xe Xe (a) Radon is obtained from the decay of
(b) TeI2 , XeF2
F F radium
(c) IBr2− ,XeF2 F F
(b) Helium is inert gas
(d) IF3, XeF2 Square pyramidal Square planar (c) Xenon is the most reactive among
Ans. (c) XeOF4 XeF4
the rare gases
Key concept Isoelectronic species have (d) The most abundant rare gas found in
equal number of valence electrons . 139 The correct geometry and the atmosphere is helium
Both IBr2− and XeF2 are linear and hybridisation for XeF4 are Ans. (d)
number of valence electrons present in [NEET 2016, Phase II] The amount of noble gases present in
both the species is same, i.e. they are
(a) octahedral, sp 3d2 atmosphere (in percent by) is given
also isoelectronic.
(b) trigonal bipyramidal, sp 3d below:
Number of (c) planar triangle, sp 3d 3 Element Abundance (Volume%)
S.No. Compounds valence Geometry
(d) square planar, sp 3d2
electrons He 5.24 × 10 −4
Ans. (a)
1. BeCl 2 2 + 14 = 16 Linear Ne 1.82 × 10 −3
Key Idea Geometry is determined by
2. XeF2 8 + 14 = 22 Linear electron pair arrangement whereas Ar 0.934
shape is determined by arrangement of Kr 1.14 × 10 −3
3. TeI2 6 + 14 = 20 Bent or
atoms around the centre atom.
V-shape Xe 8.7 × 10 −6
4. IBr2− 7 + 14 + 1 = 22 Linear F
F F
F So, argon is most abundant, not helium.
5. IF3 7 + 21 = 28 T-shape Xe 142 Noble gases do not react with

F
F F
F
other elements because
138 Match the compounds given in [CBSE AIPMT 1994]
column I with the hybridisation and (a) they are monoatomic
shape given in column II and mark Geometry – octahedral, (b) they are found in abundance
the correct option. Hybridisation – sp3d2 (c) the size of their atoms is very small
[NEET 2016, Phase I] Thus, option (a) is correct. (d) they are completely paired up and
have stable electron shells
Column I Column II 140 XeF2 is isostructural with Ans. (d)
A. XeF 6 1. Distorted [NEET 2013] In general, noble gases are not very
octahedral
(a) TeF2 (b) ICl2− (c) SbCl3 (d) BaCl2 reactive. Their chemical inertness is due
B. XeO 3 2. Square planar Ans. (b) to the fact that they have completely
filled ns 2 np6 electronic configuration of
C. XeOF 4 3. Pyramidal Species having the same number of their valence shells. The other reasons
bond pairs and lone pairs are are very high ionisation enthalpy and
D. XeF 4 4. Square pyramidal isostructural (have same structure). almost zero electron affinity.
18
d- and f-Block Elements
TOPIC 1 03 Match the followings aspects with Catalyst Process
Characteristics of the respective metal. 3. PdCl 2 iii. Oxidation of SO 2 in
the manufacture of
d-Block Elements Aspects Metal
H2SO 4
A. The metal which reveals a I. Scandiu
01 The calculated spin only magnetic maximum number of m 4. Nickel complexes iv. Polymerisation of
ethylene
moment of Cr 2+ ion is oxidation states
[NEET (Sep.) 2020] B. The metal although II. Copper Which of the following is the
(a) 4.90 BM (b) 5.92 BM placed in 3d block is correct option? [NEET (Odisha) 2019]
considered not as a
(c) 2.84 BM (d) 3.87 BM 1 2 3 4
transition element.
Ans. (a) (a) (iii),(iv), (i), (ii)
C. The metal which does not III. Mangan
Electronic configuration of Cr2 + ion is exhibit variable oxidation ese (b) (i), (ii), (iii), (iv)
2+ 4 states
Cr : [Ar]3d or [Ar] (c) (i), (iii), (ii), (iv)
(22e–)
3d 4 D. The metal which in +1 IV. Zinc
oxidation state in aqueous (d) (iii), (i), (iv), (ii)
It has four (n = 4) unpaired electrons. solution undergoes Ans. (a)
∴Spin only magnetic moment disproportionation
(1) V2 O5 –(iii) Oxidation ofSO2 in the
(µ) = n(n + 2 ) BM manufacture of H2SO4 by contact
= 4 (4 + 2 ) BM = 4.90 BM Select the correct option. process.
[NEET (Oct.) 2020]
(2) TiCl 4 + Al(CH3) 3– (Ziegler-Natta
02 Identify the incorrect statement. A B C D A B C D catalyst)– (iv) Polymerisation of
[NEET (Oct.) 2020] (a) I IV II III (b) III IV I II ethylene.
(a) The transition metals and their (c) III I IV II (d) II IV I III (3) PdCl2 –(i) Oxidation of ethyne to
compounds are known for their ethanal.
Ans. (b)
catalytic activity due to their ability
(4) Nickel complexes–(ii) Polymerisation of
to adopt multiple oxidation states (A) Mn shown six oxidation states in its
alkynes.
and to form complexes. compounds, viz, + 2, + 3, + 4, + 5, + 6 and
Thus, the correct match is
(b) Interstitial compounds are those + 7 ⇒(III)
that are formed when small atoms (1) → (iii), (2)→ (iv), (3) → (i), (4) → (ii)
(B) Zn is a pseudo transition element like
like H, C or N are trapped inside the Cd and Hg of group12 (d 10 -configuration)
crystal lattices of metals. ⇒(IV) 05 When neutral or faintly alkaline
(c) The oxidation states of chromium in (C) Sc does not exhibit variable oxidation KMnO 4 is treated with potassium
CrO24− and Cr2O27− are not the same. states. Only + 3 state is shown by to Sc in iodide, iodide ion is converted into ‘
(d) Cr2 + (d 4 ) is a stronger reducing agent its compounds ⇒(I)
than Fe2 + (d 6 ) in water.
X’. ‘X’ is [NEET (Odisha) 2019]
(D) Cu+ disproportionaton in aqueous (a) I2 (b) IO −4
Ans. (c) solution as,
(c) IO −3 (d) IO −
Statements in options (a), (b) and (d) are 2Cu+ → Cu0 + Cu2 + ⇒(II)
Ans. (c)
correct.
Statement in option (c) is incorrect, 04 Match the catalyst with the process When neutral or faintly alkalineKMnO4 is
because oxidation states of Cr in CrO24 − treated with potassium iodide,KMnO4 is
(chromate) and Cr2O27 − (dichromate) are
Catalyst Process converted intoMnO2 while iodide ( I− ) ion
same and it is +6. 1. V2O 5 i. The oxidation of is converted inotIO−3 (iodate). The
x ethyne to ethanal reaction takes place as follows:
i.e., CrO24 − ⇒ x + 4 (− 2) = 2 ⇒x = + 6 –
y 2. TiCl 4 + Al(CH3) 3 ii. Polymerisation of KMnO4 + I– +OH → MnO2 +IO–3 + H2O
Cr2O27 − ⇒ 2y + 7 (− 2 ) = − 2 ⇒y = + 6 alkynes 'X'
06 Match the metal ions given in The complex which contains unpaired 09 Which of the following does not
electrons exhibitd-d transition and
Column I with the spin magnetic give oxygen on heating? [NEET 2013]
paramagnetism.
moments of the ions given in (a) KClO 3 (b) Zn(ClO 3)2
(i) In MnO−4 ,
Column II and assign the correct (c) K2Cr2O 7 (d) (NH4 )2 Cr2O 7
The electronic configuration ofMn7 + is
code : [NEET 2018]
[Ar]3d 0 . Ans. (d)
Column I Column II Number of unpaired electrons = 0 Oxygen rich compounds like chlorate,
3+ perchlorate, K2 Cr2O7 , etc. when heated
1. Co i. 8 BM Therefore, it will be diamagnetic and
gives oxygen but ammonium dichromate
will not showd-d transition.
2. Cr 3+ ii. 35 BM gives nitrogen gas when heated.
(ii) In Cr2O27− ,
3. Fe 3+ iii. 3 BM ∆
2KClO3 → 2KCl + 3 O2 ↑
The electronic configuration of Cr 6 + is
4. Ni 2 + iv. 24 BM [Ar]3d 0 . ∆
2Zn(ClO3)2 → ZnCl2 + 3 O2
v. 15 BM Number of unpaired electrons = 0
∆
So, it will be diamagnetic and will not 4K2 Cr2O7 → 4K2 CrO4
1 2 3 4 1 2 3 4 show d-d transition. Potassium Potassium
(a) iv i ii iii (b) i ii iii iv dichromate chromate
(iii) In CrO24− ,
(c) iv v ii i (d) iii v i ii + 2Cr2O3 + 3 O2 ↑
The electronic configuration of Cr 6 + is Chromic
Ans. (c) [Ar]3d 0 . oxide
∆
Key Concept Spin magnetic moment can Number of unpaired electrons = 0 (NH4 )2 Cr2O7 → N2 ↑ + Cr2O3 + 4H2O
be calculated as Therefore, it is also diamagnetic and
µ = n(n + 2) BM will not showd-d transition. 10 Which of the following statements
where, µ = magnetic moment (iv) In MnO24− , The electronic about the interstitial compounds is
BM = Bohr Magneton (unit of µ) configuration of Mn is [Ar] 3d 1.
6+
incorrect? [NEET 2013]
n = number of unpaired electrons Number of unpaired electrons = 1 (a) They retain metallic conductivity
in d-orbital. Since, it contains one unpaired (b) They are chemically reactive
The electronic configuration of Co3+ is electron so it will exhibit bothd-d (c) They are much harder than the pure
[Ar] 3d 6 . transition and paramagnetism. metal
Here, n = 4 (d) They have higher melting points than
08 Magnetic moment 2.84 BM is given the pure metals
µ = 4(4 + 2) = 24 BM
The electronic configuration of Cr 3+ is by (At. no. Ans. (b)
[Ar]3d 3. Ni =28, Ti=22, Cr =24, Co = 27) Interstitial compounds are obtained
Here, n = 3 [CBSE AIPMT 2015, 2014] when small atoms like H, B, C, N, etc., fit
into the interstitial space of lattice
µ = 3 (3 + 2) = 15BM (a) Ni2 + (b) Ti3+
3+ metals. These retain metallic
The electronic configuration ofFe3+ is (c) Cr (d) Co2+ conductivity. These resemble the parent
[Ar]3d 5 . Ans. (a) metal in chemical properties (reactivity)
Here, n = 5 Magnetic moment,µ = n(n + 2) BM but differ in physical properties like
where, hardness, melting point, etc.
µ = 5 (5 + 2) = 35 BM
n = number of unpaired electrons 11 The d-electron configurations of
The electronic configuration ofNi2 + is
[Ar] 3d 8 . µ = 2. 84 (given) Cr 2+ , Mn2+ Fe 2+ and Co 2+ are
Here, n = 2 ∴ 2.84 = n(n + 2) B.M d 4 , d 5 , d 6 and d 7 respectively.
µ = 2 (2 + 2) = 8 BM (2. 84)2 = n(n + 2)
Which one of the following will
So, the correct option is (c). 8 = n2 + 2n exhibit minimum paramagnetic
n + 2n − 8 = 0
2
behaviour? [CBSE AIPMT 2011]
07 Which one of the following ions n2 + 4n − 2n − 8 = 0
exhibits d-d transition and (At. no.
n (n + 4) − 2(n + 4) = 0 Cr = 24, Mn = 25, Fe = 26, Co = 27)
paramagnetism as well? [NEET 2018]
n=2 (a) [Fe(H2O) 6] 2+ (b) [Co(H2O) 6] 2+
(a) MnO −4 (b) Cr2O2− 2− 2−
7 (c) CrO 4 (d) MnO 4 2+
Ni = [Ar]3d 8 4s 0 (two unpaired
Ans. (d) (c) [Cr(H2O) 6] 2+ (d) [Mn(H2O) 6] 2+
electrons)
Ans. (b)
Key Concept In d-d transition, an electron Ti3+ = [Ar] 3d14s 0 (one unpaired
in a d-orbital of the metal is excited by a Cr2+ : d4 (4 unpaired
electrons) electrons)
photon to another d-orbital of higher
energy. Cr 3+ = [Ar] 3d 3, (three unpaired Mn2+ : d5 (5 unpaired
electrons)
Paramagnetism The complex compound electrons)
(4 unpaired
which contains unpaired electrons shows Co2 + = [Ar], 3d 7 , 4s 0 (three unpaired Fe2+ : d6 electrons)
paramagnetism while which contains electrons) (3 unpaired
paired electrons shows diamagnetism. Co2+ : d7
So, only Ni2 + has 2 unpaired electrons. electrons)
d- and f-Block Elements 137
∴ [Co(H2O) 6 ]2 + has minimum number of Ans. (c) (a) Ni2+ , Ti3+ (b) Sc 3+ , Ti3+
unpaired electrons and thus, shows In general, the atomic and ionic radii (c) Sc 3+ , Co2+ (d) Ni2+ , Cu +
minimum paramagnetic behaviour. increases on moving down a group but Ans. (a)
Higher the unpaired e – . the elements of second transition series
(Zr, Nb, Mo) have almost same radii as 28 Ni = 1s 2 , 2 s 2 2p6 ,3 s 2 3 p6 3d 8, 4s 2
Higher the magnetic moment 2+
the elements of third transition series Ni = 1s 2 , 2 s 2 2p6 , 3 s 2 3p6 3d 8
µ = n(n + 2)
(Hf, Ta, W, etc). This is because of
n = Number of unpaired e – 3d
8
lanthanoid contraction, i.e. imperfect
shielding of one4f e − by another. (2 unpaired electrons)
12 For the four successive transition
22 Ti = 1s , 2 s 2p6 , 3 s 2 3p6 3d2 ,4s 2
2 2
elements (Cr, Mn, Fe and Co), the 15 Which one of the following ions is 3+
stability of +2 oxidation state will the most stable in aqueous Ti = 1s 2 , 2 s 2 2p6 , 3 s 2 3p6 3d 1
be there in which of the following solution? [CBSE AIPMT 2007]
(1 unpaired electron)
order ? [CBSE AIPMT 2011] Sc = 1s 2
, 2 s 2
2p 6
, 3 s 2
3p6 3d 1,4s 2
(At. no. Ti = 22, V = 23,Cr = 24, 21
3+
(At. no. Cr = 24, Mn = 25, Sc = 1s , 2 s 2p , 3 s 3p6
2 2 6 2
Mn = 25)
Fe = 26, Co = 27) (a) Cr 3+ (b) V 3+ (c) Ti3+ (d) Mn3+
(no unpaired electron)
(a) Fe > Mn > Co > Cr 29 Cu = 1s 2
, 2 s 2
2p 6
, 3s 2 3p6 3d 10 ,4s 1
Ans. (d) +
(b) Co > Mn > Fe > Cr Cu = 1s , 2 s 2p , 3 s 2 3p6 3d 10
2 2 6
Stability of transition metal ions is (no unpaired electron)
(c) Cr > Mn > Co > Fe
directly proportional to the unpaired
(d) Mn > Fe > Cr > Co
electrons. The exactly half-filled and Hence, in the above ions,Ni2 + and Ti3+
Ans. (d) completely filled d-orbitals are extra are coloured in aqueous solution due to
stable. the presence of unpaired electrons in d
This can be understood on the basis of
subshell.
E ° values for M2 +/M. Cr 3+ (21) = 3d 3, 4s 0 (3 unpaired electrons)
E °/V Cr Mn Fe Co V 3+ (20) = 3d2 , 4s 0 (2 unpaired electrons) 18 The aqueous solution containing
M2 +/M – 0.90 –1.18 –0.44 –0.28 Ti3+ (19) = 3d 1, 4s 0 (1 unpaired electron) which one of the following ions will
E ° value for Mn is more negative than Mn3+ (22) = 3d 4 , 4s 0 (4 unpaired electrons) be colourless ?
expected from general trend due to So, Mn3+ ion is most stable in aqueous
extra stability of half-filled electronic solution. (At. no. Sc = 21, Fe = 26, Ti = 22,Mn
configuration of Mn2 + ion. = 25) [CBSE AIPMT 2005]
Thus, the correct order should be 16 The d electron configurations of (a) Sc 3+ (b) Fe2+
Mn > Cr > Fe > Co Cr 2+ , Mn 2+ , Fe 2+ and Ni 2+ are 3d 4 , (c) Ti3+ (d) Mn2+
An examination of E ° values for redox 3d 5 ,3d 6 and 3d 8 respectively. Ans. (a)
couple M3 / M2 + shows that Cr2 + is strong
Which one of the following aqua 21Sc = 1s 2 , 2 s 2 2p6 , 3s 2 3p6 3d 1, 4s 2
reducing agent (E ° 3 + 2 + = 0.41 V) and So, Sc = 1s 2 , 2 s 2 2p6 , 3s 2 3p6
3+
M /M complexes will exhibit the
liberatesH2 from dilute acids. minimum paramagnetic behaviour? (It is colourless due to the absence of
2Cr2 + (aq) + 2H + (aq) → 2Cr 3+ (aq) + H2 ↑ (g) unpaired electrons in d sub-shell)
(At. no. of Cr = 24,Mn = 25, Fe = 26,
26 Fe = 1s , 2 s 2p , 3s 3p 3d , 4s
2 2 6 2 6 6 2
∴ The correct order is Mn > Fe > Cr > Co.
Ni = 28) [CBSE AIPMT 2007] 2+
Fe = 1s , 2 s 2p , 3s 3p 3d
2 2 6 2 6 6
13 Which one of the following ions has (a) [Fe(H2O) 6] 2+ (b) [Ni(H2O) 6] 2+
d
(c) [Cr(H2O) 6] 2+ (d) [Mn(H2O) 6] 2+
electronic configuration [Ar]3 d 6 ?
Ans. (b)
(At. no. Mn = 25, Fe = 26,
As the number of unpaired electron (It is coloured due to the presence of
Co = 27, Ni = 28)
increases, the magnetic moment four unpaired electrons in d sub-shell)
[CBSE AIPMT 2010]
22 Ti = 1s , 2 s 2p , 3s 3p 3d , 4s
increases and hence, the paramagnetic 2 2 6 2 6 2 2
(a) Ni3+ (b) Mn3+ (c) Fe 3+ (d) Co 3+ behaviour increases. 3+
Ti = 1s , 2 s 2p , 3s 3p 3d
2 2 6 2 6 1
Ans. (d) So, Cr2 + (22) = 3d 4 (4 unpaired electrons)
d
Ni3+ (28) = [Ar] 3d 7 Mn2 + (23) = 3d 5 (5 unpaired electrons)
Mn3+ (25) = [Ar] 3d 4 Fe2 + (24) = 3d 6 (4 unpaired electrons)
Fe3+ (26) = [Ar] 3d 5 Ni2 + (26) = 3d 8 (2 unpaired electrons) (It is coloured due to the presence of an
3+ unpaired electron ind sub-shell)
Co (27) = [Ar] 3d So, [Ni(H2O) 6 ]2 + exhibit minimum
6
Hence, Co3+ has 3d 6 electronic paramagnetic behaviour. 25

Mn = 1s 2 , 2 s 2 2 p6 , 3s 2 3p6 3d 5 , 4s 2
configuration correct answer is (d). Mn2 + = 1s 2 , 2 s 2 2 p6 , 3s 2 3p6 3d 5
17 In which of the following pairs are
14 Which of the following pairs has both the ions coloured in aqueous d
the same size? [CBSE AIPMT 2010] solution?
(a) Fe2 + , Ni2 + (b) Zr 4 + , Ti4 + (At. no. Sc = 21, Ti = 22, Ni = 28, Cu (It is coloured due to the presence of five
(c) Zr 4 + , Hf 4 + (d) Zn2 + , Hf 4 + = 29, Co = 27) [CBSE AIPMT 2006] unpaired electrons in d sub-shell).
19 Four successive members of the 21 Which one of the following Ans. (d)
first row transition elements are characteristics of the transition The electronic configuration of Sc is
listed below with their atomic metals is associated with their 1s 2 , 2 s 2 2 p6 , 3 s 2 3p6 3d 1, 4s 2
numbers. Which one of them is catalytic activity? and configuration of Sc 3+ is
expected to have the highest third [CBSE AIPMT 2003] 1 s 2 , 2 s 2 2 p6 , 3 s 2 3 p 6
3+
ionisation enthalpy? (a) Colour of hydrated ions So, Sc is colourless due to absence of
[CBSE AIPMT 2005] (b) Variable oxidation states electrons in d-orbital.
(a) Vanadium (Z = 23) (c) High enthalpy of atomisation
(b) Chromium (Z = 24) (d) Paramagnetic behaviour 25 Bell-metal is an alloy of
[CBSE AIPMT 1999]
(c) Iron (Z = 26) Ans. (b)
(a) Cu + Pb (b) Cu + Sn
(d) Manganese (Z = 25) The catalytic activity of transitional
(c) Cu + Zn (d) Cu + Ni
metals is due to their variable oxidation
Ans. (d) Ans. (b)
states.
In 23V = 1s 2 , 2s 2 2p6 , 3s 2 3p6 3d 3, 4s 2 Bell-metal is an alloy of copper and tin.
Third electron which is removed to give 22 The basic character of the Cu = 80% and Sn = 20%.
third ionisation potential, belongs to3d 3 transition metal monoxides follows It is used for making bells, utensils, etc.
subshell. the order [CBSE AIPMT 2003]
24 Cr = 1s 2 , 2s 2 2p6 , 3s 2 3p6 3d 5 , 4s 1 (At. no. Ti = 22, V = 23, Cr = 24, 26 Which of the following has more
Third electron which is removed to give Fe = 26) unpaired d-electrons?
third ionisation potential, belongs to3d 5 (a) TiO > FeO > VO > CrO [CBSE AIPMT 1999]
(b) TiO > VO > CrO > FeO +
subshell. (a) Zn (b) Fe2+
26 Fe = 1s , 2s 2p , 3s 3p 3d , 4s
2 2 6 2 6 6 2 (c) VO > CrO > TiO > FeO (c) N3+ (d) Cu +
(d) CrO > VO > FeO > TiO Ans. (b)
Third electron which is removed to give
third ionisation potential, belongs to3d 6 Ans. (b)
Zn+ (at. no.= 30) = 1s 2 ,2 s 2 2p6 ,
subshell. The order of basic character of the 3 s 2 3p6 3d 10 ,4s 1
Mn = 1s 2 , 2s 2 2p6 , 3s 2 3p6 3d 5 , 4s 2 transition metal monoxide is TiO > VO >
25 (no unpaired d-electrons)
CrO> FeO because basic character of
Third electron which is removed to give oxides decreases with increase in Fe2 + (at .no.= 26) = 1s 2 , 2 s 2 2p6 ,
third ionisation potential, belongs to3d 5 atomic number. Hence, oxides of 3 s 2 3 p6 3 d 6
subshell. transitional metals in low oxidation
3d 6
state, i.e. +2 and +3 are generally basic
In all elements shell and subshells are
except Cr2O3 .
same. Required amount of energy
4-unpaired d-electrons
(enthalpy) is based upon the stability of
23 In the following transition metals, N3+ (at. no.= 7) = 1s 2 , 2 s 2 2p0
d- subshell.
the maximum number of oxidation (no unpaired d-electrons)
The 3d 5 -subshell has highest stability in
states are exhibited by Cu+ (at. no.= 29) = 1s 2 , 2 s 2 2p6 ,
all because it is half-filled subshell. So,
[CBSE AIPMT 2002, 2000]
Mn shows highest third ionisation 3 s 2 3p6 3d 10
potential. (a) chromium (Z = 24)
(no unpaired d-electrons)
(b) manganese (Z = 25)
(c) iron (Z = 26) So, maximum number of unpaired
20 Among the following series of electrons are present in Fe2 + .
(d) titanium (Z = 22)
transition metal ions, the one in
Ans. (b) 27 Which one of the following ionic
which all metal ions have 3 d 2
Manganese shows maximum number of species will impart colour to an
electronic configuration is oxidation states because it has 5 aqueous solution?
(At. no. Ti =22,V =23,Cr =24, unpaired electrons in 3d and also [CBSE AIPMT 1998]
Mn =25) [CBSE AIPMT 2004] contains 2 electrons in 4s sub-shell.
(a) Ti4+ (b) Cu + (c) Zn2 + (d) Cr 3 +
(a) Ti3+ , V2+ , Cr 3+ , Mn4+ + 2 +3 +4+ 5+6+ 7
Other given metals show the following Ans. (d)
(b) Ti+ , V 4+ , Cr 6+ , Mn7 + oxidation states Cr 3+ = 1s 2 , 2 s 2 2 p6 , 3s 2 3p6 3d 3 (coloured)
(c) Ti4+, V 3+ , Cr2 + , Mn3+ Cr = + 2 + 3 + 4 + 5 + 6 (Cr 3 + contains 3 unpaired e − , so it gives
(d) Ti2+ , V 3+ , Cr 4+ , Mn5+ Fe = + 2 + 3 ; Ti = + 2 + 3 + 4 colour)
Ans. (d) 24 Which one of the following forms a Zn2 + = 1s 2 , 2 s 2 2p6 , 3s 2 3p6 3d10
(colourless)
Ti2 + = 1s 2 , 2s 2 2p6 , 3 s 2 3p6 3d2 , 4s 0 colourless solution in aqueous
Cu+ = 1s 2 , 2 s 2 2p6 , 3s 2 3p6 3d 10
V 3 + = 1s 2 , 2s 2 2p6 , 3 s 2 3p6 , 3d2 , 4s 0 medium? (colourless)
Cr 4 + = 1s 2 , 2s 2 2p6 , 3 s 2 3p6 3d2 , 4s 0 (At. no. Sc = 21, Ti = 22, V = 23, Ti4+ = 1s 2 , 2 s 2 2p6 , 3s 2 3p6 (colourless)
Mn5 + = 1s 2 , 2s 2 2p6 , 3 s 2 3p6 3d2 , 4s 0 Cr = 24) [CBSE AIPMT 2000] (Colour is produced due to presence of
(a) V2+ (b) Cr 3+ (c) Ti3+ (d) Sc 3+ unpaired electrons.)
28 Which of the following elements is Ans. (b) ∆

(b) Cr2O3 + 2Al → Al2O3 + 2Cr;
responsible for oxidation of water During electrolysis, copper is deposited
(Metal displacement reaction)
to O 2 in biological processes? at the cathode while oxygen is liberated
∆
[CBSE AIPMT 1997] at anode. The following reactions occur (c) Fe + 2HCl → FeCl2 + H2 ;
at the electrodes
(a) Fe (b) Cu (c) Mn (d) Mo (Displacement reaction)
At anode
Ans. (c) (d) 2Pb(NO3)2 → 2PbO + 4NO2 + O2 ;
2H2O → 4H+ + O2 + 4e −
Manganese is responsible for oxidation (Decomposition reaction)
(Oxidation)
of water to O2 in biological processes. Metal displacement reaction is a
At cathode
displacement reaction in which a more
Cu2 + + 2e − → Cu(s ) (Reduction) reactive metal displaces/replaces the
29 Which of the following does not
represent the correct order of the less reactive metal. In option (c),
32 The transition elements have a hydrogen is a non-metal. So, it is
properties indicated? general electronic configuration. displacement reaction but not a metal
[CBSE AIPMT 1997]
[CBSE AIPMT 1991] displacement reaction.
(a) Ni2 + > Cr2 + > Fe2 + > Mn2 + (size)
(a) ns 2np 6nd 1− 10
(b) Sc > Ti > Cr > Mn (size) 35 The manganate and permanganate
(b) (n − 1) d 1− 10, ns 0−2 , np 0− 6
(c) Mn2 + > Ni2 + > Co2 + > Fe2 +
(c) (n − 1) d 1− 10, ns 1−2 ions are tetrahedral, due to
(unpaired electron)
(d) nd 1− 10ns 2 [NEET (National) 2019]
(d) Fe2 + > Co2 + > Ni2 + > Cu2 + (a) there is no π-bonding
Ans. (c)
(unpaired electron) (b) the π-bonding involves overlap of
In the transition elements, the d-orbitals p -orbitals of oxygen with p -orbitals
Ans. (a)
are successively filled. The general of manganese
In a period on moving from left to right electronic configuration of d-block is
ionic radii decreases. So, the order of (c) the π-bonding involves overlap of
(n − 1)d 1− 10 ns 1−2 d-orbitals of oxygen with d-orbitals
cationic radii is
Where (n − 1) stands for inner shell and of manganese
Cr2 + > Mn2 + > Fe2 + > Ni2 + d-orbitals may have one to ten electrons (d) the π-bonding involves overlap of
In Sc > Ti > Cr > Mn (correct order of and the s-orbital of the outermost shell p-orbitals of oxygen with d-orbitals
atomic radii) (n) may have one or two electrons. of manganese
In Ans. (d)
Mn2 + > Ni2 + < Co2 + < Fe2 + 33 Which of the following metals
↓ ↓ ↓ ↓ The structures of manganate and
corrodes readily in moist air? permanganate ions are as follows :
Five Two Three Four [CBSE AIPMT 1988]
unpaired unpaired unpaired unpaired (a) Gold (b) Silver O– O
electrons electrons electrons electrons (c) Nickel (d) Iron Mn Mn
In Ans. (d) O O– O O–
Fe2 + > Co2 + > Ni2 + > Cu2 + O O
↓ ↓ ↓ ↓ Iron corrodes readily in moist air
Manganate Permanganate
4 3 2 1 because iron is more reactive than Ni, Au 2–
(MnO4 )
–
(MnO4 )
Number of unpaired electrons and Ag. In other words the reduction
potential of iron is very less, so its The manganate and permanganate
oxidation takes place readily. ions are tetrahedral and contain
30 The common oxidation states of Ti
are [CBSE AIPMT 1994] π-bonds of dπ - pπ -type, oxygen does
(a) +2, +3 (b) +3, +4 TOPIC 2 not have any d-orbital.
Hence, the π-bonding takes place by
(c) 3, −4 (d) +2, +3, +4 Important Compounds overlap of p-orbital of oxygen and
Ans. (b)
of d-Block Elements d-orbitals of manganese.
The most common oxidation state of
titanium are +3 and +4. 34 Which of the following reactions is 36 The number of hydrogen bonded
the metal displacement reaction ? water molecule(s) associated with
31 When CuSO 4 is electrolysed using CuSO 4 ⋅ 5H2O is [NEET (Odisha) 2019]
Choose the right option. [NEET 2021]
platinum electrodes? ∆
(a) 2KClO 3 → 2KCl + 3 O2 (a) 3 (b) 1
[CBSE AIPMT 1993] (c) 2 (d) 5
∆
(a) Copper is liberated at cathode, (b) Cr2O 3 + 2Al → Al2O 3 + 2Cr
Ans. (b)
sulphur at anode (c) Fe + 2HCl→ FeCl2 + H2 ↑
Cu2 + ion has 17 electrons in its
(b) Copper is liberated at cathode, (d) 2Pb(NO 3)2 → 2PbO + 4 NO2 + O2 ↑ outermost orbital. 4H2O molecules
oxygen at anode
Ans. (b) donate 4 pairs of electrons for
(c) Sulphur is liberated at cathode, coordinate covalent sharing. The oneH2O
∆
oxygen at anode (a) 2KClO3 → 2KCl + 3O2 ; molecule is attached to the sulphate ion
(d) Oxygen is liberated at cathode, by hydrogen bonding, the oxygen being
(Decomposition reaction)
copper at anode oriented to the hydrated cupirc ion.
H2O OH2 H----O O and when conc.HNO3 is used, reaction ∴ Formation of Fe(CO) 5 from Fe does not
Cu O S proceeds as involve oxidation of iron because there is
H2O OH2 H----O O Cu + 4HNO3 (conc.) → Cu(NO3) 2 no change in oxidation state.
+ 2NO2 + 2H2O
Thus, the number of hydrogen bonded 43 The pair of compounds that can
water molecule associated with CuSO4 . exist together is [CBSE AIPMT 2014]
5H2O is 1. 40 Which one of the following
statements is correct when SO 2 is (a) FeCl3, SnCl2 (b) HgCl2 , SnCl2
37 Name the gas that can readily passed through acidified K 2 Cr 2 O 7 (c) FeCl2 , SnCl2 (d) FeCl3, Kl
decolourise acidified KMnO 4 solution? [NEET 2016, Phase I] Ans. (c)
solution. [NEET 2017] (a) The solution is decolourised The compounds with lower oxidation
(a) CO2 (b) SO2 (c) NO2 (d) P2O 5 (b) SO2 is reduced number and which cannot reduced by
(c) Green Cr2 (SO 4 ) 3 is formed one another can exist together. Thus,
Ans. (b) FeCl2 and SnCl2 can exist together as
(d) The solution turns blue
SO2 gas can readily oxidise acidified Fe2 + cannot be reduced bySn2 + .
KMnO4 solution becauseKMnO4 is an Ans. (c)
oxidising agent andSO2 act as reducing When SO2 is passed through acidified 44 The reaction of aqueous KMnO4
agent. K2 Cr2O7 solution, green chromium
2MnO−4 + 5SO2 + 2H2O → 2Mn2 + sulphate is formed. In this reaction, with H2O 2 in acidic conditions gives
[CBSE AIPMT 2014]
+ 5SO24− + 4H+ oxidation state of Cr changes from +6 to
+3. (a) Mn4 + and O2 (b) Mn2 + and O2
While other options such asNO2 (strong
oxidising agent), CO2 (neither oxidising K2 Cr2O7 + H2SO4 + 3SO2 → K2SO4 (c) Mn2 + and O 3 (d) Mn4 + and MnO2
OS of Cr = +6
agent nor reducing agent) cannot Ans. (b)
+ Cr2 (SO4 ) 3 + H2O
decolourise acidifiedKMnO4 Solution. OS of Cr = + 3 The reaction of aqueousKMnO4 with H2O2
Green
in acidic medium is
38 HgCl 2 and I 2 both when dissolved in The appearance of green colour is due to
3H2SO4 + 2KMnO4 + 5H2O2 →
the reduction of chromium metal.
water containing I − ions the pair of 5 O2 + 2MnSO4 + 8H2O + K2SO4
species formed is [NEET 2017] 41 Assuming complete ionisation, In the above reaction,KMnO4 oxidises
(a) HgI2 , I3− (b) HgI2 , I− H2O2 to O2 and itself i.e. [MnO−4 ] gets
same moles of which of the
(c) HgI24− , I−3 (d) Hg2I2 , I− reduced toMn2 + ion as MnSO4 . Hence,
following compounds will require aqueous solution of KMnO4 with H2O2
Ans. (c) the least amount of acidified yields Mn2 + and O2 in acidic conditions.
HgCl2 and I2 both when dissolved in water KMnO 4 for complete oxidation?
containing I− ions, the pair of species [CBSE AIPMT 2015] 45 Identify the alloy containing a
formed is HgI24− and I−3 . (a) FeSO 4 (b) FeSO 3 non-metal as a constituent in it.
In aqueous solution, I2 reacts with I − and (c) FeC2O 4 (d) Fe(NO2 )2 [CBSE AIPMT 2012]
maintains the following equilibrium. Ans. (a) (a) Invar (b) Steel
I2 + I− q I−3 (c) Bell-metal (d) Bronze
2+ FeSO4 will require the least amount of
Hg gives ppt. of HgI2 on reaction with acidifiedKMnO4 for complete oxidation. Ans. (b)
I− .
But HgI2 is soluble in excess of I − 42 Which of the following processes
Alloy Constituents
Hg2 + + 2I− → HgI2 ↓ + 2Cl − does not involve oxidation of iron?
Invar Fe + Ni
Red ppt.
[CBSE AIPMT 2015] Steel Fe + C
HgI2 + 2I− q [HgI4 ]2 − Bell-metal Cu (80%) + Sn(20%)e
(a) Rusting of iron sheets
(b) Decolourisation of blue CuSO4 Bronze Cu(75.90%) + Sn(10.25)%
39 When copper is heated with conc. solution by iron
HNO 3 it produces (c) Formation of Fe(CO) 5 from Fe
Among these alloys, only steel contains
[NEET 2016, Phase I] carbon which is a non-metal.
(d) Liberation of H2 from steam by iron a
(a) Cu(NO 3)2 and NO high temperature
(b) Cu(NO 3)2 , NO and NO2 46 Acidified K 2Cr 2O 7 solution turns
Ans. (c)
(c) Cu(NO 3)2 and N2 O 0 III
green when Na 2SO 3 is added to it.
(d) Cu(NO 3)2 and NO2 (a) Fe + H2O + O2 → Fe2 O3 ⋅x H2O] This is due to the formation of
1424 3
Ans. (d) from air [CBSE AIPMT 2011]
Nitric acid acts as an oxidising agent

0
(b) Fe + CuSO4 → FeSO4 + Cu
II (a) CrO2–
4 (b) Cr2 (SO 3) 3
while reacting with copper. When dil. 0 0
(c) CrSO4 (d) Cr2 (SO 4 ) 3
HNO3 reacts, reaction proceeds as: (c) Fe + 5CO → Fe (CO) 5 Ans. (d)
3Cu + 8HNO3 (dil.) → 3Cu(NO3) 2 0 III K2 Cr2O7 is oxidising reagent.
(d) Fe + H2O → Fe2 O3 + H2
+ 2NO + 4H2O K2 Cr2O7 + 3Na2SO3 + 4H2SO4 →
Steam
3Na2SO4 + K2SO4 + Cr2 (SO4 ) 3 + 4H2O
47 Copper sulphate dissolves in 50 In which of the following (c) diamagnetic nature

excess of KCN to give compounds, transition metal has (d) insolubility in water
[CBSE AIPMT 2006] zero oxidation state? Ans. (a)
(a) CuCN (b) [Cu(CN) 4] 3– [CBSE AIPMT 1999] Cuprous compound contains Cu+ ion
(c) [Cu(CN) 4] 2– (d) Cu(CN)2 (a) Fe(CO) 5 (b) NH2 ⋅NH2 which has small size, so the hydration is
Ans. (b) (c) NOClO 4 (d) CrO 5 maximum and hence, the system has
lower energy which result in stability of
Copper sulphate when react with KCN Ans. (a)
the compounds.
first give precipitate of cupric cyanide Oxidation state of Fe inFe(CO) 5 is zero
which reduce into Cu2 CN2 and dissolve in because CO is a neutral ligand and it
excess of KCN to give soluble
54 Stainless steel contains iron and
shows zero oxidation state. [CBSE AIPMT 1995]
K3 [Cu(CN) 4 ] complex salt
[CuSO4 + 2KCN → Cu(CN)2 + K2SO4 ] × 2 51 When a substance A reacts with (a) Cr + Ni (b) Cr + Zn
Cupric water it produces a combustible (c) Zn + Pb (d) Fe + Cr + Ni
cyanide
gas B and a solution of substance C Ans. (a)
2Cu(CN)2 → Cu2 (CN)2 + NC—CN
Cyanogen in water. When another substance Stainless steel is resistant to rusting. It
D reacts with this solution of C, it contains 73% iron, 18% chromium and
Cu2 (CN)2 + 6KCN → 2K3 [Cu(CN) 4 ]
8% nickel. Stainless steel is used in
Soluble complex salt also produces the same gas B on
utensils, cycle, cutlery and automobile
2CuSO 4 + 10KCN → 2K 3 [Cu(CN) 4] + 2K 2SO 4
warming but D can also produce parts.
+ (CN)2
gas B on reaction with dilute
sulphuric acid at room 55 By pasing H2S gas in acidified
48 CuSO 4 when reacts with KCN temperature. A imparts a deep KMnO 4 solution, we get
golden yellow colour to a [CBSE AIPMT 1995]
forms CuCN which is insoluble in
smokeless flame of Bunsen burner. (a) S (b) K2 S
water. It is soluble in excess of KCN
A, B, C and D, respectively are (c) MnO2 (d) K2 SO 3
due to the formation of the
[CBSE AIPMT 1998] Ans. (a)
complex [CBSE AIPMT 2002]
(a) Na, H2 , NaOH, Zn
(a) K2 [Cu(CN) 4] (b) K 3 [Cu(CN) 4] 2KMnO4 + 5H2S + 3H2SO4 →
(b) K, H2 , KOH, Al
(c) Cu(CN)2 (d) Cu[KCu(CN) 4] K2SO4 + 5S + 2MnSO4 + 8H2O
(c) CaH2 , Ca(OH)2 , Sn
Ans. (b) (d) CaC2 , C2H2 , Ca(OH)2 , Fe 56 When (NH4 ) 2 Cr 2O 7 is heated, the
CuSO4 reacts with KCN to give a white Ans. (a)
precipitate of cuprous cyanide and gas evolved is [CBSE AIPMT 1994]
cyanogen gas. The cuprous cyanide Only Na gives golden colour to bunsen
(a) N2 (b) NO2
dissolves in excess of KCN forming flame. So, A is Na
(c) O2 (d) N2O
K3 [Cu(CN) 4 ]. 2Na + 2H2O → 2NaOH + H2 ↑
A C B Ans. (a)
CuSO4 + 2KCN → K2SO4 + Cu(CN) 2 Zn + 2NaOH —→ Na2ZnO2 + H2 ↑
Unstable D C
When ammonium dichromate is heated,
B
Zn + dil. H2SO4 → ZnSO4 + H2 ↑ it form nitrogen gas, Cr2O3 and water.
2Cu(CN)2 → 2CuCN + CN  CN D ∆
Insoluble cyanogen
B
(NH4 )2 Cr2O7 → Cr2O3 + 4H2O + N2
Na, produces golden yellow colour with
CuCN + 3KCN → K3 [Cu(CN) 4 ] smokeless flame of Bunsen burner
Soluble 57 The most durable metal plating on
49 In the silver plating of copper, 52 K 2Cr 2O 7 on heating with iron to protect against corrosion is
K[Ag(CN) 2] is used instead of aqueous NaOH gives [CBSE AIPMT 1994]
[CBSE AIPMT 1997] (a) nickel plating (b) tin plating
AgNO 3 . The reason is
[CBSE AIPMT 2002] (a) CrO2–
4 (b) Cr(OH) 3 (c) copper plating (d) zinc plating
(a) a thin layer of Ag is formed on Cu (c) Cr2O2–
7 (d) Cr(OH)2 Ans. (d)
(b) more voltage is required Ans. (a)
Zinc is commonly used for covering iron
(c) Ag + ions are completely removed K2 Cr2O7 + 2NaOH → K2 CrO4 surfaces. The process of covering iron
from solution + Na2 CrO4 + H2O with zinc is called galvanisation. If some
(d) less availability of Ag + ions, as Cu Hence, CrO24– ion is obtained. scratches occur on the protective zinc
cannot displace Ag from [Ag(CN)2 ] – film on coated iron, even then iron will
ion 53 Cuprous compounds such as CuCl, not be rusted. This is due to the fact that
Ans. (d) CuCN and CuSCN are the only salts because of scratches, both zinc and iron
get exposed to oxidation but zinc
In the silver plating of copper, stable in H2O due to undergoes oxidation in preference to
K [Ag(CN)2 ] is used instead of AgNO3.The [CBSE AIPMT 1996]
iron, because the reduction potential of
reason is less availability of Ag + ions, as (a) high hydration energy of Cu+ ions zinc is less than the reduction potential
Cu cannot displace Ag from [Ag(CN)2 ] – (b) their inherent tendency not to of iron. So, zinc coating is the best and
ion. disproportionate durable method for protection of iron.
58 Nitriding is the process of surface The surface area increases when (c) [Xe] 4f 7 6s 2 , [Xe] 4f 7 5d 16s 2 and
actinoids are finely divided which results [Xe] 4f 9 6s 2
hardening of steel by treating it in
in exposure of more reactant molecules (d) [Xe] 4f 7 6s 2 , [Xe] 4f 8 6s 2 and
an atmosphere of to react. Hence, rate increases and so, [Xe] 4f 8 5d 16s 2
[CBSE AIPMT 1989] actinoids are highly reactive metals Ans. (c)
(a) NH3 (b) N2 when finely divided.
(c) O 3 (d) H2 S Electronic configuration of
∴ Statement (d) is correct.
63Eu = [Xe] 54 4f 6s
7 2
Ans. (a)
Electronic configuration of
Nitriding is the process of heating of 61 Zr (Z = 40) and Hf (Z = 72) have
64 Gd = [Xe] 54 4f 5d 6s
7 1 2
steel in the presence of ammonia. In this similar atomic and ionic radii
process the layer of iron nitride is Electronic configuration of
because of [NEET 2021]
formed which prevent the rusting of 65
Tb = [Xe] 54 4f 9 6s 2
iron. (a) belonging to same group
(b) diagonal relationship 64 Which one of the following
59 Photographic plates and films have (c) lanthanoid contraction statements related to lanthanons is
an essential ingredient of (d) having similar chemical properties incorrect? [NEET 2016, Phase II]
(a) silver nitrate [CBSE AIPMT 1989] Ans. (c) (a) Europium shows +2 oxidation state
(b) silver bromide Zr (Z = 40) → 1s 2 , 2s 2 2p6 3s 2 3p6 (b) The basicity decreases as the ionic
3d 10 , 4s 2 4p6 4d2 , 5s 2 radius decreases from Pr to Lu
(c) sodium chloride
(c) All the lanthanons are much more
(d) oleic acid Hf(Z = 72) → 1s 2 , 2s 2 2p6 , 3s 2 3p6 3d 10 , reactive than aluminium
Ans. (b) 4s 2 4p6 4d 10 , 5s 2 5p6 4f 14 5d2 , 6s 2 (d) Ce (+4) solutuion are widely used as
The photographic plate of film consists Hf is a post lanthanoid element. Due to oxidising agent in volumetric
of a glass plate or thin strip of celluloid presence of4f-orbitals which have poor analysis
which is coated with the thin layer of an shielding effect, the effective nuclear Ans. (c)
emulsion of silver bromide dispersed in charge on valence shell electrons is
more which result in the decrease of the Eu(63) = 4f 7 ⋅ 5d 0 , 6s 2 , Eu2 + = 4f 7
gelatin.
size of Hf. This effect is known as In lanthanoids series, ionic radius
lanthanoid contraction. decreases and covalent character
TOPIC 3 increases, thus basicity decreases.
Lanthanons are less reactive than
Inner Transition Elements 62 The reason for greater range of aluminium due to high ionisation
oxidation states in actinoids is potential. The reason for this high
60 The incorrect statement among the attributed to [NEET 2017] ionisation potential is lanthanoid
following is [NEET 2021] (a) the radioactive nature of actinoids contraction. Ce4+ is a good oxidising
(a) actinoid contraction is greater for (b) actinoid contraction agent, it is easily converted to Ce3+
element to element than lanthanoid (c) 5f, 6d and 7s levels having
contraction. comparable energies 65 Gadolinium belongs to 4f series. It’s
(b) most of the trivalent lanthanoid ions (d) 4f and 5d levels being close in atomic number is 64. Which of the
are colourless in the solid state. energies following is the correct electronic
(c) lanthanoids are good conductors of Ans. (c) configuration of gadolinium?
heat and electricity. [CBSE AIPMT 2015]
The reason for greater range of
(d) actinoids are highly reactive metals,
oxidation states in actinoid is attributed (a) [Xe]4 f 8 6d2 (b) [Xe]4 f 9 5 s 1
especially when finely divided. to the 5f, 6d and 7s levels having (c) [Xe]4f 7 5d1 6s 2 (d) [Xe]4 f 6 5 d2 6 s 2
Ans. (b) comparable energies. Ans. (c)
The shielding effect of 5f-orbitals in The 5f-orbitals extend into space beyond 64 Gd = [Xe] 4f 7 5d 1 6s 2
actinoids is poor than the shielding the 7s and 6p-orbitals and participate in
effect of 4f-orbitals. So, the effective bonding. This is in direct contrast to the 66 Because of lanthanoid contraction,
nuclear charge on valence electrons is lanthanides where the4f-orbitals are which of the following pairs of
more in actinoids. Hence, actinoid buried deep inside the atom, totally elements have nearly same atomic
contraction is greater than lanthanoid shielded by outer orbitals and thus radii? (Numbers in the parenthesis
contraction. unable to take part in bonding.
are atomic numbers).
∴ Statement (a) is correct. [CBSE AIPMT 2015]
Trivalent lanthanoid ions are coloured in 63 The electronic configurations of Eu (a) Ti (22) and Zr (40)
the solid state due to presence of (Atomic no. 63), Gd (Atomic no. 64) (b) Zr (40) and Nb (41)
f-electrons. and Tb (Atomic no. 65) are (c) Zr (40) and Hf (72)
∴ Statement (b) is incorrect. [NEET 2016, Phase I] (d) Zr (40) and Ta (73)
Lanthanoids are inner transition metals. (a) [Xe] 4f 6 5d 16s 2 , [Xe] 4f 7 5d 16s 2 and Ans. (c)
So, they are good conductors of heat [Xe] 4f 9 6s 2
and electricity. Because of the lanthanoid contraction Zr
(b) [Xe] 4f 6 5d 16s 2 , [Xe] 4f 7 5d 16s 2 and
(atomic radii 160 pm) and Hf (atomic radii
∴ Statement (c) is correct. [Xe] 4f 8 5d 16s 2
158 pm) have nearly same atomic radii.
Lanthanoids include the elements from 69 Which of the following ions will (b) lesser energy difference between 5f
lanthanum La (Z = 57) to lutetium and 6d-orbitals than that between 4f
exhibit colour in aqueous
Lu(Z = 71). zirconiumZr (40) belong to the and 5d-orbitals
second transition series (4d) and Hf (72) solutions? [CBSE AIPMT 2010]
(c) greater metallic character of the
belongs to third transition series (5d). (a) La3+ (Z = 57) (b) Ti3+ (Z = 22) lanthanides than that of the
Lanthanoid contraction is associated (c) Lu 3+ (Z = 71) (d) Sc 3+ (Z = 21) corresponding actinides
with the intervention of the4f orbitals Ans. (b) (d) more active nature of the actinides
which are filled before the 5d-series of
Key Idea Colour is obtained as a Ans. (b)
elements starts. The filling of4f orbitals
before 5d-orbitals results in regular consequence of d-d (or f-f) transition, and More number of oxidation states are
decrease in atomic radii which for d-d (or f-f ) transition, presence of exhibited by the actinides than by the
compensates the expected increase in unpaired electrons is the necessary corresponding lanthanides due to lesser
atomic size with increasing atomic condition. energy difference between 5f and 6d
number. As a result of this lanthanoid Electronic configuration of orbitals than that between4f and
contraction, the elements of second and La3+ (Z = 57 ) = [Xe] 4f 0 5 d 0 6s 0 5d-orbitals.
third transition series have almost (no unpaired electron)
similar atomic radii. Ti3+ (Z = 22) = [Ar] 3 d 14s 0 72 Lanthanides are
(one unpaired electron) [CBSE AIPMT 2004]
67 Reason of lanthanoid contraction is 3+
Lu (Z = 71) = [Xe]4f 14 5 d 0 6s 0 (a) 14 elements in the sixth period
[CBSE AIPMT 2014]
(no unpaired electron) (At. no. = 90 to 103 ) that are filling4f
(a) negligible screening effect of
Sc3+ (Z = 21) = [Ar] 3d 0 4s 0 sub-level
f-orbitals
(no unpaired electron) (b) 14 elements in the seventh period
(b) increasing nuclear charge (At. no. = 90 to 103) that are filling 5f
(c) decreasing nuclear charge sub-level
(d) decreasing screening effect
70 Identify the incorrect statement
(c) 14 elements in the sixth period
among the following.
Ans. (a) (At. no. = 58 to 71) that are filling4f
[CBSE AIPMT 2007]
Lanthanoid contraction is the regular sub-level
(a) There is a decrease in the radii of the (d) 14 elements in the seventh period
decrease in atomic and ionic radii of atoms or ions as one proceeds from
lanthanides. This is due to the imperfect (At. no. = 58 to 71) that are filling4f
La or Lu sub-level
shielding [or poor screening effect] of
(b) Lanthanide contraction is the
f-orbitals due to their diffused shape Ans. (c)
accumulation of successive
which unable to counterbalance the Lanthanides are the 14 elements of IIIB
shrinkages
effect to the increased nuclear charge.
(c) As a result of lanthanide contraction, group and sixth period (at. no. = 58 to 71)
Hence, the net result is a contraction in
the properties of4d series of the that are filling4f sub-shell of
size of lanthanoids.
transition elements have no antipenultimate shell from 1 to 14.
similarities with the 5d series of Actually, they are placed below the
68 Which of the following lanthanoid elements periodic table in horizontal row as
ions is diamagnetic? (d) Shielding power of4f electrons is lanthanide series.
(At. no. Ce = 58, Sm = 62 , Eu = 63, quite weak
Yb = 70) [NEET 2013] Ans. (c) 73 The correct order of ionic radii of
(a) Ce2+ (b) Sm2+ (c) Eu2+ (d) Yb2+ The regular decrease in the radii of Y 3 + , La 3 + , Eu 3 + and Lu 3+ is
Ans. (d) lanthanide ions fromLa3+ to Lu3+ is [CBSE AIPMT 2003]
known as lanthanides contraction. (At. no. Y = 39, La = 57, Eu = 63, Lu
Lanthanoid ion with no unpaired electron
is diamagnetic in nature. It is due to the greater effect of the = 71)
increased nuclear charge than that of
Ce58 = [Xe] 4f2 5d 0 6s 2 (a) Lu 3+ < Eu 3+ < La3+ < Y3+
screening effect (shielding effect).
Ce2 + = [Xe] 4f2 (b) La3+ < Eu 3 + < Lu 3+ < Y3+
As a result of lanthanide contraction, the
(two unpaired electrons) atomic radii of element of4d and 5d (c) Y3 + < La3+ < Eu 3+ < Lu 3+
Sm62 = [Xe] 4f 6 5 d 0 6s 2 come closer, so the properties of4d and (d) Y3+ < Lu 3+ < Eu 3+ < La3+
Sm2 + = [Xe] 4f 6 5d-transition element shows the
similarities.
Ans. (d)
(six unpaired electrons)
The correct order of ionic radii of
Eu63 = [Xe] 4f 7 5 d 0 6s 2 71 More number of oxidation states Y 3 + , La3 + , Eu3 + and Lu3 + , is
Eu2 + = [Xe] 4f 7 are exhibited by the actinides than Y 3+ < Lu3+ < Eu3+ < La3 + because Eu and
(seven unpaired electrons) Lu are the members of lanthanide series
by the lanthanides. The main (so they show lanthanide contraction)
Yb70 = [Xe] 4f 14 5 d 0 6s 2 reason for this is and La is the representative element of
Yb2 + = [Xe] 4f 14 [CBSE AIPMT 2006, 2005] all elements of such series and Y 3+ ion
(no unpaired electrons) (a) more energy difference between 5f has lower radii as comparison toLa3+
Because of the absence of unpaired and 6d-orbitals than that between 4f because it lies immediately above it in
electrons, Yb2 + is diamagnetic. and 5d-orbitals the periodic table.
74 General electronic configuration 76 Which one of the following elements have the same radius and also known as
twins.
of lanthanides are shows maximum number of different
[CBSE AIPMT 2002] oxidation states in its compounds?
(a) (n − 2) f 1− 14 (n − 1) s 2 p 6d 0− 1ns 2 [CBSE AIPMT 1998]
78 Among the lanthanides, the one
obtained by synthetic method is
(b) (n − 2) f 10− 14 (n − 1) d 0− 1ns 2 (a) Eu (b) La (c) Gd (d) Am
[CBSE AIPMT 1994]
(c) (n − 2) f 0− 14 (n − 1) d 10ns 2 Ans. (d)
(a) Lu (b) Pm
(d) (n − 2) d 0− 1 (n − 1) f 1− 14 ns 2 Oxidation states shown by elements are as (c) Pr (d) Gd
follows:
Ans. (a) Ans. (b)
La = + 3
In lanthanides (at. no. of elements 57 Promethium (Pm) is the element which is
Eu and Gd = + 2 and + 3 prepared only by synthetic methods. It is
to 71) the electronic configuration of
outermost shells are Am = + 2 + 3 + 4 + 5 not present in nature. It is the only
(n − 2)f 1 − 14 (n − 1) s 2 p6d 0 to 1ns 2 . and +6 synthetic radioactive lanthanoid.
Am shows maximum number of different
75 Which of the following oxidation state due to its larger size and low 79 Actinides [CBSE AIPMT 1994]
statements is not correct? ionisation energy. (a) are all synthetic elements
[CBSE AIPMT 2001] (b) include element 104
(a) La(OH) 3 is less basic thanLi(OH) 3 77 The lanthanide contraction is (c) have any short lived isotopes
(b) In lanthanide series, ionic radius responsible for the fact that (d) have variable valency
of Ln3+ ion decreases [CBSE AIPMT 1997]
Ans. (d)
(c) La is actually an element of (a) Zr and Yt have about the same radius
transition series rather lanthanide (b) Zr and Nb have similar oxidation state All actinides show different oxidation
(d) Atomic radius of Zr and Hf are states such as +2 +3 +4 +5 and +7.
(c) Zr and Hf have about the same radius
same because of lanthanide However, +3 oxidation state is most
(d) Zr and Zn have the same oxidation state
contraction common among all the actinides. The
Ans. (c) wide range of oxidation states of
Ans. (a) actinides is attributed to the fact that
The elements of second and third transition
La3 + ions larger thanLi3 + . So, it easily series resembles more in properties than the 5f,6d and 7s energy levels are of
gives OH− ion La (OH) 3 is more basic the elements of first and second transition comparable energies. Therefore, all
than Li(OH) 3. In lanthanides the basic series. It is due to lanthanide contraction. these three sub-shells can participate.
character of hydroxides decreases as So, due to lanthanide contraction Zr and Hf
the ionic radius decreases.
19
Co-ordination Compounds
TOPIC 1 number of Co is 6 with octahedral 3d
geometry. Ni(CO)4 ×× ×× ×× ××
Nomenclature, Isomerism
Cl Cl
and Werner’s Theory Cl
CO CO CO CO
en Co en Co en sp3-hybridised
01 Ethylene diaminetetraacetate (Tetrahedral geometry)
(EDTA) ion is [NEET 2021] en
Cl There is no unpaired electron, hence,
(a) hexadentate ligand with four O and cis-isomer trans-isomer
two N donor atoms (Optically (Optically Ni(CO) 4 is diamagnetic with tetrahedral
active) inactive) geometry.
(b) unidentate ligand CO
(c) bidentate ligand with two N donor Thus, [CoCl2 (en)2 ] show geometrical
atoms isomerism. Ni
(d) tridentate ligand with three N CO
OC
donor atoms 03 The geometry and magnetic CO
Ans. (a) behaviour of the complex [Ni(CO) 4]
Ethylene diaminetetraacetate (EDTA) are [NEET 2018] 04 The correct order of the
ion. (a) square planar geometry and stoichiometrics of AgCl formed
O O paramagnetic when AgNO 3 in excess is
(b) tetrahedral geometry and treated with the complexes:
O—C—CH2 CH2—C—O
N ––CH2 —CH2—N
diamagnetic CoCl 3 ⋅ 6NH3 , CoCl 3 ⋅ 5NH3 ,
O CH2
CH2—C—O (c) square planar geometry and CoCl 3 ⋅ 4NH3 respectively is
diamagnetic (a) 1 AgCl, 3 AgCl, 2 AgCl [NEET 2017]
C (d) tetrahedral geometry and
(b) 3 AgCl, 1 AgCl, 2 AgCl
paramagnetic
(c) 3 AgCl, 2 AgCl, 1 AgCl
Ans. (b)
EDTA is a hexadentate ligand with four ‘O’ (d) 2 AgCl, 3 AgCl, 1 AgCl
and two ‘N’ donor atoms. Key Concept The complexes having Ans. (c)
sp3-hybridisation are tetrahedral while
having dsp2 -hybridisation are square According to Werner’s theory,
02 The type of isomerism shown by
planar. The magnetic behaviour of CoCl 3 ⋅6NH3 → [Co(NH3) 6 ] 3 + 3Cl −
the complex [COCl 2 (en) 2] is complexes can be paramagnetic and
[NEET 2018] diamagnetic based on the presence and CoCl 3 ⋅ 5NH3 → [Co(NH3) 5 Cl]2 + 2Cl −
(a) ionisation isomerism absence of unpaired electrons, CoCl 3 ⋅4NH3 → [Co(NH3) 4 Cl2 ] + Cl −
(b) coordination isomerism respectively. When AgNO3 in excess is treated with
(c) geometrical isomerism Electronic configuration of Ni (Z =28) is these complexes then following
(d) linkage isomerism [Ar] 18 3d 8 4s 2 . Due to presence of CO reactions takes place :
Ans. (c) (neutral ligand), oxidation state of Ni in [Co(NH3) 6 ] 3+ 3Cl − + AgNO3 → 3AgCl
[Ni(CO) 4 ] is 0. (Excess)
Isomers in which the atoms or ligands 3d + [Co(NH3) 6 ] 3+
occupy different positions around 2+ −
central metal/ion are called geometrical
Ni-atom [Co(NH3) 5 Cl] 2Cl + AgNO3 →
4s 4p (Excess)
isomers. Complexes having coordination
number of central atom/ion 6 with 2AgCl + [Co(NH3) 5 Cl]2 +
formula M(AA)2 B 2 exhibit geometrical + −
[Co(NH3) 4 Cl2 ] Cl + AgNO3 → AgCl
isomerism [where, AA is a bidentate Since, CO is a strong field ligand, it pair (excess)
ligand]. In [CoCl2 (en)2 ], coordination up the unpaired electrons of Ni. + [Co(NH3) 4 Cl2 ] +
05 The correct increasing order of 08 Number of possible isomers for the (c) Geometrical isomerism
trans-effect of the following species complex [Co(en) 2 Cl 2]Cl will be (d) Linkage isomerism
is [NEET 2016, Phase II] (en = ethylenediamine) Ans. (b)
(a)NH3 > CN > Br > C 6H−5
− −
[CBSE AIPMT 2015] The complexes [Co(NH3) 6 ][Cr(CN) 6 ] and
(b)CN− > C 6H−5 > Br − > NH3 (a) 2 (b) 1 (c) 3 (d) 4 [Cr(NH3) 6 ][Co(CN) 6 ] are the examples of
(c)Br − > CN− > NH3 > C 6H−5 Ans. (c)
coordination isomerisms. This
isomerism occurs only in those
(d)CN− > Br − > C 6H−5 > NH3 [Co(en)2 Cl2 ]Cl complexes in which both cation and
Ans. (b) Possible isomers are anion are complex. It occurs due to
Trans effect is the effect of a Cl Cl exchange of ligands between cation and
coordinated group upon the rate of Cl anion.
substitution at the position trans to itself
in a square or octahedral complex.As the en Co en Co en 12 The complex, [Pt(Py)(NH3 )BrCl] will
rate of substitution of the trans ligand
increases, the intensity of trans effect en have how many geometrical
cis Cl isomers? [CBSE AIPMT 2011]
also increases. Thus, correct order is, Optically active trans
Optically inactive
CN− > C6H–5 > Br – > NH3 Stereoisomers =2 Stereoisomers =1 (a) 4 (b) 0 (c) 2 (d) 3
Ans. (d)
Hence, total number of stereoisomers
06 Jahn-Teller effect is not observed The complex is square planar and is of
= 2 + 1 = 3.
in high spin complexes of the type [M(abcd)]. It has three
[NEET 2016, Phase II] geometrical isomers.
09 The sum of coordination number
(a) d 7 (b) d 8 (c) d 4 (d) d 9 Py NH3 Py Br
and oxidation number of the metal
Ans. (b) M in the complex [M(en) 2 (C 2O 4 )]Cl Pt Pt
Key Idea Jahn-Teller distortion is (where, en is ethylenediamine) is
observed in those octahedral complexes [CBSE AIPMT 2015] Cl Br ; Cl NH3 ;
in which d-electrons are filled
(a) 9 (b) 6 (c) 7 (d) 8
unsymmetrically.
Ans. (b) Py NH3
Given complex compound is Pt
eg eg
[M(en)2 (C2O4 )]Cl
Let oxidation number of M is x. Br Cl
t2g t2g
d4 d7 ∴ x −2−2= − 1
or x=+3 13 The existence of two different
eg eg
Now, as coordination number is defined coloured complexes with the
as the total number of binding sites composition of [Co(NH3 ) 4 Cl 2] + is
t2g t22g attached to the metal. Hence, in the due to [CBSE AIPMT 2010]
d8 d9
given complex coordination number is 6. (a) linkage isomerism
Except d 8 , all are unsymmetrically filled, (b) geometrical isomerism
thus d 8 complex will not show 10 The name of complex ion, (c) coordination isomerism
Jahn-Teller distortion. [Fe(CN) 6] 3− is [CBSE AIPMT 2015] (d) ionisation isomerism
(a) hexacyanoiron (III) ion
07 Cobalt (III) chloride forms several Ans. (b)
(b) hexacyanitoferrate (III) ion
octahedral complexes with (c) tricyanoferrate (III) ion Key Idea Complexes of [MA4 B2 ] type
ammonia. Which of the following exhibit geometrical isomerism.
(d) hexacyanidoferrate (III)ion
will not give test for chloride ions The complex [Co(NH3) 4 Cl2 ] + is a [MA4 B2 ]
Ans. (d) type complex and thus, fulfills the
with silver nitrate at 25°C?
Key Concept When complex ion is an conditions that are necessary to exhibit
[CBSE AIPMT 2015]
anion, the name of the metal ends with geometrical isomerism. Hence, it has two
(a) CoCl3 ⋅ 3NH3 (b) CoCl3 ⋅4NH3 suffix -ate along with its oxidation geometrical isomers of different colours
(c) CoCl3 ⋅5NH3 (d) CoCl3 ⋅ 6NH3 number in the complex ion. as :
Ans. (a) [Fe(CN) 6 ] 3 − = Hexacyanoferrate (III) ion The structure of the geometrical
[Co (NH3) 6 ]Cl 3 → [Co(NH3) 6 ] 3+ + 3Cl − isomers is as
11 The complex [Co(NH3) 6][Cr(CN) 6] Cl
[Co (NH3) 3 Cl 3] → [Co(NH3) 3 Cl 3] H3N Cl
[Co(NH3) 4 Cl2 ] Cl → [Co(NH3) 4 Cl2 ] + and [Cr(NH3 ) 6][Co(CN) 6] are the
+ Cl − examples of which type of Co
[Co(NH3) 5 Cl] Cl2 → [Co(NH3) 5 Cl] 2+
isomerism? [CBSE AIPMT 2011]
+ 2Cl − (a) Ionisation isomerism H3N NH3
NH3
So, [Co (NH3) 3 Cl 3] does not ionise so (b) Coordination isomerism Cis-form
does not give test for chloride ions.
Co-ordination Compounds 147
Cl Ans. (b) 17 Which one of the following is

H3N NH3 Enantiomorphs or Enantiomers A pair expected to exhibit optical
of molecules related to each other as an isomerism?
Co object and its mirror images are known
as enantiomorphs or enantiomers.
(en = ethylenediamine)
H3N These are not superimposable on its
[CBSE AIPMT 2005]
NH3
Cl mirror image. (a) Cis-[Pt(NH3)2 Cl2]
Trans-form The example is [Co(en)2 Cl2 ] + (b) Trans-[Co(en)2 Cl2] +
For linkage isomerism, presence of Dichlorobis (ethylene diamine) cobalt (III) (c) Trans-[Pt(NH3)2 Cl2]
ambidentate ligand is necessary. Mirror (d) Cis-[Co(en)2 Cl2] +
For coordination isomerism, both the en Ans. (d)
en
cation and anion of the complex must be Cl
Cl Cis- [Co(en)2 Cl2 ] + is able to show the
complex ions.
Co Co phenomenon of optical isomerism
For ionisation isomerism, an anion because it can form a superimposable
different to the ligands must be present Cl Cl mirror image.
outside the coordination sphere. All en en
Cl +
these conditions are not satisfied by this Mirror image
complex. Hence, it does not exhibit Enantiomorphs en Co en
other given isomerisms.
16 [Co(NH3 ) 4 (NO 2 ) 2]Cl exhibits Cl
14 Which of the following does not
[CBSE AIPMT 2006] It gives super imposable structure.
show optical isomerism?
(en = ethylenediamine) (a) linkage isomerism, geometrical but trans-form is optically inactive
[CBSE AIPMT 2009]
isomerism and optical isomerism Cl
(b) linkage isomerism, ionisation
(a) [Co(en)2 Cl2] +
isomerism and optical isomerism Transform en Co en
(b) [Co(NH3) 3Cl3] 0
(c) linkage isomerism, ionisation
(c) [Co(en)Cl2 (NH3)2] + Cl
isomerism and geometrical
(d) [Co(en) 3] 3+ isomerism
Optically active form
Ans. (b) (d) ionisation isomerism, geometrical
Optical isomerism is exhibited only by isomerism and optical isomerism 18 Which of the following coordination
those complexes in which plane of Ans. (c) compounds would exhibit optical
symmetry are absent. Octahedral isomerism? [CBSE AIPMT 2004]
complexes of the types [M(aa) 3], The compound [Co(NH3) 4 (NO2 )2 ]Cl
[M(aa) x2 , y2 ] and [M(aa)2 x2 ] have absence exhibits linkage, ionisation and (a) Pentaamminenitrocobalt (III)
of plane of symmetry, thus exhibit geometrical isomerism. Hence, iodide
optical isomerism. Here, aa represents (i) its linkage isomers are (b) Diamminedichloroplatinum (II)
bidentate ligand, x or y represents [Co(NH3) 4 (NO2 )2 ] Cl and (c) Trans-dicyanobis
monodentate ligand and M represents [Co(NH3) 4 (ONO)2 ]Cl (ethylenediamine) chromium (III)
central metal ion. (ii) its ionisation isomers are chloride
Hence, [Co(NH3) 3 Cl 3] 0 due to presence [Co(NH3) 4 (NO2 )Cl]NO2 and (d) Tris-(ethylenediamine) cobalt (III)
of symmetry elements does not exhibit [Co(NH3) 4 (NO2 )2 ]Cl bromide
optical isomerism. (iii) its geometrical isomers are
Ans. (d)
or +
NH3 Tris-(ethylenediamine) cobalt (III)
Octahedral complexes of [M(AA)2 B2 ] bromide [Co(en) 3]Br3 exhibits optical
type, e.g. [Co(en)2 Cl2 ] + , [M(AA) B2C2 ] H3N NO2
isomerism :
type, e.g. [Co(en)Cl2
Co 3+
(NH3)2 ] and [M(AA) 3] type, e.g. [Co(en) 3] 3+ en
show optical isomensim, whereas H3N NO2
complexes of [ MA3 B3 ] type, e.g.
[Co(NH3)Cl2 ] 0 do not show optical NH3 en Co
isomerism. Cis-isomer
+
NO2 en
15 Which of the following will give a
H3N NH3 d-form Mirror
pair of enantiomers? 3+
en
(en =NH2CH2CH2NH2 ) and Co
[CBSE AIPMT 2007]
(a) [Cr(NH3) 6] [Co(CN) 6] H3N NH3 Co en
(b) [Co(en)2 Cl2]Cl NO2
(c) [Pt(NH3) 4] [PtCl6] Trans-isomer en
(d) [Co(NH3) 4 Cl2]NO2 l-form
19 According to IUPAC nomenclature 23 Which one of the following 25 The total number of possible
sodium nitroprusside is named as complexes will have four isomers? isomers for the complex compound
[CBSE AIPMT 2003] [CBSE AIPMT 2000] [CuII (NH3 ) 4] [PtII Cl 4] are
(a) sodium pentacyanonitrosyl ferrate (a) [Co(en) 3]Cl3 [CBSE AIPMT 1998]
(II) (b) [Co(en)2 Cl2]Cl (a) 5 (b) 6
(b) sodium pentacyanonitrosyl ferrate (c) [Co(PPh3)2 (NH3)Cl2]Cl (c) 3 (d) 4
(III) Ans. (d)
(d) [Co(PPh3) 3Cl]Cl2
(c) sodium nitroferricyanide
Ans. (b) Given complex gives four isomers that
(d) sodium nitroferrocyanide are as follow.
Complex [Co(en)2 Cl2 ]Cl will have four
Ans. (b) (i) [Cu(NH3) 4 ] [PtCl 4 ]
different isomers.
IUPAC name of sodium nitroprusside (i) Geometrical isomers (ii) [Cu(NH3) 3 Cl] [Pt(NH3)Cl 3]
Na2 [Fe (CN) 5 NO] is sodium pentacyanoni + + (iii) [Pt(NH3) 3 Cl] [Cu(NH3)Cl 3]
Cl Cl
trosyl ferrate (III) because in it NO is Cl (iv) [Pt(NH3) 4 ] [CuCl 4 ]
neutral ligand and the oxidation number
en Co en en Co
of Fe is +3. Which is calculated as 26 IUPAC name of
Na2 [Fe (CN) 5 NO] Cl en [Pt(NH3 ) 3 (Br) (NO 2 ) Cl] Cl is
2 × (+1) + x + 5 × (– 1) + 1 × 0 =0 Trans Cis [CBSE AIPMT 1998]
[where x = oxidation state of Fe] (ii) Optical isomers (a) triamminebromochloronitroplatinum
2+ x − 5=0 + + (IV) chloride
Cl Cl
x −3=0 ⇒ x = +3 Cl Cl (b) triamminebromonitrochloroplatinum
(IV) chloride
en Co Co en
20 Which one of the following (c) triamminechlorobromonitroplatinum
octahedral complexes will not show en en (IV) chloride
geometrical isomerism? (A and B (d) triamminenitrochlorobromoplatinum
Optically active cis-[Co(en)2Cl2]Cl (IV) chloride
are monodentate ligands)
[CBSE AIPMT 2003] Ans. (a)
24 A coordination complex compound
(a) [MA4B2] (b) [MA5B] The IUPAC name of
of cobalt has the molecular formula [Pt(NH3) 3 (Br)(NO2 )Cl]Cl is
(c) [MA2B4] (d) [MA3B3]
containing five ammonia triamminebromochloronitroplatinum (IV)
Ans. (b)
molecules, one nitro group and two chloride.
[MA 5 B] due to absence of symmetry of chlorine atoms for one cobalt (Oxidation number ofPt = + 4, and ligands
B cannot exist in the form of
cis-trans-isomer.
atom. One mole of this compound are arranged in alphabetical order)
produces three mole ions in an
21 The hypothetical complex chloro aqueous solution. On reacting this 27 The number of geometrical
diaquatriammine cobalt (III) solution with excess of isomers of the complex
chloride can be represented as AgNO 3 s olution, we get two moles [Co(NO 2 ) 3 (NH3 ) 3] is
of AgCl precipitate. The ionic [CBSE AIPMT 1997]
[CBSE AIPMT 2002]
(a) [CoCl(NH3) 3 (H2O)2]Cl2 formula for this complex would be (a) 4 (b) 0
[CBSE AIPMT 1998] (c) 2 (d) 3
(b) [Co(NH3) 3 (H2O)Cl3]
(c) [Co(NH2 ) 3 (H2O)2 Cl] (a) [Co(NH3) 5 (NO2 )]Cl2 Ans. (c)
(d) [Co(NH3) 3 (H2O) 3]Cl3 (b) [Co(NH3) 5 Cl] [Cl(NO2 )] Geometrical isomers of the complex
(c) [Co(NH3) 4 (NO2 )Cl] [(NH3)Cl] [Co(NO2 ) 3 (NH3) 3] are two. These are
Ans. (a)
(d) [Co(NH3) 5] [(NO2 )2 Cl2] NO2 NO2
Chlorodiaquatriammine cobalt (III)
chloride is [CoCl(NH3) 3 (H2O)2] Cl2 . Ans. H3N NO2 H3N NO2
(a)
Co Co
22 Which of the following will give The complex gives three ions in aqueous
solution. H3 N NH 3 H N NO2
maximum number of isomers? 3
[CBSE AIPMT 2001] ∴The complex should be NO2 NH3
(a) [Co(NH3) 4 Cl2] [CO(NH3) 5 NO2 ]Cl2 . Maridonal isomers Facial isomers
(b) [Ni(en)(NH3) 4] 2+ It will give three ions on dissociation as
(c) [Ni(C2O4 )(en)2] 2– follows : 28 The formula of dichlorobis (urea)
(d) [Cr(SCN)2 (NH3) 4] + [Co(NH3) 5 NO2 ] Cl2 → [Co(NH3) 5 NO2 ]2 + copper (II) is [CBSE AIPMT 1997]
1 mol
Ans. (d) (a) [Cu{O == C(NH2 )2 Cl}] Cl
+ 2Cl − (Counter ion) (b) [CuCl2 {O == C(NH2 )2 }2]
+
[Cr(SCN)2 (NH3) 4 ] Oxidation number of 2 mol
Cr is 6 shows linkage, geometrical and (c) [Cu{O == C(NH2 )2 }] Cl2
2Cl + 2AgNO3 → 2AgCl + 2NO–3
–
(d) [CuCl2 {O == C(NH2 )2 H2 }]
optical isomerism. Silver ppt
Ans. (b) Ans. (d) 32 Urea reacts with water to form A

The formula of dichlorobis (urea) copper A. [Fe(CN)6 ]3− Oxidation number of which will decompose to form B. B
(II) is [CuCl2 {O == C(NH2 )2 }2 ]. Fe = x + 6 (−1) = − 3 when passed through Cu 2+ (aq),
x − 6 = −3 ⇒ x = + 3 deep blue colour solutionC is formed.
29 The number of geometrical Electronic configuration of
isomers for [Pt(NH3 ) 2]Cl 2 is What is the formula of C from the
Fe → [Ar] 3d 6 4s 2
[CBSE AIPMT 1995] Electronic configuration of
following? [NEET (Sep.) 2020]
(a) 3 (b) 4 Fe3+ → [Ar] 3d 5 4s 0 (a) [Cu(NH3) 4] 2+
(c) 1 (d) 2 (b) Cu(OH)2
3d 5 4s 0
Ans. (d) (c) CuCO 3 ⋅Cu(OH)2
Geometrical isomers for [Pt(NH3)2 Cl2 ] is (d) CuSO 4
CN− is a strong field ligand so, pairing
Cl NH3 Ans. (a)
of electrons occurs.
Complete reaction is
Pt 3d 5 4s 0
[Fe(CN) ] =
3– O O
6
Cl NH3
(Cis) Number of unpaired electrons = 1 H2N—C—NH2 + H2O H2N—C—ONH4
Urea A
pale yellow µ s = n(n + 1) = 1 (1 + 2) = 3 Ammonium
Cl carbonate
NH3 = 1.73 BM
Pt B. [Fe(H2O)6 ]3+ Oxidation state of Fe

CO2(g) + NH3(g)
is +3.
H3N Cl 2+ B
(Trans) Water is weak field ligand, so pairing [Cu(NH3)4] (aq)
Cu2+(aq)
dark yellow of electron do not take place. C
Deep blue solution
eg
30 An example of a double salt is
(∆O<P) 33 Which of the following is the
[CBSE AIPMT 1989]
d5 correct order of increasing field
(a) bleaching powder t2 g
(b) K 4 [Fe(CN) 6] strength of ligands to form
Number of unpaired electrons = 5.
(c) hypo coordination compounds?
µ s = n(n + 2 ) = 5 × (5 + 2 ) [NEET (Sep.) 2020]
(d) potash alum
Ans. (d) = 5 × 7 = 35 = 5.92 BM (a) SCN− < F − < CN− < C2O24−
Double salts are additon or molecular C. [Fe(CN)6 ] 4− Oxidation state of Fe
(b) F − < SCN− < C2O24− < CN−
compounds which are formed by two is +2. (c) CN− < C2O24− < SCN− < F −
apparently saturated compounds but Electronic configuration of (d) SCN− < F − < C2O24− < CN−
they lose their identity when dissolved in Fe2 + = [Ar] 3d 6 4s 0 Ans. (d)
water. The most common example of CN− is a strong field ligand, so pairing
double salt is potash alum Increasing field strength of ligands to
of electrons take place.
K2SO4 ⋅ Al2 (SO4 ) 3 ⋅24H2O. form coordination compounds, we have
eg to follow the spectrochemical series.
I− < Br − < SCN− < Cl − < S2 − < F − < OH− <
TOPIC 2 (DO>P)
C2O24 − < H2O < NCS − < EDTA4 − < NH3 < en <
d6
Bonding in Coordination t2g CN− < CO
Compounds Number of unpaired electrons = 0 So, the order given in option (d) :
µ s = 0 (0 + 1) = 0 BM SCN− < F − < C2O24 − < CN − is correct.
31 Match List-I with List-II. [NEET 2021] D. [Fe(H2O)6 ]4− Oxidation state of Fe
List-I List-II is +2 (3d 6 ). 34 The Crystal Field Stabilisation
Water is weak field ligand, so pairing Energy (CFSE) for [CoCl 6] 4− is
A. [Fe(CN) 6] 3 − 1. 5.92 BM
of electron do not take place. 18000 cm −1 . The CFSE for
B. [Fe(H2O) 6] 3 + 2. 0 BM
eg [CoCl 4] 2− will be
C. [Fe(CN) 6] 4 − 3. 4.90 BM [NEET (Odisha) 2019]
(∆O<P)
D. [Fe(H2O) 6] 2 +
4. 1.73 BM d6 (a) 6000 cm −1 (b) 16000 cm −1
t2g
(c) 18000 cm −1 (d) 8000 cm −1
Choose the correct answer from
Number of unpaired electrons = 4 Ans. (d)
the options given below µ s = 4(4 + 2) = 4 × 6
A B C D A B C D [CoCl 6 ] 4− is an octahedral while
= 24 = 4.90 BM [CoCl 4 ]2 − is a tetrahedral complex.
(a) 4 2 1 3 (b) 2 4 3 1 Hence, correct match is
∆ octahedral = 18000 cm −1
(c) 1 3 4 2 (d) 4 1 2 3 A → 4, → B → 1, C → 2, D → 3.
We know that, 37 What is the correct electronic The examples of dinuclear, trinuclear
4 complexes are Co2 (CO) 18 , Fe3 (CO) 12
∆ tetrahedral = ∆ octahedral configuration of the central atom in
9 respectively.
K 4 [Fe(CN) 6] based on crystal field
4
= × 18000 cm −1 = 8000 cm −1 theory? [NEET (National) 2019]
9 39 An example of a sigma bonded
(a) t26g e g0 (b) e 3 t23 (c) e 4 t22 (d) t24g e2g organometallic compound is
35 Aluminium chloride in acidified Ans. [NEET 2017]
aqueous solution forms a complex ‘ (a) (a) ruthenocene
A’, in which hybridisation state of Al In K4 [Fe(CN) 6 ], (b) Grignard’s reagent
is ‘B’. What are ‘A’ and ‘B’, Fe2 + = [Ar] 3d 6 4s 0 . (c) ferrocene
CN− is a strong field ligand and as it (d) cobaltocene
respectively? [NEET (Odisha) 2019] approaches the metal ion, the electrons
(a) [Al(H2O) 6] 3+ , sp 3d2 Ans. (b)
must pair up.
(b) [Al(H2O) 4] 3+ , sp 3 The splitting of thed-orbitals in two sets The organometallic compounds having
orbitals in an octahedral complex, sigma bond between carbon and metal
(c) [Al(H2O) 4] 3+ ,dsp2 are sigma bonded organometallic. An
K4 [Fe(CN) 6 ] may be represented as :
(d) [Al(H2O) 6] 3+ ,d2 sp 3 example of a sigma bonded
Ans. (a) organometallic compound is Grignard’s
d-orbitals dx2–y2 dz2 reagent.
Aluminium chloride in acidified aqueous free ion
solution forms an octahedral complex. eg R Mg  X
12
4 43
Aqueous solution is mostly water and σ− bond
when the compound is dissolved in

dxy dxz dyz Whereas, ruthenocene, ferrocene and
acidified aqueous solution, the water
Average energy of the t2g cobaltocene are not sigma bonded
d-orbitals in spherical
fills its vacancies and an octahedral crystal field Splitting of d-orbitals organometallic compound.
in octahedral
complex, ‘A’ which is [Al(H2O) 6 ] 3+ is crystal field
formed. Hence, the electronic configuration of
Al(13) = s ,22s 2 , 2p6 , 3s 2 , 3p1 the central atom inK4 [Fe(CN) 6 ] is t26g e g0 . Ru Fe Co
Al 3+ =1s 2 , 2s 2 , 2p6 .
2s 2p 38 Iron carbonyl, Fe(CO) 5 is
Ruthenocene Ferrocene Cobaltocene
Al3+= [NEET 2018]
(a) trinuclear (b) mononuclear
2s 2p 40 Correct increasing order for the
(c) tetranuclear (d) dinuclear
[Al(H2O)6]3+ = wavelengths of absorption in the
Ans. (b)
3p
visible region for the complexes of
3s 3d Key Concept Compounds of transition
CO 3+ is [NEET 2017]
metal with carbonyls (carbon monoxide)
are known as metal carbonyls. These are (a) [Co(en) 3] 3+ , [Co(NH3) 6] 3+ ,
H2O H2O H2O H2O H2O H2O classified into mononuclear, dinuclear, [Co(H2O) 6] 3+
trinuclear and so on based on the number (b) [Co(H2O) 6] 3+ , [Co(en) 3] 3+ ,
sp3d2
of central metal atoms/ions present in a [Co(NH3) 6] 3+
Thus, the hybridisation state of Al in complex. (c) [Co(H2O) 6] 3+ , [Co(NH3) 6] 3+ ,
[Al(H2O) 6 ] 3+ is sp3d2 (B). Complexes following EAN rule have EAN [Co(en) 3] 3+
of central metal/ion equal to nearest (d) [Co(NH3) 6] 3+ , [Co(en) 3] 3+ ,
36 Which of the following species is inert gas configuration and hence, are [Co(H2O) 6] 3+
not stable? stable.
[NEET (Nationa) 2019] Ans. (a)
(a) [GeCl6] 2− (b) [Sn(OH) 6] 2− Effective atomic number (EAN) of the
metal in a complex is given by Key concept Wavelength (λ) of
(c) [SiCl6] 2− (d) [SiF6] 2− absorption is inversely proportional to
EAN = Atomic number (Z) CFSE (∆O value) of ligands attached with
Ans. (c)
− Oxidation number (O.N) the central metal ion
[SiCl 6 ]2 − is not stable and does not exist + 2 (Coordination number) 1
because i.e. λ∝
= 26 − 0 + 2 (5 ) = 36 ∆O
(i) six large chloride ions cannot be
accomdated around Si4 + due to Thus, Fe(CO) 5 is a stable complex/ion. According to spectrochemical series.
Since, there is only one central metal
limitation of its size. I − < Br − < S2 − < SCN − < Cl − < F − < OH−
atom present in iron carbonyl,Fe(CO) 5 ,
(ii) interaction between lone pair of < C2O24− < O2 − < H2O < NSS − < NH3 < en <
chloride ion andSi4 + is not very thus it is mononuclear. The structure of
Fe(CO) 5 is shown below: NO2− < CN −
strong.
CO Weak field Increasing order of ∆ Strong
On the other hand, due to presence of o field
OC ligands
ligands
d-orbital in Si, Ge and Sn they form Fe CO
species like [SiF6 ]2 − , [GeCl 6 ]2 − and OC
[Sn(OH) 6 ]2 − . Hence, option (c) is correct. The CFSE of ligands attached with Co3+
CO
ion is in the order
en > NH3 > H2O (From spectrochemical (b) [Co(CN) 6] 3– has four unpaired 45 Among the following complexes,
series) electrons and will be in a low-spin the one which shows zero crystal
1 configuration.
Q Wavelength of absorbed light (λ) ∝ field stabilisation energy (CFSE) is
∆o (c) [Co(CN) 6] 3– has four unpaired [CBSE AIPMT 2014]
∴ For ligand the order of wavelength of electrons and will be in a high-spin 3+
configuration. (a) [Mn(H2O) 6] (b) [Fe(H2O) 6] 3+
absorption in the visible region will be :
en < NH3 < H2O (d) [Co(CN) 6] 3– has no unpaired (c) [Co(H2O) 6] 2+ (d) [Co(H2O) 6] 3+
or, [Co(en) 3] 3+ < [Co(NH3) 6 ] 3+ < electrons and will be in a high-spin Ans. (b)
[Co(H2O) 6 ] 3+ configuration. The CFSE for octahedral complex is
Ans. (a) given by
41 Pick out the correct statement
[Co(CN) 6 ] 3− CFSE = [−0.4 t2 g e − + 0.6 e g e − ]
with respect to [Mn(CN) 6] 3−
[NEET 2017]
Co3+ = 1s 2 2s 2 2p6 3s 2 3p6 3d 6 For Mn3+ , [3d 4 ] → t23g e g1
3 2 CN− is a strong field ligand and as it ∴ CFSE = [(−0.4 × 3) + (0.6 × 1)] = −0.6
(a) It is sp d hybridised and
approaches the metal ion, the electrons
octahedral For Fe3+ , [3d 5 ] → t23g e2g
must pair up.
(b) It is sp 3d2 hybridised and
The splitting of thed-orbitals into two CFSE = [− (0.4 × 3) + (0.6 × 2)] = 0
tetrahedral
(c) It is d2 sp 3 hybridised and
sets of orbitals in an octahedral For Co2 + , [3d 7 ] → t25g e2g
[Co(CN) 6 ] 3− may be represented as
octahedral CFSE = [(−0.4 × 5) + (2 × 0.6)] = −0.8
(d) It is dsp2 hybridised and square eg For Co3+ , [3d 6 ] → t24g e2g
3d
planar dx2–y2 dz2 ∇orbital CFSE = [(−0.4 × 4) + (2 × 0.6)] = −0.4
o
Ans. (c)
t2g
[Mn(CN) 6 ] 3− is d2 sp3-hybridised and 46 A magnetic moment of 1.73 BM will
octahedral complex. In [Mn(CN) 6 ] 3− , Mn dxy dxz dxz orbital
be shown by one among the
is in +3 oxidation state
Here, for d 6 ions, three electrons first following
Mn3+ = 3d 4 4s 0 [CBSE AIPMT 2013]
enter orbitals with parallel spin put the
3d 4s 4p remaining may pair up int2 g orbital giving (a) [Cu(NH3) 4] 2+ (b) [Ni(CN) 4] 2−
Orbitals of
3+ = rise to low spin complex (strong ligand) (c) TiCl4 (d) [CoCl6] 4−
Mn ion
3d 4s 4p field. Ans. (a)
[Mn (CN)6]3– = ∴ [Co(CN) 6 ] 3− has no unpaired electron
and will be in a low spin configuration. Magnetic moment,µ is related with
d2sp3-hybridised number of unpaired electrons as
(Octahedral)
44 The hybridisation involved in µ = n (n + 2) BM
complex [Ni(CN) 4] 2− is (Atomic (1.73)2 = n (n + 2)
42 Which of the following has longest On solving n= 1
C—O bond length? (Free C—O bond number of Ni = 28)
[CBSE AIPMT 2015] Thus, the complex/compound having
length in CO is 1.128 Å.) one unpaired electron exhibit a magnetic
[NEET 2016, Phase I] (a) dsp 2 (b) sp 3
moment of 1.73 BM.
(c) d 2 sp 2 (d) d2sp 3
(a) [Co(CO) 4] − (b) [Fe(CO) 4] 2 − (a) In [Cu(NH3) 4 ]2 +
(c) [Mn(CO) 6] + (d) Ni(CO) 4 Ans. (a)
Cu2 + = [Ar] 3d 9
Ans. (b) [Ni(CN) 4 ]2 −
Let oxidation state of Ni in [Ni(CN) 4 ]2 − is
As negative charge on metal carbonyl
x.
complex increases, back π-bonding
increases and hence bond length of C—O ∴ x −4= −2 (Although in the presence of strong field
bond increases while bond length of or x =2 ligand NH3, the unpaired electron
gets excited to higher energy level but it
metal-carbon bond decreases. Now, Ni2 + = [Ar] 3d 8 4s 0
still remains unpaired).
Hence, [Fe(CO) 4 ]2 − has longest C—O
(b) In [Ni(CN) 4 ]2 −
bond length among the given complexes.
The correct order of bond length of the
3d 3s 4p Ni2 + = [Ar] 3d 8
given complexes is Q CN– is a strong field ligand. Hence, all
[Mn(CO) 6 ] + < [Ni(CO) 4 ] < [Co(CO) 4 ] − unpaired electrons are paired up.
< [Fe(CO) 4 ]2 − But CN− being strong field ligand pair up
3d 3s 4p the unpaired electrons and hence in this
43 Which of these statements about complex, number of unpaired electrons
[Co(CN) 6] 3– is true? = 0.
[CBSE AIPMT 2015] CN– CN– CN– CN– (c) In [TiCl 4 ]
(a) [Co(CN) 6] 3– has no unpaired Ti 4+ = [Ar]
∴ Hybridisation of [Ni(CN) 4 ]2 − is dsp2 no unpaired electron.
electrons and will be in a low-spin
configuration.
(d) In [CoCl 6 ] 4− (c) In [Cr(NH3) 6 ] 3+ , Ans. (a)

Co2 + = [Ar] 3d 7 Cr 3+ = [Ar] 3d 3 Key Idea For the absorption of visible
light, presence of unpairedd-electrons is
[Cr(NH3)6]3+ =
the necessity.
3d 4s 4p
(a) In [Ni(CN) 4 ]2 − , Ni is present asNi2 + .
It contains three unpaired electrons.
Thus, [Cu(NH3) 4 ]2 + is the complex that Ni2 + = [Ar] 3d 8 4 s 0
{
exhibits a magnetic moment 1.73 BM. Three d2sp3 hybridisation ∴ [Ni(CN)4]2– =
unpaired
electrons 3d 4s 4p
47 Which one of the following is an Because of the involvement of (n − 1)d,
outer orbital complex and exhibits i.e.3d-orbital in hybridisation, it is an 14444244443
paramagnetic behaviour? inner orbital complex. Its nature is dsp2 hybridisation
[CBSE AIPMT 2012] paramagnetic because of the presence (Pairing occurs because CN− is a strong
(a) [Ni(NH3) 6] 2+
(b) [Zn(NH3) 6] 2+ of three unpaired electrons. field ligand).
(d) In [Co(NH3) 6 ] 3+
(c) [Cr(NH3) 6] 3+ (d) [Co(NH3) 6] 3+ Since, in [Ni(CN) 4 ]2 − , no unpaired
Co3+ = [Ar] 3d 6 electron is present in d-orbitals so it
Ans. (a)
3d does not absorb visible light.
Outer orbital complex utilises
(n − 1) d-orbitals for bonding and exhibit (b) In [Cr(NH3) 6 ] 3+ , Cr is present as Cr 3+ .
paramagnetic behaviour, only if there Cr 3+ = [Ar] 3d 34 s 0 (Three unpaired
present unpaired electrons. [Co(NH3)6]3+ =
4p electrons)
3d 4s
(a) In [Ni(NH3) 6 ]2 + : (c) In [Fe(H2O) 6 ] 3+ , Fe is present asFe2 + .
Ni2 + = [Ar] 3d 8 4 s 0 [Ar]3d 6 4 s 0 (Four unpaired electrons)
3d
[Ni(NH 3)6 ]2+ =

3d
4s { d2sp3
⇒ Inner orbital complex
Because of the involvement of (n − 1) d
orbital in hybridisation, it is an inner
orbital complex. As all the electrons are
paired, it is a diamagnetic complex.
(d) In [Ni (H2O) 6 ]2 + , Ni is present asNi2 + .
Ni2 + = [Ar] 3d 8 4 s 0 (Two paired electrons)
The complex given in option (b), (c), (d)
have unpaired electrons, thus absorb
visible light.
NOTE In presence ofNH3 and H2O pairing
does not occur as they are strong field
48 Of the following complex ions ligand.
Two
which is diamagnetic in nature?
Unpaired
electrons
[CBSE AIPMT 2011]
50 Crystal field stabilisation energy for
4s 4p 4d (a) [Ni(CN) 4] 2– (b) [CuCl4] 2−
(c) [CoF6] 3– (d) [NiCl4] 2–
high spin d 4 octahedral complex is
[CBSE AIPMT 2010]
Ans. (a)
sp 3d 2 hybridisation
(a) −1.8 ∆ o (b) − 1.6 ∆ o + P
Electronic configuration of Ni2 + in (c) −1.2 ∆ o (d) −0.6 ∆ o
[Ni(CN) 4 ]2 – is
So, this is an outer orbital complex as it Ans. (d)
involve 4d- orbitals for bonding, but Ni2+ = 3d8 4s0
Key Idea In case of high spin complex,
having paramagnetic character.
∆ o is small. than the pairing energy. That
(b) In [Zn(NH3) 6 ]2 + : means, the energy required to pair up the
Zn2 + = [Ar] 3d 10 3d 4s 4p fourth electron with the electrons of
3d Ni2 + has dsp2 hybridisation, as CN− is a lower energyd-orbitals would be higher
strong field ligand. than that required to place the electrons
in the higher d-orbital. Thus, pairing does
not occur.
[Zn(NH3)6]2+ =
×× ×× ×× ×× For high spind 4 octahedral complex,
3d eg
0.6∆
CN– CN– CN– CN–
0.4∆
2−
4s 4p 4d ∴ [Ni(CN) 4 ] is diamagnetic (because of Degenerate t2g
the absence of unpaired electrons). d-orbitals
∴Crystal field stabilisation energy

49 Which of the following complex
{
sp3d2 hybridisation = (− 3 × 0.4 + 1 × 0.6) ∆ o

ions is not expected to absorb
= ( − 1.2 + 0.6) ∆ o
Thus, it is also an outer orbital complex as visible light? [CBSE AIPMT 2010]
= − 0.6 ∆ o
it involve4d- orbitals for bonding but it is (a) [Ni (CN) 4] 2− (b) [Cr (NH3) 6] 3+
diamagnetic as all the electrons are (c) [Fe (H2O) 6] 2+ (d) [Ni (H2O) 6] 2+
paired.
51 Out of TiF62− , CoF63− , Cu 2Cl 2 and Ans. (c) Hence, complex [Co(ox)2 (OH)2 ] − has
As in all the given complex the central maximum number of unpaired electrons,
NiCl 2−
4 (At. no. Z of Ti = 22, Co = 27, thus show maximum paramagnetism.
metal atom is same and contains same
Cu = 29,Ni= 28), the colourless number of d electrons, thus CFSE is
species are [CBSE AIPMT 2009] decided by ligands. In case of strong 55 [Cr(H2O) 6]Cl 3 (at. no. of Cr = 24)
(a) TiF62 − and CoF63− field ligand, CFSE is maximum. CN− is a has a magnetic moment of 3.83
(b) Cu2Cl2 and NiCl2− strong field ligand, Hence, in [Co(CN) 6 ] 3−
4
magnitude of CFSE i.e. ∆ 0 is maximum. BM, the correct distribution of 3d
(c) TiF62 − and Cu2Cl2 electrons in the chromium of the
(d) CoF63− and NiCl24− complex is
54 Which of the following complexes [CBSE AIPMT 2006]
Ans. (c) 1
(a) 3 dxy 1
, 3 dyz , 3 dz1 2
exhibits the highest paramagnetic
In TiF62 − , Ti is present asTi4+ . behaviour? (b) 3 d 2 2 , 3 dz1 2 , 3 dxz
1
(x – y )
Ti = [Ar] 3d 4s
4+ 0 0
where, gly = glycine, en = (c) 3 dxy , 3 d 1
, 3 dyz
Hence,TiF62 − is colourless due to the (x 2 − y 2 )
absence of unpaired electrons. ethylenediamine and bpy =
1 1 1
bipyridyl moities) (d) 3 d xy , 3 d yz , 3 d zx
In Cu2 Cl2 , Cu is present as Cu+ .
(At. no. of Ti = 22,C = 23,Fe = 26, Ans. (d)
Cu+ = [Ar]
3d 10
4s Co = 27) [CBSE AIPMT 2008] Magnetic moment (µ ) = n(n + 2) BM
(a) [V(gly)2 (OH)2 (NH3)2] + or 3 .83 = n (n + 2)
(b) [Fe(en)(py)(NH3)2] 2+ or 3 .83 × 3 .83 = n2 + 2n
Due to absence of unpaired electrons,
Cu2 Cl2 is colourless. (c) [Co(ox)2 (OH)2] − 14 .6689 = n2 + 2n
(d) [Ti(NH3) 6] 3+ n ~− 3
52 Which of the following complex Ans. (c) Hence, number of unpaired electrons in
ions is expected to absorb visible d-subshell of chromium (Cr= 24) = 3.
The electronic configuration of
light? (At. no. of So, the configuration of chromium ion is
V(23) = [Ar] 4s 2 , 3d 3
Zn = 30, Sc = 21, Ti = 22, Cr = 24) Cr 3+ = 1s 2 , 2 s 2 2p6 , 3s 2 3p6 3d 3
Let in [V(gly)2 (OH)2 (NH3)2 ] + oxidation
[CBSE AIPMT 2009] state of V is x. In [Cr(H2O) 6 ]Cl2 , oxidation state of Cr is +3.
x + (−1) × 2 + (−1)2 + (0 × 2) = + 1 Hence, in3d 3 the distribution of
(a) [Sc(H2O) 3 (NH3) 3] 3+
electrons
(b) [Ti(en)2 (NH3)2] 4+ x=+5 1 1 1
3d xy ,3d yz ,3d zx ,3d 02 2 ,3d 02
(c) [Cr(NH3) 6] 3+ V5 + = [Ar] 4s 0 , 3d 0 x −y z
(d) [Zn(NH3) 6] 2+ (no unpaired electrons) 56 Which one of the following is an

Ans. (c) The electronic configuration of inner orbital complex as well as
In [Cr(NH3) 6 ] 3+ , Cr is present as Cr 3+ . Fe(26) = [Ar] 4s 2 , 3d 6 diamagnetic in behaviour?
Cr 3+ = [Ar] 3d 3, 4s 0 Let the oxidation state of Fe in
[Fe(en)(ppy)(NH3)2 ]2 + is x. (At. no. of Zn = 30, Cr = 24, Co =
3d 4s
[x + (0) + (0) + (0) × 2] = + 2 27, Ni = 28) [CBSE AIPMT 2005]
x = +2 (a) [Zn(NH3) 6] 2+ (b) [Cr(NH3) 6] 3+

[Cr(NH3) 6 ] 3+ = [Ar] 3d 3 Fe2 + = [Ar],3d 6 (c) [Co(NH3) 6] 3+ (d) [Ni (NH3) 6] 2+
3d 4s 4p (Q 4 unpaired electron) Ans.
but, bpy, en and NH3 all are strong field (c) In [Co(NH3 )6 ] 3+ , oxidation state of
NH3 NH3 NH3 NH3 NH3 NH3 ligands, so pairing occurs and thus,Fe2 + Co = +3 and its coordination number is
contains no unpaired electron. six.
{
27 Co = 1s , 2s 2p , 3s 3p 3d , 4s
Electron donated by NH3 ligand 2 2 6 2 6 7 2
The electronic configuration of
hybridisation d 2sp3 3+
Co = 1s , 2s 2p , 3s 3p 3d
2 2 6 2 6 6
Co(27) = [Ar] 4s 2 , 3d 7
Since, this complex has three unpaired Let the oxidation state of Co in
d s p
electrons, excitation of electrons is [Co(ox)2 (OH)2 ] − is x
possible and thus, it is expected that this
complex will absorb visible light. x + (−2) × 2 + (−1) × 2 = − 1
x=+5 d 2sp 3
53 In which of the following Co5 + = [Ar], 3d 4 [4 unpaired electrons] [Co(NH3) 6 ] 3+ is an inner orbital complex
coordination entities the as well as diamagnetic in behaviour (due
ox and OH are weak field ligands, thus
to absence of unpaired electrons).
magnitude of ∆ o (CFSE in pairing of electron units does not occur.
octahedral field) will be maximum? The electronic configuration of [Zn(NH3) 6 ] 2 + → sp3d2
(At. no. of Co = 27) Ti(22) = [Ar] 4s 2 , 3d2 hybridisation (outer orbital complex and
[CBSE AIPMT 2008] Oxidation state of Ti in [Ti(NH3) 6 ] 3+ is 3. diamagnetic in nature).
Ti3+ = [Ar] 3d 1 [Cr(NH3) 6 ] 3+ → d2 sp3
(a) [Co(H2O) 6] 3+ (b) [Co(NH3) 6] 3+
hybridisation (inner orbital complex and
(c) [Co(CN) 6] 3– (d) [Co(C2O 4 ) 3] 3− (one unpaired electron)
paramagnetic in nature).
57 Among [Ni(CO) 4], [Ni(CN) 4] 2– , of weak field, ligand there will be no 62 Atomic number of Cr and Fe are
pairing of electrons in 3d. So, it will respectively 24 and 26, which of
[NiCl 4] 2– species, the hybridisation form high spin complex due to
states of the Ni atom are, the following is paramagnetic with
presence of five unpaired electrons.
respectively (At. no. of Ni = 28) the spin of electron?
[CBSE AIPMT 2002]
59 CN − is strong field ligand. This is
[CBSE AIPMT 2004]
3
(a) sp , dsp dsp 2, 2 3
(b) sp , dsp , sp 2 3 (a) [Cr(CO) 6] (b) [Fe(CO) 5]
due to the fact that (c) [Fe(CN) 6] 4– (d) [Cr(NH3) 6] 3+
(c) sp 3, sp 3, dsp2 (d) dsp2 , sp 3, sp 3 [CBSE AIPMT 2004]
Ans. (b) Ans. (d)
(a) it carries negative charge
In Ni(CO) 4 , nickel is sp3 hybridised (b) it is a pseudohalide Atoms, ions or molecules having
because in it oxidation state of Ni is zero. unpaired electrons are paramagnetic. In
(c) it can accept electrons from metal [Cr(NH3) 6 ] 3+ , Cr is present as Cr (III).
So, configuration of species
Cr 3+ = 1s 2 , 2 s 2 2p6 , 3s 2 3p6 3d 3
28 Ni = 1s , 2 s 2p , 3 s 3p 3d , 4s
2 2 6 2 6 8 2
(d) it forms high spin complexes with
d s p In excited state
metal species
d s p
Ans. (b)
CN− is a strong field ligand because it is
sp 3 an example of pseudohalide.
(CO is a strong field ligand, hence pairing Pseudohalide ions are stronger d 2sp3 hybridisation
of electrons will occur) coordinating ligands and they have the Number of unpaired electrons = 3, so it is
In [Ni(CN) 4 ]2 – , nickel is present asNi2 + , ability to form σ and π-bonds. paramagnetic while rest of the species
so its configuration are diamagnetic.
= 1s 2 ,2s 2 2p6 , 3s 2 3p6 3d 8 60 Among the following which is not
d s p the π-bonded organometallic 63 Which of the following
compound? [CBSE AIPMT 2003] organometallic compounds is σ and
(a) K[PtCl3 (η2 − C2H4 )] π-bonded? [CBSE AIPMT 2001]
dsp 2
(b) Fe(η5 − C 5H5 )2 (a) [Fe(η5 —C 5H5 )2]
−
CN is strong field ligand, hence it makes (b) K[PtCl3 (η2 —C2H4 )]
Ni2 + electrons to be paired up. (c) Cr (η6 –C 6H6 )2
(c) [Co(CO) 5 NH3] 2+
In [NiCl 4 ] 2 − , nickel is present as Ni2 + , so (d) (CH3) 4 Sn (d) Fe(CH3) 3
its configuration Ans. (d)
= 1s 2 , 2s 2 2p6 , 3 s 2 3p6 , 3d 8 Ans. (c)
d s p In (CH3) 4 Sn (organometallic compounds [Co(CO) 5 NH3]2 + . In this complex,
of tin) single bonds are present in form Co-atom attached with NH3 through
of sigma bond. pi-bonded σ-bonding and with CO through dative
organometallic compound includes π-bond.
sp 3 alkenes, alkynes and some other carbon
Cl − is a weak field ligand, hence inNi2 + containing compounds having
64 Coordination number of Ni in
electrons are not paired. pi-electrons in their molecular orbitals.
[Ni(C 2O 4 ) 3] 4– is
CH3 [CBSE AIPMT 2001]
58 Considering H2O as a weak field 
Sn (a) 3 (b) 6
ligand, the number of unpaired H3C CH3 (c) 4 (d) 2

electrons in [Mn(H2O) 6] 2+ will be CH3 Ans. (b)
(At. no. of Mn = 25) Coordination number of nickel in
[CBSE AIPMT 2004] [Ni(C2O4 ) 3] 4– is 6 because C2O24– is a
(a) 3 (b) 5 (c) 2 (d) 4 61 The number of unpaired electrons bidentate ligand.
Ans. (b) in the complex ion [CoF6] 3– is
[CBSE AIPMT 2003]
In [Mn(H2O) 6 ] 2 + , Mn is present asMn2 + or 65 Which statement is incorrect?
Mn (II), so its electronic configuration (At. no. of Co = 27) [CBSE AIPMT 2001]
= 1s , 2 s 2 p , 3s 3p , 3d
2 2 6 2 6 5 (a) 3 (b) 2 (a) Ni(CO) 4 -tetrahedral, paramagnetic
(c) 4 (d) 0 (b) [Ni(CN) 4] 2− -square planar,
d
Ans. (c) diamagnetic
p In complex ion[CoF6 ]3 – , Co is present in (c) Ni(CO) 4 -tetrahedral, diamagnetic
s d
+3 oxidation state (d) [Ni(Cl) 4] 2– tetrahedral,
27 Co = 1s , 2 s 2p , 3s 3p 3d , 4s
2 2 6 2 6 7 2
paramagnetic
3+
Co = 1s , 2 s 2p , 3 s 3p 3d
2 2 6 2 6 6
Ans. (a)
sp 3d 2
Therefore, the number of unpaired
In [Mn(H2O) 6] 2+ the coordination electrons in3d subshell of [CoF6 ] 3− is 4.
In Ni(CO) 4 , Ni has zero oxidation state. It
number of Mn is six, and in presence is sp3 hybridised.
Ni(CO) 4 → 68 Shape of Fe(CO) 5 is atoms. These compounds contain both

3d σ and π-bonded complexes.
[CBSE AIPMT 2000]
σ-bond between metal and carbon atom
(a) octahedral is formed when a vacant hybrid orbital of
4s 4p (b) square planar the metal atom overlaps with an orbital
(c) trigonal bipyramidal on C-atom of carbon monooxide
(d) square pyramidal containing a low pair of electron.
sp3 hybridisation Formation of π-bond is occurs when a
Ans. (c)
filled orbital of the metal atom overlaps
Hence, it has no unpaired electron so, it In Fe(CO) 5 , the Fe-atom is indsp3 with a vacant antibonding π- orbital of
shows the property of diamagnetism and hybridised state, therefore the shape of C-atom of Co.
has tetrahedral structure. molecule is trigonal bipyramidal. The
NOTE The valence shell electronic hybridisation is as follows : 71 Which of the following ligands is
26 Fe = 1s , 2s 2p , 3s 3p 3d , 4s 4p
configuration of ground state Ni atom is 2 2 6 2 6 6 2 0
3d 8 4s 2 . The two electrons of 4s are

expected to be bidentate?
In presence of strong field ligand (CO),, [CBSE AIPMT 1994]
pushed into3d orbitals and get paired up the electrons of4s are pushed in3d
because of the presentce of strong (a) CH3NH2
orbital and get paired up.
ligand (CO). (b) CH3C ≡≡N
In Fe(CO) 5 , the Fe-atom is
(c) Br
66 Which of the following will exhibit (d) C2O2–
4
maximum ionic conductivity? 3d Ans. (d)
[CBSE AIPMT 2001]
C2O24– is a bidentate ligand because it has
(a) K 4 [Fe(CN) 6] (b) [Co(NH3) 6]Cl3 two donor atoms (sites) and can
(c) [Cu(NH3) 4]Cl2 (d) [Ni(CO) 4] 4s 4p coordinate to the central ion at two
Ans. (a) dsp3 hybridised positions.
Ionic conductivity depends upon the – M + + + C O
CO CO
number of ions produced in aqueous
solution. K4 [Fe(CN) 6 ] produces
CO Fe C
maximum number of ions, i.e. 5. – M O
4K+ + [Fe(CN) 6 ] 4 − CO
144424443 CO 72 Which one of the following
Total 5 ions
[Co(NH3) 6 ]Cl 3 produces 3, [Cu(NH3) 4 ] Cl2
statements is not correct?
produces 3 and [Ni(Co) 4 ] gives zero ions. 69 The coordination number and [CBSE AIPMT 1994]
oxidation state of Cr in (a) Mercury (II) iodide dissolves in
67 In the separation of Cu 2+ and Cd 2+ K 3 [Cr(C 2O 4 ) 3] are respectively excess of potassium iodide
[CBSE AIPMT 1995] solution
of IInd group in qualitative analysis
(a) 3 and +3 (b) 3 and 0 (b) Tin (IV) chloride is made by
of cations, tetrammine copper (II)
(c) 6 and +3 (d) 4 and +2 dissolving tin solution in
sulphate and tetrammine cadmium concentrated hydrochloric acid
(II) sulphate react with KCN to form Ans. (c)
(c) Zinc dissolves in sodium hydroxide
the corresponding cyano Coordination number of Cr is 6 (oxalate is solution
complexes, which one of the bidentate ligand) and oxidation state of
(d) Carbon monoxide reduces iron (III)
Cr in K3 [Cr(C2O4 ) 3] is calculated below.
following pairs of the complexes oxide to iron
3 (1) + x + 3(−2) = 0
and their relative stability enables Ans. (b)
3 + x + (−6) = 0
the separation of Cu 2+ and Cd 2+ ? SnCl 4 is obtained by passing chlorine
[CBSE AIPMT 2000] x =6−3
over tin.
(a) K 3 [Cu(CN) 4] : less stable and x = +3
So Sn (IV) chloride is made by dissolving
K2 [Cd(CN) 4] : more stable tin solution in concentrated solution
70 In metal carbonyl having general statement is incorrect and answer is (b).
(b) K 3 [Cu(CN) 4] : more stable and
formula M (CO) x where, M = metal,
K2 [Cd(CN) 4] : less stable
x = 4 and the metal is bonded to 73 The complex ion [Co(NH3 ) 6] 3+ is
(c) K2 [Cu(CN) 4] : less stable and
K2 [Cd(CN) 4] : more stable
[CBSE AIPMT 1995] formed by sp 3d 2 hybridisation.
(a) carbon and oxygen Hence, the ion should possess
(d) K2 [Cu(CN) 4] : more stable and
(b) C ≡≡O [CBSE AIPMT 1990]
K2 [Cd(CN) 4] : less stable (c) oxygen (a) octahedral geometry
Ans. (b) (d) carbon (b) tetrahedral geometry
K3 [Cu(CN) 4 ] is more stable while in Ans. (d) (c) square planar geometry
K2 [Cd(CN) 4 ] is less stable.
In metal carbonyl M(CO) 4 , metal is (d) tetragonal geometry
Here, Cu in + 1 oxidation state. bonded to the ligand CO through carbon
Ans. (a) 75 Which of the following does not CH2

Since the hybridisation of central metal have a metal-carbon bond? Cl
tin [Co(NH3) 6 ] 3+ complex ion is sp3d2 and (a) Al(OC2H5 ) 3 [CBSE AIPMT 2004]
(a) Pt CH2
coordination number of Co3+ is 6. So, its Cl Cl
geometry is octahedral. (b) C2H5MgBr
(c) K[Pt(C2H4 )Cl3]
(d) Ni(CO) 4 Cl Cl
TOPIC 3 (b) Pt
Ans. (a) Cl Cl
Importance of Al(OC2H5 ) 3 does not have metal-carbon
Co-ordination Compounds bond, (i.e. it is not an example of
H3N Cl
organometallic compound) (c) Pt
Structure H3N Cl
74 Which of the following complexes
H H
is used to be as an anticancer
H3N Cl
agent? [CBSE AIPMT 2014] O—C—C—H (d) Pt
(a) Mer- [Co(NH3) 3Cl3] H H Cl NH3
(b) Cis- [PtCl2 (NH3)2] H H
H—C—C—O—Al Ans. (c)
(c) Cis- K2 [PtCl2Br2] H H
Cis-platin is the isomer of [Pt(NH3)2 Cl2 ]
(d) Na2CoCl4 H H
O—C—C—H which is used as an anticancer drug for
Ans. (b) treating several types of malignant
Cis-platin is known as anticancer agent. H H tumours.
The formula of cis-platin is cis-
Cl Cl
[PtCl2 (NH3)2 ]. Here, the word cis refers 76 Which of the following is Pt
to cis geometrical isomer of considered to be an anticancer
[PtCl2 (NH3)2 ]. It is used as an antitumour Cl Cl
species? [CBSE AIPMT 2004]
agent.
20
Purification and
Characterisation
of Organic Compounds
TOPIC 1 H H-bonding 03 The best method for the separation
O O
Methods of Purification of naphthalene and benzoic acid
N from their mixture is
O
01 The most suitable method of (a) chromatography [CBSE AIPMT 2005]
separation of 1 : 1 mixture of ortho (b) crystallisation
and para-nitrophenols is Intramolecular H-bonding
(c) distillation
[NEET 2017, CBSE AIPMT 99, 94] in o-nitrophenol (d) sublimation
(a) sublimation H-bonding Ans. (d)
O
(b) chromatography ---HO— —N The best method for the separation of
O---HO
(c) crystallisation naphthalene and benzoic acid from their
(d) steam distillation O mixture is sublimation because it is
 —N
O--- applicable for those organic compounds
Ans. (d)
which pass directly from solid to vapour
Steam distillation is used to purify the Intermolecular H-bonding in p-nitrophenol state on heating and vice versa on cooling.
substances which In these compounds naphthalene is
(i) are volatile in steam but are volatile and benzoic acid is non-volatile
immiscible with water. 02 Which of the statements is not due to the formation of dimer via hydrogen
(ii) possess sufficiently high vapour true? [CBSE AIPMT 2012] bonding (intermolecular).
pressure at the boiling point of water.
(a) On passing H2 S through acidified
(iii) contain non- volatile impurities.
K2Cr2O 7 solution, a milky colour 04 Camphor is often used in molecular
The process of steam distillation can also is observed mass determination because
be used to separate a mixture of two [CBSE AIPMT 2004]
(b) Na2Cr2O 7 is preferred over
organic compounds one of which is (a) it is readily available
K2Cr2O 7 in volumetric analysis
steam volatile while the other is not.
(c) K2Cr2O 7 solution in acidic (b) it has a very high cryoscopic constant
In ortho and para-nitrophenol,
medium is orange (c) it is volatile
ortho-nitrophenol has intramolecular
H-bonding. So, it has lower boiling point. (d) K2Cr2O 7 solution becomes yellow (d) it is solvent for organic substances
Intermolecular H-Bonding more strong on increasing the pH beyond 7 Ans. (c)
then intramolecular H-bonding. Whereas Ans. (b) Camphor is used in molecular mass
para-nitrophenol has intermolecular Being hygroscopic, sodium determination due to its volatile nature.
H-bonding. So, it has higher boiling point. dichromate,Na2 Cr2O7 cannot be used The method is called Rast’s camphor
Due to difference in boiling points ortho in volumetric analysis. method. Camphor acts as a solid solvent
and para-nitrophenol can be separated which is volatile, hence can be removed
All other given statements are true.
from each other by distillation. easily.
05 In steam distillation of toluene, the 08 Prussian blue is formed when Ans. (b)
pressure of toluene in vapour is [CBSE AIPMT 1989] Lassaigne’s test is given by only those
[CBSE AIPMT 2001] (a) ferrous sulphate reacts with FeCl3 compounds which contain both carbon
(b) ferric sulphate reacts with and nitrogen. When compounds
(a) equal to the pressure of barometer
Na4 [Fe(CN) 6] containing C and N heated with sodium,
(b) less than the pressure of then it form NaCN which is easily
barometer (c) ferrous ammonium sulphate
detected byFeCl 3.
(c) equal to vapour pressure of reacts with FeCl3 Or
toluene in simple distillation (d) ammonium sulphate reacts with
Some compounds live hydrazine
(d) more than vapour pressure of FeCl3 (NH2 ⋅ NH2 ) although contain nitrogen but
toluene in simple distillation Ans. (b) they do not respond Lassaigne’s test
Ans. (b) When the sodium fusion extract is added because they do not have any carbon
with FeCl 3 and then the resulting solution and hence, NaCN is not formed.
In steam distillation of toluene, the
pressure of toluene in vapour is less than is acidified with dilute hydrochloric acid,
pressure of barometer, because it is the appearance of Prussian blue 11 In sodium fusion test of organic
carried out when a solid or liquid is colouration confirms the presence of compounds, the nitrogen of the
insoluble in water and is volatile with nitrogen in the organic compound. organic compound is converted
steam but the impurities are Na + C + N → NaCN into [CBSE AIPMT 1991]
non-volatile. FeSO4 + 2NaCN → Fe(CN) 2 + Na2SO4 (a) sodamide (b) sodium cyanide
Fe(CN)2 + 4NaCN → Na4 [Fe(CN) 6 ] (c) sodium nitrite (d) sodium nitrate
06 Which of the following techniques
3Na4 [Fe(CN) 6 ] + 4FeCl 3 → Ans. (b)
is most suitable for purification of
Fe4 [Fe(CN) 6 ] 3 + 12NaCl When the nitrogen containing compound
cyclohexanone from a mixture Prussian blue is heated with sodium, then nitrogen and
containing benzoic acid, isoamyl carbon of organic compound converted
alcohol, cyclohexane and into sodium cyanide.
cyclohexanone? [CBSE AIPMT 1997] TOPIC 2 Na + C2
1 +3
N → NaCN
(a) Crystallisation (b) IR spectroscopy Qualitative Analysis From organic compound
(c) Sublimation (d) Evaporation
Ans. (b) 12 Lassaigne’s test is used to detect
09 The Lassaigne’s extract is boiled
IR spectroscopy is used for the with conc. HNO 3 while testing for [CBSE AIPMT 1990]
purification of cyclohexanone from a (a) nitrogen (b) sulphur
mixture of benzoic acid, isoamyl alcohol,
halogens. By doing so it
[CBSE AIPMT 2011] (c) chlorine (d) All of these
cyclohexane and cyclohexanone
because in IR spectroscopy each (a) helps in the precipitation of AgCl Ans. (d)
functional group appears at a certain (b) increases the solubility product of The detection of chlorine, sulphur and
peak. IR spectroscopy exploits the fact AgCl nitrogen in organic compounds is done
that molecules absorb specific (c) increases the concentration of by Lassaigne’s test.
frequencies that are characteristic of NO –3 ions
their structure. (d) decomposes Na2 S and NaCN, if
formed
07 A is a lighter phenol and B is an Ans. (d)
TOPIC 3
aromatic carboxylic acid. Separation Quantitative Analysis
Na2S and NaCN, if present in the extract,
of a mixture of A and B can be will be decomposed toH2S and HCN by
carried out easily by using a HNO3 . 13 In Duma’s method for estimation of
solution of [CBSE AIPMT 1992] NaCN + HNO3 → NaNO3 + HCN nitrogen, 0.25g of an organic
(a) sodium hydroxide Na2S + 2HNO3 → 2NaNO3 + H2S compound gave 40 mL of nitrogen
(b) sodium sulphate These will escape from the solution and
(c) calcium chloride
collected at 300 K temperature and
will not interfere with the test for
(d) sodium bicarbonate halogens.
725 mm pressure. If the aqueous
tension at 300 K is 25 mm, the
Ans. (d)
10 Lassaigne’s test for the detection percentage of nitrogen in the
Carboxylic acids are soluble in sodium
bicarbonate but phenol are not dissolve of nitrogen fails in compound is [CBSE AIPMT 2015]
in it, so they are separated because [CBSE AIPMT 1994] (a) 17.36 (b) 18.20 (c) 16.76 (d) 15.76
carboxylic acid react withNaHCO3 and (a) NH2CONHNH2 ⋅HCl Ans. (c)
form sodium carboxylate. (b) NH2NH2 ⋅HCl Mass of the substance taken = 0.25 g
R — COOH + NaHCO3 (c) NH2CONH2 Volume of nitrogen collected = 40 mL
→ R — COO−Na+ + H2 CO3 (d) C 6H5NHNH2 ⋅HCl Atmospheric pressure = 725 mm
Purification and Characterisation of Organic Compounds 159
Room temperature = 300 K 14 In Duma’s method of estimation of T1 = t + 273 = 300 K

Aqueous tension at 300 K = 25 mm nitrogen 0.35g of an organic V1 = 55 mL = volume of moist nitrogen in
Actual pressure of the gas nitrometer
compound gave 55 ml of nitrogen
= (725 − 25) mmHg = 700 mm (715 − 15) × 55 273
collected at 300K temperature and ∴ V2 = ×
To convert the volume at experimental 300 760
175 mm pressure. The percentage
conditions to volume at STP. = 46098
. mL
composition of nitrogen in the
Experimental value At STP % of nitrogen in given compound
compound would be (Aqueous V
p1 = 700 mm p2 = 760 mm =
28
× 2 × 100
tension at 300 K = 15mm]
V1 = 40 ml V2 = ? 22400 W
[CBSE AIPMT 2011]
T1 = 300 k T2 = 273 k =
28
×
.
46098
× 100
(a) 16.45 (b) 17.45
Substituting these values in the gase eq. 22400 0.35
(c) 14.45 (d) 15.45
p2V2 p1V1
= = 1645
. %
Ans. (a)
T2 T1
According to combined gas equation, 15 Kjeldahl’s method is used in the
760 × V2 700 × 40
we get, = p1V1 p2V2
estimation of [CBSE AIPMT 1990]
273 300 =
T1 T2
700 × 40 273 (a) nitrogen (b) halogens
V2 = × Where, p2 = pressure of N2 at STP
300 760 (c) sulphur (d) oxygen
= 33.53 mL = 760 mm Ans. (a)
To convert volume at STP into mass T2 = Temperature ofN2 at STP = 273 K Kjeldahl’s method is simpler and more
22400 ml of nitrogen at STP weigh = 28 g V2 = ? convenient than Duma’s method. This
∴ 33.53 ml of nitrogen at STP will Volume of N2 at STP (By gas equation) method is largely used for the estimation
28 × 33.53  ρ − ρ1  273 of nitrogen in food stuff, drugs,
weigh =   V1 × = V2 fertilisers and many other organic
22400 × 0.25  t + 273  760
compounds. However, this method
To calculate percentage of nitrogen Where, p1 = ρ − ρ1 cannot be used for organic compounds
28 × 33.53 ρ = 715 mm (pressure at whichN2 containing nitrogen in the ring such as
= × 100
22400 × 0.25 collected) pyridine, quinoline and organic
ρ1 = aqueous tension of water = 15 mm compounds containing nitro (—NO2 ) and
= 16.76 %
diazo (—N == N—) groups.
21
Some Basic Principles of
Organic Chemistry
TOPIC 1 iso-butyl group in an organic compound 04 The correct IUPAC name of the
is
Nomenclature CH3
compound [CBSE AIPMT 2011]

01 The IUPAC name of the compound CH3  C  CH2 
[NEET 2017]  is
H
(a) 3-keto-2-methylhex-4-enal
(‘yl’ suffix is used to represent one —H
(b) 5-formylhex-2-en-3-one (a) 3-ethyl-4-ethenylheptane
less than the parent hydrocarbon.)
(c) 5-methyl-4-oxohex-2-en-5-al (b) 3-ethyl-4-propylhex-5-ene
(d) 3-keto-2-methylhex-5-enal (c) 3-(1-ethyl propyl) hex-1-ene
03 Which nomenclature is not
Ans. (a) according to IUPAC system? (d) 4-ethyl-3-propylhex-1-ene
O [CBSE AIPMT 2012] Ans. (d)
O
H C (a) Br CH2 CH == CH2 1
1 2
3 4 1-bromo prop-2-ene 2
5 CH3 3
6
4

— CHO group gets higher priority over > (b) CH 3CH 2 CCH 2CH  CH 3 5
C == O and 6
 
C == C group in numbering of 4-ethyl-3-propylhex-1-ene
Br CH3
principal carbon chain. 4-bromo-2, 4-dimethylhexane Priority order→ = > −
IUPAC name =
3-keto-2-methylhex-4-enal. (c) CH3CHCHCH2CH3 05 The IUPAC name of the compound
  having the formula
02 The structure of isobutyl group in CH3 CH≡≡C—CH==CH2 is
an organic compound is [NEET 2013] 2-methyl-3-phenylpentane
[CBSE AIPMT 2009]
CH3 (a) 3-butene-1-yne
(a) CH CH2  (d) CH3C—CH2CH2CH2COOH (b) 1-butyn-3-ene
CH3  (c) but-1-yne-3-ene
O
(b) CH3 CH CH2  CH3 5-oxohexanoic acid (d) 1-butene-3-yne
 Ans. (a) Ans. (d)
(c) CH3 CH2 CH2 CH2  In IUPAC system of nomenclature, In IUPAC nomenclature, double bond is
CH3 given more preference than triple bond.
preference is given to multiple bond than
 halogen substituent, so the correct 4 3 2 1
(d) CH3 C  CH ≡≡ C  CH == CH2
name of
 1-butene-3-yne
3 2 1
CH3 Br  CH2  CH==CH2 is
Ans. (a) 3-bromoprop-1-ene 06 The state of hybridisation of
Priority is given to double bond than C 2 , C 3 , C 5 and C 6 of the
‘Iso’ mean’s one Me group is present in
side chain. Hence, the structure of halogen. hydrocarbon,
Some Basic Principles of Organic Chemistry 161
CH3 respectively. Due to higher s-character (a) 2, 3-diethylheptane

 electron attracting tendency, i.e. (b) 5-ethyl-6-methyloctane
electronegativity increases.
CH3 C  CH == CH (c) 4-ethyl-3-methyloctane
7 6 5 4
 (d) 3-methyl-4-ethyloctane
CH3 09 The IUPAC name of is
CH3 Ans. (c)
 Cl The IUPAC name of the given compound is
CH C ≡≡ CH CH3
3 2 1 5 7
O H3C 1 2 3
4 6
is in the following sequence [CBSE AIPMT 2006] 8 CH3
[CBSE AIPMT 2009]
(a) 3, 4-dimethylpentanoyl chloride
(a) sp, sp 3, sp2 and sp 3 CH3
(b) 1-chloro-1-oxo-2,
(b) sp 3, sp2 , sp2 and sp 4-ethyl-3-methyl octane
3-dimethylpentane
(c) sp, sp2 , sp2 and sp 3
(c) 2-ethyl-3-methylbutanoyl chloride 12 IUPAC name of the following is
(d) sp, sp2 , sp 3 and sp2
(d) 2, 3-dimethyl pentanoyl chloride [CBSE AIPMT 2002]
Ans. (a)
Ans. (d) CH2 ==CH — CH2 — CH2 — C ≡≡ CH
If number of σ bonds = 2; hybridisation is
IUPAC name of the given compound is (a) 1, 5-hexenyne (b) 1-hexene-5-yne
sp.
CH3 (c) 1-hexyne-5-ene (d) 1, 5-hexynene
If number of σ bonds = 3; hybridisation is 4 
sp2 , CH2 2CH
Cl
Ans. (b)
5 3 1
If number of σ bonds = 4; hybridisation is CH3 CH C The double bond gets more priority over
sp3.  triple bond. So, the IUPAC name of
CH3 H H CH3 CH3 O compound is
σ σ σ σ σ 2, 3-dimethyl pentanoyl chloride 1 2 3 4 5 6
σ σ σ σ
H3C—C—–C C—C—C CH CH2 == CH— CH2 — CH2 — C ≡≡ CH
σ5 3 σ
σ 4 2 1
10 Names of some compounds are hex-1-en-5-yne or 1-hexene-5-yne
CH3 H
given. Which one is not correct in
4s-bonds 3s-bonds 4s-bonds 2s-bonds
IUPAC system? [CBSE AIPMT 2005] 13 The incorrect IUPAC name is
(sp3) (sp2) (sp3) (sp) [CBSE AIPMT 2001]
(a) CH3 CH  CH  CH3
  (a) CH3  C CH  CH3
07 In the hydrocarbon OH CH3  |
O CH3
CH3 — CH==CH — CH2 — C ≡≡ CH 3-methyl-2-butanol
2-methyl-3-butanone
6 5 4 3 2 1 (b) CH3 C ≡≡C  CH(CH3)2
4-methyl-2-pentyne (b) CH3 CH  CH  CH3
the state of hybridisation of | |
(c) CH3 CH2 C  CH  CH3
carbons 1, 3 and 5 are in the || | CH3 CH2 —CH3
following sequence CH2 CH3 2, 3-dimethyl pentane
[CBSE AIPMT 2008] 2-ethyl-3-methylbut-1-ene
(c) CH3 —C ≡≡ CCH(CH3)2
(a) sp2 , sp, sp 3 (b) sp, sp 3, sp2 (d) CH3  CH2  CH2 CH3
4-methyl-2-pentyne
(c) sp, sp2 , sp 3 (d) sp 3, sp2 , sp 
 CH  CH  CH2CH3 (d) CH3 CH CH CH3
Ans. (b) | |

6 5 4 3 2 1 CH2CH3 Cl Br
CH3CH CHCH2C CH 3-methyl-4-ethyl heptane
2-bromo-3-chloro butane
sp3 sp2 sp2 sp3 sp sp Ans. (a)
Ans. (d)
1 2 3 4
Thus, the hybridisation of C1, C3 and C5 CH3 CH3  C  CH  CH3
are sp, sp3, sp2 respectively. 6 5 4 3 2 1 || |
CH 3CH 2CH 2CHCHCH 2 CH 3 O CH3

08 The correct order regarding the CH2—CH3 Correct name is 3-methyl-2-butanone.
electronegativity of hybrid orbitals Correct IUPAC name is 4-ethyl-3-methyl
of carbon is [CBSE AIPMT 2006] heptane. 14 IUPAC name of the compound
(a) sp > sp2 < sp 3 (b) sp > sp2 > sp 3 [CBSE AIPMT 1998]
(c) sp < sp2 > sp 3 (d) sp < sp2 < sp 3 11 Name of the compound given Cl CH2CH3
Ans. (b) below [CBSE AIPMT 2003] C ==C is
The correct order regarding the CH3 H 3C I
electronegativity of hybrid orbitals of H3C
carbon is sp > sp2 > sp3 because in sp, sp2 CH3
and sp3 hybrid orbitals, s-orbital (a) trans-3- iodo-4-chloro-3-pentene
character is 50%, 33.3% and 25% CH3 (b) cis-2-chloro-3-iodo-2-pentene
(c) trans-2-chloro-3-iodo-2-pentene 17 The IUPAC name of

(d) cis-3-iodo-4-chloro-3-pentene CH3 — CH — CH==C — CHO
TOPIC 2
Ans. (c)   Isomerism
Cl CH2 — CH3 OH CH3
C == C 20 Identify the compound that will
[CBSE AIPMT 1992]
H3C I react with Hinsberg’s reagent to
(a) 4-hydroxy-1-methyl pentanal
In this compound groups preferential give a solid which dissolves in
(b) 4-hydroxy-2-methyl pent-2-en-1-al
order is alkali. [NEET 2021]
(c) 2-hydroxy-4-methyl pent-3-en-5-al
 Cl >  CH3 and I >  CH2  CH3 (d) 2-hydroxy-3-methyl pent-2-en-5-al CH 2
Hence, more preferential order (a) CH 3 NO 2
Ans. (b)
containing groups are attached at CH 2 CH 3
opposite sides. So, it is E (trans)-isomer. 5 4 3 2 1 (b) CH 3 NH
Thus, its name is CH3CHCH CCHO
CH 2
trans-2-chloro-3-iodo-2-pentene. OH CH3 (c) CH 3 NH 2
CH 2 CH 2
15 The IUPAC name of 4-hydroxy -2-methyl pent -2-en-1-al
(d) CH 3 N CH 3
CH3 —CH— CH— CH2
 18 2-methyl-2-butene will be
 CH3
CH3 CH3 represented as [CBSE AIPMT 1992]
Ans. (c)
CH3
—CH2 — CH — CH3 is  Hinsberg test is used to test the amine
 (a) CH3 — CH —CH2CH3 compounds. Only 1° and 2° amines give
CH3 [CBSE AIPMT 1996] product after reacting with Hinsberg
(b) CH3 —C ==CH — CH3 reagent (benzene sulphonyl chloride). 3°
(a) 1,3-isopropyl-3-methyl propane  amines do not react.
(b) 2,3,6-trimethyl heptane CH3 The product formed can be
(c) 2,5,6-trimethyl heptane (c) CH3 — CH2 —C ==CH2 distinguished by dissolving in alkali. If it
(d) 2,6,3-trimethyl heptane  dissolves, then amine is 1° otherwise the
Ans. (b) CH3 reactant is secondary amine.
1 2 3 4 5 CH3  CH2NH2 + C6H5SO2 Cl →
CH3 — CH — CH — CH2 — CH2 (d) CH3 —CH — CH == CH2
Ethyl Amine Hinsberg reagent
  
CH3 CH3 6 7 CH3 C6H5SO2NHCH2 CH3 + HCl
— CH— CH3 Alkali KOH
 Ans. (b) C6H5SO2NHCH2 CH3 →
CH3 s
The structure of 2-methyl-2-butene is C6H5SO2 N CH2 CH3K⊕
Its IUPAC name is 2, 3, 6-trimethyl CH3 Soluble in alkali medium
heptane.
CH3—C CH—CH3 21 With respect to the conformers of
1 2 3 4
16 For the compound ethane, which of the following
H3C — CH — CH — CH2 — CH3 statements is true?
19 Which of the following possesses a
  sp-carbon in its structure? (a) Bond angle remains same but
CH3 CH2CH3 [CBSE AIPMT 1989] bond length changes [NEET 2017]
(a) CH2 == CCl — CH ==CH2 (b) Bond angle changes but bond
which of the following IUPAC length remains same
names is correct? (b) CCl2 == CCl2
(c) CH2 ==C ==CH2 (c) Both bond angle and bond length
[CBSE AIPMT 1994]
change
(a) 2-methyl-3-ethyl pentane (d) CH2 ==CH — CH ==CH2
(d) Both bond angles and bond length
(b) 3-ethyl-2-methyl pentane Ans. (c) remain same
(c) 2-ethyl-3-methyl pentane In structure CH2 == C == CH2 , the middle Ans. (d)
(d) 3-methyl-2-ethyl pentane carbon is attached with two π-bonds, so
it have sp hybridisation. Isomers which are possible by rotation
Ans. (b) about single bonds without cleavage of
5 4 3 2 1 CH2==C==CH2
CH3—CH2—CH—CH—CH3 any bond are called conformers. In
sp2 sp sp2 ethane, an infinite number of
C2H5 CH3 Also, called allenes. conformations are possible. There are
3-ethyl-2-methyl pentane two extreme forms, the staggered
conformation, which is the most stable
and the eclipsed conformation which is H H H H (a) 18 sigma bonds and 2 pi-bonds
least stable. Among the conformers of (b) 16 sigma bonds and 1 pi-bond
H H
ethane, bond angle and bond length (c) 9 sigma bonds and 2 pi-bonds
remains same while their energy, H H H H
(d) 9 sigma bonds and 1 pi-bond
stability and dihedral angle are different.
all carbons are sp2 -hybridised. Ans. (a)
22 The correct statement regarding a 24 Which among the given molecules The enolic form of ethyl acetoacetate
carbonyl compound with a has 16 single bonds i.e. 16 σ-bonds and 2
can exhibit tautomerism? double bonds i.e. 2 σ-bonds and 2
hydrogen atom on its alpha-carbon, [NEET 2016, Phase II] π-bonds.
is [NEET 2016, Phase I] O O
Hence, the given structure has 18
(a) a carbonyl compound with a O Ph σ-bonds and 2 π-bonds.
hydrogen atom on its Ph
alpha-carbon rapidly equilibrates I II III H
with its corresponding enol and (a) III Only (b) Both I and III H3C O
C
this process is known as C C
(c) Both I and II (d) Both II and III
aldehyde-ketone equilibration
(b) a carbonyl compound with a Ans. (a) O H OC2H5
hydrogen atom on its In tautomerism,α −hydrogen must be H
alpha-carbon rapidly equilibrates present in the molecule. Thus, molecule σ Hσ H
with its corresponding enol and II will not show tautomerism. As at σ σ
H C s σ C σ O
this process is known as bridge, double bond is highly unstable. σ C σ p-bond
C
carbonylation Thus, molecule I will also not show H σ p-bond σ Hσ Hσ
(c) a carbonyl compound with a tautomerism. O O C σ C
σ σH
hydrogen atom on its For III molecule, σ σ
alpha-carbon rapidly equilibrates H H
with its corresponding enol and O OH
this process is known as keto-enol 27 Which of the following compounds
H
tautomerism
III H
will undergoes racemisation when
(d) a carbonyl compound with a Enol form
Keto form solution of KOH hydrolysis?
hydrogen atom on its
[CBSE AIPMT 2014]
alpha-carbon never equilibrates So only, III molecule will show CH2  Cl
with its corresponding enol tautomerism. Thus, correct option is (a). (a)
Ans. (c)
In keto-enol tautomerism, a carbonyl 25 Two possible stereo-structures of (b) CH3  CH2  CH2  Cl
compound with a hydrogen atom on its CH3CHOH⋅ COOH, which are
alpha-carbon rapidly equilibrates with its optically active, are called CH3
corresponding enol. [CBSE AIPMT 2015]
O OH (c) CH3  CH  CH 2  Cl
(a) diastereomers (b) atropisomers
 
R —C—CH2 R ′ r R —C—CHR ′ (c) enantiomers (d) mesomers CH3
Ketone Enol Ans. (c)
(d) C
(containing α-hydrogen) H Cl
COOH COOH
C2H5
23 In which of the following H OH HO H
Ans. (c)
molecules, all atoms are coplanar?
CH3 CH3 Option (c) is most probable answer. Out
Both are enantiomers. of compound (c) or (d), the (d) results in
(a) (b) formation of racemic product due to
chirality. Compound (c) although not
26 The enolic form of ethyl
chiral but can form racemic product.
acetoacetate as below has After removal of Cl − gives a carbocation
[CBSE AIPMT 2015] which in turn undergo racemisation after
H rearrangement.
CH3 CN H3C C O
(c) C C (d) C C
CH3 CN 28 The order of stability of the
Ans. (a) OH OC2 H5 H2 following tautomeric compound is
The molecule in which all the carbon H3C O [NEET 2013]
C
atoms are sp2 -hybridised will be C C OH O
coplanar. Thus, in option (a) i.e.  
O OC2 H5 CH2 == C  CH2 C CH3 º
I
O O 30 Which of the following compounds C2H5 CH3

  will exhibit cis-trans (geometrical)  
CH3 C CH2 C CH3 º isomerism? [CBSE AIPMT 2009]
(c) Cl C  CH3 (d) H C  Cl
II  
OH (a) 2-butene (b) Butanol H C2H5
O
(c) 2-butyne (d) 2-butenol
  Ans. (c)
CH3 C == CH C CH3 º Ans. (a)
III H H CH3 — CHCl — CH2 — CH3, Priority order
(a) I > II > III (b) III > II > I CH3CH ==CHCH3 ⇒ C ==C is — Cl > — C2H5 > — CH3 > — H
(c) II > I> III (d) II > III > I 2 - butene H3C CH3 2
C2H5 No
Ans. (b) Cis -form 3 interchange
(a) H3CCCl
The enols of β-dicarbonyl compounds H3C H 1 2
are more stable because of conjugation C == C H C2H5
and intramolecular H–bonding. Thus, the H CH3 3
order of stability is H3CCCl S
Trans-form 1
OH O
  CH3CH2 CH2 CH2OH ⇒no geometrical H
H3C  C == CH  C  CH3 Butanol 2
C2H5
isomers
(Stabilised by conjugation 4 3
and H− bonding) CH3C ≡≡ CCH3 ⇒no geometrical isomers (b) HCCH3
Interchange
O III O CH3CH2 C(OH) ==CH2 ⇒no geometrical 3

CH3
  isomers. 1 Cl
1 2
> CH3  C  CH2  C  CH3 ClCC2H5 S
II 31 How many stereoisomers does this
OH 4
O molecule have? [CBSE AIPMT 2008] H
  2
> CH2 == C  CH2  C  CH3 CH3CH== CHCH2CHBrCH3 C2H5 No
(a) 4 (b) 6 1 3 interchange
I (c) ClCCH3
Less stable as (== ) bond (c) 8 (d) 2 2
is not in conjugation with carbonyl group 4
Ans. (a) H C2H5
1 3
H ClCCH3 R
29 Which of the following acid does
not exhibit optical isomerism? CH3C== CCH 2CCH
* 3
4H
[CBSE AIPMT 2012] 3
Br CH3
H H
(a) Maleic acid (b) α-amino acid 4 1 Interchange
(c) Lactic acid (d) Tartaric acid C* = asymmetric carbon (d) HCCl
Ans. (a) Number of optical isomers = 2n 2C 1
2H5 Cl
Only those compounds exhibit optical where, n = number of asymmetric
2 3
isomerism, which have chiral centre carbon atoms = 21 = 2 H5C2CCH3 S
and/or absence of symmetrical Number of geometrical isomers = 2n 4
elements. (Chiral carbon is the carbon in where, n = number of double bonds H
which all the four valencies are satisfied = 21 = 2
by four different groups.) Hence, total number of stereoisomers = 33 If there is no rotation of plane
R—CH—COOH
* Total optical isomers + Total geometrical polarised light by a compound in a
CHCOOH
(a)  (b)  isomers specific solvent, though to be
CHCOOH NH2 = 2 + 2= 4 chiral, it may mean that
Maleic acid a-amino acids
(one chiral centre, [CBSE AIPMT 2007]
(no chiral centre,
so, optically
so, optically active) 32 CH3  CHCl  CH2  CH3 has a (a) the compound is certainly a chiral
inactive
* chiral centre. Which one of the (b) the compound is certainly meso
CH(OH)COOH
* following represents its (c) there is no compound in the
(c) CH3CH(OH)COOH (d) ∗
CH(OH)COOH R-configuration? solvent
Lactic acid
(one chiral centre, Tartaric acid [CBSE AIPMT 2007] (d) the compound may be a racemic
so, optically (two chiral centre,
so, optically active) C2H5 C2H5 mixture
active)
  Ans. (b)
Thus, maleic acid does not exhibit
optical isomerism. (a) H3C  C  Cl (b) H  C CH3 The compounds in which asymmetric
NOTE If R == H, theα-amino acid is   carbon atom is present, are called
H Cl optically active, they rotate the plane
achiral.
polarised light but the compounds which
do not show optical activity inspite of the 36 Which one of the following pairs 38 Which of the following pair of
presence of chiral carbon atoms are
represents stereoisomerism? compounds are enantiomers ?
called meso-compounds. The absence
of optical activity in these compounds is
(a) Chain isomerism and rotational CH3 CH3
due to the presence of plane of
symmetry in the molecule. isomerism H OH H OH
(b) Structural isomerism and (a) and
HO H H OH
geometrical isomerism
CH3 CH3
34 Which of the following is not chiral? (c) Linkage isomerism and
[CBSE AIPMT 2006] geometrical isomerism CH3 CH3
(a) 2-butanol (d) Optical isomerism and geometrical HO H HO H
isomerism (b) and
(b) 2, 3-dibromo pentane H OH HO H
(c) 3-bromo pentane Ans. (d)
CH3 CH3
(d) 2-hydroxy propanoic acid Pair of optical isomerism and
geometrical isomerism are able to CH3 CH3
Ans. (c)
exhibit the phenomenon of H OH HO H
(a) 2-butanol (c) and
stereoisomerism because both type of HO H H OH
H Chiral ‘C’ isomers differ only in their orientation in
| space. CH3 CH3
CH3CCH2CH3
| CH3 CH3
OH 37 The molecular formula of diphenyl
(b) 2,3-dibromo pentane H OH HO H
methane (d) and
H H HO H HO H
  CH3 CH3
CH3CCCH2CH3
CH 2 is C13H12
  Ans. (c)
Br Br Enantiomers are mirror images of each
Chiral ‘C’ How many structural isomers are other but they are not superimposable
(c) 3-bromo pentane possible when one of the on each other.
H hydrogen is replaced by a chlorine CH3 CH3
 atom? [CBSE AIPMT 2004] H OH HO H
CH3CH2CCH2CH3 e.g. and
 (a) 6 (b) 4 HO H H OH
Br (c) 8 (d) 7 CH3 CH3
Not chiral ‘C’ Ans. (b)
(d) 2-hydroxy propanoic acid The molecular formula of diphenyl 39 Geometrical isomers differ in
H methane shows four isomers in form of [CBSE AIPMT 2002]
 mono chloro derivatives. (a) position of functional group
CH 3 CH 2 CH 2 CCOOH
 (b) position of atoms
OH CH2  (c) spatial arrangement of atoms
Chiral ‘C’ (d) length of carbon chain
Hence, 3-bromopentane is not a chiral (diphenyl methane) Ans. (c)
molecule due to absence of chiral C13H12 Geometrical isomers The isomers
C-atom. Monochloro derivatives having same molecular formula but
Cl differ in the position of atoms or groups
35 The chirality of the compound in space due to hindered rotation about a
[CBSE AIPMT 2005]
(i) CH2 double bond.
Br
s
••
C H is 40 CH2 —C —CH3 and CH2==C — CH3

H3C (ii) Cl— CH2  
Cl O • •
• O•
(a) R (b) S (c) Z (d) E •• s
Cl
Ans. (a)
are [CBSE AIPMT 2002]
1 Br
Br (iii) CH2 (a) resonating structures
4 4
(b) tautomers
C H H (c) geometrical isomers
3 3 C [R]
H3C Cl H3C (iv) CH2 (d) optical isomers
|
Cl Cl
Ans. (a) 43 The (R)- and (S)- enantiomers of an O

– optically active compound differ in R—CH2—N
CH2CCH3 CH2==C CH3 [CBSE AIPMT 2000]
Nitro form
O OH
|| |
O O – (a) their solubility in a chiral solvent R—CH N
Structure I Structure II (b) their reactivity with a chiral Azo form O
reagent
Structure I and structure II are the (c) their optical rotation of plane 47 Which of the following will not
resonating forms because the position polarised light show cis-trans-isomerism?
of atoms remains the same and only [CBSE AIPMT 1996]
redistribution of electrons take place.
(d) their melting points
Ans. (c) (a) CH3 — CH == CH — CH3
41 CH3 — CH2— CH CH3 obtained R and S forms of an optically active (b) CH3 — CH2 — CH ==CH — CH2 — CH3
| compound differ in their behaviour (c) CH3 — CH ==CH — CH2 — CH3
towards plane polarised light. The 
Cl
species which rotate the plane polarised CH3
by chlorination of n-butane, will be light towards right is called R-form (d) CH3 — CH — CH ==CH — CH2 — CH3
[CBSE AIPMT 2001] (rectus form) or d-form (dextro-form) and 
the species which rotate the plane
(a) meso form
polarised light towards left is known as Ans. (c) CH3
(b) racemic mixture
S-form (sinister-form) or l-form CH3 — C == CH — CH2 — CH3 will not
(c) d-form (laevo-form). 
(d) l-form CH3
Ans. (b) 44 But-2-ene exhibits show cis-trans isomerism because
Chlorination of n-butane takes place by cis-trans-isomerism due to double bonded carbon atom have two
free radical mechanism as follows: [CBSE AIPMT 2000] same groups (—CH3, methyl group).
• •
Step I Cl2 → Cl + Cl (a) rotation around C2 —C 3 double
48 Which of the following will exhibit
•
bond
Step II CH3CH2 CH2 CH3 + Cl →
chirality? [CBSE AIPMT 1996]
(b) rotation around C 3 —C 4 sigma bond
• (c) rotation around C 1 —C2 bond (a) 2-methyl hexane
CH3 C HCH2 CH3 + HCl (b) 3-methyl hexane
(d) restricted rotation around C ==C
• (c) Neopentane
Step III CH3 C HCH2 CH3 + Cl2 → bond
(d) Isopentane
Ans. (d)
Ans. (b)
CH3 CH3 Due to presence of>C == C <in
| | but-2-ene, it shows restricted rotation. 3-methyl hexane contains chiral carbon
H—C—Cl + Cl—C—H Hence, give two types of arrangements atom. Here it exhibits chirality.
| | around the space of >C == C< as cis and H
C2H 5 C2H 5 
trans-forms. CH3— CH2 — C *— CH2 CH2 CH3

Racemic mixture 45 Which of the following compounds CH3
is not chiral ? [CBSE AIPMT 1998]
42 A compound of molecular formula (a) DCH2CH2CH2Cl (b) CH3CH2CHDCl 49 The number of possible isomers of
C 7 H16 shows optical isomerism, (c) CH3CHDCH2Cl (d) CH3CHClCH2D the compound with molecular
compound will be Ans. (a) formula C 7 H8O is [CBSE AIPMT 1995]
[CBSE AIPMT 2001] (a) 3 (b) 5 (c) 7 (d) 9
Chiral carbon is that carbon whose all
(a) 2, 3-dimethyl pentane the four valencies are satisfied by four Ans. (b)
(b) 2, 2-dimethyl butane different groups. The possible isomers of C7H8O are
(c) 2-methyl hexane Due to absence of asymmetric (chiral) C-
OCH3 CH2OH OH
(d) None of the above atom
D — CH2 — CH2 — CH2 Cl CH3
Ans. (a)(b)
2,3-dimethylpentane molecule is not a chiral molecule.
Chiral carbon 46 Tautomerism will be exhibited by Anisole Benzyl alcohol o-cresol

CH3  CH  *CH  CH2  CH3
  [CBSE AIPMT 1997] OH OH
CH3 CH3 (a) (CH3) 3 CNO (b) (CH3)2 NH
shows the property of optical isomerism (c) R3CNO2 (d) RCH2NO2
due to presence of an asymmetric Ans. (d)
* CH3
C-atom. It is due to the presence ofα-hydrogen
m-cresol
atom in NO2 and NO compounds. CH3
p-cresol
50 The process of separation of a Ans. (c) TOPIC 3

racemic modification into d and The main conditions for geometrical
Bond Fission and
l-enantiomers is called isomerism are
[CBSE AIPMT 1994] (i) The molecule must have a double Electric Displacement
bond and the double bond should
(a) resolution (b) dehydration
have restricted rotation 56 The compound that is most
(c) revolution
(ii) The two atoms or groups attached to difficult to protonate is
(d) dehydrohalogenation the same carbon atom must be [NEET (National) 2019]
Ans. (a) different. O
O
The process of separation of a racemic These two conditions are only obeyed by (a) H3C H (b) H3C CH3
mixture into d- or l-forms (enantiomers) Cl — CH==CH — Cl, so it shows
O O
is called resolution. The racemic mixture geometrical isomerism. (c) Ph (d) H H
H
of enantiomers is resolved by treating
with an enantiomers of some chiral 54 Which of the following is an Ans. (c)
compound. The products are optically active compound? In CH3OH and CH3OCH3,  CH3 group
diastereomers which can be separated [CBSE AIPMT 1988] shows + I-effect due to which oxygen
by usual methods such as acquires partial negative charge in both
(a) 1-butanol
recrystallisation, chromatography, etc. the compounds.
(b) 1-propanol
δ– δδ–
51 The most important chemical (c) 2-chlorobutane O O
method to resolve a racemic (d) 4-hydroxybutanal H3C H CH3 CH3
(+I-effect) (+I-effect) (+I-effect)
mixture makes use of the Ans. (c)
2-chlorobutane has the structure On the other hand inPh OH, Phshows
formation of [CBSE AIPMT 1994]
−I effect due to which oxygen acquire
Cl
(a) a meso-compound partial positive charge.
 Chiral carbon
(b) enantiomers CH3 — C* — C2H5 δ+
(c) diastereomers  O
(d) racemates H Ph H
Ans. (c) It is optically active due to the presence Along with, the lone pair of oxygen also
of asymmetric carbon atom (C*). show conjugation with benzene ring
Diastereomers have different physical
properties such as melting point, boiling which further increases the positive
point, solubilities in a given solvent,
55 How many chain isomers could be charge on oxygen as:
obtained from the alkane, C 6H14 ? δ+
densities, refractive index, etc. Because O—H O—H
of the differences in the boiling points [CBSE AIPMT 1988]
and the solubilities, they can be (a) Four δ– δ–
separated by fractional distillation and (b) Five
fractional crystallisation. (c) Six δ–
(d) Seven Thus, further decreasing the process of
52 Isomers of a substance must have protonation.
Ans. (b)
the same [CBSE AIPMT 1991]
Therefore, incoming proton will not be
Hexane (C6H14 ) has five chain isomers
(a) structural formula able to attack easily on partial positive ‘O’
and these are
(b) physical properties (i) CH3  CH2  CH2  CH2 atom. Hence, phenol is most difficult to
(c) chemical properties protonate. Thus, option (c) is correct.
 CH2  CH3
(d) molecular formula
Ans. (d) (ii) CH3  CH2  CH2  CH  CH3 57 Which of the following is correct
 with respect to −I effect of the
Two or more compounds having the CH3
same molecular formula but different CH3 substituents? (R = alkyl) [NEET 2018]
physical, chemical properties and  (a) NH2 > OR > F
(iii) CH3  CH2  CH  CH2  CH3
structural formula are called isomers. (b) NR2 < OR < F
(iv) CH3  CH  CH  CH3 (c) NH2 < OR < F
53 Which one of the following can  
CH3 CH3
(d) NH2 > OR > F
exhibit cis-trans-isomerism? Ans. (b, c)
[CBSE AIPMT 1989] CH3
 –I effect is related to the ability of
(a) CH3  CHCl  COOH (v) CH3  CH2  C  CH3 substituent for the electron attraction
(b) H  C ≡≡C  Cl  capacity from the attached carbon
(c) Cl  CH==CHCl CH3 atom.
(d) ClCH2  CH2Cl
i.e. It is based on electronegativity of an H

60 Consider the following compounds
atom. This effect increases with 
[CBSE AIPMT 2015] H3C  C == CH  CH2  Cl ←→
increase in the electronegativity of an
CH3 Ph H
atom.
From above we can conclude that 
CH3 C CH Ph C Ph H3C  C  CH == CH2 ←→
options (b) and (c) are correct. +
−NR2 < − OR < − F (−I effect) 2°-allyl cation H
CH3 (II)
−NH2 < −OR < −F (−I effect)  +
(I) H3C  C == CH  CH2
Also, options (a) and (d) shows the order 1°-allyl cation
of +I effect. CH3 Hence, it undergoes nucleophilic
— NH2 > −OR > −F (+I effect) reaction readily.
(III)
—NR2 > −OR > −F (+I effect)
Ans. (c) 62 The total number of π- bond
58 In pyrrole Hyperconjugation occurs through the electrons in the following structure
3 H-atoms present on the carbon atom
4 is [CBSE AIPMT 2015]
next to the double bond i.e.α-hydrogen
H H H
5 2 atoms. H3C
N1 There is noα-H in the structures I and II.
H3C CH3
H So, hyperconjugation occurs in structure
III only i.e. H2C H CH3
the electron density is maximum
on [NEET 2016, Phase II] (a) 4 (b) 8
(a) 2 and 3 (b) 3 and 4 CH3 (c) 12 (d) 16
(c) 2 and 4 (d) 2 and 5 Ans. (b)
H α-hydrogen
Ans. (d) In a given structure there are4π-bonds.
The conjugation (delocalisation) of H Hence, total number of π-electrons are
electrons in pyrrole can be visualised as H C 8.
C C H H
s H CH3 H
4 3 CH2 π-bond d
H CH3 b on π-
5 2 s C C CH3 π- bo CH3
r r nd
N 1 N N H C
π-bond
H α-hydrogen CH3
H H H H2C H
I II III H
s
s 61 Which of the following is the most 63 The correct order of decreasing

r
N
r
N correct electron displacement for a acidic strength of trichloroacetic
H H nucleophilic reaction to take place? acid (A), trifluoroacetic acid (B),
IV V
[CBSE AIPMT 2015] acetic acid (C) and formic acid (D) is
As resonating structures III and IV are [CBSE AIPMT 2012]
H H2
more stable than II and V. Thus, (a) H3C →– C == C  C  Cl (a) B > A > D > C (b) B > D > C > A
maximum electron density will be found H (c) A > B > C > D (d) A > C > B > D
on carbon 2 and 5.
H H2 Ans. (a)
(b) H3C →– C == C  C  Cl If an electron withdrawing group
59 The pair of electron in the given H
(−I-showing group) is present, e.g.  CF3
carbanion, CH3C ≡C − , is present in H H2 has more (−I-effect) withdrawing power
which orbitals? (c) H3C →– C == C  C  Cl than  CCl 3, it makes the removal of
[NEET 2016, Phase I] H proton more easy by stabilising the
(a) sp 3 (b) sp2 H H2 remaining carboxylate ion and thus,
(c) sp (d) 2p (d) H 3C →– C == C  C  Cl makes the acid more acidic.
H The order of acidity of given compounds is
Ans. (c)
Ans. (d) F Cl
Number of σ -electrons
Hybridisation = Allylic and benzylic halides show high
2 F CCOOH > Cl CCOOH
reactivity towards S N 1 reaction.
2 + 2 (negative ion)
= Further, due to greater stabilisation of F Trifluoroacetic Cl Trichloroacetic
2 allyl and benzyl carbocations acid acid
= 2 = sp intermediates by resonance, primary (B) (A)
Hence, in the carbanion, CH3C ≡ C! , pair allylic and primary benzylic halides
> HCOOH > CH3COOH
of electron as (–)ve charge is present in show higher reactivity in S N 1 reactions Formic Acetic
acid acid
sp-hybridised-orbital. than other simple primary halides.
(D) (C)
(a) (i) > (ii) > (iii) > (iv) H H

64 The correct order of increasing
bond length of (b) (ii) > (iii) > (iv) > (i) +
H C C H HC C H, etc.
C  H, C  O, C  C and C == Cis (c) (iv) > (ii) > (iii) > (i) H+
[CBSE AIPMT 2011] (d) (i) > (iii) > (ii) > (iv) H CH3 CH3
(a) C—C < C == C < C — O < C — H Ans. (a) CH3
|
(b) C—O < C—H < C—C < C == C The carbanion with more s-character is CH3 — C+ shows nine resonating
(c) C—H <C— O <C—C <C ==C more stable. Thus, the order of stability |
(d) C—H <C == C <C—O <C—C is CH3
s s s structures due to the presence of nine
Ans. (d) RC ≡≡ C > C6Hs > R2 C==CH > R 3C — CH2
5 α- C  H bonds.
C — H :0.109 nm
Greater theα H-atom greater will be the
C ==C : 0.134 nm 67 Base strength of hyper conjugation resonating structure
C — O :0.143 nm s and therefore, greater will be the
C — C :0.154 nm
(i) H3CC H2 stability.
∴ Bond length order is
s +
(ii) H2C== CH CH3 does not show the property of
C — H < C == C < C — O < C — C +
(iii) H—C ≡≡ C s resonance while CH3 — CH2 shows three
65 Which one of the following resonating structures due to presence
is in the order of
of three α- C H bonds. Hence, larger
compounds has the most acidic [CBSE AIPMT 2008]
number of resonating structures are
nature? [CBSE AIPMT 2010] (a) (ii) > (i) > (iii) (b) (iii) > (ii) > (i) possible in (b), so it is most stable. The
CH2OH (c) (i) > (iii) > (ii) (d) (i) > (ii) > (iii) above order of stability is also explained
(a) Ans. (d) with the help of (+) I-effect of —CH3
group. More the number of — CH3 group
Weaker the acid, stronger is its
more will be tendency to displace the
OH conjugate base. Among alkane, alkene
electrons towards positively charged
(b) and alkyne, alkynes are most acidic and
carbon of carbocation. Thus, positive
alkanes are least acidic, so the order of
charge is decreased or compensated
base strength is
OH and stability of carbocation is increased.
alkane > alkene > alkyne or
(c) s s
CH3 C H2 > H2 C == C H > H — C ≡≡ C
s 69 In HS − , I − , RNH2 , NH3 order of
OH proton accepting tendency will be
68 Which amongst the following is the [CBSE AIPMT 2001]
CH most stable carbocation? (a) I– > NH3 > RNH2 > HS–
(d) [CBSE AIPMT 2005] (b) NH3 > RNH2 > HS– > I–
CH3 (c) RNH2 > NH3 > HS– > I–
+  (d) HS– > RNH2 > NH3 > I–
Ans. (b)
(a) CH3 — C — H (b) CH3  C + Ans. (c)
Key Idea Presence of electron | 
withdrawing substituent increases the CH3 CH3 Basic strength ∝ rate of accepting a
acidity while electron releasing + + proton.
(c) CH3 (d) CH3CH2 ••
substituent, decreases the acidity. In R  N H2 ,N — has lone pair of
Phenyl is an electron withdrawing Ans. (b) electron which increases the intensity
substituent while CH3 is an electron
The most stable carbocation is t-alkyl due to electron releasing R-group and
releasing substituent. Moreover,
carbocation. The order of stability of increases the tendency to donate lone
phenoxide ion is more resonance
alkyl carbocation is pair of electrons toH+ . Secondly as the
stabilised as compared to benzyloxide
ter-alkyl>sec-alkyl> pri-alkyl > CH+3 size of the ion increases, there is less
ion, thus releases proton more easily.
carbocation. This stability order is attraction for H+ and form weaker bond
That’s why phenol is a strong acid among
described with the help of with H-atom and less basic. The order of
the given compounds.
hyperconjugation and inductive effect. the given series is
On the basis of hyperconjugation, RNH2 > NH3 > HS – > I–
66 The stability of carbanions in the +
following (CH3)2 CH shows six resonating
70 Which one of the following orders
s structures due to the presence of six
s α- C  H bonds,
is correct regarding the –I-effect of
(i) RC C (ii) the substituents ?
H
[CBSE AIPMT 1998]
s s
| + H+
HC——CH HC C H (a) —NR2 < —OR > —F
(iii) R 2C==CH (iv) R 3C —CH2 |
| (b) —NR2 > — OR > —F
is in the order of H CH3 H CH3 (c) —NR2 < —OR < —F
[CBSE AIPMT 2008] (d) —NR2 > —OR < —F
Ans. (c) NO2 NO2 The above given reaction is known as

H Riemer-Tiemann reaction. In this
The electronegativity follows the order r
N < O < F.So, due to electronegative (c) (d) Y
reaction, electrophile involved is
character the order of −I-effect is r dichlorocarbene (•• CCl2 ) which is formed
in theIst step of mechanism. It is given as
 NR2 < − OR < − F
Y H follows :
Ans. (a) Mechanism
71 Correct the increasing order of
NO2 group is an electron withdrawing Step I Generation of electrophile
acidity is as [CBSE AIPMT 1994]
group and exhibit −I effect. This effect CHCl 3 + OH− r – CCl 3 + H2O
(a) H2O,C2H2 ,H2CO 3, phenol
increases with decrease in distance of • CCl + Cl −
(b) C2H2 ,H2O,H2CO 3, phenol
–
CCl 3 → • 2
positive charge present on C-atom and (Electrophile)
(c) Phenol, C2H2 ,H2CO 3,H2O hence lesser is the stability of Dichlorocarbene
(d) C2H2 ,H2O, phenol and H2CO 3 carbocation. Step II Reaction of etectrophile with
In option (a), the positive charge is at phenoxide
Ans. (d) maximum distance toNO2 group, so −I
effect due to NO2 group will be minimum O– O
C2H2 have acidic nature but it is less H
and stability will be maximum.
acidic than water. Phenol is more acidic
NO2 –
than water due to resonance + CCl2 CCl2
stabilisation of phenoxide ion.H2 CO3 is
most acidic due to resonating H O–
stabilisation of carbonate ion (CO23– ).
Thus, the correct order is Y r CHCl2
C2H2 < H2O < phenol < H2 CO33 In option (b) and (d) the positive charges
is at minimum distance toNO2 group
hence the stability will be minimum. o-dichloromethyl
NO2 NO2 phenoxide
TOPIC 4 H Step III Hydrolysis
r
Reaction r
Y O– O– OH
Intermediates CHCl2 CH
2 OH– OH
Y H
72 The most stable carbocation, Also, in option (c) the distance of positive
among the following is charge to NO2 group is more than ortho
[NEET (Odisha) 2019] but less than para, so it will be less stable O– OH
⊕ as compared to option (a). CHO CHO
(a) (CH3) 3C CH CH3 NO2 –H2O H+
⊕
(b) CH3 CH2 CH CH2 CH3
⊕ Salicylaldehyde
(c) CH3 CH CH2 CH2 CH3
r
⊕
(d) CH3 CH2 CH2 Y H
75 The correct statement regarding
electrophile is [NEET 2017]
Ans. (c)
+ 74 In the reaction (a) Electrophile is a negatively charge
CH3 CH CH2 CH2 CH3 is the most stable OH O–Na+ species and can form a bond by
carbocation among the given accepting a pair of electrons from
carbocations. It is because the number CHO a nucleophile
of α-H atom attached to carbocation is + CHCl3+NaOH (b) Electrophile is a negatively
+
maximum in CH3 CH CH2 CH2 CH3. Thus, it charged species and can form a
has maximum number of hyperconjugating
the electrophile involved is bond by accepting a pair of
[NEET 2018] electrons from another
structure hence, it is most stable. –
(a) dichloromethyl anion (C HCl2 ) electrophile
+ (c) Electrophiles are generally neutral
73 Which of the following (b) formyl cation (CHO)
+ species and can form a bond by
carbocations is expected to be (c) dichloromethyl cation (CHCl2 ) accepting a pair of electrons from
most stable? [NEET 2018] (d) dichlorocarbene (•• C Cl2 ) a nucleophile
NO2 NO2
Ans. (d) (d) Electrophile can be either neutral
s
r OH O Na+ or positively charged species and
(a) (b) CHO can form a bond by accepting a
H pair of electrons from a
+ + CHCl3+NaOH nucleophile
Y Y H
Ans. (d) Cl Ans. (d)

An electrophile is defined as electron NO2 —Cl-atom shows + R-effect that
deficient species which attacks on (c) (d) o/p-directive influence but deactivate
electron rich areas. Being electron the benzene ring. While —OH, —CH3
deficient, the electrophiles behaves as groups also shows o/p-influence but
Lewis acids. Ans. (b) activate the benzene ring. But in these
+ +
e.g. + + +
H , Cl , Br , NO2 ,NO etc. The group showing electron-donating —OH group activates more than — CH3.
effect (such as —NH2 , —OH) should Hence, order of electrophilic
The electrophiles can be seen in the
stabilise the intermediate ions, i.e. substitution is
form of neutral molecules also
•• makes the ring more reactive towards
e.g. •• CR , N R,BF etc. OH CH3 Cl
2 3 electrophilic substitution than benzene
Thus, we can say that electrophile can and are called activating group while
be either neutral or positively charged electron withdrawing group (such as —Cl, > > >
species and can form a bond by NO2 ) increases the positive charge on
accepting a pair of electrons from a ring, thus deactivates the ring. Hence,
phenol is more readily attacked by an 81 Which one of the following
nucleophile.
electrophile and is most reactive
compounds is resistant to
towards an electroptile .
76 Which of the following statements nucleophilic attack by hydroxyl
is not correct for a nucleophile? 79 The order of decreasing reactivity ions? [CBSE AIPMT 1998]
[CBSE AIPMT 2015] (a) Methyl acetate
towards an electrophilic reagent,
(a) Nucleophile is a Lewis acid for the following (b) Acetonitrile
(b) Ammonia is a nucleophile (c) Dimethyl ether
(i) Benzene
(c) Nucleophiles attack low electrons (d) Acetamide
density sites (ii) Toluene Ans. (c)
(d) Nucleophiles are not electron (iii) Chlorobenzene Dimethyl ether does not show
seeking (iv) Phenol nucleophilic attack due to absence of
Ans. (a) multiple bond.
Nucleophiles are electron rich species. (a) (i) > (ii) > (iii) > (iv) Other compounds have multiple bonded
Hence, act as a Lewis base but not Lewis C-atom and bears partial positive
acid.
(b) (ii) > (iv) > (i) > (iii) charges, therefore they undergo
(c) (iv) > (iii) > (ii) > (i)
nucleophilic attack byOH− ions.
(d) (iv) > (ii) > (i) > (iii)
77 The radical CH2 is
Ans. (d) 82 The reaction is described as
aromatic because it has [NEET 2013] Benzene having any activating group, i.e. [CBSE AIPMT 1997]
(a) 6p-orbitals and 6 unpaired OH, R, etc, undergoes electrophilic
H
electrons substitution very easily as compared to
CH3(CH2)5
(b) 7p-2orbitals and 6 unpaired benzene itself. Thus, toluene (C6H5 CH3), OH –
electrons phenol (C6H5OH) undergo elecrophilic CBr
(c) 7p-orbitals and 7 unpaired substitution very readily than benzene. H3C
Chlorine with + E and + M-effect H
electrons
deactivates the ring due to strong (CH2)5CH3
(d) 6p-orbitals and 7 unpaired
−I-effect. So, it is difficult to carry out HO C
electrons the substitution in chlorobenzene than
Ans. (a) CH3
in benzene, so the correct order is
H Because of the Phenol >Toluene >Benzene (a) SE2 (b) SN1
presence of (iv) (ii) (i) (c) SN2 (d) S N0
C
6p-orbitals and 6 > Chlorobenzene
H C C H unpaired electrons, it (iii) Ans. (c)
is aromatic in nature When the attack of nucleophile takes
H C C H as these unpaired place on the opposite side of the leaving
electrons delocalise 80 Which one of the following
group in the substrate molecule, a
C in p-orbitals. compounds will be most easily transition state is obtained. It is partially
H attacked by an electrophile? bonded to both the attacking
[CBSE AIPMT 99, 1998] nucleophile and the leaving group and
78 Which one of the following is most Cl results in the formation of product. Such
reactive towards electrophilic reactions are called asS N 2 (bimolecular
(a) (b)
nucleophilic substitution reaction)
attack? [CBSE AIPMT 2008]
because in such reactions, rate depends
CH2OH OH CH3 OH on the concentration of both, the
(a) (b) (c) (d) substrate and the nucleophile.
TOPIC 5 It is an example of electrophilic addition

reaction.
Ans. (b)
In S N 1 reaction, there is slight more
Types of Organic (c) CH4 
Br2
hν
→ CH3Br + HBr inversion product than retention product
Reactions It is a free radical substitution reaction,
because S N 1 reaction also depend on
shielding effect of the front side of the
which have free radical intermediates reacting carbon.
83 Which of the following compound like Br •, CH3•, H• etc.
is most reactive in electrophilic HBr / (C 6H 5 COO) 2
(d) CH3  CH == CH2   → 87 Which of the following organic
aromatic substitution? (Organic peroxide)
compounds has same hybridisation
[NEET (Oct.) 2020] CH3CH2 CH2Br
(Major) as its combustion (CO 2 ) product?
Cl NO2
[CBSE AIPMT 2014]
It is a free radical addition reaction.
Hence, option (c) is correct.
(a) Ethane (b) Ethyne
(a) (b)
(c) Ethene (d) Ethanol
OH 85 Among the following, the reaction Ans. (b)
that proceeds through an Hybridisation of carbon
(c) (d) electrophilic substitution, is = sp3 − number ofπ - bonds
[NEET (National) 2019] In CO2 , (O==C==O) hybridisation of
AlCl3 carbon 1π 1π
Ans. (d) (a) + Cl2
Electron Donating Group (EDG : + R > + = sp3− 2 = sp
hyperconjugation) increases electron —Cl + HCl In ethyne or acetylene, C2H2 ,
density of benzene nucleus (which acts 2π
as nucleophile) and make it more UV light
(H  C ≡≡≡ C  H) hybridisation of carbon
susceptible for electrophilic attack in (b) + Cl2 = sp3− 2 = sp
electrophilic aromatic substitution Cl Cl
(ArSE2) reaction. 88 Which one is most reactive
Lone pair of electrons on the central Cl Cl towards nucleophilic addition
atom of a group (substituent) show + R or reaction? [CBSE AIPMT 2014]
+ M effect with the benzene ring, like- Cl Cl
Heat
CHO
(c) —CH2OH + HCl (a)
Cl OH (Power of +R effect)
whereas NO2 group shows − R effect —CH2Cl O

and makes the benzene nucleus least + H2O
reactive in ArSE2 reaction. C CH3
+ Cu2Cl2
(b)
O O –R (d) —N2Cl–
O H +R N
—Cl + N2 CHO
–R +R
Ans. (a) (c)
So, with the options, order of reactivity Halogenation of benzene is an example
in ArSE2 reaction will be of electrophilic substitution reaction.
(d) > (a) > (c) > (b) AlCl3
CH3
+ Cl2 —Cl + HCl
CHO
84 Which of the following is a free Chlorobenzene
radical substitution reaction?
Reaction given in option (b) is an example (d)
[(NEET (Oct.) 2020]
of addition reaction, reaction in option
(a) Benzene with Br2 / AlCl3 (c) is an example of nucleophilic
(b) Acetylene with HBr substitution and option (d) is an example
(c) Methane with Br2 /hv of substitution reaction. NO2
(d) Propene with HBr/(C 6H5COO)2 Ans. (d)
Ans. (c) 86 In an SN 1 reaction on chiral centres Reactivity of carbonyl compounds
Br / AlCl
(a) C6H5 H  
2
3→ C6H5 Br there is [CBSE AIPMT 2015] towards nucleophilic addition reactions
−HBr
(a) 100% racemisation depends on the presence of substituted
It is an electrophilic group.
aromatic substitution (ArSE2) reaction.
(b) inversion more than retention
leading to partial racemisation Electron withdrawing (−I, − M) groups
HBr
(b) HC ≡≡ CH → CH2 == CH Br (c) 100% retention
increase reactivity towards nucleophilic
HBr addition reactions. Thus, correct order is
→ CH3  CHBr2 (d) 100% inversion
CHO CHO (iv) Double bond character

90 Which one of the following is most
reactive towards electrophilic CX bond acquire some double bond
character due to resonance. Presence of
reagent? [CBSE AIPMT 2011]
> >
CH3 electron withdrawing groups like NO2
at ortho and para-positions facilitate the
(a)
nucleophilic displacement of X of aryl
NO2 (–I, –M) OH halide. Among alkyl halides, 3° halides
O CH3 are more reactive as compared to 2°
(b) halides due to the formation of more
CHO C CH3 stable carbocation. Hence, the order of
NHCOCH3
reactivity of CX bond towards
CH3
nucleophile is as
> (c)
X X
CH2OH
NO2 < (CH3) CH—X
2
CH3
CH3 (+I) < IV
(d)
OCH3
89 Among the following compound I
Ans. (a) < (CH3)3C—X
one that is most reactive towards NO2
electrophilic nitration is CH3 II III
[CBSE AIPMT 2012]
(a) benzoic acid (b) nitrobenzene OH 92 Which of the following reactions is an
(o-cresol) example of nucleophilic substitution
(c) toluene (d) benzene
Due to + M-effect of —OH group and reaction? [CBSE AIPMT 2009]
Ans. (c)
hyperconjugation of — CH3 group, the
Presence of electron releasing groups (a) RX + KOH → ROH + K X
benzene of o-cresol is highly reactive
like  R, OH, etc. increases the towards electrophilic substitution. (b) 2 RX + 2 Na → R — R + 2 NaX
electron density at o/p-position and (c) RX + H2 → RH + HX
thus, makes the benzene ring more 91 The correct order of increasing (d) R X + Mg → RMg X
reactive (at o/p-positions) towards an
electrophile. On the other hand, electron reactivity of C X bond towards Ans. (a)
withdrawing groups like COOH, NO2 , nucleophile in the following KOH → K+ + OH−
etc. if present, reduces electron density compounds is [CBSE AIPMT 2010] RX + OH → R — OH+ X –
–
and thus, reduces the activity of Nucleophile

X X
benzene nucleus towards an NO2 −
OH is a stronger nucleophile than
electrophile. Thus, the order of the given
halogen. So it easily replace the weaker
compounds towards electrophilic
nucleophile.
nitration is
Electron Nucleophiles are either negative charge
withdrawing group (EWG) NO2 or lone pair of electrons bearing species,
I II ••
e.g. OH− , NH3, etc.
NO2 COOH (CH3)3C—X (CH)2CH—X
III IV 93 Which of the following is least
< (a) I < II < IV < III (b) II < III < I < IV reactive in a nucleophilic
(c) IV < III < I < II (d) III < II < I < IV substitution reaction?
Nitrobenzene Benzoic
acid
Key Idea Alkyl halides are more reactive (a) (CH3) 3C — Cl (b) CH2 == CHCl
Electron releasing towards nucleophilic substitution. (c) CH3CH2Cl (d) CH2 == CHCH2Cl
group (ERG)
Reactivity depends upon the stability of Ans. (b)
carbocation intermediate formed.
CH3 Chlorine of vinyl chloride (CH2 == CHCl) is
Among the given halides, aryl halide non-reactive (less reactive) towards
(C6H5 X) is least reactive towards nucleophile (in nucleophilic substitution
nucleophile, due to the four possible reaction) because it shows the following
< < reason resonating structure due to + M-effect
Benzene Toluene (i) Reasonance effect of — Cl-atom.
•• δ– δ+
Thus, toluene is most reactive towards (ii) Hybridisation CH2 == CH — Cl •• ↔ CH2 — CH== Cl
electrophilic nitration. (iii) Unstability of phenyl cation I •• II
In structure II, Cl-atom have positive CH2 CH2Cl Ans. (b)

charge and partial double bond In —CH3, —OCH3 and CF3, CH3 and —OCH3
character with C of vinyl group, so it is are electron donating group. Hence, they
more tightly attracted towards the (b) + Cl2 + Cl activate the benzene nucleus. In these,
nucleus and does not get replaced by order of activation is —OCH3 > — CH3
nucleophile inS N reaction. Benzylic free radical while —CF3 group deactivates the
is resonating stable. benzene nucleus. So, it shows lower rate
94 Which one of the following is a free of electrophilic substitution on benzene
(III) Cl + Cl Cl2 (termination)
radical substitution reaction ? ring. Thus, order of electrophilic
[CBSE AIPMT 2003] substitution is
95 The correct order of reactivity
CH2Cl CF3
towards the electrophilic
(a) + AgNO2 substitution of the compounds
< <
aniline (I), benzene (II) and
CH2NO2
nitrobenzene (III) is
[CBSE AIPMT 2003] CH3 OCH3
(a) II < III > I (b) I > II > III
(b) CH3CHO + HCN CH3CH(OH)CN (c) III > II > I (d) II > III > I <
CH3 Ans. (b)
(c) Boiling In aniline —NH2 group is attached with
+ Cl2 97 Among the following compounds
benzene ring. —NH2 group shows
+M-effect. So, it activates the benzene (I–III), the correct order of reaction
CH2Cl
ring. Hence, rate of electrophilic with electrophile is
substitution is increased due to increase
in the electron density at o/p-position. In OCH3 NO2
case of nitrobenzene, (—NO2 ) −M-effect
Anhy. AlCl3 deactivates the benzene ring. So in
(d) + CH3Cl nitrobenzene, rate of electrophilic
substitution is lower than benzene.
CH3 Hence, order ofSE reaction is I II III
NH2 NO2 [CBSE AIPMT 1997]
(a) II > III > I
Ans. (c) (b) III < I < II
> >
(c) I > II > III
At higher temperature the reaction of
toluene with chlorine is an example of I II III (d) I > III > II
free radical substitution. Ans. (c)
96 Among the following compounds Due to +I as well as + R-effect of —OCH3
(I) Cl — Cl 2Cl the decreasing order of reactivity group, it activates the benzene ring.
Free radical (Initiation) towards electrophilic substitution While —NO2 deactivates the benzene
CH3
is [CBSE AIPMT 2000] ring due to its −I-effect and also
decrease the reaction rate, as well as
−R-effect.
(II) (a) + Cl So, order of SE reaction is
CH2 OCH3 NO2
CH3 OCH3 CF3
+ HCl I II III IV > >
(Propagation) (a) II > I > III > IV (b) III > I > II > IV
(c) IV > I > II > III (d) I > II > III > IV I II III
22
Hydrocarbons
TOPIC 1 Ans. (b)
04 The correct statement regarding
Key Idea Alkanes which contain all
Alkanes equivalent hydrogen atoms forms only
the comparison of staggered and
one monochloro derivative on eclipsed conformations of ethane,
01 Which of the following alkane halogenation. is [NEET 2016, Phase I]
cannot be made in good yield by CH3 (a) The eclipsed conformation of
Wurtz reaction? [NEET 2020]  ethane is more stable than
Neo-pentane,H3C  C  CH3 contains all staggered conformation, because
(a) 2, 3-dimethylbutane 
(b) n-heptane eclipsed conformation has no
CH3 torsional strain
(c) n-butane equivalent hydrogen atoms. So, it will (b) The eclipsed conformation of
(d) n-hexane give only one monochloro derivative on ethane is more stable than
Ans. (b) halogenation. staggered conformation even
In Wurtz reaction, an alkyl halide (R  X) though the eclipsed conformation
give a symmetrical alkane (R  R) of 03 Hydrocarbon (A) reacts with has torsional strain
even number of carbon atom with 100% bromine by substitution to form an (c) The staggered conformation of
yield. ethane is more stable than
alkyl bromide which by Wurtz
2Na/ether
2R  X → R  R ( 100%) reaction is converted to gaseous eclipsed conformation, because
−2NaX staggered conformation has no
hydrocarbon containing less than
An unsymmetrical alkane (R  R ′) with torsional strain
odd number of carbon atom can be four carbon atoms. A is [NEET 2018]
(d) The staggered conformation of
obtained with 33% yield only, if we take a (a) CH3  CH3 (b) CH2 == CH2 ethane is less stable than
mixture of two different alkyl halides, (c) CH ≡≡CH (d) CH4 eclipsed conformation, because
R  X and R ′ X. staggered conformation has
Ans. (d)
R  X + R ′ X → R  R + R ′ − R ′ torsional strain
1442443 The given reaction takes place as follows
67%
Br2 / hν Na / dry ether
+ R − R′ CH4 → CH3Br → Ans. (c)
123 (A ) Step 1 Wurtz reaction
33% (Step 2) Due to the absence of torsional strain
CH3  CH3 staggered conformation of ethane is
So, here n-heptane (C7H16 ) cannot be (A ) more stable than eclipsed conformation
obtained with good yield. Step I Alkyl halide is formed by free of it.
Hydrocarbons in options (a), (c) and (d) radical halogenation of alkane in the
H
have even number of carbon atom presence of UV-light. HH
(symmetrical, alkanes). H H
Step II The formed alkyl halide reacts
with sodium in presence of dry ether to H H
02 The alkane that gives only one form alkane containing double number H
H H
H H
mono-chloro product on of carbon atoms present in alkyl halide. Staggered conformation Eclipsed conformation
chlorination with Cl 2 in presence of This reaction is known as Wurtz
diffused sunlight is reaction. 05 The compound that will react most
[NEET (Odisha) 2019] From the above mechanism, it is readily with gaseous bromine has
(a) 2, 2-dimethylbutane concluded that option (d) is correct as in the formula [NEET 2016, Phase II]
(b) neopentane all other cases the hydrocarbon formed (a) C 3H6 (b) C2H2
(c) n-pentane in step 2 will contain more than four (c) C 4H10 (d) C2H4
(d) isopentane carbon atoms.
Ans. (c) 08 Which of the following reactions is H

In gaseous state, Br2 forms free radicals expected to readily give a
and saturated hydrocarbons are more hydrocarbon product in good H H
prone to have free radical substitutions.
As C4H10 reacts most readily with
yields ? [CBSE AIPMT 1997]
gaseous bromine via free radical Electrolytic H
(a) RCOOK → CH3
mechanism as shown below: oxidation
C4H10 + Br2 → C4H9Br + HBr 2 I CH3

(b) RCOOAg →
(Structure III)
Therefore, option (c) is correct. Cl2 Gauche or
(c) CH3CH3 → Skew form
hν
06 Liquid hydrocarbons can be C2H 5 OH
converted to a mixture of gaseous (d) (CH3)2 CCl → Staggered conformation has minimum
repulsion, so it is the most stable. The
hydrocarbons by Ans. (a) order of stability is
[CBSE AIPMT 2010]
Electrolysis of sodium or potassium salt staggered > gauche > eclipsed
(a) oxidation
of carboxylic acid gives good yield of Energy order eclipsed> gauche >
(b) cracking hydrocarbon staggered
(c) distillation under reduced pressure Electrolytic
(d) hydrolysis 2RCOOK → 2 RCOO–
oxidation
Anode 11 The distance between two
Ans. (b) + 2K +
adjacent carbon atoms is largest in
Key Idea Lower hydrocarbons exist in Cathode [CBSE AIPMT 1994]
At anode
gaseous state while higher ones are in • (a) benzene (b) ethene
liquid state or solid state. 2 RCOO → 2 RCOO+2 e
– –
(c) butane (d) ethyne
•
On cracking or pyrolysis, the 2 RCOO → R  R +2CO2 Ans. (c)
hydrocarbon with higher molecular mass
gives a mixture of hydrocarbons having At cathode The C—C bond length is maximum for
lower molecular mass. Hence, we can 2K+ + 2 e – → 2K single bond, butane have largest C—C
bond length because it contains
say that by cracking a liquid hydrocarbon 2K + H2O → 2KOH +H2 ↑
can be converted into a mixture of carbon-carbon single bond.
gaseous hydrocarbons. 09 In the commercial gasolines, the
12 In the free radical chlorination of
type of hydrocarbons which is more methane, the chain initiating
07 In the following the most stable
desirable, is [CBSE AIPMT 1997]
step involves the
conformation of n-butane is
(a) branched hydrocarbon formation of [CBSE AIPMT 1994]
[CBSE AIPMT 2010]
(b) straight chain hydrocarbon
CH3
(a) chlorine free radical
CH3 (c) linear, unsaturated hydrocarbon
(b) hydrogen chloride
H CH3 H H (d) toluene
(c) methyl radical
(a) (b) Ans. (a) (d) chloromethyl radical
H H H H On increasing the number of branches, Ans. (a)
knocking is decreased and octane
H CH3 hν
number is increased. So, branched chain CH4 + Cl2 → CH3Cl
hydrocarbons have less knocking and is
Chain initiation step involves the fission
CH3 CH3 more desirable.
of Cl2 molecule into chlorine free radical.
CH3 H
Cl2 → Cl • + Cl •
hν
10 The most stable configuration of
(c) (d) n-butane will be [CBSE AIPMT 1997]
H H
H H H H (a) skew boat (b) eclipsed 13 Which of the following compounds
H H3C (c) gauche (d) staggered-anti has the lowest boiling point?
Ans. (d) [CBSE AIPMT 1994]
Ans. (b)
Conformations of n-butane are as under (a) CH3CH2CH2CH2CH3
Key Idea The conformation in which the
CH3 (b) CH3CH ==CH —CH2CH3
heavier groups are present at maximum CH
possible distances, so that the forces of
3 (c) CH3CH ==CH —CH ==CH2
repulsion get weak, is more stable. H H H H (d) CH3CH2CH2CH3
Among the given conformations of H Ans. (d)
n-butane, the conformation shown in Boiling points of alkanes increase as the
H H
option (b), i.e. anti conformation is most H number of carbon atom increases or
stable as in it the bulkier group, i.e. CH3 CH3 molecular mass increases. Alkenes have
CH3 group are present at maximum (Structure I)
(Structure II) high boiling point, so CH3CH2 CH2 CH3 has
Staggered or
possible distance and get lower energy. Eclipsed form the lowest boiling point.
anti-form
Hydrocarbons 177
CH2 CH2 CH3 CH3

14 Reactivity of hydrogen atoms |
attached to different carbon atoms (d) Cl  CH2  CH2  CH
in alkanes has the order (c) |
[CBSE AIPMT 1993] CH3
(a) tertiary > primary > secondary Ans. (b)
CH CH CH3
(b) primary > secondary > tertiary The given road map problem is
(c) Both (a) and (b) O3
(d) tertiary > secondary > primary (d) Alkene (A)
Zn/H2O
Ans. (d) Addition
HCl
Ans. (b) reaction
Tertiary alkanes are more reactive as
they form tertiary free radical which is Let us identity the ozonolysis [(i) O2 /THF, B
(Major product) H3C
more stable. On the other hand, (ii) Zn/H2O] products from each of the
primary alkanes are less reactive C = O + O = CH—CH3
following : H3C Ethanal
because they form 1° free radicals
oo Propanone
which are less stable.
CH3 CH3 H H (a) —CH2CH2CH3 The products of first reaction, i.e.
    ozonolysis can give an idea about the
•
CH3 —C > CH3 —C > CH3 — C > H — C•
• • O O probable alkene as C — —O
   
CH3 H CH2CH2CH3
H H group of these arose from the π-bonds
Stability decreases of alkene. Thus, most probable alkene
oo will be
(b) —CH2CH== CH2
TOPIC 2 H3C H
C== O O ==C
Alkenes —CH2CH==O+ CH2==O H3C CH3
(Methanal)
H3C H
15 The correct structure of C == C
oo
2,6-dimethyl-dec-4-ene is (c) CH2CH2CH3 H3C CH3

Alkene
[NEET 2021] O
The reaction taking place will be
CH2CH2CH3 H3C O3
(a) (b) O C===CHCH3 Zn/H2O
H3C 2-methyl but-2-ene
oo H3C
(d) —CH==CH CH3 (A)
C == O+O ==CHCH3
(c) (d) H3C Ethanal
—CH==O + CH3  CH==O Propanone
Ans. (a) HCl

Addition
reaction
Structure of 2,6-dimethyl-dec-4-ene is We get, methanal from the hydrocarbon
4 in option (b) only. H3 C
2
5 3 C—CH2—CH3 +
1
10
17 An alkene ‘A’ on reaction with O 3 H3 C
6 8 Cl
7 9 and Zn -H2O gives propanone and 2-chloro-2-methylbutane
The structure can be identified with the ethanal in equimolar ratio. Addition (B)
(major product)
help of branches at 2 and 6 positions and of HCl to alkene ‘A’ gives ‘B’ as the Cl
a double bond at 4 position. H3 C
major product. The structure of CH—CH—CH3
product ‘B’ is [NEET (National) 2019] H3 C
16 An alkene on ozonolysis gives CH2 Cl 2-chloro-3-methylbutane
methanal as one of the product. Its | (minor product)
structure is [NEET (Sep.) 2020] (a) H3C  CH2  CH  CH3
CH2 CH2 CH3 CH3 18 Which of the following molecules
| represents the order of
(b) H3C  CH2  C  CH3
| hybridisation sp 2 , sp 2 , sp, sp from
(a)
Cl left to right atoms? [NEET 2018]
CH2 CH CH2 CH3 (a) CH2 == CH  CH == CH2

| (b) CH2 == CH C ≡≡ CH
(c) H3C  CH  CH (c) CH ≡≡ C C ≡≡ CH
| |
(b)
Cl CH3
(d) CH3 CH == CH  CH3
Ans. (b) H2 H-shift ⊕ −

→ Br
CH3 — C — CH2 — CH3 →
(d) H3C  C  CH2Br
Key Idea While judging the hybridisation 
in the given type of organic molecules Ans. (c) CH3
3° carbocation
always look for the number of σ and π The said reactions can be visualised as (more stable)
bonds formed by C-atom involved. Br
Br
H2C CH2 
The hybridisation of the given molecules HBr CH3 — C — CH2 CH3
CH3 CH2 CH2
are. C Electro- 
2 2 2 2 H2 philic CH3
sp sp sp sp addition
(i) CH2 == CH  CH == CH2 Elimination
H3C CH CH2
sp 2 sp 2 sp sp 22 Which of the following compounds
(ii) CH2 == CH  C ≡≡ CH HBr
CH3  CH2  CH2  OH → with molecular formula, C 5H10
sp sp sp sp Electrophilic addition
(iii) CH ≡≡ C  C ≡≡ CH yields acetone on ozonolysis?
sp 3
sp 2
sp 2
sp 3 CH3  CH2  CH2 Br [CBSE AIPMT 2007]
(iv) CH3  CH == CH  CH3 Elimination (a) 2-methyl-2-butene
→ H3C  CH == CH2 (b) 3-methyl-1-butene
Therefore, the correct option is (b).
Br (c) Cyclopentane

19 2,3-dimethyl-2-butene can be HBr
CH2 == C== O → H2 C== C OH (d) 2-methyl-1-butene
Nucleophilic
prepared by heating which of the Ans. (a)
addition
following compounds with a strong O 2-methyl-2-butene (molecular formula
acid? [NEET 2016, Phase I]  C5H10 ) yields acetone on ozonolysis.
q H3C  C Br
(a) (CH3)2 CH —CH — CH == CH3

Direct elimination 23 Which one of the following alkenes
CH3  CH2  CH2  Br →
CH3 will react faster with H2 under
CH3  CH == CH2 catalytic hydrogenation conditions ?
(b) (CH3) 3C —CH == CH2
Thus, option (c) is correct.
(c) (CH3)2 C ==CH — CH2 — CH2
(R =alkyl substituent)
[CBSE AIPMT 2005]
(d) (CH3)2 CH — CH2 — CH == CH2 21 H3C —CH—CH== CH2 + HBr → A
R H R R
 (a) (b)
Ans. (b)
CH3 R R R
CH3 H
H
+ A (predominantly) is R R R R
CH3 C CH CH2 [CBSE AIPMT 2008]
(c) (d)
CH3 CH3 (a) CH3 — CH — CH— CH2Br H H R H

CH3
Ans. (a)
CH3 C CH CH3
Br Stability of alkene
CH3
 1
∝
CH3 CH3 (b) CH3 — C  CH2 CH3 Heat of hydrogenation of alkene
 Greater the number of alkyl groups
1-2-methyl CH3
shift
CH3 C CH CH3 attached to the double bonded carbon
(c) CH3 — CH — CH — CH3 atoms, more stable is the alkene. Hence,
CH3 CH3
  given alkene follow the following order
D
CH3 C CH CH3 Br CH3 of stability.
–H
(d) CH3 — CH — CH— CH3 R R R R
20 Which of the following compounds   = > =
CH3 Br
shall not produce propene by R R R H
reaction with HBr followed by Ans. (b)
R R R H
elimination or direct only H3C — CH — CH == CH2 + HBr → = > =
elimination reaction?  −Br −
CH3 R H R H
[NEET 2016, Phase II] R R R H
(a) H2C CH2 H = > =
C  ⊕
CH3  C  CH  CH3 H H R H
H2
 Hence, faster hydrogenation occurs in
H2 CH3
(b) H3C  C  CH2OH 2° carbocation R H
(less stable) =
(c) H2 C == C ==O R H
Hydrocarbons 179
24 Reaction of HBr with propene in 25 The compound, the decreasing order of stability is
the presence of peroxide gives CH3 [CBSE AIPMT 2000]
[CBSE AIPMT 2004]  (a) II > I > III (b) III > II > I
(a) iso-propyl bromide CH3 —C == CH—CH3 on reaction (c) III > I > II (d) I > II > III
(b) 3-bromo propane with NaIO 4 in the presence of Ans. (b)
(c) allyl bromide KMnO 4 gives [CBSE AIPMT 2003] Stability of alkene
(d) n-propyl bromide (a) CH3COCH3 + CH3CHO 1
∝
Ans. (b) CH3CHO + CO2 Heat of hydrogenation of alkene
(d) Reaction of HBr with propene in the (c) CH3COCH3 Stability of an alkene depends upon the
presence of peroxide gives n-propyl (d) CH3COCH3 + CH3COOH heat of hydrogenation of an alkene.
bromide. This addition reaction is an Therefore, lower the heat of
example of anti-Markownikoff’s addition Ans. (d)
hydrogenation of an alkene, higher will
reaction. H3C be stability.
NaIO
(i.e. it is completed in form of free radical C == CH— CH3 + 3[O]  
4
→ Order of stability is
in presence
addition) H3C of KMnO4
trans-but-2-ene > cis-but-2-ene >
Peroxide H3C but-1-ene.
CH3 — CH == CH2 + HBr →
C ==O + CH3COOH Heat of hydrogenation (kJ/mol) are 115.5,
CH3 — CH2 —CH2Br 119.6 and 126.8 respectively.
H3C
n− propyl bromide
Mechanism of this reaction is
28 In a reaction,
represented asfollows : 26 Which alkene on ozonolysis gives
Hypochlorous
Step I Formation of free radical of CH3CH2CHO and CH3 C CH3 ? CH2 == CH2 →M
acid
peroxide by means of decomposition. 
C6H5 — C—O O— C — C6H5 → ∆ O CH2OH
  [CBSE AIPMT 2001] →
R

O O
Benzoyl peroxide CH3 CH2OH
•
2C6H5 — COO (a) CH3CH2 CH==C
Benzoate free radical CH3 M = molecules, R = reagent. M and R
Step II Benzoate free radical forms are [CBSE AIPMT 1997]
(b) CH3CH2 CH ==CHCH2 CH3
bromine free radical with HBr. (a) CH3CH2 Cl and NaOH
(c) CH3CH2 CH==CHCH3
• • (b) CH2 Cl ⋅ CH2OH and aq. NaHCO3
C6H5 COO + H  Br → C6H5 COOH + Br (d) CH3 — C==CHCH3 (c) CH3CH2OH and HCl
Step III Bromine free radical attacks on 
CH3 (d) CH2  CH2 and heat
C== C of propene to form intermediate
free radical. Ans. (a)
•
O
•
CH3 — CH==CH2 +Br → CH3 — CH— CH2 + When O3 reacts with alkene, it forms Ans. (b)
| ozonide, which on reaction with Zn and CH2OH
Br acid or H2 / Ni gives aldehydes and/or HOCl
CH2 == CH2 → 
1° free radical ketones. These products helps in CH2 Cl
(less stable) locating the position of a double bond as
•
‘ M’ CH2OH
CH3 R
CH3  C H  CH2Br → 
2° free radical NaHCO 3 ( aq ) CH2OH
(more stable)
CH3—CH2—CH == C + O3
Glycol
• CH3
Hence, CH3 — C H — CH2Br is the major CH2OH
O So, M is  and R is NaHCO3.
product of this step.
CH3 CH2 Cl
Step IV More stable free radical accept CH3—CH2—CH C
hydrogen free radical from benzoic acid CH3
and give final product of reaction. i.e. 29 In the presence of platinum
n-propyl bromide. O O
Ozonide
•
catalyst, hydrocarbon A adds
(Reduction)
CH3 — CH— CH2Br + C6H5 COOH → CH3—CH2—CHO + CH3COCH3 hydrogen to form n-hexane. When
Zn/H2O
• + ZnO + H2O hydrogen bromide is added to A
CH3 — CH2 — CH2Br + C6H5 COO
n-propyl bromide instead of hydrogen only a single
Step V Benzoate free radicals are 27 Among the following alkenes, bromo compound is formed. Which
changed into benzoyl peroxide for the 1-butene cis-2-butene of the following is A?
termination of free radical chain. I III [CBSE AIPMT 1996]
• •
C6H5 COO + C6H5 COO → (C6H5 COO)2 trans-2-butene (a) CH3 —CH2 —CH ==CH —CH2 —CH3
II (b) CH3 —CH2 —CH2 —CH ==CH —CH3
(c) CH3 —CH ==CH — CH2 —CH2 —CH3 (c) R —C == O (d) R — CH — CH2 alkene thus formed has
(d) CH2 ==CH —CH2 —CH2 —CH2 —CH3    cis-configuration.
Ans. (a) CH3 OH OH —
H3C—C=
=C—CH3
H2, Pd/C
Quinoline
CH3 — CH2 — CH == CH— CH2 — CH3 Ans. (b) But-2-yne
(A) 1 H3C CH3

Here, mole of B2H6 react with alkene by
HBr Pt H2 2 C=
=C
Markownikoff’s addition and form H H
trialkylborone called Hydroboration, cis-2-butene
CH3CH2 CH2 CH2 CH2 CH3 (syn addition)
n-hexane H2O2 / OH− gives oxidation. So,
trialkyborone oxidise in alcohols and
CH3CH2 CH CH2 CH2 CH3 reaction is also called 34 The number of sigma (σ) and pi (π)
 Hydroboration-oxidation. bonds in pent-2-en-4-yne is
Br
3-bromohexane BH [NEET (National) 2019]
3R —CH == CH2 →
2 6
(a) 8σ-bonds and 5π-bonds
30 When 3,3-dimethyl-2-butanol is ( R — CH2 — CH2 ) 3 — B (b) 11σ-bonds and 2π-bonds
heated with conc. H2SO4 , the major H2 O2 /H +
‘ B’ (c) 13σ-bonds and no π-bonds
product obtained is → 3R — CH2 — CH2 —OH (d) 10σ-bonds and 3π-bonds
[CBSE AIPMT 1995] Ans. (d)
(a)
2,3-dimethyl-2-butene
Single bond = 1σ, Double bond = 1σ + 1 π,
(b)
3,3-dimethyl-2-butene TOPIC 3 Triple bond = 1σ + 2 π.
(c)
2,3-dimethyl-1-butene Alkynes The structure of pent-2-en-4-yne is
(d)
cis and trans-isomers of
2,3-dimethyl-2- butene H H
32 How many (i) sp 2 hybridised carbon 1σ | 1σ 1σ | 1σ 1σ 1σ
Ans. (a) H  C  C ==C 1σC ≡≡C H
•• atoms and (ii) π bonds are present 1σ | 1σ | 1π 2π
1σ
CH3 O H in the following compound? H H
  ∴ The number of sigma (σ) bonds are 10
CH3 — C —– C — CH3 + H+ → —C—C—COOCH3
  Protonation and pi ( π) bonds are 3.
CH3 H
⊕
[NEET (Oct.) 2020] 35 Which one is the correct order of
CH3 OH2
  (a) 7, 5 (b) 8, 6 acidity? [NEET 2017]
Dehydration
CH3 — C —– C — CH3 → (c) 7, 6 (d) 8, 5 (a) CH2 == CH2 > CH3  CH == CH2
  –H2 O
> CH3  C ≡≡ CH > CH ≡≡ CH
CH3 H Ans. (c)
sp2 sp2 O (b) CH ≡≡ CH > CH3 C ≡≡ CH >
CH3
CH2 == CH2 >CH3 CH3
 ⊕ sp2
sp2
CH3  C   C  CH3 C C C
sp2
OCH3 (c) CH ≡≡ CH > CH2 == CH2 > CH3
  sp2 sp2  C ≡≡ CH > CH3 CH3
CH3 H (d) CH3  CH3 > CH2 == CH2 > CH3
2° carbocation Number of sp2 -carbon atom = 7
 C ≡≡ CH > CH ≡≡ CH
CH3 π-bonds = 6
Ans. (b)
Methyl  ⊕ Hence, option (c) is correct.
→ CH3 — C —– C — CH3 Greater the s-character of C-atom in
shift
  hydrocarbons, greater the
CH3 H 33 The most suitable reagent for the
electronegativity of that carbon and thus
3°carbocation following conversion, is
greater the acidic nature of the H
attached to electronegative carbon.
CH3 H3C CH3
−H +  H3C—C≡≡C—CH3 CH ≡≡ CH CH2 == CH2 CH3  CH3
→ CH3 — C == C — CH3 H H
rearrangement
 cis-2-butene Hybridisation : sp sp 2 sp 3
CH3
(a) H2 , Pd/C, quinoline s-character : 50% 33% 25%
(b) Zn/HCl
31 The alkene R—CH== CH2 reacts (c) Hg2+ /H+ , H2O
Electronegativity: ←
Max.

readily with B 2H6 and formed the (d) Na/liquid NH3
Acidic character of ←
Max.
product B which on oxidation with 
Ans. (a) terminal H
alkaline H2O 2 produces Hydrogenation of alkynes in the
[CBSE AIPMT 1995] presence of Pd/C, quinoline proceeds Thus, CH ≡≡ CH > CH3C ≡≡ CH
(a) R —CH2 CHO through syn addition of hydrogen and the > CH2 == CH2 > CH3  CH3
(b) R —CH2 —CH2 — OH
Hydrocarbons 181
36 In the reaction, (a) CH3 — CH—CH2CH2I Ans. (d)

(i) NaNH /liq.NH  Hydration of alkyne,
2
HC ≡CH →
3
Cl Hg 2 + /H+
(ii) CH3 CH2Br I CH ≡≡ CH + H2O → CH2 == CH
(i) NaNH /liq.NH  
2
X →
3
Y (b) CH3 — CH2 — CH2 —C — H OH
Unsaturated
(ii) CH3 CH2Br  alcohol
Cl (unstable)
X and Y are [NEET 2016, Phase I] I
(a) X = 2 -butyne; Y = 3 -hexyne  Tautomerisation
 ↓
(b) X = 2 -butyne; Y = 2 -hexyne (c) CH3 — CH2 — CH — CH2Cl
CH3  CHO
(c) X = 1 -butyne; Y = 2 -hexyne I
(d) X = 1 -butyne; Y = 3 -hexyne 
Ans. (d) (d) CH3CH2  C  CH3 41 The cylindrical shape of an alkyne
 is due to [CBSE AIPMT 1997]
Since,NaNH2 /liq.NH3 behaves as a base, Cl
so it abstracts proton from acetylene to (a) three sigma C—C bonds
form acetylide anion followed by Ans. (d) (b) three π C—C bonds
alkylation to give compound (X) i.e. Followed by Markownikoff’s rule. (c) two sigma C—C and one π C—C
1-butyne. (X) further reacts with bonds
NaNH2 /liq.NH3 followed by alkylation with
CH3 — CH2 — C ≡≡ CH + HCl → (d) one sigma C—C and two π C—C
ethyl bromide yields 3-hexyne (Y). bonds
HI
CH3CH2 — C == CH2 →
H  C ≡≡ CH (1)

NaNH2/Liq.NH3
Cl Ans. (d)
H — C ≡≡ Cs
I In alkynes C ≡≡ C is present, out of these
(2) CH3CH2—Br
alkylation  three bonds one sigma and two π-bonds
CH3 — CH2 — C — CH3 are present. Sigma bond is formed by
HBr + H — C ≡≡ C — CH2CH3
X  sp-hybrid orbitals whereas π-bonds are
Cl formed by unhybridised orbitals.
1-butyne
2-chloro-2 -iodobutane
(1) NaNH2/liq.NH3
Hence, it shows cylindrical shape.
(2) CH3CH2—Br s 39 Products of the following reaction
C ≡≡ C — CH2CH3 42 A compound is treated with NaNH2
alkylation
[CBSE AIPMT 2005]
to give sodium salt. Identify the
H3CH2C — C ≡≡ C — CH2CH3 + HBr (i) O
(Y) CH3C ≡≡ C ⋅ CH2CH3 →
3
compound. [CBSE AIPMT 1993]
(ii) Hydrolysis
3-hexyne (a) C2H2 (b) C 6H6 (c) C2H6 (d) C2H4
… are Ans. (a)
37 Which of the following reagents will (a) CH3CHO + CH3CH2CHO Sodamide is strong base. Therefore it
be able to distinguish between (b) CH3COOH + CH3COCH3 attracts the more acidic hydrogen and
1-butyne and 2-butyne? (c) CH3COOH + HOOC ⋅CH2CH3 gives sodium salt
[CBSE AIPMT 2012] (d) CH3COOH + CO2 H— C ≡≡ C —H + NaNH2 →
1
(a) NaNH2 (b) HCl Ans. (c) H— C ≡≡ C–Na+ + H2
(c) O2 (d) Br2 Sodium ethynide 2
O
Ans. (a) CH3  C ≡≡ C  CH2  CH3 →
3
NaNH2 is used to distinguish between O 2H2O 43 Reduction of 2-butyne with sodium

1-butyne and 2-butyne. CH3C CCH2CH3 in liquid ammonia gives
NaNH
  predominantly [CBSE AIPMT 1993]
CH3CH2 C ≡≡ CH →
2
CH3CH2 C ≡≡ CNa O O
CH3COOH + CH3CH2COOH (a) cis-2-butene (b) trans-2-butene
1
+ H2 ↑ Acetic acid Propanoic acid (c) no reaction (d) n-butane
2
Ans. (b)
NaNH 2
CH3  C ≡≡ C H → No reaction 40 When acetylene is passed through In presence of Na and liquidNH3 liq ⋅NH3.
dil ⋅ H2SO4 in presence of HgSO 4 , Trans addition of hydrogen on alkene
38 Predict the product C obtained in the compound formed is occurs.
Na, liq ⋅NH
the following reaction of butyne-1. [CBSE AIPMT 1999] CH3 — C ≡≡ C — CH3 →
3
but -2-yne Birch reduction

[CBSE AIPMT 2007] (a) ether (2-butyne)
(b) ketone
CH3CH2  C ≡≡ CH + HCl → H3C H
(c) acetic acid
C == C
HI (d) acetaldehyde
B → C H CH3
Trans -but-2-ene
Reagent Ans. (d) towards the carbon atom and help in the
44 R—CH2 —CCl 2 —R → Acetylene have shortest C—C bond release of H+ ions.
R —C ≡≡ C —R. The reagent is length because it have C ≡≡ C triple bond. For a example ethyne react with sodium
[CBSE AIPMT 1993] The bond length follows the following metal and release theH+ ions.
(a) Na (b) HCl in H2O order CH≡≡ CH + Na → HC ≡≡ C−Na+
(c) KOH in C2H5OH (d) Zn in alcohol C — C > C ≡≡ C > C ≡≡ C
Ans. (c)
Dehydrohalogenation reaction,
48 Which is the most suitable reagent TOPIC 4
among the following to distinguish
Cl
compound (III) from rest of the
Aromatic
 C 2 H 5 OH + KOH
RCH2 — C — R →
–KCl, –H 2 O
compounds? [CBSE AIPMT 1989] Hydrocarbons

Cl I. CH3 —C ≡≡ C —CH3
KOH + C H OH II. CH3 —CH2 —CH2 —CH3 50 In the following reaction,
RCH== C — R → 2 5

–KCl, –H2 O III. CH3 — CH2 — C ≡≡ CH H3C C ≡≡ CH →
Red hot iron tube
A,
873 K
Cl IV. CH3 — CH== CH2
R — C ≡≡ C — R (a) Br2 / CCl4 (b) Br2 / CH3COOH the number of sigma (σ) bonds
In presence of ethanolic KOH, substrate (c) Alk. KMnO 4 present in the product A is
gives elimination reaction. (d) Ammoniacal AgNO 3 [NEET (Odisha) 2019]
Ans. (d) (a) 21 (b) 9
45 Select the true statement about (c) 24 (d) 18
It may be noted that only the terminal
benzene amongst the following. alkynes react with ammoniacal silver Ans. (a)
[CBSE AIPMT 1992] nitrate. Therefore, this reaction can be Key Idea Single bond = 1σ, Double bond
(a) Because of unsaturation benzene used to distinguish between 1-alkynes = 1σ, 1 π; Triple bond = 1σ and 2π.
easily undergoes addition and others such as alkane, alkenes and Alkynes form aromatic compounds when
(b) There are two types of C—C bonds non-terminal alkynes. their vapours are passed over red hot
in benzene molecule CH3 — CH2 — C ≡≡ CH + 2[Ag(NH3) 2 ]NO3 copper or iron tubes.
(c) There is cyclic delocalisation of → CH3CH2 C ≡≡ CAg ↓ Red hot iron tube
3CH3—C≡≡CH
pi-bonds in benzene White ppt. 873 K
(d) Monosubstitution of benzene gives CH3
49 Acetylenic hydrogens are acidic
three isomeric products because [CBSE AIPMT 1989]
Ans. (c) (a) sigma electron density of C—H
According to the orbital concept, each bond in acetylene is nearer to H3C CH3
carbon atom in benzene is Mesitylene
carbon which has 50% s-character (A)
sp2 -hybridised and one p-orbital of each (b) acetylene has only one hydrogen
carbon remains unhybridised. The The number of sigma (σ) bonds present
on each carbon in the product (A) is 21.
π-electron charge in benzene is not
(c) acetylene contains least number
confined to space between two carbon H
of hydrogens among the possible σ|
atoms as in ethylene, but is spread over σ
a greater area. This is known as the hydrocarbons having two carbons H—
σ C—H
delocalisation of the electron charge. (d) acetylene belong to the class of σ
σ σ σ σ
alkynes with molecular formula H H
C nH2 n −2 π
46 Which one of the following has the H σ π σ H
shortest carbon-carbon bond Ans. (a) σ| σ π σ |σ
σ C σ σ C
length? [CBSE AIPMT 1992] Acidic character of alkynes can be
H σ σ| σ H
σ|
(a) Benzene (b) Ethene explained on the basis of H H
sp-hybridisation state of the carbon H
(c) Ethyne (d) Ethane
atom in alkynes. We know that an
Ans. (c) electron in s orbital is more tightly held 51 In the given reaction
Ethyne (acetylene) have shortest C—C than in a p orbital because s-electrons
HF
bond length because it have C ≡≡ C i.e. are more closer to the nucleus. In +
0°C
P
triple bond. The bond length follows the sp-hybridisation, s-character is more
following order (50%) as compared to sp2 -(33%) or
the product P is
C ≡≡ C < C == C < C  C sp3-(25%) hybrid orbitals. Due to very
large s-character, the electrons in
sp-hybrid orbitals are held tightly by the F
47 The shortest C—C bond distance is (a) (b) F
nucleus and are quite electronegative.
found in [CBSE AIPMT 1991]
Consequently, the electron pair of
(a) diamond (b) ethane (c) F — C ≡≡ bond gets displaced more
benzene (d) acetylene
Hydrocarbons 183
53 Given, Ans. (c)

(c) (d) H3 C CH3 H3C Nitro group being electron withdrawing,
CH2
deactivates the benzene nucleus to such
an extent . that an electrophile cannot
attack on benzene ring easily due to
deactivation of benzene ring. Hence
Ans. (c) CH3 CH3 becomes incapable to give
Key Idea It is an example of Friedel-Craft (I) (II) Friedel-Craft’s reaction.
reaction. First π-electrons of H2C CH2 NOTE Nitrobenzene because of its
cyclohexene attack at H + ion of HF and unreactivity towards Friedel-Craft’s
form carbocation. This carbocation reaction is used as a solvent for this
further reacts with benzene and forms reaction.
addition product. CH2
(III) 55 Some meta-directing substituents
in aromatic substitution are given.
r The enthalpy of hydrogenation of
HF Which one is most deactivating?
these compounds will be in the [NEET 2013]
H
Electrophile
order as [CBSE AIPMT 2015] (a) C ≡≡ N (b) SO 3H
(a) I > II > III (b) III > II > I (c) COOH (d) NO2
Thus, the correct option is (c).
(c) II > III > I (d) II > I > III Ans. (d)
52 In the reaction with HCl, an alkene Ans. (b)
The deactivating tendency of given
reacts in accordance with the The enthalpy of hydrogenation of given groups follows the order O
Markownikoff’s rule, to give a compounds is inversely proportional to 
stability of alkene. NO2 >  SO3H >  C ≡≡ N >  C OH
product 1-chloro-1-
+ +
methylcyclohexane. The possible H2C CH2 H2C CH2 Thus, NO2 is the most deactivating
– –
alkane is [CBSE AIPMT 2015] group.
CH2 CH3 – 56 The reaction of toluene with Cl 2 in
CH2
+
CH2 the presence of FeCl 3 gives ‘X’ and
(a) (b) reaction in presence of light gives
III Less stable
+ ‘Y ’. Thus, ‘X’ and ‘Y’ are
CH3 H3C CH2 H3C 3 CH2
2 [CBSE AIPMT 2010]
–
(a) X = benzal chloride,
(c) (a) and (b) (d) Y = o-chlorotoluene
H
(b) X = m-chlorotoluene,
CH3 CH3
Ans. (c) II
Y = p -chlorotoluene
For structure A, (c) X = o and p-chlorotoluene,
H2C – CH3
H3C CH3 Y = trichloromethyl benzene
CH2 CH3 H3C Cl
+ (d) X = benzyl chloride,
+
H+ Cl–
Y = m-chlorotoluene
Ans. (c)
CH3 CH3
Key Idea In the presence of halogen
For structure B, Stable carrier, electrophilic substitution occurs
The rearrangement of carbocation occur while in the presence of sunlight,
H3C CH3
because 3°-carbocation is more stable substitution, occurs at the side chain.
than 2°-carbocation. = Already aromatic CH3 CH3
CH3 CH3 compound, more stable.
Cl
+ CH3 Cl2
H Rearrangement
FeCl3
I
2º-carbocation Hence, correct order is III > II > I. o-chlorotoluene
CH3 H3C Cl CH3
54 Which of the following compounds
Cl– will not undergoes Friedel-Craft’s
reaction easily? [NEET 2013]
+
3º-carbocation (a) Cumene (b) Xylene
(c) Nitrobenzene (d) Toluene
Cl
p-chlorotoluene
FeCl 3 + Cl2 → FeCl −4 + Cl + (c) H2C ==CH2 + C 6H6 62 Which one of these, is not
Electrophile attacking species (d) H3C —CH3 + C 6H6 compatible with arenes?
(Q—CH3 is an o/p-directing group.) Ans. (c) (a) Greater stability [CBSE AIPMT 1998]
In presence ofhν, reaction is free radical From the reaction of benzene with (b) Delocalisation of π-electrons
substitution reaction. ethylene in the presence of anhy. AlCl 3, (c) Electrophilic additions
CH3 CH2Cl ethylbenzene isproduced. (d) Resonance
CH2 — CH 3
Ans. (c)
Cl2 Cl2
Anhy. AlCl3 Arenes gives an electrophilic
hν hν + CH2 ==CH 2 95°C substitution reactions. They do not give
electrophilic addition reaction in normal
CHCl2 CCl3 60 In Friedel-Craft’s synthesis of state due to resonance stabilisation.
toluene, the reactants in addition
Cl2 to anhydrous AlCl 3 are 63 Which is the correct symbol
hν [CBSE AIPMT 2000] relating the hetero Kekule
(a) C 6H5Cl + CH4 (b) C 6H5Cl + CH3Cl structure of benzene?
Trichloromethyl
(c) C 6H6 + CH4 (d) C 6H6 + CH3Cl [CBSE AIPMT 1993]
benzene
Ans. (d) (a) º (b) → (c) ≡≡ (d) ←→
57 Nitrobenzene can be prepared Friedel-Craft’s alkylation of benzene Ans. (d)
from benzene by using a mixture of (Ar—H) Kekule in 1865 proposed a ring
conc. HNO 3 and conc.H2SO4 . In Mechanism of this reaction is structure for benzene in which the
the mixture, nitric acid acts as a/an represented as follows : position of the three double bonds are
[CBSE AIPMT 2009] Step I not fixed. He suggested that the
(a) reducing agent (b) acid + double bond keeps on changing their
CH3Cl + AlCl 3 → C H3 + AlCl –4
(c) base (d) catalyst Electrophilie position and this is called resonance.
Ans. (c) According to Kekule, benzene is a
Step II
resonance hybrid of two structures (a)
Conc. H2SO4 and conc. HNO3 react in the H CH3
and (b) and the hybrid structure may
following manner be represented as (c). The (a) and (b)
+ Slow
HNO3 +H2SO4 → H2NO+3 + HSO–4 + CH3 + are called resonating structures and
Base Acid are represented by putting ( ←→)
Intermediate
H2NO+3 → NO2+ + H2O carbocation double headed arrow between them.
Nitronium
ion Step III
Attacking species
(electrophile) H CH3 CH3
Hence, in this reactionHNO3 acts as a
– Fast (a) (b) (c)
base andH2SO4 as an acid. + + AlCl4
64 Benzene reacts with n-propyl
58 Benzene reacts with CH3Cl in the + AlCl3 + HCl chloride in the presence of
presence of anhy. AlCl 3 to form Thus, C6H6 and CH3Cl are required in anhydrous AlCl 3 to give
[CBSE AIPMT 2009] addition to AlCl 3. [CBSE AIPMT 1993]
(a) toluene (b) chlorobenzene (a) 3-propyl-1-chlorobenzene
(c) benzylchloride (d) xylene 61 In Friedel-Craft’s alkylation, besides (b) n-propyl benzene
Ans. (a) CH3 AlCl 3 the other reactants are (c) no reaction
[CBSE AIPMT 1999] (d) iso-propyl benzene
Anhy. AlCl3 (a) C 6H6 + NH2 (b) C 6H6 + CH4 Ans. (d)
+ CH3Cl (c) C 6H6 + CH3Cl (d) C 6H6 + CH3COCl Electrophilic substitution reaction of
Ans. (c) benzene ring yields iso-propyl benzene.
Benzene Toluene
This reaction is known as Friedel-Craft’s Friedel-Craft’s alkylation When
alkylation of benzene. benzene reacts with alkyl halide in + Cl—CH2—CH2—CH3 Anhy. AlCl3
presence of anhy. AlCl3 , toluene is n-propyl chloride
obtained. It is called Friedel-Craft’s H3C—CH—CH3
59 Using anhy. AlCl 3 as catalyst, which alkylation reaction. Friedel-Craft’s
Benzene
one of the following reactions reaction is type of an electrophilic

produce ethylbenzene (PhEt)? substitution reaction.
+ HCl
[CBSE AIPMT 2004] Anhy. AlCl 3
C6H6 + CH3Cl →
(a) H3C —CH2OH + C 6H6 C6 H5 CH3 + HCl Iso-propyl benzene
(b) CH3 —CH ==CH2 + C 6H6 Toluene (Cumene)
23
Organic Compounds
Containing Halogens
Strong base
CH3CH2—CH2—CH==CH2
TOPIC 1 –HBr
Pent-1-ene
(c) (i) is substitution, (ii) and (iii) are
addition reactions
Haloalkane (Hofmann product)
[Minor] (d) (i) and (ii) are elimination reactions
+ CH3CH2—CH==CH—CH3 and (iii) is addition reaction
+?
01 CH3CH2COO − Na + NaOH
  → Pent-2-ene (cis+trans)
Heat (Zaitsev product) Ans. (a)
CH3CH3 + Na 2CO 3 [Major]
(i) CH3CH2 CH2Br + KOH→
In the above reaction,β-elimination CH3CH == CH2 + KBr + H2O
Consider the above reaction and takes placevia E2 mechanism
identify the missing Elimination reaction
(anti-elimination).
reagent/chemical. (ii) H3C CH3
[NEET 2021] According to Zaitsev rule, β-carbon + KOH
(a) B2H6 (b) Red phosphorus carrying lesser number of H-atoms get
(c) CaO (d) DIBAL-H involved in the elimination to give a more Br
substituted alkene (pent-2-ene) as the Substitution reaction
Ans. (c)
major product. H3C CH3
In this reaction, removal of carbon Here, loss of HBr, i.e. + KBr
dioxide takes place. So, this is a dehydrobromination
decarboxylation reaction. A (dehydrohalogenation) takes place. OH
decarboxylation reaction takes place (iii) Br
So, 1, 2 and 3 are correct combination.
with soda lime (NaOH + CaO). + Br2
So, missing reagent is CaO. Br
03 For the following reactions, Addition reaction
02 Elimination reaction of
2-bromo-pentane to form (i) CH3CH2CH2Br + KOH→ 04 In a SN2 substitution reaction of the
pent-2-ene is CH3CH == CH2 + KBr + H2O
DMF
(ii) H3C CH3 type R —Br + Cl– →
1. β-elimination reaction. + KOH R —Cl + Br − ,
2. Follows Zaitsev rule.
Br H3C CH3 Which one of the following has the
3. Dehydrohalogenation reaction.
+ KBr highest relative rate?
4. Dehydration reaction. [CBSE AIPMT 2008]
[NEET (Sep.) 2020] OH (a) CH3 — CH2 — CH2Br
(a) (1), (3), (4) (b) (2), (3), (4) Br
+ Br2 (b) CH3 — CH — CH2Br
(c) (1), (2), (4) (d) (1), (2), (3) (iii)

Ans. (d) Br CH3
Br Which of the following statements
β β′ is correct? CH3
CH3CH2CHCHCH2 
α (a) (i) is elimination reaction, (ii) is (c) CH3 —C — CH2Br
H H substitution and (iii) is addition 
Zaitsev or Hoffmann elimination reaction CH3
Saytzeff elimination centre for β′-H (b) (i) is elimination, (ii) and (iii) are
centre for β-H (three β′-H atoms) (d) CH3CH2Br
(two β-H atoms)
substitution reactions
Ans. (d) Step (ii) Ans. (b)

+
Aprotic solvents like DMF increases the C6H5  CH2 + Nu – Fast
→ C6H5 CH2Nu NaNH 2 ( Sodamide)
reactivity of nucleophile and favoursS N 2 CH3 — CH2 — CHCl2 →
∆
reaction.
NaNH
The relative reactivity of alkyl halides 06 Chloropicrin is obtained by the 2
CH3 — CH== CHCl →
∆
towards S N 2 reactions is as follows reaction of [CBSE AIPMT 2004]
CH3 — C ≡≡ CH
CH3 X >Primary > Secondary > (a) steam on carbon tetrachloride
Final product
Tertiary (b) nitric acid on chlorobenzene
However, if the primary alkyl halide or (c) chlorine on picric acid Ni/H
NaCN 2
the nucleophile/base is sterically (d) nitric acid on chloroform 09 CH3CH2Cl → X → Y
hindered the nucleophile will have
Ans. (d) Acetic anhydride
difficulty to getting the back side of the → Z
α-carbon as a result of this, the Chloroform on reaction with nitric acid
elimination product will be predominant. gives chloropicrin (nitro chloroform). Its In above reaction sequence, Z is
Here, CH3CH2Br is the least hindered, reaction is shown below [CBSE AIPMT 2002]
hence it has the highest relative rate CHCl 3 + HNO3 → C(NO2 )Cl 3 + H2O (a) CH3CH2CH2NHCOCH3
towards S N 2 reaction. Chloroform Nitro chloroform
(chloropicrin)
(b) CH3CH2CH2NH2
05 Which of the following undergoes (c) CH3CH2CH2CONHCH3
nucleophilic substitution exclusively 07 Which of the following is (d) CH3CH2CH2CONHCOCH3
bySN 1 mechanism? responsible for depletion of the Ans. (a)
[CBSE AIPMT 2005] ozone layer in the upper strata of CH3CH2 Cl NaCN
→ CH3 — CH2 — CN
(a) Benzyl chloride the atmosphere? X
(b) Ethyl chloride [CBSE AIPMT 2004] Ni/H2 Acetic
(c) Chlorobenzene (a) Polyhalogens (b) Ferrocenes → CH3 — CH2 CH2NH2 →
anhydride
Y
(d) Isopropyl chloride (c) Fullerenes (d) Freons
CH3 — CH2 — CH2 — NHCOCH3
Ans. (a) Ans. (d) Z
AliphaticS N 1 reaction is carried out in Freons or chlorofluoro carbons are
two steps. In form of slow step responsible for depletion of the ozone 10 Reactivity order of halides for
Step (i) carbonium (carbocation) ion is layer in the upper strata of the dehydrohalogenation is
formed and its formation is based upon atmosphere. They are used as [CBSE AIPMT 2002]
the stability propellants, aerosol spray caps,
(a) R—F > R—Cl > R—Br > R— I
Stability order of carbocation benzylic refrigerants, fire fighting reagents, etc.
They are stable and chemically inert (b) R—I > R—Br > R—Cl > R—F
carbocation (resonating stable)
+ + compounds. They absorb UV-radiation (c) R—I> R—Cl> R—Br > R—F
C6H5 CH2 > CH3  CH  CH3 and break down liberating free atomic (d) R—F> R—I> R—Br> R—Cl
2° carbocation + chlorine which causes decomposition of
> CH3  CH2 Ans. (b)
ozone through free radical reaction. This
1° carbocation results in the depletion of the ozone layer. F, Cl, Br and I are the elements of VII A
and in step (ii) nucleophile is attracted group. In a group atomic radii increases
They form free radical of chlorine in
towards the carbonium ion in form of fast from top to bottom and the bond
presence of UV-radiation. Such free
step to give final product. dissociation energy decreases as
radical decomposesO3 as follows :
Hence, in benzyl chloride, ethyl chloride R—F > R— Cl > R—Br > R—I
and isopropyl chloride order ofS N 1 Cl• + O3 → ClO• +O2
So, during dehydrohalogenation R—I
reaction is benzyl chloride > isopropyl ClO + O3 →
•
Cl •
+ 2O2
Chlorine free bond breaks more easily than R—I bond.
chloride > ethyl chloride. radical Hence, order of reactivity will be
In chlorobenzene, mechanism of S N 1
reaction differ to aliphatic alkyl halide. R—I > R—Br > R—Cl > R—F
08 When CH3CH2CHCl 2 is treated with
The aryl halides are much less reactive
as compared to alkyl halides, towards NaNH2 , the product formed is 11 An organic compound A(C 4 H9 Cl) on
nucleophilic reagents in either S N 1 or [CBSE AIPMT 2002]
reaction with Na/diethyl ether gives a
S N 2 reaction. (a) CH3 — CH == CH2 hydrocarbon which on
The carbon-halogen bond in the aryl (b) CH3 — C ≡≡ CH monochlorination gives only one
halide is quite strong and only forcing
conditions can break up this bond. NH2 chloro derivative, then A is
Hence, (c) CH3CH2CH [CBSE AIPMT 2001]
Step (i) NH2 (a) t-butyl chloride

+ (b) s-butyl chloride
Slow C H CH + Cl –
C6H5 CH2 — Cl → 6 5 2 Cl (c) iso-butyl chloride
(d) CH3CH2CH (d) n-butyl chloride
Rate ∝ [C6H5 CH2 Cl]
NH2
(First order kinetics)
Organic Compounds Containing Halogens 187
Ans. (a) 14 When chlorine is passed through 17 Chlorobenzene reacts with Mg in

Alkyl halides reacts with Na in presence propene at 400°C, which of the dry ether to give a compound (A)
of dry ether to form alkanes. This following is formed? which further reacts with ethanol
reaction is known as Wurtz reaction.
(a) PVC [CBSE AIPMT 1993] to yield [CBSE AIPMT 1993]
R  X + 2Na + X  R (b) Allyl chloride (a) phenol
Dry ether (c) Nickel chloride (b) benzene
→ R  R + 2NaX
(d) 1,2-dichloro ethane (c) ethyl benzene
In the given question t-butyl chloride
C4H9 Cl is A. It reacts with Na metal in dry Ans. (b) (d) phenyl ether
ether to form a hydrocarbon that on When chlorine gas is reacted with Ans. (b)
chlorination gives only one monochloro propene at high temperature (400°C),
Cl MgCl
derivative. then substitution occurs in place of
CH3 CH3 addition reaction. Hence, allyl chloride is
| | formed Dry ether
+ Mg
CH3 — C — Cl + 2Na + Cl — C — CH3 400 ° C
CH3 — CH == CH2 + Cl2 → CH2 —
| | (Allylic substitution)  Chlorobenzene Phenyl magnesium
CH3 CH3 Cl chloride
CH3 CH3
CH == CH2 + HCl C2H5OH
Dry ether   + C2H5OMgCl
→ CH3  C —— C —
—CH3
–2NaCl
  15 Industrial preparation of
CH3 CH3 chloroform employs acetone and Benzene Alcohols contains
[CBSE AIPMT 1993] active hydrogen
2, 2, 3, 3—tetramethnyl-butane
(a) phosgene
(b) calcium hypochlorite 18 HBr reacts fastest with
12 2-bromopentane is heated with [CBSE AIPMT 1992]
(c) chlorine gas
potassium ethoxide in ethanol. The (a) 2-methyl propan-1-ol
(d) sodium chloride
major product obtained is (b) 2-methyl propan-2-ol
[CBSE AIPMT 1998] Ans. (b)
(c) propan-2-ol
(a) 2-ethoxypentane The industrial preparation of chloroform
involves the following steps : (d) propan-1-ol
(b) pentene-1
(c) trans-pentene-2 (i) CaOCl2 + H2O → Ca(OH) 2 + Cl2 Ans. (b)
(ii) CH3COCH3 + 3Cl2 → CCl 3COCH3 2-methylpropan-2-ol gives 3°
(d) cis-pentene-2
+3HCl carbocation, so it reacts with HBr at
Ans. (c) faster speed.
O H CCl 3 — COCH3
–
C 2 H5 O K + (iii) Ca + → CH3
CH3 — CH— CH2 — CH2 — CH3 → 
| O H CCl 3 — COCH3
CH3  C  CH3 + H+ →
Br CH3COO 
2-bromopentane OH
2CHCl 3 + Ca 2-methylpropan-2-ol
+ –
(–Br ) CH3COO
CH3 — CH— CH2 — CH2 — CH3  + → CH3 CH3
–H
 
16 When hydrochloric acid gas is CH3  C  CH3 → CH3  C  CH3
CH3 H treated with propene in presence  –H2 O ⊕
OH2 3 ° carbocation
C == C of benzoyl peroxide, it gives +
H CH2 — CH3 [CBSE AIPMT 1993] CH3

Trans-pentene-2
(a) 2-chloropropane Br − CH  
→ C  CH3
(b) alkyl chloride 3

(c) no reaction Br
13 The alkyl halide is converted into an (d) n-propyl chloride
alcohol by [CBSE AIPMT 1997]
Ans. (a) 19 In compound ‘X’ all the bond angles
(a) addition
(b) substitution
Kharasch effect or peroxide effect is are exactly 109°28′, ‘X’ is
only observed in case of addition of HBr [CBSE AIPMT 1991]
(c) dehydrohalogenation to unsymmetrical alkenes, so the
(d) elimination addition of HCl with propene takes place (a) chloromethane
as usual by Markownikoff’s rule (b) carbon tetrachloride
Ans. (b)
Benzoyl
(c) iodoform
RCl + NaOH(aq) —→ ROH + NaCl CH3 CH == CH2 + HCl → (d) chloroform
peroxide
It is an example of nucleophilic Cl
Ans. (b)
substitution reaction. 
CH3  CH  CH3 Carbon tetrachloride (CCl 4 ) have sp3
2-chloropropane hybridisation and symmetrical
structure, so it have all the bond angle CH3

(d) CBrCH2CH3 –Cl–
of 109° 28′. (d) CH2Cl
CH3
Cl r
Ans. (a) CH2
109°28'
C Addition of HBr to an alkene in presence
Cl of a peroxide (benzoyl peroxide Benzyl-1°-carbocation
Cl (stable)
sp3 hybridised
[(C6H5 CO)2 O2 ] gives an anti-
Markownikoff’s product. So, option (c) will not undergoS N 1
Cl
Tetrahedral
Anti-Markownikoff’s rule states that reaction withOH− .
structure hydrogen is added to a more substituted
carbon atom of an unsymmetrical 24 The compound C 7 H8 undergoes
20 The Cl—C—Cl angle in 1,1,2,2-tetra- alkene.
CH3
the following reactions :
chloroethene and CHCH CH2+HBr
(C6H5CO)2O2 3Cl2 / ∆ Br2 / Fe Zn / HCl
tetrachloromethane will be about CH3 C 7 H8 → A → B → C
3-methylbutene
[CBSE AIPMT 1988]
CH3 The product ‘C’ is [NEET 2018]
(a) 120° and 109 °28′ CHCH2CH2Br +
CH3 (a) 3-bromo-2, 4, 6-trichlorotoluene
(b) 90° and 109.5° 1-bromo-3-methyl (b) o-bromotoluene
(c) 109.5° and 90° butane (Major)
(c) m-bromotoluene
(d) 109.5° and 120° CH3
CHCHCH3 (d) p-bromotoluene
Ans. (a) CH3
Cl Cl Ans. (c)
Br
C == C 2-bromo, 3-methyl
butane (Minor) Given,
Cl Cl
3Cl2 / ∆ Br2 /Fe
Carbon sp2 hybridised Zn/HCl
23 Which of the following will not C7H8 → A → B → C
1,1,2,2-tetrachloro ethene
undergo SN 1 reaction with OH ? The reaction in the above road map can
21 Phosgene is a common name for [NEET (Oct.) 2020] be explained by the following steps.
[CBSE AIPMT 1988] (a) CH2 == CH CH2Cl Step I Toluene (A) undergoes side chain
(a) phosphonyl chloride (b) (CH3) 3CCl halogenation with excess of chlorine to
(b) thionyl chloride CH2CH2Cl give benzotrichloride (A).
(c) carbon dioxide and phosphine CH3 CCl3
(d) carbonyl chloride (c)
3Cl2
Ans. (d)
CH2Cl D
Chloroform is slowly oxidised into a
poisonous compound called phosgene in C7H8 (A)
the presence of air or light. This (d) (Benzotrichloride)
(Toluene)
compound is also called carbonyl
chloride (COCl2 ) Ans. (c) Step II In compound (A), the substituent
1 CCl 3 is an electron withdrawing group, so
CHCl 3 + O2 → Air COCl2 An SN1 reaction proceeds through the electrophile will attack at m-position.
2 light formation of a stable carbocation as
Carbonyl chloride Thus, benzotrichloride reacts with
(phosgene) an intermediate. Here, bromine in presence of Fe- catalyst to
+HCl –Cl–
(a) CH2 CH CH2Cl give m-bromobenzotrichloride (B).
r
TOPIC 2 CH2 CH CH2
CCl3 CCl3
Allyl-1°-carbocation
Haloarene (stable) Br2/Fe
⊕
− Cl−
22 The major product of the following (b) (CH3) 3 CCl → CH3  C  CH3 Br
chemical reaction is [NEET 2021]
 (A) (B)
CH3 m-bromobenzotrichloride
CH3 (C6H5CO)2O2
CHCH CH2+HBr ? tert-butyl carbocation (stable) Step III m-bromobenzotrichloride
CH3 (9 hyper conjugation) undergoes reduction with Zn in presence
CH3
CHCH2CH2Br of HCl to give m-bromotoluene (C).
(a)
(c) –Cl–
CH3 CH2CH2Cl
CCl3 CH3
CH3 –I
(b) CHCH2CH2OCOC6H5 r
CH3
CH2CH2 Reduction
CH3 Zn/HCl
(c) CHCHCH3
CH3 Br Br
1°-carbocation (less stable due (B) (C)
Br to –I effect of the phenyl group) m-bromotoluene
Organic Compounds Containing Halogens 189
hyperconjugative structures) three +I +

25 Which of the following can be used C6H5  CH  CH2  CH3 + Br − →
Fast
groups.
as the halide component for H
CH3 CH3 C6H5  CH  CH2  CH3
Friedel-Crafts reaction?  + 
[NEET 2016, Phase II] (b) C  Cl → CH Br
2° − Cl − Addition product
(a) Chlorobenzene CH3 CH3
(b) Bromobenzene Electrophilic addition reaction takes
2°
carbocation containing
place via more stable carbocation.
(c) Chloroethene 6 α-hydrogen showing six
(d) Isopropyl chloride hyperconjugative structure along
Ans. (d) with two +I group. 28 What products are formed when
Key Idea In chlorobenzene,
(c) H the following compound is treated
bromobenzene and chloroethene, lone CH Cl with Br 2 in the presence of FeBr 3 ?
pair of halogen is delocalised with – + [CBSE AIPMT 2014]
–Cl
π-bonds so it attains double bond CH2 CH3
character. Thus, these are not suitable as
a halide component for Friedel-Crafts Benzyl carbocation
reaction. It has slightly lesser stability as
Anhd. AlCl3
compared to 3°-alkyl carbocation due to CH3
+ CH3 CH Cl presence of three electron donating
CH3 alkyl group in3°-alkyl carbocation. CH3 CH3
CH3 Although the stabilities of 3° and benzyl
C Br
H CH3 carbonium ion are almost same and
(a) and
cannot be compared in solution but
whenever a comparison is made CH3 CH3
Other halides, i.e. chloro and between Resonance (the cause of
bromobenzene along with chloroethene Br
stability in benzyl carbonium ion) and No
have carbon halogen bond as bond resonance (the cause of stability in CH3 CH3
3° carbonium ion) then the former is
Br Br
C always preferred hence here in this
X (b) and
question benzyl carbonium ion is more
stable than 3° carbonium ion. CH3 CH3
26 In which of the following (d) H
– CH3 CH3
–Cl
compounds, the C—Cl bond C Cl
ionisation shall give most stable H –
Br
O2NH2C O and
carbonium ion? [CBSE AIPMT 2015] + + (c)
N C CH2 CH3 CH3
H3C H3C H2
(a) (b) O
CH Cl C Cl Br
1° carbocation less stable than all present here.
H3C H3C CH3 CH3 CH3
H
CH Cl 27 The reaction of C 6 H5 CH==CHCH3
(d) and
H with HBr produces
(c) (d) CH Cl [CBSE AIPMT 2015] CH3 CH3
Br
O2NH2C (a) C6H5 C HCH2 CH3 Br
Ans. (c)  Ans. (c)
Br
The stability of carbocation follow the CH3 is a o/p-directing group, thus
order 3° > 2° > 1° > methyl. More the (b) C 6H5CH2 C HCH3 electrophilic substitution reaction of
number of alkyl group attached with the  toluene
carbon atom carrying the positive Br
CH3 CH3
charge greater would be the tendency to (c) C 6H5CH2CH2CH2Br
stabilise positive charge via inductive CH CHCH3 Br
effect and hence more stable is that Br2/FeBr3
carbocation. Electrophilic
CH3 CH3 (d) CH3 substitution CH3
 + CH3
(a) CH3  C  Cl → CH3  C
 3° — Cl  Br
CH3 CH3 Ans. (a) +
Slow
tert-butyl C6H5 CH == CHCH3 + H+ → CH3
carbocation
+
This carbocation is more stable due C6H5  CH  CH2  CH3 Br
to nine α-hydrogen and (nine Stable carbocation
CH3 CH3 O
H H —Cl |
Br MgBr C—O—MgBr
Br2/FeBr3
Electrophilic Cl3C C O+
CH3 substitution Trichloroacetaldehyde CO2 +
CH3 H3O
H —Cl
Not possible
due to steric Chlorobenzene
O
hinderance
Conc. H2SO4 –H2O ||
C—O—H
29 Trichloroacetaldehyde, CCl 3CHO
reacts with chlorobenzene in the H —Cl + Mg(OH)Br
presence of sulphuric acid and Cl3C C
P
produces [CBSE AIPMT 2009]
Cl —Cl
31 Replacement Cl of chlorobenzene
(a) Cl C Cl Dichlorodiphenyl to give phenol requires drastic
trichloroethane (DDT) conditions but chlorine of 2,
CH2Cl 4-dinitro chlorobenzene is readily
Cl 30 MgBr replaced. This is because
[CBSE AIPMT 1997]
(i) CO2
+ P (a) NO2 makes the ring electron rich at
(ii) H3O
ortho and para-positions
In the above reaction product ‘P ’ (b) NO2 withdraw electrons from
meta-position
(b) Cl C Cl is [CBSE AIPMT 2002]
(c) NO2 donates electrons at
CHO COOH meta-position
H
OH (d) NO2 withdraw electrons from ortho/
(a) (b) para-positions
(c) Cl C Cl Ans. (d)
Cl OH —NO2 group is electron withdrawing
O group, so it deactivates the benzene ring.
||
(d) Cl CH Cl (d) C6H5—C—C6H5 Due to electron withdrawing nature of
(c) —NO2 group, it develops positive charge
CCl3 at o/pposition. This cause easier for the
Ans. (d) Ans. (b) removal of —Cl-atom.
24
Organic Compounds
Containing Oxygen
TOPIC 1 Ans. (a) Ans. (a)
δ+ δ– Least substituted
EDG (+ R, + I) decreases acidity and EWG
Alcohols and Phenols (− R, − I) increases acidity of phenol. H OH sp2 carbon
(i) B2H6
(a) OH CH3CH2 CH CH2
01 The major product formed in (ii) H2O, H2O2, OH
–
dehydrohalogenation reaction of
2-bromo pentane is pent-2-ene. Anti-Markownikoff's
addition of H2O (overall)
This product formation is based on H OH
[NEET 2021]
NO2
(a) Saytzeff’s rule (b) Hund’s rule CH3CH2—CH—CH2
(Z )
(c) Hoffmann rule (d) Huckel’s rule –R from para position Butan-1-ol
Ans. (a) makes its a stronger acid
It is hydroboration-oxidation (HBO)
Saytzeff’s rule states that more (b) OH reaction of an alkene which undergoes
substituted alkene is formed in a hydration to give an alcohol.
dehydrohalogenation reaction. Here, anti-Markownikoff’s addition of H2O
In dehydrohalogenation of takes place.
2-bromopentane, pent-2-ene is formed
as major product which is a more 04 The structure of intermediate A in
substituted alkene. OCH3
the following reaction, is
Br +R from para-position [NEET (National) 2019]
–HBr
deceases its acid remarkably CH3
CH
2-bromopentane Major (pent-2-ene) OH CH3
+ O2 H+
A H2O
Minor (pent-1-ene) (c, d)
(R = CH3, C2H5) OH
O
02 Which of the following substituted
R
phenols is the strongest acid? + H3C CH3
[NEET (Oct.) 2020] +I from para position
decreases its acidity CH3
OH OH
Thus, option (a) is correct.
(a) H3CCOOH
(a) (b) B2H6
03 CH3CH2CH== CH2  −→ Z
H2 O,H2 O2 ,OH
NO2 OCH3
what is Z? [NEET (Oct.) 2020]
OH OH CH3
(a) CH3CH2CH2CH2OH
(b) OOCH
(b) CH3 CH2 CHCH3
(c) (d) 
CH3
OH
C2H5 CH3 (c) CH3CH2CH2CHO (d) CH3CH2CH2CH3
CH2OOH which is a mild oxidising agent forms 07 When vapours of a secondary

aromatic aldehydes.
HC alcohol is passed over heated
CH3 CH2OH CHO copper at 573 K, the product
(c)
PCC formed is [NEET (Odisha) 2019]
(Pyridinium
chlorochromate) (a) a carboxylic acid
CH3 Benzaldehyde (b) an aldehyde
CH In the remaining options benzoic acid is (c) a ketone
O formed as follows: (d) an alkene
CH3
CH2OH COOH Ans. (c)
K2Cr2O7 When vapours of alcohols are passed
(d)
over heated copper at 573 K, primary and
Ans. (a) Benzoic acid secondary alcohols undergo
dehydrogenation to give aldehydes and
The given reaction is of cumene process COCH3 ketones, respectively. While tertiary
for phenol production and intermediate ( (i) NaOCl
alcohols undergo dehydration to give
A) is cumene hydroperoxide. In the (ii) H3O+ alkenes.
process, cumene (isopropylbenzene) is COOH
oxidised in the presence of air to H3C H Cu/573 K
H3C
+ CHCl3 C C=
=O+H2
cumene hydroperoxide. Which is then
converted to phenol and acetone by H3C OH H3C
Benzoic acid Propan-2-ol Propanone
treating with dilute acid. Acetone, a (Ketone)
(2°)
by-product of this reaction is also CH2OH
obtained in large quantities by this KMnO4/H+ Thus, option (c) is correct.
method. The reaction takes place as
COOH
follows :
CH3 08 The compound A on treatment with
CH3 Na gives B, and with PCl 5 gives C. B
CH H3CCOOH Benzoic acid and C react together to give diethyl
CH3 Thus, option (c) is correct.
O2
ether. A, B and C are in the order
[NEET 2018]
06 The hydrolysis reaction that takes (a) C2H5Cl, C2H6 , C2H5OH
Cumene Cumene
place at the slowest rate, among
hydroperoxide (b) C2H5OH, C2H5Cl, C2H5ONa
(A) the following is
[NEET (Odisha) 2019] (c) C2H5OH, C2H6 , C2H5Cl
OH
(d) C2H5OH, C2H5ONa, C2H5 Cl
aq.NaOH
H+ (a) Cl Ans. (d)
H2O + CH3COCH3
Acetone
According to given question and options
CH3
Phenol ONa (A) must be C2H5OH, as it reacts with Na
to give C2H5ONa. The reaction sequence
05 The reaction that does not give CH3 is as follows.
− +
benzoic acid as the major product aq. NaOH Na
(i) C2H5OH → C2H5 ONa
(b) H3C CH2 Cl →
is [NEET (Odisha) 2019] Ethanol Sodium ethoxide
CH2OH H3C CH2 OH (A ) (B)
(a) K2Cr2O7
(c) H2 C == CH  CH2 Cl →
aq. NaOH PCl5 
↓
COCH3 aq.NaOH C2H5 Cl
(i) NaOCl (d) CH2Cl Ethyl chloride
(b) (C )
(ii) H3O+ − S N2
+
CH2OH (ii) C2H5 O N a + C2H5 Cl →
CH2OH
PCC C2H5  O  C2H5 + NaCl
(c) Ans. (a) Diethyl ether
(Pyridinium
chlorochromate)
Cl is a benzylic halide. Thus, The above reaction is known as
CH2OH Williamson’s ether synthesis. It involves
KMnO4/H + there is a partial double bond character
(d) nucleophilic attack of alkoxide ion on
between sp3-hybridised C atom next to
alkyl halide according toS N 2
an aromatic ring and Cl. It is most
mechanism.
Ans. (c) difficult to break this bond and hence it
C2H5O− + CH3  CH2 Cl →
Slow
undergoes hydrolysis reaction with
Primary aromatic alcohols on reaction
slowest rate. Nucleophile Substrate
with pyridinium chlorochromate (PCC) (Alkoxide ion) (Alkyl halide)
Organic Compounds Containing Oxygen 193
+ Fast
C2H5 O… CH2 … Cl − → OH OH Ans. (d)
 O2N NO2 OH OH
CH3 (c) (d) CHO
Dil./NaOH
C2H5 O  C2H5 + Cl − + CHCl3
NO2 NO2 Phenol Chloroform Major
09 Compound A, C 8H10 O, is found to
OH
react with NaOI (produced by Ans. (d)
reacting Y with NaOH) and yields a Thinking process This problem is based
yellow precipitate with on the acidic character of phenol. +
characteristic smell. Electron -withdrawing group ato and
p-position w.r.t. —OH group of phenol, CHO
A and Y are respectively. increase the acidic strength. Minor
[NEET 2018]
Picric acid (2, 4, 6-trinitrophenol) is This is Reimer-Tiemann reaction. So
extremely more acidic than given finally —CHO group is introduced
(a) CH CH3 and I2
compounds because its pKa value is
OH close to zero also due to the presence of 13 Which of the following reaction(s)
three strong electron withdrawing group
( NO2 group) at ortho and
can be used for the preparation of
(b) CH2 CH2 OH and I2
para-positions, picric is more acidic alkyl halides? [CBSE AIPMT 2015]
anh.ZnCl
compound. I. CH3CH2OH+ HCl  2→
(c) H3C CH2 OH and I2
11 Which of the following reagents II. CH3CH2OH+ HCl →
CH3 would distinguish cis-cyclopenta-1, III. (CH3 ) 3 COH+ HCl →
2-diol from the trans-isomer? IV. (CH3 ) 2 CHOH+ HCl  2→
anh.ZnCl
(d) CH3 OH and I2 [NEET 2016, Phase II]
(a) Ozone (a) I, III and IV (b) I and II
Ans. (a) (b) MnO2 (c) Only IV (d) III and IV
Iodoform reaction with sodium (c) Aluminium isopropoxide Ans. (a)
hypoiodite is used for the detection of (d) Acetone In (I) and (IV) due to the presence of
CH3CO group. Also compounds Ans. (d) Lucas reagent (HCl + anh. ZnCl2 )
containing CH3CH(OH) group shows alcohols give alkyl halides while in (III)
cis-cyclopenta-1,2-diol when reacts alkyl halide is formed due toS N 1
positive iodoform test as it produces
CH3CO group on oxidation.
with acetone, forms cyclic ketal reaction.
whereas trans-isomer of cyclopenta-1,
Since, among the compounds,
2-diol can not form cyclic ketal. 14 Which of the following is not the
CH3CH(OH) group is given only in the
substrate of option (a) hence, it is OH
CH3 product of dehydration of
correct. The reaction of compound A + O == C
with NaOI is given as follows : CH3
OH
2NaOH + I2 → NaOI + NaI + H2O cis – cyclopenta Acetone
?
-1, 2-diol
OH
NaOI O CH3
CH CH3
C [CBSE AIPMT 2015]
OH O CH3
(A) C CH3 Cyclic ketal
But, (a) (b)
O OH
Acetophenone CH3
I2/NaOH + O == C
- CH3
CONa++ CHI3 OH
Iodoform Trans-cyclopenta -1, 2-diol (c) (d)
O (yellow ppt.)
Sodium benzoate No reaction
Ans. (b)
10 Which one is the most acidic 12 Reaction of phenol with chloroform Key Concept When
compound? [NEET 2017] in the presence of dilute sodium intermediate carbocation is
OH OH hydroxide finally introduces, which stable, no rearrangement takes place in
one of the following functional carbocation.
group? [CBSE AIPMT 2015]
(a) (b)
(a)  CH2Cl (b) COOH
(c)  CHCl2 (d) CHO
CH3
CH3
18 Which one is a nucleophilic
∆ 
OH
–H2O
+ (a) H3C—C—CH—CH3 substitution reaction among the
  following? [CBSE AIPMT 2011]
OH CH3
(a) RCHO + R′ MgX → R — CH— R′
+ CH3 
 OH
(b) CH2—C—CH2—CH3 CH3
15 Which of the following will not be   
soluble in sodium hydrogen OH CH3 (b) CH3 CH2 CH  CH2 Br
carbonate? [CBSE AIPMT 2014] CH3 + NH3 → CH3 CH2
(a) 2,4,6-trinitrophenol  CH3
(c) H3C—C—CH—CH3 
(b) Benzoic acid
   CH  CH2 — NH2
(c) o-nitrophenol CH3OH
(d) Benzenesulphonic acid CH3 (c) CH3CHO + HCN → CH3 —CH(OH)CN
Ans. (c) 
H+
OH (d) H3C—C—CH2—CH2 (d) CH3 CH == CH2 + H2O →
 
NO2 CH3 OH CH3 CH  CH3
NaHCO3
1No reaction 
Ans. (a)
OH
CH3 CH3
O-nitrophenol is insoluble in sodium | | + Ans. (b)
H+
hydrogen carbonate. While H3CCCH== CH2 H3CCCHCH3
| | (a) RCHO+ R ′MgX →
2,4,6-trinitrophenol, benzoic acid and CH3 (Nucleophilic
CH3 addition)
benzene sulphonic acid are soluble in 2° carbocation
NaHCO3. R  CH  R ′
Infact, Acid + NaHCO3 → Salt + H2 CO3 CH3 CH3 
OH
This reaction is possible in forward H3C CCHCH3
(i) H2O 
direction if acid is more acidic than H+ | | (ii) –H+
(b) CH3  CH2  CH  CH2Br + NH3
H2 CO3. o-nitrophenol is less acidic than CH3 OH CH3
H2 CO3. Hence, it is not soluble in sodium Minor product 
hydrogen carbonate. ‘B’ → CH3  CH2  CH  CH2NH2
CH3 (Nucleophilic
| substitution)
16 In the following sequence of CH3  C  CH  CH3 → (c) CH3CHO + HCN →
reactions, | | (Nucleophilic
KCN H 3O + LiAlH 4 CH3 O+ addition)
CH3 Br → A → B → C CH3CH(OH)CN
ether H
H CH3
the end product C is | (d) CH3  CH == CH2 + H2O
[CBSE AIPMT 2012] CH3  C  CH  CH3 H+
| + → CH3  CH  CH3
(a) acetone (b) methane (Electrophilic

CH3 addition)
(c) acetaldehyde (d) ethyl alcohol 2° carbocation OH
(less stable)
Ans. (d)
H O+ CH3 CH3
KCN
CH3Br → CH3CN →
3
CH3COOH 19 In the following reactions,
Methyl −KBr Ethane Complete Ethanoic 1, 2-Me shift   H 2O [CBSE AIPMT 2011]
bromide nitrile hydrolysis acid H3CCCCH3
CH3
A B +

→
4LiAlH
CH3CH2OH H  H + /Heat
Ether
Ethanol 3° carbocation I. CH3—CH—CH—CH3 →
C (more stable)

In the presence ofLiAlH4 carboxylic acid CH3 H OH
reduce in alcohols directly.
  –H+ A + B
17 In the following reaction, H3CCCCH3 Major Minor
CH3   product product
+ O CH3 HBr, dark
 H 2O/H + H H CH3 CH3 II. A →
H3C C  CH==CH2 →   in absence of peroxide
 H3CCCHCH3 C + D
CH3   Major 
 product 
 Major 
 product 
OH    
A + B
Major product Minor product
2,3-dimethyl butan-2-ol the major products A and C are
(major product) respectively
[CBSE AIPMT 2012] ‘ A’
CH3 CH3 (a) Reimer-Tiemann reaction

 HBr (dark)  (b) Cannizaro reaction
(a) CH3 C == CH CH3 and → CH3  C  CH2  CH3
In the absence
 (c) Wurtz reaction
CH3 of peroxide
Br (d) Friedel-Crafts’s acylation
 Major C
CH3 —C — CH2 —CH3 Ans. (b)
CH3
 (a) Reimer-Tiemann reaction,

Br + CH3  C  CH  CH3 (Here, a new C — C bond is formed.)
CH3   Riemer-Tiemann reaction is an
H Br electrophilic substitution reaction.
 Minor D
(b) CH 3 C ==CH CH3 and OH
20 Given are cyclohexanol (I), acetic
CH3
acid (II), 2, 4, 6-trinitrophenol (III)
 +CHCl3 + NaOH
CH3— CH— CH —CH3 and phenol (IV). In these, the order OH
 of decreasing acidic character will
Br CHO
be [CBSE AIPMT 2010]
CH3 (a) III > II > IV > I (b) II > III > I > IV + NaCl + H2O
 (c) II > III > IV > I (d) III > IV > II > I
(c) CH 2 C ==CH2 CH3 and
Ans. (a) (b) Cannizaro reaction,
CH3
 Key Idea Higher the tendency to give a (disproportionation
CH3—C— CH2 —CH3 proton, higher is the acidic character and reaction)
 tendency to lose a proton depends upon In this reaction, 1-molecule of HCHO
Br the stability of intermediate, i.e. convert in methanol and another
CH3 carbanion formed. molecule convert in salt.
2, 4, 6-trinitrophenol after the loss of a Conc. NaOH
 2 HCHO → CH3OH
(d) CH2 = = C— CH2 —CH3 and proton gives 2,4,6-trinitrophenoxide ion
which is stabilised by resonance, + HCOO−N+ a
CH3 –I-effect and –M-effect, thus is most (No new C—C bond is formed in this
 acidic among the given compounds. reaction.)
CH2 — CH— CH2 —CH3 (c) Wurtz reaction,
Phenol after losing a proton form
 phenoxide ion which is also stabilised by R  X + 2Na + R ′ X + dry Na
Br resonance, − M and – I effects but is less Ether
stabilised as compared to → R  R
Ans. (a)
CH3 2, 4, 6-trinitrophenoxide ions. Thus, it is Here, R and R ′ must be equal
less acidic as compared to 2, 4, otherwise mixture of alkanes will

(I) CH3  CH  CH  CH3 6-trinitrophenol. (CH3COOH) after losing form
  O  (One new C—C bond is formed).
OH a proton gives acetate  CH3C  ion
  (d) Friedel-Craft’s acylation,
 O− 
CH3
Carboxylate ion
+
H /∆  ⊕
+CH3COCl
Anhy. AlCl3
→ CH3  C H  C  CH3 which is stabilised by only resonance.
Protonation However, it is more resonance stabilised
and dehydration 2° carbocation COCH3
as compared to a phenoxide ion, thus
CH3 more acidic as compared to phenol.
1, 2-hydride  2, 4, 6-trinitrophenol, however, is more
→ CH3  C  CH2  CH3
shift + acidic than acetic acid due to the
More stable 3°carbonium ion presence of three electron withdrawing
CH3 —NO2 groups. Cyclohexanol gives an (New C—C bond is formed)
+  anion that is least stable among the Thus, among the given reactions,
H
→ CH3  C == CH  CH3 given, thus, it is least acidic. only Cannizaro reaction does not
Rearrangement Major A
Hence, the correct order of acidic involve the formation of a new C—C
CH3 strength is bond.
 2, 4, 6-trinitrophenol > acetic acid >
+ CH3  CH  CH == CH2 22 Consider the following reaction,
phenol > cyclohexanol
Minor B
III > II > IV > I PBr
A part is major because more Ethanol →
3
X →
Alc. KOH
Y
substituted alkenes are more stable. (i) H SO , room temperature
CH3 21 Which of the following reactions →
2 4
Z
 will not result in the formation of (ii) H2 O, heat
(II) CH3  C == CH  CH3 carbon-carbon bonds?
Major A The product Z is
–
(a) CH2 ==CH2 (b) CH3CH2OCH2CH3 CH3 COOH OH O
(c) CH3CH2OSO 3H (d) CH3CH2OH
Ans. (d) Alk. KMnO4
PBr3 h + H+
C2H5OH → C2H5Br
Ethanol Toluene Benzoic acid Phenol Phenoxide ion
→
Alc. KOH
CH2 == CH2 Y Z
–K Br
–H 2 O Phenoxide ion is stabilised due to
β- elimination
25 Ethylene oxide when treated with following resonating structures :
H SO
2 4 H O/ ∆ Grignard reagent yields s
→ CH3  CH2OSO3H →
2
O O O
–H2 SO4 [CBSE AIPMT 2006]
CH3CH2OH (a) secondary alcohol s
Ethanol (b) tertiary alcohol
23 H2COH⋅ CH2OH on heating with (c) cyclopropyl alcohol
periodic acid gives (d) primary alcohol s
[CBSE AIPMT 2009] I II III
Ans. (d)
(a) 2CO2 (b) 2HCOOH s
Ethylene oxide on treatment with O O
CHO H Grignard reagent give additive product s
(c)  (d) 2 C==O which undergo hydrolysis to give primary
CHO H alcohol as final product
OH
CH2CH2 + RMgX RCH2CH2OMg IV V
Grignard’s
KOH
O reagent
+ CHCl3 –NaCl, Ethylene oxide 28 The enzyme which hydrolysis
Hydrolysis triglycerides into fatty acids and
–H2O RCH2CH2OH –Mg(OH)X
Phenol
OH Primary alcohol glycerol is called
[CBSE AIPMT 2004]
CHO
(a) maltase (b) lipase
26 The general molecular formula, which
(c) zymase (d) pepsin
represents the homologous series of
Ans. (b)
Salicylaldehyde alkanols is [CBSE AIPMT 2006]
CH2OOCR CH2OH
Ans. (d) (a) C nH2 nO2 (b) C nH2 nO
Lipase
CH2OH (c) C nH2 n + 1O (d) C nH2 n + 2O CHOOCR + 3H2O hydrolysis
CHOH
 + HIO4 → Ans. (d)
CH2OH Periodic acid CH2OOCR CH2OH
Alkanols are the derivatives of alkanes Triglycerides Glycerol
Ethylene glycol (Oxidising agent) which are derived by the replacement of
H —H of alkanes with —OH (hydroxyl + RCOOH
2 C==O + HIO3 Fatty acid
H groups).
–H C H
CnH2 n + 2 → 29 Which of the following will not form
n 2 n + 1 OH
24 Consider the following reaction, Alkanes
+OH Alkanols
a yellow precipitate on heating with
Phenol or CnH2 n + 2O an alkaline solution of iodine?
Alk. [CBSE AIPMT 2004]
Zn -dust CH Cl KMnO4
→ X →
3
Y → Z 27 Which one of the following (a) CH3CH(OH)CH3
Anhy. AlCl 3
compounds is most acidic ? (b) CH3CH2CH(OH)CH3
The product Z is [CBSE AIPMT 2005] (c) CH3OH
[CBSE AIPMT 2009] (d) CH3CH2OH
OH
(a) toluene (b) benzaldehyde (a) ClCH2—CH2OH (b) Ans. (c)
(c) benzoic acid (d) benzene
NO2 An organic compound form yellow
Ans. (c) precipitate of iodoform with I2 in
OH OH
OH presence of alkali, if it has
Friedel-Craft's
(c) (d) CH3CO — group directly or it has
reaction
CH3 H
Zn-dust CH3Cl

–ZnO anhy. AlCl3 Ans. (c) CH3  C  group.
reduction 
Phenol of Phenol Benzene Phenols are much more acidic than OH
X alcohols, due to the stabilisation of
NaOH
phenoxide ion by resonance (a) CH3CH(OH)CH3 + I2 → CH3COCH3
+ 2HI + 3NaI + CH3COO−N+ a + 3H2O
CH3COCH3 + 3I2 + 4NaOH → CHI3 ↓ OH 34 Which of the following is correct?

Yellow ppt CHO [CBSE AIPMT 2001]
+ 3NaI + CH3COO−N+ a + 3H2O + 3NaCl + 2H2O (a) Cycloheptane is an aromatic
(b) CH2  CH2 CH(OH) CH3 + I2 → compound
CH3  CH2  C  CH3 + 2HI Major product (b) Diastase is an enzyme
 (Salicylaldehyde) (c) Acetophenone is an ether
O
Ethyl methyl ketone OH (d) All of the above
+
It gives iodoform test H Cl Cl +H2O Ans. (b)
C C Diastase is an example of enzyme which
CH3CH2  C  CH3 + 3I2 + 4NaOH → is used for the conversion of starch into
 Cl Cl Cl +Cl– maltose by hydrolysis
O
CHI3 ↓ + 3NaI + CH3CH2 COONa + 3H2O Diastase
2(C6H10O5 ) n + nH2O → nC12H22O11
Yellow ppt Dichlorocarbene enzyme
(starch) (maltose)
(attacking species)
(c) CH3OH + I2 → HCHO + 2HI
It does not have methyl ketonic 35 Which one of the following is
group, so it does not give yellow ppt. 32 n-propyl alcohol and iso-propyl correct? [CBSE AIPMT 2001]
with I2 in presence of alkali. alcohol can be chemically (a) Reduction of any aldehyde gives
(d) CH3CH2OH+ I2 → CH3  C  H + 2HI distinguished by which reagent? secondary alcohol
 [CBSE AIPMT 2002] (b) Reaction of vegetable oil withH2SO4
O gives glycerine
(a) PCl5
CH3  C  H+ 3I2 + 4NaOH → CHI3
(b) reduction (c) Alcoholic iodine with NaOH gives
 Yellow ppt.
O (c) oxidation with potassium iodoform
+ HCOONa + 3NaI + 2H2O (d) Sucrose on reaction with NaCl gives
dichromate
Due to the presence of —COCH3 invert sugar
(d) ozonolysis
group, it gives Haloform test. Ans. (c)
Ans. (c)
C2H5OH + 4I2 + 6NaOH → CHI3 ↓
30 The —OH group of an alcohol or the n-propyl alcohol and iso-propyl alcohol
Iodoform
—COOH group of a carboxylic acid gives different products on oxidation
with K2 Cr2O7 + HCOO−N+ a + 5NaI + 5H2O
can be replaced by —Cl using
[CBSE AIPMT 2004] [O] Iodoform is a pale yellow solid.
CH3 CH2  CH2OH →
K Cr O /H SO
(a) phosphorus pentachloride 2 2 7 2 4
n -propyl alcohol 36 The correct acidic order of following
(b) hypochlorous acid 1° alcohol CH3 — CH2 — CHO is [CBSE AIPMT 2001]
(c) chlorine Propionaldehyde
(a) I > II > III (b) III > I > II
(d) hydrochloric acid [O] (c) II > III > I (d) I > III > II
Ans. (a) CH3 CH  CH3 →
| K2 Cr2 O 7 /H2 SO 4 Ans.
The —OH group of alcohol or the —COOH OH OH OH OH
Iso-propyl alcohol
group of a carboxylic acid is replaced by 2° alcohol
—Cl using phosphorus penta chloride (i.e.
PCl 5 ) CH3  C  CH3 (I) (II) (III)
ROH + PCl 5 → RCl + POCl 3 + HCl 
Alcohol
O
Acetone CH3 NO2
RCOOH + PCl 5 → RCOCl + POCl 3 + HCl
Acid 33 In preparation of alkene from (a) I > II > III (b) III > I > II
alcohol using Al 2O 3 , which is (c) II > III > I (d) I > III > II
31 When phenol is treated with CHCl 3 effective factor? Ans. (b)
[CBSE AIPMT 2001] The acidic behaviour of phenols may be
and NaOH, the product formed is
(a) Porosity of Al2O3 explained on the basis of two following
[CBSE AIPMT 2002]
(b) Temperature reasons.
(a) benzaldehyde (b) salicylaldehyde (a) Due to resonance (which is not
(c) salicylic acid (d) benzoic acid (c) Concentration
possible in alcohols), the oxygen
(d) Surface area of Al2O3
Ans. (b) atom of the — OHgroup acquires a
Ans. (b) positive charge which helps in the
Reimer-Tiemann reaction When
phenol is treated with chloroform and Temperature is the effective factor for release of a proton.
dehydration of alcohol by +
NaOH, salicylaldehyde is obtained.
Al2O3(dehydrating reagent). OH OH
OH
Al2 O
R — CH2 — CH2OH →
3 –
350 ° - 380 ° C
+ CHCl3 + 3NaOH R — CH==CH2 + H2O
While at 220-250°C, it forms ether.
+1
+
+
OH OH (c) phenoxide ion is stabilised through R CH2 CH2 OMgX
delocalisation Mg(OH) X +
– (d) phenoxide ion is less stable than
H O/H+
ethoxide R  CH2  CH2 OH ←
2
Ans. (c)
Resonance
– representation Resonance stabilisation of phenoxide ion 40 The boiling point of p-nitrophenol is
of phenol
– higher than that of o-nitrophenol
δ +OH O O O
OH because [CBSE AIPMT 1994]
δ- d- – (a) NO2 group at p-position behaves in a

different way from that at o-position
(b) intramolecular hydrogen bonding
δ- – exists in p-nitrophenol
(b) In the dissociation of phenol to – (c) there is intermolecular hydrogen
O O
phenoxide ion and a proton the bonding in p-nitrophenol
equilibrium lies mainly towards the – (d) p-nitrophenol has a higher molecular
right hand side as the resulting weight than o-nitrophenol
phenoxide ion is more stabilised by Ans. (c)
resonance as compared to phenol.
The boiling point of p-nitrophenol is
– C2H5  O —H ºCH 2 5 O +H– +
O O higher than that of o-nitrophenol
Stable Unstable
because p-nitrophenol have
– ethoxide ion
intermolecular hydrogen bonding
(due to absence of resonance) whereas o-nitrophenol have
Phenoxide ion is more stable than intramolecular H-bonding as given
ethoxide ion due to resonance. below.
O Therefore, the ionisation constant of H
O phenol is higher than ethanol. O O
–
N
38 Propan-1-ol may be prepared by + O
reaction of propene with
– Resonance
[CBSE AIPMT 2000]
representation
of phenoxide ion
O o-nitrophenol easily give
 steam volatile
O
– δ- O (a) CH3  C O O H
+ O
δ- δ-
(b) H3BO 3 HO —N
(c) B2H6 /NaOH H2O2 O---HO
(d) H2 SO4 / H2O + O
δ- Ans. (c) N
Ar — OH ArO + H – + O
º
The acidic strength of phenols depends
Hydroboration-oxidation reaction
B H
on the nature of substituents present in 6CH3CH == CH2 →
2 6
2(CH3CH2 CH2 ) 3 B 41 What is formed when a primary
the benzene nucleus. alcohol undergoes catalytic
Propene Tri-n-propylborane
Electron withdrawing groups like NO2 , – dehydrogenation?
H2 O2 / OH
—CN, — CHO, — COOH, etc, when [CBSE AIPMT 1993]
present at the ortho and para-positions 6CH3CH2 CH2OH
Propan-1-ol (a) Aldehyde (b) Ketone
with respect to phenolic group increases
the acidity of phenol due to greater 39 Reaction of H2 C CH2 with RMg X (c) Alkene (d) Acid
stabilisation of phenoxide ion. While the Ans. (a)
presence of electron releasing group like O Aldehydes can be prepared by the
—NH2 , — CH3, etc, decrease the acidity leads to formation of dehydrogenation of primary alcohols. It
of phenols. This explains the following [CBSE AIPMT 1998] is carried out by passing the vapour of
order of acidity primary alcohol over reduced copper at
(a) RCHOHR (b) RCHOHCH3
p-nitrophenol > phenol > p-cresol. R 573 K.
H
(c) RCH2CH2OH (d) CHCH2OH 
37 The ionisation constant of phenol is R — C— O — H → Cu , 573 K
higher than that of ethanol because R

[CBSE AIPMT 2000] Ans. (c) H
δ− +δ
(1° alcohol) R — C == O + H2
(a) phenoxide ion is bulkier than
ethoxide CH2  CH2 + R MgX → 
H
(b) phenoxide ion is stronger base than O Aldehyde
ethoxide Ethylene oxide
1° alcohol gives aldehyde by catalytic Ans. (d) (a) KMnO 4 (alkaline)

dehydrogenation Phenol reacts with bromine water (b) Osmium tetroxide (OsO 4 / CH2Cl2 )
e.g. (aqueous solution to give a precipitate of (c) B2H6 and alk H2O2
Cu + 573 K 2,4,6-tribromophenol) due to polar (d) O 3 / Zn
CH3  CH  O → CH3CHO
 solvent.
 OH Ans. (c)
H H OH
B H
Br Br 3CH3 CH == CH2 →
2 6
42 Which one of the following on + 3Br2(aq) + 3HBr (CH3  CH2  CH2 ) 3B

oxidation gives a ketone?
H2O2 /OH–
[CBSE AIPMT 1993]
phenol → CH3  CH2  CH2 OH
(a) Primary alcohol Br Propan-1-ol
(b) Secondary alcohol 2,4,6-tribromophenol Here, half mol of (B2H6 ) diborane react
(c) Tertiary alcohol (d) All of these (White ppt) with propane by Markownikoff's addition
it gives tripropyl borane called
Ans. (b)
45 Methanol is industrially prepared by hydroboration. In presence ofH2O2 in
Ketones can be prepared by the basic medium tripropyl borane gives
[CBSE AIPMT 1992]
oxidation of secondary alcohols by using alcohol. Remember that product is
oxidising agent such asK2 Cr2O7 / H2SO4 (a) oxidation of CH4 by steam at 900°C
Anti-Markownikoff’s rule that is
H3C (b) reduction of HCHO using LiAlH4 1-propanol. Reaction is called
CHOH + [O] → (c) reaction of HCHO with a solution of
H3C hydroboration oxidation.
NaOH
2° alcohol H3C
C == O + H2O (d) reduction of CO usingH2 and 48 The compound which reacts
H3C ZnO − Cr2O3
Dimethyl ketone fastest with Lucas reagent is (at
Ans. (d)
room temperature)
43 Increasing order of acidic strength Commercially methanol is prepared from [CBSE AIPMT 1989]
among p-methoxy phenol (I), water gas which is a mixture of carbon (a) butan-1-ol
monoxide and hydrogen. In this method,
p-methyl phenol (II) and CO gas is mixed with its half volume of
(b) butan-2-ol
p-nitrophenol (III) is hydrogen and is passed over heated (c) 2-methyl propan-1-ol
[CBSE AIPMT 1992] Cr2O3 − ZnO catalyst at 673 K under high (d) 2-methyl propan-2-ol
(a) III, I, II (b) II, I, III (c) III, II, I (d) I, II, III pressure. Ans. (d)
Ans. (d) Cr2 O -ZnO In Lucas test when Lucas reagent is
CO + 2H2 →
3
CH3OH
OH OH OH 673 K, high pressure treated with 1°, 2° and 3° alcohols, then
turbidity appears, if turbidity is appeared
46 How many isomers of C 5 H11 OH will immediately, then alcohol is tertiary.
, , 2-methyl propan-2-ol is a tertiary
be primary alcohols? alcohol. Hence, it reacts fastest with
[CBSE AIPMT 1992] Lucas reagent.
OCH3 CH3 NO2 (a) 5 (b) 4 (c) 2 (d) 3
I II III Ans. (b) 49 Which chloro derivative of benzene
Nitro group is an electron withdrawing among the following would undergo
The primary alcohols isomers of C5H11OH
group, so increases the acidic character
are hydrolysis most readily with aq.
of phenol. Whereas —CH3 and —OCH3 NaOH to furnish the corresponding
(i) CH3  CH2  CH2  CH2  CH2 OH
both are electron releasing groups, so it
decrease the acidic character of phenol. (ii) CH3  CH  CH2  CH2 OH hydroxy derivative?
But —CH3 group is less electron CH3
donating or releasing, so p-methyl (iii) CH3  CH2  CH  CH2  OH NO2
phenol is slightly more acidic as compare 
to p-methoxy phenol and p-nitro phenol CH3 CH3 (a) O2N— —Cl
is most acidic. So, the order of acidic 
character is (iv) CH3  C  CH2 OH
p-methoxy phenol < p-methyl phenol  NO2
CH3
< p-nitro phenol.
(b) O2N— —Cl
44 When phenol is treated with excess 47 Propene, CH3  CH == CH2 can be
of bromine water, it gives
[CBSE AIPMT 1992]
converted into 1-propanol by
oxidation. Indicate which set of (c) Me2N— —Cl
(a) m-bromophenol
(b) o- and p-bromophenols
reagents amongst the following is
(c) 2,4-dibromophenol ideal to affect the above (d) C6H5—Cl
(d) 2,4,6-tribromophenol conversion? [CBSE AIPMT 1989]
Ans. (a) of functional group are known as (b) H3C CH2 CH2 OH and
Cl OH metamers and this phenomenon is I C(CH3) 3
O2N NO2 NO2 NO2
known as metamerism. (c) H3C CH2 CH2 I and
(a) C5H12 contains no functional group. HO C(CH3) 3
H2O
Warm
So, it cannot show metamerism. (d) H3C  CH2  CH2 OH and
dil. HCl (b) C3H8O has ether functional group in HO C(CH3) 3
NO2 NO2 which only one arrangement is Ans. (a)
Picric acid possible. So, it does not show
or 2, 4, 6-trinitrochlorobenzene metamerism. Ethers are readily cleaved by heating in
presence of halogen acids to form
CH3 — O — CH2 — CH3
alcohol and an alkyl halide. In case of
50 When phenol is heated with CHCl 3 (c) C3H6O has carbonyl functional group unsymmetrical ethers, halogen goes
and alcoholic KOH, salicylaldehyde is in which following two arrangements preferentially with smaller alkyl group or
are possible. more stable carbocation.
produced. This reaction is known as
[CBSE AIPMT 1989, 88]
O If excess of acid is used then only alkyl

(a) Rosenmund’s reaction CH3 — C— CH3, CH3CH2 CHO halide is formed because alcohol formed
(b) Reimer-Tiemann reaction reacts further with halogen acid to form
So, it shows functional group corresponding alkyl halide.
(c) Friedel-Craft’s reaction isomerism and does not show
HI
(d) Sommelet reaction metamerism. CH3CH2CH2OC(CH3)3
∆
Ans. (b) (d) C4H10O has ether functional group in CH3CH2CH2OH + (CH3)3 I
which following two arrangements
When phenol is heated with chloroform ‘D’
are possible. So, it shows ∆ Excess
(CHCl 3) and alcoholic KOH, metamerism.
HI
salicylaldehyde is formed. This reaction CH3CH2CH2I
is known as Reimer-Tiemann reaction. CH3 O  CH2  CH2  CH3
Methoxy propane ‘C’
OH
CH3  CH2  O  CH2  CH3
Ethoxy ethane 55 The heating of phenyl-methyl
+ CHCl3
KOH
53 Anisole on cleavage with HI gives: ethers with HI produces. [NEET 2017]
–NaCl,
–H2O [NEET (Sep.) 2020] (a) ethyl chlorides (b) iodobenzene
OH I I
(c) phenol (d) benzene
Phenol
CHO Ans. (c)
(a) + CH3OH (b) + C2H5I Thinking Process This problem is based

on the resonance stabilisation.
Salicylaldehyde OH In anisol, methyl phenyl oxonium ion is
I
formed by protonation of ether. The
bond between O — CH3 is weaker than
51 Lucas reagent is [CBSE AIPMT 1988] the bond between O — C6H5 , because the
(c) + C2H5OH (d) + CH3I
(a) conc. HCl and anhy. ZnCl2 carbon of phenyl group is sp2 -hybridised
(b) conc. HNO 3 and anhy. ZnCl2 and there is a partial double bond
(c) conc. HCl and hydrous ZnCl2 Ans. (d) character. Thus, the reaction yields
(d) conc. HNO 3 and hydrous ZnCl2 H phenol and alkyl halide.
Ans. (a) H—I H + CH3
OCH3 OCH3 I OCH3 O OH
The equimolar mixture of concentrated –I
(Anisole) SN2
hydrochloric acid and anhydrousZnCl2 is attack
H I I
–
called Lucas reagent. Lucas reagent is No SN2-attack + CH3I

used to distinguish between 1°, 2° and 3° of I to OH + CH3I
the aryl carbon Anisol Phenol
alcohols. is possible Option (d)
So, even with excess of HI anisole will 56 The reaction

TOPIC 2 give always phenol and methyl iodide (as
NaH
in option-d) OH OsNa+
Ethers
54 The major products C and D formed MeI O
Me
52 The compound which shows in the following reactions
metamerism is [NEET 2021]
respectively are can be classified as
(a) C 5H12 (b) C 3H8O (c) C 3H6O (d) C 4H10O [NEET (Odisha) 2019] [NEET 2016, Phase I]
Ans. (d) H3C CH2 CH2 OC(CH3 ) 3 (a) Alcohol formation reaction
Metamerism compound which have Excess HI (b) Dehydration reaction
same molecular formula but different → C + D (c) Williamson alcohol synthesis reaction
∆
number of carbon atoms on either sides (d) Williamson ether synthesis reaction
(a) H3C CH2 CH2 I and I C(CH3) 3
Ans. (d) (c) CH3 (CH2 ) 4  O  CH3 product with hot conc. HI. The order of
The formation of ether from alcohol in stability of carbocation is
the presence of base followed by (d) CH3CH2  CH(CH3) O CH2CH3 3° > 2° > 1°
alkylation is known as Williamson ether CH3
Ans. (a)
synthesis reaction. 
HBr / H2 O2 Thus, CH3  C  OCH3 gives CH3OH as
OH
NaH
OsNa+
CH3CH2 CH == CH2 → 
–H2 Anti - Markownikoff' s rule
CH3
Alkylation MeI CH3CH2 CH2 CH2Br → one of the product. The reaction
Bromo-butanane (1° product) proceeds as
NaI + O
Me C 2 H ONa CH3
⋅⋅
CH3CH2 CH2 CH2Br →
5

⋅⋅
SN 2 reaction
H3C  C  O  CH3 + H+
57 The reaction, (Williamson’s synthesis) 
CH3 CH3CH2 CH2 CH2OC2H5 CH3
 Ethoxy-butane CH3
CH3 C ONa + CH3CH2Cl  +
59 Among the following sets of → H3C C  O CH3

CH3 reactants which one produces  
anisole? [CBSE AIPMT 2014] CH3 H
CH3 CH3
(a) CH3CHO, RMgX
 
→
−NaCl
CH3 C O − CH2 − CH3 (b) C 6H5OH, NaOH, CH3 I → H3C  C+ +CH3OH
 (c) C 6H5OH, neutral FeCl3 
CH3 (d) C 6H5 —CH3, CH3COCl, AlCl3 CH3
3°carbocation
is called [CBSE AIPMT 2015] Ans. (b) CH3
(a) Williamson synthesis Williamson’s synthesis +I È 
→ CH3  C  I + CH3OH
(b) Williamson continuous etherification OH O-N+a  Methanol
process CH3
(c) Etard reaction
(d) Gatterman-Koch reaction + NaOH
61 The reaction
Ans. (a)
CH3
The reaction of alkyl halides with sodium OCH3
alkoxide or sodium phenoxide to form 
ethers is called Williamson synthesis. H3C CH  CH2 O CH2 CH3
CH3I
Here, in this reaction alkyl halide should Heated
be primary and alkoxide, should be SN2 + HI → ---
bulkier as shown below, Anisole Which of the following
R  X + R ′  ONa → compounds will be formed?
Alkyl
halide
Sodium alkoxide 60 Among the following ethers which [CBSE AIPMT 2007]
R O  R ′+NaX one will produce methyl alcohol on CH3
Ether treatment with hot concentrated 
CH3 (a) H3C CH  CH2 I + CH3CH2OH
 HI? [CBSE AIPMT 2013]
CH3  C ONa + CH3CH2 Cl → (a) CH3 CH2 CH2 CH2 O  CH3 (b) CH3 CH  CH3 + CH3CH2OH
 −NaCl 
CH3 (b) CH3 CH2 C H  O CH3 CH3
CH3 
(c) CH3 CH  CH2OH + CH3CH3
 CH3
CH3  C O  CH2  CH3 
CH3
 CH3
CH3 
(c) CH3 C  O CH3 CH3
 
58 Identity Z in the sequence of CH3 (d) H3C CH  CH2OH + CH3 CH2 I
reactions, [CBSE AIPMT 2014] Ans. (d)
(d) CH3 CH  CH2 O CH3
HBr /H2O 2  When conc. HI or HBr reacts with ether,
CH3CH2CH == CH2 → Y
CH3 the corresponding alcohol and alkyl
C 2H ONa
5
→ Z Ans. (c) iodide is formed. When there is a case of
mixed ethers the halogen atom attaches
(a) CH3  (CH2 ) 3 O CH2CH3 The ether which gives more stable to the smaller alkyl group, due to steric
carbocation, forms CH3OH as one of the effect.
(b) (CH3)2 CH2  O  CH2CH3
CH3 (c) Phenol 66 Match List-I with List-II.

 (d) None of the above
CH3  CH  CH2 O  CH2  CH3 + HI List-I List-II
Ans. (a)
CH3 1. Hell-Volhard-
When sodium phenoxide (C 6H5O −N+ a)
CO, HCl
 A. Anhyd. AICI3/CuCl Zelinsky
∆
→ CH3  CH  CH2 OH + CH3CH2I is heated with ethyl iodide (C2H5I) it reaction
form ethyl phenyl ether which is also O 2. Gattermann-
called phenetole. This reaction is  Koch
62 The major organic product in the called Williamson’s synthesis B. R C CH 3 + NaOX → reaction
reaction, CH3OCH(CH3 ) 2 + HI →
C. R CH 2 OH + R ′ COOH 3. Haloform
Product, is/are [CBSE AIPMT 2006] -+ Conc. H 2SO 4 reaction
—ONa + IC2H5  →
(a) CH3OH + (CH3)2 CHI
D. R CH 2 COOH 4. Esterification
(b) ICH2OCH(CH3)2
(c) CH3OC (CH3)2 OC2H5 + NaI (i) X /Red P
 2 →
(ii) H 2O
|
I Phenetole [NEET 2021]
(d) CH3I + (CH3)2 CHOH Choose the correct answer from
Ans. (d) the options given below.
TOPIC 3
CH3 O  CH(CH3)2 + HI →
373 K
CH3I A B C D A B C D
Aldehydes and Ketones (a) 4 1 2 3 (b) 3 2 1 4
Unsymmetrical ether + (CH3)2 CHOH
(c) 1 4 3 2 (d) 2 3 4 1
In case of unsymmetrical ether, the alkyl 65 The product formed in the
halide is always formed from smaller alkyl Ans. (d)
group. This happens, becauseI− ion being
following chemical reaction is
[NEET 2021] A. Gattermann-Koch reaction Benzene
larger in size approaches smaller alkyl
O O or its derivatives are treated with CO and
group to avoid steric hindrance.
HCl in presence of anhydrous AlCl 3/ CuCl.
CH2  C  OCH3
NaBH4 CHO
63 Ethanol and dimethyl ether form a ? CO, HCl
C2H5OH
pair of functional isomers. The CH3 Anhy. AlCl3/CuCl
boiling point of ethanol is higher OH H Benzene Benzaldehyde
than that of dimethyl ether due to CH2COCH3 B. Haloform reaction Treatment of
the presence of [CBSE AIPMT 1993] (a) carbonyl compound having atleast one
OH methyl group attached to the C==O with
(a) H-bonding in ethanol CH3
(b) H-bonding in dimethyl ether X2 / NaOHor NaOX.
O O
(c) —CH3 group in ethanol 
CH2CH2OH
(d) —CH3 group in dimethyl ether R  C  CH3 + NaOX →
(b)
Ans. (a) Aldehyde
CH3 O
Alcohols have higher boiling points as H 
OH R  C Os Na⊕ + CHX3
compared to other organic compounds
of similar molecular masses such as CH2CCH3 C. Esterification Carboxylic acid reacts
ethers. This is due to the presence of (c) with an alcohol in acidic medium.
OH
CH3
intermolecular hydrogen bonding in R  CH2 OH + R ′ COOH
alcohols which is absent in ethers. O Alcohol Acid
OH
Because of hydrogen bonding in
alcohols, these exist as associated CH2COCH3 O
molecules rather than discrete (d) 
molecules. Consequently, a large CH3 R  CH2 O  C  R ′
Ester
amount of energy is required to break Ans. (d) D. Hell-Volhard Zelinsky reaction
these bonds and therefore, their boiling
NaBH4 is a weak reducing agent. It can Treatment of carboxylic acid having
points are high.
reduce aldehyde/ketone to alcohol but α-hydrogen withPX3 or X2 / Red P.
R R R O
   cannot reduce ester group.
- - - O H- - - O H- - - O H- - - O  (i) X 2 / Red P
O R  CH2  C OH →
H-bonding (ii) H 2 O
CH2COCH3 Carboxylic acid O
NaBH4 
64 Which one is formed when sodium C2H5OH R  CH  C OH
CH3
phenoxide is heated with ethyl 
OH O X
iodide? [CBSE AIPMT 1988] α-halocarboxylic acid
CH2COCH3
(a) Phenetole Hence, correct match is
(b) Ethyl phenyl alcohol A→ 2, B→ 3, C→ 4, D→ 1.
CH3
67 What is the IUPAC name of the Mechanism Ans. (a)

organic compound formed in the O O O
following chemical reaction? (i) PhCCH2
OH
PhCCH2 C Cl
Enolate ion
[NEET 2021] H2
H
(i) C2H5MgBr, Dry ether Tautomerism Pd/BaSO4
Acetone → product (Lindlar catalyst)
(ii) H O, H+ O —H O Benzoyl chloride
2
H2O (A) CHO
(a) 2-methyl propan 2-ol PhC==CH2 Ph C==CH2
–OH
(b) pentan-2-ol Oδ
–
O
(c) pentan-3-ol H2O Benzaldehyde
(ii) Ph CH + CH2  C  Ph
(d) 2-methyl butan-2-ol +
δ –OH s
It is Rosenmund reaction, in which an
Ans. (d) OH O acid chloride gets converted into an
–H2O aldehyde.
Acetone on reaction with Grignard Ph CH CH C Ph
reagent and on further hydrolysis gives
2-methyl butan-2-ol as follows H 71 Predict the correct intermediate
Aldol PhCH==CH COPh
– + and product in the following
O OMgBr
69 Identify compound X in the reaction. [NEET 2017]
(i) C2H5MgBr H2 O, H2 SO4
CH3CCH3 CH3CCH3 following sequence of reactions. H3C C ≡≡ CH  →
Dry ether
Acetone HgSO4
C2H5 CH3 CHO
OH Intermediate → Product
( A) ( B)
Cl2/hv H2O
(ii) H2O, H+ CH3—C—CH3 X 373 K (a) A =H3C  C == CH2 ;
CH2 
[NEET (Sept.) 2020] SO4
CH3 CH2Cl CHCl2 B=H3C  C  CH3
(Product)

IUPAC name of product is O
(a) (b)
2-methylbutan-2-ol. (b) A =H3C  C == CH2 ;

CCl2 Cl OH
68 Reaction between benzaldehyde
and acetophenone in presence of B =H3C  C == CH2
dilute NaOH is known as (c) (d) 
[NEET (Sept.) 2020] SO4
(a) Cannizzaro’s reaction Ans. (b) (c) A =H3C  C  CH3;
(b) Cross Cannizzaro’s reaction 
An 1, 1-gem-dihalide on hot hydrolysis O
(c) Cross aldol condensation (H2O/373 K) can produce an aldehyde.
(d) Aldol condensation B =H3C  C ≡≡ CH
Cl
Ans. (c) CH3 CH (d) A =H3C  C == CH2 ;
Cl 
Dilute NaOH is the reagent for aldol OH
condensation. Dilute NaOH process 2Cl2
hν B =H3C  C  CH3
enolate ion from acetophenone which
CHO 
attacks benzaldehyde to give aldol. (X)
O
Ans. (d)
O H2O
PhCH==O + CH3CPh 373 K
Benzaldehyde Acetophenone
OH O 70 Identify compound (A) in the
Dil. NaOH
PhCHCH2CPh following reaction.
[NEET (Oct.) 2020]
O
–H2O CHO
PhCH==CHCPh
(Cis + trans) H2/Pd/BaSO4
A
It is cross aldol condensation or
Claisen-Schmidt reaction or Claisen (a) Benzoyl chloride (b) Toluene
reaction. (c) Acetophenone (d) Benzoic acid
OH

Identify A, X , Y and Z [NEET 2017] 75 The correct structure of the
Therefore, A = CH3  C == CH2 (a) A-methoxymethane, X-ethanoic acid, product A formed in the reaction
O Y-acetate ion, Z-hydrazine [NEET 2016, Phase II]
 (b) A-methoxymethane, X-ethanol, O
B = CH3  C  CH3 Y-ethanoic acid, Z-semicarbazide
H2 (gas, l atmosphere)
(c) A-ethanal, X-Acetaldelyde, A is
72 Of the following which is the Y-but-2-enal, Z-semicarbazone Pd/carbon, ethanol
product formed when (d) A-ethanol, X-acetaldehyde,
cyclohexanone undergoes aldol Y-butanone, Z-hydrazone OH O OH OH
condensation followed by heating? Ans. (c) r
[NEET 2017] (a) (b) (c) (d)
O Aldehydes gives silver mirror test so, ‘X’
may be alcohol which is oxidised by Cu
gives aldehydes. Ans. (b)
(a)
Therefore, In presence of Pd-catalyst, selective
A is acetaldehyde (CH3CHO) reduction of α,β-unsaturated carbonyl is
OH observed as hydrogenation takes place
Cu/573 K
C 2H5OH → CH3CHO of carbon-carbon double bond only.
oxidation
(b) Acetaldehydol
(A ) O O
[Ag(NH3 )2]
O → Silver H2 (gas 1, atmosphere)
OH /D
Tollen's reagent mirror observed Pd/ Carbon, Ethanol
(c)
2
NH
OH 76 Treatment of cyclopentanone
O
O
C
OH/∆ CH3 — CH == CH—C—H O with methyl lithium

(d)
NH
Aldol But-2-en-1-al
(Y)
condensation gives which of the following
O O
2
species?
NH
[CBSE AIPMT 2015]

Ans. (b) O
(a) Cyclopentanonyl anion
Aldehydes and ketones containingα H CH3 — CH == NH—NH—C—NH2 (b) Cyclopentanonyl cation
atoms undergo aldol condensation in Semicarbazone
(Z) (c) Cyclopentanonyl radical
presence of dilute alkali as catalyst and
gives α, β unsaturated compound with (d) Cyclopentanonyl biradical
the elimination ofH2O molecule. 74 The product formed by the reaction Ans. (a)
H H of an aldehyde with a primary amine H
– is α
OH –
–
2 O O O +
(a) Ketone [NEET 2016, Phase I] O + CH3 Li
(b) Carboxylic acid Methyl lithium
– Cyclopentanone +
OH O (c) Aromatic acid
H2O Li
(d) Schiff base –
– O
– OH Ans. (d)
H + CH4
O O s
O O H Lithium
∆ –H2O  + cyclopentanoyl anion
R  C  H + R′  NH2 R  C  N  R′ (Intermediate)
Aldehyde Primary  
amine H H Here, CH3Li abstract is an active proton
from cyclo pentanone forming methane
O r leaving behind an intermediate lithium
(α, β- unsaturated OH2 OH cyclopentanoyl anion.
compound)  
H+
R  C  N  R′ R  C  N  R′ 77 A single compound of the structure is
73 Consider the reactions,    
+ H H H H CH3 CH3
Cu [Ag(NH3)2]
X A –OH ∆ Dehydration –H2O
(C2H6O)
573 K OHC C C
–OH, ∆ r –H+
C H C O
Y R  C== N  R′ R  C==N  R′ H2 H2
O   
H H H obtainable from ozonolysis of
NH2 NH C NH2 Schiff's base which of the following cyclic
Z compounds? [CBSE AIPMT 2015]
Silver mirror observed
H3C H3C Ans. (a) Ans. (*)

(a) CH3 (b) In keto-enol tautomerism keto form Reaction of carbonyl compounds with
should haveα-hydrogen (structure I and II). ammonia derivatives give addition
H3C
CH3 CH3 CH3 CH3 product followed by the elimination
H3C reaction. Slightly acidic medium
CH3
generate a nucleophilic centre for the
(c) (d) I. attack of weak base like ammonia
CH3 derivatives.
CH3 O OH
81 The oxidation of benzene by V2O 5
CH3 CH3
Ans. (a) in the presence of air produces
CH3 II.
1 α CH3 CH3 [CBSE AIPMT 2015]
O3 (a) benzoic anhydride
CH3 Zn,H
2 2 O OH (b) maleic anhydride
CH3 CH3 H γ H (c) benzoic acid
(d) benzaldehyde
OHC1 C C2 β
CH2 CH2 O III. CH3 CH3 Ans. (b)
H α O
H3C CH3 CH3
O OH Air
CHC
O3 O
2 Here, γ-H participates in tautomerism. V2O5
Zn,H2 CHC
H3C 1
O CH3
79 An organic compound X having O
Maleic anhydride
molecular formula C 5H10 O yields
H C CH2 CH CH CHO phenyl hydrazone and gives
1 2 82 Reaction by which benzaldehyde
negative response to the iodoform
CH3 cannot be prepared? [NEET 2013]
test and Tollen's test. It produces
H3C CH3
CH3 n-pentane on reduction. X could be CH3
1 [CBSE AIPMT 2015] (a) + CrO2Cl2 and CS2
O3
Zn,H2
OHC C CH2 (a) pentanal
2 1 followed by H3O+
(b) 2-pentanone
CH3 (c) 3-pentanone COCl
CH2 CHO (d) n-amyl alcohol (b) + H2 in presence of
2 Pd-BaSO4
Ans. (c)
CH3 O
2 Since, the compound X yields phenyl
O3
1 H3C C CH2 hydrazone and gives negative response (c) + CO + HCl in presence of
Zn,H2 to the iodoform test and Tollen’s test , it
CH3 1 anhy. AlCl3
O must contain a C == O group but is
neither a methyl ketone nor an aldehyde.
CH2 CH2 C CH COOH
The structure of X could be
2
O
(d) + Zn / Hg and conc. HCl
78 Given, 
CH3  CH2  C  CH2  CH3 Ans. (d)
CH3 CH3 3-pentanone
CH3 CH3
having molecular formula C5H10O. (a)
2CrO2Cl2
CH3 CS2
CH3
80 Reaction of a carbonyl compound CH3.2CrO2Cl2
CH3 with one of the following reagents
O O O
(I) (II) (III) involves nucleophilic addition Brown
(addition product)
followed by the elimination of
Which of the given compounds CHO
water. The reagents is
can exhibit tautomerism? [CBSE AIPMT 2015] H2O
[CBSE AIPMT 2015]
(a) a Grignard reagent
(a) I and II (b) hydrazine in presence of feebly Benzaldehyde
(b) I and III acidic solution
(c) II and III This reaction is known as Etard
(c) hydrocyanic acid
reaction.
(d) I, II and III (d) sodium hydrogen sulphite
O O Ans. (c)
C Cl  When benzaldehyde is treated with 50%
(b)
Pd/BaSO4, S (a) CH 3CH 2CH 2CCH 3 alkali, it undergoes oxidation to give an
(Boiling xylene) acid salt as well as reduction to give an
O
Benzoyl  alcohol. This reaction is called
chloride CHO (b) CH 3 CH 2 CH 2 C CH 2 CH 2 CH 3 Cannizaro’s reaction.
OH CHO CH2OH
+ HCl (c) (CH3)2C  3½
This reaction is called Rosenmund OC2H5 50% KOH 2
reaction. +
OC2H5
Anhy. AlCl3 (d) (CH3)2C Cl 1 Cl
(c) + CO + HCl 3-hydroxy methyl
OC2H5
chlorobenzene
CHO Ans. (d)
–+ or
1 COOK
+ HCl When carbonyl compounds are treated COO–
with alcohol, they form hemiacetal
The above reaction is known as 2
(hemiketal and acetal/ketal.)
Gattermann-Koch aldehyde synthesis. 3

COOH (CH3)2C ==O+ C2H5OH
HCl
Cl 
Conc. HCl Acetone ethanol
Potassium-3-chloro Cl
(d) + Zn/Hg benzoate
(2-propanone) OH
COCl (CH3)2C
OC2H5 86 Clemmensen reduction of a ketone
Hemiketal
+ H2O is carried out in the presence of
C2H5OH OC2H5
Thus, from the reactants given in option (excess)
(CH3)2C which of the following?
(d) benzaldehyde is not obtained. OC2H5 [CBSE AIPMT 2011]
HCl Ketal
NOTE Formation of hemiketal is a (a) Zn-Hg with HCl
83 CH3CHO and C 6H5CH2CHO can be nucleophilic addition reaction. (b) LIAlH4
distinguished chemically by (c) H2 and Pt as catalyst
[CBSE AIPMT 2012] 85 Predict the products in the given (d) Glycol with KOH
(a) Benedict test reaction, [CBSE AIPMT 2012] Ans. (a)
(b) iodoform test CHO The reducing agent used in Clemmensen
(c) Tollen’s reagent test reduction is Zn-Hg and HCl.

(d) Fehling solution test Zn-Hg /HCl
50% KOH C == O → CH2
Ans. (b)
CH3CHO and C6H5 CH2 CHO both being Cl
aliphatic aldehydes react with Tollen’s – 87 Acetophenone when reacted with a
CH2OH CH2COO
reagent, Fehling solution and Benedict base, C 2H5ONa, yields a stable
solution. So, these reagents cannot be (a) compound which has the structure
used to distinguish them. + [CBSE AIPMT 2008]
CH3CHO due to the presence of  
 O  Cl Cl C CHC
   (a)
 CH — C —  group reacts with NaOH CH2OH OH O
 3  CH3
  (b)
  + CHCH2C
and I2 to give yellow crystals of iodoform   (b)
while C6H5 CH2 CHO does not react with it. OH OH CH3 O
CH3CHO + 3I2 + 4NaOH → CHI3
CH2OH COO– CH3 CH3
+ HCOONa + 3NaI + 3H2O
C6H5 CH2 CHO + I2 + NaOH → (c) CC
+ (c)
No reaction
  OH OH
Thus, CH3CHO and C6H5 CH2 CHO can be Cl Cl
distinguished by iodoform test.
CHCH
CH2OH COO– (d)
84 Acetone is treated with excess of (d) OH OH
ethanol in the presence of + Ans. (a)
hydrochloric acid. The product  
obtained is [CBSE AIPMT 2012] OH OH Aldehydes and ketones withα-hydrogen
atom, when reacted with a base yields
aldol which on heating loses water (c) an alpha-hydroxy aldehyde or ketone Ans. (a)
molecule to giveα, β-unsaturated (d) an alpha, beta unsaturated ester Clemmensen reduction Aldehydes and
aldehydes or ketones. This reaction is Ans. (b) ketones are reduced to the
called aldol condensation reaction. corresponding alkanes by means of
Condensation between two molecules of
C2H5ONa iC2H5O– + Na+ amalgamated zinc and HCl.
an aldehyde or a ketone having atleast
Base one α-hydrogen atom in presence of a Zn-Hg /HCl
C==O +4[H] → CH2 + H2O
C O base to form a β-hydroxy aldehyde or
+ C2H5O
– β-hydroxy ketone is known as aldol
CH3 Base condensation. Aldol condensation are 92 Nucleophilic addition reaction will
divided into two parts one is self aldol be most favoured in
condensation and another is cross-aldol [CBSE AIPMT 2006]
(Abstract the acid hydrogen) condensation, when both molecules are
O O
s same then it is called self aldol and vice 
CH2—C versa. (a) CH3  CH2  CH2 C  CH3
C2H5OH + H H
  (b) (CH3)2 C ==O
O O OH −
H  C C +H C C 3 (c) CH3CH2CHO
(Attacking species)  H  H
(d) CH3CHO
(Nu) H H
CH3 O α -hydrogen Ans. (d)
s H H
—C O + CH2C   O Slow
→ CH3  C  C  C Nu C==O
α β H Nucleophile Carbonyl
OH H compound
CH3 O 3-hydroxy butanal or
b-hydroxy aldehyde O– H+ OH
CCH2C C C
Fast
Nu
– 90 Which one of the following on Tetrahedral Adduct Nu
O
CH3 O
treatment with 50% aqueous intermediate
sodium hydroxide yields the The carbonyl compounds undergo
H
+ C−CHC corresponding alcohol and acid? nucleophilic addition reaction because
[CBSE AIPMT 2007] oxygen is more electronegative than
OH H (a) C 6H5CH2CHO carbon. As such, it withdraws shared
π-electron pair towards itself and gets
CH3 O (b) C 6H5CHO
partial negative charge, therefore
(c) CH3CH2CH2CHO carbon get partial positive charge and
—C CHC O becomes susceptible to nucleophilic
–H2O  attack.
(d) CH3  C  CH3
Aldehydes are more reactive than
Ans. (b) ketones towards nucleophiles. This can
88 A strong base can abstract an Aldehydes which do not have any be explained on the basis of inductive
α-hydrogen from α-hydrogen atom when heated with a effect as well as steric effect. The
[CBSE AIPMT 2008] concentrated solution of NaOH undergo addition of nucleophiles is based upon
(a) alkene (b) amine a simultaneous oxidation and reduction the positive charge present on carbon
(c) ketone (d) alkane (disproportionation) forming a salt of atom of C==O group. In aldehyde
carboxylic acid and alcohol. This
Ans. (c)
reaction is called Cannizaro reaction. C==O group is present with at least
Since the carbonyl carbon is electron 2C6H5 CHO + NaOH → C6H5 CH2OH
deficient, so most susceptible to attack
Benzyl alcohol one alkyl group (except formaldehyde)
by nucleophilic reagents or base. A base − + which has +I-effect (electron donating
increases the acidity of hydrogen atom + C6H5 COONa
effect) and which decreases the positive
attached to theα-C of the ketones or Sodium benzoate
charge of carbon, thereby making the
aldehydes. That’s why α-hydrogen is
attack to nucleophile difficult. The
easily abstracted from ketones by a 91 Reduction of aldehydes and nucleophilic attack becomes more
base, e.g. in aldol condensation reaction,
α-hydrogen atom of aldehyde or ketone
ketones into hydrocarbons using difficult in ketones having minimum of
zinc amalgam and conc. HCl is two alkyl groups.
is abstracted by a strong base.
called [CBSE AIPMT 2007] Hence, by means of attachment of alkyl
groups (due to +I-effect) rate of
89 The product formed in aldol (a) Clemmensen reduction nucleophilic addition decreases. That
condensation is [CBSE AIPMT 2007] (b) Cope reduction means e − density at C-atom decreases,
(a) a beta-hydroxy acid (c) Dow reduction nucleophilic addition reaction increases.
(b) a beta-hydroxy aldehyde or a (d) Wolff-Kishner reduction Order of +I-effect in alkyl group
beta-hydroxy ketone
R R H H OH (a) A = RR′CH2CN, B = NaOH

 CH3 < R  CH2−
< CH—< R C C ==O + HCN C OH
(b) A = RR′ C , B = CH3
R R H H CN COOH
Formaldehyde
Order of nucleophilic addition in given H2O H OH
CN
carbonyl compound is C (c) A = RR′ C , B = CH3
COOH
CH3CHO > CH3  CH2  CHO > (CH3) 2 CO > H COOH
O It is not optically active
CN
 (d) A = RR′C , B =LiAlH4
CH3  CH2  CH2  C  CH3 OH
94 The major organic product formed
from the following reaction Ans. (d)
93 A carbonyl compound reacts with [CBSE AIPMT 2005] In the presence ofLiAlH4 , cyanide group
hydrogen cyanide to form O gives amine by reduction.
(i) CH3NH2 OH
cyanohydrin which on hydrolysis ... is R R
forms a racemic mixture of (ii) LiAlH4 C ==O →
HCN
C
KCN
α-hydroxy acid. The carbonyl (iii) H2O R′ R′ A CN
CH3 Cyanide
compound is [CBSE AIPMT 2006] (a) (b)
(a) acetaldehyde (b) acetone OH NHCH3 R OH
LiAlH (B )
(c) diethyl ketone (d) formaldehyde →
4
C
ONHCH3 NHCH3
(c) (d) R′ CH2NH2
Ans. (a)
OH OH Amine
OH
C==O + HCN C R OH
Ans. (b) Hence, A is C and B is
CN O CH3NH2 R′ CN
H2O OH
C Ketone LiAlH4
NCH3 [H]
COOH
(i) LiAlH4 97 In this reaction,
(It is α-hydroxy acid) Schiff base (ii) H2O
CH3CHO + HCN→ CH3CH(OH)CN
In this reaction, by the complete NHCH3 H⋅ OH
hydrolysis of cyanide gives acid and or → CH3CH(OH)COOH
partial hydrolysis gives amide. NHCH3
2° amine an asymmetric centre is
If it is racemic mixture, therefore such
C-atom must be asymmertic carbon generated. The acid obtained
95 Which one of the following can be
atom. would be [CBSE AIPMT 2003]
oxidised to the corresponding
CH3 CH3 OH (a) 50% D + 50% L-isomer
carbonyl compound ?
C==O + HCN C [CBSE AIPMT 2004] (b) 20% D + 80% L-isomer
H H CN (c) D-isomer
Acetaldehyde (a) 2-hydroxy propane
CH3 CH3 (b) Ortho-nitro phenol (d) L-isomer
| | Ans. (a)
H2O (c) Phenol
HCOH + HO—C—H
| | (d) 2-methyl-2-hydroxy propane Lactic acid obtained in the given
COOH COOH Ans. (a) reaction is an optically active compound
d- l- due to the presence of chiral C-atom. It
2-hydroxy propane or secondary alcohol exits as d and l-forms whose
Racemic mixture is oxidised into propanone ratio is 1:1.
CH3 CH3 OH (corresponding because in 2-hydroxy CH3
C==O + HCN C propane, secondary alcoholic group is
C ==O + HCN→
CH3 CH3 present and it is oxidised into ketone).
CN H
Acetone CH3 CH3
[O]
H2O CH3 OH CH3  CH  CH3 → CH3  C  CH3  
C |  H  C  OH + HO  C  H
CH3 COOH OH O  
2-hydroxy propane Propanone CN CN
It is not optically active (Ketone)
racemic mixture is nor formed (2° alcohol) 50% L-isomer 50% D-isomer
Cyanohydrine
C2H5 C2H5 OH 96 A and B in the following reactions
C==O + HCN C are [CBSE AIPMT 2003]
C2H5 C2H5 CN 98 Polarisation of electrons in acrolein
HCN/
R — C — R ′ → A →
Diethyl ketone B
C2H5 OH may be written as
KCN
H2O
C  [CBSE AIPMT 2000]
δ+ δ−
C2H5 COOH O OH (a) CH 2 ==CH —CH==O
It is not optically active R —C
R′ CH2NH2 δ+ δ+
(b) CH 2 ==CH —CH==O
δ+ δ+
CH3  COCH2  CH2 CH3 + 3I2 + 4NaOH → (c) oxidation of tertiary alcohol
(c) CH 2==CH —CH==O
δ– δ+ CHI3 ↓ + CH3CH2 CH2 COONa (d) reaction of acid halide with alcohols
(d) CH2 ==CH — CH ==O Iodoform + 3NaI +3H2O Ans. (c)
(yellow ppt.)
Ans. (a) By oxidation of tertiary alcohol with
CH3 CHO + 3I2 +4NaOH —→ stronger oxidising agents, ketones may
In CH2 ==CH— CHO due to – M-effect of
—CHO group, polarisation of electron CHI3 ↓ + HCOONa + 3NaI + 3H2O be formed along with carboxylic acid.
Iodoform 4 [O]
takes place as follows : (yellow ppt) → CH3COCH3 + CO2 + 2H2O
+ – 2 I (CH3) 3 COH 8 [O]
CH2==CHC==O CH2—CH= CO C2H5OH → CH3CHO → CH3COOH + 2CO2 + 3H2O
| |
H H CH3CHO+ 3I2 + 4NaOH → CHI3 ↓
Iodoform 104 (CH3 ) 3 C  CHO does not undergo
99 During reduction of aldehydes with + HCOONa + 3NaI+ 3H2O aldol condensation due to
hydrazine and potassium But due to absence of CH3  CH [CBSE AIPMT 1996]
hydroxide, the first is the formation  (a) three electron donating methyl
of [CBSE AIPMT 2000]
OH groups
or CH3  C == O group in 3-pentanone, it (b) cleavage taking place between
(a) R—CH==N—NH2 
—C—CHO bond
(b) R—C ≡≡N
does not give iodoform. (c) absence of alpha hydrogen atom in
(c) R—C —NH2 O the molecule
 
CH3  CH2  C  CH2  CH3 + I2 + NaOH (d) bulky (CH3) 3 C — group
O
(d) R—CH==NH 3-pentanone Ans. (c)
→ No reaction. CH3
Ans. (a)

R CH3 — C — CHO does not undergo aldol
KOH 102 1-phenyl ethanol can be prepared 
C ==O + N H2 —NH2 →
H by the reaction of benzaldehyde CH3
Aldehyde Hydrazine
with [CBSE AIPMT 1997] condensation because it does not
R (a) methyl bromide contain α-hydrogen atom.
C ==N —NH2 + H2O (b) ethyl iodide and magnesium
H (c) methyl iodide and magnesium 105 Acetone reacts with iodine (I 2 ) to
Aldehyde hydrazone (d) methyl bromide and aluminium
form iodoform in the presence of
bromide
[CBSE AIPMT 1995]
100 Aldol condensation will not take Ans. (c)
place in (a) CaCO 3 (b) NaOH
1-phenyl ethanol is prepared by reacting (c) KOH (d) MgCO 3
[CBSE AIPMT 1999]
benzaldehyde with methyl magnesium Ans. (b)
(a) HCHO (b) CH3CHO iodide (mixture of methyl iodide and
(c) CH3COCH3 (d) CH3CH2CHO O
magnesium as )

Ans. (a) Dry ether CH3  C  CH3 + 3I2 + 4NaOH →
CH3I+ Mg → CH3MgI Acetone
Aldol condensation in aldehydes is due − +
to presence ofα-hydrogen atoms. Those C6H5 CHI3 + CH3COONa + 3NaI + 3H2O
aldehydes which does not have CH3  MgI + C == O → Iodoform
α-hydrogen atom like HCHO, does not H
give aldol condensation reaction. C6H5 106 Which of the following compounds
CH — O—MgI will undergo self aldol
101 Iodoform test is not given by CH3 condensation in the presence of
[CBSE AIPMT 1998]
C6H5 cold dilute alkali?
(a) 2-pentanone HO
→
2
HOHC [CBSE AIPMT 1994]
(b) ethanol –Mg(OH)I
CH3 (a) CH2 ==CH  CHO
(c) ethanal (1-phenyl ethanol) (b) CH ≡≡C—CHO
(d) 3-pentanone (c) C 6H5CHO (d) CH3  CH2CHO
Ans. (d) 103 Ketones[R —C—R 1 ], where Ans. (d)
The compounds which contain either ||
O Only those aldehyde undergoes aldol
CH3  CO  group or CH3 —CH group condensation which haveα-hydrogen, so
give positive  R = R 1 = alkyl group, can be CH3CH2 CHO give this reaction because it
OH
iodoform test. In 2-pentanone, obtained in one step by contains α-hydrogen atom. Aldol
(CH3CH2 CH2 COCH3), CH3CHO and C2H5OH, [CBSE AIPMT 1997] condensation proceed in presence of
required groups are present, thus they (a) hydrolysis of esters strong base. Aldol condensation are
give iodoform as follows divided into two parts one is self aldol
(b) oxidation of primary alcohol
condensation and another is cross-aldol So, its IUPAC name is oxygen atom. The actual structure may
condensation. When both molecules are 3,3-dimethyl-2-butanone be represented as
same called as self aldol and vice versa. δ+ δ−
(Colourless liquid) (Camphor odour) C==O or  O
C --------
107 Aldehydes and ketones will not 110 (CH3 ) 2 C==CHCOCH3 can be Consequently, the carbonyl carbon is
form crystalline derivatives with positively charged while the oxygen is
[CBSE AIPMT 1994] oxidised to (CH3 ) 2 C==CHCOOH by negatively charged. The positively
[CBSE AIPMT 1993] charged carbon is easily attacked by a
(a) sodium bisulphite
(a) chromic acid (b) NaOI nucleophilic reagent (Nu− ).
(b) phenyl hydrazine
(c) semicarbazide hydrochloride (c) Cu at 300°C (d) KMnO 4 Slow O–
C == O + Nu– → C
(d) dihydrogen sodium phosphate Ans. (b) Nu
Aldehyde Intermediate
Ans. (d) Haloform reaction, or ketone
O
Dihydrogen sodium phosphate  sp2 hybridisation planar structure.
(NaH2PO 4 ) does not react with (CH3)2 C==CHCOCH3 contains CH3 — C — H + OH
aldehydes and ketones because → C
unit so it can be oxidised to fast Nu
NaH2PO 4 does not have any lone pair (CH3)2 C==CH— COOH by NaOI. Addition product
of electron on phosphorus atom, so it O sp3 hybridisation tetrahedral structure.
cannot act as a nucleophile.  NaOI
CH3  C == CH  C  CH3 →
 113 The reagents which can be used to
108 Benzaldehyde reacts with ethanolic CH3 distinguish acetophenone from
KCN to give [CBSE AIPMT 1994]
CH3  C == CH  COOH + CHI3 benzophenone is (are)
(a) C 6H5CHOHCN  [CBSE AIPMT 1990]
(b) C 6H5CHOHCOC 6H5 CH3
(a) 2,4-dinitrophenyl hydrazine
(c) C 6H5CHOHCOOH 111 In which of the following the (b) aqueous solution of NaHSO3
(d) C 6H5CHOHCHOHC 6H5 number of carbon atoms does not (c) Benedict reagent
Ans. (b) remain same when carboxylic acid (d) I2 and Na2 CO3
H H is obtained by oxidation? Ans. (d)
[CBSE AIPMT 1992]
C O C O The structures of acetophenone and
(a) CH3COCH3 (b) CCl3CH2CHO benzophenone are
(c) CH3CH2CH2OH (d) CH3CH2CHO O
KCN Ans. (a)
+
C2H5OH
Ketones are not easily oxidised. CH3C
OH O However, under drastic conditions or Acetophenone O
with powerful oxidising agents such as
HCC conc. HNO3, KMnO4 / H2SO4 or C
K2 Cr2O7 / H2SO4 , cleavage of
carbon-carbon bond takes place giving a Benzophenone
mixture of carboxylic acids having less When acetophenone containing
number of carbon atoms than the O
Benzoin original ketone. 
(hydroxy ketone) O CH3  C  unit, is treated withI2 and
This reaction is also called benzoin  [O] Na2 CO3 it forms yellow precipitate of
condensation. Benzoin is chiral and it CH3  C  CH3 → HCOOH
Acetone conc. HNO3 Formic acid CHI3 whereas benzophenone does not
exists as a pair of enantiomer, i.e. give this test.Acetophenons gives
R-benzoin and S-benzoin. + CH3COOH iodoform test due to presence of
Acetic acid
COCH3 group.
109 Pinacolone is [CBSE AIPMT 1994] 112 Acetaldehyde reacts with
HCl
(a) 2,3-dimethyl-2,3-butanediol
[CBSE AIPMT 1991]
114 3CH3COCH3 →
(a) only electrophiles –H 2O
(b) 3,3-dimethyl-2-butanone (A)
(b) only nucleophiles
(c) 1-phenyl-2-propanone (CH3 ) 2 C==CH—CO—CH==C(CH3 ) 2
(c) only free radicals
(d) 1,1-diphenyl-2-ethanediol (B)
(d) both electrophiles and nucleophiles
Ans. (b) This polymer (B) is obtained when
Ans. (b)
The structure of pinacolone is
The carbonyl group is highly reactive acetone is saturated with HCl gas,
CH3 O polar group. It is polarised due to the B can be [CBSE AIPMT 1989]
higher electronegativity of oxygen in (a) phorone
CH3CCCH3 (b) formose
4 3 2 1 comparison to carbon. As a result, the
electrons present between carbon and (c) diacetone alcohol
CH3
oxygen are more attracted towards (d) mesityl oxide
Ans. (a) CH2 O TOPIC 4

O 116 O CH2 , the

CH3
C == O + H2 CH  C  CH H2 CH2 O Carboxylic Acids
CH3
shown polymer is obtained when a
CH3 Dry HCl carbonyl compound is allowed to
+ O == C → 119 Which of the following acid will
CH3 –2H2O stand. It is a white solid. The form an (i) anhydride on heating
O polymer is [CBSE AIPMT 1989]
and (ii) acid imide on strong heating
CH3  CH3 (a) trioxane
C == CH  C  CH == C with ammonia? [NEET (Oct.) 2020]
CH3 CH3 (b) para-formaldehyde
2,6-dimethylhepta-2,5-diene-4-one (c) formose COOH
(Phorone) (B) COOH
(d) meta-aldehyde
Phorone is self condensation product of (a) (b)
Ans. (a)
acetone. It can also be obtained from COOH COOH
certain camphor compound. Phorone is When formaldehyde is allowed to
COOH OH
combustible when exposed to heat or stand at room temperature, it slowly
flame. undergoes, polymerisation and forms
a white solid called (c) (d)
CH3
meta-formaldehyde or trioxane. COOH
CH2 CH2 COOH

115 , the compound O O O O
Allowed to Ans. (a)
stand
H3C CH3 CH2 CH2 H2C CH2 An α, β-dicarboxylic acid with same-side
O O (syn) orientation of — COOH group is able
meta-formaldehyde
describes a condensation polymer (Trioxane)
to form anhydride (cyclic) and imide
which can be obtained in two (cyclic).
ways, either treating 3 molecules 117 Formalin is an aqueous solution of Among isomeric benzene dicarboxylic
of acetone (CH3COCH3 ) with conc. acids, only benzene-1,2-dicarboxylic acid
[CBSE AIPMT 1988]
(phthalic acid) will respond to the below
H2SO 4 or passing propyne (a) fluorescein (b) formic acid reactions.
(CH3 —C ≡≡ CH) through a red hot (c) formaldehyde (d) furfuraldehyde
O O
tube, the polymer is Ans. (c)
[CBSE AIPMT 1989] C C
The 40% solution of formaldehyde in
(a) phorone (b) deacetonyl alcohol OH Heating
water is sold in market under the name O
(c) mesityl oxide (d) mesitylene O –H2O
of formalin. Formaldehyde in the form of
C H C
Ans. (d) formalin (40% formaldehyde, 8%
methanol and 52% water) is used for O O
When acetone is treated withH2SO4 ,
preserving biological specimens. Phthalic anhydride
three molecules get condensed to give
mesitylene, Formaline solution also used as a O
disinfectants and commonly used in
CH3 COOH Strong C
hardeness and nail varnish.
heating
C O H2 HN
CH H2 NH3
O 118 If formaldehyde is heated with COOH –H3O C
H2SO4 (conc.)
H2 KOH, then we get
–3H2O Phthalic acid
CH O [CBSE AIPMT 1988] O
CH3 (a) methane
C C –H2O
CH3 O H2 HC CH3 C (b) methyl alcohol O
HC CH (c) ethyl formate
(d) acetylene C
C C—CH3
CH3 CH Ans. (b) NH
Mesitylene When α-hydrogen is absent in carbonyl C
CH3 group, those compound gives cannizaro
CH Red hot tube reaction. O
C Phthalimide
HC C This reaction show disproportionation.
CH3 CH3
C The oxidation product is salt of 120 The major product of the following
CH3 CH carboxylic acid and reduced product is
C reaction is : [NEET (National) 2019]
HC CH alcohol.
KOH (conc. ) COOH
C C HCHO + HCHO → CH3OH Strong heating
H3C CH3 + NH3
C Methyl alcohol
H COOH
Mesitylene + HCOO–K+
O The hydrogen bonds are not Ans. (a)

COOH completely broken in the vapour state. Electron withdrawing group attach to
(a) NH (b) In fact mostly carboxylic acids exist as the benzene ring increases the reactivity
NH2
dimer in the vapour state or aprotic towards nucleophilic sustitution
solvent. –
reaction. Since, NO2 group is strong
O δ δ+ electron withdrawing group. Hence, in
O H O
NH2 COOH basic medium ester containing NO2
R C H-bonds C R
(c) (d) group will hydrolysed most easily.
O H+ O–
δ δ
NH2 CONH2 OCOCH3
Ans. (a) 122 The correct order of strengths of
Carboxylic acids react with ammonia to the carboxylic acids O2N
give ammonium salt which on further [NEET 2016, Phase II]
heating at high temperature give
COOH COOH 124 In a set of reactions, ethyl benzene
amides. Further, on strong heating,
ammonia is removed from phthalamide yielded a product D.
and phthalimide is formed. O [CBSE AIPMT 2010]
I II
The reaction takes place as follows : CH2CH3
COOH KMnO4
– + Br2
COOH COONH4 B
O
is KOH FeCl3
+ NH3
– +
COOH COONH4 III C2H5OH
Phthalic Ammonium (a) I > II > III (b) II > III > I C D
H+
acid phthalate
(c) III > II > I (d) II > I > III D would be
O ∆ –2H2O Ans. (b) CH2 CHCOOC2H5
C CONH2 Key Idea Order of strengths of the given (a)
Strong heating carboxylic acids can be determined by the Br
NH – NH3 concept of I-effect.
C CONH2 Br
Phthalamide The oxygen atom present in the ring
O shows I-effect. As the distance between
Phthalimide oxygen and COOH group increases,
(b)
–I-effect of oxygen decreases.
121 Carboxylic acids have higher boiling Thus, corresponding carboxylic acid will Br
points than aldehydes, ketones and show less acidic nature.
CH2COOC2H5
even alcohols of comparable The correct order of strengths of the
carboxylic acids is COOH
molecular mass. It is due to their
[NEET 2018] COOH COOH COOH
(a) more extensive association of > >
(c)
carboxylic acid via van der Waals’
force of attraction II III I OC2H5
More-effect Less I-effect No I-effect
(b) formation of carboxylate ion (Most acidic) (Moderately (Least acidic) COOC2H5
(c) formation of intramolecular acidic)
H-bonding
(d) formation of intermolecular 123 Which one of the following esters (d)
H-bonding gets hydrolysed most easily under Br
Ans. (d) alkaline conditions?
Ans. (d)
Carboxylic acids have higher boiling [CBSE AIPMT 2015]
points than aldehyde, ketones and Alkaline KMnO4 converts complete
OCOCH3
carbon chain (that is directly attached to
even alcohols of comparable (a) benzene nucleus) to COOH group. Br2
molecular mass because of the extent
of intermolecular-hydrogen bonding O2N in the presence of halogen carrier
OCOCH3 causes bromination by electrophilic
with water, due to which they exist as
associated molecules. (b) substitution reaction and ethyl alcohol in
H3CO acidic medium results in esterification.
O
OCOCH3 CH2CH3 COOH
H O
C δ+ (c)
R O H C R KMnO4 Br2/FeCl3
H OCOCH3
δ– KOH
O δ– δ+ O O δ–
C O H H (d)
R δ+ (m-directing)
Cl B
COOC2H5 Cl – < RCOO– < R ′O– > NH2–
COOH The structure of D would be
Thus, order of reactivity is [CBSE AIPMT 2006]
C2H5 OH RCOCl > (RCO)2 O > RCOOR ′ (a) CH3CH2CH2NH2 (b) CH3CH2CONH2
H+ Acyl chloride Acid anhydride Ester
(c) CH3CH2NHCH3 (d) CH3CH2NH2
Br Br >RCONH2
C
D Amide Ans. (d)
127 Which of the following represents For the reaction,
125 Propionic acid with Br 2 —P yields a the correct order of acidity in the SOCl2
given compounds? CH3CH2 COOH → CH3 CH2 COCl
dibromo product. Its structure [CBSE AIPMT 2007]
– SO2
–HCl
(a) FCH2 COOH > CH3COOH > BrCH2 COOH
A B
(a) CH2Br CHBr COOH > ClCH2 COOH NH
3 4KOH + Br
Br → CH3CH2 CONH2 →
2
(b) BrCH2 COOH > ClCH2 COOH > – HCl (–2KBr, –K 2 CO3 ,
 FCH2 COOH > CH3COOH C –2H2 O)
(b) H  C CH2COOH
(c) FCH2 COOH > ClCH2 COOH > BrCH2 COOH
 CH3CH2NH2
Br > CH3COOH
D
(d) CH3COOH > BrCH2 COOH > ClCH2 COOH
(c) CH2Br  CH2  COBr (Ethyl amine)
< FCH2 COOH
Br Hence, it is also called Hofmann
Ans. (c)
 bromamide degradation reaction.
(d) CH3  C  COOH The acidity of halogenated acid
 increases with increase in Hence, compound ‘D’ is
Br electronegativity of the halogen present. CH3  CH2  NH2 .
The electronegativity of halogen Hofmann bromamide reaction degrade
Ans. (d)
decreases in order asF > Ce > Br. the one C in amine product from amide
H Br
 Br2 /P  Therefore correct order of given
CH3  C  COOH → CH3  C  COOH compounds is 130 In a set of reactions, acetic acid
−2HBr
  FCH2 COOH > ClCH2 COOH > BrCH2 COOH yielded a product D.
H Br
> CH3COOH SOCl2 Benzene
Propionic acid CH3COOH A anhy. AlCl3
B
Carbonylic acids reacts with Cl2 or Br2 in
presence of red P to give exclusively
128 Self condensation of two moles of HCN HOH
C D
α-chloro or α-bromo acids. ethyl acetate in the presence of
sodium ethoxide yields The structure of D would be
This reaction is called [CBSE AIPMT 2005]
Hell-Volhard-Zelinsky (HVZ) reduction. [CBSE AIPMT 2006]
This reaction is example of (a) ethyl butyrate (b) acetoacetic ester OH
α-H-substitution. |
(c) methyl acetoacetate CCOOH
(d) ethyl propionate (a) |
126 The relative reactivities of acyl CH3
Ans. (b)
compounds towards nucleophilic COOH
On condensation, two moles of ethyl |
substitution are in the order of acetate in the presence of sodium CH2 CCH3
[CBSE AIPMT 2008] ethoxide, gives ethyl acetoacetate (b) |
(a) acyl chloride > acid anhydride > ester OH
(ester). This condensation is an example
> amide of Claisen condensation because it is
(b) ester > acyl chloride > amide > acid possible in those ester which have OH
|
anhydride α-hydrogen atom. CH2 CCH3
(c) acid anhydride > amide > ester > acyl O (c) |
chloride  CN
CH3  C O  C2H5 + H  CH2 COOC2H5
(d) acyl chloride > ester > acid anhydride CN
> amide O |
NaOC2H5  CCH3
Ans. (a) → CH3C CH2 COOC2H5 + C2H5OH (d) |
In acyl compounds (i.e. acyl chloride, OH
Ethyl acetoacetate
acid anhydride, ester and amide) RCO— (ester)
Ans. (a)
group is same, thus reactivity depends
upon the nature of group Z (i.e. Cl − , 129 In a set of reactions propionic acid SOCl2
CH3COOH CH3COCl
RCOO− , R ′O − ,NH2– , etc.) yielded a compound D.
A
If group Z is a weak base, then it is a SOCl NH COCH3
strong leaving agent and its reactivity CH3CH2COOH →
2
B →3
C Benzene
KOH
towards nucleophilic substitution is → D Anhy. AlCl3
high. Br2
The order of basic nature of Z groups is B
OH Ans. (d)
COCH3
H2 O
C—CH3 R  COOR ′ → R  COOH + R ′OH
HCN (i) C2H5MgBr
C6H6 LiAlH4 / ether
CN Anhy. AlCl3 (ii) Ether hydrolysis
R — CH2OH + R ′OH
C
OH B C6H5 C2H5 According to the above equation, it is
C clear that reduction of hydrolysed
C—CH3 CH3 OH product of ester byLiAlH4 gives two
2HOH alcohols.
C
COOH
OH 136 Which one of the following esters
D 133 In the following reaction, product P
C—COOH cannot undergo Claisen
is
or
self-condensation ?
CH3 H [CBSE AIPMT 1998]
R —C —Cl → 2
P
Pd -BaSO 4 (a) CH3CH2CH2CH2COOC2H5

131 Which one of the following orders O (b) C 6H5COOC2H5
[CBSE AIPMT 2002] (c) C 6H5CH2COOC2H5
of acidic strength is correct ?
[CBSE AIPMT 2003] (a) RCH2OH (b) RCOOH (d) C 6H11CH2COOC2H5
(c) RCHO (d) RCH3
(a) RCOOH > HOH > HC ≡≡ CH > ROH Ans. (b)
(b) RCOOH > HC ≡≡ CH > HOH > ROH Ans. (c)
The ester which containsα-hydrogen
(c) RCOOH >ROH > HOH > HC ≡≡ CH The given reaction is Rosenmund atom undergoes Claisen-self
reaction
(d) RCOOH > HOH > ROH > HC ≡≡ CH condensation :
H2
Ans. (d) R —C— Cl → R — C—H + HCl (a) CH3(CH2)3 COC2H5 + HCHCOOC2H5
Pd -BaSO4 |
Carboxylic acid is stronger than alcohol   O CH2CH2CH3
and water because after removal of O O
( P) Claisen
proton, carboxylate ion is stabilised by
Condensation
resonance. Hence, correct order of acid
strength is 134 Benzoic acid may be converted into CH3CH2CH2CH2CCHCOOC2H5
ethyl benzoate by reaction with 
RCOOH > HOH > ROH > HC ≡≡ CH O CH2CH2CH3+C2H5OH
Which is based upon the rate of donation [CBSE AIPMT 2000]
(a) sodium ethoxide (b) C6H5 COOC2H5 + C6H5 COOC2H5
of proton or strength of base, thus order
(b) ethyl chloride No reaction, because for Claisen
of basic strength is
– – condensation an ester with
C ≡≡ CH > R — O > OH– > RCOO– (c) dry HCl, C2H5OH α-hydrogen atoms is required.
O– (d) ethanol
O (c) C6H5CH2CO OC2H5 + H CHCOOC2H5
C Ans. (c) 
—
—
—C —
C6H5
—
Ethyl benzoate is prepared by reacting

—
O
O– Claisen
benzoic acid and ethanol in the presence C6H5CH2COCHCOOC2H5
Resonating structures of carboxylate ion Condensation
of dry HCl. This reaction is known as 
esterification reaction. C6H5
132 In a set of the given reactions, Dry
acetic acid yielded a product C. C6H5 COOH + C2H5OH C6H5 COOC2H5 (d) C6H11CH2CO OC2H5 + HCHCOOC2H5
C H Benzoic acid Ethanol

3HCl
Ethyl benzoate

6 6 C6H11
CH3COOH + PCl 5 → A → B + H2O Claisen
anhy. AlCl 3 Condensation
This reaction proceed with equilibrium.
C H MgBr
2 5 C6H11CH2COCHCOOC2H5 + C2H5OH
→ C Therefore, H2O continuously removed 
Ether
from reaction for preparation of ester C6H11
Product C would be product.
[CBSE AIPMT 2003] 137 An ester (A) with molecular formula
(a) CH3CH(OH)C 6H5 135 Reduction by LiAlH4 of hydrolysed
C 9 H10 O 2 was treated with excess of
C2H5 product of an ester gives
CH3MgBr and the complex so
(b) CH3  C(OH) C 6H5 (a) two acids
formed was treated with H2SO 4 to
(b) two aldehydes give an olefin (B). Ozonolysis of (B)
(c) CH3CH(OH)C2H5
(c) one molecule of alcohol and gave a ketone with molecular
(d) CH3COC 6H5
another of carboxylic acid formula C 8H8O which shows
Ans. (b)
(d) two alcohols positive iodoform test. The
CH3COOH+ PCl 5 → CH3COCl structure of (A) is [CBSE AIPMT 1998]
A
(a) C 6H5COOC2H5 139 An ester is boiled with KOH. The (c) glycerol is heated with oxalic acid at
(b) C 6H5COOC 6H5 373 K
product is cooled and acidified with
(d) acetaldehyde is oxidised withK2 Cr2O7
(c) H3CCOOC 6H5 conc. HCl. A white crystalline acid and H2SO4
(d) p -H3COC 6H4COCH3 separates. The ester is
Ans. (c)
COOH
Glycerol
OMgBr (a) methyl acetate (b) ethyl acetate  → == HCOOH + CO2 ↑
CH3MgBr  (c) ethyl formate (d) ethyl benzoate COOH Heat 373K Formic acid
C6H5COOC2H5 C6H5COC2H5 Oxalic acid
A  Ans. (d)
CH3
KOH 143 Among acetic acid, phenol and
–(C2H5O)MgBr
C6H5 COOC2H5 → C6H5 COOK+
Boiling
Ethyl benzoate n-hexanol which one of the
OMgBr O + C2H5OH following compound will react with
 CH3MgBr ||
C6H5CCH3 C6H5CCH3 H+ /H O NaHCO 3 solution to give sodium
 C6H5 COOK →
2
C6H5 COOH ↓ salt and CO 2 ? [CBSE AIPMT 1993, 99]
CH3 Benzoic acid
(white precipitate) (a) Acetic acid
H2O
(b) n-hexanol
OH 140 Schotten-Baumann reaction is a (c) Acetic acid and phenol
 Conc. H2SO4 reaction of phenols with (d) Phenol
C6H5CCH3 C6H5CCH2
 –H2O [CBSE AIPMT 1994] Ans. (a)

CH3 CH3 (a) benzoyl chloride and NaOH +
CH3COOH + NaHCO3 → CH3COON a
(B) (b) acetyl chloride and NaOH Sodium
Acetic acid
carbonate
O3/H2O (c) salicylic acid and conc. H2 SO 4 + H2O + CO2 ↑
C6H5C==CH2 C6H5CCH3
 || (d) acetyl chloride and conc. H2 SO 4
CH3 O Ans. (a) 144 Sodium formate on heating yields.
B (C8H8O) [CBSE AIPMT 1993]
Schotten-Baumann reaction
(a) Oxalic acid and H2
I Aq NaOH .
C6H5 COCl + C6H5OH →
2
C6H5CCH3 NaOH CHI3 + C6H5COONa (b) Sodium oxalate and H2
| Iodoform pyridine
O (c) CO2 and NaOH
C6H5 COOC6H5 + HCl (d) Sodium oxalate
138 Consider the following 141 The preparation of ethyl Ans. (b)
transformations acetoacetate involves COONa
+
CaCO3 HCOONa
Heat Heat
→ + H2 ↑
CH3COOH → A → B [CBSE AIPMT 1994] +  +
HCOONa
I2 (a) Wittig reaction Sodium formate
CO ONa
Hydrogen
→ C The molecular formula of (b) Cannizaro’s reaction
Sodium
NaOH oxalate
C is (c) Reformatsky reaction
[CBSE AIPMT 1996]
OH (d) Claisen condensation 145 Benzoic acid gives benzene on
 Ans. (d) being heated with X and phenol
(a) CH3  C  CH3 (b) ICH2 COCH3 gives benzene on being heated with
Claisen condensation

I O Y. Therefore, X and Y are respectively
 –
C2 H5 ONa+ [CBSE AIPMT 1992]
(c) CHI3 (d) CH3I CH3 C OC2H5 + HCH2 COOC2H5 →
(a) sodalime and copper
Ans. (c) O
(b) Zn dust and NaOH
CH COO
CaCO 3 
2CH3COOH → 3 Ca CH3 C CH2 COOC2H5 + C2H5OH (c) Zn dust and sodalime
CH3COO (d) sodalime and zinc dust
Ethyl acetoacetate
A
Ans. (d)
Heat
→ Na2 CO3 + H2O 142 Formic acid is obtained when COOH
– CaCO 3
[CBSE AIPMT 1994]
2 I +NaOH
+ CHI3 ← CH3COCH3 (a) calcium acetate is heated with conc. NaOH + CaO
C Acetone H2SO4 Decarboxylation
B
(b) calcium formate is heated with
+ CH3COONa calcium acetate Benzoic acid Benzene
OH CO — NH (i) Methanoic acid

CH2 C == O
CO — NH
(ii) Ethanoic acid
Barbituric acid
Zn (iii) Propanoic acid
Dust
147 Among the following the strongest (iv) Butanoic acid
Phenol acid is [CBSE AIPMT 1988] (a) (i) > (ii) > (iii) > (iv) (b) (ii) > (iii) > (iv) > (i)
Here x = NaOH + CaO (soda line) (a) CH3COOH (b) CH2ClCH2COOH (c) (i) > (iv) > (iii) > (ii) (d) (iv) > (i) > (iii) > (ii)
y = Zn dust (c) CH2ClCOOH (d) CH3CH2COOH Ans. (a)
Ans. (c) The correct order of acidic strength is
146 The compound formed when Inductance effect distance depending methanoic acid > ethanoic acid >
malonic acid is heated with urea, is factor. It decreases rapidly with propanoic acid > butanoic acid because
[CBSE AIPMT 1989] distance. Therefore, as the distance of the +I–effect of alkyl group increases in
(a) cinnamic acid (b) butyric acid Cl-atom increases the acidic character the order.
(c) barbituric acid (d) crotonic acid decreases. CH3 < C2H5 < C3H7 < C4H9
Ans. (c) − I - effect (EWG)
Acidic Nature ∝
COOH H2N
148 Which of the following represent +I - effect (ERG)
Heat
CH2 + C == O → the correct decreasing order of
COOH H2N −H2 O −I-effect increases hence, acidic nature
Malonic acid
acidic strength of following? increases.
Urea
[CBSE AIPMT 1988]
25
Organic Compounds
Containing Nitrogen
TOPIC 1 NH2 NH2
Aliphatic Amines  
CH3  C  CH2 CH2 CH3,
(c) CH3 C C H2CH2CH3

01 Reaction of propanamide with 
CH3
CH3
ethanolic sodium hydroxide and 1° amine
CH3
bromine will give [NEET (Oct.) 2020]  CH3
(a) ethylamine (b) methylamine (d) CH3 C  CH  NH2 
CH3  C  CH  NH2
(c) propylamine (d) aniline  
 
Ans. (a) CH3 CH3
CH3 CH3
O Ans. (a) 1° amine
NaOH-C2H5OH Secondary amines on reaction with Thus, option (a) is correct.
CH3CH2 C NH2 Hinsberg’s reagent (benzene sulphonyl
Br2
Propanamide
(No. of C-atoms =3) chloride) forms N,N-dialkyl benzene 03 The correct order of the basic
sulphonamide. strength of methyl substituted
CH3CH2 NH2 + Na2CO3+NaBr The product formed is not acidic as no amines in aqueous solution is
Ethylamine (1°-amine) H-atom is attached to N thus it is
(No. of C-atoms =2) [NEET (National) 2019]
insoluble in alkali.
(a) (CH3) 3N > CH3NH2 > (CH3)2 NH
It is Hofmann bromamide reaction The reaction of 2º amine given in option
(a) takes place as follows: (b) (CH3) 3N > (CH3)2 NH > CH3NH2
through which an acid amide degrades
into an one carbon less primary (1°) (c) CH3NH2 > (CH3)2 NH > (CH3) 3N
O
amine. (d) (CH3)2 NH > CH3NH2 > (CH3) 3N
Here, the carbon atom of the amide —S—Cl+CH3—CH—NH—CH—CH3 Ans. (d)
 O 
   O CH3 CH3 Basic strength of methyl substituted
group   C NH2  gets decarboxylated 2º amine amines in aqueous solution depends upon
  the ease of formation of cation by
  O CH3 accepting a proton from the acid.
 
H H
in the form of carbonate salt (Na2 CO3). —SNCHCH3 + HCl
+ +
RN +H RNH
O H3C— CH
02 The amine that reacts will H H
CH3
Hinsberg’s reagent to give an alkali The basic strength can be decided by
insoluble product is On the other hand, 1° amines react with
both inductive effect and solvation
[NEET (Odisha) 2019] Hinsberg’s reagent to yield N-alkyl
effect of alkyl group. In aqueous phase,
benzene sulphonamide which is soluble +
(a) CH3  CH NH  CH CH3 in alkali and 3° amines do not react with the substitutedNH4 cations get
  C6H5SO2 Cl. The remaining options stabilised not only by electron releasing
CH3 CH3 contain 1° and 3° amines. effect of alkyl group (+ I) but also by
solvation with water molecules. Greater
CH2 CH3
CH2CH3 the size of ion, lesser will be solvation
 and less stabilised is the ion. The order is
 CH3CH2  N  CH2 CH3,
(b) CH3 CH2 N CH2C H3 as follows :
3° amine
O
Inductive effect  06 Consider the reaction
s
(CH3) 3N > (CH3)2 (NH) > (CH3)NH2 Step III CH3  C N  Br → CH3CH2CH2Br + NaCN →
H O
H3C H----OH2 CH3CH2CH2CN + NaBr
+ +  •• s
H3C—N—H----OH2 > N This reaction will be the fastest in
CH3  C N •• + Br
H3C H----OH2 (a) ethanol [NEET 2016, Phase II]
H
Step IV
(2°) O (b) methanol
OH2
 •• (c) N, N′-dimethylformamide (DMF)
(1°) H3C + CH3  C N •• intermolecular
→ CH3NCO (d) water
> N—H----OH2 alkyl migration
H3C
Ans. (c)
∆
CH3 StepV CH3NCO + 2OH− → CH3NH2 + CO23− The given reaction followsS N 2
(3°) mechanism andS N 2 reactions are
Strong +I-effect and hydrogen bonding 05 Which one of the following nitro- favoured in polar aprotic medium like
favours higher basic strength of 2º DMSO, DMF... etc.
compounds does not react with
amine. Thus, the correct order of basic CH3CH2 CH2Br + NaCN → DMF
strength in aqueous media will be nitrous acid? [NEET 2016, Phase II]
CH3CH2 CH2 CN + NaBr
(CH3)2 NH > CH3NH2 > (CH3) 3N H2
H2 H3C C So, the correct option is (c).
(a) H3C C (b)
04 Which of the following reactions is CH NO2
C NO2 H3C
appropriate for converting acetamide H2 07 Method by which aniline cannot be
to methanamine? [NEET 2017] CH3 prepared is [CBSE AIPMT 2015]
H3C
(a) Carbylamine reaction (a) hydrolysis phenyl isocyanide with
(c) H3C C NO2 (d) H3C C acidic solution
(b) Hofmann hypobromamide reaction H3C
H NO2 (b) degradation of benzamide with
(c) Stephens reaction O bromine in alkaline solution
(d) Gabriels phthalimide synthesis Ans. (c) (c) reduction of nitrobenzene with
Ans. (b) H2 / Pd in ethanol
Key Idea 1° and 2° nitro compounds
The conversion of amide with no react withHNO2 while 3°-nitro compound (d) potassium salt of phthalimide
substituent on nitrogen to an amine does not. treated with chlorobenzene followed
containing one carbon less by the action The reactions of given compounds with by the hydrolysis with aqueous NaOH
of alkaline hypobromide or bromine in HNO2 are as follow solution
presence of NaOH. It involves the Ans. (d)
HON == O
migration of alkyl or aryl group with its CH3CH2 CH2NO2 → Due to resonance in chlorobenzene C—Cl
electron pair to electron deficient N 1° -nitro bond acquires double bond character
from adjacent carbon. The reaction compound
CH3  CH2  C NO2 hence, C—Cl bond is inert towards
involves the intermediates of  nucleophile (phthalimide ion). Therefore
isocyanate. N OH
aniline cannot be prepared.
O H2
 H3C C HO N O
∆
CH3  C  NH2 + Br2 + NaOH → CH NO2 08 The number of structural isomers
Acetamide H3C possible from the molecular
1°-nitro compound N OH
CH3NH2 + NaBr + Na2 CO3 + H2O formula C 3H9 N is
Mathanamine CH3 CH C NO2 [CBSE AIPMT 2015]
O CH3 (a) 4 (b) 5
 (c) 2 (d) 3
Step I CH3  C NH2 + Br2 CH3
Ans. (d)
O HO N O
CH3 C CH NO2 Structural isomers of C3H9N are

→ CH3  C N Br O CH3CH2 CH2NH2 ,CH3  CH  CH3
 CH3 CH C NO2
1°-nitro compound 
H
CH3 N NH2
O OH 1444442444443
1° -amine
 H3C
Step II CH3  C N Br + OH− HO N O
No reaction

H3C C NO2 CH3  CH2 NH  CH3, CH3 N  CH3
H
H3C 2 ° -amine 
O 3°-nitro compound
CH3
 3° - amine
→ CH3  C N Br + H2O Thus, option (c) is incorrect.
s
Organic Compounds Containing Nitrogen 219
−
09 Acetamide is treated with the OH – •• 15 In the reaction,
(ii) RCONHBr → R  CO N Br + H2O
following reagents separately. CH3CN + 2H →
HCl
X →
2
Y,
Boiling H O
−
Which one of these would yield •• K+ •• SnCl2
(iii) R  C  N Br → R  C  N + KBr
methyl amine? [CBSE AIPMT 2010]
  • • the term Y is [CBSE AIPMT 1999]
(a) NaOH/ Br2 O O (a) acetone (b) ethanamine
(b) Sodalime (iv) On rearrangement
•• ••
(c) acetaldehyde (d) dimethyl amine
(c) Hot conc. H2 SO 4
(d) PCl5
R  C— N
 ••
º R  N == C == O Ans. (c)
HCl
Ans. (a) O CH3CN + 2H → CH3  CH == NH
SnCl 2
•• X
Key Idea The reagent which can convert (v) R  N == C == O + 2KOH → RNH2 Imide
CONH2 group into —NH2 group is used H2 O
for this reaction. + K2 CO3 CH3  CH ==O ←
Boil
Y
Among the given reagents only NaOH/
Br2 converts CONH2 group to NH2 12 Amides can be converted into Acetaldehyde
amines by a reaction named after So, Y is acetaldehyde.

group, thus it is used for converting
acetamide to methyl amine. This [CBSE AIPMT 1999]
reaction is called Hoffmann bromamide (a) Perkin (b) Claisen 16 The compound obtained by heating
reaction, in which primary amides on (c) Hofmann (d) Kekule a mixture of primary amine and
treatment withBr2 / NaOH form primary Ans. (c) chloroform with ethanolic
amines. potassium hydroxide (KOH) is
Amides can be converted into amines by
CH3CONH2 + NaOH+ Br2 → CH3NH2 [CBSE AIPMT 1997]
Acetamide Methyl amine Hofmann’s bromamide reaction. This
reaction is named after Hofmann. The (a) an alkyl isocyanide
+ NaBr + Na2 CO3 + H2O reaction is as follow. (b) an alkyl halide
 CONH2 + Br2 (l ) + 4KOH → NH2 (c) an amide
10 Which one of the following on +2KBr + K2 CO3 +2H2O (d) an amide and nitro compound
reduction with LiAlH 4 yields a Ans. (a)
secondary amine? 13 The decomposition of organic RNH2 + CHCl 3 + 3KOH (alc.) →
[CBSE AIPMT 2007] compounds, in the presence of
(a) Methyl isocyanide RNC + 3KCl + 3H2O
oxygen and without the development Alkyl isocyanide
(b) Acetamide of odoriferous substances, is called This reaction is known as
(c) Methyl cyanide [CBSE AIPMT 1999] carbylamine test.(only 1° amine gives
(d) Nitroethane (a) decay (b) N2 -fixation this reaction)
Ans. (a) (c) nitrification (d) denitrification
LiAlH Ans. (a) 17 Consider the following sequence of
CH3 N ≡≡ C + 4[H] →
4
CH3NHCH3
Dimethylamine Decomposition of organic compounds
reactions
in the presence of oxygen is generally Reduction HNO 2
On catalytic reduction or with lithium Compound [A] → [B] →
aluminium hydride (LiAlH4 ) or with called decay. The remaining three
CH3CH2OH
nascent hydrogen, alkyl isocyanide yield reactions takes place in the presence of
bacteria. The compound [A] is
2° amine whereas cyanide gives 1° amine
[CBSE AIPMT 1996]
on reduction.
14 Phenyl isocyanides are prepared (a) CH3CH2CN (b) CH3NO2
11 Intermediates formed during from which of the following (c) CH3NC (d) CH3CN
reaction of RCNH2 with Br 2 and reaction? [CBSE AIPMT 1999] Ans. (d)
 (a) Rosenmund’s reaction CH3C ≡≡ N →
Reduction
O (b) Carbylamine reaction A LiAlH4
KOH are [CBSE AIPMT 2001]
(c) Reimer-Tiemann reaction HNO
(a) RCONHBr and RNCO CH3  CH2 NH2 →
2
CH3CH2OH
(d) Wurtz reaction B
(b) RNHCOBr and RNCO
(c) RNHBr and RCONHBr Ans. (b) 1° amine (Ethanamine)
(d) RCONBr2 Both aliphatic and aromatic primary ∴ A is CH3CN.

Ans. (a) amines react with chloroform and alc.
KOH to give isocyanides or carbylamines 18 Which is formed when acetonitrile
The reaction, and the reaction is known as
is hydrolysed partially with cold
RCONH2 + Br2 + KOH → RNH2 carbylamine reaction.
conc. HCl? [CBSE AIPMT 1995]
is known as Hofmann bromamide C6H5NH2 + CHCl 3 + 3KOH → C6H5NC
reaction. The mechanism of this (alc. ) Phenyl (a) Acetic acid (b) Acetamide
reaction is given as : isocyanide (c) Methyl cyanide
(i) RCONH2 + Br2 → RCONHBr + HBr + 3KCl +3H2O (d) Acetic anhydride
Ans. (b) 22 Mark the correct statement. Ans. (d)

The partial hydrolysis of alkyl cyanides [CBSE AIPMT 1989] In strongly acidic medium, aniline is
with cold conc. HCl or H2SO4 gives (a) Methyl amine is slightly acidic protonated to form the anilinium ion.
amides. (b) Methyl amine is less basic than ammonia +
Conc. HCl NH2 NH3
CH3  C ≡≡ N → – CH3CONH2 (c) Methyl amine is a stronger base than
Alkylcyanides H2 O/OH
Acetamide NH3
H+
(d) Methyl amine forms salts with alkalies
19 Acetamide and ethyl amine can be Ans. (a)
Aniline Anilinium ion
distinguished by reacting with Methyl amine is a stronger base thanNH3.
[CBSE AIPMT 1994] This is due to the reason that alkyl Since, anilinium ion so formed is meta
(a) aq. HCl and heat groups are electron releasing groups directing, thus besides ortho and para
(+I-effect). As a result of which it derivatives, significant amount of meta
(b) aq. NaOH and heat
increase the electron density on the derivative is also formed.
(c) acidified KMnO 4 nitrogen atom and therefore, they can NH2 NH2 NH2
(d) bromine water donate electron pair more easily than
HNO3,
Ans. (b) ammonia. H2SO4
+
When acetamide is heated with aq. 288K
NaOH it forms NH3 gas but ethylamine TOPIC 2 Aniline
NO2
cannot form NH3. NO2 m-nitroaniline
NaOH ∆
Aromatic Amines (47%)
CH3CONH2 + H2O → CH3COONa + NH3 p-nitroaniline
(51%) NH 2
NaOH ∆
CH3CH2NH2 + H2O → No reaction 23 Which of the following amine will
NO2
give the carbylamine test?
[NEET (Sep.) 2020] +
20 For carbylamine reaction, we need
NHCH3 N(CH3)2
hot alc. KOH and [CBSE AIPMT 1992] o-nitroaniline
(2%)
(a) any primary amine and chloroform
(b) chloroform and silver powder (a) (b) 25 Identify A and predict the type of
(c) a primary amine and an alkyl halide reactions. [NEET 2017]
(d) a mono alkyl amine and NHC2H5 NH2 OCH3
trichloromethane
NaNH2
Ans. (a) (c) (d) A
Aliphatic and aromatic primary amines Br
when warmed with chloroform and an OCH3
alcoholic solution of KOH, form Ans. (d)
isocyanide or carbylamine which has Carbylamine test is responded by and substitution
(a)
very unpleasant smell. primary or 1°-amine (aliphatic or reaction
Warm aromatic) only. NH2
CH3CH2NH2 + CHCl 3 + 3KOH →
CHCl 3 OCH3
R NH2  → R NC + KCl + H2O
CH3CH2NC + 3KCl + 3H2O KOH/ ∆ NH2
CHCl 3 and elimination
Ar NH2  → Ar NC + KCl + H2O (b)
KOH/ ∆ Carbyl amine addition reaction
21 Indicate which nitrogen compound Options
amongst the following would OCH3
(a) Ph NH  CH3; 2° amine
undergo Hofmann reaction? (b) Ph N(CH3)2 ; 3° amine
Br
and cine substitution
[CBSE AIPMT 1989] (c) reaction
(c) Ph NH  C2H5 ; 2° amine
(a) RCONHCH3
(d) Ph NH2 ; 1° amine (aniline) OCH3
(b) RCOONH4
It responds to carbylamine test.
(c) RCONH2 and cine substitution
(d)
(d) RCONHOH 24 Nitration of aniline in strong acidic reaction
Ans. (a) medium also gives m-nitroaniline Ans. (a)

When amides react with bromine in the
because [NEET 2018]
OCH3 OCH3 OCH3
presence of caustic alkali to form a (a) in absence of substituents nitro
group always goes to m-position NH2
primary amine carrying one carbon atom NaNH2
less than the parent amide, then the (b) in electrophilic substitution reactions +
reaction is known as Hofmann amino group is meta directive
(c) in spite of substituents nitro group Br 2NH
bromamide reaction. direct cine
Heat always goes to only m-position substitution substitution
RCONH2 + Br2 + 4KOH → RNH2 + K2 CO3
(d) in acidic (strong) medium aniline is
+ 2KBr + 2H2O present as anilinium ion
If nucleophile occupies same position of In III, CH3 group is an electron NH2

the leaving group, product is called direct donating ando / p directing group which (a)
substitution product. increase the electron density on
If nucleophile occupies adjacent position benzene ring at ortho or para position NO2
of the leaving group, product is called while in II, NO2 group is an electron (b)
cine substitution product. Intermediate withdrawing group which decrease the
formed in this reaction is benzyne. electron density on benzene ring. Hence, CN
OCH3 OCH3 the III is more basic than II. (c)
In I, there is no substituent attached, due
s to which I is more basic than II and less CONH2
H + NH2
basic than III. (d)
Br Therefore, the correct order of basic
Benzyne
strength of above compounds is II < I < III.
OCH3 OCH3 Ans. (b)
s
27 The correct statement regarding The complete road map of the reaction
s
+ NH2 + HNH2 the basicity of arylamines is can be seen as
NH2 [NEET 2016, Phase I] + –
NO2 NH2 N2Cl
Attack of nucleophile (a) Arylamines are generally more basic
at the original position OCH3 than alkylamines because the Sn/HCl HNO2
(from where Br– leaves)
nitrogen lone-pair electrons are not Reduction
delocalized by interaction with the (A) (B)
NH2 aromatic ring π-electron system
Aniline
Nitro benzene Benzene diazonium
Direct substitution (b) Arylamines are generally more basic chloride unstable
product than alkylamines because of aryl PhOH
N N OH
OCH3 OCH3 group
Red colour dye
NH2 (c) Arylamines are generally more basic
s than alkylamines, because the
+ NH2
s nitrogen atom in arylamines is 29 The following reaction,
Attack of H—NH2 sp-hybridized
nucleophile at (d) Arylamines are generally less basic NH2
the adjacent OCH3 than alkylamines because the + Cl NaOH
carbon
NH2 nitrogen lone-pair electrons are
delocalized by interaction with the O
aromatic ring π-electron system. H
Cine substitution
Ans. (d) N
product
NH2 O
26 The correct increasing order of
basic strength for the following Ans. (d)
compounds is [NEET 2017] R — NH2 Schotten-Baumann reaction is a
NH2 NH2 NH2 Aryl amine Alkyl amine method to synthesise amides from
(less basic) (more basic) amines and acid chlorides.
Due to delocalisation of lone pair of
electrons of N-atom to the benzene ring, 30 Nitrobenzene on reaction with
it losses its basicity and becomes less conc. HNO 3 /H2SO4 at 80-100°C
NO2 CH3 basic than alkyl amine.
forms which one of the following
(I) (II) (III) On the other hand, alkyl amine has free
products? [NEET 2013]
(a) II < III < I (b) III < I < II lone pair of electron as well as +I-effect
of alkyl group increases electron density (a) 1, 2-dinitrobenzene
(c) III < II < I (d) II < I < III
on N-atom enhancing its basic nature. (b) 1, 3-dinitrobenzene
Ans. (d)
(c) 1, 4-dinitrobenzene
Thinking process This type of problem 28 A given nitrogen-containing (d) 1, 2, 4-trinitrobenzene
can be solved by application of electron- aromatic compound A reacts with Ans. (b)
withdrawing and electron donating group. Sn/HCl, followed by HNO 2 to give NO2 group being electron withdrawing
NH2 NH2 NH2 an unstable compound B. B, on that’s why it reduces the electron
treatment with phenol, forms a density at ortho and para-positions.
beautiful coloured compound C Hence, as compare to ortho and para
with the molecular formula the meta-position is electron rich on
C 12H10 N 2O. The structure of which the electrophile (nitronium ion)
NO2 CH3
compound A is [NEET 2016, Phase II] can easily attacks during nitration.
(I) (II) (III)
COOH NH2
HNO 3 + H2 SO 4 → H2NO 3+ + HSO 4− HNO2
C6H5NH2 → C6H5 N2+ Cl
(a) (b) 0 - 5° C
 Aryl amine
(273-278K)
↓
H2O + ↓NO2+ at 0-5°C temperature
NH2 Br
Electrophile NaNO2 + HCl → HNO2 + NaCl
CONH2 SO2NH2
(nitronium ion) Thus, HNO2 does not convert aryl amines
(c) (d) into phenol.
NO2 NO2
Br Br 34 The correct order of increasing

+ NO2+ reactivity of C X bond towards
Ans. (b)
NO2 COOH COCl nucleophile in the following
m-dinitrobenzene compounds is [CBSE AIPMT 2010]
or 1, 3-dinitrobenzene SOCl2 NH3 X X
Br Br NO2
31 What is the product obtained in the B
,
following reaction? CONH2 NH2 (CH3)3CX (CH)2CHX
[CBSE AIPMT 2011] III IV
NaOH I
NO2 NO2
Zn +Br2 II
.............? Br Br
NH4Cl C D (a) I < II < IV < III (b) II < III < I < IV
The conversion of ‘C’ to ‘D’ is an (c) IV < III < I < II (d) III < II < I < IV
N
N
example of Hofmann bromamide
(a) Ans. (a)
degradation reaction.
Key Idea Alkyl halides are more reactive
– towards nucleophilic substitution.
O 33 Which of the following statements
Reactivity depends upon the stability of
about primary amines is false ? carbocation intermediate formed.
N===N [CBSE AIPMT 2010]
(b) + Among the given halides, aryl halide
(a) Alkyl amines are stronger bases than (C6H5 X ) is least reactive towards
aryl amines nucleophile as in it the CX bond acquire
NH2
(b) Alkyl amines react with nitrous acid some double bond character due to
(c) resonance. Presence of electron
to produce alcohols
(c) Aryl amines react with nitrous acid to withdrawing groups like NO2 at ortho
NHOH and para-positions facilitate the
produce phenols
(d)
(d) Alkyl amines are stronger bases than nucleophilic displacement of X of aryl
ammonia halide. Among alkyl halides, 3° halides are
more reactive as compared to 2° halides
Ans. (d) Ans. (c) due to the formation of more stable
Reduction of nitrobenzene with Zn/ Key Idea (i) Presence of electron carbocation. Hence, the order of
NH4Cl (neutral medium) gives phenyl withdrawing substituent decreases the reactivity of CX bond towards
hydroxyamine. basicity while the presence of electron nucleophile is as follows:
releasing substituent like, X X
NO2
 CH3,  C2H5 , etc, increases the
NO2
acidity.
Zn/NH4Cl
+4[H] (ii) HNO2 converts NH2 group of < < (CH3)2 CH—X
(Neutral medium)
aliphatic amine into OHwhile that of IV
NH—OH aromatic amines into N == NCl.
I < (CH3)3C—X
+H2O Since, phenyl group is a electron NO2
withdrawing group, it decreases the II III
basicity. Alkyl group, on the other hand,
32 In a set of reactions, being electron releasing, increases the 35 Which of the following is more basic
basicity. Thus, alkyl amines are more than aniline?
m-bromobenzoic acid gave a basic as compared to aryl amines as well
[CBSE AIPMT 2006]
product D. Identify the product D. as ammonia. (a) Diphenylamine (b) Triphenylamine
HNO2
[CBSE AIPMT 2011] R  NH2 → R OH (c) p-nitroaniline (d) Benzylamine
COOH Alkyl Ans. (d)
amine ••
Benzylamine, C6H5 CH2 —NH2 is more
SOCl2 NH3 NaOH Thus, HNO2 (nitrous acid) converts alkyl
B C Br2
D amines to alcohols. basic than aniline because benzyl group
Br But aryl amines react with nitrous acid to (C6H5 CH2 —) is electron donating group
due to +I-effect. So, it is able to increase
form diazonium salt.
the electron density of N of NH2 NHCOCH3 NH2 Ans. (d)

group. Thus, due to higher electron Br Br NO2 NH2 N C
density, rate of donation of free pair of H2O/H+
electron is increased, i.e. basic Red P CHCl3
character is higher. Phenyl and nitro HI KOH
group are electron withdrawing groups,
Nitrobenzene Aniline Aryl isocyanide
so they decreases the electron density CH3 CH3
•• A B C
on N of —NH2 group. Hence, they are less B C
Catalytic
4H reduction
basic than aniline. C—
—N
38 H—N—CH3
36 Electrolytic reduction of
nitrobenzene in weakly acidic + CH3MgBr P
medium gives [CBSE AIPMT 2005] OCH3
N-methylaniline
(a) aniline Product P in the above reaction is
(b) nitrosobenzene [CBSE AIPMT 2002] 40 Aniline is reacted with bromine water
(c) N-phenyl hydroxylamine OH O and the resulting product is treated
|
(d) p-hydroxyaniline
CHCH3 CCH3
with an aqueous solution of sodium
Ans. (a) nitrite in presence of
NO2 NH2 dilute hydrochloric acid. The
(a) (b)
compound so formed is converted
+ 4H
Electrolytic
+H2O
OCH3 OCH3 into a tetrafluoroborate which is
Reduction in weakly
CHO COOH subsequently heated. The final
acidic medium
Aniline product is [CBSE AIPMT 1998]
37 The final product C, obtained in this (a) 1, 3, 5-tribromobenzene
(c) (d)
reaction (b) p-bromofluorobenzene
OCH3 OCH3 (c) p-bromoaniline
NH2
Ans. (b) (d) 2, 4, 6-tribromofluorobenzene
Ac2O Br2 H2O CH3 Ans. (d)
A B C
CH3COOH H+ | NH2 group is greatly activating group.
C—
—N C==N.MgBr Hence, reaction takes place rapidly.
CH3 δ+
δ– δ+ NH2
+ CH3MgBr
NH2 NHCOCH3 OCH3 OCH3 δ– δ–
+ –NH3
2H3O –Mg(OH)Br
Br Br
(a) (b) O δ–
C—CH3 It is an o,p-directing group.
H3C—C==O
NH2 NH2
CH3 CH3
Br Br
Or NaNO2
NH2 COCH3 + 3Br2
OCH3 OCH3 (water) dil. HCl
COCH3 Br P
(c) (d) Br
39 An organic compound A on + –
N2Cl N2BF4
reduction gives compound B which
CH3 CH3 on reaction with chloroform and Br Br Br Br
NaBF4
Ans. (a) potassium hydroxide forms C. The (–NaCl)
NH2 NHCOCH3 compound C on catalytic reduction
gives N-methylaniline. The Br Br
Ac2O Br2 F
compound A is [CBSE AIPMT 2000]
CH3COOH
(a) nitrobenzene Br Br
∆
(b) nitromethane
–N2, –BF3
CH3 CH3 (c) methylamine
A (d) aniline Br
2,4,6-tribromofluorobenzene
41 A reagent suitable for the Ans. (d) Ans. (a)

determination of N-terminal This is Etard reaction in which reaction
residue of a peptide is —CHO +H2N—C6H5 of toluene with chromyl chloride in CCl 4
[CBSE AIPMT 1996] Aniline followed by hydrolysis gives
Benzaldehyde benzaldehyde. Toluene reacts with
(a) p-toluene sulphonyl chloride chromyl chloride to form a precipitate
(b) 2,4-dinitrophenyl hydrazine called the Etard complex.
(c) carboxypeptidase —CH N—C6H5 + H2O
CH3 CH(OCrOHCl2)2
(d) 2,4-dinitrofluorobenzene CS
Benzal aniline + CrO2Cl2 2
Ans. (d)
(Schiff’s base, anils)
2,4-dinitrofluorobenzene is called Toluene (X)
CHO
Sanger’s reagent. When this reagent 44 What is the decreasing order of H3O
+
reacts with amino group of peptide

basicity of 1°, 2° and 3° ethyl
chain, it form 2,4-dinitrophenyl
derivatives which on hydrolysis form amines and ammonia? Benzaldehyde
DNP derivatives of amino acids. [CBSE AIPMT 1994]

(a) NH3>C2H5NH2 > (C2H5 )2 NH> (C2H5 ) 3N 46 Consider the nitration of benzene
42 Aniline is an activated system for (b) (C2H5 ) 3N> (C2H5 )2 NH >C2H5NH2 > NH3 using mixed conc. H2 SO 4 and
electrophilic substitution. The (c) (C2H5 )2 NH> C2H5NH2> (C2H5 ) 3N> NH3 HNO 3 . If a large amount of KHSO 4
compound formed on heating (d) (C2H5 )2 NH> (C2H5 ) 3N> C2H5NH2> NH3 is added to the mixture, the rate of
aniline with acetic anhydride is Ans. (d) nitration will be [NEET 2016, Phase I]
[CBSE AIPMT 1996] As the number of alkyl groups increases, (a) slower
the electron density on nitrogen atom (b) unchanged
NH2
also increases, so the basic character (c) doubled
increases but 3° amines are less basic (d) faster
(a) than 2° amines due to steric hindrance Ans. (d)
of 3° amines, so the correct order of
COCH3 In the nitration of benzene in the
basicity is
presence of conc.H2SO4 and HNO3,
Ammonia < 1° < 3° < 2°
(b) nitrobenzene is formed.
NH3 < C2H5NH2 < (C2H5 ) 3N < (C2H5 )2 NH
HNO3 + H2SO4 r NO2+ +
NH2
HSO−4 + H2O
(c) TOPIC 3 Electrophile Nucleophile
COCH3
Diazonium Salts If large amount of KHSO 4 is added to this
NHCOCH3 mixture, moreHSO−4 ion furnishes and
hence the concentration ofNO2+ , i.e.
(d) 45 The intermediate compound ‘X’ in electrophile decreases.
the following chemical reaction is As concentration of electrophile
Ans. (d) [NEET 2021]
decreases, rate of electrophilic
NH2 NHCOCH3 CH3
CS2 H3O– aromatic reaction also decreases.
CH3CO +CrO2Cl2 X
O O
CH3CO 47 Which of the following will be most
C stable diazonium salt RN +2 X − ?
H [CBSE AIPMT 2014]
Aniline Acetanilide
(a) CH3N2+ X −
CH(OCrOHCl2)2
43 When aniline reacts with oil of (b) C 6H5N2+ X −
(a)
bitter almonds (C 6H5CHO) (c) CH3CH2N2+ X −
condensation takes place and CH(OCOCH3)2 (d) C 6H5CH2N2+ X −
benzal derivative is formed. This is (b) Ans. (b)
known as [CBSE AIPMT 1995] Cl Diazonium salt containing aryl group
CH
(a) Millon’s base (c)
Cl directly linked to the nitrogen atom is
most stable due to resonance
(b) Schiff’s reagent Cl
CH stabilisation between the benzene
(c) Schiff’s base H
(d) nucleus and N-atom. Diazonium ion
(d) Benedict’s reagent act as a electrophile.
H3C CH3 CH3
+ + – + – N==NCl N
N N N N N N
NH
+ + NaNO2
+ + HCl or HNO2
+ N-methylaniline CH3
(2°amine)
+ +
N N N N
– H N N O
X N,N-dimethylaniline
+
CH3
—N==N— —N N-nitroso-N-methylaniline
CH3 (nitroso compound)
[Resonance structure of benzene diazonium ion] (yellow oily liquid)
Coupling product
Y
48 Aniline in a set of the following 50 In a reaction of aniline a coloured
49 Predict the product, products C was obtained.
reactions yielded a coloured [CBSE AIPMT 2009]
product Y. [CBSE AIPMT 2010] CH3
NHCH3 NH2 —N
NH2 NaNO2 CH3
+ NaNO2+HCl Product B C
HCl Cold
NaNO2/HCl N, N-dimethylaniline A
(273-278 K) X Y
CH3
The structure of C would be
The structure of Y would be N N O [CBSE AIPMT 2008]
CH3 (a)
(a) —N==N —N CH3 (a) N NCH2
CH3
NNO2
CH3 CH3 (b) N
(b) HN —NH —NH CH3

NHCH3 NHCH3 CH3 CH3
(c) H3C N==N NH2 NO N N

(c) + (b)
CH3 CH3
(d) HN  N==N  —NH NO CH3

NHNH N
OH (c) CH3
Ans. (a)
NCH3 CH3
Key Idea NaNO2 /HCl causes (d) —N==N  N
diazotisation of —NH2 group and the (d) CH3
diazonium chloride gives a coupling
product with active aryl nucleus. Ans. (a)
Both aliphatic and aromatic secondary Ans. (d)
NH2 N==NCl amines reacts with + –
NH2 N NCl
NaNO2 + HCl or (HNO2 ) to form NaNO2
NaNO2 /HCl N-nitrosamines which are insoluble in HCl

(273-278-K) dilute mineral acids and separate out as 273-278 K
A B
neutral yellow oily compounds. Aniline Benzene diazonium chloride
X
Ch3
Ans. (d) (a) CH3NH N==N  NHCH3
H N
CH3 NH2 + –
N + N2Cl
NaNO2
Cold
HCl (b) CH3 N==N  NH2
p-(N,N-dimethyl) amine azobenzene (Diazotisation)
(azodye) A
Benzene diazonium
CH3
chloride (c) (CH3)2N N==N 
N N
CH3 CN
CuCN H2 /Ni
C
(Sandmeyer's (Reduction) (d) (CH3)2N N==N  —CH3
reaction)
B
51 Aniline in a set of reactions yielded Cyanobenzene Ans. (c)
a product [CBSE AIPMT 2005]
Aniline on diazotisation in cold (at0° to
CH2NH2
NH2 5° C) gives benzene diazonium chloride.
NaNO2 CuCN H2 CH2OH
HNO2
A B C 0-5°C
HCl Ni NH2 + NaNH2 + 2HCl Diazotisation
C
Benzyl amine
HNO2 D + _
D Benzyl alcohol N==N—Cl + NaCl + 2H 2 O
The structure of the product D Benzene diazonium
would be 52 Aniline when diazotised in cold and chloride
(a) C 6H5CH2NH2 then treated with dimethyl aniline, This benzene diazonium chloride on
(b) C 6H5NHCH2CH3 gives a coloured product. Its coupling with dimethyl aniline gives a
structure would be coloured product, i.e. p-(N,N-dimethyl)
(c) C 6H5NHOH amino azobenzene (azo dye).
[CBSE AIPMT 2004]
(d) C 6H5CH2OH
26
Polymers
TOPIC 1 Isoprene shows 1, 4-addition with glycine (H2N  CH2  COOH) and amino
themselves to give cis-1, 4-polyisoprene caproic acid (H2N(CH2 ) 5 COOH).
Classification of or natural rubber. The remaining polymers, i.e. nylon-6,6,
Polymers CH3 CH3 ( NH(CH2 ) 6 NHCO(CH2 ) 4 CO)n ,
nylon-6- ( CO(CH2 ) 5 NH  ) n and buna-S
----CH2==CCH==CH2 CH2==C—CH==CH2----
01 Which of the following statement is 1 2 3 4 1′ 2′ 3′ 4′ C6H5
correct about bakelite? 1, 4-addition 
[NEET (Oct.) 2020] polymerisation ( CH2  CH == CH  CH2  CH 
)n
(a) It is a cross linked polymer. H3C H H3C H are non-biodegradable polymers.
(b) It is an addition polymer. C==C C==C Hence, option (a) is correct.
2 3 2′ 3′
(c) It is a branched chain polymer. CH2 CH2 CH2 CH2
1 1′ 4′
(d) It is a linear polymer. Natural rubber 05 Regarding cross-linked or network
Ans. (a)
All polymers mentioned in options (a), (b) polymers, which of the following
Bakelite is a cross linked condensation and (c) are synthetic 1,4-addition statements is incorrect? [NEET 2018]
thermosetting copolymer of phenol and polymers. Where (a) and (c) are buna-S
formaldehyde. (a) Examples are bakelite and melamine
and buna-N respectively.
(b) They are formed from bi- and
OH tri-functional monomers
03 The polymer that is used as a (c) They contain covalent bonds
–
H+or OH (catalyat)
substitute for wool in making between various linear polymer chains
+ CH2 O
Laderer Manasse commercial fibres is (d) They contain strong covalent bonds
reaction [NEET (Odisha) 2019] in their polymer chains
OH OH (a) melamine (b) nylon-6, 6 Ans. (d)
(c) polyacrylonitrile (d) buna-N Cross-linked or network polymers are
CH2 CH2 CH2
Ans. (c) formed from bi-functional and
Polyacrylonitrile or orlon or acrilan, tri-functional monomers and contain
CN strong covalent bonds between various
CH2 CH2
 linear polymer chains. These are hard,
( CH2  CH ) n is an addition rigid and brittle due to cross-links
homopolymer of monomer CH2 == CHCN e.g. bakelite, melamine etc. Thus, option
CH2 CH2 CH2 (d) is incorrect.
(vinyl cyanide). It is used in making
OH OH
synthetic fibres and synthetic wool.
Bakelite or Phenol Thus, it is a substitute for wool in making 06 Natural rubber has
formaldehyde resin commercial fibres. [NEET 2016, Phase I]
(a) All trans-configuration
02 Which of the following is a natural 04 The biodegradable polymer is (b) Alternate cis- and trans-
polymer? [NEET (Sep.) 2020] configuration
(a) nylon-2-nylon-6 (b) nylon-6 (c) Random cis- and trans-configuration
(a) Poly (Butadiene-styrene)
(c) buna-S (d) nylon-6,6 (d) All cis-configuration
(b) Polybutadiene
(c) Poly (Butadiene-acrylonitrile) Ans. (a) Ans. (d)
(d) Cis-1, 4-polyisoprene Nylon-2-nylon-6 The repeating unit in natural rubber has
O
Ans. (d) the cis-configurations with chain


( HN  CH2 CONH(CH2 ) 5 C  is a extensions on the same side of the
Natural polymer (soft) is an addition )n
ethylene double bond, which is essential
homopolymer of isoprene which is a biodegradable polymer. It is an for elasticity. If the configuration is
conjugated diene. alternating polyamide copolymer of
trans, the polymer is either a hard plastic Ans. (b)

(b) CH2 ===C  CH === CH2
or a substance like gutta-percha. Nylon-66 is a fibre not a elastomer. As in

CH3 H CH3 it the forces of attraction are H-bonding
C == C CH2 CH2 . All other given statements are true.
H2C CH2 C == C (c) CH2 === C  CH === CH2
H3C H 12 Of the following which one is

Cl classified as polyester polymer?
H3C H [CBSE AIPMT 2011]
C == C (d) CH2 === CH  CH === CH2
(a) Bakelite
CH2 CH2 Ans. (c) (b) Melamine
Neoprene is synthetic rubber and is a (c) Nylon-66
07 Which one of the following is an polymer of chloroprene which is (d) Terylene
example of a thermosetting chemically 2-chlorobuta- 1,3-diene. Ans. (d)
polymer? [CBSE AIPMT 2014] Terylene (or dacron) is a polyester
n CH2 C CH CH2
because it contains ester groups and
(a) (CH2  C ==CH  CH2 )n Cl formed by the monomer units

Cl
Chloroprene CH 2 C CH CH 2 terephthalic acid and ethylene glycol
CH2 — OH
(b)  ( CH2  CH  )n Cl n  
 Neoprene  
CH2 — OH
Cl  
H H O 09 Nylon is an example of [NEET 2013]
   (a) polyester (b) polysaccharide
(c) (N  (CH2 ) 6  N  C (c) polyamide (d) polythene
13 Structures of some common
O
polymers are given. Which one is
 Ans. (d)
 (CH2 ) 4  C) not correctly presented?
n The general structure of any nylon [CBSE AIPMT 2009]
OH OH polymer is
(a) Teflon 
( CF2 —CF2 
)n
CH2 CH2 O
(b) Neoprene
(d) R C N R
n  CH2 C ===CH CH2 CH2 
n  
H
  
Ans. (d) Amide linkage  Cl 
 n
OH OH Because of the presence of amide
linkage, nylon belongs to polyamides. (c) Terylene
CH2 CH2
—OC
( COOCH2CH2O
)n
10 Which one of the following is not a
n condensation polymer? (d) Nylon 66
Novolac, a condensation polymer of [CBSE AIPMT 2012] —[ NH(CH2 ) 6 NHCO(CH2 ) 4 — CO —]n
phenol and formaldehyde is a (a) Melamine (b) Glyptal Ans. (b)
thermosetting polymer. (c) Dacron (d) Neoprene
Neoprene rubber Neoprene is a polymer of chloroprene
Ans. (d) (2-chloro-1,3-butadiene) and also
(a) 
[ CH2  C == CH  CH2  ]n and PVC
 Condensation polymers are obtained by called homopolymer addition
Cl bifunctional molecules (monomers) with polymer).
(b) 
[ CH2  CH  ]n the elimination of smaller molecules nCH2 CCH CH2
Polymerisation
 whereas additional polymers are

Cl obtained from multiple bond containing Cl
are thermoplastic polymers while monomers. Neoprene is a polymer of Chloroprene
chloroprene (CH2 ==C(Cl)  CH==CH2 ) CH2C CHCH2
nylon-66
O so it is an addition polymer, not a
condensation polymer. Cl
 Neoprene
n
(c) 
[ NH  (CH2 ) 6 NH  C  (CH2 ) 4 (synthetic rubber)
O 11 Which of the following statements
 is false? [CBSE AIPMT 2012] 14 [NH(CH2 ) 6 NHCO(CH2 ) 4 CO]n
C  ] n is a polyamide which is (a) Artificial silk is derived from cellulose
commonly known as fibre. (b) Nylon-66 is an example of elastomer is a [CBSE AIPMT 2006]
(c) The repeat unit in natural rubber is (a) copolymer
08 Which is the monomer of neoprene isoprene (b) addition polymer
in the following? [NEET 2013] (d) Both starch and cellulose are (c) thermo-setting polymer
polymers of glucose
(a) CH2 ==CH C ==CH (d) homopolymer
Polymers 229
Ans. (a) O
17 Natural rubber is a polymer of H2 H
 [ NH(CH2 ) 6 NHCO(CH2 ) 4 CO 
] n is a [CBSE AIPMT 1999] (d) C C C N (CH2)6
C
copolymer. Polymers whose repeating (a) butadiene (b) ethyne H2 2
structural units are derived form two (c) styrene (d) isoprene O
or more types of monomer units are NH
Ans. (d)
called copolymer
n H2N(CH2 ) 6 NH2 + nHOOC(CH2 ) 4 COOH Polyisoprene is the natural rubber n
Polymerisation
which is the polymer of isoprene. Ans. (d)
→  
–nH2O   Nylon-6, 6 polymer is formed as
 CH2== CH — C ==CH2 —
n— 
   | 
HOOC(CH2)4COOH + H2N(CH2)6NH2
 NH(CH2 ) 6 NHCO(CH2 ) 4 CO 
—
 CH3  Adipic acid Hexamethylene
  n Isoprene
diamine
(monomer) Polymerisation
Polymerisation
15 Cellulose is a polymer of → O O
[CBSE AIPMT 2002]   C (CH2)4CNH (CH2)6NH
 
n
(a) glucose (b) fructose Nylon-6,6
(c) ribose (d) sucrose
— CH2 — CH == C  CH2 —
 Thus, option (d) is correct.
 | 
Ans. (a)  CH3 
Cellulose is a polymer of glucose, i.e. Polyisoprene (natural rubber) n 20 Biodegradable polymer which can be
(polymer) produced from glycine and
C6H12O6 .
aminocapric acid is
18 In elastomer, the intermolecular
16 Which one of the following is not [CBSE AIPMT 2015]
forces are [CBSE AIPMT 1996]
correctly matched? (a) nylon 2-nylon 6
[CBSE AIPMT 2001] (a) strong (b) weak (b) PHBV
(a) Neoprene (c) nil (d) None of these (c) buna-N
  Ans. (b) (d) nylon-6, 6
  In elastomers, the polymer chains are Ans. (d)
 CH2  C == CH — CH2 
 held together by weak van der Waals’
 |  forces, e.g. natural rubber. Nylon-2-nylon-6
 Cl n It is an alternating polyamide of glycine
(b) Nylon-66 (containing two carbon atoms) and
TOPIC 2 amino caproic acid or 6-aminohexanoic
acid (containing six carbon atoms).
NH(CH 2) 6NH Methods of nH2N  CH2  COOH
CO(CH 2) 4CO 
n
Polymerisation Glycine
+ nH2N  (CH2 ) 5  COOH →

(c) Terylene
O O 19 Which one of the following Amino caproic acid
structures represents nylon 6, 6  
 
—OCH2CH2C C polymer? [NEET 2016, Phase II] NH CH2  C NH( CH2 )5  C 

n    
H2 H H2 H   n
  C C C C O O
CH3
   (a) Nylon - 2 - nylon - 6
 CH2  C 
(d) PMMA   NH2 CH3 It is a biodegradable step-growth
   66 copolymer.
 COOCH  H2 H H2 H
 3 n C C C C 21 Caprolactum is used for the
Ans. (c) (b) manufacture of
NH2 NH3
Terylene is formed by the condensation 66 [CBSE AIPMT 2015]
of dimethyl terephthalate and glycol. H2 H H2 H (a) nylon-6 (b) teflon
Its structure is C C C C (c) terylene (d) nylon-6 6
O O (c)
|| || Ans. (a)
NH2 Cl
6 O
OCH2CH2OC C— O
H2 H H2 H H
n
C C C C NH 533K N
Terylene (Dacron) N2 n
6 Nylon-6
Hence, the structure of terylene given in CH2 COOH
question is incorrect.
22 Which of the following organic 24 Which one of the following (a) Starch
compounds polymerises to form statements is not true? (b) Nucleic acid
the polyester dacron? [CBSE AIPMT 2008] (c) Polystyrene
[CBSE AIPMT 2014] (a) In vulcanisation, the formation of (d) Protein
(a) Propylene and para sulphur bridges between different Ans. (c)
HO  (C6H4 ) OH chains make rubber harder and Chain growth polymerisation requires an
(b) Benzoic acid and ethanol stronger initiator (such as organic peroxides) to
(c) Terephthalic acid and ethylene glycol (b) Natural rubber has the produce a free radical to which the
(d) Benzoic acid and para trans-configuration at every double monomers are added in a chain fashion.
HO  (C6H4 ) OH bond Initiators are added in a very small
Ans. (c) (c) Buna-S is a copolymer of butadiene and quantities and are decomposed by heat,
styrene light or oxidation-reduction reaction to
Dacron, commonly known as terylene, is (d) Natural rubber is a 1,4-polymer of produce reactive species, e.g. free
obtained by heating a mixture of isoprene radical.
terephthalic acid and ethylene glycol at
Ans. (b) Polystyrene is an example of chain
420-460 K in the presence of zinc
growth polymer because in it styrene
acetate and antimony trioxide as a Natural rubber is cis-1, 4-polyisoprene
molecules are associated in the form of
catalyst. and has all cis configurations about the
monomer
double bond as shown below. It is
nHOOC COOH prepared from latex which is obtained in CH 2CH 3
cis form called Havia Rubber latex is
Terephthalic acid obtained from rubber tree (Havea
∆ CH 2== C H 2
+ nHOCH2CH2OH brasiliensis).
– HCl AlCl3
Ethylene glycol
H 3C H
C C CH 2 CH 2 CH==CH2

[ O  CH2  CH2  O—CO H 2C CH 2 C C
H 3C H
Polyesteric bond Dacron H 3C H Fe2O 3 /C r 2O 3
C C 650°C
CH 2 CH 2
CO ] n
25 The monomer of the polymer —— CHCH2

23 Which of the following structures CH3
represents neoprene polymer?  +
CH3 ( C 6 H 5CO )2O 2
[CBSE AIPMT 2010] CH2  C  CH2  C is

(a) (CH2 C == CH CH2 )  CH3 n
n
CH3 Polystyrene

Cl
[CBSE AIPMT 2005]
CN 27 Which one of the following
CH3
| monomers gives the polymer
(b) —( CH2 CH— )n (a) H2C == C
neoprene on polymerisation?
Cl CH3 [CBSE AIPMT 2003]
|
(b) (CH3)2 C == C(CH3)2 Cl
(c) —( CH2  CH—)n |
(c) CH3CH ==CH⋅CH3
(d) —( CH CH2—) n (a) CH2 == C CH == CH2
(d) CH3CH == CH2
| (b) CF2 ==CF2
C 6H5 Ans. (a)
(c) CH2 == CHCl
The monomer of polymer
Ans. (a) (d) CCl2 == CCl2
CH3
Neoprene (synthetic rubber) is a  CH3 Ans. (a)
+
polymer of chloroprene, i.e. — CH2 — C — CH2 — C is Neoprene is an addition polymer of
2-chloro-1, 3-butadiene.  CH3
CH3 chloroprene or chloro-1,3-butadiene
Polymerisation (monomer).
nH2C==C—C==CH2
CH3
Cl
Cl H CH2 == C because  Polymerisation
2-chloro-1,3-butadiene CH3 nCH2 == CH  C == CH2 →
(chloroprene) Chloroprene
2-methylpropene shows cationic
 
polymerisation. Cl
CH2—C==C—CH2  
  
26 Which one of the following is a  CH2  CH ===C  CH2 
Cl H n  
Neoprene chain growth polymer ?  n
(synthetic rubber) [CBSE AIPMT 2004]
Polymers 231
28 Acrilan is a hard, horny and a high Ans. (b) Ans. (b)

melting material. Which of the F2 C == CF2 is a monomer of well known The monomer units of nylon-66 are
following represents its structure? plastic teflon, a material inert to almost obtained by the reaction of
[CBSE AIPMT 2003] all chemicals. hexamethylene diamine and adipic
 CH2 CH   Polymerisation acid.
  n
[ F2C== CF 2 
]
(a)  | H2O2, ∆
COOC2H5  Monomer
34 Bakelite is prepared by the reaction
 
 n (Tetra-flouroethene) F F between [CBSE AIPMT 1995]
| |
 —CH2 — CH — — C— C— (a) urea and formaldehyde
  | | (b) ethylene glycol
(b)  | 
 Cl  F F n (c) phenol and formaldehyde
 n
(Teflon polymer) (d) tetramethylene glycol
CH2 — CH — Ans. (c)
 |  31 Terylene is a condensation polymer
(c)  Bakelite is a polymer obtained by the
 CN  of ethylene glycol and
 n condensation reaction between
[CBSE AIPMT 1999] phenol and formaldehyde. It is a
(a) benzoic acid (b) phthalic acid condensation polymer and basic unit
CH3 (c) salicylic acid (d) terephthalic acid of Bakelite is Novolac.
|
(d) — CH2 — C  Ans. (d)
| Terylene is a condensation polymer of
35 The reagent ‘R’ in the given
COOCH3 n ethylene glycol and terephthalic acid. It sequence of chemical reaction is
is also called polyester [NEET 2021]
Ans. (c) +
NH2 N2CI–
Acrilan (or acrylonitrile) is monomer unit n[HOCH2CH2OH]+ n HOOC COOH
Br Br Br Br
of polyacrylonitrile (PAN). Its structure is Ethylene glycol NaNO2, HCl
Terephthalic acid
 CH2 — CH —  0-5°C
 |  Condensation
 CN  Polymerisation
  Br Br
 n
 CH3  —OCH2CH2OC C— Br Br
 |  || || R
29 Monomer of  — C — CH2  is
— O O n
 |  Esteric Terylene
 CH3  bond
 n Br
[CBSE AIPMT 2002] 32 Which one of the following is used (a) H2O (b) CH3CH2OH
(a) 2-methylpropene to make ‘non-stick’ cookware ? (c) HI (d) CuCN/KCN
(b) styrene [CBSE AIPMT 1997] Ans. (d)
(c) propylene (a) PVC Mild reducing agents like alcohol are
(d) ethene (b) Polystyrene used to reduce diazonium salts to arene.
Ans. (a) (c) Polyethylene terephthalate Alcohol (ethanol is oxidised to aldehyde
(d) Polytetrafluoro ethylene (ethanal).
 CH3 
|  Ans. (d)
Monomer of —  C— CH2— is NH2 N2Cl
|  Polytetrafluoro ethylene (C2F4 ) n or
  teflon is used to make non-stick Br Br Br Br
NaNO2+HCl
 CH3 n cookware, because it is a tough 0-5°C
2-methylpropene material, resistant to heat and also
or isobutene, H3C  C == CH2 the bad conductor of electricity.
| Br Br
CH3 2, 4, 6 tribromoaniline
33 Nylon-66 is a polyamide obtained
30 CF2 == CF2 is a monomer of Br Br
by the reaction of CH3CH2OH
(a) buna-S (a) COOH(CH2 ) 4 COOH +H2NC 6H4NH2- (p)
(b) teflon (b) COOH(CH2 ) 4 COOH + NH2 (CH2 ) 6 NH2 Br
1, 3, 5.-tribromobenzene
(c) glyptal (c) COOH(CH2 ) 6 COOH + NH2 (CH2 ) 4 NH2
(d) nylon-6 (d) COOHC 6H4COOH- (p) + NH2 (CH2 ) 6 NH2 ∴ Reagent used is CH3CH2OH (ethanol).
27
Biomolecules, Chemistry
in Everyday Life and
Environmental Chemistry
TOPIC 1 Ans. (a) 05 Which of the following is a basic
Conc.H2SO4 removes water, i.e. amino acid?
Biomolecules dehydrates carbohydrates into carbon (a) Alanine
[NEET (Sep.) 2020]
(b) Tyrosine
(black residue) or charred sugar. (c) Lysine (d) Serine
Conc.H 2 SO 4
01 Given below are two statements. C12H22O11 or C12 (H2O) 11   → 12 C Ans. (c)
− 11 H 2 O (Black )
Statement I Aspirin and
NH2
paracetamol belong to the class of 03 Deficiency of which vitamin causes (a) Alanine ⇒ CH3CH
narcotic analgesics. osteomalacia? [NEET (Oct.) 2020] COOH
Statement II Morphine and heroin (a) Vitamin A (b) Tyrosine ⇒
are non-narcotic analgesics. (b) Vitamin D NH2
In the light of the above statements, HO —CH2—CH
(c) Vitamin K COOH
choose the correct answer from the (d) Vitamin E
options given below. NH2
Ans. (b) (c) Lysine ⇒ H2N(CH2)4CH
[NEET (Oct.) 2021] COOH
Deficiency of
(a) Both Statement I and Statement Il NH2
Vitamin A causes—Xerophthalmia
are true. (d) Serine ⇒ HOCH2CH
(b) Both Statement I and Statement lI Vitamin D causes—Osteomalacia and COOH
are false. Rickets Since, lysine contains more number of
(c) Statement I is true but Statement Il Vitamin E causes—Fragility of RBCs —NH2 groups as compared to —COOH
is false. Vitamin K causes—Increase in blood groups, hence it is a basic amino acid.
(d) Statement I is false but Statement I clotting time.
is true. Hence, option (b) is correct. 06 The non-essential amino acid
Ans. (b) among the following is
04 Which of the following statements [NEET (National) 2019]
Narcotic analgesics They are the
is not true about glucose?
analgesics drugs that are used to reduce (a) leucine (b) alanine
[NEET (Oct.) 2020]
pain. They are obtained from opium (c) lysine (d) valine
poppy, so they are also called opiates. (a) It is an aldohexose.
Ans. (b)
They are addictive in nature. Morphine (b) It contains five hydroxyl groups.
and heroin are narcotic analgesics. (c) It is a reducing sugar. The amino acids that can be synthesised
in our body and hence are not essentially
Non-narcotic analgesics They are (d) It is an aldopentose.
required in our diet are called
non-addictive in nature and are not Ans. (d) non-essential amino acids. e.g. glycine,
obtained from opium poppy. Aspirin and
Glucose (C6H12O6 ) can be simply shown as, alanine, serine, proline, cysteine,
paracetamol are non-narcotic analgesics.
⇒Shows reducing property. glutamine, tyrosine, aspartic acid,
So, both statements I and II are false.
So, glucose is an aldohexose (made of glutamic acid, asparagine. Rest given
six carbon atoms) and it is a reducing options are essential amino acids, i.e.
02 The reaction of concentrated those can’t be synthesised in our body
sugar. Containing five OHgroups.
sulphuric acid with carbohydrates Hence, option (d) is incorrect statement.
hence essentially required in our diet.
(C 12H22O 11 ) is an example of Their other examples are isoleucine,
HO CH2 (CHOH)4 CH O phenylalanine, methionine, tryptophan,
[NEET (Oct.) 2020]
(a) dehydration (b) oxidation one Four aldehyde
threonine, arginine and histidine.
(c) reduction (d) sulphonation 1°– OH group 2°– OH group group Hence, option (b) is correct.
Biomolecules, Chemistry in Everyday Life and Environmental Chemistry 233
CH2OH CH2OH
07 Which of the following compounds can form a Zwitter O 5
O
ion? [NEET 2018] H H H H H H
4 1 4 1
(a) Benzoic acid (b) Acetanilide —O OH H O OH H a-Link
(c) Aniline (d) Glycine 2
H OH H OH Branch at C6
Ans. (d)
Key Concept Ion containing positive as well as negative charge is O
6
called Zwitter ion. CH2OH CH2 CH2OH
Among the given options, only glycine (H2N  CH2  COOH) is an O 5
O O
amino acid which contains both acidic (acquiring negative H H H H H H H H H
4 1 4 1 4 1
charge) and basic group (acquiring positive charge). —O OH H O OH H O OH H O—
Glycine can form a Zwitter ion. It is because glycine behave like 3 2
salts rather than simple amines or carboxylic acids. In aqueous H OH H OH H OH

solution, the carboxyl group can lose a proton and amino group a-Link a-Link
can accept a proton giving rise to a dipolar ion known as Zwitter Amylopectin
ion.
H 09 Which of the following statements is not correct?

H  C  COO− [NEET 2017]
 (a) Insulin maintains sugar level in the blood of a human body
NH3 (b) Ovalbumin is a simple food reserve in egg white
+ (c) Blood proteins thrombin and fibrinogen are involved in blood
Zwitter ion
clotting
Zwitter ion is a cation in acidic medium and migrates to cathode (d) Denaturation makes the proteins more active
on passing electric current. It is an anion in basic medium and Ans. (d)
migrates to anode on passing electric current.
Deprotonation of protein occur when it is subjected to physical
−
OH H+ change like change in temperature or chemical change like
− −
H  C H  COO ← H  C H  COO → H C H  COOH change in pH, the hydrogen bonds are disturbed. As a result,
   globules unfolds and helix get uncoiled and protein losses its
NH2 NH3 NH3 biological activity. Hence, the denaturation of protein makes the
+ +
Anion in basic Cation in acidic protein inactive.
medium medium
Thus, amino acid bears a positive charge in acidic solution (low 10 In a protein molecule various amino acids are linked
pH) and a negative charge in basic solution (high pH). The pH at together by [NEET 2016, Phase I]
which the amino acid has no net charge is called isoelectric point. (a) β-glycosidic bond (b) peptide bond
The isoelectric point of glycine is 5.97. (c) dative bond (d) α-glycosidic bond
Ans. (b)
08 The difference between amylose and amylopectin is
[NEET 2018] Two amino acids in a protein are linked by a peptide bond.
(a) amylopectin have 1 → 4 α-linkage and 1 → 6 β-linkage e.g. glycylalanine is formed when carboxyl group of glycine
(b) amylose have 1 → 4 α-linkage and 1 → 6 β-linkage combines with the amino group of alanine.
(c) amylopectin have 1 → 4 α-linkage and 1 → 6 α-linkage H2N  CH2  CO OH + H2 N  CH COOH
(d) amylose is made up of glucose and galactose
–H2O CH3
Ans. (c) Alanine
Starch contains two components amylose and amylopectin. H2N  CH2  CO  NH  CH  COOH
Chemically, amylose is a long unbranched chain with 200-1000
Peptide linkage
α-D- (+ )-glucose units held by C1-C4 glycosidic linkage. CH3
6 Glycylalanine (Gly-Ala)
CH2OH CH2OH CH2OH
O 5
O O
H H H H H H H H H 11 The correct statement regarding RNA and DNA,
4 1 4 1 4 1
—O
OH H O OH H O OH H O— respectively is [NEET 2016, Phase I]
3 2 (a) The sugar component in RNA is ribose and the sugar
H OH H OH H OH component in DNA is2′-deoxyribose
a-link a-link (b) The sugar component in RNA is arabinose and the sugar
Amylose component in DNA is ribose
(c) The sugar component in RNA is2′-deoxyribose and the sugar
Amylopectin is a branched chain polymer ofα -D-glucose units in component in DNA is arabinose
which chain is formed by C1-C4 glycosidic linkage where (d) The sugar component in RNA is arabinose and the sugar
branching occurs by C1-C6 glycosidic linkage. component in DNA is2′-deoxyribose
Ans. (a) 14 The correct corresponding order of Ans. (d)

In DNA, two helically twisted strands names of four aldoses with D-(+)-glucose contains aldehydic group
connected together by steps. Each configuration given below which reacts with hydroxyl amine
strand consists of alternating molecules (NH2OH) to yield an oxime. The complete
of deoxyribose at 2′-position and CHO CHO reaction is
phosphate groups. H OH HO H CH NOH CH NOH
On the other hand, in RNA, the pentose H OH H OH
sugar has an identical structure with CH2OH CH2OH H C OH H C OH
deoxyribose sugar except that there is CHO CHO HO C H HO C H
an —OH group instead of —H on carbon HO H H OH
+ NH2OH – H2O
atom 2′. H C OH H C OH
HO H HO H
Hence, it is only called ribose. H C OH H C OH
CH2OH CH2OH
respectively, is [NEET 2016, Phase II] CH2OH CH2OH
12 Which one given below is a Glucoxime
D-(+)-glucose
non-reducing sugar? (a) L-erythrose, L-threose, L-erythrose,
[NEET 2016, Phase I] D-threose
(b) D-threose, D-erythrose, L-threose, 16 Which of the following hormones is
(a) Lactose (b) Glucose
(c) Sucrose (d) Maltose L-erythrose produced under the condition of
(c) L-erythrose, L-threose, D-erythrose, stress which stimulates
Ans. (c)
D-threose glycogenolysis in the liver of human
Sucrose is non-reducing sugar because (d) D-erythrose, D-threose, L-erythrose,
O beings? [CBSE AIPMT 2014]
L-threose
 (a) Thyroxin (b) Insulin
reducing part of glucose (  C H) and Ans. (c) Adrenaline (d) Estradiol
fructose (> C == O) are involved in CHO CHO
Ans. (c)
glycosidic linkage. H OH HO H
Adrenaline hormones increases pulse
CH2OH rate and controls blood pressure. It
H OH H OH
O releases glucose from liver glycogen and
H H CH2OH CH2OH fatty acids from fats in emergency.
H D-erythrose D-threose
OH H CHO CHO
HO O Glycosidic 17 Which one of the following sets of
linkage HO H H OH monosaccharides forms sucrose?
H HO [CBSE AIPMT 2012]
HO H HO H
(a) α-D-galactopyranose and
O
HOH2C CH2OH CH2OH α-D-glucopyranose
OH CH2OH L-erythrose L-threose (b) α-D-glucopyranose and
H
H Thus, the correct option is (d). β-D-fructofuranose
H (c) β-D-glucopyranose and
OH α-D-fructofuranose
Sucrose 15 D-(+)-glucose reacts with hydroxyl
(d) α -D-glucopyranose and
amine and yields an oxime. The
While, lactose, glucose and maltose are β-D-fructopyranose
reducing sugars. structure of the oxime would be
[CBSE AIPMT 2014]
Ans. (b)
CH NOH CH NOH Sucrose is composed of
13 The central dogma of molecular α-D-glucopyranose and a
genetics states that the genetic H C OH HO C H β-D-fructofuranose units which are
information flows from joined byα, β-glycosidic linkage between
[NEET 2016, Phase II] HO C H HO C H C-1 of the glucose unit and C-2 of the
(a) (b)
(a) amino acids → proteins → DNA HO C H H C OH fructose unit
(b) DNA → carbohydrates→ proteins CH2OH 1
H C OH H C OH
(c) DNA → RNA → proteins HOH2C
H H O
(d) DNA → RNA → carbohydrates CH2OH CH2OH
Ans. CH NOH CH NOH OH H O
HO Glycosidic
(c) The central dogma of molecular
HO C H H C OH H HO linkage
genetics states that
Transcription H C OH HO C H O H
DNA → RNA (c) (d)
HO C H H C OH 2 H OH
Translation
→ Protein 3
H C OH H C OH CH2OH
Thus, option (c) is correct. OH H
CH2OH CH2OH Structure of sucros
18 Which one of the following undergo mutarotation in aqueous (c) chiral phosphate ester units
solution. (d) D-sugar component
statements is not true regarding (+)
Among the given carbohydrates, only Ans. (d)
lactose? [CBSE AIPMT 2011]
sucrose is a non-reducing sugar as in it
(a) (+) lactose is a β-glycoside formed by the hemiacetal and hemiketal groups of RNA and DNA molecules have ribose and
the union of a molecule of D-(+)- glucose and fructose are linked together deoxyribose sugar respectively. Both are
glucose and a molecule of D-(+)- through O-atom and thus, not free. Due chiral, their chirality is due to D-ribose or
galactose to the absence of free hemiacetal or deoxyribose sugar components.
(b) (+) lactose is a reducing sugar and hemiketal group, sucrose does not
does not exhibit mutarotation exhibit mutarotation. 25 Which one of the following vitamins
(c) (+) lactose, C12H22O11 contains is water-soluble?
8 O  H groups 21 Which of the following hormones [CBSE AIPMT 2007]
(d) On hydrolysis (+) lactose gives equal
contains iodine? (a) Vitamin-B (b) Vitamin-E
amount of D-(+)- glucose and D-(+)-
[CBSE AIPMT 2009] (c) Vitamin-K (d) Vitamin-A
galactose
(a) Insulin (b) Testosterone Ans. (a)
Ans. (b)
(c) Adrenaline (d) Thyroxine Vitamins are classified as
CH2OH
Glycosidic linkage Ans. (d) (i) Fat soluble vitamin-A, D, E, K
O
HO Thyroxine is 3, 5,3′, 5′-tetra (ii) Water soluble vitamin-B complex, H
H O
iodothyronine. It is secreted by follicular and C
OH H
H H H cells of thyroid glands. So, vitamin-B is water soluble.
Its structure is given as
H OH Lactose H
I 26 Which one of the following is a
H OH CCOOH
peptide hormone?
HO I
[CBSE AIPMT 2006]
OH NH2 (a) Glucagon
OH H
I O (b) Testosterone
H
H (c) Thyroxin
O I
CH2OH Thyroxine stimulates the consumption
(d) Adrenaline
of oxygen and thus, the metabolism of all Ans. (a)
19 Which one of the following is cells or tissues in the body. Glucagon is a peptide hormone because
employed as antihistamine? in it peptide linkage is present.
[CBSE AIPMT 2011] 22 The segment of DNA which acts as
(a) Diphenyl hydramine the instrumental manual for the 27 The human body does not produce
[CBSE AIPMT 2006]
(b) Norethindrone synthesis of the protein is
(c) Omeprazole [CBSE AIPMT 2009] (a) DNA (b) vitamins
(d) Chloramphenicol (a) nucleotide (b) ribose (c) hormones (d) enzymes
Ans. (a) (c) gene (d) nucleoside Ans. (b)
Diphenylhydramine (benadryl) is used as Ans. (c) The organic compounds other than
an antihistamine. The segment of DNA which acts as the carbohydrates, proteins which maintain
instrumental manual for the synthesis of normal growth and nutrition in the human
body (but not produced in human body) are
20 Which of the following does not the protein is gene. Every protein in a
called vitamins.
exihibit the phenomena of cell has a corresponding gene.
mutarotation? [CBSE AIPMT 2010] 28 During the process of digestion,
23 Which one of the following is an
(a) (+) Sucrose (b) (+) Lactose the proteins present in food
amine hormone?
(c) (+) Maltose (d) (−) Fructose [CBSE AIPMT 2008]
materials are hydrolysed to amino
Ans. (a) (a) Thyroxin (b) Oxypurin
acids. The two enzymes involved in
Key Idea Reducing sugars that exist in (c) Insulin (d) Progesterone the process
hemiacetal and hemiketal forms, exhibit Ans. (a) Enzyme (A)
the phenomenon of mutarotation in Proteins →
aqueous solution. During mutarotation, Thyroxin is an amine hormone which is
Enzyme (B)
the ring open upto give the open chain secreted by thyroid gland. → Amino acids,
form which then reclose either in the are respectively
inverted position or in the original 24 RNA and DNA are chiral molecules, [CBSE AIPMT 2006]
position giving an equilibrium mixture of their chirality is due to (a) amylase and maltase
two anomers with a small amount of [CBSE AIPMT 2007]
(b) diastase and lipase
open chain form. Thus, all reducing (a) L-sugar component
monosaccharides and disaccharides (c) pepsin and trypsin
(b) chiral bases (d) invertase and zymase
Ans. (c) 36 Which one of the following

HO H
In the process of digestion the proteins
C
* structures represents the peptide
present in food material are hydrolysed chain?
to amino acid. In this process two
HC*OH H
enzymes pepsin and trypsin are involved  C* | 
as follows: HOC* H O (a)  N  C  N  C  NH
 || | 
Pepsin
Proteins → Polypeptide H  C* OH O H O
(Enzyme A) ||
| 
Trypsin | HC*  C NH 
Amino acid ←— — H H
(Enzyme B ) 
CH2OH     
Chiral (Asymmetric) (b)  N  C  C  C  C  N
29 Which functional group carbon atom ||   
participates in disulphide bond O
  
formation in proteins? 33 The correct statement in respect C  C  C 
[CBSE AIPMT 2005] of protein haemoglobin is that it   
(a) Thiolactone (b) Thiol [CBSE AIPMT 2004] H H H
    
(c) Thioether (d) Thioester (a) functions as a catalyst for biological (c) N  N  C  C  N  C  C 
Ans. (b) reactions  ||  ||
(b) maintains blood sugar level O O
Disulphide bond may be reduced to thiol H H
(c) act as an oxygen carrier in the blood    
by means of reagents, i.e. NaBH4 which
shows the presence of thiol group in (d) forms antibodies and offers N CC N C
disulphide bond formation. resistance to diseases  || 
O
Ans. (c)
H O
30 The cell membranes are mainly Haemoglobin acts as oxygen carrier in
     
composed of [CBSE AIPMT 2005] the blood because fourFe2 + ions of each (d)  C  N  C  C  C  N C
(a) carbohydrates (b) proteins haemoglobin can bind with four     
molecules of O2 and form H
(c) phospholipids (d) fats H
oxyhaemoglobin
Ans.    
4Hb + 4O2 → Hb4O8 C N CCC
(c) The cell membranes are mainly ||  
Oxy -haemoglobin 
composed of phospholipids. O
34 The hormone that helps in the Ans. (c)
31 The helical structure of protein is
conversion of glucose to glycogen The peptide linkage ( NH  CO ) is
stabilised by [CBSE AIPMT 2004]
is [CBSE AIPMT 2004] formed by the condensation of amino
(a) dipeptide bonds acids molecules
(a) cortisone
(b) hydrogen bonds HNH C H  COH
(b) bile acids
(c) ether bonds | ||
(c) adrenaline R O
(d) peptide bonds
(d) insulin + H ⋅NH C H  C OH →
Ans. (b)  
Ans. (d)
The helical structure of protein is R O
Insulin hormone helps in the conversion
stabilised by hydrogen bonds between
amide group of the same peptide chain.
of glucose into glycogen by the liver and HN CH  C NH CH  C  Hence,
These bonds are formed by —NH—group of
skeletal muscle. Insulin is secreted by    
pancreas that lower blood glucose level. R O R O
one unit and oxygen of carbonyl group of
the other unit. It takes 3.6 amino acid to following structure represents the
complete one turn of the helix to enable. 35 A sequence of how many peptide chain
Such H-bonding and a 13 memberring is nucleotides in messenger RNA H H H O
formed by H-bonding. This H-bonding is makes a codon for an amino acid?       
responsible for holding helix in a position. [CBSE AIPMT 2004] N  C  C N  C  C N  C  C 
(a) Three (b) Four     
32 Number of chiral carbon atoms in (c) One (d) Two O O
β-D-(+)-glucose is Ans. (a)
[CBSE AIPMT 2004] 37 Chargaff’s rule states that in an
A sequence of three nucleotides in
(a) five (b) six organism [CBSE AIPMT 2003]
messenger RNA makes a codon for an
(c) three (d) four amino acid because four bases in (a) amount of adenine (A) is equal to that
Ans. (a) messenger RNA adenine, cytosine, of cytosine (C) and the amount of
guanine and uracil have been shown to thymine (T) is equal to that of
The number of chiral carbon atoms in guanine (G)
β-D-(+) glucose are five act in the form of triplet.
(b) amounts of all bases are equal 41 Which is not true statement? Ans. (a)
(c) amount of adenine (A) is equal to that [CBSE AIPMT 2002] Starch is also known as amylum which
of thymine (T) and the amount of (a) α-carbon of α-amino acid is occurs in all green plants. A molecule of
guanine (G) is equal to that of asymmetric starch (C6H10O5 ) n is built of a large
cytosine (C) number of α-glucose ring joined through
(b) All proteins are found in L-form
(d) amount of adenine (A) is equal to that oxygen atom.
(c) Human body can synthesise all proteins
of guanine (G) and the amount of
they need
thymine (T) is equal to that of
(d) At pH = 7 both amino and carboxylic 45 Which of the following is correct
cytosine (C) about H-bonding in nucleotide?
groups exist in ionised form
Ans. (c) Ans. (b)
[CBSE AIPMT 2001]
Chargaff ’s rule states that amount of (a) A–T, G–C (b) A–G, T– C
All proteins are not found in L-form but
adenine (A) is equal to that of the amount they may be present in D or L- form. (c) G–T, A–C (d) A–A, T–T
of thymine (T) and the amount of guanine Ans. (a)
(G) is equal to that of the amount of 42 Enzymes are made up of
cytosine (C). [CBSE AIPMT 2002] The structure of DNA molecule is a
double helical structure. In this structure
(a) edible proteins
double helix are made up of two right
38 Glycolysis is [CBSE AIPMT 2003] (b) proteins with specific structure handed helical polynucleotide chains
(a) oxidation of glucose to pyruvate (c) nitrogen containing carbohydrates which are held together by H-bonds. In
(b) conversion of glucose to haem (d) carbohydrates these helixes the adenine (A) base is
(c) oxidation of glucose to glutamate Ans. (b) linked with thymine (T) by two H-bonds
(d) conversion of pyruvate to citrate and guanine (G) is linked with cytocine
Enzymes are made up of proteins with
(C) by three H-bonds as A==T, and G ≡≡ C.
Ans. (a) specific structure and acts as a catalyst
for biochemical reactions.
Glycolysis is the first stage in the 46 Which one of the following gives
oxidation of glucose. It is an anaerobic 43 Which statement is incorrect about positive Fehling’s solution test?
process and involves the degradation of O [CBSE AIPMT 2001]
glucose into two molecules of pyruvate || • • (a) Sucrose (b) Glucose
with the generation of two molecules of peptide bond C NH  ? (c) Fats (d) Protein
ATP. [CBSE AIPMT 2001]
Ans. (b)
(a) C—N bond length in proteins is longer
39 Phospholipids are esters of than usual bond length of C—N bond Glucose reduces Fehling solution to give
glycerol with [CBSE AIPMT 2003] red ppt. of Cu2O.
(b) Spectroscopic analysis show planar
(a) one carboxylic acid residue and two structure of  C NH  group CHO COOH
phosphate groups ||  
O (CHOH) 4 + 2CuO → (CHOH) 4 + Cu2O ↓
(b) three phoshate groups 
(c) C—N bond length in proteins is  Fehling
Red ppt.
(c) three carboxylic acid residues smaller than usual bond length of CH2OH solution CH2OH
(d) two carboxylic acid residues and one C—N bond Glucose
phosphate groups (d) None of the above
Ans. (d) Ans. (c) 47 The hormone which controls the
Phospholipids are esters of glycerol with Peptide bond is formed by the reaction processes like burning of fats,
two carboxylic acid residue and one of —COOH group of one amino acid with proteins and carbohydrates to
phosphate group. the —NH2 group of another amino acid liberate energy in the body is
Hence, phospholipids may be regarded and represented as [CBSE AIPMT 2000]
as derivative of glycerol in which two – (a) cortisone (b) thyroxine
O O
hydroxyl groups are esterified with fatty (c) adrenaline (d) insulin
acid, while third is esterified with
  +
CNH C NH Ans. (b)
phosphoric acid.
As partial double bond character found Thyroxine is a hormone secreted by
between C—N bond, the bond length of thyroid gland. This hormone controls
40 Vitamin-B 12 contains C—N in protein should be smaller than various biochemical reactions involving
[CBSE AIPMT 2003] usual C—N bond. burning of proteins, carbohydrates, fats
(a) Zn (II) to release energy.
(b) Ca (II) 44 Which of the following is correct
It is an iodinated derivatirve of amino
(c) Fe (II) statement? [CBSE AIPMT 2001]
acid tyrosine.
(d) Co (III) (a) Starch is a polymer ofα-glucose
(b) Amylose is a component of cellulose
Ans. (d) 48 α-D-(+)-glucose and β-D-(+)-glucose
(c) Proteins are composed of only one
The molecular formula of vitamin-B12 is type of amino acid are [CBSE AIPMT 2000]
C63H88 N14O14PCo and the chemical name (d) In cyclic structure of fructose, there (a) anomers (b) epimers
is cyanocobalamine. So, cobalt is are four carbons and one oxygen (c) enantiomers
present in vitamin-B12 . atom (d) geometrical isomers
Ans. (a) 52 Aspirin is an acetylation product of Thus, three phenyl hydrazine molecules
Those diastereomers which differ only in [CBSE AIPMT 1998] and one molecule of glucose is required
configuration at C-1 are known as to form osazone.
(a) o -hydroxybenzoic acid
anomers (b) o -hydroxybenzene
(c) m -hydroxybenzoic acid 54 Haemoglobin is [CBSE AIPMT 1997]
H—C—OH HO—C—H
| | (d) p -dihydroxybenzene (a) an enzyme
H—C—OH H—C—OH Ans. (a) (b) a globular protein
| | OCOCH3 (c) a vitamin
O O
HO—C—H HO—C—H (d) a carbohydrate
| | COOH
Structure of Aspirin is Ans. (b)
H —C —OH H—C—OH
| | Haemoglobin is a globular protein of four
H—C H—C It is prepared by the reaction of acetic sub-units, it contains 94% globin.
| | anhydride with salicyclic acid in the
CH 2OH CH 2OH presence of a catalyst (H2SO4 ) 55 The function of enzymes in the
α-D-(+)-glucose β-D-(+)-glucose OH living system is to
Anomers COOH [CBSE AIPMT 1997]
H2SO4
+ (CH3CO)2O (a) transport oxygen
49 Which one of the following has (b) provide immunity
magnesium? [CBSE AIPMT 2000] Salicylic OCOCH3
(c) catalyse biochemical reactions
(a) Vitamin-B 12 (b) Chlorophyll acid
COOH (d) provide energy
(c) Haemocyanin (d) Carbonic + HCl Ans. (c)
anhydrase
Acetyl salicylic acid C Enzymes are globular proteins which
Ans. (b)
(Aspirin) catalyse biochemical reaction in the
Formula of chlorophyll is C55H72MgN2O6 . CH3 —C—OH living systems.
So Mg is present in chlorophyll. It is the
green colouring matter of leaves and
green stems.
53 Glucose molecule reacts with ‘ X ’ 56 Which one of the following
Vitamin-B12 contains cobalt, number of molecules of phenyl chemical units is certainly to be
haemocyanin contains copper and hydrazine to yield osazone. The found in enzyme?
carbonic anhydrase contain zinc. value of ‘ X ’ is [CBSE AIPMT 1998] [CBSE AIPMT 1997]
50 Which of the following is the (a) four (b) one (c) two (d) three OH O
sweetest sugar? [CBSE AIPMT 1999] Ans. (d) (a)
O |
(a) Sucrose (b) Glucose H CH N·NHC6H5 HO | O
H OH
(c) Fructose (d) Maltose C O C
Ans. (c) H2N·NHC6H5 OH N
CHOH (b)
Fructose is the sweetest sugar and –H2O (CHOH)3
highly soluble in water and slightly (CHOH)3 N
soluble in alcohol. It is insoluble in ether CH2OH
fructose in laevorotatory hence, called CH2OH glucose phenyl hydrazone H
laevulose. glucose |
(c) NC
CH NH ||
51 In DNA, the complementary bases O
are [CBSE AIPMT 1998, 2008] C O CH NH
NHC6H5 O
(a) adenine and thymine, guanine and –C6H5NH2
cytosine C O H O O R
(CHOH)3
C6H5NH·NH2
(b) uracil and adenine, cytosine and

H2O
(CHOH)3 (d)
guanine CH2OH O R
O
(c) adenine and guanine, thymine and imino ketone CH20H O R
cytosine hydrogen bonded
(d) adenine and thymine, guanine and intermediate Ans. (c)
CH NH
uracil Peptide bonds are present in enzyme
C3H5NH·NH2
Ans. (a) C N·NHC6H5 CH N·NH·C6H5 because enzymes are made up of
–NH3
DNA has a double helical structure. These proteins, and proteins are the polymer
(CHOH)3 C N·NH·C6H5
helix contains polynucleotide chains and  H 
these chains are held together by CH2OH  | 
hydrogen bonds. In these polynucleotide (CHOH)3  — N— C — 
chain of DNA, adenine has thymine  || 
CH2OH  O 
opposite to it and guanine has cytosine glycosazone
opposite to it. (yellow crystalline solid)
57 Sucrose in water is dextrorotatory, (b) Insulin combined with biopolymers (known as

nucleic acids). Nucleic acids are
[α] D = + 66.4° when boiled with dil. (c) Chromoprotein
(d) Phosphoprotein biologically important polymers which
HCl, the solution becomes are present in all living cells. DNA is the
leavorotatory, [α] D = − 39.9° . In this Ans. (a) polymer of nucleotides.
process the sucrose breaks into Antibodies are the proteins which
[CBSE AIPMT 1996] protect the body against toxic 63 Diazo coupling is useful to prepare
(a) L-glucose + D-fructose substances and infections. When an some [CBSE AIPMT 1994]
antigen enter in the body cells, the
(b) L-glucose + L-fructose (a) pesticides (b) dyes
antibodies present in the body destroyed
(c) D-glucose + D-fructose the antigen. (c) proteins (d) vitamins
(d) D-glucose + L-fructose Ans. (b)
Ans. (c) 60 The α-D-glucose and β-D-glucose Diazo coupling is the reaction in which
The aqueous solution of sucrose is differ from each other due to phenol, or aniline reacts with
dextrorotatory having [α] D = + 66.4° .On difference in carbon atom with benzenediazonium salt to produce dyes
hydrolysis with dilute acids or enzyme with (—N==N —) azo groups.
invertase, cane sugar (sucrose) gives respect to its [CBSE AIPMT 1995]
equimolar mixture of D-(+)-glucose and (a) conformation
+ –
D-(–)-fructose (b) configuration —N2Cl + H— —NH2
HCl (c) number of OH-groups
C12H22O11 + H2O → C6H12O6
Cane sugar
(d) size of hemiacetal ring
D -glucose —N N— —NH2
[α] D = 66.4° [α] D = + 52.5 Ans. (b) –HCl
azo dye
+ C6H12O6 The isomer having the hydroxyl group
D-fructose (—OH) on the right is calledα-D-glucose
[α] D = – 92.4° and one having the hydroxyl group (—OH) 64 The couplings between base units
on the left is calledβ-D-glucose. Such
So, sucrose is dextrorotatory but after of DNA is through
pairs of optical isomers which differ in
hydrolysis gives dextrorotatory glucose [CBSE AIPMT 1992]
the configuration only around C1 atom
and laevorotatory fructose. (a) hydrogen bonding
are called anomers. Thus α-D-glucose
D-(–)-fructose has a greater specific
and β-D-glucose are anomers. (b) electrostatic bonding
rotation than D-(+)-glucose. Therefore,
(c) covalent bonding
the resultant solution is laevorotatory in
nature with specific rotation of –39.9°. 61 Chemically considering digestion is (d) van der Waals’ forces
basically [CBSE AIPMT 1994] Ans. (a)
58 In reference to biological role, Ca 2+ (a) anabolism In DNA the two strands are held together by
ions are important in (b) hydrogenation hydrogen bonds. For example guanine is
[CBSE AIPMT 1996] (c) hydrolysis bonded to cytosine and adenine to thymine
(a) triggering the contraction of (d) dehydrogenation by hydrogen bonding.
muscles Ans. (c)
(b) generating the right electrode 65 On hydrolysis of starch, we finally
Digestion is basically hydrolysis reaction
potential across cell membrane
in which large molecules are hydrolysed
get [CBSE AIPMT 1991]
(c) hydrolysis of ATP to give smaller molecules. For example (a) glucose (b) fructose
(d) defence mechanism when we eat proteins, it will hydrolyse (c) Both (a) and (b) (d) sucrose
Ans. (b) and form amino acids. Ans. (a)
The Ca2 + ion generates the right Starch is hydrolysed with dilute acids or
electrical potential across cell 62 An example of biopolymer is enzymes and break down to molecules
membrane. [CBSE AIPMT 1994]
of variable complexity and finally gives
(a) teflon (b) neoprene D-glucose.
59 Which of the following protein (c) nylon-66 (d) DNA (C6H10O5 ) n → (C6H10O5 ) n ′ →
destroy the antigen when it enters Ans. (d) Starch Diastase
in body cell? [CBSE AIPMT 1995] All living cells contains nucleoproteins, C12H22O11 → C6H12O6
(a) Antibodies i.e. substances made up of proteins D-glucose
Maltose
TOPIC 2 67 Which of the following will not OH CH2 OH

Cl
Chemistry in undergo SN 1 reaction with OH ? O2N CH CH NHCOCH
[NEET (Oct.) 2020] (Chloramphenicol) Cl
Everyday LIfe (a) CH2 ==CH CH2Cl
(b) (CH3) 3CCl Narrow-spectrum antibiotics are
effective against gram-positive or
66 Which one of the following CH2CH2Cl CH2Cl
gram-negative bacteria.
polymers is prepared by addition Bactericidals show cidal or killing effect
polymerisation? [NEET 2021] (c) (d) on microbes.
(a) Teflon (b) Nylon-66
(c) Novolac (d) Dacron Ans. (c) 69 Which of the following is a cationic
Ans. (a) An S N 1 reaction proceeds through detergent? [NEET (Sep.) 2020]
formation of a stable carbocation as an (a) Sodium stearate
Addition polymerisation Monomers are intermediate. Here,
added one after other in addition (b) Cetyltrimethyl ammonium bromide
–Cl– (c) Sodium dodecyl benzene sulphonate
polymerisation. (a) CH2 CH CH2Cl
Teflon Addition polymerisation. r (d) Sodium lauryl sulphate
CH2 CH CH2
F F F F Allyl-1°-carbocation
Ans. (b)
n (stable) (a) Solution stearate, C17H35 COONa is a
F F F F n − ⊕ soap.
− Cl
Tetrafluoro Teflon (b) (CH3) 3 CCl → CH3  C  CH3 (b) Cetyltrimethyl ammonium bromide,
ethene  ⊕ È
CH3 CH3  (CH2 ) 15 N(CH3) 3 Br is a
Nylon-6, 6 Condensation polymerisation.
(9 hyper cationic detergent.
O
conjugations) (c) and (d) are anionic detergents.
HO ( CH2
( COH Sodium dodecyl benzene sulphonate :
4 tert-butyl carbocation (stable)
O È ⊕
Adipic acid + H2N( CH2
( 6 NH2 p- CH3 (CH2 ) 11  C6H4 SO 3 N a
(c) –Cl–
Hexamethylene CH2CH2Cl
Sodium lauryl sulphate:
diamine –I È ⊕
r CH3  (CH2 ) 10  CH2 OSO 3 N a
O O
CH2CH2
–H2O ( C( CH 
 2 ( C 4
(
70 Among the following, the narrow
NHCH2NH
( (
6 n 1°-carbocation (less stable due spectrum antibiotic is
Nylon-6, 6 to –I effect of the phenyl group) [NEET (National) 2019]
Novolac Condensation polymerisation. –Cl–

(a) ampicillin
(d) CH2Cl (b) amoxycillin
OH OH
CH2OH r (c) chloramphenicol
H+ CH2 (d) penicillin G
+ HCHO
OH– Ans. (d)
Formaldehyde Benzyl-1°-carbocation (stable)
Phenol Key Idea Antibiotics which are effective
OH So, option (c) will not undergoS N 1 mainly against either gram positive or
reaction withOH− . gram negative bacteria are called narrow
CH2 CH2
n spectrum antibiotics.
68 Which of the following is not true Penicillin G has a narrow spectrum.
Novolac about chloramphenicol? Ampicillin and amoxycillin are synthetic
Dacron Condensation polymerisation. [NEET (Oct.) 2020] modifications of penicillin.
(a) It inhibits the growth of only These have broad spectrum. Also,
COOH
gram-positive bacteria chloramphenicol is a broad spectrum
OH –H2O (b) It is a broad spectrum antibiotic antibiotic.
+ (c) It is not bactericidal Hence, option (d) is correct.
HO
Glycol (d) It is bacteriostatic
COOH Ans. (a) 71 The artificial sweetner stable at
Terephthalic acid
cooking temperature and does not
O O Chloramphenicol is a bacteriostatic
(inhibitory) broad spectrum antibiotic, provide calories is
O( CH2
2
OC ( C which shows inhibitory effect on wide [NEET (Odisha) 2019]
n range of gram-positive and (a) saccharin (b) aspartame
Dacron
gram-negative bacteria (microbes). (c) sucralose (d) alitame
Ans. (c) 74 Bithional is generally added to the concentration (1%) as disinfectant.

Chlorine and iodine are strong
Sucralose is a trichloro derivative of soaps as an additive to function as
sucrose and is about 650 times sweeter disinfectants whereas dilute solutions of
a/an [CBSE AIPMT 2015] boric acid and hydrogen peroxide are
than cane sugar. It is a zero calorie sugar
and stable at cooking temperature.
(a) softener (b) dryer mild antiseptics.
H (c) buffering agent (d) antiseptic
OH
Ans. (d) 77 Which one of the following is
O
Cl H Bithional is added to soap to impart employed as a tranquilizer drug?
OH [CBSE AIPMT 2010]
antiseptic properties. It reduces odours
HO
OH produced by bacterial decomposition of (a) Promethazine (b) Valium
H organic matter on the skin . (c) Naproxen (d) Mifepristone
OH H
OH OH Ans. (b)
CH2Cl Cl S Cl Tranquilizer are the chemicals that
O
H HO reduce anxiety and mental tensional.
Tranquilizer is the strain reliever also
ClH2C O H used for mild and essential component
Sucralose Cl Cl of sleeping pills. Thus, they are
IUPAC Name 2,2sulfanediylbis sometimes called psychotherapeutic
72 Mixture of chloroxylenol and (4, 6-dichlorophenol) drugs. Equanil, valium and serotonin and
barbiturates (hypnotic) are some
terpineol acts as [NEET 2017]
commonly used tranquilizers.
(a) analgesic (b) antiseptic 75 Artificial sweetener which is stable
(c) antipyretic (d) antibiotic under cold conditions only is 78 Which one of the following is
[CBSE AIPMT 2014] employed as a tranquiliser?
Ans. (b)
(a) saccharine (b) sucralose [CBSE AIPMT 2009]
(a) The medicines which are used to
reduce pain are known as analgesics. (c) aspartame (d) alitame (a) Equanil (b) Naproxen
For example paracetamol, ibuprofen, Ans. (c) (c) Tetracycline (d) Chlorpheninamine
morphine, etc. Aspartame is the only artificial Ans. (a)
(b) The chemicals which either prevent sweetener which is stable at lower The drugs which are used to reduce
the growth of microorganisms or kill temperature and decomposes at higher anxiety and for the treatment of mental
them but are not harmful to the living temperature. It is also called Nutra diseases, are called tranquilisers. These
tissues are known as antiseptics. sweet. It’s relative sweetness value is drugs are also known as
e.g. savlon, dettol. Dettol is one of 180. pyschotherapeutic drugs. Luminal,
the most commonly used
seconal and equanil are some commonly
antiseptics. It is a mixture of 76 Antiseptics and disinfectants either used and are the example of tranquiliser.
chloroxylenol and α-terpineol.
kill or prevent growth of
(c) The chemical substances which are 79 Which of the following can possibly
used to bring down body temperature microorganisms. Identify which of
during fever are called antipyretics, the following is not true. [NEET 2013] be used as analgesic without
e.g. aspirin, novalgin, etc. (a) A 0.2% solution of phenol is an causing addiction and mood
(d) The chemicals which are obtained antiseptic while 1% solution acts as a modification? [CBSE AIPMT 1997]
from microorganisms such as disinfectant (a) Morphine
bacteria, fungi, etc., or by synthetic (b) Chlorine and iodine are used as (b) Diazepam
methods and used to inhibit the strong disinfectants (c) Tetrahydrocational
growth or even kill the (c) Dilute solutions of boric acid and (d) N-acetyl-para-aminophenol
microorganisms are called hydrogen, peroxide are strong
antibiotics, e.g. penicillin, antiseptics Ans. (d)
chloramphenicol, etc. (d) Disinfectants harm the living tissues N-acetyl-para-aminophenol or
Ans. (c) paracetamol is used as analgesic as well
73 Which of the following is an as antipyretic.
Antiseptics and disinfectants both either
analgesic? [NEET 2016, Phase I]
kill or prevent the growth of 80 Commonly used antiseptic ‘Dettol’
(a) Penicillin (b) Streptomycin microorganisms. The main point of is a mixture of [CBSE AIPMT 1996]
(c) Chloromycetin (d) Novalgin difference between these two is that the
former (antispetics) are used for living (a) o-chlorophenoxylenol + terpineol
Ans. (d)
beings whereas disinfectants are not (b) o-cresol + terpineol
Novalgin (Dipyrone) is a non-narcotic (c) phenol + terpineol
safe for living tissues. These are actually
analgesic used as pain reliever.
used for inanimate objects like floors, (d) chloroxylenol + terpineol
Penicillin is an antibiotic used for tiles, etc.
curing rheumatic fever. Ans. (d)
A substance like phenol in its lower
Streptomycin is an antibiotic drug. Dettol is an antiseptic. It is a mixture of
concentration (0.2%) behaves as
Chloromycetin is an antibiotic drug. chloroxylenol and terpineol in a suitable
antiseptic, whereas in higher
solvent.
TOPIC 3 (c) It is produced due to incomplete 87 Which one of the following is not a
combustion.
Environmental common component of
(d) It forms carboxyhaemoglobin.
photochemical smog?
Chemistry Ans. (b)
(a) Ozone [CBSE AIPMT 2014]
Statements (a), (c) and (d) are correct (b) Acrolein
81 The RBC deficiency is deficiency about carbon monoxide (CO).
(c) Peroxyacetyl nitrate
disease of [NEET 2021] Statement (b) is not correct about CO,
(d) Chlorofluorocarbons
because carboxyhaemoglobin
(a) vitamin-B 12 (b) vitamin-B 6 Ans. (d)
(haemoglobin bound to CO) is about 300
(c) vitamin-B 1 (d) vitamin-B2 times more stable than oxyhaemoglobin Among the given chlorofluorocarbons
Ans. (a) complex. are the compounds that are responsible
for the ozone depletion which degrade
VitaminB12 deficiency disease-RBC ozone into moleculer oxygen. It is not a
deficiency (anaemia). 84 Among the following, the one that
component of photochemical smog
VitaminB6 deficiency disease–Dermatitis, is not a green house gas is while other are component of smog.
epilepsy. [NEET (National) 2019]
VitaminB1 deficiency disease – Beri-beri (a) methane (b) ozone 88 Which one of the following
VitaminB2 deficiency disease – (c) sulphur dioxide (d) nitrous oxide statements regarding
Ariboflavinesis. Ans. (c) photochemical smog is not correct?
Sulphur dioxide (SO2 ) is not a green [CBSE AIPMT 2012]
82 Which of the following statement is house gas. Carbon dioxide (CO2 ), (a) Carbon monoxide does not play any
not true about acid rain? methane (CH4 ), water vapour, nitrous role in photochemical smog
[NEET (Oct.) 2020] oxide (N2O), CFCs and ozone (O3) are the formation
(a) It is due to reaction ofSO2 , NO2 and green house gases. These gases are (b) Photochemical smog is an oxidising
CO2 with rain water. responsible for global warming. agent in character
(b) Causes no damage to monuments (c) Photochemical smog is formed
like Taj Mahal. 85 The liquified gas that is used in dry through photochemical reaction
involving solar energy
(c) It is harmful for plants. cleaning along with a suitable (d) Photochemical smog does not cause
(d) Its pH is less than 5.6 detergent is [NEET (Odisha) 2019] irritation in eyes and throat
Ans. (b) (a) water gas (b) petroleum gas Ans. (d)
Air pollutants likeSO2 , NO2 and CO2 get (c) NO2 (d) CO2
Photochemical smog is formed in warm
dissolved in rain water to produce acid Ans. (d) and sunny climate during day time by the
rain which constitutes mainlyH2SO4 ,
Solvents used to dry clean clothes are action of sunlight on primary pollutants. It
HNO3 and H2 CO3.
usually chlorinated compounds which contains nitrogen oxides, ozone, PAN,
2SO2 (g) + O2 (g) + 2H2O(l ) → 2H2SO4 (aq) are carcinogenic. Suitable detergents etc., which are oxidising in nature. So,
4NO2 (g) + O2 (g) + 2H2O(g) → 4HNO3 (aq) which work in liquid carbon dioxide have photochemical smog is an oxidising agent
been discovered to replace the in character. It causes irritation in eyes
CO2 (g) + H2O(l ) → H2 CO3 (aq) and throat.
chlorinated compounds. Thus, CO2 is the
Due to the presence of these acids, pH liquified gas that is used in dry cleaning
of rain water drops below 5.6. along with a suitable detergent. 89 Green chemistry means such
Acid rain damages marbles of Taj Mahal. reactions which [CBSE AIPMT 2008]
CaCO3 (s ) + H2SO4 (aq) → CaSO4 (aq) 86 Which of the following is a sink for (a) produce colour during reactions
Marble + H2O(l ) + CO2 (g) CO ? [NEET 2017]
(b) reduce the use and production of
hazardous chemicals
Thus, Taj Mahal gets disfigured, (a) Haemoglobin
discoloured and lustreless. (c) are related to the depletion of ozone
(b) Microorganisms present in the soil layer
(c) Oceans (d) study the reactions in plants
83 Which of the following statements (d) Plants Ans. (b)
is not correct about carbon Ans. (b) Green chemistry means, the production
monoxide? [NEET (Sep.) 2020]
Microorganisms present in the soil act as of chemicals of our daily needs by using
(a) It reduces oxygen carrying ability of biggest source and sink. A sink is a such reactions and chemical processes
blood. natural or artificial reservoir that which neither use toxic chemicals, nor
(b) The carboxyhaemoglobin accumulates and stores some chemical emit such chemicals into atmosphere.
(haemoglobin bound to CO) is less compound for an indefinite period. Thus Thus, green chemistry is an alternative
stable than oxyhaemoglobin. (b) is correct option. tool for reducing pollution.

Arihant NEET 34 Years Chapterwise Solutions Chemistry 2022

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Arihant NEET 34 Years Chapterwise Solutions Chemistry 2022

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34

Arihant Prakashan (Series), Meerut

Administrative & Production Offices

Whenever a student decides to prepare for any examination his/her

We feel great pleasure in presenting before you this book containing

We hope this chapterwise solved papers would be highly beneficial to

1. Some Basic Concepts in Chemistry 1-8

2. Atomic Structure 9-16

3. Chemical Bonding and Molecular Structure 17-32

4. Chemical Thermodynamics 33-43

5. States of Matter 44-49

6. Solid State 50-55

8. Chemical Equilibrium 65-69

9. Ionic Equilibrium 70-79

10. Redox Reactions and Electrochemistry 80-89

11. Chemical Kinetics 90-99

12. Surface Chemistry 100-103

13. Classification of Elements and Periodicity in Properties 104-108

14. General Principles and Processes of Isolation of Metals 109-112

15. Hydrogen 113-114

16. s-Block Elements 115-118

17. p- Block Elements 119-134

18. d and f-Block Elements 135-144

20. Purification and Characterisation of Organic Compounds 157-159

21. Some Basics Principles of Organic Chemistry 160-174

22. Hydrocarbons 175-184

23. Organic Compounds Containing Halogens 185-190

24. Organic Compounds Containing Oxygen 191-216

25. Organic Compounds Containing Nitrogen 217-226

26. Polymers 227-231

27. Biomolecules , Chemistry in Everyday Life and Environmental Chemistry 232-242

UNIT II Structure of Atom

UNIT III Classification of Elements and Periodicity in Properties

UNIT IV Chemical Bonding and Molecular Structure

UNIT V States of Matter: Gases and Liquids

UNIT VII Equilibrium

UNIT X s-Block Elements (Alkali and Alkaline Earth Metals)

UNIT XI Some p-Block Elements

UNIT XII Organic Chemistry- Some Basic Principles and Techniques

UNIT XIII Hydrocarbons

UNIT XIV Environmental Chemistry

UNIT III Electrochemistry

UNIT IV Chemical Kinetics

UNIT V Surface Chemistry

UNIT VI General Principles and Processes of Isolation of Elements

UNIT VII p- Block Elements

UNIT XI Coordination Compounds

UNIT X Haloalkanes and Haloarenes

UNIT XI Alcohols, Phenols and Ethers

UNIT XII Aldehydes, Ketones and Carboxylic Acids

UNIT XIII Organic Compounds Containing Nitrogen

UNIT XIV Biomolecules

UNIT XVI Chemistry in Everyday Life

% At. Molar Simple soluble product potassium

abundance wt. ratio ratio

250 1 23 Volume occupied by one molecule 25 Percentage of Se in peroxidase

3 NaCl in equal volume with the help of

16.0 Ans. (c)

Ans. (d) 25 If uncertainty in position and 27 The value of Planck’s constant is

44 The correct set of four quantum 48 Consider the following sets of

Ans. (d) 52 The electronic configuration of Ans. (b)

Ans. (a) (a) d-orbital (b) f-orbital Ans. (b)

(a) Hund’s rule (a) 4l − 2 (b) 4l + 2

When azimuthal quantum number is 3