Chemistry

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C
CHEMISTRY
h apter
ontents
01. SOLID STATE 03
02. SOLUTION 21
03. ELECTROCHEMISTRY 47
04. CHEMICAL KINETICS 70
05. SURFACE CHEMISTRY 91
06. THE P-BLOCK ELEMENTS 109
07. THE D & F-BLOCK ELEMENT 146
08. COORDINATION COMPOUND 166

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accordingly.
So strictly follow the given study material by ALLEN.
CBSE Syllabus
ALLEN
CLASS XII (2020-21)
(THEORY)
Total Periods (Theory 98 + Practical 36)
Time : 3 Hours 70 Marks
Unit No. Title No. of Periods Marks
Unit I Solid State 8
Unit II Solutions 8
Unit III Electrochemistry 7 23
Unit IV Chemical Kinetics 5
Unit V Surface Chemistry 5
Unit VII p -Block Elements 7
Unit VIII d -and f -Block Elements 7 19
Unit IX Coordination Compounds 8
Unit X Haloalkanes and Haloarenes 9
Unit XI Alcohols, Phenols and Ethers 9
Unit XII Aldehydes, Ketones and Carboxylic Acids 10 28
Unit XIII Amines 7
Unit XIV Biomolecules 8
Total 98 70
Unit I: Solid State 8 Periods

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.
Unit II: Solutions 8 Periods

Types of solutions, expression of concentration of solutions of solids in liquids, solubility of
gases in liquids, solid solutions, Raoult’s law, colligative properties - relative lowering of vapour
pressure, elevation of boiling point, depression of freezing point, osmotic pressure,
determination of molecular masses using colligative properties.
Unit III: Electrochemistry 7 Periods

Redox reactions, EMF of a cell, standard electrode potential, Nernst equation and its application
to chemical cells, Relation between Gibbs energy change and EMF of a cell, conductance in
electrolytic solutions, specific and molar conductivity, variations of conductivity with
concentration, Kohlrausch’s Law, electrolysis.
Unit IV: Chemical Kinetics 5 Periods

Rate of a reaction (Average and instantaneous), factors affecting rate 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).
Unit V: Surface Chemistry 5 Periods

Adsorption - physisorption and chemisorption, factors affecting adsorption of gases on solids,
colloidal state: distinction between true solutions, colloids and suspension; lyophilic, lyophobic,
multi-molecular and macromolecular colloids; properties of colloids; Tyndall effect, Brownian
movement, electrophoresis, coagulation.
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Unit VII: p-Block Elements 7 Periods
Group -15 Elements: General introduction, electronic configuration, occurrence, oxidation states,
trends in physical and chemical properties; Nitrogen preparation properties and uses;
compounds of Nitrogen: preparation and properties of Ammonia and Nitric Acid.
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
properties and uses of Sulphur-dioxide, Sulphuric Acid: 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 7 Periods

General introduction, electronic configuration, occurrence and 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.
Lanthanoids - Electronic configuration, oxidation states and lanthanoid contraction and its
consequences.
Unit IX: Coordination Compounds 8 Periods

Coordination compounds - Introduction, ligands, coordination number, colour, magnetic
properties and shapes, IUPAC nomenclature of mononuclear coordination compounds. Bonding,
Werner's theory, VBT, and CFT.
Unit X: Haloalkanes and Haloarenes 8 Periods

Haloalkanes: Nomenclature, nature of C–X bond, physical and chemical properties, optical
rotation mechanism of substitution reactions.
Haloarenes: Nature of C–X bond, substitution reactions (Directive influence of halogen in
monosubstituted compounds only).
Unit XI: Alcohols, Phenols and Ethers 8 Periods

Alcohols: Nomenclature, methods of preparation, physical and chemical properties (of primary
alcohols only), identification of primary, secondary and tertiary alcohols, mechanism of
dehydration.
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 10 Periods

Aldehydes and Ketones: Nomenclature, nature of carbonyl group, methods of preparation,
physical and chemical properties, mechanism of nucleophilic addition, reactivity of alpha
hydrogen in aldehydes, uses.
Carboxylic Acids: Nomenclature, acidic nature, methods of preparation, physical and chemical
properties; uses.
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CBSE Syllabus
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Unit XIII: Amines 7 Periods
Amines: Nomenclature, classification, structure, methods of preparation, physical and chemical
properties, uses, identification of primary, secondary and tertiary amines.
Unit XIV: Biomolecules 7 Periods

Carbohydrates - Classification (aldoses and ketoses), monosaccahrides (glucose and fructose),
D-L configuration
Proteins -Elementary idea of - amino acids, peptide bond, polypeptides, proteins, structure of
proteins - primary, secondary, tertiary structure and quaternary structures (qualitative idea
only), denaturation of proteins.
Nucleic Acids: DNA and RNA.
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SOLID STATE
Distinction between Crystalline and Amorphous Solids
Property Crystalline Solids Amorphous Solids

Shape Definite characteristic geometrical shape Irregular shape
Melting point Melt at a sharp and characteristic Gradually soften over a range of
temperature temperature
Cleavage When cut with a sharp edged tool, they When cut with a sharp edged tool, they
property split into two pieces and the newly cut into two pieces with irregular
generated surfaces are plane and smooth surfaces
Heat of fusion They have a definite and characteristic They do not have definite heat of fusion
heat of fusion
Anisotropy Anisotropic in nature Isotropic in nature
Nature True solids Pseudo solids or super cooled liquids
Order in Long range order Only short range order.
arrangement
of constituent
particles
TYPES OF THE CRYSTALLINE SOLID

Constituent Bonding/ Physical Electrical Melting
Types of Solid Examples
Particles Attractive forces Nature Conductivity Point
(1) Molecular Solids
(i) Non polar Molecules Disppersion or Ar, CCl4, H2, I2 Soft Insulator Very low
London forces CO2
(ii) Polar Dipole-dipole HCl, SO 2 Soft Insulator Low
node06\B0B0-BA\Kota\Board Material\Chemistry\CBSE\CBSE Booklet\English\Updated booklet-21\New Pattern CBSE Booklet\Part wise boocklet\Part 1\01_PC\01_Solid State
(iii) Hydrogen Hydrogen Hard Insulator Low

H2O (ice)
bonded bonding
(2) Ionic Solids Ions Coulombic or Hard but Insulator in High
NaCl, MgO,
electrostatic brittle solid state but
ZnS, CaF2
conductors
in molten
state and in
aqueous
solutions
(3) Metallic Solids Positive ions Metallic Hard but Conductors in Fairly
Fe, Cu, Ag, Mg
in a sea of bonding malleable solid state as high
delocalised and well as in
electrons ductile molten state
(4) Covalent or Atoms Covalent SiO2 (quartz) Hard Insulators Very
network Solids bonding high
SiC,
C (diomond)
AIN,
C(graphite) Soft Conductor
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THE SEVEN CRYSTAL SYSTEMS
Name of Axes Angles Bravais Lattices
System
1. Cubic a=b=c a = b = g =90° Primitive, Face-centred,
Body centred = 3
2. Tetragonal a= b ¹ c a = b = g = 90° Primitive, Body centred = 2
3. Rhombohedral a = b= c a = b = g ¹ 90° Primitive = 1
or Trigonal
4. Orthorhombic a¹b¹ c a = b = g = 90° Primitive, Face-centred,
or Rhombic Body centred End centred
5. Monoclinic a¹b¹c a = g = 90°; Primitive, End - centred = 2
b ¹ 90°
6. Triclinic a¹b¹c a ¹ b ¹ g ¹ 90° Primitive = 1
7. Hexagonal a=b¹c a = b = 90° Primitive = 1
g = 120° Total = 14
CUBIC UNIT CELL
Unit cell Relation Packing Co-ordinatin Effective number
between fraction number of particle
r and a
a
Simple cubic r= 52.4% 6 1
2
Body centred
a 3
cubic r= 68% 8 2
4
a 2
Face centred r= 74% 12 4
4
cubic
l HCP and CCP have equal efficiency i.e., 74% of space is occupied and coordination number is 12.
CCP arrangement has FCC lattice.
l Coordination number is the number of nearest neighbouring points surrounding a particular lattice
point (point may be atom, ions or molecules).
l Packing efficiency in simple cubic unit cell is 52.4%, in bcc arrangement is 68% and in fcc is 74%.
l Unoccupied spaces in solids are called interstitial voids or interstitial sites.
l Two types of interstitial voids are :
(i) tetrahedral void
(ii) octahedral void
· No. of tetrahedral voids = 2 × N (where N is number of closed packed particles).
· No. of octahedral voids = N.
l Valency defect lowers the density of a crystal.
l Interstitial defect increases the density of a crystal.
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l Point defects in the ionic crystal may be classified as :
(i) Stoichiometric defect also known as intrinsic or thermodynamic defect. Ratio of cations and
anions is the same in defective crystal as in ideal crystal.
(ii) In non-stoichiometric defect ratio of cations to anions is the difference in defective crystal from
the ideal crystal.
(iii) Impurity defect (due to presence of some other ions at the lattice sites).
l Schottky defect arises due to missing of equal number of cations and anions from lattice sites in the crystalline
solid of the type A+B– and it lowers and density of alkali metal halides, e.g., NaCl, KCl etc.
l Frenkel defect is the combination of vacancy and interstitial defects. Cations leave their actual lattice
sites and occupy the interstitial space in the solid. Density remains the same in Frenkel defect. AgBr
is the compound which shows both Schottky defect as well as Frenkel defect.
l Non-stoichiometric defect
(i) Metal excess defect due to anion vacancies.
(ii) Metal excess defect due to presence of extra cations.
(iii) Metal deficiency due to absence of cations.
l F-Center : In metal excess defect, electrons are trapped in the anion vacancies which act as colour
centres, e.g., NaCl gives yellow colour when heated in sodium vapour.
l Calculation of number of particles/atoms/ions in a unit cell :
Type of unit cell Number of particles Relationship between edge
per unit cell length (a) and radius (r) of
atom/ion
Simple cubic (SC) 1 a = 2r
4
Body centred cubic (BCC) 2 a= r
Face centred cubic (FCC) 4 a =2 2r

l Density of unit cell :
ZM
d=
a 3NA
where Z is rank of unit cell (number of atoms per unit cell), M is molar mass/atomic mass, a is edge
length of the cube, a3 is volume of cubic unit cell and NA is Avogadro constant.
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Z ´ pr 3
l Packing efficiency, PE = 3 ´100
a3
Here, M is molar mass, r is radius of atom, d is density and NA is Avogadro’s constant (6.022 × 1023 mol-1).
Rank of unit cell can be computed by packing ef
ciency value :
Type of unit cell Packing efficiency Rank of unit cell (Z)
SC 52.4% 1
BCC 68% 2
FCC 74% 4
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EXERCISE-1 NCERT IMPORTANT QUESTION
1. Why are solids rigid ?

Ans. The intermolecular forces of attraction that are present in solids are very strong. The constituent
particles of solids cannot move from their positions i.e., they have fixed positions. However, they
can oscillate about their mean positions. This is the reason solids are rigid.
2. Why do solids have a definite volume ?
Ans. The intermolecular forces of attraction that are present in solids are very strong. The constituent
particles of solids have fixed positions i.e., they are rigid. Hence, solids have a definite volume.
3. Classify the following as amorphous or crystalline solids :
Polyurethane, naphthalene, benzoic acid, teflon, potassium nitrate, cellophane, polyvinyl chloride,
fibre glass, copper.
Ans. Amorphous solids
Polyurethane, teflon, cellophane, polyvinyl chloride, fibre glass
Crystalline solids
Naphthalene, benzoic acid, potassium nitrate, copper
4. A compound forms hexagonal close-packed structure. What is the total number of voids in 0.5
mol of it? How many of these are tetrahedral voids?
Ans. Number of close-packed particles = 0.5 × 6.022 × 1023 = 3.011 × 1023
Therefore, number of octahedral voids = 3.011 × 1023
And, number of tetrahedral voids = 2 × 3.011 × 1023 = 6.022 ×1023
Therefore, total number of voids = 3.011 × 1023 + 6.022 × 1023 = 9.033 × 1023
5. A compound is formed by two elements M and N. The element N forms ccp and atoms of M
occupy 1/3rd of tetrahedral voids. What is the formula of the compound?
Ans. The ccp lattice is formed by the atoms of the element N.
Here, the number of tetrahedral voids generated is equal to twice the number of atoms of the element N.
1 2 1
According to the question, the atoms of element 2 ´ = rd M occupy rd of the tetrahedral
3 3 3
voids.
Therefore, the number of atoms of M is equal to of the number of atoms of N.
Therefore, ratio of the number of atoms of M to that of N is M: N = 2 :1 = 2 : 3
3
Thus, the formula of the compound is M2 N3.
6. An element with molar mass 2.7 × 10–2 kg mol–1 forms a cubic unit cell with edge length 405 pm.
If its density is 2.7 × 103 kg m–3, what is the nature of the cubic unit cell?
Ans. It is given that density of the element, d = 2.7 × 103 kg m–3
Molar mass, M = 2.7 × 10–2 kg mol–1
Edge length, a = 405 pm = 405 × 10–12 m = 4.05 × 10–10 m
It is known that, Avogadro’s number, NA = 6.022 × 1023 mol–1
Applying the relation,
zM
d=
a3 × N
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d × a3NA
z=
M
2.7 ´103 kg m –3 ´ (4.05 ´10 -10 m)3 ´ 6.022 ´10 23 mol -1
=
2.7 ´10-2 kg mol –1
= 4 (fcc or ccp).
This implies that four atoms of the elements are present per unit cell. Hence the unit cell is FCC or
CCP.
7. What type of defect can arise when a solid is heated? Which physical property is affected by it
and in what way?
Ans. When a solid is heated, vacancy defect can arise. A solid crystal is said to have vacancy defect
when some of the lattice sites are vacant.
Vacancy defect leads to a decrease in the density of the solid.
8. Explain how vacancies are introduced in an ionic solid when a cation of higher valence is added
as an impurity in it.
Ans. When a cation of higher valence is added to an ionic solid as an impurity to it, the cation of higher
valence replaces more than one cation of lower valence so as to keep the crystal electrically
neutral. As a result, some sites become vacant. For example, when Sr2+ is added to NaCl, each
Sr2+ ion replaces two Na+ ions. However, one Sr2+ ion occupies the site of one Na+ ion and the
other site remains vacant. Hence, vacancies are introduced.
9. Ionic solids, which have anionic vacancies due to metal excess defect, develop colour.
Explain with the help of a suitable example.
Ans. The colour develops because of the presence of electrons in the anionic sites. These electrons
absorb energy from the visible part of radiation and get excited.
For example, when crystals of NaCl are heated in an atmosphere of sodium vapours, the sodium
atoms get deposited on the surface of the crystal and the chloride ions from the crystal diffuse to
the surface to form NaCl with the deposited Na atoms. During this process, the Na atoms on the
surface lose electrons to form Na+ ions and the released electrons diffuse into the crystal to
occupy the vacant anionic sites. These electrons get excited by absorbing energy from the visible
light and impart yellow colour to the crystals.
10. What makes a glass different from a solid such as quartz ? Under what conditions could quartz be
converted into glass ?
Ans. Glass is an amorphous solid while quartz is a crystalline solid. Quartz can be converted into glass
by melting and rapid cooling.
11. How can you determine the atomic mass of an unknown metal if you know its density and the
dimension of its unit cell? Explain.
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Ans. Volume of the unit cell = (a pm) a = edge lenth of a unit cell of a crystal
3 –30 3
= a × 10 cm d = density of the metal
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Mass of the unit cell
Density = m = mas of one atom of metal
Volume of the unit cell
Atomic mass M
where m = Z = number of atoms kc in the unit cell
Avogadro 's number N 0
Z ´ M / N0 Z´M
\ Density = i.e., r = 3 -30
g / cm 3
a ´ 10
3 -30 a ´ N 0 ´ 10
12. Calculate the efficiency of packing in case of a metal crystal for

(i) simple cubic
(iii) body-centred cubic
(iii) face-centred cubic (with the assumptions that atoms are touching each other).
Ans. Packing efficiency (P. E.) :-
4 3
volumeof atoms present in unit cell n ´ 3 pr
P.E= =
volume of unit cell V
3
4 æaö
1´ ´ p´ç ÷
3 è2ø p a
(i) for SCC : P.E. = = = 0.524 or 52.4% [Q r = and V = a 3 , n = 1]
a 3
6 2
3
4 æ 3a ö
4 3 2 ´ ´ p çç ÷÷
n´ pr 3
3 è 4 ø 3p 3a
(ii) for BCC: P.E. = = = = 0.68 or 68% [Q n = 2, r = , V = a3]
V a3 8 4
3
4 4 æ a ö
n ´ pr 3 4 ´ 3 p ´ ç ÷ a
(iii) for FCC : P.E. = 3 = è 2 2 ø = p = 0.74 or 74% [Q n =4, r = , V = a3]
V a 3
3 2 2 2
13. Silver crystallises in fcc lattice. If edge length of the cell is 4.077× 10–8 cm and density is 10.5g cm–
3
, calculate the atomic mass of silver.
Ans. Given that a = 4.077 × 10–8 cm, Crystal density = 10.5 gm cm–3 , for fcc, n = 4
n ´ Mw
Q Crystal density = V ´ N v = a3
A
4 ´ Mw
10.5 =
( 4.077 ´ 10 )
3
-8
´ 6.023 ´ 1023
10.5 ´ 67.76 ´ 10-24 ´ 6.023 ´ 1023

Mw = = 107.13 g/mol
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14. Niobium crystallizes in body centred cubic structure. If density is 8.55 g cm–3, calculate atomic
radius of niobium. (Mw of niobium = 93)
Ans. Given that Crystal density = 8.55 g cm–3 for Bcc, n = 2 , Mw of niobium = 93
n ´ Mw
Q Crystal density =
V ´ NA
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(V = a3)
2 ´ 93
\ V = = 3.6 × 10–23 cm3 or a3 = 36 × 10–24 cm3
8.55 ´ 6.023 ´ 1023
\ a = 3.3 × 10–8 cm
for Bcc 4r = 3 a
1.732 ´ 3.3 ´ 10-8

\ r= = 1.43 × 10–8 cm. = 14.32 nm
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15. If the radius of an octahedral void is r and the radius of the atom in close packing is R, derive the
relation between r and R ?
Ans. In the triangle ABC
R 1 C
cos 45º = =
R+r 2 R
B q A
r r
1+ = 2 or = 0.414
R R
16. Copper crystallises into a fcc lattice with edge length 3.61 × 10–8 cm. Show that the calculated
density is in agreement with its measured value of 8.92 g cm–3.
Ans. Given that a = 3.61 × 10–8 cm
for fcc, n = 4 and Mw of Cu = 63.5
n ´ Mw 4 ´ 63.5
Q Crystal density = = = 8.96 g cm–3
( )
3
V ´ NA 3.61 ´ 10 -8 6.023 ´ 1023
It is agreement with measured value 8.92 g cm–3

17. Analysis shows that nickel oxide has formula Ni0.98 O1.00. What fractions of the nickel exist as Ni2+
and Ni3+ ions?
Ans. Ni0.98O1.00
Let Ni2+ be a and Ni3+ be (1–a),
Total charge on cation = Total charge on anion (oxide)
2 ´ 1.00
a × 2 + (1–a) × 3 =
0.98
\ a = 0.959
\ Ni2+ = 0.959, Ni3+ = 0.041
The percentage of Ni2+ is 95.9% » 96% and that of Ni3+ » 4%.
18. Aluminium crystallises in a cubic close-packed structure. Its metallic radius is 125 pm
(a) What is the length of the side of the unit cell ?
(b) How many unit cells are there in 1.00 cm3 of aluminium ?
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Ans. Given that r = 125 pm
for fcc n = 4
(a) 4r = 2a
4r 4 ´ 125
\ a= = = 354 pm
2 1.414
(b) No. of unit cell = Total volume / Volume of a unit cell
1.00 1
= = [V = a3]
( )
3
V 3.54 ´ 10 -8
= 2.26 × 1022
19. If NaCl is doped with 10–3 mol % of SrCl2, what is the concentration of cation vacancies ?
Ans. It is given that NaCl is doped with 10–3 mol % of SrCl2.
This means that 100 mol of NaCl is doped with 10–3 mol of SrCl2.
10-3
Therefore, 1 mol of NaCl is doped with mol of SrCl2 = 10–5 mol of SrCl2.
100
Cation vacancies produced by one Sr2+ ion = 1
\ Concentration of the cation vacancies
Produced by 10–5 mol of Sr+2 ions = 10–5 × 6.022 × 1023
= 6.022 × 1018 mol–1
Hence, the concentration of cation vacancies created by SrCl2 is 6.022 × 1018 per mol of NaCl.
20. What is the total number of atoms pert unit cell in a face-centred (crystal structure ?
Ans. Total number of atoms per unit cell in (face–centred cubic) fcc structure = 6.
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21. Silver crystallises in a fcc lattice. The edge length of its unit is 4.077 × 10–8 cm and its density is
10.5 g cm–3. Calculate on this basis atomic mass of silver. (NA = 6.02 × 1023 mol–1)
Ans. Here a = 4.077 × 10–8 cm, d = 10.5 g cm–3
NA = 6.02 × 1023 mol–1
for fcc lattice, z = 4
z.M
d=
a3 .NA
( )
-8 3
d ´ a 3 ´ N A 10.5 ´ 4.077 ´ 10 ´ 6.02 ´ 10 23
\ M= = = = 107.09 g mol–1
z 4
22. Silver crystallises with face-centred cubic unit cells. Each side of the unit cell has a length of
409 pm. What is the radius of an atom of silver ?
(Assume that each face atom is touching the four corner atoms.)
Ans. Here side of unit cell, a = 409 pm
The radius of f.c.c. unit cell,
a
r=
2 2
= 0.3535 a
= 0.3535 × 409 = 144.5815 pm
23. What type of interactions hold the molecules together in a polar molecular solid?
Ans. The molecules in a polar molecular solids are held together by relatively stronger dipole–dipole
interactions.
24. The density of copper metal is 8.95 g cm-3. If the radius of copper atom be 127.8 pm, is the copper unit
cell simple cubic, body-centred cubic or face-centred cubic? (Given: atomic mass of
Cu = 63.54 g mol-1 and NA = 6.02 × 1023 mol-1)
Ans. Here d = 8.95 g cm–3 , r = 127.8 pm = 127.8 × 10–10 cm
M = 63.54 g mol–1 , NA = 6.02 × 1023 mol–1, Z = ?
\ a3 = ( 2 2r ) = 8r3
3
= 8 × (127.8 × 10–10)3
= 4.723 × 10–23 cm3
Z.M
Using the formula, d =
a3 .N A
Z ´ 63.54
8.95 =
4.723 ´ 10 -23 ´ 6.023 ´ 10 23
8.95 ´ 4.723 ´ 6.023 254.597
\Z= = = 4.006 » 4
63.54 63.54
Hence copper unit cell has fcc structure.
25. Calculate the packing efficiency of a metal crystal for a simple cubic lattice.
Ans. In a simple cubic unit cell: Suppose the edge length of the unit cell
= a and radius of the sphere = r [\ a = 2r]
1
No. of spheres per unit cell = ´ 8 = 1
8
4 3 r r
Volume of the sphere Þ p r
3
Volume of the cube = a3 = (2r)3 = 8r3 a
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æ4 3ö
ç pr ÷ p
Fraction occupied, i.e., packing fraction = è 3 ø = = 0.524
8r 3 6
Persentage = 52.4%
26. Explain how you can determine the atomic mass of an unknown metal if you know its mass density
and the dimensions of unit cell of its crystal.
Ans. Suppose,
a pm = edge of the unit cell
z = No. of atom present per unit cell
M = atomic mass
\ Volume of the unit cell = (a pm)3 = a3 × 10–30 cm3
a pm
Mass of the unit cell
Density =
Volume of the unit cell
Atomic mass M
where M = =
Avogadro's number N 0
z ´ M / N0 z´M
\ Density = i.e., d = 3 g / cm 3
a ´ 10
3 -30 a ´ N0 ´ 10 -30
27. Copper crystallises with face centred cubic unit cell. If the radius of copper atom is 127.8 pm, calculate the
density of copper metal.
(Atomic mass of Cu = 63.55 u and
Avogadro's number NA = 6.02 × 1023 mol–1)
M´Z
Ans. (i) d =
NA ´ a 3
4r 4(127.8 ´ 10 -10 cm)
a= =
2 2
z = 4, d = 8.92 gm/cc
28. Aluminium crystallizes in an FCC structure. Atomic radius of the metal is 125 pm. What is the length
of the side of the unit cell of the metal?
Ans. As it is fcc structure
Hence We can write
3 a = 2r + r + r
3 a = 4r
3 a = 4 × 125
Hence a = 289.0173 pm
29. An element with density 2.8 g cm–3 forms a fcc unit cell with edge length 4 × 10–8cm. Calculate the
molar mass of element. (NA= 6.022 × 1023 mol –1 )
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Ans. Here a = 4 × 10 –8 cm, d = 2.8 g cm–3
NA = 6.02 × 1023 mol–1
for fcc lattice, z = 4
z.M
d=
a3 .NA
( )
-8 3
d ´ a 3 ´ N A 2.8 ´ 4 ´ 10 ´ 6.022 ´ 10 23
\ M= = = = 28.31 g mol–1
z 4
30. What type of non-stoichiometric point defect is responsible for the pink colour of LiCl
Ans. F-centre
31. What type of stoichiometric defect is shown by NaCl.
Ans. Schottky defect.
32. Which ¯ stoichiometric defect does not change the density of the crystal.
Ans. Frenkel defect
33. Which stoichiometric defect ¯ the density of crystal.
Ans. Schottky
34. Which stoichiometric defect in crystal ,increases the density of a solid
Ans. Interstitial defect
35. What type of stoichiometric defect is shown by AgCl.
Ans. Frenkel defect.
36. Name the type of point defect that occurs in a crystal of zinc sulphide
Ans. Frenkel defect

37. What is the effect on the density of a crystal due to Schottky defect ?
Ans. Density of solid decreases
38. Why is the Frenkel defect not found in pure alkali metal halides ?
Ans. Alkali metals halides have similar size of cations and anions, thus Frenkel defect is absence in them.
39. What type of defect is produced when NaCl is doped with SrCl2 ?
Ans. Impurity defect is produced
E 13
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EXERCISE-2 PREVIOUS YEARS QUESTION
1. Analysis shows that FeO has a non-stoichiometric compostion with formula Fe0.95O. Give reason.
(CBSE 2018)
Ans. In FeO, Fe present in both +2 & +3 oxidation state. So, FeO has non-stoichometric composition.
2. An element ‘X’ (At. mass = 40 g mol –1) having f.c.c. structure, has unit cell edge length of 400 pm.
Calculate the density of ‘X’ and the number of unit cells in 4 g of ‘X’. (NA = 6.022 × 1023 mol–1)
(CBSE 2018)
Ans. Atomic mass = 40g/mol
A = 400pm = 400 × 10–10 cm or 4 × 10–8 cm
z´M
d= [1/2]
a 3 ´ NA
4 ´ 40
= -8 3 [1/2]
(4 ´ 10 ) ´ 6.023 ´1023
160 160
d= =
64 ´ 6.023 ´10 -1 6.4 ´ 6.023
= 4.18 gm/cc
1 mole of 'X' atom contains = 6.023 × 1023 atoms = 40 g [1]
6.023 ´1023
1 g contains = atoms
40
6.023 ´10 23
4 g contains = ´ 4 atoms = 6.023 × 1022 atoms
40
6.023 ´ 1022
So, the no. of unit cells = = 1.50 ´ 1022 unit cell [1]
4
3. Calculate the number of unit cells in 8.1 g of aluminium if it crystallizes in a face-centred cubic
(fcc) structure. (Atomic mass of Al = 27 g mol–1) (CBSE 2017)
Ans. n = given mass / molar mass
= 8.1 / 27 mol [1/2]
8.1
Number of atoms = ´ 6.022 ´1023 [1/2]
27
Number of atoms in one unit cell = 4 (fcc) [1/2]
é 8.1 ù
Number of unit cells = ê ´ 6.022 ´10 ú / 4
23
[1/2]
ë 27 û
= 4.5 × 10 22 [1]
Or
27g of Al contains = 6.022 × 1023
atoms
23
8.1g of Al contains = (6.022 × 10 /27) × 8.1
No. of units cells = total no of atoms / 4
é 8.1 ù
= ê ´ 6.022 ´10 ú / 4
23
= 4.5 × 1022
ë 27 û
14 E
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4. (a) Based on the nature of intermolecular forces, classify the following solids : (CBSE 2017)
Benzene, Silver
(b) AgCl shows Frenkel defect while NaCl does not. Give reason.
(c) What type of semiconductor is formed when Ge is doped with Al?
Ans. (a) Benzene – molecular solid [1]
Silver – metallic solid
(b) Size of Ag+ ion is smaller than Na+ ion [1]
(c) p-type [1]
5. ZnO turns yellow on heating. Why ? (CBSE 2016)
Ans. Due to presence of free electrons at interstitial sites, or metal excess defect
6. An element crystallizes in a f.c.c. lattice with cell edge of 400 pm. The density of the element is
7g cm–3. How many atoms are present in 280 g of the element ? (CBSE 2016)
3
Ans. Volume of the unit cell = a
= (400 pm)3
= (4 x 10–8 cm)3
= 64 × 10–24 cm3 [1]
Volume of 280 g of the element = mass / density
= 280/7 cm3
= 40 cm3
Number of unit cells in this volume = 40 / 64 × 10–24 = 6.25 × 1023 unit cells. [1]
Since z = 4 ,
Therefore, total no. Of atoms in 280g = 4 × 6.25 × 1023
= 2.5 × 1024 atoms. [1]
7. Write the formula of a compound in which the element Y forms ccp lattice and atoms of X
occupy 1/3rd of tetrahedral voids.
(CBSE 2015)
Ans. X2Y3
8. Examine the given defective crystal : (CBSE 2015)
X +
Y –
X +
Y –
X +
Y– X+ Y– X+ Y–
X+ Y– X+ e
–
X+
Y– X+ Y– X+ Y–
Answer the following questions :
(i) Is the above defect stoichiometric or non-stoichiometric?
(ii) Write the term used for the electron occupied site.
(iii) Give an example of the compound which shows this type of defect.
Ans. (i) Non- stoichio meteric defect
[1]
(ii) F- centre/farbe centre [1]
(iii) NaCl , KCl, CsCl [1]
E 15
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EXERCISE-3 R AC E
Type–1 : Passage question 1 :
Examine the given defective crystal :-
+ – + – +
X Y X Y X
– – + –
Y Y X Y
+ – + +
X Y X X
– + – + –
Y X Y X Y
(i) What type of the above defect is -
(a) stoichiometric defect (b) Non-stoichiometric defect
(c) Both (a) & (b) (d) None of these
(ii) Write the term used for this type of defect is -
(a) Frenkel (b) Schotky (c) Both (a) & (b) (d) None of these
(iii) An example of the compound which shows this type of defect -
(a) NaCl (b) ZnS (c) CsCl (d) AgI
(iv) In this stoichiometric defect the density of crystal is -
(a) Decrease (b) Increase (c) No change (d) None
OR
Write the term used for non ionic type of defect is -
(a) Vacancy (b) interstitial (c) Both (a) and (b) (d) None of these
Type–2 : Assertion and Reason :

Question 2 to 6:-Note:- in the following questions a statement of assertion followed by a reason . choose
the correct answer out of the following choices –
(A) both assertion and reason are true , and reason is the correct explaining of the assertion
(B) both assertion and reason are true but reason is not the correct explaining of the assertion
(C) Assertion is not true but reason is true
(D) Both assertion and reason are false
2. Assertion : The total number of atoms present in a simple cubic unit cell is one.
Reason : Simple cubic unit cell has atoms at its corners, each of which is shared between eight adjacent
unit cells.
3. Assertion : Graphite is a good conductor of electricity however diamond belongs to the category of
insulators.
Reason : Graphite is soft in nature on the other hand diamond is very hard and brittle.
4. Assertion : Total number of octahedral voids present in unit cell of cubic close packing including
the one that is present at the body centre, is four.
Reason : Besides the body centre there is one octahedral void present at the centre of each of the
six faces of the unit cell and each of which is shared between two adjacent unit cells.
5. Assertion : The packing efficiency is maximum for the fcc structure.
Reason : The cordination number is 12 in fcc structures.
6. Assertion : AgBr possese both schotky and Frenkel defect.
Reason : ZnS shows Frenkel defect.
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Type–3 : Multiple choice question (One correct answer) Question 7 to 16 :
7. Cations are present in the interstitial sites in __________.
(i) Frenkel defect (ii) Schottky defect (iii) Vacancy defect (iv) Metal deficiency defect
8. Schottky defect is observed in crystals when __________.
(i) some cations move from their lattice site to interstitial sites.
(ii) equal number of cations and anions are missing from the lattice.
(iii) some lattice sites are occupied by electrons.
(iv) some impurity is present in the lattice.
9. Which of the following is a network solid?
(i) SO2 (Solid) (ii) I2 (iii) Diamond (iv) H2O (Ice)
10. What is the coordination number in a square close packed structure in two dimensions?
(i) 2 (ii) 3 (iii) 4 (iv) 6
11. Which of the following defects is also known as dislocation defect?
(i) Frenkel defect (ii) Schottky defect
(iii) Non-stoichiometric defect (iv) Simple interstitial defect
12. Which of the following is not a characteristic of a crystalline solid?
(i) Definite and characteristic heat of fusion.
(ii) Isotropic nature.
(iii) A regular periodically repeated pattern of arrangement of constituent particles in the entire
crystal.
(iv) A true solid
13. Which of the following is an amorphous solid?
(i) Graphite (C) (ii) Quartz glass (SiO2 )
(iii) Chrome alum (iv) Silicon carbide (SiC)

14. Iodine molecules are held in the crystals lattice by ____________.
(i) london forces (ii) dipole-dipole interactions
(iii) covalent bonds (iv) coulombic forces
15. Which of the following point defects are shown by AgBr(s) crystals?
(A) Schottky defect (B) Frenkel defect
(C) Metal excess defect (D) Metal deficiency defect
(i) (A) and (B) (ii) (C) and (D) (iii) (A) and (C) (iv) (B) and (D)
16. The total number of tetrahedral voids in the face centred unit cell is __________.
(i) 6 (ii) 8 (iii) 10 (iv) 12
Answer key :
Q. No. 1 (i) (ii) (iii) (iv) 2 3 4 5 6 7 8
Ans. a b b a or a A B C B C i ii
Q. No. 9 10 11 12 13 14 15 16
Ans. iii iii i ii iii i i ii
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EXERCISE-4 MOCK TEST
1. Write any one example of network solid. [1]
2. Dislocation of which ion in "AgBr" develops Frenkel defect? [1]
3. Copper shows electrical conductance in solid as well as molten state whereas copper chloride shows
electrical conductance only in molten state. Give reason. [1]
4. Write any two differences between Schottky and Frenkel defects. [2]
5. Give any one difference between anisotropy and isotropy nature of solid. [2]
6. ZnO turns yellow on heating. Why ? [2]
7. Write the formula of a compound in which the element Y forms ccp lattice and atoms of X occupy
1/3rd of tetrahedral voids. [2]
8. How can you determine the atomic mass of an unknown metal if you know its density and the
dimension of its unit cell? Explain. [3]
9. An element crystallizes in a f.c.c. lattice with cell edge of 400 pm. The density of the element is
7g cm–3. How many atoms are present in 280 g of the element ? [3]
10. An element with density 2.8 g cm–3 forms a fcc unit cell with edge length 4 × 10–8cm. Calculate
the molar mass of element. (NA= 6.022 × 1023 mol–1) [3]
11. If NaCl is doped with 10–3 mol % of SrCl2, what is the concentration of cation vacancies ? [5]
18 E
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MOCK TEST SOLUTIONS
1. Diamond
2. Dislocation of Ag+ ion in "Ag and Br" develops Frenkel defect. When cation or anion from ionic solid
leaves the regular site and moves to occupy a place between the lattice site, Frenkel defect is observed.
This defect is also called interstitial defect.
3. In case of Cu metal free e¯ are present which conduct electricity in both liquid and solid states.Where
as in CuCl2 ions conduct electricity which become free under molten state only but not in solid state.
4. Schottky Defect:
(i) It occurs when oppositely charged atoms leave their corresponding lattice sites and create a pair
of vacancy defect.
(ii) Size of the anion is almost the same as the size of the colour.
Frenkel Defect:
(i) It is one type of point defect where an ion, especially cation leaves it's original lattice site and
occupies an interstitial position at the same crystal.
(ii) Size of the anion is substantially large than the size of a cation.
The ability of crystalline solids to change values of physical properties when measured in different
directions is called anisotropy. It arises because the composition of solid changes with direction.
On the other hand, the values of the physical properties for amorphous solids do not change with change
of direction. The properties remain same in all the directions. It is called isotropy.
6. Due to presence of free electrons at interstitial sites, / metal excess defect
7. X2 Y3
8. The formula relating density and atomic mass is given below:
Zm da 3
d= or m = .....(1)
a3 Z
Here, d = density, Z = number of atoms per unit cell, m= mass of an atom and a = edge length
M
Also, m = N .....(2)
A
Here, m is the mass of an atom, M is the atomic mass (mass of 1 mole of atoms) and NA is the Avogadro's
number. Thus, we can determine the atomic mass of an unknown metal if we know its density and the
dimension of its unit cell.
9. Volume of the unit cell = a3
= (400 pm)3
= (4 × 10–8 cm)3
= 64 × 10–24 cm3
Volume of 280 g of the element = mass / density
= 280/7 cm3 = 40 cm3
Number of unit cells in this volume = 40 / 64 × 10 –24 = 6.25 × 1023 unit cells.
Since z = 4,
Therefore, total no. Of atoms in 280g = 4 × 6.25 × 10 23
= 2.5 × 10 24 atoms.
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10. Density = 2.8 g/cm3
FCC: No. of atoms in unit cell = 4
Edge length = 4 × 10 –8
NA = 6.022 × 10 23 mol –1
Z´m
d = a3 ´ N
A
Where d = density ,Z= No. of atoms in unit cell, m= molar mass, a3 = volume , NA = Avogadro number
d ´ a3 ´ NA
m=
Z
2.8 ´ (4 ´ 10 –8 )3 ´ 6.022 ´ 10 23
=
4
m = 26.97 g/mol
11. It is given that NaCl is doped with 10 –3 mol % of SrCl 2 .
This means that 100 mol of NaCl is doped with 10 –3 mol of SrCl 2 .
10 -3
Therefore, 1 mol of NaCl is doped with mol of SrCl 2 = 10 –5 mol of SrCl 2 .
100
Cation vacancies produced by one Sr2+ ion = 1

Concentration of the cation vacancies produced by 10 –5 mol of Sr+2 ions = 10 –5 × 6.022 × 10 23
= 6.022 × 10 18 mol –1
Hence, the concentration of cation vacancies created by SrCl2 is 6.022 × 10 18 per mol of NaCl.
20 E
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SOLUTION
l Solution : A solution is a homogeneous mixture of two or more substances whose compositioin can
be varied within certain limits.
Type of solution :
Type of Solutions Solute Solvent Common Example
Gaseous Solutions Gas Gas Mixture of oxygen and nitrogen gases

Liquid Gas Chloroform mixed with nitrogen gas
Solid Gas Camphor in nitrogen gas
Liquid Solutions Gas Liquid Oxygen dissolved in water

Liquid Liquid Ethanol dissolved in water
Solid Liquid Glucose dissolved in water
Solid Solutions Gas Solid Solution of hydrogen in palladium

Liquid Solid Amalgam of mercury with sodium
Solid Solid Copper dissolved in gold
l The component that is having more number of moles is known as solvent. Solvent determines the
physical state of the solution. Water is an universal solvent.
l As the temperature increases Henry.s law constant, KH increases so the lower is the solubility of the
gas in the liquid.
l 11.7% w/w Helium is added to air used by scuba divers due to its low solubility in the blood.
0
l Raoult¢s law becomes a special case of Henry.s law in which KH becomes equal to PA , i.e., vapour
node06\B0B0-BA\Kota\Board Material\Chemistry\CBSE\CBSE Booklet\English\Updated booklet-21\New Pattern CBSE Booklet\Part wise boocklet\Part 1\01_PC\01_Solutions
pressure of pure solvent.

l Azeotropic mixtures :
Some liquids on mixing form azeotropes which are binary mixture having same composition in liquid
and vapour phase and boil at a constant temperature. Azeotropic mixture cannot be separated by
fractional distillation.
l Types of Azeotropic mixtures
(i) Minimum boiling Azeotropic mixtures
The mixture of two liquids whose boiling point is less than either of the two pure components. They are
formed by non-ideal solutions showing positive deviation. For example (95.5%) + water (4.5%) +
water boils at 351.15 K.
(ii) Maximum boiling Azeotropic mixtures
The mixture of two liquids whose boiling point are more than either of the two pure components.
They are formed by non-ideal solutions showing negative deviation. For example HNO3 (68%) +
water (32%) mixture boils at 393.5 K.
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l Azeotropes arise due to very large deviation from Raoult.s law. Maximum boiling azeotropes form
when solutions exhibit negative deviation from Raoult’s law whereas minimum boiling azeotropes
form when solutions exhibit positive deviation from Raoult¢s law.
l Relative lowering in vapour pressure is a colligative property but lowering in vapour pressure is not.
l Mole fraction (X)
If the number of moles of A and B are nA and nB respectively, the mole fractions of A and B will be
nA nB
XA = and XB =
n A + nB nA + nB
XA + XB = 1
l Mole fraction (X) is a unitless quantity.
Molesof solute -1
l Molarity (M) = Volume of solution in litres mol L
l Molality (m) and mole fraction are temperature independent quantities whereas molarity decreases
with increase in temperature.
l If volume V1 of a solution of molarity M1 is mixed with volume V2 of the solution of molarity M2,
then molarity M3 of the final solution is
M1V1 + M2V2 = M3(V1 + V2)
Moles of solute -1
l Molality (m) = Mass of solvent in kilograms molkg
l Parts per million (ppm)

Number of partsof the compound
= Total number of partsof allcomponentsof thesolution ´10
6
l Raoult¢s law for a solution of volatile solute in volatile solvent :

0
pA = pA XA
0
pB = pB XB
Where pA and pB are partial vapour pressures of component ‘A’ and component ‘B’ respectively in
solution. p0A and p0B are vapour pressures of pure components ‘A’ and ‘B’ respectively.
l Raoult¢s law for a solution of non-volatile solute and volatile solvent :
p 0A - p T n W ´ MA
= XB; B = B
p 0A n A M B ´ WA
p 0A - p T
Where XB is mole fraction of solute, p0A
is relative lowering of vapour pressure.
l Elevation in boiling point (DTb) :
DTb = Kb m
0
Where DTb = Tb – Tb
l Depression in freezing point (DTf) :
DTf = Kfm
0
Where DTf = Tf – Tf
l Osmotic pressure (p) of a solution :
pV = nRT or p = CRT
22 E
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DEVIATION FROM RAOULT'S LAW
Positive deviation Negative deviation Zero deviation

(DH=+ve) (DH=–ve) (DH=0)
(i) ethanol + cyclohexane acetone + chloroform benzene + toluene
(ii) acetone + carbon disulphide benzene + chlorform
n-hexane + n-heptane
(iii) acetone + benzene nitric acid + chloroform ethyl bromide + ethyl iodide
(iv) ethanol + aceton acetone + aniline chlorobenzene + bromo
benzene
(v) ethanol + water water + nitric acid
(vi) carbon tetrachloride diethyl ether +
chloroform chloroform
l Ideal solution are formed by liquids having same intermolecular interactions e.g., benzene + toluene.
l If intermolecular interactions increase on mixing the two liquids, the solution show negative deviations
e.g., chloroform + acetone.
l If intermolecular interactions decrease on mixing the two liquids, the solution show positive deviations
e.g., ethylalcohol + cyclohexane.
l Intramolecular H-bonding lowers boiling point.
l Benzoic acid and acetic acid dimerises in benzene.
l When egg is kept in saturated salt solution affter removing the hard shell using dil. HCl, egg will shrink
due to osmosis.
l CaCl2 acts as a non-volatile solute and results depression in freezing point. Thus, snow is reduced
(as it melts) and prevents blocking of roads in cold region.
l Ethylene glycol is mixed with radiator water to lower the freezing point of water in cold region.
l To increase the solubility of CO2 in soft dringks, the bott is sealed under high pressure.
l Helium-oxygen mixture is used by deep divers because of its low solubility in blood.
l Henry's law – states that the partial pressure of gas (p) is proportional to the mole fraction of gas (x)
in the solution.
l Vapour pressure – The pressure exerted by the vapours above the liquid surface in equilibrium with
the liquid at a given temperature is called.
l Edema – People taking a lot of salt of salty food experience water retention in tissue cells and
intercellular spaces because of osmosis. This resulting puffness of swlling is called.
l Reverse osmosis – In the solvent flows from solution side towards pure solvent if external pressure
is higher than osmotic pressure applied on solution side. It is used for desalination of sea water. Solvent
moves from solution to pure solvent side.
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1. Calculate the mass of urea (NH2CONH2) required in making 2.5 kg of 0.25 molal aqueous solution.
Ans. Molar mass of urea (NH2CONH2) = 2(1 × 14 + 2 × 1) + 1 × 12 + 1 × 16 = 60 g mol–1
0.25 molar aqueous solution of urea means:
1000 g of water contains 0.25 mol = (0.25 × 60)g of urea
= 15 g of urea
That is,
(1000 + 15) g of solution contains 15 g of urea
15 ´ 2500
Therefore, 2.5 kg (2500 g) of solution contains = g
1000 + 15
= 36.95 g
2. H2S, a toxic gas with rotten egg like smell, is used for the qualitative analysis. If the solubility of H2S
in water at STP is 0.195m, calculate Henry’s law constant.
Ans. It is given that the solubility of H2S in water at STP is 0.195 m, i.e., 0.195 mol of H2S is dissolved in
1000 g of water.
1000g
Moles of water = = 55.56 mol
18g mol-1
Molesof H 2S
\ Mole fraction of H2S, x =
Molesof H 2S + Moles of water
0.195
= = 0.0035
0.195 + 55.56
At STP, pressure (p) = 0.987 bar
According to Henry’s law: p = KHX
p 0.987
Þ KH = = bar
x 0.0035
= 282 bar
3. Henry’s law constant for CO2 in water is 1.67 × 108 Pa at 298 K. Calculate the quantity of CO2 in
500 mL of soda water when packed under 2.5 atm CO2 pressure at 298 K.
Ans. It is given that:
KH = 1.67 × 108 Pa
p CO 2 = 2.5 atm = 2.5 × 1.01325 × 105 Pa
= 2.533125 × 105 Pa
According to Henry’s law:
pCO2 = K H x
CO p
Þ x= K
2
24 E
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ALLEN
2.533125 ´105
=
1.67 ´108
= 0.00152
n CO2 n CO 2
We x CO = » can write,
2
n CO2 + n H 2 O n H2O
(Since1 n CO is negligible as compared to n H O )

2 2
In 500 mL of soda water, the volume of water = 500 mL

[Neglecting the amount of soda present] We can write:
500 mL of water = 500 g of water
500
= mol of water
18
= 27.78 mol of water
n CO2
Now, =x
n H 2O
n CO2
= 0.00152
27.78
n CO2 = 0.042 mole
Hence, quantity of CO2 in 500 mL of soda water = (0.042 × 44)g

= 1.848 g
4. The vapour pressure of pure liquids A and B are 450 and 700 mm Hg respectively, at 350 K. Find
out the composition of the liquid mixture if total vapour pressure is 600 mm Hg.
Also find the composition of the vapour phase.
Ans. (i) It is given that:

PA0 = 450 mm of Hg Þ Ptotal = PA0 x A + PB0 (1 - x A )
PB0 = 700 mm of Hg Þ Ptotal = PA0 x A + PB0 - PB0 x A
Ptotal = 600 mm of Hg Þ Ptotal = ( PA0 - PB0 ) x A + PB0

From Raoult’s law, we have: Þ 600 = (450 – 700)xA + 700
PA = PA0 x A Þ –100 = –250xA Therefore, total pressure,
PB = PB0 x B = PB0 (1 - x A ) Þ xA = 0.4 Ptotal = PA + PB
xB = 1 – xA
Therefore,
= 1 - 0.4
= 0.6
Now, PA = PA0 x A
= 450 × 0.4 = 180 mm of Hg
PB = PB0 x B
= 700 × 0.6
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= 420 mm of Hg
P
(ii) Now, in the vapour phase: Mole fraction of liquid A = P + P
A
A B
180
=
180 + 420
180
=
600
= 0.30
And, mole fraction of liquid B = 1 – 0.30
= 0.70
5. Vapour pressure of pure water at 298 K is 23.8 mm Hg. 50 g of urea (NH2CONH2) is dissolved in
850 g of water. Calculate the vapour pressure of water for this solution and its relative lowering.
Ans. It is given that vapour pressure of water, P10 = 23.8 mm of Hg
Weight of water taken, w1 = 850 g
Weight of urea taken, w2 = 50 g
Molecular weight of water, M1 = 18 g mol–1
Molecular weight of urea, M2 = 60 g mol–1
Now, we have to calculate vapour pressure of water in the solution. We take vapour
pressure as P1.
Now, from Raoult’s law, we have:
P10 - P1 n2
=
P10 n1 + n 2
w2
P10 - P1 M2
Þ =
P10 w1 W2
+
M1 M 2
50
23.8 - P1 60
=
Þ 23.8 850 50
+
18 60
23.8 - P1 0.83
Þ =
23.8 47.22 + 0.83
23.8 - P1
Þ = 0.0173 Þ P1 = 23.4 mm of Hg
23.8
Hence, the vapour pressure of water in the given solution is 23.4 mm of Hg and its relative
lowering is 0.0173.
6. Boiling point of water at 750 mm Hg is 99.63°C. How much sucrose is to be added to 500 g of
water such that it boils at 100°C. Molal elevation constant for water is 0.52 K kg mol–1.
Ans. Here, elevation of boiling point DTb = (100 + 273) – (99.63 + 273) = 0.37 K
26 E
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Mass of water, wl = 500 g
Molar mass of sucrose (C12H22O11), M2 = 11× 12 + 22 × 1 + 11 × 16 = 342 g mol–1
Molal elevation constant, Kb = 0.52 K kg mol–1
We know that:
K b ´1000 ´ w 2
DTb =
M 2 ´ w1
DTb ´ M 2 ´ w1
Þ w2 = K b ´1000
0.37 ´ 342 ´ 500
=
0.52 ´1000
= 121.67 g
Hence, 121.67 g of sucrose is to be added.
7. Calculate the mass of ascorbic acid (Vitamin C, C6H8O6) to be dissolved in 75 g of acetic acid to
lower its melting point by 1.5°C. Kf = 3.9 K kg mol–1.
Ans. Mass of acetic acid, w1 = 75 g
Molar mass of ascorbic acid (C6H8O6), M2 = 6 × 12 + 8 × 1 + 6 × 16 = 176 g mol–1
Lowering of melting point, DTf = 1.5 K
We know that:
K f ´ w 2 ´1000
DTf =
M2 ´ w 2
DTf ´ M 2 ´ w1
Þ w2 = K f ´1000
1.5 ´176 ´ 75
= = 5.08 g
3.9 ´1000
Hence, 5.08 g of ascorbic acid is needed to be dissolved.

8. Calculate the osmotic pressure in pascals exerted by a solution prepared by dissolving 1.0 g of
polymer of molar mass 185,000 in 450 mL of water at 37°C.
Ans. It is given that:
Volume of water, V = 450 mL = 0.45 L
Temperature, T = (37 + 273)K = 310 K
1
Number of moles of the polymer, n = mol
185000
We know that:
n
Osmotic pressure, p = RT
V
1 1
= mol ´ ´ 8.314 ´103 Pa L K–1 mol–1 × 310 K
185000 0.45 L
= 30.98 Pa
9. An aqueous solution of 2% non-volatile solute exerts a pressure of 1.004 bar at the normal boiling
point of the solvent. What is the molar mass of the solute ?
E 27
Chemistr y
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Ans. Here,
Vapour pressure of the solution at normal boiling point (p1) = 1.004 bar
Vapour pressure of pure water at normal boiling point (p01) = 1.013 bar
Mass of solute, (w2) = 2g
Mass of solvent (water), (w1) = 98 g
Molar mass of solvent (water), (M1) = 18 g mol–1
According to Raoult's law.
p10 - p1 w 2 ´ M1
=
p10 M 2 ´ w1
1.013 - 1.004 2 ´ 18
Þ =
1.013 M2 ´ 98
0.009 2 ´ 18
Þ =
1.013 M2 ´ 98
1.013 ´ 2 ´ 18
Þ M2 =
0.009 ´ 98
= 41.35 g mol–1
Hence, the molar mass of the solute is 41.35 g mol–1.
10. Heptane and octane form an ideal solution. At 373 K, the vapour pressure of the two liquid
components are 105.2 kPa and 46.8 kPa respectively. What will be the vapour pressure of a
mixture of 26.0 g of heptane and 35 g of octane ?
Ans. Vapour pressure of heptane (p10) = 105.2 kPa
Vapour pressure of octane (p20) = 46.8 kPa
We know that,
Molar mas of heptane (C7H16) = 7 × 12 + 16 × 1 = 100 g mol–1
26
\ Number of moles of heptane = = 0.26 mol
100
35
\ Number of moles of octane = mol = 0.31 mol
114
[Molar mass of octance (C8H18) = 8 × 12 + 18 × 1 = 144 gmol]
0.26
Mole fraction of heptane, x1 = = 0.456
0.26 + 0.31
And, mole fraction of octane, x2 = 1 – 0.456 = 0.544
Now, partial pressure of heptane, p1 = x1p10
= 0.456 × 105.2 = 47.97 kPa
Partial pressure of octane, P2 = x2p20
= 0.544 × 46.8 = 0.544 kPa
Hence, vapour pressure of solution, ptotal = p1 + p2
= 47.97 + 25.46 = 73.43 kPa
11. The vapour pressure of water is 12.3 kPa at 300 K. Calculate vapour pressure of 1 molal solution of
a non-volatile solute in it.
28 E
CBSE
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Ans. 1 molal solution means 1 mol of the solute is present in 1000 g of the solvent (water).
Molar mass of water = 18 g mol–1
1000
\ Number of moles present in 1000 g of water = = 55.56 mol
18
1
Therefore, mole fraction of the solute in the solution is x2 = = 0.0177
1 + 55.56
It is given that,
Vapour pressure of water, p10 = 12.3 kPa
p10 - p1
Applying the realtion, = x2
p10
12.3 - p1
Þ = 0.0177
12.3
Þ 12.3 – p1 = 0.2177
Þ p1 = 12.0823
= 12.08 kPa (approximately)
Hence, the vapour pressure of the solution is 12.08 kPa.
12. Calcualte the mass of a non-volatile solute (molar mass 40 g mol–1) which should be dissolved in
114 g octane to reduce its vapour pressure to 80%.
Ans. Let the vapour pressure of pure octane be p10.
80 0
Then, the vapour pressure of the octane after dissolving the non - volatile solute is p1 = 0.8p10
100
Molar mass of solute,M2 = 40 g mol–1
Mass of octane, w1 = 114 g
Molar mass of octane, (C8H18), M1 = 8 × 12 + 18 × 1 = 114 g mol–1
p10 - p1 w 2 ´ M1
=
p10 M 2 ´ w1
p10 - 0.8p10 w 2 ´ 114 0.2p10 w 2 w2

Þ = Þ = Þ 0.2 = Þ w2 = 8 gm
p10 40 ´ 114 p10 40
40
Hence, the required mass of the solute is 8 g.
13. A solution containing 30 g of non-volatile solute exactly in 90 g of water has a vapour pressure of
2.8 kPa at 298 K. Further, 18 g of water is then added to the solution and the new vapour pressure
becomes 2.9 kPa at 298 K. Calculate :
(i) molar mass of the solute
(ii) vapour pressure of water at 298 K.
Ans. (i) Let, the molar mass of the solute be M g mol–1
90 g
Now, the no. of moles of solvent (water), n1 = = 5mol
18 g mol -1
30 g 30
And, the no. of moles of solute, n2 = M mol -1 = M mol
p1 =2.8 kPa
E 29
Chemistr y
ALLEN
Applying the relation :
p10 - p1 n2
0
=
p1 n1 + n 2
30
p10 - 2.8 M
Þ =
p10 30
5+
M
p10 5M + 30
Þ = .........(1)
2.8 5M
After the addition of 18 g of water :
90 + 18g
n1 = = 6mol
18
p1 = 2.9 kPa
Again, applying the relation :
30
p10 - p1 n2
= Þ p10 - 2.9 M
p10 n1 + n 2 =
p10 30
6+
M
p10 6M + 30
Þ = .........(2)
2.9 6M
Dividing equtation (i) by (ii), we have :
5M + 30
2.9
= 5M
2.8 6M + 30
6M
2.9 6M + 30 5M + 30
Þ ´ =
2.8 6 5
Þ 2.9 × 5 × (6M + 30) = 2.8 × 6 × (5M + 30)

Þ 87 M + 435 = 84M + 504
Þ 3M = 69
Þ M = 23 u
Therefore, the molar mass of the solute is 23 g mol–1
(ii) Putting the value of 'M' in equation (i), we have :
p10 5 ´ 23 + 30
=
2.8 5 ´ 23
p10 145
Þ = Þ p10 = 3.53
2.8 115
Hence, the vapour pressure of water at 298 K is 3.53 kPa.
30 E
CBSE
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14. A 5% solution (by mass) of cane sugar in water has freezing point of 271 K. Calculate the freezing
point of 5% glucose in water if freezing point of pure water is 273.15 K.
Ans. Here, DTf = (273.15 – 271) K = 2.15 K
Molar mass of sugar (C12H22O11) = 12 × 12 + 22 × 1 + 11 × 16 = 342 g mol–1
5% solution (by mass) of cane sugar in water means 5 g of cane sugar is present in (100 – 5) g = 95g
of water.
5
Now, number of moles of cane sugar = mol = 0.0146 mol
342
0.0146mol
Therefore, molality of the solution, m = = 0.1537 mol kg–1
0.095kg
DTf = Kf × m
DTf 2.15 k
Þ Kf = = 0.1537 mol kg-1
m
= 13.99 K kg mol–1
Molar mass of glucose (C6H12O6) = 6 × 12 + 12 × 12 × 1 + 6 × 16 = 180 g mol–1
5% glucose in water means 5g of glucose is present in (100 – 5) = 95 g of water.
5
\ Number of moles of glucose = mol = 0.0278 mol
180
0.0278 mol
Therefore, molality of the solution, m = = 0.2926 mol kg–1
0.095 kg

DTf = Kf × m
= 13.99 K kg mol–1 × 0.2926 mol kg–1

= 4.09 K (approximately)
Hence, the freezing point of 5% glucose solution is (273.15 - 4.09) K = 269.06 K.
15. Two element A and B form compounds having formula AB2 and AB4. When dissolved in 20 g of
benzene (C6H6), 1 g of AB2 lowers the freezing point by 2.3 K whereas 1.0 g of AB4 lowers it by
1.3 K. The molar depression constant for benzene is 5.1 K kg mol–1. Calculate atomic masses of A
and B.
Ans. We know that,
1000 ´ w 2 ´ k f
M2 =
DTf ´ w1
1000 ´ 1 ´ 5.1
Then, M AB = = 110.87 g mol–1
2
2.3 ´ 20
1000 ´ 1 ´ 5.1
M AB4 = = 196.15 g mol–1
1.3 ´ 20
Now, we have the molar masses of AB 2 and AB4 as 110.87 g mol–1 and 196.15 g mol–1 respectively.
E 31
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Let the atomic masses of A and B are x and y respectively.
Now, we can write :
x + 2y = 110.87 ...........(i)
x + 4y = 196.15 ...........(ii)
Subtracting equation (i) from (ii), we have
2y = 85.28
y = 42.64
Putting the value of 'y' in equation (1), we have
x + 2 × 42.64 = 110.87
x = 25.59
Hence, the atomic masses of A and B are 25.59 u and 42.64 u respectively.
16. At 300 K, 36g of glucose present in a litre of its solution has an osmotic pressure of 4.98 bar. If the
osmotic pressure of the solution is 1.52 bars at the same temperature, what would be its concentration?
Ans. Here,
T = 300 K
p = 1.52 bar
R = 0.083 bar L K–1 mol–1
Applying the relattion,
p = CRT
p 1.52 bar
Þ C= = = 0.061 mol
RT 0.083 bar,L.K -1mol -1 ´ 300 K
Since the volume of the solution is 1 L, the concentration of the solution would be 0.061 M.
17. Vapour pressure of water at 293 K is 17.535 mm Hg. Calculate the vapour pressure of water at
293 K when 25 g of glucose is dissolved in 450 g of water.
Ans. Vapour pressure of water, p10 = 17.535 mm of Hg
Mass of glucose, w2 = 25 g
Mass of water, w1 = 450 g
We know that,
Molar mass of glucose (C6H12O6), M2 = 6 × 12 + 12 × 1 + 6 × 16 = 180 g mol–1
Molar mass of water, M1 = 18 g mol–1
25
Then, number of moles of glucose, n2 = = 0.139 mol
180 g mol -1
450 g
And, number of moles of water, n1 = = 25 mol
18 g mol -1
We know that,
é n1 ù
P1 = P 0 ´ ê ú
ë n1 + n2 û
é 25 ù 17.535 ´ 25
Þ P1 = 17.535 ê ú = 25.139 Þ 17.535 – p1 = 0.097 Þ p1 = 17.44 mm of Hg
ë 25 + 0.139 û
Hence, the vapour pressure of water is 17.44 mm of Hg.
32 E
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18. (a) Define the following terms:
(i) Molarity
(ii) Molal elevation constant (Kb)
(b) A solution containing 15 g urea (molar mass = 60 g mol–1) per litre of solution in water has
the same osmotic pressure (isotonic) as a solution of glucose (molar mass = 180 g mol–1) in
water. Calculate the mass of glucose present in one litre of its solution.
Ans. (a) (i) Molarity
Molarity (M) is defined as the number of moles of the solute dissolved in one Litre of solution.
It is expressed as :
Moles of solute
Molarity (M) =
Volume of solvent in Litre
(ii) When molality (m) of solution is taken as unity then Kb = Tb

(b) For isotonic solution
p1 = p2
Hence C1 = C2
w1 w2
=
M1 M 2
15 w2
=
60 180
w2 = 45 gm
Hence glucose is 45% by weight present in aqueous solution.
19. (a) What type of deviation is shown by a mixture of ethanol and acetone? Give reason.
(b) A solution of glucose (molar mass = 180 g mol–1) in water is labelled as 10% (by mass). What
would be the molality and molarity of the solution?

(Density of solution = 1.2 g mL–1)
Ans (a) In case of negative deviations from Raoult’s law, the intermolecular attractive forces between
A-A and B-B are weaker than those between A-B and leads to decrease in vapour pressure
resulting in negative deviations. A mixture of ethanol and acetone forms a solution with
negative deviation from Raoult’s law. This is because ethanol molecule is able to form
hydrogen bond with acetone molecule as shown.
This decreases the escaping tendency of molecules for each component and consequently the
vapour pressure decreases resulting in negative deviation from Raoult’s law.
(b) 10% w/w solution of glucose in water means that 10 g of glucose in present in 100 g of the
solution i.e., 10 g of glucose is present in (100 – 10) g = 90 g of water.
Molar mass of glucose (C6H12O6) = 6 × 12 + 12 × 1 + 6 × 16 = 180 g mol–1
10
Then, number of moles of glucose = mol = 0.056 mol
180
0.056
\ Molality of solution = = 0.62 m
0.09kg
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If the density of the solution is 1.2 g mL , then the volume of the 100 g solution can be given as :
–1
100g
V = 1.2g mL-1 = 83.33 mL = 83.33 × 10–3 L
0.056 mol
\ Molarity of the solution = = 0.67 M
83.33 ´ 10-3 L
20. (a) State Raoult’s law for a solution containing volatile components.
How does Raoult’s law become a special case of Henry’s law ?
(b) 1.00 g of a non-electrolyte solute dissolved in 50 g of benzene lowered the freezing point of
benzene by 0.40 K. Find the molar mass of the solute. (Kf for benzene = 5.12 K kg mol–1)
Ans. (a) (i) Raoult s law states that for a binary solution containing two volatile components.
A B
XA XB
PA = partial pressure of A
in gas phase above the solution
PB = partial pressure of B
in gas phase above the solution
PT = Total pressure of A & B in gas phase above the solution then
PT = PA + PB
According Raoult’s law
PA µ XA
Þ PA = PA° XA ..... (1)
Similarly PB= PB°XB
So PT = PA°XA + PB°XB
(b) w2 = 1.00 g w1 = 50 g, DTf = 0.40 K
m2 = ?
kf = 5.12 k. Kg mol–1.
w2 / m 2
Q DTf = kf Xm = k f ´
w1 / 1000
k f ´ w2 ´ 1000
m2 =
w1 ´ DTf
5.12k.kgmol -1 ´ 1.00g ´1000

=
50gm ´ 0.40k
= 256 gm
(ii) According to Rooult’s law–
PA = PA0 ´ A .....(i)
According to Henris law
Pg = KH × g ....(ii)
If PA0 = K H , Raoult’s law become a speical case of Henry’s law.
34 E
CBSE
ALLEN
21. (a) Define the following terms :
(i) Mole fraction
(ii) Ideal solution
(b) 15.0 g of an unknown molecular material is dissolved in 450 g of water. The resulting solution
freezes at –0.34°C. what is the molar mass of the material ? (Kf for water = 1.86 K kg mol–1)
Ans. (a) (i) Mole fraction - ratio of moles of solute and sum of moles of solute and moles of solution.
(ii) Ideal solution - A solution which follows Roult's law for a wide range of concentration
and temp.
(b) DTf = Kf × m
15
0.34 = 1.86 M
450
1000
0.34 ´ 450 15
=
1.86 ´ 1000 M
1000 ´ 1.86
or M = = 182.35 gm/mol
0.34 ´ 30
22. (a) Define the following terms :
(i) Azeotrope
(b) 100 mg of a protein is dissolved in enough water to make 10.0 mL a solution. If this solution
has an osmotic pressure of 13.3 mm Hg at 25°C, what the molar mass of protein ?
–1 –1
(R = 0.0821 L atm mol K and 760 mm Hg = 1 atm)
Ans. (a) (i) Azeotrope - A type of liquid mixture having definite composition and boiling like a pure
liquid, is called a constant boiling mixture or an azeotropic mixture.

So PT = PA°XA + PB°XB
1
it means PA° = if solvent is non volatile.
KH
(b) Here w = 100 mg = 0.100 = 0.1 g

V = 10.0 mL = 0.01 L
13.3
p = 13.3 mm Hg = atm
760
T = 25°C = 25 + 273 = 298 K
–1 –1
R = 0.0821 L atm mol K
M=?
wRT
\ Molar mass M =
pV
E 35
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ALLEN
0.1 ´ 0.0821 ´ 298 0.1 ´ 0.0821 ´ 298 ´ 760 1859.4008
M= = =
13.3 13.3 ´ 0.01 0.133
´ 0.01
760
–1
M = 13980.4 g mol
23. Define the term 'osmotic pressure'. Describe how the molecular mass of a substance can be determined
on the basis of osmotic pressure measurement.
Ans. (i) Osmotic pressure : It is the pressure of the solution column that can prevent the entry of solvent
molecules through a semipermeable membrane, when the solution and the solvent are separated
by the same. It is shown by p. It's unit is mm of Hg of atmosphere.
(ii) Relation between osmotic pressure and molar mass :
We know that pV = hBRT (Solution equation)
WBRT
or pV =
MB
WB
(Q hB = , where WB is mass of the solute and MB is molecular mass of the same)
MB
Thus pV MB = WBRT
WBRT
or, M B =
pV
This is the required relation.
24. A solution containing 8g of a substance in 100 g of diethyl ether boils at 36.86 °C, whereas pure
ether boils at 35.60 °C. Determine the molecular mass of the solute.
–1
(For ether Kb = 2.02 K kg mol )
Ans. We have, mass of solute, w2 = 8g
mass of solvent, w1 = 100g
elevation of boiling point,
DTb = 36.86 – 35.60 = 1.26°C
Kb = 2.02
\ Molecular mass of the solute
1000 ´ w2 ´ K b 1000 ´ 8 ´ 2.02 161.6
M2 = = = = 128.25 g mol -1
DTb ´ w1 1.26 ´ 100 1.26
25. Calculate the temperature at which a solution containing 54 g of glucose, C6H12O6, in 250 g of
–1
water will freeze. [Kf for water = 1.86 K kg mol ]
Ans. Molecular mass of glucose , MB = 72 + 12 + 96 = 180
K f ´ W2 ´ 1000 1.86 ´ 54 ´ 1000 100440

DTf = = = = 2.23
M 2 ´ W1 180 ´ 250 45000
Freezing point of solution = 0 – 2.23 = – 2.23°C
36 E
CBSE
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1. Identify which liquid will have a higher vapour pressure at 90°C if the boiling points of two liquids A
and B are 140°C and 180°C, respectively. [1]
(CBSE 2020)
Ans. (A)
2. For a 5% solution of urea (Molar mass = 60 g/mol), calculate the osmotic pressure at 300K.
[R = 0.0821 LatmK-1mol-1] : (CBSE 2020)
OR
Visha took two aqueous solutions - one containing 7.5 g of urea (Molar mass = 60 g/mol) and the
other containing 42.75 g of substance Z in 100 g of water, respectively. It was observed that both the
solutions froze at the same temperature. Calculate the molar mass of Z. [2]
Ans. p = CRT (Volume of solution = 100 mL)
n
p= RT
v
5 0.0821 ´ 300
p= ´
60 0.1
p = 20.5 atm
OR
DTf(urea) = DTf(Z)
w urea 1000 wz 1000

kƒ ´ ´ = kf ´ ´
Murea w solvent Mz w solvent
7.5 1000 42.75 1000

´ = ´
60 100 Mz 100
42.75 ´ 60
Mz = = 342 g / mol
7.50
3. Calculate the mass of ascorbic acid (Molar mass = 176gmol-1) to be dissolved in 75g of acetic acid,
to lower its freezing point by 1.5°C. (Kf = 3.9 K kgmol -1) [3]
(CBSE 2020)
Ans. DTf = K f m
3.9 ´ w B 1000
1.5 = ´
176 75
mass of ascorbic acid = 5.08 g
E 37
Chemistr y
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4. Give reasons : [2]
(a) Cooking is faster in pressure cooker than in cooking pan. (CBSE 2019)
(b) Red Blood Cells (RBC) shrink when placed in saline water but swell in distilled water.
Ans. (a) Due to increase of pressure in cooker, boiling point of water increases
(b) RBC looses water in saline water and absorb water in distilled water due to osmosis.
5. A solution containing 1.9 g per 100 mL of KCl (M = 74.5 g mol–1) is isotonic with a solution
containing 3 g per 100 mL of urea (M = 60 g mol–1). Calculate the degree of dissociation of KCl
solution. Assume that both the solutions have same temperature. [3]
Ans. p1(urea) = p2[KCl] (CBSE 2019)
C1RT = iC2RT
n1 n
=i 2 ( V1 = V2 )
V1 V2
3 1.9
= i´
60 74.5
i = 1.96
i -1
µ=
n -1
1.96 - 1
=
2 -1
= 0.96 or 96%
(a) A decrease in temperature is observed on mixing ethanol and acetone. (CBSE 2019)
(b) Potasium chloride solution freezes at a lower temperature than water.
Ans. (a) Due to positive deviation.
(b) Due to more van't hoff factor.
(a) An increase in temperature is observed on mixing chloroform and acetone. (CBSE 2019)
(b) Aquatic animals are more comfortable in cold water than in warm water.
Ans. (a) Due to negative deviation
(b) In water, oxygen is in dissolved state & as temperature rises, the solubility of oxygen
decreases, It means the solubility of oxygen is less in warm, because of this reason Aquatic
animals are more comfortable in cold water than in warm water.
8. Calculate the freezing point of a solution containing 60 g of glucose (Molar mass = 180 g mol–1)
in 250 g of water.
(CBSE 2018)
(Kf of water = 1.86 K kg mol–1)
Ans. W1 = 250 g ; w2 = 60g ; M2 = 180g/mol or 180g mol–1 [1/2]
Kf = 1.86 k kg mol –1
DTf = Kf m
w 2 (g) ´1000 60 ´1000
DTf = Kf × = 1.86 ´ [1/2]
M 2 ´ w1 (g) 180 ´ 250
= 2.48 K [1/2]
DTf = t(solvent) – t(solution) [1/2]
t(solution) = t(solvent)–DTf
= 273.15 – 2.48 = 270.67 K [1]
38 E
CBSE
ALLEN
9. Give reasons for the following : (CBSE 2018)
(a) Measurement of osmotic pressure method is preferred for the determination of molar masses of
macromolecules such as proteins and polymers.
(b) Aquatic animals are more comfortable in cold water than in warm water.
(c) Elevation of boiling point of 1 M KCl solution is nearly double than that of 1 M sugar solution.
Ans. (a) Protein are high molecular mass material, the magnitude of colligative property depends inversely
on the molecular mass and osmotic pressure is the only colligative property have measurable
magnitude. So, the Osmotic pressure method is preferred for the determination of molar mass
of macromolecules as proteins & polymers. [1]
(b) In water, oxygen is in dissolved state & as temperature rises, the solubility of oxygen decreases,
It means the solubility of oxygen is less in warm, because of this reason Aquatic animals are
more comfortable in cold water than in warm water. [1]
(c) The value of Van't Haff factor is twice in 1M KCl than 1M sugar solution due to which elevation
of Bioling point is more.
The solvent is somewhat but KCl is ionic due to which it dissociates completely.
The elevation of B.P. is DTb = iK b m {In both 1 M KCl & 1M sugar solution} [1]
10. (a) A 10% solution (by mass) of sucrose in water has a freezing point of 269.15 K. Calculate the
freezing point of 10% glucose in water if the freezing point of pure water is 273.15 K.
Given :
(Molar mass of sucrose = 342 g mol–1)
(Molar mass of glucose = 180 g mol–1)
(b) Define the following terms :
(i) Molality (m) (ii) Abnormal molar mass
OR
–1
(a) 30 g of urea (M = 60 g mol ) is dissolved in 846 g of water. Calculate the vapour pressure of
water for this solution if vapour pressure of pure water at 298 K is 23.8 mm Hg.
(b) Write two differences between ideal solutions and non-ideal solutions. (CBSE 2017)
Ans. (a) (i) DTf = Kf × m
w2 / m 2
= kf ´
w1 /1000
k f ´ w2 ´1000
=
m 2 ´ w1
k f ´ 10 ´1000
273.15 – 269.15 =
342 ´ 90
\ kf = 12.3 k kgmol–1. [1]
(ii) DTf = Kfm
= 12.3 × 10 × 1000 × 180 × 90 [1]
= 7.6 K
Tf = 273.15 – 7.6 = 265.55 K [1]
(b) (i) Number of moles of solute dissolved in per kilo gram of the solvent. [1]
(ii) Abnormal molar mass : If the molar mass calculated by using [1]
any of the colligative properties to be different than theoretically
E 39
Chemistr y
ALLEN
OR
(a) (PA0 - PA ) / PA0 = (wB × MA)/(MB × wA)
23.8 - PA
= (30 ´ 18) / 60 ´ 846
23.8
23.8 – PA = 23.8 × [(30 × 18)/60 × 846]
23.8 – PA = 0.2532
PA = 23.55 mm Hg
(b) Ideal solution Non ideal solution
(a) It obeys Raoult's law over the (a) Does not obey Rauolt's
entire range of concentration. law over the entire range of concentration.
(b) Dmix H = 0 (b) Dmix H is not equal to 0.
(c) Dmix V = 0 (c) DmixV is not equal to 0.
(any two correct difference) [3+2=5]
11. (i) Write the colligative property which is used to find the molecular mass of macromolecules
(CBSE 2016)
(ii) In non-ideal solution, what type of deviation shows the formation of minimum boiling azeotropes?
Ans. (i) Osmotic pressure [1]
(ii) Positive deviation from Raouts’ law/ Positive deviation [1]
–1
12. Calculate the boiling point of solution when 2 g of Na2SO4 (M = 142 g mol ) was dissolved in
50 g of water, assuming Na2SO4 undergoes complete ionization. (Kb for water = 0.52 K kg mol–1)
(CBSE 2016)
K bw b ´ 1000
Ans. DTb = i [1/2]
Mb ´ wa
3 ´ 0.52 ´ 2 ´ 1000
DTb = [1/2]
142 ´ 50
[1/2]
= 0.439 K
0
DTb = Tb – Tb [1/2]
Tb = 0.439 + 373 = 373.439 K [1]
13. (i) Why are aquatic species more comfortable in cold water than in warm water? (CBSE 2015)
(ii) What happens when we place the blood cell in saline water solution (hypertonic solution)? Give reason.
Ans. (i) As solubility of gases decreases with increase of temperature, less oxygen is available in summer
in the lakes / as cold water contains more oxygen dissolved. [1]
(ii) They will shrink , due to osmosis. [1]
14. Vapour pressure of water at 20°C is 17.5 mm Hg. Calculate the vapour pressure of water at 20°C
when 15 g of glucose (Molar mass = 180 g mol–1) is dissolved in 150 g of water. (CBSE 2015)
o
Ans. PA = 17.5 mm of Hg WB = 15 g MB = 180 g/mol
WA = 150 g PS = ?
PAo - PS WB ´ M A PAo - PS 15 ´ 18 [1]
= \ = = 0.01
PAo M B ´ WA PAo 180 ´ 150
PAo - PS 17.5 - PS
= = 0.01 [1]
PAo 17.5
\ PS = 17.325 mm of Hg [1]
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EXERCISE-3 R AC E
Type 1 : Passage question 1 :-
Henry was the first to give a quantitative relation between pressure and solubility of a gas in a solvent
which is known as Henry’s law. The law states that at a constant temperature, the solubility of a gas
in a liquid is directly proportional to the pressure of the gas. Dalton, a contemporary of Henry, also
concluded independently that the solubility of a gas in a liquid solution is a function of partial pressure
of the gas. If we use the mole fraction of a gas in the solution as a measure of its solubility, then it
can be said that the mole fraction of gas in the solution is proportional to the partial pressure of the
gas over the solution. The most commonly used form of Henry’s law states that “the partial pressure
of the gas in vapour phase (p) is proportional to the mole fraction of the gas (x) in the solution” and
is expressed as: p = KHx
(i) “The partial pressure of the gas in vapour phase (p) is proportional to the mole fraction of the gas
(x) in the solution” is
(a) Raoult’s law (b) Dalton’s law
(c) Henry’s law (d) None of these
(ii) Value of Henry’s constant KH ____________.
(a) increases with increase in temperature. (b) decreases with increase in temperature.
(c) remains constant. (d) first increases then decreases.
(iii) The value of Henry’s constant KH is _____________.
(a) greater for gases with higher solubility. (b) greater for gases with lower solubility.
(c) constant for all gases. (d) not related to the solubility of gases.
(iv) KH value for Ar(g), CO2(g), HCHO (g) and CH4 (g) are 40.39, 1.67, 1.83×10–5 and 0.413
respectively. Arrange these gases in the order of their increasing solubility :-
(a) HCHO < CH4 < CO2 < Ar (b) HCHO < CO2 < CH4 < Ar
(c) Ar < CO2 < CH4 < HCHO (d) Ar < CH4 < CO2 < HCHO
OR
What do we do to avoid the bend in scuba divers kit :-
(a) air is diluted with He
(b) air is diluted with N2
(c) increase the concentration of O2
(d) decrease the concentration of O2
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Type 2 : Assertion and Reason :-
Question 2 to 6:-Note:- in the following questions a statement of assertion followed by a reason . choose
2. Assertion : Molarity of a solution in liquid state changes with temperature.
Reason : The volume of a solution changes with change in temperature.
3. Assertion : When methyl alcohol is added to water, the boiling point of water increases.
Reason : When a volatile solute is added to a volatile solvent elevation in the boiling point is observed.
4. Assertion : When NaCl is added to water a depression in freezing point is observed.
Reason : The lowering of vapour pressure of a solution causes depression in the freezing point.
5. Assertion : When a solution is separated from the pure solvent by a semipermeable membrane, the
solvent molecules pass through it from pure solvent side to the solution side.
Reason : Diffusion of solvent occurs from a region of high concentration solution to a region of low
concentration solution.
6. Assertion : Low concentration of oxygen in the blood and tissues of people living at high altitude
suffer from anoxia
Reason : due to low atmospheric pressure
Type 3 : Multiple choice quation (one correct answer) (Queations 7 to 16):-
7. On dissolving sugar in water at room temperature solution feels cool to
touch. Under which of the following cases dissolution of sugar will be
most rapid?
(i) Sugar crystals in cold water.
(ii) Sugar crystals in hot water.
(iii) Powdered sugar in cold water.
(iv) Powdered sugar in hot water.
8. At equilibrium the rate of dissolution of a solid solute in a volatile liquid solvent is __________.
(i) less than the rate of crystallisation (ii) greater than the rate of crystallisation
(iii) equal to the rate of crystallization (iv) zero
9. A beaker contains a solution of substance ‘A’. Precipitation of substance ‘A’ takes place when small
amount of ‘A’ is added to the solution. The solution is _________.
(i) Saturated (ii) supersaturated
(iii) unsaturated (iv) concentrated
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10. Maximum amount of a solid solute that can be dissolved in a specified amount of a given liquid solvent
does not depend upon ____________.
(i) Temperature (ii) Nature of solute
(iii) Pressure (iv) Nature of solvent
11. Low concentration of oxygen in the blood and tissues of people living at high altitude is due to
____________.
(i) low temperature
(ii) low atmospheric pressure
(iii) high atmospheric pressure
(iv) both low temperature and high atmospheric pressure
12. Considering the formation, breaking and strength of hydrogen bond, predict which of the following
mixtures will show a positive deviation from Raoult’s law?
(i) Methanol and acetone. (ii) Chloroform and
acetone.
(iii) Nitric acid and water. (iv) Phenol and aniline.
13. Colligative properties depend on ____________.
(i) the nature of the solute particles dissolved in solution.
(ii) the number of solute particles in solution.
(iii) the physical properties of the solute particles dissolved in solution.
(iv) the nature of solvent particles.
14. The unit of ebulioscopic constant is _______________.
–1 –1 –1 –1
(i) K kg mol or K (molality) (ii) mol kg K or K (molality)
–1 –1 –1 –1 –1
(iii) kg mol K or K (molality) (iv) K mol kg or K (molality)
15. An unripe mango placed in a concentrated salt solution to prepare pickle, shrivels because
_____________.
(i) it gains water due to osmosis. (ii) it loses water due to reverse osmosis.
(iii) it gains water due to reverse osmosis. (iv) it loses water due to osmosis.
16. If two liquids A and B form minimum boiling azeotrope at some specific composition then
_______________.
(i) A–B interactions are stronger than those between A–A or B–B.
(ii) vapour pressure of solution increases because more number of molecules of liquids A and
B can escape from the solution.
(iii) vapour pressure of solution decreases because less number of molecules of only one of the
liquid
Answer key :
Q. No. 1 (i) (ii) (iii) (iv) 2 3 4 5 6 7 8
Ans. c a b c or a A D A B A iv iii
Q. No. 9 10 11 12 13 14 15 16
Ans. ii iii ii i ii i iv i
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1. Define the term 'osmotic pressure. [1]
2. Define the Mole fraction. [1]
3. Define the Azeotrope. [1]
4. State the Raoult’s law in its general form in reference to solutions. [2]
5. State the Henry’s law about partial pressure of a gas in a mixture. [2]
6. Explain the Boiling point elevation constant for a solvent. [2]
7. What type of deviation is shown by a mixture of ethanol and acetone? Give reason. [2]
8. Write three differences between ideal solutions and non-ideal solutions. [3]
9. A solution of glucose (molar mass = 180 g mol–1) in water is labelled as 10% (by mass). What would
be the molality and molarity of the solution? [3]
(Density of solution = 1.2 g mL–1)
10. Calculate the freezing point of a solution containing 60 g of glucose (Molar mass = 180 g mol–1) in
250 g of water. (Kf of water = 1.86 K kg mol–1) [3]
11. (a) Give reasons for the following : [5]
(i) Measurement of osmotic pressure method is preferred for the determination of molar masses of
macromolecules such as proteins and polymers.
(ii) Aquatic animals are more comfortable in cold water than in warm water.
(iii) Cooking is faster in pressure cooker than in cooking pan.
(b) 30 g of urea (M = 60 g mol–1) is dissolved in 846 g of water. Calculate the vapour pressure
of water for this solution if vapour pressure of pure water at 298 K is 23.8 mm Hg.
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MOCK TEST SOLUTIONS
1. When two liquids of different conc. are separated by SPM, solvent flows from low conc. to high conc.
amount of external pressure required to be applied on conc. side to stop movement of solvent in known
as osmotic pressure.
2. Mole fraction - ratio of moles of solute and sum of moles of solute and moles of solution.
3. The binary mixture (liquid mixtures) having the same composition in liquid and vapour phase and
boil at constant temperature are called azeotropic mixtures or azeotropes.
4. It states that for a solution of volatile liquids, the partial vapour pressure of each component in the
solution is directly proportional to its mole fraction.
5. Henry's law : It states that at constant temperature, the solubility of a gas in a liquid is directly
proportional to the pressure of the gas.
6. When molality (m) of solution is taken as unity then Kb = Tb.
7. In case of positive deviation from Raoult's law, A-B interactions are weaker than those between A-
A or B-B, i.e., in this case the intermolecular attractive forces between the solute-solvent molecules
are weaker than those between the solute-solute and solvent-solvent molecules. This means that in
such solutions, molecules of A (or B) will find it easier to escape than in pure state. This will increase
the vapour the hydrogen bonds between them. Due to weakening of interactions, the solution shows
positive deviation from Raoult's law.
8. Ideal solution Non ideal solution
(a) It obeys Raoult's law over the (a) Does not obey Rauolt's
entire range of concentration. law over the entire range of concentration.
(b) Dmix H = 0 (b) Dmix H is not equal to 0.

(c) Dmix V = 0 (c) Dmix V is not equal to 0.
9. 10% w/w solution of glucose in water means that 10 g of glucose in present in 100 g of the solution
i.e., 10 g of glucose is present in (100 - 10) g = 90 g of water.
Molar mass of glucose (C6H12O6) = 6 × 12 + 12 × 1 + 6 × 16 = 180 g mol–1
10
Then, number of moles of glucose = mol = 0.056 mol
180
0.056
Molality of solution = 0.09 kg = 0.62 m
If the density of the solution is 1.2 g mL–1, then the volume of the 100 g solution can be given as:
100 g
V = 1.2 g mL-1 = 83.33 mL = 83.33 × 10–3 L
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0.056 mol
Molarity of the solution = = 0.67 M
83.33 ´ 10 -3 L
10. W1 = 250 g ; w2 = 60g ; M2 = 180g/mol or 180g mol–1

Kf = 1.86 k kg mol–1
DTf = Kf m
w 2 (g) ´ 1000 60 ´ 1000

DTf = Kf × M ´ w (g) = 1.86 ´ 180 ´ 250
2 1
= 2.48 K
DTf = t (solvent) - t (solution)
t(solution) = t(solvent) – DTf
= 273.15 – 2.48 = 270.67 K
11. (i) Protein are high molecular mass material, the magnitude of colligative property depends inversely
on the molecular mass and osmotic pressure is the only colligative property have measurable
magnitude. So, the Osmotic pressure method is preferred for the determination of molar of
macromolecules as proteins & polymers.
(ii) In water, oxygen is in dissolved state & as temperature rises, the solubility of oxygen decreases,
It means the solubility of oxygen is less in warm, because of this reason Aquatic animals are more
compertable in cold water than in warm water.
(iii) Due to increase of pressure in cooker, boiling point of water increases
(b) (PA0 - PA ) / PA0 = (wB × MA) / (MB × wA)
23.8 - PA
= (30 ´ 18) / 60 ´ 846
23.8
23.8 – PA = 23.8 × [(30 × 18)/60 × 846]

23.8 - PA = 0.2532
PA = 23.55 mm Hg
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ELECTROCHEMISTRY
l Electrochemistry may be defined as the branch of chemistry which deals with the quantitative study
of inter-relationship between chemical energy and electrical energy and inter-conversion of one form
into another relationships between electrical energy taking place in redox reactions.
l Electrochemical cell : The cell which converts chemical energy into electrical energy is known as
electrochemical cell.
A cell is of two types :
I. Galvanic cell
II. Electrolytic cell
l In Galvanic cell, the chemical energy of a spontaneous redox reaction is converted into electrical work.
l In Electrolytic cell, electrical energy is used to carry out a non-spontaneous redox reaction.
l Representation of a cell ( IUPAC conventions ):
Let us illustrate the convention taking the example of Daniel cell.
(i) Anodic half cell is written on left and cathodic half cell on right hand side.
Zn(s) | ZnSO4 (sol) || CuSO4 (sol) | Cu(s)
(ii) Two half cells are separated by double vertical lines: Double vertical lines indicate salt bridge or any
type of porous partition.
(iii) EMF (electromotive force) may be written on the right hand side of the cell.
(iv) Single vertical lines indicate the phase separation between electrode and electrolyte solution.
Zn | Zn2+ || Cu2+ | Cu
(v) Inert electrodes are represented in the bracket
Zn | ZnSO4 || H+ | H2, Pt
node06\B0B0-BA\Kota\Board Material\Chemistry\CBSE\CBSE Booklet\English\Updated booklet-21\New Pattern CBSE Booklet\Part wise boocklet\Part 1\01_PC\01_Electrochemistry
V
l Resistance (R) =
I
Unit of R : Ohms
1
l Conductance (G) =
R
–1
Unit of G : mho, ohm or Siemen’s
l
l Cell constant (G*) =
A
–1
Unit of G* : cm
l Resistivity of specific resistance (r)
l
R =r
A
unit of r : ohm cm
l Specific conductance / conductivity
1 l
K(Kappa) = r = A ´ R = G ´ G *
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where R is Resistance, l/A = cell constant (G*) and r is resistivity.
3 3
conductance of 1 cm (m ) solution of an electrolyte is called conductivity
–1 –1
unit of K : ohm cm
l Relation between k and L m

1000 ´ k
Lm =
C
where Lm is molar conductivity, k is conductivity and C is molar concentration.
l In case of electrolytic solution, the specific conductance is defined as the conductance of a solution of
definite concentration enclosed in a cell having two electrodes of unit area separated by 1 cm apart.
l Equivalent Conductance
Equivalent conductance is the conductance of an electrolyte solution containing 1 gm equivalent of
electrolyte. It is denoted by Ù .
Ù=Kx V
( Ù = ohm cm-1 x cm3 = ohm-1 cm2)
-1
Usually concern ration of electrolyte solution is expressed as C gm equivalent per litre.

1000
Thus, V=
C
{Volume having 1 gm equivalent electrolyte in the solution} Thus, Ù=K ´ 1000
C
l Molar Conductance
Molar conductance may be defined as conductance of an electrolyte solution having 1 gm mole
electrolyte in a litre. It is denoted by Ù m .
Ùm=K!V
Usually concentration of electrolyte solution is expressed as ‘M’ gm mole elecrtrolyte per litre.
1000
Thus, V=
M
1000
Hence, Ù m =K x
M
Relation between and m : m = n × Ù
Ù Ù Ù
l Kohlrausch¢s law :
(a) In general, if an electrolyte on dissociation give g+ cations and g– anions, then its limiting molar
o
conductivity (L m) is given by
o o o
L m = g+l + + g–l –
o o
Here, l + and l – are the limiting molar conductivities of cation and anion respectively and g+ and g–
are the number of cations and anions furnished by one formula unit of the electrolyte.
(b)Degree of dissociation (a) is given by :
L cm
a=
L om
c o
Here, L m = is molar conductivity at the concentration C and L m is limiting molar conductivity of the
electrolyte.
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(c) Dissociation constant (K) of weak electrolyte :
2
æ L cm ö
C ç o ÷
Ca 2 L
K= = è mø
1- a æ Lm ö
ç1 - Lo ÷
è m ø
l Nernst Equation for electrode reaction :

n+ –
M (aq) + ne ® M(s)
2.303RT 1 0.059 1
E = E0 - log = E0 - log
nF [M n+ ] n [M n+ ]
The cell potential of electrochemical reaction : aA + bB ¾¾®
ne cC + dD is given by :
-
2.303RT 0.059 [C ] [ D ]
c d
E 0
= log [ Q c ] = E 0 - log
cell
nF n [ A ]a [ B]b
l Relation between Ecell and equilibrium constant (Kc) :
2.303RT 0.059
E0cell = log K c = V log K c
nF n
0
l DG = –nF E 0cell
0
where DG = standard Gibbs energy change and nF is the number of Faradays of charge passed. E 0cell
is standard cell potential.
l Cell potential – The potential between the two half-cells is called the.
Electromotive force (emf) is the potential
0 0 0
E cell = Ecathods - Eanode
l Electrolytic cells—are those cells in which electrical energy is used to carry out non-spontaneous
chemical reactions and the reaction takes place in an electrolytic cell is called.
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1. Can you store copper sulphate solutions in a zinc pot?
Ans. Zinc is more reactive than copper. Therefore, zinc can displace copper from its salt solution.
If copper sulphate solution is stored in a zinc pot, then zinc will displace copper from the copper
sulphate solution.
Zn + CuSO4 ¾® ZnSO4 + Cu
Hence, copper sulphate solution cannot be stored in a zinc pot.
2. Calculate the potential of hydrogen electrode in contact with a solution whose pH is 10.
+ - 1
Ans. For hydrogen electrode, H + e ¾¾
® H2 , it is given that pH = 10
2
\ [H+] = 10–10 M
Now, using Nernst equation:
RT 1
Hæ = E 1æ - ln +
+ 1 ö
ç H / H2 ÷
è 2 ø
+ 1 ö
ç H / H2 ÷
è 2 ø
nF [ H ]
0.0591 1
= E 1æ - log +
+ 1 ö
ç H / H2 ÷
è 2 ø
1 [H ]
0.0591 1
= 0- log -10
1 [10 ]
= –0.0591 log 1010
= –0.591 V
3. Calculate the emf of the cell in which the following reaction takes place:
Ans. Ni ( s ) + 2Ag + ( 0.002 M ) ® Ni 2+ ( 0.160 M ) + 2Ag (s)
Applying Nernst equation we have:
E1(cell) = 1.05V
0.0591 [ Ni 2+ ]
E (cell) = E 1(cell) - log 2
n éë Ag + ùû
0.0591 ( 0.160)
= 1.05 - log
2 ( 0.002 )2
0.16
= 1.05 - 0.02955log
0.000004
= 1.05 – 0.02955 log 4 × 104
= 1.05 – 0.02955 (log 10000 + log 4)
= 1.05 – 0.02955 (4 + 0.6021)
= 0.914 V
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4. The cell in which the following reactions occurs:
2Fe3(aq+ ) + 2I(aq)
- 2+
® 2Fe (aq) + I 2(s)
has E 0cell = 0.236 V at 298 K.

Calculate the standard Gibbs energy and the equilibrium constant of the cell reaction.
Ans. Here, n = 2, E 0cell = 0.236 V, T = 298 K
We know that:
DrG° = –nf E cell
º
= –2 × 96487 × 0.236
= –45541.864 J mol–1
= –45.54 kJ mol–1
Again, DrG1 = –2.303RT log Kc
DrG1
Þ log K c = - 2.303RT
-45.54 ´103
=- = 7.981
2.303 ´ 8.314 ´ 298
\ Kc = Antilog (7.981) = 9.57 × 107
5. Why does the conductivity of a solution decrease with dilution?
Ans. The conductivity of a solution is the conductance of ions present in a unit volume of the solution.
The number of ions (responsible for carrying current) decreases when the solution is diluted. As
a result, the conductivity of a solution decreases with dilution.
6. Suggest a way to determine the L 0m value of water.
Ans. Applying Kohlrausch’s law of independent migration of ions, the L 0m value of water can be
determined as follows:
NaOH) - L m( NaCl) = l 4+ + l OH-
0 0
L 0m(H 2O) = l 0H + + l 0OH - L 0m(HCl) + L m(
0 0
= ( l 0H+ + l Cl
0
- ) + ( l Na + l
0
OH - )
0
- ( l 0Na + l 0Cl- ) \ L m (H2 O) = L m (HCl) + L m (NaOH) - L m (NaCl)
0 0 0 0
Hence, by knowing the L 0m values of HCl, NaOH, and NaCl, the L 0m value of water L m (H 2O) can be
0
determined.
7. The molar conductivity of 0.025 mol L–1 methanoic acid is
46.1 S cm2 mol–1.
Calculate its degree of dissociation and dissociation constant. Given l0(H+)
= 349.6 S cm2 mol–1 and l0 (HCOO–) = 54.6 S cm2 mol
Ans. C = 0.025 mol L–1
Lm = 46.1 S cm2 mol–1
l0 (H+) = 349 S cm2 mol–1
l0 (HCOO–) = 54.6 S cm2 mol–1
L 0m (HCOOH) = l0 (H+) + l0 (HCOO–)
= 349.6 + 54.6
= 404.2 S cm2 mol–1
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Now, degree of dissociation :
L m (HCOOH)
µ = L 0 (HCOOH)
m
46.1
=
404.2
= 0.114
Thus, dissociation constant:
c µ2
K =
(1- µ)
( 0.025mol L-1 ) ( 0.114 )2

=
(1 - 0.114 )
= 3.67 × 10–4 mol L–1
8. Calculate the standard cell potentials of galvanic cells in which the following reactions take
place :
(i) 2Cr(s) + 3Cd2+(aq) ¾® 2Cr3+(aq) + 3Cd(s)
E Q Cr 3+ / Cr =–0.74 V ; E Q Cd 2+
/ Cd = –0.40 V
(ii) Fe2+(aq) + Ag+(aq) ¾® Fe3+(aq) + Ag(s)
E Q Fe+3 / Fe +2 = 0.77 V ; E Q Ag +
/ Ag = 0.80 V
Calculate the DrGQ and equilibrium constant of the recations.
Ans. (i) The galvanic cell of the given reaction is depicted as :
Cr(s) Cr 3+ (aq ) Cd 2+ (aq ) Cd (s)
Now, the standard cell potential is

E Qcell = E RQ - E LQ
= –0.40 – (–0.74)
= +0.34 V
D r GQ = -nFE cell
Q
In the given equation,

n=6
F = 96487 C mol–1
E Qcell = +0.34V
Then, Dr GQ = –6 × 96487 C mol–1 × 0.34 V

= – 196833.48 CV mol–1
= –196833.48 J mol–1
= –196.83 kJ mol–1
Again,
D r G Q = –RT ln K
Þ D r G Q = –2.303 RT log K
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Dr G
Þ log K = –
2.303RT
-196.83 ´ 103
=
2.303 ´ 8.314 ´ 298
= 34.496
\ K = antilog (34.496)
= 3.13 × 1034
(ii) E Q Fe 3+ / Fe2+ = 0.77 V
E Q Ag+ / Ag = 0.80 V
The galvanic cell of the given reaction is depicted as :
Fe2+ (aq ) Fe3+ Ag + Ag( s )
(aq ) (aq )
Now, the standard cell potential is

EQcell = E QR - EQL
= 0.80 – 0.77
= 0.03 V
Here, n = 1,
Then, D r GQ = -nFE cell
Q
= –1 × 96487 C mol–1 × 0.03 V.

= –2894.61 J mol–1
= –2.89 kJ mol–1
Again, D r G Q = 2.303 RT Iog k
Dr G -2894.61
Þ log K = = = 0.5073
2.303 RT 2.303 ´ 8.314 ´ 298
\ K = antilog (0.5073)
= 3.2 (approximately)
9. Write the Nernst equation and emf of the following cells at 298K :
(i) Mg(s) Mg2+ (0.001M) Cu 2+ ( 0.0001M ) Cu(s)
(ii) Fe(s) Fe2+ (0.001M) H + (1M) H2 (g) (1bar) Pt(s)
(iii) Sn(s) Sn2+ (0.050M) H + (0.020 M ) H2 (g) (1bar) Pt(s)
(iv) Pt(s) Br2 (l) Br - ( 0.010M ) H + (0.030M ) H 2 (g) (1bar) Pt(s)

Ans. (i) For the given reaction, the Nernst equation can be given as :
Q 0.0591 [Mg2+ ]
E cell = E cell - log
n [Cu2+ ]
0.0591 .001
= {0.34 - ( -2.36 )} - log
2 .0001
0.0591
= 2.7 - log10
2
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= 2.7 – 0.02955
= 2.67 V
(ii) For the given reaction, the Nernst equation can be given as :
Q 0.0591 [Fe2+ ]
E cell = E cell - log + 2
n [H ]
0.0591 0.001
= {0 - ( -0.44)} - log
2 12
= 0.44 – 0.02955(–3)
= 0.52865
= 0.53 V
(iii) For the given reaction, the Nernst equation can be given as :
Q 0.0591 [Sn2+ ]
E cell = E cell - log + 2
n [H ]
= {0 - ( -0.14)} - 0.0591 log 0.050 2

2 ( 0.020)
= 0.14 – 0.0295 × log 125
= 0.14 – 0.062
= 0.078 V
= 0.08 V
(iv) For the given reaction, the Nernst equation can be given as :
Q 0.0591 1
E cell = Ecell - log
n [Br - ]2 [H + ]2
0.0591 1
= ( 0 - 1.09) - 2
log
( 0.010) ( 0.030)2
2
1
= 1.09 - 0.02955 ´ log
0.00000009
1
= 1.09 - 0.02955 ´ log
9 ´ 10-8
= 1.09 – 0.02955 × log(1.11 × 107)
= –1.09 – 0.02955 (0.0453 + 7)
= –1.09 – 0.208 = –1.298 V
10. In the button cells widely used in wanted and other devices the following reaction takes place :
Zn(s) + Ag2O(s) + H2(O) (l) ¾® Zn2+(aq) + 2Ag(s) + 2OH–(aq)
Determine Dr GQ and E Q for the reaction.
Ans. Zn( s ) ¾¾® Zn2+ (aq ) + 2e - ;E Q = 0.76V
Ag2 O(s) + H2 O( l ) + 2e - ¾¾® 2Ag (g) + 2OH- ( aq ) ;E Q = 0.344 V

________________________________________________
Zn(s) + Ag2O(s) + H2O(f ) ¾¾® Zn2+ ( aq ) + 2Ag (s) + 2OH - ( aq ) ;E Q = 1.104 V
\ EQ = 1.104 V
54 E
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ALLEN
We know that,
D r GQ = -nFE Q
= –2 × 96487 × 1.04
= –213043.296 J = –213.04 kJ
11. Conductivity of 0.00241 M acetic acid is 7.896 × 10–5 S cm–1. Calculate its molar conductivity
and if L 0m for acetic acid is 390.5 S cm2 mol–1, what is its dissociation constant?
Ans. Given, k = 7.896 × 10 –5 S cm–1
C = 0.00241 mol L–1
k
Then, molar conductivity, L m =
c
7.896 ´ 10-5 Scm -1 1000 cm3
= 0.00241mol L-1 ´ L
= 32.76 S cm2 mol–1
Again, L 0m = 390.5 S cm2 mol–1

L m 32.76 S cm2 mol -1
Now, a = = = 0.084
L 0m 390.5 S cm2 mol -1
ca 2
\ Dissociation constant, K a =
(1 - a )
( 0.00241mol L ) (0.084)
-1 2
= = 1.86 × 10–5 mol L–1

(1 - 0.084)
12. Calculate DrGº for the reaction
Mg(s) + Cu2+ (aq) ® Mg2+ (aq) + Cu (s)
Given : Eºcell = + 2.71 V, 1F = 96500 C mol–1
Ans. DG° = –nFE°
= –2 x 96500 × (2.71) = –523030 J

13. Define the following terms:
Molar conductivity ( Ù m )
Ans. Molar conductivity of a solution of a given concentration is the conductance of volume V of a
solution containing 1 mole of the electrolte kept between two electrodes with the ara of cross
section (A) distance of units length (l).
14. The standard electrode potential (E°) for Daniel cell is +1.1 V. Calculate the DG° for the reaction.
Zn (s) + Cu2+ (aq) ¾® Zn2+ (aq) + Cu (s)
(1F = 96500 Cmol–1).
Ans. Zn (s) + Cu2+ (aq) ¾® Zn2+ (aq) + Cu (s)
E° = 1.1V
DG° = –nFE°
= –2x96500 × (l.l) = –212300 J
A
Lm = K
l
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15. Calculate the emf of the following cell at 25°C:
Ag (s) | Ag+ (10–3 M)|| Cu2+ (10–1 M)| Cu(s)
Given E° = + 0.46 and log 10n = n.
Ans. Ag (s) | Ag+ (10–3 M)|| Cu2+ (10–1 M)| Cu(s)
E°cell, = +0.46 V
Cell reaction is Cu2+ + 2Ag(s) ® Cu + 2AgÅ
0.059 [Ag+ ]2
Ecell = E°cell – log
2 [Cu 2+ ]
0.059
Ecell = 0.46 – log10 -5
2
= 0.46 + .147 = .6075 V

16. Express the relation among cell constant, resistance of the solution in the cell and conductivity of
the solution. How is molar conductivity of a solution related to its conductivity ?
1 1 l K ´ 1000
Ans. K = r = R ´ A lm =
C
17. The molar conductivity of a 1.5 M solution of an electrolyte is found to be 138.9 S cm2mol –1.
Calculate the conductivity of this solution.
K ´ 1000
Ans. lm =
C
138.9 ´ 1.5
K= = 0.20835Scm–1
1000
18. The electrical resistance of a column of 0.05 M NaOH solution of diameter 1 cm and length
50 cm is 5.55 × 103 ohm. Calculate its resistivity, conductivity and molar conductivity.
l RA 5.55 ´ 10 3 W ´ 0.785cm 2
Ans. R = r or r = = = 87.135 Wcm
A l 50cm
1 æ 1 ö
Conductivity = K = =ç –1
÷ Scm = 0.01148 Scm
–1
r è 87.135 ø
K ´ 1000
Molar conductivity lm = cm3L–1
C
0.01148Scm -1 ´ 1000cm 3 L-1
= -1 = 229.6 Scm2mol–1
0.05molL
19. Calculate the potential for half-cell containing
3+ -4 +
0.10 M K2 Cr2O7 (aq), 0.20 M Cr (aq) and 1.0 × 10 M H (aq)
The half-cell reaction is
Cr2 O27- (aq) + 14 H + (aq) + 6e - ® 2 Cr 3+ (aq) + 7H 2O(l),
and the standard electrode potential is given as Eº = 1.33 V.
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Ans. The cell reaction for the cell:
Cr2 O 27- (aq) + 14 H + (aq) + 6e - ® 2Cr 3+ (aq) + 7H 2O( l)
0.059 [Cr 3+ (aq)]2

E = Eº Cell - log +
n [H (aq)]14 [Cr2O 27- ]
0.059 (0.2)2
E Cell = 1.33 - log
( )
14
6 1.0 ´10 -4 (0.1)
Ecell = 1.33 – 0.556 = 0.774

20. What is meant by ‘limiting molar conductivity’?
Ans. Limiting molar conductivity: The molar conductivity of a solution at infinite dilution is called limiting
molar conductivity and is represented by the symbol Ù º m .
21. A copper-silver cell is set up. The copper ion concentration in it is 0.10 M. The concentration of silver
ion is not known. The cell potential measured 0.422 V. Determine the concentration of silver ion in
the cell.
Given : E 0Ag +
/ Ag
= + 0.80 V, E Cu
0
2+
/ Cu
= + 0.34V
Ans. Half cell reactions :

+ – 2+ –
A t cathode : 2A g (aq) + 2e ® 2Ag(s) ; At anode : Cu(s) ® Cu (aq) + 2e
The cell reaction is
+ 2+
Cu(s) + 2Ag (aq) ® Cu (aq) + 2Ag(s)
The cell can be represented as
2+ +
Cu(s) | Cu (aq) || Ag (aq) | Ag(s)
0 0 0
\ Ecell = Ecathod – Eanode
= 0.80 – 0.34 = 0.46 V
0.059 [Cu 2 + ]
\ E cell = E cell -
0
log
n [Ag+ ]2
0.059 0.1
0.422 = 0.46 - log
2 [Ag + ]2
0.059 +2
0.422 – 0.46 = – [log (0.1) – log[Ag | ]
2
0.038 ´ 2 +2
= = [log (0.1) – log[Ag | ]
0.059
+ 2
= 1.286 = –1– log [Ag ]
+
= 2.286 = –2log|Ag |
+
log [Ag ] = –1.143;
+
[Ag ] = 0.074 M
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22. Express the relation between the conductivity and the molar conductivity of a solution.
Ans. The relationship between conductivity (K) and molar conductivity of a solution is given by
K
Ùm =
C
where C is concentration of solution.
23. Depict the galvanic cell in which the reaction
+ 2+
Zn (s) + 2Ag (aq) ¾® Zn (aq) + 2 Ag (s)
takes place. Further indicate what are the carriers of the current inside and outside the cell. State
the reaction at each electrode..
Ans. The cell reaction is
+ 2+
Zn (s) + 2Ag (aq) ¾® Zn (aq) + 2 Ag (s)
2+ +
The cell is represented as, Zn(s) | Zn (aq) || Ag (aq) | Ag(s)
24. The resistance of a conductivity cell containing 0.001 M KCl solution at 298 K is 1500 W.
What is the cell constant if the conductivity 0.001 M KCl solution at 298 K is
–3 –1
0.146 × 10 S cm ?
–3 –1
Ans. Here conductivity (K) = 0.146 × 10 S cm
resistance (R) = 1500 W
conductivity
Cell constant =
conductance
= conductivity × Resistance
1
= k × R [\ conductance = ]
resistance
–3 –1
Cell constant = 0 0.146 × 10 × 1500 = 0.219 cm
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1. (a) Calculate G° for the reaction (CBSE 2020)
Zn(s) + Cu2+(aq) ® Zn2+(aq) + Cu(s) (3+2=5)
Given : E° for Zn2+/Zn = -0.76 and
E° for Cu+2/Cu = +0.34 V
R = 8.314 JK–1mol–1
F = 96500 mol–1
(b) Give two advantage of fuel cells.
OR
(a) Out of the following pairs, predict with reason which pair will allow greater conduction of electricity:
(i) Silver wire at 30°C or silver wire at 60°C.
(ii) 0.1 M CH3COOH solution or 1 M CH3COOH solution.
(iii) KCl solution at 20°C or KCl solution at 50°C.
(b) Give two points of difference between electrochemical and electrolytic cells. (2)
°
Ans. (a) Eº cell = E Cu +2
/Cu
- E °Zn +2 /Zn
= 0.34 – (-0.76)
= 1.10 V
DGº = –nFEº
= -2×1.10×96500
= -212300 J/mol or -212.3 kJ/mol
(b) (i) Pollution free
(ii) High efficiency
OR
(a) (i) Silver wire at 30ºC because as temperature decreases, resistance decreases so conduction
increases.
(ii) 0.1 M CH3COOH, because on dilution degree of ionization increases hence conduction
increases.
(iii) KCl solution at 50ºC, because at high temperature mobility of ions increases and hence
conductance increases.
(b)
Electrochemical Electrolytic
(1) Anode –ve Anode +ve
Cathode +ve Cathode –ve
(2) Convert chemical Convert electrical
Energy to electrical energy Energy of chemical energy
2. (a) The conductivity of 0.001 mol L–1 acetic acid is 4.95 × 10–5 S cm–1. Calculate the dissociation
constant if L 0m for acetic acid is 390.5 S cm2 mol–1. (CBSE 2019)
(b) Write Nernst equation for the reaction at 25°C :
2Al(s) + 3Cu2+(aq) ¾® 2Al3+(aq) + 3Cu(s)
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(c) What are secondary batteries ? Give an example. [5]
OR
(a) Represent the cell in which the following reaction takes place : [5]
2Al(s) + 3Ni2+(0.1 M) ¾® 2Al3+(0.01 M) + 3Ni(s)
Calculate its emf if E 0cell = 1.41V
(b) How does molar conductivity vary with increase in concentration for strong electrolyte and
weak electrolyte ? How can you obtain limiting molar conductivity ( L 0m ) for weak electrolyte?
k 4.95 ´ 103 Scm 2 1000 cm3

Ans. (a) Lm = = ´ = 49.5Scm 2 mol –1
c 0.001 mol L-1 L
L m 49.5 Scm 2 mol-1

a= = = 0.126
L 0m 390.5Scm 2 mol -1
0.001 mol L-2 ´ ( 0.126 )

2
ca 2
k= = = 1.8 ´ 10 4 mol L-1
(1 - a ) 1 - 0.126
(If K = ca2, then K = 1.6 × 10–5 mol L–1)

2
° 0.059 éë Al3+ ùû
(b) E cell = E cell - log 3
6 éëCu 2+ ùû
(c) Batteries which are rechargeable

Example- Lead storage, Ni-Cd batteries (Or any other one example)
OR
(a) Al(s) | Al (0.01 M) || Ni (0.1 M) | Ni(s)
3+ 2+
2
° 0.059 éë Al3+ ùû
E ( cell) = E ( cell ) - log 3
6 éë Ni 2 + ùû
[ 0.01]
2
0.059
E ( cell) = 1.41V - log
[ 0.1]
3
6
E(cell) = 1.4198 V or E(cell) = 1.42 V

(b) Lm decreases with increase in concentration for both strong & weak electrolyte L 0m can be
obtained for weak electrolyte by applying Kohlrausch law
3. (a) Write the cell reaction and calculate the e.m.f. of the following cell at 298 K : (CBSE 2018)
Sn (s) | Sn2+ (0.004 M) || H+ (0.020 M) | H2(g) (1 bar) | Pt (s)
0
(Given : ESn / Sn
= -0.14V )
2+
(b) Give reasons :

(i) On the basis of Eº values, O2 gas should be liberated at anode but it is Cl2 gas which is
liberated in the electrolysis of aqueous NaCl.
(ii) Conductivity of CH3COOH decreases on dilution.
60 E
CBSE
ALLEN
OR
(a) For the reaction
2AgCl(s) + H2 (g) (1 atm) ¾® 2Ag (s) + 2H+ (0.1 M) + 2Cl– (0.1 M),
DGO = – 43600 J at 25°C.
Calculate the e.m.f. of the cell.
[log 10–n = –n]
(b) Define fuel cell and write its two advantages.
Ans. (a) Sn(s) |Sn2+ (0.004 M) || H+(0.020 M)| H2(g), 1 bar |Pt(s)
(given ® ESn
0
2+
/Sn
= -0.14V )
Reaction at Anode ®
Sn(s) ® Sn (aq
2+
) + 2e
-
[1/2]
Reaction at Cathode ®
+
2H (aq.) + 2e - ® H 2 (g) [1/2]
–––––––––––––––––
Overall Net Reaction ® Sn(s) + 2H (aq.)
+ 2+
® Sn (aq.) + H 2 (g) [1/2]
°
Ecell = (-0.14) V = 0.14 V [1/2]
0.0591 [Sn 2+ ]
E°cell = Ecell
°
- log + 2 [1/2]
2 [H ]
0.0591 0.004
= 0.14 - log = 0.11045 V [1/2]
2 [0.020]2
(b)
(i) E° value of O2 is higher Cl2 but O2 will be liberated from H2O only when higher voltage is
applied. NaCl ® Na+ + Cl–
H2O H+ + OH– [1]
Due to over potential of O2
(ii) Conductivity changes as the concentration of electrolyte changes.
The conductivity will always decrease with decrease in the concentration because the no. of
ions per unit volume carrying current decreases on dilution. Hence, the conductivity of CH3COOH
decreases on dilution. [1]
OR
(a) 2AgCl (s) + H2(g) (1 atm) ¾® 2Ag(s) + 2H+(0.1 M) + 2Cl–(0.1M)
DG° = - nF E°cell [1/2]
-DG° ( -43600)
E°cell = =- = 0.23V [1/2]
nF 2 ´ 96500
0.0591
= 0.23 - log (0.1) 2 (0.1)2 [1/2]
2
0.0591
= 0.23 - log (0.0001) [1/2]
2
0.0591
= 0.23 - log (10)4
2
= 0.23 + 0.1182 = 0.3482 V
E cell » 0.35 V [1]
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(b) The are galvanic cell, designed to convert the energy of combustion of fuel like hydrogen,
methane, methanol directly into electrical energy. Eg , H2 – O2 Fuel cell [1]
2 advantages of fuel cells ®
(1) These cells never becomes dead because due to the continuous supply of fuels. [1/2]
(2) Do not cause only pollution like thermal plant. [1/2]
4. Write the name of the cell which is generally used in inverters. Write the reactions taking place at the
anode and the cathode of this cell. (CBSE 2017)
Ans. Lead storage battery
Anode : Pb(s) + SO42–(aq.) ® PbSO4(s) + 2e– [1/2]
Cathode : PbO2 + SO4 (aq) + 4H + 2e ® PbSO4(s) + 2H2O(l)
2– + – [1/2]
5. (a) The cell in which the following reaction occurs :
2 Fe3+(aq) + 2 I–(aq) ¾® 2Fe2+(aq) + I2(s)
has E ocell = 0.236 V at 298 K, Calculate the standard Gibbs energy of the cell reaction.
(Given: 1 F = 96,500 C mol–1)
(b) How many electrons flow through a metallic wire if a current of 0.5 A is passed for 2 hours ?
(Given : 1 F = 96,500 C mol–1) (CBSE 2017)
Ans. (a) DG0 = –nFE0cell [1/2]
n=2
DG0 = –2 × 96500 C/mol × 0.236 V
= –45548 J/mol
= – 45.548 kJ/mol [1]
(b) Q = I × t = 0.5 × 2 × 60 × 60 [1/2]
= 3600 C
96500 C = 6.023 × 1023 electrons
3600 C = 2.25 × 1022 electrons [1]
6. (a) Calculate E°cell for the following reaction at 298 K:
2Cr(s) + 3Fe2+(0.01M) ® 2Cr3+(0.01M) + 3Fe(s)
Given : Ecell = 0.261V
(b) Using the E° values of A and B, predict which one is better for coating the surface of iron
[E°(Fe2+/Fe) = –0.44 V] to prevent corrosion and why ?
Given : E°(A2+/A) = –2.37 V : E°(B2+/B) = –0.14V (CBSE 2016)
-0.059 [Cr 3+ ]2
Ans. (a) E cell = Ecell
0
log [1/2]
n [Fe 2+ ]3
-0.059 [0.01]2
0.261V = E0cell log [1/2]
6 [0.01]3
-0.059 [1/2]
0.261V = E0cell log100
6
E 0cell = 0.261 + 0.0197
= 0.2807 V [1/2]
(b) A because low value of SRP [1]
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7. (a) The conductivity of 0.001 mol L–1 solution of CH3COOH is 3.905 × 10–5 S cm–1. Calculate its
molar conductivity and degree of dissociations(a).
Given l°(H+) = 349.6 S cm2 mol–1 and l°(CH3COO–)= 40.9 S cm2 mol–1.
(b) Define electrochemical cell. What happens if external potential applied becomes greater than
E °cell of electrochemical cell? (CBSE 2016)
Ans. (a) Ùmc
= k × 1000/C
= 3.905 × 10–5 × 1000/0.001
= 39.05 S cm2/mole [1]
CH3COOH ® CH3COO– + H+
L 0 CH 3COOH = l 0CH COO- + l 0H+
3
= 40.9 + 349.6
L CH 3COOH = 390.5 S cm2/mol
0
Ùm
a=
Ù 0m
= 39.05/390.5
= 0.1 [1]
(b) An electrochemical cell is a device in which chemical energy of the redox reaction is converted
into electrical energy. While electrolytic cell do the reverse.
® e– flow from Cu to Zn and current flows from Zn to Cu. [1]
8. Calculate the time to deposit 1.5 g of silver at cathode when a current of 1.5 A was passed through
the solution of AgNO3. (Molar mass of Ag = 108 g mol–1, 1 F = 96500 C mol–1) (CBSE 2015)
Ans. Wt. of Ag = 1.5g
Current = i = 1.5amp
Molecular mass = 108 g/mol
F = 96500 C/mol
n = number of electron transferred
M´I´t
W= [1]
n´F
M ´ n ´ F 1.5 ´ 1 ´ 96500
\ t= = [1]
M´I 108 ´ 1.5
= 893.51 s or 14.89 min [1]
9. Calculate E0cell and DrG0 for the following reaction at 25°C :
A2+ + B+ —® A3+ + B
Given : Kc = 1010, 1 F = 96500 C mol–1 (CBSE 2015)
Ans. A2+ + B+ ® A3+ + B (n = 1)
Kc = 1010 F = 96500C/mol T = 25ºC = 298K
o o
DG = ? E =? R = 8.314JK–1mol–1
DGo = –2.303RT log Kc [1]
DGo = –2.303 × 8.314 JK–1mol–1 × 298K × log 1010.
\ DGo = –57058.4 J/mol or –57.0584 kJ/mol
DGo = –57058.4 J/mol = –nFEo = –1 × 96500 × Eo [1]
-57058.4
\ Eo = = 0.591V [1]
-96500
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EXERCISE-3 R AC E
Molar conductivity of solution is the conductance of solution containing one mole of electrolyte, kept
between two electrodes having unit length between them and large cross-sectional area, so as to contain
the electrolyte. In other words, molar conductivity is the conductance of the electrolytic solution kept
between the electrodes of a conductivity cell at unit distance but having area of cross-section large
enough to accommodate sufficient volume of solution that contains one mole of the electrolyte. It is
denoted by Lm.
(i) The mathematical expression for molar conductivity is.
ca 2 k G*
(a) ka = (b) L m = (c) k = (d) L m = a L °m
1– a C R
(ii) The units of molar conductivity Lm is.
2 –1 –1 –2 –1
(a) Scm mol (b) Scm (c) Smolcm (d) cm
(iii) Solutions of two electrolytes ‘A’ and ‘B’ are diluted. The Lm of ‘B’ increases 1.5 times while
that of A increases 25 times. Which of the two is a strong electrolyte?
(a) electrolyte A (b) electrolyte B (c) electrolyte A & B (d) None of these
(iv) Molar conductivity of ionic solution depends on ___________.
(a) pressure (b) distance between electrodes
(c) concentration of electrolytes in solution (d) surface area of electrodes
Question 2 to 6:-Note:- In the following questions a statement of assertion followed by a reason . choose
2. Assertion : Specific conductance of a cell depends upon area of its electrode.
-1
Reason : Unit of cell constant is cm
3. Assertion : Tin can displace lead from lead bromide solution.
Reason : The standard reduction potential of tin is less than that of lead.
4. Assertion : For spontaneity of cell
+2 +2
Cu/Cu (C1) || Cu (C2)|Cu,
C1 must be less than C2.
Reason : It is not a concentration cell.”
5. Assertion : The conductivity of solutions of different electrolytes in the same solvent and at a given
temperature is same
Reason : The conductivity depends on the charge and size of the ions in which they dissociate, the
concentration of ions or ease with which the ions move under potential gradient.
6. Assertion : Cu is high reactive than hydrogen.
Reason : E 0Cu 2+
/ Cu
is negative.
64 E
CBSE
ALLEN
7. Which of the following statement is correct?
(i) ECell and DG of cell reaction both are extensive properties.
(ii) ECell and DG of cell reaction both are intensive properties.
(iii) ECell is an intensive property while DG of cell reaction is an extensive property.
(iv) ECell is an extensive property while DG of cell reaction is an intensive property.
8. The cell constant of a conductivity cell _____________.
(i) changes with change of electrolyte.
(ii) changes with change of concentration of electrolyte.
(iii) changes with temperature of electrolyte.
(iv) remains constant for a cell.
9. Which cell will measure standard electrode potential of copper electrode?
+ 2+
(i) Pt (s) H2 (g,0.1 bar) H (aq.,1 M) Cu (aq.,1M) Cu
+ 2+
(ii) Pt(s) H2 (g, 1 bar) H (aq.,1 M) Cu (aq.,2 M) Cu
+ 2+
(iii) Pt(s) H2 (g, 1 bar) H (aq.,1 M) Cu (aq.,1 M) Cu
+ 2+
(iv) Pt(s) H2 (g, 1 bar) H (aq.,0.1 M) Cu (aq.,1 M) Cu
10. The difference between the electrode potentials of two electrodes when no current is drawn through
the cell is called ___________.
(i) Cell potential (ii) Cell emf
(iii) Potential difference (iv) Cell voltage
11. An electrochemical cell can behave like an electrolytic cell when ____________.
(i) Ecell = 0 (ii) Ecell > Eext
(iii) Eext > Ecell (iv) Ecell = Eext
12. Which of the statements about solutions of electrolytes is not correct?

(i) Conductivity of solution depends upon size of ions.
(ii) Conductivity depends upon viscosiy of solution.
(iii) Conductivity does not depend upon solvation of ions present in solution.
(iv) Conductivity of solution increases with temperature.
13. L °m [NH 4OH] is equal to ______________.
(i) L°m[NH OH] + L°m[ NH Cl] – L °[HCl ]

4 4
(ii) L°m[NH Cl] + L°m[NaOH] – L°[ NaCl]
4
(iii) L°m[NH Cl] + L°m[NaCl] – L°[NaOH]

4
(iv) L°m[NaOH] + L°m[NaCl] – L°[NH Cl]
4
14. E 1Cell = 1.1V for Daniel cell. Which of the following expressions are correct description of state
of equilibrium in this cell?
2.303RT
(i) 1.1 = Kc (ii) log K c = 1.1
2F
1.2
(iii) log Kc = (iv) log Kc = 1.1
0.059
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15. Conductivity k, is equal to ______________.
1 l æ 1 Aö G*
(i) ç ÷ (ii)
R A èR l ø R
l
(iii) Lm (iv)
A
2+ 2+
16e. For the given cell, Mg|Mg || Cu |Cu
(i) Mg is cathode
(ii) Cu is anode
2+ 2+
(iii) The cell reaction is Mg + Cu ¾® Mg + Cu
(iv) Cu is the oxidising agent
Answer key :
Q. No. 1 (i) (ii) (iii) (iv) 2 3 4 5 6 7 8
Ans. b a b c B A D C D iii iv
Q. No. 9 10 11 12 13 14 15 16
Ans. iii ii iii iii ii ii ii iii
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ALLEN
1. What is meant by ‘limiting molar conductivity’? [1]
2. Define the Molar conductivity ( Ù m ) [1]
3. Express the relation between the conductivity and the molar conductivity of a solution. [1]
4. Conductivity of CH3COOH decreases on dilution. Why ? [2]
5. Define electrochemical cell. What happens if external potential applied becomes greater than E °cell of
electrochemical cell? [2]

6. Calculate DrGº for the reaction [2]
Mg(s) + Cu2+ (aq) ® Mg2+ (aq) + Cu (s)

Given : Eºcell = + 2.71 V, 1F = 96500 C mol–1
7. On the basis of Eº values, O2 gas should be liberated at anode but it is Cl2 gas which is liberated in
the electrolysis of aqueous NaCl. Explain. [2]
8. The conductivity of 0.001 mol L–1 solution of CH3COOH is 3.905 × 10–5 S cm–1. Calculate its
molar conductivity and degree of dissociations(a).
Given l°(H+) = 349.6 S cm2 mol–1 and l°(CH3COO–)= 40.9 S cm2 mol–1. [3]
9. How does molar conductivity vary with increase in concentration for strong electrolyte and weak
electrolyte ? How can you obtain limiting molar conductivity ( L 0m ) for weak electrolyte? [3]
10. Calculate the emf of the following cell at 25°C: [3]

Ag (s) | Ag+ (10–3 M)|| Cu2+ (10–1 M)| Cu(s)

Given E° = + 0.46 and log 10n = n.
11. (a) For the reaction [5]
2AgCl(s) + H2 (g) (1 atm) ¾® 2Ag (s) + 2H+ (0.1 M) + 2Cl– (0.1 M),
DGO = – 43600 J at 25°C.
Calculate the e.m.f. of the cell.
[log 10–n = –n]
(b) Calculate the potential for half-cell containing
3+ -4 +
0.10 M K2 Cr2O7 (aq), 0.20 M Cr (aq) and 1.0 × 10 M H (aq)
The half-cell reaction is
Cr2 O27- (aq) + 14 H + (aq) + 6e - ® 2 Cr 3+ (aq) + 7H 2O(l),
and the standard electrode potential is given as Eº = 1.33 V.
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MOCK TEST SOLUTIONS
1. The molar conductivity of a solution at infinite dilution is called limiting molar conductivity and is
represented by the symbol Ù º m .
2. Molar conductivity of a solution of a given concentration is the conductance of volume V of a solution
containing 1 mole of the electrolte kept between two electrodes with the ara of cross section (A) distance
of units length (l).
3. The relationship between conductivity (K) and molar conductivity of a solution is given by
K
Ùm =
C
where C is concentration of solution.
4. Conductivity changes as the concentration of electrolyte changes.
The conductivity will always decrease with decrease in the concentration because the no. of ions per
unit volume carrying current decreases on dilution. Hence, the conductivity of CH3COOH decreases
on dilution.
5. An electrochemical cell is a device in which chemical energy of the redox reaction is converted into
electrical energy. While electrolytic cell do the reverse.
® e¯ flow from Cu to Zn and current flows from Zn to Cu.
6. G° = – nFE°
= – 2 × 96500 × (2.71) = – 523030 J
7. E° value of O2 is higher Cl2 but O2 will be liberated from H2O only when higher voltage is applied.
NaCl
® Na+ + Cl¯
H+ + OH¯
H2O
Due to over potential of O2
8. Ùcm = k × 1000/C
= 3.905 × 10–5 × 1000/0.001

= 39.05 S cm2/mole
CH3COOH ® CH3COO¯ + H+
L 0 CH 3 COOH = l 0CH - + l 0H +
3 COO
= 40.9 + 349.6
L 0 CH 3 COOH = 390.5 S cm2/mol
Ùm
= a=
Ù 0m
= 39.05/390.5
= 0.1
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9. Ù m decreases with increase in concentration for both strong & weak electrolyte Ù 0 can be obtained
m
for weak electrolyte by applying Kohlrausch law.

10. Ag (s) | Ag+ (10–3 M) || Cu2+ (10–1 M) | Cu(s)
E°cell, = +0.46 V
Cell reaction is Cu2+ + 2Ag(s) ® Cu + 2AgÅ
0.059 [Ag + ]2
Ecell = E°cell – log
2 [Cu 2 + ]
0.059
Ecell = 0.46 – log10 -5
2
= 0.46 + .147
= .6075 V
11. (a) 2AgCl (s) + H2(g) (1 atm) ¾® 2Ag(s) + 2H+ (0.1 M) + 2Cl¯(0.1M)
DG° = - nF E°cell
-DG° (-43600)
E°cell = = =- = 0.23V
nF 2 ´ 96500
0.0591
= 0.23 - log (0.1) 2 (0.1)2
2
0.0591
= 0.23 - log (0.0001)
2
0.0591
= 0.23 - log (10) 4
2
= 0.23 + 0.1182 = 0.3482 V
E cell » 0.35 V
(b) The cell reaction for the cell:
Cr2 O27- (aq) + 14 H + (aq) + 6e - ® 2Cr 3+ (aq) + 7H 2 O( l)
0.059 [Cr 3 + (aq)]2

E = Eº Cell - log +
n [H (aq)]14 [Cr2 O 27 - ]
0.059 (0.2)2
E Cell = 1.33 - log
( )
14
6 1.0 ´ 10 -4 (0.1)
Ecell = 1.33 – 0.556 = 0.774
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CHEMICAL KINETICS
l Chemical Kinetics : The branch of physical chemistry which deals with the study of rate of reaction
and factors affecting rate.
l Rate of chemical reaction : The change in concentration of any reactant or product per unit time is
called rate of reaction.
l Reaction –m1A + m2B ® n1C + n2D
Rate of reaction
1 d[A] 1 d[B] 1 d[C] 1 d[D]
=- =- =+ =+
m 1 dt m 2 dt n1 dt n 2 dt
l Types of Rate of Reaction :
1. Average rate of reaction : The rate of reaction measured over the long time interval is called
average rate of reaction.
Avg rate Dx/Dt = –D[R]/Dt = +D [p]/Dt
2. Instantaneous rate of reaction : The rate of reaction measured at a particular time is called
instantaneous rate of reaction.
(Rate)i = (Instantaeous rate) dx/dt = –d[R]/dt=+d[P]/dt
l Factors affecting Rate of Reaction
1. Concentration of reactant 2. Surface area
3. Temperature 4. Nature of reactant
5. Presence of catalyst 6. Radiation in photochemical reaction
l Rate constant (k) : It is equal to the rate of reaction when molecular concentration of reactant is at
unity.
l Rate law : The rate of reaction is directly proportional to the product of concentration of reactant and
each concentration is raised to some power which may or may not be equal to stereochemistry
experimentally.
For a reaction, aA + bB ® cC + dD
node06\B0B0-BA\Kota\Board Material\Chemistry\CBSE\CBSE Booklet\English\Updated booklet-21\New Pattern CBSE Booklet\Part wise boocklet\Part 1\01_PC\04_Chemical Kinetics.p65
p q
Rate law = k[A] [B]
where powers p and q are determined experimentally.
l Molecularity : The total number of reactants taking part in elementary chemical reaction is called
molecularity.
l Order of reaction : The sum of powers to which the concentration terms are raised in a rate law
expression is called order of reaction.
For above case, Order = P + Q
Orders of reaction is determined experimentally.
l Half-life period : The time during which the concentration of the reactant is reduced to half of its
initial concentration is called half-life period.
l Integrated rate law equation for zero order reaction is given as below :
[ R]o -[ R]t
(a) k =
t
Where k is rate constant and [R]0 is initial molar concentration.
[ R ]o
(b) t1/2 = [ ] t1/2 is half-life period of zero order reaction.
R t
l Integrated rate law equation for first order reaction :
2.303 [ R ]o
(a) k = log
[ R ]t
t
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where k is rate constant, [R]0 is initial molar concentration and [R] is final concentration at time ‘t’.
(b) Half-life period (t1/2) for first order reaction :
0.693
t1/ 2 =
k
l Zero Order Reactions
(i) Decomposition of Gases on metal surface. (ii) Photochemical Reaction.
Differential Rate Equation :
0
r=-d[A]/dt = K[A]
Integrated Rate Equation
0
[A]t = [A] — Kt ; x=Kt
[A]0 [A]0
t1/2 = t50%= ; t100% = =2t1/2
2K K
l First Order Reactions

Eg. 1. All Radioactive decay 2. Pseudo First order reaction.
Differential Rate Equation

r=-d[A]/dt = K[A]1
Integrated Rate Equation
[A]0
Kt = 2.303 log
[A]t
t½=t 50%=0.693
K
t¾=t75%=2t½
l Important kinetic expression for reaction of type A ¾® B :

Order Zero 1st
Differential Rate = k Rate= k[A]
rate law
[A]0
Integrated [A0]–[A]= kt kt = In
[A]
rate law
[A]0 ln 2
Half life (t1/2) t1/2 = 2k t1/2 =
k
(t3/4) t3/4=1.5 t1/2 t3/4= 2 t1/2
l Pseudo chemical reaction : The chemical reaction which looks like higher order reaction but in real
it follows lower order reaction.
CH3COOC2H5 + H2O ® CH3COOH + C2H5OH
1
Rate = k[CH3COOC2H5]
Order = 1
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1. In a reaction, 2A ® Products, the concentration of A decreases from 0.5 mol L–1 to 0.4 mol L–1 in 10
minutes. Calculate the rate during this interval?
1 D[A]
Ans. Average rate = -
2 Dt
1 [A]2 - [A]1
=-
2 t 2 - t1
1 (0.4 - 0.5)
=-
2 10
1 -0.1
= ´
2 10
= 0.005 mol L–1 min–1
= 5 × 10–3 M min–1
2. Time required to decompose SO2Cl2 to half of its initial amount is 60 minutes. If the decompositon is
a first order reaction, calculate the rate constant of the reaction.
Ans. We know that for a 1st order reaction,
0.693
t1/ 2 =
k
It is given that t1/2 = 60 min
0.693
\ k= t
1/ 2
0.693
=
60
= 0.01155 min–1
= 1.155 × 10–2 min–1
k = 1.925 × 10–4 s–1
3. A first order reaction has a rate constant 1.15 × 10–3 s–1 . How long will 5g of this reactant take to
reduce to 3g ?
Ans. We know that for a 1st order reaction,
2.303 [R] 2.303 5 2.303
t= log 0 = log = ´ 0.2219 = 444.38 s = 444 s
k [R] 1.15 ´ 10-3 3 1.15 ´ 10-3
4. For the reaction : 2A + B ® A2B
the rate= k [A][B]2 with k=2.0 × 10–6 mol–2L2s–1. Calculate the initial rate of the reaction when
[A]=0.1mol L–1. [B] = 0.2 mol L–1 . Calculate the rate of reaction after [A] is reduced to 0.06 mol L–1.
Ans. The initial rate of the reaction is
Rate = k[A][B]2 = (2.0 × 10–6 mol–2 L2 s–1) (0.1 mol L–1) (0.2 mol L–1)2 = 8.0 × 10–9 mol–2 L2 s–1
when [A] is reduced from 0.1 mol L–1 to 0.06 mol–1, the concentration of A reacted = (0.1 – 0.06) mol
L–1 = 0.04 mol L–1
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1
Therefore, concentraction of B reacted = ´ 0.04 mol L-1 = 0.02mol L-1
2
Then, concentration of B available, [B] = (0.2 – 0.02) mol L–1 = 0.18 mol L–1
After [A] is reduced to 0.06 mol L–1, the rate of the reaction is given by.
Rate = k [A][B]2 = (2.0 × 10–6 mol–2 L2 s–1) (0.06 mol L–1) (0.18 mol L–1)2 = 3.89 × 10 –9 mol L–1 s–
1
5. The decomposition of NH3 on platinum surface is zero order reaction. What are the rate of
production of N2 and H2 if k = 2.5 × 10–4 mol litre–1 s–1.
Ans. 2NH3 ® N2 + 3H2.
1 d[NH3 ] d[ N 2 ] 1 d[H2 ]
Rate of reaction (r)= – = =
2 dt dt 3 dt
Rate (r) = K[NH3]° = K (Q zero order reaction)
= 2.5 × 10–4
d[ N 2 ]
\ = r = 2.5 × 10–4 mol lit–1s–1
dt
d[H2 ]
= 3r = 3 × 2.5 × 10–4 = 7.5 × 10–4 mol lit–1sec–1
dt
6. A reaction is first order in A and second order in B :
(i) Write rate equation.
(ii) How is the rate affected when the concentration of B is tripled?
(iii) How is the rate affected when the concentration of both A and B is doubled?
Ans. (i) Rate = k [A]1[B]2
(ii) r0 = k [A]1[B]2
r1 = k [A]1[3B]2
\ r1 = 9 × r0
(iii) r0 = k [A1][B]2
r2 = k [2A]1[2B]2
\ r2 = 8 × r0
7. In a reaction between A and B, the initial rate of reaction (r0) was measured for different initial
concentrations A and B as given below :
–1
A/mol L 0.20 0.20 0.40
B/mol L–1 0.30 0.10 0.05

–1 –1 –5 –5 –4
r0/mol L s 5.07 × 10 5.07 × 10 1.43 × 10
What is the order of the reaction with respect to A and B ?

Ans. Let the order of the reaction with respect to A be x and with respect to B be y.
Therefore,
r0 = k [A]x [B]y
5.07 × 10–5 = k [0.20]x [0.30]y (i)
5.07 × 10 = k [0.20] [0.10]
–5 x y
(ii)
1.43 × 10 = k [0.40] [0.05]
–4 x y
(iii)
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Dividing equation (i) by (ii), we obtain
5.07 ´ 10 -5 k[0.20]x [0.30] y
=
5.07 ´ 10 -5 k[0.20]x [0.10] y
0 y
[0.30]y æ 0.30 ö æ 0.30 ö
Þl= Þç =ç Þ y =0
[0.10]y è 0.10 ÷ø è 0.10 ÷ø
Dividing equation (iii) by (i), we obtain
1.43 ´ 10 -4 k[0.40]x [0.05]y
=
5.07 ´ 10 -5 k[0.20]x [0.30]y
1.43 ´ 10-4 [0.40]x é Since y = 0 ù

Þ = ê[0.05]y = [0.30] y = 1ú
5.07 ´ 10-5 [0.20]x ë û
Þ 2.821 = 2x Þ log 2.821 = x log 2 (Taking log on both sides)
log2.821
Þx= = 1.496 = 1.5
log2
Hence, the order of the reaction with respect to A is 1.5 and with respect to B is zero.
8. The following results have been obtained during the kinetic studies of the reaction :
2A + B ® C + D
–1 –1
Experiment A/mol L B/mol L
–1
Initial rate of formation of D/mol L
–1
min
I 0.1 0.1 6.0 × 10–3
II 0.3 0.2 7.2 × 10–2
III 0.3 0.4 2.88 × 10–1

–2
IV 0.4 0.1 2.40 × 10
Determine the rate law and the rate constant for the reaction.
Ans. Let the order of the reaction with respect to A be x and with respect to B be y.
Therefore, rate of the reaction is given by,
Rate = k[A]x [B]y
According to the question,
6.0 × 10–3 = k[0.1]x [0.1]y (i)
7.2 × 10 = k[0.3] [0.2]
–2 x y
(ii)
2.88 × 10–1 = k[0.3]x [0.4]y (iii)
2.40 × 10–2 = k[0.4]x [0.1]y (iv)
Dividing equation (iv) by (i), we obtain
2.4 ´ 10-2 k[0.4]x [0.1]y
=
6.0 ´ 10-3 k[0.1]x [0.1]y
x
[0.4]x æ 0.4 ö
Þ ( 4 ) = 4x Þ x = 1
1
Þ4= x
Þ4=ç ÷
[0.1] è 0.1 ø
Dividing equation (iii) by (ii), we obtain
2.88 ´ 10-1 k[0.3]x [0.4]y
=
7.2 ´ 10-2 k[0.3]x [0.2]y
y
æ 0.4 ö y 2 y
Þ4=ç ÷ Þ4 =2 Þ2 =2 Þ y =2
è 0.2 ø
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Therefore, the rate law is
Rate = k[A] [B]2
Rate
Þk=
[A][B]2
From experiment I, we obtain

6.0 ´ 10-3 mol L-1 min-1
k= = 6.0L2 mol -2 min -1
( )( )
2
0.1mol L-1 0.1mol L-1
9. The half life for radioactive decay of 14C is 5730 yr. An archaeological artifact contained wood had
only 80% of the 14C found in a living tree. Estimate the age of the sample.
2.303 a
Ans. t = log (a - x )
k
0.693
t1/2 of 14C = 5730 yr ; k = yr–1 ; Also a = 100, (a - x) = 80
5730
2.303 ´ 5730 100
t= log = 1845 yr.
0.693 80
10. During nuclear explosion, one of the products is 90Sr with half-life of 28.1 years. If l mg of 90Sr was
absorbed in the bones of a newly born baby instead of calcium, how much of it will remain after
10 years and 60 years if it is not lost metabolically.
0.693 0.693 -1
Ans. Here, k = = y
t1/ 2 28.1
It is known that,
2.303 [R] 2.303 1

t= log 0 Þ 10 = log
k [R] 0.693 [R]
28.1
2.303
Þ 10 =
0.693
( - log[R])
28.1
10 ´ 0.693
Þ log[R] = -
2.303 ´ 28.1
Þ [R] = anti log ( -0.1071)
= anti log(1.8929) = 0.74814 mg
Therefore, 0.7814 mg of 90Sr will remain after 10 years.

Again,
2.303 [R] 2.303 1 60 ´ 0.693

t= log 0 Þ 60 = log Þ log[R] = -
k [R] 0.693 [R] 2.303 ´ 28.1
28.1
Þ [R] = antilog (–0.6425) = 0.2278 mg

Therefore, 0.2278 mg of 90Sr will remain after 60 years.
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11. For a first order reaction, show that time required for 99% completion is twice the time required for
the completion of 90% of reaction.
Ans. For a first order reaction, the time required for 99% completion is
2.303 100 2.303 2.303
t1 = log = log100 = 2 ´
k 100 - 99 k k
For a first order reaction, the time required for 90% completion is
2.303 100 2.303 2.303
t2 = log = log10 =
k 100 - 90 k k
Therefore, t1 = 2t2
Hence, the time required for 99% completion of a first order reaction is twice the time required for the
completion of 90% of the reaction.
12. A first order reaction takes 40 min for 30% decomposition. Calculate t1/2.
Ans. For a first order reaction,
2.303 [R]
t= log 0
k [R]
2.303 100 2.303 10

k= log = log = 8.918 ´ 10 -3 min -1
40min 100 - 30 40min 7
Therefore, t1/2 of the decomposition reaction is
0.693 0.693
t1 / 2 = = min = 77.7 min
k 8.918 ´ 10 -3
13. For the decomposition of azoisopropane to hexane and nitrogen at 543 K, the following data are
obtained.
t(sec) P(mm of Hg)
0 35.0
360 54.0
720 63.0
Calculate the rate constant.

Ans. The decomposition of azoisopropane to hexane and nitrogen at 543 K is represented by the
following equation.
(CH3)2 CHN = NCH (CH3)2(g) ¾® N2(g) + C6H14(g)
At t = 0 P0 0 0
At t = t P0– p p p
After time, t, total pressure, Pt = (P0 – p) + p + p
Þ Pt = P0 + p Þ p = Pt – P0
Therefore, P0 – p = P0 – (Pt – P0) = 2P0 – Pt
For a first order reaction,
2.303 P0 2.303 P0
k= log = log
t P0 - p t 2P0 - Pt
2.303 35.0 -3 -1
When t=360 s, k = 360s log (2 ´ 35.0 - 54.0) = 2.175 ´ 10 s
2.303 35.0
When t=720 s, k = log = 2.235 ´ 10-3 s -1
720s 2 ´ 35.0 - 63.0
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Hence, the average value of rate constant is
k=
(2.175 ´ 10 ) + (2.235 ´ 10 ) = 2.205 ´ 10
-3 -3
-3 -1
s
2
14. Consider a certain reaction A ® Products with k = 2.0 × 10–2 s–1. Calculate the concentration of A
remaining after 100s if the initial concentration of A is 1.0 mol L–1.
Ans. Since the unit of k is s–1, the given reaction is a first order reaction.
2.303 [A]
Therefore, k = log 0
t [A]
2.303 1.0
Þ 2.0 ´ 10-2 s -1 = log
100s [A]
2.303
Þ 2.0 ´ 10-2 s -1 =
100s
( - log[A])
-2.0 ´ 10-2 ´ 100
Þ log[A] =
2.303
æ -2.0 ´ 10 -2 ´ 100 ö
Þ [A] = anti log ç ÷ = 0.135 mol L-1
è 2.303 ø
Hence, the remaining concentration of A is 0.135 mol L–1.
15. Sucrose decomposes in acid solution into glucose and fructose accorting to the first order rate
law, with t1/2 = 3.00 hours. What fraction of sample of sucrose remains after 8 hours ?
Ans. For a first order reaction,
2.303 [R]
k= log 0
t [R]
It is given that, t1/2 = 3.00 hours

0.693 0.693 -1
Therefore, k = = h = 0.231h -1
t1 / 2 3
Then, 0.231h -1 = 2.303 log [R]0

8h [R]
-1
[R]0 0.231h ´ 8h [R]
Þ log = Þ 0 = anti log ( 0.8024 )
[R] 2.303 [R]
[R]0 [R]
Þ = 6.3445 Þ = 0.1576 » 0.158
[R] [R]0
Hence, the fraction of sample of sucrose that remains after 8 hours is 0.158.
16. For a chemical reaction R ® P, the variation in the concentration (R) vs. time (t) plot is given
as
(R)
t
(i) Predict the order of the reaction.
(ii) What is the slope of the curve ?
Ans. (i) Zero order (ii) Slope = –K
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17. The following data were obtained during the first order thermal decomposition of SO2Cl2 at a constant
volume :
SO2Cl2(g) ® SO2 (g) + Cl2 (g)
Experiment Time@s
–1
Total pressure/atm
1 0 0.4
2 100 0.7
Calculate the rate constant.

(Given log 4 = 0.6021, log 2 = 0.3010)
Ans. The thermal decomposition of SO2Cl2 at a constant volume is represented by the following equation.
SO2Cl2(g) ¾® SO2(g) + Cl2(g)
At t = 0 P 0 0
At t = t P0– p p p
After time, t, total pressure, Pt = (P0 – p) + p + p
Þ Pt = P0 + p Þ p = Pt – P0
Therefore, P0 – p = P0 – (Pt – P0) = 2P0 – Pt
For a first order reaction,
2.303 P0 2.303 P0
k= log = log
t P0 - p t 2P0 - p t
2.303 0.4
When t = 100 s, k = log = 1.386 ´ 10-2 s–1
100s 2 ´ 0.4 - 0.7
18. (a) For a reaction A + B ® P, the rate law is given by,
r = k[A]1/2 [B]2.
What is the order of this reaction ?
(b) A first order reaction is found to have a rate constant k = 5.5 × 10–14 s–1. Find the half life of
the reaction.
Ans. (a) 2.5
0.693 0.693
(b) t1/2 = = = 0.126 × 1014sec.
k 5.5 ´ 10 -14
19. A reaction is of second order with respect to a reactant. How is its rate affected if the concentration
of the reactant is (i) doubled (ii) reduced to half ?
Ans. Rate = K[A]2
(i) 4 times (ii) 1/4 times
20. Define ‘order of a reaction’.
Ans. Order of reaction : Order of a reaction is the sum of the powers of the concentration terms
in the experimentally determined rate equation.
21. Identify the order of a reaction if the units of its rate constant are:
-1 -1 -1 -1
(i) L mol s (ii) L mol s
Ans. (i) Zero order (ii) Second order
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O
-3 -1
22. The thermal decomposition H–C–OH is a first order with a rate constant of 2.4 × 10 s at a certain
O
temperature. Calculate how long will it take for 3/4 of initial quantity of H–C–OH to decompose.
(log 0.25 = – 0.6021).
Ans. The first order reaction is
2.303 [A]0
t= log
K [A]
where [A]0 = 1,
3
[A] ,
4
log 0.25 = - 0.6021,
k = 2.4 ´ 10 -3
2.303
t= [log(A)0 - log(A)2 ]
2.4 ´ 10 -3
2.303
t= [log1 - log 25]
2.4 ´ 10 -3
2.303
t= [10 - (-0.6021)] = 578 s
2.4 ´ 10 -3
23. Explain the following terms:
Molecularity of a reaction
Ans. Molecularity of a reaction: The number of reacting species (atoms, ions or molecules) taking
part in an elementary reaction which must collide simultaneously in order to bring about a
chemical reaction is called molecularity of a reaction.

24. Define the following :
(i) Elementary step in a reaction.
(ii) Rate of a reaction
Ans. (i) Elementary step in a reaction : The study of reactions have three main aspects.
(a) Whether the reaction at all takes place or not i.e. spontaneity of a reaction.
(b) If it is spontaneous, then to what extent the reaction takes place before equilibrium is
attained.
(c) Rates of speeds of reactions.
(ii) Rate of reaction : The rate of a reaction is the change in the concentration of any one of
the reactants or products per unit time.
25. List the factors that determine the rate of a chemical reaction.
Ans. The important factors on which the rate of a chemical reaction depends are
(i) nature of the reacting species.
(ii) concentration of the reacting species.
(iii) temperature at which a reaction proceeds.
(iv) surface area of the reactants.
(v) presence of a catalyst.
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1. Will the rate constant of the reaction depend upon T if the Eact (activation energy) of the reaction is
zero ? [1]
(CBSE 2020)
Ans. No.
2. Assertion (A): The molecularity of the reaction H2 + Br2 ® 2HBr [2]
(CBSE 2020)
Reason (R) : Two molecules of the reactants are involved in the given elementary reaction.
Ans. (i) Both Assertion (A) and Reason (R) are correct statements, and Reason (R) is the correct explanation
of the Assertion (A).
3. Analyse the given graph, drawn between concentration of reactant vs. time : [1 × 2 = 2]
1.6
Concentration of reactant
0.8
0.4
0.2
0 10 20 30
time ®
(a) Predict the order of reaction.
(b) Theoretically, can the concentration of the reactant reduce to zero after infinite time ? Explain.
Ans. (a) Ist order
(b) No, due to exponential relation / the curve never touches the x-axis
4. How will the rate of the reaction of affected when (CBSE 2020)
(a) Surface area of the reactant is reduced,
(b) Catalyst is added in a reversible reaction, and
(c) Temperature of the reaction is increased ? [3]
Ans. (a) Decreases (b) Increases (c) Increases
5. Define order of reaction. Predict the order of reaction in the given graphs : [2]
t1/2 t1/2
(a) (b) (CBSE 2019)
[R]0 [R]0
where [R]0 is the initial concentration of reactant and t1/2 is half-life.
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Ans. It is defined as the sum of powers to which the concentration terms are raised in the rate law equation.
(a) First order (b) zero order
6. The following data were obtained for the reaction : [3]
A + 2B ¾¾ ®C (CBSE 2019)
Initial rate of formation
Experiment [A]/M [B]/M
of C/M min–1
1 0.2 0.3 4.2 × 10–2
2 0.1 0.1 6.0 × 10–3
3 0.4 0.3 1.68 × 10–1
4 0.1 0.4 2.40 × 10–2
(a) Find the order of reaction with respect to A and B.
(b) Write the rate law and overall order of reaction.
(c) Calculate the rate constant (k).
Ans. Rate = k[A]p[B]q
On solving
(a) Order with respect to A = 2, B = 1
(b) Rate = k[A]2[B]1 ; overall order = 3
(c) Experiment 1 4.2 × 10–2 = k(0.2)2(0.3) ; k = 3.5
Experiment 2 6.2 × 10 = k(0.1) (0.1)
–3 2
;k=6
7. A first order reaction is 50% completed in 40 minutes at 300 K and in 20 minutes at 320 K. Calculate
the activation energy of the reaction. (Given : log 2 = 0.3010, log 4 = 0.6021, R = 8.314 JK–1 mol–1).
(CBSE 2018)
2.303 100 2.303
Ans. T1 = 300 K ; K1 = log = log 2 = 0.0575 ´ 0.3010 = 0.0173 [1/2]
t1 100 - 50 40
2.303 2.303
T2 = 320 K ; K 2 = t log 2 = 20 log 2 = 0.1151´ 0.3010 = 0.0346 [1/2]

2
K2 E a æ T2 - T1 ö
log = [1]
K1 2.303R çè T1T2 ÷ø
æ 0.0346 ö Ea æ 320 - 300 ö

log ç ÷= ç ÷
è 0.173 ø 2.303 ´ 8.314 è 320 ´ 300 ø
20E a 0.3010 ´ 2.303 ´ 8.314 ´ 320 ´ 300

log2 = Þ Ea = [1/2]
2.303 ´ 8.314 ´ 320 ´ 300 20
Ea = 27663.79 J mol–1 = 27.663 kJ mol–1 or kJ/mol [1/2]
8. For the reaction (CBSE 2018)
2N2O5(g) ¾® 4NO2(g) + O2(g),
the rate of formation of NO2 (g) is 2.8 × 10–3 M s–1. Calculate the rate of disappearance of N2O5(g).
Ans. Given Reaction :
2N2O5(g) ¾® 4NO2(g) + O2(g),
D[NO2 ]
(given Þ = 2.8´10-3 M/ sec. or M sec–1)
Dt
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Rate of the Reaction Þ
1 D[N2O5 ] 1 D[NO2 ] D[O2 ]

- = = [1/2]
2 Dt 4 Dt Dt
1 D[N2O5 ] 1 D[NO2 ]
- = [1/2]
2 Dt 4 Dt
D[N2O5 ] 2 D[NO2 ]
- =
Dt 4 Dt
1
= ´ 2.8 ´10-3 M sec–1 [1/2]
2
D[N2O5 ]
- = 1.4 ´10-3 M sec–1 or M/sec. [1/2]
Dt
9. What is the effect of adding a catalyst on : (CBSE 2017)
(a) Activation energy (Ea), and
(b) Gibbs energy (DG) of a reaction ?
Ans. (a) Decreases [1]
(b) No change [1]
10. A first order reaction takes 20 minutes for 25% decomposition. Calculate the time when 75% of the
reaction will be completed. (CBSE 2017)
(Given : log 2 = 0.3010, log 3 = 0.4771, log 4 = 0.6021)
2.3 03 [A ] o
Ans. t = log
k [A ]
2.303 100
20 min = log ...(i) [1/2]
k 75
2.3 03 10 0
t= log ...(ii) [1/2]
k 25
Divide (i) equation by (ii)
2.303 100
log
20 75 = log 4 / 3
= k
t 2.303 100 log 4 [1]
log
k 25
20/t = 0.1250/0.6021
t = 96.3 min [1]
11. For a reaction : 2NH3(g) ¾¾® Pt N2(g) + 3H2(g) (CBSE 2016)
Rate = k
(i) Write the order and molecularity of this reaction.
(ii) Write the unit of k.
Ans. (i) zero order , bimolecular/ unimolecular [1]
(ii) mol L–1 s–1 [1]
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12. The rate constant for the first order decomposition of H2O2 is given by the following equation:
(CBSE 2016)
1.0 ´ 10 4 K
log k = 14.2 -
T
Calculate Ea for this reaction and rate constant k if its half-life period be 200 minutes.
(Given : R = 8.314 JK–1 mole–1)
Ans. log k = log A – Ea/2.303RT [1]
Ea / 2.303 RT = 1 × 104 k/ T
Ea =1.0 × 104 × 2.303 × 8.314
=191471.4 J/mol [1]
t1/2 = 0.693/ k
0.693
k=
t 1/2
k = 0.693/200
= 0.0034 min–1
= 3.4 × 10–3 min–1 [1]
13. For the hydrolysis of methyl acetate in aqueous solution, the following results were obtained :
(CBSE 2015)
t/s 0 30 60
-1
[CH 3 COOCH 3 ]mol L 0.60 0.30 0.15
(i) Show that it follows pseudo first order reaction as the concentration of water remains constant.
(ii) Calculate the average rate of reaction between the time interval 30 to 60 seconds
Ans. (i) A0 = 0.60 A = 0.30 when t = 30s
2.303 [A ]
k= log 0 [1/2]
t [A]
2.303 0.60
k= log [1/2]
30 0.30
2.303 2.303
k= log2 = ´ 0.3010
30 30
0.693
k= = 0.231 s -1 [1/2]
30
When A0 = 0.60 A = 0.15 when t = 60s
2.303 0.60
k= log [1/2]
t 0.15
2.303 0.60
k= log [1/2]
60 0.15
2.303 2.303
k= log 4 = ´ 0.6021
60 60
1.3866
k= = 0.231s-1 [1]
60
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As for both cases k is approximately same reaction is of pseudo first order
Change in concentration
(ii) Average rate during the interval 30 – 60 sec =
Change in time
0.15 - 0.30
=- [1/2]
60 - 30
-0.15
=- = 0.005 mol L-1S-1 [1/2]
30
14. (a) For a reaction A + B ® P, the rate is given by (CBSE 2015)
Rate = k [A] [B]
2
(i) How is the rate of reaction affected if the concentration of A is doubled ?

(ii)What is the overall order of reaction if B is present in large excess ?
(b)A first order reaction taken 23.1 minutes for 50% completion. Calculate the time required for 75%
completion of this reaction.
(Given : log 2 = 0.301, log 3 = 0.4771, log 4 = 0.6021)
Ans. (a) (i) Rate increases by 4 times [1]
(ii) 2nd order [1]
(b) Reaction is 50% completed in 23.1 min i.e. Half-life is 23.1 min
0.693
\ k=
t1 / 2
0.693
= = 0.03 min -1 [1]
23.1
2.303 [A ]
k= log 0
t [A]
2.303 100
0.03min -1 = log [1]
t 25
2.303
0.03 = log 4
t
2.303 1.3866
t= ´ 0.6021 = = 46.22 min [1]
0.03 0.03
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EXERCISE-3 R AC E
Rate µ [A]x [B]y
This form of equation is known as differential rate equation, where k is a proportionality constant
called rate constant. The equation like which relates the rate of a reaction to concentration of
reactants is called rate law or rate expression. Thus, rate law is the expression in which reaction
rate is given in terms of molar concentration of reactants with each term raised to some power,
which may or may not be same as the stoichiometric coefficient of the reacting species in a
balanced chemical.
(i) Identify the reaction order from each of the following rate constant.
k = 2.3 × 10–5 L mol–1 s–1
(a) first order (b) zero order (c) second order (d) pseudo first roder
(ii) For a reaction, A + B ? Product; the rate law is given by,
r = k [ A]1/2 [B]2 . What is the order of the reaction?
(a) 1.5 (b) 2.5 (c) 2.0 (d) 0

(iii) The slope in the plot of ln [R] Vs. time gives
+k -k
(a) + k (b) (c) – k (d)
2.303 2.303
(where [R] is the final concentration of reactant.)
(iv) The unit of rate constant is:
(a) (conc.)1–n time–1 (b) (conc.)n time–1 (c) (conc.)n–1 time–1 (d) (conc.)1–n time

2. Assertion : Order of the reaction can be zero or fractional
Reason : We cannot determine order from balanced chemical equation.
3. Assertion : Order and molecularity are same
Reason : Order is determined experimentally and molecularity is the sum of the stoichiometric
coefficient of rate determining elementary step.
4. Assertion : For zero order reaction, the rate v/s time graph is a straight lineparallel to x-axis.
Reason : The rate of change of concentration per unit time in zero order reaction remains constant.
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5. Assertion : For the first order reaction half-life period is expressed as
2.303
t (1 / 2) = log2
K
Reason : The half-life time of a first order reaction is not always constant and it depends upon the
initial concentration of reactants.
6. Assertion : An increase in surface area decrease the rate of reaction.
Reason : Stronger the inter molecular attractive forces, faster is the rate.
7. Which of the following statements is not correct about order of a reaction.
(i) The order of a reaction can be a fractional number.
(ii) Order of a reaction is experimentally determined quantity.
(iii) The order of a reaction is always equal to the sum of the stoichiometric coefficients of reactants in
the balanced chemical equation for a reaction.
(iv) The order of a reaction is the sum of the powers of molar concentration of the reactants in the rate
law expression
8. Which of the following statements is correct?
(i) The rate of a reaction decreases with passage of time as the concentration of reactants dereases.
(ii) The rate of a reaction is same at any time during the reaction.
(iii) The rate of a reaction is independent of temperature change.
(iv) The rate of a reaction decreases with increase in concentration of reactant(s).
9. Rate law for the reaction A + 2B ¾® C is found to be
Rate = k [A][B]
Concentration of reactant ‘B’ is doubled, keeping the concentration of ‘A’ constant, the value of rate
constant will be______.
(i) the same (ii) doubled (iii) Quadrupled (iv) halved
10. A first order reaction is 50% completed in 1.26 × 10 s. How much time would it take for 100%
14
completion?
(i) 1.26 × 1015 s (ii) 2.52 × 1014 s
(iii) 2.52 × 1028 s (iv) Infinite
11. The value of rate constant of a pseudo first order reaction ____________.
(i) depends on the concentration of reactants present in small amount.
(ii) depends on the concentration of reactants present in excess.
(iii) is independent of the concentration of reactants.
(iv) depends only on temperature
12. Which of the following statements are applicable to a balanced chemical equation of an elementary
reaction?
(i) Order is same as molecularity.
(ii) Order is less than the molecularity.
(iii) Order is greater than the molecularity.
(iv) Molecularity can be zero.
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13. At high pressure the following reaction is zero order
2NH 3 (g) ¾¾¾¾¾®1130 K
Platinum catalyst
N 2 (g) + 3H 2 (g)
Which of the following options are incorrect for this reaction?

(i) Rate of reaction = Rate constant
(ii) Rate of the reaction depends on concentration of ammonia.
(iii) Rate of decomposition of ammonia will remain constant until ammonia disappears completely.
(iv) Further increase in pressure will change the rate of reaction.
14. Which of the following graphs is correct for a first order reaction?
t1/2 t1/2
(i) (ii)
[R]0 [R]0
k
slope =
concentration[P]
2.303
[R]0
log
Molar
(iii) (iv) [R]
Time Time
15. In any unimolecular reaction ______________.

(i) two reacting species is involved in the rate determining step.
(ii) the order and the molecularity of slowest step are equal to one.
(iii) the molecularity of the reaction is one and order is zero.
(iv) both molecularity and order of the reaction are one.
16. Rate law can be determined from balanced chemical equation if _______.
(i) reverse reaction is involved. (ii) it is an elementary reaction.
(iii) it is a sequence of elementary reactions. (iv) any of the reactants is in excess.
Answer key :
Q. No. 1 (i) (ii) (iii) (iv) 2 3 4 5 6 7 8
Ans. c b c a D C C B D iii i
Q. No. 9 10 11 12 13 14 15 16
Ans. ii ii ii i ii iv ii ii
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1. Explain the Molecularity of a reaction. [1]
2. Define ‘order of a reaction’. [1]
3. Define the rate of a reaction? [1]

4. For a reaction A + B ® P, the rate law is given by, [2]
1/2 2
r = k[A] [B] .
What is the order of this reaction ?
5. A reaction is of second order with respect to a reactant. How is its rate affected if the concentration
of the reactant is (i) doubled (ii) reduced to half ? [2]
6. For a chemical reaction R ® P, the variation in the concentration (R) vs. time (t) plot is given as
(R)
(i) Predict the order of the reaction. (ii) What is the slope of the curve ? [2]
7. For a reaction A + B ® P, the rate is given by [2]
Rate = k [A]2 [B]
(i) How is the rate of reaction affected if the concentration of A is doubled ?
(ii)What is the overall order of reaction if B is present in large excess ?
8. A first order reaction is found to have a rate constant k = 5.5 × 10–14 s–1. Find the half life of
the reaction. [3]
9. The decomposition of NH3 on platinum surface is a zero order. What would be the rates of
–4 –1 –1
production of N2 and H2 if k = 2.5 × 10 mol Ls ? [3]
14
10. The half-life for decay of radioactive C is 5730 years. archaeological artifact containing wood had
14
only 80% of the C activity found in a living tree. Calculate the age of the artefact. [3]
11. The decomposition of phosphine, (PH3) proceeds according to the following equation: [5]
4 PH3 (g) ® P4 (g) + 6 H2 (g)
It is found that the reaction follow the following rate equation:
Rate = k [PH3]
The half-life of PH3 is 37.9 s at 120ºC.
th
(i) How much time is required for 3/4 of PH3 to decompose?
(ii) What fraction of the original sample of PH3 remains behind after 1 minute?
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MOCK TEST SOLUTIONS
1. The number of reacting species (atoms, ions or molecules) taking part in an elementary reaction which
must collide simultaneously in order to bring about a chemical reaction is called molecularity of a
reaction.
2. The sum of powers of the concentration of the reactants in the experimental rate law expression is
called the order of that chemical reaction.
3. The rate of a reaction can be defined as the change in concentration of a reactant of product in unit
time.
4. Order :- 2.5
5. Rate = K[A]2
(i) 4 times (ii) 1/4 times
6. (i) Zero order (ii) Slope = – K
7. (i) Rate increases by 4 times (ii) 2nd order
0.693 0.693
8. t1/2 = = = 0.126 × 1014 sec.
k 5.5 ´ 10-14
9. 2NH3 ® N2 + 3H2.
1 d [ NH 3 ] d [ N 2 ] 1 d[H 2 ]
Rate of reaction (r)= – = =
2 dt dt 3 dt
Rate (r) = K[NH3]° = K (Q zero order reaction)

= 2.5 × 10–4
d [N2 ]
= r = 2.5 × 10–4 mol lit–1s–1
dt
d [N2 ]
= 3r = 3 × 2.5 × 10–4 = 7.5 × 10–4 mol lit–1 sec–1
dt
2.303 a
10. t= log
k (a - x)
0.693
t1/2 of 14C = 5730 yr ; k = yr–1 ; Also a = 100, (a – x) = 80
5730
2.303 ´ 5730 100

t= log = 1845 yr.
0.693 80
11. (i) Here t1/2 = 37.9 s
Let initial concentration = a
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3
\ x= a
4
Using the formula
2.303 a
t= log
k a-x
2.303
a é 0.693 ù
t = 0.693 log 3 êQk = ú
t1/2 a- a ë t1/2 û
4
t1/2 a
t = 2.303 ´ log
0.693 1
a
4
2.303 ´ t1/2 2.303 ´ t1/2 ´ log 2

t= ´ log 4 =
0.693 0.693
2.303 ´ 37.9 ´ 2 ´ 0.3010

t= [\ t1/2 = 37.9s]
0.693
52.544
= = 75.82 sec.
0.693
(ii) Here t = 1 min = 60s and t1/2 = 37.9s
Using the formula
2.303 [A]0 0.693
t= log and k =
k [A]t t1/2
2.303
[A]0
\ t = 0.693 log [A]
t 1/2 1
t1/2 [A]0
t = 2.303 ´ ´ log
0.693 [A]t
2.303 ´ 37.9 [A]0

1= log
0.693 [A]1
[A]0 1 ´ 0.693 0.693

\ log = = = 0.0079
[A]t 2.303 ´ 37.9 87.2837
[A]0
= anti - log (0.0079) = 1.018
[A]t
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SURFACE CHEMISTRY
l The branch of chemistry which deals with boundary separating two bulk phases is termed as surface
chemistry.
l Adsorption : The phenomenon of attracting and retaining the molecules of a substance on the surface
of a liquid or solid leading to a higher concentration on the surface in comparision to the bulk is called
adsorption. Examples are : (i) water vapour on silica get, (ii) H2, O2, NH3 on activated charcoal.
l Adsorption occurs because of unbalanced forces acting inwards on the surface of the solid or a liquid.
l The substance adsorbed is called adsorbate and substance on which adsorption takes place is
adsorbent.
l In physical adsorption, adsorbate is held to adsorbent by weak van der Waals forces. In chemisorptions,
adsorbate is held to adsorbent by strong chemical bond type of foces.
l Water vapours are adsorbed in silica gel but absorbed in CaCl2.
l If the concentration of adsorbate is more on the surface with respect to bulk, it is called positive
adsorption. If it is less on the surface with respect to bulk, it is called negative adsorption.
l Greater the surface area of the adsorbent, the more is the extent of adsorption.
l Higher the critical temperature of a gas, greater is its extent of adsorption.
l Physical adsorption is due to van der Waals forces and is reversible. Chemisorption involves the
formation of compounds on the surface and is irreversible.
l At constant temperature, adsorption generally increases with pressure. The lower the temperature, the
greater is the effect of pressure.
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COMPARISON OF PHYSI-SORPTION AND CHEMI-SORPTION

Physical Adsorption Chemical Adsorption (Activated ad.)
1. It is caused by intermolecular vander waal’s forces. It is caused by chemical bond formation.
2. It is not specific. It is highly specific.
3. It is reversible. It is irreversible.
4. Heat of adsorption is low. – 20 to –40 KJ/mol Heat of adsorption is high. –80 to –240 KJ/mol
5. No appreciable activation is energy is involved. High activation energy involved.
6. It forms multimolecular layers on adsorbent surface. It forms unimolecular layer under high pressure.
l Absorption : It is the phenomen in which a substance is uniformly distributes the rough out the bulk,
i.e., it is the penetration of the substance through the surface into bulk of the solid. Example water
vapour are absorbed by anhydrous CaCl2.
l Sorption : Sometimes the adsorbate appears on surface of adsorbent and later basis into the body
of adsorbent. Thus adsorption changes into absorption such side by side occurence of absorption and
adsorption is called sorption.
l Desorption : The process of removing on adsorbed substance from a surface on which it is adsorbed
is called desorption.
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l Application of adsorption :
® Production of high vacuum.
® Gas masks is coal mines.
® Removal of calourling matter from solutions.
® Separation of inert gases.
l Freundlich adsorption isotherm is
x x 1
= kP1/ n (n > 1) i.e., log = log k + log P
m m n
1
slope = n
log x/m
log k
log P
The plot of log x/m vs log P gives a straight line with slope = 1/n and y-intercept = log k.
l Adsorption is generally temperature dependent. Generally adsorption is exothermic and, therefore,
adsorption decreases with the increase in temperature.
l For adsorption from solution, pressure (P) is replaced by equilibrium concentration (C).
l Colloidal solutions are intermediate between true solutions and suspensions.
Their size ranges in the order 1 nm to 1000 nm.
l A colloidal system consists of two phases : the dispersed phase and dispersion phase.
TYPES OF COLLOIDS ACCORDING TO THEIR SIZE

Multi Molecular Macro Molecular Associated colloids
Formation by aggregation of Formation by aggregation of big size These are the substances which
a large number of atoms or molecules. These are polymers with behave as normal electrolytes at low
smaller molecules of substance. high molecular mass. concentration but get associated
at higher concentration and behave
as colloidal solutions. These associated
particles are also called micelles.
Ex. ® Gold Sol (Au) Ex. ® Starch, Cellulose, Ex. ® Soap & Detergent
Sulphur sol (S8) Protein etc.
l Lyophilic sols : There is strong attraction between dispersed phase and dispersion medium. These are
formed by organic substances like gum, starch, protein etc. These are reversible and more stable.
l Lyophobic sols : There is very little interaction between dispersed phase and dispersion medium and
are formed by inorganic substances like metals, their sulphides etc. These are irreversible and less
stable.
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COMPARISION OF LYOPHOBIC AND LYOPHILIC SOLS
Property Lyophilic sol (Emulsoid) Lyophobic sol (suspensoid)
1. Preparation Can be easily prepared by shaking or Can not be prepared easily special
warming the substance with solvent methods are required
2. Stability are more stable are less stable
3. Reversibility are reversible are irreversible
4. viscocity viscocity is much higher than that of solvent viscocity is nearly same as that of the solvent
5. Surface tension Surface tension is usually low Surface tension is almost same as that of solvent
6. Hydration or These are highly solvated as the particles These are less solvated as the particles have less
solvation have great affinity for solvent affinity for the solvent
7. Charge The particles have little charge or no The particles carry a characteristic charge
charge at all either positive or negative
8. Visibility Particles can not be seen under microscope Particles can be seen under microscope
9. Coagulation or Precipitated by high concentration of Precipitated by low concentration of electrolytes
precipitation electrolytes
10. Tyndall effect Less Scattering More Scattering
11. Migration in may or may not migrate as they may migrate towards anode or cathode as these
electric field or may not carry charge. particles carrry charge.
12. General Ex. Mostly of organic nature Mostly of Inorganic nature
Ex. Gelatin, Starch, Ex. Transiton metal salt in water like
Gum, Albumin & Cellulose Solution Gold, As etc.
l The stability of lyophilic sols is due to their greater hydration in the solution.
l The colloidal systems show Brownian movement, Tyndall effect and electrophoresis.
l Tyndall effect : When a beam of light is passed through colloidal solution placed in dark room, the
path of beam gets illuminated with a bluish light, it is known as Tyndal effect.
l Aggregate of ions in an associated colloidal sol is called ionic micelle. The concentration above
which these are formed is called critical micelle concentration (CMC) and the temperature above
which these are formed is called Kraft temperature (Tk).
l Conversion of a freshly precipitated substance into colloidal sol by shaking with a suitable electrolyte
is called peptization.
l Peptising agent—is the process of convertying freshly prepared precipitate into colloidal sol by shaking
it with the dispersion medium in the presence of small amount of electrolyte. The electrolyte added
is called the Peptising agent.
l Dialysis : It is a process of removing a dissolved substance from a colloidal solution by means of diffusion
through a suitable membrane when dialysis is made by applying an electric field, it is called
electrodialysis.
l The movement of colloidal particles under the infuence of an electric field is called electrophoresis.
l The process of changing the colloidal particles in a sol into the insoluble precipitate by the addition of
some suitable electrolytes is known as coagulation.
l Hardy Schulze Rule - This rule states that the precipitating effect of an ion on dispersed phase of
opposite charge increases with the valency of the ion.
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The higher the valency of the flocculating ion, the greater is its precipitating power. Thus for the
precipitation of As2S3 sol (–ve) the precipitating power of Al3+, Ba2+, and Na+ ions is in the order
Al3+ > Ba2+ > Na+
Similarly for precipitating Fe(OH)3 sol (positive) the precipitating power of [Fe(CN)6]–3, SO42– and Cl–
ions is in the order
[Fe(CN)6]3– > SO42– > Cl–
The minimum concentration of an electrolyte in milli moles required to cause precipitation of 1 litre
sol in 2 hours is called FLOCCULATION VALUE. The smaller the flocculating value, the higher
will be the coagulating power of the ion.
1
Flocculation value a
Flocculation power
l According to Hardy Schulze rule, greater the valency of the flocculating ion of the electrolyte, the
faster is the coagulation.
l The potential difference between the fixed layer and the diffused layer of opposite charges in colloids
is called electrokinetic potential or zeta potential.
l Blood—is an albuminoid suspended in water, which implies that blood is a colloid. Alum and FeCl3
solution stop bleeding due to coagulation.
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1. Why does physisorption decrease with the increase of temperature?
Ans. Physisorption is exothermic in nature. Therefore, in accordance with Le-Chateliere’s principle, it
decreases with an increase in temperature. This means that physisorption occurs more readily at
a lower temperature.
2. Why are powdered substances more effective adsorbents than their crystalline forms?
Ans. Powdered substances are more effective adsorbents than their crystalline forms because when a
substance is powdered, its surface area increases and physisorption is directly proportional to the
surface area of the adsorbent.
3. Why is the ester hydrolysis slow in the beginning and becomes faster after sometime?
Ans. Ester hydrolysis can be represented as:
Ester + Water ¾® Acid + Alcohol
The acid produced in the reaction acts as a catalyst and makes the reaction faster.
Substances that act as catalysts in the same reaction in which they are obtained as products are
known as autocatalysts.
4. What modification can you suggest in the Hardy-Schulze law?
Ans. Hardy-Schulze law states that ‘the greater the valence of the flocculating ion added, the greater is
its power to cause precipitation.’
This law takes into consideration only the charge carried by an ion, not its size. The smaller the
size of an ion, the more will be its polarising power. Thus, Hardy-Schulze law can be modified in
terms of the polarising power of the flocculating ion. Thus, the modified Hardy-Schulze law can
be stated as ‘the greater the polarising power of the flocculating ion added, the greater is its
power to cause precipitation.’
5. Why is it essential to wash the precipitate with water before estimating it quantitatively?
Ans. When a substance gets precipitated, some ions that combine to form the precipitate get adsorbed
on the surface of the precipitate. Therefore, it becomes important to wash the precipitate before
estimating it quantitatively in order to remove these adsorbed ions or other such impurities.
6. What is the difference between physisorption and chemisorption ?
Ans. Physisorption Chemisorption
In this type of adsorption, the In this type of adsorption ,
adsorbate is attached to the strong chemical bonds are
1. surface of the adsorbent with formed between the adsorbate
weak van dar Waal’s forces of and the surface of the
attraction. adsorbent.
No new compound is formed New compounds are formed at
2.
in the process. the surface of the adsorbent.
It is generally found to be It is usually irreversible in
3.
reversible in nature. nature.
Enthalpy of adsorption is low Enthalpy of adsorption is high
as weak van dar Waal’s forces as chemical bonds are formed.
4. of attraction are involved . The The values lie in the range of
values lie in the range of 20- (80-240) kJ mol-1
40 kJ mol-1
It is favoured by low It is favoured by high
5.
temperature conditions. temperature conditions.
It is an example of multi – It is an example of mono –
6.
layer adsorption layer adsorption.
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7. What is an adsorption isotherm ? Describe Freundlich adsorption isotherm .
T constant at high paressure

m at intermediate
pressure
x
x
m = kP°
Extent of adsorption
1
x n
Ans. m = kP Ps = saturated pressure
x
m = kP
Pressure (P) Ps
at low paressure
x
The plot between the extent of adsorption æç ö÷ against the pressure of gas (P) at constant
è mø
temperature (T) is called the adsorption isotherm.
Freundlich adsorption isotherm :
Freundlich adsorption isotherm gives an empirical relationship between the quantity of gas adsorbed
by the unit mass of solid adsorbent with pressure and at a specific temperature.
Form the given plot it is clear that at pressure PS , x reaches the maximum value. Ps is called the
m
saturation pressure. Three cases arise from the graph now.
Case I - At low pressure :
x
The plot is straight and sloping, indicating that the pressure is directly proportional to
m
x
i.e., aP .
m
x
=kP (k is a constant)
m
Case II- At high pressure :
x
When pressure exceeds the saturated pressure, becomes independent of P values.
m
x
µ P°
m
x
= k P°
m
Case III- At intermediate pressure :
x
At intermediate pressure, depends on P raised to the powers between 0 and 1. This relationship
m
is known as the Freundlich adsorption isotherm.
1
x
µ Pn
m
1
x
= kP n n>1
m
Now, taking log :
x 1
log = log k + log P
m n
æx ö
On plotting the graph between log çè m ÷ø and log P, a straight line is obtained with the slope equal
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1
to and the intercept equal to log k.
n
Slope= 1
n
x
log m
Intercept = log k
log p
8. Why is adsorption always exothermic ?

Ans. Adsorption is always exothermic. This statement can be explained in two ways.
(i) Adsorption leads to a decrease in the residual forces on the surface of the adsorbent. This
causes a decrease in the surface energy of the adsorbent. Therefore, adsorption is always
exothermic.
(ii) DH of adsorption is always negative. When a gas is adsorbed on a solid surface, its movement
is restricted leading to a decrease in the entropy of the gas i.e., DS is negative. Now for a process
to be spontaneous. DG should be negative.
\ DG = DH – TDS
Since DS in negative, DH has to be negative to make DG negative. Hence, adsorption is always
exothermic.
9. Explain what is observed
(i) When a beam of light is passed through a colloidal sol.
(ii) An electrolyte. NaCl is added to hydrated ferric oxide sol.
(iii) Electric current is passed through a colloidal sol.

Ans. (i) When a beam of light is passed through a colloidal solution, then scattering of light is observed.
(ii) When NaCl is added to ferric oxide sol, it dissociates to give Na+ and Cl– ions. Particles of
ferric oxide sol are positively charged. Thus they get coagulated in the presence of negatively charged
Cl– ions.
(iii) The colloidial particles are charged and carry either a positive or negative charge. The
dispersion medium carries an equal and opposite charge. This makes the whole system neutral.
Under the influence of an electric current, the colloidal particles move towards the oppositely
charged electrode. When they come in contact with the electrode, they lose their charge and
coagulate.
10. Action of soap is due to emulsification and micelle formation. Comment.

Ans. The cleansing action of soap is due to emulsification and micelle formation. Soaps are basically
sodium and potassium salts of long chain fatty acids, R-COO—Na+. The end of the molecule to
which the sodium is attached is polar in nature, while the alkyl end is non-polar. Thus a soap
molecule contains a hydrophilic (polar) and a hydrophobic (non-polar) part.
When soap is added to water containing dirt, the soap molecules surround the dirt particles in
such a manner that their hydrophobic parts get attached to the dirt molecule and the hydrophilic
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parts point away from the dirt molecule. This is known as micelle formation. Thus, we can say
that the polar group dissolves in water while the non-polar group dissolves in the dirt particle.
Now, as these micelles are negatively charged, they do not collapse and a stable emulsion is
formed
11. What are micelles ? Give an example of a micelle's system.
Ans. Micelle formation is done by substances such as soaps and detergents when dissolved in water.
The molecules of such substances contain a hydrophobic and a hydrophilic part. When present in
water, these substances arrange themselves in spherical stuctures in such a manner that their
hydrophobic parts are present towards the centre, while the hydrophilic parts are pointing towards the
outside (as shown in the given figure). This is known as micelle formation
Na+
Na+
+
Na
Hydrophilic Hydrophobic
end end
Na + Na+
Water molecule
12. Define the following terms with an example in each case:

(i) Macromolecular sol
(ii) Peptization
Ans. (i) Macro molecular sol. ¾® When certain substances having big sized molecules, called
macromolecules, having large molecular masses are dissolved in a suitable liquid, they form
a solution in which the molecules of the substance, i.e., the dispersed particles have size in
the collidal range. E.g. polyethene, nylon, polystyrene, strach & protein.
(ii) Peptization ¾® is a process of converting a fresh precipitate into colloidal particles by shaking
it with the dispersion medium in the presence of small amount of a suitable electrolyte. The
electrolyte added is called peptizing agent.
13. Explain the following terms giving a suitable example for :
Aerosol
Ans. Aerosol – A colloidal solution having a gas as the dispersion medium and solid as dispersed phase
is called as aerosol. Ex. Smok, Dust
14. How are the colliodal solution classified on the basis of physical states of dispersed phase and
dispersion medium.
Ans. Classification of Colloids: Bases on the physical state of dispersed phase and dispersion medium:
Depending upon whether the dispersed phase and the dispersion medium are solids, liquids or
gases, eight types of colloidal systems are possible. A gas mixed with another gas forms a
homogeneous mixture and not a colloidal system. The examples of the various types along with
their typical names are :
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Dispersed phase Dispersion medium Type of colloid Examples
Solid Solid Solid sol Some coloured glasses and gem stones
Solid Liquid Sol Paints, Cell fluids
Solid Gas Aerosol Smoke, Dust
Liquid Solid Gel Cheese, butter, jellies
Liquid Liquid Emulsion Milk, hair cream
Liquid Gas Aerosol Fog. mist, cloud, insecticide sprays
Gas Solid Solid sol Pumic stone, foam rubber
Gas Liquid Foam Froth, whipped cream, soap lather
15. Describe the following:
(i) Tyndall effect
(ii) Coagulation
Ans. (i) Tyndall effect : This phenomenon of scattering of light by colloidal particles as a result of
which the path of beam becomes visible is called tyndall effect.
(ii) Coagulation : The phenomenon of precipitation of a colloidal solution by the addition of
excess of an electrolyte is called coagulation or flucculation.
16. What happens in the following activities and why ?
An electrolyte is add to a hydrated ferric oxide sol in water.
Ans. When an electrolyte like KCl is added of Fe(OH)3 sol, the positively charged colloidal particles
–
of Fe(OH)3 get coagulated by the oppositely charged Cl ions provided by KCl.
17. Which type of adsorption has higher enthalpy of adsorption ?
–1
Ans. Enthalpy of chemisorption is high (80–240 kJ mol ) as it involves chemical bond formation.
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1. Hardening of leather in tanning industry is based on [1]

(A) Electrophoresis (CBSE 2020)
(B) Electro-osmosis
(C) Mutual coagulation
(D) Tyndall
Ans. (C)
2. Explain the cleansing action of soaps. [2]
(CBSE 2020)
Ans. Soap molecules form micelle around the oil droplet or dirt in such a way that hydrophobic part
interacts with the oil droplet and hydrophilic part projects out.
Micelles can be washed away on rinsing with water. Thus soap helps in emulsification and washing
away of oil and fats.
3. Give three points of difference between physisorption and chemisorption. [3]
(CBSE 2020)
Ans. Physisoption Chemisorption
1. It arises because of van der walls force. 1. It is caused by chemical bond formation.
2. It is not specific in nature 2. It is highly specific in nature
3. It is reversible in nature 3. It is irreversible.
4. What type of colloid is formed when a solid is dispersed in a liquid ? Give an example. [1]
Ans. Type of colloid is Sol, Example-Paints (CBSE 2019)
5. (a) Write the dispresed phase and dispersion medium of dust.
(b) Why is physisorption reversible whereas chemisorption is irreversible ? (CBSE 2019)
(c) A colloidal sol is prepared by the method given in the figure. What is the charge on AgI
colloial particles formed in the test tube ? How is this sol represented ? [3]
KI solution
PPt of AgI
AgNO3
solution
Ans. (a) Dispersed phase = solid ; Dispersion medium = gas

(b) Due to weak van der Waal’s forces in physisorption whereas strong chemical forces in
chemisorptions.
(c) Positively charged, AgI/Ag+
6. (a) Write the dispersed phase and dispersion medium of milk. (CBSE 2019)
(b) Why is adsorption exothermic in nature ?
(c) Write Freundlich adsorption isotherm for gases at high pressure. [3]
Ans. (a) Liquid is dispersed in water. So liquid is dispersed phase and water is dispersion medium
(b) Adsorption is always exothermic. This statement can be explained in two ways.
(i) Adsorption leads to a decrease in the residual forces on the surface of the adsorbent. This
causes a decrease in the surface energy of the adsorbent. Therefore, adsorption is always
exothermic.
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(ii) DH of adsorption is always negative. When a gas is adsorbed on a solid surface, its movement
is restricted leading to a decrease in the entropy of the gas i.e., DS is negative. Now for a process
to be spontaneous. DG should be negative.
\ DG = DH – TDS
Since DS in negative, DH has to be negative to make DG negative. Hence, adsorption is always
exothermic.
x
(c) =k
m
7. (a) Write the dispresed phase and dispersion medium of butter. (CBSE 2019)
(b) Why does physisorption decrease with increase in temperature ?
(c) A colloidal sol is prepared by the method given in the figure. What is the charge on AgI colloidal
particles formed in the test tube ? How is this sol represented ? [3]
AgNO3 solution
KI solution
Ans. (a) Water is oil
(b) Due to exothermic process
(c) Negative sol, AgI/I–
8. CO(g) and H2(g) react to give different products in the presence of different catalysts. Which ability
of the catalyst is shown by these reactions? (CBSE 2018)
Ans. CO2(g) & H2(g) react to give different products in the presence of different catalysits, it specify
selectivity of a catalyst in this reaction, which menas a catalyst for one reaction can be unhibitors for
another.
9. What happens when (CBSE 2018)
(a) a freshly prepared precipitate of Fe(OH)3 is shaken with a small amount of FeCl 3 solution ?
(b) persistent dialysis of a colloidal solution is carried out ?
(c) an emulsion is centrifuged ?
Ans. (a) When precipitate of Fe(OH)3 added in small amount of FeCl 3 solution, peptization occur. The
common ion Fe3+ adsorbed on precipitate partides & converts to smaller colloidal, particles.
(b) To increase the stability of colloids, small amount of electrolyte is added, so during the electrolyte
almost remove & the colloidal solution will coagulate.
(c) An emulsion is centrifuged, when it demulsified the immicible mixture of two liquids & both
get separate out.
10. What type of colloid is formed when a solid is dispersed in a liquid ? Give an example. (CBSE 2017)
Ans. Example - Paints cell fluids (any one)
11. Write one difference in each of the following : (CBSE 2017)
(a) Multimolecular colloid and Associated colloid
(b) Coagulatin and Peptization
(c) Homogeneous catalysis and Heterogeneous catalysis
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OR
(a) Write the dispersed phase and dispersion medium of milk.
(b) Write one similarity between physisorption and chemisorption
(c) Write the chemical method by which Fe(OH)3 sol is prepared from FeCl3
Ans. (a) Multimolecular colloid (a) Associated colloid
Aggregation of large Aggregation of large
number of small atoms or number of ions in
molecules. concentrated solutions.
(b) Coagulation Peptization
(a) Setting down of colloidal (a) Conversion on precipitate into
particles. colloidal sol by adding small
amount of electrolyte.
(c) Homogenous catalysis Heterogeneous catalysis
(a) Reactants and catalyst (a) Reactants and catalyst
are in same phase. are in different phases.
OR
(a) Dispersed phase-liquid, Dispersion medium-liquid
(b) Both are surface phenomenon / both increases with increase in surface area (or any other
correct similarity)
(c) Hydrolysis / FeCl3 + 3H2O hydrolysis Fe(OH)3(sol) + 3HCl
12. Write the reason for the stability of colloidal sols. (CBSE 2016)
Ans. Like Charged particles cause repulsion/ Brownian motion/ solvation
13. Define the following terms: (CBSE 2016)
(i) O/W Emulsion (ii) Zeta potential (iii) Multimolecular colloids
Ans. (i) Oil as dispersed phase and water as dispersion medium
(ii) The potential difference between fixed layer and diffused / double layer of opposite charges.
(iii) Large number of atoms or smaller molecules of a substance aggregate together to form species
having size in colloidal range.
14. Out of AlCl3 and NaCl, which is more effective in causing coagulation of a negative sol and why?
(CBSE 2015)
3+
Ans. AlCl3, due to greater charge on Al .
15. Define adsorption with an example. Why is adsorption exothermic in nature ? Write the types of
adsorption based on the nature of forces between adsorbate and adsorbent. (CBSE 2015)
Ans. The accumulation of molecular species at the surface rather than in the bulk of a solid or liquid is
termed adsorption.
eg: gas like O2, H2, CO, Cl2, NH3 or SO2 is taken in a closed vessel containing powdered charcoal
Due to bond formation / interaction between adsorbent and adsorbate
Physical (van der Waal’s adsorption) & Chemical (Langmuir adsorption)
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EXERCISE-3 RACE
There are mainly two types of adsorption of gases on solids. If accumulation of gas on the surface
of a solid occurs on account of weak van der Waals’ forces, the adsorption is termed as physical
adsorption or physisorption. When the gas molecules or atoms are held to the solid surface by
chemical bonds, the adsorption is termed chemical adsorption or chemisorption. The chemical
bonds may be covalent or ionic in nature. Chemisorption involves a high energy of activation
and is, therefore, often referred to as activated adsorption. Sometimes these two processes occur
simultaneously and it is not easy to ascertain the type of adsorption?
(i) Which of the following is an example of absorption?
(a) Water on silica gel (b) Water on calcium chloride
(c) Hydrogen on finely divided nickel (d) Oxygen on metal surface
(ii) Extent of physisorption of a gas increases with ___________.
(a) increase in temperature. (b) decrease in temperature.
(c) decrease in surface area of adsorbent. (d) decrease in strength of van der Waals forces.
(iii) The term ‘sorption’ stands for ____________.
(a) absorption (b) adsorption
(c) both absorption and adsorption (d) desorption

(iv) Which process increases initially with temperature?
(a) physisorption (b) Chemisorption (c) Both (d) None of these

2. Assertion : colloidal solution show colligative properties.
Reason : colloidal particles are larger in size
3. Assertion : adsorption decreases with increasing in temperature.
Reason : adsorption depends upon surface area.
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4. Assertion : Small pieces of wood burn faster than a log of wood of same mass.
Reason : Surface area of small pieces is larger than the single log.
5. Assertion : On adding KI to blue CuSO4 solution, the color changes to dark brown.
Reason : This is due to the formation of CuO.

3+ +
6. Assertion : Coagulation power of Al is more than Na .
Reason : Greather the valency of the flocculating ion added, greather is its power to cause
percipitation .
7. A colloidal system having a solid substance as a dispersed phase and a liquid as a dispersion
medium is classified as ____________.
(i) solid sol (ii) gel (iii) Emulsion (iv) sol

+
8. Which of the following electrolytes will have maximum coagulating value for AgI/Ag sol?
(i) Na2 S (ii) Na3PO4 (iii) Na2SO4 (iv) NaCl
9. At high concentration of soap in water, soap behaves as ____________.
(i) molecular colloid (ii) associated colloid
(iii) macromolecular colloid (iv) lyophilic colloid
10. Method by which lyophobic sol can be protected.
(i) By addition of oppositely charged sol.
(ii) By addition of an electrolyte.
(iii) By addition of lyophilic sol.
(iv) By boiling.
11. Physical adsorption of a gaseous species may change to chemical adsorption with ______________.
(i) decrease in temperature
(ii) increase in temperature
(iii) increase in surface area of adsorbent
(iv) decrease in surface area of adsorbent
12. Extent of adsorption of adsorbate from solution phase increases with ________.
(i) increase in amount of adsorbate in solution. (ii) decrease in surface area of adsorbent.
(iii) increase in temperature of solution. (iv) decrease in amount of adsorbate in solution.
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13. Which of the following will show Tyndall effect?
(i) Aqueous solution of soap below critical micelle concentration.
(ii) Aqueous solution of soap above critical micelle concentration.
(iii) Aqueous solution of sodium chloride.
(iv) Aqueous solution of sugar.
14. Freshly prepared precipitate sometimes gets converted to colloidal solution by ___________.
(i) coagulation (ii) electrolysis
(iii) diffusion (iv) peptisation
15. The values of colligative properties of colloidal solution are of small order in comparison to those
shown by true solutions of same concentration because of colloidal particles __________________.
(i) exhibit enormous surface area.
(ii) remain suspended in the dispersion medium.
(iii) form lyophilic colloids.
(iv) are comparatively less in number.
16. Which of the following process is responsible for the formation of delta at a place where rivers
meet the sea?
(i) Emulsification (ii) Colloid formation
(iii) Coagulation (iv) Peptisation
Answer key :
Q. No. 1 (i) (ii) (iii) (iv) 2 3 4 5 6 7 8
Ans. b b c b B B A D A i ii
Q. No. 9 10 11 12 13 14 15 16
Ans. ii iii iv i ii iv iv iii
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1. Of physisorption and chemisorption which type of adsorption has higher enthalpy of
adsorption ? [1]
2 What is especially observed when a beam of light is passed through a colloidal solution? [1]
3. Out of AlCl3 and NaCl, which is more effective in causing coagulation of a negative sol and why?
[1]
4. Write the reason for the stability of colloidal sols. [2]
5. What type of colloid is formed when a solid is dispersed in a liquid ? Give an example. [2]
6. Write the dispersed phase and dispersion medium of milk. [2]
7. Write one similarity between physisorption and chemisorption [2]
8. What happens when [3]
(a) a freshly prepared precipitate of Fe(OH)3 is shaken with a small amount of FeCl 3 solution ?
(b) persistent dialysis of a colloidal solution is carried out ?
(c) an electric current is passed through a sol
9. Describe the following: [3]
(i) Brownian moment
(ii) Coagulation
(iii) Peptization
10. Define the following terms with an example in each case: [3]
(i) Macromolecular sol
(ii) Multimolecular colloids
(iii) Zeta potential
11. What is an adsorption isotherm ? Describe Freundlich adsorption isotherm. [5]
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MOCK TEST SOLUTIONS
1. Chemisorption
2. Tyndall effect
3. AlCl3, due to greater charge on Al3+
4. Like charged particles cause repulsion / Brownian motion / solvation.
5. Sol, Example-Paints
6. Fat is dispersed phase and water is dispersion medium.
7. Both are surface phenomenon / both increases with increase in surface area.
8. (a) When precipitate of Fe(OH)3 added in small amount of FeCl3 solution, peptization occur. The
common ion Fe3+ adsorbed on precipitate particles & converts to smaller colloidal, particles.
(b) To increase the stability of colloids, small amount of electrolyte is added, so during the electrolyte
almost remove & the colloidal solution will coagulate.
(c) On passing the electric current, colloidal particles move towards the oppositely charged electrode
where they lose their charge and get coagulated.
9. (i) Zig-Zag motion of colloidal particles in dispersion medium.
(ii) Coagulation : The phenomenon of precipitation of a colloidal solution by the addition of excess
of an electrolyte is called coagulation or flocculation.
(iii) Peptization ¾® is a process of converting a fresh precipitate into colloidal particles by shaking
it with the dispersion medium in the presence of small amount of a suitable electrolyte. The
electrolyte added is called peptizing agent.

10. (i) Macromolecular sol. ¾® When certain substances having big sized molecules, called
macromolecules, having large molecular masses are dissolved in a suitable liquid, they form a
solution in which the molecules of the substance, i.e., the dispersed particles have size in the colloidal
range. E.g. polyethene, nylon, polystyrene, starch & protein.
(ii) Large number of atoms or smaller molecules of a substance aggregate together to form species
having size in colloidal range.
(iii) The potential difference between fixed layer and diffused / double layer of opposite charges.
T constant
11.
xm
x
m = kP°
n
ito 1
x n
rp
o m = kP
ds
a
f
o
t
n
te x
x
E m = kP
Pressure (P) Ps
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æxö
The plot between the extent of adsorption ç m ÷ against the pressure of gas (P) at constant temperature
è ø
(T) is called the adsorption isotherm.

Freundlich adsorption isotherm :
Freundlich adsorption isotherm gives an empirical relationship between the quantity of gas adsorbed
by the unit mass of solid adsorbent with pressure and at a specific temperature.
Form the given plot it is clear that at pressure reaches the maximum value. Ps is called the saturation
pressure. Three cases arise from the graph now.
Case I - At low pressure :
x x
The plot is straight and sloping, indicating that the pressure is directly proportional to i.e., aP
m m
x
= k P . (k is a constant)
m
Case II- At high pressure :
x
When pressure exceeds the saturated pressure, becomes independent of P values.
m
x x
µ P° = k P°
m m
Case III- At intermediate pressure :
x
At intermediate pressure, depends on P raised to the powers between 0 and 1. This relationship
m
is known as the Freundlich adsorption isotherm.
1 1
x x
µ Pn n>1
= kP n
m m
Now, taking log :
x 1
log = logk + logP
m n
æ x ö
On plotting the graph between log ç m ÷ and log P, a straight line is obtained with the slope equal
è ø
1
to and the intercept equal to log k.
n
Slope= 1n
x
log m
Intercept = log k
log p
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THE p-BLOCK ELEMENTS
Anomalous behavior of first element in the p-block elements is attributed to small size, large (charge/radius) ratio,
high ionization enthalpy, high electronegativity and unavailability of d-orbitals in its valence shell.
Consequences :
1. The first element in p-block element has four valence orbitals i.e., one 2s and three 2p. Hence maximum
covalency of the first element is limited to four. The other elements of the p-block have vacant
d-orbitals in their valence shell, e.g., three 3p and five three 3d orbitals. Hence, these elements show
maximum covalence greater than four. Following questions can be answered :
(i) Nitrogen (N) does not form pentahalide while P forms PCl5, PF5 and PF6–{. Why ?
(ii) Sulphur (S) forms SF6 but oxygen does not form OF6. Why ?
(iii) Though nitrogen forms pentoxide but it does not form pentachloride. Why ?
(iv) Fluorine forms only one oxoacid while other halogens form a number of oxoacids. Why ?
2. The first member of p-block elements displays greater ability to form pp-pp bond(s) with itself,
(e.g., C=C, CºC, N=N, NºN) and with the other elements of second period, for example, C=O,
CºN, N=O compared to the subsequent members of the group.
This is because p-orbitals of the heavier members are so large and diffuse that they cannot have
effective sideways overlapping. Heavier members can form p p-dp bonds with oxygen.
Nitrogen rarely forms pp-dp bonds with heavier elements as in case of trisilylamine (SiH3)3N.
O dp–pp O pp–pp
P N
node06\B0B0-BA\Kota\Board Material\Chemistry\CBSE\CBSE Booklet\English\Updated booklet-21\New Pattern CBSE Booklet\Part wise boocklet\Part 1\02_IOC\06_The p-Block Elements.p65
O O O O
O
SiH 3
N=O pp–dp
N
pp–pp H3Si (Trisilylamine) SiH3
Now, the following questions can be explained using the above mentioned reasoning :
(i) Nitrogen forms N2 but phosphorus forms P4 at room temperature. Why ?
(ii) Oxygen exists as O2 but sulphur as S8. Why ?
(iii) Explain why (CH3) 3P=O is known but (CH3)3N=O is not known.
3. Due to small size and high electronegativity and presence of lone pair(s) of electrons, elements N, O,
F when bonded to hydrogen atom, forms hydrogen bonds which are stronger than other intermolecular
forces. This results in exceptionally high m.p. and b.p. of the compounds having
N–H/O–H/F–H bonds.
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Isostructural species have same number of bond pairs and lone pairs if present around the central
atom in a molecule/ion. Thus, they have the same geometry/ shape/structure and the same hybridisation
scheme. For example, ICl4–/XeF4,BrO3–/XeO3, BH4–/NH4+ are the pairs of isostructural species.
Inert pair effect : Due to poor shielding effect of intervening d and/or f-electrons, the effective
nuclear charge increases. This increased nuclear charge holds the ns2 electrons of heavier elements
strongly and the tendency of ns2 electrons to take part in bonding is more and more restricted down
the group. Consequently, more stable lower oxidation state which is two units less than higher oxida-
tion state, becomes more and more stable than the higher oxidation state. Following questions can be
explained with the help of inert pair effect :
(i) For N and P, + 5 oxidation state is more stable than + 3 oxidation state but for Bi + 3 oxidation state
is more stable than + 5. Explain why ?
(ii) NaBiO3 is a strong oxidizing agent. Why ? [Hint : Bi (V) is least stable.]
(iii) In group 16, stability of +6 oxidation state decreases and the stability of + 4 oxidation state
increases down the group. Why ?
(iv) SO2 acts as reducing agent. Explain why ?
(v) Why is BrO4– a stronger oxidizing agent than ClO -4 ?
[Hint : It is because + 7 oxidation state is less stable in BrO4–{ due to which Br – O bond becomes
weaker.]
(vi) AsCl5 is less stable than SbCl5.
[Hint : More effective nuclear charge in As than Sb.]
(vii) The stability of highest oxidation state of 4p element is less than those of 3p and 5p elements of
the same group. Why ?
Bond length : Resonance averages bond lengths. The two oxygen-oxygen bond lengths are identical
in the O3 molecule because it is resonance hybrid of following two canonical forms.
In case of HNO3, two nitrogen-oxygen bonds are identical and smaller than the third nitrogen-oxy-
gen bond. This is because the third N–OH bond is not involved in resonance.
Now the following questions can be explained on the basis of this concept :
(i) In SO2, the two sulphur-oxygen bonds are identical. Explain why ?
(ii) In NO3– ion, all the three N–O bonds are identical. Why ?
Bond angle : In regular structures (where no lone pairs are present in the valence shell of the central
atom in a molecule/ion), the bond angle does not depend upon the size/electronegativity of the central
or terminal atoms.
110 E
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In presence of lone pair(s) on the central tom, the geometry is distorted and the bond angle is changed.
Comparison of HNH and HPH bond angles

Since N is more electronegative than P, the bonding electron pair of N–H bond will shift more
towards N atom than the bonding electron pair of P–H bond would shift towards P atom. This results
in more bond pair-bond pair repulsion in NH3 molecule than PH3 molecule. Because of more Ip-bp
repulsion, the N–H bonds are pushed closer to a lesser extent than in PH3. Consequently, HNH bond
angle is greater than HPH angle.
Now, the following questions can be explained using the above mentioned concept :
(i) Bond angle in PH4+ ion is higher than in PH3. Why ?
(ii) H–O–H bond in H2O is greater than H–S–H angle in H2S. Why ?
Boiling and melting points of hydrides depends upon the molar mass (or surface area) of molecules.
More the molar mass, the higher is the m.p. and b.p. Hydrides forming intermolecular hydrogen
bonds have exceptionally high m.p. and b.p. since intermolecular hydrogen bonds are stronger than
the van der Waals forces.
Increasing order of melting point and boiling point of hydrides is as given below :
PH3 < AsH3 < SbH3 < NH3 Melting point
PH3 < AsH3 < NH3 < SbH3 Boiling point
H2S < H2Se < H2Te < H2O Melting point and boiling point
HCl < HBr < HI < HF Boiling point
HCl < HBr < HF < HI Melting point
(i) NH3 has higher boiling point than PH3.
(ii) H2O is liquid and H2S is gas or H2S is more volatile than H2O.
Thermal stability, reducing power and acid strength of hydrides depend upon bond dissociation
enthalpy of E–H bond (E = group 15, group 16, and group 17 element). Due to the increase in size
down the group, bond dissociation enthalpy of E–H bond decreases. Consequently, thermal stability,
reducing power and acid strength of hydrides increases down the group.
The following questions can be explained using the above concepts.
E 111
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Explain why :
(i) HF is weaker acid than HCl.
(ii) Among hydrogen halides, HI is the strongest reducing agent.
(iii) H2Te is more acidic than H2S.
(iv) NH3 is mild reducing agent while BiH3 is the strongest reducing agent among the group-15 hydrides.
(v) H2S is weaker reducing agent than H2Te.
Basic nature of hydrides EH3 of group 15 elements
All the hydrides EH3 of group 15 elements has one lone pair of electrons. In ammonia, the lone pair
of electrons is present in sp3 hybrid orbital of the N-atom. The sp3 hybrid orbital is directional and
further N is more electronegative than H, the bond pair of N–H is shifted towards N atom which
further increases the electron density on N atom. In PH3, the lone pair of electrons is present in large
and more diffuse 3s orbital which is non-directional. As a result, PH3 is less basic than NH3 and basic
character decreases down the group. NH3 donates electron pair more readily than PH3. (SiH3)3N has
less Lewis basic nature than that of (CH3)3N because lone pair of electrons in p-orbital of N atom in
(SiH3)3N is transferred to the vacant d-orbital of Si atom forming dp–Pp bond.
Covalent/Ionic Character of Halides
Pentahalides are more covalent than trihalides since the element (E) in higher oxidation state (+ 5) in
pentahalides has more polarizing power than element (E) in lower oxidation state (+ 3) in trihalides,
similarly, SnCl4, PbCl2, SbCl3 and UF4 respectively. Compounds having more ionic character have
more m.p. and b.p. than the compounds having more covalent character.
Following questions can be explained by using this concept.
Explain why :
(i) SnCl2 has more b.p. than SnCl4.
(ii) SbCl5 is more covalent than SbCl3.
(iii) PCl5 has lower boiling point than that of PCl3.
Strength of Oxo Acids
Strength of oxoacids depends upon the polarity of O–H bond which in turn, depends
on the electron withdrawing power (or electronegativity) of the element E. Strength of oxoacids
increases if the number of oxygen atoms bonded with E increases.
Strength of oxoacids of halogens in the same oxidation state depends on the electronegativity of the
halogen. The more the electronegativity, stronger is the oxoacid.
Strength of oxoacid of a halogen in different oxidation state increases with the increase in oxidation
state. This is because the stabilization of the oxoanion increases with the number of the oxygen atoms
bonded to the halogen atom. More the number of oxygen atoms, the more the dispersal of –ve charge
present on the oxoanion and stronger will be the oxoacid.
Oxidising Power of Halogens
–DegH
X(g) X(g)
q aq –DhydHq
+1/2DdissH
–DrHq
1/2X2(g) X(aq)
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The more negative the value of DrHq = ½Ddiss Hq – Deg Hq –Dhyd Hq the higher will be oxidizing
property of the halogen and more positive will be standard reduction potential Eq red of the halogen.
Following questions can be explained on the basis of parameters, like Ddiss Hq, Deg Hq and Dhyd Hq
(i) Why does F2 have exceptionally low bond dissociation enthalpy ?
(ii) Although electron gain enthalpy of uorine (F) is less negative as compared to chlorine (Cl),
Fluorine gas (F2) is a stronger oxidizing agent than Cl2 gas. Why ?
Group 15 Elements :
l Ammonia (NH3)
Colorless, Pungent Smell, basic in nature liquified easily, uses as coolant
Preparation :
(i) 2NH4Cl + Ca(OH)2 CaCl2 + 2NH3 + 2H2O
NH3
(ii) Mg3N2 +HOH Mg(OH)2 + 2NH3
Fe+Mo
Manufacturing Haber Process : N2+3H2 750K
2NH3
200-300atm
Properties :
4NH3 + 3O2 N2+6H2O
NH3 4NH3 +5O2 Pt/Rh

1100K
4NO + 6H2O
Ostwald's
process
8NH3 + 3Cl2 6NH4Cl+N2

excess
NH3+3Cl2 NCl3 + 3HCl

excess
l Nitric Acid (HNO3) :

HNO3, nitric acid was earlier called as aqua fortis (meaning strong water). It usually acquires yellow
colour. due to its decomposition by sunlight into NO2.
It acts as a strong oxidising agent. Non-metals converted into highest oxyacids by hot and conc.
HNO3. NO2 gas is evolved (S to H2SO4; P to H3PO4; C to H2CO3; I2 to HIO3; As to H3AsO4; Sb to
H3SbO4 and Sn to H2SnO3). Most of the metals except noble metals are attacked by HNO3. It plays
double role in action on metals, i.e., it acts as an acids as well as an oxidising agent.
Concentration Main products

Metal
of nitric acid
Mg, Mn H2+ metal nitrate
Very Dilute HNO3 Fe, Zn, Sn NH4NO 3 + metal nitrate
Cu, Ag, Hg No reaction
Dilute HNO3 Fe, Zn N2O + metal nitrate
Zn, Fe, Pb, Cu, Ag NO + metal nitrate
NO2 + H2SnO3
Conc. HNO3 Sn
(Metastannic acid)
Conc. HNO3 Fe, Co, Ni, Cr, Al rendered passive
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Structure of oxides of nitrogen :
Oxide of Nitrogen Oxid. Physical Structure
state appearance
N2O nitrous oxide +1 Colourless gas NºN®O
NO Nitric oxide +2 Colourless gas N=O
O O
N2O3 Dinitrogen trioxide +3 Blue colour solid N–N
O
N2O4 Dinitrogen tetraoxide +4 Colourless solid O O
N–N
O O
NO2 Nitrogen dioxide +4 Brown gas N
O O
N2O5 Dinitrogen pentaoxide +5 Colourless solid O O O
N N
O O
Group 16 Elements :
l Hydrides
All these elements form stable hydrides of the type H2M
2H2 + O2 2H2O
FeS + H2SO4 ¾® H2S + FeSO4
Na2Se + H2SO4 ¾® H2Se + Na2SO4
l H2O is a liquid due to hydrogen bonding. Others are colourless gases with unpleasant smell.
l Compound : H2O > H2S > H2Se > H2Te
Bond angle : 104.5° 92.5° 91° 90°
(all sp hybridised)
3
l The weakening of M–H bond with the increase in the size of M (not the electronegativity) explains
the increasing acidic character of hydrides down the group.
l Halides % All these elements form a number of halides. The halides of oxygen are not very stable.
Selenium does not form dihalides.
e.g. OF2, Cl2O6, I2O5, etc.
l Oxides : Oxides of other elements are as follows :
Element Monoxide Dioxide Trioxide
S SO SO 2 SO 3
Se – SeO2 SeO3
Te TeO TeO2 TeO3
Po PoO PoO2 –
l SO2 is a gas having sp2 hybridisation and V-shape
é1pp - pp ù p S p S S
ê ú
ë1pp - dp û
119.5°
O O O O O O
l SO3 is a gas, sp2 hybridised and planar in nature.
O
é1pp - pp ù
S ê ú
ë 2 pp - dp û
O O
O O O
S S S
O O O O O O
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Oxygen (O2) :
Preparation : By action of heat on oxygen rich compounds :
l From oxides :
D
2Hg O ¾¾® 2Hg + O2
l From peroxides :
2Na2O2 + 2H2O ¾® O2 + 4NaOH
D
2BaO2 ¾¾® 2BaO + O2
l From decomposition of certain compounds
D
2KClO3 ¾¾¾¾
MnO
® 2KCl + 3O
22
2KNO3 ¾® 2KNO2 + 3O2

l Properties : It is colourless, odourless, tasteless gas, slightly heavier than air, sparingly soluble in
water but soluble in pyrogallol.
l Chemical properties : On heating it combines directly with metals and non-metals, causing
oxidation.
C + O2 ¾® CO2
S + O2 ¾® SO2
Pb + O2 ¾® PbO2
2CH3OH + O2 ¾® 2HCHO + 2H2O
Uses %
l When mixed with He or CO2, it is used for artificial respiration.
l In welding and cutting.
l As a fuel in rockets.
Ozone (O3) :
Preparation :
Lab method :

2O3 (DH = +ve)
Electric discharge
3O2
l Properties : Pale blue gas with characteristic strong smell, slightly soluble in water but more soluble
in turpentine oil or glacial acetic acid.
l Decomposition:
2O 3 ¾¾¾
573K
® 3O 2 + 68kcal
l Oxidising action:
O3 ¾® O2 + O
PbS + 4O ¾® PbSO4
l Reducing action:
H2O2 + O3 ¾® H2O +2O2
BaO2 + O3 ¾® BaO + 2O2
l Structure :
O O
B.O. = 1.5
O O O O
Oxidation state of O is +1 and –1.
E 115
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Uses :
l Bleaching ivory, flower, delicate fabrics, etc.
l As germicide and disinfectant, for sterilising water.
l Manufacture of KMnO4 and artificial silk.
Sulphur Dioxide (SO2) :

Preparation %
By heating sulphur in air. D
l S + O 2 ¾¾® SO 2
l Lab method :
By heating Cu with conc. H2SO4.
Cu + 2H2SO4 ¾® CuSO4 + SO2 + 2H2O
Properties :
l As reducing agent %
SO2 + Cl2 + 2H2O ¾® H2SO4 + 2HCl
2KMnO4 + 5SO2 + 2H2O ¾® K2SO4 + 2MnSO4 + 2H2SO4
l As oxidising agent :
2H2S + SO2 ¾® 2H2O + 3S¯
l Bleaching action :
Its bleaching action is due to reduction.
SO2 + 2H2O ¾® H2SO4 + 2H
Coloured matter + H ¾® Colourless matter.
2(Nascent hydrogen)
Uses :
l In the manufacture of sulphuric acid,sulphites and hydrogen sulphide.
l As a disinfectant and fumigate.
l For bleaching delicate articles.
Sulphuric Acid (H2SO4) :
It is also known as oil of vitriol and king of chemicals.
l Contact process :
The steps involved are :
(a) Production of SO2 : It is produced by burning sulphur or iron pyrites and purified by treating with
steam to remove dust particles.
(b) Conversion of SO 2 to SO 3 : It is done in container or catalyst chamber after being
pre-heated to 450°C.

2SO2 + O2 2SO3 + x cal
Catalyst : Formerly, platinised asbestos was used which is costly and easily poisoned. These days
V2O5 is used.
(c) SO3 is absorbed by conc. H2SO4 and then water is added to produce the acid of desired concentration.
H2SO4 + SO3 ¾® H2S2O7
H2S2O7 + H2O ¾® 2H2SO4
Properties : Its specific gravity is 1.8 and it is 98% by weight.
l It is strong dibasic acid.

H2SO4 2H+ + SO42–
l It acts as an oxidising agent.
H2SO4 ¾® H2O + SO2 + O
116 E
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l Non metals are oxidised to their oxides and metals to the corresponding sulphates.
C + 2O ¾® CO2
l Dehydrating agent : It is strongly dehydrating in nature.
H2 SO4
C12H22O11 ¾¾¾¾ ® 12C + 11H2O
(Charring of sugar)
Uses :
l In lead storage batteries.
l In manufacture of paints and pigments.
l In metallurgy for electrolytic refining of metals.
Group 17 Elements :
l Reactivity : All halogens are chemically very reactive elements. This is due to their low dissociation
energy and high EN. Fluorine is the most reactive and iodine is the least reactive halogen.
l Oxidising power : F is the most oxidising element due to high hydration enthalpy.
F2 > Cl2 > Br2 > I2.
Hydrogen Halides :
Bond strength, bond length and thermal stability :
l Since size of halogen atom increases from F to I down the group, bond length of H – X bond increases
down the group.
\ reactivity and acidic character .
HF < HCl < HBr < HI.
l Bond strength is inversely, proportional to bond length i.e., larger the bond length, lower the bond
strength is
HF > HCl > HBr > HI.
l Higher the bond dissociation energy. greater will be thermal stability. Thus, thermal stability follows
the order.
HF > HCl > HBr > HI.
Reducing character :
The reducing character of hydrogen halides increases down the group as
2HX ¾® H2 + X2
A less thermally stable compound has more tendency to release hydrogen easily and show greater
reducing property.
Acidic strength :
The acidic strength of these acids increases down the group and hence follows the order.
Since H–I bond is weakest, it can be easily dissociated into H+ and I– ions while HF with greater bond
dissociation energy can be dissociated with maximum difficulty.
Chlorine (Cl2) :
l Preparation : By oxidation of conc. HCl.
PbO2 + 4HCl ¾® PbCl2 + 2H2O + Cl2
2KMnO4+16HCl ® 2KCl+2MnCl2+8H2O+5Cl2
E 117
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l Manufacture :
Weldon’s process : By heating pyrolusite with conc. HCl.
MnO2 + 4HCl ¾® MnCl2 + 2H2O + Cl2
Properties : It is a yellowish green gas, poisonous in nature, soluble in water. Its aqueous solution is
known as chlorine water which on careful cooling gives chlorine hydrate Cl2.8H2O.
Bleaching action and oxidising property
(i) Cl2 + H2O ¾® HOCl + HCl
HOCl ¾® HCl + [O]
Coloured matter + nascent [O] ® Colourless matter
The bleaching action of chlorine is permanent and is due to its oxidising nature.
(ii) SO2 + Cl2 + 2H2O ¾® H2SO4 + 2HCl
l Action of hydrogen :
H2 + Cl2 2HCl
l Displacement reactions :
2KBr + Cl2 ¾® 2KCl + Br2
2KI + Cl2 ¾® 2KCl + I2
l Action of NaOH :
2NaOH+ Cl 02 ® NaCl-1 + NaOCl +1 + H 2 O

(cold) dry sodium hypo chlorite
+5
6NaOH + 3Cl 02 ® 5NaCl -1 + Na ClO 3 + 3H 2 O
(hot and conc.) (dry) sodium chlorate
l Addition reactions :
SO2 + Cl2 ¾® SO2Cl2
CO + Cl2 ¾® COCl2
USES :
l It is used as a
(i) bleaching agent
(ii) disinfectant
(iii) in the manufacture of CHCl3, CCl4, DDT, bleaching powder, poisonous gas phosgene (COCl2),
tear gas (CCl3NO2) and mustard gas (ClC2H4SC2H4Cl).
Hydrochloric Acid, (HCl) :

Preparation : By dissolving hydrogen chloride gas in water. Hydrogen chloride gas required in turn
can be prepared by the following methods:
l By the direct combination of hydrogen and chlorine.
H2(g) + Cl2(g) ¾¾¾¾¾
Sunlight
® 2HCl(g)
l Hydrogen chloride gas can also be obtained by burning hydrogen in chlorine.
l Properties : Hydrogen chloride is a covalent compound but when dissolved in water it ionizes to form
hydrogen ions and chloride ions.
HCl(aq) ¾® H+(aq) + Cl–(aq)
Thus anhydrous HCl does not show acidic properties. Only aqueous HCl or in presence of moisture,
HCl behaves as an acid.
118 E
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l Metal + Hydrochloric acid ¾® Metal chloride + Hydrogen
Mg + 2HCl ¾® MgCl2 + H2
l It react with bases and basic oxides or hydroxides to form their respective chlorides and water.
CaO + 2HCl ¾® CaCl2 + H2O
l It reacts with metal carbonates, bicarbonates, sulphides, sulphites, thiosulphates and nitrites, etc, to
form their respective chlorides.
Na2CO3 + 2HCl ¾® 2NaCl + H2O + CO2
l It reacts with silver nitrate and lead nitrate solution to form white precipitates.
AgNO3 + HCl ¾® HNO3 + AgCl¯
l Reducing property :
HCl is a strong reducing agent.
MnO2 + 4HCl ¾® MnCl2 + 2H2O + Cl2
Uses :
l In the production of dyes, paints, photographic chemicals, etc.
l Used in the preparation of chlorides, chlorine, aqua-regia, etc.
l Used as a laboratory reagent.
Interhalogen Compounds :
l These compounds are regarded as halides of more electropositive (i.e. less elecronegative) halogens.
l Types of interhalogen compound :
AB type : ClF, BrF, BrCl, ICl, IBr
AB3 type : ClF3, BrF3, ICl3
AB5 type : BrF5, IF5
AB7 type : IF7
Some Important Reactions

1. ( NH 4 )2 Cr2 O7 ¾¾¾
Heat
® N 2 + 4H 2 O + Cr2 O3
2. FeCl3 (aq) + NH4OH (aq) ® Fe2O3.xH2O (s) + NH4Cl (aq)

2+
3. Cu 2 + ( aq ) + 4NH 3 ( aq ) ® éëCu ( NH 3 )4 ùû ( aq )
4. AgCl (s) + 2NH3 (aq) ® [Ag(NH3)2]Cl
5. 2Pb ( NO 3 )2 ¾¾¾
673K
® 4NO 2 + 4PbO + O 2
6. 4HNO3 + P4O10 ® 4HPO3 + 2N2O5

7. 3Cu + 8HNO3 (dil.) ® 3Cu(NO3)2 + 2NO + 4H2O
8. Cu + 4HNO3 (conc.) ® Cu(NO3)2 + 2NO2 + 2H2O
9. 4Zn + 10HNO3 (dil.) ® 4Zn(NO3)2 + N2O + 5H2O
10. Zn + 4HNO3 (conc.) ® Zn(NO3)2 + 2NO2 + 2H2O
11. I2 +10HNO3 (conc.) ® 2HIO3 + 10NO2 + 4H2O
12. S8 + 48HNO3 (conc.) ® 8H2SO4 + 48NO2 + 16H2O
E 119
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13. Chemistry of ring test :
NO3–+ 3Fe2+ + 4H+ ® NO + 3Fe3+ + 2H2O
[Fe(H2O)6]2+ + NO ® [Fe(H2O)5NO]2+ + H2O
14. 4HCl + O2 ¾¾¾

CuCl2
® 2Cl2 + 2H 2O
15. 2Fe3+ + SO2 + 2H2O ® 2Fe2+ + SO42– + 4H+

16. 5SO2 + 2MnO4– + 2H2O ® 5SO42– + 4H+ + 2Mn2+
17. 2F2 (g) + 2H2O (l) ® 4H+ (aq) + 4F– (aq) + O2 (g)
18. X2 (g) + H2O (l) ® HX (aq) + HXO (aq) (X = Cl, Br)
19. 4I–(aq) + 4H+ (aq) + O2 ® 2I2 (s) + 2H2O (l)
20. MnO2 + 4HCl ® MnCl2 + Cl2 + 2H2O
21. 2NaOH (dil) + X2 ¾¾¾
Cold
® NaX + NaOX + H2O
22. 6NaOH (conc) + 3X2 ¾¾¾

heat
® 5NaX + NaXO3 + 3H2O(X2 = Cl2, Br2, I2)
23. 2Ca(OH)2 + 2Cl2 ® Ca(OCl)2 + CaCl2 + 2H2O
24. NaCl + H2SO4 ¾¾¾

heat
® NaHSO4 + HCl
25. XeF2 + PF5 ® [XeF]+[PF6]–

26. XeF6 + MF ® M+[XeF7]– (M = Na, K, Rb or Cs)
27. 6XeF4 + 12H2O ® 4Xe + 2XeO3 + 24HF + 3O2
28. XeF6 + 3H2O ® XeO3 + 6HF
29. XeF6 + H2O ® XeOF4 + 2HF
30. XeF6 + 2H2O ® XeO2F2 + 4HF
F
105 pm
F
O S S
102°
H 104.5° H H 92° H
3 3
H2O(sp ) H2S(sp )
17
V-shape V-shape F
3°
F
Trigonal pyramidal sp3d
Oxy-acids of sulphur
F
F F
F
F F
F
I F
Cl F Cl
F F F
F F F
Bent-T-shaped (sp3d) CIF3 Square pyramidal Pentagonal bipyramidal

CIF5(sp3d2) IF5(sp3d3)
120 E
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F F
F F F F
Xe
Xe Xe
F F F F F
XeF2
F
XeF2 Linear (sp3d) XeF4 Square Planer XeF6 (sp3d2)
(sp3d2 ) Distorted octahedral
F F
F F
O
Xe Xe Xe
O O
O F F
F
sp3 Pyramidal Square pyramidal XeOF2 (sp3d)

XeO3 XeOF2 (sp3d2) T-shaped
O O O O O
S S S S S S
OH O OH O O O O O O O O
HO HO OH HO OH HO
Sulphurous acid Sulphuric acid Peraoxodisulphuric acid Pyrosulphuric acid (Oleum)
(H2SO3) (H2SO4) (H2S2O3) (H 2S2O 7)
O O
H H
H F H Cl
O O
Hypofluorous acid Hypochlorous acid
(HOF) (HClO)
Cl Cl
O
O
O O O
H Cl
O O
Chlorous acid
(HClO2) Chloric acid Perchloric acid
(HClO3) (HClO4)
E 121
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1. Why is BiH3 the strongest reducing agent amongst all the hydrides of Group 15 elements?
Ans. As we move down a group, the atomic size increases and the stability of the hydrides of group 15
elements decreases. Since the stability of hydrides decreases on moving from NH3 to BiH3, the
reducing character of the hydrides increases on moving from NH3 to BiH3.
2. Why is N2 less reactive at room temperature?
Ans. The two N atoms in N2 are bonded to each other by very strong triple covalent bonds. The bond
dissociation energy of this bond is very high. As a result, N2 is less reactive at room temperature.
3. Mention the conditions required to maximise the yield of ammonia.
Ans. Ammonia is prepared using the Haber’s process. The yield of ammonia can be maximized under
the following conditions: (i) High pressure ( 200 atm) (ii) A temperature of 700 K
(iii) Use of a catalyst such as iron oxide mixed with small amounts of K2O and Al2O3
4. How does ammonia react with a solution of Cu2+?
Ans. NH3 acts as a Lewis base. It donates its electron pair and forms a linkage with metal ion.
2+
Cu 2( aq+ ) + 4NH 3( aq ) ® éë Cu ( NH 3 )4 ùû
( aq )
Blue Deep blue

5. Discuss the general characteristics of Group 15 elements with reference to their electronic
configuration, oxidation state, atomic size, ionisation enthalpy and electronegativity.
Ans. General trends in group 15 elements :
(i) Electronic configuration : All the elements of group 15 have 5 valence electrons. Their
general electronic configuration is ns2 np3.
(ii) Oxidation states : This group show a formal oxidation state of –3 in their covalent
compounds. In addition to the –3 state, N and P also show –1 and –2 oxidation states.
All the elements present in this group show +3 and +5 oxidation states. However, the stability
of +5 oxidation state decreases down a group, whereas the stability of +3 oxidation state
increases. This happens because of the inert pair effect.
(iii) Ionization energy and electronegativity : Decreases on moving down the group due to increase in size.
(iv) Atomic size : Increases on moving down the group.
6. Why does the reactivity of nitrogen differ from phosphorus?
Ans. Bond dissociation energy of N2 is very high in comparison to P4.
N º N (914.4 kJ/mol), P–P = (213 kJ/mol)
7. Why does NH3 form hydrogen bond but PH3 does not?
Ans. Nitrogen is highly electronegative as compared to phosphorus.
8. Discuss the trends in chemical reactivity of group 15 elements.
Ans. General trends in chemical properties of group 15 :
(i) Reactivity towards hydrogen : The elements of group 15 react with hydrogen to form
hydrides of type EH3, where E = N, P, As, Sb, or Bi. The stability of hydrides decreases on
moving down from NH3 to BiH3.
(ii) Reactivity towards oxygen : The elements of group 15 form two types of oxides : E2O3 and
E2O5, whre E = N, P, As, Sb, or Bi. The oxide with the element in the higher oxidation state is
more acidic than the lower one. However, the acidic character decreases on moving down the
group.
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(iii) Reactivity towards halogen : The group 15 elements react with halogens to form two series
of salts: EX3 and EX5. However, nitrogen does not form NX5 as it lacks the d-orbital.
(iv) Reactivity towards metals : The group 15 elements react with metals to form binary
compounds in which its exhibit –3 oxidation states.
9. How is nitrogen prepared in the laboratory? Write the chemical equations of the reactions involved.
Ans. An aqueous solution of ammonium chloride is treated with sodium nitrite.
NH4Cl(aq) + NaNO2(aq) ¾® N2(g) + 2H2O(l) + NaCl(aq)
10. How is ammonia manufactured industrially?
Ans. Ammonia is prepared on a large-scale by Haber's process.
N2(g) + 3H2(g) 2NH3(g) DfH° = –46.1 kJ/mol
The optimum conditions for manufacturing ammonia are :
(i) Pressure (around 200 × 105 Pa)
(ii) Temperature (~700K)
(iii) Catalyst such as iron oxide with small amounts of Al2O3 and K2O.
11. Illustrate how copper metal can give different products on reaction with HNO3.
Ans. Concentrated nitric acid is a strong oxidizing agent. It is used for oxidizing most metals. The products
of oxidation depend on the concentration of the acid, temperature, and also on the material undergoing
oxidation.
3Cu + 8HNO3 ¾® 3Cu(NO ) + 2NO + 4H O

3 2 2
(dilute)
Cu + 4HNO3 ¾® Cu(NO3)2 + 2NO2 + 2H2O
(conc.)
12. The H–N–H angle value is higher than HPH, HAsH and HSbH angles. Why?
Ans. The above trend in the H–M–H bond angle can be explained on the basis of the electronegtivity of the
central atom. Since nitrogen is highly electronegative, there is high electron density around nitrogen.
This causes greater repulsion between the electron pairs around nitrogen, resulting in maximum bond
angle.
This can also be explained on the basis of hybridisation. In NH3 there in sp3 hybridization whereas
only sp3 bonding takes place between hydrogen and other elements of groups.
13. Why does R3P = O exist but R3N = O does not? (R = alkyl group)
Ans. N(unlike P) lacks the d-orbital. This restricts nitrogen to expand its coordination number beyond
four. Hence, R3N=O does not exist.
14. Explain why NH3 is basic while BiH3 is only feebly basic.
Ans. NH3 is distinctly basic while BiH3 is feebly basic. Becasue nitrogen has a small size due to which
the lone pair of electrons is concentrated in a small region. This means that the charge density per
unit volume is high. On moving down a group, the size of the central atom increases and the
charge gets distributed over a large area decreasing the electron density. Hence, the electron
donating capacity of group 15 element hydrides decreases on moving down the group.
15. Why does nitrogen show catenation properties less than phosphorus?
Ans. Catenation is much more common in phosphorous compounds than in nitrogen compounds. This
is because of the relative weakness of the N–N single bond as compared to the P–P single bond.
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16. Write balanced equations for the following:
(i) NaCl is heated with sulphuric acid in the presence of MnO2.
(ii) Chlorine gas is passed into a solution of NaI in water.
Ans. (i) 4NaCl + MnO2 + 4H2SO4 ¾® MnCl2 + 4NaHSO4 + 2H2O + Cl2
(ii) Cl2 + Nal ¾® 2 NaCl + I2
17. List the important sources of sulphur.
Ans. Sulphur mainly exists in combined form in the earth’s crust primarily as sulphates [gypsum
(CaSO4.2H2O), Epsom salt (MgSO4.7H2O), baryte (BaSO4)] and sulphides [(galena (PbS), zinc
blende (ZnS), copper pyrites (CuFeS2)].
18. Write the order of thermal stability of the hydrides of Group 16 elements.
Ans. The thermal stability of hydrides decreases on moving down the group. This is due to a decrease
in the bond dissociation enthalpy (H-E) of hydrides on moving down the group. Therefore,
Thermal stability decreases
H2O, H2S, H2Se, H2Te, H2Po
19. Why is H2O a liquid and H2S a gas ?
Ans. H2O has oxygen as the central atom. Oxygen has smaller size and higher electronegativity as
compared to sulphur. Therefore, there is extensive hydrogen bonding in H2O, which is absent in
H2S. Molecules of H2S are held together only by weak van der Waal’s forces of attraction.
Hence, H2O exists as a liquid while H2S as a solid.
20. Which of the following does not react with oxygen directly?
Zn, Ti, Pt, Fe
Ans. Pt is a noble metal and does not react very easily. All other elements, Zn, Ti, Fe, are quite
reactive. Hence, oxygen does not react with platinum (Pt) directly.
21. Complete the following reactions :-
(i) C2H4+O2® (ii) Al + 3 O2®
Ans.
22. Why does O3 act as a powerful oxidising agent?
Ans. Ozone is not a very stable compound under normal conditions and decomposes readily on heating to
give a molecule of oxygen and nascent oxygen. Nascent oxygen, being a free radical, is very reactive.
Therefore, ozone acts as a powerful oxidising agent.

23. How is O3 estimated quantitatively ?
Ans. Quantitatively, ozone can be estimated with the help of potassium iodide. When ozone is made to
react with potassium iodide solution buffered with a borate buffer (pH 9.2), iodine is liberated.
This liberated iodine can be titrated against a standard solution of sodium thiosulphate using
starch as an indicator. The reactions involved in the process are
2I - + H 2 O + O3 ¾¾
® 2OH - + I 2 + O 2
Iodide Ozone Iodine
I 2 + 2Na 2S2 O 3 ¾¾
® Na 2S4 O 6 + 2Nal
Sodium Sodium
thiosulphate tetra thionate
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24. What happens when sulphur dioxide is passed through an aqueous solution of Fe(III) salt?
Ans. SO2 acts as a reducing agent when passed through an aqueous solution containing Fe(III) salt. It
reduces Fe(III) to Fe(II) i.e., ferric ions to ferrous ions.
2Fe3+ + SO 2 + 2H 2 O ¾¾
® 2Fe2 + + SO 24 - + 4H +
25. Comment on the nature of two S–O bonds formed in SO2 molecule. Are the two S–O bonds in this
molecule equal ?
Ans. The electronic configuration of S is 1s2 2s2 2p6 3s2 3p4.
It is a resonance hybrid of structures I and II.
Both S-O bonds are equal in length (143 pm) and have a multiple bond character.
26. How is the presence of SO2 detected ?
Ans. SO2 is a colourless and pungent smelling gas. It can be detected with the help of potassium
permanganate solution. When SO2 is passed through an acidified potassium permanganate solution,
it decolourises the solution as it reduces MnO 4- ions to Mn 2 + ions .
5SO2 + 2MnO4– + 2H2O ® 5SO42– + 4H+ + 2Mn2+
27. Why is Ka2<<Ka1 for H2SO4 in water ?
® H3O(+aq ) + HSO 4-(aq ) ; K a > 10
Ans. H2 SO4(aq ) + H 2 O( t ) ¾¾ 1
HSO4-( aq ) + H2 O( t ) ¾¾
® H3 O(+aq ) + SO4-( aq ) ; K a2 = 1.2 ´ 10 -2
It can be noticed that Ka2<<Ka1
This is because a neutral H2SO4 has a much higher tendency to lose a proton than the negatively
–
charged HSO4 . Thus, the former is a much stronger acid than the latter.
28. Considering the parameters such as bond dissociation enthalpy, electron gain enthalpy and
hydration enthalpy, compare the oxidising power of F2 and Cl2.
Ans. Fluorine is a much stronger oxidizing agent than chlorine. The oxidizing power depends on three
factors.
1. Bond dissociation energy
2. Electron gain enthalpy
3. Hydration enthalpy
The electron gain enthalpy of chlorine is more negative than that of fluorine. However, the bond
dissociation energy of fluorine is much lesser than that of chlorine. Also, because of its small
size, the hydration energy of fluorine is much higher than that of chlorine.
Therefore, the two factors more than compensate for the less negative electron gain enthalpy of
fluorine. Thus, fluorine is a much stronger oxidizing agent than chlorine.
29. Give two examples to show the anomalous behaviour of fluorine.
Ans. Anomalous behaviour of fluorine
(i) It forms only one oxoacid as compared to other halogens that form a number of oxoacids.
(ii) Ionisation enthalpy, electronegativity, and electrode potential of fluorine are much higher
than expected.
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30. Sea is the greatest source of some halogens. Comment.
Ans. Sea water contains chlorides, bromides, and iodides of Na, K, Mg, and Ca. However, it primarily
contains NaCl. The deposits of dried up sea beds contain sodium chloride and carnallite,
KCl.MgCl2.6H2O. Marine life also contains iodine in their systems. For example, sea weeds
contain upto 0.5% iodine as sodium iodide. Thus, sea is the greatest source of halogens.
31. Give the reason for bleaching action of Cl2.
Ans. When chlorine reacts with water, it produces nascent oxygen. This nascent oxygen then combines
with the coloured substances present in the organic matter to oxidise them into colourless
substances.
Cl 2 + H 2 O ® 2HCl + [ O ]
Coloured substances + [O] ® Oxidized colourless substance
32. Name two poisonous gases which can be prepared from chlorine gas.
Ans. Two poisonous gases that can be prepared from chlorine gas are
(i) Phosgene (COCl2)
(ii) Mustard gas (ClCH2CH2SCH2CH2Cl)
33. Why is ICl more reactive than I2?
Ans. ICl is more reactive than I2 because I–Cl bond in ICl is weaker than I–I bond in I2.
34. Why is helium used in diving apparatus ?
Ans. Air contains a large amount of nitrogen and the solubility of gases in liquids increases with
increase in pressure. When sea divers dive deep into the sea, large amount of nitrogen dissolves
in their blood. When they come back to the surface, solubility of nitrogen decreases and it separates
from the blood and forms small air bubbles. This leads to a dangerous medical condition called
bends. Therefore, air in oxygen cylinders used for diving is diluted with helium gas. This is done
as He is sparingly less soluble in blood.
35. Balance the following equation: XeF6 + H2O ® XeO2F2 + HF
Ans. Balanced equation
XeF6 + 2 H2O ® XeO2F2 + 4 HF
36. Why has it been difficult to study the chemistry of radon?
Ans. It is difficult to study the chemistry of radon because it is a radioactive substance having a half-
life of only 3.82 days. Also, compounds of radon such as RnF2 have not been isolated.
They have only been identified.
37. Justify the placement of O, S, Se, Te and Po in the same group of the periodic table in terms of
electronic configuration, oxidation state and hydride formation.
Ans. The elements of group 16 are collectively called chalcogens.
(i) Electronic configuration :
Element of group 16 have six valence electrons each. The general electronic configuration of
these elements is ns2 np4, where n varies from 2 to 6.
(ii) Oxidation state :
As these elements have six valence electrons (ns2 np4), they should display an oxidation state of -
2. However, only oxygen predominantly shows the oxidation state of –2 owing to its high
electronegativity. It also exhibits the oxidation state of –1(H2O2), zero (O2), and +2 (OF2).
However, the stability of the –2 oxidation state decreases on moving down a group due to a
decrease in the electronegativity of the elements. The heavier elements of the group show an oxidation
state of +2, +4, and +6 due to the availability of d-orbitals.
(iii) Formation of hydrides :
These elements form hydrides of formula H2E, where E = O, S, Se, Te, PO. Oxygen and sulphur also
form hydrides of type H2E2. These hydrides are quite volatile in nature.
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38. Why is dioxygen a gas but sulphur is a solid?
Ans. Oxygen is smaller in size as compared to sulphur. Due to its smaller size, it can effectively form
pp–pp bonds and form O2(O=O) molecule. Also, the intermolecular forces in oxygen are weak van dar
Wall's forces, which cause it to exist as gas. On the other hand, sulphur does not form S2 molecule but
exists as a puckered structure (S8) held together by strong covalent bonds. Hence, it is a solid.
39. Knowing the electron gain enthalpy values for O ® O– and O ® O2– as –141 and 702 kJ mol–1
respectively, how can you account for the formation of a large number of oxides having O2–
species and not O–?
(Hint: Consider lattice energy factor in the formation of compounds).
Ans. Stability of an ionic compound depends on its lattice energy. More the lattice energy of a compound,
more stable it will be.
40. Which aerosols deplete ozone?
Ans. Freons or chlorofluorocarbanes (CFCs) are aerosols that accelerate the depletion of ozone. In the
presence of ultraviolet radiations, molecules of CFCs break down to form chlorine-free radicals
that combine with ozone to form oxygen.
41. How is SO2 an air pollutant?
Ans. Sulphur dioxide causes harm to the environment in many ways :
1. It combines with water vapour present in the atomsphere to form sulphuric acid. This causes acid
rain. Acid rain damages soil, plants, and buildings, especially those made of marble.
2. Even in very low concentrations, SO2 causes irritation in the respiratory tract. It causes throat and
eye irritation and can also affect the larynx causing breathlessness.
3. It is extremely harmful for plants. Plants exposed to sulphur dioxide for a long time lose colour
from their leaves. This condition is known as chlorosis. This happens because the formation of
chorophyll is affected by the presence of sulphur dioxide.
42. Why halogens are strong oxidising agents?
Ans. The general electronic configuration of halogens is ns2 np5, where n = 2-6. Thus, halogens need
only one more electron to complete their octet and to attain the stable noble gas configuration.
Also, halogens are highly electronegative with low dissociation energies and high negative electron
gain enthalpies. Therefore, they have a high tendency to gain an electron. Hence they act as
strong oxidizing agents.
43. Explain why fluorine forms only one oxoacid, HOF.
Ans. Fluorine forms only one oxoacid i.e., HOF because of its high electronegativity and small size.
44. Explain why inspite of nearly the same electronegativity, nitrogen forms hydrogen bonding while
chlorine does not.
Ans. Both chlorine and nitrogen have almost the same electronegativity values, but chlorine rarely
forms hydrogen bonding. This is because in comparison to chlorine, nitrogen has a smaller size
and as a result, a higher electron density per unit volume.
45. Write two uses of ClO2.
Ans. Uses of ClO2 :
(i) It is used to purifying water. (ii) It is used as a bleaching agent.
46. Why halogens are coloured?
Ans. Almost all halogens are coloured. This is because halogens absorb radiations in visible region. This
results in the excitation of valence electrons to a higher energy region. Since the amount of energy
required for excitation differ for each halogen, each halogen displays a different colour.
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47. Write the reactions of F2 and Cl2 with water.
Ans. (i) Cl2 + H2 O ¾¾® HCl
Hydrochloric acid
+ HOCl
Hypochlorous acid
(ii) 2F2( g) + 2H2 O ( f) ¾¾® 4H + (aq ) + 4F - ( aq ) + O2( g)
48. How can you prepare Cl2 from HCl and HCl from Cl2? Write reactions only.
Ans. (i) Cl2 can be prepared from HCl by Deacon's process.
CuCl2
4HCl + O2 ¾¾¾® 2Cl2 + 2H2O
(ii) HCl can be prepared from Cl2 on treating it with water.
Cl2 + H2 O ¾¾® HCl + HOCl
Hydrochloric acid Hypochlorous acid
49. What inspired N. Bartlett for carrying out reaction between Xe and PtF6?
Ans. Neil Bartlett initially carried out a reaction between oxygen and PtF6. This resulted in the formation of
a red compound, O2+ [PtF6]– was formed.
50. Write balanced equations for the following:
(i) NaCl is heated with sulphuric acid in the presence of MnO2.
(ii) Chlorine gas is passed into a solution of NaI in water.
Ans. (i) 4NaCl + MnO2 + 4H2SO4 ¾® MnCl2 + 4NaHSO4 + 2H2O + Cl2
(ii) Cl2 + Nal ¾® 2 NaCl + I2
51. How are xenon fluorides XeF2, XeF4 and XeF6 obtained ?
Ans. XeF2, XeF4 and XeF6 are obtained by a direct reaction between Xe and F2. The condition under
which the reaction is carried out determines the product.
673 K.1 bar
Xe( g) + F2(g) ¾¾¾¾¾ ® XeF2(s)
( Excess )
873 K.7 bar

Xe(g) + 2F2(g) ¾¾¾¾¾ ® XeF4(s)
(1:5 ratio)
573K.60 -70 bar
Xe( g ) + 3F2( g ) ¾¾¾¾¾¾ ® XeF6(s )
(1:20 ratio)
52. With what neutral molecule is ClO– isoelectronic ? Is that molecule a Lewis base?
Ans. ClO– is isoelectronic of ClF. since both species contain 26 electrons in all as shown.
Total electrons ClO– = 17 + 8 + 1 = 26
In ClF = 17 + 9 = 26
ClF act like a Lewis base because it can donate a lone pair of electrons.
53. How are XeO3 and XeOF4 prepared?
Ans. (i) XeO3 can be prepared in two ways as shown.
6XeF4 + 12H2O ¾® 4Xe + 2XeO3 + 24 HF + 3O2
XeF6 + 3H2O ¾® XeO3 + 6HF
(ii) XeOF4 can be prepared using XeF6.
XeF6 + H2O ¾® XeOF4 + 2HF
54. Arrange the following in the order of property indicated for each set:
(i) F2, Cl2, Br2, I2 - increasing bond dissociation enthalpy.
(ii) HF, HCl, HBr, HI - increasing acid strength.
(iii) NH3, PH3, AsH3, SbH3, BiH3 – increasing base strength.
Ans. (i) I2 < F2 < Br2 < Cl2
(ii) HF < HCl < HBr < HI
(iii) BiH3 £ SbH3 < AsH3 < PH3 < NH3 62. Which one of the following does not exist?
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55. Which one of the following does not exist ?
(i) XeOF4 (ii) NeF2 (iii) XeF2 (iv) XeF6
Ans. NeF2 does not exist.
56. Give the formula and describe the structure of a noble gas species which is isostructural with :
(i) ICl4– (ii) IBr2– (iii) BrO3–
Ans. (i) XeF4 is iso structural with ICl–4 and has square planar geometry.
F F
Xe
F F
(ii) XeF2 is iso structural with IBr–2 and has a linear structure.
Xe
(iii) XeO3 is iso structural with BrO–3and has a pyramidal molecular structure.
Xe
O O
O
57. Why do noble gases have comparatively large atomic sizes?

Ans. Noble gases do not form molecules. In case of noble gases, the atomic radii corresponds to
vander Waal's radii. On the other hand, the atomic radii of other elements correspond to their
covalent radii. By definition, van dar Waal's radii are larger than covalent radii. It is for this
reason that noble gases are very large in size as compared to other atoms belonging to the same
period.
58. List the uses of Neon and Argon gases.
Ans. (1) Use of Neon :
(i) It is used in discharge tubes and fluorescent bulbs for advertisement display purpose.
(ii) Neon blubs are used in botanical gardens and in green houses.
(2) Uses of Argon :
(i) It is used mainly, to provide an inert atmosphere in high temperature. Metallurgical process
(welding of metals or alloys) and for filling electric bulbs.
(ii) It is also used in the laboratory for handing substances that are air sensitive.
59. Complete the following equations :
(i) C + conc. H2SO4 ®
(ii) XeF2 + H2O ®
Ans. (i) C + 2H2SO4(conc.) ® CO2 + 2SO2 + 2H2O
(ii) 2XeF2(s) + 2H2O(l) ® 2Xe (g) + 4 HF(aq) + O2(g)
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60. Draw the structures of the following :
(i) XeO3
(ii) H2 SO 4
O
Xe
S
Ans. (i) O O
(ii) OH O
O HO
Pyramidal Sulphuric acid
(H 2SO 4)
61. Why does NH3 act as a Lewis base.
Ans. Nitrogen atom in NH3 has one lone pair of electrons which is available for donation. Therefore, it acts as
a Lewis base.
62. Give reasons for the following :
(i) (CH3)3 P = O exists but (CH3)3 N= O does not.
(ii) Oxygen has less electron gain enthalpy with negative sign than sulphur.
Ans. (i) In nitrogen the absence of d orbitals in its valence shell. Besides restricting its covalency to four, nitrogen
cannot form dp–pp bond as the heavier elements can e.g., R3P = O or R3P = CH2 (R = alkyl group).
Phosphorus and arsenic can form dp–dp bond also with transition metals when their compounds like
P(C2H5)3 and As(C6H5)3 act as ligands.
(ii) Because of the compact nature of oxygen atom, it has less negative electron gain enthalpy than sulphur.
63. How are inlerhalogen compounds formed? What general compositions can be assigned to them?
Ans. All interhalogen compounds are prepared either by direct combination between the halogens by the
action of halogen on a lower inter halogen. The product formed, however depends upon the conditions.
Cl2(g) + F2(g) ¾¾¾
473K
® 2C1 F(g)
Cl2(g) + 3F2(g) ¾¾¾
573K
® 2ClF3(g)
475 - 573K
ClF(g) + F2(g) ¾¾¾¾ ® ClF3(g)
Þ Br2(l) + 5F2(g) ¾® 2BrF5(l)
Þ I2(g) + 7F2(g) ¾® 2IF7(g)
64. Draw the structures of the following molecules :
XeF2
Xe
Ans.
F
Linear
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65. Give reasons for the following :
(i) Though nitrogen exhibits +5 oxidation state, it does not form pentahalide.
(ii) The two oxygen - oxygen bond lengths in ozone molecule are identical.
Ans. (i) NX5 cannot exist as nitrogen cannot form 5 bonds as compared to P, As etc as there are no
empty d orbitals in it.
(ii) Attraction dominates
Å
O O O
O O O O O O
(I) (II)
O3 can be written as a resonance hybrid of above two structures as (1) and (II) are identical so
both will contribute equally to the hybrid giving a bond order of 1.5 to each bond.
66. Which is a stronger reducing agent, SbH3 or BiH3, and why ?
Ans. BiH3, due to less bond dissociation enthalpy.
67. Explain the following facts giving appropriate reason in each case :
(i) NF3 is an exothermic compound where as NCl3 is not.
(ii) All the bonds in SF4 are not equivalent.
Ans. (i) B'coz N & F are second period element (2p – 2p) but N & Cl are both second and Third
period elements(2p – 3p).
(ii) B'coz axial bonds suffer more repulsion.
68. (a) Draw the molecular structures of the following compounds :
XeOF4
(b) Explain the following observations :
(i) Sulphur has a greater tendency for catenation than oxygen.
(ii) ICl is more reactive than I2.
(iii) Despite lower value of its electron gain enthalpy with negative sign, fluorine (F2) is a srtonger
oxidising agent than Cl2.
Ans. (a)
O
F
F
Xe
Xe
F
F
Square pyramidal
(b) (i) Due to formation of pp-pp multiple bond in case of oxygen. while sulphur forms single
covalent linkage.
(ii) due to weaker X–X' bonding than X–X bond.
(iii) low enthalpy of dissociation of F–F bond.
(iv) high hydration enthalpy of F
69. (a) Complete the following chemical equations :
(i) Cu + HNO3 (dilute) ¾®
(ii) XeF4 + O2F2 ¾®
(i) Phosphorous has greater tendency for catenation than nitrogen.
(ii) Oxygen is a gas but sulphur a solid.
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(iii) The halogens are coloured. Why ?
Ans. (a) (i) 3Cu + 8HNO3(dilute) ¾® 3Cu(NO3)2 + 2NO + 4H2O
(ii) XeF4 + O2F2 ¾® XeF6 + O2
(b) (i) due to formation of pp-pp multiple bond in case of nitrogen while phosphorus forms single
covalent bond.
(ii) due to formation of pp-pp multiple bond in case of oxygen while sulphur forms single covalent
linkage and exists as 3d network solid.
(iii) Due to absorption of radiations invisible region which results in the excitation of outer
electrons to higher energy level.
70. How would you account for the following:
(i) H2S is more acidic than H2O.
(ii) Both O2 and F2 stabilize high oxidation states but the ability of oxygen to stabilize the higher
oxidation state exceeds that of fluorine.
Ans. (i) The size of central atom in H2S is larger than H2O. Hence H2S is more acidic than H2O.
(ii) Size of O > Size of F.
Because oxygen has highest oxidation state is –2 and fluorine has highest oxidation state is
–1.
71. (a) Draw the structures of the following molecules :
BrF3
(b) Complete the following chemical equations:
(i) HgCl2 + PH3 ®
(ii) SO3 + H2SO4 ®
(iii) XeF4 + H2O ®
F
Ans. (a) BrF3 ® Br F
F
Bent- T shape
(b) (i) 3 HgCl2 + 2 PH3 ® Hg3 P2 + 6HCl

Mercuric Mercuric
chloride phosphide
(ii) SO3 + H2SO4 ® H2S2O7

Sulpher Oleum
trioxide (Pyrosulphuric acid)
(iii) 6 XeF4 + 12H2O ® 4XeO3 + 24HF + 3O2

72. (a) What happen when
(i) Chlorine gas is passed through a hot concentrated solution of NaOH?
(ii) sulphur dioxide gas is passed through an aqueous solution of a Fe (III) salt?
(b) Answer the following:
(i) Why does fluorine not play the role of a central atom in interhalogen compounds?
(ii) Why do noble gases have very low boiling points?
Ans. (a) (i) 3Cl2 + 6NaOH ® NaCl + NaClO3 + 3H2O.
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When chlorine gas is passed through sodium hydroxide solution then some quantity of water
is released with the formation of sodium chloride and sodium oxychloride.
(ii) Fe (III) Salt is reduced to Fe (II Salt)
2Fe3+ + SO 2 + 2H 2 O ® 2Fe2 + + SO 24- + 4H +
(b) (i) Fluorine does not play the role of a central atom in interhalogen compounds because
it is most electronegative element and cannot exhibit any positive
oxidation state.
(ii) Because, noble gases have weak interatomic attraction forces (London dispersion force)
73. Fluorine does not exhibit any positive oxidation state. Why?
Ans. Fluorine is the most electronegative element & cannot exhibit any positive oxdation state.
74. Draw the structural formulae of the following compounds :
XeF4
Ans. Structure of XeF4 :
F F
Xe
F F
75. How would you account for the following:

(i) XeF2 is linear molecule without a bend.
(ii) The electron gain enthalpy with negative sign for fluorine is less than that for chlorine,
still flurine is a stronger oxidising agent that chlorine.
Ans. (i) Since there are two Xe-F covalent bonds in XeF2. According to VSEPR theory, the shape
of XeF2 is linear.
(ii) The electron gain enthalpy of fluorine is less negative than that of chlorine due to the small
size of fluorine atom.
76. Complete the following chemical reaction equation :

(i) XeF2 + H2O ® (ii) PH3 + HgCl2 ®
Ans. (i) 2XeF2 + 2H2O ® 2Xe + 4HF + O2
(ii) 2PH3 + 3HgCl2 ® Hg3P2 + 6HCl
77. (a) Draw the structures of the following :
(i) H2S2O8 (ii) HClO4
(b) How would you account for the following :
(i) NH3 is stronger base than PH3
(ii) Sulphur has a greater tendency for catenation than oxygen.
(iii) F2 is a stronger oxidising agent than Cl2 .
Ans. (a) (i) H2S2O8 (Peroxodisulphuric acid)
O O
S S
O O O O
OH HO
(ii) HCl O4(Perchloric acid)
O
H–O–Cl=O
O
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(b) (i) Size of N-atom is smaller as compair to P -atom, hence charge density of lone pair is
more concentrated on N-atom.
(ii) The property of catenation depends upon the strength of the between elements bond.
Since sulphur S–S bond strength is much more than O–O bond strength. So sulphur has
greater tendency for catenation than oxygen.
(iii) Since the oxidising power of halogens decreases from F2 to I2. There fore F2 is the
stronger oxidising agent than Cl2 due smaller size and absent of d-orbital.
78. (a) Draw the structures of the following :
(i) H2S2O7 (ii) HClO3
(i) In the structure of HNO3, the N–O bond
(121 pm) is shorter than the N–OH bond (140 pm)
(ii) All the P–Cl bonds in PCl5 are not equivalent.
(iii) ICl is more reactive than I2 .
Ans. (a) (i) Structure of H2S2O7 (Oleum)
O O
S S
O O O
OH OH
(ii) HClO3 (Chloric acid)
Cl
O O
OH
(b) (i) Due to smaller size of N–O than N–OH, the N–O bond length in HNO3 is smaller than
N–OH bond length.
(ii) All the P–Cl bonds in PCl5 are not equivalent due to the fact that the axial bond pairs
suffer more repulsion as compared to equatorial bond pairs.
(iii) ICl is more reactive than I2 (except F2). Because X–X' bond in interhalogens is weaker
than X–X bond in halogens except F–F bond.
79. Why is the bond angle in PH3 molecule lesser than that in NH3(107¢8°) molecule ?
Ans. The bond angle in PH3 is much lower (93.6°) than that in NH3 due to less repulsion between bond
pairs.
80. Answer the following :
–
(i) Which neutral molecule would be isoelectronic with ClO ?
(ii) Of Bi (V) and Sb (V) which may be a stronger oxidising agent and why ?
–
Ans. (i) ClO has 17 + 8 + 1 = 26 electrons.
A neutral molecule with 26 electrons is OF2 (8 + 2 × 9 = 8 + 18 = 26 electrons).
(ii) On moving down the group, the stability of +5 oxidation state decreases while +3 oxidation
state increases due to inert-pair effect. Thus, +5 oxidation state of Bi is less stable then
+5 oxidation state of Sb. Therefore, Bi (V) is stronger oxidising agent than Sb (V)
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81. Assign reasons for the following :
(i) Sulphur vapour is paramagnetic.
(ii) Ammonia (NH3) has greater affinity for protons than phosphine (PH3).
(iii) SF6 is much less reactive than SF4.
(iv) Of the noble gas only xenon is known to form well established chemical compounds.
Ans. (i) In vapour state sulphur partly exists as S2 molecule which has two unpaired electrons in the
antibonding p* orbitals like O2 and hence it exahibits paramagnetism.
(ii) When NH3 or PH3 accepts a proton, an additional N-H or P-H is formed.
+
+ + +
H3N : + H ® NH4 and H3P : + H ® PH 4
Due to the bigger size of P than N, P-H bond is weaker than N-H. As a result PH3 has less
tendency than NH3 to accept a proton. Therefore, has higher proton affinity than PH3.
(iii) In SF6, six F atom protect the sulphur atom from attack by reagents to such an extent that even
thermodynamically most favourable reactions like hydrolysis do not occur.
But in SF4, S is not sterically protected since it is surrounded by only four F atoms, hence SF4
undergoes hydrolysis.
(iv) Except radon which is radioactive Xe has least ionisation energy among noble gases and hence
it is readily forms chemical compounds particularly, With oxygen & fluorine.
82. (a) Describe the favourable conditions for the manufacture of
ammonia by Haber's process,
(b) Draw the structures of the following :
(i) PCl5(g) (ii) S8 (g) (iii) ClF3(g)
Ans. (a) On a large scale, ammonia is manufactured by Haber's process.
N2(g) + 3H2(g) 2NH3(g)
The optimum conditions for the production of ammonia are a pressure with 200 atm, a
temperature of about 700 K and the use of catalyst such as iron oxide with small amount
of K2O and Al2O3 .
(b) (i) Structure of PCl 5 (g) (ii) Structure of S8(g)
Cl 204
S pm S S
Cl
S
240 pm
S 107°
P 202 p
m
S
Cl
Cl
Cl S S
[Trigonal bipyramidal] [Crown shape]
(iii) Structure of ClF3 (g)
F
Cl F
F
[Bent T-shaped]
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1. Assertion (A) : F-F bond in F2 molecule is weak. (CBSE 2020)

Reason (R) : F atom is small in size. (1)
Ans. (ii) Both Assertion (A) and Reason (R) are correct statements, and Reason (R) is the correct explanation
of the Assertion (A)
2. Draw the shape of the following molecules : (CBSE 2020)
(a) XeOF4 (b) BrF3 1×2=2
F
O
F F Br F
Ans. (a) xc (b)
F .. F F
3. Account for the following : (CBSE 2020)

(a) Sulphurous acid is a reducing agent. [1×3=3]
(b) Fluorine forms only one oxoacid.
(c) Boiling point of noble gases increases from He to Rn.
OR
Complete the following chemical reactions :
(a) MnO2 + 4HCl ¾®
(b) XeF6 + KF ¾®
(c) I- (aq) + H+(aq) + O2(g) ¾®
Ans. (a) Because sulphur readily gets oxidized itself to more stable +6 state.
(b) Because of absence of d-orbital in Fluorine
(c) Because size increases from Helium to Radon/dispersion or van der wall force increase from
Helium to Radon.
OR
(a) MnO2 + 4HCl ® MnCl2 + Cl2 + 2H2O
(b) XeF6 + KF ® K+ [XeF7]–
(c) 4I¯(aq) + 4H+(aq) + O2(g) ® 2I2(g) + 2H2O(l)
4. Write balanced chemical equations for the following processes : [2]
(a) Cl2 is passed through slaked lime. (CBSE 2019)
(b) SO2 gas is passed through an aqueous solution of Fe(III) salt.
Ans. (a) 2Ca(OH)2 + 2Cl2 ® CaCl2 + Ca(OCl)2 + 2H2O
(b) SO2 + 2Fe3+ + 2H2O ® 2Fe2+ + SO42– + 4H+
5. (a) Account for the following : [5]
(i) Tendency to show 3-oxidation state decreases from N to Bi in group 15. (CBSE 2019)
(ii) Acidic character increases from H2O to H2Te.
(iii) F2 is more reactive than ClF3, whereas ClF3 is more reactive than Cl2.
(b) Draw the structure of (i) XeF2, (ii) H4P2O7
OR
(a) Give one example to show the anomalous reaction of fluorine. [5]
(b) What is the structural difference between white phosphorus and red phosphorus ?
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(c) What happens when XeF6 reacts with NaF ?
(d) Why is H2S a better reducing agent than H2O ?
(e) Arrange the following acids in the increasing order of their acidic character :
HF, HCl, HBr and HI
Ans. (a) (i) Due to increase in size and metallic character.
(ii) Due to decrease in bond dissociation enthalpy
(iii) Due to lower bond dissociation enthalpy of F-F bond than Cl-F bond whereas Cl–Cl
bond has higher bond dissociation enthalpy than Cl-F bond.
(b)
(i) (ii)
OR
(i) 2F2(g) + 2H2O(l) ® 4H (aq) + 4F (aq) + O2(g)
+ –
(ii) White phosphorous is discrete tetrahedral whereas red phosphorous is polymeric/or

structures drawn
(iii) It forms Na+[XeF] / XeF6 + NaF ® Na+[XeF7]–
(iv) Due to lower bond dissociation enthalpy of H–S bond than H–O bond
(v) HF < HCl < HBr < HI
6. Write balanced chemical equations for the following processes : [2]
(a) Cl2 is passed through slaked lime.

(b) SO2 gas is passed through an aqueous solution of Fe(III) salt. (CBSE 2019)
OR
(a) Write two poisonous gases prepared from chlorine gas.
(b) Why does Cu2+ solution give blue colour on reaction with ammonia ?
Ans. (a) 2Ca(OH)2 + 2Cl2 ® CaCl2 + Ca(OCl)2 + 2H2O
(b) SO2 + 2Fe3+ + 2H2O ® 2Fe2+ + SO42– + 4H+
OR
(a) Mustard gas, tear gas, phosgene
(b) Because it forms blue coloured complex [Cu(NH3)4]+2 (aq)
7. (a) Give reasons : (CBSE 2018)
(i) H3PO3 undergoes disproportionation reaction but H3PO4 does not.
(ii) When Cl2 reacts with excess of F2, ClF3 is formed and not FCl3.
(iii) Dioxygen is a gas while Sulphur is a solid at room temperature.
(b) Draw the structures of the following :
(i) XeF4 (ii) HClO3
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OR
(a) When concentrated sulphuric acid was added to an unknown salt present in a test tube a
brown gas (A) was evolved. This gas intensified when copper turnings were added to this
test tube. On cooling, the gas (A) changed into a colourless solid (B).
(i) Identify (A) and (B).
(ii) Write the structures of (A) and (B).
(iii) Why does gas (A) change to solid on cooling ?
(b) Arrange the following in the decreasing order of their reducing character :
HF, HCl, HBr, HI
(c) Complete the following reaction :
XeF4 + SbF5 ¾®
Ans. (a)
(i) In H2PO3 oxidation state of central atom is +3 & on dissociation it undergoes both oxidation
+5 & reduction –3 in their respective compound
–3
D
4H 3PO3 3H3PO4 + PH3
+3 +5
(ii) When Cl2 reacts with excess of F2, ClF3 is formed and not FCl3, due to high electronegativity
& small size & absence of higher vacant orbital, fluorine exhibit only –1 oxidation state.
(iii) Dioxygen is a gas while sulphur is a solid at room temperature because electron in oxygen
atom, auring to small size of atom and tightly held, so less induced dipole - dipole attraction
while electron of sulphur atom, auring to large size of atom reach farther & cause, strong
dipole induced dipole attraction.
(b) Structure of compounds
(i) XeF4 (ii) HCl O3
F F OH
:
Xe O=Cl
F F O
:
OR
(a) (i) A ® NO2 (Nitrogen dioxide) and B ® N2O4 (dinitrogen tetraoxide)
(ii) Structure of A and B Þ NO2 N2O4
1
(Angular O Å
O (Planar)
N N—N
1
O O O O
(iii) NO2 contains odd number of valence electron & behave as odd molecule and also
dimerized to convert into stable N2O4 molecule.
(b) Decreasing order of Reducing character Þ
HI > HBr > HCl > HF
(c) XeF4 + SbF5 ® [XeF3]+ [SbF6]–
8. Among the hydrides of Group-15 elements, which have the (CBSE 2018)
(a) lowest boiling point?
(b) maximum basic character ?
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(c) highest bond angle ?
(d) maximum reducing character ?
Ans. (a) PH3 has a lowest boiling point
(b) NH3 has a maximum basic character
(c) NH3 has a highest, bond angle.
(d) BiH3 has maximum reducing character
9. Write the formula of the compound of sulphur which is obtained when conc. HNO3 oxidises S8.
(CBSE 2017)
Ans. H2SO4
10. Draw the structures of the following : (CBSE 2017)
(a) H2S2O8 (b) CIF3
O O F
S S Cl F
Ans. (a) O O (b)
O O
OH HO F
11. Give reasons for the followings : (CBSE 2017)

(a) Red phosphorus is less reactive than white phosphorus
(b) Electron gain enthalpies of halogens are largely negative
(c) N2O5 is more acidic than N2O3.
Ans. (a) Red phosphorous being polymeric is less reactive than white phosphorus which has discrete
tetrahedral structure.
(b) They readily accept an electron to attain noble gas configuration.
(c) Because of higher oxidation state(+5) of nitrogen in N2O5
12. On heating Pb(NO3)2 a brown gas is evolved which undergoes dimerization on cooling. Identify the gas.
(CBSE 2016)
Ans. NO 2
13. Write the structures of the following : (CBSE 2016)
(i) (HPO3) 3 (ii) XeF4
O O O
F F
P P
Ans. (i) HO (ii) Xe
OH
O O F F
P
O OH
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14. Assign reason for the following : (CBSE 2016)
(i) H3PO2 is a stronger reducing agent than H3PO4.
(ii) Sulphur shows more tendency for catenation than Oxygen.
(iii) Reducting character increases for HF to HI.
Ans. (i) Due to presence of two P-H bonds in H3PO2 / In H3PO2 O.S of P = +1 which can increase but in
H3PO4 O.S of P =+5 (max.)
(ii) Due to stronger S-S bond than O-O bond.
(iii) Size of halogen increases / bond length increases /bond dissociation enthalpy decreases (any one)
15. Write the formulae of any two oxoacids of phosphorus. (CBSE 2015)
Ans. H3PO2, H3PO3, H4P2O5, H4P2O6, H3PO4, H4P2O7, H3PO5, H4P2O8, (HPO3)3, (HPO3)n (Any two)
16. (a)Account for the following (CBSE 2015)
(i) Bond angle in NH4+ is greater than that in NH3.
(ii) Reducing character decreases from SO2 to TeO2.
(iii) HClO4 is a stronger acid than HClO
(b)Draw the structures of the following
(i) H2S2O8 (ii) XeOF4
Ans. (a) (i) Due to lone pair of electron on nitrogen in NH3
(ii) Due to inert pair effect / Stability of higher oxidation state decreases down the group from
S to Te / Stability of lower oxidation state increases down the group
(iii) ClO4– is more stable than ClO– / ClO4– is weak conjugate base than ClO–
O O O
F F
(b) (i) S S (ii) Xe
O O O
O OH F F
OH
17. (a)Which poisonous gas is evolved when white phosphorus is heated with conc. NaOH solution ?
Write the chemical equation.
(b)Write the formula of first noble gas compound prepared by N. Bartlett. What inspired N.
Bartlett to prepare this compound ?
(c)Fluorine is a stronger oxidizing agent than chlorine. Why ?
(d)Write one use of chlorine gas
(e)Complete the following equation (CBSE 2015)
CaF2 + H2SO4 ®
Ans. (a) PH3 Þ P4 + 3NaOH + 3H2O ® 3NaH2PO2 + PH3
(b) Xe+ [PtF6]– , Approximately same molecular size of Xe & O2 / Comparable ionisation energies
of Xe & O2
(c) It is due to (i) low enthalpy of dissociation of F-F bond (ii) high hydration enthalpy of F– .
(d) (i) for bleaching wood pulp (required for manufacture of paper and rayon), cotton and textiles.
(ii) In the metallurgy (extraction) of gold and platinum.
(iii) In the manufacture of dyes, drugs and organic compounds such as CHCl3, CCl4, DDT,
refrigerants (CCl2F2, freon), and bleaching powder.
(iv) In the preparation of poisonous gases such as phosgene (COCl2), tear gas (CCl3NO2), mustard
gas (ClCH2CH2SCH2CH2Cl), etc. Mustard gas was used by Germany in World War I.
(v) In sterilizing drinking water. (Any one use)
(e) CaF2 + H2SO4 ® CaSO4 + 2HF
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EXERCISE-3 R AC E
Sulphuric acid is manufactured by the Contact Process. Sulphuric acid is a colourless, dense, oily
liquid with a specific gravity of 1.84 at 298 K. The acid freezes at 283 K and boils at 611 K.
It dissolves in water with the evolution of a large quantity of heat. Hence, care must be taken
while preparing sulphuric acid solution from concentrated sulphuric acid. The concentrated acid
must be added slowly into water with constant stirring.
(i) Hot conc. H2SO4 acts as moderately strong oxidising agent. It oxidises both metals and
nonmetals. Which of the following element is oxidised by conc. H2SO4 into two gaseous products?
(a) Cu (b) S (c) C (d) Zn
(ii) What is the favourable condition for making sulphuric acid ?
(a) Low temp./high pressure (b) High temp./low pressure
(c) High temp./high pressure (d) low temp./low pressure
(iii) What is the oxidation state of sulphur in sulphuric acid ?
(a) 4 (b) 6 (c) 0 (d) 2
(iv) The formula of oleum is :-
(a) H2SO4 (b) H2S2O6 (c) H2S2O8 (d) H2S2O7
Question 2 to 6:-Note:- In the following questions a statement of assertion followed by a reason .
choose the correct answer out of the following choices –

2. Assertion : HI cannot be prepared by the reaction of KI With concentrated H2SO4
Reason : HI has lowest H–X bond strength among halogen acids.
3. Assertion : SF6 cannot be hydrolysed but SF4 can be.
Reason : Six F atoms in SF6 prevent the attack of H2O on sulphur atom of SF6.
4. Assertion : N2 is higher reactive than P4.
Reason : Nitrogen has more electron gain enthalpy than phosphorus.
5. Assertion : Both rhombic and monoclinic sulphur exist as S8 but oxygen exists as O2.
Reason : Oxygen forms pp – pp multiple bond due to small size and small bond length but pp –
pp bonding is not possible in sulphur.
6. Assertion : HNO3 makes iron passive.
Reason : HNO3 do not forms a protective layer of ferric nitrate on the surface of iron.

7. Affinity for hydrogen decreases in the group from fluorine to iodine. Which of the halogen acids
should have highest bond dissociation enthalpy?
(i) HF (ii) HCl (iii) HBr (iv) HI
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8. Bond dissociation enthalpy of E—H (E = element) bonds is given below. Which of the compounds
will act as strongest reducing agent?
Compound NH3 PH3 AsH3 SbH3
Ddiss (E—H)/kJ mol 389 -1
322 297 255
(i) NH3 (ii) PH3 (iii) AsH3 (iv) SbH3
9. A brown ring is formed in the ring test for NO3- ion. It is due to the formation of
(i) [Fe(H2O)5 (NO)]2+ (ii) FeSO4.NO2 (iii) [Fe(H2O)4(NO)2]2+ (iv) FeSO4.HNO3
10. Which of the following statements are true?
(i) Only type of interactions between particles of noble gases are due to weak dispersion forces.
(ii) Ionisation enthalpy of molecular oxygen is very high that of xenon.
(iii) Hydrolysis of XeF6 is a redox reaction.
(iv) Xenon fluorides are not reactive.
11. Which of the following elements does not show allotropy?
(i) Nitrogen (ii) Bismuth (iii) Antimony (iv) Arsenic
12. On heating ammonium dichromate and barium azide separately we get.
(i) N2 in both cases
(ii) N2 with ammonium dichromate and NO with barium azide
(iii) N2O with ammonium dichromate and N2 with barium azide
(iv) N2O with ammonium dichromate and NO2 with barium azide
13. Which of the following are peroxoacids of sulphur?
(i) H2SO5 and H2S2O8 (ii) H2SO5 and H2S2O7
(iii) H2S2O7 and H2S2O8 (iv) H2S2O6 and H2S2O7
14. In the preparation of compounds of Xe, Bartlett had taken O2+ Pt F6– as a base compound. This is
because :-
(i) both O2 and Xe have same size.
(ii) both O2 and Xe have same electron gain enthalpy.
(iii) both O2 and Xe have almost same ionisation enthalpy.
(iv) both Xe and O2 are gases.
15. Which of the following is isoelectronic pair?
(i) ICl2, ClO2 (ii) BrO2– , BrF2+ (iii) ClO2, BrF (iv) CN–, O3
16. Which of the following statements are incorrect?
(i) Among halogens, radius ratio between iodine and fluorine is maximum.
(ii) Leaving F—F bond, all halogens have weaker X—X bond than X—X' bond in interhalogens.
(iii) Among interhalogen compounds maximum number of atoms are present in iodine fluoride.
(iv) Interhalogen compounds are more reactive than halogen compounds.
Answer key :
Q. No. 1 (i) (ii) (iii) (iv) 2 3 4 5 6 7 8
Ans. c a b d B A C A D i iv
Q. No. 9 10 11 12 13 14 15 16
Ans. i i i i i iii ii ii
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1. Write one use of chlorine gas [1]
2. SF6 is much less reactive than SF4. [1]
3. Of the noble gas only xenon is known to form well established chemical compounds. [1]
4. Fluorine does not exhibit any positive oxidation state. Why? [2]
5. Explain the Sulphur has a greater tendency for catenation than oxygen. [2]
6. The halogens are coloured. Why ? [2]
7. HClO4 is a stronger acid than HClO. Why ? [2]
8. (a) Fluorine is a stronger oxidizing agent than chlorine. Why ? [3]
(b) The negative value of electron gain enthalpy of fluorine less than that of chlorine.
(c) Assign reason for the reducting character increases for HF to HI.
9. (a) What happen when Cl2 reacts with excess of F2, ClF3 is formed and not FCl3. [3]
(b) Complete the following reaction :
XeF4 + SbF5 ¾®
(c) XeF2 is linear molecule without a bend. Why ?
10. How is ammonia manufactured industrially? [3]
11.(a) How would you account for the following:
(i) H2S is more acidic than H2O.
(ii) Both O2 and F2 stabilize high oxidation states but the ability of oxygen to stabilize the higher
oxidation state exceeds that of fluorine.
(iii)Bi (V) and Sb (V) which may be a stronger oxidising agent and why?
(b) Draw the structures of the following : [3+2=5]
(i) XeF4 (ii) HClO3
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MOCK TEST SOLUTIONS
1. (i) for bleaching wood pulp (required for manufacture of paper and rayon), cotton and textiles.
(ii) In the metallurgy (extraction) of gold and platinum.
(iii) In the manufacture of dyes, drugs and organic compounds such as CHCl 3, CCl4, DDT, refrigerants
(CCl2F2, freon), and bleaching powder.
(iv) In the preparation of poisonous gases such as phosgene (COCl2), tear gas (CCl3NO2), mustard
gas (ClCH2CH2SCH2CH2Cl), etc. Mustard gas was used by Germany in World War I.
(v) In sterilizing drinking water. (Any one use)
2. In SF6, six F atom protect the sulphur atom from attack by reagents to such an extent that even
thermodynamically most favourable reactions like hydrolysis do not occur.
But in SF4, S is not sterically protected since it is surrounded by only four F atoms, hence SF4 undergoes
hydrolysis.
3. Except radon which is radioactive Xe has least ionisation energy among noble gases and hence it
is readily forms chemical compounds particularly, With oxygen & fluorine.
4. Fluorine is the most electronegative element & cannot exhibit any positive oxidation state.
5. Due to formation of pp -pp multiple bond in case of oxygen. while sulphur forms single covalent
linkage.
6. Due to absorption of radiations invisible region which results in the excitation of outer electrons to
higher energy level.
7. ClO4¯ is more stable than ClO¯ / ClO4¯ is weak conjugate base than ClO¯
8. (a) It is due to (i) low enthalpy of dissociation of F-F bond (ii) high hydration enthalpy of F¯.
(b) The electron gain enthalpy of fluorine is less negative than of chlorine due to the small size of
fluorine atom.
(c) Size of halogen increases / bond length increases /bond dissociation enthalpy decreases (any one)
9. (a) When Cl2 reacts with excess of F2, ClF3 is formed and not FCl3, due to high electronegativity
& small size & absence of higher vacant orbital, fluorine exhibit only -1 oxidation state.
(b) XeF4 + SbF5 ¾® [XeF3]+ [SbF6]¯
(c) Since there are two Xe-F covalent bonds in XeF2. According to VSEPR theory, the shape of
XeF2 is linear.
10. Ammonia is prepared on a large-scale by Haber's process.
2NH3(g)
N2(g) + 3H2(g) DfH° = – 46.1 kJ/mol
The optimum conditions for manufacturing ammonia are :
(i) Pressure (around 200 × 105 Pa)
(ii) Temperature (~700K)
(iii) Catalyst such as iron oxide with small amounts of Al2O3 and K2O.
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11. (a) (i) The size of central atom in H2S is larger than H2O. Hence H2S is more acidic than H2O.
(ii) Size of O > Size of F.
Because oxygen has highest oxidation state is -2 and fluorine has highest oxidation state is -1.
(iii) On moving down the group, the stability of +5 oxidation state decreases while +3 oxidation state
increases due to inert-pair effect. Thus, +5 oxidation state of Bi is less stable then +5 oxidation state
of Sb. Therefore, Bi (V) is stronger oxidising agent than Sb (V).
(b) Structure of compounds
(i) XeF4 (ii) HCl O3
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THE d & f - BLOCK ELEMENTS
l Introduction
d-block elements are present from fourth period onwards. There are mainly three series of the
transition metals – 3d series (Sc to Zn), 4d series (Y to Cd) and 5d series (La to Hg, omitting Ce to Lu).
d-block elements are known as transition elements because their position in the periodic table is
between the s-block and p-block elements. Electronic configuration of the d-block elements is
(n – 1)d1-10ns0–2 but Cu+, Zn, Cd, Hg etc. [(n – 1)d10] are d-block elements, but not transition metals
because these have completely filled d-orbitals.
Transition Metals of d-block Elements
3rd 4th 5th 6th 7th 8th 9th 10th 11th 12th
group group group group group group group group group group
Sc Ti V Cr Mn Fe Co Ni Cu Zn
Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
La Hf Ta W Re Os Ir Pt Au Hg
l General Properties of the Transition Elements

(i) Atomic and Ionic Radii
In transition metals, left to right net nuclear charge increases due to poor shielding effect. Due to this,
the atomic and ionic radii for transition elements for a given series show a decreasing trend for first
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five elements and then becomes almost constant for next five elements of the series.
(ii) Enthalpies of Atomisation
Transition elements exhibit higher enthalpies of atomization because of large number of unpaired
electrons in their atoms. They have stronger interatomic interaction and hence, stronger bond.
(iii) Ionisation Enthalpies
· In a series from left to right, ionization enthalpy increases due to increase in nuclear charge.
· The irregular trend in the first ionization enthalpy of the 3d metals, though of little chemical
significance, can be accounted for by considering that the removal of one electron alters the
relative energies of 4s and 3d orbitals.
(iv) Oxidation States
· Transition metals shows variable oxidation state due to two incomplete outermost shells.
Only stable oxidation states of the first row transition metals are Sc(+ 3), Ti(+ 4), V(+ 5), Cr(+ 3, + 6),
Mn(+ 2, + 7), Fe(+ 2, + 3), Co(+ 2, + 3), Ni(+ 2), Cu(+ 2), Zn(+ 2)
· The transition elements in their lower oxidation states (+ 2 and + 3) usually forms ionic
compounds. In higher oxidation state compounds are normally covalent.
· Only Os and Ru show + 8 oxidation states in their compounds.
· Ni and Fe in Ni(CO)4 and Fe(CO)5 show zero oxidation state.
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Transition elements exhibit variable oxidation state due to small energy difference of ns and (n–1)d
electrons.
· Sc(+3) and Zn(+2) exhibit only one oxidation state
· Common oxidation state is +2
· 3d series highest oxidation state is +7 (Mn)
· In d-block series highest oxidation state is +8 (Os, Ru)
· In carbonyl compound oxidation state of metals is zero due to synergic effects.
· Their higher oxidation states are more stable in fluoride and oxides.
· Higher oxidation states in oxides are normally more stable than fluorides due to capability of oxygen
to form multiple bonds.
eg. stable fluoride in higher ox. st. of Mn is MnF4 while oxide is Mn2O7
· Some more stable oxidation states of d-block elements
Cu +2 Mn +2 Pt +4 Ag +1
Cr +3 Sc +3 Au +3 Ni +2
· Common oxidation states
Ti(+4), V(+5) Cr(+3,+6) Mn(+2,+4,+7)
Fe(+2, +3), Co(+2,+3) Ni (+2) Pt (+2+4)
· In p-block lower oxidation states of heavier elements are more stable while in d-block heavier element,
higher oxidation state are more stable.
eg. In VIB gp Mo(+6) & W(+6) are more stable than Cr(+6)
(v) Trends in the Standard Electrode Potentials
· Transformation of the solid metal atoms to M2+ ions in solution and their standard electrode
potentials.
· If sum of the first and second ionization enthalpies is greater than hydration enthalpy
standard potential (E M° 2+
/M
) will be positive and reactivity will be lower and vice-versa.
(vi) Trends in Stability of Higher Oxidation States

The higher oxidation numbers are achieved in TiX4, VF5 and CrF6. The + 7 state for Mn is not
represented in simple halides but MnO3F is known and beyond Mn no metal has a trihalide
except FeX3 and CoF3 and increasing order of oxidizing power in the series VO2+ < Cr2O72– <MnO4.
(vii) Magnetic Properties
· When a magnetic field is applied to substances, mainly two types of magnetic behavior
are observed : diamagnetism and paramagnetism. Paramagnetism due to presence of
unpaired electrons, each such electron having a magnetic moment associated with its
spin angular momentum.
· The magnetic moment is determined by the number of unpaired electrons.
Magnetic moment = n(n + 2)
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where, n = number of unpaired electrons.
If all electrons are paired, substance will be diamagnetic and magnetic moment will be zero.
(viii) Formation of Coloured Ions
· The d-orbitals are non-degenerated in presence of ligands. When an electron from a lower
energy d-orbital is excited to a higher energy d-orbital, the energy of required wavelength
is absorbed and rest light is transmitted out. Therefore, the colour observed corresponds
to the complementary colour of the light absorbed.
· In V2O5, V is in + 5 oxidation state. It is coloured due to defects in crystal lattice.
· Colour in transition metal ions is associated with d–d transition of unpaired electron from t2g to eg set
of energies.
This is achieved by absorption of light in the visible spectrum, rest of the light is no longer white.
Colourless – Sc3+, Ti4+, Zn2+ etc
Coloured – Fe3+ yellow , Fe2+ green, Cu2+ blue, Co3+ blue etc
(ix) Formation of Complex Compounds
· Transition metals have small size high nuclear charge which facilitates the acceptance of
lone pair of electron from ligands.
· They have vacant d-orbitals of appropriate energy in order to accommodate the lone pair
of electrons.
(x) Catalytic Properties
· Transition metals have two outermost shells incomplete and ability to adopt multiple
oxidation states and to form complexes, therefore used as a catalyst.
· Transition metals also provide larger surface area for the reactant to be adsorbed.
(xi) Formation of Interstitial Compounds
· Small size of non-metals (H, C, N) fit into the voids of crystalline solid of transition
metals and form interstitial compounds.
· The principal physical and chemical characteristics of these compounds are as follows:
(i) They have high melting points, higher than those of pure metals.
(ii) They are very hard, some borides approach diamond in hardness.
(iii) They retain metallic conductivity.
(iv) They are chemically inert.
(xii) Alloy Formation
Alloy is the homogeneous mixture of two or more metals. Transition metals have approximate
same size therefore, in molten form they can fit to each other crystalline structure and form
homogeneous mixture and form the alloy.
E.g., Brass (copper-zinc) and bronze (copper-tin) etc.
l d-block elements—Elments having partially or fully filled d-orbitals in ground or most common
oxidation state are called d-block elements. These are also called transition elemetns because their
properties are intermediate of s-and p-block elements. General electronic configuration of this block
1-10 1-2
is (n - 1) ns .
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l Atomic radius
3d series Sc > Ti > V> Cr >Mn ³ Fe ; CO ; Ni £ Cu < Zn
In a group 3d to 4d series increases but 4d and 5d series nearly same due to poor shielding of f
electron.
(Lanthanide contraction)
3d < 4d ; 5d
Smallest radius – Ni
e.g.% Ti < Zr ; Hf Largest radius – La
l Melting point :s-block metals < d-block metals

In a series on increasing number of unpaired e– mpt increases upto Cr then decreases.
Sc < Ti < V < Cr > Mn < Fe > Co > Ni > Cu > Zn
¯ ¯ Zn > Cd > Hg
Half filled d 5 Fully filled d10 Melting point (data based)
\ weak metallic bond \weak metallic bond Cu > Ag £ Au
E.N. Exception Zn < Cd < Hg

l Density : s-block metals < d-block metals.
3d series Sc < Ti < V < Cr < Mn < Fe < Co £ Ni < Cu > Zn
Density in a Group 3d < 4d << 5d
l Metallic character : They are solid, hard, ductile, malleable, good conductor of heat and electricity
and exhibit metallic lusture, high tensile strength. Hg is liquid
Elect. cond. Ag > Cu > Au > Al
E5555555555F p - block
d - block
10
l Zn, Cdm Hg of group 12 have full d configuratio in their ground state as well as in their common
oxidation states thus, they are not regarded as transition metals.
+
l Cu is unstable in aqueous solution and undergoes disproportionation.
+ 2+
2Cu + ® Cu 2 + + Cu; Cu 2+ is more stabe than Cu due to much more (-) ve DH (hydration) of Cu (aq)
+
than Cu . This is more than requires to compensate high lE2 of Cu.
l Transition elements exhibit colour due to d-d transition, structure defects and charge transfer. Electrons
of lower energy level of d-orbital absorb energy from visible region for excitation to higher level.
l The Inner Transition Elements (f-Block)
The f-block consists of the two series, lanthanoids and actinoids. Lanthanoids are known as rare earth
metals and actinoids are known as radioactive elements (Th to Lr).
Lanthanoids
General characteristics
· General configuration [Xe] 4f1–14, 5d0–1, 6s2.
· Atomic and ionic size from left to right, decreases due to increase in nuclear charge. This is
known as lanthanoid contraction.
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· All the lanthanoids are silvery white soft metals and tarnish rapidly in air.
· Many trivalent lanthanoid ions are coloured both in the solid state and in aqueous solutions.
Neither La3+ nor Lu3+ ion shows any colour but the rest do so.
· The lanthanoid ions other than the f 0 type (La3+ and Ce4+) and the f14 type (Yb2+ and Lu3+) are
all paramagnetic. The paramagnetism arises to maximum in neodymium.
· Oxidation states ® Ce4+; (Some elements) is favoured by its noble gas con
guration, but it is a
strong oxidant reverting to the common + 3 state. The Eovalue for Ce4+/Ce3+ is + 1.74 V, the
reaction rate is very slow and hence, Ce(IV) is a good analytical reagent. Pr, Nd, Tb and Dy
also exhibit + 4 state but only in oxides. Eu2+ is formed by losing the two s-electrons and its f7
configuration accounts for the formation of this ion. However, Eu2+ is a strong reducing agent
changing to the common + 3 state. Similarly, Yb2+ which has f14 configuration is a reductant,
Tb4+ has half-filled f-orbitals and is an oxidant.
· Lanthanoid are very reactive metals like alkaline earth metals.
+O2
M2O 3
+N2
MN
+S
M
Lanthanide metal +C MC2
(M) +X MX3
+H2O M(OH) 3+H2
· Misch metals, contain lanthanoids about 90-95% (Ce 40-5%, Lanthanum and neodymium 44%)
iron 4.5%, calcium, carbon and silicon about 10.5% are used in cigarette and gas lighters, toys,
tank and tracer bullets.
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1. Silver atom has completely filled d orbitals (4d10) in its ground state. How can you say that it is a
transition element?
Ans. The d-orbital now becomes incomplete (4d9) in their common oxidation state. Hence, it is a transition
element.
2. In the series Sc (Z = 21) to Zn (Z = 30), the enthalpy of atomization of zinc is the lowest, i.e., 126 kJ
mol-1. Why?
Ans. Due to the absence of these unpaired electrons, the inter-atomic electronic bonding is the weakest in
Zn.
3. Which of the 3d series of the transition metals exhibits the largest number of oxidation states and
why?
Ans. Mn (Z = 25) = 3d5 4s2
Mn has the maximum number of unpaired electrons present in the d-subshell (5 electrons).
4. The Eº(M2+/M) value for copper is positive (+0.34V). What is possibly the reason for this?
Ans. Copper has a high energy of atomization and low hydration energy. Hence, the Eº(M2+/M) value for
copper is positive.
5. How would you account for the irregular variation of ionization enthalpies (first and second) in the
first series of the transition elements?
Ans. Ionization enthalpies are found to increase in the given series due to a continuous filling of the inner
d-orbitals. The irregular variations of ionization enthalpies can be attributed to the extra stability of
configurations such as d0, d5, d10. Since these states are exceptionally stable, their ionization enthalpies
are very high.
In case of first ionization energy, Cr has low ionization energy. This is because after losing one
electron, it attains the stable configuration (3d5). On the other hand, Zn has exceptionally high first
ionization energy as an electron has to be removed from stable and fully-filled orbitals (3d10 4s2).
Second ionization energies are higher than the first since it becomes difficult to remove an electron
when an electron has already been taken out. Also, elements like Cr and Cu have exceptionally high
second ionization energies as after losing the first electron, they have attained the stable configuration
(Cr+: 3d5 and Cu+: 3d10). Hence, taking out one electron more from this stable configuration will require
a lot of energy.
6. Why is the highest oxidation state of a metal exhibited in its oxide or fluoride only?
Ans. Due to high EN of oxygen and fluorine it easily promote the electron from G.S. to E.S.
7. Which is a stronger reducing agent Cr2+ or Fe2+ and why?
Ans. Cr3+ is stable 3d3 configuration then that of d5 Fe2+
8. Calculate the ‘spin only’ magnetic moment of M2+(aq) ion (Z = 27).
Ans. Z = 27
Þ [Ar] 3d7 4s2
\ M2+ = [Ar] 3d7
3d7 =
i.e., 3 unpaired electrons
\n=3
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Þ µBM= n(n + 2)
Þ µBM = 3(3 + 2)
Þ m BM = 15
µ » 4 BM
9. Explain why Cu+ ion is not stable in aqueous solutions?
Ans. Cu2+ has high HE hence it undergoes disproportionation.
2Cu+ ® Cu2+ + Cu
10. Write down the electronic configuration of :
(i) Cr3+ (ii) Pm3+ (iii) Cu+ (iv) Ce4+
(v) Co2+ (vi) Lu2+ (vii) Mn2+ (viii) Th4+
Ans. (i) Cr3+ : 1s2 2s2 2p6 3s2 3p6 3d3
[Ar]18 3d3
(ii) Pm3+ : 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d10 5s2 5p6 4f4
[Xe]54 4f4
(iii) Cu+1 :1s2 2s2 2p6 3s2 3p6 3d10
[Ar]18 3d10
(iv) Ce4+ : 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d10 5s2 5p6
[Xe]54
(v) Co2+ : 1s2 2s2 2p6 3s2 3p6 3d7
[Ar]18 3d7
(vi) Lu2+: 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d10 5s2 5p6 4f14 5d1
[Xe]54 4f14 5d1
(vii) Mn2+ :1s2 2s2 2p6 3s2 3p6 3d5
[Ar]18 3d5
(viii) Th4+ : 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d10 4f14 5s2 5p6 5d10 6s 2 6p6
[Rn]86
11. Why are Mn2+ compounds more stable than Fe2+ towards oxidation to their +3 state ?
Ans. Electronic configuration of Mn2+ is [Ar]18 3d5. (half filled stability)
Electronic configuration of Fe2+ is [Ar]18 3d6. (After losing one electron it gain half filled stability).
12. Explain briefly how +2 state becomes more and more stable in the first half of the first row transition
elements with increasing atomic number ?
Ans. The oxidation states displayed by the first half of the first row of transition metals are given in the
table below.
Sc Ti V Cr Mn
+2 +2 +2 +2
+3 +3 +3 +3 +3
Oxidation state +4 +4 +4 +4
+5 +5 +6
+6 +7
13. To what extent do the electronic configurations decide the stability of oxidation states in the first
series of the transition elements ? Illustrate your answer with examples.
Ans. The elements in the first - half of the transition series exhibit many oxidation states with Mn exhibiting
maximum number of oxidation states (+2 to +7). The stability of +2 oxidation state increases with the
increase in atomic number. This happens as more electrons are getting filled in the d-orbital.
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14. What may be the stable oxidation state of the transition element with the following d electronic
configurations in the ground state of their atoms : 3d3, 3d5, 3d8 and 3d4 ?
Ans.
Electronic configuration Stable oxidation states
in ground state
(i) 3d3 (Vanadium) +2, +3, +4 and +5

(ii) 3d5 (Chromium) +3, +4, +6
5
(iii) 3d (Manganese) +2, +4, +6, +7
8
(iv) 3d (Cobalt) +2, +3
There is no 3d4 configuration in
(v) 3d4
in ground state.
15. Name the oxometal anions of the first series of the transition metals in which the metal exhibits the
oxidation state equal to its group number.
Ans. (i) Vanadate, VO3– Oxidation state of V is +5.
(ii) Chromate. CrO24- Oxidation state of Cr is +6
(iii) Permanganate, MnO4– Oxidation state of Mn is +7.
16. What is lanthanoid contraction ? What are the consequences of lanthanoid contraction ?
Ans. A regular decrease (contraction) in the atomic and ionic radii of lanthanoides with increasing atomic
number is known as lanthanoid contraction.
Alloy containing lanthanoid metals is mischmetal.
Consequences of lanthanoid contraction
(i) There is similarity in the properties of second and third transition series.
(ii) Separation of lanthanoids is possible due to lanthanide contraction.

(iii) It is due to lanthanide contraction that there is variation in the basic strength of lanthanide hydroxides.
(Basic strength decreases from La (OH)3 to Lu (OH)3.)
17. What are the characteristics of the transition elements and why are they called transition elements ?
Which of the d-block elements may not be regarded as the transition elements ?
Ans. Transition elements are those elements in which the atoms or ions (in stable oxidation state) contain
partially filled d-orbital. These elements lie in the d-block and show a transition of properties between
s-block and p-block. Therefore, these are called transition elements.
Elements such as Zn, Cd and Hg cannot be classified as transition elements because these have
completely filled d-subshell.
18. In what way is the electronic configuration of the transition elements different from that of the non-
transition elements ?
Ans. Transition metals have a partially filled d-orbital and the non-transition elements have a fully filled d-
orbital.
19. What are the different oxidation states exhibited by the lanthanoids ?
Ans. In the lanthanide series, +3 oxidation state is most common i.e., Ln (III) compounds are predominant.
However, +2 and +4 oxidation states can also be found in the solution or in solid compounds.
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20. Explain giving reasons :
(i) Transition metals and many of their compounds show paramagnetic behaviour.
(ii) The enthalpies of atomisation of the transition metals are high.
(iii) The transition metals generally form coloured compounds.
(iv) Transition metals and their many compounds act as good catalyst.
Ans. (i) Due to presence unpaired electrons.
(ii) Transition elements have high effective nuclear charge and a large number of valence electrons.
(iii) This is because of the absorption of radiation from visible light region to promote an electron
from one of the d-orbitals to another.
(iv) Variable oxidation states, large surface area, high effective nuclear charge.
21. What are interstitial compounds ? Why are such compounds well known for transition metals ?
Ans. Transition metals are large in size and contain lots of interstitial sites. Transition elements can trap
atoms of other elements (that have small atomic size), such as H, C, N, in the interstitial sites of their
crystal lattices. The resulting compounds are called interstitial compounds.
These compound are well known for transition metals because small atoms can easily occupy the
position in the void present in the crystal lattice of transition metals.
22. How is the variability in oxidation states of transition metals different from that of the non-transition
metals ? Illustrate with examples.
Ans. In transition elements, the oxidation state can vary from +1 to the highest oxidation state by removing
all its valence electrons. Also, in transition elements, the oxidation states differ by 1 (Fe2+ and Fe3+;
Cu+ and Cu2+). In non-transition elements, the oxidation states differ by 2, for example, +2 and +4 or
+ 3 and +5, etc.
23. For M2+/M and M3+/M2+ systems, the EQ values for some metals are as follows :
Cr2+/Cr – 0.9 V
Cr3/Cr2+ – 0.4V
Mn2+/Mn – 1.2V
Mn3+/Mn2+ + 1.5 V
Fe2+/Fe – 0.4 V
Fe3+/Fe2+ + 0.8V
Use this data to comment upon :
(i) The stability of Fe3+ in acid solution as compared to that of Cr3+ and Mn3+ and
(ii) The ease with which iron can be oxidised as compared to a similar process for either chromium or
manganese metal.
Ans. (i) The EQ value for Fe3+/Fe2+ is higher than that for Cr3+/Cr2+ and lower than that for Mn3+/Mn2+. So,
the reduction of Fe3+ to Fe2+ is easier than the reduction of Cr3+ to Cr2+, but not as easy as the reduction
of Mn3+ to Mn2+. Hence, Fe3+ is more stable than Mn3+, but less stable than Cr3+. These metal ions can
be arranged in the increasing order of their stability as: Mn3+< Fe3+ < Cr 3+
(ii) The reduction potentials for the given pairs increase in the following order.
Mn2+/Mn<Cr2+/Cr < Fe2+/Fe
So, the oxidation of Fe to Fe2+ is not as easy as the oxidation of Cr to Cr2+ and the oxidation of Mn to
Mn2+. Thus these metals can be arranged in the increasing order of their ability to get oxidised :
Fe < Cr < Mn
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24. How would you account for the following :
(i) Of the d4 species, Cr2+ is strongly reducing while manganese(III) is strongly oxidising.
(ii) Cobalt(II) is stable in aqueous solution but in the presence of complexing reagents it is easily oxidised.
(iii) The d1 configuration is very unstable in ions.
Ans. (i) Cr2+ is strongly reducing in nature. It has a d4 configuration. While acting as a reducting agent, it
gets oxidized to Cr3+ (electronic configuration, d3). This d3 configuration can be written as t 32g
configuration, which is a more stable configuration. In the case of Mn3+ (d4), it acts as an oxidizing
agent and gets reduced to Mn2+ (d5). This has an exactly halffilled d-orbital and is highly stable.
(ii) Co(II) is stable in aqueous solutions. However, in the presence of strong field complexing reagents,
it is oxidized to Co(III). Although the 3rd ionization energy for Co is high, but the higher amount of
crystal field stabilization energy (CFSE) released in the presence of strong field ligands overcomes
this ionization energy.
(iii) The ions in d1 configuration tend to lose one more electron to get into stable d0 configuration.
Also, the hydration or lattice energy is more than sufficient to remove the only electron present in the
d-orbital of these ions. Therefore, they act as reducing agents.
25. Which metal in the first series of transition metals exhibit +1 oxidation state most frequently and why?
Ans. In the first transition series, Cu exhibits +1 oxidation state very frequently. It is because Cu (+1) has
an electronic configuration of [Ar] 3d10. The completely filled d-orbital makes it highly stable.
26. Calculate the number of unpaired electrons in the following gaseous ions: Mn3+, Cr3+, V3+ and Ti3+.
Which one of these is most stable in aqueous solution ?
Ans. Gaseous ions Number of uppaired electrons
(i) Mn3+, [Ar]3d4 4
(ii) Cr3+, [Ar] 3d3 3
(iii) V3+, [Ar]3d2 2
(iv) Ti3+[Ar] 3d1 1
Cr3+ is most stable in aqueous solutions owing to a t 32g half filled configuraion.
27. Give examples and suggest reasons for the following features of the tranistion metal chemistry :
(i) The lowest oxide of transition metal is basic, the highest is amphoteric/acidic.
(ii) A transition metal exhibits highest oxidation state in oxides and fluorides.
(iii) The highest oxidation state is exhibited in oxoanions of a metal.
Ans. (i) In the case of a lower oxide of a transition metal, the metal atom has a low oxidation state. This
means that some of the valence electrons of the metal atom are not involved in bonding. As a result,
it can donate electrons and behave as a base.
On the other hand, in the case of a higher oxide of a transition metal, the metal atom has a high
oxidation state. This means that the valence electrons are involved in bonding and so, they are
unavailable. There is also a high effective nuclear charge.
As a result, it can accept electrons and behave as an acid.
For example, MnIIO is basic and Mn2VII O 7 is acidic.
(ii) Oxygen and fluorine act as strong oxidising agents because of their high electronegatives and
small sizes. Hence, they bring out the highest oxidation states from the transition metals. In other
words, a transition metal exhibits higher oxidation states in oxides and fluorides. For example, in
OsF6 and V2O5, the oxidation states of Os and V are +6 and +5 respectively.
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(iii) Oxygen is a strong oxidising agent due to its high electronegativity and small size. So, oxo-anions of a metal
have the highest oxidation state. For example, in MnO4–, the oxidation state of Mn is +7.
28. What are alloys ? Name an important alloy which contains some of the lanthanoid metals. Mention its uses.
Ans. An alloy is a solid of two or more elements in a metallic matrix. It can either be a partial solid solution
or a complete solid solution. Alloys are usually found to possess different physical properties than
those of the component elements.
An important alloy of lathanoids is Mischmetal. It contians lanthanoids (94-95%), iron (5%), and
traces of S, C, Si, Ca and Al.
Uses:
(1) Mischmetal is used in cigarettes and gas lighters.
(2) It is used in flame throwing tanks.
(3) It is used in tracer bullets and shells.
29. Account for the following%
(i) Zn is not considered as a transition element.
(ii) Transition metals form a large number of complexes.
(iii) The Eº value for the Mn 3+ /Mn2+ couple is much more positive than that for Cr3+ /Cr2+ couple.
Ans. (i) Zn, cannot be classified as transition elements because these have completely filled d-subshell.
In their ground state as well as in their common oxidation state.
(ii) Due to high nuclear charge presence of vacant d-orbital and variable oxidation state it have
great tendency to from complex.
(iii) Due to high sum of first two consquetive (IP1 + IP2).
30. (i) Name a member of the lanthanoid series which is well known to exhibit + 4 oxidation state.
(ii) Out of Mn3+ and Cr3+ , which is more paramagnetic and why ?
(Atomic nos. : Mn = 25, Cr = 24)
Ans. (i) Ce+4
(ii) Mn+3 due to four unpaired electron in their 3d orbital.
31. Give reasons for the following:
Although ‘F’ is more electronegative than ‘O’. the highest Mn fluoride In MnF4,
whereas the highest oxide is Mn2O7.
Ans. This is because F can form only one bond and structure of MnF4 which is tetrahedral but
F
F Mn F
F
In Mn2O7 as 0 is present which can form 2s bonds or 1s and 1p bond so 0 can be present in
between two Mn atoms giving it a structure.
O O
Mn Mn
O O O
O
O
Such budge cannot

be formed by F
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32. (a) Why do transition elements show variable oxidation states?
(i) Name the clement showing maximum number of oxidation states among the first series of tran-
sition metals from Sc (Z = 21) to Zn (Z = 30).
(ii)Name the element which shows only +3 oxidation state.
Ans. (a) Transition elements have d orbitals which can accommodate a maximum of 10 electrons so there
is more scope for loss of any number of electron resulting into variable oxidation states.
(i) Mn shows maximum number of oxidization states.
(ii) Sc shows only +3
33. How would you account for the following
(i) Among lanthanoids, Ln(III) compounds are predominant. However, occasionally in solutions
or in solid compounds, +2 and +4 ions are also obtained.
(ii) The E°M2+ / M for copper is positive (0.34 V). Copper is the only metal in the first series of
transition elements showing this behaviour.
(iii) The metallic radii of the third (5d) series of transition metals are nearly the same as those
of the corresponding members of the second series.
Ans. (i) This irregularity arises mainly from the extrastability of empty, halffilled or filled f subshell.
(ii) B'coz of high atomisation and low hydration enthalpy.
(iii) Poor shielding effect of 4f electrons known as Ln contraction.
34. Explain the following observations:
3+ 3+
(i) La (Z = 57) and Lu (Z = 71) do not show any colour in solutions.
(ii) Among the divalent cations in the first series of transition elements, manganese exhibits the
maximum paramagnetism.
Ans. (i) Because they have empty outer most shell.
2+
(ii) Mn has maximum number of unpaired electrons
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1. Out of the following transition elements, the maximum number of oxidation states are shown by
(CBSE 2020)
(A) Sc (Z = 21) (B) Cr (Z = 24) [1]
(C) Mn (Z = 26) (D) Fe (Z = 26)
Ans. (C)
2. (a) Account for the following : (CBSE 2020)
(i) Copper (I) compounds are white whereas Copper (II) compounds are coloured. [1×3=3]
(ii) Chromates change their colour when kept in an acidic solution.
(iii) Zn, Cd, Hg are considered as d-block elements but not as transition elements.
(b) Calculate the spin-only moment of Co2+ (Z=27) by writing the electronic configuration of Co
and Co2+
OR
(a) Give three points of difference between lanthanoids and actinoids. [3]
(b) Give reason and select one atom/ion which will exhibit asked property : [1×2=2]
(i) Sc+3 or Cr3+ (Exhibit diamagnetic behaviour)
(ii) Cr or Cu (High melting and boiling point)
Ans. (a) (i) Cu+1 (3d10) compounds are white because of absence of unpaired electrons while Cu+2 (3d9)
compounds are coloured due to unpaired e-/shows d-d transition.
(ii) chromate (CrO42–) changes to dichromate (Cr2O72-) ion in acidic medium.
(iii) due to completely filled d-orbitals in their ground state as well as in oxisized state.
(b) Co = [Ar]4s23d7, Co+2 = [Ar]3d7
m = n(n + 2)
= 3(3 + 2) = 15 = 3.92 B.M.
OR
(a)
Lanthanoids Actinoids
(1) most of them are not radioactive All are radioactive
(2) don't show a wide range of oxidation state Show a wide range of oxidation states
(3) Most of their ions are colourless Most of their ions are coloured
(b) (i) Sc+3, because of absence of unpaired electron
(ii) Cr, because of presence of strong intermetallic bonding than Cu.
3. When FeCr2O4 is fused with Na2CO3 in the presence of air it gives a yellow solution of compound
(A). Compound (A) on acidification gives compound (B). Compound (B) on reaction with KCl
forms an orange coloured compound (C). An acidified solution of compound (C) oxidises Na2SO3 to
(D). Identify (A), (B), (C) and (D). [2]
(CBSE 2019)
Ans. A = Na2CrO4 ; B = Na2Cr2O7 ; C = K2Cr2O7 ; D = Na2SO4
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4. Give reasons for the following : [3]
(a) Transition metals form complex compounds. (CBSE 2019)
(b) E° values for (Zn 2+ / Zn) and (Mn2+ / Mn) are more negative than expected.
(c) Actinoids show wide range of oxidation states.
Ans. (a) Due to small size, high ionic charge and availability of d-orbital
(b) Due to stable 3d10 configuration in Zn2+ and 3d5 configuration in Mn2+.
(c) Due to comparable energies of 5f, 6d and 7s orbitals/level
5. Give reasons for the following : [3]
(a) Transition metals have high enthalpies of atomization. (CBSE 2019)
(b) Manganese has lower melting point even though it has a higher number of unpaired electrons
for bonding.
(c) Ce4+ is a strong oxidising agent.
Ans. (a) Because of strong interatomic interactions/strong metallic bonding between atoms.
(b) Due to stable 3d5 configuration, interatomic interaction is poor between unpaired electrons.
(c) Because Ce is more stable in +3 oxidation state.
6. Give reasons : (CBSE 2018)
(a) E0 value for Mn3+/Mn2+ couple is much more positive than that for Fe3+/Fe2+.
(b) Iron has higher enthalpy of atomization than that of copper.
(c) Sc3+ is colourless in aqueous solution whereas Ti3+ is coloured.
Ans. (a) E° value for Mn3+/Mn2+ couple is much more positive than that for Fe3+/Fe2+, due to the Mn2+
have higher stability than M3+ due to half filled d5 configuration.
(b) Iron has higher enthalpy of atomization than that of copper because Iron has higher number of
unpaired e– than Cu due to which extent of covalent bonding is more.
(c) Sc3+ is colourless is due to the absence of unpaired e– as it attains 3d° configuration while Ti+3
has 3d1-configuration
7. Complete and balance the following chemical equations : (CBSE 2018)
(a) Fe 2+ + MnO-4 + H + ¾¾
®
(b) MnO-4 + H 2O + I- ¾¾
®
Ans. 5Fe2+ + MnO4- + 8H+ ® Mn 2+ + 4H2O + 5Fe+3
2MnO -4 + H 2O + I- ® 2MnO2 + 2OH - + IO3-

8. (a) Account for the following : (CBSE 2017)
(i) Transition metals show variable oxidation states.
(ii) Zn, Cd and Hg are soft metals.
(iii) Eo value for the Mn3+/Mn2+ couple is highly positive (+1.57 V) as compared to Cr3+/Cr2+
(b) Write one similarity and one difference between the chemistry of lanthanoid and actinoid elements.
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OR
(a) Following are the transition metal ions of 3d series :
Ti4+, V2+, Mn3+, Cr3+
(Atomic numbers : Ti = 22, V =23, Mn = 25, Cr = 24)
Answer the following :
(i) Which ion is most stable in an aqueous solution and why ?
(ii) Which ion is a strong oxidising agent and why ?
(iii) Which ion is colourless and why ?
(b) Complete the following reactions :
(i) 2MnO4– + 16H+ + 5 S2– ¾®
(ii) KMnO4 ¾¾ ¾
heat
®
Ans. (a) (i) Availability of partially filled d-orbitals/comparable energies of ns and (n-1) d orbitals
(ii) Completely filled d-orbitals/absence of unpaired d electrons cause weak metallic bonding
(iii) Because Mn2+ has d5 as a stable configuration whereas Cr3+ is more stable due to stable t32g
(b) Similarity-both are stable in +3 oxidation state/both show contraction/irregular electronic
configuration (or any other suitable similarity) Difference-actinoids are radioactive and
lanthanoids are not/actionoids show wide range of oxidation states but lanthanoids don't
(or any other orrect difference)
OR
(a) (i) Cr3+, half filled t32g
(ii) Mn3+, due to stable d5 configuration in Mn2+
(iii) Ti4+, No unpaired electrons
(b) (i) 2MnO4– + 16H+ + 5S2– ® 2Mn2+ + 8H2O
(ii) 2KMnO4 ® K2MnO4 + MnO2 + O2
9. (a) Account for the following (CBSE 2016)
(i) Mn shows the highest oxidation state of +7 with oxygen but with fluorine it shows the highest oxidation
state of +4.
(ii) Zirconium and Hafnium exhibit similar properties.
(iii) Transition metals act as catalysts.
(b) Complete the following equations:
D
(i) 2MnO2 + 4KOH + O2 ¾¾ ® (ii) Cr2O72- + 14H+ + 6I– ¾¾®
Ans. (a) (i) Ability of oxygen to form multiple bond .
(ii) Due to lanthanoid contraction.
(iii) Due to variable oxidation state/unpaired electrons
(b) (i) 2MnO2 + 4KOH + O2 ® 2K2MnO4+ 2H2O
(ii) Cr2O72 – + 14 H+ +6I– ® 2Cr3++ 7H2O + 3I2
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10. The elements of 3d transition series are given as: (CBSE 2016)
Answer the following:
(i) Write the element which is not regarded as a transition element. Give reason.
(ii)Which element has the highest m.p ?
(iii) Write the element which can show an oxidation state of +1.
(iv) Which element is a strong oxidizing agent in +3 oxidation state and why ?
Ans. (i) Zn, because of not having partially filled d-orbital in its ground state or ionic state.
(ii) Cr
(iii) Cu
(iv) Mn, because Mn+2 has extra stability due to half filled d-orbital
11. (i) E0 value for the Mn3+/Mn2+ couple is positive (+ 1.5 V) whereas that of Cr3+/Cr2+ is negative (– 0.4 V). Why?
(ii) Transition metals form coloured compounds. Why? (CBSE 2015)
(iii) Complete the following equation :
2MnO–4 + 16 H+ + 5C2O2–4 ®
Ans. (i) The large positive E0 value for Mn3+ / Mn2+ shows that Mn2+ (3d5 / half filled d orbital) is much
more stable than Mn3+ Whereas Cr3+ (t2g3 ) is more stable than Cr2+
(ii) Due to d – d transition / due to presence of unpaired electrons in d – orbitals which absorb light in
visible region
(iii) 2MnO4– + 16H+ + 5C2O42– ® 2Mn2+ + 8H2O + 10CO2
12. Why do transition elements show variable oxidation states? How is the variability in oxidation states
of d-block different from that of the p-block elements? (CBSE 2015)
Ans. Due to comparable energies of ns & (n–1)d orbitals / due to presence of unpaired electrons in (n–1)d orbitals.
In transition elements, oxidation states differ from each other by unity whereas in case of p- block
elements, the oxidation states differ by units of two / In transition elements, the higher oxidation states
are more stable for heavier elements in a group. In p – block elements, the lower oxidation states are
more stable for heavier members due to inert pair effect. (Any one difference)
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EXERCISE-3 R AC E
The d-block of the periodic table contains the elements of the groups 3 – 12 and are known as transition
elements. In general, the electronic configuration of these elements is (n – 1) d1–10 ns1–2. The d-orbitals
of the penultimate energy level in their atoms receive electrons giving rise to the three rows of the
transition metals i.e., 3d, 4d and 5d series. However, Zn, Cd and Hg are not regarded as transition
elements. Transition elements exhibit certain characteristic properties like variable oxidation states,
complex formation, formation of coloured ions and alloys, catalytic activity, etc. Transition metals are
hard (except Zn, Cd and Hg) and have a high melting point.
(i) Zn, Cd and Hg non-transition elements due to :-
10 5 3 3 2
(a) Full filled nd (b) Half filled nd (c) nd orbital (d) t2g eg
(ii) Which transition metal of 3d series does not show variable oxidation states ?
(a) Zn (b) Sc (c) Mn (d) Cr
(iii) The melting points of transition metals are high ?
(a) Unpaired electrons (b) Paired electrons
2+ 2+
(iv) Cu ion coloured while Zn ion is colourless in aqueous solution due to :-
–
(a) e jump from eg to t2g (b) d-d transition
2. Assertion : Cu2+ iodide is not known.
Reason : Cu2+ oxidises I– to iodine.
3. Assertion : Transition metals have low melting points.
Reason : The involvement of greater number of (n – 1)d and ns electrons in the interatomic metallic
bonding.
4. Assertion : Separation of Zr and Hf is difficult.
Reason : Because Zr and Hf lie in the same group of the periodic table.
5. Assertion : Cu cannot liberate hydrogen from acids.
Reason : Because it has positive electrode potential.
6. Assertion : The highest oxidation state of osmium is +8.
Reason : Osmium is a 5d-block element
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7. Electronic configuration of a transition element X in +3 oxidation state is [Ar]3d5. What is its atomic
number?
(i) 25 (ii) 26 (iii) 27 (iv) 24
8. Which of the following oxidation state is common for all lanthanoids?
(i) +2 (ii) +3 (iii) +4 (iv) +5
9. Transition elements show magnetic moment due to spin and orbital motion of electrons. Which of the
following metallic ions have almost same spin only magnetic moment?
(i) Co3+ (ii) Cr2+ (iii) Mn2+ (iv) Cr3+
10. Which of the following statements is not correct?
(i) Copper liberates hydrogen from acids.
(ii) In its higher oxidation states, manganese forms stable compounds with oxygen and fluorine.
(iii) Mn3+ and Co3+ are oxidising agents in aqueous solution.
(iv) Ti2+ and Cr2+ are reducing agents in aqueous solution.
11. Interstitial compounds are formed when small atoms are trapped inside the crystal lattice of metals.
Which of the following is not the characteristic property of interstitial compounds?
(i) They have high melting points in comparison to pure metals.
(ii) They are very hard.
(iii) They retain metallic conductivity.
(iv) They are chemically very reactive.
12. The electronic configuration of Cu(II) is 3d9 whereas that of Cu(I) is 3d10. Which of the following is
correct?
(i) Cu(II) is more stable
(ii) Cu(II) is less stable
(iii) Cu(I) and Cu(II) are equally stable
(iv) Stability of Cu(I) and Cu(II) depends on nature of copper salts
13. The magnetic nature of elements depends on the presence of unpaired electrons. Identify the
configuration of transition element, which shows highest magnetic moment.
(i) 3d7 (ii) 3d5 (iii) 3d8 (iv) 3d2
14. Which of the following is amphoteric oxide?
Mn2O7, CrO3, Cr2O3, CrO, V2O5, V2O4
(i) V2O5, Cr2O3 (ii) Mn2O7, CrO3 (iii) CrO, V2O5 (iv) V2O5, V2O4
15. Transition elements form binary compounds with halogens. Which of the following elements will
form MF3 type compounds?
(i) Cr (ii) Co (iii) Cu (iv) Ni
16. Generally transition elements form coloured salts due to :-
(i) presence of unpaired e– (ii) Presence of paired e–
(iii) Both (i) & (ii) (iv) None of these
Answer key :
Q. No. 1 (i) (ii) (iii) (iv) 2 3 4 5 6 7 8
Ans. a b a b A D B A B ii ii
Q. No. 9 10 11 12 13 14 15 16
Ans. iv i iii i ii i ii i
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1. Mn3+ is a good oxidizing agent. Why ? [1]
2. Name a member of the lanthanoid series which is well known to exhibit + 4 oxidation state. [1]
3. Transition metals form a large number of complexes. [1]
4. Although ‘F’ is more electronegative than ‘O’. the highest Mn fluoride In MnF4, whereas the highest
oxide is Mn2O7. Why ? [2]
5. Out of Mn3+ and Cr3+ , which is more paramagnetic and why ? (Atomic nos. : Mn = 25, Cr = 24) [2]
6. (a) Transition metals form coloured compounds. Why? [2]
(b) Transition metals act as catalysts.
7. (a) Mn shows the highest oxidation state of +7 with oxygen but with fluorine it shows the highest
oxidation state of +4. [2]
(b) Copper (I) compounds are white whereas Copper (II) compounds are coloured.
8. The elements of 3d transition series are given as: [3]
Answer the following:
(i) Write the element which is not regarded as a transition element. Give reason.
(ii) Which element has the highest m.p ?
(iii) Write the element which can show an oxidation state of +1.
9. Following are the transition metal ions of 3d series : [3]
Ti4+, V2+, Mn3+, Cr3+
(Atomic numbers : Ti = 22, V =23, Mn = 25, Cr = 24)
Answer the following :
(i) Which ion is most stable in an aqueous solution and why ?
(ii) Which ion is a strong oxidising agent and why ?
(iii) Which ion is colourless and why ?
(a) E0 value for Mn3+/Mn2+ couple is much more positive than that for Fe3+/Fe2+.
(b) Iron has higher enthalpy of atomization than that of copper.
(c) Sc3+ is colourless in aqueous solution whereas Ti3+ is coloured.
11. (a) Account for the following : [5]
(i) Transition metals show variable oxidation states.
(ii)Zn, Cd and Hg are soft metals.
(iii) Eo value for the Mn3+/Mn2+ couple is highly positive (+1.57 V) as compared to Cr3+/Cr2+
(b) Write one similarity and one difference between the chemistry of lanthanoid and actinoid
elements.
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MOCK TEST SOLUTIONS
1. Mn3+ easily changes to Mn2+ and Mn2+ is more stable due to half filled d5 configuration and hence
Mn3+ is oxidising.
2. Ce+4
3. Due to high nuclear charge presence of vacant d-orbital and variable oxidation state it have great
tendency to from complex.
4. This is because F can form only one bond and structure of MnF4 is which is which is tetrahedral
but
F
F Mn F
F
In Mn2O7 as 0 is present which can form 2 s bonds or 1s and 1p bond so 0 can be present in between
two Mn atoms giving it a structure.
O O
Mn Mn
O O O
O
O
Such budge cannot

be formed by F
5. Mn+3 due to four unpaired electron in their 3d orbital.
6. (a) Due to d - d transition / due to presence of unpaired electrons in d - orbitals which absorb light
in visible region.
(b) Due to variable oxidation state/unpaired electrons.
7. (a) Ability of oxygen to form multiple bond.
(b) Cu+1 (3d10) compounds are white because of absence of unpaired electrons while Cu+2 (3d9)
compounds are coloured due to unpaired e¯/shows d-d transition.

8. (i) Zn, because of not having partially filled d-orbital in its ground state or ionic state.
(ii) Cr
(iii) Cu
9. (i) Cr3+, half filled t32g
(ii) Mn3+, due to stable d5 configuration in Mn2+
(iii) Ti4+, No unpaired electrons
10. (a) E° value for Mn3+ / Mn2+ couple is much more positive than that for Fe3+ / Fe2+, due to the Mn2+
have higher stability than M3+ due to half filled d5 configuration.
(b) Iron has higher enthalpy of atomization than that of copper because Iron has higher number of
unpaired e¯ than Cu due to which extent of covalent bonding is more.
(c) Sc3+ is colourless is due to the absence of unpaired e¯ as it attains 3d° configuration while Ti+3
has 3d1-configuration
11. (a) (i) Availability of partially filled d-orbitals/comparable energies of ns and (n-1) d orbitals
(ii) Completely filled d-orbitals/absence of unpaired d electrons cause weak metallic bonding
(iii) Because Mn2+ has d5 as a stable configuration whereas Cr3+ is more stable due to stable t32g
(b) Similarity-both are stable in +3 oxidation state/both show contraction/irregular electronic
configuration (or any other suitable similarity) Difference-actinoids are radioactive and lanthanoids
are not/actionoids show wide range of oxidation states but lanthanoids don't (or any other orrect
difference)
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COORDINATION COMPOUNDS
l Complex Compound
Representation of coordination compound
K4 [Fe(CN)6] C.N.
(coordination no.)
Ionisation sphere / Counter Ion
Coordination sphere / Entity
Central metal atom/ion
Ligand
l Double salts—are the addition compounds that lose their identity in solution. They exist only in solid
state and have properties same as those of constituent compounds,
e.g. Mohr's salt FeSO4. (NH4)2SO4. 6H2O, Potash alum K2SO4. Al2 (SO4)3 24H2O
l Coordination compounds or complexes—don't completely lose their identity in solution. They exist
in solid state as well as in solution. Their properties are different from their constituents.
l denticity—The number of donor sites present in a ligand is called their denticity e.g. en (ethylene
4–
diamine) is a bidentate (didnetate) ligand and EDTA is a hexadentate ligand.
Monodentate : have only one donor sites.
Eg. H2O, NH 3
Bidentate : Contain two donor sites.
Eg. CH2=CH2, COO—
|
COO—
l Co-ordination compound are the compounds in which the central metal atom is linked to a number
of ions are neutral molecules by co-ordinate bond.
l Ligand : The donar atoms, molecules or ions which donate a pair of electrons to the metal atom and
form a co-ordinate bond with it are called ligands.
node06\B0B0-BA\Kota\Board Material\Chemistry\CBSE\CBSE Booklet\English\Updated booklet-21\New Pattern CBSE Booklet\Part wise boocklet\Part 1\02_IOC\08_Coordination Compound.p65
l Ambidentate ligand : Unidentate ligands with more than one co-ordinating atoms. e.g.
–CN—, and –NC—, –SCN— and –NCS—, NO2 — and ONO—, –OCN— and NCO—.
These ligands are responsible for linkage isomerism.
l Polydentate ligand : Those ligands which possess two or more than two donar atoms which can
4–
link to metal ions are called polydentate ligands. e.g. EDTA . (ethylene diamine tetra acetate) ion
hexadentate ligand.
l Chelating ligand: These are the polydentate ligands which bind to the central metal to form a puckered
ring structure. Chelation leads to extra stability, for example, EDTA (ethylene diamine tetra acetate).
l On the basis of crystal field splitting energy (CFSE) ligands are of 2 types –
(1) Strong ligands : They possess high CFSE values e.g. –CO, CN, NH3, H2O etc.
– – – –
(2) Weak ligands : They possess less CFSE values e.g. –F , Cl , Br , I etc.
LIGANDS
On the basis On the basis On the basis of

of charge of denticity lp donation/accepting e —s
Neutral Monodentate
Classical Non-classical
Anionic Bidentate
Cationic Polydentate
Flexidentate —
pe p acid
Ambidentate donating ligand ligand
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l The colour of coordination compounds can be explained on the basis of d-d transition.
l Carbonyl complexes : Complexes made by metals and carbonyl ligands are called carbonyl complex
e.g., [Ni(CO)4], [Fe(CO)5], [Cr(CO)6]. etc. In metal carbonyl complex both s and p M—C bonds
are present. L ® M is s bond while M ® L is p bond.
l Importance and applications of co-ordination compounds.
1. Co-ordination compounds are used in purification of metals.
2. In biological systems like Vitamin B-12 cyanocobalamine is a complex of cobalt metal. cis-Platin
is used to treat cancer is a complex of platinum.
3. In photography, hypo solution is used to remove additional AgBr.
AgBr + 2Na2S2O3 ¾® Na3 [Ag(S2O3)2] + NaBr
l Bonding in Coordination Compounds
l Werner.s Theory
(i) In complex compounds, metal atom exhibit two types of valencies. primary valency and
secondary valency.
Primary valency Secondary Valency
It is oxidation no. of metal. It is coordination number
It is variable It is non variable.
Satisfied by anions (present in Satisfied by ligands
coordination or ionisable sphere). (present in coordination sphere)
Ionisable Nonionisable
Ionic \ nondirectional Directional \ decide geometry
of complex ion.
Represented by dotted line in Represented by solid lines in
Werner structure. Werner structure.
NH 3 Cl
H 3N
COCl3.4NH3 [Co(NH3)4Cl2]Cl 3 do tte d lin e sh o ws -
Eg. Co Cl Primary Valence
Molecular formula complex formula
H3 N 6 so lid lin e sh o ws -
NH 3 Cl Seco n da ry Valen ce
Werner structure
l Valence Bond Theory
According to this theory, the metal atom or ion under the influence of ligands form inner orbital and
outer orbital complex. These hybridized orbitals are allowed to overlap with ligand orbitals that can
donate electron pairs for bonding.
(i) Six ligands (unidentate) (octahedral entity) Generally central atom belongs 3d series and
ligands can be monodentate or didentate but coordination number should be six and shape of
complexes will be octahedral and form two types of complexes.
(a) Inner orbital complexes, which are formed due to participation of (n –1)d orbitals in
hybridisation is (d2sp3) and shape of complex will be octahedral.
(b) Outer orbital complexes, which are formed due to participation of nd orbitals in
hybridisationis (sp3d2).
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Coorination No. Type of hybrid orbital
2 sp
2
3 sp
square planar -dsp2
4
tetrahedral -sp3
dsp3
5
sp3d
sp3d2 - outer orbital complex (high spin)
6
d2sp3 - inner orbital complex (low spin)
Coordination No. 4: Example

[NiCl4]2— sp3 -----Tetrahedral
2— 2
[Ni(CN)4] dsp ----- Square planar
[Ni(CO) 4] sp3 -----Tetrahedral
2+ 3
[Zn(NH3)4] sp -----Tetrahedral
[Cu(NH3)4] 2+ dsp2 -----Square planar
Coordination No. 6 : Example
4— 2 3
[Fe(CN)6] d sp
3— 2 3
[Fe(CN) 6] d sp
[Co(NH 3) 6] 3+ d sp3
2
[Ni(H2O)6]2+ sp3d2
l Crystal Field Theory
The five d-orbitals are split into lower and higher energy level due to approach of ligands is known as
crystal field theory. The five d-orbitals in a gaseous metal atom/ion have same energy.
l The splitting of five degenerate d-orbitals of the metal into different sets of orbitals having different
energies in the presence of electrostatic field of ligands is called crystal field splitting.
egset – dx2–y2 , dz2 t2g set – dxy, dyz, dxz
l Crystal field splitting energy, (D0 for octahedral structure and Dt =4/9D0 tetrahedral structure) is the
difference between the various sets of energy levels formed by crystal field splitting.
l Weak field ligands are those ligands which cause a small degree of crystal field splitting
e.g. I¯, Br¯, Cl¯, F¯, OH¯, C2O42¯, H2O, etc.
l Strong field ligands are those ligands which cause a high degree of splitting e.g. CO, CN–, NO2–,
etc. Spectrochemical series
I¯ < Br¯< Cl¯ < NO3¯ < F¯ < OH¯ < ox2– < H2O < py ~ en < dipy < o-phen < NO2¯ < CN¯ < CO.
( C and N donar act as SFL except N3¯)
(i) Crystal field splitting in octahedral coordination entities.

· Energy separation is denoted by Do (the subscript o is for octahedral).
· The energy of the two eg orbitals (higher energy orbitals) will increase by (3/5)Do and that
of the three t2g (lower energy orbitals) will decrease by (2/5)Do.
· If Do < p, the fourth electron enters one of the eg, orbitals giving the configuration t 32g e1g .
Ligands for which Do < p are known as weak field ligands and form high spin complexes.
· If Do > p, it becomes more energetically favourable for the fourth electron to occupy a t2g
orbital with configuration t 42g eg . Ligands which produce this effect are known as strong
field ligands and form low spin complexes, where p represents the energy required for
electron pairing in a single orbital.
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(ii) Crystal field splitting in tetrahedral coordination entities.
· In tetrahedral coordination entities, Dt = (4/9)Do. Consequently the orbital splitting energies
are not sufficiently large for forcing pairing and, therefore, low spin configurations are rarely
observed.
· Due to less crystal field stabilization energy, it is not possible to pair electrons and so all
the tetrahedral complexes are high spin.
4
· The value of Dt (CFSE for tetrahedral complexes) for tetrahedral complexes is D t = D 0
9
l Coordination number—The total number of ligands to which the metal is directly attached is called
3+
coordination number (C.N) e.g. [Co(NH3)6] , C.N. = 6
3+
[Co(en3)] , C.N. = 3 × 2 = 6 (Q en is bidentate)
l According to CFT, degenerate d-orbitals in the presence of ligand split up into two sets of energy
viz t2g and eg set.
l Crystal Field Stabilisation Energy—The diffenrence of energy between the two sets of degenerated
orbitals (as a result of crystal field splitting) is known as crystal Field Stabilisation Energy (CFSE).
It is denoted by D0 (for octahedral complex).
IUPAC nomenclature of complex compounds :

(A)For anionic complex (like K4[Fe(CN)6])
Common name of normal cation (without numeral prefix) + name of ligands (with numeral prefix)
+ latin name of CMI along with suffix ate + Ox. St (in roman number).
eg. : Potassium hexacyanoferrate (II)

(B) For cationic comlex like [Cu(NH3)4]SO4
Name of ligands (with numeral prefix) + Common name of CMI + Ox. St (In roman number) + Name
of anion (without numeral prefix)
eg. : Tetraammine copper (II) sulphate.
(C) For neutral complex (like [Fe(CO)5)
Name of ligands (with numeral prefix)
+ Common name of CMI + Ox. St.
(In roman number)
eg. : Pentacarbonyl iron (O)
(D)Rule same just apply alphabetical order when write the name of ligands.
e.g. [Pt(NH3)2Cl2]
Diamminedichloroplatinum (II)
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1. Write the formulas for the following coordination compounds:
(i) Tetraamminediaquacobalt(III) chloride
(ii) Potassium tetracyanonickelate(II)
(iii) Tris(ethane-1,2-diamine) chromium(III) chloride
(iv) Amminebromidochloridonitrito-N-platinate(II)
(v) Dichloridobis(ethane-1,2-diamine)platinum(IV) nitrate
(vi) Iron(III) hexacyanoferrate(II)
Ans. (i) [CO(H2O)2 (NH3)4]Cl3
(ii) K2[Ni(CN)4 ]
(iii) [Cr(en)3]Cl3
(vi) [Pt(NH)3BrCl(NO2)]–
(v) [PtCl2(en)2](NO3)2
(vi) Fe[Fe(CN)6]3
2. Write the IUPAC names of the following coordination compounds:
(i) [Co(NH3)6]Cl3
(ii) [Co(NH3)5Cl]Cl2
(iii) K3[Fe(CN)6]
(iv) K3[Fe(C2O4)3]
(v) K2[PdCl4]
(vi) [Pt(NH3)2Cl(NH2CH3)]Cl
Ans. (i) Hexaamminecobalt(III) chloride
(ii) Pentaamminechloridocobalt(III) chloride
(iii) Potassium hexacyanoferrate(III)
(iv) Potassium trioxalatoferrate(III)
(v) Potassium tetrachloridopalladate(II)
(vi) Diamminechlorido(methylamine)platinum(II) chloride
3. Explain on the basis of valence bond theory that [Ni(CN)4]2– ion with square planar structure is
diamagnetic and the [NiCl4]2– ion with tetrahedral geometry is paramagnetic.
Ans. In tetrahedral complexes the hybridisation involved is sp3. In [NiCl4]2–, nickel is in +2 oxidation state and
the ion has the electronic configuration 3d8.
Each Cl– ion donates a pair of electrons Cl – being a weak ligand is unable to pair up the unpaired
electrons. The compound is paramagnetic.
In the square planar complexes, the hybridisation involved is dsp2. In [Ni(CN)4]2–, nickel is in +2 oxidation
state and has the electronic configuration 3d8.
Each of the hybridised orbitals receives a pair of electrons from a cyanide ion. CN¯ being a strong ligand
is pair up the unpaired electrons. The compound is diamagnetic due to the absence of unpaired electron.
4. [NiCl4]2– is paramagnetic while [Ni(CO)4] is diamagnetic though both are tetrahedral. Why?
Ans. In Ni(CO)4 Ni is in zero oxidation state whereas in NiCl 42–, it is in +2 oxidation state. In the presence
of CO ligand, the unpaird d electrons of Ni pair up but Cl¯ being a weak ligand is unable to pair up
the unpaired electrons.
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5. [Fe(HO2)6]3+ is strongly paramagnetic whereas [Fe(CN)6]3– is weakly paramagnetic. Explain ?
Ans. In both , [Fe(H2O)6]3+ and [Fe(CN)6]3– , Fe exists in the +3 oxidation state i.e., in d5 configuration.
d5
Since CN– is a strong field ligand, it causes the pairing of unpaired electrons. Therefore, there is only
one unpaired electron left in the d-orbital.
eg
Therefore, For
m = n(n + 2) SFL
5
d D0>P
= 1(1 + 2) (n = 1) (Fe+3)
= 3 = 1.732 BM
–t2g–
On the other hand, H2O is a weak field ligand. Therefore, it cannot cause the pairing of electrons.
This means that the number of unpaired electrons is 5.
Therefore,
eg
m = n(n + 2) For
WFL
D0<P
5
d
= 5(5 + 2) (\n=5)
tg
= 35 = 6 BM
Thus, it is evident that [Fe(H2O)6]3+ is strongly paramagnetic, while [Fe(CN)6]3– is weakly paramagnetic.
6. Explain [Co(NH3)6]3+ is an inner orbital complex whereas [Ni(NH3)6]2+ is an outer orbital complex.
Ans. In the presence of NH3, the 3d electrons pair up leaving two d orbitals empty to be involved in the
d2sp3 hybridisation formaing inner orbital complex in case of [Co(NH3)6]3+. In [Ni(NH3)6]2+, Ni is in
+2 oxidation state and has d8 configuration, the hybridisation involved is sp3d2 forming outer orbital
complex.
7. Predict the number of unpaired electrons in the square planar [Pt(CN)4]2– ion.
Ans. [Pt(CN)4]2–
In this complex, Pt is in the +2 state. It forms a square planar structure. This means that it undergoes
dsp2 hybridization. Now, the electronic configuration of Pd(+2) is 5d8.
8
3d
CN– being a strong field ligand causes the pairing of unpaired electrons. Hence, there are no unpaired
electrons in [Pt(CN)4]2–
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8. The hexaqua manganese(II) ion contains five unpaired electrons, while the hexacyanoion contains
only one unpaired electron. Explain using Crystal Field Theory.
Ans.
[Mn(H2O)6]2+ [Mn(CN)6]4–
Mn is in the +2 oxidation state. Mn is in the +2 oxidation state.
The electronic configuration is d5. The electronic configuration is d 5.
The crystal field is octahedral. The crystal field is octahedral.

Water is a weak field ligand. Cyanide is a strong field ligand.
Therefore, the arrangement of the Therefore, the arrangement of the
electrons in [Mn(H2O)6]2+ is electrons in [Mn(CN)6]4– is
t2g3eg2 t2g5eg0.
Hence, hexaaquo manganese (II) ion has five unpaired electrons, while hexacyano ion has only one
unpaired electron.
9. FeSO4 solution mixed with (NH4)2 SO4 solution in 1:1 molar ratio gives the test of Fe2+ ion but
CuSO4 solution mixed with aqueous ammonia in 1:4 molar ratio does not give the test of Cu2+ ion.
Explain why ?
Ans. ( NH4 )2 SO4 + FeSO4 + 6H2 O ¾¾® FeSO4 . ( NH4 )2 SO4.6H2O
Mohr 's salt
CuSO4 + 4NH3 + 5H2 O ¾¾® éëCu(NH 3 ) 4 ùûSO4 .5H2O
tetraamminecopper (II) sulphate
Both the compounds i.e., FeSO4. (NH4)2 SO4. 6H2O and [Cu(NH3)4] SO4. 5H2O fall under the category
of addition compounds with only one major difference i.e., mohr’s salt is an example of a double salt,
while the tetraamminecopper (II) sulphate is a coordination compound.
10. Draw figure to show the splitting of d obitals in an octahedral crystal field.
Energy dx2– y2,dz2

Ans. z eg
y +3/5
Barycentre
–2/5
x
Average energy t2g
of the d orbitals dxy dyz dxz
in a spherical field
Splitting of the d
Metal orbitals in a
d orbitals octahedral crystal field
dx2–y2, dz2dxy, dyz, dxz
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11. What is spectrochemical series ? Explain the difference between a weak field and a strong field
ligand.
Ans. Spectrochemical series is an experimentally determined series based on the absorption of light by complexes
with different ligands. A spectrochemical series is the arrangement of common ligands in the increasing
order of their crystal - field splitting energy (CFSE) values. The ligands present on the R.H.S of the
series are strong field ligands while that on the L.H.S are weak field ligands. Also, strong field
ligands cause higher splitting in the d orbitals than weak field ligands.
I–< Br– <S2– <SCN– <Cl– <N3– <OH– <C2O42– <~H2O < NCS– <edta4– < NH3 < en– <CN– < CO
12. Give the oxidation state, d- orbital occupation and coordination number of the central metal ion in the
following complexes :
(i) K3[Co(C2 O4)3 ] (ii) cis-[Cr(en)2Cl2]Cl
(iii) (NH4 )2[CoF4 ] (iv) [Mn(H2 O)6]SO4

Ans. (i) K3[Co(C2 O4)3 ]
The central metal ion is Co3+.
Its coordination number is 6.
The oxidation state can be given as:
x – 6 = –3
x = +3
The d orbitals occupation for Co3+ is t 62g e0g .
(ii) cis-[Cr(en)2Cl2]Cl
The central metal ion is Cr3+.
The coordination number is 6.
The oxidation state can be given as :

x + 2(0) + 2(–1) = +1
x – 2 = +1
x = +3
The d orbitals occupation for Cr3+ is t 32g .e0g .
(iii) (NH4 )2[CoF4 ]
The central metal ion is Co2+.
x – 4 = –2
x = +2
The d orbitals occupation for Co2+ is t2g5.eg2
(iv) [Mn(H2 O)6]SO4
The central metal ion is Mn2+.
x + 0 = +2
x = +2
The d orbitals occupation for Mn2+ is t 32g e2g .
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13. Explain the following terms giving a suitable example in each case :
(i) Ambidentate ligand
(ii) Denticity of a ligand
(iii) Crystal field splitting in an octahedral field
Ans. (i) Ambidentate ligand : Ligand which can link through two different atoms is called ambident
ligand. Example - SCN , CNO , CN , NO -2 can link through ‘N’ as well as O while SCN can
- – - –
link through ‘S’ as well ‘N’ atom.

(ii) Denticity of a ligand : Total number of lone pair donated by a ligand when it is bonded with
metal- is called denticity
-
or number of doner sites on a ligand is called denticity.
CN has 1, COO
-
has 2,
COO
H2N - CH2 - CH2 - NH - CH2 - CH2 - NH2 has 3.
(iii) Crystal field spliting in an octahedral field : In a octahedral complex, the co-ordination number
is 6. The metal ion is at the centre and the ligands occupy the six corners of the octahedron as
shown in figure.
We know that two orbitals, d x - y and d z are oriented along the axis while the remaining three
2 2 2
orbitals, viz., dxy, dyz and dzx are oriented in between the axis.
The two orbtials dx - y and d z are designated as eg orbitals while the three orbitals dxy, dyz and
2 2 2
dzx are designated as t2g orbitals. As the six ligands approach the central ion along the axis, eg orbitals,
is repelled more by the ligand than the t2g orbitals.
Z
In other words, the energy of the d z and d x - y orbitals increases much more than the energy of the
2 2 2
dxy, dyz and dzx orbitals.

Thus, in octahedral complexes, the five d-orbitals split up into two sets : one set consisting
of two or bitals ( d x and d z ) of higher energy (eg orbitals) and the other set consisting of
2
-y 2 2
three orbitals (dxy, dyz and dzx ) of lower energy (t2g orbitals).
eg
.6 D0
D0
–.4 D0
t2g
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The state I represents degeneracy of al the five d-orbitals in the isolated central ion. The state II represents
hypothetical degeneracy of all the orbitals at a higher energy level if the negative charge of all the
ligands is assumed to be uniformly affecting the electrons in the d-orbitals of the metal ion. The state
III represents crystal field splitting discussed above.
14. Explain the following cases giving appropriate reasons:
(i) Nickel does not form low spin octahedral complexes.
(ii) The p-complexes are known for the transition metals only.
2+ +3
(iii) Co is easily oxidised to Co in the presence of a strong ligand.
Ans. (i) Since nickel in zero oxidation state contain no unpaired electron.
(ii) The transition metal/ions have electrons in d- orbitals which can be shared to p ligands through
synergic bonding.
For example : CH2 = CH2 and C6 H6 etc.
3+
(iii) Co can from very stable low spin octahedral complex.
15. Giving a suitable example for each, explain the following :
(i) Crystal field splitting
(ii) Ambidentate ligand
Ans. (i) Crystal field splitting : In a free transition metal ion, all the five orbitals are degenerate, but when
it is involved in a complex formation, the degeneracy split. This is called crystal field splitting.
(ii) Ambidentate ligand : Unidentate ligands containing more than one coordinating atoms are called
ambidentate ligands. For example,
– – –
NO 2, CN , SCN are all ambidentate ligands.
16. Compare the following complexes with respect to structural shapes of units, magnetic behaviour and
hybrid orbitals involved in units :
3+ 3+
[Co(NH3)6] , [Cr(NH3)6 ] , Ni(CO)4
(At. Nos. : Co = 27, Cr= 24, Ni = 28)
Ans. S. No. Complexes Magnetic behaviour Hybridisation Shape

1 [Co(NH 3 )6]3+ Diamagnetic 2
d sp
3
Octahedral
3+ 2 3
2 [Cr(NH3 )6] Paramagnetic d sp Octahedral
3
3 [Ni(C O) 4] Diamagnetic sp Tetrahedral
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1. Assertion (A): Linkage isomerism arises in coordination compounds becauses of ambidentate ligand.
Reason (R) :Ambidentate ligand like NO2 has two different donor atoms i.e., N and O.(CBSE 2020)
Ans. (i) Both Assertion (A) and Reason (R) are correct statement and Reason (R) is the correct explanation
of the Assertion(A)
2. Give the formulae of the following compounds : (CBSE 2020)
(i) Potassium tetra hydroxydozincate[II]

(ii) Hexaammine platinium [IV] Chloride
Ans. (i) K2[Zn(OH)4]
(ii) [Pt(NH3)6]Cl4
3. Write IUPAC name of the complex [Co(en)2(NO2)Cl]+. What type of structural isomerism is shown
by this complex ? [2]
OR
Using IUPAC norms, write the formulae for the following complexes : [2]
(a) Hexaaquachromium(III) chloride (CBSE 2019)
(b) Sodium trioxalatoferrate(III)
Ans. Chloridobis(ethane-1,2-diamine)nitrito-N-cobalt(III)ion
Linkage isomerism
OR
(i) [Cr(H 2O)6]Cl3 (ii) Na3[Fe(OX)3]
4. (a) Although both [NiCl4]2– and [Ni(CO)4] have sp3 hybridisation yet [NiCl4]2– is paramagnetic
and [Ni(CO)4] is diamagnetic. Give reason. (Atomic no. of Ni = 28) [2]
5
(b) Write the electronic configuration of d on the basis of crystal field theory when
(i) D0 < P and (CBSE 2019)
(ii) D0 >P
Ans. (a) In [NiCl4]2, Cl is a weak field ligand due to which there are two unpaired electrons in 3d orbital
whereas in [Ni(CN)4]2, CN is a strong field ligand due to which pairing leads to no unpaired electron
in 3d-orbital/Or structural representation.
(b) (i) t2g3eg2 (ii) t2g5eg0
5. Defind the following terms with a suitable example of each : [2]
(a) Chelate complex (CBSE 2019)
(b) Ambidentate ligand
OR
(a) Tetraamminediaquacobalt(III) chloride
(b) Dibromidobis(ethane-1,2-diamine)platinum(IV) nitrate
Ans. (a) When a di- or polydentate ligand uses its two or more donor atoms to bind a single metal ion, it
is said to be a chelate ligand. The number of such ligating groups is called the denticity of the ligand.
Such complexes, called chelate complexes
(b) Ligand which can ligate through two different atoms is called ambidentate ligand.
OR
(a) [Co(NH3)4(H2O)2] Cl3 (b) [Pt Br2(en)2] [NO3)2]
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6. Using valence bond theory, write the hybridisation and magnetic character of the complex [Fe(CN)6]4.
(Atomic no. of Fe = 26) [2]
Ans. d2 sp3; Diamagnetic nature (CBSE 2019)
7. Defind the following terms with a suitable example of each : [2]
(a) Polydentate ligand (CBSE 2019)
(b) Homoleptic complex
OR
(a) Potassium tri(oxalato)chromate(III)
(b) hexaaquamanganese(II) sulphate
Ans. (a) Polydentate ligands range in the number of atoms used to bond to a central metal atom or ion.
e.g. EDTA
(b) Homoleptic complex are those which has all identical ligand. e.g. metal compound
OR
(a) K3 [Cr(OX)3]
(b) [Mn(H2O)6]SO4
8. Write the corrdination number and oxidation state of Platinum in the complex [Pt(en)2Cl2]. (CBSE 2018)
Ans. Given complex [Pt (en)2 Cl2]
Coordination no. = denticity × no. of ligands
= 2 × 2 + 2× 1 = 6
Charge on ligand + oxidation state = charge on complex of metal ion
–2 + x = 0
x = +2
9. (a) Write the formula of the following coordination compound : (CBSE 2018)
Iron(III) hexacyanoferrate(II)
(b) What type of isomerism is exhibited by the complex [Co(NH3)5Cl]SO4?
(c) Write the hybridisation and number of unpaired electrons in the complex [CoF 6] 3–.
(Atomic No. of Co = 27).
Ans. (a) Fe4[Fe(CN)6]3
(b) [CO(NH3)5Cl]SO4 (Ionisation isomers)
(c) [COF6]–3
(i) Hybridisation ® Sp3d2
(ii) Unpaired e– ® 4 unpaired electrons.
10. Using IUPAC names write the formulae for the following : (CBSE 2017)
(a) Tris (ethane-1,2-diamine)chromium(III)chloride
(b) Potassium tetrahydroxozincate(II)
Ans. (a) [Cr(en)3]Cl3
(b) K2[Zn(OH)4]
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11. (a) What type of isomerism is shown by the complex [Co(NH3)5(SCN)]2+ ? (CBSE 2017)
2– 2–
(b) Why is [NiCl4] paramagnetic while [Ni(CN)4] is diamagnetic ?
(Atomic number of Ni = 28)
(c) Why are low spin tetrahedral complexes rarely observed
Ans. (a) Linkage isomerism
(b) In [NiCl4]2–, due to the presence of Cl–, a weak field ligand no pairing occurs whereas in [Ni(CN)4]2–
, CN–is a strong field ligand and pairing takes place.
(c) Because of very low CFSE which is not able to pair up the electrons.
12. When a coordination compound NiCl2.6H2O is mixed with AgNO3, 2 moles of AgCl are precipitated
per mole of the compound. Write (CBSE 2016)
(i) Structural formula of the complex
(ii) IUPAC name of the complex
Ans. (i) [Ni(H2O)6] Cl2
(ii) Hexaaquanickel(II) chloride
13. (a) For the complex [Fe(CN)6]4–, write the hybridization, magnetic character and spin type of the
complex. (At. number : Fe = 26) (CBSE 2016)
(b)Draw one of the geometrical isomers of the complex [Co(en)2Cl2]+ which is optically active.
Ans. (a) d2sp3,
Diamagnetic,
low spin
Cl +
Cl
(b) en Co
en
14. (i) Write down the IUPAC name of the following complex : (CBSE 2015)
[Pt(NH3)(H2O)Cl2 ]
(ii) Write the formula for the following complex :
tris(ethan-1, 2-diamine)chromium(III) chloride
Ans. (i) Ammineaquadichloridoplatinum(II)
(ii) [Cr(en)3]Cl3
15. (i) What type of isomerism is shown by [Co(NH3)5ONO]Cl2? (CBSE 2015)
(ii) On the basis of crystal field theory, write the electronic configuration for d4 ion if D0 < P.
(iii) Write the hybridization and shape of [Fe(CN)6]3–.
(Atomic number of Fe = 26)
Ans. (i) Linkage isomerism
(ii) t2g3 eg1 / Diagrammatic representation
(iii) d2sp3, Octahedral
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EXERCISE-3 RACE

In an octahedral coordination entity with six ligands surrounding the metal atom/ion, there will be
repulsion between the electrons in metal d orbitals and the electrons (or negative charges) of the ligands.
Such a repulsion is more when the metal d orbital is directed towards the ligand than when it is away
from the ligand. Thus, the dx2-y2and dz2 orbitals.
Which point towards the axes along the direction of the ligand will experience more repulsion and
will be raised in energy; and the dxy, dyz and dxz orbitals which are directed between the axes will
be lowered in energy relative to the average energy in the spherical crystal field. Thus, the degeneracy
of the d orbitals has been removed due to ligand electron-metal electron repulsions in the octahedral
complex to yield three orbitals of lower energy, t2g set and two orbitals of higher energy, eg set.?
(i) The relation between Dt and DO is :-
æ4ö æ4ö æ9ö æ9ö
(a) Dt = ç ÷ DO (b) DO = ç ÷ Dt (c) DO = ç ÷ Dt (d) Dt = ç ÷ DO
è9ø è9ø è4ø è4ø
(ii) For SFL what is relation between pairing energy and crystal field splitting for octahedral :-
(a) DO > P (b) DO < P (c) DO = P (d) None of these
(iii) eg orbital experience more repulsion that t2g orbitals due to ?
(a) d orbital are on axis (b) d orbital are on equatorial
(c) d orbital between axis (d) None of these
4
(iv) Write the electronic configuration of d on the basis of SFL when DO < P :-
4 0 3 1 2 2 0 4
(a) t2g eg (b) t2g eg (c) t2g eg (d) t2g eg

Question 2 to 6 :- Note:- In the following questions a statement of assertion followed by a reason . choose
2. Assertion : [Pt Cl2 (NH3)2] is square planner
Reason : Cl- is a weak field ligand
3. Assertion : [Cr(H2O)6]Cl2 and [Fe(H2O)6]Cl2 are reducing in nature.
Reason : Unpaired electrons are present in their d-orbitals.
4. Assertion : ([Fe(CN)6]3– ion shows magnetic moment corresponding to two unpaired electrons.
Reason : Because it has d2sp3 type hybridization.
5. Assertion : The [Ni (en)3]Cl2 has lower stability than [Ni (NH3)6]Cl2
Reason : In [Ni (en)3]Cl2 the geomectory of Ni is trigonal bipyramidal.
6. Assertion : [Ni(CO)4] is SP3 hybridized
Reason : It is diamagnetic in nature.
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7. When 1 mol CrCl3.6H2O is treated with excess of AgNO3, 3 mol of AgCl are obtained. The formula
of the complex is :
(i) [CrCl3 (H2O)3].3H2O (ii) [CrCl2(H2O)4]Cl.2H2O
(iii) [CrCl(H2O)5]Cl2.H2O (iv) [Cr(H2O)6]Cl3
8. The correct IUPAC name of [Pt(NH3)2Cl2] is :-
(i) Diamminedichloridoplatinum (II)
(ii) Diamminedichloridoplatinum (IV)
(iii) Diamminedichloridoplatinum (0)
(iv) Dichloridodiammineplatinum (IV)
9. The stabilisation of coordination compounds due to chelation is called the chelate effect. Which of the
following is the most stable complex species?
(i) [Fe(CO)5] (ii) [Fe(CN)6]3- (iii) [Fe(C2O4)3]3- (iv) [Fe(H2O)6]3-
10. A chelating agent has two or more than two donor atoms to bind to a single metal ion. Which of the
following is not a chelating agent?
(i) thiosulphato (ii) oxalato (iii) glycinato (iv) ethane-1,2-diamine
11. Which of the following options are correct for [Fe(CN)6]3– complex?
(i) dsp2 hybridisation (ii) sp3d2 hybridisation
(iii) paramagnetic (iv) diamagnetic
12. Which of the following complexes are homoleptic?
(i) [Co(NH3)6]3+ (ii) [Co(NH3)4 Cl2]+
(iii) [Ni(CN)2(NO)2]2– (iv) [Ni(NH3)4Cl2]
13. Which of the following complexes are heteroleptic?
(i) [Cr(NH3)6]3+ (ii) [Fe(CN)6]4– (iii) [Mn(CN)6]4– (iv) [Co(NH3)4Cl2]
14. Identify the incorrect statements for the behaviour of ethane-1, 2-diamine as a ligand.
(i) It is a neutral ligand. (ii) It is a didentate ligand.
(iii) It is a chelating ligand. (iv) It is a unidentate ligand.
15. How many ions are produced from the complex [Co(NH3)5Cl] Cl2 in solution ?
(i) 4 (ii) 2 (iii) 3 (iv) 5
16. The oxidation state of Ni in [Ni(CO)4] is :-
(i) 0 (ii) 2 (iii) 3 (iv) 4
Answer key :
Q. No. 1 (i) (ii) (iii) (iv) 2 3 4 5 6 7 8
Ans. b a a b B B D D C iv i
Q. No. 9 10 11 12 13 14 15 16
Ans. iii i iii i iv iv iii i
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1. Define Homoleptic complex. [1]
2. Write the hybridization and shape of [Fe(CN)6]3–. (Atomic number of Fe = 26) [1]
3. What do you mean by chealate ligand. [1]

4. Why is [NiCl4]2– paramagnetic while [Ni(CN)4]2– is diamagnetic ? (Atomic number of Ni = 28) [2]
5. Why are low spin tetrahedral complexes rarely observed [2]
6. Write the corrdination number and oxidation state of Platinum in the complex [Pt(en)2Cl2]. [2]
7. Write the hybridisation and number of unpaired electrons in the complex [CoF 6 ] 3– .
(Atomic No. of Co = 27). [2]
8. When a coordination compound NiCl2.6H2O is mixed with AgNO3, 2 moles of AgCl are precipitated
per mole of the compound. Write [3]
(i) Structural formula of the complex
(ii) IUPAC name of the complex

9. Using IUPAC norms write the formulae for the following : [3]
(a) Tris (ethane-1,2-diamine)chromium(III)chloride
(b) Potassium tetrahydroxozincate(II)

(c) Hexaammine platinium [IV] Chloride

10. For the complex [Fe(CN)6]4–, write the hybridization, magnetic character and spin type of the
complex. (At. number : Fe = 26) [3]
11. (a) What is meant by crystal field splitting energy? On the basis of crystal field theory, write the
electronic configuration of d4 in terms of t2g and eg in an octahedral field when [5]
(i) D0 > P
(ii) D0 < P
(b) (i) Write the IUPAC name of the complex [Cr(NH3)4 Cl2] Cl.
(ii) Write IUPAC name of the complex [Co(en)2(NO2)Cl]+.
(iii) Why is [NiCl4]2– paramagnetic but [Ni(CO)4] is diamagnetic ?

(At. nos. : Cr = 24, Co = 27, Ni = 28)
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MOCK TEST SOLUTIONS
1. Homoleptic complex are those which has all identical ligand. e.g. metal compound.
2. d2sp3, Octahedral
3. When a di- or polydentate ligand uses its two or more donor atoms to bind a single metal ion, it is
said to be a chelate ligand. The number of such ligating groups is called the denticity of the ligand.
Such complexes, called chelate complexes.
4. In [NiCl4]2–, due to the presence of Cl¯, a weak field ligand no pairing occurs whereas in [Ni(CN)4]2,
CN¯ is a strong field ligand and pairing takes place.
5. Because of very low CFSE which is not able to pair up the electrons.
6. Given complex [Pt (en)2 Cl2]
Coordination no. = denticity × no. of ligands
=2×2+2×1=6
Charge on ligand + oxidation state = charge on complex of metal ion
–2+x=0
x = +2
7. [COF6]–3
(i) Hybridisation ® Sp3d2
(ii) Unpaired e¯ ® 4 unpaired electrons.
8. (i) [Ni(H2O)6] Cl2
(ii) Hexaaquanickel(II) chloride
9. (i) [Cr(en)3]Cl3
(ii) K2[Zn(OH)4]
(iii) [Pt(NH3)6]Cl4
10. d2sp3,
Diamagnetic,
low spin
11. (a) The difference of energy two sets of d-orbitals (which are no longer degenerate under different
kinds of electric fields).
Is called crystal field stabilization energy or (CFSE) represented by symbol D0.
d4 when D0 > P t42g eg°.
d4 when D0 < P t32g eg1.
(b) (i) Tetraamminedichloridochromium(III) chloride.
(ii) Chloridobis(ethane-1,2-diamine)nitrito-N-cobalt(III)ion.
(iii) In Ni(CO)4, Ni is in zero oxidation state whereas in NiCl42–, it is in +2 oxidation state. In the
presence of CO ligand, the unpaired d electrons of Ni pair up but Cl¯ being a weak ligand is unable
to pair up the unpaired electrons.
182 E

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1

04. CHEMICAL KINETICS 70

05. SURFACE CHEMISTRY 91

06. THE P-BLOCK ELEMENTS 109

07. THE D & F-BLOCK ELEMENT 146

08. COORDINATION COMPOUND 166

Guidelines for Chemistry

3. We already provide chapter wise key points, NCERT important question

syllabus is reduced in 2020-21 session and we have designed your course

Unit I: Solid State 8 Periods

Unit II: Solutions 8 Periods

Unit III: Electrochemistry 7 Periods

Unit IV: Chemical Kinetics 5 Periods

Unit V: Surface Chemistry 5 Periods

Unit VIII: d and f Block Elements 7 Periods

Unit IX: Coordination Compounds 8 Periods

Unit X: Haloalkanes and Haloarenes 8 Periods

Unit XI: Alcohols, Phenols and Ethers 8 Periods

Unit XII: Aldehydes, Ketones and Carboxylic Acids 10 Periods

Unit XIV: Biomolecules 7 Periods

Distinction between Crystalline and Amorphous Solids

Property Crystalline Solids Amorphous Solids

TYPES OF THE CRYSTALLINE SOLID

(iii) Hydrogen Hydrogen Hard Insulator Low

Face centred cubic (FCC) 4 a =2 2r

1. Why are solids rigid ?

12. Calculate the efficiency of packing in case of a metal crystal for

10.5 ´ 67.76 ´ 10-24 ´ 6.023 ´ 1023

1.732 ´ 3.3 ´ 10-8

It is agreement with measured value 8.92 g cm–3

(a) What is the length of the side of the unit cell ?

Ans. Given that r = 125 pm

(b) No. of unit cell = Total volume / Volume of a unit cell

Ans. It is given that NaCl is doped with 10–3 mol % of SrCl2.

Cation vacancies produced by one Sr2+ ion = 1

\ Concentration of the cation vacancies

Produced by 10–5 mol of Sr+2 ions = 10–5 × 6.022 × 1023

= 6.022 × 1018 mol–1

Ans. Frenkel defect

Type–2 : Assertion and Reason :

(iii) Chrome alum (iv) Silicon carbide (SiC)

1. Write any one example of network solid. [1]

2. Dislocation of which ion in "AgBr" develops Frenkel defect? [1]

electrical conductance only in molten state. Give reason. [1]

6. ZnO turns yellow on heating. Why ? [2]

1/3rd of tetrahedral voids. [2]

the molar mass of element. (NA= 6.022 × 1023 mol–1) [3]

Cation vacancies produced by one Sr2+ ion = 1

Type of Solutions Solute Solvent Common Example

Gaseous Solutions Gas Gas Mixture of oxygen and nitrogen gases

Liquid Solutions Gas Liquid Oxygen dissolved in water

Solid Solutions Gas Solid Solution of hydrogen in palladium

pressure of pure solvent.

l Types of Azeotropic mixtures

(i) Minimum boiling Azeotropic mixtures

(ii) Maximum boiling Azeotropic mixtures

l Parts per million (ppm)

l Raoult¢s law for a solution of volatile solute in volatile solvent :

Positive deviation Negative deviation Zero deviation

(Since1 n CO is negligible as compared to n H O )

In 500 mL of soda water, the volume of water = 500 mL

n CO2 = 0.042 mole

Hence, quantity of CO2 in 500 mL of soda water = (0.042 × 44)g

Ans. (i) It is given that: