Chemestry Guide

Based on the Board's New Textbook
Salient features :
1. A complete reference book on Chemistry XII.
2. I mportant Terms, Units, Laws, Formulae, Properties and Reactions given in the beginning of
each chapter for instant revision.
3. M odel answers to all the textual questions and many additional questions for understanding
basic and advanced concepts given in the Textbook.
4. A nswers to inquisitive and brain stimulating questions under the titles ‘Can you tell ?’, ‘Just
think’, ‘Use your brain power’, etc. are given or provided wherever necessary.
5. G raded and varied solved numerical problems, supplemented by a large number of problems
for practice.
6. Includes ample number of Multiple Choice Questions (MCQs).
7. Simple and learner-friendly language.
8. Neat fully-labelled, authentic and easily-reproducible diagrams in two colours.
9. Very useful book to understand the subject well and to prepare thoroughly for HSC Board
Examination as well as other competitive examinations like NEET, JEE MAIN, MHT-CET, etc.
By
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Published by : Navneet Education Limited, Dantali, Gujarat. 2001

CTP
Printed by : Navneet Education Limited, Dantali, Gujarat. (5-6-2020)
2
PREFACE
It gives us great pleasure to present you this first edition of Navneet Chemistry Digest (Part I) for
Standard XII. This book is prepared according to the Maharashtra Board’s New Textbook.
We understand that the Higher Secondary Examination is very crucial in a student’s career. As in the
past, this Navneet Digest will help you to triumph.
Each chapter of the Digest begins with important Terms, Units, Laws, Formulae, Properties, Reactions,
etc. for instant revision. This book includes all the questions given in the Board’s Textbook as well as
many additional questions with their model answers so as to cover every concepts given in the Textbook.
Graded and varied solved numerical problems, supplemented by a large number of problems for practice
gives students an opportunity to master the subject through thorough practice.
Besides these, all the other questions or informations given in various boxes in the textbook such as
'Can you tell?', ‘Do you know?’, 'Use your brain power', 'Observe and discuss', etc. are also included.
Ample number of Multiple Choice Questions (MCQs) have been given to enable the students to prepare
for any type of competitive examination, such as NEET, JEE MAIN, MHT-CET, etc.
Neat, accurate and easily reproducible diagrams are given in an attractive two-colour style.
In short, this Chemistry Digest contains a lucid and clear exposition of the subject matter in simple
language.
We hope this Digest will help the students to master the subject. Besides it will also help them to secure
very good marks in the examination and pave the way for realising their dreams of a fruitful, bright
career.
We have taken utmost care to see that this Digest proves to be very useful to the students as well as
the teachers. Suggestions for improvement of the Digest are most welcome and will be gratefully
acknowledged and appreciated.
—The Publishers
3
CONTENTS
Page No.
1. Solid State . . . 155
2. Solutions . . . 147
3. Ionic Equilibria . . . 89
4. Chemical Thermodynamics . . . 120
5. Electrochemistry . . . 183
6. Chemical Kinetics . . . 248
7. Elements of Groups 16, 17 and 18 . . . 307

8. Transition and Inner transition Elements . . . 362
Chapter Nos. 9 to 16 are included in Chemistry Digest: Part 2, published separately.
4
1. SOLID STATE
1 SOLID STATE
CHAPTER OUTLINE
.... Important Terms and Formulae
.... Exercises Page No.
1.1 Introduction … 7
1.2 Types of solids … 7
1.2.1 Crystalline solids … 7
1.2.2 Amorphous solids … 7
1.2.3 Isomorphism and polymorphism … 7
1.3 Classification of crystalline solids … 11
1.3.1 Ionic crystals … 11
1.3.2 Covalent network crystals … 11
1.3.3 Molecular crystals … 11
1.3.4 Metallic crystals … 11
1.4 Crystal Structure … 14
1.4.1 Crystal, lattice and basis … 14
1.4.2 Unit cell … 14
1.4.3 Types of unit cell … 14
1.4.4 Crystal systems … 14
1.5 Cubic system … 15
1.5.1 Number of particles in cubic unit cell … 15
1.5.2 Relationship between molar mass, density of the substance and unit cell edge
length … 15
1.6 Packing of particles in crystal lattice … 19
1.6.1 Close packed structures … 19
1.6.2 Coordination number in close packed structure … 19
1.6.3 Number of voids per atom in hcp and ccp … 19
1.7 Packing efficiency … 23
1.7.1 Packing efficiency of metal crystal in simple cubic lattice … 23
1.7.2 Packing efficiency of metal crystal in body-centred cubic lattice … 23
1.7.3 Packing efficiency of metal crystal in face-centred cubic lattice (or ccp or hcp
lattice) … 23
1.7.4 Number of particles and unit cells in x g of metal crystal … 23
1.8 Crystal defects or imperfections … 32
1.9 Electrical properties of solids … 35
1.9.1 Band theory … 35
1.9.2 Metals … 35
1.9.3 Insulators … 35
1.9.4 Semiconductors … 35
1.9.5 Extrinsic semiconductors and doping … 35
1.10 Magnetic properties of solids … 41
.... Multiple Choice Questions … 42
.... Examples for Practice … 45
1. SOLID STATE 5
; Crystalline
1. Solids IIIII
; Amorphous
; Ionic crystals
; Covalent network crystals
2. Crystalline solids IIIII
; Molecular crystals
; Metallic crystals
; Cubic
; Orthorhombic
; Tetragonal
3. Crystal systems IIIII; Monoclinic
; Rhombohedral
; Triclinic
; Hexagonal
4. Classification of crystal systems (Bravais lattices) :
; (i) Simple cubic or primitive
Cubic lattice IIIII; (ii) Body centred cubic
; (iii) Face centred cubic
5. Number of atoms in the unit cell : Unit cell scc bcc fcc hcp
Number of atoms 1 2 4 3
6. Packing efficiency : scc bcc fcc hcp

52.4 % 68 % 74 % 74 %
7. Number of tetrahedral voids:2 Number of atoms

Number of octahedral voids:Number of atoms
8. Relation between radius (r) of an atom and edge length (a) of cubic unit cell :
scc bcc fcc
r:
a (3 a
2 r: a r:
4 2(2
n;M
9. Density of the crystal : :
a;N

6 NAVNEET CHEMISTRY DIGEST : STANDARD XII (PART I)

10. Defects in solids :
; (i) Vacancy defects (Schottky defects)
(1) Point defects IIIII; (ii) Interstitial defects (Frenkel defects)
; Substitutional impurity defects
; (iii) Impurity defects IIIII
; Interstitial impurity defects
; Metal deficiency defect
(2) Nonstoichiometric defects IIIII
; Metal excess defect
; Conductors
11. Conducting solids IIIII; Semiconductors
; Insulators
; Intrinsic
12. Semiconductors IIIII ; n-type
; Extrinsic IIIII
; p-type
; Diamagnetic
13. Magnetic properties IIIII; Paramagnetic
; Ferromagnetic
14. (1) Diamagnetism is due to the presence of all paired electrons in the substance.
(2) Paramagnetism is due to the presence of one or more unpaired electrons in the substance.
; heat ; heat
Solid Liquid Gas
(★ ) Indicates question from the textbook. 9 heat 9 heat
(cool) (cool) ■
Unit
1.1 Introduction Q. 2. What are the constituents of solids ? (1 mark)
Q. 1. What are physical states of matter ? How can Ans. The smallest constituent particles of various solids
they be changed into one another ? (2 marks) are atoms, ions or molecules. All such small consti-
Ans. tuents are referred to as ‘particles’. ■
(1) There are three physical states of matter namely

Units
solid, liquid and gas.
1.2 Types of solids
(2) They differ in intermolecular or interatomic or 1.2.1 Crystalline solids
interionic forces which are strongest in the solid 1.2.2 Amorphous solids
state. 1.2.3 Isomorphism and polymorphism
(3) By raising the temperature of solids to their melting
point, solids are converted into liquids while heat- Q. 3. What are the characteristic properties of
ing liquids to their boiling points, they can be solids ? (2 marks)
converted into vapour or gaseous state. Ans.
(4) On the contrary, by cooling the gases to very low (1) The solid state of matter is characterised by strong
temperature and subjecting to high pressure they interparticle forces of attraction.
can be transformed into liquid which on further (2) There is regularity and periodicity in the arrange-
cooling can be transformed into solid state. ment of constituent particles of solid.
The equilibrium existing between three states of (3) Generally solids are hard, incompressible and rigid
matter may be represented as, except some solids like Na, K, P which are soft.
1. SOLID STATE 7
(4) The constituent particles of solids like molecules,
atoms or ions have fixed stationary positions in
solid and can only oscillate about their equilibrium
or mean positions. Hence, they have fixed shape and
cannot be poured like liquids.
(5) Crystalline solids have sharp melting points and
they melt at a definite temperature. Amorphous
solids do not have sharp melting points.
(6) They are anisotropic or isotropic. ■
Particle 1 Particle 2
Q. 4. Give classification of solids. (1 mark)
Ans. Depending on orderly arrangement of the constitu- Fig. 1.1 : Anisotropy in crystals : Different arrangements of
ent particles, the solids are classified into two constituent particles about different directions, AB, CD and EF.
■
types :
(1) Crystalline solids. For example, diamond, NaCl, Try this ...
(Textbook page 1)
K SO , etc.
Observe the figure 1.1 carefully. The two types of
(2) Amorphous solids or non-crystalline solids. For
circles in this figure represent two types of constituent
example, tar, glass, plastics, rubber, butter, etc. ■
particles of a solid.
Q. 5. Define : (1) Crystalline solid. (1) Will you call the arrangement of particles in
(2) Amorphous solid. (1 mark each) this solid regular or irregular ?
Ans. Ans. The arrangement of particles in this solid is
(1) Crystalline solid : A homogeneous solid in which regular.
the constituent particles like atoms, ions or mol- (2) Is the arrangement of constituent particles in
; ; ;
ecules are arranged in a definite repeating pattern directions AB, CD and EF same or different ?
;
throughout the solid is called crystalline solid. For Ans. AB represents arrangement of identical particles
example, NaCl, KNO , etc. of one type.
;
CD represents arrangement of identical particles
(2) Amorphous solid : A substance which appears like
of another type.
solid but does not have perfectly ordered crystalline ;
EF represents regular arrangement of two differ-
structure and no regular arrangement of constituent
ent particles in alternate positions.
particles in structure is called amorphous solid. For
example, glass, rubber, plastics, etc. ■
Q. 6. Define the term anisotropy. (1 mark) Do you know ?

(Textbook page 2)
OR
● A single crystal has ordered (regular and periodic)
Define and explain the term anisotropy. arrangement of constituent particles throughout its
(2 marks) bulk.
Ans. Anisotropy : The ability of crystalline solids to ● Majority of crystalline solids, including metals, are
change their physical properties when measured in polycrystalline in nature. Single granule of a poly-
different directions is called anisotropy. crystalline solid is made of many single crystals or
Explanation : This property is due to different crystallites packed together with different orienta-
arrangement of constituents in different directions. tions.
Different types of particles fall on the way of ● Single crystals are difficult to obtain. Diamond is an
measurements in different directions. Hence the example of naturally formed single crystal.
composition of crystalline solid changes with direc-
tions changing their physical properties.

(5) Amorphous substances appear like solids but they
do not have perfectly ordered crystalline structure,
hence they are not real solids. Therefore they are
pseudo solids.
(6) They are isotropic and exhibit the same magnitude
of any property in every direction. ■
Q. 10. What is isomorphism ? (1 mark)

Ans. Isomorphism : A phenomenon in which two or
Fig. 1.2 : Arrangement of particles more crystalline substances show same crystalline
structure is called isomorphism and the crystals are
Q. 7. Define and explain isotropy. (2 marks) said to be isomorphous. For example, NaNO and
Ans. Isotropy : The ability of amorphous solids to
CaCO . They have atomic ratios 1 : 1 : 3. ■
exhibit identical physical properties even though
measured in different directions is called isotropy. Q. 11. What is isomorphous ? (1 mark)
Explanation : This property arises because there is Ans. Isomorphous : When two or more crystalline
no long range order of regular pattern of arrange- substances have the same crystalline structure, they
ment in them and hence the arrangement is irregular are said to be isomorphous. For example, NaF and
along all the directions. Therefore the magnitude of MgO, NaNO and CaCO . ■

any physical property would be identical along all
Q. 12. What is polymorphism ? (1 mark)
directions. ■
Ans. Polymorphism : A phenomenon in which when a
Q. 8. Why does crystalline solid show different single substance crystallises in two or more forms
refractive indices in different directions ? under different conditions of solidification is called
(2 marks) polymorphism and the substance is called polymor-
Ans. phous. For example, calcite and oragonite are two
(1) Crystalline solid has long range order of regular forms of CaCO . ■
pattern of arrangement which repeats periodically
over entire crystal. Q. 13. What is polymorphous ? (1 mark)
(2) Within the given pattern, the arrangements of Ans. Polymorphous : A single substance which
different atoms or ions or molecules is different in crystallises in two or more forms under different
different directions. Hence the properties like conditions of solidification is called polymorphous.
refractive indices in the different directions are Polymorphic forms of an element are called allot-
different. ropic forms or allotropes. For example, carbon
exists as diamond and graphite, or sulphur exists in
This shows that the crystalline solids are anisotropic
in nature. ■
rhombic and monoclinic allotropic forms. ■
Q. 9. Explain the properties of amorphous solids. Q. 14. Identify isomorphous and polymorphous
(2 marks) substances in the following :
Ans. K SO , graphite, -quartz, Na SeO , CaCO ,

(1) The constituent particles in amorphous solids are diamond, cristobalite, CsNO . (2 marks)

arranged randomly. Ans.
(2) They have short range ordered structure. Isomorphous Polymorphous
(3) Amorphous solids are called supercooled liquids
K SO , Na SeO graphite, diamond
having very high viscosity.
CaCO , CsNO -quartz, cristobalite
(4) They do not have sharp melting points and they
melt gradually over a temperature interval. ■
1. SOLID STATE 9
Use your brain power ! (3) Hence the heat and temperature needed to melt the
(Textbook page 2) solid are same, and therefore solids have sharp
Identify the arrangements A and B as crystalline melting points. ■
or amorphous.
Q. 16. Amorphous solids do not have sharp melting
points. Explain. (2 marks)
Ans.
(1) Amorphous solids do not have perfectly ordered
crystalline structure.
(2) They have short range order of regular pattern
Fig. 1.3 (A) Fig. 1.3 (B) hence periodically repeating regular pattern is over
Ans. Arrangement in 1.3 A indicates the substance a short distance.
is crystalline. (3) The thermal energy required to break the structure
Arrangement in 1.3 B indicates the substance is and separate constituent particles is not uniform.
amorphous. (4) Hence the temperature needed to melt the solid is
not same, therefore amorphous solids do not have
Do you know ?
(Textbook page 3) sharp melting points but melt over a range of
Many crystalline forms of silica (SiO ) are found temperature. ■

in nature. Three of them are -quartz, -quartz and Q. 17. Give examples of (1) crystalline solids and
cristobalite. (2) amorphous solids. (2 marks)
Ans.
(1) Crystalline solids : Metallic solids (Cu, Fe, etc.)
crystalline salts (NaCl, K SO , etc.)

(2) Amorphous solids : Glass, plastics, rubber, etc. ■
Q. 18. Distinguish between crystalline solids and

Fig. 1.4 (A) : -quartz Fig. 1.4 (B) : -quartz amorphous solids. (2 marks)
Ans.
Crystalline solids Amorphous solids
1. They have definite charac- 1. They have irregular shape.

teristic geometrical shape.
2. They have long range 2. They have short range
Fig. 1.4 (C) : cristobalite
order of regular pattern of order of regular pattern of
arrangement of constituent arrangement of constituent
Q. 15. Why does a crystalline solid has a sharp particles. particles.
melting point ? (2 marks) 3. They are true solids. 3. They are pseudo solids or
Ans. supercooled liquids.
(1) Crystalline solid is a homogeneous solid and it has 4. They have sharp melting 4. They do not have sharp
long range order of regular pattern of arrangement points. melting points.
which repeats periodically over entire crystal. 5. They are anisotropic in 5. They are isotropic in
nature. nature.
(2) The interatomic or intermolecular forces are ident-
6. They have definite heat of 6. They do not have definite
ical, hence the thermal energy required to break the
fusion. heat of fusion.
regular structure by overcoming the intermolecular
forces is uniform throughout. (Any four points : 12 mark each) ■

Units (3) Since there are no free electrons, they are not
1.3 Classification of crystalline solids malleable and on applying a shearing force, ionic
1.3.1 Ionic crystals crystals break into small units. Hence they are
1.3.2 Covalent network crystals brittle. ■
1.3.3 Molecular crystals
Q. 23. What are covalent network crystals ?
1.3.4 Metallic crystals
(1 mark)
Q. 19. How are crystalline solids classified ? Ans. The crystals in which the constituent particles are
(2 marks) atoms linked by covalent bonds forming a continu-
Ans. Crystalline solids are classified as follows : ous network are called covalent network crystals.
(1) Ionic crystals For example, diamond, quartz. ■
(2) Covalent network crystals
★ Q. 24. What are the types of particles in each of the
(3) Molecular crystals
(4) Metallic crystals ■
four main classes of crystalline solids ?(1 mark)
Ans. The smallest constituents or particles of
Q. 20. What are crystalline solids ? (1 mark)
various solids are atoms, ions or molecules. ■
Ans. The solids in which the constituent particles are
charged ions namely cations and anions held Q. 25. What are the characteristics of covalent
together by electrostatic force of attraction are network crystals ? (2 marks)
called crystalline solids. ■ Ans. The characteristics of covalent network crystals are
Q. 21. What are the characteristics of ionic crystals ? as follows :
(2 marks) (1) The constituent particles in these solids are atoms.
Ans. The characteristics of ionic crystals are as follows : (2) The atoms in these crystals are held by covalent
(1) The constituents of ionic crystals are charged ions bonds forming a rigid three dimensional network
namely cations and anions. They differ in ionic size. which gives a giant molecule. Hence, the entire
(2) The ions in these crystals are held by strong crystal is a single molecule.
electrostatic force of attraction. (3) These crystals are very hard (or hardest) and most
(3) Ionic crystals have high melting points and they are incompressible.
hard and brittle. (4) They have high melting points and boiling points.
(4) In solid state they are nonconductors of electricity
(5) Since the electrons are localised they are poor
but they are good conductors when melted or
conductors of heat and electricity.
dissolved in water.
(6) Example : Quartz (SiO ), diamond. ■
(5) In aqueous solution they dissociate forming ions.
(6) Example : NaCl, KCl, CaF , K SO , etc. ■ Q. 26. Give the examples of network solids.

(1 mark)
Q. 22. Explain why ionic solids are hard and brittle.
Ans. The examples of covalent network solids are as
(2 marks)
follows :
Ans.
Quartz (SiO ), diamond, boron nitride carborun-
(1) In ionic crystalline solids, constituent particles are
dum. ■
positively charged cations and negatively charged
anions placed at alternate lattice points. Do you know ?
(Textbook page 3)
(2) The ions are held by strong coulombic electrostatic
● Diamond is the hardest known material.
forces of attraction compensating opposite forces.
Hence they are hard.
1. SOLID STATE 11
Try this ... Q. 27. What are allotropes ? (1 mark)
(Textbook page 3) Ans. Allotropes : When a substance exists in two or
Graphite is a covalent solid yet soft and good more forms then they are called allotropes. They are
conductor of electricity. Explain. polymorphous. For example, carbon has allotropes
Ans. diamond and graphite. ■
Q. 28. What are molecular crystals ? (1 mark)

Ans. The crystals in which the constituent particles are
molecules (or unbonded single atoms) of the same
substance held together by intermolecular forces of
attraction. For example solidified Cl , CO , etc. ■

Q. 29. What are the characteristics of molecular
crystals ? (2 marks)
Ans. The characteristics of molecular crystals are as
follows :
(1) The constituent particles of these solids are mol-
ecules (or unbonded single atoms) of the same
substance.
Fig. 1.5 : Layer structure of graphite (2) The atoms within the molecules are bonded by
(1) Each carbon atom in graphite is sp hybridised covalent bonds.
and covalently bonded to other three sp hybrid- (3) The molecules are held together by intermolecular
ised carbon atoms forming bonds and the fourth forces of attraction. ■
electron in 2pz orbital of each carbon atom is used Q. 30. What are intermolecular forces of attraction
in the formation of a bond. This results in the involved in molecular crystals ? (3 marks)
formation of hexagonal rings in two dimensions. Ans. The intermolecular forces involved in molecular
(2) In graphite, the layers consisting of hexagonal crystals are as follows :
(1) Weak dipole-dipole interactions :
carbon network are held together by weak van der
The solids constituting polar molecules like HCl,
Waal’s forces imparting softness.
H O, SO , etc. which possess permanent dipole
(3) The electrons in bonds in the ring are delocalised
moment involve weak dipole-dipole interactions.
and free to move in the delocalised molecular
(2) Very weak dispersion or London forces :
orbitals giving good electrical conductance.
The solids consisting of nonpolar molecules like
CH , H , etc. involve weak dispersion forces. They
Remember ...
(Textbook page 4) are also involved in monoatomic solids like Ar, Ne.
● Both ionic and covalent crystals are hard and have (3) Intermolecular Hydrogen bonds :
high melting and boiling points. We can use electri- (i) In this crystalline solids, the constituent par-
cal properties to distinguish between them. Both are ticles are the molecules which contain hydro-
insulators at low temperature. gen atom linked to highly electronegative
● Ionic solids become good conductors only at high atom like F, O or N.
temperature, above their melting points. (ii) In these, molecules are held by hydrogen
● The conductivity of covalent solids is in general low bonds in which H atom of one molecule is
bonded to electronegative atom (like F, N or
and increases with temperature. However, there is
O) of another molecule.
no abrupt rise in conductivity when substance is
(iii) Since hydrogen bonding is weak, these solids
melted.
have very low melting points and generally at

room temperature they exist in the liquid or (1) Metallic crystals are solids formed by atoms of the
gaseous state. same metallic element held together by metallic
(iv) They are non-conductors of electricity. ■ bonds.
Q. 31. What are metallic crystals ? (1 mark) (2) Metallic crystals have high melting point and
Ans. These are crystalline solids formed by atoms of the boiling point.
same metallic element held together by metallic (3) Metals are malleable and can be hammered into thin
bonds. ■ sheets.
Q. 32. What are the characteristics of metallic (4) Metals are ductile and can be drawn into thin wires.
crystals ? (2 marks) (5) Metals are good conductors of heat and electricity.
Ans. (6) Examples are Cu, Ag, Au, Ni, etc. ■
Table 1.1 : Properties of four types of crystalline solids
Type Ionic solids Covalent network Molecular Metallic

Property solids solids solids
1. Particles of unit cell Cations and anions Covalently bonded Monoatomic or Metallic ions floating in
atoms polyatomic molecules a sea of electrons
2. Interparticle forces Electrostatic Covalent bonds London, dipole–dipole Metallic bonds (attrac-
forces and/or hydrogen tion between cations and
bonds mobile valence electrons)
3. Hardness Hard and brittle Very hard Soft Variable from soft to
very hard
4. Melting points High High Low Wide range

600 °C to 3000 °C 1200 °C to 4000 °C (9272 °C to 400 °C) (939°C to 3400 °C)
5. Thermal and Poor electrical Poor conductors Poor conductor of heat Good conductor of heat
electrical conductors in solid Exceptions : and electricity and electricity
conductivity state. Good (i) Graphite : good
conductors when conductor of electricity
melted or dissolved (ii) Diamond : good
in water. conductor of heat
6. Examples NaCl, CaF diamond, silica ice, benzoic acid Na, Mg, Cu, Au

★ Q. 33. Distinguish between ionic solids and Ans.

molecular solids. (2 marks)
Solid Type
Ans. For answer refer to Table 1.1. ■
(i) Plastic Covalent network crystal
Q. 34. Classify the following solids into different (ii) P molecule Covalent network crystal

types : (iii) S molecule Covalent network crystal

(i) Plastic (ii) P molecule (iii) S molecule
(iv) Iodine molecule Covalent network crystal
(iv) Iodine molecule (v) Tetra phosphorus (v) Tetra phosphorus decoxide Covalent network crystal
decoxide (vi) Ammonium phosphate (vii) Brass
(vi) Ammonium phosphate Ionic crystal
(viii) Rubidium (ix) Graphite (x) Diamond
(vii) Brass Metallic crystal
(xi) NaCl (xii) Silicon.
(viii) Rubidium Metallic crystal
(Each classification 12 mark)
1. SOLID STATE 13
constituent particle like an atom, ion or a molecule
(ix) Graphite Covalent crystal
in the crystal lattice is called lattice point or lattice
(x) Diamond Covalent crystal
site. OR
(xi) NaCl Ionic crystal
Any point at the intersection of the lines in the
(xii) Silicon Covalent crystal
unit cell occupied by a constituent particle like an
■ atom, an ion or a molecule in the crystalline solid is
Q. 35. Mention the types of the following solids : called a lattice point. ■
(i) CaF (ii) SiC (iii) Ice (iv) SO (v) CaCO
★ Q. 40. What is a unit cell ? (1 mark)
(vi) ZnS (vii) HCl (viii) CO (Each type 12 mark)
Ans.
Ans. (1) Unit cell : It is the smallest repeating structural unit
Solid Type of a crystalline solid (or crystal lattice) which when
repeated in different directions produces the crystal-
(i) CaF Ionic crystal
line solid (lattice).
(ii) SiC Covalent crystal
(2) The crystal is considered to consist of an infinite
(iii) Ice Hydrogen bonded molecular crystal
number of unit cells.
(iv) SO Molecular crystal
(3) The unit cell possesses all the characteristics of the
(v) CaCO Ionic crystal
crystalline solid. ■
(vi) ZnS Ionic crystal
Q. 41. What are the parameters of a unit cell ?
(vii) HCl Polar molecular crystal
(2 marks)
(viii) CO Non-polar molecular crystal
Ans. A unit cell is characterised by following
■ parameters :
Q. 36. What is a giant solid ? (1 mark) (1) Edges or edge lengths : The intersection of two
Ans. Covalent solid formed by covalent bonds between faces of crystal lattice is called as edge. The three
neighbouring constituent atoms of non-metallic edges denoted by a, b and c represent the dimen-
solid is called a giant solid. For example, graphite. sions (lengths) of the unit cell along three axes.
■ These edges may or may not be mutually perpen-
dicular.
Units
1.4 Crystal Structure
1.4.1 Crystal, lattice and basis
1.4.2 Unit cell
1.4.3 Types of unit cell
1.4.4 Crystal systems
Q. 37. What is lattice ? (1 mark)

Ans. Lattice is a geometrical arrangement of points in a
three dimensional periodic array. ■
Q. 38. What is crystal lattice (space lattice) ? Fig. 1.6 : Parameters of a unit cell
(1 mark)
(2) Angles between the edges (or planes) : There are
Ans. Crystal lattice (space lattice) : A regular arrange- three angles between the edges of the unit cell
ment of the constituent particles (atoms, ions or represented as , and .
molecules) of a crystalline solid having similar (i) The angle is between edges b and c.
environment in three dimensional space is called (ii) The angle is between edges a and c.
crystal lattice or space lattice. ■ (iii) The angle is between edges a and b.
Q. 39. What is a lattice point ? (1 mark) The crystal is defined with the help of these
Ans. Lattice point : A position occupied by a crystal parameters of its unit cell. ■

Q. 42. Represent space lattice and unit cell diagram- (4) Base-centred unit cell : A unit cell in which the
matically. (2 marks) constituent particles are present at the corners as
Ans. well as at the centres of two opposite faces is called
end-centred unit cell. ■
Q. 45. Explain briefly crystal systems. (2 marks)

Ans.
(1) The constituent particles like atoms, ions or mole-
cules of the crystal can be arranged in seven
different ways changing edges (a, b, c) and angles
(, , ) and accordingly they form seven systems
or types of the crystal.
(2) These seven crystal system are named as :
(a) Cubic system, (b) Tetragonal system
Fig. 1.7 : Representation of space lattice and unit cell (c) Orthorhombic system (d) Rhombohedral sys-
■
tem (e) Monoclinic system (f) Triclinic system
Q. 43. What do you understand by the basis of
(g) Hexagonal system. ■
crystal lattice ? (2 marks)
Ans. Units
(1) A crystal structure is formed by attaching a consti- 1.5 Cubic system
tuent particle to lattice points. 1.5.1 Number of particles in cubic unit cell
(2) The constituent particles attached to the lattice 1.5.2 Relationship between molar mass, density
points form the basis of the crystal lattice. of the substance and unit cell edge length
(3) The crystal structure is obtained by attaching a basis
to each of the lattice points. Q. 46. What are Bravais lattices ? (2 marks)
(4) This is represented by the following schematic Ans.
equation :
(1) There are seven crystal systems according to the
edges (a, b, c) and angles (, , ).
(2) The constituents of the crystal may be present at
corners, face centres, body centres, edge centres and
voids.
(3) By mathematical analysis, it has been proved that
Fig. 1.8 : Arrangement in crystal ■ only fourteen different kinds of space lattices are
Q. 44. What are the types of unit cells ? (2 marks) possible.
Ans. Basically unit cells are of two types as follows : (4) Hence there are fourteen different ways of arrange-
(1) Primitive unit cells : The unit cells in which the ment of the lattice basis.
constituent particles like atoms, ions or molecules (5) These fourteen lattices of seven crystal systems are
are present only at the corners of the unit cell are called Bravais lattices. ■
called primitive unit cells or simple unit cells.
(2) Body-centred unit cell : A unit cell in which the Q. 47. Explain Bravais lattices of a cubic system.
constituent particles are present at the corners as (3 marks) OR
well as at its body-centre is called body-centred unit Explain unit cells of a cubic system. (3 marks)
cell. Ans. Cubic lattice : For this, edges are a:b:c and
(3) Face-centred unit cell : A unit cell in which the angles are :::90°. In this cubic system,
constituent particles are present at the corners as there are three Bravais lattices.
well as at the centre of each face is called face- (1) Simple (or primitive) cubic unit cell (SCC) : In
centred unit cell or cubic close packed (CCP) unit this unit cell, atoms are present only at 8 corners of
cell. the cube.
1. SOLID STATE 15
(In cubic close packing unit cell, the lattice points
are also at edge centres and body centre.)
(3) Body-centred cubic unit cell : In this, the lattice

points are at 8 corners and one at body centre. ■
Q. 49. Find the number of atoms per unit cell in the

following crystal structures.
Fig. 1.9 : Simple cubic unit cell (1) Simple cubic unit cell (2) Body-centred
cubic unit cell (3) Face-centred cubic cell.
(2) Body-centred cubic unit cell (BCC) : In this,
(2 marks each)
atoms are present at 8 corners along with one
Ans.
additional atom at the body-centre of the cube.
(1) Number of atoms in
primitive simple cubic
(scc) unit cell :
In simple or primitive cubic
unit cell, there are 8 atoms
at 8 corners. Each corner
contributes 1/8th atom to
the unit cell. Fig. 1.12 : Simple or
Fig. 1.10 : Body-centred cubic
Primitive cubic unit cell
(3) Face-centred cubic unit cell (FCC) : In this unit Number of atoms present in the unit cell
cell, atoms are present at 8 corners and at 6 face 1
: ;8:1
centres. 8
Hence the volume of the unit cell is equal to the
volume of one atom.
(2) Number of atoms in body-

centred cubic (bcc) unit
cell :
In this unit cell, there are
8 atoms at 8 corners and
Fig. 1.11 : Face-centred cubic one additional atom at the
■
body centre. Each corner
Q. 48. Give the number of lattice points in one unit contributes 1/8th atom, to
cell of the following crystal structures : the unit cell, hence due to 8 Fig. 1.13 : Body-centred
(1) Simple cubic corners. cubic unit cell
(2) Face-centred cubic
1
(3) Body-centred cubic. (1 mark each) Number of atoms:8;
8
Ans. Lattice points in one unit cell represent the posi- :1 atom.
tions of atoms, ions or molecules in the unit cell. An atom at the body centre wholly belongs to the
(1) Simple cubic unit cell : In this primitive unit cell, unit cell.
the lattice points are at 8 corners of the unit cell. Total number of atoms present in bcc unit
Hence there are 8 lattice points. cell:1;1:2.
(2) Face-centred cubic unit cell : In this unit cell, the Hence the volume of unit cell is equal to the volume
lattice points are at 8 corners and 6 face centres. of two atoms.

(3) Number of atoms in face- Each face centre contributes half of the atom to the
centred cubic (fcc) unit unit cell, hence due to 6 face centres,
cell : 1
Number of atoms: ;6:3.
In this unit cell, there are 2
8 atoms at 8 corners and Total number of atoms present in fcc unit cell
6 atoms at 6 face centres. :1;3:4.
Each corner contributes Hence the volume of the unit cell is equal to the
1/8th atom to the unit cell, volume of four atoms. ■
hence due to 8 corners, Fig. 1.14 : Face centred ★ Q. 50. Calculate the number of atoms in fcc unit
unit cell
1 cell. (2 marks)
Number of atoms: ;8:1.
8 Ans. For answer refer to Q. 49 (3). ■
Do you know ?
(Textbook page 7)
Table 1.2 : The names of fourteen Bravais lattices (unit cells) for each of the seven crystal system are shown below :
Crystal system Bravais lattices
Name Unit cell structure
1. Cubic i. simple or primitive

ii. body-centred
iii. face-centred
2. Orthorhombic i. simple or primitive

ii. body-centred
iii. face-centred
iv. base-centred
3. Tetragonal i. simple or primitive

ii. body-centred
4. Monoclinic i. simple or primitive

ii. base-centred
1. SOLID STATE 17
Crystal system Bravais lattices
Name Unit cell structure
5. Rhombohedral i. simple or primitive
6. Triclinic i. simple or primitive
7. Hexagonal i. simple or primitive
Remember ... Q. 52. Obtain a relation for the density of the unit cell
(Textbook page 8) and radius of atom or sphere for the following :
Each corner particle of a cube is shared by 8 cubes, (1) Simple cubic (scc) crystal (2 marks)
each face particle is shared by 2 cubes and each edge (2) Body centred cubic (bcc) crystal (2 marks)
particle is shared by 4 cubes. (3) Face centred cubic (fcc) crystal. (2 marks)
Ans.
★ Q. 51. Obtain the relationship between density of a
(1) Consider a unit cell of a simple cubic crystal. It has
substance and the edge length of unit cell. OR
8 atoms at 8 corners of the unit cell.
Derive relationship between molar mass,
1
density of the substance and unit cell edge length Total number of atoms in unit cell: ;8:1
8
of the crystal. (2 marks) If a is the length of edge of cubic unit cell and r is
Ans. the radius of the atom, then r:a/2 or a:2r.
(1) Consider a cubic unit cell of edge length ‘a’. Volume of the unit cell:a:(2r):8r
The volume of unit cell:a If M is atomic mass of the element, then mass of
(2) If there are ‘n’ particles per unit cell and the mass of one atom is M/NA where NA is Avogadro number.
particle is ‘m’, then If there are ‘n’ atoms in one unit cell then,
Mass of unit cell:m;n. M
(3) If the density of the unit cell of the substance is Mass of unit cell:n;Mass of one atom:n;
NA
then Mass of unit cell
Mass of unit cell Density:
Density of unit cell: Volume of unit cell
Volume of unit cell n;M/NA n;M
m;n : :
: ■ a NA ;a
a

Since there is one atom present in one unit cell, Q. 53. What is coordination number? What is its
M significance? (2 marks)
:
NA ;a Ans.
(2) Consider a unit cell of body centred cubic (bcc) (1) Coordination number : The number of the closest
crystal. It has 8 atoms at 8 corners and one neighbouring constituent particles like atoms, ions
additional atom at the centre of body of unit cell. or molecules which are in contact with a particular
1 particle or an atom in the crystal lattice is called
Number of atoms due to 8 corners: ;8:1
8 coordination number of that particle.
Body centred atom, wholly belong to the unit cell. (In the crystal lattice, all atoms may have same or
Hence total number of atoms in the unit cell is two. different coordination numbers.)
If M is atomic mass of an element then M/NA is (2) The magnitude of the coordination number is a
mass of one atom where NA is Avogadro number. measure of compactness of spheres in close-packed
Mass of unit cell:Mass of 2 atoms in unit cell structures.
:2M/NA (3) The higher the coordination number, the closer are
If a is the edge length or lattice parameter then, the spheres to each other. ■
Volume of cubic unit cell:a
Q. 54. Explain linear packing in one direction.
Mass of unit cell
Density of unit cell: (2 marks) OR
Volume of unit cell
2M/NA 2M Explain close packing in one dimension.
: : . (2 marks)
a NA a
Ans. Linear packing in one direction or close packing
(3) Consider a unit cell of face centred cubic (fcc)
in one dimension :
crystal.
The constituent particles of the crystal may be of
It has 8 atoms at 8 corners and 6 atoms at 6 face
centres. varying shapes but for better understanding we
Total number of atoms in unit consider particles as hard spheres of equal size.
1 1
cell: ;8; ;6:1;3:4
8 2
If M is the atomic mass of an element, then mass of
one atom is M/NA , where NA is Avogadro number. Fig. 1.15 : The dimensional arrangement of spheres
Mass of unit cell:Mass of 4 atoms There is only one way of arranging or packing
M
:4; spheres placed in a horizontal row touching one
NA
another. Since one sphere is in contact with two
If a is the edge length of this cubic unit cell then,
neighbouring spheres except the end atoms, the
volume of unit cell:a
coordination number in this arrangement is two.
Mass of unit cell
Density of unit cell: This packing may be in any one direction x, y or z.
Volume of unit cell
■
4;M/NA
: Q. 55. Explain the following :
a
4M Planar packing arrangement of spheres.
:
NA a ■ (2 marks) OR
Close packing in two dimensions. (2 marks) OR
Units
★ AAAA type (2 marks) and ABAB type of two
1.6 Packing of particles in crystal lattice
dimensional arrangement. (2 marks) OR
1.6.1 Close packed structures
(i) Square close packing (2 marks)
1.6.2 Coordination number in close packed
(ii) Hexagonal close packing. (2 marks)
structure
Ans. Two dimensional close packing crystal structure
1.6.3 Number of voids per atom in hcp and ccp
can be generated by placing one dimensional linear
1. SOLID STATE 19
crystal structure over another to form multiple In this arrangement, crests of the spheres of one
layers. This staking of linear rows may be taking row are placed into the depressions or troughs
place in two different ways giving two different two formed between adjacent spheres of next row. This
dimensional structures as follows : arrangement is repeated consecutively throughout.
(i) AAAA type two dimensional close packing or In this arrangement, crests of the spheres of one
square close packing : row are in contact with depressions or troughs of
In this arrangement, various one dimensional rows next row.
are placed on one over other so that each sphere in If one row of spheres is labelled as A then the
one row is over the another sphere of another row next row will be B, third row will again be A, fourth
forming planar structure. In this, spheres have row B and so on. Hence this planar or two dimen-
horizontal as well as vertical alignment. All the sional close packing is called ABAB... type pack-
rows of spheres are identical in planar structure. All ing.
crests as well as all the depressions or troughs
In this arrangement, each sphere is in contact
formed by the arrangement are also aligned.
with six other spheres around it hence the coordina-
tion number of each sphere is six and the packing is
called two dimensional or planar hexagonal close
packing. In this, the packing efficiency is 60.4 %
which is more than linear close packing. ■
Q. 56. Explain close packing in three dimensions.

(4 marks)
Ans. Close packing in three dimensions :
Fig. 1.16 : Square close packing Three dimensional crystal structures are obtained
by stacking of two dimensional layers. Simple cubic
If the first row is labelled as A type, then second
lattice is obtained by stacking of two dimensional
and all subsequent rows are also identical, hence are
square layers.
of A type. Therefore this planar two dimensional
The stacking of two dimensional hexagonal close
close packing is called AAAA…… type packing.
packed layers gives two structures namely hexag-
In this arrangement, each sphere is in contact
onal close packed (hcp) structure and face centred
with (or touching) four other spheres around it,
(fcc) structure.
hence the coordination number of each sphere is
(i) Stacking of square close packed layers :
four and the packing is called two dimensional
or planar square close packing. In this, packing
efficiency is 52.4 %.
(ii) ABAB type two dimensional packing or hexag-
onal close packing :
Fig. 1.18 : Stacking of square close packed layers

In this arrangement, the two dimensional AAAA
type square closed packed layers are placed one
over the other in such a way that the crests of all
Fig. 1.17 : Hexagonal ABAB type close packing spheres are in contact with successive layers in all
in two dimension (planar packing) directions. All spheres of different layers are per-

fectly aligned horizontally and vertically forming If the first layer is labelled A and second layer
unit cells having primitive or simple cubic struc- B, then the arrangement of packing will be of
ture. Since all the layers are identical and if each ABAB type. This is also called hexagonal close
layer is labelled as layer A, then whole three packing (hcp) as shown in the figure. In this,
dimensional crystal lattice will be of AAAA... type. packing efficiency is 74 %. The coordination
Each sphere is in contact with six surrounded number of each sphere is 12. The metals Be,
spheres, hence the co-ordination number of each Mg, Zn, Cd crystallise in HCP crystalline
sphere is six. structure.
(ii) Stacking of two hexagonal close packed layers :
A close packed three dimensional structure can be
generated by arranging hexagonal close packed
layers in a particular manner.
In this the spheres of second layer are placed in
the depression of the first layer.
In this if first layer is labelled as A then second
layer is labelled as B since they are aligned differ-
ently.
Fig. 1.20 : Hexagonal close packing (hcp)
(b) Cubic close packing (ccp) : If the crests of

spheres of third layer are placed in the positions
of tetrahedral void ‘a’ having apex upward of
Fig. 1.19 : Two layers of closed packed spheres first layers, then the third layer will not be
In this, all triangular voids of the first layers are identical to the first, and may be labelled as C,
not covered by the spheres of the second layer. The which is different from A and B layers. Fourth
triangular voids which are covered by second layer layer may be arranged above third layer such
spheres generate tetrahedral void which is sur- that the spheres are aligned, so that the first
rounded by four spheres. The triangular voids in layer and fourth layer are identical, second and
one layer have above them triangular voids of fifth layers are identical and so on.
successive layers.
The overlapping triangular voids from two layers
together form an octahedral void which is sur-
rounded by six spheres.
(iii) Placing third hexagonal close packed layer :
(a) Hexagonal close packing (hcp) : If the crests
of spheres of third layer are placed on the
triangular shaped tetrahedral voids C of the
second layer, then three dimensional closest
packing structure is obtained in which the
spheres of third layer lie directly above the
spheres of first layer, i.e., first and third layers
are identical. Following same placing of layers,
fourth layer will be identical to second layer. Fig. 1.21 : Cubic close packing (ccp)
1. SOLID STATE 21
If first, second and third layers are labelled as
A, B and C respectively then the arrangement
of packing will be ABCABC type. This is also
called cubic close packing (ccp) as shown in
the figure. This is similar to face centred cubic
(fcc) packing.
In this, arrangement packing efficiency is Fig. 1.22 : Tetrahedral void
74 % and the coordination number of each The arrangement of four spheres around the void
sphere is 12. ■ is tetrahedral. A tetrahedral void is formed when a
triangular void made by three coplanar spheres is in
★ Q. 57. How are the spheres arranged in first
contact with fourth sphere above or below it.
layer of simple cubic close-packed structures ?
(2) Characteristics of tetrahedral void :
How are the successive layers of spheres placed (i) The volume of the void is much smaller than
above this layer ? (4 marks) that of atom or sphere.
Ans. For answer, refer to answers (i) and (ii) of Q. 56. (ii) Larger the size of sphere, more is the size of
■ void.
(iii) If R is the radius of the constituent atom, then
★ Q. 58. Third layer of spheres is added to second
the radius of the tetrahedral void is 0.225 R.
layer so as to form hcp or ccp structure. What is
(iv) Coordination number of tetrahedral void is
the difference between the addition of third layer four.
to form these hexagonal close-packed struc- (v) There are two tetrahedral voids per sphere, in
tures ? (2 marks) the crystal lattice. If the number of closed
Ans. packed spheres is N then the number of
(1) In the formation of hexagonal closed-packed (hcp) tetrahedral voids is 2N. ■
★ Q. 60. Sketch a tetrahedral void. (2 marks)

structure, the first one dimensional row shows
Ans. For a figure of tetrahedral void, refer to fig. 1.22
depressions between neighbouring atoms.
■
(2) When a second row is arranged so that spheres fit
Q. 61. Explain octahedral void. (2 marks)
in these depressions then a staggered arrangement is
Ans.
obtained. If the first row is A then the second row (1) Octahedral void : The vacant space or void at the
is B. centre of six spheres (or atoms) which are placed
(3) When third row is placed in staggered manner in octahedrally is called octahedral void.
contact with second row then A type arrangement is
obtained.
(4) Similarly, the spheres in fourth row can be arranged
as B type layer. This results in ABAB ... type setting
of the layers. This gives hexagonal close packing
(hcp) structure.
(For diagram refer to Fig. 1.20) ■
Q. 59. Explain tetrahedral void. (2 marks)

Fig. 1.23 : Octahedral voids
Ans.
(2) Characteristics of octahedral void :
(1) Tetrahedral void : The vacant space or void
(i) The volume of the void is small.
among four constituent particles having tetrahedral (ii) There is one octahedral void at the body centre
arrangement in the crystal lattice is called tetrahed- and twelve octahedral void positions at twelve
ral void. edge centres.

(iii) If R is the radius of constituent atom, then the Q. 64. What is packing efficiency? (2 marks)
radius of the octahedral void is 0.414 R. Ans.
(iv) The coordination number of octahedral void is (1) Packing efficiency : It is the fraction or a percen-
six. tage of the total space (of the unit cell) occupied by
(v) There is one octahedral void per sphere in the the particles (spheres).
crystal lattice. If the number of closed packed
Packing efficiency
spheres is N then the number of octahedral
Volume occupied by particles in unit cell
voids is N. ■ :
Total volume of unit cell
Remember ... (2) The magnitude of packing efficiency gives a measure
(Textbook page 10)
● It is important to note that the triangular shapes of of how tightly particles are packed together. ■
depressions in A and B layer do not overlap. The Q. 65. Calculate packing efficiency in simple cubic
apices of two triangular depressions in A and B lattice. OR
layer point in opposite directions. ★ Calculate the packing efficiency of metal crys-
● The depressions in which spheres of second layer tal that has simple cubic structure. (2 marks)
rest are tetrahedral voids while the depressions in Ans. Step 1 : Radius of sphere : In simple cubic lat-
which no sphere rests are octahedral voids. tice, the atoms (spheres) are present at eight corners
and in contact along the edge in the unit cell.
Q. 62. What are number of voids per atom in hcp
If ‘a’ is the edge length of the unit cell and ‘r’ is
and ccp ? (2 marks)
the radius of the atom, then
Ans. The tetrahedral and octahedral voids occur in hcp
a:2r or r:a/2
and ccp/fcc structures. There are two tetrahedral
voids associated with each atom. The number of
octahedral voids is half that of tetrahedral voids.
Thus, there is one octahedral void per atom. ■
Remember ...
(Textbook page 11)
● If N denotes number of particles, then number of
tetrahedral voids is 2N and that of octahedral voids
is N. Fig. 1.24 : scc structure
Step 2 : Volume of sphere :
★Q. 63. How are tetrahedral and octahedral voids 4
formed ? (2 marks) Volume of one particle: ;r
3
Ans. For tetrahedral void, refer to answer (1) of 4 a
: ;(a/2) :
Q. 59 and for octahedral void, refer to answer (1) of 3 6
Q. 61. ■ Step 3 : Total volume of particles : Since the unit
cell contains one particle, Volume occupied by one
Units
a
1.7 Packing efficiency particle in unit cell:
6
1.7.1 Packing efficiency of metal crystal in
Step 4 : Packing efficiency :
simple cubic lattice
Packing efficiency
1.7.2 Packing efficiency of metal crystal in
body-centred cubic lattice : ;100
Volume of unit cell
1.7.3 Packing efficiency of metal crystal in face-
a/6
centred cubic lattice (or ccp or hcp lattice) : ;100
a
1.7.4 Number of particles and unit cells in x g of 3.142;100
metal crystal : :52.36%
6
1. SOLID STATE 23
Packing efficiency:52.36% Step 4 : Packing efficiency
Percentage of void space:100952.36 Packing efficiency
:47.64% ■ Volume occupied by particles in unit cell
: ;100
Q. 66. Calculate packing efficiency in body-centred Volume of unit cell
cubic lattice. (2 marks) (3a/8
: ;100
Ans. Step 1 : Radius of sphere : a
In the unit cell of body-centred cubic lattice, there (3;3.142
are 8 atoms at 8 corners and one atom at the centre : ;100
8
of the cube. :68%
Packing efficiency:68%
Percentage of void space:100968
:32%
■
Q. 67. Calculate packing efficiency in face-centred

cubic lattice. (2 marks)
Ans. Step 1 : Radius of sphere :
Fig. 1.25 : bcc structure In the unit cell of face-centred cubic lattice, there 8
The atoms are in contact along the body diagonal atoms at 8 corners and 6 atoms at 6 face centres.
BF. Let a be the edge length and r the radius of an Consider the face ABCD.
atom. The atoms are in contact
Consider a triangle BCE. along the face diagonal BD.
BE:BC;CE:a;a:2a
Let a be the edge length and
Consider triangle BEF,
r, the radius of an atom.
BF:BE;EF:2a;a:3a
Consider a triangle BCD.
BF:(3a.
BD:BC;CD
From figure, BF:4r
:a;a:2a
4r:(3a Fig. 1.26 : fcc structure
(3 BD:(2a
r: a. From figure, BD:4r
4
Step 2 : Volume of sphere : 4r:(2a
4 (2
Volume of one particle: r r: a:
a
3 4 2(2
4
:
3 4
a

(3
r:
a
2(2
4 ((3)
: ; ;a Step 2 : Volume of sphere :
3 64
4
(3 a Volume of one particle: r
: 3
16
Step 3 : Total volume of particles :
The unit cell of bcc structure contains 2 particles.
:
4
3
;

a
2(2
Volume occupied by 2 particles:

2;(3a
16
4
: a
3 1
2(2
(3a a
: :
8 12(2

Step 3 : Total volume of particles : Q. 68. Which of the three types of packing used by
The unit cell of fcc crystal lattice contains 4 particles. metals makes the most efficient use of space and
a which makes the least efficient use ?
Volume occupied by 4 particles:4; Ans. fcc has the most efficient packing of particles while
12(2
scc has the least efficient packing. ■
a
: Use your brain power !
3(2
(Textbook page 13)
Step 4 : Packing efficiency :
Q. Which of the three lattices scc, bcc and fcc has the
Packing efficiency
most efficient packing of particles ? Which one has the
: ;100 least efficient packing ?
Volume of unit cell
For answer refer to Q. 68.
a/3(2
: ;100
a Q. 69. Calculate the number of particles and unit
3.142 cells in ‘x’ g of metallic crystal. (3 marks)
: ;100
3(2 Ans. Consider ‘x’ gram of a metallic crystal of molar
:74% mass M and density . If the unit cell of the crystal
Packing efficiency:74% has edge length ‘a’ then, volume of unit cell:a.
M
Percentage of void space:100974 Mass of one metal atom: . If ‘n’ number of
NA
:26% atoms are present in one unit cell then
Table 1.3 : Edge length and particle parameters n;M
in cubic system Mass of unit cell: .
NA
Unit cell Relation Volume of Total volume
If ‘a’ is the edge length of the unit cell then,
between a one particle occupied by
Volume of unit cell:a
n;M 1
and r particles in Density of unit cell:: ;
NA a
unit cell
;NA ;a
1. scc r:a/2: a/6: a/6:
M:
n
0.5000 a 0.5237 a 0.5237 a B Molar mass M gram contains NA particles
x;NA
2. bcc r:(3a/4 (3a/16 (3a/8 x gram contains particles.
M
:0.4330a :0.34a :0.68a
Substituting the value M,
3. fcc/ r:(2a/4: a/12(2 a/3(2 (i) Number of particles in x g crystal
ccp 0.3535 a :0.185 a :0.74 a x;NA
:
;NA ;a/n
Table 1.4 : Coordination number and packing x;n
efficiency in systems : particles
;a
Lattice Coordination Packing (ii) Number of unit cells in x g crystal :
number of atoms efficiency B n particles are present in 1 unit cell
x;n x;n 1
1. scc 6 : four in the same layer, 52.4% are present in, ;
;a ;a n
one directly above and one
x
directly below : unit cells
;a
2. bcc 8 : four in the layer below 68% V
(iii) Number of unit cells in V volume of crystal:
and four in the layer above a
[ Alternative method :
3. fcc/ccp/ 12 : six in its own layer, 74%
Consider ‘x’ g metal of atomic mass M g mol\.
hcp three above and three below
x
Number of moles of metal:
■ M
1. SOLID STATE 25
x 1
(a) Number of atoms (particles) of metal: ;NA Number of C atoms: ;8:1.
M 8
(b) If unit cell contains ‘n’ atoms, 1
Number of D atoms: ;6:3.
x N 2
Number of unit cells: ; A
M n Thus unit cell contains one C atom and three D
(c) If ‘a’ is the edge length then, atoms.
Volume of unit cells:a Hence the formula of the compound is CD .

Number of unit cells in V volume of Ans. Formula of the compound:CD .

------------------------------------------------------------------------------------
V ■
crystal: . ]
a (3) A cubic unit cell contains atoms A at the corners,
★ Q. 70. Mention two properties that are common to
atoms B at face centres and atom C at the body
both hcp and ccp lattices. (1 mark) centre. What is the formula of the crystalline
Ans. In hcp and ccp crystal lattices coordination number compound ? (2 marks)
is 12 and packing efficiency is 74%. ■
Solution :
Given : Atoms A are at 8 corners, atoms B at the 6
Solved Examples 1.5 – 1.7
face centres and one atom C at body centre.
Q. 71. Solve the following : 1
Total number of atoms of A: ;8:1.
[1 m:10 dm:100 cm:10 nm:10 pm, 8
1 At :10\ cm:100 pm] 1
Total number of atoms of B: ;6:3.
2
(1) A cubic unit cell of a crystal consists of atoms of One atom of C at the body centre.
A and B elements. Atoms of A occupy corners of Therefore the unit cell contains one atom of A, three
the unit cell while one B atom is present at the atoms of B and one atom of C.
body centre. Determine the formula of the cry- Hence the formula of the compound is AB C.
stalline compound. (2 marks)
Ans. The formula of the crystalline compound is
Solution : AB C.
Given : Atoms of A are at the corners while atom B
------------------------------------------------------------------------------------
is at the body centre of the cubic unit cell. (4) An element A and B constitute bcc type crystal-
1 line structure. Element A occupies body centre
Since th atom is contributed at each corner and
8
position and B is at the corners of cube. What is
there are 8 corners in unit cell, number of atoms of
the formula of the compound ? What are the
1
A due to corners is ;8:1. coordination numbers of A and B ? (2 marks)
8
Solution :
In addition there is one atom of B at body centre.
Given : Crystalline structure is bcc type.
Hence this unit cell contains one atom of each, A
Atoms A are at 8 corners and atom B is at body
and B, therefore the formula of the compound is AB.
centre.
Ans. The formula of the compound:AB.
------------------------------------------------------------------------------------ Number of atoms of A in a unit cell
1
★ (2) Atoms C and D form fcc crystalline structure. : ;8:1.
8
Atom C is present at the corners of the cube and
Number of atom B in a unit cell:1.
D is at the face centres of the cube. What is the
Since unit cell contains one atom each of A and B,
formula of the compound ? (2 marks)
the formula of the compound is AB.
Solution :
The coordination number of an atom A at corner is 8.
Given : Crystal has fcc structure.
The coordination number of an atom B at body
Atoms C are at 8 corners while atoms D are at 6 face
centre is 8.
centres of the cubic unit cell.
Ans. Formula of the compound:AB.
1
At the corner, th of each C atom is present while at Coordination number of A:8
8
Coordination number of B:8.
each face centre, half of each D atom is present. ------------------------------------------------------------------------------------

(5) Mention the number of atoms in the following (iii) Number of ZnS molecules:4
unit cells : (iv) Molecular formula of zinc blende:ZnS.
(a) scc (b) bcc (c) fcc (d) hcp. (2 marks) ------------------------------------------------------------------------------------
Ans. (8) In a crystalline compound, atoms A occupy ccp
lattices while atoms B occupy 2/3 rd tetrahedral
Unit cell Number of atoms
voids. What is the formula of the compound ?
(a) scc 1 (2 marks)
(b) bcc 2 Solution :
(c) fcc 4 In ccp unit, lattice points are 8 corners and 6 face
(d) hcp 3 centres where atoms A are present.
------------------------------------------------------------------------------------ Number of A atoms
1 1
(6) 0.1 mole of Buckminster fullerene of molar mass : ;8; ;6:1;3:4
8 2
720 gmol 91 contains how many Kg of carbon ? (corners) (face centres)
(1 mark) In cubic unit cell, there are 8 tetrahedral voids.
Solution : Hence,
Molar mass of fullerene, C :720 gmol 91 2 16
.. Number of B atoms: ;8: .
. Mass of 1 mole of fullerene:720 g:0.72 kg 3 3
Mass of 0.1 mole of fullerene:0.72;0.1 Hence the formula should be A B16/3 or A B or

:0.072 kg A B .

Ans. 0.072 kg. Ans. The formula of the compound is A B .
------------------------------------------------------------------------------------

------------------------------------------------------------------------------------
★ (9) In an ionic cystalline solid atoms of element Y
(7) In a cubic crystalline structure of zinc blende
form hcp lattice. The atoms of element X occupy
(ZnS), sulphide ions are at corners and face
one third of tetrahedral voids. What is the
centres while zinc ions occupy half of tetrahedral
formula of the compound? (2 marks)
voids.
Solution :
Find in the unit cell : (i) Number of Zn> ions
In the given hcp lattice, Y atoms are present at
(ii) Number of S\ ions
12 corners and 2 face centres.
(iii) Number of ZnS molecules
1 1
(iv) Molecular formula of zinc blende.(2 marks) Number of Y atoms: ;12;2; :3
6 2
Solution : There are 6 tetrahedral voids, the number of X
Given : S\ ions are at 8 corners and 6 face 1
atoms: ;6:2
centres. 3
Zn> ions occupy half of tetrahedral voids. Formula of the compound is X Y .

------------------------------------------------------------------------------------
Number of S\ ions in unit cell
1 1 (10) A compound forms hcp structure. What is the
: ;8; ;6 number of (a) octahedral voids, (b) tetrahedral
8 2
(corners) (face centres) voids, (c) total voids formed in 0.2 mol of the
:1;3:4 compound? (3 marks)
Cubic unit cell has 8 tetrahedral voids. Since half of Solution :
them are occupied by Zn> ions, there are 4Zn> Number of atoms in 0.2 mol of the compound
ions in the unit cell. :0.2;NA :0.2;6.022;1023
Hence number of zinc sulphide (ZnS) molecules is 4. :1.2044;10 atoms
Molecular formula of zinc blende is ZnS. (a) Number of octahedral voids
Ans. (i) Number of Zn> ions:4 :Number of atoms
(ii) Number of S\ ions:4 :1.2044;10
1. SOLID STATE 27
(b) Number of tetrahedral voids Total number of Cu atoms
:2;Number of atoms 1 1
: ;8; ;6:1;3
:2;1.2044;10 8 2
:2.4088;10 :4
(c) Total number of voids Mass of one Cu atom
:1.2044;10;2.4088;10 63.5
: :1.054;10\ g
:3.6132;10 6.022;10
Ans. (a) Number of octahedral voids Mass of 4 Cu atoms:4;1.054;10\
:1.2044;10 :4.216;10\ g
(b) Number of tetrahedral voids Mass of unit cell:Mass of 4 Cu atoms
:2.4088;10 :4.216;10\ g
(c) Total number of voids:3.6132;10 Volume of unit cell:a:(3.61;10\)
------------------------------------------------------------------------------------
:4.7;10\ cm
★ (11) Cesium chloride crystallizes in cubic unit cell
Mass of unit cell
with Cl 9 ions at the corners and Cs ; ion in the Density of unit cell:
Volume of unit cell
centre of the cube. How many CsCl molecules
4.216;10\
are there in the unit cell ? (2 marks) : :8.97 g cm\
4.7;10\
Solution :
Ans. Density of Cu:8.97 g cm\.
Number of Cs ; ion at body centre:1 ------------------------------------------------------------------------------------
1
Number of Cl 9 ions due to 8 corners:8; :1 (14) Niobium is found to crystallise with bcc struc-
8
ture and found to have density of 8.55 g cm\
Hence unit cell contains 1 CsCl molecule.
------------------------------------------------------------------------------------ (OR 8.55 kg m\). Determine the atomic radius
★ (12) Cu crystallizes in fcc unit cell with edge length of niobium if its atomic mass is 93.
of 495 pm. What is the radius of Cu atom ? (3 marks)
(2 marks) Solution :
Solution : Given : Density of Niobium (Nb) crystal:8.55
Given : a:495 pm g cm\
Radius, r:? Crystalline structure is bcc.
For fcc structure, Atomic mass of Nb:93 g mol\
a 495
radius:r: : :175 pm Avogadro number:NA :6.022;10 mol\
2(2 2;(2
Atomic radius of Niobium:?
Ans. Radius of Cu atom:175 pm
------------------------------------------------------------------------------------ In bcc unit cell, there are 8 atoms at 8 corners and
(13) Copper crystallises into a fcc structure and the 1 atom at the body centre.
unit cell has length of edge 3.61;10\ cm. 1
Number of Nb atoms: ;8;1:1;1:2.
8
Calculate the density of copper. Atomic mass
of copper is 63.5 g mol\. (3 marks) Mass of one Nb atom
Solution : 93
: :1.544;10\ g
Given : Crystalline structure of Cu is fcc. 6.022;10
Edge length:a:3.61;10\ cm Mass of 2 Nb atoms:2;1.544;10\
Atomic mass of Cu:63.5 g mol\ :3.088;10\ g
Avogadro number:6.022;10 mol\ Mass of unit cell
Density:d:? :Mass of 2Nb atoms:3.088;10\ g
In fcc structure, there are 8 Cu atoms at 8 corners If a is edge length of bcc unit cell,
and 6 Cu atoms at 6 face centres. volume of unit cell:a

Mass of unit cell :6.777;10\ dm
Density:
Volume of unit cell :6.777;10\ cm
3.088;10\ a:(6.777;10\)1/3 :(67.77;10\)1/3
:
a
:4.077;10\ cm
3.088;10\ 3.088;10\
a: : If r is the radius of Au atom, then for fcc unit cell,
8.55
a
:0.361;10\ cm:36.1;10\ cm r:
2 (2

a:(36.1;10\) :3.3;10\ cm 4.077;10\
: :1.442;10\ cm:144.2 pm
If r is the radius of 1 Nb atom, then in bcc 2 (2
structure Ans. Radius of Au atom:144.2 pm.
(3 (3 ------------------------------------------------------------------------------------
r: a: ;3.3;10\ ★ (16) The density of iridium is 22.4 g/cm. The unit
4 4
:1.43;10\ cm cell of iridium is fcc. Calculate the radius of
:1.43;10\ m iridium atom. Molar mass of iridium is 192.2
:1.43;10\;10 nm g/mol. (3 marks)
:0.143 nm Solution :
Ans. Atomic radius of niobium atom:0.143 nm Given : Crystal structure of iridium:fcc
------------------------------------------------------------------------------------ Molar mass of iridium:192.2 gmol 91
Density::22.4 gcm 93
(15) Gold occurs as face centred cube and has a Radius of iridium:?
density of 19.30 kg dm\. Calculate atomic In fcc structure, there are 8 Ir atoms at 8 corners
radius of gold. (Molar mass of Au:197) and 6 Ir atoms at 6 face centres.
(3 marks) 1 1
Total number of Ir atoms: ;8; ;6
Solution : 8 2
Given : Density of Au:19.3 kg dm\ :1;3
Molar mass:197 g mol\ :4
Avogadro constant:NA :6.022;10 mol\ 192.2
Mass of Ir atom:
Atomic radius of Au:? 6.022;10
In fcc unit cell, there are 8 atoms of Au at 8 corners :31.92;10 923 g
and 6 atoms at 6 face centres. Mass of 4 Ir atoms:4;31.92;10 923 g
Number of Au atoms in the unit :1.277;10 921 g
1 1 Mass of unit cell:1.277;10 921 g
cell: ;8; ;6 Mass of unit cell
8 2
Density of unit cell:
:4 atoms Volume of unit cell
Mass of 1 Au atom 1.277;10 921
22.4 :
197 a
: :3.271;10\ g 1.277;10 921
6.022;10 a:
Mass of 4 Au atoms:4;3.271;10\ g 22.4
:1.308 g;10\ g :57;10 924 cm
Mass of unit cell:1.308;10\ g a:(57;10 924):3.848;10 98 cm
Mass of unit cell If r is the radius of iridium atom, then for fcc
Density of the unit cell: structure,
Volume of unit cell
1.308;10\ a
: r:
a 2(2
1.308;10\ 1.308;10\ 3.848;10 98
a: : :
19.3 2;1.414
1. SOLID STATE 29
:1.36;10 98 cm Hence the nature of unit cell:face-centred cubic
:136 pm unit cell
Ans. Radius of iridium atom:136 pm Ans. Radius of Al atom:125 pm
------------------------------------------------------------------------------------
The nature of cubic unit cell is fcc.
------------------------------------------------------------------------------------
★ (17) Aluminium crystallizes in cubic close packed
structure with unit cell edge length of 353.6 pm. (19) A compound is formed by two elements X and Y.
What is the radius of Al atom ? How many unit The atoms of Y form ccp structure. The atoms of
cells are there in 1.00 cm of Al ? (3 marks) 1
A occupy of tetrahedral voids. Find the for-
Solution : 3
Given : Structure of Al mula of the compound. (2 marks)
:Cubic close packed structure Solution :
:ccp structure In ccp structure, Y atoms are present at 8 corners
Edge length of unit cell:a:353.6 pm and 6 face-centres of the ccp structure.
r:?
:3.536;10 98 cm The number of Y atoms: ;8 ; ;6

1
8
1
2
Number of unit cells in 1.00 cm of Al:? corners face centres
a 353.6 :1;3:4
Radius of Al atom:r: : 1
2(2 2(2 There are 8 tetrahedral voids of which rd are
3
353.6
: :125 pm 8
2;1.414 occupied by atoms X. Hence unit cell has atoms of
3
Volume of one unit cell :a:(3.536;10 98)
X and 4 atoms of Y. The formula will be,
:4.421;10 923 cm
X8/3 Y or X Y or X Y
1.00
Number of unit cells: Ans. Formula of the compound:X Y .
4.421;10 923
------------------------------------------------------------------------------------
:2.26;10
(20) A metal crystallises into two cubic faces namely
Ans. Radius of Al atom:125 pm
face centered (FCC) and body centered (BCC),
Number of unit cells:2.26;10
------------------------------------------------------------------------------------ whose unit cell edge lengths are 3.5 At and 3.0 At
respectively. Find the ratio of the densities of
★ (18) An element with molar mass 27 g/mol forms FCC and BCC. (3 marks)
cubic unit cell with edge length of 405 pm. If Solution :
density of the element is 2.7 g/cm. What is the Given : Edge length of unit cell of fcc metal
nature of cubic unit cell ? (fcc or ccp) (3 marks) :3.5At
Solution : :3.5;10\ cm
Given : Molar mass:M:27 g mol 91 Edge length of unit cell of bcc metal
Nature of crystal:cubic unit cell :3 At :3;10\ cm
Edge length:a:405 pm:4.05;10 98 cm
n;M
Density::2.7 g cm 93 Density d:
a;NA
Nature of unit cell:?
n;M where, n:Number of Fe atoms in the unit cell
: M:Atomic mass of metal
a;NA
;a;NA a:Edge length of unit cell
n: NA :Avogadro number
M
2.7;(4.05;10 98);6.022;1023 For fcc unit cell:n:4
: For bcc unit cell:n:2
27
:3.997 Density of fcc unit cell dfcc
:
X4 Density of bcc unit cell dbcc

nfcc ;M Avogadro number:NA :6.022;10 mol\
a ;NA Number of Al atoms:?
: fcc
nbcc ;M Number of unit cells:?
abcc ;NA 1 gram atom of Al:27 g Al contains 6.022;10

abcc
nfcc Al atoms
:
nbcc afcc Number of Al atoms in 10 g

4 3;10\ 10;6.022;10
: :
2 3.5;10\ 27
:1.26 :2.23;10
dfcc In fcc structure, each unit cell contains 4Al atoms.
Ans. Ratio of densities, :1.26. 2.23;10
dbcc Number of unit cells:
------------------------------------------------------------------------------------ 4
(21) The density of silver having atomic mass 107.8 :5.575;10
gram mol 91 is 10.8 gram cm 93. If the edge length Ans. Number of Al atoms:2.23;10
of cubic unit cell is 4.05;10 98 cm, find the Number of unit cells:5.575;10.
------------------------------------------------------------------------------------
number of silver atoms in the unit cell. (2 marks)
(NA :6.022;10, 1At :10 98 cm) (23) The density of iron crystal is 8.54 gram cm 93.
Solution : If the edge length of unit cell is 2.8 At and atomic
Given : d:10.8 g cm 93 mass is 56 gram mol 91, find the number of atoms
M:107.8 g mol 91 in the unit cell. What is the type of crystal ?
a:4.05;10 98 cm (3 marks)
Number of Ag atoms in unit cell:n:? Solution :
107.8 Given :
Mass of one Ag atom: Density of Fe crystal:d:8.54 g cm 93
6.022;10
:1.79;10 922 g a:2.8 At :2.8;10 98 cm
If there are n atoms, then Atomic mass:M:56 g mol 91
Mass of unit cell:n;1.79;10 922 g Number of atoms in unit cell, n:?
Volume of unit cell:a:(4.05;10 98 ) Mass of one atom:
56
:9.3;10 923 g
:6.643;10 923 cm 6.022;10
Mass of unit cell Volume of unit cell:a:(2.8;10 98 )
Density of unit cell: :2.195;10 923 cm
Volume of unit cell
n;1.79;10 922 If there are n atoms in the unit cell, then
10.8:
6.643;10 923 Mass of unit cell:n;9.3;10 923 g
10.8;6.643;10 923 Mass of unit cell
n: :4 Density of unit cell:
1.79;10 922 Volume of unit cell
Ans. Number of silver atoms (Ag) atoms in unit n;9.3;10 923
8.54:
cell:4. 2.195;10 923
------------------------------------------------------------------------------------ 8.54;2.195;10 923
n:
(22) Aluminium having atomic mass 27 g mol\ crys- 9.3;10 923
tallises in face centred packed cubic crystal. Find :2.016
the number of Al atoms in 10 g aluminium. How X2
many unit cells will be present in it ? (2 marks) Since unit cell contains 2 atoms, the crystal has bcc
Solution : structure.
Given : Atomic mass of Al:27 g mol\ Ans. Number of atoms in unit cell:2
Mass of Al:10 g Type of crystal:bcc ■
1. SOLID STATE 31
Unit (2) The defect can be developed by heating the substance.
1.8 Crystal defects or imperfections
Q. 72. What is meant by crystal defects or imper-

fections? (2 marks)
Ans.
(1) Defect in crystalline structure : Any deviation
from orderly and stoichiometrically perfect ar-
rangement of atoms, ions or molecules in the crystal Fig. 1.27 : Vacancy defect
lattice is called a defect in the crystalline structure. (3) The mass of solid decreases due to absence of
(2) Defects are created during the crystallisation pro- particles in regular sites.
cess. If the process occurs at faster rate, the defects (4) Since the volume remains the same the density of
are more. the substance decreases. ■
(3) The properties of solids are affected due to imper-

Q. 77. Explain self interstitial defect in elemental
factions. ■
solid. (2 marks)
Q. 73. Mention the types of defects in the solids or Ans. Self Interstitial defect in elemental solid :
crystal structures. (2 marks) The empty spaces or voids in between the particles
Ans. The defects in crystalline solids are of two types at lattice points represent interstitial defective sites
viz., (1) Point defect and (2) Line defect. or self interstitial defects.
(1) Point defects are further classified as : This defect arises in the following two ways :
(a) Vacancy defect or Schottky defect (1) An extra particle occupies the empty interstitial
(b) Interstitial defect or Frenkel defect space. This extra particle is similar to those already
(c) Impurity defect : present in the crystal.
This is further classified as (2) (i) A particle gets shifted from its original regular
(i) Substitution impurity defect site to an empty interstitial space in the crystal.
(ii) Interstitial impurity defect.
(2) Line defects are further classified as
(a) Edge dislocation (b) Screw dislocation. ■
Q. 74. What are point defects ? (1 mark)

Ans. Point defects : These defects arise due to irreg-
ularities produced in the arrangement of basis of
lattice points in crystalline solids. ■
Fig. 1.28 : Self interstitial defect
Q. 75. What are major classes of point defects ? (ii) This displacement of a particle produces a
(1 mark) vacancy defect at its regular site.
Ans. There are three major classes of point (iii) This defect is referred to as a combination of
defects : stoichiometric point defects, impurity de- vacancy defect and self interstitial defect.
fects and nonstoichiometric point defects. (iv) Since there is neither loss or gain in mass of the
There are four types of stoichiometric point defects substance, the density of it remains unchanged.
■
as vacancy defect, self interstitial defect, Schottky
defect and Frenkel defect. ■
Q. 78. How does Schottky defect arise ? (2 marks)
Q. 76. Explain vacancy defect. (2 marks) Ans.
Ans. Vacancy defect : (1) Schottky defect arises in ionic solids due to missing
(1) During crystallisation, some of regular sites in solid of equal number of cations and anions from their
remain unoccupied and the missing particle creates regular positions in the crystal lattice creating
a vacancy defect. vacancies.

(1) Frenkel defect : This defect arises when an ion of
an ionic compound is missing from its regular site
and occupies interstitial vacant position between
lattice points.
(2) Cations have smaller size than anions, hence gen-
erally cations occupy the interstitial sites.
(3) This creates a vacancy defect at its original position
and interstitial defect at new position.
(4) Frenkel defect is regarded as the combination of
interstitial defect and vacancy defect.
Fig. 1.29 : Schottky defect (5) Conditions for the formation of Frenkel defect :
(2) There arises formation of two holes per loss of ion (i) This defect arises in ionic compounds with a
pair. large difference between the sizes of cation
(3) Conditions for formation of Schottky defect : and anion.
Characteristics of ionic solids showing Schottky (ii) The ionic compounds must have ions with low
defect : coordination number. ■
(i) High degree of ionic character
Q. 81. What are the consequences of Frenkel defect ?
(ii) High coordination number of anion
(2 marks)
(iii) Small difference between ionic size or radii of
Ans. Consequences of Frenkel defect :
r
cation and anion. The ionic ratio cation is not (1) Since there is no loss of ions from the crystal lattice,
ranion
the density of the solid remains unchanged.
below unity. ■
(2) The crystal remains electrically neutral.
★ Q. 79. What are the consequences of Schottky (3) This defect is observed in ZnS, AgCl, AgBr, AgI,
defect ? (2 marks) CaF , etc. ■

Ans. Consequences of Schottky defect : Do you know ?
(1) Since the number of ions (cations and anions) (Textbook page 18)
decreases but volume remains unchanged, the den- Frenkel defect is not found in pure alkali metal
sity of a substance decreases. halides because cations of alkali metals due to large
(2) As the number of missing cations and anions is size cannot occupy interstitial space.
equal, the electrical neutrality of the compound
remains same. Q. 82. Explain with diagram, Frenkel defect. What
(3) This defect arises in ionic crystals like NaCl, AgBr, are the conditions for its formation ? What is its
KCl, etc. ■
effect on density and electrical neutrality of the
crystal ? (3 marks)
Q. 80. How does Frenkel defect arise ? (2 marks)
Ans. For answer refer to answers of Q. 80 and Q. 81.
Ans. ■
Q. 83. Explain impurity defect in solids.

(3 marks) OR
What is an impurity defect ? What are its types ?
Explain the formation of vacancies through
aliovalent impurity with example. (3 marks)
Ans. Impurity defect : This defect arises when foreign
atoms, that is, atoms different from the host atoms
are present in the crystal lattice.
There are two types of impurity defects namely
(1) Substitutional defects and (2) Interstitial
Fig. 1.30 : Frenkel defect defects.
2/Navneet Chemistry Digest : Std. XII (Part I) E0288 33
(1) Substitutional defects : These defects arises when Q. 84. Explain nonstoichiometric defect. (4 marks)
foreign atoms occupy the lattice sites in place of Ans. Nonstoichiometric defect : This defect arises
host atoms, due to their displacements. when the ratio of number of one kind of atoms to
Examples : Solid solutions of metals (alloys). For that of other kind of atoms (or ratio of number of
example, Brass in which host atoms are of Cu which cations to anions) becomes different from the actual
are replaced by impurity of Zn atoms. In this Zn stoichiometric formula. This involves the change in
atoms occupy regular sites while Cu atoms occupy stoichiometry of the compound.
substituted sites. There are two types of nonstoichiometric defects as
follows :
(1) Metal deficiency defect : This defect arises in
compounds of metal which show variable oxidation
states. In some metal crystals, positive metal ions
are missing from their regular lattice sites. The extra
Fig. 1.31 : Brass negative charge is balanced by cations of the same
Vacancy through aliovalent impurity : metal with higher oxidation state than that of
By addition of impurities of aliovalent ions : missing cation at site.
Fig. 1.32 : Vacancy through aliovalent ion

When aliovalent ion like Sr2; in small amount Fig. 1.34 : Nonstoichiometric Ni0.97O1.0
is added by additing SrCl to NaCl during its (ii) Consider a crystal of NiO. When one Ni2; is

crystallisation, each Sr2; ion (oxidation state 2;) missed from its lattice point, it creates a vacant
removes 2 Na ; ions from their lattice points, to site.
maintain electrical neutrality. Hence one of vacant The deficiency of two positive charges is
lattice site is occupied by Sr2; ion while other site compensated by two Ni3; ions at other lattice
remains vacant. points of Ni2; ions and the composition of NiO
crystal becomes Ni0.97O1.0.
(2) Interstitial impurity defect : (2) Metal excess defect : There are two types of metal
excess defect as follows :
(a) Presence of a neutral atom or an extra positive
ion at interstitial position :
Fig. 1.33 : Stainless steel

A defect in solid in which the impurity atoms
occupy interstitial vacant spaces of lattice structure
is called interstitial impurity defect.
For example, in steel, normal lattice sites are
occupied by Fe atoms but interstitial spaces are
occupied by carbon atoms. ■ Fig. 1.35 : Neutral Zn atom at interstitial site

There are two types or ways of metal excess The released electrons diffuse into the crystal and
defects in ZnO. In the first case, Zn atom is occupy vacant sites of anions Cl 9 in the crystal.
present in the interstitial space as shown in The anion vacant sites occupied by electrons are
figure. called F-centres or colour centres. Due to colour
(b) Metal ions and electrons at interstitial sites :
centres NaCl shows yellow colour.
The second case arises when ZnO is heated,
(6) Now NaCl crystal has excess of Na atoms having
Zn2; and electrons are obtained,
1 nonstoichiometric formula Na1;xCl1.0. ■
ZnO IIIIIJ Zn2; ; O ;2e 9
2 Can you think ?
(Textbook page 20)
Q. When ZnO is heated it turns yellow and returns
back to original white colour on cooling. What
could be the reason ?
Ans. When colourless ZnO is strongly heated, the
metal atoms are deposited on crystal surface and
anions O29 migrate to the surface producing
vacancies at anion lattice points.
Fig. 1.36 : Zn2; ions and electrons at interstitial sites
These anions combine with Zn atoms forming
The excess Zn2; ions are trapped in inter-
ZnO and release electrons.
stitial sites in the crystal lattice. Electrons
occupy interstitial sites by diffusing into the Zn;O29 IIIIJ ZnO;2e 9
interstitial sites. These released electrons diffuse into the crystal
In above both cases, the nonstoichiometric and occupy vacant sites of anions and produce F-
formula of ZnO is Zn1;xO1.0 ■ centres. Due to these colour centres, ZnO turns
Q. 85. Explain defects due to anion vacancies. yellow.
(3 marks) OR
Explain colour of crystals or F centres. (3 marks) Unit
Ans. 1.9 Electrical properties of solids
(1) The defect due to anion vacancies imparts colour to 1.9.1 Band theory
the colourless crystal. 1.9.2 Metals
(2) When a colourless crystal of NaCl is heated in the 1.9.3 Insulators
atmosphere of sodium vapour, the sodium atoms are 1.9.4 Semiconductors
deposited on the crystal surface.
1.9.5 Extrinsic semiconductors and doping
(3) Due to diffusion of Cl 9 ions to the crystal surface
vacancies are created at their regular sites.
(4) These diffused Cl 9 ions combine with Na atoms on Q. 86. How are solids classified according to elect-
the surface forming NaCl along with releasing rical conductivity ? (3 marks)
electrons from sodium atoms. Ans. According to electrical conductivity, solids are
Na;Cl 9 IIIIIJ NaCl;e 9 classified as follows :
(5) (1) Conductors :
(i) The solids having electrical conductivity in the
range of 10 to 10 Ohm 91m 91 are called
conductors.
(ii) The examples of conductors are metals and
electrolytes.
(iii) Electrical conductivity in metals is due to free
movement of electrons while electrolytes con-
Fig. 1.37 : An F-centre in a crystal duct electricity due to migration ions.
1. SOLID STATE 35
(2) Insulators : (ii) Band gap decides whether electrons from val-
(i) Solids having very low electrical conductivity ence band can be promoted to vacant conduc-
in the range of 10 920 to 10 910 Ohm 91 m 91 are tion band or not.
called insulators. (iii) The conductors like metals have very small or
(ii) The examples of insulators are nonmetals and no band gap and electron can be promoted by
molecular solids. thermal energy. The nonconductors have large
(3) Semiconductors : band gap. The insulators have very large band
(i) Solids having conductivity in the range of gap.
10 96 to 10 Ohm 91m 91 are semiconductors.
(ii) The conductivity range is intermediate be-
tween conductors and insulators.
(iii) The examples of semiconductors are silicon
and germanium. ■
★ Q. 87. A solid is hard, brittle and electrically non-
conductor. Its melt conducts electricity. What

type of solid is it ? (1 mark) Fig. 1.38 : Metal, semiconductor and insulator ■
Ans. A solid crystalline electrolyte like NaCl is hard,
★ Q. 89. What are valence band and conduction
brittle and electrically nonconductor. But its melt
band ? (3 marks)
conducts electricity. ■
Ans. For answer, refer to point (4) of Q. 88 ■
Q. 88. Explain band theory. (3 marks) OR
Do you know ?
Explain the origin of electrical properties in (Textbook page 21)
solids. (3 marks) The band gap energy values of a few solids are as
Ans. shown here.
(1) Metals are good conductors of heat and electricity.
This is explained on the basis of band theory which Solid EgapeV
involves the presence of free electrons. Diamond 5.47
(2) According to band theory, the atomic orbitals of
metal atoms overlap to form molecular orbitals Sodium 0
which are spread all over the crystal structure.
Silicon 1.12
(3) The energy difference between adjacent molecular
orbitals decreases as the number of molecular Germanium 0.67
orbitals increases and when it becomes very less,
the orbitals merge into one another forming con-
Q. 90. Metals are good conductors of electricity.
tinuous bands which extent over the entire crystal.
Explain. (2 marks)
(4) There are two types of bands of molecular orbitals
as follows : Ans.
(i) Valence band : The atomic orbitals with filled (1) Metals are good conductors of electricity since the
electrons from the inner shells form valence outermost electrons of atoms in metallic crystal
bands, where there are no free mobile electrons occupy conduction bands.
since they are involved in bonding.
(ii) Conduction band : Atomic orbitals which are
partially filled or empty on overlapping form
closely placed molecular orbitals giving con-
duction bands where electrons are delocalised
and can conduct, heat and electricity.
(5) Band gap :
(i) The energy difference between valence band
and conduction band is called band gap. Fig. 1.39 : Metallic conductor

(2) The number of electrons in conduction bands is
MOs together called 3p band. This is the vacant band.
very large.
The filled 3s band and vacant 3p band overlap each
(3) The conduction bands in metals can be labelled as
other. As a result, higher energy electrons move from
‘s’ band, overlapping s and p bands etc. according
to overlapping of orbitals. 3s band to 3p band.
(4) This results in delocalisation of outermost electrons
forming metal ions. Hence, this is analogous to Q. 92. Explain insulators. (2 marks)
metal cations immersed in the sea of electrons. ■ Ans.
(1) In insulators the valence band is completely filled
Q. 91. Why does metallic conductivity decrease by by electronics while conduction band is empty.
increasing temperature ? (2 marks)
Ans.
(1) In metals a large number of outermost electrons of
atoms occupy conduction bands.
(2) Band formation in metals results in delocalisation
of outermost electrons forming metal ions or cations.
(3) The metallic cations occupying crystal lattice sites
vibrate about mean positions.
(4) As temperature increases the vibrational motion
increases which interrupts flow of electrons
decreasing electrical conductivity. ■ Fig. 1.40 : Insulators
(2) The energy gap between valence band and conduc-
Do you know ? tion band in insulator is very large.
(Textbook page 22)
● Metallic sodium is an example of conductor where (3) Thermal energy is not sufficient to promote elec-
the conduction band is partially filled and there is no trons from valence band to conduction band.
band gap. Electronic configuration of Na is [Ar]3s. (4) Therefore, the conduction band in insulator remains
Interaction of the partially filled 3s AOs of all the Na vacant and does not allow the conduction of elec-
atoms gives rise to same number of MOs. All these tricity. ■
closely spaced MOs together form a continuous
Q. 93. What are semiconductors ? Mention the types
band of energies which is called 3s band. Lower half
of semiconductors. (3 marks)
of 3s band corresponds of BMOs and is filled while
Ans.
the upper half of 3s band corresponds to AMOs and
is empty. There is no gap between these two halves. (1) Semiconductors : The substances like silicon,
The 3s band in sodium is the conduction band which germanium which have poor electrical conductance
contains same number of electrons as the sodium at low temperature but the conductance increases
atoms. This is responsible for the high conductivity with the increase in temperature are called semi-
of metallic sodium. conductors.
● Metallic magnesium is an example of conductor
with overlapping bands. Electronic configuration of
Mg is [Ar]3s3p. Interaction of completely filled 3s
AOs of all the Mg atoms gives rise to the same
number of MOs all of which are filled. These
together form the 3s band which is a completely
filled band. Interaction of vacant 3p AOs of all the
Mg atoms gives rise to the same number of vacant
Fig. 1.41 : Semiconductors
1. SOLID STATE 37
(2) Their conductivity lies between metallic conductors (i) n-type semiconductor contains increased
and insulators. number of electrons in the conduction band.
(3) The energy difference between valence band and (ii) When Si semiconductor is doped with 15th
conduction band is relatively small, hence the group element phosphorus, P, the new atoms
occupy some vacant sites in the lattice in place
electrons from valence band can be excited to
of Si atoms.
conduction band by heating.
(4) Types of semiconductors : There are two types of
semiconductors :
(a) Intrinsic semiconductor
(b) Extrinsic semiconductor
(a) Intrinsic semiconductor :
(i) A pure semiconductor material like pure Si, Ge
which have a very low but finite electrical
Fig. 1.43 : P atom occupying regular site of Si atom
conductivity is called intrinsic semiconductor.
(iii) P has five valence electrons, out of which four
(ii) The electrical conductivity of a semiconductor
are involved in covalent bonding with neigh-
increases with the increase in temperature.
bouring Si atoms while one electrons remains
(b) Extrinsic semiconductor :
free and delocalised.
(i) Semiconductor doped with different element is
(iv) These free electrons increase the electrical
called extrinsic semiconductor. conductivity of the semiconductor.
(ii) By doping with elements like Ga or P, the
(v) The semiconductors with extra non-bonding
electrical conductivity is increased. free electrons are called n-type semiconduc-
Q. 94. Explain extrinsic semiconductor and doping. tors.
(3 marks) (B) p-type semiconductor :
Ans. (i) p-type semiconductor is obtained by doping a
(1) A semiconductor obtained by doping intrinsic pure semiconductor by an element of 13th
semiconductor with elements of third group and group like B.
fifth group is called extrinsic semiconductor. (ii) 13th group element has less number of valence
(2) This extrinsic semiconductor has higher electrical electrons. When pure Si is doped with B
conductivity than pure intrinsic semiconductor. atoms, these atoms occupy Si lattice points.
Fig. 1.42 : n-type and p-type semiconductor Fig. 1.44 : B atom occupying regular site of Si atom
(3) There are two types of extrinsic semiconductors : (iii) Boron ( B) has only 3 valence electrons which

(A) n-type semiconductor : form covalent bonds with the neighbouring Si

atoms, while one bond has shortage of one Q. 95. What are the uses of semiconductors ?
electron. (2 marks)
(iv) This creates a vacancy or a hole, hence the Ans. The uses of semiconductors are as follows :
electron from neighbouring Si atom jumps into
(1) They are used in transistors, digital computers and
this hole creating a vacancy in itself. This
cameras.
process continues, i.e., positive holes move in
one direction while electrons moves in oppo- (2) They are used in solar cells and television sets.
site direction. (3) By combining n-type and p-type semiconductors,
(v) Due to electron deficient positions, this n-p junctions are formed which are effectively used
semiconductor is called p-type semiconductor.
in rectifiers or to convert light energy into electrical
(vi) When p-type semiconductor is connected to
energy. ■
the external source of electricity, electrons
from neighbouring silicon atoms jump into the ★ Q. 96. What are n-type semiconductors ? Why is
holes so that electrons move towards positive the conductivity of doped n-type semiconductor
electrode and holes migrate towards negative higher than that of pure semiconductor ?
electrode.
Explain with diagram. (3 marks)
(vii) Hence electrical conduction in p-type
Ans. For answer refer to point (3) (A) of Q. 94. ■
semiconductor is due to electrons and holes.
■ ★ Q. 97. Classify the following semiconductors into
Remember ... n or p-type.
(Textbook page 24)
(i) B doped with Si
● Whether intrinsic or extrinsic semiconductor, the material
is electrically neutral. (ii) As doped with Si
● An n-type semiconductor such as Si doped with P has (iii) P doped with Si
1
more electrons than those needed for bonding and thus (vi) Ge doped with In. ( 2 mark each)
has electrons in the partially filled conduction band. Ans.
● A p-type semiconductor such as Si doped with B has the
less electrons than needed for bonding and thus has Semiconductor Type
vacancies (holes) in the valence band.
(i) B doped with Si p-type
Remember ... (ii) As doped with Si n-type
(Textbook page 23)
● Electrical conductivity of metals decreases and that of (iii) P doped with Si n-type
semiconductor increases with increasing temperature. (iv) Ge doped with In p-type
Can you tell ? ■

(Textbook page 23)
II
Let a small quantity of phosphorus be doped into pure

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silicon.
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(1) Will the resulting material contain the same

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number of total number of electrons as the

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original pure silicon ?

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Ans. Total number of electrons in doped silicon will

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be more than in original silicon.

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(2) Will the material be electrically neutral or

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charged ?
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Ans. Material will be electrically neutral.

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1. SOLID STATE 39
Q. 98. Distinguish between conductor, insulator and semiconductor. (3 marks) OR
★ Distinguish with the help of diagrams metal conductors, insulators and semiconductors from each other.
(3 marks)
Ans.
Conductor Insulator Semiconductor
(1) A substance which conducts heat A substance which cannot conduct A substance which has poor electri-
and electricity to a greater extent heat and electricity under any condi- cal conductance at low temperature
is called conductor. tions is called insulator. but higher conductance at higher
temperature is called semiconductor.
(2) In this, conduction bands and In this, conduction bands and valence In this, conduction bands and
valence bands overlap or are very bands are far apart. valence bands are spaced closely.
closely spaced.
(3) There is no energy difference or The energy difference between con- The energy difference between con-
very less energy difference duction bands and valence bands is duction bands and valence bands is
between valence bands and very large. small.
conduction bands.
(4) There are free electrons in the There are no free electrons in the The electrons can be easily excited
conduction bands. conduction bands and electrons can’t from valence bands to conduction
be excited from valence bands to bands by heating.
conduction bands due to large energy
difference.
(5) The conductance decreases with No effect of temperature on conduc- Conductance increases with the
the increase in temperature. ting properties. increase in temperature.
(6) E.g., Metals, alloys. Wood, rubber, plastics. Si, Ge.
(7) The conducting properties can’t No effect of addition of any sub- By doping, conducting properties
be improved by adding third stance. improve. E.g. n-type, p-type
substance. semiconductors.
(8)

Unit repel the applied magnetic field. This phenomenon
1.10 Magnetic properties of solids is called diamagnetism and the substance is said to
be diamagnetic.
Q. 99. Explain the origin of magnetic properties
in solids. (2 marks)
Ans.
Fig. 1.47 : Paired electrons
(1) The magnetic properties of a substance arise due to
the presence of electrons in their atoms or mol- For example : Zn, Cd, H O, NaCl, etc. ■

ecules. Q. 101. Explain paramagnetism. (2 marks) OR
(2) The electrons while re- ★ What are paramagnetic substances ? Give
volving around the nucleus examples. (2 marks)
in various orbits, also spin Ans.
around their own axes. Both (1) The magnetic properties of a substance arise due to
these motions of electrons the presence of electrons.
result in generating magnet- (2) An electron while revolving around the nucleus,
ic field and magnetic mo- Fig. 1.45 : also spins around its own axis and generates a
ments. Hence electron be- Magnetic property magnetic moment and magnetic properties.
haves as a tiny magnet. of an electron (3) If an atom or a molecule contains one or more
(3) An atomic orbital can accommodate maximum two unpaired electrons spinning in same direction,
electrons with opposite spins, clockwise and anti-
clockwise or anticlockwise, then the substance is
clockwise. The degenerate orbitals like p, d and f
associated with net magnetic moment and magnetic
orbitals can accommodate electrons with same
properties. They experience a net force of attraction
spins until they are half filled.
when placed in the magnetic field. This pheno-
(4) When a substance contains one or more unpaired
menon is called paramagnetism and the substance is
electrons spinning in same direction, then their
said to be paramagnetic.
magnetic moments and magnetic properties add and
For example, O , Cu>, Fe>, Cr>, NO, etc. ■
the substance is said to be paramagnetic.
Q. 102. Explain ferromagnetism. (1 mark) OR
★ What are ferromagnetic substances ? (1 mark)
Ans.
Fig. 1.46 : Unpaired electrons
(1) The substances which possess unpaired electrons
If a substance contains all electrons paired then
their spins are balanced and magnetic moments and and high paramagnetic character and when placed
magnetic properties are cancelled and the substance in a magnetic field are strongly attracted and show
is said to be diamagnetic. ■
permanent magnetic moment even when the exter-
nal magnetic field is removed are said to be
Q. 100. Explain diamagnetism. (2 marks)
Ans. ferromagnetic. They can be permanently magnetised.
(1) The magnetic properties of a substance arise due to (2) In the solid state, the metal ions of ferromagnetic
presence of the electrons. substance are grouped together into small regions
(2) An electron while revolving around the nucleus, called domains, where each domain acts as a tiny
also spins around its own axis and generates a magnet.
magnetic moment and a magnetic property.
(3) If an atom or a molecule of the substance contains
all electrons paired, spinning clockwise and anti- Fig. 1.48 : Ferromagnetic property
clockwise, their magnetic moments and magnetic
For example : Fe, Co, Gd, Ni, CrO , etc.
properties get cancelled. Hence they oppose and ■
1. SOLID STATE 41
★ Q. 103. The following pictures show population of Activity ...
bands for materials having different electrical
(1) With the help of plastic balls, prepare models of
properties. Classify them as insulator, semicon-
(i) tetrahedral and octahedral voids.
ductor or a metal. (3 marks)
(ii) simple cubic, bcc and fcc unit cells.
(iii) ccp and hcp lattices.
(2) Draw structures of network of carbon atoms in
diamond and graphite. Discuss with reference to
the following points :
(i) Are the outermost electrons of carbons in
diamond localized or delocalized ?
(ii) Is the energy gap between BMOs and AMOs
in diamond expected to be large or small ?
[Note : Students are expected to carry out this activity on their own.]
Fig. 1.49 : Ferromagnetic property
Ans. Picture A represents metal conductor,
Picture B represents insulator, Q. 106. Select and write the most appropriate
Picture C represents semiconductor. answer from the given alternatives for each sub-
question : (1 mark each)
★ Q. 104. How does electrical conductivity of a ★ 1. Molecular solids are
semiconductor change with temperature ? (a) crystalline solids (b) amorphous solids
Why ? (2 marks) (c) ionic solids (d) metallic solids
★ 2. Which of the following is n-type semiconductor ?
Ans.
(a) Pure Si (b) Si doped with As
(1) Since the energy difference between valence band
(c) Si doped with Ga (d) Ge doped with ln
and conduction band in semiconductor is not large,
★ 3. In Frenkel defect
the electrons from valence band can be promoted to (a) electrical neutrality of the substance is
conduction by heating. changed.
(2) Hence electrical conductivity of a semiconductor (b) density of the substance is changed.
increases with temperature. ■
(c) both cation and anion are missing
(d) overall electrical neutrality is preserved
★ Q. 105. The picture represents bands of MOs for Si. ★ 4. In crystal lattice formed by bcc unit cell the void
Label valence band, conduction band and band volume is
gap. (1 mark) (a) 68% (b) 74% (c) 32% (d) 26%
★ 5. The coordination number of atoms in bcc crystal
Ans.
lattice is
(a) 2 (b) 4 (c) 6 (d) 8
★ 6. Which of the following is not correct ?
(a) Four spheres are involved in the formation of
tetrahedral void.
(b) The centres of spheres in octahedral voids are
at the apices of a regular tetrahedron.
(c) If the number of atoms is N the number of
octahedral voids is 2N.
(d) If the number of atoms is N/2, the number of
Fig. 1.50 : MOs for Si ■ tetrahedral voids is N.

★ 7. A compound forms hcp structure. Number of 19. The packing fraction for a body centred cubic
octahedral and tetrahedral voids in 0.5 mole of structure is
substance is respectively (a) 0.42 (b) 0.53 (c) 0.68 (d) 0.82
(a) 3.011;10, 6.022;10 20. If r is the radius of an atom and a is an edge length of
(b) 6.022;10,3.011;10 fcc unit cell, then
(c) 4.011;10, 2.011;10 (3 a
(a) r: a (b) r:
(d) 6.011;10, 12.022;10 4 2(2
★ 8. Pb has fcc structure with edge length of unit cell a
(c) r: (d) r:2(2a
495 pm. Radius of Pb atom is 2
(a) 205 pm (b) 185 pm 21. The ratio of packing efficiency in scc, bcc and fcc
(c) 260 pm (d) 175 pm crystalline structures is
9. A substance which on cutting will give irregular (a) 1 : 1.2 : 1.3 (b) 1 : 1.12 : 1.23
cleavage is (c) 1 : 1.3 : 1.4 (d) 1 : 1.25 : 1.38
(a) glass (b) KBr (c) ZnS (d) NaCl 22. The correct sequence of the atomic layers in cubic
10. A solid which has definite heat of fusion is close packing is
(a) plastic (b) CaCl (a) ABABA (b) ABACABAC

(c) glass (d) soda lime glass (c) ABCABC (d) AABBAABB
11. In solids the constituent particles may be 23. The major binding force in diamond is
(a) atoms (b) ions (a) Covalent bond
(c) molecules (d) any one of the above three (b) Ionic bond
12. A single substance that exists in two or more (c) Metallic bond
forms is called (d) Coordinate covalent bond
(a) polymorphous (b) amorphous 24. The ratio of close packed atoms to octahedral holes
(c) isomorphous (d) monomorphous in cubic packing is
13. Graphite is a (a) 1 : 1 (b) 1 : 2 (c) 2 : 1 (d) 1 : 3
(a) metallic crystal (b) covalent crystal 25. A defect present in AgCl is
(c) ionic crystal (d) molecular crystal (a) Frenkel defect
14. Anisotropy is observed in (b) Schottky defect
(a) Pyrex glass (b) plastic (c) point defect
(c) K SO (d) fullerene (d) interstitial impurity defect

15. The number of crystal systems (or types) is 26. An ionic solid crystallises in bcc structure. If the
(a) 4 (b) 7 (c) 8 (d) 12 ionic radii of cation and anion are 0.84 At and 1.07 At ,
16. The number of Bravais lattices are the length of the body diagonal is
(a) 6 (b) 8 (c) 12 (d) 14 (a) 1.91 At (b) 2.75 At
17. Face centred cubic crystal is (c) 3.82 At (d) 2.32 At
(a) Cubic lattice of Bravais system 27. The type of defect in NaCl crystal will be
(b) Bravais lattice of HCP (a) point defect (b) interstitial defect
(c) Bravais lattice of cubic system (c) vacancy defect (d) impurity defect
(d) Cubic lattice with 5 atoms 28. Schottky defects are observed in which solid among
18. The number of tetrahedral sites per sphere in the following ?
ccp structure is, (a) Brass (b) Cesium chloride
(a) 1 (b) 2 (c) 3 (d) 4 (c) Zinc sulphide (d) Stainless steel
1. SOLID STATE 43
29. An ionic compound crystallises in FCC type (a) 128.6 g mol\ (b) 108.7 g mol\
structure with ‘A’ ions at the centre of each face and (c) 217.3 g mol\ (d) 57.86 g mol\
‘B’ ions occupying corners of the cube. The formula 40. An element crystallises in fcc structure. If the atomic
of compound is – mass of the element is 72.7 U, the mass of one unit
(a) AB (b) A B (c) AB (d) AB cell of it will be

30. Total number of different primitive unit cells are (a) 2.9;10\ g (b) 4.83;10\ kg
(a) 6 (b) 7 (c) 12 (d) 14. (c) 1.2;10\ g (d) 2.41;10\ kg
31. The volume of atoms present in body centred cubic 41. Edge length of a cubic unit cell is 354 pm. The
unit cell of a metal of atomic radius r is, distance between two atoms diagonally opposite on
16 8 12 24 the face is
(a) r (b) r (c) r (d) r.
3 3 3 3 (a) 500 pm (b) 354 pm
32. The substances which can be permanently magnet- (c) 708 pm (d) 627 pm
ised are 42. The unit cell has an edge length 403 pm. The
(a) diamagnetic (b) paramagnetic distance between two atoms placed opposite ends of
(c) ferromagnetic (d) non-magnetic body diagonal will be
33. CrO is (a) 806 pm (b) 201.5 pm

(a) diamagnetic (b) paramagnetic (c) 698 pm (d) 578 pm
(c) metallic (d) ferromagnetic
43. An element having atomic mass 115 u, crystallises in
34. A metallic element crystallises in face centred cubic bcc structure. The number of unit cells in 1 g of the
structure. If the radius of metal ion is 0.92 At , the element will be
edge length of the unit cell of the crystal is (a) 2.6;10 (b) 3.8;10
(a) 0.8464 At (b) 1.252 At (c) 8.7;10\ (d) 6.17;10
(c) 5.187 At (d) 2.6 At
44. The edge length of a bcc unit cell of a metallic
35. The volume of unit cell of a metallic crystal of bcc
crystal is 2.9 At . Hence the diameter of an atom is
type is 8.4;10 923 cm3. The volume occupied by 10
(a) 1.025 At (b) 2.512 At
atoms in the crystalline structure is
(c) 1.45 At (d) 1.31 At
(a) 4.2;10 922 cm (b) 3.12;10 923 cm
45. An element crystallises in fcc structure. If the atomic
(c) 1.74;10 923cm (d) 2.856;10 922 cm
radius is 130 pm, the edge length of unit cell is
36. Copper crystallises in face centred cubic structure. If
(a) 332.5 pm (b) 410 pm
the unit cell length is 360 pm, the radius of copper
(c) 390 pm (d) 367.6 pm
atom is
(a) 180 pm (b) 156 pm 46. The arrangement of layers in hexagonal close pack-
(c) 127 pm (d) 110 pm ing is
(a) ABCABC (b) ABAB
37. If all the lattice points in ccp structure namely
(c) ABBABBA (d) ABBCABBC
corners, face and edge centres and body centre are
occupied by atoms then the total number of atoms in 47. For square close packing, the planar arrangement is
the unit cell will be (a) AAAA (b) ABAB
(a) 8 (b) 12 (c) 14 (d) 16 (c) ABCABC (d) AABBAA
38. Gold crystallises in face centred cubic structure. 48. Semiconductors are manufactured by addition of
If atomic mass of gold is 197 g mol\, the mass of impurities of
the unit cell of gold will be (a) p-block elements (b) actinoids
(a) 3.25;10\ kg (b) 6.5;10\ kg (c) Lanthanoids (d) s-block elements
(c) 3.9;10\ kg (d) 1.3;10\ kg 49. p-type semiconductor is formed when trace
39. The mass of a unit cell of a body centred cubic amount of impurity is added to silicon. The number
crystal of a metal is 72.2;10\ g. The atomic of valence electrons in the impurity atom must be
mass of the metal is (a) 3 (b) 5 (c) 1 (d) 2

50. n-type semiconductor is formed when trace amount volume of a unit cell, that is occupied by Ag atoms,
of impurity is added to silicon. The number of (d) the per cent of empty space.
valence electrons in the impurity atom must be (Problem 1.3 of textbook page no. 15)
(a) 3 (b) 5 (c) 1 (d) 2 [Ans. (a) a:4.085;10 98 cm)
(b) Volume of Ag atom:1.261;10 923 cm
Answers
(c) Per cent of volume occupied by Ag atoms:74%
1. (b) amorphous solids 2. (b) Si doped with As
(d) Per cent of empty space:26%]
3. (d) overall electrical neutrality is preserved
4. A compound is formed by two elements A and B.
4. (c) 32% 5. (d) 8 6. (c) If number of atoms is N the
The atoms of element B forms ccp structure. The
number of octahedral voids is 2N 7. (a) 3.011;10,
atoms of A occupy 1/3rd of tetrahedral voids. What
6.022;10 8. (d) 175 pm 9. (a) glass
is the formula of the compound ?
10. (b) CaCl 11. (d) any one of the above three
(Problem 1.4 of textbook page no. 15) (Ans. A B )
12. (a) polymorphous 13. (b) covalent crystal
14. (c) K SO 15. (b) 7 16. (d) 14 17. (c) Bravais 5. Niobium forms bcc structure. The density of niobium
is 8.55 g/cm and length of unit cell edge is 330.6
lattice of cubic system 18. (b) 2 19. (c) 0.68
a pm. How many atoms and unit cells are present in
20. (b) r: 21. (c) 1 : 1.3 : 1.4 0.5 g of niobium ?
2(2
(Problem 1.5 of textbook page no. 15)
22. (c) ABCABC 23. (a) covalent bond 24. (a) 1 : 1
(Ans. Number of unit cells:1.62;10)
25. (a) Frenkel defect 26. (c) 3.82 At 27. (c) vacancy
defect 28. (b) Cesium chloride 29. (b) A B 6. A compound forms hcp structure. What is the
number of (a) octahedral voids. (b) tetrahedral voids
8
30. (d) 14 31. (b) r 32. (c) ferromagnetic (c) total voids formed in 0.4 mol of it.
3
33. (d) ferromagnetic 34. (d) 2.6 At (Problem 1.6 of textbook page no. 16)
35. (d) 2.856;10 922 cm 36. (c) 127 pm 37. (a) 8 [Ans. (a) Number of octahedral
38. (d) 1.3;10 924 kg 39. (c) 217.3 gmol 91 voids:2.4098;10
40. (b) 4.83;10 925 kg 41. (a) 500 pm (b) Number of tetrahedral voids:4.8196;10
42. (c) 698 pm 43. (a) 2.6;10 44. (b) 2.512 At (c) Total number of voids:7.229;10]
45. (d) 367.6 pm 46. (b) ABAB 47. (a) AAAA 7. An element germanium crystallises in bcc type
48. (a) p-block elements 49. (a) 3 50. (b) 5. crystal structure with edge of unit cell 288 pm and
the density of the element is 7.29 cm\. Calculate
the number of atoms present in 52 g of the crystalline
element. Also calculate atomic mass of the element.
1. When gold crystallizes, it forms face-centred cubic (Ans. Number of atoms:6.046;10; Atomic
cells. The unit cell edge length is 408 pm. Calculate mass:51.8 g mol\)
the density of gold. Molar mass of gold is 197 g/mol. 8. Naturally occurring gold crystallises in face centred
(Problem 1.1 of textbook page no. 8) cubic structure and has density 19.3 g cm\. Find
(Ans. 19.27 g cm 93, 19.27;10 kg dm\) atomic radius of gold. (Au:137 g mol\)
2. A compound made of elements C and D crystallizes (Ans. 144 pm)
in fcc structure. Atoms of C are present at the corners 9. If the density of a crystalline element having atomic
of the cube. Atoms of D are at the centres of faces of mass 50 is 6.8 g cm\ and the crystalline structure is
the cube. What is the formula of the compound ? body centred cubic, find the edge length.
(Problem 1.2 of textbook page no. 14) (Ans. 290 pm)
(Ans. Formula of compound:CD ) 10. The density of silver having atomic mass 107.9 u is

3. The unit cell of metallic silver is fcc. If radius of Ag 10.5 g cm\. If its crystalline structure is fcc find the
atom is 144.4 pm, calculate (a) edge length of unit edge length and radius of silver atom.
cell (b) volume of Ag atom, (c) the per cent of the (Ans. 408.5 pm; 144 pm)
1. SOLID STATE 45
11. Unit cell of NaCl contains 4 NaCl molecules. If the 17. Sodium metal crystallises in body centred cubic unit
density of NaCl crystal is 2.17 g cm\, find the edge cell. If the distance between nearest Na atoms is
length of the cube. (Ans. 5.618 At ) 368 pm, calculate the edge length of unit cell.
12. Copper crystallises in fcc type unit cell. The edge (Ans. 425 pm)
length of unit cell is 360.8 pm. The density of 18. Copper having atomic radius 1.28 At has density
metallic copper is 8.92 g cm\. Determine atomic 8.94 g cm\. If the atomic mass of copper is
mass of copper. (Ans. 63.07 g mol\)
63.54 g mol\, determine the number of Cu atoms in
13. The density of mercury is 13.6 g cm\. If each atom the unit cell and crystal structure of copper.
of mercury occupies a cube of edge length equal to
(Ans. Number of Cu atoms in unit cell:4;
the diameter of mercury atom, find the radius of
Crystal structure of Cu is face centred cubic.)
mercury atom. (Atomic mass of mercury is
19. Lithium crystallises in body centred cubic structure
200 g mol\.) (Ans. 1.45 At )
with edge length 350 pm. Determine the density of
14. The density of aluminium is 2.7 g cm\. The edge
lithium. (Atomic mass of lithium is 6.95 u.)
length of cubic unit cell of aluminium is 405 pm.
(Ans. Density of lithium:0.529 g cm\)
Find the structure of aluminium.
20. In crystalline compound AB , atoms A occupy
(Ans. Aluminium has face centred cubic structure.)
corners. Which lattice points will be occupied by
15. An element of atomic mass 96 u has density
10.3 g cm\. Find the distance between the nearest B atoms? (Ans. Six face centres)
neighbouring atoms of the element. 21. Silver crystallises in face centred cubic structure.
(Ans. 2.718;10\ cm) The edge length of unit cell is found to be 408.7 pm.
16. The crystal lattice of an element has fcc structure. Calculate density of silver (Ag:108 g mol\)
If the radius of an atom of the element is 127.6 pm, (Ans. Density:10.51 g cm\)
calculate the edge length of the unit cell of the
crystal. (Ans. 360.8 pm)

2. SOLUTIONS
2 SOLUTIONS
CHAPTER OUTLINE
.... Important Terms and Formulae
.... Exercises
2.1 Introduction … 49
2.2 Types of solutions … 49
2.3 Capacity of a solution to dissolve a solute … 49
2.4 Solubility … 50
2.4.1 Factors affecting solubility … 50
2.5 Vapour pressure of liquids in liquids … 54
2.5.1 Raoult’s law … 54
2.5.2 Ideal and nonideal solutions … 54
2.6 Colligative properties of nonelectrolyte solutions … 57
2.7 Vapour pressure lowering … 57
2.7.1 Raoult’s law for solutions of nonvolatile solutes … 57
2.7.2 Relative lowering of vapour pressure … 57
2.7.3 Molar mass of solute from vapour pressure lowering … 57
2.8 Boiling point elevation … 62
2.8.1 Boiling point elevation as a consequence of vapour pressure lowering … 62
2.8.2 Boiling point elevation and concentration of solute … 62
2.8.3 Molar mass of solute from boiling point elevation … 62
2.9 Depression in freezing point … 68
2.9.1 Freezing point depression as a consequence of vapour pressure lowering … 68
2.9.2 Freezing point depression and concentration of solute … 68
2.9.3 Molar mass of solute from freezing point depression … 68
2.10 Osmotic pressure … 72
2.10.1 Osmosis … 72
2.10.2 Osmotic pressure … 72
2.10.3 Isotonic, hypertonic and hypotonic solutions … 72
2.10.4 Osmotic pressure and concentration of solution … 72
2.10.5 Molar mass of solute from osmotic pressure … 72
2.10.6 Reverse osmosis … 72
2.11 Colligative properties of electrolytes … 75
2.11.1 van’t Hoff factor (i) … 75
2.11.2 Modification of expressions of colligative properties … 75
2.11.3 van’t Hoff factor and degree of dissociation … 75
.... Multiple Choice Questions … 82
.... Examples for Practice … 86
2. SOLUTIONS 47
1. Henry’s law : S:KHP
2. Raoult’s law : Psoln :x P

3. Mole fractions, x ;x :1

4. Psoln :Px ;Px

5. Psoln :(P 9P) x ;P

x P x P
6. Mole fractions of components in vapour phase : y : and y :
P P
7. For ideal solutions : Vmix :0; mixH:0
P9P P9P
8. Relative lowering of vapour pressure: ,x :
P P
P9P W ;M
9. :
P W ;M

10. Tb :Kb ;m and Tf :Kf ;m
W ;1000
11. Tb :Kb ;
W ;M

W ;1000
12. Tf :Kf ;
W ;M

WRT
13. :cRT and :
M;V
Colligative property of electrolyte solution
14. i:
Colligative property of nonelectrolyte solution of the same concentration
Tb(ob) P(ob) Tf(ob) ob Mth
15. van’t Hoff factor (i): : : : :
Tb(th) P(th) Tf(th) th Mob
16. Colligative properties considering van’t Hoff factor :
P 9P W ;M
(a) :i; (c) Tf :i;Kf ;m
P W ;M

W ;1000
(b) Tb :i;Kb ;m Tf :i;Kf ;
W ;M

W ;1000
Tb :i;Kb ; W;RT
W ;M (d) :iCRT:i;
M;V
i91
17. : (for dissociation)
n91

Types of solutions Solute Solvent Examples
(★ ) Indicates question from the textbook.
(A) Gaseous solution
Units
(A) (1) Gas in gas Gas Gas Air, mixture of
2.1 Introduction
non reacting
2.2 Types of solutions gases and
vapours
Q. 1. What is solution ? (1 mark)
(2) Liquid in gas Liquid Gas Chloroform
Ans. The solution is a homogeneous mixture of two or
mixed with
more components or pure substances. When the nitrogen gas
size of particles of the components is of the order of (3) Solid in gas Solid Gas Smoke, fumes,
10 910m, then the solution is called a true solution. I in air

E.g. An aqueous solution of sugar. ■
(B) Liquid solution
Q. 2. Explain : (1) Homogeneous solution (A) (1) Gas in liquid Gas Liquid CO in water,

(2) Heterogeneous solution. (1 mark each) N in chloroform

Ans. (2) Liquid in liquid Liquid Liquid Alcohol in water
(1) Homogeneous solution : A solution in which sol- (3) Solid in liquid Solid Liquid NaCl or sugar in
water
ute and solvent form uniform homogeneous one
phase due to attraction between their (C) Solid solution
(A) (1) Gas in solid Gas Solid H gas in
molecules/particles is called homogeneous sol-
palladium metal,
ution.
pumice stone
E.g. A solution of NaCl or sugar.
(2) Liquid in solid Liquid Solid Sodium
(2) Heterogeneous solution : A solution consisting of amalgam
two or more phases is called a heterogeneous sol- (3) Solid in solid Solid Solid Alloys, brass,
ution. E.g. A colloidal solution of starch. bronze, Cu in
■ gold.
Q. 3. Define : (1) Solvent (2) Solute. (1 mark) ■
Ans.
Q. 5. Mention the solvent and solute in the follow-
(1) Solvent : The component in which solution forma-
ing :
tion takes place and which constitutes larger pro-
(1) Smoke (2) Moisture
portion of a solution is called solvent. For example,
(3) Alloy (4) Soda water. (2 marks)
in an aqueous solution of sugar, water is the solvent.
Ans.
(2) Solute : In a solution the component which dis-
Substance Solvent Solute
solves and constitutes smaller proportion of a sol-
ution is called a solute. For example, in a sugar (1) Smoke Gas Solid
solution, sugar is the solute. ■ (2) Moisture Gas Liquid
(3) Alloy Solid Solid
Q. 4. What are the different types of solutions?
(4) Soda water Liquid Gas
(3 marks)
Ans. A solution consists of a solvent and a solute. Since ■
the physical states of a solvent and a solute may be Unit

gaseous, liquid or a solid, there are nine types of 2.3 Capacity of a solution to dissolve a solute
solutions.
Q. 6. What is a saturated solution ? (1 mark)
Ans. A solution which contains the maximum amount of
2. SOLUTIONS 49
dissolved solute and further the solute can’t be increases, solubility of solid increases and that of
dissolved is called a saturated solution. gases decreases.
There exists a dynamic equilibrium which is (5) Pressure :
represented as, (i) Pressure has no effect on the solubilities of
dissolution solids and liquids since they are incompress-
Solute;Solvent Solution.
ible.
crystallisation
■ (ii) The effect of pressure is important only for
Q. 7. What is a supersaturated solution ? (2 marks) solutions which involve gases as solutes. With
Ans. A solution containing a solute more than that the increase in pressure and decrease in tem-
required to form a saturated solution at equilibrium perature, the solubility of gases increases. ■
is called a supersaturated solution. ★ Q. 10. What is the effect of temperature on solubil-
When a tiny crystal of a solute is added to ity of solids in water ? Give examples. (2 marks)
supersaturated solution, the excess solute separates Ans. The solubility of a solid solute depends upon
out and forms saturated solution. ■ temperature.
Units (1) Generally rise in temperature increases the solubil-
2.4 Solubility ity. This is due to expansion of holes or empty
2.4.1 Factors affecting solubility spaces in the liquid solvent. Generally 10 °C rise in
temperature, increases the solubility of solids two
Q. 8. What is solubility of a solute ? (1 mark) fold.
Ans. Solubility : It is defined as amount of a solute
present per unit volume in its saturated solution at a
specific temperature.
It is expressed in mol L 91 or mol dm 93. ■
Q. 9. Explain the factors on which the solubility of a
substance (solute) depends. (3 marks)
Ans. The extent of dissolution of a substance (solute)
depends upon the following factors :
(1) Nature of a solute : A solute may be crystalline,
amorphous, ionic or covalent. Hence accordingly its
tendency to dissolve changes. The substances hav-
ing similar intermolecular forces tend to dissolve in
each other.
(2) Nature of solvents : Solvents are classified as
polar and nonpolar. Polar solutes dissolve in polar Fig. 2.1 : Variation of solubilities of some ionic solids with
solvents. For example, ionic compounds dissolve in temperature
polar solvent like water. A solvent other than water
(2) Dissolution process may be endothermic or
is called a nonaqueous solvent. For example, C H ,
exothermic.
CCl , etc. Solutions in these solvents are called
(3) The solubility of the substances like NaBr, NaCl,
nonaqueous solutions.
The solvent may be a gas, a liquid or a solid. KCl, etc. changes slightly with the increase in
(3) Amount of a solvent : More amount of a solvent, temperature.
will dissolve more quantity of the solute. (4) The solubility of the salts like NaNO , KNO , KBr,

(4) Temperature : Depending on the nature of a sol- etc. increases appreciably with the increase in
vent and a solute the solubility changes with tem- temperature.
perature. The effect depends on the heat of solution, (5) The solubility of Na SO first increases and after

hydration energy, etc. Generally as the temperature 30 °C decreases with the increase in temperature.

This variation in solubility with temperature can be H CO , while NH forms NH OH in aqueous

used to separate the salts from the mixture by solutions.
fractional crystallisation. ■ (4) The solubility of gases in liquids increases with the
Can you tell ? increase in pressure and the decrease in tempera-
(Textbook page 29) ture. ■
Q. Why naphthalene dissolves in benzene but not Q. 13. Why does the solubility of a gas decrease with
in water ? increase in temperature ? (2 marks) OR
Ans. Since naphthalene is a covalent nonpolar sub- How does solubility of a gas in water varies with
stance, it is soluble in a nonpolar solvent like temperature ? (2 marks)
benzene but insoluble in polar solvent like water.
Ans.
(1) The gases are soluble in water and other liquids.
Q. 11. Explain with the help of Le Chatelier’s prin-
(2) According to Charles’ law, the volume of a given
ciple the effect of temperature on solubility.
(2 marks) mass of a gas increases with the increase in tem-
Ans. perature at constant pressure.
(1) The effect of temperature on solubility depends on (3) Hence, the volume of the dissolved gas increases
enthalpy of solution. with the increase in temperature.
(2) For example, dissolution of KCl in water is an (4) This enormous increase in volume of the gases
endothermic process since heat is absorbed during cannot be accommodated by the solvent molecules,
dissolution. In this according to Le Chatelier’s hence excess of the gases escape out in the form of
principle by increasing temperature the solubility of bubbles.
KCl increases. Therefore, the solubility of gases in liquids
(3) Dissolution of CaCl , Li SO , H O in water is an decreases with temperature. ■

exothermic process since heat is evolved during Q. 14. Explain the effect of pressure on the solubility
dissolution. In this, according to Le Chatelier’s of the gases. (2 marks) OR
principle by increasing the temperature the solubil- State and explain Henry’s law. (2 marks)
ity decreases. ■ Ans.
(1) Since the gases are compressible, their solubility in
Can you tell ?
(Textbook page 29) the liquids is influenced by external pressure of the
Q. Anhydrous sodium sulphate dissolves in water gas. The solubility of gases increases with the
with the evolution of heat. What is the effect of increase in pressure.
temperature on its solubility ? (2) Henry’s law : It states that the solubility of a gas in
Ans. Since the dissolution of anhydrous sodium a liquid at constant temperature is proportional to
sulphate in water is an exothermic process due to the pressure of the gas above the solution.
evolution of heat, according to Le Chatelier’s (i) If S is the solubility of a gas in mol dm\ at a
principle its solubility decreases with the increase pressure P and constant temperature then by
in temperature. Henry’s law,
S . P or S:KH ;P
Q. 12. Explain the solubility of gases in liquids.
where KH is called Henry’s law constant.
(2 marks)
Ans. (ii) If P:1 atm, then S:KH.
(1) Gases are soluble in water and other liquids and (iii) If several gases are present, then the solubility
their solubility depends upon the nature of the gas. of any gas in the mixture is proportional to its
(2) Non-polar gases like O , have less solubility in partial pressure at given temperature.

polar solvents. (3) Illustration of Henry’s law : In case of aerated or
(3) Polar gases like CO , NH , HCl, etc. are more carbonated drink beverage, the bottle is filled by

soluble in polar solvent like water. CO forms dissolving CO gas at high pressure and then sealed.

2. SOLUTIONS 51
Above the liquid surface there is air and undissol-
Solved Examples 2.4
ved CO . Due to high pressure, the amount of

dissolved CO is large. Q. 18. Solve the following :

When the cap of the aerated bottle is removed, (1) For a gas, the Henry’s law constant is
the pressure on the solution is lowered, hence 1.25;10\ mol dm\ atm\ at 25 °C. Calculate
excess of CO and air escape out in the form of the solubility of the given gas at 2.5 atm and

effervescence. Thus by decreasing the pressure, 25 °C. (2 marks)
solubility of CO is decreased. ■ Solution :

Q. 15. What are the exceptions to Henry’s law ? Given : Henry’s law constant:KH
Why ? (2 marks) :1.25;10\ mol dm\ atm\
Ans. Pressure of the gas:P:2.5 atm
(1) The gases like NH and CO do not obey Henry’s Solubility of the gas:S:?

law. By Henry’s law
(2) This is because, these gases react with water, S:KH ;P
NH (g) ;H O(l) IIIIIJ NH ; (aq) ;OH 9(aq) :1.25;10\ mol dm\ atm\;2.5 atm

CO (g) ;H O(l) IIIIIJ H CO (aq) :3.125;10\ mol dm\

(3) Due to reactions of the gases like NH , CO (g), they Ans. Solubility of gas:3.125;10\ mol dm\

have higher solubilities than expected by Henry’s ------------------------------------------------------------------------------------
law. ■ (2) The solubility of dissolved oxygen to 27 °C is
2.6;10\ mol dm\ at 2 atm. Find its solubility
Q. 16. Oxygen gas is slightly soluble in water but it is
highly soluble in blood. Explain. (1 mark) at 8.4 atm and 27°C. (2 marks)
Ans. The vital constituent of blood, namely haemo- Solution :
Given : Solubility of O
globin reacts with oxygen increasing the solubility
of oxygen. :S :2.6;10\ mol dm\

Haemoglobin;4O (g) IIIIIJ Haemoglobin O Initial pressure of O :P :2 atm

This oxygenated blood is circulated to the vari- Final pressure of O :P :8.4 atm

ous parts of body, for the supply of oxygen. ■ Solubility of O :S :?

Q. 17. Obtain the units of Henry’s law constant. (i) By Henry’s law,
(1 mark) S :KH ;P

Ans. By Henry’s law, S:KH ;P, where S is solubility Henry’s law constant KH is,
of the gas in mol dm\, P is the pressure of the gas S 2.6;10\
KH : :
in atmosphere (or in bar) and KH is Henry’s law P 2

constant. :1.3;10\ mol dm\ atm\
S(mol dm\) (ii) Now, S :KH ;P :1.3;10\;8.4
KH: mol dm\ atm\ or mol dm\
P(atm) :10.92;10\
bar\ :1.092;10\ mol dm\
Hence the units of Henry’s law constant KH are Ans. Solubility of O :1.092;10\ mol dm\

------------------------------------------------------------------------------------
mol dm\ atm\. ■
(3) Henry’s law constant for the solubility of
Do you know ? methane in benzene is 4.27;10\ mm\ Hg
(Textbook page 31)
mold dm\ at constant temperature. Calculate
O gas has very low solubility in water. However, its
the solubility of methane at 760 mm Hg
solubility in blood is exceedingly high. This is because
pressure at same temperature. (2 marks)
of binding of O molecule to haemoglobin present in
Solution :
blood.
Given : Henry’s law constant:KH
Hb;4O & HB(O )
:4.27;10\ mm\ Hg mol dm\

Pressure of the gas:P:760 mm Hg S :2.5;10\ g dm\

KH :4.27;10\ mm\ mol dm\ 2.5;10\
: mol dm\
:4.27;10\;760 atm\ mol dm\ 28
:3245;10\ atm\ mol dm\ :8.93;10\ mol dm\
:3.245;10\ atm\ mol dm\ P :
760
:1 atm
760 760
P:760 mm: atm:1 atm 20,000
760 P : :26.32 atm
By Henry’s law, 760
S:KH ;P:3.245 ;10\ atm\ mol dm\;1atm By Henry’s law,
:3.245;10\ mol dm\ S :KH ;P

S 8.93;10\
Ans. Solubility of methane:3.245;10\ mol dm\ KH : :
P 1
------------------------------------------------------------------------------------

(4) The solubility of ethane at 25 °C is 0.92;10\ g :8.93;10\ mol dm\ atm\
dm\ at 1000 mm Hg pressure. Calculate S :KH ;P :8.93;10\;26.32

Henry’s law constant. (2 marks) :2.35;10\ mol dm\
Ans. Solubility of N gas
Solution :
Given : Solubility of ethane :2.35;10\ mol dm\.
[Alternative method :
:S:0.92;10\ g dm\
S :KHP and S :KHP
Pressure of ethane:P:1000 mm Hg
S KHP P
Molar mass of ethane (C H ):30 g mol\ : :
S KHP P
Henry’s law constant:KH :?
P 20,000
S:0.92;10\ g dm\ S :S ; :8.93;10\;
P 760
0.92
: ;10\ :2.35;10\ mol dm\ ]
30 ------------------------------------------------------------------------------------
:3.067;10\ mol dm\
★ (6) Fish generally needs O concentration in water
1000
P:1000 mm: atm:1.316 atm at least 3.8 mg/L for survival. What partial
760
pressure of O above the water is needed for the
By Henry’s law,
survival of fish ? Given the solubility of O in
S:KH ;P
water at 0 °C and 1 atm partial pressure is
S 3.067;10\
KH : : 2.2;10\ mol/L. (2 marks)
P 1.316 Solution :
:2.33;10\ mol dm\ atm\ Given : Required concentration of O
Ans. Henry’s law constant:KH
:3.8 mg/L
:2.33;10\ mol dm\ atm\ 3.8;10\
------------------------------------------------------------------------------------ : mol L\
32
(5) The solubility of nitrogen at 30 °C is 2.5;10\
Solubility of O :2.2;10\ mol L\
g dm\ at 760 mm pressure. What will be its
P:1 atm
solubility in mol dm\ at 20,000 mm and same Partial pressure of O needed:Po :?
temperature ? (2 marks)
S:KH ;Po
Solution :
S 2.2;10\
Given : Initial solubility of N KH : :
Po 1

:S :2.5;10\ g dm\ :2.2;10\ mol L\ atm\

Initial pressure:P :760 mm S 3.8;10\ 1
Po : : ;
Final pressure:P :20,000 mm KH 32 2.2;10\

Final solubility:S in mol dm\:? :0.05397 atm

Molar mass of N gas:28 g mol\ Ans. Pressure needed:Po :0.05397 atm. ■

2. SOLUTIONS 53
Q. 19. Marine life like fish prefers to stay at lower the mole fraction of a solvent then by Raoult’s law,
level in water. Explain. (2 marks) OR P:x ;P .

Explain, why do aquatic animals prefer to stay at Explanation : Consider a solution containing two
lower level of water during summer ? (2 marks) volatile components A and B having mole fractions
Ans. x and x respectively.

(1) The solubility of oxygen gas decreases with the Let P and P be the vapour pressures of pure
increase in temperature.
components (or liquids) A and B respectively.
(2) In sea or lake water, the temperature of upper level Then by Raoult’s law, vapour pressure of compo-
is higher than the lower level. nent A:P :x ;P , vapour pressure of compo-

(3) Therefore the dissolved oxygen content in water is nent B:P :x ;P.
more at lower level than at higher level required for
Here P and P represent partial vapour press-
the marine life.
ures of the two liquid components in the solution.
Hence marine life like fish prefers to stay at lower Hence the total vapour pressure, PT of the
level than upper level of water. ■
solution will be,
PT :P ;P
(Textbook page 30)
PT :x P ;x P
● In United States about 1000000 billion gallons of
B x ;x :1
water from rivers and lakes are used for industrial
x :19x
cooling. The cooling process heats water. The hot
PT :(19x ) P ;x P
water then returns to rivers and lakes. The solubility
:P 9x P ;x P
of oxygen decreases in hot water thereby affecting
:(P 9P)x ;P
the life of cold blooded animals like fish.
With the help of above equation, the vapour
pressures of solutions having different concentra-
(Textbook page 30) tions (or mole fractions) can be calculated. ■
Demonstration of Henry’s law. Q. 21. Explain the variation of vapour pres-

Before sealing the bottle of soft drink, it is pressur- sure with mole fraction of a solute in a liquid
ised with a mixture of air, CO saturated with water mixture. (3 marks)

vapour. Because of high partial pressure of CO , its Ans. Consider a liquid mixture of two liquid components

amount dissolved in soft drink is higher than the A and B having vapour pressures P and P and

solubility of CO under normal conditions. mole fractions x and x respectively.

When the bottle of soft drink is opened, excess By Raoult’s law, the vapour pressures P and P

dissolved CO comes out with effervescence. are,

P :x P and P :x P
Units
The vapour pressure of the solution is,
2.5 Vapour pressure of liquids in liquids PT :P ;P :x P ;x P
2.5.1 Raoult’s law
2.5.2 Ideal and nonideal solutions
Q. 20. State and explain Raoult’s law. (2 marks)

Ans. Statement of Raoult’s law : The law states that, at
constant temperature, the partial vapour pressure of
any volatile component of a solution is equal to the
product of vapour pressure of the pure component
and the mole fraction of that component in the
solution.
Let P and P be the respective vapour pressures
Fig. 2.2 : Variation of vapour pressure with
of a pure volatile component and a solution. If x is mole fraction of solute

PT :(P 9P) x ;P and the volume of solution is equal to the sum of

The plot of PT versus x is a straight line. The volumes of two liquid components.

plots of P versus x and P versus x are straight mixV:0

lines passing through the origin. (4) In the ideal solution, solvent-solvent, solute-solute
When x :1, x :0, PT :P and when x :0, and solvent-solute interactions are comparable.

x :1, PT :P as shown by lines I and II in Fig. 2.2 (5) The vapour pressure of an ideal solution lies

■ between vapour pressures of two pure components.
■
Q. 22. Explain the composition of vapour phase
Q. 25. Give an example of an ideal solution.
above a liquid mixture. (2 marks)
(1 mark)
Ans. Consider a liquid mixture of two liquids A and B
Ans. A liquid mixture of benzene and toluene which
having vapour pressures PA and PB and mole
have nearly identical physical properties and inter-
fractions x and x respectively in the liquid phase.
molecular forces forms an ideal solution. ■
By Raoult’s law, the vapour pressures of two
liquids will be, Q. 26. What are the characteristics of nonideal
PA :x PA and PB :x PB solutions. (2 marks)

The total vapour pressure of this liquid mixture Ans.
is, (1) Nonideal solutions do not obey Raoult’s law over
PT :PA ;PB the entire range of concentrations.
PT :x PA ;x PB (2) The vapour pressures of these solutions may be

The vapour above liquid surface contains A and higher or lower than ideal solutions.
B. If y and y are the mole fractions of A and B (3) These solutions exhibit two types of deviations

components respectively in the vapour phase, then from Raoult’s law namely (a) positive deviation
by Dalton’s law of partial pressures, and (b) negative deviation.
PA :y PT and PB :y PT (4) These solutions give azeotropic mixtures. ■

and total vapour pressure is, Q. 27. Explain solutions with positive deviations
PT :y PT ;y PT. ■
from Raoult’s law. (2 marks)
Q. 23. What are ideal and nonideal solutions ? Ans.
(2 marks) (i) A solution or a liquid mixture which has higher
Ans. vapour pressure than theoretically calculated by
(1) Ideal solutions : These are solutions which obey Raoult’s law or higher than those of pure compo-
Raoult’s law over an entire range of concentrations nents is called a nonideal solution with positive
at constant temperature. deviation.
(2) Nonideal solutions : These are solutions which do
not obey Raoult’s law over the entire range of
concentrations. ■
Q. 24. What are the characteristics of ideal solu-

tions ? (2 marks)
Ans.
(1) The ideal solutions obey Raoult’s law over entire
range of concentrations at constant temperature.
(2) In the formation of an ideal solution, heat is neither
evolved nor absorbed and enthalpy change for Fig. 2.3 : Positive deviations from Raoult’s law
mixing is zero, i.e. H:0. (ii) In these solutions, solute-solvent intermolecular
mix
(3) In the formation of an ideal solution, there is no attractions are weaker than those between solvent-
volume change on mixing two liquid components solvent and solute-solute interactions.
2. SOLUTIONS 55
(iii) For example, solutions of acetone and ethanol, nA 0.1667
xA : : :0.07693
carbon disulphide and acetone, etc. ■ n 2.1667
n 2
Q. 28. Explain solutions with negative deviations xB : B : :0.9230
n 2.1667
from Raoult’s law. (2 marks)
Psoln :xAPA ;xBPB
Ans.
:0.07693;400;0.9230;600
(1) A solution or a liquid mixture which has lower
:30.772;553.8
vapour pressure than theoretically calculated by
:584.572 mm Hg
Raoult’s law or lower than those of pure compo-
Ans. Vapour pressure of solution
nents is called a nonideal solution with negative
:Psoln :584.572 mm Hg
deviation. ------------------------------------------------------------------------------------
(2) 2.5 mol of a liquid A is mixed with 4.5 mol of

liquid B at 25 °C. If the vapour pressures of A
and B at 25 °C are 160 mm Hg and 230 mm Hg
respectively, calculate the vapour pressure of the
liquid mixture. (2 marks)
Solution :
Given : nA :2.5 mol; nB :4.5 mol,
PA :160 mm Hg; PB :230 mm Hg, Psoln :?
Total number of moles:n:nA ;nB
Fig. 2.4 : Negative deviations from Raoult’s law :2.5;4.5
(2) In these solutions, the intermolecular interactions :7.0 mol
between solvent and solute molecules are stronger n 2.5
Mole fraction of A:xA : A : :0.3571
than solvent-solvent or solute-solute interactions. n 7
(3) For example, solutions of phenol and aniline, Mole fraction of B:19xA :190.3571
chloroform and acetone, etc. ■ :0.6429
Psoln :xAPA ;xBPB
Solved Examples 2.5 :0.3571;160;0.6429;230
Q. 29. Solve the following : :57.136;147.9
(1) The vapour pressures of two liquids A and B are :205 mm Hg
400 mm Hg and 600 mm Hg respectively at Ans. Psoln :205 mm Hg
------------------------------------------------------------------------------------
47° C. A solution is prepared by dissolving 10 g
of A of molar mass 60 g mol 91 in 80 g of B of (3) The vapour pressures of pure liquids A and B
molar mass 40 g mol 91. Find the vapour press- are 400 mm Hg and 650 mm Hg respectively at
ure of the solution. (3 marks) 330 K. Find the composition of liquid and vapour
Solution : if total vapour pressure of solution is 600 mm
Given : PA :400 mm Hg; PB :600 mm Hg, Hg. (3 marks)
WA :10 g and WB :80 g. Solution :
MA :60 g mol 91; MB :40 g mol 91, Psoln :? Given : PA :400 mm Hg; PB :650 mm Hg,
W 10 PT :600 mm Hg, T:330 K; xA :? xB :?, y :?
nA : A : :0.1667 mol
MA 60 y :?

W 80 (x is mole fraction in liquid phase while y is mole
nB : B : :2 mol
MB 40 fraction in vapour phase.)
Total number of moles:n:nA ;nB PT :(PB 9PA) xB ;PA
:0.1667;2 600:(6509400) xB ;400
:2.1667 mol :250 xB ;400

6009400 Units
xB : :0.8
250 2.6 Colligative properties of nonelectrolyte
B xA ;xB :1 solutions
xA :19xB :190.8:0.2 2.7 Vapour pressure lowering
The composition of A and B in liquid mixture is, 2.7.1 Raoult’s law for solutions of nonvolatile
xA :0.2 and xB :0.8. solutes
If P and P are vapour pressures (or partial 2.7.2 Relative lowering of vapour pressure

pressures) of A and B in vapour phase then by 2.7.3 Molar mass of solute from vapour pressure
Raoult’s law, lowering
P :xA ;PA :0.2;400:80 mm Hg Q. 30. Define the term colligative property. Give

P :xB ;PB :0.8;650:520 mm Hg examples. (2 marks)

If y and y are mole fractions of A and B Ans.

respectively in vapour phase then, by Dalton’s law, (1) Colligative Property : The property of a solution
P :y PT which depends on the total number of particles of

P 80 the solute (molecules, ions) present in the solution
y : : :0.1333
PT 600 and does not depend on the nature or chemical
P :y PT composition of solute particles is called colligative
property of the solution.
P 520
y : : :0.8667 (2) Examples of colligative properties : (a) lowering
PT 600
(or y :19y :190.1333:0.8667) or relative lowering of vapour pressure of a solution
(b) elevation in the boiling point (c) depression in
Ans. Composition of liquid : xA :0.2 and xB :0.8
the freezing point (d) osmotic pressure. ■
Composition of vapour : yA :0.1333 and yB :0.8667
------------------------------------------------------------------------------------ Q. 31. Explain and define the term vapour pressure
of a liquid. (2 marks) OR
(4) A mixture of two liquids A and B have vapour What is vapour pressure of a liquid ? (2 marks)
pressures 3.4;10 Nm 9 and 5.2;10 Nm 9 . Ans.
If the mole fractions of A is 0.85, find the vapour
pressure of the solution. (2 marks)
Solution :
Given : Vapour pressure of pure liquid A
:P A :3.4;10 Nm 9
Vapour pressure of pure liquid B
:P B :5.2;10 Nm 9
Fig. 2.5 : Evaporation of a liquid
Mole fraction of A:xA :0.85
Mole fraction of B:xB :19xA (1) If a volatile liquid is placed in an open vessel, the
:190.85 liquid molecules have a tendency to escape in a
gaseous state forming vapour and diffuse into
:0.15
surroundings. Hence evaporation takes place
The vapour solution is given by
continuously, and no equilibrium is attained.
Psoln :XAP A ;XB P B
(2) If a liquid is placed in a closed vessel, the vapour
:0.85;3.4;10;0.15;5.2;10
molecules get accumulated on its surface. These
:2.89;10;0.78;10 vapour molecules are in continuous random motion.
:(2.89;0.78);10 They collide with each other, with walls of a
Psoln :3.67;10 Nm 9 container and surface of the liquid, and return to the
Ans. Vapour pressure of a solution:3.67;10 liquid state. This reverse phenomenon is called
Nm9 ■ condensation.
2. SOLUTIONS 57
(3) After some time, rates of evaporation and condensa- ★ Q. 33. Why vapour pressure of a solvent is lowered
tion become equal and an equilibrium is established by dissolving a nonvolatile solute into it ?
between liquid and vapour phases. At this stage the (1 mark)
vapour exerts a constant pressure called vapour Ans. For answer refer to answer (2) of Q. 32. ■
pressure on liquid surface at constant
Q. 34. State and explain Raoult’s law for solutions of
temperature.
nonvolatile solutes. (3 marks)
(4) Vapour pressure : The pressure exerted by the Ans.
vapour of a liquid (or solid) when it is in equilib- (a) Statement of Raoult’s law : The law states that the
rium with the liquid (or solid) phase at a constant vapour pressure of a solvent over the solution of a
temperature is called the vapour pressure of the nonvolatile solute is equal to the vapour pressure of
liquid (or solid). the pure solvent multiplied by mole fraction of the
(5) The vapour pressure of a liquid increases with the solvent at constant temperature.
increase in temperature. ■ (b) Explanation : Let P and P be the vapour press-

Q. 32. Explain the following terms : ures of a pure solvent and a solution respectively. If
(1) Relative vapour pressure of a solution x is the mole fraction of the solvent then Raoult’s

(2) Lowering of vapour pressure of a solution law can be represented as,
(3) Relative lowering of vapour pressure. P:x P

(1 mark each) For a binary solution containing one solute, if x

Ans. and x are mole fractions of a solvent and a solute

(1) Relative vapour pressure of a solution : If P is respectively then,

the vapour pressure of a pure liquid (solvent) and P x ;x :1

is the vapour pressure of a solution after adding a x :19x

nonvolatile solute, then, relative vapour press- P:x P

P :(19x ) P
ure: .
P :P 9x P

(2) Lowering of vapour pressure of a solution : P 9P:x P

When a nonvolatile solute is added to a pure P 9P
x :
solvent, the surface area is covered by the solute P

molecule decreasing the rate of evaporation, hence P 9P:P is the lowering of vapour pressure

its vapour pressure decreases. This decrease in P
x :
P
vapour pressure is called lowering of vapour press-
In the equation, P 9P/P is called relative
ure.
lowering of vapour pressure.
If P is the vapour pressure of a pure solvent
Hence Raoult’s law can also be stated as the
(liquid) and P is the vapour pressure of the solution,
relative lowering of vapour pressure is equal to
where P
P , then, (P 9P) is the lowering of the
mole fraction of the solute. ■
vapour pressure.
★ Q. 35. State Raoult’s law for a solution containing
(3) Relative lowering of vapour pressure : If P and
a nonvolatile solute. (1 mark)
P are the respective vapour pressures of a pure
liquid (solvent) and the solution containing a non- Ans. For answer refer to answer (a) of Q. 34. ■
volatile solute then P

P . Hence, P 9P repre- Q. 36. Show that relative lowering of vapour press-

sents the lowering of the vapour pressure due to ure is a colligative property. (2 marks)
addition of a nonvolatile solute. Ans. Consider a binary solution containing a nonvolatile
Relative lowering of vapour pressure solute. If P and P are vapour pressures of a pure

P 9P P solvent and the solution respectively then,
: : . ■
P P Lowering of vapour pressure:P:P 9P

Relative lowering of vapour pressure: Ans. Consider a solution in which W gram of a solvent

P 9P of molar mass (or molecular weight) M contains

P W gram of a solute of molar mass M . Then

By Raoult’s law, W
P 9P number of moles of a solvent:n :
:x M
P
W
where x is mole fraction of the solute. Therefore Number of moles of a solute:n :
M
the relative lowering of vapour pressure is a col-
Total number of moles:n:n ;n
ligative property. ■

n
Q. 37. Explain the variation of vapour pressure with Mole fraction of the solvent:x :
n
mole fraction of a solvent in solution. n
(2 marks) OR Mole fraction of the solute:x :
n
Explain the variation of vapour pressure with
n n
the concentration of a solution. (2 marks) x ;x : ;
n n
Ans. The vapour pressure of a pure solvent decreases
n ;n
when a nonvolatile solute is dissolved in it. Con- :
n
sider a pure solvent with vapour pressure P and
n
mole fraction x . For a solution containing a non- :
n
volatile solute, if x and x are the mole fractions of
x ;x :1
a solvent and a solute respectively, then x ;x :1
In the case of an ideal solution which is a dilute
and x
1.
solution, the concentration and the number of moles
of the solute are very low, i.e. n
n

n ;n X n

n
Now, x :
n
n
:
n ;n

n
X
n

W /M
x :
W /M
Fig. 2.6 : Variation of vapour pressure of solution with

W ;M
mole fraction of solvent in solution x :
W ;M
By Raoult’s law, P:x ;P . As the mole
If P and P are the vapour pressures of a pure
fraction of a solvent in the solution increases the
vapour pressure increases as shown in the above solvent and a solution respectively, then relative
figure 2.5. When x becomes equal to 1, the vapour P 9P
lowering of vapour pressure:
pressure becomes P , i.e. the vapour pressure of a P

pure solvent. By Raoult’s law
If at any mole fraction of a solvent, the vapour of P P 9P
: :x
the solution is P, then the lowering of vapour P P

pressure will be, P:P 9P.
P 9P W ;M
:
■ 1
( 2 mark)
P W ;M
Q. 38. Derive a relation between relative lowering
of vapour pressure and molar mass of non- P W ;M
OR :
volatile solute. (2 marks) P W ;M

2. SOLUTIONS 59
Hence by measuring the vapour pressure of a :0.35;10 Nm 9
pure solvent and a solution, the molar mass of the :3.5;10 Nm 9
dissolved nonvolatile substances can be deter- (C) Relative lowering of vapour pressure is given
mined. ■ by,
P 9P 4;1093.65;10
★ Q. 39. Using Raoult’s law, how will you show that :
P 4;10
P:Px ? Where x is the mole fraction of
0.35;10
solute in the solution and P is vapour pressure
:
4;10
of pure solvent. (2 marks)
:0.0875
Ans. If x and x are the mole fractions of solvent and
Ans. (A) 0.9125 (B) 3.5;10 Nm 9 (C) 0.0875
solute respectively, then ------------------------------------------------------------------------------------
x ;x (2) A pure liquid has vapour pressure 5.2;10 Pa

By Raoult’s law, at 298 K. When a solute is dissolved, the mole
P:x ;P fraction of it is 0.02 in the solution. Find the

where P is the vapour pressure of a pure solvent vapour pressure of the solution. (2 marks)
and P is the vapour pressure of the solution at given Solution :
temperature. Given : P :5.2;10 Pa

P x :0.02
:x
P P:?

P
19 :19x P 9P
:x
P
P

P 9P P
:x 19 :x
P P

If P 9P:P, P
:19x
P P
then :x . ■
P :x

P:x ;P
Solved Examples 2.6 – 2.7
:(190.02);5.2;10
Q. 40. Solve the following : :5.096;10 Pa
(1) The vapour pressure of a pure liquid at 298K is Ans. Vapour pressure of the solution
4;10 Nm 9 . When a nonvolatile solute is :5.096;10 Pa
------------------------------------------------------------------------------------
dissolved the vapour pressure becomes
★ (3) The vapour pressure of water at 20°C is 17
3.65;10 Nm\. Calculate (A) relative vapour
mm Hg. Calculate the vapour pressure of a
pressure, (B) lowering of vapour pressure and
solution containing 2.8 g of urea (NH CONH )
(C) relative lowering of vapour pressure.
in 50 g of water. (2 marks)
(3 marks)
Solution :
Solution :
Given : Vapour pressure of pure solvent
Given : P :4;10 Nm 9
(water):P
P:3.65;10 Nm 9
P :17 mm Hg
(A) Relative vapour pressure: Weight of solvent:W :50 g
P

3.65;10 Weight of solute (urea):2.8 g
:
4;10 Molecular weight of a solvent:M :18

:0.9125 Molecular weight of a solute (urea):M

(B) Lowering of vapour pressure: P:P 9P :60 g mol 9

:4;1093.65;10 P 9P W ;M
:
:(493.65);10 P W ;M

179P 2.8;18 P 9P W ;M
: :0.0168 :
17 50;60 P W ;M

179P:17;0.0168 B P 9P:P

179P:0.2856 P W ;M
:
P:1790.2856 P W ;M

P W ;M
:16.7144 mm Hg M : ;
P W
Ans. Vapour pressure of solution:16.7144 mm
17.535;18.04;18
Hg :
------------------------------------------------------------------------------------ 0.309;100
(4) The vapour pressure of pure benzene is 640 mm :184.3 g mol\
of Hg. 2.175;10 9 kg of nonvolatile solute is Ans. Molar mass of mannitol:184.3 g mol\
------------------------------------------------------------------------------------
added to 39 gram of benzene, the vapour press- (6) The vapour pressure of 2.1% solution of a
ure of solution is 600 mm of Hg. Calculate molar non-electrolyte in water at 100 °C is 755 mm Hg.
mass of solute (C:12, H:1). (3 marks) Calculate the molar mass of the solute. (3 marks)
Solution : Solution :
Given : P :640 mm Hg Given : At 100 °C, vapour pressure of water:P

W1 :39 g benzene:39;10 93 kg :760 mm Hg
W2 :2.175;10 93 kg Vapour pressure of the solution:P:755 mm Hg
P:600 mm Hg Since the solution is 2.1 % by mass,
M1 :78;10 93 kg M2 :? Mass of solute (nonelectrolyte):W :2.1 g

P 9P W2 ;M1 Mass of water:W :10092.1:97.9 g
:
P W1 ;M2 Molar mass of water:M :18 g mol\

Molar mass of nonelectrolyte:M :?
6409600 2.175;10 93 ;78;10 93
: P 9P W ;M
640 39;10 93 ;M2 :
2.175;10 93 ;78;10 93 P W ;M
640
M2 : ;

93
39;10 (6409600) P W ;M
M : ;
P 9P W
:69.6;10 93 kg mol 91
760;2.1;18
Ans. Molar mass of a solute:69.6;10 93 kg :
(7609755);97.9
mol 91
------------------------------------------------------------------------------------ :58.69 g mol\
(5) In an experiment, 18.04 g of mannitol were Ans. Molar mass of nonelectrolyte
dissolved in 100 g of water. The vapour pressure :58.69 g mol\
------------------------------------------------------------------------------------
of water was lowered by 0.309 mm Hg from (7) Calculate the mass of a nonvolatile solute (molar
17.535 mm Hg. Calculate the molar mass of man- mass 40;10\ kg/mol) which is dissolved in
nitol. (2 marks) 114;10\ kg octane to reduce its vapour
Solution : pressure to 80%. (3 marks)
Given : Mass of a solute (mannitol) Solution :
:W :18.04 g Given : Molar mass of solute:M :40;10 93

Mass of a solvent (water):W :100 g kg mol 91

Vapour pressure of a solvent (water) Mass of solvent (octane):W :114;10 93 kg

:P If vapour pressure of octane:P :100

:17.535 mm Hg Vapour pressure of solution:P:80
Lowering of vapour pressure:P:0.309 mm Hg Molar mass of octane (C H ):114;1093 kg

Molar mass of H O:M :18 g mol\ mol 91

Molar mass of solute (mannitol):M :? Mass of solute:W :?

2. SOLUTIONS 61
In this solution, since the vapour pressure is Q. 41. Explain the effect of temperature on the
decreased by greater extent, 100980:20% the vapour pressure of a liquid. (1 mark)
solution must be concentrated and number of moles Ans. The vapour pressure of a liquid is the pressure of the
of solute must be large so that n ;n " n vapour in equilibrium with the liquid at a given

Hence Raoult’s law must be represented as, temperature.
P 9P n The evaporation of a liquid requires thermal
:
P n ;n
energy. Hence, as temperature rises, the vapour
P 9P n W ;M
(Hence equation, : : , cannot pressure rises until it becomes equal to the external
P n W ;M
pressure, generally the atmospheric pressure,
be used.)
101.3 kNm 92 (1 atm). This temperature is called
W 114;10\
Now n : : :1 mol the normal boiling point of the liquid. ■
M 114;10\

P 9P n Q. 42. What is boiling point of liquid ? (1 mark)
:
P 1;n OR

100980 n Define boiling point. (1 mark)
:
100 1;n
Ans. The boiling point of a liquid is defined as the
n :0.25 mol
temperature at which the vapour pressure of the
Mass of solute dissolved:W
liquid becomes equal to the external pressure, i.e.,
:moles;molar mass
the atmospheric pressure (1 atm), e.g., the boiling
:0.25;40;10\
point of water at 1 atm is 373 K.
:0.01 kg ■
Ans. Mass of solute dissolved: 0.01 kg Q. 43. Explain the elevation in the boiling point
------------------------------------------------------------------------------------
of a solution. (1 mark)
(8) The vapour pressure of water is 16.8 mm Hg at a
Ans. The elevation in the boiling point of a solution is
certain temperature. If the vapour pressure of
defined as the difference between the boiling points
the solution is 16.78 mm, find the molality of the
of the solution and the pure solvents at a given
solution. (2 marks)
pressure, e.g. If T0 and T are the boiling points of a
Solution :
Given : P :16.8 mm Hg; P:16.78 mm Hg pure solvent and a solution, then the elevation in
boiling point, Tb :T9T0. It is a colligative
Molar mass of water:M :18 g mol\
property. ■
Molality of the solution:m:?
P 9P M Q. 44. ★ Explain with diagram the boiling point elev-
: ;m
P 1000 ation in terms of vapour pressure lowering.

1000 P 9P 1000

16.8916.78 (3 marks) OR
m: ; : ;
M P 18 16.87 ★ How is vapour pressure lowering related to a rise

:0.66 mol\ kg in boiling point of solution ? (3 marks)
Ans. Molality of the solution:0.66 m ■ Ans.
Units (1) The boiling point of a liquid is the temperature at
2.8 Boiling point elevation which the vapour pressure of the liquid becomes
2.8.1 Boiling point elevation as a consequence equal to the external pressure, generally 1 atm
of vapour pressure lowering (101.3;10 Nm92 ).
2.8.2 Boiling point elevation and concentration (2) When a liquid is heated, its vapour pressure rises
of solute till it becomes equal to the external pressure.
2.8.3 Molar mass of solute from boiling point
If the liquid has a low vapour pressure, it has a
elevation
higher boiling point.

Remember ...
(Textbook page 36)
● Kb and Tb are the differences between two tem-
peratures. Hence, their values will be same in K or
in °C.
Q. 46. What are the units of molal elevation cons-

tant ? (1 mark)
Ans. Boiling point elevation, Tb is given by,
Fig. 2.7 : Vapour pressure curve showing Tb :Kb ;m
elevation in boiling point
where m is molality in mol kg 91 and Kb is molal
(3) When a nonvolatile solute is added to a solvent, its elevation constant or abullioscopic constant.
vapour pressure decreases, hence the boiling point k
increases. T
Kb : b
m
This is explained by graphical representation of mol kg 91
the vapour pressure and the boiling point of the pure Kb has units K kg mol 91 (or °C kg mol 91)
solvent and the solution. Therefore, molal elevation constant is the elev-
If T and T are the boiling points of a pure solvent ation in boiling point produced by 1 molal solution

and a solution, then the elevation in the boiling of a nonvolatile solute. ■
point is given by, Q. 47. Derive the relation between molar mass of the
Tb :T9T
solute and boiling point elevation. (2 marks)
The curve AB, represents the variation in the Ans. The boiling point elevation, Tb of a solution is
vapour pressure of a pure solvent with temperature directly proportional to molality (m) of the solution.
while curve CD represents the variation in the Tb . m
vapour pressure of the solution. Tb :Kb m
(4) This elevation in the boiling point is proportional to where Kb is a proportionality constant
the lowering of the vapour pressure, i.e., P 9P, If m:1 molal, then
Tb :Kb
where P and P are the vapour pressures of the pure
where Kb is called molal elevation constant.
solvent and the solution.
[ Tb . (P 9P) or Tb . P ] ■ The molality of the solution is given by,
Number of moles of the solute
★ Q. 45. Write the equation relating boiling point m:
Weight of the solvent in kg
elevation to the concentration of solution.
Let W :Weight (in gram) of a solvent,
(2 marks)
W :Weight (in gram) of a solute
Ans. The elevation in the boiling point of a solution is
M :Molecular weight of the solute
directly proportional to the molal concentration
Then the molality (m) of the solution is given by
(expressed in mol kg91 ) of the solution.
kg
Hence, if Tb is the elevation in the boiling point W ; 1000 W
m: : mol kg\
of a solution of molal concentration m then, W M W ;M
kg kg mol\
Tb . m
Tb :K b m W ; 1000
Tb : K b ;
where K b is a proportionality constant. W M

If m:1 molal, Kb ;W ;1000
M :
Tb :Kb Tb ;W

K kg mol\ kg
Kb is called the ebullioscopic constant or molal K ;W
elevation constant. K b is characteristic of the OR M : b kg mol\
Tb ;W
solvent. K
kg
2. SOLUTIONS 63
If the weights and molecular weight are (i) Tb :Kb ;m
expressed in kg, then, :0.52;0.05
W :0.026K
Tb : K b ; ■
W M
(ii) The elevation in the boiling point is given by,
Q. 48. Define molal elevation constant (Ebullioscopic Tb :T b 9T
constant) ? Does it depend on the nature of a
Boiling point of a solution,
solute ? What are its units ? (3 marks) T b :T ; Tb
Ans.
:373;0.026
(1) Molal elevation constant (Ebullioscopic con- :373.026 K
stant) : It is defined as the elevation in boiling Ans. Tb :0.026 K, T b :373.026 K
point, produced by dissolving one mole of a solute ------------------------------------------------------------------------------------
in 1 kg (or 1000 gram) of a solvent (i.e. 1 molal
(2) 0.18 molal aqueous solution of a substance boils
solution).
at 373.25 K. Calculate the molal elevation
The elevation in the boiling point,
constant of water. (Boiling point of water is
Tb is given by
373.15 K) (2 marks)
Tb :Kb ;m
Solution :
where Kb is molal elevation constant and m is
Given : Concentration of solution:m:0.18 m
molality of the solution.
Boiling point of water:T :373.15 K
When m:1, Tb :Kb
Boiling of the solution:Tb :373.25
(2) Kb depends only on the nature of the solvent.
Molal elevation constant:Kb :?
(3) Kb does not depend on the nature of the solute.
Elevation in boiling point:Tb
(4) It does not depend on concentration of the solution.
:Tb 9T
(5) The units of molal elevation constant are :
:373.259373.15
(A) K kg mol 9 and (B) K m 9 . ■
:0.1 K
★ Q. 49. What is the effect on the boiling point of
Tb :Kb ;m
water if 1 mole of methyl alcohol is added to
T 0.1
1 dm of water ? Why ? (2 marks) Kb : b : :0.5556 K kg mol\
m 0.18
Ans. Ans. Molal elevation constant of water
(a) The boiling point of water (or any liquid) depends
:0.5556 K kg mol\
on its vapour pressure. ------------------------------------------------------------------------------------
(b) Higher the vapour pressure, lower is the boiling ★ (3) A solution of citric acid C H O in 50 g of acetic

point. acid has a boiling point elevation of 1.76 K. If Kb
(c) When 1 mole of volatile methyl alcohol is added to for acetic acid is 3.07 K kg mol 91, what is the
1 dm of water, its vapour pressure is increased molality of solution ? (2 marks)
decreasing the boiling point of water. ■ Solution :
Given : W :50 g acetic acid
Solved Examples 2.8
Tb :1.76 K
Q. 50. Solve the following :
Kb :3.07 K kg mol 91
(1) Calculate the (i) elevation in the boiling point
m:?
and (ii) the boiling point of 0.05 m aqueous
Tb :Kb ;m
solution of glucose. (Kb :0.52 Km 9 ) (2 marks)
T
Solution : m: b
Kb
Given : Concentration of the solution:m:0.05 m
1.76
Molal elevation constant:Kb :1.86 K kg mol 9 :
3.07
Boiling point of pure water:T :373 K
:0.5733 m
Elevation in the boiling point: T b :?
Ans. Molality of solution:0.5733 m
Boiling point of solution:Tb :? ------------------------------------------------------------------------------------

(4) The boiling point of benzene is 353.23 K. When boiling point of CS is 319.45 K.

1.80 gram of non-volatile solute was dissolved in (Given that Kb for CS :2.42 K kg mol 91 and

90 gram of benzene, the boiling point is raised to atomic mass of S:32.) (3 marks)
354.11 K. Calculate the molar mass of solute. Solution :
[Kb for benzene:2.53 K kg mol 91 ] (2 marks) Given : W :3.795 g; W :100 g CS

Solution : Tb :319.81 K; T0 :319.45 K
Given : T b :353.23 K; Tb :354.11 K Kb :2.42 K kg mol\ M :?

W :90 g; W :1.8 g; Kb :2.53 K kg mol 91 Tb :Tb 9T0 :319.819319.45:0.36 K

Molar mass:M :? W ;1000
Tb :Kb ;
RTb :Tb 9T b :354.119353.23:0.88 K W ;M

W ;1000 Kb ;W ;1000
RTb :Kb ; M :
W ;M W ;Tb

Kb ;W ;1000 2.42;3.795;1000
M : :
RTb ;W 100;0.36

2.53;1.8;1000 :255.1 g mol\
:
0.88;90 255.1
:57.5 g mol 91 Number of S atoms in molecule:
32
Ans. Molar mass:M :57.5 g mol 91 :7.972

------------------------------------------------------------------------------------
X8
(5) Boiling point of a solvent is 80.2°C. When 0.419 g Ans. Formula of sulphur in CS solution:S

of the solute of molar mass 252.4 g mol\ is ------------------------------------------------------------------------------------
dissolved in 75 g of the above solvent, the boiling (7) Calculate the mass in grams of an impurity of
point of the solution is found to be 80.256 °C. molar mass 100 g mol 9 which would be
Find the molal elevation constant. required to raise the boiling point of 50 g of
(2 marks) chloroform by 0.30°C. (2 marks)
Solution : (K b for chloroform:3.63 K kg mol 9 )
Given : T :(273;80.2) K Solution :

Tb :273;80.256 (K) Given : M :100 g mol 9
W :75 g
W :50 g chloroform
W :0.419 g
W :?
M :252.4 g mol 91
T b :0.30°C.
Kb :?
K b :3.63 K kg mol 9
T b :T b 9T
W ;1000
:(273;80.256)9(273;80.2) T b :K b ;
:0.056 K W ;M

W ;1000 T b ;W ;M
T b :K b ; W :
W ;M K b ;1000

W ;M :
0.30;50;100
K b : T b ;
W ;1000 3.63;1000

75;252.4 :0.4132 g
:0.056;
0.41 g;1000 Ans. Weight of impurity:0.4132 g
:2.53 K kg mol 9 ------------------------------------------------------------------------------------
Ans. Kb :2.53 K kg mol 9 (8) A solution containing 0.5126 g of naphthalene

------------------------------------------------------------------------------------ (molar mass:128.17 g mol 9 ) in 50.0 g of CCl

(6) 3.795 g of sulphur is dissolved in 100 g of CS . gives a boiling point elevation of 0.402°C. While

This solution boils at 319.81 K. What is the a solution of 0.6216 g of unknown solute in the
molecular formula of sulphur in solution ? The same mass of the solvent gives a boiling point
3/Navneet Chemistry Digest : Std. XII (Part I) E0288 65
elevation of 0.647°C. Find the molar mass of the For camphor solution,
unknown solute. (K b for CCl :5.03 K kg mol9 T b :Tb 9T0

of solvent) (2 marks) :(273;56.55)9(273;56.3)
Solution : :0.25 K
Given : For naphthalene solution : W ;1000
T b :Kb ;
W :0.5126 g W ;M

W :50 g T b ;W ;M 0.25;36.8;152
Kb : :
W ;1000 0.73;1000
M :128.17 g mol 9
:1.916 K kg mol 9
K b :5.03 K kg mol 91
For a solution of unknown compound
T b :0.402°C
T b:T b – T
For unknown solute :
:(273;56.46)9(273;56.3)
W :50 g
:0.16 K
W :0.6216 g
W ;1000
T b :0.647°C T b:Kb ;
W ;M
M :?
Kb ;W ;1000
M :
For the solution of unknown substance, T b;W

W ;1000 :
1.916;0.564;1000
T b :K b ;
W ;M 0.16;36.8
:183.5 g mol 9
K ;W ;1000
M : b Ans. Molar mass of the compound:183.5 g mol 91
W ; T b
------------------------------------------------------------------------------------
5.03;0.6216;1000 (10) 0.12 molal solution of a substance boils at

: 373.21°K. Calculate molal elevation constant of
50;0.647
:96.65 g mol 9 the solvent. (2 marks)
Ans. Molecular weight of unknown substance Solution :
:96.65 g mol 9 Given : Concentration of solution:m:0.12
Boiling point of the solution:T b :373.21 K
------------------------------------------------------------------------------------
(9) A solution containing 0.73 g of camphor (molar For solvent (water) T :373.15 K

mass 152 g mol\) in 36.8 g of acetone (boiling Molal elevation constant, K b :?
point 56.3°C) boils at 56.55°C. A solution of 0.564 g T b :T b 9T

of unknown compound in the same weight of :373.219373.15
acetone boils at 56.46°C. Calculate the molar :0.06 K
mass of the unknown compound. (3 marks) T b :K b ;m
Solution : Tb
K b:
Given : Mass of solute:W :0.73 g camphor m
0.06
Mass of solvent:W :36.8 g : :0.5 K kg mol 9
0.12
Molar Mass of solute:M :152 g mol\
Ans. Molal elevation constant:K b :0.5 K kg mol 9
Boiling point of acetone:T :(273;56.3) K
------------------------------------------------------------------------------------
Mass of unknown solute:W :0.564 g (11) Boiling point of water at 750 mm of Hg is

Mass of solvent:W :36.8 g 99.63°C. How much sucrose must be added to

Boiling point of solution of camphor 500 g of water so that it boils at 100°C?
:Tb :(273;56.55) K (Kb :5.02 K kg mol 91) (2 marks)
Boiling point solution of unknown compound Solution :
:Tb :(273;56.46) K Given : Boiling point of water:T :273;99.63

Molar mass of unknown compound:M :? :372.63 K

Boiling point of a solution:Tb :273;100:373 K Number of atoms in a molecule of phosphorus
Mass of a solvent (water):W :500 g molar mass of phosphorus
:
Molar mass of sucrose (C H O ):M atomic mass of phosphorus

:342 g mol 91 125
:
31
Kb :5.02 K kg mol 91
:4.032
Mass of solute (sucrose):W :?
X4
Tb :Tb 9T
Hence the molecular formula of phosphorus is P
:3739372.63
in CS .
:0.37 K
Ans. Molecular formula of phosphorus:P

------------------------------------------------------------------------------------
W ;1000
Tb :Kb ; (13) Boiling point of water at 750 mm of Hg is
W ;M
99.63 °C. How much sucrose must be added to
Tb ;W ;M 500 g of water so that it boils at 100 °C?
W :
Kb ;1000 (Kb :0.52 K kg mol\) (3 marks)
0.37;500;342 Solution :
:
5.02;1000 Given : Pressure:P:750 mm Hg
W :12.60 g sucrose T :273;99.63:372.63 K

Ans. Mass of sucrose required to be added:12.60 g Tb :273;100:373 K
------------------------------------------------------------------------------------
Kb :0.52 K kg mol\
(12) A solution of phosphorus prepared by dissolving
Molar mass of sucrose (C H O )
0.0175 kg of phosphorus in 0.08 kg of CS has a
:342;10\ kg mol\
boiling point 319.87 K. If Kb for CS is
W :500 g:0.5 kg
2.4 K kg mol\ and atomic mass of phosphorus
Mass of sucrose to be added:W :?
is 31;10\ kg mol\, find the formula of phos-
Tb :Tb 9T :3739372.63:0.37 K
phorus. (Boiling point of CS :319.45 K)
W
(3 marks) Tb :Kb ;
W ;M
Solution :
Tb ;W ;M
W :
Given : Mass of solvent (CS ):W :0.08 kg Kb

Mass of phosphorus:W :0.0175 kg K kg kg mol\

Boiling point of CS :T :319.45 K 0.37;0.5;342;10\
:
Boiling point of solution:Tb :319.87 K 0.52
K kg mol\
Molal elevation constant:Kb :2.4 K kg mol\ :121.7;10\ kg
Atomic mass of phosphorus:31;10\ kg mol\ :121.7 g
Molecular formula of phosphorus:? Ans. Mass of sucrose to be added:121.7;10\ kg
Tb :Tb 9T :319.879319.45:0.42 K :121.7 g

Kb ;W ------------------------------------------------------------------------------------
Tb :
W ;M (14) 35% (W/W) solution of ethylene glycol in water,

Kb ;W an anti-freezer used in automobiles in radiators
M :
Tb ;W as a coolant. It lowers freezing point of water to

K kg mol\ kg 917.6 °C. Calculate the mole fraction of the
2.4;0.0175 components. (3 marks)
:
0.42;0.08 Solution : 35% (W/W) means 100 g solution con-
K kg tains 35 g ethylene glycol (CH OH–CH OH) and

:125 g mol\ 65 g H O.

2. SOLUTIONS 67
-Molar mass of water:18 g mol\ which the liquid and the solid have the same vapour
Molar mass of ethylene glycol (CH OH–CH OH) pressure.

:62 g mol\ Addition of a nonvolatile solute to a liquid
65 decreases the freezing point, i.e., the freezing point
Number of moles of water:n : :3.611 mol
18
of the solution is less than that of the pure solvent.
35
Number of moles of ethylene glycol:n : This is due to the lowering of the vapour pressure of
62
the solvent by the addition of the nonvolatile solute.
:0.5645 mol
Total moles:n:n ;n :3.611;0.5645 When a liquid is cooled from the point A, its

:4.1755 mol vapour pressure decreases and at the point B, it
Mole fraction of ethylene glycol:x freezes (solidifies).

n 0.5645
: : :0.1352
n 4.1755

Mole fraction of water:19x :190.1352

:0.8648
Ans. Mole fraction of water:0.8648
Mole fraction of ethylene glycol:0.1352 ■
Units
2.9 Depression in freezing point
2.9.1 Freezing point depression as a conse-
quence of vapour pressure lowering
2.9.2 Freezing point depression and concentra-
tion of solute
2.9.3 Molar mass of solute from freezing point Fig. 2.8 : The variation of vapour pressure with
depression temperature of pure solvent, solid solvent and solution
In case of a solution, since the vapour pressure is

Q. 51. Define freezing point of a liquid. (1 mark)
lowered, the freezing point decreases. Hence, if the
Ans. The freezing point of a liquid is defined as the
solution is cooled from the point A, it freezes at
temperature at which the solid coexists in the
lower temperature B, than the pure liquid. This is
equilibrium with the liquid and the vapour pressure
of the liquid and the solid are equal. ■
also due to separation of solvent molecules due to
solute molecules decreasing their intermolecular
Q. 52. Explain the depression in the freezing point of
a solution. (2 marks) attraction.
Ans. The depression in the freezing point of a solution is If T and T are the freezing points of a pure

defined as the difference between the freezing solvent and the solution, then, the depression in the
points of a pure solvent and that of the solution. freezing point is given by,
If T and T are the respective freezing points of a Tf : T 9T.

pure solvent and a solution, then the depression in This depression Tf depends on the lowering of
the freezing point Tf is given by,
the vapour pressure (P 9P). Tf . (P 9P),
Tf :T 9 T (T
T )
where P and P are the vapour pressures of the pure
The depression in the freezing point ( Tf ) is a
liquid and the solution. ■
colligative property. ■
Q. 54. What is a relationship between freezing
Q. 53. What causes depression in freezing point ?
(2 marks) OR point depression and concentration of solute (or
Explain, freezing point depression as a conse- solution) ? (2 marks)
quence of vapour pressure lowering. (2 marks) Ans. It is observed experimentally that as the concentra-
Ans. The freezing point of a liquid is the temperature at tion of a solution increases, the freezing point of the

solution decreases and hence the depression in the If the weights are expressed in kg then,
freezing point (Tf ) increases. W
The depression in the freezing point of a solution Tf :Kf ;
W M

is directly proportional to the molal concentration
The unit of Kf is K kg mol 91.
(expressed in mol kg 91 ) of the solution.
Thus, Hence, from the measurement of the depression
Tf . m in the freezing point of the solution, the molar mass
where m is the molality of the solution. of the substance can be determined. ■
Tf : Kf m, where Kf is a constant of propor- Q. 57. Write the formula to determine molar mass of
tionality. If m:1 molal, a solute using freezing point depression method.
Tf :Kf. Hence Kf is called the cryoscopic constant
(1 mark)
or molal depression constant. Kf is characteristic of
K ;W ;1000
the solvent. ■ Ans. M : f
W ;Tf
Q. 55. What are the units of molal depression con-
where
stant or cryoscopic constant ? (2 marks) Kf :Molal depression constant
Ans. The freezing point depression, Tf is given by,
Tf :Depression in freezing point
Tf :Kf ;m
W :Mass of a solvent
where m is molality in mol kg\ and Kf is molal
W :Mass of a solute.
depression constant or cryoscopic constant.
M :Molar mass of solute ■
T
Kf : f K
m Q. 58. Define cryoscopic constant (or molal depress-
mol kg\
ion constant). (1 mark)
Kf has unit K kg mol\ (or °C kg mol\)
Ans. Molal depression constant : It is defined as the
Therefore cryoscopic constant is the depression
depression in freezing point, produced by dissolv-
in freezing point produced by 1 molal solution of a
ing one mole of a solute in 1 kg (or 1000 g) of a
nonvolatile solute. ■
solvent (i.e. 1 molal solution). ■
★Q. 56. Obtain the relationship between freezing
point depression of a solution containing non- ★ Q. 59. Which of the following solutions will have
volatile nonelectrolyte and its molar mass. higher freezing point depression and why ?
(2 marks) (a) 0.1 m NaCl (b) 0.05 m Al (SO ) . (2 marks)

Ans. The freezing point depression, Tf of a solution is Ans.
directly proportional to molality (m) of the solution. (1) Freezing point depression is a colligative property,
Tf . m hence depends on the number of particles in the
Tf :Kf m solution.
where Kf is a molal depression constant. (2) More the number of particles in the solution, higher
The molality of a solution is given by, is the depression in freezing point.
Number of moles of the solute (3) The number of particles (ions) from electrolytes are,
m:
Weight of the solvent in kg 0.1m
If W grams of a solvent contain W grams of a Na ; ;Cl 9 Total ions:0.1;0.1
(a) NaCl IIIIJ
solute of the molar mass M , then the molality m of

0 0.1 m 0.1 m :0.2 m
the solution is given by,
0.05 m
g kg
W ;1000 (b) Al (SO ) IIIIJ 2Al3; ;3SO 9
Total ions
W
m: : mol kg\ :0.1;0.15
W M W ;M 2;0.05 3;0.05

g g mol\ kg kg mol\ :0.1 m :0.15 m :0.25 m
W ;1000 (4) Therefore Al (SO ) solution will have higher
Tf :Kf ;
W M freezing point depression. ■

2. SOLUTIONS 69
★ Q. 60. While considering boiling point elevation :273 K9272.8 K
and freezing point depression a solution concen- :0.2 K
tration is expressed in molality and not in molar- M : Molecular mass of the solute

ity. Why ? (1 mark) :342;10\ kg mol\
Ans. K f : Molal freezing point depression constant for
(1) Boiling point elevation and freezing point depress- water :1.86 K kg mol\
ion involve temperature changes, (Tb and Tf). W : Mass of the solute : ?

(2) Since molarity depends on temperature but molality Tf :T 9 T f

is independent of temperature we use molality and KfW
: ; 1000
not molarity in considering boiling point elevation M W

and freezing point depression. ■ Tf M W log 68.4 :1.8351
W :
K f ; 10 9log 1.86 :0.2695
Solved Examples 2.9
0.2;342;10\;1 1.5656
Q. 61. Solve the following : :
1.86
Antilog : 1.5656
(1) 1.35 g of a substance when dissolved in 55 g 68.4
: ; 10\ :36.78
acetic acid produced a depression of 0.618°C in a 1.86
freezing point. Calculate the molar mass of the : 36.78;10\ kg
dissolved substance. (K f :3.865 K kg mol 9 ) Ans. Mass of sucrose:36.78;10\ kg
(2 marks) ------------------------------------------------------------------------------------
Solution : (3) The freezing point of a pure solvent is 315 K. On

Given : Mass of a solvent:W :55 g addition of 0.5 mole of urea in 1 kg of the solvent,

Mass of a solute:W :1.35 g the freezing point decreases by 3 K. Calculate the

Depression in freezing point: T f :0.618°C molal depression constant for the solvent.
Molal depression constant:K f :3.865 K kg mol 9 (2 marks)
Molar mass of a solute:M :? Solution :

W ;1000 Given : m:Molality of urea:0.5 m
T f :K f : Tf :Depression in the freezing point:3 K
W ;M
K f :Molal depression constant for the solvent : ?
K f ;W ;1000
M : Tf :K f ;m
W ;T f
Tf
3.865;1.35;1000 Kf :
: m
55;0.618
3
:153.5 g mol 9 :
0.5
Ans. Molar mass of the substance:153.5 g mol 9 : 6 K kg mol\
------------------------------------------------------------------------------------
(2) When certain amount of sucrose is dissolved in Ans. Molal depression constant:6 K kg mol\
------------------------------------------------------------------------------------
1 kg of water, the freezing point of the solution is
(4) The freezing point of pure benzene is 278.4 K.
found to be 272.8 K. If the molecular mass of
Calculate the freezing point of the solution when
sucrose is 342 g mol\ and K f for water is
2 g of a solute having molecular weight 100 is
1.86 K kg mol\, calculate the amount of sucrose
added to 100 g of benzene.
present in the solution. (3 marks)
(Kf for benzene:5.12 K kg mol\)
Solution :
(2 marks)
Given : W : Mass of the solvent:1 kg Solution :

T : Freezing point of pure water:273 K Given : K f for benzene:5.12 K kg mol\

Tf : Freezing point of the solution : 272.8 K T : Freezing point of the solvent:278.4 K

Tf :T 9T f :Depression in freezing point W : Mass of the solvent:100 g:0.1 kg

W : Mass of the solute:2 g:2;10\ kg Kb :0.52 K kg mol\; Kf :1.86 K kg mol\
Boiling point of water:T :373 K
M : Molecular mass of the solute:100 g mol\
Tf :?
:100;10\ kg mol\
T : Freezing point of the solution : ? Tb :Tb 9T :373.189373:0.18 K

If m is the molality of the solution, then
KfW
Tf : Tb :Kb ;m and Tf :Kf ;m
M W
Tf Kf ;m Kf
5.12;2;10\ : :
Tf : Tb Kb ;m Kb
100;10\;0.1
K
10.24 Tf :Tb ; f
: :1.024 K Kb
10 1.86
Tf :T 9T :0.18;
0.52
T:T 9Tf :0.6438 K

:278.491.024:277.376 K Freezing point of water:T :273 K

Ans. Freezing point of the solution:277.376 K Tf :T 9Tf
------------------------------------------------------------------------------------
Hence the freezing point of the solution is,
(5) 0.635;10\ kg of a substance of molar mass
Tf :T 9 Tf :27390.6438:272.3562 K
190;10\ kg mol\ was dissolved in
OR Freezing point of solution is 90.6438 °C.
30.5;10\kg of a solvent. If the depression in Ans. Freezing point of the solution
the freezing point is 0.62 °C, find the molal :272.3562 K
depression constant of the solvent. (2 marks) : 90.6438 °C
Solution : ------------------------------------------------------------------------------------
Given : Mass of solvent:W :30.5;10\ kg (7) 1.0;10 9 kg of urea when dissolved in 0.0985

Mass of solute:W :0.635;10\ kg kg of a solvent, decreases freezing point of the

Depression in freezing point:Tf :0.62 °C (or K) solvent by 0.211 K. 1.6;10 9 kg of another
Molar mass of the substance:M :190;10\ kg nonelectrolyte solute when dissolved in 0.086 kg

mol\ of the same solvent depresses the freezing point
Molal depression constant:Kf :? by 0.34 K. Calculate the molar mass of the
another solute. (Given molar mass of urea:60)
W
Tf :Kf ; (3 marks)
W ;M
Solution :
Tf ;W ;M
Kf : Given : Mass of Urea:W :1;10 9 kg
W
Mass of solvent:W :0.0985 kg
K kg kg mol\
Depression in freezing point:Tf :0.211 K
0.62;30.5;10\;190;10\ Molar mass of urea:M :60 g mol 9
: K kgmol\
0.635;10\
kg
:60;10 9 kg mol 9
Mass of another solute:W :1.6;10 9 kg
:5.66 K kg mol\
Mass of solvent:W :0.086 kg
Ans. Molal depression constant:Kf
Depression in freezing point:T f :0.34 K
:5.66 K kg mol\
------------------------------------------------------------------------------------ Molar mass of another solute:60;10 9 kg
(6) The boiling point of an aqueous solution is mol 9
100.18 °C. Find the freezing point of the solution. From urea solution :
(Given : Kb :0.52 K kg mol\, W
Tf :Kf :
Kf :1.86 K kg mol\) (3 marks) W ;M

Solution : W ;M
Kf :Tf ;
Given : Tb :100.18 °C;273:373.18 K W

2. SOLUTIONS 71
kg kg mol 9
Units
0.0985; 60;10 9 2.10 Osmotic pressure
: 0.211 ;
1;10 9 kg 2.10.1 Osmosis
K
2.10.2 Osmotic pressure
:1.248 mol 9 kg K 2.10.3 Isotonic, hypertonic and hypotonic solutions
For solution of another solute : 2.10.4 Osmotic pressure and concentration of
W solution
T f :Kf ;
W ;M 2.10.5 Molar mass of solute from osmotic
pressure
K ;W 2.10.6 Reverse osmosis
M : f
T f ;W
Q. 62. What do you understand by the terms :
mol 9 kg K kg (1) permeable membrane
1.248 ; 1.6;10 9 (2) semipermeable membrane? (1 mark each)
:
0.34 ;0.086 Ans.
K kg (1) Permeable membrane : A membrane which
allows free transfer of the solute molecules from a
:68.23;10 9 kg mol 9
solution of a higher concentration to a solution of a
:68.23 g mol 9 lower concentration through it is called a permeable
Ans. Molar mass of solute:68.23 g mol 9 . membrane and the transfer is called diffusion,
------------------------------------------------------------------------------------
e.g., a membrane of a paper.
★ (8) A 5% aqueous solution (by mass) of cane (2) Semipermeable membrane : A membrane which
sugar (molar mass 342 g/mol) has freezing point allows free passage of only the solvent molecules
of 271 K. Calculate the freezing point of 5% but not the large solute molecules or ions of large
aqueous glucose solution. (2 marks) molecular mass from a solution of a lower concen-
tration (or a pure solvent) to a solution of higher
Solution :
concentration through it, is called a semi-permeable
Given : W :5 g cane sugar; W :10095:95 g
membrane, e.g., parchment paper, complex like
M :342 g mol\; Tf :271 K; Cu [Fe (CN) ], etc. ■

Tf :2739271:2 K; Tf :? Q. 63. Define and explain osmosis. (2 marks)

W :5 g glucose, W :10095:95 g, Ans.

M :180 g mol\, Tf :? (1) Definition : It is defined as a spontaneous uni-

directional flow of the solvent molecules from a
W ;1000
Tf :Kf ; pure solvent or a dilute solution to the more
W ;M
concentrated solution through a semipermeable
Tf ;W ;M
Kf : membrane.
W ;1000
Example : A flow of water molecules from a dilute
2;95;342 solution into a concentrated glucose solution
:
5;1000 through a parchment paper.
:12.996 K kg mol\
X 13 K kg mol\
W ;1000
Tf :Kf ;
W ;M

13;5;1000
:
95;180
:3.801 K
Freezing point of solution:Tf
:27393.801:269.2 K
Ans. Freezing point of solution:269.2 K. ■ Fig. 2.9 : Osmosis

(2) Explanation : Consider a vessel divided into two ★ Q. 65. A solvent and its solution containing a non-
compartments by a semipermeable membrane. volatile solute are separated by a semipermeable
When one compartment is filled with a pure solvent membrane. Does the flow of solvent occur in both
or a dilute solution and another by concentrated
directions ? Comment giving reason. (2 marks)
solution, there is a spontaneous of solvent mol-
Ans.
ecules to the concentrated solution. This arises due
to higher vapour pressure of a pure solvent or dilute (1) When a solvent and a solution containing a non-
solution than concentrated solution. ■ volatile solute are separated by a semipermeable
Q. 64. Define and explain osmotic pressure. membrane, there arises a flow of solvent molecules
(3 marks) OR from solvent to solution as well as from solution to
★ What is osmotic pressure ? (3 marks) solvent.
Ans. (2) Due to higher vapour pressure of solvent than
(1) Definition : The osmotic pressure is defined as the solution, the rate of flow of solvent molecules from
excess mechanical pressure required to be applied solvent to solution is higher.
to a solution separated by a semipermeable mem-
(3) As more and more solvent passes into solution due
brane from pure solvent or a dilute solution to
to osmosis, the solvent content increases, and the
prevent the osmosis or free passage of the solvent
molecules at a given temperature. The osmotic rate of backward flow increases.
pressure is a colligative property. (4) At a certain stage an equilibrium is reached where
both the opposing rates become equal attaining an
equilibrium. ■
Q. 66. Explain the relation between osmotic pressure

and concentration of solution. (2 marks)
Ans.
(1) Consider V dm of a solution in which n moles of a

solvent contains n moles of a nonvolatile solute at

absolute temperature T.
(2) The osmotic pressure, of a solution is given by,
Fig. 2.10 : Osmosis and osmotic pressure nRT
(2) Explanation : Consider an inverted thistle funnel :
V
on the mouth of which a semipermeable membrane
R is gas constant having value 0.08206 dm atm
is firmly fastened. It is filled with the experimental
K\ mol\ (OR L atm K\ mol\). Since concen-
solution and immersed in a solvent like water. As a
result, solvent molecules pass through the mem- tration, C of a solution is in mol dm\ or molarity is,
brane into the solution in the funnel causing rising n
C: mol dm\ or M
of level in the arm of thistle funnel. This increases V
the hydrostatic pressure. At a certain stage this :CRT
rising level stops indicating an equilibrium between (If concentration C is expressed in mol m\ and
the rates of flow of solvent molecules from solvent R:8.314 J K\mol\, then will be in SI units,
to solution and from solution to solvent. The
pascals or Nm\.) ■
hydrostatic pressure at this stage represents osmotic
pressure of the solution in the thistle funnel. ■ ★ Q. 67. How is molar mass of a solute determined by
Remember ... osmotic pressure measurements ? (2 marks)
(Textbook page 40)
Ans. Consider V dm (litres) of a solution containing
● It is important to note that osmotic pressure is not
W mass of a solute of molar mass M at a
the pressure produced by a solution. It exists only
temperature T.
when the solution is separated from the solvent by a
W
suitable kind of semipermeable membrane. Number of moles of solute, n : .
M

2. SOLUTIONS 73
The osmotic pressure is given by, CA :CB
W RT n n
: A: B
M V V V

W RT nA :nB
M :
V Hence, equal volumes of the isotonic solutions at
By measuring osmotic pressure of a solution, the the same temperature will contain equal number of
molar mass of a solute can be calculated. moles (hence, equal number of molecules) of the
Since osmotic pressure can be measured more substances.
precisely, it is widely used to measure molar masses (2) Hypotonic solutions : When two solutions have
of the substances. ■ different osmotic pressures, then the solution having
★ Q. 68. A solution concentration is expressed in lower osmotic pressure is said to be a hypotonic
molarity and not in molality while considering solution with respect to the other solution.
osmotic pressure. Why ? (2 marks) Explanation : Consider two solutions of the
Ans. substances A and B having osmotic pressures A
(1) While calculating osmotic pressure by equation, and B. If B is less than A, then the solution B is a
:CRT, the concentration is expressed in molarity hypotonic solution with respect to the solution A.
but not in molality. Hence, if CA and CB are their concentrations,
(2) This is because the measurements of osmotic press- then, CB
CA. Hence, for equal volumes of the
ure are made at a certain constant temperature.
solutions, nB
nA.
(3) Molarity depends upon temperature but molality is
(3) Hypertonic solutions : When two solutions have
independent of temperature.
different osmotic pressures, then the solution hav-
(4) Hence in osmotic pressure measurements, concen-
ing higher osmotic pressure is said to be a hyper-
tration is expressed in molarity. ■
tonic solution with respect to the other solution.
Q. 69. Explain the terms :
Explanation : Consider two solutions of sub-
(1) Isotonic solutions
stances A and B having osmotic pressures A and
(2) Hypotonic solutions
B. If B is greater than A, then the solution B is a
(3) Hypertonic solutions. (1 mark each)
hypertonic solution with respect to the solution A.
Ans.
Hence, if CA and CB are their concentrations, then
(1) Isotonic solutions : The solutions having the same
CB CA. Hence, for equal volume of the solutions,
osmotic pressure at a given temperature are called
nB nA. ■
isotonic solutions.
★ Q. 70. What are (i) isotonic and (ii) hypertonic
Explanation : If two solutions of substances A
and B contain nA and nB moles dissolved in volume solutions ? (2 marks)
V (in dm) of the solutions, then their concentra- Ans. For the answers refer to answers of Q. 69 (1) and
tions are, (3) respectively. ■
n ★ Q. 71. Explain reverse osmosis. (2 marks) OR

CA : A (in mol dm 93 ) and
V How can pure water be obtained from sea
n water ? (2 marks)
CB : B (in mol dm 93 )
V Ans. Reverse osmosis : The phenomenon of the passage
If the absolute temperature of both the solutions of solvent like water under high pressure from the
is T, then by the van’t Hoff equation, concentrated aqueous solution like sea water into
A :CART and B :CBRT, where A and B are pure water through a semipermeable membrane is
their osmotic pressures. called reverse osmosis.
For the isotonic solutions, The osmotic pressure of sea water is about
A :B 30 atmospheres. Hence when pressure more than

30 atmospheres is applied on the solution side, trolytic solutions with same concentration ?
regular osmosis stops and reverse osmosis starts. (2 marks)
Hence pure water from sea water enters the other Ans.
side of pure water. (1) The electrolytes in polar solvents or aqueous sol-
utions dissociate into two or more ions whereas
nonelectrolytes do not dissociate.
(2) Consequently the number of particles in electrolytic
solutions are considerably higher than equimolar
nonelectrolytic solutions.
(3) Therefore the colligative properties of electrolytes
are greater than nonelectrolytes with same concen-
tration in solution. ■
Fig. 2.11 : Purification of sea water by reverse osmosis ★ Q. 74. Which of the four colligative properties is
For this purpose of suitable semipermeable mem- most often used for molecular mass determina-
brane is required which can withstand high pressure tion ? Why ? (2 marks)
conditions over a long period. Ans.
This method is used successfully in Florida since (1) Since osmotic pressure has large values, it can be
1981 producing more than 10 million litres of pure measured more precisely.
water per day. ■
(2) The osmotic pressure can be measured at a suitable
constant temperature.
Remember ...
(Textbook page 41) (3) The molecular masses can be measured more accu-
● Osmotic pressure is much larger and therefore more rately.
precisely measurable property than other colligative (4) Therefore, it is more useful to determine molecular
properties. It is therefore, useful to determine molar masses of expensive substances by osmotic press-
masses of very expensive substances and of the ure. ■
substances that can be prepared in small quantities. Q. 75. What is abnormal colligative property?
Explain the reasons. (3 marks)
Units Ans. Abnormal colligative property : When the
2.11 Colligative properties of electrolytes experimentally measured colligative property of a
2.11.1 van’t Hoff factor (i) solution is different from that calculated theoreti-
2.11.2 Modification of expressions of col- cally by the van’t Hoff equation or by the laws of
ligative properties osmosis, then the solution is said to have abnormal
2.11.3 van’t Hoff factor and degree of dissociation colligative property.
Explanation : The colligative property depends
Q. 72. Explain colligative properties of electrolytes. on the number of solute particles in the solution but
(2 marks) it is independent of their nature. Abnormal values of
Ans. them arise when the dissolved solute undergoes a
(1) The electrolytic solutions do not exhibit colligative molecular change like dissociation or association in
properties similar to nonelectrolytes. the solution.
(2) The colligative properties of electrolytes are higher The observed colligative property (or abnormal
than those shown by equimolar solutions of colligative property) may be higher or lower than
nonelectrolytes. the theoretical value.
(3) The molar masses of electrolytes determined by (i) Dissociation of the solute molecules : When a
colligative properties are found to be considerably solute like an electrolyte is dissolved in a polar
lower than their actual molar masses. ■ solvent like water, it undergoes dissociation, which
Q. 73. Why are the colligative properties of electro- results in the increase in the number of particles in
lytic solutions greater than those for nonelec- the solution.
2. SOLUTIONS 75
Hence, the observed value of the colligative The van’t Hoff factor can be represented as,
property becomes higher than the theoretical value, Observed value of colligative property
i:
e.g., when one mole of KCl is dissolved in the Theoretical value of the
solution then due to dissociation, colligative property
; 9
KCl ; K ;Cl , the number of particles in- This colligative property may be the lowering of
creases, hence, the colligative properties like osmo- vapour pressure of a solution, the osmotic pressure,
tic pressure elevation in the boiling point, etc. the elevation in the boiling point or the depression
increase. in the freezing point of the solution. Hence,
(ii) Association of the solute molecules : When a Observed lowering of vapour pressure
i:
solute like a nonelectrolyte is dissolved in a nonpo- Theoretical lowering of vapour pressure
lar solvent like benzene, it undergoes association : P(ob) / P(th)
forming molecules of higher molecular mass.
Observed elevation in boiling point
Hence, the number of the particles in the solution i:
Theoretical elevation in boiling point
decreases. Therefore the colligative properties like
: Tb(ob) / Tb(th)
osmotic pressure, elevation in the boiling point,
Observed depression in freezing point
etc., are lower than the theoretical value, e.g., i:
Theoretical depression in freezing point
nA ; An.
: Tf(ob) / Tf(th)
2CH COOH ; (CH COOH)

2C H COOH ; (C H COOH) Observed osmotic pressure
■ i:
Theoretical osmotic pressure
Q. 76. Explain abnormal osmotic pressure. (1 mark)
(ob)
Ans. :
(th)
(1) When the experimentally observed osmotic press-
(i) When the solute neither undergoes dissociation or
ure is different than theoretically calculated value
association in the solution, then,
by van’t Hoff’s equation then it is called abnormal
i:1
osmotic pressure.
(2) This arises when the dissolved solute undergoes a (ii) When the solute undergoes dissociation in the
molecular change like association or dissociation. solution, then,
■ i1
Q. 77. Explain abnormal molecular masses. (iii) When the solute undergoes association in the solu-
(1 mark) tion, then
Ans. When the observed molecular masses obtained i
1
from their colligative properties of the substances From the value of the van’t Hoff factor, the degree
are different (higher or lower) than the theoretical of dissociation of electrolytes, degree of association
or normal values calculated from their molecular of nonelectrolytes can be obtained.
formulae, then they are called abnormal molecular van’t Hoff factor gives the important information
masses. ■ about the solute molecules in the solution and
Q. 78. Define and explain van’t Hoff factor, i. chemical bonding in them. ■
(2 marks) Q. 79. How is van’t Hoff factor related to molecular

★ What is van’t Hoff factor ? (2 marks) mass of the substance ? (2 marks)
Ans. Definition of the van’t Hoff factor, i : It is defined Ans. The van’t Hoff factor is also defined as,
as a ratio of the observed colligative property of the actual moles of particles in solution after
solution to the theoretically calculated colligative dissociation
i:
property of the solution without considering mol- moles of formula units dissolved in solution
ecular change. (2.23)

formula mass of substance At equilibrium,
:
observed molar mass of substance AxBy & xAy>;yBx\
Mtheoretical For 1 mole of electrolyte : 19 x y
:
Mobserved and For ‘m’ moles of an electrolyte : m(19), mx,
In case of nonelectrolytes, i
1.
my are the number of particles.
In case of electrolytes, i 1. For example for
Total number of moles at equilibrium, will be,
KNO and NaCl, i:2, for Na SO , CaCl , i:3,
Total moles:m(19);mx;my
etc. ■
:m[(19);x;y]
Q. 80. Write modification of expressions of colli-
:m[1;x;y9]
gative properties with the help of van’t Hoff
:m[1;(x;y91)]
factor. (2 marks)
Ans. The modified expressions of colligative properties The van’t Hoff factor i will be,
with the help of van’t Hoff factor i are as follows : Observed colligative property
i:
(1) By Raoult’s law : Theoretical colligative property
P 9P P 9P W ;M m [1; (x;y91)]
:ix OR :i; :
P P W ;M m

(2) For elevation in boiling point : i:1; (x;y91)
Tb :i;Kb ;m If total number of ions from one mole of electrolyte
W ;1000 is denoted by n, then (x;y):n
Tb :i;Kb ;
W ;M i:1; (n91)

W
(n91):i91
Tb :i;Kb ;
W ;M i91
: … (1)
(3) For depression in freezing point : n91
Tf :i;Kf ;m This is a relation between van’t Hoff factor i and
W ;1000 degree of dissociation of an electrolyte. ■
Tf :i;Kf ;
W ;M
Q. 82. Obtain a relation between degree of dissocia-
W
Tf :i;Kf ; tion and molar mass for an electrolyte.
W ;M
(2 marks)
(4) Osmotic pressure :
Ans. Consider an electrolyte AxBy.
:iCRT
AxBy & xAy>;yBx\
nRT
:i; Initially 1 0 0
V
WRT At equilibrium 19 x y
:i;
M;V If i is van’t Hoff factor and n is total number of
■
ions produced from dissociation of one mole of
Q. 81. ★ How is van’t Hoff factor related to degree
electrolyte then, the degree of dissociation is
of ionisation ? (2 marks) OR
given by,
★ Derive the relationship between degree of disso-
i91
ciation of an electrolyte and van’t Hoff factor. :
n91
(2 marks)
Now if Mth and Mob are theoretical and observed
Ans.
Consider 1 dm of a solution containing m moles of molecular (or molar) masses respectively, then,
an electrolyte AxBy. The electrolyte on dissociation Mth
i:
gives x number of Ay> ions and y number of Mob
Bx\ ions. Let be the degree of dissociation. B (n91):i91
2. SOLUTIONS 77
Mth
: 91
Mob (a) KCl IIIJ K>; Cl\ Total particles in
M 9Mob 0.1 m 0.1 m 0.1 m solution:0.2 mol
: th
Mth (b) NaCl IIIJ Na>; Cl\ Total particles in
:
1
(n91) Mth
Mth 9Mob
… (2) 0.05 m
(c) AlPO

IIIJ
0.05 m 0.05 m
Al>; PO \

solution:0.1 mol
Total particles in
This is a relation between degree of dissociation 1m 1m 1m solution:2.0 mol
and molecular masses of the dissolved electrolyte (d) MgSO IIJ Mg>; SO \ Total particles in

AxBy. 0.1 m 0.1 m 0.1 m solution:0.2 mole
AlPO solution contains highest moles and hence
(Textbook page 42)
highest number particles and in turn, the maximum
Q. If 1.25 m sucrose solution has Tf of 2.32 °C,
Tb. NaCl solution has minimum moles and particles.
what will be the expected value of Tf for 1.25 m
it has minimum Tf.
CaCl solution ?

Ans. Sucrose being nonelectrolyte, it has i:1 but for
CaCl , (Textbook page 44)

9
(CaCl IIIIJ Ca 2;
;2 Cl ) the value of i:3. Q. Arrange the following solutions in order of

Hence increasing osmotic pressure. Assume complete
Tf :i;2.32 ionization. (a) 0.5 m Li SO (b) 0.5 m KCl

:3;2.32 (c) 0.5 m Al (SO ) (d) 0.1 m BaCl .

:6.92 °C Ans. Consider 1 dm of each solution.
Tf :6.92 °C. 0.5 m Total particles
;
(a) Li SO IIIJ 2Li ;SO 29

0 2;0.5 0.5 m 1;0.5:1.5 m
(Textbook page 44) :1 m
● Which of the following solutions will have maxi- 0.5 m
mum boiling point elevation and which have (b) KCl IIIJ K ; ; Cl 9 0.5;0.5
minimum freezing point depression assuming the 0 0.5 m 0.5 m :1 m
complete dissociation ? (a) 0.1 m KCl (b) 0.05 m 0.5 m
NaCl (c) 1m AlPO (d) 0.1 m MgSO . (c) Al (SO ) IIIJ 2Al3; ; 3SO 29

Solution : Boiling point elevation and freezing 0 2;0.5 3;0.5 m 1;1.5
point depression are colligative properties that de- :1 m :1.5 m :2.5 m

0.1 m
pend on number of particles in solution. The sol-
(d) BaCl IIIJ Ba2; ; 2Cl 9 0.1;0.2
ution having more number of particles will have
0 0.1 m 2;0.1 :0.3 m
large boiling point elevation and that having less
:0.2m
number of particles would show minimum freezing
Osmotic pressure being a colligative property,
point depression.
it depends on number of particles in the solution.
Therefore, increasing order of osmotic pressure
is,
BaCl
KCl
Li SO
Al (SO )

0.3 m 1m 1.5 m 2.5 m

Solved Examples 2.10 & 2.11 (4) A solution of cane sugar containing 18 g L 9 has
an osmotic pressure 1.25 atm. Calculate the
Q. 83. Solve the following :
temperature of the solution. (Molar mass of
(1) 300 mL solution at 27 °C contains 0.2 mol of a
cane sugar:342. R:0.082 lit atm mol 9 K 9 )
nonvolatile solute. Calculate osmotic pressure of
(2 marks)
the solution. (2 marks)
Solution :
Solution :
Given : V:300 ml:0.3 dm; Given : Amount of cane sugar:W:18 g L 9
T:273;27:300 K Osmotic pressure::1.25 atm
n:0.2 mol, :? Molar mass of cane sugar:M:342 g mol 9
nRT Temperature:T:?
:
V Number of moles of cane sugar
0.2;0.08206;300 W
: :
0.3 M
:16.41 atm 18
Ans. Osmotic pressure::16.41 atm. :
342
------------------------------------------------------------------------------------
:0.05263 mol
(2) 200 mL solution at 27 °C contains 10 g of a
Concentration of solution:C
nonvolatile solute of molar mass 65 g mol 91.
n
What is osmotic pressure of the solution ? :
V
(2 marks)
0.05263
Solution : :
1
Given : V:200 mL:0.2 dm; W:10 g
M:65 g mol 91; T:273;27:300 K; :? :0.05263 mol lit 9
W 10 :CRT
n: : :0.1538 mol
M 65
T:
nRT CR
:
V 1.25
:
0.1538;0.08206;300 0.05263;0.08206
:
0.2 :289.4 K
:18.93 atm Ans. Temperature of solution:289.4 K
Ans. Osmotic pressure::18.93 atm. ------------------------------------------------------------------------------------
------------------------------------------------------------------------------------ (5) Equal volumes of two solutions, one containing
(3) Calculate the osmotic pressure of 0.2 M glucose glucose and another urea have osmotic pressures
solution at 300 K. (R:8.314 J mol 9 K 9 ) 12.6 atm and 23.8 atm at 25 °C. Calculate the
(2 marks) ratio of number of moles of urea to glucose.
Solution : (2 marks)
Given : Concentration of the solution Solution :
:C:0.2 M Given : Osmotic pressure of glucose solution:
:0.2 mol dm 9
:12.6 atm
:0.2;10 mol m 9 Osmotic pressure of urea solution:
Temperature:T:300 K
:23.8 atm
R:8.314 J mol 9 K 9
Number of moles of glucose:n
The osmotic pressure, is given by,
Number of moles of urea:n
:CRT
n RT n RT
:0.2;10;8.314;300 : ; :
V V
:4.988;10 Nm 9 (or Pa)
n RT/V n
Ans. Osmotic pressure:4.988;10 Nm 9 : :
n RT/V n
------------------------------------------------------------------------------------

2. SOLUTIONS 79
n 23.8 W RT
: : :1.889 : ;
n 12.6 M V

Number of moles of urea W;R;T
Ans. :1.889 M:
Number of moles of glucose ;V
------------------------------------------------------------------------------------ 1 8;0.08206;280
.
(6) One litre of a solution containing 25 g glucose has :
0.52;1
osmotic pressure 3.4 atm at 300 K. If by diluting :79.53 g mol\
the solution the osmotic pressure becomes Ans. Molar mass:M:79.53 g mol 91
2.0 atm at the same temperature, what would be ------------------------------------------------------------------------------------
its concentration ? (Molar mass of glucose:180) (8) An organic substance (M:169 gram mol 9 ) is
dissolved in 2000 cm of water. Its osmotic
(3 marks)
pressure at 12°C was found to be 0.54 atm. If
Solution :
R:0.0821 L atm K 9 mol 9 , calculate the mass
Given : Mass of solute (glucose):25 g
of the solute. (3 marks)
Volume of solution:1.0 L
Solution :
Osmotic pressure: :3.4 atm Given : M:169 g mol 9

After dilution osmotic pressure: :2 atm V:200 cm:0.2 dm

Final concentration:c :? T:273;125:285 K

25 :0.54 atm
The number of moles of glucose:n:
180 R:0.0821 L atm K 9 mol 9 ; W:?
:0.1389 mol :
W;RT
n M;V
Initial concentration:c : ;M;V
V W:
R;T
0.1389
: 0.54;169;0.2
1 :
0.08206;285
:0.1389 mol L 9
:0.78 g
At constant temperature, by van’t Hoff-Boyle’s
Ans. Mass of solute:0.78 g
law, ------------------------------------------------------------------------------------
c
: (9) A solution containing 10 g glucose has osmotic
c
pressure 3.84 atm. If 10 g more glucose is added

c :c ; to the same solution, what will be its osmotic

pressure. (Temperature remains constant)
2 (2 marks)
:0.1389; :0.0817 M
3.4 Solution :
Ans. Concentration of solution:0.0817 mol L 9 Given : Mass of glucose:W :10 g
------------------------------------------------------------------------------------
Mass of more glucose added:W :10 g
(7) A solution of a substance having mass
Initial osmotic pressure: :3.84 atm
1.8;10\ kg has the osmotic pressure of
Final osmotic pressure: :?
0.52 atm at 280 K. Calculate the molar mass of
Total mass of glucose in final solution:W ;W
the substance used.
W:10;10
[Volume:1 dm, R:8.314 J K\ mol\] :20 g
(2 marks) W RT
: ;
Solution : M V
Given : W:1.8;10\ kg:1.8 g W RT
: ;
:0.52 atm; V:1 dm M V
T:280 K; WRT/M;V W
: :
Molar mass:M:? W RT/M;V W

W 20 ★ (11) At 25 °C 0.1 molal solution of CH COOH is
: ; :3.84; :7.68 atm
W 10 1.35% dissociated in an aqueous solution.

Ans. Osmotic pressure of the solution:7.68 atm
------------------------------------------------------------------------------------
Calculate freezing point and osmotic pressure
★ (10) A mixture of benzene and toluene contains of the solution assuming molality and molarity
30% by mass of toluene. At 30 °C, vapour to be identical. (3 marks)
pressure of pure toluene is 36.7 mm Hg and Solution :
that of pure benzene is 118.2 mm Hg. Assuming
Given : T:273;25:298 K
that the two liquids form ideal solutions, calcu-
C:0.1 m X0.1 M; Kf :1.86 K kg mol 91
late the total pressure and partial pressure of
each constituent above the solution at 30 °C. Per cent dissociation:1.35
(3 marks) Freezing point:tf :?
Solution : :?
Given : 30% by mass of toluene (T) and 70% by 1.35
mass of benzene (B). : :0.0135
100
WT :30 g; WB :70 g
CH COOH & CH COO 9 ; H ;
PT :36.7 mm Hg; PB :118.2 mm Hg
19
MT :92 g mol 91; MB :78 g mol 91
i:19;;:1;:1;0.0135:1.0135
PT :? PB :? Psoln :?
W 30 (i) Tf :i;Kf ;m
nT : T : :0.3260 mol
MT 92 :1.0135;1.86;0.1
W 70
nB : B : :0.8974 mol :0.1885 °C
MB 78
Freezing point of solution:090.1885
Total number of moles:nTotal :nT ;nB
:0.326;0.8974 : 90.1885 °C
:1.2234 mol (ii) :iCRT
Mole fractions : :1.035;0.1;0.08206;298
n
xT : T :
0.326
:0.2665 :2.53 atm
nTotal 1.2234
xB :190.2665:0.7335 Ans. (i) Freezing point of solution:90.1885 °C
Psoln :xT ;PT ;xB ;PB (ii) Osmotic pressure::2.53 atm
:0.2665;36.7;0.7335;118.2 ------------------------------------------------------------------------------------
:9.780;86.7 ★ (12) A 0.1 m solution of K SO in water has

:96.48 mm Hg
freezing point of 90.43 °C. What is the value of
Partial pressures :
van’t Hoff factor if Kf for water is 1.86 K kg
PT :xT ;Psoln
mol 91 ?
:0.2665;96.48
:25.71 mm Hg Solution :
PB :xB ;Psoln Given : m:0.1 m, Tf :09(90.43):0.43 °C
:0.7335;96.48 Kf :1.86 K kg mol 91, i:?
:70.77 mm Hg Tf :i;Kf ;m
Ans. Total pressure:Psoln :96.48 mm Hg Tf 0.43
Partial pressures : PToluene :25.71 mm Hg i: : :2.312
Kf ;m 1.86;0.1
PBenzene :70.77 mm Hg
Ans. van’t Hoff factor:i:2.312
------------------------------------------------------------------------------------
------------------------------------------------------------------------------------
2. SOLUTIONS 81
★ (13) A 0.15 m aqueous solution of KCl freezes at
90.510 °C. Calculate i and osmotic pressure at
0 °C. Assume volume of solution equal to that Q. 84. Select and write the most appropriate answer
of water. (3 marks) from the given alternatives for each subques-
Solution : tion : (1 mark each)
Given : c:0.15 m KCl X 0.15 M KCl ★ 1. The vapour pressure of a solution cotaining 2 moles
Tf :09Tf :09(90.510):0.510 °C of a solute in 2 moles of water (vapour pressure of
T:273 K; Kf :1.86 K kg mol 91 pure water:24 mm Hg) is
(a) 24 mm Hg (b) 32 mm Hg
i:?; :?
(c) 48 mm Hg (d) 12 mm Hg
Tf :i;Kf ;m
★ 2. The colligative property of a solution is
Tf
i: (a) vapour pressure (b) boiling point
Kf ;m
(c) osmotic pressure (d) freezing point
0.510
: ★ 3. In calculating osmotic pressure the concentration of
1.86;0.15
solute is expressed in
:1.828
(a) molarity (b) molality
:iCRT
(c) mole fraction (d) mass per cent
:1.828;0.15;0.08206;273
★ 4. Ebullioscopic constant is the boiling point elev-
:6.143 atm
ation when the concentration of solution is
Ans. i:1.828, Osmotic pressure::6.143 atm
------------------------------------------------------------------------------------
(a) 1 m (b) 1 M
(c) 1 mass% (d) 1 mole fraction of solute
★ (14) The osmotic pressures of CaCl and urea sol-
★ 5. Cryoscopic constant depends on
utions of the same concentration at the same
(a) nature of solvent
temperature are respectively 0.605 atm and
(b) nature of solute
0.245 atm. Calculate van’t Hoff factor for
(c) nature of solution
CaCl . (2 marks)
(d) number of solvent molecules
Solution :
★ 6. Identify the correct statement
Given : CaCl :0.605 atm; (a) vapour pressure of solution is higher than that

urea :0.245 atm of pure solvent.
For urea solution, van’t Hoff factor, (b) boiling point of solvent is lower than that of
i:1 solution
CaCl :i;(CRT)CaCl (c) osmotic pressure of solution is lower than that

urea :(CRT)urea of solvent
CaCl i(CRT)CaCl (d) osmosis is a colligative property.
:
urea (CRT)urea ★ 7. A living cell contains a solution which is isotonic
CaCl 0.605 with 0.3 M sugar solution. What osmotic pressure
i: : :2.47
urea 0.245 develops when the cell is placed in 0.1 M KCl
Ans. van’t Hoff factor:i:2.47 ■ solution at body temperature ?
(a) 5.08 atm (b) 2.54 atm
Activity (c) 4.92 atm (d) 2.46 atm
★ 8. The osmotic pressure of blood is 7.65 atm at 310 K.
● Boil about 100 mL of water in a beaker. Add about
10 to 15 g of salt (NaCl) to the boiling water. Write An aqueous solution of glucose isotonic with blood
your observations and conclusions. has the percentage (by volume)
(a) 5.41% (b) 3.54%
[Note : Students are expected to carry out this activity on their own.] (c) 4.53% (d) 53.4%

★ 9.Vapour pressure of a solution is 15. 5;10 93 kg of urea is dissolved in 2;10 92 kg of
(a) directly proportional to the mole fraction of the water. The percentage by weight of urea is
solute (a) 15% (b) 20%
(b) inversely proportional to the mole fraction of the (c) 25% (d) 30%
solute 16. Vapour pressure of solution of a nonvolatile solute
(c) inversely proportional to the mole fraction of the is always
solvent (a) equal to the vapour pressure of pure solvent
(d) directly proportional to the mole fraction of the (b) higher than vapour pressure of pure solvent
solvent (c) lower than vapour pressure of pure solvent
(d) constant
★ 10.Pressure cooker reduces cooking time for food
17. According to the Raoult’s law, the relative lower-
because
ing of vapour pressure is equal to the
(a) boiling point of water involved in cooking is
(a) mole fraction of solvent
increased
(b) mole fraction of solute
(b) heat is more evenly distributed in the cooking
(c) independent of mole fraction of solute
space
(d) molality of solution
(c) the higher pressure inside the cooker crushes the
18. Partial pressure of solvent in solution of non-
food material
volatile solute is given by equation,
(d) cooking involves chemical changes helped by a
(a) P:x P (b) P:xP
rise in temperature
(c) P:x P (d) P:x P

★ 11. Henry’s law constant for a gas CH Br is 0.159 19. When partial pressure of solvent in solution of

mol dm 93 atm at 250 °C. What is the solubility of nonvolatile solute is plotted against its mole frac-
CH Br in water at 25 °C and a partial pressure of tion, nature of graph is

0.164 atm ? (a) a straight line passing through origin
(a) 0.0159 mol L 91 (b) 0.164 mol L 91 (b) a straight line parallel to mole fraction of
(c) 0.026 M (d) 0.042 M solvent
★ 12.Which of the following statement is NOT correct (c) a straight line parallel to vapour pressure of
for 0.1 M urea solution and 0.05 M sucrose solvent
solution ? (d) a straight line intersecting vapour pressure axis
(a) osmotic pressure exhibited by urea solution is 20. Colligative property depends only on ……… in a
higher than that exhibited by sucrose solution solution.
(b) urea solution is hypertonic to sucrose solution (a) Number of solute particles
(b) Number of solvent particles
(c) they are isotonic solutions
(c) Nature of solute particles
(d) sucrose solution is hypotonic to urea solution
(d) Nature of solvent particles
13. A molal solution is one that contains one mole of
21. Lowering of vapour pressure of solution
solute in
(a) is a property of solute
(a) one litre of the solvent (b) is a property of solute as well as solvent
(b) 1000 g of the solvent (c) is a property of solvent
(c) one litre of the solution (d) is a colligative property
(d) 22.4 litre of solution 22. Raoult’s law is not applicable to
14. 10.0 grams of caustic soda when dissolved in (a) solutions of volatile solutes
250 cm of water, the resultant molarity of solution is (b) solutions of electrolytes
(a) 0.25 M (b) 0.5 M (c) dilute solutions
(c) 1.0 M (d) 0.1 M (d) concentrated solutions
2. SOLUTIONS 83
23. The relative lowering of vapour pressure of a 32. Which of the following solutions shows maximum
solution is proportional to the depression in freezing point ?
(a) mole fraction of the solvent (a) 0.5 M Li SO (b) 1 M NaCl

(b) mole fraction of the solute (c) 0.5 M Al (SO ) (d) 0.5 M BaCl

(c) amount of the substance 33. If the freezing point of 0.1 m solution is 272.814 K,
(d) volume of the solvent then the freezing point of 0.2 m solution will be
24. The vapour pressure of an aqueous solution of (a) 545.628 K (b) 265.64 K
glucose at 100 °C is 710 mmHg. Hence the molal- (c) 272.628 K (d) 0.482 K
ity of the solution is 34. At a freezing point,
(a) 2.83 m (b) 3.65 m (a) Vapour pressure of a solution:Vapour press-
(c) 16.47 m (d) 12.5 m ure of a solid
25. Relative vapour pressure lowering depends only on (b) Vapour pressure of a liquid:Vapour pressure
(a) Mole fraction of solute of a solid
(b) Nature of solvent (c) Vapour pressure of a liquid Vapour pressure
(c) Nature of solute of a solid
(d) Nature of solute and solvent (d) Vapour pressure of a solid Vapour pressure
of a liquid
26. A solution having mole fraction of a solute equal
35. In osmosis
to 0.05 has vapour pressure 20;10 Nm 92.
(a) solvent molecules pass from high concentra-
Hence the vapour pressure of a pure solvent is
tion of solute to low concentration
(a) 21.05;10 Nm 92 (b) 4;10 Nm 92
(b) solvent molecules pass from a solution of low
(c) 1;10 Nm 92 (d) 2;10 Nm 92
concentration of solute to a solution of high
27. The addition of the nonvolatile solute into the pure
concentration of solute
solvent ……… .
(c) solute molecules pass from low concentration
(a) increases the vapour pressure of solvent
to high concentration
(b) decreases the boiling point of solvent
(d) solute molecules pass from high concentration
(c) decreases the freezing point of solvent
to low concentration
(d) increases the freezing point of solvent
36. As temperature increases
28. A solution having the highest vapour pressure is (a) Osmotic pressure and vapour pressure decrease
(a) 1 M Al (SO ) (b) 0.1 M NaNO
(b) Vapour pressure and osmotic pressure increase
(c) 1 M BaCl (d) 1 M Ca(NO )
(c) Vapour pressure increases but osmotic pressure
29. Molal elevation constant is elevation in boiling decreases
point produced by (d) Osmotic pressure increases but vapour press-
(a) 1 g of solute in 100 g of solvent ure decreases
(b) 100 g of solute in 1000 g of solvent 37. A mango kept in a salt solution shrinks. Hence the
(c) 1 mole of solute in one litre of solvent liquid content in mango with respect to the salt
(d) 1 mole of solute in one kg of solvent solution is
30. The determination of molar mass from elevation in (a) isotonic (b) hypertonic
boiling point is called (c) hypotonic (d) equimolar
(a) cryoscopy (b) osmometry 38. The osmotic pressure of 5% glucose solution at
(c) ebullioscopy (d) spectroscopy 300 K is
31. Which of the following aqueous solutions will (a) 6.93;10 Nm 92 (b) 6.93;10 Nm92
have minimum elevation in boiling point ? (c) 6.83 Pa (d) 6.00;10 Pa
(a) 0.1 M KCl (b) 0.05 M NaCl 39. 0.1 M solution of A has osmotic pressure x Nm 92
(c) 1 M AIPO (d) 0.1 M MgSO at 300 K. If 200 ml of A and 100 ml of 0.2 M

solution of nonreactive solute B are mixed then the 49. The osmotic pressure of 0.1 M HCl solution at
osmotic pressure will be 27 °C will be
(a) 3x (b) 0.05 x (c) 1.33 x (d) 0.75 x (a) 2.46 atm (b) 0.164 atm
40. The solution A is twice hypertonic to the solution B (c) 4.92 atm (d) 0.0082 atm
at a given temperature. If the solution A contains 50. If a, b, c and d are the van’t Hoff factors for
8.6;10 molecules, then the number of mole- Na SO , glucose and K [Fe(CN) ] then

cules present in B are, (a) a b c (b) a
b
c
(a) 8.6;10 (b) 1.73;10 (c) b
a
c (d) c
a
b
(c) 3.24;10 (d) 4.3;10 51. The osmotic pressure of 0.2 M KCl solution at
41. Isotonic solutions are the solutions having the 310 K is
same (a) 10.17 atm (b) 5.084 atm
(a) surface tension (b) vapour pressure (c) 8.36 atm (d) 12.2 atm
(c) osmotic pressure (d) viscosity 52. A temperature at which 0.1 M KCl solution will
42. If Kb for water is 0.52 Km 91, the boiling point of have osmotic pressure 10 atm will be
0.2 m solution of a nonvolatile solute will be (a) 408 °C (b) 263 °C
(c) 310 °C (d) 337 °C
(a) 371.96 K (b) 373.104 K
(c) 373.52 K (d) 374.0 K 53. 5% solution of glucose is isotonic with a solution
of urea (M:60). Hence the weight of urea
43. The vapour pressure of water is 15.5 mm at 20 °C.
present in the solution is
The lowering of vapour pressure of 0.02 m K Br
(a) 1.67 g (b) 6.0 g
solution will be
(c) 18.6 g (d) 1.2 g
(a) 0.0112 mm Hg (b) 0.0056 mm Hg
54. Abnormal molar mass is produced by
(c) 0.056 mm Hg (d) 0.31 mm Hg
(a) association of solute
44. Which of the following 0.1 M aqueous solutions (b) dissociation of solute
will exert highest osmotic pressure ? (c) both association and dissociation of solute
(a) Al (SO ) (b) Na SO (d) separation by semipermeable membrane

(c) MgCl (d) KCl
55. The van’t Hoff factor for an aqueous solution of an
45. If equimolar solutions of urea, NaCl, sucrose and electrolyte is
BaCl have boiling points A, B, C and D, then (a) less than 1 (b) zero

(a) A:C
B
D (b) A:D
B
C (c) greater than 1 (d) equal to 1
(c) A B C
D (d) A
B
C
D 56. The value of van’t Hoff factor will be minimum
46. The molar mass of acetic acid obtained by measur- for
ing depression in freezing point is 115.8 g mol\. (a) 0.05 M AlCl (b) 0.2 M NaNO

Hence the degree of association is (c) 5.0 M glucose (d) 0.1 M H SO

(a) 0.482 (b) 0.964 (c) 0.883 (d) 1.12 57. van’t Haff factor for K [FeC(N) ] dissociated

47. Tb /m for NaBr solution will have value 10% is
(Kb :0.52 K kg mol\) (a) 1.1 (b) 1.4
(a) 0.52 K mol\ (b) 0.104 K kg mol\ (c) 0.86 (d) 1.6
(c) 1.24 kg mol\ (d) 1.04 K kg mol\ Answers
48. 0.2 M urea solution can be isotonic with 1. (d) 12 mm Hg 2. (c) osmotic pressure 3. (a) molar-
(a) 0.1 M K Br solution ity 4. (a) 1 m 5. (a) nature of solvent 6. (b) boiling
(b) 0.1 M glucose solution point of solvent is lower than that of solution 7. (c) 4.92
(c) 0.15 m NaCl solution atm 8. (a) 5.41% 9. (d) directly proportional to the
(d) 0.2 M K Br solution mole fraction of the solvent 10. (a) boiling point of
2. SOLUTIONS 85
water involved in cooking is increased 11. (c) 0.026 M pressure is 600 mm. (Ans. x :0.4 and x :0.6,

12. (c) they are isotonic solutions 13. (b) 1000 g of the y :0.3 and y :0.7)

solvent 14. (c) 1.0 M 15. (b) 20% 16. (c) lower than (Problem 2.3 of Textbook page 32)
vapour pressure of pure solvent 17. (b) mole fraction of
4. A solution is prepared by dissolving 394 g of a
solute 18. (c) P:x P 19. (a) a straight line passing
nonvolatile solute in 622 g of water. The vapour
through origin 20. (a) Number of solute particles
pressure of solution is found to be 30.74 mm Hg at
21. (d) is a colligative property 22. (d) concentrated sol-
30 °C. If vapour pressure of water at 30 °C is 31.8
utions 23. (b) Mole fraction of the solute 24. (b) 3.65 m
mm Hg, what is the molar mass of solute ?
25. (a) mole fraction of the solute 26. (a) 21.05;10
(Ans. Molar mass:342 g mol\)
Nm 92 27. (c) decreases the freezing point of solvent
(Problem 2.4 of Textbook page 35)
28. (b) 0.1 M NaNO 29. (d) 1 mole of solute in one kg

of solvent 30. (c) ebullioscopy 31. (b) 0.05 M NaCl 5. The vapour pressure of pure benzene (molar mass 78
32. (c) 0.5 M Al (SO ) 33. (c) 272.628 K 34. (b) Vapour g/mol) at a certain temperature is 640 mm Hg. A

pressure of a liquid:Vapour pressure of a solid nonvolatile solute of mass 2.315 g is added to 49 g of
35. (b) solvent molecules pass from a solution of low concen- benzene. The vapour pressure of the solution is 600
tration of solute to a solution of high concentration of solute mm Hg. What is the molar mass of solute ?
36. (b) Vapour pressure and osmotic pressure increase (Ans. Molar mass:72.23 g mol\)
37. (c) hypotonic 38. (a) 6.93;10 Nm 92 39. (c) 1.33 x (Problem 2.5 of Textbook page 35)
40. (d) 4.3;10 41. (c) osmotic pressure 42. (b) 373.104
6. The normal boiling point of ethyl acetate is 77.06 °C.
K 43. (a) 0.0112 mm Hg 44. (a) Al (SO )
A solution of 50 g of a nonvolatile solute in 150 g of
45. (a) A:C
B
D 46. (b) 0.964 47. (d) 1.04 K kg
ethyl acetate boils at 84.27 °C. Evaluate the molar
mol\ 48. (a) 0.1 M KBr solution 49. (c) 4.92 atm
mass of solute if Kb for ethyl acetate is 2.77 °C kg
50. (c) b
a
c 51. (a) 10.17 atm 52. (d) 337 °C
53. (a) 1.67 g 54. (c) both association and dissociation of mol\. (Ans. Molar mass:128 g mol\)
solute 55. (c) greater than 1 56. (c) 5.0 M glucose (Problem 2.6 of Textbook page 35)
57. (b) 1.4. 7. 3.795 g of sulphur is dissolved in 100 g of carbon
disulfide. This solution boils at 319.81 K. What is the
molecular formula of sulphur in solution ? The
boiling point of the solvent is 319.45 K.
1. The solubility of N gas in water at 25 °C and 1 bar is
(Ans. Molecular formula of sulphur:S )

6.85;10\ mol L\. Calculate (a) Henry’s law
constant (b) molarity of N gas dissolved in water
8. 1.02 g of urea when dissolved in 98.5 g of certain
under atmospheric conditions when partial pressure
of N in atmosphere is 0.75 bar. solvent decreases its freezing point by 0.211 K.
1.609 g of unknown compound when dissolved in 86
(Ans. (a) KH :6.85;10\ mol L\ bar\
(b) S:5.138;10\ mol L\) g of the same solvent depresses the freezing point by
(Problem 2.1 of Textbook page 31) 0.34 K. Calculate the molar mass of the unknown
2. Henry’s law constant of methyl bromide (CH Br), is compound. (Molar mass of urea:60 g mol\)
(Ans. Molar mass:67.3 g mol\)
0.159 mol L\ bar\ at 25 °C. What is the solubility
of methyl bromide in water at 25 °C and at pressure (Problem 2.8 of Textbook page 38)
of 130 mm Hg ? (Ans. S:0.271 M) 9. What is the molar mass of a solute if a solution
(Problem 2.2 of Textbook page 31) prepared by dissolving 0.822 g of it in 300 mdm of
3. The vapour pressures of pure liquids A and B are 450 water has an osmotic pressure of 149 mm Hg at
mm Hg and 700 mm Hg, respectively at 350 K. Find 298 K ? (Ans. Molar mass:342 g mol\)
the composition of liquid and vapour if total vapour (Problem 2.9 of Textbook page 41)

10. 0.2 m aqueous solution of KCl freezes at 90.680 °C. 40 g CH Cl at the same temperature.

Calculate van’t Hoff factor and osmotic pressure of (Ans. 90.98 mm Hg)
solution at 0 °C. (Kf :1.86 K kg mol\) 20. The vapour pressure of pure benzene at a certain
(Ans. i:1.83; :8.2 atm) temperature is 640 mm Hg. A nonvolatile solute of
(Problem 2.10 of Textbook page 43) mass 2.175;10 93 kg is added to 39.0;10 93 kg of
11. 0.01 m aqueous formic acid solution freezes at benzene. The vapour pressure of the solution is
90.021 °C. Calculate its degree of dissociation. 600 mm Hg. What is the molecular mass of the
Kf :1.86 K kg mol\. solute? (Given atomic masses C:12, H:1)
(Ans. :0.13 OR dissociation:13%) (Ans. 69.6 g mol 9 )
(Problem 2.11 of Textbook page 43) 21. A solution is prepared from 26.2;10 93 kg of an
12. 3.4 g of CaCl is dissolved in 2.5 L of water at 300 K. unknown substance and 112.0;10 93 kg of acetone
at 313 K. The vapour pressure of pure acetone at this
What is the osmotic pressure of the solution ? van’t
Hoff factor for CaCl is 2.47. (Ans. :0.745 atm) temperature is 0.526 atm. Calculate the vapour
pressure of the solution if the molar mass of sub-
stance is 273.52;10 93 kg. (Ans. 0.5 atm)
13. Assuming complete dissociation, calculate the
22. 0.15 molal solution of a substance boils at 373.23 K.
molality of an aqueous solution of KBr whose
Calculate molal elevation constant of water. (Given
freezing point is 92.95 °C. Kf for water is 1.86 K kg
boiling point of water:373.15 K)
mol\. (Ans. molality:m:0.793 mol kg\)
(Ans. 0.53 K kg mol 9 )
23. Calculate molality of a solution of a substance
14. The solubility of a gas at 27 °C and 3.8 atmosphere
dissolved in benzene having boiling point 353.71 K.
is 5.354;10\ mol dm\. Find Henry’s law
Given that Kb for benzene is 2.53 K kg mole 9 and
constant (KH). (Ans. 1.41;10\ mol dm\ atm\)
boiling point of solution is 353.35 K.
15. The vapour pressure of a solution containing
(Ans. 0.1423 mol kg91)
13;10 93 kg of solute in 0.1 kg of water at 298 K is
24. A solution is prepared by dissolving 1.9;10 92 kg
27.371 mm Hg. Calculate the molar of the solute.
ammonia in 400 g of water. Calculate elevation in
Given that the vapour pressure of water at 298 K is
boiling point if Kb for water is 0.52 K kg mol\.
28.065 mm Hg. (Ans. 94.63 g mol 9 )
(N:14, H:1, O:16) (Ans. T b :1.45 K)
16. The solubility of oxygen in water at 280 K and 500 25. 0.440;10 93
kg of a substance (molar mass:
mm Hg is 0.01 g dm\. Hence what is the solubility 178.9;10 kg mol 9 ) dissolved in 22.2;10 93 kg
93
of O at 750 mm Hg at same temperature.

of benzene lowered the freezing point of benzene
(Ans. 0.015 g dm\) by 0.567 K. Calculate the molal depression constant
17. The vapour pressures of two liquids A and B are 80 for benzene. (Ans. K f :5.12 K kg mol 9 )
mm and 60 mm respectively at 25 °C. What is the 26. The observed depression in the freezing point of
vapour pressure of the solution obtained by mixing water for a particular solution is 0.087 K. Calculate
3 mol of A and 2 mol of B ? (Ans. 72 mm Hg) the molality of the solution if molal depression
18. A liquid mixture is prepared by mixing liquids A and constant for water is 1.86 K kg mol 9 .
B having vapour pressure 250 mm Hg and 330 mm (Ans. 0.0467 mol kg91)
Hg respectively. If the mole fraction of A in the 27. 1.02 g of urea when dissolved in 98.5 g of certain
solution is 0.6, what is the mole fraction of B in solvent decreases its freezing point by 0.211 K 1.60 of
vapour phase ? (Ans. yB :0.47) unknown compound when dissolved in 86.0 g of the
19. Vapour pressures of chloroform (CHCl ) and dich- same solvent depresses the freezing point by 0.34 K.

loromethane (CH Cl ) at 25 °C are 200 mm Hg and Calculate the molar mass of the unknown com-

415 mm Hg respectively. Calculate vapour pressure pound. (Urea NH CONH , N:14, C:12, O:16,

of a solution obtained by mixing 25.5 g CHCl and H:1) (Ans. 67.9 g mol 9 )

2. SOLUTIONS 87
28. A solution of glucose (C H O ) was prepared by 30. Calculate the osmotic pressure of 4.5 g of glucose

dissolving a certain amount in 100 g of water. The (molar mass:180) dissolved in 100 mL of water at
298 K. (R:0.0821 L-atm mol 9 K 91 )
depression in freezing point is 0.0410 K. If molal
(Ans. 6.116 atm)
depression constant for water is 1.86 K kg mol 9 ,
31. A solution of cane sugar (molar mass:342 g
calculate the weight of glucose dissolved. (C:12, mol 9 ) containing 17.8 g L 91 has an osmotic
H:1,O:16) (Ans. 0.40 g) pressure 1.2 atm. Calculate the temperature of the
solution. (R:0.082 L-atm mol 9 K 91 )
29. Calculate the freezing point of solution prepared by (Ans. 281.4 K)
32. 30 g of glucose present per litre has an osmotic
dissolving 4.5 g of glucose (Molar mass:180 g
pressure of 4.91 atm at 303 K. If the osmotic pressure
mol 9 ) in 250 g of bromoform. Given, Freezing
of the same solution is 1.5 atm at the same tempera-
point of bromoform:7.8°C and K f for bromo- ture, what would be its concentration ?
form: 14.4 K kg mol 9 . (Ans. 6.36°C) (Ans. 0.0509 M)

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Based on the Board's New Textbook

★ Navneet Bhavan, Bhavani Shankar Road, Dadar (West),

Published by : Navneet Education Limited, Dantali, Gujarat. 2001

1. Solid State  . . . 155

2. Solutions . . . 147

3. Ionic Equilibria . . . 89

4. Chemical Thermodynamics . . . 120

5. Electrochemistry . . . 183

6. Chemical Kinetics . . . 248

7. Elements of Groups 16, 17 and 18 . . . 307

Chapter Nos. 9 to 16 are included in Chemistry Digest: Part 2, published separately.

6. Packing efficiency : scc bcc fcc hcp

7. Number of tetrahedral voids:2 Number of atoms

scc bcc fcc

6 NAVNEET CHEMISTRY DIGEST : STANDARD XII (PART I)

(1) There are three physical states of matter namely

Q. 6. Define the term anisotropy. (1 mark) Do you know ?

8 NAVNEET CHEMISTRY DIGEST : STANDARD XII (PART I)

Q. 10. What is isomorphism ? (1 mark)

Q. 18. Distinguish between crystalline solids and

Crystalline solids Amorphous solids

1. They have definite charac- 1. They have irregular shape.

10 NAVNEET CHEMISTRY DIGEST : STANDARD XII (PART I)

Q. 28. What are molecular crystals ? (1 mark)

12 NAVNEET CHEMISTRY DIGEST : STANDARD XII (PART I)

Table 1.1 : Properties of four types of crystalline solids

Type Ionic solids Covalent network Molecular Metallic

4. Melting points High High Low Wide range

★ Q. 33. Distinguish between ionic solids and Ans.

Q. 37. What is lattice ? (1 mark)

14 NAVNEET CHEMISTRY DIGEST : STANDARD XII (PART I)

Q. 45. Explain briefly crystal systems. (2 marks)

(3) Body-centred cubic unit cell : In this, the lattice

Q. 49. Find the number of atoms per unit cell in the

(2) Number of atoms in body-

16 NAVNEET CHEMISTRY DIGEST : STANDARD XII (PART I)

Crystal system Bravais lattices

Name Unit cell structure

1. Cubic i. simple or primitive

2. Orthorhombic i. simple or primitive

3. Tetragonal i. simple or primitive

4. Monoclinic i. simple or primitive

Name Unit cell structure

5. Rhombohedral i. simple or primitive

6. Triclinic i. simple or primitive

7. Hexagonal i. simple or primitive

18 NAVNEET CHEMISTRY DIGEST : STANDARD XII (PART I)

Q. 56. Explain close packing in three dimensions.

Fig. 1.18 : Stacking of square close packed layers

20 NAVNEET CHEMISTRY DIGEST : STANDARD XII (PART I)

Fig. 1.20 : Hexagonal close packing (hcp)

(b) Cubic close packing (ccp) : If the crests of

★ Q. 60. Sketch a tetrahedral void. (2 marks)

Q. 59. Explain tetrahedral void. (2 marks)

22 NAVNEET CHEMISTRY DIGEST : STANDARD XII (PART I)

Q. 67. Calculate packing efficiency in face-centred

Volume occupied by 2 particles:

24 NAVNEET CHEMISTRY DIGEST : STANDARD XII (PART I)

26 NAVNEET CHEMISTRY DIGEST : STANDARD XII (PART I)

28 NAVNEET CHEMISTRY DIGEST : STANDARD XII (PART I)

30 NAVNEET CHEMISTRY DIGEST : STANDARD XII (PART I)

Q. 72. What is meant by crystal defects or imper-

(3) The properties of solids are affected due to imper-

1. Solid State . . . 155

2. Solutions . . . 147

3. Ionic Equilibria . . . 89

4. Chemical Thermodynamics . . . 120

5. Electrochemistry . . . 183

6. Chemical Kinetics . . . 248

7. Elements of Groups 16, 17 and 18 . . . 307

Ans. Kb :2.53 K kg mol 9 (8) A solution containing 0.5126 g of naphthalene