PMT Class XII Chemistry Solid State

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MEDICAL
THE SOLID STATE
C H E MI S T R Y
S T U D Y M A T E R I A L
NARAYANA INSTITUTE OF CORRESPONDENCE COURSES
F N S H O U S E , 6 3 K A L U S A R A I M A R K E T
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2004 NARAYANA GROUP
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CONT ENT S CONT ENT S CONT ENT S CONT ENT S CONT ENT S
THE SOLID STATE
Theory
Exercises
True and False Statements
Fill in the Blanks
Assertion-Reason Type Questions
Multiple Choice Questions
MCQs Asked in Competitive Examinations
Subjective Questions
Answers
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FNS House, 63, Kalu Sarai Market, Sarvapriya Vihar, New Delhi-110016 ! Ph.: (011) 32001131/32 Fax : (011) 41828320
1
Chemistry : The Solid State NARAYANA
INSTITUTE OF CORRESPONDENCE COURSES
CONTENTS
! !! !! Introduction
! !! !! Classification of Solids
! !! !! Types of Symmetry
! !! !! Types of Unit Cells
! !! !! Crystal Defects
! !! !! Radius Ratio
! !! !! Structure of Simple Ionic
Compounds
! !! !! Closest Packing
! !! !! Properties of Solids
! !! !! Metal Silicates
! !! !! Exercise
! !! !! Answers
THE SOLID STATE
M ost of the things around us are solids
having different shapes and size. In a solid,
the molecules have fixed positions and their
motion is restricted to just vibrations. The
constituent particles in a solid are closely
packed and this leads to the properties like
incompressibility, rigidity, non-fluidity, slow
diffusion and mechanical strength. In this
unit, we will classify solids on the basis of
binding forces, understand structure of solids
describe the imperfections in solids and their
effects on properties and their application in
industries.
Chemistry : The Solid State
2
NARAYANA
A substance is said to be solid if its melting point is above the room temperature. Some of the important
characteristics of solids are as follows :
(i) Solids have definite shapes, size and volume
(ii) Solids are almost incompressible and generally have high density
(iii) The diffusion of solid is negligible or rather very slow as the particles have permanent positions from
which they do not move easily.
CLASSIFICATION OF SOLIDS
Solids can be classified broadly into two types.
1. Crystalline Solids 2. Amorphous Solids
Difference Between Crystalline and Amorphous Solids
Crystalline Solids Amorphous Solids
1.
They have definite and regular geometry due to definite and
orderly arrangement of atoms, ions or molecules in three
dimensional space
They do not have any pattern of arrangement
of atoms, ions or molecules and thus, do not
have any definite geometrical shape.
2. They have sharp melting points and change abruptly into liquids
Amorphous solids do not have sharp melting
points and do not change abruptly into liquids.
3.
Crystalline solids are anisotropic. Some of their physical
properties are different in different directions
Amorphous solids are isotropic. Their physical
properties are same in all directions.
4. These are considered as true solids.
These are considered pseudosolids or
supercooled liquids.
5.
Crystalline solids are rigid and their shape is not distorted by
mild distoring forces.
Amorphous solids are not very rigid. These can
be distorted by bending or compressing forces.
6.
Crystals are bound by plane faces. The angle between any two
faces is called interfacial angle. For a given crystalline solid, it is
definite angle and remains always constant no matter how the
faces develop. When a crystalline solid is hammered, it breaks
up into smaller crystals of the same geometrical shape.
Amorphous solids do not have well defined
planes.
When an amorphous solid is broken, the
surfaces of the broken pieces are generally not
flat and intersect at random angles.
7.
Crystals have some sort of symmetry. (i) plane of symmetry,
(ii) axis of symmetry or (iii) centre of symmetry
Amorphous solids do not have any symmetry.
INTRODUCTION
G
ases and liquids belong to fluid state. The fluidity of liquids and
gases is due to relative free motion of their molecules. In solids,
molecules or atoms or ions oscillate around their fixed positions
due to strong intermolecular or interatomic or interionic forces. This brings
rigidity and long range order in solids. Solids are classified as crystalline
and amorphous. In crystalline solids atoms, ions or molecules are held in
an orderly array. In amorphous solid there is only short range order.
Industrial applications of solids in based on their electrical, magnetic and
dielectric properties.
3
TYPES OF CRYSTALLINE SOLIDS
Crystalline Solid
Ionic crystal
Covalent crystal
Metallic crystal
Molecular crystal
Characteristics of the Different types of crystalline Solids

Characteristics Ionic Crystal Covalent Crystal Metallic Crytsal Molecular crystal
1
Constituent
particles
Cat ions (positive
io ns ) a nd a nio ns
(negative ions)
Atoms Atoms Small molecules
2
Binding
forces
Strong electrostatic
forces
Covalent forces
Electrostatic attraction
between positive ions and
mobile electrons
Weak van der Waal's
forces
3
Physical
properties
Brittle, high m.p. and
b.p., good conductors
of electricity in molten
state and aqueous
solution, high heats of
fusion.
Generally hard,
high m.p. and b.p.,
poor conductors of
heat, high heats of
fusion.
Hard and high m.p., very
good conductors of heat
and electricity, exhibit
properties such as lustre.
malleability ductility etc.,
moderate heats of fusion.
Generally soft, low m.p.
volatile, poor
conductors of electricity
( ins ula t or s ) , poor
conductors of heat, low
heats of fusion.
4 Examples
NaCl, KF, CuSO
4
,
NaNO
3
etc.
Diamond, silicon
carbide (SiC)
quartz (SiO
2
) etc.
Cu, Ag, Fe, Na, K etc.
Solid CO
2
, Iodine,
Naphthalene, Argon
ice etc.
TYPES OF SYMMETRY IN CRYSTALS
(i) Centre of Symmetry : It is such an imaginary point within the crystal that any line drawn through
it intersects the surface of the crystal at equal distances in both directions. A crystal always possesses
only one centre of symmetry.
(ii) Plane of symmetry : It is an imaginary plane which passes through the centre of a crystal and
divides it into two equal parts such that one part is exactly the mirror image of the other.
A cubical crystal like NaCl possesses, in all, nine planes of symmetry; three rectangular planes
of symmetry and six diagonal planes of symmetry. One plane of symmetry of each of the above
is shown in fig.(a) and (b).
(iii) Axis of symmetry : It is an imaginary straight line about which, if the crystal is rotated, it will
present the same appearance more than once during the complete revolution. The axes of
symmetry are called diad, triad, tetrad and hexad, respectively, if the original appearance is
repeated twice (after an angle of 180), thrice (after an angle of 120), four times (after an
angle of 90) and six times (after an angle of 60) in one rotation. These axes of symmetry are
also called two-fold, three-fold, four fold and six-fold, respectively.
In general if the same appearance of a crystal is repeated on rotating through an angle of
360
,
n

around an imaginary axis, the axis is called an n-fold axis.
In all, these are 13 axes of symmetry possessed by a cubical crystal like NaCl as shown in fig.(c),
(d) and (e).
4
NARAYANA
(iv) Elements of symmetry: The total number of planes, axes and centre of symmetry possessed by a
crystal are termed as elements of symmetry. A cubic crystal possesse a total of 23 elements of
symmetry.
Planes of symmetry = (3 + 6) = 9 Fig (a) and (b)
Axes of symmetry = (3 + 4 + 6) = 13 Fig (c), (d) and (e)
Centre of symmetry = 1 Fig. (f)
The total number of symmetry elements = 23
CRYSTAL LATTICE
The regular three dimensional arrangement of the points in a crystal is called space lattice. The space
lattice is also called crystal lattice. The locations of the points in the space lattice are called lattice points
or lattice sites.
UNIT CELL
The smallest but complete unit in the space lattice which when repeated over and over again in the three
dimensions, generates the crystal of the given substance.
TYPES OF UNIT CELLS
Unit cells are basically of two types. These are primitive and non primitive.
Primitive unit cells : A unit cell is called primitive unit cell if it has particles (or points) only at the
corners. It is also called simple unit cell.
Non-primitive unit cells : In this type of unit cells, particles (or points) are present not only at the
corners but also at some other positions. These are of three types :
(i) Face centred : Particles (or points) are located at the corners and also in the centre of each face.
(ii) Body centred : Particles (or points) are located at the corners and also at the centre within the
body.
(iii) End centred : Particles (or points) are located at the corners and also at the centres of the end
faces.
5
Simple or Primitive unit cell Body centred unit cell
Face centred unit cell End centred unit cell
Fig. Primitive and non-primitive unit cells
SEVEN CRYSTAL SYSTEMS
It we take into consideration the symmetry of the axial distances (a, b, c) and also the axial angles
between the edges ( , , ) , the various crystals can be divided into seven systems. These are also
called crystal habits. These crystals alongwith suitable examples are listed in the table
The seven crystal systems
System Axial distance Axial angles Examples
Cubic a = b = c 90 NaCl, KCl, Diamond, Cu, Ag
Tetragonal a = b
c 90 White tin, SnO

2
Orthorhombic a
c 90 Rhombic sulphur, KNO

3
, K
2
SO
4
, BaSO
4
, PbCO
3
Monoclinic a
c 90 , 90 Monoclinic sulphur, Na
2
SO
4
.10H
2
O
Hexagonal a = b
c 90 , 120 Graphite, ZnO, CdS

Rhombohedral a = b = c 90 Calcite (CaCO
3
), quartz, NaNO
3
Triclinic a
c 90 CuSO
4
.5H
2
O, K
2
Cr
2
O
7
BRAVAIS LATTICES
The seven crystal systems listed above can be further classified on the basis of the unit cells present.
Although each crystal system is expected to have four different unit cells, but actually all of them cannot
exist in each case. Bravais in 1848 has established fourteen different types of lattices called Bravais
lattices according to the arrangement of the points in the different unit cells involved listed below:
Crystal System Types of Lattices
Cubic Simple, Face centred, Body centred
Tetragonal Simple, Body centred
Orthorhombic Simple, Face centred, Body centred, End centred
Monoclinic Simple, End centred
Rhombohedral Simple
Triclinic Simple
Hexagonal Simple
In various unit cells, there are three kinds of lattice points : points located at the corners, points in the face
centres and points that lie entirely within the unit cell. In a crystal, atoms located at the corner and face-
centre of a unit cell are shared by other cells and only a portion of such an atom actually lies within a
given unit cell.
6
NARAYANA
(i) A point that lies at the corner of a unit cell is shared among eight unit cells and, therefore, only one-
eighth of each such point lies within the given unit cell.
(ii) A point along an edge is shared by four unit cells and only one-fourth of it lies within any one cell.
(iii) A face-centred point is shared by two unit cells and only one half of it is present in a given unit cell.
(iv) A body-centred point lies entirely within the unit cell and contributes one complete point to the cell.
Types of lattice point Contribution to one unit cell
Corner 1/8
Edge 1/4
Face-centre 1/2
Body-centre 1
Total number of constitutent units per unit cell
8
1
occupied corners +
4
1
occupied edge centres +
2
1
occupied face centres + occupied
body centre.
Determination of Number of Constitutent units per unit cell :
Let edge length of cube = a cm
Density of substances = d g cm
3
Volume of unit cell = a
3
cm
3
Mass of unit cells = volume density = (a
3
d) g
Number of mole per unit cell =
M
d a
3
;
where M = molar mass
Number of molecules per unit cell = Number of mole Avogadros Number
3
a d N
Z
M

EXAMPLES - 1
The density of KCl is 1.99 g cm
3
and the length of a side of unit cell is 6.29 as determined by X-ray
diffraction. Calculate the value of Avogadros number.
SOLUTION :
KCl has face-centred cubic structure,
i.e., Z = 4
Avogadros number =
V d
M Z
Given, d = 1.99; M = 74.5; V = (6.29 10

8
)
3
cm
3
Avogadros number =
23
8 3
4 74.5
6.01 10
1.99 (6.29 10 )

EXAMPLES - 2
An element occurs in bcc structure with a cell edge of 288 pm. The density of element is 7.2 g cm
3
. How
many atoms does 208 g of the element contain?
7
SOLUTION :
Volume of the unit cell = (288 10
10
)
3
= 23.9 10
24
cm
3
Volume of 208 g of the element =
3
cm 88 . 28
2 . 7
208
Number of unit cell in 28.88 cm

3
=
24
10 9 . 23
88 . 28
= 12.08 10
23
unit cells
So, total no. of atoms in 12.08 10
23
unit cells = 2 12.08 10
23
[since each bcc unit cell contain 2
atoms]
= 24.16 10
23
EXAMPLES : 3
The density of potassium bromide crystal is 2.75 g cm
3
and the length of an edge of a unit cell is 654 pm.
The unit cell of KBr is one of three types of cubic unit cells. How many formula units of KBr are there
in a unit cell? Does the unit cell have a NaCl or CsCl structure?
SOLUTION :
We know that
1
]
1

A
3
N
M
a
N
M
N a
N
A
3

10 3 23
2.75 (654 10 ) 6.023 10
3.89 4
119

!
Number of mass points per unit cell = 4
Thus , , has NaCl type crystal is fcc structure.
EXAMPLES : 4
A cubic solid is made up of two atoms A and B. Atoms A are present at the corners and B at the centre
of the body. What is the formula of the unit cell?
SOLUTION :
Contribution by the atoms A present at eight corners = 1/8 8 = 1
Contribution by the atom B present in the centre of the body = 1
Thus, the ratio of atoms of A : B = 1 : 1
Formula of unit cell = AB
EXAMPLES : 5
If three elements P, Q and R crystallise in a cubic unit cell with P atoms at the corners. Q atoms at the
cubic centre and R atoms at the centre of each face of the cube, then write the formula of the compound.
SOLUTION :
Contribution made by the atoms of P present at all the eight corners of the tube = 1/8 8 = 1
Contribution made by the atoms of Q present in the centre of the body = 1
Contribution made by the atoms of R present at the centre of all the six faces = 1/2 6 = 3
Formula of the compound = PQR
3
8
NARAYANA
RELATION BETWEEN EDGE LENGTH (A) AND THE RADIUS OF SPHERE (R)
We have calculated the number of atoms (or spheres since an atom or particle may be regarded as the
sphere) in different types of cube unit cells. Now, let us calculate the relation between the edge length (a)
and the radius (r) of the spheres present in these unit cells in case of pure elements i.e. elements composed
of the same type of atoms.
(a) Distance between the centres of the spheres present on the corners of the edges of the cubic is
called edge length (a).
(b) Distance between the centres of the two nearest spheres is called nearest neighbour distance (d)
and is equal to r + r = 2r. (Here r is the radius of the spheres or the atomic radius)
FOR SIMPLE CUBIC LATTICE
In a simple cubic unit cell, there is one atom (or one sphere) per unit cell. If r is the radius of the sphere,
volume occupied by one sphere present in the unit cell =
3
4
3
r
Since the spheres at the corners touch each other;
Edge length (a) = r + r = 2r = d
No of atom on the corners =
1 8
8
1

a
Total no. of atoms in a unit cell = 1
Radius of an atom = r
Distance between nearest neighbour (d) = a
Volume of cube = a
3
= (2r)
3
= 8r
3
Packing fraction =
cube of Volume
sphere of Volume
=
524 . 0
6 r 8
r 3 / 4
3
3
% volume occupied by atom = 52.4

% volume unoccupied = 100 52.4 = 47.6
FOR FACE CENTRED CUBIC LATTICE
No. of atoms on the corners =
1 8
8
1

a
B
C
A
No. of atoms on the faces =
3 6
2
1

Total no. of atoms in a unit cell = 1 + 3 = 4
Volume occupied by atoms =
3
r
3
4
4
From , ABC AC
2
= AB
2
+ BC
2
AC
2
= a
2
+ a
2
= 2a
2
AC = 2 a.
Distance between nearest neighbour (d) =
AC a 2 a
2 2 2

9
Radius of the atom (r) =
d
2
=
2 2
a
Volume occupied by atoms in a unit cell

3
2 2
a
3
4
4

,
_

Thus packing fraction
74 . 0
a
2 2
a
3
4
4
3
3
,
_
% volume occupied by unit cell = 74

% volume unoccupied by unit cell = 100 74 = 28
FOR BODY CENTRED CUBIC LATTICE
No. of atoms on the corners =
1 8
8
1

No. of atoms in the body = 1
Total no. of atoms in a unit cell = 1 + 1 = 2
a
B
C
A
D
From ADC , AD
2
= AC
2
+ CD
2
=
( )
2 2
2
a 3 a a 2 +
AD =
3 a
Distance between nearest neighbour (d) =

2
3 a
2
AD
Radius of an atom (r) = d/2 =

4
3 a
Volume occupied by atoms =
3
4 a 3
2
3 2
_

,
Packing fraction =
cube of . Vol
atoms by occupied . Vol
3
3
4 a 3
2
3 2
0.68
a
_
% volume occupied in a unit cell = 68

% volume unoccupied in a unit cell = 32
Lattice type Radius (r) Distance between Nearest neighbour Packing fraction
Simple cube
2 / a r
d = 2r = a 0.524
Face centred r =
2 2
a
2 d a
0.74
Body centred
4
3 a
r
2
3 a
d 0.68
10
NARAYANA
EXAMPLES : 6
The radius of copper atom is 128 pm. If it crystallises in a face centred cubic lattice (fcc). what will be
the length of the edge of the unit cell?
SOLUTION :
For face centred cubic crystal
Edge length (a) = pm 362 ) pm 128 ( ) 4142 . 1 ( 2 r 2 2
EXAMPLES : 7
Xenon crystallises in a face centred cubic lattice and the edge of the unit cell is 620 pm. Calculate the
nearest neighbouring distance and the radius of the xenon atom?
SOLUTION :
Nearest neighbour distance (d) =
pm 4 . 438
4142 . 1
) pm 620 (
2
a

Radius of xenon atom (r) =
pm 2 . 219
4142 . 1 2
) pm 620 (
2 2
a
EXAMPLES : 8
The face diagonal of a cubic closed packed unit cell is 4. What is its face length?
SOLUTION :
Face diagonal =
2 2
a a a 2 +
; 83 . 2
4142 . 1
) 4 (
2
4
2
diagonal Face
a
EXAMPLES : 9
An element A crystallises in face-centred cubic lattice with edge length of 100 pm. What is the radius of
its atom A and the nearest neighbour distance in the lattice? What is the length of its face-diagonal?
SOLUTION :
For a face centred cubic lattice (fcc)
Radius (r) =
pm 4 . 35
4142 . 1 2
) pm 100 (
2 2
a
Nearest neighbour distance (d) = 2r = 2 35.4 pm = 70.8 pm

Length of face diagonal = 4r = 4 35.4 pm = 141.6 pm
CRYSTAL DEFECTS OR IMPERFECTIONS IN SOLID
Crystal defects
Electronic
imperfection
Atomic imperfection
or
point defect
Stoichiometric defect Non-stoichiometric defect
Impurity defect
Schottky defect
Frenkel defect Metal excess
Metal deficiency
Anion vacancy defect
Extra cation
Impurity defect
in covalent solid
Impurity defect
in Ionic solid
11
SCHOTTKY DEFECT
It consists of a pair of holes in the crystal lattice i.e one positive and one negative ion are absent from
their proper position. This sort of defect occurs mainly in highly ionic compounds where the +ve and -ve
ions are of similar size and hence co-ordination no. is high e.g.
NaCl, CsCl, KCl, KBr etc.
No of Schottky defect formed for cm
3
(n
s
) is given by
n
s
=
s
w
N.exp.
2kT
_

,
where N = No. of sites per cm
3
that could be left vacant
A B A B A
A
+
B B A B
A
+
B A A A
A
+
B A A B B
+ + +
+
+ + +
+ + +
W
S
= work necessary to form a schottky defect.
K = gas constant
T = absolute temp.
At room temp. NaCl has one defect in 10
15
lattice site.
At 500C, the value rising to one in 10
6
sites.
FRANKEL DEFECT
It consists of a vacant lattice site (a hole) and the ion
which ideally should have occupied the site now
occupies an interstitial position.
In this type of defect metal ions are generaly smaller
than the anion i.e. large difference in size and co-
ordination number is low. e.g. AgCl, AgBr, AgI.
The no. of Frenkel defect formed per cm
3
(N
f
) is
given by
f
f
w
N NN' exp
2kT
_

,
A
+
B
A
+
A
+
B
A
+
A
+
B
A
+
A
+
A
+
B
A
+
A
+
B
A
+
A
+
A
+
B
A
+
B
A
+
where N is the number of sites per cm
3
that could be left vacant
N is the no. of alternative interstitial per cm
3
.
w
f
is the work necessary to form a Frenkel defect, K is the gas constant and T is absolute
temp.
METAL EXCESS DEFECT
F-centres : This arises due to absence of anion from its Lattice
site, leaving a hole which is occupied by an electron thereby
maintaining the electrical balance. When compound such as
NaCl, KCl LiH or TiO are heated with excess of their
constituent metal vapours or treated with high energy radiation,
they become deficient in negative ion and their formula may be
1
AX , where = small fraction.
Anion sites occupied by electrons in this way are called F
centres.
More the no. of F-centres, more is the colour of compound.
A
+
B A
A
+
B B A
A
+
A A
A
+
B A A B
B
B
A
+
+ +
+ +
+ +
e

12
NARAYANA
Interstitial ions and electrons : Metal excess defect also occur when an extra +ve ion occupies on
interstitial position in the lattice, the electrical neutrality is maintained by the inclusion of an interstitial
electron. The composition may be represented by general formula X A
1 +
. The example include ZnO,
CdO, Fe
2
O
3
and Cr
2
O
3
.
METAL DEFICIENCY DEFECT
This type of compound is represented by the formula X A
1
. This deficiency can occur in two ways :
(i) Positive ion absent : If a positive ion is absent from its lattice site, the charges can be balanced by
an adjacent metal ion having an extra +ve charge. e.g. FeO, NiO, -TiO, FeS and CuI.
A B A
A
+
B B A
A
+
B A A
A
+
B A A B
B
B
+ +
+
2+
+
+ +
A B A
A
+
B B A
A
+
B A A
A
+
B A A B
B
B
A
+ +
+ +
+ 2+
+ +
B
Positive ion absent Extra interstitial negative ion
(ii) Extra interstitial negative ion : It is possible to have an extra negative ion in an interstitial
position and to balance the charges by means of an extra charge on an adjacent metal ion.
RADIUS RATIO
The ratio of the radius of cation to that of anion in an ionic crystalline solid, is called radius ratio.
Radius ratio =
) r ( anion of Radius
) r ( cation of Radius
+
The relation between the radius ratio (r
+
/ r
) and co-ordination number is quite often known as Radius

ratio rule. This helps in predicting the structures of ionic crystals. The same has been depicted in the
table.
Radius ratio Possible Co-ordination Structural Examples
(r
+
/ r
) number of cation Arrangement

155 . 0
2 Linear
0.155 0.225 3 Trigonal planar B
2
O
3
0.225 0.414 4 Tetrahedral ZnS, CuCl, CuBr, HgS
0.414 0.732 6 Octahedral NaCl, KBr, MgO, CaO, CaS, NaBr
0.732 1 8 Cubic CsCl, CsBr, CsI, NH
4
Br
Larger the cation more will be its co-ordination number due to increase of its radius ratio.
As the radius ratio increases more and more beyond 0.732, anion more farther and farther apart and
cubic void are generated.
13
EXAMPLES : 10
In the crystal of an ionic compound, the anions B
2
form a closed packed lattice and cations A
+
occupy all
the tetrahedral voids. What is the simplest formula of the compound ?
SOLUTION :
We know that in a close packed lattice involving anions B
2
having tetrahedral voids, there are two
tetrahedral sites for each anion and both are occupied by the cations A
+
.
Thus, for one anion (B
2
), there are two cations (A
+
)
Formula of the compound = A

2
B.
EXAMPLES : 11
A solid AB has the NaCl structure. If radius of the cation A
+
is 120 pm. Calculate the maximum value
of the radius of the anion B.
SOLUTION :
Since NaCl has octahedral structure.
The limiting ratio
A
B
r
0.414
r
+

,
or pm 290
414 . 0
120
414 . 0
r
r
A
B

+
STRUCTURE OF SIMPLE IONIC COMPOUNDS

Anions (large in size) form a close packed arrangement but cations (smaller in size) occupy the interstitial
sites resulting from the close packing of the anions e.g. NaCl, ZnS, CsCl etc.
In CaF
2
, Ca
2+
ions from the close packed arrangement while the F
ions fit in the interstitial sites.

In a close packed arrangement, the number of octahedral sites is half the number of tetrahedral sites.
For the radius ratio more than a minimum value or limiting value, close packed arrangement may open
slightly to accommodate the anions that are of bigger size.
Greater the co-ordination number (CN) more is the stability of ionic crystal due to greater forces of
attraction.
The different ionic compounds can have the following type of structures.
(i) Ionic compounds of AB type
(ii) Ionic compounds of AB
2
type
(iii) Ionic compounds of A
2
B type
STRUCTURES OF IONIC COMPOUNDS OF AB TYPE
Ionic compounds of the type AB suggest that in their crystal lattice A
+
and B
ions are present in the ratio of

1 : 1. These compounds have following three types of structures.
Rock salt (NaCl) type structures.
Cesium chloride (CsCl) type structure.
Zinc blende (ZnS) type structure.
14
NARAYANA
ROCK SALT (NaCl) TYPE STRUCTURE
Cl ion surrounded
octahedrally by six Na ions

+
Na surrounded
octahedrally by six Cl ions
+
ion
Fig. Sodium Chloride Structure
Characteristics:
NaCl is composed of Na
+
ion and Cl
ions.
The ionic radius of Na
+
and Cl
ion are 95 pm and 181 pm respectively. Thus radius ratio is

Na
Cl
r
95
0.525
r 181
+

The structure is octahedral in which Cl
ion constitute a cubic closed packed and Na

+
ions occupy
the octahedral voids.
The coordination number is 6 : 6 ie. each Na
+
ion is surrounded by six Cl
ions and vice versa.

A unit cell of NaCl consists of four NaCl units.
Other examples having similar structure are
(i) Halide of Li, Na, K, Cs.
(ii) Halide of Ammonium.
(iii) Oxides and sulphides of Mg, Ca, Sr & Ba.
(iv) Halides of Ag (Except AgI)
(v) CaCO
3
and CaC
2
CESIUM CHLORIDE (CsCl) TYPE STRUCTURES
Characteristics :
(i) The crystal is composed of Cs
+
and Cl
ions and their ionic radii are 160 pm and 181 pm respectively.
The radius ratio for the crystal is :
r Cs 160 pm
0.889
r Cl 181pm
+

The radius ratio suggests a body centred cubic structure. However, it is more than the ideal ratio which is
0.732.
(ii) The Cl
ions are present at the eight corners of the unit cell while one Cs
+
ion is present in the centre
of the body as shown in the fig.(a)
15
(iii) Each Cs
+
ion is surrounded by 8 Cl
ions and each Cl
ion by 8 Cs
+
ions. Thus, the coordination
number of each ion is 8 or these are in 8 : 8 co-ordination.
(iv) The contribution by all the 8 Cl
ions at the corners is 1 while by the Cs

+
ion present in the centre of
body is also 1. Therefore, the unit cell of CsCl consist of one Cs
+
ion and one Cl
ion and the formula

of cesium chloride is CsCl.
= Cs
+
= Cl
(a) (b)
Fig. Cesium chloride structure
ZINC BLENDE (ZnS) TYPE STRUCTURE
Fig. Structure of Zinc Blende (ZnS)
Characteristics :
(i) The sulphide ions (S
2
) with radius = 184 pm adopt cubic close packed arrangement (ccp) i.e. S
2
ions are present at all the corners as well as at the centre of each face.
(ii) The radii of Zn
2+
and S
2
ions are 74 pm and 184 pm respectively. Therefore, the radius ratio is :
2
2
Zn
S
r
74 pm
0.402
r 184 pm
+

(iii) Each Zn
2+
ion present occupies a tetrahedral site. As there are two tetrahedral sites per atom in a
close packed arrangement one half of these sites are occupied by Zn
2+
ions whereas the remaining
half are vacant. Thus Zn
2+
ions are present at the alternative sites as shown in fig.
(iv) Each Zn
2+
ion is surrounding by four S
2
ions which are directed towards the four corners of a
tetrahedron. Similarly each S
2
ion is also surrounding by four Zn
2+
ions. Thus, coordination number
of both these ions is 4 and these are also present in the ratio of 4 : 4.
(v) Other examples of this type are : Chloride, bromides and iodides of copper, silver iodide, beryllium sulphide
etc.
STRUCTURES OF IONIC COMPOUNDS OF AB
2
TYPE
These are the crystalline ionic solids in which cations and anions are in the ratio 1 : 2. Most of these
compounds have calcium fluoride (CaF
2
) type structure which is also knows as fluorite structure.
16
NARAYANA
= Ca
2+
= F
Fig. Structure of Calcium Fluoride (Fluorite Structure)

Characteristics
(i) The number of F
ions is twice the number of Ca

2+
ions i.e. Ca
2+
and F
ions are in the ratio 1 : 2.

The radii of Ca
2+
and F
ions are 99 pm and 136 pm respectively. Therefore, radius ratio is :

Ca
F
r
(99pm)
0.73
r (136pm)

2+
(ii) The radius ratio suggests a body centred cubic structure in which the Ca
2+
ions are present at the
corners and at the centre of each face of the cube.
(iii) The radius ratio suggests that each Zn
2+
ion present occupies a tetrahedral site. As there are two
tetrahedral sites per atom in a close packed arrangement, one half of these sites are occupied by
Zn
2+
ions whereas the remaining half are vacant. Thus, Zn
2+
ions are present at the alternative sites.
(iv) Each Zn
2+
ion is surrounded by four S
2
ions which are directed towards the four corners of a
tetrahedron. Similarly each S
2
ion is also surrounded by four Zn
2+
ions. Thus, coordination number
of both these ions is 4 and these are also present in the ratio of 4 : 4.
The other example of this type of Lattice are: BaF
2
, BaCl
2
, SrF
2
, SrCl
2
, CdCl
2
, PbF
2
etc.
ANTIFLUORITE STRUCTURE IN IONIC COMPOUNDS OF A
2
B TYPE
= Na
O ion
(in fcc arrangement)
2
Na ion
(at tetrahedral hole)
+
= O
+
2
Fig. Structure of Na
2
O (Antifluorite Structure)
(a) The compounds of A
2
B type structure is known as antifluorite structure.
(b) In this structure, the positions of the cations and anions as compared to fluorite structure get reversed
i.e. the smaller cations occupy the position of fluoride ions while the anions with bigger size occupy
the positions of calcium ions.
(c) Sodium oxide (Na
2
O) is an example of antifluorite structure.
(d) The oxide ions (O
2
) have ccp arrangement and Na
+
ions occupy the tetrahedral voids.
17
(e) Thus there are two tetrahedral sites per atom in close packed arrangement and these are occupied
by Na
+
ions.
(f) Each Na
+
ion is surrounded by four O
2
ions and each O
2
ions is surrounded by eight Na
+
ions. The
C.N. is 4 : 8.
(g) There are several oxides and sulphides of the metals with antifluorite structure e.g. Li
2
O, K
2
O,
Rb
2
O and Rb
2
S.
EFFECT OF PRESSURE AND TEMPERATURE ON CRYSTAL
STRUCTURE
At ordinary temperature and pressure, chlorides, bromide and iodides of alkali metals lithium, sodium,
potassium and rubidium and halides of silver have NaCl type structure with 6 : 6 co-ordination.
NaCl structure transform to CsCl structure at high pressure in which the ions are in the ratio 8 : 8.
When high temperature of 760 K is applied on cesium chloride (CsCl), with co-ordination of 8 : 8, it
changes sodium to chloride with co-ordination of 6 : 6.
BRAGGS LAW
When X-rays are incident on a crystal face, they penetrate into the crystal and strike the atoms in
different planes. From each of these planes, X-rays are deflected. Bragg presented a relationship between
the wavelength of the X-rays and the distance between the planes, such as
sin d 2 n
where n is an integer such as, 1, 2, 3, ..., is the wavelength, d is the distance between repeating planes
of particles and the angle of deflection or glancing angle. Two parallel layers of the crystals are shown
with the help of horizontal lines separated from each other by distance d. Two waves comprising X-rays
that are in plane strike against the crystal and after reflection emerge from the crystal.

C
D B
A
d
E
Fig. X-ray diffraction by regularly spaced constituents in a crystal
Further, the wave emerging along path AE is ahead of the wave that follows the path CD. The difference
in the distance travelled by the two rays after reflection also called path difference is :
Path difference = BC + CD = AC sin
+ AC sin = 2d sin
This must be an integral multiple of wave length i.e. n . Therefore.
n 2d sin (Bragg Equation)
EXAMPLES : 12
X-rays of wavelength 1.54 strike a crystal and are observed to be deflected at an angle of 22.5A.
Assuming that n = 1. Calculate the spacing between the planes of atoms that are responsible for this
reflection.
18
NARAYANA
SOLUTION :
According to Braggs law,
sin d 2 n
Given n = 1, , 54 . 1
22.5 A
01 . 2
383 . 0 2
54 . 1
5 . 22 sin 2
54 . 1
d
EXAMPLES : 13
If NaCl is doped with 10
3
mol percent of SrCl
2
what is the concentration of cation vacancy?
SOLUTION :
Na
+
Cl
Na
+
Cl
Cl
Cl
Na
+
Sr
2+
Cl
Na
+
Cl
Cl
Na
+
Cl
Na
+
Number of cationic vacancies per mol
18
23 3
10 023 . 6
100
10 023 . 6 10

vacancies per mol.

CLOSEST PACKING
In crystals the atoms, ions or molecules are arranged in a
regular way in a three-dimensional space. The arrangement
has minimum energy and hence maximum stability. For
maximum stability, a constituent in the aggregate must be
surrounded by the maximum number of neighbours. For
maximum number of contacts, each constituent of the
crystal must be packed as closely as possible. In a two-
dimensional plane the closest arrangement being that in
which each sphere is in contact with six other spheres.
This layer
is denoted by A.
To obtain the closest packing in space, the spheres are
placed over the layer obtain the closest packing in space,
the spheres are placed over the layer A in a regular manner.
There are six vacant sites or triangular pockets around
any sphere in layer A. In fig around a sphere X these sites
are labelled as 1, 2, 3, 4, 5 and 6. We can place only three
spheres touching each other in alternate vacant sites, e.g.
either in 1, 3 and 5 or in 2, 4 and 6.
Suppose the second layer is constructed by placing the
spheres in the vacant sites labelled as 1, 3 and 5 then the
sites marked 2, 4 and 6 are left unoccupied. This layer is
denoted by B.
A
B
A
C
B
A
B
A
B
A
Y
6
5
4
3
2
1
Close packed structures
(a) Hexagonal closest packing
(b) Cubical closest packing
(a)
(b)
x
The second layer again has two types of vacant sites.
Around any atom in the second layer, one set of vacant
sites lies just above the vacant sites 2, 4 and 6 of the first
layer and the other set lies above
19
the centres of the spheres of the first layer. Thus after the second layer is complete, there are two
different ways of placing the spheres in the third layer. If the spheres in the third layer are placed in the
vacant sites which are above the centres of the spheres of the first layer, then the third layer repeats the
arrangement of the first layer and we have only two types of layers, viz., ABAB .... etc. This is called a
hexagonal closest packing, hcp. fig (a) On the other hand, if the spheres are placed in the vacant sites
above 2, 4 and 6, a new arrangement (C) of the spheres in produced. Fig (b) The entire arrangement is
now of the type ABCABC ........... etc., and is referred to as a cubical closest packing, ccp or face
centred cubical closest packing, fcc.
The number of nearest neighbours (known as the coordination number) in each arrangement is twelve;
six in the same layer three in the layer above and three in the layer below it.
In the fcc structure, there are two types of vacant sites or holes : tetrahedral and octahedral. A tetrahedral
hole is surrounded by four spheres while an octahedral hole is the empty space surrounded by six spheres.
These vacant sites can accommodate other smaller atoms or molecules giving rise to a variety of different
structures.
(a) (b)
Fig. (a) Tetrahedral holes and (b) Octahedral holes in an fcc structure
In an fcc structure, there are eight tetrahedral holes per unit cell as shown in fig.(a) The number of
octahedral holes in the unit cell of the fcc structure is four as can be deduced from the following
considerations. In fig(b) each (X) mark represent a vacant site and there are twelve such vacant sites at
the edges of unit cubic lattice. The vacancy at an edge is common to four unit cells and hence the number
of such vacant sites per unit cell is
12
3
4

. In addition to these vacancies there is one octahedral hole at
the centre of the unit cell. Thus the total number of octahedral holes per unit cell is four.
Fig. Body centered cubical close-packed structure
Another less packed arrangement of spheres is the body centered cubic arrangement as shown in figure
above in which each sphere has eight nearest neighbours; four in the same plane, two above and two
below it in the adjacent layers. Since the coordination number in fcc or hcp structure is greater than that
in the bcc structures, the latter are therefore less denser.
PROPERTIES OF SOLIDS
There are three main types of properties.
1. ELECTRICAL PROPERTIES
Based on their conductivity, solids can be divided into three categories :
20
NARAYANA
(i) Conductors
(ii) Insulators
(iii) Semi-conductors
(i) Conductors : The solids through which electricity can flow to a large extent are called conductors.
They are either metallic conductors or electrolytic conductors. In the metallic conductors, the flow
of electricity is due to flow of electrons (electronic conductors) without any chemical change occurring
in the metal. While in electrolytic conductors like NaCl, KCl etc, the flow of electricity takes place
to a good extent only when they are taken in the molten state or in aqueous solution. The flow of
electricity is due to flow of ions.
(ii) Insulators: The solids which almost do not allow the electricity to pass through them are called
insulators e.g. S, P, plastics, wood, rubber etc.
(iii) Semi-conductors : The solids whose conductivity lies between those of metallic conductors and
insulators are called semi-conductors. The electrical conductivity of semi-conductors and insulators
is due to the presence of impurities and defects. Their conductivity increases with increase of
temperature as the defects (such as holes) increase with increase of temperature.
(a) Pure substances that show conductivity similar to that of silicon and germanium are called
intrinsic semiconductors.
(b) Electrical conductivity of semiconductors increases with increase of temperature because
with increase of temperature, large number of electrons can jump from valence band to
conduction band.
(c) Electrical conductivity of silicon and germanium is very low at room temperature. It can be
increased by doping with elements of Group 15 or Group 13.
(d) Similar to combination of Group 14 elements with those of Group 15 or Group 13, semiconductors
have been prepared by combination of elements of Group 13 and 15 (e.g. InSb, AlP and GaAs)
or Group 12 and 16 (e.g. ZnS, CdS, CdSe and HgTe)
(e) n- and p-type semiconductors are combined suitably to form a number of electronic components.
2. MAGNETIC PROPERTIES
Solids are divided into following categories on the basis of magnetic properties.
(i) Diamagnetic substances : Substances which are weakly repelled by the external magnetic field
are called diamagnetic substances e.g. TiO
2
, NaCl, benzene etc. The property thus exhibited is
called diamagnetism. This property is shown only by those substances which contain fully filled
orbitals i.e. no unpaired electron is present.
(ii) Paramagnetic substances : Substances which are attracted by the external magnetic field are
called paramagnetic substances. The property thus exhibited is called paramagnetism. This property
is shown by those substances whose atoms, ions or molecules contain unpaired electrons e.g. O
2
,
Cu
2+
, Fe
3+
etc. These substances, however, lose their magnetism in the absence of the magnetic
field.
(iii) Ferromagnetic substances : Substances which show permanent magnetism even in the absence
of the magnetic field are called ferromagnetic substances, e.g. Fe, Ni, Co, CrO
2
show ferromagnetism.
Such substances remain permanently magnetised, once they have been magnetised. This type of
magnetism arises due to spontaneous alignment of magnetic moments due to unpaired electrons in
the same direction, as shown in fig.(a)
21
(c) Ferrimagnetism (a) Ferromagnetism (b) Anti-ferromagnetism
(iv) Anti-Ferromagnetic substances : Substances which are expected to possess paramagnetism or
ferromagnetism on the basis of unpaired electrons but actually they possess zero net magnetic
moment are called anti-ferromagnetic substances, e.g. MnO. Antiferromagnetism is due to the
presence of equal number of magnetic moments in the opposite directions as shown in fig.(b)
(v) Ferrimagnetic Substances : Substances which are expected to possess large magnetism on the
basis of the unpaired electrons but acutally have small net magnetic moment are called ferrimagnetic
substances e.g. Fe
3
O
4
, ferrites of the formula M
2+
Fe
2
O
4
where M = Mg, Cu, Zn etc. Ferrimagnetism
arises due to the unequal number of magnetic moments in opposite direction resulting in some net
magnetic moment, as shown in fig(c). Each ferromagnetic substance has a characteristic temperature
above which no ferromagnetism is observed. This is known as curie temperature.
3. DIELECTRIC PROPERTY
(i) Piezoelectricity or Pressure electricity : Electricity is produced due to displacement of ions,
when mechanical stress is applied on such crystal. The electricity thus produced is called
piezoelectricity and the crystals are called piezoelectric crystals.
+ + + + + + +
+ + +
+ + +
Electric field
Dipoles aligned in
an ordered manner
Voltmeter
Mechanical stress
Mechanical stress
Fig. Production of electricity on applying mechanical stress on piezoelectric crystals
A few examples of piezoelectric crystals include titanates of barium and lead, lead zirconate (PbZrO
3
),
ammonium dihydrogen phosphate (NH
4
H
2
PO
4
) and quartz. These crystals are used as pick-ups in
record players where they produce electrical signals by application of pressure. They are also used
in microphones, ultrasonic generators and sonar detectors.
(ii) Pyroelectricity : Some piezoelectric crystals when heated produce a small electric current. The
electricity thus produced is called pyroelectricity (pyre means heat).
(iii) Ferroelectricity : In some of the piezoelectric crystals, the dipoles are permanently polarized even
in the absence of the electric field. However on applying electric field, the direction of polarization
changes. This phenomenon is called ferroelectricity due to analogy with ferromagnetism. Some
examples of the ferroelectric solids are barium titanate (BaTiO
3
), sodium potassium tartarate (Rochelle
salt) and potassium dihydrogen phosphate (KH
2
PO
4
). It may be pointed out here that all ferroelectric
solids are piezoelectric but the reverse is not true.
22
NARAYANA
(iv) Anti-ferroelectricity : In some crystals, the dipoles align themselves in such a way that alternately,
they point up and down so that the crystal does not possess any net dipole moment. Such crystals
are said to be anti-ferroelectric. A typical example of such crystals is lead zirconate (PbZrO
3
).
METAL SILICATES
Metal silicates have wide range of structures ranging from simple monomers to complex polymers,
however, the basic unit of all the silicate ions is tetrahedron nature. These tetrahedral occur singly, or by
sharing oxygen atoms in small groups, in small cyclic groups, in infinite chains or infinite sheets giving
various structures.
1. Simple orthosilicates : In these silicates SiO
4
4
tetrahedra do not share oxygen atoms with one
another and exist as discrete SiO
4
4
orthosilicate anions e.g. Mg
2
SiO
4
, Fe
2
SiO
4
and Zn
2
SiO
4
. In all
these compounds SiO
4
4
ion is linked to M
2+
ions through co-ordinate bond. [See Fig. (a)]
2. Pyrosilicates or islands : In these two SiO
4
4
tetrahedral share a common oxygen, island structures
having formula (Si
2
O
7
)
6
e.g. Pyrosilicates. [See Fig. (b)]
3. Ring or cyclic silicate anions : Ring anions are obtained when two oxygen atoms of each
tetrahedron are shared with others. (Si
3
O
9
)
6
and (Si
6
O
18
)
12
. General formula of any such anion
must be (Si
n
O
3n
)
2n
. [See Fig. (c)&(d)]
(a) SiO
4
4
(b) (Si O )
2 7
5
(c) (Si O )
3 9
6
(d) (Si O )
6 18
12
(e) (SiO ) chain
3 n
2
(f) (Si O ) layer
2 5 n
2
23
4. Infinite chain silicates : These are of two types the pyroxenes which contain single strand chains
of composition (SiO
3
2
)
n
and amphiboles which contain double strand cross-linked chains of composition
(Si
4
O
11
6
)
n
. General formula of the anion in a pyroxene is the same as in a silicate with cyclic anion
e.g. Diopside (MgCaSi
2
O
6
). Various asbestos minerals are examples of chain silicates (amphiboles).
5. Infinite sheet Silicates : When three oxygen atoms of each SiO
4
tetrahedron are shared, the two
dimensional sheet structures with general formula of (Si
2
O
5
2
)
n
are obtained e.g. clay.
[See Fig. (e)]
6. Framework silicate : Three dimensional network is obtained when all the four oxygen atoms of
each of SiO
4
tetrahedron are shared. e.g. Quartz and zeolites. The general formula of framework
silicate is SiO
2
. [See Fig. (f)]
24
NARAYANA
EXERCISE
Section A : (i) True and False Statements
(ii) Fill in the Blanks
(iii) Assertion-Reason Type Questions
Section B : (i) Multiple Choice Questions
(ii) MCQs asked in Competitive Examinations
Section C : Subjective Questions
25
EXERCISES
SECTION- A
TRUE AND FALSE STATEMENTS
1. The number of atoms in a unit cell having f.c.c. structure is 2
2. The electricity produced by applying mechanical stress on a crystal is called piezoelectricity.
3. Quartz is amorphous whereas silica is crystalline.
4. Frankel defect not found in pure alkali metal halides.
5. Fe
0.95
O is called stoichiometric oxide of iron.
6. Crystalline solids are anisotropic.
7. Silicon carbide is a covalent crystal.
8. In (hcp) systems, each sphere is surrounded by eight other spheres.
9. The number of atoms per unit cell of body-centred cube is 2.
10. Schottky defect in crystal results in appreciable increase in its density.
FILL IN THE BLANKS
1. On applying __________________ pressure, NaCl structure changes to CsCl type strucgture.
2. As the radius of cation increases, C.N. __________________
3. No. of tetrahdral voids is __________________ the no. of octahidal void.
4. Iron, Nickel, copper, silver and gold crystallises in __________________ structure.
5. It is observed that NaCl crystal at room temperature there are about 10
22
ions and 10
6
schottky pairs per
cm
3
. It means that there is one schottky pair per __________________ ions.
6. The crystal structure of CsCl is __________________ .
7. A face-centred point is shared by __________________ unit cells.
8. In face-centred cubic structure the empty space is __________________ %.
9. In hcp mode of packing, a sphere has coordination number __________________ .
10. The presence of a trace of arsenic in germanium makes it __________________ .
26
NARAYANA
ASSERTION-REASON TYPE QUESTIONS
I n each of the following questions two statements are given as Assertion A and Reason R. Examine the
statements carefully and answer the questions according to the instructions given below :
" Mark (1) if both A and R are correct and R is the correct reason of A.
" Mark (2) if both A and R are correct and R is not the correct reason of A.
" Mark (3) if A is correct and R is wrong.
" Mark (4) if both A and R are wrong.
1. Assertion A : In crystal lattice the size of the cation is larger in octahedral hole than in tetrahedral hole.
Reason R : Cations occupy more space than anions in crystal packing.
(1) (2)
(3) (4)
2. Assertion A : In a ccp lattice made up of Y
ions, all the tetrahedral voids are occupied by X

+
ions;
hence the formula of the solid is X
2
Y.
Reason R : In a ccp lattice number of tetrahedral voids formed is twice the number of ions making the
lattice.
(1) (2)
(3) (4)
3. Assertion A : NaCl crystal unit cell has fcc arrangement.
Reason R : There are 4 units of NaCl present per unit cell.
(1) (2)
(3) (4)
4. Assertion A : A crystal having fcc structure is more closely packed than a crystal having bcc structure.
Reason R : Packing fraction for fcc structure is double that of bcc structure.
(1) (2)
(3) (4)
5. Assertion A : The two ions A
+
and B
have radii 88 and 200 pm respectively. Coordination number of

A
+
will be 6.
Reason R : When r
+
/r
= 0.414 0.732, the coordination number is 6.

(1) (2)
(3) (4)
6. Assertion A : Covalent crystals have the highest melting point.
Reason R : Covalent bonds are stronger than ionic bonds.
(1) (2)
(3) (4)
7. Assertion A : CsCl as body-centred cubic arrangement.
Reason R : CsCl has one Cs
+
ion and 8 Cl
ions in its unit cell.

(1) (2)
(3) (4)
8. Assertion A : Triclinic system is the most unsymmetrical system.
Reason R : No axial angle is equal to 90 in triclinic system.
(1) (2)
(3) (4)
9. Assertion A : Antiferromagnetic substances on heating to high temperature become paramagnetic.
Reason R : On heating, randomisation of spins occur.
(1) (2)
(3) (4)
10. Assertion A : In any ionic solid, [MX], with Schottky defects, the number of positive and negative ions
are same.
Reason R : Equal number of cation and anion vacancies are present.
(1) (2)
(3) (4)
27
SECTION- B
MULTIPLE CHOICE QUESTIONS
1. A mineral having the formula AB
2
crystallizes in the c.c.p. lattice, with A atoms occupying the lattice
points. The CN of A is 8 and that of B is 4. What percentage of the tetrahedral sites is occupied by B
atoms?
(1) 25% (2) 50%
(3) 75% (4) 100%
2. CsBr has b.c.c. structure with edge length 4.3. The shortest inter ionic distance in between Cs
+
and Br
is
(1) 3.72 (2) 1.86
(3) 7.44 (4) 4.3
3. The formula for determination of density of cubic unit cell is
(1)
3 0
3
cm g
M z
N a

(2)
3
3
0
cm g
a M
N z

(3)
3
0
3
cm g
N z
M a

(4)
3
3
0
cm g
a N
M z

4. The closest-packing sequence ABAB ..... represents

(1) Primitive cubic packing (2) Body-centred cubic packing
(3) Face-centred cubic packing (4) hexagonal packing
5. In Braggs equation for diffraction of X-rays n represents
(1) The number of mole (2) Quantum number
(3) The order of reflection (4) Avogadros number
6. Tetragonal crystal system has the following unit cell dimensions
(1) a = b = c and 90
(2) 90 and c b a
(3) 90 and c b a
(4) 120 , 90 and c b a
7. In a solid lattice, the cation has left a lattice site and is located at interstitial position, the lattice defect is
(1) Interstitial defect (2) Vacancy defect
(3) Frenkel defect (4) Schottky defect
8. Each unit cell of NaCl consists of 13 chloride ions and _______.
(1) 13 Na
+
ions (2) 14 Na
+
ions
(3) 6 Na
+
ions (4) 8 Na
+
ions
9. Germanium or silicon becomes semi-conductor due to
(1) Schottky defect
(2) Chemical impurity
(3) Frenkel defect
(4) None of these
28
NARAYANA
10. Which one of the following is correct?
(1) Schottky defect lowers the density
(2) Frenkel defect increases the dielectric constant of the crystals
(3) Stoichiometric defects make the crystals good electrical conductors
(4) All of these
11. The electrons trapped in anion vacancies in metal excess defects are called
(1) Mobile electrons (2) Trapped electrons
(3) Valence electrons (4) F-centres
12. The correct statement regarding F-centre is
(1) Electrons are held in the voids of crystals
(2) F-centre provides colour to the crystals
(3) Conductivity of the crystal increases due to F-centre
(4) All of these
13. Crystals where dipoles may align themselves in an ordered manner, so that there is a net dipole moment,
exhibit
(1) Pyro-electricity (2) Piezo-electricity
(3) Ferro-electricity (4) Anitferro electricity
14. Some of the polar crystals, on heating produce a small electric current called
(1) Pyro-electricity (2) Piezo-electricity
(3) Ferro-electricity (4) Anitferro-electricity
15. Germanium is an example of
(1) An intrinsic semiconductor (2) An n-type semiconductor
(3) A p-type semiconductor (4) Insulator
16. Which type of semiconductor is obtained on mixing the arsenic into the silicon?
(1) n-type (2) p-type
(3) Internal (4) both (1) and (2)
17. If indium is added in small quantity of Ge metal, we get
(1) An n-type semiconductor (2) A p-type semiconductor
(3) Rectifier (4) Insulator
18. When n- and p-type semiconductors are allowed to come into contact
(1) Some electrons will flow from n to p (2) Some electrons will flow from p to n
(3) The impurity element will flow from n to p (4) The impurity element will flow from p to n
19. The electrical conductivity of semiconductors
(1) Increases with temperature (2) Decreases with temperature
(3) Remains constants on heating (4) None of the above
20. Super conductors are substances which
(1) Conduct electricity at low temperature (2) Conduct electricity at high temperatures
(3) Offer high resistance to the flow of current (4) Offer no resistance to the flow of current
29
21. The phenomenon of superconductivity was first discovered by
(1) Einstein (2) Soddy
(3) Hund and Mulliken (4) Kammerlingh Onnes
22. Which substances possess zero resistance at 0 K?
(1) Conductors (2) Semiconductors
(3) Superconductors (4) Insulators
23. Amorphous solids are
(1) Solid substances in real sense (2) Liquids in real sense
(3) Supercooled liquids (4) Substances with definite M.P.
24. Which of the following is not an example of molecular crystal?
(1) Hydrogen (2) Iodine
(3) Ice (4) Sodium chloride
25. The pure crystalline substance on being heated gradually first forms a turbid liquid at constant temperature
and still at higher temperature turbidity completely disappears. The behaviour is a characteristic of
substance forming
(1) Allotropic crystals (2) Liquid crystals
(3) Isomeric crystals (4) Isomorphous crystals
26. The co-ordination number of a body-centred atom in cubic structure is
(1) 4 (2) 6
(3) 8 (4) 12
27. The radius of an ion in a body centred cube of edge a is
(1)
2
a
(2)
2
4
a
(3)
3
4
a
(4) a
28. The fraction of the total volume occupied by atoms in a simple cube is
(1)
2
(2)
8
3
(3)
6
2
(4)
6
29. A substance A
x
B
y
crystallizes in an f.c.c. lattice in which atoms of A occupy each corner of the cube
and atoms of B occupy the centres of each face of the cube. Identify the correct composition of the
substance A
x
B
y
.
(1) AB
3
(2) A
4
B
3
(3) A
3
B (4) Composition cannot be specified
30. In a closed packed lattice, the number of octahedral sites as compared to tetrahedral ones will be
(1) Equal (2) Half
(3) Double (4) None of these
30
NARAYANA
31. CsCl on heating to 760 K changes into
(1) Liquid (2) NaCl structure
(3) ZnS structure (4) None of these
32. Compounds having NaCl type structure when subjected to high pressure changes into
(1) Unstable compound (2) CsCl type structure
(3) ZnS type structure (4) None of the three
33. In a face centred cubic cell, an atom at the face centre is shared by
(1) 4 unit cells (2) 2 unit cells
(3) 1 unit cell (4) 6 unit cells
34. Ionic solids are characterised by
(1) Good conductivity in solid state (2) High vapour pressure
(3) Low melting point (4) Solubility in polar solvents
35. Silicon is a
(1) Conductor (2) Semiconductor
(3) Non conductor (4) Metal complex
36. On adding a little phosphorus to silicon, we get a/an
(1) n-Type semiconductor (2) p-Type semiconductor
(3) Metallic conductor (4) Insulator
37. Piezoelectric crystals are used in
(1) Radio (2) TV
(3) Record player (4) Refrizerator
38. Glass is
(1) Supercooled liquid (2) Crystalline solid
(3) Liquid crystal (4) None of these
39. In a crystal pair of ions are missing from normal sites. This is an example of
(1) F-centres (2) Interstitial defect
40. Frenkel defect generally appears in
(1) AgBr (2) ZnS
(3) AgI (4) All of these
41. Missing of one cation and one anion from the crystal lattice is called :
(1) Ionic defect (2) Crystal defect
(3) Schottky defect (4) Frenkel defect
42. In a closed packed array of N spheres, the number of tetrahedral holes are
(1) N/2 (2) N
(3) 4N (4) 2N
43. For an ionic crystal of general formula AX and co-ordination number 6, the value of radius ratio will
be
(1) Greater than 0.73 (2) In between 0.732 and 0.414
(3) In between 0.41 and 0.22 (4) Less than 0.22
31
44. Close packing is maximum in the crystal lattice of:
(1) Face-centred cubic (2) Body-centred cubic
(3) Simple-centred cubic (4) None of these
45. In the crystal of CsCl, the nearest neighbours of each Cs ion are
(1) Six chloride ions (2) Eight Cs ions
(3) Six Cs ions (4) Eight chloride ions
46. Schottky defect in crystals is observed when
(1) An ion leaves its normal site and occupies an interstitial site
(2) Equal number of cations and anions are missing from the lattice
(3) Unequal number of cations and on ions are missing from the lattice
(4) Density of the crystal is increased
47. Pick up the correct statement
(1) The ionic crystal of AgBr does not have Schottky defect
(2) The unit cell having crystal parameters, a=b
c, == 90, =120 is hexagonal

(3) In ionic compounds having Frenkel defect, the ratio r
+
/r
is high
(4) The coordination number of Na
+
ion in NaCl is 4
48. When NaCl is dopped with MgCl
2
the nature of defect produced is
(1) Interstitial defect (2) Frenkel defect
(3) Schottky defect (4) None of these
49. The second order Bragg diffraction of X-rays with 1.00 from a set of parallel planes in a metal
occurs at an angle of 60. The distance between the scattering planes in the crystal is
(1) 0.575 (2) 1.00
(3) 2.00 (4) 1.15
50. If we mix a pentavalent impurity in a crystal lattice of germanium, what type of semiconductor formation
will occur?
(1) p-Type (2) n-Type
(3) Both (1) and (2) (4) None of the two
32
NARAYANA
MCQS ASKED IN COMPETITIVE EXAMINATIONS
1. The fraction of total volume occcupied by the atoms present in a simple cube is: [CBSE PMT 2007]
(1)
4
(2)
6
(3)
3 2
(4)
4 2
2. The appearance of colour in solid alkali metal halides is generally due to [CBSE PMT 2006]
(1) Interstitial positions (2) F-centres
(3) Schottky defect (4) Frenkel defect
3. CsBr crystallises in a body centred cubic lattice. The unit cell length is 436.6 pm. Given that the atomic
mass of Cs=133 and that of Br = 80 amu and Avogadro number being 6.02 10
23
mol
1
, the density of
CsBr is
(1) 4.25 g/cm
3
(2) 42.5 g/cm
3
(3) 0.425 g/cm
3
(4) 8.25 g/cm
3
[CBSE PMT 2006]
4. In face-centred cubic unit cell, edge length is [DPMT 2005]
(1)
4
r
3
(2)
4
r
2
(3) 2r (4)
3
r
2
5. In a face-centred cubic lattice,unit cell is shared equally by how many unit cells?[CBSE P MT 2005]
(1) 4 (2) 2
(3) 6 (4) 8
6. If Z is the number of atoms in the unit cell that represents the closest packing sequence.... ABC
ABC....., the number of tetrahedral voids in the unit cell is equal to [A.I.I.M.S. 2005]
(1) Z (2) 2Z
(3) Z/2 (4) Z/4
7. What type of crystal defect is indicated in the diagram below? [A.I.I.M.S. 2003]
Na Cl Na Cl Na Cl
+ + +
Cl Cl Na Na
Na Cl Cl Na Cl
Cl Na Cl Na Na
+ +
+ +
+ + +
(3) Interstitial defect (4) Frenkel and Schottky defects
8. The crystal system of a compound with unit cell dimensions a = 0.387, b = 0.387 and c = 0.504 nm and
= = 90 and = 120 is [A.I.I.M.S 2004]
(1) cubic (2) hexagonal
(3) orthorhombic (4) rhombohedral
9. The liquefied metal expanding on solidification is [A.I.I.M.S 2004]
(1) Ga (2) Al
(3) Zn (4) Cu
33
10. The pyknometric density of sodium chloride crystal is 2.165 10
3
kg m
3
while its X-ray density is
2.178 10
3
kg m
3
. The fraction of the unoccupied sites in sodium chloride crystal is
[C.B.S.E. P.M.T 2002]
(1) 5.96 (2) 5.96 10
2
(3) 5.96 10
1
(4) 5.96 10
3
11. Which of the following metal oxides is anti-ferromagnetic in nature? [M.P.P.E.T. 2002]
(1) MnO
2
(2) TiO
2
(3) VO
2
(4) CrO
2
12. To get n-type doped semiconductor, impurity to be added to silicon should have the following number of
valence electrons [K.C.E.T. 2001]
(1) 1 (2) 2
(3) 3 (4) 5
13. Addition of arsenic to germanium makes the latter a [Tamilnadu, CET 2002]
(1) Metallic conductor (2) Intrinsic semiconductor
(3) Mixed conductor (4) Extrinsic semiconductor
14. Semiconductors are derived from compounds of [Kerala MEE 2002]
(1) p-block elements (2) Lanthanides
(3) Actinides (4) Transition elements
15. A semiconductor of Ge can be made p-type by adding [Manipal PMT 2002]
(1) Trivalent impurity (2) Tetravalent impurity
(3) Pentavalent impurity (4) Divalent impurity
16. Due to Frenkel defect the density of ionic solids [M.P.P.E.T. 2002]
(1) Decreases (2) Increases
(3) Does not change (4) Changes
17. Which of the following crystals does not exhibit Frenkel defect? [M.P.P.E.T. 2000]
(1) AgBr (2) AgCl
(3) KBr (4) ZnS
18. The packing fraction for a body centred cubic is [M.P.P.M.T. 2000]
(1) 0.42 (2) 0.53
(3) 0.68 (4) 0.82
19. The number of octahedral sites per sphere in fcc structure is [M.P.P.M.T. 2000]
(1) 1 (2) 2
(3) 4 (4) 8
20. The interionic distance for cesium chloride crystal will be [M.P.P.E.T. 2002]
(1) a (2) a/2
(3) 2 / a 3 (4)
3 / a 2
34
NARAYANA
SECTION- C
SUBJECTIVE QUESTIONS
1. What is the contribution of the atom when it is placed at the centre of the edge in a unit cell of a cube ?
2. What is the atomic radius of the atom in body-centred cubic structure ?
3. What is the coordination number in hcp and ccp arrangements ?
4. Explain, why ionic crystals do not conduct electricity in solid state ?
5. Name the two important kinds of holes normally encountered in a closed packed structure. How many
such holes are present per sphere in a close packed structure ?
6. Explain the term dislocation in relation to crystal.
7. Which type of crystals exhibit piezo-electricity.
8. What is the coordination no of each sphere in ccp of spheres in three dimensions.
9. Mention one property which is caused due to presence of F-centre in solid.
10. What is the effect of pressure on NaCl type crystals.
11, A given solid can belong to one of the four crystal types, i.e., ionic, molecular, covalent and metallic.
Indicate the crystal type of the following :
(a) Diamond (b) Sodium chloride (c) Ice (d) Copper
(e) Boron nitride (f) Zinc oxide (g) Paraffin wax.
12. X-rays of wavelength 1.54 strike a crystal and are observed to be deflected at an angle of 22.5.
Assuming that n = 1, calculate the spacing between the planes of atoms that are responsible for this
reflection.
13. At room temperature, sodium crystallises in body-centred cubic lattice with a = 4.24. Calculate the
theoretical density of sodium (at. mass of Na = 23.0)
14. A compound formed by elements A and B crystallises in cubic structure where A atoms are at the
corners of a cube and B atoms are at the face centre. What is the formula of the compound ?
15. A solid AB has the NaCl structure. If radius of the cation A
+
is 120 pm, calculate the maximum value of
the radius of the anion B
.
16. In a cubic lattice, the closed packed structure of mixed oxides of the lattice is made up of oxide ions; one
eighth of the tetrahedral voids are occupied by divalent ions (A
2+
) while one half of the octahedral voids
are occupied by trivalent ions (B
3+
). What is the formula of the oxides?
17. If NaCl is doped with 10
3
mol percent of SrCl
2
, what is the concentration of cation vacancy?
18. A metal crystallises into two cubic phases, face-centred cubic (f.c.c.) and body-centred cubic (b.c.c.)
whose unit lengths are 3.5 and 3.0 respectively. Calculate the ratio of densities of f.c.c. and b.c.c.
19. Calculate the Miller indices of crystal planes which cut through the crystal axes at (i) (2a, 3b, c) (ii) (a,
b, c) (iii) (6a, 3b, 3c), (iv) (2a, 2b, )
20. The unit cell length of NaCl is observed to be 0.5627 nm by X-ray diffraction studies; the measured
density of NaCl is 2.164 g cm
3
. Correlate the difference of observed and calculated density and calculate
% of missing Na
+
and Cl
ions.
35
ANSWERS
SECTION - A
(True and False Statements)
1. False 2. True
3. False 4. True
5. False 6. True
7. True 8. False
9. True 10. False
(Fill in the Blanks)
1. High 2. increases
3. double 4. ccp
5. 10
16
6. B.c.c.
7. Two 8. 26
9. 12 10. Semi-conductor
(Assertion-Reason Type Questions)
1. (3) 2. (1)
3. (1) 4. (3)
5. (1) 6. (3)
7. (3) 8. (2)
9. (1) 10. (1)
36
NARAYANA
SECTION - B
(Multiple Choice Questions)
1. (4) 2. (1) 3. (4) 4. (4) 5. (3)
6. (2) 7. (3) 8. (2) 9. (2) 10. (4)
11. (4) 12. (4) 13. (2) 14. (1) 15. (1)
16. (1) 17. (2) 18. (1) 19. (1) 20. (4)
21. (4) 22. (3) 23. (3) 24. (4) 25. (2)
26. (3) 27. (3) 28. (4) 29. (1) 30. (2)
31. (2) 32. (2) 33. (2) 34. (4) 35. (2)
36. (1) 37. (3) 38. (1) 39. (4) 40. (4)
41. (3) 42. (4) 43. (2) 44. (1) 45. (4)
46. (2) 47. (2) 48. (3) 49. (4) 50. (2)
(MCQs asked in Competitive Examinations)
1. (2) 2. (2) 3. (1) 4. (2) 5. (3)
6. (2) 7. (2) 8. (2) 9. (1) 10. (4)
11. (1) 12. (4) 13. (4) 14. (1) 15. (1)
16. (3) 17. (3) 18. (3) 19. (1) 20. (3)
SECTION - C
(Subjective Questions)
Answers are given in the separate booklet.

PMT Class XII Chemistry Solid State

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000000000.

c 90 White tin, SnO

c 90 Rhombic sulphur, KNO

c 90 , 120 Graphite, ZnO, CdS

Given, d = 1.99; M = 74.5; V = (6.29 10

Number of unit cell in 28.88 cm

% volume occupied by atom = 52.4

Volume occupied by atoms in a unit cell

% volume occupied by unit cell = 74

Distance between nearest neighbour (d) =

Radius of an atom (r) = d/2 =

% volume occupied in a unit cell = 68

Nearest neighbour distance (d) = 2r = 2 35.4 pm = 70.8 pm

Chemistry : The Solid State

) and co-ordination number is quite often known as Radius

) number of cation Arrangement

Formula of the compound = A

STRUCTURE OF SIMPLE IONIC COMPOUNDS

ions fit in the interstitial sites.

ions are present in the ratio of

ion are 95 pm and 181 pm respectively. Thus radius ratio is

ion constitute a cubic closed packed and Na

ions and vice versa.

ions and each Cl

ions at the corners is 1 while by the Cs

ion and the formula

Fig. Structure of Calcium Fluoride (Fluorite Structure)

ions is twice the number of Ca

ions are in the ratio 1 : 2.

ions are 99 pm and 136 pm respectively. Therefore, radius ratio is :

vacancies per mol.

ions, all the tetrahedral voids are occupied by X

have radii 88 and 200 pm respectively. Coordination number of

= 0.414 0.732, the coordination number is 6.

ions in its unit cell.

4. The closest-packing sequence ABAB ..... represents

c, == 90, =120 is hexagonal

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