Chapter - 2

SOLID STATE
Introduction
We know solids are the substances which have a definite volume and definite shape. A solid is nearly
incompressible state of matter with well definite shape, rigidity and definite volume. In case of solid
intermolecular forces are very strong. Whereas intermolecular distance is very small.

2.1 Classification of Solids:

Solids can be broadly classified into two types :
(1) Crystalline (2) Amorphous

Difference Between Crystalline and Amorphous Solids

S.No. Property Crystalline solids Amorphous solids

1. Geometry These have definite regular geometry These do not have definite orderly
which extends throughout the crystals arrangment.
i.e., these solids have long range order.

2. Melting Points These have sharp m.p. These do not have sharp m.p.

3. Symmetry These possess symmetry. These do not possess any symmetry.

4. Heat of Fusion These have definite heat of fusion These do not have definite heat of
fusion.

5. Interfacial Crystals are always guarded by planes These do not possess interfacial angle.
angles so that a definite angle exists between
two planes called interfacial angle.

6. Volume change There is a sudden change in volume There is no sudden change in volume
when it melts. on melting.

7. Isotropy and These are anisotropes i.e., their physical They are isotropic i.e., their physical
Anisotropy properties such as refractive index, properties such as refractive index
conductivity etc. have different values in conductivity etc. have same value in
different directions. all the directions.

Types of crystalline solids:

On the basis of the nature of the constituent particles, and the interparticle forces, crystalline solids
may be divided into four classes
(a) Covalent network solids
(b) Ionic solids
(c) Metallic solids
(d) Molecular solids

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Characteristics of Various Types of Solids

Characteristic Molecular Solids Covalent Network Metallic Solids Ionic Solids

1. Units that occupy Atoms or molecules Atoms Positive ions in a Positive and
Lattice points ‘sea of electrons’ negative ions
2. Binding forces Van der Waal’s forces Covalent bonding Metallic bonding ionic bonding
(weak intermolecular (shared pair of (extreme deloc- (electrostatic
forces) of following electrons) alised bond)– attraction
two types positively charged between positive
(i) London (dispersion) atomic cores and negative
forces surrounded by ions)
(ii)Dipole-dipole ‘sea’ of deloc-
forces alised electrons
3. Physical (i) Very soft. (i) Very hard (i) Hard or soft (i)Quite hard
Properties (ii) Low melting (ii) Very high (ii) Moderate to and brittle
points melting points high melting (ii)Fairly high
points melting
(iii) Non conductors (iii) Non conductors (iii) Good points
conductors
4. Examples Solid Ne, Solid NH3, Diamond, Cu, Fe, Ag NaCl, KNO3
ice (solid H2O), Carborundum(SiC), Na2SO4
dry ice (solid CO2) quartz(SiO2)

. Space Lattice : It may be defined as a three dimensional arrangement of points that shows, how
the atoms or ions are arrayed in space. Each point is individually called a lattice point.

Space Lattice z

c
Lattice point

a
x
b
Unit Cell c
 a
 y Representation of
b dimension of unit cell

. Crystal Lattice : When the lattice points in the space are replaced by actual atoms or ions then the
space lattice is called crystal lattice.

Crystal System : The unit cell in a 3-dimensions lattices is characterized by the length a, b, c and
their angles , , . These are known as unit cell parameters.

BRAVAIS LATTICES : An arrangement of spheres as given above leads to simple or primitive

unit cell, when there are points only at the corner of the unit lattice. However certain unit cells have
lattice points at other sides in additions to the corners. Such unit cell are called non-primitive unit

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cells. Bravais (1848) showed from geometrical considerations that there can be only 14 different
ways in which similar points (spheres) can be arranged.

These fourteen types of lattice are known as Bravais lattices. They can be divided into seven
crystal systems as shown below :

Crystal Systems Table

S.No. Crystal System Axial Characteristics Examples

1. Cubic a=b=c NaCl, KCl, CsCl, zinc blende,

 =  =  = 90º Cu, Ag, diamond
2. Tetragonal a=bc
 =  =  = 90º White tin, SnO2, TiO2
3. Orthorhombic abc
 =  =  = 90º Rhombic sulphur, KNO3,
PbCO3, PbSO4
4. Monoclinic a  b  c; Monoclinic sulphur, CaSO4,
 =  = 90º;   90º 2H2O,, Na2SO4, 10H2O
5. Rhombohedral a = b = c; Calcite, quartz,
or trigonal  =   90º As, Sb, NaNO3, ICl
6. Triclinic a  b  c; K2Cr2O7, H3BO3, CuSO4, 5H2O
      90º
7. Hexagonal a  b  c; Graphite
 =  = 90º;  = 120º

In case of cubic system which is the simplest crystal system, there are three types of lattices
depending upon the unit cell. These are :

(i) Simple Cubic Lattice. In this type of lattice, there are lattice points only at corners of each
unit cell.

(ii) Face Centred Lattice (fcc) :- In this type of lattice, there are points at the corners of the cube
with additional points at the centre of each face.

(iii) Body Centred Cubic Lattice (bcc) :- This type of lattice has points at the corners of a cube
with an additional point in the centre of the cube.

The Bravais lattice associated with the seven crystal systems are shown below.

 b

a 
Simple or Primitive Body centred Cubic
Face Centre

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CUBIC

Body centred End centred

Simple or Primitive
Face Centre

ORTHORHOMBIC

Simple Body centred Simple Body centred

TETRAGONAL MONOCLINIC

c
c

 
a
a  b
A B G
B b A
a G c b

RHOMBOHEDRAL
TRICLINIC
HEXAGONAL

Bravais lattices corresponding to different crystal systemsTable

S.No. System Number of Bravais Description of the lattices

lattices

1. Cubic 3 Simple, Face-centred, Body centred.

2. Tetragonal 2 Simple, Body-centred
3. Orthorhombic or Rhombic 4 Simple, Face-centred, End centred
Body - centred
4. Monoclinic 2 Simple, End-centred
5. Triclinic 1 Simple
6. Rhombohedral or trigonal 1 Simple
7. Hexagonal 1 Simple

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Types of symmetry in crystal Centre of

Symmetry H
H H
1. Centre of Symmetry :- Centre of symmetry of a crystal may
be defined as an imaginary point within a crystal such that any H
H
line through it intersects the crystal at equal distances in both H

directions e.g. staggered form of ethane possesses a centre of

symmetry.

The centre of symmetry is also called the centre of inversion because if the crystal is inverted
through the centre of symmetry, it is distinguishable from the original.

Every Crystal Possesses Only One Centre of Symmetry

2. Plane Of Symmetry : It is an imaginary plane passing through the crystal which can divide
crystal into two equal parts such that one part is exact mirror image of the other . These are
therefore also called mirror planes.

There are two types mirror planes.

(a) Rectangular mirror planes

(b) Diagonal mirror plane

Rectangular mirror plane Diagonal mirror plane

Axis of Symmetry or Axis of Rotation

An axis of symmetry or axis of rotation is an imaginary line, passing through the crystal such that
when the crystal is rotated about this line, it presents the same appearance more than once in one
complete rotation. i.e. through 360º.

360º
When the same appearance of crystal is repeated, on rotating through an angle of around an
n
imaginary axis it is called n-fold axis of symmetry where n– is known as order of axis.

Two-Fold Axis: If a similar appearance occurs two times in one complete rotation i.e. after a
rotation through 180º, the axis is called two fold axis of symmetry or diad axis.

Three-Fold Axis: If the original appearance occurs thrice it is called three fold axis of symmetry.

Two fold axis Three fold axis

of symmetry Four Fold Axis

(a) (b) (c)

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Four-Fold Axis : It is a line about which if a crystal is rotate then it regenerate its structure
after 90°.

Nearest Neighbouring Distance In Case of Identical Spheres: Nearest neighbouring distance

is the distance between the centres of any two touching spheres.

1. In case of SCC (Simple Cubic Lattice)

d
a

In a simple cubic lattice the edger length (a) = Nearest neighbouring distance

a = d = 2r

 r = a /2

2. Body Centred
B
(AB)2 = (AC)2 + (BC)2
r
 Body Diagonal)2 = (Face Diagonal)2 + (edge)2
r
= 2 (edge)2 + (edge)2
C
= 3 (edge)2 Ar

 (Body diagonal ) 2  3 (edge ) 2 

d est g
 ear orin
Also Body Diagonal = r + 2r + r = 4r N hb ce
ig a n
Ne dist
 (4r)2 = 3a2  4r = 3a

3
 r a
4

3
d = 2r  d a = nearest neighbouring distance
2

3. Face Centred Cubic Lattice

A B
Here (Face diagonal)2 = (edge)2 + (edge)2. r
r
Also face diagonal = r + 2r + r = 4r r


r
d


(4r)2 = 2 (edge)2 C D

4r = 2a

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2 1
r a  r a
4 2 2

2 1
 d a  a
2 2

Hence we can say

Unit Cell Distance between Radius

nearest neighbour

Simple cubic a a
2

a 2a a 2
Face Centred Cubic  a
2 = 2 2 2 4

3 3
Body Centred Cubic a a
2 4
4. Packing Fraction in Case of Identical Spheres

Packing fraction is the ratio of volume occupied by spheres to the total volume of the cube.

4
Volume occupied by sphere  r3  z
Packing Fraction = = 3
Total volume of cube
a3

where a = edge of cube

z = number of spheres per unit cell
Packing fraction for SCC

a
r= z=1
2
3
4 a
   z 4 
PF = 3  2  = 
8 3 6
a3

 PF =
6


 % volume occupied by spheres = × 100 = 53.4%
6

 
 % Free space = 100 1  6  = 47.6%
 

Packing fraction for BCC

3
r= z=2
4

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3
4  3 
 a 2 4 3 3 2
 
PF = 3  4  = 
3 64
a3

3
PF =
8
 % volume occupied = 68.04%
% Free space = 100 – 68.04 = 31.96%
Packing Fraction for FCC

2
r= a z=4
4

3
4  2 
 a 4
3  4  4 2 2
 PF = 3
=  4
a 3 64

2
=   0.7407
6

2
PF = 
6

% Volume occupied = 74.07%

% Free space = 25.93%

Calculation of Density of a System Crystal

Cubic Crystal

Let number of atom per unit lattice = n

Mass of unit cell = number of atom per unit cell (n) × Mass of one atom

Atomic Mass of Atom

Mass of each atom = Avogadro' s number N
A

n  M0 n  A0
Mass of unit cell = NA or NA

Mass of unit cell

Density of unit cell = Volume of unit cell

Length of edge = a pm

Volume of cube = a3 pm3 = a3  10–30cm3

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nM
Density = N  a 3  10 30 gm/cc
o

nM 10 30 nM 10
7
Density = 3 = 3
No  a 6.023  a

Unit Cell : The smallest repeating pattern in space lattice is called a unit cell.

Illustration 1: Metallic gold crystallizes in the face-centered cubic lattice. The length of the cubic unit cell
is a = 4.070 Å.
(a) What is the closest distance between gold atoms ?
(b) How many “nearest neighbours” does each gold atom have at the distance calculated in (a) ?
(c) What is the density of gold ?
(d) Prove that the packing factor for gold, the fraction of the total volume occupied by the
atoms themselves, is 0.74.

Solution: (a) Consider a corner gold atom. The closest distance to another corner atom is a. The
distance to an atom at the center of a face is one-half the diagonal of that face, i.e.,

1 a
(a 2 ) = <a
2 2

4.070
Thus the closest distance between atoms is 2 = 2.878 Å.

Fig. (1) Fig. (2)

(b) The problem is to find how many face centers are equidistant from a corner atom. Point
A in figure may be taken as the reference corner atom. In that same figure, B is one of
the face-center points at the nearest distance to A. In plane ABD in the figure there are
three other points equally close to A: the centers of the squares in the upper right, lower
left, and lower right quadrants of the plane, measured around A. Plant ACE, parallel to
the plane of the paper, also has points in the centers of each of the squares in the four
quadrants around A. Also, plane ACF, perpendicular to the plane of the paper, has points
in the centers of each of the squares in the four quadrants around A. Thus there are 12
nearest neighbors in all, the number expected for a close-packed structure. The same
result would have been obtained by counting the nearest neighbors around B, a face-
centered point.

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(c) For the face-centered cubic structure, with 8 corners and 6 face centers,

1 1
Mass per uniot cell = (8m) + (6m) = 4 m
8 2
where m is the mass of a single gold atom, 197.0 amu. Converting to grams,

 1g 
 
m = (197.0)  6.023  10 23  = 3.27  10–22 g
 

4m 4(3.27  10 –22 g)
and Density = = = 19.4 g/cm3
a3 (4.070  10 –8 cm) 3

(d) Since atoms at closest distance are in contact in a close-packed structure, the closest
distance between centers calculated in (a), a / 2 , must equal the sum of the radii of the
two spherical atoms, 2r. Thus, r = a/23/2. From (c), there are 4 gold atoms per unit cell.
Then,
3
4 3 4   a  a 3
Volume of 4 gold atoms = 4 3 r  = 4 3   4 3/2   =
    2  3 2

volume of 4 gold atoms a 3 / 3 2 

and Packing fraction = = 3 = 3 2 = 0.7405
vlume of unit cell a

rNa 
Illustration 2: KCl crystrallizes in the same type of lattice as does NaCl. Given that r  = 0.5 and
Cl
rNa 
rK  = 0.7, calculate (a) the ratio of the side of the unit cell for KCl to that for NaCl, and (b)
the ratio of density of NaCl to that of KCl.

Solution : Since NaCl crystallizes in the fcc unit cell, so

a
rNa   rCl – 
2
Where a = edge length of unit cell.

rNa 
Now rCl – = 0.5

rNa 
or 1 + r – = 1 + 0.5
Cl

rNa   rCl –
rCl – = 1.5 .....(1)

rK  rK   
 rCl  0.5 
rCl – = rNa  / 0.5 
 rNa 


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0.5 0.5  r  
= r  /r  =  Na  0.7 
0.7  rK  
Na K  

rK  0.5
or 1 + r  = 1 +
Cl 0 .7

rK   rCl – 1 .2
or rCl – = ....(2)
0.7

Divide (2) by (1)

rK   rCl – rCl – 1 .2
rCl –  r   r – = 0 .7  1 .5
Na Cl

rK   rCl –
or rNa   rCl – = 1.142

 a 
 rK   rCl   KCl 
aKCl/2  2 
or a NaCl/2 = 1.142  aKCl 
 and rNa   rCl   
 2 

aKCl
or a NcCl = 1.142

N M
density (d) = .
a 3 N0

Where N = number of atoms per unit cell

M = Molecular mass
N0 = Avogadro number
a = Edge length of unit cell

d NaCl N × M NaCl / (a NaCl ) 3 .N 0

=
d KCl N × M KCl / (a KCl )3 . N 0
3
 aKCl   M NaCl 
= a  .  
 NaCl   M KCl 
 58.5 
= (1.142)3   74.5 
 
= 1.169

Illustration 3: Calculate the glancing angle on the cube of a rock salt (a = 2.814 Å) corresponding to
second order diffraction maximum for X-rays of wavelength 0.710 Å. The distance between
two consecutive lattice planes is 2.814 Å.

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 Solid State

Solution : According to Bragg’s equation

2d sin = n  .... (i)
From equation (i)
2  2.814  10–8 sin = 2  0.710  10–8

2  0.710  10 8
sin = = 0.2533
2  2.2814  10 8

sin = 0.2533
  = sin–1 (0.2533)
or  = 14º 3640

Illustration 4: The nearest neighbour Ag atoms in silver crystal are 2.87  10–10 m apart. What is the
density of silver ? Silver crystallizes in f.c.c. form (At. mass Ag = 108)

Solution : In f.c.c. structure, atoms along the face diagonal of the unit cell touch each other. As there
are three atoms on each face diagonal, therefore, distance between nearest neighbour Ag
atoms,

Face diagonal 2a a
d = = = 2 ( where a = edge length of cubic unit cell)
2 2
–10 –10
 a= 2  d = 1.414  2.87  10 = 4.059  10 m = 406 pm
In f..c.c. unit cell of an element (silver) number of atoms per unit cell = 4

4  Atomic mass of Ag 4  108

 Mass of unit cell = Avogadro's number (N ) = g = 7.18  10–22 g
0 6.02  10 23
Volume of unit cell = a3 = (406  10–10)3 cm3 = 6.692  10–23

Mass of unit cell 7.18  1022

Density = = = 10.72 g cm–3
Volume of unit cell 6.292  10 23

Illustration 5: A metal crystallises into two cubic phases, face centred cubic (FCC) and body centred
cubic (BCC), whose unit cell lengths are 3.5 and 3.0 Å, respectively. Calculate the ratio of
densities of FCC and BCC.

Solution : We know that

Z  Formula mass of substance

= N0  a
3

Since for FCC, Z = 4 and for BCC, Z = 2

4  Formula mass of mall 4  Formula mass of mall
dFCC = N 0  (3.5)
3 and dBCC = N 0  (3)
3

Dividing dFCC by dBCC

3
d FCC 4 (3)
 
d BCC 2 (3.5) 3
= 2  0.6297 = 1.259

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Illustration 6: Chromium metal crystallizes with a body centred cubic lattice. The length of the unit cell is
found to be 287 pm. Calculate the atomic radius. What would be the density of chromium in
g/cm3 ? (At . wt. of Cr = 51.99)

Solution : For bcc, we know that

3 3
r = a=  287
4 4

4r = 3  287

r = 124. 27 pm
Further we know that

Mass of one unit cell Atomic mass  Z

Density = = N  Volume of one unit cell
Vol. of one unit cell 0

Here, Z = 2, a = 287 pm = 287 10–10 cm

Vol. of unit cell a3 = (287 × 10–10 cn)3

51.99  2
Thus, Density = 23 10 3 = 7.30 g cm–3
6.023 10  (287  10 )

SAMPLE PROBLEMS 2.1 (MCQ)

Problem 1: Lead (II) sulphide crystal has NaCl structure. What is its density ? The edge length of the
unit cell of PbS crystal is 500 pm. [N0 = 6.023  1023 mole–1 ; At. masses Pb = 207.2
S = 32]
(a) 1.27 g cm–3 (b) 12.7 g cm–3
(c) 12.7 g m–3 (d) 12.7 kg cm–3

Solution : (b) M = 239.2 amu a = 500 pm = 500  10–10 cm

Z = 4 N0 = 6.023  1023

239.2  4
So  = 23 10 3 = 12.7 g cm–3
6.023  10  (500  10 )

Problem 2: A compound, formed by elements X and Y, crystallises in the cubic structure, where Y atoms
are at the corner of a cube and X atoms are at alternate faces. The formula of the
compound is?
(a) XY (b) X2Y3
(c) XY3 (d) XY4

 1
Solution : (a) Number of atoms ‘Y’ at eight corners of a cubic unit cell =  8   = 1
 8

 1
Number of atoms ‘X’ present on alternate face of unit cell =  2   = 1
 2
 Formula of compound = XY

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Problem 3: A fcc lattice cube is formed by atoms A and B. If atom A is present at the corner of the cube
and the atom B at the faces of the cube. The formula of the compound is
(a) AB (b) AB3
(c) AB2 (d) A2B3

1
Solution : (b) Contribution of atom “A” at eight corners of the cube =  8 = 1 atom
8

1
Contribution of atom at each face = atom
2
1
 The atom “B” at six faces of the cube =  6 = 3 atoms
2
 Formula of the compound = AB3

Problem 4: Cesium chloride crystallises with a body centred cubic lattice, the length of the side of the
unit cell is 5.34 Å.The interionic distance will be
(a) 2.67Å (b) 5.34 3 Å

(c) 4.62Å (d) 1.29Å

Solution : (c) If R is the radius of anion & r is the radius of cation, then the interionic distance in a bcc
lattice is
a 3 5.34  3
R+r=  = 4.62Å
2 2
Problem 5: Sodium metal crystallizes in a body centred cubic lattice with the cell edge a = 4.29Å.
what is the radius of sodium atom?

(a) 1.8674Å (b) 2.8674Å

(c) 3.8674Å (d) 4.8674Å

3a 3  4.29
Solution: (a) Radius of Na (if bcc lattice) =  = 1.8674Å
4 4

Problem 6: Chromium metal crystallizes with a body-centred cubic lattice. The length of the unit cell
edge is formed to be 287 pm. Calculate the atomic radius. What would be the density of
chromium in g/cm3?
(a) 7.30 g/mL (b) 7.10 g/mL
(c) 7.20 g/mL (d) 6.30 g/mL

3a 3
Solution: (a) For bcc lattice r    287  124.57 pm
4 4
n  at. wt. n  at. wt.
Now, Density = V  Av. no.  a 3  Av. no.
n = 2 for bcc, a = 287 × 10–10 cm
2  51.99
 D  7.30 g / mL
(287  1010 )3  6.023  10 23

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Problem 7: At room temperature, sodium crystallises in a body-centred cubic lattice with a = 4.24Å.
Calculate theoretical density of sodium (At. wt. of Na = 23).
Solution: A body-centred cubic unit cell contains 8 atoms at the 8 corners and one in the centre.
(a) 1.002 g cm–3 (b) 1.000 g cm–2
(c) 1.012 g cm–1 (d) 2.012 g cm–3

1
(a)  Total numer of atoms per unit cell = 8   1  2
8

n  at.wt. 2  23
 Density =  –3
Av. no.  a 3 6.023 1023  (4.24  104 )3 = 1.002 g cm

Problem 8:. Lithium borohydride crystallizes in an orthorhombic system with 4 molecule per unit cell.
The unit cell dimensions are a × 68Å, b = 44Å and c = 7.2Å. If the molar mass is 21.76,
calculate the density of crystal.

(a) 1.154 × 10–22 cm3 (b) 2.154 × 10–22 cm3

(c) 0.154 × 10–22 cm3 (d) 1.154 × 10–22 cm3

n  mol.wt.
Solution: (b)  Density = V  Av. no.
n = 4, M = 21.76, Av. no. = 6.023 × 1023 and V = a × b × c
 V = 6.8 × 10–8 × 4.4 × 10–8 × 72 × 10–8
= 2.154 × 10–22 cm3

Problem 9: A compound CuCl has face centred cubic structure. Its density is 3.4 g cm–3. What is the
length of unit cell.
(a) 5.783Å (b) 2.783Å
(c) 1.783Å (d) 4.783Å

Solution: Molecular mass of CuCl = 99

n = 4 for face-centred cubic cell

n  mol.wt. 4  99
 Density =  3
V  Av. no. a  6.023  1023

4  99
or 3.4  3
 6.023 1023
a

 a  5.783 108 cm = 5.783Å

Problem 10: The edge length of unit cell of a metal having molecular weight 75 g mol–1 is 5Å which
crystallizes in cubic lattice. If the density is 2 g/cm3, calculate the radius of metal atom
(NA = 6 × 1023)
(a) 212.5 pm (b) 213.5 pm
(c) 211.5 pm (d) 216.5 pm

[ 83 ]
 Solid State

n  mol.wt.
Solution: (a) Density = V  Av. no.
a = 5 × 10–8 cm, d = 2 g/cm3
n  75
2  8 3
n  2
(5 10 )  6 10 23
i.e., the metal crystallizes in bcc, thus,
3 3
radius  a   5 = 2.165 Å = 216.5 pm
4 4

2.2 Close Packing in Solids

Close Packing in Two Dimension

Let us consider the packing of hard spheres of equal size

(i) The spheres can be arranged side by side in a row (horizontal alignment) as shown below

Close Packing of Spheres in one dimension

(ii) The spheres are packed in such a way that the rows have both horizontal as will as vertical
alignment. In this arrangement the spheres are found to form a square. This packing is called
square close packing.

Square closed packing layer

(iii) The spheres may also be packed in such a way that the second row are placed in the depression
between spheres of first row. Similarly the spheres in the third row are placed in the depression
between the spheres of second row and so on. This gives rise to a hexagonal closed packing of
spheres.

Hexagonal Closed Packed Layer

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 Solid State

Closed Packing in Three Dimension

1. If in a square arrangement of layers with spheres touching each other, the second layer is
placed right above the first layer of spheres then the repetition of layers become AAAA......
Such a 3-D packing gives rise to a simple cubic closed packing structure.

Simple Cubic Closed Packing

2. Where in the square packing of layers we have spheres not touching each other i.e.

Void

I-Layer

If the second layer spheres are placed in the voids of the first layers spheres and the third layer
spheres are placed in the voids of the second layer spheres then the repetition becomes
AB AB.....

I-Layer
A A A A

B B B

II-Layer
A A A A

Such a 3-D arrangement leads to Body centred cubic closed packing.

(a) (b)

3. If in the hexagonal arrangement of layers, the second layer is placed in the voids of the first
layer then we come across two types of voids
Voids - A – Octahedral Voids
Voids - B – Terahedral Voids

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 Solid State

A A A A
B
B B

B
B B

Tetrahedral void : When the void of one layer is covered by the sphere of other layer then
such a void is called a tetrahedral void. e.g.

After sliding After sliding

 slightly the  slightly the
black sphere black sphere

Octahedral Void : When the voids of two layers mix together, such voids are called octahedral
voids.

I-layer

II-layer

Octahedral Vol.
4. When the third layer is placed on the tetrahedral voids of the first layer then the repetition
become ABAB because the third layer will be right above the first layer. Such a 3-D arrangement
is called Hexagonal closest packing as in fig (a)

B
A

Hexagonal
Closed Packing B
(a) (b)

A
A

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 Solid State

5. When the third layer is placed on the octahedral voids of the second layer then the repetition
becomes ABC....... Such a 3-D arrangement is called cubic closed packing or face centred
cubic closed packing.

Face centred
Cubic Close parking

CRYSTAL STRUCTURES OF AB TYPE OF IONIC COMPOUNDS

The three basic structure of this type are NaCl, CsCl and Zinc sulphide. The ionic compound of type
AB have one of these three of structure

IONIC RADIUS AND RADIUS RATIO

Ionic radius of an ion is the distance from the nucleus of that ion upto which it has its influence
in an ionic bond.

Co-ordination number. It is the number of oppositely charged ions surrounding a particular ion in
the ionic crystal.

Radius ratio. In an ionic solid, the central cation can touch only that number of anions which should
lead to maximum electrostatic attraction and minimum electrostastic repulsions. These interactions
depend upon the sizes of the cation and anion. Thus, the arrangement of ions in a crystal is greatly
influenced by the ratio of radius of the cation and the anion.

Thus, Radius ratio is defined as the ratio of the radius of the cation to that of the anion.

Radius of the cation (r )

Radius ratio=
Radius of the anion (r– )

Larger the cation, greater will be the number of anions surrounding it and greater will be its co-
ordination number.

Significance. Radius ratio helps to predict co-ordination number and the structure of the ionic
crystal as follows :

Radius ratio Co-ordiation number Structure Example

0.155 – 0.225 3 Trigonal planar B2O3

0.225 – 0.414 4 Tetrahedral ZnS
0.414 – 0.732 6 Octahedral NaCl
0.732 – 1 8 Cubic CsCl

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 Solid State

(a) Rock Salt NaCl type

(i) rNa+ = +96 pm rCl– = 181 pm

rNa  96
 r – = = 0.524 this ratio lies between 0.414 and 0.732 and coordination number is
Cl 181

thus 6.
(ii) Cl– forms FCC type packing
(iii) Na+ ions occupy all octahedral voids
(iv) Coordination number for Na+ = 6
coordination number for Cl– = 6
(v) Number of Na+ ions per unit lattice = 4
number of Cl– ions per unit lattice = 4
Hence total number of ions = 8
Hence for each Na+ ions there is only one Cl– ions (A unit lattice consists of 4 formula units
of NaCl or vice versa if Na forms unit lattice
(vi) Number of Cl– ions used = 14
Number of Na+ ions used = 13
Other examples of this type are halides of Li, Na, K, Rb, fluoride of Cs oxides and sulphides
of Mg, Ca, Sr, Ba, AgCl, AlBr, AgF

(b) Cesium Chloride CsCl Type

(i) rCs+ = 169 rCl– = 181

rCs  169 r

rCl – 181 = 0.93 Hence r lies between
–

0.732 to 1.0 thus coordination number is = 8

CsCl has BCC type structure
(ii) Cl– form SCC packing
(iii) Cs+ ions occupy the body centred void of
(iv) Each Cs+ is surrounded by 8 Cl– ion
Cs
– +
each Cl is surrounded by 8 Cs cl
–

(v) Number of Cl– ions

per unit lattice = 1
Number of Cs+ ions per unit lattice = 1
(vi) A unit cell of cesium chloride has one formula unit of CsCl i.e. one Cs+ and one Cl– ion.
Other examples of this type an CsBr, CsI, NH4 Br, NH4I, thallous cyanide, thallous chloride.

(c) Zinc Blende ZnS (Sphalerite structure)

(i) rzn 2  74 rs – –  184

rzn 2 
 0.4 this value lies between 0.225 and 0.411
rs – –
hence a tetrahedral void is occupies coordination number = 4

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 Solid State

(ii) S2– ions are arranged in FCC type structure

(iii) Zn2+ ions occupy half the tetrahedral void
(iv) Number of Zn2+ ions = 4
Number of S2– ions = 4

r
The should have been 0.225 but the value is 0.40. The close packed arrangement of S2–
r

ion opens up and accumulates the larger S2– ions

(v) Coordination number of Zn2+ = 4
Coordination number of S2– = 4
(vi) The formula unit for ZnS type lattice = 4 other examples are
CuCl, CuBr, CuI, in which cations is smaller than anion.
AgI, Beryllium oxides all have Zinc blende structure.

Crystal Lattice of the Type AB2 & A2B

1. Calcium Fluoride CaF2 (Fluorite Type)

(i) Ca2+ is arranged in FCC type structure

(ii) F– occupy all tetrahedral voids

(iii) Each Ca2+ surrounded by 8 F– ion

Each F– is surrounded by 4 Ca2+ ion. Thus gives a 8 : 4 coordination number. CaF2 type unit
cells an SrF2, CdF2

2. Sodium oxide Na2O (Anti Fluorite Type)

(i) O2– form FCC

(ii) Na+ occupies tetrahedral voids

(iii) Coordination number of O2– = 8; Coordination number of Na+ = 4

Illustration 1: In a crystal of an ionic compound, the anions B form a close packed lattice and the cations
A occupy one half of the tetrahedral voids. What is the formula of the compound?

Solution: In a close packed array of B ion the number of tetrahedral voids per ion of B is two. Since,
half of the tetrahedral voids is occupied by the cations A the number of cations in the same
as that of the anion in the crystal and the formula of the compound is AB.

Illustration 2: In an ionic oxide, oxide ions are arranged in hcp array and positive ion occupy two thirds of
octahedral void. Suggest the formula assuming metal as M.

Solution: For ccp or hcp array of oxide ion

No. of octahedral voids are occupied by metal ion = 1

2
Since of octahedral voids are occupied by metal ion
3

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 Solid State

2 2
Thus each oxide ion has metal ion or whole number ratio of oxide and metal ion is 1:
3 3
or 3 : 2. Thus formula is M3O2.

Illustration 3:. In a close packed structure of mixed oxides, the lattice is composed of oxide ions, one
eighth of tetrahedral voids are occupied by divalent cations while one half of octahedral
voids are occupied by trivalent cations. What is the formula of the oxide?

Solution: Number of oxide ions (O) per unit cell = 1

Number of tetrahedral voids per ion in lattice = 2

1 1
Number of divalent cation (A) = 2 
8 4
Number of octahedral voids per ion in lattice = 1

1 1
Number of trivalent cations (B) = 1 
2 2
Formula = A1/4B1/2O = AB2O4

Illustration 4: In a crystal of an ionic compound, the anions B form the close packed lattice and the ions A
occupy all the tetrahedral voids. What is the formula of the compound?

Solution: In closed packed array of B ion the number of tetrahedal voids per ion of B is two. Since,
tetrahedral voids are occupied by A ions, there are two A ions per B ion in the crystal.
Therefore, the formula of the compound is A2B.

Illustration 5:. A compound AB has rock salt structure A : B = 1 : 1. The formula weight of AB is 6.023 y
amu and the closest A – B distance is y1/2 nm. Calculate the density of lattice

Solution: AB has rock salt (A : B = 1) structure, i.e., fcc structure (n = 4) and formula weight of BB
is 6.023 y g having closest distance A – B y1/3 nm. Therefore, edge length of unit cell.

a  2(A   B )  2  y1/3  109 m

n  molecular weight n  molecular weight

Density of AB  
Atomic number  V 6.023  1023  n 2
4  6.023  y 103
 (molecular weight in kg)  5.0 kg m3
6.023  1023  (2y1/3  109 )3

Illustration 6: A unit cell of sodium chloride has four formula units. The edge length of the unit cell is 0.564
nm. What is density of sodium chloride?

n  atomic weight
Solution: Density of NaCl =
Average number  a 3

4  58.5
 23 8 3
 2.16 g / cm 3
6.023 10  (5.64 10 )

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 Solid State

Illustration 7:. You are given marbles of diameter 10 nm. They are to be placed such their centres are lying
in a square bond by four lines each of length 40 nm. What will be the arrangement of
marbles in a plane so that maximum number of marbles can be placed inside the area?
Sketch the diagram and derive expression for the number of molecules per unit area.

Solution: Area of square having spherical marbles in it

= 40 × 10–1 × 40 × 10–1 cm2 = 16 cm2
The maximum number of spheres of 10
mm diameter in hcp packing can be seen
in fig.1.
Total length covered by spheres
= 5 + 4 × CD = 5 + 4 = 10 sin 60
= 5 + 4 × 5 3 = 40 mm
Maximum number of spheres (s) = 14 (full) + 8 (full) = 18

18
Number of spheres per cm2 = = 1.125
16

SAMPLE PROBLEMS 2.2 (MCQ)

Problem 1: Metallic gold crystallises in fcc lattice with edge length 4.070Å. Closest distance between
gold atoms is:
(a) 2.035 Å (b) 8.140Å
(c) 2.878 Å (d) 1.357 Å

a 2 9
Solution: (c) Closest distnace in fcc lattice   = 2.878 Å
2 2

Problem 2: How many “nearst-neighbours” does each gold atom have in fcc lattice?
(a) 10 (b) 12
(c) 14 (d) 6

Solution: (b) Coordination number in fcc = 12

Problem 3: Potassium crystallizes in a bcc lattice with a unit cell length a = 52Å. Distnace between
nearest neighbour is
(a) 5.2Å (b) 4.5Å
(c) 2.6Å (d) 2.4Å

Solution: (b) Distance between nearest neighbours in bcc structure

3a
 = 4.5Å
2
Problem 4: Distance between the next-nearest neighbour in Problem 3 is
(a) 5.2Å (b) 2.6 Å
(c) 2.4 Å (d) 10.04 Å

Solution: (a) In bcc distance between next nearest neighbour is (a).

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 Solid State

Problem 5: ABC ABC types of arrangement of diffeent layes, in a closed packed structure is called
(a) hcp (b) bcc
(c) fcc (d) cubic closed packed (ccp)

Solution: (d) Factual

Problem 6 The hcp arrangement of lons is described by

(a) ABAB (b) ABABA
(c) ABCABC (d) ABCABCABC

Solution: (b) Coordination number in hcp = 12

Problem 7: The C.N. of ccp structrue is

(a) 16 (b) 12
(c) 8 (d) 4

Solution: (b) Coordination number in fcc = 12

Problem 8: Zinc blende structure is obtained when Zn2+

(a) all tetrahedral sites (b) half tetrahedral sites
(c) all octahedral sites (d) half octahedral sites

Solution: (b)

Problem 9: Edge length M+X– (fcc structure) is 7.2Å. Assuming M+ – X– contact along the cell edge,
radius of X– ion is (rM = 1.6Å)
(a) 2.0Å (b) 5.6 Å
(c) 2.8 Å (d) 3.8 Å

Solution: (a) 2(rM  rX )  7.2

rX   2.0 Å

Problem 10: The hcp structure, the packing fraction is

(a) 0.68 (b) 0.74
(c) 0.50 (d) 0.54

volume of effective atoms

Solution: (b) Packing fraction =
volume of unit cell

2.3 Imperfections in Solids and Properties of Solids

The crystal structures of ionic compounds of the type AB and AB2 discussed earlier represent ideal
structures in which there is a completely ordered arrangement of constituent particles. However, in
real crystals the arrangement of constituent particles is not regular and thus crystals have imperfect
structures. Such imperfections are deviations from the perfectly ordered arrangement of atoms.
Thus any deviation from the completely ordered arrangement in a crystal constitutes disorder.
The disorder in a crystal of an element depends upon :

(i) Temperature and (ii) Presence of impurities

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 Solid State

Electronic Imperfections
In a perfectly covalent or ionic crystal such as silicon or germanium or sodium chloride, the
electrons are present in the fully occupied lowest energy states at 0K. The valence electrons are
mainly concentrated around the electronegative component in ionic crystals. As the temperature is
raised above 0K, some of the electrons gain energy and move to higher energy states. The electron-
deficient bond produced as a result of the removal of an electron is called hole. As the electrons
have moved away from their normal positions creating holes, the electrons and holes in solids are
considered electronic imperfections or defects. Electrons and holes are generally designated
by the symbols ‘e’ and ‘h’ respectively and their concentrations by ‘n’ and ‘p’ respectively. So
Si and Ge behave as semiconductors or intrinisic semiconductors.

Thus the promotion of electrons causes holes which results in increased electrical conductivity. The
electrical conductivity of silicon increases with increasing temperature (this behaviour is opposite to
that of metals).

The electrons and holes can also be produced by adding certain impurities to a covalent crystal. For
example, electrical conductivity of silicon or germanium can be greatly enhanced by adding traces
of aluminium or arsenic as an impurity.

Atomic Imperfections
These can be classified into two categories Lattice imperfections and point defects.

Lattice Imperfections
These arise due to a deviation from periodic repetition of the lattice points over a large
section of the crystal. Lattice imperfections may extend along lines known as line defects or
dislocations or these may extend along surface known as plane defects. Two common types of
dislocation are edge dislocation and screw dislocation. Edge dislocation is formed when a layer
of particles discontinues within the crystals.

Points Defects
These are caused by a departure from the periodic arrangement in the vicinity of an atom or
a group of atoms. Point defects in crystals may be classified as :

(a) Defects in stoichiometric solids also called stoichiometric defects.

(b) Defects in non-stoichiometric solids also called non-stoichiometric defects.

(c) Impurity defects

Defects in Stoichiometric Solids

Stoichiometric solids are those in which the number of positive and negative ions are exactly in the
ratio indicated by their chemical formulae. These are of 2 types

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 Solid State

(i) Schottky defect

(ii) Frenkel defect

+ – + +
A B A B
–
A
(i) Schottky defect : A pair of ‘holes’ or
vacancies exists in the crystal lattice due to
one cation and one anion missing from the B
–
B
–
A
+
B
–

normal lattice sites. The crystal as a whole

remains neutral because the number of missing
+ +
A B
–
A
+
A
cations and anions remains the same. This sort
of defect occurs in highly ionic compounds
with a high coordination number and where B– A+ B
–
A
+
A
+

the ions (both cations and anions) are of

similar size. Alkali metal halides such as NaCl, KCl, KBr, and CsCl show this defect. In NaCl
crystal, at room temperature, there will be one Schottky defect per 1016 ions.

Since the presence of a large number of Schottky defects in a crystal leads to decrease in
the number of ions in the lattice, this results in lowering the density of the solid markedly.

(ii) Frenkel defect :

A+ B– A+ B– A+
When a ‘hole’ or ‘vacancy’ exists in the
A+
crystal lattice because an ion occupies an
B– B– A+ B–
interstitial lattice site, it gives rise to Frenkel
defect. The crystal remains neutral. The
defect occurs more frequently in solids A+ A+ A+ A+
B–
which have low coordination number and
possess ions (cations and anions) of
different sizes. Since cations are generally B– A+ B– A+ A+

smaller than anions, it is more common to

find the cations occupying the interstitial
sites. For example, in AgBr and

ZnS crystals, Ag+ ions and Zn2+ ions are missing from their normal lattice sites and are present
in the interstitial positions. AgBr, AgCl and AgI contains Schottky defects also.

Since the presence of Frenkel defects does not change the number of ions in the
lattice, the density of the solid remains the same. The defect causes increase in dielectric
constant of the crystals as similar charges come closer.

Defects in Non-Stoichiometric Solids

Non-Stoichiometric solids are those in which the ratio of positive and negative ions present differs
from that indicated by the ideal chemical formula. In compounds such as FeO, FeS, CuO, TiO, ZrO,
VO and Cu2S the real composition of the constituent ions can vary. Curprous sulphide, for example,
may contain anything between Cu1.96 S and Cu2S. Similarly, in vanadium oxide, VOx, x can be
anywhere between 0.6 and 1.3. The balance of positive and negative charge is maintained either by
having extra electron or extra positive charges present.
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 Solid State

Metal Excess Defects

These defects may arise in two ways:
+ + –
A B– A B
(i) Metal excess due to anionic vacancies. A negative ion
may be missing from its lattice site, leaving a hole which is
– –
occupied by an electron which was associated with the negative B e B– A+

ion and remains trapped in the vacancy thereby maintaining

the electrical neutrality. When NaCl is treated with sodium A
+
B– A
+
B
–

vapours, a yellow coloured non-stoichiometric form of NaCl

is obtained in which there is an excess of sodium ions. Sodium – + – +
B A B A
atom removes chlorine atom from the anionic lattice

site leaving its electron trapped in the vacancy and makes the lattice excess of solid ions.
Similarly excess of potassium in KCl makes the crystal to appear violet and excess lithium in
LiCl makes it pink. The electrons trapped in anion vacancies are referred to as ‘F’ centres
(F = Farben in German means colour).

These electrons absorb energy of the white light, giving yellow colour to NaCl, pink colour to
LiCl and violet colour to KCl.

(ii) Metal excess due to extra cations: + + –

A B– A B
In this case, the excess metal occurs when an extra positive A
+

ion occupies an interstitial position in the lattice. The free B

–
A
+
B– A+
electron is trapped in another interstitial site close to the vicinity
of the interstitial cation. This electron helps to maintain the
e–
A
+
B– A
+
A+
electrical neutrality.

When zinc oxide is heated at high temperatures, it loses oxygen – + – +

B A B A
reversibly and turns yellow in colour. The excess metal ion is
accommodated in the interstitial sites giving rise to electrons
trapped in the neighborhood. The higher electrical conductivity
of the non-stoichiometric ZnO is due to these electrons.

1
ZnO  Zn 2   O 2  2e –
2
ZnO is yellow when hot and white when cold.

Metal Deficiency Defects

A+ B– A+ B– A+ B–
These defects occur in metals with variable
oxidation states, i.e., the transition metals. A cation
B– B– A2+ B– A+
may be missing from its lattice site but the electrical
neutrality is maintained when the adjacent metal
ion acqires higher oxidation state (fig.) Examples A+ B– A+ B– A+ B–
include FeO, FeS and NiO. metal deficient
compounds conduct electricity throw positive hole B– A+ B– A+ B– B–
conduction mechanism and are therefore p-type
semi-conductors

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 Solid State

Impurity Defects
These defects aries due to the presence of foreign atoms or ions at the lattice sites. Thus depending
upon the nature of impurity, two types of impurity defects are possible.

(i) Impurity defect due to neutral atoms : Foreign atoms can occupy interstitial or substitutional
sites in a crystal. The electronic structure of impurity is of importance in the case of substitutional
solid solutions while the size of the impurity atom determines the formation of interstitial or
substitutional solid solution. Solid solutions of group 13 or group 15 as impurities with
group 14 elements such as Ge or Si (act as host) are of great interest in electronic industry
in making transistors. Group 13 elements such as Ga and Al and Group 15 elements such as P
and As enter Ge or Si substitutionally.

(a) Group 15 elements such as P, As etc. have one excess valence electron (electron
to Si or Ge) after forming four covalent bonds with Group 14 element. The excess
electrons give rise to electronic conduction known as n-type semiconduction. (as
the current is carried by electrons in the normal way).

(b) On the other hand a Group 13 element such as Ga, Al or In which has only three
valence electrons (i.e. one electron less than required for forming four covalent
bonds) creates an electron deficient bond or a ‘hole’. Such ‘holes’ can move in the
crystal giving rise to electrical conductivity known as p-type semiconduction.

(ii) Impurity defect due to ions :

+ +
Na Cl– Na Cl–
This defect is brought about by adding impurity ions in ionic
solid. If the impurity ions are in different valence state from – 2+ – +
Cl Sr Cl Na
that of the host ions, vacancies are created.

For example, addition of CdCl2 to AgCl (or of SrCl2 or MgCl2 Na+ Cl

–
Cl
–

to NaCl) yields solid solutions where the divalent cation

Cd2+ (or Sr2+ + Mg2+) occupies the Ag+ (or Na+) sites and Cl– Na
+
Cl
–
Na
+

produces cation vacancies equal in number to that of the

divalent ions. The SrCl 2 doped NaCl has much higher
electrical conductivity than that of pure NaCl.

Properties of Solids

There is a close relationship between the properties of a solid and its structure and composition.
Some of these properties are :

(i) Electrical properties

(ii) Magnetic properties

(iii) Dielectric properties

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Electrical Properties (Electrical Conductivity)

Based on their electrical conductivity, solids can be broadly classified into three types :

(i) Metals or conductors : They are good conductors of electricity as the electrons can move
freely without much resistance. Their conductivity value is of the order of 108 ohm–1 cm–1 at
room temperature which decreases with rise in temperature.

Some mono oxides of transition metals (which possess NaCl structure) like TiO, VO behave
like metallic conductors. CrO2 also behaves as metal conductor.

(ii) Insulators or Non-conductors: These solids do not allow the electricity to pass through
them. Non-metals like diamond, P and S, solutions of non-electrolytes like sugar and urea,
substances like wood, rubber and plastics are all examples of insulators. Their conductivity
value is extremely low and is of the order of less than 10–12 ohm–1 cm–1 at room temperature.

(iii) Semi-conductors: These solids possess conductivity values which are intermediate between
those of typical metals and insulators i.e. in the range 102 – 10–9 ohm–1 cm–2. The conductivity
of such solids increases with temperature.

Electrical conductivity of solids may arise through the motion of electrons and holes (electronic
conductivity) or ions (ionic conductivity). Substances such as pure solid alkali metal halides
where the conduction is only through ions, are generally insulators as their ions cannot move.
Presence of vacancies or other imperfections, however, greatly increase the conductivity of
ionic solids.

Magnetic Properties

Materials can be divided into different classes depending upon the effect of magnetic fields on
them.

(i) Diamagnetic materials : These materials are weakly repelled by a magnetic field. Examples
are TiO2, NaCl and benzene.

(ii) Paramagnetic materials : These materials are attracted by a magnetic field. Examples are
O2, Cu2+, Fe2+. Paramagnetism is observed due to the presence of permanent magnetic dipoles
as a result of unpaired electrons in atoms, ions or molecules. Paramagnetic materials, however,
lose their magnetic character in the absence of a magnetic field.

Paramagnetic materials sometimes show a special type of magnetic behaviour and are classified
as:

(a) Ferromagnetic materials : Unlike paramagnetic substances ferromagnetic materials

show permanent magnetic property even when the magnetic field is removed. These
materials exhibit unusually large paramagnetism. Examples are Fe, Co, Ni, CrO2.

(a) Ferromagnet

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 Solid State

(b) Antiferromagnetic materials : These materials show much reduced paramagnetism

(almost zero) than expected from their electronic structures. Examples are MnO, FeO,
CoO, NiO, and many other oxides.

Anti-Ferromagnet
(b)

(c) Ferrimagnetic materials : These materials show small paramagnetic character.

Examples are Fe3O4 ferrites of the formula M2+Fe2O4, when M = Mg, Cu, Zn. In these
materials the alignment of magnetic moments are in parallel and antiparallel directions
in unequal numbers.

(c) Ferrimagnet

As a result the material has net magnetic moment and shows

ferrimagnetism fig (c).

All magnetically ordered solids (ferromagnetic, ferrimagnetic and anti-ferromagnetic solids)

transform to the paramagnetic state at some temperature due to the randomisation of
spins. Thus ferrimagnetics, Fe3O4 becomes paramagnetic at 850 K.

Magnetic Properties of Typical Transition Metal Oxides

Diamagnetic Paramagnetic Ferromagnetic Antiferromagnetic Ferrimagnetic
TiO2 TiO, Ti2O3 CrO2 V2O3, Cr2O3 Fe3O4
V2O 5 VO, VO2 MnO, MnO2
CuO Mn2O3
Mn2O3 FeO, Fe2O3, Co3O4

Dielectric Properties
In insulators, electrons are closely bound to individual atoms or ions and they do not generally
migrate under an applied electric field.

(i) These dipoles may align themselves in an ordered manner under the influence of an applied
electric field such that there is net dipole moment in the crystals.

(ii) They may align themselves in such a manner that the dipole moments cancel each other.

(iii) It is also possible that there are no dipoles in the crystal, but only ions are present.

Properties of Piezoelectric Crystals :

Crystals where situation (i) is found, exhibit piezoelectricity. When mechanical stress is applied
on such crystals so as to deform them, electricity is produced due to displacement of ions.

(a) Electrical mechanical transducer : When such a crystal is deformed by mechanical stress,
electricity is produced due to the displacement of ions crystal, or conversely if an electric

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field is applied to the crystal, there will be atomic displacements causing mechanical strain.
Thus, a piezoelectric crystal acts as a mechanical electrical transducer.

(b) Pyroelectricity : Some of the polar crystals, when heated, produce a small electric current
called pyroelectricity.

Illustration 1: Calculate the concentration of cation vacancies if NaCl is doped with 10–3 mole % of SrCl2.

Solution: Doping of SrCl2 to NaCl brings in replacement of two Na+ ion by each Sr2+ ion, but each S2+
occupies only one lattice point. This produces one cation vacancy.
Thus, doping of 10–3 mole of SrCl2 in 100 moles
 100 mole of NaCl will have cation vacancies after doping = 10–3

103
 1 mole of NaCl will have cation vacancies =  105
100
 Total cationic vacancies = 10–5 × Av. no. = 6.02 × 1018

Illustration 2: In a closed packed structure of mixed oxides, the lattice is composed of mixed oxides ions.
One eight of tetrahedral voids are occupied by divalent cations (A2+) while one half of
octahedral voids are occupied by trivalent cation (B3+). The formula of mixed oxide is:

Solution: (d) Number of tetrahedral voids per ion in lattice = 2

2 1 1
Number of A   2 
8 4
Number of octahedral voids per ion in lattice = 1
3 1 1
Number of B  1 
2 2
Formula AB2O4

SAMPLE PROBLEMS 2.3 (MCQ)

Problem 1: Ferrimagnatism is in
(a)  (b) 
(c)  (d) None
Solution: (c)

Problem 2: Ferromagnetism is in
(a)  (b) 
(c)  (d) None

Solution: (a)

Probem 3: Which is true?

(a) piezoelectricity is due to net dipole moment
(b) some electric current is produced on heating polar crystals, this is pyroelectricity.
(c) ferroelectricity is due to alignment of dipole in same direction
(d) all true

Solution: (d)

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Problem 4: Frenkel defect is the

(a) Schottky defect (b) Interstitial defect
(c) combination of (a), (b) (d) None of these

Solution: (c)

Problem 5: Schottky defect is due to:

(a) missing of ions from normal lattice site
(b) missing of an atom from normal lattice site
(c) Both (a) and (b)
(d) None of these

Solution: (a)

Problem 6: An electon trapped in an anion vacancy within the crystal is called

(a) n-type conductor (b) p-tyope conductor
(c) F-centre (d) Insulator

Solution: (c)

Problem 7: The n-type semiconductance is obtained when Si is doped with

(a) Al (b) Ge
(c) B (d) As

Solution: (d)

Problem 8: Antifluorite structure is for

(a) ThO2 (b) Na 2O
(c) Both (a) and (b) (d) None of these

Solution: (b)

Problem 9: 6 : 6 of NaCl coordiantion changes to 8 : 8 coordiantion on:

(a) Applying high P (b) Increase in temperature
(c) Both (a) and (b) (d) No effect on coordination

Solution: (a)

Problem 10: ZnS does not crystallise in the NaCl structure. It is due to:

r
(a) The ratio is 0.402, too low to avoid anion-anion contact in the Nacl structure
r

r
(b) The ratio is 0.402, too high to avoid cation-cation contact in the Nacl structure
r
(c) Both correct

(d) None of these

Solution: (a)

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CHAPTER ASSIGNMENT
MULTIPLE CHOICE QUESTIONS (Single Correct)
1. A compound formed by element A and B crystallizes in the cubic structure, where A atoms are at the
corners of a cube and B atoms are at the centre of the body. The formula of the compounds is
(a) AB (b) AB2 (c) A2B3 (d) AB3

2. The number of octahedral sites in a cubical close pack array of N spheres is

(a) N (b) 4N (c) N/2 (d) 2N

3. The radius of Ag+ ion is 126 pm while that of I– ion is 216 pm. The co-ordination number of Ag in
AgI is
(a) 2 (b) 4 (c) 6 (d) 8

4. The yellow colour of ZnO and conducting nature produced in heating is due to
(a) Metal excess due to interstital cation (b) Extra positive ions present in an interstital site
(c) Trapped electrons (d) All of these

5. The space occupied by spheres in a FCC arrangement is

(a) 46.4% (b) 52.4% (c) 74% (d) None of these

6. The number of space lattices and crystal systems are ______ and ________ respectively
(a) 7 and 14 (b) 14 and 7 (c) 32 and 7 (d) 7 and 32

7. A binary solid A+B– has a zinc blende structure with B– ions constituting the lattice and A+ ions
occupying 50% tetrahedral holes. Formula of the solid is
(a) A2 B (b) AB (c) AB2 (d) AB4

8. A solid has a bcc structure. If the distance of closest approach between the two atoms is 1.73 Å.
The edge length of the cell is
(a) 200 pm (b) 3 / 2 pm (c) 142.2 pm (d) None of these

9. The packing fraction is maximum in the crystal lattice of

(a) FCC (b) BCC (c) SCC (d) None of these

10. An element crystallises in a bcc lattice with a unit cell length of 200 pm. What is the radius of copper
atom in pm?
(a) 157 (b) 181 (c) 108 (d) 86.6

11. For a solid with the structure, the co-ordination number of point Z is

Z
(a) 3 (b) 4 (c) 5 (d) 6

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12. In a compound, atoms of element Y form ccp lattice and those of element X occupy 2/3rd of octahedral
voids. The formula of the compound will be
(a) X2Y (b) X3Y4 (c) X4Y3 (d) X2Y3

13. The wavelength of the x-rays which give a diffraction angle of 16.80o for crystal with interplanar
distance of 0.200 nm will be (only first order diffraction, sin 16.80 = 0.2890) ?
(a) 0.0485  10-9 m (b) 0.0584  10-9 m (c) 0.0548  10-9 m (d) None of these

14. What is the volume of a face centred cubic unit cell, when its density is 2.0 g cm–3 and the molar
mass of the substance is 60.223g mol–1 ?
(a) 4  10–22 cm3 (b) 2  10–22 cm3 (c) 44  10–22cm3 (d) 22  10–22cm3

15. CaO and NaCl have the same crystal structure and nearly the same radii. If ‘a’ is the lattice energy
of NaCl, the lattice energy of CaO is very nearly
(a) 4 a (b) 2 a (c) a (d) a/2

INTEGER TYPE QUESTIONS

16. PbS has NaCl structure. Its density is 12.7 gm/cm3. Molar mass if PbS is 239. Calculate inter ionic
distance in pm units, answer divided by 50 and express the number.

17. Chromium (At. wt.= 52) crystallizes with bcc lattice. The length of the unit cell edge is found to be
290 pm. The value of density in gm/cm3 is.

18. Find ratio of body diagonal length to that of nearest distance between centres of tetrahedral and
octahedral voids in fcc system.

19. In a FeO crystal lattice, 4% of cations sites are vacant and electroneutrality is maintained by oxidation
of some Fe(II) into Fe(III). The number of Fe(III) ions present per hundred of O–2 ions are.

20. An ionic substance AB has NaCl like structure in which ions A occupy corners of the cubic unit cell.
If all the face centred ions along one of axes are removed. The total no of effective ions of A and B
in one unit cell will be.

21. Density of Lithium atom is 0.53 g/cm3. the edge length of Li is 3.5 Å. The number of Lithium atoms
in a unit cell will be........... (atomic mass of Lithium is 6.94).

22. The concentration of cation vacancies if NaCl is droped with 10–3 mole percentage of SrCl2 is
6.023 × 10(x + y). If x is 10 they y is .

23. A cubic is made up of two elements X and Y. X is present at corners and Y present at body centre.
The Co. no. of X is.

24. In ABC packing no. of tetrahedral voids present per unit cell is.

25. How many number of effective Na+ ions, present in unit cell of Rock salt structure is.

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MULTIPLE CHOICE QUESTIONS (More than one Correct)

26. The intermetallic compound LiAg has a cubic crystalline structure in which each Li atom has 8
nearest neighbour silver atoms and vice-versa. What is the type of unit cell?
(a) Body -centred cubic
(b) Face-centred Cubic
(c) Simple cubic for either Li atoms alone or Ag atoms alone
(d) None of the above

27. Which of the following statements are correct?

(a) The lattice positions left vacant by anion and occupied by electrons are called F-centres.
(b) The presence of F-centres make lattice electrically neutral and diamagnetic.
(c) The presence of F-centres give colours to the crystal.
(d) F-centres contains unpaired electrons.

28. Which of the following are correct with respect to Zinc blende structure?
(a) Zn+2 ions are present at corners and at the centre of each face.
(b) Only alternate tetrahedral holes occupied by Zn+2 ions.
(c) The coordination number of Zn+2 and S–2 is 4 each.
(d) The number of ZnS units in unit cell is 4.

29. Select the correct statements among following:

(a) Nearest neighbour distance in NaCl = a/2 (b) Nearest neighbour distance in CaF2= a3/4
(c) Nearest neighbour distance in Na2O= a3/4 (d) Nearest neighbour distance in CaCl= a3/2

30. In the unit cell of NaCl, which of the following statements are correct?
(a) Na+ ions have six Cl– ions in its nearest neighbourhood.
(b) Cl– ions have six Na+ ions in its nearest neighbourhood.
(c) Second nearest neighbour of Na+ ion are twelve Na+ ions.
(d) NaCl has 68% of occupied space.

31. The number of nearest neighbours with which a given sphere of packing is in contact, is called co-
ordination number. The correct statements about co-ordination number are
(a) Coordination number decreases on heating.
(b) Coordination number increases on applying pressure.
(c) CsCl acquires NaCl type structure on heating.
(d) Coordination number of octahedral site is 6.

32. Which of the following is/are a Bravais lattice?

(a) Face centred orthorhombic (b) Face centred cubic
(c) Body centred tetragonal (d) End centred monoclinic

33. Which of the following statements are correct?

(a) ccp structure has 3-layers
(b) In ccp structure first and fourth layers are repeated.
(c) In hcp structure first and third layers are repeated.
(d) In hcp structure first and third layers are repeated.

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 Solid State

34. The correct statement(s) regarding defects in solids is(are)

(a) Frenkel defect is usually favoured by a very small difference in the sizes of cation and anion.
(b) Frenkel defect is a dislocation defect.
(c) Trapping on an electron in the lattice leads to the formation of F-centre.
(d) Schottky defects have no effect on the physical properties of solids.

35. The composition of a sample of wustite is Fe0.93O1.00. Which of the following statements are correct
related to this compound?
(a) The percentage of Fe(III) by mass is 11.5%
(b) The ratio of Fe(III) to Fe(II) ion is 0.17
(c) The percentage of Fe(II) ion 11.5%
(d) The amount of Fe3+ is 7.84 g

MATRIX MATCH TYPE QUESTIONS

36. Column - I Column - II

(A) Rock salt structure (p) Co-ordination number of cation is 4

3a
(B) Zinc blend structure (q)  r  r
2
(C) Anti Fluorite structure (r) Coordination number of cation and anion are
same
(D) Bcc Structure (s) Distance between two nearest anions is a/2

37. Match the crystal system/unit cell mentioned in Column I with their characteristic features mentioned
in Column II
Column I Column II
(A) Zinc Blende (p) Anion and Cation have similar coordination number
(B) Rock Salt (q) Voids along one face plane are not occupied
(C) Fluorite (r) All the voids along one of the body diagonal line are not occupied
 gm  4× molar mass
(D) Anti fluorite (s) d  3  =
 cm  volumeof unit cell×Avogardo's number

COMPREHENSION TYPE QUESTIONS

Comprehension - I

A cubic unit cell contains Manganese ions at the corners and Fluoride ions at the centre of each edge.

38. What is the empirical formula?

(a) MnF (b) MnF2 (c) MnF3 (d) MnF4

39. What is the edge length of the cell if the radius of Mn ion is 0.65 Å and F-ion is 1.36 Å?
(a) 2.01Å (b) 4.02Å (c) 5.68 Å (d) 2.89 Å

40. What is the density of the compound? (Mn = 55, F = 19)

(a) 2.86 gm/cm3 (b) 5.72 gm/cm3 (c) 11.45 gm/cm3 (d) 8.59 gm/cm3

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 Solid State

Comprehension - II

Atoms in a solid can be closely packed resulting into either cubical close packing (ccp) or hexagonal close
packing (hcp). There exists two type of voids tetrahedral and octahedral. Atoms can be closely packed
resulting ccp having arrangement ABC, ABC, .... while in hcp it is AB, AB, .... type

41. The number of tetrahedral void around an atom in ccp is

(a) 12 (b) 8 (c) 4 (d) 2

42. Which is correct about densities

(a) ccp > hcp (b) hcp > ccp
(c) ccp = hcp (d) ccp > or < or = hcp depending upon the actual size of atoms

43. The ratio of coordination numbers of atoms of ccp : hcp is

(a) 1 : 1 (b) 1 : 2 (c) 2 : 1 (d) 2 : 3

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 Solid State

PREVIOUS YEAR QUESTIONS

1. Which of the following FCC structure contains cations in alternate tetrahedral voids? [IIT]
(a) NaCl (b) ZnS (c) Na 2 O (d) CaF 2

2. When I– is oxidised by MnO4– in alkaline medium, I– converts into [IIT]

(a) IO 3 – (b) I 2 (c) IO 4 – (d) IO –

3. A metallic crystal crystallizes into a lattice containing a sequence of layers AB AB AB ...... Any
packing of spheres leaves out voids in the lattice. What percentage of volume of this lattice is empty
space? [IIT]
(a) 74% (b) 26% (c) 50% (d) none of these

4. The coordination number of a metal crystalling in a hexagonal close packed structure is [IIT]
(a) 12 (b) 4 (c) 8 (d) 6

5. In a solid AB having the NaCl structure, ‘A’ atoms occupy the corners of the cubic unit cell. If all the
face-centred atoms along one of the axes are removed, then the resultant stoichiometry of
the solid is [IIT]
(a) AB 2 (b) A 2 B (c) A4 B 3 (d) A3 B 4

6. A subsance AxBy crystallizes in a face centred cubic (FCC) lattice in which atoms ‘A’ occupy each
corner of the cube and atoms ‘B’ occupy the centres of each face of the cube. Identify the correct
composition of the substance AxBy [IIT]
(a) AB 3 (b) A4 B 3
(c) A 3 B (d) composition cannot be specified

7. The correct statement(s) regarding defects in solids is (are) [IIT]

(a) Frenkel defect is usually favoured by a very small difference in the sizes of cation and anion
(b) Frenkel defect is a dislocation defect
(c) Trapping of an electron in the lattice leads to the formation of F-center
(d) Schottky defects have no effect on the physical properties of solids

8. Match the crystal system/unit cell mentioned in Column I with their characteristic features mentioned
in Column II. Indicate your answer by darkening the appropriate bubbles of the 4 × 4 matrix given
in the ORS. [IIT]
Column I Column II
A. simple cubic and face-centred cubic (p) have these cell paramaters
a = b = c and 
B. cubic and rhombohedral (q) are two crystal systems
C. cubic and tetragonal (r) have only two crystallographic angles of 90°
D. hexagonal and monoclinic (s) belong to same crystal system

9. The coordination number of Al in the crystalline state of AlCl3 is [IIT]

[ 106 ]
 Solid State

10. The packing efficiency of the two-dimensional square unit cell shown below is [IIT]
(a) 39.27%
(b) 68.02%
(c) 74.05%
(d) 78.54% L

11. Silver (atomic weight = 108 g mol–1) has a density of 10.5g cm–3. The number of silver atoms on a
surface of area 10 –12 m2 can be expressed in scientific notation as y × 10 x. T he
value of x is [IIT]

12. A compound MpXq has cubic close packing (ccp) arrangement of

M=
X. Its unit cell structure is shown below. The empirical formula of
X=

the compound is
(a) MX (b) MX2
(c) M2X (d) M5 X14 [IIT]

13. The arrangement of X– ions around A+ ion in solid AX is given in

the figure (not drawn to scale). If the radius of X– is 250 pm, the
radius of A+ is
(a) 104 pm (b) 125 pm
(c) 183 pm (d) 57 pm [JEE-Advance]

14. All crystals of same substance posess the same elements of symmetry. This is a statement
of [DCE]
(a) Bragg’s law (b) Law of crytals (c) Law of symmetry (d) None of these

15. Lithium metal has a body centred cubic structure. Its density is 0.53 g cm–3 and its atomic mass is
6.94 g mol–1. Calculate the edge length of a unit cell of lithium metal [DCE]
(a) 153.6 pm (b) 351.6 pm (c) 257.4 pm (d) 263.7 pm

16. In a solid lattice, cation is absent from lattice site and present at an interstitial position, the lattice
defect is [DCE]
(a) Frenkel (b) interstitial (c) Schottky (d) None of these
17. Monoclinic crystal has dimension [DCE]
(a) a  b  c,  = 90°,  90° (b) a  b  c,  =  90°
(c) a  b  c,  = 90° (d) a  b  c,   90°

18. Shine at freshly cut sodium is because of [DCE]

(a) oscilation of free electrons (b) weak metallic bonding
(c) absorption of light in crystal lattice (d) presence of free valency at the surface

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 Solid State

19. For a crystal system a = b = c and  =  = 90° [DCE]

(a) tetragonal (b) hexagonal (c) rhomohedral (d) monoclinic

20. An ionic compound has a unit cell consisting of A ions at the corners of a cube and B ions on the
centres of the faces of the cube. The empirical formula for this compound would be [AIEEE]
(a) AB (b) A 2 B (c) AB 3 (d) A 3 B

21. What type of crystal defect is indicated in the diagram below? [AIEEE]
Na+ Cl– Na+ Cl– Na+ Cl–
Cl– Cl– Na+ Na+
Na+ Cl– Cl– Na+ Cl–
Cl– Na+ Cl– Na+ Na+
(a) Interstitial defect (b) Schottky defect
(c) Frenkel defect (d) Frenkel and Schottky defects

22. Percentages of free space in cubic close packed structure and in body centered packed structure
are respectively [AIEEE]
(a) 32% and 48% (b) 48% and 26% (c) 30% and 26% (d) 26% and 32%

23. In a face centred cubic lattice, atom A occupies the corner positions and atom B occupies the
face centre position. If one atom of B is missing from one of the face centred points, the formula
of the compound is: [AIEEE]
(a) A 2 B (b) AB 2 (c) A2 B 3 (d) A2 B 5

24. Lithium forms body centred cubic structure. The length of the side of its unit cell is 351 pm. Atomic
radius of the lithium will be [AIEEE]
(a) 75 pm (b) 300 pm (c) 240 pm (d) 152 pm

25. Experimentally it was found that a metal oxide has formula M0.98O. Metal M, is present as M2+ and
M3+ in its oxide. Fraction of the metal which exists as M3+ would be: [JEE-Mains]
(a) 6.05% (b) 5.08% (c) 7.01% (d) 4.08%

26. CsCl crystallises in body centred cubic lattice. If ‘a’ is its edge length then which of the following
expressions is correct? [JEE-Mains]
3 3a
(a) rCs  rCl  a (b) rCs  rCl  3a (c) rCs  rCl  3a (d) rCs  rCl 
2 2

27. Which of the following compounds is metallic and ferromagnetic? [JEE Mains]
(1) MnO2 (2) TiO2 (3) CrO2 (4) VO 2

28. The CORRECT statement(s) for cubic close packed (ccp) three dimensional structure is(are)
(A) The number of the nearest neighbours of an atom present in the topmost layer is 12
(B)The efficiency of atom packing is 74%.
(C)The number of octahedral and tetrahedral voids per atom are 1 and 2, respectively
(D) The unit cell edge length is 2 2 times the radius of the atom [JEE Advance]

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 Solid State

29. A metal crystallises in a face centred cubic structure. If the edge length of its unit cell is ‘a’, the
closed approach between two atoms in metallic crystal will be [JEE Mains]
a
(a) 2a (b) 2 2 a (c) 2a (d)
2

30. A crystalline solid of a pure substance has a face-centred cubic structure with a cell edge of 400 pm.
If the density of the substance in the crystal is 8 g cm–3, then the number of atoms present in 256 g
of the crystal is N × 1024. The value of N is [JEE Advanced

31. Which type of defect has the presence of cations in the interstitial sites? [JEE Mains]
(a) Metal deficiency defect (b) Schottky defect
(c) Vacancy defect (d) Frenkel defect

32. Consider an ionic solid MX with NaCl structure. Construct a new structure (Z) whose unit cell is
constructed from the unit cell of MX following the sequential instructions given below. Neglect the
charge balance. [JEE Advanced]
(i) Remove all the anions (X) except the central one
(ii) Replace all the face centered cations (M) by anions (X)
(iii) Remove all the corner cations (M)
(iv) Replace the central anion (X) with cation (M)
 number of anions 
The value of  number of cations  in Z is ____.
 

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 Solid State

CHAPTER TEST
SECTION - I: MULTIPLE CHOICE QUESTIONS (Single Correct)

1. How many unit cells are present in a cube shaped ideal crystal of NaCl of mass 1.00 g?
[Atomic masses: Na = 23, Cl = 35.5]
(a) 5.14 × 1021 (b) 1.28 × 1021 (c) 1.71 × 1021 (d) 2.57 × 1021
2. Total volume of atoms present in a face-centred cubic unit cell of a metal is (r is atomic radius)
16 3 20 3 24 3 12 3
(a) r (b) r (c) r (d) r
3 3 3 3
3. In a compound, atoms of element Y form ccp lattice and those of element X occupy 2/3 rd of
tetrahedral voids. The formula of the compound will be
(a) X2 Y3 (b) X2 Y (c) X3 Y4 (d) X4 Y3
4. Copper crystallises in fcc with a unit cell length of 361 pm. What is the radius of copper atom?
(a) 127 pm (b) 157 pm (c) 181 pm (d) 108 pm
5. The edge length of a face centered cubic cell of an ionic substance is 508 pm. If the radius of the
cation is 110 pm, the radius of the anion is
(a) 618 pm (b) 144pm (c) 288 pm (d) 398 pm

SECTION - II: MULTIPLE CHOICE QUESTIONS (More than one correct)

6. For the Schottky defect which of the following is/are not correct
(a) Some of lattice sites are vacant
(b) An ion occupies interstitial positions between lattice point
(c) A lattice site is occupied by electron
(d) The ratio r+/r– is low

7. Which of the following statements is/are false?

(a) Crystals of particular substance have the same shape no matter what the conditions of
crystallization are.
(b) There is no regularity in the shapes of the crystals of a particular substance.
(c) While differing in appearence, different crystals of the same substance have identical angles
between corresponding faces.
(d) Any difference in the appearance of two crystals of the same substances known as polymorphism.

8. Choose the correct statement for ionic solids:

(a) The radius ratio r+/r– increases as coordination number increases.
(b) As the difference in size of ions increases, coordination number increases.
(c) When coordination number is eight, r+/r– ratio lies between 0.225 to 0.414.
(d) In ionic solid of the type AX (ZnS, wurtzite), the coordination number of Zn 2+ and S 2–
respectively are 4 & 4.

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 Solid State

9. In a AB unit cell (Rock salt type) assuming A forming FCC,.

(a) The nearest neighbour of A+ is 6B– ion (b) The nearest neighbour of B– is 6A+ ion
(c) The second neighbour of A+ is 12A+ (d) The packing fraction of AB crystal is 0.52

10. The HCP and CCP structure for a given element would be expected to have
(a) the same co-ordiantion number (b) the same density
(c) the same packing fraction (d) all of these

SECTION - III: INTEGER TYPE QUESTIONS

11. How many Na+ ions are present in the NaCl unit cell

12. FeO crystal has a cubic structure and each edge of the unit cell is 5.0 Å. Taking density of the oxide
as 4.0 g cm–3, calculate the total number of Fe+2 and O–2 ions per unit cell.

13. The density of crystalline sodium chloride is 2.165 gcm–3. What would be the dimension of a cube
containing one mole of NaCl?

14. In a solid compound A atoms are present at corner, B atoms are at edge center and body centered
were as C atoms are face centered. If all the atoms along one of hte body diagonal plane are
removed. then how many atoms are missing.

15. Potassium metal crystallises in BCC manner, the number of next nearest neightbour of K is

16. Solid AB crystalises in a BCC manner. A atoms are present at the corner whereas B atoms are body
centered. If two A atoms are remove from each unit cell then the coordination number of A is

17. Silver (atomic weight = 109 g mol–1) has a density of 0.5 g/cm2. The number of silver atoms on a
surface area of 10–13 m2 can be expressed in scientific notations is Y × 10X. The value of X is:

18. Number of hexagonal faces that are present in a truncted octahedran.

SECTION - IV: MATRIX MATCH

19. Column - I (Shape) Column - II (Radius ratio r+/r–)
(A) Planar triangle (p) 0.732
(B) Square planar (q) 0.225
(C) Body centred cubic (r) 0.155
(D) Tetrahedral (s) 0.414.
(a) (A – r), (B – s), (C – p), (D – q) (b) (A – p), (B – q), (C – r), (D – s)
(c) (A – q), (B – q), (C – s), (D – r) (d) (A – s), (B – r), (C – q), (D – p)

SECTION - V: COMPREHENSION TYPE QUESTIONS

Comprehension

In hexagonal systems of crystals, a frequently encountered arrangement of atoms is described as a hexagonal

prism. Here, the top and bottom of the cell are regular hexagons and three atoms are sandwiched in between
them. A space-filling model of this structure, called hexagonal close-packed (HCP), is constituted of a sphere

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on a flat surface surrounded in the same plane by six identical spheres as closely as possible. Three spheres
are then placed over the first layer so that they touch each other and represent the second layer. Each one of
these three spheres touches three spheres of the bottom layer. Finally, the second layer is covered with a
third layer that is identical to the bottom layer in relative position. Assume radius of every sphere to be ‘r’.

20. The number of atoms in this HCP unit cell is

(a) 4 (b) 6 (c) 12 (d) 17

21. The volume of this HCP unit cell is

64 3
(a) 24 2 r3 (b) 16 2 r3 (c) 12 2 r3 (d) r
3 3

22. The empty space in this HCP unit cell is

(a) 74% (b) 47.6% (c) 32% (d) 26%

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ANSWERS
CHAPTER ASSIGNMENT
MULTIPLE CHOICE QUESTIONS (Single Correct )

1. (a) 2. (a) 3. (c) 4. (d) 5. (c)

6. (b) 7. (b) 8. (a) 9. (a) 10. (d)
11. (d) 12. (d) 13. (d) 14. (b) 15. (a)

INTEGER TYPE QUESTIONS

16. (5) 17. (7) 18. (4) 19. (8) 20. (7)
21. (2) 22. (8) 23. (8) 24. (8) 25. (4)

MULTIPLE CHOICE QUESTIONS (More than one Correct )

26. (a,c) 27. (a,c,d) 28. (b,c,d) 29. (a,b,c,d) 30. (a,b,c)
31. (a,b,c,d) 32. (a,b,c,d) 33. (a,b,d) 34. (b,c) 35. (b,d)

MATRIX MATCH TYPE QUESTIONS

36. (A) – (r), (s); (B) – (p), (r), (s); (C) – (p), (s); (D) – (q), (r)
37. (A) – (p), (q), (s); (B) – (p), (r), (s); (C) – (q), (r), (s); (D) – (q), (r), (s)

COMPREHENSION TYPE QUESTIONS

38. (c) 39. (b) 40. (a) 41. (b) 42. (c)
43. (a)

PREVIOUS YEAR QUESTIONS

1. (b) 2. (b) 3. (b) 4. (a) 5. (d)

6. (a) 7. (b,c) 8. A-(p),(s); B-(p),(q); C-(p),(q); D-(q),(r) 9. 4
10. (d) 11. 7 12. (b) 13. (a) 14. (c)
15. (b) 16. (a) 17. (a) 18. (a) 19. (c)
20. (c) 21. (b) 22. (d) 23. (d) 24. (d)
25. (d) 26. (a) 27. (3) 28. (b), (c), (d) 29. (d)
30. (2) 31. (d) 32. (3)

CHAPTER TEST
1. (d) 2. (a) 3. (d) 4. (a) 5. (b)
6. (b, c,d ) 7. (a, b, d) 8. (a, b,d) 9. (a, b) 10. (a, c)
11. (4) 12. (8) 13. (3) 14. (9) 15. (6)
16. (6) 17. (6) 18. (8) 19. (a) 20. (b)
21. (a) 22. (d)

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HINTS AND SOLUTIONS

MULTIPLE CHOICE QUESTIONS (Single Correct)
A B, or AB
1. (a) 8
1
8

2. (a) No. of octahedral voids = No. of effective atoms

r  126
3. (c)    0.583
r 216
Hence coordination will be six
4. (d) Factual
5. (c) In FCC packing efficiency =74%
6. (b) For solid only 7 type of crystal are exist and 14 bravious lattice.

A B4 , A 4 B 4 , AB
7. (b) 8
1
2

a 3
8. (a)  1.73  a  2Å  200 Pm
2
9. (a) In FCC packing fraction is 0.74.

a 3
10. (d) Use this formula r 
4
11. (d) Z indicates octahedral voids
X 2 Y4  X8Y12
12. (d) 4 or X2Y3
3

13. (d) nλ  2d sin Q

1 λ  2  0.2 109 sin16.80

λ  2  0.2 109  0.2890
λ  1.156  10 10 meter

Z M
14. (b) d  N  V
A

4  60.223
2
6.022 1023 V
V  2 1022 cm3
15. (a) Lattice energy depends upon both charge and radius.

INTEGER TYPE QUESTIONS

ZM
16. (5) d  N  a 3
A
4  239
12.7 
6.022  1023  a 3

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a 3  125  1024

a  5  108  2r   2r 
–8
r   r  = 2.5 × 10 cm

r   r  = 250 pm
25.0
r  r   5
50
Z m 2  52
d  7
17. (7) N A  V 6.022 1023  4 π  (2.9 108 )3
3
a 3
Ratio  4
18. (4) a 3 Where a is edge length
4
19. (8) 2x  3(96  x)  200

x = 88
Fe3+ ions for 100 oxide ions required = 96 – 88 = 8
20. (7) If all the face centre atom along one of the x-axis are removed then total no. of effective atom
left in unit cell = 3A + 4B = 7 atoms
Z m
21. (2) d  N  V
A
Z  6.94
0.53  Z = 1.97 2
(0.032  10 23 )(3.5  10 8 )3

103
22. (8) Cation vacancy = 105 mole = 6.023  1023 105  6.022  1018 y = 8
100

23. (8) In BCC coordination no. of each atoms will be 8

24. (8) In FCC tetrahedral voids = 2 × octahedral voids = 8
25. (8) In NaCl 4Na+ and 4Cl– ions are present effectively per unit cell.

MATRIX MATCH TYPE QUESTIONS

36. (A) – (r), (s); (B) – (p), (r), (s); (C) – (p), (s); (D) – (q), (r)
(A) In rock salt co-ordination number of both cation and anion is 6.
In rock salt r+ + r– = a/2
(B) In ZnS co-ordination number of Zn2+ is 4
In ZnS, 4Zn2+ and 4S2– are present per unit cell.
(C) In Na2O co-ordination number of Na+ is 4.
  a 3
(D) In bcc structure r  r 
2
In bcc co-ordination number both cation and anion are 8.

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37. (A) – (p), (q), (s); (B) – (p), (r), (s); (C) – (q), (r), (s); (D) – (q), (r), (s)
(A) Both Zn2+ and S2– ion have co-ordination number 4.
In ZnS only one tetrahedral void is occupied along body diagonal.
4M
For ZnS d  N  V
A

(B) In rock salt co-ordination number of both cation and anion is 6.

In rock salt only octahedral voids are occupied along the body diagonal.
4M
For rock salt d  N  V
A
4M
(C) For CaF2 d  N  V
A
–
In fluorite, F ions are present in only tetrahedral void.
4M
(D) For Na2O d  N  V
A
+
In Na2O, Na ions are present only in tetrahedral voids.

COMPREHENSION TYPE QUESTIONS

Mn F  MnF3
38. (c) 8
1
12
1
8 4

39. (b) A  2rMn 3  2rF

= 2 × 0.65 + 2 × 1.36 = 4.02Å

ZM
40. (a) d  N  a 3
A

Z = 1, M = 112
NA = 6.022 × 1023 a = 4.02Å
Hence a = 2.86 g/cc
41. (b) In ccp two tetrahedral voids are formed in each body diagonal at one fourth distance from the
corner. Hence number of tretrahedral voids = 2 × 4 = 8.
42. (c) In hcp and ccp both have equal density.
43. (a) In hcp and ccp both have coordination number 12.

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