1 | SOLID STATE CHEMISTRY

1 | SOLID STATE
Introduction

Solids have a definite shape and rigidity. This is due to the fact that constituent particles cannot posses enough
energy to move about to kept up different positions.
Solids are characterized by their definite volume which does not depend on the size and shape of the container. This
is due to the close packing of molecules and strong short range intermolecular forces between them.

Amorphous and Crystalline Solids

Solids are divided into two classes on the basis of haphazard and regular arrangement of the building constituents.
(i) Amorphous solids:
(ii) Crystalline solids:

Difference between crystalline and amorphous solids

S.N. Crystalline Solids Amorphous solids

1 The have a definite and regular geometry due to They do not have any pattern of arrangement of
definite and orderly arrangement of atoms, ions or atoms, ions or molecules and thus, do not have
molecules in three–dimensional space. any definite geometrical shape.
2. They have sharp melting points and change abruptly Amorphous solids do not have sharp melting
into liquids. points and do not change abruptly into liquids.
They melt over a range of temperature.
3. Crystalline solids are anisotropic. Some of their Amorphous solids are isotropic. Their physical
physical properties like refractive index, electrical properties like refractive index, electrical
conductivities etc. are different in different directions. conductivities etc. are same in all directions.
4. These are considered as true solids. These are considered pseudo–solids or
supercooled liquids of high viscosity. Window
glass panes of old buildings are thicker at the
bottom because glass has the property to flow.
5. They undergo clean cleavage. They undergo rough or irregular cut.
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Classification of Crystalline Solids

Crystalline solids can be further categorized as ionic, covalent, molecular or metallic depending upon the nature of
bonding.
S. Characteris Ionic solid Covalent or network Molecular solid Metallic solid
No. tics solid
1. Constituent Positive and negative ions Neutral atoms Molecules (polar or Positive ions and
particles non–polar) electrons
(delocalised)

2. Bonding/ Electrostatic or coulombic Shared pairs of Weak polar forces electrostatic attraction
Attractive electrons (covalent) or between positive ions
forces Vander Waal's and electrons
forces or hydrogen
bonding

3. Hardness Hard and brittle Very hard Very soft Hard or soft
4. Melting High – 1500 Very high  4000 Low High or low
point (k)
5. Electrical Bad conductors (insulators) Bad conductors Bad conductors Good conductors
conductivity due to absence of free ions. (insulators) with few (insulators)
Good conductors in fused exceptions like
state or in aqueous solution graphite
due to presence of free ions.
6. Examples NaCl, MgO, KCl, CsCl,ZnS, Diamond (C), Ice,Solid CO2, s–block and d–block
Na2 SO4, KNO3,CuSO4.5H2O Graphite (C), Sulphur (S8), metals and some p–
Carborundum (SiC), Glucose, block elements. Na,
Quartz (SiO2), Boron– Naphthalene, etc. Cu, Ag, Au, Ni, Pt.
nitride (BN) Cr. etc.
The sites which are occupied by constituent units (atoms, molecules and ions) are called lattice sites or lattice points.
When lattice points are joined together then they form crystal lattice.

Unit Cells:
It can be defined as the smallest repeating unit in space lattice which, when repeated over and over
again results in a crystal of the given substance.
Each unit cell is characterized by two parameters shown in fig. 1.1 The lengths of the edges of the
unit cell (a, b and c) and (ii) The angles between three imaginary axes OX, OY and OZ,
respectively ( and .
Fig. 1.1
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Crystal System
There are seven types of basic or primitive unit cells that have been recognized between crystals. These are cubic,
orthorhombic, tetragonal, monoclinic, triclinic, hexagonal and rhombohedral.
S. System Edges Angles Examples
No.
1. Cubic, a = b = c,  =  All the three All right angles NaCl, KCl, ZnS, diamond, alums, Cu
=  = 90º are equal
2. Orthorhombic all unequal All right angles KNO3, BaSO4, K2SO4, rhombic sulphur
a  b  c,  =
90º
3. Tetragonal Two equal All right angles TiO2, SnO2, NH4Br, CaSO4, white tin
a = b c,  =  =  = 90º
4. Monoclinic all unequal Two right Monoclinic sulphur
a  b  c, 90º ,  angles KClO3, CaSO4.2H2O, Na2B4O7.10H2O,
= 90º CuSO4.5H2O,H3BO3,K2Cr2 O7
5. Triclinic all unequal None of right CuSO4. 5H2O, H3BO3,K2Cr2O7
    c,   angles
90
6. Hexagonal Two equal Angle between ZnO, CdS, HgS, SiC, AgI
a  b  c, 90º ,  equal edges =
= 120º 120º
7. Rhombohedral All these equal All equal but NaNO3 , ICl, quartz, (CaCO3 ) calcite
a = b = c, none 90º CaCO3.HgS (cinnabar)
90º
Unit cells are divided into two main types:
(a) Primitive or simple unit cells: In this type of unit cell, constituent particles are present only at the corners.
(b) Non–Primitive unit cells: In these unit cells, constituent units are located not only at corners but also at some
other positions like face centres, body centres etc.
There are three types of non–primitive unit cells:
(i) Body–centred unit cells : There are lattice points at the corners as well as in the body centre of unit
cell.
(ii) Face–centred unit cells : There are lattice points at the corners as well as at the centre of each face of
the unit cell.
(iii) End centred unit cell : In this type of unit cells, the constituent particles are situated at each corner and
at the centres of any two opposite faces.

Simple Cubic bcc fcc

Coordination number:
In case of ionic solids the coordination number of a particular ion is the number of oppositely charged ion
surrounding that particular ion.
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CALCULATION OF NUMBER OF PARTICLES IN A UNIT CELL
Types of lattice points Contribution to one unit cell
Corner 1/8 particle / atom / ion
Edge ¼ particle / atom / ion
Face–centred ½ particle / atom / ion
Body–centred 1 particle / atom / ion

(a) Simple or Primitive cubic unit cell:

1
Z  8  1
8
(b) Body centred cubic unit cell (bcc)
1
Z  8   1 2
8
(c) Face–centred cubic unit cell (fcc) :
1 1
Z  8  6   4
8 2

Example 1.1
In a face–centred cubic arrangement of 'A' and 'B' atoms, 'A' atoms occupy the corners and 'B' atoms
occupy the face centres of the unit cell. One of the corners in each unit cell remains vacant. What is the
simplest formula of the compound?

Ans. Seven of the corners of the unit cell are occupied by 'A' atoms. Thus,
1 7
Its contribution of the unit cell = 7  
8 8
1
Contribution of 'B' atoms to the unit cell = 6   3
2
7 7 24
A:B  :3  :  7:24
8 8 8
 Simplest formula of the compound is A7 B24 .

Example 1.2
A unit cell consists of a cube in which there are anions 'Y' at each corner and cations 'X' at the centre of
alternate faces of a unit cell. What is the simplest formula of the compound?

1
Ans : Contribution of the anions to the unit cell  8  1
8
1
Contribution of the cations to the unit cell  2   1
2
X : Y = 1 : 1 The simplest formula of the compound is XY.
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Close Packing in Solids

Packing in one dimension:

In one dimension, spheres are placed linearly in a horizontal row, touching each other as shown in fig. 1.3

Fig. 1.3

Packing in two dimensions:

(a) Square close packing: In this arrangement, the rows have horizontal and vertical alignment, Fig. 1.4
In this packing the coordination number is found to be 4 as each central sphere is in contact with four other
spheres.

(b) Hexagonal close packing: In this arrangement, the rows are so arranged that sphere in every second row
occupy the depressions between the spheres of first row (fig.1.5). The spheres in the third row are vertically
aligned with the spheres in the first row and those in the fourth row are vertically aligned with the spheres in
the second row. The similar pattern is followed throughout. Each sphere is surrounded hexagonally by six
other spheres. In this packing, the coordination number is 6.

Fig. 1.4 Fig. 1.5

Packing in three dimensions:

In order to develop three dimensional close packing, let us retain the

hexagonal close packing in the first layer. For close packing, each spheres in
the second layer rests in the hollow at the centre of three touching spheres in
the layer as shown in figure 1.6.
The spheres in the first layer are shown by solid lines while those in second
layer are shown by broken lines. It may be noted that only half of the
triangular voids in the first layer are occupied by spheres in the second layer (i.e., either b or c). The unoccupied
hollows or voids in the first layer are indicated by (c) in figure
There are two alternative ways in which species in third layer can be arranged over the second layer,
(i) Hexagonal close packing: The third layer lies vertically above the first and the spheres in third layer rest in
one set of hollows on the top of the second layer. This arrangement is called ABAB type and 74% of the
available space is occupied by spheres.
(ii) Cubic close packing: The third layer is different from the first and the spheres in the third layer lie on the
other set of hollows marked ‘C’ in the first layer. This arrangement is called ABCABC. type and in this also
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74% of the available space is occupied by spheres. The cubic close packing has face centred cubic (fcc) unit
cell. The coordination no. in both type of packing is l2.

Voids or Interstitial Voids or Interstitial Sites

In a close packing of spheres, there is always some empty space left. The empty space is called hole or void or
interstitial site. Common interstitial sites in closely packing spheres are tetrahedral and octahedral.
Number of octahedral voids = Number of constituent units at packing sites.
Number of tetrahedral voids = 2  Number of constituent units present at packing sites.

Example 1.5
Magnetite, magnetic oxide of iron used on recording tapes, crystallize with iron atoms occupying 1/8 of the
tetrahedral holes and ½ of the octahedral holes in a closed packed array of oxide ions. What is the formula
of the magnetite?
Sol. Let number of oxide ions in packing = n
 Number of tetrahedral voids = 2n
and Number of octahedral voids = n
1
Number of iron atoms =  number of octahedral voids
8
1 1
  2n   n
8 2
n n 3n
  
4 2 4
3n
Ratio of iron and oxygen atoms (Fe : O) =  :n 3:4
4
 Molecular formula of magnetic = Fe3O4

Example 1.6
In a cubic lattice, the closed packed structure of mixed oxides of the lattice is made up of oxide ions; one
eight of the tetrahedral voids are occupied by divalent ions (A2+) while one–half of the octahedral voids are
occupied by trivalent ions (B3+). What is the formula of the oxide?
Ans. Let there be 80 O2– ions in the crystal
Octahedral voids = 80
Tetrahedral voids = 160
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1
A2+ ions = 160  20
8
1
B3+ ions =  80  40
2
A2 : B3 :O2  20:40:80 1:2:4
 Molecular formula of oxide will be AB2O4

Example 1.7
In corundum, oxide ions are arranged in hcp array and the aluminium ions occupy two–third of octahedral
voids. What is the formula of corundum?
Ans. Number of O2– ions present in packing = n
 Number of octahedral voids = n
2
Number of Al3+ ion   n
3
2
Al3+ : O2–  n :n  2:3
3
 Simplest formula of corundum is Al2O3.

Derivation of the relationship between radius (r) of the octahedral void and the radius
(R) of the atoms in close packing:
An octahedral void is shown in fig.. The shaded sphere represents an octahedral void. Let the radius of the
void be r. Cross–section of octahedron is represented by square ABCD. Let the radii of the spheres used in packing
be R.
Length AB = Length BC = 2R
Length AC = 2R + 2 r
In  ABC, AC2 = AB2 + BC2
(2R + 2r)2 = (2R)2 + (2R)2
= 8 R2
or 2R + 2r = 8R
or 2r  8R  2 R
r
or  2  11.414 1 0.414
R
r
Thus, for an octahedral void, void  0.414
R sphere