SOLID STATE

Solids are characterised by the state of matter in which particles are closely packed and
held together by strong inter molecular attractive force.

1 Properties of Solids :

(a) In solid state the particles are not able to move randomly.

(b) They have definite shape and volume.

(c) Solids have high density.

(d) Solids have high and sharp melting point which is depend on the strength or value of
binding energy.

(e) They are very low compressible.

(f) They show very slow diffusion.

Classification of Solids
Solids are divided into two classes, namely crystalline and amorphous solids. A solid is said to be
crystalline if the constituents arrange themselves in regular manner throughout the threedimensional
network. The ordered arrangement of building constituents extends over a large distance (long
range order). On the other hand, in amorphous solids, the arrangement of building constituents is
not regular (short range order).
Crystalline solids :
(a) In this type of solids the atoms or molecule are arranged in a regular pattern in the three
dimensional network.

(b) They have well defined geometrical pattern, sharp melting point, definite heat of fusion and
anisotropic nature.

(c) Anisotropic means they exhibit different physical properties in all directions.
e.g. The electrical and thermal conductivities are different directions.

(d) They are generally incompressible.

(e) The general examples of crystalline solids are as Quartz, diamond etc.
Amorphous Solids :
(a) In this type of solids, the arrangement of building constituents is not regular.

(b) They are regarded as super cooled liquids with high viscosity in which the force of attrac-
tion holding the molecules together are so great, that the material becomes rigid but there
is no regularity in structure.

(c) They do not have sharp melting points.

(d) They are isotropic as they exhibit same physical properties in all the directions.

(e) The general examples of this solids are as glass, Rubber, plastics etc.

Defference between crystalline and amorphous solids :

Property Crystalline solids Amorphous Solids

1. Shape They have definite and regular They do not have definite and
geometrical form. regular geometrical form.

2. Melting point They have definite melting pointThey do not have definite melting
point

3. Heat of fusion They have a definite heat of fusion They do not have definite heat of
fusion

4. Compressibility They are rigid and incompressible. These may be compressed to

any appreciable extent.

5. Cutting with a They give cleavage i.e. they They are given irregular cleavage
Sharp edged tool break into two pieces with plane i.e.they break into two pieces with
surfaces. irregular surface.

6. Isotropy and They are anisotropic. They are isotropic.

Anisotropy

Questions based on types of solids :

1. A solid X melts slightly above 273K and is a poor conductor of heat and electricity. To
which of the following categories does it belong -
(1) Ionic solid (2) Covalent solid (3) Metallic (4*) Molecular
2. In a crystal, the atoms are located at the position of -
(1) Zero P.E. (2) Infinite P.E. (3*) Minimum P.E. (4) Maximum P.E.
3. Graphite is an example of -
(1) Ionic solid (2*) Covalent solid
(3) Vander Waal’s crystal (4) Metallic crystal
4. Amorphous solids -
(1) Possess sharp melting points
(2) Undergo clean cleavage when cut with knife
(3*) Do not undergo clean cleavage when cut with knife
(4) Possess orderly arrangement over long distances
 Types of crystalline solids

Ionic Metallic Covalent molecular

Particles Anions, Metal ions in Atoms Molecules (or
occupying cations electron cloud atoms)
lattice points
Binding force Electrostatic Metallic Covalent Van der waals
attraction bonds bonds dipole-diople
Properties Hard, Brittle, Soft to very Very hard, Soft, poor
poor thermal hard, good poor thermal thermal and
and electrical thermal and and electrical electrical
conductors electrical conductors conductors
conductors
Example NaCl, CaBr2, Li, K, Ca, Cu, C(diamond) H2O, H2,
KNO2, etc Na, etc. SiO2 (quartz), CO2, Ar etc
etc

Terms and concepts

(i) Space lattice or crystal lattice
It may be defined as a regular three dimensional arrangement of identical points in space.
The positions which are occupied by atoms, ions or molecules in the crystal lattice are called
lattice points or lattice sites.
Y

Lattice Points

c
O b
X
a
Z
Space lattice and a Unit cell

(ii) Unit Cell

A space lattice can be subdivided into a number of small cells known as unit cells. It can be
defined as the smallest block from which entire crystal can be built up by its translational
repetition in three dimensions.
 The unit cell shown in figure is characterizes by a, b & c along the three edges of the unit cell
& the angles &  between the pair of edges

c

 X
 b
a
Z

The angle  is between the edges b & c. Angle is between the edges c & a
Angle is between the edges a & b

Edge
Corner
2. face
dge
1. E
3. Corner
8. B
ody
dia

nal
gon
al

o
diag
ace
5. Edge 4. body
7. F
centre centre

6. Face
centre

1. Total number of edges in a cube = 12

2. Total number of faces in a cube = 6
3. Total number of corners in a cube = 8
4. Total number of body centre in a cube = 1
5. Total number of edge centre in a cube = 12
6. Total number of face centre in a cube = 6
7. Total number of face diagonals in a cube = 6 × 2 = 12
8. Total number of body diagonals in a cube = 4

LAW OF CONSTANCY OF SYMMETRY :

According to this law, all crystals of a substance have the same elements of symmetry, A
crystal possess following three types of symmetry.

Plane of symmetry :
It is an imaginary plane which passes through the centre of a crystal can divide it into two
equal portions which are exactly the mirror images to each other.
 Planes of symmetry

Axis of symmetry :
(a) It is an imaginary line about which the crystal may be rotated so that it presents the same
appearance more than once in a complete rotation through 360º.
(b) The axes of symmetry are called diad, triad, tetrad and hexad respectively. It is the original
appearance and is repeated twice (180º), thrice (120º), four times (90º) and six times (60º)
in one rotation.
(c) These axes of symmetry are also called as two fold, four and six fold respectively.
(d) Five fold symmetry is not found in crystals.

(i) Axis of two fold symmetry. (ii) Axis of three fold symmetry.

(iii) Axis of four fold symmetry. (iv) Axis of six fold symmetry.
 Centre of symmetry :
(a) It is a point in the crystal that any line drawn through it intersects the surface of the crystal
at equal distance on either side.

Centre of
symmetry

X
Z

Note : Only simple cubic system have one centre of symmetry. Other system do not have centre
of symmetry.

ELEMENTS OF SYMMETRY :
(a) The total number of planes, axes and centre of symmetries possessed by a crystal is
termed as elements of symmetry.
(b) A cubic crystal possesses total 23 elements of symmetry.
(i) Plane of symmetry (3 + 6) = 09
(ii) Axes of symmetry (3 + 4 + 6) = 13
(iii) Centre of symmetry (1) = 01

Total symmetry = 23

Types of Lattices and Types of Unit Cell

(i) Primitive or simple Unit Cells: In a primitive unit cell, the same type of particles are
present at all the corners of the unit cell.
 
 

 
 
simple cubic
(ii) Non-primitive or centered unit cells:
There are three types of nonprimitive unit cells as follows:
(a) Face Centered : When atoms are present in all 8-corners and six face centres in a
cubic unit cell then this arrangement is known as FCC.
 

 

 

 

 
face centred cubic (fcc)
(b) End-Centered : When in addition to particles at the corners, there are particles at the
centres of the end faces.
 

 

 

 
end centred cubic (fcc)
c) Body Centered : When atoms are present at 8 corners as well as in the body centre in a
cubic unit cell then this arrangement is known as BCC.
 
 

 
 
Body centred cubic (bcc)

Seven Crystal Systems

Parameters of Unit Cell

Crystal System Bravais Lattices Example
Intercepts Interfacial angle
1. Cubic Primitive, Face Centered, a = b = c  =  =  = 90o Pb,Hg,Ag,Au
Body Centered = 3 Diamond,
NaCl, ZnS
2. Tetragonal Primitive, Body Centered =2 a = b  c  =  =  = 90o TiO2,SnO2
3. Orthorhombic Primitive, Face Centered, a  b  c  =  =  = 90o KNO2, K2SO4
Body Centered, End
Centered = 4
4. Hexagonal Primitive = 1 a=bc  =  = 900, Mg, SiO2, Zn, Cd
 = 120o
5. Rhombohedral Primitive = 1 a=b=c  =  = 90o, 90o As, Sb, Bi, CaCO3
6. Monoclinic Primitive, End Centered = 2 abc  =  = 90o, CaSO4,2H2O
  90o
7. Triclinic Primitive = 1 abc       900 K2Cr2O7,
CaSO45H2O
Total = 14 (Total 14 type of lattices are called Braivais lattices )
Seven Crystal Systems and Fourteen Bravais Lattice

CUBIC

a
a
a
Simple Face Centred Body Centred

ORTHORHOMBIC

b
a Simple End Centred Body Centred Face Centred

TETR AG O N AL M O N O C L IN IC

c c

a b b
a a
Simple Body Centred End Centred
Simple

RHOMBOHEDRAL TRICLINIC HEXAGONAL

a

c
a c

a b g 120o a
a a b a
a
Calculation of number of particles in a unit cell (Z)
In a crystal atoms located at the corner and face center of a unit cell are shared by other cells and
only a portion of such an atom actually lies within a given unit cell.
(i) A point that lies at the corner of a unit 6 8
cell is shared among eight unit cells
and therefore, only one eighth of each 5 7
such point lies within the given unit cell. 2 4

1 3

(ii) A point along an edge is shared by four unit cells and only onefourth of it lies within any
one cell.

1 2


4 3

(iii) A facecentered point is shared by two unit cells and only one half of it is present in a given
unit cell.
2 3
1 4

5
6
8 7
(iv) A bodycentered point lies entirely within the unit cell and contributes one complete point
to the cell.
2
 3
1 4

5 6
8 
7

Type of Lattice point Contribution to one unit cell

Corner 1/8
Edge 1/4
Facecenter 1/2
Body Center 1
 Calculation of number of particles in a unit cell
Type of unit cell Lattice points Lattice points Lattice points Z = no. of lattice
at corners at face-centered at body centered points per unit cell
1
SCC 8 0 0 8× =1
8
1
BCC 8 0 1 8× +1×1 = 2
8
1 1
FCC 8 6 0 8× +6 × = 4
8 2

Relation between edge length of unit cell and radius of atoms

(i) Simple cubic or Primitive –
(a) edge length of unit cell a = 2 r (b) atomic radius r = a/2

r r

(c)
(ii) Body centre cubic
4 3a
(a) edge length of unit cell = r (b) atomic radius, r =
3 4

3a a

(iii) Face centre cubic/cubic close packed

4r 2a
(a) edge length of unit cell a = (b) atomic radius r =
2 4

a
2a
1: A solid has a cubic structure in which X atoms are located at the corners of the cube,
Y atoms are at the cube centres and O atoms are at the edge centres. What
is the formula of the compound?

2: Potassium crystallizes in a body centered cubic lattice. What is the approximate number of unit
cells in 4.0g of potassium? Atomic mass of potassium = 39.

3. A compound formed by elements X and Y crystallizes in the cubic structure where Y atoms
are at the corners of the cube and X atoms are at the alternate faces. What is the formula of
the compound.
4. Xenon crystallises in the face centered cubic lattice and the edge of the unit cell is 620 pm.
What is the nearest neighbour distance and what is the radius of xenon atom.
Co-ordination number (C.N.) :
(a) It is defined as the number of nearest neighbours or touching particles with other particle
present in a crystal is called its co-ordination number.
(b) It depends upon structure of the crystal.
(c) For simple cubic system CN = 6.
(d) For bcc CN = 8.
(e) For fcc CN = 12.

Density of lattice matter :

(a) It is defined as the ratio of mass per unit cell to the total volume of unit cell.
mass per unit cell Z  At. wt.
(b) Density of lattice matter = volume of unit cell = N  volume of unit cell

Where Z is the number of atoms per unit cell and N is the Avogadro number.

Packing fraction (P.F.) :

It is defined as ratio of the volume of the unit cell that is occupied by spheres of the unit cell
to the total volume of the unit cell.
(a) Simple cubic unit cell :
Let the radius of atom in packing = r
Atoms are present at the corner of the cube, each of the eight atom present at the eight
corners shared amongst eight unit cells.
1
Hence number of atoms per unit cell = 8 × =1
8
a
again r=
2
4 3
r
therefore, P.F. = 3 3 = 0.52 % P.F. = 52%
( 2r )
% of void = 100 – 52 = 48%

(b) Body centered cubic unit cell :

1
Number of atoms per unit cell = 8 × +1=2
8

3a
r=
4

4 3
2 r
3
3
P.F. =  4r  = 0.68
 
 3
% P.F. = 68%
% of void = 100 – 68 = 32%
(c) Face centered cubic unit cell :
Number of atoms per unit cell = 4

2a
r=
4

4 3
4 r
3
3
P.F. =  4r  = 0.74 % P.F. = 74% % of void = 100 – 74 = 26%
 
 2

1: Calculate the packing fraction for the Ca unit cell, given that Ca crystallizes in a face-centered
cubic unit cell.
2 : Gold has a close-packed structure which can be viewed as-spheres occupying 0.74
of the total volume. If the density of gold is 19.3 g/cc, calculate the apparent
radius of a gold ion in the solid
3: An element occurs in bcc structure with a cell edge of 288 pm. The density of metal
is 7.2 g cm–3. How many atoms does 208 g of the element contain?
4: When heated above 916ºC, iron changes its crystal structure from body-centered cubic
to cubic closed packed structure. Assuming that the metallic radius of the
atom does not change, calculate the ratio of density of the bcc crystal to that
of the ccp crystal.
5. An element occurs in the BCC structure with cell edge of 288 pm. The density of the element
is 7.2 g/cm3. How many atoms of the element does 208 g of the element contain.
6. An element crystallizes in a structure having fcc unit cell of an edge 200 pm. Calculate the
density if 200 g of this element contains 24 × 1023 atoms.
7. Chromium crystallizes in a body-centered cubic lattice whole density is 7.20 g/cm3. The
length of the edge of the unit cell is 288.4 pm. Calculate Avogadro’s number.
8. An element occurs in BCC structure. It has a cell edge of 250 pm. Calculate it molar mass if
its density 8.0 g cm-3.