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90

Starts at
17th May 2021,
End at
26th June 2021
MASTER CLASS
TEACHER TEACHER
Solid State
L-1
Solid State
Solid State
General characteristics of solids

● Definite shape and volume

● Incompressible in nature

● Spaces between particles are minimum.

● Interparticles forces are higher

● High melting and boiling points

● High density
 Classification of solids

Solids

Crystalline solids Amorphous solids

 Comparison between crystalline solids and amorphous solids

Crystalline solids Amorphous solids

Particles are regularly arranged. Irregular arrangement of particles.

Comparison between crystalline solids and amorphous solids

Crystalline solids Amorphous solids

Considered as supercooled liquids of pseudo
Considered as true solids
solids
 Comparison between crystalline solids and amorphous solids

Crystalline solids Amorphous solids

They show cleavage property. They do not show cleavage property

 Comparison between crystalline solids and amorphous solids

Crystalline solids Amorphous solids

They are anisotropic in nature. They are isotropic in nature

B D
B
D

C
C
A
A
 Comparison between crystalline solids and amorphous solids

Crystalline solids Amorphous solids

They are anisotropic in nature. They are isotropic in nature

 Summary

Property Crystalline solids Amorphous solids

Shape Definite geometric shape Irregular shape

Gradually soften over a range of

Melting point Sharp melting point
temperature

Cleavage property Sharp cleavage property Irregular cleavage property

Heat of fusion Definite heat of fusion Irregular heat of fusion

Anisotropy Anisotropic in nature Isotropic in nature

Nature True solids Pseudo solids / supercooled liquids

Order in arrangement Long range order Short range order

 Let’s Solve!

Q Which of the following is not a characteristic of a crystalline solid?

A Definite and characteristic heat of fusion

B Isotropic nature

C A true solid

D A regular periodically repeated pattern of arrangement of constituent

particles in the entire crystal
 Let’s Solve!

Q Which of the following is not a characteristic of a crystalline solid?

A Definite and characteristic heat of fusion

B Isotropic nature

C A true solid

D A regular periodically repeated pattern of arrangement of constituent

particles in the entire crystal
 Let’s Solve!

Q Which of the following is an amorphous solid ?

A Graphite (C)

B Quartz glass (SiO2 )

C Chrome alum

D Silicon Carbide(SiC)
 Let’s Solve!

Q Which of the following is an amorphous solid ?

A Graphite (C)

B Quartz glass (SiO2 )

C Chrome alum

D Silicon Carbide(SiC)
 Let’s Solve!

Q Which of the following is true about the value of refractive index of quartz glass ?

A Same in all directions

B Different in different directions

C Cannot be measured

D Always zero
 Let’s Solve!

Q Which of the following is true about the value of refractive index of quartz glass ?

A Same in all directions

B Different in different directions

C Cannot be measured

D Always zero
 Classification of crystalline solids

Ionic solids
Polar molecular solids

Molecular solids Non polar molecular solids

Crystalline solids Hydrogen bonded molecular solids

Metallic solids

Covalent or network-like solids

 Ionic solids
● Binding force : Ionic Bond

● Properties :
○ Hard and brittle
○ High melting point
○ Poor thermal and electrical conduction in solid state
○ Electrical conductivity is seen in molten state.
● Examples : NaCl , KCl , CsCl , ZnS
 Molecular solids
● Type : Polar molecular solids

● Binding force : Dipole - dipole force

● Properties :
○ Soft
○ Moderate melting point
○ Poor thermal and electrical conduction in
solid state

● Examples : Sold SO2 and Solid NH3

 Molecular solids
● Type : Non-Polar molecular solids

● Binding force : Weak dispersion force or London force

● Properties :
○ Soft
○ Low melting point
○ Poor thermal and electrical conduction in
solid state

● Examples : H2 , Cl2 , I2
 Molecular solids
● Type : Hydrogen bonded molecular solids

● Binding force : Hydrogen bond

● Properties :
○ Moderately high melting
○ Poor thermal and electrical
conduction in solid state

● Examples : ice (H2O)

 Metallic solids

● Binding force : Metallic bond (due to kernels)

● Properties :
○ Soft to very hard
○ High melting point
○ Excellent conductor of heat
and electricity.

● Examples : Gold , iron , Zinc etc.

 Covalent or network-like solids

● Binding force : Covalent Bond

● Properties :
○ Soft to very hard
○ High melting point
○ Poor conductor of heat and electricity.
○ Exception : Diamond is the good conductor of heat and graphite is
the good conductor of electricity.
● Examples : Diamond , graphite
 Covalent or network-like solids

Graphite Diamond
 Let’s Solve!

Q Which of the following is not the characteristic of ionic solids?

A Very low value of electrical conductivity in the molten state.

B Brittle nature

C Very strong forces of interactions

D Anisotropic nature
 Let’s Solve!

Q Which of the following is not the characteristic of ionic solids?

A Very low value of electrical conductivity in the molten state.

B Brittle nature

C Very strong forces of interactions

D Anisotropic nature
Unit cell and crystal lattice
 Unit cell and crystal lattice

Crystalline solids can be studied based on smaller repeating units which form the complete
crystal.
 Unit cell

The smallest possible GEOMETRICAL SHAPE which can act as a repeating unit for a
crystal.
 Unit cell

The smallest possible GEOMETRICAL SHAPE which can act as a repeating unit for a
crystal.
 Crystal lattice

A regular three dimensional arrangement of points in space is called a Crystal Lattice

 Parameters of unit cell

A unit cell is characterised by six parameters: a, b, c, α, β and γ

 Crystal System

Crystal System Edge length Axial angles

Cubic a=b=c α = β = γ = 90o

Tetragonal a=b≠c α = β = γ = 90o

Hexagonal a=b≠c α = β = 90o , γ = 120o

Rhombohedral or trigonal a=b=c α = β = γ ≠ 90o

Orthorhombic a≠b≠c α = β = γ = 90o

Monoclinic a≠b≠c α = γ = 90o , β ≠ 90o

Triclinic a≠b≠c α ≠ β ≠ γ ≠ 90o

Crystal System
 Variations within a Crystal System

Primitive unit cell :

When constituent particles are present only on the corner positions of a unit cell, it is
called as primitive unit cell.
 Variations within a Crystal System

Body Centred unit cell :

When a unit cell contains constituent particles present at the body centre and at the
corners of the unit cell, it is called a body-centred unit cell.
 Variations within a Crystal System

Face-Centred unit cell :

When a unit cell contains constituent particles present at the centre of each face and at the
corners of the unit cell, it is called a face-centred unit cell.
 Variations within a Crystal System

End-Centred unit cell :

When a unit cell contains constituent particles present at the centre of end faces (as shown
in the figure) and at the corners of the unit cell, it is called an end-centred unit cell.
Seven Primitive Unit Cells and their Possible Variations as
Centred Unit Cells
 Bravais lattice

There are 14 unit cells under 7 crystal system. These are called as Bravais lattice.
 Contribution of Corner atom in a Cube

1 atom is contributing equally in 8 unit cells.

Therefore, in 1 unit cell, the contribution at each corner is ⅛
 Contribution of Body centered atom in a cubic unit cell

1 atom present at body centred contributing entirely in the unit cell. Hence its contribution
is 1
 Contribution of Face centered atom in a cubic unit cell

1 atom present at each face centre, sharing with the face of another unit cell. Hence its
contribution is ½
 Contribution of edge centered atom in a cubic unit cell

And 1 atom present at the centre of the edge,

contributing equally in 4 unit cells. Hence its
contribution is ¼ in each unit cell.
 Calculation of formula of a cubical unit cell

● In the cubical unit cell :

○ A atoms are at all the corners
○ B atoms are at all face centres
○ C atoms are at all edge centres
○ D atoms are at all body centres.
Calculate formula of the unit cell.
 Calculation of formula of a cubical unit cell

Corner Face Edge Body

A B C D

no. of atoms 8 6 12 1

Contribution ⅛ ½ ¼ 1

No of effective atoms in
8×⅛=1 6×½=3 12 × ¼ = 3 1×1=1
1 unit cell

● Hence formula of unit cell = AB3C3D

 Calculation of formula of a cubical unit cell

● In the cubical unit cell, if 25 % A, 50 % B and

75 % C are removed, then calculate the
formula of the unit cell
 Calculation of formula of a cubical unit cell

Corner Face Edge Body

A B C D

no. of atoms 8 6 12 1

Contribution ⅛ ½ ¼ 1

Atoms removed 2 (25 %) 3 (50 %) 9 (75 %) 0

No of effective atoms
6 × ⅛ = 6/8 3 × ½ = 3/2 3 × ¼ = 3/4 1×1=1
in 1 unit cell

● Hence formula of unit cell = A6/8B3/2C3/4D

● On multiplying by 4, formula for complete solid = A3B6C3D4

 Calculation of formula of a cubical unit cell

Corner Face Edge Body

A B C D

no. of atoms 8 6 12 1

Contribution ⅛ ½ ¼ 1

Atoms removed 2 0 1 0

Remaining 6 6 11 1

No of effective atoms
6 × ⅛ = 6/8 6×½=3 11 × ¼ = 11/4 1×1=1
in 1 unit cell

● Hence formula of unit cell = A6/8B3C11/4D1

● On multiplying by 4, formula for complete solid = A3B12C11D4

 Packing fraction (P.F) of unit cell

It represents effectiveness of packing

Packing fraction (P.F) of unit cell
 Packing fraction (P.F) of unit cell

Packing for 3D

Volume occupied by all atoms in one unit cell

Packing for 3D =
Total volume of one unit cell
 Packing fraction (P.F) of unit cell

Packing for 3D
 Packing fraction in 2D unit cell

1. Square packing
d c

Unit cell area = abcd

= (2R)2 = 4R2
Effective number of atoms = 1
a b
Area of 1 atom = 𝝅R2

It means 78 % is occupied by atoms and 22 % is void.

 Packing fraction in 2D unit cell

2. Hexagonal packing
e d

Unit cell area = abcdef

= 6 × Δabo (area of triangle)
f c
o
= 6√3 R2

a b
 Packing fraction in 2D unit cell

2. Hexagonal packing
e d
Effective number of atoms in
1 unit cell = 1 + 6 × ⅓ = 3
f c
o
Area occupied by 1 atom = 𝝅R 2

Total area occupied by 3 atoms = 3𝝅R2

a b

It means 91 % is occupied by atoms and 9 % is void/empty space

Hence hexagonal packing is better than square packing
 Coordination Number

● It means number of atoms touching( nearest) to a particular atom.

For smaller circle, CN is 3

In an ionic crystal, both cations and anions have different CN, depending upon their size.
 Packing fraction (P.F) for 3D

Volume occupied by all atoms in one unit cell

PF =
Total volume of one unit cell

● In the cubical unit cell, if a is the edge length, then

volume of the unit cell = a3
● If all atoms are identical , then
 Density of solid

Mass of unit cell

Density of unit cell =
Volume of unit cell

Mass of atoms in unit cell

Or , Density of unit cell =
Volume of unit cell
 Cubical unit cell

a. Primitive type/ Simple cube

❖ Atoms are present at the corners of the cube.

In simple cubic unit cell, the contribution at each corner is 1/8 and there are total 8 corners.
1. Zeff in Simple cubic unit cell = 1/8 × 8 = 1 atom
 Cubical unit cell

a. Primitive type/ Simple cube

 Cubical unit cell

a. Primitive type/ Simple cube

5. Packing fraction (PF)

It means 52 % is occupied by atoms and 48 % is

void/empty space
 Cubical unit cell

a. Primitive type/ Simple cube

6. density (d)
 Let’s Solve!

An element X (molecular weight 100) crystallizes as simple cubic , if radius of atom is 5 Å

Q . Calculate density in g/cc or g/ml . Take N A = 6 × 1023
 Solution !!!

An element X (molecular weight 100) crystallizes as simple cubic , if radius of atom is 5 Å

. Calculate density in g/cc or g/ml . Take N A = 6 × 1023
Cubical unit cell

b. Body centred Cubic

 Cubical unit cell

b. Body centred Cubic

The contribution at each corner is ⅛ and ,

the contribution at body centre is 1
So,
1. Zeff in body centred unit cell = (⅛ × 8) + (1 × 1) = 2 atoms
 Cubical unit cell

b. Body centred Cubic

Packing fraction (PF)

It means 68 % is occupied by atoms and 32 % is void/empty

space
 Cubical unit cell

b. Body centred Cubic

Density (d)

2
Cubical unit cell

c. Face- centred Cubic

 Cubical unit cell

c. Face- centred Cubic

The contribution at each corner is ⅛ and,

The contribution at each face centre is ½
There are 6 faces in the unit cell.
So,
1. Zeff in face-centred unit cell = (⅛ × 8) + (½ × 6) = 4 atoms
 Cubical unit cell

c. Face- centred Cubic

Packing fraction (PF)

It means 74 % is occupied by atoms and 26 % is

void/empty space
 Cubical unit cell

c. Face- centred Cubic

Density (d)

4
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 90

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