Physical Chemistry

Solid State

Deepak Poonia
(IIT Delhi)
Interparticle force of attraction and thermal energy
Shape

Volume
 Characteristics of solids

(i) They have definite mass, volume and shape.

(ii) Intermolecular distances are short.

(iii) Intermolecular forces are strong.

(iv) Their constituent particles (atoms, molecules or ions) have fixed

positions and can only oscillate about their mean positions.

(v) They are incompressible and rigid

 Classification of solids
1. On the basis of arrangement of particles
(i) Crystalline solids
(ii) Amorphous solids
(i) Crystalline solids

The arrangement of constituent particles (atoms, molecules or ions) in a crystal is

ordered and repetitive in three dimensions.
(i) Crystalline solids

The arrangement of constituent particles (atoms, molecules or ions) in a crystal is

ordered and repetitive in three dimensions.

If we observe the
pattern in one region of
the crystal, we can
predict accurately the
position of particles in
any other region of the
crystal however far they
may be from then place
of observation.
 Sodium chloride
and quartz are
typical examples
of crystalline
solids.

Quartz
(ii) Amorphous solids

Amorphous means No form.

A regular and periodically repeating pattern is observed over short distances only

Like liquids, amorphous solids have a tendency to flow, though very slowly. Therefore,
sometimes these are called pseudo solids or super cooled liquids.
quartz (crystalline) quartz glass (amorphous)
Q. Refractive index of a solid is observed to have the same value along all
directions. Comment on the nature of this solid.
Most of the solid substances are crystalline in nature.

Metallic Elements iron, copper and silver

Non - Metallic Elements sulphur, phosphorus and iodine

Compounds sodium chloride, zinc sulphide and naphthalene

2. On the basis of different binding forces
(i) Molecular solid

(ii) Ionic solids

(iii) Metallic solid

(iv) Covalent or Network solid

(i) Molecular solid

Constituent particle : Molecule

Non polar Molecular Solids

(i) Molecular solid

Constituent particle : Molecule

Polar Molecular Solids

Solid NH3 and Solid SO2

(i) Molecular solid
Constituent particle : Molecule

Hydrogen Bonded Molecular Solids

(ii) Ionic solid

Constituent particle : ions

These solids are hard and brittle in nature.

They have high melting and boiling points
Q Ionic solids conduct electricity in molten state but not in solid state.
Explain.
(ii) Ionic solid

Since the ions are not free to move about, they are electrical insulators in the solid
state. However, in the molten state or when dissolved in water, the ions become
free to move about and they conduct electricity.
(iii) Metallic solid
Constituent particle : Metal
• Positive ions surrounded by and held together by a sea of free electrons.

• These free and mobile electrons are responsible for high electrical and thermal
conductivity of metals.
(iv) Covalent or Network solid

They have extremely high melting points and may even decompose before melting.
They are insulators and do not conduct electricity.
BUT…

• Graphite is a good
conductor of
electricity.
• Different layers can
slide one over the
other. This makes
graphite a soft solid
and a good solid
lubricant
Q Classify the following solids in different categories based on the nature of
intermolecular forces operating in them:
Potassium sulphate,
tin
Benzene
urea
ammonia
water
zinc sulphide
graphite
rubidium
argon
silicon carbide
Crystal lattice

Following are the characteristics of a crystal lattice:

(a) Each point in a lattice is called lattice point or lattice site.
(b) Each point in a crystal lattice represents one constituent particle which may be an
atom, a molecule (group of atoms) or an ion.
(c) Lattice points are joined by straight lines to bring out the geometry of the lattice.
Unit cell
Unit cell
Unit cell
Parameters of a Unit cell
Types of Unit cell :

(i) Primitive or Simple Unit cell :

(ii) Centered Unit cell :

Body centered Unit cell :

Face centered cell :

End centered Unit cell :

Packing in solids
1D Packing
2D Packing

(i) AAAA ... type packing (ii) ABABAB... type packing

(i) AAAA ... type packing
(i) Relation between edge length (a) and r :
(ii) Coordination Number (No of nearest neighbours) :
(iii) % Packing efficiency :
(ii) ABAB ... type packing
(i) Relation between edge length (a) and r :
(ii) Coordination Number (No of nearest neighbours) :
(iii) % Packing efficiency :
Packing in Three Dimensions (3D)
Packing in Three Dimensions (3D)
 Packing in Three Dimensions (3D)

Using hexagonal closed packing (2D)

3D Packing
Cubic system
Q. Explain how much portion of an atom located at
(i) corner
(ii) body Centre of a cubic unit cell
is part of its neighboring unit cell.
(i) Simple cubic lattice

Simple cubic (sc)Unit cell

(i) Simple cubic lattice
(i) Relation between edge length (a) and r :
(i) Simple cubic lattice

(ii) Effective number of particles in a unit cell (Z):

(i) Simple cubic lattice
(iii) Coordination Number (No of nearest neighbours) :
(i) Simple cubic lattice
(iv) % Packing efficiency :
(i) Simple cubic lattice

(v) Density :
(ii) Body centered cubic lattice

Body centered cubic unit cell

(ii) Body centered cubic lattice
(i) Relation between edge length (a) and r :
(ii) Body centered cubic lattice

(ii) Effective number of particles in a unit cell (Z):

(ii) Body centered cubic lattice
(iii) Coordination Number (No of nearest neighbors) :
(ii) Body centered cubic lattice

(iv) % Packing efficiency :

(ii) Body centered cubic lattice
(v) density
(iii) Face centered cubic lattice
(iii) Face centered cubic lattice
(i) Relation between edge length (a) and r :
(iii) Face centered cubic lattice
(ii) Effective number of particles in a unit cell (Z):
(iii) Face centered cubic lattice
(iii) Coordination Number (No of nearest neighbours) :
(iii) Face centered cubic lattice

(iv) % Packing efficiency :

(iii) Face centered cubic lattice
(v) density
Hexagonal closed packing
Voids
2D voids
(i) Triangular Void (ii) Square void
3D voids
(iii) Cubic void
(i) Tetrahedral Void (ii) Octahedral void
Location of Tetrahedral and Octahedral voids in FCC lattice
Octahedral void
Tetrahedral void
Q A compound is formed by two elements M and N. The element N forms
ccp and atoms of M occupy 1/3rd of tetrahedral voids. What is the
formula of the compound?
Density of a solid
Q An element has a body-centred cubic (bcc) structure with a cell edge of
288 pm. The density of the element is 7.2 g/cm3 . How many atoms are
present in 208 g of the element?

Ans 24.16×1023 atoms

Q An element with molar mass 2.7×10-2 kg mol-1 forms a cubic unit
cell with edge length 405 pm. If its density is 2.7×103 kg m-3, what is
the nature of the cubic unit cell?
Q Silver forms ccp lattice and X-ray studies of its crystals show that the edge
length of its unit cell is 408.6 pm. Calculate the density of silver (Atomic
mass = 107.9 u).

Ans 10.5 g cm-3

Defects in solids
Defects in solids
Point defects

Vacancy defect Interstitial defect

Stoichiometric defect / intrinsic / Thermodynamic Defect
Schottky defect Frenkel defect
Stoichiometric defect / intrinsic / Thermodynamic Defect
Schottky defect
Stoichiometric defect / intrinsic / Thermodynamic Defect

Frenkel defect
Non-Stoichiometric defect
Metal excess defect
Non-Stoichiometric defect
Metal deficiency defect
Impurity defect