The Solid State

General Characteristics

On the basis of the forces of attraction between the constituent particles, matter exists in gaseous
state, liquid state and solid state.

The constituent particles in solids are held together by strong forces of attraction.

Solids have definite shape and volume, lack the ability to flow, and are incompressible and rigid.

A solid with the desired properties can be prepared by altering its structure.

The study of the structures of solids has immense significance in science and technology.

Amorphous and Crystalline Solids

Based on arrangement, solids are classified into two types:

• Crystalline solids
• Amorphous solids

Crystalline solids have definite geometrical shapes.

Amorphous solids do not have any definite geometrical shapes.

Crystalline solids have sharp melting points.

Amorphous solids do not have sharp melting points.

Crystalline solids are true solids.

Amorphous solids are pseudo solids or super-cooled liquids.

Crystalline solids are anisotropic in nature.

Amorphous solids are isotropic in nature.

Crystalline solids show plane of symmetry, axis of symmetry and centre of symmetry.

Amorphous solids so not show any symmetry.

Crystalline Solids: Molecular and Ionic Solids

On the basis of the type of forces holding the constituent particles together, crystalline solids
are broadly classified into molecular solids, ionic solids, metallic solids and covalent or
network solids.

Solid helium, solid argon, solid neon, solid dihydrogen, solid carbon dioxide, iodine and
carbon tetra chloride are some examples of non-polar molecular solids.

Non-polar molecular solids have low melting and boiling points, and are non-conductors of
electricity.

Solid sulphur dioxide and solid hydrochloric acid are examples of polar molecular solids.

Polar molecular solids have relatively high melting and boiling as when compared to non-
polar molecular solids, and are non-conductors of electricity.

Ice and solid hydrofluoric acid are hydrogen-bonded molecular solids.

Hydrogen-bonded molecular solids have high melting point and are non-conductors of
electricity.

Ionic solids have high melting and boiling points, and are hard but brittle.
Ionic solids are non-conductors of electricity in solid state, but good conductors of electricity
in fused state or in aqueous solutions.

Crystalline Solids: Metallic and Covalent Solids

The constituent particles in a metallic solid are positive ions in a sea of delocalized electrons.

Free and mobile electrons make metallic solids good conductors of electricity and heat.

The presence of free electrons also accounts for the luster and colour of some metals.

Diamond, graphite and quartz are some network solids.

Diamond is the hardest substance known, and has a melting point of 3550 oC.

Graphite is a good conductor of electricity, and is extremely soft.

The presence of free and mobile electrons account for the exceptional electrical conductivity
in graphite.

Crystal Lattices and Unit Cells

An arrangement of an infinite set of particles is called a crystal lattice.

There are only 14 possible three dimensional lattices. These are called Bravais lattices.

A crystal lattice can be subdivided into several unit cells.

A unit cell is characterized by distance a, b and c along three edges, and angles α, β and γ
between pairs of edges.
Unit Cells: Types

Unit Cells in which all the constituent particles are present only at the corners are called
Primitive Unit Cells.

Unit Cells in which one or more constituent particles are present at positions other than its
corners in addition to those at the corners is called a Centred Unit Cell.

Centred Unit cells are categorised into Body- centred, Face-centred and End-centred.

Based on lattice parameters, there are seven popular crystal systems, namely Cubic,
Tetragonal Orthorhombic, Hexagonal, Rhombohedral, Monoclinic and Triclinic.

Unit Cells: Number of Atoms in a Unit Cell

Every Crystal Lattice is made of an infinite number of Unit Cells, and every Lattice site is
occupied by a Constituent Particle.

There is one Atom in a Simple Cubic Unit Cell.

There are two Atoms in a Body-centred Unit Cell.

There are four Atoms in a Face-centred Unit Cell.

Close Packed Structures: Packing in One and Two Dimensions

A close packing is a way of arranging equi-dimensional objects in space, to fill the available
space efficiently.
The number of nearest neighbors of a particle is defined as its co-ordination number.

The co-ordination number of a particle or sphere in one dimensional close packing is 2.

In two dimensional square close packing the co-ordination number is 4.

In two dimensional hexagonal close packing the co-ordination number is 6.

Two dimensional hexagonal close packing is more efficient than two dimensional square
close packing.

The vacant spaces in an arrangement are called voids or interstitial sites.

Close Packed Structures: Packing in Three Dimensions

AAA type packing of spheres results in the formation of a simple cubic lattice.

ABAB type packing of spheres is referred to as hexagonal close packing.

ABCABC type packing of spheres is referred to as cubic close packing (CCP) or face-
centred close packing (FCC).

In hexagonal close packing and cubic close packing a sphere has the coordination number 12.

In hexagonal close packing and cubic close packing 74% of the space in the crystal is filled
up.

In hexagonal close packing and cubic close packing, if there are N spheres in the packing per
unit cell, then the number of octahedral voids is the same, while the number of tetrahedral
voids is equal to 2N.
Deriving Formula of a Compound

The anions being larger in size form the basic crystal lattice and the cations being smaller in
size occupy the voids.

A smaller cation occupies the tetrahedral void while a relatively bigger cation occupies the
octahedral void.

The fraction of octahedral or tetrahedral voids occupied in a given lattice depends upon the
chemical formula of the compound.

One tetrahedral void is present in each of the small eight cubes of the ccp or fcc unit cell.

The octrahedral voids are present at the body centre and at the centre of each edge in the ccp
or fcc unit cell.

Packing Efficiency: HCP and CCP Lattice

The packing efficiency in the HCP arrangement of particles is 74%.

The packing efficiency in the CCP arrangement of particles is 74.06%.

Packing Efficiency: BCC and Simple Cubic Lattice

The packing efficiency in the BCC arrangement of particles is 68.05%.

The packing efficiency in the CCP arrangement of particles is 52.4%.

Calculations Involving Unit Cell Dimensions

We can calculate the volume of a Unit Cell by knowing its Dimensions.

The Volume of a Cube = a3.

The Density of a Unit Cell =

The Density of a Crystal, ρ = g cm-3

Imperfections: Stoichiometric Defects

If the constituent particles in a solid crystal are arranged in a regular fashion, then the crystal
is said to be an ideal or a perfect crystal.

No crystal in the universe is perfect.

Defects in solids are broadly classified into point defects and line defects.

A Frenkel defect is caused if some ions of the lattice occupy interstitial sites by leaving a
corresponding number of normal lattice sites vacant.

A Schottky defect is caused if some of the lattice sites remain unoccupied.

Imperfections: Impurity and Non-Stoichiometric Defects

If a foreign atom or ion or molecule is present in a crystal, then it has an impurity defect.
Stoichiometric and impurity defects do not influence the stoichiometry vacancies or the
presence of extra cations at the interstitial sites.

A metal deficiency defect may occur due to cationic vacancies.

Electrical Properties: Conduction in Metals

On the basis of their electrical conductivities solids can be classified into conductors,
insulators and semi-conductors.

In conductors the valence band overlaps the conduction band.

In insulators, the large gap region between the valence band and the conduction band is
called the forbidden zone.

In semiconductors, the energy gap between the valence band and the conduction band is
smaller than in insulators.

Silicon and germanium are examples of intrinsic or undoped semiconductors.

Electrical Properties: Conduction in Semiconductors

The addition of a pentavalent impurity to silicon or germanium produces an n-type

semiconductor.

The addition of a trivalent impurity to silicon or germanium produces a p-type

semiconductor.

Holes are the majority carriers in p-type semiconductors, while electrons are the majority
carriers in n-type semiconductors.
Important applications of semiconductors are the p-n junction diode, transistor and
photodiode.

Gallium arsenide is an important compound semiconductor of groups 13 and 15.

Zinc sulphide, cadmium selenide and mercuric telluride are examples of groups 12 and 16
compounds.

Magnetic Properties

Materials are classified as diamagnetic, paramagnetic, ferromagnetic, anti-ferromagnetic and

ferrimagnetic.

Diamagnetic materials are materials that are repelled by magnets.

Paramagnetic materials are materials that are weakly attracted by magnets.

Ferromagnetic materials are materials that are strongly attracted by magnets.