Solid State

A substance is said to be solid state if its melting point is above room

temperature under atmospheric pressure.
A substance will exist as a solid, a liquid or a gas depends upon the net effect
of the following two opposing forces.
(i) Intermolecular forces: forces existing among the constituent
particles which try to keep the constituent particles close together.
(ii) Thermal energy: energy possessed by the constituent
particles due to temperature. This energy tries to keep constituent particles
apart as it tends to make them move faster.

At low temperature, the thermal energy is quite low, but intermolecular

forces are so strong that the particles are brought very close together. As a
result, the constituent particles occupy fixed positions and are unable to
move except that they can oscillate about mean positions. Hence the
substance exists in the solid state.

General Characteristics
➢ They have definite mass, volume and shape.
➢ Intermolecular distances are short.
➢ Intermolecular forces are strong.
➢ Their constituent particles (atoms, molecules or ions) have fixed positions
and could oscillate only about their mean positions.
➢ They are incompressible and rigid.

Classification of solids
Solids can be classified as Crystalline and Amorphous
(1)Crystalline solid : these are the solids in which the constituent particles
have a regular orderly arrangement throughout and it gets repeated again and
again in a definite pattern . These solids have long range order.
Example: NaCl, quartz
(2)Amorphous solid: These are the solids the constituent particles do not
possess the regular arrangement throughout. Amorphous solids are short range
order because periodically repeating pattern is observed for short distance only.
 Amorphous solids are called super cooled liquids because they possess some
characteristics similar to the liquid also. Glass is a typical example which softens
upon heating to a certain temperature and behaves like a fluid.
Example: glass, rubber, plastic
Give reason: Window panes of old buildings look milky.
Windows or doors of old building are found to be somewhat thicker at the
bottom than at the top.
Glass is pseudo solid. It slowly flows down with changing temperature
conditions and as a result, the bottom portion becomes thicker. In fact due to
continuous heating in the day and cooling t night, glass acquires somewhat
crystalline characteristics. This is called annealing of glass. Though glass is of
amorphous nature, it becomes crystalline due to annealing. That is why; window
panes of old buildings look milky.

Difference between crystalline and amorphous solids

Properties of crystalline and amorphous solids

Property Crystalline Amorphous

Nature of arrangement Definite and regular
arrangement of particles
in space
Shape They have definite
characteristic shapes
Order of arrangement They have long
arrangement of the
particles
Do not have any regular
arrangement of the
constituent particles in
space
They have irregular
shapes
These have short order
arrangement
Melting point They have sharp melting
point
Cleavage property They undergo a clean
cleavage when cut
Heat of fusion They have definite heat of
fusion
Nature of physical Anisotropic in nature
properties
They melt over a certain
range of temperature
They undergo irregular
cleavage when cut
They do not have definite
heat of fusion
Isotropic in nature

➢ Crystalline solids are anisotropic in nature.

➢ Anisotropy in crystals is due to different arrangement of particle in different
directions

The substances which have the same physical properties such as electrical
conductivity, thermal conductivity, mechanical strength, refractive index etc. in all
the direction in the space are called isotropic substances. The substances which
have these properties different in different directions are regarded as anisotropic
substances.

Classification of crystalline solids

Based on the nature of intermolecular forces operating in them, solids are classified
into:
➢ Molecular solids
i. Polar molecuar solids
ii. Non polar molecular solids
iii. Hydrogen bonded molecular solids
➢ Metallic solids
➢ Covalent or Network solids
➢ Ionic solids
Crystal lattices and Unit cells
Crystal lattice: is the regular three dimensional arrangement of particles (atoms
or molecules or ions) in space

Characteristics of crystal lattice

There are 14 possible three dimensional lattices called Bravais lattices. Their
characteristics are
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 or molecule or ion.
c) Lattice points are joined by straight lines to bring out the geometry of the
lattice.
Unit cell: is the smallest portion of a crystal lattice which when repeated in
three dimension generates the crystal lattice.
Characteristics of unit cell
Unit cell is characterized by
i. Its dimensions along three edges, a, b, c which may or may not be mutually
perpendicular.
ii. Angles between the edges , α (between b and c), β (between a and c)and γ
(between a and b)

Unit cells can broadly divided into two categories

Primitive unit cells
Centered unit cells
Primitive unit cells: when constituent particles are present in corner positions of a
unit cell it is called as primitive unit cell.

Centred unit cells: when a unit contains one or more constituent particles present
at positions other than corners in addition to those at corners it is called a centered
unit cell.
They are of three types

(1) Body centered unit cell : such type of unit cell contain one constituent particle at
its body centered besides the ones that are at its corner.
 (2) Face centered unit cell :such a unit cell contains one constituent particle resent at
the center of each face beside the ones that are at its corners

(3) End centered unit cell: in such unit cell one constituent particle is present at the
center of any two opposite faces besides the ones present at its corners.

Seven primitive unit cell in crystals

Calculating number of particles in Primitive or simple cubic unit cell

In a simple cube each corner is shared by 8 unit cells

Each corner particle is shared to eight unit cells.
The contribution of corner particle is 1/8
1
The total number of atoms in one unit cell of simple cubic lattice is 8 ×8 = 1 atom

Calculating number of particles in Body centred cubic (BCC) unit cell

Body centered cubic lattice contain 8 corner particles and one particle at the
centerof the body.
In a BCC, there are 8 corners atoms
Each corner particle is shared to eight unit cells.
The contribution of corner particle is 1/8
1
From 8 corners the contribution to per unit cell is 8 ×8 = 1 atom
The particle present at the center of the body is not shared by other unit cell.
The contribution of body center atom to the unit cell =1
1
Number of particles in the unit cell of bcc =(8 ×8) +(1x1)=1+1 =2
∴ Total number of atoms per unit cell of body centered cubic lattice is = 2 atoms

Calculating number of particles in face centered cubic (FCC) unit cell

A face-centered cubic (fcc) unit cell contains atoms at all the corners and at the
center of all the faces of the cube. Each corner particle is shared to eight unit cells.

The contribution of corner particle is 1/8

1
From 8 corners the contribution to per unit cell is 8 ×8 = 1 atom
Each atom located at the face-center is shared between two adjacent unit cells and
only 1/2 of each atom belongs to a unit cell.
1
From 6 faces the contribution per unit cell = (6 ×2)
1 1
Number of particles in the unit cell of bcc =(8 ×8) +(6 ×2) =1+3
∴ Total number of atoms per unit cell of face centered lattice = 4 atoms

Close packing in crystals

The arrangement at which maximum number of particles occupies
minimum space is called close packing arrangement.
Co-ordination number:
The number of particle adjacent to each particle in a crystal is
called coordination number.
Build up of three dimensional structures in 3 steps
1. Close packing in one dimension

In this arrangement, each sphere is in contact with two of its neighbours. The
number of nearest neighbours of a particle is called its coordination number. Thus,
in one dimensional close packed one dimension arrangement, the coordination
number is 2.
2. Close packing in two dimensions
a) Square close packing
AAA type arrangement
In this arrangement, second row is placed in contact with the first one such that the
spheres of the second row are exactly above those of the first row. Each sphere is in
contact with four of its neighbours. Thus, the two dimensional coordination
numbers is 4. Also, if the centres of these 4 immediate neighbouring spheres are
joined, a square is formed.

3.Close packing in three dimensions

i) From two dimensional square close-packed layers simple cubic lattice formed by
AAA arrangement.
In this arrangement spheres of both the layers are perfectly aligned horizontally as
well as vertically. The lattice thus generated is the simple cubic lattice, and its unit
cell is the primitive cubic unit cell

3.Close packing in three dimensions

ii) From two dimensional hexagonal close-packed layers
a)Placing second layer over first layer
A stack of two layers of close packed spheres and voids generated in them.
T=Tetrahedral void;
O= Octahedral void
Tetrahedral void
A tetrahedral void is formed when four spheres are in direct contact with each
other

Octahedral void
An octahedral void is formed when six spheres are in direct contact with each other
The number of these two types of voids depends upon the number of close packed
spheres.
Let the number of close packed spheres be N, then:
The number of octahedral voids generated = N
The number of tetrahedral voids generated = 2N

b) Placing third layer over second layer

i) Covering of tetrahedral voids
When tetrahedral voids of second layer are covered by spheres of third layer, first
and third layers are aligned resulting in ABAB pattern and hexagonal close packed
structure. Eg: Mg, Zn
b) Placing third layer over second layer
ii) Covering of octahedral voids
When the third layer is placed above second layer in such away that its spheres
covers the octahedral voids, it leads to ABCABC type arrangement and forms cubic
close packed or face structure is formed.

Formula of a compound and number of voids filled

The number of octahedral voids present in a lattice is equal to the number of close
packed particles, while the number of tetrahedral voids generated is twice this
number.
In ionic solids, the bigger ions (usually anions) form the close packed structure and
the smaller ions (usually cations) occupy the voids.
If the latter ion is small enough then tetrahedral voids are occupied, if bigger, then
octahedral voids. Not all octahedral or tetrahedral voids are occupied.

Locating tetrahedral void

Each small cube has atoms at alternate corners. In all, each small cube has 4 atoms.
When joined to each other, they make a regular tetrahedron. Thus, there is one
tetrahedral void in each small cube and eight tetrahedral voids in total. Each of the
eight small cubes has one void in one unit cell of ccp structure. We know that ccp
structure has 4 atoms per unit cell. Thus, the number of tetrahedral voids is twice
the number of atoms.
The body center of the cube, C is not occupied but it is surrounded by six atoms on
face centers. If these face centers are joined, an octahedron is generated. Thus, this
unit cell has one octahedral void at the body center of the cube. Besides the body
center, there is one octahedral void at the center of each of the 12 edges. It is
surrounded by six atoms, three belonging to the same unit cell (2 on the corners and
1 on face center) and three belonging to two adjacent unit cells.

Packing efficiency
Packing efficiency is the percentage of the total space filled by the particles.
Packing Efficiency in Simple cubic Lattice

In a simple cubic lattice the atoms are located only on the corners of the cube.
The particles touch each other along the edge.
Thus, the edge length or side of the cube ‘a’, and
the radius of each particle, r are related as a = 2r
The volume of the cubic unit cell(cube) = a3 = (2r)3 = 8r3
Since a simple cubic unit cell contains only 1 atom
The volume of one sphere (atom) = 4/3∏ r3
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑜𝑛𝑒 𝑎𝑡𝑜𝑚
Packing efficiency= 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑐𝑢𝑏𝑖𝑐 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 x100

4/3πr3
Packing efficiency = 𝑥 100
8r3

Packing efficiency =52.4%

Packing efficiency in body centered cubic lattic

The atom at the center will be in touch with the other two atoms diagonally
arranged. The number of atoms per unit cell in bcc structures is two. Each atom is
considered as one sphere.
Let the edge length of the unit cell = a
Radius of the sphere=r
Length of the body diagonal =c
Length of the face diagonal =b

In Δ EFD,
FD2 =EF2 + ED2
b2 = a2 + a2 = 2a2
b = √2a
Now in Δ AFD
AF2 = AD2 +FD2
c2 = a2 + b2 = a2 + 2a2 = 3a2
c =√3a
The length of the body diagonal c=4r, where r is the radius of the sphere, as all the
spheres along the diagonal touch each other.
Therefore, √3a = 4r, a=4r/√3, r = (√3/4)a
In bcc, total number of atoms is 2
Volume of two spheres = 2 × (4/3) πr3
Volume of the cube, a3 = (4r/√3)3
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑡𝑤𝑜 𝑎𝑡𝑜𝑚
Packing efficiency= 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑐𝑢𝑏𝑖𝑐 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 x100

2x 4/3π𝑟3
Packing efficiency = 𝑥 100
(4r/√3)3
Packing efficiency =(8/3)πr3×100/64/√3)r3)% = 68%

Packing efficiency in face centered cubic lattice

The number of atoms per unit cell in fcc structures is four. Each atom is considered
as one sphere.
Let the edge length of the unit cell = a
Radius of the sphere=r
Length of the face diagonal =b

In Δ ABC,
AC2 =BC2 + AB2
b2 = a2 + a2 = 2a2
b = √2a
but b=4r
√2a=4r
4𝑟
a=√2 =2√2r
In fcc, total number of atoms is 4
Volume of four spheres = 4 × (4/3) πr3
Volume of the cube, a3 = (2√2r)3
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑓𝑜𝑢𝑟 𝑎𝑡𝑜𝑚
Packing efficiency= 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑐𝑢𝑏𝑖𝑐 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 x100

4x 4/3π𝑟3
Packing efficiency = 𝑥 100 =74%
(2√2r)3

Calculation of density of unit cell

Suppose, edge length of a unit cell of a cubic crystal determined by X-ray diffraction
is ‘a’,
‘d ‘the density of the solid substance and M the molar mass. In case of cubic crystal:
Volume of a unit cell = a3
Mass of the unit cell = number of atoms in unit cell × mass of each atom = z × m
(Here z is the number of atoms present in one unit cell and m is the mass of a single
atom)
Mass of an atom present in the unit cell
m =M/NA (M is molar mass)
mass of unit cell
Therefore, density of the unit cell = 𝑣 𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙

zm
d=𝑎3

𝒛𝑴
d=
𝒂𝟑 𝑵𝑨

If a is in cm
M is in gmol-1
unit of d is gcm-3
SI unit of density
a is in m
M is in kgmol-1
Unit of d is kgmol-1
Imperfection in solids

A crystal is said to be ideal if the entropy of its constituent at absolute zero

temperature is zero.
In a regular solid , there is a regular arrangement of constituent particles. This
arrangement is not found to be perfect because solid contains large number of small
crystal and some of these may not have a perfect regular arrangement of the
constituent particles.
Any departure from perfectly ordered arrangement of constitutent particles in
crystal is called imperfection or defect
The defect may also arise due to the heat absorbed by the crystal from
surroundings or due to the presence of impurites in the crystal.
There are two types of defects point defect and lattice defect.
Lattice defect
If the deviation from the periodic arrangement extend over microscopic regions ,
then the defect are called Lattice defect.
Lattice defect is of two types Line defect and plane defect .
When the deviation from the ideal arrangement exists in the entire row of
lattice points , the defect is called line defect.
When the irregularites extend along surfaces ie along the lattice plane , the
defect is known as plane defect.

Point defect
When deviation or irregularites exist from the ideuaul aurrangement aruoiuund a
point or a atom in a crystalline substance the defect is called point defect
Types of point defect
1. Stoichiometric defects
2. Non-Stoichiometric defects
3. Impurity Defects
Stoichiometric defects
These are defects that do not disturb the stoichiometry of the solid (if imperfection
in the crystal are such that the ratio between cations and anions remain the same as
represented by the molecular formula)
Types of stoichiometric defects
Vacancy defect: when some lattice sites in a crystalline solid are vacant, then the
crystals suffer from vacancy defect. This defect can be created upon heating. As
result, the density of solid decreases. This is generally shown by non- ionic solids.

Interstitial defect: when some extra constituent particles are present in the
interstitial sites, the crystal is said to have interstitial defect. As a result, the density
of solid increases. This defect is generally shown by the non -ionic solids.

Frenkel Defect: is shown by ionic solids. The smaller ion (usually cation) is
dislocated from its normal site to an interstitial site .It creates a vacancy defect at its
original site and an interstitial defect at its new location.
Also called dislocation defect, it does not change the density of the solid. Frenkel
defect is shown by ionic substance in which there is a large difference in the size of
ions.Eg: ZnS, AgCl, AgBr and AgI.

Schottky Defect: It is basically a vacancy defect in ionic solids. In order to maintain

electrical neutrality, the number of missing cations and anions are equal. Schottky
defect also decreases the density of the substance.
Schottky defect is shown by ionic substances in which the cation and anion are of
almost similar sizes. Eg:NaCl, KCl, CsCl and AgBr.
Difference between Schottky and Frenkel defect

Schottky defect Frenel defect

It is missing of both cation and anion
from the crystal lattice
Density decreases
It is found in ionic solids havinf high co-
ordination number
Found in ionic soilds having similar sizes
of cation and anion
It is the isloction of cation from its
normal site to the interstial site
Density emain same
It is found in ionic solids having low co-
ordination number
Shown by the ionic solids in which there
is a large difference in the size of the ions

Impurity Defects
If molten NaCl containing a little amount of SrCl2 is crystallized, some of the sites of
Na+ ions are occupied by Sr2+ . Each Sr2+ replaces two Na+ ions.
It occupies the site of one ion and the other site remains vacant. The cationic
vacancies thus produced are equal in number to that of Sr2+ ions. eg; Solid solution
of CdCl2 and AgCl.

Non-Stoichiometric defects
When alkali metal halides are heated in an atmosphere of alkali metal vapor, the
alkali metal atoms are deposited on the surface of the crystal. The halide ions diffuse
to the surface of the crystal and combine with alkali metal. The released electrons
diffuse into the crystal and occupy anionic sites

The anionic sites occupied by unpaired electrons are called F-centres (from the
German word Farbenzenter for colour centre). They impart colour to the crystals.
The colour results by excitation of these electrons when they absorb energy from
the visible light falling on the crystals.

Metal excess defect: due to the presence of extra cations at interstitial sites:
Zinc oxide is white in colour at room temperature. On heating it loses oxygen and
turns yellow.
Now there is excess of zinc in the crystal and its formula becomes Zn 1+xO. The excess
Zn 2+ ions move to interstitial sites and the electrons to neighbouring interstitial
sites.

Metal deficiency defect

The non-stoichiometric compounds may have metal deficiency due to the absence
of a metal from its lattice site. The deficiency in charge is balanced by an adjacent
ion having higher positive charge. Eg: FeO. In crystals of FeO some Fe 2+ ions are
missing and the loss of positive charge is made up by the presence of required
number of Fe3+ ions.
Electrical properties
Solids can be classified into three types on the basis of their conductivities.
(i) Conductors: The solids with conductivities ranging between 10 4 to 107 ohm–1m–
1 are called conductors. Metals have conductivities in the order of 107 ohm–1m–1 are

good conductors.
(ii) Insulators: These are the solids with very low conductivities ranging between
10-20 to 10-10ohm-1m-1
(iii) Semiconductors: These are the solids with conductivities in the intermediate
range from 10-6 to 104 ohm-1 m-1.
Conduction of electricity in metals
Metals conduct electricity both in solid as well as molten state.
The conductivity of a metal depends on the number of valence electrons in its atom.
.in metals, the atomic orbitals form molecular orbitals .the se molecular orbitals are
so close in energy that they form a band.
In metals, the valence band and conduction band are overlapping each other and
electrons can flow freely in an applied electric field and the metal shows
conductivity.

Conductivity in insulators
If the gap between filled valence band and the next higher unoccupied band
(conduction band) is large, electrons cannot jump to it and such a substance
has very small conductivity and it behaves as an insulator
Conductivity in semi-conductors
If the gap between valence band and conduction band is small, some
electrons can jump to conduction band and show some conductivity, and are
called semiconductors. Electrical conductivity can be increased by increasing
temperature and by the addition of suitable impurity. There are two types of
semiconductors .
Intrinsic semiconductors
Extrinsic semiconductors
Intrinsic semiconductors
Electrical conductivity increase with temperature as the number
Of electrons jumping to valence band increases and they are called
Intrinsic semiconductors.
E.g.: Ge, Si

Extrinsic semiconductors
Electrical conductivity can be increased by the addition of suitable impurity
this is called doping and such conductors are called extrinsic semiconductors.

n-type semiconductors: the semi-conductors obtained by doping pentavalent

impurity atom like phosphorus, arsenic ,antimony, bismuth(group15 element) to
a tetravalent silicon or germanium (group 14) are called n-type semi-
conductors.
When silicon is doped with phosphorus, silicon forms 4 covalent
with 4 electrons of phosphorus. The 5 th electron of phosphorus is extra and
becomes delocalized which conducts electricity .so in n- type semi-
conductors, the charge carriers are electron.
p-type semiconductors: the semiconductor obtained by doping trivalent
impurity atoms like Al, B ,Ga (group 13 element) to tetravalent Si or Ge
(group 14 element) are called p –type semiconductors.
 When silicon is doped with boron silicon forms only 3 covalent bonds
with boron which creates hole or electron vacancy. in p type semiconductors
holes are charge carries.

Applications of n-type and p-type semi conductors

1. Diode is a combination of n- type and p-type semiconductors. Its is used in
rectifiers
2. Transistors are sandwich semiconductors where a layer of one type
semiconductor is sandwiched between two layers of the other type of
semiconductor.
They are npn and pnp type .they are used to detect radio signals.
3. Solar cell is efficient photo diode.

Magnetic properties
Magnetic properties of substance have their origin in electron. Electrically
charged particle in motion produces magnetic field. Negatively charged
electron exhibits orbital motion around the nucleus and spin around its own
axis.
Each electron may be considered as a small magnet having small resultant
permanent magnetic moment.
Based on the magnetic properties substances are classified into

a) orbital motion b)spin motion

(i) Paramagnetic: Paramagnetic substances are weakly attracted by a magnetic

field. They are magnetized in a magnetic field in the same direction. Due to
presence of one or more unpaired electrons
 Eg.O2, Cu2+ Fe2+
(ii) Diamagnetism: Diamagnetic substances are weakly repelled by a magnetic
field. They are weakly magnetized in a magnetic field in opposite direction. All the
electrons are paired they do not contain any unpaired electron.
Eg.H2O, NaCl
iii) Ferromagnetism: Substances which are attracted very strongly by a magnetic
field and can be permanently magnetized. The metal ions of ferromagnetic
substances are grouped together into small regions called domains. When the
substance is placed in a magnetic field all the domains get oriented in the direction
of the magnetic field and a strong magnetic effect is produced.

iv) Anti-ferromagnetic: Substance having unpaired electrons but not attracted by

magnetic field because equal number of unpaired electrons are moving in opposite
directions are called anti-ferromagnetic substances.
E.g. MgO

v) Ferrimagnetic: Substances having more unpaired electrons but weakly attracted

by magnetic field because unequal number of unpaired electrons are moving in the
opposite directions are called ferromagnetic substances.
E.g.Fe3O4, MgFe2O4