Types of solids : Depending on orderly arrangement of the constituent particles,

the solids are classified into two types :

 • Crystalline solid : A homogeneous solid in which the constituent particles like
atoms, ions or molecules are arranged in a definite repeating pattern
throughout the solid is called crystalline solid. Examples: NaCl, KNO3, etc.
• Amorphous solid : A substance which appears like solid but does not have
perfectly ordered crystalline structure and no regular arrangement of
constituent particles in structure is called amorphous solid. Examples: glass,
rubber, plastics, etc.

Characteristic properties of solids :

• The solid state of matter is characterised by strong interparticle forces of
attraction.
• There is regularity and periodicity in the arrangement of constituent particles
of solid.
• Generally solids are hard, incompressible and rigid except some solids like Na,
K, P which are soft.
• The constituent particles of solids like molecules, atoms or ions have fixed
stationary positions in solid and can only oscillate about their equilibrium or
mean positions. Hence, they have fixed shape and cannot be poured like
liquids.
• Crystalline solids have sharp melting points and they melt at a definite
temperature. Amorphous solids do not have sharp melting points.
• All crystalline substances except those having cubic structure are anisotropic.
Their properties like refractive index, thermal and electrical conductivity, etc,
are different in different directions. They are anisotropic or isotropic.
Anisotropy : The ability of crystalline solids to change their physical properties
when measured in different directions is called anisotropy.
Explanation : This property is due to different arrangement of constituents in
different directions. Different types of particles fall on the way of measurements in
different directions. Hence the composition of crystalline solid changes with
directions changing their physical properties.

Fig. Anisotropy in crystals : Different arrangements of

constituent particles about different directions, AB, CD and

EF.

The two types of circles in this figure represent two

types of constituent particles of a solid.
The arrangement of particles in this solid is regular.
• ⃗→ represents arrangement of identical particles of one type.
⃗𝐴⃗⃗⃗𝐵

• ⃗→ represents arrangement of identical particles of another type.

⃗𝐶⃗⃗⃗𝐷

• ⃗𝐸⃗⃗⃗𝐹⃗⃗→ represents regular arrangement of two different particles in alternate

positions.
• Majority of crystalline solids, including metals, are polycrystalline in nature.
Single granule of a polycrystalline solid is made of many single crystals or
crystallites packed together with different orientations.
• Single crystals are difficult to obtain. Diamond is an example of naturally formed
single crystal.

Isotropy : The ability of amorphous solids to exhibit identical physical properties

even though measured in different directions is called isotropy.
Explanation : This property arises because there is no long range order of regular
pattern of arrangement in them and hence the arrangement is irregular along all the
directions. Therefore the magnitude of any physical property would be identical
along all directions.

Q. Why does crystalline solid show different refractive indices in different

directions ?
Ans. Crystalline solid has long range order of regular pattern of arrangement which
repeats periodically over entire crystal.
Within the given pattern, the arrangements of different atoms or ions or molecules is
different in different directions. Hence the properties like refractive indices in the
different directions are different.
This shows that the crystalline solids are anisotropic in nature.

Properties of amorphous solids :

 • The constituent particles in amorphous solids are arranged randomly.
• They have short range ordered structure.
• Amorphous solids are called supercooled liquids having very high viscosity.
• They do not have sharp melting points and they melt gradually over a
temperature interval.
• Amorphous substances appear like solids but they do not have perfectly
ordered crystalline stmcture, hence they are not real solids. Therefore they are
pseudo solids.
• They are isotropic and exhibit the same magnitude of any property in every
direction.
• Glass, plastic, rubber, tar, and metallic glass (metal-metalloid alloy) are a few
examples of amorphous solids.
lsomorphism : A phenomenon in which two or more crystalline substances show
same crystalline structure is called isomorphism and the crystals are said to be
isomorphous. For example, NaNO3 and CaCO3. They have atomic ratios 1 : 1 : 3.
Polymorphism : A single substance that exists in two or more forms or crystalline
structures is said to be polymorphous.
• Polymorphs of a substance are formed under different conditions. For example:
Calcite and aragonite are two forms of calcium carbonate, α-quartz, b-quartz
and cristobalite CsNO3 are three of the several forms of silica.
• Polymorphism occuring in elements is called allotropy. For example: three
polymorphic (allotropic) forms of carbon are diamond, graphite and fullerene.
Q. Why does a crystalline solid has a sharp melting point ?
Ans.
• Crystalline solid is a homogeneous solid and it has long range order of regular
pattern of arrangement which repeats periodically over entire crystal.
• The interatomic or intermolecular forces are identical, hence the thermal
energy required to break the regular structure by overcoming the
intermolecular forces is uniform throughout.
• Hence the heat and temperature needed to melt the solid are same, and
therefore solids have sharp melting points.
Q. Why Amorphous solids do not have sharp melting points. Explain.
Ans.
• Amorphous solids do not have perfectly ordered crystalline structure.
• They have short range order of regular pattern hence periodically repeating
regular pattern is over a short distance.
• The thermal energy required to break the structure and separate constituent
particles is not uniform.
• Hence the temperature needed to melt the solid is not same, therefore
amorphous solids do not have sharp melting points but melt over a range of
temperature.

Distinguish between crystalline solids and amorphous solids :

Crystalline solids Amorphous solids
They have definite characteristic They have irregular shape.
geometrical shape.
They have long range order of regular They have short range order of regular
pattern of arrangement of constituent pattern of arrangement of constituent
particles. particles.
They are true solids. They are pseudo solids or supercooled
liquids.
They have sharp melting points. They do not have sharp melting points.
They are anisotropic in nature. They are isotropic in nature.

They have definite heat of fusion. They do not have definite heat of fusion.

Classification of crystalline solids : The solids in which the constituent particles

are charged ions namely cations and anions held together by electrostatic force of
attraction are called crystalline solids. Crystalline solids are further classified into
four categories :
Crystalline solids are classified as follows :
• Ionic crystals.
 • Covalent network crystals
• Molecular crystals.
• Metallic crystals.
Characteristics of ionic crystals :
• The constituents of ionic crystals are charged ions namely cations and anions.
They differ in ionic size.
• The ions in these crystals are held by strong electrostatic force of attraction.
• Ionic crystals have high melting points and they are hard and brittle.
• In solid state they are nonconductors of electricity but they are good
conductors when melted or dissolved in water.
• In aqueous solution they dissociate forming ions.
• Example : NaCl, KCI, CaF2, K2S04, etc.
In ionic crystalline solids, constituent particles are positively charged cations and
negatively charged anions placed at alternate lattice points. The ions are held by
strong coulombic electrostatic forces of attraction compensating opposite forces.
Hence they are hard. Since there are no free electrons, they are not malleable and
on applying a shearing force, ionic crystals break into small units. Hence they are
brittle.
Covalent network crystals : The crystals in which the constituent particles are
atoms linked by covalent bonds forming a continuous network are called covalent
network crystals. For example, diamond, quartz.
In each of the four main classes of crystalline solids, the smallest constituents or
particles of various solids are atoms, ions or molecules.
Characteristics of covalent network crystals :
• The constituent particles in these solids are atoms.
• The atoms in these crystals are held by covalent bonds forming a rigid three
dimensional network which gives a giant molecule. Hence, the entire crystal is
a single molecule.
• These crystals are very hard (or hardest) and most incompressible.
• They have high melting points and boiling points.
 • Since the electrons are localised they are poor conductors of heat and
electricity.
• Example : Diamond, Quartz (SiO2), Boron nitride, Carborandum.

Q. Why Graphite is a covalent solid yet soft and good conductor of

electricity. Explain.
Ans.

• Each carbon atom in graphite is sp2 hybridized and covalently bonded to other
three sp2 hybridized carbon atoms forming  bonds and the fourth electron in
2pz orbital of each carbon atom is used in the formation of a  bond. This
results in the formation of hexagonal rings in two dimensions.
• In graphite, the layers consisting of hexagonal carbon network are held
together by weak van der Waal’s forces imparting softness.
• The electrons in  bonds in the ring are delocalized and free to move in the
delocalised molecular orbitals giving good electrical conductance.
Remember.
• Both ionic and covalent crystals are hard and have high melting and boiling
points. We can use electrical properties to distinguish between them. Both
are insulators at low temperature.
• Ionic solids become good conductors only at high temperature, above their
melting points.
 • The conductivity of covalent solids is in general low and increases with
temperature. However, there is no abrupt rise in conductivity when
substance is melted.

Allotropes : When a substance exists in two or more forms then they are called
allotropes. They are polymorphous. For example, carbon has allotropes diamond and
graphite.

Molecular crystals : These are crystals in which the constituent particles are
molecules (or unbonded single atoms) of the same substance held together by
intermolecular forces of attraction. For example, solidified C12, CO2, etc.
Characteristics of molecular crystals :
• The constituent particles of these solids are molecules (or unbonded single
atoms) of the same substance.
• The atoms within the molecules are bonded by covalent bonds.
• The molecules are held together by intermolecular forces of attraction.

Intermolecular forces of attraction involved in molecular crystals :

Weak dipole-dipole interactions : The solidsconstituting polar molecules like HCl,
H2O, SO2, etc. which possess permanent dipole moment involve weak dipole-dipole
interactions.
Very weak dispersion or London forces : The solids consisting of nonpolar
molecules like CH4, H2, etc. involve weak dispersion forces. They are also involved in
monoatomic solids like Ar, Ne.
Intermolecular Hydrogen bonds :
• In this crystalline solids, the constituent particles are the molecules which
contain hydrogen atom linked to highly electronegative atom like F, O or N.
• In these, molecules are held by hydrogen bonds in which H atom of one
molecule is bonded to electronegative atom (like F, N or O) of another
molecule.
 • Since hydrogen bonding is weak, these solids have very low melting points and
generally. They exist in the liquid or gaseous state at room temperature.
• They are non-conductors of electricity.

Metallic crystals : These are crystalline solids formed by atoms of the same
metallic element, held together by a metallic bond.
Characteristics of metallic crystals ;
• Metallic crystals are solids formed by atoms of the same metallic element held
together by metallic bonds.
• Metallic crystals have high melting point and boiling point.
• Metals are malleable, that is, they can be hammered into thin sheets.
• Metals are ductile, that is, they can be drawn into wires.
• Metals have good electrical and thermal conductivity.
• Examples : metals such as Na, K, Ca, Li, Fe, Au, Ag, Co, etc.
Giant solid : Covalent solid formed by covalent bonds between neighbouring
constituent atoms of non-metallic solid is called a giant solid. For example, graphite.
Crystal Structure :
Lattice : Lattice is a geometrical arrangement of points in a three dimensional
periodic array.
Crystal lattice (space lattice) : A regular arrangement of the constituent particles
(atoms, ions or molecules) of a crystalline solid having similar environment in three
dimensional space is called crystal lattice or space lattice.

Lattice point : A position occupied by a crystal constituent particle like an atom, ion
or a molecule in the crystal lattice is called lattice point or lattice site.
0R
Any point at the intersection of the lines in the unit cell occupied by a constituent
particle like an atom, an ion or a molecule in the crystalline solid is called a lattice
point.
Basis of crystal lattice :
• A crystal structure is formed by attaching a constituent particle to lattice
points.
• The constituent particles attached to the lattice points form the basis of the
crystal lattice.
• The crystal structure is obtained by attaching a basis to each of the lattice
points.
This is represented by the following schematic equation :
Unit cell : It is the smallest repeating structural unit of a crystalline solid (or crystal
lattice) which when repeated in different directions produces the crystalline solid
(lattice).
• The crystal is considered to consist of an infinite number of unit cells.
• The unit cell possesses all the characteristics of the crystalline solid.
Parameters of a unit cell : . A unit cell is characterised by following parameters.
Edges or edge lengths : The intersection of two faces of crystal lattice is called as
edge. The three edges denoted by a, b and c represent the dimensions (lengths) of
the unit cell along three axes. These edges may or may not be mutually
perpendicular.

Angles between the edges (or planes) : There are three angles between the
edges of the unit cell represented as ,  and .

• The angle  is between edges b and c.

• The angle  is between edges a and c.

• The angle  is between edges a and b.

The crystal is defined with the help of these parameters of its unit cell.
Types of unit cells : Basically unit cells are of four types as follows :
Primitive unit cell : The unit cell in which the constituent particles like atoms, ions
or molecules are present only at the comers of the unit cell is called primitive unit
cell or simple unit cell.
Body-centred unit cell : A unit cell in which the constituent particles are present at
the comers as well as at its body-centre is called body-centred unit cell.
Face-centred unit cell : A unit cell in which the constituent particles are present at
the corners as well as at the centre of each face is called face centred unit cell or
cubic close packed (CCP) limit cell.
Base-centred unit cell : A unit cell in which the constituent particles are present at
the corners as well as at the centres of two opposite faces is called end-centred unit
cell.
Crystal systems : The constituent particles like atoms, ions or molecules of the
crystal can be arranged in seven different ways changing edges (a, b, c) and angles
(, , ) and accordingly they form seven systems or types of the crystal.
These seven crystal system are named as :
(a) Cubic system (b) Tetragonal system (c) Orthorhombic system (d) Rhombohedral
system (e) Monoclinic system (f) Triclinic system (g) Hexagonal system.

Cubic system : There are seven crystal systems according to the edges (a, b, c)
and angles (, , ).
• The constituents of the crystal may be present at comers, face centres, body
centres, edge centres and voids.
• By mathematical analysis, it has been proved that only fourteen different kinds
of space lattices are possible.
• Hence there are fourteen different ways of arrangement of the lattice basis.
• These fourteen lattices of seven crystal systems are called Bravais lattices.

Bravais lattices of a cubic system (Unit cells of a cubic system) :

Cubic lattice : For this, edges are a = b = c and angles are  =  =  = 90°. In this
cubic system, there are three Bravais lattices. Lattice points in one unit cell
represent the positions of atoms, ions or molecules in the unit cell.
Simple (or primitive) cubic unit cell (SCC) : In this unit cell, atoms are present
only at 8 comers of the cube.
Number of atoms in primitive simple cubic (scc) unit cell :
In simple or primitive cubic unit cell, there are 8 atoms at 8 corners. Each comer
contributes 1/8th atom to the unit cell.
 Number of atoms present in the unit cell = (1/8) X 8 = 1
Hence the volume of the unit cell is equal to the volume of one atom.
Body-centred cubic unit cell (BCC) : In this, atoms are present at 8 comers along
with one additional atom at the body-centre of the cube.

Number of atoms in body-centred cubic (bcc) unit cell :

In this unit cell, there are 8 atoms at 8 comers and one additional atom at the body
centre. Each corner contributes 1/8th atom, to the unit cell, hence due to
8 comers.
 Number of atoms present in the unit cell = (1/8) X 8 = 1
An atom at the body centre wholly belongs to the unit cell.
Total number of atoms present in bCC cell = 1 + 1 = 2.
Hence the volume of unit cell is equal to the volume unit of two atoms.
Face-centred cubic unit cell (FCC) : In this unit cell, atoms are present at 8
corners and at 6 face centres.
Number of atoms in face-centred cubic (fcc) unit cell :
In this unit cell, there are 8 atoms at 8 corners and 6 atoms at 6 face centres.
Each comer contributes 1/8th atom to the unit cell, hence due to 8 corners,
 Number of atoms present in the unit cell = (1/8) X 8 = 1
Each face centre contributes half of the atom to the unit cell, hence due to 6 face
centres,
Number of atoms =1/2 x 6 = 3.
Total number of atoms present in fcc unit cell = 1 + 3 = 4.
Hence the volume of the unit cell is equal to the volume of four atoms.

The names of fourteen Bravais lattices (unit cells) for each of the seven
crystal system are shown below.
1. Cubic :

2. Orthorhombic :

3. Tetragonal :
4. Monoclinic :

5. Rhombohedral :

6. Triclinic :

7. Hexagonal :
 Remember...
Each corner particle of a cube is shared by 8 cubes, each face particle is shared by
2 cubes and each edge particle is shared by 4 cubes.

Relationship between density of a substance and the edge length of unit

cell. OR Relationship between molar mass, density of the substance and unit
cell edge length of the crystal :
Consider edge length of cubic unit cell is a, the
 Volume of unit cell = a3.
Suppose that mass of one particle is m and that there are n particles per unit cell.
 Mass of unit cell = m × n
The density of unit cell (ρ), which is same as density of the sub-substance is given
by
𝒎𝒂𝒔𝒔 𝒐𝒇 𝒖𝒏𝒊𝒕 𝒄𝒆𝒍𝒍
Density of Unit Cell =
𝑽𝒐𝒍𝒖𝒎𝒆 𝒐𝒇 𝒖𝒏𝒊𝒕 𝒄𝒆𝒍𝒍
(𝒎×𝒏)
ρ=
𝒂𝟑

Relation for the density of the unit cell and radius of atom or sphere for the
Simple cubic (scc) crystal :
Consider a unit cell of a simple cubic crystal. It has 8 atoms at 8 corners of the unit
cell.
 Total number of atoms in unit cell = (1/8) X 8 = 1
If a is the length of edge of cubic unit cell and r is the radius of the atom, then
r = a/2 or a = 2r.
Volume of the unit cell = a3 = (2r)3 = 8r3
If M is atomic mass of the element, then mass of one atom is M/NA where NA is
Avogadro number.
If there are ‘n’ atoms in one unit cell then,
Mass of unit cell = n x Mass of one atom = n x (M/NA)
𝒎𝒂𝒔𝒔 𝒐𝒇 𝒖𝒏𝒊𝒕 𝒄𝒆𝒍𝒍
Density of Unit Cell =
𝑽𝒐𝒍𝒖𝒎𝒆 𝒐𝒇 𝒖𝒏𝒊𝒕 𝒄𝒆𝒍𝒍
𝒏 × 𝑴/𝑵𝑨
ρ=
𝒂𝟑
𝒏×𝑴
ρ=
𝑵𝑨 × 𝒂𝟑

Since there is one atom present in one unit cell,

𝑴
ρ=
𝑵𝑨 × 𝒂𝟑

Relation for the density of the unit cell and radius of atom or sphere for the
Body centred cubic (bcc) crystal :
Consider a unit cell of body centred cubic (bcc) crystal. It has 8 atoms at 8 corners
and one additional atom at the centre of body of unit cell.
 Number of atoms due to 8 comers = (1/8) X 8 = 1
Body centred atom, wholly belong to the unit cell.
Hence total number of atoms in the unit cell is two.
If M is atomic mass of the element, then mass of one atom is M/NA where NA is
Avogadro number.
Mass of unit cell = Mass of 2 atoms in unit cell
= 2(M/NA)
If a is the edge length or lattice parameter then,
Volume of cubic unit cell = a3
𝒎𝒂𝒔𝒔 𝒐𝒇 𝒖𝒏𝒊𝒕 𝒄𝒆𝒍𝒍
Density of Unit Cell =
𝑽𝒐𝒍𝒖𝒎𝒆 𝒐𝒇 𝒖𝒏𝒊𝒕 𝒄𝒆𝒍𝒍
𝟐 × 𝑴/𝑵𝑨
ρ=
𝒂𝟑
𝟐𝑴
ρ=
𝑵𝑨 × 𝒂𝟑
Relation for the density of the unit cell and radius of atom or sphere for the
Face centred cubic (fcc) crystal :
Consider a unit cell of face centred cubic (fcc) crystal.
It has 8 atoms at 8 comers and 6 atoms at 6 face centres.
1
 Total number of atoms in unit cell = 1 ×8+ × 6 = 1+3=4
8 2

If M is atomic mass of the element, then mass of one atom is M/NA where NA is
Avogadro number.
Mass of unit cell = Mass of 4 atoms in unit cell
= 4(M/NA)
If a is the edge length or lattice parameter then,
Volume of cubic unit cell = a3
𝒎𝒂𝒔𝒔 𝒐𝒇 𝒖𝒏𝒊𝒕 𝒄𝒆𝒍𝒍
Density of Unit Cell =
𝑽𝒐𝒍𝒖𝒎𝒆 𝒐𝒇 𝒖𝒏𝒊𝒕 𝒄𝒆𝒍𝒍
𝟒 × 𝑴/𝑵𝑨
ρ=
𝒂𝟑
𝟒𝑴
ρ=
𝑵𝑨 × 𝒂𝟑

Packing of particles in crystal lattice :

Coordination number and its significance :
Coordination number : The number of the closest neighbouring constituent
particles like atoms, ions or molecules which are in contact with a particular particle
or an atom in the crystal lattice is called coordination number of that particle.
(In the crystal lattice, all atoms may have same or different coordination numbers.)
• The magnitude of the coordination number is a measure of compactness of
spheres in close-packed structures.
• The higher the coordination number, the closer are the spheres to each other.

Linear packing in one direction or close packing in one dimension : .

The constituent particles of the crystal may be of varying shapes but for better
understanding we consider particles as hard spheres of equal size.
There is only one way of arranging or packing spheres placed in a horizontal row
touching one another. Since one sphere is in contact with two neighbouring spheres
except the end atoms, the coordination number in this arrangement is two.
This packing may be in any one direction x, y or z.
Close packing in two dimensions :
Two dimensional close packing crystal structure can be generated by placing one
dimensional linear crystal structure over another to form multiple layers. This staking
of linear rows may be taking place in two different ways giving two different two
dimensional structures as follows :
AAAA type two dimensional close packing or square close packing :
In this arrangement, various one dimensional rows are placed on one over other so
that each sphere in one row is over the another sphere of another row forming
planar structure. In this, spheres have horizontal as well as vertical alignment. All
the rows of spheres are identical in planar structure. All crestsas well as all the
depressions or troughs formed by the arrangement are also aligned.

If the first row is labelled as A type, then second and all subsequent rows are also
identical, hence are of A type. Therefore this planar two dimensional close packing is
called AAAA…. type packing.
In this arrangement, each sphere is in contact with (or touching) four other spheres
around it, hence the coordination number of each sphere is four and the packing is
called two dimensional or planar square close packing. In this, packing efficiency is
52.4 %.
ABAB type two dimensional packing or hexagonal close packing :
In this arrangement, crests of the spheres of one row are placed into the depressions
or troughs formed between adjacent spheres of next row. This arrangement is
repeated consecutively throughout.
In this arrangement, crests of the spheres of one row are in contact with depressions
or troughs of next row.
If one row of spheres is labelled as A then the next row will be B, third row will again
be A, fourth row B and so on. Hence this planar or two dimensional close packing is
called ABAB... type packing.
In this arrangement, each sphere is in contact with six other spheres around it hence
the coordination number of each sphere is six and the packing iscalled two
dimensional or planar hexagonal close packing. In this, the packing efficiency is
60.4% which is more than linear close packing.

Close packing in three dimensions : Three dimensional crystal structures are

obtained by stacking of two dimensional layers. Simple cubic lattice is obtained by
stacking of two dimensional square layers.
The stacking of two dimensional hexagonal close packed layers gives two structures
namely hexagonal close packed (hcp) structure and face centred (fcc) structure.
(i) Stacking of square close packed layers :
In this arrangement, the two dimensional AAAA type square closed packed layers are
placed one over the other in such a way that the crests of all spheres are in contact
with successive layers in all directions.
All spheres of different layers are perfectly aligned horizontally and vertically forming
unit cells having primitive or simple cubic structure. Since all the layers are identical
and if each layer is labelled as layer A, then whole three dimensional crystal lattice
will be of type.
Each sphere is in contact with six surrounded spheres, hence the co-ordination
number of each sphere is six.
(ii) Stacking of two hexagonal close packed layers :
A close packed three dimensional structure can be generated by arranging hexagonal
close packed layers in a particular manner.

In this the spheres of second layer are placed in the

depression of the first layer. In this if first layer is
labelled as A then second layer is labelled as B since
they are aligned differently.
In this, all triangular voids of the first layers are not
covered by the spheres of the second layer.
The triangular voids which are covered by second layer
spheres generate tetrahedral void which is surrounded by four spheres. The
triangular voids in one layer have above them triangular voids of successive layers.
The overlapping triangular voids from two layers together form an octahedral void
which is surrounded by six spheres.
Placing third hexagonal close packed layer :
(i) Hexagonal close packing (hcp) : If the crests of spheres of third layer are
placed on the triangular shaped tetrahedral voids C of the second layer, then three
dimensional closest packing structure is obtained in which the spheres of third layer
lie directly above the spheres of first layer, i.e., first and third layers are identical.
Following same placing of layers, fourth layer will be identical to second layer.
If the first layer is labelled A and second layer B, then the arrangement of packing
will be of ABAB type. This is also called hexagonal close packing (hcp) as shown in
the figure.

In this, packing efficiency is 74%. The coordination number of each sphere is 12.
The metals Be, Mg, Zn, Cd crystallise in HCP crystalline structure.
(ii) Cubic close packing (ccp) : If the crests of spheres of third layer are placed in
the positions of tetrahedral void ‘a’ having apex upward of first layers, then the third
layer will not be identical to the first, and may be labelled as C, which is different
from A and B layers. Fourth layer may be arranged above third layer such that the
spheres are aligned, so that the first layer and fourth layer are identical, second and
fifth layers are identical and so on.
If first, second and third layers are labelled as A, B and C respectively then the
arrangement of packing will be ABCABC type. This is also called cubic close packing
(ccp) as shown in the figure. This is similar to face centred cubic (fcc) packing.
In this, arrangement packing efficiency is 74 % and the coordination number of each
sphere is 12.
Tetrahedral void: All triangular voids of the first layers are not covered by the
spheres of the second layer. The triangular voids that are covered by spheres of the
second layer generate tetrahedral void.

The vacant space or void among four constituent particles having tetrahedral
arrangement in the crystal lattice is called tetrahedral void.
The arrangement of four spheres around the void is tetrahedral. A tetrahedral void is
formed when a triangular void made by three coplanar spheres is in contact with
fourth sphere above or below it.
Characteristics of tetrahedral void :
• The volume of the void is much smaller than that of atom or sphere.
• Larger the size of sphere, more is the size of void.
• If R is the radius of the constituent atom, then the radius of the tetrahedral
void is 0.225 R.
• Coordination number of tetrahedral void is four.
• There are two tetrahedral voids per sphere, in the crystal lattice. If the number
of closed packed spheres is N then the number of tetrahedral voids is 2N.
 Octahedral void : The overlapping
triangular voids from the two layers
together form an octahedral void which is
surrounded by six spheres.

The vacant space or void at the centre of six spheres (or atoms) which are placed
octahedrally is called octahedral void.
Characteristics of octahedral void :
• The volume of the void is small.

• There is one octahedral void at the body centre and twelve octahedral void
positions at twelve edge centres.
• If R is the radius of constituent atom, then the radius of the octahedral void is
0.414 R.
• The coordination number of octahedral void is six.
• There is one octahedral void per sphere in the crystal lattice. If the number of
closed packed spheres is N then the number of octahedral voids is N.
Number of voids per atom in hcp and ccp : The tetrahedral and octahedral voids
occur in hcp and ccp/fcc structures. There are two tetrahedral voids associated with
each atom. The number of octahedral voids is half that of tetrahedral voids.
Thus, there is one octahedral void per atom.
 • If N denotes number of particles, then number of tetrahedral voids is 2N and
that of octahedral voids is N.

Remember :
It is important to note that the triangular shapes of depressions in A and B layer do
not overlap. The apices of two triangular depressions in A and B layer point in
opposite directions.
The depressions in which spheres of second layer rest are tetrahedral voids while
the depressions in which no sphere rests are octahedral voids.

Packing efficiency : Packing efficiency is the fraction or a percentage of the total

space occupied by the spheres (particles).
The magnitude of packing efficiency gives a measure of how tightly particles are
packed together.
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑐𝑐𝑢𝑝𝑖𝑒𝑑 𝑏𝑦 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒𝑠 𝑖𝑛 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙
Packing efficiency = × 100
𝑡𝑜𝑡𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙

Packing efficiency of metal crystal in simple cubic lattice :

Step 1 : Radius of sphere : In simple cubic unit cell, particles (spheres) are at the
corners and touch each other along the edge.

A face of simple cubic unit cell is shown in Fig. It is evident that

a = 2r or r = a/2 ………(1)
where r is the radius of atom and ‘a’ is the length of unit cell edge.
4 3
Step 2 : Volume of sphere : Volume of a sphere = 𝑟 .
3
Substitution for r from Eq. (1)
 4 𝑎 3 𝑎3
 Volume of one particle = ( ) =
6
3 2
Step 3 : Total volume of particles : Because simple cubic unit cell contains only
𝑎3
one particle, volume occupied by particle in unit cell =
6
Step 4 : Packing efficiency
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑐𝑐𝑢𝑝𝑖𝑒𝑑 𝑏𝑦 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒𝑠 𝑖𝑛 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙
Packing efficiency = × 100
𝑡𝑜𝑡𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙
𝜋𝑎3/6
= × 100 = 𝜋 × 100 = 3.142×100 = 52.36%
𝑎3 6 6
Thus, in simple cubic lattice, 52.36 % of total space is occupied by particles and 100
- 52.36 = 47.64 % is empty space,
∴ void volume or a percentage of void space = 46.64%
Packing efficiency of metal crystal in body-centred cubic lattice :
Step 1 : Radius of sphere (particle) : In the unit cell of body-centred cubic
lattice, there are 8 atoms (particle) at 8 comers and one atom at the centre of the
cube.

Figure shows that the particle at the centre of the cube touches two corner particles
along the diagonal of the cube.
To obtain radius of the particle (sphere) Pythagorus theorem is applied.
• For triangle FED, ∠ FED = 900.
∴ FD2 = FE2 + ED2 = a2 +a2 = 2a2 (because FE = ED = a) …….(1)
• For triangle AFD, ∠ ADF = 900
∴ AF2 = AD2 + FD2 ........... (2)
Substitution of Eq. (1) into Eq. (2) yields
AF2 = a2 + 2a2 = 3a2 (because AD = a)

∴ AF = √3 𝑎 ………(3)
The Fig. shows that AF = 4r.
Substitution for AF from equation (3) gives

∴ √3 𝑎 = 4r
√3
∴ r= 𝑎 ….. (4)
4
4 3
Step 2 : Volume of sphere : Volume of sphere particle = 𝑟 .
3
Substitution for r from Eq. (4),
3
4 √3 √3𝜋𝑎3
∴ Volume of one particle = ( 𝑎) = .
3 4 16
Step 3 : Total volume of particles : Unit cell bcc contains 2 particles. Hence,
√3𝜋𝑎3
volume occupied by particles in bcc unit cell = 2 ×
16

√3𝜋𝑎3
=
8
Step 4 : Packing efficiency
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑐𝑐𝑢𝑝𝑖𝑒𝑑 𝑏𝑦 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒𝑠 𝑖𝑛 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙
Packing efficiency = × 100
𝑡𝑜𝑡𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙

√3 𝜋𝑎3/8 √3×𝜋 √3×3.142×100 = 68 %

=
𝑎3
× 100 = 8
× 100 = 8
Thus, 68% of the total volume in bcc unit lattice is occupied
∴ Percentage of void space = 100 - 68 = 32 %

Packing efficiency of metal crystal in face-centred cubic lattice (or ccp or

hcp lattice)
Step 1 : Radius of particle/sphere : The corner particles are assumed to touch
the particle at the centre of face ABCD as shown in Fig.
The triangle ABC is right angled with ∠ABC = 900. According to Pythagorus theorem,
AC2 = AB2 + BC2 = a2 +a2 = 2a2
(because AB = BC = a)
Hence, AC = √2 a …. (1)
From figure AC = 4 r. Substitution for AC from Eq. (1.) gives

√2 a = 4r
√2 𝑎
∴r= 𝑎= ….(2)
4 2√2
4 3
Step 2 : Volume of sphere : Volume of one particle = 𝑟
3
Substitution for r from Eq. (2)
4 3 4 𝑎3 1 3
𝑎
∴ Volume of one particle = ×( ) = ×( )
3 2√2 3 2√2

 𝑎3
=
12√2
Step 3 : Total volume of particles : The unit cell of fcc lattice contains 4 particles.
Hence, volume occupied by particles in fcc unit cell
 𝑎3
=4×
12√2
 𝑎3
=
3√2
Step 4 : Packing efficiency :
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑐𝑐𝑢𝑝𝑖𝑒𝑑 𝑏𝑦 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒𝑠 𝑖𝑛 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙
Packing efficiency = × 100
𝑡𝑜𝑡𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙
 3.142
𝜋𝑎3/3√2 × 100 = × 100 == 74 %
=
𝑎3 3√2
Thus in fcc/ccp/hcp crystal lattice, 74% of the total volume is occupied by particles
∴ Percentage of void space = 100 - 74 = 26 %

Q. Which of the three types of packing used by metals makes the most
efficient use of space and which makes the least efficient use ?
Ans. fcc has the most efficient packing of particles awhile scc has the least eflicient
packing.

Below Table shows the expressions for various parameters of particles in

terms of unit cell dimension for cubic systems.

Below Table shows the summary of coordination number of particles and

packing efficiency in various cubic systems.
Number of particles and unit cells in ‘x’ g of metallic crystal :

Consider ‘x’ gram of a metallic crystal of molar mass M and density ρ.

If the unit cell of the crystal has edge length ‘a’ then, volume of unit cell = a3.
𝑚𝑎𝑠𝑠 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒𝑠 𝑖𝑛 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙 𝑀
ρ= = ×
𝑣𝑜𝑙𝑢𝑚𝑒 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 𝑁𝐴
𝑛 𝑀
∴ρ = 3 ×
𝑎 𝑁𝐴
𝜌 𝑎3𝑁𝐴
∴M =
𝑛
where 'n' is the number of particles in unit cell and 'a3' is the volume of unit cell.
i. Number of particles in 'x' g metal :
∴ Molar mass, M, contains NA particles
𝑥𝑁𝐴
∴ x g of metal contains particles
𝑀
substitution of M gives
 𝑥𝑁𝐴 𝑥𝑛
Number of particles in 'x' g = =
𝜌𝑎3𝑁𝐴/𝑛 𝜌𝑎3

ii. Number of unit cells in 'x' g metal :

∴ 'n' particles correspond to 1 unit cell
𝑥𝑛 𝑥𝑛 1
∴ 3 particles correspond to 3 × unit cells.
𝜌𝑎 𝜌𝑎 𝑛
𝑥
∴ Number of unit cells in 'x' g metal = 3
𝜌𝑎
𝑉
iii. Number of unit cells in volume 'V' of metal =
𝑎3
Crystal defects or imperfections : The real, naturally occurring crystalline
substances do not have perfect crystal structures. They have some disorders or
irregularities in the stacking of atoms. Such irregularities in the arrangement of
constituent particles of a solid crystal are called defects or imperfections.
• Defect in crystalline structure : Any deviation from orderly and
stoichiometrically perfect arrangement of atoms, ions or molecules in the
crystal lattice is called a defect in the crystalline structure.
• Defects are created during the crystallization process. If the process occurs at
faster rate, the defects are more.
• The properties of solids are affected due to imperfections.

There are three types of defects: point defects, line defects and plain defects. Only
point defects will be discussed in this chapter.
Point defects : These defects arise due to irregularities produced in the
arrangement of basis of lattice points in crystalline solids.
There are three major classes of point defects :
• stoichiometric point defects,
• impurity defects
• non-stoichiometric point defects.
a. Stoichiometric point defects : Chemical formula of a compound shows fixed
ratio of number of atoms or number of cations and anions. This fixed ratio is the
stoichiometry of the compound.
In stoichiometric defect, the stoichiometry remains unchanged. In other words, the
ratio of number of atoms or number of cations and anions of compound remains the
same as represented by its chemical formula.
There are four types of stoichiometric point defects as
• vacancy defect,
• self interstitial defect,
• Schottky defect
• Frenkel defect.
Vacancy defect :

• During crystallisation, some of regular sites in solid remain unoccupied and the
missing particle creates a vacancy defect.
• The defect can be developed by heating the substance.
• The mass of solid decreases due to absence of particles in regular sites.
• Since the volume remains the same the density of the substance decreases.
Self Interstitial defect in elemental solid :
The empty spaces or voids in between the particles at lattice points represent
interstitial defective sites or self interstitial defects.
This defect arises in the following two ways :
(1) An extra particle occupies the empty interstitial space. This extra particle is
similar to those already present in the crystal.
(2) A particle gets shifted from its original regular site to an empty interstitial space
in the crystal.

• This displacement of a particle produces a vacancy defect at its regular site.

• This defect is referred to as a combination of vacancy defect and self-
interstitial defect.
• Since there is neither loss or gain in mass of the substance, the density of it
remains unchanged-
Schottky defect :
 • Schottky defect arises in ionic solids due to missing of equal number of cations
and anions from their regular positions in the crystal lattice creating vacancies.
• There arises formation of two holes per loss of ion pair.
Conditions for formation of Schottky defect :
Characteristics of ionic solids showing Schottky defect :
• High degree of ionic character
• High coordination number of anion
• Small difference between ionic size or radii of cation and anion. The ionic ratio
𝑟𝑐𝑎𝑡𝑖𝑜𝑛
is not below unity.
𝑟𝑎𝑛𝑖𝑜𝑛

Consequences of Schottky defect

• As the number of ions decreases, mass decreases. However, volume remains
unchanged. Hence, the density of a substance decreases.
• The number of missing cations and anions is equal, the electrical neutrality of
the compound is preserved.
• This defect is found in ionic crystals such as NaCl, AgBr and KCl.

Frenkel defect : This defect arises when an ion of an ionic compound is missing
from its regular site and occupies interstitial vacant position between lattice points.

• Cations have smaller size than anions, hence generally cations occupy the
interstitial sites.
• This creates a vacancy defect at its original position and interstitial defect at
new position.
 • Frenkel defect is regarded as the combination of interstitial defect and vacancy
defect.
Conditions for the formation of Frenkel defect :
• This defect arises in ionic compounds with a large difference between the sizes
of cation and anion.
• The ionic compounds must have ions with low coordination number.
Consequences of Frenkel defect :
• As no ions are missing from the crystal lattice as a whole, the density of solid
and its chemical properties remain unchanged.
• The crystal as a whole remains electrically neutral because the equal numbers
of cations and anions are present.
• This defect is found in ionic crystals like ZnS, AgCl, AgBr, AgI, CaF2.
Impurity defect : This defect arises when foreign atoms, that is, atoms different
from the host atoms are present in the crystal lattice.
There are two types of impurity defects namely
(1) Substitutional defects and (2) Interstitial defects.
i. Substitutional impurity defect : In this defect, the foreign atoms are found at
the lattice sites in place of host atoms. The regular atoms are displaced from their
lattice sites by impurity atoms.
For example : Solid solutions of metals (alloys) : Brass is an alloy of Cu and Zn. In
brass, host Cu atoms are replaced by impurity of Zn atoms. The Zn atoms occupy
regular sites of Cu atoms as shown in Fig.

Vacancy through aliovalent impurity :

By addition of impurities of aliovalent ions

When aliovalent ion like Sr2+ in small amount is added by adding SrCl2 to NaCl during
its crystallisation, each Sr2+ ion (oxidation state 2 +) removes 2 Na+ ions from their
lattice points, to maintain electrical neutrality. Hence one of vacant lattice site is
occupied by Sr2+ ion while other site remains vacant.
ii. Interstitial impurity defect :

A defect in solid in which the impurity atoms occupy interstitial vacant spaces of
lattice structure is called interstitial impurity defect.
For example, in steel, normal lattice sites are occupied by Fe atoms but interstitial
spaces are occupied by carbon atoms. .

Nonstoichiometric defects :
Nonstoichiometric defect arises when the ratio of number of atoms of one kind to
that of other kind or the ratio of number of cations to anions becomes different from
that indicated by its chemical formula. i.e. stoichiometry of the compound is
changed.
 • The change in stoichiometry does not cause any change in the crystal
structure.
• There are two types of nonstoichiometric defects
i. Metal deficiency defect : This defect arises in compounds of metal which show
variable oxidation states. In some metal crystals, positive metal ions are missing
from their regular lattice sites.
The extra negative charge is balanced by cations of the same metal with higher
oxidation state than that of missing cation at site.

For example, in the compound NiOone Ni2+ ion is missing creating a vacnacy at its
lattice site. The deficiency of two positive charges is made up by the presence of two
Ni3+ ions at the other lattice sites of Ni2+ ions as shown in Fig. The composition of NiO
then becomes Ni0.97O1.0
ii. Metal excess defect : There are two types of metal excess defect as follows :
(a) Presence of a neutral atom or an extra positive ion at interstitial position :
There are two types or ways of metal excess defects in ZnO. In the first case, Zn
atom is present in the interstitial space as shown in figure.
(b) Metal ions and electrons at interstitial sites :
The second case arises when ZnO is heated,
Zn2+ and electrons are obtained,
ZnO → Zn2+ + ½O2 + 2e−

The excess Zn2+ ions are trapped in interstitial

site in the lattice. The electrons also diffuse in
the crystal to occupy interstitial sites as shown
in Fig.
In both the cases, nonstoichiometric formula of
ZnO is Zn1+xO1.0

Defects due to anion vacancies OR colour of crystals or F centres :

The defect due to anion vacancies imparts colour to the colourless crystal.
• When a colourless crystal of NaCl is heated in the atmosphere of sodium
vapour, the sodium atoms are deposited on the crystal surface.

• Due to diffusion of Cl− ions to the crystal surface vacancies are created at their
regular sites.
• These diffused Cl− ions combine with Na atoms on the surface forming NaCl
along with releasing electrons from sodium atoms.
• Na + Cl− → NaCl + e−
 • The released electrons diffuse into the crystal and occupy vacant sites of
anions Cl− in the crystal.
• The anion vacant sites occupied by electrons are called F-centres or colour
centres. Due to colour centres NaCl shows yellow colour.
• Now NaCl crystal has excess of Na atoms having nonstoichiometric formula
Na1+xCl1.0
Q. When ZnO is heated it turns yellow and returns back to original white
colour on cooling. What could be the reason ?
Ans.
• When colourless ZnO is strongly heated, the metal atoms are deposited on
crystal surface and anions O2− migrate to the surface producing vacancies at
anion lattice points.
• These anions combine with Zn atoms forming ZnO and release electrons.
• Zn + O2− —> ZnO + 2e−
• These released electrons diffuse into the crystal and occupy vacant sites of
anions and produce F-centres.
• Due to these colour centres, ZnO turns yellow.

Electrical properties of solids :

Solids show very wide range of electrical conductivity. According to electrical
conductivity, solids are classified as follows :
(i) Conductors :
• The solids having electrical conductivity in the range of 104 to 107 Ohm−1m−1
are called conductors.
• The examples of conductors are metals and electrolytes.
• Electrical conductivity in metals is due to free movement of electrons while
electrolytes conduct electricity due to migration ions.
(ii) Insulators :
• Solids having low electrical conductivities in the range 10-20 to 10-10 Ohm−1m−1
are called insulators.
• Examples : Nonmetals and molecular solids belong to this category.
(iii) Semiconductors :
• Solids having electrical conductivities in the range 10-6 to 104 Ohm−1m−1 are
semiconductors.
• This range is intermediate between conductors and insulators.
• For Examples : Metalloids like silicon, germanium belong to this category.

Band theory (origin of electrical properties in solids) : Electrical conductivities

of solid metals, nonmetals and metalloids are explained in terms of band theory,
which involves the presence of free electrons.
• According to band theory, the atomic orbitals of metal atoms overlap to form
molecular orbitals which are spread all over the crystal structure.
• The energy difference between adjacent molecular orbitals decreases as the
number of molecular orbitals increases and when it becomes very less, the
orbitals merge into one another forming continuous bands which extent over
the entire crystal.
There are two types of bands of molecular orbitals s follows :
• Valence band : The atomic orbitals with filled electrons from the inner shells
form valence bands, where there are no free mobile electrons since they are
involved in bonding.
• Conduction band : Atomic orbitals which are partially filled or empty on
overlapping form closely placed molecular orbitals giving conduction bands
where electrons are delocalised and can conduct, heat and electricity.
Band gap : The energy difference between valence band and conduction band is
called band gap.
• Band gap decides whether electrons from valence band can be promoted to
vacant conduction band or not.
• The conductors like metals have very small or no band gap and electron can be
promoted by thermal energy. The nonconductors have large band gap. The
insulators have very large band gap.
The band gap energy values of a few solids are as shown here.

Metals :
• Metals are good conductors of electricity since the outermost electrons of all
the atoms in the metallic crystal occupy conduction band.
• The number of electrons in conduction bands is very large.

• The conduction bands in metals can be labelled as ‘s’ band, overlapping s and
p bands etc. according to overlapping of orbitals.
• This results in delocalisation of outermost electrons forming metal ions. Hence,
this is analogous to metal cations immersed in the sea of electrons.
Q. Why does metallic conductivity decrease by increasing temperature ?
Ans.
• In metals a large number of outermost electrons of atoms occupy conduction
bands.
• Band formation in metals results in delocalisation of outennost electrons
forming metal ions or cations.
• The metallic cations occupying crystal lattice sites vibrate about mean
positions.
• As temperature increases the vibrational motion increases which interrupts
flow of electrons decreasing electrical conductivity.
Insulators : In insulators the valence band is completely filled by electronics while
conduction band is empty.

• The energy gap between valence band

and conduction band in insulator is very large.
• Thermal energy is not sufficient to
promote electrons from valence band to

conduction band.
• Therefore, the conduction band in insulator remains vacant and does not allow
the conduction of electricity.
Semiconductors : Electrical conductivity of a semiconductor material is
intermediate between that of metals and insulators.

• The substances like silicon, germanium which have poor electrical conductance
at low temperature but the conductance increases with the increase in
temperature are called semi-conductors.
 • The energy difference between valence band and conduction band is relatively
small, hence the electrons from valence band can be excited to conduction
band by heating.
Types of semiconductors : There are two types of semiconductors :
• Intrinsic semiconductor
• Extrinsic semiconductor
(a) Intrinsic semiconductor :
• A pure semiconductor material like pure Si, Ge which have a very low but finite
electrical conductivity is called intrinsic semiconductor.
• The electrical conductivity of a semiconductor increases with the increase in
temperature.
(b) Extrinsic semiconductor :
• Semiconductor doped with different element is called extrinsic semiconductor.
• By doping with elements like Ga or P, the electrical conductivity is increased.

Remember...
Electrical conductivity of metals decreases and that of semiconductor increases
with increasing temperature.

Extrinsic semiconductors and doping :

Doping : The conductivity of a semiconductor can be increased by doping. The
process of addition of minute quantity of impurities to a semiconductor to increase
its conductivity is called doping. The added impurity is called dopant.
Extrinsic semiconductors : A doped semiconductor, having higher conductivity
than pure intrinsic semiconductor, is an extrinsic semiconductor.
• A semiconductor obtained by doping intrinsic semiconductor with elements of
third group and fifth group is called extrinsic semiconductor.
• This extrinsic semiconductor has higher electrical conductivity than pure
intrinsic semiconductor.
There are two types of extrinsic semiconductors :
(A) n-type semiconductor :
• n-type semiconductor contains increased number of electrons in the
conduction band.
• When Si semiconductor is doped with 15th group element phosphorus, P, the
new atoms occupy some vacant sites in the lattice in place of Si atoms.

• P has five valence electrons, out of which four are involved in covalent bonding
with neighbouring Si atoms while one electrons remains free and delocalised.
• These free electrons increase the electrical conductivity of the semiconductor.
• The semiconductors with extra non-bonding free electrons are called n-type
semiconductors.
(B) p-type semiconductor :
• p-type semiconductor is obtained by doping a pure semiconductor by an
element of 13th group like B.
 • 13th group element has less number of valence electrons. When pure Si is
doped with B atoms, these atoms occupy Si lattice points.

• Boron (SB) has only 3 valence electrons which form covalent bonds with the
neighbouring Si atoms, while one bond has shortage of one electron.
• This creates a vacancy or a hole, hence the electron from neighbouring Si
atom jumps into this hole creating a vacancy in itself. This process continues,
i.e., positive holes move in one direction while electrons moves inopposite
direction.
• Due to electron deficient positions, this semiconductor is called p-type
semiconductor.
• When p-type semiconductor is connected to the external source of electricity,
electrons from neighbouring silicon atoms jump into the holes so that electrons
move towards positive electrode and holes migrate towards negative electrode.
• Hence electrical conduction in p-type semiconductor is due to electrons and
holes.
Remember :
• Whether intrinsic or extrinsic semiconductor, the material is electrically neutral.
• An n-type semiconductor such as Si doped with P has more electrons than those
needed for bonding and thus has electrons in the partially filled conduction band.
• A p-type semiconductor such as Si doped with B has the less electrons than
needed for bonding and thus has vacancies (holes) in the valence band.
 Activity : If a small quantity of phosphorus be doped into pure silicon.
• Total number of electrons in doped silicon will be more than in original
silicon.
• Material will be electrically neutral.

Uses of semiconductors :
• They are used in transistors, digital computers and cameras.
• They are used in solar cells and television sets.
• By combining n-type and p-type semiconductors, n-p junctions are formed
which are effectively used in rectifiers or to convert light energy into electrical
energy.
Magnetic properties of solids : Magnetic properties of solids can be understood
easily in terms of classical picture of electron.

• The electrons spin about their own axis. The spinning electrons act like tiny
magnets because their spinning action generates induced magnetic field.
• If an orbital contains one electron, the unbalanced spin exhibits magnetism.
• However, when electrons are paired their spin is balanced and no magnetic
property is observed.
On the basis of magnetic properties solids are classified into three major classes :
diamagnetic, paramagnetic and ferromagnetic.
Diamagnetism :
The magnetic properties of a substance arise due to presence of the electrons.
An electron while revolving around the nucleus, also spins around its own axis and
generates a magnetic moment and a magnetic property.
 • If an atom or a molecule of the substance contains all electrons paired,
spinning clockwise and anticlockwise, their magnetic moments and magnetic
properties get cancelled. Hence they oppose and repel the applied magnetic
field. This phenomenon is called diamagnetism and the substance is said to be
diamagnetic.

• N2, F2, NaCl, H2O and benzene are some examples of diamagnetic substances.
Paramagnetism: (Paramagnetic substances) :
The magnetic properties of a substance arise due to the presence of electrons.
An electron while revolving around the nucleus, also spins around its own axis and
generates a magnetic moment and magnetic properties.
• If an atom or a molecule contains one or more unpaired electrons spinning in
same direction, clockwise or anticlockwise, then the substance is associated
with net magnetic moment and magnetic properties. They experience a net
force of attraction when placed in the magnetic field. This phenomenon is
called paramagnetism and the substance is said to be paramagnetic.
• For example : Oxygen, Cu2+, Fe3+, Cr3+ are some examples of paramagnetic
substances.
Ferromagnetism :
• The substances containing large number of unpaired electrons are attracted
strongly by magnetic field. These substances are said to be ferromagnetic.
• These substances can be permanently magnetised. They retain magnetism
even after the removal of external magnetic field.
• In the solid state, the metal ions of ferromagnetic substance are grouped
together into small regions called domains, where each domain acts as a tiny
magnet.
• Some example of ferromagnetic substances are Fe, Co, Ni, Gd, CrO2