CHAPTER: 01 THE SOLID STATE

INTRODUCTION:
Matter generally exists in three physical forms namely:
1. Solids 2. Liquids and 3. Gases
Solids are rigid substances having definite shape and volume.
Characteristic of solids: In solids
a. Interparticle distances are short.
b. Interparticle forces of attractions are strong.
c. The constituent particles have fixed positions and can oscillate only about their mean
positions.

CLASSIFICATION OF SOLIDS:
On the basis of arrangement of constituent particles solids are classified into two types as
follows,
1. CRYSTALLINE SOLIDS:
Solids with orderly arrangement of constituent particles in the three dimensional
space are called crystalline solids.
2. AMORPHOUS SOLIDS:
Solids with no orderly arrangement of constituent particles in the three
dimensional space are called amorphous solids.

DIFFERENCES BETWEEN CRYSTALLINE AND AMORPHOUS SOLIDS:

PROPERTY CRYSTALLINE SOLID AMORPHOUS SOLID

Orderly arrangement of No orderly arrangement of
Arrangement of
constituent particles in the constituent particles in the three
1. constituent
three dimensional space (long dimensional space (short range
particles
range order) order)
Pseudo solids or super cooled
2. Nature True solids
liquids.
3. Shape Definite geometrical shape Irregular shape
Do not have sharp melting point.
4. Melting point Sharp melting point They melt over a range
temperatures
Anisotropic In nature. i.e
Physical properties such as Isotropic nature. i.e Various
5. Anisotropy/Isotropy refractive index, conductivity, physical properties are same in
and thermal expansion, etc. are all directions.
different in different directions.

7. Order Range Long range order Short range order

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 Split into pieces with plain and Split into pieces with irregular
6. Cleavage property
smooth surface surface
Crystals of NaCI, CsCI,
7. Examples Rubber, glass, plastics, etc
Graphite, Diamond, ice, etc.

CLASSIFICATION OF CRYSTALLINE SOLIDS:

On the basis of nature of constituent particles and nature of forces operating between
them crystalline solids are classified into four types as follows.
1. Ionic solids 2. Covalent / network solids 3. Metallic solids 4. Molecular solids

Ionic Covalent Metallic

Property Molecular solids
solids solids solids
Non-polar Polar H-bonded
Molecular Molecular Molecular
Particles Non- solids solids solids
Anions and
occupied by metallic Metal ions Polar
Cations Atoms / Non
lattice points atoms Polar Molecules
polar
Molecules containing
Molecules
H,O,F and N
London
Nature of forces/ Dipole-dipole
Ionic Covalent Metallic Hydrogen
bonding dispersion interactions
bonding
forces
Strength
Strength Hard Hard Soft Soft Soft
varies
Varies over
a wide
Melting point High High Low Low Low
range of
temperature
Conducts
either in
molten
Electrical state or in Good
Insulator Insulator Insulator Insulator
conductance dissolved conductor
state, but
not in the
solid state
Soft: Na, Atoms: Ar,
NaCI, Diamond, Solid SO2.
K,…etc. He..etc Ice
Examples CaF2, ZnS, graphite, Solid CO2
Hard: W, Molecules: (H2O)..etc.
etc. quartz etc. (Dry ice)
Mo…etc. H2, CI2, I2.etc.

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1. IONIC SOLIDS
Solids in which the lattice points are occupied by cations (+ve) and anions (-ve) that are
held by electrostatic force of attraction are called ionic solids.

PROPERTIES OF IONIC SOLIDS:

 They are hard and brittle.
 They have high melting point.
 In solid state, they do not conduct electricity because ions are net free to move but,
in the molten state or when dissolved in water, the ions become free to move and
hence they conduct electricity.
Example: NaCl, CaF2, ZnS, etc.

2. COVALENT SOLIDS (NETWORK SOLIDS):

Solids in which the lattice points are occupied by non-metallic atoms that are held by
strong covalent bonds forming a three dimensional network (giant molecule) are
called covalent solids.

PROPERTIES OF COVALENT SOLIDS:

 They are very hard and brittle.
 They have very high melting points and high enthalpies of fusion.
 Except graphite, all other covalent crystals are bad conductors of electricity.

Note:
 Diamond is the hardest substance.
 The exceptional properties of graphite are due to its structure. In graphite, carbon atoms
are arranged in different layers. Each carbon atom is covalently bonded to three 3 other
atoms in same plane. The four valency of carbon is satisfied by bonding with carbon atoms
of adjacent layers. The electron involved in the fourth valency is highly mobile. This is
responsible for good thermal and electrical conductivity of graphite.

Example: Diamond, graphite, quartz etc.

3. METALLIC SOLIDS:
Solids in which the lattice points are occupied by metal ions called Kernels immersed
in a sea of mobile electrons which are held by strong metallic bonds are called
metallic solids.
PROPERTIES OF METALLIC SOLIDS:
 Metallic solids are malleable and ductile.
 They are good conductors of heat and electricity due to mobile electrons.
 They possess a bright metallic lustre.
 They have high melting and boiling points.
 The nature of metals generally varies from quite soft (Eg. Na, K, …etc.) to very hard (Eg.
W, Mo…etc.).
Note: Electron gas theory / Electron sea model (Drude and Lorentz): Metallic bond is an
array of metal ions called kernels immersed in a sea of mobile electrons resulting in strong
cohesive forces / electrostatic forces of attraction between them.

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4. MOLECULAR SOLIDS:
Solids in which the lattice points are occupied by Polar / Non polar covalent
molecules held by relatively weak intermolecular forces like Vander Waals forces,
hydrogen bonding or dipole - dipole interactions are called molecular solids.

Based on the nature of forces of attraction molecular solids are further classified in to three
types.

(i) Non-polar molecular solids

(ii) Polar molecular solids
(iii) Hydrogen bonded molecular solids

(i) NON-POLAR MOLECULAR SOLIDS:

Molecular solids composed of either atoms (Eg. Ar, He..etc) OR non-polar molecules
(Eg. H2, CI2, I2..etc) formed by non-polar covalent bonds which are held by weak
dispersion forces or London forces,

PROPERTIES OF NON-POLAR MOLECULAR SOLIDS:

 They are soft and insulators.
 They have low melting points.

(ii) POLAR MOLECULAR SOLIDS:

Molecular solids composed of polar-molecules which are held by dipole-dipole
interactions.
PROPERTIES OF POLAR MOLECULAR SOLIDS:
 They are soft and insulators.
 They have low melting point but higher than those of non polar molecular solids.
Example: Solid SO2.

(iii) HYDROGEN BONDED MOLECULAR SOLIDS:

Molecular solids composed polar covalent molecules containing H, F, O and N atoms
which are held by hydrogen bonds.

PROPERTIES OF POLAR MOLECULAR SOLIDS:

 They are soft and insulators.
Example: ice (H2O).

CRYSTAL LATTICE (OR SPACE LATTICE):

It is an array of points, which indicates the three-dimensional arrangement of atoms,
ions or molecules in a crystal.
Space lattice gives the information regarding arrangement of the constituents of a
crystal in space. The space lattice represents the structure of a macroscopic crystal.

LATTICE POINT:
Each point in a space lattice is called a lattice point which indicates the position of the
constituent particles (atoms, ions or molecules).

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SIGNIFICANCE OF LATTICE POINT:
It indicates the position of the constituent particles (atoms, ions or molecules).

UNIT CELL:
A group of lattice points of a space lattice which when repeatedly joined in three
dimensions gives the entire space lattice of the crystalline solid is called a unit cell.
OR
It is the smallest structural repeating unit of a crystalline solid when repeated in three
dimensional space form the entire crystal lattice.
Note: Here constituent particles/Sphere means atoms, ions or molecules

TYPES OF CRYSTAL SYSTEMS:

On the basis of difference in the three unit cell edge lengths (a, b and c) and three
interfacial angles or axial angles (α, β and γ). Crystal systems are classified into 7 crystal
systems and 14 Bravais lattices. Unit cells meet the following criteria:

Bravais unit cells /Unit cells can be broadly divided into two types as follows.
1) PRIMITIVE UNIT CELLS: In primitive unit cells, constituent particles are present only at
the corners of the unit cell.

2) CENTERED UNIT CELLS: In centred unit cells, constituent particles are present at other
positions in addition to the corner of the unit cell. There are three types of centered unit cells

a) BODY CENTERED UNIT CELL (bcc): In body centered unit cells, constituent particles
are present at the corners of the unit cell and one particle at the body center.
b) FACE CENTERED UNIT CELL (fcc): In face centered unit cells, constituent particles are
present at the corners of the unit cell and one particle at the center of each face of the unit
cell.
c) END CENTERED UNIT CELL (ece): In end centered unit cells, constituent particles are
present at the corners of the unit cell and one particle at the center of any two opposite faces
of the unit cell.

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 Crystal Axial Types of unit
Axial angles Examples
systems distances cells
Primitive , Mn, Ag, Cu,
1. Cubic a=b=c α = β = γ = 90 0
Body centered , Diamond, NaCl,
Face centered CsCl
Primitive , TiO2, SnO2, Tin,
2. Tetragonal a=b≠c α = β = γ = 900
Body centered NH4Br, CaSO4
Primitive ,
Rhombic sulphur,
Orthorhombic Body centered ,
3. a≠b≠c α = β = γ = 90 0
KNO3, CaCO3,
(or Rhombic) Face centered,
BaSO4, K2SO4
End-centered
α = β =900 , Graphite, Mg, ZnO,
4. Hexagonal a=b≠c Primitive
γ = 1200 CdS
Trigonal a=b=c α = β = γ ≠ 900 Primitive Quartz, HgS
5.
(Rhombohedral)
α = γ =900, Primitive, Monoclinic sulphur,
6. Monoclinic a≠b≠c
β ≠ 900 End-centered CaSO4.2H2O
K2Cr2O7,
7. Triclinic a≠b≠c α ≠ β ≠ γ ≠ 900 Primitive
CuSO4.5H2O
Crystal
Types of unit cells / Bravias lattices
systems

1. Cubic

Simple / primitive Body centered Face centered

2. Tetragonal

Simple / primitive Body centered

Orthorhombic
3.
(or Rhombic)

Simple / primitive Body centered Face centered End centered

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4. Hexagonal

Simple / Primitive

Trigonal (or
5.
Rhombohedral)

Simple / primitive

6. Monoclinic

Simple / primitive End centered

7. Triclinic

Simple / primitive

Out of the seven crystal systems cubic system is the simplest among the unit cells. In the
cubic system; all sides are of same length and angle between faces is 90°. There are three
types Bravais lattices in cubic unit cells. They are 1) Primitive / Simple 2) body centered
and 3) face centered.
CALCULATION OF NUMBER OF PARTICLES PER UNIT CELL IN A CUBIC SYSTEM:
i. A particle present at the centre of the body of the cube is not shared by any other unit
cell. Hence, its contribution per unit cell is 1.
ii. A particle present at the centre of each face of the cube is shared by 2 unit cells.
Hence, its contribution per unit cell is 1/2.

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iii. A particle present at the edge of the cube is shared by 4 unit cells. Hence, its
contribution per unit cell is 1/4.
iv. A particle present at the corner of the cube is shared by 8 unit cells. Hence, its
contribution per unit cell is 1/8.

(A) IN SIMPLE CUBE (PRIMITIVE CUBIC UNIT CELL):

There are 8 lattice points at the corners of the cube

1
Therefore, number of particles per unit cell = 8  1
8
Coordination number = 6 , % of occupancy = 52% (52.4%), % of void = 48%

(B) IN BODY CENTRED CUBIC UNIT CELL:

There are 8 lattice points at the corners of the cube and 1 lattice point at the centre of the
cube.
 1
Therefore, number of particles per unit cell =  8    1  2
 8
Coordination number = 8 , % of occupancy = 68%, % of void = 32%

(C) IN FACE CENTRED CUBE OR CUBIC CLOSED PACKING UNIT CELL:

There are 8 lattice points at the corners of the cube and 6 lattice points at the face centres
of the cube.
 1  1
Therefore, number of particles per unit cell =  8     6    4
 8  2
Coordination number = 12 , % of occupancy = 74%, % of void = 26%

COORDINATION NUMBER:
The number of immediately neighbouring particles (spheres) to a given particle
(sphere) is called the coordination number of the particle.

VOID:
The unoccupied space or depressions left over unoccupied in the crystal lattice is
called a void.

CLOSE PACKED STRUCTURES:

In formation of crystals the constituent particles (atom, ion or molecules) are closely
packed in such a way that maximum available space is occupied leaving minimum
vacant space. This phenomenon is called closed packed structures.
This way of close packing leads to maximum possible density. Greater the Close packing
greater is the stability of the crystal system.
For better understanding of closed packed structures, Let us consider the constituent
particles (atom, ion or molecules) as identical hard spheres of equal size and construct the
close packing in the following dimensions.

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 CLOSE PACKING ARRANGEMENT:
The arrangement of given number of identical spheres in minimum space is called
close packing arrangement.

I. CLOSE PACKING IN ONE DIMENSION: In one dimensional closed packed structure the
sphere can be arranged in only one way i.e. by arranging them in horizontal row touching
each other having the co-ordination number 2.

II. CLOSE PACKING IN TWO DIMENSIONS: In two dimensional closed packed structures
the spheres can be arranged in two ways.

a) AAAA… TYPE OR TWO DIMENSIONAL SQUARE CLOSE PACKING:

In this way of arrangement the second row of spheres are placed in contact with the
spheres of first row in such a way that the spheres of second row of spheres are exactly
above the spheres of first row. If we consider the arrangement of first row spheres as ’A’
type, since all the rows have the same type of arrangement it is called AAAA..… type. In
this type of arrangement each sphere is in contact with 4 immediate neighboring spheres
hence it is called two dimensional square close packing and has a coordination number 4.
A

A
Square close packing in 2D

b) ABAB….. TYPE / TWO DIMENSIONAL HEXAGONAL CLOSE PACKING:

A
B
A
B
A
Hexagonal close packing in 2D
In this way of arrangement the second row spheres are placed in the depressions of the first
row in a staggered manner. If we consider the arrangement of the first row spheres as ’A’
type and arrangement of second row spheres as ’B’ type. These two rows are arranged
alternatively one above the other. Hence this arrangement is called ABAB…. type. In this
type of arrangement each sphere is in contact with 6 immediate neighboring spheres hence
it is called two dimensional/hexagonal close packing and a coordination number of 6.

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 III. CLOSE PACKING IN THREE DIMENSIONS:
All real structures are three dimensional structures which are obtained by stacking (joining)
two dimensional structures one above the other. The different types of three dimensional
structures are obtained as follows.

i. 3-D CLOSE PACKING FROM TWO DIMENSIONAL SQUARE CLOSE PACKED

LAYERS:
On placing the 2-D square close packed layers of spheres one above the other this type of
arrangement is obtained. If we consider the first layer as ‘A’ the next successive layers are
also identical to the first layer where the spheres are placed one above the other. Thus this
lattice has AAAA…. type pattern. This type of arrangement gives a simple cubic lattice
having the Coordination number 6.

A
A

A
Simple cubic lattice
(formed by AAAA.....type arrangement from 2D square close packing)

ii. 3-D CLOSE PACKING FROM TWO DIMENSIONAL HEXAGONAL CLOSE PACKED
LAYERS:
There are three types of arrangement in this type
a) PLACING SECOND LAYER OVER THE FIRST LAYER:
This type of arrangement is obtained by placing the second layer of two dimensional
hexagonal closed packed layers in the depressions of the first layer. After arranging the
second layer on the first layer in this form we can notice that all the triangular voids of
first layer are not covered by the spheres of the second layer. This gives raise to two
types of voids namely tetrahedral void & octahedral void.
Tetrahedral void is formed when the sphere of the second layer is above the (or covers
the) void of the first layer or vice versa. These voids are called tetrahedral voids because
a regular tetrahedron is formed when the centers of these spheres are joined.
Similarly octahedral voids are obtained when the triangular voids of second layer are
above the triangular voids of first layer. In these voids one of the apex of the triangular
void is pointing upwards & the other downwards. Octahedral void is surrounded by six
spheres. These voids are called octahedral voids because a regular octahedron is
formed when the centers of these spheres are joined.

If a crystal lattice contains ‘N’ spheres then Number of octahedral voids = N and
Number of tetrahedral voids = 2N.

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 A
B
Octahedral void
T T T T T T Tetrahedral void

T T T T T T Octahedral void

T T T T T T

T T T T T T

Stack of two layersof 2D hexagonal close packed spheres Tetrahedral void

b) PLACING THIRD LAYER OVER THE SECOND LAYER:

There are two possibilities of placing the third layer over the second layer.

1) COVERING TETRAHEDRAL VOIDS:

When the third layer of spheres is placed over the second layer of spheres in such a way
that the tetrahedral voids of second layer gets covered by the sphers of third layer then
the third layer gets exactly aligned to that of the first layer of spheres. Thus the pattern of
arrangement of spheres is repeated in alternate layers having ABAB….pattern. This
type of arrangement leads to hexagonal closed packed (hcp) structure having the co-
ordination number-12.
Example: Mg, Zn,….etc

2) COVERING OCTAHEDRAL VOIDS:

When the third layer of spheres is placed over the second layer of spheres in such a way
that the octahedral voids of second layer gets covered by the spheres of third layer then
the third layer is not aligned to either the first layer nor the second layer of spheres, but
when the fourth layer of spheres are placed over the third layer of spheres covering the
octahedral voids then the fourth layer of spheres gets exactly aligned to that of the first
layer of spheres. Thus this pattern of arrangement of spheres is called

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 ABCABC….pattern. This type of arrangement leads to cubic closed packed (ccp)
structure or face centered cubic structures (fcc) having the co-ordination number-12.
Example: Ag, Cu,….etc

FORMULA OF A COMPOUND AND NUMBER OF VOIDS FILLED:

When particles are close packed, they get packed either in simple cubic (sc) / primitive or
ccp (fcc) Or hcp structure, this type of close packing leads to formation of two types of voids,
namely
a) Octahedral void and b) Tetrahedral void.
Number of octahedral voids present in a lattice is equal to the number of close packed
particles (n), and the the number of tetrahedral voids generated is twice this number of close
packed particles (2n).
In ionic solids, the bigger ions are usually anions which form the close packed
structure and the smaller ions are usually cations which 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.
In a given compound, the fraction of octahedral or tetrahedral voids that are occupied,
depends upon the chemical formula of the compound.

PACKING EFFICIENCY:
The percentage of the total space filled by the particles is called packing efficiency.
Different types of packing arrangement have different Packing efficiency.

Packing efficiency of Simple cubic structure:

a
Let us consider a simple cubic unit cell whose edge length is ‘a’ and ‘r’
be the radius of the sphere.

We know that, volume of the cube =a3

Simple / primitive
4
volume of the sphere =  r 3
3

A simple cubic unit cell consists of only One atom/ particle/ sphere per unit cell.

4 4
 Total volume of the spheres = 1  r 3   r 3
3 3

In a simple cubic unit cell the spheres/ lattice points at the corners of the cube are
touching each other. Therefore edge length, a = 2r

Hence volume of the cube = a3 = (2r) 3 = 8r3

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 4
Volume of the sphere
 r3
% of the space occupied by spheres   100  3 3  100
Volume of the cube 8r

4  100  22
  52.38 %  52.4% is the packing fraction in simple cubic lattice .
837

PACKING EFFICIENCY OF BODY CENTERED CUBIC STRUCTURE (BCC):

Let us consider a Body centered cubic unit cell whose edge length is ‘a’ A
a
B
and ‘r’ be the radius of the sphere.
C

We know that, volume of the cube =a3

D
4
volume of the sphere =  r 3 Body centered
3

A Body centered cubic unit cell consists of only Two atoms/ particles/ spheres per unit cell.

4 8
 Total volume of the spheres = 2   r 3   r 3
3 3
In the bcc unit cell the spheres at the corners of the cube are not in contact with each
other but all are in contact with the centre sphere as shown in the diagram. As a result
the diagonal AD is equal to 4 times the radius of the sphere. i.e AD = 4r

In the right angled triangle ABC Face diagonal AC  AB 2  BC 2  2a 2

AB=BC=CD=a

Similarly, in the right angled triangle ACD

  a
2
Body diagonal AD  AC 2  DC 2  2a 2 2
 3a

4r
AD  4r  3 a  a
3
3
 4r  64 r 3
Hence, Volume of the unit cell = a  
3
 
 3 3 3
8
Volume of the sphere
 r3
  100  3  100
% of the space occupied by spheres Volume of the cube 64 r 3
3 3

8 100  22  3  3
  68.04 %  68% is the packing fraction in Body centered cubic lattice
3  7  64

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PACKING EFFICIENCY OF FACE CENTERED CUBIC CLOSE PACKING OR CUBIC
CLOSE PACKING OR HEXAGONAL CLOSE PACKING (fcc /ccp/hcp):
a
A B
Let us consider a Face centered cubic unit cell whose edge length is ‘a’
and ‘r’ be the radius of the sphere. C

We know that, volume of the cube =a3

4
volume of the sphere =  r 3
3 Face centered

A Face centered cubic unit cell consists of only Four atoms/ particles/ spheres per unit cell.

4 16
 Total volume of the spheres = 4   r 3   r 3
3 3

In fcc / ccp/ hcp unit cell, the spheres at the corners are in contact with sphere at the
face centre but are not touching each other.
Therefore face diagonal AC = 4r
In the right angled triangle ABC

Face diagonal AC  AB 2  BC 2  a 2  a 2  2a 2  2 a

4r
Therefore, AC  4r  2 a  a
2
3
 4r  64 r 3
Hence, Volume of the unit cell = a  
3
 
 2 2 2

16
Volume of the sphere
 r3
% of the space occupied by spheres   100  3  100
Volume of the cube 64 r 3
2 2

16 100  22  2  2
  74 % is the packing fraction in Face centered cubic lattice
3  7  64

CALCULATIONS INVOLVING UNIT CELL DIMENSIONS:

From unit cell dimensions it is possible to calculate the volume of the unit cell and by
knowing the density of the unit cell it is possible to calculate the mass of the unit cell.

DERIVATION OF RELATIONSHIP BETWEEN MOLECULAR MASS AND DENSITY OF

THE UNIT CELL:
From x-ray diffraction studies it is seen that the edge length of the unit cell is ‘a’
Let the density of the unit cell be ‘d’ and ‘M’ be the molar mass.

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For a cubic crystal,
Volume of the unit cell = a3
Mass of a unit cell = No. of atoms per unit cell x Mass of each atom = Z x m
M
Mass of an atom (m) =
NA
Mass of the unit cell Zxm ZxM
Density of the unit cell =  3
 3
Volume of the unit cell a a x NA

ZxM
d
a3 x N A
Where,
d = density of the unit cell Z = No. of particles present per unit cell,
M = Molar mass (GAM / GAM) a = edge length NA = Avogadro No.

Note: Density of the unit cell is the same as the density of the substance. The density of the
solid can always be determined by other methods. Out of the five parameters (d, Z, M, a and
NA), if any four are known, we can determine the fifth one.

IMPERFECTIONS IN SOLIDS:
Although crystalline solids have short range as well as long range order in the
arrangement of their constituent particles, yet crystals are not perfect. Usually a solid
consists of an aggregate of large number of small crystals. These small crystals have
defects in them. This happens when crystallisation process occurs at fast or moderate rate.
Single crystals are formed when the process of crystallisation occurs at extremely slow rate.
Even these crystals are not free of defects.
Note: Only at absolute zero crystals have a perfect orderly arrangement.

CRYSTAL DEFECTS:
The irregularities in the arrangement of constituent particles are called crystal
defects. There are two types of crystal defects namely,
1. Point defects and 2. Line defects

1. POINT DEFECTS: Irregularities or deviations from ideal arrangement around a

lattice point or an atom in a crystalline substance is called as Point defects.

2. LINE DEFECTS: Irregularities or deviations from ideal arrangement in entire row of

lattice points are called as line defects.
Our study here is confined only to point defects.

TYPES OF POINT DEFECTS: Point defects can be classified into three types:
(a) Stoichiometric defects
(b) Impurity defects
(c) Non-stoichiometric defects.

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 a) STOICHIOMETRIC DEFECTS: These are the point defects that do not disturb the
stoichiometry of the solid i.e the ratio of number of constituent particles present in the
solid compound are exactly the same in the ratios as indicated in the chemical formula.
They are also called intrinsic or thermodynamic defects.
There are two types of stoichiometric defects namely (i) Vacancy defects and (ii)
Interstitial defects.

i. VACANCY DEFECT: In a crystal when some of the lattice sites are vacant, then such a
crystal is said to have vacancy defect. This results in decrease in density of the
substance. This defect can also develop when a substance is heated.

ii. INTERSTITIAL DEFECT: In a crystal when some constituent particles (atoms or

molecules) occupy the interstitial sites, the crystal is said to have interstitial defect. This
defect increases the density of the substance.

Vacancy defect Interstitial defect

The above explained Vacancy and interstitial defects are shown by non-ionic
solids.

Ionic solids must always maintain electrical neutrality. Rather than simple
vacancy or interstitial defects, they show these defects as Frenkel and Schottky
defects.

iii. FRENKEL DEFECT: This defect is shown by ionic solids in which there is a large
difference in the size of ions (anions and cations) and low co-ordination number.
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.
Frenkel defect is also called dislocation defect. It does not change the density of the
solid.
Example: ZnS, AgCl, AgBr and AgI due to small size of Zn2+ and Ag+ ions.

iv. SCHOTTKY DEFECT: This defect is shown by ionic solids in which similar ionic sizes
(anions and cations) and high co-ordination number. It is basically a vacancy defect
in ionic solids. In order to maintain electrical neutrality, the number of missing cations
and anions are equal It decreases the density of the solid.
Example: In NaCl there are approximately 106 Schottky pairs per cm3 at room
temperature. In 1 cm3 there are about 1022 ions. Thus, there is one Schottky defect per
1016 ions. Schottky defect is shown by ionic substances in which the cation and anion
are of almost similar sizes.
Example: NaCl, KCl, CsCl and AgBr.

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 Note: AgBr shows both, Frenkel as well as Schottky defects.

+ + + + + +
++ + + + + +
+
+ + + + + +
+ + + + + + +
Frenkel defect Schottky defect

a) IMPURITY DEFECTS: Defects in solids due to presence of foreign atoms in the

interstitial or substitutional sites in a crystal is called impurity defects. If the
impurity ions have different valence state than that of the host ions vacancies are
created.
Example: If molten NaCl containing a little amount of SrCl2 is crystallised, 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. The same thing happens when molten AgCl
containing little amount of CdCl2 is crystallised.
+ - + - + - + -
Na Cl Na Cl Na Cl Na Cl
- + - + - 2+ - +
Cl Na Cl Na Cl Sr Cl Na

+ - + - + - + -
Na Cl Na Cl Na Cl Na Cl
- - + - - +
Cl Cl Na Cl Cl Na

+ - - - + -
Na Cl Sr2+ Cl Na
+
Cl Na Cl

Impurity defect

b) NON-STOICHIOMETRIC DEFECTS: Compounds in which the ratio of constituent

particles present in the compound differs from the chemical formula composition
are called Non-stiochiometric compounds or Berthollide compounds.
In these compounds the composition may vary over a wide range. A large number of
nonstoichiometric inorganic solids are known which contain the constituent elements in
non-stoichiometric ratio due to defects in their crystal structures. These defects are of
two types:
(i) Metal excess defect and (ii) Metal deficiency defect.

(i) METAL EXCESS DEFECT:

a) METAL EXCESS DEFECT DUE TO ANIONIC VACANCIES: A compound may have

excess of metal ions if anions are missing from its lattice site, leaving a hole in
that site which is occupied by electron to maintain electrical neutrality. Then such
solids are said to posses metal excess defect due to anionic vacancies.
Example: Alkali halides like NaCl and KCl show this type of defect.

INTRODUCTION OF THE DEFECT: When crystals of NaCl are heated in an

atmosphere of sodium vapour, the sodium atoms are deposited on the surface of the

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 crystal. The Cl- ions diffuse to the surface of the crystal and combine with Na atoms to
give NaCl. This happens by loss of electron by sodium atoms to form Na+ ions. The
released electrons diffuse into the crystal and occupy anionic sites. As a result the
crystal now has an excess of sodium ions and the vacant anionic sites are occupied by
unpaired electrons, these centers are called F-centres (from the German word
Farbenzenter for colour centre). They impart yellow colour to the crystals of NaCl. The
colour results by excitation of these electrons when they absorb energy from the visible
light falling on the crystals. Similarly, excess of lithium makes LiCl crystals pink and
excess of potassium makes KCl crystals violet (or lilac).

F-CENTRES:
Vacant anionic centers occupied by unpaired electrons which impart colour to the
solids are called F-centers.
+ - + - + - + -
Na Cl Na Cl Na Cl Na Cl
- + - + - + - +
Cl Na
e Na Cl Na Cl Na

+ - + - + - + -
Na Cl Na Cl Na e Na Cl F-Center
- - + - + - +
Cl Na
+
Cl Na Cl Na Cl Na

+ - + - + - + -
Na Cl Na Cl Na Cl Na Cl

Metal excess defect due to anionic vacancies

b) METAL EXCESS DEFECT DUE TO THE PRESENCE OF EXTRA CATIONS AT

INTERSTITIAL SITES:
A compound may have excess of metal ions in the interstitial sites and also the
electrons in the neighbouring interstitial sites to maintain electrical neutrality.
Then such solids are said to posses metal excess defect due to extra cations in
the interstitial sites.
Example: 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
Zn1+xO. The excess Zn2+ ions move to interstitial sites and the electrons to neighbouring
interstitial sites.

(II) METAL DEFICIENCY DEFECT:

Many solids which are difficult to prepare in the stoichiometric composition and contain less
amount of the metal as compared to the stoichiometric proportion as represented in the
chemical formula, such solids are said to poses metal deficiency defect.
Example: FeO which is mostly found with a composition of Fe0.95O. It may actually range
from Fe0.93O to Fe0.96O. In crystals of FeO some Fe2+ cations are missing and the loss of
positive charge is made up by the presence of required number of Fe3+ ions.

ELECTRICAL PROPERTIES:
Solids exhibit an amazing range of electrical conductivities, extending over 27 orders of
magnitude ranging from 10–20 to 107 ohm–1 m–1. Solids can be classified into three types on
the basis of their conductivities.

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 (i) CONDUCTORS: The solids with conductivities ranging from 104 to 107 ohm–1m–1 are
called conductors. Metals having conductivities in the order of 107 ohm–1m–1 are good
conductors.

(ii) INSULATORS: These are the solids with very low conductivities ranging from 10–20 to
10–10 ohm–1m–1.

(iii) SEMICONDUCTORS: These are the solids with conductivities ranging from 10–6 to 104
ohm–1m–1 which is in the intermediate range of conductors and insulators.

BAND THEORY explains the conductivity of solids.

According to band theory,

BAND: A group of closely spaced energy levels is called band.

VALENCE BAND: The highest occupied energy level is called valence band.

CONDUCTION BAND: The lowest unoccupied energy level is called conduction band.

BAND GAP: The energy difference separating the valence band and the conduction
band is called band gap or energy gap (Eg).

FORBIDDEN BANDS: The spaces separating the Energy bands are called forbidden.
In these forbidden bands there are no allowed energy states.

i. CONDUCTION OF ELECTRICITY BY CONDUCTORS:

ELECTROLYTIC CONDUCTORS: Conductors which conduct electricity through movement

of ions are called electrolytic conductors. Electrolytes conduct electricity only in dissolved
state or in molten state.
Example: NaCl, KCl…etc.

METALLIC CONDUCTORS:

Conduction band
(Empty)

Valence band
Energy

(Filled)

Partialy filled band Overlapping bands

Conductors (Metals)
Conductors which conduct electricity through movement of electrons are called metallic
conductors. Metals conduct electricity in solid state as well as molten state.

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 The conductivity of metals depends upon the number of valence electrons available per
atom. The atomic orbitals of metal atoms form molecular orbitals which are so close in
energy to each other as to form a band. If this band is partially filled or it overlaps with a
higher energy unoccupied conduction band, then electrons can flow easily under an applied
electric field and the metal shows conductivity.

ii. CONDUCTION OF ELECTRICITY BY INSULATORS: In insulators the gap between

filled valence band and conduction band (the next higher unoccupied band ) is so large,
so that the electrons cannot jump from the valence band to the conduction band easily
hence these substances show very small conductivity and hence behaves as an
insulator.

Conduction band
(Empty)

Forbidden zone
(Large energy gap)
Energy

Valence band
(Filled)

Insulators

iii. CONDUCTION OF ELECTRICITY BY SEMICONDUCTORS:

In semiconductors, the gap between the valence band and conduction band is small.
Therefore, some electrons may jump from valence band to conduction band and show some
conductivity.
Electrical conductivity of semiconductors increases with rise in temperature, since
more electrons can jump from valence band to the conduction band. Substances like silicon
and germanium show this type of behaviour and are called intrinsic semiconductors.

Conduction band
(Empty)

Small energy gap

Energy

Valence band
(Filled)

Semi conductors

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TYPES OF SEMICONDUCTORS:
There are 2 types of semiconductors:
1. Intrinsic semiconductors 2. Extrinsic semiconductors

1. INTRINSIC SEMICONDUCTOR: Semiconductors containing pure Si and Ge are called

intrinsic semiconductors.
In Si or Ge at 0 (zero) Kelvin no free electrons are available to conduct electricity
since all the electrons are involved in the bond formation. If they are heated some of the
covalent bonds get broken and the electrons become free to conduct electricity under an
applied potential.
The conductivity shown by intrinsic semiconductors is too low; however the conductivity
can be increased by adding an impurity such as group-13 or group-15 elements. The
phenomenon of adding impurity to an intrinsic semiconductor is called doping. Such
impurities introduce electronic defects in them.

Si Si Si Si

Si Si Si Si

Si Si Si Si

Si Si Si Si

Intrinsic semiconductors
(Pure silicon)
DOPING: The conductivity of intrinsic semiconductors is too low to be of practical
use. Their conductivity is increased by adding an appropriate amount of suitable
impurity. This process is called doping.
Doping can be done with an impurity which is electron rich or electron deficient as compared
to the intrinsic semiconductor silicon or germanium.

2. EXTRINSIC SEMICONDUCTOR: Si and Ge (Intrinsic semiconductors) can be made a

better semiconductor at room temperature by increasing the number of either free electrons
or holes. This is done by doping it with impurity elements from either group 13 or 15 to an
extent of 100 to 1000 ppm (parts per million). By adjusting the amount of impurity, the
conductance of the semiconductors can be varied.
Based on the type of impurity doped, two types of extrinsic semiconductors are formed. They
are
a) n- type semiconductors b) p- type semiconductors

a) n- TYPE SEMICONDUCTORS (ELECTRON – RICH IMPURITIES): Silicon and

germanium belong to group 14 of the periodic table and have four valence electrons
each. In their crystals each atom forms four covalent bonds with its neighbours when Si
/Ge is doped with the 15th group element like phosphorus or Arsenic or antimony which

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 contains five valence electrons n- type semiconductor is obtained. Out of 5 electrons
available 4 electrons are used for bonding with the neighboring Si / Ge atoms. The fifth
electron is extra and becomes delocalised. These delocalised electrons increase the
conductivity of doped silicon (or germanium). Here the increase in conductivity is due to
the negatively charged electron, hence silicon doped with electron-rich impurity is called
n-type semiconductor.

Si Si Si Si Si Si Si
. Si
. + Positive hole
Extra electron
Si P Si Si Si Si B Si

Si Si Si Si Si Si Si Si

Si Si Si Si Si Si Si Si

n-type semiconductors p-type semiconductors

(Doped with G-15 element) (Doped with G-13 element)

b) p- TYPE SEMICONDUCTORS (ELECTRON – DEFICIENT IMPURITIES): when Silicon

and germanium is doped with the 13th group element like boron, aluminium or gallium p-
type semiconductor is obtained.
Group-13 elements have 3 electrons in the valence shell; which are completely used for
bonding with the neighboring Si atoms hence Group-13 elements can form bonds with
three Si atoms. The fourth electron in Si is left unbounded and hence each Group-13
element produces a positive hole and the valency remains unsatisfied.
Each electrons from the adjacent bonds jump to fill the positive hole, as a result
the positive hole shifts to the adjacent site from where the electron has jumped. The
process continues. Hence p-type semiconductor conducts electricity by the movement of
positive holes. So the conductor is called p- type semiconductor.
Note: It would appear as if electron holes are positively charged and are moving towards
negatively charged plate under the influence of electric field.

Applications of n-type and p-type semiconductors:

Various combinations of n-type and p-type semiconductors are used for making electronic
components.

1. DIODE: It is a combination of n-type and p-type semiconductors and is used as a

rectifier.
2. TRANSISTORS: are made by sandwiching a layer of one type of semiconductor
between two layers of the other type of semiconductor, npn and pnp type of transistors
are used to detect or amplify radio or audio signals.
3. SOLAR CELL: It is an efficient photo-diode used for conversion of light energy into
electrical energy.

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SPECIAL TYPE SEMICONDUCTORS:
Germanium and silicon are group 14 elements and therefore they have a characteristic
valence of four and form four bonds as in diamond.
A large variety of solid state materials have been prepared by combination of groups 13 with
15 and 12 with 16 to simulate average valence of four as in Ge or Si.
 Compounds of groups 13 – 15 are InSb, AlP and Ga As.
 Compounds of groups 12 – 16 are ZnS, CdS, CdSe and HgTe.
Gallium arsenide (GaAs) semiconductors have very fast response and have
revolutionised the design of semiconductor devices.
In these compounds, the bonds are not perfectly covalent and the ionic character
depends on the electronegativities of the two elements.

CONDUCTIVITY OF TRANSITION METAL OXIDES:

Transition metal oxides show marked differences in electrical properties.
 TiO, CrO2 and ReO3 behave like metals.
 ReO3 (Rhenium oxide) is like metallic copper in its conductivity and appearance.
 Certain other oxides like VO, VO2, VO3 and TiO3 show metallic or insulating properties
depending on temperature.

MAGNETIC PROPERTIES:
INTRODUCTION: Every substance has some magnetic properties associated with it. The
origin of these properties lies in the electrons. Each electron in an atom behaves like a tiny
magnet. Its magnetic moment originates due to two types of motions of electrons. They are
(i) ORBITAL MOTION OF ELECTRON around the nucleus
(ii) SPIN MOTION OF ELECTRON around its own axis
Electron being a charged particle and undergoing these motions can be considered as a
small loop of current which possesses a magnetic moment. Thus, each electron has a
permanent spin and an orbital magnetic moment associated with it.
Magnitude of this magnetic moment is very small and is measured in the unit called
Bohr magneton, μB. It is equal to 9.27 × 10–24 Am2.
On the basis of their magnetic properties, substances can be classified into five categories:
(1) Paramagnetic (2) Diamagnetic (3) Ferromagnetic (4) Antiferromagnetic
(5) Ferrimagnetic

1. PARAMAGNETISM: Paramagnetic substances are weakly attracted by a magnetic

field. They are magnetised in a magnetic field in the same direction. They lose their
magnetism in the absence of magnetic field. Paramagnetism is due to presence of
one or more unpaired electrons which are attracted by the magnetic field. Examples:
O2, Cu2+, Fe3+, Cr3+ ..etc

2. DIAMAGNETISM: Diamagnetic substances are weakly repelled by a magnetic field.

They are weakly magnetised in a magnetic field in opposite direction.
Diamagnetism is shown by those substances in which all the electrons are paired (no

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 unpaired electrons). Pairing of electrons cancels their magnetic moments and they lose
their magnetic character. Examples: H2O, NaCl, O3, C6H6 ..etc

3. FERROMAGNETISM: Ferromagnetic substances are very strongly attracted by a

magnetic field. Besides strong attractions, these substances can be permanently
magnetised. In solid state, the metal ions of ferromagnetic substances are grouped
together into small regions called domains. Thus, each domain acts as a tiny
magnet. In an unmagnetised piece of a ferromagnetic substance the domains are
randomly oriented and their magnetic moments get cancelled. 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. This ordering of domains persist even
when the magnetic field is removed and the ferromagnetic substance becomes a
permanent magnet.
Examples: Fe, Co, Ni, Gd (gadolinium) and CrO2..etc

Schematic alignment of magnetic moments in ferromagnetic substances

4. ANTIFERROMAGNETISM: Antiferromagnetic substances have domain structure

similar to ferromagnetic substances, but their domains are oppositely oriented in
equal numbers and hence they cancel out each other's magnetic moment as a result of
this they are not attracted by magnetic field.
Examples: MnO

Schematic alignment of magnetic moments in antiferromagnetic substances

5. FERRIMAGNETISM: Ferrimagnetic substances have domain structure aligned both

in parallel and anti-parallel directions in unequal numbers as a result of this they
have net magnetic moment and hence these substances are weakly attracted by
magnetic field when compared to ferromagnetic substances. Ferrimagnetic substances
lose ferrimagnetism on heating and become paramagnetic.

Examples: Fe3O4 (magnetite) and ferrites like MgFe2O4 and ZnFe2O4.

Schematic alignment of magnetic moments in ferrimagnetic substances

*********

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