UNIT 1: SOLID STATE

Introduction
Physical states of matter- solid, liquid & gas
Heat Heat
Solid Liquid Gas
Cool Cool

Solids: solids have fixed chemical composition i.e. they have fixed mass, volume,
shape and density.

These change slightly with the change in temperature & pressure

The smallest constituent particles of solids are atoms, ions or molecules.

These smallest constituents will be called as 'particles’ in this chapter.

Solids have strong inter particle forces of attraction.

 Classification of Solids
SOLIDS

CRYSTALLINE AMORPHOUS

MOLECULAR IONIC METALLIC COVALENT

HYDROGEN
POLAR NON-POLAR
BONDED
 Crystalline Solids

Crystalline solids are homogeneous solids,

in which constituent particles/atoms/ions/
molecules
are arranged in a definite repeating pattern
over a long range

Crystalline solids have sharp melting points

i.e. they melt at a definite temperature

.E.g. Ice, salts like NaCl, metals like Cu,

Au & materials like diamond,
graphite, ceramics
All crystalline solids except those
having a cubic structure are
anisotropic in nature i.e.
the magnitude of properties like
refractive index, thermal &
electrical conductivities etc. are
different in different directions.
Amorphous Solids
-Substances appear like solids, but do not
have well developed, perfectly ordered
crystalline structure are amorphous solids

-They are not real solids, but truly

supercooled liquids

- Constituent particles are randomly

arranged.

- Particles do not have a long range ordered

structure, but have a short range order

-Amorphous solids do not have ordered

internal structure & do not have sharp
Amorphous Solids - On heating amorphous solids soften
gradually & continuously & start to
flow

-The magnitude of physical properties

like refractive index, conductivity do
not change with change in direction.
- Hence they isotropic.

-ex. Tar, glass, rubber, plastic , metallic

glass( metal & metalloid alloys)
Isomorphism- Two or more
substance having same crystal
structure
[e.g.- NaF ( atoms in ratio 1:1),
MgO (ratio 1:1) ]

Chemical composition of
substance have same atomic ratio

The same atomic ratio, similar molecular

formula or similar chemical properties of
solid does not mean that they are isomorphous.

E.g. NaCl & KCl.

In these solids all properties are identical, but crystal structure are different.
•Polymorphism:
•Single substance existing in 2 or more forms or crystalline structures is
said to be polymorphous.
→Polymorphs are formed in different conditions
Eg. Calcite & orognite are the 2 forms of calcium carbonate
α- quartz, β- quatrz , cristobalite are 3 of several forms of silica.
→ Elements showing polymorphism exhibit allotropy.
Eg. Diamond , graphite & fullerene are the 3 allotropic or
polymorphic forms of carbon.
 CLASSIFICATION OF CRYSTALLINE SOLIDS

Ionic crystals
Covalent Crystals
Molecular Crystals
Metallic crystals
 Classification of Crystalline Solids
1.Ionic Crystals-
Characteristics
- Constituent particles of ionic crystals
are charged ions( cations & anions)
of different sizes.

- The oppositely charged ions are held together by

electrostatic force of attraction ( coulomb force)

- They are hard & brittle with high melting points & can act as insulators at low
temperature

- In solid state they are non conductors of electricity, but when melted or dissolved in
water they become good conductors.
 Classification of Crystalline Solids
2. Covalent Network Crystals:
Characteristics
Constituent particles in covalent network solids
are atoms

The atoms are linked together by continuous

covalent bonds, which gives rise to 3 dimensional
network forming a giant molecule.

The entire crystal is a single molecule

Covalent network crystals are very hard & incompressible of all materials
due to rigid & strongly bonded structure.
2. Covalent Network Crystals:
Characteristics
Covalent solids are poor conductors of heat & electricity as electrons are localised
in covalent bonds & not mobile.

They have high Melting & boiling points & can be used as
insulators at low temperature.

Eg. Diamond, silica ( quartz), boron nitride,

Carborundum (SiC)

Although Conductivity of covalent soilds is in general low &

increases with temperature; there is no abrupt rise in conductivity.
3. Molecular Solids:
molecular solids like Cl2, CH4, H2 CO2, O2 on solidification give rise to molecular solids.
Crystalline organic compounds are also molecular solids.
Characteristics:
1. Constituent particles of molecular solids are molecules ( or unbonded single atoms)
of same substance.
2. The bonds within the molecules are covalent.
The molecules are held together by various intermolecular forces of attraction like:

a) Weak dipole dipole interaction: it is seen in molecules like HCl, H2O, SO2 which have
permanent dipole moment
b) Very weak dispersion forces or London Forces: These are the forces present
among non polar molecules like solid CH4, H2, & in mono atomic solids like Ar,
Ne (gases at room temp.) hence called noble gases.

c) Intermolecular hydrogen bonds:

These are the bonds seen in H2O (ice) ,
NH3, HF & so on….

3. Since the intermolecular attractive

forces are weak, molecular solids
are soft with low melting points.

4. Molecular solids are poor conductors

of electricity & act as good insulators.
4. Metallic Solids: They are crystalline solids formed by atoms of same
metallic elements held together by metallic bond.
Metallic Bond:→ In a solid metal, the valence electrons are delocalised over
the entire crystal leaving behind positively charges ions.
→Thus the metal crystals always seems like to be an array of positive ions in a
sea of mobile electrons.
→This interaction between cations & mobile electrons constitute metallic
bond.
Characteristics:
1. metals are malleable & can be drawn into thin sheets.

2. Metals are ductile & can be drawn into wires.

3. Metals have good electrical & thermal conductivity.

Eg. Metals like Na, K, Ca, Li, Fe, Au, Ag etc
 CRYSTAL STRUCTURE
-Crystal structure can be well explained
by using 2 terms:
1. Crystal lattice 2. Basis

- Lattice is the geometrical arrangement

of points in a 3 dimensional periodic
array

-constituent particles
(atoms/ions/molecules) attached to the
lattice points forms basis of crystal
lattice.

-Crystal structure is obtained when you

attach the basis to the lattice points.
 Unit Cell
Defn: The smallest repeating structural unit of
a crystalline solid is called a unit cell.

-The geometric shape of a unit cell will always

be that of the macroscopic crystal
i.e. If the crystal has cubic shape the unit cell
will also be in the cubic form

The dimensions ( edges) of unit cell along the

3 axes are denoted by a,b,c.

The angles between these axes is denoted by

α, β & γ
 TYPES OF UNIT CELLS

1.Primitive/Simple unit cell:

The constituent particles are present
at its corners only

2. Body centered unit cell:

In body centered unit cell one
particle is present at the centre of
the body in addition to the corner
particles.
3. Face centered unit cell:
In this type one particle is present at the
centre of each face of the unit cell in
addition to the corner particles

4.Base centered unit cell:

This unit cell consists of one particle at
the centre of any two faces opposite to
each other in addition to the corner
particles.
 CRYSTAL SYSTEMS
•Mathematical analysis shows that the lattice points can be
arranged in 14 different ways in 3 dimensional order

•These 14 lattice describes the crystal structure & is called

‘Bravais Lattice’

•The spacing of the combinations of lattice points (a, b & c) along

the 3 axes & the angles between these axes (α,β& γ) gives rise to
7 different crystal systems.
 CUBIC SYSTEM

1) Simple Cubic Unit Cells/Primitive (SCC)-

It has one particle at the 8 corners of a cube

2) Body centered unit cell:

It has a particle at the 8 corners & a particle
at the centre of the cube

3) Face centered cubic unit cell Fcc:

It has a particle at the centre of each of its
faces in addition to a particle at the 8
corners of the cube
 Number of particles in Cubic Unit Cells
1)Simple Cubic Unit Cell( scc):

→In scc there are constituent particles present at the 8 corners.

→ If these unit cells are stacked together,

particles at each corner of the unit cell
is shared by 7 other
neighbouring unit cells.

→ Thus the corner particle contributes its ⅛th part to the

given unit cell

Therefore scc has ⅛ X 8 = 1 particle per unit cell

2) Body centered unit cell (bcc):
→ In a bcc unit cell there are 8 corner particles in addition to one more
particle at its centre.
→ There is ⅛th of a particle at the eight corners of the unit cell & one
particle at the centre of a given cube which is not shared by any other unit
cell.
→ Hence a bcc unit cell has one particle from eight corners & one particle
in the centre of the cube
→ Thus bcc has
⅛ X 8 = 1 particle(corners) + 1 particle at centre
= 2 particle/unit cell
3) Face centred Cubic (FCC) Unit Cell-
-There are 8 spheres at 8 corners of cube In addition there is one sphere at centre of
each face. No. of atoms at 8 corners of unit cell of FCC are also 1/8 x 8 = 1
- Spheres at the centres of each face of unit cell are shared betn. 2 faces. Hence ½
sphere is present at face of each unit cell & there are total 6 faces of cube
-Total spheres present in faces of unit Cell = ½ x 6 = 3
-Total spheres in FCC unit cell = 1+3 = 4
RELATION BETN. MOLAR MASS, DENSITY OF SUBSTANCE
AND UNIT CELL EDGE LENGTH
If unit cell edge length is ‘a’, then volume of unit cell = a3
Let ‘m’ be the mass of a particle & Let ‘n’ be the no. Of particles
Hence the Mass of unit cell = m X n

Density of unit cell(ρ) = Density of substance

= Mass of unit cell/volume of unit cell

= m X n / a3....................(1)
Molar mass of substanceMass
(M) isofgiven
oneasparticle X No. Of particle per mole
M =

i.e. M = m X NA ( NA ( particle per mole) = Avogadro’s number)

Hence, m = M/ NA ................... (2) ρ = M X n / a3 X NA
 PACKING OF PARTICLES IN CRYSTAL LATTICE

When packing of particles are studied , individual particles are considered as

spheres of equal size.
→ The number if spheres that touch any given sphere is its coordination
number (CN)
→ Magnitude of the CN gives you the compactness of the spheres in closed
pack structures.
1) CLOSED PACKING IN ONE DIMENSION:
This structure arises when the spheres are arranged in a row so that every
sphere comes in contact with 2 neighbouring spheres.
2) CLOSED PACKING IN TWO DIMENSIONS:
A closed packing two dimensional structure results by stacking the one dimensional rows
in such a manner
that every row is in contact with
each other.
This gives rise to 2 types of packing:

a)SQUARE CLOSE PACKING STRUCTURE:

→One dimensional rows of closed packing spheres are stacked over each other such that
the sphere allign with each other vertically & horizontally
→ If first row is ‘A’ , the second row being same as A is also labelled as ‘A’. This
arrangement is called ‘AAAA’ type 2 dimensional arrangement.
→ CN in this arrangement is 4.
→ If the centres of all spheres are
joined a square is obtained
→ Voids in square closed packing
is square shaped large enough to
hold one sphere
b) HEXAGONAL CLOSED PACKING STRUCTURE:
→ In one dimensional close packed structure depressions can be observed
between neighbouring spheres.
→ If second row is stacked in such a way
that the spheres of second row fits in the
depression of first row.
A staggered arrangement is observed.
→ If the first row is ‘A’; second row being different is called ‘B’
→ When a third row is placed in the
staggered second row ; the sphere of the
third row alligns with the sphere of the
first row, hence the third row is ‘A’ type.
→ similarly spheres of the fourth row alligns
with the spheres of the second row & so it
will be ‘B’ type.
→ The resulting 2 dimensional arrangement
will be of ‘ABAB’ type
b) HEXAGONAL CLOSED PACKING STRUCTURE:
→ In this type of structure each sphere is in contact with 6 spheres ,
hence the CN is 6.
→ If the centres of these spheres are joined a regular hexagon is
obtained.
→ Such a 2 dimensional close packing is called hexagonal close packing
in 2 dimensions.
 3) CLOSED PACKING IN 3-DIMENSION
2- Dimensional structure when stacked
gives rise to 3 dimensional structure
i)Stacking of square closed packed layers:
→ When square close packed layers are stacked
One above other, such that the spheres of
second layer is exactly above the spheres of the first layer,
it gives rise to 3 dimensional SIMPLE CUBIC STRUCTURE.
→ In this arrangement spheres of all layers are
alligned vertically & horizontally & hence all
layers are alike & labelled as ‘A’ layers.
→ This arrangement is called ‘AAAA’ type
→ In simple cubic structure CN is 6 as each
sphere is in contact with 6 spheres ; 4 in its own
layer & one in the lower layer & one in the above
layer.
→ Eg. POLONIUM crystallizes in
simple cubic closed packed structure
ii) Stacking of 2 hexagonal closed packed layers:
→ 3 dimensional closed packed structure is obtained by stacking hexagonal
close packed layers.
→ The second layer is placed in the depression of the first layer
→ The spheres of second layer do not align with the spheres of first layer
hence the first layer is labelled as ‘A’ & the second layer as ‘B’
→ Only half of the triangular voids are
covered totally by second layer.
→ This gives rise to a new void called
tetrahedral voids which is formed
from 4 spheres
→ Remaining half of the triangular voids have above them the triangular
voids of second layer.
→ These overlapping triangular voids of two layers forms another void
called octahedral voids
→ these voids are formed by 6 spheres.
iii) Placing the third hexagonal close packed layer:
→ This can be done in 2 ways:
a)First way is placing the spheres of third layer in the
tetrahedral voids of second layer
→ The spheres of the third layer
align with the spheres of first layer
& hence will be of ‘A’ type.
→Similarly spheres of fourth layer
aligns with the second layer &
hence called as ‘B’ type.
→ The resulting arrangement will be
‘ABAB’ type.
→ The structure so obtained is 3D
Hexagonal closed packed structure
→Eg. Mg, Zn, have hcp structure
b) In this type the third layer is placed in the octahedral voids of second layer
→ The spheres of the third layer do
Not align with spheres of previous
layers & is called the ‘C’ layer.
→ When the fourth layer is placed
In the octahedral voids of third layer, spheres align with the first layer & hence the fourth
layer will
be of ‘A’ type.
→ Similarly fifth & sixth layer will be of ‘B’
& ‘C’ type respectively.
→Such an arrangement is called ‘ABCABC’
type of arrangement & the structure is called
cubic close packed structure(ccp) similar to fcc structure.
Eg. Cu, Ag have ccp structure
Coordination Number in hcp & ccp structure
PACKING EFFICIENCY:

DEFN: It is the fraction or the percentage of the space occupied by the

spheres (particles)
Thus
Packing Efficiency = Volume occupied by particles in unit cell X 100
Total volume of unit cell

1.Packing efficiency of simple cubic lattice:

STEP 1: Radius of sphere:

In Scc spheres at corner touching each other along
the edge.
In the above fig a = 2r or r = a/2...........(1)
Where a = egde length & r = radius
Step 2: Volume of sphere:
Volume of a sphere = 4/3πr3
Substitute r from eqn 1
Volume of a sphere = 4/3π(a/2)3

= πa3 /6

Step 3: Total volume of particles:

As scc unit cell consists of 1 particle
Volume occupied by one particle = 1 X πa3 /6 = πa3 /6

Step4: Packing efficiency:

Packing Efficiency = Volume occupied by particles in unit cell X 100
Total volume of unit cell
= πa3 /6 X100 = 100π/6 =100 X 3.142/6 = 52.36%
a3
Hence in simple cubic unit cell 52.36% space is occupied & 47.64% is empty
2) Packing efficiency in bcc unit cell:
→ In bcc particles are present at the 8
corners in addition to one at the centre.
→Centre sphere touches the 2 corner particles
diagonally.
Step1: Radius of sphere:
Pythagoras theorem
In ∆FED FED = 900 hence (FD)2 = (FE)2 + (ED)2
(FD)2 = a2 + a2 = 2a2
Consider ∆AFD ADF = 900 (AF)2 = (AD)2 + (FD)2
(AF)2 = a2 + 2a2 = 3a2
(AF) = √3a
But (AF) = 4r hence 4r = √3a
Therefore r = √3a/4………………………………(1)
Step 2: Volume of one sphere:
Volume of a sphere = 4/3πr3 Substitute r from eqn. 1
Volume of a sphere = 4/3π(√3a/4)3

= √3πa3 /16
Step 3: Total volume of particles:
As bcc unit cell consists of 2 particles
Volume occupied by 2 particles = 2 X √3πa3 /16 = √3πa3 /8

Step4: Packing efficiency:

Packing Efficiency = Volume occupied by particles in unit cell X 100
Total volume of unit cell
= √3πa3 X 100 =100 X 3.142 X 1.732/8 = 68%
8Xa3
Hence in body centered cubic unit cell 68% space is occupied & 32% is
empty.
3) Packing efficiency in fcc unit cell (hcp or ccp)
→ In fcc particles at the corner are assumed to touch the particle at the centre of the face ABCD
Step1: Radius of sphere:
By Pythagoras theorem
In ∆ABC ʟABC = 900 hence
(AC)2 = (AB)2 + (BC)2
(AC)2 = a2 + a2 = 2a2
(AC) = √2a
But (AC) = 4r hence 4r = √2a
Therefore r = √2a/4 = a/2 √2 ………(1)
Step 2: Volume of one sphere:
Volume of a sphere = 4/3πr3
Substitute r from eqn. 1
Volume of a sphere = 4/3π(a/2√2 )3
3
Step 3: Total volume of particles:
As fcc unit cell consists of 4 particles
Volume occupied by 4 particles = 4X πa3 /12√2 = πa3 /3√2

Step4: Packing efficiency:

Packing Efficiency = Volume occupied by particles in unit cell X 100
Total volume of unit cell
= πa3 X 100 =100 X 3.142 /3 X 1.414 = 74%
3√2 X a3
Hence in face centered cubic unit cell 74% space is occupied & 26% is empty or void
 CRYSTAL DEFECTS OR IMPERFECTIONS
→ Real & naturally occurring crystalline substances are not perfect, they have
some disorders or irregularities in arrangement of constituent particles (spheres)
→ These irregularities are known as defects or imperfections.
→ Defects are mostly caused during crystal formation specially if crystallization
takes place faster.
→ Ideal crystals without any defects are possible at absolute zero of temperature,
above it no crystals are 100% pure.
→ Even if the crystals have defect in them , electrical neutrality of solids are
always maintained.
→ There are 3 types of defects
1] point defect 2] line defect 3] plain defect
Point Defect: Its the irregularities that are produced in the arrangement of basis
at the lattice points.
a) Stoichiometric b) impurity c) Non stoichiometric defects
 a) STOICHIOMETRIC DEFECTS
→In this defect the stoichiometry is unchanged i.e. the ratio of the number of
cations & anions of a compound remains the same as is represented by the
chemical formula.

Types:
1] VACANCY DEFECT: During crystallization a particle goes missing from its
regular site in crystal lattice
→ This creates a vacant space at the lattice sites .
→ Crystal thus exhibits vacancy defect.
→ Due this defect the mass of the substance decreases
with no appreciable change in volume ,
thus the density of the substance decreases.
→ Vacancy defect can also be
developed when the substance is heated.
 a) STOICHIOMETRIC DEFECTS
2] Self interstitial defect in chemical solids:
→ Space or voids in between the constituent particles at lattice points are
called interstitial points.
→ When a particle of crystalline elemental solid occupy interstitial space in
crystal structure , it is called self interstitial defect.

It Can be caused in 2 ways

A)An extra particle same as the existing particle
occupies empty interstitial space at the lattice
points

This extra particle increases the mass of the

substance without increase in volume &
hence the density increases
 a) STOICHIOMETRIC DEFECTS
2] Self interstitial defect in chemical solids:
B] Particle leaves its original lattice point &
occupies interstitial space in crystal.

→ Due to the displacement of the

particle from its original site a vacancy is
created at the regular site & interstitial
defect results at a new position.

→ Here we find a combination of vacancy & interstitial defect.

→ There being no increase or decrease in mass of the substance the density of

the substance remains the same
 a) STOICHIOMETRIC DEFECTS
3] Schottky Defect: This defect occurs in ionic solids
→ Equal number of cations & anions disappear
from their regular positions thereby creating
vacancies.

→ a vacancy caused by the loss of cation is always

accompanied by a vacancy formed by the loss of
Anion.

→ two voids are created by the loss of a pair of ions.

This vacancy is called Schottky defect.
Conditions for Schottky defects:

→ This defect is found in ionic comps. Having high degree of ionic character.
→ High Coordination number of anion
→ Small difference between the size of cation & anion.
 a) STOICHIOMETRIC DEFECTS
Consequences of Schottky Defect:
→ Number of ions decreases causing a decrease in
mass with no appreciable change in volume &
hence density of substance decreases.

→ Since the number of Cations & anion missing are

the same , electrical neutrality of the substance is
maintained.

Eg. NaCl, AgBr, KCl show Schottky defect

 a) STOICHIOMETRIC DEFECTS
4] FRENKEL DEFECT: In this defect in an ionic
compound, an ion (cation) moves away
from its regular lattice site & occupy
interstitial positions between lattice points.
→ Frenkel defect is a combination of vacancy
& interstitial defect.
Conditions for Frenkel defect:
1.can be seen in ionic compounds having large difference of size between
cation & anion.
2. Ions of ionic compound may be having low coordination number.
Consequences of Frenkel defect:
1.Since no ions are missing from crystal structure , the density & chemical
properties remain unchanged.
2. Crystal remains electrically neutral due to equal number of cations &
anions
 b) IMPURITY DEFECT
This defect is due to the presence of foreign atoms in the crystal lattice.
There are 2 types of impurity defect:
i)Substitutional Impurity Defect:

→Atoms other than the host atoms are found at the lattice sites.

→ The regular atoms are replaced from their

lattice sites by the impurity atoms.
Eg. Solid solutions of metals ( alloys)

→ Brass is an alloy of Cu & Zn

Here the host copper atom is replaced by an
impurity i.e. Zinc atom

Regular site of copper atoms are replaced by zinc atoms

 Vacancy created by an Aliovalent Impurity
→ Vacancies can be created by addition of aliovalent ions as impurities
( ions having oxidation state different from host ions)
→ Eg. Suppose small amount of SrCl2 (impurity)
is added to NaCl during crystallization .

→ The Sr2+ ( ox.no. +2) occupy some of the

regular sites of Na+ (ox.no.+1)

→ To maintain electrical neutrality every Sr2+

ions remove 2 Na+ ions.

→ Sr2+ ions occupies one of the vacant space

caused by the removal of 2Na+ ions keeping
the other Na+ ion site vacant
 b) IMPURITY DEFECT
ii) Interstitial Impurity Defect:

In this defect the impurity atoms

occupy interstitial spaces of lattice
structure.

→ Eg. In steel normal sites are

occupied by Fe atoms & carbon
atoms are present in the interstitial
spaces.
 c) NON STOICHIOMETRIC DEFECTS
In non Stoichiometric defects the ratio of number of cations to anions is
different from those indicated by its chemical formula.
→ Change in stoichiometry does not change the crystal structure.
Its of 2 types:
i) Metal deficiency defect: This defect is seen in compounds of metals that
show variable oxidation states.

→ In some crystals the positive metal ion go missing from their original sites
creating an extra negative charge.

→ This charge is balanced by the

presence of cation of the same metal
but with a higher oxidation state
than that of the missing cation
 c) NON STOICHIOMETRIC DEFECTS
i.Metal deficiency defect contd...
Eg. Let us consider a compound NiO, where
one Ni2+ is missing & creates a vacancy.
This deficiency of 2 positive charges is made
up by two Ni3+ ions at the lattice sites .
Composition of NiO becomes Ni0.97O1.0
 c) NON STOICHIOMETRIC DEFECTS
ii) Metal excess defect:
metal excess defects are of 2 types

a)A neutral atom or extra positive ion occupies interstitial position.

→ This defect is shown by ZnO in 2 ways:
→ 1. Neutral Zn atom is present in interstitial space
→ 2. When ZnO is heated Zn2+ ions are trapped in interstitial space &
electrons also diffuse in the crystal to occupy interstitial sites
b) By anion vacancies ( Colour or F - centres):

→ This defect imparts colour to the colourless crystal.

Eg. NaCl when heated in the atmosphere of
sodium vapours Na atoms are deposited on crystal surface.

→ Chloride ion diffuse to the crystal surface

creating vacancy at its original site.

→ This chloride ion combines with Na on the

surface to form NaCl with the release of
electrons from sodium atom.

Na + Cl Θ → NaCl + e –

→ electrons released diffuse into the crystal

& occupy the vacant space of anion.

→ These vacant sites of anion occupied by the

electrons are called F-centres or colour centres

Nacl thus shows yellow colour due to the formation of F- centre

Number of particles and unit cells in x g of metallic crystal :

The number of particles and the number of unit cells in given mass of a metal
can be calculated from number of particles 'n' per unit cell and volume 'a 3' of
unit cell.
Density (ρ) and molar mass (M) of a metal are related to each other through
unit cell parameters as:
ρ = mass/volume

= number of particles in unit cell x M

volume of unit cell x NA

∴ ρ= n×M
a 3x N A
∴ M = ρxa3 xNA
n
where 'n' is the number of particles in unit cell and 'a 3' is the volume of unit
Number of particles in 'x' g metal :
Since Molar mass, M, contains NA particles

∴ x g of metal contains xNA particles.

M

Since M= ρxa3 xNA

n

substitution of M gives

Number of particles in 'x' g = xN A

ρa3NA
n
= xn
Number of unit cells in 'x' g metal :

Since 'n' particles Ξ to 1 unit cell

∴ xn particle Ξ xn
ρa3 ρa3/n

= x
ρa3
Electrical properties of solids:
solids are classified into the following three categories :

conductors insulators

semiconductors

i. Conductors :

Solids having electrical conductivities in the range 10 4to 107 Ohm-1m-1 are called conductors.

Metals and electrolytes (ionic solids) are examples of electrical conductors.

Metals conduct electricity by movement of electrons

Electrolytes conduct electricity by movement of ions.

ii. Insulators :

Solids having low electrical conductivities in the range 10-20 to 10-10

Ohm-1m-1 are called insulators.

Most nonmetals and molecular solids belong to this category.

iii. Semiconductors :

Solids having electrical conductivities in the range 10-6to 104Ohm-1m-1

are semiconductors.

This range is intermediate between conductors and insulators.

Metalloids like silicon, germanium belong to this category.

Band theory :
Conductivities of metals, non metals & metalloids can be explained by Band
Theory.

A band is made of closely spaced electronic energy levels.

Band formation can be correlated to formation of molecular orbitals (MOs) by

interaction of atomic orbitals.

According to MO theory interaction of atomic orbitals of combining atoms results

in formation of equal number of MOs which spread over the entire molecule.

Similar to this, interaction of energy levels of electrons in the closely spaced

constituent atoms in solids result in formation of bands.

Band theory considers formation of two types of bands, namely, conduction band
and valence band.
i. Conduction band :

The highest energy band containing electrons is the

conduction band.

It is formed by interaction of the outermost energy

levels of closely spaced atoms in solids.

Conduction band may be partially occupied or vacant.

Electrons in conduction band are mobile and

delocalized over the entire solid.

They conduct electricity when electrical potential is

applied.

ii. Valence band :

The band having lower energy than conduction
band is the valence band.

The electrons in valence band are not free to move

iii. Band gap :
The energy difference between
valence band and conduction band is called
band gap.

Size of the band gap decides whether

electrons from valence band can be promoted
to vacant conduction band or not

when band gap is too large to promote electrons

from valence band to vacant conduction band
by thermal energy, it is called forbidden zone.

When band gap is small, electrons from higher

energy levels in valence band can be promoted
to conduction band by absorption of energy
(such as thermal, electromagnetic).
Metals :
Metals are good conductors of electricity.

The outermost electrons of all the atoms in

the metallic crystal occupy conduction band.

The number of electrons in conduction band

of metals is large.

Hence metals are good conductors of electricity.

The conduction bands in metals can be further

labelled as 's' band , overlapping s and p bands
and so on.

This depends on the atomic orbitals involved in

band formation.
Band formation in metallic conductors, thus,
results in delocalization of the outermost electrons
of all the metal atoms leaving behind metal ions.

This is described as ‘cations of metal are

immersed in the sea of electrons'.

The cations of metal atoms occupying lattice sites

vibrate about their mean positions.

At higher temperatures, metal cations undergo

increased vibrational motion about their lattice
sites.

The flow of electrons is interrupted by

increased vibrational motion.

As a result conductivity of metals decreases

with increase in temperature.
Insulators :
In insulators the valence
band is completely filled with electrons
and the conduction band is empty.

The valence band and conduction

band in insulators are separated by a large
energy gap called forbidden zone .

Here, thermal energy is insufficient

to promote electrons from valence band to
conduction band.

As a result the conduction band

remains vacant. The material is, therefore, an
insulator.
Semiconductors :
Electrical conductivity of a semiconductor material
is intermediate between that of metals and insulators.

The metalloids Si and Ge are semiconductors.

Like insulators, the valence band in semiconductor is

completely filled with electrons and conduction band
is empty.

However, the energy gap between the two bands is

smaller than that in an insulator.

At a temperature above absolute zero a few electrons

in the valence band have enough thermal energy to
jump through the small band gap and occupy higher
energy conduction band.
Semiconductors :
The conduction band, thus, becomes partially filled and the
valence band becomes partially empty.

The electrons in conduction band are free to move.

When electric potential is applied to a semiconductor,

it conducts a small amount of electricity.

Such a pure semiconductor material which has a very

low but finite electrical conductivity is called
intrinsic semiconductor.
The electrical conductivity of a semiconductor
increases with increasing temperature.

This is because, the number of electrons with sufficient

energy so as to get promoted to the conduction band
increases as temperature rises.

Thus, at higher temperatures, there are more mobile

electrons in the conduction band and more vacancies
in the valence band than at lower temperature.

semiconductors are insulators at low temperatures

and conductors at high temperatures.
Extrinsic semiconductors and doping :

The conductivity of a semiconductor can be increased by doping.

Defn:
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.

A doped semiconductor, having higher conductivity than pure intrinsic

semiconductor, is an extrinsic semiconductor.

There are two types of extrinsic semiconductors, namely,

n- type semiconductor p-type semiconductor

n-type semiconductor :
n-type semiconductor contains increased
number of electrons in the conduction bond.
An n-type semiconductor is obtained by adding
group 15 element to intrinsic semiconductor which
belongs to group 14.
For example, consider, doping of Si with phosphorus.
Si has a crystal structure in which each Si atom
is linked tetrahedrally to four other Si atoms.
When small quantity of phosphorous is added to
pure Si, the P atoms occupy some vacant sites in
the lattice in place of Si atoms.
The overall crystal structure of Si remains unchanged.
Four of the five valence electrons of P are
utilized in bonding the closest of four Si atoms.
Thus, P has one extra electron than needed for
bonding.
Therefore, Si doped with P has more
number of electrons in the conduction band
Thus the conductivity of Si doped with P is
higher than that of pure Si.

The electrons in conduction band move

under the influence of an applied potential
and conduct electricity.

Since the charge carriers are the

increased number of electrons, Si or Ge doped
with group 15 elements such as P, As, Sb or Bi
is an n-type semiconductor.
p-type semiconductor :
A p-type semiconductor is produced by
doping a pure semiconductor material (Si or Ge)
with an impurity of group 13 elements.
These elements contain less number of
valence electrons than that of the pure
semiconductor.
Consider, for example, pure Si doped with boron.
The B atoms occupy normal positions of some of
the Si atoms in the lattice.
Boron atom has only three valence electrons.
It does not have enough electrons to form
bonds with its four Si neighbours.
B atom forms bonds with three Si atoms only.
The missing fourth electron creates an electron
vacancy.
It is called a hole.
A hole has a tendency to accept electron
from its close vicinity.

Thus, a hole behaves as if it has a positive charge.

The electrons in partially filled valence band

move under the influence of an applied potential.

The holes move in the opposite direction.

Since the charge carriers are holes

which behave like positive charge, the Si or
Ge doped with group 13 elements like B, Ga
or In (indium), is a p-type semiconductor.
 MAGNETIC PROPERTIES OF SOLIDS
1.Diamagnetic solids: The substance in which all electrons are paired
weakly repel in magnetic field . Such substances are called diamagnetic
substances.
Spinning of paired electrons balances the spins & cancels the magnetic
moment.
Eg. Nitrogen , Flourine, NaCl, Water & benzene are diamagnetic

2.Paramagnetic Solids: Substance with unpaired electrons are weakly

attracted by the magnetic field. These are called paramagnetic
substances.
Spinning of unpaired electrons gives rise to magnetic moment .
These substance exhibit magnetism in magnetic field but loses magnetic
properties once the external magnetic field is removed
Eg. Oxygen, Cu2+, Fe3+ ,Cr3+ are paramagnetic in nature.
 MAGNETIC PROPERTIES OF SOLIDS
3) Ferromagnetism: Substances having large number of unpaired
electrons are attracted strongly by magnetic field. These
substances are called ferromagnetic substances.
These substances can be permanently magnetised as they retain
magnetic properties even after the removal of external magnetic
field.
Eg. Fe, Co, Ni, CrO2, Gd( gadolium)
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