Associate Professor and Head

Department of Chemistry
Shaiva Bhanu Kshatriya College ,
Aruppukkottai 626101, Tamilnadu ,India .
 SOLID STATE CHEMISTRY

The branch of physical chemistry which

deals about structure and properties of solid.
Types of solid :
 Crystalline solid

 Amorphous solid
 SOLID STATE CHEMISTRY

CRYSTALLINE SOLID AMORPHOUS SOLID

 Ordered arrangement  No ordered arrangement

 Anisotropic  Isotropic
 Sharp melting point  No sharp melting point
 Electrical and thermal  Not conduct electricity
conductivity and heat
 Crystallography
It is the experimental science of determining the
arrangement of atoms in crystalline solids

Laws of crystallography:

Crystallography is based on the fundamental laws

 Law of constancy of interfacial angles

 Laws of rational indices

 Law of constancy of symmetry

Crystal Morphology
Law of Constancy of Interfacial Angles
This law states that angle between

adjacent corresponding faces is interfacial

angles of the crystal of a particular substance

is always constant inspite of different shapes

and sizes and mode of growth of crystal.

 Law of Rational indices
This law states that the ratio of intercepts of
different faces of a crystal with the three axes are
constant and can be expressed by rational numbers
that the intercepts of any face of a crystal along the
crystallographic axes are either equal to unit
intercepts (i.e., intercepts made by unit cell) a, b, c
or some simple whole number multiples of them
,e.g.. na,n’a,n’’a etc. are simple whole numbers .
 Law of constancy of symmetry
 This law states that all crystals of a substance have the same elements
of symmetry is plane of symmetry, axis of symmetry and Centre
of symmetry.
 The total number of Planes ,Axes and Centre of symmetries possessed
by a crystal is called elements of symmetry.
Total number of elements of symmetry in cubic crystal=23
i.e., Plane of symmetry number is 9
Axes of symmetry number is 13
Centre of symmetry number is 1
Elements of symmetry in cubic crystals

Rectangular plane of symmetry = 3

Diagonal plane of symmetry = 6

Elements of symmetry in cubic crystals

The 13
Elements of symmetry in cubic crystals

Order of centre of symmetry =1

 Symmetry operation in crystal
A symmetry operation is an operation performed on a crystal of
such that the crystal transformed into a state indistinguishable from the
starting state.

Three types of symmetry operation :

Plane of symmetry
 Axis of symmetry
Centre of symmetry
 Plane of symmetry in crystal
It is an imaginary plane on a crystal system with
respect to this plane the crystal is divided into two halves, one half
is the mirror image of the other half.

Two types of plane symmetry:

Rectangular plane of symmetry
Diagonal plane of symmetry
 Rectangular plane of symmetry
It is an imaginary plane passing through the mid points of
two opposite faces of a crystal with respect to this plane the crystal
is divided into two halves ,one half is the mirror mage of other.
 Diagonal plane of symmetry
It is an imaginary plane passing through the diagonal of two
opposite faces of a crystal with respect to this plane the crystal is divided into
two halves ,one half is the mirror mage of other
 Rotational axis of symmetry in crystal
It is imaginary line passing through the crystal system with respect to this
axis the crystal is rotated by an angle gives same appearance of the crystal
system.

Types of Rotational axis of symmetry:

Two - fold Rotational axis of symmetry
Three - fold Rotational axis of symmetry
 Four - fold Rotational axis of symmetry
 Six - fold Rotational axis of symmetry
 Two –fold rotational axis of symmetry
It is the rotation of a crystal with respect to an imaginary line passing
through the crystal by an angle 180° gives similar appearance of the crystal
system

The total number of two –fold axis of symmetry in cubic crystal = 6

 Three–fold rotational axis of symmetry
It is the rotation of a crystal with respect to an imaginary line
passing through the crystal by an angle 120° gives similar appearance of
the crystal system

The total number of three –fold axis of symmetry in cubic crystal = 4

 Four –fold rotational axis of symmetry
It is the rotation of a crystal with respect to an imaginary line passing
through the crystal by an angle 90° gives similar appearance of the crystal
system

The total number of three –fold axis of symmetry in cubic crystal =3

 Six –fold rotational axis of symmetry
It is the rotation of a crystal with respect to an imaginary line passing
through the crystal by an angle 60° gives similar appearance of the crystal
system.

60°

The total number of six –fold axis of symmetry in hexagonal crystal = 7

Order of rotational symmetry = 6
 Centre of symmetry in crystal
It is a point in the crystal with respect to this point a line
drawn in opposite direction that intersects the surface of the crystal at equal
distance in both directions.

All crystal system has only one Centre of symmetry

 Miller indices
It is a set of integers {h,k,l} which are used to describe a given plane in
a crystal.
The procedure for determining the miller indices are as follows:
 Prepare a three column table with the unit cell axes at the top of the columns

 Enter in each column the intercept [expressed as a multiple of a,b,c ] of the

plane with these axes

 Invert all numbers

 Clear fractions to obtain h,k,l

 Calculation of miller indices
Calculation of the miller indices of crystal plane which cut through the
crystal axes at (2a,3b,c) is shown below:

Unit intercept a b c
Intercept multiple for 2 3 1
a plane

Reciprocal of all 1/2 1/3 1

number

Convert the fraction 3 2 6

into whole number

So , the miller indices are (3,2,6) for a plane (2a,3b,c)

Calculation of Interplanar distance of crystal system
Miller indices are used to calculate interplanar distance of a crystal system. That
means the relationship between miller indices and interplanar distance is given as :

[1]

Where h,k,l are the miller indices of the planes and a,b,c are the unit intercepts of the
plane.
For a cubic system : a = b = c ,so that equation [1] becomes

[2]
Calculation of Interplanar distance of crystal system
For tetrahedral system : a = b ≠ c , so that equation [1] becomes

[] [3]

For an orthorhombic system : a ≠ b ≠ c , so that equation [1] becomes

[4]
Calculation of Interplanar distance of crystal system

Example :
The Parameters of an orthorhombic unit are a = 50pm , b = 100 pm
and c = 150pm . Determine the spacing between the (123) planes.
For an orthorhombic unit cell, the interplanar distance is given as:

on substituting the values of a , b , c , h , k and l in the above equation gives

Calculation of Interplanar distance of crystal system
2 2 2
1 1 1 2 3
2 = 2 = + +
𝑑ℎ𝑙𝑘 𝑑123 50𝑝𝑚 100𝑝𝑚 150𝑝𝑚
1 3
2
= 2
𝑑123 50𝑝𝑚

1 3 3
= 2 =
𝑑123 50𝑝𝑚 50𝑝𝑚

1 50𝑝𝑚
= = 29pm
𝑑123 3
 X-ray diffraction
Scattering of x-rays by crystal atoms or ions ,producing a
diffraction pattern that yields information about the structure of the crystal.
 Bragg equation
The reflections of x-rays can takes place only at certain angles which
are related by the wavelength of the x-rays and the interplanar distance in the
crystal in an equation called Bragg equation.

Where,
n = order of reflection d = interplanar distance

θ = angle of scattering λ = wavelength of x-rays

Experimental determination of interplanar distance for a
crystal

 On the basis of X-ray diffraction , interplanar distance for a crystal is determined

by an instrument called x-ray spectrometer or x-ray diffractometre

 Methods used in the determination of interplanar distance are :

1. Rotating crystal method

2. Powder method(Debye Scherrer method)

 Rotating crystal method
• X-ray spectrometer for the rotating crystal method is shown in figure.
• x-ray generated in the tube T allow to strike a single crystal mounted on a
turned table
 Rotating crystal method
• The crystal is rotated so as to increase the glancing angle at which the x-rays are incident
at the exposed face of the crystal
• The intensity of the reflected rays are measured on the recording device R
• The angles for which reflections are maximum give the value of θ
• The lowest angle at which the maximum reflection occurs corresponds to n = 1 . This is
called first order reflection
• The next higher angle at which the maximum reflection occur is corresponds to second
order reflection (n = 2) , and so on
• Substituting wavelength of x-ray ( λ ) , θ and n values in Bragg equation , the interplanar
distance for a crystal can be calculated
𝑛𝜆
d=
2𝑠𝑖𝑛𝜃
 Debye - Scherrer method (powder method)

 The experimental arrangement of powder crystal method is shown in figure

 Debye - Scherrer method (powder method)
 A is a source of X-rays which can be made monochromatic by a filter
 Allow the X-ray beam to fall on the powdered specimen P through the slits S1 and
S2 . The function of these slits is to get a narrow beam of X-rays
 Fine powder P , struck on a hair by means of gum is suspended vertically in the axis
of a cylindrical camera .This enables sharp lines to be obtained on the photographic
film which is surrounding the powder crystal in the form of a circular arc
 The X-rays after falling on the powder passes out of the camera through a cut in the
film so as to minimize the fogging produced by the scattering of the direct beam
 As the sample and detector are rotated , the intensity of the reflected X-rays is
recorded
 When the geometry of the incident X-rays impinging the sample satisfies the Bragg
equation ,constructive interference occurs and a peak in intensity occurs
 Debye - Scherrer method (powder method)
 A detector records and processes this X-ray signal and converts the signal to a count
rate which is then output to a device such as a printer or computer monitor

 The peaks represent positions where the X-ray beam has been diffracted by the
crystal lattice. The set of interplanar distances can be calculated from the 2-theta
values by using Bragg equation (d = nλ / 2Sinθ) where, θ is the half of the 2-theta
value obtained from the X-ray diffraction spectrum
 Types of crystal

Solid crystals classified into four types :

 Molecular crystals
 Covalent crystals
 Ionic crystals
 Metallic crystals
 Molecular crystals
 Lattice points are occupied by neutral molecules.
 The molecules are held together by Vander Waal's forces and dipole –dipole
interaction.
 Very soft solids.
 Low melting point and boiling point.
 Poor conductors of electricity.
 Volatile nature.

Example :water and ammonia.

Structure of Molecular crystal -Water
Structure of Molecular crystal - Ammonia
 Ionic crystals
 Lattice points are occupied by positive and negative ions.

 Hard and brittle solids.

 High melting and boiling points due to very strong electrostatic forces of attraction.

 Poor conductors of electricity in solids state but good in molten state.

 Heat of vaporization is high.

 Soluble in water.

Example: NaCl , KCl and CsCl.

 Structure of Ionic crystal- NaCl
• Face Centred cubic crystal type
• Co-ordination number 6:6
• Calculation of number of NaCl unit in an unit cell is
as follow :
 Cl- at corners (8 Х 1/8) =1
 Cl- at face centres (6 X 1/2) = 3
 Na+ at edge centres (12 X 1/4)=3
 Na+ at body centres =1
 Unit cell contents are 4(Na+ Cl-)
 thus number of NaCl units per unit cell is 4
 Structure of Ionic crystal- CsCl
• Body Centred cubic crystal type

• Co-ordination number 8:8

• Calculation of number of CsCl unit in an unit

cell is as follow :

 Cl- at corners (8 Х 1/8) =1

 Cs+ at body centres =1

 Thus number CsCl units per unit cell is 1

 Covalent crystals

 Lattice points are occupied by neutral atoms

 Atoms are held together by covalent bonds

 Hard solids

 High melting point

 Poor conductors of electricity

 Examples: diamond and graphite

 Covalent crystal - Diamond
 Each carbon atom is covalently bonded to
four other carbon atoms by involving sp3
hybridization

 Rigid three dimensional regular tetrahedron

network

 Very hard ,high density and melting point

 Shiny , transparent and unreactive

 Bad conductor of electricity

 Covalent crystal - Graphite
 Each carbon atom covalently bonded to three other carbon
atom by involving sp2 hybridization
 All atoms in a single plane are linked to give flat hexagons
 The hexagons are held together in sheet like structures,
parallel to one another i.e. layer lattices structure
 Each layer are held together by Van der Waals forces
 Good conductor of electricity because of availability of non
bonded free electrons
 Soft and used as lubricants
 Metallic crystal
 Lattice points are occupied by positive metal ions
surrounded by a sea of mobile electrons
 Soft to very hard
 Metals have high tensile strength
 Good conductors of electricity
 Malleable and ductile
 Bonding electrons in metals remain delocalized over
the entire crystal
 High density
Examples: All metals
 Defects in crystal-point defects
 The imperfection in crystal structure due to the missing or dislocation of atoms or ions is
called point defects

 This can be arise due to thermal vibration and imperfect packing during the
crystallization
Types of point defects:

 Frenkel defect

 Schottky defect
 Frenkel defect
 A Frenkel defect is also known as frenkel pair or
frenkel disorder ,it is a type of point defect in a
crystal lattice

 The defect forms when an atom or smaller ion

leaves its place in the lattice, creating a vacancy
,and becomes an interstitial by lodging in a
nearby location.

 Example: AgBr
 Schottky defect
 Schottky defects arise if some of the lattice points
in a crystal unoccupied
 The points which are called lattice vacancies
 The existence of two vacancies , one due to a
missing of Na+ ion and the other due to a missing
Cl- ion in a crystal NaCl
 The crystal remain neutral because the number of
missing positive of negative ions is the same
 Example: NaCl
 Electrical property of crystal
On the basis of electrical property , crystalline materials are
classified into three types
 Conductor
 Insulator
 Semi conductor
Types of semiconductor:
• p-type semiconductor
• n-type semiconductor
 Conductor
• Crystalline materials that conduct electricity are
called conductor
• The energy gap between conduction band and
valence band is very low shown in figure
• Availability of more number of free electrons in the
conduction band is the responsible for electrical
conductivity
• Conductivity of conductor decreases as the
temperature increase
• Example : All metals
 Insulator
• Crystalline materials that does not conduct
electricity are called insulator

• The energy gap between conduction band and

valence band is very high shown in figure

• Non availability of free electrons in the conduction

band is the responsible for its insulating property

• Example : diamond and quartz

 Semi conductor
• Crystalline materials that has a conductivity between
conductor and insulator are called semiconductor

• The energy gap between conduction band and valence

band is moderate shown in figure

• Availability of few number of free electrons in the

conduction band is the responsible for electrical
conductivity

• Conductivity of semi conductor increases as the

temperature increase
 Types of Semi conductor

Semi conductor can be classified as :

 Intrinsic semiconductor

 Extrinsic semiconductor

Extrinsic semiconductor are further classified as:

 n-type semiconductor

 p-type semiconductor
 Intrinsic semiconductor
• Semiconductor in pure form is known as
intrinsic semiconductor

• Conductivity is only slight

• Conductivity increases with rise in

temperature

• At room temperature number of electrons

equal to number of holes

• Example : pure germanium and pure silicon

 Extrinsic Semiconductor

• An extrinsic semiconductor is an improved intrinsic semiconductor with a

small amount of impurities by a process known as Doping .

• Doping process improves and control the conductivity of semiconductor

• Doping process produces two groups of semiconductor:

 n-type semiconductor

 p-type semiconductor
 n-type semiconductor
• The pure crystalline silicon(Si) form a crystal
lattice by having each atom share all of its 4
valence electrons with neighboring atoms

• The crystalline array is “doped” with arsenic

which has five valence electrons, the behavior of
the lattice will change

• Four bonds will be still be made but there will be a

leftover electron that can wander through the
crystal. This is called n-type semiconductor
 p-type semiconductor
• The pure crystalline silicon(Si) form a crystal
lattice by having each atom share all of its 4 valence
electrons with neighboring atoms

• The crystalline array is “doped” with boron which

has three valence electrons, the behavior of the
lattice will change

• Boron offers 3 of the four electrons that a silicon

atom needs, each silicon center is left with a hole.
This is called p-type
 Determination of Avogadro number
• The number of atoms or molecules in a mole of any substance called Avogadro
number. This number was found to be 6.022 × 1023 ( NA )
𝑍 𝑀
• Density of Unit Cell : d= Х
𝑎3 𝑁𝐴
Where,
d = Density (g/cm3 ) Z = number of atoms per unit cell
a = Edge length in cm M = Molar mass in g/mol
• So the Avogadro number:
𝑍 𝑀
𝑁𝐴 = Х
𝑎3 𝑑
• On substituting Z ,M , a and d in the above equation the Avogadro number ( NA) can
be calculated
 Determination of Avogadro number
* Example :
The density of a solid compound KCl is 1.9893g/cm3 and the length of a side unit cell is 6.29082 A0 as
determined by X-ray diffraction. Calculate the Avogadro`s number. Molar mass of KCl is 74.55g/mol
* Given parameters :
Since KCl belongs to fcc type the no. of ions per unit cell ( Z ) for fcc is 4
d = 1.9893g/cm3 a = 6.29082 A0 = 6.29082 x 10-8
M= 74.55g/mol Z= 4
* On substituting the above parameters in the following equation:

𝑍 𝑀
𝑁𝐴 = Х
𝑎3 𝑑
4𝑋74.55 298.2 𝑋 1024
= 3 = = 6.02 𝑋 1023
6.26082𝑋10 −8− 𝑋1.9893 495.26
NA = 6.023 x 1023