SCHOOL OF SCIENCE AND HUMANITIES

DEPARTMENT OF CHEMISTRY

UNIT-I – BONDS TO BANDS – SCYA1101

 1. Introduction
In this chapter, we shall give an overview of the properties of solids and how quantum
mechanics helps us to understand these properties. In
the solid state, a material at a given temperature and pressure has a well definite shape. The
forces of interaction between the atoms in the solid must be strong and the bonds between
them are stable under existing conditions. In subsections, we used quantum mechanics to
understand how these bonds are formed. We have considered the crystalline solids, in which
the bonds allow the formation of regular arrays of atoms within the solid. In other
subsections, we give an introductory treatment of energy bands and the band theory of solids
to explain the electrical conductivity and why some solids are conductors, whereas others are
semiconductors or insulators. Most important among these is the idea of a bond, and the use
of frontier-orbital arguments. Interpretative constructs, such as the density of states, the
decomposition of these densities and crystal orbital overlap population, allow a recovery of
bonds, a finding of the frontier orbitals that control structure and reactivity in extended
systems as well as discrete molecules.
Electromagnetic Wave
Electromagnetic wave or radiation is a wave that consists of oscillating electric and magnetic
fields which is characterized by wavelength λ and frequency ν (number of oscillations per
second). The wavelength and frequency of the wave is related to velocity c (3 x 108 ms-1) of
the wave by 𝑐 = 𝜆𝜈
Black Body Radiation
An ideal black body is an object that absorbs all the radiations falling on it. A hollow
enclosure or chamber having a small hole is an appropriate black body because it absorbs all
the radiation entering it due repeated reflections inside the enclosure. The radiation emitted
from such a black body is called black body radiation. A perfect absorber is also a perfect
emitter of radiation. The intensity of the total radiation emitted per unit surface area from a
black body depends on temperature (T) and is independent of the nature of the solid.
 Fig 1: Black body radiation

Laws of Radiation
The radiation emitted by a heated body is explained by the laws of radiation.
1. Wien’s law
The wavelength λm corresponding to the maximum energy density ρ(ν)dν is inversely
proportional to the temperature T.
1
𝜆𝑚 ∝
𝑇
𝑏
𝜆𝑚 =
𝑇
𝜆𝑚 𝑇 = 𝑏
where b is called Wien’s constant and value of b is 2897 microkelvin.
2. Rayleigh-Jean’s law
Rayleigh derived an equation for the distribution of energy density called the Rayleigh-Jean’s
law
8𝜋𝜈 2
𝜌(𝜈)𝑑𝜈 = 𝐾 𝑇𝑑𝜈
𝑐3 𝐵
where ρ(ν)dν is the radiation density and KB is the Boltzmann constant (1.38 x 10-23 JK-1).
3. Planck’s law of radiation
Max Planck derived an expression for energy density of a black body radiation called as
Planck’s radiation law and is given by
8𝜋ℎ𝜈 3 1
𝜌(𝜈)𝑑𝜈 = 𝑑𝜈
𝑐 3 (𝑒 (ℎ𝜈⁄𝐾𝐵 𝑇) − 1)
Planck introduced a constant h known as Planck’s constant (value of h = 6.626 x 10-34 Js). He
proposed a Planck’s quantum theory based on energy quantization to explain the black body
radiation.
The black body emits radiation in a wide spectrum of wavelengths. The distribution of energy
of emitted radiation over different frequencies is called as energy density and is given by
ρ(ν)dν. At any temperature T, the energy density ρ(ν)dν increases with increase in ν, reaches
a maximum and then drops to zero. With increase in T, the maximum of curve shifts to
higher frequency (i.e) shorter wavelength side.

Fig 2: Planck’s law of Black body radiation

Planck’s quantum theory of radiation
According to this theory
1. Energy is absorbed or emitted in the form of discrete sets of small bundles of energy
known as quanta.
2. Each quantum is associated with certain amount of energy E = hν, where h is Planck
constant and ν is the frequency of radiation.
3. A body can emit or absorb energy only in integral multiples of quantum (i.e) 1hν, 2hν,
3hν………nhν.
Photoelectric effect
In 1905, based on the Planck’s idea of energy quantization, Albert Einstein discovered law of
the photoelectric effect. According to photoelectric effect, when a light photon of a certain
frequency ν strikes the surface of metal, electrons are emitted from the metal. The photon
transfers its energy hν to the electrons and this is used to overcome the binding energy (ω)
1
and to increase kinetic energy (2 𝑚𝓋 2 ) of the emitted electrons.
 1
ℎ𝜈 = 𝜔 + 𝑚𝓋 2
2
since 𝜔 = ℎ𝜈0 , where ν0 is the threshold frequency
1
ℎ𝜈 = ℎ𝜈0 + 𝑚𝓋 2
2
1
𝑚𝓋 2 = ℎ𝜈 − ℎ𝜈0
2
1
𝑚𝓋 2 = ℎ(𝜈 − 𝜈0 )
2
This equation is called the Einstein photoelectric equation.

Fig 3: Photoelectric effect

Observations
1. Light with minimum frequency called the threshold frequency ν0 is necessary to cause
emission of electron by photoelectric effect. (If ν < ν0 there is no photoelectric effect)
2. Kinetic energy of emitted electrons is directly proportional to frequency and
independent of intensity of incident radiation.

Wave – Particle duality of electrons – de Broglie’s hypothesis

Louis de Broglie in 1924 proposed that the quantization of energy of an atom can be
explained only when electrons exhibit wave-particle dual behaviour. This hypothesis was
verified through electron diffraction experiment by Davisson and Germer. The electrons
produce diffraction patterns similar to light waves when passed through a nickel crystal
which confirms the wave nature of electrons. de Broglie hypothesis can be derived by using
Einstein’s energy mass relationship
𝐸 = 𝑚𝑐 2 … . .1
where c is velocity of photon and m is mass of photon.
According to Planck’s, the energy of photon is quantized which inherently possess the duality
nature of particle, since energy of photon E is a particle property and frequency ν is a wave
property.
𝐸 = ℎ𝜈 … . .2
Thus from equations 1 and 2

2
𝑚𝑐 2
ℎ𝜈 = 𝑚𝑐 ⇒𝜈=
ℎ
In wave theory of light, the frequency ν and wavelength λ is related to each other by the
equation 𝜈𝜆 = 𝑐
Therefore,
𝑐 𝑐ℎ ℎ ℎ
𝜆= = 2
= =
𝜈 𝑚𝑐 𝑚𝑐 𝑝
where p is the momentum of the photon p = mc
de Broglie proposed that the wavelength or frequency of electron similar to the photon is
related to the momentum of the electron
ℎ ℎ
𝜆= 𝑜𝑟
𝑚𝑐 𝑝
where λ = wavelength of electron, m = mass of electron, p = momentum of electron, h =
Planck’s constant.
de Broglie hypothesis of wave-particle duality is applicable to all subatomic particles such as
neutrons, protons etc.

Heisenberg’s Uncertainty Principle

Heisenberg stated that “it is not possible, even in principle to measure both position and
momentum of an electron simultaneously”. This is known as Heisenberg Uncertainty
principle. Mathematically it is expressed as
ℎ
∆𝑥 . ∆𝑝 ≥
4𝜋
where ∆x is the uncertainty in position of the electron, ∆p is the uncertainty in momentum of
the electron and h is the Planck’s constant. If the position of an electron is determined with
high accuracy then its momentum becomes uncertain. Similarly, if the momentum of the
electron is measured precisely then its position will be uncertain. This principle holds good
only for microscopic particles however, it does not apply to larger bodies (i.e) both
momentum and position can be determined accurately at the same time.
 2. Theory of Wave Motion
The de Broglie, Heisenberg uncertainty principle and electron diffraction experiments
established the dual nature of electrons as particle as well as wave. A particle is localized it
cannot be present in more than one place at same time whereas wave cannot be localized at a
point and varies from a point to point in space. In order to insight the behaviour of electrons it
is necessary to understand the characteristics of wave motion.

Classical Waves and Wave Equation

Consider the wave motion in vibration of a string, the vertical displacement of string from its
mean position is called the amplitude of wave or vibration. This amplitude is a function of
position (x) and time (t) and denoted as Ψ(x,t).

Fig 4: Classical wave

Here the wave makes same amplitude at regular intervals of ∆x which is λ the wavelength of
the wave. The velocity of wave c is given by λ/t, the frequency ν (number of waves per unit
time) will be c = λ/t⇒ 1/t = c/λ (ν=c/λ) and the wave number (number of waves per unit
distance) will be ῡ = 1/λ. The periodic nature of Ψ(x,t) propose the sine or cosine function of
x and t where x is position coordinate and t is time coordinate. The expression for wave
function is obtained by solving the equation of the wave motion which is not in the scope of
this book
𝜕 2𝛹 1 𝜕 2𝛹
= … . .1
𝜕𝑥 2 𝑐 2 𝜕𝑡 2
where Ψ=Ψ(x,t). By applying separation of variables method, function Ψ(x,t) is separated
into a product of two functions
 𝛹(𝑥, 𝑡) = 𝛹(𝑥). 𝛷(𝑡) … . .2
where Ψ(x) is a function of x only and Φ(t) is a function of t only. Substituting equation 2 in
1 and diving by Ψ(x). Φ(t) on both sides gives
𝑐2 𝜕 2𝛹 1 𝜕 2𝛷
. = . … . .3
𝛹 𝜕𝑥 2 𝛷 𝜕𝑡 2
The left hand side of equation 3 depends only on x and right hand side depends only on t
however both sides are equal and are equated to a constant -k2
𝑐2 𝜕 2𝛹 1 𝜕 2𝛷
. 2 = . 2 = −𝑘 2 … . .4
𝛹 𝜕𝑥 𝛷 𝜕𝑡
Thus two equations are obtained from equation 4
𝜕 2𝛹 𝑘2
= − 2 𝛹 … . .5
𝜕𝑥 2 𝑐
𝜕 2𝛷
= −𝑘 2 𝛷 … . .6
𝜕𝑡 2
Here equation 5 is the time-independent wave equation called as amplitude equation. The
general solutions for equations 5 and 6 are
𝑘𝑥 𝑘𝑥
𝛹(𝑥) = 𝐴 𝑠𝑖𝑛 ( ) + 𝐵𝑐𝑜𝑠 ( ) … . .7
𝑐 𝑐
𝛷(𝑡) = 𝐶 sin(𝑘𝑡) + 𝐷 cos(𝑘𝑡) … . .8
where A,B,C and D are arbitrary constants.
The other solutions of equation 5 are
2𝜋𝑖𝑥
𝛹(𝑥) = 𝐴 exp (± ) … . .9
𝜆
These exponential functions are expressed in trigonometric functions as
exp(±𝑖𝑘𝑥) = 𝑐𝑜𝑠𝑘𝑥 ± 𝑖 𝑠𝑖𝑛𝑘𝑥 … . .10

Stationary Waves
Waves expressed by the equation 5 are called running waves in which Ψ is a function of time.
However, electron waves in atoms and molecules are stationary waves in which Ψ does not
change with time. A classical example of such wave is the wave in a vibrating string clamped
at two ends.
Thus equation 5 may be expressed as
𝜕 2𝛹 4𝜋 2
= − 2 𝛹 … . .11
𝜕𝑥 2 𝜆
𝑘 2𝜋
∵ =
𝑐 𝜆𝑐
here Ψ(x) is expressed as Ψ. The wave does not vibrate at the ends x = 0 and x = L and
this is called as boundary conditions.
The first boundary condition x = 0, Ψ becomes 0 from equation 7 and B becomes zero
2𝜋 2𝜋
0 = 𝐴 𝑠𝑖𝑛 ( .0) + 𝐵𝑐𝑜𝑠 ( .0) = 𝐵 … . .12
𝜆 𝜆
The second boundary condition x = L and B = 0, Ψ becomes 0

2𝜋
0 = 𝐴 𝑠𝑖𝑛 ( . 𝐿) … . .13
𝜆
Equation 13 is satisfied when
1. A = 0, but Ψ becomes zero everywhere and for all values of x which is not acceptable.
2𝜋
2. . 𝐿 = 𝑛𝜋, where n = 0, ±1, ±2, ±3 …
𝜆
2𝐿
or 𝜆 = and is acceptable.
𝑛
𝑛𝜋𝑥
The solution of the wave equation is 𝛹 = 𝐴 sin where A is maximum amplitude of the
𝐿

wave. The equation becomes zero at boundary conditions and integral number of half
wavelength between the clamped ends of the string. The points where Ψ becomes zero is
called node.

Fig 5: Stationary wave - Vibration in clamped string

For example when n = 0, Ψ = 0 everywhere, when n = 1, Ψ = 0 only at x = 0 and x = L, and

there is no node, when n = 2, Ψ becomes zero at x = L/2 which is a node, for n = 3, Ψ
becomes zero at x = L/3 and 2L/3 thus two nodes are present and so on.
Schrodinger Equation for Particle Waves
Erwin Schrodinger proposed that if electrons have both particle and wave behaviour the
equation of wave motion can be applied to them. He used the time-independent wave
equation to explain the particle wave. For an electron of wavelength λ moving along x-
coordinate,
𝜕 2𝛹 4𝜋 2
= − 2 𝛹 … . .14
𝜕𝑥 2 𝜆
ℎ
From de Broglie relationship, 𝜆 = 𝑚𝑣 and substituting in equation gives

4𝜋 2 𝑚2 𝑣 2 8𝜋 2 𝑚𝑇𝛹 8𝜋 2 𝑚(𝐸 − 𝑉)
− 𝛹 = − = − 𝛹 … . .15
ℎ2 ℎ2 ℎ2
𝜕 2𝛹 8𝜋 2 𝑚(𝐸 − 𝑉)
= − 𝛹 … . .16
𝜕𝑥 2 ℎ2
where Ψ = Ψ(x), T is kinetic energy, V is potential energy and E is total energy of the
electron (E=T+V). This is known as Schrodinger equation for particle (electron) of mass m
moving in one dimensional motion. For three dimensional motion, the equation will be a
partial differential equation with three coordinates x,y and z.
𝜕 2𝛹 𝜕 2𝛹 𝜕 2𝛹 8𝜋 2 𝑚(𝐸 − 𝑉)
+ + = − 𝛹 … . .17
𝜕𝑥 2 𝜕𝑦 2 𝜕𝑧 2 ℎ2

Conditions for Acceptable Wave Function

The conditions for an acceptable wave function Ψ are
1. It must be finite.
2. It must be single-valued at all points.
3. It must be continuous.
If these three conditions are obeyed then the function Ψ is called a well-behaved wave
function.

Motion of Quantum Mechanical Particle

The quantum mechanical particle such as electrons in atoms and molecules can execute
translational, rotational and vibrational motion. However, the common type of motion is
translational or linear when they move freely.
For linear motion of free particle which is not affected by any force or potential barrier and
free to move in limitless space, the equation 16 becomes Schrodinger equation for free
particle is given by
 𝜕 2 𝛹 8𝜋 2 𝑚𝐸
+ 𝛹 = 0 … . .18
𝜕𝑥 2 ℎ2
Here potential energy V is a constant and assumed to be zero since the free particle is not
subjected to any potential barrier.

3. Particle in one dimensional box

Consider a particle is moving in a limited space like bounded electrons in atoms and
molecules serves as particle in a box model. If the limited space is a one dimensional box of
length L with infinite high walls at the two ends, the particle is not subjected to any force
inside the box where potential energy V = 0 and outside the box it is infinity thus V = ∞.

Fig 6: Particle in one dimensional box of length L

Hence the potential energy is discontinuous (high at x = 0 and x = L and inside the box is
zero), thus the Schrodinger equation should be considered inside and outside the box
separately.
The Schrodinger equation outside the box (where V = ∞) will be
𝜕 2 𝛹 8𝜋 2 𝑚(𝐸 − ∞)
+ 𝛹 = 0 … . .19
𝜕𝑥 2 ℎ2
ℎ2 𝜕 2 𝛹
− + ∞𝛹 = 𝐸𝛹 … . .20
8𝜋 2 𝑚 𝜕𝑥 2

The Schrodinger equation inside the box 0 ≤ x ≥ L (where V = 0)

𝜕 2 𝛹 8𝜋 2 𝑚 (𝐸 − 0)
+ 𝛹 = 0 … . .21
𝜕𝑥 2 ℎ2
 ℎ2 𝜕 2 𝛹
− 2 = 𝐸𝛹 … . .22
8𝜋 𝑚𝐸 𝜕𝑥 2
The probability of finding a particle outside the box, (i.e) Ψ2 = 0 due the large potential
energy (V = ∞) present in these regions x < 0 and x > L and thus Ψ = 0. Since Ψ must be
continuous (i.e) it cannot rise and fall suddenly thus Ψ must be zero at x = 0 and x = L. This
is the boundary condition for this system.
The Schrodinger equation inside the box is written as
𝜕 2𝛹
+ 𝑘 2 𝛹 = 0 … . .23
𝜕𝑥 2
8𝜋 2 𝑚𝐸
𝑘2 = … . .24
ℎ2
Equation 23 is satisfied by well behaved functions such as sin kx, cos kx, eikx and e-ikx.

Wave function and Energy of the particle

The wave function is described either in terms of real form such as sin kx and cos kx and
complex forms such as eikx and e-ikx.
The general solution of real form of wave function is given as
𝛹 = 𝐴 𝑠𝑖𝑛 𝑘𝑥 + 𝐵 cos 𝑘𝑥 … . .25
where A and B are arbitrary constants. The values of A, B and k are determined by applying
boundary conditions to equation 25
i. At x = 0, Ψ becomes 0
0 = 𝐴 𝑠𝑖𝑛 (𝑘. 0) + 𝐵 cos (𝑘. 0)
Thus B = 0 and hence 𝛹 = 𝐴 𝑠𝑖𝑛 𝑘𝑥 for all values of x
ii. At x = L, Ψ becomes 0
0 = 𝐴 𝑠𝑖𝑛 (𝑘. 𝐿) + 0 cos (𝑘. 𝐿)
Thus 0 = 𝐴 sin 𝑘𝐿
This expression is satisfied if either A = 0 or kL = nπ.
Case 1: If A = 0, B = 0, then Ψ becomes 0 everywhere which not acceptable.
Case 2: Thus kL = nπ or k = nπ/L where n is an integer (1,2,3…) but not zero (if n = 0, Ψ
becomes 0)
The wave function and energy of the particle in one dimensional box is given as
𝑛𝜋𝑥
𝛹 = 𝐴 𝑠𝑖𝑛 … . .26
𝐿
𝑛2 ℎ2
𝐸= … . .27
8𝑚𝐿2
Quantization
In the energy equation 27, the terms h, m and L are constants and energy E depends only on
integer n. Thus energy is quantized (i.e) have discrete set of values and the integer n is a
quantum number. Hence a particle confined to move in a limited space and its energy is
quantized.

Energy levels
The figure 1.7 shows the quantization of energy of a particle in one dimensional box. The
allowed energy levels are drawn as horizontal lines which shows that for a value of n, energy
E does not change with position x of the particle.
ℎ2
The lowest energy level E1 is not zero but (n = 1) and is also called the “zero point
8𝑚𝐿2

energy”. The energy E depends on n2 which shows that increase in n, increases the spacing
between energy levels
∆𝐸 = 𝐸𝑛+1 − 𝐸𝑛 = [(𝑛 + 1)2 − 𝑛2 ]𝐸1 = (2𝑛 + 1)𝐸1
1
Since E is proportional to 𝐿2

Fig 7: Energy levels for particle in one dimensional box

Case 1: when the box is small the energy spacing (∆E) is greater (i.e) the quantization is
pronounced.
Case 2: when the box is wider, ∆E decreases and in limiting case of L⟶∞ (free particle) the
quantization vanishes.
 1
Similarly ∆E is also proportional to thus for macroscopic system (large m) the energy
𝑚

levels are closely spaced and there is no quantization.

Value of A
The value A is determined by the normalization of wave function which is given by
𝐿 𝐿
𝑛𝜋𝑥
∫ 𝛹 2 𝑑𝜏 = ∫ 𝐴2 𝑠𝑖𝑛2 𝑑𝑥 = 1
0 0 𝐿
(1 − 𝑐𝑜𝑠 2𝑥)
𝑤𝑒 𝑘𝑛𝑜𝑤 𝑡ℎ𝑎𝑡 𝑠𝑖𝑛2 𝑥 =
2
𝐿
𝑛𝜋𝑥
2
𝐴2 𝐿
2
2𝑛𝜋𝑥
∫ 𝐴 𝑠𝑖𝑛 𝑑𝑥 = ∫ (1 − 𝑐𝑜𝑠 ) 𝑑𝑥 = 1
0 𝐿 2 0 𝐿
𝐿
𝐴2 sin 2𝑛𝜋𝑥 ⁄𝐿
{[𝑥]𝐿0 − [ ] }=1
2 2𝑛𝜋⁄𝐿 0

𝐴2 𝐿
=1
2

2
𝐴=√
𝐿

2 𝑛𝜋𝑥
Thus the normalized wave function is 𝛹 = √𝐿 𝑠𝑖𝑛 𝐿

Physical meaning of wave function Ψ- Probability density

In Schrodinger wave equation, Ψ is not a physically observable quantity and does not have
any direct physical meaning. However it is used to explain all the observable physical
quantities and this function is known as wave function. The physical interpretation of square
of wave function Ψ2 is a measure of the probability of finding a particle in specified small
volume of space. Ψ2 is considered if Ψ is real function and ΨΨ* is considered when Ψ is
complex and Ψ* is its complex conjugate but the product ΨΨ* is always real.
The normalized wave function is used to calculate the probability density (i.e) the probability
of finding the particle at different points in the one dimensional box. The probability density
is given as
2 𝑛𝜋𝑥
𝛹2 = 𝑠𝑖𝑛2
𝐿 𝐿
2
varying between 0 and . The probability of particle in a box has maximum probability at
𝐿

certain points depending on value of n and is given as

 𝑏
2
2 𝑏 2 𝑛𝜋𝑥
𝑃 = ∫ 𝛹 𝑑𝑥 = ∫ 𝑠𝑖𝑛 𝑑𝑥
𝑎 𝐿 𝑎 𝐿
2 𝐿
i. For n = 1, the maximum probability (𝐿) occurs at x = 2
𝐿 3𝐿
ii. For n = 2, the maximum probability occurs at x = and x = on both side of the
4 4
𝐿
middle point and is zero at x = 2 and so on.

The probability will never be negative and these curves are always symmetric about the
reflection plane at the middle of the box.

Fig 8: Probability density curves of particle in one dimensional box for n = 1

and n = 2 energy levels

4. Schrodinger equation for hydrogen atom

Hydrogen atom is a two particle system which contains one electron (of mass m and charge –
e) and one proton (nucleus of mass M and charge +Ze). Consider x1,y1,z1 and x2,y2,z2 as the
Cartesian coordinates for the proton and electron respectively which are separated by a
distance r. Since the proton mass is very much greater than electron, the reduced mass
calculated will be considered as the mass of the electron.
 Fig 9: Relationship between Cartesian and spherical coordinates
In hydrogen atom two types of motions are involved i) translational motion of hydrogen atom
as a whole and ii) the internal motion of electron and nucleus relative to each other. The
Schrodinger equation involving these motions is
Ĥ𝛹𝑇 = 𝐸𝑇 𝛹𝑇
where ΨT = Ψ (x1,y1,z1, x2,y2,z2) and ET is the total wave function and total
energy(translational energy and internal energy) of the hydrogen atom. The spatial rotation of
electron around the nucleus (containing proton) can be explained by two angular variables φ
(azimuthal angle) and θ (zenith angle) and radial distance r from the nucleus.
The Schrodinger equation of hydrogen atom is

Ĥ(𝑟, 𝜃, 𝜑)𝛹(𝑟, 𝜃, 𝜑) = 𝐸𝛹(𝑟, 𝜃, 𝜑)

The hydrogen atom Hamiltonian contains kinetic energy operator T in terms of spherical
coordinates and spherically symmetrical potential energy. The potential energy is given by
𝑍𝑒 2
𝑉=
(4𝜋𝜀0 )𝑟

The Cartesian coordinates are converted to spherical coordinates in terms of radius r and
angle φ measured between 0 to 2π and angle θ measured between 0 to π. The relationship
between x, y and z and r, θ and φ is given as
PT = OP' = r sin θ
x = OP' cos φ = r sin θ cos φ
y = OP' sin φ = r sin θ sin φ
z = OT = r cos θ
Thus the time-independent Schrodinger equation for hydrogen atom

ℎ2 1 𝜕 2
𝜕 1 𝜕 𝜕 1 𝜕2 𝑧𝑒 2
{ 2 [ (𝑟 ) + (𝑠𝑖𝑛𝜃 ) + ] − } 𝛹 (𝑟, 𝜃, 𝜑)
8𝜋 𝑚 𝑟 2 𝜕𝑟 𝜕𝑟 𝑟 2 𝑠𝑖𝑛𝜃 𝜕𝜃 𝜕𝜃 𝑟 2 𝑠𝑖𝑛2 𝜃 𝜕𝜑2 4𝜋𝜀0 𝑟
= 𝐸𝛹(𝑟, 𝜃, 𝜑)
This equation can be separated into spherical harmonic function Y(θ,φ) and radial function
R(r) by using product wave function.

𝛹(𝑟, 𝜃, 𝜑) = 𝑅(𝑟) 𝑌(𝜃, 𝜑)

Here the spherical harmonic functions give the information about the position of electron
around the proton and the radial function R(r) tells the distance of electron form the proton.
The energy term En and the solution for R(r) and Y(θ,φ) depends only on one quantum
number n (principal quantum number. However, the other three quantum numbers are
necessary for proper description of complete wave function.
𝑚𝑒 4
𝐸𝑛 =
8𝜀02 ℎ2 𝑛2

5. Quantum Numbers
Four quantum numbers are necessary to define an orbital. The combination of these four
quantum numbers of electrons in an atom is described by a wave function satisfied by
Schrodinger equation. The quantum numbers are used to account for the electronic
configuration of an electron in an atom and the probable position of electron in an atom.
The quantum numbers explain the shells, subshell, orbitals and spin of electrons. The four
quantum numbers are

1. Principal quantum number (n)

The principal quantum number characterizes the principal electron shell which decides the
energy of an electron and the probable position of the electron from the nucleus. Thus n
describes the size of the orbital and energy level in which the electron is placed. The larger
the value of n, larger is the size of orbital which show that the electron is at longer distance
from the nucleus. When n = 1, it belongs to first principal shell (ground state) and lowest
energy level. When electron absorb energy it is excited to the higher principal shells (n = 2, 3,
4,…). Thus n takes integral values 1, 2, 3… ∞ except zero since when n = 0, the energy of
atom becomes zero and the atom doesn’t exists. The value of n describes the shells K, L, M,
N…. in the atom.

2. Azimuthal quantum number ( l )

The azimuthal quantum number or orbital quantum number characterize the shape of the
orbital and the subshell to which electron belong to. Each l value indicates subshell which is
designated as s, p, d, f. Each subshell corresponds to unique shape. It also determines the
number of angular nodes of the orbital which will be equal to the number of l values. The
value of l is subshell to which electrons belong to and it depends on n values and can have
integral values from 0 to n-1. Thus
l = 0, 1, 2…. (n-1).

3. Magnetic quantum number (ml)

The magnetic quantum number represents the number of orbitals and orientation of orbitals in
a subshell. The value of ml is based on the value of l and can have a total of (2l+1) values.
Thus magnetic quantum number has values as 𝑚𝑙 = −𝑙, … ,0, … , +𝑙
Table 1: l and ml value for s, p, d, f subshells

Subshell l value 𝒎𝒍 value

S 0 0
P 1 -1, 0, +1
D 2 -2, -1, 0, +1, +2
F 3 -3, -2, -1, 0, +1,
+2, +3
 Table 2: Total number of orbitals in subshells

Principal Subshell Magnetic Name of the Total

quantum corresponding quantum subshell number of
number to azimuthal number orbital orbital in
(n) quantum (ml) subshells
number ( l )
s (l =0) ml = 0 𝑠 1
ml = 0 𝑝𝑧
p (l = 1) 𝑝𝑥 3
ml = ±1
𝑝𝑦
ml = 0 𝑑𝑧 2
𝑑𝑥𝑧
ml = ±1
d (l = 2) 𝑑𝑦𝑧 5
n = 1, 2, 3,
𝑑𝑥𝑦
… ml = ±2
𝑑𝑥 2 −𝑦 2
ml = 0 𝑓𝑧 3
𝑓𝑥𝑧 2
ml = ±1
𝑓𝑦𝑧 2
f (l = 3) 𝑓𝑥𝑦𝑧 7
ml = ±2
𝑓𝑧(𝑥 2 −𝑦 2)
𝑓𝑥(𝑥 2 −3𝑦 2)
ml = ±3
𝑓𝑦(3𝑥 2 −𝑦 2)
4. Spin quantum number (ms)
The spin quantum number refers the direction of spin of an electron in an orbital. The
direction of spin can be clockwise (ms = + ½) or anticlockwise (ms = - ½).
Assigning Electrons to Orbitals
Three set of rules govern the filling of electrons in the orbital. They are
1. Aufbau principle
Aufbau principle states that the electrons in an atom occupy the orbital of lowest energy
before filling the higher energies. Thus electrons are filled in increasing order of energy
1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s,…..
 Fig 10: Aufbau principle

2. Pauli-Exclusion principle
It states that no two electrons in the same atom can have all the four quantum number the
same. The electrons in each orbital have three quantum numbers n, l and ml same but the
fourth quantum number ms will be different. Thus a single orbital can accommodate a
maximum of two electrons with opposite spin. The s-orbital can accommodate 2 electrons, p-
orbital can hold till 6 electrons (each 3 orbitals hold 2 electrons), the five d-orbitals can
accommodate 10 electrons and seven f-orbitals can hold 14 electrons.
3. Hund’s rule
According to Hunds rule, every orbital in a subshell should be filled with atleast one electron
before pairing of electrons takes place. Further the electrons in singly filled orbitals of
subshell have the same spin.

6. Angular and Radial Wave Functions

Thus the complete wave fuction of hydrogen-like atoms is given as
𝛹𝑛𝑙𝑚 (𝑟, 𝜃, 𝜑) = 𝑅𝑛𝑙 (𝑟) 𝑌𝑙𝑚 (𝜃, 𝜑)

Each wave function has two parts the radial wave function Rnl(r) and angular wave function
(spherical harmonics) Ylm(θ,φ). The radial wave function depends on the quantum numbers n
and l whereas the angular wave function depends on only l and m. The radial wave function
describes the size of the atomic orbital (i.e) the distance between the electron and nucleus.
The angular wave function describes the shape of the atomic orbital. The real forms of radial
and angular wave functions and complete wave function for s and p orbitals of hydrogen
atom (Z = 1 and a0 = 1) is given below
Table 3: Radial, Angular wave function and complete wave function of
s and p orbitals

Quantum numbers Radial wave function Angular wave function Complete wave function

n,l,m (Rnl) (Ylm) (Ψnlm)

n =1, l =0, m=0

𝑅10 = 2𝑒 −𝑟 1 1
𝑌00 = 𝛹1𝑠 = 𝛹100 = 𝑒 −𝑟
√4𝜋 √𝜋
n =2, l =0, m=0
𝑅20 1 1 −𝑟⁄
𝑌00 = 𝛹2𝑠 = 𝛹200 = (2 − 𝑟)𝑒 2
1 −𝑟⁄ √4𝜋 4√2𝜋
= (2 − 𝑟)𝑒 2
2√2
n =2, l =1, m= +1 1 −𝑟⁄ 𝛹2𝑝𝑥 = 𝛹21+1
𝑅21 = 𝑟𝑒 2 3
2√6 𝑌1 +1 = √ 𝑠𝑖𝑛𝜃 𝑐𝑜𝑠𝜑 1
4𝜋 = 𝑟𝑒
−𝑟⁄
2 𝑠𝑖𝑛𝜃 𝑐𝑜𝑠𝜑
4√2𝜋
n =2, l =1, m= -1 1 −𝑟⁄ 𝛹2𝑝𝑦 = 𝛹21−1
𝑅21 = 𝑟𝑒 2 3
2√6 𝑌1 −1 = √ 𝑠𝑖𝑛𝜃 𝑠𝑖𝑛𝜑 1
4𝜋 = 𝑟𝑒
−𝑟⁄
2 𝑠𝑖𝑛𝜃 𝑠𝑖𝑛𝜑
4√2𝜋
n =2, l =1, m= 0 1 −𝑟⁄ 1 −𝑟⁄
𝑅21 = 𝑟𝑒 2 3 𝛹2𝑝𝑧 = 𝛹210 = 𝑟𝑒 2 𝑐𝑜𝑠 𝜃
2√6 𝑌10 = √ 𝑐𝑜𝑠 𝜃 4√2𝜋
4𝜋

7. Wave Function and Orbital Shapes

The wave function Ψ(r,θ,φ) of hydrogen atom is known as atomic orbitals. Atomic orbital is a
wave function that explains the behavior of an electron in atom or region of space. Orbital of
different systems varies only with nuclear charge Z. The probability of finding an electron in
atom is described by Ψ2 (square of wave function of atomic orbital).
Orbital Shapes
Each orbital is represented by a number and a letter where the number (1, 2, 3, …) indicates
the energy level of the electron in the atom and letter (s, p, d, f) denotes the shape of the
orbital. From the solution of Schrodinger wave equation, diagrammatic representation of
shapes of atomic orbitals is drawn using the boundary surface diagrams. A boundary surface
diagram is a boundary surface for an orbital represented in a space where the value of
probability density Ψ2 is a constant.
1. s-orbital
Boundary surface diagram of s-orbital is spherical with nucleus at the center. All the s-
orbitals 1s, 2s, 3s,… are spherically symmetrical but their size and energy increases with
increase in principal quantum number (n) values (1s < 2s < 3s…..).
 Fig 11: Boundary surface diagram of s-orbital

2. p-orbital
Boundary surface diagram of p-orbital show two lobes on either side of plane passing through
the center of the nucleus called nodal plane that bisects the two lobes. Unlike s-orbital, the p-
orbital has three orientations that are designated as px, py and pz which lie on x, y, z axes
which are mutually perpendicular to each other. These three p-orbitals have same energy, size
and shape. The size and energy of the p-orbital increase with increase in n values (2p < 3p <
4p…).
 Fig 12: Nodal planes and Boundary surface diagram of p- orbitals

3. d-orbital
Boundary surface diagram of four of the five d-orbitals (𝑑𝑥𝑧 , 𝑑𝑦𝑧 , 𝑑𝑥𝑦 , 𝑑𝑥 2−𝑦 2 ) consists of
four lobes arranged in a plane which is intersected by two perpendicular nodal planes. The
fifth d-orbital 𝑑𝑧 2 show two lobes in z-axis and a doughtnut of electron density in the xy
plane. However the energy of all five d-orbitals is same. The size and energy of d-orbital
increases with increase in n values (3d < 4d < 5d…).
 Fig 13: Nodal planes and Boundary surface diagram of d-orbitals
4. f-orbital
When n = 4 and l = 3, the subshell consists of seven f-orbitals. The boundary surface
diagrams show that each f-orbital has three nodal surfaces and thus their shapes are complex
and difficult to represent by simple diagram.

8. Theory of Bond Formation

Two theories which explain the bond formation are
1. Valence bond theory
2. Molecular orbital theory

1. Valence Bond Theory (VB Theory)

Valence bond theory explains the formation of covalent bonds in molecules based on the
number of valence electrons and does not consider the other electrons in the atom. The VB
theory is based on the concept of atomic orbital overlap. Atomic orbital overlap is the
interaction of two atomic orbitals of two atoms followed by sharing of electrons of atoms.
Salient features of Valence bond theory
1. According to this theory covalent bonds are formed between atoms that are
sufficiently closer and can overlap their atomic orbitals.
2. Covalent bond is formed by a pair of electrons shared by two atoms.
3. Lone pair of electrons does not involve in bond formation.

Formation of covalent bond in H2 molecule

Consider two hydrogen atoms HA and HB which are far away from each other. Each hydrogen
atom contains one electron in 1s atomic orbital. When the two hydrogen atoms come closer
there is overlap of these two 1s atomic orbitals resulting in the covalent bonding. Now the
electron in HA can revolve around nuclei of HB and vice versa. Thus after bond formation the
two electrons lose their identity and cannot distinguish which electron belong to HA and HB.
The two electrons can move into orbitals of two atoms. These electrons are equally shared
between the orbitals and form a covalent bond.

• Pairing of electrons results in decrease of energy of the system

• This leads to the formation of bond between the atoms which produce a molecule
• It increases the stability of the system, thus a molecule of hydrogen is more stable
than two hydrogen atoms
• The atoms involved in the bond formation attain stable electronic configuration
(Noble gas configuration)
• A pair of electrons shared by two atoms creates a covalent bond
• Bond pair and Lone pair
• A pair of electrons between two bonded atoms constituting the bond is known as bond
pair and pair of electrons which does not involve in bonding is known as lone pair.
 • Atom may contain non-bonding electron pair (i.e) a pair of valence electrons present
on a bonded atom which does not involve in bonding. For example, NH3 contains
three bond pair and one non-bonding electron pair (lone pair) and water has two bond
pair and two lone pairs.

VB theory to some molecules

1. HF: In HF molecule, singly filled 1s orbital of H atom overlap with singly filled 2p orbital
of F to form H – F covalent bond. The three lone pair of electrons remains as non-bonding
electron pair on F atom.

2. H2O: In H2O molecule, O atom contains two singly filled 2p orbitals which overlap with
singly filled 1s orbital of each H atom to form two O – H bonds. Two lone pair of electrons is
present as non-bonding electron pair on O atom.

3. NH3: In NH3 molecule, N atom contains three singly filled 2p orbitals which overlap with
singly filled 1s orbital of each H atom to form three N – H bonds. One lone pair of electrons
is present as non-bonding electron pair on N atom.
Types of orbital overlap
Depending on the types of atomic orbital involve in bonding, different types of bonds are
possible.
1. σ bond: A covalent bond formed by end-to-end or head-to-head overlap of atomic orbitals
of two atoms such as overlap of s – s, s – px px – px atomic orbitals is called a σ bond.
2. π bond: when p orbitals of two atoms approach along and have a lateral overlap such as
overlap of pz – pz or py – py atomic orbitals is called a π bond.
Success of VB theory
1. It successfully explains the covalent bond formation in molecules by using concept of
atomic orbital overlap.
2. According to this theory electron pairing results in decrease of energy of the system
which contributes to stability of the system.
3. It also explains the geometries of many covalent molecules.
4. It clearly depicts the strength of σ bond and π bond.
5. Application of VB theory has lead to development of stereochemistry of carbon
compounds.
Limitations of VB theory
1. This theory ignores the electrons other than the valence electrons.
2. It does not explain the partial ionic character of bonds.
3. It does not explain the bond formation in complex multi-atom molecules.
4. It cannot account for coordinate bond in which one atom donates both the electrons
required for bond formation.
5. It does not explain the bond formation in molecules like H2+ and He2+ which involves
sharing of single electron.

2. Linear Combination of Atomic Orbitals–Molecular Orbitals (LCAO-MO)

In the VB theory even after the formation of the molecule, the atomic orbitals remain as such
and retain their identity with respect to their atoms.
In the MO theory, after the formation of the molecule, the valence electrons lose their identity
and they no longer belong to individual atoms but belong to molecule as a whole.
Salient features of Molecular Orbital theory
1. According to MO theory the atomic orbitals (AO) of the atoms combine to form new
orbitals known as molecular orbitals (MO).
2. Molecular orbitals are described by wave functions based on quantum chemistry.
3. Overlapping of two AO results in formation of two MO (i.e) one bonding MO and
one antibonding MO.
Wave function
1. Every atom can possess full set of s,p,d,f orbitals but not all of them will have
electrons
2. The space where there is more probability of finding electrons is called atomic orbital.
3. The representation of AO is called electron probability density diagram which show
the most probable distribution of electron cloud around the nuclei.
4. Each AO is described by a wave function.
5. For example wave function of 1s and 2p orbital is shown below where r is the
distance between electron and nucleus.

Fig 14: wave function of 1s orbital and 2p orbital

• The wave function of the 1s orbital is always positive sign (above the reference axis)
• The wave function of 2p orbital is sometimes positive sign (above the axis) and
sometimes negative (below the axis). Thus changes sign from positive to negative.
• The above fact is represented as electron probability density diagram (AO) with + or –
sign. These two sign indicates the relative probabilities and – sign does not show that
the probability is negative.
 • The probability density diagram describes the shape of the atomic orbital. Shapes of
1s orbital and 2pz orbital are shown below.

Fig 15: Probability density diagram of 1s orbital and 2p orbital

Combination of wave function: Bonding and Antibonding molecular orbitals

Two waves can overlap in two different ways to form bonding molecular orbital or
antibonding molecular orbital. The overlap of the positive part of one AO with positive part
of another AO and negative part of one AO with negative part of another AO reinforces and
produce a larger wave known as bonding molecular orbital. Similarly the overlap of the
positive of one AO with the negative part of another AO results in destruction of wave and
produces an antibonding molecular orbital.
Fig 16: Formation of bonding and antibonding molecular orbital by
reinforcement and destruction of two AO waves

9. LCAO – MO of H2
Molecular orbital is described by wave function similar to atomic orbital. The wave function
of MO is obtained by Linear combination of atomic orbitals method. This concept can be
explained by considering hydrogen molecule H2. Hydrogen molecule has two hydrogen
atoms HA and HB whose atomic orbitals are described by wave function φA and φB. These
two atomic orbitals overlap (i.e) φA ± φB and produce a new wave function known as
molecular orbital. Such algebraic sum of functions is called as linear combination. The two
normalized LCAO wave functions are

𝛹𝑏 = 𝑁𝑏 (𝜑𝐴 + 𝜑𝐵 ) … . . .1

𝛹𝑎 = 𝑁𝑎 (𝜑𝐴 − 𝜑𝐵 ) ……2
where Ψb and Ψa are wave function, Nb and Na are Normalization constant of bonding and
antibonding molecular orbitals respectively. The numerical value of Nb and Na was calculated
to be 0.71 (~√½). The energy of LCAO-MO’s Ψb and Ψa is represented as Eb and Ea and is
given as

∫ 𝛹𝑏 Ĥ 𝛹𝑏 𝑑𝜏 𝑁𝑏2 ∫(𝜑𝐴 + 𝜑𝐵 ) Ĥ (𝜑𝐴 + 𝜑𝐵 )𝑑𝜏

𝐸𝑏 = = … . .3
∫ 𝛹𝑏 𝛹𝑏 𝑑𝜏 1

𝐸𝑏 = 𝑁𝑏2 ∫ 𝜑𝐴 Ĥ 𝜑𝐴 𝑑𝜏 + ∫ 𝜑𝐴 Ĥ 𝜑𝐵 𝑑𝜏 + ∫ 𝜑𝐵 Ĥ 𝜑𝐴 𝑑𝜏 + ∫ 𝜑𝐵 Ĥ 𝜑𝐵 𝑑𝜏 … .4
where Ĥ is the Hamiltonian operator (total energy operator). Substituting the integrals with
symbols

𝑄𝐴 = ∫ 𝜑𝐴 Ĥ 𝜑𝐴 𝑑𝜏 … . .5

𝑄𝐵 = ∫ 𝜑𝐵 Ĥ 𝜑𝐵 𝑑𝜏 … . .6

𝛽 = ∫ 𝜑𝐴 Ĥ 𝜑𝐵 𝑑𝜏 = ∫ 𝜑𝐵 Ĥ 𝜑𝐴 𝑑𝜏 … . .7

Since both the atoms A and B are H atom, QA = QB = Q and the energy equation 4 becomes
𝐸𝑏 = 2𝑁𝑏2 (𝑄 + 𝛽) … . .8
Similarly
𝐸𝑎 = 2𝑁𝑎2 (𝑄 − 𝛽) … . .9
Here integral Q represents the energy of an electron in the orbital φA or φB that is equal to the
ground state energy of hydrogen atom. The integral β represents the energy of interaction
between the orbitals φA and φB. It is called exchange integral and is inherently negative. Thus
an electron occupying bonding MO, Ψb is more stable and an electron in Ψa is less stable than
electron in in a pure atomic orbital, φA or φB. The actual energy of stabilization and
destabilization is obtained by substituting Normalization constant Na and Nb (Na = Nb = √½)
in equation 8 and 9.
𝐸𝑏 = (𝑄 + 𝛽) … . .10

𝐸𝑎 = (𝑄 − 𝛽) … . .11
This is depicted in the energy level diagram as

Fig 17: Energy level diagram for formation of bonding and antibonding MO of H2
molecule
As the bonding and antibonding orbitals are formed when the AO overlap, energy changes
occur. The formation of the bonding MO (Ψb) decreases the energy and that of antibonding
MO (Ψa) increases the energy.
• The energy of the bonding MO is lower than that of antibonding MO.
• The energy difference between AO and bonding MO is called stabilization energy and
it is denoted as β.
• The energy difference between AO and bonding MO is denoted as β.
• Each MO can accommodate two electrons with opposite spins similar to AO.
• The energy of each electron is decreased by β and hence the total reduction in energy
of the system is 2β. This denotes the bond energy.
• This reduction in energy is the driving force for bond formation.
• When two AO of H atoms combine, it forms lower energy bonding MO which is
designated as σ 1s and higher energy antibonding MO which is designated as σ* 1s.
• The two electrons each from AO of H atom occupy the lower energy bonding MO
with opposite spins.
• In homonuclear diatomic molecule such as H2 molecule, each H atom has an electron
and they occupy the lower energy MO σ1s. Hence the MO configuration for H2 is
σ1s2.

Fig 18: Combination of s – s atomic orbitals to form bonding and antibonding

molecular orbitals
Fig 19: Combination of s – p atomic orbitals to form bonding and
antibonding molecular orbitals

Fig 20: Combination of px – px atomic orbitals to form bonding and

antibonding molecular orbitals
Fig 21: Combination of py– py atomic orbitals to form bonding and
antibonding molecular orbitals

10. Band Theory

Band theory is a quantum model which gives an insight about the possible energies of
electrons in the solids in order to understand the electrical and optical properties of solids. It
is the molecular orbital theory of covalent bands extended to solids. A single atom has
discrete energy states or energy levels of electrons, however in the case of assembly of atoms,
situation is somewhat different. Like when two atoms come closer, their atomic orbitals get
overlapped to form new orbits called molecular orbitals (bonding and antibonding).When
large number of atoms are in close association as in case of solids, the discrete nature of
energy levels of atoms vanishes and there are formation of large number of energy levels
having close energy differences, which in the other sense can be called a band of energy
levels or energy bands.
In order to understand band theory of solids, let us imagine the construction of lithium metal
by adding Li-atoms one at a time, forming Li2 then Li3, Li4, Li5 and so on, until we have LiN,
where N is a very large number of the order of 1020.
Illustration of band theory: (a) single Li-atom with one 2s-valence electron, (b) Li2 with
two M.O., one filled and one vacant, (c) Li3 with three M.O., (d) Li4 with four M.O., (e)
Li9 with nine M.O., half-filled, (f) LiN with a band of N M.O.

Electrons in the solids having allowed energies belong to the allowed energy bands. The
allowed energy bands can be separated by forbidden band to which the electron energy in the
solid does not belong. The allowed energy bands are of two types called valence band and
conduction band. In a solid valence band and conduction band can be separated by a
forbidden band as incase of semiconductors and insulators. Hence the solids have three types
of energy bands which are valence band, forbidden band and conduction band.

Fig 22: Energy bands in solids

Salient features of band theory:
Solids are made up of giant molecules, in which a very large number of spherical atoms are
arranged in a regular close-packed pattern in the form of crystals.
When the atoms are brought together in solids, the atomic orbitals of the valence shells
‘interact’ forming molecular orbitals. During interaction between these atoms, they influence
each other and constitue one single system of electrons while the inner shells remain intact
and are not affected.
The individual energies within an energy band are so-close together and considered to be
continuous. Consequently, an electron in a solid crystal can occupy any of these large number
of energy level, within the band. Thus, a band is a group of infinitesimally energy levels in a
solid/crystal.
Depending upon the composition of a solid/crystal, the bands are of three types.
1. Valence band:
Valence band is the band of energy levels occupied by the valence electrons. It is lowest in
energy among three types of bands. Valence band is generally fully filled in insulators,
however incase of conductors valence band is partially filled by electrons. This band is below
the forbidden band and valence electrons are present in this band. In conductors valence
electrons are free to move in this band and are easily transferred into the conduction band
without giving any external energy.

2. Conduction band:
The next permitted band, above the valence band, is called the conduction band and the
electrons occupying this band are called conduction electrons. It is the band of orbitals in
which electrons are present which have been jumped from the valence band. It is higher in
energy than the valence band and forbidden band. Electrons in this band have enough energy
to move freely and if some external force is applied in the form potential difference across the
ends of solid, electrons flow in a particular direction which we called the flow of charge or
electric current. This band is responsible for the conduction of electricity.

3. Forbidden band:
Electrons are not present in this band. Conductors do not have this band. Insulators have
stronger forbidden band and is wider. The solid acts as a conductor when the valence
electrons are transferred into conduction band. This band restricts the electrons to move into
 Fig 23: Valence, conduction and forbidden (band gap) in solids

conduction band. Being stronger and wider in solids, electrons cannot be transferred into
conduction band, so they are bad conductors of electricity.

On the basis of presence of forbidden band gap energy and band gap size, solids can be
distinguished into three types namely conductors, insulators and semi-conductors.
A. Conductors:
In conductors there is zero band gap energy. Valence band and conduction band are
overlapped. So the electrons in the valence band can easily move into conduction band.
Presence of large number of free electrons in the conduction band results in the flow of
electric current. Metals have zero band gap energy. So the electrons in the valence band are
free to move into the conduction band without gaining any additional energy and hence they
are good conductors of electricity.
B. Insulators:
Insulators have large band gap energy and band gap size .It is difficult for an electron from a
valence band to gain energy and move into conduction band. Absence of free electrons in the
conduction band of insulators restricts the flow of electric current in insulators. So the
insulators are poor conductors of electricity. The conductivity of semiconductors is 24 orders
of magnitude less than conductors.
C. Semiconductors:
Semiconductors have small band gap energy and band gap width. The band gap in
semiconductors is approximately 1 eV and it is possible for an electron in the conduction
band to gain this small amount of energy and enter into conduction band to have some
conductivity. Conductivity of semiconductors is between that of insulators and conductors
which is about 4-16 orders of magnitude less than conductors. It is further possible for the
semiconductors to decrease or tailor this band gap energy, which find its useful applications
in electronics and photoelectronics. Semiconductors are being used in the electronic devices
such as radios, computers, mobile phones, televisions, automobiles, amplifiers.
Semiconductors are being used in the formation of integrated circuits, transistors, diodes,
photovoltaic cells etc.
Examples of semiconductors include silicon, germanium, antimony, boron, tellurium,
selenium etc.

Type of semiconductors
Semiconductors are classified into two types as:
i. Intrinsic semiconductors.
Intrinsic semiconductors are extremely pure (above 99.9999% pure) elements like silicon,
germanium and selenium, having four valence electrons in their atoms and their forbidden
gap energy is about 1 eV. These metals have crystalline structures, in which each atom forms
four covalent bonds by sharing with four neighbouring atoms. In such semiconductors, the
energy gap is so small (about 1 eV) that even at ordinary temperature, there are many valence
electrons, which possess sufficient energy to jump across the forbidden gap to conduction
band. Intrinsic semiconductors are also called undoped semiconductors.

Fig 24: Intrinsic semiconductor

ii. Extrinsic semiconductors.
Extrinsic semiconductor are basically intrinsic semiconductors, whose conducting properties
have been improved by adding extremely small amounts of specific substitutional impurities
called doping agent or dopants. The addition of doping agent reduces the energy gap (Eg),
thereby allowing more electrons to flow from valence band to the empty conduction band.
Usually, 1 part of doping agent is added to 106 parts of parent element (Si, Ge, etc.). By
appropriate doping, the conductivity of an intrinsic semiconductor may be increased by
10,000 times. Dopants added to the extrinsic semiconductor gives desired electrical and
optical properties to the semiconductor.

Fig 25: Extrinsic semiconductor

Based on the nature of the doping agent added, the extrinsic semiconductors are of following
two classes:
Doping
Doping is a process of adding an impurity to the semiconductor in order to modulate the
properties and obtain the desired electrical, optical and structural properties of the
semiconductor. The impurity added to the semiconductor is called dopant. Dopants are of two
types which include n-type and p-type dopants. Generally doping is done to increase the
conductivity of semiconductors. Doping increases the charge carriers that results in the
increased electrical conductivity of semiconductor. Higher the increase in the number of
charge carriers in the semiconductor higher is its electrical conductivity. Doping atoms
occupy the lattice positions of the semiconductor. They increase the number of charge
carriers of the semiconductor in the form of electrons and holes. Electrons are negatively
charged but the holes attain the positive charge. Generally group III and group V elements of
periodic table are extensively used as dopants.
Types of Extrinsic semiconductor:
1. n-type semiconductor :
It is an excess negatively charged electrons containing semiconductor and obtained by adding
extremely small quantitye of a pentavalent element impurity like phosphorus, arsenic or
antimony to pure intrinsic semiconductor crystal lattice like silicon, germanium, tellurium
etc.

Conduction Process: The doping atom forms four covalent bonds with the surrounding four
Si atoms of intrinsic semiconductor with the help of four of its five valence electrons, while
the fifth excess electron remains loosely bound to the donor atom. This loosely bound excess
electron is easily excited from the valence band to the conduction band, when an electric field
is applied. Thus, conduction is due to movement of excess electrons present in an n-type
semiconductor. In other words, the electrical conductivity of an n-type semiconductor is
dependent only on the number of free or excess electrons present in the conduction band.
This results in the increase of negatively charged electrons and hence n-type semiconductor is
formed. Here n stands for negative charge or sign. Increase of charge carriers in the form of
negatively charged electrons increases the electrical conductivity of semiconductor.

Fig 26: n-type semiconductor

2. p-type semiconductor :
It is an excess positively charged holes-containing semiconductor and is obtained by adding
an extremely small quantity of trivalent element like boron, aluminum to the pure intrinsic
semiconductor crystal lattice like silicon, germanium, etc.

Conduction process: All the three valence electrons present in the trivalent doping agent (an
acceptor atom) form three covalent bonds with the surrounding three of the four atoms,
thereby one bond in one of the four surrounding Ge atoms is left incomplete. This gives rise
to a positive hole. The positive holes so formed in the crystal lattice conduct current, when
electric field is applied. During this type of conduction process, a hole travels to an adjacent
atom by acquiring an electron and re-establishing a new covalent bond, by breaking an
existing covalent bond in the adjacent atom and creating a new hole of it. In this way, holes
are filled by electrons from one atom to another and creating new holes in sequence in the
crystal lattice. The movement of holes through the crystal of a p-type extrinsic semiconductor
is nothing but movement of a positive electric charge. Holes carry the current by accepting
electrons and move in the opposite direction to that of electrons during the flow of electric
current. Thus, in such a semiconductor, the positively charged holes are in excess and the
only charge-carriers during conduction.

Fig 27: p-type semiconductor

Role of Arsenic doping on Silicon:

Arsenic is a V group element or pentavalent.It is doped with silicon semiconductor to form
n-type semiconductor. Arsenic atom enters into lattice position of silicon atom and bonds
covalently with four silicon atoms. The fifth electron of arsenic is free to move in the
semiconductor which results in the increase of charge carriers and hence conductivity of
semiconductor. Not only with silicon, arsenic can also be doped with other semiconductors.

Fig 28: Doping of arsenic with silicon

Role of Gallium doping on Silicon:

Gallium belongs to third group of periodic table. It is trivalent element. It can be doped with
silicon to form p-type semiconductor. It has only three valence electrons in its outer most
shell. In the lattice structure, it is surrounded by four silicon atoms and hence creating
electron deficient sites called holes. These holes are ready to accept the electrons and increase
the electrical conductivity of semiconductor. Germanium can also be doped with gallium to
form p-type semiconductor.

Fig 29: Doping of gallium with silicon

 11. Superconductors

Ordinary metals conduct electricity and their specific conductivity is around 106 ohm-1cm-1.
It has been found that for a number of metals and alloys, the electrical resistance disappears
abruptly and completely at temperatures, a few degrees above absolute zero. Low
temperature research has led to the discovery of an amazing phenomenon of
superconductivity.

Superconductors are materials which conduct electricity without any electrical resistance.
The maximum temperature in which a superconducting material exhibits superconductivity,
is called its critical temperature (Tc). Materials in superconducting state become diamagnetic
and are repelled by magnets. The phenomenon of superconductivity was first observed by
Heiki Kammerlingh Onnes, a Dutch physicist in 1913 and found that mercury became
superconducting at 4K (at boiling point of liquid helium). This astonishing work earned him
the 1973 Nobel Prize in physics. Thereafter in 1986 scientists Karl Muller and Johannes
Bednorz developed superconductors by cooling oxide of copper, lanthanum and barium to 40
degrees Kelvin, greater than zero degree Kelvin as was thought to be required for the material
to be a superconductor. Decades after, superconductors have been developed at 164 degrees
Kelvin under high pressure.

Fig 30: Electrical resistivity on going to zero absolute in a superconducting material.

Properties of superconductors:

1. They posses greater resistivity than other elements at room temperature.

2. The transition temperature for different isotopes of a superconductive element
decreases with the atomic mass of the isotope.
3. On adding impurity to a superconducting element, the critical temperature is lowered.
4. During transition, neither thermal expansion nor elastic properties change.
5. In superconducting state, all electromagnetic effects disappear.
6. When a low magnetic field is applied to a superconductor and this if cooled to low
temperature below its transition temperature, then the superconductor expels all
magnetic flux. This is known as Meissner effect.

High temperature superconductors:

In 1986, George Bednorz and Alexmuller found that an oxide of La, Ba and Cu lost its
reisitance around 35k. In 1987, Paul Chu and Wu Jr reported that a ceramic compound,
YBa2Cu3O7-y (y ≤ 0.5) is superconducting upto 100K. This compound is also known as 1:2:3
compound, due to its Y:Ba:Cu stoichiometry.

Preparation of 1: 2: 3 compound:

0.750g of yttrium oxide (Y2O3), 2.622g of barium carbonate (BaCO3) and 1.1581g of cupric
oxide (CuO) is taken in a mortar and grind the mixture to fine powder with the help of pestle.
Then, transfe the powder to a porcelain crucible and place it in a furnace maintained at 920-
9300 C for about 10-12 hours. Allow the mixture to cool gradually in the furnace itself, when
the mixture absorbs the requisite amount of oxygen from the atmosphere. When the
temperature of the furnace becomes about 1000C, the crucible is taken out and cooled in air.
The resulting compound is 1: 2: 3 having composition YBa2Cu3O7-y and exhibits
superconductivity well above 77K. The structure of 1: 2: 3 compound is similarly like
mineral perovskite (CaTiO3) structure.

Applications of superconductivity:
The phenomenon of superconductivity has many applications such as:
1. Superconducting magnets capable of generating high fields with low power
consumptions are being employed in scientific tests and research equipments.
 2. They are also used for magnetic resonance imagind (MRI) in the medical field as a
diagnostic tool.
3. It is used as a magnet for high-energy particle accelerators.
4. It is used as a memory or storage elements in computers.
5. It is used in high-speed magnetically levigated trains.
6. It is used in high-speed switching and signal transmission for computers.

Solved Problems

1. When a radiation of wavelength 500 nm strikes a metal surface, electrons are emitted from
the surface of a metal. The kinetic energy for one electron emitted from the metal is 1 x 10 -
19
J. Calculate the minimum energy required to remove an electron from a metal (binding
energy).
Solution:
Wavelength λ =500 nm
Incident radiation energy
ℎ𝑐 6.626 × 10−34 × 3 × 108
𝐸 = ℎ𝜈 = = = 3.975 × 10−19 𝐽
𝜆 500 × 10−9

1
ℎ𝜈 = 𝜔 + 𝑚𝓋 2
2
The minimum energy required to remove an electron from a metal is
1
𝜔 = ℎ𝜈 − 𝑚𝓋 2 = (3.975 × 10−19 ) − (1 × 10−19 ) = 2.975 × 10−19 𝐽
2

2. Calculate the wavelength of an electron having velocity 6 x 106 ms-1and mass 9.1 x 10-31
Kg.
Solution: The wavelength of an electron
ℎ ℎ 6.626 × 10−34 𝐽𝑠
𝜆= = =
𝑝 𝑚𝑣 (9.1 × 10−31 𝐾𝑔) × (6 × 106 𝑚𝑠 −1 )

= 1.2 × 10−9 𝑚 𝑜𝑟 1.2 𝑛𝑚

3. Calculate the uncertainty in position for a ball of mass 0.2 Kg moving with a speed of 10
ms-1is measured at an accuracy of 1%.
Solution: The momentum of the ball is given by
𝑝 = 𝑚𝓋 = 0.2 𝐾𝑔 × 10𝑚𝑠 −1 = 2 𝐾𝑔. 𝑚𝑠 −1
Thus uncertainty in momentum is calculated from momentum and % of accuracy
∆𝑝 = 2 × 0.01 = 0.02 𝐾𝑔. 𝑚𝑠 −1

ℎ 6.626 × 10−34 𝐽𝑠
∆𝑥 = = = 3.31 × 10−32 𝑚 ∵ 1 𝐽 = 1 𝐾𝑔. 𝑚2
∆𝑝 0.02 𝐾𝑔. 𝑚𝑠 −1

4. Calculate the zero point energy of an electron of mass 9.1 x 10-31Kg in one dimensional
box of length 1Å.
Solution: The energy of electron in one dimensional box is
𝑛2 ℎ2 𝑛2 × (6.626 × 10−34 𝐽𝑠)2
𝐸= =
8𝑚𝐿2 8 × (9.1 × 10−31 𝐾𝑔) × (1 × 10−10 𝑚)2

= 𝑛2 × 4.16 × 10−20 𝐽𝑠 2
The zero point energy is the lowest energy level or first energy level
𝐸1 = 12 × 4.18 × 10−20 𝐽𝑠 2

5. Calculate the energy difference between E4 and E3 for an electron in a one dimensional box
of length 12Å.
Solution: The energy of electron in one dimensional box is
𝑛2 ℎ2 𝑛2 × (6.626 × 10−34 𝐽𝑠)2
𝐸= = = 𝑛2 × 4.16 × 10−20 𝐽𝑠 2
8𝑚𝐿2 8 × (9.1 × 10−31 𝐾𝑔) × (12 × 10−10 𝑚)2
The electron in lowest energy level or first energy level
𝐸1 = 12 × 4.18 × 10−20 𝐽𝑠 2
∆𝐸 = 𝐸4 − 𝐸3 = (2𝑛 + 1)𝐸1 = (6 + 1) × 4.16 × 10−20
= 2.912 × 10−20 𝐽𝑠 2 𝑜𝑟 𝑊𝑎𝑡𝑡 𝑠𝑒𝑐𝑜𝑛𝑑

6. Determine the value of A in wave function of particle in one dimensional box of length L
and find out the normalized wave function of it by normalization method.
Solution: The value A is determined by the normalization of wave function which is given
by
 𝐿 𝐿
𝑛𝜋𝑥
∫ 𝛹 𝑑𝜏 = ∫ 𝐴2 𝑠𝑖𝑛2
2
𝑑𝑥 = 1
0 0 𝐿
(1 − 𝑐𝑜𝑠 2𝑥)
𝑤𝑒 𝑘𝑛𝑜𝑤 𝑡ℎ𝑎𝑡 𝑠𝑖𝑛2 𝑥 =
2
𝐿
𝑛𝜋𝑥 𝐴2 𝐿 2𝑛𝜋𝑥
∫ 𝐴2 𝑠𝑖𝑛2 𝑑𝑥 = ∫ (1 − 𝑐𝑜𝑠 ) 𝑑𝑥 = 1
0 𝐿 2 0 𝐿
𝐿
𝐴2 sin 2𝑛𝜋𝑥 ⁄𝐿
{[𝑥]𝐿0 − [ ] }=1
2 2𝑛𝜋⁄𝐿 0

𝐴2 𝐿
=1
2

2
𝐴=√
𝐿

2 𝑛𝜋𝑥
Thus the normalized wave function is 𝛹 = √𝐿 𝑠𝑖𝑛 𝐿

QUESTIONS:
PART-A
1. What is a black body radiation?
2. Recall Rayleigh-Jean’s Law.
3. What is Planck’s law of radiation?
4. Summarize the photoelectric effect.
5. How is kinetic energy of emitted electrons related to frequency and intensity of
incident light?
6. Tell de Broglie’s hypothesis.
7. Define Heisenberg’s Uncertainty principle.
8. What are the conditions for acceptable wave functions?
9. Define zero point energy for 1D box.
10. What happens to spacing of energy levels when length of one dimensional box
increases?
11. Outline the wave function and energy for a particle in 1D box.
12. What is probability density?
13. List out the types of quantum numbers.
14. Define Aufbau principle.
15. Explain Pauli’s exclusion principle.
 16. Define Hund’s rule.
17. Draw the structure of p-orbitals.
18. Determine the number of orbitals in d subshell.
19. Compare the bonding and antibonding molecular orbitals.
20. Explain conductors, semiconductors and insulators with a neat diagram.
21. What are super conductors? Give example.
22. Differentiate between n-type and p-type semiconductor.
23. List out the properties of superconductors.
24. List out the applications of superconductors.
25. Define Meissner effect.

PART-B
1. Elaborate the LCAO-MO method in the formation of hydrogen molecule.
2. Formulate the Schrodinger wave equation for a particle in one dimensional box and
determine the wave function and energy of the particle.
3. Determine the value of A in the wave function of particle in 1D box by Normalization
method.
4. Outline the time-independent Schrodinger equation of hydrogen atom using φ and θ.
5. Explain the various shapes of atomic orbitals with neat sketch.
6. Summarize the significance of four quantum numbers.
7. Explain band theory of solids with neat diagram.
8. Discuss the various types of semiconductors with suitable examples.
9. Explain the role of doping of arsenic and gallium on silicon with neat diagram.
10. Write a note on superconductor with suitable example.

References
1. A.K.Chandra, Introductory Quantum Chemistry, Tata McGraw-Hill, 4th edition, 1994.
2. R. K. Prasad, Quantum Chemistry, New Age International (P) Limited Publishers, 4th
edition, 2010.
3. Ira N. Levine, Quantum chemistry, 7th Edition, 2013.
4. R. Gopalan, Text book of Inorganic Chemistry, University press (India) Private
Limited, 2012.
5. P.C. Jain, Monica Jain, Engineering Chemistry, Dhanpat Rai Publishing Company,
16th edition, 2013.
 SCHOOL OF SCIENCE AND HUMANITIES
DEPARTMENT OF CHEMISTRY

UNIT-II – MOLECULAR SPECTROSCOPY – SCYA1101

 1. Introduction
Spectroscopy is the branch of science dealing with the study of interaction of electromagnetic
radiation with matter like atoms and molecules. The interaction of EMR with matter gives rise to
two types of spectra namely atomic spectra and molecular spectra. Atomic spectrum arises from
the transition of electrons from one energy level to another due to changes of energy in the atom.
Molecular spectrum involves transition of electrons between rotational and vibrational energy
levels in addition to electronic transition. Therefore molecular spectrum is much more complicated
than the atomic spectrum. Moreover, molecular spectrum consists of bands composed of
innumerable closely packed lines. Molecular Spectroscopy provides a clear image of how diatomic
and polyatomic molecules interact by looking at the Frequency, Wavelength, Wave number,
Energy, and molecular process also provides most useful information regarding the shape and size
of molecules, the bond angles, bond lengths, strength of bonds and bond dissociation energies.
Hence molecular spectroscopy is of great use in determining structure and constitution of
compounds. Before taking up their systematic study, it is necessary that the students must learn
about electromagnetic spectrum and molecular energy levels.

Electromagnetic Radiations (EMR)

Electromagnetic radiation is a form of energy that is produced by oscillating electric and
magnetic fields, traveling through a vacuum or matter. They propagate through space along a linear
path and with a constant velocity. The oscillations in the electric and magnetic fields are
perpendicular to each other, and to the direction of the wave’s propagation. Figure 1 shows an
example of plane-polarized electromagnetic radiation, consisting of a single oscillating electric
field and a single oscillating magnetic field.
 Fig 1: Electromagnetic radiation
Characterization of EMR
The electromagnetic radiations are generally characterized by wavelength (λ), frequency(ν), wave
number (ῡ) and energy(E).
Wavelength (λ): The linear distance between successive crests or trough of a wave is known as
wavelength. It is usually expressed in centimetre or millimetres.
Frequency (ν): The number of vibrations or oscillations per second is known as frequency. It is
expressed in Hertz.
Wave number (ῡ): The reciprocal of wavelength is known as wave number. It is expressed in cm-
1
.
Energy of EMR (E): Electromagnetic radiations consist of particles having small packets of
energies called quanta or photons. Photons possess the characteristic of wave and travel with the
speed of light. The amount of energy corresponding to one photon is expressed by Planck’s
equation as
ℎ𝑐
E = hν or E = 𝜆

Where h – Planck’s constant (6.62x10-34J)

ν - frequency in Hz
λ – wavelength in cm.
Unit conversion:
1 μm = 10-6 m
1 nm = 10-9 m = 10 Å
Interaction of EMR with Matter
In order to interact with the electromagnetic radiation, the molecules must have some electric or
magnetic effect that could be influenced by the electric or magnetic components of the radiation.
1. In NMR spectroscopy, for example, the nuclear spins have magnetic dipoles aligned with
or against a huge magnetic field. Interaction with radiofrequency of appropriate energy
results in the change in these dipoles.
2. Rotations of a molecule having a net electric dipole moment, such as water will cause
changes in the directions of the dipole and therefore in the electrical properties.
3. Vibrations of molecules can result in changes in electric dipoles that could interact with
the electrical component of the electromagnetic radiation.
4. Electronic transitions take place from one orbital to another. Owing to the differences in
the geometry, size, and the spatial organization of the different orbitals, an electronic
transition causes change in the dipole moment of the molecule
5. The above examples suggest that a change in either electric or magnetic dipole moment in
a molecule is required for the absorption or emission of the electromagnetic radiation.

Electromagnetic spectrum
Electromagnetic spectrum is the arrangement of various types of electromagnetic radiations in
order of their increasing wavelengths or decreasing the frequencies.
Regions of the electromagnetic spectrum
MICRO INFRA VISIBLE
NMR ESR X-RAY γ- RAY Unit
WAVE RED &UV
Wavelength
10 m 100 cm 1 cm 100 μm 1 μm 10 nm 100 pm
(λ)
Wave number
10-1 10-2 1 100 104 106 108
(cm-1)
Energy
10-3 10-1 10 103 105 107 109
(Joules/mole)
Since, cosmic rays have the highest frequencies while radio waves have the lowest frequencies.
All the types of radiations of electromagnetic radiations travel with the same speed of light but
they differ in their wavelength from each other. The arrangement of different types of emr with
increasing order of their wavelength are cosmic rays < γ-rays < X-rays < ultraviolet rays < visible
< infrared rays <micro waves<radio waves.

Energy levels in molecules

The electronic transitions in an atom are due to absorption or emission of electromagnetic
radiation. We have further stated that electronic transitions in an atom are quantized and the
resulting line emission spectra correlate with the difference between the electronic energy levels.
There are more possibilities for transition between various energy levels in the polyatomic
molecules than those in individual atoms. The total energy of a molecule is the sum of four
different types of energy, viz., translational, rotational. vibrational and electronic. Therefore,
absorption or emission of energy (electromagnetic radiation) may cause changes in some or all of
these types of energy, and molecular spectra provide a method of measuring these changes. Before
going into further details of molecular energy changes, their measurements and interpretation, let
us first define the energy types present in molecules. Energy can be stored either as potential
energy or kinetic energy, in a variety of ways including:
• Translational energy (Etrans): Translational Energy (Etrans) is concerned with the overall
movement of the molecules along the three axes. It is significant only in gases and to a lesser extent
for liquids. In solids, translational energy is minimum. Here small amounts of energy stored as
kinetic energy. This is unquantized (can take any value) and hence is not relevant to spectroscopy
.
• Rotational energy (Erot): involves the spinning of molecules about the axes passing through
their centre of gravity. Here, kinetic energy associated with the tumbling motion of molecules.
This is quantized.

• Vibrational energy (Evib): is associated with vibrations within a molecule such as the
stretching or the bending of bonds. In stretching type, the bond length varies but in bending type,
bond angle varies. Here, the oscillatory motion of atoms or groups within a molecule (potential
energy ↔ kinetic energy exchange). This is quantized.

• Electronic energy (Eelec): involves changes in the distribution of electrons by the promotion
of electrons to higher levels on absorption of energy. This is similar to electronic energy changes
in atoms. Here energy stored as potential energy in excited electronic configurations. This is
quantized.
If E is the energy of a molecule, it can be expressed as the sum of translational, rotational,
vibrational and electronic contributions.
E = Etrans + Erot + Evib + Eelec
The energies of molecules with spacing of energy levels of different types of energy as shown in
fig 2. It is clear that electronic levels are much more widely spaced than vibrational levels, which
in turn are more widely spaced than rotational levels.

Fig 2: Representation of Electronic, Vibrational and Rotational energy levels

2. Microwave Spectroscopy

When a gas molecule is irradiated with microwave radiation, a photon can be absorbed through
the interaction of the photon’s electronic field with the electrons in the molecules. For the
microwave region this energy absorption is in the range needed to cause transitions between
rotational states of the molecule. However, only molecules with a permanent dipole that changes
upon rotation can be investigated using microwave spectroscopy. This is due to the fact that their
must be a charge difference across the molecule for the oscillating electric field of the photon to
impart a torque upon the molecule around an axis that is perpendicular to this dipole and that passes
through the molecules center of mass.
This interaction can be expressed by the transition dipole moment for the transition between two
rotational states
Probability of Transition = ∫ ψrot (F)μ^ ψrot(I) dτ
Where Ψrot(F) is the complex conjugate of the wave function for the final rotational state, Ψrot(I) is
the wave function of the initial rotational state , and μ is the dipole moment operator with Cartesian
coordinates of μx, μy, μz. For this integral to be nonzero the integrand must be an even function.
This is due to the fact that any odd function integrated from negative infinity to positive infinity,
or any other symmetric limits, is always zero.

Selection Rule:
In addition to the constraints imposed by the transition moment integral, transitions between
rotational states are also limited by the nature of the photon itself. A photon contains one unit of
angular momentum, so when it interacts with a molecule it can only impart one unit of angular
momentum to the molecule. This leads to the selection rule that a transition can only occur between
rotational energy levels that are only one quantum rotation level (J) away from another.
ΔJ=±1
Where J is the rotational quantum number

Degrees of Freedom
A molecule can have three types of degrees of freedom and a total of 3N degrees of freedom,
where N equals the number of atoms in the molecule. These degrees of freedom can be broken
down into 3 categories.
• Translational: These are the simplest of the degrees of freedom. These entail the movement
of the entire molecule’s center of mass. This movement can be completely described by three
orthogonal vectors and thus contains 3 degrees of freedom.
• Rotational: These are rotations around the center of mass of the molecule and like the
translational movement they can be completely described by three orthogonal vectors. This again
means that this category contains only 3 degrees of freedom. However, in the case of a linear
molecule only two degrees of freedom are present due to the rotation along the bonds in the
molecule having a negligible inertia.
• Vibrational: These are any other types of movement not assigned to rotational or translational
movement and thus there are 3N – 6 degrees of vibrational freedom for a nonlinear molecule and
3N – 5 for a linear molecule. These vibrations include bending, stretching, wagging and many
other aptly named internal movements of a molecule. These various vibrations arise due to the
numerous combinations of different stretches, contractions, and bends that can occur between the
bonds of atoms in the molecule.
Each of these degrees of freedom is able to store energy. However, In the case of rotational and
vibrational degrees of freedom, energy can only be stored in discrete amounts. This is due to the
quantized break down of energy levels in a molecule described by quantum mechanics. In the case
of rotations the energy stored is dependent on the rotational inertia of the gas along with the
corresponding quantum number describing the energy level.
Classification of Molecules Based on Moment of Inertia:
Microwave rotational spectroscopy uses microwave radiation to measure the energies of rotational
transitions for molecules in the gas phase only (due to intermolecular interactions hindering
rotations in the liquid and solid phases of the molecule). It accomplishes this through the
interaction of the electric dipole moment of the molecules with the electromagnetic field of the
exciting microwave photon. In microwave spectroscopy, molecules may be classified in to 5
categories based on their shape and the inertia around their 3 orthogonal rotational axes. These 5
categories include diatomic molecules, linear molecules, spherical tops, symmetric tops and
asymmetric tops.
The moment of inertia I of any molecule about any axis through the centre of gravity is given by

𝐼 = ∑ 𝑚𝑖 𝑟𝑖2

Where mi and ri are the mass and distance of atom i from the axis. There is one of these axes,
conventionally labeled the c axis, about which the moment of inertia has its maximum value and
a second axis, labeled the a axis, about which the moment of inertia has its minimum value. It can
be shown that the a and c axes must be mutually perpendicular. These with a third axis, the b axis,
which is perpendicular to the other two, are called the principal axes of inertia and the
corresponding moments of inertia IA, IB and IC are the principal moments of inertia. In general,
according to convention IC≥ IB≥IA.
1. Linear molecules: In these molecules, atoms are arranged in a straight line, such as HCl,
HCN, Carbon oxy sulphide (O=C=S) etc., the three directions of rotations may be taken as a)
about the bond axis b) end-over-end rotations in the plane of the paper, and c) end-over-end
rotation at right angles to the plane. It is evident that the moments of b and c are the same (i.e. IB
= IC) while that of IA is very small, taken as approximation, IA = 0, For a linear molecule the
separation of lines in the rotational spectrum can be related directly to the moment of inertia of the
molecule. Since the moment of inertia is quadratic in the bond lengths, the microwave spectrum
yields the bond lengths directly, provided the atomic masses are known. Thus, for linear molecules
we have
IB = IC, IA = 0

2. Symmetric tops: In symmetric top, two moments of inertia are the same. For example, methyl
fluoride, where three hydrogen atoms are bonded tetrahedrally to the carbon as shown below.
As in the case of linear molecules, the end-over-end rotation in, and out of, the plane of the paper
are still identical and so we have IB = IC. The moment of inertia about the C-F bond axis is small,
so such a system of molecules spinning about this axis can be imagined as a top.
Symmetric tops: IB = IC ≠ IA IA ≠0.
There are two subdivisions of this class,
if IB = IC > IA, then the molecule is said to be prolate. For example: Methyl fluoride, Methyl iodide,
since the heavy iodine nucleus makes no contribution to Ia.
Where as if IB = IC < IA, then it is said to be oblate. For example: Boron trichloride which is planar
and symmetrical. In this case, IA = 2IB=2IC.
3. Asymmetric tops: These molecules have three orthogonal rotational axes that all have
different moments of inertia and most molecules fall into this category. Unlike linear molecules
and symmetric tops, these types of molecules do not have a simplified energy equation to
determine the energy levels of the rotations. These types of molecules do not follow a specific
pattern and usually have very complex microwave spectra. For example H2O and vinyl chloride.

Asymmetric tops : IA ≠ IB ≠ IC
4. Spherical tops: Spherical tops are molecules in which all three orthogonal rotations have
equal inertia and they are highly symmetrical. This means that the molecule has no dipole and for
this reason spherical tops do not give a microwave rotational spectrum. For example: Methane.
Spherical tops : IA = IB = IC
3. Rotational Spectra of Diatomics
Consider a linear rigid diatomic shown in Fig 3.

Fig 3: A rigid diatomic with masses m1 and m2 joined by a thin rod of length r = r1 + r2 the
centre of mass is at C.
The two independent rotations of this molecule are with respect to the two axes which pass though
C and are perpendicular to the “bond length” r. The rotation with respect to the bond axis is
possible only for “classical” objects with large masses. For quantum objects, a “rotation” with
respect to the molecular axis does not correspond to any change in the molecule as the new
configuration is indistinguishable from the old one.
The center of mass is defined by equating the moments on both segments of the molecular axis.
m1 r1 = m 2 r2 (1)
The moment of inertia is defined by
I = m1 r12 + m2 r22 (2)

= m2 r2 r1 + m1 r1 r2

= r1 r2 (m1 + m2 ) (3)

Since m1 r1 = m 2 r2 = m2 (r − r1 ) , (m1 + m2 ) r1 = m2 r Therefore,

m2 r m1 r
r1 = and r2 = (4)
m1 + m2 m1 + m2

Substituting the above equation in (3), we get

m1 m2 r 2 m1 m2
I = =  r2,  = (5)
(m1 + m2 ) m1 + m2

Where μ, the reduced mass is given by

1 1 1
= + (6)
 m1 m2
The rotation of a diatomic is equivalent to a “rotation” of a mass μ at a distance of r from the origin
C. The kinetic energy of this rotational motion is K.E. = L2/2I where L is the angular momentum,
Iω where ω is the angular (rotational) velocity in radians/sec. The operator for L2 is the same as
the operator L2 for the angular momentum of hydrogen atom and the solutions of the operator
equations L2 Υlm = l (l + 1) Ylm, where Ylm are the spherical harmonics.
The quantized rotational energy levels for this diatomic are
h2
EJ = J ( J + 1) (7)
8 2 I
The energy difference between two rotational levels is usually expressed in cm-1. The wave
number corresponding to a given ∆E is given by
 = ∆E /hc, cm-1 (8)
The energy levels in cm-1 are therefore,
h
EJ = B J ( J + 1) where B = (9)
8 2 Ic
The rotational energy levels of a diatomic molecule are shown in Fig 4.
Fig 4: Rotational energy levels of a rigid diatomic molecule and the allowed transitions
The selection rule for a rotational transition is,
∆J = ±1 (10)
In addition to this requirement, the molecule has to possess a dipole moment. As a dipolar
molecule rotates, the rotating dipole constitutes the transition dipole operator μ. Molecules such
as HCl and CO will show rotational spectra while H2, Cl2 and CO2 will not. The rotational
spectrum will appear fig 5 as follows

Fig 5: Rotational spectrum of a rigid diatomic. Values of B are in cm-1. Typical values of B
in cm-1 are 1.92118 (CO), 10.593 (HCl), 20.956 (HF), 1H2 (60.864), 2H2 (30.442), 1.9987 (N2).
From the value of B obtained from the rotational spectra, moments of inertia of molecules I, can
be calculated. From the value of I, bond length can be deduced.
Calculation of “J” for CO molecule
Example 1: Calculate J value of first three rotational transitions of CO molecule if its bond length
is 112.8 pm. Given C12 = 12.0001 amu and O16 = 15.9994 amu.
(Note: to convert amu in to mass multiplied by 1.66 x 10-24)
Solution:
I = μr2
m1 m2 15.9994 x12.001
 = = x 1.66 x 10-24
m1 + m2 15.9994 + 12.001

μ = 1.1383 x 10-23g
therefore I = 1.1383 x 10-23g x (112.8 x 10-10 )2 = 1.447 x 10-39
we know that
B = h/(8π2 Ic) = 6.626 x 10 -34/(8 x (3.14)2 x 1.447 x 10-39x 3 x 1010)
= 1.9351 cm-1
Therefore the rotational transition of CO molecule for first three transition levels is as follows
∆ν (J = 0 to J = 1) = 2B
= 2 x 1.9351 = 3.870 cm-1
∆ν (J = 1 to J = 2) = 4B
= 4 x 1.9351 = 7.7404 cm-1
∆ν (J = 2 to J = 3) = 6B
= 6 x 1.9351 = 11.6106 cm-1

4. Rotational Spectra of Polyatomics

Linear molecules such as OCS and HC≡CCl have spectra similar to diatomics. In diatomics as
well as linear triatomics, IA = IB; IC = 0. IA, IB and IC are the three moments of inertia of molecules
along three independent axes of rotation. Just as any translation can be decomposed into three
independent components along three axes such as x, y and z, any rotation can be decomposed into
rotations along three axes A, B, and C. The way to choose these axes is to have the simplest values
of IA, IB and IC. Since triatomics are heavier than the constituent diatomics, their moments of
inertia are larger and the values of rotational constants, B, are smaller, in the range of 1 cm-1. The
value of IA or IB determined from the B value gives the total length of the triatomic. To determine
the two bond lengths in the linear triatomic, we need to determine the moment of inertia IA’ of an
isotope of the triatomic. From two values of IA and IA’ , we can determine the two bond lengths.
The rotational spectra of asymmetric molecules for whom IA ≠ IB ≠ IC can be quite complicated.
For symmetric tops, two moments of inertia are equal ie.,
 IA = IB ≠ IC ; IC ≠ 0
In CH3Cl for example, the main symmetry axis is the C – Cl axis. We need two quantum numbers
to describe the rotational motion with respect to IA and IC respectively. Let J represent the total
angular momentum of the molecule and K the angular momentum with respect to the C – Cl axis
of the symmetric top. J takes on integer values and K cannot be greater than J (recall that ml ≤ ‫ ׀‬l
‫ ׀‬for orbital angular momentum). The (2J + 1) “degeneracy” is expressed through the 2J + 1
values that K can take.
K = J, J – 1, ….. 0, - (J – 1), - J
The rotational energies of a symmetric top are given by
E J ,K / hc = BJ ( J + 1) + ( A − B ) K 2 , cm −1

The moments of inertia are related to B and A as

h h
B = and A =
(8 I c .c)
2
(8 I A c)
2

As the energy depends on K2, energies for states with + K and – K are doubly degenerate. Thus
there will be J + 1 levels and (2J + 1) states for each values of J.
The selection rules for the symmetric top are,
ΔJ = ± 1 and ΔK = 0
It can be easily shown hat
(EJ +1, K – EJ,,K)/hc = 2 BJ (J +1)
This implies that the spectrum is independent of the value of K. The physical meaning is as
follows. K refers to the rotation about the symmetry axis such as the C - Cl axis. A rotation about
this axis does not change the dipole moment. We mentioned in the section on the rotational spectra
of diatomics that the molecular dipole moment has to change during the rotational motion
(transition dipole moment operator of Eq 5) to induce the transition. Rotation along the axis A and
B changes the dipole moment and thus induces the transition.
By using rotational or microwave spectroscopy, very accurate values of bond lengths can be
obtained. For example, in HCN, the C-H length is 0.106317 ± 0.000005 nm and the CN bond
length is 0.115535 ± 0.000006 nm. The principle of the microwave oven involves heating the
molecules of water through high speed rotations induced by microwaves. The glass container
containing water however remains cold since it does not contain rotating dipoles.
 5. Vibrational Spectroscopy
The pure vibrational spectra and the vibrational – rotational spectra are observed in near IR region.
Since the energy changes in vibrational transitions are always larger than those in pure rotational
transitions, so the molecules in the gaseous state exhibit vibrational-rotational spectra. This
spectrum is shown only by molecules possessing either permanent dipole moment or the dipole
moment arising due to vibration of atoms in molecules. These molecules are IR active for example
CO, NO, HCl, CN etc. The homo nuclear diatomic molecules like O2, N2 and Cl2 have no
permanent dipole moment of their own however, when they are subjected to electromagnetic
radiation it induces an oscillating dipole moment and excite them to undergo vibrational –
rotational transitions. Pure vibrational spectroscopy can be observed only in liquid, where
interaction between the molecules inhibit rotation. The IR spectroscopy is highly useful in the
determination of molecular structure and for identification of functional groups in organic
compounds.

Definition: Interaction of Infrared radiation with matter

Spectral Range of IR Radiation:

Near IR: 12000 cm-1 to 4000 cm-1

MID IR: 4000 cm-1 to 620 cm-1
Far IR: 300 cm-1 to 10 cm-1

Principle: Vibrational spectroscopy principle can be explained in two different approaches.

1. Classical Approach
Oscillating polar group produces stationary alternate electric fields (SAEF). These SAEFs can be
presented in the form of frequency or energy. If the SAEF energy matches with IR radiation, the
oscillating group absorbs energy and shows signal at corresponding frequency in the IR spectrum.

2. Quantum Approach
Irradiation of sample with IR radiation brings about changes in vibrational levels of molecules.
The transition of molecule from lower vibrational energy level to higher vibrational energy level.
The transition is induced by absorption of photon of IR light of appropriate frequency, which
matches with energy gap between the two levels.
 v2

Absorption takes place when E= v2 v

E = IR Frequency

v

IR transition in a molecule

6. Vibrations of Diatomic Molecules (Simple Harmonic Oscillator)

Taking the simple case where a diatomic molecule may be considered as a simple harmonic
oscillator. Consider a diatomic molecule in which the atoms are linked by a covalent bond. The
bond acts like a spring. The stiffness or elasticity of the spring (bond) is determined by a factor
called force constant. The force constant is a measure of bond strength between two atoms.
An oscillator in which the resorting force(F) is directly proportional to the displacement , in
accordance with Hook’s we have
F=-kx
Where x is the displacement and is equal to the distance to which the atoms have been stretched
(R) minus equilibrium distance between the atoms (Re) i.e. x = R – Re, k in equation is called
force constant. The negative sign indicates that the force is the restoring force, and has a direction
opposite to that of the displacement. Thus if x=1 cm, k= -F. Hence force constant may be defined
as the restoring force per unit displacement (or per cm) of a harmonic oscillator. It is found to be
related to the equilibrium vibration frequency ωe according to equation

1 k
e =
2 

Where μ is the reduced mass of the system.

To calculate k, equation can be rewritten as follows:
k = 4 2 e2 

m1 m2
k = 4 2 e2
m1 + m2
Where m1 and m2 are the masses of the oscillating atoms.
Vibration of Polyatomic Molecules
Degrees of freedom:
The number of variables required to describe the motion of molecule or atom
Translational motion:
The atom shifts from one point to another point in 3 dimensional space. It is a permanent
displacement.
Rotational motion:
Roational of an atom through fixed axis.
Vibrational motion:
The motion brings change in bond angle and bond distance between connecting atoms
Normal mode:
It is a molecular vibration where some or all atoms vibrate together with the same frequency
in a defined manner.
Poly atomic molecules show more than one fundamental vibrational absorption bands. The
number of these fundamental bands is related to the degrees of freedom in a molecule. The number
of degrees of freedom is equal to the sum of coordinates necessary to locate all the atoms of a
molecule in space. Each atom has three degrees of freedom corresponding to the three Cartesian
coordinates (X, Y, Z) which necessary to describe its position on relative to other atoms in a
molecule(fig 2.6.).
Therefore the total number of degrees of freedom in a molecule containing N-atoms is equal to 3N
which includes rotational, vibrational and translation degrees of freedom.
Total number of degrees of freedom (3N) = Translational + Vibrational + Rotational
 Z

H
Movement of molecule from one place to
another place is translational motion
C
H H
H

H
Rotational of atom or molecule through fixed
axis is rotational motion

C
H H
H

H
Change in bondlength or bond angle is
vibrational motion
C
Y
H H
H

Fig 6: Representation of degrees of freedom of a methane molecule

Poly atomic
S.No. degrees of freedom Monoatomic Non linear
Linear molecule
molecules
1 Total 3 3N 3N
2 Translational 3 3 3
3 Rotational 0 2 3
4 Vibrational 0 3N-5 3N-6

We need 3-coordinates to specify the centre of gravity of a molecule in space. Hence the centre of
gravity of the molecule has three independent translational degrees of freedom.
Vibrational Degrees of Freedom for Linear Molecule
If the molecule is linear then two independent modes of rotation about x and y axis are possible.
Therefore the number of coordinates or degrees of freedom necessary to specify the vibrational
transition is
Total degrees of freedom for polyatomic molecule = Translational + Rotational + Vibrational
3N = 3 + 2 + Vibrational
Vibrational Degrees of freedom = 3N-5
For example: CO2, CO, HCl, Acetylene
Vibrational Degrees of freedom for CO = 3N-5 = 3 x 2 – 5 = 1
Vibrational Degrees of freedom for C2H2 = 3N-5 =3 x 4 – 5 = 7
Vibrational Degrees of freedom for CO2 = 3N-5 =3 x 3 – 5 = 4

Degrees of Freedom of Vibration for Non-linear Molecule

In case of non-linear molecules, 3 rotational coordinates(x,y,z) are needed to specify the molecular
orientation about the centre of gravity.
Total degrees of freedom for polyatomic molecule = Translational + Rotational + Vibrational
3N = 3 + 3 + Vibrational
Vibrational degrees of freedom = 3N – 6
Vibrational Degrees of freedom for H2O = 3N-6 = 3 x 3 – 6 = 3
Vibrational Degrees of freedom for CH4 = 3N-6 = 3 x 5 – 6 = 9
Vibrational Degrees of freedom for NH3 = 3N-6 = 3 x 4 – 6 = 6
Vibrational Degrees of freedom for C6H6 = 3N-6 = 3 x 12 – 6 = 30

7. Types of Molecular Vibration

Vibration: Periodic displacement of atoms or nuclei from their equilibrium position is the
vibration.
Classification: There are two types of molecular vibrations namely stretching and bending
vibrations.
1. Stretching Vibration: The change in bond length between connecting atoms without altering
the bond axis or bond angle is known as Stretching vibration. Stretching vibration are two types
(Fig.)
a. Symmetric stretching vibration:
At the time of vibration reference bonds subjected to either expansion or compression (i.e.
Opposite direction of movement)

b. Asymmetric stretching vibration:

At the time of vibration reference bonds subjected to compressed and other is expanded (i.e.
same direction of movement)
2. Bending Vibrations: The change in bond angle between connecting atom by changing the
bond angle in and out of the bond axis plane is known as bending vibration. Bending vibration are
four types (Figure).

Classification of Vibrations

Stretching Vibrations Bending Vibrations

Symmetric Stretching Asymmetric Stretching Inplane bending Out of plane bending

Vibrations Vibrations Vibrations Vibrations

Scissoring Rocking Wagging Twisting

Schematic Representations of types of Vibrational Modes

 Expansion Compression

B A B B A B Symmetric stretching vibration

Compression Expansion
Expansion Compression
Asymmetric stretching vibration
B A B B A B

B B
A A Inplane bending vibration

B B

Inplane Scissoring Inplane Scissoring

B B
A A Inplane bending vibration

B B

Inplane Rocking Inplane Rocking

B B
A Outplane bending vibration
A

B B

Outplane Wagging Outplane wagging

B B
A A Outplane bending vibration

B B

Out plane twisting Out plane twisting

a. Scissoring: The connecting atoms joined to a central atom move towards and away from each
other in the same plane and change the bond angle.
b. Rocking: The connecting atoms joined to a central atom move back and forth in the same
direction.
c. Twisting: One of the atom moves up the plane while the other atom moves down the plane
with respect to the central atom.
d. Wagging: The two atoms move up or below the plane with respect to the central atom.
In pending vibrations, rocking and scissoring vibrations occur in the same plane (in plane
vibrations) whereas twisting and wagging occur out of plane. In some cases, because of symmetry
factors two or more vibrational modes may be identical with same energy. Such vibrations are
generally referred to as degenerate modes
Vibration Modes of CO2 Molecule
CO2 is a linear triatomic molecule, therefore it has 3N – 5 = 3 x 3 – 5 = 4 fundamental modes of
vibration. The four modes of vibration are symmetrical stretching, antisymmetrical stretching and
two bending modes (fig 2.7.). During the stretching vibration, there is no change in the dipole
moment. Hence, this symmetrical stretch will not absorb radiation, and hence it is IR inactive.
Expansion Compression

O C O Inactive
O C O

Expansion Compression Compression Expansion

O C O O C O 2565 cm-1

Inplane bending vibration 526 cm-1

O C O

Degenerative

O C O Outplane bending vibration 526 cm-1

Fig 7: Representation of stretching and bending molecular

vibrations of CO2 Molecule
During the asymmetrical stretching, there is a change in the dipole moment and hence this mode
is IR active. Two bending modes have the same energy and are said to be degenerate, i.e. only one
absorption band is expected due to the two bending modes of vibrations. Therefore for linear CO2
molecule we get total two absorption band in the spectrum.
Vibrations modes of H2O molecule
Symmetrical stretching

O O
-1
3686cm
H H
H H
Expansion Compression

Asymmetrical stretching

O O -1
3606cm
H H
H H

Inplane scissoring

O O
-1
1885cm

H H H H

Fig 8: Representation of stretching and bending molecular

vibrations of H2O Molecule
Water is a bent, non-linear triatomic molecule. Therefore it has 3N – 6 = 3 x 3 – 6 = 3 fundamental
modes of vibrations (fig 2.8.). The three modes of vibrations are a bending mode, a symmetrical
stretching and an unsymmetrical stretching mode. All the three modes of vibration involve
changing in dipole moment and hence they are IR active.
8. Determination of Force Constant
Calculate the force constant of CO molecule having ῡ = 2143 cm-1
For C ≡ O molecule the ῡ = 2143 cm-1
In 12
C – 16O the atomic mass of C = 12.00 amu and O = 16.00 amu
𝑚1 𝑚2 192
The reduced mass is calculated from 𝜇 = 𝑚 = = 6.857 𝑎𝑚𝑢
1 +𝑚2 28

1 amu = 1.66 x 10-27 Kg

The reduced mass
𝜇 = 6.857 𝑎𝑚𝑢 × (1.66 × 10−27 𝐾𝑔) = 1.1383 × 10−26 𝐾𝑔
𝑐
We know that 𝜈 = 𝜆 ⇒ 𝜈 = 𝑐ῡ = (3 × 1010 𝑐𝑚 𝑠 −1 ) × (2143 𝑐𝑚−1 )

Thus 𝜈 = 6.429 × 1013 𝑠 −1

The angular frequency is given as ω = 2πν
𝜔 = 2𝜋𝜈 = 2 × 3.14 × 6.429 × 1013 𝑠 −1 = 4.037 × 1014 𝑠 −1
From classical mechanics, the angular frequency ω is

𝑘
𝜔=√
𝜇

𝑘
𝜔2 =
𝜇
Thus 𝑘 = 𝜇𝜔2 = (1.1383 × 10−26 𝐾𝑔) × (4.037 × 1014 𝑠 −1 )2 = 1855 𝐾𝑔 𝑠 −2
∵ 1 𝑁𝑒𝑤𝑡𝑜𝑛 = 1𝐾𝑔 𝑚 𝑠 −2
The force constant 𝑘 = 1855 𝑁𝑚−1
9. Electronic Spectroscopy
The spectroscopy deals with study of electromagnetic radiation with matter. Thus it gives the
information about the transition between rotational and vibrational energy levels with the addition
of electronic energy levels. It is observed in the visible and ultraviolet region of spectrum.
Absorption spectra are obtained when the electrons in the molecule are promoted from the lower
electronic state to higher electronic excited state by the absorption of radiation. On the other hand,
emission spectra are obtained from the transition of electrons from higher excited state to lower
electronic state. An Electronic transition in molecules is accompanied by vibrational transition and
the spectra consist of a series of bands. Each band has a number of lines due to rotational transition.
Hence, the whole rotational – vibrational spectrum is superimposed on the electronic spectrum and
this process produces a very complex band system.
Types of Electronic Transitions in Organic Molecules
Electrons in a molecule can be classified into three different types
1. Bonding σ–orbital: electron in a single covalent bond is tightly bound and hence radiation of
high energy is required to excite them.
2. Non-bonding n-orbital: electrons attached to atoms as loan pair. These electrons are not
involved in bonds. For example: Oxygen, Nitrogen and Chlorine. The non-bonding electrons can
be excited at a lower energy than tightly bound bonding electrons.
3. Bonding π-orbital: electrons in double or triple bond can be excited relatively easily.
Molecules containing a series of alternating double bonds, the π-electrons are delocalized and
require less energy for excitation.
According to molecular orbital theory, when a molecule is excited by the absorption of energy, its
electrons are promoted from a bonding to anti bonding orbital (higher energy states). The anti
bonding orbital associated with σ-bond is called σ* orbital and the electron transition is represented
as σ – σ*. The anti bonding orbital associated with the π-bond is known as π* orbital and the
corresponding transition is denoted as π – π*. Since non-bonding electrons are not directly
involved in bonding, there is no corresponding anti-bonding orbital for them. So the major
electronic transitions within the electronic transitions are σ – σ*, n – σ*, π – π* and n – π*. When
the selection rules are applied, the first three transitions are usually allowed whereas n – π*
transition is forbidden. The energy required for various transitions follows the order σ – σ* > n –
σ*> π – π* > n – π*.

Electronic Energy levels

Antibonding electrons 

Antibonding electrons 

Nonbonding electrons n

Bonding electrons 

Bonding electrons 
Characteristics of electronic transitions:
1. Electronic transitions are appeared as broad bands due to their higher energy transitions.
2. During electronic transition there should be change in dipole moment (i.e. Ground state and
Excited state dipole moment should not be the same)
3. During electronic transition retention of multiplicities is allowed
4. During electronic transition change in angular momentum should be zero or +/- 1

Types of Electronic Transitions in Organic Compounds

1. σ → σ * transition: The energy required for this transition is high (i.e. very short wavelengths;
150nm), which is not coming under UV spectral range. The saturated alkanes will undergo this
type of transition.
2. n → σ * transition: The saturated hydrocarbons attached to hetero atoms will undergo this
type of transition. Example: Alcohols, amines, ether and water. The energy required for this
transition is 180-190 nm.
3. π → π * transition: The unsaturated hydrocarbons, carbonyl compounds, cyanides and azo
compounds will undergo this type of transition. Ex: Alkenes, Alkynes, Aldehyde and Ketone. The
energy required for this transition is very low (i.e. very longer wavelengths).
4. n → π * transition: The carbonyl compounds will undergo this type of transition. Ex:
Aldehydes, Ketone and cyanide.
The differences between π → π * and n → π *

S.No. π → π * n→π*
1 Allowed transition Forbidden transition
2 High energy transition Lower energy transition
3 Molar extinction coefficient (ε) Molar extinction coefficient (ε)
value lies between 100 to 10000 value is < 100
4 More intense than n → π * More intense than π → π *
 10. Mathematical Derivation of Beer- Lambert’s Law
Beer- Lambert’s law:
When a beam of monochromatic radiation passes through a transparent absorbing medium, the
rate of decrease of intensity of radiation with the thickness of the absorbing medium is proportional
to the intensity of incident radiation and concentration of the medium.
dI
−  cI
dx
dI
where − = decrease of intensity of radiation with the thickness of the absorbing medium
dx
c = concentration of the absorbing medium
dI = Change in intensity of incident light (range is from I0 to I)
dx = Change in thickness of medium (range is from 0 to b)
dI
− = cdx
I
 = Molar extintion coefficient
dI
− = cdx
I
I x =b
dI
I I = −x=0 cdx
o

log[I]IIo = −c[x]0b

log I − log Io = −bc

I
log = −bc
Io
T = −bc
T = Transmittance
Io
log = bc
I
A = bc
A = Absorbance or Optical density
Beer – Lamberts Law:
The absorbance of a solution is directly proportional to the concentration of the medium when
thickness of the medium is fixed and directly proportional to the thickness of the medium when
the concentration is fixed.

11. LASER
LASER is an abbreviation for Light Amplification by Stimulated Emission of Radiation.
Properities of LASER light
1. Coherence: It is a crucial property of laser, that exists due to stimulated emission. It simply
denotes that the wavelength of the waves of emitted light is in phase. When we talk about the
ordinary light source for example LED, then it does not show the property of coherence because
it gets generated due to the process of spontaneous emission of a photon.
2. Monochromaticity: A light emitted by the laser diode is monochrome in nature that means that
it has a single wavelength.
3. Brightness: Brightness of a light is basically determined by the power per unit surface area per
unit solid angle.
4. Directionality: A laser light is highly directional this means that the light emitted by a laser
diode does not show much divergence.

Construction of Laser
Basically, every laser system essentially has an active/gain medium, placed between a pair of
optically parallel and highly reflecting mirrors with one of them partially transmitting, and an
energy source to pump active medium. The gain media may be solid, liquid, or gas and have the
property to amplify the amplitude of the light wave passing through it by stimulated emission,
while pumping may be electrical or optical. The gain medium used to place between pair of mirrors
in such a way that light oscillating between mirrors passes every time through the gain medium
and after attaining considerable amplification emits through the transmitting mirror.
 Fig 9: Basic geometry of laser cavity 1) 100% 2) 95% reflecting mirror 3) active medium 4)
Pumping source and 5) Laser output
Stimulated Emission
Let us consider an active medium of atoms having only two energy levels: excited level E2 and
ground level E1. If atoms in the ground state, E1, are excited to the upper state, E2, by means of
any pumping mechanism (optical, electrical discharge, passing current or electron bombardment),
then just after few nanoseconds of their excitation, atoms return to the ground state emitting
photons of energy
hν = E2 − E1.
Spontanious emission Stimulated emission
Before emission
During emission After emission
Excited state E2

h
h
h
E h
Incident photon

Ground state E1
atom in excited state atom in ground state

E − E = E = h
2 1

Fig 10: Representation of Spontaneous and Stimulated emission

According to Einstein’s 1917 theory, emission process may occur in two different ways, either it
may induced by photon or it may occur spontaneously.
The former case is termed as stimulated emission, while the latter is known as spontaneous
emission. Photons emitted by stimulated emission have the same frequency, phase, and state of
polarization as the stimulating photon; therefore they add to the wave of stimulating photon on a
constructive basis, thereby increasing its amplitude to make lasing. At thermal equilibrium, the
probability of stimulated emission is much lower than that of spontaneous emission (1 : 1033),
therefore most of the conventional light sources are incoherent, and only lasing is possible in the
conditions other than the thermal equilibrium.
Laser Diode
A semiconductor device that generates coherent light of high intensity is known as laser diode.
Semiconductor lasers also known as quantum well lasers are smallest, cheapest, can be produced
in mass, and are easily scalable.
Construction of Laser Diode
The active layer of undoped GaAs is placed between the P and N type of AlGaAs layers. The
thickness of this active layer is of few nanometers. The aim of sandwiching this layer in between
p and n-type layers is to increase the area of electron and hole combination. Resultantly increasing
the emitted radiation. The laser output is taken from active region of the laser diode.
Anodic

Polished p-type layer Undoped GaAs

AlGaAs (P)
Laser
AlGaAs (N)

Polished n-type layer

Cathodic

Fig 11: Laser Diode

The working of a laser diode involves 3 processes: absorption, spontaneous emission and
stimulated emission.
i. Absorption: The ground state electron will absorb energy from pumping source and excites to
the excited state. This is known as absorption.
ii. Spontaneous Emission: The excited electron decays without external influence and emits a
photon, that is called "spontaneous emission".
iii. Stimulated Emission: The excited-state atom is perturbed by an electric field of frequency, it
may emit an additional photon of the same frequency and in phase, thus augmenting the external
field, leaving the atom in the lower energy state. This process is known as stimulated emission.
Advantages of laser diode
1. The operational power in case of laser diodes is less as compared to other light emitting
devices.
 2. It is small in size thus allows better handling.
3. Laser diodes generate light of high efficiency.
Disadvantages of laser diode
1. As it provides a light of high density, thus sometimes puts adverse effects on eyes.
2. It is expensive.
Applications of laser diode
1. Telecommunication and in defence industries.
2. Optical fiber communication also uses a laser beam for signal transmission as optical fibers
requires highly focused beam.
3. It is highly used in laser printers also.
Gas Lasers
Gas lasers are widely available in almost all power and wavelengths and can be operated in pulsed
and continuous modes. Based on the nature of active media, there are three types of gas lasers.
1.Atomic Gas lasers: He:Ne Laser
2.Ionic Gas lasers: Argon Ion Laser
3.Molecular Gas lasers: CO2, N2 Lasers, Excimer lasers
Most of the gas lasers are pumped by electrical discharge. Electrons in the discharge tube are
accelerated by electric field between the electrodes. These accelerated electrons collide with
atoms, ions or molecules in the active media and induce transition to higher energy levels to
achieve the condition of population inversion and stimulated emission.
The argon-ion laser (Fig 12), one of a number of ‘ion lasers’, consists of argon at about 1 Torr,
through which is passed an electric discharge. The discharge results in the formation of Ar+ and
Ar2+ ions in excited states, which undergo a laser transition to a lower state. These ions then revert
to their ground states by emitting hard ultraviolet radiation (at 72 nm), and are then neutralized by
a seriesof electrodes in the laser cavity. One of the design problems is to find materials that can
withstand this damaging residual radiation. There are many lines in the laser transition because the
excited ions may make transitions to many lower states, but two strong emissions from Ar+ are at
488 nm (blue) and 514 nm (green); other transitions occur elsewhere in the visible region, in the
infrared, and in the ultraviolet.
 Power supply

Prism
Gas filled discharge tube

M2 M1

Fig 12: Construction of gas laser system (argon ion laser with prism-based wavelength
tuning)
Excimer Laser
Excimers are molecules such as ArF, KrF, XeCl, and so on, that have repulsive or dissociating
ground states and are stable in their first excited state. Usually, there are less number of molecules
in the ground state; therefore direct pumping from ground state is not possible. Molecules directly
form in the first excited electronic state by the combination of energetic halide and rare gas ions.
Usually a mixture of halide such as F2 and rare gas such as Ar is filled into the discharge tube.
Electrons in the discharge tube dissociate and ionize halide molecules and create negative halide
ions. Positive Ar+ and negative F− ions react to produce ArF∗ molecules in the first excited bound
state, followed by their transition to the repulsive ground state to commence lasing action. Various
excimer lasers are developed in the wavelength range of 120–500 nm with 20−15% efficiency and
up to 1 J peak and 200 W average powers. These lasers are widely used in materials processing
and characterizations as well as for the pumping of dye lasers.
Applications:
1. Refractive surgery in ophthalmology
2. Gene manipulation in bioengineering.
QUESTIONS
PART-A
1. What is an electromagnetic spectrum?
2. Draw an electromagnetic spectrum with variable energy
3. What is rotational energy?
4. Define basic principle of microwave spectroscopy
5. Write down the selection rule for rotational spectroscopy
 6. Define degrees of freedom
7. Which of the following diatomic molecules have a rotational microwave spectrum: IF, O2,
KCl, Cl2.
8. Identify the molecules that will exhibit a pure rotational absorption microwave
spectrum: N2O, NO2, CClF3, NF3, SF6, CH4, CO2.
9. What are the various types of electronic transitions.
10. What is the necessary condition for a molecule to absorb infrared radiation?
11. Calculate vibrational degrees of freedom for CO2.
12. Calculate fundamental bands for the linear molecules.
13. How many fundamental bands are observed in the IR spectrum of benzene?
14. Define spontaneous emission
15. Define stimulated emission
16. Differences between π → π * and n → π * electronic transitions
17. Define LASER
PART-B
1. Explain in detail about the classification of molecules based on moment of inertia.
2. Explain rotational spectra of diatomic molecules with energy level spectrum.
3. Explain rotational spectra of polyatomic molecules.
4. Calculate J (1 to 3) values of CO molecule.
5. Explain the types of vibrations and its diagrammatic representation.
6. Calculate the force constant of CO molecule having ῡ = 2143 cm-1
7. Explain the construction, working principle and advantages and disadvantages of diode
laser
8. Explain the electronic transitions in organic molecules with suitable examples.
9. Define Beer Lamberts law and derive its mathematical formulae.
References
1. D.N. Sathyanarayana, Vibrational Spectroscopy: Theory and Applications, New Age
International (P) Ltd, 2000.
2. J. M. Hollas, Modern Spectroscopy, 4th edition, Wiley Publishing, 2004.
3. C. N. Banwell, Fundamentals of Molecular Spectroscopy, 4th edition, Mc Graw Hill
publishing, 2017.
 SCHOOL OF SCIENCE AND HUMANITIES
DEPARTMENT OF CHEMISTRY

UNIT-III – FUNCTIONAL MATERIALS – SCYA1101

 1. Introduction
Functional Materials comprises all materials including inorganic, organic, hybrid, nano materials,
ceramics, soft materials with specific functions as
• Adaptive Materials: Materials which response to stimuli as sensors, actuators and as energy
harvesters.
• Electronic Materials: Materials like semiconductors, dielectrics, ferroelectrics,
superconductivity materials used in health care and molecular devices.
• Magnetic Materials: Materials with spintronics, superconductivity and molecular magnets
finds its application in diagnosis as body scanner as well in data storage.
• Optical Materials: Materials like lenses, mirrors, polarizers, detectors, modulators used in
photonics and in advanced optical technologies.
Of these functional materials, electronic materials have attained a giant leap in the last few decades
through the development of conducting polymers. These polymers are considered as an alternative
to semiconductor silicon based electronic technology. They can be tuned from insulating to
semiconducting to metallic by chemical modification and possess unique properties like light
weight, flexible, easier processability and fabrication. These materials have in-filtered into our
day-to-day life with a wide range of products including consumer goods like LED television,
AMOLED (Active Matrix Organic Light Emitting Diode) in cell phones display to their
applications in space, aeronautics and non- linear optics. Hence, the conducting polymers with
wide applicability and unique properties can be regarded as "Materials of 21st century".
2. Conducting Polymers
Conventional Polymers like polyethylene, polypropylene, polyvinyl chloride etc., are usually
characterized by their light weight, ease of fabrication, insulating nature have replaced materials
in several areas of application from household water bottles to rockets. Their insulating property
has been in renaissance through the invention of certain class of polymers called "Conducting
Polymers." Researchers have focused for more than a decade on the synthesis of these polymers
as they exhibit semiconducting properties. Conducting polymers possess unique characteristics in
their structure by exhibiting conjugation (those possess an extended π bond along the polymeric
back bone) and are linear in nature. The increase in conductivity in these polymers can be described
as, conventional polymers usually consists of σ bonds and the charge created on any given atom
in the polymeric chain is not mobile while in case of conducting polymer, the charges created on
the polymeric chain are mobile due to the presence extended π conjugation.
Some of the examples of conducting polymers with their properties are given in Table 1

Table 1: Characteristics of conducting polymer

Maximum
Conducting Band gap
Structure Conductivity Scm-
Polymer (eV) 1

Trans Polyacetylene 1.5 1.5 105

Polypyrrole 3.0 2000

Polythiophene 2.0 100

Polyaniline 3.6 10

Polyphenylene 3.4 1000

Polyphenylene-
2.32 1000
vinylene
Examples of Conducting Polymers
A. Polyacetylene (PA)
The first conducting polymer synthesized was polyacetylene which dates back to last century.
Polyacetylene is the simplest molecular framework possessing conjugated polymer.
In 1977, Shirakawa and his colleagues (Japan) prepared polyacetylene as shiny metallic film by
contacting acetylene gas with a soluble Ziegler-Natta catalyst and their reactions are given below.

Polyacetylene formed can exists in two isomeric forms namely

i. Cis-Polyacetylene: The hydrogen atoms are arranged on same side of C=C bond . 2)Trans
Polyacetylene : The hydrogen bonds are arranged alternatively to C=C bond.
The PA films are insoluble, infusible and are unstable in nature which renders it as an unattractive
material for technological applications.
The major resurgence in the discovery of PA has been made through collaboration with
MacDiarmid (USA) where the conductivity of the PA is increased by 10 orders of magnitude by a
process known as doping. The conduction mechanism in PA by doping was developed by Heeger.
H.Shirakawa, AG MacDiarmid and A J Heeger were awarded Nobel prize in Chemistry in the year
2000 for the discovery and development of conductive polymers. A brief biography of the Nobel
laureates is given in box 3.1.
B. Polyaniline (PAni)
Polyaniline is a aromatic conjugated polymer, synthesized by electrochemical oxidation of aniline
using ammonium peroxodisulphate or potassium iodate as oxidizing agent.

Biography of Nobel Laureates in Discovery of Polyacetylene

Alan Graham MacDiarmid was born April 14, 1927, in Masterton, New Zealand.
Coming from a self-described “poor family,” he was forced to leave high school at
age 16 in order take a part-time job after his father retired . His job allowed him to
apply himself as a part-time student and he was able to complete his B.Sc. in 1948.
MacDiarmid then received a Fulbright fellowship to attend the University of
Wisconsin, earned aa Ph.D. in 1953. MacDiarmid maintained his Chair position at
Penn until the end of his career, but also held positions at the University of Texas at
Dallas, becoming the James Von Ehr Chair of Science and Technology and professor
of chemistry and physics there in 2002.

Hideki Shirakawa (1936-) was born August 20, 1936, in Tokyo. Spending his
childhood in in the small city of Takayama, he entered Tokyo Institute of Technology in April of 1957 and
received a Doctor of Engineering degree in March of 1966. In 1979, he moved to
the University of Tsukuba, where he was appointed associate professor. He was
later promoted to full professor in 1982 and formally retired from the University of
Tsukuba as professor emeritus at the end of March 2000, shortly after being
awarded the Nobel Prize in Chemistry with Heeger and MacDiarmid.

Alan Jay Heeger was born January 22, 1936, in Sioux City, Iowa.
mathematics . After completing his B.S. in 1957, he began graduate studies
in physics at Berkeley, ultimately joining the research group
of Alan Portis After completing his Ph.D. in 1982, Heeger
moved to the University of California, Santa Barbara
(UCSB), where he still actively pursues research in conjugated materials. Learning
that MacDiarmid had some experience with sulfurnitride chemistry, he approached
him about working together on a study of this new polymer
 Polyaniline has a
unique structure consisting of an alternating arrangement of benzene rings and nitrogen atoms.
The nitrogen atoms exist either as an imine (in an sp2 hybridized state) or as amine( in an sp3
hybridized state). Depending on the relative concentration of nitrogen, polyaniline exists in three
different oxidation state.
i. Leucoemeraldine: When X=1, a completely reduced state of PAni exists, consisting of only
benzenoid amine structure.

ii. Emeraldine: When X=0.5, PAni consists of a partially reduced benzenoid amine and partially
oxidized quinoid imine.

The protonated emeraldine is green in colour and is highly conductive in nature.

iii. Pernigraniline: When X=0, PAni consists of a completely oxidized quinoid imine structure.
 3. Electrical Conductivity in Conjugated Conducting Polymers
The electrical conducting in conducting polymers is different from inorganic semiconductors in
two aspects:
1. Polymers are macromolecular in nature and lack long range of orderliness.
2. Doping in a polymer is a charge-transfer process.
Doping
Doping involves a partial redox or non-redox reaction (acid reaction) occurring at the polymeric
chain. It is carried out by exposing the polymeric film or powder to dopants. Dopants are chemical
species or agents which are used in doping process. a ) Redox doping is of two types
i. p-Doping (oxidation Doping): It is an oxidation reaction where an electron is removed from the
valence band leaving the polymer with a positive charge.
Polymer + X [Polymer]n+ + Xn- X=I2, Br2, AsF5
ii. n-Doping (Reduction doping): It is reduction reaction where an electron is added to the
conduction band leaving the polymer with a negative charge.
Polymer + M [Polymer]n- + Mn+ M=Na, Li, K Naphthalide.
iii. Non-Redox doping (Protonic acid): It is an acidic reaction where a proton is added to the
polymeric chain leaving the polymer with a positive charge.
Polymer + HCl [Polymer-H]+ + Cl-
These doping reactions occur in conjugated polymers with π electrons, since the electrons can be
easily added or removed from the polymeric chain to form polyions which exhibit high electrical
conductivity.
Conduction Mechanism in Polymers
The interaction of a polymer unit cell with all its neighbours in a polymeric chain leads to the
formation of electronic band. The highest occupied electronic levels or molecular orbitals
constitute the valence band(VB) and the lowest unoccupied levels represent the conduction band
(CB). The difference in energy between the VB and CB is known as band gap energy which
determines the intrinsic electrical property of polymers. On doping, the electrical conductivity of
the polymer is increased due to the formation of self-localized excitations such as solitons, polaron
and bipolaron (quasi-particles). These particles arises from strong interaction between the charge
on the polymeric chain (electron or hole) acquired as a result of doping and the molecular structure.
Thus, the charge carrying species in doped conjugated polymers are not free electrons or holes but
quasi-particles which move relatively free through the polymeric chain.
Conduction in PA
The nature of charge carriers and the mechanism of doping in trans-polyacetylene (PA) is
explained as follows;
The trans-PA exists in two alternate structures (A and B) with same ground state energies known
as degenerate state. When these two degenerate states dimerizes, a structural defect (kink) occurs
in the chain with a change in bond alternation. A single unpaired electron exists where the
structural defect occurs and it produce an energy level at the centre of the band gap, known as
neutral, positive or negative soliton. The neutral soliton carries a single electron which possess 1/2
spin and exhibit paramagnetic behaviour. It can move along the chain without any distortion. In a
pure (undoped) trans PA, there are only neutral solitons which are on an average of 1 in every
3000 CH units.

Fig 1: A) and B) Degenerate States of trans-PA C )PA chain with a defect (neutral, Positive and Negative
soliton)
When trans-PA is doped a number of neutral solitons is used (at very low doping level) to form
charged solitons. In some cases, a charge transfer can occur directly between a doping agent and
VB or CB to produce an ion radical in the chain (i.e a defect pair). The mechanism of p and n-
doping in trans-PA is as follows and the reactions are given in Fig 2.
During doping, an electron is added (or removed) to the bottom of the conduction band (or from
the top of the valence band) of trans-PA, the conduction (valence) band is partially filled and a
radical anion (or cation), polaron is formed. The formation of polaron causes the injection of states
from the bottom of the CB and top of the VB into the band gap. The polaron carries both charge
and spin exhibiting paramagnetic behaviour. The addition (or removal) of second electron on the
chain with a negative (positive) polaron results in bipolaron (spinless). The bipolaron further lower
their energy by dissociating into two spinless charged soliton (positive charge in p-doping and
negative charge in n-doping)which occupies at one-half of the band gap energy. The number of
polaron, bipolaron and soliton formed increases with the doping level. At high doping, polaron,
bipolaron and soliton near to the individual dopant ions could overlap leading to new band between
(or even overlapping) the VB and CB through which electrons can flow. Doping of trans-PA by
I2/CCl4 introduces positive charges which is delocalized over 12-15 CH units to give positive
soliton thereby the conductivity increases from 10-7 to 103 S/cm (or by the order of 1010).

Conduction in PAni
The emeraldine base of polyaniline consists of equal proportion of amino (-NH-) and imine (=N-
) sites. On doping with acids like HCl, dl-camphor sulphonic acid as given in Fig 3, the imino
nitrogen are protonated to form bication salt, bipolaron. It is highly unstable due to the presence
of C=N bonds of quinoid imine which dissociates to form polaron. The positive charges on the
polaron are delocalized over the entire polymeric chain which are stabilized by resonance. The
resulting emeraldine salt has a conductivity of 300 S/cm, increased by the order of 1011 magnitude.

Fig 2: a) p-doping b) n-doping in trans-PA

In general, polymers forming soliton energy level can accomodate either 0, 1 or 2 electrons with
unusual spin and charge property. When the electrons are removed (i.e) Zero, a positive soliton
of zero spin results. When two electrons are accommodated, a negative soliton of zero spin is
observed. Both these charged solitons are non-magnetic. A neutral soliton carries a single electron
and exhibits paramagnetic behaviour.

Fig 3: Protonic acid doping in Polyaniline.

Conduction Conduction
Band Band

Valence Band Valence Band Valence Band

a) S0 b) S+ c) S-
Fig 4: Charge and spin separation in a) Neutral Soliton (S0), b) Positive Soliton (S+) c)
Negative Soliton (S-)
Factors influencing the electrical conductivity
The conductivity in organic polymers is influenced by the following factors:
1. Conjugation length: Conductivity of the polymer increases with the increase in the length
of the polymer chain as well as the number of conjugation.
2. Doping level: Conductivity of the polymer increases with increase in doping level until the
saturation point.
3. Temperature: Conductivity of the polymer increases with increase in temperature and
becomes constant at a particular temperature.
4. Frequency: Conductivity increases with increase in frequency of current.
Applications of conducting polymer
• In rechargeable light weight batteries
• In optically display devices.
• In electronic devices such as diodes, transistors.
• In solar cells, drug delivery system for human body.
• In molecular wires and switches.
• In photovoltaic devices.
• In antistatic coatings for clothing.

4. Organic Solar Cell (osc)

The process by which light is converted into electricity using conducting polymers is the basis of
photovoltaics. A photovoltaic cell consists of a silicon PN junction diode with a glass window at
the top surface of P material with nickel plated ring act as positive terminal (anode) and a metal
contact at the bottom act as cathode as shown in Fig 5.
Working of Photovoltaic cell
When solar light falls on the photovoltaic cell, the photon excites some of the electrons in the
semiconductor to form electron-hole (negative-positive) pairs. since there is an internal electric
field (due to p-n structure) these pairs are induced to separate. As a consequence, electrons move
to the negative electrode while the holes move to the positive electrode. A conducting wire
connects the negative electrode, load and positive electrode in series to form a circuit. As a result,
current is generated and is applied to the external load.
 Fig 5: Structure and working of Solar photovoltaic cell
Organic solar cell (OSC) possess same architecture as photovoltaic cell except the PN junction
diode is replaced by the doped conducting polymer. The advantages of organic solar cell (OSCs)
are it offers low cost solution processing, flexible substrates and high speed processing. The major
disadvantage of OSC is the low power conversion efficiency.
Structure of OSC
All organic solar cells have a planar layered structure where the organic active layer is sandwiched
between two different electrodes, one of them is transparent conductive Indium tin oxide (ITO)
and the other electrode is aluminium. The polymer solar cells have different architectures.
i. Single layer cell: An organic polymer is sandwiched between two electrodes. The photoactive
region is very thin and the positive and negative photoexcited charges travel through the same
material where recombination losses are high.
 Electrode I
(ITO, Metal)
Conjugated Polymer

Electrode 2
(Al, Mg, Ca)

Fig 6: Single Layer organic solar cell.

ii. Bi-layer cell: The sandwiched organic polymer consists of two constituents, electron donor and
electron acceptor layer at ITO and Al electrodes respectively. The donor constituents are
conjugated polymers of PPV, polythiophene and their derivatives with low band gap energy. The
electron acceptor materials are C60 and conjugated polymer with cyano group having strong
electron affinity. The lowest occupied molecular orbital (LUMO) level of donor material should
be 0.3 -0.4 eV higher than that of acceptor.

Electrode I(ITO, Metal)

Electron Donor
Electron Acceptor
Electrode 2
(Al, Mg, Ca)

Fig 7: Bi Layer organic solar cell.

iii. Bulk heterojunction: The organic polymer consists of a nanoscale blend of donor and acceptor
materials. The size of the blend is of nms allowing excitons to dissociate at the interface. It requires
a percolating network that allows charge separation to occur. It has an advantage over other
structures as they can be made thick enough for effective photon absorption.

Electrode I(ITO, Metal)

Dispersed Heterojunction
Electrode 2
(Al, Mg, Ca)

Fig 8: Dispersed heterojunction organic solar cell.

Principle and Working of OSC
The process of conversion of light into electricity by organic polymers takes place in following
steps:
1. Exciton generation
2. Exciton diffusion
3. Exciton dissociation
4. Charge transport.
1. Exciton Generation: Absorption of photon from the solar spectrum by organic conducting
polymers with bandgap energy 1.1eV - 2.0 eV produces electrostatically coupled electron-hole
pairs called excitons.
2. Exciton diffusion: The photogenerated excitons are characterized by small life time of few
picoseconds which limits the mobility of excitons to 5-10nm called exciton diffusion length. As
the excitons are dissociated within this range, exciton diffusion length play a crucial role in the
performance of the OSCs.
3. Exciton dissociation: It refers to splitting of electrostatically bounded electron-hole pair into
free charges. The dissociation of excitons occurs at the donor-acceptor interfaces or junctions. The
donor and acceptor materials are designed in such a way that there exists a difference in LUMO
levels of the donor and acceptor materials. For efficient dissociation, the difference in energy level
of LUMO of donor and acceptor should be higher than that of exciton binding energy.
∆(LUMOD- LUMOA) >exciton binding energy.
4. Charge transport: The charges produced travel through specific electrode materials which are
connected to external circuit. The donor material serves to transport holes while the electrons travel
within the acceptor material.
 Fig 9: Principle and Working of Organic solar cell.
Advantages of OSC
• The cells are light in weight, flexible and semi-transparent in nature.
• They are 1000 times thinner than silicon solar cells.
• They are easy to integrate and offers short energy payback time.
Disadvantages of OSC
• Low efficiency compare to silicon solar cells.
• They are stable in dark but degrade in light conditions.
• Lifetime is less compare to silicon cells as they degrade rapidly in moisture and air.
3.4.3 Applications of OSC
• Portable power supply.
• Emergency power source.
• Electric Fences.
• Toys, calculator and watches.
 5. Organic Light Emitting Diode(oled)
Light Emitting Diode (LED) works on the principle of electroluminescence ( The process of
converting electricity to light energy is known as electroluminescence.) An electroluminescent
structure presented in Fig 10 consists of 4 layers, two inorganic electroluminescent material
(doped semiconductor) capable of emitting electrons and holes with two electrodes.

Fig 10: Structure of Electroluminescent Cell

One of the electrode, anode is Indium Tin oxide (ITO) and the other is a metallic layer act as
cathode. On applying voltage, holes and electrons are created on the luminescent material
connected to anode and cathode respectively. The emission of light occurs by radiative
combination of electron-hole pair to form exciton. The relaxation of excess exciton energy occurs
by the emission of monochromatic light. When the electroluminescent doped semiconductor is
substituted by conjugated polymer with same functionality, the LED is referred as organic light
emitted diode (OLED).
Structure of OLED
An OLED is a light emitting diode consists of emissive electroluminescent organic film which
emits light in response to electric current. The construction of single layer OLED is represented
in Fig 11. An OLED consists of a glass substrate which is coated by a transparent ITO, act as
anode. A conjugated polymer (Poly phenylenevinylene (PPV) or Poly alkyl thiophene (PAT) or
Poly ethylene dioxythiophene(PEDOT)) is deposited onto the substrate by spin coating technique.
On the top of the polymer layer, a metallic layer of Al or Ca is deposited by vacuum evaporation
, forms the cathode. By applying bias voltage at the electrodes, emission of light is obtained
through the transparent electrode.

Fig 11: Structure of single layer Organic Light Emitting Diode.

Components of OLED
1. The components of OLED consists of
2. Substrate : It may be plastic, glass which holds the OLED.
3. Transparent Anode: It is a transparent material of ITO which injects holes to the polymeric
material .
4. Conjugated Polymer: It is an emissive layer where light is emitted. eg: PPV, PAT,
PEDOT.
5. Hole transport layer: It is placed between anode and emissive layer in order to increase the
hole transport. eg: Triphenyl amine derivatives.
6. Electron Transport layer: It is placed between cathode and emissive layer and act as hole
blocking layer. eg: 1,3,4-Oxadiazole derivatives.
7. Cathode: A metallic layer of Al or Ca which injects electrons to the polymeric material.
Working of OLED
According to Su, Schrieffer and Heeger theory, electron-electron interactions are neglected and
the electroluminescent properties of polymeric substances are based on strong electron-phonon
interactions. Based on this theory, for non-degenerate ground state polymers, injection of charges
leads to the formation of either singly or doubly charged polarons. Neutral species, excitons can
be generated either by the fusion of two polarons with opposite charges or by photoexcitation due
to electron-hole separation. The steps involved in the operation of OLED is as follows and is
illustrated in Fig 12
 1. By applying bias voltage, charges of opposite sign are injected into the active polymeric
material to form positive and negative polarons (P+ and P-).
2. The charges (P+ or P-)move in the polymer towards oppositively charged electrode,
driven by electric field.
3. Polarons of opposite sign combine to generate excitons.
4. The excitons undergoes radiative combination by the emission of monochromatic light.

Fig 12: Working of Organic Light Emitting Diode.

The factors controlling the polymeric structures are as follows and it plays a significant role in the
development of OLEDs.
1. The band gap of the conducting polymer should be in the range of 2.0- 3.0 eV, is
responsible for electroluminescence.
2. The electron affinity and ionization potential of the polymer strongly affects the injection
of charges into the electrode.
3. The solid state packing of the polymer influences the stability and emission efficiencies of
the polymer.
4. The surface polarity of the polymer is responsible for the adhesion between the active
polymer and the electrodes, an important factor in charge injection.
5. The active polymeric layer is resistant to oxidation and temperature for the lifetime of the
device.
Advantages of OLED
1. Light weight, flexible and can be easily processed.
2. High Resolution and high reliability.
3. Consumes less power.
4. Highly energy efficient.
5. High levels of brightness and intensity.
Disadvantages of OLED
1. OLEDs exhibit colour imbalance on long usage due to the lifetime of the organic
materials.
2. Expensive in nature.
3. Poor resistance to water and moisture.
Applications of OLED
1. Used in flat panel display screen such as cell phones, laptops, digital cameras.
2. Used in remote controls, indicator lights.
3. Used in fibre data communication.

6. Liquid Crystals
Liquid crystals possess unique properties and play an important role in modern technology. In
1988, an Austrian botanist , Friedrich Reinitizer observed that a material, Cholesteryl benzoate
shows two melting points. On heating the solid benzoate, it changes into a hazy liquid which on
further heating becomes a clear transparent material. Liquid crystals are characterized by rod-like
molecular structure with strong dipole and rigidity along the molecular axis. The tendency of the
molecules (mesogens) in liquid crystal points to a common axis, called director leads to a condition
called anisotropy.
Liquid crystals are highly anisotropic fluids which exists between the boundaries of a solid phase
and conventional liquid phase. The structure of the liquid crystal is described by the following
parameters:
1. Positional Order: The average molecules or group of molecules exhibits translational symmetry.
2. Orientational Order: The molecules align along the director axis on a long-range basis.
3. Bond orientational order: The adjacent molecules are joined by the line without regular spacing.
 (a) Solid (b) Liquid Crystals (c) Liquids
Fig 13: Molecular orientations in different States of matter.
The chemical structure of the liquid crystal consists of
1. Long, narrow elongated molecules with molecular interaction leading to attraction between the
molecules. The most common liquid crystal molecule are of the type:

A central core of benzene rings is linked by X, may be diazo, azoxy, nitrones, esters or Schiff
bases. The end groups R1 and R2 may be alkyl, alkoxy or acyl group.
2. Presence of unsaturation in their structure increases the polarizability as well as intermolecular
attractions for the formation of mesophase.
3. Presence of carboxylic groups at the end of the chain and the absence of bulky functional groups
are responsible for the stability of the liquid crystal.
Thermography

Liquid F G
Temperature

Liquid crystalD E

Solid B C
A

Time

Fig 14: Thermographic behaviourof a solid showing mesomorphism

The phase change observed on heating a solid showing mesomorphic behaviour is represented in
the form of temperature-time graph known as thermography. On heating a solid, its temperature
starts rising until it changes to liquid crystal as shown by the curve AB in Fig 14.
The temperature now remains constant as long as both the phases (solid and Liquid crystal) are
present as presented by the curve BC. When the solid completely changes to liquid crystal, the
temperature again starts rising as seen in curve CD until the liquid crystal changes to liquid. The
temperature remains constant as long as the two phases (liquid crystal and liquid) are present
together as seen in curve DE. When the liquid crystal completely changes to liquid, the
temperature again starts rising (curve EF) and continues till it reaches a vapour state. The
temperature again becomes constant as long as the liquid and vapour are present together (Curve
FG).
Classification of Liquid Crystal
Liquid crystals are states of matter consisting of long range molecules, exhibiting optical activity,
ability to form mono crystals in the presence of electric or magnetic field and are sensitive to
temperature. They are broadly classified into two types:
1. Thermotropic liquid crystals: They are formed by the variation of temperature and is of three
types: a. Nematic structure b. Cholesteric structure C. Smectic
a) Nematic Structure: The molecules in nematic structure are arranged parallel or nearly parallel
to each other along the long molecular axes. The structure is one dimensional and are mobile in
three directions. It is the highest temperature mesophase in thermotropic liquid crystal. The
molecules possess no translational order with rod-like molecules tend to align parallel to each other
with uniaxial symmetry. Eg: p-methoxybenzylidene-p'-n-butyl aniline (MBRA), p-azoxyanisole
(PAA), p-n-hexyl-p'-cyanobiphenyl, p-quinquephenyl.
b) Cholesteric Structure: It is composed of nematic mesogenic molecules containing a chiral
centre, which produces intermolecular forces that favours alignment between molecules at a slight
angle to one another. It is a stack of two-dimensional nematic -like layers forming a continuous
helical pattern. A byproduct of the helical structure has the ability to selectively reflect colour
light at wavelength in the visible spectrum equal to the pitch length ( the distance the director
takes to rotate one full turn in the helix). Eg: Cholesterylnonanoate, 2-methylbutyl-pp(p'-
methoxybenzylidene-amino) cinnamate.
c) Smectic structure: The word "smectic " is derived from the Greek word for soap. The molecules
show a degree of translational order and tend to align themselves in layers or planes. There are
eight sematic structures observed and their properties with characteristics are given in the Table.
3.2
 Fig 15 : Molecular Orientation in Smectic, Nematic and Cholesteric phase.

Table 3.2 Characteristic Features of Smectic A-H Liquid crystal structures.

Optical Properties
Unstructured
Optical
Smectics Molecular Organization Textures
figure
Smectic A Layer structure, Molecular axes are Uniaxial Focal conic (Fan
orthogonal to the layers, Random Positive shaped or polygon),
arrangement of mesogens within the Homogeneous,
layers. pseudoisotropic
Eg: ethyl p-(p'-phenylbenzal amino)
benzoate
Smectic C Layer structure, Molecular axes are titled Biaxially Broken focal conic,
to the layers, Random arrangement of positive Homogeneous
mesogens within the layer Eg: p-n-
octyloxybenzoic acid
Smectic D Cubic Eg: p'-n-octadecyloxy-3'- Isotropic Mosaic
nitrodiphenyl-p-carboxylic acid
Smectic F Layer structure Uniaxially Broken focal conic
Eg: 2-(p-pentylphenyl)5-(p- positive with concentric axes
pentyloxyphenyl) pyrimidine
Structured Smectics
 Optical Properties
Unstructured
Optical
Smectics Molecular Organization Textures
figure
Smectic B Layer structure, Molecular axes are Uniaxial or Mosaic,
orthogonal or titled to the layers, biaxial pseudoisotropic and
hexagonal arrangement of mesogens positive Homogeneous
within the layers.
Eg: ethyl p-ethoxybenzal-p'-
aminocinnamate
Smectic E Layer structure, Molecular axes are Uniaxial Mosaic,
orthogonal to the layers, ordered positive pseudoisotropic
arrangement of mesogens within the
layers.
Eg: diethylp-terphenyl-p,p"-carboxylate

Smectic G Layered structure with ordered Uniaxial Mosaic

arrangement within the layers positive
Eg: 2-(p-pentylphenyl)-5-(p-
Pentyloxyphenyl) pyrimidine
Smectic H Layered structure with ordered Uniaxial or Mosaic
arrangement within the layers biaxial
Eg: 4-butyloxybenzl4-ethylaniline positive
2. Lyotropic Liquid crystal: Lyotropicmesophases occur in concentrated solution of rod-like
molecules in an isotropic solvent , water. They are important in soaps, gels and colloids. The
amphiphilic soap molecules are arranged in bilayer structure with a minimum contact between the
hydrocarbon chain and the water molecules.
There are also lamellar, cubic and hexagonal arrangement of amphiphilic molecules in water
solution. Eg: sodium stearate, α-Lecithin
 7. Liquid Crystal Display(LCD)
Liquid crystal technology has been applied in many areas of science and device technology. They
are used as displays in digital wrist-watches, calculators, television displays and panel meters.
They can be used to record, store and display images.
The liquid crystal cell design shown in Fig 16 consists of a thin film of liquid crystal at room
temperature which is sandwiched between two electrodes (glass coated with metal or ITO).
The thickness of the liquid crystal film is 6-25 micrometers and is controlled by a glass spacer
which is chemically inert. The cell is hermetically sealed in order to eliminate oxygen and moisture
both of which chemically attacked by the liquid crystal.
Principle
A thin film of liquid crystal is placed between two sheets of glass, one of which is coated with an
electrically conductive material (electrode) as shown in Fig 17. When an electric current is not
applied, the molecules are uniformly oriented so that the light can pass through the cell. When
the current is applied, the molecular alignment changes and the cell appears opaque or dark. Hence,
a number is displaced in black against a silvery background.

Fig 16: Design of

Liquid crystal cell.
Fig 17: Principle of Liquid Crystal cell. (a) Light passes through Nematic crystal (b) Light
is scattered due to disorderliness of the molecules.
Working
The cell with the nematic liquid crystal is placed between the two crossed polarizer as shown in
Fig 18. Polarized light entering the cell follows the twist of the nematic liquid crystal and is
rotated 900 allowing the passage of light through the second polarizer. When an electric field is
applied, the molecular alignment in the liquid crystal changes in such as a way that polarization is
not altered and no light is transmitted. Hence, if a mirror is placed behind the second polarizer it
appears black or if a electrode is shaped in a numeric pattern of segment is placed , then a
numeric display will appear on a black back ground on applying the current.

(a)

(b)
Fig 18: Working of Liquid crystal display . (a) in the absence of electric field (b) in the presence of electric field.
There are two modes by which liquid crystal operates namely 1) Dynamic scattering and 2) field-
effect scattering.1) In dynamic scattering, when the electric field is not applied, the cell containing
twisted nematic liquid crystals is transparent. On applying the electric field, the cell becomes
opaque. The cell is prepared by rubbing the glass surface directionally or by chemically treating
the surface by adding a chiral compound to nematic liquid crystals. Digital display are made by
photoetching a seven-segment pattern onto one of the ITO coated onto glass electrodes. 2) In
Field-effect display is mostly used in watch and pocket-calculator displays. A liquid crystal watch
displays hours and minutes, the quartz crystal controls the oscillating circuit with a frequency of
32,768 Hz. Each of the time pulses is decoded to give outputs that are needed for seven-segment
display.
Advantages of LCD
• Less power consumption
• Better clarity even in the presence of bright light.
Disadvantages of LCD:
• LCD can be viewed up to 1650 and the picture suffers from side.
• Non-flexible .
Compare and contrast between LCD and OLED.
• OLEDs displays are light in weight, flexible and are in deeper-blacks compare to LCD.
• OLED offers a much better viewing angle at 1700 while LCD can be viewed up to 1650
and the picture suffers from side.
• OLEDS offers high contrast ratio, sharper picture and fast response time compare to LCD.
• OLEDs consumes less power than LCD.
• No geographical constraints with OLED while LCD screens lose contrast at high
temperature and lose brightness and speed at low temperature environment.
• OLED consists organic compounds which emits light in response to electric field while
LCD uses twist and untwist mechanism in response to electric field.
• Both OLED and LCD are vulnerable to water damage and degrades more rapidly in the
presence of oxygen.
• Both OLED and LCD have poor readability and display in bright ambient light.
• Pixels get stuck in both OLED and LCD either through usage or during initial
manufacturing process.
QUESTIONS
PART-A
1.What are conducting Polymers?
2.Define doping.
3.Give the isomeric forms of PA.
4.Draw the different oxidation states of polyaniline.
5.What are solitons?
6.Differentiate soliton and polaron.
7.Define Electroluminescence.
8.Give the merits and demerits of OLED.
9.What are excitons?
10. What is an organic photovoltaics?
11. What are the advantages and limitations of OSC?
12. What are liquid crystal?
13. Classify liquid crystals.
14. Differentiate between thermotropic and lyotropic liquid crystals.
15. Compare OLED and LCD.
PART-B
1.Describe the synthesis of polyacetylene and explain its isomeric forms.
2.Describe electronic conduction in conjugated conducting polymers.
3.Explain in detail the mechanism of p-doping in trans-PA.
4.Explain in detail the mechanism of n-doping in trans-PA.
5.Describe the mechanism of protonic acid doping in polyaniline.
6.Explain the principle, construction and working of OLED.
7.Describe the construction and working of OSC.
8.Explain in detail the classification of liquid crystals with their characteristics.
9.Give a detailed account on liquid crystal display.
10. Write short note on polyaniline.
References
1. Y. Li. (Ed.) Organic optoelectronic Materials, Springer Publications, 2015.
2. A.K. Bakshi and GeetikaBhalla , Electrically conducting polymers: Materials of the twenty
first century, J SciInd Res., 2004 , Vol.63, pp. 715-728.
3. S. Ramakrishnan, Conducting polymers - From laboratory curiosity to the market place,
Resonance, 2011, Vol.2,December, pp.1254-1265.
4. Bredas_Jl, Street_ Gb, Polarons, Bipolarons and solitons in conducting polymers,
"Accounts of chemical research,1985, Vol.18 (10) pp.309-315.
5. B.R. Puri, L.R. Sharma and Madan S. Pathania, Principles of Physical Chemistry, 47th
Edition, Vishal Publishing Company, 2018.
6. P.C.Jain and Monika Jain, Engineering Chemistry, 16th Edition, DhanpatRai Publishing
company, 2016.
7. Kalluri R. Sarma, "Liquid crystal Displays" in Hand book of conducting polymers. CRC
press LLC, 2000.
 SCHOOL OF SCIENCE AND HUMANITIES
DEPARTMENT OF CHEMISTRY

UNIT-IV – Carbon Materials for Health, Stealth & Energy – SCYA1101

 1. Introduction to Carbon and its Materials
Carbon (C) is a nonmetallic element belonging to Group 14 (IV a) of the periodic table. Though
it makes only upto 0.025% of the earth’s crust, it forms more compounds than all the other
elements combined. The cosmic product of the “burning” of three helium nuclei of atomic number
4 is the carbon nucleus of atomic number 12. Elemental carbon is a minor component on the earth’s
crust. However, carbon compounds form minerals such as dolomite, magnesite, marble and
limestone by combining with the carbonates of calcium and magnesium. Carbon occurs widely in
the form of coal and as organic compounds in the form of petroleum, natural gas, plant and animal
tissue. Carbon gets recycled through carbon cycle where the carbon dioxide present in the
atmosphere is converted into carbohydrates by plants during photosynthesis and the reverse
reaction of the release of the carbon dioxide back into the atmosphere during metabolism by
animals. More than a million carbon compounds are known to exist and several new carbon
compounds are getting added to the already existing list on a day to day basis. This diversity and
complexity is due to the tendency of carbon atoms for bonding with each other in forming ring,
chain and three dimensional conformations and also due to its capacity to bond with other atoms.
Allotropes of Carbon
Elemental carbon exists in several forms having different physical properties. The well known
allotropes are graphite and diamond. They differ in their physical properties due to differential
arrangements of carbon atoms in their structure. Diamond and graphite occur naturally on earth
and are chemically inert. Diamond (composed of a three-dimensional crystalline array of carbon
atoms) is the hardest naturally occurring substance and is a poor conductor of heat and electricity.
Graphite (composed of stacked sheets of two-dimensional hexagonal arrays of carbon atoms), on
the other hand, is soft and slippery and is a good conductor of heat and electricity. The third
allotrope of carbon is fullerene, consisting of a variety of molecules made of only carbon atoms.
Spheroidal, closed-cage fullerenes are called buckminsterfullerenes or buckyballs. Cylindrical
fullerenes are called carbon nanotubes (CNTs). They were discovered in 1985 while simulating
the chemical reactions occurring in the atmosphere of giant stars under laboratory conditions.
Fourth form of carbon molecule which is crystalline and magnetic is the Q-carbon. They are also
synthetic and the scientists have speculated its formation within the planetary cores containing hot
environmental conditions. Other types of carbon molecules which are amorphous or are less
crystalline are carbon black, charcoal, lamp black, coal and coke.
 2. Fullerenes
Fullerene or Buckminsterfullerene denotes a series of hollow carbon molecules forming either a
closed cage (“buckyballs”) or a cylinder (carbon “nanotubes”) structure. Fullerene was found to
have the structure of a truncated icosahedron and was first discovered by Sir Harold W. Kroto,
Richard E. Smalley and Robert F. Curl in the year 1985. During an experiment with laser to
vaporize graphite rods in the atmosphere of helium, the chemists obtained a cage like molecules
composed of 60 carbon atoms (C60) joined by single or double bonds to form a hollow sphere
comprising of 12 pentagonal faces and 20 hexagonal faces, a structure resembling a soccer ball.
The C60 molecule was named buckminsterfullerene (or buckyball) after the American architect R.
Buckminster Fuller constructed a geodesic dome on the same structural principles. The most stable
form of a carbon aggregate containing several thousands of atoms is found to be the closed bucky
ball. Discovery of fullerenes have led to an entirely new understanding of the behavior of sheet
materials and their properties.

Fig 1: Buckminsterfullerene (C60)

Studies on fullerenes indicated that C60 and C70 are exceptionally stable and provided convincing
evidence for the cage structure proposal. There were developments in the discovery of other
metastable species, such as C28, C36, and C50 and also confirmed the presence of “endohedral”
complexes, in which an atom is trapped inside the cage and the size of the entrapped atom
determining the size of the smallest surrounding possible cage.
Fullerenes are the only pure, finite form of carbon which due to its high symmetry, need no atoms
to satisfy their surface chemical bonding requirements as in the case of other allotropes of carbon
such as the diamond and graphite.
Related to this are the carbon “onions” consisting of carbon cages one inside the other. They have
millions of carbon particles in dozens of concentric shells.
Preparation
The first method of production of fullerenes was by laser vapourization of carbon in an inert
atmosphere. This method resulted in the synthesis of microscopic amounts of fullerenes. In the
year 1990, a new apparatus was developed by Wolfgang Krätschmer and Donald R. Huffman
where an arc was used to vaporize graphite to produce fullerenes in substantial yield. Macroscopic
quantities of fullerenes can be synthesized by this method. Metals like alkali, alkaline earth metals
and lanthanoids can be trapped in a fullerene cage by vaporizing graphite rods impregnated with
the selected metal.
Method of Synthesis
Fullerenes are produced by Kratschmer–Huffman method. It is a straightforward and low cost
method for generating large quantities of fullerene containing carbon soot. It consists of a chamber
which is filled with helium gas at a pressure of 100 torr. An electric arc is produced by a power
supply for 10-15 seconds. This results in the vapourization of graphite to form soot inside the
chamber. The chamber is then cooled for 5-10 minutes and the pressure inside is brought down to
atmospheric pressure. By scraping the deposited soot, around 10% yield of C60 can be obtained.
The fullerenes in the soot can be extracted by dissolving it in a small amount of toluene. After
extraction, toluene is removed by rotary evaporator which leave behind a solid mixture of mostly
C60 along with small amounts of larger fullerenes. Pure C60 can be obtained by liquid
chromatography where the mixture is dissolved in toluene and by passing through a column of
activated charcoal mixture of silica gel, the magenta colored C60 comes out first followed by the
red colored C70. The colored solutions are collected separately and the toluene is removed using
rotary evaporator.
In the Krätschmer-Huffman (KH) experiment, carbon radicals are produced by slow evaporation
of a resistively heated graphite rod where the density of the carbon vapour is far lower than that
obtained with the pulsed laser vaporization. Also, the rate of cooling of the condensing carbon
vapour is much slower in the KH method that greatly assists the clustering in the critical size range
to form C60. By adjusting the helium buffer gas pressure, the rate of migration of the carbon
vapours from the hot graphite rod can be controlled for the C60 formation. The experimental factors
that can be modified to maximize the yield of the fullerene clusters in the soot are the vaporization
current density and the helium partial pressure.
Another method of synthesis involves the use of AC (alternating current) or DC (direct current) to
produce C60 and the other fullerenes in good yield and is followed in the commercial synthesis of
fullerenes.
Other techniques for the synthesis of fullerenes include hydrocarbon combustion, low-pressure
helium sputtering, electron beam evaporation and inductively coupled RF evaporation for the
vaporization of the graphite targets.

Fig 2: Synthesis of fullerenes

Properties
In fullerene, each carbon is bonded to three other carbom atoms and are sp 2 hybridised. The C60
molecule has two bond lengths – the 6:6 ring bonds are the double bonds and are shorter than 6:5
bonds. C60 molecule is not superaromatic as it tends to avoid double bonds in the pentagonal rings,
resulting in poor electron delocalization. Hence it behaves as an electron deficient alkene and
therefore reacts readily with electron rich species. The molecule can readily accept and donate
electrons. The molecule can readily add atoms of hydrogen and halogens. The halogen groups can
be replaced by other functional groups, such as phenyl, thus opening new routes to the synthesis
of wide range of novel fullerene derivatives exhibiting advanced materials behaviour.
Important crystalline compounds of C60 with alkali and alkaline earth metals have shown to exhibit
superconductivity at relatively high temperatures above 19 K. Superconductivity is observed in
the range of 19-40 K, equivalent to -254 to -233ᵒC or -425 to -387ᵒF.
Metals can be physically trapped in a fullerene cage (M@C60) and the resulting compounds have
been extensively studied. Alkali, alkaline earth metals and early lanthanoides may be trapped by
fullerenes cages by using graphite rods containing the metal.
Fullerenes are soluble in common solvents such as benzene, toluene and chloroform.

Applications
Fullerene applications are wide ranging from additives to polymers, photoconductors, photoresists
and from bio-active agents to cosmetics. Buckminsterfullerenes have a wide range of electrical
properties. It may alternately exist in insulating, conducting, semiconducting, or superconducting
forms.
• Fullerenes are active molecules and are used as antioxidants as they can readily react with
radicals due to its high affinity for electrons. This property is due to the presence of large
number of conjugated double bonds. Fullerenes have low energy unoccupied molecular
orbital and can react with a number of radicals. A single C60 molecule can interact with
upto 34 methyl radicals and therefore is called “radical sponge”. Radical sponge is added
to cosmetics for preventing skin damage and premature aging without any side effects.
• Fullerenes are used as antiviral agents. This application is due to its unique molecular
structure, antioxidant effect and biological compatibility. The important and the most
exciting aspect of fullerene is its ability to suppress the replication of human
immunodeficiency virus (HIV) so as to delay the onset of the acquired immunodeficiency
syndrome (AIDS).
• Fullerenes form conjugates with proteins and DNA which has a potential application in
developing anticancer therapy. Fullerenes get excited upon light irradiation and while
returning to the ground state they releases energy which splits up oxygen to generate singlet
oxygen that is cytotoxic in nature.
• Fullerenes are a class of inorganic carriers showing good biocompatibility, greater
selectivity, retain biological activity and can undergo easy diffusion. Fullerenes are used
in the delivery of hydrophobic drugs for their slow release with safety and great efficacy
at the site of action. The surface of fullerene is covered with a chemotherapeutic agent
which gets transported and target the cancer cell.
• Fullerene reagent forms a protective layer on DNA and helps in extending the life of DNA
of the endosomes.
• Fullerenes are excellent electron acceptors and are used in organic photovoltaic cells in
complexed and polymer forms to produce bulk heterojunctions.
• Fullerenes have optical limiting properties and are used in protective eye wear and sensors
for protecting the eyes or the sensor.
 • A Fullerene molecule can hold upto 36 hydrogen atoms during the breaking and the
formation of the C=C bonds. The color of the hydrogenated fullerenes changes from black
to brown, red, orange and finally to yellow depending on the increase in the hydrogen
content. These materials are highly promising in the development of a better, safer and
more efficient hydrogen storage devices.
• Fullerenes can form lightweight metals with greater tensile strength without compromising
on the ductility of the metal. This is due to the small size and high reactivity of the sp2
hybridized carbon atom. This enables dispersion strengthening metal matrix by the
interaction of fullerenes with the metals.
• Closed fullerene structures containing sulfides of tungsten and molybdenum are found to
exihibit excellent solid-lubricant properties. They act as dry lubricants in coating
application.
3. Vander Waals Solid
A. Graphene
Graphene is the thinnest compound known to man at one atom thick. It is the lightest material
known (with 1 square meter weighing around 0.77 mg), the strongest compound discovered (100-
300 times stronger than steel with a tensile strength of 130 GPa and Young’s modulus of 1 TPa),
the best conductor of heat at room temperature and also the best conductor of electricity. Graphene
has uniform light absorbing ability across the visible and near-infrared parts of the spectrum.
Structure of Graphene
Graphene is a monolayer of carbon atoms, tightly bound in a honeycomb lattice. It is an allotrope
of carbon in the form of a plane of sp2 hybridized carbon atoms with a molecular bond length of
0.142 nm. Layers of graphene stacked on top of each other form graphite with an interplanar
spacing of 0.335 nm. The layers of graphene are held together by van der Waals forces, which can
overcome during exfoliation of graphene from graphite.

Fig 3: Structure of Graphene

Preparation
Graphene was synthesized first by chemical vapour deposition (CVD) method. CVD method is an
expensive and complex process which involves the use of toxic chemicals to grow graphene as a
monolayer by exposing platinum, nickel or titanium carbide to ethylene or benzene at high
temperatures. This method had many drawbacks that made graphene unavailable for
developmental research and commercial uses. However, studies on the graphene’s interfacial
adhesive energy has proved the possible separation of graphene effectively even from metallic
surfaces thereby reducing the toxic waste that gets generated during the synthesis. Consistent
research is being carried out to produce graphene on custom substrates with control over impurities
such as ripples, doping levels, domain size and relative crystallographic orientation of the graphene
layers.
B. Graphene Oxide
Graphene oxide is a material consisting of a monomolecular layer of graphite with various oxygen
functionalities such as epoxide, carbonyl, carboxyl and hydroxyl groups. Graphene oxide is an
exfoliated form of graphite oxide in water using sonification, ultimately producing single or few
layer of graphene called graphene oxide (GO). Graphene oxide is a dispersion consisting of a few
layers of flakes or monolayer flakes. The most common method of producing graphite oxide is the
Hummers or the Offeman method in which graphite is treated with a mixture of sulphuric acid,
sodium nitrate and potassium permanganate. Most common method of preparation of graphite
oxide is by the oxidation of graphite using oxidising agents like potassium permanganate in
sulfuric acid. Sodium nitrate is now replaced with a combination of phosphoric acid and sulphuric
acid and has been found to be more efficient with an increase in the oxidation level upto 70%.
Graphene oxide is a by-product of this oxidation where the interplanar spacing between the layers
of graphite gets increased. The main difference between graphite oxide and graphene oxide is the
interplanar spacing between the individual atomic layers of the compounds, caused by water
intercalation which disrupts the sp2 bonding network and thereby making it an electrical insulator.
During oxidation, oxygenated functionalities are introduced in the graphite structure which not
only expand the layer separation but also makes the material hydrophilic. The main difference
between graphite oxide and graphene oxide is, thus, the number of layers. Chemical reduction of
graphene oxide is currently viewed as the most suitable method of mass production of graphene.
Properties
The important advantage of graphene oxide is its easy dispersibility in water and other organic
solvents. Its dispersibility in different matrices, due to the presence of the oxygen functionalities,
is a very important property while mixing the material with ceramic or polymer matrices for the
improved mechanical and electrical properties. Graphene oxide’s properties can be altered by
introducing functional groups which results in a chemically modified graphenes with more
adaptable properties and makes it useful for various applications.
For example, substituted amines are introduced for the organic covalent functionalization in order
to increase the dispersibility of the chemically modified graphenes in organic solvents for its
utilization in optoelectronics.
C. Reduced Graphene Oxide
Reduced graphene oxide (rGO) is prepared by reduction of graphene oxide by thermal, chemical
or electrical treatment methods. It can also be prepared by reducing the electrically insulating
graphene oxide using hydrazine. Due to the toxic nature of hydrazine, alternatives to hydrazine
including NaBH4, ascorbic acid and HI have been used. Different reducing agents results in various
carbon to oxygen ratio and chemical compositions in rGO. Electrochemical reduction of graphene
oxide is a method that has been shown to form very high quality reduced graphene oxide, having
identical structure similar to pristine graphene. The reduced graphene oxide resembles graphene
and there is always some oxygen functional groups inside or on the surface of the reduced graphene
oxide causing structural defects.
Properties
rGO can be made as a thin film from an aqueous dispersion of GO in water and has moderate
conductivity. Hence it is attractive for use in electronic devices. Graphene oxide act as an electrical
insulator due to the disruption of the sp2 bonding networks. For increasing the conductivity,
graphene oxide has to be reduced during which the honeycomb hexagonal lattice would be
recovered. This reduced graphene oxide is difficult to disperse due to its tendency to form
aggregates.
Applications
Carbon forms the basis for all known life on earth, making graphene potentially an eco-friendly,
sustainable solution for an almost limitless number of applications. Applications within different
scientific disciplines have exploded since discovery of graphene with huge impact being made in
high-frequency electronics, bio, chemical and magnetic sensors, ultra-wide bandwidth
photodetectors and energy storage and generation. Other promising areas of application are
composites, energy, telecommunications, electronics, sensors and imaging and biomedical
technologies.
Nanocomposites of rGO have been used for high capacity energy storage in lithium ion batteries.
Electrically insulating metal oxide nanoparticles adsorbed onto rGO has been found to increase
the performance of these materials in batteries. Increased energy storage capacity and cycle
stability are shown to be present for Fe3O4 on rGO compared to pure Fe3O4 or Fe2O3. Large surface
area rGO has been synthesised using microwaves for exfoliation and reduction of GO and is useful
as an energy storage material in supercapacitors.
Chemically modified graphene oxides carrying porphyrin-functionalized primary amines and
fullerene-functionalized secondary amines show increasing performances in nonlinear optics.
Graphene - Mechanical properties
Graphene, a new two dimensional material containing a monolayer of covalently bonded carbon
atoms has unique mechanical and transport properties. Graphene has high in-plane stiffness-Young
modulus and superior strength. The exceptional mechanical properties of graphene makes it a
superstrong structural and functional material.
A graphene membrane which was mechanically deposited onto a substrate was found to show both
non-linear elastic behaviour and brittle fracture. Graphene has Youngs modulus (E) of 1 TPa, a
third order elastic stiffness (D = -2.0 TPa) and an internal strength (int) of 130 GPa. Extremely
high values of E and int makes graphene an attractive material for structural and other applications.
Also, graphene can be bent easily that can be exploited in practice.
The presence of defects influence the plastic deformation and fracture. Usually observed defects
in graphene are vacancies, Stone-Wales defects, dislocations and grain boundaries. Dislocations
and grain boundaries cause the most significant effects on its mechanical properties. Dislocations
serve as carriers of plastic flow in graphene whereas, grain boundaries decreases its strength
characteristics.
According to nanoindentation measurements of graphene membranes, the upper bound for the in-
plane breaking stress is found to be 35 GPa and this value is much lower than the intrinsic strength
(130 GPa) of pristine graphene.
Bending of graphene sheet during compression has been exploited in the design of polycrystalline
graphene specimens and those with tuned folded structures are found to affect both the transport
and mechanical characteristics. This feature is also found to be interesting for the design of
nanodevices based on folded graphene specimens.
Due to ultrahigh strength of graphene, its inclusions are effectively used in the enhancement of
both strength and fracture toughness in composite materials. Nanocomposites were fabricated
using ceramic matrixes and inclusions in the form of graphene platelets (GPLs) for the improved
fracture toughness of the ceramic materials. For example, silicon nitride with 1 wt% GPL
nanocomposites with homogeneously dispersed GPLs have been fabricated in which each GPL
consisted of several graphene layers of thickness in the range of 1-10 nm. The mechanism behind
the dominant toughening are crack branching, crack deflection and crack bridging. Inclusions in
the form of graphene sheets are also found to enhance the mechanical characteristics in polymer-
based nanocomposites. Youngs modulus of the nanocomposite with 0.125% weight fraction of
graphene inclusions is found to be 65% greater than that of the graphene free counterpart.
Role of graphene inclusions in the form of sheets and platelets as strengthening and toughening
structural elements in nanocomposites is a promising breakthrough compared to nanoparticles and
carbon nanotubes.
Inspite of commendable achievements, studies on the mechanical properties exhibited by graphene
are in their infancy with many important problems yet to be explored and remain unsolved in the
new and intriguing research area related to graphene.
Graphene - Electrical properties
Graphene is used to make supercapacitors with high capacities, high power densities, longevity
and also the development of electronic components has been progressing at a high rate. Batteries
and capacitors have been limiting due to size, power capacity and efficiency. Laser-scribed
graphene (LSG) supercapacitors demonstrated power density comparable to that of high-power
lithium-ion batteries. LSG supercapacitors are highly flexible, light, quick in charge, thin and very
inexpensive to produce. Graphene is used to boost capacity, charging rate and longevity. Graphene
tin oxide as an anode in lithium ion batteries has higher potential capacity and almost no reduction
in storage capacity between charges which effectively makes technology such as electronically
powered vehicles a much more viable mode of transport.
Graphene can be used to improve energy generation, including the improvement of perovskite
solar cells (PSCs) which are highly promising next-generation solar power sources with very high
efficiency. Addition of reduced graphene oxide spacer layer to a PSC, resulted in a low-cost
production of PSCs with 20% efficiency.
Graphene is used in energy storage in advanced electrodes. Graphene combined with silicon
nanoparticles form anode that maintain 92% of their energy capacity over 300 charging-discharing
cycles, with a high maximum capacity of 1500 mAh per gram of silicon. The energy density values
achieved are well above 400 Wh/kg. Thin film of graphene was produced using spray-coating
deposition technique which enabled its large-scale production for the development of
supercapacitors with very high power densities. Graphene-metal oxide hybrid electrodes exhibit
up to 1100 mAh g-1 for the first 10 cycles and the specific energy density is maintained at 1000
mAh g-1, even after 130 cycles. By hybridizing the metal oxide matrix with graphene, the
interaction between the interstitial ions and the hybrid matrix is vastly improved for enhanced
conductivity. Due to the large surface area of graphene, the metal ions can be stored via surface
adsorption and induced bonding.
Graphene is an ideal candidate for radio frequency (RF) flexible electronics. The flexible nature
of graphene allows for various electronic devices on flexible substrates such as the graphene-based
supercapacitors, wearable touch panels, strain sensors, self-powered triboelectric sensors, flexible
and robust touchscreen devices etc.
Graphene based photonic devices are becoming highly promising because of the ability of
graphene to absorb light over a large bandwidth. Graphene is an excellent heat conductor which is
highly useful in the reduction of heat consumption in graphene based photonic devices.
Graphene Hall sensors with carrier mobility in excess of 200,000 cm2V-1s-1 with current-related
sensitivity up to 5700 V/AT and voltage-related sensitivity up to 3 V/VT has been demonstrated
in graphene encapsulated boron nitride. Flexible graphene Hall sensors has been found to have
sensitivity similar to that of the rigid silicon Hall sensors.

4. Graphene based Energy Storage Devices in Space Application

Modern energy storage device for electric automobiles, small and large electronic appliances and
modern aircraft is the lithium-ion battery. The lithium-ion battery has energy densities of the order
of 100 Wh/kg and require long charging times. Ultracapacitors, on the other hand, can be recharged
in seconds. However, their energy densities are lower than that of lithium-ion batteries. Increase
in the performance of both types of devices have been made with the addition of nanostructured
electrodes to lithium-ion batteries and by the use of activated carbon in ultracapacitor electrodes.
Incorporation of the nanostructured electrodes have reduced the ion diffusion distances and
introduction of the dopants have increased the ion transport efficiency in lithium-ion batteries.
Activated carbon used in the ultracapacitors have resulted in the increase in the energy densities
which is still lower than those of the lithium-ion batteries. Development of the thin film
ultracapacitors with graphene electrodes have made possible to attain energy densities comparable
to those of thin-film lithium ion batteries and power densities comparable to those of activated
carbon ultracapacitors. The surface area of graphene is larger than that of the activated carbon,
allowing for ultracapacitors with very large capacitances. An energy storage device with these
characteristics could be used for robotic and Martian exploration missions and crewed habitats.

Graphene’s usefulness has already been established on earth and now the recent area of research
is to extend its applications in space.
One of the important possible uses of graphene in space applications is its testing in space-like
applications. Graphene was tested for its ability to enhance the performance of satellites’ cooling
systems by employing the material’s unique thermal qualities. Graphene is being used in what are
called as loop-heat pipes, which are pumps that move fluid without the need for any mechanical
parts. This mechanism is very important for space operations as there will be no wear and tear.

For space application, the metallic wick, the main element of the loop-heat pipe, would be coated
with graphene. Graphene’s thermal properties enable improved heat transfer and the porous
structure of the material increases the surface area by which the liquid comes into contact and
allows it flow through the wick. The results of this micro-gravity test revealed a high performance
of the graphene-coated wicks compared to untreated ones and the coated wicks are tested in a low-
gravity parabolic flight. With its success, researchers are working on the development of a
prototype that uses graphene on a satellite or space station for testing in space. Related to this is a
research initiative dedicated to developing new technologies based on graphene called the
“Graphene Flagship” to test graphene for light sails which could lead to a new way of propelling
satellites in space using light from lasers or the sun. “Graphene flagship” is a collaboration between
the European Space Agency and academic consortium to carry out zero gravity test during a
parabolic flight using graphene.
 5. Carbon Nanotubes
Carbon nanotubes (CNTs) are molecules consisting of rolled-up two dimensional sheets of
graphene, containing hexagons and pentagons, forming cylinder.

CNTs have carbon atoms which are sp2 hybridized and are bonded with each other forming strong
covalent bonds. This feature along with the nanotubes’ tendency to rope together through van der
Waals forces, provide the opportunity to develop ultra-high strength, low-weight materials with
highly conducting electrical and thermal properties which makes them attractive for various
applications. Carbon nanotubes are first discovered by S. Ijima in the year 1991.

Single-walled and Multiwalled Carbon Nanotubes

CNTs are of two types. They are single-walled carbon nanotubes (SWCNTs) and multi-walled
carbon nanotubes (MWCNTs). Single-walled carbon nanotubes (SWCNTs) are cylinders
containing only one cylinder made of single graphene sheet. Several graphene sheets when folded
to form cylinders one inside the other are called multi-walled carbon nanotubes.
SWCNTs have diameter in the range of 1-2 nm and length in the range of 1-100 m. MWCNTs
have outer diameter in the range of 2-20 nm and inner diameter 1-3 nm. They have length in the
range of 1-100 m with inter tubular distance of 0.34 nm. The two types of CNTs have length
reaching even millimeters starting from micrometers.

Fig 4: Types of CNTs

Synthesis of CNTs
i. Chemical Vapour Deposition (CVD) method
CVD method, also called as thermal CVD, consists of forming carbon nanotubes by decomposing
an organic gas over a substrate coated with metal catalyst nanoparticles.

Thermal CVD method consists of a quartz tube enclosed in a furnace. The substrate made of silica,
mica, quartz or alumina on which the CNTs has to be formed is placed inside the furnace. The
substrate is coated with metal catalyst nanoparticles like Fe, Co or Ni. Carbon precursors such as
acetylene (C2H2), ethylene (C2H4) or methane (CH4) gas is passed into the furnace and the
temperture inside is fixed in the range of 500-900ᵒC. At these temperatures, the carbon precursor
starts to dissolve in the metal catalyst till the point of supersaturation. The saturated carbon starts
to precipitate in the form of cylinders which are called the carbon nanotubes.The diameter of the
tube is determined by the size of the nanoparticles used as the catalyst. Thermal CVD can be used
to produce both SWCNTs and MWCNTs.

Fig 5: Thermal CVD

ii. Laser Ablation method

Laser ablation method consists of a furnace, a quartz tube with a window on one side, a graphite
target doped with metal catalyst such as cobalt or nickel at the center of the tube. An argon flow
system is maintained at a constant pressure and flow rate. A water-cooled copper collector is
present outside the furnace.
A continuous or pulsed laser beam from Nd:YAG (Neodymium-doped-yttrium aluminium garnet)
is made to fall on the graphite target through the window and the furnace temperature is maintained
at 1200ᵒC. When the laser beam falls on the graphite target, the target gets vaporised to form carbon
particles containing atoms and molecules. The formed carbon atoms and molecules are sweeped
by the flowing argon gas having a flow rate of 1 cm s-1 and a pressure of 500 torr. When the carbon
particles reaches the water cooled copper collector, they undergo condensation and grow in the
form of carbon nanotubes.

Fig 6: Laser Ablation Method

Laser ablation method has several advantages such as high quality single walled carbon nanotubes
can be produced, diameter of the nanotubes can be controlled and growth dynamics can be
followed.

Properties of Carbon Nanotubes

i. Electrical Properties
The electrical property of carbon nanotubes depends on the direction of rolling-up of the graphene
sheets, called helicity (chirality) and the diameter of the nanotube. Helicity is the rolling of the
hexagonal chains with respect to the tube axis. There are three different types of CNTs based on
helicity. They are armchair, zigzag and chiral carbon nanotubes.
 Fig 7: Types of carbon nanotubes

Turning a graphene sheet by 30 degrees will convert the configuration from armchair to zigzag or
vice versa. SWCNTs’ conductivity depends on the chiral vector. They behave like a metal and
have high electrical conductivity or can show semiconducting property or can be non-conducting.
A slight change in helicity can transform its metal conductivity to semiconducting type.

Armchair tubes (n, m) are metallic as they are highly symmetrical and the conditions for the
metallic property to dominate are n - m = 0 or (n - m)/3 = integer, where n and m are the chiral
vectors. Examples: (8, 2), (6, 3) and (7,7) tubes are metallic.

Zigzag and chiral tubes are either metallic or semiconducting. Semiconducting property dominates
when (n – m)/3 ≠ integer. Examples: (9,1), (5,3) tubes are semiconducting.

Fig 8: Vector representation of metallic and semiconducting carbon nanotubes

Metallic CNTs have high conductivity and can carry billion amperes of current per square
centimeter whereas a copper wire can carry only million amperes of current per quare centimeter
due to resistive heating which melts the copper wire at high currents. The high conductivity for
CNTs is due to minimum defects and hence imparts low resistance to the flow of current. Due to
high thermal conductivity, their is no resistive heating during the flow of high currents in CNTs.

The low conductivity in the case of chiral and zigzag forms is due to the replacement of hexagonal
rings with pentagonal or heptagonal rings. This type of defect can affect the electrical conductivity
severely in CNTs. For SWCNTs, the band gap is in the range of 0.4 – 1 eV and is found to decrease
with the increase in the inverse diameter of the nanotube.

Fig 9: Plot of Energy gap versus Diameter of carbon nanotubes

ii. Mechanical Properties
CNTs also have unique thermal and mechanical properties that render them with highly beneficial
properties for the development of new materials.

a. Tensile strength: It is the amount of stress required to pull a material. CNTs are very strong
and have tensile strength which is 100 times more than that of steel having the same diameter. The
tensile strength of CNTs is around 45 billion pascals whereas for steel it is only 2 billion pascals.
This high tensile strength for CNTs is due to the following reasons:
i) Strong interlocking of the carbon atoms through covalent bond.
ii) CNTs does not have weak points like grain boundaries, dislocations etc and is
considered to be a single molecule.

b. Youngs modulus: It is the measure of elasticity or flexibility of the material. The elasticity is
inversely proportional to the Youngs modulus value. CNTs have high Youngs modulus value
(1.28 – 1.8 TPa) compared to that of steel (0.21 TPa) which shows that CNTs are 5 to 10 times
harder than steel.
c. Thermal Conductivity:
CNTs have high thermal conductivity as they don’t get heated or get cooled very well. Thermal
conductivity of CNTs is 10 times that of silver, 15-20 times that of copper and 2 times that of
diamond. CNTs conduct heat through the material by the vibration of the covalent bonds present
between the carbon atoms. The strong covalent bonds are helpful in transmitting the heat
throughout the nanotube thereby providing good thermal conductivity.
d. Density: Density of CNTs is one fourth that of steel and half that of aluminium. Hence CNTs
are light weight materials having density in the range of 1.33 – 1.44 g/cm3.

Applications of Carbon Nanotubes

Carbon Nanotubes have wide variety of applications in different fields. Carbon nanotubes are ideal
candidates for use in electronic devices, chemical/electrochemical and biosensors, transistors,
electron field emitters, lithium-ion batteries, white light sources, hydrogen storage cells, cathode
ray tubes (CRTs), electrostatic discharge (ESD) and electrical-shielding applications.

Important applications of CNTs are:

• Carbon nanotubes (CNTs) have large surface area, high chemical stability and controlled
surface chemistry. Hence they are used as catalyst support.
• CNTs are used as additives to synthetics by removing the agglomeration in order to spread
evenly on the substrate. They can be chemically bonded with the substrate, like a plastic
material, by functionalizing it on the surface.
• CNTs can store high weight percentage of hydrogen without any leakage. Therefore used
in hydrogen-oxygen fuel cells to store hydrogen.
• CNTs are used in various biomedical applications. The physical properties of CNTs, such
as mechanical strength, electrical conductivity, and optical properties, are of great value
for creating advanced biomaterials with increased solubility and biocompatibility,
enhanced material compatibility and cellular responsiveness. CNTs are used in targeted
drug delivery due to its adaptability under different conditions.
 • CNTs are used as actuators where there is conversion of electrical energy to mechanical
energy for inducing movements.
• CNTs act as sensing materials in sensors for the detection of pressure, temperature, mass,
light, stress, strain etc. Though studies have shown that CNTs are robust and inert
structures, their electrical properties are found to be extremely sensitive to the effects of
charge transfer and chemical doping by various molecules. Sensors based on CNTs are
field effect transistors (FET). CNTs-FETs have been widely used to detect gases such as
greenhouse gases in environmental applications. Functionalization of CNTs have made
them even more selective to the target analyte. For example, flexible hydrogen sensors
have been made using single-walled carbon nanotubes decorated with palladium
nanoparticles.
• Semiconducting SWCNTs are now considered as strong candidates for the next generation
of high-performance, ultra-scaled and thin-film transistors as well as for opto-electronic
devices to replace silicon electronics. CNTs act as ideal field emitters due to high current
density, low turn-on and operting voltage. Thin film CNTs are used in making thin film
solar cells, organic LEDs and touch screens as they are transparent to visible light to
produce electricity.
• CNTs are stiff, tough and strong having superior mechanical properties and are useful in
the production of very strong, light weight materials that find applications in building,
structural engineering and aerospace.
• “Nano inks” which is an ink formulation based on CNT dispersions are found to be highly
useful in Printed electronics and in making transparent electrodes, thin-film transistors,
light-emitting devices and solar cells.
• CNTs are used in making aircraft components due to its high fatigue strength.
• Efficient water transport through carbon nanotubes with openings of less than one
nanometer have been used as high flow membranes in energy-efficient water purification.
They are found to provide protection against biological agents due to their very small pore
size which is less than 5 nanometers wide.

QUESTIONS
PART-A
 1. What are allotropes of carbon? Name them.
2. What are fullerenes?
3. Define graphene.
4. Differentiate graphene oxide and reduced graphene oxide.
5. Why graphene called as van der Waals solid?
6. Mention any two applications of fullerenes.
7. List out any two important properties of graphene oxide.
8. Mention two appliactions of rGO.
9. What are carbon nanotubes?
10. Name the two types of CNTs.
11. How are SWCNTs classified based on chirality?
12. Differentiate SWCNT and MWCNT.
13. Give the advantages of Laser ablation method of synthesis of CNTs over thermal CVD
method.
PART-B
1. Explain in detail about the various allotropes of carbon.
2. What are fullerenes? Explain the Krätschmer and Huffman method of synthesis of
fullerenes with a neat diagram.
3. Comment on the important properties of fullerenes.
4. Discuss the applications of fullerenes.
5. Write short note on graphene, graphene oxide and reduced graphene oxide.
6. Explain the structure of graphene with a neat diagram.
7. Write short note on the mechanical properties of graphene.
8. Explain the electrical properties of graphene.
9. Elaborate on the use of graphene in space applications.
10. Differentiate SWCNT and MWCNT with appropriate diagrams.
11. Explain in detail the thermal method of synthesis of CNTs with a neat diagram.
12. Explain laser ablation method of synthesis of CNTs with a diagram.
13. Discuss on the mechanical properties of CNTs.
14. Elaborate the electrical properties of CNTs with respect to chirality.
15. Write in detail the various applications of CNTs.
References
1. Graphene: Fundamentals and emergent applications Jamie H. Warner, Franziska Schaffel,
Alicja Bachmatiuk, Mark. H. Rummeli, First Edition, 2013, Elsevier.
2. https://www.nanowerk.com/nanotechnology/introduction/introduction_to_nanotechnology
_22.php
3. Carbon Nanotubes, Edited by Morinubo Endo, Sumio IIjima, Mildred S. Dresselhaus, First
Edition, 1996, Pergamon.
4. Handbook of Carbon, Graphite, Diamond and Fullerenes: Properties, Processing and
Applications, Hugh O. Pierson, 1993, Noyes Publications.
5. https://www.sciencedirect.com/topics/materials-science/fullerenes
6. A new method of fullerene production: pyrolysis of acetylene in high- frequency thermal
plasma, Yiming Chen, Haiyan Zhang, Yanjuan Zhu, Ding Yu, Zhenfang Tang, Yanyang
He, Chunyan Wu, Jinhua Wang, 2002, Materials Science and Engineering B95.
 SCHOOL OF SCIENCE AND HUMANITIES
DEPARTMENT OF CHEMISTRY

UNIT-V – ENGINEERING MATERIALS – SCYA1101

 1. Introduction: Phase Equilibria

A system is a part of the universe, which is focused for chemical study. The rest of the system is
called surroundings. The system and surroundings are separated by a real or imaginary surface
called boundary. When a system is uniform throughout physically and chemically, it is called as
homogeneous system. When a system has two or more parts, it is a heterogeneous system. If
equilibrium is present between these parts, it is called heterogeneous equilibria. Phase rule explains
heterogeneous equilibria. It predicts qualitatively the effect of pressure, temperature and
concentration on heterogeneous equilibria. That is, it gives information about the behaviour of
heterogeneous equilibrium systems when they are subjected to changes in variables like
temperature, pressure and concentration.

2. The Gibbs Phase Rule

Phase Rule Statement: Phase rule was discovered by J.W. Gibbs in 1875 and is known as Gibbs
Phase Rule. For a heterogeneous system in equilibrium at a definite temperature and pressure,
Gibbs phase rule relates that the number of degrees of freedom equals to the difference in the
number of components and the number of coexisting phases plus two provided the equilibrium is
not influenced by external effects such as gravity, electrical and magnetic forces, surface tension,
etc.
Mathematical Statement: The phase rule is mathematically stated as: F = C – P + 2
Where,
✓ P is the number of Phases present in equilibrium.
✓ C is the number of Components for the system.
✓ F is the number of Degrees of Freedom for the equilibrium.
✓ 2 indicate the variables: Temperature and Pressure.

Terms Involved in Phase Rule

i. Phase
Definition: Phase is a homogeneous, physically distinct, and mechanically separable part of a
system, which is separated from other parts of system by definite boundaries.
a. Freezing water system: Freezing water system consists of three phases namely liquid water,
solid ice and water vapour. Each phase is physically distinct and homogeneous.

Water vapour

Ice

Water

Floating of ice cube in water

b. Liquids: If two liquids are miscible (alcohol and water), they are considered as one liquid phase
only. If two liquids are immiscible (Oil and water), they are considered as two separate phases.

Wate Wate Oil

hol r
r Alco

Heterogeneous Oil
Homogeneous solution
solution Water

c. Gases: A pure gas or a mixture of any number of gases is considered as a single phase. This is
because gases are completely miscible in all proportions.
✓ Pure oxygen gas – Single phase
✓ Mixture of CO and N2 – Single phase
✓ Mixture of CO(g) and H2O(g) – Single phase
d. Solids: Each solid is considered as a separate phase. For example, a heterogeneous mixture of
CaCO3 and CaO consists of two solid phases. Each allotrope of a substance is considered as a
single phase. For example, carbon exhibits allotropy graphite and diamond. They are considered
as two separate phases.
e. Solution: A solution (solute and solvent) is considered as a single phase only (Glucose in water).

ii. Components
Definition: The number of components of a system is the minimum number of chemical
constituents required to express the composition of all the phases present in the system.
While expressing the chemical composition of all the phase present in the system,
✓ all the selected or chosen constituents must be included and
✓ for this purpose positive, negative or zero quantities of constituents may be used
a. The freezing water system: This system consists of three phases namely ice, water and water
vapour. All the three phases are different physical form of same chemical substance (water). Hence
this is considered as one-component system.
b. A system of saturated solution of NaCl: This system consists of three phases namely solid
NaCl, NaCl solution and water vapour. The chemical composition of all the three phases can be
expressed in terms of NaCl and H2O. Hence it is a two-component system.
c. Thermal decomposition of CaCO3

CaCO3(s) CaO(s) + CO2(g)

This system consists of three phases namely, solid CaCO3, solid CaO and gaseous CO2. Though
the system has three different constituents, it is considered as a two-component system. This is
because the chemical composition of all the three phases can be expressed in terms of any two of
the three chemical constituents present.

CaCO3 and CaO are CaCO3 and CO2 are CaO and CO2 are
chosen as Two chosen as Two chosen as Two
Components Components Components
Phase Chemical Phase Chemical Phase Chemical
Composition Composition Composition
CaCO3 CaCO3 + 0CaO CaCO3 CaCO3 + 0CO2 CaCO3 CaO + CO2
CaO 0CaCO3 + CaO CaO CaCO3 − CO2 CaO CaO + 0CO2
CO2 CaCO3 − CaO CO2 0CaCO3 + CO2 CO2 0CaO + CO2

d. Dissociation of NH4Cl in vacuum

NH4Cl (s) NH3 (g) + HCl (g)

This system consists of two phases namely, solid NH4Cl and gaseous mixture containing NH3 and
HCl. The composition of both the phases can be expressed in terms of only one constituent namely,
NH4Cl. Hence it is a one-component system.

Phase Chemical Composition

Solid NH4Cl x NH4Cl
Gaseous phase xNH4Cl x NH3 + x HCl

If the concentration of NH3 is not equal to that of HCl i.e., NH3(g) ≠ x HCl(g), then the system
becomes two component system. Suppose y mole of HCl is added to x NH4Cl, then the chemical
composition of solid and gaseous phases is expressed in terms of NH4Cl and HCl as follows.

Phase Chemical Composition

Solid NH4Cl x NH4Cl + 0 HCl
Gaseous phase x NH4Cl + y HCl x NH3 + x HCl + y HCl

iii. Degree of freedom (or) Variance of a system

Definition: The number of degrees of freedom of a system is the minimum number of independent
variable factors such as temperature, pressure and concentration (composition) required to describe
the system completely. A system having one, two, three and zero degrees of freedom are usually
called univariant, bivariant, trivariant and invariant system respectively.
a. Consider a one component system consisting of two phases

Water Water vapour

P = 2;C=1
F = C–P+2
F = 1–2+2
F = 1

To define such a system, only one variable factor (either temperature or pressure) is needed. Hence
the system is univariant.

b. Consider a one component system consisting of one phase: Water vapour.

 P = 1;C=1
F = C–P+2
F = 1–1+2
F = 2
To define such a system, two variable factors (temperature and pressure) are needed. Hence the
system is bivariant.
c. Consider a one component system:

Ice Water Water vapour

P = 3;C=2
F = C–P+2
F = 1–3+2
F = 0
To describe this equilibrium system, no need to specify any variable factors, because all the three
phases can occur in equilibrium only at a particular temperature and pressure. Hence this system
does not have any degree of freedom (invariant or zero variant).
Uses of phase rule
✓ The phase rule takes no account of the nature or amount of substances.
✓ Phase rule is applicable to macroscopic systems. Therefore it is not necessary to have
information about molecular structure.
✓ It gives information about the behaviour of systems when they are subjected to changes in
variables such as temperature, pressure and concentration.
Limitations of phase rule
✓ The phase rule takes into account only the variable factors like temperature, pressure and
the composition. The influences of factors such as electric, magnetic, gravitational, surface
forces etc. are ignored.
✓ The phase rule is applicable only to heterogeneous systems in equilibrium.
✓ In phase rule, time is not a variable factor because this rule applies to a system in
equilibrium. The equilibrium state is independent of time factor.

Phase Diagram
Definition: Phase diagram is a graph obtained by plotting one degree of freedom against another.
If temperature is plotted against pressure, it is known as temperature-pressure diagram. If
temperature is plotted against composition, it is known as temperature–composition diagram.

Significance: They help in studying and controlling the various processes such as phase
separation, solidification of metals, and change of structure during heat treatment like annealing,
quenching, tempering etc.

3. Phase Diagram of Water System (Application of Phase Rule to One

Component System)
The water system is an example of one component system. It consists of three phases namely solid
ice, liquid water and water vapour. The phase diagram of water system is given in Fig. 5.1.
Table 1: Important data for constructing phase diagram of water system
S. No. Parameters Temperature Pressure
1 Boiling point 100°C 1 atm
2 Triple point 0.0075°C 4.58 mm
3 Critical point 374°C 218 atm

B A
218atm ----------------------------------------------
----------------------------------------------
ve

Liquid Water
n cur

ve
io

ur
Fus

c
Pressure

Solid Ice on
izati
ur
1atm -----------------------------------
po
----------------------

-
---------------------

V a
4.58mm ----------------------
---
-
A' ------- e O
-----------------

rv Water Vapour
cu
tion
a
m
C Subli
273oC 0oC 0.0075oC 100oC 374oC
Temperature

Fig 1: The Phase Diagram of Water System

Salient features of phase diagram of water system
i. Curves: The phase diagram consists of three curves OA, OB and OC. Each curve separates two
phases and hence the system is “univariant” along the curve.

F = C–P+2
F = 1–2+2
F = 1

Curve OA: Curve OA is the vaporization curve because it separates the liquid region from vapour
region. Along the curve OA, water and water vapour are in equilibrium (water ↔ water vapour).
The curve OA ends at the point A, which corresponds to the critical temperature (374°C) and critical
pressure (218.5atm) of water. Beyond the point A, the liquid and vapour phases merge into each
other to form a single homogeneous phase.

Curve OB: Curve OB is the fusion or melting curve because it separates ice and water phases (ice
↔ water). The curve OB is slightly inclined towards pressure axis. This shows that melting point
of ice decreases with the application of pressure.

Curve OC: Curve OC is the sublimation curve because it separates ice and water vapour phases
(ice ↔ water vapour). At the lower limit, the curve OC terminates at absolute zero (−273°C) where
no vapour can be present and only ice exists.

ii. Point ‘O’ (Triple point): The three curves OA, OB, and OC meet at a point O, at which solid
ice, liquid water and water vapour are simultaneously in equilibrium. This is called triple point.

Solid ice Liquid water Water vapour

At the triple point, the system is ‘invariant’. The triple point of water system corresponds to a
temperature of 0.0075°C and a pressure of 4.58 mm mercury.

F = C–P+2
F = 1–3+2
F = 0
iii. Areas: The curve is divided into three areas AOB, BOC and COA. Each area represents a single
phase and hence the system is ‘bivariant’.

F = C–P+2
F = 1–1+2
F = 2

iv. Curve OA' (Meta stable equilibrium): The curve OA’ represents the vapour pressure curve
of super cooled water. Super cooling means, cooling of water below its freezing point without the
separation of solid. Super cooled water is highly unstable and it can be converted into solid by a
slight disturbance. Hence the system along the curve OA’ is said to be in “meta stable equilibrium”.

4. Application of Phase Rule to Two Component Alloy System

Classification of two component systems
Based on mutual solubility and reactive ability, the two component system is classified into the
following three types:
i. Simple eutectic formation: The two solid substances can form a simple eutectic under the
following conditions:

✓ The two solid metals must be completely miscible in the liquid state but completely
immiscible in the solid state.
✓ They should not chemically react with each other.

Therefore, eutectic has the same composition both in liquid and solid states. Also the
eutectic has a sharp melting and freezing point as the pure metals. Hence eutectic composition is
a unique mixture of two solids, which has the lowest melting point.
Examples: Lead – Silver system; Bismuth – Cadmium system.
Uses of eutectic system:
✓ De-silverisation of lead (Enrichment of silver from argentiferous lead ore) is based on the
formation of simple eutectic.
✓ The principle of a simple eutectic system is used for preparing solders (Eg: Pb-Sn solder),
which are used for joining two metal pieces together.
ii. Formation of compound with congruent melting point: When two solid substances combine
in a definite proportion, one or more stable compounds are formed. These compounds melt at
constant temperature to give liquid melt of the same composition. The temperature at which a
compound melts to give liquid phase of same composition is known as congruent melting point.
Examples: Zinc – Magnesium system; Tin – Magnesium system.

iii. Formation of compound with incongruent melting point: There are solid substances which
combine together to form one or more unstable compounds. Further, they decompose into a new
solid phase and a liquid melt of different composition. The temperature at which the unstable
compound decomposes into a new solid phase and a liquid melt (having different composition
from solid phase) is known as incongruent melting point.
Examples: Sodium – Potassium system; Gold – Antimony system.

iv. Solid solution formation: When two different metals dissolve each other in liquid and or in
solid state, the resulting phase is called solid solution. Solid solution is formed when the solvent
and solute atoms have similar sizes and electron structure.
Examples: Copper – Nickel system.

Reduced phase rule (or) Condensed system

A solid−liquid alloy system has practically no gaseous phase. Hence the effect of pressure is
negligible on this type of equilibrium. Therefore to construct the usual phase diagram with two
axes, the vapour phase is neglected. Such a solid-liquid system is called “condensed system”. In
condensed system measurements are made at constant pressure. This reduces the degree of
freedom of the system by one. Therefore, the phase rule equation for two-component alloy system
is written as: F = C – P + 1. This equation is known as “reduced phase rule equation”.

5. Thermal Method of Analysis (or) Experimental Method of Construction of

a Simple Eutectic Phase Diagram
Definition: Thermal analysis involves the study of cooling curve of various compositions of two
solids during solidification.
1. Cooling curve of a pure metal

s
Beginning of freezing
End of freezing
Temperature

a a'

x
Time

Fig.2a: Cooling Curve of Pure Metal

Definition: Thermal analysis involves the study of cooling curve of various compositions of two
solids during solidification.

s : Represents the pure metal is in molten state.

sa : Along sa, the temperature of the melt decreases gradually with time.
a : The point ‘a’ indicates the temperature at which the molten metal starts freezing at its
surface.
aa’ : Along aa’, the liquid melt and solid metal are in equilibrium. Further the temperature
remains constant until the liquid melt is completely solidified because the liquid melt
and solid metal have same chemical composition.
a’ : Indicates the end of freezing.
a’x : Along a’x, the temperature of solid metal again decreases with time.

2. Cooling curve of a mixture of solid A and solid B

 s
Freezing of either A or B starts

a
Eutectic point

Temperature
End of freezing

b b'

x
Time

Fig 2b: Cooling Curve of a Mixture of Two Solids A and B

s : Represents a mixture of solid A and solid B is in fused state.

sa : Along sa, the temperature of the mixture containing A and B decreases with time.
a : The point ‘a’ indicates the temperature, at which freezing of base metal (either A or B
depends upon their freezing point) starts from the liquid mixture.
ab : Along ab, the liquid melt and solid metal A (or solid metal B) are in equilibrium.
Further, the line ab indicates the composition of molten mixture progressively changes
due to continuous separation of solid A (or solid B) with time. Because of two different
chemical composition of the liquid mixture (containing A and B) and solid metal
(either A or B), the temperature of the liquid mixture decreases at a different rate.
b : The point at which the liquid mixture (containing both A and B) starts freezing into
solid A and solid B (eutectic mixture).
bb’ : Along bb’, the liquid mixture and solid A and solid B are in equilibrium.
b’ : Indicates the end of freezing of eutectic mixture.
b’x : Along b’x, the temperature of solids again decreases with time.

3. Cooling curve of eutectic mixture and construction of simple eutectic phase diagram

Since eutectic behaves like a pure solid metal, it also has same type of cooling curve as pure solid
metal. So, it is possible to construct a complete phase diagram for the two-component system on
the basis of large number of cooling curves of various compositions (Fig.5.3c).
 1 2 3 4 5 6 7

g .......................................................g
a ....................................................... a
f ............................................................
f
Liquid melt
b ........................................................... b
Temperature

Temperature
e........................................................

uid +
So quid
e

lt
Liq lid B
Li

me
lid m
c ....................................................... c

A elt

So
+
d
............................................ c'
b' c' d' e' f' b' d' e' f'
Solid A + Solid B

Time 100%A Composition 100%B

Fig 2c: Cooling Curves of Various Compositions of Two Solids (1) 100% A (2) 80%A+20% B
(3) 70%A+30%B (4)60%A+ 40% B (5) 45%A+55%B (6) 30%A+70% (7) 100%B
In eutectic phase diagram:
✓ Each curve corresponds to a definite composition of A and B.
✓ The break or discontinuity in the graph (a, b, c, d, e, f, g, h) denotes phase transformation
(freezing point of either A or B).
✓ The cooling curve of eutectic composition (curve 4) is similar to those of pure substances
(curve 1 and 7).
✓ The eutectic phase diagram is obtained by plotting various compositions of two substances
against the discontinuity (freezing point), which is nothing but characteristic temperature.

Salient features of simple eutectic phase diagram

i. Curves: The eutectic phase diagram consists of two curves abcd, and gfed. Along the curve, two
phases (Solid Liquid melt) are in equilibrium and hence the system is ‘univariant’ (F = 2–2+1 =
1).
ii. Point O (Eutectic Point): The curve abcd and gfed intersect at d which is called eutectic point.
At the eutectic point three phases are in equilibrium. Hence the system is non-variant (F = C–P+1
= 2–3+1 = 0).

Liquid melt Solid A + Solid B

iii. Areas: The eutectic phase diagram consists of four distinct areas (i) Above abcdefg has a single
phase (molten A and B) (ii) Below abcd (solid A + liquid melt) (iii) Below gfed (solid B+ liquid
melt) and (iv) Below the point d (solid A + solid B).

6. Construction of Simple Eutectic System (Lead-Silver System)

The lead-silver system is an example of two component system. It consists of two curves, a point
O and four areas. The phase diagram of lead-silver system is given in Fig. 5.4.

Table 2: Important Data for Constructing Phase Diagram of Pb-Ag system

S. No. Parameters Temperature/Composition
1 Melting point of Lead (Pb) 327°C
2 Melting point of Silver (Ag) 961°C
3 Eutectic Temperature 303°C
4 Eutectic Composition 97.4%Pb + 2.6%Ag

A 961oC

a
..................

Liquid melt

327oC B
Temperature

Solid Ag +
So Liquid melt
Li lid P b
qu b
id
me + O
o
303 C lt 303oC
..............

Solid Pb + Solid Ag

100%Pb 97.4%Pb 100%Ag

+ 2.6%Ag
Composition wt%

Fig 3: The Lead-Silver System

Salient features of phase diagram of Pb-Ag system
i. Curves

Curve AO: Pure Ag melts at 961°C. Addition of Pb lowers the freezing point of Ag along the curve
AO. Therefore AO is the freezing point curve of silver. Along AO, solid Ag and liquid melt are in
equilibrium. Hence the system along the curve is ‘univariant’ (F = C–P+1 = 2–2+1 = 1).

Curve BO: Pure Pb melts at 3270C. Addition of Ag lowers the freezing point of Pb along the curve
BO. Therefore BO is the freezing point curve of Pb. Along BO, solid Pb and liquid melt co-exist
and hence the system is ‘univariant’ (F = C–P+1 = 2 – 2 + 1 = 1).

ii. Point O (Eutectic point)

The curve AO and BO intersect at O which is called eutectic point. At this point three phases are
in equilibrium.

Liquid melt Solid Ag + Solid Pb

Hence the system is non-variant (F = C–P+1 = 2–3+1 = 0). Below the point O, both silver and lead
exist in the solid state. Therefore, eutectic point is the lowest temperature at which a mixture of
two solids melts (eutectic = easy melting). The corresponding temperature and composition are
called “eutectic temperature” and “eutectic composition” respectively. The eutectic point of Pb-
Ag system corresponds to a temperature 303°C and composition 97.4%Pb+2.6%Ag.

iii. Areas

The area above AOC has a single phase (molten Pb and Ag). Applying the reduced phase rule F =
C–P+1 = 2–1+1 = 2, the system is bivariant. The area below AO (solid Ag + liquid melt), below
BO (solid Pb + liquid melt) and below O (solid Ag + solid Pb) have two phases and hence the
system is univariant (F = C–P+1 = 2–2+1 = 1).
Application of Pb-Ag system (Pattinson’s Process)

The process of recovery of silver from argentiferous lead is called as desilverisation.

Desilverisation of lead is based on the formation of eutectic mixture. Argentiferous lead consists
of a very small amount of silver (0.1%). The ore is heated to a temperature well above its melting
point, so that it exists as liquid melt (point a in Pb-Ag system). When it is allowed to cool, the
temperature of the melt falls along the line ab. As soon as point b is reached, lead is crystallized
out. On repeating the process of melting and cooling, more and more lead is separated along the
line BO. At O a eutectic mixture containing 2.6%Ag and 97.4%Pb is obtained. The eutectic alloy
is then treated for recovery of silver.
Melting Point, Triple Point and Eutectic Point
a. Melting point: It is the temperature at which, the solid and liquid having the same composition
are in equilibrium (Solid Liquid).
b. Triple Point: It is the point at which three phases (any types) are in equilibrium.

Solid Liquid Vapour

Solid A Solid B Liquid melt

c. Eutectic point: It is the point at which two solids and a liquid are in equilibrium.

Solid A Solid B Liquid melt

Hence all the eutectic points are triple points but all the triple points are need not be eutectic
points.

Problems Based on Phase Rule

1. Is it possible to have a quadruple point in phase diagram of a one-component system?

“No”. Quadruple point means 4 phases are simultaneously in equilibrium.

F = C–P+2
F = 1–4+2
 F = –1

F = – 1 is meaningless. Hence the answer is “No”.

2. How many number of phases, components and degrees of freedom are available in the
following systems:

(i) BaCO3 (s) BaO (s) + CO2 (g)

(ii) MgCO3 (s) MgO (s) + CO2 (g)
(iii) CaCO3 (s) CaO (s) + CO2 (g)

All the above systems have 2 solid phases and one gaseous phase.

Number of phases, P = 3
Number of components, C = 2
Number of degrees of freedom, F = C–P+2
F = 2–3+2
F = 1(univariant)

3. How many phases, components, and degrees of freedom are present in:

(i) Water at 0.0075°C and 4.58mm Hg

(ii) Water Water vapour at 30°C
(iii) Pb–Ag alloy system at constant pressure [composition 2.6%Ag
and 303°C]

(i) This indicates triple point of water system,. At the triple point, solid ice, liquid water and
water vapour are simultaneously in equilibrium.

Number of phases, P = 3
Number of components, C = 1
Number of degrees of freedom, F = C–P+2
F = 1–3+2
 F = 0 (invariant)

(ii) Water ↔ Water vapour at 30°C.

Number of phases, P = 2
Number of components, C = 1
Number of degrees of freedom, F = C–P+2
F = 1–2+2
F = 1(univariant)

(iii) This indicates eutectic point of Pb-Ag system. At the eutectic point, solid Ag, solid Pb and
liquid melt are in equilibrium.

Number of phases, P = 3
Number of components, C = 2
Number of degrees of freedom, F = C–P+1
F = 2–3+1
F = 0 (invariant)

4. In the phase diagram of water, point out the phase in equilibrium with ( i) One degree of
freedom and (ii) No degrees of freedom.

(i)
Number of phases, P = ?
Number of components, C = 1
Number of degrees of freedom, F = 1
F = C–P+2
P = C+2–F
P = 1+2–1
P = 2 (bivariant)
Any two phases can be in equilibrium.

Water Water vapour

Ice Water
Ice Water vapour

(ii)
Number of phases, P = ?
Number of components, C = 1
Number of degrees of freedom, F = 0
F = C–P+2
P = C+2–F
P = 1+2–0
P = 3 (trivariant)

All the three phases are simultaneously in equilibrium.

Solid ice Liquid water Water vapour

5. Fe(s) + H2O (g) ↔ FeO(s) + H2 (g). Calculate P, C and F for the above system.

Number of phases, P = 3 (2 solids; 1 gaseous)

Number of components, C = 3 (Fe, O2 and H2)
Number of degrees of freedom, F = C–P+2
F = 3–3+2
F = 2 (bivariant)

6. Determine the number of phases, components, and degrees of freedom available for the
following systems:

(i)
Number of phases, P = 3 (2 solids; 1 gaseous)
Number of components, C = 2 (Na2SO4 & H2O)
 Number of degrees of freedom, F = C–P+2
F = 2–3+2
F = 1 (univariant)

(ii)
Number of phases, P = 1 (all together constitute a single
phase)
Number of components, C = 2 (any two)
F = C–P+2
F = 2–1+2
F = 3 (trivariant)

(iii)
(a) When PPCl3(g) = PCl2(g) , only one constituent is sufficient to express the system.

Number of phases, P = 1
Number of components, C = 1
Number of degrees of freedom, F = C–P+2
F = 1–1+2
F = 2 (bivariant)

(b) When PPCl3(g) ≠ PCl2(g) , minimum of two constituents are needed to express the system.

Number of phases, P = 1
Number of components, C = 2
Number of degrees of freedom, F = C–P+2
F = 2–1+2
F = 3 (trivariant)

7. Write the number of phases and components in the following heterogeneous system:
CuSO4 (s) + 5 H2O (l) ↔ CuSO4. 5 H2O (s).

Number of phases, P = 3 (2 solids; 1 liquid)

 Number of components, C = 2 (CuSO4 & H2O)
Number of degrees of freedom, F = C–P+2
F = 2–3+2
F = 1 (univariant)

8. A system consists of benzene and water. What is the number of phases?

Number of phases, P = 2
Number of components, C = 2 (Benzene & water)
Number of degrees of freedom, F = 2–2+2
F = 2–2+2
F = 2 (bivariant)

9. Calculate the number of phases present in the following systems:

(i) MgCO3(s) MgO(s) + CO2 (g)

(ii) Rhombic sulphur (s) Monoclinic sulphur (s)
(iii) Solid ice Liquid water Water vapour
(iv) An emulsion of oil in water

(i) MgCO3(s) MgO(s) + CO2 (g)

Number of phases, P = 3
Number of components, C = 2
Number of degrees of freedom,F = C–P+2
F = 2–3+2
F = 1 (univariant)

(ii) Rhombic sulphur (s) Monoclinic sulphur (s)

Number of phases, P = 2
Number of components, C = 1
Number of degrees of freedom,F = C–P+2
F = 1– 2 + 2
F = 1 (univariant)
 (iii) Solid ice Liquid water Water vapour
Number of phases, P = 3
Number of components, C = 1
Number of degrees of freedom, F = C–P+2
F = 1–3+2
F = 0 (invariant)

(iv) An emulsion of oil in water

Number of phases, P = 2
Number of components, C = 2 (Benzene & water)
Number of degrees of freedom, F = 2–2+2
F = 2–2+2
F = 2 (bivariant)

10. 100 kg of a sample of argentiferous lead containing 0.5% Ag is melted and then allowed
to cool. If eutectic contains 2.6% Ag, (1) what mass of eutectic will be formed and (2) what
mass of lead will separate out?

Given: In 1 kg argentiferous lead, silver content is 0.5%; (i.e: 5 gm).

(or) In 100 kg argentiferous lead, = 500 gm = 0.5 kg
silver content
In the given eutectic system, 2.6% is silver and hence 97.4% is lead.
Corresponding to 0.5 kg silver, the 0.5  97.4
= 18.73 kg
amount of lead (Pb) present in eutectic = 2.6

(1) The mass of eutectic formed from = 0.5 + 18.73

100 kg ore
= 19.23 kg
(2) The mass of lead, which is = 100 − 18.73
separated out from 100 kg ore
= 81.27 kg
 7. Introduction: Fuels

Fuels are major sources of energy for industries. They are classified mainly into two general
classes’ namely fossil fuels and nuclear fuels. Fossil fuels are those, which have been derived from
fossil remains of plant and animal life. They are found in the earth’s crust. All conventional fossil
fuels whether solid, liquid or gaseous (coal, petroleum or Natural gas) contain basically carbon
and/or hydrogen, which by combustion in presence of oxygen in the air release heat energy. This
heat energy can be utilized for domestic and industrial purposes.

Fuel + O2 (Air) Products + Heat

Classification of Fuels

Fuel is a substance, which on combustion produces large amount of heat that can be utilized
economically for industrial and domestic purposes. Fuels may be divided into: (1) Primary or
naturally occurring fuels and (2) Secondary or derived from primary fuels. Primary and secondary
fuels may also be divided into three classes’ namely solid, liquid and gaseous fuels (Table 3).

Table 3: Classification of fuels

S. No. Examples Solid fuels Liquid fuels Gaseous fuels
1. Primary fuel Wood, Peat, Petroleum (or) Natural Gas.
(Natural). Lignite, Crude oil.
Anthracite.
2. Secondary fuel Semi coke, Gasoline, Diesel, Coal gas,
(Manufactured). Coke, Kerosene. Producer gas,
Petroleum Water gas.
coke.

Requirements of a good fuel

A good fuel should have the following characteristics:
✓ High calorific value.
✓ Moderate ignition temperature.
✓ Low moisture content.
✓ Low contents of non-combustible matters.
✓ Free from objectionable and harmful gases.
✓ Moderate velocity of combustion.
✓ Combustion should be controllable.
✓ Easy to transport and readily available at low cost.

Calorific values
Definition: Calorific value may be defined as “the amount of heat liberated by the complete
combustion of a unit mass of the fuel”.
The quantity of heat can be measured by the following units:
✓ Calorie (cal)
✓ Kilocalorie (kcal)
✓ British thermal units (BTU)
✓ Centigrade heat units (CHU)

i. Gross calorific value (GCV) (or) Higher calorific value

Gross calorific value is defined as “the total heat generated when a unit quantity of fuel is
completely burnt and the products of combustion are cooled to room temperature”.

For example, when a fuel containing hydrogen is burnt, it undergoes combustion and will be
converted into steam. If the combustion product is cooled to room temperature, the steam gets
condensed into water and the latent heat is evolved. Therefore the latent heat of condensation of
steam so liberated is included in Gross calorific value.

ii. Net calorific value (NCV) (or) Lower calorific value

Net calorific value is defined as “the net heat produced when a unit quantity of fuel is completely
burnt and the products of combustion are allowed to escape”.

NCV = GCV – Latent Heat of Condensation of Steam Produced.

8. Determination of Calorific Values of Solid Fuels by Bomb Calorimeter

Principle: A known weight of the fuel is burnt completely and the quantity of heat liberated is
absorbed in water and measured.

Description: A bomb calorimeter consists of the followings:

(i) A stainless steel bomb: It can withstand a pressure of about 100 atmospheres. It is provided
with two electrodes and an oxygen inlet valve. One of the electrodes acts as support for the
crucible. It is placed in copper calorimeter.

(ii) A copper calorimeter: The copper calorimeter contains a known weight of water. It has an
arrangement for inserting a thermometer and stirrer. The calorimeter is surrounded by air jacket
and water jacket to prevent the loss of heat.

(iii)A stainless steel crucible: It holds the weighed pellet of fuel sample. The crucible is fixed in
such a way that the fuse wire touches the fuel sample.

Fig 4: The bomb calorimeter

Working: A known quantity of fuel (m gm)is taken in the crucible. The bomb is charged with
oxygen to a pressure of 30 atmospheres and the oxygen charging valve is closed tightly. Then the
bomb is placed carefully in a known amount of water (W gm). The water in the calorimeter is
stirred throughout the experiment and its initial temperature is noted (T1ºC). Now the fuel is ignited
by passing current through the fuse wire. The heat produced by burning is transferred into the
water. The temperature is measured to an accuracy of 0.001°C by a Beckmann’s thermometer till
the maximum temperature (T2ºC) is reached.

Calculations:
Mass of fuel = m gm
Mass of water in calorimeter = Wg
Water equivalent of calorimeter = wg
Initial temperature of water = T1°C
Final temperature of water = T2°C
The water equivalent of the calorimeter is determined by burning a fuel of
known calorific value (Example: Benzoic acid, CV = 26565 kcal/kg)
By heat balance, heat produced by the = Heat absorbed by water and
fuel due to combustion calorimeter
If x is the calorific value of fuel, heat = (x × m) cal
produced
Heat absorbed by water and = (W + w) × (T2 − T1)
calorimeter
(x × m) ≡ (W + w) × (T2 − T1)

(W + w)  (T2 − T1 )
cal/g
m
x =

For calculating the more accurate calorific value of a fuel, the following corrections should be
considered.

(i) Fuse wire correction (C1): Since the fuse wire also gives additional heat on heating, it
must be subtracted from the heat.
(ii) Cotton/Thread correction (C2): If fuel is ignited with the help of a cotton or cotton thread,
it will give extra heat and that must also be subtracted from the heat.

(iii) Acid correction (CA): On combustion, the fuels having N and S atoms may produce nitric
acid and sulphuric acid respectively. Formation of these acids are exothermic in nature, this
additional heat must also be subtracted.

(iv) Cooling correction (TC): The temperature difference (T2 − T1) must be higher than what is
actually observed in the calorific value determination. This is because, the process of cooling adds
certain temperature differences and it is known as cooling correction. The cooling correction can
be obtained by plotting time versus temperature. From the rate of cooling (difference of two
temperature per minute, dT°/min) and the actual time taken (t), the cooling correction, dT° × t can
be determined. This cooling correction must be added to the measured temperature rise.

By considering all the corrections, the actual calorific value of a fuel is calculated as follows:

(W + w)  (T2 − T1 + TC ) − (C1 + C2 + C A )
cal/g
HCV, x ≡ m

9. Manufacture of Synthetic Petrol By Fischer-Tropsch Method

The raw materials used in this process are hard coke and steam to produce water gas. i.e.: water
gas is obtained by passing steam over red hot coke.

1200oC
C + H2O CO + H2
Water Gas

The first step in this process is purification of water gas. To remove H2S, the gas is passed through
Fe2O3 and to remove organic sulphur compounds, the gas is again passed through a mixture of
Fe2O3 and Na2CO3.
The purified gas is compressed to 5-25 atmospheres over a catalyst containing oxides of Th, Co
and Mg on Kieselguhr at 2500C (Fig. 5.5). The reaction products mainly contain straight chain
paraffins and olefins.

nCO + (2n+1)H2 CnH2n+2 + nH2O

n-Paraffins
nCO + 2nH2 CnH2n + nH2O
Olefins

Mixture of
Hydrocarbons

Fractionating Column
Catalyst Chamber Gasoline

Purifying
Mixer
CO + H2 Chamber,
Fe2O3+ Heavy Oil
Na2CO3
Cracking
Compressor
Gasoline

Fig 5: Fischer-Tropsch Process

Since the reactions are exothermic, the vapours leaving the vessel are condensed in the
condenser to give petroleum. It is fractionally distilled to yield petrol and heavy oil. Heavy oil is
used for cracking to get more amount of gasoline.

10. Knocking in Spark Ignition (SI) Engines

Causes of knocking in SI engines (petrol engines)

Knocking is a kind of mild explosion, which occurs in internal combustion (IC) engines due to
sudden increase of pressure developed by spontaneous combustion of fuel–air mixture. Internal
combustion engines (IC) are classified into spark ignition (SI) engine and compression ignition
(CI) engine. The spark ignition engine consumes petrol whereas compression ignition engine
operates on diesel oil.

Petrol is one of the lightest fractions of petroleum. Chemically, it is a low boiling hydrocarbons in
terms of carbon atoms C5–C8. Its boiling point range is 40 – 120°C. Its calorific value is 11, 250
kcals/kg. It is used as fuel for petrol (SI) engines.

 Knocking in SI engine is due to pre-ignition or pre-mature ignition of fuels.

 Knocking causes mechanical damage in cylinder; and reduction in power output.

Chemical structure and knocking in petrol engines

The knocking tendency in SI engines decreases with increase in the compactness of molecules,
double bonds and cyclic structure.

 n-Paraffins show poor knocking resistance. Their resistance to knock decreases with increase
in the length of the hydrocarbon chain.

n-Butane → n-Pentane → n-Hexane → n-Heptane

Octane 90 60 30 0
Number:

 Iso-paraffins have better knocking resistance than n-paraffin. Their resistance increase with
increasing number of branches.

 Olefins have better knocking resistance than n-paraffin and iso-paraffins.

 Aromatic hydrocarbons such as benzene and toluene have highest anti-knock values.

In general, knocking tendency in SI engines decreases in the following order:

 n-Paraffin → Iso-paraffins → Olefins → Naphthenes → Aromatics

 It means that aromatics have highest antiknock value whereas n-alkanes have lowest
antiknock value.

 So the presence of maximum quantity of aromatics and minimum quantity of n-alkanes in

petrol is desirable.

Octane rating of fuels (Measurement of knocking in SI engines)

Octane number expresses the knocking characteristics of petrol. n-Heptane (a constituent of petrol)
knocks very badly, so its antiknock value has been arbitrarily given zero. On the other hand, iso-
octane (also a constituent of petrol) gives very little knocking, so its anti-knock value has been
arbitrarily given 100.

CH3 CH3
5 4 3 2 1
CH3 CH CH2 C CH3 CH3 CH2 CH2 CH2 CH2 CH2 CH3
CH3
Iso-octane (2,2,4 trimethyl pentane) n-Heptane
(Octane Number = 100) (Octane Number = 0)

To measure octane number of a gasoline sample, binary mixtures of the two standard oils (iso-
octane + n-heptane) are prepared and tested in a test standard engine.

% of iso-octane % of n-heptane Octane Number Amount of Knocking

100 0 100 Nil
80 20 80 A
60 40 60 B
50 50 50 C
0 100 0 D (maximum)

If a gasoline sample produces same amount of knocking (A) as 80% iso-octane and 20% n-heptane,
then the sample has an octane number of 80.
Definition of octane number: Octane number is defined as “percentage of iso-octane in iso-
octane–n- heptane mixture, which matches the same knocking characteristics of gasoline mixture
[iso-octane-n-heptane mixture of various proportions] when burnt in a standard test engine under
standard conditions”.

Improvement of antiknock value (or) Leaded petrol (or) Advantages of using tetra ethyl lead
(TEL: The octane number of gasoline may be improved by adding about 1-3ml of ethyl fluid (60%
Tetra ethyl lead + 29% Ethylene dibromide + 9% Ethylene chloride + 2% Red dye) to 1 gallon of
petrol. Petrol containing TEL is known as leaded petrol.

Mechanism (prevention) of knocking (or) Action of TEL: TEL decomposes to form (i) lead metal
particles (ii) ethyl free radicals. Lead particles act as oxidation centers and thereby making
combustion homogeneous and uniform. Ethyl free radicals convert straight chain paraffins into
iso-paraffin. Sometimes ethyl free radical combines with the free radicals of knocking process and
terminates the chain growth.

Role of ethylene dibromide: Lead particles produced by TEL may deposit in spark plug of SI
engines. To prevent this deposit, ethylene dibromide is added. It reacts with lead particles to form
lead dibromide (PbBr2) and goes out with exhaust gases.

Disadvantage of using TEL: TEL causes lead pollution and creates atmospheric pollution.

11. Knocking in Compression Ignition (CI) Engines

Causes of knocking in CI engines (diesel engines)

Diesel is one of the heavier fractions of petroleum. Chemically, it is a mixture of hydrocarbons in
terms of carbon atoms C15–C18. Its boiling point range is 250 – 320°C. Its calorific value is 11,000
kcals/kg. It is used as fuel for diesel engines.

In a CI engine, air is alone compressed. This raises the cylinder temperature as high as 300°C.
When the diesel oil is injected or sprayed, it ignites spontaneously and the combustion products
expand and power stroke begins.
Sometimes, even after the compression stroke is over and even after the diesel oil is sprayed,
burning may not start. So, more and more fuel is injected automatically and sudden ignition may
occur and burn the whole of the oil. This delayed ignition results an uncontrolled, excessive
combustion known as ‘diesel knock’. So in CI–engines, knocking is due to delayed ignition or
ignition lag.

Chemical structure and knocking in diesel engines

In general, knocking tendency in CI engines increases in the following order.

n-Paraffin → Iso-paraffins → Olefins → Naphthenes → Aromatics

It means that n-paraffin have the highest antiknock value whereas aromatics have lowest antiknock
value. So the presence of maximum quantity of n-paraffin and minimum quantity of aromatics in
diesel is desirable. Therefore, an oil of high octane number will have a low cetane number and
vice-versa. Consequently, petroleum crude will give petrol of high octane number and diesel of
low cetane number

Cetane rating of fuels (Measurement of knocking in CI engines)

The quality of diesel oil is expressed in terms of cetane number. Based on cetane number, diesel
oil is classified as (i) high speed diesel (cetane number 45 and above) (ii) medium speed diesel
(cetane number 35 – 44) and (iii) low speed diesel (cetane number 25 – 34). Diesel oil having more
cetane number will have the highest ignition temperature. It is possible to increase the cetane
number (ignition temperature) by using certain additives like acetylene, alkyl nitrates, diethyl
ether, nitronaphthalene.

Cetane number expresses the knocking characteristics of diesel. Cetane (C16H34) has a very short
ignition delay and hence its cetane number is arbitrarily taken as 100. On the other hand, α–methyl
naphthalene has very large ignition delay and hence its cetane number is arbitrarily taken as zero.
To measure cetane number of a diesel sample, binary mixtures of the two standard oils (n-cetane
+ α-methyl naphthalene) are prepared and tested in a test standard engine.
 CH3
CH3 ( CH2 )14CH3

n-Cetane o -Methyl naphthalene

(Cetane Number = 100) (Cetane Number = 0)

Definition of cetane number: Cetane number is defined as “the percentage of cetane in cetane-α–
methyl naphthalene mixture, which has the same ignition delay as the diesel oil when burnt in a
standard test engine under standard conditions”.

Improvement of antiknock value (or) Cetane number enhancers: Cetane number of diesel oil
can be improved by adding additives called dopes. Examples: Ethyl Nitrate, Isoamyl Nitrate.

Table 4: Comparison of petrol and diesel as internal combustion engine fuel

S. No. Petrol Diesel
1. Low boiling fraction of High boiling fraction of
petroleum. petroleum.
(Boiling point range: 40-120°C) (Boiling point range: 320-400°C)
2. Chemical composition range Chemical composition range
(C5-C8). (C15-C18).
3. Fuel for SI engine. Fuel for CI engine.
4. Knocks due to premature Knocks due to ignition delay.
ignition.
5. Knocking tendency measured in Knocking tendency measured in
octane rating. cetane rating.
6. Anti-knocking is improved Anti-knocking is improved by
through addition of Tetra Ethyl doping with isoamyl nitrate.
Lead.
7. Lower thermal efficiency. Higher thermal efficiency.
8. Less consumption. More consumption.
 12. Introduction: Nanomaterials

Nanochemistry is a branch of nanoscience which deals with synthesis and characterisation of

materials at nanoscale. They find applications from nanoelectronics to nanomedicine. Nanometer
is so small that if you imagine ten hydrogen atoms placed in a line touching each other, it will
measure one nanometer. A bacterial cell measures a few hundred nanometers (200 nm) across and
a human hair measures about 50,000nm across. The smallest things seeable with the unaided
human eye are 10,000nm across. With only reduction in size and no change in substance, the
characteristics such as electrical conductivity, colour, melting point, strength, we usually consider
as constant for a given material can all change. Nanotechnology is the manipulation of individual
molecules or groups of atoms to make useful materials and devices. Nanotechnology can create a
computer laptop screen that has the thickness and weight of a piece of paper, micro devices to
make toxic waste inert, nanodevices to perform surgery or to detect cancer cells inside the human
blood stream etc.

Nanomaterials Terminology

❖ Nano: The literal meaning of nano is “dwarf” an abnormal short person. In scientific
language, nano is “billionth” on some unit scale.

❖ Nanometer: It is a billionth of a meter.

1
1nm = m = 10 −9 m
1,000,000,000

❖ Nanotechnology: Nanotechnology refers to the manipulation or self assembly of atoms or

molecules to create nanodevices with new and different properties.

❖ Nanochemistry: Nanochemistry is a branch of nanoscience which deals with synthesis

and characterization of materials at nanoscale. They find applications from nanoelectronics to
nanomedicine.
❖ Nanomaterials: Materials which possess an average size of less than 100 nm at least in
one coordinate (dimension) are called nanomaterials or nanostructured materials.

❖ Nanoparticles: Particles or powders with grain size (diameter) less than 100 nm are called
nanoparticles.

❖ Nanoclusters: Aggregate of atoms or molecules in nanoscale dimension (1–10 nm) is

known as nanoclusters. Individual atoms/molecules can form clusters.

❖ Nanorods: Nanorods are one dimensional cylindrical solid with an aspect ratio
(length/diameter) of less than 20 with a diameter ranging from 10 – 100 nm.

❖ Nanowires: Nanowires are one dimensional cylindrical solid with an aspect ratio
(length/diameter) of greater than 20 with a diameter ranging from 10 – 100 nm.

❖ Nanotube: When a graphite sheet is folded into a cylinder or tube, it is considered as

carbon nanotube.

❖ Bucky ball (or) Fullerene, C60: The Bucky ball (or) Fullerene, C60 (short term of buck
Minster Fullerene) is a single, stable molecule containing 60 carbon atoms arranged in a soccer
ball. It is of about 1nm in diameter. Every Bucky ball surface contains 12 pentagons and 20
hexagons. The pentagon’s permit the sheet of carbon atoms to curve into the shape of a sphere.
The Fullerene family is often identified by the letter C followed by the number of carbon atoms.
For example, C60, C70, C80 etc., out of which C60 is more stable and spherical in shape.

❖ Dendrimers: Dendrimers are nanomolecules with regular branching structures. The

number of branching determines the size of the dendrimer which can be controlled.

❖ Quantum dots: Quantum dots (QDs) are small devices that contain a tiny droplet of free
electrons. QDs are colloidal semiconductor nanocrystals ranging from 2 to 10 nm in diameter.

Examples: The most commonly used QDs are cadmium selenide (CdSe), cadmium telluride
(CdTe), indium phosphide (InP), and indium arsenide (InAs).
❖ Bottom-up nanofabrication: The process of making nanostructures starting with small
components such as atoms or molecules is called bottom-up approach.

Examples: Chemical vapour deposition; Sol-gel process; Chemical reduction.

❖ Top-down nanofabrication: The process of making nanostructures starting with larger

structures and taking parts away is called top-down approach.

Examples: Lithography; Ball Milling; Epitaxy.

Classification of Nanomaterials on the Basis Dimensions

Nanomaterials can be classified as: zero dimensional (0-D), one dimensional (1-D), and two
dimensional (2-D) objects. This classification is based on the number of dimensions, which are
not confined to the nanoscale range (1–100 nm).

Table 5: Classification of nanomaterials on the basis of dimensions

S. No. Reduction in size Nanoobjects Examples
in different
coordinates
1. 0-Dimensional Nanoparticles;
d <100 nm
nanomaterials: All Quantum dots.
dimensions x, y, z
are at nanoscale.
2. 1-Dimensional Y Nanotubes;
nanomaterials: Two Nanorods;
d < 100 nm X
dimensions x, y are L Nanowires.
at nanoscale and
other dimension,
length (L) is not at
nanoscale.
 3. 2-Dimensional Nanofilms;
LX
nanomaterials: One LY Nanocoatings.
dimension, t < 100 nm
thickness, t is at
nanoscale and other
two dimensions,
Lengths along LX
and LY are not at
nanoscale.

Classification of Nanoparticles on the Basis Chemical Composition

The currently existing nanoparticles are classified by their chemical composition, namely:

1. Metallic nanoparticles (Au, Ag, Cu, Fe, Zn etc.).

2. Nanoparticles of metal and non-metal oxides (FeO, VO, AlO, ZnO etc.).
3. Semiconductor nanoparticles (ZnS, CdSе, ZnSe, CdS, etc.).
4. Carbon nanoparticles (fullerenes, nanotubes, graphene, diamond).
5. Nanoparticles of organically modified layered silicates and alumosilicates (nanoclays of
different compositions).
6. Nanoparticles of organic dendrite polymers (dendrimers of different composition).
7. Quantum dots.

Distinction between Molecules, Nanomaterials and Bulk Materials

Table 6: Differences between Molecules, Nanomaterials and Bulk Materials
S. No. Property Molecules Nanomaterials Bulk Materials
1. Size Exhibit few Exhibit 1 – 100 Exhibit more
Angstrons (Å) nm at least in than Microns
one dimension (μ)
2. Number of Consist of more Made up of one Consist of
constituents than one atom. to several infinite number
thousand
 depends upon of atoms and/or
their size. molecules.
3. Electronic Confined. Confined. Continuous.
structure
4. Geometric Well defined Well defined Depends upon
structure and predictable. and predictable. crystal
structure.
5. Tools for SEM; TEM. SEM; TEM. SEM; X-ray
characterisat diffraction etc.
-ion depends upon
the properties of
bulk.
6. Examples O2; C2H2;KCl. Fullerene; Bulk copper;
Carbon gold.
nanotubes.

13. Size Dependent Properties of Nanomaterials

The various properties, which get tremendously altered due to the size reduction in at least one
dimension are:
✓ Chemical properties: Reactivity; Catalysis.
✓ Thermal property: Melting point temperature.
✓ Electronic properties: Electrical conduction.
✓ Optical properties: Absorption and scattering of light.
✓ Magnetic properties: Magnetization.

i. Chemical properties
Size reduction in bulk materials leads surface to volume effects. It has been observed that the
surface area to volume ratio increases with decrease of particle size diameter. Therefore size
reduction in Nanomaterials leads to more number of surface atoms with enhanced surface area.
This effect leads more reactivity and catalytic activity of materials in nanoform in turn increases
the reaction rate and efficiency of various chemical reactions.
Examples: Au and Ag in bulk form are chemically inert. But they become good catalyst in
nanoform.

-1
day
1x10-5

-2
Reaction rate , mole m
7.5x10-6
5x10-6
2.5x10-6
1x10-6

0 10 20 30 40 50
Particle diameter, nm

ii. Thermal properties

The melting point of bulk material is directly related with the bond strength. In bulk materials all
the atoms are compactly packed and eletrovalently bonded and hence they exhibit higher melting
points.
In Nanomaterials, surface atoms are not bonded in direction normal to surface plane and hence
surface atoms will have more freedom to move. Hence the melting point of Nanomaterials is size
dependent and it decreases with decrease of particle size diameter.

Examples: Bi (in bulk form: 660K): Bi (6nm: 500K); Bi (4nm: 480K) and Bi (2nm: 400K).

1350 Bulk

1325
Temperature, K

1300

1275
1250

0 10 20 30 40 50
Radius of particle size, nm
iii. Electronic properties
In bulk materials, conduction of electron is delocalized (i.e: the electrons can move freely in all
directions). When the scale is reduced to nanoscale, quantum confinement dominates. Due to
electron confinement, the energy bands are replaced by discrete energy states of electrons, which
make the conducting materials to behave like semiconductors or insulators.
For 0-D nanomaterials, all the dimensions are at nanoscale and hence electrons are confined in 3-
D space. Therefore no delocalization occurs. For 1-D nanomaterials, electron confinement occurs
in 2-D space and electron delocalization occurs along the axis of Nanowires / Nanotubes /
Nanorods.
Examples: Si and Ge are well known semiconductors in single crystal bulk form. But in nanoform,
due to electron confinement, they do not show semiconducting properties.

iv. Optical properties

When a beam of visible light falls on certain substances, they absorb light radiations and get
excited. In order to come back to their original state, they emit energy in the form of light
radiations. This phenomenon is known as photoluminescence.
Because of quantum confinement, size reduction in Nanoparticles shifts the emission of light
towards shorter wavelength (Blue shift).

1 nm 2 nm 3 nm
Photoluminescence

520 570 620

Wavelength maximum, nm
Examples:

CdS (Bulk) + hγ → CdS* (Excited state)

CdS* (Excited) → CdS (Ground state) + Energy as red light
CdS* (6nm) (Excited) → CdS (6nm) (Ground state) + Energy as orange light
CdS* (4nm) (Excited) → CdS (4nm) (Ground state) + Energy as yellow light
CdS* (2nm) (Excited) → CdS (6nm) (Ground state) + Energy as blue/white light

v. Magnetic properties

The size of magnetic nanoparticles influences the value magnetization. The figure 5.4 illustrates
the effect of particle size on the saturation magnetization of zinc ferrite.

The magnetization increases significantly below a grain size of 20nm. Hence, by decreasing the
particle size of a granular magnetic material it is possible to improve the quality of magnets
fabricated from it.

0.95
Remanent Magnetisation

0.9
0.85
(Tesla)

0.8
0.75

0 20 40 60 80 100
Particle diameter, nm

14. Synthesis of Gold Nanoparticles by Chemical Reduction Method

Gold nanoparticles exhibit various sizes ranging from 1 nm to 8 μm. They exhibit different shapes
such as spherical, sub-octahedral, octahedral, decahedral, multiple twined, irregular shape,
tetrahedral, nanotriangles, nanoprisms, hexagonal platelets and nanorods.
1. Synthesis of gold nanoparticles by citrate reduction process
The reduction of a tetrachloroauric acid (HAuCl4) has been initiated by trisodium citrate
(Na3C6H5O7) by injecting specified amount of preheated trisodium citrate solution to a boiled gold
solution in a double walled reactor, which is heated by a bath thermostat to control the water bath
temperature. The mixture liquid was vigorously stirred by Teflon coated magnetic bars.
The color of the solution changed gradually from transparent light yellow, dark black, and finally
to the characteristic wine-red, which indicated the formation of gold nanoparticles.

HAuCl4+ Na3C6H5O7 → Auo (NP) + HCl + [C6H5O7]3– + 3NaCl

2. Synthesis of gold nanoparticles by NaBH4 reduction process

In the NaBH4 reduction process, NaBH4 is used as reduction agent, the citrate acts as a stabilizing
agent and tetrachloroauric acid (HAuCl4) as the precursor.

When the mixture liquid is vigorously stirred by Teflon coated magnetic bars, the color of the
mixture solution immediately changes into pink. Continue stirring the solution for another 15
minutes finally turn the solution wine-red, which indicated the formation of gold nanoparticles.

The reaction rate in this single aqueous system was controlled by the reaction conditions. Different
reaction parameters (e.g. reaction temperature, reactant concentration, addition rate for NaBH4)
can be optimised to get gold nanoparticles with uniform size distribution.

HAuCl4+ 4 NaBH4→ Auo (NP) + 5/2 H2 + 2B2H6 + 4NaCl

3. Synthesis of Silver Nanoparticles by Chemical Reduction Method

In chemical reduction method, silver nitrate (AgNO3) is used as a starting material while trisodium
citrate (C6H5O7Na3) and ascorbic acid (C6H8O6) are used as the reducing agent and surfactant
respectively.

During the synthesis process, the reductant (C6H5O7Na3) directly reduced Ag+ to generate metallic
Ag atoms. The coalescence of atoms led to the formation of metal clusters, which are normally
stabilized by surfactants.
In this method, it is believed that the ascorbic acid acts as surfactant and adsorbs onto the surface
of the Ag atoms, and thus prevented the nanoparticles from agglomerating.

Indication of the formation of silver nanoparticles can be observed by change in the solution
colour. During this process, the solution becomes greenish before it stabilised. Later it changes
into light yellow colour indicates the growth of the AgNPs.

4Ag+ + C6H5O7Na3 + 2H2O → 4Ago + C6H5O7H3 + 3Na+ + H+ + O2

Applications of Nanomaterials in Medicine

1. Drug discovery and Drug delivery

 CNTs can be widely used as drug carriers for drug delivery, as they can easily adapt
themselves and enter the nuclei of the cell. The most important use of CNT in drug delivery is that
they can be equipped with miniaturized video cameras, which help in colonscopic and endoscopic
procedures.
 Dendrimers carrying different materials on their branches can do several things at one time,
such as drug delivery recognizing diseased cells, diagnosing disease states including cell death.
 The pharmaceutical applications of dendrimers include nonsteroidal anti-inflammatory
formulations, antimicrobial and antiviral drugs, anticancer agents, pro-drugs, and screening agents
for high-throughput drug discovery.

2. Surgery
 Gold coated nanoparticles can be used as flesh welders. In this technique, a greenish liquid
containing gold-coated nanoshells is dribbled along the seam. An infrared laser is traced along the
seam, causing the two sides to weld together using laser. This could solve the difficulties and blood
leaks caused when a surgeon tries to re-stitch the arteries that have been cut during organ
transplant.

3. Cancer diagnosis and cancer therapy

 Silver nanoparticles can be used as a promising candidate in chemotherapy,
photosensitizers and/or radiosensitizers, biodiagnostics, bioimaging, transfection vectors, and
antiviral agents; some of these have been entered into clinic trials.
 Gold nanoparticles have become an interesting research area in cancer diagnosis, imaging
and especially treatment. The gold nanoparticles that are located at a site of cancer cells can be
irradiated with infrared to heat them up and destroy the nearby cancer cells.
 Cadmium selenide nano particles in the form of quantum dots are used in detection of
cancer tumors because when exposed to ultraviolet light, they glow. The surgeon injects these
quantum dots into cancer tumors and can see the glowing tumor, thus the tumor can easily be
removed.
 In a recent study, antibody-conjugated magnetic poly-(D, L-lactide-co-glycolide) (PLGA)
nanoparticles with doxorubicin (DOX) were synthesized for the simultaneous targeted detection
and treatment of breast cancer. DOX and magnetic nanoparticles were incorporated into PLGA
nanoparticles, with DOX serving as an anticancer drug and Fe2O3 nanoparticles used as an imaging
agent.

4. Tissue engineering applications.

 Nanoparticles such as graphene, carbon nanotubes, molybdenum disulfide and tungsten
disulfide are being used as reinforcing agents to fabricate mechanically strong biodegradable
polymeric nanocomposites for bone tissue engineering applications.

5. Dental diagnostics
 The metallic nanoparticles as iron nanoparticles single or conjugated with polysaccarides,
and gold nanoparticles single or conjugated with antibodies or peptides for specific cellular
biomarkers were used in dental diagnostic. They have recently been investigated as optical or
magnetical contrasting agents in medical imaging techniques for early detection of oral cancer,
and for identifying and differentiating infectious pathogens.

6. Cell labeling and bio-imaging

 A class of nanoparticles known as ‘quantum dots’, which can emit different types of light
depending on their size, have wide applications in biotechnology for cell labelling and bioimaging,
including imaging in cancer studies.
 The enhanced magnetic properties of iron (III) oxide nanoparticles make them suitable for
use as contrast agents in magnetic resonance imaging (MRI).
 Fluorescent CdSe/ZnS quantum dots could produce a higher contrast image, when used in
combination with MRI (magnetic resonance imaging), and are used for tumor targeting, tumor
angiogenesis imaging, and metastasis cell tracking.

QUESTIONS
PART-A
1. State phase rule.
2. State mathematical statement of phase rule.
3. Define the term phase.
4. Define the term components.
5. Define the term degrees of freedom.
6. What is meant by phase diagram? State its significance.
7. What are the limitations of phase rule?
8. What are the advantages of phase rule?
9. What is meta-stable equilibrium?
10. What is triple point?
11. State reduced phase rule.
12. State the conditions under which two substances can form a simple eutectic.
13. Eutectic is a mixture and not a compound. Explain.
14. Mention the differences among melting point, triple point and eutectic point.
15. What are fuels? Give one example each for primary and secondary solid, liquid and gaseous
fuels.
16. What are the requirements of an ideal fuel?
17. Distinguish between GCV and NCV.
18. Why is net calorific value? Less than gross calorific value? When are they equal?
19. What is synthetic petrol?
20. What is meant by knocking in IC engines?
21. Distinguish between knocking in SI engine and CI engine.
22. Define octane number of petrol. How can it be improved?
23. What is leaded petrol?
24. Define octane number.
 25. What are the advantages and disadvantages of leaded petrol?
26. Why is ethylene dibromide added, when TEL is used as antiknock?
27. How does TEL improve the octane number of petrol?
28. Select the compound which possesses highest octane number and cetane number out of n-
heptane, n-hexadecane, n-octane and isooctane.
29. Arrange n-octane, naphthalene, isooctane in increasing order of their knocking tendency.
30. Which is having higher octane number, natural gasoline or cracked gasoline?
31. Define cetane number of diesel. How can it be improved?
32. Differentiate petrol and diesel as IC engine fuels.
33. Define nanochemistry.
34. Define nanotechnology.
35. What are nanomaterials?
36. How are nanomaterials classified on the basis of dimensions?
37. How are nanomaterials classified on the basis of chemical composition?
38. Define the terms: top-down nanofabrication and bottom-up nanofabrication.
39. Mention any four methods for the synthesis of nanomaterials.
40. What is Bucky ball?
41. What are dendrimers?
42. Define quantum dots.
43. Differentiate between molecules, nanomaterials and bulk materials.
44. Mention the various properties which get altered by size reduction.
45. What are nanoparticles?
46. Mention some of the applications of nanoparticles.

PART-B
1. State phase rule and explain the terms involved in it with examples.
2. Draw and explain the labeled phase diagram of water system.
3. What is thermal analysis? How is it used for constructing a eutectic phase diagram?
4. Discuss in detail the lead silver system. Explain Pattison’s process.
5. Describe bomb calorimeter with neat diagram for the determination of calorific value of a
solid fuel.
6. What is synthetic petrol? Discuss the method of preparation of synthetic petrol by Fischer-
Tropsch process.
 7. What is meant by knocking in petrol engines? How is knocking prevented?
8. Discuss the size dependent properties of nanomaterials.
9. What are the properties that change from its bulk form to nano size form? Explain with
each example.
10. Discuss the synthesis of gold nanoparticlessnanoparticles by chemical reduction method.
11. Discuss the synthesis of silver nanoparticlessnanoparticles by chemical reduction method.
12. Explain any six applications of nanomaterials in medicine.

References
1. Jain P C and Monika Jain, 2018, “Engineering Chemistry”, Dhanpat Rai Publishing
Company.
2. Dara S S and Umare S S, 2010, “Text Book of Engineering chemistry”, S. Chand & Co.
Ltd., New Delhi.
3. Sheik Mideen A, 2019, “Engineering Chemistry”, Airwalk Publications, Chennai.