LECTURE 1

MOLECULAR ORBITAL THEORY

INTRODUCTION AND POSTULATES
Postulates of Molecular Orbital Theory

Molecular Orbital Theory was given by R.S. Mulliken and

F. Hund.
According to MOT the valence electrons are associated
with all the nuclei in the molecule.

1. Atomic orbitals with same energy & symmetry combine

to form molecular orbitals by LINEAR COMBINATION OF
ATOMIC ORBINTALS (LCAO)

i. If ΨA&ΨB are wave functions of atoms A & B then

according to LCAO: ΨM.O = ΨA ± ΨB
ii. Two types of molecular orbitals are formed: bonding
and anti bonding molecular orbitals.

iii. Molecular orbitals formed the additive overlap of two

atomic wave functions is known as Bonding Molecular
orbital. i.e. Ψb = ΨA + ΨB

iv. Molecular orbitals formed by subtractive overlap of

two atomic orbitals wave function is called Anti-bonding
molecular orbital i.e. Ψa = ΨA -ΨB
Linear combination of atomic orbitals
S-orbital linear combination
Linear combination of atomic orbitals
P-orbital linear combination
2. The no. of molecular orbitals formed is always equal is
the number of atomic orbitals taking part in bond
formation.
3. Energy level of bonding M.O. is less than that of
individual atomic orbitals. So, electrons present in bonding
M.O stabilizes the molecule.

4. Energy level of anti-bonding M.O is more than that of

individual atomic orbitals. So electrons present in anti-
bonding M.O destabilizes the molecule.

5. Molecular orbitals that do not participate in bonding are

called non-bonding M.O & their energy is equal is that of
individual atomic orbitals.

6. Molecular orbitals are polycentric.

7. The atomic orbitals involved in the formation of M.O.
completely lose their identity after the formation of
molecular orbitals.

8. Electrons filling in the molecular orbitals follow Aufbau

principle, Pauli’s exclusion principle & Hunds rule of
maximum multiplicity.
9. The electrons are filled in the molecular orbitals
according to the following order:

From H2 to N2:

σ1s, σ*1s, σ2s, σ*2s, π2px = π2py, σ2pz, π*2px= π*2py,

σ*2pz

From O2 to Ne2:

σ1s, σ*1s, σ2s, σ*2s, σ2pz, π2px = π2py, π*2px= π*2py,

σ*2pz
[Link] or ions with one or more unpaired e- in
molecular orbitals are paramagnetic while those with all
paired electrons in M.O. are called diamagnetic.

[Link] & strength of a chemical bond is expressed in

terms of bond order.
[Link] Order – Bond order is equal to one half of the
difference between the number of electrons in bonding
M.O & the no. of e- is anti-bonding M.O.

B.O. = ½ (Nb -Na)

Nb = electrons is B.M.O.
Na = electrons is anti B.M.O.
Significance of bond order:

▪ Zero B.O.: Molecule does not exist.

▪ Negative bond order is not possible.
▪ Positive value of B.O.: Molecule exists & is stable.
▪ Bond order of +1, +2, +3 indicates the molecule has
single, double or triple bond respectively.

▪ Bond order α Bond stability α 1/ Bond length

Differences between bonding and anibonding
molecular orbitals.
ANTIBONDING MOLECULAR
BONDING MOLECULAR ORBITALS
ORBITALS
They are formed by additive They are formed by subtractive
overlapping of atomic orbitals. overlapping of atomic orbitals.
Ψb = ΨA + ΨB (A and B are two atomic Ψa = ΨA - ΨB (A and B are two
orbitals) atomic orbitals)
Electrons contribute to the formation Electrons do not contribute to the
of bond. formation of bond.
They have low energy and high They have high energy and low
stability. stability.
They are shown as σ ,π etc. They are shown as σ*, π* etc.
Maximum electrons are located in
Electrons are scattered.
between the two nuclei.
Electron density is higher. Electron density is lower.
LECTURE - 2
Application of Molecular orbital theory to
Homo-nuclear diatomic molecules
Molecular Orbital Diagrams of some
homo-diatomic molecules

HOMODIATOMIC MOLECULES: These are the

molecules formed of same atoms. Example: O2, H2 etc.
Following order of configuration is followed for various
molecules:

From H2 to N2 :
σ1s, σ*1s, σ2s, σ*2s, π2px= π2py, σ2pz, π*2px= π*2py,
σ*2pz

From O2 to Ne2 :
σ1s, σ*1s, σ2s, σ*2s, σ2pz, π2px= π2py, π*2px= π*2py,
σ*2pz
From H2 to N2 From O2 to Ne2
Hydrogen (H2) and Hydrogen ion (H2 +)

Hydrogen (H2): (2e-): σ1s2, σ*1s0

The molecule is diamagnetic due to paired electrons.

H2+: σ 1s-1

Less stable than H2 as its bond order is less than H2.

Paramagnetic due to presence of one unpaired electron
Molecular orbital diagrams of
Hydrogen (H2) and Hydrogen ion (H2+)
Dihelium (He2) and dihelium ion (He2 +)

He2+: (3e-): σ1s2

It is paramagnetic in nature

He2: (4e-): σ1s2, σ*1s2

He2 cannot exist as its bond

order is zero, So Helium exists
in mono atomic form (He).
Be2 does not exist in nature:

Be2 (8e-): σ1s2, σ*1s2, σ2s2, σ*2s2

As the bond order

of Be2 is zero, the
molecule cannot be
formed. So, it exists
in mono atomic
form (Be).
O2 (16e-):
2 2 1 1
σ1s2, σ*1s2, σ2s2, σ*2s2, σ2pz2, π2px = 2py , π*2px = π*2py

Magnetic Behaviour:
Paramagnetic due to
presence of two unpaired
electrons in the
molecular orbitals.
N2 (14e-):

Magnetic
Behaviour: It is
diamagnetic in
nature since all the
electrons in
molecular orbitals
are paired.
Superoxide (O2 - ) and peroxide (O2 2- ) ions

Paramagnetic Diamagnetic
B.O. of O2 = ½ (Nb-Na) = ½ (8-4) = 2

B.O. of O2- = ½ (Nb-Na) = ½ (8-5) = 1.5

B.O. of O2-2 = ½ (Nb-Na) = ½ (8-6) = 1

Since, B.O. α stability.

So, the order of stability will be: O2 ˃ O2- ˃ O2-2
Also, B.O. α 1 / Bond Length
So, the order of bond length will be: O2-2 ˃ O2- ˃ O2
LECTURE - 3

Application of Molecular orbital theory to

Hetero-nuclear diatomic molecules
Hetero-diatomic molecules

▪ Molecules that contain two different atoms.

▪ Molecular orbital energy level diagram is always

skewed towards the more electronegative atom.

▪ More electronegative atomic orbital lies closer to

bonding M.O. and less electronegative atomic orbital
lies closer to antibonding M.O.
MO Diagram of NO
MO Diagram of NO (15 e-):

Its bond order is calculated as :

Bond order = ½ [10 – 5]

= ½ [5] = 2.5

NO molecule is paramagnetic in nature due to an

unpaired electron in π*2px orbital
MO Diagram of CO
MO Diagram of CO: (14 e-):

σ(1s2) < σ∗(1s2) < σ(2s2) < π(2px)2 =π(2py)2 < σ(2pz)2 <
σ∗(2s2) π∗(2px)0 π∗(2py)0

Its bond order is calculated as :

Bond order = ½ [10 – 4]
= ½ [6] = 3

Diamagnetic in behavior as it does not contain any

unpaired electron.
HF (10 e-) : σspz2
1s and 2s electrons as well as 4 electrons of p orbital of
fluorine do not participate in the formation of
molecular orbital of HF and exist as lone pairs.1s of
hydrogen pairs up with 2p unpaired electron of
fluorine to form σspz molecular orbital.

It is a stable molecule as the bond order is 1.

HF is diamagnetic in nature.
Ques. On the basis of MO theory calculate the bond order of
NO. Will NO be paramagnetic or diamagnetic?
Ans. The electronic configuration of NO =
σ(1s2) σ∗(1s2) σ(2s2) σ∗(2s2) σ(2px)2 π(2py)2 π(2pz)2 π∗(2py)1
Bond order = Bonding electron – non-bonding electron
2
Bond order =10−5
2
Bond order = 2.5
Hence, the bond order of NO will be 2.5.
LECTURE - 4
Liquid crystals: Classification, Properties and
Applications
LIQUID CRYSTALS
Liquid Crystals are state of matter which has properties
between those of conventional liquids and
solid crystals. For example, a liquid crystal may flow like a
liquid, but its molecules may be oriented in a crystal-like
way.
The liquid-crystalline state is often called mesomorphic
state (mezos meaning "intermediate"), and the liquid
crystals are called mesophase.

Friedrich Reinitzer, Austrian botanist studied about it first in

1888 in a material known as cholesteryl benzoate .
Following character describe the
crystalline structure:

Positional order: the extent to which an average molecule

or group of molecules shows translational symmetry (as
crystalline material shows).

Orientational order: represents a measure of the

tendency of the molecules to align along the director on a
long-range basis.
Bond Orientational Order: describes a line joining the
centres of nearest neighbour molecules without
requiring a regular spacing along that line.

Positional order + Orientational order = crystal phase

Varying Positional order + Orientational order = LC

phase
▪ Positional order + Orientational order =
Crystal Phase

▪ Positional order + No Orientational order = Plastic

Phase
▪ Varying Positional order + Orientational order = Liquid
crystalline Phase
▪ No positional order + No Orientational order =
Isotropic (Liquid) Phase
Properties of liquid crystals

▪ The molecules are rod shaped or disc shaped.

▪ All liquid crystals are mesogens but all mesogens are
not liquid crystals.
▪ Molecules are anisotropic in nature.
▪ Assuming that the direction of preferred orientation
in a liquid crystal (LC) is ↑, this direction can be
represented by an arrow, called the director of the
LC.
▪ Each molecule is orientated at some angle to the
director.

▪ These molecules possess very strong dipole moment.

▪ The liquid crystal molecules prefer to align parallel to
each other because of the strong intermolecular
attraction (π-π interaction).
▪ A typical Liquid Crystal molecule is represented by a
central rigid part, known as mesogen (generally
aromatic) and the flexible ends (generally aliphatic
groups).
▪ It consists of two or more ring systems connected by a
central linkage group.
Essential requirements for a molecule
to be a liquid crystal
▪ Shape of the molecule must be rod like or disc like.
▪ Molecule must be anisotropic in nature.
▪ Molecule must have some rigidity in its central
region and the ends must be flexible.
▪ Although LC’s combine the properties of a crystalline
solid and an isotropic liquid, they exhibit very
specific electro-optical phenomena, which have no
equivalent analogues in solids or in liquids.
 Classification of liquid crystals:

Liquid Crystals

Thermotropic L.C. Lyotropic L.C.

(Temperature dependent) (Solvent dependent)

Calamatic L.C. Discotic L.C. Lamellar Hexagonal Cubic

(Rod shaped) (Disc Shaped)

Smectic Nematic
Discotic Nematic Discotic Columnar
L.C. L.C.

▪ Smectic A ▪ Ordinary Nematic

▪ Smectic C ▪ Nematic Cholesteric
1. Thermotropic liquid crystals:

They are formed by change of temperature. They occur

as liquid crystals over a certain temperature range
between the solid and liquid phase. Example – LCD TV’s,
alarm clocks.
 Thermotropic liquid crystals are further classified into:
a) Calamatic L.C.(Rod like or elongated molecules)
b) Discotic Liquid Crystals (Disc shape molecules)
Calamatic liquid crystals are elongated, rod shaped
molecules. They are further classified as Nematic and
Smectic liquid crystals.
Nematic liquid crystals
▪ Word Nematic derived from Greek word Nema which
means "thread".
▪ No positional order, but possess orientational order.

▪ Molecule have elongated rod like shape and are

thread like.
▪ Do not have layered structure.
▪ Flow like normal liquids.

▪ They have low viscosity.

▪ Formed at relatively higher temperature.
▪ Can be aligned by the
application of electric on
magnetic field.
▪ Molecules are free to
move in all the directions.
▪ Flow in all directions & not
in layers.
▪ E.g.- p-azoxy anisole (first
synthetic liquid crystal to
be produced).
Nematic liquid crystals cab be further classified as:
a) Ordinary nematic phases: These molecules possess
ordinary nematic phase characteristics as discussed
earlier.
b) Cholesteric nematic phases: This phase is also
known as chiral nematic phase. The molecules are
essentially chiral and resembles nematic molecules in
nature.
Cholesteric Liquid Crystals
(Chiral Nematic)
▪ This phase is usually observed from cholesterol
derivatives.
▪ The molecules are essentially chiral.

▪ The molecules are arranged in layers.

▪ These are formed by adding chiral twisting agent to
the nematic liquid crystals.
▪ Each layer in Cholesteric liquid crystal is tilted with
respect to the other one, and hence the molecules
take a one complete turn of 360 degrees to make a
helix.
▪ The distance covered by the director in making a one
complete turn is known as pitch.
▪ Cholesteric Liquid
crystal reflects light
approximately equal
to pitch.
▪ Pitch is inversely
proportional to the
temperature.
▪ Pitch is affected by
temperature,
pressure as well as
by electric and
magnetic fields.
Smectic Liquid Crystals:
▪ Molecules are cigar shaped.
▪ Have short range orientational as well as positional
order.
▪ These are arranged in layers i.e. have layered structure.
▪ They do not flow like normal liquids and has limited
mobility.
▪ They have high viscosity.
▪ Not affected by external electric or magnetic field.
▪ Molecules are free to
move within the layers,
but not from one layer
to another.
▪ Flow in layers and
difference layers can
slide over one another.
▪ Are of two types:
Smectic A and C.
▪ E.g.: Ethyl-para-azoxy
phenetole.
Discotic Liquid Crystals:

▪ Molecules are essentially disc shaped.

▪ Discotic mesogens are typically composed of an
aromatic core surrounded by flexible alkyl
chains. The aromatic cores allow charge transfer in
the stacking direction through the π conjugate
systems. The charge transfer allows the discotic liquid
crystals to be electrically semi conductive along the
stacking direction.

▪ They are of two types: Discotic nematic Phase and

Columnar Phase.
Disc-shaped molecules have a tendency to lie on top of
one another forming either discotic nematic phases
(with discs oriented similar to that of nematic phase i.e.
not having position order but having orientation order)
or columnar phases (have column-like structure).
Lyotropic Liquid Crystals:

▪ Lyotropic liquid crystals are two component

systems, where an amphiphile is dissolved in a
solvent.
▪ Thus, lyotropic mesophases are solvent and
concentration dependent.
▪ The amphiphillic compounds are characterized by
two different moieties, a hydrophilic polar head
and a hydrophobic tail.
▪ LLC are made by adding solvent to the solid until critical
micelle concentration (CMC) is reached. On further
addition of solvent LLC changes into liquid phase.
▪ Examples: molecules of soaps, phospholipids (present
in cell membranes), toothpaste, many proteins and cell
membranes, tobacco mosaic virus.
Three types of lyotropic liquid crystals are well known.
These are: lamellar, hexagonal and cubic phases.
i) The simplest liquid crystalline phase that is formed by
spherical micelles is the ‘micellar cubic’, denoted by the
symbol I1. This is a highly viscous, optically isotropic phase
in which the micelles are arranged on a cubic lattice.
ii) At higher amphiphile concentrations the micelles fuse to
form cylindrical aggregates of indefinite length, and these
cylinders are arranged on a long-ranged hexagonal lattice.
This lyotropic liquid crystalline phase is known as the
‘hexagonal phase’, and is generally denoted by the
symbol HI.
iii) At higher concentrations of amphiphile the ‘Lamellar
Phase' is formed. This phase is denoted by the symbol
Lα. This phase consists of amphiphilic molecules are
arranged in bilayer sheets separated by layers of water.
 Applications of liquid crystals:

▪ Liquid crystals are used for decorative purpose in

cosmetics.
▪ LLC’s based delivery system such as cream, ointment,
transdermal patches etc have been used in
pharmaceutical.
▪ Thermotropic Cholesteric liquid crystals are used in
body care cosmetics.
▪ Due to their colour effect Cholesteric liquid crystals are
used in nail paints, eye shadows etc.
▪ Discotic liquid crystals are used in photovoltaic
devices, organic light emitting diodes (OLED), and
molecular wires.
▪ Liquid crystals are used for displays in LCD's,
Calculator, wrist watches etc.
▪ Have Medical applications like localized drug
delivery.

▪ To detect radiations& pollutants in atmosphere.

▪ Used in non-destructive testing.
▪ Cholesteric liquid crystals are used in coloured
thermometers.
▪ Used to locate tumours, veins, arteries, infections,
foetal placenta etc.
Industrially important Liquid Crystal
Liquid Crystal have been intensively studied as
functional materials. Industrially important
materials based on liquid crystals are
nonmaterial, polymer blends, reinforced
materials, elastomers, flexible glass are follows.
1. Liquid Crystal polymer (LCP’s)
2. Liquid Crystal Elestomers (LCE’s)
3. Liquid Crystal Glass
4. Nonmaterial enhanced liquid crystalline Material
5. Liquid Crystal as reinforced material
1. Liquid Crystal polymer (LCP’s)

▪ Liquid crystal polymers are polymers with the

property of liquid crystal, usually containing
aromatic rings as mesogen. They have excellent
mechanical and electrical properties and
outstanding chemical resistance.

▪ E.g. Ultra-high strength and light weight fibers and

cables, bulletproof vest, tennis strings and hockey
sticks. These includes Kevlar and vectra polymer.
2. Liquid Crystal Elestomers (LCE’s)

▪ LCE films can be used as optical retarders due

to their anisotropic structure because they can
control the polymerization state of transmitted
light . They are commonly used in 3D-glass,
patterned retarders for transflective displays
and flat panel LC display.

▪ LCEs are used to make actuators and artificial

muscles for robotics.
▪ Azobenzene containing liquid crystal elastomers
(AzBz-LCE) can be chosen as one of the
optimal electronic liquid crystal elastomer for
structuring organic electronic systems used for
application in drugs and foods because they
have properties of both liquid crystal and
elastomers.
3. Liquid Crystal Glass

▪ Liquid Crystal glasses are most widely used in

digital devices industry. These glasses provide
the flexibility and reduced thickness in the
displays.

▪ Eg. Amorphous silicon active matrix LCD (AM

LCD)
4. Nonmaterial enhanced liquid
crystalline Material

▪ Nonmaterial enhanced liquid crystalline

properties such as threshold voltage, response
time, viscosity, dielectric anisotropy, refractive
index which are important in the area of LC
displays (LCD’s)
5. Liquid Crystal as reinforced
material
▪ By the copolymerization of p-hydroxy benzoic
acid and phthalic acid with ethylene glycol
resulted in the reinforced material which
provide the strength and stiffness to
thermotropic polymer. These are also used as a
reinforcing fillers in thermoplastic fillers.
LECTURE - 5
Structure and Applications of Graphite and
Fullerenes
Graphite: An allotrope of Carbon
Structure of graphite:

▪ Graphite is an allotrope of carbon (it is made up of

only pure carbon atoms).

▪ Each carbon atom in graphite is sp2 hybridised.

▪ 6 such carbon atoms join with the covalent bonds to
form hexagons.
▪ In hexagons each carbon atom forms three covalent
bonds (C-C distance is 1.42 Ǻ) with other carbon
atoms.
▪ Fourth electron of each carbon atom is free to move
within the layer.
▪ Various hexagons join together to form a plane or sheet
called graphene.

▪ Various sheets (graphene) are arranged one above the

other.
▪ Different layers of graphite are attached to each other
with weak Vander Waals forces.

▪ Distance between two successive sheets is 3.41 Ǻ.

▪ Graphite has planar, two dimensional structure.
Name of the Molecule Graphite
Molecular Formula C
Hybridization Type sp2
Bond Angle 120o
Geometry Trigonal Planar

Hybridisation of C in graphite:

Ground state Excieted state

STRUCTURE OF GRAPHITE
Properties of Graphite:
▪ It is greyish black and greasy substance.
▪ Has metallic luster and is opaque to light.
▪ High Melting point because the strong covalent bonds
take long time to break.
▪ Slippery nature / Layers can slide one another due to
weak Vander Waal forces of attraction between the
two layers.

▪ Low coefficient of friction.

▪ Ineffective in vaccum conditions.
▪ Thermodynamically more stable than diamond.
▪ Graphite exists in two forms: α-graphite and β-
graphite.
▪ In spite of being non-metal, graphite is a good
conductor of electricity due to the presence of free
electron in pz orbital of each carbon

▪ Density 1.25g/cm3
Applications of Graphite:

▪ Used as a lubricant as layers can slide over one

another due to weak vanderwaals forces.
▪ Used in pencil leads due to soft, slippery nature and it
leaves a black mark on paper when rubbed against it.
▪ It is used in the preparation of electrodes as it
conducts electricity due to presence of free electron on
each carbon atom.
▪ Due to high melting point it is used to prepare
crucible for making high grade steel.
▪ It is used as moderator in nuclear reactors as it
absorbs fast moving neutrons.

▪ Used as conductive ink for screen printing.

Crucibles made of graphite Graphite conductive ink for

screen printing
Uses of Graphite
Fullerene

(Discovered by Kroto&Smalley)

▪ It is an allotrope of carbon, also called buckminster

fullerene or Bucky Ball.
▪ Fullerenes exist as C60, C70, etc. The canonical
structure, C60, has icosahedral symmetry and an
electronic structure similar to that of graphene.
▪ C60 is the most stable & widely used member of
fullerene family.
Structure of C60
▪ Made up of 60 carbon atoms.
▪ Each carbon atom is sp2 hybridised, forming three
bonds and having one unpaired electron.
▪ There are 12 pentagons& 20 hexagons of C atoms.
▪ No two pentagons touch each other i.e. each
pentagon is surrounded by hexagons from all the
sides.
▪ Diameter of C60 molecule is 7A°; geometry-
truncated icosahederon or geodesic dome.
▪ There are 30 (C=C) double bonds in C60.
▪ There are 60 vertices,32 faces.
▪ C-C single bond length-1.45A°; C=C double bond
length=1.38A°
▪ It is highly symmetrical molecular & is said as zero
dimensional.
▪ Has tendency to avoid double bonds in pentagon
rings.

▪ Fullerene crystal structure is FCC.

▪ Its density is 1.65 gm /cc.
Structure of fullerene
Preparation of Fullerene:

▪ Fullerenes are prepared by Arc Discharge Method.

▪ In this the graphite rods are vapourised in an inert
atmosphere of helium gas.
▪ Graphite rods evaporate to form a mixture of
fullerenes ( C60, C70 etc).
▪ From this mixture pure C60 is isolated by column
chromatography.
Preparation of Fullerene:
Graphite rods kept in an inert atmosphere (He gas)
at .05 to .1 atm pressure.
Electric current

Rods evaporate to give fullerene soot (light and fluffy dust)

Containing 5 to 15 % fullerenes.

Sublimation

Fullerene mixture
Chromatography using alumina
hexane
C60
Properties

▪ Mustard colored solid and looks brown and black as its

thickness increases.
▪ Basically semiconductors but on doping with alkali
metals can be converted into conductor or super
conductor.
▪ Shows poor aromatic nature.
▪ Strongest known material to man.
▪ Exists as discrete molecule unlike graphite or diamond.
▪ Pentagon of a fullerene are more strained than the
hexagon, so at higher temp., fullerene molecule break
at pentagon sites.
▪ It is possible to trap some ions inside fullerene cage or
attach some functional molecules to fullerene from
outside.

▪ Can be compressed to lose 30% of its original volume,

without destroying the carbon edge structure.
Uses of Fullerene

▪ Have powerful antioxidant properties, so used in health

& personal care areas.

▪ C60 shows catalytic process.

▪ Act as drug delivery agent.
▪ C60 derivatives act as potential inhibitors to HIV.
▪ Used in preparation of superconductors.
▪ In optical devices.
▪ In preparation of soft Ferro magnets.
▪ Used in batteries as charge carriers.
Carbon Nanotube

 Introduction
 Silent feature
 Properties
 Types of CNT
 Introduction
CNT is one of the most important nanomaterial at
present time. Before 1991,only 2 allotropes of
carbon were known namely Diamond and
Graphite. But in 1991, Japanese physicist Sumio
Lizima discovered another allotrope of carbon
called carbon nanotube. When we roll up 2D
graphite (Graphene) sheet into a cylindrical tube,
we get CNT. The diameter of CNT is about 1-3
nm and can have length upto few micrmeter.
CNT exhibit extraordinary mechanical properties
 Silent feature of CNT
▪ They are stiff as diamond.
▪ They are light weight.
▪ Their density is 1/4th of that of steel and thermal
opacity is 20 times more than steel.
▪ In CNT each carbon atom is bounded to 3 other
carbon atoms through covalent bonds and forms a
lattice in the shape of hexagons
▪ Outer diameter : 2-20 nm
▪ Inner diameter: 1-3 nm
▪ Length: 1-6 µm
▪ MWCNT are different from carbon nanofibre (CNF).
CNF have diameter of 200 nm and they are not hollow
from inside.
▪ CNF have been in use for several decades to
strengthen compound but their lattice is different from
CNT.
▪ CNT is improved version of CNF

MW- CNT
SW- CNT
Properties of Carbon nanotubes

▪ CNT as elastic-tensile strength of CNT is about 200 Giga

Pascal and therefore CNT can be stretched 20% of their
rest length and can be bent and even tied a knot with no
resulting effect.

▪ CNT are good conductor of heat- they have very high

thermal capacity. So thermal expansion produced in CNT
is very small

▪ CNT have good electrical conductivity – CNTs have very

few defect so they can carry billion ampere of current /cm

▪ CNT are very strong- CNTs are 10 times stronger than

steel.

▪ Chemically stable- They are resistant to corrosion.

Type of Carbon nanotube
▪ Single Walled Carbon Nanotube
(SW-CNTs)
▪ Diameter 0.5-2.5 nm , length 2 µm
▪ Aspect ratio is typically greater and
often goes up to 10,000
▪ It posses 1-D structure and is called
Nanowire. Eg. Armchair and Zig Zag
SWCNT
▪ SWCNT is used in electronics
▪ Their band gap is from 0 to 2 eV and
they can exhibit both metallic and
semiconducting behavior.
Type of Carbon nanotube

▪ Multi Walled Carbon Nanotube

(SW-CNTs): It consist of several
nested coaxial single walled
CNTs. E.g. Chiral MW-CNT
▪ Aspect ratio is typically between
50 and 4,000
Preparation Method of CNTs
1. synthesis of CNTs by Electric arc discharge
method

In this method, a potential of 20–25 V is applied

across the pure graphite electrodes separated by
1 mm distance and maintained at 500 torr
pressure of flowing helium gas filled inside the
quartz chamber
2. Carbon Nano Tubes (CNTs) are prepared by
the catalytic deccomposition of Methane (CH4)
at 680 degree Celcius for 120 minute, by using
Nickel Oxide- Silica binary aerogels as the
catalyst.
Application of CNTs
1. Composite material containing CNT are
being used in sports accessories like bicycle
frames, tennis rackets, hockey sticks etc.

2. CNTs are used to make Bullet Proof

Jackets

3. CNTs can reduced the weight of aircraft

and spacecraft upto 30%.
APPLICATIONS OF CNTs

4. CNTs can be used to build high performance

transistors to replace silicon based transistors
because of semi-conducting properties of
SWCNT.

5. CNTs can be used to manufacture biosensors

and electrochemical sensors which are used to
sense green house gases (CO2, CH4) in
environment.

6. CNTs can be used to make electrodes.

LECTURE - 7
Concepts, Properties and Applications of
Nano- Sciences and Nano- materials
Nanomaterials

Nanomaterials: are materials having at-least one of its

dimensions in the nanometre scale (1 nm= 10-9 m).

Nanotechnology: is the technology of manipulating a

material and its properties at the nanoscale (atomic or
molecular scale) for target-specific applications.

Nanostructured materials: Nanomaterials can be zero,

one, two or three dimensional.
Various nano materials:
▪ Nano-particles
▪ Nano-wires
▪ Nano-tubes
▪ Nano-rods
▪ Nano-porous materials
Effects of Nano size:

▪ Properties depends on size, composition and structure

▪ Nano size increases the surface area
▪ Change in surface energy (higher)
▪ Change in the electronic properties
▪ Change in optical band gap
▪ Change in electrical conductivity
▪ Higher and specific catalytic activity
▪ Change thermal and mechanical stabilities
Nanomaterials synthesis approach:

1. Top down approach: The synthesis of nano

particles using this approach includes built up of the
structure by accumulation of each atom or molecule
by molecule
2. Bottom up approach: This approach includes
synthesis of nano particles by breaking down of bulk
materials gradually into smaller sizes

Buildup of material: Atom→ molecule→ cluster

Applications of nanomaterials:

In major view nanomaterials has found their applications

in many major areas:
▪ Electronics
▪ Medicine
▪ Engineering and technology
▪ Industries
▪ Environment
▪ Sensors
▪ Catalysis
▪ Nano transistors, Field effect transistors.
▪ Field emission.
▪ Nano electrodes.
▪ Nano medicine, drug delivery systems, disease
diagnosis.
▪ Chemical , bio, pressure, thermal sensors
▪ Nano devices.
LECTURE - 8
Introduction, 12 principles and importance of green Synthesis, Green
Chemicals, Synthesis of typical organic compounds by conventional and
Green route (Adipic acid and Paracetamol), Environmental impact of Green
chemistry on society
Green chemistry
▪ Green chemistry referred to as sustainable chemistry is the branch
of chemistry that deals with the design and optimization of
processes and products in order to lower, or remove altogether,
the production and use of toxic substances. Green chemistry is not
the same as environmental chemistry.
12 Principles of Green Chemistry
▪ Prevention of waste: Preventing the formation of waste products is
always preferable to the clean-up of the waste once it is generated.
▪ Atom economy: The synthetic processes and methods that are devices
through green chemistry must always try to maximise the consumption
and incorporation of all the raw materials into the final product. This
must strictly be followed in order to minimise the waste generated by
any process.
▪ Avoiding the generation of hazardous chemicals: Reactions and
processes that involve the synthesis of certain toxic substances that
pose hazards to human health must be optimised in order to prevent
the generation of such substances.
▪ The design of safe chemicals: During the design of chemical products
that accomplish a specific function, care must be taken to make the
chemical as non-toxic to humans and the environment as possible.
▪ Design of safe auxiliaries and solvents: The use of auxiliaries in
processes must be avoided to the largest possible extent. Even in the
circumstances where they absolutely need to be employed, they must
be optimized to be as non-hazardous as possible.
▪ Energy efficiency: The amount of energy consumed by the process
must be minimized to the maximum possible extent.
▪ Incorporation of renewable feedstock: The use of renewable
feedstock and renewable raw materials must be preferred over the
use of non-renewable ones.
▪ Reduction in the generation of derivatives: The unnecessary use of
derivatives must be minimalized since they tend to require the use of
additional reagents and chemicals, resulting in the generation of
excess waste.
▪ Incorporation of Catalysis: In order to reduce the energy requirements
of the chemical reactions in the process, the use of chemical catalysts
and catalytic reagents must be advocated.
▪ Designing the chemicals for degradation: When designing a chemical
product in order to serve a specific function, care must be taken during
the design process to make sure that the chemical is not an
environmental pollutant. This can be done by making sure that the
chemical breaks down into non-toxic substances.
▪ Incorporating real-time analysis: Processes and analytical
methodologies must be developed to the point that they can offer real-
time data for their monitoring. This can enable the involved parties to
stop or control the process before toxic/dangerous substances are
formed.
▪ Incorporation of safe chemistry for the prevention of accidents: While
designing chemical processes, it is important to make sure that the
substances that are used in the processes are safe to use. This can help
prevent certain workplace accidents, such as explosions and fires.
Furthermore, this can help develop a safer environment for the process
to take place in.
EXAMPLES
▪ Green solvents
▪ Synthetic techniques
▪ Carbon dioxide as processing agent
▪ Carpet tile backings
▪ Transesterification of fats
Green Chemicals
Green chemical is one that provides higher performance and
functionality while being more environmentally benign throughout its
entire life-cycle. This approach has been codified in the Twelve
Principles of Green Chemistry that provide a framework for innovation
and design.
Synthesis of adipic acid by conventional
and Green route
Synthesis of Paracetamol by conventional route
Step-1
When nitric acid is added to phenol, phenol undergoes nitration to form
Nitrophenol and p-Nitrophenol, p-Nitrophenol is a major product.

Step -2
Reduction of Nitro group (-NO2) to amine group (- NH2) group
Step 3
▪ Nucleophillic addition reaction of p-aminophenol with acetic anhydride
(CH3CO-O-OCH3) in the presence of sodium acetate (CH3COONa)
Green Synthesis of Paracetamol from Phenol
Step 1: Phenol reacts with acetic anhydride in the presence of strong acid like HF
To undergo acylation reaction to give 4-hydroxy acetophenone.

Step 2 :Reaction of aldehydes and ketones with hydroxylamine (NH2OH) gives

oximes. 4- hydroxyacetophenon e reacts with hydroxylamine to give corres
ponding ketoxime.
Step 3: Oximes in acidic medium (trifluroacetic acid, CF3COOH)
undergoes Beckmann rearrangement to produce substitute amides.
Beckmann rearrangement of the above ketoxime gives paracetamol.

Uses of Paracetamol
 It is used as antipyretic drug to reduce body temperature in case of high
fever.

 It is also used as a weak analgesic to reduce the mild to moderate pain

(examples: head ache,tooth pain, menstrual pain, etc.)
 Advantages of Green Chemistry :

▪ Plants and animals suffers less harm from toxic chemicals in the
environment.
▪ Lower potential for Global Warming.
▪ Ozone depletion and smog formation.
▪ Less chemical disruption of ecosystem.
▪ Less use of landfills, especially hazardous waste landfills.
Environmental impact of Green Chemistry on
Society:
Through the practice of green chemistry, we can create alternatives
to hazardous substances. The environmental impact of green
chemistry on socitey can be listed as-
• Green chemistry is a proactive approach to pollution prevention
• Plants and animals suffer less harm from toxic chemicals in the
environment.
• Lower potential for global warming, ozone depletion, and smog
formation
• Less chemical disruption of ecosystems
• Less use of landfills, especially hazardous waste landfills.
• Cleaner air - Less release of hazardous chemicals to air leading to
less damage to lungs
• Cleaner water - less release of hazardous chemical wastes to
water leading to cleaner drinking and recreational water
• Less exposure to toxic chemicals
The four R of Green Chemistry