Module IV

Polymers & Green Fuels

Introduction
Polymers are the high molecular weight compounds obtained by repeated union of
simple molecules (Monomers).
Ex: Starch, silk, wool, Polyvinyl chloride, Polyethylene, Nylon 6,6 etc.

Classification of polymers.
Polymers are classified into two types as follows:
i) Natural polymers: These are the polymers obtained naturally by plants and animals.
Ex: Silk, wool, natural rubber, protein, starch, cellulose, etc.
ii) Synthetic Polymers: These are artificially prepared polymers also known as manmade
polymers. Ex: PVC, Nylon 6.6, Polyethylene, Phenol formaldehyde resin etc.,

Terms used:
Monomer: These are the simple molecules, which combine with each other to form polymers.
These are the building blocks of Polymer.
Ex: - Ethylene, Vinyl Chloride, Styrene, etc…
Polymerization: The process of linking of monomers to form polymers with or without the
elimination of by-products is called as polymerization.

Degree of Polymerisation (n): The total number of monomers present in a single chain of
polymer is called as degree of polymerization.

Molecular weight of Polymers: -

The molecular weight of polymer depends on the number of monomer molecules in the
polymer chain. The experimental measurement of molecular weight gives average molecular
weight of a polymer.

Average molecular weight of a polymer is expressed as,

̅ 𝒏]
1. Number average molecular weight [𝐌
̅ 𝐰]
2. Weight average molecular weight [𝐌

̅ 𝒏 ]:-
Number average molecular weight [𝐌

It is the mass obtained when total mass of all the molecules of a sample is divided by
the total number of molecules.

𝑵𝟏 𝑴𝟏 + 𝑵𝟐 𝑴𝟐 + 𝑵𝟑 𝑴𝟑 + − − − − − −
̅𝒏 =
𝑴
𝑵𝟏 + 𝑵𝟐 + 𝑵𝟑 + − − − − − −

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 ̅ 𝐧 = ∑ 𝐍𝐢𝐌𝐢
𝐌 ∑𝐍 𝐢
Where 𝑀𝑖 = 𝑀𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝐶ℎ𝑎𝑖𝑛
𝑁𝑖 = Number of chains of that molecular weight.

Weight average molecular weight: -

It is the mass obtained when sum of all the products of total mass of groups of molecules
and their respective molecular masses is divided by total mass of all the molecules.

𝑵𝟏 (𝑴𝟏 )𝟐 +𝑵𝟐 (𝑴𝟐 )𝟐 +𝑵𝟑 (𝑴𝟑 )𝟐 +⋯..

̅ W=
M
𝑵𝟏 𝑴𝟏 +𝑵𝟐 𝑴𝟐 +𝑵𝟑 𝑴𝟑 +⋯

∑ 𝑵𝒊 (𝑴𝒊 )𝟐
̅ W=
M
∑ 𝑵𝒊 𝑴𝒊

Where Mi = Molecular Weight of Chain

Ni = Number of chains of that molecular weight.
Numerical on Molecular weight of Polymers: -

1. A polymer sample containing 5 molecules having molecular weight of 2000, 4

molecules having molecular weight of 3000 and 3 molecules having molecular weight
of 4000. Calculate number average and weight average molecular weights.

̅ 𝒏 ]:-
Solution: - 1. Number average molecular weight [𝑴

𝐍𝟏 𝐌𝟏 + 𝐍𝟐 𝐌𝟐 + 𝐍𝟑 𝐌𝟑 ± − − − − −
̅𝐧 =
𝐌
𝐍𝟏 + 𝐍𝟐 + 𝐍𝟑 ± − − − − −
[5 × 2000 + 4 × 3000 + 3 × 4000]
̅n =
M
[ 5 + 4 + 3]

̅ 𝒏 = 𝟐𝟖𝟑𝟑. 𝟑 g/mol
𝑴

̅ 𝑾 ]:-
Weight average molecular weight [𝑴

𝑵𝟏 (𝑴𝟏 )𝟐 +𝑵𝟐 (𝑴𝟐 )𝟐+𝑵𝟑 (𝑴𝟑 )𝟐 +⋯..

̅ W=
M
𝑵𝟏𝑴𝟏 +𝑵𝟐 𝑴𝟐 +𝑵𝟑 𝑴𝟑 +⋯

[(5 ×(2000) 2)+(5 ×(3000) 2 ) +(3 ×(4000) 2 )]

M̅W = [(5 ×2000)+(4 ×3000)+(3 ×4000)]

̅ W = 3058.8 g/mol
M

 In a polymer sample, 20% of molecules have molecular mass 15000g/mol, 35%

molecules have molecular mass 25000 g/mol and remaining molecules have molecular

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 mass 20000 g/mol. Calculate the number and weight average molecular weights of the
polymer.
 A polymer sample contains 100,200,300 and 400 molecules having molecular mass
1000, 2000, 3000 and 4000 respectively. Calculate the number and weight average
molecular weights of the polymer.

 A polymer sample containing 50, 100 and 150 molecules having molar mass 1000,
2000 and 3000 respectively. Calculate the number and weight average molecular
weights of polymer. [Dec.2015/ Jan 2016]

 In a polymer sample, 20% of molecules have molecular mass 15000g/mol, 45%

molecules have molecular mass 25000 g/mol and remaining molecules have molecular
mass 27000 g/mol. Calculate the number and weight average molecular weights of the
polymer. [Dec.2015/ Jan 2016]

 A polymer sample contains 200 molecules of molecular mass 2000, and 200 molecules
of molecular mass 40,000 g/mol. Calculate the number and weight average molecular
weights of polymer.

 A polymer sample contains 100 molecules of molecular mass 20,000 g/mol , 300
molecules of molecular mass 3000 and 500 molecules of molecular mass 5000.
Calculate the number and weight average molecular weights of polymer. [June/July-
2016]
Conducting Polymers: -
Definition -“An organic polymer with highly delocalized pi-electron system having electrical
conductance of the order of a conductor” is called Conducting polymer.
They are also called synthetic metals. Few polymers which conduct electricity upon doping are
polyacetylene, Polyacetylene, Polyaniline, polypyrrole, polythiophene, polyphenylene,etc

Ex: Polyaniline, Polypyrrole, Polythiopene, Polyacetylene, etc.

Conducting polymers are obtained by doping an oxidizing or reducing agent into organic
polymers. With the carbon backbone consisting of alternate double bond & single bonds doping
results in delocalization of electrons responsible for conduction.
Polyacetylene
Synthesis –It is obtained by addition polymerisation of acetylene in presence of zigler natta
catalyst gives Polyacetylene.

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Conducting Mechanism of Polyacetylene: -

The conducting polymers are synthesized by doping, in which charged species are
introduced in organic polymers having pi-back bone.

1. Oxidative doping (p-doping)

2. Reductive doping (n-doping)

1. Oxidative doping (p-doping):

In this process, pi-back bone of a polymer is partially oxidized using a suitable
oxidizing agent such as iodine in CCl4 solvent. This creates positively charged sites on
polymer back bone, which are current carriers for conduction.
Other oxidizing agents used in p-doping are iodine vapor, , HBF4, perchloric acid
and benzoquinone.

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 2. Reductive doping (n-doping):

In n-doping, pi-back bone of a polymer is partially reduced by a suitable reducing

agent such as sodium naphthalide in tetra hydro furan. This creates negatively charged
sites on polymer backbone. These negatively charged sites are responsible for the
conduction.

Commercial Applications: -

 Fabrication of organic thin transistors.

 Non-volatile memory devices based on organic transistors.
 Development of novel conjugated polymers for photovoltaic device applications.
 Fabrication of organic photovoltaic cells.
 Fabrication of organic light-emitting devices (OLED).
 Ferroelectric polymers for thin film devices.
 Gene Sensors.
 Printed electronics.
 Conducting polymer actuators and Micro pumps.
 Responsive membranes/Hybrid Plastics.
 An antistatic material.

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Kevlar fibres:
Synthesis
Kevlar is synthesized in solution from the monomers of Terephthaloyl chloride (1,4 benzene
dicarbonoyl chloride) & Para Phenylene diamine (1,4-phenylenediamine) in a condensation
reaction yielding hydrochloric acid as a by-product.

Properties Applications
Kevlar is crystalline, light weight and Used in reinforcement material for some
nonflammable. tyres.
Resistant to heat, impact and scratch. Used in making of light weight boat hulls and
aerospace industry.
Good Chemical resistance. Used in formula one racing car .
Good tensile strength. Used in bullet proof vests and combat
helmets.
Abrasion & Corrosion resistant Used in making puncture resistant tyres

Graphene Oxide: -

Graphene is an allotrope of carbon made of a single layer carbon atoms that are bonded
together in a repeating pattern of hexagons.

Graphene oxide is an oxidized form of graphene. It is obtained by treating graphene with

strong oxidizers and acids.

Preparation of Graphene Oxide: - (Hummer’s Method)

 Take graphene (2gm) and Sodium Nitrate (NaNO3) (2gm) were combined with H2SO4
(90ml) and stirred for 30 min in an ice bath.
 For the resulting mixture add KMnO4 (10gm) and the solution was then kept for 2h.
 Then add deionized water (200ml) and H2O2 (12ml) slowly to the above solution, then the
resulting solution was wash with HCl (300ml 10%).
 The obtained product was dried gives graphene oxide powder.

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 Graphene Graphene Oxide

Properties of Graphene Oxide: -

 High thermal conductivity.

 High electrical conductivity.
 High elasticity and flexibility.
 High hardness.
 High resistance....
 Ionizing radiation is not affected.
 Able to generate electricity by exposure to sunlight.
 Transparent material.

Commercial Applications of Graphene Oxide: -

 Electronic devices.
 Energy storage devices.
 Bio- sensors.
 Biomedical applications.
 Super capacitors.
 Membranes, catalysts, and water purification.

Green Fuel:-

Green fuels are liquid or gaseous fuels produced with electricity from renewables.

Ex: - Synthetic Natural Gas (SNG), Hydropower, Solar Power, Wind Power, Biomass etc.,

Solar Energy:

Introduction:

Solar energy is one of the solutions for sustainable energy conversion processes. Solar
radiation coming from sun is highly useful in photosynthesis and is the major energy source

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for ecosystem. Solar energy is non-depleting, non-polluting and available freely & can be
utilized for various applications.

Radiations from the sun constitute solar energy.

It is a clean and renewable source of energy available in abundance.

Photovoltaic Cells:-

Photovoltaic cells are semiconductor device which convert solar energy into electrical
energy.

Photovoltaic cells can generate electricity as long as Sun light is available.

Construction and working of Photovoltaic cells:-

Photovoltaic cell is composed of a thin mater consisting of an ultra-thin layer of

phosphorous doped [n-type] silicon on the top of boron doped [p-type] silicon. Hence P-n
junction is formed b/w the two.

 A metallic grid forms one of the electrical contacts of the diode and allows light to fall on
the semiconductor b/w grid lines.
 An antireflective layer b/w the grid lines increase the amount of light transmitted to the
semiconductor.
 The cells other electrical contact is formed by a metallic layer on the back of the solar cell.

Sunlight
Antireflective layer

Metal grid
N-type layer

h+ P- Type layer
e
-

e-
Metallic layer

Working: -

 When light radiation falls on the P-n junction diode, electrons-hole pairs are generated by
the absorption of the radiation.
 The electrons are drifted and collected at n-type end and the holes are drifted and collected
at the P-type end.

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 When these two ends are electrically connected through a conductor, there is a flow of
current b/w the two ends through the external circuit. Thus Photoelectric current is produced
and available for use.

Advantages: -

 They are Environmental friendly.

 They need no recharging.
 They do not corrode.
 They operate at low temperature.
 No emission, no combustion.
 High public acceptance and excellent record.
 Low operating cost.
 No moving parts and so no wear and tear.

Disadvantages: -

 High installation cost.

 Energy can be produced only during the day time.
 Poor reliability of auxiliary elements including storage.
 Sun light is a diffuse, ie, it is relatively low density energy.

Green Hydrogen: -

It is hydrogen produced by splitting water by electrolysis.

Electrolysis of Water: -

It is a process of splitting of water into a hydrogen and oxygen using electricity.

Process:- It consists two pair of platinum electrodes with water and H2SO4 electrolyte.

 At the anode, water is oxidized to oxygen gas and hydrogen ions.

 At the cathode, hydrogen ions are reduced to hydrogen.

Anode Cathode

Electrolyte

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 -
Anode Reaction: H2O 2H+ + 1/2 O + 2e
2

Cathode Reaction: 2H+ + 2e -

H2

Net Reaction: H2O 2H+ + 1/2 O 2

Properties of Hydrogen pertaining to fuel:-

 Hydrogen can be produced from renewable resources.

 Hydrogen burns with a pale-blue.
 Hydrogen is highly flammable.
 It has a high energy.
 It combines with oxygen, gives water.

Proton Exchange Water Electrolysis:-

It is an electrolysis of water in a cell equipped with a proton exchange membrane.

Construction:-

 It consists of anode electrode with iridium as catalyst.

 It consists of anode electrode with platinum as catalyst.
 It consists of proton exchange membrane between anode and cathode.
Working: -

It is carried out by pumping of water to the anode, where it is split into oxygen (O 2), protons
and electron.
The liberated protons are moved to cathode through proton exchange membrane. In which
proton and electrons combine to produce hydrogen (H2).

Anode Reaction: H2O 2H+ 1/2 O2 2e-

+ +
Cathode Reaction: 2H+ 2e-
+ H2

Net Reaction: H2O 2H+ 1/2 O2

+

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 2. Photo Catalytic Water Splitting: -

 Splitting of water to get hydrogen by using photo catalyst and solar energy
is called photocatalytic water splitting.
 When solar energy interacts the photo catalyst, produces charge carrier’s holes and
electrons due to absorption of energy.
 Thus produced hole will react with the neighbouring water molecule liberates the
hydrogen ion and oxygen.
 Later electrons reduce the H+ ions in to hydrogen gas

QUANTUM DOT SENSITIZED SOLAR CELLS (QDSSC’S) :-

Introduction: -
Quantum dots are the small semiconducting nanoparticles with dimensions of nanometre. Quantum
dots are referred as Artificial atoms.
Ex :- Cadmium Selenide (CdSe), Cadmium Sulfide (CdS), Lead Sulfide (PbS), Zinc Sulphide(ZnS),
etc.,
In Quantum dots, the electrons and holes are confirmed in all three dimensions, leading todiscrete
energy levels.
Construction and Working of Quantum Dot Sensitized Solar Cells (QDSSC’s) :-
QDSSC’s - These are the type of Photovoltaic cells that uses Quantum dots as the light
absorbing material which converts solar energy into electrical energy.

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Construction –
A QDSSCs consists of 3 components
Photo anode: It is a conducting glass, over which a wide band gap semiconductor likeTiO2, ZnO
SnO2 etc. is coated.
Electrolyte: Poly sulphide redox couple which can effectively take up the holes from QDsis most
commonly used electrolyte.
Cathode electrode (CE): It is used to regenerate electrolyte and to complete the circuit.

Working: - the following steps are involved in the working of QDSSC

 Quantum dots present on photo anode is exposed to sunlight it is excited from ground stateto
higher energy state and absorption solar energy results in generation of electron – hole pairs.
Excitation: 𝑄𝐷𝑠 + ℎ𝜈⟶ 𝑄𝐷𝑠∗
Electron hole – pair formation: 𝑄𝐷𝑠∗ ⟶𝑄𝐷𝑠 (𝑒−∗+ ℎ+∗)
 The excited electron moves from valance band to conduction band of TiO2 semiconductor,
leaving holes on the surface of quantum dots.
Injection process: 𝑄𝐷𝑠 (𝑒−∗+ ℎ+∗) + 𝑇𝑖𝑂2 ⟶ 𝑇𝑖𝑂2 (𝑒−∗) + 𝑄𝐷𝑠 (ℎ+∗)
 The electrons transported between the TiO2 nano particles and then it moves to photo anode,
from photo anode it moves to cathode electrode (CE) through external circuit bygenerating
electricity.
Energy generation: 𝑇𝑖𝑂2 (𝑒−∗) + 𝐶𝐸 ⟶ 𝑇𝑖𝑂2 + 𝐶𝐸 (𝑒−∗) + 𝐸𝑙𝑒𝑐𝑡𝑟𝑖𝑐𝑎𝑙 𝑒𝑛𝑒𝑟𝑔𝑦
 Electrolyte takes up the holes from surface of quantum dots and it gets reduced andregenerate
by taking up electron from cathode.
Properties: -
 High light absorption.
 Tunable band gap.
 Low cost
 Long life span.

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 APPLICATIONS: -
 Portable electronics.
 Building – integrated photovoltaics.
 Off – grid power.
 Automotive (Electric Vehicles).
 Space applications.
 Artificial photosynthesis

Perovskite Solar Cells (PSCs)- Construction, working, and applications:

Perovskite solar cells (PSCs) are a type of photovoltaic device that use a perovskite-structured
compound as the light-harvesting active layer.

The perovskite material has a general formula ABX₃, where:

 A is a cation (e.g., methyl ammonium, formamidinium, or cesium),

 B is a metal ion (commonly lead or tin),
 X is a halide ion (chlorine, bromine, or iodine).

These solar cells are gaining popularity due to their high efficiency, low cost, and ease of
fabrication compared to traditional silicon solar cells.

Construction

A typical perovskite solar cell has the following layers:

1. Transparent Conductive Electrode (TCO):

o Usually made of indium tin oxide (ITO) or fluorine-doped tin oxide (FTO).
o Allows light to pass through while conducting electricity.
2. Electron Transport Layer (ETL):
o Made of materials like TiO₂, SnO₂
o Facilitates the transport of electrons from the perovskite layer to the electrode.
3. Perovskite Layer:
o The active layer responsible for absorbing sunlight and generating charge carriers.
o Example: CH₃NH₃PbI₃ or CsPbBr₃.
4. Hole Transport Layer (HTL):
o Facilitates the transport of holes to the opposite electrode.
5. Metal Electrode:
o Made of gold, silver, or aluminum, which collects the electrons and complete the
circuit.

Working Principle

The operation of a perovskite solar cell involves the following steps:

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The perovskite solar cells which consists of perovskite structured materials, when these
materials exposed to light, exciting electrons from the valence band to the conduction band,
creating electron-hole pairs. These pairs are called exiton. The holes and electrons are separated
due to less binding energy of exiton. The electrons are move through the electron transport
layer and holes are move through the hole transport layer. The electrons and holes are collected
at their respective electrodes, generating a current flow when the cell is connected to an external
circuit.

Applications
1. Solar Energy Generation

2. Building-Integrated Photovoltaics

3. Portable and Wearable Devices

4. Space Applications

5. Internet of Things (IoT) Devices

6. Agriculture (Agri-Voltaics)

7. Automotive Industry

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