Module-4

Polymers and Green Fuels

A polymer is a giant or macro molecule formed by the repeated union of several simple
molecules called monomers. The repeating units (monomers) are linked through strong covalent
bonds.
Monomers
A monomer is a simple molecule having two or more bonding sites through which each can link
to the other monomers to form a polymer chain.
Types of polymerization
Addition polymerization (Chain polymerization)
The reaction in which a rapid self addition of several bifunctional monomers to each other takes
place by chain reaction without elimination of any by products.

addition
Eg: n H2C CH2
H2 C CH2
polymerization n
Ethene Polythene

addition
n H2C CH H2C CH
polymerization n
Cl Cl
Vinyl Chloride Poly vinyl chloride

addition
n F 2C CF 2
F2C CF2
polymerization n
Tetra fluoro ethene Teflon

Condensation polymerization (Step growth polymerization)

Condensation polymerization takes place by linking together different monomer molecules and
is accompanied by the elimination of small molecules like H2O, NH3 and HCl. The polymer
obtained is called copolymer.

Available at KCT Engg College App

Example:

Eg: Synthesis of nylon 6,6

n HOOC CH2 COOH + n H2N CH2 NH2

4 6
Adipic acid Hexamethylene diamine

OC CH2 CONH CH2 NH + 2n H2O

4 6 n
Nylon 6,6

Eg: Synthesis of Terylene

n HOOC C6H4 COOH + n OH C2H4 OH

Terephthalic acid Ethylene glycol

OC C6H4 CO O C2H4 O + 2n H2O

n

As the polymers are made up of mixture of molecules having different properties, its molecular
weight can be determined in two different ways:
Number average molecular mass: (Mn) It is determined by measuring the colligative properties
such as freezing point depression, boiling point elevation, osmotic pressure and lowering of
vapour pressure. It is defined as total mass of all the molecules in a polymer sample divided by
total number of molecules present.

M n  W  N   Ni

NiMi 𝑤 𝑁1𝑀1+𝑁2𝑀2+𝑁3𝑀3+⋯.
Mn = =
 ∑𝑁 𝑁1+𝑁2+𝑁3+⋯

where Ni is the number of molecules of mass Mi..

Available at KCT Engg College App

No. average molecular weight assumes that each molecule makes an equal contribution to
polymer properties regardless of size or weight.

Weight average molecular mass ( M W ): It gives representation to various molecular species in

proportion to their weight in the given material. It is obtained from light scattering and ultra
centrifugation technique which measures molecular size.I n the averaging process molecular
weight of each individual species is multiplied by weight and not by number.

MW  
 WiMi
Wi
Where Wi is the weight fraction of the molecules whose mass is Mi.
We have Wi = NiMi

MW 
N M Mi i i

N Mi i
2

N M i i N Mi i

∑𝑤𝑖𝑀𝑖 𝑁1 𝑀12 +𝑁2𝑀22 +𝑁3𝑀32 ……

Mw = =
∑𝑊𝑖 𝑁1𝑀1+𝑁2𝑀2+𝑁3𝑀3……

Problems:

1. A polymer sample contain 100 molecules of molecular mass 1000g/mol 200 molecules of
molecular mass 2000g/mol, 500 molecules of molecular mass 5000 g/mol. Calculate number
average and weight average molecular weight.
𝑤 𝑁1𝑀1+𝑁2𝑀2+𝑁3𝑀3+⋯.
Number average molecular weight= Mn = =
∑𝑁 𝑁1+𝑁2+𝑁3+⋯
100𝑋 1000+200𝑋2000+500𝑋5000
= 100+200+500
1𝑋105 +4𝑋 105 +25𝑋105
= 800

= 3.75 x 103 g/mol

∑𝑤𝑖𝑀𝑖 𝑁1 (𝑀1)2 +𝑁2(𝑀2)2 +𝑁3(𝑀3)2 ……
Weight average molecular weight = Mw = =
∑𝑊𝑖 𝑁1𝑀1+𝑁2𝑀2+𝑁3𝑀3……

100𝑋 (1000)2 + 200𝑋(2000)2 + 500𝑋(5000)2

100𝑋1000 + 200𝑥2000 + 500𝑥5000

1𝑋108 +8𝑋108 +125𝑋108

= 30𝑋(10)5

Available at KCT Engg College App

 = 4.46 x 103 g/mol

2. A polymer sample contains 5 molecules having molecular weight 2000, 4 molecules having
molecular weight 3000, 3 molecules having molecular weight 4000. Calculate number average
and weight average molecular weight.

𝑤 𝑁1𝑀1+𝑁2𝑀2+𝑁3𝑀3+⋯.
No. average molecular weight = Mn = =
∑𝑁 𝑁1+𝑁2+𝑁3+⋯

5𝑋 2000+4𝑋3000+3𝑋4000
= 5+4+3

10000+12000+12000
= 3+4+5

= 2833.3 g/mol

∑𝑤𝑖𝑀𝑖 𝑁1 (𝑀1)2 +𝑁2(𝑀2)2 +𝑁3(𝑀3)2 ……

Weight average molecular weight = Mw = =
∑𝑊𝑖 𝑁1𝑀1+𝑁2𝑀2+𝑁3𝑀3……

5𝑋 (2000)2 +4𝑋(3000)2 +3𝑋(4000)2

= 5𝑋2000+4𝑥3000+3𝑥4000

20𝑋106 +36𝑋106 +48𝑋106

= 10𝑋(10)3 + 12𝑋(10)3 +12𝑋(10)3

106 (20+36+48)
= = 3058.8 g/mol
103 (10+ 12+12

Conducting polymers:
An organic polymer with highly delocalized pi- electron system, having electrical conductance
of the order of a conductor is called a conducting polymer.
Synthesis:
The conducting polymers are synthesized by doping in which charged species are introduced in
organic polymers having pi- back bone. The important doping reactions are

Available at KCT Engg College App

 1. Oxidative doping ( p-doping )
2. Reductive doping( n- doping )
3. Protonic acid doping ( p- doping )
Oxidative doping (p- doping): In this process pi- back bone of a polymer is partially oxidized
using a suitable oxidizing agent. This creates positively charged site on polymer backbone,
which are current carriers for conduction.
The oxidising agents used in p- doping are iodine vapour, iodine in CCl4, HBF4,
perchloric acid and benzoquine.
Mechanism of conduction in polyacetylene by Oxidative doping
CH2 Polyacetylene
H2C

I oxidation
I2 in CCl4

CH2 Radical ion

H2C (polaron)
+ I3 -
II oxidation
I2 in CCl4

+ I3 - CH2 Biradical ion

H2C (bipolaron)
+ I3 -
Recombination of radicals
-
+ I3 CH2 Conducting
H2C
+I - Polyacetylene
3

The removal of an electron from the polymer pi- back bone using a suitable oxidising agent leads
to the formation of delocalized radical ion called polaron. The second oxidation of the chain
containing polaron followed by radical recombination yields two charge carriers on each chain.
The positively charged sites on the polymer chains are compensated by anions I-3 formed by the
oxidising agent during doping.
The delocalized positive charges on the polymer chain are mobile, not the dopant
anions. Thus these delocalized positive charges are current carriers for conduction. These
charges must move from chain to chain as well as along the chain for bulk conduction.

Available at KCT Engg College App

Reductive doping (n- doping): In n- doping, pi back bone of a polymer is partially reduced by a
suitable reducing agent. This creates negatively charged sites on polymer backbone. These
negatively charged sites are responsible for the conduction. Reducing agent is solution of sodium
naphthalide in tetrahydrofuran
Mechanism of conduction in polyacetylene by Reductive doping
CH2 Polyacetylene
H2C

I reduction
Sodium naphthalide in THF

CH2 Radical ion

H2C (polaron)
Na+
II reduction
Sodium naphthalide in THF
Na+ CH2 Biradical ion
H2C (bipolaron)
Na+

Recombination of radicals
Na+
CH2 Conducting
H2C Polyacetylene
Na+

The addition of an electron to the polymer backbone by using a reducing agent generates a
radical ion or polaron. A second reduction of chain containing polaron followed by the
recombination of radicals yields two charge carriers on each chain. These charged sites on the
polymer chains are compensated by cations (Na+ ions) formed by the reducing agent.
The negative charges on the polymer chains are mobile and are responsible for
conduction.
Applications
 As electrode material for commercial rechargeable batteries(coin type batteries).
 As conductive tracks on printed circuit boards.
 As sensors-humidity sensor, gas sensor, radiation sensor, biosensor for glucose,galactose
etc.
 In electrochromic display windows.
 In information storage devices.

Available at KCT Engg College App

  As film membranes for gas separations.
 In light emitting diodes.
 In fuel cells as the electro catalytic materials.

Graphene oxide:

Carbon can able to form different allotropes such as Diamond, graphite,

buckminsterfullerene, nanotubes, nano buds, and nanoribbons because of its valency.
Graphene is a single atomic layer of carbon in which a layer of sp2 bonded carbon atom
arranged in a hexagonal or honeycomb lattice.
Graphene oxide is two-dimensional materials stack together to form graphite oxide is a
compound of carbon, oxygen, and hydrogen arranged in variable ratio. It contains a
hydroxyl (-OH), alkoxy (C-O-C), carbonyl (C=O), the carboxylic acid (-COOH), and
other oxygen-based functional groups. The oxygen-containing functional group
introduces both sides of a single graphite sheet and overcome the inter -sheet in van der
Waals force and enlarges the interlayer spacing and disturbs the sp2 bond of graphene so
reduces the conductivity of graphene oxide.

Available at KCT Engg College App

 Structure of Graphene Oxide

Preparation of Graphene Oxide:

Hummer’s method of synthesis Graphene oxide was synthesized by Hummers method
through oxidation of graphite. The stepwise preparation is given as follows:
1. Graphite flakes (2 g) and NaNO3 (2 g) were mixed in 50 mL of H2SO4 (98%) in 1000
mL volumetric flask kept under at ice bath (0-5°C) with continuous stirring.
2. The mixture was stirred for 2 hrs at this temperature and potassium permanganate (6 g)
was added to the suspension very slowly. The rate of addition was carefully controlled to
keep the reaction temperature lower than 15°C.
3. The ice bath was then removed, and the mixture was stirred at 35°C until it became
pasty brownish and kept under stirring for 2 days.
4. It is then diluted with slow addition of 100 ml water. The reaction temperature was
rapidly increased to 98°C with effervescence, and the color changed to brown color.
5. Further this solution was diluted by adding additional 200 ml of water stirred
continuously.
6. The solution is finally treated with 10 ml H2O2 to terminate the reaction by appearance
of yellow color.
7. For purification, the mixture was washed by rinsing and centrifugation with 10% HCl
and then deionized (DI) water several times.

Available at KCT Engg College App

8. After filtration and drying under vacuum at room temperature, the graphene oxide
(GO) was obtained as a powder.

Green Fuels:
Energy can neither be created nor be destroyed; it can only be changed from one form to another.
Thus, we cannot produce energy to do certain work. Therefore, we use certain substances which
help us to transform one form of energy into another form. Hence a fuel is defined as a
combustible substance, which on burning produces significant amount of heat which can be used
economically for industrial and domestic purposes.

Types of Fuels:

Fuels can be generally classified on the basis of two factors:

1. On the basis of their fuels state:

 Solid Fuels
 Liquid Fuels
 Gaseous Fuels
2. On the basis of their occurrence:
 Natural Fuels
 Artificial Fuels

Green fuels are carbon-neutral or even carbon-free alternatives to fossil fuels. Produced
from hydrogen and electricity from renewable sources, they are seen as crucial to

Available at KCT Engg College App

decarbonize heavy industries, shipping or head generation in the future. In sectors, where
direct electrification is not feasible, green fuels allow a smooth transition from fossil to
sustainable energy sources – as they can be used in existing storage and propulsion
systems.
Past and future perspective of green fuels:

Due to their high energy density, green fuels are well suited for both transport and power
generation. However, their production is energy-intensive and not yet economically viable. Even
though they are being tried and tested extensively, there is still a lack of infrastructure for mass
production. Therefore, facilities have to be scaled-up to reduce costs, and renewable power
generation must be expanded.

Today, most hydrogen is not produced from carbon-neutral energy sources, but with natural gas
(gray hydrogen), coal (brown or black hydrogen), nuclear power (pink or red hydrogen) or from
fossil fuels combined with carbon capture (blue hydrogen). But in order to reduce the carbon
footprint, green hydrogen is paramount. Hydrogen requires storage and transportation at either
high-pressure or very low temperatures; conversion to other green fuels with higher energy
density can mitigate that issue.

SOLAR ENERGY

Introduction:

A wide range of power technologies exist which can make use of the solar energy
reaching earth and converting them into different useful forms of energy. Solar energy utilization
can be of two types, direct solar power and indirect solar power.

Direct solar power: It involves only one step transformation into a usable.

Ex: 1) Sun light hits photovoltaic cell (also called photoelectric cell) generating electricity.

2) Sun light hits the dark absorbing surface of a solar thermal collector and the surface warms.
The heat energy may be carried away by a fluid circuit.

Indirect Solar Power: It involves more than one transformation to reach a usable form.

Available at KCT Engg College App

Ex: 1) Vegetation uses photosynthesis to convert solar energy to chemical energy, which can
later be burnt as fuel to generate electricity (biofuel). Methane (natural gas) may be derived from
the biofuel.

Photovoltaic cells:

Introduction: Photovoltaic cells or solar cells are semiconductor devices that convert
sunlight into direct current electricity. As long as light is shining on the solar cell, it generates
electrical power. When the light stops, electricity stops.

Groups of photovoltaic cells are electrically configured into modules and arrays, which
can be used to charge batteries, operate motors and to power any number of electrical loads.
With the appropriate power conversion equipment, photovoltaic systems can produce alternating
current (AC) compatible with any conventional appliances.

Working principle of photovoltaic cells:

All electromagnetic radiations including sunlight consist of particles called photons. The
photons carry a certain amount of energy given by E = hc/λ

Where h is Planck’s constant, c is the velocity of light, λ is the wave length of radiation.

When electromagnetic radiation (sunlight) is incident normal to the plane of the solar cell, the
photons which possess energy sufficient to overcome the barrier potential are absorbed &
electron-hole pairs are formed. Electrons are driven out into the external circuit & could be
stored & used for various applications.

Construction of a photovoltaic cell & its working:-

A typical silicon photovoltaic cell is composed of a thin wafer consisting of an ultra thin
layer of Phosphorous doped (n-type) silicon on top and Boron doped (p-type) silicon at the
bottom. Hence a p-n junction is formed between the two. A metallic grid forms one of the
electrical contacts of the diode and allows light to fall on the semiconductor between the grid
lines. An antireflective layer between the grid lines increases 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.

Available at KCT Engg College App

 When light radiation falls on the p-n junction diode, electron-hole pairs are generated by
the absorption of the radiation. The electrons are drifted to and collected at the n-type end
and the holes are drifted to and collected at the p-type end. When these two ends are
electrically connected through a conductor, there is a flow of current between the two ends
through the external circuit. Thus photoelectric current is produced and available for use.

Solar energy is the energy which has a greatest potential of acting as alternate source of energy
because of the reason that the reserves of fossil fuels are very limited and are depleted very fast.

Advantages:
1) Fuel source is vast and essentially infinite.
2) No emission, no combustion or radioactive residues for disposal. Does not contribute to global
climate change or pollution.
3) Low operating costs (no fuel).
4) No moving parts and no wear or tear.
5) Quick installation
6) High public acceptance and excellent safety record.

Disadvantages:
1) Sunlight is a diffuse source; i.e. it is relatively low density energy.
2) High installation costs.
3) Energy can be produced only during the day time.

Available at KCT Engg College App

Green hydrogen:
Hydrogen is a colorless, odorless, tasteless, and nonpoisonous gas under normal conditions on
Earth. It typically exists as a diatomic molecule, meaning each molecule has two atoms of
hydrogen; this is why pure hydrogen is commonly expressed as “H2”. Hydrogen is the most
abundant element in the universe, accounting for 90 percent of the universe by weight. However,
it is not commonly found in its pure form, since it readily combines with other elements. It is
also the lightest element, having a density of 0.08988 grams per liter at standard pressure.
Hydrogen has several important chemical properties that affect its use as a fuel:

 It combines with oxygen to form water, which is absolutely necessary for life on this
planet.
 It has a high energy content per weight (nearly 3 times as much as gasoline), but the energy
density per volume is quite low at standard temperature and pressure. Volumetric energy
density can be increased by storing the hydrogen under increased pressure or storing it at
extremely low temperatures as a liquid. Hydrogen can also be adsorbed into metal
hydrides.
 Hydrogen is highly flammable; it only takes a small amount of energy to ignite it and make
it burn. It also has a wide flammability range, meaning it can burn when it makes up 4 to 74
percent of the air by volume.
 Hydrogen burns with a pale-blue, almost-invisible flame, making hydrogen fires difficult to
see.
 The combustion of hydrogen does not produce carbon dioxide (CO2), particulate, or sulfur
emissions. It can produce nitrous oxide (NOX) emissions under some conditions.
 Hydrogen can be produced from renewable resources, such as by reforming ethanol (this
process emits some carbon dioxide) and by the electrolysis of water (electrolysis is very
expensive).

Green hydrogen is the most basic electrofuels (e-fuels). It is created by splitting water (H2O) into
oxygen (O) and hydrogen (H2) in a process called electrolysis, using power from renewables.
Hydrogen can then be used either directly as fuel e.g. for internal combustion engines – or as
core component for the synthesis of other green fuels such as ammonia (with nitrogen) or
methanol, SNG (with carbon, captured from the air, biomass or industrial plants' exhaust gases).

Generation of hydrogen by electrolysis of water: Alkaline water electrolysis

Available at KCT Engg College App

Water electrolysis is one of the simplest methods used for hydrogen production. Water
electrolysis is mainly carried out to yield pure hydrogen and oxygen gases. It involves passing an
electric current through the water which results in the decomposition of water into hydrogen and
oxygen.
Alkaline Water Electrolysis
Two electrodes or plates that are made from an inert metal such as platinum or iridium are placed
in the water. A DC electrical power source is connected to these plates. At the cathode (where
electrons enter the water) part Hydrogen will appear. On the anode side, oxygen will appear. If
we consider the ideal faradaic efficiency, hydrogen will be produced twice the amount of
oxygen. On the other hand, both will be proportional to the total electrical charge conducted by
the solution. However, in some cells side reactions can occur and different products are formed
with less than ideal faradaic efficiency.

The cell potential of electrolysis of pure water is negative and hence is thermodynamically
unfavourable. Because of the low concentration of ions and the interfaces to be crossed electrons
an extra voltage (Overvoltage) at each electrode is needed to about 0.6V. In practice, continuous
electrolysis of pure water is possible only at an external voltage of 2.4V. Since the electrolysis of
pure water is thermodynamically non-feasible, methods to make it kinetically feasible are being
investigated. One of the methods is to increase the conductivity by increasing the number of ions
available by adding acid, base, or non-reacting salts.

Additional hydroxyl ions, release their electrons to anode, while electrons at the cathode oxidize
water molecules near it.

Available at KCT Engg College App

Half reactions of electrolysis in the presence of a base are-

Like electrolysis in an acid medium, electrolysis in the basic medium also needs much lower
potential.

Advantages of Alkaline water electrolysis:

Available at KCT Engg College App

 1. It has the advantage of being able to produce hydrogen using only renewable
energy.
2. The main advantage of alkaline water electrolysis over other water electrolysis
technology lies in the fact that alkaline electrolysers can be made of abundant and
inexpensive materials.
3. Simple iron or nickel steel electrodes are used to produce hydrogen and nickel
used for oxygen production.
4. Higher gas purity due to lower gas diffusivity in alkaline electrolyte.

Electrolysis of water – Proton Exchange Membrane Electrolysis

Hydrogen can be obtained from different sources of raw materials including water.
Among many hydrogen production methods, eco-friendly and high purity of hydrogen
can be obtained by water electrolysis. However, In terms of sustainability and
environmental impact, PEM water electrolysis was considered as most promising
techniques for high pure efficient hydrogen production from renewable energy sources
and emits only oxygen as byproduct without any carbon emissions.

In PEM water electrolysis, water is electrochemically split into hydrogen and oxygen at
their respective electrodes such as hydrogen at the cathode and oxygen at the anode. PEM
water electrolysis is accrued by pumping of water to the anode where it is spilt into
oxygen (O2), protons (H+ ) and electrons (e). These protons are traveled via proton
conducting membrane to the cathode side. The electrons exit from the anode through the
external power circuit, which provides the driving force (cell voltage) for the reaction. At
the cathode side the protons and electrons re-combine to produce the hydrogen, the
following mechanism as shown in Figure. Typically, in PEM water electrolysis noble
metal based electrocatalysts are used such as Pt/Pd-based catalysts as cathode towards the
hydrogen evolution reaction (HER) and RuO2/IrO2 catalysts as anode for oxygen
evolution reaction (OER).

Available at KCT Engg College App

Advantages of PEM water electrolysis:
1. PEM water electrolysis has great advantages such as compact design.
2. High current density (above 2 A cm-2)
3. High efficiency, fast response, small footprint.
4. Operates under lower temperatures (20–80oC) and produced ultrapure hydrogen
and also produced oxygen as a byproduct.

Available at KCT Engg College App