Department of Chemistry 2022

Module – 4: Polymers and Green Fuels (8hr)

Syllabus:
Polymers: Introduction, Molecular weight – Number average, weight average and numerical
problems. Preparation, properties and commercial applications of kevlar. Conducting
polymers – synthesis and conducting mechanism of polyacetylene and commercial
applications.
Green Fuels: Introduction, construction and working of solar photovoltaic cell, advantages,
and disadvantages. Generation of energy (green hydrogen) by electrolysis of water and its
advantages.
Self-learning: Regenerative fuel cells
…………………………………………………………………………………………………………………………………………………………….

POLYMERS

Introduction:

The word polymer is derived from the two Greek words ‘polys’ and ‘merous’ meaning
‘many’ and ‘parts’ or ‘units’ respectively.

Polymer: It is a macromolecule formed by the repeated unit of several simple molecules

called monomers. The repeating units in a polymer are linked through covalent bonds.

The properties of polymer are different from those of the monomers from which it is formed.
The average masses of polymers vary from 103 to 107.

Monomers: These are simple molecules, which combine with each other to form polymers.
Monomers are also called “building blocks” of polymers.

A monomer is a molecule should contain at least two bonding sites (in the form of double or
triple bonds or functional groups such as –OH, -COOH, -NH2, -NCO, etc.,).

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Polymerization: It is the process of conversion of substances having low molecular mass

(monomers) into substances having high molecular mass (polymers) with or without the
elimination of by products like water, hydrochloric acid, ammonia, etc.,

Polymerization reaction usually takes place in the presence of initiators.

Degree of Polymerization: The number of repeating units present in a polymer is called

degree of polymerization.

Where n is the degree of polymerization. ‘n’ value is very large (in the range of hundreds/
thousands, the polymers are called high polymers). When ‘n’ value is less than 10, the
polymers are called oligomers.

If n = 2 dimer

n = 3 trimer

n = 4 tetramer and so on

Molecular mass of polymers

Molecular mass of a polymer decides various physical properties of the polymer like solution
viscosity, softening temperature, heat resistance, tensile strength and impact strength, etc.

Polymers with low molecular masses are generally soft and gum like substances.

Polymers with high molecular masses are tougher and more heat resistant.

Thus control of molecular mass of polymer is often important for industrial polymerization.
Therefore, the determination of molecular mass is of great importance in both the research
and industry.

The molecular mass of polymer depends up on the degree of polymerization. But the
polymerization chains are broken at different stages; therefore the final product will contain
the macromolecules of different mass. Most of the polymers are polydisperse, i.e. the
molecules of the polymer sample do not have identical molecular mass (M). Hence, it is
necessary to take average molecular mass.

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There are two types of average molecular mass of polymers:

Number average molecular mass (𝐌𝐧 ):

In this method, let us assume a polymer sample containing ‘n’ number of molecules.
Out of ‘n’ molecules, ‘n1’ numbers of molecules have ‘M1’ molecular mass.

Similarly, ‘n2’ numbers of molecules have ‘M2’ molecular mass.

………………………………………………………………………
‘ni’ numbers of molecules have ‘Mi’ molecular mass.

nimi
n1m1 n4m4
n2m2
n3m3

Now, we have a total number of molecules (n) given by

n = n1 + n2 + n3+ ----------+ ni = ∑ ni

Number of molecules in fraction 1 = n1

Number of fraction of fraction 1 = =

∑

Molecular mass contribution by fraction 1 =

∑

Similarly, molecular mass contribution by other fractions will be as follows:

, ,----------
∑ ∑ ∑

The number average molecular mass of the whole polymer will be given by

M = + + + ------- -+
∑ ∑ ∑ ∑

∑𝐧𝐢 𝐌𝐢
𝐌𝐧 =
∑𝐧𝐢

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Where ni = number of monomer molecules

Mi = masses of simple monomer molecules

This method assumes that each molecule makes an equal contribution to polymer properties
regardless of the size or mass.

Weight average molecular mass (𝐌𝐰 ):

Let us consider a polymer sample containing ‘n’ number of molecules having different
weights.

‘n1’ number of molecules having ‘M1’ molecular mass

Similarly, ‘n2’ number of molecules having ‘M2’ molecular mass

‘n3’ number of molecules having ‘M3’ molecular mass

………………………………………………………….

‘ni’ number of molecules having ‘Mi’ molecular mass

Total weight of the polymer = W = ∑n M

Weight of fraction 1 = W1 = n1M1

Weight fraction of fraction 1 = = =

∑ ∑

Similarly, the molecular weight contribution by the other fractions will be

, , , ………………..
∑ ∑ ∑ ∑

The weight average molecular mass contribution by the whole polymer will be

M = + + + + ……………..+
∑ ∑ ∑ ∑ ∑

∑
M =
∑

For all synthetic polymer, M is greater than M . When all molecules are of the same weight,
then

M =M .

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The molecular mass of the polymer can be determined by using the following methods:
1. Colligative property measurement such as osmometry, Ebullioscopy & cryoscopy.
2. Light scattering measurements
3. Viscosity measurements
4. Ultracentrifuge and
5. Chemical analysis

Poly Dispersity Index [PDI]: Index of polydispersity or PDI is used as a measure of

molecular weight distribution and is defined as PDI.
Mw
𝑃𝐷𝐼 =
Mn
If PDI = 1 then the polymer is mono disperse and homogeneous
PDI > 1 then the polymer is poly disperse and less homogeneous

KEVLAR FIBER

Polymer Composite: A polymer composite is a material made of two or more types of

polymers with different physical and chemical properties that, when combined, produce a
material with characteristics different from the individual components.

Polymer composites are usually made of two components, Fibre and Matrix.

Synthesis, Properties and Applications of Kevlar Fibre:

Kevlar is an aramide (aromatic polyamide), in which all the amide groups are separated by
para phenylene groups. The chemical composition of Kevlar is poly para phenylene
terephthalamide.

Synthesis: Kevlar is synthesized from the monomers, 1,4-phenylene diamine (para-

phenylenediamine) and terephthaloyl chloride through a condensation reaction with the
liberation of HCl as a byproduct.

Kevlar is fiber embedded in an epoxy resin polymer matrix is called polymer composite.

O O

H 2N N H2 + Cl C C Cl

p -P h e ny l e ne d i a m in e (P PD ) T e re p ht h a lo y ld ic h lo r id e (T D C )

H H
N N C C
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O O
n
K e v l ar f ib re
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Properties of Kevlar
1. Kevlar is crystalline, lightweight and non-flammable.
2. Resistant to heat, impact, scratch
3. Withstands harsh environmental conditions
4. Abrasion and corrosion resistant
5. High tensile strength
6. Resistant to Chemicals

Applications
1. It is used in lightweight boat hulls. Aircraft panels, Race cars
2. Bulletproof vests and combat helmets
3. Reinforce material for car tires, bicycle tires, which reduces puncture rate
4. Marine current turbine and wind turbine
5. Ropes and cables
6. Fiber-optic cables for communication, data transmission and ignition

CONDUCTING POLYMERS

An organic polymer with highly delocalized pi-electron systems, having electrical

conductance of the order of a conductor is called a conducting polymer.

ex: Polyacetylene, polypyrrole, polyaniline, etc.,

Conducting polymers are classified as:

1. Intrinsic conducting polymers &

2. Extrinsic conducting polymers

In intrinsic conducting polymers, conductivity is due to organic polymers themselves which

start conducting upon doping with suitable agents.

Extrinsic conducting polymers are prepared by mixing polymers with conducting fillers like
metal fibres, metal oxides, carbon black, etc., here conductivity is not due to the matrix
polymer but due to the added conducting fillers.

The conducting polymers are also known as synthetic metals. Few polymers which conduct
electricity upon doping are Polyacetylene, polypyrrole, polyaniline, polythiophene,
polyphenylene, etc. An organic polymer to conduct electricity upon doping should have:

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1. Linear structure with relatively rigid chains &

2. Extensively conjugated polymeric backbone.

SYNTHESIS OF POLYACETYLENE

Acetylene undergoes addition polymerization in the presence of Zeigler Nutta catalyst,

polyacetylene is formed.

Polyacetylene is an insulator in its original form. But on suitable doping, its conductivity can
be increased considerably. Conductivity of polyacetylene is 4.4x10-5S/cm, whereas, that of
doped polyacetylene is 400 S/cm. Doping creates charge carriers like holes or electrons in the
polymer backbone and make the polymer conducting material.

The important doping techniques are:

Oxidative Doping (p - type doping): Here the polymer is treated with an oxidizing agent
like iodine, aluminium chloride, perchloric acid, etc. Oxidizing agent takes away electrons
from pi - back bone of the chain. Thus, polymer becomes p - type conductor as it conducts by
free mobile holes.

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Mechanism of conduction on oxidative doping:

 The polymer chain is partially oxidised by using a mild oxidising agent such as iodine
in carbon tetrachloride.
 In the first step, one electron is removed from pi-backbone of the chain leaving a
positive charge on one of the carbon atoms.
 One more electron left out on another carbon atom makes it a free radical.
 The free radical-cation thus formed is called polaron.
 Similarly, on second oxidation, another free radical-cation is formed, is called
bipolaron.
 The radicals migrate towards each other and combine to form a double bond.
 The chain now has two positive charges (holes).
 The positive charges are compensated by I3- ions and thus the polymer is electrically
neutral.
 As positive charges are mobile, on applying potential they move and make the
polymer conductor in soliton form.
 This type of doping is known as p - doping.

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Reductive doping (n - type doping): Here the polymer is treated with a reducing agent like
sodium or lithium naphthalides. Reducing agent supplies electrons to pi - back bone of the
chain. Thus, polymer becomes n - type conductor as it conducts by the movement of
electrons.

Mechanism of conduction on reductive doping:

 The polymer chain is partially reduced by using a mild reducing agent such as Na-
Naphthalide in tetrahydrofuran (THF) as solvent.
 In the first step, one electron is added to pi-backbone of the chain leaving a negative
charge on one of the carbon atoms.
 One more electron left out on another carbon atom makes it a free radical.
 The free radical-anion thus formed is called polaron.
 Similarly, on second reduction, another free radical-anion is formed, is called
bipolaron.
 The radicals migrate towards each other and combine to form a double bond.
 The chain now has two negative charges.
 The negative charges are compensated by Na+ ions and thus the polymer is
electrically neutral.
 As negative charges are mobile, on applying potential they move and make the
polymer conductor in soliton form.
 This type of doping is known as n - doping.

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Commercial applications:

1. Doped polyacetylene offers a particularly high electrical conductivity therefore it can

be used in electric wiring or electrode material in lightweight rechargeable batteries.
2. Tri-iodide oxidized polyacetylene can be used as a sensor to measure glucose
concentration.

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Green Fuels

Introduction

Green fuel provides real benefits for the environment since the power comes from natural
resources such as sunlight, wind and water. Green hydrogen is effectively produced from
energy sources that are renewable in nature and also maintains the process of electrolysis by
effectively splitting water.

Advantages of green fuel

The usage of green fuels has successively reduced the emission of greenhouse gases by
around 30 per cent of the combustion rate. A proper balance is maintained by effectively
focusing on fuel sensitivity with respect to the environment.

Furthermore, it is also noted that the application of green energy is responsible for producing
more energy referred to as “energy bounce”

Photovoltaic Cells: Photovoltaic cells are semiconductor device which convert solar energy
into electrical energy. (Photovoltaic cell is based on the principle of photoelectric effect).

Construction
Sunlight e-
Metal grid
Antireflective
layer n - type

e - h+
e - h+

p - type
Metal contact

 A typical PV cell of silicon consists of thin wafer of thickness of around 300µm of

p- type silicon on one side of this, an ultra thin (say 0.2 µm) layer of n- type is
placed. On the other side of this p - type silicon wafer, metal electrodes made up of
titanium – silver are attached to the back of p-type silicon, so that it covers completely.
 Metal electrode is placed over n- type silicon as fingers and are called as metal grids.
 An antireflection coating of silicon nitride or silicon oxide of thickness of about
0.1 µm is placed on the metal grid to increase the amount of sunlight on the cell.
 The metal grids and metal sheet which are attached to n-type and p-type are
respectively termed as –ve electrode and + ve electrode.

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 n-type silicon is rich in electrons, p-type rich in holes at p-n junction potential
difference is developed.

Working

PV cell works on the principle of photoelectric effect: E = hγ. 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 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.
Importance of PV cells:
 With the conventional energy reserves are fast depleting photovoltaics is considered to
be the future sustainable energy system. Solar energy, being unlimited, inexhaustible and
renewable, photovoltaic cells are the means to this continuous energy source.
 Photovoltaic energy conversion is highly modular this is important with respect to the
development of electrical supply systems in many rural and remote areas where grid
extension is economically not feasible.
 The photovoltaic electricity can contribute considerably to the lessening of the man
made global warming due to carbon dioxide.
 Photovoltaic cells provide power for spacecraft and satellites.

Developments in the field of photovoltaic cells will boost the semiconductor industry and
storage battery industries.

Applications:

PV can meet the need for electricity for parking meters, temporary traffic signs, emergency
phones, radio transmitters, water irrigation pumps, stream-flow gauges, remote guard posts,
lighting for roadways, and more.

Advantages of PV cells:

1. Fuel source is vast and infinite.

2. No emissions, no combustion or radioactive residues for disposal.
3. Does not contribute to global warming or pollution.
4. Low operating cost and high reliability.
5. No moving parts and so no wear and tear.
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6. No recharging is required.
7. They do not corrode.

Disadvantages of PV cells:

1. Sunlight is relatively low density energy.

2. High installation cost.
3. Energy can be produced only during daytime.

Green Hydrogen
Properties of hydrogen pertaining to fuel

Hydrogen is colourless, odourless and combustible gas having the following properties:

1. Wide range of flammability: 4% to 75% at 25℃

2. Low ignition energy: 0.02 mJ
3. Small quenching distance: 0.6 mm
4. High auto ignition temperature: 585℃
5. High octane number: 130
6. High flame speed
7. High diffusivity
8. Very low density
9. Produce no pollution; eco-friendly
10. Very pale blue flame and almost invisible in day light due to the absence of soot.
11. High calorific value of 1,41,790 kJ/kg which is higher than any other chemical fuel.

Generation of energy (green hydrogen) by electrolysis of water and its advantages

Green hydrogen is defined as hydrogen produced by splitting water into hydrogen and
oxygen using renewable electricity.

Water electrolysis

Water Electrolysis is the breakdown of water (H2O) into oxygen (O2) and hydrogen gas (H2)
by passing an electric current through it. Water electrolysis, also known as electrochemical
water splitting.

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Principle of water electrolysis

The electrolytic cell is made up of a pair of platinum electrodes immersed in water with a
small amount of an electrolyte such as KOH. The electrolyte is required because pure water
cannot carry enough charge due to a lack of ions. Water is oxidized to oxygen gas and
hydrogen ions at the anode. Water is reduced to hydrogen gas and hydroxide ions at the
cathode.

OR

When a direct current (DC) is passed through water taken in an electrolytic cell containing
two inert metal (Platinum or Iridium) electrodes which are separated by a proton exchange
membrane (PEM) or an oxygen ion exchange ceramic membrane. The water undergoes
dissociation and hydrogen & oxygen are liberated at cathode and anode respectively.

Alkaline Electrolyser of water

Construction

The Alkaline electrolysis cell (is also known as alkaline electrolyser) consists

Electrodes: Nickel metal (which is cheaper than Platinum)

Electrolyte: ∼20 – 30%W/V KOH or NaOH

Separator: Asbestos sheet or diaphragm

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Working

Water to be electrolysed is added with KOH or NaOH electrolyte, which increases the
conductivity of water. During the electrolysis, the water molecules move to the cathode by
diffusion and liberation of hydrogen takes place. The hydroxides formed at the cathode move
towards the anode, the additional hydroxide as KOH or NaOH releases more electrons and
increases the liberation of hydrogen at the cathode. The Asbestos sheet or diaphragm having
in the middle of the cell and it separates the cathode and anode also separates the produced
gases from their respective electrodes and avoiding the mixing of produced gases during the
electrolysis process.

At cathode: 2H2O(l) + 2e– → H2(g) + 2OH–, E° = - 0.83 V

At anode: 2OH– → 1/2O2 + H2O + 2e– , E° = + 0.4 V

Net reaction: H2O → 1/2O2 (g) + H2 (g) , E° = - 1.23 V

(Note: 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.

H2O → 1/2O2 (g) + H2 (g), E° = - 2.43 V )

PEM electrolyzer (Polymer electrolyte Membrane)

A proton exchange membrane (PEM) electrolyzer uses a polymer membrane as an ion

conductor to produce hydrogen gas through the process of electrolysis.

Principle of PEM water electrolysis

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 occurred by pumping of water to the anode where it is spilt into oxygen (O 2),
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.

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Construction

The major components of a PEM electrolyzer include

i) a proton exchange membrane (Nafion - polytetrafluoroethylene (PTFE) backbone with

perfluorinated-vinyl-polyether side chains containing sulphonic acid end groups )
ii) Platinum electrodes,
iii) Gas diffusion layers, and
iv) Bipolar plates.

The proton exchange membrane serves as the ion conductor, allowing protons to pass through
while blocking electrons and other ions. The electrodes are typically made of a catalytic
material, such as platinum, which promotes the electrochemical reactions that produce
hydrogen. The gas diffusion layers help distribute the reactant gases evenly across the surface
of the electrodes, and the bipolar plates serve as the current collectors and provide
mechanical support for the electrolyzer.

Working
The mechanism of operation of a PEM electrolyzer is based on the principles of electrolysis,
where an electric current is passed through an electrolyte to produce chemical reactions at the
electrodes. In a PEM electrolyzer, water is supplied to the electrolyzer and is split into its
constituent elements, hydrogen and oxygen, at the electrodes. At the anode, oxygen is
produced by the oxidation of water, and at the cathode, hydrogen is produced by the
reduction of protons from the proton exchange membrane.

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Applications
 Used in fuel cell vehicles,
 Renewable energy storage systems, and
 Industrial processes.

These proton exchange membranes having many advantages such as

 lower gas permeability,
 high proton conductivity (0.1 ± 0.02 S cm−1),
 lower thickness (Σ20–300 µm) and
 high-pressure operations.

Limitations
 Cost of electrodes is too high
 Maintenance cost is high

Solid oxide electrolyzer

Solid oxide electrolysis operates at high pressure and high temperatures 500 - 850°C and
utilizes the water in the form of steam. Solid oxide electrolysis process conventionally uses
the O2− conductors which are mostly from nickel/yttria stabilized zirconia.

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Solid oxide electrolyzers, which use a solid ceramic material as the electrolyte (YSZ) that
selectively conducts negatively charged oxygen ions (O2- ) at elevated temperatures, generate
hydrogen in a slightly different way.
• Steam at the cathode combines with electrons from the external circuit to form hydrogen
gas and negatively charged oxygen ions.
• The oxygen ions pass through the solid ceramic membrane and react at the anode to form
oxygen gas and generate electrons for the external circuit.
The main characteristics of solid oxide electrolysis (SOE) technology is higher operating
temperature which makes advantageous compared to low temperature electrolysis.

Limitation: SOE having some issues related to lack of stability and degradation.

The advantages of using hydrogen as a fuel in fuel cells are:

• It has high electrochemical reactivity,
• It has high theoretical energy density,
 Unlimited availability (as long as you can break down the water
• It produces harmless combustion product (H2O) for the environment.

Hydrogen production:
Solar-to-hydrogen conversion based on photocatalytic and photoelectrocatalytic water
splitting is considered as a promising technology for sustainable hydrogen production.
Photocatalytic (PC) water splitting for the production of hydrogen
Splitting of water to generate hydrogen and oxygen using solar energy in the presence
of photocatalyst is known as photocatalytic water splitting. This process can be more efficient
if the photocatalyst is directly suspended in water so that the reaction takes place in one step.
The photocatalytic production of hydrogen represents a fascinating way to convert and store
solar energy as chemical energy, in the form of renewable hydrogen, the ideal fuel for the
future.

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When a beam of light is made to fall on water containing suitable photocatalyst

(semiconducting material) having an energy gap of 1.23 eV, the light energy (hν) excites an
electron (e-) in the catalyst from valence band to conduction band. The produced (h+) will
reacts with neighbouring water molecule producing oxygen gas.

H2O (l) + [hν] + 2 h+ 2H+ (aq) + 1/2O2(g)

The H+ ions combine to produce hydrogen at the surface of the co-catalyst.

2H+ (aq) + 2 e- H2(g)

The produced hydrogen can be used as a fuel in hydrogen oxygen fuel cell.

Photo electrocatalytic (PEC) water splitting for the production of hydrogen

Photo electrocatalytic (PEC) water splitting is the artificial photosynthesis approaches for the
hydrogen fuel production. It involves photogenerated carriers on the surface and reactants
adsorbed on the surface or in the electrolyte. The reaction takes place at the electrode
electrolyte interface.

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The light energy excites an electron (e-) in the semiconducting material made as an anode.
The produced hole (h+) will reacts with the neighbouring water molecule forming oxygen and
is liberated at the anode.

H2O (l) + [hν] + 2 h+ 2H+ (aq) + 1/2O2(g)

The H+ ions formed will then migrated towards the cathode and discharged as hydrogen and
liberated. The liberated hydrogen is stored and used as fuel in hydrogen oxygen fuel cell for
the production of electricity.

2H+ (aq) + 2 e- H2(g)

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