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Module -4
Polymers and Green Fuels

Syllabus
Polymers: Introduction, Molecular weight - Number average, weight average and numerical
problems. Conducting polymers – Synthesis and conducting mechanism of polyacetylene and
commercial applications. Preparation, properties, and commercial applications of Kevlar

Green Fuels: Introduction to different types of fuels, past and future perspective of green
fuels. construction and working of solar photovoltaic cell, advantages, and disadvantages.

Green hydrogen: Introduction to properties of hydrogen pertaining to fuel. Introduction to

electrolysis of water. Generation of hydrogen by electrolysis of water, (Explain the electrolysis
of water with diagram and electrode reactions) and mention any 4 advantages

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Polymers
Polymers are large molecules made by bonding (chemically linking) a series of building
blocks. The word polymer comes from the Greek words for “many parts.” Each of those parts is
scientists call a monomer (which in Greek means “one part”).

Monomers: Small molecules of low molecular weight, which combine to give a polymer, are
called monomers.

Degree of polymerization: The number of monomers used in the process is called degree of
polymerization.

Functionality: The total number of functional groups or bonding sites present in a monomer
molecule is called the functionality of the monomer.
Polymerization
Is the process of conversion of low molecular weight substances into high molecular weight
substances with or without the elimination of by products such as HCl, H2O, NH3 etc.

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Molecular weight
Polymer molecular weight determines various physical properties such as melt viscosity,
tensile strength, toughness, thermal behavior, chemical resistance, and weatherability.
Universally, higher molecular weights are associated with higher physical properties whereas,
lower molecular weights are associated with lower properties.

During formation of polymers, different polymers have different degrees of polymerization

i.e. they have different chain lengths. Thus, molecular masses of individual macromolecules in
a particular sample of polymer are different. Hence, an average value of the molecular mass is
taken. There are two ways through which average molecular masses can be calculated.

1. Number average molecular mass (Mn)

2. Mass average molecular mass (Mw)

1. Number average molecular mass (Mn)

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

For example, in a particular sample, suppose

N1 molecules have molecular mass M1 each

N2 molecules have molecular mass M2 each and so on….

Then, we have
Total mass of all the N1 molecules = N1M1

Total mass of all the N2 molecules = N2M2 and so on….

Therefore, total mass of all the molecules = N1M1 + N2M2 + N3M3 + …… = Σ NiMi

total number of all the molecules = N1 + N2 + N3 + …… = Σ Ni

N1M1 + N2M2 + N3M3 + …

Mn = N1 + N2 + N3 + ……

ΣNiMi
Mn = ΣNi

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2. Mass average molecular mass (Mw)

Mw is the mass obtained when sum of the products of total mass of groups of molecules
(having different molecular masses) and their respective molecular masses is divided by total
mass of all the molecules.

For example, in a particular sample, suppose

N1 molecules have molecular mass M1 each

N2 molecules have molecular mass M2 each and so on….

Then, we have
Total mass of all the N1 molecules = N1M1

Total mass of all the N2 molecules = N2M2 and so on….

The products of total mass of groups of molecules (having different molecular masses) and
their respective molecular masses = (N1M1 M1), (N2M2 M2), (N3M3 M3), …...

= (N1M12), (N2M22), (N3M32), …...

= Σ NiMi2
The total mass of all the molecules = N1M1 + N2M2 + N3M3 + …… = Σ NiMi

(𝑁1 𝑀12 )+ (𝑁2 𝑀22 )+ (𝑁3 𝑀32 ),…

Mw = N1M1 + N2M2 + N3M3 + …

Σ(𝑁𝑖 𝑀𝑖2 )
Mn = Σ𝑁𝑖 𝑀𝑖

Conducting polymers
As the name suggests organic polymers that conduct electricity are known as conducting
polymers. They are also known as intrinsically conducting polymers (ICPs) and they have
alternating single and double bonds along the polymer backbone (conjugated bonds) or that
are composed of aromatic rings such as Phenylene, naphthalene, anthracene, pyrrole, and
thiophene which are connected through carbon-carbon single bonds.
Examples: Polyacetylene, Polypyrrole, Polyaniline, etc
Synthesis
The first conducting polymer synthesised was poly(acetylene). The first reports on acetylene
polymers date back to the last century. Cuprene, a highly crosslinked and extremely irregular
product of acetylene polymerisation in the presence of copper containing catalysts being a
typical example for the initial efforts.

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Reaction conditions allow to control the morphology of the conjugated polymer obtained as
powder, gel, spongy mass or a film. Iodine doping renders these polymers conducting and
values of up to 105 S/cm have been claimed. Films can be stretched.
Conducting mechanism of polyacetylene
Conducting polymers comes in two forms that are doped conducting polymers and non-
doped conducting polymers. The conductivity of non-doped conjugated polymers is due to
the existence of a conductivity band similar to a metal. In a conjugated polymer, three of the
four valence electrons form strong sigma bonds through sp² hybridization where electrons are
strongly localized. The remaining unpaired electron of each carbon atom remains in a P𝘻
orbital. It overlaps with a neighbouring P𝘻 orbital to form a pi bond. The pi electrons of these
conjugated P𝘻 orbitals overlap to form an extended P𝘻 orbital system through which electrons
can move free (delocalization of pi electrons). However, the conductivity of non-doped
polymers is low.

In the case of doped conjugated polymers, an electron is removed from the valence band by
oxidation (p-doping) or is added to the conducting band by reduction (n-doping). P-doping
increases the mobility of electrons in these delocalized orbitals and the polymer becomes
highly conductive.

Polyaniline is a semiconductor on its own, but when doped, its conductivity increases. It can
be doped by oxidation with halogen (I2) called P-doping or by reduction with alkali metal
(Na) called N-doping.

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P-doping mechanism:

In this process Pi-electrons of polymer are partially oxidized using a suitable oxidizing agent
like I2 vapor. This creates positively charged sites on polymer backbone, which are current
carriers for conduction. The removal of an electron (oxidation) from polymer pi-back bone
using I2 as oxidizing agent leads to the formation of delocalized radical ion called “polaron”.
A second oxidation of a chain containing polaron followed by radical recombination yields 2
charge carriers on each chain. The positive charge sites on the polymer chain are compensated
by anions I3¯ formed by oxidizing agent during doping. The delocalized positive charges on
the polymer chain are mobile. Thus, these delocalized positive charges are current carriers for
the conduction. These charges must move from chain to chain as depicted below.

Stepwise conduction mechanism of polyacetylene

Applications of Polyacetylene
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.

Kevlar
Kevlar belongs to a family of aramids. It is a aromatic polyamide with the name poly

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[para-phenylene terephthamide]. The linkage through para positions of the phenyl rings gives
Kevlar a strong ability to stretch and hence its extra strength.

Synthesis
Kevlar can be synthesized in a solution from monomers para-phenylenediamine and
terepthaloyl chloride in a condensation reaction in which molecules of HCl are terminated as a
byproduct in a solution of N-methyl pyrrolidone and CaCl2.

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Properties:
1. Strong but relatively light weight

2. Tensile strength of Kevlar 49 and Kevlar 29 is over 8 times greater than that of steel wire

3. It has very low compressive strength

4. It suffers from corrosion if exposed to chlorine

5. It quickly reacts with UV light, hence, stabilizers are required for outdoor applications

Applications: Kevlar or its composites are used in the manufacturing of following products

1. Reinforced tyres

2. Sports shoes, snow boards, skate boards, rackets etc.

3. Bullet proof vests

4. Fire fighting apparel, body pads, industrial gloves

5. Military helmets, body armors, tactical vests

Green Fuels
Solar Energy
The amount of sunlight that strikes the earth's surface in an hour and a half is enough to
handle the entire world's energy consumption for a full year. Solar technologies convert
sunlight into electrical energy either through photovoltaic (PV) panels or through mirrors that
concentrate solar radiation. This energy can be used to generate electricity or be stored in
batteries or thermal storage.
Photovoltaic cell
Photovoltaic cell is semiconductor device that convert sunlight into direct current electricity.
Photovoltaic cell is based on photoelectric effect.

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Construction and working of a solar cell/photovoltaic cell

Construction
Polycrystalline silicon wafers are made by block-cast silicon ingots into very thin
wafers/slices (250-350m). The wafers etched slightly to remove saw damage. Wafer is lightly
p- doped to make a solar cell form wafer, surface diffusion of n-type dopant is done on the
front side, this forms a p-n-junction few hundred nanometers below the surface (10-9m).
Antireflecting coating of silicon nitride/TiO2 is then applied in a layer using plasma enhanced
chemical vapor deposition (PECVD) technique. The wafer is then metallized. The metal grid
contact made by using silver paste. The rare contact is made by screen printing using
aluminium paste. Metal rods are then given to make ohmic contact with the silicon.

Photovoltaic cell.

Working
Photovoltaic cells or Solar cells are the semiconductor devices which converts sunlight into
electricity. Sunlight consists of Electromagnetic radiation of particles called Photons (hν). The
photons carry a certain amount of energy given by the Planck quantum equation,
E=hc / λ
Where h is Planck’s constant, c is the velocity of light and λ is the wavelength of the radiation.
When light radiation falls on the p-n-junction diode, electron-hole pairs are generated by the
absorption of radiation. The electron is drifted and collected at n-type end and holes are
drifted 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 the external circuit. Thus,
photoelectric current is produced and available for the use.

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Importance of Solar cell

• Photovoltaic cells can serve for both off grid and on grid application- telecommunication and
solar home systems.
• Photovoltaic energy conversion is highly modular.
• Photovoltaic electricity contributes considerably to the abatement of the man-made global
warming due to CO2
Photovoltaic cells provide power for spacecraft and satellites in extra-terrestrial

Green hydrogen
Green energy is any energy type that is generated from natural resources, such as sunlight,
wind or water. As a source of energy, green energy often comes from renewable energy
technologies such as solar energy, wind power, geothermal energy, biomass and hydroelectric
power.
In order to be deemed green energy, a resource cannot produce pollution, such as is found
with fossil fuels. This means that not all sources used by the renewable energy industry are
green. For example, power generation that burns organic material from sustainable forests
may be renewable, but it is not necessarily green, due to the CO 2 produced by the burning
process itself.

Production of green hydrogen

Electrolysis is a promising option for carbon-free hydrogen production from renewable and
nuclear resources. Electrolysis is the process of using electricity to split water into hydrogen
and oxygen. This reaction takes place in a unit called an electrolyzer. Electrolyzers can range
in size from small, appliance-size equipment that is well-suited for small-scale distributed
hydrogen production to large-scale, central production facilities that could be tied directly to
renewable or other non-greenhouse-gas-emitting forms of electricity production.

How Does it Work?

Electrolyzers consist of an anode and a cathode separated by an electrolyte. Different

electrolyzers function in different ways, mainly due to the different type of electrolyte material
involved and the ionic species it conducts.

Polymer Electrolyte Membrane Electrolyzers

In a polymer electrolyte membrane (PEM) electrolyzer, the electrolyte is a solid specialty

plastic material.

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• Water reacts at the anode to form oxygen and positively charged hydrogen ions
(protons).
• The electrons flow through an external circuit and the hydrogen ions selectively move
across the PEM to the cathode.
Anode Reaction: 2H2O → O2 + 4H+ + 4e-
• At the cathode, hydrogen ions combine with electrons from the external circuit to form
hydrogen gas.
Cathode Reaction: 4H+ + 4e- → 2H2

Alkaline Electrolyzers (AEL)

Alkaline electrolyzers operate via transport of hydroxide ions (OH-) through the electrolyte
from the cathode to the anode with hydrogen being generated on the cathode side.
Anode Reaction: 2 OH- → 1/2O2 + H2O + 2e-
Cathode Reaction: 2H2O + 2e- → H2 + 2OH-

Solid Oxide Electrolyzers

Solid oxide electrolyzers, which use a solid ceramic material as the electrolyte 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.
They operate a high temperature, typically 600°C to 1000°C to allow electrolysis of water. The high
temperature operation reduces the need of electrical energy required for the electrolysis and instead uses
heat energy to split water & carbon dioxide.

Anode (Oxygen electrode) Reaction: O2- → 1/2O2 + 2e-

Cathode (hydrogen electrode) Reaction: 2H2O + 2e- → H2 + O2-

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Production of green hydrogen (exam point of view)

Electrolysis is based on the splitting of water by means of an electrical potential (dissociation
of the water molecule in an electrical field). Hydrogen is evolved on the cathode (−) and
oxygen on the anode (+). Between the electrodes is an electrolyte, which acts as an electrical
insulator and ionic conductor. The ions transferred between the electrodes are, either H+, OH−
or O2− and the corresponding electrolysers are called polymer electrolyte membrane (PEM),
alkaline or solid oxide electrolyte (Figure 2.3). The electrolysers are operated under different
conditions such as pressure and temperature. Typically, PEM and AEL devices operate at
moderate temperatures (<80˚C and <220˚C, respectively) while solid oxide electrolysers
operate at elevated temperatures (>600˚C).

Operation principles of alkaline, PEM (proton-exchange membrane) and solid oxide water
electrolysis. The overall reaction is H2O → H2 + 1/2O2. Oxygen evolution occurs at the anode,
hydrogen evolves at the cathode. The case of solid oxide electrolysis shown is that of an O 2−-
conducting electrolyte, with a nickel/yttria-stabilized zirconia cathode and a lanthanum
strontium manganite (LSM) anode.
Bibliography
https://www.azonano.com/article.aspx?ArticleID=4044

Nano Materials Science 1 (2019) 31–47

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J. Am. Chem. Soc. 1958, 80, 6, 1339

Energy.Gov
https://www.h2epower.net/solid-oxide-electrolyser-cell/
Progress in Energy and Combustion Science 58 (2017) 1–35

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