Dept.

of Chemistry/PACE/Mangalore
(22CHES12/22)

MODULE 4 -POLYMERS AND GREEN FUELS

A polymer is a compound of high molecular weight made by the combination of large number of
small repeating units (monomers).
Example: Polythene is formed by linking a large number of ethene molecules together.

n CH2=CH2 ( CH2-CH2 )n
ethene (monomer) polythene (polymer)

POLYMERIZATION: The chemical process by which the monomers (low molecular weight)
are converted into polymers (high molecular weight) is called polymerization. All
polymerization reactions need suitable initiators.

Temperature
Monomers + Initiator Polymer
Pressure

Molecular weight of a polymer:

Molecular weight of a polymer is the product of degree of polymerization and the molecular
weight of repeating unit.
M = DP x Mol. Wt of repeat unit.

Number average molecular weight (Mn):

Number average molecular mass is the mass obtained when total mass of all molecules of a
sample is divided by the total number of molecules
Assume there are ‘n’ number molecules in a polymer sample.
n1 have M1 molecular weight, n2 have M2 molecular weight………………….till ni have Mi
molecular weight.
Total number of molecules= n1 + n2+ n3 + ……………..+ ni = ∑ ni

Molecular weight contribution from all the species = n1M1 + n2M2 + n3M3 + ….+niMi = ΣniMi

Then, the number average molecular mass (Mn) of a polymer is given by the equation,

n1M1 + n2M2 + .................niMi

Mn =
n1 + n2 + .................ni
Σ niMi
Mn =
Σ ni

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 Dept. of Chemistry/PACE/Mangalore
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Where, n and M represent the number and molecular mass of each species present in the
polymer.
Weight average molecular weight (Mw):
Weight average molecular mass is the mass obtained when sum of the products of total mass of
groups of molecules and their respective molecular masses is divided by the total mass of all
molecules
Total weight of polymer = Wi = niMi
Then weight average molecular mass of a polymer is given by the equation,

W1M1 + W2M2 + .................WiMi

Mw =
W1 + W2 + .................Wi

Where, W and M represent the weight and molecular mass of each species present in the
polymer. Since W = nM, the above equation can be represented as,

n1M12 + n2M22 + .................niMi2

Mw =
n1M1 + n2M2 + .................niMi

Σ niMi2
Mw =
Σ niMi

Numerical Problems:
1. A polymer sample contains 1,2,3 and 4 molecules having molecular weights 10 5, 2 x 105, 3 x
105, and 4 x 105, respectively. Calculate the number average and weight average molecular
weight of the polymer.
Number average molecular weight of the polymer,

Σ niMi
Mn =
Σ ni
5 5 5 5
= 1 (1 x 10 ) +2(2 x 10 ) +3(3 x 10 ) +4(4 x 10 )
1+2+3+4

= 3.0 x 105

Weight average molecular weight of the polymer,

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 Dept. of Chemistry/PACE/Mangalore
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Σ niMi2
Mw =
Σ niMi

1(1 x 105)2 +2 (2 x 105)2 + 3(3 x 105)2 + 4(4 x 105)2

=
1(1 x 105) + 2(2 x 105) + 3(3 x 105) +4(4 x 105)

= 3.3 x 105

2. A polymer of polypropylene is found to have the following composition.

CH3

a. R CH2 CH R
20 %
400
CH3

b. R CH2 CH R
30 %
500
CH3

c. R CH2 CH R
50 %
600

Calculate the number average and weight average molecular mass of the polymer. [Atomic mass
of C = 12, H = 1, Neglect the molecular mass of R.]
Molecular mass of (a) = [(12 x 3) + (6 x 1)] x 400 = 16 800
Molecular mass of (b) = [(12 x 3) + (6 x 1)] x 500 = 21 000
Molecular mass of (c) = [(12 x 3) + (6 x 1)] x 600 = 25 200

n1M1 + n2M2 + .................niMi

Mn =
n1 + n2 + .................ni
n1 = 20, n2 = 30, n3 = 50, M1 = 16800, M2 = 21000, M3 = 25200

20x16800 + 30x21000 + 50x25200

Mn =
20 + 30 + 50
= 22 260

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 Dept. of Chemistry/PACE/Mangalore
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n1M12 + n2M22 + .................niMi2

Mw =
n1M1 + n2M2 + .................niMi
2 2 2
= 20x(16800) + 30x(21000) + 50x(25200)
20x16800 + 30x21000 + 50x25200

= 22 715
3. A polydisperse sample of polystyrene is prepared by mixing three mono disperse samples
in the following proportions. 1g of 10000 molecular weight, 2g of 50000 molecular
weight and 2g of 100000 molecular weight. Determine number average and weight
average molecular weight. Find the index of polydispersity

W1= n1 M1 =1 g M1 =10000
W2= n2 M2 =2 g M2 =50000
W3= n2 M2 =3 g M3 =100000

We know that W1= n1 M1

Hence n1 = W1 / M1
n1 =1/ 10000
Thus n2 =1/ 50000 n3 =1/ 100000
∑ 𝑛𝑖 𝑀𝑖
Numbera average molecular weight Mn =
∑ 𝑛𝑖

𝑛1 𝑀1 + 𝑛2 𝑀2 + 𝑛3 𝑀3
Mn =
𝑛1 + 𝑛2 + 𝑛3

1+2+3
Mn =
1 2 3
+ +
10000 50000 100000

=31250
∑ 𝑛𝑖 𝑀𝑖2
weight average molecular weight MW =
∑ 𝑛𝑖 𝑀𝑖

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 Dept. of Chemistry/PACE/Mangalore
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𝑛1 𝑀12 + 𝑛2 𝑀22 + 𝑛3 𝑀32

MW =
𝑛1 𝑀1 + 𝑛2 𝑀2 + 𝑛3 𝑀3

𝑊1 𝑀1 + 𝑊2 𝑀2 + 𝑊3 𝑀3
MW =
𝑊1 + 𝑊2 + 𝑊3
(1𝑥 1000) + (2 𝑥 50000) + (2𝑥 100000)
MW =
1+2+3

=62000

4. 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. .( Answer: Mn = 3.75x103 g/mol
Mw =4.43x103 g/mol)
5. 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.( Answer: Mn = 2833.3 g/mol
Mw =3058.8 g/mol)
Conducting polymers:

An organic polymer with highly delocalized pi- electron having electrical conductance in the
order of a conductor is called a conducting polymer.
Example for conducting polymer: ploy aniline, poly acetylene
Synthesis of polyacetylene
Poly acetylene is synthesized using zeigler-Natta catalyst (mixture of tetra butoxy titanium and
triethyl aluminum). Catalyst is suspended in silicon oil through which acetylene gas is passed, is
stirred for 2 hour at 120˚ C, and then cooled slowly to room temperature resulting in thin sheets
of poly acetylene.

Mechanism of conduction in polyacetylene:

Polyacetylene can be converted into conducting polymer by 2 methods.

1. Oxidative doping (p-doping)
2. Reductive doping (n-doping)
1. The oxidative doping ( p-doping) of a polyacetylene:

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 Dept. of Chemistry/PACE/Mangalore
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 In this process, polymer chain is partially oxidized using mild oxidizing agent iodine in
CCl4
 In the first step, one electron is removed from the pi backbone of the chain leaving a
positive charge on one of the carbon atoms.
 This creates a polaron (radical cation) on polymer back bone on first stage of oxidation.
 On second stage of oxidation, another radical cation is formed called bipolaron.
 The radical migrates towards each other and combine to form double bond.
 The chain have positive charges (hole), this is responsible for conduction.

2. The reductive doping ( n-doping) of a polyacetylene:

 In this process, polymer chain is partially reduced using mild reducing agent sodium
naphthalide in tetra hydro furan
 In the first step, one electron is added to the pi backbone of the chain leaving a negative
charge on one of the carbon atoms.
 This creates a polaron (radical anion) on polymer back bone on first stage of oxidation.
 On second stage of oxidation, another radical anion is formed called bipolaron.
 The radical migrates towards each other and combine to form double bond.
 The chain have negative charges (carrier), this is responsible for conduction

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 Dept. of Chemistry/PACE/Mangalore
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Applications:
1. As an electrode material for commercial rechargeable batteries
2. As conductive tracks on printed circuit board.
3. As sensors - humidity sensor, gas sensor, radiation sensor, biosensor for glucose,
galactose etc.
4. In electro chromic display windows.
5. In information storage devices.
6. As film membrane for gas separation
7. In fuel cell as the electro catalytic material
8. In light emitting diodes

Kevlar:
Kevlar is an aramide (aromatic polyamide). Chemical composition of Kevlar is poly (para-
phenylene terephthalamide). It belongs to a family of nylons.
Synthesis:
It is synthesized from the monomers 1, 4- phenylene-diamine and terephthaloyl chloride through
a condensation reaction with elimination of HCl as a byproduct.

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 Dept. of Chemistry/PACE/Mangalore
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Properties:
 Stronger than steel
 Light weight and high strength
 High impact and abrasion resistance
 High tensile strength
 High temperature resistance
Application:
Used in lightweight boat hulls, aircraft fuselage panels, pressure vessels, high performance race
cars, bullet proof vests, puncture resistance tyres, combat helmets and ballistic face masks.

GREEN FUELS

INTRODUCTION TO DIFFERENT TYPES OF FUEL

Green fuels also called green hydrocarbons, biofuels, are fuel produced from biomass sources
through a variety of biological and thermo chemical. Various numbers of green fuels are found on
earth that can be used instead of non-renewable energy sources thereby, effectively decreasing
their usage and exploitation. Green Fuel offers environmentally friendly and sustainable
renewable vehicle fuel and electricity that reduces greenhouse gas emissions and improve air
quality. Some of the types of green fuels are methanol, hydrogen, ethanol, Biogas, Biodiesel and
solar energy etc. With ever-growing awareness of the climate crisis and global warming,
everyone is turning towards sustainable alternatives to tackle them. Green fuels offer a game-
changing solution. Environment-conscious people all across the world have slowly been
switching to biofuels, leaving the traditional fuels. There are various advantages of biofuels both
short and long-term. In comparison to fossil diesel, biofuel is created from renewable resources
and is less combustible. Its lubricating qualities are greatly improved. When compared to
conventional diesel, it emits fewer hazardous carbon emissions.

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Types of Fuels:
Fuels can be generally classified on the basis of two factors:
1. On the basis of their 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
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.
PHOTO VOLTAIC CELLS OR SOLAR CELLS:
It is a semiconductor device which converts solar energy into electrical energy. This
conversion is called photovoltaic effect.
COSTRUCTION & WORKING OF A PHOTOVOLTAIC CELL:
Construction
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 Dept. of Chemistry/PACE/Mangalore
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The device used in photovoltaic cell is p-n junction diode made from silicon semiconductor. p-
n junctions are formed by joining n-type and p-type semiconductor materials. It has two
electrical contacts one is a metallic grid over n type and other is a layer of silver metal at back of
p type semiconductor. A photovoltaic cell consists of thin wafer of p type silicon about 300
micron thickness. A thin wafer of n-type silicon is placed above this to create p-n junction. A rod
of Titanium-silver solder is covered completely on p-side and n-type is covered by finger like
grids of metal, so that light can pass through. A thin coating of antireflective layer is placed in
between the grids to increase the transmission of light.
Working:
When sunlight with their photons carrying energy E=hγ falls on p-n diode, electrons hole
pairs are generated by the absorption of the radiation. The electrons are drifted to and collected at
the n type end and 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.

Advantages of photovoltaic cells:

 They are Environmental friendly
 No emissions, no combustion or radioactive waste for disposal.
 Low operating costs (no fuel).
 They need no recharging
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 Dept. of Chemistry/PACE/Mangalore
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 They don’t suffer wear and tear as they have no movable parts
 No corrosion
 They operates at ambient temperature
Disadvantages of photovoltaic cells:
 Sun light is a diffuse source. i.e it is relatively low density energy.
 High installation costs.
 Silicon required for PV cell is of high purity so high cost of silicon purification leads to
the higher cost of PV cell
 Storage difficulties.
 Energy can be produced only during day time.

Green hydrogen

Generation of hydrogen by electrolysis of water- Alkaline water electrolysis

Green hydrogen is produced by using electricity to power an electrolyser that splits the
hydrogen from water molecules.This reaction takes place in a unit called an
electrolyzer. Electrolyzers consist of an anode and a cathode placed in a liquid alkaline
electrolyte solution of potassium hydroxide (KOH) or sodium hydroxide (NaOH). The electrodes
are made up of nickel and are separated by a diaphragm, separating the product gases and
transporting the hydroxide ions (OH−) from one electrode to the other. Water undergoes
reduction at cathode to give hydrogen gas and hydroxyl ions. Hydroxyl ions moves towards
anode through the membrane and undergoes oxidation at anode to give oxygen and water.
Reactions:
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 Dept. of Chemistry/PACE/Mangalore
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Cathode reaction (reduction): 2 H2O + 2e− → H2 + 2 OH−

Anode reaction (oxidation): 2 OH− → 1/2 O2 + H2O + 2 e−
Overall reaction 2 H 2O → H2 + 1/2 O2

Advantages alkaline water electrolysis:

 Alkaline water electrolysis is an easier cheaper and simple method for hydrogen
production.
 Electrodes are made of cheaper nickel metal.
 Pure carbon free hydrogen is obtained.
 Zero emission of Carbon dioxide
 Long term stability

Generation of Green Hydrogen from water electrolysis- Proton Exchange

Membrane(PEM) Electrolyzer
PEM water electrolysis systems provide several advantages over the alkaline electrolysis
technologies, such as higher rate of hydrogen production, more compact design, and greater
energy efficiency. In a proton exchange membrane (PEM) electrolyzer, the electrolyte is a solid
proton conducting polymer membrane. Green hydrogen is produced by using electricity to
split the hydrogen from water molecules
Anode: Iridium metal particles dispersed on porous carbon is used as anode.
Cathode: platinum particles coated on porous carbon are used as cathode.
Electrolyte/separator: A porous solid polymer electrolyte made of sulfonated tetra fluoro
ethylene polymer (NAFION) used as an electrolyte as well as separator,
Anode is connected to positive end and cathode is connected negative end of the DC source.
Deionised water is circulated in the anodic chamber where it is oxidised liberating oxygen gas
and hydrogen ions (protons). The electrons flow through an external circuit and the hydrogen
ions(protons) move through solid polymer electrolyte membrane to the cathode. At cathode
hydrogen ions undergo reduction to liberate hydrogen gas. The hydrogen gas obtained from
electrolysis of water is used a fuel.

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Reactions

Anode reaction (oxidation): 2 H2O → O2 + 4H+ + 4e-

Cathode reaction (reduction): 4H+ + 4e- → 2H2
Overall reaction 2 H2O → O2 + 2H2

Advantages of PEM electrolysis

 Polymer membrane is chemically stable and noncorrosive
 Pure carbon free hydrogen is obtained from this method
 It is possible to produce hydrogen using only renewable energy.
 It emits only oxygen as a by-product without any carbon emissions.
 Ecofriendly
 An operational cost is low.
 Highly efficient

GRAPHENE OXIDE (GO)

 A single sheet of carbon atom taken out of graphite is called as graphene.
 When oxygen containing functional groups like epoxide, carbonyl, carboxyl and
hydroxyl groups added to graphene layer then the resulting material is Graphene oxide

Synthesis
 Graphene oxide is synthesized by hummer’s method developed by Hummers and
Offeman, it is a oxidised derivative of graphite.
 It is prepared by subjecting graphite with anhydrous mixture of conc.sulphuric acid,
sodium nitrate and potassium permanganate.
 Oxidation reaction is completed within 2 hour at temperature below 45˚C

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 Dept. of Chemistry/PACE/Mangalore
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PROPERTIES
 The structure and chemical composition of GO is not fixed
 GO is more hydrophilic due to polar functional group. It can be dispersed in water and
other polar solvent.
 GO exhibit tunable electrical and optical properties. The band gap Go can be varied from
0.5 to 2.2 eV depending on the synthesis procedure. Go can be transferred from insulator
to semiconductor and further to semi metal.
 GO exhibits high specific surface area and highly effective in desalination of water and
removal of toxic heavy metals from water.
 It is bio compatible and can be functionalized easily.
 Thin films of GO exhibit a high optical transparency.

Applications

 Graphene oxide can be used in electronic devices, energy storage devices, bio sensors,
biomedical applications, super capacitors, catalysts, and water purification.
 As an electronic device, GO is used in field-effect transistors (FETs) as chemical sensors
 GO also used in light-emitting diodes (LEDs) as a transparent electrode
 GO, the material is used as an electrode in double-layered capacitors, batteries, fuel cells,
and solar cells
 Corrosive acids can be stored in glass or copper containers that are covered inside with
such graphene paint
 In order to improve shelf life in medical infrastructure, graphene-coated plastic films may
be used.

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 Dept. of Chemistry/PACE/Mangalore
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Important questions:

1. Preparation, properties, and commercial applications of Kevlar

2. Explain the construction and working of photovoltaic cells
3. Explain the synthesis of polyacetylene and mention its applications
4. Explain the mechanism of conduction in Polyacetylene
5. Explain the generation of hydrogen by Alkaline water electrolysis and mention its
application
6. Explain the generation of hydrogen by proton exchange membrane Electrolysis and
mention any 4 advantages
7. EXPLAIN THE SYNTHESIS OF GRAHENE OXIDE. WRITE THE PROPERTIES
AND APPLICATIONS
8. A polydisperse sample of polystyrene is prepared by mixing three mono disperse samples
in the following proportions. 1g of 10000 molecular weight, 2g of 50000 molecular
weight and 2g of 100000 molecular weight. Determine number average and weight
average molecular weight.
9. A polymer sample contains 10,20,30 and 40 molecules having molecular weights 104, 2 x
104, 3 x 104, and 4 x 104, respectively. Calculate the number average and weight average
molecular weight of the polymer

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