Module-4

POLYMERS AND GREEN FUELS

Lecture-1
POLYMERS
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 are the building blocks of polymer.

polythene (polymer)
Classification
Based on the origin polymers are classified as natural polymers and synthetic polymers.
Natural polymers
These are obtained from natural sources such as plants and animals.
Example: Silk, starch, cellulose, proteins, wool etc.
Synthetic polymers
These are synthesized from simple molecules (i.e man made polymers)
Example: Polyethylene, PVC, polystyrene, nylon, plexiglass, polyesters, Teflon etc.
Polymerization
The chemical process by which the monomers are converted into polymers is called the
polymerization reaction.
Types of polymerization
Addition polymerization (Chain polymerization)
Addition polymerization takes place by linking together simple unsaturated molecules like alkenes
or substituted alkenes without elimination of any by products.
 addition
Eg: n H2C CH2
H2C CH2
polymerization n
Ethene Polythene

addition
n H2C CH H2 C CH
polymerization n
Cl Cl
Vinyl Chloride Poly vinyl chloride

addition
n F2C CF2
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 H 2O, NH3 and HCl. The polymer
obtained is called copolymer.
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

Molecular weight of Polymers:

The length of a polymer chain can be expressed in terms of molecular mass of the polymer. The
molecular mass (M) of a homopolymer is related to the degree of polymerization (DP) by the
relation M = DP x M, where, M is the molecular mass of the repeating unit.
The molecular mass of a hetero polymer is the sum of the products DP x M for each type of
repeating unit. Polymers have varying chain lengths; hence two types of average molecular masses
have been recognized namely, number average and weight average molecular mass.
Number average molecular mass:
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
Let the polymer chain consist of ‘n’ polymer chains of which n1 of M1 mol.wt., n2 of M2
mol.wt…… till ni of Mi mol.wt.
Then, total no. of molecules = n1 + n2 + n3 + ….+ ni = Σni
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

Where, n and M represent the number and molecular mass of each species present in the polymer.

Weight average molecular mass:

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
Weight of n1 species = W1 = n1M1
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

Review Questions

1. What is a polymer?
2. Give an example of synthetic polymer.
3. Give an example of natural polymer.
4. What is polymerization?
5. Name the two types of polymerization.
Lecture-2
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,

Σ n i M i2
Mw =
Σ n iM i

1 (1 x 1 0 5 ) 2 + 2 (2 x 10 5 ) 2 + 3(3 x 1 0 5 ) 2 + 4(4 x 1 0 5 ) 2
=
1 (1 x 1 0 5 ) + 2 (2 x 1 0 5 ) + 3(3 x 1 0 5 ) + 4(4 x 1 0 5 )

= 3 .3 x 1 0 5

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

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

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

= 22 715

Review Questions
1. What is number average molecular mass of polymer?
2. What is weight average molecular mass of polymer?

Lecture-3
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.
The polymer should have the extensive conjugation of pi-bond, linear backbone chain and easily
oxidizable and reduceable to become a conducting polymer. Few polymers which conduct
electricity are polyacetylene, polyaniline, polythiophene etc.
Synthesis:
Polyacetylene are synthesized using Zeigler-Natta catalyst. The catalyst is suspended in silicone oil
through which acetylene gas is passed, is stirred for two hours at 120 oC. Later it is cooled slowly to
room temperature resulting in thin sheets of Polyacetylene.

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
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. Oxidizing agent takes away electron from pi-backbone of the polymer
chain creating a hole. This creates positively charged site on polymer backbone, which are current
carriers for conduction. The oxidizing agents used in p-doping are iodine in CCl 4 etc.
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

Step 1: The Polyacetylene is treated with suitable oxidizing agent such as Iodine in CCl 4 leads to
the formation of delocalized free radical ion called polaron.one electron is removed from pi-
backbone of the polymer chain leaving behind positive charge on one carbon atom.
Step 2: The second oxidation with the same oxidizing agent of the chain containing polaron
produces two positive charges. The positively charged sites on the polymer chains are compensated
by anions I-3.and thus polymer is electrically neutral.
Step 3: Next the radical recombination takes place to form a double bond. The delocalized positive
charges on the polymer chain are mobile, not the dopant anions. Thus, by applying potential the
delocalized positive charges move and thus making a conductive polymer.
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

Step 1: The Polyacetylene is treated with suitable reducing agent such as sodium naphthalide in
tetrahydrofuran leads to the formation of delocalized free radical ion called polaron. One electron is
added to the polymer chain.
Step 2: The second reduction with the same reducing agent of the chain containing polaron
produces two negative charges. The negative charged sites on the polymer chains are compensated
by cations Na+ and polymer as a whole is electrically neutral.
Step 3: Next the radical recombination takes place to form a double bond. The delocalized negative
charges on the polymer chain are mobile, not the dopant cations. Thus, these delocalized negative
charges are current carriers for conduction. These charges must move from chain to chain as well as
along the chain for bulk conduction.
Applications
 As electrode material for commercial rechargeable batteries (coin type batteries).
 As sensors-humidity sensor, gas sensor and radiation sensor etc.
 In electrochromic display windows.
 In light emitting diodes
 Corrosion inhibitors
 Solar Cells
Review Questions

1. What are conducting polymers?

2. Give an application of conducting polymer.

3. Name the catalyst used in preparation of polyacetylene.

Lecture-4
Polymer composites
A combination of two or more distinct components to form a new class of material suitable for
structural applications is referred to as composite materials. When one of the components is a
polymer, the resulting composite is called a polymer composite.
Polymer composites are produced by suitably bonding a fibre material with a polymer matrix
and curing the same under pressure and heat.
The fibres used are glass fibre, carbon fibre, polyethylene, aramid, alumina fibre, silicon carbide
fibre etc.
Matrix is usually a thermoset material such as epoxy resins, polyesters, phenolic resins, silicon
resins, melamine resins, vinyl derivatives and polyimide.
Polymer composites are light in weight, stronger than steel. They have good corrosion
resistance.

Synthesis of Kevlar
Kevlar is an aramid (aromatic polyamide). Its chemical name is poly para-
phenyleneterephthalamide, and it is known as a para-aramid.
Kevlar is synthesized by the condensation of 1,4-phenylene-diamine and terephthaloyl chloride in a
solution of N-methyl-pyrrolidone and calcium chloride with the liberation of HCl as a byproduct.
Properties

 High tensile strength

 Chemically stable at high temperatures
 Flame retardant
 Low electrical conductivity
 High resistance to abrasion & impact.
 Light weight
 Difficult to drill and cut.
Uses

 In high performance race cars

 Bullet proof vests
 Aerospace industries
 Combat helmets
 Industrial Gaskets
 Racing Canoes

Graphene Oxide
Graphene oxide (GO) is the oxidized derivative of graphite. A single sheet of carbon atom taken
out of graphite is graphene. Graphene oxide is a compound of carbon, oxygen, and hydrogen
arranged in variable ratio. When functional groups such as epoxide, hydroxyl, carboxyl, and
carbonyl group are added to graphene layer resulting material is graphene oxide.
Preparation
Graphene oxide can be prepared from Hummer method from pure graphite powder. In this method
graphite is subjected to reaction with anhydrous mixture of concentrated sulphuric acid, sodium
nitrate and potassium permanganate. The oxidation reaction is completed within 2 hours at a
temperature below 45oC. Next the hydrolysis of Graphite oxide in presence of polar solvent
Dimethylformamide (DMF) and sonication results in complete exfoliation in water, yielding
individual graphene oxide sheets.

Properties
 The presence of oxygen functional groups such as hydroxyl, epoxide, alkoxy, carbonyl
group make it hydrophilic, so it can easily dissolve in water and organic solvent.
 It can also mix with a matrix such as a polymer and ceramic to improve their mechanical
and electrical properties.
 GO has more surface area, so it is more reactive.
 Thin films of GO exhibit a high optical transparency.
 Reduction of GO increases its electrical conductivity.

Applications
 It is used as membranes in water purification.
 Graphene oxide has been used in DNA analysis applications.
 Store hydrogen
 It is used as electrodes in batteries.
 Graphene oxide finds uses in a wide variety of nanomedical applications including
 tissue engineering, cancer treatment, medical imaging, and drug delivery.
Review Questions

1. Mention any applications of Kevlar.

2. Mention any two properties of Kevlar.
3. Mention any applications of Graphene oxide.
4. What is graphene oxide?
5. Mention any two properties of Graphene oxide.
Applied chemistry For CSE Stream 12

Lecture-5
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 reactions.
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. Some of the
types of green fuels are methanol, hydrogen, ethanol, Biogas 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.
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.
Advantages of Green fuels
 Zero emission Fuel Source
 Eco-friendly with high energy efficiency
 Reduce greenhouse gases
 Reduce dependence on fossil fuel
 High quality engine performance
 Positive economic impact

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 Reduces landfills and waste

 Biodegradable

Photovoltaic cells
Definition: Photovoltaic cells or solar cells are semiconductor devices they convert sunlight
falling on them into direct electricity.
Working of a Photovoltaic cells

Solar cells consist of p-n junction formed from a semiconductor diode obtained when n - type
and p- type semiconductor is brought together to form a metallurgical junction. The diode has
two electrical contacts one of which is in the form of a metallic grid and other is a layer of
noble metal on the back of the solar cell. The metallic grid allows light to fall on the
semiconductor between the grid lines. An anti-reflective layer between the grid lines
increases the amount of light transmitted to the semiconductor.
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
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 two ends through the
external circuit. Thus, photoelectric current is produced and available for use.
Advantages of photovoltaic cells
 Energy source is unlimited
 No emissions and does not cause environmental pollution.
 Low operating costs
 No moving parts and no wear and tear

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 Operates at ambient temperature

 Quick installation
Disadvantages of photovoltaic cells
 High installation costs
 Energy can be produced only during day time / Weather dependent
 Large space needed
 Less efficient
Review Questions

1. What is green fuel?

2. What is photovoltaic cell?
3. Mention the application of photovoltaic cell.
4. What are the advantages of green fuel?
Lecture-6
Green Hydrogen
Green hydrogen is produced by using electricity to power an electrolyser that splits the
hydrogen from water molecules. This process produces pure hydrogen, with no harmful
by-products. Green hydrogen has significantly lower carbon emissions. Green hydrogen can
be used in industry and can be stored in existing gas pipelines to power household appliances.
The current problem is that green hydrogen currently costs three times as much as natural
gas. High energy requirement in compressed hydrogen storage, due to low specific gravity is
needed. While temperature and pressure requirements are needed in storing hydrogen in solid
form.
Generation of Green Hydrogen from water electrolysis- Alkaline Electrolyzer

 Electrolysis is the process of using electricity to split water into hydrogen and oxygen.
This reaction takes place in a unit called an electrolyzer.
 Alkaline electrolysers use an aqueous KOH solution (caustic) as an electrolyte that
usually circulates through the electrolytic cells.
 Electrolyzers consist of an anode and a cathode placed in potassium hydroxide (KOH)
solution.
 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.

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 Hydroxyl ions moves towards anode through the membrane and undergoes oxidation
at anode to give oxygen and water.

Reactions

Cathode reaction (Reduction): 2 H2O + 2e− → H2 + 2 OH−

Anode reaction (Oxidation): 2 OH− →1/2 O2 + H2O + 2 e−

Fig: Alkaline Electrolysis

Advantages

 Zero emission of Carbon dioxide

 Easiest and simplest method
 Cost effective materials used
 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.

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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,
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.
Reactions

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

Cathode reaction (Reduction): 4H+ + 4e- →2H2

Advantages

 Carbon free hydrogen produced

 Highly efficient
 Compact design
 Eco-friendly
 Polymer membrane is chemically stable and noncorrosive
 An operational cost is low.

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Fig: PEM Electrolysis

Review Questions

1. What is Green Hydrogen?

2. Name the electrolyte used in PEM Electrolyser.
3. Name the electrolyte used in Alkaline Electrolyser.
4. What are the advantages of PEM Electrolyser?
Tutorial -7

Numerical Problems on Number average molecular mass

Tutorial -8

Numerical Problems on weight average molecular mass

*********************************************************************

Questions on Polymers & Green Fuels

1. What are conducting polymers? Explain the synthesis of Polyacetylene and
mention its applications.
2. Explain the generation of Hydrogen by Alkaline water electrolysis.
3. Explain the generation of Hydrogen by PEM electrolysis.
4. Explain construction and working of photovoltaic cell.
5. Explain mechanism of conduction in polyacetylene.
6. Explain synthesis properties and applications of Kevlar.
7. Explain synthesis properties and applications of Graphene oxide.
8. What are Green fuels? Mention the advantages of green fuels.

Dr.Lavanya D Kateel
Asst.Professor

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