CMR INSTITUTE OF TECHNOLOGY

MODULE 4: Polymers and Green Fuels

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.

Polymers
Polymers are high molecular weight organic compounds in which a large
number of simple units repeat themselves in a regular fashion. The simple units are
called monomers.

Molecular Weight of Polymers

The molecular weight of polymers is very important because their molecular
weight affects the physical properties of macromolecules.

The polymer molecular weights are usually given as average. Because the polymers are
not always composed of identical molecules.

There are several ways to calculate the molecular weight of polymers like

 Number average molecular weight

 Weight average molecular weight

Number average molecular weight (Mn)

The number average molecular weight is the total weight of the polymer, divided
by the number of polymer molecules. The average molecular weight (Mn) is given by,

Mn = ∑ NiMi / ∑ Ni

where Mi is the molecular weight of a molecule, and Ni is the number of molecules of that
molecular weight.

Weight average molecular weight (Mw)

The weight average molecular weight is the weight fraction of molecules in a polymer
sample. Mw is defined as,
Mw = ∑ NiMi2 / ∑ NiMi

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The Poly Disparity index (PDI) is the ratio between weight average molecular weight
and number average molecular weight.
PDI = Mw/ Mn
Difference Between Number Average and Weight Average Molecular Weight

Number Average Molecular Weight Average Molecular

Weight Weight
Definition Number Average Molecular Weight Average Molecular
Weight is the mole fraction of Weight is the weight fraction of
molecules in a polymer sample. molecules in a polymer sample.
Equation Mn = ∑ NiMi / ∑ Ni Mw = ∑ NiMi2 / ∑ NiMi
Value Always lesser than weight Always greater than number
average molecular weight average molecular weight.
Determination By using gel permeation By using static light scattering,
chromatography, viscometry small angle neutron scattering, X-
and vapor pressure osmometry ray scattering

Kevlar
Kevlar is a manmade manufactured fibre in which the fibre-forming substance is a
long-chain synthetic polyamide (-CONH) attached directly to two aromatic rings.

Preparation of Kevlar
Kevlar is prepared by polycondensation between aromatic dichloride like terephthaloyl
acid chloride and aromatic diamines like p-phenylenediamine.

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Properties of Kevlar
 It is exceptionally strong, 5 times stronger than steel and 10 times stronger than
aluminium.
 It is thermally stable up to 450°C.
 It is also stable at very low temperatures (up to -196°C )
 Kevlar can resist attacks from many different chemicals,

Applications of Kevlar
 Kevlar is widely used in the production of bulletproof vests, military helmets and
body armour.
 Kevlar is used in protective clothing for military personnel, law enforcement
officers and firefighters.
 Kevlar is used in various industrial applications, such as conveyor belts, hoses,
and gaskets
 Kevlar is employed in the aerospace and aviation industries for its lightweight
properties and ability to withstand high temperatures.

Conducting polymers
Generally, organic polymers are very good electrical insulators and poor conductors.
Certain polymers conduct electricity due to the presence of conjugated multiple bonds
along the polymer chain backbone or ring structure.
 In conducting polymers, sp2 hybridized carbon chain constitutes the backbone for
conduction
 On each sp2 hybridized carbon, there will be a single electron in the unhybridized
pz orbital.
 The unhybridized pz is orthogonal to sp2 hybridized orbitals.
 This conductivity is because of delocalized mobile electrons.

The polymers that can conduct electricity due to the presence of a conjugated system
of delocalized electrons are called conducting polymers.

Examples of conducting polymers:

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Polyacetylene
Polyacetylene consists of a long chain of carbon atoms with alternate single and
double bonds.

Their conductivities are 10-8 to 10-7 S.m-1 for cis-Polyacetylene and 10-3 to 10-2 S.m-1 for
trans-Polyacetylene.

Synthesis of Polyacetylene
When acetylene gas is bubbled through heptane/toluene solvent containing
Ziegler-Natta catalyst, Polyacetylene solid film is formed at the gas-liquid interface

Conducting mechanism of polyacetylene

Conductivity can be increased by doping the polymer. The conducting polymers are
synthesized by doping, in which charged species are introduced in polymeric pi-back
bone. The important doping reactions are:
 Oxidative doping (p-doping)
 Reductive doping (n-doping)

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Oxidative doping (p-doping)

When the polymer is doped with an oxidant, it acquires a positive charge and the acceptor
gets a negative charge. The oxidizing agent used in the p-doping of polyacetylene is iodine
in CCl4.

Mechanism:
 The removal of an electron from the polymer pi-backbone using a suitable
oxidising agent leads to the formation of a delocalized radical ion (polaron).
 Second oxidation of a chain containing polaron, followed by the radical
recombination yields two positive charge carriers of each chain.
 Positive charge sites on the polymer chains are compensated by I3- ions formed by
the oxidizing agent.
 The delocalized positive charges on the polymer chain are mobile and are
responsible for current carriers for conduction.

Reductive doping (n-doping)

When the polymer is doped with a reducing agent, it acquires a negative charge and the
donor gets a positive charge. The commonly used reducing agent is sodium naphthalide
in THF.

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Mechanism:
 The addition of an electron to the polymer pi-backbone using a suitable reducing
agent generates a radical ion (polaron).
 Second reduction of a chain containing polaron, followed by the recombination of
radical yields two negative charge carriers of each chain.
 Negative charge sites on the polymer chains are compensated by Na+ ions formed
by the reducing agent.
 The delocalized negative charges on the polymer chain are mobile and are
responsible for current carriers for conduction.

Application of conducting polymers

 Non-volatile memory devices based on organic transistors.
 Fabrication of organic photovoltaic cells.
 Fabrication of organic light-emitting devices (OLED).
 Conducting polymer actuators and Micropumps.
 Polymer membranes that incorporated electronically conducting polymers

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Graphene Oxide
It contains hydroxyl (-OH), alkoxy (C-O-C), carbonyl (C=O), carboxylic acid (-
COOH) and other oxygen-based functional groups.

Preparation of GO
 Hummers' method is commonly used approach for the preparation of Graphene
oxide (GO).
 This method involves the oxidation of graphite powder using a mixture of
concentrated sulfuric acid (H2SO4), sodium nitrate (NaNO3) and potassium
permanganate (KMnO4).
 Stir the mixture in a round-bottom flask at a low temperature (~5°C) for few
hours.
 Slowly add deionized water or ice to the reaction mixture to quench the reaction
and obtain graphite oxide suspension.
 Wash the resulting graphite oxide suspension with acid and water to remove
impurities and unreacted chemicals.

Properties of Graphene Oxide

1. It is highly hydrophilic due to the presence of hydroxyl and carboxyl groups.
2. It exhibits lower thermal stability due to the presence of oxygen-containing
functional groups.
3. It is an insulator due to the presence of oxygen functional groups.
4. It possesses good mechanical strength and flexibility.
5. It has unique optical properties. It exhibits strong absorption in the ultraviolet
(UV) range.

Commercial Applications of Graphene Oxide

1. It is used in optoelectronic devices such as solar cells, photodetectors, light-
emitting diodes (LEDs), and flexible displays.
2. It has applications in biomedical field due to its biocompatibility and unique
physicochemical properties.
3. Graphene oxide-based sensors are being developed for various applications,
including gas sensing, biosensing, and environmental monitoring.
4. It can be utilized in energy storage devices such as lithium-ion batteries,
supercapacitors, and fuel cells.

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Green fuels
Green fuels are energy sources that can be used as substitutes for traditional fuels, such
as diesel and natural gas. These fuels are considered "green" because they have lower
carbon emissions making them more environmentally friendly.
Examples of green fuels are biodiesel, hydrogen, wind power and solar power.

Photovoltaic cells (Solar cells)

The device, which converts solar energy into electrical energy, is called photovoltaic cell
and the phenomenon is called photovoltaic effect.

Construction:
 Photovoltaic Cells consists of p-n junction semiconductor diode made of silicon
coated with anti-reflective layer (TiO2) at the top.
 Two electrical contacts are provided, one in the form of metallic grid at the top of
the junction and the other is a silver layer at the bottom of the cell
 The antireflective layer coated in between the metallic grids which allow light to
fall on the semiconductor.

Working of photovoltaic cell:

 Electromagnetic radiation consists of particles called photons (hv). They carry a
certain amount of energy given by the Plank quantum equation. E = hc/λ
Where, h = Planck's constant, c = velocity of light, λ = wavelength of the radiation
 The photons of solar radiations enter n-type semiconductor breaks barrier
potential and moves to p-type semiconductor where photons knock the electrons
in p-type to form electron-hole pair.
 The free electrons so formed will travels through the circuit from n-type and
recombines with holes again in the p-type region.
 The movement of electrons from n-type to p-type generates electric current. The
electrical energy produced by the solar cell is used for various applications

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Advantages of PV cells:
 It is unlimited, inexhaustible and renewable source of energy.
 The solar cell operates reliably for a long period of time with no maintenance.
 Easy to operate
 Quick installation.
 Completely pollution free during its use.
Disadvantages of PV cells:
 High installation cost.
 Energy can be produced only during the day-time.
 The efficiency of solar cells depends on climate.
 Space required to generate unit power output is relatively more.
 Solar cell generates DC current. It needs to be converted to AC for use.

Generation of hydrogen by electrolysis of water

This is the process of splitting of water into oxygen and hydrogen gas by electrolysis.
 It consists of two electrodes i.e. anode and cathode.
 Both are separated by membranes.
 When electricity is passed, oxidation takes place at anode, it gives H+ ions and
electron, also liberates oxygen gas.
At Anode: 2 H2O(l) → O2(g) + 4 H+(aq) + 4e−
 The H+ ions move into cathodic compartment through membranes and electrons
move from anode to cathode through external circuit.
 At cathode the H+ ions accepts electrons and forms H2 gas. This liberated
hydrogen gas is used as a fuel

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At Cathode: 4H+(aq) + 4e− → 2H2(g)

Overall cell reaction: 2H2O (aq) → 2H2 (g) + O2 (g)

Alkaline Water Electrolysis

 It consists of two electrodes i.e. anode and cathode.

 Both electrodes are made up of Ni based metal, because it is more stable during
the oxygen evolution.
 These electrodes are immersed in KOH solution (25-35%).
 Both electrodes are separated by porous diaphragm prevent gases crossover and
allows only hydroxide ions.
 When electricity is passed, at anode hydroxide ions lose electrons and forms water
molecules.
 At cathode, water molecules accept electrons and liberate hydrogen gas and forms
hydroxide ions.
 These hydroxide ions move from cathode to anode through diaphragm and
process continues.

Anode Reaction (Oxidation process): 4 OH− (aq) → O2 (g) + 2H2O + 4 e−

Cathode Reaction (Reduction process): 4 H2O + 4 e− → 2H2 (g) + 4 OH− (aq)
Overall cell reaction: 2H2O (aq) → 2H2 (g) + O2 (g)

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Advantages
 Well established technology
 Low cost technology
 The energy efficiency is 70–80%
 Commercialized
Proton Exchange Membrane Electrolysis
Proton Exchange Membrane (PEM) isolates the anode and cathode to avoid direct
contact between oxidation and fuel. The purpose of this membrane to conduct protons
only and block the electrons. It incorporates numerous proton conductive functional
groups that allow protons to move one side to other.

 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 travelled 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 recombine to produce the hydrogen
gas.

At Anode: 2 H2O(l) → O2(g) + 4 H+(aq) + 4e−

At Cathode: 4H+(aq) + 4e− → 2H2(g)
Overall cell reaction: 2H2O (aq) → 2H2 (g) + O2 (g)

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Advantages
 Compact system design
 Quick Response
 Greater hydrogen production rate with High purity of gases (99.99%)
 Higher energy efficiency (80–90%)
 High dynamic operation

Numerical problems

Q1. In a sample of a polymer, 100 molecules have molecular mass 103 g/mol, 250
molecules have molecular mass 104 g/mol, and 300 molecules have molecular mass 105
g /mol, calculate the number average and weight average molecular mass of the polymer,
Calculate PDI and comment on it.
Solution:
It is given that,
N1 =100 & M1 = 103 g/mol,
N2 =250 & M2 = 104 g/mol,
N3 =300 & M3 = 105 g/mol.

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Q2. In a sample of a polymer, 20% molecules have molecular mass 15000 g/mol, 35%
molecules have molecular mass 25000 g/mol, and remaining molecules have molecular
mass 20000 g /mol, calculate the number average and weight average molecular mass of
the polymer, Calculate PDI and comment on it.
Solution:
It is given that,
N1 =20 & M1 = 15000 g/mol,
N2 =35 & M2 = 25000 g/mol,
N3 =45 & M3 = 20000 g/mol.

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