Dept of Chemistry, CMR Institute of Technology BCHES102/202

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.

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 Dept of Chemistry, CMR Institute of Technology BCHES102/202

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

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 Weight Average Molecular Weight

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

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 Dept of Chemistry, CMR Institute of Technology BCHES102/202

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.

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.

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 Dept of Chemistry, CMR Institute of Technology BCHES102/202

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:

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

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 Dept of Chemistry, CMR Institute of Technology BCHES102/202

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)

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.

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 Dept of Chemistry, CMR Institute of Technology BCHES102/202

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.

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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 Dept of Chemistry, CMR Institute of Technology BCHES102/202

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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 Dept of Chemistry, CMR Institute of Technology BCHES102/202

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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 Dept of Chemistry, CMR Institute of Technology BCHES102/202

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
At Cathode: 4H+(aq) + 4e− → 2H2(g)

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 Dept of Chemistry, CMR Institute of Technology BCHES102/202

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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 Dept of Chemistry, CMR Institute of Technology BCHES102/202

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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 Dept of Chemistry, CMR Institute of Technology BCHES102/202

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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 Dept of Chemistry, CMR Institute of Technology BCHES102/202

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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