MODULE 4

Polymers and Green fuels

Polymers: Introduction, Molecular weight - Number average, weight average and

numerical problems. Preparation, properties and commercial application 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.
Self -Learning Topics: Regenerative fuel cells

Introduction
The word polymer is coined from two Greek words: poly means many and mer
means unit or part. The term polymer is defined as very large molecules having high
molecular mass (103-107 u). These are also referred to as macromolecules, which are
formed by joining of repeating structural units on a large scale. The repeating structural
units are derived from some simple and reactive molecules known as monomers and
are linked to each other by covalent bonds.
Definition for polymers: Polymers are materials with large molecular masses obtained
by the covalent linkage of several small repeating chemical units called monomers. This
process of formation of polymers from respective monomers is called polymerization.
Definition for monomers: The low molecular weight simple molecules containing two
or more bonding sites involved in the formation of polymer are called as monomers.
Molecular weight of polymers
Molecular weight of a polymer influences various properties of a polymer such
as solution viscosities, softening temperature, heat resistance, tensile and impact
strength etc. the low molecular weight polymers are generally soft and gum like
substances. The high molecular weight polymers are tougher and more heat resistant.
Thus control of molecular weight of polymer is often important for industrial
polymerization. Therefore determination of molecular weight is of great importance in
both the research and industry.
Polymers have distribution of chain lengths and therefore they possess varying
degree of polymerization and molecular weight. The molecular weight of polymer
depends on the number of polymer molecules in the solution. The experimental
measurement of molecular weight gives average molecular weight of a polymer.
Average molecular weight of a polymer is expressed as
 1. Number average molecular weight (Mn)
2. Weight average molecular weight (Mw)
Number average molecular weight (Mn)
The number average molecular weight is the statistical average molecular weight
of all the polymer chains in the sample. It is obtained by dividing the total weight of the
dispersed material with the number of molecules present i.e.,

Where n1, n2 n3 are the number of molecules having molecular masses M1, M2, M3
respectively. The above equation may also be written as:

Where Mi = masses of simple monomer molecules

ni = number of monomer molecules

The number average molecular weight Mn assumes that each molecule makes an equal
contribution to polymer properties regardless of the size or weight. For commercial
polymers, Mn = 10000 – 100000. Mn is determined on the basis of colligative property
such as osmotic pressure measurement.
Weight average molecular weight (Mw)
Weight average molecular weight is of significant when polymer property
depends not just on the number of polymer molecules but on the size or weight of each
molecule. It gives representation to various molecular species in proportion to their
weight in the given material. Weight average molecular weight is determined by light
scattering method and sedimentation technique. These techniques not only depend on
the number of particles in a given mass or volume but also on the molecular size.
Hence, in the averaging process molecular weight of each individual species is
multiplied by the weight and not by the number.

If n1, n2, n3, … denotes the number of molecules having masses M1, M2, M3, …
then m1 = n1M1, m2 = n2M2, m3 = n3M3, … hence, the above equation may be written as
 The molecular weight of the polymer can be determined by using the following
methods.
1. Colligative property measurements such as Osmometry, Ebullioscopy and
Cryoscopy.
2. Light scattering measurements.
3. Viscosity measurements.
4. Ultracentrifuge.
5. Chemical analysis.
Numerical problems:
Problem 1: If average degree of polymerization of polyvinyl chloride is 2 x 102, calculate
the weight average molecular weight of polymer.
Solution: Monomer unit of polyvinyl chloride is –CH2-CHCl and its molecular weight
is 62.
Weight average molecular weight = Molecular weight of repeat unit x DP
Mw = 62 x 2 x 102
= 12,400
Problem 2: The Mn of polymer polythene is 104 gm/mole. Find its degree of
polymerization.
Solution: Monomer unit of polythene is –CH2-CH2- and its molecular weight is 28.
As we know that,

Where, ‘m’ is molecular weight of the monomer unit and

‘M’ is molecular weight of the polymer
Therefore, 104
DP =
28

= 357.14
Problem 3: A polymer sample contain 5 molecules having a molecular weight of 2000, 4
molecules having a molecular weight of 3000 and 3 molecules having a molecular
weight of 4000. Calculate the number average and weight average molecular weight.
Solution: Number average molecular weight

= 2833.3

Weight average molecular weight

Kevlar [poly(p-phenyleneterephthalamide)]
Kevlar is a polymer, it was first developed as a replacement for steel in radial
tyres, but now is the most well-known for bullet proof vests and also has many other
uses including wind suits and in high friction apparatus such as break parts and gears.
It is also extremely strong and light substance. Five times stronger weight for weight
than steel.
Synthesis
Kevlar is synthesized from the monomes such as 1,4, phenylenediamide and
terephthaloylchloride. They react through condensation polymerization in presence of
conc. H2SO4.

Kevlar has a low density because the polymeric chain consist only C, H, N and O
atoms, all have small relative atomic masses. It is resistant to heat and this can be
attributed to the close packing of the molecular sheets and the strength of the hydrogen
bonding between the polymer chains within each sheet. Large amount of energy is
required to break down the structure and Kevlar only begins to decompose and char
when heated to temperature above 400 ºC
Properties
1. It is five times stronger than steel.
2. It is extremely light weight.
3. It does not rust or corrode and it absorbs vibrations readily.
4. It has high impact resistance.
5. It also exhibits the highest tensile strength and highest resistance to damage.
6. It has very good resistance to high temperature.
7. It is resistant to fire, chemical attack and abrasion.
Applications
1. It can be used to make tyres (in bicycle and race cars), racings sails for boats.
2. Popularly used for making bullet proof vests.
3. It is used in industrial cables, asbestos replacements and brake linings.
4. It is used in plastic reinforcement for boat hulls, airplanes.
5. In the construction of aircraft, space vehicles.
6. It is used in the manufacture of gloves, sleeves, jackets, chaps and other articles
of clothing designed to protect users from cuts, abrasions and heat.
7. In anterior part of basketball shoes and its laces.
8. The Kevlar fibre/epoxy matrix composite materials can be used in marine
current turbine or wind turbine.
Conducting polymers

Definition: an organic polymer with highly delocalized polymer systems, having

electrical conductance of the order of a conductor is called as conducting polymer.

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)

Mechanism of conduction:
1. Oxidative doping (p-doping):
In this process, an appropriate oxidizing agent is added to bring partial oxidation of
polymer pi backbone. Thus, positively charged sites are generated on the polymer
backbone and facilitates the movement of charge carriers in the chain. Most commonly
used oxidative doping or p-doping agents are iodine vapor, iodine in CCl4, HBF4,
perchloric acid and benzoquinone.
  The removal of an electron from the polymer pi-back bone using a suitable
oxidizing agents leads to the formation of delocalized radical ion called polaron.
 A second oxidation of a chain containing polaron followed by radical
recombination yields two charge carriers on each chain.
 The positive charges sites on the polymer chains are compensated by anions I 3-
formed by the oxidizing agent during doping.
 The delocalized positive charges on the polymer chain are mobile, not the dopant
anions.
 Thus, these delocalized positive charges are current carriers for conduction.
These charges must move from chain to chain as well as along the chain for bulk
conduction.
 On doping polyacetylene using iodine in CCl4, for partial oxidation, the
conductivity increases from 10-5 S.cm-1 to 103-105 S.cm-1.

Mechanism of conduction:
2. Reductive doping (n-doping):
In reductive doping technique, pi-backbone of a polymer is partially reduced by a
suitable reducing agent. This facilitates the formation of negative charged sites on the
pi-backbone and are responsible for conduction. The most commonly used reducing
agents are: sodium napthalide in tetra hydro furan.
 The addition of an electron to the polymer back bone by using a reducing agent
generates a radical ion polaron.
 A second reduction of chain containing polaron, followed by the recombination
of radicals yields two charged (-ve) carriers on each chain.
 These charge sites on the polymer chains are compensated by cations (Na+ ions)
formed by the reducing agent.
Applications of Polyacetylene
 Doped polyacetylene offers a particularly high electrical conductivity therefore it
can be used in electric wiring or electrode material in lightweight rechargeable
batteries.
 Tri-iodide oxidized polyacetylene can be used as a sensor to measure glucose
concentration.
Green Fuels
Introduction
Solar radiation is believed to be the only realistic alternative to fossil fuel. It is a
clean and renewable source of energy available in abundance. As per an estimate, if
solar energy received by earth surface per day is converted into electrical energy, it is
sufficient to meet the energy requirements of whole world for 16 years.
Photovoltaic (PV) cells
Photovoltaic cells or solar cells are often referred to as semiconductor devices
that convert sunlight into direct current electricity.
Principle:
When electromagnetic radiation (sunlight) is incident normal to the plane of the solar
cell, the photons, which possess energy (photons carry certain amount of energy given
by Plank’s quantum equation, E = hc/λ, where h is Plank’s constant, c is the velocity of
the light and λ is the wavelength of the radiation) sufficient to overcome the barrier
potential are absorbed and electron-hole pairs are formed. Electrons are driven into the
external circuit and used for various appliances.
Construction:
 A typical silicon photovoltaic cell is composed of a thin wafer consisting of an
ultra-thin layer of phosphorous doped (n-type) silicon on top of boron doped (p-
type) silicon. Hence, a p-n junction formed between the two.
 A metallic grid on the top of n-type silicon forms one of the electrical contacts of
the diode.
 An antireflective layer (coating of silicon nitride or titanium dioxide) is coated
between the metallic grids to prevent the reflection of solar light.
 The cell’s other electrical contact is formed by a layer of silver metal at the back
of p-type semiconductor.
 The two metallic ends are electrically connected through the external circuit.
 A conventional solar cell structure is shown below:
Working:
 Electrical energy obtained from PV cell is directly proportional to area of cell
exposed to light radiation and intensity of light radiation which can eject
electrons.
 When a photon from sunlight carrying energy E = hc/λ (which is enough to
cross the barrier potential) falls on the p-n diode through the antireflective layer,
electrons are ejected from p-type semiconductor creating an electron-hole pair.
 These ejected electrons move to n-side through p-n junction.
 Since, p-n junctions allows only one way movement of electrons, these electrons
must flow through the external circuit to recombine with holes present in p-side
of semiconductor.
 This movement of electrons from n-side to p-side through the external circuit
generates an electric current.
Advantages of PV Cells:
 Energy source is vast, essentially infinite and low maintenance.
 They are environmental friendly (No emissions, no combustion or radioactive
residues for disposal. Does not contribute to global change or pollution.
 PV cells do not suffer wear and tear as they have no movable parts.
 Economical except the initial set up expenses.
 They do not corrode.
 They operate at ambient temperature.
 High reliability in modules (>20 years).
Disadvantages of PV Cells:
 Power efficiency of a commercial Si based PV cell is very low (16%).
 Silicon required for PV cell is of high purity (99.999%). High cost of Si
purification has resulted in higher price of crystalline silicon solar cells.
  Sunlight is a diffuse source, i.e., it is relatively low density energy.
 Energy cannot be produced at night and the efficiency decreases when there is
cloud cover, decreasing the reliability of peak output performance.
 Batteries are required To store the electricity
 Produce DC power and must be converted to the AC power when used in
distribution grids.
Generation of energy (green hydrogen) by electrolysis of water:
Electrolysis is a promising option for carbon-free hydrogen production from renewable
and nuclear resources. It 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.
Construction
Like fuel cells, 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. A direct
current (DC) is applied from the negative terminal of the DC source to the cathode (seat
of the reduction reaction), where the hydrogen is produced. At the anode, the electrons
produced by the electrochemical reaction return to the positive terminal of the DC
source.
(a) Alkaline Electrolyzers

 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.
 Electrolyzers using a liquid alkaline solution of sodium or potassium hydroxide
as the electrolyte have been commercially available for many years.
 Newer approaches using solid alkaline exchange membranes (AEM) as the
electrolyte are showing promise on the lab scale.

(b) Polymer Electrolyte Membrane Electrolyzers

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

specialty plastic material.
 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.
  At the cathode, hydrogen ions combine with electrons from the external circuit to
form hydrogen gas.
Anode Reaction: 2H2O → O2 + 4H+ + 4e-
Cathode Reaction: 4H+ + 4e- → 2H2
(c) 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.
 Solid oxide electrolyzers must operate at temperatures high enough for the solid
oxide membranes to function properly (about 700°–800°C, compared to PEM
electrolyzers, which operate at 70°–90°C, and commercial alkaline electrolyzers,
which typically operate at less than 100°C).
 Advanced lab-scale solid oxide electrolyzers based on proton-conducting
ceramic electrolytes are showing promises for lowering the operating
temperature to 500°–600°C. The solid oxide electrolyzers can effectively use heat
available at these elevated temperatures (from various sources, including nuclear
energy) to decrease the amount of electrical energy needed to produce hydrogen
from water.
The advantages of using hydrogen as a fuel in fuel cells are:
 It has high electrochemical reactivity,
 It has high theoretical energy density,
 Unlimited availability (as long as you can break down the water),
 It produces harmless combustion product (H2O) for the environment.