Bhasin, S. K. - Sharma, Vijay - Essentials of Engineering Chemistry-Himalaya Pub. House (2010) PDF

ESSENTIALS OF
ENGINEERING
CHEMISTRY
By
Dr. S.K. Bhasin
(Professor of Chemistry)
M.M.E.C., Mullana (Ambala)
(Formerly, Head of P. G. Chemistry Dept.
M.L.N. College, Yamuna Nagar
Dr. (Mrs.) Vijay Sharma

(Senior Lecturer)
P.G. Dept. of Industrial Chemistry,
Head of Bio-Chemistry Dept.
Guru Nanak Khalsa College,
Yamuna Nagar
mal
Gflimalaya GpublishingGflouse
MUMBAI • DELHI • NAGPUR • BANGALORE • HYDERABAD
© Dr. S.K. Bhasin, Dr. (Mrs.) Vijay Sharma
[No part of this publication should be reproduced, stored in a retrieval system, or
transmitted in any form or by any means, electronic, mechanical, photocopying, recording
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ISBN : 978-93-5024-340-4
Revised Edition :2010
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[ CONTENTS I
Chapter Pages
1. Chemical Energy Sources ............................................................................ 1

1A.1 Introduction; 1A.2 Fuels; 1A.3 Classification of Fuels; 1A.4 Importance
of Hydrocarbons as Fueld; 1A.4.1 Some important Hydrocarbon Fuels from
Petroleum; 1AA.2 Aromatic Hydrocarbons from coal; 1AA.3 Characteristics
of a Good Fuel; 1A.5 Calorific Value; 1A.6 Determination of Calorific Value;
1 A.7 Petroleum Cracking; 1A.S Catalytic Reforming; 1A.9 Knocking;
1A.10 Octane Number; 1A.10.1 Improvement of Octane Number;
1A.1 0.2 Gasoline additives (anti-knocking agents); 1A.1 0.3 Unleaded Petrol;
1A.11 Cetane Number; 1A.12 Synthetic Petrol; 1A.13 Power Alcohol;
lA. Solar Energy .................................................................................................. 40

1B.1 Introduction; 1B.2 Alternate Source of Energy; 1B.2 Composition of Solar
Energy; 1B.3 Solar Cells (Prospects); 1B.4 Renewable and Non-Renewable
Source of Energy; 1B.4 Solar Cell; 1B.5 The Single Crystal Silicon Cell;
1B.6 Principle of Working of a Solar Cell; 1B.7 Photo-Voltaic Cell; 1B.8
Photovoltaic Conversion; 1B.9 Importance; 1B.1 0 Silicon Solar Cell; 1B.11
Properties of Silicon; 1B.14 Production of Solar Grade Silicon; 1B.12 Semi-
conductor; 1B.13 Doping of Silicon.
2. Electrochemical Energy Systems (Electrode Potential and Cells) .......... . 59

2.1 Introduction; 2.2 Single Electrode Potential; 2.3 Derivation of Nernst
Equation (Concentration Dependence of Electrode Potential); 2.3.1 Application
of Nernst Equation; 2.4 Standard Electrode Potential; 2.5 Measurement of
Single Electrode Potential; 2.6 Electrochemical Cells or Galvanic Cells; 2.6.1
Functions of Salt Bridge; 2.6.2 Difference Between an Electrochemical Cell
and Electrolytic Cell; 2.6.2 Representation of Galvanic Cells; 2.7 Reference
Electrodes; 2.8 Cell Potential Or E.M.F. of a Cell; 2.8.1 Calculation of E.M.F.
of a cell: 2.9 Types of Cells; 2.10 Concentration Cells; 2.11 Determination of
pH; 2.11.1 Determination of pH using Hydrogen Electrode; 2.11.2
Determination of pH using Glass Electrode; 2.12 Ion Selective Electrode.
3A. Battery Technology ....................................................................................... 100
3A.1 Introduction; 3A.2 Basic Cocnepts; 3A.3 Battery Characteristics; 3A.4
Classification of Batteries; 3A.5 Classical Batteries; 3A.5.1 Primary Batteries;
3A.5.2 Alkaline Cells; 3A.5.4 Secondary Batteries; 3A.5.5 Nickel-Metal
Hydnde Cells; 3A.5.6 Lithium Batteries;
3B. Fuel Cells .......................................................................................................
3B.1 Introduction; 3B.2 Types of Fuel Cells; 3B.2.1 Alkaline Fuel Cells;
3B.3 Hydrogen-Oxygen Fuel Cell; 3B.4 Methanol-oxygen Fuel Cell; 3B.2.2
Phosphoric Acid Fuel Cells (PAFC); 3B.2.3 Molten Carbonate Fuel Cell
(MCCFs); 3B.2.4 Solid Oxide Fuel Cells (SOFC); 38.2.5 Ion Exchange
Membrane Fuel Cells or Solid Polymer Electrolyte Fuel Cells (SPEFCs);
3B.2.6 Biochemical Fuel Cells;
4. Corrosion Science ........................................................................................ 134

4.1 Introduction; 4.2 Types of Corrosion; 4.3 Dry or Chemical Corrosion;
4.4 Wet or Electrochemical Corrosion; 4.5 Comparison of Chemical with
Electrochemical Corrosion; 4.6 Types of Electrochemical Corrosion;
4.6.1 Other Forms of Corrosion; 4.7 Factors Influencing Corrosion; 4.8
Corrosion Control (Protection from Corrosion); 4.8.1 Protective Coating or
Barier Protection; 4.8.2 Sacrificial or Anodic Protection; 4.8.3 Electrical
Protection; 4.8.4 Corrosion Inhibitors;
5. Metal Finishing .............................................................................................. 166

5.1 Introduction; 5.2 Technological Importance of Metal Finishing; 5.3 Basis
of Electroplating; 5.3.1 Polarisation; 5.3.2 Decomposition Voltage; 5.3.3
Overvoltage or Overpotential; 5.4 Electroplating; 5.4.1 Mechanism of
Electrodeposition; 5.5 Effect of Plating Variables on the Properties of
Electrodeposit; 5.6 Electroplating Process; 5.7 Surface Preparation of
Electrodes (Pre-Treatment); 5.8 Electroplating of Copper; 5.9 Electroplating
of Nickel; 5.10 Electroplating of Chromium; 5.11 Electroplating of Gold; 5.12
Electroless Plating; 5.12.1 Electroless Plating of Copper; 5.12.2 Electroless
Plating of Nickel;
GA. Liquid Crystals and Their Applications'...................................................... 194

6A.1 Introduction; 6A.2 What are Liquid Crystals; 6A.3 Theory of Liquid
Crystals; 6A.4 Classification of Liquid Crystals; 6A.5 Chemical Constitution
and liquid Crystalline Behaviour; 6A.6 Difference Between Solids, Liquids
and Liquid Crystals; 6A.7 Molecular Arrangement in Various States of Liquid
Crystals; 6A.8 Homologues Series (PPAAND MBBA Series); 6A.8
Applications of Liquid Crystals;
68. Instrumental Methods of Analysis .............................................................. 214
6B.1 Introduction; 6B.2 Colorimetry; 6B.3 Instrumentation; 6B.4 Working:
6B.5 Applications; 6B.6 Potentiometry; 68.7 Theory; 68.8 Measurement of
Electrode Potential; 6B.9 Potentiometric Titrations; 6B.10 Applications of
Potentiometric Titrations; 6B.11 ConductomtStric Titration; 68.12 Types of
Conductometric Titrations; 68.13 Flame Photometry; 6B.14 Instrumentation;
6B.15 Applications;
7. High Polymers ............................................................................................... 239

7.1 Introduction; 7.2 Classification of Polymers; 7.3.2 Nomenclature of
Polymers; 7.3.3 Functionality; 7.4 Addition and Condensation Polymers;
7.4.1 Difference Between Addition and Condensation Polymerisation;
7.5 General Methods of Polymerisation; 7.6 Mechanism of Addition
Polymerisation; 7.6.1 Chain Transfer; 7.6.2 Inhibitation and Retardation;
7.7 Polymerization Techniques; 7.8 Glass Transition Temperature; 7.9
Structure-Properties Relationship of A Polymer; 7.10 Moulding Constituents
of A plastic; 7.11 Plastics and Resins; 7.12.1 Difference between
Thermoplastic and Thermosetting Polymer; 7.13 Description of
Some Commercially Important Thermoplastic Materials; 7.13.1
Polyterafluoroethylene (PTFE) or Teflon; 7.13.2 Polymethyl methacrylate
(PMMA); 7.14 Description of Some Commercially Important Thermosetting
Materials; 7.14.1 Bakelite (Phenol Formaldehyde, PF); 7.14.2 Polynurethanes;
7.15 Elastomers or Rubbers; 7.15.1 Vulcanisation of Rubber; 7.15.2 Synthetic
Rubbers; 7.16.1 Classification of Adhesives; 7.15.2 Chemical Factors
Influencing Adhesive Action; 7.15.3 Epoxy Resins; 7.16 Conducting Polymers;
7.16.1 Bond Theory of Conductance Mechanism; 7.16.2 Mechanism of
Conduction in Conducting Polymers; 7.16.3 Factors Affecting the
Conductivities of Organic Polymers; 7.17 Polyaniline.
8. Water Technology ......................................................................................... 312

8.1 Introduction; 8.2 Impurities in Water; 8.3 Hard Water; 8.3.1 Difference
between Hard Water and Soft Water; 8.3.2 Type of Hardness; 8.4 Units of
Hardness; 8.5 Determination of Hardness; 8.5.1 Numerical Problems on
Hehner's Method; 8.5.2 Numerical Problems on Soap Titration Method; 8.5.3
Numerical Problems on EDTA Method; 8.6 Alkalinity of Water; 8.6.1 Numerical
Problems Based on Alkalinity; 8.7 Determination of Chlorides; 8.8
Determination of Nitrates (N0 3-); 8.9 Determination of Sulphate (S042-); 8.10
Determination of Fluoride (F-); 8.11 Determination of Dissolved Oxygen; 8.12
Bio-Chemical Oxygen Demand (BOD);' 8.12.1 Method for Determination of
BOD; 8.12.2 Importance of BOD; 8.13 Chemical Oxygen Demand; 8.13.1
Method for Determination of COD; 8.13.2 Importance of COD; 8.14 Numerical
Problems on BOD and COD; 8.15 Sewage Treatment; 8.16 Potable Water;
8.17 Purification or Treatment of Water for Domestic Use; 8.17.1 Break Point
Chlorination; 8.18 Desalination; 8.18.1 Distillation by Flash Evaporation; 8.18.2
Freezing; 8.18.3 Electrodialysis; 8.18.4 Reverse Osmosis; 8.19 Hazardous
Chemicals; 8.19.2 Various Chemical Substances Present in Water Affecting
Health;
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I
CHEMICAL ENERGY SOURCES
SYLLABUS
Introduction to energy, fuels-Definition, classification, importance of hydrocarbons as fuels;
Calorific value-Definition, gross and net calorific values (in SI units) determination of
calorific value of a solid / liquid fuel using Bomb calorimeter, Petroleum cracking-fluidised
catalytic cracking, reforming of petrol, knocking-mechanism, octane number, cetane number,
prev(Jntion of Knocking, antiknocking agents, Unleaded petrol; Synthetic petrol-Bergius
process and Fischer Tropsch process; Power alcohol.
IA.I INTRODUCTION
Man has ne~ded energy at an increasing rate for his well-being ever since he came on the
earth. Primitive man required energy primarily in the form of food. He derived this by eating
plants or animals which he hunted. Subsequently he discovered fire and use wood and other
biomass for cooking as well as for keeping himself warm. With the passage of time, man started
cultivating land for agriculture. He added a new dimension to the use of energy by training
animals to work for him. With further demand for energy, man began to use the wind for
sailing ships and for driving windmills, and the force of falling water to turn water wheels.
Till this
f
time, it would not be wrong to say that the sun was supplying all the energy needs of
man either directly or indirectly.
We know that sun is the ultimate source of energy of many kinds. This energy is being
ra~iated to mankind in the form of heat and light. The heat energy causes evaporation of sea
water which falls back as rain after condensation. The mechanical energy of the flowing water
is utilized to generate electricity. The light energy of the sun brings about photosynthesis in
plants to produce carbohydrates which act as food for the animals. The carbohydrate (cellulose)
is nothing but wood which acts as a fuel again. Thus sun is the primary source of all the available
and future sources of energy.
2 Essentials of Engineering Chemistry
The Industrial Revolution which began with the discovery of the steam engine (AD 1700)
brought about a great many changes. For the first time, man began ta use a new source .of
energy, viz . coal, in large quantities. A little later, the internal cambustion engine was invented
(AD 1870) and the ather fossil fuels, oil and natural gas began to be used extensively. The
invention of heat engines and the use of fossil fuels made energy portable and intraduced the
much needed flexibility in man's movement. For the first time, man could get the power of a
machine where he required it and was not restricted to a specific site. This flexibility was
enhanced with the discovery of electricity and the development of central power generating
statians using either fossil fuels .or water power.
A new source of energy-nuclear energy-came on the scene after the Second World War.
The first large nuclear power station was commissianed about 40 years ago, and already, nuclear
energy is providing a small but significant amount of the energy requirements of many
countries.
Thus to.day, every country draws its energy needs from a variety of sources. We can broadly
categorize these sources as commercial and nancommercial. The commercial sources include
the fossil fuels (coal, oil and natural gas), hydroelectric power and nuclear power while the non-
commercial sources include wood, animal wastes and agricultural wastes. In an industrialized
country like the USA, most of the energy requirements are met from commerci\ll sources,
while in an industrially less d~veloped country like India, the use of c.oI!lmercial and non-
commercial sources is about equal. But the fossil fuel resources are fast depleting and that
the fossil fuel era is gradually coming to an end.
It is worthnoting that while man's large scale use of commercial energy had l~a to a better
quality of life, it has also created many problems. Perhaps the most seriouS' of t.l;1ese is the
harmful effect on the environment. The combustion of fossil fuels has cau'sed se~ous air pollution
problems. It has also resulted in the phenamenon' of global warming which is now a matter .of
great concern. Similarly, the release of large am~nts of waste heat frnm power plants has
caused thermal pollution in lakes and rivers leading to the destruction of many forms of plant
and animal life. In the case .of nuclear power plants, there is also concer..n over th'e possibility
of radioactivity being released into the atmosphere. N.ow, as man embarks .on the search for
alternative sources of energy, he should keep the environment in mind.
lA.2FUELS
Definition
Fuel may be defined as : "Any combustible substance which on combustion in air gives
large amount of heat that can be used economically for domestic and industridl Rurposes. "
The important common fuels are: Wood, coal, petrol, kerosense, diesel .oil, coal gas, oil
gas, water gas, producer gas etc.
Fuels are primarily used for heating purposes and heat energy is the main sourCEl of power,
but they also perform several other important functions. For example, coal in locomotive engines
and petrol in internal combustion (I.e.) engines is used to da some mechanical work. Similarly,
coke is used in blast furnace in the manufacture .of ir.on, it provides not only heat, but also
acts as a reducing agent.
The main sources of fuel are c.oal and petroleum oils, but due to rapidly growing industries
these are reducing day by day. These are fossil/stored fuels available in earths crust. In the
Chemical Energy Sources 3
near future, the primary source of fuels may get exhausted with the progressive consumption
and great demand all over the world. Thus, attempts are being made to use uranium (nuclear
fuel), sea water and solar energy etc. as fuels.
It is now well established that combustion is not necessary for a fuel to give out energy.
For example, electrical energy which is used as a source of heat does not involve combustion
but it is also called fuel. Nuclear energy may also be used as a source of heat. Chemical
compounds. such as power alcohol, hydrazine, ammonia etc. are used as fuels.
According to a modified definition, a fuel is anYlfissionable material, chemical or reactant
which on combustion or by any other mean produce energy in any form that can be used
for producing power.
For example, in electrochemical cells and fuel'cells, the chemical energy of the reactants
is converted into electrical energy by a suitable devices. Similarly, in a nuclear reactor
fissionable materials like U-235 can be broken in~o smaller fragments and the loss in mass
appears in the form of energy. The huge amount of energy thus produced can be controlled
and used for steam generation which in turn can produce electricity. The materials used in
these devices which act as a source of energy in an[y form are nothing else but fuels. A fuel in
the broader sense of the term is not essentially a combustible substance, it should be a source
of energy through combustion or even otherwise.
IA.a CLASSIFICATION OF FUELS
(A) Fuels may be classified on the basis of (i) their occurrence or preparation and (ii) physical
"'state. Thus on the basis of the occurrence or prepatation fuel may be of two types :
(a) Natural or primary fuels: Fuels which occur in nature as such are called natural
fuels. Common examples are wood, coal, peat, petrqleum and natural gas.
(b) Artificial or secondary fuels: Fuels which are manufactured artificially
generally from primary fuels are called artificial flfels or secondary fuels. Common examples
are coke, coal gas, producer gas etc. obtained from coal and kerosene oil, petrol, diesel etc.
obtained from petroleum.
Fuel may exist types in the solid, liquid andl gaseous form. So, primary (natural) and
secondary (artificial) fuels may also be classified on the basis of physical state as tabulated
below:
i
Classification of Fuels
TYpe of Fuel Natural or Primary Artificial or Secondary
Solid Wood, peat, lignite, bituminous coal Charcoal, charred peat, coke and
and anthracite coal petroleum coke
LIquid Crude petroleum Various fractlOns of petroleum
viz. kerosene oil, petrol, diesel oil,
fuel oil etc.
Gaseous Natural gas Liquefied Petroleum Gas (LPG), coal
gas, oil gas, water gas, blast furnace
gas etc.
(B) Fuels may also be classified on the basis of the main use for which they are employed.
(i) Motor or yehicular fuels: Fuels such as petrol, diesel oil, CNG etc. which provide
energy for running vehicles (Cars, Buses, Scooters, Aeroplanes etc. are called motor
fuels.
(ii) Domestic fuels: Fuels like LPG, kerosene oil, biogas, coal, wood etc. used for cooking
food are called domestic fuels.
(iii) Industrial fuels : Which are used in the industry.
These are further classified into two groups.
(a) Power generating fuels : These are burned in power plants for generating
energy. For example coal in thermal plants and uranium, thorium etc. in nuclear
plants.
(b) Process fuels: These are used in industrial furnaces and driers to produce heat needed
in various industrial processes.
lA.4 IMPORTANCE OF HYDROCARBONS AS FUELS
Hydrocarbons (aliphatic as well as aromatics) are not only the starting materials for the
synthesis of a very large number of organic compounds, but they are extensively used as
domestic, industrial and vehicular fuels. The different classes of hydrocarbons are quite
abundantly distributed in nature particularly in the form of petroleum and coal. It is from
these two sources that these hydrocarbons are obtained on an industrial scale. Petroleum is.
the major source of aliphatic hydrocarbons while coal is a source of aromatic hydrocarbons.
Aliphatic Hydrocarbons from Petroleum (Refining of Petroleum)
Petroleum obtained by mining is a mixture of dissolved gases, liquids with different boiling
points and semi-solids and solids of widely varying viscosities. The process of separation of
this mixture by fractional distillation into useful components and the removal of undesirable
materials is known as refining or processing of petroleum.
The petroleum obtained by mining is viscous and dark coloured liquid having an unpleasant
smell because of the presence of sulphur compounds. It also contains impurities of sand and
brine or sea water. It is technically known as crude oil.
The refining of crude oil is done in big refineries situated at a large distance from oil field.
The main products obtained by refining of the crude petroleum, along with their uses have
been summarised in Table I below.
Table I. Fractions of Petroleum
Fraction Approximate Boiling Range Uses
Composition (10
1. Gaseous hydrocarbons 100 to 300 As fuel gas, manufacture of

gasoline (by polymerization).
rubber, hydrogen and ammonia,
carbon black.
2. Curde naphtha. 300-425
On refraction further gives : I
(i) Petroleum ether C5-C7 3004345 As solvent in varnish and rubber

industries, for dry cleaning.
(ii) Petrol or gasoline C7-C9 345-':'395 As motor fuel, for making petrol
gas and for dry cleaning.
(iii) Benzine C9-C ll 395-425 For dry Cleaning.
3. Kerosene C12-C 15 425-575 As fuel, illuminant and manu-
facture of oil gas.
4. Diesel oil (Gas oil or fuel oil) C1S-C 18 575-625 As fuel for diesel engines and for
making gasoline by cracking.
5. :Residual oil, it gives: C18 upwards Above 625 As lubricant.
(i) Lubricating oils and
greases
(ii) Paraffin wax C20 upwards Above 675 In the manufacture of candles,
monuments, shoe polishes, vaseline
and toilet goods.
(iii) Petroleum coke and C30 onwards Resi ue As a fuel, for making electrodes
asphalt and road building.
lA.4.1 Some Important Hydrocarbon Fuels from ,~etroleum

Out of the several petroleum products, following are
,
used as fuels for various purposes :
1. Gasoline
2. Kerosene oil
3. Diesel oil
4. Natural gas
5. Compressed Natural Gas (CNG)
6. Liquified Petroleum Gas (LPG)
1. Gasoline or petrol: It is a mixture of hydrocarbons such as CSH12 (Pentane) to CSHlS
(Octane) and this fraction is obtained between 40-120°C. It calorific value is about 11250 k
Cal/kg.
It is obtained from crude petroleum by fractioIl1al distillation, by cracking of heavier
fraction of crude petroleum or by synthetic process s ch as polymerisation of gaseous alkenes
and alkylation of iso-butane. It is the most impor ant vehical fuel having the following
characteristics.
Characteristics of Ideal Gasoline
(i) It must be cheap and readily available.
(ii) It should have high calorific value.
(iii) It should not pre-ignite easily.
(iv) It must burn clean and produ~e no corrosion in the engine.
(v) It should not decrease the volumetric efficiency of engine.
(vi) It should readily mix with air and should be easy to vapourise.
(vii) It must be knock resistant.
2. Kerosene oil : Kerosene oil is a mixture of several hydrocarbons ranging from
C12-C 16. Besides alkane it contains, napthenes and aromatic compounds also. The hydrocarbons
present in it are higher the that of gasoline. Due to the presence of higher hydrocarbons,
kerosene has a higher boiling point range and therefore is not vapourised easily. Hence it is
not a suitable fuel for ordinary internal combustion engines, but however, it is a good fuel for
jet engines. The properties of kerosene vary from sample to sample. It is used as domestic
fuel, illuminant, aviation turbine fuel, tractor fuel, jet engine fuel, preparing gas for laboratories
etc.
3. Diesel oil : It is the fraction of petroleum distillation which is collected in the
temperature range of 300-350°C. It is heavier than gas oil and lighter than the residual oil.
Its specific gravity lies between 0.86-0.95. Its calorific value is about 11,000 kcal/kg. It is used
as a fuel in diesel engines. Diesel fuel is used in engines where the fuel is directly ignited into
cylinders and is atomised before it is ignited and burnt. In a diesel engine the fuel is exploded
by the application of heat and pressure and not by a spark. The main characteristic of a diesel
engine fuel is that, it should easily ignite below compression temperature. Chemically, diesel
oil consists of straight-long chain hydrocarbons with minimum amount of branched chain and
aromatic hydrocarbons.
4. Natural gas: Natural gas is generally associated with petroleum (crude oil) deposits
and is obtained from well dug in the oil bearing regions. It is very cheap and convenient fuel
consisting of mainly methane and other saturated hydrocarbons. When natural gas occurs
alongwith petroleum in oil wells is it called wet gas and contains higher hydrocarbons along
with methane. The wet gas is then suitably treated to remove propane, propene, propyne,
butane and butene, which is used as LPG. On the other hand, when the gas is associated with
crude oil it is called 'dry gas' and consists of lower hydrocarbons chiefly methane and ethane,
with impurities such as CO, CO 2, H 2, H 2S, N2 and inert gases in small proportions.
The natural gas is purified before uses to remove the objectionable impurities, such as
water, dust, H 2S, CO 2, N2 and heavier hydrocarbons (propane, butane and butene etc.) Natural
gas is also called 'Marsh' gas because mainly it contains methane which is generally formed
by the decomposition of vegetable matter in marshy land. It occurs in coal gas and produced
as a by product as LPG during petroleum, cracking process. The approximate composition of
natural gas is :
CH 4 = 86%, C 2H 6 = 8%, propane (C3HS) = 4%, Butane (C 4 H 10 ) = 1.5% and higher
hydrocarbons = 1.5%. The calorific value of natural gas varies from 8000 to 14000 kcaIlm 3.
Uses: It is an excellent gaseous fuel, which burns with a hot blue flame. Hence it is used
as a fuel for domestic and industrial purposes.
5. Compressed natural gas (CNG): The dry natural gas can also be compressed by
applying high pressure at low temperature and this is called compressed natural gas (CNG). It
consists mainly of methane and can be used as a fuel for the internal combustion engines. On
combustion, it gives only CO 2 and water vapour and reduces air pollution caused due to the
exhaust from the vehicles. The use of CNG as a fuel of I.C. engines is being recommended in
metropolitan cities in India also to minimise air pollution.
Natural gas in the form of LPG and CNG is mainly used as a domestic and motor fuel
even today. Only 10% of the natural gas is being used as chemical feedstock. With the growing
scarcity of chemical feedstock, natural gas consumption in the chemical field will increase in
the near future.
6. Liquefied petroleum gas (LPG) : It is also known as bottled or refinery gas, LPG
consists mainly of light paraffin hydrocarbons (upto C4) like propane (C 3H s)' propene (CaHs)'
butane (C 4H lO ) and butene (C 4H s ) which can be readily liquefied under pressure but can exist
as gases under atmospheric pressure.
LPG is obtained as a by-product, during the cracking of heavy oils 01' from natural gas.
LPG so produced is dehydrated, desulphurised in which, traces of organic sulphides are added
to give warning of the leakage of gas. It is usually supplied under pressure in cylinders with
different trade names like Indane, Esso, Burshane etc.
The main constituents of LPG are n-butane, propane and butylenes with little or no
proportion of ethane and propylene.
Uses: LPG is largely used as domestic fuel and industrial fuel. However, there is increasing
trend to use it as a motor fuel as it easily mixes with air and burns cleanly without residue
and is knock resistant. As it has to be handled under pressure and can be better used only
with engines working under high compression ratios. LPG containing liquid butane is mainly
used for domestic purposes whereas liquid propane is mainly used for industrial purposes. LPG
(chiefly C3 H 8 ) has the calorific value of about 25000 kcallm a.
Note: Odourous organic sulphides (mercaptans) are added to give warning to gas leakage.
7. Bio gas: The most common example of biogas is gobar gas. Gobar gas is obtained by
the fermentation of gobar (dung) in absence of air by anaerobic bacteria.
The dung in form of slurry is introduced in the fermentation well. The dung is subjected
to fermentation by anaerobic bacteria (present in stale dung) in the absence of free air. Such
bacteria digest this slurry forming a gas containing mainly methane and CO 2 . The optimum
temperature for fermentation of dung slurry is 34-48°C and the fermentation of dung starts in
a week.
lA.4.2 Aromatic Hydrocarbons from Coal
Carbonisation of coal: When coal is heated to about 1270 K out of contact with air, it
gives a number of products including coal tar. The process is known as destructive
distillation or carbonisation or pyrolysis.
The products obtained by the usual process of carbonisation are shown below :
Coal (heated to nearly 1270 K)
I
J
Coke (= 70%)
1
Hot vapours and gases
(Solid residue) (Cooled and passed through water)
J I 1
Condensed liquid is allowed to Coal gas
stand and the two layers formed (Mixture of uncondensed
are separated gases like H 2 , CH 4 , N2 etc.)
I
r
Ammoniacal liquor
1
Coaltar
(Upper layer =8 to 10%) (Lower layer =4 to 5%)
Essentials ofEngineering Chemistry
The amount of coal tar produced increases if the carbonisation is carried out at about 870
K under reduced pressure. Coal tar is further used in the isolation of aromatic compounds as
given below. The products obtained by pyrolysis of coal are used in different fields as outlined
below.
(i) Coke: The solid residue left after the destructive distillation of coal is mainly used
as a fuel and a reducing agent in metallurgy.
(ii) Coal gas: It is a mixture of uncondensed gases like H 2 , CH4 , C2H 4 and N2 etc. and
is used as a fuel gas.
(iii) Ammonicalliquor: It is the upper aqueous layer which is a source of ammonia. It
is recovered by absorbing ammonia in dil. H 2S04 as ammonium sulphate which is
used as fertilizer.
(iv) Coal tar : It is the lower black viscous layer with unpleasant smell. It is the main
source of aromatic compounds containing as many as about 200 compounds. The
important compounds are recovered from it by fractional distillation of coal tar.
Thus the main source of hydrocarbons used as fuels is petroleum and not coal.
lA.4.3 Characteristics of a Good Fuel
A good fuel should have the following characteristics :
(i) Calorific value : "It is amount of heat liberated when a unit mass or volume
of fuel is burnt completely." A good fuel must have a high calorific value, since the
amount of heat obtained from a definite weight of the substance depends upon this
factor.
(ii) Moderate velocity of combustion : The highest temperature achieved by
combustion of a fuel depends upon the calorific value and the velocity of combustion.
For a continuous supply of heat, fuel must burn with a moderate velocity.
(iii) Proper ignition point: A good fuel must have a moderate ignition point, since low
ignition temperature of fuels is mostly accompanied by fire hazards, while high ignition
point makes the fuel safe for transportation and storage but not favourable for starting
a fire.
(iv) Low contents of non-combustible material: A good fuel must have low contents
of non-combustible material as the non-combustible matter is left in the form of ash
which will naturally decreases the calorific value of the fuel. Moreover, disposal of
ash is itself a big problem and it increases the cost of operation.
(v) Highest pyrometric effect: The highest temperature obtained with the fuel on is
burning known as pyrometric burning effect. A good fuel should have a high pyrometric
effect. Gaseous fuels have the highest pyrometric effect.
(vi) Low moisture content : The moisture content of the fuel should be low, because
moisture reduces its calorific value. Since moisture in fuel (coal) evaporates and is
removed as steam during its burning and some of the heat liberated is utilised during
the conversion of moisture into steam. Therefore, the presence or moisture in fuel
(coal) reduces its calorific value. Moreover, moisture also increases the transport
charges.
(vii) Products of combustion should not be harmful : Fuels on burning should
not produce any objectionable and harmful gases which may act as physiological
poisons for human lives in nearby area. It should produce minimum amount
of smoke. In other words, the gaseous products of combustion of fuel should
not pollute the atmosphere. Gases like carbon monoxide (CO), sulphur di-oxide
(S02)' hydrogen sulphide (H 2S) and phosphine (PH 3 ) etc. are some of the harmful
gases.
(viii) Low cost: A good fuel should be readily available in bulk at a low cost. Its supply
must be reliable i.e. a fuel should not be adulterated.
(ix) Easy to transport : A good fuel is that which can be easily handled, stored and
transported at a low cost. Solid and liquid fuels can easily be transported from one
place to other. On the other hand, transportation of gaseous fuels is costly and can
even cause fire hazards.
(x) The storage cost offuel in bulk should be low.
(xi) A fuel should burn in air with efficiency, without producing much smoke.
(xii) The combustion of fuel should be easily controllable.
(xiii) A fuel should not undergo spontaneous combustion. The spontaneous ignition can
cause fire hazards.
(xiv) In case of solid fuels, size should be uniform, so that combustion is regular.
lAS CALORIFIC VALUE
Definition:
Calorific value is the important property of fuel. It is defined as "the total quantity
of heat liberated in calories by the complete combustion of unit weight (or volume)
of fuel in air/oxygen."
There are two types of calorific values i.e. higher and lower calorific values, also known as
gross calorific values and net calorific values respectively.
(a) High calorific value (HCV) or gross calorific value (GCV) : Almost all fuels contain
hydrogen and when the calorific value of such fuel is determined hydrogen is converted in to
steam. If the products of combustion are condensed to the room temperature (25°C or 77°F)
the latent heat of condensation of steam gets also included in the measured heat. The total
value calculated is then called higher or gross calorific value.
It may be defined as the total amount of heat produced when one unit weight (or vol.) of
the fuel is burnt completely and the products of combustion have been cooled to room
temperature.
(b) Lower calorific value (LCV) or net calorific value (NCV) : In actual practice the
water vapour and moisture etc. present in fuel are not condensed and escape as such along
with fuel gases. Hence a lesser amount of heat is available. The amount of heat, so, available,
is called lower or net calorific values.
It may be defined as the net heat produced when unit mass (or volume) of the fuel is
burnt completely and the com bustion products are allowed to escape.
Thus, NCV = GCV - Latent heat of water vapours formed.
Since 1 part by weight of hydrogen gives 9 parts by weight of water, the above equation
becomes
NCV =GCV - Wt. of hydrogen x 9 x Latent heat of steam.
The latent heat of steam is 587 kcallkg at room temperature (i.e., at 25°C).
Units of Calorific Value
The units of calorific value of fuel can be expressed in the following ways:
10 Essentials ofEngineering Chemistry
(i) C.G.S. System : In this system, the unit of heat is calorie and it is defined as the
amount of heat required to raise the temperature of 1 g of water from 14.5° - 15.5°C i.e., by
1°C. Since, solids and liquids are measured in terms of their masses, unit of calorific value is
callg.
(ii) M.K.S. System: In this system, the unit of heat is keal which is defined as the quantity
of heat required to raise the temperature of 1 kg of water from 14.5° - 15.5°C by 1°C." Thus,
1 kcal = 1000 cal.
:. Units of calorific value: kcal/kg (M.K.S. system for solid and liquid fuels)
1 kcallm 3 (M.K.S. system for gaseous fuels)
J/m 3 (S.I. system for gaseous fuels)
(iii) F.P.S. (or British System): In this system, the unit of heat is B.Th.U., which is
defined as the amount of heat required to raise the temperature of 1 pound of water by 1°F.
Unit of calorific value: B.T.U./lb ..... (For solid and liquid fuels)
3
B.T.U. ft ..... (For gaseous fuels)
Where B.Th.U. stands for British Thermal Unit.
(iv) S.I. System: Unit of calorific value = joule/kg
The inter conversion of units are as follows:
1 kcal/kg = 1.8 B.Th.U/1b or 1.8 B.Th.UlPound
3
1 kcallm = 0.1077 B.Th.U'/ft3
1 kcal =4.18687 kJ
[ PRACTICE PROBLEMS FOR TUTORIALS )
1. Define a chemical fuel.

2. What is meant by calorific value of a fuel?
3. Distinguish between gross and net calorific value of a fuel.
4. What is meant by ignition temperature?
5. Why should an ideal fuel have moderate ignition temperature?
6. What is meant by calorific intensity of a fuel ?
7. Mention four characteristics of a good quality coal.
8. Give five examples of artificial fuels.
9. Why is net calorific value less than gross calorific values?
10. Why are gaseous fuels more advantageous than solid fuels?
11. What is the main sources of hydrocarbons?
12. Name five hydrocarbon fuels. What is their main source.
13. What is the modern definitions of a fuel ?
14. What is the compositions and mains uses of petrol and kerosene oil ?
15. What is the main difference between LPG and CNG ?
16. What is the ultimate source of energy ?
17. Give examples of renewable and non-renewable sources of energy.
18. What chemical conversion takes place when a fuel is burnt?
[ ANSWERS)
1. A combustible substance containing carbon as the main constituent, which an

combustion liberates large amount of heat which can be used economically for
domestic as well industrial purposes, is called a chemical fuel.
2. It is the total quantity of heat liberated when a unit mass (or volume) of the fuel is
burnt completely in presence of sufficient quantity of air/oxygen.
3. Gross calorific value is the total quantity of heat liberated, when one unit of the fuel
has been burnt completely and the products of combustion have been cooled to room
temperature. On the other hand, net calorific value is the net heat evolved when
one unit of the fuel is burnt completely and the hot products allowed to escape as
such.
4. The lowest temperature at which the fuel must be pre-heated so that it starts burning
smoothly is called ignition temperature.
5. Low ignition temperature can cause fire hazards and involves danger in fuel storage
and transport; while high ignition temperature causes difficulty in starting ignition
of fuel. Hence, an ideal fuel should have moderate ignition temperature.
6. The maximum temperature reached, when the coal is completely burnt in the
theoretical amount or air is called the calorific intensity of a fuel.
7. (i) High calorific value, (ii) low moisture con~ent, (iii) low ash content, and (iv) high
calorific intensity.
8. Charcoal, coke, petrol diesel oil and oil gas.
9. Gross calorific value is the total amount of heat liberated, including latent heat of
steam, when one unit of the fuel is burnt completely. On the other hand net calorific
value is the net amount of useful heat liberated, excluding the latent heat of steam,
when one unit of the fuel is completely burnt. In other words, net calorific value is
less than gross calorific value by the amount of latent heat of steam formed during
the complete combustion of one unit of the fuel. However, if the fuel does not contain
hydrogen (e.g., pure carbon, sulphur, etc.) then two types of calorific values are same
in magnitude.
10. Gaseous fuels possess advantages over solid fuels: (i) they can be distributed and
transported easily through pi,aelines, (ii) they can be ignited at moment's notice, (iii)
their combustion can be controlled easily, (iv) they burn without producing smoke
and ash, (v) they possess high calorific values, (vi) their thermal efficiency is high,
(vii) they do not affect the quality of metal produced, when used in metallurgy as
fuel etc.
11. Petroleum and coal.
12. (i) Natural gas, (ii) petrol, (iii) diesel oil, (iv) kerosene oil, and (v) LPG. Their mains
source is petroleum.
13. A fuel is any fissionable material, chemical or a reactant which on combustion or by
any other mean can supply energy to generate power.
14. Petrol contains mainly aliphatic hydrocarbons ranging from C7 to Cg • It is mainly
used as motor fuel, for making petrol gas and as a solvent in drycleaning.
Kerosene oil contains aliphatic hydrocarbons from C 12-C 15 . It is mainly used as a
domestic fuel, illuminant and for the manufacture of oil gas.
15. LPG is liquid petroleum gas consisting mainly oflighter hydrocarbons up to C 4 . It is
mainly mixture of propane (C 3R s )' propene (C 3R 6), butane (C 4R lO ) and butene (C 4R s)·
It is used as domestic fuel.
CNG is compressed natural gas consisting mainly of methane (CR 4 ). It is used as a
fuel for the internal combustion engines because it gives pollution free exhaust gases.
16. Sun is the ultimate source of energy from where energy is being released in the form
of heat and light. The cause of this unlimited source of energy is the nuclear fusion
of hydrogen into helium taking place at high temperature of the sun.
17. Petroleum and coal are the examples of non-renewable sources of energy. These
sources are depletable and would be exhausted due to their enormous use. These
are also called fossil fuels. The renewable sources of energy are biomass, wind, ocean
and lidal waves and solar energy as such. These resources are not exhaustible.
18. Chemical energy of a solar reaction is converted into heat and light energy.
lA.6 DETERMINATION OF CALORIFIC VALUE
1. By Bomb Calorimeter
This apparatus is used for determining the calorific value of solid and liquid fuels.
Construction: A simple sketch of bomb calorimeter is shown in Fig. 1.1. It consists of a
strong cylindrical stainless steel vessel called bomb in which the combustion of fuel is made to
take place. The bomb is capable of withstanding high pressures. The bomb is provided with a
lid, which can be screwed to the body of bomb to make a perfect gas tight seal. The lid is
provided with two stainless steel electrodes and an oxygen inlet value. Th one of the electrodes,
a small ring is attached. In this ring a silica or stainless steel crucible can be supported.
The bomb is placed in a copper calorimeter which is surrounded by air-jacket and water
jacket to prevent loss of heat due to radiation. The calorimeter is provided with an electrically
operated stirrer and Beckmann's thermometer, which can read accurately temperature
difference upto 1I100th of a degree centigrade.
Working: A known weight (about 0.5 to 1.0 gram) of the given fuel is taken in the silica
crucible. The crucible is supported over the ring. A fine magnesium wire touching the fuel
sample is stretched, across the electrodes. The bomb lid is tightly screwed and the bomb filled
with oxygen to 25-30 atmospheric pressure. The bomb is then lowered into copper calorimeter
To battery
Backmanns
thermometer
Bomb (mode of
stainless steel)
Platinum ...-.c:~---t-1l
electrodes : -.
w~..+--+:,-:-r- Mg wire
-.
~1--t-~tt-::::~:ilo...o' ---4+~I-~_ .'-.t-Ring
Weighed
sample
.-' ~
_'0 ,
'p'" Copper calorimeter

:·i: containing a known
Air jacket :_-j: quantity of water
W;ter jacke~ - ~ =_-; :~':-.
"'-.:....:=-=-"------- ---- ----
Fig.!.!.
containing the known weight of water. Initial temperature of the water is noted after through
stirring. The electrodes are then connected to 6-volt battery and circuit is completed. The fuel
in the crucible burns with the liberation of heat. The heat produced by burning of the fuel is
transferred to water; which is stirred throughout the experiment by the electric stirrer.
Maximum temperature shown by thermometer is recorded. The calorific value of the fuel can
now be calculated as below:
Observations
Weight of the fuel taken in crucible = xgm
Weight of water in the calorimeter = Wgm
Water equivalent of the calorimeter
stirrer, thermometer and bomb = wgm.
(water equivalent of apparatus =
wt. of apparatus x sp. heat)
Initial temperature of water in calorimeter = t 10
Final temperature of water in calorimeter = t 20
Higher or gross calorific value of fuel = C cal/gm
Calculations
(a) Determination ofgross (higher) calorific value:
Heat gained by water = W (t 2 - t 1) cal
Heat gained by calorimeter stirrer. = w (t 2 - t 1) cal
thermometer and bomb
Total heat gained = W (t2 - t 1) + w (t2 - t 1) cal
= (W + w) (t2 - t 1 ) cal
Heat liberated by fuel = x •C
Now, Heat liberated by fuel = Heat obtained by water and calorimeter
x •C = (W + w)(t 2 - t 1 ) cal
:. Gross Calorific Value, C (W +w )(12 -t 1) II ... (1)
= ca gm
x
(b) Determination of net (lower) calorific value
Let the percentage of hydrogen in fuel be H
:. Wt. of water produced from 1 gm of fuel = -9H gm = 0.09 H gm.

100
:. Heat taken by water in forming steam = 0.9 H x 587 cal.
(:. Latent heat of steam = 587 cal/gm)
:. Net (lower) calorific value = Gross (higher) calorific value-Latent heat of water formed
:. Net calorific value = (C - 0.9 H x 587) cal/gm ... (2)
Corrections: In addition to the hydrogen correction, following three corrections must be
considered while calculating the calorific value of a fuel.
(i) Cooling correction (t) : Rate and time taken for cooling the water in calorimeter from
maximum temperature to room temperature must be considered from the above r~te of cooling
dto/minute and the actual time time taken for cooling (x minutes), the cooling correction
(t = dt x x) must be added to the rise in temperature (t 2 - t 1 ).
(ii) Acid correction (a): During ignition Sand N (if present) in the fuel are oxidised to
H 2S04 and HN0 3 along with the evolution of heat.
S + 2H + 202 ~ H 2S04 + Heat
2N + 2H + 302 ~ 2 HN0 3 + Heat
So this heat is also included in the measured heat and hence it must be subtracted as this
is not the part of calorific value. The amounts of these acids are analysed from washings of
bomb by titration. While H 2S0 4 alone is determined by precipitation as BaS0 4 correction for 1
mg of Sis 225 cal: while for 1 ml. ofN/10 HN0 3 format it is 1.43 cal.
(iii) Fuse wire correction (f) : The measured heat also includes the heat given by ignition
ofthe fuse wire (f cal.) and hence it must be subtracted from entire total value.
Thus, Gross (higher) calorific value c
(W -w)(t2 -t1 + cooling correction)-(Acid + fuse wire correction)

= CaVgm
weight of the fuel taken
Corrected formula: Grass C.V. = (W -w ) <! 2 -( 1 +() - (a + f) CaVgm

x
IA.5.1 Dulong's Formula For Calorific Value
The approximate calorific value of a fuel can be calculated by noting the amount of
combustible elements of the fuel. The higher calorific values of some of the main combustible
elements of fuels are given below :
Combustible elements HCV (k call kg)
Hydrogen 34,500
Carbon 8,080
Sulphur 2,240
The oxygen, if present in the fuel, is assumed to be present in combined form with
hydrogen, i.e., in the form of fixed hydrogen as H 20. So, the amount of hydrogen available for
combustion is given as :
Available hydrogen in the fuel =Total mass of hydrogen - Fixed mass
1 (mass of oxygen)
= Total mass of hydrogen -"8 in the fuel
It is because 8 parts of oxygen combine with one part of hydrogen from H 20. (The ratio of
H: ° = 1 : 8)
Knowing the chemical composition of the fuel, its HCV can be calculated by applying
Dulong's formula
HCV = 1~0[8,080C+34,500(H-~)+2,240S]kCal/kg
where C, H, ° and S represent the percentage of carbon, hydrogen, oxygen and sulphur in
the fuel respectively. In this formula, oxygen is supposed to be present in combination with
hydrogen as water.
Therefore, the LCV can be calculated as :
LCV = [HCV - 1 ~O H x587 ] k callkg = [HCV - 0.09 H x 587] k callkg

We know that one part of H by mass gives nine parts of H 20 and that latent heat of steam
is 587 k cal/kg.
( NUMERICAL EXAMPLES)
Examples 1 : On burning 0.83 g of a solid fuel in a bomb calorimeter, the temperature of

3,500 g of water increased from 26.5 to 29.2°C. Water equivalent of calorimeter and latent heat
of steam are 385.0 g and 587.0 cal/g respectively.lfthe fuel contains 0.7% hydrogen, calculate
its gross and net calorific value.
Solution: Here wt. of fuel (x) = 0.83 g; wt. of water (W) == 3,500 g; water equivalent of
calorimeter (w) = 385 g; (t 2 - t 1) = (29.2 °C - 26.5 DC) = 2.7 DC; percentage of hydrogen (lI) =
0.7%; latent heat of steam = 587 ca]Jg.
Gross calorific value = (W - w)(12 - I) ) == (3,500 + 385) x 2.7
x 0.83
= 12, 638 ca]fg
Net calorific value = [GCV - 0.09 H x 5871 (12,683 + 3,500 x 0.7 x 587) ca1Jg.
= (12,638 - 37) ca]Jg = 12,601 ca1/g.
Example 2 : A sample of coal contains: C = 93% and ash = 1%. The following data were
obtained when the above coal was tested in bomb calorimeter:
(i) Wt of coal brunt -- 0.92 g
(ii) Wt. of water taken = 550 g
(iii) Water equivalent of bomb and calorimeter = 2,200 g
(iv) Rise in temperature = 2.42 °C
(v) Fuse wire correction = 10.0 cal
(vi) Acid correction = 50.0 cal
Calculate gross and net calorific value of the coal, assuming the latent heat of condensation
of steam as 580 cal / g.
Solution: Wt. of coal sample (x) = 0.92 g; wt. of water (W) == 550 g; water equivalent of
calorimeter (w) = 2,200 g; temperature rise (t 2 - t 1 ) = 2.42°C; and correction = 50.0 cals; fuse
wire correction = 10.0 cals; latent heat of steam = 580 ca]Jg. percentage of H = 6%.
(W +w )(12 -I) )-(Acid + fuse correction)
GCV = x
500+2,200x2.42-(50+10) cals
0.92 g
= 7,168.5 ca1/g.
NCV =
[GCV - 0.09 H x latent heat of stearn]
= 7,168.5 - 0.09 x 6 x 580 ca1/g = 6,855.3 callg.
Example 3 : A coal has the following composition by weight : c = 90%; 0 = 3.0%; S =
0.5%; N = 0.5% and ash = 2.5%. Net calorific value of the coal was found to be 8,490.5 k cal.
Calculate the percentage of hydrogen and higher calorific value of coal.
Solution: RCV = (RCV + 0.09 R x 587) kca1/g
= (8,490.5 + 0.09 R x 587) kcal/kg ... (i)
= (8,490.5 + 52.8 R) kcal/kg
Also RCV = l~O [8,080X90+34,SOO(H - 3~O )+2,240XO.S] kcal/kg
= [7,272 + 345 H - 129.4 + 11.2] kcal/kg ... (ii)
= [7.754.8 + 345 H) kcal/kg
From (i) and (ii) we get:
7,754.8 + 345 H = 8,490.5 + 52.8 R
or 292.2 R =8,490.5 -7,154.8 = 1,335.7
or percentage ofH = 1,335.7/292.2 = 4.575% ... (iii)
RCV = (8,490.5 + 52.8 x 4.575) kcal/kg [From (i) and (iii)]
= (8,490.5 + 241.3) kcal/kg = 8,731.8 kcallkg.
Example 4 : Calculate the gross and net calorific value of coal having the following
compositions: carbon = 85%, hydrogen = 8%, sulphur = 1%, nitrogen = 2%, ash = 4% latent
heat of steam = 587 cal / g.
Solution: Gross calorific value (GCV)
= 1~O[8,080XC+34,500( H- ~)+2,240XS ]kCal/kg
= l~O [8,080X85+34,SOO( 8- ~ )+2,240XI] kcal/kg

I
= 100 [686,800+276,000+2,240] kcal/kg
1
= 100 [985,040]kcal/kg = 9,650.4 kcallkg.
Net calorific value (NCV) = (GCV - 0.09 + 1 x 587) kcal/kg = (9,650.4 - 0.09 x 8 x 587)
kcal/kg = 9,227.8 kcallkg.
Example 5 : The following data were obtained in a bomb calorimeter experiment:
Weight of coal burnt = 0.996 g
Weight of water in calorimeter = 2490 g
Weight of bomb, calorimeter, etc. = 3900 g
Rise in temperature of water = 2.592°C
Mean specific heat of the apparatus = 0.099.
Find the higher calorific value of the fuel. If the contains 6% hydrogen, calculate its lower
calorific value allowing 587 cal / g of steam.
Solution: It is given that x = 0.996 gm, W = 2490 gm,
(t 2 - t 1) = 2.592 °C H = 6
w = weight of apparatus x sp. heat
= 3900 x 0.099 = 386 gm
L.C.V. = (W +w )(12 -I) = (2490 +386)(2.592) = 7 484 call

x 0.996 ' gm
Now since L.C.V. = Higher C.v. -
0.09 H x 587 cal/gm
= 7484 - 0.09 H x 587 cal/gm = 7,167 callg
Example 6 : The determination of the calorific value of a coal sample gave the following
data:
Weight of coal sample = 0.9g
Water equivalent of calorimeter = 440g
Weight of water = 2560g
Rise in temperature = 2.42°C
Cooling correction = 0.052°C
Fuse wire correction = 10.0 cal.
Calculate the gross calorific value and net calorific value if the coal contains 6% hydrogen
and assume latent heat of steam equal to 600 callg.
Solution: Here x = 0.9 gm, w =440 gm, W = 2560 gm, t2 - tl = 2.42°C
Cooling correction = 0.052°C, Fuse wire correction = 10.0 cal
Latent heat of steam = 600 cal/g H = 6
(W +w )(t2 -II +cooling correction)-fuse wire correction
We know, G.C.v. = x
(2560 + 440)(2.42 + 0.0552) + 10 (3000 x 2.472) -I 0

= = -'------'---
0.9 0.9
7416.0-10
= 0.9
=8228.88 callg
N.L.C.V. = H.C.V. -
0.09 H x latent heat of stem
= 8228.88 - 0.09 H x 6 x 600 = 8228.88 - 324 = 7904.88 cal/g
Example 7 : Calculate the gross and net calorific value of a coal having following
compositions. C = 8% H = 7%, 0 =3%, S =3.5%, N =2.1% and ash = 4.4%.
Solution: According to Dulong formula,
Grass calorific value (GCV) = I~O [8080 C+34500( H - ~ )+22405] kcal/kg.
GCV = 1~0[8.080 x 80+34,500( 7-i)+2,240X3.5] kcaJ/kg.

1
= 100 [646400 + 228562.5 + 7840] kcal/kg.
1
= 100 [8828802.5] kcal/kg = 8828.025 kcal/kg
Net calorific value (NCV) = (GCV - 0.9H x 587) kcal/kg
(8828.025 - 0.09 x 7 x 587) kcallkg
= (8828.025 - 369.81) kcallkg
= 8458.215 kcallkg
( PRACTICE PROBLEMS FOR TUTORIALS)
1. Liquid fuel weighing 0.98 g and containing 90% of carbon and 8% of hydrogen gave
the following results in a bomb calorimeter experiment : Amount of water taken in
the calorimeter = 1450 g; water equivalent of the calorimeter = 450 g; rise in
temperature of water l.8°C. If the latent heat of steam is 587 kcal/g. Calculate the
gross and net calorific value of the fuel.
2. The temperature of 950 g of water increased from 25.5°C to 28.5°C on burning 0.75
g. of a solid fuel in a bomb calorimeter. Water equivalent of calorimeter and latent
heat of steam are 400 g and 587 cal/g respectively. If the fuel contains 0.65% of
hydrogen, calculate its net calorific value.
3. A sample of coal containing 92% C; 5% H; 3% ash. When this coal was tested in the
laboratory for its calorific value in the bomb calorimeter, the following data were
obtained:
Weight of coal burnt = 0.95 g
Weight of water taken = 700g
Water equivalent of bomb and calorimeter = 2000g
Cooling correction
Fuse wire correction = 10.0 cal
Acid correction = 60.0 cal.
Calculate the net and gross calorific values of the coal in cal/g; (Assume the latent
heat of condensation of steam as 580 cal/g).
4. The determination of the calorific value of a coal sample gave the following data:
Wt. of coal sample = 0.9 g
Water equivalent of calorimeter = 440 g
Wt. of water = 2500 g
Cooling correction = 0.052°C
Fuse-wire correction = 10.0 calories.
Calculate the gross and net calorific values, if the coal contains 6% hydrogen and
assume latent heat of steam equal to 600 cal/g.
5. 0.834 g of a fuel on complete combustion in excess of oxygen increased the
temperature of water in a calorimeter from 14.36°C to 18.lOoC. The mass of water in
calorimeter was found to be 1365 g. Calculate the higher calorific value of the fuel, if
the water equivalent of calorimeter, etc. is 135 g.
6. Calculate the gross and net calorific values of coal having the following composition:
carbon = 85%, hydrogen = 8%, sulphur = 1%, nitrogen = 2% and ash = 4%. Latent
heat of steam = 587 kcal/kg.
7. A coal has the following composition by weight. C = 90%, 0 = 3.0%, S = 0.5%,
N = 0.5% and ash = 2.5%. Net calorific value of coal was found to be 8490.5 kcal/kg.
Calculate the percentage of hydrogen and higher calorific value of coal.
(Mumbai, May 1997; G.G.S.I.P., March 2001)
(ANSWERS)
1. GCV = 3,490 cal/g; NCV = 3,067 cal/g
2. 5.366 cal/g
3. GCV = 7031.6 cal/g; NCV = 6770.6 cal/g
4. (i) 8064.1 cal/g (ii) 7740.1 cal/g
5. 6726.6 cal/g
6. GCV = 9650.4 kcallkg; NCV = 9227.8 kcal/kg
7. H = 4.58%, HVC = 8731.8 kcallkg.
1A.7 PETROLEUM CRACKING
The process of decomposition of less volatile higher hydrocarbons into more volatile lower
hydrocarbons with the application of heat and catalysts is known as cracking.
As the yield of petrol from the distillation of petroleum is small (about 16%), the petrol or
gasoline is prepared by cracking of less useful and cheap straight run oils like heavy oils and
residual oils. In fact approximately 50% of gasoline is now prepared by this method. The
cracking, besides increasing the yield of petrol, also improves the quality of gasoline in terms
of antiknock properties.
The fractions like heavy oil or residual oil contain alkanes of higher hydrocarhons having
C 12 or more carbon atoms. When they are cracked these large hydrocarbon molt'cuk bn'ak
up to give hydrocarbons with lesser number of carbon atoms. This decrease in size or llumOel
of carbon atoms is accompanied with a change in the boiling range or volatility ofthe resulting
product.
b.p. 216°C
jC7HI6+CsHIO)
C12H2o~ C6H14+C6H12 Boilingr:.nge C I6 H 34 ~ C q Hzo+C 7HI4
Ollllccalle C SHI2 +C 7H 14
etc.
30-150 C Hexdecanc
{CsHIS+CsHI6)
C lo H 22 +C 6H 12
etc.
Boi~ingr:.nge
j(}-150 (
The nature of products formed depend on the following:

(i) Structure of the hydrocarbon.
(ii) Temperature and pressure applied in the cracking.
(iii) Presence or absence of catalyst.
Changes occurring during cracking: Besides the decrease in the size of the molecule
which results in increased volatility or lower boiling fractions, the other important changes
taking place are as follows:
(i) Cracking results in formation of a mixture of large number of hydrocarbons-all having
lower b.pt. than initial alkane.
(ii) Straight chain alkanes are converted to branched chain hydrocarbons
(isomerization).
(iii) Saturated hydrocarbons are converted to unsaturated hydrocarbons.
(iv) Ring closure or cyclization of aliphatic alkanes may occur.
Types of cracking: There are two main processes used for cracking: (a) Thermal cracking,
and (b) Catalytic cracking.
(a) Thermal cracking: When the cracking is carried out simply by the appbcation of
heat and pressure, it is known as thermal cracking. The furnace used for thermal cracking is
made of special chromium nickel alloy and the design is such that it allows high oil velocity
in the tubes and very low residence time. The reaction products are then passed through
fractionating towers to separate gasoline from other fractions formed in cracking. Thermal
cracking is done in either liquid phase or vapour phase.
(i) Liquid phase cracking: In this process the cracking of the stock (consisting of either
heavy oil or residual oil) is done at a temperature of 475-530°C under high pressure,
usually 7 to 10 atmospheric pressure, to keep the reaction product in liquid state.
The yield of petrol on fractionation is approximately 60-65% and the octane number
is in the range 65 to 70.
(ii) Vapour phase cracking: In this process the stock is first converted to vapour state by
heating to about 600°C and then subjected to 3.5 to 10.5 atmospheric pressure for a
very short time for cracking. The yields are good (approx. 70%) but the octane number
is again below 70. However, it is disadvantageous to subject heavy oil or residual oil
to this process because they cannot be vaporized completely.
(b) Catalytic cracking: When the cracking is done in the presence of catalysts, high
pressure and temperature are usually not necessary. The feedstock used is generally in the
boiling range of 350-550 D C. The catalytic cracker may be fixed bed, moving bed or fluid bed
type. Nowadays generally the latter types are used.
The product mix obtained from a catalytic cracker depends on a number of variable viz.
nature of feedstock, catalyst, cracking conditions, etc.
(i) Fixed bed catalytic cracking : In this process the catalyst is used in the form of a
fixed bed and cracking is carried out at around 500°C. A number of cracking furnaces are
used, so that if the catalyst is spent in one furnace, because of carbon, deposition, the other
one is used while the spent catalyst is being regenerated by burning the carbon in a current
of air.
Process: The oil vapours are heated in a preheater to cracking temperature (420-450°C)
and then forced through a catalytic chamber (containing artificial clay mixed with
zirconium oxide) maintained at 425-450 C and 1.5 kg/cm 2 pressure. During their passage
D
through the tower, about 40% of the charge is converted into gasoline and about 2-4% carbon
is formed.
Carbon gets absorbed on the catalyst bed. The catalyst, stops functioning, due to the
deposition of black layer of carbon, formed during cracking. This is re-activated by burning off
the deposited carbon. During the re-activation interval, the vapours are diverted through other
catalyst chamber. The vapours produced are then passed through a fractionating column, where
heavy oil fractions condense. The vapours are then led through a cooler, where some of the
gases are condensed along-with gasoline and uncondensed gases move on. The gasoline
containing some dissolved are is then sent to a 'stabilizer, where the dissolved gases are
removed and pure gasoline is obtained (see Fig. 1.2).
t
Cracked Cooler
'"P'l ~, St'~LF'"G:::,un,
Heavy
- a ••••
of charge~f---- - Heavyoil ,.:, •.
Pre-heater Catalyst Fractionating Gasoline

chamber column containing
(425-450°C) dissolved gas
Fig. 1.2. Fixed-bed catalytic cracking.
(ii) Fluid bed (or moving bed) catalytic cracking : To carry out catalytic
cracking continuously, fluidized catalyst is used. The catalyst is suspended in a stream of oil
vapours. The spent catalyst continuously flows out of the bottom of the furnace and
can be regenerated while fresh amounts of catalysts are continuously added from the
top. The temperature is maintained between 450 to 550°C and the pressure is between 1 to 2
atmosphere .
. Process
. In the fluid catalytic cracking, oil preheated to about 300°C is sprayed from the bottom
into the reactor containing the catalyst (Fig. 1.3). Formerly natural zeolites and now synthetic
molecular sieves in the powdered form are used catalysts. In the reactor the oil mixes with
the powdered catalyst to produce a reaction temperature of about 530°C. At this stage steam
is introduced, which converts the catalyst and the oil mixture in a fluidized state into the
reactor. The oil undergoes cracking in less than a contact time of 3 second. The products are
then transferred into a fractionating column not shown in the figure. The deactivated (spent)
catalyst is conveyed into a regenerator where the excess oil is stripped by steam and the carbon
deposited on the deactivated catalyst is burnt off using hot air. The regenerated catalyst is
again introduced into the reactor by a current of air. The advantage of fluidized cracking process
is that a high degree of mixing is achieved and consequently a good contact is established
between the catalyst and the vapour. This results not only into a higher yield, but a gasoline
of better quality with higher octane number.
r;:=.- To fractionating
column
Reactor
Regenerator
...__Steam/oil
Fig. 1.S. Fluidized catalytic cracking.

Most of the gasoline petrol that is being used is obtained by the cracking process rather
than by direct refining of Petroleum. It also gives several gaseous hydrocarbons employed ill
the manufacture of petrochemical. A comparison of catalytic and thermal cracking processes
is given below:
Process Thmperature Pressure Quality of Compositions

Gasoline of flue gases
Thermal 550°C 5 atm Octane No. 65-68 mainly C 1-C 2
cracking it contains
mainly normal
alkanes and
alkenes
Catalytic 500°C 0.1 atm Octane No. 80-85 C3-CS
cracking branched chain
alkanes aromaties
The yields of gasoline by catalytic cracking are generally higher and the octane number is
also above 80. The resulting product is fractionated in a tower to give gasoline and other heavy
fractions which are again subjected to cracking.
Applications of Cracking
1. Obtaining petrol: The most important single application is the preparation of gasoline
or petrol by converting high boiling fractions into petrol. Roughly more than 50% of petrol
produced is by cracking processes, as it also given as better quality petrol in terms of
antiknocking properties.
2. Preparation of oil gas and petrol gas: Oil gas is obtained by cracking of kerosene oil by
dropping it over red hot iron retorts. The kerosene is converted to a mixture of gaseous
hydrocarbons like methane, ethane, propane, butane etc., which are the main constituents of
oil gas, together with small amounts of other hydrocarbons and hydrogen. The gas used in
laboratory burners is generally oil gas which is stored in iron gas holders over water and supplied
to laboratory through pipe lines.
The petrol gas is prepared by cracking of petrol by passing it through electrically heated
coils or retort. The petrol is converted to a mixture of simple gaseous hydrocarbons. The petrol
gas is also used in laboratory as it is convenient to prepare and the cost of the plant is low as
compared to oil gas plant.
3. Obtaining petrochemicals: The alkanes obtained from natural gas namely ethane,
propane, butane and pentane are subjected to thermal cracking to yield mainly ethylene and
to some extent propylene, which are the first generation petrochemicals and source of many
important chemicals. Similarly, naphtha and gas oil fractions obtained from petroleum refining
when subjected to thermal cracking and reforming yield aromatic raw materials (BTX) for
petrochemicals.
lA.S CATALYTIC REFORMING
It involves reshaping or reforming the petroleum hydrocarbon molecules to enhance their
octane number for gasoline blending. In this process, normally paraffin and naphthene (Alicyclic
hydrocarbon) molecules are reshaped into aromatics. For instance, n-heptane (C 7H 16) is changed
to toluene (C 7 H s)' n-octane (CSH 1S ) to ortho-xylene (CSH lO ), cyclo-octane (CSH 16 ) to p and m-
xylenes. The process is carried out at a temperature range of 250-550 C in an adiabatic reactor
D
at a pressure of 10 kg/cm 2 in the presence of bimetallic catalysts platinum and rhenium, tin
or germanium on a silica-alumina support. Although hydrogen is obtained as a by product, the
feed is mixed with hydrogen and sent to the reformer. Reforming reactions are accompanied
by cracking and coking. In order to suppress the latter, undesirable reactions; optimum
pressures and temperatures are used.
Catalytic reforming is not only used to improve the quality of petrol i.e., to improve its
octane number, but the higher boiling petroleum fractions and light naphtha give a large
number of petrochemicals by reforming operation. The products of reforming are high octane
number petrols and aromatic hydrocarbons such as benzene, toluene and xylenes etc. The
reactions taking place are dehydrogenation, dehydrocyclisation, isomerization and
hydrocracking. At lower temperatures alkanes are isomerised and naphthanes are converted
to aromatics, while at higher temperature the paraffins are also converted into aromatics.
The reaction takes place under pressure (10 - 40 atm) and at 450 - 540°C under reducing
conditions. About 15% of products formed are H 2, CH 4, C 2H s ' C3HS and C4HlO' The
remaining products consist of highly branched hydrocarbons and aromatic hydrocarbons. This
process is employed for the manufacture of benzene, toljlene, xylenes etc. and high octane
aviation fuels.
Examples:
(a) Isomerisation (n-pentane to isopentane)
(i) H3C-CH2-CH2-CH2-CH3 ~ H3C-CH-CH2-CH3

I
CH3
isopentane
(ii) Isomerisation of ethyl cyclopentane to methyl cyclohexane (aromatisation)
CH,
I CH3
CH, I
I CH
H,C
I
/CH",
H,C---CH,
CH,
I-
Ethyl cyclopentane
- H,C
H,C\
I
/
CH,
"'-
/CH,
CH,
I
Methyl cyclohexane
(b) Cyclisation and isomerization (n-heptane to methyl cyclo hexane)
CH,
H,C CHa HaC CH, t
I
H,C
I
CH,
I I
HC - - C H
Cyclisatilln
~
H2C/ \H,
I
H,C"
I
/CH,
I
H,C
I
/CH,
-H,
H)" )H. CH,
CH, "CH,
Methyl cyclo h )xane
Dimethyl cyclopentane
n-pentane
24 Essentials of Engineering Clil'misl n
(c) Cyc/isation and aromatisation (n-heptane is converted to toluene)
Cyclis8 tion •
-H2
A_"~"o" ~
-.'3H2 ~ ~
Toluenp
(d) Reforming of n-octane : n-octane under reaction conditions can undergo cyclisation at
three positions namely 1, 6; 2, 7; or 3, 8 giving rise to ethyl cyclohexane or 1, 2- dimethyl
cyclohexane. These two on aromatisation would yield ethyl benzene or 1, 2-dimethyl benzene
(o-xylene).
1 2 3 4 5 (j 7 8
H 3C---CH 2 - - - C H 2- - - CH 2 CH 2 CH 2.---CH,---CH
1.6
,
1 2 3 4 5
I
6 'I Ii
C---C---C--- C C C c---c
t tL.....--+--_ _ _t-...----J!
1
1: 6
1 2 7
: 1 3 :8
Q-- ~~ >
<0>- 9 CH,-CH,
CHa
CH., H,C-H,C--< 0>
n-octane under ideal laboratory conditions predominantly yield ethyl benzene and ortho
xylene. Under actual commercial conditions isomerization and rearrangement leads to several
other compounds such as benzene, toluene, meta xylene and para xylene.
Main Routes during Reforming
From the above cited examples it may be concluded that the aromatic hydrocarbon~ aft)
formed during reforming via three main routes.
(i) Dehydrogenation of cyclo hexane and homologues, e.,. cyclohexane gives
benzene and methyl cyclohexane gives toluene
Chem.ical Energy Sources 25
CHI
dehydr()gonatlon
•
Methyl ~'Yclohexanc Toiu(,lle
(ii) Dehydroisomerisation of cyclopentane homologues, e.g. I, 2 dimethyl

cyclopentane gives toluene.
+ 3H~
1,2 dimethyl cyc\opentane Toluene

(iii) Dehydrocyclisation of alkanes, e.g. n-hexane gives benzene and n-heptane
gives toluene.
d~hydrncyclu;ati{ln
C'i H 16 lit + 1H~
N - heptane
TohUlI1!!
Reaction (i) is the fastest being simply a dehydrogenation reaction. It does not require a
dual function catalyst. Reactions (ii) and (iii) do require a dual function catalyst, because they
involve a combination of two types of reactions and carbo cation rearrangements. These reactions
are c&talysed by both platinum sites and acidic sites (alumina). Their mechanisms are
complicated and by no means fully understood.
IA.9 KNOCKING
Gasoline (or petrol) is used as fuel in the internal combustion engines of scooters, cars
and aeroplanes. For this purpose, the vapours of gasoline are mixed with air. The mixture is
compressed to a small volume and then ignited by the spark from the spark plug. The mixture
explodes and the petrol burns to form a large number of gaseous products which pushes back
the piston. This thrust provides the power for moving the automobile.
For maximum efficiency, the fuel mixture must be highly compressed belore firing in the
cylinder. But in some cases, due to over compression of the fuel mixture, pre-ignition of fuel
takes place in the cylinder before sparking which causes a violent jerk to the piston. The
violent jerk gives rise to a metallic sound or rattle known as knocking. This causes damage to
the piston and decreases the efficiency of the engine.
Knocking is an undesirable property. However, it depends on nature of fuel. Straight-chain
compounds have a greater tendency of knocking than branched-chain compounds which are
said to have an anti-knoching quality.
Mechanism
In an internal combustion engine, a mixture of air and petrol vapour is compressed and
ignited by an electric spark, which causes oxidation of hydrocarbon molecules.
It is essential that the combustion offuel in the cylinder ofl.C. engine should proceed in a
regular way. After the combustion reaction is initiated by spark in the cylinder, a flame should
spread rapidly and smoothly through the gas mixture and the expanding gas drives the piston
down the cylinder.
In certain circumstances, however, Cylinder
the rate of oxidation is so great that the
mixture detonates, producing the sound
~-+~~ ~~~~
called engine 'Knock'. The rate of
II
Compression
oxidation of a hydrocarbon molecule . V
depends on the number of carbon atoms RatIO = _ 2
V1
T
in the molecule, on the structure and on
the temperature. The temperature
depends upon the 'compression ratio' i.e.
the ratio of the cylinder volume at the end (a) Top-dead centre (b) Bottom dead centre
of suction stroke to that at the end of the Fig. 1.4. Compression ratio.
compression stroke of the piston. In other
words, the 'compression ratio' is the ratio of the volume of the gas above the piston in its bottom
dead-centre position to the gas volume above the top-dead centre position as shown in Fig. 1.4.
Chemical Structure and Knocking
The tendency of knock depends upon the nature of fuel, engine speed, and air-fuel ratio.
In general, the tendency to knock varies with change in the nature of fuel as follows :
Straight chain paraffins> Branched chain paraffins> Olefines > Napthenes > Aromatic-
hydrocarbons.
Straight chain paraffins have poor anti-knock properties and it improves with increasing
length of hydrocarbon chain. Branched chain paraffins have better anti-knock properties than
straight chain paraffins and it improves with increase in number of branches. In olefines, the
anti-knock property increases as the double bond approaches the middle of carbon chain. In
cracked gasoline, due to the presence of olefines, branch chain paraffins and aromatic
hydrocarbons the anti-knocking property is increased.
IA.IO OCTANE NUMBER
The octane number of a fuel introduced by Edger (1927) is a measure of its tendency to
knock, when burnt in a spark-ignition engine. When gasoline or any other fuel is used to
operate an engine, it burns with air inside the cylinder in a very rapid way with the result
that the pressure inside the chamber is at once increased. The rapid rise in pressure sets up
vibration of the cylinder walls and other metallic surfaces giving a distinct knock or noise.
The tendency of knocking of fuel depends upon the nature of fuel, engine speed and air-fuel
ratio etc. The knocking of engine causes, a loss in power with the result that the efficiency of
the engine is decreased.
The anti-knock quality of the gasoline used as a fuel is determined by its octane rating or
octane number. It has been found that the hydrocarbon n-heptane produces maximum knocking
when used as the fuel. Due to its very poor antiknock quality, it has been arbitrarily assigned
an octane number of zero. On the other hand, 2, 2 4-trimethylpentane (incorrectly called iso-
octane) produces minimum knocking and has been assigned an octane number of 100.
CHs-CH2-CH2-CH2-CH2-CH2-CHs
n-Heptane
(Octane number = zero)
CHa CHa
I I
CHa -C-CH2 -CH-CH3
I
CH3
2, 2, 4-Trimethylpentane
(Octane number = 100)
This means that n-heptane is the worst and iso-octane the best fuel. All other fuels are
rated between zero and 100.
Thus. the octane number or octane rating of a given fuel may be defined as the percent of'
iso-octane in the mixture of iso-octane and n-heptane which has the same anti-lmocking
qualities as the fuel being tested under the similar experimental conditions. For instance if
the octane number of a fuel is 80, it meant that this behaves like a mixture of 80 percent
iso-octane and 20 percent n-heptane.
Generally, gasolines having an octane number of 74 are used in motor cars, scooters and
motor-cycles. Such gasolines are known as regular gasolines. Fuels having octane number lower
than this value are called third grade gasoline. Gasolines having an octane number of 81 and
above are known as premium gasolines. Aviation gasoline (gasoline used in aeroplane) has an
octane number of 100. Gasolines with rating even higher than 100 have been produced. FoT'
example, the octane number of 2, 2, 3-trimethylbutane (Triptane) has an octane number of
124, n-nonane has given octane number of -45.
CH3-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH3
n-Nonane (octane no - 45)
CH3
I
CH 3 -C-CH- CH3
I I
CH3 CH3
2, 2, 4-Trimethyl butane (Triptane) octane no. 124.
Hence. it lS clear that higher the octane number offuel, the lesser will be its Imoc!?ing tendency,
and better is the quality offuel, for internal combustion (I.C.) engine.
Now-a-days, gasoline (petrol) used as a fuel in aeroplanes known as aviation gasoline is
having high octane rating as 135 or even more have been produced.
IA.I0.1 Improvement of Octane Number
A good fuel possesses higher value of octane number. The octane number of fuels can be
improved by two ways:
(i) By catalytic cracking or catalytic reforming: These are the methods to produce
artificial gasoline mixture that contain hydrocarbons with high octane numbers. The octan(~
number changes with the change in the structure ofthe hydrocarbons as follows:
Straight chain alkanes < Branched chain alkanes < Olefins < Cycloalkanes < Aromatics.
(i) Straight-chain alkanes have low octane number. As the chain length increases, the
octane number decreases, e.g., octane number of n·nonane is less than zero.
(ii) Branched-chain alkanes have higher octane numbers than the isomeric straight chain
alkanes, e.g., Octane numbers ofn-heptane and 2,2, 3-Trimethylbutane are zero and
125 respectively.
(iii) Octane number of cycloalkanes is higher than that of corresponding open-chain
alkanes.
(iv) Alkenes and aromatic hydrocarbons have higher octane numbets than alkanes.
For the same reason, the gasoline obtained through the process of catalytic cracking or
reforming which contains higher percentage of alkenes, branched-chain alkanes and aromatics
has higher octane number than the gasoline obtained by direct distillation of petroleum.
lA.lO.2 Gasoline additives (anti-knocking agents)
The octane number of a fuel (gasoline) can also be increased by the addition of anti-knock
agents like tetra-ethyl-lead or TEL (C 2H 5 )4 Pb and di-ethyl telluride (C 2H 5 )2 Te and this process
is called 'doping'. In motor fuel (about 0.5 ml) and in aviation fuels (about 1-15 ml) of TEL is
added per liter of petrol. In addition to tetra-ethyl-lead (60%) small amounts of ethylene di-
bromide (C 2H 4 Br2) (26%), ethylene chloride (9%) and red dye (2%) or mixture of 1-3 ml under
the name ethyl-fluid' is added to gasoline to increase antiknock properties, Gasoline containing
tetraethyllead is known as leaded or ethyl gasoline.
According to the most accepted theory, TEL is converted into a cloud of finely divided lead
oxide particles in the cylinder. These particles react with any hydrocarbon peroxide molecules
formed, thereby slowing down the chain oxidation reaction and thus decreasing the chances of
any early detonation. It is also believed that tetraethyllead dissociates to give ethyl free radicals
which stop the premature burning of the fuel.
However, deposition of lead oxide or lead is harmful to the engine life. In order to eliminate
the lead oxide formed in the engine, a small amount of ethylene dibromide (C 2H 4 Br2 ) is also
added to petrol. As soon as explosive combustion occurs due to the spontaneous ignitions, the
last portions of the compressed mixture of petrol and air in petrol engine, the lead oxide is
rapidly reduced to metallic lead. Thus, the lead is deposited on the spark plug points, the
cylinder walls and the piston head. The added ethylene dibromide reacts with lead to form
lead bromide, which is volatile at engine temperature and removes along with the exhaust
gases.
CH 2 Br
Pb + I ~ PbBr2 + CH 2 =CH2
CH2 Br
Ethylene bromide Lead bromide Ethylene
The presence of sulphur compounds in petrol reduces the effect of TEL. Moreover TEL, is
more effective on saturated hydrocarbons than on unsaturated ones.
Pollution problem: A gasoline-engine discharges various substances into the atmosphere.
These are carbon dioxide, water vapours, carbon monoxide, nitrogen oxides, unburnt
hydrocarbons and from leaded gasoline, certain compounds oflead. Some of these substances
are highly poisonous. Their emission into atmosphere, with the increasing use of automobiles,
ChemlCal Energy Sources 29
is a serious pollution problem. Certain devices are now being used to oxidize the unburnt
hydrocarbons and carbon monoxide to carbon dioxide and decompose nitrogen oxides into
nitrogen and oxygen. The addition of tetra ethyl lead in gasoline can be avoided by increasing
the octane number of fuel by adding certain aromatics and branched chain hydro carbons.
The gasoline so obtained with improved octane number is known as unleaded gasoline.
lA.10.3 Unleaded Petrol
The octane number of petrol may also be increased by mixing hydrocarbons with high
octane number in the petrol whose octane number is increased without the addition of lead
compounds, but by mixing other compounds into it is called unleaded petrol. Nowadays, the
following two ways are adopted-to improve the quality of engine fuel.
(i) Catalytic Reforming : The process already discussed (section lA.S) increases the
amount of branched chain and aromatic hydrocarbons in the fuel and consequently the octane
number of the fuel is increased. The common branched chain hydrocarbons introduced as a
result of reforming are isopentane and isooctane and the aromaties are ethyl benzene and
isopropyl benzene.
(ii) Methyl Tertiary Butyl Ether (MTBE) : It is also added to boost the octane number
of the fuel. MTBE [R'C-O-~::CR, J has oxygen in its structure, which is supplied for
the combustion of petrol in internal combustion engine and the formation of peroxide
compounds is reduced. The use of leaded petrol in automobiles is being phased out because of
the pollutions caused by lead compounds.
The advantages of using unleaded petrol are
(a)The deposition of lead from leaded petrol in different parts of the engine decrease the
efficiency of engine. Moreover, inspite of the use of diethyl bromide, the air pollution due to
lead is not ruled out. So, the use of unleaded petrol not only increases the efficiency of the
engine, but it avoids the lead pollution in the atmosphere.
(b)It allows the use of catalytic converters attached to the exhaust in automobiles. To convert
the toxic gases of the automobile exhaust such as CO and oxides of nitrogen to harmless CO2
and free N 2' sodium is used as a catalyst. Lead acts as a catalytic poison for the catalyst, so
use of leaded petrol hinder the working of catalytic converters. The use of unleaded petrol
permits the use of catalytic converters which is essential to reduce air pollution due to CO,
NOx and unburnt hydrocarbons.
lA.ll Cetane Number
Cetane number is a measure of knocking characteristics of a diesel oil. It is desirable for a
fuel to ignite without delay when it is injected into the cylinder of a compression ignition engine.
The time-interval between the beginning of injection and the start of combustion is known as
the period of ignition delay. Cetane (n-hexadecane C16H 34 ) is a saturated hydrocarbon, which
ignites very quickly and without delay, while-methyl naphthalene (CnHlO) (an aromatic
hydrocarbon) does not ignite quickly and thus has a long ignition delay. Thus a cetane number
scale has been set up in which cetane is rated as '100' cetane and a methyl naphthalene is
rated as '0' cetane. So cetane number of fuel oil is obtained by comparing the ignition quality
by mixture of cetane and a-methyl naphthalene.
L
Cetane (n-hexadecane, C 16H s4 ) ignites rapidly and is given a cetane number of 100, whereas
a-methylnaphthalene ignites slowly and is given a cetane number of zero.
H 3C-<CH2)14-CH S
Cetane (n-Hexadecane)
(Centane No = 100)
u-Methylnaphthalene
(Centane No = Zero)
Thus the cetane number of a diesel oil is defined as :
The percentage by volume of cetane in a mixture of cetane (a-hexadecane) and a-methyl
naphthalene which has the same ignition quality under the same conditions as the fuel
under test.
When a diesel oil has cetane number 40, it means that the spontaneous ignition temperature
of oil is just same as that of a mixture of 40% cetane and 60% of a-Methyl naphthalene.
The cetane numbers of high speed, medium speed and low speed diesel engines should be
at least 45, 35 and 25 respectively. The cetane number of an oil can be improved by adding
(about 2%) substances (called dopes) like acetylene, ethyl nitrite, ethyl nitrate, acetone, di-
ethyl ether and alkyl nitrates etc.
In petrol engines, knocking is due to the sudden spontaneous combustion of the last portions
of the fuel, whereas, knocking in a diesel engine is due to the delay in the spontaneous
combustion of the first part of the fuel. Thus, an oil of high octane number has a low cetane
number and vice versa. Further, a crude oil which gives petrol of high octane number gives a
diesel oil of low cetane number.
lA12 SYNTHETIC PETROL
Need for the manufacture of synthetic petrol was felt during second world war, when
Germany was cut off from oil producing countries. At that time, scientists thought about getting
hydrocarbons of desired chain length from coal, which was mainly consisting of carbon.
Moreover, to meet the ever increasing demand of petroleum due to its unlimited use as
vehicular fuel, chemists have developed some methods for synthesising petroleum artificially
mainly from coal. '!\vo important techniques employed for the production of synthetic petroleum
are described below:
1. Bergius Process 2. Fisher Tropsch Process
1. Bergius Process: In this method, low ash coal free from impurities of sulphur is finely
powdered and mixed with heavy oil to give a paste. The paste is heated with hydrogen at 450-
500°C for about two hours at a pressure of about 250 atm in presence of a catalyst (8n or Ni
Oleate). The coal undergoes hydrogenation to form saturated hydrocarbon, which decompose
at the prevailing high temperature and pressure to yield low boiling liquid hydrocarbons, which
are then separated to give various fractions.
Paste of Coal Powder + H2 catalyst) Petroleum like product in heavy oil

A line sketch of the plant has been shown in Fig. 1.5. The gases coming out ofthe converter
are firstly passed through a cooler where a liquid resembling crude oil is obtained, which is
passed through fractionator to give following fractions:
(a) Gasoline, (b) Middle oil, (c) Heavy oil
Coal
powder Catalyst
~ ~ Petrol
Mixture
Middle
Oil
Coal
Heavy oil
Fig. 1.5. Synthetic petroleum from Coal by Bergius process.

Middle oil fractions can again be converted into gasoline by hydrogenation under pressure.
Heavy oil is withdrawn from the bottom and is used again for making paste with fresh sample
of coal.
2. Fischer Tropsch Process : In this process, firstly steam is passed over red hot coke
to give water gas.
C + H 20 ~ CO+H2
Woke) (Steam) (Water gas)
Water gas is mixed with more hydrogen and is passed over iron oxide to remove sulphur
and its compounds. Further the mixture is passed over sodium carbonate to remove organo
sulphur compounds. Thereafter, the purified mixture is passed over a catalyst consisting of
cobalt (100 parts), thoria (5 parts), magnesia (8 parts) and kiesulguhr (200 parts) at about
200 - 250°C temperature and 25 atm pressure.
The process can be represented in a line sketch (Fig. 1.6).
Cooler
Water
gas
'--...--"'..... Heavy
Convertor oil
Compressor (200-300"C)
Purification of <5-25ATM) Fractionating
gas column
Fig. 1.6. Fischer-Tropsch method.
It is essentially a catalytic reduction of carbon monoxide with hydrogen to give straight
chain alkanes and olefins.
Catalyst
nCO + 2nH2 ---'=="-~) CnH2n + n140
Olefins
Essentials of Engineering Chemistry
nCO + (2n + 1)H2 ~ Cn H2n+2 + nH 20
Paraffins
By adjusting the proportion of reactants and the working conditions, products having
mixtures of different constituents can be obtained. The gasses coming out of the convertor
are passed through cooler, which gives a crude oil like liquid. It is passed through a fractionator
to l,-riv0 heavy oil and gasoline.
The heavy oil can be further converted into gasoline by cracking.
Coal based projects require much more capital than petroleum based projects. For example,
a coal based ethylene plant requires three times the investment as compared to naptha based
of comparable size. Due to repeated increase in petroleum prices, the interest in such processes
has been revived and various countries including India are considering setting up of synthetic
petrol plants.
lA.13 POWER ALCOHOL
Power alcohol is ethyl alcohol (C 2H s0H). It is a non-petroleum fuel used as a fuel in internal
combustion engines when blended with petrol.
Sources: Power alcohol is manufactured from:
1. Saccharine matenals containing sugar e.g. molasses, beet, sugarcane.
2. Starchy materials containing starch e.g. potatoes, cereals like corn, barley.
3. Cellulose materials ('.,~. waste sulphite liquors from paper and pulp industry. They
contain sugar produced by hydrolysis of cellulose and hemi-cellulose.
4. Hydrocarbon Gases: Obtained by hydration of ethylene or conversion of gases into
CO-H2 mixture which is passed over hydrogenation catalysts.
Importance of power alcohol as fuel
Power alcohol when mixed with petrol is used fuel in I.C.E. The blends contain 25% alcohol
.lI1d 7f)(/; petrol.
Industrial alcohol containing 95% alcohol and 5% water does not mix with petrol. But on
.lcicl!tlOI1 of blending agents like ether, benzene etc. it can be blended with petrol and used as a
Illl'l.
Merits of alcohol-blended petrol
1. Alcohol has octane number of about 90. Addition of alcohol to petrol increases its
octane number and consequently increases its antiknock property.
2. Alcohol blends because of its better anti-knock property can be used in engines with
"higher compression ratio". Increase in compression ratio is required for the blend
to compensate the low calorific value of alcohol in the blend.
3. An alcohol-petrol blend gives equal mileage per gallon as compared to neat petrol.
4 Starting difficulties are not produced when alcohol-blend petrol is used.
5. There is no abnormal corrosion when alcohol-blend petrol is used.
6. Lubrication in case of alcohol-blend petrol is the same as that of neat petrol.
7. Alcohol-petrol blend does not decrease power output and does not increase fuel
consumption.
Demerits of alcohol·blend petrol
1. It has a tendency to absorb moisture from tanks or any other source. This results in
separation of layer of alcohol and petrol especially at low-temperatures. An addition
of benzene, toluene etc. eliminates this tendency.
2. Ethyl alcohol reacts with Mg and Al at high temperature leading to corrosion.
3. When temperature falls below 70°C, starting troubles arise due to "low vapour
pressure" of alcohol. Therefore for proper starting, heating of the carburator and in
take system in motor engine has to be provided.
4. Air required for complete combustion of the blend is less than the air required for
petrol. So the air-inlet in the motor engine to be modified so as to regulate the entry
of air into the engine cylinder.
5. Alcohol lowers the calorific value of petrol.
1. What is meant by the term cracking?

2. What is straight-run-gasoline ?
3. What is synthetic petrol?
4. What is reforming?
5. What is meant by compression-ratio of an I.C. engine?
6. What is meant by knocking?
7. Arrange n-octance, naphthalene, isooctance in increasing order of their knockill,:.!
tendency.
8. What is meant by octane number of a gasoline?
9. What is cetane value of a diesel fuel ?
10. Select the compound which possesses highest octane number and highest cet(lllC
number out of n-heptane, n-hexadecane, n-octane and isooctane.
11. What is power alcohol?
12. Compare the octane rating of alcohol with that of gasoline.
13. Mention two advantages of using alcohol-gasoline blend in internal combustion engine.
14. Mention two disadvantages of using alcohol-gasoline blends in I.C. engine.
15. What is wet gas?
16. Gasoline containing tetra ethyl lead is used in internal combustion engines. Give
reason.
17. What is meant by cat cracker '?
18. Why is octane number of 2, S·dimethylpentane higher than that of n,.heptane ?
19. Why is gasoline containing tetra ethyl lead used in internal comb\\stion engines?
20. Why catalyst requires regeneration in catalytic cracking?
21. Why should fuel for cars not evaporate too easily?
22. Is catalytic reforming an exothermic or endothermic process?
23. How might the products of the cracking be separated?
24. What are fossil fuels and how are they formed?
25. In a bomb calorimeter, does the reaction take place under conditions of instant
pressure or constant volume?
26. Mention a few advantages of diesel over petrol as a fuel.
27. Why does volatility decrease with increasing number of carbon atoms in different
fractions of petroleum ?
28. Why does the petrol-air mixture expand on ignition?
29. How does dehydroisomerization differ from dehydrocyclisation ?
30. What are petrochemicals?
31. What are major applications of petrochemicals?
[ANSWERS)
1. The decomposition of higher chain hydrocarbon molecules into simple, low boiling
hydrocarbons of lower molecular masses is called cracking.
2. The gasoline obtained directly from the fractionation of crude oil is called straight
run gasoline.
3. Petrol synthesised either by polymerization of low molecular mass olefins and alkanes
or form finely powdered coal and heavy oil is called synthetic petrol.
4. A process of bringing about structural modifications in the component of straight
run gasoline, with the object of improving its antiknock characteristics is called
reforming.
5. The ratio of the gaseous volume in the cylinder at the end of the suction-stroke to
the volume at the end of compression-stroke of the piston is called compression ratio.
6. Premature instantaneous ignition of fuel-air mixture in an I.e. engine, leading to
production of an explosive violence, is known as knoching.
7. Naphthalene < isooctane < n-octane.
8. The percentage of isooctane in a mixture of isooctane and n-heptane, which matches
the gasoline under test in knocking characteristics is termed as octane number.
9. The percentage of hexadecane in a mixture ofhexadecane and 2-methyl naphthalene,
which possesses the same ignition characteristics as the diesel fuel in question is
called cetane number.
10. Highest octane number: Isooctane.
Highest cetane number: n-hexadecane.
11. When ethyl alcohol is used as a fuel (alongwith petrol) for internal combustion engine,
it is called power alcohol.
12. Octane rating of alcohol is about 90 while that of gasoline is 60-70.
13. Blend possesses : (i) higher octane rating than gasoline alone, (ii) lesser starting
problems, (iii) capacity to absorb any traces of moisture.
14. Blend: (i) lowers the calorific value of petrol, (ii) may cause corrosion, since alcohol
is easily oxidised to acids.
15. When natural gas occurs along-with petroleum in oil wells, its is called wet gas.
16. Due to the inherent presence of some constituents in gasoline, its use in internal
combustion engine causes knocking thereby resulting in loss of efficiency. In order
to improve efficiency of petrol used in internal combustion engine, its octane number
is raised by adding tetra ethyl lead. This so-called leaded-gasoline possesses less
knocking tendency and improved efficiency as internal combustion fuel. Hence, leaded-
gasoline is used in internal combustion engines.
17. Cat cracker is used for cracking heavy oil fractions of petroleum in presence of suitable
catalyst. This method produces gasoline of high quality and in high yield.
18. Structure of :
CH 3 CH 3
I I 2, 3-dimethylpentane
CH 3 -CH-CH-CH2 -CH3
(Branched structure paraffin)
CH3-CH3-CH2-CH2-CH2-CH2-CH3 n-heptane
(Straight-chain paraffin)
Now we know that knocking tendency of: straight-chain paraffin> branched-chain
paraffin. so anti-knocking tendency (or octane rating) of branched-chain paraffin>
straight-chain paraffin. Hence, octane number of 2, 3-dimethylpentance (a branched-
chain paraffin with 5 C-atoms chain) is higher than that of n-heptane (a straight-
chain paraffin with 7 C-atoms chain).
19. TEL, used to improve the anti-knocking characteristic of an I.C. engine fuel (gasoline),
gets converted into finely divided lead oxide particles, which react with knocking-
causing hydrocarbon peroxides formed in the cylinder. This in-turn decreases the
chances of any early detonation (or knocking). However, deposit of these lead oxide
particles inside the cylinder is harmful to the engine life. Consequently, a small
quantity of ethyl bromide (C2HsBr) is also added to gasoline and this helps in the
simultaneous elimination of lead oxide in the form of volatile lead bromide alongwith
the exhaust gases.
20. The catalyst loses its catalytic activity during the process due to deposition of carbon.
The catalyst is, therefore, regenerated by burning carbon deposited on it.
21. It would be dangerous on a hot day. Moreover, if the petrol vaporises in the lines, a
bubble of vapour would prevent the petrol from flowing properly.
22. Endothermic, since the strong C-H bonds require sufficient amounts of energy to break
them. This energy is not retrieved by converting the bonds into double bonds during
reforming.
23. By fractional distillation.
24. The fossil fuels include coal, petroleum and natural gas. They are formed in dead
plants and animals, whose remains are subjected to heat and high pressures.
25. Constant volume.
26. Diesel engines are more efficient, give better fuel economy and produce only about
one tenth of CO than petrol engines.
27. The intermolecular forces of attraction decrease with decreasing molecular loss of
hydrocarbons.
28. It produces CO 2 (g) and water. The volume produced is greater than the petrol-air
mIxture, because 1 mole of petrol with x C-atoms gives x moles of CO 2 (g).
29. Drhydroisomerization involves dehydration, followed by a molecular rearrangement
to give a different structural isomer; while dehydrocyclisation involves
dehydrogenation, followed by a molecular rearrangement which converts an open-
chain compound to a cyclic compound.
30. Those derive from the crude oil or natural gas. They include light hydrocarbons
(ethene, butene and propene) obtained by fractional distillation or catalytic cracking.
31. They serve as basic building blocks for producing pharmaceuticals, agrochemicals,
polymers, dyestuffs, antiseptics, etc.
[ REVISION QUESTIONS)
1. (a) What are chemical fuels? Give complete classification of chemical fuels with
examples. (Tripura, 2K; PT, Dec. 2K; UPT, Jan. 01)
(b) What are different types of fuels? What are the characteristics of a good fuel?
(SV, Aug. 01; GGSlp, Dec. 2K)
2. (a) Give modern definition of fuels. How are they classified on the basis of their
utility?
(b) Mention the criteria for selecting good fuel. (Tripura,2K)
(c) Distinguish between solid, liquid and gaseous fuels. (Dibrugarh, Dec. 2K)
3. (a) What is meant by calorific values of a fuel?
(UPT, Jan. 01; VT, Aug; 2K, March 01, Aug. 01; RGT, May 01)
(b) Distinguish between gross and net calorific values offuel.
(MK, April 01; PT, Dec. 2K; UPT, Jan. 01; GGSlp, March 2K; Anna, July 2K)
4. Describe how the calorific value of a solid fuel is determined using a bomb calorimeter.
(vT, April2K, March 01, Aug. 01; Sv, Aug 01; Tripura, 2K; MK, April 01; PT,
Dec. 2K; Ku, June 2K; UPT, May 01; GGSlp, Dec. 2K)
5. What is crude oil ? Write short note on refining of crude petroleum. What are the various
fractions obtained from petroleum? Mention the industrial uses to which they are put.
(Tripura, 2K; MD, Dec. 99; Jan. 01; KU, June 2K; Amravati, May 01;
Dibrugarh, Dec. 2K)
6. (a) What is meant by cracking of petroleum? Explain fluidized-bed catalytic method of
obtaining gasoline.
(Dibrugarh, Dec. 2K; Sindri, May 01; VT, April2K; MD, May 2K, May 01; PT,
Dec. 2K; RGT, May 01,' Anna, Nou. 2K; Amrauati, May 01)
7. (a) What are the advantages of catalytic cracking process? Describe, with a neat diagram,
the fixed-bed catalytic cracking process. (Anna, July 2KJ
(b) Differentiate between thermal and catalytic cracking.
(c) What are the advantages of catalytic cracking over thermal cracking?
(Dibrugarh, Dec. 2K)
8. (a) What is reforming of petrol? How does reforming increase octane number? Give
any two reforming reactions. (VT, Aug. 01; MD, May 2K; Jan. 01; Ku, June 2K)
(bl What is meant by knocking in IC engine? Explain the mechanism of knocking in
chemical terms. (Amravati, May 01; VT, March 01, Aug. 01)
9. What is meant by knocking? How is it related to chemical constitution? Describe the
function of TEL. Explain octane number and cetane number. (GGSlp, Dec. 2K)
10. (a) Describe any two methods used for the synthesis of gasoline.
(MD, Dec. 98; Dibrugarh, Dec. 2K)
(b) Describe the manufacture of gasoline by Fisher-Tropsch method.
(GGSIP March 2K, Dec. 2K)
11. Define octane number and cetane number. What are the structural features of
hydrocarbons in unlead petrol and diesel ? What are the structural factors that promote
its high value?
(Sambalpur, July 01; MK, April 01; Ku, June 2K; MD. May 2K,
Jan. 01, May 01; SY, Aug. 01)
12. (a) What is the significance of octane number and cetane number and for which these
are used? How these can be improved? (Ku, Jan. 01)
(b) Why is C2H 4 Br2 added, when TEL is used as an antiknock? (RGT, May 01)
(c) What types of compounds, now-a-days, are being added to petrol to improve octane
rating? (MD, May 01)
13. Distinguish between the following:
(i) Grobs and Net calorific value of a fuel.
(ii) Thermal cracking and catalytic cracking.
(iii) Fixed bed and fluidised cracking.
(iv) Cr~cking and reforming.
(vl Octane number and cetane number.
(vi) Knocking and Antiknocking.
14. (a) Enumerate the characteristics of a good fuel.
(b) Differentiate between gross calorific value and net calorific value.
(c) A coal sample has the following composition by weight C = 90%; 0 =3.0%; S =6.5%;
N = 6.5%, and a$h = 2.5%. Net calorific value ofthe coal was found to be 8;490
kcal/kg. Calculate the percentage of hydrogen and gross calorific value of hydrogen.
[GGSIPU, 1st Sem., B.Tech, Feb.-March, 2000J
15. (a) What is meant by knocking? How is it related to chemical constitution? Describe
the function of TEL. Explain octane number and cetane number.
[GGSIPU, 1st Sem., B.Tech, Feb.-March, 2000J
16. (a) Describe the manufacture of gasoline by Fisher-Tropsch method.
(b) Differentiate between chemical fuel and nuclear fuel.
(c) Write notes on : (i) Fischer-Tropsch process (ii) Octane number.
17. With the help of a neat diagram, explain how the calorific value of a fuel can be
determined by static oxygen bomb calorimeter. What are the fuels used for the
determination of water equivalent of bomb calorimeter and why?
[GGSIPU, 1st Sem., B. Tech., Dec., 2000]
18. Explain the process of catalytic reforming. Give examples of the different type of
reactions taking place in the process.
19. What is aromatisation ? Explain the possible products obtained from the aromatisation
of n-octane.
20. Write a short note on use of hydrocarbons as fuels.
21. (a) Describe the moving bed catalytic cracking method to obtain petrol from crude oil.
Why this method is preferred to fixed bed catalytic cracking method.
(b) Write short note on bomb calorimeter. (GGSIPU, March 2001)
22. (a) Why should an ideal fuel have moderate ignition temperature?
(b) What is power alcohol? What are its merits over petrol as a fuel?
(c) What do you know about leaded and unleaded petrol.
23. (a) What do you understand by centane number of fuel ? Distinguish between high speed
diesel (HSD) and low speed diesel (LSD).
(b) What is power alcohol ? How it is obtained from molassies.
(c) Write short note on catalytic converters.
(d) Discuss how octane number of gasoline and cetane number of diesel oil are improved
by changing the compositions of an oil.
24. What is cracking of Petroleum? Explain fluidized catalytic cracking.
25. What is meant by knocking in Ie engines? Explain its mechanism.
(VTU, B.E., March 1999)
26. What are chemical fuels? Give complete classification of chemical fuels with examples.
(VTU, B.E., August/ Sept. 1999)
27. (a) Describe how the calorific value of a solid fuel is determined using a bomb calorimeter.
(b) How in gasoline obtained by fludized bed catalytic cracking process?
(VTU, B.E., April 2000)
28. (a) Define calorific value of a chemical fuel. How in calorific value of a solid fuel
determined using bomb calorimeter.
(b) What is reformation of Petrol ? How does reforming increase octane number? Give
any two reforming reactions. (VTU, B.E., August 2001)
29. (a) Explain the experimental method of determining calorific value of gaseous fuel.
(b) A coal sample with 93% C, 5% H2 and 2% ash in subjected to combustion and a
bomb calorimeter. Calculate the gross and net bomb calorimeter. Calculate the gross
and net calorific value given that mass of coal sample taken in 0.95 mass of water
in the copper calorimeter in 2000g, water equivalent of calorimet!=lr in 700 g, rise in
temperature of water. 2.8°C and latent heat of steam in 587 co]Jg. Specific heat of
water = 1 cal g/O°C. (VTU, B.E., August 2002)
30. (a) Give the classification of fuels with examples.
(b) Explain the process offludised bed catIytic cracking of petroleum.
(c) Dscribe the bomb calorimetric method of determination of calorific value of a solid
fuel.
(d) Calculate the calorific value of a coal sample from the following data :
Mass of coal 1.0 g, water equivalent of calorimeter 2.0 g. Specific heat of water:
4.187 kJlKg-l C-l and rise in temperature 4.8°C. (VTU, R.E., Jan. / Feb. 2003)
31. (a) Define gross and net calorific value. Explain bomb calorimetric method of determining
calorific value of a solid fuel.
(b) Calculate gross calorific value and net calorific value of a coal sample from the
following data.
Weight of coal sample taken =8.5 x 10-4 kg.
Weight of water taken in the calorimeter = 3.5 kg
Water equivalent of calorimeter = 0.5 kg
Initial temperature of water =25°C
Final temperature of water = 27.5°C
Percentage of H2 in the coal sample = 2.5
Latent heat of steam = 2455 kJ/kg (VTU, R.E., August, 2004)
32. (a) Define gross and net calorific value of a fuel. Describe how the calorific value of a
solid fuel fuel is determined using bomb calorimeter.
(b) Calculate the gross calorific value of a coal sample from the following data :
Weight of total sample taken =5.5 x 10-3 kg.
Weight of water taken in the calorimeter = 2.5 kg
Water equivalent of calorimeter = 0.5 kg
Initial temperature of water = 29°C
Final temperature of water =28°C (VTU, R.E., Feb. / March 2005)
SOLAR ENERGY
SYLLABUS
Photovoltaic cells-Introduction, definition, importance, working of a PV ce~l; solar grade
silicon-physical and chemical properties of silicon relevant to photovoltaics, production of
solar grade (crystalline) silicon and doping of silicon.
lB.l INTRODUCTION
The sun is the ultimate source of energy for the planets revolving around it. It is believed
that the star (sun) is a store of unlimited amount of energy, which is generated due to nuclear
fusion reaction of hydrogen into other elements taking place in the sun. It radiates energy in
the form of heat and light. The heat energy evaporates sea water into clouds and thus causes
rain. The rain water flows into rivers, streams and water falls, etc. and ultimately goes back
to the sea. The mechanical energy of flowing water is used to run the turbines that generate
electricity. The hydroelectric power thus generated can playa significant role as a source of
energy. The heat energy from the sun also causes winds, tides and ocean waves. These are
again the renewable sources of energy in the future.
Plants absorb energy from the sun in the form of a light through the process of
photosynthesis. Carbon dioxide and water combine in the presence of light and chlorophyll
(green colouring matter in plants) to form carbohydrates. These carbohydrates are the buildings
blocks for the plants and source of energy as food for the animals. Plants serve as food for
animals and also supply wood which act as a fuel again. Plants as well as animals die and
decay and change to coal, petroleum and natural gas. These are the sources of energy of the
present civilisation but these are depletable sources. It has been summed up in Fig. 1.7 that
sun is the primary source of energy for all the available and future sources of energy.
Increasing consumption of energy to meet the demands of civilization has led to many
environmental issues, e.g., air and water pollution, spread of toxic materials, scarring of land
by strip mining, etc. In the last few year, clear signals have immerged about increased
Solar Energy 41
commitment to save energy. It has been evident that the stock of fossil fuel is limited and'
may be exhausted within 100 years leading to energy crisis. Hence it is time to find out and
develop alternative energy sources which should be without delay. Solar energy is one viable
alternative. The total energy output of the sun is estimated at 3.45 x 1023 Kwh. India is located
between 7° Nand 37°N latitudes and the prospect of using solar energy is very bright indeed.
~e~
~~C-au-s-es-l-'a~in-a-n~d--~ Causes winds
Photosynthesis tides and
thus streams, Tlvers in plants
water falls etc. ocean waves
Renewable Food Renewable

energy energy
sources sources
Depletable Renewable
energy energy
source source
Marine animals
fossilised to
petroleum and
natural gas
Depletable
energy source
Fig. 1.1. Sun as the ultimate energy source.

IfIndia can tap one percent of the incident radiation, it can generate many times the energy
of its actual requirement at present. The most convenient application of solar energy is in
heating of buildings and providing hot water.
Solar energy can be utilized in two different ways. One is to convert it directly into
electricity by making use of photovoltanic devices. Solar cell made of silicon is the most elegant
method of converting solar energy into electricity which can operate all electrical devices for
lighting, domestic applications, tele communication, signaling, water pumping etc. This system
in generally known as photovoltanic system. About 66% of the total energy used in the industry
is in the form of heat which is provided by burning fossil fuels or electricity. Conventional
fossil fuels may be saved by producing part of the process heat by solar energy.
m.2 ALTERNATE SOURCE OF ENERGY
Different sources of energy are :
(i) Heat energy: The requirements of energy are mainly met by the combustion of fuels
such as coal, hydrocarbons (kerosene, petrol, natural gas, cooking gas, etc). These are known
as fossil fuels since they were formed from the remains of extinct life forms when subjected to
the high temperatures and pressures in the interior of the earth. Fossil fuels are mainly used
for transportation (bus, trains, tractors, etc,) and production of electricity. In addition, charcoal,
wood and cow dung; and recently gobar gas are being developed as a source of energy in a
rural area. In all these cases the chemical reaction is the exothermic combustion and the heat
of reaction is converted into other forms of energy. In the production of electricIty. foJ' example>
the heat is used to convert water into steam, which runs a turbine that generates electncity.
The transformation is thus:
Chemical Mechanical
Stored 1--t·L':H~e~at:..JI----••1 Encrg,v ---.!l<:leetriclty I
EIlI!l'!~Y
(ii) Mechanical energy: Another important source of energy is the mechanical energy
in water, when it is rushing at high velocities (kinetic energy), hydroelectric power, statiolls,
such as at Bhakra or Shivasamudaram utilize the kinetic energy of fast moving water to run
turbines that generate electricity.
(iii) Nuclear energy: Man has also learnt to harness the energy stored in the nucleus of'
the atom and nuclear power stations are being set-up in the country, such as at "Tarapul'
(Maharashtra), Kota (Rajasthan) and Kalpakkam (Tamil Nadu).
(v) Tidal waves, Ocean currents, the hot gases and hot steam that rushes out of the
earth's interior in the form of gysers, hot springs, etc. (known as geothermal sources) are yet
other forms of energy awaiting exploitation.
(iv) Wind energy: Wind is another SO'lrce of energy which is not yet fully tapped
significantly in India.
Consumption of energy: The standard of life and the prosperity of a nation is judged to
a large extent by the amount of electrical power consumed by its population. India is one of
those countries which are very backward in this respect. Coal has been the main sourcE' and
it is only during the last ten years that adequate crude oil (in Assam, GUJarat and from
underneath the ocean surface in the Arabian sea) hus been found to meet more than half (about.
70%) pf oil demands without imports. Hydroelectricity has been developed considerably since
independence. Even then demands to increase with development and the search for additional
sources of energy must continue.
IB.2 COMPOSITION OF SOLAR ENERGY
Nuclear fusion reactions in the interior of the sun continuously liberate enormous amount
of energy. This energy is radiated by it in all directions in space. The earth and other solar
planets receive only a small fraction of this energy. It is estimated that the earth directly
receives only 0.000000045792% of the sun's total energy output. The radiation from the sun,
besides heat (or infra-red radiation) and visible light, also carries energy in the form of
ultraviolet and gamma rays.
The solar energy reaching the periphery of the earth's atmosphere is considered to l)t~
constant fin' all practical purposes, and is known as the solar constant. The exact vahw of
the solar constant is not known with certainty because it is difficult to take accurate
measurements. However, it is estimated to be approximately 1.4 kJ per second per square
metre. or 1.4 kW/m 2 . The value of solar radiation received on a unit area exposed
perpendicularly to the rays of the sun at an average distance between the sun and the earth.
A little less than half of the solar energy, approximately 47% that strikes the periphery of
the earth, reaches its surface. The atmosphere absorbs a significant portion of the solar energy
that percolates down towards the earth's surface is mostly in the form of heat (or infra-red
radiation) and visible light.
Solar Energy 43
Nearly, one third of the sunlight consists of infra-red while the rest is in the form visible
light. Although infra-red radiation is not visible to us, it heats up the objects that lie in its
path. We can also say that all bodies that are hot, radiate energy in the form of infra-red rays.
However, the wavelength of infra-red emitted by a hot body depends on its temperature. Higher
the temperature of body, shorter is the wavelength of infra-red emitted by it. Therefore,
wavelengths of infra-red emitted by it. Therefore, wavelengths of infra-red radiation emitted
by a hot body are much longer than that present in the sunlight. This is because the
temperature of the sun is very high.
Solar energy is utilised in many activities like drying of grain and clothes, obtaining salt
from seawater, etc. However, we have now developed technology that enables us to harness
solar energy in a more efficient and convenient manner. The devices commonly used for
harnessing solar energy are solar cookers, solar water heaters, solar water pumps and
photo voltaic cells or solar cells. these are known as sG}ar energy devices. Solar energy devices
can be broadly classified into two categories on the basis of their principle of working. In one
type of device, the solar energy is collected in the form of heat, for example, solar cookers
and solar water heaters. In the other type solar energy is converted into electricity, like in
a solar cell.
IB.3 SOLAR CELLS (PROSPECTS)
The devices that convert solar energy directly into electricity are known as solar cells.
Direct conversion of solar energy into electricity is much simpler as compared to that through
heating systems. A little over hundred years ago, it was found that when sunlight falls on a
wafer thin sheet of selenium, electricity is produced. However, a solar cell made of selenium
wafer could covnert only 0.7% of the solar energy into electricity. This output was so small
that it was considered to be impractical to use it for generating electricity.
The first practical solar cell was fabricated in 1954. It could convert about 1% of solar energy
into electricity. Modern solar cells have efficiencies as high as 25%. Silicon is the most commonly
used material to manufacture solar cells. Silicon has the advantage that it is
environmental friendly and is also available in abundance. Research and development
efforts throughout the world have resulted in a considerable reduction in the cost of production
of solar cells in the last fifty years. Recently, solar cells have been designed that consist of a
number of thin layers of silicon. These multilayer silicon solar cells have been found to
convert energy from both the visible, as well as the infra-red radiation into electricity.
This has increased the efficiency of solar cells to a great extent.
A typical solar cell consists of a 2 cm square piece of almost pure silicon. A 2 cm 2 single
solar cell can produce about 0.7 watt of electricity when exposed to sun, which also is quite
small. However, a large number of solar cells combined together can produce enough electricity.
When a large number of solar cell are used together, the arrangement is known as
solar panel.
Prospects
Solar cells provide a clean, pollution free and environment-friendly source of electricity.
Another advantage is that these can be used anywhere as a self-generating source of electricity.
Yet, at present solar cells are being used for a limited purpose, mainly because of high cost for
their installation. Although silicon is second most abundant element found on the earth,
availability of special grade silicon required for making solar cells is only limited. The technology
to obtain silicon in pure form, too, is quite expensive. Another factor that adds to the cost of
solar cells is the material used to connect them in a solar panel. Usually, the best conducting
metal, that is silver, is used for this purpose. Otherwise, a substantial fraction of electricity
generated by solar cells will get used up in overcoming the resistance of the connectors.
A major practical problem associated with the use of solar cells is availability of efficient
systems that can store electricity generated by them and make it available when required.
The electricity produced by solar panels is conventionally stored by using it to charge storage
batteries, which can deliver only direct current or DC. To operate devices that required
alternating current or AC, the direct current (or DC) produced by batteries needs to be
converted into AC that further adds to effciency, as well as to the cost.
Uses
In spite of low efficiency and high cost, solar cells are being extensively used for many
purposes. (i) Solar cells are used as the main source of energy in all artificial satellites.
(ii) They are used as a source of electricity for radio or wireless transmissions, at TV relay
stations, traffic lights and research centres located in remote areas. (iii) You might have seen
calculators and toys fitted with solar cells. (iv) The use of solar cells as a source of electricity
for domestic purposes is also becoming popular day by day.
IBA RENEWABLE AND NON·RENEWABLE SOURCE OF ENERGY
Fossil fuels are sources of energy that nature has developed over the ages and at present
it is being consumed at a rate much faster than their rate of formation. It is estimated that
fossil fuels will be consumed before the middle of the 21st century. Fossil fuels are termed as
"depletable" or "non renewable" sources of energy for this reason.
On the other hand, the solar energy, energy harnessed from flowing water, winds, tides,
ocean waves and biogas are some energy 60urces that are directly or indirectly derived from
the sun. These sources can be harnessed as long as the earth continues receive light and heat
of the sun. Nuclear energy and geothermal energy are examples of some other sources of
energy that are likely to be available for a longtime. But these do not relate to the energy of
the sun. These sources of energy are, therefore, classified as Renewable Sources.
It is important to identify "alternate source of energy". Below is a partial list of such possible
sources which are known as renewable sources of energy.
Sources Renewable (non depletable)
or non renewable (depletable)
1. Biomass Renewable
2. Wind Renewable
3. Ocean waves Renewable
4. Tidal waves Renewable
5. Solar energy (direct utilisation) Renewable
6. Nuclear fusion (This is to create Renewable since hydrogen would be the
energy the way stars produce energy) prime source and is available in plenty.
Note: Nuclear fission power is a non-renewable source of energy.

IBA SOLAR CELL
A solar cell or solar battery is basically a P-N junction diode which converts solar energy
into electrical energy. It is also called a solar energy converter and is simply a photo diode
operated at Zero bias voltage.
Construction: A solar cell consists of a P-N junction diode generally made of Ge or Si. It
may also be constructed with many other semiconducting materials like gallium arsenide (GaAs),
indium arsenide (lnAs) and cadmium arsenide (CdAs). The P-N diodes so formed is packed in
Solar Energy 45
a can with glass window on top so that light may fall upon P and N type materials. The thickness
of the P-region is kept very small so that electrons generated in this region can diffuse to the
junction before recombination takes place. Thickness of N-region is also kept small to allow
holes generated near the surface to diffuse to the junction before they recombine.
A heavy doping of P and N region is recommended to obtain a large photo voltage. A nickel
plate ring is provided around the P-Iayer which acts as the positive output terminal. A metal
contact at the bottom serves as the negative output terminal. The schematic symbol of a solar
cell is shown in Fig. 1.8 (b). The inward arrow indicates the incoming light.
Sun light -I
Glass \
Metal ring
!l . ....
..
Crll ~ P
~
~ Ge
,. ...... .... .. .... "
N
.
~
-
l
Metal contact
(a) (b)
Fig. 1.8. (a). Solar cell circuit, (b) Solar cell symbol.
Working: The working of solar cell may be understood with reference to Fig. 1.8 (a) and
1.8 (b). When light is allowed to fallon P-N junction diode, photons collide with valence electrons
and impart them sufficient energy enabling them to leave their parent atoms. Thus electron-
hole pairs are generated in both the P and N-sides of the junction, as shown in Fig. 1.8 (a).
These electrons and holes reach the depletion region W by diffusion Fig. 1.8 (a), and then
separated by the strong barrier field existing there. However, the minority carriers, electrons
in the P-side, slide down the barrier potential to reach the N-side and the holes in the N-side
move to P-side, as shown in Fig. 1.8 (b). Their flow constitutes the minority current which is
directly proportional to the illumination and also depends on the surface area bring exposed
to light.
The accumulation of electrons and holes on the two sides of the junction gives rise to an
open circuit voltage VoC' which is a function of illumination.
However, significant developments have taken place in the last few years. New types of
cells have been developed, innovative manufacturing processes introduced, conversion
efficiencies of existing types increased, costs reduced and the volume of production steadily
increased. The present anr:ual world production of photovoltaic devices is already about 60
MWp*, while production in India is about 1.5 MWp. As a result of the above developments,
solar cells are now being used extensively in many consumer products and appliances,
and it is possible that in the future they may become one of the important sources of power
for providing small amounts of electrical energy for localized use, particularly in remote
locations.
IB.5 THE SINGLE CRYSTAL SILICON CELL
The first solar cells were made in the fifties from single crystal silicon. Even today silicon
is the material generally used for making most cells. Single crystal silicon cells are thin wafers
about 300 ~lm in thickness, sliced from a single crystal of p-type doped silicon (Fig. 1.9). A
Metal electrode finger
on front side
- 0.2 J.lm "'--.--L

T ~===========:::::=====9
-300 ~lm
P-silicon Metal electrode

on backside
Fig. 1.9. Cross-sectional Diagram of a Silicon Cell.
shallow Junction is formed at one end by diffusion of the n-type impurity. Metal electrodes
made from a Ti-Ag solar are attached to the front and back side of the cell. On the front side,
the electrode is in the form of a metal grid with fingers which permit the sunlight to go through,
while on the back side, the electrode completely covers the surface. An anti-reflection coating
of SiO, having a thickness of about 0.1 ~m, and a thin transparent encapsulating sheet are
also put on the top surface to complete the assembly. A typical cell develops a voltage of 0.5-1
V and a current density of 20-40 mAlcm 2. In order to obtain higher voltages and currents,
individual cells are fixed side by side on' a suitable back-up board are connected in series and
parallel to form a module. In turn, a number of modules are interconnected to form an array.
Earlier the cells used to be circular in shape with diameters ranging from 6 to 15 cm. Now
they are often rectangular in shape, resulting in more compact modules. Apart from single
crystal silicon, silicon solar cells are now also made in large numbers from polycrystalline silicon
and amorphous silicon.
IB.6 Principle of Working of a Solar Cell
Two Important steps are involved in the principle of working of a solar cell. These are,
1. Creation of pairs of positive and negative charges (called electron-hole pairs) in the
solar cell by absorbed solar radiation.
2. Separation of the positive and negative charges by a potential gradient within the
cell.
For the first step to occur, the cell must be made of a material which can absorb the energy
associated with the photons of sunlight. The energy (E) of a photon is related to the wavelength
(A) by the equation
E = he/A (1)
where h = Planck's consta It = 6.62 x 10-27 erg-s

and e = velocity of light = 3 x 108 mls.
*The term 'peak watt' or 'watt peak' (Wp) is used for power produced by a photovoltaic device around noon on a
clear day with the beam radiation falling normally on the device.
Solar Energy 47
Substituting these values, we get
E = 1.24/11. (2)
where E is in electron-volts (eV) and Ais in /Jm.
The only materials suitable for absorbing the energy of the photons of sunlight are
semiconductors like silicon cadmium sulphide, gallium arsenide, etc. In a semiconductor, the
electrons occupy one of two energy bands-the valence band and the conduction band. The
valence band has electrons at a lower energy level and is fully occupied, while the conduction
band has electrons at a higher energy level and is not fully occupied. The difference between
the energy levels of the electrons in the two bands is called the band gap energy Eg . Photons
of sunlight having energy E greater than the band gap energy Eg are absorbed in the cell
material and excite some of the electrons*. These electrons jump across the band gap from
the valence band to the conduction band leaving behind holes in the valence band. Thus electron-
\. hole pairs are created.
The electrons in the conduction band and the holes in the valence band are mobile. They
can be separated and made to flow through an external circuit (thereby executing the second
step of the photovoltaic effect) if a potential gradient exists within the cell. In the case of silicon,
the potential gradient is obtained by making the cell as a sandwich of two types of silicon, p-
type and n-type. Silicon of p-type is silicon 'doped' with some atoms of boron, while silicon of
n-type is silicon 'doped' with some atoms of phosphorus. The energy levels of the conduction
and valence bands inp-type silicon are slightly higher than the corresponding levels in n-type
silicon. Thus when a composite of the two types of'silicon is formed, a jump in energy levels
occurs at the junction interface. This potential gradient is adequate to separate the electrons
and holes, and cause a direct electric current to flow in the external load.
In a silicon cell, the junction is the thin region separating the n-type and p-type portions.
Since the basic material is all silicon, such a junction is more specifically called a
•
Teo nduction band
~
t::
.S
.....
c:I
c:I
~
~
.
\
Elcctron-
hole pair
Eg
/ lv"~
:...
:...
~
~
~
nee band
~ 0
Front side rti, t I---

0
Junction
p-typ'
Backside
n-type
t Externalload I Current
Fig. 1.10. Principle of Working of a Solar Cell.
'"The excess energy (E - Eg) is lost as heat.

homojunction. Solar cells can also be made from dissimilar materials. For example, in one
type a layer of copper sulphide is deposited on a layer of cadmium sulphide, the junction being
formed along the contact between the two materials. Such a junction is called a heterojunction.
IN.7 PHOTO-VOLTAIC CELL
Becquerel in 1839 discovered that when a pair of electrodes is immersed in an electrolyte
and light is allowed to incident on one of them, a potential difference is created between the
electrodes. This phenomenon is called photo-voltaic effect. Devices based on this effect are
known as photo-voltaic cells.
r----Definition----------------------------------------------------------~
Thus photo voltaic cells are the devices in which light energy is used to create a potential
difference. The potential difference so developed is directly proportional to the frequency
and intensity of incident light.
Construction and Working
A basic photo voltaic cell, consists of a piece of
semiconducting material bonded to a metal plate.
Materials like selenium and silicon are mostly used for
Metal
preparing photovoltaic cells.
When light is made to fall on semiconducting
material, valence electrons and holes are liberated from
its crystal structure. The electrons so liberated move R
towards the metal plate whereas holes flow in opposite
direction. Thus a potential difference is created between
the semiconducting material and the metal plate.
Fig. 1.11 ..
Consequently a conventional current flows in the
external circuit through a load resistor R as shown in
Fig. 1.11.
In an actual form of photo-voltaic cell a
thin metallic film of silver, gold or platinum
is deposited on a semiconducting layer like
cuprous oxide (Cu 20) or iron selenide. The ~~===:::::==~
wh ole arrangement is then attached to a CU 20 _- Q.-r
metal base plate (say, copper), as shown in R
Fig. 1.12. eu plate
When external light is allowed to fall on
metallic film F, it penetrates easily and at
the barrier layer between the metallic film
Fig. 1.12. Photo-voltaic cell.
and the semiconductor, photo-electric
emission occurs. The photoelectrons so emitted from the layer, move towards the metallic
film. Consequently, the metallic film F becomes negatively charged and the copper base plate
positively charged. Hence a potential difference is developed between the two and a current
flows in the external circuit. The strength of the current is proportional to the intensity of
light and flows without any bias, i.e. out any external source of e.m.f.
These cells are used as
Solar Energy 49
(i) Operation of relays
(ii) Photographic exposure metre
(iii) Direct reading illumination metre.
IB.8 PHOTOVOLTAIC CONVERSION
The devices used in photovoltaic conversion are called solar cells. When solar radiation
falls on these devices, it is converted directly into dc electricity. The principal advantages
associated with solar cells are that they have no moving parts, require little maintenance,
and work quite satisfactorily with beam or diffuse radiation. Also they are readily adapted for
varying power requirements because a cell is like a 'building block'. The main factors limiting
their use are that they are still rather costly and that there is very little economy associated
with the magnitude of power generated in an installation.
Different technologies have been used for the commercial production of solar photovoltaic
cells. The important techniques are: Single crystalline silicon, Poly-crystalline silicon,
semiconductors and amorphous silicon.
Solar panels or a large number of solar cells are connected in series-parallel combination
to obtanied the required amount of power. These cells when exposed to solar radiation give
direct current (DC) which can be converted in to AC using inverters. Photovoltaic cells can
generate power ranging from a few watts to hundreds of megawatts. This power can be used
to operate space satellities, space air crafts and aeroplanes etc.
IB.9 IMPROTANCE
Solar power has now started replacing conventional power in some area with the
development of more efficient solar cells to tap this clean source of almost limit less energy.
(i) In Germany, bus stops, (i) shelters, ticket machines and speed warning signs are powered
by photo voltaic cells. The solar panels store the solar energy during the day and deliver light
at night. Light emitting diodes and low energy lamps are used which use the power stored in
the panels. These cells are non polluting. They have been able to match the use of other
renewable energy sources.
(ii) Manufacture of solar cells from mono-crystalline silicon in the most common technology
in India because due to lower cost of refining and casier availability of its basic raw material.
The public sector units CEL and BHEL are the major manufacture of solar cells in India.
(iii) Thin film technology is another technology that holds promise for replacing
mono crystalline silicon as the future cell material. CdslCdTe films are the most likely to be
used. Most PV systems are provided with an energy storage medium for storing the energy
generated from the PV array during the sunlight day, so that the same can feed the load during
night time.
(iv)Lighting using PV has always been a popular application for remote, unelectrified rutal
areas. Such lighting is in the form of street lighting, domestic light and portable lantherns.
Lighting is done using compact fluorescent lamps for 5 watts, 9 watts or 11 watts for domestic
and street light respectively.
(v)PV systems have now been used to improve rural communication other applications of
PV for communication purposes are powering microwave repeater station located at till tops.
(iv) PV is also used for deep well pumping system. A photovoltaic system for supplying
drinking water is Gastalled in a village in Rajasthan as part of the National Drinking water
50 Essentials ofEngineenng Chemist,.,v
rnl."sion. They have been designed to pump water from depths 20 to 100 metres as shown in
Fig 1.1:3.
StoJ'a~e
bmk
Suhnl"l ~lhl ..
thtlllj'"'II(lt,1l
Fig. 1.13. A Phot()\'(J\talc Water-pumping System.
With all the above applications and mam' more under development, it is quite E~vidGnt that
PV power is playing an increasingly 1l11j1ortant role as a source of energy, specially t()l' rural
electrification. The rising cost of com'£'ntional energy, the reducing cost of photovoltaic
technology and incentives given by Governments are the various factors which are inf1uencing
the use of photovoltmc cell as a viable source of energy.
18.10. SILICON SOLAR CELL
The silicon solar cell, developed for the space programme, consists of a sandwich of n-
type and p-type silicon semi conductors. The charge seperation in developed across the junction
between them, p-type silicon conducts +ve charges while n-type silicon conducts -ve charges.
The silicon cell produces electricity, but is quite expensive, since very high grade crystalline
Si is reqmred. The efficiency of conversion of light in 10 to 1f)(/r. With innovation in
manufacturing processes and more advanced technology, the prices are likely to he reduced.
Silicon cell are of two type, (a) n-type silicon cell (b) p-type silicon cell.
(a) n-type silicon cell (Semi-condutor): When Si lattice contains an impurity of As,
whi.ch contains 5 electrons in its outer shell, four of these electrons forms bonds with Si while
the fifth electron in available for conducting current. Such solids are called n-type semi
conductors (negative charge flows).
Solar Energy 51
p-type Silicon Cell (Semi-conductor) : When Si lattice contain some atom of Indium
(In), with three electrons in the outer shell, the covalent bonding is incomplete. 80l1W sites
being vacant, which then constitute positive (+ve) holes. If these holes are filled with a(~jacent
electrons, they form other holes and by migration in this way, they carry current. Sm:h solids
are called p type silicon cells or semiconductors.
Silicon cells are made by growing large crystal of pure silicon containing definite quantities
of boron under controlled conditions of temperature and pressure. The large crystals so grown
are sliced into wafers and phosphorous is added as impurity in a diffusion process. As a result
p-n type of junction is formed.
The photons falling on the doped wafer cause positive and negative charges to be creat.('!d
Because p-n junction is capable of conducting in one hI' 1~L\nhghiJ
direction only, a flow of electric current takes place in
one direction. The potential difference so created between
the two sides of the wafer can be used as a source of
electric power.
Different technologies have been used for the
commercial production of solar photovoltaic cells. The
important techniques are: (a) Single crystalline silicon
(b) Polycrystalline silicon, (c) Semi conductors (such as
gallium arsnide) and amorphous silicon. Cells are made Fig. 13. Solar cell for generatlOll (II
from these materials by growing ingots, casting molten electricity.
material, growing crystals and drawing ribbons from them or by depositing thm films of atomc:
on glass or metallic sheet or fabricated multilayered devices.
(a) Single crystalline silicon : It is an excellent technology with a good efficiency of
conversion (13 - 15%) and is stable too. The cost of manufacture is however, higher
because of loss or wastage during slicing of wafers. Another disadvantages in that
the round cells produced cannot be efficiently laid in a module. With recent advances
in technology higher efficiency cells (upto 20%) have been produced.
(b) Poly crystalline silicon: It has advantages of the single crystal silicon but its efficiency
is lower, its cost is high. Polycrystalline silicon polyvoltaic cells are made from
compound semi conductors with small cyrstal grain size. Materials used are calcium
telluride or copper indium diselenide. These cells are made by thin film tPchniqUl"
where compounds are deposited as thin films over large areas.
(c) Ribbon silicon: It has an efficiency of 10 - 12.5%, does not requires slicing and hence
its cost of manufacture is low because oflesser wastage.
(d) Amorphous silicon: Its efficiency of conversion is low (4.0 - 8.0%). It enables us high
automation and rapid production of cells. A major disadvantages in these cells is that
they become unstable because of charge trapping.
The single crystalline silicon cells show improved efficiency as compared to other cells,
therefore these cells are likely to be most suitable in near future.
Originally, solar cells were produced mainly for space applications. Now solar cells arc
manufactured for terrestrial use by using highly automated and expensive equipment. The cost
is high because raw materials used are also expensive. But with advancement in technology and
skill. the module cost per watt ofPV power has now been reduced considerably. They have been
used in street lighting, village electrification, microwave telecommunications links, railway signal
systems. power sources for water pumps, irrigation systems and other agriculture applications.
IB.ll PROPERTIES OF SILICON
Silicon is the most abundant element in earth's crust after oxygen as silica (sand or quartz)
and silicates. Silicon and germainum both belong to group 14 of the Periodic table. The electronic
configuration is given below:
Silicon (Si), Atomic number 14, [Ne] 3s 2 3p2. It has four electrons in its outermost shell,
Germanium (Ge), Atomic number 32, [Ar] 3s 2 3p2. It has four electrons in its outermost shell.
Silicon is used as n-type or p-type semiconductors when doped with group 15 or group 13
elements of the periodic table respectively. Both Si x Ge are extensively used in very pure
forms in devices. which are the basis of whole electronic industry including computer hardware.
Silicon is very important component of ceramics, glass and cement. It is added to steel or iron
as such or more usually in the form of ferro silicon to increase its resistance to attach by acids.
Very pure silicon is used to Computer chips. Its alloys such as silicon bronze and
manganese silicon bronze strength and hardness even greater than steeL
Germanium has largest use in transistor technology, in making transistors ane! othel'
semiconductor devices. It is transparent to infrared light and therefore is also used for making
prisms and lenses and windows in infrared spectrophotometers and other scientific apparatus.
IB.14 PRODUCTION OF SOLAR GRADE SILICON
Silicon is isolated commercially by heating silica with carbon or calcium carbide. Pure silicon
is obtained either by the thermal decomposition of SiH4 or by the reduction of tetrachloride
with sodium.
Si0 2 + 2C ~ Si + 2CO; SiCl4 + 4Na~ Si + 4NaCI
SiH4 ~ Si + 2H2
Exceedingly pure silicon, that is required for use as semiconductor, may be prepared by
purifying the element by zone refining.
(i) Silicon exists in two forms namely amorphous and crystalline. Amorphous silicon is
a dark-brown hygroscopic powder having asp. qr. 2.35. The crystalline variety give:,;
pale yellow crystals having a density of 2.5. Structurally, there is no difference between
the two forms, both have the diamond structure.
(ii) It is not attacked by water or any single acid. But it is acted upon by a mixture of
nitric acid and hydrofluoric acids and also by concentrated solution of alkali hydroxide
and fused carbonate.
Si + 2 KOH + H 20 ~ KzSi 0 3 + 2H2 t
Si + Na2C0 3 ~ Na2 Si0 3 + C
(iii) Silicon is employed as a de-oxidizer.
(w) Silicon forms a number of hydrides which are analogous to hydrocarbons.
(v) Being a semiconductor with a few electrons, solar cell can be made by doping
crystalline silicon with elements such as boron and phosphours inorder to increase
the conducting capacity ofthe material.
(vi) Silicon forms large crystal of pure silicon containing definite quantity of boron under
control conditions 0; temperature and pressure.
Solar Energy 53
IB.12 Semi-Conductor
In this class of crystals the forbidden gap is of the order of about lev, and the two energy
bands are distinctly separate with no overlapping. At absolute 0, no electron has any energy
to jump the forbidden gap and reach the conduction band. Therefore the substance is an
insulator. But when we heat the crystal and thus provide some energy to the atoms and their
electrons, it becomes an easy matter for some electrons to jump the small (,., lev) energy gap
and go to the conductor band. Thus, at higher temperatures the crystal becomes a conductor.
This is the specific property of the cyrstal which is known as a semi-conductor. Higher the
temperature, greater are the chances of electrons to jump to conduction bands and greater is
the conductivity. Germanium (Ge, Z = 32) and silicon (Si, Z = 14) are important semiconductor.
Characteristics of Semi-conductors:
1. The energy gap between the valence band and conduction band is very small (,., I e v).
2. At absolute zero, a semi-conductor behaves as an insulator because no electron is
'able to cross over the energy gap.
3. The electrical conductivity increases with increase in temperature.
4. When a moderately high potential difference is applied across a semi-conductor, it
break down.
5. When the temperature of a semi-conductor is raised to moderately large values, it
breaks down.
6. The electrical properties can be controlled by controlling the quantity ofimpurity added.
What are Intrinsic Semi-Conductors?
Pure semi-conductors are called intrinsic semi conductors. The examples of intrinsic semi-
conductors are silicon and germanium having 4 valence electrons each. The four valence
electrons of each atom of silicon form covalent band with its four neighbours. Sufficient amount
of energy is required to free these electrons from their bonds to the free state in the conduction
band. There is small energy gap (,., lev) between the conduction band and the valence band.
Some electrons have sufficient thermal energy to break away from the covalent bond and enter
into the conduction band even at room temperature.
\...
Hole Free electron
·· ... " . ..
, ... ...
"
........Is;\.~ ...............\).~.~ ......... ····.·0·.... ·

• • • • • I
··_-·,·Y ... ~- .. -............... y. . ........... ....... y. ..:....... .

. .. . . . .
·· .. .. .
,
,
"
" " "
"" " I
' "
' .
"
, • "• I ""
· ....··0
.....:' ···.·· ..........··.·.0...:' ................. Gj'"............
I • " "
Si • • Si·. .' Si
....... ···.0 .............. ··· ...................... . ..... ..
.......
,,
... ..... ,
·····B)~········;G~·····;{~·····
"--""(.• ) ..................... (.• j ................... (.• ) ...... .
Fig. 1.15.
When an electron in free form its band by thermal excitation, a vacancy is created in the
band which is called a hole. The hole can be regarded as a positive charge carrier as shown in
Fig. 1.15 when an electric field is applied, electrons and holes move in opposite directions.
For an intrinsic semi conductor
n~o) = nhO)
where n;O) is the electric density in conduction band.
and n~O) is the hole density in the valence band.

The value of intrinsic carrier concentration (n) at 300 K for Ge is 2.4 x 10 19 m-3 and for Si
is 2.4 x 10-16 m-3 respectively.
What are Extrinsic Semi-Conductors?
A doped semi-conductor or a semiconductor with impurity atoms added into it is called
extrensic semi-conductors. The amount of impurity added is small say 1 or 2 atoms of in purity
for 106 atoms of semiconductors crystal. Depending upon the nature of the impurity atoms
added the extrinsic semi-conductors are divided into two categories.
(i) n-type semi-conductors
(ii) p-type semi conductors.
IB.13 Doping of Silicon
As the conductivity of intrinsic semi-conductor is poor, so intrinsic semi-conductors
are of little practical importance. The conductivity of pure semi-conductors can be increased
by the addition of some pentavalent or trivalent substance called impurity in a very small
amount.
Therefore, the process of adding desirable impurity to a pure semiconductor in a controlled
manner is called doping. The impurity atoms added are called dopants. The dopants added to
the crystal will not distort the structure of the crystal. The concentration of dopant atoms
should not be large (not more than 1% of the crystal atoms).
Doping of a semi conductor increases its electrical conductivity to a greater extent. The
doping is done in many ways :
(i) The impurity atoms are added is the molten form of the semi conductor.
(ii) By heating the crystalline semi conducting material in an atmosphere containing
dopant atoms or molecules.
(iii) By bombarding the semi-conductor by ions of dopant atoms.
A doped semi conductor is called extrinsic semi conductor. They are divided into two
categories: (i) n-type semi conductors (ii) p-type semi conductors.
(i) n-type semiconductors: When an impurity atom belonging to group 15 of the periodic
table like P, As, Sb, Bi is added to the pure semi conductor (Ge or Si) then four of the five
impurity electrons form covalent bonds by sharing one electron with each of the four nearest
GelSi atoms and fifth electron from each impurity atoms is almost free as in Fig. 1.16 to conduct
electricity. Since these additional electrons cannot be accommodated in the valence band, they
occupy some discrete energy levels just near the bottom of the conduction band as shown in
Fig. 1.16. The electrons are easily excited from these levels into the conduction band. The
impurity so added is called donor impurity.
Solar Energy 55
· ,. . .. ,. .. ....
~•• ,: .~ •••• " •• '.'" ~•• ~••
••••
··· ....'1';\'.
v· . ·· ......... ····
.:......
"0".................................
'. ',;0;'. ,;.~--;
0'
.........
.................
...... :.......
: •••••••••••• !, ••:.,.....-.....
~~
::···••• e~
i· .~ ~. .. .j ~ ~
. . .
-..: '
',.:
····~·t;,\;;···········-;·--~··;· .. ·······~0;
',.: ',.:
~t;;;Y.-
·.... D· .................~·· ............. · ................... ~
; ..........
Valence
..: •..., .~ :.'e\, ./...... ,... e'".., band
::
. ::
.... . : ~ :!
. . ............~.>~~:..
~ ;.~~
"
..... (1.................
! "
(.)--~
.•...•// !.........
(a) (b)
Fig. 1.16.
Electrons which are in majority are called majority carriers. The holes are also
present but they are in minority in comparison to electrons. Hence they are called minority
carriers.
A silicon semi-conductor doped with a pentavalent impurity is called n-type silicon semi
conductor, because it has an excess of negative change carriers. In n-type semi conductors
electrons are majority carriers and holes are, minority carriers.
(ii) p-type Semiconductors
If a trivalent impurity like Indium, boron, aluminium, gallium is added to a pure semi
conductor, the impurity atoms can provide only three valence electrons as shown in Fig. 16
for covalent bond formation. Thus a gap is left in one of the covalent bonds. The gap act as a
hole that tends to accept electrons. Such impurity is called acceptor impurity. The crystal so
formed is called p-type semiconductor where p stands for positive charge carrier. Addition of
each impurity atoms results in the formation of one hole. The energy of these positive holes
is slightly greater than the top of the filled valence band as shown in Fig. 1.17 .
·
•
. •
..
• •
..
, • I
.. •
. --. !,.:' ................ \ ••: .............. ~•• : .................. !, ••:,.,---....
.....
· ...~0:~·
·.•..
......... ··!:0:~
.....
......... .:;0:~·
.....
....... ·J~.!-
.:, '.; . ~. f. {. ~.
· . . . . . . .
· . ..............................
; ........... . --.- ......
~·0s:
.~ ... ~
',.:
~.;
.....
~l' ............. ~.0. ............ ~.t;,Y.-

',.:
~ ...... --.- ......... ~

. . . 0'
:... e e - : ... :.', :.'.

:' .. ! o+-Hole ! .. ! ..
:: :: :: Hole: :
.... . . . / ....... ..\:L. .......---... .·. .d ~\./

~.0..~.. ...~ ~®~
......(.) ................. (.) (. ,.: (.)--
(a) (b)
Fig. 1.17.
The electrons from the valence band get easily excited by thermal energy to enter these
holes. This results in the formation of hole in t~e valence band which is again filled by another
electron producing another hole. Thus a hole can move freely in the valence band. The
conductivity increases considerably due to positive charge carriers. In this, holes are the
majority carrier and electrons are the minority carriers.
56 Essentials of Engineering Chellustry
1. What do you mean by Non-conventional sources of energy ?

2. What are the various examples of Non-conventional sources of energy?
3. What is solar energy ?
4. How can the solar energy be harnessed ?
5. What are solar power plants?
6. What is the principle of solar power plant?
7. What is a solar cell ?
8. What is the working principle of solar cells?
9. What-type of material are used in solar cells?
10. What are the various applications of solar cells?
11. What are silicon solar cells?
12. What are n-type silicon cells?
13. What are p-type silicon cells?
14. What are the various advantages of solar energy ?
15. What are the various limitation of solar energy for power generation?
16. What are the various types of silicon solar cells?
17. What are the advantages ofphotovoltaics?
18. What do you mean by doping?
(ANSWERS)
1. Non-conventional source of energy are being continuously generated in nature and

are non-exhaustible.
2. Solar energy, tidal energy, wind energy, geothermal energy, water energy, ocean
energy, biogas energy, etc.
3. The energy (heat and light) obtained from the sun, is called solar energy_ Sun is the-
source of all energies.
4. Solar energy can harnessed either directly or indirectly through some device.
5. Solar Power Plant is a device which produce electricity by using solar energy.
6. In solar power plant, sun rays are reflected by huge concave reflectors on black painted
coil type pipes (containing water) kept inside dark boxes painted black from inside.
Infrared rays of sun are dropped inside the large box to heat up the water and convert
it into steam. The hot steam under pressure rotate the steam-turbine, and there by
produce electricity.
7. Solar cell is a device which converts solar energy directly into electricity.
8. Light is absorbed in material, with the generation of positive and negative charges
which are collected at electrodes at either side. In this way the cell generate electricity.
9. A P-N-Junction diode made of Ge and Si is generally used in solar cells.
Solar Energy 57
10. The various applications of solar cells are :
(i) Solar cells store the solar energy during the day and deliver light at night.
(ii) They are used at bus stops in ticket machines and speed warning signs.
(iii) Solar cells are used for communication purposes also.
(iv) PV is also used for deep well pumping system.
11. Silicon solar cells consist of sandwich of n-type and p-type silicon semiconductor
separated across the junction.
12. When Si lattice containssome atoms of As with 5 electrons in its outer shell, Four of
these electrons form bonds with Si, while fifth electron is available for' conducting
current. Such solids are called n-type semi conductors. The fifth electron is provided
by the impurity element which has five electron in its outermost she!.
13. When Si lattice contains some atoms of Indium (In) with three electrons in the outer
shell. There is shortage of one electron to form four covalent bonds which constitutes
a positive hole. If these holes are filled with adjacent electrons, they form other holes
and by migration in this way, they carry current. Such solids are called p-type Si
semiconductors.
14. The various advantages of solar energy are:
(i) Solar energy is a kind of universal, decentralised and non-polluting energy.
(ii) Solar energy is essential for every kind of living organism.
(iii) Solar energy helps in maintaining the ecological balance through the process of
photosynthesis and green house effect.
, 5. Solar energy has some limitations such as :
(i) The density of solar energy is low as compared to oil, gas or coal etc.
(ii) The intensity of solar energy is not constant. It varies from morning to evening
with a maximum around 2 pm.
16. The various type of silicon cells are :
(i) Single crystal silicon cell
(ii) Polycrystalline silicon cell
(iii) Ribbon silicon cell
(iv) Amorphous silicon cell.
17. The various advantages of photovoltaic cell are :
(i) Photovoltaics are non-polluting.
(ii) Photovoltaics have modular constraction.
(iii) Photovoltaics have simple operational aspects coupled with easy maintenance.
(iv) Photovoltaic have been able to match the use of other renewable energy sources.
18. The process by which the performance of semiconductors is enhanced by introducing
a small number of suitable replacement atoms as impurities into the semi conductor
lattice is called doping.
1. What do you mean by non-renewable sources of energy and renewable sources of

energy ?
2. Give some examples of renewable and non-renewable sources of energy.
3. How solar energy is converted into other forms of energy ?
4. What are the applications of photovoltaic systems?
5. How does solar energy is trapped in space?
6. Why solar systems are failing?
7. What are the various applications of solar energy ?
8. How does silicon cells are made and discuss their types?
9. How does photocells trap solar energy ?
10. What are the properties of silicon in relation photocells?
11. Discuss the various types of silicon cells.
12. Write a short note on doped semiconductors?
13. What do you mean by extrinsic and inrinsic semiconductors?
14. Write a short note on the construction and working of solar cell.
15. Differentiate between n-type and p-type semiconductors.
ELECTROCHEMICAL ENERGY
SYSTEMS
(ELECTRODE POTENTIAL AND CELLS)
SYLLABUS
Single electrode potential-<1efinition, origin, sign conventions; Derivation of Nernst equation;
Standard electrode potential-definition; construction of a galvanic cell, classification of
galvanic cells-primary, secondary and concentration cells, EMF of a cell-Definiton, notation
and conventions; Reference electrodes-calomel electrode, Ag / Agel electrode,' Measurement
of single electrode potential; numerical problems oT' electrode potential and EMF. Ion
selective electrode- glass electrode, determination of pH using glass electrode.
2.1 INTRODUCTION
We know that electric current can be employed to bring about chemical reaction
(electrolysis). But it is possible to carry out the reverse process i.e. to a chemical reaction for
producing electric current. The chemical reactions employed for generating electric current
are oxidation-reduction reactions and are called redox reactions. In these reactions electrons
are lost (oxidation) by one substance and are accepted (reduction) by a second substance. In
genera, a chemical change which is accompanied by flow of electrons is known as electro-
chemical change. The electrochemical changes are of two types and corresponding to these
two types of changes there are two types of cells namely (i) Electrolytic cells and (ii)
Electrochemical cells.
(i) Electrolytic cells: There are chemical changes which are brought about by passing
electric current through electrolytes in the molten state or through their aqueous chemical
energy i.e., current can be employed to bring about a chemical reaction. This phenomenon of
decomposition of an electrolyte with the help of electric current is called electrolysis. A device
in which electrolysis is carried out is called an Electrolytic Cell.
(ii) Electrochemical cells: There are chemical changes which produce electric current
as a result of the electron transfer from one substance to another. A device employed to convert
the chemical energy of a redox reaction into electrical energy is called an electrochemical cell.
Electroche,mical reactions can be accomplished by two methods.
(a) Direct Redox Reaction (b) Indirect Redox Reaction
(4) Direct redox reaction: When a redox reaction is carried out directly, chemical energy
in the form of heat is produced. For example, if we place a zinc rod in a solution of copper
sulphate, the following reaction occurs and a rise in temperature of the solution in noticed.
Zn(s) + Cu2+ (aq) ~ Zn2+ (aq) + Cu(s)
(b) Indirect redox reaction: When a redox reaction is carried out indirectly, chemical
energy is changed in the form of electrical energy. In this case, oxidation half reaction and
reduction half reaction are carried out in separate beakers. These cells are very important,
because of their many practical applications. An early example of a galvanic cell is a Daniell
cell which was invented by the British chemist John Daniell in 1836. This cell was constructed
on the basis of the above given redox reaction. The important differences between electrolytic
cell and galvanic cell are discussed later in the chapter.
Electrochemical energy plays an important role in many chemical reactions. The branch
of science which deals with the relationship between electrical energy and chemical energy and
interconversion of one form into another is called electrochemistry. We come across many
processes in daily life such as supply of electrical energy by cells and batteries to run different
appliances like radios, transistors, watches, telephones etc.
2.2 SINGLE ELECTRODE POTENTIAL
Origion
The flow of electric current in an electrochemical cell indicates that a potential difference
exists between two electrodes. Th understand the potential difference between two electrodes
let us consider the redox reactions occurring at these electrodes.
When an electrode say a metal, is immersed in a solution of its ions, then either of the
following three possibilities can take place:
(a) The metal ions (Mn+) may collide with the electrode and do not undergo any change.
(b) Mn+ ions may collide with the electrode, gain electrons and get converted into metal
atoms (i.e. the ions are reduced).
(Reduction)
(c) M atoms on the electrode may loses electrons to the electrode and become Mn+ ions
and go in to the solution (i.e., oxidation occurs).
M ~ Mn+ + ne- (Oxidation)
These possibilities are shown in Fig. 2.1.
Now if the metal has relatively high tendency to get oxidised, its atoms will lose electrons
readily and Mn+ ions will go into the solution. The electrons lost on electrode would be
accumulated on the metal electrode and the electrode acquires a slight negative charge with
respect to the solution. Some of Mn+ ions form the solution will take up electrons and become
M atoms. After some time, an equilibrium will be established as :
M cs ) ~ Mn+ + 2ne-
electrode Boluiton (on electrode)
When such an equilibrium is attained, it results in separation of charges (negative on the
electrode with respect to the solution).
Similarly, if the metal ions have relatively greater tendency to get reduced, they will take
electrons from the electrode. As a result, a net positive charge will be developed on the electrode
with respect to the solution. This will also result in to separation of charges (positive on the
electrode with respect to the solution).
Due to separation of charges between the electrode and the solution, an electrical potential
is set up between metal electrode and its solution. The electrical potential difference set up
Electrochemical Energy Systems (Electrode Potential and Cells) 61
Metal rod
M
(aJ Metal ions collide but do not undergo any change.
Metal ions gain electrons and get converted to metal i.e.,

(b)
reduction occurs, (electrons are lost by metal rod and it
acquires + ve charge).
Metal atoms on electrode lose electrons to form matel ions i.e.,

(c)
oxidation occurs. Electrons lost by metal accumulates on
metal rod. (Metal rod acquires -ve charge)
Fig. 2.1. Electrode equilibrium.

between the metal and its solution is known as electrode potential. Thus, the electrode
potential is a measure of tendency of an electrode in a half cell to gain or lose electrons.
Definition
When metal is immersed in an aqueous solution containing the metal ions, the metal atoms
have some tendency to pass into solution as cations or metals ion start depositing on the metal
surface (Fig. 2.2). In the beginning, both these changes occur with different speeds but soon
an equilibrium is established.
M =:::::=====
T=,
Oxidation
Reduction
"The equilibrium potential difference between the metal electrode and the solution
surrounding it" is called the electrode potential. It is also defined as the tendency of an
electrode to lose or gain electrons.
The electrode potential is commonly
expressed in two way : ()
Metal
The electrode potential is further termed as : : : : : : : f<lC! : : : : .. ... : )'nd:
oxidation potential, if oxidation takes place at the
electrode. Oxidation involves loss of electrons.
So, the tendency of an electrode to lose

electrons is called oxidation potential.
M ~ Mn+ + ne-;
....... , . ..... . ........ .... . ..
The metal ions go into solution and (a) Electrode potential: (b) Electrode potential:
electrons remain on the metal rod making it Oxidation (deelcctronation) Reduction re1cc·tronation )
negatively charged. The tendency of the metal
to change into ions is also known as Fig. 2.2.
electrolytic solution pressure.
The electrode potential is called reduction potential if reduction takes place at the electrode.
Reduction involves gain of electrons so, the tendency of an electrode to gain electrons is
called its reduction potential.
Mn++ne- ~ M;
As metal ions start depositing on the metal surface leading to positive charge on the metal
rod. Since oxidation is just a reverse of reduction, therefore, reduction potential is obtained
from the oxidation potential by simply changing the sign.
In general, for an electrode
Oxidation potential = - Reduction potential
For example, Zinc electrode, standard oxidation potential is represented as
E~n /zn2+ = O.76V

and standard reduction potential asE~n 2+/Zn =- O.76V
It is common practice to express all the electrode potentials as reduction potentials.
The difference between oxidation potential and reduction potential
may be summarized as
Oxidation Potential Reduction Potential
1. The tendency of an electrode to lose electrons The tendency of an electrode to gain electrons
when in contact with the solution of its own when in contact with solution of its own ions in a
ions in a half cell is known as oxidation half cell is known as reduction potential.
potential.
2. It is inversely proportional to the It is directly proportional to the concentration of
concentration of ions ofthe electrode. ions of the electrode.
Sign Convention
According to the latest convention, if oxidation takes place at the electrode, it is allotted
a negative electrode potential and if reduction takes place on the electrode it is
allotted a positive electrode potential, when the electrode is combined with a
standard hydrogen electrode (NHE) to form an electrochemical cell. Also, according to
the convention, the half reactions are always written as reduction half reactions and
their potential are reduction potential.
On making a cell between the given electrode and the standard hydrogen electrode, the
direction of flow of electrons (as shown by the direction: of deflection of voltmeter needle) shows
whether oxidation or reduction takes place at the given electrode. Since the electrons move
from anode to the cathode, the needle is deflected away from the anode (where oxidation takes
place). In other words, if oxidation takes place at the electrode on combination with hydrogen
electrode, its oxidation potential is taken as positive and consequently its reduction potential
will be negative. On the other hand, if reduction takes place at the electrode, its reduction
potential is taken as positive and consequently tts reduction potential will be negative.
2.3 DERIVATION OF NERNST EQUATION (CONCENTRATION DEPENDENCE OF
ELECTRODE POTENTIAL)
The e.m.f of a cell depends both on (i) Standard e.m.f of cell i.e. its nature (ii) the
concentrations of the species involved in the cell reaction and (iii) temperature.
For a general cell reaction of the type,
aA+bB ~ IL+mM
In thermodynamics, the free energy (LlG) accompanying the above general equation is given
as:
LlG
where LlGo is the free energy change of the reaction under standard conditions.
Since LlG =-n FE and LlGo =- nFEo
[L]' [M]"'
-nFE = - nFEo + RT In [A t
[B t
or E = ° RT
E - -
[L]' [M
In -=--=--=-----=--
r
nF [A t
[B t
2.303 RT [L]' [M]m
E = EO - log ..::.........:'--..::...---=-:--
nF [At [Bt
where E is the e.m.f. of the cell, EO is the standard e.m.f. of the cell :
[1\], [B], [L] and [M] are the molar concentration of the species A, B, Land M respectively.
a, b, I and m are the stoichiometric coefficients in the chemical equation, n is the number
of electrons involved, R is the gas constant, T is the absolute temperature, F is one Faraday
(96500 coulombs).
The equation is known as Nernst Equation.
As 25°C, R = 8.314 Joules/Kelvinlmole, T = 25°C + 273 = 298 K (at Standard conditions)
and F = 96500 coulombs
2303RT 2.303 x 8.314 x 298
= - - -96500
- - - - =0.0591
F
2303RT
Substituting the value of F in equation above, we get:
E = P _ 0.0591 10 [L]I [M ]m
... (2.1)
n g [A [Bt t
or E = P+ 0.0591 10 [At [Bt
n g [L]I [M r
It is seen from Nernst equation, that if the product of the molar concentration of products
is more than the product of the reactants, e.m.f., (E) is less than the standard e.m.f., (EO). On
the other hand, if the product of the molar concentration of the reactants is greater than that
of the molar concentration of products, E is greater than EO.
2.3.1 Application of Nernst Equation
(i) Calculation of the e.m.f. of a cell. Consider for example the cell :
Zn I Zn2 + II Cu2+ I Cu
The cell reaction may be written as :
Zn + Cu2+ = Cu + Zn2+
Applying Nemst equation (2.1) :
E = E _ 0.0591 10 [Cu][Zn 2+]

2 g [Zn][Cu 2+]
Here, number of electrons involved in the half cell reaction is 2.

In the standard state, the activity (molar concentration) of a solid is taken as unity.
E = EO - 0.0591 log
2 Cu 2+
[zn2+ 1
From this equation, it is obvious that E may be equal to EO or may be greater or less than
EO. E depends on the ratio of the concentration ofZn2+ ions and Cu2+ ions.
(ii) Calculation of the single electrode potential: Although the standard electrode
potential is fixed, the concentration of the ion in the half-cell affects its single reduction electrode
potential. This is also given by Nernst's equation.
Zn2+ + 2e- ~ Zn
° RT In [Zn] =Eo_RT I n _1_=E o + RT In [Zn2+]

E = E - nF [Zn2+] nF [Zn2+] nF
[.,' Zn being solid, its concentration is taken as unity]
E = EO _ RT In [Zn2] = P + 2.303RT log [Zn2+] = EO + 0.0591 log [Zn 2+]

nF nF n
Where E and EO are the single electrode potential and standard potential, n, Rand F have
the usual significance.
The general expression for electrode potential of a metal in contact with Mn+ ions reaction
involving the electrode may be written as
MD+ +ne- = M
E = EO + 0.0591 log [Mn+]
n
Calculation of equilibrium constant: At the equilibrium concentration of the two
(iii)
metal ions, there is no potential difference between the two electrodes and the e.m.f. of the
cell becomes zero.
Consider a reaction at equilibrium
aA + bB ~ cC + dD
[ct [D]d
KG = [A]a [B]b
The Nernst equation can be represented as
0.0591 1 [C]C [D]d
Eeen = EOeen - n og [A]a [B]b
At the stage of equilibrium, Eeen =0
Therefore, the above equation can be written as
o _ 0.0951
Zero =E ce
II
n log Kc
0.0591 .
or EO cell = log Kc' where Ke is the equilIbrium constant for the reaction.
n
Knowledge of standard electrode potential can thus be employed for calculating the
equilibrium constant (Ke) for the reaction.
2.4 STANDARD ELECTRODE POTENTIAL
The electrode potential of a half cell, in which the metal is suspended in a solution of one
molar (1M) concentration and the temperature is kept at 25°C (298K) is called standard
electrode potential. It is usually by EO.
It is not possible to determine the absolute value of electrode potential of a single electrode.
It is because a single electrode constitutes only a half cell. Ahalf cell, not be lose or gain electrons
by itself. The loss or gain of electrons can take place only in a complete circuit containing two half
cells connected to each other. So, the electrode potential can only be measured by using some
electrode as reference electrode. The reference electrode commonly employed is the standard or
normal hydrogen electrode (NHE Fig. 2.3). The
potential ofNHE is taken as zero.
Hydrogen electrode: It is a familiar example of
gas electrodes. It consists of a platinized platinum strip H2 gas of
1 atm
di pped in an acid solution through which hydrogen gas pressure
can be bubbled as shown in Fig. 2.3. In the Normal
Hydrogen Electrodes (NHE), H2 gas at 1 atmospheric
pressure is passed into 1M-HCI at 298 K.
1 M -Hel
The reversible change are represented as Holulion :-.d~~--t--Platinum
foil
2 H (aq) + 2e- ~ H 2(g)
and Fig. 2.3. Normal hydrogen electrode (NHE).
Normal hydrogen electrode is represented as Pt; H2 (1 atmIHCI (1M) when placed as anode
and HCI (lM)1H 2 (1 atm); Pt when placed as cathode.
2.5 MEASUREMENT OF SINGLE ELECTRODE POTENTIAL
To measure the relative value of electrode potential of any given electrode, a cell is set up
which consists of the given electrode as one of the electrode and the second electrode is NHE.
The e.m.f. of the cell is measured. The measured e.m.f. of the cell would give the electrode
potential of the electrode under investigation because the electrode potential of NHE is taken
as zero. The direction of flow of current further indicates whether oxidation takes place or the
reduction take place at the electrode under investigation with respect to hydrogen electrode.
Accordingly the electrode potential is termed as oxidation or reduction potential.
Sign conventions:
According to IUPAC convention, potential is given a positive sign if reduction occurs and
a negative sign if oxidation occurs at the electrode under investigation with respect to
the hydrogen electrode. Accordingly the electrode potential is termed as oxidation or
reduction potential.
For measurement of standard electrode Voltmeter
potential, a cell is set up in which one-half of
the cell consists of metal and its ion at 1 M
concentration and the other half of the cell
consists of the hydrogen electrode. The
temperature in both half cells is kept at 25°C.
(a) Measurement of electrode potential
of Zn2+/Zn electrode : When coupled with
NHE, some electrodes undergo spontaneous
oxidation and permit loss of electrons. Zinc
electrode when combined with NHE is oxidized
to Zn2+ ions. In other words, the zinc electrode
pushes electrons into the external circuit and
forms the anode. By convention the anode is
Zn° --+ Zn2+ + 2e- 2H+ + 2e- --+ H2
shown on the left (Fig. 2.4) and it is said to
possess a negative value of reduction electrode Fig. 2.4. Zinc electrode acts as anode when
it is connected to NHE.
potential (- 0.76 volts).
(b) Measurement of electrode potential Voltmeter
of Cu2+/Cu electrode : In case the electrode
e e
coupled with NHE undergoes spontaneous
reduction, it allows oxidation of NHE. When
copper electrode dipped in Cu2+ solution coupled
with NHE, Cu2+ ions are reduced to Cu(s) and
at NHE, H2 is oxidized to H+ ion by pushing
f
electrons into the external circuit (Fig. 2.5).
Copper electrode acts as cathode and it is said
to have positive value of reduction electrode
potential (0.34 volts)
2.6 ELECTROCHEMICAL CELLS OR
GALVANIC CELLS
A device employed to convert the chemical H2 --+ 2H+ + 2e- Cu 2+ + 2e- --+ Cu
energy of a redox reaction into electrical Fig. 2.5. Copper electrode acts as cathode when it
energy is called an electrochemical cell or is connected to NHE.
simply a chemical cell.
It is also commonly referred to as a galvanic or voltaic cell after the names of Galvani
(1780) and Volta (1800), the pioneer in this field.
The main requirements of a electrochemical cell are :
(i) A suitable redox reaction is carried out indirectly in the two separate half cells.
The electrons are lost in one cell and gained in the other.
(ii) The substance which loses the electrons and the one which accepts the electrons
should not be in direct contact with each other. The electron transfer must take place
through an external circuit.
Let us illustrate the principles of an electrochemical cell by taking example of Daniel cell,
i.e., an electrochemical cell in which Zn - CuS0 4 reaction takes place.
Zn(s) + CuSOiaq) ~ ZnSOiaq) + Cu(s)
The Ionic equation for this reaction is :
Zn(s) + Cu2+ (aq) ~ Zn2+ (aq) + Cu(s)
Construction : It consists of two beakers one containing solution of ZnS0 4 (say O.lM)
and zinc plate is dipped in it. The other beaker contains CuS04 solution (say O.lM) and a copper
plate is dipped in it. The two solutions are connected by means of a salt bridge. A salt bridge is
V-shaped tube containing concentrated solution of an electrolyte like KCI, KN0 3 , NH4 N0 3
etc., or solidified solution of an electrolyte in Agar-Agar and gelatine. The ends of the bridge
are plugged with glass wool or cotton. The salt in the bridge is such that it does not react
chemically with either of the two solutions connected by it Fig. 2.6 (a). The transport number
(dependent upon ionic mobilities) of the cation and the anion of the electrolyte used in the salt
bridge should be almost equal.
Volt meter
Volt meter
of conventional
~\O~l"el1t
e ~ Salt bridge ~ liB
-- -- -- -- --. Cathode
~~~_
~ Porous
plugs ---A"E~I
(a) Daniel cell. (b) Daniel cell

Fig. 2.6.
Working and reactions: When the two metallic plates are joined through a connecting
wire, the reaction takes place due to the fact that electrons flow from zinc to the copper plate.
This flow of electrons constitutes electric current, since electrons, i.e., negative electricity flows
from zinc to the copper plate, the conventional current, i.e., positive electricity flows from
copper to zinc plate. Thus zinc plate serves as negative electrode and copper plate serves as
positive electrode.
The following observations are recorded.
(i) Zinc plate loses its weight.
It is due to the fact that zinc gets oxidized to zinc ions which go into the solution.
Zn (s) ~ Zn2+ (aq) + 2e-
Such an electrode at the surface of which oxidation, i.e., loss of electrons takes place is
known as anode.
(ii) Copper plate gains weight.
It is due to the fact that copper ions gain electrons at the copper plate.
Cu2+ (aq) + 2e- ~ Cu (s)
Such an electrode at the surface of which reduction i.e., gain of electrons takes place is
known as cathode.
(iii) The solution remains electrically neutral.
For details see functions of salt bridges.
(iv) The loss in weight of zinc and gain in weight of copper are in the ratio of their equivalent
weights, i.e.,
Loss in wt. of Zn Eq.wt ofZn 32.70
= =
Gain in wt. ofCu Eq. wt ofCu 31.75
(v) Electrical energy is obtained due to conversion of chemical energy.
It is due to the fact that chemical gets transformed to electrical energy as evident from
the deflection in the voltmeter.
(vi) The reaction and working of cell, i.e., flow of electric current stops after sometimes.
Reason: It is due to the fact that reduction potentials of both zinc and copper plates become
same after sometime. Thus the e.m.f. of the cell, i.e., the driving force becomes zero.
The e.m.f. of the cell is made up of two half cells in each of which a half reaction takes
place as shown below:
Zn(s) ~ Zn2-(aq) + 2e- (Oxidation half-cell reaction)
Cu + (aq) + 2e- ~ Cu(s)
2 (Reduction half-cell reaction)
2.6.1 Functions of Salt Bridge
(i) To complete the circuit.
(ii) To maintain electrical neutrality of the solutions in both the half cells.
AB the reaction progresses, in the oxidation half cell, Zn will lose electrons and would change
to Zn2+ ions and positive charge may accumulate in this cell due to excess of Zn2+ ions. This
will prevents the release of electrons from zinc plate.
Similarly, in the reduction half cell, Cu 2+ ions would gain electrons and would be deposited
as Cu on the electrode. So the negative charge would accumulate due to the excess of SO 2-
ions in this half cell. This prevents the flow of electrons upto the copper plate. 'lb maintain the
electrical neutrality in the two half cells, the negative ions (anions) of the electrolyte in the
salt bridge would move to the oxidation half cell in order to neutralize excess of zinc ions.
Similarly the positive ions (cation) move to the reduction half cell, in order to neutralize the
excess of sulphate ions.
In the absence of salt bridge, the current would have stopped flowing in the circuit due to
accumulation of opposite charge in the two half cells.
(iii) To prevent intermixing of the solutions of both half cells.
2.6.2 Difference Between an Electrochemical Cell and Electrolytic Cell
An electrochemical cell converts chemical energy into electrical energy while an electrolytic
coverts electrical energy into chemical energy.
Galvanic cell Electrolytic cell
l. In galvanic cell, electrical energy is produced. In electrolytic cell, electrical energy is consumed.
2. In galvanic cell, reaction taking place is In electrolytic cell, reaction taking place is non-
spontaneous. spontaneous.
3. The two half-cells are set up in different Both the electrodes are placed in the solution
containers and are connected through salt or molten electrolyte in the container.
bridge or porous partition.
4. In galvanic cell, anode is negative and cathode In electrolytic cell, the anode is positive and
is positive. cathode is negative.
5. The electrons, move from anode to cathode in The electrons are supplied by the external source.
external circuit. Electrons enter through cathode and come out
through anode.
Electrochemical Energy Systems (Electrode Potential and Cells) . 69 "
2.6.2 Representation of Galvanic Cells
The galvanic cells are represented with the help of certain notations and conventions, which
are given below:
I
(1) The interfaces across which a potential difference exists are shown by a semi-colon (;)
or a single vertical line ( I ). For example, in the half-cell zinc in contact with Zn2+ ion is shown
as
Zn; Zn2+ or Zn I Zn2+
This indicates that the potential difference exists at the zinc and Zn2+ ion interface. In the
formulation of another half-cell.
Ag, AgCI I Cl-
The comma or the plus sign between Ag and AgCI indicates that these two materials taken
together constitute the electrode.
(2) The contact between two solutions with the help of a salt bridge is indicated by a double
vertical line (" ) between them. For example, two solutions containing Zn2+ ions and Cu2+ ions
respectively connected by a salt bridge or a porous barrier are shown by
Zn2+/ salt bridge / Cu2+ represented Zn2+ II Cu2+
(3) The oxidation half-cell is written on the left hand side and the reduction half-cell on
the right-had side with the metal electrodes always on the outside extremes. For example,
Daniel cells is formulated as :
Zn; Zn2+ II Cu2+; Cu
or Zn I Zn2+ II Cu2+ I Cu
Sometimes negative and positive signs are put on the electrodes to show that they are
negative and positive electrodes as shown below:
E> Ell
Zn I Zn2+" Cu2+ I Zn
(4) An arrow when drawn below the cell formulation gives the direction of the positive
current inside the cell while an arrow drawn above the cell formulation gives the direction in
which the electrons flow in the outer circuit.
~
Znl Zn 2+11 Cu 2i Cu
~
(5) The concentration of solutions, pressures of gases and physical state of the
solid or liquid involved are indicated by suitable signs within brackets as in the following
cells:
(a) Daniel cell
Zn I Zn2+ (0.1 M) II Cu2+ (0.1 M) I Cu
(b) Copper-silver nitrate cell
Cu; Cu2+ (0.1 M) 1IAg+ (0.1 M) I Ag
(c) Zinc-hydrochloric acid cell
Zn; Zn 2+ (0.1 M) II H2+ (0.1 M); (1 atm.) H 2, Pt
(d) Zinc-silver nitrate cell
Zn; Zn2+ (0.1 M) 1IAg+ (0.1 M); Ag
2.7 REFERENCE ELECTRODES
'11 electrode whose electrode potential in accurately !mown or whose electrode potential
has been arbitrarily fixed is called a reference electrode. In other words it is an electrode
of standard jJotential with which we can compare the potentials of other electrodes.
It is conbined with any electrode whose electrode potential has to be determined to form
an electro chemical cell through a salt bridge. The e.m.f. of the cell thus formed is noted and
the electrode potential of the electrode under test can be known. In case of normal hydrogen
electrode (NHE) the electrode potential is taken as zero. So, the e.mJ. ofthe cell itself becomes
the electrode potenti.al of the electrode concerned. A reference electrode should satisfy the
following conditions ':
Condition for a reference electrode
,(i) It should be easily set up.
'(ii'l It should not be bulky or space occupying.
(iii) It should not be easily poisoned by the impurities.
(iv) It should be usable even when the solutes are volatile.
tv) Its electrode potential should not change even by change in pH of the solution.
Reference electrode are broading divided into two types:
1. Primary Reference electrodes
Standard Hydrogen electrode: For details please refer to article 2.4 (Standard Electrode
Potential). It is primary reference electrode employed for cell potential measurements. It
potential is taken as zero. It is combined with the electrode whose electrode polenlial has to
be measured to form a cell. The e.m.f. of the cell so constituted is measured, which gives the
potential of the electrode since potential of SHE is taken as zero. But it is quite difficult to spt
up a hydrogen electrode. Moreover, it can not be used in solutions containing redox solution.
It is also affected by oxidising agents like MnO;;:, Cr2 0?- ,
Fe 3 + etc. and some compounds of
Hg, As, S etc. Consequenty this eletrode can not be used for solutions containing these ions.
In such cases some other electrodes are employed which are standarised using SHE. These
electrodes_ are called secondary reference electrodes.
2. Secondary Reference Electrodes
They include calomel electrode, Ag-AgCI electrode, glass electrode, quinhydrone electrode
etc.
(i) Calomel electrode : It consist of a tube, at the bottom of which there is a layer of
mercury and mercurous chloride Hg 2 C1 2 Fig. 2.7. The remaining portion of the cell is filled
with a solution of normal or decinormal or saturated solution of KCl. A platinum wire dipping
into the mercury layer is used for making electrical contact. The electrode is connected with
the help of side tube through a salt bridge with other electrode to make a complete cell. A
compact form of the electrode is shown in Fig. 2.7 (b).
The electrode may be represented as :
Hg; Hg2 CIz (s) KCI (solution);
When oxidation occurs at this electrode, the following reaction takes place:
2Hg ( I ) ~ H g22+ + 2e-
Hg~+ + 2CI" -~ Hg 2CI 2 (s)
2Hg(l) + H g2CI2 (s)+ 2e-
Electrochemical Energy Systems (Electrode Potential and Cells) ,,71
Electrical contact
Calomel paste
:~l-_rIJrUl-''' disc or asbestos

thread
(a) (b)
Fig. 2.7. The calomel electrode.
When reduction occurs at this electrode, the following reaction takes place:
Hg2CI2(S)~Hg~+ +2Cr
Hg~+ +2e- ~ 2Hg(l)
The electrode is thus, reversible with respect to chloride ion (anion). The equilibrium
reaction may be represented as :
•
2Hg + 2 CI- ~ Hg2 Cl2 (s) + 2e-
The potential of the calomel electrode depends upon the concentration of the potassium
chloride solution. If potassium chloride is saturated, the electrode is known as Saturated Calomel
Electrode (SCE) and if potassium chloride is IN, the electrode is known as Normal Calomel
Electrode (NCE) while for O.lN potassium chloride the electrode is referred as Decinormal
Calomel Electrode (DNCE). The reduction potentials of calomel electrodes on hydrogen scale
at 298k are as follows :
Saturated KCI 0.2422 V
1.0 KCI 0.2800 V
0.1 NKCI 0.3338 V
Calomel electrode is preferred to NHE for using as reference
electrode. Because it can be set up conveniently and once set it can be
used for long. In case of NHE, it is difficult to maintain the supply of
H2 gas at 1 atm pressure for long.
(U) Silver-Silver chloride electrode: The electrode is
represented as :
Ag : Ag CI (s) KCI solution; or Ag + AgCI / CI- (ACI-)
Its electrode reaction is :
Ag(s) + CI- AgCI(s) + e-
It is prepared by depositing a thin layer of AgCI electrolylically on
a silver or platinum wire and is then immersed in a solution containing
CI- ions. Fig. 2.7 (c).
The chloride ion concentration i.e. of hydrochloric acid solution must
be indicated, or any of other sparingly soluble chloride solution. Other
insoluble salts employed in making electrode of this type are AgBr, AgI, Hg2 C1 2 , sparingly
soluble sulphates and oxalates.
The Ag - AgCI electrode is reversible with respect to chloride ion. Its potential at 298 K
with saturated KCI is 0.290 V and that with 0.1 N KCI is 0.199 V w.r.t. SHE.
(iii) Glass electrode: When two solutions of different pH are separated by a glass membrane,
a potential is established across the membrane whose magnitude depends on the difference in pH
of the two solution, a potential iA established between the glass and the solution. The value ofthe
potential is a function of the particular glass used and is given by the equation.
Eg = EOg + ~T In (H+)=P g _(2.30: RT)PH
The electrode reaction is assumed to involve the reduction of H+ ions. The glass electrode,
thus function in the same manner as a reversible hydrogen electrode.
Construction of glass electrode : It consists of a thin walled glass bulb with a long neck
and is made up of a special type of glass oflow melting point and comparatively high conductivity
(Fig. 2.8(a)(b). A solution of known pH (usually 1 N-HCl) is taken in the bulb. A platinum
electrode is introduced into the solution and a pinch of quinhydrone is added to it. A glass
electrode is used for determining pH of solution, especially for coloured solutions and solutions
containing oxidizing and reducing agents. The combination representing the half cell for glass
electrode is represented as
Glass
Glass vessel
vessel
N-HCI
saturated with
quinhydrone
Glass
membrane
(a) (b)
Fig. 2.8. Glass electrode.
Pt 11.0 N-HCII Glass
Sometimes a silver-silver chloride electrode in place of platinum is also employed. It is
then represented as: Ag/AgCI(s) 1 0.1 MHCII glass
Advantages of glass electrode:
(i) It is the most simple and convenient to use and its gives accurate results.
(ii) It can be used in turbid, coloured and even colloidal solutions.
(iii) It can used in alkaline as well as in solutions containing oxidising agents.
(iv) It is not easily poisoned by any kind of cations and anions present in solutions.
(v) It can measure pH value of solutions available in small quantities (only a few mili
litres of the solutions is required).
(vi) Equilibrium is attained rapidly.
(viii) It does not require the use of any salt bridge.
Limitations of glass electrode
(i) For e.m.f. measurement using glass electrodes ordinary potentiometers can not be
employed because of high resistance glass. Either quadrant electrometers or vacuum
tube voltameters (VTVM) which require practically no current for their operations
must be employed.
(ii) It can be used upto a pH of 13 but being sensitive to Na+ ions above a pH of 9, the
linear relationship between glass electrode and pH is altered. So an alkaline error is
introduced beyond a pH of 9, which should be taken into consideration.
(iii) In strongly acidic solutions of pH < 1, the salt effect due to anions is observed.
(iv) It does not function properly in some organic solvents like pure alcohol.
2.8 CELL POTENTIAL OR E.M.F OF A CELL
An electrochemical cell consists of two electrode which have different electrode potentials.
The difference in electrode potential which causes the current to flow from the electrode
at a higher potential to the electrode at lower potential is known as the cell potential.
The differences of potential between the electrodes of a cell can be measured by using a
voltmeter. It is the potential differences due to which the cell is sending the current to the circuit.
This potential differences is called the electromotive force (e.m.fj of the cell, ifno or very little
current is allowed to flow at the time of measurement. It is measured by a potentiometer.
The difference between e.m.f. of a cell and potential difference is summarized below:
Cell Potential or e.m.f. Potential difference

Definition Def'mition
1. It is the difference between electrode potentials It is the difference between electrode potentials
of two electrodes when no current is flowing of two electrodes when current is flowing through
through the circuit i.e. open circuit. the circuit i.e. closed circuit.
2. It is determined by means of the potentiometer. It is determined by means of a simple voltmeter.
3. It is the maximum voltage obtainable from a It is less than maximum voltage obtainable from
cell. a cell.
4. The work calculated from e.m.f. is the The work calculated from gotential difference is
maximum work obtainable from a cell. less than maximum work 0 tainable from a cell.
5. It is responsible for the flow of steady current It is not responsible for the flow of steady current
through the circuit. through the circuit.
2.8.1 Calculation of E.M.F. of a cell

An electrochemical cell is always based upon a redox reaction which can be split into two
half reactions namely the oxidation half reaction and the reduction half reaction. The standard
e.m.f. of a cell (EO cell) is given by the relation.
EO _ [standard oxidation potential] _[standard oxidation potential]
Cell - of oxidation half reaction of reduction half reaction
Since oxidation potential = - reduction potential
The above expression may be written as :
EO _ [standard reduction potential] _ [standard reduction potential]
Cell - of reduction half reaction of oxidation half reaction
74 Essentials o{Engineering Chemist1:\'
Notation and Convention
In the representation of a cell, the electrode at which oxidation takes place in shown on
the left hand side and the electrode at which reduction takes place is shown on the right
hand side. Hence the above expression is written as
EO cell -- EO (Right electrode) - EO (Left electrode) -- EO (cathode) - EO (annel,,)
[Both the electrode potentials being reduction potentials.J
Thus the E.M.F. of a galvanic cell (E°cf!lI) is calculated through the following steps:
Step I : The overall electrochemical cell reaction is split into two half reaction I.e. o"tdatioll
half reaction and reduction half reaction.
Step II : Equate the number of electrons in the two half reactions by multiplying with a
suitable number, if necessary. However, EO values are not multiplied.
Step III : Formulate the galvanic cell in such a way that the electrode on which oxidation
takes place and acts as anode in shown on the left hand side while the electrode on which
reduction takes place and acts as cathode is shown on the right hand side.
Step 4: The standard E.M.F. ofthe cell is given by the relationship:
EO cell = EO cathode - EO anode
= EO right - EOleft
The electrode potentials ofthe cathode as well as anode should be in terms of reduction potentials.
Note: On calculation, if EOcell has a positive value, the cell reaction is feasible. On the
other hand, ifEocell has a negative value, the cell reaction is not feasible.
SOLVED NUMERICAL PROBLEMS

Based on the Calculation of E.M.F.
Example 1 : Determine the standard e.m.f. of the cell :

Cu + 2Ag+ ~ Cu2+ + 2Ag
Given E~g/Ag+ ~ - 0.80 (oxidation potential)
~ 0.34 (reduction potential)

Solution: The given cell reaction
Cu + 2Ag+ ~ Cu 2++ 2Ag
The cell for the above cell reaction is represented is
Cu I Cu2+ IIAg+ lAg
EOcell = EO(right) - E°(left) =EO(cathode) =EO(anode)
= 0.80 - 0.34 = 0.46
So, the e.m.f. of the given cell reaction = 0.46 V
Example 2 : Predict the feasibility of the given reaction.
2Ag+ Cu2+ ~ 2Ag+ + Cu
Solution: Cell involving the given reaction is :
Ag IAg+ II Cu 2+ I Cu
We know
= EO, '. (0
(u- , u
- EO,. g + • •'g
,
= 0.34 - (0.80) = - 0.46 volt.

Since the Value EO cell comes out to be negative; the given reaction is not feasible.
Example 3 : Can a solution of 1 M CuSO 4 be stored, in a vessel made of Ni metal?
Given that EO Ni. Ni 2+ = + 0.25 volt and EO eu, eu 2+ = - 0.34 volt.
SoJutJon :The reduction potentials of the two electrodes i.e. £:,2+INI ::::: - 0.25V and £;:112+1("11
::::: + 0.34V. suggest that Nickel will act as anode and copper will act as cathode. Now we wish
to know whether the follovlling reactions take place or not.
Ni + CuS0 4 ~ NiS0 4 + Cu
or Ni + Cu2+ ~ Ni2+ + Cu
The cell involving this reaction can be represented as :
Ni I Ni 2+ II Cu2+ I Cu
we know; EOcell ::::: EO(Right) - EO(Left)::::: 0.34 - (- 0.25)::::: 0.59 volt.
Since EO cell is positive. It means that CuS04 reacts with Ni. Hence CuS0 4 cannot be stored
Ni vessel.
Example 4 : Predict whether silver reacts with 1M H 2S04 to give out hydrogen
gas or not. Given that standard reduction potential of Ag is 0.80 volt.
Solution: If silver reacts with sulphuric acid, the following reaction should take place.
Ag + H 2S04 ~ Ag2S0 4 + H2
or 2Ag + 2H+ ~ 2Ag+ + H2
The cell involving the above reaction is represented as: Ag I Ag+ I I H+ I H2
EOcell : : : EO(Right)- EO(Left)
::::: Zero - 0.80 ::::: - 0.80 volt.

Since EO cell of the supposed reaction comes out to be negative, this reaction does not take
places. Hence silver cannot liberate hydrogen from the acid.
Example 5 : State whether the following representation of a galvanic cell is
correct or not. Pb/pb2+ (lM) II Mg2+ (lM)IMg
Given that E~b2+.Pb ::::: -1.126 and E~g2+'l\1g = - 2.36 V.

Solution: The representation is correct if EO cell comes out to be positive.
EOcell ::::: - 2.363 - (- 0.126)::::: - 2.363 + 0.126::::: - 2.237V
Since EO is negative, the position of the cathode and anode must be interchanged i.e., the
representation is not correct.
Example 6 : Calculate l1Go for the cell reaction at 25°C: Zn + FeSO4 ~ Fe + ZnSO4'
The standard reduction potentials are : E;zn2+, Zn) ::::: - 0.76 and E~e2+, Fe) ::::: - 0.44 V.
Predict whether the reduction is spontaneous or not. (Anna mE, Nov. 01)
Solution: For the given cell reaction, the cell can be represented as :
Zn I Zn2+ II Fe2+ I Fe Standard e.m.f. of the cell (EO cell)::::: EOcathode - EO anode
::::: - 0.44V - (- 0.76 V)::::: 0.32 V
Now l1GO ::::: -nFEo::::: - 2 X 96500 C X 0.32V::::: -61760 CV::::: -61760 J
Since the free energy change (l1Go) is negative, so the reaction is spontaneous.
( PRACTICE PROBLEMS FOR TUTORIAL )
1. Determine whether the following reactions are feasible under standard conditions
(i) Cu(s) + 2H+ (aq) -+ Cu2+ (aq) + H 2(g), Given E~u2+ , Cu =0.34 V
(ii) C~(g) + 21- (aq) -+ 2Cliaq) + I2(g)' Given.: EO C~ / Cl- Pt = +1.359 V & E;D/r-Pt =+0.534 V
2. Can Cd(NOa)2 solution be kept in a vessel made of zinc.
Given E~d+2 ICd =- 0.403 V & E~2+ =+0.76 V
S. Predict the reaction of 1 M H 2S04 with the following metals. (i) copper (ii) iron
Given E~U2+ =-0.34 V & EO Fe/Fe2+=0.44 V
4. State whether the following representation of a Galvanic cell is correct or not.
Ag IAg+ (1M) II Zn2+ (1M) I Zn, Given: E~2+, Ag =0.80 V, E~n2+ ,Zn =-0.76 V
5. A cell uses Zn2+/Zn and Ag+/Ag electrodes. Write the cell representation, half cell
reaction and net cell reaction. Calculate the EMF of the cell. Given E~ZIl2+!ZIl) =- 0.76 V and
E;AltIAg) =- 0.80 V. (VT., Aug 2K)

6. Two half cell reactions with their oxidation potentials are :
Pb(s) - 2e- --+ Pb2+ (aq); EO = + 0.13V
Ag(s) - e- --+ Ag+(aq); EO =- 0.80 V
Write the cell reaction and calculate its EMF. (Dibrugarh, June 01)
(ANSWERS )
1. (i) No ai) Yes 2. No S. (i) No (ii) Yes 4. No
5.1.56 V 6.0.67V
( BASED ON NERNST EQUATION)
Example 7 : Calculate the half cell potential at 298 K for the reaction.
Zn2+(aq) + 2e- --+ Zn(s)
If [Zn2+aq] • 0.1 M and EO =-
0.76 V
Solution: Given: n =2, [Zn2+ aq] =0.1 M and EO =- 0.76 V
According to N ernst equation:
E = EO + 0.0591 log [Mn+]

n
= - 0.76 + -0.059
- l o g 0.1 = -
2
0.7895 V
Thus half cell potential is - 0.7895 V.

Example 8 : Calculate the e.m.f. of the cell in which the reaction is :
Mg(s) + 2Ag+ (aq) --+ Mg2+ (aq) + 2Ag(s)
When [Mg2+] • 0.IS0 M and [Ag+] • 1.0 )( 10-' M,
Given thatE~g+/Ag = O.80V andE~g2/Mg = - 2.37 V

Solution: The cell is represented as
Mg(s) I Mg2+ (0.130) II Ag+ (1.00 x 1()-4 M) I Ag
Electrodes reactions are :
Mg(s) ------+ Mg2+ (aq) + 2e- ...... (oxidation)
2Ag+(aq) + 2e- ------+2Ag(s) ...... (reduction)
Overall reaction:
Mg(s) + 2Ag+(aq) ------+ Mg2+(aq) + 2Ag(s)
Since reaction involves two moles of electrons, therefore n = 2 mol. The cell e.m.f.
expression is written as :
E = EO + 0.0591 10 [Ag+]2
2 g [Mg2+]
= EO + _ EO + + 0.0591 10 (1.0 x 10-4)2

Ag lAg Mg2 IMg 2 g (0.130)
1
= [0.80 _ (_ 2.37 V) _ 0.0591 10 1.30 x 10-
2 g 1.00 x 10-8
= 3.17-0.059110g(1.30xl0')=3.17-0.21 =2.96V
2
Example 9 : For the concentration of Ag+ (aq) will the e.m.f. of the given cell be
zero at 25°C, if concentration of Cu2+(aq) is O.lM'?
Cu(s) I Cu2+ (O.lM) II Ag+ (aq) IAg(s)
(Given E : g+/Ag =+O.80V;E~u2+/cu =O.34V
Solution: We know
EOcell = EOcathode - EOAnode = 0.80 V - 0.34 V = 0.46 V
The cell reaction can be written as : Cu(s) + 2Ag+ ------+ Cu2+ + 2Ag
According to N ernst:
o= 0.46+ 0.0591 log (X)2

2 0.1
or - 0.46 = 0.0295 x 2 log x - 0.0295 log 0.1
or - 0.4895 = 0.059 log x
- 0.4895
logx = 0.059 =-8.2969
x = Antilog (- 8.2969)
Antilog of 8.2969 = 1.981 x 108 M = 5.04 X 10-9 M
Example 10 : Calculate the cell potential of the given cell at 25°C [R = 8.31 JK-l
mo)-l F = 96500 C mol-l]
Ni(s) I Ni2+ (0.01 M) II Cu2+ (0.1 M) I Cu(s)
(Given E~u2+/CU =+0.34V; E~i2+/Ni =-0.25V

Solution : For the given cell,
= EOCathode - EOAnode = 0.34 V - (- 0.25 V) =0.59 V
2.303 RT I [Cu2+]
= EOCelt + nF og [Ni2+]
0.0591 10 O.IM
0.59V +
= 2 g O.OIM
= 0.59V + 0.0295 log 10 = 0.59 V + 0.0295 V = 0.6195V
Example 11 : Calculate the voltage generated in the following cell :
Fe I Fe2+ II Mn2+ I Mn
When iron rod is immersed in 1.0 M FeSO4 solution and Mn rod is immersed in
0.1 M MnS04 solution. Given EO for Fe2+lFe is -0.40V and Mn2+/Mn is - 1.18V.
(VT, March 01)
Solution: EO cell = EOCathode - EOAnode = EO right - E01eft = (- 1.18 + 0.40)V =- 0.78V
. .. ° 0.0591 [Mn2+]
10 g [Fe2+]
Accordmg to Nernst equatlOn . Ecelt =E Cell + 2
0.1
= - 0.78 V + 0.0296 log TO
= - 0.78V + 0.0296 (-1) =- 0.809GV
Minus sign shows that the actual cell should be represented as
Mn I Mn2+ II Fe 2+ I Fe, whose E.M.F. is 0.8096 V.
Example 12 : Calculate the equilibrium constant for the reaction:
Fe2+(aq) + Ag+(aq) ~ Fe3+(aq) + Ag(s) at 25°C
If E~el+/Fe~+ =0.77Vand E : g +/Ag =0.80V (Sindri, May 01)

Solution: The cell for the given cell reaction is represented as :
Fe2 + I Fe3+ II Ag+ IAg
Now EO cell = EOCathode - EOAnode =0.80 V - (0.77V) =0.03 V
We know that, EOCell = 0.~59 log Kc or log Kc = O~O~~Il

n
1 x 0.03 V
or log KC = 0.059 V = 0.50847
or RC = Antilog 0.50847 = 3.2245

Example 13 : What is concentration of Ni2+ in the cell at 25°C, if the e.m.f. is
0.601 V?
Ni(s) I Ni2 + (a =?) " Cu2 + (0.75M) I Cu(s)
Given E ~ilNil+ =0.25 V, and E~u1+/CU =0.34 V (Sindri, May 01)

Solution: we know that EOcell = EOright - E01eft , where EOright and E01eft are reduction
potentials of cathode and anode respectively.
Given E ~'/NI2+ = 0.25V is the oxidation potential. Therefore, the reduction potential
E~i2+lNi = - 0.25 V
EO Cell = 0.34V - (- 0.25V) =0.59V
According to Nemst equation:
0.75
0.601V = 0.59V + 0.0296 log [Ni 2 +]
0.75
0.011 = 0.0296 log [Ni2+]
0.75 0.011
or log [Ni2+] = 0.0296 = 0.37162
0.75
[Ni2+] = Antilog 0.37162 =2.3529
0.75
or [Ni2+] = 2.3529 =0.3188 M
1. An rod is dipped in a solution of O.lM ZnSO 4 solution. EO for Zn2+/Zn is - 0.76Y. What
is its electrode potential?
2. Calculate the e.m.f. of the cell Zn I Zn2+ (a = 0.01) II Fe2+ (a = 0.005) I Fe at 25°C
when EO (Zn 2+/Zn) =- 0.763 volts and EO(Fe 2+lFe) =- 0.44 volts.
3. Calculate the cell potential for the following cell :
Pb I Pb2 + (1 X 10+3M) II (0.1M) 1/2 C12, Pt
Given that E~b2+. Pb = 0.13 V and E;/2C1 2 /CI = 1.358 V
4. Represent schematically the cell made up of the half cell reactions:

Mg ~ Mg2+ (0.01M) + 2e-, EO = 2.34V
Sn2+ (0. 1M) + 2e-~ Sn, EO =- 0.136V
Calculate the e.m.f. of the above cell at 25°C.
(ANSWERS)
1.-0.82V 2.2.314V 3.1.110V 4.2.234V

2.9 TYPES OF CELLS
There are mainly two types of galvanic cells : (i) primary cells and (ii) secondary cells.
(i) In primary cells, the reaction occurs only once and the battery then becomes
dead over a period of time and cannot be used again. (For example, dry cell, mercury
cell).
(ii) Secondary cells can be recharged by passing current through them so that they can
be used again and again. (For example lead storage battery, nickel-cadmium storage
cell).
A. Primary Cells
(a) Dry cell: The most familiar type of battery is the dry cell, which is a compact version
of Laclanche cell (Fig. 2.9) In this cell, the anode consists of a zinc container and the cathode
is a graphite rod surrounded by powdered Mn0 2 and carbon. The space between the electrodes
is filled with a moist paste of NH 4CI and ZnCI 2 . The electrode reactions can be written
approximately as.
At anode: Zn(s) ~ Zn2+ + 2e-
At cathode:
In the cathode reaction, manganese is reduced from the +4 oxidation state to the +3 state.
Ammonia is not liberated as a gas but combines with Zn2+ to form [Zn( NH3 )4]2+ ion. Dry cells
do not have an indefinite life as acidic NH 4CI (+)
corrodes the zinc container even while not in r-"--"~_- Metal cap
use. Dry cells have a potential of approximately
........,P"'!"III"' ....... Pitch seal
1.25 to 1.5V. An improved form of dry cell in
which NH 4CI is replaced by KOH as an container
electrolyte avoids corrosion of zinc container (anode)
since zinc does not dissolve readily in a basic
medium. In this cell, zinc in powdered form is cover
mixed with KOH to get a gel. This cell is called Graphite cathode
alkaline cell.
As the life of alkaline cell is longer and
maintains better voltage than dry cell, it finds
application in use of calculators, watches,
camera etc.
H
(b) Mercury cell: A new type of dry cell,
Fig. 2.9. A dry cell.
which has found use in small electrical circuits
(such as hearing aids, digital watches and cameras), is the mercury cell. Here zinc mercury-
amalgam is the anode; a paste of HgO and carbon is the cathode. The electrolyte is a paste of
KOH and ZnO. The reaction of the cell is as follows:
At Anode: Zn (amalgam) + 20H- ~ ZnO (s) + H 20 + 2e-
At Cathode: HgO(s) + H 20 + 2e- ~ Hg (l) + 2 OH-
Overall reaction: Zn (amalgam) + HgO(s) ~ ZnO(s) + Hg(1)
Since the overall cell reaction does not involve any ion in solution whose concentration
can change, the cell shows constancy in potential through out its life. The cell potential is
approximately 1.35V.
B. Secondary Cells
The most important secondary cell is the lead storage battery containing six
cells of 2 V
each connected in series. A lead accumulator for cars consists of six acid storage cells connected
is series and it is capable of delivering 12V (Fig. 2.9). Each cell of a battery consists of a lead
grid fill~d with spongy lead as anode and a lead grid packed with lead dioxide as cathode
(Fig. 2.10). A solution of sulphuric acid (38% by mass of density of 1.3g cm-3 ) is used as an
electrolyte in which a number of the electrode pairs, containing inert powers partition is
between are dipped. The reactions taking place in the cells during use or discharge are:
I..eaddioxide
IPbO)
!.tad (Pb)
---------
Fig. 2.9 (a). Lead storage battery of 6 volts.
At Anode :
Pb(s) ~ Pb 2 + + 2e-
Pb2+ + S042-- (aq) ~ PbS04 ,j,
At Cathode:
Pb02(s) + 4H+(aq) + 2e- ~ Pb2 + + 2H20
Pb2+ + SOl- ~ PbS04 ,j,
Overall reaction: Pb(s) + Pb02(s) + 4H+(aq) + 2S042--(aq) ~ 2PbSOis) + 2H20
Source of
Meter direct current
(i) Discharging (ii) During recharging

(Act as electrolytic cell)
Fig. 2.10. Discharging and recharging of a lead storage cell.

During discharge, H 2S04 is used and its density falls. When the density falls below 1.2 g
cm-3 , the battery, can be recharged after use by passing electric current.
During recharging, the cell reaction gets reversed at the respective electrodes as under:
At Anode :
Pb80 4 (s) + 2e-~
Pb + 8042- (aq)
At Cathode:
Pb80 is) + 2H20 ~
Pb0 2 (s) + 8°42-(aq)
+ 4 H+ (aq) + 2e-
Overall reaction:
2Pb80 4 + 2 H 20 ~
Pb (s) + Pb02 (s) + 4 H+ (aq) + 2 8°42- (aq)
Pb(s) + Pb02(s) + 4H+(aq) + 28042-(aq) ~ 2Pb80is) + 2H20
This is possible because solid Pb80 4 formed during the working of the cell sticks to the
electrodes and can gain or lose electrons during recharging.
(c) Nickel-cadmium storage cell : Another secondary cell is the nickel-cadmium
storage cell, which has a longer life than the lead storage cell but is more expensive to
manufacture.
It consists of Cd as anode and metal grid containing Ni(IV) oxide as cathode immersed in
KOH solution. The cell reaction is given below:
Atanode:
Cd(s) + 2 OH- (aq) ~ Cd(OH)2 (s) + 2e-
At cathode:
Ni0 2(s) + 2H20 + 2e- ~ Ni(OH)zCs) + 2 OH- (aq)
The overall reaction is :
Cd + Ni0 2 + 2H20 ~ Cd (OH)zCs) + Ni (OH)2 (s)
In this cell, the reaction products adhere to the electrodes and the reaction can be reversed
by charging. Since no gases are evolved during charging or discharging, so tl1is cell has very
long life and its potential is about 1.4V
It is widely used in cordless phones, cordless electronic shavers and electronic flash unitH.
2.10 CONCENTRATION CELLS
There are different kinds of cells as shown below :
Cl<~LLS
~
Electrochemical cells Concentration cells
(Galvanic cells) Here e.m.f. arises due to change in concentration of
either the electrolyte or the electrode
I-Jere e,m.f_ arises from dE:crease in free
enenrv due to chemical reaction occuring in cell I
", \ + t
~ +
Without transference
Electrolyte
concentration cell
Electrode
concentration cell
WIth transference
I
With transference Without transference
We have already discussed the details about electro-chemical cells. We will now take up
the details of concentration cells. .
A concentration cell is galvanic cell in which electrical energy is produced by the transference
of a substance from a system of high concentration to one of low concentration and there
is no net chemical reaction involved.
In general, there are two types of concentration cells.
(1) Those having an electrolyte of two different concentrations but identical electrodes
are called Electrolyte concentration cells.
(2) Those having electrodes of two different concentrations but the electrolyte of same
strength are called Electrode concentration cells.
(A) Electrolyte Concentration Cell Without Transference
When the two electrolytic solutions are not in direct contact with each other and
transference of ions from one solution to other does not take place directly. The two solutions
are separated by means of salt bridge.
Concentration cells with same electrodes but having different concentrations of electrolytes
and are connected by a salt bridge.
Flow of electrons
When the concentration of an electrolyte
is altered there occurs corresponding change Et----.Zmc r o d - - -
in the potential of the electrodes in contact
with the electrolyte. Thus a cell can be
constructed by dipping two identical electrodes
ZnS04
in solutions of different concentration of the
ZnSO, solution
same electrolyte. The source of electrical (C 2 )
energy in the cell is the tendency of the solution
(C l )
electrolyte to diffuse from a solution of higher
concentration to that of lower concentration.
Thus with passage of time the two Salt bridge
concentrations tend to become equal. For this
reason the e.m.f. of a concentration cell is Fig. 2.10. Typical concentration cell where C2 > C1·
maximum at the start and it gradually falls to zero as the two concentration become equaL
(i) A concentration cell (Fig. 2.10) with zinc electrodes and the solution of zinc sulphate of two
different concentrations C l and C 2 joined together through a salt bridge can be represented by
o ffi
Zn I Zn 2 + (Cd II Zn 2+ (C2 ) I Zn
The concentration C 2 is greater than C l . The electrode reaction on the left-hand is
oxidation:
Zn ~ Zn2+ (C l ) + 2e-
While that on the right hand is :
Zn2 + (C 2) + 2e- ~ Zn
So that the net reaction is
Zn2+ (C ) ~ Zn2+ (C l )
Evidently there is no chemical reactfon. There is merely transference of zinc ionR from
the solution of higher concentration (C 2 ) to the solution oflower concentrating (C/
o 2.303 RT I C
Eel (R.H.S.) = E e1 + nF og 2
E el (L . H . S)
.
= EOel + 2.3 0n 3F RT IogC 1
The e.m.f. of such a cell is given by the expression
Ecell = Eel (R.H.S.) - Eel (L.H.S.)
= 2.303 RT log C 2
nF C1
By substituting the value of R = (8.314 Jules) and F = (96500 coulombs), we can calculate
the e.m.f. of the cell at the given temperature. At 25°C, we have
= 2.303 x 8.314 x (273 + 25) log S
E n x 96500 C!
0.0591
2 C
E = -n- 1og-
C!
(ii) Another example of this type of
concentration cell is given below in which both the
electrodes are hydrogen electrodes (Fig. 2.11)
In each electrode H2 gas at one atmospheric
pressure is passed but the activity of H+ in the two
same electrolytes is different. These electrodes are
joined by a salt bridge. 1 atm
Pt, H2 (1 atm) I H+ (a l ) II H+ (a2) I H2 (1 atm), Pt
(a2 > a l )
On the L.H.S. electrode oxidation takes place
and the electrode reaction is
1/2 H2 (atm) ~ H+ (a l ) + e-
Th apply Nernst equation, the reduction half of
the above reaction is written as : Fig. 2.11. Concentration cells consisting of
H+ (a l ) + e- ~ 1/2 H2 (1 atm) hydrogen electrode.
:. Electrode potential of this electrode will be
o RT I
El = E(W/H) - - In -
2 F al
o RT
= E(H+/H 2 )+T lna l
RT
= -Ina!
F
On the RHS electrode reduction takes pace. The electrode reaction is
H(a2) + e- ~ ~ H2 (1 atm)
By Nernst equation, the e.m.f. of this electrode will be
RT
E2
F= - I n a?
-
The overall reaction is obtained by adding two half reaction. This gives
H ea2 ) ~ H(ad
The e.m.f. of cell is given by
E = E 2 -E l
RT RT
= - I n a2 - - I n a1
F F
RT In-2
= F al
(B) Electrolyte Concentration Cell with Transference
Concentration cells with same electrodes but having different concentrations of electrolytes
which are directly in contact with each other. In these cases the cells are represented as :
(i) Zn I Zn SOia1): Zn S04 (~) I Zn
(ii) Pt, H2 (1 atm) I HCI (a 1) : HCI (a 2) I H2 (1 atm), Pt
(The double line has been replaced by a dotted line
showing the two solutions are in direct contact.)
These cells can be set up by putting two solutions
in a V-tube very carefully so that there is no mixing of
the two solutions (Fig. 2.12) The junction at which the
two solutions meet is called the liquid junction potential.
Activity =a 1
The expression for e.m.f. of these concentration cells
have already been given.
Liquid junction
(a) Concentration cells Obtained by the
Combination of Two Chemical Cells Fig. 2.11. Concentration cell with a liquid
junction.
Consider a cell in which the H2 electrode and Ag,
AgCI electrode are dipped. in the same solution of HCI of activity a 1
Pt, H2 (1 atm) I HCI (a1) IAgCI (s), Ag
The cell reaction is
1/2 H2 (1 atm) + AgCI(s) ~ Ag(s) + HCI (a1)
By Nernst equation, e.m.f. of this cell is
o RT
E1 = E - - In a I (n = 1)
F
The activities of solids Ag, AgCI and that of H2 (1 atm) is unity.
Let us have another'similar cell but with different activity of HCI (a2). The e.m.f. of this
cell is
o RT
E2 = E - - I n a2 (n = 1)
F
If the two cells are connected so as to oppose each other and then make one concentration
cell.
Pt, H2 (1 atm) I HCI (a1), AgCI(s), Ag lAg, AgCI(s), HCl(~) I' H2 (1 atm) Pt
The overall reaction of this cell will be the difference of the cell reaction which will come
out to be
Similarly e.m.f. is given by
E = E _E _
1 2-
(EO - RT In al ) -
F
(EO - RT In a 2)
F
= - -RT
F
I n al
RT RT a2
+-In a2 = - I n -
F F al
(b) Chemical Cell with Transfer
The common example of this type of cells is Daniel cell.
Zn I Zn 2+ "Cu 2+ I Cu
There is liquid junction potential in the cell because of two different electrolytes in the
cells.
Electrode Concentration Cell
The electrodes may have different concentration. Mostly these electrons are gas electrodes
operating at different pressure or these are amalgams .(Hg + metals) with different
concentration. For example,
Cd{Hg) (Coo =C1) I Cd2+ I Cd(Hg) (Coo =C2)
Electrode Reaction
Oxidation
Reduction
Over all Reaction Cd(Cd ~ Cd(cz)
e.m.f. of cell E = ER-~

E -- 0.0591 1og-
Ct
2 C2
If C2 < C1 then e.m.f. will be positive and the reaction will be spontaneous i.e. Cd 2+ will go
from higher to low concentration of amalgam.
In case of gas electrode concentration cell, for example
Pt I H 2(P1) I HCII H 2(P2) I Pt
Reduction 2H+ + 2e- ~ ~(P2)
Oxidation H 2(P1) ~ 2H+ + 2e-

Overall H 2(P 1) ~ H 2(P2)
E = P - 0.0591 log !2.

2 Pt
If P2 < P1 then e.m.f. is +ve, so process will be spontaneous.
Example 14 : Determine the e.m.f. of the concentration cell consisting of zinc
electrodes, one immersed in a solution of 0.01 M concentration and the other in a
solution of 0.1 M concentration of its ions at 25°C.
Solution: The cell may be shown as
Zn;Zn2- (C = 0.01) I I Zn2+ (C = 0.1); Zn
2.303 RT 0.1 0.0591
e.m.f. of the cell, E = 2F
log - - =
0.01 2
log 10 =0.0295 Volt.
Example 15 : Calculate the e.m.f. of the following cell at 25°C.
= = =
Cd I CdS04 (m 0.01, Y 0.383) II CdS04 (m 1.00, Y 0.42) I Cd =
Solution: It is given that m 1 = 0.01, Y1 = 0.383, m 2 = 1.00, Y2 = 0.02
And for a Cd/Cd+2 electrode, n =2
We know E
= RT In ~ = 0.059 log m2Y2
nF at 2 mtYt
We know that a = ym,
where a = activity, y = activity coefficient and m =molality of the electrolyte
0.59 10 1 x 0.042 _ I
= 2 g 0.01 x 0.383 - 0.307 vo t
1. The EMF of the cell Zn I 0.045 M ZnS0 4 11 ZnS0 4 (unknown conc.) I Zn is 0.0089 volt
at 25°C. Calculate the concentration of ZnS0 4 in the right hand compartment. The
salt in both the cells is completely dissociated.
2. Calculate voltage generated in a cell at 25°C in which a half cell consists of a
1 M AgN0 3 solution and silver wire electrode in other half cell a silver wire dips into
0.01 M AgN0 3 solution?
3. Calculate the EMF of the following concentration cell at 25°C.
Cu I CuS0 4 (m =0.02, Y = 0.32) II CuS0 4 (m =0.2, y =0.11) I Cu
( ANSWERS)
1.0.09M 2. 0.1182 volt 3. 0.0158 volt

2.11 DETERMINATION OF pH
One of the extensive application of e.m.f. measurements is in determining the pH of various
solutions. In all potentiometric measurement of pH, the procedure followed is very much the
same.
First a cell is assembled from the following two types of electrodes :
(i) One of the electrodes (indicator electrode) is reversible to hydrogen ion and dips in
the solution whose pH is to be determined. Its potential depends on the activity
(concentration) of the hydrogen ions of the solution in which it is dipped.
(ii) The other electrode is a reference electrode usually a standard calomel electrode.
The electrode potential of this electrode has a constant value at a given temperature
and under similar conditions.
Junction between the two is made either through a salt bridge or by immersing the
reference electrode directly into the solution.
The cell thus obtained may be represented as :
Indicator electrode I Salt Bridge I Reference electrode
The position of the electrodes on the R.H.S. or L.H.S. is determined from the respective
values of their reduction potentials. The electrode with rugher value of reduction potential is
placed on the R.H.S.
Next the n.m.f. of the cell (combination of two electrodes) is measured with a suitable
potentiometer.
From the e.m.f. of such a cell and the electrode potential of a reference electrode (which
is known), we can calculate the activity of hydrogen ions (i.e., concentration of hydrogen ions)
or the pH of the solution by the relationship
EceU = E (R.H.S.) -E(L.H .s.)
Electrode potential of reference electrode (constant) -
Electrode Potential of Indicator electrode
Electrode potential of indicator electrode involving the reaction H+ + e- ~ 1/2 H2 electrode
is given by N ernst equation as :
EO + _ RT In (aH2)1/2
E H + ,H 2 = H 'H2 F (a) +
H
If H2 gas is at 1 atm pressure a~ =1
E H+ H
, 2
= EO
H
+
,
H
2
+ RFT In a
H
+
Replacing the activity of H+ ion by its molar concentration, we have
E H +,H 2 = RT In [H+] =0.0591 log [H+] at 25°C

F
Since the standard electrode potential hydrogen electrode is taken as zero.
Here Ew H
, 2
= EO
H
+
,
H
2
+ RT
F
In [H+] at 25°C
Ecell = constant - 0.0591 log [H+]
= constant + 0.0591 pH [.,' pH = -log (H-)]
or 0.0591 pH = Ecell - constant
Ecell - constan~
or pH =
0.0591
The value of constant depends on the reference electrode used. For standard or normal
hydrogen reference electrode, the constant is equal to zero, whereas for a standard calomel (1
molar KCI solution) reference electrode, the value of constant is equal to 0.2810. In case
reference calomel electrode used is in contact with saturated solution of KCI, the value of
constant is 0.2422.
2.11.1 Determination of pH using Hydrogen Electrode
Solution whose pH is to be determined is taken in a vessel and a platinum electrode is
half dipped in the solution. A slow current of hydrogen gas at 1 atmosphere is bubbled through
the solution. The potential of this hydrogen electrode depends on the pH value of the solution
with which it is in contact.
The above half-cell so formed is connected to a standard or normal hydrogen electrode.
The complete cell may be represented as :
Pt I H2 (1 atm) I H+ (aH-) I H+ (a = 1) I H2 (1 atm) Pt
The e.m.f. of the full cell is then determined by means of a potentiometer. Since electrode
potential of standard hydrogen electrode is zero, therefore,
Ecel1 - 0 Ecel1
pH = 0.0591 or pH = 0.0591
The, hydrogen electrodes used in these measurements require the following conditions for
the efficient operations :
(i) The platinum electrodes should be in the form of foils and freshly platinised so that
the oxidation and reduction reactions are equally catalysed.
(ii) Hydrogen gas used should be free from oxygen.
2.11.2 Determination of pH using Glass Electrode
In order to determine the pH of solution
the above halken €.e., glass electrode is placed
in the solution under test and a potential so
Calomel
established is measured by combining it with electrode Glass
a reference saturated calomel electrode H!Jo--lo:fl-"'; electrode
(Fig. 2.13) Saturated
KCl solution
The cell may be represented as
Calomel electrode I Experimental solution
of unknown pH I Glass electrode mercury Solution
Because of the high internal resistance of under test
the glass electrode, which may amount to as Fig. 2.13. Determining of pH by glass electrode.
much as 100 million ohms; an ordinary
potentiometer cannot be used to measure e.m.f. of the cell. Either quadrant electrometers or
vacuum tube voitmeters (V.T.V.M.) which require practically no current for their operation must
be employed. For this purpose, vacuum tube circuits have been developed which not only are
sensitive to 0.01 pH unit or better, but also are portable and very rugged.
The e.m.f. of the complete cell is given by :
Ecell = EOg - 0.0591 pH - 0.2422
EO g - 0.2422 - Eeell
or pH = 0.0591
where EO is the potential for the given glass electrode. The value of this constant can be
determin~d, for the system, by using a solution of known pH in the vessel containing the glass
electrode and measuring the overall potential.
After knowing EO , the e.m.f. is measured using unknown solution and its pH determined
by the above equatioJ.
Note all glass electrodes in a particular assembly have the same value of EO g (because of
asymmetry potential). For this reason, it is best to determine EOg for each electrode before
use.
Advantages of Glass Electrode : (i) The glass electrode is the nearest approach to a
universal pH electrode known at present. (ii) It is not poisoned easily, nor it is affected by
oxidising or reducing agents or by organic compounds. (iii) Further, it can be used on quantities
of solution as small as a fraction of a cubic centimeter.
Limitations: Its only limitation arises in strongly alkaline solutions where the glass is
attacked, and in solutions of pH = 9 and above where presence of various cations, particularly
sodium, leads to appreciable errors.
Example 16 : EMF of the cell
Pt, H2 (1 atm) solution of unknown pH II Hg2CI2(s) KCl(s) I Hg
is 0.366 volts. Ignoring the junction potential, determine the pH of the given solution.
EMF of S.C.E. being + 0.242 volts. .
Solution: According to EMF of the cell is given by
Ecell = E(R.H.S.) -E(L.H.S.)
= Ecalomel - E H +,H 2
EWH
, 2 = Ecalomel- Ecell
Now by N ernst eqn. E H + •H 1 = 0.059 log [H+] =- 0.059 pH

-0.059 pH = Ecalomel - Ecell
90 Essentials of Engl.neenng CherrusllY
Ecell - Ecalomel
or pH = 0.059
0.366 - 0.242
= 0.59
=0.098
2.12 ION SELECTIVE ELECTRODE
Electrodes which can selectively detect and quantitatively measure a particular chemical
species neglecting others in a system are called ion selective electrodes.
They have the capability to respond to certain specific loss present in a mixture inespective
of any other species present alongwith. The potential developed is a measure of the concentration
of the species concerned. These electrodes use membranes which are sensitive to particular
chemical species generally following four types of membranes are used.
(a) Glass membranes, (b) Solid state membranes, (c) Liquid membranes and
(d) Heterogeneous membranes.
Construction of Ion Selective Membranes
For solid state membranes the material used is a pressed pellet of lanthanum trifluoride
crystal doped with europium difluoride for the detection of fluoride ions and that of Ag 2 S and
AgCI for chloride ions. Similarly suitable materials for the detections of other cations and anions
have been developed for use. The crystal is held in position with epoxy resin and the body of
the electrode is made of Teflon. Fig. 2.14(b).
For liquid membranes the material used is commonly a large organic molecules (usually
esters or ethers) capable of specifically interacting with a cations or an anions. The active organic
molecule is adsorbed on in insert proous support. Fig. 2.14(c) For alkali and alkaline earth
metal cations, the material used are the phosphate diesters and neutral monocylclic crown
ethers, whereas for anions iron phenanthroline complex namely [tris - 1, 10 phenanthroline,
Fe 2+(CI0 4)2 is commonly employed.
Ion selective electrodes are used as interface between certain chemical systems and
electronic devices that display, record and manipulate data. For instruments employing ion
selective electrodes a very sensitive voltmeter is required for the measurement of potential
difference between the ion selective electrode and the external reference electrode. It is because
an enor of 0.1 mV in the measurement of potential difference may result in 1(7(! error in the
ion analysis.
Principle of Membrane Electrode
For the measurement of concentration of a metal ions using an ion selective electrode,
the following cell is set up:
Reference solution to Internal stan dard Reference
electrode 1 be analyzed solution electrode 2
[M n+] =C 1 ~M"+] = C2
External refe;ence electrode Ion-seleebv .. pleetl "ell'
The membrane potential is given by the equation
EM ,,+ = -RT
I n C2 /C 1
nF ".(i)
Glass
TefJonbody_
l}~
Reference_
electrode
Internal
electrolyte Internal - ~:~,;~,
Reference electrolyte
electrode
~=-IiE:;:r-- Pellet
iii~~I~tli~€I€;iiI'illY :~~~~r
Glass electrode
membran..
Fig. 2.14. Ion-selective electrodes with different types of membranes (a) glass (b) solid state
(pellet) (c) liquid membrane on a porous polymer.
where C 1 and C2 are the concentrations of Mn+ in the solution to be analysed and the internal
reference electrode respectively.
Suppose in a cell the reference electrode is anode and the membrane electrode is cathode,
the cell potential (Ecell ) is given as
RT
EceII = constant - -
nFIn C ...(ii)
where C 1 is the concentration ofMn+ in the solution to be analyzed.

Thus the cell potential depends on the selectivity of the membrane for the ion Mn+, which
is to be analyzed. The potential depends on the relative concentration of Mn+ as given by
equation (i) and does not depend on the concentration of other ions present.
If other ions are also present, then
EceU = constant - :! In { C + ~ KiC i}
where Ci is the concentration of other ions present in the system.

For the membrane to selectively work I\ should be as small as possible.
Applications of ion-selective electrodes
(i) Determination of concentration of a gas: Let us take as example of measurement
ofthe concentration of CO 2 gas in blood samples. In this case we makes use of a glass electrode
which as used for mesuring pH. The glass electrode is in contact with a very thin silicon rubber
membrane permeable to CO 2, The membrane is soaked in a dil solution of NaHCOa. When
the electrode is dipped in the blood sample, it allows the CO 2 to permeate into the membrane.
CO 2 then reacts with NaHCO a and alters the pH. This change in pH is then noted the glass
electrode. Thus, the potential of the glass electrode gives a measure of the CO 2 in the blood
sample.
(ii) Determination of concentration of cations : These electrodes are used in
determining the concentrations of a number of cations such as Li+, Na+, K+, Ag+, NH4 +, Pb2+,
Cd2+, Cu2+, Ca2+, Mg2+ etc.
For instance, calcium ion concentration can be determined by making use of an ion selective
electrode sensitive to Ca2+ ion. This analysis has important applications in physiological
investigations because Ca2+ ion is known to influence bone formation, muscle contraction,
cardiac expansion & contraction and nerve conduction.
(iii) Determination of concentration of anions: The ion-selective electrodes can also
be used for finding out the concentration of anions such as F-, N0 3-, CN-, S2- and other halide
ions. A suitable electrode material which is sensitive to the anion under consideration has to
be selected. For instance, F- ions are sensitive to lanthanum trifluoride doped with europium
difluoide.
(iv) H+-ion selective electrode is used for determining the pH of the solution just as glass
electrode. A suitable internal electrolyte for the glass electrode has to be chosen to make it
act as an ion selective glass electrode.
( SOLVED SHORT ANSWER PROBLEMS)
Problem 1 : In an electrolytic cell, anode is referred as an oxidation electrode

and cathode is referred to as reduction electrode. Why ?
Solution : When an electric current is passed through the electrolytic liquid, the ions are
attracted by oppositely charged electrodes.
Positive ions as cations move towards cathode, where they gain electrons (i.e., they get
reduced and converted into neutral particles. Thus reduction takes place at cathode. Hence
cathode is called reduction electrode.
Anions move towards anode where they lose their charge by losing electrons i.e., they get
oxidised. Thus oxidation takes place at anode. Hence Anode is called oxidation electrode.
Problem 2 : When zinc rod is dipped in copper sulphate the blue colour of copper
sulphate is slowly discharged. Explain.
Solution: A metal having lower reduction potential can displace a metal having higher
reduction potential from the solution of its salt.
Since E~n 2+ IZn < E ~u 2+ leu' zinc can displace copper from the solution of copper sulphate
solution. When zinc rod is dipped in copper sulphate, the colour will gradually fade away and
the solution will become colourless due to the formation of zinc sulphate while the copper will
settle down.
Zn(s) + CuS04 (aq) ~ ZnSOiaq) + Cu(s)
Blue Colourless
Problem 3 : Why does an electro-chemical cell stop giving current after
sometime?
Solution : The flow of electric current is due to the potential difference between the two
electrodes. With the passage of time, the reduction potential of anodic half cell increases while
that of the cathodic half cell decreases and a stage is reached when the two electrode potentials
equal each other and hence the flow of current stops. With the passage of time the concentration
of Zn2+ ions in the anodic half cell increases resulting in the decrease of reduction potential.
On the other hand, the concentration of Cu2+ ions in the cathodic half cell decreases resulting
in the increase of reduction potential. When the two reduction potentials become equal to each
other, there remains no potential difference between the electrodes and hence the cell stops
giving current.
Problem 4 : Explain giving reason, why zinc and iron decompose steam whereas
copper and mercury do not.
Solution: A metal can displace hydrogen from water and a dilute acid only if its reduction
potential is less than that of hydrogen. Since the potential of hydrogen is arbitrarily taken as
zero, metals having negative value of reduction potential can displace hydrogen from water or
dilute acids. In other words, only those metals which lie above hydrogen in the electrochemical
series can displace hydrogen and the metal which lie below hydrogen in the electrochemical
series cannot displace hydrogen from water or dilute acids. Since zinc and iron having negative
reduction potentials lie above hydrogen in the electrochemical series, they can displace hydrogen
from steam, whereas copper and mercury having positive reduction potentials lie below hydrogen
in the electrochemical series, they cannot decompose steam.
Problem 5 : Is it safe to stir 1 M AgN03 solution with a copper spoon? Given
E ~giAg = 0.80V, E~U2+/CU = 0.34V. Explain.
Solution : No copper spoon will dissolve as Cu2+ ions. It can be shown that the redox
reaction. Cu + 2Ag+ ~ Cu2+ + 2 Ag is feasible. The electrochemical cell for this reaction is :
Cu/Cu2+ II Ag+/Ag. The standard e.m.f. of
=0.80 - 0.34 =0.46

The value of EOcell being positive, the value of AG comes out to the negative from the relation
(-AG = nFEO). The reaction is, therefore, spontaneous. So, it is not safe to stir AgN0 3 solution
with a copper spoon.
Problem 6 : What is the change in free energy for (a) galvanic cell and
?
(b) Electrolytic cell
Solution: (i) For galvanic cell, free energy decreases i.e. AG < O.
(ii) For electrolytic cell, free energy increases, i.e. AG > O.
Problem 7 : Can we measure the absolute value of the electrode potential?
Solution: Voltage is a measure of flow of electric charge. An electrode has to be coupled
with a reference electrode to set up an electrochemical cell. Hence, the absolute value of the
electrode potential cannot be measured. It is the relative value of electrode potential with
reference to a standard electrode (such as standard hydrogen electrode) which is expressed
since no current flows through an isolated half cell, neither the voltage nor the electrode
potential can be measured.
Problem 8 : By referring to the data given below explain. Why zinc protects iron
more effectively than tin, once the protecting coating has been scratched.
Zn2+ + 2e- ~ Zn; - 0.76 V
Fe 2+ + 2e- ~ Fe; - 0.44 V
Sn2 + + 2e- ~ Sn; - 0.14 V
Solution: Zinc prrvides sacrificial protection to iron against corrosion because reduction
potential of zinc is less than that of iron. In case some scratches occur on the protective zinc
layer of the galvanized iron even than iron will not be rusted. This is because zinc and exposed
iron set up an electrochemical cell in which zinc acts as anode (having lower reduction potential)
and iron acts as cathode (having higher reduction potential). The zinc anode undergoes corrosion
saving the iron cathode. Although iron can also be protected against corrosion by coating with
tin, yet it cannot be saved when scratches occur. Here also the exposed iron sets up an
electrochemical cell with tin but iron acts as anode (having lower reduction potential) and tin
acts as cathode (having higher reduction potential). The iron anode undergoes corrosion and
the tin is unable to save it.
Problem 9 : Define the terms (i) Electrode potential (ii) Reduction potential and
(iii) oxidation potential.
Solution: Electrode potential is the tendency of an electrode to change into ions and vice
versa, when it is placed in contact with a solution containing its own irons. In other words, it
is the tendency of the electrode to gain or to lose electrons when in contact with its own ions ..
The tendency of an electrode to get reduced i.e. to gain electrons when it is in contact
with its own ions in solution is called reduction potential. The tendency of an electrode to get
oxidized i.e. to lose electrons when in contact with its own ions is called oxidation potential.
Reduction potential is nothing but oxidation potential with a negative sign.
Problem 10 : Write Nernst's equation for an electrode. How can you increase the
value of reduction potential of an electrode?
Solution: For an electrode, M(a~) + ne- ~ M(s)
o 2.303 RT I n+
N ernst equation is : = E M+/M +
nF
og M(aq)
The reduction potential of an electrode can be increased by increasing the concentration

of the metal ions in contact or by increasing the temperature.
Problem 11 : Differentiate between (i) Electrochemical cell (ii) Concentration cell
and (iii) Fuel cell.
Solution: Electrochemical cell is a device to convert the chemical energy of a redox reaction
into electrical energy.
A concentration cell is a device to get electrical energy from the tendency of two solutions
to equalize their concentration in two half cells. A fuel cell is a device for converting the energy
of a fuel (H 2 , CH 4 , CH 30H etc.) directly into electrical energy.
Problem 12 : The emf of a concentration cell gradually decreases. Why?
Solution: The emf of a concentration cell is given as :
2.303 RT C
Ecell = nF log C~ , where C2 is greater than Cl·
The concentration works due to transfer of ions from the solution of higher concentration
to the solution of lower concentration. As the process continues, the difference in concentration
between two half concentration cells decreases. Consequently the emf of the cell also decreases.
The ratio of concentration, C/C l goes on decreasing gradually and finally the cell stops working
when C 2 becomes equal to Cl.
Problem 13 : Why does a dry cell become dead after a long time, even if it has
not been used?
Solution: In a dry cell, NH 4CI is packed in zinc container. The salt being acidic in nature
gets hydrolyzed and corrodes the zinc container, even if the cell is not functioning.
Problem 14 : Why is salt bridge used in the construction of a cell ?
Solution: Salt bridge completes the electrical circuit and permits the ions to move from
one solution to another without direct contact of the two. It avoids mixing ofthe two solutions.
Moreover, it maintains electrical neutrality of the solutions in the two half cells. A wire can
not be used to connect the two electrodes internally because it produces voltage drop.
Consequently, accurate measurement of the emf can not be made.
Problem 15 : Voltmeter cannot be used in the precise measurements of emf of the
Galvanic cell. Why?
Solution: The emf of a cell cannot be measured accurately by using a voltmeter, because
a part of the current is drawn by the voltmeter itself, thereby giving lower value of emf than
the actual one. So, it is better to make measurement of emf potentiometrically.
Problem 16 : Electrode potential of zinc is assigned a negative value, whereas
that of copper a positive value. Give reason.
Solution: Zinc electrode is anodic w.r.t. NHE, i.e. the electron flow is from zinc electrode
to hydrogen electrode. So its reduction potential is assigned a negative value. On the other
hand, copper electrode is cathodic w.r.t. NHE i.e. the electron flow is from hydrogen electrode
to copper electrode. So, its reduction potential is assigned a positive value.
Problem 17 : What is lead-acid accumulator? Lead is oxidized or reduced during
its working?
Solution: A secondary cell consisting oflead electrodes, the positive plate: lead grill fllled
with Pb02 and negative plate: lead grills filled with spongy lead and both dipped into ~SO4
solution. Lead is reduced from Pb4+in Pb0 2 to Pb 2+ in PbS04.
Problem 18 : Why do we use NH4N0 3 or KCI for preparing salt bridge?
Solution: We use NH4N0 3 of KCI in salt bridge, because the transport numbers of NH4 +
and NO g- ions (or K+ and CI- ions) are nearly equal to each other (around 0.5 each). So, there
is no net transfer of these ions during the functioning of the cell.
Problem 19 : Can we use KCI in the salt bridge in a cell having Ag or Pb as one of
the electrodes?
Solutions: We can not use KCI in the salt bridge in both cases, because Ag+ ions or Pb 2+
ion from the solution would combine with CI- ions from KCI to form AgCI or PbC~. Both the
salts formed are insoluble. As a result of the reaction, the concentration of the solutions of
the two half cells would change. The emf of the cell will change accordingly.
Problem 20 : Which electrode is anode and cathode in a cell made from aluminium
and silver half cells?
Solutions: The AI-half cells is more negative to the Ag-half cell. So oxidation will take
place at the AI electrode when combined with Ag-electrode. The electron flow would be from
AI to Ag in the external circuit. Tllerefore, AI-half cell will act as anode and Ag-half cell would
act as cathode in the cell.
Problem 21 : Glass electrode is preferred to quinhydrone electrode in measuring
pH of a solution. Give reason.
Solution: Glass electrode is s1mple, not easily oxidized and attains eqUilibrium rapidly. It
can safely be used upto pH of 10. On the other hand, quinhydrone electrode can be used upto
a pH of 8 only. Moreover, it cannot be used in solutions containing redox systems. Hence use
of glass electrode is preferred over quinhydrone electrode in pH measurements.
Problem 22 : What is a reference electrode? Why use of calomel electrode as a
reference electrode preferred?
Solution : The electrode which is used for measuring the electrode potential of another
electrode by combining with it to form a cell is called a reference electrode. The electrode
potential of NHE electrode is taken as zero and it can be used as a reference electrode. NHE
is obtained by dipping platinum foil in 1M - HCI solution through which hydrogen gas is passed
at 298K under 1 atm. pressure. The use of NHE as a reference electrode is not convenient
because of the following:
(i) It is difficult to maintain a pressure of H2 gas at 1 atm. pressure and [H+] ion
concentration of solution at 1M.
(ii) The platinum electrode used get poisoned by the traces of impurities.
(iii) Handling of NHE is difficult.
It is, therefore, replaced by other reference electrodes. The most commonly used is calomel
electrode represented as Hg; Hg2CI 2(s) KCI solution.
Its reduction potential depends upon the concentration ofKCI solution used.
When saturated KCI solution is used, it is referred as SCE (Saturated Calomel electrode.
it has a reduction potential of O.5415Y. With l.ON KCI solution (known as NCE), the potential
is O.3338V The calomel electrode, once set, can be used for long.
Problem 23 : How commercial electrochemical cells are classified?
Solution: There are three important classes of commercial electrochemical cells:
(i) Primary cells (ii) Secondary cells (iii) Fuel cells
The primary cells can not be recharged once they are dead after use. The reaction in them
is not reversible. They can be used only when the active materials in them are present. For
example, dry cell, Rubber-Mallory cell. Secondary cells can be recharged as the cell reactions
in them can be reversed. They can be used again and again by recharging. For example, lead
storage cell, Nicad or Nickel-cadmium. Fuel cells from which energy can be withdrawn
indefinitely as long as the outside supply of fuel is maintained. They do not store energy. For
example, hydrogen-oxygen fuel cell find great importance in space vehicles because of its light
weight and the product water is valuable source of fresh water for astronauts.
( REVISION QUESTIONS)
1. What is a galvanic cell? Describe a Daniel cell.

2. Differentiate between an electro chemical cell and an electrolytic cell.
3. Given two important differences between e.m.f. and potential difference.
4. What do you understand by a reversible electrode? Describe one reversible electrode.
S. Describe the construction and working of the following electrodes :
(i) Hydrogen electrode (ii) Calomel electrode
6. (a) Write down the reaction taking place at the separate electrode and in
the complete reversible cell given below: Pt H2 (g) / HCI (aq) / KCI (aq) /
AgCI (s)/ Ag
(b) Give an example where a metal chloride behaves reversibly with respect to an
ion.
7. (a) Explain the meaning of an electrode potential being positive or negative with
respect to hydrogen electrode.
(b) What is a reference electrode? Describe briefly.
8. (a) How is electrode potential experimentally determined ? Distinguish between
single electrode potential and standard electrode potential
(b) How is single electrode potential determined ?
(e) Represent a concentration cell according to IUPAC convention.
9. (a) What is standard electrode potential? Give its importance.
(b) Why is NH4NO a or KCI used for preparing salt bridge? (PTU, DEc. 2K)
10. Derive N ernst equation for single electrode potential and explain the terms involved
in it. Write its application. (MD. May 2K; Amrawati Dec, 2L; Tripura 2K;
MKApril 01; SK, June 01, PTU Dec. 2K)
11. (a) Differentiate between the characteristics of an electrolytic cell and those of
Galvanic cell. What do your mean by standard electrode potential? How can it
be measured? (Dibrugarh, June 2K)
(b) What are reference electrodes? Describe the construction of calomel electrode.
(VT, Aug 01; PTU, Dec. 2K; Anna., Jan 01)
12. (a) Describe the construction and working of Daniel cell and hydrogen electrode.
(Anna, Jan 01; Dibrugarh, June 01)
(b) Explain the function of salt bridge. (Calicut, June 01)
13. (a) Explain the emf method for determination of pH of a solution (SK, Aug. 01)
(b) Explain the measurement of pH of a solution using glass electrode. Mention the
advantages of this electrode. (VT. Aug. 2K; March 01)
14. (a) What is a concentration cell? Explain with example. Derive the equation for
emf of a concentration cell without"transference.
(DDIT, Aug. 01; Aug 2K, Calicut, June 01)
(b) Describe the construction of lead acid battery with the reaction occurring during
discharge. (VT, March 99)
(e) Discuss the working principle of primary batteries? (VT, April, 2K)
15. (a) Write briefly about (i) Primary cells (ii) Secondary cells (S.K, Aug. 01)
(b) Distinguish between a cell and a battery. Give the classification of cells with
examples.
16. What is alkaline battery ? Describe the construction and working of Ni-Cd battery
with relevant reactions taking place during discharge. Mention its advantages and
applications. (Calicut, June 01; VT, Apri12L; Aug. 01)
17. (a) How is glass electrode constructed? Write the cell reactions.
(b) What is the effect of electrolyte concentration on electrode potential ?
(e) Explain the construction of Ni-Cd cell.
18. (a) The electrode potential of Zn is assigned a negative value whereas that of Cu of
is assigned a positive value. Give reasons.
(b) For the Daniel cell involving the cell reaction:
Zn (s) + Cu2+ ~ Zn2+ eq + CU(s)'
the standard free energies of formation for Cu2+ (eCJLand Zn2+ (e9) are 15.66kcals
mol- 1 and -35.14 kcal mol- 1 respectively. Calculate ~o of the cell.
(e) Calculate the EMF of the Zn-Ag cell at 25°C when [Zn2+] = O.OIM and [Ag+] =
10M. EO cell at 25°C = 1.56 Volt.
(d) Write a short note on calomel Electrode (PTU, Dec., 2002)
19. (a) Why do electrochemical cells stops functioning after some time?
(6) The EMF ofthe cell Cd, CdCI2, 2.5 H 20 (saturatedlAgCI(s) Ag in which the cell
reaction is : Cd + 2AgCI(s) + aq ~ CdCl2 2.5 H 20 (Sat) + 2Ag, is 0.6753 volt at
25°C and 0.6915 volt at O°C. Calculate ilG, ilH and ilS ofthe cell at 25°C.
(c) What do you understand by electrochemical series? (PrU, June, 2003)
(d) Write down the cell for which the overall reaction is
Cd + Cu2 + (a = 1) ~ Cd2+ (a = 2) + Cu (PrU, Dec. 2003)

20. (a) Derive Nernst equation for the calculation of cell e.m.f.
(b) The standard electrode potential for H g2 2+/Hg and Hg2+/Hg are 0.799V and 0.855V
respectively. Calculate at 298K the equilibrium constant for the reaction.
(PrU, June, 2004)
(c) What is the cell reaction and cell e.m.f. at 298 K of the cell ?
ZnlZn2+ (a = 1) II Pb 2+ (a = 1) I Pb (PrU, June, 2004)
21. What is standard electrode potential ? A galvanic cell consists of a copper plate
immersed in a 10.0 M solution of copper sulphate and an iron plate immersed in a
1.0 M solution offerrous sulphate and 298 K. Calculate the voltage for the cell. Given
EOCu++! Cu = 0.34 V, EOF++ Fe = - 0.44 V. (VTU, B.E., March 1999)
22. (a) What are Ion selective electrodes? Explain the determination of pH ofa solution
using glass electrode.
(b) Compute the cell potential of the Ag+ Ag couple with respect to Cu 2 + Cu if the
2 6
concentration of Ag+ and Cu + are 4.2 x 10- M and 1.3 x 10-3 M respectively
EOcell = 1.50 volts. (VTU, B.E., March 1999)
23. (a) Define standard electrode potential. Derive Nernst equation for electrode
potential.
(b) Explain the construction and working ofAg/AgCI electrode.
(VTU, B.E., August 1999)
24. (a) How is pH of a solution measured by using glass electrode?
(b) A concentration ceil wall constructed by immersing two silver electrodes in O.OIM
and 10 M AgNO s solutions. Write the cell scheme, electrode reactions and
calculate e.m.f. of the cell. (VTU, B.E., August 1999)
25. (a) How in potential of an electrode measured using a calonel electrode?
(b) Write the half cell reaction and net all reaction for the cell.
Cd(s) Cd2+ + (0.01 M/Cu 2 + + Co .5)/Cu(s)
The standard reduction potentially of cadmium and copper are - 0.4 V and 0.14
V. respectively calculate the e.m.f. of the cell. (VTU, B.E., April 2000)
26. What is single electrode potential? Derive Nernst equation for single electrode
potential ?(VTU, B.E., August 2001)
27. (a) What are reference electrode? Describe the construction of Calomal electrode.
(b) A cell was Zn 2++ Zn and Ag+/Ag electrode write the cell representation
EO Zn 2+ Zn = 0.76 V, EO Ag/Ag = 0.8 V. (VTU, B.E., August 2001)
28. Define standard electrode potential and derived Nernst equation for single electrode
potential.(VTU, B.E., August 2002)
29. (a) Explain the construction and working of a calomel electrode. Indicate the role
of calomel electrode.
(b) What are ion selective electrodes? (VTU, B.E., August 2002)
30. (a) Define single electrode potential and standard electrode potential? Derive the
Nernst equation for electrode potential.
(b) Explain the construction and working of calomel electrode. mention its
advantages.
(c) Write a short note on ion slective electrode. (VTU, B.E., JanlFeb. 2003)
31. (a) Discuss the origin of electrode potential and derive Nernst 15 equation for electrode
potential.
(b) What are Ion-selective electrodes? Give the construction of glass electrode and
explain the experimental method of determining pH glass electrode.
(c) An electrochemical cell consists of iron electrode dipped in 0.1 M FeS04 and silver
electrode ipped in 0.05 M AgN0 3 . Write teh cell respresentation, cell reaction
and calculate e.m.f. of the cell at 298 K. Given that the standard reduction
potentials of iron and silver electrodes are - 0.44 and + 0.80 V respectively.
(VTU, B.E., July/Aug. 2004)
32. (a) Derive Nerst equation for single electrode. Explain the determination of single
electrode potential using standard hydrogen electrode.
(b) Write brief notes on :
·(i) Calomel electrode
(ii) Glass electrode.
(c) Write the electrode reactions and calculate the e.m.f. ofthe following cell at 298
K given Ecello n = 1.3 V
Cu(s). Cu2+ + (1 X 10-2 M) 11 Ag+ (1 X 10-1 M) Ag(s)
(VTU, B.E., FeblMarch 2005)
CONVERSION AND STORAGE OF
ELECTROCHEMICAL ENERGY
BATTERY TECHNOLOGY
SYLLABUS
Batteries-Basic concepts, battery characteristics, Classification of batteries-primary,
secondary and reserve batteries; Classical batteries-construction, working and applications
of zinc-air, Nickel-metal hydride and lithium-Mn02 batteries.
3A.I INTRODUCTION
"Batteries are storehouses of electrical energy on demand". They provide well contained
energy conversion devices which greatly contribute to the needs of mankind. Battery is a device
which transforms chemical energy of a redox reaction into electrical energy. Batteries can
thus generate power and act as portable sources of electrical energy. Now-a-days portability
of electronic equipments in the form of hand sets has been made possible by batteries. A
variety of electronic gadgets have been made mor e useful and popular with the introduction
of rechargeable storage batteries having reliability to serve, better shelf life and tolerance
to service. The amount of energy which can be provided by an electrochemical cell depends
upon the amount of chemical reaction taking place within the cell.
Tiny coin and butter sized cells are used for electronic applications requiring only small
capacity. A liter-contains sized batteries are commonly used in motor vehicle for starting,
lighting and ignition purposes. Very large house sized batteries are used for utility storage
of electrical energy. The basis for battery technology is that the chemical energy derived
from the chemical reaction in the battery is converted into electrical energy. Further, the
conversion of electrical energy to mechanical energy is quite efficient because of the inherent
simplicity and low friction of electrical motors. This is the basis of applications of batteries.
Conversion of electricity to light or sound in also efficient and easily controlled.
Battery technology has acquired great importance in recent times because petroleum
resources of the world are fast depleting and there is a need for alternate energy sources.
Moreover, the revolution in microelectronics and the increased demand for portable gadgets
Battery Technology 101
powered by batteries has all the more increased its importance for industry. In modern times,
the portability of electronic equipments such as mobile phones, portable computers, calculators,
watches, electronically controlled cameras, hearing aids, pace makers for heart etc. has been
made possible by the use of batteries. Besides these applications, batteries are used in car
engines, emergency lights, stand by power supplies, electroplating, industrial, military and space
applications.
Secondary storage or accumulator batteries are constructed in such a way that they can
be recharged after partial or complete discharge. They are used as a source of d.c. power to
meet the following requirements.
(i) Batteries are the primary source of power and large number of discharge-
recharge cycles are required for use in trucks, submarines, mines or switching
locomotives.
(ii) Batteries are used to supply large, short-term repetitive power requirements, as in
automotive and air-plane batteries.
(iii) A very large capacitance to the circuit is required as in case of telephone exchanges.
(iu) A low-current-rate discharge for long periods is required for use in navigation boats
and ships.
(u) When a stand-by power is required and the battery is continuously connected to a
voltage-controlled d.c. circuit. As in the case of emergency light, power batteries and
telephone exchange.
For all commercial purposes, batteries are constructed for their specific service, to get the
best performance consistent with cost, weight, space and operational requirements. For
instance, batteries for automotives and aircrafts require thin anodes and cathodes
having very small separation to conserve space and weight and to provide high rates of current
discharge at low temperatures. But stand-by batteries use thick electrodes and thick
separators to provide long life.
3A.2 BASIC CONCEPTS
A commercial cell, used as a source of electrical energy is basically an electrochemical cell
where oxidising and reducing agents are made to react by using a suitable device. In principle,
Seal with vent

Anode +-l~+.~.~:~:~~:~.~,~~ Cathode
::~ ~ : : :::::: :::~: :
::~:: ~ :::::: :!:~::
::!:: t ::~~: :~:~::
::: : : t ::::~: :~:::: :
Anodic compartment +--t7.;';:;';j:H : :
"." ....
f :: : r :~';:': :
;. ...... ".\,' ·01·
Cathodic compartment
"'" ............ ·01·....•· .... ..
::~ : : t : :::~: :~:~:.. :..
"'J .... ~ ...... \" 'oI'~
Anode active material

• ',r
,'" ............
'OJ> ......
..
"" .... r ...... ".

.. ...... .
'\0 •
\,
• .,t ......
,/
'01 ...... ..
..
:::~,.::::: ~ ::::::.:::". Cathode active material

." .. " ..........
............ . . .. ' ".....
~
..." .... ..
Separator .... · .. ·t::::::::
: : : ici.~dt!r~i~t~:
:................ : : :.
..............
~
Fig. 3.1. Principal components of a battery.

any redox reactions can be used as the basis of electrochemical cell, but there are some
limitations to the use of many reactions Two or more electrochemical cells connected is
series constitute a battery. In common use, the term battery is often applied to a single
cell or a number of cells connected in series to form a unit. The components of such a celli
battery are shown in Fig. 3.1.
Main Components of a CelllBattery
(i) Anode,' An electrode at the surface of which oxidation takes place i.e., loss of
electrons take place is known as anode. It gives out electrons to the external circuit
by undergoing oxidation. It is a negative electrode.
(ii) Cathode,' An electrode at the surface of which reduction takes place i.e., gain of
electrons takes place is known as cathode. It accepts electrons from the external circuit
by undergoing reduction. It is a positive electrode.
(iii) Electrolyte " It is the material which provides ionic conductivity between the
positive and negative electrodes of the cell. It is the active mass in the cathodic
and anodic compartments in the form of a solution or a slurry of an acid, alkali or
salt having high ionic conductivity.
(iv) Separator,' It is a physical barrier between the anode and the cathode to prevent
direct short circuiting of the electrodes. Separators are permeable to ions but do not
conduct electrons. They must be inert in the total environment. Fibrous forms of
regenerated cellulose, veinyl polymers, polyolefins and cellophane are commonly
used as separators.
Requisits of the Above Components
(a) Anode material,' It should have (i) low reduction potential i.e., it should be easily
oxidised. (ii) It should have the capacity to deliver high coulombic output. (iii) It should
have good conductivity, good stability, ease of fabrications and low cost.
Zinc is mostly used as anode because it possesses these properties Lithium the being
the lightest metal is also used as anode in the modern batteries.
(b) Cathode material " It should have the capacity to facilitate the reduction of active
material and to provide resistance to the electrolyte.
(c) Electrolyte material,' (i) It should possess good ionic conductivity but poor electrical
conductivity to prevent internal short circuiting. (ii) It should be resistant to the
electrode material and safe to handle.
(d) Separator material,' (i) It should be permeable to the passage of ions from anodic to
cathodic compartments and vice versa during discharging and charging. (ii) It should
have the ability to prevent mixing of active materials in the two compartments.
(iii) It should possess high ionic conductivity but should be electronically insulator.
The cellslbatteries are fabricated in many shapes and configurations such as cylindrical,
flate plates, buttons and prismatic. The components are designed according to the desired
shape of the cell. To prevent leakage and drying of the materials, the cells are sealed by
different methods. Some cells are also provided with venting devices for the escape of
accumulated gases.
Discharging and Recharging of a Battery
A secondary storage battery involves two operations (i) Discharge (delivering power),
(ii) Recharge.
(i) Discharge: This is the operation of a cell when current flows spontaneously from the
battery into an external circuit.
During discharging (Fig. 3.2a) oxidation takes place at the anode to form cations (positive
ions) and electrons. The electrons liberated flow from the anode to the cathode through the
external circuit. These electrons are accepted by the active species is the cathode compartment
which is reduced to form anions (negative ions). The anions and cations formed at the respective
electrodes then move across the separator to bring about electroneutrality and to complete
the electric circuit.
The discharge reactions are given below:
MA ~ MA n+ + At negative electrode (Anode)
Anode Cation
Me n + X"- + ne- ~ Me + nX- At positive electrode (Cathode)
Active speCIes At Cathode Anion
in the cathode
compartment
Flow of electrons
!
Flow of electrons
- DC power supply 1
+1
i -ve
-ve.. ,.+ve
Anod.~+=r--r----1==l-----. Cathode .--+==t-jl--r:==4Anode
r:--:- r.:-. I r.-:-. r.:-
I!
Active species
"'......., ; ' ,.1 , " '" "
;;~:,;;
,' ..... :.-
,•• '..........
:::f:
, ....... ..... .
\
J.- .'........... ..
;~~~;~: ::
~-I:~I
M~X
(a) Discharging (b) Recharging
Fig. 3.2.
(ii) Recharging: This is operation of a cell when an external source of current reverses
the electrochemical reactions of the cell to restore the battery to its original charged state.
The negative terminal of the dc power supply is connected to the negative electrode of the
battery and the positive terminal to the positive electrode ofthe battery as shown in fig. (3.2b).
During charging, the active species formed at the anode compartment undergoes reduction
forming the metal. At the same time, at the cathode, oxidation takes place liberating the active
species. Thus, during charging, the positive electrode is the anode and the negative electrode
the cathode. The electrode reactions occurring during recharging are exactly the reverse of
those occurring during discharging.
Me + nX- ~ Me n+ xn- + ne- At negative electrode (Cathode)
MAn+xn- + ne- ~MA + nX- At positive electrode (Anode)
Active species At Anode Anion
in the anode
compartment
3A.3 BATrERY CHARACTERISTICS

A few characteristics of a battery for commercial applications are given below-
(i) Size: Both type of batteries (Primary as well as secondary) are manufactured in
many sizes according to various application, from the small electric wrist watch
battery to a single cell heavy weight in tonnes. Automotive and aircraft use thin
plates with thin separation to provide high rates of current discharge at low
temperatures. Thick plates and thick separations are used in stand-by-batteries.
(ii) Life: Life of the batteries varies from the single discharge obtainable from primary
type or more discharges obtainable from some secondary cells operating at very
high rates for very short times. All the automotive batteries give approximately
300 cycles or to last for 2 years. Industrial truck sizes may give 1,500 to 3,000
cycles i.e., may last 5 to 10 years. Stand by batteries may be expected to last for
8 to 30 years.
(iii) Voltage: The voltage of a battery depends on the magnitude of free energy change
in the overall cell reaction and hence on the choice of electrode systems. The voltage
is also affected by the over potential and resistance of the cell. To obtain maximum
voltage from the cell, a high potential difference is required. The ,electrode
reactions should be fast so that over potential is minimised and the internal
resistance of the cell should be low. The voltage of the cell given by the reaction :
Ecell = (Ee - EA) - (llA) - (lle) - iRcell
where Ee and E A are the electrodes potentials expressed as reduction potentials of
cathode and the anode respectively.
llA and lle are the over potential at the anode and the cathode respectively and iRcell is
the voltage drop. It is clear from the relation that the cell voltage depends or (i) the
difference in the electrode potentials. (ii) the over potential and (iii) The voltage drop.
The cell should be designed in such a way that it gives a high negative free energy change.
To achieve it the following points should be kept in mind: (i) (E e - E A) factor should be
maximum. The chosen electrode reactions should ensure that the molar concentrations at
the cathode reduces readily and that at the anode increases readily. (ii) The over potential
should be minimised. (iii) The voltage drop should also be minimised which can be done by
keeping the electrodes close to each other and also by using an electrolyte of high
conductivity.
(iv) Capacity: The power that can be obtained from a cell varies with its temperature
and the rate of current discharge. Capacity is the charge in ampere hours
designated as (AT]) that could be obtained from the battery. A popular automotive
battery capable of giving 2.5 A for 20 h is rated at 50 amphere - hours. The
capacity of a battery depends on its size and is determined by the faraday
relation
C = wn FIM
where
C = the capacity in All.
w = the mass of active material
M = the molar mass
n = the number of electrons involved in the cell.
The capacity of a battery is determined by the amount of active materials actually consumed
during its discharge.
Faradays First law of electrolysis states:
The amount of any substance deposited or dissolved as a result of passage of an electric
current is proportional to the quantity of electricity passed. If 'w' grams of a chemical material
is deposited or dissolved by passing/amperes of current for t seconds, then
wa. I xt ampere seconds
w = Zxlxt
where Z is called electrochemical equivalent (ECE)
when I and t in equal to unity, then
w=Z
Thus the electrochemical equivalent is defined as the weight of the substance deposited
when one coulomb of electricity (3.0 x 109 esu., 1 ampere second) is passed.
Therefore the capacity is also dependent on the discharge conditions. It is measured
by finding, for a fixed current discharge (Ci amperes), the time t taken for the battery to
reach a minimum voltage, Emin cell. A plot of V against t at a fixed current discharge in
shown in Fig. 3.3. The length of the flat portion of the curve tells us about the capacity of a
battery. The longer the flat portion of the curve, the better capacity of the battery.
Time
Fig. 3.3. Battery voltage against time at constant current discharge.
(v) Energy density : The ratio of the energy available from a battery to its weight is
called energy density. It is expressed as :
It Eavecell
Energy density = W
where I ~
is the fixed current
t1~ is the time taken
Eave cell ~ is the average voltage.
Energy density depends on the cell voltage. Good battery should have continuous
energy density above a certain value or a very high energy density for a short period.
·106 Essentials ofEngineering Chemistry
It is determined by noting the average voltage of the battery during its discharge and
knowing the total weight of the battery. Its capacity in terms of !.t. i.e., Ah is also
calculated. Putting these values in the above relation, energy density can be evaluated.
(vi) Energy efficiency: The energy efficiency for storage batteries is given by the relation
energy released on discharge

Energy efficiency (percentage) = . d fi h . x 100
energy reqUIre or c argmg
Batteries should have high energy efficiency. It depends on the rate of charging and
discharging. It also depends on the current efficiency of the electrode processes. The
overpotentials during charging and discharging and the internal resistance of the
battery.
(vi) Storage density: It is a measure of the charge per unit weight stored in the battery.
In other words, it is the capacity per unit weight. The weight includes the weight
of the electrolyte current collectors, terminals, the case and other subsidiary
elements, i.e., the weight of complete battery.
A high storage density indicates a good battery design i.e., minimum weight of all
subsidiary element and appropriate selection of electrode reactions. For instance,
use of lightest metal (Li) as anode would give one Faraday of charge for just
7 g ofLi.
(vii) Power density: It is the ratio of the power available from a battery to its weight
(W / kg) or volume (WIL). A continuous power density above a certain value and a
very high value for a short period are the requirements of a battery. Power density
decreases during discharge of battery.
(viii) Cycle life: The term has significance in case of secondary batteries which are
rechargeable. The number of charge / discharge cycles that can be achieved before
failure of secondary batteries is referred to a as cycle life. It is essential for the
discharge/charge cycle to regenerate the active material in a suitable state for
further discharge. The discharge/charge cycle thus depends on the chemical
composition, morphological changes and distribution of active materials in the cell.
The common reasons for a battery to have low cycle life include (i) corrosion at
contact points, (ii) shedding of the active material from the plates, (iii) shorting
between the electrodes due to irregular crystal growth and changes in morphology.
To achieve high life cycle, the manufacture should try to minimize the effect of
these factors.
(ix) Shelf life: It is the duration of storage under specified conditions when a cell or
battery retains the ability to give specified performance. The battery would have
long shelf life if there is no self discharge. Self discharge occurs due to reaction
between the anode and the cathode active material or corrosion of current
collectors.
In addition to the above characteristics, commercial batteries should have high
tolerance to service condition such as variation in temperature, vibration and shock.
Commercial batteries have wide range of applications, so they should give reliable
output depending upon the requirement. Commercial batteries in general should
have:
(i) High capacity, (very small variation of voltage during discharge),
(ii) High energy efficiency,
(iii) High cycle life, (cycle life means number of charging, discharging cycles before failure
occurs),
(iu) Long shelf life,
(v) Tolerance to different service conditions such as variation in temperature, vibration,
shock etc. and
Un) Reliability.
But for heart pace-maker battery, the required characteristics are: low voltage, very
small size, low power density and very high reliability. For this purpose, Al iodine cell is
suitable.
Thus, depending upon the requirement, the above discussed characteristics of a battery
are accordingly modified.
3A.4 CLASSIFICATION OF BATTERIES
Batteries are broadly classified into three categones :
(i) Primary battery: Main feature of primary battery is that it is designed to be
discharged only once and then discarded. These batteries cannot be recharged
because the chemicals with in the batteries are to be replaced when their entire
chemical energy is converted into electrical energy. Chemical reaction taking place
within the primary batteries are irreversible. Examples are Zn-Mn0 2 battery and
Li-Mn02 battery.
(ii) Secondary battery: Secondary batteries are those batteries in which chemical
reaction taking place are reversible. These are rechargeable batteries. They do
not possess inherent chemical energy. Electrical energy is first converted into
chemical energy by passing electrical current through the battery. The electrical
energy which is supplied to the battery is stored into the cell as chemical energy.
The chemical energy stored into the cells can be reconverted into electrical energy
by reversing the chemical reaction taking place with in the battery. Secondary
batteries, therefore, act as store house for electrical energy which can be used
when ever required. Examples are lead storage battery and nickel-cadmium
battery.
(iii) Reserve battery: In these batteries the active materials are kept separated by
a special arrangement. When it has to be actually used, an activation device makes
it ready. Such a battery is designed for long storage before use. The activation of
such a battery is done by adding the missing component just before use. Usually,
the missing component is water, which is poured by using valves and pistons etc.
Reserve batteries are used to deliver high power for relatively short periods of
time after activation in applications such as missiles, radios order etc. Examples
are Zn-Ag 20 batteries and Mg- water activated batteries.
3A.5 CLASSICAL BATTERIES
The invention of lead acid battery in 1859 by Plants and zinc manganese dioxide cell by
Leclanche in 1866 is the Land marks in the development and invention of several types of
batteries. The "dry cell" was invented in the first part of the 20th century by Gassner.
Rechargeable batteries were dominated by Lead acid system. Nickel-cadmium and nickel-iron
batteries were invented and developed as storage cells during the same period. The Ruben
cell, which is nothing but a zinc-mercuric oxide battery with alkaline electrolyte was also
developed for the electronic circuit used for military applications during the second world war.
Many new batteries came in the latter part of the 20th century. Edison cells (alkaline batteries)
made of Ni-Fe were introduced in 1919, Adama copper chlorine battery in 1943, the mercury
cell in 1945 and the alkaline Mn02 dry cell in 1955.
3A.5.1 Primary Batteries
Voltaic cell, Daniel cell, Laclanche cell,
Mercury cell and dry cells are examples of
primary batteries. -. -'
R - ....
_ ,.
Gr'lphit~ roil
- '.,
Some important primary cells (Daniel cell, +--++-Paste ofMn0 2 "nd graphlLt
Dry cell, Mercury cell) have already been -. : ... I- Paste of N~Cl + ZnC1 2
discussed in unit II (article 2.9) -.:::: .''I !--- Zinc cylinder
Dry Cells _ ~ f. . I+- Plastic coating
-~'-:--
Leclanche cell, Zn-Mn0 2 cell : It
(i)
consisted of an amalgamated zinc rod as anode Fig. 3.4. Leclanche (Zn-Mn0 ) dry cell.
2
and a carbon plate surrounded by a mixture of
granular carbon and Mn02 as a cathodes, dipping into a 20% solution ofNH 4Cl as electrolyte.
The dry cell is represented as :
Zn I Zn2+, NH4 +I Mn0 2, C
In the "dry cell" which is a modified version of Lechanche cell, the electrolyte is immobilized
by using the electrolyte in the form of a paste. Such a cell is called dry cell because of the
absence of any liquid or mobile phase. The dry cell consists of a zinc anode, which is shaped as
a container for the electrolyte and a carbon cathode surrounded by Mn02 and a paste ofNH 4 CI
and ZnCl 2 as a cathodic depolarizer. It facilitates the H+ -discharge reaction by removing the
adsorbed hydrogen atoms. Corrosion inhibitors such 3.S chl'omates and mercuric chloride are
also added to the electrolyte. The cell is encased in polypropykne cylinder and given a plastic
coating to reduce leakage Fig. 3.4.
The cell reaction is represented as :
The half cell reactions during discharge are
Anode Reactions : Zn(s) -+ Zn2+ (aq) + 2e
Cathode Reactions : 2MnOis) + 2NH/(aq) + 2e -+ Mn20aCs) + 2NH3 (aq) + H 20(/)
The overall reaction is
Zn(s) + 2Mn0 2(s) + 2NH4 + -+ Zn2+(aq) + ~Ois) + 2NH3 (aq) + H 20(l)
The oxidation state ofMn in Mn02 is IV and in Mn20 3 is III. So it has been reduced.
Alternatively, the cell reaction may also be written in which the secondary reactions
have been included.
Anode reaction
(Primary reaction) Zn -+ Zn2+ + 2e- .. .(i)
(Secondary reaction) 2NH4 Cl + 2(OH-) -+ 2NH3 + 2CI- + 2H20
Zn2+ + 2NH3 + 2CI- -+ [Zn (NH 3)2]CI 2
Cathode reaction: 2Mn0 2 + 2H 20 + 2e- ~ 2MnO(OH) + 20H- .. .(ii)
or
Overall all reaction: Adding (i) and (ii), we get

Zn + 2Mn02 + 2H20 ~ Zn2+ + 20H- + 2MnO(OH)
But, a reaction between OH- thus formed at cathode and NH4 + (derived from NH4Cl) evolves
NH3 (g). This liberated NH3 (g) disrupts the current flow.
NH:(aq)+ OH-(aq) ~ NH 3 (g)+H 20(l)
This is prevented by a reaction of NH3 (g) with Zn2+ (from ZnC1 2) to form the complex
[Zn(NH 3 )2]C!z(s ).
The voltage of the cell, which is due to the primary electrode reaction, is about 1.5 V.
However, the secondary reactions consume the 2Zn2+ and OH- as shown above and once the
cell is discharged, it can not be charged again.
A cut away view of a typical pasted cylindrical cell is shown in Fig. 3.5.
Carbon
electrode
(Cathode)
<±>
(min 02 + C +
Paste spllrator
electrolyte)
made of
polythylene bonded tube
Fig. 3.5. Cut-away view of a typical pasted cylindrical Leclanche cell.

Carbon-zinc cells are the most commonly and the most widely used primary cells all over
the world. These cells are used in small portable appliances such as flash lights, radios, toys
and electrically operated articles.
The reactions involved in the dry cell cannot be reversed by passing electricity back through
the cell . Hence, the dry cell is a primary cell.
Advantages
(i) It is easier to fabricate. So, jts price is low.
(ii) It gives voltage of about 1.5 V.
Disadvantages
(i) If current is rapidly drawn from it, products are build up on the electrodes thereby
causing drop in voltage.
(ii) The cell may run down slowly, even if it is not in use. This is because the electrolytic
medium is acidic, so that Zn metal slowly dissolves.
3A.5.2 Alkaline cells
Early alkaline cells were of wet cell type. However, the alkaline cells of the 1990s are
mostly of the limited electrolyte i.e., the dry cell type. In primary alkaline cells, sodium
hydroxide or potassium hydroxide is used as the electrolyte. Zinc is used as the anode
material while a variety of materials can be used as cathodes.
An example of alkaline cell is the mercury cell which is represented as :
Zn(Hg), ZnO(s)iOH- (8M)i HgO(s), Hg
The electrode reactions are :
At Anode:
Zn(s) + 20H- (aq) ~ ZnO(s) + H 20(l) + 2e
At Cathode:
HgO(s) + H 20(l) + 2e ~ Hg(l) + 20H- (aq)
The overall reaction :
Zn(s) + HgO(s) ~ ZnO(s) + Hg
Alkaline batteries normally have a longer shelf life in comparison to the Leclanche cell
because Zn is corroded slowly by the weakly acidic NH 4 Cl, which is replaced by NaOH in
alkaline batteries.
They are of two types :
(a) The larger cylindrical shaped batteries.
(b) The miniature, button type cells.
(a) Cylindrical shaped batteries
These are mainly produced by using zinc-Mn0 2 chemistry. These batteries use alkaline
electrolyte and are constructed in standard cylindrical sizes. Their can be used in the same
type of devices as ordinary Leclanche cells and zinc chloride cells. This high level of
performance makes them ideally suited for applications like cameras, toys and audio devices.
A cross sectional representation of a typical cylidrical alkaline cell in shown in Fig. 3.6.
The battery is housed in a steel can which contains dense, compacted cathode material
consisting of Mn02 and carbon. The anode mix consists of alkaline electrolyte, zinc powder
and a small quantity of gelling material to immobilize the electrolyte and suspend the zinc
powder. A plastic seal assembly is provided to the cell to keep the electrolyte to prevent the
leakage of electrolyte out of the cell. Alkaline cell derives its power from the reduction of the
Mn02 cathode and the oxidation of the zinc anode . The simplified electrode reactions are given
below:
Anode reaction Zn + 20H- ~ ZnO + H 2 0 + 2e-
Cathode reaction 2Mn02 + 2H 20+ 2e- ~ 2MnO(OH) + 2(OH)-
Overall reaction Zn + 2Mn02 + H 20 ~ ZnO + 2MnO(OH)
The actual anodic and cathodic reactions are much more complicated.
Steel plated cover_-r-~_~::c=:::=~:::=:::::::

(positive)
_~_-+-_Steel can
Electrolyte
(KOH)
Cathode Anode
(Mn0 2 + C) (Powdered zinc)
Separator -+-+~~l+
steel cell
..I~~::::~::::~~::::=::~~....::::~ Steelcover
plated cover
(negative)
Metal spur Brass rivet
Fig. 3.6. Cross-sectional view of a typical cylindrical alkaline cell.
Alkaline batteries have high output capacity and high current carrying ability are being
manufactured by many companies all over the world, which are competing with each other
to improve the performance of the cylindrical alkaline batteries.
(b) The miniature, button type cell
Miniature alkaline cells are small,
button shaped cells, which use zinc
anodes, alkaline (NaOH or KOH)
electrolyte and a variety of cathodic
materials e.g., Mn02' HgO, Ag 20 or
even air (in case of Zn-air batteries).
While the chemistry of the anode in
identical as in the larger cylindrical
alkaline cells, the cathode chemistry
varies with the type of cathode
material used. These batteries are
used in watches, calculators cameras, Insulating
hearing aids and other miniature
devices. The construction of a typical Separator mix
miniature alkaline cell in illustrated Fig~ 3.7. Cut-away view of a miniature alkaline cell.
in Fig. 3.7.
3A.5.3 Zinc-air Battery
In this type of cell, the zinc anode and the porous carbon cathode are immersed in 20%
solution of NaOH.
Anode reaction
Cathode reaction H 20 + [0] + 2e- ~ 2 (OH-)
Overall cell reaction Zn + 2 (OH-) + [0] ~ Zn 02 + H 20
Since OH- ions take part in the
electrode reaction, the alkali gets
diluted. The voltage of the cell is
1.45V. The zinc-air batteries offer the
possibility of obtaining very high _--f_+-.lU1.oue cap
energy densities. In place of a
cathode material placed in the
battery during manufacture, oxygen
from the atmosphere is used as Gasket
cathode material, thus allowing for a
more efficient design. The cutaway
view of miniature air cell is shown Anode
in Fig. 3.8.
It resembles a typical miniature Air access .
hole Air diffusion
cell, except for the air access holes layer
in the can. The 8:Il0de occupies more
internal volume of the cell. Fig. 3.8. Cross-sectional view of a miniature air cell battery.
However, in place of a thick cathode
pellet, it is provided with a thin layer containing the cathode catalyst and air distribution
passages. Air enters the cell through the holes in the can and the oxygen reacts at the surface
of the cathode catalyst. The air access holes are generally covered with a protective tape, which
can be removed when the cell is used.
Small amounts of metal oxides can also be used as catalysts. If the reaction is well catalyzed,
the battery can operate at a higher and more useful voltage.
Air cells are ideal for use in such applications where the usage is largely continuous. They
are not general purpose cells. They have to be carefully designed for particular application.
They are mainly used in hearing aids, in railway and the locations where the electric supply
by cables is either expensive or impossible.
The zinc-Mn0 2 miniature alkaline cells are used where economical power source is desired.
Miniature Zinc-HgO alkaline batteries have higher capacity than the Zn-Mn02 batteries. The
cathode reaction is
HgO + H 20 + 2e- ~ Hg + 2 (OH-)
But the toxicity of Hg causes serious disposal problem.
Miniature Zinc-Ag20 batteries have high energy density, almost as high as that of mercury
cells. The cathode reaction is
Ag2 0 + H 2 0 + 2e- ~ 2Ag + 2 (OH-)
Miniature zinc-Ag2 0 batteries are used in electronic watches and in such application where
high energy density is needed. They have good storage life too.
3A.5.4 Secondary Batteries
Secondary cells are those cells in which chemical reactions taking place are reversible.
These batteries are divided into following three categories :
(i) Lead acid accumulators or Acid batteries.
(ii) Alkaline storage batteries.
(iii) Other including Lithium / Lithium ion batteries.
(a) Lead Acid Accumulators: "Batteries are storehouses of electrical energy on demand".
They provide well contained energy conversion devices which greatly contribute to the needs
of mankind. Battery is a device which transforms chemical energy of a redox reaction into
electrical energy. Batteries can thus generate power and act as portable sources of electrical
energy. Now-a-days portability of electronic equipments in the form of hand sets has been made
possible by batteries. A variety of electronic gadgets have been made more useful and popular
with the introduction of rechargeable storage batteries having reliability to serve, better shelf
life and tolerance to service. The amount of energy which can be provided by an electrochemical
cell depends upon the amount of chemical reaction taking place within the cell.
Tiny coin and butter sized cells are used for electronic applications requiring only small
capacity. A liter-contains sized batteries are commonly used in motor vehicle for starting,
lighting and ignition purposes. Very large house sized batteries are used for utility storage of
electrical energy. The basis for battery technology is that the chemical energy derived from the
chemical reaction in the battery is converted into electrical energy. Further, the conversion of
electrical energy to mechanical energy is quite efficient because of the inherent simplicity and
low friction of electrical motors. This is the basis of applications of batteries. Conversion of
electricity to light or sound in also efficient and easily controlled.
Battery technology has acquired great importance in recent times because petroleum
resources of the world are fast depleting and there is a need for alternate energy sources.
Moreover, the revolution in microelectronics and the increased demand for portable gadgets
powered by batteries has all the more increased its importance for industry. In modern times,
the portability of electronic equipments such as mobile phones, portable computers, calculators,
watches, electronically controlled cameras, hearing aids, pace makers for heart etc. has been
made possible by the use of batteries. Besides these applications, batteries are used in car
engines, emergency lights, stand by power supplies, electroplating, industrial, military and space
applications.
Secondary storage or accumulator batteries are constructed in such a way that they can
be recharged after partial or complete discharge. They are used as a source of d.c. power to
meet the following requirements.
(i) Batteries are the primary source of power and large number of discharge-
recharge cycles are required for use in trucks, submarines, mines or switching
locomotives.
(ii) Batteries are used to supply large, short-term repetitive power requirements, as in
automotive and air-plane batteries.
(iii) A very large capacitance to the circuit is required as in case of telephone exchanges.
(iv) A low-current-rate discharge for long periods is required for use in navigation boats
and ships.
(v) When a stand-by power is required and the battery is continuously connected to a
voltage-controlled d.c. circuit. As in the case of emergency light, power batteries and
telephone exchange.
For all commercial purposes, batteries are constructed for their specific service, to get the
best performance consistent with cost, weight, space and operational requirements. For
instance, batteries for automotives and aircrafts require thin anodes and cathodes having
very small separation to conserve space and weight and to provide high rates of current
discharge at low temperatures. But stand-by batteries use thick electrodes and thick
separators to provide long life.
Note: The details of Lead Acid Accumulations have already been discussed in unit II, article
2.9 (secondary cells).
Overall reaction: 2PbS04 + 2H20 ~ Pb(s) + PbOls) + 4H+(aq) + 2S04 2- (aq)
This is possible because solid PbS0 4 formed during the working of the cell sticks to the
electrodes and can gain or lose electrons during recharging.
(b) Nickel-cadmium storage cell : Another secondary cell is the nickel-cadmium
storage cell, which has a longer life than the lead storage cell but is more expensive to
manufacture.
It consists of Cd as anode and metal grid containing Ni(IV) oxide as cathode immersed in
KOH sQlution. The cell reaction is given below:
At anode :
Cd(s) + 2 OH- (aq) ~ Cd(OH)2 (s) + 2e-
At cathode:
Ni0 2(s) + 2H20 + 2e- ~ Ni(OH)2(s) + 2 OH- (aq)
The overall reaction is :
Cd + Ni0 2 + 2H20 ~ Cd (OH)2(S) + Ni (OH)2 (s)
In this cell, the reaction products adhere to the electrodes and the reaction can be reversed
by charging. Since no gases are evolved during charging or discharging, so this cell has very
long life and its potential is about 1.4V.
It is widely used in cordless phones, cordless electronic shavers and electronic flash units.
3A.5.5. Nickel-Metal Hydride Cells
The cell has been developed more recently and is produced in two different versions using
different alloy types.
(a) A B2 types where A is group IV metal such as titanium and B is a group VIII metal
such as nickel.
(b) A B5 type where A is a rare earth metal such as lanthanum and B is a group VIII
metal such as nickel.
Many additional alloying elements have been incorporated into both the above two base
formulations to improve the hydride formation properties. The voltage of this cell is comparable
to that of nickel-cadmium cells, whereas its energy density is comparable to the most advanced
types of nickel-cadmium cells (i.e., 110 - 150 Wh/L).
Electrodes are made of porous nickel foil or grid on which the active materials are either
coated or pasted. The electrolyte is an aqueous solution of KOH and polypropylene is used as
the separator. The anode and the cathode are stacked in a stainless steel container alternatively,
and then connected in series to get desired voltage. The Nickel metal-hydride battery is
represented as
MH 2 1KOH (5.35 M) INI(OH)2' NiO(OH)
The reaction occurring during discharging and charging are given below:
Discharge
At anode.'
Charge
Nickel hydroxide is reduced to Ni(OH)2

Discharge
At cathode: 2NiO(OH) + 2H20 + 2e 2Ni(OH)2 + 20H-
Charge
Overall reaction :
Discharge
MH2 + 2 NiO(OH) 2Ni(OH)2 +M
Charge
Nickel-metal hydride batteries have wide range of applications.
The shelf life of this cell is better than that of hydrogen cells because the nickel alloy is
designed to reduce the pressure of hydrogen gas to only a few bars as compared to 50 bars in
case of nickel-air battery. Further the negative electrode is the limiting electrode to forestall
the evolution of oxygen from the electrode during charge, thereby avoiding any explosive mixture
of hydrogen and oxygen in the cell. These batteries are used for portable high power and high
energy applications. Further improvement in cycle life and shelf properties may enable potential
use of this cell as source of power for portable computers, portable telephones, etc. Recently
the battery is being used in cellular phones, camcorders and laptop computers.
3A.5.6 Lithium Batteries
Cells having Lithium anodes are called Lithium cells. They can be broadly classified into
the following two types :
(i) Cells with solid cathodes,' These may have solid or liquid electrolytic solid electrolyte
systems, other than lithium-iodine systems, are yet to develop into commercial level.
(ii) Cells with liquid cathodes,' These have liquid electrolytes. Further, at least one
component of the electrolyte solvent and the cathode active material are identical.
The lithium cells take advantage of the high energy film-forming property. This is possible
because the film formed in conductive to lithium ions, but not to electrons. Water, alcohol and
some other compounds which are thermodynamically unstable with lithium, do not form such
a passivating film. Organic compounds such as propylene carbonate ether, butyrolactone,
dimethoxy ethane, tetrahydro furan are the best solvents that were found to be useful in lithium
batteries. Lithium perchlorate, Lithium tetrafluoroporate, lithium trifluoromethane sulfonate
are used as electrolyte.
Lithium-Mn02 Batteries
The lithium-manganese dioxide is emerging as the most widely used 3-volt solid cathode
lithium primary battery. The electrolytic Mn02 should be heated to> 300°C to effectively remove
water, before incorporating it in the cathode. Lithium cells in available in many configurations
such as coin, bobbin, spirally wound and cylindrical. The anodic and cathodic reaction taking
place in the cell as follows :
Anodic reaction Li ~ Li+ + e-
Cathodic reaction Mn 02 + Li+ + e ~ Mn IIl 02 (Li+)
lV
Overall reaction Mn lV0 2 + Li ~ MnIlI 02 tLi+)

Mn is reduced from the tetravalent state in (Mn0 2) to the trivalent state [in MnIII 0 2(Li+)]
by lithium. Mn IlI 02 (Li+) indicates that Li+ ion enters the Mn02 crystal lattice. It gives a
potentials of 3.0 V and an energy density of 230 Wh/kg. The performance of the cylindrical
cell in superior to alkaline cells at all rates of discharge. The cell is widely used as power
source for electronic camera flash guns which yield 3 to 5 times more flashes than those obtained
with alkaline cells.
There is a revolution in microelectronic in modern times which has led to the
miniaturizations of electronic gadgets. These gadgets require batteries with high voltage, high
energy density, high energy efficiency and long life cycle. The outcome of researches since
1990's has resulted in the invention of lithium batteries. These batteries offer voltage upto 4V
as compared with 1.5V offered by other primary batteries. Lithium batteries are being used in
many consumer electronic devices, automatic cameras, calculators, watches, memory back up
devices and safety devices.
( PRACTICE PROBLEMS FOR TUTORIALS )
1. What is an electrochemical cell ?

2. What are the different types of a cell ?
3. What is the difference between Primary batteries and Secondary batteries?
4. What do you mean by internal resistance and capacity of a cell ?
5. What are alkaline batteries? Mention their advantages?
6. Why ampere hour efficiency of a lead acid cell is more than the watt hour efficiency?
7. What are the different methods of charging a lead acid battery ?
8. Define capacity of cell. On what factors capacity of a lead acid cell depends?
9. What is lead-acid accumulator?
10. What is the purpose of Mn02 in dry cell ?
11. Write the overall equation for the reaction taking place in an alkaline battery.
12. Write the reaction occurring during discharge of Zn-air battery.
13. What are reserve batteries?
14. What are the various characteristics of zinc-air battery ?
15. Write the overall reaction oflead storage battery.
16. Enlist some of the desirable and undesirable features of a lead storage battery.
17. Explain why a porous plate or a salt bridge is not required in a lead storage cell ?
18. Explain why the lead storage cell
(a) has a relatively constant potential.
(b) can be recharged.
19. Comment on the statement. 'A storage cell can operate both as an electrochemical
and as an electrolytic cell.'
20. Why Zinc-Air battery is at the fore front of modern battery technology?
21. Write the charge-discharge cell reactions of Zinc-Air battery.
22. Why Nickel-metal hydride batteries are gaining superiority over classical batteries.
23. How is Ni-MH battery represented? Write its electrode reactions.
24. What are the advantages of using lithium in batteries?
25. Give the construction and electrode reactions of Li-Mn02 cell.
(ANSWERS)
1. An electrochemical cell is an arrangement in which chemical redox reactions take place
indirectly at a steady rate so as to convert chemical energy into electrical energy.
2. Cells are of two types :
(i) Primary cells,' In these cells the cell reaction is not completely reversible. These
are not rechargeable and once discharged have no further electrical use.
(li) Secondary cells : In these cells the cell reaction are reversible and therefore are
rechargeable. After discharge, these can be recharged by passing current through
them in the opposite direction.
3. Primary batteries can discharged only once and then discarded. Secondary batteries
are those batteries in which chemical reaction taking place are reversible. These
batteries are rechargeable batteries.
4. Internal resistance of the cell is the resistance offered by the cell itself to the flow of
current. Capacity of the cell is given by product of current in amperes and time in
hours during which the cell can supply current. For example, lead storage battery can
supply current till its voltage falls to 1.8 V.
5. Alkaline batteries are improved forms of the dry cells, in which the NH4Cl is replaced
by KOH as the electrolyte. Graphite rod is surrounded by a paste containing Mn0 2•
The out side body is made of zinc. The main advantages are :
(i) Zinc does not dissolve readily in basic medium.
(li) The alkaline battery maintains better voltage.
(iii) The life of alkaline battery is longer than dry cell.
s. It is found that during discharge the e.m.f. of the cell falls from about 2.1 volts to 1.8
volts whereas during charging, it rises from 1.8 volt to about 2.6 volt. As the average
voltage during charge is more than that during discharge, the watt hour efficiency is
always found to be less than Ampere efficiency.
7. The different methods of charging lead acid batteries are :
(i) Normal voltage DC supply method.
(ii) A low voltage motor-generator method.
(iii) A rectifier unit method.
8. Capacity of the cell is given by product of current in amperes and time in hours during
which the cell can supply current until its e.m.f. falls to 1.8 volt. It is measured in
amp hours. It depends upon the following factors:
(i) Rate of discharge
(ii) Density of electrolyte
(iii) Temperature
(iv) Amount of active material.
9. Lead acid accumulators is a battery consisting of a number of cells and each cells of a
battery consists of a grid of Lead-antinomy alloy coated with lead dioxide as a positive
pole and spongy lead as a negative pole.
10. Mn02 is used as an oxidising agent in a dry cell.
11. Zn(s) + 2Mn0 2(s) ~ ZnO(s) + ~03'
12. 2 Zn + 02 ~ 2 ZnO.
13. In reserve batteries, the active materials are kept separated by a spatial arrangement.
When it has to be actually used, an activation device makes it ready. Such a batteJ'f is
designed for long storage before use.
14. The various characteristic of zinc-air battery are:
(i) More stable voltage at high current.
(ii) Relatively flat discharge curve.

(iii) Most effective in applications that consume battery capacity in a few weeks.
(iv) Highest capacity to volume ratio for miniature batteries.
15. The net reaction during the discharging of lead acid storage cell is
Pb + Pb02 + 4H+ + 28042- ~ 2Pb804 ,J, + 2H20 + energy
16. The desirable features which are characteristic of a lead storage battery are:
Rechargeability, Portability, Relatively constant potential and inexpensiveness.
Undesirf,Lble features which are characteristic of a lead storage battery are :
The use of concentrated sulphuric acid (dangerous), somewhat fragile nature of battery
and the use of lead which causes pollution.
17. In a cell, the half-cells must be separated only if the oxidizing and/or reducing agent
can migrate to the other half-cell.
In the lead storage cell, the oxidizing agent, Pb02, and the reducing agent, Pb, as well
as their oxidat~on and reduction product, Pb80 4 , are solids. That's why the half-cells
do not need to be in separate vessels; they can be put into the same vessel, eliminating
the necessity for a salt bridge or a porous partition.
18. (a) Lead storage cell has a relatively constant potential because the reagents are solids
or concentrated solutes.
(b) The solid nature of each oxidizing and reducing agent prevents direct contact no
matter which way the reactions are run.
19. A storage cell can operate both as an electrochemical cell and as an electrolytic cell. It
has the ability to work both ways, to receive electrical energy and also to supply it.
When it operates an electrochemical cell, it supplies electrical energy and as a result
it eventually stops working. It then needs to be recharged. When being recharged, the
cell operates as an electrolytic cell.
20. Zinc-Air battery is at the fore front of modern battery technology because one of the
active materials (air) does not contribute to the mass of the battery and hence offers a
very high energy density. It has an energy density of about 100 Wh kg-I which is three
times that of the classical lead acid battery or twice that of Ni-Cd battery. It finds
applications n railways and military radio receivers.
21. When air is passed through the Zinc-Air cell, zinc gets oxidized to ZnO at the anode,
during discharge. The oxygen of the air reacts with water at the cathode.
The cell reactions are :
Discharge
2Zn + 40H - ~(~~=::t (anode)
Charge
Di..charge )
( Charge
40H- (cathode)
22. Zinc-Metal hydride batteries have gained superiority over the classical batteries because
the active material of the anode i.e., metal hydrides such as VH 2' ZrH2 and TiH2 with
a hydrogen storage metal alloy such as LaNi5 or TitTi pOSsesses exceptional qualities.
The anode material has (i) a good hydrogen storage capacity capable of adsorbing and
desorbing hydrogen as the battery is discharged and charged repeatedly (ii) high
resistance to chemical oxidation and corrosion and (iii) high!electrochemical reactivity.
The anode and the cathode are stacked alternately in a stainless steel container and
connected in series to get the desired voltage.
23. The Ni-MH battery is represented as :
MH21 KOH(5.35M) I Ni(OH)2' NiO(OH)
The reactions occurring during discharging and charging are given below:
Discharge)
MH 2 +20H- ( Charge -anode
Nickel oxyhydroxide is reduced to Ni(OH)2

Discharge )
2NiO(OH) + 2H20 + 2e ( Charge
2Ni(OH)2 + 20H- -cathode
Overall reaction
Discharge )
MH2 + 2NiO(OH) ( Charge 2Ni(OH)2+ M
24. Lithium metal is used in batteries because of the following characteristics of lithium.
(i) It is the lightest metal.
(ii) It has very good electrical conductivity because of its low ionisation potential.
(iii) It has highest electrochemical equivalence (3.86 Ahg-l).
(iv) It has highest standard reduction potential (-3.05) V. It occupies the ~st position
in the electrochemical series.
25. Li-Mn02 cell consists of lithium as anode, a specially prepared heat-treated Mn02 as
the cathode active material and an electrolyte containing lithium salt (LiCl, LiBr, LiCI04,
LiAICl 4 or LiCF38°3) in a mixed organic solvent (propylene carbonate and 1,2-
dimethoxyethane). A non-woven polypropylene separator separates the anode and the
cathode.
The electrode reactions and overall reaction occurring during discharge are
Anode Li -+ Li+ + e
Cathode -Mn02 + Li+ + e -+ Mn0 2(Li+)
Overall Mn02 + Li -+ Mn02(Li+)
Mn is reduced from the tetravalent state (in Mn02) to the trivalent state [in Mn02(Li+)]
by lithium. Mn02(Li+) indicates that Li+ ion enters the Mn02 crystals lattice. It gives a
potential of 3.0 V and an energy density of 230 Wh/kg.
1. What is the difference between a cell and a battery? What are primary and secondary
batteries? Give examples of each.
2. Explain the principle components of a battery. What are the requisites of each
component.
3. What are reversible and irreversible cells? Which of them is recharged ? Explain the
principle of charging and discharging in a battery.
4. What do you mean by battery characteristics ? Explain any four characteristics of a
battery.
5. Explain the following battery characteristics:
(i) Voltage (ii) Capacity (iii) Energy density and (iv) Cycle life.
6. Justify the statement "The design and characteristics of a battery depend upon
requirement of the battery."
7. Describe the various points of difference between a primary batteries and secondary
batteries. Give two examples of each type.
8. Discuss the various characteristics of a battery? .
9. Describe the construction and working of lead acid battery with the reaction oecurring
during discharge.
10. Discuss the working principle of any two primary batteries.
11. What are electrode reactions involved in a Zinc-air battery ? Mention the various
characteristics and applications of Zn-air battery.
12. Distinguish between a cell and a battery. Give the classification of batteries with
examples.
13. Discuss the various factors that affect the e.m.f. of a battery.
14. Describe the construction working and applications of Lithium-Mn02 batteries.
15. What are Nickel-metal hydrides cells? How is it represented ? What are its main
applications.
16. Write the overall reaction of Nickel-metal hydride cell. Give its components and
applications.
17. What is alkaline battery? Discuss the construction and working of Ni-Cd battery with
relevant reaction taking place during discharges.
18. Discuss the construction and working of a dry cell. What are its limitations? How can
these be removed.
19. Why are dry cells not rechargeable ? Why does a dry cell become dead after a long
time even ifit has not been used?
"
20. What are rechargeable dry cells? Discuss one example. What is the role of ZnCl2 in a
dry cell?
21. Explain the construction and working of Lead storage battery giving the reactions
involved during its discharge and recharge.
22. Why the life of a lead storage battery is limited even when it can be recharged ?
Overcharging damages the battery or not. Explain.
23. Discuss the construction of Zn-Mn02 battery with the working principle.
(VTU, B.E. Aug. / Sept., 2001)
24. Describe the construction of Ni-Cd battery with relevant reactions occurring during
its discharge. Mention its applications. (VTU, B.E. August, 2001)
FUEL CELLS
SYLLABUS
Introduction, types offuei cells-Alkaline, phosphone acid and molten carbonate fuel cells,
solid polymer electrolyte and solid oxide fuel cells, description and working of H 2-02 and
MeOH-02fuel cells.
3B.IINTRODUCTION
A fuel cell is an electrochemical cell which can convert the chemical energy contained in a
readily available fuel-oxidant system into electrical energy by an electrochemical process, in
which the fuel in oxidised at the anode. Fuel cell consists of an electrolyte and two electrodes,
similar to any electrochemical cell. However, the fuel and the oxidizing agents are continuously
and separately supplied to the electrodes of the cells, at which they undergo reactions. These
cells can capable of supplying current as long as the reactants are supplied.
Fuels cells work at high efficiency and the resulting emission levels are far below the
permissible limits. Fuels cells are about three times for effective than any other method of
providing electricity on board and hence are used as auxiliary power generators in space
vehicles. Fuel cells systems are modular and hence can be built in a wide range of power
requirements from a few hundred watts.upto multi kilo watt and even megawatt sizes.
At present, motor vehicles accounts for about one-half of total hydrocarbons and nitrogen
oxides pollution and they combine to form photochemical among that pollutes the atmosphere.
Use of storage batteries like Nickel and lead batteries air discharge toxic chemicals and pollutes
the environment. An electric car equipped with a fuel cell is the only viable option to reduce
the pollution load due to battery operated motor cars. Further, due to low emission levels fuel
cell power plants can be installed on site where energy is actually required for consumption
even in densely populated area.
The basic principles of fuel cells are identical to those of the well known electrochemical
batteries. The only difference is that in fuel cell, the chemical energy is provided by a fuel and
,
122 Essentials ofEngineering Chemistr:t
an oxidant stored outside the cell in which the chemical reaction takes place. Thereforel
electrical power can be obtained as long as the cell is supplied with the fuel and the oxidant. \
It has been estimated that replacement of 10000 petrol-based vehicles by fuel cell based
vehicles would reduced oil consumption by 6.98 million gallons per year. There will be millions
of fuel cells vehicles on the road by 2010. Air pollutants would be reduced by one million tons
per years and 60 million tons of the green gas e02 would be eliminated.
The history of fuel cell dates back to 1839 with the experiments of the British Scientist,
Sir William Grove. Upto 1950, the fuel cells are used for few applications only. The most
important applications have been their use or the main source of electrical energy in the space
crafts. Attempts to develop fuel cells systems for terrestrial applications were made in the .
1980's. The most important applications for load levelling for energy utilities, for remote power '
plants, industrial waste utilization and emergency power supply. -
Fuel cells have the following advantages:
(i) Their power efficiency is high.
(ii) They are capable of supplying current as long as the reactants are supplied.
(iU) They are eca-friendly, since no polluted toxic chemicals produce.
(iv) Fuel cell systems are modular and hence can be built in a wide range of power
requirements.
(v) Low noise pollution and 1000 thermal pollution.
(vi) Low cost fuels can be used with high temperature systems.
Juii} Fuel cells are suitable for the future nuclear-solar-hydrogen economy.
(viii) Low maintenance costs.
Fuel cell automotive batteries can render electric vehicles efficient and reliable.
(ix) .
(.x) Saves fossils fuels.
The fuel cells are expected to playa vital role in the future energy scenario, particularly
when hydrogen is projected as the main energy source of the 21st century.
3B.2 TYPES OF FUEL CElLS
Fuel cells are classified on the basis of the temperature of operation. They are of three
types :.
(i)Low temperature fuel cells.
(ii) Medium or moderature temperature fuel cells.
(iii) High temperature fuel cells.
(i) Low temperature fuel cells: These cells operate below 1000 e. These are simple in design.
The electrodes processes have to be accelerated by using special type of catalysts. The fuels
used are hydrogen (produced by reforming of steam or cracking of ammonia). Pure oxygen is
used as oxidant. The electrolyte used for hydrogen-oxygen fuel cells in potassium hydroxide
solution.
(U) Medium or moderature temperature fuel cells: These are operated at temperature range
of 100° to 250oe. The fuel used is pure hydrogen. The oxidants are pure oxygen free from all
impurities. Electrolyte in aqueous potassium hydroxide.
Fuel Cells 123
(iii) High temperature fuel cells: These operate generally at temperature 7500°C. These
cells require fused salts (eg., alkali metal carbonates or hydroxides) or solid electrolytes with
appreciable electrical conductivity. Generally hydrocarbons fuels are used.
Fuels cells are also classified sometimes on the basis of the operating pressure. Accordingly
they are referred to as high pressure, medium pressure or atmospheric pressure systems. Many
of these are co-generation type where a by product in industry is used up or a reactant in the
fuel cell thus generating electricity. Some times heat generated in industrial processes are
utilized to run a fuel cell.
FrQIn the practical point of view, fuel cells are distinguished on the basis of the type of
electrolyte used :
(i) Alkaline fuel cell.
(ii) Molten carbonate fuel cells.
(iii) Phosphoric acid fuel cells.
(iv) Solid oxide fuel cell.
(v) Proton exchange membrane fuel cells.
Some of these are mentioned below :
3B.2.1 Alkaline Fuel Cells
In these cells, 30-45 wt. % aqueous solution of potassium hydroxide is used as electrolyte,
depending on the system. Acidic impurities such as CO 2 should not be present in the reactants
CO2 impurities from air can be removed by passing it through the absorption tower containing
soda lime. Alkaline fuel cells work at optimum temperature of SO°C. These make use of
inexpensive materials such as oxygen, hydrogen and alkali. These systems usually used high
purity hydrogen from electrolysis plants as fuel and oxygen as oxidant. The cell and electrodes
can be built from low cost carbon and plastics. The battery, when started at room temperature
will have low power efficiency but gets warmed up during the operation and the efficiency
Circulating
KOH lIo1ution
t
-+ ::::t:==!==::::::::
Pressure
:=:::=~:==):::: -
Pressure' .
H,
°2
Condenser
HzO lIsO
Fig. 3.11. Alkaline Fuel Cell equipped with dual-loop water removal system with circulating jets.
rises to the optimum value. This is the advantage over other types of fuel cells working at
intermediate temperatures. A wide range of electrodes can be used in alkaline fuel cells. Noble
metals have to be used as electrodes when acid electrolytes are used but they are expensive.
H 2-02 fuel cell in an example of alkaline fuel cell. Alkaline fuel cells are used in potable power
generation equipments.
3B.3 HYDROGEN·OXYGEN FUEL CELL
Hydrogen-oxygen fuel cell consists of two electrodes made of porous graphite impregnated
with finely divided platinum, or a 75/25 alloy of palladium and silver, or nickel. The secret of
8ucces8ful,fuel cells probably lies in the development of inexpensive electrodes that are powerful
catalysts for the electrode. reactions. The electrodes are placed in a concentrated solution of
KOH in water. Hydrogen and oxygen gases are bubbled through the anode and the cathode
compartments respectively. The gases diffuse through the electrode pores in to the electrolyte,
" where the following reactions take place:
Anode : 2~(g) + 40Hiaq) -+ 4~O(l) + 4e-
Cathode: 02(g) + 2~O(l) + 4e -+ 4QH-(aq)
Net : 2~(g) + 02(g) -+ 2~O(l)
The standard emf of the cell,
Ell = E°Q.% + EOred =0.83 V + 0.40 V =1.23 V
It may be noted that the only product discharged by the cell is water. Water should be ·
.removed at the same rate as it is formed. Otherwise, water dilute the KOH and the cell becomes
. inoperative. Therefore, the electrolyte is kept not so that water evaporates as fast as it formed.
Usually, a large number of these cells are stacked together in series to make a battery, called
fuel cell battery or fuel battery. A typical H 2-02 fuel cell is shown in Fig. 3.12.
1.23 V
Porous graphite
electrode coated with
platinum electrocatalyst
--+-PolY!ltyrene suI phonic

acid ion exchange
membrane in KOH
H 2- -
~--:---. Wicks for

maintaming
water
balance
Fig. 3.12. ~-O2 fuel cells.

H 2-02 fuel cell is used as an electric power source for space vehicles, mobile power systems
and military.
FueiCells 125
Anode
Gas chambers ~_...I
PoroUB electrodes
Lon-exchange
membrane
Oxidizer (oxygen)
lIsO
Fig. 3.13. Hydrogen-oxygen fuel cell.
3B.4 METHANOL-OXYGEN FUEL CELL

This cell is operate below 100°C. It
Cathode +
is simple in design. Methanol is one of
the most electro active organic fuels in
the low-temperature range due to low
carbon content and possesses a readily
oxidisable OH group. Dilute sulphuric
acid is used as the electrolyte in case
of methanol-oxygen fuel cell. A typical
methanol-oxygen fuel cell is shown in
Fig. 3.14.
Cathode 4-+---
----1--. Anode
Methanol containing some Membrane

sulphuric acid is circulated through the
anode chamber. Pure oxygen is passed
through the cathode chamber and
sulphuric acid, (which is an
ExcesaO.
electrolyte). Both the electrodes are and water
made of platinum. A membrane is
inserted adjacent to the cathode on the
inner ·side to minimise diffusion of '--~-----. CO 2
methanol in to the cathode, otherwise
Fig. 3.14. Methanol-oxygen fuel cell.
methanol undergoes oxidation.
The following reaction takes place at the electrodes :
At anode: CHsOH(l) + ~O(l) --+ CO2(g) + 6H+(aq) + 6e
At cathode: 121 02(g) + 6H+(aq) + 6e --+ 3~O(l)
1
Overall reaction: CHsOH(l) + 12 02(g) --+ CO 2(g) + 2~O(l)
The emf of the cell is 1.20V at 25°C. It is used in military applications and in large scale
power production. An advantage of this cell is that the CO2 , a product of the reaction can be
removed easily.
SB.2.2 Phosphoric Acid Fuel Cells (PAFC)
These are considered at the most advfulced
fuel cells after the alkaline fuel cells used in
space-crafts. Phosphoric acid fuel cells have
been operated in a wide range of power out- Cathode
Anode
put (1 Kw to 5 Mw). They operate at Electrolyte
temperature around 200°C. The high HaPO.
temperature improves the conductivity of the (matrix) Air
phosphoric acid. The electrodes are made of
Teflon bonded gas diffusion platinum catalysts.
The oxygen reduction reaction is the rate
determining factor for the performance of the
cell. The reaction occurring in a PAFC with a
matrix electrolyte in shown in Fig. 3.15. The
electrolyte is contained in a silicon carbide Fig. 3.15. Reactions occurring in a Phosphoric Acid
Fuel Cell with a matrix electrolyte.
matrix deposited on or placed between the
electrodes. PAFC can operate with reformed hydrocarbons or alcohols. Reforming of fuel into
a hydrogen-rich gas takes place in separate reforming units which are coupled with the fuel
cell stacks. Catalyst poisoning due to CO is minimum because of the high operating
temperature. Air is used as oxidant and also for cooling.
PAFC power plants using methanol as fuel were developed for U.S. army systems producing
20 KW on that basis were used for electric vehicle power plants. At temperature greater than
150°C the acid polymerizes to pyrophosphoric acid (HsP207) which has higher conductivity and
hence the efficiency of the battery increases. Several such cells are stacked to give 4.8 MW
energy.
SB.2.S Molten Carbonate Fuel Cell (MCFCs)
These operates generally at temperature> 500°C. These cells require fused salts (e.g., alkali
metal carbonates or hydroxide) or solid electrolytes.
The cell reactions are
At anode: H2 + COS-2 --+ CO2 + H 20 + 2e-
1 _ 2-
At cathode : 2 02 + CO 2 + 2e --+ COs
Overall reaction
Nickel electrode with 10% Cr is used as anode and the cathode consists ofNiO containing
1-2% cobalt. The electrolyte consists of a mixture of LiAl02, Li 2COS and ~COs'
Fuel Cells 127
A great advantage of MCFC is that the waste heat is useful for cogeneration. Therefore,
most MCFC development programs are aimed at medium to high power range (l00 KW to 10
MW) plants for electric utility or industrial use. Coal-fueled MCFC power plants have been
dev~loped by International Fuel cells for electric utility.
3B.2.4 Solid Oxide Fuel Cells (SOFC)

In these cells, a solid electrolyte e.g., a mixture of yttrium dioxide and zirconium dioxide
is used. The cells operate at a temperature of about 1000°C. Charge transfer in the electrolyte
is done by oxygen ions. The anodes are made of nickel/zirconium oxide whereas the cathodes
are made oflanthanum manganate (LaMnO a). Reformate gases (H 2 + CO) are used as fuel and
oxygen is used as oxidant. The electrodes reaction may be summarized as follows:
Anode reaction :XC H 2(g) + YCO(g) + (X + Y) 02-~ XH20(g) + YC0 2(g) + 2 (X + Y)e-
Cathode reaction: "21 (X + Y) 02(g) + 2(X + Y)e- ~ (X + Y) 02-

Overall reaction:
1
"2 (X + Y) 02(g) + ~(g) + XH2(g) + YCO(g) ~ XH20(g) + YC0 2(g)
Since the cathode reaction uses only oxygen (or air) as oxidant, recirculation of carbon
dioxide from the anode exhaust is not needed. Carbonmonoxide does not poison the electrodes
and indeed it is also used as fuel. During their operation, SOFC produce large quantities of
heat, which can be used for space heating, water heating etc. These cells may also be used in
locomotives. The essential features of solid oxide fuel cell are shown in Fig.
3B.2.5 Ion Exchange Membrane Fuel Cells or Solid Polymer Electrolyte Fup.l Cells
(SPEFCs)
The General Electric Company, USA in 1960 demonstrated the first practical application
of an ion-exchange membrane fuel cell with a 1 KW fuel cell. Initially, polystyrene sulfonates
were used as membrane materials. They were later replaced by more stable sulfonated
polytetrafluoroethylene. The membrane is chemically and electrochemically stale even at 200°C,
has high conductivity and in very thin. The membrane is about 1 mm thick and is sandwiched
between two porous metal electrodes. Hydrogen and oxygen are fed into the anode and the
cathode respectively giving rise the following reaction.
Anode: 2H2 + 2H20 ~ 4HaO+ + 4e-
Cathode: 02 + 4HaO+ + 4e- ~ 6H20
Such a fuel cell was used in the Gemini V-rocket in 1965. The Gemini SPE power plant
contained a stack of 32 cells which were built into a power module. Gemini power plant had a
voltage of about 25V and was rated at 2 KW.
The General Electric Company has also developed a regenerative fuel cell system for space
station applications.
3B.2.6 Biochemical Fuel Cells
In 1911, potter demonstrated a bio-cell in which disintegration of organic compounds by
micro-organisms could generate electricity.
In biochemical fuel cells, organic substrates (e.g., urea and glucose) act as a fuel which is
oxidised with the help of living organisms such as bacteria or enzymes derived from bacteria.
These function as bio-anodes. It is possible to accomplish direct reduction of oxygen or some
other oxidant at the cathode (biocathode). Biochemical agent promote one or both the electrode
reactions. Bio-chemical fuel cell should be operated at temperature range (0-40°C) and pH 7.0.
A bio-chemical fuel cell mechanism at the anode is presented below. The enzyme-catalyzed
reaction involving glucose is a two-electron process with methylene blue serving as an
intermediate. The reaction uses coenzymes of glucose oxidase' (FAD) which plays an important
role in enzyme activity.
CSH120S + FAD ~ CSHlOOS + FADH2
FADH2 + MB ~ FAD + MBH2
MBH2 ~ MB + 2H+ + 2e-
CSH120S ~ CSHlOOS + 2H+ + 2e- at anode
The electrons released are used up for the cathode reduction process
Mg2+ + 2e- ~ Mg at cathode
In the indirect approach, the- biological system can be used to generate reactants that
are consumed at the electrodes. For instance, pseudomonas mathranica bacteria can utilize
the carbon from methanol or methane to liberate hydrogen which can be subsequently used
as fuel. Such system can be used to control pollution due to organic waste and at the same
time generating electricity.
1. What is a fuel cell ?

2. What is the basic difference in the working of fuel cell and an electrochemical cell ?
3. How does a fuel cell differ from a battery ?
4. What is nature of fuel cells-primary or secondary ?
5. How can you classify fuel cell? Give an example of each type.
6. What are the main advantages of fuel cells ?
r 7. "Give the reactions taking place in the H -0
2 2 fuel cell.
8. Why and How the water balance is maintained in H 2-02 fuel cell ?
9. Why methanol and not some other organic compound is used as a fuel in a fuel cell
?
10. Give the reactions taking place at the electrode and overall reaction of methanol-
oxygen fuel cell.
11. Name the electrolyte used in molten carbonate fuel cell and give the reactions taking
place in the cell.
12. Name the materials used as anode, cathode and electrolyte in a solid oxide fuel cell.
What is the advantage of using this cell.
13. Show that the overall reaction taking place in a molten carbonate fuel cell is the same
as in H 2-02 fuel cell.
14. Comment on the statement 'Solid polymer electrolyte fuel cell is modification of
H 2-0 2 fuel cell'.
15. List some limitations of fuel cells.
16. What are the characteristics of fuel cells?
17. Enlist the requirements to be fulfilled for the successful functioning of a fuel cell.
Fuel Cells 129
( ANSWERS)
1. A fuel cell is an electrochemical cell in which the chemical energy contained in an easily
available fuel supplied to the system continuously is converted into electrical energy.
2. The basic principle of a fuel cell is, identical to that of an electrochemical cell. The
only difference is that in fuel cell, the chemical energy is provided by a fuel and an
oxidant stored outside the cell. However, the fuel and the oxidizing agent are
continuously supplied to the electrodes of the cell, at which they undergo reactions.
In case of an electrochemical, the redox reactions is allowed to take place indirectly
for the conversion of chemical energy into electrical energy.
3. A fuel cell differs from a battery in the following respects :
(i) In a fuel cell, the reactants are fed from outside the cell and do not form an
integral part as in a battery.
(ii) Unlike batteries, fuel cells do not store chemical energy.
(iii) Reactants are constantly supplied and the products are constantly removed from
a fuel cell.
4. Fuel cells are also primary cells and they are capable of supplying current as long as
the reactants are supplied.
5. There are three classes of fuel cells (i) Low temperature fuel cells which use water-
based electrolytes; For example, Methanol-Oxygen fuel cell. (iT.) Medium temperature
(about 600°C) fuel cells which use molten salts. For example, Molten carbonate fuel
cell. (iii) The most efficient high temperature fuel cells operating at lOOO°C which use
ceramic electrolytes. For example, solid oxide fuel cells.
6. Advantages of Fuel Cells
(i) The energy conversion (from chemical to electrically) is highly efficient (75 to
82.8%) by fuel cells.
(ii) Hydrogen-oxygen fuel cell produces drinking water of potable quality.
(iii) Noise and thermal pollution are low.
(iv) They offer excellent method for efficient use of fossil fuels and thus saves fossil
fuels.
(v) They are modular and have low maintenance costs.
(vi) The regenerative Hydrogen-oxygen fuel cell is an energy storage system for space
applications.
(vii) They are eco-friendly since the products of the overall reactions are not toxic
and hence pose no pollution problems.
(viii) Low cost fuels can be used with high temperature systems.
(ix) Fuel cell automotive batteries can render electric vehicles efficient and reliable.
(x) Fuel cells are suitable for the future nuclear, solar, hydrogen economy.
(xi) Fuel cells hold promise in the energy scenario where hydrogen is projected as
the main energy carrier of the twenty first century.
7. The reactions occurring in H 2-02 fuel cell at the electrodes and overall reaction are
given below :
Anode: H 20 + 20H-(aq) ~ 2H20 + 2e-
Cathode: i 02(g) + H 20(l) + 2e- ~ 20H-(aq)
Overall reaction H 2(g) + i 02(g) ~ H2°(l)

8. Water, the product of the overall reaction, should be removed at the same rate as it is
formed the inside. Otherwise, water dilutes the KOH and the cell becomes inoperative
Therefore, electrolyte is kept hot so that water evaporates as fast as it is formed. A
wick placed the electrolyte helps in maintaining water bahmce.
9. Methanol is one of the most elector active organic fuels in the low temperature range.
It is mainly because,
(i) It has a low carbon content;
(ii) It possesses a readily oxidisable OH group; and
(iii) It has high solubility in aqueous electrolytes.
10. Reactions at the electrodes and overall reaction are as follows :
At anode: CH30H (l) + H 20(l) ~ CO 2(g) + 6H+ (aq) + 6e-
1 .
At cathode: 1202(g) + 6H+(aq) + 6e- ~ 3Hp(l)
Overall reaction:
1
CH30H (l) + 1'2 02(g) ~ CO2(g) + 2~0(l)
11. The electrolyte used in the molten carbonate fuel cell consists of a mixture of LiAI0 2,
LiC03 and ~C03'
The cell reactions are :
At anode: H2 + C0 32- ~ CO 2 + H 20 4- 2e-
At cathode: Yz 02 + CO 2 + 2e ~ C032-
Overall reaction:
H2 + Yz 02 ~ H20
12. The anode consists of Ni on Zr0 2.
The cathode is porous strontium doped LaMn03.
The electrolyte is a solid and generally consists of Zr0 2 - Y203' The advantage of so
electrolyte is that it is less corrosive.
13. The reactions taking place in a molten carbonate fuel cell are :
At anode: H2 + C032- ~ CO 2 + H 20 + 2e-
1
At cathode: 2 02 + CO2 + 2e- ~ C032-
Overall reaction:
In case of H 2-02 fuel cell, reactions occurring at the electrodes and overall reaction
are as follows:
Anode:
Fuel Cells 131
Cathode:
Overall reaction:
It is clear that the overall reaction in the two fuel cells is the same.
14. The cell reactions in a solid polymer electrolyte fuel cell are given below:
At anode: H2 (g) ~ 2H+ + 2e-
At cathode: Y; 02 (g) + 2H+ + 2e- ~ 2H20 (l)
Overall reaction :
The protons liberated at the anode pass through the thin membrane. On the other
side of the membrane, the protons react with the oxygen at the cathode forming water.
No bulk liquid water is required for the cell to function.
The overall cell reaction of this fuel cell being the same as in case of H 2-0 2 fuel cell.
It is, therefore, just a modification of H 2-02 fuel cell.
15. Limitations of Fuels Cells
(i) Life-times of fuel cells are not accurately known.
(ii) Their initial cost is high.
(iii) Pure hydrogen is very costly.
(iv) Liquefaction of hydrogen requires 30% of the stored energy.
(v) There is lack of infrastructure for the distribution of hydrogen.
(vi) Large weight and volume of gas-fuel storage systems.
(vii) There is necessity of further research and development efforts for direct oxidation
of hydrocarbons in the fuel cells.
(viii) Most of the alkaline cells suffer from CO 2 degradation and hence CO 2 should be
removed from the fuels and the air.
16. Important characteristics of fuel cells
(i) They have high efficiency,
(ii) Their emission levels are far below the permissible limits,
(iii) They are modular and hence can be built in a wide range of power requirements,
(iv) Their noise levels are also low,
(v)They are free from vibration, heat transfer and thermal pollution.
17. Basic requirements to be fulfilled for the successful functioning of a fuel
cdl:
1. The fuel and the oxidants must be relatively cheap and readily available.
2. A stable interface between solid electrode, the liquid electrolyte and the gaseous
fuel promotes high rate of electrode processes and this is provided by suitable
fuel cell electrode design.
3. Higher temperatures and suitable catalyst are sometimes needed to promote high
rate of electrode processes.
4. In order to have an appreciable conductivity and to minimize the effect of
concentration polarization, fairly concentrated a~ueous solutions of the electrolytes
should be used as far as possible.
1. What is a fuel cell ? How is it different from the convention galvanic cells ? List at
least five advantages of fuel cell.
2. Describe with reactions the construction of hydrogen oxygen fuel cell drawing a line
diagram.
3. Explain the construction of methanol-oxygen fuel cell and give the reactions taking
place in the cell. Explain the suitability of methanol as a fuel in the cell.
4. Give an account of the different type of fuel cells. Give one exam pIe of each type giving
the cell reactions in each case.
5. Write short notes on any three of the following:
(a) Phosphoric acid fuel cells.
(b) Ion exchange membrane fuel cells.
(c) Solid oxide fuel cells.
(d) Molten carbona.te fuel cells.
6. Write informative notes on any two of the following:
(a) Advantages and limitations of fuel cells.
(b) Alkaline fuel cell systems.
(c) Solid oxide fuel cells.
7. Write the electrode and electrolyte material of the following fuel cells. Give also the '
reactions taking place in the cells.
(i) Proton Exchange Membrane Fuel Cell.
(ii) Alkaline Fuel Cell.
S. What are fuel cells? Describe the construction and working of H 2-0 2 Fuel cell.
(Y.T. U., B.E., Aug. / Sept. 1999)
(a) How does fuel cell differ from a battery? Explain the factors influencing the EMF
of batteries. (Y.T.u., B.E., March 1999)
(b) Mention any two advantages of fuel cells. Give the half cell reactions
occurring in H 2-02 fuel cell. Why is the water forced in the above cell removed
continuously? (Y.T. U., B.E., March 1999)
9. Give the construction of Hydrogen-oxygen fuel cell. Write the reaction involved.
(Y.T.U., B.E., April 2000)
10. Explain the working principle of methanal-oxygen fuel cell with reactions.
(Y.T.U., B.E., August 2001)
Fuel Cells 133
11. What are fuel cells? Explain the construction and working of H 2-0 2 fuels.
NT.U., B.E., August 2002)
12. Explain fuel cells containing polymer Electrolyte and Molten carbonate.
NT. U., B.E., Jan. / Feb 2003)
13. What are fuel cells ? Indicate the advantages of fuel cells ? Explain Methanol oxygen
fuel cells with the reaction involved. NT. u., B.E., July / August 2004)
14. Describe the construction and working of methanol oxygen fuel cell.
NT. u., B.E., Feb. / March 2005)
CORROSION SCIENCE
SYLLABUS
Corrosion-Definition chemical corrosion; electrochemical theory of corros~on; Types of
corrosion-Differential metal corrosion, differential aeration corrosion (pitting and water line
corrosion), stress corrosion; Factors affecting the corrosion; Corrosion Control: Inorganic
coating-anodizing and phosphating, Metal coatings-galvanization and tinning, corrosion
inhibitors, cathodic and anodic protection.
4.1 INTRODUCTION
As soon as the metals are extracted from their ores, the reverse process begins i.e., nature
tries to convert the metals back into the form in which they occur. This is due to the chemical
attack of the gases present in the atmosphere on the surface of the metal converting it into
compounds such as oxides, sulphides, carbonates, sulphates etc. It can also take place due to
electrochemical interaction of metal with the environment.
Definition
The process of slow destruction of metals due to chemical or electrochemical attack of

the environment at their surfaces resulting into the formation of compounds such as
oxides, carbonates, sulphides, sulphates etc. is called corrosion.
The most common example of corrosion is the rusting ofiron. Rust is hydrated ferric oxide,
Fep3'xHp. The reddish brown precipitate of iron oxide is a mixture of Fe(II & III) oxide namely
Fe30 4 (FeO.Fep3)' Some other examples include tarnishing of silver, development of green
coating of basic carbonate [CuC03 + CU(OH)2Jon copper and bronze etc.
Corrosion Science 135
Let us look into the cause of corrosion of metals. Most of the metals excepting noble metals
(Au, Pt etc.) exist in nature in the combined forms such as oxides, chlorides, sulphates, sulphides
etc. In the combined form they have lower energy as compared to their energy in the pure or
isolated metals. The metals are thermodynamically unstable and have a tendency to acquire
thermodynamic stability i.e., lower energy. Therefore, the metals easily undergo interaction
with the environment either chemically or electrochemically to form a stable compound by
the process of corrosion. Hence we conclude that corrosion is a oxidation process in which
some metallic compound (oxide, sulphide etc.) having lower energy is formed and energy in
liberated.
Corrosion (oxidation)
Metal (Higher energy) ~,:::::;¢::¢.===:=~=.::::;:='
Metallurgy (reduction)
Metallic compound (lower energy) + energy
Corrosion occurs at the surface of metal and is a slow process, but its ill effects are
numerous. Due to corrosions metals lose their malleability, ductility, electrical conductance
etc. and ultimately get destroyed slowly. It destroys metallic equipments, machines and
instruments and reduces their efficiency. It is, therefore, important to study its mechanism
and measures to control it to minimize the loss due to corrosion.
4.2 TYPES OF CORROSION
Corrosion of metals can take place in many ways. Various types of corrosion processes are
given in the chart below. Their mechanisms has also been discussed.
By Other Liquid
oxygen gases metal Interm-anular Erosion Microbiological
J +
Galvanic or Pitting Crevice Concentra- Water Stress
(Differential tion cell or line
metal) (Differential
aeration)
4.3 DRY OR CHEMICAL CORROSION

The direct chemical action of atmospheric gases such as oxygen, halogens, sulphur dioxide
and hydrogen sulphide with metals resulting into the formation of compounds such as oxides,
halides, sulphates and sulphides is referred to as chemical corrosion. It is mainly of the following
three types :
(a) Corrosion by Oxygen (Oxidation Corrosion)
Atmospheric oxygen reacts with metals in the absence of moisture forming their respective
oxides:
Alkali metals (Li, Na, K etc.) and alkaline earth metals (Be, Ga, Sr, etc.) are oxidized at
low temperatures, whereas all other metals (except, Ag, Au, and Pt) are oxidized at high
temperatures.
Mechanism : The process of oxidation starts at the exposed surface of metal. The metal
loses electrons and changes to metal ions, whereas oxygen accepts the electrons and changes
to oxide ion.
M ~ Mn+ + ne- (Oxidation of metal)
%[~02 + 2e- ~ 0 2- ] (Reduction of oxygen)
overall reaction 0 2- ~
Metal ion Oxide ion

At the point of contact of Mn+ and 0 metallic oxide M 2 0 n is formed. This oxide layer
2
-,
formed acts as a barrier towards further oxidation. The continuation of the oxidation process
depends upon two factors : (i) the nature of the oxide film formed (ii) the rate of diffusion of
the metal ion and the oxide ion through the layer formed.
(i) Nature of Oxide Film Formed on the Surface
(a) When the oxide film is stable, tightly adhering and impervious in nature, it acts as
a protective coating and further action of atmospheric oxygen on the metal is
prevented. For example, oxide films formed on AI, eu, Sn and Pb are of this type.
(b) When the film formed is unstable and decomposes back to metal and oxygen, oxidation
corrosion can not continue further. Metals like Ag, Au and Pt form this type of oxide
films.
(c) When the volatile film is formed, it gets volatilized as it is formed making the metal
surface available for continuous attack. For example, Mo forms volatile oxide and it
is corroded completely with passage of time at a fast rate.
4Mo + 302 ~ 2M0 20 a (Volatile)
(d) When the oxide film is porous in nature, the metal is attacked by oxygen through
the pores and crack~ and the corrosion continues till the entire metal is converted
into its oxide. Metals like iron form this type of film.
Pilling-Bedworth Rule
This rule is helpful in deciding whether the oxide film formed on the metal surface is porous
or non-porous. According to this rule,
"An oxide film is non-porous i.e., protective, if the volume of oxide is at least equal to or
greater than the volume of metal from which it is formed. However, if the volume of the
oxide is less than the volume of the metal, the oxide film is porous i.e., non-protective. This
rule can also be stated in terms of specific volume ratio, which is calculated as under:
·fi 1 t· Volume of metal oxide
S pecI c vo ume ra 10 = - - - - - - - - - -
Volume of metal
(i) If the volume of the metal oxide> volume of the parent metal i.e. specific volume is
greaterthan one, then the oxide film will be non-porous.
(ii) If the volume of the metal oxide < volume of the parent metal i.e. the specific volume
is less than one, then it will be porous for diffusion of Mn+ and 0 2- and oxidation will
take place.
Metals like AI from oxide having greater volume as compa,red to the metal, so they form
non-porous oxide layer and further oxidation of the metal is prevented. On the other hand,
alkali and alkaline earth metals form oxides having lesser volume as compared to the metal,
they form porous oxide films which allow further attack to atmospheric oxygen through the
pores and the metals are completely corroded.
(ii) Rate of diffusion of metal ions: The metal oxide film formed at the surface of metal
acts as an interface. For the oxidation to continue further, the metal ions (Mn+) must diffuse
outwards and the oxide ion (02-) inward through the interface for further action between them.
This happens through the pores of the porous film only and not through the non-porous film.
The metal ions being smaller in size as compared to the oxide ions diffuse outward at a faster
rate than the oxide ions diffusing inward.
(b) Corrosion by Other Gases
Besides oxygen, gases like C12, S02' H 2S, CO2 and F2 also react with metals. The corrosive
effect of these gases depend upon their chemical affinity for the metal and also upon the nature
of the compound formed by them i.e., whether the film formed is protective or non-protective.
For example, Cl2 reacts with silver forming a protective (non-porous) film of AgCI which prevents
further attack of Cl2 on Ag. But Cl2 forms a volatile chloride of tin. Similarly, HzS gas at high
temperature reacts with iron forming a porous FeS film and corrodes iron.
(c) Liquid Metal Corrosion
When liquid metal flows over solid metal at high temperature, corrosion takes place which
is called liquid metal corrosion. It weakens the solid metal due to (i) penetration of the liquid
metal, (ii) dissolution of the solid metal in liquid metal. A common example of this type of
corrosion is the corrosion of cadmium rods taking place due to sodium metal acting as coolant
in nuclear reactors.
4.4 WET OR ELECTROCHEMICAL CORROSION
Wet corrosion is more common than dry corrosion. It occurs mostly under wet or moist
conditions through the formation of electrochemical cells and is, therefore, referred to as
electrochemical corrosion. The mechanism of electrochemical corrosion is given below :
(i) The metal should have separate anodic and cathodic areas between which electron
may flow through the conducting solution.
(ii) Oxidation (loss of electrons) take place at the anodic area and the metal is destroyed
by either dissolution or combination with oxygen. Hence, corrosion always takes place
at the anode.
M ~ Mn+ + ne- (oxidation)
Mn+ forms compounds such as oxides or dissolves in solution
(iii) Reduction (gain of electrons) takes place at the cathode. The electrons from the anode
are accepted by the dissolved oxygen forming ion such as OH- or 02- ions .
.!.02 + H 20 + 2e- ~ 20H- (Reduction)
2
or 02 + 2e- ~ 202- (Reduction)
(iv) The metallic ions formed at the anode and non-metallic ions formed at the cathode
diffuse through the conducting medium and combine to form the corrosion product
some where between anodic and cathodic area.
Wet corrosion involves flow of electrons between the anodic and cathodic areas. The anodic
reaction involves dissolution of metal as corresponding metallic ions with the liberation of free
electrons. Whereas, the cathodic reactions accept electrons by two ways: (i) evolution of
hydrogen or (ii) by absorption of oxygen. The evolution of hydrogen and absorption of oxygen
in cathodic reaction depend on the nature of corrosive environment.
(i) Evolution of hydrogen : The process of corrosion in which Hz is liberated is called
evolution of hydrogen type corrosion. This type of corrosion usually takes place in acidic
environment. Thus, in acidic medium (absence of oxygen) hydrogen ions acquire electrons with
the liberation of H2 gas in cathodic reaction, whereas the anodic metal atoms lose their electrons
to the environment and pass into solution in the form of +ve ions.
2H~O+2e- ~ 2~O+H2 t (Cathodic reaction)

or 2H+ + 2e- ~ H2t
In neutral and alkaline medium (in the absence of oxygen) the reaction taking place will be
2H20 + 2e- ~ 20H-+ H2 t (cathodic reaction)
whereas in the anodic area, the dissolution of iron as Fe2+ions with the liberation of electrons
takes place.
Fe Oxidation) Fe 2+ + 2e-
These electrons flow through the metal, from anode to cathode, where H+ ions of acidic solution
are eliminated as H 2.
Fe + 2H+ ~ Fe2+ + H2
Therefore, this type of
1~G~~~~Fc~~~~~~~~~~-ACidiC
corrosion causes displacement of
hydrogen ion from the acidic W solution
(electrolyte)
solution by metal ions.
The above mechanism can
be easily understood from
Fig. 4.1.
It is clear that anodic areas Iron metal
are very large in comparison to
cathodic areas. All the metals,
above hydrogen in the electro-
chemical series have a tendency Fig. 4.1. Mechanism of wet corrosion by hydrogen evolution.
to get dissolved in acidic solution
with simultaneous liberation of hydrogen.
(ii) Absorption of oxygen: This type of corrosion occurs in neutral environment (such
as NaCI solution used as electrolyte). The popular examples of absorption of oxygen type
corrosion is, rusting of iron in neutral aqueous solution of NaCI in the presence of oxygen
(atmospheric). ................ .... ......... .............. ............... .... .................. .. .... ..
The surface of iron is usually Ui!~::i;i:i)i:!i::+iri::i:::!!!::::h'::::~~~:ii:i::i.:.i .::::.:.:.::.;·;;:i:::.:i!·: ::':::: NaCl solution
~~:;:e:r:~:m: ~~:c~: :::::~:il:~flll;;~~~'f~'l\~~~I!l (.Ioctroly")

film, an anodic area is developed on the Iron oxide
surface, whereas the wet metal part film
acts as cathodic area. In this corrosion
reaction, cathodic area is much more Iron metal
large in comparison to anodic area.
The above overall reaction Fig. 4.2. Mechanism of wet corrosion by absorption of oxygen
mechanism is represented type corrosion.
diagrammatically in Fig. 4.2.
Thus, from the above diagram it is clear that at the anodic area, iron metal dissolves with
the liberation of electrons as
Fe Oxidation) Fe2+ + 2e-
The above evolved electrons flow from anodic areas through iron metal where electrons
are taken up by the dissolved oxygen as
Ih 02 + H 0 + 2e- Reduction) 20H-

2
The OH- ions formed at cathode as well as Fe2+ ions formed at anode combine and from
ferrous hydroxide Fe(OH)2 as precipitate
Fe 2+ + 20H- ~ Fe(OH)2..l-
In the presence of sufficient oxygen, Fe(OH)2 can be easily oxidized into ferric hydroxide
[Fe(OH)aJ
4Fe(OH)2 + 2Hp + 02 ~ 4Fe(OH)a..l-
Actually hydrated ferric oxide 2Fe(OH)3 corresponds to Fep3.3Hp.
If the supply of oxygen is limited we get mixture of FeU I and III) hydrated oxide i.e.,
ferrosoferric oxide hydrated. It is black rust.
3Fe(OH)3 ~ Fe30 4 ·6Hp or Fepa.FeO.6H20
As we know that Fe + ion is smaller in size than OH- ion, the Fe 2+ ion will diffuse more
2
rapidly, so corrosion occurs at the anode, but rust is deposited at the cathode or near the
cathode.
4.5 COMPARISON OF CHEMICAL WITH ELECTROCHEMICAL CORROSION
S.No. Chemical Corrosion Electrochemical Corrosion
(i) It occurs in dry condition. It occurs in wet condition in the presence
of moisture and electrolyte.
(ii) It involves the chemical attack of oxygen It involves electrochemical attack of
or other gases. corrosive environment on the surface of the
metal.
(iii) It can occur at homogeneous as well as It occurs only on heterogenous metal
heterogenous metal surfaces. surfaces.
(iv) It is uniform in nature throughout the It is not uniform. If the area of anode is
surface of the metal. small, pitting corrosion takes place.
(v) It is a slow process taking place by It is a fast electrochemical process. It
chemical reaction of atmospheric gases. proceeds through the cells.
(vi) Corrosion products accumulate at the place Corrosion products accumulate somewhere
where corrosion occurs i.e., at the anode. between the area of anode and cathode.
(vii) Its mechanism is explained on the basis Its mechanism is explained on the basis
of absorption. of electrochemical reactions.
4.6 TYPES OF ELECTROCHEMICAL CORROSION

Electrochemical corrosion is mainly classified into two categories:
(a) Metal Differential Corrosion (b) Differential aeration corrosion.
(a) Metal Differential Corrosion
It is also known as Bi-metallic or Galvanic corrosion.
When two different metals are in contact and jointly exposed to atmosphere, the
metal with lower reduction potential i.e., higher position in the electrochemical series gets
corroded. This type of corrosion is called galvanic corrosion e.g., Zn and Cu, Zn and Ag, Fe
and Cu.
Zinc with higher oxidation potential than copper acts as anode and the electrons flow from
anodic metal (Zn) to cathodic metal (Cu). The anodic metal is corroded, while cathodic metal
remains protected.
In acidic solution, the corrosion occurs by the evolution of hydrogen as under.
Zn + 2H+ ~ Zn2++ H2
In neutral or slightly alkaline medium, oxygen absorption takes place.
H 20 + ~02 +2e- ~ 20H-
Control : The following factors favour differential metallic corrosion. Keeping in view,
the above factors, galvanic corrosion can be minimized by (i) avoiding galvanic couples i.e.,
minimising the potential difference between the concerned metals; (ii) providing an insulating
material between the two metals; (iii) avoiding the suitable medium for corrosion; (iv) by
polishing the metals.
Some common examples of bimetallic corrosion are (i) steel screws in brass or bronze
equipment, (ii) lead-antimony solder around copper wire, (iii) steel pipe connected to copper
plumbing. These combinations should be avoided.
(i) Greater the potential difference between the two metals forming the galvanic cell,
greater is the corrosion.
(ii) A suitable medium is required for the flow of electrons.
(iii) Exposed surface area ofthe metal.
Cu(cathode)
.--------------
----_.--
--- .. -----
... -----------
--------------
---------------
--------------
---------------
------- ------
------- Conducting
------- ------
--------------- solution
..--------------
--------------
--------------
~~~~
---------------
--------------
Fig. 4.3. Diagrammatic representation of galvanic corrosion.

(b) Differential aeration corrosion or
Concentration cell corrosion.
This type of corrosion occurs when the metal ZnRod
surface is exposed to an electrolyte of varying
concentration or of varying aeration. It also occurs
when one part of the metal is exposed to a different
air concentration from the other part. It has been
observed that poorly oxygenated parts become anodic
and are corroded, whereas more oxygenated portion Electrolyte
acts as cathode. solution
It occurs when a metallic surface is partially
immersed in a solution and partially exposed to the
atmosphere. Consider a metal (say Zn) is partially
immersed in a dilute solution of NaCI and solution Fig. 4.4. Differential aeration corrosion.
is not agitated for long. The part of the metal immersed in solution has less access to oxygen
and act as anode, whereas the part above and closely adjacent to the waterline is more strongly
aerated and act as cathode (Fig. 4.4). So, a difference of potential is created which causes flow
of electrons between two differentially aerated areas of the same metal. Zinc change to Zn2+
ions at the anodic area and oxygen take up electrons at the cathodic area of the metal to form
hydroxial ions. The Zn2+ and OH- ions interact to form Zn(OH)2
At anode 0:
Zn ~ Zn2++ 2e- (oxidation)
At cathode :
lh O2 + Hp + 2e- ~ 20H- (reduction)
Zn2+ + 20H- ~ Zn (OH)2
Differential aeration corrosion may further be classified into the following types:
(i) Crevice Corrosion
A crevice (joint) between different Cathode
metallic objects i.e., bolts, rivets etc. also
cause corrosion. The joint area has lack of
oxygen and becomes anodic and the
exposed area becomes cathodic. The Metal
corrosion is acceleration at the joint area Metal
acting as anode. This type of corrosion
acting at the junction of two metals
Bolt
exposed to corrosive environment is called
crevice corrosion (Fig. 4.5). To minimise Fig. 4.5. Crevice corrosion.
this type of corrosion, fixing of bolts, nuts, rivets etc. to metallic equipments should be avoided.
(ii) Pitting Corrosion
A small part of the metal surface covered by an impurity or water has a low oxygen
concentration and it acts as an anode, whereas the uncovered metal surface acts as a cathode
due to high oxygen concentration. The small covered area acting as anode gets corroded giving
rise to localized spots (pits), pinholes and cavities in the metal. Once a small pit is formed, the
rate of corrosion increases. The electrochemical reaction may be represented as :
At anode: Fe ~ Fe 2+ + 2e-
At cathode: .!.02 + H 20 + 2e- ~ 20H-
2
Fe2+ + 20H- ~ Fe(OH)2 Oxidation) Fe(OH)a
Pitting corrosion is usually caused due to cracking of the protective film on a metal at
specific points. The cracks serve as initiators of corrosion by creating two areas, one fairly
accessible to oxygen and the remaining poorly accessible. The presence of impurities such as
dust, sand, scale etc. also cause pitting corrosion. It is a non-uniform corrosion commencing
from a localised attack and results in the formation of pits, cavities and pin-holes in the metal.
Once a small pit in formed the corrosion will be accelerated.
(iii) Water Line Corrosion
When water is stored in a metallic tank, it is observed that corrosion takes place along a
line just below the level of water in the container. The area below the level of water is poorly
oxygenated and acts as anode, whereas area above the water level is highly oxygenated and
acts as a cathode. The part of the steel tank just below the water level is corroded, whereas
the area above the water level remains protected from corrosion (Fig. 4.6.).
At anode: Fe ~ Fe2+ + 2e- (oxidation)
At cathode:
Fe2++ 20H- ~ Fe(OH2)--,0xi='da=ti=on,,---+) Fe(OH)s
Waterline corrosion is a problem for the marine engineers when marine plants are attached
to the ships in ocean, waterline corrosion comes into action and it can be checked by anti-
fouling paints to some extent. Water level
(iv) Stress Corrosion
During the manufacture of metals and
different metallic equipment, metals undergo Anodic part
1
..................................._....
....................................
...................................
.. ::::::::::::::::::::::::::::
Cathodic part
....... -...-- ....... -........ --...- ..- Anodic part

certain processes such as bending, pressing, .. :::::::::::::=::::::::::::
................._.....................--... -
....................................
---::::::::::::::::::::::::::::.... -
rolling, quenching and annealings etc., which ::::::::::::::::::::::::::::::::::
..........
.... -... -................................
_......_...._....._.. .....
cause stress on certain areas of the metal. --__.........................
..._...............................
............................................ _.
Such areas under stress act as anode,
whereas other areas act as cathode. The
potential difference is thus developed between Fig. 4.6. Water line corrosion.
the strained (under stress) and unstrained
part of the metal. This accelerates corrosion of the strained portion of the metal in corrosive
environment. For stress corrosion to take place, the basic requirements are (i) stressed metallic
areas and (ii) corrosive environment, which is specific for particular metals and alloys. For
instance, caustic alkali is specific corrosive environment for mild steel, acid chloride solutions
for stainless steel and traces of ammonia for brass. The stressed part of the metal acquires a
higher electrode potential and becomes chemically active, towards the corrosive environment
and gets corroded. The following are some examples of stress corrosion.
(i) Stress corrosion of brass : The main components of brass are zinc and copper. Both the
components are prone to stress corrosion in ammonical environment. The metal (Zn as well as
Cu) lose electrons to change to their respective ions at the stressed portion ofthe equipment. The
ions so formed interact with NHa or amines to form their respective complexes as shown below:
Zn ~ Zn2++ 2e- and Cu ~ Cu 2++ 2e-
Zn2+ + 4NHa ~ [Zn(NHa)4]2+ and Cu2++ 4NHa ~ [Cu(NHa)4]2+
Stress corrosion of brass is also called season cracking. The complexes formed are soluble
and their, dissolution ultimately results in the formation of cracks in the brass.
Caustic Embrittlement
It is type of corrosion which is caused due to presence of alkalies in feed water. In case of
high pressure boilers, excess Na2COa (soda ash) added during lime soda process for removal of
hardness causing impurities, hydrolyses to give NaOH and makes water alkaline.
Na2COa + H 20 ~ 2NaOH + CO2
This makes the boiler feed water slightly alkaline. When this dilute alkaline water solution
flows into the minute hair cracks in boiler walls, water evaporates and concentration of sodium
hydroxide increases. The concentrated sodium hydroxide dissolves iron as sodium feroate, which
decomposes as follows:
3Na2Fe0 2 + 4Hp ~ 6NaOH + Fea0 4 + H2
(Sod.feroate)
6Na2Fe0 2 + 6H20 + 02 ~ 12NaOH + 2Fea0 4
'-----.r----'
MagnetIte
Therefore, sodium hydroxide is regenerated and magnetite is precipitated.
Caustic embitterment can also be explained on basis of electro-chemical theory. Following
electro-chemical cell due to differential aeration formed inside a boiler.
Cone. Dil. Iron present
Iron present at surface of
,-__in_c'V'r_ac_k_s_~, NaOH NaOH boiler walls
An~de
Cathode
Due to non-availability of oxygen, in the cracks, the iron present behaves as anode. Similarly
due to easy availability of oxygen on the boiler walls, iron behaves as cathode. Therefore, iron
present in the cracks undergoes oxidation and gets dissolved. Thus, the boiler walls become
weak.
Prevention of caustic embrittlement
(i) Using sodium phosphate in place of sodium carbonate for softening of water.
(ii) Applying tannin, oil, which fills the cracks present in boiler walls.
(iii) Applying sodium sulphate, which also fills the minute hair cracks in the boiler walls.
4.6.1 Other Forms of Corrosion

1. Atmospheric Corrosion
Atmospheric corrosion is the result of combined effect of two substances namely, oxygen
and moisture. Corrosion does not take place if one of these is missing, e.g., if iron is exposed
to an atmosphere containing more than 60% humidity (critical humidity) rusting of iron begins
and increases with increase in humidity. Corrosion appears to be negligible even at high relative
humidities, so long as the atmosphere is dust free. It has been also observed that steel does
not rust if it is covered with ice. This is because electrochemical attack require liquid water
for corrosion to take place. In the absence of liquid water which acts as an electrolyte for the
electrochemical ~ell, corrosion will not take place. Impurities like smoke, dust and gases like
S02 in the atmosphere also increase the rate of atmospheric corrosion. In industrial areas,
atmospheric corrosion is accelerated due to the presence of pollutants in the air.
Due to atmospheric corrosion, copper is corroded and its surface is covered with an adherent
layer of basic copper sulphate, CuS0 4 .Cu(OH\ and basic copper carbonate, CuC0 3.Cu(OH)2'
which gives adequate protection to the metal from further attack.
2. Soil Corrosion
In soil, corrosion of metals takes place due to the following factors :
(i) Moisture and electrolyte contents: The conductivity of the non-acidic soil depends
upon moisture and electrolyte content of the soil. This is the major factor governing
the corrosive nature of the soil, which is further promoted by differential aeration.
When a cable or pipeline passes under a paving, the portion under the paving has
less access to oxygen than the one lying under unpaved soil. Hence the portion under
the paving becomes anodic and suffers corrosion. The rate of corrosion mainly depends
upon the resistance between the anodic and cathodic areas and the rate of arrival of
oxygen to the cathode areas.
(ii) Acidity of the soil: In highly acidic soils, the corrosion taking place is of hydrogen
evolution type with anodic and cathodic areas very close to each other. The conductivity
of the soil is not of much importance in this case.
(iii) Physical properties of the soil: Burried pipelines and cables passing from one
type of soil to another suffer corrosion due to differential aeration. Soils rich in: gravel
and sand are more porous as compared to clay rich soils. For example, lead pipelines
passing through clay and then through sand are corroded because the area covered
under clay are less aerated as compared to that covered under sand. Consequently,
clay covered areas become anodic and get corroded. Air pockets in the soil, if present,
may also cause corrosion due to differential aeration.
(iv) Organic matter content of the soil: If the soils contain large amount of organic
matter,_ the formation of soluble metal complexes and the precipitation of corrosion
products may accelerate the corrosion process as compared to the soils relatively free
from organic matter.
(v) Presence of micro-organisms in the soil: In water logged soils the amount of
free oxygen is less and it may generate anaerobic bacteria, which may create conditions
of microbiological corrosion.
3. Microbiological Corrosion
Corrosion caused by the metabolic activities of various micro-organisms is called
microbiological corrosion. The microorganisms can develop and propagate in an environment
in the presence as well as absence of oxygen. They are, therefore, termed as aerobic and
anaerobic. The following three types of micro-organisms are responsible for this type of
corrosion:
(i) Aerobic microorganism: They include (a) sulphur bacteria and (b) iron and
manganese bacteria. Sulphur bacteria belong to thiobacillus family and they oxidize
the sulphur present in their body cells to sulphuric acid, which causes the corrosion
of metals, concrete and limestone. Such type of bacteria grow in acidic conditions
say pH from 0 to 1.
Iron and manganese microorganism are also aerobic bacteria and they live by taking
iron and manganese ions into their body cells which they digest in the presence of
oxygen forming insoluble hydrates of iron and manganese dioxide. These bacteria
grow in stagnant or running water at 5 to 40°C and pH between 4 to 10.
(ii) Anaerobic micro-organisms : Sulphur reducing bacteria, the sporovibrio
desulphuricous are responsible for anaerobic corrosion of iron and steel. They require
sulphur and-oxygen for their propagation and grow at 25 to 30°C and pH between 5
to 9.
(iii) Film forming micro-organisms: Bacteria, fungi, algae and diatoms are film
forming microorganisms. They can form microbiological film on an iron surface. Such
films are capable of maintaining concentration gradients of dissolved salts, acids and
gases on the iron surface, thereby leading to the formation of local biological
concentration cells and consequent corrosion.
4. Intergranular Corrosion
This type of corrosion takes place in alloys (solid solutions) due to faster precipitation of a
phase at grain boundaries. The precipitated compound acts as a cathode and the grain boundary
as an anode. Thus, a potential difference is developed which leads to the preferential dissolution
of anodic part of the system. For example, stainless steel is an alloy of iron, carbon and
chromium. During its formation, a precipitate of chromium carbide is formed at the grain
boundaries. Consequently, the composition of chromium becomes less in the region adjacent
to grain boundaries but the grain centre and the chromium carbide precipitate, both are richer
in chromium. Thus, the regions adjacent to the grain boundaries are anodic and more
susceptible to corrosion. It t? kes place on a very small scale, following the path of grain
boundaries until the affected grain is totally dislodged. There is no external indication of this
attack and the slow corrosion in progress leads to sudden failme of the equipment.
Intergranular corrosion can be minimized by avoiding heterogeneous precipitation which
takes place due to slow cooling of the alloy. Thus, proper heat treatment followed by rapid
quenching is essential. Heat treatment of the alloy dissolves the chromium carbide precipitate
which may be formed during the formation of the alloy.
5. Stray-Current Corrosion
Electric current from electric traction systems such as electric trains can leak into adjacent
conducting structures. The point from which the current leaves the structure acts as anode and
it starts corroding. This is known as stray-current corrosion and is aided by dissolved electrolytes.
This type of corrosion can lead to pitting and serious damage to underground structures.
6. Erosion Corrosion
In condensers and agitators, usually streams of gases, vapours or liquids emerge from an
opening and strike on the side-walls with high velocities. This results into the break down of a
protective film at the striking point on the surface of metals. This results in the formation of
differential cells at such areas and localized corrosion takes place at the anodic regions. This type
of corrosion is known as erosion corrosion and it damage the anodic regions of the equipment.
PRACTICE PROBLEMS FOR TUTORIALS)
1. What is corrosion of metals? [U.P. Tech., Jan. 2001J

2. What is meant by rusting of iron?
3. What is rust?
4. What is electrochemical corrosion ?
5. What is galvanic corrosion?
6. The rate of metallic corrosion increases with increase in temperature. Give reason.
7. Iron corrodes faster than aluminium, even though iron is placed below aluminium in
the electrical series. Why ?
8. Impure metal corrodes faster than pure metal under identical conditions. Give reason.
9. Wire mesh corrodes faster at the joints. Why ?
10. Corrosion of water filled steel tanks occur below the waterline. Give reason.
[PTU, Dec. 2002J
11. A pure metal rod half-immersed vertically in water starts corroding at the bottom. Give
reason.
12. Iron carro des under drops of salt solution. Give reason.
13. What are factors which promote electrochemical corrosion ?
14. What are the factors that contribute to the rusting of iron ?
15. Why does corrosion occur in steel pipe connected to copper plumbing?
16. Bolt and nut made of the same metal is preferred in practice. Why ?
17. State the two conditions for wet corrosion to take place.
18. A steel screw in a brass hardware corrodes. Give reason.
19. Rusting of iron is quicker in saline water than m ordinary water. Why?
20. What is the effect of CO 2 on electrochemical corrosion"
[ ANSWERS)
1. Corrosion is the process of gradual destruction of a metal from its surface due to the
unwanted chemical or electrochemical interaction of metal with its environment.
For example, formation of a layer of reddish scale of hydrated ferric oxide Fe20 s.3Hp
on the surface of iron, also known as "rusting of iron".
2. The atmospheric corrosion of iron and steel, leading to the formation of a layer of reddish
scale and powder of iron oxide (Fep 4) on the surface is called rusting of iron.
3. Hydrated ferric oxide (F'e 2 0s.xHP) is called rust. Mixed ferrous and ferric oxides
(FeS 0 4 = FeO.Feps) is called black rust.
4. This type of corrosion occurs due to the existence of separate 'anodic' and 'cathodic' areas
between which current flow through the conducting solution. At anodic area oxidation
occurs and thus, it gets corroded.
5. When two different metals are in contact and jointly exposed to atmosphere, the metal
with lower reduction potential i.e. higher position in the electrochemical series gets
corroded. For example, Zn gets corroded when combined with copper.
6. With increases of temperature of the environment, the rate of reaction as well as rate
of diffusion increase, thereby corrosion rate increases.
7. This is because aluminium forms a non-porous, very thin, tightly adhering protective
oxide film (Al2 0 S) on its surface and this film does not permit corrosion to occur.
S. Impurities in a metal generally cause heterogeneity, and form minute electrochemical
cells at the exposed parts, whereby the anodic parts get easily corroded.
9. The joints of wire mesh are stressed (due to welding), so these becomes anodic w.r.t.
the joined wires. At these anodic parts, oxidation takes place and the metal is corroded
fast, while the cathodic parts remain unaffected.
10. This is because the area above the waterline is highly oxygenated and acts as cathode
while the fully immersed part is poorly-oxygenated and acts as anode. 80 the anodic
part (below the waterline) gets corroded, due to electrochemical corrosion); while the
cathodic part (above the waterline) remains completely unaffected.
11. This is due to differential aeration. The rod above and adjacent to the waterline is more
strongly aerated and hence becomes cathodic; while the lower part of rod immersed in
water is less oxygenated and hence becomes anodic. This causes corrosion of the anodic
part. Hence, metal rod starts corroding at the bottom.
12. This is due to differential aeration. Areas of iron covered by drops, having poor access
to oxygen, become anodic w.r.t. other areas which are freely exposed to air. Due to
electrochemical corrosion, the areas under drops (anodic) undergo corrosion; while the
freely exposed parts remain unaffected.
13. (i) Reactivity of the metal : More active metals are readily corroded.
(ii) Presence of impurities: Presence of impurities in metals enhances the chances of
corrosion. Pure metals do not corrode e.g., pure iron does not rust.
(iii) Presence of air and moisture : Air and moisture accelerate corrosion. Presence of
gases like 802 and CO 2 in air catalyse the process of corrosion. Iron when placed
in vacuum does not rust.
(iv) Strains in metals: Corrosion (e.g., rusting of iron) takes pla(,!e rapidly at bends,
scratches, nicks and cuts in the metal.
(v) Presence of electrolytes: Electrolytes, if present, also increase the rate of corrosion.
For example, iron rusts faster in saline water than in pure water.
14. The factors that contribute to the rusting of iron are:
(i) Both oxygen and water are essential for rusting. Iron will not rust in water that is
completely free from oxygen. It will not rust in dry air also.
(ii) Rust formation is also enhanced by :
(a) the presence of acids and electrolytes
(b) the contact with less reactive metals like copper
(c) the presence of impurities, and
(d) rust itself
15. Because steel (or iron) is higher in the electrochemical series so it forms the anode and
undergoes corrosion when steel pipe connected to copper plumbing is exposed to an
corroding environment. This type of corrosion is called galvanic corrosion.
16. Because such a combination will not permit galvanic corrosion to take place.
17. (i) Immersion or partial dipping oftwo dissimilar metals or alloys in a solution.
(ii) A metal in contact with the conducting liquid.
18. This is due to galvanic corrosion. Iron having lower reduction potential i.e. higher
position in the electrochemical series as compared to copper in brass becomes anodic
and gets corroded. Copper having higher reduction potential becomes cathodic and is
not corroded.
19. The presence of N aCI in water increases the conductivity of water in contact with iron
surface. As a result susting of iron becomes quicker.
20. CO 2 gets dissolved in water to form carbonic acid (H 2C0 3), which makes the electrolyte
acidic. It is a weak acid and ionises as: H 2C03 ~ 2H+ + C032-. The conductivity of the
electrolyte also increases and the corrosion is promoted.
4.7 FACTORS INFLUENCING CORROSION
Following are the two main factors influencing the rate and extent of corrosion; which in
turn depend upon number of factors as explained below:
(a) Nature of the Metal
(i) Physical state of the metal (ii) Purity of metal (iii) Position in the galvanic series
(iv) Nature of the oxide films (v) Over voltage (vi) Volatility of corrosion product
(vii) Solubilities of the product of corrosion (viii) Relative areas of the anode and
cathode.
(b) Nature of Environment
(i) Temperature (ii) Humidity (iii) pH (iv) Nature of electrolyte (v) Conductance of
corroding medium (vi) Presence of impurities in atmosphere (vii) Formation of oxygen
concentration cell.
(a) Nature of the Metal
(i) Physical state of the metal: 'I he rate of corrosion is influenced by the physical state
of the metal such as grain size, orientatJ.on of crystal, stress, etc. The smaller the grain size of
the metal or alloy, the greater will be its solubility in corroding medium and hence greater
will be its corrosion. Moreover, areas u'lder stress, even in a pure metal, tend to be anodic
and corrosion takes place at these areas
(ii) Purity of metal : Metals are generally corrosion resistant. The rate and extent of
corrosion increases with the increase of the impurities, because the impurities present in the
metal form minute galvanic cells and anodic part gets corroded, while in an alloy, the solid
solutions are homogeneous and do not form galvanic cells.
(iii) Position in the galvanic series: The extent of corrosion depends upon the position of
the metal in the electrochemical series and galvanic series. When two metals are in electrical
contact in the presence of an electrolyte, the more active metal (or higher up in the series)
suffers corrosion. The rate and severity of corrosion depends upon the difference in their
positions, and greater is the difference, the faster is the corrosion of the anodic metal or alloy.
A metal high in the series is more anodic and undergoes corrosion faster than the metal below
it. For example, Li corrodes faster than Mg, Zn corrodes faster than Fe; eu corrodes faster
than Ag and so on.
However, some exceptions to this generalisation have been noticed. For instance, Zn which
is below Al in the electrochemcial series is corroded faster than AI. Similarly Ag which is below
Ti in the series is corroded faster than Ti. These observations contrary to that predicted by
electrochemical series have been explained on the basis that metals like Al and Ti form
strongly adhering oxide layers on their surface, which resist corrosion (Passivity). Due to
formation of oxide layer, their effective electrode potentials become positive or less negative.
As a result the electrochemical series do not account for the corrosion behaviour of all
metals. Hence, another series called galvanic series (Table 4.1), which provides a more
Table 4.1. Galvanic series (on the basis of relative oxidation
potential in sea water)
Magnesium
Magnesium alloys
Zinc
Aluminium
Aluminium alloys
Low carbon steel
Cast iron
Stainless steel (active)
Lead-tin alloys
Lead
Tin
Brass
Copper
Bronze
Copper-nickel alloys
Inconel
Silver
Stainless steel (passive)
Monel
Graphite
Titanium
Gold
Platinum
reliable information about the corrosion of not only metals but alloys also, has been framed.
These series have been prepared by studying the corrosion behaviour of metals and alloys in
a given environment like sea water. The difference between these two series has been
summarized below:
Electrochemical Series Galvanic Series
1. This series predicts the relative displace- 1. This series predict the corrosion tendencies
ment tendencies of metals and non-metals of metals and non-metals in actual environ-
in electrolytes containing particular ment.
concentration (1M) of salts of the same
metal.
2. It comprises metals and non-metals. 2. It comprises metals and alloys.
3. The position of a metal in this series is 3. The position of a given metal may shift in
permanently fixed. this series. The position of a metal, when
present in the form of alloy, is different
from that of pure metal.
4. The electrode potentials are measured 4. The electrode potentials are measured
by using standard hydrogen electrode by using calomel electrode as a reference
(SHE) as a reference electrode. electrode.
5. It gives no information regarding 5. The corrosion behaviour of alloys can also
position of alloys. be studied from their position in this series.
(iv) Nature of the Oxide Films: In aerated atmosphere practically all metals get covered
with a thin surface film of metal oxide having a thickness of a few angstroms'(l A =
10-10 m). The ratio of the volume of the metal oxide to the metal is known as specific
volume ratio. Greater the specific volume ratio, lesser is the oxidation corrosion
rate e.g., the specific volume ratio of Ni, Cr and W are 1.6, 2.0 and 3.6 respectively,
which indicates that the rate of oxidation at elevated temperature is least for
tungsten (W).
(v) Over voltage: The details of this factor have been discussed in the next unit on metal
finishing.
(vi) Volatility of Corrosion Product: If the corrosion product is volatile, then metal surface
is exposed for further attack, i.e., corrosion rate will be more e.g., Molybdenum oxide
M02 0 S' the oxidation corrosion product of molybdenum is volatile.
(vii) Solubilities of the Corrosion Product: If the corrosion product is soluble, corrosion
of the metal will proceed faster. On the other hand, if corrosion product formed is
insoluble, then the protective film formed tends to suppress corrosion.
(viii) Relative areas of the Anode and Cathode: When two steel plates of the same area
are separately connected one to a copper plate (cathode) having the same area and
the other to a copper plate having a much larger areas, it can be observed that the
latter couple produces greater amount of current and the corrosion of the steel anode
in this case will be much greater than the first one. It may be broadly concluded that
when anodic polarization is negligible and conductance remaining more or less same,
corrosion of the anode is directly proportional to the area of the cathode.
(b) Nature of the Environment
(i) Temperature: With increase of temperature of environment, the reaction as well as
diffusion rate increase, thereby corrosion rate is generally increased.
(ii) "
Humidity: The higher the moisture content in the atmosphere, the greater is the
rate and extent of the corrosion because moisture acts as medium for oxygen in air
and behaves as an electrolyte in air e.g., atmospheric corrosion of iron is slow in dry
air compared to moist air.
(iii) pH: Acidic media are generally more corrosive than alkaline and neutral media. The
amphoteric metals such as AI, Zn, Pb, etc. dissolve, corroded in alkaline solution.
The corrosion ~ate of iron in oxygen free water is slow, until pH is below 5. The
corresponding corrosion rate in presence of oxygen in much higher. Zinc is rapidly
corroded, even in weakly acidic solutions such as carbonic acid suffers minimum
corrosion at pH = 11.
(iv) Nature of Electrolyte: Chloride ions present in the medium destroy the passive film
and corrode many metals and alloys. On the contrary, some anions like silicate may
form an insoluble product (silica gel) which inhibit corrosion.
(v) Conductance of Corrosion Medium: The corrosion current depends upon the internal
resistance of the short circuited cells, which in turn depends on the conductance of
the electrolytic medium. If the conductance of the soil is more, the corrosion of
underground structures will also be more, consequently there will be more severe
damage to the metallic structures in the presence of stray currents from power
leakage. Conductance of clay and mineral soil is more than that of dry sandy soil,
hence corrosion of underground metallic structures is more in clay and mineralized
soil.
(vi) Presence of Impurities in atmosphere: Atmosphere, in the vicinity of industrial areas,
eontains corrosive gases like S02' H 2S and CO2 and fumes ofHCI and H 2S04 etc. In
the presence of these gases, the acidity of the liquid, adjacent to the metal surfaces,
increases and its electrical conductivity also increases. This consequently results in
an increase of corrosion on the exposed metal surfaces. Similarly, in marine
atmosphere, presence of N a+ and Cl-Ieads to increase the conductivities of liquid layer
in contact with the metal surfaces thereby increases the corrosion.
(vii) Presence of Suspended Particles in atmosphere: Two types of suspended particles are
present in atmosphere viz., chemically active and chemically inactive. The chemically
active suspended particles like N aCI, (NH 4 )2 SO4 absorb moisture and thus act as
strong electrolytes, thereby enhance corrosion, whereas chemically inactive suspended
particles like charcoal, sulphur absorb both moisture as well as gases and thus slowly
enhances corrosion rate.
(viii) Formation of Oxygen Concentration Cell : The rate of corrosion increases with
increasing supply of oxygen. Further differential aeration will also promote corrosion
by the formation of concentration cells. The region where the oxygen concentration
is less becomes anodic and suffers corrosion. The mechanism of corrosion by
differential aeration has already been discussed under the electrochemical theory of
corrosion.
4.8 CORROSION CONTROL (PROTECTION FROM CORROSION)
Protection against corrosion means not allowing corrosion reactions to take place. Noble
metals do not corrode but they cannot be used for common purposes, because of their high
cost. We have to use other metals and alloys in the fabrication of many kinds of machinery
and equipments and adopt measures to protect these from corrosion.
Pre·treatment of Metals
The metal should be cleaned or de scaled before protective measures are adopted. This
pretreatment usually consists of degreasing and descaling. Oily and greasy surface films are
dissolved out by exposure to volatile organic solvents such as trichloroethylene (CHCI = CCI2),
tetrachloroethylene (CI 2 C = CCI2 ), etc. Descaling can be affected either mechanically or
chemically. Acid pickling is more convenient method of removing scale than mechanical
cleaning. Metals like iron and steel are cleaned by immersing in warm dil H 2S04 or in cold
HCI solution, whereas copper, brass or nickel ~e dipped in dil HN0 3 or a mixture of dil HNO a
and dil H 2S04 • However, AI is not pickled in acid solution, but in alkaline solution.
Before any coating can be applied it is necessary to properly prepare the metal surface, if
the metal surface has not been properly cleaned, the protective coating will not stick to the
surface and more severe corrosion may result at points exposed to the corrosive environment.
Oil and grease are removed from the surface by washing with soap or alkali solution in
water. Several patented compositions containing alkaline phosphates and silicates are marked
for removing oil also. Rust or scale is mostly removed by dipping the material in dil (5 to 10%)
H 2S04 and by mechanical rubbing with a wire brush. Large equipments or bridges are cleaned
by the use of wire brush or by sand blasting.
The process of sand blasting consists in throwing a blast of sand mixed in air under a
pressure of 25 to 100 atmospheres on the metal surface to be cleaned. The sand blast removes
any scale (especially oxide scales) present and also hardens the metal surface. The process is
especially suitable for large steel surfaces. Paint coatings on sand blasted surfaces are more
durable than those on surfaces cleaned by other methods, because beside cleaning it make
the surface rough. However, the process requires expensive equipment and is injurious to the
health of the workers.
Another method of cleaning is by applying flame from a kerosene burner. The old paint,
oil or grease burns and the scale is removed because of sudden expansion of the metal.
Corrosion can be controlled by a number of ways. Some of these protective measures are
explained below:
4.8.1 Protective Coating or Barrier Protection
The metal surface may be coated for protection against corrosion. Most of these coatings
act as a barrier between the metallic surface and the corrosive environment and therefore
this method is, also called .
barrier protection.
(a) Metallic coating
(b) Inorganic non-metallic
coating
(c) Organic coating
(A) Metallic Coating
The metals used for coating
may be put under two
categories, so metallic coating is
of the following two types: Steel
(i) Anodic coating :
Metals such as Zn, Mg, Fig. 4.7. Functioning of anodic coating.
Cd, AI etc. which are
anodic as compared to the metal to be protected, they stand above Fe in the galvanic
series, the metals under this category being more anodic get themselves corroded,
saving the iron which is to be protected. Anodic coating protect the underlying base
metal sacrificially. In such cases even if the surface is scratched the metal to be
protected does not get corroded. The functioning of anodic category has been
represented by taking
Zn as an example in
== === === ==== ===- === == === ======+--Corrosive
----------
Fig. 4.7. ========== Exposed iron part ====: ===== environment
These metals may ========== (ANODE) ====: =====
===========-~-~-~-~-==-~-~-~-~-:::=:=====
be applied on the
surface by hot dipping
_=========ii~fi~~j~==========
---------------t--------------
or spraying.
(ii) Cathodic coatings :
Metals such as Sn, Ni,
eu etc., which are Steel
cathodic as compared
to the metal to be Fig. 4.8. Functioning of cathodic coating.
protected, they stand
below Fe in the galvanic series. The metals which fall in this category being cathodic
to iron are more resistant to corrosion and offer protection so long as the surface is
completely covered. If the coating breaks or is applied in a manner that pinholes are
left, these points at which the iron surface is exposed get very severely corroded because
they are anodic to the large cathodic surface. Hence great care has to be exercised
while applying these coating. The functioning of cathodic metals has been represented
by taking Sn as an example and is explained in Fig. 4.8.
Generally, the cathodic metal coating is applied by electroplating because by this method
a more uniform coating which completely covers the surface is produced.
(B) Inorganic Coatings
Inorganic coatings also known as non-metallic protective coatings, mainly include:
(i) Surface conversion or chemical conversion coating or ceramic coatings :
These coatings are produced by covering the surface of a metal or alloy, by
chemical or electrochemical methods. These coatings afford good protection
of the base metal from corrosion in some environments and sometimes are of
decorative value. Further, many of these coatings are particularly useful to serve as
excellent bases for the application of paints, enamels and other organic protective
coatings.
Important surface conversion coatings are :
(a) Phosphate coatings: These coatings are produced by the reaction of the base
metal with an aqueous solution of phosphoric acid and phosphates of zinc, iron or
manganese. This reaction is slow and can be accelerated by adding copper
nitrate. The copper nitrate acts as accelerator for the formation of phosphate coating.
The resultant surface film consists of crystalline zinc-iron or manganese-iron
phosphates.
Phosphate coatings are applied frequently to iron, steel and zinc, and to small extent
to aluminium, cadmium and tin. Such coatings do not offer complete resistance to
atmospheric corrosion. Iron and manganese phosphate coatings are used to reduce
wear due to friction in piston rings, cylinder lining of automobiles and wire drawing
equipment. Phosphate coatings are principally used as an adherent base/primer-coat
for paint, lacquers, oils etc. Phosphate coating is usually grey in colour. The colour
may be modified to black by adding zinc sulphide (bonderizing) to the bath, if it is not
intended to paint, etc., the phosphate coated parts afterwards.
(b) Chromate coatings: Chromate coatings are obtained by the immersion of the metal
in a bath having sodium dichromate and dilute sulphuric acid. At some critical
pH, basic chromium chromate (Cr 20 g.CrO g.x H 20) gets precipitated on the metal
surface. Chromate coatings are non-porous, amorphous, and more corrosion-resistant
than phosphate coatings. Chromate coatings are specially used for the protection of
Mg, AI and Zn surfaces. Sometimes, they are also used as base for paints, lacquers
and enamels.
(c) Chemical Oxide coatings: Oxide coatings can be obtained by treating the metal
with alkaline oxidizing agents. Protective films of magnetic oxide on iron can be
obtained by passing steam over the heated metal. These coatings are provided on
the surface of the base metal by treating them with alkaline oxidizing agent or gas.
This treatment increases the thickness of the original oxide film on the metal, thereby
increasing its corrosion-resistance. A good corrosion resistant black oxide coating on
stainless steel is made by immersing steel in cone. N aOH solution containing oxidising
agents like sodium nitrite or sodium chlorate at 80-90°C. Oxide coatings possess little
absorptive power compared with that of phosphate coatings, but they form a good
base for paints, lacquers and oils.
(ii) Anodized oxide coatings: Anodized oxide coatings are, generally, produced on non-
ferrous metals like AI, Zn, Mg and their alloys by anodic oxidation process, in which
the base metal is made as anode. It is carried out by passing a moderate direct electric
current through a bath in which the metal or alloy is suspended from anode.. The
bath usually contains sulphuric, phosphoric, chromic, oxalic or boric acid. After
anodizing, the oxide coating is 'sealed' by immersing in boiling water. These oxide
films are protective, corrosion resistant and electrically insulating in nature. As the
anodized coatings are somewhat thicker than the natural oxide films, so they possess
improved resistance to corrosion as well as to mechanical injury.
For example anodising on AI is carried out by making it anode in an electrolytic bath
containing a suitable acid at 35-40°C. A plate of lead or stainless steel is made the cathode.
When a current of moderate density is passed, the oxygen liberated at the anode combines
with it to form the oxide which takes the form of a thick film. The outer part of the oxide film
formed is quite porous and softer than the layer adjoining the metal surface. The anodised
surface is made impermeable by dipping in hot water. This process converts the oxide into
monohydrate form Al20 a.H20. The volume of the hydrated oxide be higher, the pores are sealed.
Sealing can also be done by immersing the film in boiling dilute sodium dichromate (Na2 Cr2 0 7 )
solution. Similarly, zinc can be anodised by making Zn as anode in an electrolytic both
containing chromic acid solution or chromates.
For decoration, the anodised coatings may be coloured by organic dyes or
inorganic pigments. In case of coloured coatings, the anodising is carried out at higher
temperature and in higher concentrations of the acidic electrolyte. This gives a porous coating
and the article is then immersed in the dye solution or the pigment solution before the sealing
operation.
(iii) Vitreous or Enamel Coating: Vitreous or porcelain enamel coatings are modified
glass-like materials having different compositions which are usually applied on steel
and cast iron equipment. The metal part to be enameled is first cleaned carefully.
"Frit" is prepared by fusing together refractory acidic substance with basic fluxes (e.g.
borax, cryolite, soda ash, feldspar, etc.). The 'frit' is applied to the metal either by
wet or by dry process.
High proportion of silica and feldspar and lower proportions of fluxes give acid-resistant
enamel. Ceramic protective coatings made from high refractory oxides such as Crpa afford
protection of the metal from corrosion even at high temperatures.
These coatings are widely applied for ferrous materials used for equipment in the
pharmaceutical, chemical, dairy, food and beverage industries. Enamelled steel is used for
refrigerators, stoves, table tops, kitchen utensils, etc. Enamelled cast iron is widely used for
bath tubs, sanitary wares, pans, basins etc. used in hospitals.
(c) Organic Protective Coating
Organic coatings are inert organic barriers applied on metallic surfaces and other
constructional materials for both corrosion protection as well as decoration. They include (i)
Paints (ii) Varnishes (iii) Enamels (iv) Lacquers (v) Emulsions (vi) Plastic coating. The protective
value of such coatings depends on:
(i)its chemical inertness to the corrosive environment (ii) its good surface adhesion
(iii) its impermeability to water, salts and gases and (iv) its proper application method.
The details of organic coating have not been included in the syllabus.
(d) Plastic Coating
These days costly metallic components like micrometers, gauges, verniers and surgical
tools are coated with plastics such as PVC, PVA, PMMA, Teflon etc. These polymers prevent
corrosion of the metal because they have chemical resistance better than any other coating.
But a crack in the coating will lead to corrosion which should be avoided. The material
to be coated is thoroughly cleaned and dipped in liquid plastic or solution of plastic in a
volatile solvent. When the plastic layer adheres to the metallic surface, it is removed, cooled
and dried.
4.8.2 SACRIFICIAL OR ANODIC PROTECTION
Sacrificial protection means covering the metal (iron) surface with a layer of another metal
which is more active (electropositive) than iron and thus prevents the iron from losing electrons.
The more active metal loses electrons in preference to iron and converts itself into ionic state
by losing electrons. With the passage of time, the
Water area
more active metal gets consumed but so long as
0 3 (g)
it is present there, it will protect the iron from
rusting and does not allow even the nearly
O2 + 4H' + 4e-
exposed surface of iron to react. The metal which Zn . .2H20
is most often used for covering iron with more
active metal is zinc and the process is called Zn anode Iron cathode
galvanization (Fig . 4.9). Zn being more
electropositive than Fe acts as anode and it gets Fig. 4.9. Galvanised iron. A Cathodic protection
corroded, whereas iron remains protected till Zn of iron in contact with zinc provided by
is present. galvanization.
The layer of zinc on the surface of iron, when comes in contact with moisture, oxygen and
carbon-dioxide in air it forms a protective invisible thin layer of basic zinc carbonate. ZnC03 •
Zn(OH)2' When such a layer is formed on the galvanised iron sheets, the sheets lose their
luster, but such a layer tends to protect it form further corrosion.
Iron can be coated with copper by. electro-deposition from a solution of copper sulphate or
with tin by dipping into molten metal. This process of coating tin over metal surfaces is called
Tinning. The tinning of copper or brass utensils is a familiar example. Tinning of household
cooking utensils made of copper and brass is essential to avoid the dissolution of poisonous
metals like eu into the food. But tinning of metals like iron is avoided. Now if the coating is
broken, iron is exposed and iron being more active than both copper and tin, is corroded.
Deposition of tin or copper on iron is not very useful because the corrosion of iron is increased
in case of any scratch or crack on the coating.
(E~n2+,zn = -0.76 V and E~e2+,Fe = -0.44 V)
(Egn2+,sn = -0.14 Vand Egu2' ,Cu = -034 V)
Here iron corrodes more rapidly than it does in the absence of tin. At times zinc, magnesium
and aluminium powders mixed with paints provide decorative protective coating also.
4.8.3 Electrical Protection
Cathodic Protection Earth surface
The iron object to be protected from corrosion
is connected to a more active metal either directly
or through a wire. The iron object acts as cathode
and the protecting metal acts as anode. The anode
is gradually used up due to the oxidation of the
metal to its ions due to loss of electrons. Hydrogen
ions collect at the iron cathode and prevent the rust
formation . The iron object gets protection from
rusting as long as some of the active metal is
present. Metals widely used for protecting iron
objects from rusting are magnesium, zinc and Fig. 4.10. Cathodic protection of underground
aluminum which are called sacrificial anodes. iron pipes.
Magnesium is oftenly employed in the cathodic
protection of iron pipes buried in the moist soil, canals, storage tanks etc. Pieces of magnesium
are buried along the pipeline and connected to it by the wire as shown in Fig. 4.10.
Impressed Current Cathodic Protection
Source of current (d.c.)
In this method, current is applied from
opposite direction to nullify the corrosion
current, and convert the corroding metal from
anode to cathode. Usually, the impressed
,current is derived from a direct current
source with an insoluble anode (like graphite
or platinum). Usually, a sufficient d.c. current
is applied to an insoluble anode, buried in the Back fill
soil, and connected to the metallic structure
to be protected (Fig. 4.11). 1b increase the
electrical contact between the anode and the
soil, the anode is buried in a back fill such as
gypsum under the earth. Thus electrons are //////////////////////
supplied from an external cell so that the object
itself becomes cathodic and is not oxidized. Fig. 4.11. Impressed current cathodic protection.
This type of cathodic protection has been
applied to open water box coolers, water-tanks, ships, etc. This kind of protection technique
is, particularly, useful for large structures for long term operations.
4.8.4 Corrosion Inhibitors
Corrosion inhibitors are the substances which retard or stop the corrosion reaction Some
of these are polarisers and act by retarding cathodic or anodic reactions. They usually act as
corrosion retarders in two way (i) formation of an insoluble salt or oxide on the .metal surface
(ii) adsorption on the metal surface, etc.
Based upon their mode of action. Corrosion inhibitors are of the following three types :
(i) Anodic Inhibitors : These inhibitors react with the ions coming to the anode i.e.,
anions and change them to insoluble precipitates. These are adsorbed on the metal
surface forming a protective film and thus the corrosion rate is reduced. Common
examples are inorganic inhibitors such as alkalies, phosphates, chromates and
molybdates.
(ii) Cathodic Inhibitors: These inhibitors get absorbed over the cathodic metal surface
which act as a protective layer. In acidic solutions, the cathodk reaction is : 2H+ +
2e- ~ H 2 . The diffusion of H+ was through the cathode is slowed down. Organic
inhibitors such as amines, heavy metal soaps, urea and thio-urea absorb on the
cathodic metal surface and act as a protective layer. Inorganic inhibitors like antimony
and arsenic oxides deposit adherent film of metallic antimony and arsenic at the
cathode, thereby increasing considerably the over-voltage for hydrogen evolution.
The cathodic reaction in a neutral solution is :
H 20 + ~02 + 2e- ~ 20H-
The formation of OH- ions is dependent on the amount of 0 2 available. So, corrosion can
be controlled in two ways :
(a) By eliminating 02 from the corroding medium which may be achieved by adding
reducing agents such as Na2S0 3 or by deaeration.
(b) By retarding diffusion of 02 to the cathodic areas which can be done by adding salts
of Zn, Mg forming their insoluble hydroxides which are deposited at the cathode. These
deposits retard the diffusion of 02 to the cathode.
(iii) Vapour Phase Inhibitors: These inhibitors readily sublime and form a protective
layer at the surface of the metal. Organic inhibitors being volatile are suitable for the purpose.
Examples are given in organic inhibitors.
Based upon their structure, the corrosion inhibitor are of the following two types:
1. Inorganic Inhibitors
Inorganic inhibitors such as silicates, chromates, borates, etc. suppress the rate of corrosion
by acting as the anode. Some common examples of inorganic inhibitors are:
(a) Alkaline sodium nitrite alone or in combination with other inhibitors such as phosphates
have been used to control the corrosion of tankers and pipelines.
(b) Sodium benzoate has been used as an inhibitor for mild steel and in preventing corrosion
in cooling systems such as automobile radiators.
(c) A mixture containing 0.1% NaN0 2 and 1.5% sodium benzoate has been used as inhibitor
in antifreeze solutions.
(d) Lime acts as a cathodic inhibitor by precipitating CaCOa in water containing temporary
hardness or dissolved CO 2,
(e) Colloidal particles of CaCOa having +ve charge are attracted to the cathodic areas and
get deposited there, thus reducing the corrosion current.
2. Organic Inhibitors
Organic inhibitors act by different mechanisms, some examples are :
(a) Organic colloidal inhibitors form protective layers on the metal surface by adsorption.
(b) Surface active reagents known as surfactants, containing polar groups promote spreading
to the surface, thus, forming a protective film.
(c) Organic bases e.g., amines, pyridines, quinoline and their derivatives contain hydrophobic
groups a or radicals. These +vely charged cationic groups attach themselves to the cathodic
areas through the nitrogen and provide inhibition. The efficiency of inhibition depends upon
size and number of the alkyl groups, e.g., primary amyl amine (C5H u NH 2) has been found to
be more effective as inhibitor than primary ethyl amine (C 2H 5NH2).
td) High molecular weight amines derived from rosin have been used as corrosion inhibitors.
The product obtained by rosin amine and pentachlorophenol was used in castings for
underground pipelines to protect them from corrosion by soil bacteria.
(e) Organic inhibitors such as soluble salts of rosin, e.g, stearate or naphthenate have been
used as inhibitors in the various metal cleaning operations like acid "pickling" of metals, cleaning
of boilers, condensers, heat exchangers, chemical equipment, pipelines, etc., to prevent undue
and excess corrosion of the metals while removing rust, scales and deposits.
(f> Some vapour phase inhibitors (VPl) such as Dicyclohexylammonium nitrite and
cyclohexylamine carbonate are used to inhibit the corrosion in restoring aircraft engines as
well as during storage packing, shipping etc.
(g) Octadecylamine, hexadecylamine and dioctadecylamine do not come under VPI but they
provide protective action by forming impervious non-wettable surface films. These are used in
radiator compounds and boiler waters.
(h) Amine salts, morpholine and sodium benzoate are particularly useful for impregnation
of packing materials.
It should be emphasized here that an inhibitor should be used with caution. Improper and
insufficient use of an inhibitor may even accelerate corrosion, e.g., addition of chromate as
inhibitor in the presence of hydrogen polarization may have depolarization effect and corrosion
may be accelerated, while insufficient use of an inhibitor may not provide the protective film
over the entire anode and the small areas left exposed, suffer intense corrosion leading
to pittings.
1. What is the effect of pH on corrosion ?

2. What is cathodic protection ?
3. Why does part of a nail inside the wood undergoes corrosion easily?
4. Why is deposition of extraneous matter on metal surfaces for a long period
undesirable?
5. Why does a steel pipe in a large copper tank corrode causing rapid destruction?
6. Why should nickel plated steel articles be free from pores and pin holes?
7. Small anodic area results in intense corrosion. Give reason.
8. A copper equipment should not possess a small steel bolt. Give reason.
[PTU, Dec. 2002J
9. How is cathodic protection of iron different from its galvanization?
10. How is cathodic protection different from galvanization?
11. An iron object is plated with a coating of nickel to protect against corrosion. Does the
nickel protect iron by cathodic protection ? Explain.
12. Explain atmospheric corrosion in brief.
13. Why iron does not rust if covered with ice?
14. Summarise the various factors for soil corrosion.
15. What is stray current corrosion ?
16. How the cast iron pipelines carrying oil, gas and water are corroded? Give some
prevention methods.
17. What is Pilling-Bedworth Rule? [pTU, June 2003J
18. What is meant by Differential Aeration ? [pTU, June 2003J
20. What is galvanising?
21. Comment on the use of aluminium in place of zinc for cathodic protection of iron from
rusting. [U.P. Tech., Jan. 2001]
22. How much rust (Fepa.3H20) will be formed, when 100 kg of iron have completely rusted
away? [U.P. Tech., Jan. 2001]
23. What are the factors which affect corrosion? [U.P. Tech., Jan. 2001]
( ANSWERS)
1. The lower the pH (or more acidic), greater is the corrosion.
2. It is protection of the parent metal from corrosion by connecting it with a more active
metal (more anodic metal) like Mg, Al etc. The connected active metal undergoes
corrosion thereby protecting the parent metal from corrosion.
3. The part of the nail inside the wood is not exposed to atmospheric conditions; whereas
the remainder part is exposed directly to atmospheric air. Due to differential aeration,
the nail inside the wood (not oxygenated part) becomes anodic, while the upper part of
nail (well-oxygenated) becomes cathodic. Consequently, a differential current starts
flowing, whereby the anodic part gets corroded easily.
4. Deposition of extraneous matter (dirt, sand, scale, etc.) on metal surfaces restrict the
access of oxygen below it, thereby unexposed surface of metal becomes anodic w.r.t. to
well-aerated exposed surface of the metal. Consequently, a differential current starts
flowing, whereby the unexposed metal surface (covered by extraneous matter) undergoes
localized corrosion.
5. Iron or steel is anodic w.r.t. to copper. When a steel pipe fitted in a large copper tank
is exposed to atmosphere, galvanic corrosion starts and the anodic metal (iron or steel)
starts corroding. Moreover, small-sized pipe (anode) in a large-sized copper tank
(cathode) causes rapid and intense corrosion (or destruction) of steel pipe.
6. Iron (or steel) is anodic w.r.t. nickel. Presence of pores and pinholes in nickel plated
steel articles expose the anodic metal (steel) to atmosphere at these points. A galvanic
cell is set up and an intense localized corrosion at these small exposed parts occurs,
thereby resulting in severe pitting and perforation of the base metal, steel.
7. Corrosion is more rapid, intense and highly localized, if the anodic area is small, because
the current density at a smaller anodic area is very large, and the demand for electrons
by the large cathodic area can be met by the smaller anodic area only by .undergoing
corrosion more briskly.
8. Iron (higher in electrochemical series) acts as anodic end is attached and corroded while
copper equipment (lower in electrochemical series) acts as cathode and is not attacked
at all. Since anodic area is very small. So it is completely corroded in due course of
time and the action of bolt is finished, i.e., equipment loses its bolt after sometimes.
9. In cathodic protection, the iron article/equipment is made cathode by connecting it with
a more anodic metal Zn, AI, etc. On the other hand, in galvanization, the iron article
is protected from corrosion by coating it with a thin layer of zinc only.
10. The cathodic protection of iron consists in connecting the iron surface to a more active
metal (having lower reduction potential) like zinc, aluminium or magnesium. This
assembly sets up an electrochemical cell in which the active metal zinc acts as anode
and iron acts as cathode. The zinc anode undergoes corrosion saving the iron cathode.
On the other hand, galvanization is the process of coating the iron surface with zinc.
The clean iron sheet is dipped into molten zinc when zinc gets deposited as a thin
layer over iron. In case some scratches occurs on the protective zinc layer of the
galvanized iron, even then iron will not be rusted. This is because zinc being more
electropositive (having lower reduction potential) undergoes oxidation in preference to
iron.
11. No. The potential for oxidation of Ni to Ni2+ (= +0.284 V) is lower than that for Fe to
Fe 2 (= +0.44 V). For cathodic protection, the protecting metal must be more easily
oxidized than iron. Iron is more easily.oxidized that nickel due to its higher oxidation
potential.
12. Atmospheric corrosion takes by the simultaneous action of oxygen and moisture. When
iron is exposed to an atmosphere containing more than 60% humidity (critical humidity),
rusting starts and increases rapidly with increase in relative humidity. Atmospheric
corrosion increases in air polluted with smoke or gases like S02' Solid suspended
particle and common industrial pollutants in air also accelerate it.
13. Iron does not rust if covered with ice, since the electrochemical attack requires water
in the form of liquid and the presence of oxygen also to act as an electrolyte.
14. The various factors promoting soil corrosion are:
(i) Soils having high porosity are more corrosive due to greater degree of aeration.
(ii) Soils having higher conductivity (low electric resistivity) due to the presence of
moisture and dissolved electrolytes are more corrosive than other.
(iii) Soil corrosion also depends upon the diffusion of dissolved oxygen and bacteria in
the soil.
15. Leakage of electric current from electric traction system such as electric trains to
adjacent conducting systems gives rise to stray-current corrosion. The point from which
the current leaks becomes anodic and gets corroded. This type of corrosion is also aided
by dissolved electrolytes. It can lead to pitting and serious damage to underground
structures.
16. Underground corrosion of the pipeline is due to following factors:
(i) Electrochemical action in which iron acts .as anode and impurities in cast iron
such as carbon act as cathode.
(ii) Anaerobic microbiological corrosion of iron, and
(iii) Stray current corrosion.
Some preventive measures are: (i) Coating of the pipelines with bituminous material
can prevent the access of air and moisture, (ii) Choice of well aerated soil and avoiding
water logged and porous soil prevents microbiological corrosion.
17. Pilling-Betworth rule is helpful in deciding whether the oxide, film formed on the metal
surface is porous or non-porous. According to this rule "An oxide film is non-porous
i.e., protective, if the volume of oxide is at least equal to or greater than the volume of
metal from which it is formed. However, if the volume of the oxide is less than the
volume of the metal, the oxide film is porous i.e., non-protective. Metal like AI from
oxide having greater volume as compared to the metal, so they form non-porous oxide
layer and further oxidation of the metal is prevented. On the other hand, alkali and
alkaline earth metals form oxides having lesser volume compared to the metal, they
from porous oxide films which allow further attack to atmospheric oxygen through the
pores and the metals are completely corroded.
18. When a metallic surface is partially increased in a solution and partially exposed to
atmosphere, the part of the metal immersed in solution has less access to oxygen as
compared to the exposed part. It has been observed that poorly oxygenated part of the
metal becomes anodic and strongly oxygenated part becomes cathodic. So, a difference
of potential is created which causes flow of electrons between two differentially aerated
areas of the same metal. The anodic part of metal gets corroded. This type of corrosion
is called differential aeration corrosion. It can also occur when the metal surface is
exposed to an electrolyte of varying aeration or concentration of the electrolyte and is
termed as concentration cell corrosion also.
20. The process of covering metals like iron with more active metals like zinc to prevent
the corrosion of iron is called galvanising. It is called sacrificial protection of iron by
zinc. Zinc being more electropositive than iron acts as an anode and it gets corroded,
whereas iron remains protected till zinc is present. The reduction potential of Zn is
higher than that of Fe, its position in the electrochemical series being higher, it loses
electrons more easily as compared to iron.
21. In cathodic protection, the metal (here iron) to be protected from corrosion is connected
by a wire to a more anodic metal (like AI, Zn etc.), so that all the corrosion occurs at
this more active metal. Thus, the parent metal is protected while the more active metal
gets corroded slowly.
As the standard electrode potential of aluminium is more than that of zinc so AI is
more anodic than Zn.
Thus, we can better use aluminium in place of zinc for cathodic protection of rusting
of iron.
22. We know that atomic weight of Fe =56,0 = 16, and H = l.
So, molecular weight of rust
Fe20 a.3Hp = (2 x 56) + (3 x 16) + 3 (2 x 1 + 16) =214 gmlmole
Each Fepa.3H20 has 2 Fe atoms or 112 gm iron.
Since 214 gm of rust contains = 112 gm iron
.. 112 gm of iron produces rust = 214 gm
or 100 kg ofiron produces rust = 214 x 100 = 191.07 kg.
112
23. Rate and extent of corrosion depends on :
S.No. Nature of the metal Nature of the environment
l. Purity of metal, Temperature,

2. Physical state of the metal, Humidity,
3. Nature of the oxide film, Effect of pH,
4. Position in the galvanic series, Nature of electrolyte,
5. Relative areas of the anode and cathode, Conductance of the corroding medium,
6. Solubilities of the product of corrosion, Formation of oxygen concentration cell,
Presence of suspended particles in
atmosphere
7. Volatility of corrosion products. Presence of impurities in atmosphere.
( REVISION QUESTIONS) ..
1. Define corrosion of metals. What are different types of corrosion ? Explain the
electrochemical theory of wet corrosion, giving its mechanism.
(Tripura, 2K; SV, Aug. 01; Anna, May 01; UPT, Jan 01;
PT, Dec. 2K; SK, June 01; Surat, Nov. 2K; Calicut, June 01)
2. (a) Explain rusting of iron with the help of elecrochemical theory of corrosion.
(KU, May 99; VT, March 99; Raj., May 01)
(b) Differentiate between chemical corrosion and electrochemical corrosion.
(Anna, July 2K)
(c) What will happen when stainless is immersed in aerated and deaerated sodium
3.
chloride solution? .
. (Surat, June 01)
(a) Write chemical reactions taking place during stress corrosion of brass.
(b) Illustrate the reactions involved in differential aeration corrosion with reference
to the iron materials. (VT, Aug. 2k)
(c) Define corrosion. Explain dry corrosion and its mechanism. (Simbalpur, April2k)
4. Explain the mechanism of following types of corrosions :
(a) Chemical corrosion (Andhra, June 01)
(b) Stress corrosion
(c) Water-line corrosion (KU; Dec. 2k; Amravati, Dec. 2k; Sindri, May 01)
(d) Pitting corrosion (Anna, Nov. 2k, May 01; Amravati, Dec. 2k)
(e) Bimetallic or galvanic corrosion. (Surat, Nov. 2k; Anna, Nov. 2k)
5. (a) Mention different methods used for prevention of corrosion of metals and discuss
anyone method. (Tripura, 2K)
(b) How is steel protected cathodically? Discuss with an example.
(c) Write short note on cathodic protection.
(Anna, Nov. 2K; V T, March 01; KU, Jan. 03)
6. (a) Explain sacrificial anodic protection of controlling corrosion.
(Amravati, Dec. 2K; Surat, Nov. 2K, Anna, May)
(b) What are the factors which affect corrosion? (U.P Tech., 2001)
7. What are metallic coatings? Explain the functioning of two types of metallic coatings.
Explain the methods employed for coating metals over a base metal.
8. (a) Corrosion can be considered as the reverse of the process of metal extraction. JustifY
the statement.
(b) What is meant by anodic sacrificial protection, how does it work? Mention its
application with neat diagram. {MREC, 2002}
(c) Why impure metals are more susceptible to corrosion than pure metals?
{MREC, 2001}
9. (a) Explain "rusting of iron" with the help of electrochemical theory of corrosion.
(b) Distinguish between galvanizing and tinning.
10. Suggest the preventive measures to control corrosion. [Raj. Univ., 2001}
11. Explain the mechanism of following types of corrosion:
(a) Pitting corrosion
(b) Galvanic corrosion [Anna, Nov. 2000J
(c) Oxidation corrosion. [Anna, May 2001J
12. (a) How is steel protected cathodically? Discuss with an example. [Anna, Nov. 2000J
(b) Explain sacrificial anodic protection meth,od of controlling corrosion.
(c) Write in brief on impressed current method of cathodic protection.
[Anna, July 2000J
13. Answer any four from the following:
(i) Define corrosion.
(ii) Discuss the mechanism of electrochemical corrosion.
(iii) What is meant by the term "passivity" ?
(iv) What are the factors which affect corrosion ?
(v) Comment on the use Aluminium is place of Zinc of cathodic protection of iron from
rusting.
(vi) How much rust (Fe2 0 3 .3H20) will be formed when 100 kg of iron have completely
rusted away? [U.P. Tech., B. Tech., 1st Sem., 2000-01J
14. (a) Corrosion involves the ..... of iron and the chemical formula of rust is .... (Fill in
the blanks).
(b) Describe the process of galvanization of iron. How does it prevent the corrosion of
iron? [U.P. Tech., B. Tech., 2nd Sem., 2000-01J
15. (a) What are corrosion inhibitors? Explain with examples how anodic and cathodic
inhibitors provide protection against corrosion?
(b) Describe passivity and its significance.
[U.P. Tech., B. Tech., 1st/2nd sem., 2001-02J
16. Define corrosion by giving an example. How does 02 gas corrode the metal? Explain
Pilling Bed worth rule in Brief. [J.M.I., B. Tech., Part-I, 2000J
17. Name the factors which are responsible for corrosion of boiler tubes, plates and pipe
lines. [RGPv, B.E., 1st Sem., 2001J
18. What are electrochemical and galvanic series? Distinguish between the two and point
out their role in corrosion.
19. What do you understand by hydrogen over voltage ? What is its role in corrosion of
metals.
20. What is sacrificial protection from corrosion ? Give examples and explain anyone in
detail.
21. What are corrosion inhibitors? Give some examples of organic and inorganic inhibitors.
Enlist two applications where volatile inhibitors are used?
22. (a) Comment on the use of Al in place of Zn for the cathodic protection of iron from
rusting. (U.P. Tech., Jan. 2001)
(b) What is meant by corrosion inhibitors? Give two examples. (PTIJ, Jan. 2001)
(c) Write a short note on corrosion by Differential Aeration.
23. (a) Explain hydrogen evolution type corrosion. (PI'U, Jan. 2001)
(b) Explain the difference in the use of Anodic and Cathodic coatings for corrosion
prevention.
24. (a) Give reasons for the following:
(i) Corrosion of water filled steel tanks occurs below the water line.
(ii) I).. copper equipment should not possess a small steel bolt.
(b) Wirte short notes on :
(i) Atmospheric corrosion.
(ii) Cathodic protection against corrosion. (PI'U, Dec. 2002)
25. (a) Discuss the mechanism of wet corrosion.
(b) Write a short note on metallic coatings for corrosion prevention.
(PI'U, June 2003)
26. Describe different types of corrosion and discuss the factors that effect corrosion.
(PI'U, Dec. 2003)
27. (a) What is galvanizing?
(b) What is corrosion and how can it be prevented? (PI'U, June, 2004)
28. What is anodising? Explain anodising of AI. (VTU, B.E., March & Aug., 2001)
29. What is metallic corrosion ? Pin poles on tin coated iron are more prone to corrosion of
iron than those on zinc coated iron. Why? (VTU, B.E., March 1999)
30. (a) Discuss the corrosion of iron metal based on electrochemical theory.
(b) Explain the type of corrosion occuring in the following cases.
(i) Bolt and nut made from different metals are in contact with each other.
(ii) Deposition of small particles of dust on iron surface. (VTU, B.E., March 1999)
31. (a) How is metal structure protected by cathodic protection method?
(b) Explain the effect of the following factors on the rate of corrosion
(i) nature of corrosion product
(ii) Anodic and cathodic areas,
(iii) pH (VTU, B.E., April 2000)
32. (a) Discuss the influences of following factors on the rate of metallic corrosion.
(i) Nature of corrosion product.
(ii) Polarizertion of the electrode surface.
(b) Explain the cathodic protection given to metals exposed to corrosion environmen.
(VTU, B.E., August 2001)
33. Define corrosion. How electrochemical theory of corrosion accounts for rusting of
iron ? Give the reaction inclued. (VTU, B.E., August 2002)
34. (a) Describe the electrochemical theory of corrosion.
(b) Discuss the following factors influencing the rate of corrosion.
(i) Nature of corrosion product.
(ii) Temperature
(iii) pH.
(c)Explain the differential metal, water line and pitting corrosion with examples.
(VTU, B.E., Jan./Feb. 2003)
35. (a) What in corrosion? Explain the rusting of iron based on electrochemical theory.
(b) Explain the effect of the following factors on the rate of corrosion:
(i) Nature of the metal.
(ii) Relative areas of the anode and cathode.
(iii) Nature ofthe corrosion product. (VTU, B.E .. July/Aug. 2004)
36. (a) What in metallic corrosion? Explain the electrochemical theory of corrosion taking
iron as an example.
(b) Explain what type of corrosion occurs when
(i) Screw and washer are made of different metals.
(ii) Presence of NaOH in mild steel boiler under stress. (VTU, B.E., Feb. 2005)
METAL FINISHING
SYLLABUS
Technological importance of metal finishing. Significance ofpolarization, decomposition
potential and over voltage in electroplating process. Electroplating-Process, effect of
plating variables on the nature of Electro deposit, surface preparation and electroplati.ng
ofCrandAu.
Electroless plating-Distinction between electroplating and electroless plating, advantages
of Electroless plating, electroless plating of copper and PCB and nickel.
5.1 INTRODUCTION
Modification for improving the surface of a metal is referred to as the metal finishing. It
can be done by deposition of a layer of another metal or a polymer or by the formation of an
oxide film on the surface of the metal. The main purpose of metal finishing is to impart desirable
surface characteristics such as resistance to corrosion and abrasion. It also provides desirable
mechanical and physical property at the surface of the metal. It improves resistance to corrosion,
wear, chemical attack, high temperature, frictional and galling behaviour and increases
hardness of the surface. It is also done to improve the appearance of industrial and house-hold
metallic equipments i.e., for decoration purposes. Metal finishing is widely used in the
manufacture of automobiles, aircrafts, refrigerators, washing machines and other domestic
articles, electrical appliances such as fans, hot plates, ovens, toasters etc., building materials
such as door handles, locks, hinges, screws, bolts etc, jewellery, radios, cameras, type-writer,
watches, purses, umbrellas etc. In fact, for our aesthetic appeal we want every article of our
use to look attractive and, therefore, the list of metal equipments which are subjected to metal
finishing after their manufacture is endless.
The important metal finishing techniques are: (i) Electroplating, (ii) Electroless plating,
(iii) Immersion plating (or chemical displacement of meta~s), (iv) Electrophoretic plating,
(v) Inorganic coatings such as chemical conversion coatings, anodised coating, vitreous or
porcelain enamel coating, (vi) Metal cladding, (vii) Metal spraying, (viii) Cementation, (ix) Plastic
coating and, (x) Organic coatings such as paints, varnishes and lacquers etc.
Metal Finishing 167
Chemical
conversion
coatings
Anodised
IVarnishes 1..----1 oxide
coatings
enamel
coatings
Fig. 5.1.
Depending upon the nature of the metallic equipment to be given finishing touch and the
requirements and specific purpose for use, any of the above techniques can be employed.
Keeping in view the syllabus, the details of only first two techniques are being discussed in
this chapter.
. 5.2 TECHNOLOGICAL IMPORTANCE OF METAL FINISmNG
For the manufacture of any metallic equipment different ferrous and non-ferrous base
metals or alloys are used. But after manufacture their finishing is essential not only for
decoration and surface protection but for providing desirable surface characteristics such as
resistance towards corrosion, chemical action, surface protection, abrasion, temperature etc.
Metal finishing techniques are important for improving the engineering performance i.e.,
physical, mechanical and electrical properties of different parts of the equipment. Besides
decoration, the technical importance of metal finishing includes the following:
(i) In the manufacture of electrical and electronic components such as printed circuit
boards, capacitators and contacts.
(ii) In electrotyping i.e., to reproduce finely engraved dies or similar finely divided articles
such as gramophone records.
(iii) In electroforming i.e., to manufacture metal articles entirely by electroplating. The
radio, radar, aircraft, automobile, glass, rubber, steel and printing industries use
several products made either partly or fully by electro forming. This method helps in
the manufacture of articles where other methods have been totally ineffective.
(iv) Even non-metallic materials such as synthetic resins, cloth, paper, wood, porcelain,
leather etc., are usually electroplated for decoration, preservation or to prepare
light weight materials with metal surface characteristics, surface conductance and
strength. Non-metallics are also plated in connection with electroforming and
electroplating.
(v) In electrochemical machining, polishing and etching.
(vi) To provide electrical and thermal conducting surface for some specific parts of
equipments.
(vii) Electrophoretic painting for painting of motor car body or any other electrically charged
conducting surface.
(viii) To impart metallic surface properties, metals are plated over non-metallic materials
like plastics, rubbers etc.
(ix) To acquire the capability of thermal and optical reflection certain devices based
on solar energy conversions are coated with paints containing specific desired
chemicals.
(x) To impart surface characteristics such as resistance to corrosion, chemical action,
abrasion, wear and impact, metal finishing of the machinery in different industries
is carried out.
Applications of Electroplating
(i) Base metals such as Fe, Cu, AI and their alloys are electroplated with gold and silver
so as to increase commercial as well as decorative value.
(ii) Steel articles used in automobile industry are generally given three successive coatings
of Cu, Ni and Cr. This is done for corrosion protection and to impart shining and
clear metal appearance.
(iii) In internal combustion engines, an electroplated chromium coating not only avoids
the wear but also improves the running performance.
(iv) Many parts used in aircraft, radio, radar and automobile industries are electroforming
products. Electroforming means electro-deposition of thick layer of metal for the
formation of articles.
5.3 BASIS OF ELECTROPLATING
Metal finishing technique namely electroplating is based on the process of electrolysis, which
means the decomposition of an electrolyte in solution or in the molten form by the passage of
electric current through it. On passing electric current through the solution of an electrolyte
the ions move towards the oppositely charged electrodes. The positively charged ions move
towards the cathode and are called cations, whereas the negatively charged ions move towards
move towards the anode and all call est anions. On reaching the respective electrodes, the
ions are discharged by gaining or losing the required number of electrons and get deposited
on their respective electrodes.
The article to be electroplated is made the cathode in an electrolytic both containing the
ions of the metal to be deposited. Anodes are usually either the metal to be deposited or an
inert material of good electrical conductivity (graphite). The conditions are so adjusted that
the rate of deposition at the cathode is equal to the rate of dissolution of the ions from the
cathode, so that the composition of electrolyte remain unchanged. A uniform layer of the desired
metal thus gets deposited on the article made cathode.
The process of electrolysis is governed by two important laws called Faraday first and second
law of electrolysis. The basic knowledge of the following terms namely (i) Polarisation (ii)
Decomposition potential and (iii) Overvoltage is essential to understand the process of electrolysis
on which the electroplating technique is based let us explain these terms one by one before
taking up our discussion on electroplating.
5.3.1 POLARISATION
According to Ohm's Law, C =EIR
Where E is the e.m.f. of the external source, R the resistance and C the current flowing
through the circuit.
But when current flows through a solution of some electorolyte, it is found that the current
C is not equal in magnitude to EIR, it may be appreciably less. In fact, the chemical changes
that occur at the electrodes have converted the electrolytic cell to a voltaic cell with an E.M.F.
(e), the direction of which is opposite to that of the applied E.M.F.(E). Consequently, the current
Metal Finishing 169
in the circuit is given by the equation, C = E - e . The E.M.F., e may be called the counter or
back E.M.F. of the electrolytic cell. R
This phenomenon of back E.M.F. brought about by the products of electrolysis is known as
polarisation. The electrochemical cell thus set up, sends current in the opposite direction to
that of the external battery. This reverse current is known as polarisation current. For instance,
in a hydrogen-chlorine cell the gases go on accumulating on the electrodes, till the back E.M.F.
is equal to the applied E.M.F., when the current stops.
Electrode polarization is a process due to inadequate supply of metal ions from the bulk
of the solution to the metal electrode leading to variation of electrode potential.
Concentration polarisation: The E.M.F. required to bring about decomposition of an
electrolyte is not determined solely by the magnitude of the polarisation, due to the products
of electrolysis. The current also causes concentration changes at the electrodes, and these
changes always act in opposition to the E.M.F. driving current through the cell. This effect is
known as concentration polarisation.
So, the phenomenon of the departure of the electrode potential (increase or decrease)
from the reversible value as a result of the change of concentration in the vicinity of electrode
is known as concentration polarisation.
Cause of polarization : According to Nernst equation, the electrode potential in a cell is
given b y ; ' 2 303 RT
E = EO + . log [M n +]
where [Mn+] is the concentration of the m~fal ion surrounding the electrode surface at
equilibrium.
When a current is passed through the electrolytic cell, the metal ion concentration in the
vicinity of the electrode surface decreases due to the reduction of some of the metal ions to
metal atoms {Mn+ + ne- ~ MI.
However, the equilibrium is re-established because of the concentration gradient. The ions
from the bulk of the solution diffuse towards the electrode. If the diffusion is slow, the delay
in establishing the equilibrium causes a change in the electrode potential. Thus, it leads to
the polarization of the electrode.
There will be no concentration polarisation i.e., no change in the electrode potential if the
increase or decrease in the concentration of the ions produced in the immediate vicinity of
the electrode, as a result of discharge of ions or dissolution of metal is instantaneously
compensated by the quick migration ofthe ions in the opposite direction.
The polarisation effect can be demonstrated by connecting an electric bell to the two
electrodes of a simple cell. When the cell works, the sound of the bell is loud in the beginning,
but it becomes fainter and fainter with time and finally it stops ringing, the cell becomes
completely polarised.
Factors Mfecting Electrode Potential
The magnitude of concentration polarisation at an electrode decreases if we increase the
rate of diffusion of the ion from or to the electrode. Thus, concentration polarisation can be
minimised by stirring the electrolyte, raising the temperature and by increasing the
concentration. It is, however, not completely eliminated, because diffusion of ions is in fact a
slow process.
Thus Electrode polarization d,epends on
(i) Electrolyte concentration and its conductivity,·
(ii) Size, shape and compositio~ of tne electrode,
(iii) Products formed at the electrodes,
(iv) Rate of stirring of the electrolyte, and
(v) Temperature.
Polarization effects can be decreased by
(i) Using highly conducting solutions,
(ii) Using electrod~s having large surface areas, and
(iii) Low concentrations of the electrolyte.
Elimination of polarisation: The polarisation in simple cells can be checked by different
ways:
(i) In mechanical method, the bubbles of hydrogen that are formed are brushed off from
time to time from the copper plate. In some cases, the surface of the copper electrode
is made rO'ught so that the bubbles may not stick to it.
(ii) In electrochemical method, the two solutions are taken so that hydrogen meets with
a second solution from which ions of the same metal as that of the positive plate are
liberated or some such gas is liberated which does not produce polarisation.
(iii) In chemical method, the polarisation may be prevented or at least minimised by using
some strong oxidising agents such as chromic acid, nitric acid, manganese dioxide
etc. to convert hydrogen into water, according to the reaction:
H2 + (112) 02 = H 20
Any substance which tends to diminish the polarisation in a cell is termed depolariser. It
may act as a catalyst in accelerating the changes at the electrodes, e.g., platinised platinum in
the liberation of hydrogen, or it may alter the change taking place at the electrodes to one
that takes place more easily, e.g., use of ~Cr207 in a bichromate cell.
5.3.2 DECOMPOSITION VOLTAGE
The decomposition potential or the decomposition voltage is the minimum external
potential (or voltage) that must be applied in-order to bring about the electrolysis of an
electrolyte. Electrolysis of an electrolyte in solution takes place only when the applied
voltage is greater than the decomposition potential of the electrolyte.
When a small amount of current (say 1 volt) is
passed through a solutions of HCI, it is observed that it
fall of practically to zero after sometime. This is due to
r
the back e.m.f. If we increase the applied voltage, a point
is reached when electrolysis re-starts and proceeds ~
continuously. This will occur only when the applied e.m.f. "C§
is just sufficient to overcome the back e.m.f. d
When a plot of current density against the e.m.f. is ~a
plotted (Fig. 5.2), it is seen that the current density Co)
increase is very small to begin with, but at a certain '--.......:="--_ _
L -_ _ _ _ __
e.m.f. - - .
point there is a sudden rise in the current with a v e r y . .. .
small change in the e.m.f. The voltage at which the Flg. 5.2. Decomposltion potential
sudden increase of current occurs is the decomposition potential of the electrolyte in the cell.
The value of e. m.t corresponding to point D on the X axis is the decomposition potential of the
electrolyte.
It may also be defined as the minimum e.m.t that is required to bring about electrolysis
of an electrolyte of the same magnitude as the electrolyte without any hindrance.
Metal Finishing 171
Decomposition voltage depends upon the nature of electrolyte solution and the material of
the electrode. It is, however, independent of the shape of the cell and the distance between
the electrodes.
Measurement of decomposition voltage: The decomposition potential (or voltage) of
an electrolyte may be determined in two ways:
(i) An electrolytic cell consisting of two platinum electrodes immersed in the electrolyte
solution (Fig. 5.3) is set up. The voltage is changed by moving the contact maker (X)
on the wire between points A and B. The current density is measured from the
ammeter used. The external e.m.f. applied to the electrodes is gradually raised and
the point noted at which there is a sudden increase in the current. The decomposition
potential can also be obtained by extrapolation of the curve as shown in the figure
above.
(ii) The electrodes are charged upto the atmospheric pressure by using an e.m.f. greater
than the back e.m.f. The external circuit is then broken and the e.m.f. of polariaation
is measured. This method depends upon the fact, that the decomposition voltage is
that e.m.f. which is just sufficient to overcome the e.m.f. of polarisation.
Battery
.....--------iII 11t---------.
Ar-----------------------~Tr----~B
Electrolytic
cell
Fig. 5.3. Electrolytic cell for determination of decomposition potential.

Applications of decomposition voltage : Decomposition voltage varies from solution
to solution. Metal ions migrate towards the cathode during electrolysis. It is obvious, that a
metal with a high solution pressure, such as zinc, iron, etc., will be more difficult to deposit
on the cathode, than the metals with low solution pressure, e.g., copper etc. Therefore, zinc
and iron will have higher decomposition voltages than that of copper etc. This fact is used in
electro-refining, electro-metallurgy and electroplating of metals. Some examples illustrating the
applications of decomposition potential are given below:
(i) Separation ofCu and Zn by electro-refining: The decomposition potential ofCuS0 4
for copper ele.ctrode is 1.5 volts and of ZnS0 4 for Zn electrode is 2.55 volts. When an e.m.f. of
less than 2.5 volts is applied across the Cu electrodes, copper will be deposited on the cathode
whereas Zn remains in the solution. It is because a voltage slightly higher (1.6 V) than the
decomposition potential of Cu (1.5 V) is required to deposit Cu. Similarly Zn will be deposited
when a voltage (2.6 V) slightly higher than the decomposition potential of Zn is applied.
(ii) Selective deposition of metals from the mixture: (Electro metallurgy) Consider a
mixture of cadmium, lead and silver nitrates. The respective metals can be deposited on suitable
electrodes by the electrolysis of the mixture depending upon the voltage applied. The
decomposition potentials of Cd, Pb and Ag are 2.3, 1.8 and 0.9 volts respectively. Silver will be
deposited when an e.m.f. slightly higher than the decomposition potential of Ag is applied i.e.,
Ag will be deposited when a voltage of around 1.0 volt is applied. Similarly other metals can
be deposited by applying voltage slightly higher than that of the concerned metal.
(iii) Electroplating: The decomposition potential is of great importance in electroplating.
For example, in nickel plating the electrolyte is usually a mixture of nickel salt (Nickel
ammonium sulphate) and dilute H 2S04 , When the acidity of the plating both exceeds beyond a
certain limit, hydrogen ions interfear with the deposition and the deposition will not be very
smooth and firm due to decomposition ofH+ ions and accumulation of hydrogen gas.
5.3.3 Overvoltage or Overpotential
Normally, electrolysis takes place continuously when the applied voltage is slightly more
than the decomposition potential. However, it has been observed in few cases that electrolysis
does not take place even when the decomposition potential is applied and an additional voltage
exceeding the theoretical value has to be applied so that the electrolysis takes place
continuously. This is known as overvoltage or overpotential represented by 11.
It is defined as the excess voltage that has to be applied above the theoretical
decomposition potential to start the electrolysis.
Over voltage (11) = Experimental decomposition potential - t'heoretical decomposition
potential. For example, for the electrolysis of dil H 2S04 using Pt and Pb electrodes, we require
a current of 1. 7 and 2.2 volts respectively against a theoretical value of 2.3 volts. This is
explained by the fact that the passage of a small current is accompanied by a relative large
polarisation which depends upon the nature of the electrode.
So, overvoltage may also be defined as, the difference between the potential of an
electrode when gas evolution is actually observed and the theoretical reversible value
for the same solution.
The concept of overvoltage was extended by Tafel (1905). He measured the excess potential
over the reversible values at a cathode at which hydrogen was being evolved at a definite current
density (defined as 'current per unit area of electrode surface'). So, the point at which the gas
bubble formation commences is termed as bubble overvoltages. The bubble overvoltages of metal
in dil. H 2S04 are as follows:
Platinised platinum 0.005v., smooth platinum 0.201 v., silver 0.15 v., lead 0.64 v. The effect
of surface on overvoltage is that a roughened surface has an invariably low overvoltage than a
smooth electrode of the same metal.
Hydrogen overvoltage : At a platinised platinum electrode, H2 is liberated practically at
the reversibly hydrogen potential of the solution. With other electrodes a more negative potential
is required to secure its liberation. The hydrogen overvoltage is defined as the difference
between the potential of an electrode at which hydrogen gas is actually evolved and the
potential of the reversible hydrogen electrode with reference to the same solution. At platinised
platinum and at zero current density, the hydrogen overvoltage is zero.
Oxygen overvoltage : Similarly, effects have been observed in the liberation of oxygen
at the anode by Coehn and Osaka. It is found that the anode potential at most metals, must
be considerable more positive than the calculated value, in order to cause the liberation of
oxygen at any appreciable rate. It will be observed that metals which have a high hydrogen
overvoltage, usually have a low oxygen overvoltage and vice versa.
Metal overvoltage : Common metals, except Fe, Co and Ni, start to be deposited from
solution at their reversible potentials. But these metal~J>f group VIII and many other metals
however, require a definite overvoltage for their deposition. It is supposed that these metals
Metal Finishing 173
are first deposited from solution in a metastable state, which is then followed by the deposition
of a solid solution of metastable and stable forms, which are considered to be deposited at
more negative potential than the reversible value for the stable metal.
The overvoltage values of hydrogen and oxygen are given in the following table.
Electrode
Hz
overvoltage
°z
overvoltage Electrode
H2
overvoltage °2
overvoltage
(volts) (volts) (volts) (volts)
Platinised 0.00 0.25 Ag 0.15 0.41

platinum
Pd 0.00 0.43 Ni 0.21 0.06
Au 0.02 0.53 Cu 0.23 -
Fe 0.08 0.25 Cd 0.48 0.43
It is to be noted that overvoltage for metal deposition is small compared to hydrogen

overvoltage. This is because, the deposition of metals over electrode surface takes place in
one step but hydrogen overvoltage is a measure of the liberation of hydrogen gas from the
electrode surface; a higher overvoltage indicates a slow release of hydrogen gas. The liberation
of a H2 gas on electrode surface takes place in three steps :
HsO+ ~ H+ + H 20
H++e- ~ H
H+H ~ H 2 (g).
Factors Affecting Overvoltage
(i) Nature and physical state of the electrode and nature of the substance: The
surface of a Pt black electrode acts as a catalyst for the combination of H atoms and
causes quick release of H2 molecules. That's why hydrogen overvoltage is negligible
on Platinum (black). It is just 0.01 V when current density of 10 Nm 2 •
(ii) Nature of the substance: The hydrogen overvoltage for soft metals like Pb is quite
large (0.67V). Mercury shows the highest overvoltage among metals. Its value is 4.04
Volt.
(iii) Current density : Provided hydrogen is not removed by reaction with oxygen or
other oxidising agents, the overvoltage increases with increasing current density.
(iv) pH: The overvoltages at most cathodes are independent of hydrogen ion concentration
over a large range of pH values. In strongly acidic or alkaline solutions, deviations
sometimes occur, which may be due to a large concentration of hydrogen or hydroxyl
ions, respectively.
(v) Temperature: Since overvoltage is due to a slow stage in the ionic discharge process,
it is clear that overvoltage will decrease with increasing temperature.
(vi) Impurity: Overvoltage is susceptible to the presence of impurities in the cathode
materials.
(vii) Pressure: It has been observed/that at higher pressures, the overvoltage is slightly
affected, while at lower pressures, it increases rapidly on cathodes of copper, nickel
etc.
(viii) Surface: On increasing the effective area of the surface, the overvoltage is decreased.
On smooth, even and polished surface, the overvoltage is greater than on a rough,
uneven surface e.g., the hydrogen overvoltages of platinised and smooth platinum in
dilut.e sulphuric acid are 0.01 and 0.09 volt, respectively.
To sum up the above factors for a given electrolyte, the overvoltage depends on :
(a) Nature and physical state of electrode,
(b) Nature of the substance deposited,
(c) Rate of stirring of the electrolyte,
(d) Temperature,
(e) Current density of the electrode surface,
(f) Impurities in cathode material, and
(g) pH value of the electrolyte.
Importance of overvoltage : The phenomenon of overvoltage is used in a number of
electrolytic processes. Some examples of its applications are:
(i) If electrodes with high overvoltages are used in electrolytic reductions, then it amounts
to the same fact, as increasing the activity of hydrogen at the electrodes. This
increases the reducing power of the electrode.
(ii) The presence of hydrogen overvoltage makes it possible to electrolytically deposit
metals (zinc, cadmium etc.) having a more negative potential than hydrogen, from
an acid solution.
(iii) The preferential liberation of IHI as compared to IH2 in the electrolysis of dilute
sulphuric acid containing both ions can only be explained on the basis of higher
overvoltage of IH2 at the platinum electrode.
(iv) The phenomenon of overvoltage plays an important part in the industrial production
of chlorine gas and sodium hydroxide by the electrolysis of sodium chloride solution.
(v) It is only due to the higher overvotlage oflead during charging in a lead accumulator
that only metal is deposited on the cathode instead of the hydrogen being evolved.
This view is confirmed that if lead is covered with a thin layer of a metal of very low
overvoltage, e.g., platinum, then it is observed that on electrolysis, no lead is deposited
on the cathode and instead hydrogen gas is liberated.
5.4 ELECTROPLATING
Electroplating is a process for deposition of a metal, by electrolysis, over the surface of
another metal, alloy, non-metal, polymer, ceramic and composite. Even different
combinations of the above material such as alloys, metal-polymers or metal composites
can also be electroplated.
In the electroplating process, a coating metal is deposited on the base metal or \alloy by
passing a direct current through an electrolytic solution containing the soluble salt of the\ coating
metal. The electroplating of common metals includes the processes in which ferrous pr non-
ferrous base material is electroplated with Nickel, Cr, Cu, Zn, PI, Cd, AI, brass, bronze or
suitable combinations thereof. If electroplating involving precious metals, a ferrous or non-
ferrous base material is plated with gold, silver, platinum, palladium, indium, iridium, rhodium,
ruthenium, osmium or combinations thereof. Besides single metals and alloys, composites and
Metal Finishing 175
metals containing dispersed solids such as teflon, aluminium oxide, tungston carbide, chromium
carbide and graphite are also electroplated.
The electroplating is done to modify the surface properties of the substrate to be
electroplated. It is carried out with the following ends in view:
(a) To make the substrate resistant to corrosion, chemical attack and wear,
(b) To increases the hardness of the base metal,
(c) To improve the appearance of the material to be electroplated.
Fundamentals
Before electroplating, the article is first cleaned with organic solvents to remove oils, greases
etc. and then treated with Hel (for eu and Ni plating) or H 2 S0 4 (dilute) (for chrome plating) to
remove oxide scales etc. The cleaned article is then made cathode in the electrolytic bath as
shown in Fig. 5.4. The anode is either the coating material or an electrode of inert material
like graphite. The electrolyte is a soluble salt solution of coating metal usually double salts
(NiSO 4. (NH 4)2 S0 4 in Ni plating or mixture of salts (euSO 4 and dil H 2S04 for eu plating) are
used to increase the conductivity of the solution. The electrodes are dipped in this electrolytic
solution and a direct current of electricity is passed. On electrolysis, the anode dissolves into
the electrolytic bath and the metal ions from the electrolyte solution are deposited as metal
over the cathode.
(Material to -il---.ofIl11l11l
be plated)
-"'!....--. - -
~ ~ Ei~rofYtiCBolution _-: -_
Anode - _. having the metal ions. :. .
Fig. 5.4. Electroplating process.
5.4.1 Mechanism of Electrodeposition

The reactions for a simple 1 : 1 electrolyte (MA) are shown below:
~aq) ~ Mn+(aq)+ An-(aq) Ionisation .. m
M ~ Mn+ + ne- (dissolution at the a..TJ.ode by oxidation) .. .(2)
Normally, the conditions, of electrolysis are so maintained that step 1 (oxidation) and step
2 (reduction) proceed at equal rates and concentration of Mn+ remains same in the electrolyte
solution. When an inert anode is used, oxygen is evolved at the anode as shown below and
metal ions (Mn+) ha"e to be added in the form of electrolyte to maintain the concentration.
Mn+ + ne- ~ M (deposition at the cathode by reduction) ... (3)
In electroplating, metal ions from acidic, alkaline or neutral media are reduced on the
articles being plated which act as cathodic surfaces. The metal ions in solution are usually
replenished by the dissolution of metal from anodes. Replenishment by metal salts is also in
practice as in the case of chromium plating. In such a case, an inert material must be used as
anode. Several types of electroplating solutions have been used commercially.
For instance, cyanide solutions are popular for Cu, Cd, Zn, Ag, Au and brass. However,
noncyanide alkaline solutions containing pyrophosphate are being used recently for Cu and
Zn. Acid sulphate solutions are commonly employed for most of the metal such as Cu, Ni etc.
Zn and Cd are sometimes electroplated from slightly acidic or neutral solutions. The most
common methods of plating are in barrels, on racks and continuously from a spool or coil.
For getting brighter and smooth deposits, low temperature, high current density and low
metal ion concentration etc. are the favourable conditions.
The deposition of metal is similar to crystal growth as metals have well defined crystal
structures. There are two distinct phases in electrode position. Formation of nuclei takes place
in the initial first phase. It requires a high overvoltage. It covers the electrode with a few
atomic layers of the metal. In the second phase growth of the deposit leading to the thickening
of the layer into a macroscopic (1 - 10 !lm thick) dimension takes place. This second phase
requires relatively low overvoltge for their rapid growth. During the plating process, the atoms
(adatoms) that are formed on the crystal plane quickly move and occupy favourable sites.
The most favourable site is known as kink site where the atom can interact with three
neighbours.
Fig. 5.5. Kink sites, edge sites and adatoms on electrodeposited surface.
Atoms also occupy less favourable sites such as the edge site (two neighbours) or just
remain as adatoms (one neighbour). The atoms occupying less favourable sites diffuse to more
favourable sites or redissolve.
1
H 20 ~ 2H+ +"2 02 + 2e-
In acidic solutions, hydrogen is liberated at the cathode
1
H++e- ~ -H
2 2
The steps in the overall phase growth are :
(i) The metal ions in solution move towards the electrode surface (cathode) by diffusion
in bulk,
(ii) Formation of adatoms by electron transfer from the cathode, and
(iii) The diffusion of the ada toms across the surface into the favourable positions (kink
sites) i.e., surface deposition.
The structure of the deposit is largely determined by steps (ii) and (iii). During plating
operation, the factors such as current density, temperature, pH ofthe electrolyte solution etc.
Metal Finishing 177
are adjusted so that steps (ii) and (iii) predominate. Depending upon the nature of deposit
obtained, the following three types of deposits have been recognised.
(a) Bad deposit: It is characterized by an outward growth (known as dendritic or whisker
growth) and has powdery (burnt) texture.
(b) Poor deposit: It is coarsely crystalline, non-uniform deposit having dull appearance.
(c) Good deposit: It has good adhesion, fine-grained texture, uniformity in thickness,
good covering power and brightness.
5.5 EFFECT OF PLATING VARIABLES ON THE PROPERTIES OF ELECTRODEPOSIT
The properties of electrodeposit depend on following plating variables :
(i) Current density: Current density is defined as the current per unit area generally
expressed in milliamperes per square centimeter (mA/cm2) of the electrode surface. As the applied
voltage is increased, the current density rises till it reaches a limiting value. As the current
density is increased surface diffusion is slowed down compared to the electron transfer. Due
to this reason, adatoms may not reach the most favourable positions.
Moreover, at higher potentials, number of nuclei formed may also increase. This results
in deposit having macroscale features and less ordered.
At different current densities, the nature of electrodeposit formed is summarized below:
(i) A low current density: The electron transfer is slow as compared with surface diffusion,
so the adatoms find the most favourable position (kink sites). As a result the deposit
is well formed.
(ii) A very high current density which is below the limiting current: The mass transport
(step (i» predominates in solution, so a poorly adherent deposit having rough and
powdery surface is obtained.
(iii) A very high current density which is above the limiting current: Hydrogen evolution
at the surface predominates causing a fast depletion of H+ ions in the vicinity of the
cathode, so a powdery deposit containing oxides and hydroxides of the metal is
obtained.
Therefore, to get a good deposit, an optimum current density for a particular deposition is
first determined and maintained during the process.
(ii) Plating Bath: It contains the solution used for electroplating, which is normally a
mixture of metal ion solution, other electrolytes, complexing agents and some organic additives
for improving the nature of the deposit.
(a) Mixture of metal-ion solution a electrolytes: The concentration of the metal
ion solution is generally kept high, typically 1 to 3 mol/dm 3 . The higher metal
concentration decreases the mass transfer at the current densities normally used.
Thus a good quality deposit is obtained.
Electrolytes are used in high concentrations as they increase the conductivity of the
plating bath and they also control the variation of pH by exerting buffer action. But
electrolytes do not participate in the electrode reactions.
(b) Complexing agents: With the help of complexing agents the metal ion is converted
into a complex ion so as to get a fine grained and more adherent deposits than that
obtained from simple ion solutions. Complex ions are used because.
Cyanide, hydroxide and sulphamate are the most frequently used complexing agents
especially in the electroplating of Au, Ag and Cd.
(i) They make the potential of the plating ion more negative, so that the plating takes
place at a lower potential.
(ii) They prevent the passivation of anodes, so that anode dissolve easily and thus increase
the efficiency of current. For example, chloride ions (in low concentrations) are used
in many baths.
(iii) They improve the throwing power of the plating bath and when the plating ion is known
to react with the cathode metal. For example, in plating copper on iron, copper ion is
complexed to prevent the reaction.
(c) Organic Additives: Organic compounds are added to the plating bath to influence
the nature of electrodeposits. They have different roles to play in modifying the nature of deposit.
They affect the structure morphology and properties of the deposit. They are added to achieve
the following four purposes.
• Levellers : Sometimes a deposit of uneven thickness is formed at certain places due to
fast diffusion of ions at these dislocations. For getting level deposit, the levellers are added
which are to adsobred at such regions so as to reduce the rate of electron transfer at such
places. For example, in nickel deposition, sodium allyl sulphonate is used as a leveller.
• Brighteners: Brighteners are used to make the deposit bright. For brightness the surface
should be light reflecting and not scattering. For this the grain size of the deposit must be
lower than the wavelength of the incident light. Brighteners are added to produce
macroscopically fine deposits. These are deposited on the metallic surface with their molecular
axis parallel to the substrate and not in a perpendicular direction.
Examples of brighteners : Molecules containing C E N, N = C = S, and C = 0 groups (like
Thiourea); aromatic sui phonates or sulphones.
• Structure modifiers (stress relievers) : They modify the structure of the deposit to
change the properties of the deposit. In fact, all electrodeposits are under stress due to lattice
defects. The deposit may be cracked on subjecting to strain due to internal stress and sometimes
this results in the microcracking of the deposit.
For example, saccharin, is most frequently used stress reliever.
• Wetting agents: During electroplating H gas is involved at the cathode. If the gas bubbles
are not removed they may get entrapped within the plated metal. These entrapped bubbles
would try to escape after the plating process. This often makes the substrate metal. This is
brittle when subjected to heat treatment after words. This is referred to as hydrogen
enbrittlement.
For this wetting agents are used. They also improve the levelling and uniformity of the
deposit and reduce its brittleness. For example, sodium lauryl sulphate is used as a wetting
agent.
(iii) pH : The optimum pH range foremost of the plating processes is either slightly acidic
or slightly alkaline. Because at high pH values i.e., highly alkaline medium the electrode
surface gets coated with insoluble hydroxides and at low pH values i.e., highly acidic medium
evolution of H2 occurs at the cathode. The desired pH (4 to 8) in the plating process is
maintained using buffers. For example, borate buffer is used in nickel plating and citrate buffer
in gold plating.
(iv) Temperature: A good deposit should be formed at elevated temperatures due to the
increase in the fusion of ions towards the surface. But high temperature permotes the corrosion
of the equipment used, hydrogen evolution at the cathode and decomposition of the organic
Metal Finishing 179
additives. Therefore, electroplating is usually carried out at moderate temperatures (35-60°C).
Within this range of temperature surface diffusion is more as compared to evolution ofH2 gas.
(v) Throwing power of the plating bath: Throwing power is the measure of the ability
of a plating bath to give a uniform and even deposit on the entire surface of the object. This is
of particular importance in objects which have complex shapes. For instance, electroplating in
holes, bends, recesses of the object is less uniform than on even surfaces. It is because these
points are comparatively at lower
Cathode 1 Anode Cathode 2
over-potential than the even surfaces.
When the distribution of the deposit
....-- -_----_
---..
------_. __ ..... . ...........
---- ::::;::. .._._....
... _..... -.........----_. _............ .
,...
is uniform, irrespective of the shape

of the object, throwing power is said ~~~~~ -.:::~ ..".~-, Insulated
to be good.
Insulated - ~
Determination of the throwing ::::::::-
power of a plating bath: Throwing
power is determined by Haring-Blum.
cell. (Fig. 5.6) The solution whose Fig. 5.6. Haring-Blum cell for the determination of throwing
throwing power is to be determined is power.
taken in the Haring-Blum cell. The
anode is placed at the centre. Two cathodes are placed at different distances (xl and x 2 where
Xl > x 2) from the anode. The surfaces of cathodes away from the anode have been insulated.
The weights WI and w 2 of the metal deposited on the cathodes are determined. The weight
w 2 deposited on cathode which is nearer to the anode is greater because of its higher
overpotential.
The following equation can be used for calculating the throwing power of the plating bath
solution:
100 (A -B)
Percentage throwing power = A+B-2
W2
where A = x/x 2' (when Xl > x 2); and B = - .
WI
When the amount deposited is same (that is WI = w 2 ), irrespective of the placement of the
electrodes, the throwing power is 100% and is considered to be very good.
Although the throwing power does not directly determine the nature of the deposit, certain
factors which determine the uniformity of the plating are expressed in terms of throwing power.
These factors are :
(a) Anodes: Uniform deposition may be achieved by optimum placement of the anodes
and use of auxiliary anodes.
(a) Conductance of the solution: The current distribution will be uniform over a
complex cathode surface in a solution of high conductance. This uniform current
distribution results in uniform deposition.
(e) Hydrogen evolution: At points of high overpotential, hydrogen evolution occurs at
the same time as the metal deposition. This leads to a reduction in the overpotential
at such points and thus results in more uniform deposits.
(d) Complexing agents: Throwing power can be improved by using complexing agents,
levellers etc.
Problem 1. Find the throwing power of the plating bath solution in a Haring-
Blum cell. Given that the distances between the two cathodes are 4 cm and 6.6 cm
from the anode and the weights of the plating on cathodes are 55 mg and 52 mg
respectively.
Solution: Given xl = 6.6cm and x2 = 4cm
wl = 52mg; w2 = 55mg
6.6cm
.. A =
Xl
-:=
4cm
:= 1.65; B = W2 = 55 mg =1.06
52mg
~ wt
Now percentage throwing power = 100(A-B) := 100 (1.65 -1.06) = 83.1

(A + B-2) (1.65 + 1.06 - 2)
5.6 ELECTROPLATING PROCESS

The electroplating assembly (Fig. 5.7) R
essentially consists of a plating tank. made of
steel with a rubber, lead or synthetic lining
inside to provide thermal insulation.
The anodes are hung from the outside
V Voltmeter
bars, connected to the positive bus bar
conducting current from a generator or
rectifier. The article to be plated is hung on
racks from the center or cathode bar. It is also Plating tank Heating or
called work bar. The racks must possess the '-------<A }-_ _- - . . . . J cooling coil
necessary current carrying capacity and enable Ammeter
uniform current distribution. A low-rpm drive
Fig. 5.7. Electroplating assembly.
motor helps in providing oscillating motion to
bring al:iout cathode agitation. The plating bath can be heated with steam or cooled with water
through coils or pipes. Immersion heaters or external heat exchangers may also be used for
heating or cooling.
Depending upon the size and number of articles to be electroplated, tanks of various sizes
and fixtures are employed. For large scale routine jobs the fixtures used are jig or rack
mounting type. For large number of small objects barred plating fixtures are used and for
large and single specialised workpieces such as motor car parts or computer frames individual
mounting is done. A rectangular tank with jigs for mounting objects as cathodes and anode
bags filled with palettes as anode.
Electroplating Baths Solutions
Electroplating baths contain acids, alkalies, metal salts and various additives used as bath
control compounds. The plating bath must be highly conducting solution of the material to be
plated. Non participating electrolytes are also added to increase the conductivity and throwing
power. Buffers are sometimes added to maintain the pH and additives to get a bright
and improve deposit. The constituents of some commonly used electroplating baths are given
below:
Electroplating process Bath composition
(i) Copper cyanide Copper cyanide, sodium cyanide, sodium carbonate,

sodium hydroxide and Rochelle salt.
(ii) Acid-Copper sulphate Copper sulphate and sulphuric acid.
(iii) Copper-fluoborate Copper fluoborate and fluoboric acid.
Metal Finishing 181
(iv) Copper pyrophosphate Copper pyrophosphate, potassium hydroxide and ammonia,
(v) Brass and Bronze Copper cyanide, zinc cyamde, sodium cyanide, sodium
carbonate, ammonia and Rochelle salt.
(vi) Gold cyanide Metallic gold, sodium phosphatE' and potassium cyanide
(vii) Silver Silver cyanide, potassium or sodium cyanide, potassium or
sodium carbonate, potassium hydroxide, potassium nitrate
and carbon disulphide.
(viii) Chromium Chromic acid and sulphuric acid. Sometimes with fluoride
catalyst.
I (ix) Nickpl (watts) Nickel sulphate, nickel chloride, nickel fluoborate, boric
acid, phosphoric acid, phosphorus acid and "stress-reducing
additives"
(x) Nickel-Acid fluoride Nickel chloride, hydrofluoric acid, citric acid, sodium lauryl
sulphate as wetting agent.
(xi) Black nickel Nickel ammonium sulphate, nickel sulphate, ammonium
Sulphate, zinc sulphate and sodium thiocyanate.
(xii) Tin-Nickel Alloy Nickel chloride, stannous chloride, ammonium fluoride,
ammonium bifluoride, sodium fluoride and hydrochloric
acid.
Nature of the Deposit

The properties of the deposit e.g., smoothness, porosity, uniformity of coverage, hardness,
condition of stress, depend upon the operating variables. These are the bath ~omposition, the
acidity or alkalinity of the bath, the temperature, the current density of deposition, the agitation
of the bath and the presence of addition agents. For instance, too high a current density gives
a rough, spongy deposed.
The capacity of tank varies from 20 to 2000,litres depending upon the type of article (work
piece) to be electroplated. Stress in electro plates can be relieved by proper heat treatment. If
stress is not properly relieved, the plate might crack upon ageing in service as a result of
WhICh some plates e.g., nickel will lose protective action against corrosion. Bright metal plates
are more susceptible to stress.
In comml'rcial electroplating applications, special attention is given to factors like (i) cathode
and anode curren.\, densIties, ILl) cathode ,lltd anode current efficiencies, (iii) rate of dep"sition
and (iv) throwing power. The cathode current efficiency relers to the amount of metal plu.~ea to
the amount that could theoretically be deposited by the same amount of current according to
Faraday second law. According to which 96,500 coulombs could theoretically deposit one
equivalent of the metal.
Anode current efficiency refers to the amount of metal dissolved at the anode. The product
of the cathode current density and efficiency gives the rate of deposition at the cathode. Throwing
power refers to the uniformity of plate thickness that can be expected on a shaped article over
the surface of which the current density will vary because of current distribution. The distribution
of the plating current is influenced by the relative distance of any given part of the surface
from the anodes.
The anodes employed are generally of the same metal as that to be deposited, so that the
dissolving anode maintains the metal ion concentration in the bath. Such anodes are referred
to as "soluble" anodes which constit.ute the main raw material consumed. However, in some
cases, "insoluble" anodes are used.
5.7 SURFACE PREPARATION OF ELECTRODES (PRET-REATMENT)
Before a metal or non-metal can be electroplated, the surface must be physically, chemically
and mechanically clean.
(i) Physical cleanliness means freedom from oils, greases, superficial dirts associated
with polishing, buffing and atmospheric dust.
(ii) Chemical cleanliness means freedom from oxides or other surface-formed compounds
of the basis metal.
(iii) Mechanical cleanliness means freedom from a surface skin of damaged metal (e.g.,
loose fragments, scratches and strains) produced by mechanical operations.
Electroplating involves a series of operations each of which is vital in determining the quality
of the final product. Following are the minimum number of steps involved in succession:
1. Mechanical preparation of the surface
2. Removal of scale or tarnish (pickling)
3. Removal of organic impurities
4. Acid dipping for chemical cleanliness
5. Rinsing
6. Electroplating
7. Rinsing, and drying
L Mechanical Preparation
Mechanical preparation of the base metal surface is generally required to achieve better
appearance, better protection and superior engineering properties. In order to achieve optimum
results from electroplating. The rought surfaces of freshly prepared articles are rendered
smooth by mechanical operations such as grinding with a grinding stone or silicon carbide
abrasion wheel. This is followed by sand blasting and scratch rubbing by a wire brush to get a
bright lustrous surface. For finer work, decorative polishing is carried out by polishing with
rouge.
2. Pickling (Removal of scale or tarnish)
This involves the removal of relatively heavy scale of oxides from hot rolling, easting and
heat treating, and also the removal of rust or tarnish due to exposure to atmosphere. Pickling
consists of immersing the article in dilute HCI or H 2S0 4 , For cleaning copper, nickel or brass
article the pickling bath consists of a dilute solution of HN0 3 or a mixture of dilute HN0 3 and
dilute H 2S0 4 ,
3. Removal of Organic Impurities (Greases etc.)
This involves the removal of oils, greases, polishing and buffing compound and other forms
dirt. This is usually accomplished by cleaning with organic solvents e.g., trichloroethylene
methylene dichloride and perchloroethylene or by aqueous cleaning agents e.g., sodium
carbonate, hydroxide, or silicate with or without electric current. To remove the surface dirt,
simple immersion in an aqueous cleaner may not be adequate. Better results may be obtained
by discharging gas on the surface of the metal by rendering it as cathode or anode, which
provides scrubbing action.
Metal Finishing 183
4. Chemical Cleanliness
Dipping in 10-30% (by volume) of HCI or H 2S0 4 after cleaning is an important step
particularly if the parts are to be first plated in an acid solution. This operation removes any
tarnish film produced during cleaning step and also neutralizes any alkaline film formed which
cannot be completely removed by rinsing. This is essential to ensure that the pH of the plating
bath is not affected. Subsequent to the acid dip and the rinse following it, neutralization by
dipping the workpiece in a dilute cyanide solution may be desirable to prevent rusting.
5. Rinsing
Rinsing with clean water is essential between the various steps in the electroplating
sequence. This is accomplished by dipping the article in clean running water or by spray:rinsing
or both depending upon the shape and drag-out characteristics ofthe article being plat~d.
Special Treatment
Some materials to be electroplated require special treatment besides usual cleaning
processes. A suitable metal is first plated on the surface before the desired plating is done. 'For
example, AI and Mg require special treatment before subjecting to electroplating. For successful
plating on Al and Mg, the oxide film is first replaced by a thin film of zinc by immersing'in a
solution containing (ZnO + NaOH).
6. Preparation of Non-metallics
Non metallics must be rendered clean, smooth and conducting before subjecting to
electroplating. Synthetic plastics such as Vinyl chloride, Vinylidene chloride, bakelite, cellulose
derivates and laminated phenolics can be polished by methods comparable to those used in case
of metals. Leather, paper, cloth etc. are cleaned to remove oils, greases and waxes and are then
rendered non-porous by coating with shellac or lacquer. A conducting surface is produced by
depositing a continuous coating of Cu or Ag by chemical reduction or metal spraying etc.
The acid CuSO 4 plating bath is generally most suitable for plating on the conductive film.
The plating solutions used for metals are also applicable for non-metallics. If a different metal
plating is needed, the acid CuSO 4 bath should be used as a first coating followed by the desired
metal plate.
5.8 ELECTROPLATING OF COPPER
The capacity of the electroplating tank is decided on the basis of the nature and number
of the article to be plated. Three copper plating namely (i) Cynide process, (ii) Acid-CuS0 4
process, and (iii) Copper fluoborate process are commonly in use depending upon the objective
of plating. The details of the first two are summarised below:
Cyanide bath Acid-Sulphate bath
Ii) Platmg bath CuCN (40 - 50 gm), CuS0 4 (200 - 250 g),
solution KCN (20 - 30 gm), H 2S0 4 (50 -75 gm!L)
K ZC0 3 (10 gIL)
1J1) Cathode Pretreated object (to Pretreated object (to
be coated) be coated)
(ii i) Anode 02 free Cu of high Phosphorus
conductivity containing rolled Cu
(Wi AddItives Sodium thiosulphate Gelatin, dextr'in, ,sulphur
containing brighteners,
suI phonic acids
(V) Operating 40 - 70°C 20 - 40°C
i temperature
(vi) Current density 10 ..40mNcm2 20-50 mNcm 2

(vii) Current 60- 90% 95 - 99%
efficiency
(viii) Throwing Good Low
power
(ix) Applications Used for iron and its In PCBs.
<I)loy plating, as an
undercoat for Cr
plating, in PCBs
Notes: (i) Before carburizing, the steel parts are Cu plated in order to avoid carburizing at undesired
portions.
, (ii.) Portion of steel is protected from nitriding in hardening process by electro-plating
of Cu.
(iii) Also used for printed circuit boards.
5.9 ELECTROPLATING OF NICKEL
The type and capacity of the electroplating bath is determined on the basis of the nature
and number of the articles to the plated. Depending upon the objective of electroplating, Nickle
plating is commonly of four types namely
(i) Nickle (watts process)
(ii) Nickle acid fluoride process
(iii) ,Black nickel process
(iv) Tin-nickle alloy.
The details of the first two are summarised below:
Sulphamate bath Sulphate bath
(i) Plating bath Nickel sulphamate NiSO 4 (250 gm),
s~lution (600 gm), NiCl 2 NiC1 2 (45 gm), boric
(5 gm), boric acid acid (30 gIL),
(40 giL), pH = 4 pH =4-5
(ii) Cathode Pretreated object to be Pretreated object to be
coated coated
(iii) Anode Ni pellets or pieces Ni pellets or pieces
(iv) Additives Naphthalene - 1, 3, 6 Coumarin, saccharin,
trisulphonic acid benzene sulphonamide
(v) Operating 50 - 60 0 C 40 -70 0 C
temperature
(vi) Current 50 - 400 mNcm 2 20-50mNcm2
density
(vii) Current 98% 95%
efficiency
(viii) Throwing power Good Good
(ix) Applications Decorative mirror As an undercoat for
finish Cr plating.
Notes : (i) Nickel plating' is mostly applied on iron. As it is cathodic to iron so corrosion may take
place at pin holes and coating pores. Thus coating should be of sufficient thickness. In order to remove
pores in Ni cuating, a thin Cu coating is first applied in between 2 coatings of nickel.
(ii) Thickness of nickel coating is thin and thick, respectively for in-door and outdoor applications.
(iii) Ni coating has good corrosion and wear resistance.
Metal Finishing 185
5.10 ELECTROPLATING OF CHROMIUM
The main objective of chromium plating is to provide a corrosion resistant and decorative
finish to the article. Chrome plating is most commonly used for decorative purposes because
of its durability, and resistance to chemical attack abrasion. It may be noted that Cr anodes
are never used in Cr plating due to the fact that Cr metal passivates strongly in acid sulphate
medium. Moreover, Cr anode on dissolution gives rise to Cr(IIl) ions which lead to the deposit
of black Cr to be formed.
(i) Plating bath solution: Chromic acid bath: Chromic acid (cr03) and H 2S04 in
100: 1
(ii) Cathode: Object to be plated
(iii) Anode: Insoluble anodes Ph - Sb or Pb - Sn coated with PbO~
or stainless steel
(w) Operating temperature: 45 - 60% C
(v) Current density: 100 - 200 mAlcm 2
(vi) Current efficiency : 8-12%
(mi) Applications : Corrosion resistant and decorative finish
Notes: (i) In the plating bath, SO/,- ions from H2S04 act as a catalyst. Cr is present in the hexavalent
state Cr (VIl as Cr03 in the bath solution. In the presence of SO /- ions the Cr (VI) is converted into Cr
(III) by a complex anodic reaction.
(ii) Pb0 2 coating on the anode oxidize Cr (III) to Cr (VI) and thus control the concentration of Cr
(III). In the presence of large concentration of Cr (III) ions, a black Cr deposit is obtained.
(iii) The cathode must be pretreated as for getting good electrodeposit, the substrate surface must
be free from dirt, oil and grease.
5.11 ELECTROPLATING OF GOLD
The main objective of gold plating is decoration where a ferrous or non-ferrous base metal
is electroplated with Au, Ag, Pt, Pd, In, Ir, Rh, Ru, Os or their combination. The base metals
and alloys that are most commonly subjected to decorative electroplating are steel, brass, copper,
nickel, silver, white metal alloys of Pb, Zn or Sn and AI alloys. The type of plating required is
determined on the basis of the appearance desired, the intended use of the finished product,
and the nature of the base metal being plated.
Gold plating is of many types depending upon the desired shade offinish product. The desired
shade is attained by a making a suitable choice of other metal to be combined with Au, which
is made anode. The nature of solution in the plating bath would also depend upon the material
of the anode selected. Cynide process is commonly used, whose main points are summarised
below:
(i) Plating bath solution: Metallic gold, sodium phosphate and potassium cyanide.
(ii) Cathode: Object to be electroplated which must be free from dirt, oil and grease etc.
in order to get a good electrodeposit.
(iii) Anode: Au pellets or pieces.
(iv) Additives: Citrate buffers are usually added to maintain the desired pH. Sodiu~ allyl
sulphonate is added to act as a leveller.
(v) Operating temperature: 40 =60°C.
(ui) Current density: 10-40 mAlcm 2.
(vii) Current efficiency: 60-90%.
(viii) Applications: Because of its acid and corrosioil. resistance, it is used for decoration
purposes especially in artificial jewellary and tombs oftemples.
5.12 ELECTROLESS PLATING
The process of deposition of a metal from its salt solution on a catalytically active surface
by a suitabie reducing ag!,!nt without using electric current is known as electroless plating.
Metallic ions are reduced to the metal with the help of reducing agents. Once a metal is
formed, it gets plated over a catalytic surface.
Metal ion + Reducing agent Catalyst Surface) Metal plated + Oxidized product
The driving force in electroless plating is an autocatalytic redox reaction over a preheated
catalytic surface instead of electric current in case of electroplating. In case of electroless plating
no separate anode is required as in the case of electroplating. Here a chemical reaction takes
place on the surface of the article to be plated.
Surface Preparation for Electroless Plating
The techniques given below are used for the preparation of the surface of the object to be
plated to get a bright deposit. .
(i) Etching by acid treatment;
(ii) Electroplating of the same or different suitable metal followed by heat treatment;
(iii) Treatment of surface with stannous chloride and palladium chloride alternately for non-
conducting surfaces such as plastics or printed circuit boards.
Composition of Electroless Plating Bath
Generally, an electroless plating bath consists of the following components:
(i) Generally metal chloride or sulphate are taken as a source of soluble, electroactive
metal in the plating solution;
(ii) Hypophosphites and formaldehyde are added as reducing agent;
(iii) .Citrate, tartrate and succinate are added as complexing agent;
(iv) Anions like succinate, glycinate and fluoride are added to increase the rate of plating;
these are also know as exaltants.
(v) Lead, calcium and thallium ions and thiourea act as stabilizers to prevent the
decomposition of bath;
(vi) Buffer are added to control pH.
Advantages of Electroless Plating
Electroless plating is superior to electroplating because of the following advantages :
(a) In electroless plating, use of electrical contacts or electrical power is elimianted;
(b) Throwing power of electroless bath is better. Consequently the intricate parts such
as bends recesses and inner parts of objects with irregular shapes can be uniformly
coated;
(c) Plastics and other insulators and semiconductors can also be plated by electroless
plating;
(d) Resulting deposits have unique chemical, mechanical and magnetic properties;
(e) There are no chances of the H gas being trapped with in the deposit in electroless
plating. It avoids crakes in the deposit with time;
Cf) Levellers are not required in elecroless plating;
Metal Finishing 187
(g) The coatings developed by electroless plating are harder as compared to that of
electroplating.
Distinction between electroplating and electroless plating
Electroplating Electroless plating

(i) Driving force Electrolysis by the passage of electrons. Autocatalytic redox reaction over a
pretreated catalytic surface.
(ii) Anode A separate anode is used which is Anode reaction takes place on the
connected to the terminal of battery. surface of the article which is not
connected to any terminal of
battery.
The object is not connected to any
(iii) Cathode The object is connected to the -Ve terminal of battery.
terminal of battery after pretreatment
of its surface.
(iv) Reading agent Reduction is brought about by electrons. It is treated to make the surface
catalytically active. Reduction is
brought about by the reducing
agent.
(v) Throwing power Good or Poor. Better.
(vi) Applicability Precoating of metal is required. Plating of insulators
semiconductors semiconductors and conductors is
and insulators easily carried out.
is difficult
5.12.1 Electroless Plating of Copper
(a) Pretreatment and activation of the surface: The surface to be treated is degreased
and etched in acid. On gold, silver, platinum, palladium, rhodium, iron, cobalt and nickel,
electroless copper gets deposited spontaneously in presence of reducing agents. But insulators
like plastics, printed circuit boards and glass are activated by dipping first in stannous chloride
and then in Palladium chloride.
(b) Plating bath solution: A solution of copper sulphate (12 gmIL); formaldehyde
(8 gmIL) as reducing agent; sodium hydroxide (15 gmIL) and rochelle salt (14 gIL) as' buffer,
EDTA as complexing agent and exaltant (20 gmIL). . .
pH of plating bath solution: 11
Temperature of plating bath solution: 25°C.
(c) Reactions
At Cathode: Cu2+ + 2e- ~ Cu
At Anode :
Overall reaction: Cu2+ + 2HCHO + 40H- Catalyst

Surface) 2 HCOO- + 2H2 0 + H2
Cu2+ ions and formaldehyde consumed during plating are replenished periodically.
(d) Applications: Printed circuit boards (pcb) are an important application of electroless
cooper plating.
In double side and multilayer boards where plating-through-holes is required, electroless
technique is the best since the holes cannot be electroplated. The technique employed to
manufacture printed circuit boards (pcb's) is called subtractive method.
This method involves the following steps which have been shown in Fig. 5.8.
'\1- hoI,
Fig. 5.8. Steps in subtractive technique of plating-through-hole in the manufacture of double-sided pcb.
(i) In pcb, the base object is a plastic material like glass reinforced plastic (GRP), epoxy
or phenolic polymer.
(ii) A layer (5 to 100 1J.Ill) of copper is electroplated on this base which are double sided.
Double-sided Cu-clad laminates with circuit patterns are preferred because of the
feasibility of packing of more components in a smaller space.
(iii) Selected areas are then protected by a phot?-resist or electroplated image.
(iv) The rest of the copper is etched away to produce the circuit pattern or the track;
(v) The connection between the two sides is done by drilling hole followed by plating-
through-holes by electroless plating.
(vi) Copper cladded tracks on each side of the plastic board are connected through hole.
5.12.2 Electroless Plating of Nickel
(a) Pretreatment and activation of the surface: By treatment with organic solvents
or alkali followed by acid treatment, the surface is decreased first. It is then activated depending
upon the substrate as given below:
(i) AI, Fe, Cu and brass: They can be directly plated without activation.
(ii) Stainless steel: By dipping in a hot solution containing 1 : 1 sulphuric acid.
Mg alloys: They are given a thin layer of Zn and Cu.
(iii)
(iv) Plastics, glass and quartz: They are sensitized in stannous chloride solution
containing HCI at 25° C followed by dipping in Palladium chloride. To get a layer
of Pd, the surface of dried.
(b) Plating bath solution: A solution of nickel chloride (20 gmIL), sodium hypo phosphite
(20 gmIL) as a reducing agent, sodium acetate buffer (10 gmIL), sodium succinate as complexing
agent and exaltant (15 gmIL).
pH of plating bath solution: 4.5
Temperature of plating bath solution: 93°C.
Metal Finishing 189
(c) Reactions:
At Cathode : Ni
At Anode : H2P03- + 2H+ + 2e-
Catalyst
Surface)
Ni + H2PO 3- + 2H+.
(d) Favourable conditions:
(i) As the overall reaction involves the liberation of H+ ions the pH of the solution
changes as the reaction proceeds. This affects the quality and the rate of plating.
The use of buffer is essential to control the pH.
(ii) Plating does not start till a temperature of 70°C is reached and it increases with
rise in temperature beyond 70°C. The rate becomes maximum at 93°C. But beyond
93°C, further rise in temperature may lead to decomposition of the plating bath
solution.
(e) Properties:
(i) Electroless nickel baths have very good throwing power. Therefore, objects having
complex shapes with bends, peaks, recesses, threads and inner surfaces can be
plated uniformly deposits.
(ii) Electroless deposits being pore free have better corrosion resistance than
electroplated deposits.
(iii) Electroless deposits are almost twice as hard as the electroplated deposit due to
the plating of Ni. - P alloy. As a result the wear resistance is also high.
(n Applications :
(i) Electroless Ni - P coatings are used extensively in electronic applications, because
depositing Ni and AI increases the solderability of AI. At the same time a non-
magnetic underlay in magnetic components is provided.
(ii) Acrylonitrile-butadiene-styrene (ABS) plastics coated with nickel by electroless
technique have functional as well as decorative applications. A wide range of
components are thus finished for automobile, electronic, domestic and consumer
sectors of industry. Knobs on quality equipments, tops on perfume bottles, costume
jewellery and car trim are some common examples.
(iii) Plastic cabinets coated with copper and nickel by electroless plating are used in
digital and electronic instruments for electromagnetic interference shielding.
1. What are the various important Metal finishing techniques?

2. The process of electrolysis is based on which laws?
3. What are the various factors which affect the Electrode Potential ?
4. What do you mean by decomposition voltage?
5. What are the various applications of decomposition voltage?
6. What do you mean by over voltage or over potential ?
7. What are the various factors which affect the over potential ?
8. What are the various applications of over voltage?
9. Discuss about the Electroplating?
10. Write the mechanism of the electroplating process.
11. What do you mean by current density ?
12. What is plating Bath?
13. Why levellers are added during electroplating process?
14. What is the role of Brightness in electroplating process?
15. What are the various operations used in electroplating?
( ANSWERS)
1. The various important metal finishing techniques are :

(i) Electroplating (ii) Electroless plating
(iii) Immersion plating (iv) Electrophoretic plating
(v) Inorganig coatings (vi) Metal cladding
(vii) Metal spraying (viii) Cementation
(ix) Plastic coating (x) Organic coatings such as paints,
varnishes and lacquers.
2. It is based on Faraday first and second laws.
3. The magnitude of concentration polarisation at an electrode decreases if the rate of
diffusion increases, by raising the temperature and by increasing the concentration.
3. The decomposition potential or the decomposition voltage in the minimum external
potential (or voltage) that must be applied in order to bring about the electrolysis of
an electrolyte.
5. The various applications of decomposition voltage are :
(i) Separation of Cu and Zn by electrorefining.
(ii) Selective deposition of metals from the mixture.
(iii) Electroplating.
6. Over voltage may be defined as the difference between the potential of an elecrode
when gas evolution is actually observed and the theortical reversible value for the same
solution.
7. The various factors which affects the over voltage are :
(i) Nature and physical state of the elecrode and the nature of the substance.
(ii) Nature of the substance.
(iii) Current density.
(iv) pH.
(v) Temperature.
(vi) Impurity and pressure.
S. The various applications of overvoltage are :
(i) The phenomenon of over voltage plays an important part in Industrial production
of chlorine gas and sodium hydroxide by the electrolysis of sodium chloride solution.
Metal Finishing 191
(ii) The presence of hydrogen overvoltage makes it possible to electrolytically deposit
metals (zinc, cadmium) having a more negative potential than hydrogen, from an
acid solution.
(iii) The preferential liberation of lHl as compared to lH2 in the electrolysis of dilute
sulphuric acid containing both ions can only be explained on the basis of higher
overvoltage of 1H2 at the platinum electrode.
9. Electroplating is a process for deposition of a metal, by electrolysis over the surface of
another metal, alloy, nonmetal, polymer, ceramic and composite.
10. The reaction for a simple 1 : 1 electrolyte are:
MA (aq) ~ Mn+(aq) + An- (aq) Ionisation ... (1)
M ~ Mn+ + ne- (dissolution at the anode by oxidation) ... (2)
Mn+ + ne- ~ M (deposition at the cathode by reduction) ... (3)
11. Current density is defined as the current per unit area generally expressed in
milliamperes per square centimeter (mAlcm 2 ) of the electrode surface.
12. It contains the solution used for electroplating, which is a mixture of metal ion solution,
other electrolytes, complexing agents and some organic additives.
13. Sometimes, during electroplating process a deposit of uneven thickness is formed at
certain places due to fast diffusion of ions at these dislocation.
For getting level deposit, the levellers are added which are to adsorbed at such region
so as to reduce the rate of electron transfer at such places. For example, sodium alekyl
sulphonate is used as leveller.
14. Brightners are used to make the deposit bright. For brightness the surface should be
light reflecting and not scattering.
15. The various operation are :
(i) Mechanical preparation of the surface.
(ii) Pickling (Removal of scale)
(iii) Removal of organic impurities.
(iv) Chemical cleanliness.
(v) Rinsing.
(vi) Preparation of non-metallics.
16. The various types of Nickel plating are :

(i) Nickel watts process.
(ii) Nickel and fluoride process.
(iii) Black nickel process.
(iv) Tin-Nickel process.

1. What is metal finishing? Write a note on technological importance of metal finishing.

2. Explain the term electrode polarization. What are the factors that affect electrode
polarization ?
3. Define electrode polarisation. Give its cause. How can it be eliminated.
4. What is decomposition potential? How is it measured?
5. Define decomposition potential. Give its important applications in electrochemical
processes.
6. What is overpotential ? How does it affect the electrolysis in an electrolytic cell ?
7. Explain the term overvoltage. What do you know about hydrogen, oxygen and metal
overvoltage. Give application of overvoltage.
8. Explain the effect of the following plating variables on the properties of electrodeposit
(i) pH, (ii) Temperature, and (iii) Current density
9. Give a brief account of electroplating of (i) Cu, (ii) Ni.
10. Give reasons :
(a) Chromium anodes are not used in electroplating.
(b) Solutions of high conductance are used in electroplating.
(c) AI and Mg require special treatment before electroplating.
11. Discuss the mechanism of electrodeposition.
12. Describe the method of electroplating process.
13. Discuss how the various constituents of the plating bath solution affect the nature of
electrodeposit.
14. Describe the term throwing power of plating bath solution. Mention the factors which
influence the throwing power. What is its significance?
15. In a Haring-Blum cell if the distances xl and x 2 of the two cathodes from the anode
are different show the throwing power is 100% if the weights of the metal deposited
w l and w 2 respectively on the two cathodes is the same.
16. Explain the method of pretreatment of the electrode surface for plating.
17. Give a brief account of electroplating of (i) chromium (ii) Gold.
18. Give the composition of plating bath solution and the nature of anode in case of
(i) copper (ii) chromium (iii) gold plating.
19. What is electroless plating? Explain the principle involved. Mention its advantages.
20. Describe the method of electroless plating of nickel.
21. Explain the various steps involved in the subtractive technique of plating-through-hole
in the manufacture of double sided PCB.
22. What is meant by electroless plating? Briefly explain the electroless plating of copper
on P. C.B. [Vru, B.E., Aug. / Sept., 2000J
23. (a) What is metal finishing? Explain the technological importance of metal finishing.
(b) Give an explanatory note on nickel plating.
[Vru, B.E., Aug. / Sept., 2000J
Metal Finishing 193
24. What is known as metal finishing? Give a brief account of electroplating of copper.
[VTU, B.E., March, 2001J
25. Give an account of nickel plating. [VTU, B.E., August, 2001J
26. (a) Explain the term decomposition potential. Mention its significance with .reference
to electrode position of metals.
(b) Explain the effect of the following plating variables on the properties of
electrodeposit.
(i) Current density
(ii) Throwing power. [VTU, B.E., August, 2001J
27. (a) Explain the term overvoltage with suitable example. [VTU, B.E., August, 2000J
(b) Define electroplating. Explain the following factors influencing the nature of
electrodeposit.
(i) Current density
(ii) Throwing power of the plating bath. [VTU, B.E., Jan. / Feb., 2003J
28. (a) Discuss the electroplating the copper.
(b) Explain the method exployed to clean the surface of metals to be electroplated.
[VTU, B.E., Jan. / Feb., 2003J
29. (a) Explain the term decomposition potential and over-voltage.
(b) Give any three objectives of electroplating and explain electroplating of chromium.
Why chromium anode is not used in electroplating of chromium.
(c) Give the advantages of Electroless plating and explain electroless plating of copper
on PCB's. [VTU, B.E., July / Aug., 2004J
30. (a) What is electroplating ? What are the advantages of electroless plating over
electroplating?
(b) Explain the electroplating of Nickel and electroless plating of copper on PCB's.
(c) Discuss the role of the following factors on the nature of electrodeposit.
(i) Current density
(ii) Throwing power of the plating path
(iii) pH. [VTU, B.E., Feb. / March, 2005J
LIQUID CRYSTALS AND THEIR
APPLICATIONS
SYLLABUS
Introduction, Classification-thermotropic & lyotropic; Types of mesophases-nematic, chiral
nematic (cholesteric), smectic and columnar-example of the compounds exhibiting the
. liquid crystaline behaviour, homologues series (PPA and MMBA series) : Application of
this liquid crystals in display systems. 4 Hours
6A.I INTRODUCTION
Liquid crystals are pure liquids which are turbid and like crystals anisotropic over a
definite range of temperature above their freezing points. Let us explain the term 'Isotropy
and Anisotropy' before proceeding further.
In case of amorphous substances, properties like electrical conductivity, refractive index,
thermal expansion etc. are identical in all directions just like in case of gases or liquids. This
property is called isotropy and the substances showing this property are called isotropic.
On the other hand, in case of crystalline substances, the properties mentioned above have
different values in different directions. This type of
behaviour is called anisotropy and the substances o • 0 • BO •
exhibiting this type of behaviour are called anisotropic.
Thus whereas amorphous substances are isotropic in
nature, the crystalline substances are anisotropic. The
anisotropy exhibited by crystalline substances is obviously
due to the fact that in making measurements in different
- 0
o •
·0-0-0
.0-
0.0
directions, different types of particles fall on the way as AO _ 0 _ 0 _

shown In Fig. 6.1 Along the direction AB only one type of C--------~----~~D
particles represented by dots (e) or by circle (0) have been -0-0-0
arranged, whereas along CD both types of particles occupy Fig. 6.1. Anisotropy exhibited by
positions one after the other. crystalline substances.
Liquid Crystals and their Applications 195
The study of liquid crystals was started in 1888 by an Austrian botanist, Freidrich
Reinitzen, who observed that solid cholesteryl benzoate on heating becomes a heavy liquids
which on further heating change into clear, transparent liquid. On cooling the liquid crystal
state change to solid which took place exactly at the same temperature. For this discovery,
Reinitzer is credited-with discovering a new phase of matters that is liquid crystal phase.
In other words, liquid crystals are liquids that can have sufficient long range order in them
to make them behave like solid. Liquid crystals are made from molecules that are long, thin
and not symmetrical in nature. Liquid crystals materials are unique in their properties and
uses. A large number of organic compounds with the following structure with long chain
molecules are used as liquid crystal materiaL
where A, B, Care substituents or carbon chains.

An example is given below:
p-azoxy anisole
For example, these organic compounds on heating melt sharply to give a milky (turbid)
liquid which on further heating becomes clear again at a definite temperature. The former is
called the transition point where as the later is called the melting point. For example p-azoxy
anisole, its transition point is 389 K and melting point is 408 K. On cooling the clear liquid the
reverse change takes place exactly at same temperature. The turbid liquids thus obtained is
found to be anisotropic-a property possessed by crystalline substances. Hence these turbid
liquids are called liquid crystals. A few examples of compounds showing this behaviour are
given in Table 1 together with their transition temperature and melting points.
Table 1. Some Typical Substances Showing Liquid Crystal Character.
Substance Tran.;ition Point ("C) Melting Point (OC)
Anisaldazine 165 180
CH30C6H 4CH : NN : CHC 6HPCH 3
p-Azoxyanisole 116 135
CH30C6H4NONC6H40CH3
p-Azoxyphenetole 137 167
C2H50C6H4NONC6H40C2H5
Diethylbenzidine 115 120
C2HGNHC6H4C6H4NHC2H5
Mercury di -(p-ethoxybenzal-aminophenyl) 204 272
Hg(C~H4N : CHC 6HPC 2H 5)2
p-Methoxy cinnamic acid 170 186
CHPC6H 4 CH : CHCOOH
6A.2 WHAT ARE LIQUID CRYSTALS

These are certain solids which when heated undei·go \.,:0 sharp phase transformations one
after the other. Liquid crystaL matenais generally have ::;~~':eral common characteristics. Among
these are a rod like molecular structure, rigidness of the long axis and strong dipole. The
characteristic of the liquid crystal is that they show anisotropy (i.e., they have different physical
properties in (Hfferent directions). The anisotropy is observed particularly in their
optical behaviour. Thus they exhibit double refraction and give interference patterns in
polarised light. True liquids on the contrary, are isotropic (i.e., they have same properties in
all directions).
The liquid crystal state is a distinct phase observed between crystalline state and isotropic
liquid state. Liquid crystal may be described as a distinct state of matter in which the degree
of molecular ordering lie intermediate between the ordered state and the completely disordered
isotropic liquid state.
The liquid crystal state is also referred to as mesophase. The compounds which exhibit
meso phase are also called mesogens. Liquid crystals do not possess properties of crystalline
state. Actually they are more like liquids having properties viz., surface tension viscosity.
Therefore the term mesomorphic state (meso-intermediate form) is also used for liquid crystals.
The rntermolecular forces in molecules ofliquid crystal are strong enough to hold the molecules
together, but not so strong as to restrict their movement too much. The unsymmetrical nature
of the molecules leads to an unsymmetrical packing of the molecules. When the packing is
unsymmetrical, we say that the arrangement is anisotropic.
6A.3 THEORY OF LIQUID CRYSTALS
It was considered the liquid crystals to be heterogeneous like emulsions. This idea was
later rejected because neither any particle could be detected microscopically nor separated in
these crystals. Recently, Lehmann showed that the turbid liquid is homogeneous and its turbid
nature is due to optical properties like double diffraction. Boss proposed another theory called
'Swarm theory'. According to this theory mesomorphic behaviour is shown by compounds
having big chains. Their free rotation is hindered and they arrange themselves in parallel
patterns in the form of swarms and a number of such swarms are obtained. The molecules in
swarm are parallel to one another but are not to those present in another. In each swarm,
large number of molecules are arranged parallel to one another and behave as a crystal. The
turbid liquid is considered to be made of large number of such swarms distributed in random
manner. Lehmann found that each swarm when viewed through microscope appears as
transparent liquid and the turbidity is only due to scattering of light at various boundaries of
the swarms. When temperature is increased gradually the turbidity starts disappearing as the
size of swarms gradually becomes smaller and smaller and the liquid becomes clear at one
sharp temperature called melting point '1'he anisotropic properties like double diffraction
di.sappears due to orientatiullof the moleculeswithin the swarms. and the clear liquid becomes
isotropic with single refraction.
6A.4 CLASSIFICATION OF LIQUID CRYSTALS
Liquid crystals are classified into two main categories, namely, (I) Thermotropic liquid
crystals. (II) Lyotropic liquid crystals.
(1)Thermotropic Liquid Crystals
The class of compounds that exhibit liquid crystalline behaviour on variation of temperature
alone are called thermotropic liquid crystals. They are of three types.
(i) Nematic or thread like liquid crystals.
(ii) Cholesteric liquid crystals.
(iii) Smectic or soap like liquid crystals.
(i) Nematic or thread like liquid crystals
Nematic is a (Qreek word nematos meaning thread
like) liquid crystals are formed by compounds that are
optically inactive. On heating they lose their planar
structure but retain a parallel alignment as shown in Fig.
6.2 (a). Thus, they retain their orientation, but lose
periodicity. In other words, the molecules have elongated
shape and are approximately parallel to one another, but
can move up or down or sideways or can relate along their
axes. Nematic phase is characterized by the total loss of
positional order and a near by normal flow behaviour
similar to its liquid phase. A typical example of nematic
liquid crystal is N-paramethoxy benzylidene P-butylaniline
changes to nematic liquid at 29°C and this persist up to Fig. 6.2 (a). Nematic liquid crystals.
43°C after which it melts to isotropic liquid.
The nematic liquid crystals do not conduct electricity, when in pure form. They flow like
liquids, but their mechanical properties like (viscosity, elasticity), electrical (dielectric constant),
all optical properties and diamagnetism etc. depend upon the direction along properties which
these are measured. The crystals are translucent i.e. less turbid and quite mobile i.e. can flow,
They scatter light strongly. Other examples of a nematic liquid crystal are:
(a) Para azoxyanizole (PAA) (Transition point H8°C and melting point 135°C)
° N-Q--OCHa
CH3-0--O-~=
Crystal 11S'C) Nematic Phase 13S'C) Isotropic liquid
(b) P-Azoxyphenetole (137-167°C)
k°
CHsCH2 0 - 0 - = N-0-0CH2CHs
(c) Anisoldazine (165-180°C)
CHs0-o-CH=N-N=CH--Q-0CH3
(d) P-Methoxy cinnamic acid (170°C-186°C)
CHs0-o-CH =
°
CH-~-OH
Cholesteric liquid crystals Chiral nematic liquid crystals also referred to as
(ii)
Cholesteric Liquid Crystals or Twisted Nematic Liquid Crystal (TNLC) are formed from optically
active compounds having chiral centers. Such liquid crystals are characterized by very high
optical rotation-thousands time greater than that of its crystalline variety. However, in these
crystals the orientation of the axes shifts in a regular way in going from one layer to the next
thereby giving a helical structure as shown in Fig. 6.2
(b). Because of this structure, cholesteric crystals have
remarkable optical property of reflecting light of different
colours under different condition e.g., at different
temperatures. Based upon their properties rings using
cholesteric liquid crystals are available which change
colour with person's mood. The name 'cholesteric' has
been given to these crystals because these substances
are all derivatives of cholesterol (but not cholesterol
itself). The first substance in which this type of
mesomorphism was detected was cholesteryl benzoate.
Its transition point in 145°C and melting point is 178°C.
The l-cholesteryl esters from formate to myristate are
amongst other examples of liquid crystals. Mixtures of Fig. 6.2 (b). Cholesteric liquid crystals.
various types of these liquids crystals are often used to
create sensors with a wide variety of responses to
temperature changes. Such sensors are used for
thermometers often in the form of heat sensitive film
to detect flow in circuit boar,l connection, fluid flow
pattern, condition of batteries and presence of a radiation.
(iii) Smectic or soap like lfquid crystals : The
world "smectic" is derived from the Greek word for soap.
On heating they retain long-range order, yielding smectic
phase. They lose periodicity with in the planes, but retain
the orientation and arrangement in equi-spaced planes
(see Fig. 6.2 (e». Thus, molecules in phase align
themselves in layers. When any stress is applied, one
plane glider over another. Soaps like cholesteryl oleyl Fig. 6.2 (c). Smectic liquid crystals.
carbonate exhibits smectic liquid state between O°C and
17°C.
These crystals are more turbid and viscous (less mobile) than nematic liquid crystals.
Frequently, a smectic substance is transformed into a nematic substance during the courS3 of
heating to a higher temperature.
Some examples of the compound yielding smectic type of liquid crystals are given below:
Ethyl p-azoxy benzoate (114--121°C)
Ethyl p-azoxy cinnamate (140--249°C)
n-octyl p-azoxy cinnamate (94--175°C)
Smectic liquid crystals also give x-ray diffraction patterns like solid crystals but it is in
one direction only. Thus smectic phase has a complex internal structure. \\Then viewed in
polarized light. smectic phases appear to have fan like appearance. They are always uniaxial
and are not affected by a magnetic field.
(2) LYOTROPIC LIQUID CRYSTALS
Lyotropic liquid crystals were actually discovered long before their thermotropic crystals.
These type of crystals occur in concentrated solutions of rod like molecules in a solvent like
water. Some compounds transform to a liquid crystal phase when mixed with as solvent. They
are usually obtained by mixing the compound in a solvent and increasing the concentrations
of compound till liquid crystal phase is observed. Such type of crystals are called Lyrotropic
liquid crystals. Lyotropic liquid crystals formation depend on two factors :
(a) Concentration of either the component or the solvent.
(b) Variation of temperature.
Examples: Soap-water mixture,
Sodium laurate in water,
Phospholipids-water mixture.
Lyotropic mesogens are typically amphiphilic, meaning that they are composed of both
lyophilic (solvent attracting) and lyophobic (solvent repelling) aparts. This causes them form
into micelles structure in the presence of a solvent, since the lyophobic ends will stay together
as the lyophilic ends extends outward towards of the solution. P. s the concentration of the
solution is increased and the solution is cooled, the micelles increase in size and this separates
the newly formed liquid crystalline state from the solvent. The amphiphilic soap molecules
arrange themselves in a bilayer in water solution so that there is minimum contact between
the paraffic tails and the water molecules. There are cubic and hexagonal arrangement of
amphiphilic molecules in water solution. There are number of application in biology of smectic
like, bilayer vesicles, the most important is the structure of the cell membrane.
6A.5 CHEMICAL CONSTITUTION AND LIQUID CRYSTALLINE BEHAVIOUR
In liquid crystals, the molecules possess orientational order i.e., the molecules tend to
remain oriented in a particular direction. The direction of preferred orientation in a liquid
crystal is called the director and may be imagined to be undirected towards the top or bottom
of the page. Since the molecules are in constant motion in liquid crystal phase, they spend
more time pointed along the director than along any other direction. Liquid crystalline
behaviour is dependent on the rigidity at the central portion of the elongated molecule. If the
molecule lacks rigidity bending may occur long its length destroying parallel arrangement of
molecules resulting in no liquid crystal formation. For example, long chain n-alkanes can have
elongated conformations but the flexible alkyl chain can coil and bend and hence no liquid
crystal can be formed from them. Very long chain n-alkanoic acids cannot form liquid crystals
because they are flexible.
CH -(CH. )-C
3 2X
/
"O-H...................................
N·alkanoic acid dimer
"
O···········..···················..·H-O
°,/'
/C-<CH 2)X CHa
If we introduce double bond this will makes the formation 01 mesophase because the
conjugated part makes the molecule rigid.
/o . . . . . . . . . . . . . . . . . .H-O "
CH.j-CH=CH-CH=CH-C /C-CH=CH-CH=CH-CHa
. "O-H................................... °,/'
Dimeric dienoic acid
Introduction of double bond in the side chain makes the formation liquid crystal phase
possible.
A very large number of chemical compounds are known to exhibit one or several liquid
crystalline phases. Besides differences in their chemical composition, these molecules have
some common features in chemical and physical properties. There are two types of thermotropic
liquid crystals.
(i) Discotics and (ii) Rod shaped molecules.
Discotics are flat disc like molecules consisting of a core of adjacent aromatic rings. This
allows for two dimensional columnar ordering. Rod shaped molecules have an elongated,
anisotropic geometry, which allows for preferential alignment along one spatial direction.
From the molecules structure it is also possible to predict whether a liquid crystal can be
formed.
(a) Salts of carboxylic acids ring with OR -CO OR, form smectic mesophase.
(b) Rings with terminal N0 2, CN, -OCH3 form nematic mesophase.
The most common rod like mesogens are given below:
-0-0- Rigid cores
o
Bridging groups are -C == C-, -N = N-, -CH = N-, -C-O-
Terminal groups are: n = Alkyl, n-alkyloxy, -CN, -CI , -N0 2 , -COR,
"
Example for low molar mass (LMM) liquid crystal, such as 5CB.
C5Hl~CN
P-n-pentyl-p' Cyanobiphenyl (PCB)
The bridging group should cause resulting compounds to have a linear planar conformation
and restrict the freedom of rotation. There groups can conjugate with phenylene rings enhancing
the anisotropic polarizability. This will help to increase
the molecular length and maintain the rigidity.
Aromatic compounds are polarizable, have a planer
structure and are rigid. Ifwe introduce an alkyl group
in suitable positions this will makes the molecule
elongated and such compounds now has mesophase. To
use the benzene nuclei for liquid crystal formation the
following condition should be fulfilled.
(i) The central part which links the two
benzene nuclei should itself be rigid. For
example, in para azoxyanisole the central
part consisting of azoxy group makes the
-.
central part rigid.
CH30-o-' N=N-o-~ OC!l3

o -
Fig. 6.3. Columnar liquid crystal.
P-Azoxyanisole
(ii) The two rings and the central part should constitute a rod like structure.
(iii) The central groups may involve a ring by dimerization. For example, in the case of
n-propyloxy benzoic acid which easily forms a mesophase. The ring in the central
part makes it rigid due to hydrogen bonding or dimerization.
/ 0 ................................... H-O ' "
n-pr-0-o-c'? /c-o-O-pr-n
"'O-H................................... O / "
n·Propyloxybenzoic acid dimer
(Pr-Propyl group)
(iv) The benzene ring should be linked through para substituents, then mesophase
formation is favoured. If it is linked through meta or ortho positions no mesophase
is there. If substituents are already present on the ortho and meta position of the
benzene nuclei and if ring linked through para position again the conditions are not
favourable for meso phase formation.
(v) Liquid crystals formed when two benzene rings are linked directly. Biphenyl have
substituents at 4,4' positions for linearity and rigidity.
For example, propyl (4-n-butoxybiphenyl)-4' carboxylate.
C4H9o--O--O-COOCH2 CH 2 CHa
These are also thermally stable.

SA.6 DIFFERENCE BETWEEN SOLIDS, LIQUIDS AND LIQUID CRYSTALS
The main difference between a solid, a liquid and a liquid crystal is in the "Long-range
order" of their molecules. In a crystalline solid, there is a complete long-range order whereas
in a liquid, there is almost complete long-range disorder or there is almost no long-range order
at all. Liquid crystals represent a "mesomorphic state" i.e., an intermediate state between a
solid and a liquid. They do not have a perfectly ordered arrangement of their molecules like
that of a solid, still they have more order than a liquid as observed from X-ray diffraction
studies. Further, as already mentioned some crystalline solids on heating form smectic liquid
crystals whereas some others give nematic liquid crystals. Both these types of liquid crystals
have less order than a solid but greater order than a liquid and also smectic liquid crystals
have more order than nematic liquid crystals. There are some crystalline solids which on heating
first form smectic types of liquid crystals which on further heating form nematic types of liquid
crystals which on further heating melt to form the clear liquid. A common example of this
type is that of cholesteryl myristate. The changes may be represented as follows :
Cholesteryl myristate , 72'C , Smectic Liquid , 78'C , Nematic Liquid ;=8=3='C~ Liquid
(Crystalline solid) Crystals Crystals
Thus there are two transition temperatures and one melting point.
To represent the structural differences between a solid, smectic liquid crystal, nematic liquid
crystal and a clear liquid diagrammatically, let us take the example of a crystalline solid of the
type of cholesteryl myristate. In the crystalline solid, there is a complete long range order in
the three dimensions i.e., all the molecules have the same orientation and have a
la) Crystalline solid (b) Smectic liquid crystals
(e) True liquid (d) True liquid
Fig. 6.4.
regular arrangement in different planes as shown in Fig. 6.4 (a). On heating, it forms a turbid,
called 'Smectic liquid crystal'. In this state, all molecules have the same orientation and they
are in equi-spaced planes but the arrangement within the planes is irregular as shown in
Fig. 6.4 (b), The substance is no longer a true crystal, although it has more order than a liquid.
On further heating, the turbidity decrease and at a particular temperature, a new state is
obtained called 'nematic state' in which molecules still have the same orientation but they are
no longer in equispaced planes as shown in Fig. 6.4 (e). Thus more disorder is introduced. Yet
some order is maintained because all the molecules still have the same orientation. On
further heating, even this order is lost and the substance is in the liquid state, as shown in
Fig. 6.4 (d).
(a) (b) (e)
These may be represented in a magnified way as follows :

{a) (b ), (c)
Fig. 6.5. Different types ofliquid crystals.
6A.7 MOLECULAR ARRANGEMENT IN VARIOUS STATES OF LIQUID CRYSTALS

Types of liquid crystals
On the basis of their molecular arrangement, the liquid crystals are classified into the
following three types:
(1) Nematic liquid crystals: In these crystals the molecules are lined up in such a way
that their long axes are parallel to each other but the molecules are not arranged in layer
(Fig. 6.5 (a». The parallel molecules can slide past each other. A magnified view of the molecular
arrangement in these three different types of liquid crystals has also been shown in Fig. 6.5
fa), (b) and (c).
(2) Smectic liquid crystals : In these crystals, the molecules not only have their long
axes parallel to each other but are also arranged in layers as shown in Fig. 6.5 (b).
These parallel molecules in places can slip past each other. Frequently, a smectic
substance is transformed into a nematic substance during the course of heating to a higher
temperature.
(3) Cholesteric liquid crystals: In these crystals, the arrangement of molecules is similar
to that of nematic liquid crystals. However, in these crystals, the orientation of the axes shifts
in a regular way in going from one layer to the next thereby giving a thereby giving a helical
structure, as shown in Fig. 6.5 (c).
6A.S HOMOLOGUES SERIES (PPAAND MBBA SERIES)

A series of compounds in which all the members have the same functional group and the
molecular formulae of adjacent members are differ by CH 2 is called a homologues series. As
the number of carbon atoms or chain length varies its thermal stability of the homologues
series all varies. It is seen that the molecular arrangement in liquid crystals is intermediate
between those of the solids and isotropic liquids. The molecules are free to move but are oriented
in a particular manner. But on heating the solid substances breakdown in stages. Therefore,
it is interesting to study how the arrangement changes on heating in a homologues. series of
liquid crystals.
PAA and MBBA homologues series
In the case of PPA (Para azoxy anisole) and MBBA (Para methoxy benzylidene para-n-
butyl aniline) the difference in the structure of two molecules is that in PAA the alkyl
group (CH3) are attached to benzene through oxygen atoms whereas in (MBBA) the alkyl group
is directly attached to the benzene from one side and through oxygen from other side.
The liquid crystals of (PAA) are stable at higher temperatures (between 118°C and 135°C)
whereas the liquid crystals of (MBBA) series are stable at lower temperatures (between 20°C
and 70°C).
CH30 - 0
_ - ' N..= N_- o - ' OCH 3
o
P-Azoxyanisole (PAA)
P -Methoxy benzylidene-P-n-butylaniline
All the different compounds of (PAA) and (MBBA) forms homologues series.
The various homologues of (PAA) as shown below:
No. of carbon atoms

inside chain
2
24
PAA has more than 12 homologues
The graphical representation of different phases and transition temperature of the

homologues series of (PAA) and (MBBA) series is shown in figure (a) and (b).
1 Vv~
140
C,)
0
Q) 120 Nematic .a ..... t::. ...
...,'::s"'
cU
'"'
Q)
Q. 100
•.••"'.. Sm.ot', C CH,O--@-N=r--@-OCH,
S
~ o
(PAA)
80 Solid
4 6 8 10 12
---.~ Number of C atoms
Fig. (a). Graphical representation of different phases and transition temperatures
of the homologues series of P-azoxy anisole.
I
C,)
0
Q)
60
40
CHaO-@-CH=N-@- C4H 9
MBBA
.EcU'"'
'0-"'
Q)
20
e: Solid
~
4 5 6 7 8
- - -..~ Number of C atoms
Fig. (b).Graphical representation of different phases and transition temperatures of
the homologues series of P-methoxy benzylidene-P-n-butylaniline (MBBA).
In these representation the upper curve shows the transition from liquid crystal state
to liquid state and the lower curve shows the transition from solid state to the liquid crystal
state. In general, in all the series, in a curve, as the number of carbon atoms increases the
transition temperature varies and for higher homologues, there is no variation in the transition
temperature with change in number of carbon atoms.
In case of (PAA), the molecules with even number of carbon atoms are generally have
higher transition temperature and those having odd number of carbon atoms. But in case of
(MBBA) the odd having higher temperature than the even number of carbon atoms. The
members of the (MBBA) series do not show smectic phase. They show transition from solid to
nematic to isotropic liquid state.
By changing the length of the flexible side chain at the terminal position, the transition
temperature of the compounds can be changed. Biphenyl, terphenyl systems also show lower
transition temperatures. Such compounds with low transition temperature have extensive
applications in liquid crystal display systems. Few examples are given below:
C5H l t @ - @ - C N
4-n-Octyloxy-4' cyanobiphenyl
CN
4-n-Pentyl 4'-cyano-P-terphenyl
[ FOLLOW-UP PROBLEMS)
1. What are liquid crystals?

2. What are main characteristics of liquid crystals?
3. Which substances generally behave as liquid crystals?
4. What is the main distinguishing character of liquid crystals?
5. What is the difference between liquid crystals, solid and liquid ?
6. How the liquid crystals are classified ?
7. What are thermotropic liquid crystals?
8. How the thermotropic liquid crystals are classified ?
9. What are Nematic liquid crystals?
10. Which type ofliquid crystals exhibit uniaxial symmetry?
11. Which type of liquid crystals form a helix and possess chiral centre?
12. What is the director in liquid crystals terminology ?
13. What are smectic liquid crystals?
14. What are cholesteric liquid crystals?
15. Which was the first substance used as cholesteric liquid crystals?
16. Why the name cholesteric has been given to these cr)Tstals ?
17. When does Lyotrophic liquid crystal formed?
18. Give an examples of Lyotrophic crystals.
19. Give an example of nematic liquid crystalline compound.
20. Give an example of Smectic liquid crystalline compound.
21. Which type ofliquid crystal are used in measuring temperature?
22. What do you mean by homologues series?
23. What do you mean by PAA ?
24. What do you mean by MBBA ?
[ANSWERS)
1. Liquid crystals are anisotropic liquids which show different physical properties in
different direction particularly in their optical behaviour. Anisotropic properties like
double refraction are associated with crystalline state, the turbid liquids are called
liquid crystals.
Or
Liquid crystals are highway anisotropic fluids that exist between the boundaries of
the solid and the isotropic liquid phase.
2. Liquid crystals are long, narrow elongated molecules having sufficient molecular
interactions and exhibit measophase i.e., optical anisotropy or easily polarizable
substituents.
3. Substances behave as liquid crystals are usually long chain organic molecules either
terminating in groups such as -OR, -COOR, or having groups like -C=N-,
-N=NO-, -C=C- in the middle. For example-Cholesteryl benzoate.
4. The main distinguishing character of the liquid crystals is the tendency of the molecules
possess orientational order i.e., the molecules tends to remain oriented in a particular
direction which is called the director.
5. The main difference between a solid, a liquid and a liquid crystals is in the "long
range order" of their molecules. In a crystalline solid, there is a complete long range
order whereas in a liquid, there is almost no long range disorder, or but liquid crystals
shows "mesomorphic state i.e., is an intermediate state between a solid and a liquid.
They do not have a perfectly ordered arrangement like that of solid still they have
more order than liquid."
6. On the basis of their molecular arrangement, the liquid crystals are classified as
nematic, smectic and Cholesteric liquid crystals.
7. The class of compounds that exhibit liquid crystalline behaviour on variation of
temperature alone are referred to as thermotropic liquid crystals.
8. They are of two types i.e., nematic and smectic liquid crystals.
9. Nematic liquid crystals are formed by a compounds that are optically inactive. They
have elongated shape and are parallel to each other along the long molecular axes.
10. Nematic liquid crystals.
11. Cholesteric liquid crystals.
12. The direction of a preferred orientation in a liquid crystal is called the director.
13. In this type of crystals the molecules have not only long axes parallel but are also
arranged in layers. Molecules remains in their ovm planes while plane slide past each
other.
14. Molecules are arranged in thin layers similar to nematic crystals but orientation of
the axes shifts regularly in going form one layer to the next.
15. Cholesteryl benzoate.
16. Because these substances are all derivatives of cholesterol.
17. This form occur in concentrated solution of rod like molecules in an isotropic solvent
(usually water).
18. Sodium laurate in water and phosphatidyl choline in water.
19. P-azoxy anisole.
20. p-n-octyloxy benzoic acid.
21. Cholesteric liquid crystal.
22. A series of compounds of the same type in which all the members have the same
functional group and the molecular formulae of adjacent members differ by CH 2 is
called a homologues series.
23. Para azoxyanisole.
24. Para methoxy benzylidene para-n-butylaniline.
6A.S APPLICATIONS OF LIQUID CRYSTALS
One of the most important application of liquid crystals (smectic and nematic type) has
been in the electronic industry. They are being used in thin light weight display devices such
as digital watches, pocket calculator and similar instruments. As this is done with the help of
liquid crystals, it is called liquid crystal display (LCD). They can be used to record, store and
display images which can be projected on to a large screen. They also have potential as
television displays.
1. Display system
The two modes most widely used in liquid Current Current
crystals displays are dynamic-scattering and field _ off on
effect. A thin film of liquid crystals, not more than
one thousandth of an inch thick is placed between
two sheets of glass, one of which is coated on one
side with a thin layer of an electrically conductive
material such as tin oxide. When no current is
passing through the conductive coating, the
molecules are uniformly oriented and the light can Ca) (b)
pass through the cell. When the current is applied Fig. 6.6. Principle of working of a liquid
the molecular alignment changes (because the liquid crystal cell.
crystal molecules are polar) and the cell appears (a) light passes through nematic
opaque or black [Fig. 6.6 (aJ and (b)]. Thus a number liquid crystal when no electrical current is
or a letter is displayed in black against a silvery passed.
background. (b) light is scattered when molecules
are disordered due to passing of electric
A liquid crystal display requires a very small current.
current i.e., it consumes very little power, electronic
watches and calculators run for years with a small battery. Most of the display in LCD watches
and calculators are composed of several 7 segments. Each 7 segment section can display one
number. The combination ofthese sections displays the numbers (Fig. 6.7).
D [J [J
1_11_1 []
1_11_11_ _ _ FI
CI FII=! _ 1=1
_
(1) (2) (3) (4) (5) (6) (7) (8) (9)
Fig. 6.7. 7-segment display.

Similarly, for alpha numeric display, there are 14 segments (A segment means an adive
area in the display or image area). The complete display panel is composed of two polarizer
that is transmit light in perpendicular directions, a mirrored surface and layer of liquid crystal
material between two glass plates as shown in Fig. 6.8 (a).
Glass plate
Ii L'lqUi'd Liquid
No voltage I+-crystal +-crystal
applied molecules
i molecules
I
Glass plate
(n)
Mirror
o (b)
Fig. 6.8 (a). All liquid crystal molecules are precisely aligned in absence of the applied voltage and light
passes through both the polarizers and reflected back.
(b). Alignment of the liquid molecules is lost when a voltage is applied to a segment in the panel.
The segment then appears black against a silvery background.
In absence of the applied voltage, the liquid crystals molecules in all segments are precisely
aligned. Therefore the entire panel appears silvery because light passes through both the
polarizers, reflects off the mirrored surface and then again passes through both the polarizers.
When voltage is applied to the segment of a display, the precise alignment of the liquid
crystal molecules is lost as shown in Fig. 6.8 (b), This results in the polarized light from the
first polarizer not being rotated by the required 90° to align with the second polarizer. The
second polarizer blocks the passage of light and causes the segment of the panel to appear
black.
Starting from the wrist watches in 1970s, the use of liquid crystal displays has grown
enormously. They are used in calculation, note book computer, cell phones, television and many
other portable devices where in low power consumption and low voltage operation are important.
Dyes used in liquid crystal display give desired colours to the display with a good contrast.
Due to less consumption of power as composed to other display they are used in :
(i) Automobile dashboards indicators, traffic signals, advertisement boards and petrol
pump indicators.
(ii) Various analytical instruments like pH meters, conductometers, colorimeters and
potentiometers.
(iii) Various electronic gadgets including watches, calculators, mobile telephones and lap
top computers.
2. Thermography
It is a technique of recording the temperature various especially of the skin on a graph.
The record thus obtained is called 'thermograph'. It is based upon the fact that because of
the helix structure of the cholesteric liquid crystals, they have the remarkable optical property
of reflecting light of different colours under different temperatures. This is because the helical
structure has a characteristics pitch length. These pitch lengths are in the range of the
wavelengths of visible light. The pitch length changing on changes the temperature, but the
chemical structure of the helix remains unaffected. The colour change may be positive or
negative. Thus. when the temperature decreases, the colour change may be from violet to
blue to green to yellow and then to red for some cholesteric meso phases while for some others
the change may be in the reverse order.
The properties of different liquid crystals are described in terms of event temperature and
clearing point temperature. The lowest temperature where liquid crystals scatter visible light
is called event temperature. At a temperature below this temperature, the liquid crystals will
be in the solid state and will appear transparent. The temperature above which it becomes
pure liquid is called the clearing point temperature. Depending upon the requirement, the
suitable liquid crystals can be selected which reflects light of different colour in the desired
temperature range. Temperature dependence of the colour reflected by liquid crystals has been
utilized for application in thermography. Temperature variations of less than O.Ol°C can be
distinguished visually with liquid crystals temperature sensors. The various applications of
thermography in different fields are as :
(i) Medical thermography: The most important application of thermography has been
in the medical field in the recent years, especially in the early detection or diagnosis
of tumour or breast cancer besides orthopedic disordes such as arthritis and back
pain etc. The basic principle is that heat changes produced in the affected skin are
different from the healthy skin. Earlier, the physicians used to point the liquid crystals
on the portion of the body to examined but this method was too rough. Now the
method is simple. The liquid crystals are pressed against the healthier part as well
as the part to be examined and the colour photographs are taken of the resulting
patterns of colours and then compared. Liquid crystals are also used in disposable
thermometers. Liquid crystal temperature sensors have also been used as bio-feed
back (heart rate, blood pressure, ECG) and in psychotherapy.
(ii I Radiation and pressure sensors : Cholesteric liquid crystals have been used in
versatile and inexpensive radiation sensors. These devices are based on the principle
of conversion of radiation energy into heat energy and the measurement of the heat
energy using a thermal transducer. From the transducer the radiation can be detected
directly by the change in colour. Ultraviolet, infrared, microwave, ultrasonic and
ionizing radiation transducers have been devised based on this principle. Liquid crystals
films have been used as recording media in holograms. (Homography is a technique
which records and reconstructs the wave front emanating from the illuminated light.)
(iii) Thermography in electronic industry: The liquid crystals devices are used to
detect the point from where the electronic components get failure. Due to failure at
certain point in the components leads to localized heating at that spot and can be
detected by the change in colour of cholesteric liquid crystals.
(iv) Detection of air pollutants : The liquid crystals have been used to detect the
impurities in the atmosphere. The colour of the liquid crystals changes in the presence
of im purities.
3. In Research work
Liquid crystals are employed as solvents, during the spectroscopic studies of structure of
anisotropic molecules. High resolution NMR spectroscopy on such partially oriented molecules
has provided a new method of determining molecular structure particularly for small molecules.
Some liquids crystals have been used in chromatographic separation, as solvent to study the
course of reaction and to study the molecular rearrangements of kinetics, also used as fluid in
ultraviolet and infrared spectroscopy to detect the structure of an organic compound.
4. Other application
They are used in medical applications, such as blood pressure instruments, digital
thermometers terminate pressure transmitted by a walking foot on the ground is measure.
Many biological systems exhibit the properties of liquid crystals. Living tissue such as muscle,
tendon, ovary, adrenal cortex and nerve show the optical birefringence (Bifringence is the
splitting of incident light into two rays vibrating at right angles to each other and causing two
images to appear.)
A liquid crystal phase has been implicated in at least two degenerative diseases, e.g.,
atherosclerosis and sickle cell anemia. In the medical profession a lyotropic liquid crystals can
coat a drug to keep it from being destroyed in the digestive tract. Lyotropic crystals are used
in making stable hydrocarbon foams. Low molar mass liquid crystals (LMM) have used in
erasable optical disks, full colours, 'electronic slides' for computer-aided drawing, and light
modulators for colour electronic imaging.
[r-F-O-LL-O-W--UP--P-R-O-B-LE-M-s---')
1. What do you mean by LCD?

2. Mention a few uses of liquid crystal display.
3. How many segments sections are in LCD watches and calculators?
4. What do you mean by a segment '?
5. How many segments section are in LCD for alphanumeric display?
6. How ma:'1Y polarizers are in a complete display panel?
7. What ar" the various uses of cholesteric liquid crystals in medicines?
8. Why llquid crystals are used in watches, calculator and other electronic gadgets?
9. How doe,1 liquid crystals help in research work?
10. What, are the various application of liquid crystals in thermography?
11. Mention me application oflyotropic crystals in medicine.
(ANSWERS )
1. Liquid crystal display.
2. They are being used in thin light weight display devices such as digital watches, pocket
calcu~ator, mobile phones, laptop computers and related electronic gadgets.
3. 7-segment section.
4. A segment means an active area in the display or image area.
5. There are 14-segments section.
6. Two polarizer.
7. Liquid crystals are used in disposable thermometer. Using the variation in colour of
liquid crystals with change in temperature, the paths of arteries and veins can be
detected. This helps in detection of blockage in veins and arteries. This also helps to
locate injections, tumors and fetal placenta, which are wormer than the surrounding
tissues.
8. Th~y operate at low voltage and consumer less power as compare to other display.
9. Liquid crystals are employed as solvent in spectroscopic studies like NMR, IR and
lTV. It is used in pH meters, conductometer, colorimeter, potentiometer and other
analytical instruments to detect the structure of various organic compound.
10. (i) They are used in disposable thermometer.
(ii) They are used to locate veins, arteries, injections, tumors.
(iii) The point of failure of electronic components can be detected.
(iv) Evaluating efficiency of heat exchangers in studies of the conversion of mechanical
to thermal energy.
11. A lyotropic crystals can coat a drug to keep it from being destroyed in the digestive
tract.
1. What are liquid crystals? Mention their characteristics. Which substances generally
behave as liquid crystals?
2. Explain the terms in brief: (i) Anisotropy (ii) Isotropy.
3. How are the liquid crystals classified? Differentiate between smectic liquid and
nematic liquid crystals?
4. Give an account of Boss's swarm theory of liquid crystals. How does this theory account
for the turbidity in liquid crystals?
5. Differentiate between thermotropic and lyotropic liquid crystals.
6. What are thermotropic liquid crystals? Write their characteristics.
7. What are lyotropic liquid crystals?
8. What is the significance of director in liquid crystal terminology ?
9. What are cholesteric liquid crystals? Explain its application in thermography.
10. Give a brief account of the molecules arrangement. Which exists in various states of
liquid crystals ? How would you account for the forbidding observed in liquid
crystals?
11. Explain the terms: anisotropy, mesomorphic state, nematic phase, smectic phase and
cholesteric phase.
12. Give an account of chemical properties ofliquid crystals.
13. Write the applications of liquid crystals in thermography.
14. Write an account of applications of liquid crystals in display.
15. What do you mean by LCD? Explain the electro-optic effect of liquid crystals.
16. Write the application ofliquid crystal in the field of medicine.
17. What is the basic principle ofliquid crystal display? How is it used as seven segment
cell ?
18. What are thermochromic liquid crystals? Discuss in brief the basic features of liquid
crystal thermography.
19. Briefly describe the applications ofliquid crystais in electronic industry. What type of
liquid crystals are used?
20. Briefly explain the application of liquid crystals in clinical field. What type of liquid
crystals are used ?
21. Explain the difference between liquid crystal, solid and liquid.
22. Write a short note on "thermography".
23. Briefly describe the principle ofliquid crystal display in watches and calculators.
24. Explain the liquid crystalline behaviour in the following homologues series with
examples:
(a) Para azoxy anisole (PAA) series
(b) MBBA series.
25 . (a) Describe the nematic and cholesteric phases of thermotropic liquid crystals.
(b) Explain the applications of liquid crystals in display systems.
(VTU, B.E., Jan. / Feb. 2003)
26. (a) What are liquid crystals? Distinguish between thermotropic and lyotropic liquid
crystals with suitable examples.
(b) Explain the applications ofliquid crystals displays. (VTU, B.E., July / Aug. 2004)
27. What are liquid crystals? Explain the molecular ordering in the following liquid crystal
phases.
(i) Nematic phase (ii) Chiral nematic phase (iii) Semectic phase.
(VTU, B.E., Feb. / March 2005)
INSTRUMENTAL METHODS
OF ANALYSIS
SYLLABUS
Theory, Instrumentation and applications of Colorimetry, Potentiometry, Conductometry
and Flame photometry.
6B.l INTRODUCTION
The goal of a chemical analysis is to provide information about the composition of a sample
under examination. In qualitative analysis, information regarding the presence or absence of
one or more components of the sample is sufficient, whereas in quantitative analysis, the
question is : How much is present? So, chemical analysis is defined as :
"The science ofidentifying what chemical component/components a sample contains and
establishing their proportions on an absolute basis." The analysis can be subdivided into two
important forms.
Qualitative analysis : determining what species are present.
Quantitative analysis: determining how much of a species is present.
Anaiytical chemistry is the science of making quantitative measurements. There are many
analytical methods employed for the detection and estimation of analytes, some of them are :
(i) Physical methods bas~d on mass, volume, colour, refractive index, thermal conductance
etc:.
(ii) Interaction with electromagnetic radiations (spectroscopy) such as absorption, emission
and scattering etc.
(iii) Related ~ith electric charge i.e., electrochemistry, potentiometry, polarogz:aphy, mass
spectrometry etc.
1'he required information is obtained by measuring some physical property that is
.characteristics of component or components of interest. In instrumental analysis, a physical
property of a substance is measured for determining its chemical composition. Instrumental
methods of analysis are ordinarily classified according to the propertY,that is observed in the
final measurement process, Some of the important properties and names of the concerned
techniques are given as under: .
Instrumental Methods ofAnalysis 215
"
Physical Property Instrumental or Analytical Method

Mass Gravimetry or Gravimetric analysis
Volume Volumetry or Volumetric analysis
Temperature Thermal methods such as TGA, DTA, DSC etc.
Conductance Conductometry or Conductometric analysis
Electric potential Potentiometry, Electrochemistry, Polarography
Absorption of radiation Spectrophotometry (X-ray, UV, Visible, IR
Colourimetry, NMR, ESR.
Emission of radiation Emission spectroscopy, Flame photometry,
Fluorescence .
Scattering of radiation Raman spectroscopy
Refraction of radiation Refractometry
Optical rotation of radiation Polarimetry
Diffraction of radiation X-ray diffraction methods
Absorption of colour Absorption spectroscopy (colourimetry)
Surface adsorption of partition Chromatography (column, thin layer, paper, ion-
exchange etc.)
Besides the above mentioned techniques, many other methods have been developed.
Keeping in view the scope of syllabus, only three techniques namely colorimetry, conductometry
and potentiometry have been discussed in this unit. .
6B.2 COLORIMETRY
Theory
This method is specially used for the systems in which substances or their solutions are
coloured. This is a spectroscopic technique, qualitative or quantitative, depending upon the
measurement of an absorption spectrum and is called absorption spectroscopy. The intensity
of colour can easily be measured by using a photoelectric colorimeter. When a beam of
monochromatic light falls on a homogenous medium a portion of the incident light is reflected,
a portion is absorbed and the remainder is transmitted.
(, = 1(1 + Ir + It
In case of aqueous solution, Ir is negligible as compared to Ia and II
10 = Ia + II'
The concentration of the solution can be obtained by using Lambert-Beer law.
According to this :
The reLte of decrease in intensity of a beam of monochromatic radiation with thickness of
the solution is proportional to the intensity of incident radiation as well as concentration of
the solu.tion.
Mathematically,
dl
x Cl
dx
dl
or
I = - r. Cdx.
It can also be stated as:
I t = I 0 lO-wl
Where C is the concentration of solute expressed in mole/liter, 1 in the length of the cell
and L is the constant characteristic of the solute called molar extinction coefficient or molar
absorptivity. Taking logarithm of both sides.
og It = log 10 - ek C l
or
Where A is called absorbance or optical density (OD).

It
Transmittance 'T' of a solution in the ratio of I o
i.e., the fraction of incident light
transmitted by solution.
T = !.L-
10
It
or -logT = log -10 =A
or A= -log T =ekCl
Therefore the study of variation in intensity of a given coloured solution with the change
in concentration of the given coloured component is termed as colorimetric analysis. The sample
absorbs a portion of the incident radiation; the remainder is transmitted on to a detector where
it is changed into an electrical signal and displayed, usually after amplification, on a meter,
chart recorder or some type of read out device.
When a species under test is colourless, then a suitable complexing agent is added to the
solution so that a coloured complex (which can absorb light in the visible region) is obtained.
For example, for the estimation of cuprous ions, complexing agent, ammonium hydroxide, is
added to get blue coloured solution.
Colorimeter offer an economic advantages over dispersive instruments, as well as increase
luminosity, particularly when utilizing the interference type filter.
6D.3 INSTRUMENTATION
In a colorimeter, a narrow beam of light of proper wave length passes through the solution
under test towards a sensitive photocell. The instrument modules are shown in schematic form
in Fig. 6.9.
Fig. 6.9. Instrument modules for measuring absorption of radiation.

The instrument include.
(i) Source:An intense source of radiant energy. The source of radiation is the important
requirement. It must generate beam with sufficient power for ready detection and
Instrumental Methods ofAnalysis 217.
measurement. It should be stable and provide continuous radiation. ~e most common
source of visible radiation is the Incandescent tungsten filament lamp.
(ii) Filters and monochromators : In general, filter isolate a wide band than the
monochromator, but some interference filters have a narrow half intensity band Width
than some monochromator. Filter photometer make use of filters and
spectrophotometers employ monochromators.
Two types of filters are used:
(a) Adsorption filters
(b) Interference filters.
A monochromator consists of entrance and exit slits and a dispersing device, either a prism
or grating, so arranged that radiant energy of a relatively narrow spectral band width is obtained.
Many modern monochromators contain two dispersing elements i.e., two prisms, two grating
or a prism and a grating. This arrangement provides greater dispersion and spectral resolution.
(iii) Cuvette : The cuvette must be constructed of such a material which is unable to
give any absorption in the selected range of measurement. For example, the cuvette
must be made of quartz if the work has been done in the UV region. For visible region
they are made of colour fused glasses. The thickness of cuvetts depends on the
absorption. They must be rectangular or cylindrical in shape. Cell thickness of 1, 2
and 5 cm are quite common.
(iv) Radiation detector and indicators : These photoelectric ·devices convert radiant
energy into an electrical signal. To be useful detector must have the following
important requirements:
(a) It must respond to radiant energy over a broad wave length range.
(b) It should be sensitive to low levels of radiant power.
(c) It should have a relatively low noise level.
(d) The signal produced be directly proportional to the power of beam striking it.
There are three basic photoelectric devices used i.e. photo voltaic cells, photo tubes or
photo conductive cells.
6B.4 WORKING
A single beam, direct reading, filter photometer or colorimeter is illustrated in Fig. 6.10.
The optical path is simply from the light source, through the futer and sample holder, and to
the detector. After passing the light from the tungsten-filament lamp through the sample
cuvette, the light strikes the surface of a photovoltaic cell, the output of which is measured by
the deflection of a rugged light spot galvanometer. The lamp is charged by a storage battery.
The accuracy of about 2% in transmittance under optimum conditions.
To operate this instrument, first blank solvent or reference solution is taken in the cuvette
and the instrument is adjusted to read 0% transmittance when no light is passes to the detector
and 100% with the shutter open and light on. Mter these adjustments have been made, then
the sample is placed in the light path and the absorption or transmittance read.
If 10 in the intensity for the light which passes through the solution and It be the intensity
of the same light when it passes through solvent, then 101 It known as transmittance: Once
10 1It Jor a pure liquid is obtained and the thickness of cell (cuvette) used is known, the absorption
Filter holtier·-__'T ,...--Light shield
Lamp control
rheostats
JBt-1~m-Photocell
6-V storage
battery or To galvanometer
voltage -lJ~c:>-"':::'"
regulator
lamp on
Colorimeter
lamp brighter
(a)
(b)
Fig. 6.10. Schematic optical and electrical diagram of a single-beam photometer,

or extinction coefficient for the given wave length can readily be calculated, Similarly from
the measured 101 It and the known values of C and t may found the molar absorption or
extinction coefficient. If log 10 1It is plotted against A. maximum absorptions will be given by
the maxima in the curves. But when log IolIt is plotted against A. then the minimum in the
curves will corresponds to the maxima in absorption. An absorption curve for benzene is shown
in Fig. 6.11 from which it is evident that benzene has the maximum absorption around 2550 A
wave length.
1.00
0.80
log 10 1I, 0.60
0.4{)
0.20
1 2200 2300 2400 2500 2600 2700 2800 2900 3000

I.A
Fig. 6.11. Absorption curve for benzene.
8D.5 APPLICATIONS
Absorption spectroscopy is one of the important useful tools for the most important
characteristics of photometry methods are their wide applicability, high sensitivity, moderate
to high selectivity, good accuracy. A wide variety of inorganic and organic species absorb in the
IN and visible region and thus susceptible to quantitative analysis. Even many non absorbing
species can be analysed after converting them to absorbing species by making use of suitable
chemical treatment.
There are numerous applications of quantitative absorption methods. A number of inorganic
species also absorb and are susceptible to direct determination. A number of other species such'
as permanganate, nitrate, chromate ions, ozone, osmium etc. have also been found to show
characteristics absorption.
A large number of reagents react with non-absorbing species to yield products that
absorb strongly is the IN and visible region. Thus substances that do not show useful
absorption can also be determined by adding a reagent to form an absorbing complex or other
chromophore. Typical inorganic reagents are thiocyanate for Fe, Co and Mo, iodide ion for
Bi, Pd and Te.
Organic chelating agents which form stable coloured complex with cations are 0-
Phenanthroline for Fe, dimethylglyoxime for Ni, diethyl dithio carbamate for Cu, Dithizone is
a very good reagent for this purpose and is soluble in chloroform. It gives red or violet complexes
when react with cations of transition metals.
Mn(lI) ion and its common salts are colourless. However oxidation ofMn2+ to Mn7+ produces
the purple coloured species Mn0 4-. This colours is very intense and hence small amount of
Mn can be detected. Some ions such as C02+, Cu2+, Ni2+ solution are pink, blue and green
respectively, but their colours are not very intens~ (because molar absorptivities are low).
Determination of Mn has widely been used in steel, alloys and ore samples where Mn is a
minor constituent.
1. What are electromagnetic radiations?

2. What are the characteristics of electromagnetic radiations?
3. How an electromagnetic radiation is produced ?
4. Name some important electromagnetic radiations.
5. What is Lambert-Beer law?
6. Define wave length and frequency of a wave. How are they related ?
7. How is the energy of a wave related to frequency or wave length?
8. What is electromagnetic spectrum?
9. What is the visible region of the electromagnetic radiations?
10. What are ultraviolet and infrared radiations?
11. What is the basis of colorimetric analysis?
12. What is a spectrophotometer?
13. What do you mean by Amax of a solution?
14. How will you determine the value of Amax ?
15. Which is the most common source use for visible radiation?
16. What type of material is used for the cuvette?
17. What are the important requirements for a good detector?
18. What should be the shape of a cuvette?
19. Name the different photoelectric devices used in the colorimeter.
20. What are the various inorganic reagents used for colorimetry ?
21. What are the various organic chelating agents used for colorimetry?
(ANSWERS )
1. Different forms of energy which are propagated in space in the form of waves and
are associated with electric and magnetic fields perpendicular to each other and to
the direction of propagation.
2. All forms of electromagnetic radiations travel with the same velocity (3.0 x 1010 cm!
sec) and require no medium for their transmission. All the radiations are characterised
in terms of their wave length, frequency, velocity, wave number and amplitude.
3. An electromagnetic radiations is produced by the oscillation of a magnet in an electric
field or by oscillation of a charged body in a magnetic field.
4. Light, ultraviolet, radio waves, television waves, micro waves, x-rays and cosmic rays
etc.
5. The rates of decrease of intensity of beam of monochromatic radiation with thickness
of the solution is proportional to the intensity of incident radiation as well as
concentration of the solution. I
6. The shortest distance between any successive crests or through or any two similar
points on the wave is called wave length. The number of waves that pass through a
fixed point per second is called frequency of the wave.
c
Frequency (v) = i
Where c is the velocity and t.. is the wave length. As the wave length of a radiation
decrease, its frequency increases and energy also increases.
7. E = hv = ~ [v = f]
where E is the energy, v is the frequency, t.. is the wave length and c is the velocity
of radiation, h is a Plank's constant (6.626 x 10-34 Joule second).
8. The arrangements of different types of electromagnetic radiations in the form of
increasing wave length (or decreasing frequency) is known as electromagnetic
spectrum as shown below:
IncreaSing wave length
Cosmic yrays x-rays UV Visible IR Micro Radar Television Radio
rays waves waves waves waves
9. Visible light is only a small portion of electroma~etic radil:~tions, which we can see
Wave length of visible region is approx. 3800 A to 7600 A. It ranges from violet
(t.. =380 nm) to red (t.. =760 nm).
10. Radiations with frequencies higher and wave length lower than those of violet
radiations are known as ultra-violet radiation. Radiations with frequencies lower than
red radiations of the visible region are called infra-red radiations.
11. The variation of colour of a solution with change in concentration of suitable ions
form the basis of colorimetry, it involves the determination of the concentration of a
substance by measurement of the relative absorption of light w.r.t. a solution of known
concentration. The analysis which involves the measurement of absorption of light
radiations in visible region of the spectrum is called colorimetric analysis.
12. It is an instrument which compares the intensity of the transmitted light with that
of the incident light. It detects the percentage transmittance of light radiation when
light of certain intensity and frequency range is passed through the sample solution.
13. The value of the wave length corresponding to the minimum value of optical density
or maximum transmittance (100%) is called Amax for a particular solution.
14. The value "'max can be obtained from the graph between wave length on the x-axis
and O.D. on the y-axis. The extra pollution of 'the curve upto the x-axis given the
value of "'max of a particular solution.
15. The most common source of visible radiation is the incandenscent tungsten filament
lamp.
16. The cuvette must be made from that material which is unable to give any absorption
in the selected range of measurement. For example, cuvette must be made from
quartz.
17. The important requirement of a good detector are:
(i) It must respond to radiant energy.
(ii) It should have a relatively low noise level.
(iii) It should be sensitive to low levels of radiant power.
18. It must be rectangular or cylindrical in shape.
19. Photovoltaic cells, photo tubes and photo conductive cells.
20. Typical inorganic reagents are thiocyanate for Fe, Co and Mo ion for Bi, Pd and Te.
21. The various organic chelating agents are O-phenanthroline, dimethyl glyoxime, diethyl
dithiocarbamate and dithizone.
6B.6 POTENTIOMETRY
It is seen that the potential of a reversible electrode, depends upon the activity of ions
with which it is in equilibrium. It is, therefore, possible to follow activity changes during a
titration by the determination of potential of such an electrode, relative to some reference
electrode. This titration known as potentiometric titration or electrometric titration may be
used as a convenient and accurate method of analysis. Potentiometric titration has the follOwing
advantages:
(i) It can be used in coloured solutions, e.g., where ordinary titration fails with suitable
indicator.
(ii) No external indicator is used in oxidation-reduction titrations.
(iii) It can be used for titrating weak acids against weak alkalies.
6B.7 THEORY
The potentiometric titration is based upon the fact, that near the end point there is a
sudden change in the E.M.F. of a hydrogen or another standard electrode. When any
potentiometric titration is being performed, interest is focused upon changes in the E.M.F. of
the electrochemical cell as a titrant of precisely known concentration is added to a solution of
the test element. The method can be applied to any titrimetric reaction for which an indicator
electrode is available to follow the activity of at least one of the substances involved.
Requirement for reference electrodes are greatly relaxed; it is only necessary that the response
of one member of a pair of electrodes be substantially greater or faster than that of the other.
In addition to the establishment of the equivalence point of a reaction, further information
about the sample and its reactions may be obtained by the complete recording of a
potentiometric titration curve.
The chief advantages of potentiometric titrations are applicability to turbid, fluorescent,
opaque or coloured solutions, or when suitable visual indicators are unavailable or inapplicable.
Equipment needed to carry out a potentiometric titration is illustrated in Fig. 6.12.
To
~_.pPotentiometer+---......
Standard
alkali solution
H2 (1 atm)
r- +-- Agar-KCI
I /bridge
~~
Acid solution
to be titrated
Automatic stirrer
running at
low speed
Fig. 6.12. Apparatus for potentiometric titrations.

The critical problem in a titration is the recognition of the point at which the quantities of
reacting species are present in equivalent amount-equivalent point. The titration curve can
be followed point by point, plotting as ordinate successive values of the cell e.m.f. versus the
corresponding volume (or milli-
equivalents) of titrant added as abscissa.
Addition of titrant should be the smallest 10.0
accurately measured increments that 9.5
provide an adequate density of points 9.0
across the pH range. Over most of the 8.5
titration range the cell e.m.f. varies pH 8.0 l4----Inflection
point
gradually, but near the end point the cell
7.5
e.m.f. change very abruptly as the
logarithm of the concentration undergoes 7.0
a rapid variation. The resulting titration 6.5
curve will shown in Fig. 6.13. 6.0 "'------,-----t----.,------
19.5 20.0 20.5
The end point can be located from the
inflection point of the. titration curve, the Volume of titrant added, ml
point which corresponds to maximum Fig. 6.13. Experimental titration curve.
rate of change cell e.m.f. per unit volume of titrant added. Once the cell e.m.f. has been
established for a given titration, it can be used to indicate subsequented points for the same
chemical reaction.
6B.8 Measurement of Electrode Potential
The absolute values of single electrode potential can be measured directly. However the
same can be evaluated by connecting the given electrode with some reference electrode such
as standard hydrogen electrode and then measuring the e.m.f. of the cell formed. Since the
potential of standard hydrogen electrode is taken to be zero, therefore, the measured e.m.f.
gives the potential of the electrode under consideration. The value of the electrode potential
depends upon:
(i) The nature of metal.
(ii) The concentration of metal ion in solution.
(iii) The temperature.
If the temperature is 25°C and concentration of metal ion is 1 M, the resulting electrode
potential is called standard electrode potential.
The e.m.f. of the cell is the difference of electrical potential which causes the current to
flow from the electrode of higher potential to that of lower potential. The e.m.f. can't be
determined accurately by connecting the two electrodes of the cell directly to a voltmeter. This
is due to the reason that while doing so a part of the cell current is drawn which causes a
change in e.m.f. due to
(i) the formation of reaction products at the electrodes and
(ii) change in concentration of the electrolyte surrounding the electrodes.
However, this problem is overcome by using potentiometric methods in which e.m.f. of
the cell is balanced another cell where e.m.f. is known, so that
virtually no current is drawn from the cell. This is detected by
means of a galvanometer connected in the circuit.
In the determination of electrode potentials, the electrode
whose potential is to be determined is connected with a standard
hydrogen electrode which acts as a reference electrode. In
general, the use of hydrogen electrode is avoided because it
needed more time and operate very difficult. Instead of KCl sol
hydrogen electrode, mostly Calomel electrode is preferred.
Calomel Electrode
It consists of metallic mercury in contact with mercurous
chloride (calomel), which, in turn, is in contact with solution Fig. 6.14. Calomel electrode.
of potassium chloride shown in Fig. 6.14. Generally, 1 N KCI
or 0.1 N KCI or saturated solution of KCI is used. At 25°C, the reduction potentials of these
electrode are given by
0.1 N KCI; E = 0.3338 V - 0.00007
1.0 N KCI; E = 0.2810 V - 0.00024.
Saturated KCI solution E = 0.2420 V - 0.00076
The values of standard reduction potentials of saturated calomel electrode at some other
temperature are:
15"C 0.2496 volt
20"C 0.2456 volt
30"C 0.2381 volt
35°C 0.2344 volt
40°C 0.2305 volt
Weston Standard Cell
A standard cell is one
which is capable of giving ~~rt---cork
constant and reproducible
t=:=:=::""=~=-",,,,~......t-=-=,;.::. ._ _ Satd. Cd SO. sol
e.m.f. and whose temperature
coefficient of the e.m.f. is
negligible. Weston standard
cell is the one which is
commonly employed for this
purpose. This consist of H- ~--Cd. amalgam
shaped glass vessel, the lower
~ifL--- Pt wire
ends of both the arms of which
are closed (Fig. 6.15). Platinum
wires are sealed into the
bottom of each arm. The
positive electrode consists of Fig. 6.15. The weston standard cell.
mercury which is covered with
a paste of mercury and mercurous sulphate, Hg2 804' The negative electrode contains cadmium
amalgam containing nearly 12 percent of cadmium by weight. Crystals of solid Cd 80 4' ~ H 20
are placed over each electrode. The remaining part of the cell is filled with a saturated solution
of cadmium SUlphate. The upper ends of each arm are corked and sealed. The cell may be
represented as :
8 Isaturated SOlutionl
Cd (Hg), Cd 8°4 , J H 20 (s) of CdSo 4 Hg2 804 (s), Hg (1)
12%
At 20°C the potential of this cell is 1.0183 volts and at 25°C, it is 1.01807 volts.
Thus, the cell, in each cell may be represented as shown in Fig. 6.16. Connect the ends of
the potentiometric wire AB (stretched over a meter scale) to a source of direct current, C.
Then connect the cell under investigation, X, to the circuit taking care that the same polls of
the two cells are connected to the same end of AB. Connect the other end of the cell X through
a two way key and a galvanometer to a sliding contact. Move it on the potentiometer wire and
detect the null point, say at D. Then disconnect the cell X and instead place the standard cell
(8' in its position. In a similar way, find now the null point, say at D'.
Let the e.m.f. of the standard cell = Es
e.m.f. of the cell C be =Ec
and e.m.f. of the cellXbe =Ex
Now since th~ potential difference A and B created by two oppositely directed currents
from sources C and X are the same
Zinc rod
,I
--
:=
--
,,,
--
:= ,,
- ----
-------- I
, I
,
=:=:=:=:=:=:=: d
ZnS0 4 soin
Fig. 6.16. Potentiometric method for determination of e.m.f. of cell.
Therefore, Ex = AD E
AB' C
In a similar manner, for the standard cell,
Ex AD
Es = AD' so that
AD
Ex = AD' .Es
Thus, the e.m.f. of the cell under investigation can be determined.
Now, applying the relations,
and knowing that reduction potential of calomel electrode is + 0.242 volt at 25°C, the standard
electrode potential of the cell under investigation can be calculated.
6B.9 POTENTIOMETRIC TlTRATIONS
Potentiometric titration may be defined as titration in which the end point of the reaction
is detected by measuring the change in the potential of a suitable electrode with the addition
of the titrant. They may be divided into the following categories:
(i) Acid-Base titrations
(ii) Precipitation titrations.
(i) Acid-base titration: Since the neutralization of acids and bases is accompanied by changes
in the concentration of hydrogen and hydroxyl ions, so, the pH of the solutions changes very
su~d~mly is the vicinity of the equivalence point, therefore, hydrogen electrode can be used.
As the potential of a hydrogen electrode gives a direct measure of pH, this potential will then
change rapidly at the equivalence point. Two methods are used for finding the equivalence
point in this type of titration. (aJ Direct method, (bJ Differential method.
(ii) Redox Titration : In this case, the potentiometric titrations may of course be either
reductions on oxidations and the methods are useful whether or not there is a colour change
at the end point, and so no indicator other than the change of potential is necessary. In this
case, the electrode reversible to H+ ions is replaced by an inert metal, like a platinum wire,
dipped in solution containing both the oxidised and reduced forms of the species to be titrated.
This electrode serves as an oxidation-reduction electrode.
(iii) Precipitation Titration: In this case of precipitation titrations, an electrode reversible
with respect to anion or the cation of the instable precipitate is used as an indicator electrode.
They carried out the titration by adding a solution of halide, sucn as potassium chloride, bromide
or iodide to AgN0 3 . The cell involves the liquid junction AgN0 3 ' KN0 3 and this difficulty was
overcome by providing a counter current to halide free KN0 3 solution from the liquid junction
being titrated. The direct method of potentiometric titration involving precipitation has been
used in the determination of magnesium in dolomite, titration of chloride, bromide and
thiocyanate with mercurous perchlorate.
6D.10 APPLICATIONS OF POTENTIOMETRIC TITRATIONS
(i) In calculating the ionisation constant of weak acids : When a standard alkali
solution is added to a solution of weak acid, salt and water are formed. For a mixture of weak
acid and a salt of a weak acid, the hydrogen ion concentration is given approximately by the
relation:
K [Acid]
[H+] = [Salt]
where K =Ionisation constant of weak acid.
or -log [H+] = log [Salt] -log [Acid] -log K
[Salt]
pH = log [Acid] -log K
At half neutralisation, [Salt] = [Acid]
Therefore pH = log K
(ii) Measurement of Instability constant and composition of Werner compounds:
Jaques gave a mathematical treatment of the composition of complexes by potentiometric means.
The equilibrium in the case of complex formation between a metal ion M+ and L- is represented
as
mM++nL- ~ [MmLn]m-n
A series of potentiometric measurements is carried out for various concentration for M+

and L-. For two such cases:
RT log { [MmLII]a rIm
!lEI = ZF [MmLII]h
and
where MI = difference
M2 =
RT
ZF log { r-
[Cl
[C1
in potential between concentrations a and b at a constant anion
concentration.
/)£2 = difference in potential between concentration c and d at a constant complex
concentration.
Thus the value of m and n can be calculated.
This method was used by Leden to show the complex formation between Cd2+ and a number
of anions such as CI-, Br, 1-, 8042 , NO; , and CNS-.
1. What is electrode potential ?

2. What are the different factors on which electrode potential depend?
3. What do you mean by e.m.f. of the cell ?
4. What are the various advantages of potentiometric titrations ?
5. What is the role of hydrogen electrode in potentiometric titration ?
6. What is calomel electrode?
7. What is standard cell ?
8. Which cell is usually employed as standard cell ?
9. How does standard cell consist of?
10. What is the potential of standard cell at 25°C?
11. What do you mean by potentiometric titration?
12. What are the different categories of potentiometric titration?
13. What do you mean by Redox titrations ?
14. From which point you can find out the point ofinflextion?
15. Why does we prefer calomel electrode instead of hydrogen electrode?
16. Why does the e.m.f. can't be determined accurately by connecting the two electrodes
of the cells directly to a voltmeter.
( ANSWERS)
1. When a metal rod is dipped in its salt solution, an equilibrium potential difference
develops between the metal red (electrode) and the surrounding solution. This is
known as electrode potential.
2. The electrode potential depends upon:
(i) the nature of metal,(ii) the concentration of metal ion in solution, (iii) the
temperature.
3. The e.m.f. of the cell is the difference of electrical potential which causes the current
to flow from the electrode of higher potential to that oflower potential.
4. The various advantages of potentiometric titration are :
(i) It can be used for titrating weak acids against weak alkalies.
(ii) It can be used in coloured solutions.
(iii) No external indicator is used in oxidation-reduction titrations.
5. Hydrogen electrode acts as a reference electrode in potentiometric titration.
6. It is also used as reference -electrode instead of hydrogen electrode. It consists of
metallic mercury in contact with mercurous chloride (calomel), which in turn, is in
contact with solution of potassium chloride.
7. A standard cell is one which is capable of giving constant and reproducible e.m.f. and
whose temperature coefficient of e.m.f. is negligible.
8. Weston standard cell is usually employed as standard cell.
9. Standard cell consists of H-shaped glass vessel, the lower end of both the arms are
closed. Platinum wires are sealed into the bottom of each arm. The positive electrode
is consists of mercury which is covered with a paste of mercury. The negative electrode
contains cadmium amalgam containing nearly 12 percent of cadmium by weight.
Crystals of solid Cd S04' f H 2 0 are placed over each electrode. The remaining part
of the cell is filled with a saturated solution of cadmium sulphate. The upper arms
are corked and sealed.
10. The potential of standard cell at 25°C is 1.01807 volts.
11. Potentiometric titrations may be defined as titrations in which the end point of the
reaction is detected by measuring the change in' pfltential of a suitable electrode with
the addition of the titrant.
12. The different categories of these titrations are :
(i) Acid-base titrations.
(ii) Redox titrations.
(iii) Precipitation titrations.
13. Redox titrations can be carried out potentiometrically in a manner similar to acid
base titrations. In this case, the electrode reversible to H+ ions is replaced by an inert
metal, like a platinum wire dipped in solution containing both the oxidised and
reduced forms of the species to be titrated.
14. The point ofinflextion can be find out from the equivalence point in the graph.
15. The calomel electrode is preferred instead of hydrogen electrode because it is more
difficult to operate and greater time is needed to reach the equilibrium with the ions
in the solution.
16. The e.m.f. can't determined accurately by connecting the two electrodes of the cell
directly to a voltmeter because a part of the cell current is drawn which causes a
change in e.m.f. due to :
(i) the formation of reactio~ products at the electrodes, and
(ii) change in concentration of the electrolyte surrounding the electrode.
6B.11 CONDUCTOMETRIC TITRATION
Principle
The principle involved in conductometric titrations is that conductance of an electrolytic

solution depends upon the nature, number, and mobility of the ions in solution.
When an ionic reaction takes place, the conductance may increase or decrease depending
upon the nature of the electrolytes undergoing reaction. The substitution of ions of one
conductivity by ions of another conductivity is the basis of conductometric titration.
The conductivity is measured after each addition of a small volume of the reagent and the
points thus obtained are plotted to give a graph which consist of two straight lines intersecting
at the equivalence point. In conductometric titrations, care should be taken to see that volume
of the solution doesn't change much. It can be achieved by employing a titrating agent which
is about 20 to 100 times more concentrated than the solution being titrated.
The plot drawn between the conductivity values against the volume of the titrant may be
curved when the reaction is not quantitative. Sometimes, the line near the end point shows
curvature which may be due to hydrolysis or dissociation of the product formed or due to
appreciable solubility of the precipitate formed in precipitation titration. In such cases, the
end point can be established by extrapolating these portions of the lines or tangents to the
curves.
Procedure: The conductometric titrations are carried out as follows:
The solution to be titrated is taken in the beaker and titrant is taken in the microburette.
A conductivity cell is also immersed in the beaker along with stirrer. The conductivity cell is
attached to the conductivity bridge or conductivity meter which give the values of electrical
conductances.
. . . - - Microburette
Conductivity
bridge .....- - - . .
l¥'I~rIt+'
......- Stirrer
Conductivity
cell
~~~~m~~~~;§H~
1111111111111- solution
Electrolyte
Fig. 6.17. Arrangement for conductometric titrations.

First of all the conductance of electrolytic solution taken in beaker is noted with the help
of conductivity bridge. Then small volumes of titrant are added drop by drop from microburette
and conductance for each addition of titrant is noted. The concentration of titrant is kept 10
times the concentration of the solution to be titrated in order to get straight line graphs. The
graphs are plotted in between the conductance values of volume
of titrant added. From the graph, end point of titration can be
determined.
~
6B.12 TYPES OF CONDUCTOMETRIC TITRATIONS
~
Acid-base titrations ='
(a) Strong acid Vs strong base: If a strong acid like Hel Q
1
is titrated against a strong base such as NaOH, the conductance
first decreases due to replacement of fast moving H+ ions by Eq. point
slow moving Na+ ions. Vol. of NaOH added
230 'I ' Essentials ofEngineering Chemistry
H+ + CI- + [Na+ + OH-] ~ Na+ + CI- + H 20

The solution being added drop by drop is shown in square brackets.
However, after the equivalence point is reached, the
conductivity rapidly rises with further addition of NaOH because
of continuous addition of fast moving OH- ions.
(b) Strong acid Vs weak base: For example, HCI Vs ~
NH 40H :1
'0
s::
H+ + Cl- + [NH: + OH-] ~ NH: + CI- + H 20 8
The conductivity, first decreases due to replacement of H+
ions by NH4 + ions, but after the equivalence point, the
conductivity almost remains constant since NH40H is a weak Vol. ofNH.OH added
electrolyte and ionizes to a small extent giving very small conductivity.
(e) Weak acid Vs strong base: For example, CHaCOOH Vs NaOH
CH3COO- + H+ + [Na+ + OH-] ~ CH3COO-+ Na+ + ~O

The conductivity decreases firstly since CH3COONa formed ~
initially suppresses the ionization of CH 3COOH. However, as .;;
~
the titration is continued, the ionising salt concentration tends '0
to produce an increase in conductance. After the neutralisation, §
further NaOH addition gives excess of OH- ions and hence Co)
Eq. point
conductivity increases rapidly.
Vol. of NaOH added
(d) Weak acid Vs weak base: For example, CHaCOOH
VsNH40H
The conductivity first decreases as CH3 COONa formed

~
suppresses the ionization of weak acid, (CH3 COOH) passes ';;
through a minima and then increases upto the end point. After ~
the equivalence point, further addition ofNH40H doesn't change §
conductivity much as its dissociation is depressed by salt present Co)
in the solution.
.. Eq, point
(e) Mixture of strong acid and a weak acid Vs strong
Vol. ofNH40H added
base: For example, (HCI- + CHaCOOH) Vs NaOH
, HCI being stronger acid than H 3 CCOOH will get
titrated first. The titration of H3CCOOH will start only
after HCI is completely neutralised. NaOH
~
Eq. Pt. A =eq. pt. due to neutralisation of HCI ';;
Eq. Pt. B =Neutralisation ofCH3 COOH ~
'0
s::
During the titration ofHCI Vs NaOH, the conductivity 8
will continuously decrease due to replacement of highly
mobile H+ ions with Na+ ions up to the end point. After
the neutralisation of HCI, the neutralisation of CH3 COOH
will start and the conductivity increases to a small extent Vol. of NaOH added
till its neutralization is complete due to excess OH- ions. After that conductivity increases
abruptly due to ionization of NaOH.
(I) Precipitation titration: e.g. KCI Vs AgNO s The
reaction involved may be represented as :
Ag+ + NO; + [K+ + CI-] ~ K+ + NO; +AgCI

(ppt)
Since mobility of K+ ions is nearly the same as that of Ag+

ions, the conductance remains almost constant initially and then
rises after the end point. Before the end point K+ ions are being
replaced by Ag+ ions. But after the end point there are no more
Ag+ ions in the solution. The conductivity increase is due to K+ Vol. of KCl added
and Cl- ions from the added KCI solution.
Advantages of conductometric titration
1. Coloured solution, which cannot be titrated by ordinary volumetric methods using
indicator can be successfully titrated by conductometric titrations.
2. This method can be used in case of very dilute solutions, where volumetric method
may not be possible.
3. Titration of weak acids against weak. bases can also be carried out by conductometric
method for which no indicator is suitable.
4. No special care is needed near end point as it is determined graphically in
conductometric titrations.
%. These titrations are more accurate. The end point determined graphically is accurate.
6. Conductometric titrations are particularly useful in analysis of alkaloids, aspirin and
vinegar.
1. What is conductance and what are its units ?

2. What is cell constant and what are its units ?
3. What is specific conductance and what are its units ?
4. What is equivalent conductance?
5. What are units of equivalent conductance?
6. What is molecular conductance?
7. What are units of molecular conductance?
8. What is the effect of dilution on conductance?
9. What is the effect of dilution on specific conductance?
10. What is a conductivity cell ?
11. What is cell constant? How is it determined?
12. Why ordinary water is unsuitable for conductivity measurements ? What is
conductivity water?
13. How does the conductance change when a weak acid like acetic acid is titrated against
a strong base like sodium hydroxide?
" 14. How/does the conductance vary when a strong acid is titrated against a weak base?
15. What are the advantages of conductometric titrations ?
16. What is the principle of conductometric titrations ?
17. Can this principle be used for other type of titrations ?
lB. Why does the conductance first decrease and then increase after end point in case of
HCI and NaOH titration?
19. Why should the solution taken in the burette be strong?
20. -How do you account for a sligh~ fall in conductance in the initial stages during titration
of a weak acid and a strong base?
(ANSWERS )
1. The reciprocal of resistance is called conductance. Its units are ohm-lor 0-1 -or mho
or Siemen (S).
Distance between parallel electrodes (I) I .. 1
2. Ce11 contant = . . ts umt lS cm- .
Area of cross sectIon of electrode (A)
3. Specific conductance is dermed as the conductance of one centimeter cube of the
solution. It is denoted by K (kappa).
Specific conductance = Cell constant . Its units are ohm-l cm-l or mho cm-l
Observed resistance
or S cm-l .
4. Equivalent conductance (Aeq) is the conductance of all the ions produced by dissociation
of one gram equivalent of a solute in solution.
sp. conductance (k) x 1000
Aeq = N
where, N = Normality of solution in gm equiv. per litre.

5. Units of equivalent conductance are ohm-l cm2 (g. eq.)-l.
6. Molecular conductance (/\ m) is the conductance of all the ions given by dissociation
of one mole of a solute in solution.
sp. conductance (k) x 1000
/\ m = M
Where, M =Molarity of solution in mol per litre.
7. Its units are ohm-l cm2 mol- l .
B. Conductance increases with dilution because on dilution dissociation increases and
hence the number of ions increases.
9. Specific conductance decreases with dilution because the number of ions per cubic
centimeter of solution decreases on dilution, although total number of ions in the
given volume increases due to increase in dissociation.
10. The vessel in which the measurement of conductivity of the solution is to be made is
known as conductivity cell. They are of various shapes and sizes depending upon the
-naturt'! of the solution taken.
11. The observed conductivity must be multiplied by a factor ;. (say x) in or4er to get the
value of specific conductance and is known as cell constant.
Specific conductivity =Observed conductivity x Cell constant.
Cell constant is determined by taking a solution of known specific conductivity and
the observed conductivity is measured. Usually, we take N/50 KCl solution in a
conductivity cell, say, at the room temperature 25°C.
Specific conductivity 0.002768
Cell constant = Observed conductivity = observed conductivity
12. Ordinary water is unsuitable for conductivity measurements because it possesses large
conductance due to the materials dissolved fr,om the conWner and due to CO2 and
NHs dissolved from air. So, water is specially purified by distilling. it a number of
times after addition of a little KMn0 4 • Such water is known as conductivity water
and should have a
conductivity not more than 2-
3 x 10-8 ohm-I.
13. Acetic acid is a weak acid, so
its conductance is low. As
NaOH is added, sodium
acetate is produced which is conductancel
highly ionized and, therefore, (ohm-I)
the conductance begins to

increase. After end point,
NaOH added introduces fast
moving OH- ions and hence Vol. ofNaOH added (ml)
the conductance begins to
increase sharply
CHsCOOH + [Na+ + OH-] --+
14. Let us consider the titration ofHCI against NH4 0H solution.
[H+ + Cl-] + NH40H --+ [NH: + CI-] + H 20

Conductance of HCI I
solution is initially high
because of the presence
of fast moving H+ ions. As
NH 4 0H solution is
added, the fast moving H+ Conductance
ions are replaced by (ohm-I)
iI
slower NH: ions and
hence conductance
decreases. When the end
point is passed, further
addition of NH 40H does Vol. of NaOH added (ml) --+
not cause much change in
the conductance because NH40H is weakly ionized.
lIS. Conductometric titrations have a number of advantages over volumetric titrations
involving the use of indicators:
(a) These titrations can be used for coloured solutions where ordinary indicators fail to
give the end point.
(b) These can be used for the titration of even very dilute solutions of the order of
IO-4M.
(c) No extra care is needed near the end point as it is simply the intersection of two
lines.
(d) These can be used for the titration of mixtures of weak and strong acids.
16. Conductometric titrations are based on the principle that the electrical conductance
dep~nds upon the number and mobilities of ions.
1'1. Yes, this can be applied to some precipitation titrations and the titrations in which
there is the formation of complex ions.
18. This is because of the fact that highly mobile H+ ions of Hel are being replaced
progressively by slow moving Na+ ions, and hence the conductance decreases. After
the end point, NaOH added gives fast moving OH- ions. Hence conductance begins
to increase.
19. In order to keep the volume change small in the titration flask.
20. It is due to common ion effect i.e., the suppression of dissociation of the weak acid by
its anions e.g., CH3COO- ions in case of acetic acid.
6.B13 FLAME PHOTOMETRY
This technique is special case of emission spectroscopy, widely used for the
analysis of metals specially alkali and alkaline earth metals in biological fluids,
tissues and other samples.
Principle:
It is based on the principle that when a solution containing a metallic compound is

sprayed into the flame, a vapour containing the metal atom will be formed. Some of
these metal atoms in vapour or gaseous state will get excited to higher energy levels.
When these return back to ground state; emission of radiation will occur which is
characteristic of the metal under consideration.
The following steps take place when a solution of a metallic salt is sprayed into a flame:
(i) The solvent is vaporized leaving particles of salt in the flame.
(ii) The salt is then vaporized and breaks up into constituent atoms.
(iii) Most of the metal atoms get excited to higher energy levels i.e., the electrons jump
into higher energy levels.
(iv) The excited atoms emit radiation as the electrons return to lower energy levels. The
spectrum obtained is characteristic of the metal atoms depending upon their specific
atomic structure.
But some other processes such as formation of molecular species besides atomization are
likely to take place. The atomization may not be possible in case of some metals. Therefore,
the technique cannot be applied in case of all metals.
This method is employed for analysis of sodium, potassium, lithium, calcium etc. because
these elements have an easily excited flame spectrum of sufficient intensity for detection by a
photocell. The ionization energies of the alkali metals and alkaline earth metals are low, so
these metals get easily excited.
6B.14 INSTRUMENTATION
A simple flame photometer is shown in Fig. 6.18. It consists of the following components:
(a) An atomizer (b) The burner system (c) An optical system (d) A photocell (e) Amplifier
and recorder.
Photocell Filter Lens
Amplifier
and read
system
Burner
Fuel ... head
Atomiser
Mixing
chamber
lFe
t
Air
~
Drain
Mixing
barnes
Fig. 6.18. A flame photometer.

Nowadays, integral atomizer burners are commonly used which can inject the entire spray
directly into the flame.
Air is passed into an atomizer at a given pressure and the suction then produced draws a
sample into the atomizer. It joins with the air stream in the form of a mist and passes into
the burner system. Before passing into the burner, it is mixed with the fuel gas usually acetylene
or hydrogen supplied under pressure in the mixing chamber. The radiation resulting from the
flame passes through an optical filter which permits only the radiation characteristic of the
element under investigation to pass through a photocell. The output from the photocell is
measured on a digital read out system:
Procedure: Firstly using solution of known concentration, a calibration curve is plotted.
It is done by aspirating the known concentration of the element into the flame and noting the
respective readings. A graph is plotted for these readings against the respective concentration
of the standard ·solutions.
After the calibration curve is ready, the concentrations of unknown samples are noted by
simple interpolation. The modern flame photometers consists of a microcomputer which stores
the calibration curve and gives a direct reading of the concentration of the sample.
Generally, stock solutions containing about 1000 IlgmL-l are prepared. However if the
solution are further diluted, these deteriorate due to adsorption of solute on walls of the glass
vessels. Hence standard solutions of low concentrations should not be stored for more than a
day or two. The characteristic wavelength of some metals are:
Metals Wavelengths Metals Wavelengths
Sodium 589 run Rubidium 421.5 nm
Potassium 766nm Caesium 455.5 nm
Lithium 670 run Magnesium 285.2 nm
Calcium 623 run Silver 328.1 nm
Barium 554nm Zinc 707.2 nm
6B.15 APPUCATIONS
(i) Flame photometry is primarily' used for the analysis of those elements which have
an easily excited flame spectrum e.g., Na, K, Li, etc.
(ti) It has also been used for the analysis of other materials such as soils, cements,
glasses, plant materials, biological fluids and natural water etc.
(iii) The technique has been used for the determination ofNa, K and Ca in blood serum,
urine, oil extracts and water samples.
(iv) It is used for the,quantitative determination of metals in solution and not merely for
their detection (qualitative analysis).
(v) Besides alkali and alkaline earth metals, some other metals such as Ag, Zn, Fe, Ce,
Ru etc. can be analysed.
LimitatioDs
Flame photometry has the following limitations:
(i) Some extra molecular entities are also formed during flame emission spectroscopy
or flame photometry which lowers the efficiency of transformation of atoms into
excited state.
(ii) It is applicable to only those metals which have easily excited flame spectrum with
sufficient intensity for detection by photocell.
(iii) The intensity of emission of radiation is very sensitive to variations in flame
temperature.
(iv) The phenomenon like self absorption and special interference possess problems during
the process.
[""P-RA-CTI--C-E-P-R-O-B-LE-MS--F-O-R-TUT--O-RJAL--S.......)
1•. Which type of element can be analysed by flame photometry ?

2. 1b which block of the periodic table the elements showing flame colouration belong?
Why is the block so named ?
3. What is the electronic configuration of S-block elements?
4. Why S-block elements show flame colouration and can be analysed by flame
photometry? .
5. Name the element among S-block which do not show flame colour. Why do they show
exceptional behaviour.? .
6. Why does each S-block element give a characteristic colouration to the flame different
from other elements ?
7. How does the frequency of the radiation emitted change among the alkali metals down
a group ?
( ANSWERS )
1. The alkali and alkaline earth metals belonging to group 1 and 2 of the periodic table
can be analysed by flame photometry.
2. The elements showing flame colouration belong to S-block of the periodic table. The
block is so named because the last electron in them enters in the S-orbital of the
outermost shell.
3. The general electronic configuration of alkali metals can be represented as [Noble gas]
nS 2 and that of alkaline earth metals as [Noble gas] ns2 •
4. Because of their low ionisation energies, the heat energy from the flame excites the
electrons in these elements to higher energy levels. When these electrons ret1:lrn to
their original orbitals, the absorbed energy is emitted as different frequencies of visible
light which determines the colour of the flame.
5. The first two elements of second group namely Be and Mg do not show flame
colouration. Be and Mg atoms are comparatively smaller and their ionisation energies
are very high. Hence their electrons are more strongly bound and are not excited by
the energy of the flame to higher energy states. These elements, therefore, do not
give any other colour to the flame.
6. The flame colouration depends upon the ionisation energy which varies from one
element to the other and consequently the ease of excitation of the electron from the
metal also changes. The ionisation energy of alkali metals or alkaline earth metals
decrease as we move down a group. With change in the ionisation energy, the frequency
of the radiation emitted also changes. So each element gives a characteristic colouration
depending upon the ionisation energy it possesses.
7. When an equal amount of energy is supplied to the alkali metals, the solitary electron
in each atom is raised to different energy levels. These differences are due to difference
in their ionisation energies. The ionisation energy is highest for lithium and decreases
down a group towards caesium. Thus the level to which an electron rises in lithium in
lower than the level to which an electron in caesium rises. The higher the ionisation
energy of an atom, the lower is the level to which the electron is raised and vice-versa.
As the electron returns to the ground state, the release of energy will be lowest in
case of lithium and will increase in the order from lithium to caesium. Consequently,
the frequency of light emitted in the flame will be minimum in case of lithium and
will increase in the order from Li to Cs.
(REVISION QUESTIONS)
1. Define spectroscopy.
2. What is the principle of colorimetry ?
3. Explain the Lambert-Beer law.
4. What is calibration curve?
5. Explain the working of colorimeter.
6. What are the various applications of colorimeter?
7. Discuss the electromagnetic spectrum.
S. What are the various advantages of potentiometric titration?
9. Explain the principle of potentiometric titration.
10. Define a reference electrode.
11. How can you increase the value of reduction potential of an electrode?
12. What is electrochemical (EMF) series? Give its applications with suitable examples.
How is it measured by potentiometric method?
13. Write short note on calomel electrode and Weston standard cell.
14. How does the potential in a calomel electrode vary with the concentration of
electrolyte ?
15. Define electromotive force. How is it measured by potentiometric method ?
16. Write a short note on potentiometric titrations ?
17. What are the various applications of potentiometric titration?
18. Explain the principle of conductometric titrations taking example of strong acid Vs
strong base titrations. Give the advantages of conductometric titrations.
19. Draw the conductometric titrations in the following cases:
(i) Strong acid-weak base titrations.
(ii) Weak acid-strong base titrations.
(iii) AgNOs-KCI titrations.
20. Explain and draw the nature of conductometric curves for:
(i) A mixture of strong acid and a weak acid Vs a strong base.
(ii) A weak acid Vs a weak base.
21. What are the advantages of conductometric titrations over ordinary titration using
indicators ? Why the concentration of the titrate is taken much higher than the
concentration of titrant in these titration ?
22. Describe the conductometric titration of the following:
(i) A solution ofHCI Vs aqueous solution ofNaOH.
(ii) A solution ofCHsCOOH Vs aqueous solution of NaOH.
(iii) A mixture of aqueous solution ofHCI and CHsCOOH Vs aq solution of NaOH.
(iv) Aq. solution of oxalic acid Vs aq. solution of NaOH.
(v) A solution ofAgNO s Vs aq. solution ofKCl.
(vi) Aq. solution ofCHsCOOH Vs aq. solution ofNH4 0H.
23. Explain the principle offlame photometry. Give the instrumentation employed. Which
type of elements can be analysed by this technique?
24. Give a self explanatory note on Flame photometry. Write its applications and
limitations.
HIGH POLYMERS
SYLLABUS
Definition, classification- Natural and synthetic with examples, polymerization - definition,
types of polymerization - addition and condensation with examples. Mechanism of
polymerization - free radical mechanism (ethylene as an example); Methods ofpolymerization-
bulk, solution, suspension and emulsion polymerization Glass transition temperature;
structure and property relationship; compounding of resins; Synthesis, properties and
applications of Teflon, PMMA, polyurethane and phenol - formaldehyde resin; Elastomers
- Deficiencies of natural rubber and advantages of synthetic rubber, synthesis and application
of neoprene, butyl rubber; Adhesives- Manufacture and applications of epoxy resins;
Conducting polymers - definition, mechanism of conduction of polypyrrole; structure and
applications of conducting polyaniline.
7.1 INTRODUCTION
The word polymer is the combination of two Greek words - poly meaning several and meros
meaning parts. Thus, polymers are high molecular weight substances consisting of large
molecules of colloidal dimensions (i.e., 10-4 - 10-7 cm), predominantly organic consisting of
long chain macromolecules. The chains in them are similar or different repeating units usually
on a backbone of carbon atoms or other polyvalent atoms. The smallest unit, with which a
polymer is made is known as monomer or repeating unit or building block. The monomers
in polymers are joined with one another through covalent bonding. Polymers form the backbone
of the modern civilization and are the chief products of the modern chemical industries. An
important attribute of the polymers is the ability to modify their inherent physical properties
by the addition of certain additives while retaining their characteristics. Most of the polymers
are of recent origin but they have made an impact on our daily life, starting from our kitchen!
drawing room to space.
Polymers are one of the iinportant products of chemical industry which have a great impact
on our modern lines. Plastics, synthetic fibres, synthetic rubber etc. are common example of
polymers. These polymers have multifarious uses ranging from household articles, automobiles,
clothes, furniture etc. to space aircraft and biomedical and surgical operations. In fact most of
the equipments which were earlier made from metals, wood and glass are now made from
ploymers because they are lighter in weight and more resistant towards corrosion and chemical
,attack.
Difference between a p~lyme;' and macromolecule: Usually one does not make much
distinction between a polymer and a macromolecule because both are high molecular weight
substances. A polymer consists of a large number of structurally similar or dissimilar repeating
units but a macromolecule mayor may not have all the repeating units structurally similar.
Let us consider, two well known biomolecules (i) starch (ii) nucleic acid. The starch should be
considered both as a polymer as well as macromolecule because it is made by the condensation
polymerization of a large number of only one type of monomer, i.e., of a-glucose molecules.
However, nucleic acid should be considered as a macromolecule and not as a·polymer because
it is made by the condensation polymerisation of three structurally as . well as chemically
different molecules, i.e., phosphoric acid, pentose sugar and nitrogen base. Similarly, polyvinyl
chloride (PVC) may be regarded both as macromolecule as well as polymer because it is made
up of only one type of monomer, i.e., vinyl chloride. Thus, all polymers are macromolecules
but all macromolcules are not polymers. Hemoglobin in macro-molecule but not a polymer. It
has no repeating unit in its structure.
7.2 CLASSIFICATION OF POLYMERS
Definition
Polymers are macro-sized molecules of high molecular masses formed by the combination
.of a large number of simple molecules by covalent bounds to form long chain compounds.
The simple molecules which combine to give polymers are called monomers. The process
by which the simple molecules (i.e., monomers) are converted into polymers is called
polymerisation. For example, or commonly known as polythene is a which is obtained from
, its monomers ethylene by the process of polymerisation.
nC~=CH2 Poiymerisation (-CH 2-CH2-)n
Ethylene Polyethylene
(monomers) (polymer)
The number of repeating units (monomers) in a chain of a polymer is called degree of
polymerisation. In the above reaction, n represents degree of polymerisation.
Polymers are classified in a number of ways as described below:
A. Classification of Polymers on the Basis of Source ofAvailability
The polymers can be broadly classified as :
1. Natural polymers, '2. Synthetic polymers, 3. Semisynthetic polymers.
1. Natural polymers: The polymers obtained from nature <plants and animals) are called
natural polymers. These occur in plants and animals and are very essential 'for life. For
example, starch, cellulose, natural rubber, proteins, nucleic acids etc. '
(i) St~h: It is a polymer of a-glucose. It is a chief food reserve of plants.
(ii) Cellulose: It is also a polymer of ~-glucose. It is a chief structural material of the
plants and provides food, clothing and shelter. Both starch and cellulose are made by
plants from glucose produced during photosynthesis.
(iii) ,Proteins : These are polymers of a-amino acids. They have generally 20 to 1000
a-amino acids joined together in a highly organized arrangement. These are building
blocks of animal body and constitute an essential part of our food.
(iv) Nucleic acids: These are polymers of various nucleotides. For example, RNA and
DNA are common nucleotides. These control heredity at molecular level.
High Polymers 241
(v) Natural rubber: It is a polymer of unsaturated hydrocarbon, 2-methyl-l, 3-butadiene
also called isoprene. It is obtained from latex of rubber trees.
Polymerisation
n~=C-CH=~
I
CH3
Isoprene
2-Methyl-l, 3-butadiene Polyisoprene (natural rubber)
In natural rubber 10,000 to 20,000 isoprene units are linked together. Rubber provides
various articles of daily use.
Note: Polymers such as polysaccharides (starch, cellulose), proteins and nucleic acids etc.
which control various life processes are also called biopolymers.
2. Synthetic polymers: The polymers which are prepared in the laboratories are called
synthetic polymers. These are also called man-made polymers. For example, polyethylene,
PVC, nylon, teflon, bakelite, terylene, synthetic rubber, etc.
These polymers find diverse uses as in clothing, shelter, electric fittings, substitute for
wood and metals, household goods etc.
3. Semisynthetic polymers: These polymers are mostly derived from naturally occurring
polymers by chemical modifications. For example, cellulose is a naturally occurring polymer.
Cellulose on acetylation with acetic anhydride in the presence of sulphuric acid forms cellulose
diacetate polymer. It is used in making threads and materials like films, glasses etc. Other
examples of semisynthetic polymers are vulcanized rubber (used in/making tyres etc.), gun
cotton which is cellulose nitrate (used in making explosives) etc.
B. Classification of Polymers on the Basis of Molecular Forces
Depending upon the intermolecular forces, the polymers have been classified into four
types:
1. Elastomers. 2. Fibres.
3. Thermoplastics. 4. Thermosetting polymers.
1. Elastomers: The polymers that have elastic character like rubber are called elastomers.
In elastomers the polymer chains are held together by intermolecular forces. Because of the
presence of weak forces, the polymers can be easily stretched by appling small stress and regains
their original shape when the stress is removed. The most important example of elastomer is
natural rubber. However a few cross-links can be introduced into the chain to convert it to
vulcanised rubber which has better tensile strength, elasticity and resistance to abrasion
than natural rubber.
2. Fibres : These are the polymers which have strong intermolecular forces between the
chains. These forces are either hydrogen bonds or dipole-dipole interactions. For example, in
case of polyamides (such as orlon), the intermolecular forces are hydrogen bonding, while in
polyesters (such as terylene, dacron) the intermolecular forces are dipole-dipole interactions
between polar carbonyl (C=O) and amine groups. Because of strong forces, the chains are packed
and, thus, impart crystalline structure. As a result, the polymers have high tensile both and
less elasticity. Therefore, these polymers have sharp melting points. These polymers are long
and thread like and can be woven into fabrics. Therefore, these are used for making fibres.
Common examples are nylon-66, dacron, silk.
3. Thermoplastics : These are the polymers which can be easily softened when heated
and hardened when cooled with little change in their properties. The molecular forces in these
polymers are intermediate between those of elastomers and fibres. There is no cross linking
between the chains. The softening occurs as the polymer chains move more and more freely
because of absence of cross links. When heated they melt and form a fluid which can be moulded
into any desired shapes and then cooled to get a desired product. Common examples of plastics
are polythene, polystyrene, polyvinyl chloride, chloride teflon etc.
4. Thermosetting polymers : These are the polymers which undergo permanent change
on heating. They become hard and infusible on heating. When heated, they get highly cross
linked to form hard, infusible and insoluble products. The cross links hold the molecules in
place so that heating does not allow them to move freely. Therefore, a thermosetting plastic
is cross linked and is permanently rigid. The common examples are bakelite, melamine
formaldehyde etc.
C. Classification of Polymers on the Basis of Structure
On the basis of structure, these can be classified as :
1. Linear polymers.
2. Branched chain polymers.
3 Cross-linked polymers.
1. Linear polymers: These are polymers in which monomeric units are linked together
to forth linear chains [Fig. 7.l(a)]. These linear polymers are well packed and therefore, have
high densities, high tensile strength and high melting points. Some common examples oflinear
polymers are: polyethylene, nylons, polyesters etc.
2. Branched chain polymers:
These are polymers in which the
monomers are joined to form long
chains with side chains or branches of
different lengths [Fig. 7.l(b)]. These Linear Polymer
branched chain polymers are
irregularly packed and therefore, they
have low density, tensile strength and
melting points than linear polymers.
Some common examples are: low Branched Chain Polymer
density polythene, glycogen,
starch etc.
3. Cross-linked polymers :
These are polymers in which
monomer units are cross-linked
together to form a three-dimensional
network. These are also called three-
dimensional network polymers. Cross-Linked Polymer
These polymers are hard, rigid and
brittle because of network structure. Fig. 7.1. Different structures of polymers
(a) Linear structure
These are shown in Fig. 7.l(c). For
(b) Branched chain structure
example, bakelite, melamine
(c) Cross-linked structure.
formaldehyde resin etc.
D. On the basis of their methods of synthesis
Synthetic polymers are further classified depending upon the method of synthesis. On this
basis they are classified as :
(i) Addi#on polymers (ii) Condensation polymers
For details refer to article 7.4.
7.3.2 Nomenclature of Polymers
Homopolymers : These are the polymers obtained by the polymerisation of only one type
of monomers. For example, polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC),
polystyrene (PS), polyisoprene (PIP), poly acrylonitrile (PAN), poly vinyl acetate (PVA),
nolymethyl methacrylate (PMMA), nylon 6, polybutadiene (PBD), Teflon, cellulose, starch,
glycog<':Il ate'
High Polymers 243
Copolymers : These are the polymers obtained by the polymerisation of two or more
monomers. For example, nylon 66, nylon 611, bakelite, urea formaldehyde, melamine
formaldehyde, styrene butadiene rubber, polyesters, epoxy resins, alkyd resins etc.
Homochain polymers : These are the polymers containing only one type of atoms i.e.,
carbon atoms in the main chain. For example, all the homo polymers except nylon 6 etc.
mentioned above constitute the homochain polymers.
Hetrochain polymer : These polymers contain two different atoms in the main chain,
one of which is usually carbon atom. For example, nylon 6, nylon 610, nylon 611, urea
formaldehyde, melamine formaldehyde etc. all have nitrogen as the other atom along with
the carbon atoms in the main chain. Similarly, polyesters, epoxy resins, alkyl resins, cellulose,
starch etc. contain oxygen as the other atom along with the carbon atoms in the main chain.
Graft polymers : These are the special type of copolymers in which the main chain is
made up of one type of monomer (AJ and the side chain by another type of monomer (B). Thus
branched chain copolymers are also known as graft polymers i.e.,
-A-A-A-A-A-A-A-A-A-A-
I I
B B
I I
B B
I I
B B
I I
Block polymers : These are another special type of copolymers in which the main chain
is made up of both types of monomers, A and B. These polymers have a long chain of
homopolymer of A joined by a second block of the homopolymer of the second monomer B.
-A-A-A-A-B-B-B-B-A-A-A-A-A-B-B-B-B-
The block polymers may further have random arrangement of monomers A and B in the
main chain to form random block copolymers. i.e.,
-A-A-B-A-A-A-A-B-B-B-B-B-A-B-A-A-B-B-A-
or in a regular alternating fashion (alternating copolymers). i.e.,
-A-B-A-B-A-B-A-B-A-B-A-B-
7.3.3 Functionality
The number of bonding sites in the monomers of a polymer is known as the functionality.
For a substance to act as a monomer, it must have atleast two bonding sites or reactive sites
(functional group). In an alkene, the double bond may be considered as a site with two free
valencies, thus the alkene monomer is bifunctional. Similarly, in alkadiene, the two double
bonds correspond to the functionality equal to four. The compounds having reactive functional
groups like -OH, -NH2, -COOH etc. on the extreme ends of the chain behave as bifunctional
monomers. For example, HO-{CH2)2-OH, HOOC-{CH2)2-COOH, H 2N-{CH 2)s-NH2, are
all bifunctional monomers. However, melamine is a well known trifunctional polymer.
Depending upon the functionality of monomers, it is possible to synthesise the different
types of polymers. A bifunctional monomer consisting of two binding sites at the extreme ends
of chain, produces a linear chain polymer. In such polymers, all the monomers are connected
with another by covalent bonds. However, the different chains are held together by van der
Waal's forces of attraction. If the monomer has polyfunctional groups, a three dimensional
network is obtained by combining these monomers.
If the bifunctinal monomer is represented by a rectangular box containing 10 01two holes,
a covalent bond by hard line and the secondary forces of molecular attractions by the wavy
line, the formation oflinear chain polymer may be shown as below in Fig. 7.2.
Fig. 7.2. Formation of linear chain polymer.

Sijilarly., if the trifunctional monomer is represented by a rectangular box containing three
holes, 000 ,the covalent bond by hard line, the formation ofthree-dimensional cross-linked
network obtained by combining these monomers, may be shown as below in Fig. 7.3.
~r:: ::1:: ::1:: ::1:: ::~

Fig. 7.3. Formation of three dimensional cross-linked network.
7.4 ADDITION AND CONDENSATON POLYMERS
On the basis of mode of synthesis, the polymers may be classified as :
.1. Addition polymers, 2. Condensation polymers.
(i) Addition polymerization: It is the process of addition of the similar or different
monomer( s) resulting in the formation of a giant product in which the molecular formula of the
repeating unit is the same as that of the starting material.
A polymer formed by direct addition of repeated monomers without the elimination of by
product molecules is called addition polymer.
In this type, the monomers are unsaturated compounds and are generally derivatives of
ethene. The addition polymers have the same empirical formula as their monomers.
Very often the molecular weight of the polymer is an integral multiple ofthe monomer. The
polymers thus obtained are termed as addition polymers. For a monomer, to undergo the addition
polymerisation, the basic requirement possessed by the monomer is the multiplicity in it i.e., the
presence of double or triple bond. For example,
n CH 2=CH 2 ~ (-CH2-CH2-)"
ethene (monomer) polyethene (polymer)
n C~ = CH-CI ~ (-CH2-CHC1-)"
vinyl chloride (monomer) polyvinyl chloride (polymer)
n CH 2=CHOCOCH 3 ~ (-CH 2-CHOCOCH 3-)n
vinyl acetate (monomer) polyvinyl acetate (polymer)
n CH 2 = CH-CH2 ~ [~H2-CH2-b:-l
,I
CH
n acrylonitrile orIon (polyacrylonitrile)
n F 2C = CF 2 ~ (-CF2 -CF2)" etc.
Tetrafluor(l~thylene teflon
(ii) Condensation polymerization: It is the process ofthe combination oftwo structurally!
chemically similar or different molecules usually with the loss of simple molecules like H 20, NH 3 ,
ROH etc. resulting in the formation of a high molecular weight substance. The polymers thus
obtained are termed as condensation polymers.
High Polymers 245
A polymer formed by the condensation of two or more than two monomers with the elimination
of simple molecules like water, ammonia, hydrogen chloride, alcohol etc. is called
condensation polymer.
For a monomer, to undergo the condensation polymerisation, the basic requirement possessed
by the monomers is the presence of some reactive functional groups like -OH, -COOH, -NH2'
etc. For example,
hexamethylenediamine adipic,acid Nylon 66
o 0
II
n(HO- C -Q-cII - OR) + n HO-(CH2)2 - OH
terephthalic acid ethylene glycol
terylene or dacron
A polymer with a given structure can be prepared starting with different monomers either
by addition polymerisation or by condensation polymerisation processes. For example, nylon 6
can be prepared either starting with caprolactum via addition polymerisation, i.e.,
/CH 2" - . 0
nH.C C~
21 1
H2C NH
...........
/
H 2C-CH 2
caprolactum nylon 6
or starting with 6-aminohexanoic acid via condensation polymerisation, i.e.,
o 0
II II
nH2 N -(CH2)s -C-OH -~20 ~ [-HN -(CH2)5 -C-O-ln
6-aminohexanoic acid nylon 6
7.4.1 Difference Between Addition and Condensation Polymerisation
Addition Polymerisation Condensation Polymerisation
1. It requires the presence of a multiple bond in 1. It requires two reactive functional groups to
the monomer. be present at both ends ofthe monomer.
2. There can be one or two monomers having 2. There should be at least two different
multiple bond or bonds. monomers having functional group which can
react with each other.
3. No by product is formed i.e., no simple 3. Generally a by-product is formed i.e., a
molecule is eliminated. simple molecule such as H 20, NHa etc. is
eliminated.
4. A homo-chain polymer, generally a 4. Hetero-chain polymer, which may be either
thermoplastic is obtained. These polymers thermoplastic or thermo-setting is obtained.
have only C atoms in the polymer chain. These polymers have some atom than C
atoms in the polymer chain.
5. The growth of chain in at one active centre 5. The growth of chain is at minimum two
only. active centres.
7.5 GENERAL METHODS OF POLYMERISATION
The polymerisation reactions occur in the following two principal types:
A. Addition polymerisation or chain growth polymerisation.
B. Condensation polymerisation or step growth polymerisation.
A. Addition polymerisation or chain growth polymerisation
This polymerisation process involves a series of reactions each of which consumes a reactive
particle and produces another similar particle resulting a chain reaction. The polymerisation
reaction is also called chain polymerisation or chain growth polymerisation because it
takes place through stages leading to increase in chain length and each stage produces reactive
intermediates for use in the next stage of the growth of the chain. Like other chain reactions,
this type of polymerisation reaction also involves an initiator which may be a free radical,
a cation or anion. The addition polymerisation reaction is very rapid and is also characterized
by three steps: Chain initiation, chain propagation and chain termination steps.
In the initiation step, the initiator produces a reactive species (free radical, cation or anion). This
reactive species combines with a molecule of a monomer forming another similar active molecule.
Then, this active molecule is added to another monomer forming another intermediate.
In this way chain propagation continues and ultimately a polymer is formed. In each of these
chain propagation step, a reactive species is consumed and a big reactive species is formed.
Finally, the chain reaction is terminated by steps (called terminating steps) which do not form
reactive species. Therefore, the polymer formed by this process is called chain growth polymer.
The various steps may be given as :
Chain initiation
(1) Initiator 1*
Reactive species free
radical, cation or anion
(2) I*+M IM*
(Monomer)
Chain propagation
(3) IM*+M IMM*
Bigger reactive species
(4) IMM*+M IMMM*
The propagation continues and results in growth of the chain forming polymer.
IMMM* + M etc. I (M)n M*
Polymer
Finally, the chain gets terminated when that active end reacts with a species which gives
a molecules which is not an active species.
Chain termination
I(M)nM* + T
High Polymers 247
Many vinyl polymers are formed by chain reaction polymerisation in which the active species
that initiates the reaction is a free radical and the chain grows by the successive addition of
monomer to a free redical at the end of the chain. The active end may also be a cation or an
anion or a coordination complex. These are not included in syllabus.
B. Condensation Poiymerisation or Step Growth Poiymerisation
Condensation polymers are formed by the condensation of two or more than two moments
with the elimination of simple molecules like water ammonia, hydrogen chloride, alcohol etc.
In this type the monomers generally contain two functional groups i.e., difunctional monomers.
In this process, no initiator is needed and each step is the same type of chemical reaction.
Since in this polymerisation reaction, the polymer is formed in a stepwise manner, it is called
step growth polymer and the process is called step growth polymerisation. The process
for two monomers A and B may be expressed as :
A +B Condense) A-B
Monomers Dimer
A- B +A Condense) A- B-A
A-B-A+B ---4) A-B-A-B

Alternatively, step growth can proceed as :
A+B ~ A-B
A-B+A-B ~ A-B-A-Bor(A-B)2
A-B-A-B+A-B-A-B ~ (A-B)n
Polymer
7.6 MECHANISM OF ADDITION POLYMERISATION

We have learnt that addition polemerisation process takes place through chain reactions,
which may be initiated by species such as free radicals, cation and anion. Keeping in view the
limitations of the course, we will discuss the mechanism of free radical addition polymerisation
only and that too in respect of ethylene and its derivatives.
Mechanism of Free Radical Addition Polymerisation
The polymerisation occurs with compounds such as alkenes and vinyl compounds i.e.,
substituted alkenes such as H 2C = CH-G, where G may any group such as -CH3 , -CI,
-CN etc.
A. Alkene polymerisation. This type of polymerisation is performed by heating the
monomer with a small amount of initiator (commonly peroxides) or by exposing the monomer
to light.
tert-Butyl peroxide, benzoyl peroxide, acetyl peroxide are commonly used initiators because
they decompose under mild conditions to form free radicals.
tert-Butyl peroxide tert-Butoxide radical

Benzoyl peroxide Benzoyloxy radical phenyl free radical
o 0
II II °
H3C - C - 0 - 0 -C -CH3 70-90·C ) 2CH a + 2C02
methyl free radical
Besides peroxides, the azo compounds have also been reported to act as initiators. For
example, NN'-bis (2 methyl propanenitrile), commonly known as azo bis isobutylonitrile (AIBN)
forms a pair of 2-methyl propanenitrile free radical.
50-70·C )
The reaction involves the following steps:

(i) Chain initiation. Organic peroxides undergo homolytic fission to form free radicals
which act as initiater(RO).
°
Peroxides ~ Rad o (shown as R)
The initiator adds to the carbon-carbon double bond of an alkene molecule to form a new
free radical.
o~~--+~ R-CH2-CH2
Free radical
Chain propagation. The new free radical adds to a double bond of monomer to form
(ii)
a larger free radical. The radical formed adds to another alkene molecule to form an even
larger free radical. This process continues until the radical is destroyed. These steps are called
propagation steps.
n~.
R-CH2-CH2-CH2-CH2 + CH2-CH2~-•• R-CH2-CH2-CH2-CH2-CH2-CH2
•
1
R---(CH2-CH2t n
Polymer
Above steps are repeated until fmally polymer is obtained.

(iii) Chain termination. The above chain reaction terminates when the two free radicals
combine. For example,
°
2 R-CH 2-CH2-CH2-CH2 ~ R CH2CH2CH2CH2CH2CH2CH2CH2R
B. Vinyl polymerisation
Most of the commercial addition polymers are vinyl polymers obtained from alkenes and
High Polymers 249
their derivatives, such as propene, H 2C = 6: b
, vinyl chloride, H 2C = H , etc. represented in
g
b
general as : CH 2 = H .
The polymerisation reaction involves the same steps

(a) Chain initiation step
Initiator ~ R
.
•
R+CH 2 =r
Vinyl compound
(b) Chain propagating step
R -CH2 -b•HCH2 =bH~ R -CH2-bH-CH2 -bH2~R<CH2

+
•
-bH)nCH -bH 2
Polymer
(c) Chain termination step
2R(-CH2 -bH-)nH2C-iH~R(CH2 -bH)n -CH2-6H -r- CH2 -<6H-CH2-)nR
7.6.1 Chain Transfer

There is yet another method of chain termination. Which takes place by the transfer
reaction. In the termination reaction brought about by coupling or disproportion, the products
formed are dead or non reactive and, hence no further chain propagation is possible. In the
case of transfer reaction, however, while the growth of one polymer chain is stopped or arrested,
forming a dead polymer, there is a simultaneous generation of a new free radical capable of
initiating a fresh polymer chain growth. This reaction takes place by the abstraction of a
hydrogen atom or some other atom from the initiator, monomer or polymer or from any other
species present in the system, including the solvent or any inadvertent impurity. This is
represented as below:
R - [CH 2 - bHJn - CH2 - bH + R'H ~ R - [CH2 - bHJn - CH2 - bH2 + R'
chain-transfer.
-wtHr CH 2 -
•
~H - CI + CCl s
• • styrene ~ polymer
CIgC + CH2 = Z.H ~ CISC - CH2 - Z.H
-wtHrr· + Inhibitor ~ -wtHr~ r + inhibitor.
Unreactive:
cannot initiate
new chain
n.C S H 13CH = CH2 + CBr4 _",pe;.:;,.roo;.:Xl;;,:·d;.:;.es,---+) n.C S H 13 b:CH2CBr3
t-Butyl peroxide or benzoyl peroxides are commonly used for free radical polymerisation.
The polymerisation reaction of alkenes and vinyl polymerisation may be written as :
~
Rad + CH 2 = CH ---+ Rad - CH 2 - CH
f. HC:dH ) Repeat ~ (-CH 2 -
2 6H-)n
Polymer
7.6.2 Inhibition and Retardation

If a foreign substance is added to a monomer and it leads to a reduction in the degree of
polymerization without completely suppressing it, the added substance is known as retarder.
An example is nitrobenzene. On the other hand, if it reacts with the chain radical to yield
non-radical products or radicals of such low reactivity that they are incapable of adding fresh
monomer units, the compound added is called an inhibitor. After the consumption of an inhibitor,
polymerization follows the normal course.
Inhibitors slow or stop polymerization by reacting with the initiator or the growing polymer
chain. The free radical formed from an inhibitor must be sufficiently unreactive that it does
not function as a chain transfer reagent and bring another growing chain. Benzoquinone is a
typical free radical chain inhibitor. The resonance stabilized free radicals usually dimerizes or
disproportionate to produce inert products and end the chain process. Hydroquinone,
nitrobenzene, dinitrobenzene and benzothiazine are some of the common inhibitors used in
the polymer industry.
The mechanism of radical termination by nitro groups may involve one of the follOWing
processes.
RM,.~/o
1,,=/- ~o
/
~< > <:M,.R
7.7 POLYMERIZATION TECHNIQUES
In principle, a polymerization reaction may be carried out in the solid phase, the liquid
phase or the gas phase. In practice, commerical scale polymerizations are almost always
conducted in the liquid phase.
The conversion of a monomer into polymer is an exothermic process, and if this heat is
not dissipated or properly controlled, serious explosions will result. The basic methods of
polymerization may be either homogeneous or heterogeneous, which are further classified as
under:
(a) Homogeneous polymerisation. In this case the polymerisation reaction take place is
one homogeneous phase consisting of either only monomer or monomer with a solvent. These
are of two types :
High Polymers 251
(i) Mass or Bulk. polymerization.
(ii) Solution polymerization.
(b) Heterogeneous polymerisation. In this case, more than one phase is involved. These
are again of two types:
(i) Emulsion polymerization.
(ii) Bead polymerization or suspension polymerization.
The water soluble initiator links to the hydrophilic end whereas the monomer is linked to
the hydrophobic end. If the amount of the surfactant added is below a certain concentration
called critical micelle concentration (cmc) the surfactant molecules are freely dispersed in the
medium and the polymers that are formed under this condition will have smaller molecular
masses (Fig. 7.4 A).
However, at concentrations of surfactant beyond cmc, the surfactant molecules aggregate
to form micelles where the nonpolar group collect together facing each other with polar ends
directing away as shown in Fig. 7.4 B. This results in the flocking of monomers within the
micelle. Now, an initiator molecule at the polar end diffuses into the micelle to initiate the
polymerization process (Fig. 7.4 C). As the polymerization progresses (Fig. 7.4 0), there will
be a depletion in the number of monomers within the micelle. They are replenished by the
medium. This continues till the polymer formed is big enough to come out. The pure polymer
is isolated from the emulsion by the addition of a de-emulsifier.
(i) Mass or Bulk Polymerization
The polymerization is carried out in two stages, in order to control the heat of the
polymerization reaction. ~e reaction is quite slow initially, till about 10% conversion, and
thereafter it is very fast. Bulk. polymerization can be carried out batch wise or in a continuous
manner. In the batch method, a g2.sseous or liquid monomer with a initiaor or catalyst is fed
into the reaction vessel and is heated to the required temperature. The first stage consists of
radical-initiated thermal polymerization of the monomer. As the proportion of the polymer
increases, the temperature also increases, and the reaction mixture is cooled by circulating
water through cooling coils. The reaction mixture becomes vircous, and when the consumption
ofthe monomer is approximately 10 to 25%-depending on the monomer. The reaction monomer
is transferred into the main reactor. The polymer encounters progressively higher temperature
ranging from 110° to 200°C. Almost 100% polymerization is ensured. The molten polymer is
extruded into rods, or fabricated into sheets. (Polystyrene, butadiene rubber). After that the
polymer body is then subjected to mechanical processing. In modern technology the bulk
polymerization is carried out in a continuous manner.
Bulk. polymerization is preferred when the reaction is not two strongly exothermic and
the mixture does not become two viscous before the polymerization reaches an advanced stage.
Bulk polymerization also be used in the free radical polymerization of methyl-methacrylate or
styrene. It is very simple and the polymer obtained by this technique is quite pure. This process
have minimum contamination and have straight forward recovery of the polymer. The polymer
obtained can even be used as such because no isolation from other component is involved.
Important Features of Bulk Polymerization
(i) This technique is very suitable for the production of medium molecular weight
polymer to high molecular weight polymer.
(ii) This technique is used for additions polymerization, free radical polymerization and
condensation polymerization.
(iii) It is minimum contaminated, hence the polymer obtained has high purity.
(iv) It is usually a homogeneous system, but in certain cases, where the polymer is
insoluble in the monomer, then the system becomes heterogeneous.
(v) The product can be easily isolated and can be used as such for moulding purposes.
(ii) Solution Polymerization
In solution polymerization the monomer is dissolved in a solvent prior to polymerization.
This technique is commonly employed for the ionic polymerization of gaseous vinyl monomers.
The solvent facilitates contact of monomer and initiator (which mayor may not be soluble in
the solvent) and assists dissipation of exothermic heat of reaction. A limitation ofthis technique
is the possibility of chain transfer to the solvent with consequent formation of low molecular
weight polymer. An added disadvantage is the need to remove the solvent in order to isolate
the solid polymer.
The solution polymerization technique has been used for the production of polyacrylonitrile
by free radical polymerization and that of poly isobutylene by cationic polymerization. This
technique involves first dissocation of monomer in a suitable solvent and then initiator is added
to start the polymerization reaction. If both the monomer and the polymer is soluble in the
solvent then a lacquer or varnish is obtained. If only monomer is soluble in the solvent, the
polymer is precipitated. The precipitate is then filtered off, washed and dried.
In this technique, the monomer, the catalyst, initiator and other admixtures are dissolved
in suitable solvent and then heated in a reaction with a stirrer under constant agitation. Heat
is removed from the reaction zone and the temperature is controlled. The polymer obtain~d
by this technique have more uniform structure but have a low molecular weight.
Important Features of Solution Polymerization
(i) The technique is used where the polymer is employed in its solution form, as in the
case of certain adhesives and varnish etc.
(ii) It is also useful in systems where the polymer formed is insoluble in its monomer or
solvent and precipitated out as a slurry.
(iii) Viscosity of the medium increases but slowly.
(iv) For very high conversions longer duration is required.
(u) This technique is most suitable for making low molecular weight products.
(vi) This technique is suitable for free radical, cationic, anionic and even co-ordination
polymerization.
High Polymers 253
(iii) Emulstion Polymerization
In emulsion polymerization, the monomer is dispersed in water containing a soap
(surfactant) to form an emulsion. Such a dispersion is stable and its existence is not dependent
on continued agitation. At the start of an emulsion polymerization, three components are
present. These are (i) a water soluble monomer (ii) a water soluble initiator and (iii) and a
surfactant i.e., emulsfier. The emulsifer is a long chain molecule with a hydropholic group at
one end and a hydrophilic group at the other end. Heat transfer is very efficient and the vincosily
build up of the polymerization mass is quite low as compared to that in the bulk and solution
techniques. Since the polymerization proceeds at the micelles, where the surface volume ratio
in very high the ratio of polymerization is quite high. For efficient making of an emulsion, it
is necessary to agitate the monomer water mixture in presence of a measured dose of an
emulsifying agent.
adqueous phase
(A) . (B)
\. ,--'
\. ,--....-
\
\.
~ \ \'
Individual surfactant
Aggregated (surfactant
molecules
molecules (micelles)
- ' - : Norpoiar hydrocarbon chain of the surfactant molecule
• : Polar head of the surfactant molecule
Polymer
chain
(D)
(C)
Initiator
molecule
diffusing
into the micelle
Fig. 7.4. Emulsion polymerization process (A) Free surfactant molecules below erne (B) Aggregation of
surfactant molecules to form micelles above erne (C) Diffusion of initiator (D) Polymer chain growth.
This technique is used to prepare PVC, PVAC, etc. The monomer is dispersed in water as
droplets which are stabilized by the addition of a soap or detergent or protective colloids (like
gum, gelatin or dextrine).
Initiators are either water soluble or monomer soluble. Usually persulphates are used.
These give rise to sulphate ion radical, SO~- . The ion radical interacts with the monomers in
the micelles and polymerization occurs. The polymers thus obtained is of very high molecular
weight and is in the form of suspension. The suspension may be coagulated with an acid in
order to get the solid polymer. The pH of the medium affects the polymerization rate and the
quality and yield of the polymer formed. The kinetics of the process and the degree of
polymerization of the polymer formed depend also on :
(i) The quality of the initiator used.
(ii) The temperature and duration.
(iii) The speed of agitation and other factors.
Mter completion of polymerization, fine particles of polymer is stabilized by the emulsifier
layer and dispersed uniformly in the aqueous phase. This dispersion is known as latex,' which
can be used as such for making adhesives and water soluble emulsion paints etc. The
polymer can also be isolated from the latex by destabilizing the emulsion by spray drying or
by freezing.
This technique is employed in industry for the production of polyethylene, polyvinyl chloride,
polystyrene, polypropylene and various rubbers.
Important Features of Emulsion Polymerization
(i) Emulsion polymerization is the most widely used industrial technique.
(ii) It is generally the heterogeneous system. In order to keep the emulsion stable,
agitation and proper control of emulsifier and stabilizer is essential.
(iii) The viscosity of the medium remains almost constant during polymerization.
(iu) The rate of polymerization is high because polymerization proceeds at the micelles,
where the surface/volume ratio is very high.
(v ) Emulsion can be used directly for paints, adhesives, etc.
(iv) Suspension Polymerization
In suspension polymerization, the polymer is dispersed in water in small droplets (generally
about 10-2 - 10-1 cm in diameter) maintained by vigorous stirring. This technique is extensively
used for the free radical polymerization of vinyl monomers. A monomer soluble initiator is
added and polymerization occurs within each droplet. Generally a material such as poly (vinyl
alcohol) or gelatin is added to provide a protective coating for the droplets; this prevents the
droplets from cohering when they are at stage of being composed of a sticky mixture of monomer
and polymer. Besides facilitating the removal of exothermic heat of reaction, suspension
polymerization has the advantage that the polymer is obtained in the form of small beads which
are easily collected and dried.
High Polymers 255
This process is largely used to manufacture PVC and polystyrene. In this technique, the
initiators used are insoluble in water, but soluble in the monomer. The monomer is dispersed
as fine droplets in water containing poly (vinyl alcohol), water-soluble cellulose derivatives and
gelatin as suspending agents to stabilize the suspension. The mixture is kept agitated at a
temperature of 50°-60°C in a sealed vessel and the gas is admitted at high pressure. The heat
of polymerization is absorbed by the water present. The polymerization is initiated by oil soluble
peroxide, soluble in monomer droplets. Polymerization takes place independently in each drop.
The process is stopped at about 90% conversion, since the reaction is slow after this stage.
The unconverted monomer is recycled. The polymer is separated by centrifuging. The resulting
polymer, which has a high molecular weight, is precipitated in the form of water soluble solid
particles, (spheres or pearls) and it is easily recovered on a drum filter. It is then washed and
dried. Methyl methacrylate can also be polymarized in this way to give a polymer which can
be melt-fabricated. It is also possible to obtain easily, separable beads, which can be used as
ion exchangers. Polyvinyl acetate beads and styrene divinyl benzene copolymer beads are
manufactured by this technique using free radical initiators.
Important Features of Suspension Polymerization
(i) Medium to high molecular weight polymer can be made by this technique.
(ii) This technique is used for free radical and poly condensation polymerization.
(iii) Proper agitation and stabilizer is essential to keep the suspension stable.
(iv) The isolation of product is early because the product is obtained in the form of beads
or pearls.
(v) The product can be used directly for moulding purposes.
7.8 GLASS TRANSITION TEMPERATURE

Amorphous polymers in the solid state are rigid, hard and transparent like glass and the
state is referred to as the glassy state. In this state, the polymer is brittle, as the
molecular chains can not move easily. When such polymers are slowly heated, two transitions
temperatures can be observed. These are p-transition temperature (T~) and glass transition
temperature (Tg)'
At T~, only sided groups in a polymer have sufficient thermal energy to rotate, whereas at
Tg segments i.e., complete blocks consisting of some C atoms of the main chain of the polymer
become free to rotate as an entity. Due to this, the behaviour of polymer also changes from
glassy to rubbery one. In the rubbery state, the molecules adopt random coiled conformations
as a result of free rotations about single covalent bonds in the chain back bone. All amorphous
polymers change on heating from glassy state to rubbery state and vice versa on cooling at a
definite temperature called glass transition temperature of the polymer.
For instance, when an ordinary rubber ball is cooled, it becomes harder and harder till its
Tg is reached. When it reaches -70°C (Tg rubber) it will break into pieces like a glass ball.
When warmed, the ball again regains its rubbery state. All amorphous polymers show this
property which is characterized by glass transition temperatures, (Tg ). Glass transition
temperature is defined as the temperature at which a polymer abruptly transforms from the
glassy (hard) to the rubbery state (soft). This transition corresponds to the beginning of a chain
reaction and is attributed to the easier molecular rotation about single bonds at Tg and beyond.
Below Tg , polymer chain motion virtually ceases and the polymer is said to be frozen in position.
Thus the polymers become hard, stiff, brittle and transparent just like inorganic glasses. The
rubbery state is also referred to as viscoelastic state. On further heating the polymer melts
and reaches a molten or viscofluid state.
Glassy state Viscoelastic state Viscofluid state
(Hard and brittle) (Rubbery) (Polymer melt)
Glass transition temperatures of a few amorphous polymers are given in Table 7.1. The
glass transition is a second order transition. In this respect it differs from true phase changes
such as melting or boiling which are known to be first order transitions.
Table 7.1. Glass transition temperature (Tg ) of polymers.
Polymer Tg' °C Contril)uting factor
Polyethylene -20 flexible backbone

Polypropylene 5 eRa groups inhibit freedom of rotation
Polyvinylchloride 80 strong polar attraction between molecules
Polytetrafluoroethylene 115 stiff backbone.
A given polymer may behave like a glass or a rubber depends on whether its Tg falls below
or above the room temperature. For example, polystyrene (Tg = 100°C) behaves like glass and
most rubbers (Tg < - 20°C) show rubbery properties at room temperature (25°C).
Factors Affecting Glass Transitions Temperature
1. Chain Flexibility. Flexibility to the polymer is provided by free rotation of backbone chains
made of C-C, C-O and C-N single bonds. Presence of rigid structures in the polymer chain
such 2.8 aromatic rings or bulky side groups on the backbone of C atoms hinder the freedom of
rotation thus lowering the chain flexibility and increase in Tg. For example Tg of polyethylene
among PE, PP and PS follows PE < PP < PS.
-CH2-CH2-CH2-CH2-CH2-CH2- (Free rotation of C chain is possible)
Polyethylene
-CH2 -yH -CH2 -yH -CH2 -yH -CH2 - (Free rotation is hindered to
CH CH CH presence of -CH3 groups)
3 3 3
(Free rotation is hindered due to
the presence of bulkier aromatic
rings)
Polystyrene
High Polymers 257
Thus Tg is affected by the nature of substituents in the side chains.
2. Intermolecular forces. Presence of large number of polar groups in the molecular chain
lead to strong intermolecular forces which restrict the molecular motions. This leads to an
increase in T g. For example, Tg of polypropylene, polyvinyl chloride and of nylon 66 follows.
the order PP < PVC < nylon 66
........ ........
~ ..........CH2
..........C=O··..·····..······· H-N,
.................. H-N" /C=O ..........._...·
/CH2 H2 C,
(No polar groups) Polyvinyl chloride (Presence of H-bonds
(presence of -CI polar group) between polar groups)
3. Branching and cross linking. A high degree of branching brings the polymer chains closer,
lowers the free volume, thus reducing the chain mobility and resulting in an increase in Tg'
Hydrogen bonds will have a similar effect on Tg . Similarly the greater the degree of cross
linking, the higher the Tg .
4. Stereoregularity of the polymer. A syndiotactic polymer has a higher Tg than atactic
polymer which in turn has higher Tg than its isotactic stereoisomer.
5. Molecular mass. Tg is directly proportional to molecular mass of the polymer. Higher
the molecular mass, more is the restriction in the molecular freedom. However, Tg is not
significantly affected by molecular masses if the degree of polymerization is above 250.
6. Plasticisation. Addition ofplaticisers decrease the Tg • It is because plasticiser molecules
cause separation of the chains and increase their mobility.
7. Copolymerisation. Copolymers have lower value ofTg's as compared to homopolymers.
It is because copolymerisation promotes disorder, reduce molecular packing and also reduce
the interchain forces of attraction.
Crystalline Melting Point (Tm)
Even a polymer with regularity in molecular structure does not exist entirely in crystalline
forms. In fact polymers have regions of crystallinity called crystallities, embeded is amorphous
material. Crystallinity in characterised by crystalline melting point (Tm)' which has a definite
value for a polymer depending upon the chemical structure of the chains present in it. Tm is
the temperature at which the polymer changes from its viscoelastic state to viscofluid state on
heating and vice versa on cooling. Tm is the temperature at which sufficient thermal energy is
available to desrupt the ordered structure of the crystalline polymers.
A material with 100% crystalline nature will have a definite value of only Tm but no Tg .
Similarly a material which is 100% amorphous will have definite value of only Tg but no Tm'
However, polymers may have both these transition points depending upon the percentages of
crystallinity possessed by them. Polymers with 100% crystalline nature or 100% amorphous
nature do not exist in practice.
Detection of Tg lmd T m
From themodynam c point of view, the glass temperature (Tg) is a second order transition.
In this respect it differs from true phase changes such as melting or boiling which are known
to be the first order transitions. However, Tm is a first order transition because there is an
abrupt change in a fundamental property such as
specific volume with temperature. But, Tg is a
second order transition as only the first derivative
of such properties changes. For the
i
<Il
S
;:l
determinations ofTg and T m , the specific volume '0
::-
of a semi-crystalline polymer sample is measured tJ ' (Vi scofluid
~
as a function of temperature. The plotting of al i (viscof1uid statp)
Po ! state)
specific volume against temperature in shown in U1 (Glussy state)! T K
Fig. 7.5.
Temperature - - .
At high temperatures, the semi-crystalline
polymer is in fluid state and as the temperature Fig. 7.5. Specific volume-temperature curve for
semicrystalline polymers.
is decreased, the specific volume of the polymer
also decreases before Tm is reached. After Tm' further decrease in temperature leads to rapid
decrease in specific volume. This is because crystallisation occurs and crystals are significantly
denser. Near Tg , the slope of the curve changes and below Tg , further contraction takes place
through the amorphous regions. Below Tg' the polymer is in solid physical state and molecules
have amorphous and crystalline regions.
The concept of free volume can be used Vf Free volume is
to analyse the glass transition. The free
i represented by
volume is the space in a solid or liquid
sample which is not occupied by polymer i the shaded area
molecules, i.e., the 'empty-space' between

molecules. Above TR' the free volume is high
so polymer mOlecules can change
conformations freely. As the temperature of
the melt is lowered, the free volume will be (Glassy state)
reduced and the chances of molecular Temperature - +
rotation to take place will be reduced. The
temperature at which of molecular rotations Fig. 7.6. Illustration ofthe variation ofsp. volume of
. . a polymer with temperature.
become mInImUm corresponds to Tg as below
this temperature the polymer glass is effectively 'frozen'. This is also shown in Fig. 7.6.
Below Tg => free volume is constant (V/).
Above Tg => free volume increases with temperature (Vr).
Significance of Glass Transition Temperature
Glass transitions temperature (Tg) can be used in the following cases:
(i) To evaluate the flexibility of a polymer and predict its response to mechanical stress.
(ii) Many polymers show an abrupt change in their physical properties at their glass
transition temperature. For instance, properties such as coefficient of thermal expansion, heat
capacity, refractive index, mechanical damping, modulus of elasticity and electrical properties
abruptly change at T g . The usefulness of a polymer over a temperature range can thus be
determined.
(iii) Polymeric materials are subjected to different processing operations such as moulding,
calendring and extrusion. A knowledge of Tg is useful in choosing appropriate temperature
range for such processing operations to be carried out.
7.9 STRUCTURE PROPERTIES RELATIONSHIP OF A POLYMER
Or
EFFECT OF POLYMER STRUCTURE ON PROPERTIES
The physical, chemical and mechanical properties of a polymer are determined by the nature
High Polymers 259
of monomer units and its structure. Polymers differ in properties to a large extent. They may
be hard or soft, elastic or rigid, transparent or opaque. They may have the strength of steel
but very light in weight. They may soften on heating and the melt may set to a hard mass on
cooling. The hard mass may be moulded to different articles and this process of moulding may
or may not be reversible. These properties may vary from one type of polymer to another and
even among the polymers of the same type, there may be differences in properties.
There are several factors which play an important role in deciding the structure and hence
the properties of a polymer. Some of the important factors whcih determine the structure and
the properties of a polymer are molecular mass polarity, crystallinity, molecular forces, nature
of polymeric chains and stereo chemistry of the molecule. The relationship of structure with
some properties are given below:
(i) Strength
This properties of the polymers depend mainly upon the magnitude and distribution of
attractive forces between the molecules, namely (i) the primary chemical bond forces and
(ii) secondary intermolecular forces. The strength increases with chain length and molecular
weights.
Polymer chains in linear polymers are held together by weak inter molecular forces which
can be easily overcome by heat and pressure. Hence, they show highest degree of plasticity.
In cross linked polymers, due to presence of cross links, the molecular sliding is restricted.
Hence, they do not become soft on heating and have high strength and low plasticity. Crystalline
polymers are also hard but the polymers with low crystallinity have low strength.
Strength of polymer depends upon its shape also. The polymer with simple and uniform
shape has low strength e.g., polythelene. However, if the hydrogen atom of alternate carbon
in PE is replaced by chlorine, the movement of the molecule gets restricted and therefore,
PVC becomes stronger than PE. In polystyrene, the H atoms are replaced by still bulkier phenyl
groups and the movements is further restricted due to stronger van der Walls forces.
Consequently, polyvinyl chloride (PVC) is stronger and tougher polymer than polyethylene (PE)
and polystyrene (PS) has all the more strength and toughness.
H H H H H H H H
H H H H I I I I
I I I I I I I I
~C-C-C-C----'IIW{"" ~?-?-r-?~ ~r-C-r-T
I I I I H Cl H CI H6H@
H H H H
(PVC) (PS)
(PE)
The relative arrangement of polymeric chains decides the shape of a polymer molecule. In
linear polymers, the polymeric chains usually stack one over another and form a well packed
structure. Due to close packing of polymeric chains, linear polymers have high densities, high
tensile strength and high melting points. The strength of linear polymers also depends upon
the slippling power of one molecule past another. For example, in high density polyethylene,
the polymer chains line up in a zig-zag fashion and can easily slip one over another because
there is only limited restriction to movement. On the other hand, in polyvinyl chloride, the
movement is much more restricted due to the presence of bulky chlorine atoms. This is why
polyvinyl chloride is a tougher and stronger polymer as compared to polyethylene.
Branched chain polymers, due to the presence of branching, are unable to pack themselves
in a compact manner. This is why they have low densities, low melting points and low tensile
strength. Low density polyethylene is an example of this type of polymers.
Cross-linked polymers possess a three dimensional network structure. Due to the presence
of cross-links, the movement of chains relative to one another is totally restricted and
consequently they are very tough and strong. Bakelite is an example of such a polymer.
(ii) Crystallinity
The relative arrangement of macromolecules with respect to each other decides the
crystalline or amorphous nature of a polymer.
When the constituent macromolecules possess a completely random arrangement, the
polymer is said to be an amorphous state. On the other hand, the crystalline state of a
polymer consists of definite crystalline regions (called crystallites) embedded in an amorphous
matrix.
In a crystalline polymer, there are regions of high order as well as random disorder. It is
highly ordered region, called crystallite, the polymer chains are aligned in a regular fashion,
while in a disordered region (amorphous region) the polymer chains are arranged randomly.
The degree to which molecules of a polymer are arranged in orderly pattern with respect to
eaeh other is regarded as a measure of the crystallinity of the polymer.
In low molecular weight solids, the individual molecules are arranged in regular
manner, whereas in high molecular weight polymers, there may be regions of high as well as
low order.
The relative amount of crystallinity and amorphousness of polymer mainly depend upon
the following factors:
(i) Megnitude of attractive intermolecular forces
riO Symmetric structure of the macromolecules
The symmetry of the structure of macromolecules play an important role in imparting
crystallinity of a polymer. Higher the symmetry of the macromolecules, greater is the
crystallinity of the polymer. When the polymeric chain is regular and does not contain bulky
side groups, the polymer has a highly crystalline structure. For example in polyethylene, the
polymeric chains are regular and can line up in a zig-zag fashion as shown in Fig. 7.7. This is
why polyethylene is highly crystalline.
On the other hand, when polymeric chains contain bulky side groups attached randomly
to the main carbon chain, the polymer has a low degree of symmetry and consequently has
amorphous nature. For example, polystyrene, polyvinyl acetate, polymethyl methacrylate have
bulky side groups attached to the main and are amorphous in nature.
Fig. 7.7. Arrangement of polymeric chains in a crystallite of polyethylene.

High Polymers 261
-CH2 -~H - CH 2 -~H - CH2-
o '0
H3 H3
Polyvinyl acetatE'
Polymer chains with polar groups causing hydrogen bonding or dipolar attraction have high
crystallinity. An example of such a material is nylon, a polyamide
Nylon (Polyamide)
In addition to the above, crystallinity is increased by copolymerization because it lowers
the structural symmetry.
(iii) Tacticity or Orientation in Polymers
The orientation of characteristic group (R) of the monomer in the polymeric chain is known
as tacticity. The head-to-tail arrangement of monomers in a given polymer may have different
orientation of the characteristic group (R), which may be either orderly or disorderly arranged
on the polymer chain. Depending upon the geometric arrangement of the characteristic group,
three different types of polymers are there.
(a) Atactic polymer (Greek - without order). In these polymers, all the characteristic
groups (RJ are arranged randomly on both the sides of the polymer chain. This type of polymer
is obtained by free radical polymerization. The polymer is elastic with a lower softening and
melting point and therefore, can be moulded comparatively at lower temperatures. The polymer
due to its poor strength can not be spun into strong fibre.
-r-~-~-~-~-~-r-~-~-
(b) Isotactic polymers (Greak - Same order). In these polymers, all the characteristic
groups are present on the same side of the polymer chain. This type of polymer is obtained by
Ziegler-Natta catalyst. The polymer has a high degree of crystallinity, are more denser and
strong because of the presence of regularity in the chain structure.
-~-~-~-~-~-~-~-~-~-
(c) Syndiotactic polymers (Greek - Contrasting order). In these polymers, the
characteristic groups are arranged regularly on alternate sides of the polymer chain. For
example gutta percha.
It must be made clear at this stage that the isotactic and syndiotactic polymers are more
crystalline than the atactic polymers. It is due to the regular orientation of the characteristic
groups in these polymers which allow the adjacent chains to approach each other to such an
extent so that the attractive forces come into operation.
Isotactic polystyrene has a regular structure and is more crystalline than atactic polystyrene
where the phenyl groups are arranged at random along the chain.
Isotactic polystyrene
Atactic polystyrene
(iv) Geometric arrangement of double bond in polymers
It also affects the properties of polymer. For example, natural rubber is isomorphous, while
gutta percha is crystalline, although both polymers are made up of the same monomeric unit
i.e., 2-methylbuta-l, 3-diene. In natural rubber, all the double bonds are cis-with the result it
is amorphous, possesses elasticity and melts comparatively at lower temperature than its trans-
isomer gutta percha. In the latter, the double bonds are trans-with the result it is crystalline,
hard substance and melts at higher temperature than natural rubber. The structures of both
gutta percha and natural rubber are shown below:
H3~
H
"c/ e=c!
H ,\H3 }J>
gutta percha (all trans - configuration)
/
H Ii
\/
\H3
e=~
H
. / ~/ '"
H3~X;= ~ /"'-. /""
""e- ~/~/ '"
/ -, H
H H H H H eH3 HH "H
(natural rubbers (all cis - configuration)
In natural rubber the -CH3 group and H atom attached to the cation joined by double
bond lie on the same side, whereas in gutta percha the groups lie on the opposite sides.
High Polymers 263
(v) Plastic deformation
When a thermoplastic polymer is subjected to heat, it gets deformed. This property of
thermoplastics is known as plastic deformation. Thermoplastic polymers get deformed due to
application of heat and pressure. It is due to weak intermolecular forces present between them.
The maximum degree of deformation is shown by linear polymers without branched or cross
linked structure. On applying heat weak vander Wall forces of attraction acting between
different molecules are easily overcome and hence under pressure they deform. On cooling,
they regain their original hardness. Repeated heating and cooling do not affect the nature of
the polymer. In case of cross linked polymers, primary covalent bonds are present throughout
the structure and hence there can be no slippage between the molecules on applying heat.
Such polymers are thermosetting polymers.
(vi) Elasticity
It is defined as the phenomenon of recovering the original shape after removal of deforming
stress. The elastic deformation is due to the presence of long chains of molecules having free
rotating groups. These groups assume irregularly coiled configuration in unstressed condition.
On stretching, the coils start to disentangle and chains become oriented. The orientation of
chain causes crystallization which enhances the attractive forces between different chains and
causes stiffness. When stress is released, the coils return back to their original conformation.
Hence they exhibit complete recovery of shape.
Thus, elasticity of a polymer material is due to the uncoiling and recoiling of the molecular
chains on the applications of force.
For a polymer to show elasticity the individual chains should not break on prolonged
stretching. When the chains slip past each other and get separated breaking will take place.
In rubbers this is avoided by (i) introduction cross linking at suitable positions (ii) avoiding
bulky side groups such as aromatic and cyclic structures and (iii) introducing more non-polar
groups on the chain so that the chains do not separate on stretching. The structure should be
amorphous so that the material has a glass transition temperature lower than the temperature
at which it is used. This can be brought about by compounding the rubber with a suitable
plasticizer liquid (external plasticizer). It may also be done by copolymerisation when the other
monomer acts as internal plasticizer. In other words to get an elastic material, any factor that
introduces crystallinity should be avoided.
(vii) Elastic deformation (rheology) of polymers
The elastic deformation of polymers (flow behaviour) is called rheology. It can be studied
by applying stress on the polymer material and determining the deformation caused. In a solid,
the deformation increases proportionately to the load and retracts instantaneously on withdrawal
of the load. Polymers, contain both crystalline and amorphous regions so they exhibit a complex
behaviour. In general, both the regions exhibit elasticity in the glassy state while in the rubber
state the amorphous components exhibit viscoelasticity. The deformation depends upon the
degree of crystallinity, degree of cross linking and the glass transition temperature. Based on
this, polymers can be classified as (i) soft and tough, (ii) soft and weak (iii) hard and tough (iv)
hard and strong, and (v) hard and brittle. Highly cross linked elastomers (e.g. vulcanized rubber)
are amorphous and exhibit soft and tough behaviour above T . Hard and strong character
against stress is shown by fibres such as nylon and hard and ~rittle character is shown by
polystyrene below their glass transition temperature.
(viii) Chemical reactivity
Chemical properties of a polymer depend upon the nature of chemical groups present in
the polymer. For example, poly alkenes such as polyethylene and polypropylene are inert as
they contain only C-C and C-H bonds. If tertiary carbon atom is present, they easily undergo
oxidation. Teflon is very stable and chemically inert due to presence of C-C and C-F bonds.
Nylon and polyester undergo hydrolysis due to presence of a mild ester linkage.
The chemical properties of polymers are also largely determined by the nature of their
monomer units. Following examples illustrate this fact:
(i) Cellulosic polymers contain the free hydroxyl groups (originally present in their
monomer units). Due to the presence of free hydroxyl groups, they react with a variety
of reagents and give products with modified properties. For example, cellulose (a
natural polymer) reacts with nitric acid to form nitro-cellulose which is used in making
gun cotton and celluloid. Similarly, it reacts with acetic acid to give cellulose-acetate
which is used for making thin films, sheets etc.
(ii) Natural rubber contains double bonds (originally present in the monomer units) and
is susceptible to the attack of ozone. On the other hand, polyethylene having no double
bond in its polymeric chains does not react with ozone.
(iii) Silicone polymers can be used at high temperatures. This is because, the Si-O linkages
present in them possess very high thermal stability.
(ix) Solubility
When a polymer is put in solvent, it involves the diffusion of solvent into the polymer.
Therefore, it swells and finally disintegrates. Polymer is soluble in that solvent which is
chemically similar to it. For example, natural rubber is soluble in CCl4 (Non-polar), whereas
it is not soluble in polar ethyl alcohol.
The solubility of polymer decreases as the molecular weight of polymer increases. It also
increases with increase in cross-linking. Crystalline polymers normally have higher chemical
resistance than the less crystalline polymers having similar chemical structure. It is due to
the dense packing of molecular chains in the more crystalline polymers, which makes the
penetration of solvent difficult.
1. Why do all simple organic molecules not produce polymers? (UPT, Jan. 01)
2. What is the minimum functionality required for a monomer to form a cross linked
polymer? (Dibrugarh, July 01)
3. Differentiate between a homopolymer and copolymer. (Ku, May 99, June 2K)
4. Write the ionisation propagation in termination reactions involved in the
polymerisation of ethylene withAIBN. (UPT, May 01)
5. How does the presence of benzoquinone inhibit the free radical polymerisation of a
vinyl derivation?
6. Are proteins natural or synthetic polymers?
7. Why should one always use purest monomer in free radical polymerisation reaction?
8. Arrange the following polymers in increasing order of their intermolecular forces.
Also classify them as addition and condensation polymers:
Nylon-66, Buna-S, Polythene.
High Polymers 265
( ANSWERS)
1. The simple organic molecules like C2H 5CI, C2H 50H, H3C-COOH etc. do not form
polymers, because they are mono functional molecules. To form a polymer, the
monomer molecule must be at least bifunctional. For example, ethylene forms
polyethylene. The double bond in ethylene provides two bonding sites per molecule.
So a large number of ethylene molecules can join with one another to form
polyethylene. Similarly, ethylene glycol (HO-CH 2-CH 2-OH) is a bifunctional
molecule and can act as a monomer for the formation of a polymer (polyethylene
terephthalate).
2. To form a cross-linked polymer, the minimum functionality required by a monomer
is three. The monomer must be trifunctional at least to form cross-links.
3. Homopolymers are obtained by the polymerisation of only one type of monomers.
For example, polyethylene, polyvinyl chloride and polystyrene.
Copolymers are obtained by the polymerisation of two or more monomers. For
example, nylon 66, bakelite and epoxy resins.
4. Just like benzoyl peroxide, azobis isobutyronitrile (AIBN) can act as initiator It
dissociates to give free radicals as under.
The free radicals then propagates the reaction by combining with the monomer (H2C =
CH2) as under:
The monomer molecules are then added to the free radical formed above.
free radical polymer

5. Benzoquinol combine with the free radical intermediate to form a non reactive radical
which is highly stabilised by resonance. Because of the lack of reactivity of the new
radical formed it inhibits the further progress of the chain reaction. Therefore, the
reactions stops.
o
¢
OR
Fremdi~~' + Q
o
---+.
'0
Benzoquinone Stabilised
6. Proteins are natural polymers.
7. In free radical polymerisation reaction, the impurities can act as chain transfer
agent and may combine with the free radical to slow down the reaction or even stop
the reactions.
8. Polythene < Buna-S < Nylon-66.
Nylon-66 : Condensation polymer
Buna-S : Addition polymer
Polythene : Addition polymer.
7.10 MOULDING CONSTITUENTS OF APLASTIC (COMPOUNDING OF RESINS)
For manufacturing different articles such an radio, television and telephone cabinets,
electrical appliances like switch, plugs, holders etc. house hold articles like combs, toys, trays,
floor tiles etc. a suitable plastic has to be moulded. But a pure polymer alone in never used
for moulding. It is always mixed with a number of constituents, which not only help in the
process of moulding, but impart certain desirable properties to the finished articles. The main
types of ingredients used are given below:
(i) Resins : It acts as a binder to hold the different constituents of the mould together.
Thermosetting resins in form of linear polymers having low molecular mass are used. Tliese
resins are fusible at this stage and therefore mouldable. During moulding cross linked are
formed and the mass becomes hard.
(ii) Plasticizers : To increase the plasticity and flexibility of the resin, certain chemical
substances are added which are called plasticizer.
The plasticizer weakens the intermolecular forces of attraction between the
macromolecules. Thus the flexibility and plasticity of the resin is increased. But at the same
time the tensile strength and chemical resistance is adversely affected. The presence of small
molecules of the plasticizer in between the long molecules of the resin reduce the attractive
forces between the larger molecules of the resin (Fig. 7.8).
:::>~
----:::::::-------
C- - - _ w-
)
. -.-
y
_L_ _ -.:::::--:::-----=-W---
--.-..----). --..::.::; - - '--
,.--.-~ .~.---:--,.-----
-:lI.~-."""
~ <
. ...'j-'-. .. ( ~ _
_. __ ..-._=::J
(a) (b)
Fig. 7.8(a) Resin without plasticizer (b) with plasticizer.
High Polymers 267
Certain plastics do not soften very much on heating. These can be easily softened by the
addition of some organic compounds which are called plasticizers. For example, polyvinyl
chloride (PVC) is very stiff and hard but it is made soft by adding di-n-butyl phthalate (a
plasticizer). Some other common plasticizers are dialkyl phthalates, cresyl phthalate.
Esters of higher acids like stearic acid, oleic acid or phthalic acids are commonly used
plasticizes. Dioctyl phthalate (D.O.P.), dibutyl phthalate (D.B.P.) are some examples of these
esters. Besides these, some phosphates like tributyl phosphate, isophenyl phosphate, and
tricresyl phosphate, tetra butyl phosphate are commonly used as plasticizers.
3. Filler: The materials added to the plastics during moulding to impart special properties
and to reduce the cost of the finished articles are called fillers. They increase the hardness,
tensile strength, opacity, finish and workability and reduce brittleness and tendency of shrinkage
on setting. The following instances illustrate the point.
(i) Addition of carbon black to natural rubber enhances its mechanical strength and its
abrasion resistance.
(ii) Addition of cellulosic fillers such as rags, cotton fibers, paper pulp, fabrics and wood
etc. to phenol-formaldehyde plastic (bakelite) increase the impact strength of the
moulded articles.
(iii) Addition of carborundum, quartz and mica provides extra hardness.
(iv) Barium salts are added to make the plastic impervious to X-rays.
Some common filler are : Gypsum, saw dust, talc, asbestos, carbon black, mica, pumic
powder, cork, husk, paper pulp, wood flour, marble flour, cotton fiber, china clay, metallic
powders (likeAl, Cu, Pb) and metallic oxide powders (like ZnO, PbO) etc. The amount of filers
to be added varies depending upon the article to be fabricated, it may go up to 50% of the total
moulding material.
4. Stabilizers: The substances added to improve the thermal stability of the plastics are
called stabilizers. Plastics such as polyvinyl chloride and polyvinylidene chloride decompose at
the moulding temperature. So heat stabilizers are used during moulding of such polymers.
Commonly used stabilizers are :
(i) Salts oflead e.g., white lead, lead chromate and lead naphthenate, which act as opaque
moulding materials.
(ii) Stearates oflead, cadmium and barium act as transparent moulding materials.
5. Lubricants: Substances added to avoid the sticking of plastic materials to the fabricating
equipment so that the article is easily removed and its glossy finish in preserved are called
lubricants for moulding purposes. Waxes, oils, stearates, oleates and soaps are usually employed
for this purpose.
6. Catalysts or Accelerators: In case of thermosetting plastics the polymerization process
is accelerated during moulding operation of the fusible resins. In much cases the cross links
are developed during the moulding of fusible resins to infusible form. Hydrogen peroxide, benzyl
peroxide, acetyl sulphuric acid, metallic oxides such as ZnO, metals such as Ag, Cu and Pb are
used as catalyst for this purpose.
7. Colouring materials: Organic dyes and opaque inorganic pigments are used to impart
suitable colour to fabricated article for improving its appearance.
7.11 PLASTICS AND RESINS

The term plastics refer to an organic macromolecule possessing the property to undergo
moulding into desired shape upon subjecting to the action of heat, pressure in the presence of a
catalyst.
Depending upon the source of recovery, plastics are of two types:
(i) Natural and (ii) Synthetic
(i) Natural plastics: Plastics materials obtained from natural sources are called natural
plastics. For instance, amber and resins come from trees and casein is obtained from
milk.
(ii) Synthetic plastics: These are man made plastics. For instance, polyethene, PVC,
Nylon-66, Buna-S etc.
The term 'Resins' is slightly different from plastics, but the two terms are considered
synonymous to each other these days. The term resin is usually applied to a polymeric material
which has a glassy appearence. Many resins can be moulded into products called plastics by
compounding with ingredients such as plasticizers, fillers and dyes.
A plastic may be defined as a material which is soft enough at some temperature to be

moulded into a desired shape and subsequently becomes hard still retaining that shape.
Resins are the basic binding materials which form a major part of the plastics.
Resins are basically binding materials which have been included among plastics as an
important class.
Classification of plastics: The plastic materials are classified into two categories:
(A) Thermoplastic materials: They remain soft as long as they are heated and become
hard upon cooling reversibly. Since these two states namely 'soft' and 'hard' forms involve only
physical changes, therefore, no chemical change occurs during heating or cooling these
materials. Generally, these materials, having a long chain molecular structure are obtained
via chain growth polymerisation. They are soluble in organic solvent, are soft, weak and less
brittle and can be reclaimed from waste materials.
Examples: Polyethylene, polypropylene, polyvinyl chloride, polyvinyl acetate, polystyrene,
polymethyl methacrylate, polytetrafluoroethylene, cellulose acetate, polycarbonates, polyamides,
acrylonitrile-butadiene-styrene rubber etc.
(B) Thermosetting materials: These are obtained by the irreversible change of fusible,
soluble materials having linear structure or non-crosslinked branched structure to produce an
infusible, insoluble material which contains cross linking between the polymer chains. The
basic requirement for synthesizing thermosetting materials is that at least one of the monomers
should have functionality more than two, otherwise the material obtained will be linear and
thermoplastic in nature. They become hard during moulding and do not undergo softening
upon subjecting to heat. These materials have 3-dimensional cross-linked networks which are
formed during moulding. Prolonged heating chars these materials. They are obtained via step
growth polymerisation. Due to the presence of strong covalent bonds and cross-linking, these
materials are insoluble in all the organic solvents. They are usually hard, strong and more
brittle than the thermoplastic materials. They can not be reclaimed from waste materials.
High Polymers 269
Examples : Bakelite, urea formaldehyde resin, polyesters, alkyd resins, epoxy resins,
polyurethanes etc.
7.12.1 Difference between Thermoplastic and Thermosetting Polymer
Basic difference between thermosetting polymers and thermoplastic polymers is that the
thermoplastic polymers can be softened repeatedly by heating and hardened on cooling without
change in properties. On the other hand, thermosetting plastics can be heated only once because
it undergo permanent change on melting and sets into a new solid which cannot be remelted.
Thermoplastics Thermosetting plastics
1. They have either linear or branched 1. They have three dimensional network
structure. structure.
2. They are formed by addition polymerisation 2. They are formed by condensation
only. polymerisation.
3. Neighbouring polymeric chains are held 3. Neighbouring polymeric chains are held
together by weak vander Waals forces or together by strong covalent bonds. The
dipole-dipole forces or hydrogen bonding. chains are cross-linked.
There are no cross links.
4. They can be softened on heating, so they can 4. They retain their shape and structure even
be reshaped or reused. on heating. So they can not be reshaped or
reused.
5. They are usually soft, weak and less brittle. 5. They are usually hard, strong and more
brittle.
6. They can be reclaimed from wastes. 6. They can not be reclaimed from wastes.
7. These polymers are usually soluble in 7. They are insoluble in almost all organic
suitable organic solvents. solvents due to strong bonds and cross-
links.
7.13 DESCRIPTION OF SOME COMMERCIALLY IMPORTANT THERMOPLASTIC

MATERIALS
There are very large number of commercially important thermoplastic polymers namely
polyethylene (LDPE and HDPE), Teflon, PMMA, PVC, PVA etc. But keeping in view the
limitations of the syllabus only two important thermoplastics namely Teflon and PMMA are
discussed below:
7.13.1 Polytetrafluoroethylene (PTFE) or Teflon
Preparation: Teflon is prepared by the polymerisation oftetrafluoro ethylene under pressure
in the presence of benzoyl peroxide as catalyst.
Polymerization
Tetrafluoro Polytetrafluoro
ethene ethene (PTFE)
Polytetrafluoroethylene is produced from a very pure monomer which is completely free
from traces of hydrogen by emulsion polymerization process using ammonium persulphate,
(NH4 )2 8 2°8 as initiator. The monomer is prepared by treating chloroform with hydrogen fluoride
and dechlorinating the resulting chlorodiflouoromethane by heating.
CHCIs + 2HF ~ CHF2CI + 2HCI
2 CHF2 CI ~ CF2=CF2 + 2HCI
Properties
(i) The small atomic radius of fluorine, high electro negativity low polarizability and high
linkage energy between carbon and fluorine give polytetrafluoroethylene a very high
softening point (350°C) and excellent resistance to chemicals.
(ii) It is highly crystalline solid having a density of 2.1-2.3 g cm-s.
(iii) Although it is a linear polymer with no branching, yet it behaves like a thermoplastic
material.
(iv) Its high melting point and melt viscosity (i.e. low melt flow rate) and poor solubility
make it impossible to fabricate by conventional means, so special methods are
required.
(v) It is extremely resistant to the action of corrosive solvents and reagent. Because of
its good weather resistance it is a very good regulator.
(vi) The strong C-F bond forces are resposible for its excellent toughness, heat resistance
and non-adhesive characteristics.
Applications
(i) It is used as an insulating material for electric motors, transformers, generators,
cables, capacitors etc.
(ii) It is used for non lubricating bearings and pads or railway bogies and long distance
gas peplines.
(iii) PTFE insulations for cross country high voltage power transmission.
(iv) It is used as vareity of reals, gaskets, pumps, and valves parts, in laboratory and
agricultural equipments.
(v) It is not wetted by oils or water, so its coatings have non-stick properties. It is,
therefore, used for coating frying pans and other kitchen utensils.
(vi) It is used as laminates for printed circuitry.
(pii) It is used as stop cocks for burettes used in laboratories.
(viii) It is used for coating and impregnating glass fibres, asbestos fibres and cloth.
(ix) It is used for tank lining and pipe lining in which different chemicals are passed or
kept for long.
7.13.2. Polymethyl methacrylate (PMMA)
It constitutes an example of polyacryloid plastics and its other trade names are plexiglass,
lucite, acrylite, perspex and crystallite. It is prepared by free radical polymerisation of
metal in presence of acetyl peroxide or hydrogen peroxide. Methyl methacrylate which is
chemically an ester of methyl acrylic acid, is synthesized from acetone as shown below:
Complete
Hydrolysis ~
High Polymers 271
c=~Ha
~
Ha
Dehydration) H C= CHgOH ) H
-H20 2 -H20 2
OOH OOCHa
methyl methacrylate
Methyl methacrylate then undergoes polymerisation to produce PMMA
~ x
Ha
n
H
~C-
/ -
(CHa
. Peroxide) [ 1
H ""-COOCHa -h-~OOCHa n
PMMA
The polymer has the structure
Properties
(i) PMMA is colourless, amorphous, transparent, hard, fairly rigid material.
(ii) Since it is prepared via free radical polymerization, therefore, it is atactic. The
atacticity in the polymer is responsible to confer the transparent nature of polymer.
(iii) It becomes a rubbey substance above 65°C and softens between 130-140°C.
(iv) It has excellent optical properties (optical clarity) and is nearest alternative to glass
owing to its non-shattering behaviour.
(v) It is very light substance and weighs about one-third as much as glass.
(vi) It can be moulded readily almost to any desired shape because of its wide range of
temperature from its rigid state to viscous state.
(vii) It has high resistance to sunlight and transmits light accurately even in curved
sections.
(viii) Due to the presence of ester groups, the polymer has low resistance to hot acids and
bases.
(ix) The polymer exhibits remarkable resistance to scratches. The scratching on PMMA
can be removed by rubbing gently a tissue !>aper moistened with acetone over the
polymer.
Uses
1. It is used for protective coating and for the manufacture of safety glass.
2. It is used for making long-lasting lenses for automobile taillights, windscreens, Tv,
computer screen guards, fibre optics.
3. It can take up beautiful colours and tints and hence is used in the manufacture of
emulsions, paints, adhesives, light shades, signboards, transparent domes and skylights
aircraft windows, bomber noses, cockpit canopies, artificial eyes, plastic jewellery etc.
7.14 DESCRIPTION OF SOME COMMERCIALLY IMPORTANT THERMOSETTING
MATERIALS
7.14.1 Bakelite (Phenol Formaldehyde, PF). It was prepared by the American chemist
Backeland (1909) by the condensation polymerisation between phenol and formaldehyde in
presence of acid/alkali. The following stages take place.
(i) In the first stage, phenol and formaldehyde in 1 : 1 molar ratio react with each other in
presence of acid or base to form 0 and p-hydroxybenzyl alcohol.
OH OH
+
H\
C= 0 ------+.
c:(CH,OH +
/
H
C~OH
If the above ratio is kept 1 : 2, the following possible products are obtained.
OH OH
CH20H HOH2C,&CH20H
H\ I~
+ 2 C=O - - -...
+ #
/
H
However, by adjusting PIF ratio as 1 : 3, the only product as shown below, is obtained.
OH
H\
+ 3 C= 0 --------+.
H
/
CH2 0H
The formation of above monosubstituted, disubstituted or trisubstituted phenols is known
as stage I aqueous.
Phenol, aquoes formaldehyde and the catalyst are introduced into a reactions vessel fitted
with a stirrer and heated upto 70-75°C by means of steam. The reaction is exothermic so heating
is required only to start the reaction.
(ii) In the two stage process, phenol and formaldehyde are heated with an acid catalyst
like HCl, H 2S0 4 , or organic acids like oxalic acid, tartaric acid etc. to form a linear polymer
known as novolac.
novolac
High Polymers 273
N ovolac are very good insulators and are used as cements for sealing electric bulbs to
their metal holders. They are also used for bonding sheets of paper, cardboard and plywood
etc.
On the other hand, when a large amount of aqueous formaldehyde mixed with phenol is
heated in the presence of an alkali calalyst, across linked thermosetting resins called resol
resin is obtained. It has the structure shown below.
Phenol, aqueous formaldehyde and the catalyst are introduced into a reaction vessel fitted
with a stirrer and heated upto 75-75°C by means of steam. The reaction is exothermic so heating
is required only to start the reaction.
OH OH
resolves
The product is dried at reduced pressure in a reactor. The resol resins can be converted to
a well known plastic called bakelite by mixing it a filler such as saw dust, dyes and other
additives.
During moulding of novolac hexamethylenetetramine [(CH2)6N4] is used which being
thermally unstable decomposes to formaldehyde and ammonia. Formaldehyde obtained so
(CH2)4N4 6H 2 0 ) 6HCHO + 4NH3
then attacks the vacant para position of the phenol mainly of novolac to form cross-linked
polymer known as bakelite.
cross linked polymer (Bakelete)

Uses
Phenol formaldehyde resins are used in a wide range of applications.
(i) Resoles and novolacs are used as coating materials. The lamination sheets are prepared
from resoles. They are used for bonding paper, cardboards, plywoods etc.
(ii) Bakelite, compounded with fillers like asbestos powder or saw dust finds uses for
moulding electrical items like telephone instruments, electric insulators parts such
as switches, plugs, switch boards, heater, pressure cookers handles.
(iii) It is also used as distributor leads of cars, adhesive for grinding wheels and brake
linings.
(iv) It is used for varnishes, electrical insulation and protective coatings.
(v) It is also used for impregnating paper, wood and other fillers, for producing decorative
laminates and wall coverings and industrial laminates for electrical parts including
printed circuits.
(vi) It is used for production of ion-exchange resins.
7.14.2 Polynurethanes
Polyurethanes werE' developed by Otto Bayer and co-workers in 1937. Because of
exceptionally good polymeric properties such as resistance to abrasion, chemical attack by
oxygen, ozone, hydrocarbons etc. polyurethanes can be used in a number of ways such as
coatings, elastomers, fibres and foams.
(i) Coatings: Due to their resistance to impact, abrasion, greases, oils etc., they are
used as coatings.
(ii) Elastomers: They have excellent abrasion resistance, good elasticity and hardness,
resistance to oils, greases and solvents. They are therefore, used as elastomers.
(iii)Fibers: Resilient PU fibers are very popular as spandex. They are used for making
swim suits and foundation garments.
(iv) Foams: Both flexible and rigid foams can be prepared which are light, and tough.
The foams also have good resistance to weathering, abrasion, heat and chemicals.
Polyurethanes contain the characteristics urethane linkage

repeat unit.
Some important polyurethanes are discussed below:
(1) Polyurethane rubber (or isocyanate rubber) is produced by reacting polyhalcohols
with di-isocyanates, eg.,
Polymerization)
Ethylene glycol Ethylene diisocyanate
Polyurethane rubber (or isocyanate rubber)

High Polymers 275
Properties : Polyurethanes are highly resistant to oxidation, because of their saturated
character. They also show good resistance to many organic solvents, but. are attacked by acids
and alkalis, especially concentrated and hot. The polyurethane foams are light, tought and
resistant to heat, abrasion, chemicals and weathering.
Uses: For surface coatings and manufacture of foams and spandex fibres.
(2) Perlon-U : A crystalline polyurethane, known as Perlon-U, is obtained by the
polymerisation of 1, 4-butanediol with 1, 6-hexane diisocyanate.
n~::: N -(CH2 )6 -N:::~ + n HO-(-CH 2 )4 _OH_R: ;,:e:. ;:a: . :r .: :an"7g: . :em=: e=nt~
Polymerization
I, 6-Hexamethylene diisocyanate 1, 4-Butane-diol
Polyurethane (Perlon-U)
Applications
(i) Polyurethanes are used as coatings at the floor of gymnasiums and dancing halls.
(ii) Elastomeric polyurethanes are used as synthetic rubbers for enhancing the life of
tyres.
(iii) They are also used for makings small industrial wheels and shoe-soles.
(iv) Perlon-U fibers (spandex) are use for making swim-suits and foundation garments.
(v) Flexible foamed polyurethanes are used for making car and furniture cushions.
(vi) They are also very good leather substitute and well known in market as cor-foams,
used for making pillows, mattresses.
Properties
(a) They are highly resistant to oxidation by 02' 03 and other oxidising gases, because
of their saturated character.
(b) In comparison with Nylons, Polyurethanes are less stable at elevated temperatures;
(c) They have good resistance to many organic solvents, but are attacked by concentrated
and hot acids and alkalis.
(d) They have excellent resistance to abrasion, weather and possess good mechanical
strength.
(e) Suitable choice of diisocyanate and diol and other additives will result in the production
of polyurethanes which can be used as coatings, elastomers fibers and foams.
7.15 ELASTOMERS OR RUBBERS
An elastomer is linear polymer which exhibits elasticity and other rubber like properties.
Elastomers elongate on stretching and revert to the original position as soon as the force is
released. They have long flexible chains with weak intermolecular forces and occassional cross-
links between the chains. The long chains do not fit together well enough for Vander walls
forces to act properly and, therefore, the intermolecular forces are weak. Moreover, there are
no polar groups or sites for hydrogen bonding. For elongation and recovery the long chains of
an elastomer must be connected to each other by occasional cross-links. These cross-links
prevent the· slipping of molecules across each other, but at the same time the flexibility of the
chain is preserved. The most important example of elastomers is natural rubber. It is a gummy
material which has poor elasticity. It becomes soft and sticky when heated and becomes
permanently deformed when streched.
+ -1
It is a polymerised form of isoprene (2, methyl-I, 3-butadiene i.e.,
general formula shown below:

H 2 -C= CH-CH 2
I
CH3 n
H 2C=C-CH=CH 2
6H3 ), having
Natural rubber (cis-!, 4-polyisoprene) has the structure.

CH3 H CH~ C~ CH 3\ H
"'-C=( / C=C/" C=C/
-CH / CH2 CH / "- H " 'CH
-/ "- C~-
3 2
2
Natural rubber
Due to the all cis-configuratioI'ls about the double bonds, the chains do not fit together
well. Hence there are only weak Vander Walls forces. Cross-linking between chains is done by
heating with sulphur (vulcanization). This results in the formation of sulfur bridges between
molecules.
7.15.1 Vulcanisation of Rubber
Natural rubber is a thermoplastic. There are no cross links between the polymer chains.
It becomes soft and sticky when heated. It is not hard and tough. The properties of natural
rubber can be modified and improved by the process of vulcanization. 'Ib improve its properties,
it is heated with sulphur at a temperature of 373 to 415 K.
The process of heating natural rubber with sulphur to improve its properties is called
vulcanization and the product formed is called vulcanized rubber.
Since the process is slow, some additives such as zinc oxide etc. are used to accelerate the
rate of vulcanization. During vulcanization, sulphur cross links are formed. The formation of
cross links makes rubber hard, tough with greater tensile strength. The vulcanized rubber
has excellent elasticity, low water absorption tendency, resistance to oxidation and organic
solvents. Vulcanized rubber has better tensile strength, elasticity, and resistance to atrasion
than natural rubber.
The double bonds in the rubber molecule act as reactive sites. During vulcanization, sulphur
forms cross links at these reactive sites. In vulcanized rubber) the polymer chains are held
together by Polysulphide bridges or cross links [Fig. 7.9(a)]. When the stretching force in applied,
the chains can straighten out but they can not slip pass each other, because of polysulphide
bridges. When the stretching force is with drawn, the chains tend to coil up again and the
rubber returns to its original shape [Fig. 7.9(b)].
High Polymers 277
~
s s' Stretched
•
Relaxed
. ~l
(a) (b)
Fig. 7.9.
The extent of hardness or toughness, however, depends upon the amount of sulphur added.
Thus, about 5% sulphur is used for making tyre rubber, 20-25%. S for making ebonite and
30% S for making battery case rubber. The process of vulcanization was discovered by Charles
Goodyear in 1893.
The comparison of the main properties of natural rubber and vulcanized rubber are given
below:
Natural rubber Vulcanized rubber
(1) Natural rubber is soft and sticky. (1) Vulcanized rubber is hard and non-sticky.
(2) It has low tensile strength. (2) It has high tensile strength.
(3) It has low elasticity. (3) It has high elasticity.

(4) It can be used over a narrow range of (4) It can be used over a wide range of
temperature (from lOOC to 600C). temperature (400C to 1000C).
(5) It has low wear and tear resistance. (5) It has high wear and tear resistances.
(6) It is soluble in solvents like ether, carbon (6) It is insoluble in all the copunon solvents.
tetrachloride, petrol etc.
7.15.2 Synthetic Rubbers
The synthetic rubbers are obtained by polymerizing butadiene derivatives. These are also
vulcanized by the process developed for natural rubber. The synthetic rubbers are either homo
polymers of 1, 3-butadiene or copolymers in which one of the monomer is 1, 3-butadiene or its
derivative so that the polymer has the availability of double bonds for its vulcanization. There
are certain deficiencies of natural rubbers such as extreme stiffness, stickiness and tackiness.
These deficiencies can be minimised by subjecting the raw rubber to vulcanisation. The
deficiencies of natural rubber have been overcome in synthetic rubbers. A comparason of natural
rubber with synthetic rubbers to show the advantages of synthetic rubbers has been
summarised below:
Natural Rubber Synthetic Rubber
(i) It is attached by sunlight and air. These are not. attached by sunlight and air.
Neoprene rubber and nitrile rubber are specially
resistant to the action of air and sunlight.
(ii) Its resistance to variation of temperature is They have higher resistance to the variation of
low. temperature. Nitrile rubber is an example for the
same.
(iii) It holds less air and water at high pressure. They hold more air and water at high pressure.
Butyl rubber is used in inner tubes of car due to
this reason.
(iv) It softens and swells on storing in organic They do not swell and can hold organic solvents
solvents. better. Polysulphide rubbers are specially used on
this account.
(v) The rubbery properties are lost at high Rubbery properties are retained over a wide of
temperatures. temperature. For instance, silicone rubber has
working range 90-316°C.
(vi) It ages quickly and loses surface luster They do not age easily. Polyurethane rubber is an
easily with use. example to this effect.
Synthetic rubbers are of following types:

(i) Strene rubber (GR-S or Buna-S)
(ii) Nitrile rubber (GR-A or Buna-N)
(iii) Neoprene (GR-M) It is polymerized product of chloroprene (2- chloro
butadiene - 1, 3)
(iv) Butyl rubber (GR-I)
(v) Polysulphide rubber (GR-P or Thiocol)
(vi) Polyurethane rubber (isocyanate rubber)
(vii) Chlorosulphonted Polyethylene rubber (Haplon)
(viii) Silicone rubber
Buna Rubbers
Out of the above list, the first two are called Buna rubbers. The first synthetic rubber was
obtained by the homopolymerisation of butadiene (H 3C-CH=CH-CH3 ). Polymerisation of
butadiene was carried out in the presence of sodium (Na) as an initiator and was reffered to a
Buna rubber. The name Buna has been derived from the first letter of butadiene and the
symbol Na for sodium. An improvement of this rubber was the copolymer rubber obtained
from butadiene and styrene.
1. Styrene Rubber (Buna-S)
Styrene butadiene rubber (SBR) is prepared by the copolymerisation of butadiene (75%)
and styrene (25%) is an emulsion system at 50°C in the presence of catalyst such as cumene
hydroperoxide.
High Polymers 279
ButadIene Styrene Polybutadiene-co-styrene

(styrene butadiene rubber, SBR)
In addition to the above 1, 4 addition product, the polymer also contain small amount of 1,
2-addition products. SBR is also known as Buna-S or GR-S.
The starting materials are styrene and butadiene. They are prepared as follows:
Styrene: It is obtained from benzene and ethylene as given below:
o +CH,=CH, AIel,
.. 0'
E thy I benzene
-H,
..
oCH,
Styrene
Butadiene: It can be prepared by the catalytic dehydrogenation of butanes at 400-660°C
under reduced pressure. Butanes are obtained from petroleum industry.
Al903-Cr20g
CH3-CH2-CH2-CH3 --"-'=-=-H2--"--~) CH2=CH-CH=CH2
n-butane 1, 3-Butadiene
Al 2 0 3 - Cr2 0 g
CH3-CH:z-CH = CH 2 ---='~_7.H,:c...2...:..2..~) CH 2=CH-CH=CH 2
I-butane 1, 3-Butadiene
Al 0 -Cr2 0 3
CH 3-CH = CH-CH3 ---"--'_7::
2 3
H-2 "'-"-~) CH 2 = CH-CH = CH 2
2-butane 1, 3-Butadiene
Properties
It resembles natural rubber in processing, characteristics as well as quality of finished
products. Styrene rubber has high abrasion resistance, high load bearing capacity, low oxidation
resistance, swells in oil and solvents, like natural rubber. SBR is also vulcanized and produce
cold rubber, which has greater tensile strength and greater abrasion resistance. However, it
gets readily oxidised, especially in the presence of'traces of 0 3 present in the atmosphere.
Uses
(i) It is used in the manufacture of those materials which arE' required to possess gi!:)ater
resistance to abrasion. For instance, it is used in motor tyres, shoes soles, footwear
components etc.
(ii) It is also used in tanks lining, floor tiles, insulation of wire and cables, carpet backing,
gasket, adhesives etc.
(iii) It is also used as cold rubber, which has greater tensile strength and resistance to
abrasion. To prepare cold rubber the emulsion polymerisation of butadiene and styrene
is carried out at -18°C to 5°C in the presence of an oxidation-resistance system.
SBR is used in motor tyres, shoes soles, footwear components, tanks lining, floor tiles,
insulation of wire and cables, carpet backing, gaskets, adhesives etc.
2. Nitrile Rubber (Buna-NINBR)
It is a copolymer of acrylonitrile and butadiene. It is prepared by the copolymerization of
acrylonitrile and butadiene in emulsion systems.
1, 3-butadiene 1
n CH2 =CH-CH =CH + n (CH2 =CHCN)
acrylonitrile
copolymerization
rH" -CH=CH -CH" -~ -CH,,-1

Nitrile rubber
Properties
Nitrile rubber (GR-A) has low swelling, low solubility, good tensile strength and abrasion
resistance even after immersion in gasoline or oils. It has good resistance to heat, sunlight,
oils, acids, but it is less resistant to alkalies than natural rubber because of the presence of
cyno groups. Vulcanized nitrile rubber is more resistant to heat and ageing than natural rubber
and may be exposed to high temperatures.
Uses
(i) It is also used for making conveyor belts, high altitude air craft components, oil
resistant foams and automobile parts etc.
(ii) It is also used in adhesives, for making fuel tanks, gasoline.
(iii) It is also used for impregnating paper, leather and textiles in the form oflates.
3. Neoprene (or GRM or polychloroprene or Ploychlorobutadiene or dupene)
It is obtained from chloroprene (2-chloro-l, 3 butadiene) which is obtained from acetylene
by catalytic dimerisation to give vinyl acetylene. The product so obtained is treated with HCl
in the presence of a catalyst to the desired monomer.
HC == CH + HC == CH di:~:a~on) HC2 =CH-C == CH

Vinyl acetylene
H2C = CH-C == CH + HCI-+- H2C = CH-~;CH2
2-Chloro-1, 3-butadiene
Neoprene is obtained by the emulsion polymerisation of chloroprene in the presence of
ammonium persulphate as an initiator.
It is a trans-isomer as shown below: Neoprene

High Polymers 281
It does not require sulphur for vulcanization. It can be vulcanised just by heating. However,
its physical properties are enhanced by compounding it with ZnO or MgO.
Properties
Chloroprene is closely related to natural rubber structurally:
(i) The substitution of one H atom by CI atom produces superior resistance to vegetable
and mineral oils, ageing and high temperatures.
(ii) But it has a greater solubility in polar solvents, being a polar polymer.
(iii) Its resistance to vegetable and mineral oils is superior to natural rubber but inferior
to nitrite rubber.
(iv) It has high tensile strength even in the absence of carbon black.
(v) It does not undergo oxidative degradation because of its good ozone and weather
resistance.
Applications
It is used for:
(a) For making industrial hoses, gaskets,
(b) Tubing for carrying corrosive gases and oils,
(c) It is also used for making sponges,
(d) Conveyor belts,
(e) Linings of reaction vessels,
(j) Adhesives,
(g) Gloves
(h) Shoe-soles
(i) Wire and cable insulations.
4. Butyl rubber (GR-I)
Preparations: It is prepared by copolymerization ofisobutene with small amounts (usually
1 to 5%) of isoprene using Alel3 anlyd as an initiator.
Isobutene Isoprene
Polyisobutene-co-isoprene (Butyl rubber)

Properties
(i) It possesses outstanding low permeability to air and other gases; less than 1I10th of
natural rubber.
(ii) It has excellent resistance to heat, abrasion, ageing, and chemicals (such as H 2S04 ,
HN0 3 , (HCI and HF).
(iii) Because of its hydrocarbon nature, it is soluble is hydrocarbon solvents like benzene,
but not soluble in polar solvents (like alcohol and acetone).
(iv) It has high resistance to ozone.
(v) Being non-polar, it has good electrical insulating properties.
(vi) It can be vulcanized, but it cannot be hardened much due to very low unsaturation.
(vii) It is amorphous under normal conditions. It does not crystallise on cooling and remains
flexible to -50°C.
Applications
It is uses for:
(i) making cycle and automobile tubes, automobile parts
(ii) conveyor belts for food and other materials
(iii) tanks-linings, insulation for high voltage wires and cables, etc.
(iv) hopes, gaskets etc.
7.16 ADHESIVES
An adhesive is a substance used for stiching two unlike bodies together due to the molecular
forces exiting in the ar~a of contact.
The bodies which are held together by an adhesive are called adherends. The entire
assembly of the adherends including the adhesive is referred to as a bond or ajoint. Bonding
of substances through adhesives have certain advantages and disadvantages over conventional
methods like welding, soldering, mechanical joining by rivets, nails etc.
Advantages
(i) They can be applied to the surfaces of any kind of materials. For instance, metals,
plastics, glasses and ceramics may be joined to each other as well as to one another.
A metal may be joined to a metal or to a plastic or to a ceramic. Similarly, a plastic
may he joined to a plastic or to a metal and so on.
(ii) The process of applying adhesives is very simple, it does not require any specialized
personals for doing the job.
(iii) Bonding with adhesives require less after finishing as compared with other bonding
processes.
(iv) Adhesives are heat as well as electric insulators, so a hard and electrical insulating
layer is introduced between the joining surfaces.
(v) Bonding by adhesives gives smoother surfaces. So, it is better suited for articles such
as brakes, cluches and aircrafts parts, where projections such as rivet heads etc. affect
their performance adversely.
(vi) Direct bonding of dissimilar metals may lead to galvanic corrosion. Joining such metals
by adhesives avoid the chances of metal corrosion.
(vii) Adhesive joints are leak proof for liquids and gases. So, bonding by adhesives is
employed for preparing water-tight wood boats etc.
High Polymers 283
(viii) Composite articles containing different materials joined together can be manufactured
to get the advantage of properties of different components bonded together. For
example, metal faced plywood articles, flush doors etc.
Limitations
(i) Adhesives are mostly organic compounds, whose bonding strength decreases with rise
in temperature. So, adhesive bonding can not be used at high temperature.
(ii) The adhesive action is specific in nature. A particular adhesIve is required for bonding
particular materials. There is no single adhesive which can be employed for bonding
any type of materials. So, selection of a stable adhesive and condition under which it
will work efficiently have to be made.
(iii) Adhesive require time for the development of full strength after their application.
Operations like setting, curing etc take time unlike other bounding methods like
welding etc.
(iv) Adhesive strength is lower than other bounding methods. Moreover, bonding by
adhesives is effective between plain and clean surfaces only.
7.16.1 Classification of Adhesives
Depending upon their chemical nature, adhesives are classified as under.
1. Thermoplastic Synthetic Resins: These are fusible i.e. they become soft on heating.
These are water soluble, so poor water resistant adhesives. Some important members of this
category are :
(a) Cellulose derivatives:
(i) Cellulose nitrate: A mixture of cellulose nitrate in alcohol is available in the market
under the trade name 'collodion'.
(ii) Cellulose acetate: A mixture of cellulose acetate with benzene is also commonly
employed as an adhesive. It is more resistant to heat then cellulose nitrate, but is a
weaker adhesive than cellulose nitrate.
(iii) Ethyl and Methyl cellulose: Both these compounds are used as adhesives after mixing
with some suitable plasticizers and making a paste with hot water.
(b) Polyvinyls : Some common examples are: Polyvinyl chloride (PVC) and polyvinyl
acetate (PVA). They act as excellent bonding materials after mixing with suitable solvents.
(c) Acrylics: A common example is polymethyl methyl acrylate (PMMA). It has excellent
optical properties and is the nearest alternative to glass. It can take up beautiful colours and
is used in the manufacture of emulsions, paints and adhesives. It forms perfect adhesive films
when used in the form of solution in suitable organic solvents.
2. Thermosetting Synthetic Resin : These resins possess good adhesive properties
because they develop cross links in between the chains forming strong bonding material
between the joining surfaces. The bonding films are infusible, insoluble and possess resistance
towards moisture, heat, insects etc. Important members of this class of adhesives are:
(a) Phenol-formaldehyde resins: The partially polymerized products (resoles and navolac)
are used as binding glues, which fonn hard films between the coated surfaces on heating and
pressing. These resins are used for making water proof plywood, laminates, bonding articles
in ships and aircrafts.
(b) Urea-formaldehyde resins: These are copolymers of urea and fonnaldehyde.
Urea formaldehyde resins have a distinct advantage over the phenolic resins in that they
are clear and colourless; and thus can be synthesized in all desired colours by adding the proper
pigment. The hardness and tensile strength of these resins is better than those of phenolics
but their impact strength and heat moisture resistance are lower. They have excellent abrasion
resistance and good adhesive characteristics.
Eposy resins: Due to the presence of stable ether linkage, these resins show
(c)
remarkable resistance towards water, heat, chemicals and electricity. Being polar, they have
excellent adhesive characteristics and are used as adhesives for glass, metals, ceramics etc.
These are popularly known as araldite.
(d) Silicone resins: Silicone resins contain alternate Si-O bonds, in which alkyl groups
are attached to the silicon atom. Thus their structure is:
R -! -!- -!-
-0 0 R where R is alkyl or phenyl radical.
These resin have strong adhesive capacity, water repelling property, thennal stability up
to 2500C, resistance to chemicals, atmospheric and bacterial action. They are therefore, used
fo.r bonding metals, ceramics, plastics and rubber etc.
(e) Polyesters: Polyesters particularly alkyd resins possess good adhesive property. These
are obtained by reacting polybasic acid (like phthalic acid) with polyhydric alcohols (like glycerol
in presence of catalysts.
They have good moisture resistance but low heat resistance. They are used for making
laminated glass and cloth.
3. Natural Resins: There are two commonly used natural adhesives namely Asphalt
and shellac Asphalt is a crude adhesive. It is used for bonding paper, cloth and metal sheets.
Shellac is being used as adhesive since long. It is applied in the molten state while hot. It
fonns a hard and strong bonding film on getting cooled. It has low thennal conductivity. It is
used in making belts and conveyers etc.
4. Starch adhesives: Starch obtained from rice, potatoes, wheat etc is suspended in water
or very dil HCI solution and boiled for sometime. Small amount of copper sulphate is also
added to prevent the attack of insects and fungi. It can be applied easily while hot or cold, dry
quickly and is quite cheap. However, they possess low bonding strength and low resistance
toward moisture. It is used for binding books, note books, cardboard boxes and applied on
envelopes and stamps.
5. Protein or Vegetable glues : These glues are obtained from plant products such as
soyabeans, peanuts, corn, albumin, casein etc. The protein glues can be used for binding paper,
card board, cloth etc just like starch glues.
High Polymers 285
6. Animal glue: These are also protein glues, but their sources are bones of dead animals,
wastes of slaughter houses and scrape from leather industry.
Animal glues have good adhesive strength, but possess poor resistance towards moisture
and fungus. These are used in the manufacture of furniture, radio cabinets, cardboard boxes
and jewelery boxes etc.
7. Inorganic adhesives: Sodium silicate (Na2SiOa) is commonly used inorganic adhesive.
It is prepared by heating soda ash (Na2CO a) with sand. The product so obtained is mixed with
litharge (PbO) or Mn02 and boiled in hot water, which gives a gel on cooling. The gel can be
redissolved in hot water and the adhesive can be applied with a brush. The bonding strength
is lowered with temperature. The bond is, however, fungus resistant. It is mostly used in paper
industry for making corrugated paper boards and cardboard boxes.
7.15.2 Chemical Factors Influencing Adhesive Action
Besides physical factors, the following are the chemical factors influencing the bonding
action and consequently the bonding strength of an adhesive:
1. Polar characteristics. Adhesives containing polar groups possess stronger bonding
strength as compared to non-polar adhesives. The higher the polar character of an adhesive,
the greater would be its bonding strength. So, organic compounds containing polar groups such
as carboxylic acids are generally added to the non-polar adhesives to increase their bonding
HQ-COOH)
action. For example, maleic acid ( H6,-cOOH' a dicarboxylic unsaturated acid is added to
thermoplastic resins like polyvinyl chloride (PVC) and polyvinyl acetate (PVA) which act as
adhesives also.
2. Degree of Polymerization. The degree of polymerisation of the polymer being used
as an adhesive should be midway between the highly polymerized and unpolymerized polymer.
In case of thermosetting resins cross-links are formed between the chains during curing which
gives additional strength to the bonded film. Highly polymerized adhesives are already hard
and infusible before use, while partially polymerized resins are fusible. During the process of
their further polymerization, they tend to develop their bonding strength. Therefore, partially
polymerized thermosetting resins such as phenol formaldehyde, urea formaldehyde are
preferred to be used as adhesives. Thermoplastic resins such as cellulose derivatives are
degraded before using as an adhesive so as to lower their degree of polymerization to the
desired range.
3. Presence of Side Chain. The side chain present on the main chains of the polymeric
molecules play a significant role in the adhesive action of the resin acting as adhesive. The
two bonded surfaces are held together by the interlocking action, in which the chemical nature
of side chains is important. The chemical nature, length and complexity of the side chain
controls the bond strength of the interlocks between the two surfaces. It has been observed
that in case of cellulose esters, the number of C atoms should lie between 6 to 14 in the fatty
acid side chain for good adhesive action. It means side chains with less than 6 carbon atoms
are not required for effective adhesive action. Similarly, the polymer obtained by the
condensation of higher aldehydes with phenol serves as better adhesives than with lower
aldehydes. So, for preparing better thermosetting adhesives formaldehyde may be replaced by
higher aldehydes.
4. Effect of pH. It has been observed that the adhesive strength is adversely affected in
the presence of strong acids and strong bases. The pH value of any solution increases from 7
to 14 as the basic character increases and it decreases from 7 to zero as the acidic character
increase. So, both high as well as low values of pH is not desirable. The effect of acids and
bases is particularly more on cellulose materials and metallic surfaces. Protein adhesives work
better in the presence of lime which provides a weak basic character. Vulcanized rubbers and
organic plastic resins possess higher adhesive strength in weakly acidic medium i.e. at pH
values lesser than 7. The pH value slightly higher than 7 is desirable for adhesives working
effectively in basic medium, whereas pH value slightly lower than 7 for adhesives working
effectively in acidic medicines.
7.15.3 Epoxy Resins
These resins are prepared by the condensation polymerisation of epichlorohydrin and bis-
phenol A. The starting materials are prepared as shown below:
(i) Preparation of epichlorohydrin : The allylic chlorination (free radical substitution)
of propylene at 400°C results in the formation of allyl chloride, i.e., 3-chloroprop-1-ene. The
latter upon reacting with chlorine-water at 300°C produces 1, 3-dichloropropan-2-ol- which when
heated with CaO at 200°C produces epichlorophydrin. All these reactions may be summarized
as:
CaO
CICH2-CH(OH}-CH2 CI --::2=OO=oC~) H2 C-CH-CH2 CI + HCI
epichlorohydrin
(ii) Preparation of Bisphenol A: Acetone and phenol (dissolved in aqueous NaOH
solution) in 1 : 2 molar ratio at -50°C form bisphenol as shown below:
r-·---·---·-------l CHa
HaC, I H--kQ)-OH N OH I U
C=iO + ! 500C~ -H:O ~ H0--<Q)-9--<O>-1

0 OH
HaC/ I H-kQ)-OH
l ________________ J CHa
Bisphenol
(iii) Condensation of ephichlorohydrin and bisphenol : In presence of alkaline
catalyst, epichlorohydrin and bisphenol undergo condensation polymerisation to form epoxy
resin. In this reaction, opening of epoxide ring takes place generating OH groups on epoxide
molecules. The OH groups than undergo cross-linked during moulding resulting in the
formation of cross-linked polymer. At first stage, a low molecular weight product is obtained.
In order to ensure that the polymer chain must terminate with the epoxide ring, an excess of
epichlorohydrin is used. The excess amount of epichlorohydrin assists in cross-linking the
polymer during thermosetting of the resins.
CHa
n Ho-<g>+--O-d.E::;~~ ---{)!I,-C,IH, 60·C

-Hel
~
CHa 0
High Polymers 287
Properties
The physical nature of the polymer depends upon its molecular weight. The resin is a
viscous liquid with the molecular weight 340 i.e., contains one bisphenol and two epoxy moieties.
However, the polymer becomes a brittle solid when its molecular weight is as high 8000. The
resin melts at 145-155°C. Due to the presence of stable ether linkage, the polymer shows
remarkable resistance towards water and other solvents.
Applications
(i) Being polar, they have excellent adhesive characteristics and are used as adhesives,
for glass, metals etc. and are popularly known as araldite.
(ii) They have excellent resistance to wear, they are also tough and heat resistant. So,
they are used for surface coatings particularly for making skid resistant surfaces for
high ways, road junctions and round abouts.
(iii) Good heat and electrical resistance, low water absorption tendency, dimensional
stability make them very good materials for electronic applications particularly in
mouldings containing inerts and encapsulations.
7.16 CONDUCTING POLYMERS

All organic polymers were considered to be insulators, until 1960. They were extensively
used as insulating materials in the electrical and electronics industries due to their insulating
characteristics. It was accidently discovered at a plastic research laboratory in Germany that
even polymers can be made to conduct electricity. Such polymers which can conduct electricity
are termed as conducting polymers. A nobel prize in chemistry for the year 2000 was awarded
jointly to three chemists for the discovery and development of electrically conducting polymers
such as polyacetylene which conducts electric current almost like a metal.
Normally, electrons in a polymer are localised and are not available for conduction of
current. But doping can delocalise the electrons and make them available for the conduction
of current.
Therefore, conducting polymers are generally obtained by doping an oxidising or a reducing

agent into the organic polymers having a conjugated system of alternating single and double
carbon bonds in the main chain.
Applications
Conducting polymers have innumerable applications in electrical, electronics and medical
fields. Some important applications are summarised below:
1. In rechargeable batteries: Conducting polymers are used in small size (button type)
weightless, long lasting batteries. These are based on perchlorate doped polyacetylene-
lithium systems.
2. In analytical sensors: These are used for making sensors for pH, 02' NO x ' S02' NH g
and glucose.
3. In electronics: Conducting polymers are used in electronic devices such as transistors,
and diodes. Photostructural lacquers based on ICP's are useful for electron beam
lithography, LED's and data storage. Emeraldine base form of polyaniline is used as
a resist for lithography (as explained later in polyaniline).
4. In Ion Exchangers: Membranes made of poly conductors have selective
permeability for ions, gases etc. So they are useful for ion exchangers and
controlled release of drugs. Conducting polymer membranes have been used for the
slow release of birth control drugs and they have potential to be used for cancer
chemotheraphy.
5. In electrochromic displays and optical filters: ICP's containging conducting polymers
can absorb visible light to give coloured products, so they can be useful for
electrochromic displays and optical filters i.e. windows with adjustable transparency.
Thus, conducting polymers are used as electrochromic materials. These materials
can change colour reversibly during the electrochemical processes of charge and
discharge.
6. In photovoltaic devices: For example, AlIconducting polymer/Au photovoltaic cells.
7. In telecommunications systems and electromagnetic sereening materials.
Classification
Conducting polymers are classified into two main types:
(i) Intrinsic conducting polymers (ii) Extrinsic conducting polymers.
These are further divided into two type each.
I Conducting Polymers I
I
j !
I Intrinsic Conducting Polymers I I Extrinsic Conducting Polymers I
I I
J ~ ~ 1
Conjugation Doped E filled Blended
conducting conducting conducting conducting
polymers polymers polymers polymers
Let us discuss each type briefly.

1. Intrinsic conducting polymers. These polymers have conjugation in the backbone
i.e. a system of alternate single and double carbon bonds in the chain, which is responsible for
conductance. These are further of two types:
(aJ Conducting polymers having conjugated 1C-electrons in, the-backbone.
These polymers contain conjugated 1C-electrons in th~ chains which increases their
conductivity. This is because, overlapping, of conjugated 1C-electrons over the entire chains results
in the formation of valence bands as well as conduction bands. The valence band and the
conduction bands are separated by a significant band gap. Thus, electrical conduction could
occur only when the electrons receive sufficient energy to jump the gapand reach conduction
bands.
High Polymers 289
Examples:
Monomers Polymers
(i) nCH=CH
Acetylene
• -CH=CHtCH=CH}.H=CH-or "C~CH"CH~~C~CH 0
Trans-polyacctylcnc
(ii) nO
N •
I
H
Pyrrole Polypyrrole
(iii) nO NH2 --+. [Co-'

[ - "J/L~J/L"~NJ
nJJ
f\.=/f\.=/~-
Aniline Leuco emerldine
1 _
~bO-~~-
Emeraldme base
1
==Cr~~~Nj Polyaniline
The above noted conducting polymers have conjugated rc-electrons in their backbone but
there conductivities are not sufficient for their use in different applications_ So they are doped
to increase their conduction to make them useful.
(b) Doped conducting polymers: The above type of polymers can be easily oxidized or reduced
as they have low ionization potentials and high electron affinities. Their conductivities can be
increased by creating positive or negative charge on polymer backbone by oxidation or
reduction.
The process is referred to as Doping which is offollowing two types.
p-doping: It is done by oxidation process. Conducting polymer of type (a) is treated with
Lewis acids (A) or with iodine vapour or iodine in CCI4 .
(CH)x + A ~ (CH)x + A- [Oxidation Process]

Polyacetylene Lewis acid p-Doped polyacetylene
For example, (CH)x + 2 FeCl3 ~ (CH)./ FeCI4- + FeCl2
2(CH)x + 3 12 ~ 2 (CHV 13- etc.
In general, p-doped type of conducting polymers are hole dominant having positive charges
being electron short materials.
Polymer + X ~ (Polymer) 1/+ + XI/-
where X = Lewis acid, 12 , FeCl3 etc.
n-doping : It is done by reduction process. For this, conducting polymer of Type (a) is
treated with Lewis bases (b) like sodium naphthalide.
CH\ + B ~ (CH)x- B+
Polyacetylene Lewis base n-doped polyacetylene
Forexample, (CH)x + Na+ (ClOHa)- ~ NaGl (CH)x - + ClOHa
In n-doping (or Reductive doping), the reduction process (i.e., the addition of an electron to
the polymer backbone using a reducing agent like sodium naphthalide. In general n-doped type
conducting polymers are free electron dominant having negative charge being electron rich
materials.
Polymer + M ~ (Polymer)n + Mn+
where M = NEl, Li etc.
(ii) Extrinstic Conducting Polymers : These polymers are conductors due to the
presence of externally added ingredients in them. These are of following two types:
(a) Element Filled Conducting Polymer: In this case the polymer acts as the binder
to hold the conducting elements such as carbon black, metallic fibers, metallic oxides, etc. to
form a solid mass.
Generally, special conducting guide C-black is used as filler which has very-high surface
area, more porosity and more of a filamentous properties.
These polymers possess reasonably good bulk conductivity; are generally low in cost; light
in weight, mechanically durable and strong and are easily processable in different forms, shapes
and sizes. Such compounds have been important, for example, in hospital operating theatres
where it was essential that static charges did not build up, leading to explosion involving an
aesthetics.
But it is to be noted that addition of as little as 10% carbon black will drastically reduce
the tensile strength, and impact strength of polypropylene mouldings.
(b) Blended Conducting Polymers: These polymers are obtained by blending a
conventional polymer with a conducting polymer. Such polymers possess better physical,
chemical, electrical and mechanical properties and they can be easily processed.
For example, up to 40% of polypyrrole will have little effect on tensile strength and also
give a much higher impact strength than obtained with a carbon-black filled compound at only
10% loading.
Such compounds are of interest in electromagnetic shielding.
*7.16.1 Bond Theory of Conductance Mechanism
Conduction in is generally explained using the band model. According to which, the orbitals
of the atoms of a solid overlap with the equivalent orbitals of their neighbouring atoms to
form molecular orbitals (MOs). The number of MO's formed is equal to the number of
overlapping orbitals, but half of them are bonding and the other half in anti-bonding orbitals.
These orbitals are being referred to as energy hands. (Fig. 7.10) The band may be completely
filled or partially filled with electrons or may be completely empty. The highest occupied band
is called the valence band (VB) while the lowest unoccupied band is called the conduction band
(CB). The energy space between the highest occupied and lowest unoccupied bands is called
the band gap or forbidden gap.
The conductivity of metals is due to the overlapping of partially filled VB with the empty
CB which results into filled VB and CB with the absence of forbidden gap. The conductivity of
semiconductors is also attributed to the narrow energy gap between the filled valence band
and empty conduction band. It is because even a weak electric field or smaH heat energy can
promote the electrons from the filled VB to empty CB. Insulators would not conduct electricitv
because the filled VB and empty CB are separated by a wide energy gap.
High Polymers 291
CB
FB
VBij VB
Metal Metal Semiconductor Insulator

(partially filled (overlap of filled (narrow for bidden (wide forbidden
valence band) VB with an gap) gap)
empty CB)
Fig. 7.10. A simple band picture explaining the difference between a conductor,
semiconductor and an insulator.
*7.16.2 Mechanism of Conduction is Conducting Polymers ,
Normal polymers have a band model identical to insulators, therefore they do not conduct
electric current. The polymers having congugated system of single and double bonds in the
backbone chain can be transformed into conductors by doping them with an electron acceptor
i.e. oxidising dopant (p-doping) or with an electron donor i.e. reducing dopand (n-doping). Let
us explains the mechanism of conduction in conducting polymers of the two types of doped
conductors one by one.
~ ~ ~ ~ ~ ~
I I CB
Polyacetylene (1)
"""""""""""""i
I1\19III VB
-e- ~ I/CC14
(Oxidation)
+
~ ~ ~ ~ ~ ~ I CB
-
0
Polaron (radical cation) (2)
• tj VB
-e 11/cc14
(Oxidation)
~ ~ I CB
Bipolaron (dication)
(3)
~+t i
1(Segregation of cations) ".i¥~"".
..."Eo.
VB
(4)
I I CB
+
Soliton pair
(p-doped polyacetylene) iilJl VB
Fig. 7.11. p-doping of polyacetylene to give a polaron, a bipolaron, and a soliton pair
[Here, VB = Valence band; CB = Conduction band; 0 = Acceptor level]
* Articles 7.16.1 and 7.16.2 are not included in the syllabus, but these form the basis for
understanding the mechanism of conduction in polypyrrole.
(i) Mechanism of conductance due to p-doping : In p-doping, conducting polymer having
conjugation in the back bone chain is partially oxidised using a suitable oxidising agent. This
oxidation process (i.e., removal of an electron from the polymer pi-chain) leads to the formation
of delocalised radical ion called polaron. This changes to a dication called Bipolaron and finally
to a p-doped polyacetylene as shown in Fig. 7.11.
This main points of this mechanism are given below:
(1) Valence band (VB) and conduction band (CB) in conjugated polymers like trans
polyacetylene are separated by a significant band gap, thus conductivity of undoped
polymer is not very high.
(2) Electron removed from polyacetylene by oxidation will lead to the formation of radical
cation (or polaron). It has a hole in between VB and CB.
(3 ) Further oxidation will lead to the formation of Bication (or Bipolaron) with two holes
in the VB and CB.
(4 ) Bication lowers its energy by segregation into two positive solitons i.e., two holes in
the mid gap energy levels. The presence of holes in the band gap allows facile jumbs
of electrons from the VB into these holes. Then holes thus created in the VB conduct
electricity. As a consequence, conductivity increases significantly.
(ii) Mechanism of conductance due to n-doping : In n-doping, conducting polymer
having conjugation in the backbone chain is partially reduced by a suitable reducing agent.
Thus addition of pi electron from the polymer chain due to reduction process leads to the
formation of delocalised anion radical called polaron. This changes to a dianions radical called
Bipolaron and finally to an-doped polyacetylene (Fig. 7.12).
CB
~ ~ ~ ~ ~ ~
Polyacetylene (a)
VB
--e- ! Na+ C1oH8f
(Reduction)
+
~ ~ ~ ~ ~ ~ CB
Polaron (radical cation) (b)
VB
--e lNa+ ClOHsf
(Oxidation)
~ ~ CB
(c)
Bipolaron (dianion)
1
(Segregation of cations)
VB
+--
+
CB
(d)
Soliton pair +
(p-doped polyacetylene) VB
Fig. 7.12. n-doping of polyacetylene to give a polaron, a bipolaron, and a soliton pair.
[Here, VB =Valence band : CB = Conduction band: • = Donar level]
High Polymers 293
The main points of this mechanism are given below:
(a) The valence band (VB) and conductance band (CB) in congugated polymers like
polyacetylene are separated by a significant band gap, so the conductivity of undroped
polymer not very high.
(b) The electron added to polyacetylene by reducing doping does not go into the conduction
band but into an intermediate electronic state within the band gap of radical anion
(or polaron).
(c) Further reduction will lead to the formation of Bianion (or Bipolaron). It contains
electrons in the energy levels residing in the band gap.
(d) Bianion lower its energy by segregating into two negative solitons at the mid gap
energy levels. Current could then be carried as the charged solitons and the defect
sites move along the chain. The position of dopant level in the band gap allows facile
jumps of electrons into the conduction band. This lead to the generation of conduction
pathways. As a consequence, conductivity increases signficiantly.
1.
H
~ c=JCB
!J
I Neutral ~
chain
H
~VB
H
2. ~
Polaron - - - +~
c=JCB
!J
~VB
3.
J Bipolaron c=JCB
~VB
Bipolaron bands ~
+
4.
+ ----+
c=JCB
,.. .......... _ ....................'1
L........_ ..................... ..:
1 ..• .. • ..•••• ..·········_···.. ···"':
p-doped polypyrrolc L........._ ......._........... ..:
~VB
Bipolaron bands
Fig. 7.13. Mechanism of conduction in polypyrrole.

(iii) Mechanism of conductance in polypyrrole* : The monomer of polypyrrole is a
heterocyclic compound (pyrrole), which under suitable conditions is polymerised to give
polypyrrole. It contains conjugated 4-electrons in the backbone chain. The overlapping of
conjugated 11 electrons results in the formations of valence bands as well as conductance bands.
These bands are separated by a significant band gap. Thus electrical conductance could occur
only after thermal or photolytic activation of electrons to give them sufficient energy to jump
the gap and reach into the lower level of conducting bands. It is, therefore, subjected to
oxidative doping i.e. p-doping with a suitable oxidising agent which could remove electrons
from the chain and create holes resulting in increase in its conductance.
In doped conjugated polymers, there are two types of 1t-electron energy bands-the 1t-bonding
MOs constitute the valence band, while 1t*-anti-bonding MOs form the conduction band. The
oxidative doping of polypyrrole leads to the removal of an electron from the 1t-system of the
backbone leading to highly conductive chain in the polymer. The stepwise conduction mechanism
ofpolypyrrole is summarised in Fig. 7.13.
1. The valence band (VB) and conductance band (CB) is conjugated polymer namely
polypyrrole are separated by significant gap, so the conductivity of un doped polymer
is not very high.
2. Electron removed from polypyrrole by oxidations will lead to the formation of a radical
cation called polaron. It has a hole between VB and CB.
3. Further oxidations will lead to the formations of a bication called bipolaron with two
holes in the VB and CB.
4. The bications lowers its energy by segregation into two positive solitons i.e. two holes
in the mid gap energy levels. The presence of holes in the band gap allows easy jumps
from the VB into the there holes. Then holes thus created in the VB conduct electricity.
As a result the conductivity increases significantly.
7.16.3 Factors Affecting the Conductivities of Organic Polymers
The factors influencing the conductivity of organic polymers are given below:
(a) Conjugation length of the polymer chain: With the increase of conjugation in a given
polymer, its conductivity increases.
(b) Doping level: On increasing in the doping level of the polymer, conductivity increases
but after some time saturation is reached.
(c) Temperature: In contrast to metals, the conductivity of conducting polymer is found
to increase with increase in temperature. At some high temperature, conductivity
becomes constant.
(d) Frequency of current: The conducvity of these materials also depend on the frequency
of current because the transport mechanism of most of these materials is dopping.
7.17 Polyaniline
Poly aniline exists in several forms with electrical conductivities varying progressively from
10- 11 S per cm to more than 105 S per cm. Only one form, called the emeraldine salt is
electrically conducting. Conductive polyaniline are made by protonic doping (i.e., protonation
of imine nitrogen atoms in the backbone of emeraldine films by dipping in acid. Doping is
reversible process as deprotonation can also be done by treatment with aqueous alkali.
Emeraldine salt is also known as 'synthetic metal'. It has conductivity like metals, metallic
lusture and metallic sound.
* Instead of drawing the full structure of polypyrrole in Fig. 7.13, the line structure given in Fig.
7.12 can be drawn.
High Polymers 295
Emeraldine base
(Conductivity - 10- 10 Scm-I)
, -0-'1H-o-ClcleO~ ,
-0- --
N
. I
H --
N
H
I
Emeraldine salt
f
--
N
I
H --
N-
I
H
(Conductivity - 103 S em-I)

Synthesis of Polyaniline
A 0.1 M aniline hydrochloride solution is made in 1.0 M aqueous HCl. To this, an aqueous
solution of 0.1 M ammonium persulphate, (NH4)2S20S is slowly added with stirring.
Polymerisation reaction being exothermic, the temperature rises. To maintain the
polymerisation temperature of 3-4°C, the reaction vessel is placed in an ice bath for some
time with constant stirring. During the polymerisation, colour changes in the following
sequence.
Light blue ---+ blue green ---+ copper tint ---+ green
Aniline (Monomer)
(i) (NH4)2S 20S' 1 MHCI
H 1 (ii) 1M NH40H-
H H
N'QNf)~Nf)N
H
H H
The structure of the green form (electrically conducting emeraldine) is given below:
~N
Polyaniline finally gets precipitated in the green form. The precipitate is filtered, washed
several times with distilled water followed by methyl alcohol or acetone washings until the
washings are colourless. The residue is then transferred to a beaker containing 1.0 M aqueous
HCI and allowed to stand overnight. The precipitate is filtered, and dried under vacuum at
60-80 C. A green coloured salt, called emaraldine salt is obtained. This salt is stirred with
D
0.1 M NH 4 0H at a pH of 9. It is then filtered, washed first with distilled water and then with
methanol. Final washings are done with diethylether. The resulting solid, p-doped polyaniline
(i.e., conducting polyaniline) is dried at 60-80 D C under vacuum.
Applications
Among various conducting polymers, polyaniline is the most important conducting polymer.
Various forms of polyaniline find applications. The blue variety is called the emeraldine base.
Some of the applications of conducting polyaniline are listed below.
1. Conducting polyaniline is used as an electrode material for rechargeable batteries in
the flat buttons. These batteries are small in size longer lasting and cars produce
current density upto 50 mAlcm 2 of commercially sold.
2. Emeraldine base has been used as a resist for lithography. Its solution in NMP (1-
methyl-2-pyrrolidine) mixed with triphenyl sulphonium hexafluroantimonate has been
used to spin coat thin films on quartz and silicon wafers. This blue film on exposure
to UV radiation of 240 nm turns green, characteristic of conducting state of polyaniline.
Conducting lines as small as 0.5 11m can be obtained using this technique.
3. Polyaniline shows a whole range of colours as a result of its protonation and oxidation
forms. Its electrochromic properties (the materials which change colour reversibly
during the electrochemical processes of charge and discharge are called electrochromic
materials) can be used to produce "smart windows" that absorb sunlight and control
solar energy.
4. Polyaniline has also attracted considerable attension as electrochemical transducer
for biosensors. Biosensots are used in clinical technology, but their major use would
be as monitoring devices to control industrial processes using biotechnology.
5. One of the major applications of conducting polyaniline is its use as a new engineering
material to control electromagnetic radiation/dissipation of static charge i.e.,
electromagnetic shielding of electronic circuits (EMl).

1. Why can not thermosetting plastics be reused and reshaped?
2. What is the monomer that would produce the polymer?
3. Classify the following into plastics, elastomers and fibers. (i) PVC (ii) Polystyrene (iii)
Natural rubber (iv) Nylon (v) Silicon rubber (vi) Terylene.
4. 28 g ethene was polymerised by radical polymerisation process and the average degree
of polymerisation of polyethene was found to be 1000. Calculate the number of ethene
molecules in original sample and number of molecules of polyethene produced.
High Polymers 297
5. 84 g of propene was polymerised by radical polymerisation process and DP was found
to be 1000. Calculate the number of molecules of polypropene produced.
6. What is bakelite? Name the monomers of bakelite.
7. Name four substances which are added during moulding of plastics.
8. What are plastics, thermoplastics and thermosetting polymers.
9. What are plasticizers? Give some examples.
10. What do you mean by Tacticity?
11. How do natural and synthetic polymers differ structurally?
12. What is vulcanisation? Why does raw rubber need valcanisation?
13. Why does natural rubber needs compounding?
14. Define glass transition temperature.
The glass transition temperature ofperspex, polystyrene and nylon-66 are 105°, 100°C
and 45°C respectively. What is likely to happen to a sample of each of them, if it
were hit by hammer at : (i) O°C, (ii) 20°C, (iii) 80°C, (iv) 120°C? Give reason.
15. What are conducting polymers? How does doping make the polymers conducting?
16. Illustrate the conductivity mechanism in polyacetylene.
17. Give on example of the practical applications of the following conducting polymers.
(a) Polyaniline (b) Polypyrrole.
18. Give one advantage of using conducting polymers in place of metals?
( ANSWERS)
1. Thermosetting polymers have three dimensional, cross linked net worked structure.
Neighbouring polymeric chains in them are held together by cross-links, which are
strong, covalent bonds. Heating does not soften them, since softening would require
breaking of covalent bond. On strong heating, they would burn without getting
softened. So they cannot be reused or reshaped.
2. The monomer propylene (HaC-CH=CH2 ) would produce the given polymer by addition
polymerisation.
3. Plastics: PVC, polystyrene
Elastomers: Natural rubber, silicone rubber
Fibers: Terylene, nylon
4. We know that:
n H 2C = CH2 polymerisation) (H2C-CH2)n
ethene polyethene
Where n is the degree of polymerisation, which is given to be 1000.
Molecular weight of ethene = 2 x 12 + 4 x 1 = 28
= 1 g mol of ethene
. t· f th Number of ethene molecules
Degree 0 f po1ymensa IOn 0 e ene =
Number of polythene molecules formed
Number of ethene molecules
Hence number of polyethene molecules formed = - - - - - - - - - - -
Degree of polymerisation
28 g x (6.023 x 1023 molecules)/28g

= 1000
= 6.023 X 10 molecules
20
28 g i.e. one mol of ethene contains Avogadro's number i.e. 6.023 x 1023 molecules
So the number of ethene molecules taken =6.023 x 1023 molecules
5. We know that degree of polymerisation of polypropene
Number of propene molecules
= Number of poly propene molecules formed
Molecular mass of propene (H3C-CH=CH2) = 3 x 12 + 1 x 6 = 42
Number of propene molecules
Number of polypropene molecules formed = Degree 0 fpo l ' t'IOn
ymensa
84g x (6.023 x 1023 moleculeS/42g)

=
1000
= 2 x 6.023 X 1020 = 1.2046 X 1021 molecules.
6. It is cross-linked thermosetting polymer made by condensing phenol with
formaldehyde.
Phenol (C 6H 50H) and formaldehyde (HCHO) are the monomers of bakelite.
7. Resin (binder), plasticizer, filter, pigment and dyes, catalyst, lubricant, etc.
8. Plastics,' The term plastics refer to an organic macromolecule possessing the property
to undergo moulding into desired shape upon subjecting to the action of heat, pressure
in the presence of a catalyst.
Thermoplastics " The polymers in which the intermolecular forces of attraction are
intermediary to those of elastomers and fibres are called thermoplastics.
Thermoplastics are linear polymers with no cross-linking between polymeric chains.
Thermosetting polymers " The polymers which on heating change irreversibly into
hard, rigid and infusible materials are called thermosetting polymers.
9. Plasticizers,' The workability of thermoplastics at relatively lower temperatures can
be increases by the addition of certain organic compounds called plasticizers.
Plasticizers help to soften thermoplastics at lower temperatures and thus make their
moulding easier. Dialkyl phthalates (e.g. dioctyl phthalate) and cresyl phosphates (e.g.
tricresyl phosphate) are commonly used plasticizers. For example, polyvinyl chloride
(a very tough thermoplastic) is usually made workable by the addition of
dibutylphthalate which makes it soft and easily mouldable.
10. Tacticity,' The orientation of monomer units in a polymer molecule can take place
in an orderly or disorderly fashion with respect to the main chain. Due to different
orientation of the group attached to the main chain, the molecule may be Atatie
(without order), Isotaetie (same order) and Syndiolaetie (contrasting order). The
difference in configuration (tacticity) do affect their physical properties.
11. Natural and synthetic rubber,' Natural rubber is a polymer of isoprene (2-methyl
buta-1,3-diene)
High Polymers 299
yH 3
CH2 =C-CH=CH2
Isoprene
rH. J~'CH-CH21
When n isoprene units combine, the polymer is formed
Po~riu'" ,
Isoprene Polyisoprene
Polyisoprene may have either a cis or a trans structure, because each repeating unit in
it contains a double bond. In fact, in natural rubber, all the double bonds have cis
configuration. In other words, natural rubber is cis-polyisoprene. On the other hand,
synthetic rubber (gutta percha) has all trans configuration. In natural rubber-CH3 group
and -H lie on the same side, whereas in trans from these groups lie on opposite sides.
12. Valcanisation of Rubber : The process of heating natural rubber with Sulphur to
improve its properties is called vulcanization. Vulcanised rubber has better tensile
strength, elasticity and resistance to abrasion than natural rubber. By this process, a
few cross linked are introduced in the chains, which increase the intermolecular forces
between the chains.
Why does raw rubber need vulcanization?
Raw rubber possesses drawbacks like high elasticity, tackiness, poor chemical
resistance, solubility in organic solvents, poor strength, large water absorption capacity,
etc. In order to improve its characteristics, raw rubber is vulcanized by adding some
sulphur to it at 100-140°C. This treatment causes anchoring of the rubber molecule
chains together, thereby elasticity is lowered and most of the above inherent defects
are partially/fully eliminated. Hence, we can easily say that raw rubber needs
vulcanization.
13. Natural rubber possesses many drawbacks. In order to improve the characteristics and
to impart desired colour, raw rubber is compounded with many ingredients like
plasticizer, vulcanizing agent, antioxidant, accelerator, reinforcing filler, colourant, etc.
14. Glass transition temperature is that temperature at which an amorphous polymer
change on heating from glassy state to rubbery state and vice versa on cooling.
(i) All would shatter, (ii) all would shatter, (iii) only nylon-66 would service the blow,
(iv) none would break.
Reason : Below the glass transition temperature, the samples would be brittle and
shatter; and above the transition temperature, they would only deform, but not break.
15. Polymers which can conduct electric current through them are called conducting
polymers. Normally polymers are insulators and electrons in a polymer are localised
and so they are not available for conduction of current. But doping can delocalise the
electrons (especially the p-electrons) and make the available for the conduction of
current. Conducting polymers are obtained by doping an oxidising or a reducing agent
into the organic polymers having a conjugated system of single and double bonds at
alternate positions. The bond being weak, the 1t electrons thus move all along the
chain ofthe polymer. Doping is of two types n-doping and p-doping. n-doping involves
reduction process and electrons transferred from the redUCing agent moves along the
chain. p-doping involves oxidation and the electrons withdrawn from the chain creat
holes, due to which current is carried along the chains.
16. Polyacetylene (CH)n has long chain of atoms in which each carbon atom is sp2
hybridized.
H H H H H
When an electron from an external source enters an unhybridized p orbital of a C
atom in the polyacetylene molecule, it moves down the chain of C-C bonds as shown
below.
Flow of current
Incoming
electron
\1357135713571357
'~\f\N: --+~ --+~ --+~.--+
2'\i/6 2'-1/6 2 '-!I 6 2,\!/6
W ~ 00 00
Incoming or or or or
electron
"" 1 3 5 7 3 5 7 3 5 7 3 5 7
"'VVV --+ VVV --+ VVV ~ VVV ~
246 246 246 246
W ~ 00 00
When the electron enters the chain at carbon atom 1, the breakage of the 7t bond
between carbon atoms 2 and 3 can be easily seen. (a) Then electrons broken from
the 7t bond pairs with the lone electron to form a new 7t bond between C atoms 1 and
2, thereby leaving an unpaired electron on C atom 3 (b) Then, the 7t bond bet~een
carbon atoms 4 and 5 is broken, one electron pairing with the lone electron on C
atom 3 and forming a new 7t bond between C atoms 3 and 4. The lone electron new
appears on carbon atom 5 (c). By the same sequence of events, the additional electron
can move to C atom 7(d). The process continues, down the chain of the molecule,
thereby turning it into a conducting path.
(a) Polyaniline is used to make rechargeable batteries in the shape as flat buttons
or as laminated rolled films.
(b) Polypyrrole is used in 'smart' windows. These smart windows can change their
colour in response to changes in temperature or amount of sunlight. The colour
change is from a transparent yellow-green to blue-black.
18. Conducting polymers are lighter and they do not corrode.
( SOLVED TYPICAL PROBLEMS)

1. Define a polymer. What is meant by degree of polymerization?
Ans. A high molecular mass macro molecule formed by linking together of a large number
of small molecules of monomer(s) is called a polymer.
The number of repeating units [of monomer(s)] in a chain of a polymer is called degree of
polymerisation.
High Polymers 301
2. Differentiate between homopolymer.
Ans. A homopolymer consists of identical monomer units; while a copolymer consists of
monomer units of different chemical structures.
3. What is meant by polymerization?
Ans. A process of uniting (or linking) together of two or more smaller and simpler molecules
of same or different types with or without the elimination of small molecules like H 20, NH g,
etc., resulting in the formation of new C-C, C-N, Si-O, etc. linkages.
4. Differentiate between addition and condensation polymerization.
Ans. Addition polymerization is a reaction that yields a product which is "exact multiple"
of the original monomeric molecule; while condensation polymerization is an intermolecular
combination through different functional groups present in the monomers, with the elimination
of small molecules like H 2 0, etc. For details refer text.
5. What is meant by functionality of a monomer? Name a trifunctional monomer.
Ans. The number of bonding sites in a monomer. Phenol.
6. What is copolymerization?
Ans. Joint polymerization of two or more monomer species, e.g., butadiene and styrene
copolymerise to yield GR-S rubber.
7. What are cross linked polymers? Give one example of this type.
Ans. The polymers in which the linear polymer chains are cross linked to form a three-
dimensional network structure are called cross linked polymers. The common example of this
type of polymer is bakelite.
8. What is the difference between two notations: nylon-6 and nylon-66?
Ans. Nylon-6 is obtained from caprolactum which is obtained from cydohexane. It has
only one compound having only 6 carbon atoms.
Nylon-66 refers to polymer obtained from 6 carbon atoms of dicarboxylic acid (adipic acid)
and 6-carbon atoms of diamine (hexamethylene diamine).
9. What are thermosetting polymers?
Ans. Thermosetting polymers are normally made from relatively low molecular mass
semifluid polymers which when heated in a mould become infusible and form hard insoluble
mass. They have extensive cross linking and form network structure. For example, bakelite.
10. How do thermoplastic differ from thermosetting polymers?
Ans. Thermoplastics when heated become soft. These can be moulded into any desired
shape. The thermoplastics can be processed again and again.
On the other hand, thermosetting plastics on heating become hard and insoluble masses.
These cannot be moulded into desired shape and cannot be reprocessed. For further details
refer text.
11. Define thermoplastics and thermosetting polymer.
Ans. A polymer which can be softened on heating and hardened on cooling reversibly, e.g.,
PVC.
A polymer which during moulding process get hardned and once set, it cannot be softened
again, i.e., it is a permanent setting polymer.
12. Name two natural and two synthetic polymers which are used as textile fibres.
Ans. Silk, wool, cotton, jute, etc.
Nylon-6 and terylene.
13. What is an elastomer? Why do rubber become stiff on streching?
Ans. Any rubber-like elastic polymer, which can be stretched to at least three times, but
it returns to its original shape and size as soon as stretching force is removed.
Unstretched rubber molecules are in the form of coils. On stretching, the macromolecular
coils get partially aligned WIt another, thereby causing crystallization and consequent stiffening,
due to increased attractive forces between the molecules.
14. What is meant by the term valcanization of rubber? What is the main purpose
of vulcanization?
Ans. The process of heating raw rubber with sulphur in order to cross-link the chains and
to get stiff and better product.
Added sulphur combines chemically at the double bonds of different rubber chains, thereby
making the product.
15. Plasticizer is used during manufacturing of plastics. Give reason.
Ans. Added plasticizer improves plasticity and flexibility of the plastic mix, thereby it causes
reduction in temperature and pressure required during moulding of plastics.
16. Why are plastics indispensible in every day life?
Ans. Plastics are indispensible due to their unique properties like: (i) lightness in weight;
(ii) corrosion resistance, (iii) low fabrication cost, (iv) good thermal and electrical insulation
properties, (v) low thermal expansion coefficient, (vi) high refractive index, (vii) decorative effect,
(l)iii) easily and quick moulding, etc.
17. What is natural rubber and gutta-percha.
Ans. It consists of long-coiled chains of polycisisoprene. A horny and tough form of
polytransisoprene.
18. Name two epoxy resins used in our daily life.
Ans. M-seal and araldite.
19. Why is teflon highly chemical resistant?
Ans. Due to presence of most electronegative element, F, in teflon, there is very strong
attractive forces between its different chains. Hence, it possesses extremely high chemical
resistance towards most chemicals.
20. What is the function of S in the vulcanization of rubber?
Ans. Sulphur makes the rubber more elastic, more ductile, less plastic and non-sticky.
21. Name of polymer which is used for making nonstick utensils.
Ans. Teflon.
22. Explain the difference between polyacrylates and polyesters.
Ans. Polyacrylates are formed from the esters of acrylic acid (HC 2 = CH-COOH), such as
H
CH 2 = CHCOOR. For example, polymethyl methaacrylate (PMMA), [ -CH 2 - X3 1
600CH3 n
These are addition polymers. Polyesters are polymers having ester linkages (-~ - 0- J.
For example, terylene, -E-O-CH 2 CH 2 0-C0-<:Q>-cO-)". These are condensation
polymers.
High Polymers 303
23. Write the structure of a reagent used for initiating a free radical chain
reactions. How does it act?
Ans. Tertiary butyl peroxide is used for initiating a free radical chain reaction. It decomposes
under mild conditions to form t-butoxide free radical which initiates the reaction.
~
H3
373-427 K ) 2CH _ _ CO
a
Ha
Free radical
24. Polythene tubings are tough, flexible and can be manipulated in hot water.
(i) Does it mean that PE is a thermosetting polymer?
(ii) Suggest the class transition temperature of polythene.
Ans. (i) No. It is a thermoplastic, because its shape can be changed as the temperature
changes.
(ii) The transition temperature must be below room temperature, since it is flexible. In
fact, Tg ofpolythene can be as low as -170°C.
25. What do you mean by chain growth polymerisation? Give an example each of
addition and condensation polymerisation.
Ans. When the polymerisation process proceeds by chain mechanism and high molecular
weight polymer is formed at once, the process is called chain growth. In this case, longer
reaction's time has no effect on the molecular mass, but gives higher yield of polymer. At· any
stage of the reaction either unreacted monomer or the high molecular mass polymer are
available. It can be either addition or condensation polymerisation.
Addition chain growth polymerisation
The high molecular weight polymers can be synthesized either by free radical or ionic
mechanism by addition chain growth. Some of the examples of monomers which undergo
addition polymerisation are given below:
/CH 3
H2C=~~ H 2C = <A.,.COOCHa
ethane vinyl chloride methyl methacrylate
Condensation chain growth polymerisation
iFriedeICrafts//.
+- @-
0 CHJ3r reaction • +-/(5\.--CH2Br~CHJ3~ ~~e~ore
~ ~ active)
!
Monomer
Dimer
(5'active sites)" " ""
3'active sites
26. Explain the mechanism of addition chain growth polymerisation.
(Surat, Nov. 21(, RGT, May 2001, Anna, June 01)
Ans. The generalized mechanism of chain growth addition polymerisation takes place with
compounds having the multiple bonds such as vinyl monomers:
H 2C=CH-G, where G is a substituent group, it can be -H, -CH 3 , -CI, -CN, -C6H5
etc.
The polymerisation proceeds in three distinct stages.
(1) Chain inition step: Interaction of monomer (M) with initiator (In) for its activation and
generation of reactive particle (M*) occurs in this step.
M~M*
The reactive particle (M·) can be a free radical, cation or anion and accordingly addition
polymerisation is classified as (i) free radical polymerisation, (ii) ionic polymerisation (a) cationic
and (b) anionic polymerisation.
(2) Chain propagation step : It consists of a series of consecutive reactions to carry the
chain growth process by the interaction of M* with other monomer molecules.
M*+M~Ml*
Ml*+M~M2*
M2*+M~M3*
number of similar steps, to generate Mn *
(n-l)
M*(n - 1) + M ~ Mn*
(3) Chain termination step: The chain growth is finally terminated i.e., arrested by this
step.
Mn*~~
Where Mn • is activated growing polymer chain and Mn is inactive polymer molecule.
27.216 g butadiene is copolymerized with 104 g of styrene. What is the molecular
formula of the copolymer?
Ans. 216 g of butadiene = 216 g/54 g mol- 1 = 4 mol
104 g of styrene = 104 g/104 g mol- 1 = 1 mol
:. Molecular formula of copolymer is:
2
[CH -CH=CH-CH 2-t;fCH2""©--+';
28. PVC is soft and flexible; whereas bakelite is hard and brittle. Give reason.
Ans. PVC is a straight-chain thermoplastic in which molecular chains are bonded to each
other through weak van der Waal's forces of attraction. Consequently, long chains can easily
be bent, slipped, twisted by the application of a small force. Hence, it is soft and flexible. On
the other hand, bakelite is a cross-linked thermosetting plastic bonded together by strong
covalent bonds only. Consequently, no deformation can take place in its molecule. Hence, it is
hard. If a large force is applied to bakelite molecule, its covalent bonds get broken, thereby
imparting it a brittle character.
29. Teflon is an addition polymer, but it behaves somewhat like a thermosetting
polymer. Give reason.
Ans. Teflon, being an addition polymer of tetrafluoroethylene, should behave as
thermoplastic like other addition polymers. However, due to the presence of most electronegative
F-atoms in regular configurations, the teflon molecules experience quite strong attractive force
(H-bonding) between H-atoms of one chain and F-atoms of other chain. This makes teflon dense,
chemically inert and high temperature softening. These are characteristics of a thermosetting
polymer. Hence, teflon behavro'3 somewhat akin to thermosetting polymers.
High Polymers 305
30. Explain the mechanism of branching and cross-linking during the free addition
polymerisation.
Ans. The macro-free radical formed during the propagation step may undergo the
abstraction of a H atom or any other univalent atom from the middle of the chain. Thus the
active center is transferred from the growing end to some where in the middle of the polymer
chain as shown :
The propagation of reaction from middle center will create branches as shown:
f
+ CH2 = H-,--+.
CH2-CH•
G I
G
There is also the possibility of the combination of the newly formed radicals at the middle
leading to the formation of cross-linkages.
31. Why do all simple organic molecules not produce polymers?
Ans. A monomers is an organic or inorganic molecule which is at least bifunctional. For

example, ethylene is bifunctional (i.e., has two bonding sites per molecule), so it is capable of
polymerizing to form polymer, polyethylene. However, organic molecules like C2H s' C2H 5CI,
etc. are only monofunctional, so they cannot form polymers. Hence, we can say that all simple
organic molecules do not produce polymers.
32. 159 g of acrylonitrile is copolymerised with 125 g of vinyl chloride. What is
the molecular formula the copolymer?
Ans. Molecular mass of acrylonitrile, H 2C =CHCN =12 x 3 + 1 x 3 + 14 =53
159
Mols of acrylonitrile = 53 = 3
Molecular mass of vinyl chloride H 2 C =CHCI =12 x 2 + 1 x 3 + 35.5 =62.5
125
Mols of vinyl chloride = 62.5 = 2
In the copolymer the ratio of mals of acrylonitrile is to vinyl chloride =3:2.
So the formula of the co-polymers is as under:
33. Explain chain terminators in polymerisation. Write the names of two chain
termination. (Surat Nov 2K, June 2001)
Ans. Chain termination. The growing polymer chain can be terminated by the following
ways:
(i) Recombination: It consists of combination of two free radicals.
-CH 2
.H+ .H-CH ~ -CH2 H+ H-CH 2
bb bb
- 2 - -
-CH2-~H+ it ~ -CH2 -
b
H-R
Polythene chain terminates mainly by recombination.

(ii) Disproportionation : It involves the transfer of a hydrogen atom of one macro-radical
to another to form two macro-molecules, one of them with a double bond at the end.
-CH, -t '~-CH'
H
+
H
- ---> -CH,
H H
-~-H + ~=CH-
At temperature less than 60°C, PMMA chain terminates mainly by disproprotionation.
(iii) Reaction with polymerisation inhibition: Growing polymer chain can be terminated
by its reaction with inhibitors like hydroqninone and trinitrobenzene.
(iv) Reaction with the solvent molecules : Solvents like CCl4 can also react with the free
radicals and terminate the reaction.
-CH, - t
H H
+ CCI. ---> -CH, -~-CI + 'CCI,
CI,C' + .CCl, -+ CI- ~:-~:-CI

34. 100 g of novolac is to cross-linked by one -CH2-groups of each benzene ring.
What weight of formaldehyde is required for achieving this?
OH
Ans. 2 molecules of ©-CH>- unit of novolac require
= 1 molecule of HCHO
High Polymers 307
2 x 96 g of novolac requires = 30 g HCHO
.
or 100 g of novolac requIres = 30gx lOOg
2x96g
HCHO =15.625 g HCHO.
35. Wby is plasticizer used during moulding of plastics?

Ans. Many polymers are not very flexible and elastic, so their moulding into intricate shapes
posses difficulty, even though they are in thermoplastic forms. In order to increase plasticity,
flexibility and mouldability of plastic resins, plasticizers are usually added to them before
moulding. The added plasticizer neutralizes partly the intermolecular forces of attraction between
the polymer chains, thereby imparting greater freedom of movement of polymeric chains wrt
one another. Consequently, addition of plasticizer facilitates the moulding operation of plastic
resins.
36. Natural rubber needs vulcanization. Give reason.
Ans. Natural rubber possesses drawbacks like plastic nature, poor strength tackiness, poor
resistance to solvents, little durability, etc. In order to improve these characteristics, raw rubber
is vulcanized by heating it with 3 to 6% sulphur at 100-140°C. By doing so, the product (called
vulcanized rubber) possesses better characteristics. Hence, natural rubber needs vulcanization.
1. Define the following terms :

(a) Polymer (UPT, Jan 2001; Dibrugarh, June 2K)
(b) Resin (vT, Aug. 1999)
(c) Monomer (KU, June 2000 2K)
(d) Homopolymer and copolymer (KU May 1999; June 2000 2K)
(e) Degree of polymerisation (vT, Aug. 1999; UPT, Jan 2001)
(fJ Functionalit.y (vT, Aug. 1999)
(g) Addition polymerisation (VT, Aug. 1999)
(h) Condensation polymerisation. (Surat, Nov. 2K)
2. (a) Differentiate between addition polymerisation and condensation polymerisation with
suitable examples. (Tripura, 2K; MD, Jan. 2001; PT, Dec. 2K;
Bharathiar, April2K; GGSlp, July 2K; Anna, Nov. 2K)
(b) Define the term functionality of monomers. How is it related to the chemical structure?
(c) Discuss the statement "All polymers are macromolecules, but all macromolecules are
not polymers."
3. Give reasons :
(a) All simple organic molecules do not product polymers. (Nagpur, May 2001)
(b) Bakelite can not be remoulded.
(c) Plasticiser is used during moulding of plastics.
4. (a) Explain addition and condensation polymerisation with suitable examples.
(Anna, Nov. 2K; PT, Dec. 2001 2K)
(b) Explain the free radical polymerisation mechanism of vinyl compound. Or Explain
mechanism of addition polymerisation.
(Surat, Nov. 2K; RGT, May 2001; Anna, June 2001; Calicut, June 01; VT, March 1999,
Aug. 1999, April 21(, Aug. 20012K)
(c) Give the salient features of condensation polymerisation. (Calicut, June 2001)
(d) Distinguish between thermoplastic and thermosetting polymers or resins.
5. (a) Explain chain terminators is polymerisation. (Surat, Nov 2001 2K)
(b) Explain disproportionation in addition polymerisation.
Write the initiation, propagation and termination reactions involved in the
(c)
polymerisation of ethylene with AIBN. (UPT, May 2001)
6. Answer the following:
(i) Why are plastics indispensible in everyday life?
(ii) Why is Teflon highly chemical-resistant? [U.P. Tech., B. Tech., ["I Sem., 2000-01j
7. (a) Illustrate with examples any two different techniques used in polymerisation.
(VT, March 2001)
(b) Describe in detail the chemistry and method of preparation of one addition polymer.
(PT, Dec. 2K)
(c) Explain the following:
(i) Solution polymerisation. (Calicut, June 2001)
(ii) Condensation polymerisation. (Calicut, June 2001)
(iii) Emulsion polymerisation. (vT, March 99)
8. (a) Explain the effect of structure on the properties of a polymers.
(MD, May 2001; Nagpur, May 2001)
9. (a) Explain strength of polymer. (Amravati, May 2001)
(b) Discuss the relation between structure of polymer and (i) crystallinity, (ii) elasticity,
(iii) strength. (VT, April 21(, March 2001, Aug. 2001)
10. (a) Distinguish between thermoplastic and thermosetting polymers or resins.
rBharathiar, May 2001; S1(, June 2001; Amravati, May 2001; Surat, June 2001; Tripura,
2K; Anna, July 2K, Jan. 2001; Ku, June 2K; RGT, May 2001; MK, Ampril 2001;
Dibrugarh; June 21(, 2001)
(b) Write the structures of three addition polymers and three condensation polymers with
their respective monomers.
11. Describe the method of preparation, properties and applications of the following:
(a) Teflon (PTFE)
(Ku, May 1999, Jan. 2001, June 2K; Sv, Aug. 2001; Surat, Nov. 21(,- Dibrugarh, July 2001)
(b) Polymethylmethacrylate (PMMA)
(Ku, June 2K; VT, March 1999, March 2001; GGSIp, July 2K)
{c) Phenol-formaldehyde (Bakelite)
(Amravati, May 2001; Ku, May 1999; VT, April2K; Tripura, 21(,' Sambalpur. July 2001;
GGSIP, July 21(,' Anna, Nov. 21(,' MD, Jan. 2001)
(d) Epoxy resins (Andhra, June 2001; Ku, Jan. 2001; VT, March 1999, Aug. 2K)
(e) Polyurethane. (VT, March 1999, Aug. 2K; MD, May 2K; RGT, May 2001; Sv, Aug. 2001)
•
High Polymers 309
12. (a) What is meant by compounding of plastics? What are the different constituents of
compounding. Write their uses. (S](, June 2001)
(b) Write the names of three moulding costituents for plastics. (Surat, Nov. 2K)
(c) Describe a moulding method for thermoplastic resins. (Surat, June 2001)
(d) Explain the functions of different ingredients used in compounding of plastics.
(VT, Aug. 1999)
(e) Explain the compounding of resin into plastics. (VT, Aug. 2001)
(j) Why bakelite cannot be remoulded? (MG, Oct. 1998)
(g) What is the role of plasticizer during moulding plastics. (PT, Dec. 210
(h) Write short note on constituents of plastics. (Raj., May 2001)
13. (a) What is vulcanization of rubber? Mention its uses.
(SK, June 2001; Andhra, June 2001; Raj., May 2001)
(b) Explain why natural rubber needs vulcanization. How is it carried out?
(PT, Dec. 2K; RGT, May 2001; Anna, July, 2K)
(c) Discuss briefly the process of vulcanization of rubber. (Anna, Nov. 2K)
(d) Write short note on vulcanization of rubber. (Tripum, 2](,· RGT, May 2001)
14. (a) Write short note on elastomers (Tripura, 2K; VT, March, 2001)
(b) Define synthetic rubber. (Ku, May 1999; Surat, Nov. 2](,- Raj, May 2001)
(c) Differentiate between elastomer and plastic. (Ku, May 1999)
(d) Write the structures of natural rubber and gutta-percha. What are the deficiencies of
natural rubber?
(e) Mention the advantages of synthetic rubber over natural rubber.
(VT, March 1999, March 2001)
15. (a) How is neoprene prepared? mention its properties and uses.
(VT, Aug. 1999, 2](, March 2001, Aug 2001; RGT, May 2001; S](, June 2001)
(b) What are polyurethanes? What is the principal linkage in polyurethane.
16. (a) Give the synthesis of epoxy resins. Mention its important uses. (vT, March 2001)
(b) Give the preparation structure and uses of the following:
(i) Styrene-butadiene rubber (SBR). (Ku, June 2K; Amravati, May 2001)
(ii) Nitrile rubber (GR-1), (Amravati, May 2001; MD, May 2](,· MG, Oct. 1998)
(iii) Butyl rubber. (RGT, May 2001)
(iv) Buna-N. (Sambalpur, July 2001)
(c) How does the structure of elastomers compare with that of plastics? (PT, Dec. 210
17. (a) What is glass transition temperature? Discuss the parameters affecting the glass
transition temperature. What is its significance? (PT, Dec. 2K; VT, March 1999)
(b) Write note on glass transition temperature. How is it important? What are the important
structural features that affect it? (vT, Aug. 1999; Dihrugarh, JUly 2001)
18. (a) Explain with examples conducting polymers.
(GGSIP, July 2](, May 2001; Andhra, June 2001)
(b) What are p-doping and n-doping conducting polymers? Explain their mechanism of
conduction.
(c) Discuss classification of conducting polymers.
19. How does the structure of polymers affect the following properties:
(i) strength (ii) plastic deformation (iii) Tacticity.
20. Explain (i) Crystallinity (ii) Elasticity (iii) Chemical reactivity are influenced by the structure
of polymer.
21. (a) Write a note on P.T.F.E. (GGSPu, B. 'leek, May 2002)
(b) What are polyurethane foams? (MK, April 2001)
22. (a) What is meant by compounding of plastics?
(b) Define the term crystallinity of polymers. How is it related to the chemical structure?
23. How is the glass temperature of a polymer determined? What is its significance?
24. How is conducting polyaniline prepared? Give applications of conducting polymers.
25. Discuss band theory of conductance mechanism and apply it to explain the conductance
mechanism of polypyrole.
26. Account for the following:
(i) Bulk polymerisation is not used on commerical scale.
(ii) When doped with oxidising agents, polymers exibit electrical conductivity.
(iii) When doped with reducing agents, polymers exibit electrical condcutivity.
27. What are adhesives? How are they classified?
28. What are plastics? How are they classified? Write down the preparation, properties and
industrial application of polyester resin or phenolic resin. (M.I., B. 'lech., 18t Sem., 2001-2002)
29. Explain the difference between thermoplastic and thermosetting resins. Give the methods of
preparation of any two types of plastic along with their physical and chemical properties.
[MDU, B.E., 1st Sem., Dec. 2002J
30. (a) PVC is soft and flexible where as Bakelite is hard and brittle. Gie reasons.
(b) What are the chief physical characteristics expected of an elastomer? How are these
achieved in a new product?
(c) Describe the preparation and technical applications of silicone fluids.
(d) What is meant by copolymerization? (KU, June 2004)
31. (a) Differentiate between a polymer and macromolecule.
(b) Though the functionality of ethene is two and the polymer obtained from it is expected
to be a linear one. However, under the impact of temperature (180°C-200°C) and pressure
(1500 atm), in presence oftraces of oxygen, a branched chain polythene is obtained. Why?
(e) Write the preparation, properties and industrial application of any thermoset.
(d) Explain the various types ofpolymerisation. (KU, Jan. 2005)
32. (a) Discuss the preparation, properties and uses of anyone thermoplastic material.
(b) Discuss the various types of polymerisation. Describe the mechanism of addition
polymerisation (any two types).
(c) Write a short note on GR-N elastomer. (KU June 2005)
33. (a) Explain the manufacture of an Epoxy Resin. Give its applications.
(b) Discuss the emulsion polymerisation technique. (VTU, B.E., March 1999
34. (a) Describe the manufacturing of phenol formaldehyde and give its uses.
(b) Discuss the relation between structure and following properties of a polymer.
(i) Crystallinity (ii) Elasticity (iii) Strength (VTU, B.E., April 2000)
35. (a) Discuss the relation between the structure and the following properties of a polymer.
(i) Crystallinity (ii) Elasticity
High Polymers 311
(b ) Describe the manufacture of the following:
(i ) Polystyrene and (i i) Neoprene (VTU, B.E., August 2001)
36 . (a) Give the manufacture and applications of Epoxy Resin.
(b ) A sample of polypropylene as 20 percent of polymer with molecular mass of 16000,30%
with a molecular mass of 1000 and rest with a molecular mass of 25,000. Calculate the
number average and weight average molecular mass. (VTU, B.E., August 2002)
37 . (a ) Discuss the addition and condensation polymerisation with examples.
(b) Explain the free radical mechanism of addition polymerisation taking ethylene as a
monomer.
(c) Give the synthesis and applications of Butyl Rubber and Epoxy Resin.
(VTU, B.E., Jan. 2003)
38. (a ) Give the manufacture and application of
(a ) Polyurethane, (ii) Epoxy Resin and (iii) Buna-S.
(b) What is conducting polymer? Give the synthesis of polyamiline and mention its
applications. (VTU, B.E., July IAugust 2004)
39 . (a ) What are polymers? Explain the free radical mechanism of addition polymerisation
taking ethylene as an example.
( b) Define Glass Transition Temperature and mention its significance.
(c ) Explain the manufacture of the following polymers and mention their use.
(a) Buna-S, and (ii) Phenol-formaldehyde (VTU, B.E., March 2005)
WATER TECHNOLOGY
SYLLABUS
Impurites in water; Water analysis-Determination of different constituents in water -hardness,
alkalinity, chloride, nitrate, sulphate, fluoride and dissolved oxygen, Numerical problems
on hardness and alkalinity. Biochemical Oxygen Demand and chemical oxygen demand,
Numerical problems on BOD and COD, sewage treatment.
Potable water, purification of water; flash evaporation, electrodialysis and reverse
osmosis. Hazardous chemicals-Introduction and classification.
8.1 INTRODUCTION
Water is surely God's greatest gift to mankind. The very existence of life cannot be imagined
without water. One can live without food, shelter or any other thing but life without water is
just not possible. Even our body contains around 70% water in it. From an engineer's point of
view, water is no less important. It is required in boilers for production of steam, which acts
as a source of energy, as a coolant in many power and chemical plants, in steel, paper, textile,
ice and n\any other such industries. Despite its incredible importance, water is receiving least
attention and is getting contaminated in ways beyond description.
Water is obtained from nature in various forms such as rain water, river water, sea water,
spring water and well water. Water is not only essential for the lives of animals and plants but
also occupies a unique position in industry. Surface and ground water is normally used for
industrial and domestic purposes. Some of the major parameters which are generally checked
for assessing the water quality for a particular use are determination of hardness, alkalinity,
turbidity, total dissolved solids, suspended solids, dissolved oxygen (DO), Biological oxygen
demand (BOD), total residual chlorine pH, temperature etc. Hence a complete analysis with
respect to these is desired for determining the suitability of water for a particular industrial ·
use.
Water Technology 313
In industries, a large amount of water is used for cooling purposes. Water used for cooling
purposes need not be completely free from the impurities. However, when water is used in
industry for preparing solutions, carrying out the reactions, dilution etc., it should be reasonably
pure. Each industry has its own specifications for water. Therefore, the treatment of water
depends on the purpose for which it is to used.
8.2 IMPURITIES IN WATER
Water, from all the natural sources, has got impurities. The sources of these impurities
are the following:
(i) Water takes up impurities from the ground, or soil with which it comes into contact.
(ii) Water becomes impure when it comes in contact with sewage or industrial wastes.
(iii) Organic impurities in water are generally introduced by the decomposition of plants
and animals remains. Certain micro-organism and bacteria are also responsible for
the organic impurities in water.
Nature of Impurities in Water
The common impurities present in natural water may be of the following types:
(i) Dissolved gases like oxygen, carbon dioxide, hydrogen sulphide etc. Water may also
contain some undesirable gases and odour due to the putrefaction of organic matter.
(ii) Suspended matter: These are mostly insoluble minerals such as clay, sand etc. These
cause turbidity to water.
(iii) Microscopic matter : These consist mainly of bacterial and other micro-organisms,
like algae and fungi.
(iv) Dissolved mineral salts: Dissolved salts are mainly the carbonates, bicarbonates,
chlorides and sulphates of calcium, magnesium, iron, sodium and potassium. The
presence of these salts imparts a sort of hardness in water, i.e., a hard water does
not produce a lather with soap. Although hard water is not always harmful for drinking
purposes, it causes a waste of soap material in the laundry work.
(v) Organic matter: It includes vegetable and animal matter i.e., decayed plants and
animals, oil globules etc.
(vi) Colloidal impurities: They consist of proteins, amino acids, ferric hydroxide, clay and
lumic acid etc.
8.3 HARD WATER
Water which does not produce lather with soap solution readily, but forms a
white scum or precipitate is called hard water.
It is due to the presence of some dissolved salts in it. Soaps are sodium or potassium salts
of higher fatty acids like stearic acid, oleic acid and palmitic acid. When hard water is treated
with soap, it does not produce lather, rather soap gets precipitated in the form of insoluble
salts of calcium and magnesium. No lather is formed until all these ions are completely removed
and hence a large amount of soap gets wasted in the process.
CaCl2 + 2Q17H35COONa ~ (C 17H 35COO)2 Ca -J, + 2NaCI
(Calcium chloride) Sddium stearate Calcium stearate
from hard water) (Soap) (Insoluble ppt.)
Such precipitates are not formed with detergents, which are sulphonates of long chained
alcohols.
Water, which easily forms lather with soap solution, is called soft water. Such
water does not contain calcium and magnesium salts in it.
8.3.1 Difference between hard water and soft water
Hard Water Soft Water
a. It does not produce lather readily on treat- a. It produces lather instantly on treatment
ment with soap solution. It forms a white with soap solution.
scum or precipitates on treatment with
soap solution.
b. More time and fuel is consumed on boiling b. Less time and fuel is consumed on boiling
hard water because boiling point is soft water.
increased due to hardness.
c. Detergent properties of soap are depressed c. Detergent properties of soap are not
in hard water so large amount of soap is depressed in soft water so less amount of
consumed during its use. soap is consumed during its use.
d. Salts of calcium and magnesium are d. No salt of calcium and magnesium are
dissolved in it. dissolved in it.
8.3.2 Type of hardness: Hardness of water is of two types :
(A) Temporary hardness (B) Permanent hardness
(A) Temporary hardness
It is caused due to the presence of bicarbonates of calcium and magnesium.

It is called temporary hardness because it can be removed easily by boiling.
On boiling, bicarbonates of calcium and magnesium get decomposed to give insoluble
carbonates or hydroxides. These carbonates or hydroxide being insoluble are removed in form
of precipitates and thus temporary hardness is removed.
Ca(HC03)2 ~ CaC03 J, + H 20 + CO2 l'

Mg(HC0 3)2 ~ Mg(OH)2 J, + 2C02 l'
Temporary hardness is also called carbonate hardness or alkaline h'ardness. It is due to
the presence of bicarbonates of Ca and Mg, carbonates of Fe and other heavy metals to small
extent and hydroxides ofthe hardness-producing metal ions. It can be determined by titration
with standard acid solution (say HCI) using methyl orange as an indicator.
(B) Permanent hardness
It is due to the presence of chlorides and sulphates of calcium and

magnesium. It is called permanent hardness, since it cannot be removed by
boiling.
However, it can be removed by using various chemical agents. Calcium and magnesium
salts are not the only salts responsible for hardness. They are mentioned because they are
most commonly present. However, all soluble salts of heavy metals cause hardness.
It is also called non-carbonate or non-alkaline hardness. It can be determined by subtracting
the alkaline hardness from the total hardness.
8.4 UNITS OF HARDNESS
As discussed above, hardness of water is due to the presence of number of salts in
it but for comparing the hardness of different samples of water of varying composition, it is
necessary to choose a reference standard. For this purpose, hardness is expressed in terms of
equivalents of calcium carbonate only. The reason of choosing calcium carbonate as a reference
standard is that it is the most insoluble salt that can be precipitated in water treatment.
Moreover, it molecular mass being 100, equivalent weight being 50, the calculation become
easy.
Hence whatever dissolved salts are present in water, they are first converted into calcium
carbonate equivalents. For example, if water contains 10 ppm of MgCl2 and 8 ppm of CaS04,
the calcium carbonate equivalents of these salts would be
10x100
MgC~ = 95
=10.53 ppm where 95 and 136 are molecular weights
8x100
caS04 = 136 = 5.88 ppm ofMgCl2 and CaS04 respectively
Thus total hardness equal to 10.53 + 5.88 = 16.41 ppm expressed as .Calcium Carbonate
__________________________________________________--,
equivalenrt=s~.
In general, CaCOs equivalent of hardness

Wt. of the substance Eq. wt of CaCOs (50)
= producing hardness x
Eq. wt. of substance
Calculation of equivalents of calcium carbonate
Dissolved salt Molar Chemical Conversion factor

mass equivalent CaCOa equivalent for calculating
Ca(HC03)2 162 81 100/162

Mg(HC03)2 146 73 100/146
CaS0 4 136 68 100/136
CaC12 111 55.5 100/111
MgS°4 120 60 100/120
MgC12 95 47.5 100/95
MgC°3 84 42 100/84
CaC03 100 50 100/100
FeS04 · 7H2O 278 139 100/278
CO 2 44 22 100/44
Mg(N03)2 148 74 100/148
HC03" 61 61 1001122
OH- 17 17 100/34
CO~- 60 30 100/60
NaAl°2 82 82 100/164
Al2(S04)3 342 57 100/114
H+ 1 1 100/2
Various units used for expressing hardness of water are as under:
1. Parts per million (ppm)
2. Milligrams per liter (mglL)
3. Degree French (OFr)
4. Degree Clark (OC)
1. Parts per million (ppm)
It is defined as number of parts of calcium carbonate equivalent hardness

present per 106 parts of water. This is most common unit for expressing the
hardness of water.
1 ppm = 1 part of CaCO a equivalent hardness in 106 parts of H20
2. Milligrams per litre (mg/L)
It is defined as the number of milligrams of CaCOs equivalent hardness

present per litre of water.
1 mglL = 1 mg ofCaCOa equivalent per 106 mL of water
= 1 part of CaCOa equivalent per 106 parts of water
= 1ppm
Thus, mathematically both the units are equal.
3. Degree French (°Fr)
It is defined as the number of parts of CaCOs equivalent hardness present

per 105 parts of water.
l°Fr = 1 part of CaCOa equivalent hardness per 105 parts of water.
4. Degree Clark (DCl)
It is the number of gains (117000 lb) of CaCOa equivalent present per gallon (10 Ibs or 70,000
grains)
Always remember that, lIb = 7000 grains and one gallon = 70,000 grains
It is defined as the number of parts of CaCOs equivalent hardness present

per 70,000 parts of water.
l°Cl = 1 part of CaCOa equivalent hardness per 70,000 parts of water
Relationship among various units of hardness
1 ppm = 1 mg/L =O.l°Fr =0.07°CI
The above relation can be derived as follows: we know that,
1 ppm = 1 part per 10,00,000 parts of water
loa = 1 part per 70,000 parts of water
l°Fr = 1 part per 1,00,000 parts of water
.. 10,00,000 ppm = 70,OOO°CI = 1,00,OOO°Fr
100 ppm = ~Cl = 1O°Fr
1 ppm = 0.07°CI = O.l°Fr
Degree of hardness
Degree of hardness of any definite quantity of water sample is the calcium

carbonate equivalent of hardness present in that sample depending upon the
units in which hardness is expressed.
[ 8.4.1 NUMERICAL PROBLEMS BASED ON UNITS OF HARDNESS)
Example 1 : A water sample contains 204 mg of CaSO4/L. Calculate the hardness

in terms of CaCOs eq.
Solution: CaS04 = CaCOa
136 gmol-1 = 100 g mol-1
136 mgIL of CaS04 = 100 mgIL of CaCOa equivalent
100 x 204
or 204 mgIL of CaS04 = mgIL of CaCOa equivalent = 150
136
Hardness = 100 mg/L or 150 ppm.
Example 2 : A sample of ground water has 150 mg/L of Ca2+ and 60 mg/L of Mg2+
ions. Find the total hardness expressed in milli-equivalent per liter and mg/L in terms
of CaC03 equivalent. (UPT, May 01)
Solution: Calculation of CaCO a equivalents.
Constituents Amount Multiplication factor CaC03 equiualent
Ca2+ 150mg/L 100/40 150 x 100/40 = 375 mg/L
Mg2+ 60mg/L 100/24 60 x 100/24 = 250 mg/L
Thtal hardness = (375 + 250) =625 mglL =625 ppm
= 625 milli-eq.1L = 12.5 m eq/L
50
Example 3 : Calculate the amount of total, temporary and permanent hardness
of water sample containing the following per liter:
Ca(HC03 )2 = 162 mg, Mg(HCOS)2 = 73 mg, MgC~ = 95 mg, CaSO4 = 136 mg
100
Solution: 162 mg of Ca(HCOa)2 = 162 x 162 = 100 mglL of CaCO a equivalent
100
73 mg of Mg(HCOa)2 = 73 x 146 =50 mglL of CaCOa equivalent
100
95 mg of MgCl 2 = 95 x 95 = 100 mglL of CaCOa equivalent
100
136 mg of CaS04 = 136 x 136 = 100 mglL of CaCO a equivalent
31S Essentials ofEngineering Chemistry
Temporary hardness = Hardness due to Ca(HC0 3)2 + Mg(HC0 3)2
= 100 + 50 =150 mg/L
Permanent hardness = Hardness due to CaS04 + MgCl2
= 100 + 100 = 200 mglL
'lbtal hardness = 150 + 200 =350 mglL
Example 4 : A sample of water upon analysis gave the following data:
MgCl2 = 0.143 °Fr, MgS04 = 0.572 °Fr, CaS04 = 0.286 °Fr, Ca(BCOs)2 = 2.316 °Fr.
Calculate the hardness in ppm.
Solution: Since l°Fr = 10 ppm.
= 1.43 ppm =1.43 x 100 ppm CaC03 equivalent = 1.51 ppm

95
100 .
= 5.72 ppm =5.72 x 120 ppm CaC03 eqUIvalent =4.77 ppm
100
= 2.S6 ppm =2.S6 x 136 ppm CaC03 equivalent =2.11 ppm
100
= 23.16 ppm =23.16 x 162 ppm CaC03 equivalent
= 14.29ppm
.. 'lbtal hardness in ppm scale = 22.68 ppm.
Example 5 : 200 mL of water sample has a hardness equivalent to 25 mL of O.OS N
MgS04 • Find the hardness in °Fr.
Solution :200 mL of water sample = 25 mL ofO.OS N MgS04
= 25 x 0.08 mL of1 N MgS04
= 2 ml of 1 N MgS04 = 2 ml 0.0021 N CaC03 eq.
= 0.002 L of 1 N CaC03 eq. =0.002 x 50 g CaC03 eq.
= 0.1 g CaC03 eq. =100 mg CaC03 eq.
100mgCaC03 eq.xlO00 mL
:.Onelitre (100 mL)ofwatersample =
200mL
= 500 mg CaC03 eq.
:. Hardness of water =500 mg L-l = 500 ppm =500 x O.l°Fr =5O°Fr.
Example 6 : Calculate the temporary hardness and permanent hardness of water
in ppm and degree Clark from the following data:
Mg(HCOS>2 =16.8 mg/L; MgCl2 = 19.0 mg/L; Mg(NOS>2 =29.6 mg/L
CaCOs =20.2 mg/L; MgSO4 = 24.0 mg/L, KCI = 74.5 mglL
Solution:
Compound mg / L Amount Factor Multiplication Equivalent ofCaC03
100 100
Mg(HCOS)2 16.8 16.8 x 146 = 11.5
146
MgS04 24.0 -100

120
100
24.0 x 120 = 20
MgC12 19.0 -100

95
100
19.0 x '95 =20
100
Mg(NOa)2 29.6 -100 29.6 x 148 = 20
148
CaCOa 20.2
KCI does not contribute toward hardness.
Temporary hardness = hardness
due to magnesium bicarbonate and calcium
carbonate
Temporary hardness = 11.5 + 20.2 = 31.7 ppm
= 31.7 x O.07°CI = 2.219°CI
Permanent hardness = hardness due to MgS04 + MgCl2 + Mg(NOs)2
Permanent hardness = 20 + 20 + 20 =60 ppm =4.20°CI
1. A sample of water is found to contain 40.5 mglL Ca(HCO S)2' 46.5 mglL Mg(HCO s)2'
27.6 mg/L MgS04 , 32.1 mg/L CaS04 and 22.45 mg/L CaCI2 . Calculate the total hardness
of water.
2. A water sample on analysis gave the following results.
Ca(HC0 3 )2 = 105 ppm, Mg(HCO S)2 = 125 ppm, CaS04 = 75 ppm, CaCl2 = 82 ppm,
MgS0 4 = 26 ppm. Calculate the temporary and permanent hardness in °Fr.
3. A sample of water has a hardness of 510 ppm. Express the hardness in °Fr and °Cl.
4. How many grams ofMgCO s dissolved per liter gives 84 ppm of hardness ?
5. Calculate the temporary and permanent hardness of water sample with following
analysis : Mg(HC0 3 )2 = 73 mglL; Ca(HCO s)2 = 162 mg/L; CaS0 4 = 136 mg/L;
MgCl 2 =95 mg/L; CaCl2 = 111 mglL and NaCI = 100 mglL.
(ANSWERS)
1. 123.7 ppm.
2. Temporary ha'dness =15.04°Fr, Permanent Hardness = 15.07°Fr
3. 35.7 °CI, 51 °Fr
4. 70.56 x 10-3 (g)
5. Temporary hardness = 25 ppm; Permanent hardness = 105 ppm,
Thtal Hardness = 130 ppm.
WATERANALYSIS
(DETERMINATION OF DIFFERENT CONSTITUENTS IN WATER)
8.5 DETERMINATION OF HARDNESS

The hardness of water is determined by the following methods :
I. Hehner's Method
1. Temporary hardness
Principle: Temporary hardness is removed by boiling of water because calcium and
magnesium bicarbonates get precipitated as calcium carbonate and magnesium carbonate.
boiling
CaCOs ,J- + H20 + CO2 t
boiling
Mg(OH)2 ,J- + 2C02 t
A known volume of water is titrated before and after boiling against standard HCl. The
difference gives the value of temporary hardness.
Procedure: It involves in following two steps:
Step 1 : A known volume of water is titrated against standard HCI using methyl orange
indicator and the volume of consumed acid is noted (say V I mI).
Step 2 : A known quantity of water sample is evaporated to dryness and the residue is
dissolved into hot distilled water. It is filtered and the volume offiltrate is made upto the original
volume (starting in step 2) by adding distilled water. Now a known volume (must be same as
in step 1) is titrated against standard HCI using methyl orange indicator and the volume of
consumed acid (HCl) is noted (say V2 ml).
Calculations
Let volume of acid used before boiling =VI ml
Volume of acid used after boiling = V2 ml
Volume of water taken for titration =X ml
Strength of acid (HCI) used = N/50
:. Volume of N/50 HCI used by temporary hardness present in x ml water = (V I - V2) ml
:. Alkalinity due to temporary hardness == (VI - V2 ) ml ofN/50 HCl
:. X ml H 2 0 - (VI - V2 ) ml ofN/50 HCI
[VI - V 2] 1
:.1 ml ---='----=- x-
X 50
:.1000 ml
I:\'I - V2 ] x 1000
Xx50
:. In terms of CaCO s equivalent = [VI - V2 ] x 50 x 100

Xx50
where the eq. wt. of CaCO a = 50.
2. Permanent Hardness
Principle: Permanent hardness is removed by boiling of water with a known excess amount
of standard N~COs' The chloride and sulphates of calcium and magnesium ¥ets precipitates
as their carbonates. The residual Na2 C03 is then determined by titrating it against a standard
HCI acid.
The following reactions take place :
CaCl2 + N~C03 ~ CaC0 3 . 1. + 2NaCI
MgCl2 + N~C03 ~ MgC03..1. + 2NaCI
CaS04 + Na2C03 ~ CaC03 . 1. + N~S04
MgS04 + Na2C03 ~ MgC0 3 . 1. + N~S04
Procedure : A known volume of water sample is boiled with the sufficient excess known
amount of standard N~C03 solution for 15-20 minutes. After cooling it is filtered and washed
the residue with distilled water. All the washings are collected in the conical flask. The unused
Na2 C0 3 present in the filtrate is calculated by titrating it against standard HCI using methyl
orange as indicator.
Calculations
Let the volume of acid used = Vml
Strength of acid used = N/50
Volume of water sample = X ml
:. Volume ofN/50 Na2C0 3 used for removing permanent hardness in
X ml water sample = (X - V) ml
:. Strength of permanent hardness in terms of CaC0 3 equivalent
[X- V]x1x50x1000
= xx50
ppm
8.5.1 Numerical Problems on Hebner's Method

Example 7 : 100 ml of a sample of hard water neutralizes exactly 12 ml of 0.12 N
HCI using methyl orange as indicator. Express the hardness in term of an equivalent
ofCaC03 •
Solution:
N1V1 = N2V2
(Hard Water) (HeI)
Nl X 100 = 12 X 12
100
12x12
Nl = 100x100
Strength of hardness in term of an equivalent of
12x12
CaC03 = 100xlOO X 50 x 1000 =720 ppm
Example 8 : Calculate the temporary, permanent and total hardness of a water
sample which gave the following analysis:
(i) 50 ml of water required 13ml of N/50 HCI for neutralization to methyl orange
end-point.
(ii) 50 ml of water after boiling required 8 ml of N/50 HCI for neutralization to
methyl orange end point.
(iii) 50 ml of water sample was boiled with 55 ml of N/50 sodium carbonate
solution and the resulting solution required 35 ml of N/50 HCI for
neutralisation to methyl orange end-point.
Solution : (i) Temporary hardness : Volume of N/50 Hel required for removing
temporary hardness of 50 mL of water sample =13-8 =5ml
Alkalinity due to temporary hardness in 50 mL water sample
= (13-8) =5mL ofN/50 HCI
Alkalinity due to temporary hardness in 50 mL of water sample in terms ofCaCOg eq.
5x1x50 _ -1
= 50x50 - 0.1 gL (Eq. wt. of CaCO a =50)
= 0.1 g ofCaCO g eq. per litre

0.1x106
Temporary Hardness = -1-Og~ = 100 ppm
(ii) Permanent haroness : Volume of N/50 N ~COg required for removing permanent
hardness of 50 mL of water = 55 - 35 =20 mL
Permanent hardness in grams per litre in terms of CaCO g eq
= 20x1x50 = 20 = ofCaCO e
50x50 50 g g q
20 x 106
Permanent hardness = 50x10g =400 ppm
Total hardness of water sample = 100 ppm + 400 ppm =500 ppm
II. Soap Titration Method
Principle : When soap is added to hard water, it does not give lather because hardness
producing metal ions (Ca2+ and Mg2+) get precipitated. After complete precipitation of Ca2+ and
Mg2+, further addition of soap gives lather.
2C 17H g5COONa + Ca(HCOg)2 ~ (C17H35COO)2Ca,J- + 2NaHCOg
Sodium Stearate (soap)
2C 17H g5COONa + MgC~ ~ (C17H35COO)~g,J- + 2NaCI
2C17H g5COONa + MgS0 4 ~ (C17HgsCOO)~g,J- + 2N~S04
The total hardness can be determined by titrating the water sample against the standard
soap solution. The end point is detected as the appearance of a stable lather.
Procedure
1. Preparation of standard hard water : Dissolve 1.0 gm of pure and dry calcium
carbonate in the minimum amount of dil HC!. Evaporate the solution to dryness. Dissolve the
residue in one litre of distilled water. The hardness of this solution is 1 gllitre or 1000 mgllitre
or 1000 ppm or 1 mg/mL.
2. Preparation and standardization of soap solution: Dissolve 10 gm of pure and
dry soap in one litre of 80% alcohol. Take this solution in the burette. Take a known volume
of standard hard water in a stoppered bottle and add to it soap solution from the burette drop
wise and with constant shaking till a permanent (at least for a minute) lather is formed. Let
the volume of soap used be V 1 mL.
3. Total hardness: Titrate known volume as above of hard water against the soap solution
as above. The end point is detected by the appearance of stable lather. The titre value (say V2)
corresponds to the total hardness of the sample.
4. Permanent hardness: The water sample is boiled for 20 :... 25 minutes. Temporary
hardness is removed. It is cooled and the same known volume is titrated again against standard
soap solution till the stable lather appearance. The titre value (say Va) corresponds to permanent
hardness of the sample.
5. Lather factor of distilled water: A blank titration of distilled water in which soap
solution is prepared is done against the prepared soap solution till the appearance of stable
lather. For pure distilled water the lather factor should be zero. The value of lather factor is
always substracted from each litre value.
Calculations
Standardization of soap solution
Let volume of standard hard water (SHW) = x ml
Volume of soap solution consumed = Viml
V 1 ml of soap solution = xmlofSHW
= x mg of CaCOa ('.' 1 ml SHW =1 mg CaCOa)
1 ml of soap solution = Vx mg of CaCO a

1
Calculations of total hardness
Let volume of water sample for titration = y ml
And volume of soap solution consumed = V2 ml
Suppose the lather factor = zero
x
1 ml soap solution = - mgofCaCOa
Vl
x
V2 ml soap solution = V
l
X V2 mg ofCaCOa
y ml of water sample = v:x

1
X V2 mg ofCaCOa
1000 ml water sample = vx1 V

x - 2 x 1000 mg CaCO
y
a
x V2
Total Hardness = - x - x 1000 ppm
Vl y
Permanent hardness
Let volume of water sample after boiling = zml
And volume of soap solution used = v:x mg of CaCOa
I
V3 ml of standard soap solution = -x X Va mg ofCaCOa

VI
x
i.e., z ml of water sample = VI X Va mg ofCaCO a
1000 ml water sample = -x xVa- x 1000 mg ofCaC0 3

VI z
i.e., Permanent Hardness X Va

= - x - x 1000 ppm
VI z
Temporary Hardness =Total hardness - Permanent hardness.
8.5.2 Numerical problems on soap titration method
Example 9: 100 ml of hard water is titrated with soap solution gave the following
datas:
total hardness = 9.4 ml soap solutions
permanent hardness =3.4 ml soap solutions
Standard hard water (100 mglL of CaC03 ) =18.4 ml soap solutions
=
lather factor 0.4 ml soap solution.
Calculate the amount of temporary and permanent hardness.
Solution: 1000 ml water contains = 100 mg CaCOa (Given)
100
1 ml water contains = 1000 mg CaCOs
100 ml water contains = 100x100 _ 10 C CO

1000 - mg a a·
The lather factor is given 0.4 ml soap solution.
Now, 100 ml hard water contains 10 mg CaC0 3 required (18.4 - 0.4) ml soap solution
= 18 ml soap solution
.: 18 ml soap solution consumes 10 mg CaCOa
:. 1 ml soap solution consumes 10 =0.55 mg CaC03

18
For Total Hardness
100 ml hard water requires 9.4 - 0.4 =9.0 ml soap solution
.: 1 ml soap solution consumes 0.55 mg CaCO a
:. 9.0 ml soap solution consumes 0.55 x 9.0 = 4.95 mg CaCOa
100 ml hard water contains = 4.95 mg CaCO a
1 ml hard water contains = 4.95 m CaCO

100 g a
1000 ml hard water contains = 4.95 x1000 =49.5 ppm.

100
For Permanent Hardness
100 ml hard water requires 3.4 - 0.4 = 3.0 ml soap solution
.. 1 ml soap solution consumes = 0.55 mg CaCOa
3.0 ml soap solution consumes = 0.55 x 3 = 1.65 mg CaC0 3
100 ml hard water contains = 1.65 mg CaCOa
1 ml hard water contains = 1.65 C CO

100 mg a a
1000 ml hard water contains = 1.65x1000 = 16.5 ppm

100
Permanent hardness = 16.5 ppm
Temporary hardness = (49.5 - 16.5) ppm
= 33 ppm.
Example 10 : Titration of 50 ml of water at each time with standard soap solution
gave the following results:
(i) Lather factor =0.4 mL (ii) Total hardness 8.2 mL =
(iii) Permanent hardness = 2.5 mL (iv) Standard hard water 19.9 mL =
Calculate each type of hardness present in water.
Solution: V = 0.4 mL VI = 19.9 mL V2 = 8.2 mL Va = 2.5 mL
Total hardness = V2 - V x 1000 ppm
VI-V
= 7.8 x 1000 ppm = 80 ppm

19.5
V3- V
Similarly, Permanent hardness = VI _ V x 1000 ppm
Permanent hardness in sample water = 2.1 x 1000 ppm =21.5 ppm

19.6
Hence, Temporary hardness = Total hardness - Permanent hardness
= (80 - 21.5) ppm = 58.5 ppm
III. EDTA Method

It is the most important and more accurate method to determine the hardness of water.
Principle: The total hardness (permanent as well as temporary) in water is determined
by titrating the water sample against standard ethylenediaminetetraacetic acid (EDTA) solution
in ammonia buffer solution having pH = 10 using eriochrome black-T as an indicator. The
calcium and magnesium ion present in hard water forms stable compound with EDTA and less
stable complex with eriochrome black-T solution.
The structure of EDTA is as follow:
- +
HOOC-H 2C " /CH 2-COONa
+ _ /N-CH 2-CH 2- N " .2H2 0
N aOOC-H 2 C (Sodium salt of EDTA) CH 2-COOH
It ionises in water to give two Na+ and a strong chelating agent. It is a hexadentate ligand
and is represented by H 2y2--. It forms complexes with bivalent cations (Ca8 +, Mg2+ etc.). The
complexes with hardness causing diavalent ions are stable in alkaline medium (pH 8-10).
Eriochrome black-T may be represented as:
o
+
Na O--S
II
II
o
Eriochrome black-T
(Sodium 4-(1-hydroxy-2-naphthylazo)-3-hydroxy-
7-nitronaphthalene-l-sulphonate)
The eriochrome black-T has two ionisable phenolic hydrogen atoms and for simplicity is
represented by Na+H2In-
H r pH 7.0 , H12- pH 11.5 , 13-
.fron ' pH 5.5 Bh:e ' pH 11.0
n
Yellowish orange
The calcium and magnesium ion present in hard water combine with the indicator
eriochrome black-T at pH 9-10 to form less stable wine red complex.
M2+ + IDn2- ~ Mln- + H+ (Where M = Ca or Mg)
(EBT, blue)
Magnesium ion produces wine red colour with the indicator.
When EDTAis added, the free Ca2+Mg2+ forms a stable complex of metal-EDTA.
Ca2++ H2y2- ~ Cay2-- + 2H+
Mg2+ + H2y2-- ~ Mgy2-- + 2H+
Mg-EDTA complex is less stable than Ca-EDTA complex but more stable than Mg-Indicator
complex.
When all Ca2+ and Mg2+ get complexed with EDTA then further addition of EDTA sets free
the metal ion from metal indicator complex and form more stable complex.
Caln- + H 2y2- ~ Cay2-- + H1n2- + H+
Mgl n- + H 2"Y2- ~ Mgy2-- + H1n2- + H+
(Wine red) (EDTA) (Metal-EDTA (Free indicator
complex, Blue)
more stable)
The metal-EDTA complex may be represented as :
where M =Mg2+ or Ca2+

To get only Mg+2 hardness, Ca+2 is removed by precipitating it as calcium oxalate by adding
calcium precipitating buffer [NH4CI+NH40H+(NH4)2C204]
COO~
I ea
COO-./'"
Calcium oxalate (White ppt.)
Precipitate is filtered and the filtrate is titrated against EDTA solution to get magnesium
hardness. Calcium hardness can be calculated by subtracting Mg-hardness from total hardness.
Procedure
(I) Standardisation of EDTA solution : Pipet out a known volume (say 20 ml) of
standard hard water and transfer it to the conical flash. Add 5 ml buffer solution and
5 drops of Eriochrome Black-T indicator solution. Colour of solution turns wine red.
Titrate the flask solution against the EDTA solution from burette until the colour
changes from wine red to clear blue at the end point. Let the concordant volume of
EDTA used be Vl'
(II) Determination of total hardness : Pipet out the same known volume of given
hard water sample in a conical flask. Add 5 ml of buffer solution and 5 drops of
indicator solution. Titrate the wine red solution against EDTA solution in burette till
the colour changes to pure blue. The titre value (say V2) correspond to the total
hardness ofthe sample.
(III) Determination of permanent hardness: Take 100 ml of hard water sample in a
500 ml beaker and boil gently for half an hour. Cool, filter into a 100 ml measuring
flask and make the volume upto the mark with distilled water. Stopper the flask and
shake well. Take the same volume of this solution and titrate with EDTA solution in
the same manner as in step I and II. The titre value (say Vg) correspond to the
permanent hardness of the sample.
(IV) Determination of magnesium hardness : Pipet out 100 ml of the hard water
sample into a 500 ml beaker. Add 25 ml of calcium precipitating buffer solution while
constantly stirring the mixture with a glass rod. Allow the precipitate to settle down
for 30-40 minutes. Filter the solution through dry filter paper (Whatman-42) in a dry
flask. Take 20 ml of filtrate and add 5 ml buffer solution and 5 drops of Erio-T indicator.
Titrate against EDTA solution till wine red colour changes to pure blue.
(V) Determination of temporary hardness: It can be obtained by subtracting the
permanent hardness from the total hardness of the sample.
(VI) Determination of calcium hardness: It can be obtained by subtraction magnesium
hardness from the total hardness of the sample.
OBSERVATIONS AND CALCULATIONS
1 ml of standard hard water = 1 mg of CaC03.
(I) Standardisation of EDTA solution:
Volume of S.H.W. taken for titration = 20ml
Let the volume of EDTA used = V I ml.
Now, VI ml of EDTA = 20 ml S.H. W. = 20 x 1 mg of CaC0 3 = 20 mg CaC0 3
20
1 ml EDTA = V mg CaC0 3·
I
(II) Determination of Total Hardness:
Volume of water sample taken for titration= 20 mI.
Let volume of EDTA solution used = V2 ml.
20
20 ml of hard water = V2 ml EDTA= V2 x - mg CaC0 3
VI
20 1 V.
1000 ml of hard water = V2 X- x - x 1000 = ~ x 1000 mg CaC0 3 •
VI 20 VI
or Thtal hardness of water = V2 x 1000 ppm.

VI
(III) Determination of Permanent Hardness:
Volume of hard water taken after boiling and filtering =20 ml
Let volume of EDTA solution used = V3 mI.
20
20mlhardwater = V3 mIEDTA=V3 x - mgCaC0 3 .
VI
20 1000 V.
1000 ml hard water = V3 x - x - - = -.2.. x 1000 mg CaC03
VI 20 VI
1000
Permanent hardness of water = V3X-- ppm.
VI
Temporary hardness of water = Thtal hardness - Permanent hardness
8.5.3 Numerical Problems or EDTA Method
Example 11 : 50 ml of water sample requires 10 ml 0.01 N EDTA when titrated
using buffer solution (pH = 10) to attain the end point. Calculate the total hardness
of a sample in terms of ppm equivalent of CaC03 per litre.
Solution:
N1VI = N 2V2
(Water) (EDTA)
1
NI x 50 = 10x-
100
10
NI = 100x50
Total hardness = 10 x 50 x 1000 (Eq wt of CaCOs =50)

100x50
= 100 mglL equivalent of CaCO s = 100 ppm.
Example 12 : 200 ml of hard water sample require 30 ml of 0.02 M EDTA with
NH4Cl- NH20H buffer and EBT indicator. Another 200 ml of the sample is boiled for
about half an hour and after filtering the precipitate, the volume of the filtrate is
made 200 ml again by the addition of distilled water. 20 ml of this boiled sample
requires 5 ml 0.01 M EDTA following the same procedure. Calculate the temporary
and permanent hardness of the sample.
Solution:
2
= 30x-
100
30x2
Ml = 100 x 200
Strength = Molarity x mol. wt.
30x2
= x 100 (mol. wt. of CaCO s = 100)
100x200
Total hardness = 30 x 2 x 100 x 1000 =300 ppm

100 x 200
Now after boiling sample contain only permanent hardness.
M1V1 = ~V2
(Water) (EDTA)
1
Ml x 20 = 5x-
100
5
Ml = 100x 20
Strength = Molarity x mol. wt.
5
= 100 x 20
x 100
Permanent hardness = 5 x 100 x 1000 =250 ppm

100x20
Temporary Hardness = Total hardness - Permanent hardness
250 =50 ppm.
= 300 -
Example 13 : 50 mL of a sample water consumed 15 mL of 0.01 M-EDTA before
boiling and 5 mL of the same EDTA after boiling. Calculate the degree of total
hardness, permanent hardness and temporary hardness. (Anna, Nov. 2K)
Solution: 50 mL of water sample = 15 mL of 0.01 M-EDTA
1000 mL of water sample = 15x1000 mLofO.01M-EDTA
50
= 300 mL of 0.01 M-EDTA
= 2 x 300 mL of 0.01 N-EDTA
(.: Molarity of EDTA =2 x Normally of EDTA)
= 600 mL (or 0.6 L) of 0.01 eq CaCO a
= 0.6 x 0.01 x 50 g CaCO a eq
Hence, total hardness = o.ao g or 300 mg of CaCOaeq
= 300 mgIL or 300 ppm
Now 50 mL of boiled water = 5 mL or 0.01 M-EDTA
1,000mLofboiledwater =
5x1000 mLofO.01M-EDTA
50
= 100 mL of 0.01 M-EDTA
= 200 mL (or 0.2 L) or 0.01 N-EDTA
= 0.2 x 01 x 50 g ofCaC0 3 eq
= 0.1 g or 100 mg ofCaCOa eq
Hence, permanent hardness = 100 mgIL or ppm
.. Temporary hardness = (300 - 100) ppm =200 ppm
Example 14 : If 50 mL of a sample of hard water consumed 15 mL of 0.01 M EDTA.
What is the hardness of water? (Anna, July 2K)
Solution: Let us first calculate the molarity of hard water sample consuming 15 mL of
0.01 M - EDTA by applying molecularity equation M1V1 =M2V2
50 mL x Molarity of hardness = 10 mL x 0.01 M - EDTA
or molarity of hard water = 15xO.01 =0.003 M

50
We know, strength in gIL =Molarity x Mol. Wt.
In order to express hardness in terms CaCO a equivalents, we should take the molecular
weight ofCaC0 3 i.e., 100.
.. strength of hardness = 0.003 x 100gIL = 0.3 gIL = 300 mg/L = 300 ppm.
Example 15 : 20 mL of standard hard water (containing 1.5 g CaCOs per litre)
required 25 mL EDTA solution for end-point. 100 mL of water sample required 18 mL
EDTA solution : while same water after boiling required 12 mL EDTA solution.
Calculate carbonate and non-carbonate hardness of water. Which buffer is used in
this titration and what is its pH. (KU, Jan. 01)
Solution:
1000 ml H 20 required for 1.5 g OaOOa
20 ml H °
2
required for 1.5)( 1000 )( 20 • 80 mg OaOOa
1000
For total hardness
25 ml EDTA required = 20 ml SHW =30 mg CaCOs
20
1 ml EDTA required = - mgCaCOs
25
30
18 ml EDTA required = 25 x 18 mg CaCOs
30
100ml H2O = 25 x 18 mg CaCO s
30x18x1000
1000ml H2O = =216 mg CaCOa per litre
25x100
= 216 ppm
For (non-carbonate) permanent hardness
30
1 ml EDTA required = - mgCaCOs
25
30
12 ml EDTA required = - x 12 mg CaCO s
25
100 ml H 20 contains = 30 x 12 mg EDTA

25
1000 ml H20 contains = . 30 x 12 x 1000 = 144 mg CaCO per litre

25x 100 s
= 144ppm
Temporary (Carbonate) Hardness =Total hardness - Non-carbonate hardness 72 ppm
= 216 - 144 =72 ppm
1. What are the sources of water in nature? Name the purest and the most impure source
giving reason.
2. Classify the common impurities present in natural water.
3. Name the gases dissolved in boiler feed water which can cause corrosion of the boiler.
4. What do you mean by hard and soft water?
5. Why does hard water consume a lot of soap?
6. What is degree of hardness? Classify water on its basis.
7. Why do we express hardness of water in terms of CaCOs equivalent?
8. What is meant by softening of water? Why water is softened before use in a boiler?
9. Write the constituents responsible for non-carbonate hardness of water. Name the
methods employed for softening this type of water.
10. Explain the difference between soft water and demineralised water.
(PTU, Jan. 02)
(ANSWERS)
1. The sources of natural water are :
Rain water, ground water or surface water, underground water and sea water.
Rain water is the purest form of natural water because it is obtained by the natural
distillation (evaporation & condensation) of surface/sea water. The most impure form
is sea water which contains maximum amount of dissolved impurities from the earth
surface.
2. The common impurities in natural water may be classified as :
(i) Dissolved minerals such as bicarbonates, carbonation, chlorides, sulphates of
sodium, calcium, magnesium etc.
(ii) Dissolved gases such as CO 2, S02' H 2S, NH g etc.
(iii) Suspended matter which may be both organic or inorganic matter.
(iv) Microscopic matter such as micro-organisms, bacteria etc.
(v) Colloidal impurities such as silica, clay etc.
3. The dissolved gases which cause corrosion of boiler are :
(i) Oxygen,
(ii) Carbon dioxide which forms carbonic acid
(iii) Sulphur dioxide and trioxide which form sulphurous and SUlphuric acid
(iv) Oxides of nitrogen which may form nitric acid.
4. Hard water is that water which does not produce lather with soap solution readily, but
forms a while precipitate. Soft water gives lather with soap solution readily. In fact,
hard water contains dissolved calcium and magnesium salts which form scum with soap
solution. Soft water does not contain these dissolved salts and so it forms lather rather
than scum or precipitate with soap solution.
5. Soaps are sodium or potassium salts of higher fatty acids such as stearic, palmitic or
oleic acids. On treating soap with hard water, Ca2+ and Mg2+ ions from hard water form
insoluble Ca or Mg soaps. So lather is not formed till the hardness causing cations are
removed form water.
e.g., 2C 17H g5 COONa + M2+ -+ (C17Hg5COO)~ + 2Na+
Sodium stearate (soap) precipitate
M = Ca2+ or Mg2+
6. Degree of hardness is the parts of calcium carbonate equivalent hardness present in a
definite number of parts of water depending upon the unit employed. It is usually
expressed in ppm of mgL units. Water can be classified into the following types on the
basis of degree of hardness.
(i) Soft water: When degree of hardness is less than 75 ppm·
(ii) Moderately hard water: When degree of hardness is between 75-150 ppm.
(iii) Hard water: When degree of hardness is between 150-300 ppm.
(iv) Strongly hard water: Degree of hardness is above 300 ppm.
7. The hardness of water is expressed in terms of CaC0 3 equivalent because CaC0 3 is
the most insoluble compound in water treatment. Moreover, its molecular mass is 100
and it makes the calculations of hardness comparatively easier. Although hardness of
water is never due to CaCO a because, being insoluble, it is not present in water as
such. The hardness of water is due to soluble salts like bicarbonates, chlorides and
sulphates of calcium and magnesium, but it is a convenient way of expressing the
hardness in terms of CaCO s equivalents of the salts causing hardness.
8. Softening of water is a process of removing hardness producing salts from water. Water
must be properly softened before use in the boilers because hard water may cause the
following problem:
(i) Scale and sludge formation {ii) Priming and foaming
(iii) Boiler corrosion (iu) Caustic embrittlement.
9. Non-Carbonate hardness is another name for the permanent hardness of water. This
hardness is due to the presence of chlorides and sulphates of Mg and Ca in water. Some
of the common constituents responsible for it are :
MgCI 2, CaCI2, MgS0 4, CaS04, FeS04, Al2(S04)3 et,c.
The methods employed for softening this type of water are:
(i) Lime-soda process (ii) Zeolite process (iii) Ion-exchange process.
10. Soft water-does not contain the hardness producing salts i.e., bicarbonates chlorides
and sulphates of Mg and Ca. It may contain some other salts soluble in water.
Demineralised water means water free from all minerals i.e., salts. It is free from all
the acidic as well as basic radicals which constitute a salt.
8.6 ALKALINITY OF WATER
The alkalinity of water is due to the presence of those substances in water which have
tendency to increase the concentration ofOH-ions either by hydrolysis or dissociation in water.
The alkalinity of water is due to the following factors:
(i) The presence of salts of weak organic acids which undergo hydrolysis and consume
H + of water. As a result concentration of OH- increases in water and water becomes
alkaline.
(ii) The presence of HCOs-' Si0 32-, etc. in water which make the water alkaline because
they have tendency to take up H+ from water. Hence concentration of OH- in water
increases.
Classification
Alkalinity of water is mainly classified as: (i) Hydroxide alkalinity (ii) Carbonate alkalinity
and (iii) Bicarbonate alkalinity.
Both alkalinity and hardness are expressed in terms of CaCOs equivalent.
Alkalinity is also expressed generally in ppm or mglL.
When alkalinity < total hardness
Carbonate hardness in ppm =alkalinity in ppm
When alkalinity ~ total hardness
Carbonate hardness in ppm = Thtal hardness in ppm and Non-Carbonate hardness
= Total hardness - Carbonate hardness.
Determination
The alkalinity of water is determined by titrimetric method. A known volume of water
sample is titrated against a standard acid (H 2S0 4 ) using phenolphthalein and methyl orange
c~:~:::
HCOa- + H+
=
indicator one after the other. The reactions take place are following :
~
:~~3-
H 20 + CO 2
1 1M
p
Here 'P' and 'M' represents the volume of consumed acid by using phenolphthalein indicator
and methyl orange indicator respectively.
From the above relations the following conclusions may be drown :
(i) When P = 0; it means that the alkalinity is due to the presence of only HCO a- ions.
Both OH- and CO a2- are absent. Thus, the alkalinity due to HCO a- =M. .
(ii) When P = M; it means that the alkalinity is due to the presence of only OH- ions.
Thus, the alkalinity due to OH- = P =M.
(iii) When P = ~ M; it means that the alkalinity is due to the presence of only COa 2- ions.
In this case phenolphthalein end point indicates the half neutralization of COa2- ions
i.e., neutralization of C0 32- upto HC0 3-.
C0 32-+H+ ~ HC03-
Whereas methyl orange end point indicates the complete neutralization of C0 32- ions
as:
COl- + H+ ~ HC03-
HC03- + H+ ~ H 2C0 3 ~ H 20 + CO 2
It is obvious that the alkalinity due to COa 2- = 2P or M.
(iv) When P > ~ M; it means that the alkalinity is due to the presence of OH- ions in
addition to C0 32- ions. In this case phenolphthalein end point indicates the complete
neutralization ofOH- ions and half neutralization ofC032- i.e., neutralization ofC0 32-
upto HC0 3- ions.
OH-+H+ ~ H 20 1P
c0 32- + H+ ~ HC0 3-
Whereas methyl orange indicator end point indicates that the complete neutralization
of OH- and C0 32- ions as :
OH-+H+ ~ H 20
C0 32-+H+ ~ HC03-
HC0 3- + H+ ~ H 2C03 ~ H 20 + CO2
Therefore, it is clear that the neutralization of HC0 3- is equal to M - P and the
complete neutralization of C0 32- is equal to 2(M - P). (Since complete neutralization
of C0 32- is twice the neutralization of HCOs- ions).
Thus, the alkalinity due to OH- = M - 2(M - P) =M - 2M + 2P =2P - M.
(I) i
When P < M; it means that the alkalinity is due to the presence of HOO s- ions in
addition to 0°3 2- ions. In this case phenolphthalein end point indicates the
neutralization of COs2- up to HCO s- i.e., half neutralization of COS2- ions.
CO 32- + H+ ~ HCO 3-
Whereas methyl orange indicator end point indicates the complete neutralization of C0 32-
ions as:
CO 32- + H+ ~ HCO 3-
HC0 3- + H+ ~ H2COS~ H 20 + CO2
It is obvious that the alkalinity due to C0 32- = 2P
and alkalinity due to HCO s- =M - 2P.
[Note: HC03 - and OH- both do not exist simultaneously because they react to form COl-
and H 2 0 as
HC03- + OH- ~ COl- + H 20
So this combination is not possible.]
The conclusions may be summarised in tabular form as follows :
Table 8.1
Result upto phenolphthalein end point (P) OB- COl- HCOa-

and methyl orange end point (M)
p=o 0 0 M
P=M PorM 0 0
1
P= 2M 0 2PorM 0
P> !M
2
2P-M 2(M - P) 0
P< !M
2
0 2P M-2P
Procedure
A known volume of water sample is titrated against standard acid (H 2S0 4 ) by using
phenolphthalein indicator. The end point is detected by disappearance of pink colour. The
volume of acid consumed is noted. Now the titrated water sample is again titrated against the
same standard acid (H 2S04 ) by using methyl orange indicator. The end point is detected by
appearance of red colour. The volume of acid consumed is noted.
Calculations
Let volume of water sample for titration = Vml
Strength of acid = N/50
Volume of acid used in case of phenolphthalein indicator = A
Volume of acid used in case of methyl orange indicator = B
For phenolphthalein indicator
N1V1 = N2V2
(Water) (Acid)
1 A
Nl = - x -
50 V
1xA
Strength = Nl x Eq. wt = - - x 50 C·: Eq. wt. ofCaC0 3 =50)
50xV
:. Phenolphthalein alkalinity = 1xAx50x1000.

ppm In terms of eq. wt. 0 f CaCO 3.
50xV
Similarly, for methyl orange indicator CThtal alkalinity)
The volume used of standard acid = CA + B) ml
. . 1xCA+B)x50
Thtal alkalInIty = x 1000 ppm.
50xV .
( 8.6.1 NUMERICAL PROBLEMS BASED ON ALKALINITY )

N
Example 16 : 200 ml of water sample required 25 ml of 50 H 2 S04 during titration
by using phenolphthalein indicator and 26 ml of the same acid by using methyl
orange indicator. Calculate the alkalinity of each type in terms of CaCOa equivalent.
Solution: P = 25 ml, M = 26 ml, P > ~ M

Volume of acid in OH- hardness = 2P-M
Volume of acid in C0 32- hardness = 2CM-P)
For alkalinity due to OH-
N1V1 = N2V2
(Water) (Acid)
1
NI x 200 = - C2P-M)
50
1x24
Nl = 50x200
Alkalinity in terms of CaC0 3 equivalent = 1 X 24 X 50 X 1000 =120 ppm

50x200
(.: Alkalinity = normality X eq. wt. ofCaC03 (50) x 100 ppm.)
For alkalinity due to C0 32-
N1V1 = N2V2
(Water) (Acid)
1
Nl X 200 = - C2M-P)
50
2
Nl =
50x200
Alkalinity in terms of CaC0 3 equivalent = 1 x 2 x 1000 x 50 - 10 ppm

50 x 200 - .
Example 17 : 100 ml of a water sample on titration with 0.03 N HCI using
phenolphthalein as an indicator gave end point with 7.5 ml of acid. Another sample
of same volume of water require 15 ml of acid (0.03 N) using methyl orange indicator
to obtain complete neutralization. Calculate the alkalinity of water in terms of
CaCOs·
Solution:
Volume of acid used in case of phenolphthalein indicator =7.5 ml
Volume of acid used in case of methyl orange indicator = 15 ml
So P = 2M
2
So alkalinity in water is due to C032-

Volume of acid = 2P
N1V1 = N 2V2
(Water) (Acid)
3
= -x2P
100
3x15
100 x 100
Alkalinity = 3 x 15 x 100 x 50 =225 ppm.

100x100
N
Example 18 : 100 ml of a water sample required 4 ml of 50 H 2 S0 4 for
neutralization to phenolphthalein end-point. Another 16 ml of same acid was needed
for further titration, to methyl orange end point. Determine the type and amount of
alkalinity.
Solution:
1
P = 4 ml, M = 4 + 16 = 20 ml, P<-M
2
Alkalinity is due to presence ofC0 32- and HCO a-
Volume of acid in COa2- type = 2P
Volume of acid in HC0 3- type = M - 2P
COa 2- alkalinity
= N2V.2
(Acid)
1
= -x2P
50
1x8
50x100
Strength = 1 x 8 x 1000
50 x 100
Alkalinity in terms of CaC03 equivalent = 1 x 8 x 1000 x 50 =80 ppm
50 x 100
HCO a- alkalinity
NV = N2~
(Water) (Aci
1
Nl X 100 = 50 x (M-2P)
1x12
Nl = 50 x 100
1x12xlOOO
Strength = 50x100
Alkalinity in term of CaCOa equivalent = 1x12x1000x50 = 120 m

50x100 pp
'Ibtal alkalinity = 120 + 80 = 200 ppm.
8.7 DETERMINATION OF Cm..ORIDES

In water, chloride ions are present in the form of compounds like CaCI2. MgCI2, N aCI, etc.
The chloride ions are estimated by titrating the water sample against a standard solution of
silver nitrate using potassium chromate as indicator.
When all the chloride ions are precipitated out as AgCI, potassium chromate (indicator)
reacts with the excess drops of AgNO a to form red coloured silver chromate (end point).
NaCI + AgNO a ~ AgCI J.. + NaN0a
~Cr04 + 2AgNOa ~ Ag2Cr04 J.. + 2KNOa
(Reddish)
The end-point of the titration will thus be the change in colour from bright yellow (due to
~Cr04) to red (due to Ag2Cr04)'
Procedure: Pippette out 100 ml of the water sample in a clean titration flask. Add to it
2 -3 drops of potassium chromate. Run N/50 AgNO a solution from the burrette to the flask
till the colour changes from yellow to brick-red. Let the titre value be V.
Calculations
Applying normality equation, N1Vl = N 2V2, we have:
(Water sample) (AgNO a Soln.)
1
Nx 100 = -xV
50
1xV
Nl (Normality of water sample w.r.t. CI- ions) =
50xlOO
Strength w.r.t. CI- ions = 1x Vx 35.5 IL (E . wt ofCI- = 35.5)

50x100 g q
Strength of chloride ions = V x 35.5 x 1000,000 mgIL = 7.1 V ppm

50 x 100 x 1000
Similarly, strength of chloride ions as CaCO a equivalent
= V x 50 x 1,000,000 =10 Vppm
50 x 100 x 1000
where V is the vol. of N/50 AgNO s used during titration.
Problem 19 : Calculate the amount of chloride ions in a water sample whose 100
ml required 10.5 ml of N/40 AgNOa solution upto potassium chloromate end-point.
N
Solution: 100 ml of water sample = 10.5 ml of 40 ~Cr04
. 1
100 x Normality of Cl- = .10.5 x 40
10.5 1
Normality of Cl- ion = - -x-
100 40
Strength of Cl- ion = 10.5 x 35.5 gm/l't

1 re
40x100
= 10.5 x 35.5 x 1000,000
40 x 100 x 1000
= 93.125ppm
Similarly, strength of Cl- ion as calcium carbonate equivalent 35.5 strength of Cl-
= 10.5 x 50 x 1000,000
40 x 100 x 1000
= X ppm.
8.8 DETERMINATION OF NITRATES (N0a-)
Nitrates are the end products of decomposition of organic matter and indicate the organic
matter present in water in fully oxidised state. The presence of nitrates is known by adding
phenol-di-sulphonic acid and KOH, the colour so formed is compared with standard colours to
ascertain the ppm content.
Determination of Nitrate by Brucine Method
This method is rapid, simple, precise and accurate.
Principle: Nitrates ions react with brucine in conc. sulphonic acid to form yellow colour
which is measured spectro photometrically.
Reagents
(i) Nitrate Standard Solution 10%
1.0 mL = 0.01 mg Nitrate nitrogen (N)
(ii) Nitrate Stock Solution: It can be prepared by dissolving 722 mg. anhydrous potassium
nitrate in 1000 mL distilled water.
1.0 mL = 0.01 mg Nitrate nitrogen (N)
(iii) Brucine-Sulphanilic Acid Solution: Dissolve 19 brucine sulphate and 100 mg sulphanilic
acid in 70 mL hot distilled water, Add, 3 mL conc. HCl, cool and dilute'to 100 mL
with distilled water.
(iv) Sodium arsenite Solution: Dissolve 1.83 g sodium arsenite in 100 mL distilled water.
(v) Sulphuric Acid Solution: Add 500 mL conc. H 2S0 4 in 75 mL distilled water and cool.
Procedure
(i) Pipette out 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5 and 5.0 mL nitrate standard solution
in 50 mL beaker along with a beaker containing 5 mL distilled water as the blank.
The standard solution is diluted to 5 mL with distilled water.
(ii) Take 5 mL of the sample in a beaker.
(iii) Add 1 mL brucine sulphanilic acid solution to standards, blank and sample with
stirring.
(iv) Place 10 mL H 2S04 in to a series of 50 mL beakers.
(v) Transfer the contents of the first series of 50 mL beakers containing standards, sample
and blank to each of second series of beaker containing H 2S0 4 and mix well.
(vi) Keep the beakers in dark for 10 minutes.
(vii) Add 10 mL distilled water to the respective beakers while the colour is developing.
Cool them for 30 minutes.
(viii) Measure absorbance of the standards and sample with the help of spectrophotometer
after setting the blank at 100% transmittance at a wave length of 510 nm.
(ix) Prepare calibration curve to find out the mg. equivalent of nitrate nitrogen in the
sample.
Interferences: All strong reducing and oxidising agents interfere. Concentration more
than 1 mglL of iron and tetravalent manganese also interfere. The presence of nitrite upto 5
mglL is eliminated by the use of sulphanilic acid. Chloride interference (5 mglL) is removed
by the addition of sodium arsenite.
Calculations
Nitrate N(mg) x 1000
Nitate N = --------===------ mg/L
sample taken for estimation
N0 3- = Nitrate N x 4.43 mglL
8.9 DETERMINATION OF SULPHATES (SOl-)
Sulphate ions in water are usually present in the form of compounds like N a 2SO4' CaSO4'
MgSO 4' etc. There are two methods commonly employed for its determination (i) Titremetric
Method (ii) Gravimetric Method.
(i)Titremetric Method: The estimation of sulphate ions in water in based on the fact
that sulphate ions react with benzidine hydrochloride to form benzidine sulphate which is
insoluble in cold and soluble in hot to form sulphuric acid.
C12H8(NH2)2·2HCI + N~S04 ~ C12HiNH2).H2S04'" + 2NaCI
Benzidine hydrochloride Benzidine sulphate
(insoluble in cold)
The free sulphuric acid can be titrated against a standard caustic soda solution using
phenolphthalein as indicator.
Procedure: Take 100 c.c. of the water sample and add to it 10 c.c. of benzidine
hydrochloride solution*. Mix the contents thoroughly and allow the precipitate to settle. Filter
off the precipitate through Whatmann filter paper. Wash the precipitate on filter paper to free
of acid with a minimum amount of cold distilled water. Transfer the filter paper along with
precipitate to a conical flask, add to 50 ml of distilled water and warm the contents to about
50°C to dissolve the precipitate. Add 2 to 3 drops of phenolphthalein and titrate the liberated
H 2SO 4 against N/50 caustic soda solution till a permanent pink colour is obtained. Let the
volume of N/50 N aOH used be V ml.
Calculations :
Applying normality equations,
N1V1 = N 2V2 , we have
(Water sample) (NaOH solutions)
=...!:.-V
50
1xV
Nl (Normality of water sample w.r.t. SOr ions) =
50 x 100
2 1xVx48 ~
Strength w.r.t. S04- ions) = ---gIL (Eq. wt of Sut = 48)
50x100 . ~
= 1 x V x 48 x 1000000 mgIL
50 x 100 x 1000
= 9.6 V ppm
Similarly, strength of SO~- ions
__ 1 x V x 50 x 1000000 mgIL
as CaC03 equivalent 50 x 100 x 1000
= 10Vppm
Where V is the volume ofN/50 NaOH used during the titration.
Example 20 : Calculate the amount of sulphate ions as calcium carbonate in 100
ml of water sample which when treated with excess of benzidine hydrochloride
followed by titration against N/50 NaOH required 14.5 mI. of alkali for complete
neutralization.
Solution: S gth fSO 2- C SO _ 14.5x50x10,00,000
tren 0 4 as a 4 - 50 x 100 x 1000
= 145p.p.m.
(ii) Gravimetric method: In this method sulphate ions are precipitated as BaSO4 in acidic
medium (by adding dil HCl), using BaCl2 solution as the precipitating agent. The precipitation
is carried out near the boiling temperature. After the completion of precipitations it is digested,
filtered and washed with hot water to remove excess of chloride ions. Usually, the precipitate
of BaSO 4 is ignited and weighed. From the weight of BaSO4 formed the percentage of SO 42-
ions can be calculated by the formula.
96 x 100
Percentage of SO42- in the given sample = 233 x w
where w is the wt of BaSO4 ppt after ignition, 233 corresponds molecular weight of BaSO4 and
96 is the weight SO 4 2- ions.
* Preparation of benzidine hydrochloride solution: Grind 4 grams of benzidine base with 5 -10 c.c. of water.
Transfer it to a litre flask, add 10 c.c. of conc. Hel and make the solution to one litre.
8.10 DETERMINATION OF FLUORIDE (F-)
Fluoride occurs in all natural water suppliers. Fluorides largly occur in chemical waste
from industries. If it is present in small concentration up to 1 ppm it effectively prevents dental
carries will out adverse effect on health. If it is found in concentration greater than 1 ppm,
it causes reduction is the cavities of teeth of young children. Excesssive fluoride in
drinking water may cause mottling of teeth or dental fluorosis, which results in discolouration
of enamel. Bone fluorosis is also observed when the concentration of fluoride is greater than
1 ppm.
Following methods are available for the determination of fluoride in water samples.
(i) SPADNS or colorimetric method
(ii) Electrode method
(iii) Scott-Samchis method
(iv) Distillations method
(v) Spectroscopic method
Electrodes and colorimetric methods are currently more satisfactory for determining
fluoride ion concentration. Both methods are susceptible to interfering substances, for example,
chlorine in the colorimetric method, and polyvalent cations, such as Al+++, through which complex
fluoride ions hinder electrode response.
Electrode Method
The fluoride ion-activity electrode is a specific ion sensor designed for use with a calomel
reference electrode and a pH meter having a millivolt scale. The key element in the fluoride
electrode is the laser type doped single lanthanum fluoride crystal across which a potential is
established by the presence of fluoride ions. The crystal contacts the sample solution
at one face and an internal reference solution at the other. The potential difference is
measured. An appropriate calibration curve must be developed that relates meter reading in
millivolts to concentration of fluoride. Fluoride activities dependent on total ionic strength of
the sample.
Colorimetric Method
The colorimetric method is based on the reaction between fluoride and a zirconium-dye
lake. (The term "lake" refers to the color produced when zirconium ion is added to SPADNS
dye.) Fluoride reacts with the reddish color-dye lake, dissociating a portion of it into a colorless
complex anion (ZrF 6-) and the yellow-color dye. As the amount of fluoride is increased, the
color becomes progressively lighter. This bleaching action is directly proportional to fluoride
ion concentration. Either a spectrophotometer or a colorimeter may be used to measure sample
absorbance for comparison against a standard curve.
o O--Zr=O
I
I
o
o
Zr-Alizarin Red Slake.
Method: To a lOO-ml sample of water add 1 drop of Na AS0 2 solution (5 gIL) to remove
reSIdual Cl. Now add 5 ml acid-zirconyl-alizarin reagent (300 mg ZroC1 2 .8H20/50 ml + 70 mg
alizarin red S/50 ml + 800 ml of 1.5 N HCI-1.2 N H 2S0 4- made up to 1 litre). Mix thoroughly
and compare the sample of water and standards after 1 hour. As the amount of fluoride is
increased. the color becomes lighter after some time.
8.11 DETERMINATION OF DISSOLVED OXYGEN
D.O. in water sample is determined by Winkler's Method. This method is based on the fact
that oxygen (dissolved in water) oxidizes potassium iodide to iodine. The librated iodine is
titrated against a standard hypo solution as usuaL However, since dissolved oxygen in water
is in molecular state, it can't oxidize potassium iodide as such. Therefore, an oxygen carrier
such as manganese hydroxide is used to bring about the reaction between KI and oxygen
Manganese hydroxide, in turn, is obtained by the action of KOH on manganese sulphate.
MnS0 4 + 2KOH ~ Mn (OH2) + ~S04
t
Mn(OH)2 + 02 ~ MnO(OH)2
MnO(0H)2 + H 2S04 ~ MnS0 4 + 2H20 + [0]
2Kl + H 2S0 4 + [0] ~ ~S04 + H 20 + 12
2Na2S20 S + 12 ~ Na2S40 6 + 2Nal
Modification: However, some samples of water like rain water contains ions like nitrites
and sulphites which can oxidize potassium iodide to iodine and thus the determination of
dissolved oxygen in their presence is liable to be wrong.
However, some samples of water like rain water contain ions like nitrites and sulphites
which can oxidise potassium iodide to iodine and thus the result determination of dissolved
oxygen in their presence is liable to be wrong. Th overcome this problem, sodium azide is
used in alkaline iodide solution to decompose the nitrite or sulphite.
2NaNs + H 2S0 4 ~ Na2S0 4 + 2HN3
HN0 2 + HNs ~ N 20 + N2 + H 20
It is referred to azide modification and is used for most of the effluents and sewage.
In the modified Winklers method, the interference due to certain oxidising agents such as
N0 2- and reducting agents such as Fe2+ and SOs2- is removed by treating the sample with
excess ofK Mn04 in acid medium. The following reactions lake place:
(i) 5 N0 2- + 2Mn04- + 6H+ ~ 5N03- + 2Mn2+ + 3H20
(ii) 5S032-+2Mn04-+6H+ ~ 5S042-+2Mn2++3Hp
(iii) 5Fe2+ + Mn0 4- + 8H+ ~ 5Fe3+ + Mn2... + 4H 20
NO s- and SO/- formed in the above reactions (i) and (ii) do not interfer. Fe3+ interfere
only when in amounts above 10 mglL. This interference is avoided by converting Fe3+ into
poorly dissociated complex FeF63- by adding KF,
Fe 3+ + 6F- ~ FeF6 3-
Excess ofKMn04 is destroyed by adding potassium oxalate.
2Mn0 4- + l6H+ + 5CPl- ~ 2Mn2 + + lOC0 2 + 8H20
Procedure: Take 250 ml of sample water, 2 ml of manganous sulphate solution and 2 ml
of alkaline potassium iodide solution in a bottle. Stopper the bottle and then shake thoroughly.
When the precipitate is settled, add 2 ml of conc. HCl or H 2 S0 4 and shake the bottle until the
precipitate has completely dissolved. Take 100 ml of this solution and titrate against N/100
hypo. solution using starch as indicator till the blue colour disappears.
Calculations: Let V ml of hypo is used against 100 ml ofthe sample solution.
Applying normality equation, we get:
N1V1 = N1V1
(Sample Solution) (Hypo)
1
N 1 x100=-xV
100
Nl (Normality of the sample w.r.t. D.O.) = ~N

10000
Strength w.r.t. D.O. = Normality x Eq. wt.
V BV
= 10000 N x B =10000 gIL
= O.OOOB V gIL =O.B V mglL or ppm
Amount of dissolved oxygen = O.OOOB~o~~OOOOOO =0.8 V ppm
8.12 BIO·CHEMICAL OXYGEN DEMAND (BOD)
Excessive nutrients, such as nitrates and phosphates, commonly originate in domestic
sewage, run offfrom domestic fertilizers, waste material from animal feed, packing plants etc.
The nutrients are responsible for water pollution primarily because they stimulate the growth
of micro-organisms which increases the Biochemical Oxygen Demand (BOD).
Micro-organisms can utilize carbohydrates, proteins and oils and fats as feed and oxidize
them to obtain energy for their life processes. Some bacteria can also utilize reduced inorganic
materials like Fe 2+, S2- and ammonia as source of energy. In the biological degradation (of
sewage and other waste material) which is brought about by a diverse group ofliving organisms
or bacteria, organic matter is first converted into fatty acids which by successive oxidation at
p-carbon atom, are broken down into fragments consisting of acetic acid. If sufficient oxygen
is present, that is in aerobic systems, oxygen is the ultimate electron acceptor which is reduced
while organic matter is being oxidised to CO 2 and H 20.
Inorganic materials like S2- and reduced nitrogen (NH 3 or NH4 +), if present are oxidised
to sulphate and nitrate.
S2- + 202 bacteria) SO42-
NHs + 202 ~:=:g) NOS- + H+ + H 20

Under anaerobic condition, i.e., in the absence of oxygen, S042-, PO/- and CO2, whatever
available, can act as electron acceptor and reduced to H 2S.
Sewage and other oxygen decaying wastes are termed as water pollutants. To avoid
development of nuisance or septic conditions, sufficient oxygen must be present or supplied
externally to maintain aerobic conditions throughout.
The amount of oxygen required by a mixed population of micro-organism in oxidising
organic matter present in a sample under strictly aerobic conditions, is generally known as
B.O.D. and is directly related to the extent pollution (by sewage or other oxygen-demanding
wastes).
The results of B.O.D. is expressed in milligrams oxygen per litre of water (mg/litre) or in
ppm. The pure drinking water, on the monthly average, should have 5 day BOD in the range
of 0.75 - 1.5 mg/litre. BOD value of sewage runs from 200 - 400 mg of oxygen per litre of
water. In fact, drinking water should have BOD less than 1 ppm.
BOD of say, 90 mgllitre of polluted water indicates that the biodegradation of organic matter
in one litre of sample consumes 90 mg of oxygen. BOD is an indicator and not an pollutant.
BOD values are very important, when we know that oxygen supply dissolved in water is so
reduced that fish no longer survive in water and when dangerous bacteria exist in water.
8.12.1 Method For Determination of BOD
The sample of water is incubated for 5 days at 20°C (roughly a mean value of temperature
of natural bodies of water) and the BOD values are reported as BODg. A polluted sample may
consume more oxygen in 5 days than present in water (nearly 9 mg/litre at 20°C) and so, before
analysis, is diluted with a specially prepared Dilution water. The diluted sample is taken in
two bottles. The 0.0 (dissolved oxygen) is one bottle is determined immediately and in the
other after 5 days of incubation. The BOD of the sample in then given by
BOD = 0 1 -02 X B mglL

A
where 01 = 0.0 of the sample in mg/L at the start of the experiment
O2 = 0.0 of the sample in mglL after 5 days
A = ml of the sample before dilution
B = ml of the sample after dilution
8.12.2 Importance of BOD
(i) BOD is most important in sewage treatment, as it indicates the amount of
decomposable organic matter in the sewage.
(ii) Greater the concentration of organic matter in the sewage, greater the BOD ..
(iii) It has special significance in pollution control, because it tells us the degree of pollution
at any time in sewage waste.
(iv) It also tells us about the amount of dissolved oxygen in water because it will be so
greatly reduced that fish no longer survive in water.
8.13 CHEMICAL OXYGEN DEMAND
It is an index of the total organic content of water oxygen demanding substances in water.
It is a satisfactory method for determining the organic load of a water body, which is preferable
to the bio-chemical oxygen demand. COD is readily measurable parameter for streams and
industrial waste water studies and control of water treatment plants. The method is based on
the chemical oxidation of material in the presence of a catalyst by Cr207 2- in 50% H 2S04 ,
COD may, therefore, be defined as the amount of oxygen required by organic matter in a
sample of water for its oxidation by a strong chemical oxidising agent such as K 2Cr20 7.lt is
expressed as ppm of oxygen taken form a K2 Cr2 0 7 solution in two hours.
8.13.1 Method For Determination of COD
A known amount of~Cr207 is added ~o a measured amount of the sample and the mixture
is boiled with concentrated sulphuric acid. After refluxing for two hours, the unreacted
dichromate (Cr20 72-) is determined by titration against a standard ferrous ammonium sulphate
(Mohr's salt) solution using ferroin as the indicator.
Ag 2S0 4 catalyses the oxidation of straight chain aliphatic compounds, aromatic
hydrocarbons and pyridine. HgSO 4 ties up Cl- ions as soluble complex and prevents its
interference. The difference between the dichromate originally present (added) and the
dichromate remaining unreacted gives the amount of dichromate used for the oxidation of
organic matter.
Therefore C.O.D = (B -A) x 9 II.

4x50 g
= (B - A) x 8 x 1000 m IL
4x50 g
= (B -A) x 40 mglL
where B - is the volume of dichromate originally present.
A - is the volume of dichromate remaining unreacted.
8.13.2 Importance of COD
1. The COD test is, therefore, widely used for measuring the pollutional strength of
domestic and industrial wastes.
2. The major advantages of COD test is that the determination is completed in 3 hours,
as compared to the 5 days required for the BOD determination.
3. COD is important in management and design of treatment plant.
4. It is used in calculating the efficiency of treatment plants and proposing standards
for discharging domestic effluents in various types of water streams.
8.14 NUMERICAL PROBLEMS ON BOD AND COD
Example 21 : 10 ml of a polluted water sample was diluted to 600 ml and equal
volumes were poured into two B.O.D. bottles. D.O in one bottle was determined
immediately (Blank) by Winkler's method and 204.4 ml solution required 3.9 ml
of N/40 Na 2 S 20 a• The second sample was incubated for 5 days and in the D.O.
determination, 204.4 ml solution required 2.1 ml of N/40 Na2S 20 a• Calculate B.O.D. of
the polluted water.
Solution: D1 = 3.9 ml
D2 = 2.1ml
A = 10 ml
B = 600 ml
B.O.D. Dl -D2 x B mglL

A
(3.9 - 2.1) _ 1.8 x 600
= 10 x600 - 10
= 108 mglL.
Example 22 : 100 ml of waste water (containing 820 ppm dissolved oxygen) was
diluted with 100 ml of distilled water and kept in a bottle at 20°C for 5 days. The
oxygen content of the resulting water was then found to be 260 ppm. Calculate the
BOD of the sample.
Solution: BOD [orginial D.O. - Final D.O.J x Dilution factor
= (820 - 260) ppm x (200 mU100 mD
= 560 x 200 =1120 ppm.
Example 23 : Calculate the COD of the effluent sample when 25 cm3 of an
effluent requires 9.3 cm3 of 0.001 M ~Cr207 for oxidation [Molecular mass of
~Cr207 =294].
Solution: 1,000 cm3 (or ml) of 0.001 M ~Cr207 =6 x 8 x 0.001 g of oxygen
6 x 8 x 0.001 x 9.3
.. 9.3 cm 3 (or ml) of 0.001 M ~Cr207 = g of oxygen
1,000
.. 6x8xO.001x9.3
25 cm3 of effiuent contains = g ofoxgyen
1,000
1,000 cm 3 of effluent contains 6x 8x 0.001x9.3x 1,000 0

or = 1,000x 25
g 2
6x8x 0.OOlx9.3
= g02
25
6x 8x O.OOlx 9.3 x 1,000 0
= 25 mg 2
= 17.85mg02
Example 24 : 50 ml of sample for COD analysis was reacted with 15 ml of 0.25 N
potassium dichromate solution and after the reaction, the unreacted dichromate
required 20 ml 0.1 N FAS for reaction. Under identical condition, 15 ml of diclu'omate
solution mixed with 25 ml of distilled water required 35 ml of 0.1 N FAS. What is the
COD of the sample?
Solution: Difference in volume of FAS required in the blank (distilled water) and the
sample = (35 - 20) ml = 15 ml
Now, 1000 ml of 1 N FAS contains = 8 g oxygen
8x15xO.1
or 15 ml of 0.1 N FAS contams = - - - - g oxygen
1,000
25 ml of water sample contains = 8 x 15 x 0.1 g 0

1000
, 2
or 1,000 ml of water sample contains =

8 x 15 x 0.1 x 1,000 0
1,000 x 50 g 2
= 0.240 g or 240 mg oxygen
Hence, COD of sample = 240 mglL.
Example 25 : 5 ml of a sewage water sample was refluxed with 10 ml of 0.25 N
~Cr207 solution in presence of dil. H 2S04 , The unreacted dichromate required 6.5
ml ofO.l N ferrous ammonium sulphate solution. 10 ml of the same ~Cr207 solution
and 25 ml of distilled water under the same conditions as the sample required 27.0
ml of FAS of 0.1 N. Calculate the COD of the sample.
Solution: Difference in volume of FAS required in the blank and sample.
= 27.0 - 6.5 =20.5 mL
Now 1,000 ml of 1 N FAS = 8 g of oxygen
or 20.5 ml ofO.l N FAS = 8x 20.5x 0.1 fO

1000
, go 2
25 ml of sample contains = 8x20.5xO.l fO

1,000 go 2
or 1,000 ml sample contains = 8x20.5xO.lxl,000 fO

1,000 x 25 g0 2
= 0.656 g of 02
= 656 mgof02
Hence, COD = 656 mg/litre or ppm.
1. If 4.0 ml of raw sewage has been diluted to 400 ml, and the DO concentration of the
diluted simple at the begining of the BOD test was 9 mglL, and 5 mg/l after 5 days
incubation at 20°C. Find the BOD of raw sewage.
2. A 2.5% solution of a sewage is incubated for 5 days at 20°C. Find the BOD of the sewage,
if the depletion of oxygen was found to be 5 mglL.
3. If 3.0 ml of raw sewage has been diluted to 300 ml, and the DO concentration of the
diluted simple at the beginning of the BOD test was 8 mglL, and 5 mglL after 5 days
incubatio at 20°C. Find the BOD of raw sewage.
4. A 1.5% solution of a sewage sample is incubated for 5 days at 20°C. Find the BOD of
the sewage, if the depletion of oxygen was found to be 3 mglL.
(ANSWERS)
1. 400 mglL. 2.200 mglL. 3.300 mglL. 4. 199.8 mglL.
8.15 SEWAGE TREATMENT

Sewage waste is the waste water from kitchens, bathrooms, lavoratories, laundries and
laboratories etc. Sewage also results from the disposal of wastes in factories. The various
minerals and organic matter in it is present as large and small particle of solid matter floating
and in suspension. It is also present in colloidal form. Apart from these inert materials sewage
also contains living organisms in solution.
The strength of sewage gives us an idea of the nuisance value of sewage. The strength of
the sewage is generally indicated by total volatile solids (both dissolved and suspended), odour,
biochemical oxygen demand (BOD), oxygen absorbed, chlorine demand and chemical oxygen
demand (COD). The ratio of carbon to nitrogen in settled domestics sewer is always much
lesser than that of Industrial wastes, because they contribute much organic matter. There are
two important type of bacteria which are present in the sewage in very high quantity. These
bacteria are-
(i) Saprophytic Bacteria (ii) Pathogenic Bacteria.
Methods of Sewage Treatment
The impurity in a particular sewage or in other words, the amount of treatment required,
is usually measured on one of the two basis :
(i) The amount of suspended solids.
(ii) The biological oxygen demand which measures the amount of impurities by the amount
of oxygen required to oxidise it.
The treatment procedures are generally of three types.
(i) Primary Treatment or (Mechanical Treatment)
(ii) Secondary Treatment or (Biological Treatment)
(iii) Tertiary Treatment or (Chemical and Physical Treatment).
(I) Mechanical Treatment
Removal of sette able solids is called primary or mechanical treatment. These solids are
removed by using screens, filters, grit chambers. Primary and secondary treatment includes
screening, grinding, flocculation or coagulation and sedimentation screens are used for the removal
of certain materials such as pieces of wood, plastic, paper floating, rags etc. are present in the
sewage.
.-------------4-------~'---------------- ....----....-......··1
Recirculated Alternate !
flow return of final !
effluent i
...
I
Influent
1-----'-.
i Effluent
Fig. 8.1. Primary treatment.
Chemical treatment precipitates the solids by flocculation or coagulation. Ferric sulphate

or aluminium sulphate are used as coagulant. The coagulates 'are then removed either by
sedimentation or by filtration. The sedimented solids are sent to digester tank where the organic
matter is decomposed in the absence of air. One ofthe decomposed product is methane gas.
A report of American Chemical Society has indicated that primary or mechanical treatment
reduces about 60% ofthe total suspended solids, 35% BOD, 30% COD, 20% total nitrogen and
about 10% of the total phosphorous.
'--- Rotating distributor
y
Filter Humous tank
Feed .OI----1 l - - -•• Effluent
Fig. 8.2. Trickling filter.

(II) The Secondary or Biological Treatment
Secondary or biological treatment includes processes such as filteration or activated sludge
processes. The eftluent from the primary clarifiers contains about 45 - 50% of unstable organic
matter originally present in the sewage. The main function of secondary treatment is to convert
the remaining organic matter of the sewage in to stable form by oxidation or nitrification.
The various filters which are commonly used for filteration of sewage in secondary treatment
are contact beds, trickling filters and miscellaneous filters. Filtration removes finely divided
suspended matter. As a result of flow of waste water through the beds, decomposition takes place
and soluble substances as well as sludge forming solids are synthesized. Bacteria, protozoa, fungi
and other living organisms are responsible for these decomposition and oxidation processes. These
bacteria decompose the dissolved organic materials and absorb nutnents and energy.
Influent Effluent
Recirculated now
Fig. 8.3. Aerofilter with single stage treatment.
In activated sludge process, sewage is treated biologically. In this process biologically active
growth are continuously circulated through organic waste in the presence of oxygen. The
activated sludge contains aerobic micro-organisms which digest the raw sewage. Some activated
sludge from the previous run is also introduced into the raw sewage and air is blown in only
in the amount needed. Aeration activates the sludge particles so as to develop an active culture
of aerobic organisms.
The matter which settles down at the bottom after treatment is called sludge and the liquid
is called eftluent. The sludge is disposed off ill many ways such as drying beds, dumping into
seas etc. The eftluent is also disposed off ill many ways such as sewage forming, letting it into
a natural drainage or sea. In this treatment remaining 45 - 50% organic matter (after primary
treatment) is converted into stable form by aerobic and anaerobic bacteria. The activated sludge
process gives clear treated liquid and the effluent is free form bad small or odour.
Influent Primary Aeration Secondary Influent

clarifier tank clarifier
Sludge Sludge
digestion drying beds
tank
Fig. 8.4. Flow diagram of activated sludge process.

Secondary treatment can reduce BOD to about 90%, COD to about 80%, total nitrogen to
about 50% and total phosphorous to about 30%. The reduction in suspended matter has been
estimated to be about 90%. In all the advanced countries nearly 60 - 70% of domestic sewage
receives the secondary treatment and used trickling filter and activated sludge treatment.
(III) Tertiary Treatment (Chemical and Physical Treatment)
The aim of tertiary treatment is further purification of waste water as well as its recycling
The most important purpose of tertiary treatment is an effective and efficient removal of
pollutants than primary and secondary treatments. Tertiary treatment is the most advanced
phase of sewage treatment which is provided to only 2% of domestic sewage. The main purpose
of tertiary treatment is to decrease the load of nitrogen and phosphorous compounds present
in the effluents by the following processes:
(i) Precipitation
<ii) Nitrogen stripping
(iii) Chlorination.
(i) Precipitation: The effluent received after secondary treatment is mixed with calcium
oxide which reacts with phosphorous present in the waste to form calcium phosphate, which
settles down at the bottom of the setting tank from wheTe the water is filtered out.
(ii) Nitrogen stripping : Nitrogen present in waste water is generally in the form of
ammonia gas, nitrates and nitrites. Nitrogen enhances eutrophication, which escalates rapidly
when abnormally high amounts of nutrients from sewage animal wastes, fertilizers and
detergents enter the lakes caming excessive growth of Phytoplanktons and aquatic weeds.
The waste water containing ammonia is directed into metal tower. This water trickles
downwards over a series of small plastic baffle plates, air is forced upward" through the effluent
which removes the ammonia gas.
(iii) Chlorination: The effluent from which nitrogen, phosphorous and dissolved organic
matter is removed, is, then chlorinated to kill disease causing micro-organisms that might be
present is waste water. The treated water is then discharged into rivers or lakes and can be
used after normal chemical treatment. The quality of chlorine in ppm although varies from 20
ppm for raw sewage to about 5 ppm for completely treated sewage.
Activated Chlorination
sludge
~
Sedi- Sedi-
mentation mentation
Trickling
filter
Anaerobic Aerobic
'-----------------------------~ '---------------------------------~
Primary treatment Secondary treatment
Fig. 8.5. Flow diagram for sewage treatment.
In recent years there are various methods that have been used for advanced waste
treatment. These are adsorption, chemical oxidation desalination, chemical coagulation and
filteration. The use of suitable treatment process, however, depends upon local requirements.
A flow chart for the treatment of combined sewage is shown below:
Simple Systems To Treat Sewage
Instead of energy consuming systems, simple sewage treatment methods such as oxidation
ponds could be used in Indian cities and towns. Oxidation ponds are lagoons or basins in which
waste water is cleaned by making use of sedimentation and action of micro-organisms. But
there are some drawbacks of oxidation ponds. For example, these ponds require land, which
is very expensive. Water from oxidation ponds can be used for irrigation and so it is desirable
to use oxidation ponds because they are more reliable.
The use of oxidation ponds of anaerobic processes in conjugation with aerobic processes
has reduced land requirements and lower power consumption. For India tropical climate,
anaerobic treatment is an ideal process. In this process 80% water purification takes place
with near-zero power requirement. For large towns, a combination of anaerobic and aerobic
treatment, followed by irrigation is probably ideal. Biogas produced in the anaerobic process
can also be collected for domestic use.
Low cost sanitation methods, such as pit latrines and soak pits are ideal in small towns
and out skirts of cities.
1. What is meant by BOD (Biological oxygen demand) ? (PTu, Dec. 2003)

2. Differentiate between BOD and COD?
3. What is the importance of BOD ?
4. What is COD?
5. Is COD the key test for determining the pollution load in water samplers? Justify
your answer?
6. What is the importance of dissolved oxygen in water?
7. What is sewage waste?
8. Which sewage is called stale sewage?
9. What is primary treatment of sewage?
10. What is secondary treatment of sewage?
11. What is the difference between primary and secondary treatment?
12. What is the main aim of primary treatment?
13. What are the various methods used for secondary treatment of sewage waste?
14. What is trickling filter process?
15. What is activated sludge?
16. How much pollutants are reduce by secondary treatment of sewage waste?
17. What is tertiary treatment?
18. What are the various methods use for tertiary methods?
19. What is the aim of tertiary treatment?
20. What do you mean by eutrophication ?
21. What are the main purposes of chlorination ?
22. What are the other simple sewage treatment processes used in India?
(ANSWERS)
1. The organic matter present in sewage or waste water is of two kinds (i) that which
can be oxidized by bacteria called biologically active or biologically degradable: and (ii)
that which can not be oxidized biologically and is called biologically inactive. We are
mainly interested in the biologically active organic matter.
Biological oxygen demand is defined as the amount of dissolved oxygen (required by
bacteria while oxidizing organic matter under aerobic conditions. It measures the oxygen
consumed by living organisms while assimilating organic matter present in waste water.
The water pollution is measured by BOD, which is a standardized measurement of the
amount of oxygen required by micro-organisms to decompose the organic matter in a
water sample over a period of five days at 20°C.
2.
BOD COD
(b) BOD is the amount of dissolved oxygen (a) COD is a measure of both biologically
required by bacteria while oxidizing oxidisable (like glucose) as well as
organic matter under aerobic conditions biologically inert (like cellulose) organic
in the waste water. matter present in the waste water.
(c) The BOD determination takes a long (b) It can be determined in short period of
period of 5 days time around 2-3 hours.
(d) BOD values are useful generally in (c) COD is important in management and
process design and loading design of treatment plants because of its
calculations, measurement of treatment rapid determination. It is used in
efficiency and operation stream calculating the efficiency of treatment
pollution control, and in determining the plants and proposing standards, for
self purifying capacity of streams discharging domestic effiuents in various
types of water streams.
354 Essentials o/Engineering Chemistry
3. BOD is most important in sewage treatment, as it indicates the amount of
decomposable organic matter in the sewage. It has special significance in pollution
control.
4. COD may be defined as the amount of oxygen required by organic matter in a sample
of water for its oxidation by a strong chemical oxidising agent such as ~Cr207'
5. Yes, COD in the key test for determining the pollution load in water sample, because
it measure all the impurities including cellulose etc. in the sewage water.
6. A high concentration of dissolved oxygen supports biodegradation of organic matter
by aerobic bacteria. Lake of dissolved oxygen means pollution by organic and other
materials requiring O2 for decomposition.
7. Sewage waste in the waste water from kitchens, bathrooms, lavatories, laundries and
laboratories etc. Sewage also results from the disposal of waste in factories.
8. The sewage in which aerobic decomposition is continuing is called stall sewage.
9. Removal of settleable solids is called primary treatment or mechanical treatment.
10. Secondary treatment decomposes organic matter by the action of aerobic bacteria
and sedimentation.
11. Primary treatment removes large and small suspended particles by filteration and
by chemical method like coagulation. Secondary treatment decomposes organic matter
by the action of aerobic bacteria and sedimentation.
12. The main aim of primary treatment is to remove large and small suspended impurities
by filteration and sedimentation.
13. The main methods used for secondary treatment are trickling filter method and
activated sludge process method.
14. Trickling filter process is used for secondary treatment. In this process the sewage
waste is pass through the filter beds of sand at regular intervals. This enable the air
to enter the interstices of the bed between doses of sewage, and thus supplies the
required aerobic bacteria.
15. Sludge through which compressed air has been blown.
16. Secondary treatment reduce 90% BOD, 80% COD, total nitrogen 50'Yc, and total
phosphorous upto 30%.
17. Tertiary treatment is the purification of waste water as well as its recycling.
18. The various methods use for tertiary treatment are:
(i) Precipitation
(ii) Nitrogen stripping.
(iii) Chlorination.
19. The main aim of tertiary treatment is the further purification of water to decrease
the load of nitrogen and phosphorous compounds present in the effluents as well as
its recycling.
20. "Eutrophication" is a natural process, derived from the Greek word 'eutrophos' means
well nourished or enriched. Therefore, it is a phenomenon through which a nutrient
rich bag in a shallow depreSSIOn changes to leached bog, deficient in nutrients.
21. The main purposes of chlorination are?
(i) To assist the process of treatment of some type of industrial wastes.
(ii) To control foaming in sludge digestion tanle
(iii) To increase the efficiency of sewage treatment plants.
22. Simple materials use for sewage treatment are:
(i) Oxidation land method
(ii) Oxidation pond method with a combination of anaerobic and aerobic treatment.
8.16 POTABLE WATER

Water used for drinking purposes is called potable water. The water used for drinking and
other domestic purposes must be free from germs and bacteria. It should be free from
objectionable impurities such as organic matter, suspended impurities etc. besides the dissolved
salts and gases. The water obtained from any source has to be treated to make it fit for drinking
purposes.
The treatment of water before use for domestic purposes is of utmost importance. Water
for domestic purposes should be clear, colourless, pleasant in taste, and free from excessive
dissolved salts, suspended impurities, and harmful microorganisms.
The Bureau of Indian Standard (BIS) and Indian Council of Medical Research (lCMR) have
prescribed minimum and maximum permissible limits of various physical and chemical
properties such as turbidity, pH value, dissolved solids, total hardness, metal ions etc. for water
to be used for drinking purposes.
Water used for domestic purposes should meet the following requirements:
(i) It should be clear, colourless and odourless.
(ii) It should have an agreeable taste.
(iii) It should be free from pathogenic micro-organisms.
(iv) Its turbidity should not exceed 10 ppm.
(v) It should be free from objectionable dissolved gases such as H 2S, NH.1 etc.
(vi) It should not contain harmful minerals such as lead, arsenic, chromium etc., salts
and mineral oil.
(vii) Its pH should be about B.O.
(viii) It should be neither too hard nor too soft. The recommended hardness is about 300
mg I L as CaCa.1 equivalent.
(ix) The total dissolved solids in it should be less than 500 ppm.
(x) Its alkalinity should not exceed 600 mg / L.
8.17 PURIFICATION OR TREATMENT OF WATER FOR DOMESTIC USE
Water used for domestic purposes must be free from germs and bacteria. It should be free
from objectionable dissolved gases like H 2S, S02' oxides of nitrogen (NO) and dissolved salts
like lead, arsenic, manganese salts. Generally, for domestic supply, surface water is used and
it is contaminated with large number of impurities, such as organic matter, suspended impurities
etc. It must be free from germs and bacteria. Therefore to make it safe for drinking purposes
following steps are be carried out.
1. Sedimentation : Sedimentation is the process of removing suspended impurities by
allowing the water to stay undisturbed for some time in large tanks when most of suspended
particles settle down due to the force of gravity. The clear water can be taken out from tank
with the help of pumps. The detention period in a settling tank may range from an hour to
several days.
The process of sedimentation is generally carried out in continuous flow type tanks in which
water flows continuously in a horizontal, or vertical direction at a slow and uniform speed.
Due to gravitational force, the suspended particles get settled down at the bottom of the tank,
from where they can be removed periodically. Sedimented water is taken out continuously.
2. Coagulation: Coagulation is the process of removing colloidal (fine sized) particles from
water by the addition of certain chemicals known as coagulants before sedimentation. The
process is usually carried out along with sedimentation.
Actually the colloidal particles present in water either do not settle down at all or take a
very long time. In order to have a quick settling of these particles, certain chemicals known
as coagulants are used. The commonly used coagulants are the salts of iron and aluminium
e.g., alum [~S04Al2(S04)3' 24 H 20], ferrous sulphate (FeS0 4.7H20) etc.
These coagulants react with bi-carbonates present in water, and form bulky gelatinous
precipitate called 'flock'. As these flocks descend through water, they absorb or catch suspended
fine particles from water and forming bigger flocks, which settle down quickly. The addition of
coagulants to water also removes colour, odour and improves its taste.
Al 2(S04)3 + 3 Ca(HC03)2 ~ 2Al(OH3) -l.. + 3CaS04 + 6C02 t
(Coagulant) Calcium (Bulky gelatinous flock)
bicarbonate
FeS0 4 + Mg(HC0 3)2 ~ Fe(OH)2 -l.. + MgS0 4 + H 20 + CO2 t
(Coagulant) (Magnesium) (Ferrous)
bicarbonate) hydroxide)
4Fe(OH)2 + 2H20 + 02 ~ 4Fe(OH)3-l..
(Dissolved oxygen) Ferric hydroxide (Heavy flock)
Colloidal particles are very small size (10-4 to 10-7 cm) particles possessing either positive
or negative charge. Due to similar charge, they repel one another and do not come together.
Therefore, they do not settle down during sedimentation. Colloidal particles of clay possess
negative charge. When alum (coagulant) is added to water, it provides positive aluminium ions
AP+. These positively charged aluminum ions neutralize negative charge of colloidal particles
of clay. As the charge is removed from the clay particles, they come nearer and combine to
from bigger particles, which settle down at the bottom of the container due to gravitational
force.
3. Filtration: Filtration is a process of removing insoluble colloidal and bacterial impurities
by passing water through a bed of proper sized material. By filtration, suspended matter,
insoluble colloidal matter, most of bacterias. colours, and odour of water are removed. Two
types of filters are commonly used in domestic water treatment.
(i) Gravity sand filter (ii) Pressure filter.
(i) Gravity sand filter: It consists of a large shallow rectangular tank made of concrete
(Fig. 8.6). At the bottom of the tank, there is a channel of bricks through which filtered water
goes out. Over this channel a layer of coarse and fine gravels (about 30 cm thick) and then, a
layer of coarse sand (about 20 cm thick) and finally a layer of fine and (about 50 cm thick) are
placed. Sedimented water enters the sand filter from the top. As the water percolates through
the sand bed, fine suspended particles, most of the germs and bacterias are retained by the
top layer. Clean filtered water is collected in the under drain channel, from where it is drawn
out.
Water level
water
~~F;;;';;;;;;;;';;;;;;;;;';;;;;;;;;;';:;;;;~Tfii" Filtered water
outlet pipe
Under drain channel
Fig. 8.6. Gravity sand filter.
The rate of filtration, after 24 hours of use, becomes slow due to clogging of pores of the
top sand layer by the impurities retained in the pores. Therefore, the portion of the top fine
sand layer is scrapped off and replaced by a new sand layer. The filter is put to use again.
These filters are best suited for municipal water supply.
(ii) Pressure filter: It consists of a cylindrical vertical steel tank containing three layers
of filtering media one above the other.
(a) Pebbles (10-35 mm grain size) layer,
(b) Coarse (5-7 mm grain size) layer,
(c) Fine sand (1-2 mm grain size) layer.
Impure sedimented water is mixed with a small amount of alum solution. It is then forced
under pressure from the top of tank (Fig. 8.7). Added alum forms an artificial slimy layer on
the filter bed and this helps in removal of colloidal and bacteriological impurities. The function
of the deflector plate provided at the top is to distribute the slimy layer uniformly over the top
of the filter bed. Filtered water as it comes out from the bottom of filter is under pressure and
can thus be pumped directly.
Pressure filter gets clogged after its use for some time and its periodical cleaning is
necessary. This is done by 'back washing'. The water under pressure is forced up the tank
which removes the matter that has clogged the sand pores. The back wash water is then allowed
to go to drain. Now-a-days, compressed air is used to agitate sand before back washing. Pressure
filters are economical only for small scale water supplies such as municipal water supply.
Slimy layer of
Al(OH)a
Fine sand
Pebbles
Compressed air inlet - . __ , __~
Wash water inlet -=~:-Filtered water outlet

Fig. 8.7. Vertical pressure filter.
4. Sterilization (Removal of bacteria and micro-organisms)
Water, after passing through sedimentation, coagulation and filtration operations, still
contain a small percentage of pathogenic (disease-producing) bacteria. Therefore it is necessary
to remove these bacteria and micro-organisms etc. from water. This process is known as
disinfection or sterilization of water. The chemicals used for sterilization/disinfection are known
as 'sterilizers'/disinfactants. The disinfection of water can be carried out by the following
methods.
(i) Boiling (ii) Chlorination (iii) Ozonisation
(iv) Permangnate addition (v) Aeration (vi) Ultraviolet rays
(vii) Removal of algae.
(i) Boiling: Sterilization, strictly speaking, is the boiling of water before using for domestic
purposes. Boiling kills all the disease-causing germs and bacteria during epidemics like cholera
and typhoid within five minutes. But this method is useful only for household purposes because
the process is yery expensive for municipal town supply of water.
(ii) Chlorination: Chlorination can be carried out by the following methods.
(a) By using chlorine gas, (b) By adding bleaching powder.
(c) By using chloramine.
(a) By using chlorine gas Cl:a : Chlot?-ne can be used directly as a gas or as chlorine
water for sterilization in municipal water supply. It reacts with water to form hypochlorous
acid which gives nascent oxygen, both of which are powerful germicides.
Cl2 + H 20 ~ HOCI + HCI
(Hypochlorous acid)
HOCI ~ HCI + [0] (Nascent oxygen)
Germs + [0] ~ Germs are oxidised.
However, excess of chlorine should be avoided because it produces unpleasant odour, taste
and irritating effect on mucous membranes. The treated water should not contain more than
0.1-0.2 ppm of free chlorine.
By adding bleaching powder (CaOCI 2>: Bleaching powder is a good sterilizer for
(b)
small water works. In practice, about 1 kg of bleaching powder per 1000 litres of water is mixed
and the resulting solution is allowed to stand for several hours. Hypochlorous acid (HOC!) and
nascent oxygen (0) produced by the reaction of water on bleaching powder are powerful
germicides.
CaOCl2 + H 20 ~ Ca(OH)2 + C~
Cl2 + H 20 ~ HOCI + HCI
HOCI ~ HCI + [0] (Nascent oxygen)
The nascent oxygen liberated oxidises germs and other harmful bacteria.
Only calculated quantity of bleaching powder should be used, because excess of it will give
a bad taste and disagreeable smell to the water.
Disadvantages
The use of the bleaching powder has the following disadvantages:
1. Bleaching powder introduces calcium in water, thereby making it more hard.
2. Bleaching powder is spoiled due to its continuous decomposition during storage. Hence
before its use, it should be analysed for its effective chlorine contents.
3. If used in excess amount, it imparts a bad taste and disagreeable smell to water.
By using chloramine (CINH2 ) : Chlorine and ammonia are mixed in the ratio of2 :1 by
volume to produce a compound known as chloramine. This process is known as chloramination.
Cl2 + NH3 ~ CINH2 + HCI
Chloramine
Chloramine is a quite stable compound and does not impart any disagreeable smell and
bad taste to water, hence is considered as better germicidal than chlorine alone.
ClNH2 + 2H20 ~ HOCI + NH40H
HOCI ~ HCI + [0] Nascent oxygen
Advantages of Chloramination
1. It removes irritating smell due to excess of chlorine.
2. It imparts good taste to water:
3. It checks the dissipation of chlorine (by stabilizing chlorine) when water is exposed
to atmosphere, especially to sunlight.
The chloramine tablets are used in the army for stabilizing water. Water is collected in
individual bottles in which chloramine tablets are added followed by sodium thiosulphate, which
removes excess of chlorine.
(iii) Ozonisation : This is an effective method of sterilization of water, Ozone (03) is
unstable and it decomposes into molecular oxygen (02) and nascent oxygen (0).
03 ~ 02 + [0] (Nascent oxygen)
The nascent oxygen thus produced is very effective and kills all the germs and bacteria.
In ozonisation, water is allowed to percolate through a tower having perforated partitions
(Fig. 8.8). Ozone is allowed to enter from the bottom which kills the germs when they come
in contact with water. Sterilized water is collected at the bottom of the tank.
This method is quite expensive and hence is not employed for sterilization of municipal
water supply.
Impure water _===::::;-, r;::======----- Waste gases
llliilt=
1 Gravel bed
Curved partition
having performation
Ozone gas
•••
-E:::=t;~~=!.~.:!.~:oJ
Sterilised water
Fig. 8.8. Ozone sterilizer.

Advantages of ozonisation
1. Ozone acts not only as a sterilizing agent, but also bleaching, and de-odouring agent.
2. It improves the taste of water.
3. In excess, it is not harmful, since it is unstable and decomposes into oxygen.
(iv) Permangnate addition: KMn0 4 is also used for sterilization of water. It is an
oxidizing agent and kills bacteria present in water. It is occasionally added into wells and
domestic water tanks. It is especially used in washing instruments and utensils in hospitals
and other public places.
(v) Aeration: The process of spraying water in the form of fine droplets into the
atmosphere is known as aeration.
This is the most modern method of purifying water for town supply. In this method, water
is forced under pressure through a perforated pipe (Fig. 8.9). As water sprays into air, it comes
in intimate contact with the oxygen of air and is exposed to the ultraviolet rays of the sun.
This kills bacteria and the oxygen oxidizes organic matter present in the water. The pure water
is collected in shallow tank placed below. It should be noted that as the exposure time is too
small, the desirable effect may not be obtained.
Spray
Purified water
Fig. 8.9. Aeration.
Natural aeration takes· place in streams and rivers when the water flows slowly in its bed
or when it forms a falL
(vi) IDtra-violet rays: The invisible ultra-violet rays are very effective in killing all types
of bacteria. This method is widely used for the disinfection of swimming pool water, because it
does not require any chemicals to be mixed with water. In this method, ultraviolet rays (from
mercury lamps enclosed iIY a quartz globe) are simply focussed on flowing water. However,
this method is very costly and can not be used for mumcipal supply water.
(vii) Removal of algae: Algae is produced in water by a type of air borne bacteria. It can
cause a lot of problem in cooling system such as air-conditioning. In air conditioning, spray
nozzles and even screens of circulating pumps are clogged by algae and thus efficiency of plant
is decreased.
Growth of algae can be prevented by the use of certain chemicals e.g., salts of mercury,
copper, silver, sodium penta-chlorophenate and quaternary ammonium compounds.
8.17.1 Break Point Chlorination
The disinfecting action of Cl2 is not so simple. It form HCi and HCIO with water and its
disinfecting forms are Cl2 and HCIO. Being an oxidising agent, it first oxidises organic matter
and other reducing agents such as NH 3, Fe2+, H 2S etc. For instance, phenol is oxidised to
chlorophenols which give peculiar odour to water. The HOCI reacts with NH3 likely to be present
in water as under
NHs + HOCI ~ NH2CI (Monochloroamine) + H 20
NH 2CI + HOCI ~ NHCl2 (Dichloramine) + H 20
NHCl2 + HOCI ~ NCls (Nitrogen trichloride) + H 20
The chloramines formed above act as C~ reserves, killing organisms that were not destroyed
during the initial treatment. Thus free Cl2 becomes available for disinfection only after the
demand for Cl2 by other reacting substances is met with. It is, therefore, important to realise
the distinction between two types of chlorines. (i) Free chlorine residual (CI 2 , HOCI, OCI-) and
(ii) Combined chlorine residuals (chloramines). For efficient disinfecting action, a greater
concentration of combined chlorine residual than of free chlorine residual is required. The
effect of passing Cl2 into water containing reducing agents such as NH 3 , H 2S etc. can be
represented in Fig. 8.10.
Oxidation of Formation of Destruction of Free residual

reducing chloro-organic chloro-organic chlorine
compounds compounds and chloramines
by chlorine and
chloramines
!
i
cI
a +-- Break point
Fig. 8.10. Applied chlorine dose.

Chlorination of water to the extent of converting all the NH3 into NCl 3 or N2 is referred to
as break point chlorination. After this point, free residual chlorine appears in water which destroy
the pathogenic bacteria. Usually, all tastes, odours disappear at break point.
It is clear from the curve that chlorination of water proceeds in the following steps :
(i) oxidation of reducing compounds by chlorine (upto a).
(ii) formation of chloro-organic compounds and chloramines from a to h.
(iii) destruction of chloro-organic and chloramines from b to c.
(iv) killing of pathogenic bacteria present in water from c to d.
Significance of break point chlorination : Thus the significance of break point
chlorination is that a chlorine dosage higher .than this point means that the chlorine demand
of the chlorine reactable materials has been completely met with and free chlorine residuals
are available for bacterial action. It also signifies complete decomposition of NH 3 , removal of
colouring matter and odour of the water sample. An over dose of chlorine produces an
unpleasant taste and odour. Moreover, excess of chlorine produces an irritation on muscus
membrane. So, information regarding break point of the water sample being chlorinated is
useful in following respects :
(i) It indicates complete oxidation of organic matter responsible for imparting colour, bad
smell and unpleasant taste of water,
(ii) It ensures complete destruction of disease producing bacteria,
(iii) It prevents the development of any weeds, :and
(iv) It prevents the presence of excess chlorine which may impart bad odour and taste to
water.
(PRACTICEPROBLEMBFORTUTO~S)
1. Name four substances used for disinfection of water. (PTu, May 2003)
2. Name the chemicals employed for disinfection of water by chlorination. Point out the
most efficient chlorinating agent with reasons.
3. Bring out the difference between disinfection and sterilization. Which process is
employed in municipal 'Nater treatment?
4. What is the function of hydrazine in water treatment ? Why is its use
preferred?
5. What is break-point chlorination? Point out its advantage.
6. What is the principle of Reverse Osmosis? Give its advantage over demineralization.
(ANSWERS )
1. The names of four disinfectants used for water are:

(a) Bleaching Powder (b) Chlorine gas (c) Chloramines and (d) ozone gas.
2. The following chemicals can be employed for the process of chlorination of
water
(i) Bleaching powder (CaOC~)
(ii) Chlorine gas on in concentrated solution form
(iii) Chloramine (ClNH2).
Bleaching powder introduces calcium in water and makes it hard. Moreover, it
decomposes during storage. Excess ofit gives a bad taste and smell to the treated water.
Although direct use of Cl2 is more effective and economical and it does not introduce
any other impurity in water, yet its excess produces irritation on the mucous membrane
and gives unpleasant taste and odour. Now-a-day, chloramine is considered to be most
efficient for disinfection. Its excess does not produce any irritating odour and it imparts
a good taste to treated water.
3. The process of destroyinglkilling the disease-producing bacteria from water to make it
safe for drinking purposes is known as disinfection. It does not ensure total destruction
of aU living organisms. On the other hand, sterilization mean complete destruction of
all living organisms. It is done by boiling the water for a period of time. It is a costly
process and is used only by individuals during the break up of epidemics. It can not be
employed at the time of boiling. .
4. The function of hydrazine in water treatment is to remove dissolved oxygen in water,
which would otherwise cause corrosion of the boiler. Dissolved oxygen reacts with
hydrazine or sodium sulphite or sodium sulphide as under.
H2N-NH2 + 02 ----+ N2 + 2H20
2N~803 + 02 ----+ 2N~804
Na 28 + 202 ----+ N~804
The use of hydrazine is preferred because it reacts with 02 forming N2 and H 20. N2
gas escapes without any adverse effect. But in the other two cases. N~804 formed
gets dissolved in water. In high pressure boiler, N a 2804 may get decomposed giving
802 which forms sulphurous acid causing corrosion ofboiier material.
5. Break point chlorination corresponds to a minimum point in the curve plotted between
the applied chlorine dosage and free residual chlorine to oxidize organic matter reducing
substances and free ammonia present in raw water and after that point the chlorine is
free for its disinfecting action against the pathogenic bacterias.
Advantages of break-point-chlorination are :
(i ) It ensures complete destruction of organic matter which impart colour, bad odour
and unpleasant taste to water.
(ii) It also ensures killing of all disease producing bacteria.
(iii) It prevents the growth of any weeds or algae in water.
6. When two solutions of different concentrations are separated by a semi-permeable
membrane, flow of solvent takes place from dilute to concentrated solution due to the
process of osmosis. But when a hydrostatic pressure greater than the osmotic pressure
is applied on the concentrated side, the solvent flow is reversed i.e., it is fprced to move
from concentrated solution to dilute solution across the membrane. On this basis, water
is separated from its impurities, rather than removing the impurities from water. This
principle of reverse osmosis is applied for treating saline water i.e., sea water.
The process of reverse osmosis has a distinct advantage over demineralisation process.
By this process we can remove not only ionic but non-ionic, colloidal and organic
substances possessing high molecular masses also. Thus colloidal silica can be removed
by reverse osmosis which can not be removed by demineralisation. Likewise, non-ionic
compounds and high molecular weight organic matter can also be removed, which can
not be removed by demineralisation.
8.18 DESALINATION
Desalination means removal of salts from saline water. The technique of desalination or
desalting is commonly used for sea waters which have around 35000 ppm of dissolved solids.
Water containing high concentrations of dissolved solids with a peculiar salty or brackish taste
is called brackish water. Sea water is an example of brackish water as it contains about 3.5%
of dissolved salts. The treatments discussed so far are used for water with relatively low
dissolved salt content. There are regions having poor water supplies of underground water,
especially localities near the sea shore, where use of sea water is essential for domestic as
well as industrial purposes. Some deep well waters have high amount of dissolved solids in
them and therefore, treatment of such waters by demineralization is very expensive. So
desalination of water having high content (10,000-35000 ppm) of dissolved salts is a promising
alternative.
Various techniques used for desalination are discussed as under:
8.18.1 Distillation By Flash Evaporation
This technique involves boiling of saline or brackish water in huge evaporators. The vapours
collected are condensed to give pure water. However, it is an expensive method for common
use. But it has been made economical b'y carrying out the evaporation and condensation i.e.,
distillation in multiple-effect evaporators :or flash evaporators as explained below ,'
This method consists in evaporating sea water at 75-80°C under reduced pressure and then
condensing the vapour under conditions of minimum heat loss. The concentrated brine is
discharged to waste. The experimental details are discussed below:
Multiple-effect or Flash Evaporation
The principle of thi$ process is based upon regenerative system of heat economy , The heat
supplied by the fuel in steam' generation in the first evaporator is utilized in heating up the
brine in the second and so on. Thus the fuel is saved.
In the multi-effect evaporators, each unit i~ maintained at a slightly lower pressure and
temperature than the previous one so that the steam produced in one unit becomes the source
of heat in the next. In each evaporator unit, the water vapour condenses on condensers
represented as C and the heat of condensation is utilized in heating the coils carrying the
saline water in them Fig. B.11.
Water
vapours +-
Pl
water
._--.
...... I
~
"W
•:I~
••
• ••
••
• I
•
Brine~~==::~milllli==1~~=iIlIlIl~==111:~~F=~~~~;~II~~==1nFi==~
----------------;-.-------------
Water Water Water
Water •
Fig. 8.11. Desalination of sea water by multi-effect flash evaporators.
The condensed water from each unit is collected. Evaporators having up to 50 units have
been constructed. The saline water moves through the coil in direction opposite to the
movement of steam (hot vapours). The hot vapours from each unit are compressed to a high
pressure. These compressed hot vapours are allowed to condense in the heat exchangers (not
shown in the Fig. B.11). The heat energy in the hot vapour is thus utilized in heating the
saline water moving inside the coil in opposite direction. The temperature as well as the
pressure falls as the vapours move from unit first to the second and so on. With decrease in
the vapour pressure, the boiling temperature in each unit goes on decreasing accordingly. As
the vapour pressure is decreased successively from P 1 to P n in different units, the temperature
at which evaporation takes place in these units also-decreases i.e., from T 1 to Tn' Thus due to
exchange of heat between the hot vapour and the saline water, the amount of fuel to be .used
for evaporation is saved.
Scale formation in the evaporators can be prevented by using evaporator compounds
consisting of a mixture of anti-foamants such as polyethylene glycol esters, sulphonated lignin
and complexing agents such as the disodium salt of EDTA, or polyphosphates. These are however
not very effective in boilers, as the complexes formed may decompose at the temperatures
and pressure prevailing in the boiler.
8.18.2 Freezing
In this method, the brackish water is cooled to freezing temperatures, when the salt is
left in the mother liquor and ice crystals are formed. These crystals can be easily separated,
washed and finally melted to give pure water. This method can be used in cold regions only.
The freezing process can be employed with an advantage over the evaporation process
because the quantity of heat which in withdrawn from a kilogram of water to freeze it is much
lower than the quantity of heat which should to supplied to evaporate one kilogram of water.
Either of the following two methods can be employed.
In the first case, sea water in evaporated by introducing it to a chamber, which has been
evacuated to very low pressure. The heat required is withdrawn from sea water itself, which
gets cooled and ice crystals are formed. The crystallized ice is filtered and washed with fresh
water to remove the adherent brine. The ice is melted and the heat required for this process
is withdrawn from the incoming saline water, which gets precooled before its introduction to
the evacuated chamber. Thus the energy required for freezing water is reduced.
In the second case, hydrocarbons such as propane, butane and isobutane with boiling points
below O°C are used for freezing the saline water. The hydrocarbon is mixed with saline water
under pressure and allowed to evaporate by releasing the pressure. The heat of evaporation is
withdrawn from the mixture, which gets cooled and ice is formed. Ice is recovered by filtration
while the hydrocarbon is recovered from the vapour and used again.
8.18.3 Electrodialysis
Principle: The method is based on the principle that charged ions move towards respective
oppositve charged electrodes through ion selective membranes when potential difference is applied
across salt water solution.
It consists of two electrodes and
ion selective membranes which are Saline water Saline water Saline water
permeable to either cation or anion.
The anode is placed near anion
selective membrane while the 11'---~i- - '
11 -.----1
!
< - - - I
11
cathode is placed near the cation
selective membrane . The anion
selective membrane has positively Cathode
charged functional groups such as
Don I
i
i Anion
i
:
Anode
R4N+ and therefore allows negatively

charged ions only to pass through ! e I:'
them. Similarly, a cation selective ~

!
:;,' :
membrane has negatively charged

functional groups such as RCOO-
and allows only positively charged 1 permeable
ion-exchange
membrane
1
I Ca~ion I I Anion· I
permeable
ion-exchange
membrane
1
ions to pass through it. Fig. 8.12. Brine Fresh Brine
When an emf is applied across water
two electrodes the cations present in Fig. 8.12. Electrodialysis of brackish water.
salt water move towards cathode
through cation selective membrane and anions move towards the anode through anion selective
membrane. As a result, the central compartment is free from all ions while the two side
compartments get rich in ions. Desalinated water is drawn out from the central compartment
while the concentrated brackish water is replaced by fresh samples.
Process : The process is carried out in a special type of cell called electrodialysis cell. It
consists of two electrodes and ion selective membranes which are permeable to either cation
or anion. The anode is placed near anion selective membrane while the cathode is placed near
the cation selective membrane. Saline water under a pressure of around 5 - 6 kmlm 2 is passed
from the top of the cell and it passes between membrane pairs. (Fig. 8.13)
When an emf is applied across two electrodes the cations present in salt water move towards
cathode through cation selective membrane and anions move towards the anode through anion
selective membrane. As a result, the concentration of ions in alternate compartments 2, 4, 6
etc. decreases, while it increases in the alternate compartment 1, 3, 5 etc. Thus water
in the even number compartments becomes pure and is collected from the bottom of
the cell. Similarly water in the odd number compartments becomes rich in the saline salts
i.e., it becomes concentrated saline water. It is collected from a separate outlet at the bottom
of the cell.
Saline water
+
c A
Anion
Cation selective
selective membrane
membrane:;-.,.-tlf-.... ~~ (A)
(C)
Cathode Anode
Fig. 8.13. Electrodialysis of saline water.

Advantages
1. It is economical.
2. It is convenient and may be applied at room temperature.
3. It is most compact in size and requires only electricity for operating.
8.18.4 Reverse Osmosis
Principle: This technique is based on the principle of osmosis. When a semi permeable
membrane separates two solutions of different concentrations, the solvent moves from the
solution of lower concentration to that of higher concentration. The phenomenon is called
Osmosis and the driving force is called osmotic pressure. If pressure is applied to the
concentrated side, the solvent will flow in the reverse direction i.e., solvent passed from high
concentration to low concentration through semi-permeable membrane. This is called reverse
osmosis Fig. 8.14. The membrane is chosen in such a way that it allows only water to pass
though it and not the salt. Therefore, two streams are obtained, one of good water with lesser
salt content and other is brine solution.
P : Pressure applied 7t : Osmotic pressure

Fig. 8.14. Reverse osmosis process.
Process: The process is carried out in a reverse osmosis cell (Fig. 8.14). In this cell, sea
water to be desalined is separated from the fresh water through a semi permeable membrane.
It consists of very thin films of nylon or cellulose ~cetate supported between perforated plates.
Recently, superior membranes consisting of polymethylacrylate and polyamide polymers have
been used. A high pressure of 15--40 kg/cm2 is applied to the saline water. As a result of reverse
osmosis, fresh water moves down and can be collected from the outlet at the bottom of the
cell (Fig. 8.15).
Pressure ( ~ 15-40 kg cm-2)
Piston
:::::13ea water ::::::::

-----------------------
---- ------------------ Stout
semi-permeable
membrane
-+ Pure water outlet
Fig. 8.15.
Advantages
1. It is economical, compact and very simple.
2. Ionic, non ionic, colloidal and high molecular weight organic matters are easily removed
by this process. Colloidal silica is not removed by demineralization process.
3. It has long life and easy to replace the membrane within two minutes.
Comparison of Ele~trodialysis and Reverse Osmosis Process
The osmosis process is preferred to electrodialysis process because of the following
advantages:
(i) It removes ionic as well as non-ionic salts present in the s~ne water.
(ii) It is effective in removing colloidal matter also.
(iii) The installation and operating cost is comparatively low.
(iv), It is suitable for converting sea water into drinking water.
(v) The water obtained from the process can be used in high pressure boilers.
Although the electrodialysis process is very compact and its installation is economical, yet
it requires skilled labour for operation. It is suitable only if the electricity is available at cheaper
rates.
8.19 HAZARDOUS CHEMICALS
Toxic chemicals which adversely effect the health of human beings, fauna and flora are called
hazardous chemicals.
There are number of chemicals ,i n the environment, some of these are toxic and the rest
non-toxic. The toxic chemicals are discharged by industries. They get into the human food
chain from the environment. Once they enter our biological system, they disturb the bio-
chemical processes. The world produces chemicals faster than it can manage. These chemicals
include extremely toxic substances which can cause allergies, damage vital organs of the human
body like the eye, brain, liver, kidney and reproductive organs, produces deformities in babies
during pregnancies of mothers and promote cancer. In case of accidental release into the
environment in large quantities, as in case of Bhopal, they can lead to mass deaths.
Industries which produce potentially toxic and hazardous wastes are pesticides, dyes and
pigments, organic chemicals, fertilizers, non-ferrous metals, steel and alkali manufacturing
plants. The various toxic chemicals, their uses and hazards are listed in Table 8.1.
Table 8.2 : Toxic Chemicals-Uses and Hazards
Name Uses Hazards ..
1 2 3
Arsenic PesticideslUnani medicines/glass 'lbxicldermatitis/muscular

par~ysis/Damage to liver
and kidneylLoss of hair/
gangrene/cancer
Asbestos Rooting/insulation!Air-conditioning Carcinogenic to workers
roofsIPlastics!fibreipaper and family members
Benzene Gasoline additive!Manufacture of Leukemia/chromosome

many chemicals damage
Beryllium Aerospace industry/Ceramic parts! Fetal lung diseaselheart
House-hold appliances and lung toxicity
.
Cadmium Electroplating/plastics/pigments! Kidney damage/carcinogenic
superphosphate fertilisers
Chlorinated Organics Pesticides/fungicides NerVous depression/carcinogenic

(DDT, BHC, etc,)
1 2 3
Chromates Tanning/PaintslPigmentsl Skin ulcerslkidney inflammation!

Corrosion inhibitorslFungicides carcinogenic
Lead Pipes/storage batteries/ Neurotoxinlblood system
paints/printing/plastics/ and brain damage
gasoline additive
Manganese Mining/welding/dry cell batteryI Nerve damage/damage to
ferromanganese material reproductive system
(alloy)
Mercury Chloralkali cellS/fungicides/ Nerve damagelk.idney damage!
Pharmaceuticals fatal effect of alkyl mercury
Polychlorobiphenyls (PCB) Transformers/insulation of Carcinogenic/nerve, skin

electricity and liver damage
Sulphur dioxide Sugar industry Irritation to eyes and Respiratory
system/damage to plants/damage
to marble structures, monuments,
etc.
Urea Fertiliser Bronchial problemslkidney damage
Vinyl chloride Plastics/organic synthesis 'lbxic/carcinogenic
Very few people have paid any attention to the dark side of industralisation,
particularly to the growing dangers it pores to the health of people. Industrialization is
creating a highly risky environment for all. But it is the poor labourers/workers, who suffer the
most. They are compelled to live in the dirtiest and toxic environment to earn their livelihood.
S.19.l Classification
Hazardous substances may be classified according to their function and effects, such as
mutagens, carcinogens, etc., or food additions., etc., or heavy metals, metal carbonyls, organo-
chlorine compounds etc.
(i)Toxic Elements in water: A list of toxic trace elements found in natural waters and
waste waters is tabulated below. Some of these elements are essential at low levels, but are
toxic at higher levels.
Table 8.3. Toxic Trace Elements in Natural Water and Waste Water
Elements Sources Effects and significance
1 2 3
Arsenic Mining by product, pesticides, Toxic and carcinogenic
chemical waste
Cadmium Industrial discharge, mining Replaces zinc biochemcially, causes
waste, metal plating, water high blood pressure, kidney damage,
pipes destruction of testicular tissue and
red blood cells, toxicity to aquatic
biota
1 2 3
Beryllium Coal, nuclear power and Acute and chronic toxicity, possibly
space industries carcinogenic
Boron Coal, detergent formulations, Thxic to some plants
industrial wastes
Chromium Metal plating cooling tower Essential trace elements; possibly
water additive. (chromate) carcinogenic as Cr (VI)
normally founds as Cr M)
polluted water
Copper Metal plating, industrial and Essential trace elements, not very
domestic waste, mining, toxic to animals, toxic to plants and
mineral leaching algae at moderate levels
Fluorine (Fluoride ion) Natural geological sources, Prevents tooth decay at about
industrial waste, water 1 mg/l, causes mottled teeth and
additive bone damage at about 5 mg/L
Lead Industry, mining, plumbing, Toxic (anaemia, kidney disease,
coal, gasoline nervous disorder), wild-life
destroyed
Manganese Mining industrial waste, acid Relatively non-toxic to animals, toxic
mine drainage, microbial to plants at higher levels, stains
action on manganese materials (both-room fixtures
minerals at low potential enerty and clothing
(pE)
Mercury Industrial waste, mining, Highly toxic
pesticides, coal
Molybdenum Industrial waste, natural Possibly toxic to animals, essential
sources for plants
Selenium Natural geological sources, Essential at low-levels but toxic at
sulphur, coal higher levels
Zinc Industrial waste, metal Essential in many metalloenzymes,
plating, plumbing toxic to plants at higher levels
(ii) Pesticides and insecticides in water: The water bodies contain a large number of
pesticides, prim,arily from the drainage of agricultural load. These pesticides belong to two
major groups of chlorinated hydrocarbons and organic phosphates, the latter group being more
biodegradable. In general, toxic chemical attack the sites of enzymes and inhibiting essential
enzyme function. Arsenic commonly occurs in insecticides, fungicides. Among its compounds
those of As (III) are the most toxic. Among the pesticides, the biological action of DPT on the
environment is more toxic.
'(iii) Carcinogens: The term carcinogens means a group of chemicals which cause cancer
in animals and humans. The carcinogers affect DNA. Table 8.3 gives a list of carcinogens to
which workers most not be exposed.
Table 8.4. Carcinogens to which workers should not be exposed
Compounds Uses Hazards
4-nitrophenlyl Chemical analysis May cause bladder cancer

Alpha-naphthylamine Ani-oxidant, dye manufacture, May cause bladder cancer
colour film manufacture
4,4-methylenebis Plastic curing agent May cause bladder cancer
(2-chloroaniline)
Methyl-chloromethylether Ion-exchange resin manufacture Usually contaminated with
carcinogenic bis (chloromthyl)
ether
3,3-dichlorobenzidine Dye manufacture Known carcinogen
Bis (Chloromethyl) ether Ion-exchange resin manu- Causes lung cancer
facture
Beta-naphthylamine Dye manufacture, reagent Causes bladder cancer
Benzidine Manufacture of dyes, rubber, Causes bladder cancer
plastics, printing ink
Ethyleneimine Paper and textile treating Known carcinogen suspected
Beta-propiolactone plastics manufacture human carcinogen
Vinyl chloride Polyvinyl chloride plastics Causes liver cancer
(PVC) manufacture
Ethylene dichloride Industrial solvent, grain fumigant Causes stomach, spleen,
and gasoline additive for lead lung cancer
scavenging-74 x 106 kg are
lost to environment each year
Besides, the above chemicals, polycyclic, aromatic hydrocarbons deserve special attention.
Typical examples are benzo (0.-) pyrene and chrysene.
Benzo (a-) Pyre~e Chrysene

All professional chemicals are required to possess a basic concept of chemical toxicology
and remain fully conscious of the chemical hazards of toxic chemicals.
8.19.2 Various Chemical Substances Present in Water Affecting Health
m Ammonia <NlIa>
Nitrogen is present in water in the form of ammonia, nitrites and nitrates. The presence
of these substances in water indicates the presence of organic contamination. Free ammonia
is formed as an initial product of decomposition of nitrogenous organic matter. The quantity
ofNHa in potable water should not be greater than 0.15 ppm.
(ii) Nitrate and Nitrite (NO-s & NO-2 )
Nitrites are the products obtained by oxidation of ammonia. Nitrites should never be present
in potable water. Nitrates are the end products of decomposition of organic matter and indicate
that the organic matter present in water is fully oxidised. The presence ofN0 3- in water causes
a child diseases known as methenoglopinemia. The permissible limit of N0 3- in drinking water
is 10 mg litre. Waters from chemical fertilizers manufacturing plants also contributes nitrates
in water.
(iii) Cyanide (CN-)
Free cyanide is a toxic and hazardous water pollutant, which usually comes in water
bodies form metal refining and cleansing, coke oven, electroplating and various industrial
processes.
(iv) Sulphate (S()2-4)
Sulphate usually occurs in natural waters. Mine drainage waters also contain high content
of sulphate. The excess of sulphate in drinking water may cause cathartic action.
(v) Sulphide (S2-)
Sulphide is generally present in ground water, .e.g, in hot springs and also in common
waste waters coming from decomposition of organic matter from industrial wastes or from
reaction of sulphides.
(vi) Fluoride (F")
Fluoride occurs in all natural water. It is found that if fluoride concentration in water is
slightly greater than 1 ppm may cause reduction in the cavities of teeth of young children.
Excessive fluorides in drinking water may cause mottling of teeth or dental fluorosis, which
results in discolouration of enamel, chipping of teeth in children in severe cases. Bone fluorosis
or cropping effects are observed in case of conceenetration of fluorides exceeds 1. 0 mgll.
(vii) Cadmium (Cd2+)
Industrial effects and wastes from textiles, printing, electroplating, chemical industries and
lead mines contribute cadmium in water. The WHO European standard for cadmium in water
is 0.05 mglL Cadmium is highly toxic and its traces are responsible for adverse renal arterial
changes in kidney in man.
(viii) Copper (Cu+ & Cu2+)
Copper rarely occur in natural water. Copper salts (0.1 to 0.5 mglL) are toxic to micro-
organism and such concentration affect the self purification of streams and causes fall in BOD
with in five days. It also causes fishy, fatty and oily tastes in milk.
(Lx) Arsenic (Ass+)
Arsenic occur in water as a result of industrial discharges, mineral dissociation or due to
application of pesticides. It is extremely toxic in drinking water. WHO prescribed the maximum
permissible limit of 0.05 mglL. It exhibit carcinogenic properties.
(x) Lead (Pb2+ & Pb4+)
Mine water, electroplating wastes, lead paint wastes, corrosion products and waste
contributes lead to raw water supplies. It is also a carcinogenic agent. Hence its determination
in water sample is very important.
(xi) Mercury (Hg+ & Hg2+)
Mercury enters into water system through agricultural pesticides, fungicides pigments,
disinfectants and medical products. Mercury compounds are highly toxic to man, animals and
plants. Excess of mercury cause brain and kidney damage and loss of muscle control. There
should be 0.001 mg/L Hg in drinking water.
(xii) Detergents
Most of the syndets contain anionic surfactants which produce surface active agents in
water. The limiting concentration of surfactants is 0.5 mg/L in drinking water. Small
concentration produce unpleasant taste. Aquatic plants and animals are adversely affected by
surfactants. They produce foams and reduce the efficiency of sewage purification.
(xiii) Phenols
Phenols and phenolic compounds do not occur in natural waters. But these are the common
pollutants in industrial waste water from oil refineries, coke-oven and coal-distillation plants.
The permissible limit in 0.001 mglL phenol in drinking water. It impart a characteristics odour
and taste to water. It can be removed by super chlorination, activated carbon adsorption and
chlorine ammonia treatment.
( NUMERICAL PROBLEMS FOR PRACTICE)
I. Based on Units of Hardness

1. A water sample contains 180 mg of MgS0 4 per litre. Calculate the hardness in terms
of CaCO s equivalent. [Ans. 150 ppm]
2
2. A sample of irrigation water sample contains 104 mg of Ca + per litre. Calculate the
hardness of water in terms of CaCO s equivalent. [Ans. 260 ppm]
3. A sample of irrigation water contains 16.8 mglL of Mg(HCOS)2' 20 mg/L of MgC12, 25
mglL of CaCI2. Calculate the total hardness in terms of CaCO s equivalent.
[Ans. 53.41 mg/L]
4. A sample of water on analysis has been found to contain following in ppm:
Ca(HCOS)2 = 10.5, Mg(HCOS)2 = 12.5,
Ca~ = 8.2, caS04 = 7.5, MgS04 =2.6
Calculate the temporary and permanent hardness in degree French.
[Ans. Temporary hardness 1.504°Fr Permanent hardness 1. 509 °Fr]
5.. 400 ml of a water sample contains 3.01 mg of CaS04 , 2.0 mg of MgC~ and 3.5 mg of
Ca(HCO S)2' Calculate the total hardness in terms of Clark's degree. [ADs. 1. 13°CI]
6. Calculate the hardness of wate:y; containing the following dissolved salts:
caS04 = 28 mg/L, Mg(HCOS)2 = 22 mg/L,
MgC~ = 30 mg/L, CaC~ = 85 mg/L.
7. A water sample contain Ca(HCO S)2 =32.4 mg/L, Mg(HCOS)2 =29.2 mg/L and CaS04 =
13.5 mg/L. Calculate temporary and permanent hardness. [Ans. 40 ppm, 10 ppm]
n. Based on Hardness Determination Methods
A O. Hehner's Method
8. 100 ml of water sample require 30 ml of ~ HCI using methyl orange indicator for
end point while the same volume after boili:~requires 20 ml of the same acid. Calculate
the temporary hardness of water. [Ans. 100 ppm]
9. 100 ml of water sample is boiled for half an hour with 20 ml of ~ NaCO a. Now it is
N 50
titrated against 50 HCI. Calculate the permanent hardness of water. [Ans. 800 ppm)
B. Soap Titration Method
10. 50 ml of water sample was titrated against soap solution gave the following data':
(i) Lather factor =0.5 ml soap solution.
(ii) Total hardness =15.5 ml soap solution.
(iii)Permanent hardness =12.5 ml soap solution.
(iu) Standard hard water (0.2 g ofCaCO a per litre) =40.5 ml soap solution.
Calculate total hardness, permanent hardness and temporary hardness of water.
[Ans. Total hardness 150 ppm
Permanent hardness = 120 ppm
Temporary hardness = 30 ppm]
n. Calculate temporary and permanent hardness of water during soap titration method,
when 50 ml of water is titrated with soap solution gave the following datas :
Lather factor 0.3 ml soap solution; total hardness = 9.3 ml soap solution; permanent
hardness = 3.1 ml soap solution; standard hard water (200 mg/L ofCaCOa) = 18.3 ml.
[Ans. Temporary hardness 68.2 ppm
Permanent hardness 30.8 ppm]
12. 40 ml of standard hard water (containing 1.5 g CaCOa per litre) required 50 ml of soap
solution for permanent lather formation. 100 ml of water sample required 20 ml of
soap solution while same volume of water after boiling required 15 ml of soap solution.
If the lather factor is zero then calculate the temporary and permanent hardness of
water. [Ans. Temporary hardness =60 ppm
Permanent hardness = 180 ppm]
13. 50 ml of standard hard water (containing 0.1 g CaCO a per litre) required 60.5 ml of
soap solution for end point whereas 50 ml of pure distilled water (in which soap solution
is prepared) required only 0.5 ml of soap solution for end point. 100 ml of water sample
required 30.5 ml of soap solution while same volume of water after boiling required
10.5 ml of soap solution. Calculate temporary and permanent hardness of water.
[Ans. Temporary hardness =166.6 ppm
Permanent hardness = 83.4 ppm]
C. EDTA Titration Method
14. 50 ml of SHW containing 1 mg of pure CaCO a per ml consumed 20 ml of EDTA. 50 ml
of water sample consumed 25 ml of same EDTA solution using Eriochrome black-T
indicator. Calculate the total hardness of water sample. [Ans. 1250 ppm]
15. 1 g of CaCO a was dissolved in dil HCI and the solution diluted of 1 litre. 50 ml of this
solution required 45 ml of EDTA solution. 50 ml of hard water required 18 ml of EDTA
solution during titration in ammonia buffer using EBT indicator. On the other hand,
50 ml of boiled water sample required 9 ml of EDTA solution under same condition.
Calculate each type of hardness in ppm.
[Ans. 'lbtal hardness =400 ppm, Permanent hardness =200 ppm, Temporary hardness
=200 ppm]
16. 0.30 g of CaCO g was dissolved in HCI and the solution made upto 1 litre with distilled
water. 100 ml of the above solution required 30 ml of EDTA solution on titration. 100
ml of hard water sample required 35 m1 of same EDTAsolution on titration. After boiling
100 ml of this water, cooling, filtering and then titration required 20 ml of EDTA
solution. Calculate the temporary and permanent hardness of water.
[Ans. 'lbtal hardness = 350 ppm, Permanent hardness = 200 ppm, Temporary hardness
= 150 ppm]
17. 0.28 g of CaCO g was dissolved in HCI and the solution made upto 1 litre with distilled
water. 100 ml of the above solution required 28 ml of EDTA solution on titration. 100
ml of a hard water sample required 33 ml of the same EDTA solution on titration.
Mter boiling 100 ml ofthis water, cooling and filtering and then titrated 10 ml of EDTA
solution. Calculate the temporary and permanent hardness. [Ans. 230 mglL, 100 mglL]
18. 100 ml of water sample required 25 ml ofMJI00 EDTA with NH 4 CI-NH4 0H buffer and
EBT indicator. Another 100 ml of the sample is boiled for about half an hour and after
filtering the precipitate, the volume of the filtrate is made up to 100 ml again by adding
distilled water. 20 ml of the boiled sample require only 4 ml of MJ100 EDTA following
the same procedure. Calculate the temporary and permanent hardness.
[Ans. 50 ppm, 200 ppm]
19. ·10 ml of standard hard water (1 ml of it = 1 mg of CaCO g) in presence of ammonical
buffer solutionlEriochrome black-T indicator consumes 13.8 ml of EDTA solution. 50
ml of a given hard water sample under the similar experimental conditions, consumes
25 ml of the same EDTA solution. 50 ml of the given hard water sample upon boiling,
cooling, filtering etc. consumes 10 ml of same EDTA solution. Calculate the various
types of hardness in terms of ppm as CaCOg equivalents. (K.U.K. Jan., 2005)
[Ans. 'lbtal hardness = 362.31 ppm, Permanent hardness = 144.92 ppm, Temporary
hardness =217.39 ppm]
III. Based on Alkalinity
20. 100 ml of water sample on titration with phenolphthalein indicator require 5 ml of
0.02 N H 2S04 , Another 100 ml of the water sample when titrated with methyl orange
end point require 5 ml of 0.02 N H 2S04 , What type of alkalinity is present in sample
and what is its magnitude? [Ans. OH- =50 ppm]
21. A sample of water was alkaline both to pehnolphthalein end methyl orange. 50 ml of
N
this water sample required 15 ml of 50 sulphuric ~cid for phenophthalein end point
and another 10 ml for complete neutralisation. Calculate the type and amount of
alkalinity in ppm. [ADs. OH- =100 ppm, COgz- =400 ppm]
N .
22. 100 ml of a water sample require 20 ml of 50 sulphuric acid for neutralization to
phenolphthalein end point. After this methyl orange indicator was added to this and
further acid required was again 20 ml. Calculate the alkalinity of water as CaCOg in
ppm. [Ans. COg2- =400 ppm]
N
23. 50 ml of alkaline water sample required 20 ml 50 sulphuric acid for phenolphthalein
876 EBSentiaZs ofEngineering Chem.istry
end point and another 5 ml for methyl orange indicator i.e., complete neutralization.
Describe about the type and magnitude of alkalinity.
=
[Ans. OH- = 300 ppm, 0082- 200 ppm]
N
24. 100 ml of water sample required 4 ml of 50 H 2S04 for neutralization to phenalphthalein
end-point. Another 16 ml of the same acid was needed for further titration to methyl
orange end point. Detern-.ine the type and amount of alkalinity. (K. U. Jan. 2004)
[Ans. C032- 80 ppm, HC03-120 ppm]
25. 100 ml of an alkaline water in presence of phenolphthalein indicator consumes 50 ml
of ~ HCI. The resulting mixture in presence of methyl orange indicator consumes
100
35 ml of same HCI. Predict the alkalinities and calculate their amounts in ppm as CaC0 3
equivalents. (K. U.K. Jan. 2005)
[Ans. OH- = 75 ppm, C0 32- 350 ppm]
26. A water sample responds to methyl orange but not to phenolphtalein. 50 ml of the
N
above water sample completely neutralizes 20 rnl of 50 HCl. Calculate the amount in
ppm as CaC03 equivalents of the alkalinity present in the sample. (K.U.K. June 2005)
[Ans. HC0 3- =400 ppm]
. ( REVISION QUESTIONS)
1. What are the sources of water in nature ? Name the purest and the most impure
source.
2. Classify the common impurities in natural waters.
3. What is meant by hardness of water? What are the common units of measurement
of hardness of water? Give relationship between various units.
(RGT, May 01; Dibrugarh Dec. 2K.U. 2005)
4. (a) Differentiate between hard water and soft water. (KU, May 99)
(b) Hard water does not lather with soap. Explain. (KU, May 99)
(c) Distinguish between carbonate and non-carbonate hardness of water with
examples. . (Anna, July 2K, Jan. 01)
(d) Why does hard water consumes a lot of soap? (UPT, Jan. 01)
(e) Explain the causes of hardness of water. (RGT, July 01)
5. (a) Write short notes on (i) Electrodialysis (U) Reverse osmosis
(Andhra, June 01; Anna July 2K)
(b) What is desalination? Name the different methods of desalination. Explain any
one in detail. (Madras, Oct. 97; Mangalore, Oct. 97)
6. Give reasons:
(a) What is sterilization of water? Name three substances for sterilization of
water.
(b) Why do we add buffer solution during titration of hard water against EDTA
solution? Name acidic and basic buffers.
(c) What is reverse osmdsis ? What are its applications?
(d) What are flocculants ? What happens when alum is dissolved in water?
7. (a) Distinguish between carbonate and non-carbonate hardness of water with example.
(b) Name anyone coagulant used to remove the turbidity of water.
(c) What is demineralised water? How is it different from soft water?
(Anna, July 2000, Jan. 2001)
8. (a) State the various methods of disinfection.
(b) What is break point chlorination? Explain showing different zones. What are the
advantages of break point chlorination? (Anna, July 2000, Jan. 2001)
(c) Write a short note on reverse osmosis? (Anna, July 2000)
9. Define BOD. How will you determine it?
10. Define COD. What is the importance of COD ?
11. (a) Which bacteria are present in high quantities in sewage waste?
(b) Write a short note on secondary treatment of sewage waste by trickling filter?
(c) What is primary treatment. Write its importance?
12. (a) Discuss about the activated sludge process?
(b) What is tertiary treatment? Discuss about the phosphorous removal by tertiary
treatment?
13. (a) Write a short note on chlorination of sewage waste ?
(b) Which method is more convenient for the sewage treatment in India?
(c) How do you remove the nitrogen impurities from sewage waste?
14. What do you understand by Multiple Effect Evaporation? Explain this process with
the help of a diagram.
15. What are hazardous chemicals ? Name ten hazardous chemicals polluting the
environment.
16. Classify hazardous chemicals giving examples of each class. Name five chemicals
present in water which are affecting oour health.
17. (a) 100 ml of a water sample required 4 ml of N/50 H 2S0 4 for neutralization to
phenolphthalein end-point. Another 16ml of the same acid was needed for
further titration to Methyl orange end-point. Determine the type and amount of
Alkalinity.
(b) How is permanent hardness of water determined? (KU, Dec. 2003)
18. (a) Describe in detail the Elctrodialysis process for desalination of Brackish water.
(b) What are water pollutants? How are they classified? Give examples.
(KU, Dec. 2004)
19. (a) Define alkalinity. How is it determined?
(b) With the help of a neat diagram, explain the use of electrodialysis for desalination
of water.
(c) Name eight disinfectants of water. (KU, June 2004)
20. (a) What are complexometric titrations ? Name the indicator used in the
determination of hardness of water.
(b) Why are the results of alkalinity and the hardness mostly expressed in terms of
CaCOa equivalents ?
(c) Why the combination of hydroxide and bicarbonate alkalinities is not possible
occurring together?
(d) A water sample is alkaline both to phenolphthalein and methyl orange. 50 ml of
the water sample requires 20 ml of N/50 H 2S04 upto phenolphthalein end point
and another 5 ml for complete neutralization. Describe the types and amounts of
the alkalinities present as CaCOg equivalents.
(e) 50 ml of a given water sample consumed 15 ml of 0.01 M EDTA solution before
boiling and 5 ml of the same EDTA solution after boiling. Calculate the various
,types of hardness in ppm as CaCOa equivalents. (KU, Jan. 2005)
21. (a) Distinguish between softening and demineralization of water.
(b) Differentiate among pure water, hard water, heavy water and boiler feed water.
(c) Draw a neat, labeled sketch of electro dialyzer. Explain its working.
(d) Write the structural formulae of EDTA and the indicator used in EDTA titrations.
(KU, Jan. 2005).
22. (a) Define the term hardness. From where is it introduced in the water? Describe a
suitable method for the determination of hardness.
(b) Comment on the statement "Distilled water containing sodium bicarbonate
exhibits only alkalinity, whereas aquesous solution of calcium bicarbonate imparts
both alkalinity and the hardness."
(c) A water sample responds to methyl orange but not to phenolphthalein. 50ml of
the above water sample completely neutralizes 20ml ofN/50 HCl. Calculate the
amount in ppm as CaCOa equivalents of the alkalinity present in the sample.
(Irn, June 2005)
23. (a) Describe the following: hard water, heavy water and boiler feed water.
(b) What do you mean by coagulants and the disinfectants? Name a chemical
compound which behaves both as coagulant as well as disinfectants.
(KU, June 2005)
24. Describe EDTAMethod for the estimation of hardness of water. (KU,2005)
25. (a) Explain the term COD of an Industrial waste water, give an account of acid rain.
(Y.T.U. B.E., August, 1999)

(b) Explan the term BOD and COD. (Y.T.U. B.E., August, 2001)
26. (a) Explain BOD and COD. Why is COD generally higher thab BOD?
(b) 25 ccj of an industrial efficient requires 12.5 cc of 0.5 N ~Cr207 for complete
oxidation. Calculate COD of the sample. Assuming that the effluents contains only
oxilic acid, calculate the amount of oxalic acid present per litre. Take equivalent
weight of oxalic acid is 63. CY.T.U. RE., August, 2002)
27. (a) what are the sources and will effect of lead, cadmium and mercury as pollutants
in water.
(b) 25 cm3 of an industrial effluent consued 5 cm 3 of 0.5 N ~Cr207 solution for
oxidation. Calculate the COD of the effiuent. ey.T.U. B.E., Jan./Feb. 2003)
28. 25 cm of an industrial effiuent when subjected to COD test required 22.5 cm2 of 0.50
3
N ~Cr207 for complete oxidation. Calculate COD ofthe effluent sample.

ey.T.U. B.E., July/Aug. 2004)
29. Calculate the COD of the effiuent sample when 2cm3 of the effiuent requires 10.5
cm 3 of 0.005 M ~Cr207' for complete oxidation. CY.T.U. B.E., Feb.lMarch 2005)

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ESSENTIALS OF

Dr. (Mrs.) Vijay Sharma

Published by Mrs. Meena Pandey

Nagpur Kundanlal Chandak Industrial Estate

Bangalore No. 16/1 (old 12/1), 1st floor,

Hyderabad No. 2-2-1167/2H, 1st Floor,

Typsetat Stylish Laser Typesetter, Delhi-l10053

Printed at New Offset Printers, New Delhi-110002

1. Chemical Energy Sources ............................................................................ 1

lA. Solar Energy .................................................................................................. 40

2. Electrochemical Energy Systems (Electrode Potential and Cells) .......... . 59

4. Corrosion Science ........................................................................................ 134

5. Metal Finishing .............................................................................................. 166

GA. Liquid Crystals and Their Applications'...................................................... 194

7. High Polymers ............................................................................................... 239

8. Water Technology ......................................................................................... 312

1. Gaseous hydrocarbons 100 to 300 As fuel gas, manufacture of

(i) Petroleum ether C5-C7 3004345 As solvent in varnish and rubber

lA.4.1 Some Important Hydrocarbon Fuels from ,~etroleum

1. Define a chemical fuel.

1. A combustible substance containing carbon as the main constituent, which an

'p'" Copper calorimeter

:. Wt. of water produced from 1 gm of fuel = -9H gm = 0.09 H gm.

(W -w)(t2 -t1 + cooling correction)-(Acid + fuse wire correction)

Corrected formula: Grass C.V. = (W -w ) <! 2 -( 1 +() - (a + f) CaVgm

LCV = [HCV - 1 ~O H x587 ] k callkg = [HCV - 0.09 H x 587] k callkg

Examples 1 : On burning 0.83 g of a solid fuel in a bomb calorimeter, the temperature of

= 1~O[8,080XC+34,500( H- ~)+2,240XS ]kCal/kg

= l~O [8,080X85+34,SOO( 8- ~ )+2,240XI] kcal/kg

L.C.V. = (W +w )(12 -I) = (2490 +386)(2.592) = 7 484 call

(2560 + 440)(2.42 + 0.0552) + 10 (3000 x 2.472) -I 0

Grass calorific value (GCV) = I~O [8080 C+34500( H - ~ )+22405] kcal/kg.

GCV = 1~0[8.080 x 80+34,500( 7-i)+2,240X3.5] kcaJ/kg.

( PRACTICE PROBLEMS FOR TUTORIALS)

The nature of products formed depend on the following:

Pre-heater Catalyst Fractionating Gasoline

Fig. 1.S. Fluidized catalytic cracking.

Process Thmperature Pressure Quality of Compositions

(i) H3C-CH2-CH2-CH2-CH3 ~ H3C-CH-CH2-CH3

(ii) Isomerisation of ethyl cyclopentane to methyl cyclohexane (aromatisation)

(b) Cyclisation and isomerization (n-heptane to methyl cyclo hexane)

(ii) Dehydroisomerisation of cyclopentane homologues, e.g. I, 2 dimethyl

1,2 dimethyl cyc\opentane Toluene

Paste of Coal Powder + H2 catalyst) Petroleum like product in heavy oil

Fig. 1.5. Synthetic petroleum from Coal by Bergius process.

( PRACTICE PROBLEMS FOR TUTORIALS)

1. What is meant by the term cracking?

Renewable Food Renewable

Fig. 1.1. Sun as the ultimate energy source.

Note: Nuclear fission power is a non-renewable source of energy.

- 0.2 J.lm "'--.--L

P-silicon Metal electrode

where h = Planck's consta It = 6.62 x 10-27 erg-s

Front side rti, t I---

Fig. 1.10. Principle of Working of a Solar Cell.

'"The excess energy (E - Eg) is lost as heat.

Fig. 1.13. A Phot()\'(J\talc Water-pumping System.

........Is;\.~ ...............\).~.~ ......... ····.·0·.... ·

··_-·,·Y ... ~- .. -............... y. . ........... ....... y. ..:....... .

where n;O) is the electric density in conduction band.

and n~O) is the hole density in the valence band.

. --. !,.:' ................ \ ••: .............. ~•• : .................. !, ••:,.,---....

~l' ............. ~.0. ............ ~.t;,Y.-