Applied Chemistry

About the Author

Dr. P. N. Palanisamy is the Professor & Head, Department of Chemistry,
Kongu Engineering College, Perundurai, Erode. He obtained his
[Link] Degree from Gandhigram Rural University and [Link] Organic
Chemistry from Annamalai University. He obtained his Ph.D from
Annamalai University during May 1996 in the field of Catalysis. He has
16 years of teaching experience. He has published 56 research papers
in reputed journals and presented more than 50 papers in national and
international conferences. He is the life member of Indian Council of
Chemists and life member and executive/advisory/Editorial board
member of Asian Journal of Experimental chemistry. His field of interest
includes the catalysis and environmental chemistry. He has completed
one major research project funded by UGC. Four [Link] and two Ph.D
scholars have completed their degree under his guidance. Presently,
eight Ph.D scholars are pursuing their research under him in the field
of Environmental Chemistry.
A. Geetha is working as an Assistant Professor in the Department of
Chemistry, Kongu Engineering College, Perundurai, Erode. She has
completed her undergraduate degree at Vellalar College for Women,
Erode during the year 2000 and post graduate degree at P.S.G.C.A.S,
Coimbatore during the year 2002. She obtained her [Link] degree from
Bharathiar University, Coimbatore during the year 2004. She has 7 years
of teaching experience. At present, she is pursuing research in the field
of Environmental chemistry. She has published 6 research papers in
international journals and also presented many papers in national and
international conferences.
K. Manjula Rani is working as an Assistant Professor in the Department
of Chemistry, Kongu Engineering College, Perundurai, Erode. She has
completed her undergraduate degree at [Link] for Women,
Palani and post graduate degree at P.S.G.C.A.S, Coimbatore. She
obtained her [Link] degree from Bharathiar University, Coimbatore
during the year 1996. She has 15 years of experience in academics. At
present, she is pursuing research in the field of pollution abatement
using Nanomaterials. She has presented few research papers in various
national conferences.
 Applied Chemistry

P N Palanisamy
Head, Department of Chemistry
Kongu Engineering College
Erode, Tamil Nadu
A Geetha
Assistant Professor, Department of Chemistry
Kongu Engineering College
Erode, Tamil Nadu
K Manjula Rani
Assistant Professor, Department of Chemistry
Kongu Engineering College
Erode, Tamil Nadu

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 Preface
Applied Chemistry aims to address the needs of the first-year BE/
BTech engineering students. This book deals with the essential and
basic concepts of chemistry, as outlined in the first-year syllabi of an
engineering course. Written in a very simple and easily understandable
manner, it helps even the average student grasp the subject matter very
easily.
The unique features of this book are the following:
• Complete syllabus coverage
• Relevant and important topical examples in each unit
• Easy understandable diagrams, equations and problems
• Rich pedagogy
• 75 Exercise Questions
• 81 Illustrations
• 90 Short-Answer Questions
The content is spread over five units.
• Unit 1 covers Water. It contains topics on Sources of Water,
Impurities in Water, Types of Water, Water-Quality Standards,
Water-Quality Parameters, Hardness of Water, Boilers, Boiler
Troubles Due to Hard Water, Water-Softening Methods, External
Treatment, Internal Conditioning (or) Internal Treatment (or) Boiler
Compounds, Desalination of Brackish Water, and Drinking Water
(or) Potable Water (or) Domestic Water Treatment.
• Unit 2 presents Electrochemistry. It deals with Cells, Representation
of a Galvanic Cell, Reversible and Irreversible Cells, Emf of an
Electrochemical Cell, Weston Standard Cadmium Cell, Electrode
Potential, Determination of Electrode Potential—Nernst Equation,
Reference Electrodes, Types of Electrodes, Electrochemical Series
or Emf Series—Importance of Electrode Potential, Potentiometric
Titration, Conductometric Titrations, Batteries, Lead Accumulator
or Acid Storage Cell, Nickel–Cadmium Batteries (NICAD), Lithium
Battery, Fuel Cells, and Solar Energy.
 • Unit 3 covers Corrosion and its Control Methods. It presents
the topics of Classification of Corrosion, Types of Electrochemical
Corrosion, Galvanic Series, Factors Influencing Rate of Corrosion,
Corrosion-Control Methods, Protective Coatings, Pre-Treatment of
Metal Surface or Preparation of Material for Coating, Electroplating
or Electrodeposition, Electroless Plating, Surface-Conversion
Coating, Anodized Coating, Hot Dipping, and Paints.
• Unit 4 deals with Fuels. It outlines Classification of Fuels,
Combustion, Theoretical Calculation of Minimum Air Required
for Combustion, Flue-Gas Analysis [Orsat’s Method], Important
Terms Related to Combustion, Solid Fuels, Metallurgical Coke,
Liquid Fuels, Gaseous Fuels, and Determination of Calorific Value
by Bomb Calorimeter.
• Unit 5 presents High Polymers. It covers Polymerization,
Nomenclature of Polymers, Functionality, Types of Polymerization,
Effect of Polymer Structure on Properties, Plastics, Individual
Polymers, Conducting Polymers, Polymer Blends and Alloys,
Compounding of Plastics, Fabrication of Plastics, Foamed Plastics,
Rubber or Elastomers, and Composites.
Apart from these, to help students perform better in examinations,
a collection of two-mark and ten-mark important questions is given
towards the end. We encourage the student community and the teaching
fraternity associated with the contents of this book to make use of it and
benefit themselves.
Suggestions and criticisms from the reader will always be welcome.

P N Palanisamy
A Geetha
K Manjula Rani
Publisher’s Note
Remember to write to us. We look forward to receiving your feedback,
comments and ideas to enhance the quality of this book. You can reach
us at [Link]@[Link]. Please mention the title and author’s
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 Contents
Preface v
1. WATER 1.1–1.65
1.1 Introduction 1.1
1.2 Sources of Water 1.1
1.3 Impurities in Water 1.2
1.4 Types of Water 1.3
1.5 Water-quality Standards 1.4
1.6 Water-quality Parameters 1.5
1.7 Hardness of Water 1.14
1.8 Boilers 1.27
1.9 Boiler Troubles Due to Hard Water 1.28
1.10 Water-softening Methods 1.35
1.11 External Treatment 1.36
1.12 Internal Conditioning (or) Internal Treatment (or)
Boiler Compounds 1.50
1.13 Desalination of Brackish Water 1.52
1.14 Drinking Water (or) Potable Water (or) Domestic
Water Treatment 1.56
Questions 1.62
2. ELECTROCHEMISTRY 2.1–2.61
2.1 Introduction 2.1
2.2 Cells 2.2
2.3 Representation of a Galvanic Cell 2.5
2.4 Reversible and Irreversible Cells 2.6
2.5 Emf of an Electrochemical Cell 2.9
2.6 Weston Standard Cadmium Cell 2.13
2.7 Electrode Potential 2.14
2.8 Determination of Electrode Potential—Nernst
Equation 2.18
2.9 Reference Electrodes 2.24
 2.10 Types of Electrodes 2.29
2.11 Electrochemical Series or EMF Series —Importance
of Electrode Potential 2.34
2.12 Potentiometric Titration 2.39
2.13 Conductometric Titrations 2.43
2.14 Batteries 2.46
2.15 Lead Accumulator or Acid Storage Cell 2.47
2.16 Nickel– Cadmium Batteries (NICAD) 2.49
2.17 Lithium Battery—The Battery of the Future 2.50
2.18 Fuel Cells 2.52
2.19 Solar Energy 2.55
Questions 2.56
3. CORROSION AND ITS CONTROL METHODS 3.1–3.47
3.1 Introduction 3.1
3.2 Classification of Corrosion 3.2
3.3 Types of Electrochemical Corrosion 3.9
3.4 Galvanic Series 3.15
3.5 Factors Influencing Rate of Corrosion 3.17
3.6 Corrosion-Control Methods 3.19
3.7 Protective Coatings 3.25
3.8 Pre-treatment of Metal Surface or Preparation
of Material for Coating 3.26
3.9 Electroplating or Electrodeposition 3.27
3.10 Electroless Plating 3.30
3.11 Surface-conversion Coating 3.33
3.12 Anodized Coating 3.34
3.13 Hot Dipping 3.35
3.14 Paints 3.38
Questions 343
4. FUELS 4.1–4.65
4.1 Introduction 4.1
4.2 Classification of Fuels 4.2
4.3 Combustion 4.4
4.4 Theoretical Calculation of Minimum Air Required
for Combustion 4.10
4.5 Flue-Gas Analysis [Orsat’s Method] 4.13
4.6 Important Terms Related to Combustion 4.15
4.7 Solid Fuels 4.16
4.8 Metallurgical Coke 4.24
 4.9 Liquid Fuels 4.27
4.10 Gaseous Fuels 4.43
4.11 Determination of Calorific Value by
Bomb Calorimeter 4.50
Questions 4.62
5. HIGH POLYMERS 5.1–5.53
5.1 Introduction 5.1
5.2 Polymerization 5.2
5.3 Nomenclature of Polymers 5.2
5.4 Functionality 5.6
5.5 Types of Polymerization 5.7
5.6 Effect of Polymer Structure on Properties 5.14
5.7 Plastics 5.18
5.8 Individual Polymers 5.20
5.9 Conducting Polymers 5.32
5.10 Polymer Blends and Alloys 5.34
5.11 Compounding of Plastics 5.36
5.12 Fabrication of Plastics 5.39
5.13 Foamed Plastics 5.42
5.14 Rubber or Elastomers 5.44
5.15 Composites 5.47
Questions 5.51
 UNIT

1
Water

1.1 INTRODUCTION
Water is one of the abundant available substances in nature. It is essential
for the survival and maintenance of all forms of life on earth and consists
of forms about 80% of the matter on earth’s crust. It also enjoys a unique
position in industries.
Although water is plenty on earth, the world’s total supply of fresh
water is only 2.5% of the total amount, the rest being in the form of
oceans. Thus, water available for drinking and other useful purposes
is limited. This limited amount of water is further polluted to a great
deal by human activities. For drinking and industrial purposes, we need
water that is free from undesirable impurities.

1.2 SOURCES OF WATER

The main sources of water are

• Surface water
• Underground water

1.2.1 Surface Water

Surface water exists as rain water, river water, sea water and lake
water.
(a) Rain Water It is the main source of water obtained as a result of
evaporation of sea water. Rain water may be the purest form of water. It
is made impure by pollution in the atmosphere. It contains a considerable
amount of industrial gases (like CO2, SO2, NO2, etc.) and suspended
solid particles, both of organic and inorganic origin.
(b) River Water It is the water that flows over the surface of the land.
It starts from spring water and is fed by rain water. It flows through
different kinds/of terrain and dissolves the soluble minerals of the soil.
Chlorides, sulphates, bicarbonates of sodium, calcium, magnesium and
iron are some of the major mineral salts present in river water. River
water also contains organic matter, produced by the decomposition of
plants and small particles of sand and rock suspension.
(c) Sea Water This is the most impure form of natural water.
Continuous evaporation of water makes it continuously richer in
dissolved impurities. It contains sodium chloride, sulphates of sodium,
bicarbonates of potassium, calcium, magnesium and a number of other
compounds.
(d) Lake Water It contains fewer amounts of dissolved materials.

1.2.2 Underground Water

A part of rain water which falls on the earth’s surface percolates into the
earth and continues it’s journey till it meets a hard rock where it may be
stored or come in the form of a spring. During its downward journey, it
dissolves a number of salts. Example: Wells and Springs.
From the point of view of industrial applications, it is not usually
feasible to use rain water and sea water. Rain water is irregular in supply
and generally expensive to collect. Sea water is too saline for most of the
industrial uses except cooling.
So river water, lake water and underground water is normally
used for industrial and domestic purposes. Each industry has its own
specifications for water and so the treatment of water depends on the
purpose for which it is to be used.
From the requisites of water for various industries, it is thus seen that
water is to be treated to remove all the undesirable substances to suit a
particular industry. The process of removing all the types of impurities
from water and making it useful for domestic or industrial purposes is
called water treatment. Before treating water, one must know the nature
as well as the amount of impurities present in a given sample.

1.3 IMPURITIES IN WATER

The main impurities present in water are classified into three types.
• Physical impurities
 • Chemical impurities
• Bacteriological impurities
Physical Impurities These include suspended and colloidal
impurities.
(a) Suspended Impurities Clay, sand, decayed vegetable and animal
matter. These make the water turbid.
(b) Colloidal Impurities Finely divided clay and silica, colouring
matter,waste products, complex proteins, amines, etc. These impart
colour, odour and taste.
Chemical Impurities include dissolved salts and dissolved gases.
(a) Dissolved Salts Chlorides, sulphates, bicarbonates, carbonates of
Ca, Mg, Na, etc.
(i) CaCl2, CaSO4, Ca (HCO3)2, MgCl2, MgSO4, Mg (HCO3) 2 make the
water hard.
(ii) Mg (HCO3)2, Ca (HCO3)2, Na2CO3, NaHCO3, etc.,make the water
alkaline.
(b) Dissolved Gases Oxygen, carbon dioxide, hydrogen sulphide, etc.
(i) Oxygen accelerates the rate of corrosion.
(ii) CO2 and H2S make the water acidic and corrosive.
Bacteriological Impurities These include pathogenic microorganism
like bacteria, which spread various diseases like typhoid, dysentery,
hepatitis, etc.

1.4 TYPES OF WATER

Water is classified into two types based on the property of it forming

lather with soap solution.
(a) Soft Water Soft water is one that gives good lather readily with
soap solution.
2RCOONa + H2O 2RCOOH + 2 NaOH
Soft water

(b) Hard Water Water that does not produce lather with soap readily
but forms an insoluble precipitate-like white scum is known as hard
water.
2RCOONa + H2O (RCOO)2 Ca + 2 NaCl
Hard water Insoluble soap
(water with CaCl2
or other impurities)
 Here, R = long chain fatty acid like palmitic, oleic and stearic acid.
When water with such hardness is used for washing, a large amount
of soap is consumed. Thus hardness of water can be defined as the soap-
consuming capacity of water.
Common hardness-producing salts present in water are chlorides,
sulphates and bicarbonates of calcium and magnesium, i.e. CaCl2, CaSO4,
MgCl2, MgSO4,Ca(HCO3)2 and Mg(HCO3)2 .Their quantity decides the
extent of hardness of water.

1.5 WATER-QUALITY STANDARDS

Water used for drinking purposes should meet certain quality criteria
with respect to appearance (turbidity, colour), potability (taste, odour),
health (bacteria, nitrates, chlorides, etc.) and toxicity (metals, organics).
These criteria are established by health or other regulating agencies
to ensure that the water quality in a resource is suitable for drinking
purposes.
The following table summarises several quality criteria and their
standards for drinking water as suggested by the following agencies.
1. Indian Council of Medical Research (ICMR)
2. World Health Organization (WHO)

Table 1.1 Standards for drinking water

Name of Agencies
[Link] Parameter
ICMR WHO
A B A B
1. Colour (units) 5 25 5 50
2. Turbidity (units) 5 25 5 25
3. Total dissolved solids – – 500 1500
4. pH 7-8.5 – 7-8.5 –
5. Total hardness as 125 350 125 350
CaCO3 equivalents
6. Iron 0.3 1.0 0.3 1.0
7. Manganese 0.1 0.5 0.1 0.5
8. Nitrate 20 50 – 50-100
9. Chloride – – – 250
10. Fluoride 1.0 2.0 0.5 1.0-1.5
11. Sulphate 200 400 200 400
12. Pathogenic micro- – 1 – 1
organisms (Coliform) coliform per coliform per
100 mL 100 mL
A Recommended concentration (mg/L); B Maximum permissible concentration (mg/L)
 1.6 WATER-QUALITY PARAMETERS

The water-quality parameters are roughly divided into three

categories.
1. Physical parameters
2. Chemical parameters
3. Biological parameters

Table 1.2 Various water-quality parameters

Physical Parameters Chemical Parameters Biological Parameters
1. Colour 1. Hardness Pathogenic
2. Turbidity 2. Acidity microorganisms
3. Taste and odour 3. Alkalinity
4. Total Dissolved Solids (TDS) 4. Dissolved oxygen
5. pH
6. Biological Oxygen Demand (BOD)
7. Chemical Oxygen Demand (COD)

Some of the important water-quality parameters are discussed

below.

1.6.1 Turbidity
(a) Definition
• Turbidity is a cloudiness or haziness of water caused by individual
particles (suspended solids) that are generally invisible to the
naked eye, similar to smoke in air.
• Water is said to be turbid if light cannot penetrate through it. The
suspended matter in water that prevents the penetration of light
inside water is called turbidity.
• Turbidity is usually expressed in Jackson Turbidity Unit (JTU),
Nephelometric Turbidity Unit (NTU), Formazin Turbidity Unit
(FTU) and milligrams/litre in silica scale.
• The recommended concentration of turbidity in drinking water
should not exceed 5 units.
(b) Sources
Presence of finely divided, insoluble impurities which remain suspended
in water reduce its clarity. These suspended impurities may be
inorganic in nature (clay, silt, silica, ferric hydroxide, CaCO3, S, etc.)
or organic (finely divided vegetable or animal matter, oil, fats, greases,
microorganisms etc.).
(c) Sanitary Significance
Turbidity in drinking water causes possible water pollution and health
hazards may occur, when used.
(d) Problems Caused by Turbidity
• Objectionable in boilers and in cooling water systems
• Interference in water-softening processes
• Reduction in the disinfection efficiency
• Causes stains on clothes, baths, sinks, porcelain, etc.
(e) Turbidity Removal Methods
Sedimentation followed by
• Coagulation and filtration
• Coagulation and settling
• Coagulation, settling and filtration
• Centrifugation
(f) Turbidity Measurements
• Turbidimeter, nephelometer are instruments used for the
determination of turbidity in water.
• Turbidity in water may be measured on a standard silica scale
(turbidity is produced by 1 part of finely divided silica in a million
parts of distilled water).

1.6.2 Colour
(a) Definition
• Pure water should be absolutely colourless. But the fact is, even
water samples obtained from natural resources have some colour
ranging from straw-yellow to dark brown.
• The colour of water may also be attributed to the dissolved and
suspended solids in water. Colour which is caused by suspended
matter is called apparent colour and the colour which is contributed
by dissolved solids that remains even after the removal of
suspended matter is known as true colour.
• Colour is usually expressed in milligrams/litre in platinum–cobalt
scale or Hazen units.
• The recommended concentration of colour in drinking water
should be less than 5 units.
(b) Sources
Colour is due to the presence of dissolved or colloidal dispersed organic
matter or of mineral origin.
Examples
• Mineral origin: Iron, copper, manganese, dyes
• Organic origin: Tannin, peat, humus, algae
• Mainly industries are the basic source of pollution, e.g. dyeing,
laundering, textiles, etc.
The major sources which contribute colour to water are the
following:
• The end products from the degradation of organic matter are
picked up by water streams and are transported to the water
resources that impart colour.
• Colour is also imparted by algal growth. Chlamydomonous
moecouse growing in many surface water bodies excretes a
yellowish substances into the water.
• Divalent ions like Fe2+ and Mn2+ impart colour to the ground water
as well as to the surface water.
• Untreated discharge from textile, dyeing, wood pulp, leather and
paper industries also impart colour to both surface and ground
water.
(c) Sanitary Significance
• It indicates the presence of metal ions and organic matter which
affects health, e.g.
Yellow—Organic matter or chromium
Yellowish red—Iron
Red brown—Peat
• Colour in water is usually repulsive.
(d) Problems Caused by Colour
• Organic compounds which contribute true colour to the water
exert a high chlorine demand, and hence more quantity of chlorine
is necessary for disinfection.
• The colour of water also restricts the penetration of sunlight, which
subsequently retards the photochemical reactions, which affects
the reoxygenation capacity of water.
(e) Colour Measurements
• The colour of a sample is usually measured with a tintometer.
 • Colour is measured by comparison with known standards.
Potassium chloroplatinate with cobalt chloride is usually prepared
as a standard to measure the colour of water. The stock solution
of 500 Hazen units and then a series of working standards are
prepared from it by dilution. The intensity of colour in water is
measured against these standards by direct visual comparison.
• Colour determination is done on the day of collection itself,
otherwise Fe3+ ion precipitates as Fe(OH)3, which may contribute
colour to the sample. Carbonates may also precipitate and exhibit
colour.
(f) Methods of Removal of Colour
Coagulation, absorption, filtration and super chlorination

1.6.3 Acidity
(a) Definition
• Acidity is the measure of the ability of water to neutralise bases or
it is the tendency of water to donate H+ ions in order to neutralise
the basic anions (HCO3– , CO32–, OH–).
• Acidity is usually expressed in terms of pH.
(b) Sources
Acidity is classified into two types.
1. Mineral acidity
2. CO2 acidity
• Mineral acidity is due to the presence of mineral acids like HCl,
H2SO4, HNO3 and other strong acids in water. This type of acidity
is usually introduced into the water resource by metallurgical
industries, chemical industries, drainage from abandoned mines,
and from many other industrial sewage.
• Carbon dioxide acidity is due to the presence of free CO2 in ground
and surface waters. CO2 is released into the water resource due
to the oxidation of organic matter by bacteria.
• Humic, fulvic and other organic acids produced by decomposing
vegetation also make the water acidic.
(c) Sanitary Significance
• Presence of carbonic acid and other organic acids in water does not
have any deleterious effects on health point of view (for example,
presence of CO2 in malt and carbonated beverages has no adverse
effects on human beings).
 • However, acidic water corrodes concrete pipes and causes
dissolution of metals such as Cu, Zn, etc.
(d) Acidity Measurements
• Acidity may be determined by using a pH meter or titrimetry
using different acid–base indicators.
• Out of these methods, determination of various types and amounts
of acidity is easily carried out by titration with a standard solution
of alkaline reagents using methyl orange indicator.
(e) Method of Removal of Acidity
To remove the acidity, a small quantity of sodium hydroxide or sodium
carbonate may be added in the water with acidity.

1.6.4 Alkalinity
(a) Definition
• Alkalinity is a measure of the ability of water to neutralise the
acid or it is the tendency of water to accept H+ ions in order to
neutralise it with the supply of OH– ions.
• It is usually expressed in terms of pOH.
(b) Sources
• Alkalinity in water is due to the presence of bicarbonates,
carbonates and hydroxides of Ca, Mg, Na and K.
• This type of alkalinity is usually introduced into the water resource
by metallurgical industries, chemical industries, drainage from
abandoned mines and from many other industrial sewage.
(c) Alkalinity in Water Analysis
In water analysis, it is often desirable to know the kinds and amounts
of the various forms of alkalinity present in water.
The alkalinity of water is due to the presence of a wide variety of salts
of weak acids such as carbonates, bicarbonates, phosphates, etc., and
also due to the presence of weak and strong bases (due to contamination
with industrial wastes). The major portion of alkalinity in natural water
is caused by the presence of bicarbonates that are formed when water
containing free carbon dioxide percolates through soils containing
calcium carbonate and magnesium carbonate.
CaCO3 + CO2 + H2O Ca(HCO3)2
The alkalinity of natural water may be taken as an indication of the
concentration of hydroxides, carbonates and bicarbonates.
(d) Classification
1. Bicarbonate alkalinity
2. Carbonate alkalinity
3. Hydroxide alkalinity
(e) Sanitary Significance
High alkalinity in natural water favours the growth of algae and
phytoplanktons. Usage of this alkaline water may cause harmful effects
on human beings.
(f) Alkalinity Measurements
• Alkalinity may be determined by the potentiometric method
or by using pH meter or titrimetry using different acid–base
indicators.
• Out of these methods, determination of various types and amounts
of alkalinity is easily carried out by titration with standard
hydrochloric acid employing phenolphthalein and methyl orange
as an indicator separately or in succession.
(g) Experimental Determination of Alkalinity
(i) Principle
The type and extent of alkalinity present in a water sample may be
determined by titrating the water with a standard acid to phenolphthalein
end point (P) and continuing the titration to methyl orange end point
(M). The following reactions may take place.
OH– + H+ H2O (1.1)
CO32– +H +
HCO3– (1.2)
HCO3– + H+ H2O + CO2 (1.3)
The volume of the acid used up to phenolphthalein end point (P)
corresponds to the completion of equations (1.1) and (1.2), while the
volume of the acid used after (P) corresponds to the completion of the
equation (1.3). The total amount of the acid used from beginning of the
experiment corresponds to the total alkalinity present which represents
the completion of equations (1.1)–(1.3).
The results are summarised in Table 1.3 from which the amount of
hydroxides, carbonates and bicarbonates present in the water sample
can be calculated.
Highly alkaline water may lead to caustic embrittlement and also may
cause deposition of precipitates and sludges in boiler tubes and pipes.
Table 1.3 Calculation of hydroxides, carbonates and bicarbonates
Alkalinity OH– (ppm) CO32– (ppm) HCO3– (ppm)
P=O 0 0 M
P=½M 0 2P 0
P<½M 0 2P (M – 2P)
P>½M (2P – M) 2(M – P) 0
P=M M 0 0
(P = Phenolphthalein alkalinity; M = Methyl orange alkalinity)

(ii) Procedure
About 20 mL of the given water sample is pipetted out into a clean
conical flask. A drop of phenolphthalein indicator is added. Now the
water sample becomes pink in colour and this solution is titrated against
standard sulphuric acid taken in the burette. The end point is the colour
change from pink to colourless. The volume of acid consumed is taken
as V1 mL. To the same water sample, a drop of methyl orange indicator
is added and the sample is again titrated against sulphuric acid taken in
the burette. The end point is the colour change from yellow to reddish
orange. The additional volume of acid consumed is taken as V2 mL.
(iii) Calculation
Volume of acid used up to phenolphthalein end point = V1 mL
Normality of acid = N1
Phenolphthalein alkalinity (P) in terms of calcium carbonate
equivalent
V1 × N1
= _______ × 50 × 1000 mg/litre
20
Additional volume of acid used up to methyl orange end point =
V2 mL
Normality of acid = N1
Methyl orange alkalinity (M) in terms of calcium carbonate
equivalent
(V1 + V2) × N1
= _____________ × 50 × 1000 mg/litre
20
Then the calculation of hydroxides, carbonates and bicarbonates is
made with the help of Table 1.3.
Thus, determination of alkalinity is of importance in
1. Water softening
2. Chemical treatment of waste water
3. Corrosion control
 4. Removal of ammonia by air stripping
5. Internal conditioning of boiler feedwater

1.6.5 Nitrogen
(a) Definition
• The nitrogen present in the saline constituents is known as
ammoniacal nitrogen and in organic constituents, albuminoid
nitrogen. Nitrogen is an inert gas and it is never determined in
the water analysis.
• The concentration of nitrogen is expressed in milligrams/litre.
• The normal permissible level of nitrogen compound concentration
is 10 mg/L of NO3– nitrogen.
(b) Sources
• Nitrogen compounds are also released from proteins and also by
the nitrogen–fixing bacteria.
• Certain microbial reactions also contribute to the release of
nitrogen. Ions like NO2–, NO3– are highly mobile in nature and
nitrites are easily converted into nitrates through microbial
conversion.
Thus, ammoniacal nitrogen can be in the form of ammonia, nitrates
and nitrites.
(i) Ammonia
Source: Free ammonia is formed as an initial product of decomposition
of nitrogenous organic matter.
Significance: The presence of ammonia indicates that the decomposition
has taken place recently.
Permissible Limit: Not greater than 0.15 ppm
Determination Method: Using Nessler’s reagent
(ii) Nitrite
Source: Nitrites are the products obtained by oxidation of ammonia.
Significance: Presence of nitrate in water indicates that organic matter
is not fully oxidised. It has no corrosive effects on metal.
Limit: Should not be present.
(iii) Nitrate
Source:
• Nitrates are the end products of decomposition of organic
matter.
 • These are produced by the aerobic stabilisation of organic
nitrogen.
• Wastes from chemical fertiliser.
Significance:
• Presence indicates that the organic matter is fully oxidised.
• Greater than 50 mg/L causes methemoglobinemia in children.
Limit:
Permissible: 10 mg/L
Admissible: 50 mg/L
Determination Method: Separation of ammoniacal and albuminoid
nitrogen followed by estimation of the nitrogen.
1. Separation of Ammoniacal and Albuminoid Nitrogen
Ammoniacal Nitrogen: The water sample is distilled after adding
phosphate buffer. The distillate contains ammoniacal nitrogen.
Albuminoid Nitrogen: The distillation is continued after removal of
ammoniacal nitrogen with addition of alkaline KMnO4 and the distillate
contains albuminoid nitrogen.
2. Estimation Method of Ammoniacal and Albuminoid Nitrogen
The above distillates are subjected with Nessler’s reagent for estimation
of nitrogen.
Total Nitrogen: This is estimated by Kjeldhal’s method.
Nitrates: By spectrophotometric method by using phenol-disulphonic
acid and KOH as reagents.
Nitrites: By spectrophotometric method, by producing a reddish purple
dye by diazotisation reaction, using N-(1-naphthyl ethylene diamine)
dihydrochloride at pH 2.0 to 2.5.
Sanitary Significance
The presence of nitrogen compounds in water increases the growth of
algal and aquatic weeds. Hence an optimum level should always be
maintained in order to ensure the safety of the drinking water.

1.6.6 Fluoride
(a) Definition
• When water resources come into contact with the fluoride
containing rocks, a large amount of soluble fluorides are
released.
• Fluorides are usually expressed in milligrams/litre.
 • The normal permissible level of fluoride concentration is
1 mg/L.
(b) Sources
• The general sources are
1. From geological minerals
2. Chemical wastes from industries
• The principal sources of fluoride to the physiology of man are
water and food.
(c) Sanitary Significance
• Fluoride, in small doses, has a remarkable influence by
strengthening the dental system by inhibiting dental cavities. In
high dosages, it may cause dental and skeletal fluorosis.
• The normal permissible level of fluoride concentration is 1 mg/L
above which it causes various destructive physiological effects.
• Again deficiency of fluorides may lead to the underdevelopment
of bones and may prevent the formation of dental enamel.
(d) Determination Method
Using zirconium–alizarin reagent in Nessler’s tube.
Method of Removal of Fluoride
1. By adsorption on activated carbon
2. Precipitation using aluminium salts
3. By using strongly basic anion-exchange resin

1.7 HARDNESS OF WATER

Hardness is the characteristic of water which does not give good lather
with soap. This property of water is due to the presence of bicarbonates,
chlorides and sulphates of calcium, magnesium and other salts.

1.7.1 Classification of Hardness of Water

Hardness of water can be classified into two categories.
(a) Temporary hardness (or) carbonate hardness
(b) Permanent hardness (or) non-carbonate hardness.
(a) Temporary (or) Carbonate Hardness
This is caused by the presence of dissolved bicarbonates of calcium and
magnesium. Temporary hardness is mostly destroyed by mere boiling
of water.
 During boiling, the bicarbonates are decomposed and form insoluble
precipitates. Carbonates and hydroxides can be removed by filtration,
while CO2 escapes out.
Ca(HCO3)2 CaCO3 Ø + H2O + CO2
Insoluble

Mg(HCO3)2 Mg(OH)2 Ø + 2CO2

Insoluble

(b) Permanent (or) Non-carbonate Hardness

This is due to the presence of dissolved chlorides and sulphates of
calcium and magnesium. Unlike temporary hardness, permanent
hardness is not destroyed on boiling.
Total Hardness of Water = Carbonate Hardness + Non-carbonate
Hardness
(or)
= Temporary Hardness + Permanent Hardness

1.7.2 Units of Hardness

The following are the common units used in hardness measurements.
(a) Parts per million (ppm) It is defined as the number of parts by
weight of CaCO3 present in million parts by weight of water.
1 ppm = 1 part of CaCO3 equivalent hardness in 106 parts of water.
(b) Milligram per Litre (mg/L) It is defined as the number of
milligrams of CaCO3 present in one litre of water.
1 mg/L = 1 mg of CaCO3 equivalent hardness in 1 litre of water.
Relationship between ppm and mg/L
Weight of 1 litre of water = 1 kg
= 1000 g
= 1000 × 1000 mg
= 106 mg
We know that,
1 mg/L = 1 mg of CaCO3 in 1 litre of water
= 1 mg of CaCO3 in 106 mg of water.
= 1 part of CaCO3 per 106 parts of water.
= 1 ppm
Hence 1 mg/litre = 1 ppm
Thus, mathematically both units are equal.
1.7.3 Expression of Hardness
Hardness of water is expressed in terms of number of parts of CaCO3
(or) its equivalent present in a particular quantity of water because
(i) CaCO3 is the most insoluble salt which can be precipitated in water
treatment
(ii) Molecular weight of CaCO3 is 100 and its equivalent weight is 50
which is easy for calculations
Calcium Carbonate Equivalent
Thus, hardness is expressed in terms of CaCO3 (or) its equivalent. If
water contains CaCO3 alone, the hardness is a measure of number of
parts of CaCO3. Usually, water contains some other salts. Hence, all
the hardness–causing impurities are first converted in terms of their
respective weights equivalent to CaCO3 by using the relation
CaCO3 Weight of hardness producing salt Molecular weight
= _______________________________ ×
equivalent Molecular weight of the salt of CaCO3

or
CaCO3 Weight of hardness producing salt Equivalent weight
= _______________________________ ×
equivalent Equivalent weight of the salt of CaCO3

Table 1.4 Molecular weights of some hardness-producing salts

[Link] Molecular Formula of Salt Molecular Weight
1 Mg(HCO3)2 146
2 Ca (HCO3)2 162
3 CaCO3 100
4 MgCO3 84
5 CaSO4 136
6 MgSO4 120
7 CaCl2 111
8 MgCl2 95
9 Ca2+ 40
10 Mg2+ 24
11 Ca(NO3)2 164
12 Mg(NO3)2 148

1.7.4 Estimation of Hardness of Water by EDTA Method

The hardness of water can be estimated by EDTA method. This is a
reliable method because of its greater accuracy.
(a) EDTA EDTA is Ethylene Diamine Tetra Acetic acid.
(b) Molecular Structure of EDTA
HOOC — H2C CH2 – COOH
N — CH2 — CH2 — N
HOOC — H2C CH2 – COOH

EDTA is insoluble in water, and its disodium salt is used as a

complexing reagent. In this complexometric method, disodium salt of
ethylene diamine tetra acetic acid is actually used.
(c) Structure of Disodium Salt of EDTA
NaOOC — H2C CH2 – COOH
N — CH2 — CH2 — N
HOOC — H2C CH2 – COONa

(d) Principle
Estimation of hardness by EDTA method is based on the principle that
EDTA forms metal complexes with hardness-producing metal ions in
water. These complexes are stable when the pH is maintained between
8 and 10. In order to maintain the pH, a buffer solution (NH4Cl-NH4OH
mixture)is added. The completion of the complexation reaction is
indicated by Eriochrome Black-T indicator. When this indicator is added
to the sample water, it forms indicator–metal complexes of wine-red
colour.
Ca2+/Mg2+ + EBT [Ca/Mg-EBT]
Indicator Unstable complex
(blue colour)
(wine-red)

This wine-red solution is titrated against EDTA, and EDTA replaces

EBT indicator from [Ca/Mg-EBT] complex. The colour of the solution
changes from wine-red to steel-blue at the end [Link] total hardness
is thus determined.
[Ca/Mg-EBT] + EDTA [Ca/Mg – EDTA] + EBT
Unstable complex Stable complex (Steel-blue)
(wine-red) (colorless)

The temporary hardness is removed by boiling and after the removal

of precipitate by filtration, the permanent hardness in the filtrate is
determined by titration with EDTA as [Link],
Total hardness – Permanent hardness = Temporary hardness
(e) Experimental Procedures
(i) Standardisation of EDTA Solution:
20 ml of standard hard water is taken in a conical flask. 5 ml of buffer
solution and a few drop of EBT indicator are added. The solution is
titrated against EDTA taken in a burette. The end point is the colour
change from wine-red to steel-blue colour. Let the volume of EDTA
consumed be V1 ml.
Calculation
V1 ml of EDTA consumes 20 ml of std. hard water
= 20 × 1 mg of CaCO3 eq. hardness
20
1 ml of EDTA consumes = ___ mg of CaCO3 eq. hardness
V1
(since 1ml of std. hard water = 1mg of CaCO3)

(ii) Estimation of Total Hardness:

20 ml of sample hard water is pipetted out into a conical flask and titrated
against EDTA taken in a burette by adding the buffer and the indicator
to get the end point. Let the volume of EDTA consumed be V2 ml.
Calculation
V2 ml of EDTA consumes 20 ml of sample hard water
We know
20
1 ml of EDTA consumes = ___ mg of CaCO3 eq. hardness
V1
20
V2 ml of EDTA consumes = ___ × V2 mg of CaCO3 eq. hardness
V1
20
20 ml of sample hard water = ___ × V2 mg of CaCO3 eq. hardness
V1
\ 1000 ml of sample hard water contains,
20 1000
= V2 × ___ × _____ mg of CaCO3 equivalent hardness
V1 20
V2
Total hardness = 1000 × ___ mg/litre (or) ppm
V1

(iii) Estimation of Permanent Hardness:

250 ml of water sample is boiled off to a volume of 50 ml in a beaker
to remove temporary hardness. The temporary hard salts settle down.
Filter and wash thoroughly and make up the solution again to 250 ml.
From this, 20 ml of the solution is titrated against the EDTA as done
before. Let the volume of EDTA consumed be V3 ml.
Calculation
V3 ml of EDTA consumes 20 ml of boiled sample hard water
We know
20
1 ml of EDTA consumes = ___ mg of CaCO3 eq. hardness
V1
20
V3 ml of EDTA consumes = V3 × ___ mg of CaCO3 eq. hardness
V1
20 ml of boiled sample hard water
20
= V3 × ___ mg of CaCO3 eq. hardness
V1
\ 1000 ml of boiled sample hard water contains
20 1000
= V3 × ___ × _____ mg of CaCO3 equivalent hardness
V1 20
V3
= 1000 × ___ mg/litre (or) ppm
V1
V3
Permanent hardness = 1000 × ___ mg/litre (or) ppm
V1

(iv) Estimation of Temporary Hardness:

This can be calculated by using the following methods.
Temporary Hardness = Total hardness – Permanent hardness
(or)

[
(V2 – V3)
]
Temporary Hardness = 1000 × ________ mg/litre (or) ppm
V1

Note: NH4Cl–NH4OH buffer is used in the titration in order to maintain

a pH of 8–10. At this pH only, the complexation of Ca2+ and Mg2+ ions
with EBT and EDTA takes place.
(f) Advantages of EDTA Method
1. This method is more accurate in the estimation of hardness of
water than other methods.
2. It is a convenient and more rapid process.
Example 1 If a sample of water contains 72 mg of Mg2+ ions per litre,
calculate its hardness in terms of calcium carbonate equivalent.
Solution Given
The amount of Mg2+ ions = 72 mg/L
Atomic weight of magnesium = 24
72
Amount equivalent to CaCO3 = ___ × 100
24
= 300 mg/L

Example 2 If a sample of water contains 80 mg of Ca2+ ions per litre,

calculate its hardness in terms of CaCO3 equivalent.
Solution Given
The amount of Ca2+ions = 80 mg/L
Atomic weight of magnesium = 40
80
Amount equivalent to CaCO3 = ___ × 100
40
= 200 mg/L

Example 3 A sample of water contains 240 mg of MgSO4 per litre.

Calculate the hardness in terms of CaCO3 equivalents.
Solution Given
The amount of MgSO4 = 240 mg/L

Weight of hardness-
producing salt
___________________ Molecular weight
CaCO3 = ×
equivalent Molecular weight of CaCO3
of the salt

We know that the molecular weight of MgSO4 =120.

240
Thus amount equivalent to CaCO3 = ____ × 100 = 200 mg/L
120

Example 4 The analysis of three samples of water gives the following results.
Sample 1 contains 20 mg/L of calcium sulphate, Sample 2 contains 20 mg/L of
magnesium bicarbonate and Sample 3 contains 20 mg/L of magnesium sulphate.
Find which sample is more hard.
Solution Sample 1
The amount of calcium sulphate = 20 mg/litre
 20
Amount equivalent to CaCO3 = ____ × 100
136
= 14.70 mg/L
Sample 2
The amount of magnesium bicarbonate = 20 mg/L
20
Amount equivalent to CaCO3 = ____ × 100
146
= 13.70 mg/L
Sample 3
The amount of magnesium sulphate = 20 mg/L
20
Amount equivalent to CaCO3 = ____ × 100
120
= 16.67 mg/L
Hence, Sample 3 is hardest.

Example 5 If a sample of water contains 70 mg of Ca2+ ions per litre,

calculate its hardness in terms of CaCO3 equivalent.
Solution Given
The amount of Ca2+ ions = 70 mg/L
We know that, the molecular weight of calcium = 40
70
Amount equivalent to CaCO3 = ___ × 100 = 175 mg/L
40

Example 6 A sample of water on analysis contains 27.2 mg/L of calcium

sulphate, 29.2 mg/L of magnesium bicarbonate, and 24 mg/L of magnesium
sulphate. Calculate the total hardness of the sample.
Solution In order to calculate the total hardness of the sample, these
salts have to be converted into their equivalents of CaCO3.
Molecular Formula of Salt Molecular Weight Quantity Present Equivalent of CaCO3
27.2 x 100
_________
CaSO4 136 27.2 = 20
136
29.2 x 100
_________
Mg(HCO3)2 146 29.2 = 20
146
24 x 100
________
MgSO4 120 24 = 20
120

Temporary hardness = 20 mg/L [Mg(HCO3)2 alone]

Permanent hardness = 20+20 = 40 mg/L (CaSO4 + MgSO4)
Total hardness = (Temporary + Permanent) hardness
= 20 + 40 = 60 mg/L (or) ppm
Example 7 Calculate the temporary and permanent hardness of a water
sample having the following data: Mg(HCO3)2 : 292 mg/L, Ca(HCO3)2 : 162
mg/L, CaSO4 : 136 mg/L, MgCl2 : 190 mg/L, CaCl2 : 222 mg/L
Solution
Salt Mol. Wt. Quantity Present CaCO3 Equivalent
292
____
Mg(HCO3)2 146 292 x 100 = 200 mg/l
146
162
____
Ca(HCO3)2 162 162 x 100 = 100 mg/l
162
136
____
CaSO4 136 136 x 100 = 100 mg/l
136
190
____
MgCl2 95 190 x 100 = 200 mg/l
95
222
____
CaCl2 111 222 x 100 = 200 mg/l
111

Temporary hardness: Due to bicarbonates of Mg and Ca

Mg(HCO3)2 + Ca(HCO3)2 = 200 + 100 = 300 mg/L (or) ppm
Permanent hardness: Due to CaSO4, MgCl2 and CaCl2
= 100 + 200 + 200
= 500 mg/L (or) ppm

Example 8 Calculate carbonate and noncarbonate hardness of a sample

of water containing dissolved solids as follows: Mg(HCO3)2 : 9.3 mg/L,
Ca(HCO3)2 : 20.50mg/L, CaSO4 : 26 mg/L, MgCl2 : 10 mg/L and NaCl : 60
mg/L
Solution
Salt Mol. Wt. Quantity Present CaCO3 Equivalent
9.3
____
Mg(HCO3)2 146 9.3 x 100 = 5 mg/L
146
20.50
_____
Ca(HCO3)2 162 20.50 x 100 = 25 mg/L
162
26
____
CaSO4 136 26 x 100 = 10 mg/L
136
10
___
MgCl2 95 10 x 100 = 22.9 mg/L
95

NaCl does not produce any hardness of water.

Carbonate hardness: Due to presence of bicarbonates of Ca and Mg
Mg(HCO3)2 + Ca (HCO3)2 = 6.4 + 12.7 = 19.1mg/l (or) ppm
Noncarbonate hardness: Due to CaSO4, and MgCl2
= 19.1 + 10.5
= 29.6 mg/L (or) ppm
Example 9 A water sample contains 408 mg of CaSO4 and 73 mg
of Mg(HCO3)2 per litre. What is the total hardness in terms of CaCO3
equivalent?
Solution
Salt Mol. Wt. Quantity Present CaCO3 Equivalent
408
____
CaSO4 136 408 × 100 = 300 mg/l
136
73
____
Mg(HCO3)2 146 73 × 100 = 50 mg/l
146

Temporary hardness: Due to Mg(HCO3)2 = 50 mg/L

Permanent hardness: Due to CaSO4 = 300 mg/L
Total hardness = 50 + 300
= 350 mg/L(or) ppm

Example 10 Sample water of 100 mL has a hardness equivalent to 25 mL

of 0.16 N MgSO4. What is the hardness of water?
Solution
100 mL of sample of water = 25 mL of 0.16 N MgSO4
25 × 0.16
Nhardness = ________
100
Hardness in terms of CaCO3 equivalent
25 × 0.16
= ________ × 50 × 1000
100
= 2000 mg/L or ppm

Example 11 Hard water of 100 mL required 30 ml of EDTA solution for

titration (1 mL of EDTA = 1 mg of CaCO3). Calculate the hardness of the
sample of water.
Solution
1 mL of EDTA = 1 mg of CaCO3 equivalent
30 mL of EDTA = 30 mg of CaCO3 equivalent
This amount of hardness is present in 100 mL of hard water. So
30
Hardness present in 1 litre = ____ × 1000
100
= 300 ppm
Example 12 Sample water of 100 mL on EDTA titration with Eriochrome
Black-T as indicator consumed 16 mL of 0.024 M EDTA till end point is reached.
Calculate the hardness of water.
Solution
1 ml of 0.01 M EDTA = 1 mg of CaCO3 equivalent
1 × 16 × 0.024
16 ml of 0.024 M EDTA = _____________
1 × 0.01
= 38.4 mg of CaCO3
This amount of hardness is present in 100 mL of water sample.
38.4
So, hardness present in 1 litre = ____ × 1000
100
= 384 ppm

Example 13 Sample of water of 200 mL required 40 mL of 0.01M EDTA

for the titration with Eriochrome Black-T indicator. 100 mL of the same sample
after boiling and filtering required 20 mL of 0.01M EDTA. Calculate the total
carbonate (temporary) and noncarbonate (permanent) hardness of the sample.
Solution Total hardness:
1 mL of 0.01 M EDTA = 1 mg of CaCO3 equivalent
40 mL of 0.01 M EDTA = 40 mg of CaCO3 equivalent
This amount of hardness is present in 200 mL of the sample water.
40
So, total hardness present in 1 litre = ____ × 1000
200
= 200 ppm
Permanent or noncarbonate hardness:
1 mL of 0.01M EDTA = 1 mg of CaCO3 equivalent
20 mL of 0.01M EDTA = 20 mg of CaCO3 equivalent
This amount of hardness is present in 200 mL of the water sample.
20
So, permanent hardness present in 1 litre = ____ × 1000
200
= 100 ppm
Carbonate or temporary hardness:
Carbonate hardness = Total hardness – noncarbonate hardness
= 200 – 100
= 100 ppm
Example 14 Calcium carbonate of 0.5 g was dissolved in dil. HCl and
diluted to 500 mL. 50 mL of this solution required 48 mL of EDTA solution
for titration. 50 mL of a hard-water sample required 15 mL of the same EDTA
solution for titration. Calculate the total hardness of water.
Solution 500 mL of CaCl2 solution = 0.5 g of CaCO3
= 0.5 × 1000 mg of CaCO3
= 500 mg of CaCO3
Standardisation of EDTA:
1 mL of CaCl2 solution = 1 mg of CaCO3
50 mL of CaCl2 solution = 50 mg of CaCO3
48 mL of CaCl2 solution = 50 mg of CaCO3
50
1 ml of CaCl2 solution = ___ × 1
48
= 1.04 mg of CaCO3
Total hardness:
1 mL of CaCl2 solution = 1.04 mg of CaCO3
15 mL of CaCl2 solution = 1.04 × 15
= 15.6 mg of CaCO3
This amount of hardness is present in 50 mL of the water sample.
15.6
So, total hardness present in 1 litre = ____ × 1000
50
= 312 ppm.

Example 15 Calcium carbonate of 0.25 g was dissolved in dil. HCl and

diluted to 250 mL. 100 mL of this solution required 20 mL of EDTA solution
for titration. 100 mL of a hard-water sample required 30 mL of the same EDTA
solution for titration. 100 mL of the same water sample on boiling, filtering
required 10 mL of EDTA. Calculate the total permanent and temporary
hardness.
Solution
250 mL of CaCl2 solution = 0.25 g of CaCO3
= 0.25 × 1000 mg of CaCO3
= 250 mg of CaCO3
1 mL of CaCl2 solution = 1 mg of CaCO3
Standardisation of EDTA:
100 mL of CaCl2 solution = 100 mg of CaCO3
20 mL of CaCl2 solution = 100 mg of CaCO3
 100
1 mL of CaCl2 solution = ____ × 1
20
= 5 mg of CaCO3
Total hardness:
30 mL of CaCl2 solution = 30 × 5
= 150 mg of CaCO3
This amount of hardness is present in 100 mL of the water sample.
150
So, total hardness present in 1 litre = ____ × 1000
100
= 1500 ppm
Permanent hardness:
10 ml of EDTA solution = 5 × 10
= 50 mg of CaCO3
This is present in 100 mL of hard water.
50
So, permanent hardness present in 1 litre = ____ × 1000
100
= 500 ppm.
Temporary hardness = Total hardness – Permanent hardness
= 1500 – 500
= 1000 ppm

1.7.5 Disadvantages of Hard Water

Some important disadvantages of hard water are the following
1. Hard water is not useful for various domestic purposes, viz.
washing, bathing, drinking, etc. The ions responsible for the
hardness convert soluble soaps to insoluble precipitates. This
causes wastage of soap in washing and bathing. Also, presence
of iron salts may result in staining of cloth.
2. Hard water is harmful for many industries such as textile, sugar,
paper, laundry, etc. Dissolved calcium, magnesium and iron salts
may react and affect the following properties:
(a) May cause coloured spots on fabrics in textile industry
(b) May cause difficulties in the crystallisation of sugar in sugar
industry
(c) May cause wastage of lot of soap in laundry
(d) Giving a smooth and glossy finish to paper in paper
industry
 3. Hard water is also not suitable in steam generation in boilers
since there arise many troubles like scales and sludge formation,
corrosion, priming and foaming and caustic embrittlement.
4. Hard water is not suitable in laboratory analysis also because the
hardness-producing ions interfere in various reactions.

1.8 BOILERS

Most of the water used in industry and powerhouses is in the form of

steam. For steam generation, boilers are almost invariably employed.

1.8.1 Classification of Boilers

Boilers are generally classified according to their pressures into three
categories.
(i) Low-pressure boilers: Up to 15 kg/cm2
(ii) Medium-pressure boilers: 15 to 30 kg/cm2
(iii) High-pressure boilers: Over 30 kg/cm2

1.8.2 Boiler Feedwater

The water fed into the boiler for the production of steam is called boiler
feedwater.
Requisites (or) Specification of Boiler Feedwater
Water used in boilers should be free from dissolved calcium and
magnesium salts and dissolved gases such as oxygen (O2) and carbon
dioxide (CO2).
Any natural source of water does not supply a perfectly suitable
boiler feedwater. The boiler feedwater must have the following
requirements.

Table 1.5 Suggested limits of tolerance for boiler feedwater

S. No Parameter Amount
1 Hardness
for 0–10 kg/cm2 boiler 80 ppm (max)
10–15 kg/cm2 boiler 40 ppm (max)
15–30 kg/cm2 boiler 10 ppm (max)
Above 30 kg/cm2 2 ppm (max)
2 pH 7.0
3 Colour Colourless
4 Odour Nil
5 Dissolved gases like O2 and CO2 0 ppm
 1.9 BOILER TROUBLES DUE TO HARD WATER

If the boiler feedwater contains impurities (or) if the hard water obtained
from natural sources is fed directly to the boilers, the following troubles
may arise:
1. Scale and sludge formation
2. Boiler corrosion
3. Caustic embrittlement
4. Priming and foaming (carry over)

1.9.1 Scale and Sludge Formation in Boilers

In boilers, water evaporates continuously and the concentration of the
dissolved salts increases progressively. When the salt concentrations
reach their saturation points, they are thrown out of water in the form
of precipitates on the inner walls of the boiler.
If the precipitated matter is soft and slimy, it is called sludge. When
the precipitate forms an adherent coating on the inner walls of the boiler,
it is called scale.
Boiler

Water

Heat Heat
Loose precipitate Hard, adhering coating
suspended in water on inner walls of boiler
(sludge) (scale)
(a) (b)

Fig. 1.1 (a) Sludge formation in boilers; (b) Scale formation in boilers

(a) Sludge Formation

1. Sludge is a soft, loose and slimy precipitate which forms inside
the boiler during steam generation.
2. The main sludge-forming substances in water are MgCO3, MgCl2,
MgSO4, CaCl2, etc.
3. Sludges are generally formed at cooler portions of the boiler.
4. Sludges can be easily scrapped off with a wire brush.
Disadvantages of Sludge Formation
1. Sludges are poor conductors of heat, so they waste a portion of
heat generated.
2. Excess of sludge formation decreases the efficiency of a boiler.
3. If sludges are formed along with scales then both will be deposited
on inner walls of boiler as scales, and then it cannot be removed
easily.
Prevention of Sludge Formation
Sludge formation in boilers can be prevented by the following
methods:
1. By using well-softened water.
2. By frequent blow-down operation a process in which a portion of
concentrated water containing large amount of dissolved salts is
replaced with fresh water frequently, during steam making)
3. It can be easily scrapped off with a wire brush
(b) Scale Formation
1. Scale is a hard, adherent coating which forms on the inner walls
of the boiler during steam generation.
2. In a low-pressure boiler, the main scale-forming substances are
Ca(HCO3)2 and MgCl2.
3. In a high-pressure boiler, the scale-forming substances are mainly
CaSO4 and Silica.

1.9.2 Scale-formation Reactions

(a) In Low-pressure Boilers
(i) Decomposition of Ca(HCO3)2
D
Ca (HCO3)2 CaCO3 Ø + H2O + CO2
Soft scale
(Insoluble)

However, scale composed chiefly of calcium carbonate is soft and is

the main cause of scale formation in low-pressure boilers. But in high-
pressure boilers, CaCO3 is soluble.
CaCO3 + H2O Ca(OH)2 + CO2
Soluble

(ii) Hydrolysis of Magnesium Salts

Dissolved magnesium salts undergo hydrolysis, forming magnesium
hydroxide precipitate.
 MgCl2 + 2H2O Mg(OH)2 Ø + 2HCl
Soft scale
(precipitate)

(b) In High-pressure Boilers

(i) Deposition of CaSO4
The solubility of calcium sulphate in water decreases with rise of
temperature. Thus, solubility of CaSO4 is 3200 ppm at 15°C and it
reduces to 55 ppm at 230°C and 27 ppm at 320°C. In other words, CaSO4
is soluble in cold water, but almost completely insoluble in superheated
water. Consequently, CaSO4 gets precipitated as hard scale on the heated
portion of the boiler. This is the main cause of scales in high-pressure
boilers.
Note: Calcium sulphate is quite adherent and difficult to remove, even
with the help of a hammer and chisel.
(ii) Presence of SiO2 (Silica)
SiO2 present in water, even in small quantities, deposits as CaSiO3 and
MgSiO3. These deposits stick very firmly to the inner side of the boiler
surface and are very difficult to remove. One important source of silica
in water is the sand filter.

1.9.3 Disadvantages of Scale Formation

(a) High Consumption of Fuel
Scale is a poor conductor of heat and thus it decreases the evaporative
capacity of the boiler. So, the consumption of fuel is much more than
usual.
(b) Danger of Explosion
Since the scale acts as a heat insulator, the boiler metal is overheated.
Due to over heating, the metal expands until the scale on it cracks. When
thick scales crack ,the water suddenly comes in contact with overheated
boiler metal. This results in the development of high pressure inside the
boiler which may lead to a dangerous explosion.
(c) Low Effiency
Due to scale formation, heat available to water is reduced and hence
more heat is required to produce steam. This causes overheating of boiler
plates and tubes and thus their life is reduced.

1.9.4 Prevention of Scale Formation

Scale formation in boilers can be prevented by the following methods:
(a) External Treatment
This method involves the removal of scale-forming impurities from water
before feeding to the boiler, for example
• Lime soda process
• Zeolite process
• Demineralisation process
(b) Internal Treatment
This method involves the addition of chemicals directly to the water
in boilers to remove the scale-forming substances which were not
completely removed during external treatment, for example
• Colloidal conditioning
• Carbonate conditioning
• Calgon conditioning
• Phosphate conditioning

Table 1.6 Differences between sludges and scales

[Link] Sludges Scales
1. Sludges are soft and non-adherent Scales are hard deposits which stick very
deposits. firmly to the inner surface of boiler during
steam generation.
2. Sludges can be removed easily. Scales are very difficult to remove.
3. Disadvantages: Sludges can transfer Disadvantages: Scales are bad conductors
heat to some extent and are less of heat and are more dangerous. Scale
dangerous. Excess of sludge formation formation also decreases the efficiency of a
decreases the efficiency of boiler. bolier. Any crack developed on the scale leads
to an explosion.
4. Formation: Sludges are formed by Formation: Scales are formed by substances
substances like MgCl2, CaCl2, etc. like CaSO4, Mg(OH)2.
5. Prevention: It is prevented by either Prevention: It is prevented by
using well softened water or by frequent (a) External treatment-removal of scale
blow down operation. (Blow down formation impurities from water before
operation is a process in which a portion feeding into the boiler(using Lime-Soda
of concentrated water containing large process, Demineralisation process) and
amount of dissolved salts and replace it (b) Internal treatment- involves the removal
by fresh water frequently during steam of scale forming substances which were not
making) completely removed in the external treatment
by adding chemicals directly in the boiler
during evaporation itself.

1.9.5 Boiler Corrosion

The decay of boiler material by its environment is termed as boiler
corrosion. Corrosion in boilers is due to the presence of
(i) Dissolved oxygen
(ii) Dissolved carbon dioxide
(iii) Dissolved salts
(a) Dissolved Oxygen
The presence of dissolved oxygen in water is the main cause of boiler
corrosion. When water containing dissolved oxygen is heated in the
boiler, the dissolved oxygen gets liberated and attacks the boiler material
as follows:
2Fe + O2 + 2H2O 2Fe(OH)2 Ø
4Fe(OH)2 Ø + O2 2[Fe2O3.2H2O] Ø
Ferrous hydroxide Rust

Removal of Dissolved Oxygen

Dissolved oxygen can be removed by chemical (or) mechanical
methods.
• Chemical Method Sodium sulphite, hydrazine (or) sodium
sulphide are some of the chemicals used for removing oxygen.
2 Na2SO3 + O2 2 Na2SO4
Sodium sulphite Sodium sulphate

N2H4 + O2 N2 + 2 H2O
Hydrazine

Na2S + 2O2 Na2SO4

• Mechanical Method Dissolved oxygen can also be removed from
water by mechanical de-aeration.
• Mechanical De-aeration It is one of the method, used to remove
dissolved gases such as O2 and CO2.
In this process, water is allowed to fall slowly on the perforated plates
fitted inside the tower.
Water

To vacuun
pump
Heater

Perforated
plates

Tower
Deaerated water

Fig. 1.2 Mechanical de-aerator

 To reduce pressure inside the chamber, the de-aerator is connected
to a vacuum pump. The sides of the tower are heated. The water
flowing down through perforated plates undergoes deaeration at high
temperature and low pressure. [(High temperature, low pressure, and
large exposed surface (provided by perforated plates) reduces the
dissolved oxygen in water.]
This is because the solubility of a gas in water is directly proportional
to pressure and inversely proportional to temperature (Dalton’s law +
Henry’s law).
(b) Dissolved Carbon Dioxide
Dissolved carbon dioxide in water produces carbonic acid, which is
acidic.
CO2 + H2O H2CO3
Carbonic acid

Carbon dioxide is also released inside the boiler if water used for
steam generation contains bicarbonates of calcium and magnesium.
Ca(HCO3)2 CaCO3 Ø + H2O + CO2
D
Mg(HCO3)2 Mg(OH)2 + 2CO2

Removal of dissolved carbon dioxide

• Carbon dioxide may be removed by adding calculated amount of
NH4OH into water.
2NH4OH + CO2 (NH4)2CO3 + H2O
• Carbon dioxide along with oxygen in water can be removed by
mechanical de-aeration.
(c) Dissolved Salts
If water used for steam generation contains dissolved magnesium salts,
they liberate acids on hydrolysis.
MgCl2 + 2H2O Mg(OH)2 Ø + 2HCl
The liberated acid reacts with iron material of the boiler in a chain
like reaction producing HCl again and again.
Fe + 2HCl FeCl2 + H2
FeCl2 + 2H2O Fe(OH)2 Ø + 2HCl
Thus, presence of even a small amount of MgCl2 will cause corrosion
of iron to a large extent.
1.9.6 Caustic Embrittlement
Caustic embrittlement is a type of boiler corrosion caused by using
highly alkaline water in the boiler. It means the inter crystalline cracking
of boiler metal.
Boiler water usually contains a certain proportion of sodium carbonate,
added for water-softening purposes. In high-pressure boilers, Na2CO3
decomposes to give sodium hydroxide and carbon dioxide, and this
makes the boiler water caustic.
Na2CO3 + H2O 2NaOH + CO2
This NaOH containing water flows into the minute hair cracking
usually present on the boiler material by capillary action. Here, water
evaporates and the dissolved caustic soda concentration increases
progressively. This caustic soda attacks the surrounding area, thereby
dissolving iron of the boiler as sodium ferroate.
Fe + 2NaOH Na2FeO2 + H2
Sodium ferroate

This causes embrittlement of boiler parts, particularly stressed parts

like bends, joints, rivets, etc., causing even failure of the boiler.
Caustic cracking can be explained by considering the following
concentration cell;

| Iron at riverts,
bends, joints, etc. | Concentrated
NaOH | Dilute
NaOH |
Iron at plane
surfaces |
The iron surrounded by the dilute NaOH becomes the cathodic
side;while the iron in contact with rather concentrated NaOH becomes
the anodic part,which is consequently dissolved or corroded.
Prevention
It can be prevented by
1. Adding sodium sulphate (or) sodium phosphate as softening
reagent instead of sodium carbonate
2. Adding tannin, lignin to the boiler water which blocks the hair
cracks
3. Adjusting the pH of the feedwater between 8 and 9

1.9.7 Priming and Foaming (Carry-over Process)

Steam sometimes may be associated with small droplets of water. Such
steam-containing liquid water is called wet steam. These droplets of
water may carry with them some dissolved salts and sludge materials
present in water. This phenomenon is called carry over process. This occurs
mainly due to priming and foaming. Priming and Foaming, usually
occur together.
(a) Priming It refers to the formation of wet steam by rapid boiling of
water at the heating surface.
Causes:
Priming may be caused by
(i) High steam velocity
(ii) Very high water level in the boiler
(iii) Improper boiler design
(iv) Sudden boiling of water
Prevention:
Priming can be controlled by
(i) Controlling the velocity of steam
(ii) Keeping the water level lower
(iii) Good boiler design
(b) Foaming The formation of stable bubbles above the surface of
water is called foaming. These bubbles are carried along with steam
leading to excessive priming.
Causes:
Foaming may be caused by presence of oil, grease in water and finely
divided sludge particles.
Prevention:
Foaming can be prevented by
1. Adding coagulants like sodium aluminate, aluminium hydroxide,
ferrous sulphate etc.
2. Adding antifoaming chemicals such as castor oil and synthetic
polyamides

1.10 WATER-SOFTENING METHODS

1.10.1 Softening of Water

Water used for industrial purposes should be pure, i.e. it should be
free from hardness, scale forming substances and corrosive agents like
dissolved O2, etc. The process of removing hardness-producing salts
from water is known as softening of water.
 Softening of water can be done by the following two ways
(a) External Treatment or External Conditioning
Treatment of water before feeding to the boiler is known as
external treatment.
(b) Internal Treatment or Internal Conditioning
Treating the raw water inside the boiler is known as internal
treatment.

Table 1.7 Differences between external and internal treatment

[Link] External Treatment Internal Treatment
1. The external treatment of water is carried The internal treatment of water is carried
out before its entry into the boiler. out in the boiler itself.
2. It includes limesoda process,permutit It includes colloidal conditioning, carbonate
process and ion-exchange process. conditioning, phosphate conditioning,
calgon conditioning, etc.
3. High-pressure boilers require Low-pressure boilers require internal
external treatment. treatment.
4. It is a preventive method. It is a corrective method.

1.11 EXTERNAL TREATMENT

It involves the removal of hardness producing salts from the water
before feeding into the boiler. The external treatment can be done by
the following methods.
(a) Lime soda process (precipitation method)
(b) Zeolite (or) Permutit process (ion-exchange method)
(c) Demineralisation (or) De-ionisation (ion-exchange method)
The above processes are the examples of water softening.
In an ion-exchange process, a reversible exchange of ions taking place
between a stationary solid phase and an external liquid mobile phase.

1.11.1 Lime Soda Process

The lime soda process is a very important method used for the softening
of water.
(a) Principle
The lime soda process involves the chemical conversion of all the soluble
hardness-causing salts by the addition of soda and lime into insoluble
precipitates which could easily be removed by settling and filtration.
In this process, water to be softened is treated with calculated amounts
of lime Ca(OH)2 and soda Na2CO3. For quick completion of reactions,
the reagents may be used in 10 % excess. The functions of lime and soda
are as follows.
(i) Functions of Lime
Lime removes
1. Temporary hardness
2. Permanent magnesium hardness
3. Dissolved iron and aluminium salts
4. Dissolved CO2 and H2S gases
5. Free mineral acids present in water
The reactions involved are as follows:
1. Removal of temporary calcium and magnesium hardness
Ca(HCO3)2 + Ca(OH)2 2CaCO3 Ø + 2H2O
Mg(HCO3)2 + 2Ca(OH)2 2CaCO3 Ø + Mg(OH)2 Ø + 2H2O
2. Removal of permanent magnesium hardness
MgCl2 + Ca(OH)2 Mg(OH)2 Ø + CaCl2
MgSO4 + Ca(OH)2 Mg(OH)2 Ø + CaSO4
3. Removal of dissolved iron and aluminium salts
Al2(SO4)3 + 3 Ca(OH)2 2Al(OH)3 Ø + 3CaSO4
FeSO4 + Ca(OH)2 Fe(OH)2 Ø + CaSO4
2Fe(OH)2 + H2O +1/2 O2 2Fe(OH)3 Ø
4. Removal of dissolved CO2 and H2S
CO2 + Ca(OH)2 CaCO3 Ø + H2O
H2S + Ca(OH)2 CaS Ø + 2H2O
5. Removal of free mineral acid
2HCl + Ca(OH)2 CaCl2 + 2H2O
H2SO4 + Ca(OH)2 CaSO4 + 2H2O
(ii) Functions of Soda
During the removal of Mg2+, Fe2+, Al3+, HCl and H2SO4 by lime,
permanent calcium hardness is introduced in the water due to formation
of calcium salts. The permanent calcium hardness, thus introduced on
account of the treatment of water with lime and the permanent calcium
hardness already present in water before lime treatment, are removed
by soda. The reactions involved are as follows:
CaCl2 + Na2CO3 CaCO3 Ø + 2NaCl
CaSO4 + Na2CO3 CaCO3 Ø + Na2SO4
The chemical reactions involved in the lime soda process are quite
slow. Moreover, the precipitates formed [particularly of CaCO3 and
Mg(OH)2] are fine and have a tendency to form super-saturated solutions.
This results in after deposition of these precipitates later in the pipes and
boiler tubes leading to their clogging and corrosion. These drawbacks
of the process can be overcome by
(a) thorough mixing of chemicals and water,
(b) allowing proper time for the completion of reactions,
(c) the use of accelerators such as active charcoal, and
(d) the use of coagulants such as alum or NaAlO2.
(b) Process
The lime-soda process can be carried out both at room temperature
as well as at higher temperatures. The process carried out at room
temperature is called cold lime soda process and that carried out at
94°–100°C is called hot lime soda process.
(i) Cold Lime Soda Process
In this method, water to be softened is treated with calculated quantities
of lime and soda at room temperature. Small amounts of a coagulant such
as alum, aluminium sulphate, sodium aluminate, etc., are also added.
The coagulant helps the finely divided precipitate formed in the process
to flocculate. Sodium aluminate also helps in the removal of silica and
oil present in water.
Method: The mixture of water, calculated quantities of lime and soda
and a small amount of a coagulant is fed from the top into the inner
chamber of a vertical circular tank (Fig. 1.3). The chamber is provided
with a vertical rotating shaft carrying a number of paddles to ensure
vigorous stirring and continuous mixing of water with the chemicals
added.

Inlet Raw water

for chemicals inlet

Softened water
outlet
Paddle Fibre filter
stirrer
Vertical circular
tank

Sludge
Outlet for
sludge

Fig. 1.3 Cold lime soda process

 The chemical reactions take place and the hardness-producing salts
get converted into insoluble precipitates which accumulate in the form of
a heavy sludge. As the softened water reaches the outer coaxial chamber,
it rises upwards and is filtered by a wood-fibre filter and finally taken
out from an outlet provided at the top of the outer cylinder. The heavy
sludge settles down at the bottom of the outer chamber and is taken out
through an outlet.
The softened water obtained from this process contains a residual
hardness of about 50–60 ppm.
(ii) Hot Lime Soda Process
In this process, water is treated with the softening chemicals at a
temperature of 94°–100°C. Since the process is carried out at a temperature
close to the boiling point of the solution, the reaction proceeds faster and
the softening capacity of the process increases several times.
Raw water
inlet

Steam
Lime + Soda inlet
(Softening
chemicals)
Reaction
Tank Sand Filter

Conical Fine
Sedimenatathdn
Tank Coarse
Gravel
Sludge

Sludge outlet Softened

water

Fig. 1.4 Hot lime soda process

At this temperature, the viscosity of water is much less than that

at room temperature. Hence, rate of aggregation of particles increases
and there is hardly any need of adding any coagulant. Moreover, the
dissolved gases also escape to some extent at the temperature of the
process.
Method: A typical hot lime soda water softening plant is shown in
Fig. 1.4. It consists of
(i) A reaction tank
(ii) A conical sedimentation vessel
(iii) A sand filter
 Raw water is fed from the top into the reaction tank where it is
thoroughly mixed with calculated quantities of softening chemicals and
is agitated with superheated steam. The reactions take place and water
gets softened. The softened water containing sludge then enters into the
sedimentation vessel where the sludge settles down. The softened water
rises up in the vessel, while precipitated sludge is taken out through an
outlet provided at the bottom of the vessel. The softened water is then
taken to a sand filter which ensures the complete removal of the sludge
from softened water.
The softened water obtained from this process contains a residual
hardness of 15–30 ppm.
Advantages of the Process
The hot lime soda process has the following advantages.
1. The process is much faster as compared to the cold soda lime
process.
2. It is very economical.
3. Lesser amounts of coagulants are needed.
4. The process increases the pH value of the treated water, thereby
reducing the corrosion of distribution pipes.
5. To a certain extent, iron and manganese are also removed from
water.
6. Much of dissolved gases in water are also removed.
7. Due to an increase in the pH, the amount of pathogenic bacteria
in treated water also gets reduced.
Disadvantages of the Process
The hot lime soda process has the following disadvantages.
1. Disposal of large amounts of sludge formed in the process poses
problems.
2. The treated water obtained by this process is not completely
softened. It still contains a residual hardness of about 15–30 ppm,
which is not good for boilers.
Table 1.8 Difference between cold and hot lime soda process
[Link] Cold L-S Process Hot L-S Process
1. Done at room temperature. Done near the boiling point of water.
2. Reactions are slow and takes hours Fast and takes only 15 minutes.
to complete.
3. Precipitate is finely divided and therefore Coarse precipitate coagulants not needed.
coagulants are needed.
4. Tank size is large. Small and compact.
5. Residual hardness 50 to 60 ppm. 15 to 30 ppm.
6. Chemicals are consumed by dissolved CO2 and temporary hardness are
gas, CO2 etc. automatically removed.
(c) Numerical Calculation
We have already seen that the lime-soda process involves the conversion
of soluble hardness-producing salts into insoluble substances which could
easily be removed. Besides the removal of hardness causing substances,
the process also removes Fe2+ and Al2+ salts, free mineral acids such as
HCl, H2SO4 and dissolved gases such as CO2 and H2S. From the chemical
reaction involved in the process it is clear that:
(i) One equivalent of temporary calcium hardness requires one
equivalent of lime
(ii) One equivalent of temporary magnesium hardness requires two
equivalents of lime
(iii) One equivalent of permanent magnesium hardness requires one
equivalent of lime
(iv) One equivalent each of Fe2+, Al2+, CO2, H2S, and H2SO4 requires
one equivalent of lime
(v) One equivalent of permanent magnesium hardness requires one
equivalent of soda
(vi) Soda not only removes permanent calcium hardness already
present in water but also removes permanent calcium hardness
introduced during the removal of permanent magnesium hardness,
Fe2+, Al2+, HCl and H2SO4 by lime.
Hence for the calculation of the amounts of lime and soda required
for the treatment of a given sample of water, it would be convenient to
convert the amounts of all the substances present in the sample in terms
of CaCO3 equivalent. As we have already seen, CaCO3 equivalent is
given by
W × 50
CaCO3 equivalent = _______
E
where
W = mass of the impurity and
E = equivalent mass of the impurity
The lime and soda requirements can be calculated as follows:
(i) Lime Requirement
100 parts by mass of CaCO3 are equivalent to 74 parts by mass of
Ca(OH)2. Hence if the amounts of impurities are expressed in terms of
their CaCO3 equivalents, the amount of lime required to soften a given
sample of water is given by
Lime required for softening
74
= ____ × [Temp. calcium hardness + 2 × Temp. magnesium hardness
100
+ Perm. magnesium hardness + CO2 + HCl + H2SO4 + Fe2+ + Al3+
+ HCO3– – NaAlO2; all expressed in terms of CaCO3].
(ii) Soda Requirement
Soda required for softening
106
= ____ × [Perm. Calcium hardness + Perm. Magnesium Hardness
100
+ HCl + H2SO4 + Fe2+ + Al3+ – HCO3– – NaAlO2; all expressed in
terms of CaCO3 equivalents]
The following points are important to be noted
• 1 equivalent HCO 3– requires 1 equivalent of lime which
simultaneously produces 1 equivalent of CO32–.
Ca(OH)2 + 2HCO3– CaCO3 + CO32– + H2O
2 equivalents 2 equivalents 2 equivalents

1 equivalent of CO32–
ions thus produced may be regarded as
equivalent to 1 equivalent of soda. This is why corresponding
quantity of HCO3– in equivalent has been subtracted in the
calculation of soda requirement.
• NaAlO2 requires neither lime nor soda. However, 1 equivalent
of NaAlO2 undergoes hydrolysis to produce 1 equivalent of OH-
which may be regarded as equivalent to 1 equivalent of lime.
NaAlO2 + 2H2O NaOH + Al(OH)3
1 equivalent 1 equivalent

This is why corresponding quantity of NaAlO2 in equivalent

has been subtracted in the calculations of both lime and soda
requirements mentioned above.

Example 16 A sample of water contains following impurities; Mg(HCO3)

= 146 mg/L, CaCl2 = 111 mg/L, MgSO4 = 60 mg/L, and Ca(NO3) = 82 mg/L.
Calculate the quantity of lime (85% pure) and soda (90% pure) needed for
softening of 10,000 litres of water.
Solution:
(i) Calculation of CaCO 3 equivalents of hardness-producing
substances:
CaCO3 equivalent
Mass of the Equivalent mass
Substance W x 50
______
Substance of Substance (E)
E
146
____
Mg(HCO3)2 146 mg/L 73 × 50 = 100 mg/L
73
111
____
CaCl2 111 mg/L 55.5 × 50 = 100 mg/L
55.5
60
___
MgSO4 60 mg/L 60 × 50 = 50 mg/L
60
82
___
Ca(NO3)2 82 mg/L 82 × 50 = 50 mg/L
82
(ii) Calculation of lime requirement:
100
Since lime is 85% pure, purity factor = ____
85
Lime is required for Mg(HCO3)2 and MgSO4. Hence, 85% pure lime
required for the treatment of 10,000 litres of water
74
= ____ × [2 × Mg(HCO3)2 + MgSO4 as CaCO3 equivalents]
100
× purity factor × volume of water
74 100
= ____ × [2 × 100 + 50] × ____ × 10,000
101 85
74 100
= ____ × 250 × ____ × 10,000
100 85
= 2176470.58 mg
= 2.176 kg
(iii) Calculation of soda requirement:
100
Since soda is 90% pure, purity factor = ____
90
Soda is required for CaCl2 and Ca(NO3)2 and CaSO4 generated as a
result of reaction of lime with MgSO4.
Hence, 90% pure soda required for softening of 10,000 litres of
water
106
= ____ × [CaCl2 + Ca(NO3)2 + MgSO4 as CaCO3 equi.]
100
× purity factor × volume of water
106 100
= ____ × [100 + 50 + 50] × ____ × 10,000
100 90
106 100
= ____ × 200 × ____ × 10,000
100 90
= 2355555.5556 mg
= 2.355 kg

Example 17 A water sample gave the following constituents on analysis:

Ca(HCO3)2 = 20 ppm, Mg(HCO3) = 18 ppm, CaSO4 = 17 ppm, MgCl2 = 24
ppm MgSO4 = 3 ppm and NaCl = 2.5 ppm. Calculate the amount of lime (95%
pure) and soda (90% pure) needed for the trearment of 20,000 litres of water.
Also calculate the cost of chemicals if costs per 100 kg each of lime and soda
are Rs.80 and Rs. 2550 respectively.
Solution
(i) Calculation of CaCO3 equivalents of impurities:
CaCO3 Equivalent
Mass of Equivalent mass
Substance W x 50
______
Substance (W) of Substance (E)
E
20
___
Ca(HCO3)2 20 ppm 81 × 50 = 12.3 ppm (or) mg/L
91
18
___
Mg(HCO3)2 18 ppm 73 × 50 = 12.3 ppm (or) mg/L
73
17
___
CaSO4 17 ppm 68 × 50 = 12.5 ppm (or) mg/L
68
24
____
MgCl2 24 ppm 47.5 × 50 = 25.3 ppm (or)mg/L
47.5
3
___
MgSO4 3 ppm 60 × 50 = 2.5 ppm (or) mg/L
60
NaCl 2.5 ppm Ignored as it does not produce hardness

(ii) Calculation of lime requirement:

100
Since lime is 95% pure, purity factor = ____
95
Lime is required for Ca(HCO3)2 and MgCl2 and MgSO4.
Hence, 95% pure lime required for the treatment of 20,000 litres of
water
74
= ____ × [Ca(HCO3)2 + 2 × Mg(HCO3)2 + MgCl2 + MgSO4 as CaCO3
100
equi.] × purity factor × volume of water
74 100
= ____ × [12.3 + 2 × 12.3 + 25.3 + 2.5] × ____ × 20,000
100 95
74 100
= ____ × 64.7 × ____ × 20,000
100 95
= 1007957.8947 mg
= 1.0079 kg

(iii) Calculation of soda requirement:

100
Since soda is 90% pure purity factor = ____
90
Soda is required for CaSO4 and the calcium hardness generated as a
result of reaction of lime with MgCl2 and MgSO4
Hence, 90% pure soda required for softening of 20,000 litres of
water
 106
= ____ × [CaSO4 + MgCl2 + MgSO4 as CaCO3 equi] × purity factor
100
× volume of water
106 100
= ____ × [12.5 + 25.3 + 2.5] × ____ × 20,000
100 90
106 100
= ____ × 40.3 × ____ × 20,000
100 90
= 949288.88 mg
= 0.949 kg
Cost of chemicals:
80
Given that the cost of lime = ____ = Rs 0.80 per kg
100
2550
The cost of soda = _____ = Rs 25.50 per kg
100
Hence, the cost of lime and soda required for the treatment of the
sample of water under consideration
= 1.0079 × 0.80 + 0.949 × 25.50
= Rs 0.806 + Rs 24.19
= Rs 24.99

1.11.2 Zeolite (or) Permutit Process

Zeolites are naturally occuring hydrated sodium alumino silicate
minerals:
Na2O . Al2O3. × SiO2 yH2O where x = 2 to 10 and y = 2 to 6.
Natural zeolites are nonporous. The synthetic form of zeolite is known
as permutit. Synthetic zeolite is represented by Na2Ze. Synthetic zeolites
are porous and have a jelly structure. They are prepared by heating
together china clay, feldspar and soda ash. These zeolites have higher
exchange capacity per unit weight than natural zeolites.
In this synthetic zeolite process, the hard water is allowed to percolate
through sodium zeolite. The sodium ions which are loosely held in Na2Ze
are replaced by Ca2+ and Mg2+ ions present in the water.
(a) Process
In this process, the hard water is passed through a bed of sodium zeolite
(Na2Ze).
 NaCl

Hard
water Hard water

Sodium
zeolite

Soft water

Fig. 1.5 Zeolite process

The hardness-causing ions (Ca2+, Mg2+) in hard water is replaced by

loosely held sodium ions in zeolite bed (Fig. 1.5). The outgoing soft water
contains only sodium ions.
Na2Ze + Ca(HCO3)2 CaZe + 2NaHCO3
Na2Ze + Mg(HCO3)2 MgZe + 2NaHCO3
Na2Ze + CaCl2 CaZe + 2NaCl
Na2Ze + MgCl2 MgZe + 2NaCl
Na2Ze + CaSO4 CaZe + Na2SO4
Na2Ze + MgSO4 MgZe + Na2SO4
As sodium ions do not give any hardness to water, the effluent water
will be soft.
(b) Regeneration
After the softening process, the zeolite is completely converted into
calcium and magnesium zeolites and it gets exhausted. At this stage,
the hard-water supply is stopped and the exhausted bed is regenerated
by treating with a concentrated 10% brine (NaCl) solution.
CaZe + 2 NaCl Na2Ze + CaCl2
MgZe + 2 NaCl Na2Ze + MgCl2
Exhausted Regenerated
zeolite zeolite

(c) Limitations of Zeolite Process

1. If the supplied water is turbid, the suspended matter must
be removed first by coagulation, filtration, etc. Otherwise, the
turbidity will clog the pores of zeolite bed making it inactive.
 2. If the water contains coloured ions (Mn2+, Fe2+), these ions should
be removed first because these ions produce manganese and iron
zeolite, which cannot be regenerated.
3. If any mineral acid present in the water, it will destroy the zeolite
bed, therefore it is neutralised first with soda (Na2 CO3).
(d) Advantages of Zeolite Process
1. Water quality of below 5 ppm hardness is obtained.
2. This equipment is compact and occupies small space.
3. It requires less time for softening.
4. It requires less skill for maintenance and operation.
5. No sludge is formed during this process.
6. Its operation is also easy.
(e) Disadvantages of Zeolite Process
1. This process cannot be used for turbid and acidic water as they
will destroy the zeolite bed.
2. This treatment replaces only cations leaving all the anions in the
soft water.
3. The zeolite process cannot be used for softening brackish water
because brackish water also contains Na+ ions. So the ion exchange
reaction will not take place.

1.11.3 Demineralisation (or) De-ionisation Process (or)

Ion-Exchange Process
In this method, ion-exchange resins are used as softening material. In
this process, cations like Ca2+, Mg2+ and anions like Cl–, SO42– which are
responsible for hardness are removed respectively by cation exchange
resins and anion exchange resins.
Ion-exchange resins are insoluble, cross-linked, long-chain organic
polymers with a microporous structure. The functional groups attached
to the chains are responsible for the ion-exchanging properties.
(a) Cation-exchange Resins (RH +)
Resins containing acidic functional groups (–COOH, –SO3H) are capable
of exchanging their H+ ions with cations of hard water, for example
(i) Sulphonated coals
(ii) Sulphonated polystyrene
R-SO3H ; R-COOH ∫ RH +
(b) Anion-exchange Resins (R’OH –)
Resins containing basic functional groups (–NH2, –OH) are capable of
exchanging their OH– ions with the anions of hard water, for example
(i) Cross-linked quaternary ammonium salts
(ii) Urea-formaldehyde resin
R-NR3OH ; R-OH ; R-NH2 ∫ R’OH –
(c) Process
The hard water first passed through a cation exchange column (Fig.1.6)
which absorbs all the cations like Ca2+, Mg2+, Na+, K+, etc., present in
the hard water and equivalent amount of H+ ions are released from this
column to water. Thus,
2RH+ + Ca2+ R2 Ca2+ + 2 H+
2RH+ + Mg2+ R2 Mg2+ + 2 H+
The cation-free water is then passed through an anion-exchange
column, which absorbs all the anions like Cl–, SO42– etc., present in the
water and equivalent amount of OH – ions are released from this column
to water. Thus,
R’(OH)– + Cl– R’ Cl– + OH–
2R’(OH)– + SO42– R2’SO42– + 2OH–
2R’(OH)– + CO32– R2’ CO32– + 2OH–
H+ and OH– ions (released from cation-exchange and anion-exchange
columns respectively) get combined to produce a water molecule.

Raw
Water

Cation Anlon
exchanger Exchanger

Acid For Alkali for

Regeneration Regeneration

Deionised
Water

Fig. 1.6 Demineralization process

 H+ + OH– H2O
Thus, the water coming out from the exchanger is free from both
cations and anions. This water is known as ion-free water (or) deionised
(or) demineralised water.
(d) Regeneration
When the cation-exchange column is exhausted, it can be regenerated
by passing a solution of dil. HCl (or) dil. H2SO4.
R2 Ca2+ + 2 H+ 2RH+ + Ca2+
R2 Mg2+ + 2 H+ 2RH+ + Mg2+
When the anion-exchange column is exhausted, it can be regenerated
by passing a solution of dil. NaOH.
R’ Cl– + OH– R’(OH)– + Cl–
R2’SO42– + 2OH– 2R’(OH)– + SO42–
R2’ CO32– + 2OH– 2R’(OH)– + CO32–
(e) Advantages
1. Highly acidic (or) alkaline water can be treated by this process.
2. It generates very low hardness of water(nearly 2 ppm). So such
water can be used in high pressure boilers.
(f) Disadvantages
1. The equipment is costly and more expensive chemicals are
needed.
2. If the water contains turbidity then the output of the process is
reduced.

Table 1.9 Comparison of zeolite and demineralisation process

[Link] Zeolite (or) Permutit Process Demineralisation (or) Deionisation Process
1. This is an ion-exchange process. This is also an ion-exchange process.
2. It exchanges only cations. Both the cation and anions are exchanged.
3. Residual hardness is 1–5 ppm. Residual hardness is 0–2 ppm.
4. Cost of plant and material is high. Cost is higher.
5. Operating expenses are low. High operating expenses.
6. Acidic water cannot be treated. Even highly acidic or highly alkaline water
can be treated.
7. Treated water contains more dissolved No dissolved solids.
solids (sodium salts).
(g) Characteristics of Soft, Deionised and Distilled Water
(i) Hard Water
It contains all hardness-producing ions.
(ii) Soft Water
1. It does not contain hardness-producing ions like Ca2+, Mg2+
2. It may contain Na+, K+, SO42–, Cl– ions and micro-organisms.
(iii) De-ionised Water (Mineral Water)
1. It does not contain any ions including hardness-producing
cations.
2. It may contain some amount of microorganisms.
(iv) Distilled Water
It does not contain any ions and microorganisms, because it is prepared
by condensing the vapour of boiling water.

1.12 INTERNAL CONDITIONING (OR) INTERNAL

TREATMENT (OR) BOILER COMPOUNDS
In this process, an ion is prohibited to exhibit its original character by
‘complexing’ or converting it into other more soluble salts by adding an
appropriate reagent. An internal treatment is accomplished by adding a
proper chemical to the boiler water either
(a) to precipitate the scale-forming impurities in the form of sludges,
which can be removed by blow down operation, or
(b) to convert them into compounds, which will stay in dissolved
form in water and thus do not cause any harm.
Note:
1. Blow-down operation is partial removal of hard water through a
tap at the bottom of boiler, when extent of hardness in the boiler
becomes alarmingly high.
2. ’Make-up’ water is addition of fresh softened water to the boiler
after blow-down operation.
Internal treatment methods are generally followed by blow-down
operation, so that accumulated sludge is removed. Important internal
conditioning/treatment methods are the following:
(a) Colloidal Conditioning
Scale formation in boilers is mainly due to crystalline precipitates. When
certain chemicals like tannin or agar agar ,kerosene, gelatin and glue
are added to water,these substances get coated on the outer surfaces of
crystalline precipitates and convert them into colloidal nonsticky and
sludge-like precipitates, which can be removed by mechanical methods
of blow operation.
(b) Carbonate Conditioning
In low-pressure boilers, scale formation can be avoided by adding
Na2CO3 to the boiler water. The scale-forming salts like CaSO4 are
partially converted to CaCO3.
CaSO4 + Na2CO3 CaCO3 + Na2SO4
The forward reaction is favoured by increasing the concentration of
CO32–. Calcium carbonate is precipitated in the boiler as loose sludge
which can be scrapped off. For the precipitation of CaCO3, the carbonate
ions added should exceed the sulphate ions present in water.
(c) Calgon Conditioning
Calgon is sodium hexa metaphosphate with the composition
Na2[Na4 (PO3)6]. During the process of softening water, four sodium ions
are replaced by double salts containing calcium inside the complex. Since
the complex is highly soluble, there is no problem of sludge disposal.
Na2 [Na4 (PO3)6] 2Na+ + [Na4(PO3)6]2–
Calgon

2 CaSO4 + [Na4 (PO3)6]2– [Ca2 (PO3)6]2– + 2 Na2SO4

Highly soluble complex

(d) Phosphate Conditioning

In high-pressure boilers, CaSO4 forms hard-type scale. This is because
the solubility of CaSO4 decreases with increase of temperature. It can be
converted into soft sludge by adding excess of soluble phosphates. The
optimum pH for the precipitation of Ca3(PO4)2 soft sludge is 9.5 – 10.5.
pH = 9.5 – 10.5
3 CaSO4 + 2 Na3PO4 Ca3 (PO4)2 + 3 Na2SO4
Soft sludge

There are three types of phosphates employed for this purpose

1. Trisodium phosphate — Na3PO4 (too alkaline)
2. Disodium hydrogen phosphate — Na2HPO4 (weakly alkaline)
3. Monosodium dihydrogen phosphate — NaH2PO4 (acidic)
The choice of salt depends upon the alkalinity of the boiler feedwater.
Hence, Na3PO4 is used for too acidic water, Na2HPO4 is used for weakly
acidic water, and NaH2PO4 is used for alkaline water in boilers.
(e) Treatment with Sodium Aluminate
When sodium aluminate is treated with boiler water, it gets hydrolysed
to give sodium hydroxide and a gelatinous precipitate of aluminium
hydroxide.
NaAlO2 + 2 H2O NaOH + Al(OH)3
The formed NaOH reacts with magnesium salts.
MgCl2 + 2 NaOH Mg(OH)2 + 2 NaCl
The flocculent precipitates of Mg(OH)2 and Al(OH)3 entrap finely
suspended and colloidal impurities like sand and oil drops which are
difficult to remove ordinarily. The flocculent precipitates then settle to
the bottom and can be removed easily.

1.13 DESALINATION OF BRACKISH WATER

Depending upon the quantity of dissolved solids, water is graded as
1. Fresh water contains < 1000 ppm of dissolved solids.
2. Brackish water contains > 1000 ppm but < 35000 ppm of dissolved
solids.
3. Sea water contains > 35,000 ppm of dissolved solids.
Water containing high concentration of dissolved salts/solids is
known as brackish water, for example sea water contains about 3.5%
salts. Brackish water is unfit for domestic and industrial applications.
Hence, it is necessary to remove the high concentration of the salts. The
process used for the removal of salts from brackish or saline water is
called desalination.
The common method for the desalination of brackish water are
1. Electrodialysis
2. Reverse osmosis
3. Distillation
4. Freezing.

1.13.1 Electrodialysis
Electrodialysis is one of the efficient techniques used for the desalination
of saline water.
(a) Principle
Electrodialysis involves the separation of dissolved salts from saline
water in the form of ions under the influence of a direct current using
particular types of membranes called ion-selective membranes.
 An ion-selective membrane is permeable for only one kind of ions
having specific charge. For example, a cation-selective membrane allows
the passage of cations only. It does not let anions to pass through it.
Similarly, an anion-selective membrane is permeable only to anions and
checks the passage of cations through it.
When a direct current is passed through saline water enclosed between
ion-selective membranes, the cations of the dissolved salt move towards
the cathode through the cation-selective membrane, whereas anions of
the salts move towards the anode through the anion-selective membrane.
This decreases the concentration of ions in saline water and after some
time, the saline water turns into fresh water.
(b) Process
The process is carried out in a special type of cell called electrodialysis
cell shown in Fig. 1.7. It consists of a large number of paired sets of ion-
selective membranes. Saline water under a pressure of about 5-6 kg/m2
is introduced from the top of the cell and is made to pass between
membrane pairs.
An electric field is applied perpendicular to the direction of flow of
water. The ions start moving towards the oppositely charged electrodes
through the membranes. On account of this, the concentration of ions in
alternate compartments 2, 4, 6, etc., decreases, while the concentration
of ions in alternate compartments 1, 3, 5, 7, etc., goes on increasing.
Saline water

C A C A C A

Cation 1 2 3 4 5 6 7
selective + + +
Anion
membrane selective
(c) + + +
membrane
+ + + (A)
+
+ + +

Cathode + + + Anode
Cation Selective
+ + + C Membrane

Anion selective
A
membrane

Pure water
Concentrated
saline water

Fig. 1.7 Electrodialysis of saline water

 Thus, water collected from compartments 2, 4, 6, etc., is pure; while
that collected from compartments 1, 3, 5, 7, etc., is more concentrated
saline water.
(c) Examples for Ion-selective Membranes
• Cation-selective membrane—polystyrene containing sulphonic
acid group
• Anion-selective membrane—polystyrene containing tetra
ammonium chloride
(d) Advantages of Electrodialysis Process
1. The equipment used in the process is very compact.
2. The cost of installation is economical.
3. The cost of operation of the process largely depends upon the cost
of electricity available.

1.13.2 Reverse Osmosis

(a) Process
It is a membrane process by which water is separated from saline water.
Osmosis is defined as the spontaneous flow of ‘water’ from dilute to
more concentrated solution through a semipermeable membrane. The
driving force in this phenomenon is called osmotic pressure.
A semipermeable membrane is one which permits only water
molecules to pass through it. Examples of semipermeable membranes
are cellulose acetate, polyamide, polymide, etc.
Pressure
Semipermeable Semipermeable
membrane membrane

Net flow of solvent Net flow of solvent

Dilute solution Conc. solution Dilute solution Conc. solution

(a) (b)

Fig. 1.8 (a) Osmosis (b) Reverse osmosis

 This natural process can be reversed by applying pressure higher than
the osmotic pressure on the concentrated side. Thus the solvent is forced
to move from concentrated side to dilute side across the membrane. This
principle is known as reverse osmosis.
In the reverse osmosis process (Fig. 1.9), the pure water (free from
ions) is separated from the contaminated brine water (salty water). This
membrane filtration is also called super filtration (or) hyper filtration.

Fig. 1.9 Desalination of sea water

(b) Advantages
1. This method has greater advantages of removing ionic, non-ionic,
colloidal and high-molecular weight organic matter.
2. The lifetime of the membrane is quite high (2 years).
3. The membrane can be replaced within a few minutes. It provides
nearly uninterrupted water supply.
4. Due to low capital cost, low operating cost and high reliability,
this method is superior than other methods.
(c) Applications
1. Reverse osmosis plays a major role in providing portable water
defined by the WHO criterion of < 500 ppm of total dissolved
solids (TDS).
2. Extremely high-quality water required for nuclear power plants
can be made from sea water by the reverse-osmosis process.
3. Sugar concentration, waste-water recovery and beverage uses are
a few of the current popular applications of the reverse-osmosis
process.
 1.14 DRINKING WATER (OR) POTABLE WATER (OR)
DOMESTIC WATER TREATMENT
Water which is safe to drink and fit for human consumption is called
drinking water or potable water.

1.14.1 Specifications for Drinking Water

The common specifications recommended by the US Public Health for
drinking water are given below.
(i) Water should be clear and odourless.
(ii) It should be cool.
(iii) It should be pleasant to taste.
(iv) Turbiditiy of water should not exceed 10 ppm.
(v) pH of the water should be in the range of 7.0–8.5.
(vi) Chloride and sulphate contents should be less than 250 ppm.
(vii) Total hardness of the water should be less than 500 ppm.
(viii) Total dissolved solids should be less than 500 ppm.
(ix) Fluoride content of the water should be less than 1.5 ppm.
(x) The water must be free from disease-producing bacteria.
(xi) Water should be free from objectionable dissolved gases like
H2S.
(xii) Water should be free from objectionable minerals such as lead,
chromium, manganese and arsenic salts.

1.14.2 Various Stages of Domestic Water Treatment

Natural water from rivers, canals, etc., does not confirm to all the
required specifications of drinking water. For removing various types of
impurities, the following treatment processes are employed.
Note:
Municipal water treatment does not aim at removing the dissolved salts
present. Consequently, municipalities do not, generally, supply softened
water.
The various stages in the treatment of water are given below.
(a) Removal of Suspended Impurities
(i) Screening
The raw water is passed through screens, having large number of holes,
where floating matter are removed.
(ii) Aeration
Aeration of water involves
• Increasing the content of oxygen in water, make it fresh and
promote taste
• Removing unwanted gases like H2S, CO2 and other volatile
substances causing bad odour
• Removing the salts of iron and manganese.
(iii) Sedimentation
In this process, water is allowed to stand undisturbed in big tanks for
2 to 8 hours. Most of the suspended particles settle down at the bottom
due to gravity. In this method, about 75% of the suspended impurities
are removed and clean supernatant water is drawn from the tank with
the help of pumps.
(iv) Sedimentation with Coagulation
The suspended and colloidal impurities are separated in the sedimentation
tank by gravitation. The main principle of sedimentation is to allow water
to rest or flow at a very slow velocity so that the heavier particles settle
down due to gravity.
However, fine particles take many hours or sometimes days to settle
down. So certain chemicals are added to speed up the sedimentation
and the process is called coagulation.
The common coagulants (chemicals) used are generally salts of
aluminium (alum, sodium aluminate) and salts of iron (ferrous sulphate,
ferric sulphate, ferric chloride).
When a congulant is added to the water and mixed thoroughly, a
thick gelatinous precipitate is formed which is insoluble in water. This
precipitate is called floc.
Some of the chemical coagulants are the following:
1. Alum [K2SO4.Al2(SO4)3.24H2O] is the most widely used in water-
treatment plants. Alum reacts with water in the presence of alkalinity of
water. If natural alkalinity is not present, sufficient lime is also added.
Al2(SO4)3 + Ca(HCO3)2 2Al(OH)3 Ø + 3CaSO4 + 6CO2
Coagulant ([Link] (Al. hydroxide
present in water) Flocculent ppt)

2. Sodium aluminate (NaAlO2) is obtained from bauxite refineries in the

form of a thick solution. This can very easily be used for treating water
having no alkalinity (pH less than 7). The pH range for best results is
5.5–8.0
NaAlO2 + 2H2O Al(OH)3 Ø + NaOH
Gelatinous floc of al. hydroxide
 The aluminium hydroxide floc causes sedimentation. The sodium
hydroxide thus produced precipitates of magnesium salts as Ma(OH)2.
MgSO4 + 2 NaOH Mg(OH)2 Ø + Na2SO4
3. Ferrous sulphate (FeSO4.7H2O) is also commonly used for coagulation
purposes. It gives good results above pH values of 8.5(slightly alkaline).
Ferrous sulphate reacts with water in the presence of alkalinity. If
alkalinity is not present, sufficient lime is also added.
FeSO4 + Mg(HCO3)2 Fe(OH)2 Ø + MgCO3 + CO2 + H2O
(Coagulant) ([Link].
present in water)

4Fe(OH)2 Ø + O2 + 2H2O 4 Fe(OH)3 Ø

Dissolved oxygen Ferric hydroxide
(heavy floc)

Fe(OH) 3 is in the form of heavy floc, which causes quick

sedimentation.
(v) Filtration
It is the process of removal of colloidal and suspended matter (remaining
after sedimentation) and bacteria by passing water through a filter bed
containing fine sand, coarse sand and gravel.
Generally, filtration is carried out by using sand filters.

(b) Removal of Microorganisms

The process of destroying or killing the disease producing bacteria,
microorganisms, etc., from the water and making it safe for use is called
disinfection. The chemicals or substances, which are added to water for
killing the bacteria, etc., are known as disinfectants. This can be carried
out by the following methods.

Water
inlet

Fine sand

Coarse sand

Fine gravel

Coarse gravel

Water outlet

Fig. 1.10 Sand filter

(i) By Boiling
The harmful disease-producing bacteria can be killed by boiling the
water to 100°C for 10 to 15 minutes.
(ii) Ultraviolet Radiations
UV rays are produced by passing electric current through mercury
vapour lamp. This is particularly useful for sterilising water in a
swimming [Link] method is found to be costly and it cannot be used
for turbid water.
(iii) Sterilisation or Disinfection by Ozone (O3 )
Ozone is a powerful disinfectant and is readily absorbed by water.
Ozone is highly unstable and breaks down, liberating nascent oxygen
[O] which is capable of destroying the bacteria. It not only kills bacteria
but also bleaches, decolorises and deodorizes water and improves the
taste of water.
O3 O2 + [O]
Ozone Nascent oxygen

The commonly used dose strength of ozone for sterilisation of water

is 2–3 ppm. The method being expensive is generally not used for the
sterilisation of municipal water supply.
(iv) Chlorination
The process of adding chlorine to water is called chlorination. Chlorine
is a strong oxidising agent, is colourless and the excess of it may easily
escape. It is mostly preferred for the disinfection of water. Chlorination
can be done by the follwing methods.
• By adding chlorine gas: Chlorine (gas or liquid form) produces
hypochlorous acid (powerful germicide)
Cl2 + H2O HCl + HOCl
Hypochlorous acid
HOCl + Bacteria Bacteria are killed
Advantages
1. About 0.3–0.5 ppm of chlorine is sufficient to act as ideal
disinfectants.
2. It is cheap.
3. For storing it requires minimum space.
Disadvantages
1. Adding excess chlorine leads to unpleasant taste and odour.
2. At higher pH values, it is less effective and at lower pH values, it
is more effective.
• By adding chloramines (ClNH2): The use of excess of chlorine gas
or bleaching powder as disinfectant often produces disagreeable odour
and unpleasant taste in water.
The unpleasant taste can be avoided by the use of chloramine which
may be obtained by treating chlorine with ammonia in the ratio of 2:1
by volume.
NH3 + Cl2 ClNH2 + HCl
Chloramine provides a greater lasting effect than that of chlorine.
H2O + ClNH2 HOCl + NH3
HOCl + Bacteria Bacteria are killed + HCl + [O]
Nascent oxygen

• Addition of bleaching powder (CaOCl2): Bleaching powder has

the constitution Ca(OCl)[Link](OH)2. It is commonly represented
as CaOCl2 It contains about 30% available chlorine. It reacts with water
to produce hypochlorous acid which is a powerful disinfectant due to
its property of liberating nascent oxygen. One kilogram of bleaching
powder is sufficient to sterilise one million parts of water.
H2O + CaOCl2 Ca(OH)2 + Cl2
Bleaching powder

H2O + Cl2 HCl + HOCl

Hypochlorous acid

HOCl + Bacteria Bacteria are killed + HCl + [O]

Nascent oxygen

The nascent oxygen thus liberated kills the pathogens by oxidation.

Drawback
1. Only calculated amount of CaOCl2 should be used, since an excess
of it gives bad taste and smell to the treated water.
2. Bleaching powder introduces calcium ions to water which increases
water hardness.
3. During storage, the water quality deteriorates, and therefore the
water should be analyzed for its effective chlorine content before
use.
(c) Break-point Chlorination (or) Free Residual Chlorination
Water contains the following impurities:
(i) Bacteria
(ii) Organic matter
(iii) Reducing substances (Fe2+, H2S)
(iv) Free ammonia
 Oxidation of reducing
Residual chlorine
Destruction

agents by chlorine
e
of chloromines rin
Formation h lo
and organic c
of chloromines compounds al
i du
s
re
e e
Fr

Chlorine dose added.

Fig. 1.11 Break-point chlorination curve

Chlorine may be added to water directly as a gas or in the form

of bleaching powder. When chlorine is applied to water, the results
obtained can be depicted graphically as in Fig. 1.14. The graph shows
the relationship between the amount of chlorine added to water and the
residual chlorine.
It is seen from the graph that initially the applied chlorine is used to
kill bacteria and oxidises all the reducing substances present in the water
and there is no free residual chlorine.
As the amount of applied chlorine increases, the amount of combined
residual chlorine also increases. This is due to the formation of
chloramines and other chloro compounds.
At one point, on further chlorination, the oxidation of chloramines
and other impurities starts and there is a fall in the combined chlorine
content. Thus the combined residual chlorine decreases to a minimum
point at which oxidation of chloramines and other impurities complete
and free residual chlorine begins to appear. This minimum point is
known as break-point chlorination.
Thus break-point chlorination eliminates bacterias, reducing
substances,organic substances responsible for the bad taste and odour
from the water.
(i) Advantages
1. It completely oxidises organic compounds, ammonia and other
reducing compounds.
2. It removes colour in water due to the presence of organic
matter.
3. It destroys completely 100% of all the disease-producing
bacteria.
 4. It removes both odour and taste from the water.
5. It prevents the growth of any weeds in water.
(d) De-chlorination
The water treated by break-point chlorination contains decomposition
products formed and may also contain excess of chlorine. These
objectionable qualities may be removed by filtering the treated water
over activated carbon. Over-chlorination of water can also be removed
by treating it with SO2 or Na2SO3.
SO2 + Cl2 + 2H2O H2SO4 + 2HCl
Na2SO3 + Cl2 + H2O Na2SO4 + 2HCl
Note:
Ozone is expensive. UV light can also be used as a disinfectant especially
for swimming-pool water. KMnO4 is a useful disinfectant for domestic
well water.

QUESTIONS

Two-Mark Questions with Answers

1. Define hard and soft water.
Soft water is one that gives good lather readily with soap solution.
Water that does not produce lather with soap readily but forms an
insoluble precipitate-like white scum is known as hard water.
2. Mention any two problems caused by turbidity.
• Objectionable in boilers and in cooling water systems
• Interference in water-softening processes
3. What is meant by apparent colour?
Colour which is caused by suspended matter is called apparent
colour.
4. Mention any two sanitary significances of acidity.
• Presence of carbonic acid and other organic acids in water
does not have any deleterious effects on human health (for
example, presence of CO2 in malt and carbonated beverages
has no adverse effects on human beings).
• However, acidic water corrodes concrete pipes and causes
dissolution of metals such as Cu, Zn, etc.
 5. Define carbonate and noncarbonate hardness of water.
Carbonate hardness is caused by the presence of dissolved
bicarbonates of calcium and magnesium. Temporary hardness is
mostly destroyed by mere boiling of water. Noncarbonate hardness
is due to the presence of dissolved chlorides and sulphates of
calcium and magnesium. Unlike temporary hardness, permanent
hardness is not destroyed on boiling.
6. Define ppm and mg/lit.
ppm is defined as the number of parts by weight of CaCO3 present
in million parts by weight of water, and mg/lit is defined as the
number of milligrams of CaCO3 present in one litre of water.
7. A sample of water contains 240 mg of MgSO4 per litre. Calculate
the hardness in terms of CaCO3 equivalents.
Given
The amount of MgSO4 = 240 mg/lit
CaCO3 Weight of hardness producing salt Molecular weight
= _______________________________ ×
equivalent Molecular weight of the salt of CaCO3

We know that the molecular weight of MgSO4 =120.

240
Thus amount equivalent to CaCO3 = ____ × 100 = 200 mg/lit.
120
8. Mention any two specification of boiler feedwater.
Water used in boilers should be free from dissolved calcium and
magnesium salts and dissolved gases such as oxygen (O2) and
carbon dioxide (CO2).
9. Give the difference between scale and sludge.
[Link] Sludge Scale
1. Sludges are soft and non-adherent Scales are hard deposits which stick very
deposits. firmly to the inner surface of boiler during
steam generation.
2. Sludges are formed by Scales are formed by substances
substances like MgCl2, CaCl2, etc. like CaSO4, and Mg(OH)2.

10. Define caustic embrittlement.

Caustic embrittlement is a type of boiler corrosion, caused by using
highly alkaline water in the boiler. It refers to the inter-crystalline
cracking of boiler metal. In high-pressure boilers, Na2CO3
decomposes to give sodium hydroxide and carbon dioxide, and
this makes the boiler water caustic. This NaOH containing water
flows into the minute hair cracking usually present on the boiler
material by capillary action. Here water evaporates and the
 dissolved caustic soda concentration increases progressively. This
caustic soda attacks the surrounding area, thereby dissolving iron
of the boiler as sodium ferroate.
Na2CO3 + H2O 2NaOH + CO2
Fe + 2NaOH Na2FeO2 + H2 Ø
Sodium ferroate

11. What are the limitations of zeolite process?

1. If the supplied water is turbid, the suspended matter must
be removed first by coagulation, filtration, etc. Otherwise
the turbidity will clog the pores of the zeolite bed, making
it inactive.
2. If any mineral acid is present in the water, it will destroy
the zeolite bed. Therefore it is neutralised first with soda
(Na2 CO3).
12. What are cationic- and anionic-exchange resins?
Resins containing acidic functional groups (–COOH, –SO3H) are
capable of exchanging their H+ ions with cations of hard water.
They are said to be cationic exchange resins, e.g., sulphonated
coals, etc.,
Resins containing basic functional groups (–NH2, –OH) are capable
of exchanging their OH – ions with the anions of hard water. They
are said to be anionic exchange resins, e.g. cross-linked quaternary
ammonium salts, etc.
14. What is reverse osmosis?
If a solvent is forced to move from concentrated side to dilute side
across the membrane by applying osmotic pressure, it is known
as reverse osmosis.
15. Write the reaction of bleaching powder with water.
H2O + CaOCl2 Ca(OH)2 + Cl2
Bleaching powder

H2O + Cl2 HCl + HOCl

Hypochlorous acid

HOCl + Bacteria Bacteria are killed + HCl + [O]

Nascent oxygen

The nascent oxygen thus liberated kills the pathogens by

oxidation.
Ten-Mark Questions
1. Define the term ‘desalination’, and with a neat diagram describe
desalination by ‘reverse osmosis’ method.
2. What are coagulants? Write the mechanism of coagulation process
with a suitable example.
3. What is meant by reverse osmosis? Describe desalination of
brackish water by reverse-osmosis method.
4. What are boiler troubles? How are they caused? Suggest steps to
minimise boiler troubles.
6. Compare the zeolite process with ion-exchange process in water
softening. How will you regenerate the used-up reagents?
7. Describe the process of demineralisation of water using ion-
exchange resins and specify its advantages over zeolite process.
8. Explain break-point chlorination.
9. Name eight methods for disinfection of water.
10. With the help of a neat diagram, explain the use of electrodialysis
for desalination of water.
11. Define alkalinity. How is it determined?
12. Write short notes on (i) carry-over process, and (ii) lime-soda
process.
13. What are the water-quality physical parameters? Explain their
significance.
14. What is the principle of the EDTA method? Describe the estimation
of hardness of water by the EDTA method.
15. What is meant by sterilisation of water? Explain how sterilisation
of water is carried out by using chlorine and ozone.
 UNIT

2
Electrochemistry

2.1 INTRODUCTION
Electrochemistry is a branch of chemistry, which deals with the chemical
applications of electricity, i.e. chemical reactions produced by passing
electric current through an electrolyte or the production of electric current
through chemical reaction.
If a chemical reaction is driven by an external applied voltage then it
is known as electrolysis, and if a voltage is created by a chemical reaction
then the electrical arrangement is called a battery.

2.1.1 History of Electrochemistry

Understanding of electrical matters began in
the sixteenth century. During this century,
the English scientist William Gilbert spent 17
years experimenting with magnetism and,
to a lesser extent, electricity. For his work on
magnets, Gilbert became known as the ‘father of
magnetism.’
Fig. 2.1 Swedish chemist
In 1800, William Nicholson and Johann
Svante Arrhenius portrait
Wilhelm Ritter succeeded in decomposing water circa 1880s
into hydrogen and oxygen by electrolysis.
Svante Arrhenius (Fig. 2.1) published his thesis in 1884 on
investigations on the galvanic conductivity of electrolytes. From his
results, Arrhenius concluded that electrolytes, when dissolved in water,
become to varying degrees split or dissociated into electrically opposite
positive and negative ions.
 Walther Hermann Nernst (Fig. 2.2) developed
the theory of the electromotive force of the
voltaic cell in 1888. In 1889, he showed how the
characteristics of the current produced could
be used to calculate the free energy change in
the chemical reaction producing the current. He
constructed an equation, now known as Nernst
equation, which related the voltage of a cell to Fig. 2.2 German scientist
its properties. Walther Nernst portrait in
the 1910s
2.1.2 Types of Conductors
The material which conducts electricity is called a conductor. Conductors
are broadly classified into two types.
(a) Metallic conductor (b) Electrolytic conductor
(a) Metallic Conductors Metallic conductors are solid substances
which conduct electric current due to the movement of electrons from
one electrode to another. The conductance decreases with increase of
temperature.
Example: All metals, graphite
(b) Electrolytic Conductors An electrolytic conductor conducts
electric current due to the movement of ions in solution or in fused state.
The conduction increases with increase of temperature.
Example: HCl, NaOH, NaCl, etc.

Table 2.1 Difference between metallic conduction and electrolytic conduction

S. No. Metallic Conduction Electrolytic Conduction
1. It involves the flow of electrons in a It involves the movement of ions in a
conductor. solution.
2. It does not involve any transfer of It involves transfer of electrolyte in the form
matter. of ions.
3. Conduction decreases with increase in Conduction increases with increase in
temperature. temperature.
4. No change in chemical properties of the Chemical reaction occurs at the two
conductor. electrodes.

2.2 CELLS
A cell is a single arrangement of two electrodes dipping into a solution
of electrolyte or electrolytes. Cells may be divided into
(a) Electrolytic cells
(b) Electrochemical cells
(a) Electrolytic Cell
Electrolytic cells are cells in which electrical energy is used to bring
about a chemical reaction. The redox reaction in an electrolytic cell
is nonspontaneous. Electrical energy Battery
is required to induce the electrolysis + –
reaction. An example of an electrolytic e
–

cell is shown in Fig. 2.3, in which molten

NaCl is electrolyzed to form liquid e– Anode Cl (g) Cathode
2
sodium and chlorine gas. The sodium ions
migrate toward the cathode, where they
are reduced to sodium metal. Similarly, – +
chloride ions migrate to the anode and Cl Na
– +
are oxidized to form chlorine gas. This Cl Na
type of cell is used to produce sodium and Molten NaCl
chlorine. The chlorine gas surrounding the
Fig. 2.3 Electrolytic cell
cell can be collected. The sodium metal is
less dense than the molten salt and is removed as it floats to the top of
the reaction container.
At anode
2Cl– Cl2 + 2 e– (oxidation)
At cathode
Na+ + e– Na (reduction)

(b) Electrochemical Cell

An electrochemical cell is a device in which a redox reaction is utilized
to get electrical energy. An electrochemical cell is also commonly referred
to as voltaic or galvanic cell. The electrode where oxidation occurs is
called the anode; while the electrode where reduction occurs, is called
the cathode.
The practical application of an electrochemical or galvanic cell is
the Daniel cell. It consists of a zinc electrode dipping in ZnSO4 solution
(where oxidation takes place) and a copper electrode dipping in CuSO4
solution (where reduction takes place). In other words, each electrode
may be regarded as a half-cell. The electrode reactions in a Daniel cell
are the following:
At anode
Zn Zn2+ + 2 e– (oxidation)
At cathode
Cu2+ + 2 e– Cu (reduction)
 – Current (By sign convention direction of current
e is opposite to that of electrons)
V –
Zinc e Copper
rod rod
(Anode) (Cathode)

Salt Bridge
2+ 2+
Zn Cu
2+ 2–
Zn SO4
CuSO4
ZnSO4 Solution
Solution 2+ – 2+ –
Zn Æ Zn + 2e Cu + 2e Æ Cu
From the Into wire From the From Deposited onto
Zinc rod solution wire copper rod

Fig. 2.4 Daniel cell

Overall reaction
Zn + Cu2+ Zn2+ + Cu
Direction of electron (e–) flow

Zn ZnSO4 || CuSO4(aq) Cu
Anode (Cathode)

Direction of electric current flow

Table 2.2 Differences between electrolytic cells and electrochemical cells

Sl. No Electrolytic Cells Electrochemical Cells
1. Electrolytic cells are cells in which Electrochemical cells are cells in which
electrical energy is converted to chemical energy is converted to
chemical energy. electrical energy.
Example: Electrolysis Example: Daniel cell
2. Sign Convention: The cathode carries Sign Convention: The cathode carries
negative charge. The anode carries positive charge. The anode carries
positive charge. negative charge.
3. Here the electrons are supplied to the But electrons are drawn from the cell,
cell from the external battery,
i.e. electrons move in through the i.e. electrons move from anode to cathode
cathode and come out from the anode. through the external circuit.
4. The amount amount of electricity passed The emf produced in the cell is measured
during electrolysis is measured by by a potentiometer or voltmeter.
coulometer or ammeter.
5. The extent of chemical reaction occurring The emf of the cell depends on the
at the electrodes is governed by concentration of the electrolytes and the
Faraday’s law of electrolysis. chemical nature of the electrode.
Points to Remember
Reaction Direction of Sign at Sign at
Cell Type DG E Reduction Oxidation
Type e-flow Cathode Anode
Electrolysis Nonspon- + – Cathode Anode e-flow to – +
taneous cathode
Galvanic Spontan- – + Cathode Anode e-flow to + –
eous cathode

2.3 REPRESENTATION OF A GALVANIC CELL

According to present conventions, a galvanic cell is represented by

keeping in view the following points.
• Two half-cells: anodic half-cell and cathodic half-cell each make
up galvanic cell.
• The anodic half-cell is also called oxidation half-cell.
• The cathodic half-cell is also called reduction half-cell.
Depending upon the cell, a half-cell can be used both as a cathode or
as an anode, i.e. a half-cell may act as an anodic half-cell in one galvanic
cell, while the same half-cell may act as a cathodic half-cell in some other
galvanic cell.
The two half-cells (or electrodes) of a galvanic cell may be represented
as follows:
1. The anodic half-cell is written on the left-hand side while the
cathodic half-cell is written on the right-hand side.
2. The anode of the cell is represented by writing the metal first and
then the electrolyte, the two separated by a vertical line (|) or slash
(/) or semicolon (;).
The oxidation half-cell is represented as
M(s) | Mn+ (aq) or M(s) / Mn+ or M(s); Mn+ (aq)
The concentration of the electrolyte is mentioned within the
bracket after the cation, e.g.
Zn(s) | Zn2+ (aq) (1M)
3. The cathode of the cell is represented by writing the electrolyte
and its cation first and then the metal, the two are separated by a
vertical line (|) or slash (/) or semicolon (;).
The reduction half-cell is represented as
Mn+ (aq) | M(s) or Mn+ (aq) / M(s) or M(s); Mn+ (aq)
 The small vertical bar (|) or slash (/) drawn between M and Mn+
(aq) represents an electrode--electrolyte interface, i.e. the plane
where the electrode and the electrolyte meet.
4. In certain galvanic cells, the two electrodes are dipped into two
different electrolytes. Using a salt bridge develops the electrical
contact between the two half-cells. Such a salt bridge between
the two solutions is denoted by a double-bar (||) or a double
slash (//) between the two solutions as shown in the cell given
below.
Zn(s) | Zn2+ (aq) (1M) || Cu2+ (aq) (1M) | Cu(s)
Electrode–electrolyte Salt Electrolyte–electrode
interface bridge interface

or
Zn(s) / Zn2+ (aq) (1M) // Cu2+ (aq) (1M) / Cu(s)
Electrode–electrolyte Salt Electrolyte–electrode
interface bridge interface

5. Species that are in the same phase (e.g., different ions in the same
solution) are separated by a comma (,).
For example, a solution of HCl containing H+ and Cl– is described
as H+ (aq), Cl– (aq).
In case of gas electrodes such as hydrogen, the inert metal
platinum, (which serves as the electrical contact) is also written
while representing the half-cell.
Pt, H2 (1 atm); H+ (1M)
6. Sometimes a negative sign is put on the anode and a positive
sign on the cathode. The electrons flow from the negative pole
(anode) to the positive pole (cathode) in the external circuit.
Conventionally, current is said to flow in the opposite direction.
The complete formula of a cell may be represented as follows:
Direction of electron (e–) flow

(–) Zn | ZnSO4 (aq)(1M) || CuSO4(aq) (1M) | Cu (+)

Anode (Cathode)

Direction of electric current flow

2.4 REVERSIBLE AND IRREVERSIBLE CELLS

When a cell works in a thermodynamically reversible manner, it is called
a reversible cell. A cell is said to work reversibly when it is sending out
an infinitesimally small current, so that the reaction of the in cell remains
in the state of equilibrium.
(a) Reversible Cells They have to satisfy the following conditions:
1. If the cell emf is exactly equal to the emf is supplied from an
external source, the cell reaction will stop and no current will be
given out by the cell.
External emf = Cell emf
(No current flow)
2. If the external emf is infinitesimally less than the cell emf, the
current will flow from the cell which is proportional to the
chemical reaction taking place in the cell, e.g. discharging of the
cells
External emf < Cell emf
(Current flow from cell to external source)
3. If the emf applied externally is greater than the cell emf, the cell
reaction is reversed and the current will flow in the opposite
direction, e.g. charging in the secondary cells.
External emf > Cell emf
(Current flow from external source to cell)
A familiar example of a reversible cell is that of the Daniel cell. It is
represented as
Zn/ZnSO4(1M)||CuSO4(1M)/Cu
(i) Condition 1
The emf of a Daniel cell is 1.1 volts. If an emf of 1.1 volts is externally
applied, the cell reaction stops.
(ii) Condition 2
When the external emf is just smaller than that of the cell, the reaction
taking place in the cell is
At anode
Zn Zn2+ + 2e–
At cathode
Cu2+ + 2 e– Cu
Overall reaction
Zn + Cu2+ Zn2+ + Cu ...(2.1)
(iii) Condition 3
When the external emf is just greater than the cell emf, the above cell
reaction is reversed.
At anode
Cu Cu2+ + 2 e–
At cathode
Zn2+ + 2 e– Zn
Overall reaction
Cu + Zn2+ Cu2+ + Zn ...(2.2)
Equation (2.2) is an exact reverse of Eq. (2.1). Therefore, the Daniel
cell is a reversible cell.
(b) Irreversible Cell A cell is called irreversible when it does not
satisfy the three conditions of reversibility. Zinc–acid cell is an example
of irreversible cell. It is represented as
Zn/H2SO4/Cu

(i) Condition 1
When the external emf is just smaller than the cell emf, the following
reactions take place.
At anode
Zn Zn2+ + 2e–
At cathode
2H+ + 2 e– H2
Overall reaction
Zn + 2H+ Zn2+ +H2 ...(2.3)

(ii) Condition 2
When the external emf is just greater than the cell emf, the following
reactions take place.
At anode
Cu Cu2+ + 2e–
At cathode
2H+ + 2 e– H2
Overall reaction
Cu + 2H+ Cu2+ +H2 ...(2.4)
 The reaction (2.4) is not exactly the reverse of the previous one, i.e.
the reaction when H2 is liberated at copper electrode. Since this does not
satisfy the conditions of reversibility, it is called an irreversible cell.

2.5 EMF OF AN ELECTROCHEMICAL CELL

‘The difference of potential which causes the flow of current from one
electrode of higher potential to another electrode of lower potential
is called the electromotive force’.
Thus the emf of a galvanic cell can be calculated using the following
relationship.

{ }{ }
Standard reduction Standard reduction
emf = potential of right-hand – potential of left-hand
side electrode side electrode
E°cell = E°right – E°left

{ }{ }
Standard reduction Standard oxidation
emf = potential of right-hand + potential of left-hand
side electrode side electrode
E°cell = E°red + E°oxi
Example
The emf of Daniel cell is calculated as follows
E°cell = E°Cu – E°Zn
The standard reduction potential of copper electrode is 0.34 volt and
the standard reduction potential of zinc electrode is – 0.76 volt.
E°cell = 0.34 – (– 0.76) = + 1.1 volts
Note: The positive value indicates that the cell reaction is feasible. But
if it is negative, the cell reaction is not feasible.

2.5.1 Determination of emf of a Cell

The cell emf cannot be directly determined with a help of a voltmeter,
because a part of the cell current is drawn by the cell reaction and
causes a change in the actual emf. Potentiometers are used for accurate
measurement of such a cell by the application of Poggendroff’s
compensation method.
 The emf of a test cell is determined by applying an equal and opposite
external potential from an external source. Consequently, there is no
current flow in the circuit. So, the applied potential is therefore equal
to the magnitude of the emf of the test cell.
The potentiometer consists of a B
uniform wire AB of high resistance.
The ends A and B are connected to R
a storage battery through a rheostat
R. The cell of unknown emf (X) is D D¢
A B
connected to the circuit in such J J¢
S
a way that its positive end is
connected to A and its negative end
is connected to a sliding contact, HR G
through a galvanometer G. The
sliding contact is moved along the X
wire AB, till there is null deflection Fig. 2.5 Measurement of emf of a cell
in the galvanometer. The position
of the sliding contact D is noted and the distance AD is measured.
EX a AD
Then the unknown cell is replaced by a standard cell in the circuit. The
sliding contact is moved along AB till there is no deflection. The position
of the sliding contact D’ is noted and the distance AD’ is measured.
ES a AD’
The emf of the unknown cell can be calculated using the following
equation
Ex ____
___ AD
=
ES AD¢
Knowing the emf of the standard cell (ES), the emf of the unknown
cell (EX) can be calculated.
AD
Ex = ____ × Es
AD¢

2.5.2 Applications of emf Measurements

(a) Determination of Solubility of a Sparingly Soluble Salt
The ionic concentration of a solution is calculated from the emf of a
concentration cell. In case of a sparingly soluble salt, the salt can be
supposed to be completely ionized even in saturated solution. Hence,
the ionic concentration is proportional to the solubility of the salt.
 For example, the solubility of the sparingly soluble salt silver chloride
can be calculated by measuring the emf of the following cell.
This can be done by the construction of a cell by placing the silver
electrode in contact with 0.01 N solution of silver nitrate as a cathodic
compartment and at the anodic compartment, we have a silver electrode
in contact with 0.01 N potassium chloride solutions. The two solutions
are connected by a salt bridge.
The cell can be represented as
Ag / AgCl, 0.01 N KCl // 0.01 N AgNO3 / Ag
A drop of silver nitrate solution is added from the burette to the
potassium chloride solution, and a small amount of silver chloride
formed is sufficient to develop the emf of the cell.
The emf of the above cell is given by the relation
0.0591 C2
E = ______
n log ___
C1
Here, the valence of the silver ion, n = 1, and concentration of the
silver in cathodic compartment, C2 = 0.01 N
0.0591 0.01
E = ______ log ____
1 C1
where C1 is the concentration of Ag+ ions furnished by AgCl in KCl
solution.
By measuring the emf of the cell, the concentration of AgCl is
calculated. Multiplying this by 143.5, the equivalent weight of AgCl, we
can get the solubility of AgCl in grams/litre.
(b) Determination of the Valency of an Ion
Consider the following concentration cell, which can be represented as
M / Mn+ (C1) // Mn+ (C2) / M
For the above cell, the Nernst equation can be represented as
0.0591 C2
Ecell = ______
n log C1
___

By substituting the measured value of emf of a concentration cell and

the values of C1 and C2 in the equation, the value of n, the number of
electrons involved in the cell reaction (called the valency of ions), can
be calculated.
(c) Determination of Standard Free Energy Change
and Equilibrium Constant
(i) The standard free energy change of a reaction can be calculated
as follows
 Free energy Free energy Potential in volts Faraday
change change constant
–DG = n E F
joule mol electrons joule/coulomb coulomb/
mol electrons
...(2.5)

(ii) The equilibrium constant of a reaction can be calculated as

follows:
DG° = – RT ln Keq
DG° = – 2.303 RT log Keq
– DG°
log Keq = ________ ...(2.6)
2.303 RT
Comparing equations (2.5) and (2.6),
nFE°
log Keq = _____
2.303
nFE°
Keq = antilog ________
2.303 RT
E° = Standard emf of the cell
Keq = Equilibrium constant

(d) Determination of pH by using a Standard

Hydrogen Electrode
A hydrogen electrode is introduced into the solution, the pH of which
is to be determined. It is coupled with a standard hydrogen electrode
through a salt bridge and the emf of the cell is determined. If E is the
emf of the cell,
2.303 RT
E = – ________ log [H+] = – 0.0591 log [H+]
nF
E
pH = ______
0.0591

Example 1 The emf of the cell,

Zn/Zn2+ (1M) || Cu2+ (1M) / Cu
is 1.1 volts. Calculate the standard free energy and predict whether the cell is
feasible or not.
Solution – DG° = nFE°
– DG° = 2 × 96500 × 1.1
 DG° = – 2,12,300
The negative value of DG° shows that the cell is feasible.

Example 2 Emf of the cell,

Zn | ZnSO4 || AgNO3 | Ag at 25°C
is 1.5621V.
Calculate the equilibrium constant of the cell.
RT
Solution E° = ___ ln Keq
nF
8.314 × 298
1.5621 = __________ × 2.303 × log Keq
2 × 96500
0.0591
= ______ log Keq
2
1.5621 = 0.02956 log Keq
1.5621
log Keq = _______
0.02956
= 52.845
Keq = 6.999 × 1052

2.6 WESTON STANDARD CADMIUM CELL

A standard cell is one which is capable of giving constant and

reproducible emf and has negligible temperature coefficient of the
emf.

2.6.1 Construction of the Cell

It consists of an ‘H’ shaped glass vessel, with the lower ends of both arms
closed, having a platinum wire sealed into the bottom of each arm.
• Positive electrode contains mercury over which a paste of
mercurous sulphate (Hg2SO4) and mercury is placed.
• Negative electrode consists of an amalgam of Cd and Hg,
containing about 12 – 15% of Cd by weight.
• Both electrodes are sprinkled with some crystals of solid
CdSO4.8/3H2O as shown in Fig. 2.6.
• Electrolyte—The remaining part of the cell is filled with a saturated
solution of cadmium sulphate. The upper ends of tube are closed
with corks and sealing wax.
 Sealing wax
Cork

Saturated CdSO4
solution

Hg + Hg2SO4 CdSO4.8/3 H2O

Cd amalgam
Hg (+) (–)

Fig. 2.6 Weston standard cadmium cell

2.6.2 Working Mechanism of the Cell

When the cell operates, the following reactions occur at the two
electrodes:
At negative electrode
Cd(s) Cd2+ (aq) + 2 e–
At positive electrode
Hg2SO4 (s) + 2 e– 2 Hg(l) + SO42– (aq)
Cell representation
12.5% Cd in Hg|3 CdSO4.8H2O (s)|| CdSO4 (satd. solution) Hg2SO4|Hg
Advantages
• The cell works for many years at a stretch, without any voltage
changes.
• Potential of this cell varies slightly about – 0.09046 volt per degree
centigrade.
Note: The purpose of solid crystals of CdSO4.8/3H2O is to keep the
electrolyte saturated at all temperatures.

2.7 ELECTRODE POTENTIAL

When a metal (M) is dipped in its own salt solution, any one of the
following reactions will occur.
(i) Positive metal ions may pass into the solution.
M Mn+ + ne– (oxidation)
 (ii) Positive metals ions from the solution may deposit over the
metal.
Mn+ + ne– M (reduction)

Example 1 When a Zn electrode is dipped in ZnSO4 solution

Solution When a Zn electrode is in contact with
its salt solution of ZnSO4, atoms of Zn from the
lattice of the electrode dissolve and move into the Zn rod
solution of ZnSO4 leaving behind its electrons on
the metal lattice of the electrode itself (Fig. 2.7).
This makes the electrode acquire a negative charge. + –– +
+ –– +
These negatively charged electrons attract the + –– +
+ –– +
2+ + –– +
positively charged Zn ions from the solution.
This produces an electrical double layer all
Fig. 2.7 Helmholtz
around the metal and its known as Helmholtz electrical double layer
electrical double layer (Fig. 2.7). This leads to a
difference of electrical potential between the metal and the solution.
Since there is loss of electrons at this electrode, oxidation is said to
have taken place and hence the potential developed at this electrode is
called oxidation potential.
Zn Zn2+ + 2e– (oxidation)

Example 2 When a Cu electrode is dipped in CuSO4 solution

Solution A Cu electrode is dipped into a solution
of CuSO4. The Cu2+ ions of the solution adhere
on the electrode and hence the electrode attains a Cu rod
positive charge (Fig. 2.8).
To counterbalance the number of positive
charges on the electrode, the negatively charged – ++ –
– ++ –
2– – ++ –
SO4 ions from the solution surround the electrode. – ++ –
– ++ –
This develops an electrical double layer which is
known as Helmholtz electrical double layer. This CuSO4
causes a difference of electrical potential between solution
the metal and the solution (Fig. 2.8). Fig. 2.8 Helmholtz
Since there is a gain of electrons at this electrode, electrical double layer
reduction is said to have taken place and hence the
potential developed at this electrode is called the reduction potential.
Cu2+ + 2e– Cu (reduction)
Definitions
(i) Oxidation Potential: It is the tendency of an electrode to lose
electrons.
(ii) Reduction Potential: It is the tendency of an electrode to gain
electrons.
(iii) Electrode Potential: It is the tendency of an electrode to lose or
gain electrons.
(iv) Single Electrode Potential (E): It is the tendency of an electrode to
lose or gain electrons when it is dipped in its own salt solution.
(v) Standard Electrode Potential (E°): It is the tendency of an
electrode to lose or gain electrons when it is dipped in its own
salt of 1M concentration at 25°C.
Note: If the oxidation potential of an electrode is + X volts, then its
reduction potential will have a value of – X volts.

2.7.1 Determination of Electrode Potential

The potential of a single electrode alone cannot be measured. But potential
difference between two electrodes can be measured potentiometrically, i.e.
we can determine the electrode potential by combining the electrode with
another electrode for which the electrode potential is known (reference
electrode). For this purpose, the potential of hydrogen electrode has been
arbitrarily fixed at zero. Electrode potentials for other metallic electrodes
can be measured in comparision with this values.
(a) Determination of Electrode Potential of Zinc Electrode
The zinc electrode half-cell and the reference electrode (SHE) half-cell
are electrically connected by Voltmeter
a voltmeter between the two 0.76 V
– + Cathode
electrodes and electrolytically Anode
by a salt bridge as shown in Zn
H2(1 atm)
Fig. 2.9.
To obtain the cell reaction,
the zinc electrode is assigned
a –ve charge and the SHE is
assigned a + ve charge, and
these electrodes are connected 1M ZnSO4 1M HCl
to the – ve and + ve terminals
of the voltmeter respectively. Fig. 2.9 Reduction potential of zinc
At anode
Zn Zn2+ + 2 e–
At cathode
2 H+ + 2 e– H2
Cell reaction
Zn + 2 H+ Zn2+ + H2
Now the voltmeter shows the cell potential as 0.76 volts.
E°cell = E°right – E°left
where,
E°cell = + 0.76 volts
E°left = electrode potential of zinc electrode = ?
E°right = electrode potential of SHE = 0 volts
0.76 V = 0.0 V – E°
Zn2+
E° = – 0.76 volts
Zn2+
i.e. the reduction potential of Zn electrode = – 0.76 volts
(b) Determination of Electrode Potential of Copper Electrode
The Cu electrode half-cell is coupled with the SHE half-cell to form a
cell. It is seen that the SHE carries a –ve charge and the Cu electrode
carries +ve charge. The following reactions take place.

Anode –
E°cell = 0.34 V +
Cathode
H2 gas Æ Salt bridge
at 1 ATM
Cu

2+
+ 1 M Cu
1 MH

1M HCl 1M CuSO4

Fig. 2.10 Reduction potential of copper

At anode
H2 (g) 2 H+ (aq) + 2 e–
At cathode
Cu2+ (aq) + 2 e– Cu
Cell reaction
H2 + Cu2+ Cu + 2H+
The voltmeter shows a cell potential of 0.34 volts.
E°cell = E°right – E°left
where,
E°cell = + 0.34 volts
E°left = electrode potential of SHE = 0 volts
E°right = electrode potential of Cu electrode = ?
0.34 V = E° + 0.0 V
Cu2+
E° = + 0.34 volt
Cu2+
i.e. the reduction potential of Cu electrode = 0.34 volt

DETERMINATION OF ELECTRODE POTENTIAL—

2.8 NERNST EQUATION
Consider the following redox reaction.
Mn+ + ne– M ...(2.7)
According to Van’t Hoff’s reaction isotherm,
DG = – RT ln K + RT ln ([Product]/[Reactant]) ...(2.8)
We know that
DGº = – RT ln K ...(2.9)
From the above equation
DG = DGº + RT ln ([Product]/[Reactant]) ...(2.10)
Free energy relates with electrode potential by the following
equation
DG = – nFE and DGº = – nFEº
which on substitution in the above equation, becomes

(
[Product]
– nFE = – nEF° + RT ln __________
[Reactant] ) ...(2.11)
 Dividing the above equation by – nF,
RT
(
[Product]
E = E° – ___ ln __________
nF [Reactant] ) ...(2.12)

Nernst Equation for Oxidation Potential

Consider the following oxidation reaction:
M Mn+ + ne– ...(2.13)
From the above oxidation reaction, the Nernst equation is modified
as,
[Mn+]
RT
(
E = E° – ___ ln ______
nF [M] ) ...(2.14)

[Mn+]
E = E° –
RT
___
nF (
______
ln a
M
) ...(2.15)

(Since [M] = aM = activity of the metal ion)

Also aM = 1 for the all the metals.
And hence the above equation is modified as
RT
Eoxi = E°oxi – ___ ln [Mn+]
nF
or
RT
Eoxi = E°oxi – 2.303 ___ log [Mn+]
nF
or
0.0591
Eoxi = E°oxi – ______ n+
n log [M ] ...(2.16)

where F = 1 Faraday = 96500 coulombs; and R = 8.314 J/K/mole;

T = 298 K

Nernst Equation for Reduction Potential

Consider the following reduction reaction:
Mn+ + ne– M ...(2.17)
From the above reduction reaction, the Nernst equation is modified
as,
RT
(
[M]
Ered = E°red – ___ ln ______
nF [Mn+] )
aM
RT
(
Ered = E°red – ___ ln ______
nF [Mn+] ) …(2.18)
(Since [M] = aM = activity of the metal ion). Also aM = 1 for the all the
metals.
Hence, the above equation is modified as
RT
nF ( 1
Ered = E°red – ___ ln ______
[Mn+] )
RT
Ered = E°red + ___ ln [Mn+]
nF
0.0591
Ered = E°red + ______
n log [M ]
n+
…(2.19)

Nernst Equation for emf of the Cell

Emf of the cell = Eoxi + Ered …(2.20)
From the above equations,
0.0591 0.0591
E = E°Oxi – ______ n+ ______ n+
n log [M ]oxi + E°red + n log [M ]red
0.0591 0.0591
E = E°Oxi + E°red + ______ n+ ______ n+
n log [M ]red – n log [M ]oxi
[Mn+]red
0.0591
E = E ° + ______
n log (
________
[Mn+]oxi ) …(2.21)

Equations (2.12), (2.16) and (2.19) are called the Nernst equation for
single electrode potential.
From the above equations, the following is clear:
1. If concentration of solution (Mn+) is increased, the electrode
potential increases and vice versa.
2. If the temperature is increased, the electrode potential increases
and vice versa.

Example 3 Calculate the oxidation potential of Cd/CdSO4, 0.5 M at 298

K. E° = – 0.403 V. Also calculate its reduction potential.
Cd2+/Cd
Cd Cd2+ + 2e– (oxidation)
Solution Oxidation potential
RT
___ [Cd2+]
______
Eoxi = E°oxi – 2.303 log
nF [Cd]
0.0591 0.5
= 0.403 – ______ log ___
2 1
 = 0.403 – 0.0295 × (– 0.3010)
Eoxi = 0.411898 V
Ered = – 0.411898 V

Example 4 Calculate the reduction potential of Cu/CuSO4 (0.8 M) at

298 K. E°red = 0.337 V. If this electrode is connected to the standard calomel
electrode, what will be the emf produced? E°red of standard calomel electrode
= 0.2422V.
Solution Cu2+ + 2 e– Cu (reduction)
0.0591 [Cu]
Ered = E°red – ______ ______
n log [Cu2+]

0.0591 1
= 0.337 – ______ log ___
2 0.8
= 0.337 – 0.002864
The reduction potential of Cu/CuSO4 = 0.3341 V
Given, E°red of standard calomel electrode = 0.2422 V (so that the
standard calomel electrode will work as anode)
The emf of the cell constituted by the experimental electrode and
standard Calomel electrode = E°red + E°oxi
= 0.3341 – 0.2422
= 0.0919 V

Example 5 Calculate the emf of a Daniel cell at 25°C, when the

concentrations of ZnSO4 and CuSO4 are 0.001 M and 0.1 M respectively. The
standard potential of the cell is 1.1 volts.
Solution The cell is
Zn(s) / Zn2+ (0.001M) // Cu2+ (0.1M) / Cu(s)
0.0591 Cu2+
Ecell = E°cell + ______ log _____
2 Zn2+
0.1
= 1.1 + 0.0296 log _____
0.001
= 1.1 + 0.0296 (2)
= 1.1592 V
Example 6 Find the cell potential of a cell in which the following reactions
take place at 25°C.
Zn(s) + Cu2+ (0.02M) Cu(s) + Zn2+ (0.4M).
Solution Given
E° 2+ = – 0.76V; E° = 0.34 V.
Zn /Zn Cu2+/Cu

0.0591 Cu2+
Ecell = E° 2+ – E° 2+ + ______ log _____
Cu /Cu Zn /Zn 2 Zn2+
0.02
= [0.34 – (– 0.76)] + 0.0296 log ____
04
= 1.1 + 0.0296 log (0.05)
= 1.1 – 0.0385
= 1.0615 V

Example 7 Calculate E° of the cell:

Zn | ZnSO4 || AgNO3 | Ag at 25°C
E° = – 0.763 V and E°Ag/Ag+ = 0.7991 V
Zn/Zn2+
Also, calculate standard free energy and equilibrium constant.
Solution Cell reaction is Zn + 2Ag+ Zn2+ + 2 Ag
Standard emf (E°) of the cell
E° = E°red + E°oxi
= 0.7991 + 0.763
E° = 1.5621 V
Standard free energy
DG° = – nFE° ...(1)
= – 2 × 96500 × 1.5621
= – 301485.3 joules mol–1
DG° = – 301.485 kJ mol–1
Equilibrium constant
DG° = – RT ln Keq ...(2)
 Comparing equations (1) and (2),
– nFE° = – RT ln Keq
E° = RT/nF ln Keq
8.314 × 298
1.5621 = __________ × 2.303 × log Keq
2 × 96500
0.0591
= ______ log Keq
2
1.5621 = 0.02956 log Keq
1.5621
log Keq = _______
0.02956
= 52.845
Keq = 6.999 × 1052

Example 8 A cell is constituted by cadmium and nickel electrodes as

Cd/Cd2+ (x M) || Ni2+ (2M) / Ni.
The emf of the cell is found to be 0.20 V. Calculate the concentration of Cd2+
ions in the solution. E° 2+ = – 0.40v; E° 2+ = – 0.25 V.
Cd / Cd Ni /Ni
Solution E° = – 0.40 V;
Cd2+/Cd
E° = – 0.25 V.
Ni2+/Ni
Ecell = 0.20 V
0.0591 [Ni2+]
Ecell = E° – E° + ______ log ______
Ni2+/Ni Cd2+/Cd 2 [Cd2+]
0.0591 [2]
0.20 = – 0.25 – (– 0.40) + ______ log ___
2 [x]
0.20 = 0.15 + 0.0295 [log [2] – log [x]]
0.05 = 0.0295 [log [2] – log [x]]
1.6949 = log [2] – log [x]
1.6949 – log 2 = – log [x]
1.6949 – 0.3010 = – log [x]
– 1.3939 = log [x]
[x] = antilog [– 1.3939]
Concentration of Cd2+ ions in the solution is = 0.04M
 2.9 REFERENCE ELECTRODES

The electrode of standard potential with which we can compare the

potentials of other electrode is called a reference electrode.
Important reference electrodes are the following:

2.9.1 Hydrogen Electrode

This is a gas electrode. It consists of a thin rectangular platinum foil
(1 cm x 1 cm) which is coated with fresh platinum black to increase the
adsorption capacity of the metal. This is welded and the end of it is fused
into the inner tube through the base. In the inner tube, a little mercury is
taken and a Pt wire is introduced to make the external electrical contact.
The inner tube is enclosed in an outer jacket having an inlet tube for
sending in H2 gas and has a perforated wider base for the escape of
excess of H2. This unit is dipped in HCl taken in a beaker such that the
metal foil remains in the solution.
Working
When pure and dry H2 gas is
passed through the inlet tube, H2 gas
a part of the gas gets adsorbed
and the excess bubbles come Platinum wire
out through the perforations.
Between the H2 gas adsorbed
on the surface of the metal and 1M HCl solution
+
H of the solution, equilibrium
is established and an electrical Platinum foil
double layer of opposite
Fig. 2.11 Standard Hydrogen Electrode
charges is formed. The potential
developed is called H2 electrode potential.
In the above system, when the H2 gas at a pressure of 1 atm is bubbled
through 1M HCl, the electrode (constructed) or formed is called Standard
Hydrogen Electrode (SHE) or Normal Hydrogen Electrode (NHE).
This is represented as Pt, H2 (760 mm of Hg)/H+ (IM)
Definition The standard hydrogen electrode potential is defined as the
potential that is developed between the H2 gas adsorbed on the Pt metal
and H+ of the solution when the H2 gas at a pressure of 760 mm of Hg
is in equilibrium with H+ of unit concentration.
Cell reaction
H+ (aq) + e– ½ H2(g)

Electrode Potential of the Hydrogen Electrode

The electrode potential of the hydrogen electrode has been arbitrarily
fixed as zero.
It is used
1. For the determination of electrode potential of a metal electrode
system
2. For the determination of pH of a solution
Determination of pH using Hydrogen Electrode
A hydrogen electrode may be employed to find the pH value of an
unknown solution. For this, the solution whose pH is to be determined
is taken in a vessel and a platinum electrode is half dipped in it. A
slow current of hydrogen gas at 1 atmosphere is bubbled through the
solution.
Potentiometer
H2 gas (1 atm)
H2 gas (1 atm)
Salt bridge

Pt foil
HCl Solution HCl Solution
(C1 = ?) (C2 = 1M)

Fig. 2.12 Measurement of pH by hydrogen electrode

The platinum catalyses the following electrochemical reaction at the

electrode.
H+ (aq) + e– ½ H2(g)
This causes the electrode to develop a definite potential, depending
on the H+ ion concentration on the solution under test.
0.0591 [H2]1/2
E = E° – ______
n log _______ at 25°C
[H+ ] (aq)

0.0591 1
= 0 – ______ log _______ at 25°C,
1 [H+(aq)]
where H2 = 1 atm
= – 0.0591 pH
The above half-cell so formed is connected to a standard or normal
hydrogen electrode (i.e. having a solution of 1N HCl and an electrode
potential of 0 volt). The two solutions are separated by a salt bridge
to eliminate liquid junction potential. The emf of the full cell is then
determined by means of a potentiometer. Since emf of the reference
electrode is zero, therefore the observed emf gives directly the emf of
the half-cell containing the solution under test.
Ecell = Eright – Eleft
Ecell = 0 – (– 0.0591 pH) = 0.0591 pH
Ecell
pH = ______
0.0591
Limitations
1. It is rather difficult to regulate the pressure of the H2 gas to be at
exactly 1 atm throughout the experiment.
2. Excess of H2 bubbling out carries little HCl with it and hence
the H+ concentration decreases. In such a system, it is difficult to
maintain the concentration of HCl at 1M.
3. Platinum foil gets easily poisoned by the impurities present in the
gas and HCl. In fact, the attainment of equilibrium is ensured by
trial and error.
4. If the solution contains any oxidizing agent, the H2 electrode
cannot be used.

Example 9 The emf of the following cell

Pt, H2 (1atm)/ H+ (unknown) || H+(1 M)/H2 (1atm), Pt, is 0.1773 V.
Calculate pH of the given solution.
Ecell
Solution pH = ______
0.0591
0.1773
= ______
0.0591
pH = 3

Example 10 Calculate the emf of the cell

Pt, H2 (1 atm)/ H+ (pH = 4.0) || H+(1 M)/H2 (1atm), Pt.
 Ecell
Solution pH = ______
0.0591
Ecell = pH × 0.0591
= 4.0 × 0.0591
= 0.2364 V

2.9.2 Some Other Reference Electrodes

Since a standard hydrogen electrode is difficult to prepare and maintain,
it is usually replaced by other reference electrodes, which are known as
secondary reference electrodes. These are convenient to handle and are
prepared easily.
Calomel Electrode
The calomel electrode is commonly
known as the mercury–mercurous
chloride electrode. It is otherwise
known as secondary reference
electrode.
(i) Construction
The calomel electrode consists Pt wire
of a glass tube. At the bottom
of the tube, a layer of mercury KCl (Satd..)
is placed, over which there is a
paste of mercury and mercurous
chloride. Hg2 Cl2 + Hg Paste

The KCl solution is filled with

the remaining portion of the Hg
cell. The cell is filled with 0.1N,
1.0N and a saturated solution Fig. 2.13 Standard calomel electrode
of potassium chloride. Then the
electrode may be called decinormal, normal and saturated calomel
electrode respectively.
The electrical contact may be made through a platinum wire sealed
with a glass tube.
The side arm is provided for making electrical contact through a salt
bridge.
Cell representation
Hg, Hg2Cl2 (s)// KCl (satd. solution)
Cell reaction
Hg2Cl2 (s) + 2 e– 2 Hg (l) + 2 Cl– (aq)

(ii) Electrode Potential of Calomel Electrode

The potential of the calomel electrode, on the hydrogen scale, has been
found to vary with the concentration of the potassium chloride solution
used. The reduction potentials for the various KCl concentrations at 25°C
are given here.
Concentration of KCl Electrode Potential in Volts at 25°C
Saturated 0.2422 V
1.0N 0.2800 V
0.1N 0.3338 V

(iii) Measurement of pH using Calomel Electrode

The electrode can be coupled with hydrogen electrode containing a
solution of unknown pH.
Pt, H2 (1atm)/ H+ (C=?)// KCl/Hg2Cl2(s), Hg
(satd)

Potentiometer

H2 gas
(1 atm)

Pt wire
Pt foil

KCl (Satd..)

HCl solution Hg2 Cl2 + Hg Paste

C1 = ?

Hg

Fig. 2.14 Measurement of pH using calomel electrode

The emf of the cell

Ecell = Eright – Eleft = 0.2422 V + 0.0591 V pH
Ecell – 0.2422
pH = ____________
0.0591

Example 11 The emf of the following cell is

 Pt, H2 (1atm), H+ (C = ?)|| KCl, Hg2Cl2(s), Hg 0.4494 V. Calculate pH
of the given solution.
Ecell – 0.2422
Solution pH = ____________
0.0591
0.4494 – 0.2422
= ______________
0.0591
pH = 3.5

Example 12 Calculate the emf of the cell

Pt, H2 (1atm), H+ (pH = 4.2)|| KCl, Hg2Cl2(s), Hg.
Ecell – 0.2422
Solution pH = ____________
0.0591
Ecell = 0.0591 × pH + 0.2422
= 0.0591 × 4.2 + 0.2422
= 0.49042 V

2.10 TYPES OF ELECTRODES

An electrochemical cell consists of two electrodes, positive and negative.

Each electrode constitutes a half-cell or a single electrode. The commonly
used electrodes in different electrochemical cells are
1. Metal–metal ion electrodes
2. Metal–insoluble metal salt electrodes
3. Gas electrodes
4. Glass electrode

2.10.1 Metal–Metal Ion Electrodes

This type of electrode consists of a metal rod (M) dipping into a solution
of its metal ions (Mn+).
Cell representation
M / Mn+
Electrode reaction
M Mn+ + n e–
If the metal rod behaves as a negative electrode (i.e. the reaction
involves oxidation), the above equilibrium will shift towards right.
Therefore, the concentration of the Mn+ ions in solution will increase.
Table 2.3 Types of electrodes
Types of Cell Repre- Electrode
Electrode Potential Examples
Electrodes sentation Reaction
RT
Metal–metal M / Mn+ M EM = E° M – ___ ln • Zinc rod dipping in ZnSO4
nF
ion Mn+ + ne– aMn+ solution (Zn/Zn2+)
electrodes • Copper rod dipping in
CuSO4 solution (Cu/Cu2+)
• Silver rod dipping in
AgSO4 solution (Ag/Ag2+)
RT 1
Metal– M / MX / M(s) + X– EM/X– = E°M/X – ___ ln ___ • Calomel electrode:
nF aX
insoluble X– (a) MX + e– mercury–mercurous
metal salt chloride in contact with
electrodes a solution of KCl
• Mercury–Mercuric
sulphate in contact with a
solution K2SO4.
• Silver wire coated with
AgCl immersed in KCl
solution.
RT
Gas Pt,X2 /X+ X+(aq)+ e– EM = E°M – ___ ln aX+ • Hydrogen electrode
nF
electrode ½ X2(g) • Chlorine electrode

Glass Ag/AgCl (s), H+ (aq)+ e– EG = E°G + 0.0591 pH • Glass electrode

electrode HCl (0.1 M)/ ½ H2(g)
Glass

On the other hand, if the metal rod behaves as a positive electrode

(i.e. the reaction involves reduction), the equilibrium will shift towards
the left. Therefore, the concentration of the Mn+ ions in solution will
decrease.
Electrode potential
RT
EM = E°M – ___ ln an+
M
nF
Examples
• Zinc rod dipping in ZnSO4 solution. (Zn/Zn2+)
• Copper rod dipping in CuSO4 solution (Cu/Cu2+)
• Silver rod dipping in AgSO4 solution (Ag/Ag2+)

2.10.2 Metal–Insoluble Metal Salt Electrodes

This type of electrode consists of a metal (M) covered by a layer of
sparingly soluble salt (MX) dipping into a solution containing a common
anion (X–).
Cell representation
M/MX/X–(a)
Electrode reaction
M(s) + X– MX + e–
Electrode potential
RT 1
EM/X – = E°M/X – ___ ln ____–
nF aX
Examples
• Calomel electrode: mercury–mercurous chloride in contact with a
solution of KCl
• Mercury–Mercuric sulphate in contact with a solution K2SO4
• Silver wire coated with AgCl immersed in KCl solution

2.10.3 Gas Electrode

Gases like hydrogen, chlorine, etc., bubble in an acid solution and can
be used to form gas electrodes. The acid employed contains the ions of
the gas used. Since these gases are nonconductors of electricity, metals
like platinum are used for making electrical contact in the circuit. These
metals are not attacked by the acids.
(a) Hydrogen Electrode
Hydrogen gas is bubbled into HCl solution.
The equilibrium is represented as
H+(aq) + e– ½ H2(g)
The electrode is represented as
Pt, H2 (1 atm)/ H+ (1M)
The reaction from left to right is reduction, where hydrogen ions
change to hydrogen gas by absorbing electrons. The electrode is
reversible with respect to hydrogen gas.
(b) Chlorine Electrode
In this electrode, chlorine gas at a given pressure is bubbled into a
solution of hydrochloric acid.
The reaction is
½ Cl2 (g) + e– Cl–
The reaction from left to right is reduction. Chlorine gas changes into
chloride ion by gaining an electron.
 The electrode is represented as
Pt, Cl2 (g)/Cl–
The electrode is reversible with respect to chloride ion.

2.10.4 Glass Electrodes (Internal Reference Electrode)

A glass electrode is the universally employed electrode for pH
measurement.
(a) Construction
The glass electrode is made of a special glass of
relatively low melting point and high electrical
conductivity. It is a special type of glass bulb
containing Na2O (22%), CaO (6%) and SiO2
(72%). This glass bulb is filled with 0.1 N
Pt wire
hydrochloric acid and a silver wire coated with
silver chloride is immersed in it. Here Ag/ AgCl
acts as an internal reference electrode.
0.1 m HCl
The glass electrode is represented as
Ag/ AgCl (s), HCl (0.1 M)/Glass Thin walled
+ glass bulb
HCl in the bulb furnishes a constant H ion
concentration. Thus, it is a silver – silver chloride Fig. 2.15 Glass electrode
electrode reversible with respect to Cl– ions.
A glass electrode is used as the ‘internal reference electrode’. The pH
of the solutions, especially coloured solutions containing oxidizing or
reducing agents, can be determined.
(b) Working Mechanism of Glass Electrode
The response of a glass electrode to H+ ion activity is a result of complex
processes at the interface between the glass membrane (50 µm) and the
solutions on either side of it. The membrane itself is permeable to Na+
and Li+ ions but not to H+ ions. The glass membrane is coated with
hydrated silica. H+ ions in the test solution modify this layer to an extent
that depends on their activity in the solution and the charge modification
of the outside layer is transmitted to the inner layer by the Na+ and Li+
ions in the glass. H+ ion activity gives rise to a membrane potential by
this indirect mechanism.
(c) Determination of pH of a Solution using Glass Electrode
The glass electrode is placed in the solution under test and coupled with
a saturated calomel electrode.
 Ordinary
Glass

Thin glass
+
permeable to H
Silver wire
coated with AgCl +
[H ]in
+
0.1 M HCl H +
+ – – +
H H
+
(pH = 1) –
+
[H ]out +
pH > 1 outside

Fig. 2.16 Mechanism of glass electrode EG = E°G + 0.0591 pH

The cell assembly is represented as

Ag/AgCl (s), HCl (0.1 M)/Glass/Solution of
Unknown pH//Satd. Calomel Electrode
The emf of the cell is measured. From the emf, pH of the solution is
calculated as follows.
Ecell = Eright – Eleft
= 0.2422 – [E°G + 0.0591 pH]
Therefore,
0.2422 – Ecell – E°G
pH = _________________
0.0591
(d) Advantages of Glass Electrode
(i) It can be easily constructed and readily used.
(ii) The results are accurate.
– +
Potentiometer

Saturated
Calomel
electrode
Glass
electrode
Saturated
KCL

Hg2Cl2
Solution
of unknown Hg
1
pH [H ] = ?

Fig. 2.17 Determination of pH by glass electrode

 (iii) It is not easily poisoned.
(iv) It can be used in turbid coloured and colloidal solutions.
(e) Limitations
(i) Since the resistance is quite high, special electronic potentiometers
are employed for measurement.
(ii) The glass electrode can only be used in solutions with a the pH
range of 0 to 10.

ELECTROCHEMICAL SERIES OR EMF SERIES —

2.11 IMPORTANCE OF ELECTRODE POTENTIAL
By measuring the potentials of various electrodes versus a standard
hydrogen electrode (SHE), a series of standard electrode potentials
has been established. When the electrodes (metals and nonmetals) in
contact with their ions are arranged on the basis of the increasing values
of their standard reduction potentials, the resulting series is called the
electrochemical or electromotive or activity series of the elements.
By international convention, the standard potentials of electrodes are
tabulated for reduction half-reactions, indicating the tendencies of the
electrodes to behave as cathodes towards SHE. Those with positive E°
values for reduction half-reactions do in fact act as cathodes versus SHE,
while those with negative E° values of reduction half-reactions behave
instead as anodes versus SHE. The electrochemical series is shown in
Table 2.4.

Table 2.4 Standard electrode potential (half-cell potentials of some metals with respect to
SHE at 25°C)
Electrode Reaction Standard Electrode Reduction
Element
(Reduction) Potential E°, Volt
Li Li+ + e– = Li –3.05 Anodic
K K+ + e– = K –2.925
Ca Ca2+ + 2e– = Ca –2.87
Na Na+ + e– = Na –2.714
2+ –
Mg Mg + 2e = Mg –2.37
Al Al3+ + 3e– = Al –1.66
2+ –
Zn Zn + 2e = Zn –0.7628
Cr Cr3+ + 3e– = Cr –0.74
2+ –
Fe Fe + 2e = Fe –0.44 Pt-Reference
Cd Cd2+ + 2e– = Cd –0.403
Ni Ni2+ + 2e– = Ni –0.25

Table Contd...
Table Contd...

Sn Sn2+ + 2e– = Sn –0.14

+ –
H2 2H + 2e = H2 0.00 Pt-Reference
Cu Cu2+ + 2e– = Cu +0.337
I2 I2 + 2e– = 2I– +0.535
Ag Ag+ + e– = Ag +0.799
2+ –
Hg Hg + 2e = Hg +0.885
Br2 Br2 + 2e– = 2Br– +1.08
Cl2 Cl2 + 2e– = 2Cl– +1.36
Au Au3+ + 3e– = Au +1.50
F2 F2 + 2e– = 2F– +2.87 Cathodic

2.11.1 Characteristics of Electrochemical Series

(i) The negative sign of standard reduction potential indicates that
an electrode when joined with SHE acts as anode, and oxidation
occurs on this electrode. For example, the standard reduction
potential of zinc is – 0.76 volt. When a zinc electrode is joined with
SHE, it acts as anode (–ve electrode), i.e. oxidation occurs on this
electrode. Similarly, the +ve sign of standard reduction potential
indicates that the electrode when joined with SHE acts as cathode
and reduction occurs on this electrode.
(ii) The metals on the top (having high negative values of standard
reduction potentials) have the tendency to lose electrons readily.
These are active metals. The activity of metals decreases from top
to bottom. The nonmetals on the bottom (having high positive
values of standard reduction potentials) have the tendency to
accept electrons readily. These are active nonmetals. The activity
of nonmetals increases from top to bottom.
(iii) The substances which are stronger reducing agents than hydrogen
are placed above hydrogen in the series. The substances which are
stronger oxidizing agents than H+ ions are placed below hydrogen
in the series.

2.11.2 Importance or Significance of Electrochemical

or emf Series or Applications of
Electrochemical Series
(a) Reactivity of Metals
The activity of the metal depends on its tendency to lose an electron or
electrons, i.e. tendency to form cations (Mn+). This tendency depends
on the magnitude of standard reduction potential. The metal which has
a high negative value (or smaller positive value) of standard reduction
potential readily loses the electron or electrons and is converted into a
cation. Such a metal is said to be chemically active.
The chemical reactivity of metals decreases from top to bottom in the
series. The metal higher in the series is more active than the metal lower
in the series. Some examples are illustrated below.
(i) Alkali metals and alkaline earth metals having high negative
values of standard reduction potentials are chemically active.
These react with cold water and evolve hydrogen. These readily
dissolve in acids forming corresponding salts and combine with
those substances which accept electrons.
(ii) Metals like Fe, Pb, Sn, Ni, Co, etc., which lie a little down in the
series, do not react with cold water but react with steam to evolve
hydrogen.
(iii) Metals like Cu, Ag and Au which lie below hydrogen are less
reactive and do not evolve hydrogen from water.
(b) Relative Ease of Oxidation or Reduction
The higher the value of standard reduction potential, the greater is the
tendency to get reduced form.
(i) The positive sign of reduction potential indicates that the electrode
reaction occurs in the forward direction, i.e. reduction direction.
Fluorine has higher positive value of standard reduction potential
(+2.65 V) and shows higher tendency towards reduction.
(ii) The negative sign of reduction potential indicates that the electrode
reaction occurs in opposite direction, i.e. backward direction. It
means the reduced form has a greater tendency to lose electrons
and get oxidized. Thus, lithium (–3.01V) has the highest negative
reduction potential and shows higher tendency to lose electrons.
(c) Displacement of One Species by the Other
We now try to predict whether a given metal will displace another from
its salt solution. A metal higher in the series will displace the metal
from its solution which is lower in the series, i.e. the metal having low
standard reduction potential will displace that metal from its salt solution
which has a higher value of standard reduction potential. A metal higher
in the series has greater tendency to provide electrons to the cations of
the metal to be precipitated.
For example, we can know whether copper will displace zinc from its
solution or vice versa. We know that E° 2+ = + 0.34 V and E° 2+
Cu/Cu Zn /Zn
2+
= – 0.76 V. Cu has much greater tendency to get Cu form than Zn2+ has
in acquiring Zn form. In other words, zinc will displace copper from its
solution.
Zn + Cu2+ Zn2+ + Cu
(d) Reducing Power of Metals
Reducing nature depends on the tendency of losing electron or electrons.
The more the negative reduction potential, more is the tendency to lose
electron or electrons. Thus, reducing nature decreases from top to bottom
in the electrochemical series. The power of the reducing agent increases
as the standard reduction potential becomes more and more negative.
Sodium is a stronger reducing agent than zinc and zinc is a stronger
reducing agent than iron.
Elements Reduction Potential Reducing Nature
Na – 2.71 Decreases
Zn – 0.76
Fe – 0.44

Alkali and alkaline earth metals are strong reducing agents.

(e) Oxidizing Nature of Nonmetals
Oxidizing nature depends on the tendency to accept an electron or
electrons. More the value of reduction potential, higher is the tendency
to accept an electron or electrons. Thus, oxidizing nature increases from
top to bottom in the electrochemical series. The strength of an oxidizing
agent increases as the value of reduction potential becomes more and
more positive.
F2 (fluorine) is a stronger oxidant than Cl2, Br2 and I2.
Cl2 (chlorine) is a stronger oxidant than Br2 and I2.
Elements Reduction Potential Oxidizing Nature
I2 + 0.53 Increases
Br2 + 1.06
Cl2 + 1.36
F2 + 2.85

Thus, in the electrochemical series,

Top (Strongest reducing agent)
Highest negative reduction potential
Reducing
Oxidising

Nature

Nature

or
(Minimum reduction potential)
Bottom (Strongest oxidising agent)
Highest positive value of reduction potential
(f) Hydrogen Displacement Behaviour
(i) Displacement of Hydrogen from Dilute Acids by Metals
The metals which can provide electrons to H+ ions present in dilute acids
for reduction evolve hydrogen from dilute acids.
M Mn+ + ne– (oxidation)
2H+ + 2e– H2 (reduction)
The metal having negative values of reduction potential possesses the
property of losing an electron or electrons.
Thus, the metals occupying top positions in the electrochemical
series readily liberate hydrogen from dilute acids and on descending
in the series, the tendency to liberate hydrogen gas from dilute acids
decreases.
The metals which are below hydrogen in the electrochemical series
like Cu, Hg, Au, Pt, etc., do not evolve hydrogen from dilute acids.

Example 1 Zinc reacts with dil. H2SO4 to give H2 but Ag does not.
Why?
Solution Zn + H2SO4 ZnSO4 + H2
E°Zn = – 0.76 volts
The metal with a positive reduction potential (i.e. the metal placed
below H2 in the emf series) will not displace hydrogen from an acid
solution.
Ag + H2SO4 No reaction
E°Ag = + 0.80 volt

(ii) Displacement of Hydrogen from Water

Iron and the metals above iron are capable of liberating hydrogen from
water. The tendency decreases from top to bottom in the electrochemical
series.
Alkali and alkaline earth metals liberate hydrogen from cold water
but Mg, Zn and Fe liberate hydrogen from hot water or steam.
(g) Calculation of Standard emf of the Cell
Using E° of anode half-cell and cathode half-cell, the standard emf can
be calculated.
E°cell or standard emf of a cell = E°cathode – E°anode
(h) Predicting Feasibility or Spontaneity of the Cell Reaction
In a reversible cell, when the cell yields electrical energy, there is a fall
in free energy (or) – D G = nFE.
Gibbs Cell Potentials Spontaneous Direction
DG < 0 Ecell > 0 Spontaneous
DG = 0 Ecell = 0 Equilibrium
DG > 0 Ecell < 0 Nonspontaneous

(i) Determination of Equilibrium Constant for a Reaction

Standard electrode potential can be used to determine the equilibrium
constant for a reaction.
We know that
– D0G = RT ln K = 2.303RT log K
– D0G
________
log K =
2.303RT
nFE°
log K = ________ [ – D0G = nFE° ]
2.303RT
So, from the value of E° for a cell reaction, its equilibrium constant
can be calculated.

2.12 POTENTIOMETRIC TITRATION

Potentiometric titration is a very important application of emf

measurement. In this method, a cell is constructed in which at least one
of the electrodes is reversible with respect to one of the ions taking part
in the titration reaction.

2.12.1 Theory
We know that the potential of an electrode dipping in a solution of an
electrolyte depends upon the concentration of active ions (i.e. which
changes the electrode potential).
RT
E = E° + ___ log C
nF
A small change in the active-ion concentration in the solution changes
the electrode potential correspondingly. During the course of titration,
the concentration of the active ion decreases, thereby the electrode
potential of the indicator electrode decreases. Thus, the measurement of
the indicator electrode potential can serve as a good indication of end
point or equivalence point of the titration reaction. The potential of the
indicator electrode is usually measured potentiometrically by connecting
it with a reference electrode like saturated calomel electrode.

2.12.2 Detection of End Point

The emf of a cell changes by the addition of a small amount of titrant.
So the concentration of reversible ion in contact with indicator electrode
changes. We thus record the change in emf with every small addition.
The change of potential will be slow at first; but at equivalence, the
point charge will be sharp or quite sudden. The values are then plotted
against corresponding volume changes. A curve like the one shown in
Fig. 2.18a is obtained. The end point corresponds to the point of inflexion,
i.e., the point where the slope of the curve is maximum as shown.
Alternatively, change in emf with every small addition of titrant (i.e.
DE/DV) is plotted against volume V. The maximum of the curve gives
the end point (Fig. 2.18 b).

Maxima
Emf of cell (E)

DE/DV

End-Point
End-Point

V (Volume of titrant) V (Volume of titrant)

(a) (b)

Fig. 2.18 (a) In potentiometric titration, the point of inflection is the end point. (b) Plot of
D E /D V against volume (maxima gives the more accurate end point)

Potentiometric titrations, are classified into three types:

(a) Acid–base titrations
(b) Oxidation–reduction (redox) titrations
(c) Precipitation titrations
(a) Acid–base Titration
In acid–base titration, quinhydrone electrode is employed as indicator
electrode. The reference electrode is, generally, the saturated calomel
electrode. A definite volume of the given acid solution is taken in a
large beaker. To it, a pinch of quinhydrone is added and a stirrer and
a platinum electrode are dipped in it. This electrode is then connected
to a saturated calomel electrode through a potentiometer. On adding a
standard alkali solution from the burette, the emf of the cell increases at
first gradually, but at the end point, the rate of change of potential will
be suddenly quite large.

Standard alkali – Potentiometer +

in burette

Saturated
Stirrer KCL

Acid solution Hg2Cl

+ little Quinhydrone Hg
Pt electrode

Fig. 2.19 Acid–base potentiometric titration

The end point of the titration is then located by plotting D E/D V versus
V as shown in Fig. 2.18 and the maximum point on the curve gives the
end point.
(b) Redox Titrations
Titrations involving oxidizing agents (K2Cr2O7 or KMnO4) and reducing
agents (like ferrous salt) can be followed potentiometrically by using a
platinum indicator electrode.
K2Cr2O7 + 6FeSO4 + 7H2SO4 K2SO4 + Cr2(SO4)3
+ 3Fe2(SO4)3 + 7H2O
The apparatus for titration of a ferrous salt with acidified K2Cr2O7 is
illustrated in Fig. 2.20.

K2Cr2O7 solution Potentiometer

in Burette

N2 Gas Trap

Saturated
KCl
Hg2Cl
Hg
FeSO4 solution
+ dil H2SO4
Pt electrode
Stirrer

Fig. 2.20 Potentiometric redox titration

 The initial concentration of an ion such as Fe2+ can be found by titrating
with a strong oxidizing agent such as Cr6+. The titration is carried out in
one side of a cell whose other half is a reference electrode:
Pt(s) | Fe2+, Fe3+ || reference electrode (calomel electrode)
Initially, the left cell contains only Fe2+. As the titrant is added, the
ferrous ion is oxidized to Fe3+ in a reaction that is virtually complete:
3Fe2+ + Cr6+ 3Fe3+ + Cr3+
The cell potential is followed as the Fe2+ is added in small increments.
Once the first drop of titrant has been added, the potential of the left cell
is controlled by the ratio of oxidized and reduced iron according to the
Nernst equation
[Fe3+]
E = 0.68 – 0.0591 log ______
[Fe2+]
On adding K2Cr2O7 from the burette, emf of the cell will increase
first slowly, but at the equivalence point, Fe2+ will have been totally
consumed (the large equilibrium constant ensures that this will be so),
and the potential will then be controlled by the concentration ratio of
Cr6+/Cr3+.
The idea is that both species of a redox couple must be present in
reasonable concentrations for a concentration to control the potential of
an electrode of this kind. If one works out the actual cell potentials for
various concentrations of all these species, the resulting titration curve
looks much like the familiar acid–base titration curve. The end point is
found not by measuring a particular cell voltage, but by finding what
volume of titrant gives the steepest part of the curve.
(c) Precipitation Titrations
In this titration, a silver electrode dipping in silver nitrate solution is
used as the working or indicator electrode. This electrode is connected
with a saturated calomel electrode through a salt bridge of ammonium
nitrate.
We may illustrate the method by the titration of AgNO3 with a
standard KCl solution run from the burette. An Ag electrode dipping in
AgNO3 solution is used as the indicator electrode. The potential of the
Ag+/Ag half-cell is measured by connecting it with saturated calomel
electrode through a salt bridge of NH4NO3. As the titration proceeds, by
the addition of standard potassium chloride solution from the burette
into the silver nitrate solution, the concentration of Ag+ ions decreases,
due to the precipitation of Ag+ ions as AgCl.
 Ag+NO3– + K+Cl– AgCl + K+NO3–
The reduction potential of the indicator electrode (Ag) goes on
decreasing progressively on the addition of KCl. At the end point, the
concentration change of Ag+ is quite rapid. At the end point, the Ag+
concentration becomes very small on account of slight solubility of AgCl.
If addition of KCl is continued, the Ag+ion concentration is not affected,
except for a very small decrease, due to decrease in solubility of AgCl
on account of common ion (Cl–) effect.
Saturated
KCl solution
Potentiaometer
– +

Saturated
NH4NO3 KCl
Saturated
Bridge
KCl

Hg2Cl2

Hg

Ag electrode AgNO3
solution

Fig. 2.21 Potentiometric precipitation titration

Therefore, addition of KCl beyond end point causes only a very small
decrease in electrode potential or emf of the cell. On plotting DE/DV
versus V, the point of maxima gives the end point.
Advantages of Potentiometric Titrations
• Potentiometric titrations can be carried out in coloured solutions,
where indicators cannot be used.
• There is no need of prior information about the relative strength
of titrant before the titration.

2.13 CONDUCTOMETRIC TITRATIONS

Conductometric titration is a volumetric method based on the

measurement of conductance of the solution during the titration.
The conductance of a solution should be based on
• The number and charge on the free ions,
• The mobility of the ions
2.13.1 Process
To
Titrations are usually carried out conductivity
by taking a solution to be titrated bridge
in a beaker kept in a water bath Conductivity cell
at constant temperature in which
a conductivity cell is dipped and
connected to a conductivity bridge.
The titrant is added from the burette.
The whole arrangement may be
represented as in Fig. 2.22. The
Water Solution to
solution is stirred and conductance bath be titrated
is measured after each addition.
Fig. 2.22 Conductometric titration
If the conductance of a solution
is recorded during the course of
titration and plotted against the volume of the titrant added, we get
straight lines. The end point can be obtained by finding out the point
of their intersection.

2.13.2 Types of Conductometric Titrations

• Acid–base titration
• Precipitation titration
• Replacement titration
• Redox (oxidation–reduction) titration
• Complexometric titration
(a) Strong Acid vs Strong Base (HCl vs NaOH)
A known amount of acid (HCl) is taken in the conductivity cell and
the alkali (NaOH) in the burette. Initially, the conductivity of the HCl
is high—this is due to the presence of fast moving H+ions (Point A in
the graph). As the NaOH is added gradually, conductance will go on
decreasing until the acid has been completely neutralized (indicated by
the line AB) in this method.
This is due to the replacement of rapid-moving H+ ions by slow-
moving Na+ ions. The point ‘B’ indicates complete neutralization of all
H+ ions.
HCl + NaOH NaCl + H2O
Acid Base Salt Water
(unionised)

Further addition of NaOH will introduce the fast-moving OH– ions.

Therefore, the conductance, after reaching a certain minimum value, will
start to increase (indicated by the line BC).
 On plotting the conductance
adjacent to the volume of alkali A C
added, the two lines cross at a point NaOH

Conductance
‘B’ to provide the end point. This HCl

method corresponds to the volume

of NaOH necessary for neutralization. B
Additional adding up of alkali hoists
the conductance piercingly as there
is a surplus of hydroxide ions. A End point
graph is drawn among the volume
of supplementary NaOH and the
Volume of NaOH
conductance of the solution.
Fig. 2.23 Plot of titration of strong
(b) Weak Acid vs Strong Base acid vs strong base
(CH3COOH vs NaOH)
The solution containing acetic acid in the beaker has a very low
conductance. During the titration of acetic acid with sodium hydroxide,
a highly ionized salt, CH3COONa, is formed.
The reaction may be represented
as A C
NaOH
CH3COOH + Na+ + OH–
CH3COO– + Na+ + H2O
Conductance

CH3COOH
For every addition of sodium B
hydroxide to the acetic acid, the
conductance value slightly increases
up to the equivalence point. At the
End point
equivalence point, further addition
of alkali introduces excess of fast-
moving OH– ions. The conductance
Volume of NaOH
therefore increases more rapidly
after the end point is reached. Fig. 2.24 Titration plot for weak acid
vs strong base
On plotting the conductance
against volume of alkali added, the two straight lines are obtained and
where they intersect give the end point.
(c) Mixture of Weak and Strong acid with Strong Base
(HCl and CH3COOH vs NaOH)
When a mixture of a weak and a strong acid like CH3COOH and HCl is
titrated against a strong base, a curve ABCD is obtained. Due to common-
ion effect, the ionization of a weak acid is suppressed in the presence of
a strong acid. So the neutralization of a strong acid occurs first and then
the neutralization of a weak acid starts.
 Therefore, the first point of
intersection refers to equivalence D
A
point of complete neutralization of NaOH

Conductance
strong acid and the second point HCl
CH3COOH
of intersection C is the equivalence C
point for the complete neutralization B
End Point 2
of the mixture.
End Point 1

2.13.3 Advantanges of
Conductometric
Volume of NaOH
Titrations
Fig. 2.25 Titration of plot of a mixture of
1. This method can be used with weak and strong acid with strong base
very diluted solutions.
2. This method can be used with coloured or turbid solutions in
which the end point cannot be seen clearly.
3. This method can be used in which there is no suitable indicator.
4. It has many applications, i.e. it can be used for acid–base, redox,
precipitation, or complex titrations.

2.14 BATTERIES

A battery is an arrangement of several electrochemical cells connected

in series that can be used as a source of direct electric current.
A cell is one that contains only one anode and cathode, but a battery
contains several anodes and cathodes.

Types of Batteries
(a) Primary Battery or Primary Cells
In the case of a primary battery, the electrode and the electrode reactions
cannot be reversed by passing an external electrical energy. The reactions
occur only once and after use, they become dead. Therefore, they are
not rechargeable.
Example: Dry cell, mercury cell
(b) Secondary Battery or Secondary Cells
In case of a secondary battery, the electrode reactions can be reversed by
passing an external electrical energy. Therefore, they can be recharged by
passing an electrical current and used again and again. These are also
called storage cells or accumulators.
Example: Lead–acid storage cell, nickel–cadmium cell
 2.15 LEAD ACCUMULATOR OR ACID STORAGE CELL
A typical lead–acid battery comprises of the following components:
(a) Anode: Pb grid with spongy lead
(b) Cathode: Pb–Sb with lead dioxide
(c) Electrolyte: 28–30% of H2SO4 acid.
The anode of the cell is a lead grid filled with spongy lead, while the
cathode of the cell is a lead–antimony grid containing PbO2. The anode
and cathode of the battery is separated by inserting an inert porous
material in between them. The electrolyte is about 28–30 % H2SO4 (sp.
gr. 1.2 at 25%C). The whole set up of a number of such cells is enclosed
inside an ebonite case.
– Anode
+ Cathode

Pb plates PbO2 plates

Aqueous
H2SO4

Fig. 2.26 Lead accumulator or acid storage cell

The cell may be represented as

Pb/PbSO4 // H2SO4 (aq)/PbO2/Pb

Discharge Reactions of a Battery

During the discharge process, the electrode reaction a cell can be as
follows:
Discharge Reaction
At anode
Pb Pb2+ + 2 e–
Pb + SO42–
2+
PbSO4
Pb + SO42– PbSO4 + 2 e– ...(2.22)
At cathode
PbO2 + 4 H+ + 2 e– Pb2+ + 2 H2O
Pb2 + SO42– PbSO4
PbO2 + 4 H+ + SO42– + 2 e– PbSO4 + 2 H2O ...(2.23)
Overall cell reaction during use (discharging)
Pb + PbO2 + 4 H+ + 2 SO42– 2PbSO4 + 2 H2O + Energy ...(2.24)
The voltage produced during the discharge process is 2.0 V. The PbSO4
formed during the discharge process gets adhered to the electrodes. The
PbSO4, thus deposited on the electrode interface is utilized again during
the charging process of the cell. As a result, the concentration of H2SO4
decreases and hence the density of H2SO4 falls below 1.2 g/ml. So the
battery needs recharging.

Charging Reaction of a Battery

The cells of a battery can be charged by reversing the electrode
reactions. This can be achieved by applying a higher emf of an external
source. During the charging process, each cell of a battery acts as an
electrolytic cell. Lead and lead dioxides are deposited on their respective
electrodes.
The electrode reactions taking place during charging are, the
following:
At anode
PbSO4 + 2 H2O PbO2 + 4 H+ + SO42– + 2 e– ...(2.25)
At cathode
PbSO4 + 2 e– Pb + SO42– ...(2.26)
The net reaction during charging is
2 PbSO4(s)+ 2H2O+ Energy Pb + PbO2 (s) + 4H+ + SO42– ...(2.27)
In general, if the lead–acid battery is reversible with a better cycle life
then the net battery cell reaction during discharging–charging processes
for a cycle can be represented as,
Discharging
+
Pb + PbO2 + 4 H + 2 SO42– 2PbSO4 + 2 H2O + Energy
Charging

Applications
1. Lead–acid batteries are widely used for SLI system (Starting-
Lighting-Ignition) of road automobiles.
2. They are also used in telephone exchanges, railway tracks,
broadcasting, power stations, etc.
Note:
(i) Overcharging or excessive charging may continue the electrolysis
of water. This results in the liberation of H2 and O2 gases at the
electrodes and may build up high pressure. Further, it may reduce
 the acid level and may damage the exposed electrode. Therefore,
a catalyst like Sb is incorporated into the Pb plate, which enables
the combination by H2 and O2 to form H2O.
(ii) During discharge, the battery functions as an electrochemical cell
(voltaic cell); while during charging the battery functions as an
electrolytic cell.
(a) Electrochemical Cell
• Negative plate—Anode; Pb undergoes oxidation to form PbSO4.
• Positive plate—Cathode; PbO2 undergoes reduction to form
PbSO4.
(b) Electrolytic Cell
• Negative plate—Cathode; PbSO4 undergoes reduction to form
Pb.
• Positive plate—Anode; PbSO4 undergoes oxidation to form
PbO2.

2.16 NICKEL– CADMIUM BATTERIES (NICAD)

Nickel–cadmium batteries are examples of rechargeable alkaline batteries.
During charging and discharging, there is no loss of products (the
products stick to the electrodes) and no gas evolution occurs at the active
electrodes (anode and cathode). They have low internal resistance, long
shelf life (> 20 years) without any significant maintenance and good
cycle life (> 1000 cycles). Their capacity varies with the size of anode and
cathode materials. They have the cell voltage of 1.35 – 1.40 V irrespective
of the size of electrodes.
The active materials used in the battery system are the following:
Anode: Cadmium as a mixture of metal oxide and/or hydroxide.
Cathode: Nickel oxyhydroxide
Electrolyte: Aqueous KOH
The nickel–cadmium battery is represented as
Cd, CdO/KOH/NiO (OH)
The OCV of a fully charged cell is about 1.35 volts.

Chemistry During Discharging

At anode
Oxidation of cadmium takes place. Cd2+ ions, so formed, combine with
OH– ions to form Cd (OH)2.
 Cd Cd2+ + 2e–
2+
Cd + 2OH– Cd (OH)2
Net anode
Cd + 2OH– Cd (OH)2 + 2e–
At cathode
Reduction of nickel oxyhydroxide takes place.
2NiO (OH) + 2H2O + 2e– 2Ni(OH)2 + 2OH–
Net cell reaction
Cd + 2NiO (OH) + 2H2O Cd(OH)2 + 2 Ni(OH)2

Chemistry During Charging

The charging process is similar to that of a lead storage battery. When
the current is passed in the opposite direction, the electrode reaction gets
reversed. As a result, Cd gets deposited on the anode and NiO(OH) on
the cathode.
The net reaction during charging is
Cd(OH)2 + 2Ni(OH)2 Cd + 2NiO(OH) + 2H2O
Applications
It is used in calculators, electronic flash units, transistors and cardless
appliances.
Advantage
1. It is smaller and lighter.
2. It has longer life than lead storage cell.
3. Like a dry cell, it can be packed in a sealed container.
Disadvantage
It is more expensive than a lead storage battery.

2.17 LITHIUM BATTERY—THE BATTERY

OF THE FUTURE

It is a solid-state battery as it uses a solid electrolyte and not a solution

or a paste. In this battery, the anode is lithium and the cathode is made
of TiS2. The solid electrolyte used in this is a polymer which permits the
passage of ions but not that of electrons. The cell reactions are
At Anode
Li (S) Li+ + e–
At Cathode
TiS2 (S) + e– TiS2–
Overall reaction
Li(S) + TiS2(S) Li+ + TiS2–
Li+ + TiS2– LiTiS2
Anode Cathode

Li +
Li TiS2
Solid electrolyte

+ – – –
Li Æ Li + e TiS2 + e Æ TiS2

Fig. 2.27 Solid state lithium battery

It produces a cell voltage of 3 V. It is rechargeable. Several other types

of secondary lithium batteries are also known; the Li/MnO2, Li/V2O5,
Li/MoO2 and Li/Cr3O8 are some among these.
The lithium battery is considered to be the cell of the future because
• Its cell voltage is high, 3 V
• Lithium being a light-weight metal, only 7 g (1 mole) of material
is required to produce 1 mole of electrons
• Li has the most negative E° value and therefore generates a higher
voltage than other types of cells
• All the constituents of the battery are solids and, therefore, there
is no risk of leakage from the battery
• This battery can be made in a variety of sizes and shapes

Lithium–Sulphur Battery
+ –
This is a rechargeable battery. Its
anode is made of lithium. Sulphur
is the electron acceptor; the electron
from lithium is conducted to sulphur
by a graphite cathode. b -alumina
b--alumina Li (I )
(NaAl11O17) is used as the solid
electrolyte.
It allows the Li ions to migrate
S (I )
through its lattice easily, to
equalize the charge, but not the big
polysulphide product ions.
Fig. 2.28 Lithium–Sulphur battery
 This battery is operated at high temperatures as S and Li must be in
their molten states for the operation of the cell reactions:
Anode
2Li (S) 2Li+ + 2e–
Cathode
S + 2e– S2–
Overall
2Li(S) + S 2Li+ + S2–
The S2– formed reacts with elemental sulphur to form the polysulphide
ion:
S2– + n S [Sn+1]2–
The direct reaction between Li and S, detrimental to current production,
is prevented by the intervening alumina in the cell.
Advantages
• The alkali metal–sulphur battery is light in weight unlike the
lead–acid battery.
• It has a high energy density.
• Its use in electric cars is being slated commercially.

2.18 FUEL CELLS

Fuel cells are electrochemical cells having a separate fuel–oxidant system

that produces the electrochemical reaction in which the fuel is oxidized
at the anode. Like other electrochemical cells, fuel cells also consist of
an electrolyte and two electrodes.
The basic principle of fuel cells are the same as that of electrochemical
cells, but the main difference in function of the cell is that the
electrochemical energy is provided by a fuel and an oxidant stored
outside the cell in which the electrochemical reaction takes place. Hence,
electrical power can be produced from these fuel cells as long as the cells
are supplied with fuels and oxidants.

Theory
In fuels, the chemical energy is converted to heat which is transformed
to mechanical energy that finally produces the electrical energy. But in
fuel cells, the chemical energy is directly converted to electrical energy.
This direct conversion of chemical energy to electrical energy has
100% efficiency. The cell representation of any fuel cell can be given as
follows.
Fuel/Electrode//Electrolyte//Electrode/Oxidant
At the anode, the fuel gets oxidized liberating electrons and the
oxidation products of the fuel. The electrons liberated from the anode
reduce the oxidant at the cathode. Thus, the electron circuit or current
density is established.
Fuel + Oxygen Oxidation Product + Electricity

Alkaline Fuel cell (AFC) or Hydrogen–Oxygen Fuel Cells

In alkaline fuel cells, the electrolyte is an alkali such as potassium
hydroxide (30–40% aqueous solution). Alkaline fuel cells make use of
high-purity hydrogen as fuel and oxygen as oxidant. This kind of fuel
cell is otherwise known as hydrogen–oxygen fuel cell. The electrodes
are generally embedded with catalysts. Wide choices of catalysts are
available for these cells such as platinum, silver, gold, metal oxides, etc.
An alkaline fuel cell with a circulating electrolyte is free from impurity
formation and it also acts as a cooling liquid.
Fuel cells combine hydrogen and oxygen to produce electricity and
water. Hydrogen is fed into the anode of the fuel cell. Air provides the
oxygen (oxidant) and enters the fuel cell at the cathode. As shown in
Fig. 2.29, the actual chemistry depends on the fuel cell type. Using the
Proton Exchange Membrane Fuel Cell (PEMFC), as an example, the
hydrogen is split into two streams at the anode: positive hydrogen
protons and negative electrons. The hydrogen proton (H+) stream passes
through the electrolyte to the cathode but the electrolyte precludes the
passage of the electron stream. The electron stream is instead driven
through an external circuit, forming an electric current. This electric
current is then available for powering a load with the electrons returning
to the cathode to bring closure to the fuel-cell electrochemical process.
In particular, the electrons combine with the hydrogen protons and the
oxygen at the cathode to create water. As noted in Fig. 2.29, while the
basic principles of all fuel cells are the same, the electrolytes, conducting
ions and operating temperatures differ between fuel-cell types.
At anode
H2 2H+
2H + 2OH–
+
2H2O + 2e–
At cathode
O2 + 2H2O + 4 e– 4OH–
Net reaction
H2 + 2 OH– 2H2O + 2 e–

–
Load
e

Fuel – – Oxidant
e e
AFC H2 –
OH O2 80°C
H2O
H2 – 700-
SOFC O O2
H2O 1000°C
PAFC + O2 200°C
and H2 H
H 2O 90°C
PEMFC
H2 – O2
MCFC CO2 CO 3
650°C
H2O CO2
Product gases Product gases
Residual Fuel Residual oxidant
Anode Cathode
Electrolyte
(Ion conductor)

Fig. 2.29 Fuel-cell operation

Five major types of fuel cells have been (or are being) developed and
are generally identified according to the type of electrolyte used.
The five major types of fuel cells are
1. Alkaline Fuel Cell (‘AFC,’ ~80oC)
2. Proton Exchange Membrane Fuel cell (‘PEM fuel cell,’ ~90oC)
3. Phosphoric Acid Fuel Cell (‘PAFC,’ ~200oC)
4. Molten Carbonate Fuel Cell (‘MCFC,’ ~650oC)
5. Solid Oxide Fuel Cell (‘SOFC,’ 700–1000oC)
Advantages of Fuel Cells
1. Fuel cells have a high efficiency of energy conversion (75% to
83%), i.e. chemical energy to electrical energy.
2. Fuel cells make use of hydrocarbon gas from fossil fuel and
the resultant emissions of pollutants are within the permissible
limits.
3. Fuel cells have low maintenance cost
4. Fuel cells have a quick start system.
 5. The regenerative hydrogen–oxygen fuel cell systems have great
applications in space research. They also produce potable water
as an end product.
6. In fuel cells, low-cost fuels can be used, provided they are operated
at higher temperatures.

2.19 SOLAR ENERGY

The sun is the ultimate source of energy, directly or indirectly for all
other forms of energy. The nuclear fusion reactions occuring inside the
sun release enormous quantities of energy in the form of heat and light.
The solar energy received by the near earth space is approximately
1.4 kilojoules/second/m2, known as solar constant.
At present, due to modern scientific development, we are using solar
energy for various purposes. In general, we can use solar energy in two
types of systems.
1. Solar photovoltaic power system
2. Solar thermal energy system

2.19.1 Solar Photovoltaic Power System

• In this method, the solar radiation is transformed into electricity
through the solar cells, called photovoltaic cells or PV cells.
• Solar cells are made of thin wafers of semiconductor materials
like silicon and gallium. When solar radiation falls on them, a
potential difference is produced which causes flow of electrons
and produces electricity.
• A group of solar cells joined together in a definite pattern forms
a solar panel which can harness a large amount of solar energy
and can produce electricity enough to run street light, irrigation
water pumps, etc.
• Household lights, radio, television, pump sets and other electrical
appliances can be operated with the electricity produced from
solar radiation.
• Electricity needed to operate railway signals are generated by this
method.
• Electricity required for satellites in space is produced from the
solar panels attached to them.
• Electricity produced from solar energy helps very much for
operating communication systems, lighthouses and offshore
platforms located in regions where electricity cannot be easily
supplied.
2.19.2 Solar Thermal System
By using solar thermal collectors, the heat received from the sun can be
converted into thermal energy.
By concentrating solar radiation, various solar thermal devices like
solar cookers, water heaters, desalination systems, solar refrigerators,
solar dryers and solar microorganism removers, etc., can be operated.
(a) Solar Cooker
A solar cooker makes use of solar heat by reflecting the solar radiation
using a mirror directly on to a glass sheet, which covers the black
insulated box within which the raw food is kept. A new design of solar
cooker is now available which involves a spherical reflector (concave or
parabolic reflector) instead of a plane mirror that has more heating effect
and hence greater efficiency.
The food cooked in solar cookers is more nutritious due to slow
heating. However, it has the limitation that it cannot be used at night or
on cloudy days. Moreover, the direction of the cooker has to be adjusted
according to the direction of sun rays.
(b) Solar Water Heater
It consists of an insulated box painted black from inside and having a
glass lid to receive and store solar heat. The inside of the box has a black
painted copper coil through which cold water is made to flow in, which
gets heated and flows out into a storage tank. The hot water from the
storage tank fitted on the rooftop is then supplied through pipes into
buildings like hotels and hospitals.
(c) Solar Furnace
Here, thousands of small plane mirrors are arranged in concave reflectors,
all of which collect the solar heat and produce as high a temperature
as 3000°C.

QUESTIONS

Two-Mark Questions with Answers

1. Differentiate between metallic and electrolytic conductors.
(i) Metallic conduction involves the flow of electrons in a
conductor, whereas electrolytic conduction involves the
movement of ions in a solution.
 (ii) In case of a metallic conductor, conduction decreases with
increase of temperature. But in an electrolytic conductor,
conduction increases with increase of temperature due to
increase in number of ions with respect to temperature.
2. Write the cell representation and cell reaction of a calomel
electrode.
Cell representation
Hg, Hg2Cl2 (s), KCl (satd. solution)
Cell reaction
Hg2Cl2 (s) + 2 e– 2 Hg (l) + 2 Cl– (aq)
3. What is an electrolytic cell? Give examples.
Electrolytic cells are cells in which electrical energy is used to
bring about chemical reaction. The redox reaction in an electrolytic
cell is nonspontaneous. Electrical energy is required to induce the
electrolysis reaction, e.g. electrolysis of water, electroplating, etc.
4. Explain galvanic cell with examples.
Galvanic cell is a device in which a redox reaction is utilized to
get electrical energy. Galvanic cell is also commonly referred to
as voltaic or electrochemical cell, e.g. Daniel cell. It consists of zinc
electrode, dipping in ZnSO4 solution (where oxidation takes
place) and a copper electrode, dipping in CuSO4 solution (where
reduction takes place).
5. Draw the diagram and cell representation of a Daniel cell.
Voltmeter
–
e
–
e
+ Cathode
Anode Salt bridge

Zinc Copper
plate plate
ZnSO4 CuSO4
Solution solution
2+ – 2+ –
Zn Æ Zn + 2e Cu 2e Æ Cu
(Oxidation) (Reduction)

Fig. 1 Diagram of a Daniel cell

Cell representation
(–) Zn | ZnSO4(aq)(1M) || CuSO4(aq) (1M) | Cu (+)
Anode (Cathode)
 6. Define standard electrode potential.
Standard electrode potential is defined as the tendency of an
electrode to lose or gain electrons when it is dipped in its own
salt of 1M concentration at 25°C.
7. Write the Nernst equation for single-electrode potential and
explain the terms involved.
RT [Product]
E = E° – ___ ln __________
nF [Reactant] ( )
E = electrode potential of the electrode
E° = standard electrode potential of the electrode
R = gas constant
T = temperature (25°C)
N = number of valency electrons involved
F = faraday
[Product] = concentration of the product
[Reactant] = concentration of the reactant
8. What is reference electrode? Give examples.
The electrode of standard potential with which we can compare
the potentials of other electrode is called a reference electrode, e.g.
Standard Hydrogen Electrode (SHE) and calomel electrode.
9. Differentiate between primary and secondary batteries.
[Link] Primary Batteries Secondary Batteries
1. In these cells, the electrode and the In these cells, the electrode reactions can
electrode reactions cannot be reversed by be reversed by passing an external electrical
passing an external electrical energy. energy.
2. The reaction occurs only once and after They can be recharged by passing electrical
use they become dead. Therefore, they current and used again and again. These are
are not rechargeable. also called storage cells or accumulators.

10. Define electromotive force.

It is defined as the difference of potential which causes the flow of
current from one electrode of higher potential to an other electrode
of lower potential.
11. Differentiate between electrolytic and electrochemical cells.
[Link] Electrolytic Cells Electrochemical Cells
1. Electrolytic cells are cells in which Electrochemical cells are cells in which
electrical energy is converted to chemical energy is converted to
chemical energy, e.g. electrolysis. electrical energy, e.g. Daniel cell.
2. The cathode carries negative charge. The cathode carries positive charge.
The anode carries positive charge. The anode carries negative charge.
3. Here the electrons are supplied to the But electrons are drawn from the cell,
cell from the external battery, i.e., electrons move from anode to cathode
i.e. , electrons move in through the through the external circuit.
cathode and comes out from the anode.
4. The extent of chemical reaction occurring The emf of the cell depends on the
at the electrodes is governed by concentration of the electrolytes and the
Faraday’s law of electrolysis. chemical nature of the electrode.

12. What is the cell reaction of a Weston standard cadmium cell?

At negative electrode
Cd(s) Cd2+ (aq) + 2 e–
At positive electrode
Hg2SO4 (s) + 2 e– 2 Hg(l) + SO42– (aq)
13. How can we determine the change in free energy value using
emf of the cell?
Change in free energy can be calculated by using the following
equation:
DG° = –nFEo
where DG° = change in free energy
n = number of valency electrons
F = faraday
E° = standard electrode potential
14. A voltmeter cannot be used in the precise measurement of emf
of a galvanic cell. Why?
The emf of the cell cannot be determined accurately by connecting
a voltmeter directly between the two electrodes of the cell, because
during such a measurement, a part of the cell current is drawn,
thereby causing a change in the actual emf.
15. Define emf series.
The various electrodes are arranged in the order of their increasing
values of standard electrode reduction potential on the hydrogen
scale. This arrangement is called electrochemical series or emf
series.
16. What are the advantages of potentiometric titrations?
• Potentiometric titrations can be carried out in coloured
solutions where indicators cannot be used.
• There is no need of prior information about the relative
strength of titrant before the titration.
 17. Write the charging and discharging reaction of an Ni–Cad
battery.
Discharging
Cd + 2 NiO (OH) + 2H2O Cd(OH)2 + 2Ni(OH)2
Charging

18. What are batteries? How do they differ from cells?

A battery is an arrangement of several electrochemical cells
connected in series that can be used as a source of direct electric
current.
A cell is one that contains only one anode and cathode, but a
battery contains several anodes and cathodes.

Ten-Mark Questions
1. Describe the construction and working of a galvanic cell.
2. What is the emf series? Discuss the importance of emf series.
3. Derive Nernst equation for single-electrode potential.
4. Describe the various types of electrodes.
5. Write short notes on the following.
1. Calomel electrode
2. Glass Electrode
6. What is emf? How is the emf of the unknown cell is measured?
7. Derive the Nernst equation for emf of a cell.
8. What is a reversible and irreversible cell? Explain with
examples.
9. Explain in detail about potentiometric titrations.
10. Calculate the emf of the cell
Zn/Zn2+ (0.1 M) ?? Ag+ (10.0 M)/Ag, given that E° 2+ = – 0.76 V
Zn /Zn

and E°Ag+/ Ag = + 0.80 V. Write down the cell reaction.

11. Explain the acid–base titration carried out in potentiometric
titration.
12. Describe Weston standard cadmium cell.
13. Discuss in detail about lead–acid battery.
14. Write the cell construction, cell reaction of Ni–Cad during charging
and discharging.
15. Describe the cell representation and cell reaction of
1. Calomel electrode
2. Chlorine electrode
16. Using emf measurements, show how the following is
determined:
1. Solubility of sparingly soluble salt
2. Valency of the ion
3. Determination of the standard free energy
 UNIT

3
Corrosion and Its
Control Methods

3.1 INTRODUCTION

Corrosion is a general term that refers to the deterioration and ultimate

destruction of a metal due to its reaction with the surrounding (or)
environment such as gaseous, moisture, liquid, etc.
In nature, metals except noble metals such Au, Pt, etc., are not found
in free state due to their reactivity. The metals are thermodynamically
unstable in their free state. They are stable in the form of certain
compounds like oxides, carbonates, hydroxyl carbonates, sulphides,
chlorides and silicates, etc. It is the ore (as their oxides, carbonates,
hydroxyl carbonates, sulphides, chlorides and silicates ) from which the
metals are extracted by metallurgical processes. A metallurgical process
requires a large amount of heat energy.

Metallurgical process
(Reduction)
Metal Ore Pure Metal
(Less energy state) (High-energy state)
Corrosion
(Oxidation)
More stable, e.g., Less stable, e.g.,
Fe2O3, ZnO, PbS, CaCO3 etc., Fe, Zn, Pb, Ca etc.,

For example, when iron is exposed to the atmosphere containing

oxygen and water vapour, it reverts to its metallic oxide Fe2O3. n H2O
which is an ore of iron.
Definition
Corrosion can be defined as any process of destructive disintegration
or alteration of a metal or alloy caused by direct chemical attack or by
electrochemical reaction with its environment. In the case of iron and
steel, corrosion is often referred to as rusting.
In other words, corrosion is a process in which the gradual dissolution
or oxidation of a metal takes place.
Industrial development and domestic applications involve the use
of metals and alloys. Corrosion causes a heavy loss to industries in
particular and imparts the economic status of a society in general. The
annual loss for corrosion in India is around 600 crores. The loss due
to corrosion includes the cost of repair or replacement of the corroded
component or equipment. By making proper use of existing corroded
materials and techniques for corrosion prevention, about 25% of the
estimated amount ( 150 crores in India) can be saved.
Since it is impossible to eliminate corrosion, extensive research work
has been undertaken to minimize corrosion rather than to prevent
corrosion.

3.2 CLASSIFICATION OF CORROSION

The corrosion process is classified on the basis of mechanisms.
1. Dry corrosion, or chemical corrosion
2. Wet corrosion, or electrochemical corrosion

3.2.1 Dry Corrosion, or Chemical Corrosion

This type of corrosion occurs through direct chemical action of the
environment or atmospheric gases such as oxygen, halogen, H2S, SO2,
N2 or anhydrous inorganic liquids in close contact with the metal.
This can be classified as follows,
(a) Corrosion by oxygen (oxidation corrosion)
(b) Corrosion by other gases (Cl2, H2S and H2)
(c) Liquid–metal corrosion
(a) Corrosion by Oxygen (Oxidation Corrosion)
Direct attack of metals by oxygen at low or high temperatures, in the
absence of moisture, leads to oxidation corrosion. The resultant metal
oxide is known as a corrosion product.
The rates of oxidation of metals at ambient temperatures are low but at
higher temperatures, oxidation is also kinetically favoured. Alkali metals
(Li, Na, K, Rb, etc.) and alkaline earth metals (Ba, Ca, Sr, etc.) are even
rapidly oxidized at low temperatures whereas at higher temperatures,
almost all metals except Ag, Au and Pt are oxidized.
2–
O Inward diffusion of
oxygen through scale

Outward diffusion of
metal ions through 2+
scale M
(Metal)

Fig. 3.1 Oxidation corrosion

Mechanism The following type of reactions may take place during the
oxidation corrosion.
(i) At Anode
Oxidation first occurs at the surface of the metal resulting in
the formation of metal ions (M2+) with the liberation of free
electrons.
M M2+ + 2 e– (Oxidation)
(ii) At Cathode
The liberated electron will be taken up by the oxygen and is
converted into oxide ion (O2–)
½ O2 + 2e– O2– (Reduction)
(Oxide ion)

(iii) Net Reaction

Metal ion combines with oxide ions forming the metal oxide
film.
M + ½ O2 M2+ + O2– MO
Metal oxide

Types of Metal Oxide Film

It is essential to know the nature of the metal oxide films formed, because
it decides the further action on the metal surface. There are generally
four types of metal oxide films.
(i) Stable film
A stable oxide layer is a fine grained in structure and forms a
compact surface adhered tightly to the metal surface. The oxide
films formed on the surface of the metals are impervious in nature
and stop further oxygen attack. Thus, the stable film acts as a
protective coating.
Examples: Al, Sn, Pb, Cu, etc.
 (ii) Unstable film
Unstable oxide layers are mainly produced on the surface of noble
metals which decompose reversibly to the metal and the oxide
which is liberated in the form of oxygen. In this case, the corrosion
is a continuous process.
Metal Oxide Metal + Oxygen
Examples: Au, Pt, Ag, etc.
(iii) Porous film
The oxide layers formed in some cases have pores or cracks. In
such a case, the atmospheric oxygen can easily move into the
metal surface through pores or cracks of the layer. So corrosion is
a continuous process.
Examples: Li, Na, K, Fe, etc.
(iv) Volatile film
The oxide layer formed in some cases is volatile. So the oxide
film volatilizes as soon as it is formed. The fresh metal surface
is kept exposed all the time for further attack. Thus it acts as a
nonprotective coating.
Example: Molybdenum oxide film (MoO3)

Pilling–Bedworth Rule
The protective or nonprotective oxide layer formation in metals is
governed by a rule known as “Pilling–Bedworth rule“. According to
this rule,
Volume of metal oxide film formed
Specific volume ratio = ________________________________
Volume of metal ion consumed
If the volume of the oxide formed is equal to or greater than the
volume of the metal from which it is formed, the oxide layer is nonporous
and therefore protective in nature.
Examples: Oxides of Al, Sn, Pb, Cu, etc.
Whereas, if the volume of the oxide formed is less than the volume of
the metal from which it is formed, the oxide layer is porous and therefore
nonprotective in nature.
Examples: Oxides of Li, Na, K, Mg, Ca, Sr, etc.
(b) Corrosion by Other Gases
Other gases such as Cl2, SO2, H2S, CO2, F2 and NOx can also cause
corrosion. In dry atmosphere, these gases react with metal and form
corrosion products which may form a protective or nonprotective film
on the metal surface.
For example,
(i) Chlorine attacks on silver forms AgCl film, which is protective
and nonporous, so it prevents further corrosion.
Cl2 + 2Ag 2AgCl
(Nonporous film)

(ii) Sn reacts with dry Cl2 gas present in the atmosphere and forms
volatile SnCl4 which volatilizes immediately. So the corrosion is
a continuous process.
2Cl2 + Sn SnCl4
(Volatile film)

(iii) Hydrogen Embrittlement or Hydrogen Corrosion

At high temperature, H2S reacts with steel containing Fe and forms
FeS scale. It is porous and corrosion is a continuous process.
Metals combine with H2S gas to liberate atomic hydrogen.
H2S + Fe FeS + 2[H]
(Atomic hydrogen)

The atomic hydrogen is very reactive, penetrates the metal and

occupies the voids of the metal.
[H] + [H] H2
The atomic hydrogen recombines inside the metal and develops
pressure which leads to cracking of the metal. This is known as
‘hydrogen embrittlement’ or ‘hydrogen corrosion’.
(iv) Decarburisation
Atomic hydrogen is formed by dissociation of H2 gas at high
temperature.
H2 [H] + [H]
C+H CH4
The atomic hydrogen is highly reactive and combines with carbon
present in the metal forming CH4 gas which leads to cracking of
the metal surface. The process of decrease in carbon content in
steel is known as ‘decarburisation of steel’.
(c) Liquid–Metal Corrosion
This type of corrosion is due to the chemical action of flowing liquid
metals on solid metal/alloys at high temperatures.
As a result of this corrosion, the solid metal becomes weak because it
involves either
 1. Dissolution of a solid metal by a liquid metal, or
2. Due to the penetration of the liquid metal into the solid metal.
Such types of corrosion are found in nuclear power plants.

3.2.2 Wet (or) Electrochemical Corrosion

The prime conditions for this type of corrosion are
1. The conducting electrolytic liquid is in contact with metal
2. Two dissimilar metals are partially dipped in the electrolyte
In the above condition, one part of the metal becomes the anode and
the remaining part becomes cathode.
(a) At Anodic Area n+ –
M M + n e (Oxidation)
Oxidation takes place with the
liberation of free electrons. Hence,
the anodic metal is destroyed either
by dissolution, or forms compounds Dissolved Forms compounds
such as oxides. like metal oxide

(b) At Cathodic Area

In this area, reduction reaction takes place (i.e. gain of electrons).
Dissolved metal ions in the medium accept the electrons to form some
ions like OH–, O2–. The metallic ions and nonmetallic ions formed (at
cathode) diffuse towards each other through a conducting medium and
form a corrosive product somewhere between the anode and cathode.
(c) Mechanism
(i) At Anodic Area
M Mn+ + n e– (Oxidation)
The anodic reaction involves dissolution of metal as corresponding
metal ions with the liberation of free electrons.
(ii) At Cathodic Area
Depending upon the nature of electrolytic solution, the cathodic reaction
consumes electrons either by
1. Hydrogen evolution mechanism or
2. Oxygen Absorption mechanism
This can be explained as follows.
1. Hydrogen Evolution Mechanism
This type of corrosion mechanism takes place when base metals are in
contact with acidic solutions or the solutions are completely free from
dissolved oxygen.
 ‘All metals above hydrogen Anodic solution (electrolyte)
in the electrochemical series Small cathodic area
have a tendency to get dissolved Anode
(undergo corrosion) in acidic
solut ion wit h si multa neous Fig. 3.2 Hydrogen evolution
evolution of hydrogen gas’.
Example When iron metal is in contact with an acidic environment,
hydrogen evolution mechanism takes place.
In this type of corrosion, the anodes usually possess very large area
whereas the cathodes have small areas.
At anodic area
Iron undergoes dissolution to give Fe2+ ions with the liberation of free
electrons.
Fe Fe2+ + 2 e– (Oxidation)
At cathodic area
The liberated electrons flow from the anodic area to the cathodic area,
where hydrogen ions (H+) get reduced to hydrogen gas (H2 ).
2H+ + 2e– H2 (Reduction)
The overall reaction is
Fe + 2H+ Fe2+ + H2
2. Oxygen Absorption Mechanism
This type of corrosion mechanism takes place when base metals are in
contact with neutral, aqueous or slightly alkaline solution with some
amount of dissolved atmospheric oxygen.
Example Rusting of paint-coated iron in neutral, aqueous or slightly
alkaline solution with some amount of dissolved atmospheric oxygen.
The surface of the iron is usually coated with a thin film of iron oxide.
However, the oxide film/paint coated iron develops some cracks on the
surface. When a water droplet falls on the crack, the crack area acts as
anode (small area) and the remaining part of the iron acts as cathode
(large area).
At anodic area
Iron metal dissolves as Fe2+ with the liberation of electrons.
Fe Fe2+ + 2 e– (Oxidation)
At cathodic area
The liberated electrons flow from the anodic area to the cathodic part
through the metal where the electrons are taken up by the dissolved
oxygen to form OH– ions.
1/2 O2 + 2 e– + H2O 2OH – (Reduction)
 Air
O2-Oxygen
Water

2+ –
Fe + 2OH Æ Fe(OH)2 2+
Fe 1 – –
O + 2e + H2O Æ 2OH
2 2
Cathode area
2+ –
Rust Femetal Æ Fe + 2e
Anode area
Metal

Fig. 3.3 Oxygen absorption mechanism

The overall reaction

The Fe2+ ions (at anode) and OH– ions (at cathode) react to produce
ferrous hydroxide precipitate Fe(OH)2.
Fe + ½ O2 + H2O Fe2+ + 2OH– Fe(OH)2
If enough oxygen is present, ferrous hydroxide is converted into ferric
hydroxide.
4Fe(OH)2 + O2 + 2H2O 4Fe(OH) 3 (or) Fe2O3 . 3H2O
Yellow Rust

Table 3.1 Differences between chemical and electrochemical corrosion

Sl. No Dry or Chemical Corrosion Wet or Electrochemical Corrosion
1. It occurs in dry state. It occurs in presence of moisture or electrolyte.
2. It involves direct chemical attack It involves the setting up of a huge number of
by the environment. galvanic cells.
3. It follows adsorption mechanism. It follows the mechanism of electrochemical
reaction.
4. Corrosion product accumulates on the Corrosion occurs at anode while products
same spot, where corrosion occurs. gather at cathode.
5. Uniform corrosion behaviour is seen, Localized corrosion occurs, i.e. one metal surface
i.e. either the whole surface of the alone is corroding even though both metal
metal in contact with the medium surfaces are in contact with the medium.
corrodes, or it does not.
6. Even a homogeneous metal surface Heterogeneous or bimetallic contact condition
gets corroded by this process. produces corrosion.
7. Only heat evolution can be observed. Due to electron flow from the site of oxidation
to site of reduction, current flow can be
observed.
8. It is a slow and self-controlled process. It is a fast and continuous process.
9. Example: Tarnishing of silver Example: Rusting of iron
 3.3 TYPES OF ELECTROCHEMICAL CORROSION

Electrochemical corrosion is of two types.

1. Galvanic (bimetallic) cell corrosion
2. Differential aeration corrosion or concentration cell corrosion

3.3.1 Galvanic (Bimetallic) Corrosion

Galvanic (also called ‘dissimilar metal corrosion’ or wrongly ‘electrolysis’)
refers to corrosion damage induced when two dissimilar materials are
coupled in a corrosive electrolyte.
When a galvanic couple forms, one of the metals in the couple becomes
the anode and corrodes faster than it would all by itself, while the other
becomes the cathode and corrodes slower than it would alone. For
galvanic corrosion to occur, three conditions must be present:
1. Electrochemically dissimilar metals must be present.
2. These metals must be in electrical contact.
3. The metals must be exposed to an electrolyte.
This is the most common type of corrosion and is also known as
bimetallic corrosion. When two dissimilar metals (e.g. Zn and Cu)
are electrically connected and are exposed to an electrolyte (aqueous
electrolyte solution or moisture), the metal higher in the electrochemical
series acts as the anode and dissolves into the solution (i.e. corrodes)
and the metal lower in the electrochemical series, or more noble, acts
as the cathode.
The cathodic reaction mechanism depends on the electrolyte, i.e. in the
acidic medium (electrolyte), the corrosion takes place with the evolution
of hydrogen gas whereas in neutral or alkaline medium (electrolyte),
absorption of oxygen takes place.

Example 1 In a Zn/Fe couple, the alloy is exposed to neutral/alkaline

electrolyte, zinc will acts as anode (higher in electrochemical series) and
undergoes corrosion whereas Fe (lower in electrochemical series) acts as
cathode and is not affected.
The following reactions are taking place at anode and cathode.
At anode
Zn Zn2+ + 2e– (oxidation)
At cathode
½ O2 + H2O + 2e– 2OH– (Reduction)

Electrolyte (cathode)
Neutral/Alkaline

Zn Fe
More Anode Cathode Less
active active

Fig. 3.4 Galvanic corrosion (Zn/Fe)

Overall reaction
Zn + ½ O2 + H2O Zn2+ + 2OH– Zn(OH)2

Example 2 In an Fe/Cu couple, the alloy is exposed to neutral/alkaline

electrolyte, Fe acts as anode (higher in electrochemical series) and undergoes
corrosion, whereas Cu (lower in electrochemical series) acts as cathode and
is not affected.

Electrolyte (cathode)
Neutral/Alkaline

Fe Cu
More Anode Cathode Less
active active

Fig. 3.5 Galvanic corrosion (Fe/Cu)

The following reactions take place at anode and cathode.

At anode
Fe Fe2+ + 2 e– (Oxidation)
At cathode
½ O2 + H2O + 2e– 2OH– (Reduction)
Overall reaction
Fe + ½ O2 + H2O Fe2+ + 2OH– Fe(OH)2
Examples:
1. Steel screws in a brass marine hardware
2. Steel pipe connected to copper plumbing
Avoidance of Galvanic Corrosion
The following methods may be followed for the avoidance of galvanic
corrosion.
(i) Avoid Mixing of Metals If only one material is used in a construction,
the problem is avoided. But in case of alloys, selection of metals
should be very close in the emf series.
(ii) Prevent Electrical Contact It is often practical to prevent electrical
contact between the dissimilar metals. This may be achieved either
by the use of nonconducting (e.g. rubber or plastic) spacers, spool
pieces or gaskets, perhaps in conjunction with sleeves around
bolts (or) providing insulating material. For the same reason, a
gap may be left between galvanized roofing and a stainless steel
down-pipe.
(iii) Prevent the Wetted Junction The third condition can be removed
by ensuring that no electrolyte remains at the intermetallic
junction—this may require extra attention to drainage or to
protection from the weather. A good covering of paint or sealant
over the junction can be effective to avoid galvanic corrosion.
(iv) Use the Area Effect to Avoid Galvanic Corrosion The area effect
should also be considered in avoiding corrosion damage, i.e. the
area of the cathode is always smaller than anodic area.

3.3.2 Concentration Cell Corrosion, or Differential

Aeration Corrosion
Concentration cell corrosion occurs when two or more areas of a metal
surface are in contact with different concentrations of the same solution
or different concentrations of dissolved oxygen in the electrolyte.
(a) Causes
1. It is due to the local difference in metal ion concentration.
2. It is caused by the local temperature difference.
3. It is due to inadequate agitation or slow diffusion of metal ions.
Differential aeration corrosion occurs when a metal is partially
immersed in a solution; the metal inside the solution has very poor
aeration when compared with the metal that is outside the solution. This
causes difference in potential between differently aerated areas.
 The area where there is less oxygen exposure will acts as anode
and the exposed to more oxygen area will behaves as cathode. (This is
acting like a concentration cell and concentration-cell corrosion current
is produced.) Concentration-cell corrosion is otherwise known as
differential aeration corrosion.
(b) Mechanism
At anode
M Mn+ + ne– (oxidation)
The electron will move to the cathodic site.
At cathode
Depending upon the electrolyte, the cathodic reaction will follow either
hydrogen evolution or oxygen absorption mechanism.
In acidic electrolyte,
2H+ + 2e– H2 (Reduction)
In alkaline/neutral electrolyte,
½ O2 + H2O + 2e– 2OH– (Reduction)
OH – ion will move faster and reach the anodic area and corrosion
will be seen in the pit. This is called ‘pitting corrosion’.

Example 3 When iron metal is partially immersed in a solution, the metal

inside the solution has very poor aeration when compared with the metal that
is outside the solution. The less aerated part acts as anode and the more
aerated part acts as cathode.

Fe Metal

Cathode
(More oxygenated
part)

Electrolyte Anode
(Less oxygenated
part)

Fig. 3.6 Concentration-cell corrosion (metal/electrolyte)

The following reactions are taking place at anode and cathode.

At anode
Fe Fe2+ + 2 e– (Oxidation)
At cathode
½ O2 + H2O + 2e– 2OH– (Reduction)
Overall reaction
Fe + ½ O2 + H2O Fe2+ + 2OH– Fe(OH)2
Thus, differential aeration corrosion occurs on the following
occasions.
1. Micropores on a metallic surface (pitting corrosion)
2. Oil, impurity (or) corrosion product on a metallic surface
3. Water in a particular spot on a metal (for a long time)
4. Crossed fencing
5. Joint of iron metals by iron washer
6. A metal surface partially immersed in water
7. A metal surface partly covered with dust, sand, etc.
Other examples for this type of corrosion are
(a) Pitting corrosion
(b) Pipeline corrosion
(c) Crevice corrosion
(d) Corrosion on wire fence
(a) Pitting Corrosion
Pitting corrosion is an electrochemical oxidation–reduction (redox)
process. It occurs within localized holes (cells) on the surface of metals
covered with a thin oxide film, which inhibits anodic dissolution. When
corrosion does occur, it sometimes hollows out a narrow hole, pits and
cavities in the metal. The bottoms of these pits tend to be deprived of
oxygen, thus promoting further growth of the pit into the metal.
Pitting corrosion starts with the small crevices (pits). Once pit
formation is established, the metallic part below the pit becomes the
anode and further corrosion takes place at the anodic area. The other
parts of the metal become the cathode and absorb the liberated electron
from the anode.

Example 4 The metal parts partially covered with dust, sand, water drops,
etc. is an example for pitting corrosion.
 Water drop

More oxygenated
part (cathode)

Less oxygenated
part (anode)
Metal

Fig. 3.7 Pitting corrosion

Liquid film on
2+ surface receives ions
Fe from metal
O2

–
e Oxide layer
protects surface but
allows electrons to
flow to oxygen

Oxygen deficient
anodic region near
bottom of corrosion pit

Fig. 3.8 Pitting corrosion

The area covered by the drop of water acts as an anode due to less
oxygen concentration and suffers corrosion. The uncovered area (freely
exposed to air) act as a cathode due to high oxygen concentration.
The rate of corrosion will be more when the area of cathode is larger
and the area of anode is smaller.
The following reactions are taking place at anode and cathode.
At anode
Fe Fe2+ + 2 e– (Oxidation)
At cathode
½ O2 + H2O + 2e– 2OH– (Reduction)
Overall reaction
Fe + 1/2 O2 + H2O Fe2+ + 2OH– Fe(OH)2

[O]

Fe(OH) 3
 This type of intense corrosion is called pitting corrsion.
(b) Pipeline Corrosion
Differential aeration corrosion may also occur in different parts of the
pipeline. The buried pipelines or cables passing from one type of soil
to another, say, from clay (less aerated) to sand (more aerated) may get
corroded due to differential aeration.
(c) Crevice Corrosion
When a crevice between different metallic objects is in contact with
liquids, the crevice becomes the anodic region due to less oxygen in the
crevice area and corrosion takes place. But the exposed area acts as the
cathode.
(d) Corrosion on Wire Fence
This type of corrosion also takes place in the wire fence. In this case, the
areas where the wires cross are less aerated than the other parts of the
fence. The corrosion takes place at the wire crossings because the less
aerated part act as anode.
Cathode

Cathode Anode Cathode

Cathode

Fig. 3.9 Corrosion on a wire fence

3.4 GALVANIC SERIES

In the emf series, a metal higher 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;
Fe corrodes faster than Sn; Cu corrodes faster than Ag, and so on. But
in some cases, this generalization is not so.
 For example, in a Zn-Al couple, Zn (below Al in the emf series) is
corroded, while Al acts cathodic and is protected. This kind of opposite
reactions are due to the fact that metals like Al develop strongly adhering
Al2O3 on the surface. This makes their electrode potential more (+) ve
or less (–) ve.
From the above observation, it is clear that emf series doesn’t account
for the corrosion of all metals and alloys.

Table 3.2 Galvanic Series (Metals in sea water at 25˚C)

Corroded end or Anodic 1. Mg

or Least noble 2. Mg alloy
3. Zn
4. Al
5. Cd
6. Al alloy
7. Low-carbon steel
8. Cast iron
9. High nickel cast iron
10. Stainless steel (active)
11. 50-50 Lead–Tin
12. Pb
13. Sn
14. Ni-Mo-Fe alloy
15. Silver
16. Ti
17. Graphite
Protected end or cathodic 18. Gold
or Most noble 19. Platinum

In order to give useful information about corrosion of metals and

alloys, a more practical series have been formulated on the basis of
studying corrosion behaviour (oxidation potential) of metals and alloys
in a given environment like sea water.
Definition
Different testing metals and alloys are coupled with a calomel electrode
and dipped in sea water. The oxidation potential of the different metals
and alloys are determined at 25˚C and tabulated in the descending order.
Metals occupying higher positions in the series undergo corrosion
in a vigorous manner. The above series is called galvanic series and it
gives more information about the corrosive tendencies of the different
metals.
Table 3.3 Differences between electrochemical series (emf) and galvanic series
Sl. No Electrochemical Series (emf) Galvanic Series
1. In this series, metals are arranged in the This series was developed by studying
order of their increasing values of standard corrosion behaviour of metals and alloys in
reduction potential on the hydrogen scale, unpolluted sea water without their
i.e. electrode potential is measured for oxide films.
a metal without any oxide film on them.
2. The position of a given metal in the emf The positions of a given metal depend on
series is permanently fixed. the other metal used for making the alloy,
(i.e position is not fixed).
3. It gives no information regarding It includes alloys in galvanic series and
the position of alloys. accounts their corrosion behaviour.
4. It comprises of metals and nonmetals. It comprises metals and alloys.
5. It predicts the relative displacement It predicts the relative corrosion
tendencies. tendencies.

3.5 FACTORS INFLUENCING RATE OF CORROSION

Corrosion is a kind of reaction that takes place in the metal by the
influence of its environment. Hence both (i) the nature of the metal, and
(ii) the nature of the environment play an equal part in the corrosion of
the metal. The following are the factors responsible for the corrosion.

3.5.1 Nature of the Metal

(a) Position of Metal in the Galvanic Series
The extent of corrosion depends upon the position of the metal in the
galvanic series. When two metals are in electrical contact, the metal
higher up in the galvanic series becomes anodic and suffers corrosion.
Further, the rate and severity of corrosion depend upon the difference
in their positions in the galvanic series. The greater the difference, the
faster the corrosion of anodic metal.
(b) Relative Areas of Anode and Cathode
Corrosion will be severe if the anodic area is small and the cathodic
area is large. Larger cathodic area of the cathode will create a demand
for more electrons, which can be met by the smaller area of the anode,
only by undergoing more corrosion.
(c) Overpotential
Corrosion rate is inversely proportional to the overvoltage of a metal
in the corrosive environment. For example, when Zn metal is placed in
1 N H2SO4, it undergoes corrosion with evolution of H2 gas. Initially,
the rate of corrosion is quite slow, because of high overvoltage of 0.7 V.
But after the addition of a few drops of CuSO4, the corrosion of zinc is
accelerated due to decrease in H2 overvoltage to 0.33 V. Thus reductions
in overvoltage of the corroding metal/alloy accelerate the corrosion
rate.
(d) Nature of the Surface Film
The rate of corrosion is influenced by the nature of the metal oxide film
formed on the metal surface. According to Pilling–Bedworth rule,
Volume of metal oxide film formed
Specific volume ratio = ________________________________
Volume of metal ion consumed
• Specific volume ratio > 1; the oxide film formed will be nonporous
and it protects the metal from further corrosion.
Example: Oxides of Al, Sn, Pb, Cu, etc.
• Specific volume ratio < 1; the oxide film formed is porous, through
which oxygen can easily diffuse and is therefore nonprotective in
nature.
Example: Oxides of Li, Na, K, Mg, Ca, Sr, etc.
(e) Purity of the Metal
Impurity present in a pure metal creates heterogeneity and leads to
galvanic corrosion. If the percentage of purity increases, the corrosion
rate decreases.
For example, iron impurity present in Zn metal forms an electro-
chemical cell and undergoes corrosion.
Metal % of purity Corrosion Rate
99.999 1
Zinc 99.99 2650
99.95 5000

(f) Stress
The metal part under stress can become the anode and undergo corrosion.
This type of corrosion is called stress corrosion.

3.5.2 Nature of the Environment

(a) Temperature The rate of chemical reactions and diffusion of ions
increases with temperature. Hence, corrosion increases with temperature.
A passive metal may become active at higher temperature.
(b) Humidity Concentration of water vapour present in the atmosphere
is known as humidity. If the humidity increases, the corrosion rate also
increases. But at a particular point, a sudden
increase in the corrosion rate is observed,
called critical humidity.

Corrosion rate
(c) Presence of Corrosive gases Corrosive Critical
gases like SO2, H2S, fumes of HNO3, H2SO4, humidity
acetic acid, etc., enhance the corrosion rate.
(d) Presence of suspended solids
Suspended particles like chemically active, Humidity
chemically inactive and chemically neutral
dust particles enhance the corrosion rate. Fig. 3.10 Critical humidity

(e) pH The corrosion rate is maximum when the environment is more

acidic (pH = 5) and minimum when the environment is more alkaline
(pH = 11). In general, an acidic medium is more corrosive than alkaline
or neutral medium.

3.6 CORROSION-CONTROL METHODS

Corrosion is very harmful for metals or alloys. Since metals and alloys
disintegrate or waste every year, corrosion costs a huge amount of money,
effort and time and it is necessary to protect the metals or alloys against
corrosion by some methods.
Some of the corrosion control methods are given below.
(a) Corrosion Control by Modifying the Metal
• By selection of the metal
• By using pure metals
• By proper alloying
• By proper design
(b) Cathodic Protection Method
• Sacrificial anodic protection
• Impressed current cathodic protection
(c) By using Inhibitors
• Anodic inhibitors
• Cathodic inhibitors
• Vapour-phase inhibitor
(d) Changing the environment
• De-aeration
• De-activation
 • Dehumidification
• Alkaline neutralization
(e) By using Protective Coating

3.6.1 Cathodic Protection Method

The anode is the electrode at which a net oxidation reaction occurs,
whereas cathodes are electrodes at which net reduction reactions occur.
All cathodic protection systems require an anode, a cathode, an electric
circuit between the anode and cathode, and an electrolyte. Thus, cathodic
protection will not work on structures exposed to air environments. The
air is a poor electrolyte, and it prevents current flowing from the anode
to the cathode. The principle involved in cathodic protection is to force
the metal to behave like a cathode.
Cathodic protection can be accomplished by two widely used
methods:
(a) Sacrificial Anodic Protection
Coupling a given structure (say Fe) with a more active metal such as
zinc or magnesium, produces a galvanic cell in which the active metal
works as an anode and provides a flux of electrons to the structure,
which then becomes the cathode. The cathode is protected and the anode
progressively gets destroyed, and is hence, called a sacrificial anode.
(b) Impressed-current Cathodic Protection
The second method involves impressing a direct current between an
inert anode and the structure to be protected. Since electrons flow to the
structure, it is protected from becoming the source of electrons (anode).
In impressed current systems, the anode is buried and a low-voltage dc
current is impressed between the anode and the cathode.
(a) Sacrificial Anodic Protection Method
A sacrificial anode, or sacrificial rod, is a metallic anode used in cathodic
protection where it is intended to be dissolved to protect other metallic
components. The more active metal is more easily oxidized than the
protected metal and corrodes first (hence the term ‘sacrificial’); it
generally must oxidize nearly completely before the less active metal
will corrode, thus acting as a barrier against corrosion for the protected
metal. In this method, the metallic structure to be protected is made
the cathode by connecting it with the more active metal (anode metal).
Because of this, all the corrosion will concentrate only on the active
metal. The artificially made anode thus gradually corrodes protecting
the original metallic structure. Hence, this process is otherwise known
as sacrificial anodic protection.
 Typical materials for sacrificial anodes are magnesium (for soil) and
aluminium/zinc/galvalum/indium alloys (for sea water or seabed).

Example 1 This method is used for the protection of ships and boats. Sheets
of Mg or Zn are hung around the hull of the ship (Fig. 3.11).
Sacrificial zinc
or magnesium

Insulated
copper wire

Ship hull

Fig. 3.11 Sacrificial anodic protection of ship

Zn or Mg act as anodes compared to iron (ship or boat is made of

iron), so corrosion concentrates on Zn or Mg. Since they are sacrificed
in the process of saving iron, they are called sacrificial anodes.
Sacrificial anodes are used on water-based vessels, such as yachts and
powerboats, to minimize the corrosion of vital metal parts such as hulls
and propellers. Conventionally made of zinc, aluminum and magnesium,
boat anodes are designed for use in particular water types and with
specific boat models. The number and size of anodes is determined by
the type of material and the surface area being protected.
Choosing the Correct Anode
Generally, boat owners should choose the anode most suitable for the
type of water they berth in. Naturally, some boats will move between salt
and freshwater, or be berthed in areas where water will change between
brackish water or freshwater. In these cases boat owners must choose a
cathodic protection system to minimize corrosion in all environments.
Not all anodes are suitable for use in every type of water. For example,
if zinc or aluminum anodes are left in freshwater they will develop a
layer of oxide which will stop the anode from working. On the other
hand, aluminum anodes will operate effectively in brackish water whilst
zinc anodes will become unreactive. If the wrong type of metal is chosen
for the water type, the anode will become useless.
 Water Metal Anode
Salt water Zinc or aluminum anodes
Brackish water Aluminum anodes
Freshwater Magnesium anodes

Other applications of sacrificial anodic protection are

(a) Protection of underground pipelines, cables from soil corrosion
[Fig. 3.12 (a)]
(b) Insertion of Mg sheets into domestic water boilers to prevent the
formation of rust [Fig. 3.12 (b)]
(c) Calcium metal employed to minimize engine corrosion.
Mg (sacrificial anode) Sacrificial Zn Insulated wire
or Mg

(a) Underground pipeline (b) Boiler

Fig. 3.12 Sacrificial anodic protection

(b) Impressed-Current Cathodic Protection Method

For larger structures, Impressed-Current Cathodic Protection (ICCP)
systems are more common because sacrificial anodes generally will
not economically deliver enough CP current to protect pipelines longer
than several dozen kilometres.
Impressed-current cathodic protection systems are thus often used for
very long-distance pipelines or large plants having many large tanks or
large buried metallic structures to protect.
I n t h is met hod, a n
Source of impressed direct current
impressed current is applied
in the opposite direction of the Anode Cathode
Land
+ –
corrosion current to nullify surface
it, and the corroding metal
is converted from anode to Back fill Graphite
(anode) Insulated
cathode.
copper wire
T h i s c a n b e done by
con nec t i ng t he negat ive
terminal of the battery to Buried pipeline Cathode
the metallic structure to be (Protected)
protected, and the positive Fig. 3.13 Impressed-current cathodic protection
terminal of the battery is connected to an inert anode. Inert anodes
used for this purpose are graphite and platinized titanium. The anode
is buried in a ‘backfill’ (containing a mixture of gypsum, coke, breeze,
sodium sulphate). The ‘backfill’ provides good electrical contact to the
anode (Fig. 3.13).
CP is used to protect steel pipelines, storage tanks, steel piles, ships,
offshore oil platforms and onshore oil-well casings, marine piers and
laid-up strips, etc.

Table 3.4 Comparison of sacrificial anode (galvanic method) and impressed-current cathodic
method
Sl. No Sacrificial Anode Method Impressed Current Method
1. It is a simple system. It is a more complex system than sacrificial
anode systems.
2. No external power supply is necessary. External power supply must be present.
3. This method requires periodical Here, anodes are stable and do not
replacement of sacrificial anode. disintegrate.
4. Investment is low. Investment is more.
5. Soil and microbiological corrosion Soil and microbiological corrosion, corrosion
effects are not taken into account. effects are taken into account.
6. This is a most economical method especially This method is well suited for large structure
when short-term protection is required. and long-term operations.
7. This method is suitable when the current This method can be practiced even if the
requirement and the resistivity of the current requirement and the resistivity of
electrolytes are relatively low. the electrolyte are high.
8. The voltage differences between anode Impressed-current systems can use larger
and cathode are limited in sacrificial anode voltage differences.
systems to approximately 1 V or even
less than 1V.
9. Fixed driving voltage. Adjustable voltage.
10. Low maintenance. Higher maintenance.
11. Does not cause stray current corrosion. Stray dc currents can be generated.

3.6.2 Corrosion Inhibitors

This is a process of modifying the environment by adding certain
chemicals to the corroding medium. These chemicals are known as
corrosion inhibitors, as they arrest the anodic or cathodic reactions, i.e. a
corrosion inhibitor is a substance which reduces the corrosion of a metal,
when it is added in small quantities to the corrosive environment.
Types of Inhibitors
(i) Anodic Inhibitors
Anodic inhibitors retard the corrosion reaction, occurring at the anode,
by forming an insoluble compound with a newly produced metal ions
of anode. This precipitate will then be adsorbed on the metal (anode)
surface, forming a protective film or barrier and thereby reducing the
corrosion rate.
Anodic inhibitors should be used in enough amounts to cover the metal
surface completely with the protective film, as otherwise corrosion will
be concentrated on the remaining areas resulting in pitting corrosion.
Examples: Chromates, molybdates, nitrates, phosphates, tungstates or
other ions of transition elements with high oxygen content.
(ii) Cathodic Inhibitors
In an electrochemical corrosion, the cathodic reactions are of two types
depending upon the environment.
1. In an Acidic Solution
In an acidic solution, the cathodic reaction is evolution of hydrogen
2H+ + 2e– H2 (Reduction)
The functions of cathodic inhibitors in acidic environment are the
following:
1. To decrease the formation of hydrogen at the cathode: This can be done
by adding organic inhibitors like amines, pyridines, etc., which
are adsorbed at the metal surfaces.
2. To increase the overvoltage of hydrogen: This can be done by adding
antimony and arsenic oxides which deposit adherent film of
metallic arsenic and antimony at the cathodic areas.
Examples: Organic inhibitors like anilines and its derivatives, mercaptans,
heterocyclic nitrogen compounds, thioureas etc.
2. In a Neutral Solution
In a neutral solution, the cathodic reaction is absorption of oxygen or
formation of hydroxyl ions.
½ O2 + H2O + 2e– 2OH– (Reduction)
Here, the formation of OH – ion is only due to the presence of oxygen.
So the corrosion can be controlled in two ways.
(a) By eliminating the oxygen from the corroding medium (neutral
solution), thereby formation of OH – ions are inhibited. This can
be done by either adding reducing agents like Na2SO3, N2H4 or
by deaeration.
(b) By retarding the diffusion of O2 to the cathodic areas eliminates the
formation of OH – ions from the neutral solution. This can be done
by adding Mg, Zn or Ni salts. These react with OH – ions form
insoluble hydroxides, which are deposited on the cathode forming
less impermeable self-barriers. Hence they retard the diffusion of
O2 to cathode.
Examples: Sodium sulphite (Na2SO3), hydrazine (N2H4).
(iii) Vapour-phase Inhibitors (VPI) or Volatile Corrosion Inhibitors (VCI)
This type of inhibitors are organic inhibitors, which readily vaporize
(sublimes) and form a protective layer on the metal surface. VPI are used
to avoid corrosion in closed spaces, storage containers, packing materials
and sophisticated equipments, etc.
Examples: Dicyclohexylammonium nitrate (DCHAN), benzotriazole,
Phenyl thiourea, etc.

3.7 PROTECTIVE COATINGS

Protective coatings are used to protect the metals from corrosion.
Protective coatings act as a physical barrier between the coated metal
surface and the environment. However, they are also used for the
decorative purpose. In addition to corrosion protection and decoration,
they impart some special properties such as hardness, electrical
properties, oxidation resistance and thermal insulating properties to the
protected surface.
(a) Main Requirements
Protective coatings should be chemically inert to the environment at any
temperature and pressure conditions.
(b) Classifications
Protective coatings are broadly of two types, i.e., inorganic and organic.
They are further classified as shown below.
Protective coatings

Inorganic coatings Organic coatings

Metallic coatings Nonmetallic coatings

1. Hot dipping 1. Surface (or) Chemical 1. Paints

(a) Galvanizing conversion coating 2. Varnishes
(b) Tinning (a) Chromate coating 3. Lacquers
(b) Phosphate coating 4. Enamels
(c) Oxide coating
2. Metal cladding 2. Anodising
3. Cementation 3. Vitreous or porcelain
(a) Sherardizing enamel coating
(b) Chromizing
(c) Calorizing
4. Electroplating
 Coatings like paints, varnishes, lacquers and enamels are called
organic coatings. They are applied on the metallic surfaces for both
corrosion resistance and decoration.

3.8 PRE-TREATMENT OF METAL SURFACE OR

PREPARATION OF MATERIAL FOR COATING

The base-metal surface is usually contaminated with rust, scale, oil,

grease, etc. For proper adhesion of plating or coating, the metal surface
(base metal) to be plated should be free from these impurities. If they
are present at the time of coating, it will give porous and discontinuous
coatings. So these impurities should be removed by proper pre-treatment
methods. This is called pre-treatment of metal surface. This usually
involves three steps.
1. Degreasing: It is a process of removal of grease, oil and other
surface contaminants.
2. Descaling: It removes loose and hard oxide scale from the metal
surface.
3. Etching: It is a treatment to secure adhesion or a polishing to
improve the appearance of applied coating.
The following methods are used to achieve the fresh metal surface
for providing protective coating.
(a) Mechanical Method
This method is used for descaling purpose, i.e., to remove loose scale and
oxides. The various methods are hammering, scraping, wire brushing
sandblasting, etc. Sandblasting is done when a slightly roughened surface
is desired. It is the process in which sand or abrasives along with an
air steam under pressure of 25–100 atm is concentrated on the metal
surface.
(b) Chemical Method
The following methods are used for both degreasing and descaling, i.e.,
for removing oils, grease and rust from the metal surface.
(i) Solvent Cleaning: Solvents such as alcohols, acetone, xylene, toluene,
chlorinated hydrocarbons, etc., are generally used in solvent cleaning.
This is followed by cleaning with steam and hot water containing wetting
agents.
In alkali cleaning, chemicals like sodium hydroxide,
(ii) Alkali Cleaning:
trisodium phosphate, sodium silicate, soda ash, etc., are used. This is
useful in removing oil paints. The base metal containing paint coating
is removed by keeping it in an alkali cleaning agent (NaOH + Na3PO4 +
Na2CO3). This cleaning is always to be followed by a thorough rinsing
with water.
(iii) Acid Pickling: Basic natures of rusty scales are removed by pickling.
It is a process of dipping the object in hot dilute acids such as H2SO4,
HCl, HF, H3PO4 and HNO3. Brass and bronze are pickled by a mixture
of H2SO4, HCl and a small amount of HNO3. Iron and steel surfaces are
pickled in H3PO4 or in H2SO4 followed by H3PO4.
(c) Electrochemical Method
This method is used where the oxide scales cannot be removed by the
other methods. The metal whose surface has to be cleaned is made either
anode (cathode pickling) or cathode (anode pickling). The electrolyte
is usually in acid solution or an alkali solution and on passing a direct
current, the dissolution of the oxide scales at anode or cathode takes
place.

3.9 ELECTROPLATING OR ELECTRODEPOSITION

3.9.1 Principle
Electroplating is the process in which the coating metal is deposited on
the base metal by passing a direct current through an electrolytic solution
containing the soluble salt of the coating metal.
Base Metal The metal which is coated upon is known as the base
metal.
Coat Metal The metal applied as coating is referred to as coat metal.
The coat metal should be chemically inert and resistant to corrosion and
should preferably have low melting point.
The base metal to be plated is made the cathode of an electrolytic cell,
whereas the anode is either made of the coating metal itself or an inert
material of good electrical conductivity.
Example: Graphite.

3.9.2 Objectives
(a) On Metals
1. To increase the resistance to corrosion of the coated metal
2. To improve the hardness and physical appearance of the article
3. To increase the decorative and commercial values of the article
 4. To increase resistance to chemical attack
5. To improve the properties of the surface of the article
(b) On Nonmetals
1. To increase strength
2. To preserve and decorate the surfaces of nonmetals like plastics,
wood, glass, etc.
3. For making the surface conductivity by utilization of light weight,
nonmetallic materials

3.9.3 Process
Electroplating is carried out in an electrolytic cell. Before electroplating,
the article to be plated is first treated with dil. HCl (or) dil. H2SO4 to
clean the surface. The cleaned article is then made the cathode of an
electrolytic cell. The anode is either the coating metal itself or an inert
material of good electrical conductivity (like graphite).
The electrolyte is a solution of a soluble salt of a metal (to be deposited).
The anode and cathode are dipped in an electrolytic solution kept in
an electroplating tank. The tank is made of glass, enameled iron, and
stoneware.

–
e

Power
–
e
– e
I
Anode Cathode
(coat metal) + – (base metal)

M M¢

+ +
M M

Electrolytic
solution

Fig. 3.14 Electroplating

The electrodes are dipped in this electrolytic solution and a direct

current of electricity is passed. On electrolysis, the anode (coat metal)
dissolves into the electrolytic bath and the metal ions from a bath solution
are migrated and deposited as metal over the cathode (base-metal article
to be plated).
M Mn+ + ne– (dissolution at the anode)
n+ –
M + ne M (deposition at cathode)
When a direct current is passed from a battery, coating metal ions
migrate to the cathode and get deposited there. Thus, a thin layer of
coating metal is obtained on the article (at cathode).
In order to get a strong, adherent and smooth deposit, certain
additives (glue, gelatin, etc.) are added to the electrolytic bath. In order
to improve the brightness of the deposit, brightening agents are added in
the electrolytic bath. The favorable conditions for a good electrodeposit
are optimum temperature, optimum current density and low metal-ion
concentrations.
Advantages of Electroplating
A very thin coating (useful for deposition of costly metals like Au,
Ag) can be obtained by adjusting suitably the factors responsible for
controlling the thickness of coating.

3.9.4 Factors Affecting Electroplating

1. Surface Treatment: Cleaning of the article is essential for a strong
adherent electroplating. Oily substances present in the base metal should
be removed by solvent cleaning.
2. Concentration of Coating Metal Ion: Low concentration of
the metal ions in the electrolyte will produce a uniform coherent
metal deposition.
3. Thickness: Thickness of the deposit should be minimized in order
to get a strong adherent coating.
4. Current Density:Current density used for electroplating should be
optimum, because high current density produces loose and powdery
deposit and low current density decreases the rate of electro-
deposition.
5. Additives: Additives like gelatin and glue are added to electrolytic
bath in order to get a strong, adherent and mirror-smooth coating.
6. Electrolyte: The electrolyte selected should have a good conductivity
of current.
7. pH: The pH of the electrolytic bath must be properly maintained
to get the deposition effectively. Usually, acidic pH 5–6 is preferred for
high conductivity.
8. Stirring: should not be fast, since it will hinder the good adherence
of coating metal atoms on the base metal and so a porous and rough
deposit will be formed. Hence, mild stirring is done.

Table 3.5 Electroplating of some metals and conditions

Metal Operating Current
Anode Cathode Electrolyte Additives
Deposited Temperature Density
Copper Pure Metal CuSO4 40–50°C 35–40 –
copper article mA cm2
plates
Nickel Pure Ni Metal Solution of 40–70°C 20–30 Saccharin
pellets or article NiSO4 + NiCl2 mA cm2
pieces in + Boric acid
Ti mesh
basket
Gold Pure gold Metal Gold + KCN 60°C 5–10 –
article mA cm2
Chromium Pb–Sn (or) Metal Chromic acid 40–50°C 100–200 SO42–
Pb-Sb alloy article + H2SO4 in mA cm2
coated with 100: 1 ratio
PbO2 (or)
stainless
steel

3.10 ELECTROLESS PLATING

Non-electrical plating of metals and plastics are used to achieve uniform
coatings by a process of controlled autocatalytic (self-continuing)
reduction. Discovered in 1944 by A Brenner and G E Riddell, electroless
plating involves the deposition of such metals as copper, nickel, silver,
gold, palladium on the surface of a variety of materials by means of a
reducing chemical bath. It is also used in mirroring, in which a clean
surface of glass is dipped into an ammoniacal silver solution mixed with
Rochelle salt or with a nitric acid–cane-sugar alcohol solution.
Nonmetallic surfaces, such as plastics, must be chemically treated
prior to electroless plating. The major expansion of electroless plating
has come in the area of plastics, as in the plating of printed electronic
circuits. A large number of consumer goods are coated by this method
to create durable and attractive surfaces.
Definition It is a process of deposition of a metal from its salt solution
on a catalytically active surface by a suitable reducing agent without
using electricity.
Process First, M-ions are formed from its salt solution and then the
reduction is accomplished by the presence of a reducing agent. Metallic
ions are reduced to the metal with the help of reducing agents. Once a
metal is formed, it gets plated over a catalytically activated surface.

S
–
e Red
+
M

MA, H2O, Red

Fig. 3.15 Electroless plating

M2+ + 2e– (from reducing agent) M + Oxidized product

(Deposited over
a catalytically
active surface)

The common reducing agents are formaldehyde, Hypophosphorous

acid, alkali borohydrides and alkali diboranes.
A number of metals like nickel, cobalt, copper and some precious
metals can be deposited by electroless plating. The most popular metal
deposited electrolessely is nickel.

3.10.1 Various Steps involved in Electroless Plating

The various steps involved are as follows:
(a) Surface Preparation for Electroless Plating
This is achieved by using any one of the following methods:
(i) Etching: Impurities are removed from the surface by acid
treatment.
(ii) Electroplating: A thin layer of the metal or any other suitable
metal is electroplated on the surface.
(iii) Treatment of Surface with Stannous Chloride and Palladium
Chloride Alternatively: Nonconducting surfaces such as plastics
or printed circuit boards are treated with Stannous Chloride and
Palladium Chloride.
(b) Preparation of Plating Bath
The main constituents of the electroless solution are
(i) Metal salts to provide metal ions for deposition (coat metal)
 (ii) Reducing agents like formaldehyde and hypophosphite for the
reduction of metal ions to metal atoms
(iii) Complexing agents like EDTA and trisodium citrate to complex
metal ions to prevent bulk decomposition
(iv) A stabilizer like thiourea to prevent the decomposition of plating
bath solution
(v) Accelerators like succinates and fluorides to accelerate the
reduction process
(vi) Brighteners like cadmium ions and lead ions to improve the
brightness of the deposit
(vii) PH controlled by the buffer

3.10.2 Advantages of Electroless Plating

1. No electrical contact or electrical power is needed.
2. Plastics, insulators and semiconductors can also be plated by
electroless plating.
3. It is readily adoptable for three-dimensional coverage.
4. This method enhances deposit uniformity.
5. Resulting deposits have unique chemical, mechanical and magnetic
properties.
Table 3.6 Differences between electroplating and electroless plating
Sl. No Electroplating Electroless Plating
1. It is carried out by passing electrical energy. Here, there is no need of electrical energy.
2. Here, a separate anode is used. Anodic reaction takes place on the surface
of the substrate.
3. Plating on semiconductors and insulators Plating on semiconductors and insulators
are difficult. are easy.

3.11 SURFACE-CONVERSION COATING

Surface conversion is done for passiving the surface. This can be done by
chemical or electrochemical reactions brought at the surface of the base
metal. The resultant adherent coating on the surface of the base metal
gives good protection from corrosion. Such coatings are also used as an
excellent base for the application of paints and enamels.
Important surface conversion coatings are
• Phosphate coatings
• Chromate coatings
• Chemical oxide coatings
3.11.1 Phosphate Conversion Coating
Phosphate coatings are used for corrosion resistance or as a foundation
for subsequent coatings. The chemicals used in this coating are the dilute
solution of phosphoric acid and phosphate salts. It is either applied via
spraying or immersion. The applied mixture reacts with the surface of the
part being coated to form a layer of insoluble, crystalline phosphates.
Some type of phosphate coatings and their uses are given below.
S. No Type of phosphate coating Mode of application Uses
1. Manganese phosphate By immersion Corrosion resistance
and lubricity
2. Iron phosphate By immersion or spraying base for further
coatings/paintings
3. Zinc phosphate By immersion or spraying rust proofing and lubricant
base layer.

(a) Process
It is the chemical conversion coating in which the base metal is treated
with a dilute solution of phosphoric acid (less than 1%) and phosphates.
Iron, zinc or manganese phosphate salts are dissolved in a solution of
phosphoric acid. When steel or iron parts are placed in the phosphoric
acid, a classic acid-and-metal reaction takes place. This causes the
dissolved salt to fall out of solution and forms an insoluble complex of
metal phosphate compound. This metal phosphate compound forms an
adherent deposit over the base metal.
The following is a typical phosphating procedure:
1. Cleaning the surface
2. Rinsing
3. Surface activation (in some cases)
4. Phosphating
5. Rinsing
6. Neutralizing rinse (optional)
7. Drying
8. Application of supplemental coatings: lubricants, sealers, oil,
etc.
(b) Uses
1. Phosphate coatings are often used to provide corrosion resistance;
however, phosphate coatings on their own do not provide this
because the coating is porous. Therefore, oil or other sealers
are used to achieve corrosion resistance. This coating is called a
phosphate and oil (P and O) coating.
 2. Most phosphate coatings are used as a base for further coating
and/or painting and also increase the resistance of the films to
humidity.
3. Zinc phosphate coatings are frequently used in conjunction with
sodium stearate (soap) to form a lubrication layer in cold and hot
forging. The zinc phosphate is, in fact, abrasive and it is the soap
which performs the actual lubrication.

3.12 ANODIZED COATING

Anodized coatings are made by anodic oxidation process. This leads to

the formation of protective, corrosion resistant, electrically insulating
oxide film on the surface of nonferrous metals like Al, Zn, Mg and their
alloys. Anodized coating is an electrochemical process in which the base
metal is the anode. Anodizing involves the electrolytic oxidation of a
surface to produce a tightly adherent oxide scale, which is thicker than
the naturally occurring film.
It is carried out by passing moderate direct current through a bath
in which the metal or alloy is suspended from anode at 35ºC to 40ºC.
The bath usually contains sulphuric acid, chromic acid, oxalic acid,
phosphoric acid or boric acid.

3.12.1 Aluminum Anodizing

Aluminum anodizing is an electrochemical process in which an oxide
(anodic) layer is chemically built on the surface of the metal. This oxide
layer acts as an insulator and can be dyed in a wide variety of colours.
Anodizing provides surface-corrosion protection along with an excellent
substrate for decorative finishes.
Anode: Aluminium (base metal)
Cathode: Any inert material of good electrical
conductivity (lead/stainless steel)
Electrolyte: Sulphuric acid, chromic acid, oxalic acid
or phosphoric acid
Temperature: 35ºC to 40ºC
Current density: Moderate current density
On electrolysis, the oxygen liberated at the anode combines with
aluminium to form oxide. An oxide film, initially very thin, grows on the
metal surface and increases in thickness. The outer part of the oxide film
formed is very porous and easily prone to corrosion. Hence, the anodized
surface containing pores can be sealed by treatment with hot water/
steam for more than a few minutes.
This treatment converts aluminium
oxide into its monohydrate (Al 2O3.

Cathode
H2O) which occupies more volume, Anode
thereby the pores are sealed. An other
solution used for sealing is dilute Power supply Sulfuric acid tank
sodium dichromate. These anodized
Fig. 3.16 Aluminium anodizing
coatings may be coloured with organic
dyes and inorganic pigments to give surface coloration for decorative
effects.
Anodized coatings on Zn can be obtained by making Zn as the anode
in an electrolytic bath containing chromic acid or chromates.
Applications Aircraft parts, refrigerators, pistons, reflectors, machine
parts, etc., are anodized by this method.
Some of the common anodizing processes used in the industries are
• Hard-coat anodizing
• Bulk anodizing
• Sulphuric acid anodizing

3.13 HOT DIPPING

It is a process of producing a coating of low-melting point metal such as

Zn, Sn, Pb, Al, etc., over the surface of Fe, steel and copper which have
high melting points.
Base metal: High-melting-point metal (Fe, steel and copper)
Coat metal: Low-melting-point metal (Zn, Sn, Pb, Al etc)
The two most widely used hot-dipping methods are
1. Galvanizing
2. Tinning

3.13.1 Galvanizing
Galvanizing is the process of coating of zinc on iron or stainless-steel
sheets.
(a) Process
The iron or stainless-steel article (e.g. sheet, pipe, wire) surface is first
cleaned by acid pickling with dilute H2SO4 solution for 15–20 minutes
at 60–90°C. This treatment removes any scale, rust (oxide layer) and
impurities on the metal surface. The article is then washed well with
water and dried. It is then dipped in the bath containing molten zinc,
maintained at 425–430°C. The surface of the bath is kept covered with
a flux, i.e. ammonium chloride, which is used for cleaning the surface
of the metal and also to prevent oxide formation. When the article is
taken out, it is found to have been coated with a thin layer of zinc. In
order to get uniform thickness, it is passed through a pair of hot rollers,
which removes any superfluous (excess) of zinc. Then, it is annealed at
a temperature of 650°C and finally, cooled slowly.

Pair of hot Rollers

Galvanized
Ammonium sheet
chloride flux

Drying
Iron Annealing
chamber Hot
sheet chamber
air
Water

Dil. H2SO4 Washing bath Molten zinc Excess zinc

at 60°–90°C at 425°–430°C removed

Fig. 3.17 Galvanizing process

(b) Uses
It is most widely used for protection of iron from atmospheric corrosion
in the form of roofing sheets, wires, pipes, bolts, screws, buckets, tubes,
etc. It may be pointed here that zinc gets dissolved in dilute acids to
form highly toxic (or poisonous) compounds. Hence, galvanized utensils
cannot be used for preparing and storing foodstuffs, especially acidic
ones.

3.13.2 Tinning
Tinning is the process of coating of tin on iron or stainless-steel
sheets.
(a) Process
In this process, iron or stainless-steel sheets are first treated with dilute
sulphuric acid to remove the oxide scale on the surface. After this, it is
passed through a bath containing zinc chloride flux. It helps the molten
metal to adhere to the metal sheet. And then it is passed through the
tank of molten tin which is kept at 230–235°C. In this process, palm oil
helps to protect the hot tin-coated surface against oxidation. In order to
get uniform thickness, it is passed through a pair of hot rollers, which
removes any superfluous (excess) of tin. Then, it is annealed and finally,
cooled slowly.
Roller

Tin plated sheet

Sh tee
Palm oil
S
ee l
t
Pair of rollers

Acid-pickling bath
Bath of zinc chloride flux
Molten tin
Tank

Fig. 3.18 Tinning process

(b) Uses
Tin-plated iron is used in food containers because of its nontoxic
nature.

Table 3.7 Differences between galvanizing and tinning

Sl. No Galvanizing Tinning
1. It is a process of coating of Zn on It is a process of coating of Sn on iron/steel.
iron/steel.
2. It cannot be used for making food It can be used for making containers for
containers, because Zn reacts with food storing and packing food products.
acids forming highly toxic zinc
compounds.

3.14 PAINTS

Paint is a mechanical dispersion of one or more finely divided pigments

in a medium (thinner + vehicle). When paint is applied to a metal surface,
the thinner evaporates, while the vehicle undergoes slow oxidation
forming a pigmented film.
(a) Requisites (or) Characteristics of a Good Paint
A good paint should satisfy the following requirements:
1. It should spread easily on the metal surface.
2. It should have high covering power.
3. It should not crack on drying.
4. It should adhere well to the surface.
5. The colour of the paint should be stable.
6. It should be corrosion-and water resistant.
7. It should give a smooth and pleasing appearance.
8. It should dry quickly.
9. The colour should be stable to the effect of atmosphere and other
agencies.
(b) Pigment Volume Concentration (PVC)
It is an important criterion or a guide for the paint manufacturer to
prepare paints with desired properties.
Generally, the characteristics of paints depend on the nature and
quantities of pigments, extenders and vehicles present in the paint. The
following equation is used to calculate the PVC.
Volume of the pigment in the paint
PVC = _________________________________________
Volume of the pigment in the paint + Volume
of nonvolatile vehicle in the paint

If the volume of PVC increases, the durability, adhesion and

consistency of the paint decreases. The pigment volume concentration
of a paint should be kept within the limit.

3.14.1 Constituents of Paints

The important constituents of paints are as follows:
1. Pigments
2. Thinner (or) solvent
3. Vehicle (or) drying oil
4. Drier
5. Antiskinning agent
6. Plasticizers
7. Fillers (or) extenders.
Table 3.8 Constituents of paints and their functions
Sl. No Constituents Function Example
1. Pigments (i) To give the desired colour White: Pb,TiO2, ZnO
It is a solid substance (ii) To cover the manufacturing Blue: Indigo, Prussian Blue
which imparts colour defects Red: Red lead, chrome red
to the paint. (iii) To protect from UV light. Green: Chromium oxide,
(iv) To provide strength to Cr-green
the paint Yellow: Cr-yellow, Cd-yellow
(v) To increase weather Black: Graphite, carbon black
resistance of the film
2. Thinner or solvent (i) Used to dilute the paints in Turpentine oil, kerosene,
This is a volatile portion order to make it easy to alcohol
of the medium. It easily apply on the surface
evaporates after (ii) Reduces the viscosity of
application of the paint. the paint
(iii) It dissolves vehicles, oil,
pigment, etc., and produces
a homogeneous mixture.
(iv) It increases the penetrating
power of the vehicle.
3. Vehicle or drying oil (i) It is used to dissolve the Coconut oil, linseed oil,
It is a nonvolatile pigment and holds the castor oil, soyabeen oil.
portion of a medium pigment on the metal surface.
and film-forming (ii) It imparts water repellency,
material. durability, and toughness
to the film.
4. Driers They act as catalysts or Litharge, borates, resinates
Substances used to oxygen carriers and increase and tungstates of heavy
accelerate the process the rate of drying process. metals of Pb,Zn,Mn and Co.
of drying
5. Antiskinning agent To prevent skinning of Polyhydroxy phenol
the paint
6. Plasticizers They increase the elasticity Triphenyl phosphate, tributyl
of the film and to minimize phosphate, trycresyl
its cracking. phosphate, tertiary amyl
alcohol.
7. Fillers or extenders (i) They increase the volume of Gypsum, asbestos, China
Inert materials which the paint and reduce the cost. clay, talc, BaSO4
improve the properties (ii) They fill the voids in the film.
of the paint (iii) It increases the durability of
the paint.
(iv) It prevents shrinkage and
cracking.
3.14.2 Mechanism of Drying of (Paints) Drying Oils
1. Drying oils are fatty oils which are extracted from seeds.
2. The fatty oils are triesters of glycerol.
3. Formula of fatty oil (drying oil) is
CH2COOR2

R1COO — CH

CH2COOR3

where, R1, R2, R3, are radicals derived from aliphatic unsaturated
acids (palmitic acid, oleic acid)
4. The paint containing these types of drying oils, when exposed to
air, becomes a cross-linked polymer by reaction with oxygen in
the atmosphere.
5. In general, oils containing fatty acids having conjugated double
bonds dry faster than those that have nonconjugated double
bonds.
The mechanism of drying oils has not been completely understood.
However, according to acceptable mechanism, the oil containing double
bond absorbs oxygen to form peroxides, diperoxides and hydroperoxides.
The film takes of oxygen continuously and decomposes. The peroxy
radicals formed are polymerized and condensed to give cross-linked
polyperoxides which are tough, elastic, coherent, hard, insoluble,
infusible and stable. These polyperoxides are decomposed by light and
heat to form ether linkages.
Mechanism
1. The oil after application to the surface becomes solidified. It is
called drying and hence the oil is called ‘drying oil’.
2. The double bonds (unsaturation centers) present in the oil absorb
oxygen from the air and form peroxides (with 0–0) linkages. These
linkages react with adjacent chain unsaturation centres and form
cross links.
O2
C=C C-C

O-O

C-C C-C

O. .O O O
+
C=C C-C
 These cross links when continued sufficiently, solidification of the
liquid oil takes place.. This is only one of the mechanisms that is
possible.
If the unsaturation centres (carbon–carbon double bonds) increase,
the capacity for O2 absorption is also increases. Then the drying process
takes place quickly.

3.14.3 Special Paints

These paints are not only used as a coating material for metal and
material parts, but also used in some special areas like fire retarding,
as water repellents and in advertising. So these paints are called special
paints.
Some of the important special paints are as follows:
(a) Fire-retardant Paints
They contain fire-retardant chemicals like calcium ammonium
phosphate, magnesium ammonium phosphate, calcium carbonate, urea
formaldehyde, chlorinated rubber, etc., which decompose at elevated
temperature producing non-inflammable gases like CO2, NH3 and HCl
respectively. At elevated temperature, they form a barrier between air
and inflammable substrates of the paint and cover the flame quickly and
extinguish the fire.
Uses They are mainly used in wooden houses.
(b) Temperature Indicating Paints
They contain thermochromes. Thermochromes are the substances which
undergo colour changes at different temperatures.
The main ingredients are amine salts of copper, iron, manganese,
cobalt and nickel, etc. They are used in outer walls of the reactors and
furnaces to indicate the temperature of the reaction, so that it can be
stopped at a particular stage.
Uses Used in the outer walls of the reactors and furnaces to indicate
the temperature by its colour change.
(c) Water-repellant Paints
The active ingredients present in the paints are silicone resins and
silicone oils. They are prepared from organo ethoxy silane and organo
chlorosilanes by hydrolysis and condensation. This is dissolved in a
suitable solvent with required amount of pigments. These are sprayed
on the surface to effectively avoid the wetting of the surface by water.
 Pai nts contai n i ng asphalt or bit umen are also used for
waterproofing.
Uses
• Used mainly for masonary surface
• Used in ships, boats and marine equipments.
(d) Luminous Paints
Luminous paints contain luminophore pigments which fluoresce under
the influence of light. There are two types of luminous paints:
1. Fluorescent paint
2. Phosphorescent paint
(i) Fluorescent Paint
The absorption of light and emission of radiation takes place
simultaneously. Such a paint emits radiation only when exposed to light.
As soon as the exciting radiation is cut off, emission of radiation ceases.
The main ingredients are ZnS mixed with cadmium sulphide, copper
sulphide or silver sulphide.
Uses They are used in TV screens, advertising signs, instrument dials,
etc.
(ii) Phosphorescent Paint
Delayed fluorescence is called phosphorescence. In this paint, the
emission of radiation continues for some time even after the light
has stopped falling. The active ingredients are a mixture of cadmium
sulphide and strontium sulphide.
Uses They are used to illuminate maps and aircraft instruments at
night.

QUESTIONS

Two-Mark Questions with Answers

1. Define corrosion.
Corrosion can be defined as any process of destructive disintegration
or alteration of a metal or alloy caused by direct chemical attack
or by electrochemical reaction with its environment.
(OR)
In other words, corrosion is a process in which the gradual solution
or oxidation of a metal takes place, e.g. rusting of iron.
 2. What is oxidation corrosion?
Oxidation Corrosion is nothing but the direct attack of metals by
oxygen at low or high temperatures in the absence of moisture.
3. State the Pilling–Bedworth rule.
The protective or nonprotective oxide layer formation in metals
is governed by a rule known as Pilling–Bedworth rule. According
to this rule,
Volume of metal oxide film formed
Specific volume ratio = ________________________________
Volume of metal ion consumed
If the volume of the metal oxide ≥ volume of the parent metal then
the oxide film will be nonporous or the volume of the metal oxide
< volume of the parent metal, the oxide layer will be porous and
tend to undergo further corrosion.
4. What is decarburization?
The atomic hydrogen is highly reactive and combines with carbon
present in the metal and forms CH4 gas which leads to cracking
of the metal surface. The process of decrease in carbon content in
steel is known as decarburization of steel.
H2 [H] + [H]
C+H CH4
5. What is hydrogen embrittlement?
Metals combine with H2S gas to liberate atomic hydrogen.
H2S + Fe FeS + 2[H]
(Atomic hydrogen)

The atomic hydrogen recombines inside the metal and develops

pressure which leads to cracking of the metal. This is known as
hydrogen embrittlement or Hydrogen Corrosion.
6. What is concentration-cell corrosion?
Concentration-cell corrosion occurs when a metal or two metals
are in contact with different concentrations of the same solution
or different concentration of dissolved oxygen in the electrolyte.
It is also known as differential aeration corrosion.
7. Write any four differences between dry and wet corrosion.
Sl. No Dry or Chemical Corrosion Wet or Electrochemical Corrosion
1. It occurs in dry state, e.g. tarnishing It occurs in presence of moisture or electrolyte,
of silver. e.g. rusting of iron.
2. It involves direct chemical attack It involves the setting up of a huge number of
by the environment. galvanic cells.
3. It follows adsorption mechanism. It follows the mechanism of electrochemical
reaction.
4. Uniform corrosion behaviour is seen. Localized corrosion occurs.
5. It is a slow and self-controlled process. It is a fast and continuous process.

8. What is critical humidity?

Concentration of water vapour present in the atmosphere is
known as humidity. If the humidity increases, the corrosion rate
also increases. But at a particular point, a sudden increase in the
corrosion rate is observed, called Critical humidity.
Corrosion rate

Critical
humidity

Humidity

Fig. 2 Plot of humidity against corrosion rate

9. What is the galvanic Series?

The oxidation potential of the different metals and alloys are
determined at 25°C and tabulated in the descending order. metals
occupying higher positions in the series undergo corrosion in vigorous
manner. The above-said series is called galvanic series and it gives
more information about the corrosive tendencies of the different
metals.
10. Write any four applications of sacrificial anodic protection
method.
1. On water-based vessels such as yachts and powerboats, to
minimize the corrosion of vital metal parts such as hulls and
propellers
2. Protection of underground pipelines, cables from soil
corrosion
3. Insertion of Mg sheets into the domestic water boilers to
prevent the formation of rust
4. Calcium metal is employed to minimize engine corrosion
 11. What are anodic inhibitors?
Anodic inhibitors are the substances which retard the corrosion
reaction occurring at the anode, by forming an insoluble compound
with a newly produced metal ion of anode.
Examples Chromates, molybdates, nitrates, phosphates, tungstates
or other ions of transition elements with high oxygen content
12. Write any two differences between sacrificial anodic protection
and impressed current cathodic protection method.
Sl. No. Sacrificial Anode Method Impressed Current Method
1. No external power supply is necessary. External power supply must be present.
2. This method requires periodical Here, anodes are stable and do not
replacement of sacrificial anode. disintegrate.
3. It is a simple system and investment It is a more complex system than sacrificial
is low. anode systems, and investment is more.

13. Why do we need pretreatment for metal surface?

The base metal surface is usually contaminated with rust, scale,
oil, grease, etc. For proper adhesion of plating or coating, the
metal surface (base metal) to be plated should be free from these
impurities. If they are present at the time of coating, it will give
porous and discontinuous coatings.
14. Define electroplating.
Electroplating is the process in which the coating metal is
deposited on the base metal by passing a direct current through
an electrolytic solution containing the soluble salt of the coating
metal, e.g. electroplating of copper.
15. Define electroless plating.
Electroless plating is a process of deposition of a metal from its
salt solution on a catalytically active surface by a suitable reducing
agent without using electricity.
16. Write any three differences between electroplating and electroless
plating.
[Link] Electroplating Electroless Plating
1. It is carried out by passing electrical Here, there is no need of electrical energy.
energy.
2. Here, a separate anode is used. Anodic reaction takes place on the surface of
the substrate.
3. Plating on semiconductors and Plating on semiconductors and insulators
insulators are difficult. are easy.
 17. What is anodized coating?
Anodized coating is an electrochemical process in which the base
metal is the anode. Anodizing involves the electrolytic oxidation of
a surface to produce a tightly adherent oxide scale which is thicker
than the naturally occurring film.
18. Write any two differences between hot dipping (galvanizing)
and tinning.
[Link] Galvanizing Tinning
1. It is a process of coating of Zn on It is a process of coating of Sn on iron/steel.
iron/steel.
2. It cannot be used for making food It can be used for making containers for
containers, because Zn reacts with food storing and packing of food products.
acids and forms highly toxic zinc
compounds.

19. What is the purpose of adding thinners to paints? Give

examples.
(i) A thinner is added to dilute the paint in order to make it easy
to apply on the surface.
(ii) It reduces the viscosity of the paint.
(iii) It dissolves vehicles, oil, pigment, etc., and produces
homogeneous mixture.
Examples Turpentine oil, kerosene, alcohol

Ten-Mark Questions
1. Describe the mechanism of electrochemical corrosion.
2. What are the types of metal oxide films formed? Explain it in
detail.
3. Write short notes on concentration-cell corrosion.
4. Explain the important factors which influence the rate of corrosion
of a metal.
5. Discuss the mechanism of
(i) Chemical corrosion
(ii) Pitting corrosion.
6. Write brief notes on
(i) Sacrificial anodic protection method
(ii) Impressed current cathodic protection method
7. Write a note on application of inhibitors in corrosion control.
 8. (i) Define corrosion inhibitors.
(ii) What are the types of corrosion inhibitors? Explain it
briefly.
9. What are the important constituents of paint? Explain its functions
in detail.
10. Discuss in detail about pretreatment of metal surface.
11. Describe the mechanisms of drying of oil in paint?
12. What are the main objectives of electroplating? Give an account
of the method used in electroplating of nickel on steel.
13. Explain the following:
(i) Pilling–Bedworth rule
(ii) Decarburization
(iii) Hydrogen embrittlement
14. Write short notes on
(i) Phosphate conversion coating
(ii) Anodization
15. With a neat diagram explain the process of
(i) Hot dipping
(ii) Tinning
 UNIT

4
Fuels
“Everything is available in the world for human need but not for human
greed”.

4.1 INTRODUCTION

In recent years, the human population has grown at a very fast rate.
Along with the increase in population, living standards have also
improved. This increase of population and living standards has
resulted in a tremendous increase in the requirement of energy. Most
of the developed and developing countries derive their energy from
fossil fuels such as petroleum, coal and natural gas. The fossil fuels
are nonrenewable—hence, they are depleting in an alarming rate. It is
the basic responsibility of every citizen to conserve the nonrenewable
resources. This chapter deals with the details of various kinds of fuels,
how they are extracted and purified, their combustion and quantity of
energy released, etc.
A fuel is any material that can be used to generate energy to produce
mechanical work in a controlled manner. In other words, it is a substance
that produces energy, mostly usable heat. Most fuels produce energy
when they are burnt in air. The processes used to convert fuel into energy
include chemical reactions, such as combustion, and nuclear reactions
such as nuclear fission or nuclear fusion. Fuels are also used in the cells
of organisms in a process known as metabolism. Hydrocarbons are,
by far, the most common source of fuel in current use, but many other
substances can be used as well.
 Any matter which on combustion (i.e. burning) produces heat energy
is called a fuel.
Example: Wood, charcoal, coal, kerosene, petrol, diesel, producer
gas, oil gas, etc.

4.2 CLASSIFICATION OF FUELS

The fossil fuels are classified into the following categories:
(i) Primary or natural fuels—These are found in nature.
(ii) Secondary or artificial fuels—These are derived from primary
fuels.
Primary and secondary fuels may also be divided into three classes,
namely solid, liquid and gaseous fuels.

Fuels

Primary or Secondary or
Natural fuels Artificial fuels

Solid fuels Liquid fuels Gaseous fuels

Example:Wood Example: Oil. Example: Natural gas

Solid fuels Liquid fuels Gaseous fuels

Example: Charcoal Example: Petrol Example: LPG

4.2.1 Fossil Fuels

Fossil fuels are those which have been derived from fossil remains of
plant and animal life.
Fossil fuels are hydrocarbons, primarily coal and petroleum (liquid
petroleum or natural gas), formed from the fossilized remains of dead
plants and animals by exposure to heat and pressure in the earth’s crust
over hundreds of millions of years. The term ‘fossil fuel’ also includes
hydrocarbon-containing natural resources that are not derived entirely
from biological sources, such as tar sands. These are properly known as
mineral fuels.
4.2.2 Requirements of a Good Fuel
A good-quality and economical fuel should have the following
characteristics:
(a) High Calorific Value
A good-quality fuel should have its calorific value as high as possible,
since the work derived is directly proportional to the heat energy
released.
(b) Moderate Ignition Temperature
Low ignition temperature may result in a fire accident during storage
and transportation. On the other hand, very high ignition temperature
may result in difficulties during the ignition. Hence, a good-quality fuel
should have moderate ignition temperature.
(c) Low Quantity of Noncombustible Matters
The presence of noncombustible matter will result in low calorific value,
high quantity of ash generation and additional cost for transportation.
Hence, a good fuel should have low level of noncombustible matter.
(d) Lesser Moisture Content
The moisture present in the fuel will consume some amount of heat for
its own evaporation and also reduce the calorific value, and increase the
transportation and storage cost. The presence of moisture is not desirable
in a good-quality fuel.
(e) Free from Objectionable and Harmful Gases like
CO, SOx, H2S
On combustion, the fuel should not release harmful and objectionable
gases like CO, SOx, H2S, NOx, etc.
(f) Moderate Velocity of Combustion
Low rate of combustion may lead to unnecessary loss of heat due to
radiation. On the other hand, a high rate of combustion leads to out-of-
control burning. For a smooth and continuous supply of heat, the fuel
must burn with moderate velocity.
(g) Controllable and Stoppable Combustion
For easy start-up and stoppage, the combustion should be
controllable.
(h) The fuel should not pose any difficulty in transportation.
(i) The fuel should have more availability at affordable cost.
 4.3 COMBUSTION

Combustion, or burning, is the sequence of exothermic chemical

reactions between a fuel and an oxidant accompanied by the
production of heat and conversion of chemical species.
The release of heat can result in the production of light in the form
of either a glow or a flame. Fuels of interest often include organic
compounds (especially hydrocarbons) in the gas, liquid or solid phase.
During the process of combustion, carbon, hydrogen, etc., combine
with oxygen with liberation of heat.
The combustion reaction can be explained as
C + O2 CO2 + 94 kcal
2H2 + O2 2H2O + 68.5 kcal
The calorific value of a fuel depends mainly on the amount of carbon
and hydrogen.

4.3.1 Principle of Combustion

Combustion refers to the rapid oxidation of fuel accompanied by the production
of heat, or heat and light. Complete combustion of a fuel is possible only in the
presence of an adequate supply of oxygen.
Carbon, hydrogen and sulphur in the fuel combine with oxygen
in the air to form carbon dioxide, water vapour and sulphur dioxide,
releasing 8080 kcal, 34500 kcal and 2240 kcal of heat respectively. Under
certain conditions, carbon may also combine with oxygen to form carbon
monoxide, which results in the release of a smaller quantity of heat
(2430 kcal/kg of carbon). Carbon burned to CO2 will produce more heat
per kg of fuel than when CO or smoke are produced.

C + O2 CO2 + 8080 kcal/kg of carbon

2C + O2 2 CO + 2430 kcal/kg of carbon
2H2 + O2 2H2O + 34500 kcal/kg of hydrogen
S + O2 SO2 + 2240 kcal/kg of sulphur

Not all of the energy in the fuel is converted to heat; some is absorbed
by the steam generation equipment. So the main challenge in combustion
efficiency is directed toward unburnt carbon (in the ash or incompletely
burnt gas), which forms CO instead of CO2.
 Heat Heat Smoke
CO2 O2CO2 CO
N2 H2O N2 H2O
Perfect Good Incomplete
combustion combustion combustion

Fig. 4.1 Types of combustion

4.3.2 Calorific Value

It is the most important characteristic property of any fuel.
Calorific value may be defined as the amount of heat liberated by the
complete combustion of a unit mass of a fuel.
The quantity of heat can be measured by the following units.
(i) Calorie (ii) Kilocalorie
(iii) British thermal units (iv) Centigrade heat units
Calorie is the amount of heat required to raise the temperature of 1
g of water by 1°C (i.e. 15 to 16°C).
Calorific value is divided into two types:
(a) Higher or gross calorific value
(b) Lower or net calorific value
(a) Gross or High Calorific Value (GCV or HCV)
It is the total heat generated when a unit quantity of fuel is
completely burnt and the products of combustion are cooled to room
temperature.
For example, when a fuel containing hydrogen is burnt, it undergoes
combustion and will be converted to steam. If the combustion product
is cooled to room temperature, the steam gets condensed into water and
the latent heat is evolved. Therefore, the latent heat of condensation of
‘steam’, so liberated, is included in gross calorific value.
Dulong’s Formula for the Calculation of Calorific Value
Calorific value of a fuel is the sum of the calorific values of all the
combustible constituents present in the fuel.
Dulong’s formula for the theoretical calculation of calorific value is
 1
[ O
( )
GCV or HCV = ____ 8080 C + 34500 H – __ + 2240 S kcal/kg
100 8 ]
where, C, H, O and S represent the percentage of the corresponding
elements in the fuel which is determined by the ultimate analysis.
It is based on the assumption that the calorific values of C, H and S
are found to be 8080, 34500 and 2240 kcal, when 1 kg of the fuel is burnt
completely. However, all the oxygen in the fuel is assumed to be present
in combination with hydrogen in the ratio H : O as 1 : 8 by weight. So
O
the surplus hydrogen available for combustion is H – __.
8
(b) Net or Lower Calorific Value (NCV or LCV)
It is the net heat produced when a unit quantity of fuel is completely
burnt and the products of combustion are allowed to escape.
NCV = GCV – Latent heat of condensation of steam produced
Consider the following combustion reaction:
H2 + 1/2 O2 H2O
2g 16 g 18 g
1 8 9

1 part by weight of H2 produces 9 parts by weight of H2O.

The latent heat of steam is 587 cal/g.
Therefore, the latent heat of condensation of steam produced by H
amount of hydrogen is
9
= ____ H × 587 = 0.09 H × 587
100
where, H = % of H2 in the fuel.
Thus,
9
NCV = GCV – ____ H × 587 kcal/kg
100
NCV = GCV – 0.09 H × 587 kcal/kg

Example 1 Calculate the gross and net calorific values of a coal sample
having the following compositions: C = 80 %, H2 = 08 %, O2 = 08 %, S = 2 %
and ash = 2. Latent heat of steam is = 587 cal/g.
Solution
(i) Gross Calorific Value (GCV)
1
[ (
O
) ]
GCV = ____ 8080 C + 34500 H – __ + 2240 S kcal/kg
100 8
 1
[ (8
) ]
= ____ 8080 × 80 + 34500 8 – __ + 2240 × 2 kcal/kg
100 8
1
= ____ [646400 + 241500 + 4480] kcal/kg
100
1
= ____ [892380] kcal/kg
100
= 8923.8 kcal/kg
(ii) Net Calorific Value (NCV)
9
= GCV – ____ H × 587 kcal/kg
100
9
= 8923.8 – ____ × 8 × 587 kcal/kg
100
= 8923.8 – 422.64 kcal/kg
= 8501.16 kcal/kg

Example 2 Calculate the gross and net calorific values of a coal sample
having the following compositions: C = 63 %, H2 = 19 %, O2 = 03 %, S = 13
% and ash = 2. Latent heat of steam is = 587 cal/g.
Solution
(i) Gross Calorific Value (GCV)
1
[ ( )
O
GCV = ____ 8080 C + 34500 H – __ + 2240 S kcal/kg
100 8 ]
= ____ [ 8080 × 63 + 34500 ( 19 – __ ) + 2240 × 13 ] kcal/kg
1 3
100 8
1
= ____ [509040 + 642562 + 29120] kcal/kg
100
1
= ____ [1180722] kcal/kg
100
= 11807.22 kcal/kg
(ii) Net Calorific Value (NCV)
9
= GCV – ____ H × 587 kcal/kg
100
9
= 11807.22 – ____ × 19 × 587 kcal/kg
100
= 11807.22 – 1003.77 kcal/kg
= 10803.45 kcal/kg
Example 3 Calculate the gross and net calorific values of a solid fuel having
80% of carbon and 20% of hydrogen. Latent heat of steam is = 587 cal/g.
Solution
(i) Gross Calorific Value (GCV)
1
[ (O
) ]
= ____ 8080 C + 34500 H – __ + 2240 S kcal/kg
100 8
Here, the % of O2 and S are zero.
1
[ (0
) ]
= ____ 8080 × 80 + 34500 20 – __ + 2240 × 0 kcal/kg
100 8
1
= ____ [646400 + 690000] kcal/kg
100
1
= ____ [1336400] kcal/kg
100
= 13364 kcal/kg
(ii) Net Calorific Value (NCV)
9
= GCV – ____ H × 587 kcal/kg
100
9
= 13364 – ____ × 20 × 587 kcal/kg
100
= 13364 – 1056.6 kcal/kg
= 12307.4 kcal/kg

Example 4 A coal sample on analysis gives C = 75 %, H2 = 6 %, O2 =

3.5 %, S = 03 % and the rest ash. Calculate the gross and net calorific values
of the fuel. Latent heat of steam is = 587 cal/g.
Solution
(i) Gross Calorific Value (GCV)
1
[ ( )
O
]
= ____ 8080 C + 34500 H – __ + 2240 S kcal/kg
100 8

= ____ [ 8080 × 75 + 34500 ( 6 – ___ ) + 2240 × 3 ] kcal/kg

1 3.5
100 8
1
= ____ [606000 + 191906 + 6720] kcal/kg
100
1
= ____ [804626] kcal/kg
100
= 80462.6 kcal/kg
(ii) Net Calorific Value (NCV)
9
= GCV – ____ H × 587 kcal/kg
100
9
= 80462.6 – ____ × 6 × 587 kcal/kg
100
= 80462.6 – 316.98 kcal/kg
= 80145.62 kcal/kg

Example 5 On analysis, a coal sample has the following composition by

weight: C = 75 %, O2 = 04 %, S = 05 %, and ash = 3%. Net calorific value
of the fuel is 9797.71 kcal/kg. Calculate the percentage of hydrogen and gross
calorific value of coal.
Solution
(i) Gross Calorific Value (GCV)
We know that,
GCV = [NCV + 0.09H × 587] kcal/kg
= [9797.71 + 0.09H + 587] kcal/kg
= [9797.71 + 52.8 H] kcal/kg …(1)
1
[ ( )
O
GCV = ____ 8080 C + 34500 H – __ + 2240 S kcal/kg
100 8 ]
= ____ [ 8080 × 75 + 34500 ( H – __ ) + 2240 × 5 ] kcal/kg
1 4
100 8
1
= ____ [606000 + 34500 H – 17250 + 11200] kcal/kg
100
= [6060 + 345 H – 172.5 + 112] kcal/kg
= 5999.5 + 345 H kcal/kg ...(2)
Equation (2) is substituted in Equation (1).
9797.71 + 52.8 H = 5999.5 + 345 H
9797.71 – 5999.5 = 345 H – 52.8 H
3798.21 = 292.2 H
3798.21
H = _______
292.2
% of H2 = 12.99 (i.e. 13 % )
Substituting the value of H2 in the GCV equation,
1
[ ( 4
)
GCV = ____ 8080 × 75 + 34500 13 – __ + 2240 × 5 kcal/kg
100 8 ]
 1
GCV = ____ [606000 + 431250 + 11200] kcal/kg
100
1
= ____ [1048450] kcal/kg
100
= 10484.5 kcal/kg

4.4 THEORETICAL CALCULATION OF MINIMUM AIR

REQUIRED FOR COMBUSTION

Any fuel which is used for combustion should be burnt completely to

ensure complete and efficient combustion of fuel. It is essential that the
fuel is burnt in sufficient quantity of air to oxidize all the combustible
matter under appropriate conditions.
The essential conditions which are maintained are
• Intimate mixing of air with combustible matter, and
• Sufficient time to allow the combustion process to be completed.
Incomplete combustion may occur if any one of these factors is
inappropriate.
• The elements usually present in common fuels which enter into
the process of combustion are mainly C, H, S and O.
• Nitrogen, ash and CO 2 (if any) present in the fuel are
incombustible matters and hence they do not consume any
oxygen during combustion.
• Air contains 21% of oxygen by volume and 23% of oxygen by
weight.
Hence, from the amount of oxygen required by the fuel, the amount
of air can be calculated.
The amount of oxygen required for complete combustion of a fuel can
be calculated from the combustion equations. By calculating the weight
and volume of oxygen required for complete combustion of a fuel, it is
easy to calculate the volume and weight of air required for the complete
combustion.

Combustion of Carbon
C + O2 CO2
By volume 1 vol 1 vol 1 vol
By weight 12 g 32 g 44 g
1 part by volume of carbon requires 1 part by volume of oxygen for
complete combustion.
 (or)
12 g of carbon requires 32 g of oxygen for complete combustion (to
give 44 g of CO2).
1 g of carbon requires 32/12 g of oxygen for complete combustion.
32C
\ C g of carbon requires = ____ g of oxygen
12
(or )
32C
C parts by weight of carbon requires = ____ parts by weight of O2
12

Combustion of Hydrogen
H2 + 1/2 O2 H2O
By volume 1 vol 0.5 vol 1 vol
By weight 2g 16 g 18 g
1 part by volume of hydrogen requires 0.5 part by volume of oxygen
for complete combustion.
(or)
4 g of hydrogen requires 32 g of oxygen for complete combustion.
1 g of hydrogen requires 32/4 g of oxygen for complete
combustion.
32 × H
\ H g of hydrogen requires = _______ g of O2
4
(or)
32 × H
H parts by weight of hydrogen requires = _______ parts by weight of
4
O2
The oxygen present in the fuel consumes some amount of hydrogen
to form water. So, the quantity of hydrogen taken up by oxygen will not
take part in the combustion reaction. Therefore, the quantity of hydrogen
taken up by the oxygen will be deduced from the total hydrogen in the
fuel.
Now, the quantity of hydrogen available for the combustion reaction
O
will be H – __ where H is the total quantity of hydrogen and O is the
8
total quantity of oxygen in the fuel. (in water, the quantity of hydrogen
in combination with oxygen is one-eighth of the weight of oxygen).
 O
H – __ × 32
( O
)
\ H – __ parts by weight of hydrogen requires
8
8
__________
4
=

( O
)
8 H – __ parts by weight of O2
8

Combustion of Sulphur
S + O2 SO2
By volume 1 vol 1 vol 1 vol
By weight 32 g 32 g 64 g
1 part by volume of sulphur requires 1 part by volume of oxygen for
complete combustion.
(or)
32 g of sulphur requires 32 g of oxygen for complete combustion.
32 × S
S g of sulphur requires = ______ = S g of O2
32
(or)
32 × S
\ S parts by weight of sulphur requires = ______ = S parts by
32
weight of O2

Combustion of Nitrogen
Since nitrogen do not undergo combustion, the oxygen requirement
is nil.
Consequently, the theoretical amount of oxygen required for the
complete combustion of 1kg of solid or liquid fuel is
32
[ O
(
Theoretical minimum O2 = ___ × C + 8 H – __ + S kg
12 8 ) ]
Since mass % of O2 in air is 23, the amount of air required theoretically
for combustion of 1 kg of the fuel is,
Air (theoretical) ____
(by weitht)
=
32
23 12[
100 ___
(O
) ]
× C + 8 H – __ + S kg
8
Air (theoretical) ____
21 [ 12
× C + 8 ( H – __ ) + S ] litre
100 ___
32 O
=
(by volume) 8

Excess Air for Combustion

It is necessary to supply excess air for complete combustion of the fuel.
It is found out from the theoretical amount of air as follows.
 The amount of air required if excess air is supplied.
Theoretical amount of air
_______________________ × [100 + % of excess air]
100

4.5 FLUE-GAS ANALYSIS [ORSAT’S METHOD]

During combustion, a fuel is burnt in the combustion chamber with

the help of air from the atmosphere. The mixture of gases (like CO2,
O2, CO, etc.) coming out from the combustion chamber is called flue
gas. The analysis of a flue gas will give an insight into the complete or
incomplete combustion process and also the efficiency of the engine.
Orsat’s apparatus is used for the analysis of flue gas.

Construction of Orsat’s Apparatus

It consists of a water-jacketed burette connected in series to a set of three
absorption bulbs, each containing a stopcock at the bottom. The other
end is provided with a three-way stopcock, and the free end is further
connected with a U-tube packed with fused CaCl2 with a coverage of
glass wool at both the ends of the U tube. The lower end of the burette
is connected to a water reservoir by means of a long rubber tubing.
The bulb I consists of ‘potassium hydroxide’ solution and it absorbs
only CO2.
The bulb II consists of ‘alkaline pyrogallol’ solution and it absorbs
only CO2 and O2.
The bulb III consists of ‘ammoniacal cuprous chloride’ solution and
it absorbs CO2, O2 and CO.
Seperating funnel
Flue gas
Gas burette

I II III

CaCl2 for drying

Absorption
bulb for CO2
Absorption Absorption Water
bulb for O2 bulb for CO jacket

Fig. 4.2 Orsat’s apparatus

Working of Orsat’s Apparatus
At the beginning of the analysis, the absorption bulbs are filled with their
respective solutions. The three-way stopcock is opened to the atmosphere
and the reservoir is raised, till the burette is completely filled with water
and air is excluded from the burette. The three-way stopcock is now
connected to the flue-gas supply, the flue gas is sucked into the burette,
and the volume of flue gas is adjusted to 100 cc by raising and lowering
the reservoir. Then the three-way stop cock is closed.
(a) Absorption of CO2
The stopper of the absorption bulb I, containing KOH solution, is opened
and all the gases is passed into the bulb I by raising the level of water
in the burette. The gas enters into the bulb I, where CO2 present in the
flue gas is absorbed by KOH.
The gas is again sent to the burette. This process is repeated several
times to ensure complete absorption of CO2. The decrease in volume of
the flue gas in the burette indicates the volume of CO2 in 100 cc of the
flue gas.
(b) Absorption of O2
The stop-cock of the bulb II is opened after closing the stopcock of the
bulb I. The gas is again sent into the absorption bulb-II, where O2 present
in the flue gas is absorbed by alkaline pyrogallol. The decrease in volume
of the flue gas in the burette indicates the volume of O2.
(c) Absorption of CO
Finally, the stopcock of the bulb II is closed and stopcock of the bulb III
is opened. The remaining gas is sent into the absorption bulb III, where
CO present in the flue gas is absorbed by ammoniacal cuprous chloride.
The decrease in volume of the flue gas in the burette indicates the volume
of CO. The remaining gas in the burette after the absorption of CO2, O2
and CO is taken as nitrogen.
Significance of Flue-gas Analysis
• Based on the composition of the flue gas, it is possible to predict
the complete or incomplete combustion process.
• If the flue gas contains any CO, it indicates the incomplete
combustion in the combustion chamber and short supply of
oxygen.
• If the flue gas contains O2, it indicates excess supply of air and it
is essential to reduce the air supply.
 4.6 IMPORTANT TERMS RELATED TO COMBUSTION

4.6.1 Ignition Temperature

It is defined as the lowest temperature to which the fuel must be
heated, so that it starts burning smoothly.
Besides sufficient supply of oxygen or air, every fuel requires heating
to a definite temperature to start active combustion. This is known as
ignition temperature. The ignition temperature of coal is about 300°C.
In the case of liquid fuels, the ignition temperature is called the flash
point, which ranges from 200 – 400°C. For gaseous fuels, the ignition
temperature is in the order of 800°C.

4.6.2 Spontaneous Ignition Temperature (SIT)

It is defined as the minimum temperature at which the fuel catches
fire (ignites) spontaneously without external heating.
If a coal, for example, is stored in such a way that heat is slowly
dissipated, slow oxidation may produce sufficient heat to raise the
temperature to ignite on its own. Fuels which have low ignition
temperature can catch fire very quickly. On the other hand, if the ignition
temperature is high, it is difficult to ignite the fuel. If the heat evolved in a
system is unable to escape, temperature of the system goes on increasing
and when SIT is reached, the system burns on its own.

4.6.3 Explosive Range or Limits of Inflammability

Most of the gaseous fuels have two percentage limits, called upper
limit and lower limit. Those limits represent the percentage by volume
of fuel present in fuel–air mixture. The range covered by these limits
is termed the explosive range of the fuel.
For continuous burning, the amount of fuel present in the fuel-air
mixture should not go below the lower limit or above the upper limit.
For example, the explosive range of petrol–air mixture is 10:1. This means
that when the concentration of a petrol–vapour in a petrol–air mixture is
between 8 and 12 by volume, the mixture will burn on ignition. When
the concentration of petrol vapour in a petrol–air mixture is below 8
(lower limit) or above 12 (upper limit) by volume, the mixture will not
burn on ignition.
4.6.4 Calorific Intensity or Flame Temperature
It is the maximum temperature reached when the fuel is completely
burnt in the theoretical amount of air.
When the fuel burns with a small flame, the entire heat is concentrated
in a small area and the calorific intensity will be high. But while burning
solid and liquid fuels as well as some gaseous fuels, much volatile
matter is given off resulting in a large flame. Here the heat liberated
gets distributed over a wide area and hence the calorific intensity will
be low.

4.7 SOLID FUELS

4.7.1 Coal and its Varieties or Ranking of Coal

Coal is classified on the basis of its rank. The rank of coal denotes its
degree of maturity. Vegetable matter, under the action of pressure, heat
and anaerobic conditions, gets converted into different stages of coal,
namely,
Peat Lignite Sub-bituminuous Bituminous Anthracite
Anthracite is the oldest coal from the geological perspective. It is a
hard coal composed mainly of carbon with little volatile content and
practically no moisture. Lignite is the youngest coal from the geological
perspective. It is a soft coal composed mainly of volatile matter and
moisture content with low fixed carbon. Fixed carbon refers to carbon
in its free state, not combined with other elements. Volatile matter refers
to those combustible constituents of coal that vaporize when coal is
heated.
(a) Peat
• Peat, considered to be a precursor of coal, has industrial importance
as a fuel in many regions, for example, Ireland and Finland.
• In its dehydrated form, peat is a highly effective absorbent for fuel
and oil spills on land and water.
(b) Lignite
• Lignite, also referred to as brown coal, is the lowest rank of coal and
used almost exclusively as fuel for electric power generation.
• Jet is a compact form of lignite that is sometimes polished and has
been used as an ornamental stone since the Iron Age.
(c) Sub-bituminous Coal
• Sub-bituminous coal, whose properties range from those of lignite
to those of bituminous coal, are used primarily as fuel for steam-
electric power generation.
• Additionally, it is an important source of light aromatic
hydrocarbons for the chemical synthesis industry.
(d) Bituminous Coal
• Bituminous coal, a dense mineral, is black or sometimes dark
brown, often with well-defined bands of bright and dull
material.
• It is used primarily as fuel in steam-electric power generation, with
substantial quantities also used for heat and power applications
in manufacturing and to make coke.
(e) Anthracite
• Anthracite, the highest-ranking coal, is a harder, glossy, black coal
used primarily for residential and commercial space heating.
• It may be divided further into metamorphically altered bituminous
coal and petrified oil, as from the deposits in Pennsylvania.
Here, peat is the most immature coal, hence it is lowest in rank
whereas anthracite is the most matured coal, and hence it is highest in
rank.
The process of conversion of lignite to anthracite is called coalification
(or) metamorphism of coal.
With the progress of coal-forming reaction, moisture content and
oxygen content reduces and percentage of carbon increases. Also, calorific
value increases from peat to bituminous.

Fig. 4.3 Transportation of Coal

Table 4.1 Classification of solid fuels and their properties
Fuel Nature Calorific Value kcal–kg Composition % Uses
Peat Highly fibrous, 4000– 5400 C = 57 Domestic fuel,
light brown H = 06 power generation
in colour O = 35
Lignite Fibrous, brown- 6500–7100 C = 67 Manufacture of
coloured coal H = 05 producer gas and
O = 26 steam
Sub- Black coloured, 7000–7500 C = 77 Manufacture of
bituminous homogenious H = 05 gaseous fuels
coal smooth mass O = 16
Bituminous Black, brittle 8000–8500 C = 83 Power generation,
coal burns with yellow H = 05 coke making,
smoky flame O = 10 domestic fuel
Anthracite Hard and most 8500–8700 C = 93 Boiler heating,
matured coal, H = 03 metallurgical
burns without O = 03 furnace
smoke

Table 4.2 Production of coal by country and year (million tons)

Country 2006 2007 2008 Reserve Life (years)
China 2380 2526 2782 41
USA 1053 1040 1062 224
EU 595 593 587 51
India 447 478 521 114
Australia 385 399 401 190
Russia 309 314 326 481

4.7.2 Analysis of Coal

Ultimate analysis and proximate analysis are used for the determination
of the quality of any coal sample. Proximate analysis determines the fixed
carbon, volatile matter, moisture and ash percentages. Ultimate analysis
is used to determine the percentage of carbon, hydrogen, nitrogen and
sulphur present in coal.
(a) Proximate Analysis
• The determination of the amount of moisture, volatile matter, fixed
carbon and ash present in coal is called proximate analysis.
• It is useful in deciding its utilization for a particular industrial
use.
(i) Estimation of Moisture Content in Coal
Accurately weigh 1 g of powdered dry coal sample in a previously
weighed, clean silica crucible. Heat the sample by placing in a hot-
air oven at 100 to 105°C for one hour. Then the sample is cooled in a
dessicator to room temperature and weighed again. The loss in weight
represents moisture.
Loss in weight of coal
\ % of moisture in coal = __________________________ × 100
Weight of coal initially taken

(ii) Estimation of Volatile Matter (VM) in Coal

After the analysis of moisture content, the crucible with the residual coal
sample is covered with a lid, and it is heated at 950 ± 20°C for 7.0 minutes
in a muffle furnace. Percentage of volatile matter can be calculated from
the loss in weight of the coal sample.

Loss in weight of
moisture-free coal
\ % of volatile matter in coal = __________________________ × 100
Weight of coal initially taken

(iii) Estimation of Ash in Coal

After the analysis of volatile matter, the crucible with the residual coal
sample is heated without lid at 700 ± 50°C for 30 minutes in a muffle
furnace.
The percentage of ash content can be calculated from the weight of
ash formed.
Weight of ash formed
\ % of ash in coal = ____________________ × 100
Weight of coal taken
(iv) Estimation of Fixed Carbon
It is determined by subtracting the sum of total moisture, volatile matter
and ash contents from 100.
% of fixed carbon = 100 – % of [moisture + VM + ash]

(v) Significance or Importance of Proximate Analysis

1. Moisture
High moisture content in coal is undesirable because it
• Reduces calorific value of coal
• Increases the consumption of coal for heating purpose
• Lengthens the time of heating
 The lesser the moisture content, the better the quality of coal.

2. Volatile Matter
The coal with higher volatile content
• Ignites easily (i.e. it has lower ignition temperature)
• Burns with long yellow smoky flame
• Has lower calorific value
• This gives more quantity of coal gas when it is heated in absence
of air.
A good-quality coal should have lesser volatile matter.

3. Ash
• Ash is the combustion product of mineral matters present in the
coal. It consists mainly of SiO2, Al2O3 and Fe2O3 with varying
amounts of other oxides such as Na2O, CaO, MgO, etc.
• Ash containing oxides of Na, Ca and Mg melts early (low melting
ash). During coke manufacture, the low-melting ash forms a fused,
lumpy, expanded mass which block the interspaces of the ‘grate’,
thereby obstructing the supply of air leading to irregular burning
of coal and loss of fuel.
• High ash content in coal is undesirable because it (a) increases
transporting, handling, storage costs, (b) is harder and stronger,
and (c) has lower calorific value.
A good-quality coal should contain lesser ash content.

4. Fixed Carbon
It is the pure carbon present in coal.
Higher the fixed carbon content of the coal, higher will be its
calorific value.

(b) Ultimate Analysis

The ultimate analysis indicates the various elemental chemical
constituents such as carbon, hydrogen, oxygen, sulphur, etc. It is useful in
determining the quantity of air required for combustion and the volume
and composition of the combustion gases. This information is required
for the calculation of flame temperature and the flue duct design etc.
The determination weight percentage of carbon, hydrogen, nitrogen,
oxygen and sulphur of the pure coal free from moisture and inorganic
constituents is called ultimate analysis.
(i) Determination of Carbon and Hydrogen in Coal
A known amount of coal is burnt in the presence of oxygen, thereby
converting carbon and hydrogen of coal into CO2 (C + O2 Æ CO2) and
H2O (H2 + ½ O2 Æ H2O) respectively. The products of combustion (CO2
and H2O) are made to pass over weighed tubes of anhydrous CaCl2 and
KOH, which absorb H2O and CO2 respectively.
The increase in the weight of the CaCl2 tube represents the weight of
water formed, while increase in the weight of the KOH tube represents
the weight of CO2 formed. The percentage of carbon and hydrogen in
coal can be calculated as follows.
Let X — the weight of coal sample taken
Y — the increase in the weight of KOH tube
Z — the increase in the weight of CaCl2 tube
Carbon
C + O2 CO2
12 32 44

44 g of CO2 contain 12 g of carbon,

12
i.e, 1 g of CO2 contains ___ g of carbon.
44
12
\ Y g of CO2 contains ___ × Y g of carbon.
44
12 Y
% of C in coal = ___ × __ × 100
44 X
Hydrogen

H2 + 1/2 O2 H2O
2 16 18

18 g of water contains 2 g of hydrogen.

1 g of water contains 2/18 g of hydrogen.
2
\ Z g of water contains = ___ × Z g of hydrogen.
18
2 Z
% of hydrogen in coal = ___ × __ × 100
18 X

(ii) Determination of Nitrogen in Coal

Nitrogen estimation is done by Kjeldahl’s method. A known amount of
powdered coal is heated with conc. H2SO4 and K2SO4 in a long-necked
flask (called Kjeldahl’s flask), thereby converting nitrogen of coal to
ammonium sulphate. When the clear solution is obtained (i.e. the whole
nitrogen is converted into ammonium sulphate), it is heated with 50%
NaOH solution.

(NH4)2 SO4 + 2NaOH Na2SO4 + 2NH3

The ammonia, thus formed, is distilled over and is absorbed in a

known quantity of standard 0.1N HCl solution. The volume of unused
0.1N HCl is then determined by titrating against a standard NaOH
solution.
Thus, the amount of acid neutralized by liberated ammonia from coal
is determined.
Let,
Volume of 0.1N HCl initially taken = A ml
Volume of unused HCl = B ml
Acid neutralised by ammonia = (A – B) ml
We know that 1000 ml of 1N HCl = 1 mole of HCl
= 1 mole of NH3
= 14 g of N2
14 × (A – B) × 0.1
\ (A – B) ml of 0.1N HCl = ________________ g of N2
1000 × 1N
14 × (A – B) × 0.1
X g of coal sample contains ________________ g of N2
1000 × 1N

14 × Volume of acid consumed × Normality

% of nitrogen = _______________________________________ × 100
1000 × weight of coal sample (X)

(iii) Determination of Sulphur in Coal

A known amount of coal is burnt completely in a bomb calorimeter in
the presence of oxygen. Ash, thus obtained, contains sulphur of coal as
sulphate, which is extracted with dil HCl. The acid extract is then treated
with BaCl2 solution to precipitate sulphate as BaSO4.
The precipitate is filtered, washed, dried and weighed to calculate the
sulphur in coal as stated below:
Let,
X = weight of coal sample taken
M = weight of BaSO4 precipitate formed.
 S + 2O2 SO4 BaSO4
32 233

233 g of BaSO4 contains 32 g of sulphur.

i.e. 1 g of BaSO4 contains 32/233 g of sulphur.
\ M g of BaSO4 contains (32/233) × M g of sulphur

32 M
% of sulphur in coal = ____ × ___ × 100
233 X

(iv) Significance or Importance of Ultimate Analysis

1. Carbon and Hydrogen
• The amount of carbon and hydrogen is vital for the calculation of
air required for complete combustion and design the combustion
chamber.
• The percentage of carbon is helpful in the classification of coal.
Good-quality coal should have more percentage of C and H.

2. Nitrogen
• Nitrogen is a noncombustible matter. Hence, it does not have any
calorific value, and its presence in coal is undesirable.
Good-quality coal should have very little nitrogen content.

3. Sulphur
• Even though sulphur is a combustible matter, the combustion
products of sulphur, i.e. SO2 and SO3, are harmful and have
corrosion effects on equipment.
• Coal containing sulphur is not suitable for the preparation of
metallurgical coke as it affects the properties of the metal.
Presence of sulphur is not desirable in coal.

4. Oxygen
• Presence of oxygen consumes hydrogen, and thereby reduces the
calorific value.
• As the oxygen content increases, the moisture content and the
moisture will consume some amount of heat for evaporation.
A good-quality coal should contain lesser moisture content.

(c) Carbonisation of Coal

Heating of coal in the absence of air at high temperature to produce a
residue coke, tar and coal gas is called carbonisation.
 (i) Caking of Coal: When coal is heated strongly, the mass becomes
soft and coherent. Then it is called caking of coal.
(ii) Coking of Coal: If the mass produced is hard, porous and strong
then it is called coking of coal.

4.8 METALLURGICAL COKE

When bituminous coal is heated strongly in the absence of air, the volatile
matter escapes out and a lustrous, dense, strong, porous and coherent
mass is left, which is called metallurgical coke.

4.8.1 Properties or Characteristics of Metallurgical Coke

The most important industrial use of coke is in the metallurgical industry,
especially in the blast furnace. Good coke for metallurgy should possess
the following characteristics.
(i) Purity High purity of coke is desirable. The moisture and ash
content should be low.
(ii) Porosity As the porosity increases, the combustion rate of the
coke will increase. This happens because the oxygen comes in
contact with coke, which helps for its complete combustion. A
good coke should possess high porosity.
(iii) Strength The coke should be strong and hard, which helps it to
withstand high temperature.
(iv) Size The size of the coke should be uniform and medium for
uniform heating.
(v) Calorific Value The calorific value of good coke should be
high.
(vi) Combustibility It should burn easily and smoothly.
(vii) Reactivity It refers to its ability to react with O2, CO2, steam and
air. The metallurgical coke must have low reactivity.
(viii) Cost It must be cheap and readily available.

4.8.2 Manufacture of Metallurgical Coke

Two types of ovens are mainly used for metallurgical coke production:
(a) Beehive coke-oven process
(b) Otto Hoffman’s by-product method
(a) Beehive Coke-oven Process
The beehive oven (due to its shape) is a primitive obsolete process. The
oven is a dome-shaped structure and made up of fire bricks. There are
two openings, one at the top and the other at the side. Coal is charged
through the top circular opening, whereas coke is removed through the
side door after carbonization. The side door also acts as an air inlet. Its
typical dimensions are, height = 2 m; base diameter = 3.5 m and capacity
= 5 tons of coal.
First, some air is supplied into the oven to ignite the coal. The volatile
matter present in coal escapes and burns inside. Therefore, heat for
carbonization is supplied by burning of volatile matter and partly by
coal itself.

Charging door
Refractory lining

2m
Coal

Door for air supply

3.5 m
and coke discharging

Fig. 4.4 Beehive coke-oven

Carbonization proceeds from top to bottom and it takes about 3 to 4

days to complete. The hot coke is then removed through the side door
and quenched with water.
Demerits
• It is a batch process.
• Not suitable for large-scale production.
• All the volatile matter present in coal escapes into the atmosphere
as waste, we cannot recover any by-product.
• Large coking time and coke yield of only 60% are its other
demerits.
(b) Otto Hoffman’s By-product Coke Oven
To recover various by-products which are lost in the beehive oven
method and also increase the thermal efficiency of the carbonization
process, Otto Hoffman developed the modern by-product coke oven.
The oven is heated externally by the hot flue gases which come out of
the combustion chamber.
 The coal is heated in a silica chamber having a size of about 10–12 m
long, 3–4 m height and 0.4–0.45 m wide. Each chamber is provided with
a charging hole at the top. It is also provided with a gas outlet valve at
the top and an iron door at each end for discharging coke.

A, B, C, D—Coke ovens
1,2,3,4-Heat re-generators Coal gas

A B C D

1 2 3 4

To chimney
To chimney
Air Producer gas

Fig. 4.5 Otto Hoffman by-product coke oven

The finely crushed coal is introduced through the charging door at

the top of the chambers which are then closed. The chambers are heated
up to 1200°C by burning pre-heated air and the producer-gas mixture
in the interspaces between the chambers.
The flue gases produced during combustion, before escaping to
the chimney, pass on their heat to the walls of chamber first and third
hot regenerators. When the first and third hot regenerators attain
the temperature for about 1000°C, the flue gas is diverted to second
and fourth hot regenerators and the incoming fuel-air mixture is
passed through first and fourth regenerators to gain heat and efficient
combustion.
For economical heating, the directions of inlet and flue gases are
changed frequently. The above system of recycling the flue gases to
produce heat energy is known as the regenerative system of heat
economy. When the process is complete, the coke is removed and
quenched with water.
In this process, complete carbonization takes about 12–18 hours. The
yield of coke is about 70%.
(c) Recovery of By-products
The gas coming out from the oven is known as coke-oven gas and is
mainly composed of ammonia, H2S, naphthalene, aromatics, tar, etc.
(i) Removal of Tar
The coke-oven gas is first passed through a tower in which liquor
ammonia is sprayed. Tar and dust get collected in a tank below, which
is heated by a steam coil to recover back the ammonia sprayed. The
ammonia is used again and again.
(ii) Removal of Ammonia
The gas is then passed through the other tower where water is sprayed.
Ammonia gets converted to NH4OH.
(iii) Benzene and Other Aromatic Compounds
The gas is then passed through the next tower in which creosote oil is
sprayed. Benzene and other aromatic compounds are dissolved in the
oil and recovered.
(iv) Hydrogen Sulphide
The gas then enters into a purifying chamber packed with Fe2O3, which
removes any sulphur compound present in coal gas.

(d) Advantages
• High thermal efficiency and less carbonization time.
• Valuable gases (like coal gas, ammonia, benzene, etc.) are recovered
as by products.
• Heating is done externally by producer gas.

4.9 LIQUID FUELS

“Loss of even one drop of oil every second can cost you over 4000
litres a year”.

4.9.1 Petroleum
Petroleum, or crude oil is a naturally occurring oily, bituminous liquid
composed of various organic chemicals. It is found in large quantities
below the surface of the earth and is used as a fuel and as a raw material
in the chemical industry. Modern industrial societies use it primarily to
achieve a degree of mobility on land, at sea, and in the air, something that
was barely imaginable less than 100 years ago. In addition, petroleum
and its derivatives are used in the manufacture of medicines, fertilizers,
foodstuffs, plastics, building materials, paints, etc.
 The approximate composition of petroleum is
C = 80 – 84%
H = 10 – 14 %
S = 0.1 – 0.5 %
N + O = Negligible
(a) Formation of Petroleum
Petroleum is formed under the earth’s surface by the decomposition of
marine organisms. The remains of tiny organisms that live in the sea and,
to a lesser extent, those of land organisms are carried down to the sea
by rivers and of plants that grow on the ocean bottoms are enmeshed
with the fine sands and silts that settle to the bottom in quiet sea basins.
Such deposits, which are rich in organic material, become the source for
the generation of crude oil.
(b) Classification of Petroleum
• Three broad classes of crude petroleum exist: the paraffin types,
the asphaltic types, and the mixed-base types.
• The paraffin types are composed of molecules in which the number
of hydrogen atoms is always two more than twice the number of
carbon atoms. The characteristic molecules in the asphaltic types
are naphthenes, composed of twice as many hydrogen atoms as
carbon atoms.
• The mixed-base group has both paraffin hydrocarbons and
naphthenes.
(i) Paraffin-based oil contains mainly n-alkanes, e.g.
Pennsylvanian and gulf coast oil.
(ii) Asphalt base oil contains aromatic and alicyclic hydrocarbons.
e.g. Californian oil.
(iii) Mixed-base oil contains higher proportion of aromatics and
naphthenes (cyclo alkanes), e.g. Mexican oil.
(c) Oil Recovery
The oil industry has developed methods for supplementing the
production of crude oil that can be obtained mostly by taking advantage
of the natural reservoir energy. These supplementary methods,
collectively known as enhanced oil-recovery technology, can increase
the recovery of crude oil. Two successful supplementary methods are
in use at this time: water injection and steam injection.
(i) Water Injection
In a completely developed oil field, the wells may be drilled upto
anywhere from 60 to 600 m (200 to 2,000 ft) from one another, depending
on the nature of the reservoir. If water is pumped into alternate wells in
such a field, the pressure in the reservoir as a whole can be maintained
or even increased. In this way, the rate of production of the crude oil
also can be increased; in addition, the water physically displaces the oil,
thus increasing the recovery efficiency. In some reservoirs with a high
degree of uniformity and little clay content, water flooding may increase
the recovery efficiency to as much as 60 per cent or more of the original
oil in place. Water flooding was first introduced in the Pennsylvania oil
fields, more or less accidentally, in the late 19th century, and it has since
spread throughout the world.
(ii) Steam Injection
Steam injection is used in reservoirs that contain very viscous oils,
those that are thick and flow slowly. The steam not only provides a
source of energy to displace the oil, it also causes a marked reduction
in viscosity (by raising the temperature of the reservoir), so that
the crude oil flows faster under any given pressure differential.
(iii) Offshore Drilling
Another method to increase oil-field production has been the construction
and operation of offshore drilling rigs. The drilling rigs are installed,
operated, and serviced on an offshore platform in water up to a depth
of several hundred metres; the platform may either float or sit on legs
planted on the ocean floor, where it is capable of resisting waves, wind,
and in Arctic regions, ice floes. Successful bore holes have been drilled
right on target, in this way, to depths of more than 6.4 km (more than 4
miles) from the surface of the ocean.
(d) Refining of Petroleum, or Crude Oil
The process of removing impurities and separating out the oil into
various fractions having different boiling points is known as refining
of petroleum.
Once oil has been produced from an oil field, it is treated with
chemicals and heat to remove water and solids, and the natural gas
is separated. The oil is then stored in a tank, or battery of tanks, and
later transported to a refinery by truck, railroad tank car, barge, or
pipeline. Large oil fields all have direct outlets to major, common-carrier
pipelines.
 Uncondensed gases

Loose cap
Petroleum ether

Gasoline
Chimney

Tray Naptha

Kerosene
Crude oil
Diesel oil

Lubricating oil
Heavy oil
Furnace at 400°C Fractionating column

Fig. 4.6 Distillation of various fractions from petroleum

(i) Removal of Impurities

The impurities present in the oil are the fine water droplets, NaCl, MgCl2,
sulphur, etc. The crude oil is an extremely stable emulsion of oil and salt
water. Water is separated from the oil by Cottrell’s process using ring
electrodes. In this method, the crude oil is allowed to flow between two
highly charged electrodes. The colloidal water droplets combine to form
large drops, which are then separated from oil.
Modern techniques like electrical desalting are used to remove NaCl
and MgCl2 from oil. Sulphur is removed by treating the oil with copper
oxide and separated by filtration.
(ii) Fractional Distillation
The purified crude oil is heated in a furnace, called oil heater, where the
temperature will be around 400°C. Here the oil gets vapourised. The hot
vapours are then sent to the fractionating column.
It is a tall cylindrical tower consisting of a number of horizontal
stainless-steel trays at short distances. Each tray is provided with a small
chimney, which is covered with a loose cap. The tower will be hot at
the lower end and comparatively cooler at the upper end. When the oil
vapours go up in the tower, they become cool and condense. The heavier
compounds having higher boiling points get cooled first and condensed
in the trays whereas the fractions having lower boiling points condense
near the top of the tower.
Lower fractions are used after purification while the high-boiling-point
fractions are subjected to a cracking operation to get more useful lower
fractions.
(e) Important Fractions of Petroleum Distillation
(i) Petrol or Gasoline
• It is a low boiling fraction of petroleum obtained between
40 – 120° C. It is a mixture of hydrocarbons pentane to octance (in
terms of carbon atoms C5 – C9).
• Its calorific value is about 11,250 kcal/kg.
• It is used as fuel in the ICE of automobiles and aeroplanes. Its
antiknock value can be improved by the addition of TEL.
(ii) Naphtha
• Naphtha is a light, colourless to straw-coloured liquid which
distills off from petroleum between 120–180° C. It is a mixture of
hydrocarbons C9 – C10 (nonane - decane) carbon atoms.
• The lightest of the distillates are used as solvents for fats and
rubber, whereas the heaviest distillates are used for the fuel.
• Naphtha is also called white spirit which is used in dry cleaning
as varnish thinner, for floor and furniture polishes, etc.
(iii) Kerosene
• It is also a high boiling fraction of petroleum obtained between
180-250° C. It is a mixture of C10 – C16 hydrocarbons.
• Its calorific value is about 11,100 kcal/kg.
• It is used as domestic fuel and jet engine fuel.
(iv) Diesel
• It is relatively a high boiling point fraction of petroleum obtained
between 250-320°C. It is a mixture of hydrocarbons in terms of
carbon atoms C15 – C18.
• Its calorific value is about 11,000 kcal/kg.
• It is used as fuel for compression ignition engines. Its antiknock
value can be improved by doping with isoamyl nitrate.
(v) Fuel Oil
• The residue of petroleum after distilling off the lighter fractions
is called fuel oil. It is distilled in vacuum into the following
fractions.
(a) Light fuel oil = 350 – 420°C
(b) Heavy neutral oil = 420 – 500°C
• A typical analysis of fuel oil is C = 86% ; H = 12% ; S = 1% ; H2O
= 0.6%; Sediments = 0.4% .
• Its calorific value is about 9200 kcal/kg.
 • It is used as industrial fuel and in the feedstock for thermal
cracking plants.
(vi) Asphalt or Tar
• Asphalts are produced by (i) the deep vacuum distillation of fuel
oil, and (ii) the oxidation of residual petroleum by air at a higher
temperature.
• Asphalts have the highest viscosity of all petroleum-refining
products. Petroleum asphalts are marketed in the liquid, semisolid
and solid forms.
• They are intended for roadmaking and as roofing material.
They are also used for waterproofing of concrete and reservoirs,
waterproofing paints and in the prevention of corrosion.

Table 4.3 Various fractions of petroleum distillation

Name of the Hydrocarbons in terms Boiling Point
S. No Uses
Fraction of Carbon Atom in °C
1. Uncondensed C1–C4 < 30 LPG—domestic fuel
gases
2. Petroleum ether C5–C7 30–70 Solvents for varnish and
rubber
3 Gasoline or C5–C8 40–120 Fuel in ICE of automobiles
petrol and aeroplanes
4 Naphtha or C9–C10 120–180 Solvent in dry cleaning
Solvent spirit
5 Kerosine oil C10–C16 180–250 Domestic fuel, Jet engine
fuel.
6 Diesel oil or C15–C18 250–320 Diesel engine fuel
gas oil
7 Heavy oil C17–C30 320–400 To produce cracked petrol

4.9.2 Petrol or Gasoline

• It is a low boiling fraction of petroleum obtained between 40–
120°C.
• It is a mixture of hydrocarbons pentane to nonane (in terms of
carbon atoms C5–C9).
• Its calorific value is about 11, 250 kcal/kg.
• It is used as fuel in ICE of automobiles and aeroplanes.
• Its antiknock value can be improved by the addition of Tetra Ethyl
Lead (TEL).
The crude oil on fractional distillation yields only about 15–20%
gasoline. This is known as straight-run-gasoline.
 The quality of straight-run gasoline is not so good. It contains mainly
straight chain paraffins, which ignite readily and more rapidly than any
other hydrocarbons and hence, it produce knocking (unwanted sound)
in IC engines.
In order to overcome these difficulties and also to improve the quality
of gasoline, high boiling fractions are cracked into more valuable low
boiling fractions suitable for SI engines. The gasoline obtained by
cracking is called cracked gasoline.
Cracking
The formation of low boiling hydrocarbons of low molecular weight
by the decomposition of high boiling hydrocarbons of high molecular
weight is called cracking.
C14H30 C5H12 + C9H18
n-tetradecane n pentane nonene
[Link]. 253.7°C B. pt : 36°C [Link]. 143°C

4.9.3 Manufacture of Synthetic Petrol

Petrol can be synthesized by any one of the following methods.
I. Polymerization
(a) Thermal polymerization
(b) Catalytic polymerization
II. Hydrogenation of coal
(a) Bergius process or direct process.
(b) Fisher–Tropsch process or indirect process.
III. Alkylation
I Polymerization
The gases produced in cracking contain C3 and C4 olefins (isopropylene,
isobutylene, etc.) and alkanes (methane, ethane, propane, butane). These
gases undergo polymerization in the presence of a catalyst, (H3 PO4) at
suitable temperature and pressure to give gasoline (polymer petrol), rich
in branched-chain hydrocarbons.
Hence, polymerization is mainly for the production of superior
gasoline and is complementary to catalytic cracking.
Polymerization is of two types:
(a) Thermal Polymerization: Polymerisation of cracked gases is carried
out at 500–600°C and 70–350 kg/cm2 pressure. The product is the gasoline
and gas oil mixture, from which gasoline is separated by fractionation.
(b) Catalytic Polymerization: This process is carried out in the
presence of a catalyst like H3PO4. By this method, isobutylene can be
polymerized to give higher olefins which is hydrogenated to gasoline
hydrocarbons.
II Hydrogenation of Coal
Coal contains 4.5 % of hydrogen, whereas petroleum contains 18 % of
hydrogen. So coal is a hydrogen-deficient compound, if coal is heated
with hydrogen at high temperature and high pressure, it is converted
in to gasoline.
The preparation of liquid fuels from solid coal is called hydrogenation
of coal.
Petrol can be synthesized by destructive hydrogenation of coal
(Bergius process) and liquification of coal (Fischer–Tropsch process).
(a) Bergius Process, or Direct Process
The raw materials used in this process are coal dust, heavy oil and nickel
oleate or tin oleate.
A coal paste is prepared by mixing coal dust with heavy oil and
catalyst. It is then pumped into the converter where the paste is heated
to 450–500°C under 200–250 atm in presence of hydrogen.

Fig. 4.7 Bergius process

The reaction products mainly contain a mixture of hydrocarbons.

Mixture of hydrocarbons
Coal dust
suspended in + H2 450°C Condensation
heavy oil 200–250 atm

Crude oil
 Since the reaction is exothermic, the vapours leaving the converter are
condensed in the condenser to give synthetic petroleum or crude oil.
The oil is then fractionally distilled to give
(i) Petrol
(ii) Middle oil
(iii) Heavy oil
Middle oil is again hydrogenated in presence of solid catalysts to
produce more amount of gasoline. Heavy oil is used for making paste
with fresh coal dust. The yield is about 60%.
(b) Fischer–Tropsch Process
The raw materials used in this process are hard coke, steam to produce
water gas, i.e. water gas is obtained, by passing steam over red-hot
coke.

Fig. 4.8 Fisher–Tropsch process

1200°C
C + H2O CO + H2
Water gas

The first step in this process is purification of gas. To remove H2S, the
gas is passed through Fe2O3 and to remove organic sulphur compounds,
the gas is again passed through a mixture of Fe2O3 and Na2CO3.
The purified gas is compressed to 5–25 atm. and passed over a catalyst
bed containing oxides of Th, Co and Mg at 200–300°C. While passing the
purified gas through this catalyst bed, it is converted to straight-chain
paraffins and olefins.
n CO + (2n + 1) H2 CnH2n + 2 + n H2O
n-paraffins

n CO + 2n H2 CnH2n + n H2O
olefins
 Since the reactions are exothermic, the vapours leaving the vessel are
condensed in the condenser to give petroleum. It is fractionally distilled
to yield petrol and heavy oil.
III Alkylation
Replacement of hydrogen atom from a hydrocarbon by an alkyl group
is known as alkylation.
Example:
H3C
Anhydrous H3C
H3C CH CH3 H2C C CH3 CH CH2 C CH3
HF
H3C
CH3 CH3 CH3

Isobutane Isobutene Iso-octane

The reaction of isobutane and isobutene in the presence of anhydrous

HF at room temperature gives iso-octane. This process is highly useful
for the production of high-quality petrol.

Table 4.4 Comparison of straight-run, cracked and polymer gasoline

[Link] Straight-run Petrol Cracked Petrol Polymer Petrol
1. Obtained from straight Obtained from heavy oil Obtained from low molecular
distillation of crude oil weight gaseous fraction
2. Contains only n-alkanes. Contains isoparaffins Contains more of branched
and aromatics. chain hydrocarbons
3. Composition range C5–C9 Narrow range Very narrow range
4. Low octane number Higher octane number Higher octane number

(c) Purification of Petrol or Gasoline

Gasoline or petrol, obtained either from crude oil or synthetic process,
may contain some undesirable impurities. They are mainly unsaturated
olefins, colouring matters, sulphur compounds, etc.
The unsaturated olefins get oxidized and polymerized thereby causing
gum and sludge formation on storing.
On the other hand, sulphur compounds lead to corrosion of ICE and
also affect tetra ethyl lead which is added to gasoline to obtain good
petrol. So these undesirable contents must be removed from gasoline.
Unsaturated olefins and colouring matter are removed by using
adsorbents like Kieselguhr, Fuller’s earth, etc.
• Sulphur containing petrol is known as sour spirit.
• The process of desulphurization of petrol is called sweetening of
petrol.
(d) Desulphurization
It can be done by Doctor’s treatment, i.e. petrol is treated with an alkaline
solution of sodium plumbite (Doctor’s solution).
The resulting disulphide (lead mercaptide) in gasoline are extracted
by using suitable solvent. After refining of gasoline, some inhibitors or
antioxidants are added in order to retard the oxidation of olefins (olefin
peroxide) which cause the formation of gum on storage.

4.9.4 Engines
Fractions like petrol and diesel oil are used as engine fuels. Piston engines
can be divided into Spark Ignition (SI) and Compression Ignition (CI)
engines. The former consumes petrol and the latter operates on diesel
oil.
SI Engines
Today, internal combustion engines in cars, trucks, motorcycles, aircraft,
construction machinery and many others, most commonly use a four-
stroke cycle. The four strokes refer to intake, compression, combustion
(power), and exhaust strokes that occur during two crankshaft rotations
per working cycle of the gasoline engine and diesel engine.
1. Intake Stroke On the intake or induction stroke of the piston, the
piston descends from the top of the cylinder to the bottom of the cylinder,
reducing the pressure inside the cylinder. A mixture of fuel and air is
forced by atmospheric (or greater) pressure into the cylinder through
the intake port. The intake valve(s) then close.
2. Compression stroke With both intake and exhaust valves closed,
the piston returns to the top of the cylinder compressing the fuel–air
mixture. This is known as the compression stroke.
3. Power stroke While the piston is close to the top-dead centre, the
compressed air–fuel mixture is ignited, usually by a spark plug (for a
gasoline or Otto cycle engine) or by the heat and pressure of compression
(for a diesel cycle or compression ignition engine). The resulting massive
pressure from the combustion of the compressed fuel–air mixture drives
the piston back down toward the bottom-dead centre with tremendous
force. This is known as the power stroke, which is the main source of the
engine’s torque and power.
4. Exhaust stroke During the exhaust stroke, the piston once again
returns to the top-dead centre while the exhaust valve is open. This action
evacuates the products of combustion from the cylinder by pushing the
spent fuel–air mixture through the exhaust valve(s).
Air

Fuel
Combustible

Intake Exhaust
valve value

Intake Compression Power Exhaust

Fig. 4.9 Various strokes on fuel engines

(i) Knocking in Internal Combustion Engines

Knocking is a tendency of a fuel (petrol and diesel), which produces
a badly and uncontrolled metallic sound in the combustion chamber
during the combustion.
(ii) Knocking in SI Engines
A good normal petrol has to burn at the beginning of the power stroke
when it is ignited with the help of a spark plug. Instead, a little amount
of petrol will start to burn at the end of the second stroke (compression
stroke). The rest of the petrol will burn in the third stroke when it is
ignited with the spark plug. This produces an unwanted sound in the
cylinder, called knocking. Petrol produces premature ignition is called
petrol knock. This type of knocking creates unwanted sound and also
reduces the efficiency of engines.
(iii) Chemical Structure and Knocking
The knocking tendency decreases as follows:
n-alkanes Isoparaffins Olefins Naphthenes Aromatics
n-alkanes have the lowest antiknock values. So the presence of
maximum quantity of aromatics and minimum quantity of n-alkanes is
desirable in petrol.
(iv) Measurement of Knocking in SI Engines (Octane Number)
Octane number expresses the knocking characteristics of petrol. The
n-heptane (a constituent of petrol) knocks very badly, so its antiknock
value has been given as zero. On the other hand, iso-octane (also a
constituent of petrol) gives very little knocking, so its antiknock value
has been given as 100.
Octane number can defined as percentage of iso-octane present in
iso-octane and n-heptane mixture, which matches the same knocking
characteristics of gasoline mixture test sample”.
For example, petrol with the same knocking characteristics as a
mixture of 90% iso-octane and 10% heptane would have an octane
rating of 90. This does not mean that the petrol contains just iso-octane
and heptane in these proportions, but that it has the same detonation
resistance properties. Because some fuels are more knock-resistant than
iso-octane, the definition has been extended to allow for octane numbers
higher than 100.
Octane rating does not relate to the energy content of the fuel. It is
only a measure of the fuel’s tendency to burn in a controlled manner,
rather than exploding in an uncontrolled manner. Where octane is raised
by blending in ethanol, energy content per volume is reduced.
It is possible for a fuel to have an octane number greater than 100,
because iso-octane is not the most knock-resistant substance available.
Racing fuels, Liquefied Petroleum Gas (LPG), and alcohol fuels such
as methanol or ethanol may have octane ratings of 110 or significantly
higher ethanol’s octane Number is 129.
(v) Improvement of Antiknock Value
(Leaded Petrol)
Typical ‘octane booster’ gasoline
additives include methyl tert-butyl
ether, ethyl tert-butyl ether, isooctane
and toluene. Lead, in the form of
tetra-ethyl lead, was once a common
additive, but since the 1970s, its use
in most of the industrialised world
has been restricted, and its use is
currently limited mostly to aviation
gasoline. Fig. 4.10 A US petrol pump offering
five different octane ratings
(vi) Mechanism of Knocking
Knocking follows free-radical mechanism, leading to a chain growth.
If the chains are terminated before their growth, knocking will cease.
TEL decomposes thermally to form ethyl-free radicals, which combine
with the free radicals of knocking process and thus the chain growth is
stopped.
Disadvantage of Using TEL
TEL forms lead oxide, which deposits on a spark plug and creates
problems. So, to remove it, ethylene dibromide is added. During burning,
lead bromide is formed which evaporates away in the heat engines
and goes out together with exhaust gases. This creates atmospheric
pollution for human beings. Hence, at present aromatic phosphates are
used instead of TEL.
CH2 Br
Pb + PbBr2 + CH2 = CH2
CH2 Br

(vii) Octane Number in India

India’s ordinary and premium petrol are of 89–91 octane numbers. The
premium petrols are generally ordinary fuels with additives that do
not really change the octane value. Two variants, ‘Speed 93’ and ‘Speed
97’, were launched, with octane-number values of 93 and 97, but Speed
97 was discontinued. India’s vehicles usually have compression ratios
under 10:1, thus enabling them to use lower-quality petrol without
engine knocking.

4.9.5 Diesel
• It is relatively a high boiling point fraction of petroleum obtained
between 250–320°C.
• It is a mixture of hydrocarbons in terms of carbon atoms
C15–C18.
• Its calorific value is about 11,000 kcal/kg. It is used as fuel for
compression ignition engine.
• Its antiknock value can be improved by doping with isoamyl
nitrate.
CI Engines
In a CI engine, air alone is compressed. This raises the cylinder
temperature as high as 300°C. Then the oil is injected or sprayed, which
must ignite spontaneously. Now combustion products expand and the
power stroke begins.
(i) Knocking in CI Engines
Sometimes, even after the compression stroke is over and even after
the diesel oil is sprayed, burning may not start. So, more and more
fuel is injected automatically and sudden ignition may occur and burn
the whole of the oil. Thus delayed ignition results and uncontrolled,
excessive combustion produces ‘diesel knock’.
 So in an SI engine, knocking is due to premature or too early ignition.
In CI engines, knocking is due to delayed ignition or ignition lag.
(ii) Measurement of Knocking in CI Engines (Cetane Number)
Cetane Number, or CN, is a measurement of the combustion quality
of diesel fuel during compression ignition. It is a significant expression
of diesel-fuel quality among a number of other measurements that
determine overall diesel-fuel quality.
Cetane (C16H34) has a very short ignition delay and hence its cetane
number is taken as 100. On the other hand, a -methyl napthalene has a
very large ignition delay and hence its cetane number is taken as zero.
Cetane number is defined as the percentage of cetane present in a
mixture of a -methyl naphthalene and cetane, which matches the same
knocking characteristics of diesel mixture test sample.
CH3

CH3–(CH2)14–CH3
n-cetane
(cetane number = 100) a-methyl napthalene
n-hexadecane (cetane number = 0)

Cetane number is actually a measure of a fuel’s ignition delay; the time

period between the start of injection and start of combustion (ignition)
of the fuel. In a particular diesel engine, higher cetane fuels will have
shorter ignition delay periods than lower cetane fuels.
Generally, diesel engines run well with a cetane number from 40 to 55.
Fuels with higher cetane numbers, which have shorter ignition delays,
provide more time for the fuel combustion process to be completed.
Hence, higher-speed diesels operate more effectively with higher cetane-
number fuels. There is no performance or emission advantage when the
cetane number is raised past approximately 55; after this point, the fuel’s
performance has no change.
(iii) Chemical Structure and Knocking
The knocking tendency in CI engines increases as follows:
n-alkane Isoparaffins Olefins Naphthenes Aromatics
Octane numbers decrease in this order. Therefore, an oil of high
octane number has a low cetane number and vice versa. Consequently,
petroleum crude gives petrol of high octane number and diesel of low
cetane number.
(iv) Additives to Improve Cetane Number
• Dimethyl ether may prove advantageous as a future diesel fuel
since it has a high cetane rating (55) and can be produced as a
biofuel.
• Alkyl nitrates (principally, 2-ethyl hexyl nitrate) and di-tert-butyl
peroxide are used as additives to raise the cetane number.
(v) Cetane-Number Specifications in Various Countries
• In Europe, diesel cetane numbers were set at a minimum of 38
in 1994 and 40 in 2000. The current standard for diesel sold in
the European Union, Iceland, Norway and Switzerland has a
minimum cetane index of 46 and a minimum cetane number of
51. Premium diesel fuel can have a cetane number as high as 60.
• Premium diesels may or may not have higher cetane, depending
on the supplier. Premium diesel often uses additives to improve
cetane number and lubricity, detergents to clean the fuel injectors
and minimize carbon deposits, water dispersants, and other
additives depending on geographical and seasonal needs.

Table 4.5 Comparison between petrol and diesel in Internal Combustion Engines (ICE)
[Link] Petrol Diesel
1. Low boiling petroleum (C5 – C10) High boiling fraction of petroleum contains
C15 – C18 hydrocarbons
2. Fuel for SI engine Fuel for CI engine
3. Knocks due to premature ignition Knocks due to ignition delay
4. Knocking tendency measured in Knocking tendency measured in cetane
octane rating rating
5. Antiknocking is improved through Antiknocking is improved by doping
addition of TEL with isoamyl nitrate
6. Lower thermal efficiency Higher thermal efficiency
7. More consumption Less consumption

4.9.6 Aviation Petrol

• Avgas is a high-octane aviation fuel used to power many aircraft
and racing cars. Avgas is a abbreviation of aviation gasoline.
• Avgas is used in aircraft that have pistons or Wankel engines.
• It has an octane number of 100 or even more. Polymerization,
alkylation, isomerization and reforming are the processes used to
produce or convert ordinary gasoline into aviation gasoline.
• Generally, aviation gasoline is made up of a higher percentage
of isoparaffins and a smaller percentage of naphthalenes and
aromatics.
 • Aviation gasoline possesses higher antiknock value, stability,
volatility than ordinary gasoline.

4.10 GASEOUS FUELS

Gaseous fuels in common use are liquefied petroleum gases (LPG),

natural gas, producer gas, blast furnace gas, coke-oven gas, etc. The
calorific value of gaseous fuel is expressed in kilocalories per cubic
metre (kcal/m3), i.e. at normal temperature (20°C) and pressure
(760 mmHg).

4.10.1 Natural Gas

• Methane is the main constituent of natural gas and accounts for
about 95% of the total volume.
• Other components are ethane, propane, butane, pentane, nitrogen,
carbon dioxide, and traces of other gases.
• Very small amounts of sulphur compounds are also present.
• Since methane is the largest component of natural gas, generally
properties of methane are used when comparing the properties
of natural gas to other fuels.
• Natural gas is a high-calorific-value fuel requiring no storage
facilities.
• It mixes with air readily and does not produce smoke or soot.
• It has no sulphur content.
• It is lighter than air and disperses into air easily in case of leak.

Trap
Derrick

Mud hose
Rotary
Engines table
Salt dome
Natural Limestone
gas
Drill Blowout
Mud
cuttings pump preventers
Casings
Cuttings
Circulating Oil reservoir Oil reservoir
fluid Drill bit

Fig. 4.11 Natural-gas reservoir

 The composition of natural gas is given below.
Constituent Percentage
Methane 88
Ethane 06
Propane 04
Butane 1–1.5
Pentane 0–0.5
3
The calorific value is 12,000–14,000 kcal/m .
Uses
• It is used as a green fuel for engines, preferably in highly populated
cities and areas having dense vehicle population. In India, at New
Delhi, all the public transportation vehicles are fitted with engines
which use CNG (Compressed Natural Gas) as the fuel.
• It is an excellent domestic and industrial fuel and can be conveyed
over very large distances in pipelines.
• It is also used in fuel cells for electricity generation.
• It has recently been used in the manufacture of a number of
chemicals by synthetic processes.

4.10.2 Water Gas or Blue Gas

Water gas is essentially a mixture of combustible gases like CO, H2 with
a little non combustible gases like CO2 and N2.
(a) Calorific Value Its Calorific value is 2800 kcal/m3.
(b) Composition The average composition is
H2 = 48 %
CO = 44 %
CO2, N2 and CH4 = rest
(c) Manufacture A water gas generator is a steel cylindrical vessel.
At the top, it is provided with a hopper for adding coke. The water-gas
outlet is provided near the top. At the bottom, it is provided with an
arrangement of taking out ash formed.
It is obtained by the action of steam on a bed of coke heated to
1000°C.
C + H2O + 28 kcal CO + H2
Since the above reaction is endothermic, the coal cools down after a
few minutes and the reaction proceeds in a different way to form CO2
and H2 instead of water gas (CO + H2).
C+ 2 H2O CO2 + 2H2 – 19 kcal
 Hopper for
coke feeding

Water gas outlet

Coke

Steam Air

Ash

Fig. 4.12 Water-gas manufacturing unit

In order to avoid the above undesirable reaction, the blow of air

replaces the blow of steam. The following reaction now occurs.
C + O2 CO2 + 97 kcal
2C + O2 2CO + 59 kcal
Due to exothermic reactions, the temperature of the bed rises and
when the temperature increases to 1000°C, air entry is stopped and steam
is passed again. Thus steam and air are blown alternatively. Therefore,
the manufacture of water gas is intermittent.
(d) Properties It has a high calorific value and burns with a
nonluminous flame. Its flame is short but very hot.
(e) Uses
• It is used for the manufacture of ammonia by Haber’s process.
• Carbureted water gas (water gas + oil gas) is used for lighting and
heating purposes.
• Water gas is also used for welding purposes.
• It is used for the manufacture of methyl alcohol.
• It is used for the manufacture of synthetic petrol.

4.10.3 Producer Gas

It is prepared by passing air mixed with a little steam over red-hot coal
or a coke bed maintained at above 1100°C in a special reactor called
‘Gas Producer’.
(a) Composition
It is a mixture of CO and N2.
 Its average composition is
N2 = 50 %
CO = 30 %
H2 = 10 %
CO2 and CH4 = rest.
(b) Calorific Value
Its calorific value is 1800 kcal/m3.
(c) Manufacture
The furnace used for the manufacture of producer gas is known as
producer. It consists of a large airtight mild steel cylindrical tower, lined
inside with refractory bricks. At the bottom, it is provided with a pipe
for blowing air and an arrangement for removing ash. Coal is added
through a hopper at the top and producer gas comes out from an exit
near the top.
(i) Combustion Zone: When a mixture of air and little steam is passed
through a bed of red hot coal, carbon (of the coal) combines with oxygen
(of the air) in the lower part of the furnace to form CO2.
C + O2 CO2 + 97 kcal
Hopper for
coke feeding
Producer-gas outlet
Distillation zone
Reduction zone
Combustion zone
Steam
and air

Ash

Fig. 4.13 Producer gas manufacturing unit

(ii) Reduction Zone:CO2, so formed, rises up through the red-hot coal

and gets reduce to CO during its passage
CO2 + C 2CO – 39 kcal
N2 of air remain unaffected throughout the process. Thus, a mixture
of CO and N2 with traces of CO2 and hydrocarbons comes out through
the exit at the upper end of the producer.
(iii) Distillation Zone This zone is the topmost in the coke bed. The
incoming coke is heated by the outgoing hot producer gas which
distillates the volatile matter present in the coke.
(d) Properties
It is a poisonous gas.
It is insoluble in water.
It is heavier than air.
(e) Uses
• It is used as fuel for heating open-hearth furnaces (used in steel
and glass manufacture), muffle furnaces (used in coal gas and
coke manufacture).
• It provides reducing atmosphere in certain metallurgical
operations.

4.10.4 Liquefied Petroleum Gas (LPG)

LPG is a predominant mixture of propane and butane with a small
percentage of unsaturates (propylene and butylene) and some lighter C2
as well as heavier C5 fractions. Included in the LPG range are propane
(C3H8), propylene (C3H6), normal and isobutane (C4H10) and butylene
(C4H8). It is obtained as one of the top fractions in the fractional
distillation of petroleum.
LPG may be defined as those hydrocarbons, which are gaseous at
normal atmospheric pressure, but may be condensed to the liquid state
at normal temperature, by the application of moderate pressures.
Although they are normally used as gases, they are stored and
transported as liquids under pressure for convenience and ease of
handling. Liquid LPG on evaporation produces 250 times more volume
of gas.
(a) Composition of LPG
n-butane = 70 %
Isobutane = 17 %
n-propane = 11 %
Butylene and ethane = rest
(b) Calorific Value
Its calorific value is 27,000 kcal/m3.
(c) Uses
• Used as a fuel for domestic cooking
• Used for heating industrial furnaces
• Used as an alternate for gasoline in automobiles

4.10.5 Coal Gas

• It is a mixture of hydrogen and methane.
• Its calorific value is 5000 kcal/m3.
• Its approximate composition is 50% H2 + 30% CH4 + 7% CO + the
rest N2, CO2 and alkenes.
(a) Manufacture Coal gas is obtained by destructive distillation of
coal at about 1200°C in a vertical coke oven. The coke oven is made up
of silica bricks. The oven is charged from the top and closed to restrict
the entry of air.
Carbonization is carried out by burning fuel and air. Coal is
decomposed into volatile products, which leave at the top of the oven.
1200°C
Coal Coke + Coal gas
Absence of air

The coal gas is mainly composed of impurities such as tar, ammonia,

benzol and other aromatic compounds, H2S, etc.
(b) Purification of Coal Gas The coal gas is passed through a
hydraulic main to a water – cooled condenser where much of tar and
ammonia are condensed and collected. Then the gas is passed through
the other tower where water is sprayed to remove the last portions of
tar and ammonia. The gas is passed through the next tower in which
creosote oil is sprayed. Benzol and other aromatic compounds are
dissolved in the oil and recovered.
Finally, the gas enters into a purifying chamber packed with Fe2O3
which removes any sulphur compound present in the coal gas. The
purified gas is collected from the exit provided at the top of the
purifier.
(c) Uses Coal gas is used as a domestic fuel. It is used for maintaining
a reducing atmosphere in metallurgy. It is also used in smelting of metals
and alloys.

4.10.6 Biogas
Biogas typically refers to a gas produced by the biological breakdown of
organic matter in the absence of oxygen. Biogas originates from biogenic
material and is a type of biofuel.
 Biogas is made from organic waste matter after it is decomposed. The
decomposition breaks down the organic matter, releasing various gases.
The main gases released are methane, carbon dioxide, hydrogen and
hydrogen sulphide. Bacteria carry out the decomposition or fermentation.
The conditions for creating biogas have to be anaerobic, that is without
any air and in the presence of water. The organic waste matter is
generally animal or cattle dung, plant wastes, etc. These waste products
contain carbohydrates, proteins and fat material that are broken down
by bacteria. The waste matter is soaked in water to give the bacteria
a proper medium to grow. Absence of air or oxygen is important for
decomposition because bacteria then take oxygen from the waste material
itself and in the process break them down.
The cheapest and easily obtainable biogas is gobar gas, which is
produced by anaerobic fermentation of cattle dung. The biogas is burnt
to raise steam, which can drive turbines to produce electricity.
(a) Gobar Gas
There are two types of biogas plants that are used in India. The first
type is the floating gas holder and the next is the fixed concrete-dome
gas-holder type. These plants, called gobar-gas plants mainly use cattle
dung. Generally, a slurry is made from cattle dung and water, which
forms the starting material for these plants.
The general composition of biogas is
Compound %
Methane 50–75
Carbon dioxide 25–50
Nitrogen 0–10
Hydrogen 0–1
Hydrogen sulphide 0–3
Oxygen 0–2
• The main constituent present in gobar gas is methane.
• The calorific value is 5400 kcal/m3.
A well is made out of concrete. This is called the digester tank. It is
divided into two parts. One side has the inlet, from where the slurry is
fed to the tank. The tank has a cylindrical dome made of stainless steel
that floats on the slurry and collects the gas generated. Hence the name
given to this type of plant is floating gas-holder type of biogas plant. The
slurry is made to ferment for about 50 days. As more gas is made by the
bacterial fermentation, the pressure inside the steel tank increases. The
gas can be taken out through an outlet pipe. The decomposed matter
expands and overflows into the next chamber in the tank. This is then
 Fig. 4.14 Diagram of a floating gas-holder type of biogas plant

removed by the outlet pipe to the overflow tank and is used as manure
for cultivation purposes.
(b) Uses of Biogas
• Biogas is used as cooking fuel. This is because biogas burns
without smoke, has high calorific value, can be piped into kitchens
directly from a plant and is cheaper in cost.
• Biogas can be used to run electric engines such as pumps, as they
cause less air pollution.
• Biogas can be used for street lighting as it does not cause any
smoke and the illumination obtained can be made to be quite
adequate.

4.11 DETERMINATION OF CALORIFIC VALUE

BY BOMB CALORIMETER
The bomb calorimeter is used for the estimation of calorific value of a
solid or nonvolatile liquid fuel.
(a) Construction It consists of a strong cylindrical stainless-steel
container (bomb) which is capable of withstanding high pressure. At
the top, a gastight screw cap is provided to which a couple of stainless-
steel electrodes and a release valve are fitted. Oxygen is passed through
one of these tubular electrodes. A small ring is attached to this electrode
which acts as a support for the crucible. The bomb is placed in a copper
calorimeter having a known weight of water.
 The copper calorimeter is surrounded by an air jacket and a water
jacket to prevent loss of heat due to radiation. The calorimeter is
provided with an electrical stirrer for stirring water and a Beckmann
thermometer.
(b) Working A known weight of the fuel sample is taken in the crucible
and the bomb lid is closed tightly. A fine magnesium wire touching the
fuel sample is stretched across the electrode. Excess oxygen of 25–30
atm pressure is filled for complete combustion of the fuel. The bomb is
kept in a copper calorimeter containing a known weight of water. Initial
temperature of water is noted after thorough stirring. When the current
is switched on, the fuel in the crucible burns. The heat liberated by the
combustion of the fuel raises the temperature of water and the maximum
temperature obtained is recorded with continuous stirring. The calorific
value of the fuel can now be calculated as follows:
+ –

Oxygen inlet

Thermometer Stirrer

Heating coil
Sample

Ignition coil
Water jacket
Air jacket

Fig. 4.15 Bomb calorimeter

(c) Calculations
Weight of the fuel taken in the crucible =mg
Weight of the water in the calorimeter =ag
Water equivalent of the calorimeter, stirrer
bomb and thermometer =bg
Initial temperature of water in the calorimeter = T1°C
Final temperature of water in the calorimeter = T2°C
Higher calorific value of the fuel =H
Heat gained by water = a (T2 – T1) cal
Heat gained by calorimeter = b (T2 – T1) cal
 Total heat gained = a (T2 – T1) + b (T2 – T1) cal
= (a + b) (T2 – T1)
Heat liberated by the fuel =m×H
Now, heat liberated by the fuel = Heat gained by water and
calorimeter
m × H = (a + b) (T2 – T1)
(a + b) (T2 – T1)
H (GCV or HCV) = ______________
m cal/g
NCV can be calculated based on Dulong’s formula.
To obtain accurate results, the following corrections are made.
(i) Fuse-wire Correction: The heat released by the magnesium fuse wire
is to be subtracted from the total calorific value.
(ii) Acid Correction:During ignition, suphur and nitrogen present in the
fuel are oxidized to the corresponding acids.
S + 2H + 2O2 H2SO4 + Heat
2N + 2H + 3O2 2HNO3 + Heat
The heat liberated by the formation of these acids must be
subtracted.
(iii) Cooling Correction:During cooling, the calorimeter will lose some
amount of heat. To calculate this heat wasted during cooling; the rate of
cooling (d t°/min) and actual time for cooling (x minutes) are measured.
The cooling correction is added to the temperature difference.
(a + b) (T2 – T1 + Cooling correction) – (Acid + Fuse-wire correction)
H = ___________________________________________________
m cal/g

Example 6 Calculate the volume of air (volume % of O2 in air = 21)

required for complete combustion of 1 litre of CO.
Solution The combustion equation of CO is written as follows:
CO + 1/2 O2 CO2
1 vol 0.5 vol

One volume (litre) of CO requires 0.5 volume (litre) of O2 for complete

combustion.
We know that,
21 litres of O2 is supplied by 100 litres of air.
100 × 0.5
\ 0.5 litres of O2 is supplied by ________ lit of air
21
= 2.38 litres of air
Result
The volume of air required for the complete combustion of 1 litre of CO
= 2.38 litres

Example 7 What is the volume of air required for the complete combustion
of 1 m3 of a mixture containing 75 % of CH4 and 25 % of C2H6?
Solution
(a) 1 m3 of the mixture contains
75
____ = 0.75 m3 of CH4
100
25
____ = 0.25 m3 of C2H6
100
(b) The combustion equations of CH4 and C2H6 are written as
follows:
(i) CH4 + 2O2 CO2 + 2H2O
1 vol 2 vol

i.e. 1 volume (or m3) of CH4 requires 2 volumes (or m3) of

O2 for complete combustion.
2 × 0.75
\ 0.75 m3 of CH4 requires = _______ = 1.5 m3 of O2
1
(ii) C2H6 + 7/2 O2 2CO2 + 3H2O
1 vol 3.5 vol

i.e. 1 volume (or m3) of C2H6 requires 3.5 volumes (or m3) of
O2 for complete combustion.
3.5 × 0.25
\ 0.25 m3 of C2H6 requires = _________ = 0.875 m3 of O2
1
(c) Total volume of O2 required
= 1.5 + 0.875 m3
= 2.375 m3
We know that
21 m3 of O2 is supplied by 100 m3 of air.
2.735 × 100
\ 2.735 m3 of O2 is supplied by __________ = 11.31 m3 of air
21
Result
The volume of air required for the complete combustion of 1 m3 of
mixture = 11.31 m3
Example 8 Calculate the minimum volume of air required for the complete
combustion of 1 m3 of a gaseous fuel containing the following composition by
volume: CO = 25 %, H2 = 10 %, CH4 = 08 %, CO2 = 5 %, N2 = 50 % and
O2 = 2 %.
Solution
1 m3 of fuel contains
25
(a) ____ = 0.25 m3 of CO
100
10
(b) ____ = 0.10 m3 of H2
100
8
(c) ____ = 0.08 m3 of CH4
100
5
(d) ____ = 0.05 m3 of CO2
100
50
(e) ____ = 0.50 m3 of N2
100
2
(f) ____ = 0.02 m3 of O2
100
N2 and CO2 are noncombustible constituents. They do not burn and
do not require any oxygen.
The combustion equations of the remaining constituents are written
as follows:
(i) CO + 1/2 O2 CO2
1 vol 0.5 vol

i.e. 1 volume (or m3) of CO requires 0.5 volume (or m3) of O2 for
complete combustion.
0.5 × 0.25
\ 0.25 m3 of CO requires = _________ m3 of O2
1
= 0.125 m3 of O2
(ii) H2 + 1/2 O2 H2O
1 vol 0.5 vol

i.e. 1 volume (or m3) of H2 requires 0.5 volume (or m3) of O2 for
complete combustion.
0.5 × 0.1
\ 0.10 m3 of H2 requires = ________ m3 of O2
1
= 0.05 m3 of O2
 (iii) CH4 + 2O2 CO2 + 2H2O
1 vol 2 vol

i.e. 1 volume (or m3) of CH4 requires 2 volumes (or m3) of O2 for
complete combustion.
0.08 × 2
\ 0.08 m3 of CH4 requires = _______ m3 of O2
1
= 0.16 m3 of O2
Total volume of O2 required = 0.125 + 0.05 + 0.16 m3
= 0.335 m3 of O2
\ net volume of O2 required = Total volume of O2 required –
O2 already present in the fuel.
3
= 0.335 – 0.02 m of O2
= 0.315 m3 of O2
We know that
21 m3 of O2 is supplied by 100 m3 of air.
0.315 × 100
\ 0.315 m3 of O2 is supplied by = __________
21
= 1.5 m3 of air.
Result
The volume of air required for the complete combustion of 1 m3 of the
gaseous fuel = 1.5 m3

Example 9 A fuel contains C = 60 %, H2 = 09 %, O2 = 08 %, S = 13 %,

and the remaining is ash. Calculate the minimum quantity of air required for
the complete combustion of 1 kg of the fuel.
Solution
1 kg of fuel contains
60
(a) ____ = 0.60 kg of carbon
100
10
(b) ____ = 0.09 kg of hydrogen
100
08
(c) ____ = 0.08 kg of oxygen
100
13
(d) ____ = 0.13 kg of sulphur
100
The combustion equations of the various elements present in the fuel
are as follows:
 (i) C + O2 CO2
12 kg 32 kg

i.e. 12 kg of carbon requires 32 kg of oxygen for complete

combustion.
32 × 0.6
\ 0.60 kg of carbon requires _______ kg of O2 = 1.6 kg of O2
12
(ii) H2 + 1/2 O2 H2O
2 kg 16 kg

i.e. 2 kg of hydrogen requires 16 kg of oxygen for complete

combustion.
16 × 0.09
\ 0.09 kg of H2 requires ________ kg of O2 = 0.72 kg of O2
2
(iii) S + O2 SO2
32 kg 32 kg

i.e. 32 kg of sulphur requires 32 kg of oxygen for complete

combustion.
32 × 0.13
\ 0.13 kg of S requires ________ kg of O2 = 0.13 kg of O2
32
Total amount of O2 required = 1.60 + 0.72 + 0.13 kgs
= 2.45 kg of O2
But the amount of O2 already present in the fuel = 0.08 kg
\ Net amount O2 required = Total amount of O2 required –
O2 already present in the fuel
= 2.45 – 0.08 kg of O2
= 2.37 kg of O2
We know that
23 kg of O2 is supplied by 100 kg of air.
2.37 × 100
\ 2.37 kg of O2 is supplied by _________ = 10.30 kg of air
23
Result
The minimum amount of air required for the complete combustion of
1 kg of the fuel = 10.30 kg.

Example 10 Calculate the minimum amount of air required for the complete
combustion of 50 kgs of coal containing C = 75 %, H2 = 10 %, O2 = 02 %,
S = 05 %, and the rest nitrogen by weight.
Solution
1 kg of fuel contains
 75
(a) ____ = 0.75 kg of carbon
100
10
(b) ____ = 0.10 kg of hydrogen
100
2
(c) ____ = 0.02 kg of oxygen
100
5
(d) ____ = 0.05 kg of sulphur
100
N2 is a noncombustible constituent. It does not burn and does not
require any oxygen.
The combustion equations of the various elements present in the coal
are as follows:
(i) C + O2 CO2
12 kg 32 kg

i.e. 12 kg of carbon requires 32 kg of oxygen for complete

combustion.
32 × 0.75
\ 0.75 kg of carbon requires ________ kg of O2 = 2.0 kg of O2
12
(ii) H2 + 1/2 O2 H2O
2 kg 16 kg

i.e. 2 kg of hydrogen requires 16 kg of oxygen for complete

combustion.
16 × 0.10
\ 0.10 kg of H2 requires ________ kg of O2 = 0.80 kg of O2
2
(iii) S + O2 SO2
32 kg 32 kg

i.e. 32 kg of sulphur requires 32 kg of oxygen for complete

combustion.
32 × 0.05
\ 0.05 kg of S requires ________ kg of O2 = 0.05 kg of O2
32
Total amount of O2 required = 2.00 + 0.80 + 0.05 kg
= 2.85 kg
But the amount of O2 already present in the fuel = 0.02 kg
\ net amount O2 required = Total amount of O2 required –
O2 already present in the fuel.
= 2.85 – 0.02 kg
= 2.83 kg
We know that
23 kg of O2 is supplied by 100 kg of air.
 2.83 × 100
\ 2.83 kg of O2 is supplied by _________ = 12.30 kg of air
23
The amount of air required for 1 kg of coal = 12.30 kg
\ the amount of air required for 50 kg of coal = 12.30 × 50 kg
= 615 kg
Result
The amount of air required for the complete combustion of 50 kg of the
coal = 615 kg

Example 11 Calculate the minimum amount of air required for the complete
combustion of 150 kg of fuel containing 70 % carbon, 15 % hydrogen, 5 %
sulphur and the rest nitrogen by weight.
Solution
1 kg of fuel contains
70
(a) ____ = 0.70 kg of carbon
100
15
(b) ____ = 0.15 kg of hydrogen
100
05
(c) ____ = 0.05 kg of sulphur
100
N2 is a noncombustible constituent. It does not burn and does not
require any oxygen.
The combustion equations of the various elements present in the coal
are as follows:
(i) C + O2 CO2
12 kg 32 kg

i.e. 12 kg of carbon requires 32 kg of oxygen for complete

combustion.
0.7 × 32
\ 0.70 kg of carbon requires _______ kg of O2 = 1.87 kg of O2
12
(ii) H2 + 1/2 O2 H2O
2 kg 16 kg

i.e. 2 kg of hydrogen requires 16 kg of oxygen for complete

combustion.
0.15 × 16
\ 0.15 kg of H2 requires ________ kg of O2 = 1.20 kg of O2
2
(iii) S + O2 SO2
32 kg 32 kg
 i.e. 32 kg of sulphur requires 32 kg of oxygen for complete
combustion.
0.05 × 32
\ 0.05 kg of S requires ________ kg of O2 = 0.05 kg of O2
32
Total amount of O2 required = 1.87 + 1.20 + 0.05 kg
= 3.12 kg
We know that
23 kg of O2 is supplied by 100 kg of air.
3.12 × 100
\ 3.12 kg of O2 is supplied by _________ = 13.57 kg of air
23
The minimum amount of air required for the complete combustion
of 1 kg of fuel = 13.57 kg
\ the minimum amount of air required for the complete combustion of
50 kg of fuel = 13.57 × 150 kg
= 2035.5 kg
Result
The minimum amount of air required for the complete combustion
of 150 kg of the fuel = 2035.5 kg

Example 12 Calculate the weight and volume of air required for the complete
combustion of 1 kg of coke or carbon.
Solution The combustion equation of carbon is as follows:
C + O2 CO2
12 kg 32 kg

12 kg of carbon requires 32 kg of O2 for complete combustion.

32 × 1
\ 1 kg of coke requires ______ = 2.67 kg of O2
12
We know that,
23 kg of O2 is supplied by 100 kg of air.
2.67 × 100
\ 2.67 kg of O2 is supplied by _________ = 11.61 kg of air.
23
We know that,
1 g mole of any substance occupies 22.4 litres
(or)
32 kg of O2 occupies 22.4 m at NTP [1 m3 = 1000 litres]
3

22.4 × 1.61
\ 11.61 kg of O2 occupies __________ = 8.127 m3
32
 We know that,
21 m3 of O2 is supplied by 100 m3 of air.
8.127 × 100
\ 8.127 m3 of O2 is supplied by __________ = 38.70 m3 of air
21
Result
1. The amount of air required for complete combustion of 1 kg of
coke = 11.61 kg
2. The volume of air required for complete combustion of 1 kg of
coke = 38.70 m3.

Example 13 Calculate the minimum theoretical quantity of air needed for

the combustion of 10 kg of coal which is 95 % pure.
Solution The combustion equation of carbon is as follows:
C + O2 CO2
12 kg 32 kg

i.e. 12 kg of carbon requires 32 kg of oxygen for complete combustion.

32 × 10
\ 10 kg of carbon requires _______ kg of O2 = 26.67 kg of O2
12
We know that
23 kg of O2 is supplied by 100 kg of air.
26.67 × 100
\ 26.67 kg of O2 is supplied by __________ kg of air
23
= 115.96 kg of air.
The amount of air required for the combustion of 10 kg of coal which
is 100 % pure = 115.96 kg
The amount of air required for the combustion of 10 kg of coal which
115.96 × 95
is 95 % pure = __________ = 110.16 kg
100
Result
The amount of air required for the combustion of 10 kg of coal which
is 95 % pure = 110.16 kg

Example 14 A sample of coal was found to have the following percentage

composition: C = 75 %, H2 = 5.2 %, O2 = 12.8 %, N2 = 1.2 %, S = 12.8 %
and the rest ash. Calculate the amount of air needed for the complete combustion
if 1 kg of the coal is burnt with 30 % excess air.
Solution
1 kg of coal contains
75
(a) ____ = 0.75 kg of carbon
100
5.2
(b) ____ = 0.052 kg of hydrogen
100
12.8
(c) ____ = 0.128 kg of sulphur
100
12.8
(d) ____ = 0.128 kg of oxygen
100
1.2
(e) ____ = 0.012 kg of nitrogen
100
N2 and ash are noncombustible constituents. They do not burn and
do not require any oxygen.
The combustion equations of the remaining constituents present in
the fuel are as follows:
(i) C + O2 CO2
12 kg kg

i.e. 12 kg of carbon requires 32 kg of oxygen for complete

combustion.
32 × 0.75
\ 0.75 kg of carbon requires ________ kg of O2 = 2.0 kg of O2
12
(ii) H2 + 1/2 O2 H2O
2 kg 16 kg

i.e. 2 kg of hydrogen requires 16 kg of oxygen for complete

combustion.
16 × 0.052
\ 0.052 kg of H2 requires _________ kg of O2 = 0.416 kg of O2
2
(iii) S + O2 SO2
32 kg 32 kg

i.e. 32 kg of sulphur requires 32 kg of oxygen for complete

combustion.
32 × 0.128
\ 0.128 kg of S requires _________ kg of O2 = 0.128 kg of O2
32
Total amount of O2 required = 2.00 + 0.416 + 0.128 kgs
= 2.544 kg of O2
But the amount of O2 already present in the fuel = 0.128 kg
\ Net amount O2 required = Total amount of O2 required –
O2 already present in the fuel.
= 2.544 – 0.128 kg of O2
= 2.416 kg of O2
We know that
23 kg of O2 is supplied by 100 kg of air.
100 × 2.416
\ 2.416 kg of O2 is supplied by __________ = 10.50 kg of air
23
Theoretical air × [100 + excess air]
If 30 % excess air is used = _______________________________
100
10.5 × [100 + 30]
= _______________
100
= 13.65 kg of air
Result
The volume of air required for the complete combustion of 1 kg of the
fuel if 30 % excess air is used = 13.65 kg

QUESTIONS

Two-Mark Questions with Answers

1. Define fuel.
Fuel can be defined as any combustible substance which on proper
burning gives large amount of energy in the form of heat, which
can be used economically for domestic and industrial purpose.
2. What is combustion?
Combustion or burning is the sequence of exothermic chemical
reactions between a fuel and an oxidant accompanied by the
production of heat and conversion of chemical species.
3. What is meant by calorific value?
It is the most important characteristic property of any [Link]fic
value may be defined as ‘the amount of heat liberated by the
complete combustion of a unit mass of a fuel’.
4. What is meant by Higher Calorific Value (HCV)?
It is the total heat generated when a unit quantity of fuel is
completely burnt and the products of combustion are cooled to
room temperature.
 5. What are the significance of flue-gas analysis?
1. Based on the composition of the flue gas, it is possible to
predict the complete or incomplete combustion process.
2. If the flue gas contains any CO, it indicates the incomplete
combustion in the combustion chamber and short supply of
oxygen.
3. If the flue gas contains O2, it indicates that excess of air is
supplied. It is essential to reduce the air supply.
6. What is ultimate analysis of coal?
The determination weight percentage of carbon, hydrogen,
nitrogen, oxygen and sulphur of the pure coal free from moisture
and inorganic constituents is called ultimate analysis.
7. Why is coke superior as a metallurgical fuel?
Coke is superior as a metallurgical fuel, because
1. Coke is stronger and more porous than coal
2. Coke contains lesser amount of sulphur than coal
3. Coke does not contain much volatile matter
8. What is metamorphism of coal?
The process of conversion of lignite to anthracite is called
coalification or metamorphism of coal.
9. Define refining of petroleum.
The process of removing impurities and separating out the oil
into various fractions having different boiling points is known as
refining of petroleum.
10. How are coals classified?
Coal is classified on the basis of its rank. The rank of coal denotes
its degree of maturity. Vegetable matter, under the action of
pressure, heat and anaerobic conditions, gets converted into
different stages of coal, namely
Peat Lignite Sub-bituminous Bituminous Anthracite
11. What is metallurgical coke?
When bituminous coal is heated strongly in absence of air, the
volatile matter escapes out and a lustrous, dense, strong, porous
and coherent mass is left, which is called metallurgical coke.
12. Define cracking.
Cracking is defined as ‘the decomposition of high boiling
hydrocarbons of high molecular weight into smaller, low boiling
hydrocarbons of low molecular weight’.
13. What are the advantages of Otto Hoffman’s by-product
method?
Otto Hoffman’s by-product method has the following
advantages:
1. High thermal efficiency and less carbonization time
2. Valuable by-products (like coal gas, ammonia, benzene, etc.)
are recovered as by products
3. Heating done externally by producer gas
14. Write any four differences between straight-run petrol and
cracked petrol.
[Link] Straight-run Petrol Cracked Petrol
1. Obtained from straight distillation of crude oil. Obtained from heavy oil
2. Contains only n-alkanes. Contains iso-paraffins and aromatics
3. Composition range C5 – C9 Narrow range
4. Low octane number Higher octane number

15. What is meant by octane number?

Octane number can be defined as ‘percentage of iso-octane present
in iso-octane and n-heptane mixture, which matches the same
knocking characteristics of a gasoline mixture test sample’.
16. Write any five differences between petrol and diesel.
[Link] Petrol Diesel
1. Low boiling petroleum (C5 – C10) High boiling fraction of petroleum contains
C15– C18 hydrocarbons
2. Fuel for SI engine Fuel for CI engine
3. Knocks due to premature ignition Knocks due to ignition delay
4. Knocking tendency measured in Knocking tendency measured in
octane rating cetane rating.
5. Anti-knocking is improved through Anti-knocking is improved by doping with
addition of TEL isoamyl nitrate

17. What is the average composition of water gas?

The average composition is
H2 = 48 %
CO = 44 %
CO2, N2 and CH4 = rest
18. Mention any two applications of producer gas.
1. It is used as fuel for heating open-hearth furnaces (used in
steel and glass manufacture), muffle furnaces (used in coal
gas and coke manufacture).
 2. It provides reducing atmosphere in certain metallurgical
operations.
19. What is meant by cetane number?
Cetane number is defined as the percentage of cetane present in a
mixture of a -methyl naphthalene and cetane, which matches the
same knocking characteristics of a diesel mixture test sample.
20. What is the average composition of liquefied petroleum gas?
Composition of LPG
n-butane = 70 %
Isobutane = 17 %
n-propane = 11 %
Butylene and ethane = rest
21. Classify the hydrocarbons based on their knocking tendency in
CI engines.
The knocking tendency in CI engines increases as follows:
n-alkane Isoparaffins Olefins Naphthenes Aromatics

Ten-Mark Questions
1. Discuss in detail the flue gas analysis using Orsat’s apparatus.
2. Explain in detail the classification of solid fuels.
3. Discuss the proximate analysis of coal with its significances.
4. Explain the manufacture of metallurgical coke by beehive coke
oven method.
5. Explain the construction and operation of Otto Hoffman’s by-
product coke oven with a neat diagram.
6. Discuss in detail the Bergius process of petrol manufacturing.
7. Explain the Fischer–Tropsch process of synthetic petrol
manufacturing.
8. What is water gas? Discuss the preparation, properties and uses.
9. Explain the manufacture of producer gas with a neat diagram.
10. Discuss the ultimate analysis of coal in detail.
11. What is knocking in Petrol and Diesel? How will you overcome
the knocking problem?
12. How is synthetic petrol manufactured by polymerization and
alkylation methods?
 UNIT

5
High Polymers

5.1 INTRODUCTION
The word polymer is derived from the Greek words poly meaning
‘many’ and mers meaning ‘units’ or ‘parts’. Polymers are generally
macromolecules formed by the repeated linking of a large number of
small molecules. The chemistry of these giant molecules is known as
‘polymer chemistry’ or ‘macromolecular chemistry’. Cellulose, starch,
proteins, rubber, resins, etc., are some common examples of naturally
occurring polymers. Polymers are widely used in automobiles, defense,
electrical goods and computer components. Polymers may be both
inorganic and organic in nature. The organic polymers, particularly
the synthetic ones, are more important and are the chief products of
modern chemical industry. Hermann Staudinger, (1881–1963), a German
chemist and one of the pioneers in polymer chemistry was awarded the
Nobel Prize in chemistry in 1953 for his outstanding research. In the
forthcoming sections, we shall study some important aspects related to
organic polymers, particularly the synthetic ones.

5.1.1 Polymers
Polymers are macromolecules built up by linking together a large number
of small molecules called monomers.
Example
Polyethylene is a polymer formed by the repeated linking of a large
number of ethylene molecules. These units are linked together by
covalent bonds.
 n CH2 = CH2 —(CH2 — CH2)—
n
Ethylene (monomer) Polyethylene (polymer)

5.1.2 Monomer
A monomer is the building block or structural unit of a polymer. It is a
small molecule that combines with other molecules to form a polymer.
Example Ethylene

5.2 POLYMERIZATION
Polymerization is a process in which a large number of small molecules
combine to form a bigger molecule with or without elimination of the
small molecules like water, methanol, etc.

5.2.1 Degree of Polymerization (DP)

The size of a polymer molecule is represented in terms of degree of
polymerization. The number of repeating units or monomers present in
a polymer chain is known as degree of polimerization (n). In a polymer
molecule, there may be hundreds or thousands or more monomer
molecules linked together. It is represented by the following relation.
Degree of Polymerization (DP)
Molecular weight of the polymeric network
= _______________________________________
Molecular weight of the repeating unit

Example

4 CH2 = CH2 —CH2—CH2—CH2—CH2—CH2—CH2—CH2—CH2—

Here, there are four repeating units present in the polymer chain. So the
degree of polymerization is 4.
They are polymers with a low degree of polymerization
(i) Oligo Polymers
and have a 500–5000 molecular mass range.
They are polymers with high degree of polymerization
(ii) High Polymers
and have a 10,000–2,00,000 molecular mass range.

5.3 NOMENCLATURE OF POLYMERS

Depending upon the nature of monomeric units, polymers can be
categorized into the following categories:
 1. Homopolymer
2. Heteropolymer
3. Homochain polymer
4. Heterochain polymer
5. Stereospecific polymer

5.3.1 Homopolymer
If the polymer consists of identical monomers, it is a homopolymer.
—M—M—M—M—M
where, M is a monomer.
Example Polyethylene, Polypropylene.
Types Homopolymers are subdivided into three types based on the
manner in which monomers are arranged.
(i) Linear Homopolymer
A polymer in which the constituent monomeric units are joined together
to form long straight chains is called a linear homopolymers.
—M—M—M—M
where M is a monomer.
(ii) Branched Homopolymer
Polymers which consist of side chains attached to the main chain are
called branched homopolymers.

—M—M—M—M—

(iii) Cross-linked Homopolymer

Polymers in which the adjacent polymeric chains link together through
side chains to form a three-dimensional network structure are called
cross-linked homopolymers.
 —M—M—M—M—

—M—M—M—M—

—M—M—M—M—

5.3.2 Copolymer (or) Heteropolymer

A polymer having different types of monomers is known as a
copolymer.
Example Nylon, Terylene.
— M1 — M2 — M1 — M2 — M1 —
where M1 and M2 are two different monomers.
Types Copolymers are subdivided into four types.
(i) Regular Copolymer Monomeric units are arranged regularly.
— M1 — M2 — M1 — M2 — M1 — M2 —
(ii) Random Copolymer Here, monomeric units are arranged
randomly.
— M1 — M2 — M1 — M1 — M2 — M1 —
(iii) Block Copolymer It is a linear copolymer in which the monomeric
units appear as blocks.
— M1 — M1 — M1 — M2 — M2 — M2 — M1 — M1 — M1 —
(iv) Graft Copolymer It is a branched copolymer with one type of
monomer (M1) in the backbone and another kind of monomer (M2) in
the branches.
—M1—M1—M1—M1—M1—

M2

M2

M2
5.3.3 Homochain Polymer
If the main chain is made up of the same species of atoms, the polymer
is called a homochain polymer.
Example Polyethylene, Polyvinyl chloride, Polystyrene, etc.
—C—C—C—C—C—C—

5.3.4 Heterochain Polymer

If the main chain is made up of different atoms, the polymer is called a
heterochain polymer.
Example Terylene, Nylon 6:6, Nylon 6, etc.
—C—C—N—C—C—N—C—C—

5.3.5 Stereospecific Polymer or Tacticity

In a polymeric molecule, the arrangement of functional groups, either by
an orderly or disorderly manner, with respect to the main chain is called
tacticity. Tacticity affects the physical properties of the polymer.
Tacticity originated from the Greek word ‘taktikos’ that means relating
to arrangement or order. This orientation results in three types of stereo-
regular polymers as follows.
(a) Isotactic Polymer
Polymers in which the functional groups are all located on the same side
of the main chain are called isotactic polymers.
Example Polystyrene
H H H H

CH CH2 C — CH2 — C — CH2 — C — CH2 — C

Styrene Isotactic polystyrene

(b) Syndiotactic Polymer

If there is arrangement of functional groups in an alternating fashion
around the main chain, the polymer is called a syndiotactic polymer.
 H H

CH CH2 C — CH2 — C — CH2 — C — CH2 — C

H H

Styrene Syndiotactic polystyrene

(c) Atactic Polymer

If the arrangement of functional groups is located at a random manner
around the main chain, the polymer is called an atactic polymer.
Example

H H H

CH CH2 C — CH2 — C — CH2 — C — CH2 — C

Styrene Atactic polystyrene

5.4 FUNCTIONALITY
All types of organic molecules cannot act as monomers. An organic
molecule acts as a monomer only when it possesses at least two reactive
sites or bonding sites. Functionality is the number of bonding sites or
reaction sites present in the monomer.
• •
Example n CH2 = CH2 (— CH2 — CH2 —)n
where • bonding site (or) reaction site
(a) Monofunctional
There is only one bonding site in the monomer and thus they are used
as terminators or chain stoppers in polymerization reactions.
• •
Example CH3COOH, CH3OH
(b) Bifunctional
There are two bonding sites in the monomer and thus a linear polymer
is formed.
• • • •
Example CH2 = CH2, CH2 = CH Cl

(c) Trifunctional
There are three bonding sites in the monomer and hence a cross-linked
three-dimensional network polymer is formed.
Example
•
CH2OH
•
CHOH
•
CH2OH

5.5 TYPES OF POLYMERIZATION

Polymerization

Addition Condensation Co-Polymerization Coordination

Polymerization Polymerization Polymerization
or or
Chain growth Stepwise
Polymerization Polymerization

5.5.1 Addition or Chain-growth Polymerization

It is a reaction that yields a polymer which is an exact multiple of the
original monomeric molecule.
Examples
(i) Polyethylene is produced from ethylene.
Heat/Pressure
n CH2 CH2 — (CH2 — CH—-
2)n
Catalyst
Ethylene Polyethylene (PE)
(ii) Polyvinyl chloride is produced from vinyl chloride.
Polymerization
n CH2 CH — (CH2 — CH)n —

Cl Cl
Vinyl chloride PVC

(iii) Polystyrene is produced from styrene.

Polymerization
n CH2 CH — (CH2 — CH)n —

C6H5 C6H5
Styrene Polystyrene

• The molecular weight of the polymer is an exact multiple of the

monomer.
• Addition polymerization occurs in monomers that contain at least
one double bond or triple bond.
• This type of polymerization takes place under suitable conditions,
i.e. in the presence of a suitable catalyst and by applying
appropriate pressure and temperature.
• An addition polymer is produced by adding a second monomer
to the first, and then the third monomer, and so on, until the long
chain is produced.

5.5.2 Mechanism of Addition Polymerization

The mechanism of addition polymerization can be explained by any one
of the following three types.
1. Free-radical mechanism
2. Ionic mechanism
3. Coordination mechanism or Zeigler–Natta mechanism
All the above mechanisms occur in three consecutive steps, namely,
(i) Initiation,
(ii) Propagation, and
(iii) Termination.
Free-radical Mechanism
Free-radical polymerization is initiated by organic peroxides which
decompose to give free radicals. Free radicals are highly reactive species
due to the presence of unpaired electrons.
(i) Initiation It involves two reactions.
1. Formation of Free Radical as well as Reactive Species
It involves formation of free radicals by homolytic dissociation of an
initiator to yield a pair of free radicals (R·)
I 2R•
(Initiator) (Free radicals)

Examples
A thermal initiator is a substance used to produce free radicals by
homolytic dissociation at high temperature.
(i) CH3COO-OOCCH3 2 (CH3COO)• (or) 2R•
Acetyl peroxide Free radicals

(ii) C6H5COO-OOC C6H5 2 (C6H5COO)• (or) 2R•

Benzoyl peroxide Free radicals

2. The free-radical, thus produced, attaches to a first monomer to produce

a chain-initiating species.
R• + M M1•
Free radical monomer Chain initiating species

Thus, polymerization of the monomer CH2 = CHY takes the form

H H
• •
R + CH2 C R — CH2 C

Y Y
(Chain-initiating species)

The radical R• is referred as initiator radical or a primary radical.

(ii) Propagation It involves the addition of monomer molecules to a
chain-initiating species facilitating the growth of polymer chain.
M1• + M M2•; M•2 + M M3•
or in general, Mn• + M M•n + 1
H H H H
• •
R — CH2 — C + n CH2 C R — (CH2 — C)n — CH2 — C

Y Y Y Y
Growing chain
(Living polymer)
 The growing chain of the polymer is known as a living polymer.

(iii) TerminationThe growth of polymer chain is terminated either by a

coupling reaction or disproportionation.

1. Coupling or Combination
In a coupling reaction, two free-radical polymer chains combine together
to form a dead polymer (macromolecule).

H H H H
• •
R — CH2 — C + C — CH2 — R R — CH2 — C — C — CH2 — R

Y Y Y Y
Macromolecule
(Dead polymer)

2. Disproportionation
This reaction involves the transfer of a hydrogen atom from one of the
free radical polymer chain to another free radical giving rise to one
saturated and one unsaturated polymer molecule.

H H H H H H H H
• •
R—C—C + C—C—R R—C C + H—C—C—R

H Y Y H Y Y H
Unsaturated Saturated
macromolecule macromolecule
(Dead polymer)

The product of addition polymerization is known as a dead

polymer.

5.5.3 Condensation Polymerization or

Stepwise Polymerization
This reaction involves the condensation of two functional groups present
in the same kind of monomer or different kind of monomers by the
elimination of small molecules like H2O, HCl, NH3, CH3OH, etc.,
(a) Condensation Reaction Between two Different Monomers
Example

–2n H2O
nH2N—(CH2)6—NH2 + n HOOC—(CH2)4—COOH
Hexamethylenediamine Adipic acid

—(NH—(CH2)6—NH—CO—( CH2)4—CO —
)n
Nylon 6 : 6 (Polyamide)

Nylon 6:6 derives its name from the starting materials, adipic acid and
hexamethylene diamine, both of which have six carbon atoms. From the
above illustration, the following conclusions can be drawn regarding
condensation polymerization.
(i) The monomer should have two reactive functional groups.
(ii) The polymerization proceeds by stepwise reaction between
reactive functional groups.
(iii) In some cases, both reactive functional groups could be present
on the same monomer. In that case, it can lead to a self-
polycondensation reaction.
(b) Self-condensation of a Monomer Having Different
Functional Groups
• Self-condensation of w-amino caproic acid
n H2N-(CH2)5-COOH —( HN-(CH2)5-CO)n—
w-amino caproic acid Nylon-6

• Self-condensation of w-amino decanoic acid

n H2N-(CH2)10-COOH —( HN-(CH2)10-CO)n—
Nylon-11

(c) Ring-opening Polymerization

In some cases, condensation polymers are obtained without the
elimination of small molecules but it takes place by just opening of cyclic
compounds. This type of polymerization is known as ring-opening
polymerization.
CH2

CH2 NH

n CH2 CO —(NH–(CH2)5 — CO)—

n
Nylon 6
CH2 CH2

Caprolactum
5.5.4 Co-polymerization
Co-polymerization is the joint polymerization of two or more different
monomeric species. High-molecular-weight polymers obtained by co-
polymerization are called co-polymers. In this process, no side products
are formed. Co-polymerization can be used to obtain polymeric materials
with new properties.
Example (i) Co-polymerization of styrene and butadiene forms Styrene-
Butadiene Rubber (SBR) which has superior properties than ordinary
synthetic butadiene rubber.
n CH2 CH — CH CH2 + n CH2 CH
Butadiene
C6H5
Styrene

—[CH2 — CH CH — CH2 — CH2 — CH]—

n

C6H5
Styrene Butadiene Rubber (SBR)

Example (ii) Co-polymerization of acrylonitrile and vinyl chloride is

readily soluble in acetone but polyvinyl chloride and polyacrylonitrile
are soluble only at higher temperatures.

n H2C CH + n H2C CH — H2C — CH — CH2 — CH —

Cl CN Cl CN n
Vinyl chloride Acrylonitrile Poly(vinylchloride-co-acrylonitrile)

• Chemical and geometrical shapes of polymers can be varied by

this reaction and hence it is used to produce unsymmetrical or
irregular shape polymers.
• Therefore, co-polymerization is superior than other polymerization
reactions because it can control various polymeric properties such
as hardness, toughness, flexibility, heat resistance, solubility,
crystallization tendency, etc.

5.5.5 Coordination or Zeigler–Natta Polymerization

Two scientists, Zeigler and Natta, were awarded the Nobel Prize in
1963 for their outstanding discovery of coordination polymerization.
They prepared a coordination complex called Zeigler–Natta catalyst,
by reacting a transition metal halide (like TiCl4, TiCl3 , TiCl2, ZrBr3,
etc.) with organometallic compounds (like triethyl aluminium,
trimethyl aluminium). Using the Zeigler–Natta catalyst, stereospecific
polymerization can be carried out. The structure of a typical Zeigler–
Natta catalyst is shown below:

R R Cl

Al Ti
R Cl Cl

Many other examples exist:

Organometallic Compound Transition Metal Salt
Triethyl aluminium Titanium tetrachloride
Diethyl AlCl3 Vanadium trichloride
Diethyl AlCl2 Triacetyl acetone vanadium
Butyl lithium Titanium tetrachloride

It yields polymers of high density and high melting points. In order

to explain the mechanism of Zeigler–Natta polymerization, the catalyst
is generally represented as Cat-R.
Mechanism
The monomers like propylene, isoprene, etc., follow this mechanism.
(i) Initiation This is the formation of chain-initiating species in which
monomer is inserted in between transition metal and alkyl group.

H H H H
Cat-R +
C C Cat — C C—R
Zeigler–Natta
Catalyst H CH3 H CH3
Monomer Chain-initiating
species

(ii) PropagationHere, the growth of a chain-initiating species is carried

out by successive insertion of more number of monomers between the
metal and alkyl group.

H H H H H H H H

Cat — C — C — R + n C = C Cat — (C — C)n — C — C — R

H CH3 H CH3 H CH3 H CH3

Growing chain
 The termination process is carried out by addition of
(iii) Termination
an active hydrogen compound (HX).

Polymerization
n CH2 CH — (CH2 — CH)n —

C6H5 C6H5
Styrene Polystyrene

5.6 EFFECT OF POLYMER STRUCTURE ON

PROPERTIES
The physical, chemical and mechanical properties of a polymer are
determined by the nature of monomer units and its structure. The
structure acquired by a polymer depends upon the formation and
arrangement of its constituent macromolecules. There are several factors
involved in deciding the structure and hence the properties of a polymer.
They are
1. Strength,
2. Plastic deformation,
3. Crystallinity, and
4. Chemical resistance.

5.6.1 Strength
The strength of a polymer is its resistance to change of shape and mainly
depends on the following three factors.
1. Type of attractive forces between molecules. These attractive forces
are of two types.
(i) Strong covalent bond forces
(ii) Weak van derWaals forces
2. Molecular weight
3. Slipping power
(a) Strength of Linear and Branched-chain Polymers
(i) Types of Attractive Forces: In straight-chain and branched-chain
polymers, the individual chains are held by weak van derWaals forces
of attraction and they are soft and flexible.
The strength can be increased by increasing the intermolecular van
derWaals forces. The intermolecular forces can be greatly increased by
the presence of the polar groups like –OH, -COOH, -Cl, -CN, etc., along
the chain length, e.g. Nylon, Teflon, etc
(ii) Molecular Weight: Polymers of low

Degree of polymerization
molecular weights are quite soft and gummy
but brittle to impact at low temperature. But
higher-chain polymers are tough and more
heat resistant. Thus, by controlling the chain
length (or molecular weight), it is possible to
vary the physical properties of the polymer
from soft and flexible to hard and hornlike
substances. Tensile strength
(iii) Slipping Power: It is the movement Fig. 5.1
of one molecule over another. Polymer
molecules greatly affect the resistance to slip and consequent deformation
of a polymer, and slipping power mainly depends on shape of the
molecule.
Example: The shape of a polyethylene molecule is simple and uniform,
and there is only limited restriction to the movement of one molecule
over another, i.e. slipping power is more.

H H H H

---- C — C — C — C ----

H H H H

Polyethylene (PE)

But, PVC molecules have large lumps of chlorine atoms in the chain,
and restrict the movement of one molecule over the another. There are
strong van derWaals forces, i.e. the slipping power is low. PVC is tough
and stronger than polyethylene.

H H H H

— C—C —C—C—

H Cl H Cl

Polyvinyl chloride (PVC)

Due to the presence of a bulky phenyl group, polystyrene possesses

greater strength compared to PE and PVC.
(b) Strength of Cross-linked Polymers
In cross-linked polymers, all the structural units are connected by ‘strong’
covalent forces resulting in a giant solid molecule. Consequently, they are
more strong and tough, since the movements of intermolecular chains
are totally restricted, e.g. Bakelite.

5.6.2 Plastic Deformation

On application of heat and pressure, there is a permanent deformation
occurs on a polymer. This property is mainly useful to classify the
polymers (thermoplastics or thermosetting plastics).
(a) Plastic Deformation in a Linear Polymer
These are polymeric substances which can be deformed by heat and
pressure. This property of thermoplastics is called plastic deformation.
Repeated heating and cooling does not affect the chemical nature of the
polymer.
Linear polymers show greatest degree of plastic deformation, as the
molecules are held by weak van derWaals forces of attraction. Under high
temperature and pressure, the forces become weaker. So slippage occurs
between the chains. On cooling, they regain their original hardness.
Repeated heating and cooling do not affect the nature of the polymer.
So plasticity of such polymers is reversible and can be remoulded many
times. They are called thermoplastics, e.g. Polyethylene.

H H H H H H H H H H H H

— C—C —C—C—C—C— — C—C —C—C—C—C—

H H H H H H H H H H H H

(b) Plastic Deformation in Cross-linked Polymer

In giant cross-linked polymers, deformation does not occur on heating
because only primary covalent bonds are present throughout the entire
structure. Due to the presence of strong covalent bonds, it cannot be
easily affected either by heat or pressure. So no slippage occurs in
between the chains. Such types of polymers, once moulded, cannot be
remoulded and they are called thermosetting plastics. Therefore, in
thermosetting polymers, plasticity does not increase with increase in
temperature.

5.6.3 Crystallinity
The relative arrangement of the polymer chains with respect to each
other results in three types of polymers.
 (i) Amorphous polymer
(ii) Crystalline polymer
(iii) Crystallites embedded in an amorphous matrix

(a) (b) (c)

Fig. 5.2 (a) Amorphous polymer (b) Crystalline polymer (c) Crystalline polymer embedded
in an amorphous matrix

(a) Amorphous Polymer

They have random arrangement of polymer chains and hence the
intermolecular forces are weak. Polymers with long chains and bulky
side groups of low degree of symmetry, do not crystallise easily and,
therefore, form an amorphous state. The amorphous region in a polymer
provides flexibility.
Example: Polystyrene, Polyvinyl acetate
(b) Crystalline Polymer
Crystallization imparts denser packing of molecules, thereby increasing
the intermolecular forces of attraction. The polymer chains are regularly
arranged in a crystalline polymer. So the intermolecular forces are
increased, resulting in high density, greater strength and sharper
softening point. The tendency of a polymer to be crystalline increases
when the polymer chains are linear without any side chain. A completely
crystalline polymer tends to acquire brittleness.
Example: Polyethylene, cellulose derivatives
(c) Crystallites Embedded in an Amorphous Matrix
Most of the polymers have crystallites embedded in an amorphous
matrix. In such cases, crystallites provide required hardness, rigidity
and heat resistance while the amorphous matrix provides flexibility.
Co-polymerization decreases crystallinity. In controlling the extent of
co-polymerization, the relative extent of crystallites and amorphous
region can be adjusted to get the required hardness and flexibility.

5.6.4 Chemical Resistance

The chemical resistance of a polymer is decided by the nature of
monomeric units and their molecular arrangement. Chemical attack
causes softening, swelling and loss of strength of material.
Examples
(a) Polymers having polar groups like –OH and –COOH are usually
soluble in polar solvents like alcohol, water, etc., but they are
chemically resistant to nonpolar solvents like benzene, toluene,
etc.
(b) Polymers of more aliphatic characters are more soluble in aliphatic
solvents.
(c) Polymers of more aromatic characters are more soluble in aromatic
solvents.
(d) Polymers having nonpolar groups like –CH3 and –C6H5 are soluble
in nonpolar solvents. But they are resistant to polar solvents like
water, ethyl alcohol, etc.
Other factors such as molecular weight, crystallinity and degree of
cross linking also determine the chemical resistance.
(i) The tendency to be soluble in a particular solvent decreases with
increase of molecular weight of the polymer.
(ii) The chemical resistance of crystalline polymers is more than that
of amorphous polymers.
(iii) Greater the degree of cross linking in the polymer, lesser is its
solubility.

5.7 PLASTICS

5.7.1 Introduction
(i) Plastics are a new group of ‘engineering materials‘.
(ii) Plastics are ’synthetic organic polymers’.
(iii) Any substance which has the property of ’plasticity‘ is called a
plastics.
(iv) Plastics are hard rigid solids at room temperature but they can be
moulded in any form with the help of heat and pressure.
5.7.2 Definition
They are organic materials (of high molecular weight). While being
processed, can be pushed into almost any desired shape and then retain
that shape on application of heat and pressure.

5.7.3 Types of Plastics

Plastics are mainly classified into two types.
(a) Thermoplastics
(b) Thermosetting plastics
(a) Thermoplastics
They soften on heating and harden on cooling. Resoftening and
rehardening is also possible.
Examples Polythene, PVC, Polystyrene, Polyester and Polypropylene
(ii) Thermosetting Plastics
They set on heating and cannot be resoftened on cooling.
Examples
• Urea-Formaldehyde
• Phenol-Formaldehyde
• Alkyl resin
• Silicon resin

Table 5.1 Differences between thermoplastics and thermosetting plastics

[Link] Thermoplastics Thermosetting Plastics

1. They are prepared by addition polymerization They are prepared by condensation

method. polymerization method.
2. They are generally linear polymers. They are generally cross-linked polymers.
3. They are softer, weaker and less brittle. They are harder, stronger and more brittle.
4. They are polymers of smaller molecular They are polymers of higher molecular
weight. weight.
5. They have low thermal stability. They have relatively high thermal stability,
but prolong heating result in charring.
6. They can be remoulded. They cannot be remoulded.
7. The process is reversible The process is irreversible.
8. They soften on heating and regain their They set on heating and cannot be
original properties on cooling. resoftened on cooling.
(Contd.)
Table 5.1 (Contd.)

[Link] Thermoplastics Thermosetting Plastics

9. They are easily broken because the molecules They are not easily broken because the
are held together by weak van derWaals forces. molecules are held together by strong
covalent bonds.
10. They expand very much on heating. They expand in a limited way.

11. Hardening is not due to chemical reaction. Hardening is due to chemical reaction.
12. Scraps can be reused. Scraps cannot be reused.

13. They are moulded by injection moulding They are moulded by compression
process. moulding process.
14. They are soluble in organic solvents. They are insoluble in organic solvents.
15. Example: Polyethylene, Polypropylene, PVC, etc. Example: Bakelite, Urea-formaldehyde, etc.

5.7.4 Advantages of Plastics

• They are very light but very strong.
• They possess low melting points.
• They can be moulded and have excellent finishing.
• They possess very good strength and toughness.
• They possess good shock-absorption capacity.
• They are corrosion resistant and chemically inert.
• They are good water resistants and possess good adhesiveness.
• They are good electrical insulators.

5.7.5 Disadvantages of Plastics

• They are soft in nature.
• They undergo deformation under load.
• They undergo embrittlement at low temperature.
• They possess low heat resistance and poor ductility.
• They have combustibility.
• Polymer tends to degrade upon exposure to heat and UV
radiation.

5.8 INDIVIDUAL POLYMERS

5.8.1 Polyethylene (PE)

Polyethylene is the simplest hydrocarbon polymer and was produced
in England during 1933 from the ethylene monomer.
(a) Low-density Polyethylene (LDPE)
It is prepared by the polymerization of ethylene under
(i) Preparation
high pressure (1000–5000 atm) in presence of oxygen (free-radical
initiator).
O2 catalyst
n CH2 CH2 — (CH2 — CH2)n —
Ethylene LDPE

(ii) Properties
• This polymer is highly branched and is 40% crystalline.
• Its softening temperature is only 115°C.
• It is soluble in CCl4, toluene and xylene at high temperature.
• It is ductile in nature.
• It is poor conductor of electricity.
(iii) Uses It is used in making packing films, tablecloths, packing
materials, moulded toys, insulation wires, etc.
(b) High-density Polyethylene (HDPE)
(i) PreparationEthylene can be polymerized at 6–7 atmospheric pressure
at 60°–70°C in presence of Zeigler–Natta catalyst.

Zeigler–Natta cataalyst
n CH2 CH2 —(CH2 — CH2)—
n

Ethylene HDPE

(ii) Properties
• This polythene is linear and 90% crystalline.
• Its softening temperature is only 135°C and it can be used at higher
temperature.
• It is almost insoluble in all the solvents.

(iv) Uses It is used in preparation of toys, containers, pipes, detergent

bottles, etc.

Table 5.2 Differences between low-density polyethylene and high-density polyethylene

[Link] Low-density Polyethylene High-density Polyethylene

1. It is prepared under high pressure using It is prepared under low pressure using
O2 as a catalyst. Zeigler–Natta catalyst.
2. It is a branched polymer and has low It is mostly a linear polymer and highly
crystallinity (40%). crystalline (90%).
(Contd.)
(Table 5.2 Contd.)

[Link] Low-density Polyethylene High-density Polyethylene

3. Density: lower (0.91–0.92 g/ml). Density: higher (0.965 g/ml).
4. Melting point is 110–125°C. Melting point is 144–150°C.
5. It is soluble in CCl4, toluene and xylene at It is almost insoluble in all the solvents.
high temperature.
6. Used for preparing films, tablecloths, Used in preparation of toys, pipes, detergent
packing materials, moulding toys, etc. bottles, containers, etc.

7. More flexible. Highly rigid.

5.8.2 Polypropylene (PP)

Polypropylene is prepared from propylene.
(a) Preparation It is obtained by the polymerization of propylene in
the presence of Zeigler–Natta catalyst (coordination catalyst)

n CH2 CH —(CH2 — CH)—

n

CH3 CH3

Propylene Polypropylene

(b) Properties
• It is a stereoregular, isotactic polymer and highly crystalline in
nature.
• It is insoluble in many solvents and soluble in boiling organic
solvents.
• It possesses good dielectric property.
• Its melting points is 160°C.
• It is more resistant than polyethylene.
Uses
• It is used in the manufacture of squeezing of bottles, textile
machinery parts, laboratory articles, sanitary wares and insulation
of electrical wires.
• It is used in making moulded parts and fibres.
• Polypropylene fibres are used in handbags, carpets, etc.

5.8.3 Polyvinyl Chloride (PVC)

PVC is the most important of all the polyvinyl plastics and is called
‘Koroseal‘.
(a) Preparation Vinyl chloride is the monomer used for preparation
of PVC. It involves the following two steps.
Step I: Vinyl chloride is prepared by treating acetylene with hydrogen
chloride at 60–80°C in the presence of metal chloride as catalyst.

CH CH + HCl CH2 CH
Acetylene
Cl
Vinyl chloride

Step II: Polyvinyl chloride is prepared by free-radical polymerization

of vinyl chloride. A water emulsion of vinyl chloride having a small
amount of benzoyl peroxide is heated under pressure

CH2 CH — CH2 CH —
Polymerization
n
Cl Cl
Vinyl chloride PVC n

(b) Properties
• PVC is a colourless, odourless, chemically inert powder and non-
inflammable.
• It is insoluble in inorganic acids and alkalies, but soluble in hot
chlorinated hydrocarbons such as ethyl chloride.
• It undergoes degradation in the presence of heat or light.
• Pure resins possess a high softening point (148°C).
(c) Uses
(i) Rigid PVC (or) Unplasticised PVC: Since it has superior chemical
resistance and high rigidity, it is used for making sheets, which are
employed for tank linings, light fittings, refrigerator components, etc.
(ii) Plasticised PVC: It is used in the production of pipes, cable
insulations, table covers and raincoats, etc.

5.8.4 Teflon or Fluon or Poly Tetrafluoro Ethylene (PTFE)

(a) Preparation It is prepared by free-radical addition polymerization
of water emulsion of tetrafluoro ethylene at high pressure in the presence
of benzoyl peroxide.

Polymerization
n (CF2 CF2) —(CF2 — CF2)—
n

Tetrafluoroethylene PTFE
(b) Properties
• Due to high electro negative fluorine atoms, they have strong
attractive forces. These forces give the material extreme toughness
and high softening point.
• It is a linear and highly crystalline polymer.
• It possesses good electrical and mechanical properties.
• It has a good chemical resistant capacity (except hot alkali metal
and hot fluorine).
• It is insoluble in most of the solvents.
(c) Uses
• It is used as a good electrical insulator in motors, cables,
transformers and electrical fittings.
• It is also used as a nonstick coating on frying pans, making gaskets,
packings, pump parts, tank linings, etc.
• It is used for preparing non-lubricating bearings, chemical carrying
pipes, etc.
• It is used for making stopcocks for burettes and in chemical
equipments.

5.8.5 Acrylics or Poly Acrylonitrile or PAN or Orlan

or Acrilan
(a) Preparation It is prepared by the polymerization of acrylonitrile
in the presence of peroxide. The starting material is prepared by passing
a mixture of propene, ammonia, steam and air over a mixture of oxides
of molybdenum, cobalt and aluminium.
Oxides of
2CH CH—CH3 + 2NH3 + 3O2 2CH2 CH—CN + 6H2O
Mo, Co and Al
Propene Acrylonitrile

Peroxide
n CH2 CH — CN — CH2 — CH —

CN n
Acrylonitrile Polyacrylonitrile

(b) Properties and Uses

• It is a highly crystalline polymer.
 • It is the major constituent of acrylic fibres.
• It is used for making fibres, adhesives, nitrile rubber and for
impregnating leather and paper.
• It has high resistance to chemicals and has good mechanical
properties.
• It is used as a substitute for wool in making fibres.
Example: Orlon.

5.8.6 Bakelite or Phenolic Resin or Phenoplast

Phenolic resins are condensation polymers obtained by condensing
phenol with formaldehyde in the presence of an acid or alkali catatyst.
It is the most important and oldest of synthetic plastics.
(a) Preparation The reaction proceeds in the following three steps.
During the first step, the reaction takes place
Step I: Methylolation:
between phenol and formaldehyde forming mono, di and tri-methylol
phenols.

OH
CH2OH
HCHO

Monomethylol phenol

OH OH
HOH2C CH2OH
2HCHO

Dimethylol phenol

OH
HOH2C CH2OH
3HCHO
CH2OH
Trimethylol phenol
Step II:
(i) Formation of A-stage Resin (Resole)

OH OH
HOH2C CH2OH CH2OH
+
Alkaline catalyst – H2O

OH OH
HOH2C CH2 CH2OH

Methylene linkage Resole

OH OH
HOH2C CH2OH + HOH2C CH2OH

Alkaline
catalyst – H2O

OH OH
HOH2C CH2 — O — CH2 CH2OH

Resole Ether linkage

• When excess of formaldehyde is heated with methylol phenols in

the presence of an alkaline catalyst, the methylol phenols condense
either through methylene linkage or through ether linkages to
form resoles.
• Resole is a linear, low-molecular-weight polymer and completely
soluble in alkaline solution.
(ii) Formation of B-stage Resin (Novolac or Resitol): When excess of
phenol is heated with methylol phenols in the presence of an acidic
catalyst, the methylol phenols condense with phenol through methylene
linkages to form novolacs.
• Novolac is a linear high-molecular weight polymer and is insoluble
in alkaline solutions.
 OH OH
CH2OH Acid catalyst
— H2O
+

OH OH OH
H2C CH2 CH2 CH2

Methylene bridge
Novolac (or) Resitol

Step III: Production of C-stage Resin (Bakelite)

Curing Agent
A stage Resin + B stage Resin Bakelite
Heating A-stage Resin or B-stage Resin or both in the presence of
a curing agent (hexamethylene tetramine) produces a hard, rigid,
infusible, cross-linked structure called Bakelite.

OH OH OH OH
H2C CH2 CH2 CH2 CH2

CH2 CH2 CH2 CH2

H2C CH2 CH2 CH2 CH2

OH OH OH OH

Bakelite

(i) Properties
• It is a hard, rigid, infusible, water resistant and insoluble solid.
• Bakelite is resistant to acids, salts and most organic solvents, but
it is attacked by alkalies because of the presence of –OH groups.
• It acts as an excellent electrical insulators.
• It can withstand high temperature.
(ii) Uses
• It is used for making moulded articles such as radio and TV parts,
etc.
• It is used as an adhesive in plywood laminations and in grinding
wheels, etc.
• It is commonly used in paints and varnishes.
• It is used for making electrical insulation parts like plugs, switches,
heater handles, etc.
• It is also used as ion-exchange resins.

5.8.7 Nylon (Polyamides)—Nylon-6,6

It is a condensation polymer. This is the first synthetic fibre produced
from simple molecules. Its chemical name is polyhexamethylene
adipamide.
(a) Preparation
Nylon-6,6 is obtained by the polymerization of adipic acid with
hexamethylene diamine.

n H2N—( CH2)6—NH2 + n HOOC—(CH2)4—COOH

Hexamethylenediamine Adipic acid

—[HN—(CH2)6—NH—CO—(CH2)4—CO]n + 2n H2O
Nylon-6,6

(b) Properties
• It is tough, strong and crystalline in nature.
• It is easily mouldable and abrasion resistant.
• It has high tensile strength and high elasticity
• It has good chemical resistance.
• It has low coefficient of friction.
• Kevlar it is an aromatic polyamide similar to nylon but instead
of aliphatic chain, a benzene ring will be present). It is highly
temperature resistant.
(c) Uses
• It is used for making nylon thread in textile materials.
• Nylons are used for making filaments for ropes, bristles for
toothbrushes and films etc.,
• It is used in automobile industries as self-lubricating bearings,
gears, etc.
 • It is also used in making shocks, dresses, carpets, etc.

5.8.8 Polyester Resins

Polyesters are the condensation products of dicarboxylic acid with
dihydroxy alcohols.
Examples: Polyethylene terephthalate (PET) or Terylene or Dacron.
(a) Polyethylene Terephthalate (PET)
(i) Preparation:It is a saturated polyester, prepared by the condensation
of ethylene glycol and terephthalic acid.

n HO — (CH2)2 — O H + HO O C — COOH

Ethylene glycol Terephthalic acid

Condensation Polymerisation

— O — (CH2)2 — O — C — C—
n
O O
PET

(ii) Properties
• It is a good fibre-forming material with high tensile strength and
can be converted into commercial fibres.
• It possesses high stretch-resistance, high-crease and wrinkle-
resistance.
• It is highly resistant to mineral and organic acids, but is less
resistant to alkalies.
• It has low moisture absorption capacity.
(iii) Uses
• It is mostly used for making synthetic fibres like Terylene, Dacron
etc.,
• It is used for blending with wool to provide better crease and
wrinkle resistance.
• It is used as a glass-reinforcing material in safety helmets, aircrafts,
battery boxes, etc.
5.8.9 Epoxy Resins or Epoxide Polymers
They are fundamentally polyethers, because the monomeric units have
an ether structure (R-O-R). Epoxy Resins are cross-linked thermosetting
resins.
(a) Preparation
Epoxy polymers, or epoxy resins, are prepared by condensing
epichlorohydrin with Bisphenol-A.
The reactive epoxide and hydroxyl groups give a three-dimensional
cross-linked structure. The value of ‘n’ ranges from 1 to 20 and the
molecular weight ranges between 350 and 8000.

CH3

n HO C OH + Cl — CH2 — HC — CH2

CH3 O
Epichlorohydrin
Bisphenol A
Alkaline
catalyst
– nHCl
CH3

—O C O — CH2 — CH — CH2 —

CH3 OH
n
Epoxy resin

(b) Properties
• Due to the presence of stable ether linkage, they have high
chemical resistance to water, acids, alkalies, various solvents and
other chemicals.
• They have high flexibility, toughness and possess very good heat
resisting property.
• Due to polar nature of the molecules, they produce excellent
adhesion property.
(c) Uses
• These are used as surface coatings, adhesives like araldite, glass-
fibre reinforced plastics.
• To impart crease resistance and shrinkage control, epoxy resins
can be applied over cotton, rayon and bleached fabrics.
 • They are used as laminating materials in electrical equipments.
• Moulds made from epoxy resins are used for the production of
aircrafts and automobile components.

5.8.10 Poly-Urethane (Perlon-U)

(a) Preparation
Poly-Urethane is commercially obtained from di-isocyanate and diol.
Perlon-U (a crystalline polymer) is obtained by the reaction of 1,4-butane
diol with 1,6-hexamethylene di-isocyanate.

O O

n C N — (CH2)6 — N C + HO — (CH2)4 — OH

1,6-hexamethylene 1,6-butane diol

di-isocyanate

O H H O

—C N — (CH2)6 — N — C — O — (CH2)4 — O —
n
Poly-Urethane or Perlon-U

(b) Properties
• They are less stable than polyamides.
• They are highly resistant to oxidation.
• They possess excellent flexibility and toughness even at subzero
temperatures.
• They are characterized by excellent resistance to abrasion and
solvents.
• They are used to produce gaskets, seals and printing rolls.
(c) Uses
• Poly-urethanes are used as coatings, films, foams, adhesives and
elastomers.
• They are also used in defence, oceanographic research,
mountaineering, etc.
• Poly-urethane fibres are used for formation of garments and
swimsuits.
• They are also used as a leather substitute.
5.8.11 Polycarbonate PC (Lexan, Merlon)
Polycarbonates are those polymers which contain a carbonate group as
a repeating unit. They are prepared by interaction of diphenyl carbonate
with bisphenol-A

CH3

n O C O + nHO C OH
2
CH3
Diphenyl Carbonate Bisphenol-A

O CH3

—O—C—O C + 2n OH

CH3 n
Phenol
Lexan

(a) Properties
• They are characterized by high tensile strength and impact
strength over a wide range of temperature (but have low scratch
resistance).
• They are soluble in organic solvents and alkalis.
(b) Uses
• They are used for preparing domestic ware, housing for apparatus
and electrical insulators in electronic and electrical industries.
• They are used to make ultralight eyeglass lenses, compact discs,
DVD’s and food storage containers.
• They are also used in production of sterilizable transparent
containers, baby bottles, safety windows in prison and jewellery
shops.

5.9 CONDUCTING POLYMERS

Polymers are generally poor conductors of electricity and some polymers

such as Teflon are used as insulators. Nowadays, such polymeric
materials have been synthesized which possess electrical conductivities,
and are called, conducting polymers.
5.9.1 Classification

Conducting polymers

Intrinsic Extrinsic Coordination

conducting
polymer
Conducting Doped Conductive Blended
polymer conducting element-filled conducting
having polymer polymer polymer
conjugation

(a) Intrinsic Conducting Polymer (ICP)

These polymers have extensive conjugation in the backbone which is
responsible for conductance.
(i) Conducting Polymer having Conjugation
Such a polymer contains a conjugated P-electron in the backbone which
increases its conductivity to a large extent. This is because overlapping of
the conjugated P-electron over the entire backbone results in formation
of valence bands as well as conduction bands.
The valence band and conduction band are separated by a band
gap. Thus, electrical conduction occurs only after thermal or photolytic
activation, to give them sufficient energy to jump the gap and reach
lower levels of the conduction band.
Example: Polyacetylene
(ii) Doped Conducting Polymer
It is obtained by exposing a polymer to a charge-transfer agent either
in gas phase or in solution. Generally, intrinsic conducting polymers
possess low conductivity. But they can be easily oxidized or reduced
as they have low ionization potential and high electron affinity. This
conductivity can be increased by creating either positive or negative
charge on the polymer backbone by oxidation or reduction. This is called
doping and is of two types.
• P-Doping: It involves treating the intrinsic conducting polymer
with a Lewis acid. Oxidation takes place and a positive charge is
created on the polymer backbone. Some of P-dopants used are
FeCl3, I2, Br2, etc.
• N-Doping: It involves treating the intrinsic conducting polymer
with a Lewis base. Reduction takes place and a negative charge
 is created on the polymer backbone. Some of N-dopants used are
sodium naphthalide.
(b) Extrinsic Conducting Polymer
In these polymers, conductivity is due to the presence of externally added
ingredients in them.
(i) Conductive Element-filled Polymer
In this, the polymer acts as a binder to hold the conducting element (such
as carbon black, metallic fibres) together in solid entity. The minimum
concentration of the conductive filler which should be added so that
polymer starts conducting, is known as percolation threshold. These
polymers possess good conductivity and are generally low in cost,
light in weight, mechanically durable, strong and easily processable in
different forms, shapes and sizes.
(ii) Blended Conducting Polymer
These polymers are obtained by blending a conventional polymer with
a conducting polymer. Such polymers possess better physical, chemical,
electrical and mechanical properties and can be easily processed.
(c) Coordination Conducting Polymers (Inorganic Polymers)
It is a charge transfer complex containing a polymer obtained by
combining a metal atom with a polydentate ligand. Degree of
polymerization in such polymers is small.
Applications
• It is used in rechargeable light-weight batteries.
• It is used in wiring aircrafts and aerospace components.
• It is also used in solar panels.

5.10 POLYMER BLENDS AND ALLOYS

5.10.1 Polymer Blends

A polymer blend is a simple physical combination of two or more
incompatible polymers, e.g. wood is a natural blend of more than one
polymer.

5.10.2 Properties
(i) A polymer blend appears as separate phases, when viewed under
a microscope.
 (ii) Between different polymeric chains, only van derWaals forces,
dipole interaction or hydrogen bonding exists.
(iii) The properties of a polymer blend are closely related to the
properties of the individual polymer component.
For example, a blend of PMMA (an amorphous polymer) with
PVDF (poly vinyldene fluoride, crystalline polymer) is amorphous
if the PVDF proportion is below 40%.
(iv) Blending usually improves the properties like processability,
impact strength, abrasion resistance, flame retardance, etc.
(v) Sensitive component of a blend may be protected from degradation
by blending.
For example, PMMA is degraded by g-radiation. However,
its blend with Styrene-Acrylonitrile (SAN) reduces the rate of
degradation.
Examples
(i) ABS plastics are made by blending acrylonitrile-stryrene
copolymer with butadiene-stryrene rubber. ABS possesses a high
impact strengh, high softening temperature and mouldability.
ABS products have a pleasing appearance. They are used in the
automobile industry for making panels, door covers, door bands
etc. Electroplated ABS is used for reflectors, nameplates and other
such jobs, where a bright reflecting surface is required.
(ii) Polycarbonate (PC)-ABS (acrylonitrile-butadiene-styrene) blend is
used for making electrical housings and machine parts.
(iii) Nylon 6-PC blend possesses improved thoughness and is employed
for making sports equipment and transport containers.
(iv) Polymide polyphenylene sulphide blend possesses properties of
both. It has processability and high temperature resistance. It is
used as an insulator and electrical connector.
(v) Polydimethylphenylene-polystyrene blend possesses low water
absorption, low moulding shrinkage, resistance to hydrolysis and
quite good dielectric properties over a wide range of temperature.
It finds use in electrical industries, automobile parts, radio and
television parts.

5.10.3 Polymer Alloy

Polymer alloy is a compatible mixture of two or more polymers, which
interact chemically in the presence of compatibilizers under specific
conditions of composition, temperature and pressure. The purpose of
a compatibilizer is to provide physical links between semicompatible
polymeric materials and to form a polymeric network. Usually, a
block of copolymers are used as compatibliers, e.g. chlorosulphonated
polythene.
Alloying of two polymers is, usually, done for achieving a specific
combination of properties which are not attainable by the use of either of
constituent polymers. Alloying of polymers, usually, improves properties
like processability, abrasion resistance, impact strength, flame retardance,
etc.
Examples
(i) ABS-PC Alloys
ABS-PC alloys possess high softening temperature (110–130oC), good
impact strength, good flexural strength, flame retardance and can be
electroplated.
Uses: For making typewriters, electronic printers, wheel caps, food
mixers, helmets, grills, pump casting and in the medical field as a
substitute for stainless steel, since it can be sterilized.
(ii) ABC-PVC Alloy
ABC-PVC alloy possesses good surface gloss, dimensional stability, creep
resistance, better flow properties, self-extinguishing property and can be
processed at low temperature. Moreover, it can be painted, screenprinted
and electroplated.
Uses: In making electronic switch devices, TVs, deflection components,
dashboards for passenger cars, connectors to busbars, liners for buses,
truck cabs, etc.

5.11 COMPOUNDING OF PLASTICS

Compounding is a process of mixing of raw plastics with other substances

to impart special properties to the product. Usually, the high-polymer
material is mixed with 4 to 10 ingredients, each of which either discharges
a useful function during moulding or imparts some useful property to
the finished article. The main types of compounding ingredients and
their functions are described below.

5.11.1 Resin or Binders

• Resin is the binder, which holds the different constituents
together.
• Thermosetting resins are usually supplied as linearpolymers of
comparatively low molecular weight, because at this stage, they
are fusible and hence mouldable.
 • The conversion of this fusible form into cross-linked infusible form
takes place during moulding itself in the presence of catalysts
etc.
• They are major portions of plastic, e.g. wood resin, litharge.

5.11.2 Plasticizer
• Plasticizers are materials that are added to resins to increase their
plasticity and flexibility.
• Their action is considered to be the result of the neutralization
of a part of the intermolecular forces of attraction between
macromolecules of resins.
• They impart greater freedom of movement between polymeric
macromolecules of resins, thereby increasing the flexibility and
plasticity of the compounded material, but at the same time
reducing its strength and also decreasing its chemical resistance.
• The most commonly used plasticizers are vegetable oil, camphor,
esters of stearic or oleic or phthalic acids and some phosphates
like tricresyl phosphate, tributyl phosphate, tetrabutyl phosphate
and triphenyl phosphate.

Polymer
molecule

Plasticizer

Fig. 5.3 Action of plasticizer in plastics

5.11.3 Fillers or Extenders

Addition of fillers leads to hardness, opacity, tensile strength, and
workability.
 They are added
• To reduce the cost
• Decrease shrinkage during setting
Examples
1. In order to improve the hardness and heat resistance, quartz and
mica are added.
2. Addition of barium salts to plastics avoids penetration of
X-rays.
Besides the above-mentioned fillers, other fillers like china clay,
gypsum, paper pulp, carbon black, metallic oxides and talc, are also
used.

5.11.4 Lubricants
They help in easy moulding of plastics and avoid plastic material from
sticking to fabrication equipment.
Examples: Waxes, oils, stearates and soaps

5.11.5 Catalysts or Accelerators

These are used only in the case of thermosetting resins, to accelerate the
condensation polymerization of fusible resin into cross linked infusible
products.
Examples: Hydrogen peroxide, benzoyl peroxide, metals like Ag, Cu
and Pb, metallic oxides, ammonia and its salts.

5.11.6 Stabilizers
• Stabilizers are added to the moulding components in order to
improve the thermal stability of the moulding mix during the
processes.
• Two classifications: Opaque moulding stabilizers and Transparent
moulding stabilizers.
Examples 1. Opaque moulding stabilizers—White lead, lead chromate
and lead naphthenate.
2. Transparent moulding stabilizers—Stearates of lead, barium and
calcium.

5.11.7 Pigments and Dyes

In order to impart suitable colours, suitable dyes and pigments are
usually added to plastics.
Examples: Chromium trioxide, carbon black, zinc oxide, etc.
• Chromium trioxide provides green colour.
• Carbon black provides black colour.
• Zinc oxide provides white colour.

5.11.8 Anti-oxidants
• The main function of an anti-oxidant is to protect the plastic
against UV radiation and oxygen.
• UV radiation weakens and breaks the primary bonds resulting
in splitting of long-chain polymer molecules. Because of this, the
polymer becomes brittle and stiff.
• Anti-oxidants such as diphenylamine, are used to prevent oxidative
degradation in polymer.

5.12 FABRICATION OF PLASTICS

Articles of different shapes can be prepared from polymeric materials
by a method called fabrication of plastics. Many methods are employed
for fabrication, which depends on the types of plastics. The above-said
process of conversion of different-shaped articles is called moulding
process.

5.12.1 Moulding Process

Some moulding processes are given below:
(a) Compression Moulding
• The compression moulding method is used for both thermo- and
thermosetting plastics.
• The raw material used is in the form of loose powder or compacted
pills.

Heat and pressure

Guide
pins
Mould
cavity filled
with material

Fig. 5.4 Compression moulding

 • The correct amount of plastic ingredients must be taken. Then they
are filled between the two half pieces of the mould as shown in
Fig. 5.4 which are capable of being moved relative to each other.
• High pressure of the order of 100 kg/cm2 and temperature of
the order of 100 to 200°C are applied to complete the curing
process.
• The cavities are filled with fluidized plastic.
• The two halves are closed very slowly.
• Finally, curing is done by cooling or heating.
• After curing, the moulded article is taken out by opening the
mould parts.
(b) Injection Moulding

Plastic feed
Top moulding
Nozzle part (cold)
Hopper Heater

Hinge
Moulding
powder

Bottom moulding
part (cold)

Extraction pin

Fig. 5.5 Injection Moulding

• This method is commonly used for thermoplastics.

• The moulding powder is fed into a heated cylinder.
• This powder softens under heat and becomes fluid.
• The temperature used in this process is 90–260°C.
• The pressure used is 10,000 to 30,000 psi (pounds/square inch).
• The molten plastic material from the cylinder is then injected
through a nozzle under high pressure into the moulding cavity.
• One is a stationary part and another is a movable part.
• After the mould is filled with the molten material under pressure,
it is cooled by cold water circulation.
 • Afterwards, the mould is opened and the moulded part is pushed
out.
• This type of moulding takes shorter time, i.e. the product is
obtained within 10 seconds.
• Radio, TV and refrigerator components are manufactured by this
type of moulding.
Advantages
This method is the most widely used for moulding of thermoplastics,
because of its high-speed production, low mould cost, very less loss of
material and low finishing cost.
(c) Extrusion Moulding
This method is mainly used for continuous moulding of thermoplastic
materials into articles of uniform cross-section such as pipes, tubes, rods,
etc. The moulding material is liquified in a heated chamber. When the
material gets softened, it is pushed into a die with the help of a screw
conveyer. The die has the required outer shape designed for the finished
article. The finished product is cooled by exposure to atmospheric air
or by spraying water over it. A long conveyer carries away the cooled
product.
Plastic moulding power
Heater Die
Hopper
Cold part
Extruted
of the die
tube

Conveyer belt

Screw Plastic in hot condition

conveyor

Fig. 5.6 Extrusion moulding

(d) Blow Moulding

Most of the hollow plastic materials like PET bottles and toys are
manufactured by this technique. Usually, thermoplastic materials like
PVC, polystyrene, HDPE, PP can be blow moulded.
A hot softened thermoplastic tube at first as parison, is placed inside
two pieces of the hollow mould. When the two halves of the mould are
closed, one end is completely closed and the other end remains in contact
with the parison through a blowing pin. Compressed air is now blown to
the parison through a blowing pin. The parison is inflated like a balloon
and goes on expanding until it comes in intimate contact with the cold
interior surface of the hollow mould. The parison ultimately takes the
shape of the hollow cavity of the mould under pressure. After cooling,
the moulded article is removed from the mould by opening it.
Blowing pin

Mould

Tube
Mould closed
Air Blow Moulded

Article

Air

Air blown into mould

Mould opened

Fig. 5.7 Blow moulding

5.13 FOAMED PLASTICS

5.13.1 Introduction
According to American Society for Testing and Materials (ASTM), foamed
plastics are biphasic wherein a gas is dispersed in a dispersion medium
(like synthetic rubber or plastics). Foamed plastics are made by adding
air or gas to a plastic resin to form a spongelike substance. The common
resins used for foamed plastics are mainly poly-urethane, polystyrene,
polyethylene, polyvinyl chloride, cellulose acetate, epoxy resin, silicones
and phenolic resins.

5.13.2 Types
Plastic foams are generally classified as open-cell and closed-cell structure
foams. An open-cell structure means that the foam has interconnected
cells or openings running through the material. A closed-cell structure
has closed cells or bubbles. The open-cell structure foam will allow any
liquid to pass through like a sponge, whereas the closed-cell structure
foam will not allow any liquid to pass through the foam. Closed-structure
foams are generally rigid.

5.13.3 Method of Preparation

It is prepared by the following three methods.
(a) Chemical Foaming
In a foamed plastic or rubber, there are two-phase systems in which
a gas or air is dispersed into a dispersion medium such as plastic or
rubber. In foamed polymers, the fluid polymers such as poly-urethane,
PVC, polystyrene, etc., are heated with blowing agents such as calcium
carbonate, halocarbons etc., which produce the inert gases that are
entrapped inside the polymer matrix.
(b) Mechanical Foaming
The resin in liquid form is vigorously agitated until it becomes a foam
of air bubbles. PVC plastisols can be mechanically agitated to produce
a foamed polymer.
(c) Physical Foaming
In this process, certain gases like nitrogen, carbon dioxide or air are
forced through the molten resin to produce the foamed polymer. Foamed
polythene is produced by forcing compressed nitrogen gas into molten
polyethylene.

5.13.4 Foamed Plastics

Example: Thermocole
(a) Preparation Thermocole is a foamed plastic, obtained by blowing
air or gas through molten polystyrene or poly-urethane.
(b) Properties
• It is white in colour and can be made into desired shapes.
• It is light, strong and chemically inert , but attacked by acids.
• Its density is about 20 kg/m3.
• Its thermal and electrical conductivities are quite low.
• It is also used as a shockproof material.
• Its compressive strength is 117–145 kg/cm2.
• It can be used up to 55oC.
• It is very soft, so that it can be easily cut by a knife and can be
scratched by a nail.
(c) Uses
• Thermocole slabs are used for false ceilings in air-conditioned
rooms and for good acoustic effect.
• Due to its outstanding thermal insulating property and lower
density, it is used as a thermal insulating material (e.g. in
refrigeration and air conditioning).
• Since it is a very good shockproof material, it is used as a packing
material for electronic equipments.
• It is used for protecting screens in radars.
• It is used for decorative purposes.
• It is also used as an insulating and vapour barrier.

5.14 RUBBER OR ELASTOMERS

Rubbers are noncrystalline in nature and are high polymers that have
elastic properties. There are two types of rubber—natural rubber and
synthetic rubber.

5.14.1 Natural Rubber

The main source of natural rubber is the tree Hevea braziliensis.
Rubber is obtained from latex collected from cuts made in the bark of
the tree. During the treatment of latex, isoprene molecules in latex get
polymerized to form poly isoprene.

n CH2 C — CH CH2 Æ [CH2 — C CH — CH2]n

CH3 CH3
Isoprene Poly-isoprene (cis form)

5.14.2 Synthetic Rubber

The first synthetic rubber was originally developed in USA during the
Second World War as a substitute for natural rubber. They are man-made
rubbers which are superior to natural rubber in certain properties.
Examples: Buna-S rubber, butyl neoprene rubber, nitrile rubber, etc.

5.14.3 Buna-S Rubber (SBR) or (GR-S)

or Ameripol Rubber
(a) Preparation
It is prepared by co-polymerization of 75% butadiene and 25% styrene
at 0°C in the presence of a peroxide catalyst
 Copolymeri
n [CH2 C — CH CH2] + n [CH2 CH] sation
Butadiene

Styrene

[ CH2 — CH CH — CH2 — CH2 — CH ]n

Styrene-butadiene rubber

(b) Properties
SBR on vulcanization gives a cross-linked polymer and posseses high
resilience, high load-bearing capacity and high abrasion resistance.
(c) Uses
• It is highly useful in manufacture of motor tyres.
• It is used in manufacture of floor tiles, cable insulations, etc.

5.14.4 Butyl Rubber (GR-I)

(a) Preparation
It is made by co-polymerization of isobutylenes with small amounts of
isoprene.

m CH C — CH3 + n CH2 C — CH3

CH3 CH3

Isobutene Isoprene

CH3

CH2 C ————CH2 — C CH — CH2 —

CH3 CH3
m n

Polyisobutene-co-isoprene (Butyl rubber)

(b) Properties
• It is amorphous under normal condition but crystalline on
stretching.
 • It is resistant to heat, chemicals, ozone, polar solvents.
• It is soluble in nonpolar solvents such as benzene.
(c) Uses
• Butyl rubber is used in making cycle and automobile tubes.
• It is used for making insulating cables

5.14.5 Vulcanization of Rubber

This process was invented by Charles Goodyear in the year 1839. Natural
rubber is a gummy material with poor elasticity. There are no cross
links and it permanently undergoes deformation on being stretched.
To improve the properties of rubber, it is compounded with sulphur,
hydrogen sulphide, etc. Rubber is heated with sulphur at 100–140°C. The
tensile strength and chemical resistance are increased. This introduces—
S—S—cross links between adjacent hydrocarbon chains and rubber thus
obtained is called vulcanized rubber.

CH3 CH3

---— CH2 — C CH — CH2 — CH2 — C CH — CH2 —---

+
---— CH2 — C CH — CH2 — CH2 — C CH — CH2 —---

CH3 CH3
Vulcanization +S

CH3 CH3

---— CH2 — C CH — CH2 — CH2 — C CH — CH2 —---

Sulphur
S S S S cross links

---— CH2 — C CH — CH2 — CH2 — C CH — CH2 —---

CH3 CH3

(a) Example
• 3–5% of sulphur is present in tyre rubber.
• 30% of sulphur is used in battery-case rubber.
(b) Advantages
• It possesses good tensile strength and low tendency to absorb
water.
• It is highly resistance to oxidation and organic solvents.
• It is highly resistance to wear and tear.
• It has excellent resilience(articles return to their original shape
when applied force is removed).
• It is a better electrical insulator.

Table 5.3 Comparison between raw rubber and vulcanized rubber

Raw Rubber Vulcanized Rubber
(i) Resistance to wear and tear is low (i) Resistance to wear and tear is high
(ii) Low oxidation resistance (ii) High oxidation resistance
(iii) High water-absorbing capacity (iii) Low water-absorbing capacity
(iv) Low tensile strength (iv) High tensile strength
(v) Less durability (v) High durability
(vi) It has high elongation (vi) Moderate elongation
(vii) Useful temperature range is 10–60°C (vii) Useful temperature range is 40–100°C
(viii) Attacked by organic solvents (viii) Resistant to organic solvents

5.15 COMPOSITES
Engineering materials belonging to different classes have different types
of properties. Materials belonging to a particular type have several
properties characteristic of their own class but they lack some important
properties needed for a particular application. In order to incorporate
additional properties in the material, it is mixed with some other materials
and a new class of materials called composites are developed.

5.15.1 Definition
A composite material may be defined as, a material system consisting
a mixture of two or more microconstituents, which are mutually
insoluble, differing in form or composition and forming distinct
phases. Such a combination of materials possesses properties which are
different from those of any of its constituents.

5.15.2 Characteristics of Composites

(i) Higher specific strength
(ii) Lower specific gravity
 (iii) Higher specific stiffness
(iv) Low electrical conductivity and thermal expansion
(v) Better creep, fatigue strength, corrosion and oxidation resistance
(vi) Maintain strength even up to high temperature

5.15.3 Constituents of Composites

Important constituents of composites are
(a) Matrix phase
(b) Dispersed phase
(a) Matrix Phase
It is the continuous body constituent, which encloses the composites.
Matrix phase may be metals, ceramics and polymers. Composites using
this matrix are called
(i) MMC—Metal Matrix Composites
(ii) CMC—Ceramic Matrix Composites
(iii) PMC—Polymer Matrix Composites
Requirement of a Good Matrix Phase
It should be ductile and corrosion resistant and possess high bonding
strength between the matrix and dispersed phase.
(b) Dispersed Phase
It is the structural constituent that determines the internal structure of
composites.
Example: Fibres, particulates, flakes, whiskers etc.

5.15.4 Types of Composites

Fibre-Reinforced Polymer Composites or Polymer Composites
They are prepared by bonding a reinforcing (fibre) material with a resin
matrix and curing them under pressure and heat. Reinforcing agents are
alumina, carbon, boron, graphite, glass, etc. The resin matrixes commonly
used are polyesters, epoxy, phenolic, silicone and polyamide polymer
resins. The choice of fibre used for reinforcing a plastic depends on
desired properties of composites thus obtained.
(a) Properties
(i) It possesses high stiffness, strength, fracture strength and fatigue
life.
(ii) Since fibre prevents slip and crack propagation, the mechanical
properties of FRP gets increased.
 (iii) It possesses heat-resistance property and high corrosion
resistance.
Properties depend mainly on nature of resin matrix:
• Polyester resin—It gives good strength and mechanical
properties.
• Epoxy resin—Imparts good mechanical properties.
• Silicone resin—Provides excellent thermal and electrical
properties.
• Phenolic resin—To withstand high temperature.
• Thermoplastics—Repeatability and repairability capacity.

5.15.5 Types of FRP Composties

There are five types of FRP composties.
(i) Glass FRP
(a) Properties
• Excellent corrosion resistance
• High tensile strength
• Low density
(b) Uses
It is used for making automobile parts, storage tanks, plastic pipes,
etc.
(ii) Boron FRP
(a) Properties
It possesses excellent stiffness and compressive strength.
(b) Uses
It is used for making horizontal and vertical tails in aeroplanes, stiffening
spares, etc.
(iii) Carbon FRP or Advanced Polymer Matrix Composites
(a) Properties
• Low density and excellent corrosion resistance
• Retention of desired properties even at elevated temperatures
(b) Uses
They are used for making sports material, recreational equipment,
antenna discs, solar panels and structural components of aircraft and
helicopters.
(iv) Aramid FRP (Kevlars)
(a) Properties
• They have high tensile strength but are weak in compression
strength.
• They also have special property of ductility and flexibility.
(b) Uses
They are used in structural components in aircraft, helicopter parts,
sports goods, pressure vessels, clutch linings, etc.
(v) Alumina FRP
(a) Properties
They possess good abrasion resistance, creep resistance and dimensional
stability.
(b) Uses
They are used for making components of engine parts in automobile
industry and components of turbine engines.

5.15.6 Metal Matrix Composites

In metal matrix composites, matrix phases used are alloys of aluminium,
titanium and nickel. The reinforced materials are Al2O3, boron, carbon
and SiC.
(a) Properties
They exhibit good thermal stability, high strength, good stiffness and low
specific weight. They can withstand elevated temperatures in corrosive
environment.
(b) Uses
• MMC’s are used in combustion chambers, engine blades, etc.
• MMC’s of aluminium and magnesium are used in automotive
industry.
• They improve fuel efficiency because of the weight reduction.
• They are also used in biomedical and sports equipment
industry.

5.15.7 Ceramic Matrix Composites

The matrix phases used are glass, ceramics, carbides, nitrides, oxides,
borides and the reinforcements are Al2O3, boron, carbon, SiC and SiO2.
(a) Properties
They possess good corrosion resistance and high compressive
strength.
(b) Uses
They are used in space vehicles, tiles, pump seal, round rings, brake
linings, etc.

QUESTIONS

Two-Mark Questions with Answers

1. What are polymers?
Polymers are macromolecules formed by the repeated linking of
large number of small molecules called monomers.
2. Define monomer.
A monomer is a micromolecule that combine with each other to
form a polymer.
3. What is meant by polymerization?
Polymerization is a process in which a large number of small
molecules combine to form a big molecule with or without
elimination of small molecules like water.
4. Define the term degree of polymerisation.
The number of repeating units (n) in a polymer reaction is known
as the degree of polymerization.
5. What is meant by oligopolymers?
Polymers with low degree of polymerisation are known as
oligopolymers and their molecular weight ranges from 500–
5000.
6. What are graft polymers?
A branched copolymer with one kind of monomer (M1) in the
main chain and another kind of monomer (M2) in the side chain
is called a graft copolymer.
7. Define the term ‘tacticity’.
The orientation of monomeric units or functional groups in a
polymer molecule can take place in an orderly or disorderly
manner with respect to the main chain, called tacticity.
8. Define the term ‘functionality’.
Functionality is the number of bonding sites present in the
monomer.
 9. What are living chain polymers and dead polymers?
The growing chain of the polymer is known as living polymer.
Growth of polymer chain is terminated either by coupling reaction
or disproportionation. The product of addition polymerization is
known as dead polymer.
10. Define crystalline polymer.
In a crystalline polymer, the polymer chains are regularly arranged.
So the intermolecular forces are increased. This results in higher
density, greater strength and shorter softening point. The tendency
of a polymer to be crystalline increases when the polymer chains
are linear without any side chain.
11. What are thermoplastics?
They soften on heating and harden on cooling. Resoftening and
rehardening is also possible, e.g. polythene.
12. How is LDPE is obtained?
Low density polyethylene is obtained by the polymerization of
ethylene under high pressure using free radical initiator.
13. How is Teflon prepared?
Teflon is prepared by the polymerization of water emulsion of
tetrafluoroethylene in the presence of benzoylperoxide under
pressure.
14. What are epoxy resins?
These are cross-linked thermosetting resins. They are polyethers
because the monomeric units in the polymer have an ether type
of structure R-O-R.
15. What is compounding of plastics?
Compounding is mixing of raw plastics with other substances to
impart special properties to the product. Usually, the high-polymer
material is mixed with 4 to 10 ingredients, each of which either
discharges a useful function during moulding or imparts some
useful property to the finished article.
16. What are the uses of lubricants in plastics?
Lubricants reduce friction during moulding process between
mould and article.
Lubricants like waxes, oils, stearates, oleates and soaps are
employed to make the moulding of plastic easier and to impart
a flawless, glossy finish to the products. Lubricants prevent the
plastic material from sticking to the fabricating equipment.
 17. What is moulding process?
This process involves fabrication of plastic material into desired
shape under the influence of heat and pressure in a closed
chamber.
18. Write down the preparation for thermocole.
Thermocole is a foamed plastic, obtained by blowing air or gas
through molten polystyrene or poly-urethane.

Ten-Mark Questions
1. Explain the term ‘Tacticity’ with examples.
2. What is Zeigler–Natta polymerization? Explain in detail.
3. Explain the mechanisms involved in addition polymerization in
detail.
4. Define the term ‘plastics’. What are its types? Mention the
advantages of plastics.
5. Write short notes on Bakelite.
6. What are LDPE and HDPE? Give their difference.
7. Write the preparation, properties and uses of (a) acrylics, and
(b) polypropylene.
8. Explain the preparation, properties and uses of Nylon and PET.
9. What are epoxy resins? Mention their preparation, properties and
uses.
10. Describe the preparation, properties and uses of Perlon-U.
11. What is compounding of plastics? Explain the ingredients and
their functions in compounding.
12. What is compression moulding? Explain in detail.
13. Write short notes on (a) extrusion moulding, and (b) blow
moulding.
14. What are foamed plastics? Explain the types and method of
preparation.
15. Describe the preparation, properties and uses of thermocole.