Engineering Chemistry

Engineering Chemistry
(Second Edition)
N. Krishnamurthy
Head
Department of Chemistry
Mepco Schlenk. Engineering College, Sivakasi
P. Vallinayagam
Associate Professor
D. Madhavan
Senior Lecturer
PHI Learning lfutmGO@ llilW1BO@ctl

New Delhi-11 0001
En .
N ~Inehering Chemistry
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2009
FOREWORD
The assimilation of the concepts of chemistry, no doubt, is essential for the success of all
engineers and technocrats. This book discusses the basic and essential topics in chemistry
required for engineering students. The authors have written the book in a simple, lucid language
for easier understanding by the students. Each topic is dealt with in adequate depth as required
for the first-year engineering students.
v.
Director (Research)
Anna University
Chennai
:;.00
EERING CHEMISTRY, Second Edition

hnamurthy, P. Vallinayagam, and D. Madhavan
by PHI Learning Private Limited, New Delhi. All rights reserved. No part of this book may be
Iced in any fonn, by mimeograph or any other means, without pennission in writing from the
er.
78-81-203-3666-7
port rights of this book are vested solely with the publisher.
'rinting (Second Edition)
Murugesan
June, 2009
led by Asoke K. Ghosh, PHI Learning Private Limited, M-97, Connaught Circus,
elhi-110001 and Printed by Raj Press, New Delhi-110012.
iii
CONTENTS
iii
Foreword
Preface
xvii
UNIT I
1
1-29
Water Technology
1.1
1.2
1.3
1.4
1.5
1.6
1.7
Introduction
1
Impurities in Water
2
2
1.2.1
Sources of Impurities in Water
Hard Water
3
3
1.3.1
Disadvantages of Hard Water
3
1.3.2
Hardness of Water
Alkalinity
6
1.4.1
Experimental Determination of Alkalinity
7
Boiler Feed Water
8
1.5.1
Essential Requirements of Boiler Feed Water
8
1.5.2
Priming
8
1.5.3
Foaming
9
1.5.4
Sludge and Scale Formation in Boilers
9
10
1.5.5
Caustic Embrittlement
Boiler Corrosion
10
1.6.1
Removal of Dissolved O 2
10
1.6.2
Removal of Dissolved CO2
11
1.6.3
Removal of Acids
12
Prevention of Scale Formation or Softening of Water
12
1.7.1
External Treatment or External Conditioning
12
1. 7.2
Internal Treatment or Internal Conditioning
16
Contents
1.8
Potable Water (Water for Domestic Supply)

17
1.8.1
Treatment Processes for Removal of Impurities
1.9
Break Point Chlorination
20
1.10 Desalination
20
1.1 0.1 Electrodialysis
21
1.10.2 Reverse Osmosis
22
Solved Examples
22
Short Questions
27
Descriptive Questions
27
Problems
28
Polymers and Composites

Introduction
30
2.1.1
Homopolymers and Copolymers
31
2.1.2
Homo-Chain and Hetero-Chain Polymers
31
2.1.3
Block and Graft Copolymers
32
2.2
Types of Polymerization
32
2.2.1
Addition Polymerization
32
2.2.2
Copolymerization
32
2.2.3
Condensation or Step Polymerization
33
2.3
Free Radical Mechanism of Addition Polymerization
34
2.4
Plastics
35
2.5
Compounding of Plastics or Constituents of Plastics
35
2.6
Advantages of Plastics Over Other Materials
36
2.7
Classification of Plastics
36
2.7.1
General Purpose Plastics or Commodity Plastics
36
2.7.2
Engineering Plastics (High Performance Plastics)
37
2.7.3
Some Important Engineering Plastics
37
2.8
Fabrication of Plastics
40
2.8.1
Compression Moulding
40
2.8.2
Injection Moulding
41
2.9
Rubber
42
2.9.1
Vulcanization of Rubber
42
2.9.2
Advantages of Vulcanized Rubber
42
2.10 Some Important Synthetic Rubbers
43
2.10.1 Buna-S Rubber (SBR)
43
2.10.2 Butyl Rubber
43
2.11 Composites
44
2.11.1 Characteristics
44
2.11.2 Constituents of Composites
44
2.11.3 Types of Composites
44
Short Questions
45
46
47-6~
surface Chemistry
Introduction
47
Types of Adsorption
48
3.2.1
Physical Adsorption (Physisorption)
48
3.2.2
Chemisorption
48
3.3
Adsorption of Gases on Solids
49
3.4
Factors Influencing Adsorption
49
3.4.1
Temperature and Pressure
49
3.4.2
Nature of the Gas and Nature of the Adsorbent
50
3.5
Adsorption Isotherm
50
3.5.1
Type I Isotherm
51
3.5.2
Types II and III Isotherms
54
3.5.3
Types IV and V Isotherms
55
3.6
Adsorption Isobar and Adsorption Isostere
55
3.7
Adsorption of Solutes from Solution
55
3.8
Applications of Adsorption
56
3.9
Role of Adsorption in Catalytic Reactions
57
3.10 Role of Adsorbents
59
3.10.1 Role of Activated Carbon in Pollution Abatement of
Air and Waste Water
59
3.10.2 Ion-Exchange Adsorption
60
Solved Example
62
Short Questions
63
64
3.1
3.2
30-46
2.1
UNIT IV
vi
UNIT III
18
UNIT II
Contents
Nuclear Energy
4.1
4.2
4.3
4.4
Introduction
65
Energy Released in Nuclear Reactions
66
4.2.1
Mass Defect (Llm)
66
4.2.2
Binding Energy
67
4.2.3
Binding Energy and Nuclear Stability
67
Nuclear Reaction
68
4.3.1
Types of Nuclear Reactions
68
Nuclear Fission
69
4.4.1
Characteristics of Nuclear Fission
69
4.4.2
Chain Reactions
70
4.4.3
Subcritical Mass and Supercritical Mass
71
4.4.4
Atom Bomb
71
4.4.5
Nuclear Energy
72
Contents
Contents
Nuclear Reactor or Atomic Pile

72
4.5.1
Components of a Nuclear Power Reactor
4.5.2
Light Water Nuclear Power Plant
73
4.5.3
Breeder Reactor
74
4.5.4
Hydrogen Bomb
74
Solved Examples
74
Short Questions
76
76
6.6
Some Important Refractory Bricks

93
6.6.1
High Alumina Bricks
93
6.6.2
Zirconia Refractory Bricks
93
6.7
Cermets
94
6.8
Selection of Refractories
94
Short Questions
94
94
4.5
7~
77-87
Batteries
Introduction
77
Primary Batteries
78
5.2.1
Lechlanche Cell or Zinc-Carbon Dry Cell
78
5.2.2
Alkaline Battery
79
5.2.3
Lithium Battery
79
5.2.4
Mercury Battery
80
5.3
Secondary Batteries or Storage Batteries or Accumulators
5.3.1
Lead-acid Accumulator or Acid Battery
81
5.3.2
Nickel-Cadmium Battery or Nicad Battery
82
5.3.3
Edison Battery or Iron-Nickel Oxide Cells
83
5.4
Solar Cells or Photovoltaic Cells
83
5.5
Fuel Cells
85
5.5.1
Hydrogen-Oxygen Fuel Cell
85
86
5.6 Wind Energy
Short Questions
87
87
Abrasives
Introduction
96
96
Abrasive Power
Properties of Abrasives
96
7.2.1
7.3
Classification of Abrasives
97
7.3.1
Natural Abrasives
97
7.3.2
Artificial or Synthetic Abrasives
98
98
7.4
Uses of Abrasives
98
7.4.1
Abrasive Paper and Abrasive Cloth
7.4.2
Grinding Wheels
99
Short Questions
100
100
81
Lubricants
8.1
8.2
UNIT V
Refractories
6.5
Introduction
88
Requisites or Characteristics of a Good Refractory
88
89
Manufacture of Refractories
Properties of Refractories
89
6.4.1
Refractoriness
89
6.4.2
Spalling Resistance or Thermal Spalling
90
6.4.3
Strength or Refractoriness Under Load (RUL)
90
6.4.4
Porosity
91
6.4.5
Dimensional Stability
91
Classification of Refractories
92
6.5.1
Acid Refractories
92
6.5.2
Basic Refractories
92
6.5.3
Neutral Refractories
92
88-95
96-100
7.1
7.2
5.1
5.2
6.1
6.2
6.3
'6.4
ix
8.3
8.4
8.5
8.6
8.7
8.8
8.9
101-117
Introduction
101
8.1.1
Functions of a Lubricant
101
Mechanisms of Lubrication or Types of Lubrication Mechanism
102
102
8.2.1
Fluid Film or Hydrodynamic Lubrication
8.2.2
Thin Film or Boundary Lubrication
103
8.2.3
Extreme Pressure Lubrication
103
Classification of Lubricants
104
Mineral Oils
104
8.4.1
Extraction of Lubricating Oils (Mineral Oils) from Petroleum
104
8.4.2
Blended or Compounded Oils or Additives to Lubricants
105
Synthetic Lubricants
106
Solid Lubricants
106
8.6.1
Graphite
107
8.6.2
Molybdenum Disulphide
107
Semisolid Lubricants
108
Emulsions
109
Properties of Lubricants
109
8.9.1
Viscosity
110
8.9.2
Flash Point and Fire Point
111
8.9.3
Cloud and Pour Points
112
112
8.9.4
Aniline Point
Contents
8.10
8.9.5
Carbon Residue Test
8.9.6
Neutralization Number
8.9.7
Saponification Number
8.9.8
Oiliness
114
Selection of Lubricants
114
113
113
114
10.10
10.11
118-121
Nanomaterials
9.3
10.8
10.9
Solved Examples
115
Short Questions
116
116
Problems
117
9.1
9.2
Contents
Introduction
118
Applications of Nanomaterials
119
9.2.1
In Medicine
119
9.2.2
In Fuel Cells
119
9.2.3
In Catalysis
120
Carbon Nanotubes
120
9.3.1
Synthesis of Carbon Nanotubes
120
9.3.2
Properties of Carbon Nanotubes
121
9.3.3
Applications of Carbon Nanotubes
121
10.12
10.13
10.14
10.15
10.16
Short Questions
121
Descriptive Question
121
10.17
UNIT VI
Electrochemistry
10.1
10.2
10.3
10.4
10.5
10.6
10.7
Introduction
122
Electrolysis
123
Conductance or Conductivity of Electrolytes
124
10.3.1 Variation of Conductance with Dilution
125
Conductometric Titrations
127
10.4.1 Titration of a Strong Acid with a Strong Base
127
10.4.2 Titration of a Weak Acid (CH 3COOH) with a Strong
Base (NaOH)
127
10.4.3 Titration of a Strong Acid (HCl) against a Weak Base
(NH40H)
128
10.4.4 Titration of a Weak Acid (CH 3COOH) against a
Weak Base (NH40H)
128
10.4.5 Titration Involving Precipitation Reaction
129
Electrochemical Cells
130
The emf of a Cell
131
Electrode Potential
131
10.7.1 Sign of Electrode Potential
132
10.7.2 Measurement of Single Electrode Potential
132
122-154
10.18
10.19
xi
Reference Electrodes
132
10.8.1 Hydrogen Electrode
132
10.8.2 Calomel Electrode
133
Nemst Equation
134
10.9.1 Calculation of Single Electrode Potential from Nernst
Equation
135
Ion Selective Electrodes
136
10.10.1 Glass Electrode
136
Determination of pH of a Solution
137
10.11.1 Determination of pH of a Solution Using Hydrogen
137
Electrode
10.11.2 Determination of pH of a Solution Using Calomel Electrode
137
10.11.3 Determination of pH of a Solution Using Glass Electrode
138
Concentration Cells
138
10.12.1 Electrode Concentration Cells
138
10.12.2 Electrolyte Concentration Cells
138
139
10.12.3 Applications of Concentration Cells
140
Reversible Cells
141
Irreversible Cells
141
Standard Cell
Measurement of emf of a Cell
142
10.16.1 Applications of emf Measurements
143
Electrochemical Series
144
10.17.1 Applications of Electrochemical Series or Electrode
Potentials
145
Galvanic Series
145
Potentiometric Titrations
146
10.19.1 Potentiometric Estimation of Ferrous Ion
146
10.19.2 Potentiometric Estimation of Silver Ion
147
Solved Examples
147
Short Questions
152
152
Problems
153
UNIT VII
11 CorroSion and Corrosion Control

ILl
11.2
11.3
Introduction
155
11.1.1 Cause of Corrosion
155
Theories of Corrosion
156
11.2.1 Direct Chemical Attack or Chemical or Dry Corrosion
1~ .2.2 Electrochemical Theory or Wet Corrosion
156
DIfferential Aeration or Concentration Cell Corrosion
157
155-169
156
di
Contents
Factors Influencing Corrosion

159
11.4.1 Nature of the Metal
159
11.4.2 Nature of the Environment
11.5 Types of Corrosion
161
11.6 Corrosion Control
164
Short Questions
168
169
11.4
160
170-183
12 Protective Coatings
Introduction
170
Pretreatment of the Surface or Preparation of Materials for Coating
171
12.2.1 Degreasing
171
12.2.2 Removal of Oxide Scales or Descaling
171
12.2.3 Mechanical Cleaning
171
12.2.4 Electrochemical Method
171
12.3 Metallic Coatings
171
12.3.1 Hot Dipping
171
12.3.2 Spraying
172
12.3.3 Cladding
172
12.3.4 Cementation
172
12.3.5 Electroplating or Electrodeposition
173
12.4 Electroless Plating
175
12.4.1 Various Steps Involved in Electroless Plating
175
12.4.2 Some Electroless Platings
176
12.4.3 Advantages of Electroless Plating over Electroplating
178
12.4.4 Limitations of Electroless Plating
178
12.5 Organic Coatings
178
12.5.1 Paints
178
Short Questions
182
183
12.1
12.2
UNIT VIII
13 Fuels and Combustion
13.1
13.2
13.3
13.4
13.5
Introduction
184
Cll:lssification of Fuel
184
185
Characteristics of a Good Fuel
Advantages and Disadvantages of Solid, Liquid and Gaseous Fuels
13.4.1 Solid Fuels
185
13.4.2 Liquid Fuels
186
13.4.3 Gaseous Fuels
186
Calorific Value
187
13.5.1 Theoretical Calculation of Calorific Value
188
184-231
Contents
188
Classification of Coal
189
Varieties of Coal
190
Analysis of Coal
191
Carbonization
194
Requisites of Good Metallurgical Coke
195
Differences between Coal, Coke and Charcoal
Manufacture of Metallurgical Coke
196
Hydrogenation of Coal
197
13.7 Liquid Fuels
199
199
13.7.1 Classification of Petroleum
13.7.2 Refining of Petroleum
200
13.7.3 Cracking
201
204
13.7.4 Synthesis of Gasoline
205
13.7.5 Refining of Petrol
13.7.6 Knocking
207
13.7.7 Leaded Petrol
207
13.7.8 Reforming
208
13.7.9 Diesel Oil
209
13.7.10 Diesel Index
210
13.8 Gaseous Fuels
210
13.8.1 Natural Gas
210
210
13.8.2 Compressed Natural Gas (CNG)
211
13.8.3 Liquefied Petroleum Gas (LPG)
13.8.4 Producer Gas
211
13.8.5 Water Gas
213
13.9 Combustion
214
13.9.1 Explosive Range or Limits of Inflammability
13.9.2 Ignition Temperature
214
13.9.3 Spontaneous Combustion
215
13.9.4 Flue Gas Analysis
215
13.9.5 Combustion Calculations
216
Solved Examples
217
Short Questions
228
228
Problems
229
13.6
xiii
Coal
13 .6.1
13.6.2
13.6.3
13.6.4
13.6.5
13.6.6
13.6.7
13.6.8
195
214
UNIT IX
185
14 Phase Rule
14.1
14.2
14.3
14.4
Introduction
232
Phase
232
Component
233
Degrees of Freedom
232-242
235
xiv
--
Contents
16.7
14.5
14.6
Phase Diagrams
235
Application of Phase Rule to One-Component Systems
235
14.6.1 Water System
235
14.7 Two-Component Systems
237
14.8 Binary Alloy System or Simple Eutectic System
23714.8.1 Lead-Silver System
237
14.8.2 Applications of ~he Phase Diagram of Two-Component
System or Pattinson's Process for the Desilverization of
Argentiferous Lead
239
240
14.9 Thermal Analysis
14.10 Uses of Phase Diagram
240
14.11 Uses of Phase Rule
241
14.12 Limitations of Phase Rule
241
Short Questions
241
242
15 Alloys
243-250
15.1
15.2
15.3
15.4
Introduction
243
Importance of Alloys
243
Manufacture of Alloys
244
Classification of Alloys
245
15.4.1 Ferrous Alloys
245
15.4.2 Non-Ferrous Alloys
246
15.5 Effects of Alloying Elements on Properties of Steel
15.6 Heat Treatment of Alloys
247
15.7 Types of Heat Treatment Processes
248
Short Questions
250
250
247
UNIT X
16 Analytical Techniques
16.1
16.2
16.3
16.4
16.5
16.6
251-276
Introduction
251
Electromagnetic Spectrum
251
Electromagnetic Radiations
252
Absorption of Radiations
253
Types of Spectroscopy
254
16.5.1 Atomic Spectroscopy: Electronic Transition
254
16.5.2 Molecular Spectroscopy: Vibrational Transition and Rotational
Transition
254
Light Absorption
255
16.6.1 Lambert's Law
255
16.6.2 Beer's Law
256
Contents
Colorimetric Analysis
257
16.7.1 Working of a Colorimeter
257
258
16.7.2 Estimation of Concentration of a Solution by Colorimetry
258
16.7.3 Estimation of Iron by Colorimetry
16.8 Flame Photometry or Flame Emission Spectroscopy
259
16.8.1 Instrumentation
260
16.8.2 Applications of Flame Photometry
261
16.8.3 Limitations of Flame Photometry
261
16.8.4 Estimation of Sodium by Flame Photometry
262
16.9 Visible and Ultraviolet Spectroscopy
262
16.9.1 Types of Electrons Involved in Organic Molecules
262
263
16.9.2 Types of Transitions in Organic Molecules
16.9.3 Chromophores
263
16.9.4 Auxochromes
263
264
265
16.9.6 Working of Visible and UV Spectrophotometer
16.9.7 Applications of Visible and Ultraviolet Spectroscopy
265
16.10 Infrared Spectroscopy
266
16.10.1 Modes of Vibrations in a Molecule
267
16.10.2 Fingerprint Region
269
269
16.10.4 Working of Infrared Spectrometer
270
16.10.5 Applications of IR Spectroscopy
270
16.11 Atomic Absorption Spectroscopy (AAS)
271
16.11.1 Principle
271
271
16.11.3 Working of Atomic Absorption Spectrophotometer
27~
16.11.4 Advantages of Atomic Absorption Spectroscopy
273
16.11.5 Quantitative Estimation of Nickel
273
Solved Examples
274
Short Questions
275
276
Problems
276
xv
PREFACE
To impart sound concepts of the principles of chemistry, different application-oriented topics

such as water technology, non-conventional energy sources and storage devices, engineering
materials, corrosion and its control, fuels and combustion, analytical techniques, etc. are
included in the first-year engineering curriculum. A chapter on nanomaterials, one of the recent
technological advancements, is also included.
To help students grasp the concepts clearly, the book is written in an easy-to-understand
style. The solutions to the problems are presented in a stepwise manner. This book covers the
topics prescribed in the new semester-pattern syllabus of Anna University (Chennai, Trichy,
Coimbatore and Tirunelveli). The second edition updates all of the essentials and includes new
topics required by the first-year engineering students for their courses in Engineering
Chemistry-I and Engineering Chemistry-II.
We wish to thank our Principal, Dr. S. Balakrishnan and Management for their constant
encouragement and support.
We are grateful to the staff of PHI Learning Pvt. Ltd., New Delhi for publishing this book
in time.
N. Krishnamurthy
P. Vallinayagam
D. Madhavan
xvii
WATER TECHNOLOGY
1.1
INTRODUCTION
Water is the most important compound for the existence of human beings, ammals and plants.
Besides these, water has great applications in industries. Water is mainly used in power generation industry for the production of electric current through steam generation. Water is also used
as a coolant in atomic reactors as well as chemical plants. It is also largely used in irrigation
for agricultural purposes.
The main sources of water are (a) rain, (b) rivers and lakes (surface water), (c) wells and
springs (ground water), and (d) sea water.
From the point of view of industrial applications, it is not usually feasible to use rainwater
and seawater. Rainwater is irregular in supply and generally expensive to collect. Sea water is
too saline for most industrial uses except cooling.
So, surface and ground 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. A few examples are given in Table 1.1.
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 types of impurities from water and making it fit for domestic or industrial purposes is called
water treatment. Before treating water one must know the nature as well as the amount of
impurities.
TABLE 1.1
Purpose
Beverages
Specification
Remark
--------------------------------------------------------------
Laundries
Power stations
(a) Cooling systems
(b) Boiler feed

Paper
Should not be alkaline
Soft, free from colour, Fe

and Mn salts
Non-corrosive, non-scale
forming, must not promote
the growth of algae
Zero hardness
Free from
(a) hardness and alkalinity
Textiles
1.2
Different uses of water
Alkalinity in water tends to neutralize

the fruit acids and destroy the taste.
Hardness increases the consumption of
soaps and detergents. Salts of Fe and Mn
give a grey or yellow shade to the fabric.
Scale formed on using untreated water

prevents efficient heat transfer.
Consumption of alum by the alkaline
water increases the cost of production.
(b) Si02
Produces cracks on the paper.
Free from turbidity,

colour, Fe and Mn
Causes uneven dyeing, leaves stains on

fabric.
IMPURITIES IN WATER
The impurities present in water may be broadly classified as follows.

1. Dissolved impurities: The dissolved impurities are mainly the carbonates, bicarbonates,
chlorides and sulphates of calcium, magnesium, iron, sodium and potassium. The presence
of these salts imparts hardness to water. The dissolved impurities also include dissolved
gases like oxygen and carbon dioxide.
2. Suspended impurities:
The following are the types of suspended impurities:
(a) Inorganic: Clay and sand

(b) Organic: Oil globules, vegetable and animal matter
The above suspended impurities impart turbidity, colour and odour to water.
3. Colloidal impurities: They are finely-divided silica and clay, organic waste products,
complex protein aminoacids, etc.
4. Microorganisms:
1.2.1
They are algae, fungi and bacteria.
Sources of Impurities in Water
The sources of impurities in water are the following:

1. Water collects impurities from the ground, rocks or soil with which it comes in contact.
2. Water becomes impure when it comes in contact with sewage or industrial wastes.
Water Technology
3. Organic impurities in water are generally introduced by the decomposition of plant and
animal remains.
4. Gases like oxygen and carbon dioxide are picked up by rainwater from the atmosphere.
1.3 HARD WATER

A sample of water which produces lather readily with soap is called soft water. If it does not
produce lather readily with soap, it is said to be hard water.
1.3.1 Disadvantages of Hard Water

The following are the disadvantages of hard water:
I. Hard water is not useful for various domestic purposes, viz. washing, bathing and
drinking. The hardness producing ions convert soluble soaps to insoluble precipitates. This
results in wastage of soaps in washing and bathing.
2. Hard water is not useful for many industries such as textile, sugar and paper. Dissolved
salts like Ca, Mg, Fe and Mn affect the following properties.
(a) Giving a smooth and glossy finish to paper in paper industry.
(b) Producing good lather in laundry.
(c) Producing good shades and colour to fabrics in textile industry.
3. Hard water is also not suitable for steam raising in boilers, since they produce scales on
inner plates. Corrosion, priming, foaming and caustic embrittlement are the other
problems caused by hard water.
4. Hard water is not suitable for laboratory analysis, because the hardness producing ions
interfere in various reactions.
1.3.2 Hardness of Water

Hardness was originally defined as the soap consuming capacity of a water sample. Soap is the
sodium salt of higher fatty acids, e.g. sodium stearate. The sodium salt is soluble in water, but
the corresponding calcium and magnesium ions are insoluble in water. When soap is added to
soft water, it dissolves and lathers readily. On adding soap solution to a sample of hard water
which contains calcium or magnesium ions, soap is precipitated as insoluble salts which prevent
the formation of lather. This reaction causes the loss of soap. No lather is obtained until all the
ions are removed. So, large amount of soap is consumed unnecessarily before lather is formed.
2C 17H3s COONa + CaCl2 ---7 (C17H35COO)2Ca + 2NaCI
sodium stearate
curdy precipitate of
calcium stearate
Hardness of water due to the presence of bicarbonates of Ca and Mg is called temporary

hardness. It is also called carbonate hardness (CH). Temporary hardness can be removed by
boiling, which converts the bicarbonates into insoluble carbonates:
Ca(HC03)2
---7
CaC03 + H 20 + CO2
. Permanent hardness is due to the presence of chlorides and sulphates of Ca and Mg and
cannot be removed by boiling. It is also called non-carbonate hardness (NCH). CH and NCH
thus constitute the total hardness.
Units of hardness
The following are the common units used in hardness measurements.
1. Parts per million (ppm): It is defined as the number of parts by weight of CaC03
present in million parts by weight of water.
1 ppm = 1 part of CaC03 equivalent hardness in 106 parts of water
2. Milligram per litre:

litre of water.
It is defined as the number of milligrams of CaC03 present in one i
1 mgll = 1 mg of CaC03 equivalent hardness in one litre of water
Since weight of 1 litre of water = 1 kg
= 1000 g
=
=
1000x 1000
106 mg
1 mg/l = 1 mg of CaC03 per 106 mg of water

=
1 part of CaC03 per 106 parts of water
1 ppm
Thus, mathematically both units are equal.

Hardness is usually expressed in terms of equivalent of CaC03 in order to simplify r
calculations in water analysis. Hence, all the hardness causing impurities are first converted in
terms of their respective weights equivalent to CaC0 3 by using the relation
weight of the hardness producing salt
molecular weight of the salt
. h
. al
. h f C CO
ent welg to a 3
- - - - - - - - - = - - - - - - ' = - - - - x mo ecu ar welg t 0
f C CO
a 3
or
weight of the hardness producing salt
--..::...-------=-------==--X
equivalent weight of the salt
eqUlV
Table 1.2 gives the multiplication factor for converting various substances into equivalents
of CaC03
TABLE 1.2
Multiplication factor for converting various substances into equivalents of CaC03
Substance
Calcium bicarbonate
Magnesium bicarbonate
Calcium sulphate
Calcium chloride
Magnesium sulphate
Magnesium chloride
Calcium carbonate
Molecular weight
Valency
Equivalent weight
162
146
136
111
120
95
100
2
2
2
2
2
2
2
81
73
68
55.5
60
47.5
50
Water Technology
Estimation of hardness
Hardness is usually determined by the EOTA method.
EDTA method:
EDTA is ethylenediaminetetraaceticacid. The structure of EOTA is
Since EDTA is insoluble in water, its disodium salt is used as a complexing reagent.
Principle: Estimation of hardness by EOTA method is based on the principle that EOTA
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, buffer solution
(NH4Cl and NH40H 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 purple red colour.
[:;.] + Eriochrome B1ack-T - > [:g Eriochrome BlaCk+omPlex

(unstable complex)
When this solution is titrated against EDTA, EOTA replaces the indicator from the indicator complex. When all the hardness causing ions are complexed by EOTA, the indicator is
set free and the end point is the sharp change in colour from purple red to blue. The total
hardness is thus determined.
[ ::Eriochrome Black-T].omPlex + EDTA -> [ : :EDTA] complex + Eriochrome Black-T

(blue)
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 EOTA as before.
Therefore,
total hardness - permanent hardness "" temporary hardness
Experimental procedure: A known volume of the sample of hard water (V ml) is treated
with about 10 ml of a buffer solution and 5 drops of Eriochrome Black-T indicator. This
solution is then titrated against the standard EOTA reagent (standardized such that 1 ml of the
reagent corresponds to I mg of CaC03). The end point is the colour change ,from purple red
to blue.
Let the volume of EDTA consumed be VI ml.

1 ml of EDTA = 1 mg of CaC03
VI ml of EDTA
VI mg of CaC0 3
This hardness is present in V ml of hard water.

Total hardness of the sample
l'I x 1000
V
ppm of CaC03 equivalent
A known volume (V ml) of sample water is taken in a beaker and boiled for 15 minutes.
After cooling the mixture, it is filtered and thoroughly washed. The filtrate is collected and
made up to a known volume (V mI). This solution is titrated against EDTA as before. The
volume of EDTA consumed is V2 ml. Then,
Permanent hardness of the sample =
V x 1000
V
ppm of CaC03 equivalent
Hence, (total hardness) - (permanent hardness) gives the temporary hardness.

From the volume of EDTA it is equated to CaC03 equivalent as follows:
1000 ml of 1M EDTA = 100 g of CaC03

1000 ml of O.OIM EDTA = 1 g of CaC03
1 ml of O.OIM EDTA = 1 mg of CaC03
1 ml of 0.02N EDTA = 1 mg of CaC03
1.4 ALKALINITY
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.
CaC03 + CO 2 + H 20
Ca(HC03h
The alkalinity of natural water may be taken as an indication of the concentration of

hydroxides, carbonates and bicarbonates.
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 reactions taking place are as follows:
OH- + H+
H2 0
(I)
C032- + H+
HC0 3-
(2)
HC0 3- + H+
H 20 + CO2
(3)
Water Technology
The volume of the acid used up to phenolphthalein end point P corresponds to the completion of equations (1) and (2), while the volume of the acid used after P corresponds to the
completion of equation (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 (l) to
(3).
The results are summarized in Table 1.3 from which the amount of hydroxides, carbonates
and bicarbonates present in the water sample can be calculated.
TABLE 1.3 Calculation of hydroxides, carbonates and bicarbonates
Alkalinity
OH- (ppm)
C0 32- (ppm)
HC03- (ppm)
0
0
0
(2P - M)
0
2P
2P
2(M - P)
M
0
(M - 2P)
0
P=Q
P = \t2 M
P< \t2M
P> \t2M
P= M
(P = Phenolphthalein alkalinity; M = Methyl orange alkalinity)
Highly alkaline water may lead to caustic embrittlement and also may cause deposition of
precipitates and sludges in boiler tubes and pipes.
The determination of alkalinity is used in the following ways:
I. In calculating the amounts of lime and soda needed for water softening
2. In corrosion control
3. In internal conditioning of boiler-feed water
1.4.1 Experimental Determination of Alkalinity

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 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 VI 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 light pink.
The additional volume of acid consumed is taken as VI ml.
Calculation
Volume of acid used up to phenolphthalein end point = VI ml
Normality of acid = NI
Phenolphthalein alkalinity (P) in terms of calcium carbonate equivalent
= \) X NI
20
X 50 x 1000 mg/litre
Additional volume of acid used up to methyl orange end point

Normality of acid = N J
V2 ml
Methyl orange alkalinity (M) in terms of calcium carbonate equivalent
= ("1 + V2 ) X Nl
20
x 50 x 1000 mgil'Ure
Then the calculation of hydroxides, carbonates and bicarbonates is made with the help of
Table 1.3.
1.5
BOILER FEED WATER
In industry, one of the chief uses of water is generation of steam by boilers. Water fed to a boiler
for the generation of steam is called boiler feed water.
1.5.1
Essential Requirements of Boiler Feed Water
Boiler feed water should be free from the following:

1. Turbidity, oil and non-scaling dissolved salts to reduce the tendency for priming and
foaming.
2. Hardness-causing and scale-forming constituents like Ca and Mg salts as the formation
of scales would result in wastage of fuel, loss in output and overheating of the boiler
tubes leading to explosion.
3. Dissolved oxygen and CO 2 in order to prevent corrosion in the boiler.
4. Caustic alkali to remove caustic embrittlement.
If the hard water obtained from natural sources is fed directly to the boilers, there arise
many troubles such as priming, foaming, sludge and scale formation and caustic embrittlement.
1.5.2
Priming
During the production of steam in the boiler, due to rapid boiling some particles of liquid water
are carried along with steam. Steam containing droplets of water is called wet steam. This
process of wet steam formation is called priming.
Priming causes the following harmful effects.
1. Wet steam carries dissolved salts of water with it to the super-heater where they are
deposited after the evaporation of water. The deposited salts hinder the flow of steam
and hence reduce the efficiency.
2. Water and dissolved salts may enter the parts of the machinery thereby decreasing the
life of the machinery.
Priming may be caused by (a) a very high water level, (b) presence of foam on the surface
and (c) high steam velocity.
Priming can be prevented by maintaining a low water level in the boiler and by removing
oily materials present in water.
Water Technology
1.5.3 Foaming
The formation of stable bubbles above the surface of water is called foaming. These bubbles
are carried over by steam leading to excessive priming. It is caused by the presence of soluble
impurities like alkali metal salts and oil which fonn a soap. Foaming can be controlled by the
action of anti-foaming agents like synthetic polyamides.
1.5.4 Sludge and Scale Formation in Boilers

In a boiler, water is continuously converted into steam. Due to this continuous evaporation of
water, the concentration of soluble matters increases progressively. Then the salts start
separating out from the solution in the order of their solubility, the least soluble one separating
out first. Some of the salts like MgCI 2, CaCl 2 and MgS0 4 separate in the body of the liquid in
the form of soft deposits which can be flushed out easily (Figure 1.1 a). Such soft and nonadherent deposits are known as sludges.
Some salts like CaS04 and Mg(OH)z fonn hard adherent deposits on the inner walls of
the boiler. They are called scales (Figure 1.1 b). Scales are so hard and adherent that they are
difficult to remove even with the help of hammer and chisel.
--..>.--- Scale
Sludge--+-..,....
.~-I-~
Water
Water--t-~
Boiler
wall
Boiler wall
(a)
FIGURE 1.1
(b)
(a) Sludge in boiler and (b) scale in boiler.
Table 1.4 shows the differences between sludges and scales.
TABLE 1.4 Differences between sludges and scales

Sludges
I. Sludges are soft and non-adherent deposits.
Scales
1. Scales are hard deposits which stick very

firmly to the inner surface of the boiler.
2. Sludges can be removed easily.
2. Scales are very difficult to remove.
3. Sludges can transfer heat to some extent

and are less dangerous.
3. Scales are bad conductors of heat and are

more dangerous.
4. Sludges are formed by substances like

MgCI2 and CaCI 2.
4. Scales are formed by substances like CaS04

and Mg(OHh.
10
Disadvantages of scale formation
The following are the disadvantages of scale formation:

1. 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.
2. Since the scale acts as a heat insulator, the boiler metal is overheated. Due to'
overheating, the metal expands until the scale on it cracks. When thick scales crack, the
water suddenly comes in contact with overheated boiler metal. This causes the
formation of a large amount of steam suddenly. This results in the development of high
pressure inside the boiler which may lead to a dangerous explosion.
3. 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.
1.5.5 Caustic Embrittlement

Caustic embrittlement is the phenomenon during which the boiler material becomes brittle due
to the accumulation of caustic substances.
It is a very dangerous form of stress corrosion occurring in mild steel boiler metals'
exposed to alkaline solution at high temperatures, resulting in the failure of the metal. Stressed
parts like bends, joints and rivets are severely affected.
Boiler water usually contains a small proportion of Na2C03. In high pressure boilers, this
breaks up to give NaOH and makes the boiler water more alkaline:
Na2C03 + H 20
2NaOH + CO2
This very dilute alkaline boiler water flows into the minute hair cracks and crevices ~
capillary action. There the water evaporates and the concentration of caustic soda increases
progressively. The concentrated alkali dissolves iron as sodium ferro ate in crevices, cracks, etc.
where the metal is stressed. This causes brittlement of boiler parts particularly stressed parts like:
bends, joints and rivets causing even failure of the boiler.
Caustic embrittlement can be avoided (a) by using sodium phosphate as softening reagent
instead ofNa2C03 and (b) by adding tannin or lignin to boiler water which blocks the hair cracks.
1.6
BOILER CORROSION
Boiler corrosion is the decay of boiler material due to chemical or electrochemical attack of its
environment. The corrosion in boilers is due to dissolved oxygen, dissolved CO2 and acids
produced by the hydrolysis of dissolved salts. Therefore, removal of these prevents the corrosion
of boilers.
1.6.1
Removal of Dissolved O2
Dissolved oxygen in water is mainly responsible for the corrosion of a boiler. The dissolve(
oxygen in water attacks the boiler material at high temperatures.
Water Technology
11
2Fe + 2H20 + O2 ~ 2Fe(OH)2

4Fe(OH)2 + O 2 + 2H20 ~ 2[Fe2033H20]
(rust)
Dissolved oxygen can be removed from water by chemical and mechanical means. Sodium
sulphite, hydrazine, etc. are some of the chemicals used for removing oxygen.
2Na2S03 + O2 ~ 2Na2S04
N2H4 + O2 ~ N2 + 2H20
Hydrazine is found to be an ideal compound for removing dissolved oxygen since the
products are water and inert N2 gas. It removes oxygen without increasing the concentration of
dissolved salts.
Dissolved O2 can also be removed from water by mechanical deaeration (Figure 1.2). In
this process, water is allowed to spray slowly by the perforated plates fitted inside the tower.
Vacuum is applied to this tower and the sides of the tower are also heated. High temperature
and low pressure reduce the quantity of dissolved O 2 in water.
Water feed
,----1
1t-----s-
~
~
Perforated
plates
Va,"om pomp
7-
Steam jacket
Deaerated water
FIGURE 1.2
Mechanical deaeration of water.
1.6.2 Removal of Dissolved CO2

Dissolved CO 2 in water produces carbonic acid which is corrosive in nature:
CO2 + H 20
H2C03
CO2 can be removed from water by chemical or mechanical means. In the chemical method CO2
is removed from water by the addition of a calculated quantity of NH 40H:
12
2NH40H + CO 2
(NH4)zC03 + HzO
Dissolved COz along with oxygen can be removed by mechanical deaeration.
1.6.3 Removal of Acids

Acids produced from salts dissolved in water are also mainly responsible for corrosion of
boilers. Certain salts like MgCI2 and CaClz on hydrolysis at higher temperatures produce
hydrochloric acid which corrodes the boiler.
MgCl 2 + 2H2 0
Mg(OH)z + 2HCl
The liberated acid can produce rust in the following way.

Fe + 2HCI
FeCl2 + 2H20
4Fe(OH)2 + O2 + 2H20
FeCl2 + Hz
Fe(OH)2 + 2HCI
2[Fez033H20]
(rust)
Hence, even a very small amount of MgCI2 can cause considerable corrosion of the boiler
metal. Corrosion by acids can be avoided by the addition of alkali to the boiler water from
outside.
1.7
PREVENTION OF SCALE FORMATION OR 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 oxygen. The process of removing
hardness producing salts from water is known as softening of water.
Softening of water can be done in two ways (a) external treatment and (b) internal
treatment.
1.7.1
External Treatment or External Conditioning
The external treatment of water is carried out before its entry into the boiler. The external
treatment can be done by the following methods.
1. Zeolite process
2. Ion exchange or de ionization or demineralization process
Zeolite process or permutit process
Zeolites are naturally occurring hydrated sodium aluminosilicate minerals. The chemical
formula is
Na20'Alz03 'xSiOzyH20
The synthetic form of this zeolite is called permutit and is represented by Na2Ze. In this process
the hard water is allowed to percolate through sodium zeolite. The sodium ions which are
loosely held in this compound are replaced by Ca2+ and Mg2+ ions.
Water Technology
13
When zeolite comes in contact with hard water, it exchanges its sodium ions with calcium
and magnesium ions of hard water to form calcium and magnesium zeolites:
Ca(HC03h + Na2Ze
CaZe + 2NaHC03
Mg(HC0 3)2 + Na2Ze
MgZe + 2NaHC03
CaCl2 + Na2Ze
CaZe + 2NaCI
MgS04 + Na2Ze
MgZe + Na2S04
As sodium ions do not give any hardness to water, the effluent water will be soft. The
exhausted zeolite is again regenerated by treating with 5-10% of sodium chloride solution.
CaZe + 2NaCI
MgZe + 2NaCI
Na2Ze + CaCl2
Na2Ze + MgCl 2
A simple zeolite softener is shown in Figure 1.3.
Brine inlet
Hard water_
----------------------------------------------:-:-:-:-:-:- Hard water .-:-:-:-:-:-:-------------- - - - - - - - - - -------------~

-----------------------Sodium zeolite
gggggg~~~gd'-Fine gravel
Coarse gravel
FIGURE 1.3
Advantages:
Zeolite softener.
The tollowing are the advantages of the zeolite process:
I. Water of nearly zero hardness is obtained.

2. This method is very cheap because the regenerated permutit is again used.
3. No sludge is formed during this process.
4. The equipment used is compact and occupies a small space.
5. Its operation is also easy.
6. The process can be made automatic and continuous.
14
Disadvantages:
The following are the disadvantages of the zeolite process:
1. The zeolite process cannot be used for turbid and acidic water as they will destroy ilil
zeolite bed.
2. This treatment replaces only the cations leaving all the anions like HC03- and col
in the soft water.
When such water is boiled in boilers CO2 is liberated. Free CO2 is weakly acidic in
nature and extremely corrosive to boiler metal.
Na2C03 + H 20 ~ 2NaOH + CO2
NaHC03 ~ NaOH + CO2
Due to the formation of sodium hydroxide, the water becomes alkaline and can callSt
caustic embrittlement.
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.
Ion exchange or deionization or demineralization process
In ion exchange process, cations like Ca2+ and Mg2+, and anions like CI- and S042- which are
responsible for hardness are removed respectively by cation exchange resins and anion
exchange resins.
Ion exchange resins are insoluble, crosslinked, long chain organic polymers with a
microporous structure. The functional groups attached to the chains are responsible for the ion
exchanging properties. Resins containing acidic groups (-COOH, -S03H) are capable of
exchanging their H+ ions cations of hard water. Resins containing basic groups (-NH2' -OH)
are capable of exchanging their anions with the anions of hard water.
Process: Water is passed through a tank having a cation exchanger which adsorbs all the
cations present in water.
RH2 + CaCl2 ~ RCa + 2HCI

RH2 + MgS04
RMg + H2S04
The cation-free water is now passed through another tank having an anion exchange!
which adsorbs all the anions present in water.
R'(OHh + 2HCI
R'CI 2 + 2H20
R'S04 + 2H20
R'(OH)2 + H2S04 ~
The water coming out of the anion exchanger is completely free from cations and anions
responsible for hardness. It is known as deionized water or demineralized water. It is as pure
as distilled water.
Regeneration: Cation exchange resins are regenerated by passing a dilute solution of hydrochloric acid through them.
RCa + 2HCI
RH2 + CaCl2
Similarly, the anion exchange resins are regenerated by passing a dilute solution of sodium
hydroxide through them.
Water Technology
R'Cl 2 + 2NaOH
15
R'(OH)2 + 2NaCI
A typical deionizer is shown in Figure 1.4.

Raw
water
regeneration
regeneration
' - - - - = : - . Deionized
' - - - - - - - water
FIGURE 1.4
Deionizer.
Advantages: The following are the advantages of the ion exchange process:
1. Highly acidic or alkaline water can be treated by this process.
2. This produces water of very low hardness (nearly 2 ppm).
Disadvantages:
The disadvantages of the ion exchange process are as follows:
1. The equipment is costly and more expensive chemicals are needed.

2. If water contains turbidity, then the output of the process is reduced.
Table 1.5 lists the difference between zeolite and demineralization processes.
TABLE 1.5 Differences between zeolite and demineralization processes
Zeolite process
Demineralization process
I. Exchanges only cations.

2. Acidic water cannot be treated because acid
decomposes the zeolite.
1. Exchanges cations as well as anions.

2. Acidic water can be treated.
3. Dissolved salt concentration of treated water

is higher than that of untreated water. Hence
the treated gives rise to priming and foaming
in boilers.
3. Dissolved salt concentration of the water is nil

or less. Hence there is no priming and foaming.
16
1.7.2
Internal Treatment or Internal Conditioning
The internal treatment or conditioning of boiler feed water refers to the conditioning of water
in the boiler itself. This treatment consists of adding chemicals directly to the water in the boiler I
for removing dangerous scale forming salts which were not completely removed in externru
treatment for water softening.
This is mainly used as a corrective treatment to remove the slight residual hardness an~
also to remove the corrosive tendencies in water.
The following methods are used in the internal softening: (a) colloidal conditionin~
(b) phosphate conditioning, (c) carbonate conditioning, (d) calgon conditioning an~
(e) treatment with sodium aluminate.
Colloidal conditioning
Scale formation can be minimized by introducing into the boiler some colloidal conditioningl
agents like starch and glue. These colloidal substances get coated over the scale forming
particles and thus the coalescence of these particles to a compact scale is prevented. Thus the
scale formed remains loose and non-sticky and can be easily removed.
Phosphate conditioning
In the boiler, scale formation can be avoided by adding sodium phosphate. The phosphate reac~
with calcium and magnesium salts in the boiler water forming easily removable soft sludges of
calcium and magnesium phosphates:
3CaS04 + 2Na3P04
Ca3(P04)2 + 3Na2S04
The main phosphates employed are as follows:

Na3P04 - Trisodium phosphate
Na2HP04 - Disodium hydrogen phosphate
NaH 2P0 4 - Sodium dihydrogen phosphate
If the water to be treated is acidic in nature, trisodium phosphate which is alkaline in
nature is normally used. If the water is neutral, disodium hydrogen phosphate is used. If the
water is alkaline, sodium dihydrogen phosphate which is acidic in nature is used.
Carbonate conditioning
Scale formation can be avoided in boilers by adding sodium carbonate to boiler water. The scale
forming salt like calcium sulphate is converted into calcium carbonate which can be removed
easily:
Calgon conditioning
Calgon conditioning involves the addition of calgon or sodium hexametaphosphate to boiler

water. This substance interacts with calcium ions forming a highly soluble complex and thus
prevents the precipitation of scale forming salt.
Water Technology
17
Treatment with sodium aluminate
When sodium aluminate is treated with boiler water, it gets hydrolyzed to give sodium
hydroxide and a gelatinous precipitate of aluminium hydroxide.
NaAl02 + 2H20
NaOH + Al(OHh
The formed NaOH reacts with magnesium salts

MgCl2 + 2NaOH
Mg(OH)2 + 2NaCI
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.
In a nutshell, Table 1.6 shows the differences between external treatment and internal
treatment.
TABLE 1.6 Differences between external treatment and internal treatment
External treatment
Internal treatment
I. The external treatment of water is carried

out before its entry into the boiler.
1. The internal treatment of water is carried out

in the boiler itself.
2. It includes colloidal conditioning, carbonate
conditioning, phosphate conditioning, calgon
conditioning, etc.
3. Low pressure boilers require internal treatment.
2. It includes lime-soda process, perrnutit process and ion-exchange process.
3. High pressure boilers require external

treatment.
4. It is a preventive method.
4. It is a corrective method.
1.8 POTABLE WATER (WATER FOR DOMESTIC SUPPLY)

Municipalities have to supply potable water, i.e. water which is safe to drink.
Characteristics of potable water
The following are the characteristics of potable water:

I. Potable water should be colourless and odourless.
It should have a good taste.
Potable water should be clear from suspended impurities.
It should be free from objectionable gases like CO2, NH3 and H 2S.
Potable water should be free from harmful bacteria.
It should not have more than 0.1-0.2 ppm of free chlorine.
2.
3.
4.
5.
6.
Rivers, lakes and wells are the most common sources of water used by municipalities. The
actual treatment methods depend directly on the impurities present. For removing various types
of impurities (see Table 1.7), the following treatment processes are employed.
18
TABLE 1.7
Types of impurities and their removal processes
Impurity
1. Floating matter such as leaves and

wood pieces
2. Suspended impurities such as clay
and sand
3. Fine suspended matter (silt)
4. Microorganisms and colloidal matter
5. Pathogenic bacteria
1.8.1
Process used for removal
1. Screening
2. Sedimentation
3. Coagulation
4. Filtration
5. Disinfection (Sterilization)
Treatment Processes for Removal of Impurities
Screening
Screening is the process of removing floating materials like wood pieces and leaves from water.
Raw water is allowed to pass through a screen having a large number of holes which removes
the small and large floating matter.
Sedimentation
Sedimentation is the process of removing suspended impurities by allowing the water to stand
undisturbed for 2-6 hours in big tanks. Due to force of gravity, most of the suspended particles
settled down at the bottom and they are removed. Sedimentation removes only 70-75% of the
suspended matter.
Coagulation
Finely-divided silica, clay, etc. do not settle down easily and hence cannot be removed by
sedimentation. Most of these are in colloidal form and are negatively charged and hence do not
coalesce because of mutul:il ]epulsion. Such impurities are removed by coagulation method.
Here, certain chemicals like alum and A12(S04)3 are added to water. When AI2(S04)3 is added
to water, it hydrolyzes to form a gelatinous precipitate of AI(OH)3' The gelatinous precipitate
of AI(OHh entraps finely divided and colloidal impurities, settles to the bottom and can be
removed easily.
Filtration
For removing bacteria, colour, taste, odour, fine suspended particles, etc. and to produce clear
water, filtration is used. In this process, water is passed through beds of fine sand, coarse sand
and other granular material. The porous material used is the filtering medium and the equipment
used for filtration is known as filter, e.g. slow sand filter.
A typical slow sand filter is shown in Figure 1.5.
It consists of a tank containing thick beds of fine sand (at the top), coarse sand, fine gravel
and coarse gravel (at the bottom). When the water passes through the filtering medium, it
flows through the various beds slowly due to gravity. The rate of filtration slowly decrease~
due to the clollllinll of imnurities in the nores of the sand bed. When the rate of flow becomes
Water Technology
Water inlet _
19
_ _J-L=
=================================================
-_-_-_-_-_-_-_-_-_-_-_-_-_-_-_-_-_-_-_-_-_-_-_-_-_-
---,----------------------------------------------------
Coarse sand
Fine gravel
Coarse gravel
Water outlet
-------------------------
FIGURE 1.5
Slow sand filter.
very slow, filtration is stopped and the bed is cleaned by scraping of a smaller layer of the
sand bed (top layer) and replacing it with the clean sand. Bacterias are partly removed by this
filtration process.
Sterilization
The complete removal of harmful bacteria is known as sterilization. The following sterilizers
are generally used for sterilizing water.
I. Sterilization by chlorine or bleaching powder: Chlorine is the most common
sterilizing agent in water treatment. Chlorine may be added in the form of bleaching
powder or directly as a gas or in the form of concentrated solution in water.
When bleaching powder is added to water, HOCI which acts as a powerful germicide
is produced. It is believed that HOCI reacts with bacteria and inactivate the enzymes
present in the cells of bacteria. These enzymes are responsible for the metabolic
activities of microorganisms. Since these enzymes are inactivated, microorganisms
become dead.
CaOCl2 + H 20
Cl2 + H20
HOCI + Bacteria
~
~
Ca(OH)2 + Cl2
HCI + HOCI
Bacteria are killed
2. Sterilization by ultraviolet radiations: Ultraviolet radiations emanating from

electric mercury vapour lamp is capable of sterilizing water. This process is particularly
useful for sterilizing swimming pool water. This process is highly expensive.
3. Sterilization by ozone: Ozone is a powerful disinfectant and is readily absorbed by
water. Ozone is highly unstable and decomposes to give nascent oxygen which is
capable of destroying the bacteria.
03~
This process is relatively expensive.
O2 + [0]
20
1.9
BREAK POINT CHLORINATION
In break point chlorination a sufficient amount of chlorine is added to oxidize (a) organic matter,
(b) reducing substances (Fe 2+, H 2 S, etc.) and (c) free ammonia in raw water leaving behiM
mainly free chlorine which destroys pathogenic bacteria.
When chlorine is added to water, initially it reacts with ammonia and there will ~
formation of chloramines:
NH3 + CI 2 ~ NH2CI + HCI
NH2CI + CI2 ~ NHCI 2 + HCI
NHCI2 + CI2 ~ NCI 3 + HCI
Thus the amount of combined residual chlorine (chloramines) increases with increasm,
dosage. Then the oxidation of chloramines and other impurities start and there is a fall in
combined chlorine content. Thus combined residual chlorine decreases to a minimum at whic~
oxidation of chloramines and other organic compounds complete. This minimum is the bre~
point (Figure 1.6). The reason for such a behaviour is due to the fact that some organit
compounds which defy oxidation at lower chlorine concentration get oxidized when tne
break point chlorine concentration is reached. Since, it is these organic compounds which aI'
generally responsible for bad taste and odour in water, it is clear that break point chlorinatiit
eliminates bad taste and odour.
Further chlorination increases the free residual chlorine (CI2 , HOCI, OCI-). Hence, ii
use chlorine as a good disinfectant, the chlorine dosage has to be given more than the breat
point.
Formation of
chloramines
Destruction of
chloramines and
organic compounds
Chlorine dose added
FIGURE 1.6 Break point chlorination.
1.10
DESALINATION
Depending upon the quantity of dissolved solids water is graded as follows:

1. Fresh water: <1000 ppm of dissolved solids
2. Brackish water: >1000 ppm but < 35,000 ppm of dissolved solids
3. Sea water: >35,000 ppm of dissolved solids
Water Technology
21
Water containing dissolved salts with a peculiar salty or brackish taste is called
brackish water. It is totally unfit for drinking purposes. Sea water and brackish water can
be made available as drinking water through desalination process. The removal of dissolved
solids (NaCl) from water is known as desalination process. The need for such a method
arises due to the non-availability of fresh water. Desalination is carried out by the following
methods:
I. Electrodialysis
2. Reverse osmosis
1.10.1 Electrodialysis
Electrodialysis is based on the fact that the ions present in saline water migrate towards
oppositely charged electrodes under the influence of an applied emf. The movement of ions
takes place through ion-selective membranes.
An electrodialysis cell consists of alternate cation- and anion-permeable membranes
(Figure 1.7). The cathode is placed near the cation-permeable membrane (C) and the anode is
placed near the anion-permeable membrane (A). Under the influence of an emf applied across
the electrodes, the anions (en move towards the anode and the cations (Na+) move towards
the cathode. The net result is the depletion of ions in the even-numbered compartments and
concentration of ions in the odd-numbered compartments. Now the compartments with evennumber are filled with pure water and the compartments with odd-number are with concentrated
brine solution. Thus the salinity is removed from salt water.
, C'
I
ca
--15 :Na
Cathode
C,
,,
,, CD,,,
I
E'
CD:
E',
,,
,,
,, ,,,
+'--
,,,
,
,,
,,,
,,,
,,
,
,,,
,,
CD'
:0:
ell,
CD,
: CICD'
a.'
,,
0'
._,
iii'
0:
,,,
,
C'
,,
+:-'Na
,
C
,,,
,,
,
I~
Na +eIl
...
.c
E
CD
E
CD
:0
CI
ell
CD
CI-
CD
a.
C:
0
'c
,,
,,
2
FIGURE 1.7
Desalination by electrodialysis.
Anode
22
1.10.2
Reverse Osmosis
When two solutions of different concentrations are separated by a semi-permeable membl'L

flow of solvent takes from a region of low concentration to high concentration untillil
concentration is equal on both the sides. This process is called osmosis. The driving force.
this phenomenon is called osmotic pressure. If a hydrostatic pressure in excess of osmoiY
pressure is applied on the higher concentration side, the solvent flow reverses, i.e. solvent~
forced to move from higher concentration to lower concentration (Figure 1.8). This is ill
principle of reverse osmosis. Thus in the reverse osmosis method pure water is separated from
its dissolved solids.
.
-------~[_=~-=s-=~-=-~=-~=-~=-___~-_~-_~-_L:Jr--~_-~_-_-_-_~-_~-_-~_-~_-~_ -_-_~-_~ ~tr~~~~~e

-_
=-=-=-=-=-=-=-=-=-=-=-=-:
~=-=-=-=-=-=-=-=-=-=-=-=-=-=-
____________ I
1- _ _ _ _ _ _ _ _ _ _ _ _ _
-:-=-:-:-:-:-:-:-:-:-:-::
:=-:-:-:-:-:-:-:-:-:-:-:-:-:-:
~S~"~~-~~~~~~i E~~~p~~~-~~;~~~~~
osmosis
------------ I 1-------------------------------------,
1-_-_-_-----------------------
-=-=-=-=-=-=-=:_-~---=----:-=--:-=-=:;.:--t-i~:-:-=:_:--:_:--- =-=--:-=--:-=--:=--=:=:--;-.:--:_:---~---:.---e--_ Di rection '
of osmosis
Piston
Semi-permeable
membrane
FIGURE 1.8
Reverse osmosis.
Using this method pure water is separated from sea water. This process is also callea
super-filtration. The membranes used are cellulose acetate, cellulose butyrate, etc.
[SOLVED EXAMPLES
I,
Example 1.1: Calculate the temporary and permanent/hardness of a water sample having~
following data: Mg(HC0 3)2: 73 mg/l, Ca(HC03)2: 162 mg/I, CaS04: 136 mg/l, MgCI1:
95 mg/l, CaCI2 : III mg/I.
Solution:
CaC03 equivalent
Salt
Mg(HC0 3 )z
73
- x 100 =50 mg/l
146
Ca(HC03h
CaS04
136 x 100 = 100 mgll

136
MgClz
95
- x 100 = 100 mg/l
95
CaCl z
111
- x 100 = 100 mg/l
111
162
162
X 100 = 100 mgll
Water Technology
Temporary hardness due to the presence of bicarbonates of Ca and Mg
= 50 +
23
100
= 150 mg/I or ppm of CaC03 equivalent
Permanent hardness due to the presence of CaS04, MgCI2 and CaCI2 = 100 + 100 + 100
= 300 mg/I or ppm of CaC0 3 equivalent
Example 1.2: Calculate the carbonate and non-carbonate hardness of a sample of water containing dissolved solids (mg/I) given as follows: Mg(HC03)2: 7.3, Ca(HC03)2: 40.5, CaS04:
13.6, MgCI2: 21.75 and NaCI: 60.
Solution:
CaC03 equivalent
Salt
7.3
-xl00=5mgll
146
40.5 x 100 = 25 mg/I
162
13.6 x 100 = 10 mgll
136
21.75 x 100 = 22.9 mg/I
95
Sodium chloride does not contribute any hardness to water.

Carbonate hardness due to the presence of bicarbonates of Ca and Mg
=
25 + 5
30 mg/I or ppm of CaC03 equivalent
Non-carbonate hardness due to the presence of CaS04 and MgCI2 = 10 + 22.9

=
32.9 mg/I or ppm of CaC0 3 equivalent
Example 1.3: 100 ml of a sample of water has a hardness equivalent to 12.5 ml of 0.08N
MgS04 What is the hardness of water?
Solution:
100 ml of sample of water
12.5 ml of 0.08N MgS04

N
_ 12.5 x 0.08
100
hardness -
tenns 0 fCC
Hardness III
a 0
. Ient
eqUlva
= 12.5 x 0.08 x 50 x 1000

100
= 500 mg/I or ppm of CaC03 equivalent
Example 1.4: 50 ml of a hard water required 15 ml of EDTA solution for titration (l ml of

EDTA = I mg of CaC0 3). Calculate the hardness of the sample of water.
24
. Solution:
1 ml of EDTA
15 ml of EDTA
=
=
1 mg of CaC03 equivalent
This amount of hardness is present in 50 ml of hard water.

So
hardness present
In
.
15
1 htre = - x 1000
50
= 300 ppm of CaC03 equivalent
Example 1.5: 250 ml of a sample of water on EDTA titration with Eriochrome Black-T 3l
indicator consumed 13 ml of 0.022M EDTA till end point is reached. Calculate the hardness of
water.
Solution:
1 ml of O.OIM EDTA
Ix 13x 0.022
13 ml of 0.022M EDTA = - - - - 1 x 0.01
= 28.6
mg of CaC03
This amount of hardness is present in 250 ml of the water sample.
So
hardness present in 1 litre
= 28.6 x 1000
250
= 114.4 ppm of CaC03 equivalent
Example 1.6: 100 ml of a sample of water required 20 ml of O.OIM EDTA for the titration
with Eriochrome Black-T indicator. 100 ml of the same sample after boiling and filtering
required 10 ml of O.OIM EDTA. Calculate the total, carbonate (temporary) and non-carbonafl
(permanent) hardness of the sample.
Solution:
Total hardness
1 ml of O.OIM EDTA
20 ml of O.OIM EDTA
= 1 mg of CaC03 equivalent
= 20 mg of CaC03 equivalent
This amount of hardness is present in 100 ml of the sample water.
So
total hardness present in 1 litre
=
=
20 x 1000
100
200 ppm of CaC03 equivalent
Water Technology
25
Permanent or non-carbonate hardness

1 ml of O.OIM EDTA = 1 mg of CaC0 3 equivalent
10 ml of O.OIM EDTA = 10 mg of CaC03 equivalent
So
permanent hardness present in 1 litre = ~ x 1000
100
Carbonate or temporary hardness

carbonate hardness = total hardness - non-carbonate hardness
= 200 - 100
txample 1.7: 0.5 g of CaC03 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 CaC03
=
0.5 x 1000 mg of CaC03
500 mg of CaC03
Standardization of EDTA
1 mg of CaC03
50 ml of CaCl2 solution
50 mg of CaC03
48 ml of EDTA solution
= 50
mg of CaC03
50
1 ml of EDTA solution = 48 x 1
1.04 mg of CaC03
1.04 mg of CaC03
Total hardness
15 ml of EDTA solution = 1.04 X 15
15.6 mg of CaC03
So
. 1 1Itre
tota1 hardness present 10
15.6
=- x 1000
50
312 ppm of CaC03 equivalent
26
Example 1.8: 0.25 g of CaC03 was dissolved in dil. HCI and diluted to 250 ml. 100 mlof
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 CaC03
0.25 x 1000 mg of CaC03
250 mg of CaC03
1 mg of CaC0 3
Standardization of EDTA
100 ml of CaCl2 solution = 100 mg of CaC03
1 ml of EDTA solution =
100 mg of CaC03
100
20 xl
= 5 mg of CaC03
Total hardness
30 X 5
150 mg of CaC03
This amount of hardness is present in 100 ml of the hard water.

So
total hardness present in 1 litre = 150 x 1000
100
Permanent hardness
10 ml of EDTA solution = 5 X 10
= 50 mg of CaC03
This is present in 100 ml of hard water.

So
permanent hardness present in 1 litre
= 50
100
x 1000
temporary hardness = total hardness - permanent hardness

=
1500 - 500
Water Technology
------
27
( SHORT QUESTIONS )
1. What is meant by soft water and hard water?

2. What are the hardness causing constituents?
3. How is hardness of water expressed?
4. What are the causes of scale formation? What are its disadvantages?
5. What are scales and sludges?
6. What is caustic embrittlement?
7. What is desalination?
8. Zeolite softeners cannot be used for softening turbid water. Why?
9. What is meant by priming and foaming?
10. Write a note on break point chlorination.
n.
Explain the principle of estimation of total hardness of water using EDTA.
12. In the determination of hardness of water by EDTA method, NH40H-NH4CI buffer is

used. Why?
13. What is colloidal conditioning?
14. What are disinfectants? Give examples.
15. What is meant by demineralization of water? How will you regenerate the exhausted
resin?
16. Distinguish between internal and external conditioning of water.
17. Why deaeration of water is done?
18. How is phosphate treatment effective in prevention of scale formation in boilers?
19. Distinguish between scales and sludges.
(DESCRIPTIVE QUESTIONS)
1. What are the problems that arise by the use of hard water in boilers? Suggest methods to
overcome the same.
2. What do you understand by internal conditioning and external conditioning methods of
boiler feed water?
3. Give a detailed account of internal conditioning methods used in the treatment of water
for boilers.
4. What are boiler troubles? How can the boiler troubles be minimized?
5. How do you estimate the hardness of water by EDTA method?
6. How is water purified for domestic purpose?
7. Why is sterilization of water necessary? Discuss the various methods of sterilization.
Briefly explain how water is treated for domestic purpose.
28
8. Write down briefly on desalination. Discuss anyone important method used.

9. Define boiler feed water. What are the specifications for boiler feed water? Discuss the
internal and external conditioning methods of boiler feed water production.
10. Enumerate the difficulties encountered with raw boiler feed water. Describe briefly any
three internal conditioning methods.
11. How is boiler feed water produced?
12. What are the factors which cause boiler corrosion? How can it be minimized?
13. With a neat diagram explain the ion exchange process for the purification of water.
14. Discuss the different types of alkalinity.
( PROBLEMS )
1. 25 ml of standard hard water consumes 12 ml of standard EDTA solution. 25 ml of hard
water consumes 8 ml of standard EDTA solution. After boiling the sample, 25 ml of the
boiled and cooled hard water consumes 6 ml of standard EDTA solution. Calculate the
total, permanent and temporary hardness.
(Ans. total hardness == 666.67 ppm, permanent hardness == 500 ppm,
temporary hardness == 166.67 ppm)
2. 50 ml of standard hard water containing I mg of CaC03 per ml consumed 17 ml of EOTA
50 ml of sample of hard water consumed 12 ml of EDTA. Calculate the total hardness in ppm.
(Ans. 705.88 ppm)
3. 100 ml of a sample of water required 15 ml of O.OIM EDTA for titration using Erio-T as
indicator. In another experiment, 100 ml of the same sample was boiled to remove the
temporary hardness, the precipitate was removed and the cold solution required 8 ml of
O.OIM EDTA using Erio-T as indicator. Calculate the total hardness, permanent hardness
and temporary hardness in mg/l of CaC03 equivalent.
(Ans. total hardness == 150 mg/l, permanent hardness == 80 mgil,
temporary hardness = 70 mgil)
4. 0.5 g of CaC03 was dissolved in dilute hydrochloric acid and diluted to 500 m!. 50 ml
of this solution required 40 ml of EDTA solution for titration. 50 ml of hard water sample
required 25 ml of EDTA solution. After boiling the sample hard water, 50 m! of it
consumed 20 ml of EDTA solution. Calculate the total hardness, permanent hardness and
temporary hardness of sample hard water.
(Ans. total hardness == 625 ppm, permanent hardness == 500 ppm,
temporary hardness == 125 ppm)
5. Ig of CaC03 was dissolved in dilute hydrochloric acid and made up to 1000 m!. 50 mI
of this solution required 46 ml of EDTA for titration. 50 ml of hard water sample required
20 ml of the same EDTA solution. After boiling the sample of hard water, 50 ml of it
Water Technology
29
consumed 12 ml of EDTA solution. Calculate the carbonate and non-carbonate hardness

of the sample.
(Ans. total hardness = 434.78 ppm, permanent hardness = 260.86 ppm,
temporary hardness = 173.9 ppm)
6. SO ml of a hard water sample required for titration 25 ml of EDTA solution. One ml of
EDTA solution is equivalent to 1.1 mg of CaC03 equivalent. Calculate the hardness of
water in ppm.
(Ans. 550 ppm)
7. 100 ml ofa sample of water has a hardness equivalent to 12.5 ml ofO.08N MgS04. What
is the hardness in ppm?
(Ans. 500 ppm)
8. 100 ml of a sample of water has a hardness equivalent to 18 ml of 0.05N CaCI2. What

is the hardness in ppm?
(Ans. 450 ppm)
9. SO ml of a sample of water has a hardness equivalent to 15 ml of 0.02N CaS04' What is
the hardness in ppm?
(Ans. 300 ppm)
10. Calculate the hardness of water sample whose 10 ml required 20 ml of EDTA. 20 ml of
CaCl2 solution whose strength is equivalent to 1.5 g of CaC0 3 per litre required 30 ml
of EDTA solution.
(Ans. 2000 ppm)
POLYMERS AND COMPOSITES
2.1
INTRODUCTION
A polymer is a large molecule which is formed by repeated linking of small molecules called
monomers. For example, the polymer polyethylene is formed by repeated linking of small
ethylene molecules which are the monomers.
CHi=CH2 ~ -CHr~H2-CHr--CH2-CHr--CH2-
The equation for polymerization is represented as shown below where n stands for a large
number.
ethylene
polyethylene
The individual small molecules from which the polymer is formed are known as monomers and the process by which the monomer molecules are linked to form a polymer is called
polymerization.
The number of repeating units in the chain so formed is called the degree of
polymerization. Consider the following example.
5CHi=CH2 ~ -CH2-CH2-CH2-CH2-CH2-CH2--CH2--CH2--CH2-CH2-
Here five repeating units are present in the polymer chain. So, degree of polymerization
is 5.
Polymers with high degree of polymerization are called high polymers and those with low
degree of polymerization are called oligopolymers. High polymers have very high molecular
weights Cl 04-10 6) and hence are called macromolecules.
The monomeric units in a polymer may be present in linear, branched or cross linked
structure:
30
31
'\-A~A-
linear
I
-A-A-A-A-A-A-A-A--A -.\
I
A
I
A
branched
-A-A-A-A-A-A-A-A-A-A-A-A-A-A-AI
I
A
A
I
I
A
~A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-
I
A
I
A
I
I
A
I
A
I
--A~A-A-A-A-A-A-A-A-A-A-A-A-A-/\
cross-linked
2.1.1 Homopolymers and Copolymers

If the polymer contains same type of monomer it is a homopolymer. If it contains two different
types of monomer it is a copolymer:
A-A-A-A-A-A-A-A-A-A-A-A-A-A
homopolymer
A-B-A-B-A-B-A-B-A-B-A-B-A-B
copolymer
2.1.2 Homo-Chain and Hetero-Chain Polymers

If the main chain is made up of the same type of atom, the polymer is called a homo-chain
polymer, e.g. polyethylene:
~-c-c-c-c-c-c~-c-c-
If the main chain is made up of different type of atoms, the polymer is called a hetero-
chain polymer, e.g. polyethyleneadipate:

~~-O-C-C-G-C-C-D-
32
2.1.3
Block and Graft Copolymers
A block copolymer is a linear copolymer in which like monomeric units occur in relatively long
sequences:
-A-A-A-A-B-B-B-B-A-A-A-A-B-B-B-B-A-A-A-AA branched copolymer with one kind of monomer in the main chain and another kind of
monomer in the side chain is called a graft copolymer:
B
I
I
B
I
-A-A-A-A-A-A-A-A-A-A-A-A-A-A-AI
B
2.2
TYPES OF POLYMERIZATION
There are mainly three types of polymerization: (a) addition polymerization, (b) copolymerization
and (c) condensation polymerization.
2.2.1
Addition Polymerization
In addition polymerization, the polymer is formed from the monomer without the loss of any
material and the product is an exact multiple of the original monomeric molecule, for example:
(a) Formation of polyethylene
nCH2=CH 2
-f-CH 2-CH 2-h
(b) Formation of polystyrene
2.2.2
Copolymerization
The polymerization of a mixture of two monomers of equal reactivity is known as

copolymerization, for example:
33
(a) Acrylonitrile and vinyl chloride combine to give a copolymer of acrylonitrile and vinyl
chloride.
nCH2=CH + nCH2=CH
CN
acrylonitrile
~ -+CH2-CH~H2-CH+n
Cl
CN
Cl
vinyl chloride
(b) Styrene and butadiene combine to give a copolymer of styrene and butadiene.
6~H' + nCH,~H-CH~CH,--->
styrene
butadiene
O-CH,-CH'-CH ~ CH-CH,+.
2.2.3 Condensation or Step Polymerization

Condensation polymers are formed by combination of monomers by elimination of simple
molecules such as water and methanol.
Terylene is the most important polyester. It is obtained by heating excess of ethylene
glycol with dimethyl terephthalate at 200C in the presence of a catalyst.
ethylene glycol
dimethyl terephthalate
HO~H2-CH2-00C-Q-c00CH3 + CHpH
further reaction at each end
+CH2-CH2-00C-Q-COO-+,;
Nylon is the most important polyamide. It is obtained by heating adipic acid and
hexamethylenediamine. Nylon 6,6 derives its name from its starting materials adipic acid and
hexamethylenediamine both of which have six carbons.
34
adipic acid
hexamethylenediamine
HOOC-(CH2k-CO-NH-(CH2)6-NH2
+ H 20
+DC-(CH2)4-CO-NH-(CH2)6-NH-t,;
Nylon 6,6
Differences between addition and condensation polymerization are given in Table 2.1.
TABLE 2.1
Differences between addition and condensation polymerization
Addition polymerization
Condensation polymerization
1. No by-product is formed.
1. Generally a by-product is obtained.
2. Homo-chain polymer is obtained.
2. Hetero-chain polymer is obtained.
3. Bifunctionality is provided due to the presence

of double bond in the monomer.
3. Bifunctionality is provided due to the presence

of reactive functional groups present at both
ends of the monomer.
4. The chain growth is at one active centre.
4. The chain growth takes place at atleast two

active centres.
5. Mostly thermosetting plastics are formed.
5. Mostly thermoplastics are formed by this

process.
6. The polymer product is formed immediately.
6. The polymer product is formed stepwise

steadily.
7. This follows a free radical or cationic or

anionic mechanism.
7. This follows the mechanism of condensation

reactions such as esterification and amide
formation.
2.3
FREE RADICAL MECHANISM OF ADDITION POLYMERIZATION
Free radical polymerization is initiated by organic peroxides which decompose to give free
radicals. The most widely used initiators are acetyl or benzoyl peroxide. The following steps are
involved.
(a) Chain initiation
Organic peroxides undergo homolytic fission to give free radicals.

C6HsCO-O-O-OCC6HS
benzoyl peroxide
2C6H sCOO
(R")
The free radical adds to an alkene molecule to form a new free radical.
35
(b) Chain propagation
The free radical can attack another molecule and so on.

R-CH 2-CH2- + n[CH 2=CH 2 ]
R-(CH2-CH2)n-CH2-CH2-
(c) Chain termination
The chain reaction can be terminated by reacting with another free radical.
R-(CH2-CH2)n-CH2-CH2 + CH2-CH2-(CH2-CH2)n-R
R-(CH2-CH2)n-CH2-CH2-CH2-CH2-(CH2-CH2)n-R
2.4 PLASTICS
Plastics are high molecular weight materials which can be moulded or formed into stable shapes
by the applications of heat and pressure.
2.5 COMPOUNDING OF PLASTICS OR CONSTITUENTS OF PLASTICS

Compounding of plastics is a process by which the high polymer resins are mixed with other
substances like fillers, plasticizers and colorants to improve the quality, ease of fabrication and
to impart certain specific properties.
Plastic may contain a number of constituents such as:
1. binders
3. dyes and pigments
5. lubricants
2. fillers
4. plasticizers
6. catalysts
1. Binders:
The main purpose of a binder is to hold the other constituents ofthe plastic
together. The binder used may be natural or synthetic resins. Two type of resins are
used: (a) thermoplastic resins and (b) thermosetting resins. On the basis of the type of
resin used in its preparation, the plastic itself is called thermoplastic or thermosetting
plastic.
2. Fillers: Fillers are added for two purposes: (a) to reduce the cost and (b) to impart
special property on the product. For example, quartz and mica are used to improve
hardness; asbestos is added to improve heat resistance.
3. Dyes and pigments: These materials provide pleasing colours to the plastic. They are
inorganic colouring pigments as well as organic colouring dyes. Table 2.2 lists different
dyes and pigments and their colours.
TABLE 2.2
Different dyes and pigments and their colours
Name of the pigment!dye!

inorganic substance
Carbon black
Zinc oxide
Chromium trioxide
Phthalocyanin dye
Colour
Black
White
Green
Blue
36
4. Plasticizers: The important functions of a plasticizer in plastics are to improve plas

ticity and flexibility so as to reduce the temperature and pressure required for moulding,
e.g. dioctylphthalate. These molecules distribute themselves between the polymer
chains thereby decreasing the attractive forces between them. This results in increased
plasticity and flexibility.
.
5. Lubricants: They help in easy moulding and also prevent the plastic material from
sticking to the fabrication equipment, e.g. oils and waxes.
6. Catalysts: Catalysts are used in the case of thermosetting plastics to accelerate the
condensation polymerization to form the cross linked products, e.g. peroxides.
2.6 ADVANTAGES OF PLASTICS OVER OTHER MATERIALS

The following are the advantSlges of plastics over other materials.
1. Plastics can be moulded to any shape or size.
2. They resist corrosion and the action of chemicals.
3. They are light weight materials but at the same time possess good strength and
rigidity.
4. Their high dielectric strength makes them suitable for electric insulation.
5. Plastics require little maintenance care.
6. They have good sound and heat absorption properties.
2.7
CLASSIFICATION OF PLASTICS
Based on the usage, plastics can be divided into two categories.

1. General purpose plastics or commodity plastics
2. Engineering plastics
2.7.1
General Purpose Plastics or Commodity Plastics
The widely used commercial plastics with low to moderate strength are commonly known as
commodity plastics. They account for about 80-85% of total polymer production. Polyethylene,
polystyrene, etc. are some examples for commodity plastics.
Properties of general purpose plastics
The properties of general purpose plastics are as follows:

1.
2.
3.
4.
5.
6.
General purpose plastics have varying strength from very low to moderate level.
They are mostly crystalline with low glass transition temperature.
They can not be used at high temperature as they have low thermal resistance.
They have low abrasion resistance.
Most general purpose plastics have densities of about 1 compared to 7.8 for iron.
The maximum use temperature varies from 54-149C for most of the thermoplastic
materials.
37
1,7,2 Engineering Plastics (High Performance Plastics)

Plastics which have higher strength, greater environmental resistance and better mechanical
properties that are mainly used in engineering fields are known as engineering plastics. These
plastics find limited applications. These plastics are generally costlier than commodity plastics.
They are mainly used in load bearing applications, generally to replace conventional materials
like metal, wood, glass and ceramics. Not only engineering plastics can replace metals but they
can also be used along with metals. The outstanding properties of engineering plastics come
primarily from their crystalline nature and strong intermolecular forces.
Properties of engineering plastics
The following are the properties of engineering plastics:

I. Engineering plastics have high softening points.
2, They have high thermal resistance (177C)
3. The densities of the engineering thermoplastics are relatively ranging from 1.06-1.42.
4. The maximum use temperature for the engineering thermoplastics varies from
82-260oC.
5, Engineering plastics have high load bearing capacity.
6, They are strong, stiff, tough and abrasion resistant materials capable of withstanding
wide range of temperatures.
7, They are resistant to attack by wiather and chemicals.
8, Engineering plastics have high performance properties, i.e. they can be used in the
same manner as metals, alloys and ceramics.
Applications of engineering plastiCS
I, Engineering plastics can be used alone or in conjunction with metals, ceramics, glass, etc.
2, They find applications in demanding areas like automobiles, defence, electrical and
electronics, telecommunication, textiles and computer components.
2,7,3 Some Important Engineering Plastics

1. Polyvinyl chloride (PVC): It is prepared by the polymerization of vinyl chloride in
presence of benzoyl peroxide.
CH2=CH
Cl
polymerization
----~)
+CH2--CH-t,;
Cl
Properties: Polyvinyl chloride is a hard and stiff amorphous plastic. It is characterized

by excellent flame resistance and low cost. It has outstanding strength, lightness and
chemical resistance.
Uses: The following are the uses of polyvinyl chloride:

1. Rigid PVC or unplasticized PVC has excellent chemical resistance and high
rigidity. It is used for making sheets, safety helmets, etc.
38
2 .. Plasticized PVC (i.e. obtained by adding plasticizers like dioctyl phthalate and
tricresyl phthalate) is used for making rain coats, table covers, cable insulations, etc.
2. Teflon (or) Polytetrafluoroethylene (PTFE): Teflon or PTFE is prepared by

polymerization of tetrafluoroethylene at higher pressures in presence of benzoyl
peroxide by emulsion polymerization.
nCF2=CF2
polymerization
)
-f--CF2-CFdn
Teflon is linear and highly crystalline polymer. It melts around 330C. It is highly
resistant to heat and chemicals. The highly nonpolar carbon backbone surrounded by
electron clouds of fluorine and high C-C and C-F bond energies make it chemically
inert (resistant).
Teflon is used as an electrical insulator even at elevated temperatures. It is also used
as non-stick coating on frying pans, solid lubricants, etc.
3. Polycarbonates (PC) [Lexan, Merlon): Polycarbonates are prepared by reaction of
bisphenol-A with phosgene in the presence of a base such as pyridine:
Properties: The following are the properties of polycarbonates:

1. Polycarbonates have good mechanical properties.
2. They have high impact strength.

3. They are resistant to water and many organic compounds.
Uses: Polycarbonates are used to make safety goggles, safety shields, telephone parts
and boat propellers.
4. Polyurethanes (Perlon-U):
Polyurethane is obtained by the reaction of 1,4

butanediol with hexamethylenediisocyanate:
C-NH(CH2)6NH-C-O-CCH2)4-1
11
11
0
polyurethanes
39
Properties: The following are the properties of polyurethanes:

1. Polyurethane possesses excellent flexibility and toughness.
2. It has high solvent resistance and abrasion resistance.
Uses: Polyurethanes are used as coatings, films, foams, adhesives and elastomers.
5. Thermocole: Thermocole is a foamed-plastic, obtained by blowing air or gas through
molten polystyrene (or) polyurethane.
Properties: The properties of thermocole are as follows:
1.
2.
3.
4.
5.
6.
7.
8.
Thennocole is white in colour and can be made into desired shades.

It is light, strong and chemically inert.
Its density is about 20 kg/m3
Its thermal and electrical conductivities are quite low.
It is also used as a shock-proof material.
Its compressive strength is 117-145 kg/cm 2
It can be used up to 55C.
It is so soft, that it can be easily cut by a knife and can be scratched by nail.
Uses: The following are the uses of thermocole:

1. Due to its outstanding thermal insulating property and lower density, it is used as
a thermal insulating material in refrigeration and air-conditioning.
2. Since it is very good shock-proof, it is used as a packing material like electronic
equipment.
3. It is used for protecting screens in radar.
4. It is used for decorative purposes.
5. It is also used as an insulating and vapour barrier.
6. Nylon 6,6: Nylon 6,6 is obtained by heating adipic acid and hexamethylenediamine.
Nylon 6,6 derives its name from its starting materials adipic acid and
hexamethylenediamine both of which have six carbons.
HOOC-(CH2)4-COOH + H 2N-(CH2)6-NH2 ~
adipic acid
hexamethylenediamine
-[OC-(CH2)4-CO-NH-(CH2)6-NH] Nylon 6,6
Properties: Nylon is tough, strong and easily mouldable. It is having good chemical
resistance and low coefficient of friction.
Uses: The following are the uses of nylon 6,6.
1. Nylon is used to make textile fibres for use in dresses, socks, undergarments,
carpets, etc.
40
2. It is also used for making filaments for ropes, bristles for toothbrush, etc.
3. It is used as a good substitute for metal in gears and bearings.
4. It is also used in making tyres, watch straps, etc.
7. Polyethyleneterephthalate (PET) or Terylene: Terylene is obtained by heating
excess of ethylene glycol with dimethyl terephthalate at 200C in the presence of a
catalyst.
ethylene glycol
dimethyl terephthalate
HO-CH 2-CH2-00C-Q-COOCH3 + CH30H
+CH2-CH2-00C-Q-COO-h
Properties: PET melts around 265C, having good mechanical strength, resistant to
heat and moisture and it is unattacked by any chemicals.
Uses: It is extensively used in the preparation of bottles. It is also used as textile
fibres and in garments resisting formation of wrinkles.
2.8
FABRICATION OF PLASTICS
The shaping of an article from a plastic material by the application of heat and pressure in a
closed chamber is called moulding.
The method by which plastics can be fabricated depends on the thermal behaviour of the
plastics, i.e. whether it is thermoplastics or thermosetting and also on the nature of the finished
product.
Compression moulding, injection moulding, etc. are some of the methods used for thr
fabrication of plastic materials.
2.8.1
Compression Moulding
The compression moulding is widely used to produce articles from thermosetting materials.
Figure 2.1 shows a typical mould employed for compression moulding.
The mould is made up of two halves, the upper and the lower halves. The lower half
usually contains a cavity and the upper half has a projection which fits into the cavity when the
mould is closed. The gap between the projected upper half and the cavity in the lower one
gives the shape of the moulded article. The thermosetting material to be moulded is placed
in the cavity of the mould. The plastic material is then subjected to heat and pressure (200oC and
70 kg/cm2 ) simultaneously. As the mould closes down under pressure, the material is
compressed between the two halves and compacted to shape inside the cavity. The excess
Heat and pressure
41
Mould cavity
filled with
thermosetting ---'~~I-----R
material
Compression moulding.
FIGURE 2.1
material flows out of the mould as a thin film is known as flash. Under the influence of heat,
the compacted mass gets cured and hardened to shape. The mould can be opened while it is still
hot to release the moulded product.
Compression moulding is not adopted for thermoplastics because the moulded piece can
be removed only after chilling the mould as the hardening of the plastic material takes place
on cooling. This results in a comparatively long time for the operation with alternate heating
and cooling.
2.8.2 Injection Moulding

A definite quantity of molten thermoplastic material is injected under pressure into a mould
which is kept at lower temperature for cooling. The molten material solidifies and takes the
shape of the mould.
The compounded plastic material in the form of pellets or powder is fed through the
hopper. The thermoplastic material softens under the influence of heat and becomes fluid. The
hot fluid is forced through a nozzle by the plunger into a tightly locked mould (Figure 2.2). The
mould is made up of two parts which can be separated. After cooling, the moulded article is
released from the mould.
It is not suited for thermosetting plastics because once heated, they begin to set in the
reservoir.
Plastic feed
;:::,.-
7'
III
Mould
FIGURE 2.2
Injection mOUlding.
42
2.9
RUBBER
Natural rubber is a polymerized form of isoprene (2-methyl-I,3-butadiene).

nCH2=C-CH=CH2
2.9.1
+CH2-C=CH-CHd;;
CH3
CH3
Isoprene
Polyisoprene
Vulcanization of Rubber
To improve the properties of rubber, it is compounded with some chemicals like sulphur,
hydrogen sulphide, etc. The most important is the addition of sulphur. When rubber is heated
with sulphur at lOO-140C, its tensile strength and chemical resistance are increased tremendously. This process is known as vulcanization. The sulphur combines chemically at the double
bonds in the rubber molecule, bringing about excellent changes in its properties.
+
-CH -C=CH-CH -CH -C=CH-CH -
CH3
CH3
Sulphur
CH3
CH3
I
I
-CHz-C-CH-CH2-CH2-C-CH-CH2I I
I I
s s
s s
I I
I I
-CH2-C-CH-CH2-CH2-C-CH-CH2-
CH3
CH3
Vulcanized rubber
2.9.2
Advantages of Vulcanized Rubber

1. Rubber has good tensile strength (2000 kglcm 2)
2. It has excellent resilience, i.e. articles made from it return to their original shape. when
the deforming load is removed.
3. It possesses low water absorption tendency.
4. It has higher resistance to oxidation.
5. It has much higher resistance to wear and tear.
43
6. Ebonite (raw rubber vulcanized with 32% sulphur) is better insulator.
7. it is resistant to organic solvents.

Table 2.3 shows a comparison between raw rubber and vulcanized rubber.
TABLE 2.3
Comparison between raw rubber and vulcanized rubber
S.No.
Raw rubber
Vulcani=ed rubber
Tensile strength is low (200 kg/cm 2)
2.
3.
4.
5.
Low oxidation resistance

Water absorption tendency is high
The chemical resistance is poor
It is attacked by organic solvents
Low resistance to wear and tear
Because of vulcanization, tensile strength is

increased (2000 kg/cm 2)
High oxidation resistance
Low water absorption tendency
Chemical resistance is high
It is resistant to organic solvents
High resistance to wear and tear
6.
2.10 SOME IMPORTANT SYNTHETIC RUBBERS

Synthetic rubbers are man-made rubbers which are superior to natural rubber in certain properties. Buna-S rubber, neoprene, nitrile rubber, etc. are some examples of synthetic rubbers.
2.10.1 Buna-S Rubber (SBR)

Buna-S rubber is produced by copolymerization of about 75% butadiene and 25% styrene.
styrene
Buna-S rubber
Buna-S rubber is used for the manufacture of motor tyres.
2.10.2 Butyl Rubber

Butyl rubber is made by copolymerization of isobutylene with small amounts of isoprene
CH3
CH3
nCH2=C + nCH2=C-CH=CH2 ~ +CH2-C-CH2-C=CH-CH2--1n
CH3
isobutylene
CH3
isoprene
CH3
CH3
butyl rubber
Butyl rubber is used in making cycle and automobile tubes. It is also used for making
insulating cables.
44
2.11
COMPOSITES
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 possesses properties different from those of its constituents.
2.11.1
Characteristics
1. The composites possess higher specific strength and lower specific gravity.
2. They possess lower electrical conductivity and thermal expansion.
3. They possess better creep, fatigue strength, corrosion and oxidation resistance.
4. They maintain very good strength even up to very high temperatures.
2.11.2
Constituents of Composites
Composites consist of two important constituents:

1. Matrix phase
2. Dispersed phase
Matrix phase
Matrix phase is the continuous body constituent which encloses the composite. Matrix phase
may be metals, ceramics or polymers. Composites using these matrixes are known as
1. Metal Matrix Composites (MMC)
2. Ceramic Matrix Composites (CMC)
3. Polymer Matrix Composites (PMC)
Dispersed phase
Dispersed phase is the structural constituent, which determines the internal structure of composites. For example, fibres, particulates.
2.11.3
Types of Composites
Metal matrix composites

In metal matrix composites, the matrix phases used are alloys of aluminium, titanium and nickel.
The reinforcement materials used are alumina (AI20 3), boron, carbon and silicon carbide (SiC).
Properties: Metal matrix composites exhibit extremely good thermal stability, high
strength, good stiffness and low specific weight. They can withstand elevated temperature in
corrosive environment than polymer composites.
Uses:
The following are the uses of metal matrix composites:
1. Metal matrix composites are used in engine blades, combustion chambers, etc.
2. They improve fuel efficiency because of weight reduction.
45
3. Apart from aerospace, defence and automotive applications, they are also used in the
biomedical and sports equipment industry.
Ceramic matrix composites
The matrix phases used are glass, ceramic, carbides, nitrides, oxides and borides, and the
reinforcements used are A12 0 3, boron, carbon, SiC and silica (Si0 2).
Properties: Ceramic matrix composites possess good corrosion resistance and high compressive strength. They are stable at elevated temperature.
Uses: Ceramic matrix composites are used in space vehicles, filter pump seal, round
rings, brake linings, etc.
Polymer matrix composites or Fibre reinforced polymer composites
Fibre Reinforced Polymers (FRP) are composite materials in which a resin is combined with a
reinforcing agent (fibre material) to improve the properties of the resin matrix. The resin matrix
commonly used in FRP are polyesters, epoxy resins, phenolic resins, silicone resins and polyamides. The reinforcing agents are glass, graphite, alumina, carbon, boron, etc.
FRP composites possess high strength, stiffness, corrosion resistance, heat resistance and
impact resistance. Different types of FRP composites are available and they are used in different
industries. The glass fibre reinforced polymer possesses lower density, higher tensile strength
and excellent corrosion resistance. It is used for making automobile parts, storage tanks, plastic
pipes, etc. The carbon fibre reinforced polymer possesses lower density and excellent resistance
to corrosion. It is used for making structural components of aircraft and helicopters, sports
materials, antenna discs, solar panels, etc. The aramid fibre reinforced polymer (aramidaromatic polyamide) is ductile like metal in nature and used for making structural components
in aircraft, helicopter parts, etc. The alumina fibre reinforced polymer possesses good abrasion
resistance, creep resistance and dimensional stability. They are used for making components of
engine parts in the automobile industry and components of turbine engine.
Preparation: Fibre reinforced polymers are prepared as follows. The mould is first
treated with release agents such as wax and silicone oil. Then the mould is given a coating of
resin matrix like polyester or epoxy. The fibre material (glass or carbon) is impregnated with
resin and placed over the mould. Now another layer of the resin coating is given over this.
Rollers are used to press the resin uniformly and also to remove the entrapped air bubbles.
Alternate layers of resin and glass or carbon are laid in a similar sequence until the required
thickness is built up. The whole set-up is then cured at appropriate temperatures. After curing,
the reinforced plastic material is removed from the mould and subjected to trimming and
finishing.
( SHORT QUESTIONS)
1. Define polymer.
2. What is polymerization?
3. What is addition polymerization? Give examples.
46
4. What are copolymers? Write down two examples.

5. How is polymerization classified? Give examples for each class.
6. What are the monomeric units in the following polymers?
(a) PVC
(b) Starch
7. Explain the homochain and heterochain polymers with examples.
8. What are block and graft copolymers?
9. What are the advantages of using plastics over other materials?
1. Define polymerizati;n. Discuss the various types of polymerization with examples.
2. Distinguish between~ apdition and condensation polymerization.
~"
3. Write a note on compopnding of plastics.

4. What are the common constituents of plastics and what are their functions?
5. Write about some engineering plastics with special characteristics.
6. What is meant by moulding? Explain the injection moulding of plastics.
7. Give the preparation, properties and industrial uses of any two engineering plastics.
8. Give the preparation, properties and industrial uses of polycarbonates and polyurethanes.
9. Explain condensation polymerization with examples.
10. Write a note on FRP.
11. Give an account of vulcanization of rubber.
SURFACE CHEMISTRY
3.1
INTRODUCTION
When solids are allowed to remain in contact with a gas, a film of gas molecules accumulates
on the surface. Like liquids, molecules or ions at the surface of a solid also have unbalanced
forces. Solid surfaces therefore have a tendency to satisfy their unbalanced forces by attracting
and accumulating other molecules on their surface.
This phenomenon of accumulation of molecules of a gas on a solid surface is called
adsorption.
The substance on which adsorption takes place is known as the adsorbent and the
substance which is adsorbed is known as adsorbate. Charcoal, silica gel, clay, Fuller's earth,
etc., are some examples for adsorbents. Due to their extremely small dimensions, colloids
possess enormous surface area and are therefore good adsorbents.
Both adsorption and absorption are different. Adsorption is a surface phenomenon
whereas in absorption a substance is not only retained on the surface but passes through the
surface and distributed throughout the body of a solid. Thus water vapours are absorbed by
anhydrous calcium chloride while they are adsorbed by silica gel. The differences between
adsorption and absorption are given in Table 3.1.
TABLE 3.1
Differences between adsorption and absorption
Adsorption
Absorption
I. It is a surface phenomenon in which the

solutes are concentrated at the surface of the
adsorbent.
2. It depends on the surface area of the adsorbent.
1. It is a bulk phenomenon in which the substance is uniformly distributed throughout the

body of the solid.
3. It is a slow process.
3. It is a fast process.
4. Equilibrium is attained slowly.
4. Equilibrium is attained immediately.
2. It is not depending on surface area.
47
48
McBain'introduced a general tenn sorption to describe a process in which both absorption

and adsorption take place simultaneously.
3.2
TYPES OF ADSORPTION
The adsorption of a gas into a solid surface is mainly of two types.

1. Physical adsorption or van der Waals adsorption
2. Chemisorption or activated adsorption
3.2.1
Physical Adsorption (Physisorption)
In this kind of adsorption, the gas molecules are held to the surface by the van der Waals forces
of attraction. The adsorption is generally observed in the adsorption of various gases on
charcoal. The heat evolved during this adsorption is of the order of 5-10 kcal per mole of
the gas.
3.2.2
Chemisorption
In this kind of adsorption, the gas molecules are held to the solid surface by chemical forces
and a chemical bond is fonned between the adsorbed molecule and the surface.
Oxygen chemisorbed on carbon and hydrogen chemisorbed on nickel are suitable
examples for this adsorption. Oxygen molecule is first adsorbed by the van der Waals forces and
then dissociates. The oxygen atoms are then chemisorbed on carbon (Figure 3.1). The heat
evolved during this adsorption is of the order of 10-100 kcal per mole.
0---0
Physical
0----------- 0
Chemisorption
adsorption
FIGURE 3.1
Physisorption and chemisorption,
Surface Chemistry
49
The differences between physisorption and chemisorption are listed in Table 3.2.
TABLE 3.2
Differences between physisorption and chemisorption
Physisorption
Chemisorption
I. Physisorption is due to the weak van der Waals

forces.
1. Chemisorption is due to the formation of

strong covalent bonds.
2. Heat of adsorption is low (5-10 kcal/mol).
2. Heat of adsorption is very high

(10-100 kcal/mol).
3. It decreases with rise in temperature.
3. It increases with increase in temperature.
4. Gases are not strongly attached to the surface.
4. Gases are strongly attached to the surface.
5. It is reversible as the gas adsorbed can be

removed easily from the adsorbent.
5. It is irreversible because a surface compound

is formed.
6. It occurs at very low temperatures.
6. It can occur at all temperatures.
7. It fonus multimolecular layer on the adsorbent

surface.
7. It forms unimolecular layer.
3.3 ADSORPTION OF GASES ON SOLIDS

All solids adsorb gases to some extent. The extent of adsorption increases with the surface area.
Thus finely divided metals like nickel and platinum, and porous substances like charcoal and
silica gel provide a large surface area and are the best solid adsorbents.
The extent of adsorption can be further enhanced by a process called activation. Thus
wood charcoal can be activated by heating between 350 and 1000C in vacuum or in air.
Heating removes all the impurities from the pores and leads to larger surface area for adsorption. Thus activated charcoal at 24C adsorbs 1.48 gram of carbon tetrachloride per gram of
charcoal whereas before activation it could adsorb only 0.011 gram per gram of charcoal.
Adsorption of a gas by a solid is accompanied by evolution of heat which is known as
heat of adsorption. Heat of adsorption is defined as the heat liberated when 1 gm mole of a gas
is adsorbed on the solid surface.
3.4 FACTORS INFLUENCING ADSORPTION

The magnitude of adsorption depends on the following factors:
Temperature
Pressure
Nature of the gas
Nature of the adsorbent
3.4.1 Temperature and Pressure

Since adsorption is accompanied by evolution of heat, the magnitude of adsorption should
increase with decrease in temperature. Further, since adsorption of a gas leads to decrease of
50
pressure, the magnitude of adsorption increases with increase in pressure. Thus, both decrease
of temperature and increase of pressure will tend to increase the adsorption of a gas on solid.
3.4.2
Nature of the Gas and Nature of the Adsorbent
More easily liquefiable gases like ammonia and chlorine are adsorbed more readily than the
so called permanent gases such as hydrogen, nitrogen and oxygen. The reason is that the van
der Waals forces which are involved in adsorption are more predominant in the former category
than in the latter.
Since adsorption is a surface phenomenon, it is evident that, greater the surface area per
unit mass of the adsorbent, greater is its capacity for adsorption under the given conditions of
temperature and pressure.
3.5
ADSORPTION ISOTHERM
A plot obtained between the amount of substance adsorbed per unit mass of the adsorbent and
the equilibrium pressure (in case of a gas) or concentration (in case of a solution) at constant
temperature is known as adsorption isotherm. Five general types of isotherms have been
observed in the adsorption of gases on solids. These are shown in Figure 3.2.
'0
<Il
'0
<Il
'0
<Il
0
CIl
'0
I1l
0
CIl
'0
I1l
CIl
::l
~
'E
::l
'E
0
'E
::l
0
Pressure
Pressure
(a) Type I
(b) Type II
(e) Type III
'0
<Il
'0
<Il
0
CIl
'0
I1l
0
CIl
'0
I1l
'E
'E
::l
::l
Pressure
Pressure
(d) Type IV
(e) Type V
FIGURE 3.2 Types of adsorption isotherms.
In case of chemisorption only Type I curves are obtained while in case of physisorption
all five curves are obtained.
51
Surface Chemistry
3.5.1 Type I Isotherm

I. Freundlich adsorption isotherm: In isotherms of type I, the amount of gas adsorbed
per given quantity of adsorbent increases rapidly with pressure and then much more
slowly as the surface is covered with gaseous molecules. To represent the variation of
the amount of adsorption per unit mass of the adsorbent with pressure at constant
temperature, Freundlich proposed the equation
(3.1)
where x is the mass of the gas adsorbed, m is the mass of the adsorbent, P is the
equilibrium pressure, k and n are constants which depend on the nature of the adsorbate
and adsorbent and on temperature. This equation is applicable only at low pressure.
In order to test Eq. (3.1), taking logarithms on both sides, we have
x
log m
If log
=log k + -1 log P
(3.2)
~ is plotted against log P, a straight line is obtained with slope equal to .!.. and
m
intercept equal to log k (Figure 3.3).
1
Slope=fj
logk
log P----.
FIGURE 3.3
Freundlich adsorption isotherm.
It was found that the actual plots were straight lines only at low pressures and showed
a slight curvature at higher pressure. This indicates that Eq. (3.2) holds good only at
low pressures.
Observations: The following are the observations about the Freundlich adsorption
isotherm.
I. At low pressures the graph is found to be a straight line proving that the adsorption
increases with pressure:
x
-ocp
m
== kP
52
2. At intermediate pressures, x depends on 0 to I power of pressure, i.e. fractional

m
power of pressure:
3. At high pressures, the adsorption is almost constant:
x
- = constant (k)
m
Limitations of Freundlich adsorption isotherm: The Freundlich isotherm is only

approximate. The equation is valid over a certain range of pressures only. It fails at high
pressures.
2. Langmuir adsorption isotherm: A much better equation for type I isothenns was
deduced by Langmuir in 1916. According to him, the magnitude of adsorption of a gas
on a solid surface at a given temperature goes on increasing with increase in pressure
until the entire surface of the solid is completely covered by a layer of unimolecular
thickness. Since adsorption is unimolecular, no further adsorption is possible.
Langmuir proposed that the adsorption process con~ists of two opposing actions:
I. Condensation of molecules from the gas phase on the surface
2. Evaporation of molecules from the surface back into the gas phase
Langmuir adsorption isotherm is derived on the basis of the following assumptions:
1. Only a unimolecular layer of gas is adsorbed on a solid surface.
2. The adsorbed layer is uniform throughout the surface of the solid.
3. The adsorbed molecules do not move around the solid surface.
4. There is no interaction between the adsorbed molecules.
Consider an adsorbing surface exposed to a gas. When adsorption starts, every molecule
colliding with the surface may condense on it. The result is that the initial rate of condensation
of molecules on a surface is highest and gradually decreases as the area of surface available for
adsorption is decreased. On the other hand, other gas molecules will evaporate from the surface
due to thermal agitation.
The rate of adsorption of the gas on the adsorbent surface is proportional to the rate at
which gas molecules strike the surface and the free surface available for adsorption. From
kinetic theory of gases, the rate of striking of gas molecules is proportional to the pressure of
the gas (P) at constant temperature. If 8 is the fraction of the surface covered by adsorbed
molecules, the fraction of bare surface is (1 - 8).
Therefore,
rate of condensation oc P(l - 0)
=
kJP(l - 8)
(3.3)
where kJ is proportionality constant.

The rate at which gas molecules evaporate from the surface will depend on the fraction
of the surface covered by gas molecules.
Surface Chemistry
53
Therefore,
rate of evaporation
oc
8
k2 8
(3.4)
where k2 is another proportionality constant.

At equilibrium,
rate of condensation
= rate
klP(l - fJ)
= k2 8
of evaporation
kiP
k2 + kiP
(3.5)
Dividing the numerator and denominator of the right hand side of Eq. (3.5) by k2,
(k/k 2 )P
1+ (k/k2 )P
bP
= 1+bP
(3.6)
where b is another constant and is equal to k l /k2

Since the amount of the gas adsorbed (x) per unit mass of the adsorbent (m) is proportional
to the fraction of the surface covered (8), then
x
y=-=k8
m
(3.7)
where k is proportionality constant. Substituting the value of 8 from Eq. (3.6) in Eq. (3.7), we
get
kbP
y= 1+bP
or
(3.8)
where the constant a = kb.

Equation (3.8) relating the amount of gas adsorbed and the pressure of the gas at constant
temperature is known as the Langmuir adsorption isotherm.
On rearranging Eq. (3.8),
P
=!+(~)p
a
Since a and b are constants, a plot of Ply versus P should yield a straight line with slope
equal to b/a and intercept equal to Va (Figure 3.4).
54
Eng~neer._in~g_C_h_e_m_is-,try=---- _ _ _ _ _ __
1000
P 600
Y
400
200
12
18
24
FIGURE 3.4 Langmuir adsorption isotherm.
It was observed that in numerous cases the actual curves obtained were straight lines thus
verifying Langmuir adsorption equation.
Consider two extreme cases of adsorption.
Case I: If the pressure is very low, the factor bP is negligibly small as compared to unity in
the denominator of Eq. (3.8) and the equation becomes
y = aP
yocP
Thus at very low pressures, the amount of gas adsorbed is directly proportional to pressure.
Case II: If the pressure is very high, unity can be neglected in comparison to bP in the
denominator of Eq. (3.8) and the equation becomes
a
y=b
Thus at high pressures, the amount of gas adsorbed reaches a constant value and becomes
independent of further rise in pressure.
Case III: At intermediate pressures y, i.e. xlm depends on 0-1 power of pressure, i.e. fractional
powers of pressure:
y
= xlm = kplln
This equation is similar to the Freundlich adsorption isotherm.
3.5.2 Types II and III Isotherms

The amount of adsorption goes on increasing in both cases of types II and III isotherms with
increase in pressure. This is attributed due to the formation of multimolecular layers of
physically adsorbed gas molecules on the surface.
Surface Chemistry
55
3.5.3 Types IV and V Isotherms

It is suggested that in types IV and V isotherms, there is not only formation of multimolecular
adsorbed layer of gas molecules but also condensation of gas molecules in the capillary pores
of the adsorbent.
3.6 ADSORPTION ISOBAR AND ADSORPTION ISOSTERE

The effect of temperature on the extent of adsorption at a given pressure of the adsorbate is also
expressed graphically as shown in Figure 3.5a.
The curve showing the effect of temperature on the extent of adsorption at a given
pressure is called an adsorption isobar. The amount of adsorption evidently decreases with rise
in temperature.
Temperature
Pressure
(a)
(b)
FIGURE 3.5
(a) Adsorption isobar and (b) adsorption isostere.
Since rise of temperature tends to lower the extent of adsorption, it is evident that in order
to get the same amount of adsorption at a higher temperature the pressure of the system should
be raised. Hence a straight line relationship between temperature and pressure is generally
obtained.
The curve showing the variation of pressure with temperature for a given amount of
adsorption is called an isostere (Figure 3.5b).
3.7 ADSORPTION OF SOLUTES FROM SOLUTION

Porous or finely divided solid substances can also adsorb dissolved substances (solutes) from
solution. Thus activated charcoal is used for decolourising sugar solution. Activated charcoal
can adsorb colouring impurities on its surface. Similarly, activated charcoal is used to remove
ammonia from solutions of ammonium hydroxide, acetic acid from its solution, etc.
It has been observed that charcoal adsorbs non-electrolytes more readily from a solution
than electrolytes. This behaviour of adsorbents to attract certain substances in preference to
other substances leads to a phenomenon of negative adsorption, i.e. the concentration of the
solute becomes more after treatment with the adsorbent. Dilute solution of potassium chloride
56
stirred with charcoal is an example for this type. The explanation suggested for the negative
adsorption is that in this case, the solvent (water) is adsorbed in preference to the electrolyte
and as a consequence the concentration of the solute is raised. However, at high concentrations,
the electrolyte (potassium chloride) exhibits positive adsorption with the salt being adsorbed in
preference to water.
Adsorption from solution in most of the cases leads to the formation of a layer of
unimolecular thickness on the surface of the solid as observed in the chemisorption of gas on
a solid.
This type of adsorption is also affected by temperature and concentration. The extent of
adsorption decreases with increase of temperature and increases with increase of concentration.
In order to represent the variation of extent of adsorption with concentration, Freundlich
suggested an empirical relation, i.e.
(3.9)
where x is the weight of the solute adsorbed, m is the mass of the adsorbent, C is the equilibrium
concentration of the solute, k and n are constants. This is similar to Eq. (3.1). Taking logarithms
of Eq. (3.9), we get
log m
= log k + -
log C
A plot of log -.::. against log C should be linear with the slope equal to ! and intercept
m
n
equal to log k. Figure 3.6 shows the adsorption of acetic acid on charcoal at 25C.
'Og~i
logC-
FIGURE 3.6
3.8
Adsorption of acetic acid on charcoal.
APPLICATIONS OF ADSORPTION
Adsorption finds extensive applications. Some of the important applications are given as
follows:
Surface Chemistry
57
1. In the production of high vacnum: Adsorption of gases on solids is employed for

creating a high vacuum between the walls of the Dewar flask designed for storing
liquid air or liquid hydrogen. This is achieved by placing activated charcoal between
the walls of the flask which has already been evacuated to the maximum extent using
a vacuum pump. The activated charcoal will adsorb any gas which may appear due to
glass imperfection.
2. In gas masks: Adsorption of gases on solids is also utilized in gas masks which
contain an adsorbent. This adsorbent purifies the air for breathing by adsorbing all the
toxic gases from the atmosphere. Similarly various adsorbents are used in industry to
recover solvent vapours from air.
3. In sugar industry: In the manufacture of cane sugar, the coloured sugar solution is
clarified (decolourized) by treating with animal charcoal or activated charcoal.
4. In controlling humidity: Silica and alumina gels are used as adsorbents for
removing moisture and for controlling humidities of rooms.
5. In heterogeneous catalysis: Adsorption also plays an important role in
heterogeneous catalysis. For example, finely divided iron is used in the manufacture of
ammonia and that of finely divided nickel in the hydrogenation of oils.
6. In froth flotation process: Sulphide ores are freed from silica and other impurities
by froth flotation process. In this process, the finely divided ore is mixed with water
and a small amount of pine oil (foaming agent). The whole mixture is stirred vigorously
by blowing compressed air. The oil forms a foam with air. These adsorb mineral
particles wetted with oil and rises to the surface. The impurities wetted by water settles
down at the bottom.
7. In chromatographic analysis: Mixtures of small quantities of organic substances
can be separated with the help of chromatography which involves the principle of
selective adsorption.
8. In medical field: Excess sodium salts can be removed from the body fluids by giving
the patient a suitable ion exchanger. Similarly if a person is suffering with hyperacidity
(excess acid in stomach) it is neutralized by a suitable medicine containing an anion
exchanger.
3.9 ROLE OF ADSORPTION IN CATALYTIC REACTIONS

Adsorption plays an important role in catalytic reactions. Particularly the adsorption of gases on
the surface of metal catalysts and the formation of products are explained by adsorption theory.
It is also called contact catalysis.
It has been suggested by Langmuir in 1916 that the catalytic activity of a surface depends
on its adsorption of the reactants. The reacting gaseous molecules are adsorbed at different
points on the surface of a catalyst. These adsorbed molecules may form an activated complex,
which then may decompose to form the products. The products are then desorbed from the
surface. This can be explained by considering the hydrogenation of ethylene in presence of
nickel catalyst as an example:
58
I I
H-C---C-H
I I
nickel
catalyst
ethane
The surface reaction (heterogeneous catalysis) involves the following steps (Figure 3.7):
1.
2.
3.
4.
Adsorption of reactant molecules

Formation of activated complex
Decomposition of activated complex
Desorption of products
H ----------H
I
I
I
I
I
I
G--c0
Step 1
Step 2
I
I
c0----
Step 3
FIGURE 3.7
Step 1.
Step 2.
Step 3.
Step 4.
@-@
Step 4
Mechanism of the hydrogenation of ethylene on nickel surface.
Hydrogen molecules are adsorbed on the surface of the nickel due to weak
forces.
The H-H bond is smaller than Ni-Ni bond. So, the H-H bond is stretched and
then becomes weak. As a result, hydrogen molecules are dissociated as
hydrogen atoms. These hydrogen atoms are then chemisorbed on the nickel
surface.
The chemisorbed hydrogen atoms are partially attached to the ethylene
molecule. This results in the formation of an activated complex, which is
unstable.
The unstable activated complex decomposes to give the product (ethane). The
ethane molecules are desorbed from the surface. The freed catalyst surface is
available for further reaction.
Surface Chemistry
59
3.10 ROLE OF ADSORBENTS

3.10.1 Role of Activated Carbon in Pollution Abatement of Air and Waste Water
Adsorption techniques are widely used for removing small quantities of pollutants present in
large volumes of air and water and also for qualitative separation of mixtures. Several solids
possess adsorptive ability with extremely large surface area. Some of the adsorbents commonly
used in pollution control are activated carbon, activated alumina, silica gel, etc. Activated
carbon is an effective adsorbent primarily due to its extensive porosity and very large
surface area.
Manufacture of activated carbon
Activated carbon is manufactured from carbonaceous materials like coal, wood and coconut
shells. The manufacturing process consists of two phases (a) carbonization and (b) activation.
In the first step, the char is produced by heating the material to red hot in a retort
(400-600C) to drive off the hydrocarbons but with an insufficient supply of air to sustain
combustion. The carbonized particles (char) are then activated by exposing them to an
activating agent such as steam at high temperature. The steam bums off the decomposition
products and develops a porous structure. This porous structure creates a large surface area
(Figure 3.8).
(a)
(b)
FIGURE 3.8 Activated carbon: (a) before activation and (b) after activation.
After activation the carbon can be separated into different sizes with different adsorption
capacities. The two size classifications are powdered, which has a diameter of less than
200 mesh and granular which has a diameter greater than 0.1 mm.
Abatement of air pollution using activated charcoal
Activated carbon is used to remove polluting gases such as hydrocarbons since it attracts
thin layers of gases and vapours on its surface leaving the carbon unchanged. The carbon
after being saturated with the pollutant, can be regenerated quickly by passing steam. A
typical fixed bed ad sorber is shown in Figure 3.9.
60
-----=---~----'---------------------
----_..---
Its other uses are given below:

1. Activated carbon is used in air filter and breathing air respirators.
2. It can be used to remove mercury and dioxin emissions from incinerator flue gas.
Polluted gas -
Steem " -
_.........................
~..
-i-U-'---l-:----~i1'i'tr;--u--u";--;:t- FIGURE 3.9
T.T
Steam out
Cleen g.,
Fixed bed adsorber.
Pollution abatement of wastewater using activated carbon
Carbon adsorption is an advanced wastewater treatment method used for the removal of organic
compounds such as oils, chlorinated hydrocarbons, dyes, phenols and pesticides, and heavy
metals.
The unit consists of a tank or tower of activated carbon through which the effluent is
passed. Surface tension on the carbon causes molecules to adhere. Greater the surface area,
greater the number of adhering molecules. Under normal conditions after treatment with carbon,
the effluent BOD is reduced from 200 ppm to 1 ppm and COD can be reduced from 200 ppm
to 20 ppm. Chlorinated hydrocarbons can be reduced from 5 ppm to 1 ppm. Depending upon
the size of the column, virtually all impurities can be removed.
3.10.2
lon-exchange Adsorption
Ion-exchange adsorption is a special type of adsorption in which the adsorbed ions can be
exchanged for other like ions. If the adsorbent exchanges its cations, it is called cation'
exchanger, and if it exchanges anions, it is called anion exchanger.
Cation exchanger
A typical modem cation exchanger is an organic synthetic resin such as polystyrene containing
sulphonic acid group. When a solution containing another cation (Ca2+) is allowed to flow
through the resin, H+ ions are exchanged for Ca2+ ions. This process involves the desorption
of H+ ions followed by the adsorption of Ca2+ ions.
RH2
+ Ca2+ ~ RCa + 2H+
Cation
exchange resin
Since the process is reversible, the resin can be regenerated by treating with an acid.
Surface Chemistry
61
Anion exchanger
Resins containing basic groups such as NH 2, OH, etc., will act as anion exchanger. It will
exchange OH- for Cl-, sOi-, etc.
R(OH)2 + S042- ~ RS04 + 20HThe original anion exchange resin can be regenerated by treatment with a base.
Applications of ion-exchange adsorption
lon-exchange adsorption is used in the softening of hard water by deionization process.

In this process, cations like Ca2+ and Mg2+ and
anions like CI- and sOi- which are responsible for hardness are removed respectively by
cation 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. Resins containing acidic groups (-COOH, -S03H) are capable of
exchanging their H+ ions with cations of hard water. Resins containing basic groups (-NH2,
-OH) are capable of exchanging their anions with the anions of hard water.
Deionization or ion-exchange process:
Process: Water is passed through a tank having cation exchanger which adsorbs all the
cations present in water.
RH2 + CaCl2 ~ RCa + 2HCI
RH2 + MgS04 ~ RMg + H 2S04
The cation-free water is now passed through another tank having an anion exchanger
which absorbs all the anions present in water.
R'(OHh + 2HCI
R'CI 2 + 2H 20
R'(OHh + H 2S04 ~ R'S04 + 2H20

The water coming out of the anion exchanger is completely free from cations and anions
responsible for hardness. It is known as deionized water or demineralized water. It is as pure
as distilled water.
Regeneration:
Cation exchange resins are regenerated by passing a dilute solution of

hydrochloric acid through them.
RCa + 2HCI
RH2 + CaCI2
Similarly, the anion exchange resins are regenerated by passing a dilute solution of sodium
hydroxide through them.
R'Ch + 2NaOH
R'(OH)2 + 2NaCI
A typical ion exchanger is shown in Figure 3.10.
62
Raw _::------,
water
-----------...------'-------------
-----------_____________1-------.
____________ .r---....,
.-------.._----------Cation
exchanger
Alkali for
regeneration
Acid for
regeneration
'----~..
Deionized
water
FIGURE 3.10 Deionizer.
SOLVED EXAMPLE
Example 3.1: In a laboratory experiment 50 cc of 0.2 N acetic acid solution was pennitted
to come to equilibrium with a 5 g sample of charcoal. At equilibrium 25 cc of the acetic acid
solution required 30 cc of 0.1 N sodium hydroxide for neutralization. Calculate the weight of
acetic acid adsorbed per gram of charcoal and the equilibrium concentration of the acid
(Equivalent weight of acetic acid is 60).
Solution:
Volume of acetic acid taken for the experiment
Concentration of acetic acid = 0.2 N
Weight of charcoal taken = 5 g
= 50
ml
Weight of acetic acid present in the original solution

Concentration of acetic acid = 0.2 N
Amount of acetic acid present in 1000 ml of the solution
= Concentration of acetic acid x equivalent weight of acetic acid
= 0.2 x 60 = 12 g
1000 ml of the solution contains 12 g of acetic acid.

Amount of acetic acid present in 50 ml of the solution is
= 12x50 =0.6
1000
Surface Chemistry
Equilibrium concentration of acetic acid (Concentration of unadsorbed acetic acid)

Volume of sodium hydroxide (VI) = 30 ml
Normality of sodium hydroxide (NI ) = 0.1 N
Volume of acetic acid (V2) = 25 ml
We have to find equilibrium concentration of acetic acid (N2 ).
VI x NI = V2 X N2
30 x 0.1 = 25 x N2
N2 = 30xO.1 =0.12 N
25
Equilibrium concentration of acetic acid = 0.12 N
Weight of unadsorbed acetic acid in the solution
Equilibrium concentration of acetic acid = 0.12 N
Weight of unadsorbed acetic acid present in 1000 ml of the solution
= Equilibrium concentration of acetic acid x equivalent weight of acetic acid
= 0.12 x 60 = 7.2 g
1000 ml of the solution contains 7.2 g of acetic acid.
So, the amount of unadsorbed acetic acid present in 50 ml is
7.2 x 50 = 0.36
1000
g
Weight of acetic acid adsorbed

Weight of acetic acid present in the original solution = 0.6 g
Weight of unadsorbed acetic acid = 0.36 g
Weight of adsorbed acetic acid = 0.6 - 0.36 = 0.24 g
5 g of charcoal adsorbs 0.24 g of acetic acid.
Amount of acetic acid adsorbed by 1 g of charcoal is
0.24
5
=0.048 g
Hence, the amount of acetic acid adsorbed per gram of charcoal is 0.048 g.
( SHORT QUESTIONS )
1. What is adsorption?
2. Define the term adsorbent and adsorbate giving suitable examples.

3. What is the effect of temperature on adsorption of gases on solids?
4. Distinguish between physical adsorption and chemisorption.
5. Define chemisorption and physisorption.
63
64
6. What is meant by adsorption isobar?

7. What is an adsorption isotherm?
8. What is adsorption isostere?
( DESCRIPTIVE QUESTIONS)
1. What is an adsorption isotherm? How can you derive the Langmuir adsorption isotherm
mathematically.
2. Give a few applications of adsorption.
3. What are the various factors influencing the adsorption of a gas on a solid?
4. Show under what conditions the Langmuir adsorption isotherm equation becomes
identical with the Freundlich adsorption isotherm equation.
NUCLEAR ENERGY
4.1 INTRODUCTION
The fossil fuels are now conventional sources of power generation. In chemical fuels the
chemical energy stored is released in the form of heat and these chemical reactions involved
only the rearrangement of outer electrons. The atomic nucleus remains intact during a chemical
reaction. Due to the exploitation of fossil fuels, they will not last for more than a few decades
to supply the demand of electric power. Now attention has been focused on the exploitation of
nuclear energy and other sources of power like solar energy, wind and tides for producing power.
During a nuclear reaction the number of protons and neutrons in a nucleus is altered. The
product is a new nucleus of another atom with a different atomic number and mass number. So
a nuclear reaction is one which proceeds with a change in the composition of the nucleus so
as to produce an atom of a new element. The energy released when the nuclei of certain atoms
undergo induced fission or fusion are very much greater than that obtained from chemical fuels.
As the fossil fuels are fast approaching exhaustion, the release of nuclear energy during a
nuclear reaction holds out great hope for the future. Table 4.1 shows the difference between
nuclear and chemical reactions.
TABLE 4.1
Differences between nuclear reactions and chemical reactions
Nuclear reactions
Chemical reactions
I. Nuclear reactions involve a change in the
1. Chemical reactions involve the rearrangement
composition of the nucleus.

2. One element is converted into another, i.e. a
new element is produced.
3. Reactions are accompanied by release or
absorption of a large amount of energy.
of outer electrons.
2. No production of new element.
3. Reactions are accompanied by release or
absorption of relatively a small amount of
energy.
4. Rate of reaction is influenced by external
factors.
4. Rate of reaction is not influenced by external
factors like concentration, temperature, pressure and catalyst.

65
66
4.2
ENERGY RELEASED IN NUCLEAR REACTIONS
The energy changes associated with nuclear reactions are million times more than that of
chemical reactions. These are generally determined by using Einstein's mass-energy relation
mel
E =
where E is the energy equivalent of mass m and c is the velocity of light. For a change of atomic
mass unit (amu), the corresponding energy change:
E = 1.6605
= 1.4924
=
1.4924
931
10-27 kg x (2.9979
x 10-10 kg m2
X
10-10 J x (
S-2 =
108 ms- I )2
1.4924
leV 19
1.602 x 10- J
10-10 J
106 eV = 931 MeV
That is a mass of 1amu is equivalent to 931 Me V of energy.

Very often in nuclear reactions the mass of the products is less than that of the reactants,
The mass difference is converted into energy. For example:
~Li
7.160 amu
~H
iHe
1.0078 amu
4.0026 amu
2He
+ energy
4.0026 amu
In the above equation, the atomic mass difference between the reactants and products is
0.1626 amu. The energy released during this nuclear reaction is calculated by the following
simple relation:
931 MeV
1 amu
x MeV
0.1626 amu
---=----
x = 931 x 0.1626 MeV
=151.4 MeV
Thus in general the nuclear energy can be determined by multiplying the loss in mass by
931 MeV.
4.2.1
Mass Defect (ilm)
Mass defect may be defined as the difference between the mass of an atom and sum of the free
masses of its protons and neutrons (collectively known as nucleons). For example, the mass
defect of helium atom having two protons (mass of one proton = 1.00815 amu) and two
neutrons (mass of one neutron = 1.00899 amu) with the measured mass of 4.0026 is calculated
as follows:
Total expected mass of helium = 2 x 1.00815 + 2 x 1.00899
= 2.0163 + 2.01798
=
4.03428 amu
Nuclear Energy
67
Measured mass of helium = 4.0026 amu

Hence, mass defect of helium = 4.03428 - 4.0026
= 0.03168 amu
The mass defect always represents the amount of disappearance of matter during the
fonnation of a nucleu; by packing together the protons and neutrons.
4.2.2 Binding Energy

The binding energy is a measure of the force that holds the nucleons (protons and neutrons)
together. In a nucleus the positively-charged protons and uncharged neutrons are bound to one
another by very powerful forces. The energy that binds the nucleons together in a nucleus is
called the binding energy. The binding energy is usually expressed in terms of millionelectronvolts (Me V). In other words energy equal to binding energy will be needed to break up
the nucleus into its constituent nucleons. Consequently, the greater is the binding energy, the
more stable is the nucleus.
When a nucleus is formed from individual protons and neutrons, there occurs a loss of
mass (mass defect). According to Einstein's theory it is this mass defect which is converted into
binding energy. Hence binding energy is the energy equivalent to the mass defect.
Mathematically, the binding energy (EB ) and the mass defect (dm) are related as follows:
EB = 931 x dm
Binding energy per nucleon can be calculated by dividing the total binding energy by the sum
of the number of protons and neutrons present in a nucleus, i.e.
I
binding energy of nucleus
d'
bm mg energy per nue eon = - - - - - - " - - - = ' - - - - - - - - number of protons + number of neutrons
4.2.3 Binding Energy and Nuclear Stability

By plotting the binding energy per nucleon against the mass number, a graph is obtained
(Figure 4.1). This shows the relative stability of various nuclei. The greater the binding energy
c
0
Q)
'0
:J
C
a;
C.
>-
Q)
Q)
C)
c
'5
c
iIi
H
2H
50
100
150
200
250
Mass number
FIGURE 4.1
Relative stability of various nuclei.
68
per nucleo'n, the more stable is the nucleus. Thus the nuclei of mass number 60 having
maximum energy per nucleon are more stable, e.g. 56Fe. The nuclei that are heavier and lighter
than this have lower binding energies per nucleon and are less stable. Thus 235U undergoes
fission to give lighter and more stable isotopes such as 139Ba and 94Kr with the release of energy.
Similarly, two or more lighter nuclei eH, 'H) with lower binding energy per nucleon combine
together to give a heavier and more stable nucleus with the release of energy.
4.3
NUCLEAR REACTION
A nuclear reaction refers to a transformation of a target atomic nucleus by bombarding it with

projectiles of light nuclei or free nucleons of adequate energy.
4.3.1
Types of Nuclear Reactions
The nuclear reactions are classified into the following groups in terms of the overall energy
transformation that occurs.
Projectile capture reactions
The bombarding particle is absorbed with or without the emission of gamma radiation. Neutron
capture is common but proton capture is also observed in the case of target nuclei with low m~I'
numbers.
85Rb + 0In
37
86Rb +r
37
Projectile capture particle emission reactions
In this case, in addition to the product nucleus a massive particle, viz. a-particle, proton and
neutron is also produced. The nature of the emitted particle is largely dependent upon the energy
of the projectile. Typical examples are given below.
Fission reactions
The splitting of a heavy nucleus into two or more smaller nuclei is called nuclear fission. The
smaller nuclei formed as a result of fission are called fission products. The process of fission
is always accompanied by the ejection of two or more neutrons with the liberation of a large
amount of energy.
235U+ln
92
0
94
I
139Ba+
56
36 Kr+3 0 n+energy
Nuclear Energy
69
Fusion reactions
In a fusion reaction two light weight nuclei combine or fuse to form a single heavy nucleus.
For example, two nuclei of deuterium undergo nuclear fusion to yield a heavy nucleus of
helium. The fusion reaction takes place at a temperature of about 100 millionC.
2~H ~ ~He + 6n
+ energy
Fusion reactions are also called thermonuclear reactions since they occur at extremely
high temperatures.
In a fusion reaction, the mass of the reacting nuclei is greater than that of the nucleus
formed:
+
3.01495 amu
iHe
1.00782 amu
+ energy
4.00260amu
The total mass of the reactants is 4.02277 amu which is 0.02017 amu greater than the mass
of the product. The loss in mass results in the release of large amount of energy.
4.4 NUCLEAR FISSION

In 1939, Hahn and Strassmann discovered that a heavy atomic nucleus such as uranium (235U)
upon bombardment by a neutron splits into two or more nuclei. 235U first absorbs a neutron to
form an unstable compound nucleus. The unstable compound nucleus then divides into two
daughter nuclei with the release of neutrons and large amount of energy. Hence nuclear fission
is defined as the splitting of a heavy nucleus into two or more smaller nuclei:
235u
92
+ 0In
236U
92
139Ba
+ 94Kr
+ 3 01n + energy
56
36
A given large nucleus can fission in many ways forming a variety of products. For
example, the fission of uranium occurs in about 35 ways. Three of them are given as follows:
94
1
56 Ba + 36Kr + 3 0n + energy
139
235 U + In
92
0
90
I
-f--_ 144
54 Xe + 38 Sr + 20n + energy
128
I
42Mo + 50Sn + 20n + energy
106
4.4.1 Characteristics of Nuclear Fission

The characteristics of nuclear fission are as follows:
1. A heavy nucleus like 235U when bombarded by slow moving neutrons cleaves into two
or more nuclei.
2. Two or more neutrons are produced by fission of each nucleus.
70
3. Large amount of energy is released as a result of conversion of small amount of mass

into energy.
4. All fission products are radioactive which then decay to stable nuclei by emitting ~- and
y -radiations.
5. The atomic masses of the fission products range between 72 and 162.
6. Every neutron set free in the fission of uranium can bring about the fission of other 235U
nucleus liberating more neutrons. Hence a self propagating or chain reaction takes
nlace (Filmre 4.2).
Enormous
energy released
I
I
I
N!O~
n)
(1
----~
__
235U
92
,,.0 / ,e;,
~.(56Ba ,\i~oln
1
'\/
Fi_SS_io_n_ _
1
on
236
U
(Unstable)
0
:Kr
Fission products:
Two smaller nuclei
Three neutrons
FIGURE 4.2
Fission of 235U.
4.4.2 Chain Reactions

We know that
235 U
nucleus when hit by a neutron undergoes the fission reaction:

235U
92
In ~ 139Ba
56
94Kr
36
+ 3 01n
In this reaction three neutrons are produced. These three neutrons in tum may cause
fission in three uranium nuclei producing nine neutrons. These nine neutrons in turn may cause
fission in nine uranium nuclei producing 27 neutrons and so on. This process of propagation
of the reaction by multiplication in threes at each fission is referred to as chain reaction
(Figure 4.3).
A chain reaction will continue until the splitting of all the 235U nucleus. It is observed that
not all the neutrons released in the reactions are used up in propagating the chain reaction. Some
neutrons may miss their targets and some escape into air and are thus lost. Thus for a chain
reaction to occur, the size of the fissionable material should be large enough to capture the
neutron. If the size is too small, more neutrons will escape from its surface thereby breaking
the chain. The minimum mass of fissionable material required to sustain a chain reaction is
called critical mass. The critical mass varies for each reaction. For 235U fission reaction, the
critical mass is about 10 kg.
Nuclear Energy
FIGURE 4.3
71
Propagation of 235U fission reaction.
This chain reaction can be controlled by absorbing a desired number of neutrons so that
on an average only one neutron remains available for carrying out further fission. Such a
reaction is called controlled chain reaction and the energy released in such a controlled chain
reaction does not go out of control. When an average of more than one neutron collides an
atomic explosion occurs. This chain reaction is the basis of the atomic explosion of 235U.
4.4.3 Subcritical Mass and Supercritical Mass

If the mass of the fissionable material is less than the critical mass, it is called subcritical mass.
As the size is low, the neutrons escape into the air and hence a chain reaction cannot be
maintained.
If the mass of the fissionable material is more than the critical mass, it is called
supercritica/ mass. As the size is big, only fewer neutrons escape and as a result a chain reaction
is set up.
4.4.4 Atom Bomb

Adesign of atom bomb is shown in Figure 4.4. It contains two subcritical masses of fissionable
material 235U or 239pu. A mass of trinitrotoluene (TNT) is placed in a separate pocket. When
TNT is detonated it drives one mass of 235U into the other. Due to this a supercritical mass of
the fissionable material is obtained. Hence an uncontrolled chain reaction takes place resulting
in a terrific explosion with the release of enormous amount of heat energy. The explosive force
produced is much greater than that of the most powerful TNT bomb.
72
TNT
Explosive charge
Subcritical
masses
235 U
FIGURE 4.4 Atom bomb.
In the Second World War (1945) two atom bombs were dropped in the Japanese cities of
Hiroshima and Nagasaki. One of these contained 235U and the other 239PU.
4.4.5
Nuclear Energy
A heavy isotope like uranium 35U) or plutonium 39pu) can undergo nuclear chain reaction
with the liberation of large amount of energy. The energy released by the fission of nuclei is
called nuclear energy.
The fission of 235U or 239pU occurs instantaneously producing vast quantities of energy.
If the reaction is uncontrolled, it is accompanied by explosive violence and can be used in atom
bombs. When the reaction is controlled in a reactor, the fission reaction is harnessed to produce
electricity.
4.5
NUCLEAR REACTOR OR ATOMIC PILE
A nuclear reactor is a device in which the nuclear fission reaction is carried out at a controlled
rate so that the liberated energy can be utilized for constructive purposes like generation of
electricity.
4.5.1
Components of a Nuclear Power Reactor
The chief components of a nuclear reactor are as follows:

Reactor core
The reactor core is the principal component of a nuclear reactor. It is that part where controlled
fission reaction is made to occur and where heat energy is liberated. It consists of an assembly
of fuel elements, moderator, coolant and control rods.
1. Fuel elemeut:
The commonly used fissionable materials are as follows:
(a) Natural uranium which contains 0.71% of fissile 235U isotope

(b) Enriched uranium in which 235U has been increased to a few per cent
2. Moderators: The function of the moderator is to slow down the highly energetic
neutrons produced in the fission reaction. Heavy water (D20), graphite, beryllium, etc.
are used as moderators. Neutrons slow down by losing the energy due to collision with
atoms or molecules of the moderator.
Nuclear Energy
73
3. Coolants:
The function of a coolant is to remove the intense heat produced in the

reactor. Through the heat exchangers, the coolants transfer the heat to the secondary
thermal system of the reactor. Ordinary water, heavy water, liquid metal (sodium), etc.
are used as coolants.
4. Control rods: The chain reactions are controlled by using movable rods made up of
boron or cadmium. These rods are having high absorption capacity for neutrons. If the
control rods are pushed into the reactor core, they absorb more neutrons and cut down
the reactivity. If the rods are raised, they will absorb less neutrons and the reaction will
be very fast.
Reflector
The reactor core is usually surrounded by a neutron reflector which reflects back many of the
neutrons that leak out from the core. The requisites of a good reflector are low absorption and
high reflection for neutrons. The material which is used as a moderator can also be used as a
reflector (D20, graphite, Be, etc).
Pressure vessel
The core and the reflector are enclosed in a pressure vessel. It can withstand a pressure of up
to 200 kg/cm 2.
Protective shield
Concrete or steel shield protects the operating personnel and environment from harmful
radiations.
4.5.2 Light Water Nuclear Power Plant

Most commercial nuclear power plants today are light water reactors. As the fuel rods are
submerged in water, this is called a light water power plant (Figure 4.5). Here the water acts
as a coolant as well as a moderator.
"l-".,
'0
'"'~
'w
'-
Movable lOB
control rods
Turbine
generator
Coolant
water
(320C)
Steam
r-
235
U
fuel rod
Stee I
shieIdConcrete
shield -
Coolant
water (280C)
~
FIGURE 4.5
Water
from sea
'-'
Pump
Coolant water
and moderator
Light water nuclear power plant.
74
The fission reaction is controlled by inserting or removing the control rods automatically
from spaces in between the fuel rods. The heat emitted by fission of 235U in the fuel core is
absorbed by the coolant (light water). The heated coolant (water at 320C) then goes to the heat
exchanger. Here the coolant transfers the heat to sea water which is converted into steam. The
steam then drives the turbines generating electricity.
The nuclear waste obtained from the reactor is packed in concrete barrels which are buried
deep in the earth or dumped in the sea.
Some of the nuclear power stations in India are given below.
1. The nuclear power station at Tarapur (Maharashtra) which started production of e1ec
tricity in 1969. This is India's first nuclear power plant.
2. The Rajasthan Atomic Power Station at Ranapratap Sagar that has two reactors which
were installed in 1972 and 1980 respectively.
3. The atomic power station at Kalpakkam has two reactors, which started production in
1984.
4.5.3
Breeder Reactor
Nuclear reactors can be designed in such a way that they can generate their own fuel by
converting non-fissionable material into fissionable material. Plutonium production reactors
belong to this category. For example the non-fissionable 238U can be converted into fissionable
material (239PU):
4.5.4
Hydrogen Bomb
The hydrogen bomb is a device which makes use of the principles of nuclear fusion. The very
high temperature required for an uncontrolled thermonuclear reaction is obtained by the
detonation of an atom bomb. It consists of a small plutonium fission bomb with a container of
isotopes of hydrogen. The fission bomb produces a very high temperature at which
thermonuclear reactions start resulting in the fusion of hydrogen isotopes to form helium:
iH
+ iH ~
i He
+ ~ n + tremendous energy
The explosion of such a bomb is much more powerful than an atom bomb.
SOLVED EXAMPLES
Example 4.1:
Calculate the mass defect and binding energy per nucleon for ~~Co given that
the atomic masses of cobalt, hydrogen atom and neutron are 58.95182 amu, 1.008142 amu and
1.008982 amu respectively.
Nuclear Energy
75
Solution:
Mass number of cobalt
59
Number of protons in cobalt or atomic number of cobalt = 27

Number of neutrons in cobalt = Mass number of cobalt - Atomic number of cobalt
= 59 - 27 = 32
Mass defect (ilm)
= Expected mass of cobalt - measured mass
Expected mass of cobalt :; mass of protons + mass of neutrons
,.
= 27 X 1.008142
= 27.219834
+ 32 x 1.008982
+ 32.287424
= 59.507258
Measured mass of cobalt = 58.95182
Mass defect = 59.507258 - 58.95182
= 0.555438 amu
Binding energy of the nucleus = 931 x 0.555438

931 x mass defect
mass no. of cobalt
Binding energy per nucleon
931 x 0.555438
59
= 8.76 MeV
Example 4.2: Calculate the binding energy in MeV per nucleon of helium atom (iHe) which
has a mass of 4.00260 amu. Mass of neutron = 1.008655 amu and mass of one hydrogen atom
=1.007825 amu.
Solution:
Helium atom (iHe) has two protons and two neutrons.
Mass defect = expected mass of helium - measured mass of helium
Expected mass of helium
mass of protons + mass of neutrons
= 2 x 1.007825
= 2.01565
Measured mass of helium
+ 2 x 1.008655
+ 2.01731
4.03296 amu
4.00260 amu
Mass defect = 4.03296 - 4.00260

= 0.03036 amu
Binding energy per nucleus

Binding energy per nucleon
= 0.03036 x 931 MeV

0.03036 x 931
mass number of helium
76
Engineering ('
0.03036 X 931
4
= 7.07 MeV
Example 4.3: Calculate the binding energy in MeV of iHe which has a mass of 4.00390 amu.
The masses of a proton, a neutron and an electron are 1.007825, 1.008668 and 0.0005852 amu
respectively.
Solution:
i He
has two protons, two electrons and two neutrons.
Expected mass of helium = mass of protons + mass of neutrons + mass of electrons

= 2 x 1.007825 + 2 x 1.008668 + 2 x 0.0005852
= 2.01565 + 2.017336 + 0.0011704
= 4.0341564 amu
Measured mass of helium = 4.00390 amu
Mass defect = 4.0341564 - 4.00390
= 0.0302564 amu
Binding energy released per nucleus = mass defect x 931 MeV
= 0.0302564 x 931
= 28.17 MeV
( SHORT QUESTIONS )
1.
2.
3.
4.
5.
6.
7.
Mention any two differences of a nuclear reaction and a chemical reaction.

Write an equation for a nuclear fission reaction.
What are moderators in a nuclear reaction?
What is a chain reaction?
Define nuclear fusion.
What do you mean by light water nuclear power plant?
What is an atom bomb?
1. What is a nuclear reactor? Describe the components of a light water nuclear power plant
2.
3.
4.
5.
with a suitable block diagram.

Define mass defect and nuclear binding energy. How are they related?
Discuss the characteristics of nuclear fission when uranium undergoes nuclear fission.
Distinguish between nuclear fission and fusion reactions.
With a neat sketch explain the functions of a nuclear reactor.
BATTERIES
5.1 INTRODUCTION
Batteries are considered as storehouses for electrical energy on demand. An electrochemical
power source or battery is a device which converts the chemical energy derived from a chemical
reaction into electrical energy.
The chemical reaction involved in a battery is a redox reaction and some of these reactions
are reversible. The reverse reaction can be brought out by supplying energy, i.e. by applying the
current to the system from an external source. This process is called charging of the battery.
Such batteries in which the cell reactions can be reversed by passing direct electric current in
opposite direction are called secondary batteries. Lead-acid accumulators, nicad battery, etc. are
secondary batteries. Batteries that cannot be charged in this manner, because the cell reactions
are irreversible, are called primary batteries. Primary batteries are the most common batteries
available today because they are cheap and simple to use. Carbon-zinc dry cells, alkaline
batteries, mercury batteries, lithium batteries, etc. are examples for primary batteries. Table 5.1
shows the differences between primary and secondary batteries. In the following sections we
will discuss in detail primary and secondary batteries.
TABLE 5.1
Differences between primary and secondary batteries
Primary batteries
Secondary batteries
l. Primary batteries can be used only once.
1. Secondary batteries can be used, recharged

and reused.
2. In primary batteries, the chemical reactions

that supply the current are irreversible.
2. In secondary batteries the chemical reactions

that provide current from the battery are
readily reversed when current is supplied to
the battery.
3. They are cheap.
3. They are costlier.
4. Initial cost is low.
4. Initial cost is very high.

77
78
5.2
5.2.1
PRI.MARY BATTERIES
Lechlanche Cell or Zinc-Carbon Dry Cell
The zinc~arbon cell uses a zinc anode, a manganese dioxide cathode and an electrolyte of
ammonium chloride dissolved in water. Powdered carbon is mixed with manganese dioxide to '
improve conductivity and retain moisture.
In the dry cell which is a modified Lechlanche cell consists of a zinc anode shaped as a
container for the electrolyte and a graphite rod as a cathode surrounded by Mn02 and a paste
of NH4CI and ZnCl2 as an electrolyte. The dry cell is so called since there is no fluid phase
present (Figure 5.1).
Chemistry:
As the cell is discharged zinc is oxidized and manganese dioxide is reduced:

Zn ~ Zn2+ + 2e(anode)
2NH4+ + 2Mn02 + 2e- ~ Mn203 + 2NH3 + H 20
(cathode)
Zn + 2NH4+ + 2Mn02 ~ Zn2+ + Mn203 + 2NH3 + H20

The voltage of the cell is about 1.5 volt. It is commonly used in flash lights and radios.
Graphite cathode
Zinc case (anode)

Manganese(IV) oxide
Moist paste of
NH4 CI
FIGURE 5.1
Drawbacks of dry cells:
Interior section of a dry cell.
The following are the drawbacks of dry cells:
1. Dry cells do not have an indefinite life period. Since the electrolyte medium is acidic, .
zinc metal dissolves slowly there by reducing the life time even if it is not in use.
2. When current is rapidly drawn from the cell, due to the building up of products on the
electrodes there is a drop in voltage.
Batteries
79
5.2.2 Alkaline Battery

An alkaline battery is an improved form of the dry cell. In this cell, the electrolyte is a
concentrated solution of potassium hydroxide (35-52%). As the electrolyte in this cell is an
alkali, it is called alkaline battery.
The cathode is made from a mixture of manganese dioxide and carbon. The anode mix
consists of alkaline electrolyte, zinc powder and small quantity of gelling agent (starch) to
immobilize the electrolyte and suspend the zinc powder. The alkaline cell derives power from
the oxidation of zinc anode and the reduction of Mn02 cathode.
Zn +
20H-~
2Mn02 + 2H20 +
2e-~
Zn + 2Mn02 + 2H20
Zn(OH)2 + 2e-
(anode)
2MnOOH + 20H-
(cathode)
Zn(OH)2 + 2MnO'OH
The emf of the cell is 1.5 volt. The advantages of an alkaline battery over a dry battery
are as follows:
I. As potassium hydroxide is used as an electrolyte, zinc does not readily dissolve.
2. Since there is no corrosion of zinc, the life of alkaline battery will be longer.
3. Its output capacity is high.
5.2.3 Lithium Battery
Lithium metal is attractive as a battery anode material because of its light weight, high voltage
and good conductivity. Lithium cells use non-aqueous solvents for the electrolyte because of the
reactivity of lithium in aqueous solutions. Organic solvents such as acetonitrile and inorganic
solvents such as thionyl chloride are typical examples.
Lithium cells can be classified into two categories based on the type of cathode material
used.
Cells with solid cathodes: lithium/manganese dioxide cell is the most widely used primary
lithium cell. It is available in many configurations such as coin, bobbin and cylindrical.
LiIMn02 cell uses lithium for the anode, an electrolyte containing lithium salt in an
organic solvent and a specially prepared high density manganese dioxide for the cathode
material.
Li
Li+ + e-
(anode)
MnlV O2 + Li+ + e- ~ MnIII02(Li+)
(cathode)
Li + MnlV O2 ~ MnIII 0 2(Li+)

Manganese dioxide (an intercalation compound) is reduced from tetravalent state to the
trivalent state by lithium. The formation of MnIII02(Li+) signifies that the Li+ ion enters the
crystal lattice of Mn02'
It is used in a wide variety of applications such as safety and security devices, cameras
and many consumer electronic devices.
80
Cells with liquid cathodes: These cells use liquid cathode materials such as thionyl chloride
(80CI 2) that dissolve the electrolyte. The lithiumlthionyl chloride cell consists of a lithium
anode, a carbon cathode and a non-aqueous 80C12 :LiAlC14 electrolyte. Thionyl chloride is both
the electrolyte solvent and the active cathodic material.
The generally accepted cell reaction is:
4Li + 280Cl 2 ~ 4LiCl + 8 + 802
They find applications in medical devices such as neuro-stimulators and drug delivery
systems.
Advantages of lithium cells
Lithium cells have many advantages over conventional batteries:

1. Lithium cells have voltages up to about 4 V compared with 1.5 V for most other
primary batteries.
2. The energy output of a lithium cell is 2-4 times better than that of conventional zinc
anode batteries.
3. Many of the lithium cells will perform over a temperature range of 40-70C.
5.2.4
Mercury Battery
A mercury battery consists of an amalgamated zinc anode, a concentrated potassium hydroxide

electrolyte and a mercuric oxide/graphite cathode. The cross section of a typical mercury button
cell is shown in Figure 5.2. Generally, a permeable barrier is placed next to the cathode to
prevent the migration of cathodic material to the anode.
Separator
FIGURE 5.2
Cathode
Interior section of a mercury battery.
The anodic, cathodic and the cell reactions are given as follows:
Zn +
20H-~
HgO + H20 +
2e-~
Zn + HgO
ZnO + H20 + 2eHg + 20HZnO + Hg
(anode)
(cathode)
(cell)
Batteries
81
As the overall reaction involves only a solid, there is no change in electrolyte

concentration. Therefore it provides a constant voltage of 1.35 V.
It is used in watches, hearing aids and heart pacemakers.
5.3 SECONDARY BATTERIES OR STORAGE BATTERIES OR

ACCUMULATORS
5.3.1 Lead-acid Accumulator or Acid Battery

A storage cell is one which can operate both as a voltaic cell and as an electrolytic cell.
When it acts as a voltaic cell it supplies electrical energy. On recharging it acts as an
electrolytic cell.
An acid battery consists of a negative electrode of porous lead (lead sponge) as the anode
and a positive electrode of lead dioxide as the cathode. A number of such electrode pairs are
immersed in an aqueous solution of 20% sulphuric acid (specific gravity: 1.15 at 25C) which
is the electrolyte (Figure 5.3).
Discharging: The electrode reactions that occur during the discharge of the cell, i.e. when
current is drawn from the cell are as follows :
Anode
Pb
Pb2+ +
Pb2+ + 2e-
sol- ~ PbS04
Cathode
Pb02 + 4H+ + 2e- ~ Pb2+ + 2H 20
Pb2+ + S042- ~ PbS04
The overall cell reaction is as follows:

Pb + Pb0 2 + 2H 2S04 ~ 2PbS04 + 2H 20
The PbS04 fonned gets precipitated on the cathode and in the solution.
Charging: When both anode and cathode become covered with PbS04, the cell stops its
functioning. Recharging is done by applying a voltage across the electrodes that is slightly
higher than the voltage that the battery can deliver.
The net reaction during discharging is as follows:
Ph + Pb02 + 2H 2S04 (
discharging
chargmg
) 2PbS04 + 2H 20
82
During the discharge process the consumption of sulphuric acid is replaced by an

equivalent quantity of water and the sulphuric acid concentration decreases. On charging the
reverse reaction takes place. During the reverse reaction water is consumed and sulphuric acid
is regenerated. Hence the original strength of acid is restored. Since both of these changes are
associated with variations in the specific gravity of the acid, the extent of charge or discharge
of the cell at any time can be determined by testing the specific gravity of the acid.
GAnode
1
Pb plates --+-_-_-?"-.-:-
o Cathode
~l===;;===I=l==;;======>
--:.: - -+--Pb02 plates
=:
--
:--=-:.. --- - - --- =-- --- - - - - - ----------------------------------
-----------"'="----- - -
--------------------------------FIGURE 5.3
Lead-acid storage cell.
Uses
The following are the uses of lead-acid storage cells:

1. Lead-acid storage cells are used in automobiles, hospitals, telephone exchanges, etc.
2. As it is rechargeable it is used in UPS (uninterrupted power supply) a power system
which maintains current flow without even a momentary break in the event of current
failure.
Maintenance
If the lead-acid batteries are properly maintained in the following ways, they can function for
long periods:
1.
2.
3.
4.
5.3.2
Avoid over discharging of the battery.

Maintain the electrolyte at the proper level by adding water (whenever required).
Keep the battery clean.
Avoid overheating of the battery.
Nickel-Cadmium Battery or Nicad Battery
A nickel-cadmium battery is a type of alkaline storage battery. This battery consists of a

cadmium anode, nickel oxyhydroxide cathode and an alkaline electrolyte (potassium
hydroxide ).
Batteries
83
During discharge cadmium metal oxidizes to cadmium hydroxide at the anode:

Cd + 20H- ~ Cd(OH)2 + 2eBy accepting the electrons, nickel oxyhydroxide [NiO(OH)] is reduced to nickel hydroxide [Ni(OH)2J at the cathode:
2NiO(OH) + 2H20 + 2e- ~ 2Ni(OH)z + 20HThe overall cell reaction is:
Cd + 2NiO(OH) + 2H20
2Ni(OHh + Cd(OHh
The emf of the cell is 1.3 volt. This is a rechargeable battery. When the discharged battery
is connected to an external voltage source, the cell reaction is reversed.
Cd + 2NiO(OH) + 2H20
discharging
>
recharging
2Ni(OH)2 + Cd(OH)2
Advantages
Nickel--cadmium cells are characterized by long life, relatively high rates of discharge and
charge and ability to operate at low temperatures.
Uses
Nicad cells are used in calculators, electrical shavers, etc. The good low temperature
performance has lead to wide use of nickel-cadmium batteries in aircraft and space satellite
power systems.
5.3.3 Edison Battery or Iron-Nickel Oxide Cells

An iron-nickel oxide cell is also an alkaline storage battery. This battery consists of an iron
anode, nickel oxide cathode and a potassium hydroxide solution with lithium hydroxide as the
electrolyte.
The basic cell reactions are as follows:
Fe + 2NiO(OH) + 4H 20
Fe(OH)2 + 2Ni(OH)z'H20
The emf of the cell is 1.4 volt.

Edison batteries are used in railway lighting.
5.4 SOLAR CELLS OR PHOTOVOLTAIC CELLS

Photovoltaic cells convert solar energy directly into electrical energy.
Description of solar cells
The conventional solar cells made up of p-type doped semiconductor (Le. silicon doped with
boron) and n-type doped semiconductor (Le. silicon doped with phosphorus) is shown in
Figure 5.4
84
Metal electrode
on front side
n-type silicon
p-type silicon
External
load
Metal electrode on back side
FIGURE 5.4 Solar cell.
The surface layer is made up of n-type semiconductor and it is extremely thin (~ 0.2 ~m)
so that sun light can penetrate through it. The bottom layer is made up of p-type
semiconductor. The electrodes made of Ti-Ag solder are attached to both the sides to provide
electrical contact. The electrode on the top surface is in the form of a metal grid with fingers
which permit sun light to pass through. On the back side, the electrode completely covers the
surface. An anti-reflection coating of silicon oxide having a thickness of 0.1 11m is also put
on the top surface.
Working
When p-type and n-type semiconductors are placed together, electrons from n-type side diffuse
across p-n junction to combine with holes present in p-type semiconductor side. As a result
positive ions (on n-type side) and negative ions (on p-type side) are created near the junction
to certain thickness. The separation of charges produces an electric field across p-n junction
which is about 0.6-0.7 volt. This potential at p-n junction prevents the charges moving across
it further.
When light strikes on the p-n junction, electron-hole pair is produced. As the potential
barrier resists the flow of charge carriers across it, they flow through the conductornoad
connected externally to produce electric current.
Since the emf of a single solar cell is about 0.6 V, they are arranged into larger groupings
called arrays in solar panels.
Applications
The following are the application of solar cells:

1.
2.
3.
4.
Solar cells are used to provide power supply for space satellites.
They are used for the distillation of water to get pure drinking water.
Solar cells provide thermal energy for solar cookers, solar furnaces, etc.
They provide electricity for street lighting in remote areas, and to run water pumps ana
radios in desert areas.
5. Solar cells provide electric power to light houses.
Batteries
85
5.5 FUEL CELLS

A fuel cell is an electrochemical cell in which the chemical energy of the fuel-oxidant system
is directly converted into electrical energy. It is an energy conversion device or electricity
generator.
A fuel cell operates like a galvanic cell with the exception that the reactants are supplied
from outside. It is an example for a primary cell. This is capable of supplying current as long
as it is provided with the supply of reactants.
5.5.1 HydrogenOxygen Fuel Cell

A fundamental and important example of a fuel cell is the hydrogen/oxygen cell. Like an
electrochemical cell, the fuel cell is also having two electrodes and an electrolyte. The two
electrodes are made up of porous graphite admixed with nickel powder. The electrolyte used is
potassium hydroxide solution maintained at 200C and 20-40 atmospheres. Hydrogen and
oxygen gases are bubbled through the anode and cathode compartments respectively. Hydrogen
is oxidized at the anode whereas the oxygen gets reduced at the cathode (Figure 5.5).
2H2(g) + 40H-(aq)
4H 20 + 4e-
Eo
Cathode: 02(g) + 2H20(l) + 4e-
40H-(aq)
Eo
= +0.4 V
2H20(l)
Anode:
-0.83 V
The overall reaction is

2H2(g) + 02(g)
Eo
= + l.23 V
The cell reaction is the same as combustion of hydrogen in air or oxygen. Generally a
large number of these cells are stacked together in series to make a battery called fuel cell
battery or fuel battery.
In the fuel celis, gaseous fuels used are hydrogen, alkanes and co. Among the liquid fuels
methanol, ethanol, etc. are very important. Oxygen, air, hydrogen peroxide, etc. are some of the
oxidants used.
---,--~-....-
H2
Porous
graphite
electrodes
02
--+~----~~~----~~
Electrolyte
(Aqueous KOH)
FIGURE 5.5
Hydrogen-oxygen fuel cell.
86
Advantages of fuel cells
The following are the advantages of fuel cells:
1. The energy conversion efficiency is very high (75-83%)

2. They are used as power sources in spacecrafts.
3. The product of a hydrogen-oxygen fuel cell is pure water which can be used for
drinking purpose.
4. Noise and thermal pollution are very low.

5. The maintenance cost is very low.
6. It saves fossil fuels.
Limitations
The following are the limitations of fuel cells:

1. The cost of power from a fuel cell is high as result of the cost of electrodes and pure
hydrogen gas.
2. As the fuels used are gases, they have to be stored in big tanks under high pressures
5.6
WIND ENERGY
Among the different renewable energy sources, wind energy is currently making a significant:
contribution. The high speed winds have a lot of energy in them as kinetic energy due to their
motion. The driving force of the winds is the sun. Wind power is the conversion of wind energy
into electricity using wind turbines or wind mills. A wind turbine works the opposite of a fan,
Instead of using electricity to make wind, a turbine uses wind to make electricity. The blades
of the wind turbine will keep on rotating continously due to the force of the striking wind. The
rotation of the blades spins a shaft, which is connected to a generator that produces electricilf
A large number of wind turbines are installed in clusters called wind farms.
Main shaft
Rotor hub
Generator
", _ _ _ Nacelle
High-speed
shaft
Tower
FIGURE 5.6
A wind turbine.
Batteries
( SHORT QUESTIONS
87
)=
l. What is a primary battery? Give an example.
2. What is a photogalvanic cell?

3. How are anodic and cathodic electroactive materials made in Ni-Cd battery?
4. List the advantages of using a lithium battery.
5. Explain the differences between a primary cell (non-rechargeable) and a storage cell
(chargeable).
6. What is a lead-acid accumulator?
7. What are the advantages of an alkaline battery over a dry battery?
l. How is a lead-acid battery constructed?
2.. Construct a nickel-cadmium cell and indicate cell reaction.
3. Lithium battery is the cell of the future. Why?

4. Write a note on a Ni-Cd battery.
5. Explain the construction and working of a lead-acid battery. Suggest means for proper
maintenance of the battery. What are the requirements of the battery to be used in
automobiles and UPS?
6. What are the important advantages envisaged for a lithium electrode? Explain the
construction of anyone battery with lithium as the negative electrode.
7. Explain the chemistry involved in the functioning of a nicad battery.
8. Outline the principle and working of a lead-acid battery.
9. Write a note on hydrogen-oxygen fuel cell.
REFRACTORIES
6.1
INTRODUCTION
Refractories are inorganic materials that can withstand high temperatures without softening or
undergoing any deformation in shape. They are mainly used in engineering as a material to
confine heat (inner lining of a furnace), to maintain high temperatures and to resist the
abrasive and corrosive action of molten metals, slags and gases at high operating
temperatures without distortion in shape. Refractories are used for the construction of the
linings of the furnaces, kilns, etc., which are employed for the manufacture of cement, glass,
metals, etc.
Refractories are available in different shapes such as bricks, crucibles, tubes and granules.
6.2
REQUISITES OR CHARACTERISTICS OF A GOOD REFRACTORY
The following are the essential characteristics of a good refractory. It should:

1. Not fuse at the operating temperature.
2. Possess good refractory properties, i.e. its physical, chemical and mechanical properties
should not undergo substantial changes at high temperatures.
3. Be chemically inert towards the corrosive action of molten metals, slags and gases
produced in the furnace.
4. Be capable of retaining its original form without cracking and splitting when subjected to
sudden temperature differences.
5. Be strong enough to bear the charge load at the working temperature.
6. Resist the abrading action by molten metal or slag.
7. Not cause contraction and expansion in a sudden but uniform manner.
88
Refractories
89
6.3 MANUFACTURE OF REFRACTORIES

The raw materials are mineral deposits like clay, sand, rocks and ores. Substances with fusing
temperatures above 1580C are normally used in making refractories. The manufacturing
process consists of the following steps.
I. Calcination:
Raw materials like dolomite, magnesite, bauxite and fire-clay are calcined at temperatures ranging from 1200 to 1700C in rotary kilns. This operation removes the volatile constituents from the raw materials.
2. Crushing and grinding:

ground in ball mills.
The raw materials are crushed in jaw crushers and then finely
3. Screening: The ground raw materials are sized into coarse and fine fractions with the
help of vibrating screens.
4. Beneficiation (mineral dressing): The impurities are removed from the raw materials
by processes like froth floatation and magnetic separation.
5. Blending and mixing: In this stage, the raw materials of the proper size distribution
are blended with binders and water so as to obtain the final product of desired porosity.
6. Moulding: The moulding may be done either manually or mechanically by the
application of high pressure. The standard form for refractories is brick but refractories
can be made in a variety of shapes to suit the needs of the industry.
7. Drying: The main purpose of drying is to remove the moisture added to develop
plasticity in the mixture before mOUlding.
8. Firing: The refractories are fired to stabilize and strengthen their structure. During
firing, the more fusible constituents form a liquid which on cooling forms a glassy matrix.
This binding of refractory particles together in a glassy matrix is referred to as the ceramic
bond. The firing temperature of different bricks are 1700C for kaolin bricks and 1870C
for some basic bricks. Firing of bricks is done in continuous chamber kilns.
6.4 PROPERTIES OF REFRACTORIES

6.4.1 Refractoriness
It is the ability of a refractory material to withstand high temperatures without appreciable
softening or deformation under working conditions. Refractoriness is usually measured by the
softening or fusion temperature of the material. A refractory material should have softening
temperature higher than the operating furnace temperature.
The softening temperature of a refractory is determined by the standard pyrometric cone
equivalent (peE) test or Seger cones test. In this test pyrometric cones or Seger cones of
standard dimensions (38 mm height with triangular base of 19 mm sides) are prepared from
various refractory materials. These are known as standard cones. When a standard cone is
heated on a base under standard conditions (1 OOC/minute), at one stage, the apex of the cone
bends and touches the base. The temperature at which this occurs is the measure of the softening
temperature of the cone. Depending upon the softening temperature, the cones are given
some numbers known as PCE:
90
peE
Softening temperature (0C)
1110
1120
37
38
1825
1850
To obtain the refractoriness of a material, the finely ground refractory is moulded into
small cones of standard dimensions. This is heated with other standard cones. The PCE value
of the test or given refractory is taken as the number of standard cone which softens along wiili
the test cone (Figure 6.1).
Pyrometric cone
FIGURE 6.1
Deformed cone
Pyrometric cone equivalent (peE) test.
If the softening temperature lies between the fusion temperature of two consecutive Seger
cones, the peE value of the test refractory is approximately measured as the average of two
values.
6.4.2
Spalling Resistance or Thermal Spalling
SpaIIing is the breaking or cracking or peeling of a refractory material. A good refractory should
be resistant to thermal spaIIing. Uneven thermal expansion or contraction due to temperature
differences, arising out of rapid heating or cooling is the main cause for thermal spalling. The
spalling tendency is directly proportional' to the coefficient of expansion. Hence to avoid
spalling, a refractory should have a low coefficient of expansion.
6.4.3
Strength or Refractoriness Under Load (RUL)
Refractories used in metallurgical operations and industries have to withstand varying loads.
Refractories like alumina do not bear loads over a range of temperature. They soften gradually
and collapse before the softening point. On the other hand, refractories like silica bricks bear
maximum loads and soften only in the vicinity of their fusion point. The strength of silica
refractories is comparatively higher than alumina bricks. Hence refractories should have hi~
mechanical strength under operating temperatures. The load bearing capacity of a refractory can
be measured by means of RUL test.
Refractories
91
Refractoriness under load or strength of a refractory is its ability to withstand high

temperatures under the influence of maximum load without breaking. RUL is performed on a
test specimen of standard size (cylinder diameter 50 mm and height 50 mm). The specimen
is heated in a furnace at a rate of lODe/minute under a load of 1.75 kg/cm 2 RUL is expressed
in terms of the temperature at which 10% deformation occurs on the specimen. A good
refractory should have a high RUL value.
6.4.4 Porosity
Due to porosity, slags, gases, etc. are likely to enter more easily to greater depth and also react
with a refractory. Hence porosity reduces the strength and resistance to corrosion. Porosity of
a material is given by the ratio of its pores volume to that of its bulk volume. Thus, porosity
is given as
p= W -D x 100
W-A
where W = weight of saturated specimen in air
D = weight of dry specimen in air
A = weight of saturated specimen submerged in water.
The saturation of the specimen may be carried out by boiling in water for two hours.
The lower porosity increases thermal conductivity due to the absence of air voids and
increases resistance to thermal spalling. The high porosity refractories possess lower thermal
conductivity due to the presence of more air voids. High porous refractories act as insulator and
hence it can be used for lining in furnace, oven, etc. A good refractory in general should have
lower porosity.
6.4.5 Dimensional Stability

Dimensional stability is the resistance of a refractory to any volume change when exposed to
high temperature over a prolonged time. These dimensional changes may be reversible or
irreversible (permanent). Irreversible changes may lead to contraction or expansion of
refractory. When a refractory is exposed to a high temperature for a long period, the low fusible
constituents of the refractory will form increasing amount of liquid. The liquid gradually fills
the pores of the refractory body causing high degree of shrinkage. For example, on heating
magnesite bricks (specific gravity 3.05) is gradually converted into more dense crystalline form
ofpericlase (sp.gr. 3.54). But in certain refractories, prolonged heating may lead to expansion.
For example, on heating there is an increase in the volume of silica bricks due to transformation
of quartz form (sp.gr. 2.65) into cristobalite (sp.gr. 2.32).
In the case of reversible dimensional changes, the refractory material will result in uniform
expansion and contraction. A good refractory material should have reversible dimensional
changes.
92
6.5
CLASSIFICATION OF REFRACTORIES
Refractories are mainly classified into three types: (a) acid refractories, (b) basic refractories ana'
(c) neutral refractories.
6.5.1
Acid Refractories
These are made up of acidic materials like silica. Acid refractories are not attacked by acidic
substances but are easily attacked by basic substances, e.g. silica and fire-clay refractories.
Fire-clay refractories
Fire-clays contain more amount of silica (50-80%) and less amount of alumina 50%). The
raw materials used in the manufacture of fire-clay refractories are fire-clay and calcined fire
clay. The raw materials are mixed with water and converted into bricks followed by firing at
1300oC.
Properties: Fire-clay refractories are slightly acidic in nature. They possess lower refractoriness
(1500-1600C), lower porosity and higher resistance for thermal spalling.
Uses: The steel industries are the largest users of these bricks. They are mainly used for lining
of blast furnaces, open hearths and lime kilns.
6.5.2
Basic Refractories
Basic refractories are made up of basic materials like calcium oxide and magnesium oxide. They
are not attacked by basic substances, but are easily attacked by acidic substances, e.g. magnesite
and dolomite refractories.
Magnesite refractories
Magnesite is calcined at 1700C to form a dense, hard crystalline variety of magnesia. This
magnesia is called dead burnt magnesite. It is ground, mixed with iron oxide (binder) and water.
moulded at high pressure, dried and fired at about 1500C to give fire bonded bricks. The)
contain 80-95% magnesium oxide, 2-7% iron oxide and <4% aluminium oxide.
Properties: The following are the properties of magnesite refractories:

1. They have high refractoriness (2000C) but poor spalling resistance due to high coefficient
of thermal expansion.
2. They have high thermal conductivity.
Uses: They are largely used in steel making furnaces and rotary kilns. Magnesite refractories
are also used in copper smelting furnaces and furnaces processing antimony ores.
6.5.3
Neutral Refractories
These are made up of neutral materials like graphite, zirconia and silicon carbide. Neutral
refractories are inert towards both acidic and basic substances, e.g. carbon and graphit'
refractories.
Refractories
93
Silicon carbide (SiC) or carborundum refractories
Silicon carbide is made by heating a mixture of 60% sand and 40% coke together with some
saw dust in an electric furnace at ISOOoe. The silicon carbide removed from the furnace is then
mixed with a bonding agent (like clay and silicon nitride) and shaped, dried and fired at about
I500C.
Properties: The following are the properties of silicon carbide refractories:

I. They have high refractoriness (2S00C).
2. They possess high resistance to spalling.
3. They have high thermal conductivity, low thermal expansion and high mechanical
strength.
Uses: They are mainly used in muffle furnaces.
6.6 SOME IMPORTANT REFRACTORY BRICKS

6.6.1 High Alumina Bricks
When the alumina content in fire-clay brick reaches above 47.S%, then it is called high alumina
refractory brick. They are generally prepared by heating a mixture of bauxite and clay at
1400C.
Properties: The properties of high alumina bricks are as follows:

I. They are having low coefficient of expansion, high porosity and little tendency to spall.
2. They are highly resistant to basic slags.
3. They are having high mechanical strength.

4. They are highly resistant to abrasion.
Uses: High alumina bricks are used in cement industry and paper mill factories. They are used
in the linings of glass furnaces, oil-fired furnaces, etc.
6.6.2 Zirconia Refractory Bricks

Zirconite mineral (zirconium oxide, zr0 2) is calcined and powdered. Powdered zirconia is
immersed in water for a long time. Then the wet zirconia is mixed with a binder (alumina). The
mass obtained is made into bricks by hand moulding or press moulding. Bricks so produced are
air dried and burnt to about 17S0oe.
Properties: The following are the properties of zirconia refractory bricks.

I. The refractoriness is very high (2240-2600C).
2. They are highly resistant to the action of slags and chemicals.
3. They are less sensitive to sudden changes in temperature.
Uses: Zirconia refractory bricks are used as a crucible for melting sodium, potassium,
aluminium, etc.
94
6.7
CERMETS
Cermets are hot-pressed or sintered materials made by the combination of ceramics and metals.
The metal serves as a binder for ceramic particles. The important characteristics of cermets are:
(a) high refractoriness of ceramics, (b) high thermal conductivity and shock resistance of metals,
and (c) high shapability.
Zirconium carbide, molybdenum carbide and tungsten carbide are some of the refractory
ceramics used in cermets manufacture. Iron, aluminium, chromium, cobalt, nickel, etc. are some
of the metals used in cermets manufacture. Cermets contain about 80% of the ceramic materials
and 20% of the metal. They are usually fabricated by powder metallurgy technique.
Uses: These are used to make rocket and jet engine parts.
6.8
SELECTION OF REFRACTORIES
The choice of a refractory depends on the following factors:

(a) The type of furnace used
(b) The temperature of operation
(c) Nature of the slags, melts and gases with which the refractory material is likely to
come into contact
(d) The nature of the materials to be handled
(e) The load applied
(f) The magnitude of temperature fluctuations.
( SHORT QUESTIONS )
1. What are refractories? How are they classified?
2. What is refractoriness?
3. What is meant by thermal spalling? How is it reduced?
4. Distinguish between refractory and refractoriness.
5. Write a note on cermets.

6. What is meant by pyrometric cone equivalent of a refractory?
1. What are the characteristics of a good refractory?
2. How is the chemical composition of a refractory related to its uses?

3. What are fire-clay refractories?
Refractories
95
4. What are the essential conditions under which a substance can function as a good
refractory material?
5. Discuss the following important properties of refractories.
(a) Refractoriness
(b) Thermal spalling
(c) RUL test
6. What are refractories? How are they classified? Give examples.
7. List out the essential requisites of a good refractory.
ABRASIVES
7.1
INTRODUCTION
Abrasives are very hard materials that can be employed to rub down other objects and help in
polishing, shaping, grinding and cutting operations.
7.2
ABRASIVE POWER
Abrasive power is the capacity of a particular abrasive to rub down other objects. It depends
upon the following three important properties: hardness, toughness and refractoriness.
7.2.1
Properties of Abrasives
1. Hardness: It is the capacity of an abrasive to scratch other substances. The harder is the
abrasive the better is its abrasive power. Normally, the abrasive should be harder than the
surfaces abraded. Hardness of abrasives is expressed on Mohs' scale where the hardest
substance diamond is given the number 10, and the softest substance talc, 1.
The common abrasives in the increasing order of hardness on Mohs' scale are given in
Table 7.1.
2. Toughness: Toughness is the opposite of brittleness. A brittle material abrades better
than a tough material because a brittle material is sharp. An abrasive can be made brittle
by altering the method of manufacture and also by reducing the size of crystal.
3. Refractoriness:
It is the capacity of an abrasive to withstand high temperature.
96
Abrasives
TABLE 7.1
Name of the abrasive
Talc
Gypsum
Calcite
Fluorite
Apatite
Feldspar
Quartz
Topaz
Corundum
Diamond
97
Mohs' scale of hardness

Chemical formula
Mohs . number
3MgO'4Si02'H 20
CaS04'2H20
CaC03
CaF2
CaF2'3Ca3(P04h
K20'AI 20 3'6Si02
Si02
AI 2Si04(F,OH)
AI 20 3
C
1
2
3
4
5
6
7
8
9
10
7.3 CLASSIFICATION OF ABRASIVES

Abrasives are divided into two types: natural abrasives and artificial or synthetic abrasives.
7.3.1 Natural Abrasives

Natural abrasives include diamond, corundum, emery, quartz, garnets, etc.
I. Diamond: Diamond is the hardest material. It is chemically inert and not attacked by
acids, alkalis and chemicals. It is used in drill points for drilling rocks and as teeth for
saws for cutting rocks. Various non-metallic materials like hard rubber and fibre may be
cut readily with diamond tools.
2. Corundum:
Corundum is the crystalline form of aluminium oxide. Corundum comes

next to diamond in hardness. It is mostly used for the manufacture of abrasive wheels used
by the metal industry.
3. Emery: Emery is a mixture of corundum (AI20 3) and magnetite (Fe304)' It is used in

the tip of cutting and drilling tools. It is also used for making emery paper.
4. Quartz: Quartz is almost pure form of silica. It is crystalline and brittle in nature. It is
mostly used for making sand paper.
S. Garnets: Garnets are hard and dense silicate minerals. The general chemical formula of
the silicate garnet group is A 3B 2(Si04)3 where the A cations are dominantly ferrous,
magnesium and calcium and the B cations are aluminium and ferric. Some of the garnets
generally used are Ca3AI2(Si04)3, Ca3Fe2(Si04)3, Fe3AI2(Si04)3, etc. Hardness of garnets
ranges from 6 to 7.5 on Mohs' scale. They are mainly used for making abrasive cloth and
paper.
98
7.3.2
Artificial or Synthetic Abrasives
1. Carborundum or Silicon carbide: Carborundum is manufactured by heating sand and

coke together with some saw dust in an electric furnace.
Si02 + 3C
SiC + 2CO
Carborundum is resistant to chemicals and can withstand high temperatures. It is hard and
brittle. It is mostly used for making grinding wheels. These wheels are employed for
grinding glass, granite, rubber and leather.
2. Alundum: Alundum is prepared by heating a mixture of calcined bauxite, coke and iron
in an electric furnace. It is more durable and tougher than silicon carbide. It is used in
grinding wheels and in making abrasive paper and cloth.
3. Boron carbide or Norbide: Boron carbide is the hardest of all the artificial abrasives.
It is made by heating boron oxide with coke in an electric furnace at 2700 oC.
2B 20 3 + 7C
B4 C + 6CO
It is generally used for cutting steel.
7.4
USES OF ABRASIVES
Most of the abrasives are used as (a) loose powder, (b) abrasive paper and abrasive cloth and
(c) grinding wheels.
In the loose form, abrasive powder is employed to clean surfaces before surface coating
is carried out.
7.4.1
Abrasive Paper and Abrasive Cloth
The abrasives are used for cleaning and polishing of different materials in the form of abrasive
paper and abrasive cloth. These abrasive paper and cloth are manufactured by passing rolls of
paper or cloth through rollers and applying a soft glue on the upper side (Figure 7.1). The glue
VO
Warm drying room
Abrasive paper
or cloth sheets
Rollers
Paper or cloth roll
FIGURE 7.1
t.:::..:::-::::::::::
Manufacture of abrasive paper or cloth.
Abrasives
99
coated paper is sprayed with abrasive grains which fall from a hopper. The paper or cloth is
again applied with a thin coating of glue followed by drying in warm rooms. Finally the dried
sheets are cut into various sizes.
Emery, silicon carbide, fused alumina and sand are the abrasives mainly used for making
abrasive paper and cloth. They are mainly used to smoothen the surfaces of wood and metal.
7.4.2 Grinding Wheels

Abrasive wheels used to grind, polish and smoothen the surfaces of other materials are known
as grinding wheels. These are commonly used in workshops to sharpen tools, edge of knives,
etc. These wheels are manufactured by mixing crushed abrasive with a suitable binder (called
bond). Then this mixture is moulded into wheels and heated well to make it sufficiently hard
for grinding. For making grinding wheels, artificial abrasives are preferred because of their
purity, uniform chemical composition and hardness.
Manufacture of grinding wheels
During the production of grinding wheels the following factors are taken into consideration.
\. Selection of abrasive: The abrasive should be selected such that it quickly removes the
material without any harmful effect on itself and the grinding wheels. Silicon carbide is
mostly used for grinding materials like copper and brass which have low tensile strengths.
Fused alumina is used for grinding materials like alloy steel which possesses high tensile
strength.
2. Selection of the grain size: The use of a particular size of grain will depend mainly on
the nature of the job to be performed by the grinding wheel. Most of the abrasives are in
the form of big lumps. The lumps are broken by jaw crushers and pulverized to fine
powder. The grains of various sizes are then separated by sieving through various types
of sieves. Coarser grains cut quickly while fine grains cut slowly but give better and
smooth finishing.
3. Type of binding materials or bonds:
Bond or binding material is a substance that binds

abrasive grains together in the form of a wheel. A good bond should break gradually when
the bonded grinding wheel is put in use. The important types of bonds used are
(a) Ceramic bond: The ceramic bond is produced by mixing the abrasive with feldspar
and clay along with water. The material is shaped, dried and fired in a kiln. The
ceramic bonded product is hard and can withstand the action of heat and chemicals.
Hence the ceramic bond finds extensive use in industry.
(b) Silicate bond: The silicate bond is obtained by mixing abrasive grains with a solution of sodium silicate and clay. The mixture is moulded, dried and fired. The silicate
bond is weaker than the ceramic bond.
(c) Resin bond: The resin bond is produced when a mixture of abrasive materials,
phenol-formaldehyde resins, filler, plasticizer, etc. is shaped by the application of heat
and pressure. The bond produced is quite strong.
100
--~------------------------------------
( SHORT QUESTIONS )
1. Define an abrasive.
2. Write down the applications of abrasives.
3. Give two examples each for natural and artificial abrasives.
4. Name two hard and soft abrasives.
1. Describe the manufacture and uses of anyone of the synthetic abrasive.
2. Describe the important characteristics of abrasives.
3. Explain the natural and artificial abrasives with examples.
4. How are carborundum, alundum and boron carbide manufactured? What are their uses1
5. Describe the manufacture of abrasive paper. What are its uses?

6. Write a note on grinding wheels.
LUBRICANTS
""'"'-------
8.1 INTRODUCTION
In all types of machines, the surfaces of moving parts tUb against each other. Due to mutual
rubbing of one part against another, a resistance is offered to their movement. This resistance
is known as friction. Friction is a force of resistance to the relative motion of two contacting
surfaces. Friction causes a lot of wear and tear of surfaces of moving parts and such parts
require repeated replacement. Due to friction, large amounts of energy are dissipated in the form
of heat, thereby causing loss in the efficiency of the machine. Moreover, the moving parts get
heated up, damaged and sometimes even result in seizure.
Lubrication may be defined as the reduction of friction and wear between two relatively
moving surfaces by the interposition of some substance between the surfaces. The substance
thus introduced is known as a lubricant. A lubricant may be defined as a substance which
reduces the friction when introduced between two tUbbing surfaces.
In lubrication, the lubricant used does not allow direct contact between the rubbing surfaces by keeping its own film in between the rubbing surfaces. In this way, injury to the surfaces
due to seizure and wear are reduced.
8.1.1 Functions of a Lubricant

The functions of a lubricant are as follows:
l. A lubricant prevents direct contact between the rubbing surfaces. Hence, it reduces
wear, tear and surface deformation of the concerned parts. Thus, it reduces the
maintenance and running cost of a machine.
2. It reduces wastage of energy and hence increases the efficiency of the machine.
3. A lubricant reduces the frictional heat and thus prevents the expansion of metals.
101
102
4. It acts as a coolant by removing the frictional heat generated due to the rubbing of
surfaces.
5. A lubricant acts as a seal preventing the entry of dust and leakage of gases at high
pressures.
8.2
MECHANISMS OF LUBRICATION OR TYPES OF LUBRICATION

MECHANISM
Lubrication is affected mainly by three mechanisms. They are as follows:
8.2.1
Fluid film or hydrodynamic lubrication

Thin film or boundary lubrication
Extreme pressure lubrication
Fluid Film or Hydrodynamic Lubrication
In this type of lubrication, the moving surfaces are separated completely by applying a thick '
uniform film of lubricant between them (Figure 8.1). The thickness of fluid film is at least
loooA.
~
Load
:::::::::':::::::::::::::::::::::
::::::::::::::::::::::::::::::::
Thick layer
of lubricant
IIIIIIA
FIGURE 8.1
Fluid film lubrication.
The fluid film covers all irregularities in the sliding surfaces and prevents the contact
between moving surfaces. Thus, the formation of welded junctions is prohibited. Since the fluid
film comes in contact with the moving surface, it offers resistance to motion due to its viscosi~.
Thus, the liquid lubricant must have sufficient viscosity so as to maintain the fluid film in its
place.
In such type of lubrication, when the load is applied, the corresponding pressure
developed in the lubricant is sufficient to keep moving surfaces apart and therefore it is known
as hydrodynamic lubricqtion. This type of lubrication is useful in delicate machinery like
watches, clocks and sewing machines. Hydrocarbon oils are very effective for this type of
lubrication.
Lubricants
103
8.2.2 Thin Film or Boundary Lubrication

Under the conditions such as high load and a very low viscosity of oil, a continuous fluid film
cannot be maintained between the rubbing surfaces. Under such conditions, the thickness of the
fluid film should be less than 1000 A. Such a thin film consists of one or two molecular layers.
To form a thin film, the lubricant has to be adsorbed on the metal surface by physical or
chemical forces. In some cases, the lubricant may chemically react with the metal surface
forming a thin film of metal soap which acts as a lubricant. This film is known as boundary
film.
The property of oil responsible for its adsorption on metal surface is known as
oiliness. Vegetable and animal oils containing fatty acids have more oiliness, e.g. oleic acid
(C'7H33COOH) and stearic acid (C 17H3SCOOH). These oils have polar carboxyl group (-COOH)
which reacts with the metal surface to form a continuous thin film of lubricant. The
hydrocarbon chain of fatty acid gets oriented outwards in a perpendicular direction as
shown in Figure 8.2.
Carboxyl
group
Alkyl group
FIGURE 8.2
Oiliness of fatty acid.
Good boundary lubrication is observed using blended oils. Solid lubricants like
molybdenum disulphide and graphite are also useful in boundary lubrication.
8.2.3 Extreme Pressure Lubrication

Under boundary lubrication conditions, a thin film of lubricant is formed between the two
moving metal surfaces which may permit a small contact between them. This results in friction
and generation of heat. Thus, welded junction and metal tearing take place. Under the
conditions of high load and extreme pressure, the contact between the metal surfaces increases
and more heat is generated due to increased friction. As a result of this, the liquid lubricant may
decompose or evaporate and thus become ineffective. For effective lubrication under these
conditions, special additives known as extreme pressure additives are used along with the
lubricants. Compounds of chlorine (e.g. chlorinated waxes), sulphur (sulphurized fats), etc. are
used as additives. Under these extreme conditions, these additives undergo a chemical reaction
with the metal surface and thus form a solid surface film of metallic chlorides, sulphides, etc.
Thus, now while moving, instead of metallic surfaces, these additive films come in contact with
each other and thus they protect the metal surfaces.
104
8.3
CLASSIFICATION OF LUBRICANTS
Lubricants may be broadly classified as follows:

1. Liquid lubricants
(a)
(b)
(c)
(d)
Vegetable oils, e.g. palm oil and castor oil

Animal oils, e.g. whale oil and lard oil
Mineral oils, e.g. petroleum fractions
Blended oils or compounded oils, e.g. mineral oils with various additives to induce
desired properties
(e) Synthetic oils or synthetic lubricants, e.g. silicones
2. Solid lubricants
(a)
(b)
(c)
(d)
(e)
Graphite
Molybdenum disulphide
Talc
Mica
Teflon
3. Semisolid lubricants
(a) Greases
(b) Vase lines
4. Emulsions
(a) Oil-in-water type, e.g. cutting emulsions
(b) Water-in-oil type, e.g. cooling liquids
8.4
MINERAL OILS
Mineral oils are obtained from crude petroleum on fractional distillation. They are cheap alIIi
have wide applications.
8.4.1
Extraction of Lubricating Oils (Mineral Oils) from Petroleum
Mineral oils are prepared from the heavy oil which is obtained from fractionation of crude o~
at atmospheric pressure.
The heavy oil is subjected to vacuum distillation and the lubricating oil fraction is co~
lected (Figure 8.3). Since the lubricating oils are of petroleum origin, they are also known III
petroleum oils.
The mineral oils obtained cannot be used as lubricants since they contain a lot of
impurities. The presence of wax is undesirable because it raises the pour point and thus t~
lubricant is unfit for use at low temperatures. Asphaltic, naphthenic and resinous impuriti~
decompose at higher temperatures leading to the deposition of carbon. Easily oxidizable
impurities (oxy and thio derivatives) cause sludge formation during the operating condition. So,
the lubricating oils are refined before being put to use. The impurities are generally removed
by the following methods of refining.
Lubricants
105
Lubricating
oil
Petroleum
-jelly
_
Greases
_
Heavy oil
Crude oil
Paraffin
wax
Diesel
Bubble
tower
L---.Pitch
Vacuum distillation tower
FIGURE 8.3
Extraction of lubricating oil from petroleum.
I. Dewaxing:
The oil is mixed with a suitable solvent (propane, trichloroethylene, etc.)

and then cooled. The wax crystallizes out and is removed by filtration. The solvent
present in the oil is then recovered by distillation.
2. Acid refining: The dewaxed oil still contains a number of undesirable constituents
like naphthenic and asphaltic impurities. For removing these, the dewaxed oil is treated
with conc. sulphuric acid and then agitated. Some of the unwanted impurities dissolve
in acid while others are converted into sludge. The sludge is removed by filtration. The
filtrate is neutralized with a calculated quantity of sodium hydroxide to remove excess
of acid. Finally, the oil is decolourized by passing through fuller's earth.
3. Solvent refining:
In this process, the oil is mixed with phenol in which it is immiscible. But, the solubility of undesirable impurities is more. The mixture is allowed to
stand for sometime. Two layers are formed--oil layer free from impurities containing
some solvent and a solvent layer containing dissolved impurities.
The two layers are continuously separated and the solvent is removed from each portion
by evaporation.
The main objective of refining methods described above is to improve the desirable
characteristics of the lubricating oils by removing the undesirable constituents.
8.4.2 Blended or Compounded Oils or Additives to Lubricants

Certain substances called additives are added to the lubricating oils in order to. further improve
Ihe properties of the refined lubricating oils. They are added in amounts up to about 10 per cent.
The oils thus prepared are known as blended oils or compounded oils.
I. Deposit inhibitors: Deposit inhibitors are detergents such as salts of phenol and
carboxylic acid. The detergents get adsorbed on the deposits and these are kept as a
suspension in the oil. In the presence of detergents, the dirt and other foreign particles
cannot agglomerate into large masses which may block the passage of oil.
106
2. Antioxidants: Oxidation may produce gum like substances which may clog the ou
holes. Antioxidants retard the oxidation of the oil and prevent the formation of gum lie
substances. The antioxidants used are aromatic phenols and amines.
3. Corrosion inhibitors: These additives are adsorbed as a film on iron and steel
surfaces thereby protecting the surface from attack by moisture, e.g. tricresyl phosphate.
4. Foam inhibitors: When the oils, containing detergents, are agitated in the presence
of air, foam is formed. The foaming results in the expulsion of lubricant. In orderla
minimize the foam formation, silicone polymers are added as additives.
5. Pour point depressants: These additives prevent the separation of wax from the
lubricating oil. In the absence of pour point depressants, wax crystals are formed 00
cooling the oil. These wax crystals hinder the flow of oil. Pour point additives suchal
alkyl naphthalenes do not allow the wax crystals to grow.
6. Oiliness: Additives are added to increase the oiliness and film strength of the lubri
cating oil, e.g. fatty acids such as stearic acid and palmitic acid.
7. Viscosity index improvers: These additives prevent the oil from thinning at higher
temperatures and thickening at lower temperatures, e.g. polyisobutylenes.
8. Extreme pressure additives: These additives are added to make lubricating oil to
bear extreme pressures, e.g. chlorinated hydrocarbons.
8.5
SYNTHETIC LUBRICANTS
For operating conditions below -26C and above 121C (e.g. aircraft engines), synthetic
lubricants are used in view of the unsatisfactory performance of other common lubricants.
Important synthetic lubricants are silicones, polyglycol ethers, fluorochloro hydrocarbons, ett.
Methyl or phenyl siloxane polymers are generally called silicones and these are used as
high temperature lubricants. The silicone fluids correspond to a general formula:
where R = CH3 or C6H5 Methyl silicones have low pour points and high viscosity index. They
have the smallest change in viscosity with temperature among the known lubricants.
The superior characteristics of synthetic lubricants are their high thermal stabili~,
oxidation resistance, rust prevention and high viscosity index values. The drawbacks of
synthetic lubricants are their high cost and some of them are toxic and corrosive.
8.6
SOLID LUBRICANTS
Solid lubricants are used in the following cases:

I. Operating conditions are such that a lubricating film cannot be maintained by using
lube oils.
Lubricants
105
.-----_- Uncondensed
~ ~::,
Lubricating
~VKerosene
~~-~ ~--~
~-
Heavy oil
Crude oil
oil
Petroleum
jelly
-Greases
_
Pipe still
Paraffin
wax
Diesel
Bubble
tower
L - - -. .
Pitch
Vacuum distillation tower
FIGURE 8.3
Extraction of lubricating oil from petroleum.
I. Dewaxing: The oil is mixed with a suitable solvent (propane, trichloroethylene, etc.)
and then cooled. The wax crystallizes out and is removed by filtration. The solvent
present in the oil is then recovered by distillation.
2. Acid refining: The dew axed oil still contains a number of undesirable constituents
like naphthenic and asphaltic impurities. For removing these, the dewaxed oil is treated
with conc. sulphuric acid and then agitated. Some of the unwanted impurities dissolve
in acid while others are converted into sludge. The sludge is removed by filtration. The
filtrate is neutralized with a calculated quantity of sodium hydroxide to remove excess
of acid. Finally, the oil is decolourized by passing through fuller's earth.
3. Solvent refining:
In this process, the oil is mixed with phenol in which it is immiscible. But, the solubility of undesirable impurities is more. The mixture is allowed to
stand for sometime. Two layers are formed--oil layer free from impurities containing
some solvent and a solvent layer containing dissolved impurities.
The two layers are continuously separated and the solvent is removed from each portion
by evaporation.
The main objective of refining methods described above is to improve the desirable
characteristics of the lubricating oils by removing the undesirable constituents.
8.4.2 Blended or Compounded Oils or Additives to Lubricants

Certain substances called additives are added to the lubricating oils in order to further improve
the properties of the refined lubricating oils. They are added in amounts up to about 10 per cent.
The oils thus prepared are known as blended oils or compounded oils.
1. Deposit inhibitors: Deposit inhibitors are detergents such as salts of phenol and
carboxylic acid. The detergents get adsorbed on the deposits and these are kept as a
suspension in the oil. In the presence of detergents, the dirt and other foreign particles
cannot agglomerate into large masses which may block the passage of oil.
106
2. Antioxidants: Oxidation may produce gum like substances which may clog the oil
holes. Antioxidants retard the oxidation of the oil and prevent the formation of gum liKe
substances. The antioxidants used are aromatic phenols and amines.
3. Corrosion inhibitors: These additives are adsorbed as a film on iron and steel
surfaces thereby protecting the surface from attack by moisture, e.g. tricresyl phosphate.
4. Foam inhibitors: When the oils, containing detergents, are agitated in the presellCt
of air, foam is formed. The foaming results in the expulsion of lubricant. In order to
minimize the foam formation, silicone polymers are added as additives.
5. Pour point depressants: These additives prevent the separation of wax from ~
lubricating oil. In the absence of pour point depressants, wax crystals are formed 00
cooling the oil. These wax crystals hinder the flow of oil. Pour point additives such as
alkyl naphthalenes do not allow the wax crystals to grow.
6. Oiliness: Additives are added to increase the oiliness and film strength of the lubri
eating oil, e.g. fatty acids such as stearic acid and palmitic acid.
7. Viscosity index improvers: These additives prevent the oil from thinning at higher
temperatures and thickening at lower temperatures, e.g. polyisobutylenes.
8. Extreme pressure additives: These additives are added to make lubricating oil to
bear extreme pressures, e.g. chlorinated hydrocarbons.
8.5
SYNTHETIC LUBRICANTS
For operating conditions below -26C and above 121C (e.g. aircraft engines), synthetic
lubricants are used in view of the unsatisfactory performance of other common lubricant!.
Important synthetic lubricants are silicones, polyglycol ethers, fluorochloro hydrocarbons, etc.
Methyl or phenyl siloxane polymers are generally called silicones and these are used as
high temperature lubricants. The silicone fluids correspond to a general formula:
R SiO
3
.[1--0]
...
I
R
SiR
where R = CH3 or C6Hs. Methyl silicones have low pour points and high viscosity index. They
have the smallest change in viscosity with temperature among the known lubricants.
The superior characteristics of synthetic lubricants are their high thermal stabilitr,
oxidation resistance, rust prevention and high viscosity index values. The drawbacks of
synthetic lubricants are their high cost and some of them are toxic and corrosive.
8.6
SOLID LUBRICANTS
Solid lubricants are used in the following cases:

1. Operating conditions are such that a lubricating film cannot be maintained by using ~
lube oils.
'
Lubricants
107
2. The operating temperature or load is very high.
3. Contamination of lube oil is unacceptable.

The commonly used solid lubricants are graphite, molybdenum disulphide, talc, mica,
teflon, etc. The most widely used solid lubricants are graphite and molybdenum disulphide.
8.6.1 Graphite
In graphite, the carbon atoms form a network of hexagons. The carbon atoms are joined together
by strong covalent bonds. The adjacent layers are held together by the weak van der Waals
forces (Figure 8.4).
Covalent bond
: "'l-,- - - (
I
I
I
I
I
I
I
Weak forces -----.:I
:I
3.41
I
I
FIGURE 8.4
The layer structure of graphite.
When graphite is incorporated as a lubricant between uneven surfaces, it fills into the
valleys on the surface and makes the surface more even. Further, the particles slide easily over
each other as the surfaces of the machinery are in motion. It can be used up to very high
temperatures.
Graphite can be used as a dry powder or as a colloidal dispersion. A dispersion of graphite
in water is called aquadag and that in oil called ai/dag. Oildag is used in internal combustion
engines as it forms a film between the cylinder and the piston rings giving a tight fit to increase
the compression of the air-fuel mixture. Aquadag is useful in air compressors and equipment
used for processing foods.
8.6.2 Molybdenum Disulphide

Molybdenum disulphide has a sandwich like structure in which a layer of molybdenum atoms
lies between two layers of sulphur atoms. The atoms in the layer are held by strong covalent
bonds and the layers are held by the weak van der Waals forces of attraction (Figure 8.5).
108
Sulphur
." /" /." /." /." /." /." /." /"
Molybdenum
/.
~,,~~,,~~~~~~~
.X.X.X.X.X.><X.XX
FIGURE 8.5
The layer structure of molybdenum disuJphide.
It has a very low coefficient of friction. The powder may be sprinkled on the sliding
surfaces to form the film. It is mainly used in heavy machineries working under heavy load ana
high temperatures.
8.7
SEMISOLID LUBRICANTS
The most important semisolid lubricants are greases and vase lines. Greases are employed in
situations where :
(a) Oil cannot be maintained in position due to high load.
(b) Spilling of the oil is undesirable because unlike oils, greases do not spill over the
articles being prepared by the machine. For example, in machines preparing paper,
textile and edible articles.
A grease is a semisolid lubricant obtained by thickening of a lubricating oil by the addition
of a metallic soap. Important functions of a soap in a grease are (a) it acts as a thickener; ~)n
enables the grease to stick to the metal surface firmly and (c) the nature of the soap detennines
the temperature up to which the grease can be used, its consistency, and its ability to stay in
place.
In the manufacture of grease, fatty oil is saponified to get the soap and this is thorough!)
mixed with the lubricant oil. The properties of a grease depend on both the base used fir
saponification and the fatty acids present in the oil.
CH 2 0H
CH 2 COOR
I
CHCOOR + 3MOH
I
CH 2 COOR
--~)
I
I
CHOH+3RCOOM
CH 2 0H
Lubricants
109
The advantages of grease over oil are (a) it withstands high temperature and pressure
under high loads, (b) it stays well at the surfaces and does not contaminate the product and (c) it
requires less attention.
The properties of some of the greases are as follows.
I. Calcium soap greases or cup greases: These are emulsions of petroleum oils with
calcium soaps. They are relatively cheap and resistant to water. They are satisfactory
for use at low temperatures because above 70C the grease separates into oil and soap.
They are suitable for lubricating water pumps, tractors, etc.
2. Sodium soap greases: These are prepared by thickening petroleum oils by sodium
soaps. They can be used up to 175C. As the sodium soaps are soluble in water, these
greases are not suitable for bearings exposed to wet conditions.
B.B EMULSIONS
In various machining operations such as cutting, sawing and drilling, the tool employed gets
heated to a very high temperature particularly at the cutting edge. Due to this overheating, the
tool may lose its temper and hardness. In order to prevent this, efficient cooling and lubrication
have to be provided. This is done by employing emulsions of oil droplet in water which are
called cutting oils or cutting fluids or cutting emulsions. Oil has a poor specific heat but it has
good lubricating properties. On the other hand, water is a poor lubricant but it is an excellent
cooling medium because of its high specific heat and a high heat of vapourisation. Hence, the
combination of the two in the form of an emulsion can provide both lubrication and cooling
effects. The corrosive action of water on the tools, the machines and the workpiece are
objectionable.
Two types of emulsions are used for lubricating jobs.
I. Oil-in-water type emulsions or cutting emulsions: They are prepared by mixing
together an oil containing about 3-20 per cent of a water soluble emulsifying agent and
a suitable quantity of water. The emulsifying agents such as water soluble soaps and
alkyl or aryl sulphonates are used. These types of emulsions are used as coolant cum
lubricant for cutting tools, in diesel motor pistons and large IC engines.
2. Water-in-oil type emulsions or cooling liquids: They are prepared by mixing

together water and oil containing 1-12 per cent of water insoluble emulsifier. The
alkaline earth metal soaps like calcium stearate is used as an emulsifier. These
emulsions have a high viscosity compared to that of oil from which they are prepared.
They are used to lubricate steam cylinders and compressors handling fuel gases.
8.9 PROPERTIES OF LUBRICANTS

Some of the important properties of lubricants, normally tested are (a) viscosity, (b) flash and
fire points, (c) cloud and pour points, (d) aniline point, (e) carbon residue test, (t) neutralization
number, (g) saponification number and (h) Oiliness. These are discussed in detail in the
following sections.
11 0
8.9.1
Viscosity
Viscosity is the most important property of a lubricant oil since it determines the operam.
characteristics of the lubricant. Viscosity is the internal resistance of a fluid during flow. It I
expressed in centipoise or centistoke. The viscosity of an oil is the time in seconds for agiv~
quantity of oil to flow through a standard orifice under the specified set of conditions. 1
viscosity can be measured using Redwood viscometer or Saybolt viscometer. In UK, the liB
required for 50 ml of the liquid to pass through the orifice of a Redwood viscometer is calloo
Redwood seconds. In USA, the time required for 60 ml of the liquid to pass through theorifia
of a Saybolt viscometer is called Saybolt universal seconds.
The viscosity of an oil decreases with increase in temperature as a result of decreasei
intermolecular attraction due to expansion. This variation of viscosity with temperature is ind'r
cated by viscosity-temperature curves (Figure 8.6) or by means of an arbitrary scale knO\\1l1
the viscosity index (VI).
L
Viscosity U
38C
(100F)
Temperature
ggoC
(210F)
FIGURE 8.6 Viscosity-temperature curve.

If the viscosity of an oil decreases rapidly as the temperature is raised, it has a low VI
If it is only slightly affected by increasing the temperature, the oil has a high VI. The
Pennsylvanian oils exhibit a relatively small change in viscosity with a rise in temperature.
are arbitrarily assigned a VI value of 100. Oils of Gulf origin exhibit a larger change in viscos~
with a rise in temperature and are arbitrarily assigned a VI value of O.
The test oil is compared at 38C (lOOF) with a zero VI oil and 100 VI oil both hav~
the same viscosity as the test oil at 99C (210F).
The VI of the test oil is given by the formula
VI= L-U x 100
L-H
where U is the viscosity of the test oil at 38C, L is the viscosity of the low viscosity indexOil
at 38C and H is the viscosity of the high viscosity index oil at 38C.
If the VI is high, the viscosity-temperature curve is flatter than if the index is low. As the luoo.
cants have to function over a wide range of operating temperatures, they should have a high VI.
Lubricants
111
8.9.2 Flash Point and Fire Point

Agood lubricating oil should not volatilise under the working temperatures. If, however, they
volatilise the vapours formed should not catch fire under the conditions of lubrication. A good
lubricant should form inflammable vapours only at a temperature beyond the working
temperature of the machine.
The flash point is the lowest temperature at which the vapours of the oil ignite for a
moment when a small flame is brought near it.
Fire point is the lowest temperature at which the vapours of the oil burn continuously for
at least 5 seconds when a small flame is brought near it. Generally the fire point is 5-40C
higher than the flash point.
Flash and fire points can be determined by Pensky Marten's apparatus (Figure 8.7).
Flame
exposure device
r_-++-- Shutter
~r--r
Stirring device
FIGURE 8.7
Pensky Marten's apparatus.
The oil cup is filled up with the lubricating oil. The oil cup is placed in the air bath and
heated by a burner. By moving the shutter, an opening in the lid is exposed to the flame
carried by flame exposure device. Periodically, a small test flame is applied over the surface
of the oil. The temperature at which a distinct flash is seen is the flash point. The heating of
the oil and the periodical application of the test flame are continued. The temperature at
which the oil vapour catches fire and burns continuously for 5 seconds is taken as the fire
point.
A knowledge of these is helpful to provide safeguards against fire hazards during storage
and use. A good lubricating oil should have flash and fire points higher than the operating
temperature of the machine.
112
8.9.3
When an oil is cooled slowly, the temperature at which it becomes cloudy in appearance ~
called the cloud point. The temperature at which an oil will no longer flow is defined as its JXlII'
point. Normally, the pour point is lower than the cloud point.
Cloud and pour points indicate the suitability of lubricants in cold conditions. LubricB
used in a machine working at low temperature should possess low pour point. Otherwise.
solidification of lubricant will cause jamming of the machine.
Most lubricating oils derived from petroleum contain dissolved paraffin wax and other
solid substances. The cloud point thus represents the temperature at which the dissolveil
substances begin to separate from the oil. As the cooling is continued, the amount of the
separating material increases until an interlocking solid structure is formed and this prevents~
flow of the oil.
The pour point apparatus is shown in Figure 8.8.
[LLLL'LI-"tII---
Flat-bottomed
test tube
_______ ~_t-+:":":":4-0il under test

Air-jacket
.......................: ..... : ........ L...,
-:-.,..,.
. -:""'."""
-:-."-:
..-:-.,..,.
.. -:.:-:1......
..
-Cooling mixture
........................................... : .........: ....: ....................................................: . : . : ..... : ........,..:+ .
FIGURE S.S
Pour point apparatus.
The apparatus consists of a flat-bottomed tube enclosed in an air-jacket. The jacket is

surrounded by ice + calcium chloride freezing mixture contained in a jar. The tube is halffilleil
with oil. Thermometers are introduced into the oil and the cooling bath. As the cooling takes
place via the air-jacket, temperature of the oil falls. The temperature at which cloudiness is firs!
noticed represents the cloud point. The cooling is further continued. The temperature at whicn
the oil does not flow in the test jar for 5 seconds, on tilting it to the horizontal position, B
reported as the pour point.
8.9.4 Aniline Point

The aniline point of an oil is the temperature at which equal volumes of oil and aniline are just
miscible. The aniline point of an oil gives an indication of the deterioration of an oil when d
112
8.9.3
When an oil is cooled slowly, the temperature at which it becomes cloudy in appearance is
called the cloud point. The temperature at which an oil will no longer flow is defined as its pour
point. Normally, the pour point is lower than the cloud point.
Cloud and pour points indicate the suitability of lubricants in cold conditions. Lubricant
used in a machine working at low temperature should possess low pour point. Otherwise,
solidification of lubricant will cause jamming of the machine.
Most lubricating oils derived from petroleum contain dissolved paraffin wax and other
solid substances. The cloud point thus represents the temperature at which the dissolved .
substances begin to separate from the oil. As the cooling is continued, the amount of the
separating material increases until an interlocking solid structure is formed and this prevents the
flow of the oil.
The pour point apparatus is shown in Figure 8.8.
R'ILLliLJ.+--- Flat-bottomed
test tube
................... .
....................
...........
....................
..
. ............ .. ................
......................
.....................
..........
..........
..
.
.....
. . . ............
. . . . . . ..........
. . . ......
. . . . ..
.. ...........
............ ...
.........
.....................
.......
. . . . . . .... .-............
. . . . . . . . . . ..
_______ ...
_ ~_h~'_'_"_-
Oil under test

Air-jacket
. : .. : .....: .....: .. : ........... ':'.. 1...

.._.__._. _._._
._._.._.--l
':':':':':'.:.::'.:.::':':':':':':':'.::':':'.::'.::': ::.:.::.: . ::.:.: . : ... ::: :-4.~.+.................................................

. . . .........................
. . . . . . . . . . . . . . . . . . . . . . . ...................
. . . . . . . . . . . . . . . . . . ..
.....
............................................................................................
FIGURE 8.8
Cooling mixture
Pour point apparatus.
The apparatus consists of a flat-bottomed tube enclosed in an air-jacket. The jacket is

surrounded by ice + calcium chloride freezing mixture contained in a jar. The tube is half-filled
with oil. Thermometers are introduced into the oil and the cooling bath. As the cooling takes
place via the air-jacket, temperature of the oil falls. The temperature at which cloudiness is first
noticed represents the cloud point. The cooling is further continued. The temperature at which
the oil does not flow in the test jar for 5 seconds, on tilting it to the horizontal position, ~
reported as the pour point.
8.9.4 Aniline Point

The aniline point of an oil is the temperature at which equal volumes of oil and aniline are just
miscible. The aniline point of an oil gives an indication of the ciptprioT~tion of an oil when n
Lubricants
113
comes into contact with rubber sealings, packings, etc. Aromatic hydrocarbons have a tendency
to dissolve natural and some synthetic rubbers. A higher aniline point means lower percentage
of aromatic hydrocarbons and hence less solvent effect on rubber sealings, packings, etc. A
higher aniline point is therefore desirable.
8.9.5 Carbon Residue Test

The carbon forming tendency is particularly significant in IC engines. Oils which deposit
minimum amount of carbon are naturally preferable. Excessive build up of carbon deposits in
the combustion chamber leads to detonation.
The determination of carbon residue is carried out in the Ramsbottom apparatus which
consists of an electrically heated small furnace which has got a number of holes at the top to
contain glass bulbs in which the samples of oil are put (Figure 8.9).
Capillary - - - - ,
inlet
Holes to contain bulbs
Electrically _ _-+/
heated furnace
(a)
(b)
FIGURE 8.9 (a) Ramsbottom apparatus, and (b) bulb containing the sample of oil.
The required quantity of the oil is weighed in a special type of thick glass bulb. The inlet
of the bulb consists of a small capillary. The oil is injected into the bulb through the capillary
inlet by means of a syringe. The temperature of the furnace is raised to 500C and then the bulb
containing the oil is placed in one of the holes in the furnace. It is kept there at 500C for
20 minutes. The bulb is then taken out, cooled and then weighed. The quantity of residue in the
bulb gives the carbon residue.
8.9.6 Neutralization Number

The neutralization number is an indication of acidic or basic impurities in the lubricating oil.
Determination of acidity is more common and is expressed in terms of acid value or acid
number.
A known weight of the oil is dissolved in neutral alcohol and titrated against 0.1 N KOH
using phenolphthalein as indicator. The number of milligrams of KOH required to neutralize the
acidic constituents in I gram of the oil is known as neutralization number or acid number of
the oil.
14
'd
b
ml of KOH used x normality x 56
ACl num er =-----------'--weight of the oil taken
In fact, the acid number greater than 0.1 is usually taken as an indication of oxidation of
the oil.
The sources of acidity in the oil may be (a) products of oxidation of oil, (b) contamination
of oil by S02 from combustion of the fuel, and (c) additives used in improving properties of
the oil.
8.9.7 Saponification Number

Saponification is the alkaline hydrolysis of ester to give alcohol and sodium or potassium salt
of the acid. The saponification number is defined as the number of milligrams of KOH required
to saponifY the fatty material present in 1 gram of oil. This is usually determined by refluxing
a known quantity of oil with a known excess of potassium hydroxide solution and titrating the
unused alkali against an acid.
Animal and vegetable oils undergo saponification but mineral oils do not. Further, mo~
of the animal and vegetable oils possess their own characteristic saponification values. Hence,
this test gives an indication of the amount of animal and vegetable oils added to mineral oils
to improve oiliness.
8.9.8 Oiliness
The capacity or power of a lubricant to stick onto the surface under conditions of heavy pressure
or load is called oiliness. Lubricants which have high oiliness stay in their position, i.e. in
between the lubricated surfaces and do not come out when they are subjected to a high pressure.
Oiliness is a very important quality of lubricants. A good lubricant should have high
oiliness. Lubricating oils with poor oiliness will be easily squeezed out when the machines work
under heavy load. Mineral oils have poor oiliness. On the other hand, vegetable and animal oils
are having high oiliness. Hence, in order to increase the oiliness of mineral oil, it is mixed with
vegetable or animal oil or fatty acids like oleic acid and stearic acid.
8.10
SELECTION OF LUBRICANTS
1. Lubricants for delicate instruments like clocks, watches, scientific equipment and
sewing machines:
Thin vegetable and animal oils like palm oil and neat foot oil.
2. Lubricants for refrigeration system:

Naphthenic base oils
3. Lubricants for cutting tools:
(a) For heavy cuttings:
Mineral oils containing additives
(b) For light cuttings:
Oil emulsions
Lubricants
115
4. Lubricants for IC engines:

Mineral oils containing additives
S. Lubricants used for machinery running at extreme pressures and low speeds, e.g. tractor
rollers and lathes:
Solid lubricants such as graphite
6. Lubricants for wire ropes:
Greases
7. Lubricants for spindles in textile industry:
Thin oils
Essential requirements or characteristics of a good lubricant are as follows:
1. It should have a high viscosity index.
2. It should have flash and fire points higher than the operating temperature of the
machine.
3. It should have high oiliness.
4. The cloud and pour points of a good lubricant should always be lower than the
operating temperature of the machine.
S. The volatility of the lubricating oil should be low.
6. It should deposit least amount of carbon during use.
7. It should have higher aniline point.
8. It should possess a higher resistance towards oxidation and corrosion.
9. It should have good detergent quality.
I SOLVED EXAMPLES
Example 8.1: An oil of unknown viscosity-index has a Saybolt universal viscosity of

58 seconds at 210F and 580 seconds at 100 c F. The high viscosity index standard (Le.
Pennsylvanian) oil has a Saybolt viscosity of 58 seconds at 210F and 430 seconds at 100F.
The low viscosity index standard (i.e. Gulf oil) has a Saybolt universal viscosity of 58 seconds
at 2JOOF and 780 seconds at lOOF. Calculate the viscosity index of unknown oil.
Solution: We know that viscosity index,

VI= L-U xlOO
L-H
Substituting the values L = 780 seconds, H = 430 seconds and U

equation, we get
VI = 780 - 580 x 100

780- 430
= 57.14
= 580
seconds in this
116
Example 8.2: Calculate the acid value of lubricating oil, 100 g of which required 5 mlof
N/25 KOH solution for complete neutralization.
Solution:
'd
b ( ) al
ml of KOH used x normality x 56
ACl num er or v ue =
weight of the oil taken
1
5x-x56
=0.112
= 25
100
( SHORT QUESTIONS )
1. What is meant by lubricant and lubrication?
2. How are lubricants classified?
3. What are greases? How are they prepared?
4.
5.
6.
7.
How is viscosity index calculated? How is it related to its usage?

What happens when suitable detergents are added to lubricating oil?
Explain the type of lubricants used for IC engines, cutting tools and delicate instruments.
Write a note on cutting fluids.
8. How is aniline point of a lubricant determined?
9. Define oiliness. How is oiliness of mineral oils improved?
10. Distinguish between flash and fire points.
11. Under what operating conditions would you use lubricating oils, greases and solid
lubricants?
12. What are the additives used to improve the following properties of lubricating oils?
(a) Viscosity index
(b) Pour point depressants
(c) Corrosion inhibitors
13. What are the characteristics of a good lubricant?
1. Discuss the various mechanisms of lubrication.
2. How are greases manufactured? Indicate the conditions in which greases are to be used.
3. What are the various types of additives used in lubricating oils and how do they contribure
to the quality of lubricants?
Lubricants
117
4. Write down the importance of solid lubricants and synthetic lubricants. Give examples for
them.
5. What are the various types of lubricating oil? How will you manufacture lubricating oils
from petroleum fractions?
6. What are the various sources of lubricants?
7. Discuss the following properties of lubricants.
(a)
(b)
(c)
(d)
Viscosity index
Carbon residue
Flash point
Pour point
8. Write a note on the structure of graphite and its uses as solid lubricant.
9. Explain any two mechanisms of lubrication.
( PROBLEMS )
1. An oil sample under test has a Saybolt universal viscosity of 64 seconds at 210F and
564 seconds at lOOF. The low viscosity index standard (Gulf oil) possesses a Saybolt
viscosity of 64 seconds at 2lOoF and 774 seconds at lOOF. The high viscosity index
standard (Pennsylvanian oil) gave the Saybolt viscosity values of 64 seconds at 210F and
414 seconds at lOOF. Calculate the viscosity index of the oil sample under test.
(Ans. 58.33)
2. A lubricating oil has Saybolt universal viscosity of 59 seconds at 210F and 564 seconds
at lOOF. The low viscosity index standard Gulf oil has Saybolt universal viscosity of
59 seconds at 210F and 758 seconds at lOOF. The high viscosity index standard
Pennsylvanian oil gave the Saybolt universal viscosity value of 59 seconds at 210F and
420 seconds at 100F. Find the viscosity index of lubricating oil.
(Ans. 57.4)
NANOMATERIALS
9.1
INTRODUCTION
The term nanD comes from a Greek word meaning dwarf. One-billionth of a metre is called a
nanometre. For comparison purposes consider that the width of human hair is approximately
80,000 nanometres. A nanometre-sized particle is smaller than a living cell and can be seen only
with the most powerful microscopes available today. Materials at the nanoscale are typically
between 0.1-100 nanometres in size.
Small things are different and have special properties at the nanoscale. Materials of this
size can display strikingly different physical and chemical properties compared with large
particles of the same material. Scientists are using these unusual properties to create novel
materials and technologies.
For example, tiny clusters of atoms of gold and silver show unique catalytic properties,
while larger pieces of the same material are relatively inert. Silver is popular in jewellery
because it is unreactive, but at the nanoscale, it shows strong antibacterial properties.
Nanoparticles of silver are currently being used in new types of wound dressing.
These properties are largely due to two factors. Smaller particles have a relatively larger
surface area compared with their volume, making them much more chemically reactive. In
addition, on scales below 100 nm quantum effects can change the optical, electronic or magnetic
qualities of materials in unpredictable ways.
Nanochemistry is defined as a field that studies the synthesis, properties and reactivity
of particles and assemblies they form, which measure less than 10 nm at least in one
direction.
118
Nanomateria/s
119
9.2 APPLICATIONS OF NANOMATERIALS

9.2.1 In Medicine
Solid gold nanoparticles have long been used to treat rheumatoid arthritis. Recently it is discovered that gold nanoparticles can be used in the detection and treatment of cancer. Binding gold
nanoparticles to a specific antibody for cancer cells could make cancer detection more easier.
Many cancer cells have a protein known as Epidermal Growth Factor Receptor (EGFR), all over
their surface while healthy cells do not expose the protein as strongly. The gold nanoparticles
can be conjugated to an antibody for EGFR. The conjugated nanoparticle solution is added to
both healthy cells and cancerous cells. It is observed that the whole cancer cell is glowing on
seeing through a microscope. The healthy cells do not bind to the nanoparticles specifically and
are dark. Thus, this technique makes the cancer detection much easier. Exposing the cells to the
correct amount of light would then cause destruction of the cancer cells only and leave the
healthy cells alone.
The gold nanoparticles have 600 per cent greater affinity for cancer cells than for noncancerous cells. The particles that worked the best were 35 nanometres in size.
9.2.2 In Fuel Cells

Fuel cells will be most likely the energy source of the future for vehicles, small electronic
devices, industrial vehicles, laptops, etc. A hydrogen fuel cell takes oxygen and hydrogen and
generates electricity and water. Hydrogen fuel cells could potentially prove to be a great power
source because they do not pollute the air. Nanomaterials are used as catalysts and key components of hydrogen storage systems.
Nanomaterials as catalysts
Catalysts are used with fuels such as hydrogen or methanol to produce hydrogen ions. Platinum,
which is very expensive, is the catalyst typically used in this process. Nanoparticles of platinum
reduce the amount of platinum needed. Using nanoparticles of other materials (palladium, cobalt
and nickel) replace platinum entirely thereby lowering the costs.
Fuel cells contain membranes that allow hydrogen ions to pass through the cell but do not
allow other atoms or ions such as oxygen to pass through. Nanotechnology is used to create
more efficient ultra thin hydrocarbon membranes which will allow them to build lighter weight
and long lasting fuel cells.
Nanomaterials for storing hydrogen
Hydrogen is the fuel mostly used in fuel cell-powered cars. If hydrogen fuel cells are to be
effective in automobiles, hydrogen storage systems should store 6 per cent (by weight) of
hydrogen compared to the weight of the storage tank. Conventionally hydrogen is stored as a
compressed gas or as a liquid. To store enough of hydrogen to power a car, a very large storage
tank is needed. So, it is necessary to develop a light weight and compact solid material that do
the same job of a storage tank. These materials would absorb hydrogen the way a sponge
absorbs water and hold until it is further needed. One such a new material proposed to store
hydrogen is made of carbon nanotubes. They can hold about 8 per cent by weight of hydrogen.
120
9.2.3
In Catalysis
Catalysis is important for the production of chemicals. Generally, catalysts are used to reduce
the amount of energy required during chemical reactions. Using nanotechnology, we can create
more efficient catalysts and save even more energy.
Catalysts have long been used to reduce the amount of energy needed for a reaction. An
example is the use of platinum as a catalyst in the catalytic converter of a car. The platinum
catalyst converts the harmful carbon monoxide and nitric oxide to harmless carbon dioxide and
nitrogen. When nitric oxide lands on platinum catalyst, the nitrogen atoms and the oxygen atoms
bond to the platinum breaking up the nitric oxide molecule. The nitrogen atoms then bond with
other nitrogen atoms and are released as nitrogen gas. The oxygen atoms combine with carbon
monoxide and carbon dioxide is released as a gas. The platinum surface is available for the
adsorption of other nitric oxide molecules and the process continues. Only less amount of
energy is used for this chemical reaction to occur. The process is also economical as the catalyst
can be reused.
A catalyst with a large surface area can be more advantageous because it interacts with
more molecules at the same time. Using nanoparticles or nanocrystals to form catalysts provide
a large surface area thus improving the performance of existing catalysts. Nanocatalysts (size
varies between 1-20 om) can also offer improved purity and size uniformity compared to
previously available catalysts. Thus the effectiveness of the catalysts can be improved at a
relatively low cost.
9.3
CARBON NANOTUBES
Carbon in the solid phase can exist in different allotropic forms: graphite, diamond,
Buckminster fullerene and nanotubes.
Diamond has a crystalline structure where each sp'3 hybridized carbon atom is bonded to
four others in a tetrahedral arrangement. Graphite is made by sp'l hybridized carbon atoms
bonded together in a hexagonal network. Fullerenes consist of spherical molecules with all the
carbon atoms sp'l hybridized.
A single sheet of graphite is called graphene. Carbon nanotubes are often described as a
graphene sheet rolled up into the shape of a cylinder. They were prepared in 1991 by Sumo
Iijima.
Carbon nanotubes are large molecules of pure carbon that are long and thin and shaped
like tubes about 1-3 om in diameter and hundreds to thousands of nanometres long. Nanotubes
are 100 times stronger than steel.
There are two types of nanotubes.
1. Single-walled carbon nanotubes (SWCNT) having a diameter of 1 nm.
2. Multi-walled carbon nanotubes (MWCNT) having a diameter of 10 nm.
9.3.1
SynthesiS of Carbon Nanotubes
The general principle of nanotube growth involves producing reactive carbon atoms at a very
high temperature; these atoms then accumulate in regular pattern on the surface of metal par
ticles resulting in a long chain of assembled carbon atoms.
Nanomateria/s
121
Laser evaporation is one of the methods used for the production of nanotubes. In this
method, graphite is mixed with iron and nickel catalysts and the mixture is heated at a
temperature of 1200C and then the material is irradiated with laser. The yield is about 50-70%.
9.3.2 Properties of Carbon Nanotubes

I. The nanotubes have remarkable strength due to C---C bond.
2. They also have high elasticity. The tubes can recover from severe structural distortion.
3. The density of SWCNT is 0.8 g/cm 3 and that of MWCNT is 1.8 g/cm3. The density of
SWCNT is approximately half that of aluminium making it an extremely light material.
4. Nanotubes are highly resistant to chemical attack and oxidation.
5. The thermal conductivity of nanotubes is two times higher than that of diamond,
whereas electrical conductivity is 100 times higher than that of copper.
9.3.3 Applications of Carbon Nanotubes

1. Due to high electrical conductivity, nanotubes are used in electronic devices such as
field effect transistors.
2. They are used as hydrogen storage systems in fuel cells.
3. By using nanotube filters, it is possible to filter out bacteria and viruses from water.
4. They are used as a composite for batteries and as field emitters for television monitors.
5. They are particularly useful in electronics field to create non-volatile memory.
( SHORT QUESTIONS)
1. Define nanochemistry.
2. What do you mean by nanomaterials ?
3. Give the different allotropic forms of carbon.
( DESCRIPTIVE QUESTION )
1. What are carbon nanotubes ? Explain the synthesis, properties and applications of carbon
nanotubes.
i"I:.:.~l1\lll.\iilllJll
_ __
ELECTROCHEMISTRY
10.1
--_....
,\~
INTRODUCTION
The study of chemical applications of electricity is electrochemistry. Electrochemistry deals

with the chemical reactions produced by passing electric current through an electrolyte or the
production of electric current through chemical reactions.
A material that allows electric current to pass through it is called a conductor. The con
ductors are broadly classified into metallic conductors and electrolytic conductors.
Some important terms related to electrochemistry are as follows:
(a) Metallic conductors or electronic conductors: These are the solid substances
except mercury which conduct electricity without producing chemical changes
in them, e.g. all metals, graphite, etc. In all these only valence electrons carry
current.
(b) Non-conductors or insulators: Materials which do not conduct electricity are
called insulators or non-conductors, e.g. wood, plastics, most of the non-metals, etc.
(c) Electrolytic conductors: In electrolytic conductors current is carried by the
ions of the electrolyte which is present in the liquid or fused state. The decom
position of the electrolyte takes place if direct current is passed, e.g. Hel, NaOH,
etc.
(d) Non-electrolytes: Substances which do not conduct electricity are called non
electrolytes, e.g., pure water, sugar solution, etc.
122
Electrochemistry
123
Table 10.1 shows the differences between metallic conductors and electrolytic conductors.
TABLE 10.1
Differences between metallic conductor and electrolytic conductor
Metallic conductor
Electrolytic conductor
I. It involves the flow of electrons.

2. There is no change in chemical properties
of the conductor.
3. It does not involve any transfer of matter.
1. It involves the flow of ions.

2. It is always accompanied by chemical
changes at electrodes.
3. It involves transfer of electrolyte in the form
of ions.
4. The resistance decreases with increase in
temperature.
5. It can conduct electricity either in molten or
fused state.
4. The resistance of a metallic conductor

increases with increase in temperature
5. It can conduct electricity only in solid
state except mercury
10.2 ELECTROLYSIS
The chemical decomposition of an electrolyte caused by the passage of electricity is called
electrolysis. Consider the electrolysis of an aqueous solution of HCI between two platinum
electrodes (Figure 10.1). It is seen that hydrogen is evolved at the cathode and chlorine is
evolved at the anode.
Hydrochloric
acid solution
------------------------------FIGURE 10.1 Electrolysis.
When HCl is dissolved in water, it dissociates into H+ and CI- ions. On passing electric
current, the W ions will move towards the cathode and the CI- ions will move towards the
anode.
At anode: At the anode, the oxidation of chloride ions takes place to give chlorine.
2CI-
CI2 + 2e-
Thus, the electrode at which the oxidation occurs is called the anode. The electrons lost
to the anode are pumped by the battery to the cathode so that the reduction of H+ ions can take
place at the cathode.
At cathode: Hydrogen ions get reduced at the cathode to give hydrogen.
2H+ +
2e-~
H2
Thus, the electrode at which reduction occurs is called the cathode.
124
10.3
CONDUCTANCE OR CONDUCTIVITY OF ELECTROLYTES
Ohm's law
The resistance of a conductor is directly proportional to its length and inversely proportional
to its cross-sectional area.
t'
Roca
S=R!!..
t'
where
R = resistance in ohms
S = specific resistance
C = length in centimetre
a = area of cross section in cm2
If C = 1 cm and a = 1 cm2, then S = R. Thus, specific resistance is defined as the

resistance of a conductor of unit length and unit cross sectional area. It is expressed in the unit
ohm cm.
Conductance
The conductance of an electrolyte is the reciprocal of its resistance.
C=!
R
It is expressed in the unit ohm-I.
Specific conductance (TCj

The reciprocal of specific resistance is called specific
conductance. Hence, it is the conductance of 1 cm 3 of
a material (Figure 10.2). It is expressed in ohm-I cm- I or
mho cm- I or Siemen cm- I.
Equivalent conductance
(AerJ
Specific conductance is a suitable property for characterizing

metallic conductors. But, it is not suited for electrolytes
because the value depends upon the concentration of the \4--1 cm--.j
solution of the electrolyte. Thus, while measuring the con- FIGURE 10.2 Specific conductance.
ductance of electrolytes in solution, we are using equivalent
conductance instead of specific conductance.
Equivalent conductance is defined as the conducting power of all the ions produced by
dissolving 1 gram equivalent of an electrolyte in a given solution. The equivalent conductance
cannot be determined directly, but it is always calculated from the relation
Electrochemistry
125
= lOOOK
eq
where C is the concentration of the solution in gram equivalent per litre and
conductance. It is expressed in ohm-I cm 2 or S cm2
is the specific
Molar conductance
Molar conductance is defined as the conductance of all the ions present in one mole of the
electrolyte in the solution.
= lOOOK
A
m
where C is the molar concentration. It is expressed in ohm-I cm2 mol-I.
10.3.1 Variation of Conductance with Dilution

The conductance of a solution depends on the number of ions in the solution. When the solution
is diluted, more ions are produced and so the conductance increases on dilution.
Variation of specific conductance with dilution

Specific conductance depends on
I. the number of ions

2. the amount of water present.
As the dilution increases, the conducting power of 1 cc of the solution decreases because
the number of ions per cc decreases.
Variation of equivalent conductance with dilution

Equivalent conductance of an electrolyte increases with increase in dilution. The conducting
power of an electrolyte depends on the number of ions and this increases with increasing
dilution since the degree of ionization of an electrolyte increases with dilution.
So, the equivalent conductance increases with increasing dilution, whereas specific
conductance decreases with increasing dilution. This is illustrated in Table 10.2 in which
specific and equivalent conductances of KCI solution at different concentrations are given.
TABLE 10.2 Specific and equivalent conductances of KCI solution at different concentrations
Concentration
(gm eq/litre)
Specific conductance
(ohm-I em-I)
(ohm- l em2)
1.0
0.1
0.0982
0.0112
98.2
112.0
0.01
0.001223
122.3
126
In Figure 10.3, the equivalent conductances of HCI, NaCI and CH3COOH are plotted
against square root of their concentration.
Ao ............ .
HCI
NaCI
- - - -......- - - - - C H 3COOH
...JCFIGURE 10.3
Variation of equivalent conductance with concentration.
The curves for HCI and NaCI indicate that conductance in these cases are always high
and slightly increase with dilution. HCI and NaCI are strong electrolytes. Strong electrolytes
are substances whose equivalent conductance does not vary appreciably with increase in
dilution. The curves for acetic acid indicates that in concentrated solution the conductivity
is very low and it increases steadily with dilution. CH 3COOH is an example of a weak
electrolyte. Weak electrolytes are substances whose equivalent conductance increases steadily
on dilution.
In strong electrolytes, there is a tendency for equivalent conductance to approach a certain
limiting value when the concentration approaches zero. The value of equivalent conductance at
this point is known as equivalent conductance at zero concentration or at infinite dilution. It may
be denoted by Ao. The relationship between A and concentration is linear for strong electrolytes.
So, Ao can be obtained by extrapolation for strong electrolytes. In the case of weak electrolytes,
the relationship is not linear and Ao cannot be obtained by extrapolation. Table 10J shows the
differences between specific conductance and equivalent conductance.
TABLE 10.3
Differences between specific conductance and equivalent conductance
Specific conductance
l.
It is the conducting power of ions present

in 1 cc of the solution.
2. The number of ions per cc decreases when
l.
2. Degree of ionization increases with increase
dilution increases.
3.
4.
It is the conducting power of ions produced

by dissolving 1 gram equivalent of the
electrolyte.
in dilution.
Specific conductance decreases with

increase in dilution.
3. Equivalent conductance increases with
Specific conductance is not suitable for

electrolytes.
4.
5. Unit: ohm- 1 cm- 1
increase in dilution.
Equivalent conductance is suitable for
electrolytes.
5. Unit: ohm- 1 cm2
Electrochemistry
127
10.4 CONDUCTOMETRIC TITRATIONS

Conductance measurements are employed to determine the end points of various titrations.
Intensely coloured or very dilute acids cannot be titrated using indicators. In such cases, this
technique is helpful. The principle involved is that electrical conductance depends upon the
number and mobility of ions. Of all the ions, H+ ions are the fastest followed by OH- ions. Acids
contain W ions and bases contain OH- ions.
10.4.1 Titration of a Strong Acid with a Strong Base

When a strong acid like HCI is titrated against a strong base (NaOH), the H+ ions are
neutralized by OH- ions. The conductivity goes on decreasing till all the acid is neutralized.
HCI + NaOH
NaCI + H 20
Further addition of alkali will result in introducing fast moving OH- ions. The
conductance will then begin to increase. On plotting the conductance against the volume of
alkali added, the points will lie on two straight lines. The point of intersection x of these two
lines gives the end point (Figure 10.4).
,,
'
End point ~';

~'
"
I'
I',
I
.
I
I
I
Volume of alkali added
FIGURE 10.4 Titration of a strong acid against a strong base.
10.4.2 Titration of a Weak Acid (CH 3COOH) with a Strong Base (NaOH)
The conductance of acetic acid is initially low due to its poor dissociation. On adding sodium
hydroxide, highly ionized sodium acetate is formed and the conductance value increases
steadily.
CH3COOH + NaOH
CH3COONa + H 20
When the acid is completely neutralized, further addition of the base introduces fast
moving hydroxide ions. This causes a sharp rise in conductance value. On plotting the
conductance against the volume of alkali added, the points will lie on two straight lines. The
point of intersection x of these two lines gives the end point (Figure 10.5).
128
Engineering C
':'1111:<
End point
~----.
x
-:; I
,/
I
I
I
I
Volume of alkali added
FIGURE 10.5 Titration of a weak acid against a strong base.
10.4.3 Titration of a Strong Acid (HCI) against a Weak Base (NH40H)

When hydrochloric acid is titrated against ammonium hydroxide, the fast moving W ions are
replaced by the slow moving NH4 + ions and so the conductance value decreases.
HCI + NH40H
NH4CI + H 20
After the neutralization of the acid, further addition of weakly ionized ammonium hydrox
ide will not cause any appreciable change in the conductance value. On plotting the conductance
against the volume ofNH40H, the points will lie on two straight lines. The point of intersection
x of these two lines gives the end point (Figure 10.6).
g
"0
()
End point
---_:/--x, '
I
I
I
"
Volume of NH 4 0H added
FIGURE 10.6 Titration of a strong acid against a weak base.
10.4.4 Titration of a Weak Acid (CH 3COOH) against a Weak Base (NH 40H)
Due to its poor dissociation, the conductance of acetic acid is very low. When it is titraled
against NH40H, the conductance value starts increasing due to the formation of highly ionized :
salt, CH3COONH4.
Electrochemistry
129
After the neutralization of the acid, further addition of NH 40H does not cause any
appreciable change in the conductance value because it is a weak base. On plotting the
conductance against the volume of NH40H, the points will lie on two straight lines. The point
of intersection x of these two lines gives the end point (Figure 10.7) .
.~
>
U
:::l
"0
c:
()
Volume of NH 40H added
FIGURE 10.7 Titration of a weak acid against a weak base.
10.4.5 Titration Involving Precipitation Reaction

The titration of silver nitrate against potassium chloride can be carried out by precipitation
method. The reaction involved may be represented as
Ag+ + N0 3- + K+ + Cl-
K+ + N0 3- + AgCI
From the equation, it is seen that the reaction can be considered as a replacement of CIby N03- having almost the same ionic conductance as CI-. Hence, the conductance remains
practically constant up to the end point. Thereafter, the addition of Ag+N0 3- increases the
number of ions in solution and conductance increases. The curves obtained are shown in
Figure 10.8. The point of intersection x of these two lines gives the end point.
.~
U
:::l
"0
c:
x"
;:''K--"
End point
I
I
I
Volume of silver nitrate added
FIGURE 10.8 Titration of silver nitrate against potassium chloride.
130
10.5
ELECTROCHEMICAL CELLS
The cells used for electrolysis are called electrolytic cells while those used for generation of
electrical energy from chemical reactions are called galvanic or voltaic cells.
Galvanic cells are electrochemical cells in which the energy liberated during a
spontaneous oxidation-reduction reaction accompanied by electron transfer is converted into
electrical energy, e.g. Daniel cell (Figure 10.9).
Zinc electrode
Copper
electrode
Zinc
sulphate
solution
Copper
sulphate
solution
FIGURE 10.9 Daniel cell.
The Daniel cell consists of a zinc electrode dipped in zinc sulphate solution and a copper
electrode dipped in copper sulphate solution. Each electrode is regarded as a half cell. The
standard zinc half cell is coupled with a standard copper half cell by means of a salt bridge. The
resulting cell will have a voltage of 1.1 volt. Since oxidation takes place in the zinc electrode
by the liberation of electrons, it is called negative electrode or anode. Since reduction takes
place in the copper electrode by the acceptance of electrons, it is termed the positive electrode
or cathode. The reactions taking place in the cell are
Zn ~ Zn2+ + 2e- (at anode)
Cu2+ + 2e- ~ Cu (at cathode)
Cu2+ + Zn ~ Zn2+ + Cu (cell reaction)
The electrons released by the oxidation reaction flow through the external wire and are
consumed by copper ions at the cathode.
According to the convention, the electrode at which the electrons are released is written
on the left while that at which the electrons are taken up is written on the right. So, the Daniel
cell is written as
Zn I Zn2+
II
Cu2+ I Cu
The 'I' implies contact between two different phases and the
potential is eliminated by a salt bridge.
'II' indicates that the liquidjunctior
Electrochemistry
131
Salt bridge
The salt bridge bridges the two half cells of the galvanic cell and hence the name. A saturated
solution of KCl or NH 4N0 3 in agar-agar gel can be used as the salt bridge.
The following are the functions of the salt bridge.
1. It prevents the physical contact of the electrolyte solution in half cells.

2. It maintains the internal continuity between the two half cells.
3. It eliminates liquid junction potential.
10.6 THE EMF OF A CELL

Electricity cannot flow from one point to another point unless there is a potential difference
between the two points. Hence, the flow of electricity from one electrode to another electrode
in a galvanic cell indicates that the two electrodes have different potentials. The difference of
potential which causes flow of current from one electrode which is at a higher potential to the
other electrode which is at a lower potential is called the electromotive force.
The emf of a galvanic cell can be calculated using the following relationship.
emf = standard reduction potential of right-hand electrodestandard reduction potential of left-hand electrode
~cell)
~right) - ~left)
0.34 - (-0.76)
+1.1 volt
The positive value indicates that the cell reaction is feasible. If it is negative, the cell reaction
is not feasible.
10.7 ELECTRODE POTENTIAL

The zinc electrode is dipped in ZnS04 solution. It goes into solution as Zn2+ ions. Now, the zinc
electrode attains a negative charge due to the accumulation of electrons on the metal. The
negative charges developed on the electrode attract the positive ions in the solution. Due to this
attraction, the positive ions remain quite close to the metal. In the other case, ions present in
solution deposit over the metal electrode by removing electrons from the electrode. The
electrode becomes deficient of electrons and therefore it attains positive charge, e.g. the copper
electrode in CUS04 solution. Thus, a sort of layer is formed all around the metal. This layer
is called the Helmholtz electrical double layer. A difference of potential is consequently set up
between the metal and the solution. The resultant potential difference between the metal and
the solution is called the electrode potential (Figure 10.10).
Thus the electrode potential of a metal is the measure of tendency of a metal electrode to
lose or gain electrons when it is in contact with its own ions in solution. Consequently the
tendency of an electrode to lose electrons is called the oxidation potential and the tendency of
an electrode to gain electrons is called the reduction potential.
132
--------------
+
+
+
+
+
Zinc electrode
+
+
Helmholtz
+""~r--- electrical
+
+
double layer
-_-_-_-_-_-_ -=-=-=-=-=- ____-_-.. ~ Zinc sulphate

- - - - - .
----- Zn
-----
2+
-
- - - - - - - -
ions -----
+
+ Copper electrode
+
+
+ -::-:-::+ ---------: Copper
sulphate
+ -------:: solution
solution
-----------------
----------------
(a) De-electronation
(b) Electronation
FIGURE 10.10
10.7.1
+
+
+
+
-::-::-: +
-----:_-: +
-----:_-: +
Electrode potential.
Sign of Electrode Potential
The electrode potential is given a positive sign if the electrode reaction involves reduction, and
a negative sign if the electrode reaction involves oxidation. According to the latest convention
of sign, the electrode at which reduction occurs with respect to the Standard Hydrogen
Electrode (SHE) is assigned a reduction potential with a positive sign and the electrode at which
oxidation occurs with respect to the standard hydrogen electrode is assigned a reduction
potential with a negative sign.
10.7.2
Measurement of Single Electrode Potential
It is very difficult to determine the potential of a single electrode. This difficulty is overcome
by fixing the potential of the standard hydrogen electrode whose electrode potential value is
arbitrarily taken as zero at all temperatures. To determine the potential of an electrode, it ~
combined with SHE to form a cell. The emf of the cell is measured and it is equal to the
potential of electrode on the hydrogen scale.
10.8
REFERENCE ELECTRODES
The electrode potential is determined by coupling the electrode with another reference
electrode, the potential of which is known or arbitrarily fixed as zero. The best reference
electrode used is the standard hydrogen electrode. The standard electrode potential of the
standard hydrogen electrode at all temperatures is taken as zero. It is very difficult to set
up a hydrogen electrode. So, other reference electrodes like calomel electrodes are also
used.
10.8.1
Hydrogen Electrode
The hydrogen electrode consists of a rectangular platinum foil that is connected to a platinum
wire and sealed in a glass tube. A jacket which is closed at the top and open at the bottom
Electrochemistry
133
surrounds this glass tube. Hydrogen gas is admitted through a side tube attached to the jacket.
Hydrogen gas at 1 atmospheric pressure is passed into 1M hydrochloric acid in which the foil
of platinized platinum remains immersed (Figure 10.11).
Hel solution
-:-:-:-:-:- :-:-:-:-:
)1'_::;-:-===:-"'=1:===-:::;-:-===:-;::,,:-:===-:+-- Platinum foil
FIGURE 10.11
Hydrogen electrode.
In a cell, when this electrode acts as the anode, the reaction taking place can be
represented as
H2
2H+ + 2e-
Thus, a part of hydrogen gas changes into ions which go into the solution.
When this electrode acts as the cathode, the electrode reaction can be represented as
2H+ + 2e-
H2(g)
Thus, some W ions from solution change into H2 gas.
10.S.2 Calomel Electrode

The calomel electrode is the most commonly used reference electrode. It consists of mercury,
solid mercurous chloride (calomel) and a solution of KCI (Figure 10.12).
Pure mercury is put at the bottom of the tube and is covered with a paste of mercurous
chloride. A solution of KCI is introduced above the paste through the side tube shown on the
right. The KCl solution also fills the side tube ending in a jet on the left. A platinum wire sealed
into a glass tube serves to make electrical contact of the electrode with the circuit. The half
cell whose electrode potential is to be determined is coupled with the calomel electrode
through a salt bridge and the emf of the cell is measured. If the electrode acts as an anode,
the reaction is
134
.,....-,0("')("')" _ _ Platinum
wire
- -"'-l'----- ___
W-
FIGURE 10.12
KCI solution
H9
Calomel electrode.
If it acts as a cathode, the reaction is
10.9
NERNST EQUATION
Consider a reversible cell, e.g. Daniel cell. The overall cell reaction occurring in the cell is
represented by the equation
Zn + Cu2+ :;;::,===> Zn2+ + Cu
In general, for a reversible cell the equation is
A+B:;;:::,==>C+D
The electrical energy of a reversible cell can be measured by the free energy decrease
(-dG) of the reaction taking place in the cell. In the cell, if the reaction involves the transfer
of n number of electrons, then n Faradays of electricity will flow. If E is the pmf "f t~{' cell
then the total electrical energy produced in the cell is
-dG = nFE
where -dG = decrease in free energy.

At standard conditions,
-dcfJ
where -dGo = standard free energy change.
nFEJ
Electrochemistry
135
Standard free energy change is the change in free energy when the concentration of
reactants and products are unity. EJ is the standard emf of the cell in which the reactants and
Jroducts are kept at 1 molar concentration at 25C !1G and !1Go are related as
!1G
!1CO + RT In K
where K is the equilibrium constant of the reaction defined as the ratio of the concentration of
the products to the concentration of the reactants.
!1G = !1Go + RT In [Products]
[Reactants]
-nFE =- nFEo
+ RT In [C][O]
[A][B]
Divide the above equation by -nF

E = EO _ RT In [C][O]
nF
[A][B]
E = EO _ 2.303 RT 10 [C][O]
nF
g [A][B]
At 25C,
T
298 K
8.314 11K/mol
F = 96 500 coulombs
Therefore,
E = EO _ 0.0591
[C][O]
10
n
g [A][B]
This is known as the Nemst equation. This equation may be used to calculate the emf of cells
when concentration of reactants and products of the cell reactions are known.
10.9.1 Calculation of Single Electrode Potential from Nernst Equation

The single electrode potential can also be calculated from the Nemst equation. Consider the
following electrode reaction:
Mn+ +
ne-~
On the basis of the Nemst equation, the electrode potential is
136
E=Eo _ 2.303RT log_l_

nF
[M/+]
where M = 1. Since it is a metal electrode, its concentration is taken as unity.

E
= EO + 2.303 RT log [M/+]

nF
=EO + 0.0591 log [M'I+]
n
Where E is the electrode potential,
is the standard electrode potential and [MIt+] is ~ ,
concentration of metal ions. The standard electrode potential is the potential developed when
all the substances taking part in the reaction are kept at one molar concentration at 25C. The I
electrode potential value (E) will vary depending upon the concentration of metal ions present
in the solution.
eo
10.10
ION SELECTIVE ELECTRODES
In recent years glass membranes have been developed which are selective for a given cation.
just as the conventional glass electrode is selective for hydrogen ions. For example, glass
electrodes are now available commercially for sodium, potassium, lithium and silver ions.
Ion selective electrodes are nearly ideal measurement tools because of their ability to
monitor selectively the activity of certain ions in solution both continuously and non
destructively.
10.10.1
Glass Electrode
The glass electrode (Figure 10.13) consists of a thin-walled

glass bulb made of special type of low melting glass. A
solution of 0.1 molar hydrochloric acid, which furnishes a
constant hydrogen ion concentration is placed inside the
bulb and a Ag/Agel electrode is inserted to make electrical
contact.
The electrode potential of glass electrode is given by
the expression
EG ;"
Eg
O.1M HCI-...w-..r::J
+ 0.0591 log [H+]
= Eg -
Eg
AglAgCI electrode
0.0591pH
The value of
is first obtained by working with
solutions of known pH values. If the glass electrode is
coupled with a calomel electrode, the measured emf is used
for determining the pH values.
Thin walled
glass bulb
FIGURE 10.13 Glass electrode.
Electrochemistry
----------------------------------------------
137
10.11 DETERMINATION OF pH OF A SOLUTION

10.11.1 Determination of pH of a Solution Using Standard Hydrogen Electrode
A hydrogen electrode is introduced into the solution, pH of which is to be determined. It is
coupled with a standard hydrogen electrode through a salt bridge. The cell is represented as
follows:
Pt,H 2(1 atm)
Ecen =
I H+ II
H+(lM)
I H2(l atm)'Pt
Eright - E 1eft
=0 -
( EO + 0.0:91 tog [H+])
1og [H+]
Ec e- l l -0.0591
- --
Ecen
= 0.0591pH
H - Ecell
P - 0.0591
In this way, the pH of the solution can be calculated using a hydrogen electrode.
10.11.2 Determination of pH of a Solution Using Calomel Electrode

The electrode can be coupled with a hydrogen electrode containing solution of unknown pH.
0.0591
= + 0.2422 - ( EO + -n-10g [H+]
=+ 0.2422 -
(0 + 0.0:91 tog [H+])
=+ 0.2422 -
0.0591 10g [H+]
= +0.2422 - 0.0591 log [H+]
Ecen = +0.2422 + 0.0591pH

H_
P -
0.2422
0.0591
Ecell -
In this way, the pH of the solution can be calculated using a calomel electrode;
138
10.11.3
Determination of pH of a Solution Using Glass Electrode
In order to determine the pH of a solution, the glass electrode is placed in the solution unda
test and it is coupled with a calomel electrode. The cell is represented as follows.
AgJAgCI,O.lM HCII Glass(unknown solution) II Hg2Cl 2 1 Hg
Eeell = E right - E 1eft
(Eg - 0.0591 pH)

= + 0.2422 - Eg + 0.0591pH
Eeell - 0.2422 + Eg = 0.0591pH
= +0.2422 -
H_
P -
Eeell -
0.2422 + Eg
0.0591
In this way, the pH of the solution can be calculated using glass electrode.
10.12
CONCENTRATION CELLS
A concentration cell is an electrochemical cell which produces electrical energy by the transfer
of material from a system of higher concentration to a system of lower concentration. The
difference in concentration may be due to the difference in concentration of the electrodes 01
electrolytes. Based on this, concentration cells are divided into two categories.
10.12.1
Electrode Concentration Cells
In electrode concentration cells, two electrodes of the same metal with different concentrations
are dipped in the same solution of the electrolyte, e.g. amalgam concentration cells. Amalgam
electrodes are produced by mixing various proportions of any metal and mercury. Depending
on the amount of metal taken during the preparation of amalgam, the concentration of electrodes
will vary.
10.12.2
Electrolyte Concentration Cells
In types of electrolyte concentration cells, the two electrodes of the same material are dippea
in the solution containing their ions at different concentrations (Figure lO. I 4). The electrode
dipped in the solution of lower concentration is an anode and the electrode dipped in solution
of higher concentration is a cathode. The overall reaction involves the transfer of material from
higher concentration to lower concentration. The two solutions are connected together by a salt
bridge.
At anode (LHE):
The electrode reaction on the left is oxidation.

Ag ----t Ag+(C\) + e-
Electrochemistry
Ag electrode
139
Ag electrode
Salt bridge
':.
'~-';';':'''''''''''''''-.;.;.:.-.;.;.:..:.:..:;'
..
Concentrated
solution
Diluted
solution
:-:-:-:-____-_-_-:-~ql.-_-_-:-:~
----------------
----------------
FIGURE 10.14 Electrolyte concentration cell.
At cathode (RHE):
The electrode reaction on the right is ,reduction.

Ag+(C2) + e-
Ag
The net reaction is

Ag+(C2)
Ag+(C,)
So, there is no net chemical reaction in the cell. The process merely involves the transfer
of one mole of Ag+ ions from a solution of higher concentration to lower concentration.
The electrode potential of the cell is given as follows.
- EO + 2.303RT Iog C,
E,nF
E2 -- EO + 2.303RT Iog C2
nF
EMF = E2 - El
= 2.303 RT log C2
nF
C,
10.12.3 Applications of Concentration Cells

Solubility of sparingly soluble salts
The solubility of a sparingly soluble salt like AgCl can be calculated by measuring the emf of
the cell.
Ag I AgCI,O.OIN KCIII O.OIN AgN0 3 1 Ag
The cell can be constructed very easily by placing one of the silver electrodes in contact
with O.OIN solution of silver nitrate and the other in contact with O.OlN solution of potassium
140
chloride. The two solutions are connected by a salt bridge. A drop of silver nitrate solution ~
added to the potassium chloride solution. The small amount of silver chloride formed u
sufficient to give its saturated solution. The cell so constructed is a concentration cell with
respect to silver ions.
The emf of the above cell is given by the relation
E
= 0.0591 log C2
n
C1
Here n == I and C2 == O.OIN.

Hence,
E == 0.0591 log 0.01
C1
From the above expression, we can calculate the concentration of AgCI in gram equivalent/litre. Multiplying this by 143.5, the equivalent weight of AgCI, we get the solubility of
AgCl in gram/litre.
Determination of the valency of ions in doubtful cases
By substituting the measured value of emf of a concentration cell and the values of C1 anti f.
in the equation
0.05911 C2
E cell = - - - og-
C1
the value of n, the number of electrons involved in the cell reaction or the valency of ions can
be calculated. For example, from the concentration cell the value of n involving mercurous ions
has been found to be 2. Hence, the formula of mercurous ion is Hg22+.
10.13
REVERSIBLE CELLS
The Daniel cell is a good example for a reversible cell. This has a theoretical emf of 1.1 volt
It is considered as a reversible cell because it satisfies the following three conditions:
1. If the cell is connected to an external source of emf equal to 1.1 volt, no current flows
and no chemical reaction takes place in the cell.
2. If the external emf is made slightly less than 1.1 volt, small current flows from the eel!
and small reaction occurs.
3. If the external emf is made slightly higher than 1.1 volt, the current will flow in ilie
opposite direction. Copper will pass into solution as copper ions and zinc will get
deposited on the zinc electrode. In other words, reverse chemical reactions take place
when the current flows in the opposite direction.
Thus, the original conditions are restored by reversing the current. Such a cell is called
a reversible cell.
Electrochemistry
141
10.14 IRREVERSIBLE CELLS

Acell consisting of zinc and copper electrodes dipped in a solution of sulphuric acid is irreversible. The cell reaction is
Zn + H 2S04 ~ ZnS04 + H2
If the applied emf of the external source is slightly greater than that of the cell, copper
goes into solution, hydrogen is liberated at the other electrode and the reaction is
Cu + H 2S04 ~ CUS04 + H2
Such a cell is said to be irreversible because in each case different sets of products are
formed.
10.15 STANDARD CELL

The emf of a standard cell remains constant over long periods of time. It is reproducible and
the change of emf with temperature is also very low, e.g. Weston cadmium cell (Figure 10.15).
Cadmium
r:-:'-:-:-J+-- sulphate
solution
Cadmium
sulphate
crystals
Mercurous
sulphate
Cadmium
sulphate
crystals
Mercury
FIGURE 10.15 Weston cadmium cell.
It consists of a H-shaped glass vessel with the lower end of both the arms closed and
having a sealed platinum wire. One limb contains mercury which serves as the positive
electrode. Mercury is covered with a paste of sparingly soluble mercurous sulphate. The other
limb contains 12.5 'per cent amalgam of cadmium which serves as the negative electrode. Both
the electrodes are covered with some crystals of cadmium sulphate. The remaining part of the
cell is filled with the saturated solution of cadmium sulphate. The emf of the cell is 1.018 volt
at 25C.
When the cell operates, the following reactions occur at two electrodes.
Cd(s) ~ Cd2+ + 2e- (at anode)
Hg2S04 + 2e- ~ 2Hg(l) + S04 2- (at cathode)
142
10.16
MEASUREMENT OF EMF OF A CELL
The emf or the potential difference of a cell can be measured accurately on the basis of
Poggendorffs compensation principle. Here the emf of the cell is just compensated or balan~
by an external emf so that no current flows in the circuit. The potentiometer consists of a
uniform wire AB of high resistance (Figure 10.16). A storage battery is connected to the emls
A and B of the wire through a rheostat. The cell of unknown emf (x) is included in the circuit
by connecting its positive pole to A and the negative pole is connected to a sliding contact
through a galvanometer G. The sliding contact is moved along the wire AB till no current flolll
through the galvanometer. The distance AD is measured. The emf Ex is directly orooortional to
the distance AD:
Ex
oc
AD
Battery
Ar------------------,~--r_------~B
Standard cell
.----0----:
VI
Unknown cell
FIGURE 10.16
Potentiometer for the measurement of emf.
Then the unknown cell is replaced by a standard cell in the circuit. The sliding contact
is again adjusted till there is null deflection in the galvanometer. The distance AD' is measured
Now, the emf of the standard cell Es is directly proportional to the distance AD'.
Es
oc
AD'
Then, the emf of the unknown cell can be calculated from the equation
Emf of the cell x
Emf of the cell S
Potential difference between A and D
= Potential difference between A and D'
Ex
AD
-=-Es AD'
AD
Ex =--xEs
AD'
Knowing the emf of the standard cell (Es), Ex can be calculated.
Electrochemistry
143
10,16,1 Applications of emf Measurements

Determination of standard free energy change and equilibrium constant
rhe standard free energy change of a reaction can be calculated using the following formula.
-/lGJ
nFIfJ
n = number of electrons involved
F = 96500 coulombs
EJ = standard emf of the cell

The relation between the standard free energy change and the equilibrium constant of a
reaction is given by
-/lGJ
nFIfJ
= RT In K
EO
RT In K
= RT In K
nF
EO
= 0.0591 log K
n
Therefore, the measurement of IfJ enables the determination of equilibrium constant for
the cell reaction,
Determination of pH
For the determination of pH, a standard hydrogen electrode is used.

A hydrogen electrode is introduced into the solution, 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
E
= - 2,303RT log [H+]

nF
Since all quantities are known, the hydrogen ion concentration or the pH of the solution can
be calculated.
Solubility of sparingly soluble salts
The solubility of a sparingly soluble salt like AgCI can be calculated by measuring the emf of
the cell.
Ag I AgCl, O.OIN KCl II O.OIN AgN0 3 1Ag
The cell can be constructed very easily by placing one of the silver electrodes in contact
with O,OIN solution of silver nitrate and the other in contact with O.OIN solution of potassium
chloride. The two solutions are connected by a salt bridge, A drop of silver nitrate solution is
added to the potassium chloride solution. The small amount of silver chloride formed is
sufficient to give its saturated solution, The cell so constructed is a concentration cell with
respect to silver ions,
144
The emf of the above cell is given by the relation
Here n = I and C2 = O.OlN. Therefore,

E
= 0.0591 log 0.01

1
C1
From the above expression, we can calculate the concentration of Agel in gram
equivalent/litre. Multiplying this by 143.5, the equivalent weight of Agel, we get the solubil~ ,
of AgCl in gram/litre.
Determination of the valency of ions in doubtful cases
By substituting the measured value of emf of a concentration cell and the values of C, and r,
in the equation.
E
- 0.0591
cell -
C
1og C2
I
the value of n, the number of electrons involved in the cell reaction or the valency of ions can
be calculated, e.g. from the concentration cell the value of n involving mercurous ions has
been found to be 2. Hence, the formula of mercurous ion is Hgi+.
10.17
ELECTROCHEMICAL SERIES
The standard electrode potentials (reduction) of a number of electrodes are given in Table 10.4.
These values are said to be on the hydrogen scale since in these determinations, the potenti~
of the standard hydrogen electrode used as the reference electrode has been taken as zero.
When the various electrodes are arranged in the order of their increasing values of standaro
reduction potentials on the hydrogen scale, then this arrangement is called electrochemical
series.
TABLE 10.4 Standard electrode potentials of some electrodes
Electrode
F!l (volts)
Li+; Li
Mg2+; Mg
Z02+; Zo
Fe2+; Fe
So2+; So
2H+; H2
Cu2+; Cu
Ag+; Ag
-3.05
-2.40
-0.76
-0.44
-0.136
0.00
+0.34
+0.80
+2.87
F2; 2F-
Electrochemistry
145
10.17.1 Applications of Electrochemical Series or Electrode Potentials

The following are the applications of electrochemical series:
I. The standard emf of a cell can be calculated if the standard electrode potential values are
known.
E1:ell =
ElRHE - ElLHE
2. The relative tendencies of metals to go into solution can be noted by the help of
electrochemical series. Metals on the top are more easily ionized into solution.
3. The metal with negative reduction potential will displace hydrogen from an acid solution:
Zn + H2S04 ~ ZnS04 + H2
ElZn
-0.76 volt
The metal with positive reduction potential will not displace hydrogen from an acid
solution.
ElAg = +0.80 volt
Ag + H2S04 ~ no reaction
4. Metals which lie higher in the series can displace from the solution those elements which
lie below them in the series. Thus, zinc can displace copper from the solution.
5. The anodic or more active metals in the series are more prone to corrosion. The cathodic
or more noble metals are less prone to corrosion.
10.18 GALVANIC SERIES

The galvanic series is used to provide sufficient information in predicting the corrosion
behaviour in a particular set of environmental conditions. Oxidation potential measurements of
various metals and alloys have been made using the standard calomel electrode as the reference
electrode and immersing the metals and alloys in sea water. These are arranged in decreasing
order of activity and this series is known as the galvanic series (see Table 10.5).
TABLE 10.5 Galvanic series
Magnesium
Magnesium alloys
Zinc
Aluminium
Aluminium alloys
Copper
Bronze
Copper Nickel alloys
Gold
Platinum
The galvanic series gives more practical information on the relative corrosion tendencies
of the metals and alloys. The speed and severity of corrosion depends upon the difference in
potential between the anodic and cathodic metals in contact.
146
10.19
POTENTIOMETRIC TITRATIONS
Potentiometric titrations are one of the important applications of the emf measurements. In these
titrations the end point is detected by measuring the potential of a suitable electrode, which ~
called indicator electrode. The potential of such an electrode depends on the concentrationoi
a particular ion present in the solution. When the concentration of the ions in the solution
changes, the electrode potential will change. During the titration the potential will change
slowly at first and then sharply near the equivalence point. The exact equivalence points are
determined graphically and this method is more advantageous for the titrations involvini
coloured solutions. Some examples for potentiometric titrations are given as follows:
10.19.1
Potentiometric Estimation of Ferrous Ion
A ferrous ion present in an unknown solution is determined by a redox titration with a standard
potassium dichromate solution potentiometrically. A known volume of Fe2+ ion solution is taken
and little amount of phosphoric acid is added. A platinum electrode is immersed in the solution.
Now it acts as the indicator electrode and is coupled with a saturated calomel electrode. The
emf of the cell is measured.
The emf of the indicator electrode depends on the relative concentration of Fe 2+ ions and
3
Fe + ions present in the solution. During the titration, standard potassium dichromate is added
to the indicator electrode in portions and Fe2+ ions get oxidized to Fe3+ ions gradually.
3Fe2+ + cr6+ ~ 3Fe3+ + Cr3+
Hence the potential of the electrode will increase slowly. At the equivalence poin~ there
will be steep increase in the potential. This is because, now the indicator electrode is formed
with respect to concentration of Cr3+/cr6+ ions. Beyond the equivalence point, the excess
addition of potassium dichromate will increase the potential slowly. The end point is determined
from a graph obtained by plotting the volume of potassium dichromate added against emf
(Figure 10.17). The end point is the point of inflexion, i.e. the point where the slope of the Curvl
is maximum.
End point
/
Volume of K2 Cr20 7 added (ml)
FIGURE 10.17
Potentiometric estimation of ferrous ion.
Electrochemistry
147
10.19.2 Potentiometric Estimation of Silver Ion

Asilver ion present in an unknown solution is determined by a precipitation titration with
standard sodium chloride solution potentiometrically. A known volume of Ag+ ion solution is
taken and a silver wire is immersed in the solution. Now it acts as the indicator electrode and
its potential depends on the concentration of silver ions present in the solution. The indicator
electrode is coupled with a saturated calomel electrode and the emf of the cell is measured.
During the titration, standard sodium chloride is added to the indicator electrode in portions and
Af ions are getting precipitated as silver chloride.
Ag+ + Cl- ~ AgCl
.!
Therefore the concentration of Ag+ ions present in the solution decreases and hence the
potential will decrease gradually. At the equivalence point, there will be steep decrease in the
potential. It is because, the silver ions are completely precipitated. The formed silver chloride
precipitate is a sparingly soluble salt and it dissolves a little to produce negligible concentration
of silver ions. Beyond the equivalence point, the excess addition of sodium chloride will not
have much variation in potential.
The end point is determined from a graph obtained by plotting the volume of sodium
chloride added against emf (Figure 10.18). The end point is inflexion, i.e. the point where the
slope of the curve is maximum.
Volume of NaCI added (ml)
FIGURE 10.18
Potentiometric estimation of silver ion.
SOLVED EXAMPLES
Example 10.1: Calculate the standard emf of the cell:
Zn I ZnS04 " CUS04 I Cu
Standard reduction potentials are EO(Zn2+/Zn) = -0.763 volt and Eo(Cu 2+/Cu) = +().337 volt.
148
Solution:
Emf = Standard reduction potential of right-hand electrode Standard reduction potential of left-hand electrode
Egell
= E~ght -
Efeft
= 0.337 - (-0.763)
= 0.337
+ 0.763
= 1.1 volt
Example 10.2: What is the potential of a lead electrode that is in contact with a solution of
0.015M in Pb2+ ions. The standard electrode potential (EJ) for Pb ~ Pb2+ + 2e- is equal to
0.13 volt.
Solution:
The standard reduction potential (EJ) for Pb2+ + 2e- ~ Pb is -0.13 volt.
E = EO + 2.303 RT log [Pb 2+]

nF
E
=EO + 0.0591 log [Pb 2+]

n
= - 0.13 + 0.0591 log (0.015)

2
= -0.13
+ 0.02955 (-1.824)
= -0.13 - 0.0539
= -0.184 volt.
Hence the corresponding value of oxidation potential is 0.184 volt.

Example 10.3:
Calculate the emf of the following cell:

Zn I Zn2+
O.lM
II
Cu2+ I Cu
O.5M
Standard reduction potentials of Zn and Cu are -0.76 and 0.34 V respectively.
Solution:
E
= EO
(right) -
EO(left)
= 0.34 - (-0.76)
= +1.1
Zn ~ Zn 2+ + 2eCu2+
+ 2e- ~ Cu
Cu2+ + Zn ~ Zn2+ + Cu
(anode)
(cathode)
(Cell reaction)
Electrochemistry
149
E = EO _ 0.0591 log [Products]

n
[Reactants]
2
E = EO _ 0.0591 log [Zn +]

n
[Cu 2+]
E = 1.1- 0.0591 log ~
2
0.5
E = l.l + 0.0207
=
l.l207 V
Example 10.4: Calculate the emf of a concentration celI at 25C consisting of two zinc
electrodes immersed in solution of zinc ions of 0.1 molar and 0.01 molar concentrations.
Solution:
- 0.0591
C
1og C2
1
n
cell -
Zn2+ + 2e- ~ Zn
Number of electrons involved, n = 2
Higher concentration, C2 = O.IM
Lower concentration, C 1 = O.OIM
E
- 0.0591
~
2 10g 0.01
cell -
= 0.0591
=
1og 10
2
0.02955 V
Example 10.5: Calculate the emf of the Zn-Ag celI at 25C when [Zn 2+] = O.1M and [Ag+]
= 1M.
(II = 1.56 volt at
25C.
Solution:
E = EO _ 0.0591
[Products]
10g
n
[Reactants]
Zn ~ Zn2+ + 2e2Ag+ + 2e-
2Ag
(anode)
(cathode)
Zn + 2Ag+ ~ Zn2+ + 2Ag

2
E = EO _ 0.0591
[Zn +]
10g
n
[Ag+f
(celI reaction)
150
~----~-----------------------------
E=1.56- 0.0591 10 [0.1]

2
g [1]2
=
1.56 + 0.02955
= 1.59 V
Example 10.6: Calculate the emf of a concentration cell at 25C consisting of zinc electrodes.
one immersed in a solution of 0.02M and the other immersed in a solution of O.OOIM solution
of its own ions at 25C.
Solution:
- 0.0591
cell -
Zn2+ + 2e-
C
1og C2
Zn

Higher concentration, C2 = 0.02M
Lower concentration, C, = O.OOIM
_ 0.0591
0.02
10
2
g 0.001
cell -
0.0384 V
Example 10.7: Two copper rods are dipped in copper sulphate solutions of concentrations
O.IM and 0.25M. Formulate the cell and calculate its emf at 25C.
Solution:
Cu I Cu2+
II
O.lM
Cu2+
- 0.0591
E cell
I Cu
O.25M
C
1og C2

Higher concentration, C2 = 0.25M
Lower concentration, C, = O.1M
= 0.0591 log 0.25
0.1
= 0.0118 volt
Example 10.8: The emf of the cell Ag I AgCI (saturated)

to be 0.1182 V. Find out the solubility of AgCl.
Solution:
E
- 0.0591
C
1og C2
n
1
cell -
II AgN03 (O.OOOIM) I Ag is found
Electrochemistry
Emf of the cell, E = 0.1182 V

Number of electrons involved, n = I
Higher concentration, C2 = O.OOOIM
Lower concentration, C 1 = ?
0.1182 = 0.0591 log 0.0001
1
C1
log 0.0001 = 0.1182 = 2
C1
0.0591
'1
f2
0.0001
--=antlogo
C1
0.0001 = 100
C,
C _ 0.0001
1 100
=1
Therefore, solubility of AgCI is I
IO--6M
10--6 M.
Example 10.9: Calculate the concentration of H+ in the following cell:
Pt, H2(p ~ 1 atm) I H\c = 10--6 M) II H+(C =
?)
Pt, H2(p =
Solution:
0.118 = 0.0591 10 ~
1
g 10--6
10 ~ = 0.118 = 1.997
g 10--6 0.0591
C~
10
= Antilog of 1.997
~=99.31
10-6
C2 = 99.31 x 10-6
= 9.931 x 10-5 M
1 atm) ; Ecell
= 0.118 V at 25C
151
152
( SHORT QUESTIONS )
1. Define an electrolyte.
2. Specific conductance decreases but equivalent conductance increases on dilution. Why:

3. Define the terms specific conductance and equivalent conductance. What are their uni~1
4. The oxidation potential of a metal is -0.34 V. Will it displace hydrogen from acids? Whf
5. Define electrode potential. How is it related to concentration of the solution?
6. What are electrolytes? How are they classified?
7. Distinguish between specific conductance and equivalent conductance.
S. Define cell constant. Indicate its unit.
9. Classify the following as electronic conductor, electrolytic conductor and insulator:
(a)
(b)
(c)
(d)
Solid NaCI
Rubber
Copper
Molten cryolite
10. Explain the chemical changes that occur at the two electrodes in a Daniel cell. Write the
cell reaction.
11. Describe the construction and working of a Daniel cell.
12. Can we use a nickel spatula to stir a solution of copper sulphate? Given that:
ENi 2+/Ni = +0.025 V and JfJ Cu2+/Cu = +0.34 V
13. Define single electrode potential.
14. Define a reference electrode. Give one example.

15. Define (a) electrode potential and (b) electrochemical cell.
16. What are reversible and irreversible cells?
17. How does a galvanic cell differ from an electrolytic cell?
1. Derive the Nemst equation. Explain how it is used to calculate the emf of a cell.
2. Draw a neat sketch of a calomel electrode and label its parts. Write the electrode reactions.
3. What is a galvanic cell? How does it function? Illustrate with an example.
4. What is electrochemical series? Discuss its applications.
5. How is standard electrode potential determined? What are the significances of electrochemical series?
6. Write down any three applications of measurements of electrode potential.
Electrochemistry
153
7. What is a standard cell? Describe the construction of a Weston cadmium cell.

8. How will you determine the specific conductivity and equivalent conductivity of an
electrolyte? What are the importance of conductivity measurements?
9. What are concentration cells? How would you determine the emf of a concentration cell?
10. Write down any four applications of emf measurements.
II. Describe the construction and working of a calomel electrode and a hydrogen electrode.
12. Define electromotive force. How is it measured by potentiometric method?

13. Describe the following electrodes giving the diagram, electrode notation and electrode
reaction: standard hydrogen electrode and calomel electrode.
14. Discuss the construction and limitations of glass and calomel electrodes.
15. Describe the potentiometric method of determining the emf of a cell.

16. How is a calomel electrode constructed? Discuss how this electrode may be used for the
detennination of pH of a solution.
17. What are the four valuable informations which can be obtained from electromotive series?
18. How will you estimate the concentration of silver ion in a solution by potentiometric
titration?
( PROBLEMS )
1. Calculate the single electrode potential of zinc on O.OIM ZnS04 solution at 25C.
tJ(Zn/Zn2+) = + 0.76 V.
(Ans. -0.819 V)
2. Calculate the electromotive force of the cell Zn I Zn2+ II Ag+ I Ag when [Zn2+] = 0.10M
and (Ag+]
= 10M.
E~ll at 25C
1.56 V.
(Ans. 1.6487 V)
3. Calculate the emf of the following cell:

(i) Zn I ZnS04 (O.IM)
Given that
II
CdS04 (O.OIM)
EJ(ZnJZn 2+) =
I Cd
+0.76 V, D(CdJCd 2+) == +0.4 V
(Ans. 0.33 V)
(ii) Mg I Mg2+ (O.2M)
II Ag+
(0.15M) lAg
Given that EJ(Mg2+/Mg) == -2.37 V, D(Ag+/Ag) == +0.8 V
(Ans. 3.142 V)
(iii) Zn I 2n2+ (O.OIM)
Given that
II
Ni 2+ (0.5M)
EJ(ZnJZn2+)
I Ni
== +0.76 V, D(NiINj2+) == +0.25 V
(Ans. 0.56 V)
154
4. Calculate the emf of the cell at 25C Zn I Zn2+(aq) II Ag+(aq) I Ag when [Zn2+] =O.lM;
[Ag+] = O.IM. The standard oxidation potential of Zn/Zn2+ = +0.76 V and AgJAg+:
-0.8 V.
(Ans. 1.53 V)
5. Using the standard reduction potentials given below
Zn2+ + 2e- ~ Zn(s) JfJ = -0.76 V
Cd2+ + 2e- ~ Cd(s) JfJ = -0.44 V
calculate the emf of the galvanic cell
Zn I ZnS04 (1M)
II
CdS04 (1M)
I Cd
(Ans. 0.32 V)
6. Calculate the potential developed when a zinc rod is kept immersed in Zn(N03h solution
of strength 0.5M at 25C. JfJ(ZnlZn2+) = +0.76 V.
(Ans. -0.7688 V)
7. Calculate the electrode potential of copper electrode which is in contact with a solution
of 0.00004M Cu2+ ions at 298 K. The standard oxidation potential of copper is -0.34 V.
(Ans. 0.21 V)
8. Calculate the standard emf of the cell Mg I Mg2+ II Zn2+ I Zn. The standard reduction
potentials of zinc and magnesium are -0.76 V and -2.37 V respectively.
(Ans. 1.61 V)
9. Calculate the emf of a Daniel cell at 25C when the concentration of zinc sulphate and
copper sulphate are O.OOIM and O.IM respectively. The standard emf of the cell is 1.1 V.
(Ans. 1.1591 V)
10. The emf of the cell Ag I AgCl(aq)(saturated) II AgN0 3(0.000IM) I Ag at 298 K is found
to be 0.1182 V. Find out the solubility of AgCl from the emf of the cell.
(1 x 10--{) gram equivalentllitre)
11. Calculate the emf of the following cell at 25C.
Zn(s) I Zn2+(0.IM) II Cu2+(1.75M) I Cu(s).
Given that JfJ(Zn2+/Zn) = -0.76 V and JfJ(Cu2+/Cu) = +0.34 V.
(Ans. 1.137 V)
12. Calculate the emf of a Daniel cell at 25C, when the concentration of ZnS04 and CuSO.
are 0.001 M and 0.1 M respectively. The standard emf of the cell is 1.1 volt.
(Ans. 1.159 V)
2
13. Calculate the emf of the cell Zn I Zn + (O.IM) II Ag+ (10.0M) I Ag. Write down the cell
reaction. Given that JfJ(Zn2+/Zn) == -0.76 V and JfJ(Ag+/Ag) = +0.80 V.
(Ans. 1.649 V)
CORROSION AND CORROSION CONTROL
11.1 INTRODUCTION
Metals and alloys are used as construction and fabrication materials in engineering. If the metal
or alloy structure is not properly maintained, they deteriorate slowly by the action of
atmospheric gases, moisture and other chemicals. This phenomenon of metals and alloys to
undergo destruction by the act of environment is known as corrosion.
Corrosion is defined as the gradual eating away or deterioration of a metal by chemical
or electrochemical reactions with its environment.
Due to corrosion the useful properties of a metal such as malleability, ductility and
electrical conductivity are lost. The most familiar example of corrosion is rusting of iron when
exposed to atmospheric conditions. During this, a layer of reddish scale and powder of
oxide (Fe304) is formed and the iron becomes weak. Another example is the formation of
green film or basic carbonate [CuC03 + CU(OH)2] on the surface of copper when exposed
to moist air containing CO 2,
It has been roughly assessed that the amount of iron wasted due to corrosion is onefourth of world production. The direct loss due to corrosion in India amounts to Rs. 200 crore/
annum while the money spent annually in controlling corrosion is of the order of Rs. 50 crore.
It is better to control rather than to prevent corrosion, since it is impossible to eliminate
corrosion.
11.1.1 Cause of Corrosion

In nature, most metals are found in a chemically combined state known as an ore. All the metals
except gold, platinum and silver exist in nature in the form of their oxides, carbonates,
sulphides, sulphates, etc. These combined forms of the metals represent their thermodynamically stable state (low energy state). The metals are extracted from these ores after
supplying a large amount of energy. Metals in the uncombined condition have a higher energy
and are in an unstable state. It is their natural tendency to go back to the low energy state, i.e.
155
156
combined state by recombining with the elements present in the environment. This is the main
reason for corrosion.
Effects of corrosion
The following are the effects of corrosion:

1.
2.
3.
4.
5.
11.2
11.2.1
Lost production during a shut down

Replacement of corroded equipment
High maintenance costs such as repainting
Loss of efficiency
Contamination of the product
THEORIES OF CORROSION
Direct Chemical Attack or Chemical or Dry Corrosion
Whenever corrosion takes place by direct chemical attack by gases like' oxygen, nitrogen and
halogens, a solid film of the corrosion product is formed on the surface of the metal which
protects the metal from further corrosion. If a soluble or volatile corrosion product is fonned,
then the metal is exposed to further attack. For example, chlorine and iodine attack silver
generating a protective film of silver halide on the surface. On the other hand, stannic chloride
formed on tin is volatile and so corrosion is not prevented.
Oxidation corrosion is brought about by direct action of oxygen at low or high
temperatures on metals in the absence of moisture. Alkali metals (Li, Na, K, etc.) and alkaline
earth metals (Mg, Ca, Sn, etc.) are readily oxidized at low temperatures. At high temperatures.
almost all metals except Ag, Au and Pt are oxidized. Alkali and alkaline earth metals on
oxidation produce oxide deposits of smaller volume. This results in the formation of a porous
layer through which oxygen can diffuse to bring about further attack of the metal. On the other
hand, aluminium, tungsten and molybdenum form oxide layers of greater volume than the metal
from which they were produced.
These non-porous, continuous and coherent oxide films prevent the diffusion of oxygen
and hence the rate of further attack decreases with increase in the thickness of the oxide film,
The protective or non-protective nature of the oxide film is determined by a rule known
as the Pilling-Bedworth rule. The ratio of the volume of the oxide formed to the volume of the
metal consumed is called the Pilling-Bedworth rule. According to it, if the volume of the oxide
layer is greater than the volume of the metal, the oxide layer is protective and non-porous. On
the other hand, if the volume of the oxide layer formed is less than the volume of the metal,
the oxide layer is non-protective and porous.
11.2.2
Electrochemical Theory or Wet Corrosion
According to the electrochemical theory, the corrosion of a metal in aqueous solution may be
a two-step process, one involving oxidation and another reduction. It is known that two metals
having different electrode potentials form a galvanic cell when they are immersed in a
conducting solution. The emf of the cell is given by the difference between the electrode
Corrosion and Corrosion Control
157
potentials. When the electrodes are joined by a wire, electrons flow from the anode to the
cathode. The oxidation reaction occurs at the anode, i.e. at the anode the metal atoms lose their
electrons to the environment and pass into the solution in the form of positive ions.
Fe ~ Fe2+ + 2eThus, there is a tendency at the anode to destroy the metal by dissolving it as ions. Hence
corrosion always occurs at anodic areas.
The electrons released at the anode are conducted to the cathode and are responsible for
various cathodic reactions such as electroplating (deposition of metals), hydrogen evolution and
oxygen absorption:
I. Electroplating: The metal ions at the cathode collect the electrons and deposit on the
cathode surface.
Cu2+ + 2e- ~ Cu
2. Liberation of hydrogen:
In an acid solution, (in the absence of oxygen)

hydrogen ions accept electrons and hydrogen gas is formed.
2H+ +
2e-~
H2
In a neutral or alkaline medium, (in the absence of oxygen) hydrogen gas is liberated
with the formation of OH- ions.
2H 20 + 2e-
H2 + 20H-
3. Oxygen absorption: In the presence of dissolved oxygen and in an acid medium,

oxygen absorption reaction takes place.
4H+ + O2 + 4e-
2H20
In the presence of dissolved oxygen and in a neutral or weakly alkaline medium, OHions are formed.
2H20 + O2 + 4e-
40H-
Thus it is clear that the essential requirements of electrochemical corrosion are as

follows:
(a) Formation of anodic and cathodic areas.
(b) Electrical contact between the cathodic and anodic parts to enable the conduction
of electrons.
(c) An electrolyte through which the ions can diffuse or migrate. This is usually provided by moisture.
11.3 DIFFERENTIAL AERATION OR CONCENTRATION CELL CORROSION

Anodic and cathodic areas may be generated even in a perfectly homogeneous and pure metal
due to different amounts of oxygen reaching different parts of the metal which form oxygen
'0ncentration cells. In such circumstances, those areas which are exposed to greater amount of
158
air become cathodic while the areas which are little exposed or not exposed to air become
anodic and suffer corrosion.
Figure 11.1 shows the part of a metal surface covered with dirt which is less accessible
to air than the rest of the metal.
Anode
FIGURE 11.1
Corrosion by differential aeration.
Hence, the area covered with dirt becomes anodic and suffers corrosion.
The anodic reaction is
Fe ~ Fe2+ + 2eThe most common reactions taking place at the cathode are
H20 + Yz0 2 + 2e- ~ 20HFe2+ + 20H- ~ Fe(OH)2
which is further oxidized to Fe(OH)3. Since the anodic area is small and the cathodic area is
large, corrosion is more concentrated at the anode. Thus, a small hole is formed on the surface
of the metal. This type of intense local corrosion is called pitting.
Figure 11.2 shows a wire fence in which the areas where the wires cross are less accessible
to air than the rest of the fence and hence corrosion takes place at the wire crossings which are
anodic.
Cathode
FIGURE 11.2 Corrosion by differential aeration.
In a similar way, iron corrodes under drops of water or salt solution. Areas covered by
droplets, having less access of oxygen become anodic with respect to the other areas which are
freely exposed to air.
159
Differential aeration corrosion occurs when one part of metal is exposed to a different air
concentration from the other part. This causes a difference in potential between differently
aerated areas. It is experimentally found that poor oxygenated parts are anodic. Consequently,
differential aeration of a metal causes a flow of current.
The differences between chemical and electrochemical corrosion are listed in Table 11.1.
TABLE 11.1
Differences between chemical and electrochemical corrosion
Chemical corrosion
Electrochemical corrosion
I. Chemical corrosion occurs in the dry state.
1. Electrochemical corrosion occurs in the presence of moisture or electrolyte.
2. It involves the direct chemical attack by the

environment.
2. It involves the setting up of a huge number of

tiny galvanic cells.
3. It follows adsorption mechanism.
3. It follows mechanism of electrochemical

reactions.
4. Even a homogeneous metal surface will be

corroded.
4. Only heterogeneous metal surface or

homogeneous metal surface with bimetallic
contact is an important condition for this type
of corrosion.
5. Corrosion products accumulate in the same

spot where corrosion occurs.
5. Corrosion occurs at the anode where products

gather at the cathode.
6. Uniform corrosion takes place.
6. Pitting is more frequent especially when the

anode area is small.
11.4 FACTORS INFLUENCING CORROSION

The rate and extent of corrosion depend mainly on (a) the nature of the metal and (b) the nature
of the environment.
11.4.1 Nature of the Metal

I. Position in the galvanic series: The extent of corrosion depends upon the position of
the metal in the galvanic series. Greater the oxidation potential, the greater is the rate of
corrosion. 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 is the
difference, the faster is the corrosion of anodic metal.
2. Relative areas of the anode and cathode: The rate of corrosion is more when the area
of the cathode is larger. When the cathodic area is larger, the demand for electrons will
be more, and this results in increased rate of dissolution of metals at anodic regions.
3. Purity of the metal: The impurities present in a metal creates heterogeneity and thus
galvanic cells are set up with distinct anodic and cathodic areas in the metal. The
higher the percentage of impurity present in a metal, the faster is the rate of corrosion
160
of the anodic metal. For instance, impurities such as Pb and Fe in zinc lead to till
formation of tiny electrochemical cells at the exposed part of the impurity and the
corrosion of zinc around the impurity takes place due to local action. The effect of
even traces of impurities on the rate of corrosion of zinc can be seen from the
following data.
Metal
Percentage of purity
Zinc
Zinc
Zinc
99.999
99.99
99.95
Corrosion rate
2650
5000
It is evident that the corrosion resistance of a metal may be improved by increasing i~

purity.
4. Physical state of the metal: Metal components subjected to unevenly distributed
stresses are easily corroded. Even in a pure metal, the areas under stress tend to be anodic
and suffer corrosion. Caustic embrittlement takes place in stressed parts such as bends,
joints and rivets in boilers.
5. Nature of the oxide film: Metals such as Mg, Ca and Ba form oxides whose volume
is less than the volume of the metal. Hence, the oxide film formed will be porous, through
which oxygen can diffuse and bring about further corrosion. On the other hand, metals
like AI, Cr and Ni form oxides whose volume is greater than that of the metal and the nonporous oxide film so formed will protect the metal from further corrosion.
6. Solubilities of the products of corrosion: Solubility of the corrosion product formed is
an important factor in corrosion. If the corrosion product is soluble in the corroding
medium, the corrosion of the metal will proceed faster. On the other hand, if the corrosion
product is insoluble, then the protective film formed tends to suppress corrosion.
11.4.2
Nature of the Environment
1. Temperature: The rate of chemical reactions and the rate of diffusion of ions increase
with temperature. Hence, corrosion increases with temperature. A passive metal rna)
become active at a higher temperature.
2. Humidity: Atmospheric corrosion of iron is slow in dry air but increases rapidly in the
presence of moisture. This is due to the fact that moisture acts as the solvent for the
oxygen in the air to furnish the electrolyte essential for setting up a corrosion cell. Rusting
of iron increases when the relative humidity of air reaches from 60 to 80%.
3. Effect of pH: The possibility of corrosion with respect to pH of the solution and the
electrode potential of the metal can be correlated with the help of a Pourbaix diagram. The
Pourbaix diagram for iron in water is shown in Figure 11.3.
The diagram shows clearly the zones of corrosion, immunity and passivity. In the diagram
x is a point where pH is 7 and the electrode potential is -0.4 V. It is present in the
corrosion zone. This shows that iron rusts in water under those conditions. This is noticed
to be true in actual practice also.
161
+1.6
Passivation
~ +0.8
1ii
*e
c.
0.0
Ol
"C
uOl
Corrosion
-0.8
[j
Immunity
-1.6
10
pH
FIGURE 11.3
Pourbaix diagram.
From FIgure 11.3, it is seen that the rate of corrosion can be altered by shifting the point
x into immunity or passivity regions. The iron would be immune to corrosion if the
potential is changed to about -0.8 V and this can be achieved by applying external
current. On the other hand, the corrosion rate of iron can also be reduced by moving into
the passivity region by applying positive potential. The diagram clearly indicates that the
corrosion rate can also be reduced by increasing the pH of the solution by the addition
of alkali without disturbing the potential.
4. Nature of the electrolyte: The nature of the electrolyte also influences the rate of
corrosion. If the electrolyte consists of silicate ions, they form insoluble silicates and
prevent further corrosion. On the other hand, if chloride ions are present, they destroy
the protective film and the surface is exposed for further corrosion. If the conductance of
electrolyte is more, the corrosion current is easily conducted and hence the rate of
corrosion is increased.
5. Concentration of oxygen and formation of oxygen concentration cells: The rate of
corrosion increases with increasing supply of oxygen. The region where oxygen
concentration is lesser becomes anodic and suffers corrosion.
Corrosion often takes place under metal washers where oxygen cannot diffuse readily.
Similarly, buried pipelines and cables passing from one type of soil to another suffer
corrosion due to differential aeration, e.g. lead pipeline passing through clay and then
through sand. Lead pipeline passing through clay get corroded because it is less aerated
than sand.
11.5 TYPES OF CORROSION

The following are the different types of corrosion:
I. Galvanic corrosion:
Galvanic corrosion is a type of electrochemical corrosion in which

two different types of metals in contact are jointly exposed to corrosive atmosphere. Here,
162
the metal with more negative electrode potential will become the anode and goes into
solution or corrode, e.g. (a) zinc and copper metals and (b) steel pipe connected to
copper plumbing. This corrosion can be minimized by (a) avoiding galvanic couples and
(b) providing an insulating material between the two metals. ,
2. Erosion corrosion: When a corrosive liquid flows very fast through a metal surface, any
protective oxide film formed on the metal surface is completely removed due to
mechanical abrasion. The underlying metal becomes exposed to the corrosive atmosphere
leading to increased corrosion. This is evidenced by the appearance of grooves and
troughs on the metal surface. The erosion corrosion is frequently observed in bends and
elbows in pipelines.
3. Pitting corrosion: Sometimes corrosion may be concentrated at some places and at
other places it may be less. Thus pits or holes are formed at corrosion-concentrated places.
Let us consider a drop of water resting on a metal surface (Figure 11.4).
Dirt
Cathode
Pit
FIGURE 11.4
Pitting corrosion.
The metal surface which is covered by the drop acts as the anode due to low oxygen
concentration and suffers corrosion. The metal surface which is uncovered acts as the
cathode due to high oxygen concentration.
Fe ~ Fe2+ + 2eAt anode:
At cathode:
H20 + \120 2 + 2e- ~ 20HFe2+ + 20H- ~ Fe(OH)2
[0])
Fe(OH)3
As the anodic area is small compared to the cathodic area, more and more metal is
removed at the same spot. Thus a small hole is formed on the surface of the metal. This
type of intense corrosion is called pitting.
4. Crevice corrosion: If a crevice between different metallic objects, e.g. bolts, nuts and
rivets is in contact with liquids, the crevice becomes an anodic region and suffers
corrosion. This is due to the lack of oxygen in the crevice area. The exposed areas act as
the cathode (Figure 11.5).
FIGURE 11.5
Crevice corrosion.
163
5. Waterline corrosion: Consider an iron pole in stagnant water (Figure 11.6a). The
position near the waterline is well aerated and acts as the cathode. Areas deep inside are
anodic since the oxygen concentration is small. Corrosion takes place in the anodic areas
and reduction of O2 to OH- ions occurs at the cathodic regions. The Fe2+ and OH- ions
interact to give Fe(OHh which is further oxidised by dissolved oxygen to rust.
Cathodic part
/~
---------------"':'
:-:-: :-:-:-:-:-:-:-:-:- -_~"'l_--Anodic

------------------------- .
part getting
corroded
--------------(a)
Water
(b)
FIGURE 11.6 Waterline corrosion.
When water is stagnant in a steel tank for long time, it is observed that corrosion takes
place just below the water level (Figure 11.6b). The concentration of oxygen above the
water surface is greater than that under the surface. This generates an oxygen
concentration cell in which the metal at the water level is cathodic with respect to the
metal below the water level. The metal just below the water level gets corroded. The
area above the water line is completely unaffected by corrosion because it is more
oxygenated.
6. Stress corrosion cracking: Corrosion of metals is also influenced by some physical

differences like internal stresses in the metals. Such differences result during manufacture,
fabrication and heat treatment. Metal components are subjected to unevenly distributed
stresses during their manufacturing process. The electrode potential thus varies from one
point to another. Areas under great stress act as the anode while areas not under stress
act as the cathode.
Various treatment of metals and alloys such as cold working or quenching, bending
and pressing introduce uneven stress and lead to stress corrosion. Corrosion takes
place so as to minimize the stress. Most of the time it ends in breaking of the
components into pieces.
Corrosion of head and point portions of a nail indicates that they have been acting as
anode to the middle portion. Actually the head and the point portions were put under
stress during their manufacture.
In the case of iron-wire hammered at the middle, corrosion takes place at the hammered
part and results in breaking of the wire into two pieces. Caustic embrittlement takes place
in stressed parts such as bends, joints and rivets in boilers.
164
7. Caustic embrittlement:
Caustic embrittlement is the phenomenon during which the

boiler material becomes brittle due to the accumulation of caustic substances.
It is a very dangerous form of stress corrosion occurring in mild steel boiler metals
exposed to alkaline solution at high temperature, resulting in the failure of the metal, '
Stressed parts like bends, joints and rivets are severely affected.
Boiler water usually contains a small proportion of Na2C03' In high pressure boilers, this I
breaks up to give NaOH and makes the boiler water more alkaline.
Na2C03 + H 20
2NaOH + CO 2
This very dilute alkaline boiler water flows into the minute hair cracks and crevices by
capillary action. There the water evaporates and the concentration of caustic soda
increases progressively. The concentrated alkali dissolves iron as sodium ferroate in
crevices, cracks, etc. where the metal is stressed. This causes brittlement of boiler parts
particularly stressed parts like bends, joints and rivets causing even failure of the boiler,
8. Underground or soil corrosion:
The various factors that are responsible for soil cor

rosion are (a) acidity of the soil, (b) moisture content, (c) electrolyte, (d) degree of
aeration and (e) physical properties of the soil.
Soils having low resistivity have high corrosivity. Low resistivity of the soil is due to
the presence of moisture and dissolved electrolyte. These two factors promote corrosion,
Buried pipelines and cables passing from one type of soil to another suffer corrosion due
to differential aeration, e.g. lead pipeline passing through clay and through sand. Lead
pipeline passing through clay gets corroded because it is less aerated than sand.
11.6
CORROSION CONTROL
Corrosion can be controlled by the following ways:
1. By selection of the material:
Selection of the right type of the material is the main

factor for corrosion control. Thus, noble metals are used for surgical instruments ana
ornaments as they are most immune to corrosion.
2. By using pure metals: Pure metals have higher corrosion resistance. Even minute
amount of impurities may lead to severe corrosion, e.g. 0.02% iron in aluminium
decreases its corrosion resistance.
Both corrosion resistance and strength of many metals can be improved ~
alloying, e.g. stainless steels containing chromium produce a coherent oxide film which
protects the steel from further attack.
3. By alloying:
4. By annealing:
Heat treatment like annealing helps to reduce internal stresses and

reduces corrosion.
If two metals have to be in contact, they should be so

selected that their oxidation potentials are as near as possible. Further, the area of the
cathode metal should be smaller than that of the anode, e.g. copper nuts and bolts on large
steel plate. The corrosion can also be reduced by inserting an insulating material between
the two metals.
5. By eliminating galvanic action:
165
6. By proper design: The corrosion of metals depends on the design of the equipment and
structures which are always in contact with any corrosive medium. The design of a
structure should be such that retention of moisture should be as low as possible because
corrosion occurs in the presence of moisture. For example, electrical boxes exposed to
the atmosphere should be so designed that water does not collect at the top. Tanks and
other containers are designed such that the whole of the liquid should be drained off
completely.
On the basis of these general guidelines, some poor and good engineering designs al-':
given in Figure 11.7.
Poor
Better
FIGURE 11.7
Best
Control of corrosion by design.
Erosion corrosion can be avoided by using smooth and curved pipe bends (Figure 11.8).
FIGURE 11.8
Corrosion prevention using curved pipelines.
Riveted joints should be avoided. In that place welded joints are used. Crevice corrosion
and caustic embrittlement can be prevented in this way (Figure 11.9).
c=--____________
FIGURE 11.9
~\~fillLi----------------~
Welding reduces corrosion.
7. By cathodic protection: The principle involved in cathodic protection is to force the

metal behave like a cathode. Since there will not be any anodic area on the metal,
corrosion does not occur. There are two types of cathodic protection.
166
(a) Sacrificial anodic protection.

(b) Impressed current cathodic protection.
(a) Sacrificial anodic protection: In this technique, a more active metal is connectedto ~
the metal structure to be protected so that all the corrosion is concentrated at the more
active metal and thus saving the metal structure from corrosion. This method is used t
for the protection of sea going vessels such as ships and boats. Sheets of zinc ~ I
magnesium are hung around the hull of the ship. Zinc and magnesium being anodic
to iron get corroded. Since they are sacrificed in the process of saving iron (anode) ;
they are called sacrificial anodes. The corroded sacrificial anode is replaced by afresli
one, when consumed completely (Figure 11.10).
Sacrificial zinc
or magnesium
,-++_ _ Insulated
copper wire
FIGURE 11.10
Sacrificial anodic protection.
Important applications of sacrificial anodic protection are as follows:

(i) Protection
from soil corrosion of underground cables and pipelines

(Figure 11.11a).
(ii) Magnesium sheets are inserted into domestic water boilers to prevent the
formation of rust water (Figure 11.11 b).
Earth surface
Mg (sacrificial anode)
Sacrificial
Zn or Mg
Insulated wire
Insulated
copper wire
...
.. ...
..
..
............
-------------
w
FIGURE 11.11
Sacrificial anodic protection (applications).
167
(b) Impressed current cathodic protection: In this method, an impressed current is applied in an opposite direction to nullify the corrosion current and converting the
corroding metal from anode to cathode. This can be accomplished by applying sufficient amount of direct current from a battery to an anode buried in the soil and
connected to the corroding metal structure which is to be protected. The anode is in
a backfill (composed of gypsum) so as to increase the electrical contact with the soil.
Since in this method current from an external source is impressed on the system, this
is called impressed current method (Figure 11.12).
Source of impressed
direct current
Anode
Cathode
+
Earth surface
Graphite
anode
Backfill
Buried pipe made cathode

(protected)
FIGURE 11.12
Impressed current cathodic protection.
This type of protection is given in the case of buried structures such as tanks and
pipelines.
8. By applying protective coating: The surface of engineering material can be protected
from corrosion by covering it by a protective coating. This coating may be of organic or
inorganic material.
9. By modifying the environment: The corrosion rate can be reduced by modifYing the
environment. The environment can be modified by the following:
(a) Deaeration: The presence of increased amounts of oxygen is harmful since it
increases the corrosion rate. Deaeration aims at the removal of dissolved oxygen.
Dissolved oxygen can be removed by deaeration or by adding some chemical
substances like Na2S03'
(b) Dehumidification: In this method, moisture from air is removed by lowering the
relative humidity of surrounding air. This can be achieved by adding silica gel which
can adsorb moisture preferentially on its surface.
(c) Inhibitors: In this method, some chemical substances known as inhibitors are added
to the corrosive environment in small quantities. These inhibitors substantially reduce
the rate of corrosion.
168
(i) Anodic inhibitors: Anodic inhibitors include alkalis, molybdates, phosphates.

chromates, etc. When these inhibitors are added, they react with the ions ofllr
anode and produce insoluble precipitates. The so formed precipitate is adsorl:cQ
on the anode metal forming a protective film thereby reducing corrosion.
(ii) Cathodic inhibitors: In an electrochemical corrosion, the cathodic reactions I!

of two types depending on the environment.
In acidic solution, the cathodic reaction is

2H+ +
2e~~
H2
In acidic solution, the corrosion can be controlled by slowing down the diffusioo
of H+ ions through the cathode. This can be done by adding organic inhibitor!
like amines and pyridine. They adsorb over the cathodic metal surface and act a\
a protective layer.
In neutral solution, the cathodic reaction is
H 20 +
~02
2e~ ~ 20H~
The formation of OH~ ions is only due to the presence of oxygen. Byeliminatill!
the oxygen from the medium, the corrosion rate can be reduced. Oxygen can ~
removed by adding some reducing agents (Na2S03) or by deaeration.
(iii) Vapour phase inhibitors: Vapour phase inhibitors (VPIs) are organic inhibito~
which readily sublime and form a protective layer on the metal surface, e,~
dicyclohexylammoniumnitrite. They are used in the protection of machinery, SI)o
phisticated equipment, etc. which are sent by ships. The condensed inhibitor can
be easily wiped off from the metal surface.
10. By passivation: Passivation is a phenomenon of converting an active surface of a melll
into passive i.e. more corrosion resistant by forming a thin, non-porous and highl)
protective film over the surface.
When the metals like aluminium and tin are exposed to the atmosphere or to the oxidizill!
environment, their surfaces rapidly get converted into oxides. The non-porous nature of
these oxide layers prevent further corrosion. In other words, the metals are passivated.
Similarly, metals which are susceptible to corrosion are made passive by alloying with Ollt
or more metals which are passive or resist corrosion. For example, iron is rendered passive
by alloying it with any of the transition metals such as chromium, nickel an~
molybdenum.
( SHORT QUESTIONS)
1. What is corrosion? How is it classified?
2. Zinc is more readily corroded, when coupled with copper than with lead. Why?
3. Name any three factors that affect chemical corrosion.
4. Explain why corrosion occurs under a rivet.
169
S. Which is more corrosive to metal, hard water or soft water? Why?

6. What happens when metals like gold, aluminium and iron are exposed to moist
atmosphere?
7. How is corrosion prevented by an oxide film?
8. Explain the Pilling-Bedworth rule.
9. Account for the corrosion resistant property of chromium.
10. Bolts and nuts made of the same metal are preferred in practice. Why?
11. Why does corrosion occur in steel pipes connected to copper plumbing?
1. Write a note on the corrosion inhibitors. Explain their functions.
2. Discuss in detail corrosion in dry atmosphere and wet atmosphere.
3. Discuss the electrochemical theory of corrosion of a metal in aqueous solution with special
reference to rusting.
4. Discuss the various factors that affect corrosion.
S. Write a note on waterline corrosion.
6. Write short notes on (a) pitting corrosion and (b) stress corrosion.
7. Discuss the various methods of controlling corrosion.
8. How may buried pipelines be prevented from corrosion?
9. Explain the cathodic protection method of corrosion control.
10. Write notes on (a) corrosion control by proper design and (b) differential aeration.
n.
What is meant by cathodic protection? Explain the two types of cathodic protection and
their applications.
12. Describe how electrochemical properties are used in protecting submerged metals from
being corroded.
13. What are the possible cathodic reactions at the different environment and only the anodic
reaction encounter in the electrochemical corrosion?
PROTECTIVE COATINGS
12.1
INTRODUCTION
Protective coatings are used to protect the metals from corrosion. The main types of protective
coatings are classified as follows.
1. Hot dipping
(a) Galvanizing
(b) Tinning
2. Metal spraying
3. Cladding
4. Cementation
(a) Sherardizing
(b) Chromizing
(c) Calorizing
1. Surface or chemical
conversion coating
(a) Chromate coating
(b) Phosphate coating
(c) Oxide coating
1.
2.
3.
4.
Paints
Varnishes
Lacquers
Enamels
2. Anodizing
5. Electroplating or
electrodeposition
The protective coatings must be chemically inert to the environment and also sufficiently
thick. Besides protection from corrosive conditions, such coatings can also give decorative
appearance to the base metals. To be more effective, these coatings should adhere well to the
surface.
170
Protective Coatings
171
12.2 PRETREATMENT OF THE SURFACE OR PREPARATION OF

MATERIALS FOR COATING
~e outennost su~ace of the base metal (which is to be protected) usually contains impurities
like rust, sca~e, 011. and grease: These substances, if present at the time of coating, will give
por~us and dlscontmuous coatmgs. In order to get a unifonn, smooth and coherent protective
coatmg, these substances are removed by the following methods.
12.2.1 Degreasing
Oil and grease may be removed by cleaning with organic solvents such as chlorofonn, toluene
and acetone. Imm~rsion in hot alkaline solutions is the most commonly used cleaning technique.
For example, sodIUm carbonate and sodium hydroxide are used for this purpose.
12.2.2 Removal of Oxide Scales or Descaling

Removal of the oxide scales and corrosion products (rust) from the surface is called descaling.
In this process, the base metal is dipped inside the acid solution at higher temperatures. The acid
penetrates through cracks and pores of the scales and then their dissolution takes place. Acids
like sulphuric acid, hydrochloric acid and nitric acid are used under dilute conditions.
12.2.3 Mechanical Cleaning

Oxide scales, rust and corrosion products are also removed by abrasion such as grinding, wire
brushing and polishing.
12.2.4 Electrochemical Method

The electrochemical method is used to remove oxide scales which are not removed by other
methods. The base metal is made either anode or cathode with an electrolyte (acid or base). At
the anode the oxide scale is dissolved in the electrolyte and leaves the base metal, whereas at
the cathode the metal oxides are reduced to metal.
12.3 METALLIC COATINGS

Surface coatings made up of metals are known as metallic coatings. These coatings separate the
base metal from the corrosive environment and also function as an effective barrier for the
protection of base metals. Metallic coatings are mostly applied on iron and steel because they
are cheap and commonly used construction materials.
Metallic coatings are usually imparted by the following methods.
12.3.1 Hot Dipping

In the process of hot dipping, the metal to be coated is dipped in the molten bath of the coating
metal and the thickness of the coating is adjusted by squeezing out the excess of the coating
metal with rollers. Such hot dip coatings are generally non-unifonn. The common examples of
hot dip coatings are galvanizing and tinning.
172
1. Galvanizing: The process of coating a layer of zinc on steel is called galvanizing. The
steel article is first pickled with dilute sulphuric acid to remove traces of rust, dust, etc,
at 60-90C for about 15-20 minutes. Then this metal is dipped in a molten zinc bath
maintained at 430C. The surface of the bath is covered with ammonium chloride flux to
prevent oxide formation on the surface of molten zinc. The coated base metal is then
passed through rollers to correct the thickness of the film.
It is used to protect roofing sheets, wires, pipes, tanks, nails, screws, etc.
2. Tinning: The coating of tin on iron is called tin plating or tinning. In tinning, the base
metal is first pickled with dilute sulphuric acid to remove surface impurities. Then it is
passed through molten tin covered with zinc chloride flux. The tin coated article is passed
through a series of rollers immersed in a palm oil bath to remove the excess tin. Tin-coated
utensils are used for storing foodstuffs, pickles, oils, etc.
Galvanizing is preferred to tinning because tin is cathodic to iron, whereas zinc is anodic
to iron. So, if the protective layer of the tin coating has any cracks, iron will corrode. If
the protective layer of the zinc coating has any cracks, iron being cathodic does not get
corroded. The corrosion products fill up the cracks, thus preventing corrosion.
12.3.2 Spraying
In spraying, the molten coat metal is sprayed over the base metal using a spray gun. The metal
thus sprayed adheres to the base metal surface. The coating formed is continuous but porous.
This method is used for applying coatings of copper, lead, nickel, etc. This method can be
applied to finished structures such as bridges, tanks and ships.
12.3.3 Cladding
Cladding is a method by which the surface to be protected is sandwiched between two layers
of the coat metal and pressed between rollers. The clad metals used are aluminium, chromium
and nickel. Copper-clad steel is used in the electrical industry, because this kind of steel has
good electrical conductivity and high strength.
12.3.4 Cementation
In cementation, the base metal is heated with the coating metal in the form of fine powder in
order to promote the diffusion of the coating metal into the base metal. The coatings obtained
are of uniforin thickness.
The base metal is generally steel and the coating metals used are zinc, chromium and
aluminium. When the coating metal is zinc, the process is called sherardizing. When the coating
metal is chromium, the process is called chromizing. When the coating metal is aluminium, the
process is called calorizing.
1. Sherardizing: Cementation with zinc powder is called sherardizing in honour of

Sherard Cowpercoles who developed the process in 1900.
The base metal is heated with zinc dust in a metal drum maintained at a temperature
of 350-370C. The drum is closed tightly and rotated with constant heating for two til
Protective Coatings
173
three hours. During this process zinc gets diffused into iron fonning an alloy of Fe-Zn
on the surface. Sherardized coatings are used for protecting small steel parts such as
nuts and bolts against atmospheric corrosion.
2. Chromizing: The base metal is heated with a powdered mixture of 55 per cent
chromium and 45 per cent alumina at a temperature of 1300-1400C for about
3-4 hours in a closed drum. The purpose of using alumina is to prevent the coalescing
of chromium particles. The outennost surface of the base metal is converted into a
chrome alloy which protects the metal against corrosion. This method is used to protect
gas turbine blades.
3. CaJorizing: Here the base metal is heated with a powdered mixture of aluminium and
alumina in a drum at a temperature of 840-930C for 4-6 hours. Calorized steel is used
for making furnace parts.
12.3.5 Electroplating or Electrodeposition

Electroplating is a process in which metals are deposited or plated on base metals from solutions
containing metallic ions by means of electrolysis. The objectives of electroplating are as
follows:
I.
2.
3.
4.
To
To
To
To
obtain improved resistance to corrosion and chemical attack

get better appearance
get increased hardness
change the surface properties of metals and non-metals
In the electroplating process, the freshly cleaned base metal which is to receive the coat
is made the cathode in a suitable electrolyte bath containing (a) a solution of the salt of the metal
10 be electrodeposited, (b) buffer solution to control the pH, and (c) additional reagents to
enhance conductivity and to aid the fonnation of smooth, dense and coherent coating.
The concentration of the salt solution is maintained by the addition of the metal salt at
regular intervals or by the use of continuously dissolving anode of the metal. The plating is
usually done at a high current density. The nature of the deposit depends upon the current
density, pH and the concentration of the bath. A typical electroplating process is shown in
Figure 12.1.
Anode (material
to be deposited)
Cathode (material
to be electroplated)
------------------------
~
Electrolyte
FIGURE 12.1
Electroplating.
174
The various' types of electroplating are as follows.

1. Chromium plating: For protecting iron, chromium plating is widely adopted. A
warm bath of chromic acid and a high current density (100-200 mA/cm2) are used. The
temperature maintained is about 45-50oC. The anode is lead and the cathode is the base
metal to be plated. Chromium coats give an excellent shining appearance and are stable
because of the formation of an invisible, strongly, adherent protective layer of Cr2~
on exposure. However, chromium coats are porous and contain fine cracks. Hence the
article to be chromium plated is given a copper coating to give protection from
corrosion which is then nickel plated. Chromium is finally placed on the nickel coat.
2. Nickel plating: A bath of nickel sulphate and nickel chloride is used. A pure nickel
sheet is used as anode and the base metal as the cathode.
The operating conditions are as follows:
Current density
: 20-50 mA/cm2
Temperature
: 45-55C
pH
: 4-5
Nickel coats are not quite stable, the highly polished surface detoriorates with age with
the appearance of rust spots.
3. Copper plating: A bath of acidified copper sulphate solution and copper anode are
used. The base metal is used as the cathode.
Current density
: 20-50 mA/cm 2
Temperature
: 30-40oC
Copper plating is used in printed circuit boards. It is coated at the bottom of the
stainless steel cooking utensils to effect better heat transfer.
4. Gold plating: Double cyanide of gold and potassium is used as the electrolytic bath.
A pure gold plate is used as the anode and the base metal as the cathode.
It
Current density
: 1-10 mA/cm2
Temperature
: 60C
pH
: 9-13
is used for high quality decoration and high oxidation-resistant coatings.
Factors affecting electroplating
The following are the factors affecting electroplating:

1. Cleaning of the article is essential for a strong adherent electroplating.
2. Concentration of the electrolyte is a major factor in electroplating.
3. Low concentration of metal ions will produce uniform coherent metal deposition.
4. Thickness of the deposit should be minimized in order to get a strong adherent coatin~
5. Additives such as glue and boric acid should be added to the electrolytic bath to get
a strong adherent and smooth coating.
Protective Coatings
175
6. The electrolyte selected should be highly soluble and should not undergo any chemical
reaction.
7. The pH of the electrolytic bath must be properly maintained to get the deposition
effectively.
Applications of electroplating
The following are the applications of electroplating:
I. Plating for decorative purposes: Gold, silver, copper, nickel, chromium, etc. are the
most widely used metals for decorative plating. The base metals used are steel, zinc,
lead, copper, aluminium alloys, etc.
2. Plating for protection: In order to protect steel from rusting and chemical attack, it
is electroplated. Protective metals applied are zinc, cadmium, tin, etc. To provide both
protection and good appearance, steel is given successive coating layers of copper,
nickel and chromium. Copper and nickel provide protection against rusting and
chemical attack. The chromium plate gives a clean metal appearance. In case of food
containers, tin plating is preferred as it not only protects steel but also does not
contaminate the food.
3. Plating for special surface and engineering effects: Electroplating occupies an

important place in engineering. A composite part can be designed in which the base
metal is an alloy. It possesses the required mechanical properties but has poor resistance
to surface attack under severe conditions. The required surface stability can be provided
by means of electroplating.
12.4 ELECTRO LESS PLATING

In electro less plating, metal ions in solution are reduced to metal atoms and are deposited on
the substrate surface without using electrical energy. [It is a technique of depositing a noble
metal from its salt solution on a catalytically active surface of a less noble metal by employing
asuitable reducing agent without using electrical energy.] The reduction is accomplished by the
presence of a reducing agent. The reducing agent supplies the electrons for the reduction of
metallic ions to metal which gets deposited over the substrate surface giving a uniform thin
coating.
M2+
+ 2e- (from the reducing agent)
~ M (Deposited over substrate surface)
Anumber of metals like nickel, cobalt, copper and some precious metals can be deposited
byelectroless plating. The most popular metal deposited electrolessly is nickel.
12.4.1 Various Steps Involved in Electroless Plating

The various steps involved are as follows:
I. Preparation of active surface of the substrate:

of the following methods.
This is achieved by using anyone
176
(a) Etching: The unwanted particles are removed from the surface by acid treatment
(b) Electroplating: A thin layer of the metal or any other suitable metal is electroplated on the surface.
(c) Treating with stannous chloride followed by dipping in palladium chloride: This
treatment yields a thin layer of palladium on the surface. This method is followed
in the case of plastics and printed circuit boards.
2. Preparation of plating bath:
mainly:
The constituents of the electroless solutions are
(a) Metal salts to provide metal ions for deposition.

(b) Reducing agents like formaldehyde and hypophosphite for reduction of metal ions
into metal atoms.
(c) Complexing agents like EDTA and trisodium citrate to complex metals ions to
prevent bulk decomposition.
(d) A stabilizer like thiourea to prevent the decomposition of plating bath solution.
(e) Accelerators like succinates and fluorides to accelerate the reduction process.
(f) Brighteners like cadmium ions and lead ions to improve the brightness of the
deposit.
12.4.2
Some Electroless Platings
Electroless nickel plating
Electroless nickel plating involves the following steps:
1. Pretreatment of the surface: The preparation of surfaces for electroless nickel

plating depends on the metal on which the deposition is to be done.
(a) Metals such as cobalt, steel and aluminium will be directly nickel plated without
any pretreatment.
(b) Metals like lead, cadmium and tin are to be given a first coating of electrodeposited
nickel prior to electro less nickel coating.
(c) Non-conductors like glass, plastics and ceramics are first activated in a solution of
SnCl2 and HCI followed by dipping in a solution of PdCl 2 and HCI. On drying, a
thin layer of Pd is formed on their surface.
2. Bath composition:
plating:
The following is the bath composition of electro less nickel
Nickel chloride (coating solution)

Sodium hypophosphite (reducing agent)
Sodium acetate (buffer)
Sodium succinate (complexing agent)
pH
Optimum temperature
:
:
:
:
:
:
30 gil
10 gil
50 gil
15 gil
4-6
85-95C
3. Process: The pretreated surface is immersed in the plating bath. The reduction of
nickel ions occurs and the nickel gets deposited over the surface.
Protective Coatings
H2P02- + H 20
Ni2+
H 2P03- + 2H+ + 2e-
+ 2e- ~ Ni
177
(anode)
(cathode)
Properties: The following are the properties of electro less nickel platings:
I. They possess better corrosion resistance than electroplated nickel deposits.
2. They give rise to harder surface with better wear resistance.
3. The coating is solderable and weldable.
Applications: The applications of the electroless nickel platings are as follows:

1. They are used in the electronic industry for fabricating printed circuits, diodes, etc.
2. They are used to prevent galling of aluminium, titanium and stainless steels.
Electroless copper plating
The process involves the following steps:
I. Pretreatment of the surface: The preparation of surfaces for electroless copper

plating depends on the metal on which the deposition is to be done.
(a) Metals like Fe, Co and Ni can directly be copper plated without any pretreatment.
(b) Non-conductors like glass, plastics and ceramics are first activated in a solution of
SnCl2 and HCl followed by dipping in a solution of PdCl 2 and HC!. On drying, a
thin layer of Pd is formed on their surface.
2. Bath composition:
plating:
The following is the bath composition of electroless copper
Copper sulphate (coating solution)

Fonnaldehyde (reducing agent)
EDTA (Complexing agent)
Buffer solution
(i) NaOH
(ii) Rochelle salt
: 12 gil
: 8 gil
: 20 gil
: 15 gil
: 14 gil
:11
pH
: 25C
Optimum temperature
3. Process: This process involves the reduction of cupric ions to their metallic state at
a controlled rate.
2HCHO + 40H- ~ 2HCOO- + 2H 20 + H2 + 2eCu2+ + 2e- ~ Cu
(anode)
(cathode)
Cu2+ + 2HCHO + 40H- ~ Cu + 2HCOO- + 2H20 + H2
Applications: The preparation of a printed circuit board is done by electro less copper
platint The process is known as substractive method.
A thin layer of copper is first electroplated over the printed circuit board (PCB) made up
of ~ass reinforced rubber. Then selected areas are protected by employing electroplated image.
178
The remaining area is now etched away so as to obtain the required type of circuit pattern. In
order to pack more number of components in a small space, usually double-sided tracks are
made. Finally the connection between the two sides of PCB is made by drilling holes followed
by electroless copper plating through holes (Figure 12.2).
Electroless copper plating is used in double or multilayered boards in which plating
through holes is required. However such holes cannot be copper electroplated.
Etching of
copper plating at
selected areas
Hole for plating

produced by
_d_ril_lin_g_~
Activation and
then electroless
copper plating
+.,---__--,
~ @11(/11d!rliiiiii_thro_ug'--.h_hol_e_~ ~
FIGURE 12.2
12.4.3
Plating through hole

I
fjfzz{;J//J/fl .
Preparation of PCB.
Advantages of Electroless Plating over Electroplating
The following are the advantages of electro less plating over electroplating:
1.
2.
3.
4.
5.
12.4.4
Uniform deposits are produced.

Deposits may be directly produced on non-conductors or insulators (plastics, glass, etc,j,
Coatings produced have unique chemical and physical properties.
No electrical energy is required.
Deposits are usually less porous.
Limitations of Electroless Plating
Though electro less plating is versatile in its applications, the process has serious limitations like
high chemical cost, slow coating rate and poor stability of the solution.
12.5
ORGANIC COATINGS
Organic coatings are inert organic barriers applied to the surface of base metals for corrosion
resistance and decoration. Paints, varnish, lacquers and enamels are the main organic
coatings.
12.5.1
Paints
Paint is a viscous suspension of finely divided solid pigment in a fluid medium which on drying
yields an impermeable film having considerable hiding power. When a paint is applied to a
metal surface, the thinner evaporates, while the drying oil slowly oxidizes forming a dJy
pigmented film.
Protective Coatings
179
Requirements of a good paint

Agood paint should essentially have the following:
I. A good paint should fonn a good impervious and unifonn film on the metal surface.
It should have a high hiding (covering) power.
The film should not crack on drying.
A good paint should adhere well to the surface.
It should spread on the metal surface easily.
6. It should give a glossy film.
7. It should be corrosion resistant.
8. A good paint should give a stable and decent colour on the metal surface.
2.
3.
4.
5.
IsOtuents of a paint and their functions
.he important constituents of a paint are as follows:

I. Pigments
2. Vehicle or drying oils or medium

3.
4.
5.
6.
7.
Thinners
Driers
Fillers or extenders
Plasticizers
Antiskinning agents
I. Pigments:
A pigment is a solid and colour-producing substance in the paint.
Characteristics: A pigment should have the following characteristics:

(a)
(b)
(c)
(d)
(e)
A pigment should be chemically inert.

It should be non-toxic.
It should be opaque and possess high covering power.
A pigment should be cheap and easily available.
It should mix freely with film fonning constituents of the oil.
The most commonly used pigments are as follows:

(a)
(b)
(c)
(d)
(e)
(f)
(g)
White pigments-White lead, BaS04 and Ti02

Blue pigments-Prussian blue and ultramarine blue
Black pigments--Graphite and carbon black
Red pigments-Red lead and Fe203
Green pigments-Chromium oxide
Brown pigments-Iron containing clays
Yellow pigments-Chrome yellow and zinc yellow
Functions: The following are the functions of the pigment:

(a)
(b)
(c)
(d)
A pigment gives opacity and colour to the film.

It provides an aesthetic appeal to the film.
A pigment gives strength to the film.
It protects the film by reflecting the destructive ultraviolet rays.
180
2. Vehicle or drying oils or medium: The liquid portion of the paint in which the
pigment is dispersed is called a medium or vehicle. This is the film fonning constituenl
of the paint. Vehicles are high molecular weight fatty acids present in animal ana
vegetable oils, e.g. linseed oil, dehydrated castor oil, soyabean oil and fish oil.
Functions: The following are the functions of vehicles:
(a) Vehicles hold the pigment particles together on the metal surface.
(b) They form the protective film by evaporation or by oxidation and polymerizatioo
of the unsaturated constituents of the oil.
(c) Vehicles give better adhesion to the metal surface.
(d) They impart water repellency, durability and toughness to the film.
3. Thinners: Thinners are added to paints to reduce the consistency or viscosity oflhe
paints so that they can be easily applied to the metal surface. Thinners are volatile in nature
and evaporate easily after application of the paint, e.g. turpentine and petroleum spirit
Functions: The following are the functions of thinners:
(a) Thinners reduce the viscosity of the paint to render it easy to handle and apply 10
the metal surface.
(b) They dissolve the oil, pigments, etc. and produce a homogeneous mixture.
(c) Thinners evaporate rapidly and help the drying of the film.
(d) They increase the elasticity of the film.
(e) Thinners increase the penetrating power of the vehicle.
4. Driers: Driers are used to accelerate or catalyze the drying of the oil film by
oxidation, polymerization and condensation, e.g. naphthenates, borates and tungstales
of lead, cobalt and manganese.
Functions: Driers act as oxygen carrier catalysts which help the absorption of oxygen
and catalyze the drying of the oil film by oxidation, polymerization and condensation.
5. Fillers or extenders: Fillers are used to reduce the cost and increase the
of the paint, e.g. talc, china clay, calcium sulphate and calcium carbonate.
durabili~
Functions: The following are the functions of fillers:

(a)
(b)
(c)
(d)
Fillers serve to fill the voids in the film.

They reduce the cracking of the paints.
Fillers increase the durability of the paints.
They reduce the cost of the paint.
6. Plasticizers: Plasticizers are chemicals added to paints to give elasticity to the film
and to prevent cracking of the film, e.g. triphenyl phosphate and tricresyl phosphate.
7. Antiskinning agents: They are chemicals added to the paint to prevent skinning of
the paint, e.g. polyhydroxy phenols.
Mechanism of drying oils
Drying oils are the film forming constituent of the paint. These are fatty oils which are extracted
from plants or animals. The fatty oils are tri-esters of glycerol:
Protective Coatings
181
R=C 15H31 (palmitic acid)
CHzOCOR
I
I
C17H31 (linoleic acid)
CHOCOR
C17H33 (oleic acid)

C17H35 (stearic acid)
CH 2 0COR
The oil film after it has been applied to the protected surface absorbs oxygen from air at
the double bonds forming peroxides which isomerize, polymerize and condense to form a tough
and highly cross linked macromolecular film.
CH2COO(CHZ)7-CH=CH-CH2-CH=CH-(CH2)4-CH3
I
CHCOO(CHz)7-CH=CH-CH2-CH=CH-(CH2)4-CH3
I
CHzCOO(CHzh-CH=CH-CHz-CH=CH-(CHz)4-CH3
Glyceride of linoleic acid
air oxidation and

polymerization
CH2COO (CHzh-CH-CH-CHz-CH = CH-(CH2)4-CH3
6I 6I
CH-COO(CHZ)7-CH-CH-CHz-CH-CH-(CHZ)4-CH3
6I 6I
CH2COO (CH2)7-CH-CH-CHz-CH-CH-(CH2)4-CH3
I
o
I
0
I
C, HzCOO (CHz}7-CH-CH-CHz-9H-9H-(CHz}4-CH3
o
I
0
I
C,H-COO(CH2k-<fH-9H-CH2-CH-CH-(CH2)4-CH3
o
I
0
I
CHzCOO (CH2)7-CH-CH-CHz-yH-yH-(CHz)4-CIT,
further
reaction
o
I
0
I
undergoes isomerization,
polymerization and condensation
Highly cross-linked macromolecular film

Methods of application of paint
Paint is applied to the surface by many methods. The important methods are given as follows:
I. Brushing:
A surface may be painted using a brush. Brushes may be made according

to the type of paint applied.
182
2. Spraying: Paint is sprayed on the surface by using a spray gun. The advantage of this
method is that paint is applied to the surface very quickly and easily. It is used for
painting articles such as automobiles and refrigerators.
3. Dipping: This method is applicable to articles which have got an uniform shape. The
articles to be coated are dipped in paint which is kept in a tank. Enamelled wire is
coated by this method.
4. Roller coating: Roller coating is applied when the article is in the form of flat sheets.
Sheet metal for containers is coated by this method.
5. Tumbling: Tumbling is applicable for small articles made of wood. The articles and
the paint to be applied are put into a barrel and the barrel is rotated for a given period.
The articles are then put on drying trays for drying.
Failure of paint
A paint may fail due to several reasons:

1. Chalking: Chalking is the gradual powdering of paint. It is caused by continuous
destructive oxidation of the oil after the original drying of paint.
It is very quick chalking.
2. Erosion:
3. Flaking: Flaking is caused due to poor adherence of a paint film to the surface
because of the presence of grease on the surface.
4. Checking:
It is a very fine type of surface cracking.
5. Alligatoring: The centre portion of the film remains attached to the surface, whereas
the portion around the centre peels off.
The failure of a paint can be prevented by the following ways:
I.
2.
3.
4.
Carefully
Applying
Applying
Allowing
preparing the surface before application of paint.

a suitable primer coat.
the paint evenly.
each paint coat to dry sufficiently before the next coat is applied.
( SHORT QUESTIONS)
1. Explain the functions of driers in a paint.
2. Mention any two methods of treatment of the surface before coating is applied.
3. Galvanizing is preferred to tinning. Why?
4. Distinguish between galvanizing and tinning.
5. Discuss the mechanism of drying.
6. Write down the factors that affect electroplating.
7. Write a note on cladding.
8. What is the principle of providing a metallic coating over a metal?
Protective Coatings
183
9. What is the galvanic protection of a metal surface? What is the mechanism of such
protection?
10. What are the main defects
o~
a paint?
11. What do you mean by electro less plating?

12. List out the advantages of electro less plating.
13. Write the principle involved in the electroless plating of nickel.
1. Write a note on surface preparation for metallic coating.
2. Explain the following terms with reference to surface coating: (a) thinner, (b) enamelling,
(c) drier and (d) pigment.
3. Discuss briefly how electroplating protects the base metals. What are the factors that
control the thickness of coating by this procedure?
4. What are drying oils? Describe their role in organic protective coatings.
5. Explain the processes of galvanizing and sherardizing.
6. Describe the various type of metallic coatings to protect the metal from corrosion.
7. What are the various constituents of a paint. Give examples and functions of each
constituent.
8. What are the properties required of organic coatings against corrosion? What are the basic
constituents of such coatings?
9. Discuss the various steps involved in electroless plating.
10. Write a note on electro less nickel plating.
FUELS AND COMBUSTION
13.1
INTRODUCTION
A fuel is a combustible substance containing carbon as the main constituent which on proper
burning gives large amount of heat that can be used economically for domestic and industrial
purposes. The calorific value of a fuel depends mainly on the two elements:
C +
02~
CO 2 + 94 kcal
2H2 + O 2 ~ 2H20 + 68.5 kcal

So, carbon compounds have been used for many centuries as the source of heat and energy.
The main source of fuel is coal and petroleum. These are stored fuels available in the
earth's crust and are generally called fossil fuels, because they were formed from the fossilized
remains of plants and animals.
13.2
CLASSIFICATION OF FUEL
Fuels are classified as follows:

1. Primary fuels which occur in nature, e.g. coal, petroleum and natural gas.
2. Secondary fuels which are derived from the primary fuels, e.g. coke, gasoline and coal gas.
Both primary and secondary fuels may be further classified based upon their physical state
as (a) solid fuels, (b) liquid fuels and (c) gaseous fuels (Table 13.1).
TABLE 13.1
Classification of fuels
Physical state
Natural or Primary
Prepared or Secondary
Solid
Liquid
Gaseous
Wood, peat, lignite

Petroleum
Natural gas
Coke, charcoal
Kerosene, diesel
Coal gas, water gas
184
Fuels and Combustion
185
13.3 CHARACTERISTICS OF A GOOD FUEL

The following are the characteristics of a good fuel:
I. A good fuel should be cheap and readily available.
2. It should have a high calorific value.
3. A good fuel should have a moderate ignition temperature. If the ignition temperature
is low, the fuel can catch fire easily and the risk of fire hazards is high. If the ignition
temperature is very high, it is very difficult to ignite the fuel. Ignition temperature is
defined as the minimum temperature at which the substance ignites and bums without
further addition of external heat.
4. The moisture content of the fuel should be very low because the moisture content
reduces the calorific value.
5. A good fuel should have low non-combustible matter content or ash content because
the ash content reduces the calorific value or heating value of the fuel. The disposal of
ash is also a big problem and it increases the cost of operation.
6. The products of combustion should not pollute the atmosphere. Gases like CO, S02 and
H2S are some of the harmful gases.
7. Combustion should be easily controllable, i.e. combustion of the fuel should start easily
I or stop when required.
8. It should not undergo spontaneous combustion.
9. It should be safe, convenient and economical for storage and transport.
13.4 ADVANTAGES AND DISADVANTAGES OF SOLID, LIQUID AND

GASEOUS FUELS
13,4,1 Solid Fuels

The following are the advantages of solid fuels:
I. Solid fuels occur widely and they are cheap.
2. They can be handled and transported very easily.
3. No complex mechanism is required for their burning.
4. They can be stored conveniently without any problem like explosion.
5, They have a moderate ignition temperature.

The disadvantages of solid fuels are as follows:
1. Solid fuels form a lot of ash during burning and disposal of ash is very difficult.
2. A lot of labour is required to transport solid fuels.
3. The burning process of solid fuels is not as clear as that of liquid and gaseous fuels.
4. A large space is required for storage of solid fuels and sometimes they may undergo
spontaneous ignition.
186
5. Sincp. a lot' of air is necessary for complete combustion of solid fuels, the thermal
efficiency is not so high.
13.4.2
Liquid Fuels
The advantages of liquid fuels are as follows:

1. Liquid fuels occupy less storage space than solid fuels.
2. As compared to solid fuels, they have a high calorific value.
3. They can be easily transported through pipes.
4. Liquid fuels do not yield any ash or residue during burning.
5. The burning process of liquid fuels is clear.
6. The combustion is uniform and very easily controllable.
7. For complete combustion of liquid fuels, less air is required than that of the solid fuels
and hence their thermal efficiency is high.
8. They can be used in IC engines, boilers and gas turbines.
9. They do not undergo spontaneous combustion.
The disadvantages of liquid fuels are as follows:
1. When the liquid fuels undergo incomplete combustion, they give unpleasant odour.
2. In comparison with solid fuels they are costly.
3. Risk of fire hazards is more in the case of inflammable and volatile liquid fuels. Thus,
they should be stored and transported more carefully.
4. Some amount of liquid fuels may escape due to evaporation during storage.
5. Special type of burners and sprayers are required for effective combustion.
13.4.3
Gaseous Fuels
The following are the advantages of gaseous fuels:

1. Gaseous fuels on burning do not produce any ash or smoke.
2. They can be very easily transported to any place as they can flow through the pipes.
3. They have a high calorific value and produce high temperature.
4. Burning of fuels can be controlled and the nature of flame can be easily made oxidizing
or reducing.
5. Gaseous fuels can be produced by the poorest quality of solid fuels.
6. Gaseous fuels can be used in IC engines, boilers and gas turbines.
7. Compared to solid and liquid fuels, they have a high thermal efficiency.
The following are the disadvantages of gaseous fuels:
1. Since gases occupy a large volume, they require large storage tanks.
2. Gaseous fuels are highlv inflammable and the Dossibilitv of fire hazards is verY hi~h.
187
13.5 CALORIFIC VALUE

The efficiency of a fuel is judged by its calorific value. The calorific value of a fuel is defined
as the total amount of heat liberated by the complete combustion of a unit mass of the fuel.
The quantity of heat can be measured by the following units.
1. Calorie: The calorie is defined as the amount of heat required to raise the temperature
of I gram of water through 1C (l5-16C).
2. Kilocalorie: It is defined as the amount of heat required to raise the temperature of
I kilogram of water through 1C.
3. British thermal unit (BTU): BTU is defined as the amount of heat required to raise
the temperature of 1 pound of water through 1of (60-61 OF).
4. Centigrade beat unit (CHU): It is defined as the amount of heat required to raise
the temperature of 1 pound of water through 1C.
Units of calorific value
The calorific values of solid and liquid fuels are expressed in cal/g or kcal/kg or btuJl b. The
calorific values of gaseous fuels are expressed in kcallm3 .
Gross calorific value and net calorific value
When a fuel containing hydrogen is burnt, the hydrogen present in the fuel undergoes
combustion and is converted into steam. As the products of combustion are cooled to room
temperature, the steam gets condensed into water and latent heat is evolved. Thus, the latent
heat of condensation of steam is also included in the calorific value determination which is
called higher calorific value or gross calorific value (GCV).
GCV is defined as the heat liberated when a unit quantity of the fuel is completely burnt
and the products of combustion are cooled to room temperature.
In actual combustion practice, the products of combustion are not cooled to room temperature and are allowed to escape into the atmosphere with the result that only a lesser amount of
heat is available. The amount of heat so available is called lower or net calorific value (NCV).
The net calorific value is defined as the net heat produced when a unit quantity of the fuel is
completely burnt and the products of combustion are allowed to escape.
Net calorific value = gross calorific value - latent heat of condensation
of water vapour produced
= GCV - mass of hydrogen per unit weight of the fuel burnt
x 9 x latent heat of condensation of water vapour
One part by weight of hydrogen produces nine parts by weight of water as follows.
H2 +
2 g
O~
16 g
H 20
18 g
189
The latent heat of steam is 587 cal/g.
188
NCV
Thus,
9H
X 587
100
= GCV - 0.09 X H X 587
=GCV -
where H = % of H2 in the fuel.
13.5.1
Theoretical Calculation of Calorific Value
Dulong's fonnula for the theoretical calculation of calorific value is

HCV =
1~ [8080C + 34500 ( H - ~) + 2240SJkcallkg
where C, H, 0 and S are the percentages of carbon, hydrogen, oxygen and sulphur in the fuel.
It is based on the assumption that 1 kg of carbon provides 8080 kcal of heat, one kg of
hydrogen provides 34500 kcal of heat and one kg of sulphur provides 2240 kcal of heat.
However, all the oxygen in coal is assumed to have combined with hydrogen in the ratio H:O as
1:8 by weight and so only the uncombined hydrogen is available for providing heat by combustion.
13.6
COAL
Coal is regarded as a fossil fuel produced from large accumulations of vegetable debris due to
partial decay and alteration by the action of heat and pressure over millions of years.
Microscopic examination of coal reveals the presence of aggregates of wood-like and
cork-like structures indicating the origin of coal from plants.
The fonnation of coal is explained by two theories namely autochthonous or in situ theory
and allochthonous or transportation theory.
1. According to in situ theory coal fonnation took place at the place of vegetation itself.
The great purity of many coals is an evidence to this theory.
2. The drift or transportation theory states that the coal seams are not fonned where Ihe
vegetation grew and accumulated originally. These materials were drifted by rivers and
got deposited there. The great thickness of coal seams supports this theory.
The fonnation of coal from vegetable matter was divided into two stages.
1. Diagenetic stage or biochemical stage
2. Metamorphism
During the first stage of coalification, the plant materials were attacked by various
microorganisms like streptococcus and micrococcus. The end product of this stage is peat or 10\\
rank lignite.
cellulose
humified residue
Since the biological bacterial processes may predominate in the first stage, this stage is
also called biochemical coalification. In the second stage, the chemical changes taking place are
188
NCV=GCV- 9H x587
100
= GCV - 0.09 X H X 587
Thus,
where H = % of H2 in the fuel.
13.5.1
Theoretical Calculation of Calorific Value
Dulong's fonnula for the theoretical calculation of calorific value is

HCV =
1~ [8080C + 34500 ( H - ~) + 2240SJkcaI/kg
where C, H, 0 and S are the percentages of carbon, hydrogen, oxygen and sulphur in the fuel.
It is based on the assumption that 1 kg of carbon provides 8080 kcal of heat, one kg of
hydrogen provides 34500 kcal of heat and one kg of sulphur provides 2240 kcal of heat.
However, all the oxygen in coal is assumed to have combined with hydrogen in the ratio H:O 8.\
1:8 by weight and so only the uncombined hydrogen is available for providing heat by combustion.
13.6
COAL
Coal is regarded as a fossil fuel produced from large accumulations of vegetable debris due to
partial decay and alteration by the action of heat and pressure over millions of years.
Microscopic examination of coal reveals the presence of aggregates of wood-like and
cork-like structures indicating the origin of coal from plants.
The fonnation of coal is explained by two theories namely autochthonous or in situ theory
and allochthonous or transportation theory.
1. According to in situ theory coal fonnation took place at the place of vegetation itself.
The great purity of many coals is an evidence to this theory.
2. The drift or transportation theory states that the coal seams are not fonned where the
vegetation grew and accumulated originally. These materials were drifted by rivers and
got deposited there. The great thickness of coal seams supports this theory.
The fonnation of coal from vegetable matter was divided into two stages.
1. Diagenetic stage or biochemical stage
2. Metamorphism
During the first stage of coalification, the plant materials were attacked by various
microorganisms like streptococcus and micrococcus. The end product of this stage is peat or lOll
rank lignite.
cellulose
humified residue
Since the biological bacterial processes may predominate in the first stage, this stage is
also called biochemical coalification. In the second stage, the chemical changes taking place are
189
mostly due to two factors, viz. pressure and temperature in varying degrees. The result is coals
of different maturity or rank.
The various agencies responsible for the conversion of plant tissues to coal include
(a) bacteria (under water), (b) time (millions of years), (c) temperature (>300C) and
(d) pressure.
The time required for the formation of young brown coals is of the order of 107 years
while that for most mature coals is 3 x 108 years.
13.6.1 Classification of Coal

Coals are classified on the basis of their rank. The rank is defined as the degree or extent of
maturation and is therefore a qualitative measure of carbon contents. Peat, lignite and subbituminous coals are referred as low rank while bituminous coals and anthracites are classed as
high rank. In European terminology, the lignite and sub-bituminous coals are called soft coals
while bituminous coals and anthracite coals are termed hard coals. In North American terminology, the coal series is written as
Wood
Peat
Lignite
Bituminous
Anthracite
The progressive transformation of wood to anthracite results in

I. increase in carbon content and decrease in hydrogen, oxygen, nitrogen and sulphur
contents
2.
3.
4.
5.
decrease in volatile matter content

increase in calorific value
decrease in moisture content
increase in hardness
The variations in average compositions from wood to anthracite are summarized in

Table 13.2.
TABLE 13.2
Average composition from wood to anthracite

Composition
Weight per cent (daf basis)
Increasing pressure,
temperature, time
Wood
Peat
Lignite
Sub-bituminous
Bituminous
Anthracite
49
60
70
75
85
7
6
5
5
5
44
34
94
25
20
10
The progressive transformation of wood to anthracite is graphically represented in

Figure 13.1.
190
9000
8000
7000
Va/an
fe matter
C
Q)
0
6000
a.
4000
I"
Wood
FIGURE 13.1
13.6.2
~I"
Peat
~I"
_ _ ~I"
~I"
~I
lignite Bituminous Anthracite
Transformation of wood to anthracite.
Varieties of Coal
Peat
1.
2.
3.
4.
Peat represents the first stage of the conversion of vegetable matter to coal.
It is fibrous compact substance varying in colour from dark brown to black.
Its calorific value is about 5450 kcal/kg.
It is an uneconomical fuel due to its higher proportion of moisture and lower calorific
value.
In India, peat deposits occur in the Nilgiri Hills.

Lignite
1. Lignite or brown coal represents the intermediate stage in the process of coalification.
2. Due to the presence of high volatile matter content, it burns with a long smoky flame.
3. Its calorific value is about 5800-7000 kcal/kg.
In India, lignite deposits occur at Neyveli.
Bituminous coal
1. Bituminous is the most common and widely used variety of solid fossil fuel.
2. Its calorific value is about 8000-8500 kcal/kg.
In India, bituminous coal reserves are located at Bihar and Assam.
Anthracite
1.
2.
3.
4.
Anthracite represents the last stage of conversion of vegetable matter into coal.
It is a superior variety of coal.
Its volatile matter, moisture and ash contents are very low.
Its calorific value is about 8600 kcal/kg.
In India, anthracite coal is found in Kashmir.
191
13.6.3 Analysis of Coal

In order to assess the quality of coal the following two types of analysis are made: proximate
analysis and ultimate analysis.
Proximate analysis
Proximate analysis includes the determination of moisture, volatile matter, ash and fixed carbon.
This gives quick and valuable information regarding commercial classification and
determination of suitability for a particular industrial use.
I. Moisture content: This may be present as surface or adsorbed moisture which is lost
on air-drying and as inherent moisture that has been retained by an air-dried sample.
In general, coals of high rank contain less of inherent moisture.
It is determined by heating 1 g of the powdered air-dried coal sample at 105-11 ooe in
an electric hot-air oven for one hour. The loss in weight of the sample is found out and
the percentage of moisture is calculated as
.
percentage 0 f mOIsture
loss in weight of the sample

100
x
weight of the air dried sample
Significance: High percentage of moisture is undesirable because it reduces the calorific value and increases the transport cost. A considerable amount of heat is wasted in
evaporating the moisture during combustion. Hence, the lesser the moisture content, the
better is the quality of coal as a fuel.
2. Volatile matter: The volatile matter varies with the rank of coal. The volatile matter
obtained during the heating of coal consists mainly of combustible gases such as H 2 ,
CO, CH4 and other hydrocarbons. It also contains incombustible gases such as CO2 and
steam.
It is determined by heating 1 g of powdered, dried-coal sample in a covered platinum
crucible at 950 20C for 7 minutes in a muffle furnace. The loss in weight of the
sample is found out and the % of volatile matter is calculated as
.
percentage of volatIle matter
loss in weight of the sample

x 100
weight of moisture free coal
Significance: High volatile matter coals give long flames, high smoke and low
calorific values. Hence, the lesser the volatile matter content, the better is the quality
of coal. Coals with low volatile matter content bum with a shorter flame. Thus, higher
the volatile matter content, larger is the combustion space required. Hence, the volatile
matter content of a coal influences the furnace design. Further, the percentage of
volatile matter in a coal denotes the proportion of the coal which will be converted into
gas and tar products by heat. Hence, high volatile matter content is preferable in coal
gas manufacture. For the manufacture of metallurgical coke, a coal with low volatile
matter content is preferred.
192
3. Ash: Ash is the inorganic material left behind when all the combustible substances
have been burnt off from the coal. Ash usually consists of silica, alumina, iron oxide
and small amounts of lime, magnesia, etc.
It is determined by heating 1g of dried-coal sample in a platinum crucible at 725 25'C
in a muffle furnace for half an hour. From the weight of the residue, the percentages
of ash is calculated as
percentage of ash
weight of ash left x 100

weight of dried coal
Significance
1.
2.
3.
4.
The ash reduces the heating value of coal.

The presence of ash also increases the transporting, handling and storage costs.
It also involves additional cost in ash disposal.
The percentage of ash determines the quality of coal. Hence, the lesser the
percentage of ash, the better is the quality of coal.
4. Fixed carbon: Fixed carbon is the material remaining after the determination of
moisture, volatile matter and ash contents. It is calculated by the formula,
per cent of fixed carbon
100 - (per cent of moisture

+ per cent of volatile matter + per cent of ash)
Significance: The higher the percentage of fixed carbon in a coal, the greater is its
calorific value.
Ultimate analysis
The ultimate analysis includes the determination of carbon, hydrogen, nitrogen, sulphur and
oxygen in coal. Since it is used for the determination of elements present in the coal, it is also
called elemental analysis. This analysis gives exact results and are useful in calculating the
calorific value of coal using Dulong's formula.
I. Carbon and hydrogen: The percentage of carbon and hydrogen in coal are usually
determined by combustion method.
A known amount of the coal sample is burnt in a current of O 2 in combustion apparatus.
The carbon and hydrogen present in the coal sample are converted into CO 2 and H20
respectively. The CO2 and H 20 vapours then formed are passed into weighted potash
bulbs and CaCl2 tubes respectively. The increase in weight of potash bulb is due to the
CO 2 formed. From the amount of CO2 formed, the percentage of carbon can be
calculated. The increase in weight of CaCl2 tube gives the amount of water vapour
formed. From the weight of water vapour formed, the percentage of hydrogen present
in the coal can be found out.
2KOH + CO 2 ~ K 2C03 + H 20
CaCl2 + 7H 2 0
CaCI 2 ' 7H2 0
12 X weight of CO 2
x 100
44 x weight of coal taken
Per cent of carbon =
Per cent of hydrogen
193
2 x weight of H 20
x 100
Significance: The higher the percentage of carbon and hydrogen, the better is the
quality of coal and higher is its calorific value. The percentage of carbon is helpful in
assessing the rank of coal.
2. Nitrogen: Nitrogen present in the coal sample is determined by the Kjeldahl method.
About 19 of the finely powdered coal sample is heated with conc. H 2S04 along with
K2S04 (catalyst) in a long necked Kjeldahl flask. Nitrogen in the coal is converted into
ammonium sulphate and a clear solution is obtaine~.
2N + 3H2 + H 2S04 ~ (NH4)2S04
It is heated with excess of NaOH and the liberated ammonia is distilled over and
absorbed in a known volume of standard acid solution. The unused acid is then determined by back titration with standard NaOH. Thus, the amount of acid neutralized by
liberated ammonia is determined.
(NH4)zS04 + 2NaOH
2NH3 + Na2S04 + 2H20
NH3 + HCI ~ NH 4CI

From this the percentage of nitrogen is calculated as follows:
Per cent of nitrogen
volume of the acid used x normality of the acid x 1.4

h
al
weight of t e co taken
Significance: Nitrogen does not have any calorific value and its presence is not of
much significance.
3. Sulphur:
The sulphur present in the coal sample is determined by the Eschka

method. In the Eschka procedure, the sulphur is converted into soluble (sodium)
sulphate by incinerating coal with a 1 : 2 mixture of sodium carbonate and calcined
magnesium carbonate. It is further treated with BaCl2 solution so that sulphates are
precipitated as BaS04. From the weight of BaS04 obtained, the sulphur present in the
coal is calculated by using the following formula:
Per cent of sulphur
= 32
x weight of BaS04 obtained x 100

Significance
1. Sulphur increases the calorific value of coal.
2. The combustion products of sulphur, i.e. S02 and S03 have corrosion effects on
equipment.
3. The harmful gases S02 and S03 will cause air pollution.
194
4. Sulphur containing coal is not suitable for the preparation of metallurgical coke as
it adversely affects the properties of the metal.
So, the presence of sulphur in coal is undesirable.
4. Oxygen:
The percentage of oxygen in coal is calculated by difference.
Per cent of oxygen
100 - (per cent of C + per cent of H

+ per cent of N + per cent of S)
Significance: High oxygen content coals are characterized by high inherent moisture
and low calorific value. The lower the oxygen content, the more is the maturity of coal
and greater is its calorific value. Thus, a good quality coal should have lower
percentage of oxygen.
13.6.4
Carbonization
When coal is heated strongly in the absence of air, it loses volatile matter and converted into
lustrous, dense, strong, porous and coherent mass known as coke. This process of converting
coal into coke is known as carbonization.
Coals on heating first lose moisture and volatile matter and at higher temperatures, the
mass becomes soft, plastic and fused to give a coherent mass. Such coals are called caking
coals. Coals which form a weakly coherent mass on heating are called non-caking coals. The
residue so formed is called coke. If the coke so produced is hard, porous and strong, then the
coal from which this coke is derived is called a coking coal. Thus, all coking coals are caking
coals but all caking coals are not coking coals.
Usually a high rank coal like bituminous coal is used for carbonization. It has good
coking power and medium volatile matter content. Caking coals with high volatile matter
content are used for gas manufacture whereas coking coals of some what lower volatile matter
or medium volatile matter are used for the manufacture of metallurgical coke and are termed
coking coals.
During carbonization non-caking coals do not produce a good coherent coke. But their
rate of carbonization is very high. So, in order to obtain a good quality coke, coking coals are
blended with non-caking coals. This type of blending is helpful in (a) increasing the rate of
carbonization and (b) producing a good quality coke from non-caking coal.
Types of carbonization
Depending upon the temperature, carbonization is classified into three categories.

1. Low temperature carbonization (LTC): 500-600C
2. Medium temperature carbonization: 600-900C
3. High temperature carbonization (HTC): 900-1200C
Table 13.3 shows the differences between low temperature carbonization and high
temperature carbonization.
TABLE 13.3
195
Differences between LTC and HTC
Low temperature carbonization (LTC)
High temperature carbonization (HTC)
I. Temperature used is 500-600C.
1. Temperature used is 900-1200C.
2. Yield of coke is 75-80%.
2. Yield of coke is 65-75%.
3. The coke obtained is known as soft coke or

semi coke.
3. The coke obtained is hard.
4. The coke obtained contains 5-15% volatile
4. The coke obtained contains 1-3% volatile
matter.
5. The mechanical strength of coke is not very
strong.
matter.
5. The mechanical strength of coke is very
strong.
6. The coke is good for domestic purposes.
6. The coke is good for metallurgical purposes.
7. Gaseous products obtained from this process

have low calorific value.
8. Quantity of gaseous products obtained is
about 130-150 m3/tonne.
7. Gaseous products obtained have high calorific

value.
8. Quantity of gaseous products obtained is
300-390 m3/tonne.
13.6.5 Requisites of Good Metallurgical Coke

I. Purity: It should be economical if the moisture, ash, sulphur and phosphorus contents
are very low. Moisture and ash reduce the calorific value. Sulphur and phosphorus may
contaminate the metal.
2. Porosity: Coke should be porous so that oxygen should have intimate contact with
carbon and combustion will be complete and unifom.
3. Strength: The mechanical strength of coke should be very high in order to withstand
high pressure of the overlying solids in the furnace.
4. Calorific value:
5. Cost:
The calorific value of coke should be very high.
It should be cheap and readily available.
6. Combustibility:
Coke should burn easily.
7. Reactivity: The reactivity of coke should not be very high because low reactive cokes
produce high temperature on combustion. Reactive cokes do not produce intense heat.
13.6,6 Differences between Coal, Coke and Charcoal

Coal: Coal is a natural fuel. It burns with a long flame due to the presence of volatile matter.
[I has low strength and porosity compared to coke. It has high sulphur content which is very
[ow in coke. The calorific value varies depending on the rank of coal.
Coke: Coke is a secondary fuel. It is obtained by the destructive distillation of coal. It burns
with a small flame and without smoke. The volatile matter content of coke is very low. The
mechanical strength is very high. Its calorific value varies between 7000-8000 kcal/kg.
196
Charcoal: Charcoal is a secondary fuel. It is obtained by heating wood in limited quantity of

air. It easily ignites and burns with a slight flame without much smoke. Its calorific value varies
between 6000-8000 kcal/kg. Its strength is very low compared to coke.
13.6.7
Manufacture of Metallurgical Coke
Coke can be manufactured by Otto-Hoffmann's method.

Otto-Hoffmann's method or by-product oven method
Otto-Hoffmann's oven consists of a number of narrow silica chambers. Each chamber is about
10-12 m long, 3-4 m high and 0.4-0.45 m wide. The chambers are tightly closed so that no
air is admitted. At the top of each chamber, there are three holes for charging the coal. It is also
provided with a gas off-take (which carries out the volatile matter) and iron door at each end
for discharging coke (Figure 13.2).
Chambers loaded with coal
-Coalgas
Hot
regenerators
Waste gases
to chimney - - - - - - '
__ Waste gases
to chimney
Air
FIGURE 13.2
Producer gas
Otto-Hoffmann's oven.
Coal is charged into the chamber and the chambers are closed. The heat for the
carbonization reaction is obtained by burning the preheated air and the producer gas in the
interspaces between the chambers. The gas and the air are preheated by means of regenerato~.
The temperature goes around 1100 0 e and the yield of coke is about 70 per cent. Each oven
holds about 20 tonnes of coal charge and the time taken for carbonization is about 12-20 hou~.
When the process is complete, the end doors are opened and coke is withdrawn. It is then cooled
by quenching with water.
197
Heat saving is done by regenerators. Hot exhaust gases after combustion are allowed to
pass through the two sets of regenerators which are stacked by brick work. The hot gases heat
up the brick work. While one regenerator is heated by the hot gases, the other regenerator is
~ for heating the incoming air and gas mixture. This process of alternately passing of hot
exhaust gases and cold air and gas through regenerators continues and this process is called
'egeneration.
Recovery of by-products: The volatile matter coming out from the oven in the form of gas,
;,nown as coke-oven gas, is composed of tar, ammonia, naphthalene, benzene, etc. These products are separated from each other.
Recovery of coal tar: The coke-oven gas is passed through a tower where liquor
ammonia is sprayed. Dust and tar along with ammonia are collected in a tank which is heated
to recover back ammonia. Ammonia is again sent to the tower.
On fractional distillation, coal tar gives benzene, toluene, naphthalene, creosote oil, etc.
which are the starting materials for obtaining numerous drugs, perfumes and explosives. Coal
tar pitch is used for road making. It is also used for preserving timber.
Recovery of ammonia: The gas free from tar is passed through another tower in
which water is sprayed. Ammonia goes into solution as ammonium hydroxide. On boiling
with milk of lime, it yields ammonia which is converted into ammonium sulphate and used
as a fertilizer.
Recovery of naphthalene: The gas is then passed through another tower where water is
sprayed at low temperature. Here naphthalene gets condensed.
Recovery of benzene: The gas is then passed through a tower where petroleum is
sprayed. Here benzene and its higher homologues are condensed.
Advantages of Otto-Roffmann's method:
Hoffinann's method:
The following are the advantages of Otto-
I. Valuable by-products like ammonia and coal gas are recovered.

2. Here heating is done externally by producer gas.
3. The carbonization time is considerably reduced.
13.6.8 Hydrogenation of Coal

Coal contains about 4.5% hydrogen compared to about 18% in petroleum based on 100 grams
of carbon. So, coal is a hydrogen deficient compound. If coal is made to react with hydrogen
at high temperatures and high pressures, solid coal will be converted into liquid fuels. The
preparation of liquid fuels from solid coal is known as hydrogenation of coal.
There are two methods available for the manufacture of liquid fuels from solid coal. They
are (a) Fischer-Tropsch process and (b) Bergius process.
rlScher-Tropsch process or indirect process
In the Fischer-Tropsch process (Figure 13.3), coal is first converted into coke. Then water gas
is produced by the action of steam over red hot coke. It is mixed with hydrogen and the mixture
198
is compressed to 5-25 atmospheres. The compressed gases are then led through a converter
which is maintained at a temperature of 200-300C. The converter is provided with a suitable
catalyst consisting of a mixture of ] 00 parts cobalt, 5 parts thoria, 8 parts magnesia and
200 parts kieselguhr. A mixture of saturated and unsaturated hydrocarbons occurs as a result of
polymerization.
nCO + 2nH2
CnH 2n + nH2 0
nCO + (2n + 1)H2
C nH 2n+2 + nH20
The reactions are strongly exothermic. Hence, the hot outcoming gaseous mixture is led
to a cooler where a liquid resembling crude oil is obtained. The crude oil thus obtained is then
fractionated to yield gasoline and high-boiling heavy oil. The heavy oil is used for cracking to
get more gasoline (Figure 13.3).
Catalyst
(Co + Th02 +
MgO + kieselguhr)
Cooler
r-----'l- Gasoline
Heavy oil
cracked
Gasoline
Fractionating
column
Compressor
FIGURE 13.3
Fischer-Tropsch process.
Bergius process or direct process
This method was developed by Bergius in Germany during the first World War. In this process,
the finely powdered coal is converted into a paste with a heavy oil and a catalyst (nickel oleate)
is mixed with it. The coal paste along with the catalyst is sent to a converter where it is heated
to 400-450C under 200-250 atmospheres in the presence of hydrogen (Figure 13.4).
Hydrogenation takes place to form higher saturated hydrocarbons. These higher saturated
hydrocarbons undergo further cracking (because of the high temperature and pressure prevailing
in the converter) to produce low molecular weight hydrocarbons. When the low molecular
weight hydrocarbons are led to a cooler, crude oil is obtained. The crude oil is then fractionated
to give gasoline, middle oil and heavy oil. The middle oil is further hydrogenated in vapour
phase to yield more gasoline. The heavy oil fraction is recycled to make a paste with fresh batch
of coal dust.
199
Powdered coal
Heavy oil Catalyst
Cooler
O(lO(lO
ODQDO
O(lO(lO
H2
ODODO
O(lO(lO
ODODO
(at 250 atm) O(lO(lO
..
ODQDO
O(lG'(lO
Converter
Fractionating
column
FIGURE 13.4 Bergius process.
13.7 LIQUID FUELS

Naturally occurring liquid fuels are mainly oils. Petroleum or crude oil is mainly known and it
fonns the major source of liquid fuels. Petroleum or rock oil means liquids which are obtained
from the ground either by natural seepage or by drilling wells into various depths.
Petroleum is a complex mixture of paraffinic, olefinic and aromatic hydrocarbons with
small quantities of organic compounds containing oxygen, nitrogen and sulphur.
The average composition of crude oil is as follows.
C: 80-87.1%
H: 11.1-15.0%
S: 0.1-3.5%
0: 0.1-0.9%
N: 0.4-0.9%
India, produces only about one-third of its total petroleum requirements within the country.
The rest is imported from the Middle East (Iran, Iraq, Saudi Arabia, Kuwait, etc.) and from
Indonesia in the East. The petroleum refineries of India are located in Trombay, Visakhapatnam,
Cochin and Manali.
13.7.1 Classification of Petroleum

Petroleum is classified into three categories according to its composition.
I. Paraffin base petroleum: It is mainly composed of saturated hydrocarbons from

CH4 to C3s Hn and a little of naphthenes and aromatics.
2. Naphthenic or asphaltic base petroleum: It contains mainly cyc10paraffins or
naphthenes with a smaller amount of paraffins and aromatics.
3. Mixed base petroleum: It contains both paraffins and asphaltic hydrocarbons.
200
13.7.2
Refining of Petroleum
The crude oil obtained from the earth is a mixture of oil and unwanted impurities like water,
sulphur compounds and dirt particles. After the removal of all the impurities, the crude oil is
subjected to fractional distillation. During distillation, the crude oil is separated into various
fractions with different boiling ranges. Thus, the process of removing unwanted impurities and
dividing petroleum into different useful fractions with different boiling ranges is called refining
of petroleum.
Separation of water by de-emulsification (Cottrell's process)
The crude oil from the oil well is an extremely stable emulsion of oil and salt water, The
commonly used method to remove water from oil is an electrical method.
In this method, a high voltage alternating current is passed to form an electric field in the
crude oil to destroy the emulsion films. Droplets of colloidal water coalesce to form large drops
which separate out from the oil.
Removal of harmful impurities
Sulphur compounds are removed by treating crude oil with copper oxide. The copper sulphide
formed is separated by filtration.
Fractional distillation
Fractional distillation is carried out in a fractionating still. A fractionating still consists of a pipestill and a bubble tower. The crude oil is heated to about 300-400C in the pipe-still and the
hot vapours are introduced into the bottom of the bubble tower (Figure 13.5).
~~~~~;densed
5;
Gasoline
~~
Kerosene
~~
Bubble tower
c:.
C
c:.
Lubricating oil
Petroleum jelly
_Greases
Paraffin wax
c:C.P;~
Vacuum
distillation tower
FIGURE 13.5 Fractional distillation of crude petroleum.
The tower is hot towards the lower end and comparatively cooler at the upper end. It ~
provided with a large number of horizontal stainless steel trays. As the vapours of the oil rise
up in the fractionating column, they become cooler and get condensed at the trays. High boiling
fractions condense at lower trays whereas the low boiling fractions condense at higher trays,
Thus, the crude oil is fraction~teci into different fractions depending upon their boiling ranges
201
and are collected at different heights of the tower. The names, approximate composition, boiling
range and uses of the various fractions are given in Table 13.4.
TABLE 13.4 Various fractions with boiling range, approximate composition and uses
Name of the fraction
Boiling range
(0C)
Uncondensed gases
Below -30
Petroleum ether
Gasoline or Petrol
30-70
40-120
Naphtha
120-180
Kerosene oil
180-250
Diesel oil
250-320
Heavy oil
320-400
Approximate
composition in terms
of hydrocarbons
containing C-atoms
Use
As domestic and industrial

fuel under the name LPG
As solvent
Fuel for IC engines
As solvent for paints and
varnishes
Fuel for stoves, jet engine
fuel and for preparing lab
gas
Diesel engine fuel
Fuel for ships and for
conversion to gasoline by
cracking
Heavy oil on vacuum distillation gives

Lubricating oils
Petroleum jelly
(Vaseline)
As lubricants
Used in cosmetics and
medicines
Grease
As lubricants
Paraffin wax
In candles, boot polishes,

etc.
Pitch
Above 400
C30 and above
Used for making roads
The gasoline obtained by this fractionation is called straight-run gasoline.
13.7.3 Cracking
The crude oil on fractionation yields about 20-30 per cent gasoline, 30-45 per cent middle oils
and 25-50 per cent heavy oils. Among these fractions, gasoline has the highest demand as
motor fuel. Further, the quality of the gasoline is not so good and hence is used only after
suitable blending. This results in the surplus of heavier fractions. To overcome these limitations
a process of thermal decomposition known as cracking was developed by means of which
stocks of high boiling fractions are converted into more valuable low boiling fraction suitable
for spark ignition engines of automobiles. Thus, the objective of cracking is to obtain greater
yields of improved gasoline by thermal decomposition of the surplus heavier fractions. It was
202
noticed that cracked gasoline give better engine performances (less knocking) than gasoline
obtained from direct distillation and consequently the demand for cracked gasoline is increased.
Cracking is defined as the decomposition of high boiling hydrocarbons of high molecular
weight into simpler, low boiling hydrocarbons of low molecular weight.
ClOH22
decane
(boiling point 174C)
+
n-pentane
(boiling point 36C)
C 5H lO
pentene
Two kinds of cracking are known, viz. thermal cracking and catalytic cracking.
Thermal cracking
When cracking is carried out without any catalyst, it is called thermal cracking. There are two
types of thermal cracking.
1. Liquid phase thermal cracking: In this method, the heavy oil is cracked at a
temperature of 475-530C under high pressures (100 kg/cm 2) to keep the reaction
product in liquid state. The cracked products are then separated in a fractionating
column. The yield is about 50-60 per cent.
2. Vapour phase thermal cracking: In this method, the cracking oil is vaporized and
then cracked at about 600-650C and under a low pressure of 10-20 kg/cm2 The yield
of petrol is about 70 per cent. This process is suitable only for those oils which are
readily vaporized. Heavy oils cannot be cracked by this method because these oils
cannot be completely vaporized under these conditions.
CatalytiC cracking
In catalytic cracking, cracking is carried out in the presence of a catalyst at much lower
temperatures and pressures. The catalysts used are aluminosilicates or zeolites. There are two
types of catalytic cracking.
1. Fixed bed catalytic cracking:
The heavy oil charge is passed through a preheater
where the oil is vaporized and heated to 400-500C. The bauxite catalyst is mixed with
clay and zirconium oxide and packed in the catalyst chamber. The hot vapours are
passed over a fixed bed of catalyst in the catalyst chamber maintained at 425-450C
and 1.5 kg/cm2 pressure. During this passage through the chamber, about 40 per cent
of heavy oil charge is converted into gasoline and about 2-4% carbon is formed. The
carbon gets adsorbed on the catalyst bed. The cracked vapours are then passed through
the fractionating column where heavy fractions condense. The vapours are then passed
through the cooler where gasoline condenses along with some gases. The gasoline
containing some dissolved gases is then sent to stabilizer where the dissolved gases are
removed and pure gasoline fraction is recovered.
The catalyst after 8-10 hours stops its functioning due to the deposition of carbon. It
is reactivated by burning off the carbon deposited in a stream of hot air. This heat is
utilized for heating the reactor (Figure 13.6).
203
Cracked
Catalyst
Vapours
Heavy
oil_~==::::Y
charge
some
dissolved
gases
Fractionating
column
Heater
Heavy
oil
FIGURE 13.6
Fixed bed catalytic cracking.
2. Moving bed or fluid bed catalytic cracking: In this process, the solid catalyst is
very finely powdered so that it behaves almost as a fluid which can be circulated in gas
stream (Figure 13.7).
Catalyst hopper
Cooler
separator
gases
Oil charge
t;;'(t;
~OJ
OJ OJ
Cl
(ijo
u>
-OJ
eQ.
(j)
FIGURE 13.7
OJ
OJ
ex:
Moving bed catalytic cracking.
To catalyst
hopper above
204
The preheated' oil vapours are cracked in a reactor which is maintained at a temperature
of 530C and at a pressure of 5 kglcm 2 The catalyst dust is removed by passing the cracked
vapours through the catalyst dust separator. The cracked vapours are then sent to the
fractionating column where heavy oil is separated. The vapours are then passed through the
cooler where gasoline condenses along with some gases. The gasoline containing some
dissolved gases is then sent to a stabilizer where the dissolved gases are removed and pure
gasoline is recovered.
The catalyst powder gradually becomes heavier due to coating with carbon and settles to
the bottom. It is regenerated and is again sent to the catalyst hopper through the elevator.
Advantages of catalytic cracking over thermal cracking
Catalytic cracking has a number of advantages :

1. The production cost is very less since high temperatures and high pressures are not
needed.
2. The yield of petrol is higher.
3. The quality of petrol produced is better.
4. No external fuel is necessary for cracking. The heat for cracking is derived by burning
the carbon deposited on the catalyst.
5. The product contains less sulphur compounds.
6. The percentage of gum and gum forming compounds is very low.
7. The octane number of cracked gasoline is higher compared to straight-run gasoline. It
is due to presence of branched paraffins and aromatic hydrocarbons in cracked
gasolines.
13.7.4 Synthesis of Gasoline

Gasoline is synthesized by the following methods.
1.
2.
3.
4.
Fischer-Tropsch process
Bergius process
Polymerization
Alkylation
The first two methods, i.e. the Fischer-Tropsch process and the Bergius process have been
discussed in Section 13.6.8.
Polymerization
Ole fins obtained as by-products during cracking can be polymerized using H2S04 as a catalyst
to give high molecular weight hydrocarbons which can be catalytically hydrogenated to give
branched alkanes. The liquid fuel thus prepared by this polymerization has a higher octane
number.
Isobutylene
205
Diisobutylene (isooctene)
catalyst H2
CH3
I
I
CH3-C-CH 2-CH-CH 3
CH 3
CH3
2,2,4-trimethylpentane (isooctane)
Alkylation
Replacement of a hydrogen atom of a hydrocarbon by an alkyl group is known as alkylation.

The most important example is the reaction of isobutane and isobutene in the presence of
anhydrous HF at room temperature to give isooctane. This process is used to produce gasoline
of improved quality.
CH 3
Anhydrous
HF
I
I
) CH3-C-CH 2-CH-CH3
CH 3
lsobutane
CH3
Isooctane (2,2,4-trimethylpentane)
Isobutene
13.7.5 Refining of Petrol

The gasoline obtained contains some sulphur compounds and easily oxidizable unsaturated
hydrocarbons. Sulphur-containing gasoline when used as fuel gives off S02 which not only
leads to corrosion of the combustion plant but also pollutes the atmosphere. The unsaturated
hydrocarbons are oxidized and polymerized and hence cause gum and sludge on storing. So,
these undesirable compounds must be removed from gasoline.
Removal of sulphur compounds
Gasoline may contain sulphur as H 2S or RSH. Sulphur-containing petrol is known as sour spirit.
The removal of sulphur from petrol is known as desulphurization. This can be achieved by
Doctor's treatment. In this process, petrol is treated with an alkaline solution of sodium plumbite
and a little of sulphur:
Na2Pb02 + 2RSH + S
RS - SR + 2NaOH+ PbS
206
The disulphides are free from odour and do not lead to corrosive products. Since the
removal of sulphur compound eliminates bad odour from petrol, this process is also called
sweetening process.
Removal of olefins
On long storing of gasoline, unsaturated hydrocarbons are oxidized and polymerized to form
gum like substances. These substances deposit on the walls of the carburettor and stop the
engine. The unsaturated hydrocarbons or olefins can be removed by treating gasoline with cold
80 per cent H 2S04 , Sulphuric acid converts olefins to tar-like substances which are removed by
filtration. The gasoline layer is then washed with sodium hydroxide solution.
Removal of colour
Gasoline can also be purified by passing through Fuller's earth which preferentially adsorbs the
colours and olefins.
A comparison of straight-run, cracked and polymer gasolines is given in Table 13.5.
TABLE 13.5 Comparison of straight-run, cracked and polymer gasolines
Straight-run gasoline
Cracked gasoline
Polymer gasoline
1. It is obtained from heavy

oil.
1. It is obtained from low
crude
2. It is physically separated
2. High molecular weight com-
2. Low molecular weight com
ponents are broken into low

molecular weight components. So, it is a chemical
process.
ponents are polymerized to

give high molecular weight
components. So, it is a
chemical process.
3. It is having a higher octane
3. It is having the highest
1. It is obtained from straight
distillation
petroleum.
of
from crude oil.
3. It is having a low octane
number.
4. It contains only normal
alkanes.
5. Composition range is wide

(C 5-C 9 )
number.
contains
more
of
aromatics, naphthenes and
branched chain hydrocarbons.
5. Composition
range
is
narrow (C 6-C g).
4. It
molecular weight compo

nents.
octane number.
4. It contains more of branched
chain hydrocarbons.
5. Composition range is very

narrow (C 7-C g).
Requisites of an ideal gasoline

Ideally gasoline should have the following properties.
1.
2.
3.
4.
5.
Gasoline
It should
Gasoline
It should
Gasoline
should have high calorific value.

be free from sulphur and moisture.
should not form gums during storage.
have a higher octane number.
should leave little carbon deposit during combustion.
207
6. It should have proper and partial vaporization on mixing with air in IC engines. If it
does not vaporize, there will be difficulty in starting the engine. On the other hand if
the volatility of gasoline is too high, it leads to vapour formation in the fuel line causing
vapour locking. This reduces the fuel supply and the engine stops.
13.7.6 Knocking
Knocking is a kind of explosion due to rapid pressure rise occurring in an IC engine. In a petrol
engine, a mixture of gasoline vapour and air (l: 17) is used as a fuel. The air and gasoline
vapours are compressed and ignited by an electric spark. The chemical reaction taking place is
the oxidation of hydrocarbons. The products of the oxidation reaction drives the piston down
the cylinder. If the combustion proceeds in a regular way, there is no problem of knocking. But
in certain circumstances, the oxidation is sudden and the mixture detonates and produces an
explosive sound called engine knock which results in the loss of power. Knocking not only
results in a decreased power output but can also cause mechanical damage by overheating of
the cylinder parts.
Agood gasoline should resist knocking. It was recognized that chemical structures of the
fuel hydrocarbons largely determine their knocking tendency. The tendency to knock decreases
in the following order:
straight chain paraffins> branched chain paraffins> cyclo-paraffins > olefins > aromatics.
Edgar introduced the octane number to express the knocking chracteristics of a
combustion engine fuel. It has been found that n-heptane knocks very badly and hence its antiknock value is arbitrarily given as zero. On the other hand, isooctane gives very little knocking
and so its anti-knock value has been given as 100. Thus, the octane number is defined as the
percentage of isooctane in the n-heptane-isooctane blend which has the same knocking
characteristics as the gasoline sample, under the same set of conditions. Since isooctane has
good anti-knock properties, it is clear that greater the octane number, greater is the resistance
to knocking.
Chemical structure and knocking: The knocking tendency decreases with increase in
compactness of the molecules, double bonds and cyclic structure. With normal paraffins, the antiknock properties decrease with the increase in length of the hydrocarbon chain. Thus, the octane
numbers of n-butane, n-pentane, n-hexane and n-heptane are 90, 60, 29 and 0 respectively.
Branched chain paraffins have higher anti-knock properties than their normal isomers.
Olefins have higher anti-knock properties than the corresponding paraffins. Aromatic hydrocarbons such as benzene and toluene have high octane numbers.
13.7.7 Leaded Petrol

The anti-knock properties of a gasoline can be improved by the addition of suitable additives.
Tetraethyl lead (TEL) is added to petrol and is called leaded petrol. This addition process is
called doping. This addition was first proposed by Thomas Midgley.
TEL reduces the knocking tendency of hydrocarbons. Knocking is a free radical
mechanism leading to a chain reaction which results in an explosion. If the chains are
208
terminated before their growth, knocking will cease. TEL decomposes thermally to form ethyl
free radicals which combine with the growing free radicals of the knocking process and thus
stop the chain growth.
When this leaded petrol is used as a fuel, lead and lead oxide vapours formed may
contaminate the atmosphere. To avoid this, ethylene dibromide is added along with TEL. This
ethylene dibromide reacts with Pb and PbO to give PbBr2 which will escape into the atmosphere.
CH 2 Br
Pb+
CH 2 Br
~ PbBr2 +CH 2 =CH 2
Improving the octane number of a fuel
The octane number of a fuel may be improved by the following:

1. The addition of anti-knock compounds like TEL.
2. Low octane petrol is blended with high octane compounds like alcohol, e.g. straight
run petrol is mixed with reformed petrol, benzol and alcohol.
3. Reforming.
13.7.8
Reforming
Reforming is a process used to improve the anti-knock characteristics of a gasoline by bringing

about structural modifications in the components of gasoline either thermally or in the presence
of catalyst. The main reactions in the reforming process are as follows:
1. Dehydrogenation
2. Hydrocracking
3. Isomerization
Dehydrogenation
-3H2
Cyclohexane
0
Benzene
Hydrocracking
CH3(CH2)gCH3
H21Pt
--=--~)
2CH3(CH2 hCH 3
n-decane
n-pentane
n-hexane
2-methylpentane
Isomerization
209
13.7,9 Diesel Oil

Diesel oil is a fraction obtained between 2S0-320C and is a mixture of C 1sH 32 and C 18H 38
hydrocarbons, Its calorific value is about 11000 kcal/kg. It is used as a diesel engine fuel.
Diesel knock
In a diesel engine, air is first drawn into the cylinder and compressed, This compression is
accompanied by a rise in temperature to about SOOC. Near the completion of the compression
stroke, oil is sprayed into the heated air, Droplets of the oil in the atomized form get vaporized
and ignited. This raises temperature as well as pressure, The piston is pushed by the expanding
gases and this constitutes a power stroke.
The combustion of a fuel in a diesel engine is not instantaneous and the interval between
the start of fuel injection and its ignition is called ignition delay and is an important quality of
the diesel fuel. This delay is due to the time taken for the vaporization of individual droplets
and raising of the vapour to its ignition temperature. Long ignition delays lead to accumulation
of more vapours in the engine and when ignited an explosion results as the combined effect of
increased temperature and pressure. This is responsible for diesel knock. In order to avoid diesel
knock, the ignition delay period should be as short as possible.
The cetane number decreases in the following order:
straight chain paraffins > cycloparaffins > olefins > brandied paraffins > aromatics
The diesel fuels are graded by means of cetane rating. Cetane, i.e. n-hexadecane
[CHJ(CH2)14CH3] having a very short ignition delay is given the value of 100 in the rating scale.
amethylnaphthalene having a longer ignition delay represents zero of the scale, The percentage
of cetane in the cetane-a-methylnaphthalene mixture which has the same ignition delay as the
fuel under test is the cetane number of the fuel.
High cetane number fuels eliminate diesel knock. The cetane number of a diesel fuel may
be increased by the addition of ethyl nitrite, amyl nitrite, etc. Table 13,6 compares diesel oil with
gasoline oil.
TABLE 13,6 Comparison of diesel oil and gasoline oil

Diesel oil
Gasoline oil
I. High boiling fraction of petroleum.
1. Low boiling fraction of petroleum.
2. It is cheaper.
3. Knocking tendency is measured in cetane

rating.
2. It is costlier.
3. Knocking tendency is measured in octane
rating.
4. Antiknocking is improved by the addition of

alkyl nitrites.
4. Antiknocking is improved by the addition of

TEL.
5. Its exhaust gases contain lesser amount of

pollutants.
5. Its exhaust gases contain higher amount of

pollutant gases.
6, Its combustion requires a more complex and

more expensive fuel injection device.
6. Its combustion requires

carburettor.
7. Fuel for compression ignition engine.
7. Fuel for spark ignition engine.
S. It contains C I5-C IS hydrocarbons.
8. It contains C S-C 9 hydrocarbons.
only a
simple
210
13.7.10
Diesel Index
According to American Petroleum Institute (API), the quality of a diesel fuel is indicated by
diesel index number. This is calculated from (a) aniline point and (b) specific gravity expressed
on API scale:
1.
b
specific gravity (API) X aniline point in OF
dlese mdex num er = - " - - - = - - " - - - - - - - - - " - - - - 100
The aniline point of an oil is defined as the temperature at which equal volumes of oil and
aniline are just miscible. The higher the diesel index number, the better is the quality of a fuel.
13.8
GASEOUS FUELS
The most important primary fuel is natural gas. The secondary fuels include producer gas, water
gas, coal gas, etc.
13.8.1
Natural Gas
Natural gas is obtained along with liquid petroleum in large amounts from oil producing wells.
It is also called marsh gas. Its main constituents are methane, ethane and other hydrocarbons.
If lower hydrocarbons like methane and ethane are present, the natural gas is called dry or lean.
If higher hydrocarbons are present along with methane, the natural gas is called rich or wet. The
average composition of natural gas is as follows:
Methane:
Ethane:
Propane:
Butane:
Pentane:
88.5%
5.5%
3.7%
1.8%
0.5%
The calorific value varies from 8000-14000 kcal/m 3

Uses of natural gas
The following are the uses of natural gas:

1. Natural gas is used as a domestic and industrial fuel.
2. It is used as a raw material for the synthesis of methanol and formaldehyde.
3. It can be used for the generation of electricity by using it in fuel cells.
13.8.2
Compressed Natural Gas (CNG)
CNG is produced by pressing natural gas up to 3600 psi in tanks. It is now used as a substitute
for petrol and diesel. The advantages are as follows:
1. Compared to petrol the octane rating of CNG is high. Higher octane rating allows
higher compression ratios and improved thermal efficiency.
2. The noise level of CNG is much lower than that of diesel.
211
3. CNG vehicle emit 40% less of nitrogen oxides (a toxic gas responsible for smog
fonnation), 90% less of hydrocarbons (carcinogens), 80% less of carbon monoxide
(poisonous pollutant) and 25% less of CO 2 (a major green house gas). Hence it is a safe
fuel.
Many countries like Argentina, USA, Italy, Australia and New Zealand are using CNG as
an automobile fuel. The conversion cost of vehicle to LPG may be lower compared to CNG but
the running cost of LPG is much higher.
The Supreme Court of India passed an order in July 1998 for converting all public
II3IlSport vehicles which are considered to be highly polluting to CNG mode in an effort to clean
the environment of Delhi. In Tamil Nadu, the government has taken initiatives to launch CNG
shortly in Chennai.
13,8,3 Liquefied Petroleum Gas (LPG)

LPG is obtained as a by-product during fractional distillation of crude oil or by cracking of
healY oil. It consists of light hydrocarbons like propane and butane which can be readily
liquefied under pressure but can exist as gases under atmospheric pressure.
The average composition of LPG is as follows:
Propane:
Butane:
Isobutane:
24.7%
38.5%
36.7%
Its calorific value is 25000 kcal/m 3 .
Uses: The uses of LPG are as follows:

I, LPG is used as a domestic and industrial fuel.
2. It is also used as a motor fuel.

As a fuel in IC engines, it has some advantages and drawbacks.
Advantages: The following are the advantages of LPG.

1. LPG is cheaper than gasoline.
2. It can easily mix with air.
3. LPG is highly knock-resistant.
Drawbacks: The drawbacks of LPG are given as follows:

1. LPG is difficult to handle.
2, LPG response to blending is very poor.
13,8.4 Producer Gas

Producer gas is a mixture of carbon monoxide, nitrogen and hydrogen. It is prepared by reacting
a mixture of air and steam over red hot coke placed in a steel furnace lined with refractory
bricks (Figure 13 .8).
212
Coke
~
__ Producer gas
V'r--"V'r--..v2~l)~~\")'~~~I-- Preheating zone
1~:~~~~~:~~~~-~~~:~i~l-- Reduction zone

~--:::-__-
Oxidation zone
Air + steam
Outlet for ash
Ash
FIGURE 13.8
Manufacture of producer gas.
The following reactions take place in the different zones of the coke bed.
I. Combustion or oxidation zone: Here the coke is oxidized to CO and CO2, Both the
reactions are exothermic. Hence, the temperature of the bed reaches around 1100C.
2. Reduction zone:
2C +
02~
2CO
C+
02~
CO2
This is the middle zone. Here CO2 and steam are reduced.
C+
C02~
2CO
C + H20 ~ CO + H2
Both the reactions are endothermic. Hence, the temperature of the fuel bed falls to
1000C.
3. Preheating zone: In this zone (400-800C), the incoming coke is heated by the
outgoing gases. In the upper part of the fuel bed, CO reacts with stearn.
CO + H 20 ~ CO2 + H2
The average composition of producer gas is as follows:
CO: 30%, N2: 51-56%, H 2: 10-15%, CO 2 : 3-6%, CH4 : 0.3-0.5%
Its calorific value is 1300 kcallm 3
Uses of producer gas
The following are the uses of producer gas:

1. Producer gas is used as a reducing agent in metallurgical operations.
2. It is also used for heating open-hearth furnaces, muffle furnaces, etc.
213
13.8.5 Water Gas

Water gas is a mixture of CO and H 2 . It is prepared by passing steam and a little air over red
hot coke. Water gas is also known as blue gas, because it bums with a blue flame due to the
combustion of CO (Figure 13.9).
Coke
_Watergas
Steam
Air blast ---.::::._---....--_---'
Outlet for ash
FIGURE 13.9
In the first step, air is passed through the coke bed to bum carbon to CO2 , This reaction
raises the temperature of the fuel bed to 11 OOC:
C
02~
CO2
In the second stage, steam is blown through the red hot coke and CO and H2 gases are
produced:
C + H20 ~ CO + H2
This reaction is endothennic and the temperature of the fuel bed falls below 1000C. In
order to maintain the temperature of fuel bed above 1000C, air and steam are passed
alternately. The duration for which steam is passed is called run period and the period for which
air is passed is called blow period.
The average composition of water gas is as follows:
CO: 41%, H 2 : 51%, N 2 : 4%, CO 2 : 4%
The calorific value of water gas is about 2800 kcal/m 3
Uses of water gas

The uses of water gas are as follows:
I. Water gas is used for the production of H2 and in the synthesis of ammonia.
2. It is used to synthesize gasoline in Fischer-Tropsch process.
3. Water gas is used in the manufacture of power alcohol.
4. It is used for the preparation of carburetted water gas.
214
13.9
COMBUSTION
Combustion is a process of rapid oxidation in which a fuel bums with the evolution of heat and
light. The rate of combustion depends upon (a) the nature of the fuel, (b) the temperature and
(c) the concentration of the fuel and air or oxygen. The combustion rate is thus increased by
(a) preheating the fuel and air, (b) increasing the surface area of the fuel and (c) increasing the
pressure of air or oxygen used for combustion.
The aim of combustion is to get the maximum amount of heat from a combustible material
in the shortest time and utilize the heat for various purposes. During combustion, a fuel may
undergo thermal decomposition to give simpler products which are oxidized to CO2, H20, etc.
All these reactions are exothermic and so a large quantity of heat is given out. During
coinbustion of coal, 70 per cent of heat is evolved by oxidation of C to CO 2 and 30 per cent
of heat is evolved by the combustion of volatile matter in the coal.
13.9.1
Explosive Range or Limits of Inflammability
Sufficient oxygen or air must be supplied for combustion of a fuel to take place. In the case
of solid and liquid fuels, even if excess of oxygen or air is supplied, the combustion will
proceed but a portion of heat is dissipated by flue gases. If oxygen or air is insufficient, partial
combustion will occur. But a gaseous fuel undergoes combustion on ignition only when its
concentration by volume in the fuel-air mixture is in between two percentage limits, the lower
and the higher combustion limits. The range covered by these limits is termed the explosive
range of the fuels. Only when the composition of the fuel-air mixture is within the explosive
range, the mixture is combustible and bums on ignition. If the composition is beyond the
explosive range, the mixture is not combustible and will not bum on ignition. For example, the
explosive range of sample of petrol is 2-4.5. This means that when the concentration of petrol
vapour in petrol-air mixture is between 2 and 4.5 by volume, the mixture will bum on ignition.
When the concentration of petrol vapour in petrol-air mixture is below 2 per cent (lower
combustion limit) or above 4.5 per cent (upper combustion limit) by volume, the mixture will
not bum on ignition. The explosive range thus decides the limit of the composition of the fuel
air mixture to be used for combustion purposes. Fire accidents may be caused by the escape of
inflammable gases into the air when the composition of the gas-air mixture falls within the
explosive range. Table 13.7 lists the explosive range of acetylene, hydrogen and natural gas.
TABLE 13.7 The explosive range of acetylene, hydrogen and natural gas
Acetylene
Hydrogen
Natural gas
13.9.2
Lower limit
Upper limit
3
4.1
5
74
80
14
Ignition Temperature
Every fuel requires heating to a definite temperature to start active combustion. This is known
as ignition temperature. It is defined as the minimum temperature at which the substance ignites
and bums without further addition of heat from outside.
215
The ignition temperature of coal is about 300C. In the case of liquid fuels, it is called
the flash point which ranges from 200-450C. For gaseous fuels, it is in the order of 800e.
13.9.3 Spontaneous Combustion

The basic cause for the spontaneous combustion of coal is oxidation. When coal is stored in a
place for a longer time, it undergoes slow oxidation. Oxidation of coal is an exothermic process
and the slow oxidation may produce sufficient heat to raise the temperature to the ignition
temperature. When this temperature is reached, coal starts burning by itself without the need of
an external flame. This phenomenon is called spontaneous combustion.
The chance of spontaneous combustion decreases with increasing maturity of the coal.
Therefore. lignite is more susceptible to spontaneous combustion than anthracite.
13.9.4 Flue Gas Analysis

The mixture of gases (mostly CO2 , CO and O 2) issuing out of the combustion chamber is called
flue gas. The analysis of a flue gas from a furnace or an exhaust gas from an engine would give
an idea about the efficiency of the combustion process.
The analysis of flue gases is carried out with the help of Orsat's Apparatus. It consists of
a horizontal tube. At one end of this tube, there is a three-way stop-cock and the other end is
connected with a burette.
The burette has graduations up to 100 cc and it is surrounded by a water jacket in order
to keep the burette at a uniform temperature. The burette is further connected by means of a
rubber tube to a separating funnel containing water. The level of water in the burette can be
raised or lowered by raising or lowering the separating funnel.
The horizontal tube is also connected with three different absorption bulbs A, Band C for
absorbing CO 2, O2 and CO. Bulb A contains KOH to absorb CO 2, bulb B contains alkaline
pyrogallol to absorb O2 and bulb C contains ammoniacal cuprous chloride to absorb CO
(Figure 13,10).
The whole apparatus is thoroughly cleaned, stoppers are greased and then tested for air
tightness. The absorption bulbs are filled with their respective solutions. Their stopcocks are
then closed. The three-way stopcock is opened to the atmosphere and the separating funnel is
raised till the burette is completely filled with water and the air is excluded from the burette.
The three-way stopcock is now connected to the flue gas supply and the flue gas is sucked into
the burette and the volume of flue gas is adjusted to 100 cc.
The stopper of the absorption bulb A containing KOH is opened and the gas is passed into
the bulb A by raising the level of water in the burette. The gas enters the bulb A and comes into
contact with KOH solution which absorbs CO 2 , The gas is again sent to the burette. This
process is repeated several times to ensure complete absorption of CO 2 , The decrease in volume
of the flue gas in the burette gives the volume of CO 2 in 100 cc of the flue gas. The volumes
of O2 and CO are similarly determined by passing the remaining gas through alkaline pyrogallol
and ammoniacal cuprous chloride respectively. The gas remaining in burette after the absorption
of CO2, O2 and CO is taken as nitrogen.
216
Gas burette
Flue gas
Separating
funnel
---=.--,
Fused calcium
chloride for
drying flue gas
Absorption bulb
(alkaline pyrogallol)
for oxygen - - - - - '
Absorption bulb
(ammonical --~
cuprous chloride)
for carbon monoxide
FIGURE 13.10
Orsat's apparatus.
Significance of flue gas analysis
1. If the flue gases contain considerable amount of CO, it indicates that incomplete
combustion is occurring and it also indicates the short supply of O2 for combustion.
2. If the flue gases contain considerable amount of O2, it indicates that the O2 supply is
very much in excess. In ordinary furnaces, 50-100 per cent excess air is generally
supplied. Too much of excess air results in the loss of heat.
So, by doing the flue gas analysis, we can increase or decrease the O2 supply.
13.9.5
Combustion Calculations
The amount (volume or weight) of oxygen and air required for the complete combustion ofa
given quantity of fuel can be calculated by taking the following points into consideration.
1. Substances always combine in definite proportions which are determined by their
molecular weights. Thus, for knowing the amount of oxygen required for the combus
tion of a fuel we must know its combustion reaction. For example. the combustion
reaction of carbon indicates that
C+02~C02
(by weight)
(by volume)
12
1
32
1
44
1
12 parts by weight of C require 32 parts by weight of O 2 and 44 parts by weight of

CO2 is produced by 12 parts by weight of C; (or) 1 volume of C requires 1 volume of
O2 and 1 volume of CO2 is produced by 1 volume of C.
217
The most commonly involved combustion reactions are as follows:

(a) 2H2 + O2 ~ 2H 20
orH2 + O~ H20
(b) S + O2 ~ S02
(c) 2CO + 02~ 2C02
or CO + 11202 ~ CO2
(d) CH4 + 202 ~ CO2 + 2H20
(e) C2H6 + 7/202 ~ 2C02 + 3H20
(f) C2H4 + 302 ~ 2C02 + 2H20
(g) C2H2 + 5/202 ~ 2C02 + H 20
N2, ash and CO2 (if any) present in the fuel or air are incombustible matters and hence
they do not take any O2 during combustion.
2. The total or theoretical amount of O 2 required by the fuel will be given by the sum of
the amounts of O2 required by the individual combustible constituent present in the
fuel. From this the net or minimum amount of O2 required is given by
net or minimum amount of O 2 required
= theoretical O 2 required - O 2 present in the fuel
3. Air contains 21 per cent of O2 by volume and 23 per cent of O 2 by weight. Hence, from
the amount of O2 required by the fuel the amount of air can be calculated:
100
x minimum O 2
23
minimum weight of air required = -
100
x minimum O 2
21
minimum volume of air required = -
4. Molecular mass of air is taken as 28.92(32 x 0.23 + 28 x 0.77
= 7.36 + 21.56 = 28.92).
5. 22.4 Htres or 22,400 cc of any gas at NTP (OC and 760 mm of Hg) has a mass equal
to its gram molecule. Thus, 22.4 Htres of CO2 at NTP will have a mass of 44 gram
because 44 is its molecular mass.
6. The volume (VI) of air/02 required at a particular temperature (TI ) and pressure (PI)
can be converted to some other volume (V2) at other temperature (T2) and pressure (P2)
using the following relationship.
~"1
P2V2
--=11
T2
SOLVED EXAMPLES
[umple 13.1: Calculate the gross and net calorific values of a coal sample having the
~llowing composition. C: 80 per cent, H 2: 7 per cent, O 2: 3 per cent, S: 3.5 per cent, N 2: 2.1
rer cent and ash 4.4 per cent.
218
Solution:
Gross calorific value (GCV)
= 1~0 [8080 x %C + 34500 ( %H = 1~O [8080 x 80 + 34500 (7 = 8080 x 0.80 + 345(7 -
o/~O) + 2240 x %S]
%) + 2240 x 3.5]
0.375) + 22.4 x 3.5
=6464 + 2285.6 + 78.4

=8828.0 kcal/kg
Net calorific value = GCV - (0.09H x 587)
=8828 -
(0.09 x 7 x 587)
= 8828 - 369.8
=8458.2 kcal/kg
Example 13.2: Calculate the minimum amount of air required for the complete combusrioo
of 100 kg of the fuel containing 80 per cent C, 6 per cent H 2, 5 per cent 02> 2 per cent Sand
the rest N2 by weight.
Solution:
1 kg of the fuel contains 0.8 kg ofC, 0.06 kg ofH 2, 0.05 kg of O2 and O.02~
of S.
C
12
+ O2
CO 2
44
H 2O
18
+ O2
S02
64
32
H2 +
2
S
32
16
32
12 kg of C requires 32 kg of 02'
0.8 kg of C requires
= 32 x 0.8 = 2.133 kg of 02
12
2 kg of H2 requires 16 kg of 02'
0.06 kg of H2 requires = 16 x 0.06 = 0.48 kg of O 2
2
32 kg of S requires 32 kg of 02'
0.02 kg of S requires = 32 x 0.02 = 0.02 kg of 02
32
N2 does not bum. Hence it does not consume any 02'
219
Theoretical O2 required for 1 kg of the fuel = 2.133 + 0.48 + 0.02 = 2.633 kg of O2

Net amount of O2 required for 1 kg of the fuel
= theoretical O2 required - O2 present in the fuel
= 2.633 - 0.05 = 2.583 kg of O2
Net amount of O2 required for 100 kg of the fuel = 2.583 x 100 = 258.3 kg
23 kg of O2 is supplied by 100 kg of air.

258.3 kg of O 2 is supplied by = 100 x 258.3 =1123 kg
23
The minimum amount of air required for the complete combustion of 100 kg of the fuel
=1123 kg.
Example 13.3: A coal sample was found to c:)ntain the following. C: 81 per cent, H 2 : 4
percent, 02: 2 per cent, N 2 : 1 per cent and the remaining being ash. Estim2te the quantity of
minimum air required for the complete combustion of 1 kg of coal sample if 40 per cent of
excess air is supplied.
Solution: 1 kg of the coal contains 0.81 kg of C, 0.04 kg of H2, 0.02 kg of O2 and
O.QI kg of N2
C
12
+ O2
H2 +
2
CO 2
44
H 20
18
32
0
16
12 kg of C requires 32 kg of O2,
0.81 kg of C requires = 32 x 0.81 = 2.155 kg of O 2
12
2 kg of H2 requires 16 kg of O2 ,
0.04 kg of H2 requires
= ~ x 0.04 = 0.32 kg of O2
2
N2 does not bum. Hence it does not consume any O2,

Theoretical 02 required for 1 kg of the fuel
= 2.155 + 0.32 = 2.475kg
Net amount of O 2 required for 1 kg of the fuel

= theoretical O 2 required - O2 present in the fuel
= 2.475 - 0.02 = 2.455 kg of O 2

2.455 kg of O 2 is supplied by = 100 x 2.455 = 10.67 kg
23
of O2
220
If 40 per cent excess air is used, amount of air required for the complete combustion of
1 kg of coal is
10.67 x 140 =14.94 k
100
g
Example 13.4: Calculate the minimum weight of air required for the complete combustion of
1 kg of coal having the following percentage composition by weight: C: 90%, H2: 3.5%,
S: 0.5%,2: 3%, N 2: 0.5% and ash 1.5%. Calculate the percentage composition by weight of
the dry products of combustion.
Solution: 1 kg of coal contains 0.9 kg of C, 0.035 kg of H2, 0.005 kg of S, 0.Q3 kg of

O2 and 0.005 kg of N 2.
C + O2
12
32
CO2
44
H2 +
2
16
H 2O
18
S02
64
S + O2
32
32
= 32 x 0.9 = 2.4 kg of 02
12
0.035 kg of H2 requires =
.!i
x 0.035 = 0.28 kg of 02
2
32 kg of S requires 32 kg of 02'
0.005 kg of S requires
= 32 x 0.005 =0.005 kg of O2
32

Theoretical O2 required for 1 kg of the fuel = 2.4 + 0.28 + 0.005
= 2.685 kg of O2
Net amount of O 2 required for 1 kg of the fuel
= theoretical O 2 required - O2 present in the fuel
= 2.685 - 0.03 = 2.655 kg of O 2
23 kg of O 2 is supplied by 100 kg of air.
2.655 kg of 02 is supplied by = 100 x 2.655 = 11.54 kg
23
221
Masses of the dry products of combustion

12 kg of C gives 44 kg of CO2.
0.9 kg of C gives = 44 x 0.9 =3.3 kg of CO 2
12
32 kg of S gives 64 kg of S02.
0.005 kg of S gives = 64 x 0.005 =0.01 kg of S02
32
Mass of N2
N2 present in the fuel + N2 present in the air
=0.005 + 11.54 x -77
100
= 0.005
=
+ 8.886
8.891 kg of N2
Total mass of combustion products = 3.3 + 0.01 + 8.891 = 12.2 kg

Percentage composition of the dry products of combustion
3.3
% of CO 2 = - - x 100
12.2
= 27.0%
0.01
% of S02 = - - x 100
12.2
= 0.08%
8.891
% ofN2 = - - x 100
12.2
= 72.9%
Example 13.5: A coal sample on analysis gives the following: C: 66.2%, H 2: 4.2%, S: 2.9%,
N2: 1.4%, 02: 6.1 % and ash 9.5%. Calculate the percentage composition of the dry products of
combustion if 1 kg of coal is burnt with 25% excess of air.
Solution: 1 kg of the coal contains 0.662 kg of C, 0.042 kg of H 2, 0.029 kg of S, 0.061

kg of O2 and 0.014 kg ofN2.
C + O2
12
32
CO2
44
H2 +
2
H 2O
18
S02
64
S
32
0
16
+ O2
32
222
= 32 x 0.662 =1.765 kg of 02
12
0.042 kg of H2 requires
= 16 x 0.042 = 0.336 kg of 02
2
32 kg of 8 requires 32 kg of 02'
0.029 kg of S requires = 32 x 0.029 = 0.029 kg of 02
32
Theoretical O2 required for 1 kg of the fuel
1.765 + 0.336 + 0.029
= 2.13 kg of O 2
Net amount of O2 required for 1 kg of the fuel

= theoretical O2 required - O2 present in the fuel
= 2.13 - 0.061 = 2.069 kg of O2

2.069 kg of 02 is supplied by = 100 x 2.069 = 9.0 kg
23
If 25% excess air is used, the amount of air required for the complete combustion of I kg
of coal is
9.0 x 125 =11.25 kg
100
Masses of the dry products of combustion

12 kg of C gives 44 kg of CO 2,
0.662 kg of C gives
= 44 x 0.662 = 2.4 kg of CO 2
12
32 kg of 8 gives 64 kg of 802'
0.029 kg of S gives
= 64 x 0.029 = 0.058 kg of S02

32
Mass of N2 = N2 present in the fuel + N2 present in the air

= 0.014
77
+ -
= 0.014 +
100
R hh
x 11.25
223
~----------~-------------------------
= 8.674 kg of N2
23
Mass of O2 = (11.25 - 9.0) x 100 = 0.5 kg
Total mass of combustion products = 2.4 + 0.058 + 8.674 + 0.5 =11.632 kg
Percentage composition of the dry products of combustion

2.4
% of CO2 = - - x 100
11.632
= 20.6%
% of S02 = 0.058 x 100
11.632
= 0.5%
0.5
% of O2 = --x100
11.632
= 4.3%
8.674
% ofN2 = - - x 100
11.632
= 74.6%
Example 13.6: Calculate the minimum volume of air required for the complete combustion
of I m) of a gaseous fuel of the following composition by volume. CO: 23%, H2: 12%, CH4 :
3%, CO2: 5%, N2: 55% and O2: 2%.
I m3 of the fuel contains 0.23 m3 of CO, 0.12 m 3 of H2, 0.03 m3 of CH 4 ,
0.05 m) of CO2, 0.55 m3 of N2 and 0.02 m3 of O 2,
Solution:
CO + 11202
1 vol
0.5 vol
H2 + 11202
1 vol
0.5 vol
CH 4 + 20 2
1 vol
2 vol
CO2
1 vol
H 2O
1 vol
CO2 + 2H 2O
1 vol
I volume of CO requires 0.5 volume of O 2,

0.23 volume of CO requires = 0.5 x 0.23 = 0.115 m 3 of O 2
1
I volume of H2 requires 0.5 volume of O2 ,
0.12 volume of H2 requires = 0.5 x 0.12 = 0.06 m 3 of O 2
1
224
1 volume of CH4 requires 2 volume of 02'

0.03 volume of CH 4 requires
= ~ x 0.03 =0.06 m3 of O2
1
Theoretical volume of O2 required = 0.115 + 0.06 + 0.06 = 0.235 m3 of O2

Net volume of O2 required for the complete combustion of 1 m3 of the fuel
theoretical volume of O2 required - O2 present in the fuel
= 0.235 - 0.02 = 0.215 m3
21 m3 of O2 is supplied by 100 m3 of air.

0.215 m 3 of O 2 is supplied by = 100 x 0.215 =1.02 m3
21
The volume of air required for the complete combustion of 1 m3 of a fuel = 1.02 mJ.
Example 13.7: The composition of a producer gas was found to be CO: 22%, H2: 14%, CH 4:
2%, CO2: 5%, N 2: 55% and 02: 2% by volume. Find the air required for perfect combustion
of 1 m3 of this gas. If 40% excess air is used, find the volume analysis of the dry products of
combustion.
Solution: 1 m3 of the fuel contains 0.22 m3 of CO, 0.14 m3 of H2, 0.02 m3 of CH4
0.05 m3 of COz, 0.55 m3 of N2 and 0.02 m3 of 02'
CO + 1/202
1 vol
0.5 vol
CO2
1 vol
H 2O
1 vol
H2 + 11202
1 vol
0.5 vol
CH 4 +
1 vol
20 2
2 vol
CO2 + 2H2O
1 vol
1 volume of CO requires 0.5 volume of 02'

0.22 volume of CO requires
= 0.5 x 0.22 =0.11 m3 of O 2

1
1 volume of H2 requires 0.5 volume of 02'

0.14 volume ofH2 requires = 0.5 x 0.14 = 0.07 m3 of O 2
1
1 volume of C~ requires 2 volume of 02'

0.02 volume of CH 4 requires = ~ x 0.02 =0.04 m3 of O 2
1
Theoretical volume of O2 required = 0.11 + 0.07 + 0.04
=
0.22 m3 of O2
225
Net volume of O 2 required for the complete combustion of I m 3 of the fuel

= theoretical volume of O2 required - O2 present in the fuel
= 0.22 - 0.02 = 0.2 m 3
21 m3 of O2 is supplied by 100 m 3 of air.

0.2 m 3 of O 2 is supplied by = 100 x 0.2 =0.95 m 3
21
If 40% excess air is used, the volume of air required for the complete combustion of 1 m 3
of the fuel is
0.95 x 140 = 1.33 m3
100
Volumes of dry products of combustion

Volume of CO2 produced = volume of CO2 present in the fuel
+ volume of CH4 x 1 + volume of CO x 1
= 0.05
+ 0.02 x 1 + 0.22 x 1
= 0.29 m 3
Volume of N2 produced = N2 present in the fuel + N2 present in air

= 0.55
79
+ 1.33 x 100
= 0.55 +
= 1.60
1.05
m 3.
21
Volume of O2 produced = (1.33 - 0.95) x 100
= 0.08 m 3
Total volume of dry products of combustion = 0.29 + 1.6 + 0.08 = 1.97 m 3
Percentage composition of dry products of combustion
% of CO2
0.29
--xl00
1.97
= 14.72%
1.6
% of N2 = - - x 100
1.97
= 81.22%
0.08
% of O 2 = - - x 100
1.97
= 4.06%
226
Example 13.8: Calculate the weight and volume of air required for the complete combustion
of 1 kg of coke.
Solution:
C +
02~
CO2
12 kg of C requires 32 kg of 02.
1 kg of coke requires = 32 xl = 2.67 kg of O 2
12
23 kg of O 2 is supplied by 100 kg of air.
2.67 kg of O 2 is supplied by = 100 x 2.67 = 11.6 kg
23
32 kg of O 2 occupies 22.4 m 3 at NTP.
2.67 kg of O 2 occupies
= 22.4 x 2.67 =1.87 Ill 3 at NTP

32
21 m 3 of O 2 is supplied by 100 m 3 of air.

1.87 Ill 3 of 02 is supplied by = 100 x 1.87 = 8.9 Ill 3
21
Weight of air required for the combustion of 1 kg of coke = 11.6 kg
Volume of air required for the combustion of 1 kg of coke
8.9 m3
Example 13.9: A fuel has the following composition by volume. co: 6%, H2: 22%, CH4:
30%, C 2H 6 : 11%, C 2H 4 : 4.5%, C 4 Hg: 2.5%, CO2: 8%, N 2: 12% and 02: 2%. Calculate the
theoretical volume of air required at 25C and 750' mm pressure for complete combustion of
1 m3 of fuel.
1 m 3 of fuel gas contains 0.06 m 3 of CO, 0.22 m 3 of H2, OJ m3 of CH 4
0.11 m of C 2H 6 , 0.045 m3 of C 2H 4 , 0.025 m3 of C 4Hg, 0.08 m 3 of CO2, 0.12 m3 of N2 and
0.02 m 3 of 02.
Solution:
3
CO
1 vol
11202
0.5 vol
CO2
1 vol
H2
1 vol
11202
0.5 vol
H 2O
1 vol
CH 4
1 vol
20 2
2 vol
C2H 6 + 7/20 2
1 vol
3.5 vol
C 2H 4
1 vol
30 2
3 vol
CO2 + 2H 2O
1 vol
2C0 2 + 3H2O
2 vol
2C02 + 2H2O
2 vol
227
60 2
6 vol
1 volume of CO requires 0.5 volume of O2,
0.06 volume of CO requires
= 0.5 x 0.06 = 0.03 m 3 of O 2

1
1 volume of H2 requires 0.5 volume of 02'

0.22 volume of H2 requires
= 0.5 x 0.22 = 0.11 m3 of O 2

1
1 volume of CH4 requires 2 volume of 02'

0.3 volume of CH 4 requires
= ~ x 0.3 =0.6 m 3 of O 2
1
1 volume of C2H6 requires 3.5 volume of 02'

0.11 volume of C 2H 6 requires
= 3.5 x 0.11 = 0.385 m 3 of O 2

1
I volume of C2H4 requires 3 volume of 02'
0.045 volume of C 2H 4 requires
=i
x 0.045 = 0.135 m 3 of 02
I volume of C4 H 8 requires 6 volume of O2,

0.025 volume of C 4 Hg requires
= ~1 x 0.025 =0.15 m 3 of 02
Theoretical volume of O2 required = 0.03 + 0.11 + 0.6 + 0.385 + O. I 35 + O. I 5

= 1.41 m3 of O2
Net volume of O2 required for the complete combustion of 1 m 3 of the fuel
= theoretical
volume of O2 required - O2 present in the fuel

= 1.41 - 0.02 = 1.39 m 3
This is the volume of0 2 at NTP (760 mm pressure and 273 K). The corresponding volume
of O2 at 25C and 750 mm pressure can be calculated by using the gas equation
11"1
2
- =PzV
-Ii
= 760
mm
VI = 1.39 m 3
T\ = 273 K
PI
T2
P2
= 750
mm
V2 =?
T2 = 273 + 25 = 298 K
760 x 1.39 _ 750 x V2

273
298
228
Engineering C'
v _ 760 x 1.39 x 298

750x 273
2 -
1.54 m3
21 m3 of O2 is supplied by 100 m3 of air.

1.54 m3 of O 2 is supplied by = 100 x 1.54 = 7.33 m 3 of air
21
Theoretical volume of air required at 25C and 750 mm pressure for complete combustion
of 1 m3 of fuel = 7.33 m3
( SHORT QUESTIONS)
1. Define gross calorific value and net calorific value.
2. Define the octane number. How is the quality of gasoline improved?

3. Define the cetane number. How is the quality of diesel improved?
4. What is metallurgical coke? How does it differ from coal and charcoal?
5. What is reforming?
6. The net calorific value of a fuel is lower than its gross calorific value. Why?
7. What are the advantages of solid fuels over liquid fuels?
8.
9.
10.
11.
Explain the term leaded petrol.

What do you understand by the term explosive range?
What is knocking of petrol? Name an anti-knock additive and explain how it functions.
What is petroleum? How is it classified?
12. Mention one important difference between the proximate and ultimate analysis of coal.
13. Name the reagents used for absorbing CO and O2 during flue gas analysis using Orsat's
apparatus?
14. What is meant by refining of petroleum?
15. Name the different varieties of coal.
16. Distinguish between LTC and HTC.
17. Which has higher octane number, natural gasoline or cracked gasoline. Why?
1. Compare solid, liquid and gaseous fuels.
2. What is proximate analysis of coal? How is it done? How does it vary with the age of
coal?
229
3. What is ultimate analysis of coal? Discuss its significance. How does it vary with the type
of coal?
4. What are the properties of metallurgical coke? How is it manufactured from coal?
5. Describe briefly the refining of petroleum, indicating the principle involved, name the
fractions obtained and state one important use of each fraction.
6. How are cracked and polymer gasolines obtained? How do they differ from straight-run
gasoline?
7. What do you mean by the term 'carbonization of coal'? Give a comparative account of
the two types of carbonization commonly employed.
8. Describe briefly (a) Bergius process and (b) Fischer-Tropsch process.
9. Write about different varieties of coal.
10. Write notes on (a) natural gas, (b) water gas (c) producer gas.
II. Distinguish between
(a)
(b)
(c)
(d)
Gross and net calorific value

Octane number and cetane number
Polymer gasoline and straight-run gasoline
Gasoline and diesel oil
12. Write briefly on synthetic petrol.

13. Write short notes on (a) petrol knock and diesel knock and (b) desulphurization of
gasoline.
14. How is knocking related to the chemical structure of the constituents of petrol?
15. Describe the determination of flue gas analysis and discuss its significance.
16. What are the differences between thermal and catalytic cracking methods?
17. What is meant by cracking? What are the advantages of catalytic cracking? Discuss in
detail fixed bed and moving bed catalytic cracking.
18. Give the composition of natural gas, water gas and producer gas. Arrange them in
ascending order of calorific value.
( PROBLEMS )
1. Calculate the gross calorific value and net calorific value of a coal sample having the
following composition: C = 80%, f{ = 7%, 0 = 3%, S = 3.5%, N = 2.1 % and ash = 4.4%.
(Ans. 8828 cal/g, 8458 cal/g)
2. A coal has the following ultimate analysis data: C = 84%, S = 1.5%, N = 0.6%, H = 5.5%
and 0 = 8.4%. Find the gross and net calorific values with the help of Dulong's formula.
(Ans. 8356 cat/g, 8065 cal/g)
230
3. Find the gross as well as net calorific value of a coal which on ultimate analysis gave the
following result: C = 70.3%, H = 5.1%, 0 = 22.4%, S = 0.8% and N = 1.4%.
(Ans. 6491 cal/g, 6222 caVg)
4. On analysis, an oil was found to have the following percentage composition: C = 48%,
H = 12% and 0 = 4%. Calculate the weight of air required for the complete burning of
1 kg of this oil.
(Ans. 9.57 kg)
5. A sample of petrol was found to contain 15.4% hydrogen and 84.6% carbon by weight
Calculate the weight and volume of air required for the complete combustion of 1 kg of
this fuel.
(Ans. 15.17 kg, 11.74 ml)
6. Calculate the volume of air required for the complete combustion of I m3 of the gaseous
fuel having the following composition by volume: H = 50%, CH4 = 36%, N = 1.5%, CO
= 6%, C 2H 4 = 4% and water vapour = 2.5%.
(Ans. 5.33 ml)
7. Calculate the volume of air at STP needed for the complete combustion of 1 kg of
methane.
(Ans. 13.33 ml)
8. A sample of coal was found to have the following percentage composition: C = 75%,
H = 5.2%, 0 = 12.8%, S = 1.2%, N = 3.7%, ash = 2.1 %. Calculate the minimum amount
of air necessary for complete combustion.
(Ans. 10.0 kg)
9. An oil on analysis gave the following results by weight: C = 86%, H = 11.75% and
o = 2.25%. Find the minimum amount of air required for burning 1 kg of the fuel.
(Ans. 14.06 kg)
10. A sample of coal was found to contain the following: C = 81 %, H = 4%, 0 = 2%,
N = 10%, the remaining being ash. Estimate the quantity of minimum air required for
complete combustion of 1 kg of the sample. Find the composition of dry flue gas by
weight, if 40% excess air is supplied.
(Ans. 10.7 kg, CO2 = 19.06%,
N2 =
74.65%, O2 = 6.29%)
11. A gaseous fuel has the following composition by volume: H = 40%, CH4 = 40%,
C 2H 6 = 6%, CO = 6% and N = 8%. Calculate the volume of air required for the
combustion of 1 m 3 of the fuel, if 20% excess air is supplied. Find out the percentage
composition by volume of the dry products of combustion.
(Ans. 6.05 m 3, CO 2 = 8.73%,
N2 =
87.45%, O2 = 3.82%)
12. Calculate the minimum weight and volume of air required for the complete combus
tion of 1 kg of coal having the following percentage composition by weight: C = 90%,
H = 3.5%, 0 = 3.0%, S = 0.5%, N = 0.5% and ash = 2.5%. Also calculate the
231
percentage composition by weight of the dry products of combustion if 25% excess

air is supplied.
(Ans. 11.54 kg, 8.93 m 3, CO2 = 21.86%, S02 = 0.07%,
N2 = 73.67% and O 2 = 4.41%)
13. 100 kg of a liquid hydrocarbon fuel containing 89.4 kg carbon by weight is burnt with
(a) theoretical amount of air and (b) 20% excess of the theoretically required amount of
air. Calculate the volumetric composition of the products in each case.
(Ans. 1036.52 kg, 1243.5 kg, CO2 = 17.27%, N2 = 79.28% and O 2 = 3.45%)
14. 1000 m3 of a producer gas having the volumetric composition CO = 22%, CO2 = 4%,
CH4 = 2%, H2 = 14%, N2 = 56%, O 2 = 2% has to be burnt for heating a furnace.
(a) Calculate the minimum quantity of air required for the complete combustion and
(b) If 40% excess air is used, what is the volumetric composition of dry flue gas?
(Ans. 952.38 m 3 , CO2 = 14.19%, N2 = 81.76% and O 2 = 4.05%)
15. A gaseous fuel has the following composition: H2 = 50%, CH 4 = 30%, C 2H6 = 6%,
CO = 8%, N2 = 6%. Calculate the volume of air required per cubic metre of the gas. Also
find out the percentage composition by volume of the dry products of combustion, if 20%
excess air is supplied.
(Ans. 5.24 m 3 , CO2 = 8.7%, N2 = 87.47% and O 2 = 3.83%)
16. The percentage composition of a sample of anthracite coal was found by weight to be
C =90, H = 3.3, 0 = 3.0, N = 0.8, S = 0.9 and ash 2.0. Calculate the minimum weight
of air required for the complete combustion of 1 kg of this fuel. If 50% excess of air is
supplied, find the percentage composition of the dry flue gases by weight.
(Ans. 11.49 kg, CO 2 = 18.31%, N2 = 74.12% and O 2 = 7.47%, S02 = 0.1%)
17. A sample of coal was found to contain the following, C = 81 %, H = 4%, 0 = 2%,
N= 10%, S = 2% and the remaining being ash. Estimate the quantity of minimum air
required for the complete combustion of 1 kg of the sample. Find the composition of dry
flue gas by weight, if 40% excess air is supplied.
(Ans. 10.78 kg, CO2 = 18.89%, N2
= 74.55%
and O 2 = 6.31%, S02
= 0.25%)
PHASE RULE
14.1
INTRODUCTION
When two or more different phases exist in equilibrium with each other then it is called a poly
phase or heterogeneous equilibrium.
CaC03(s)
CaO(s) + CO2(g)
Such a system can be conveniently studied with the help of a generalization called phase rule.
With the help of phase rule it has been possible to predict, qualitatively by means of a diagram.
the effect of changing temperature, pressure and concentration on a heterogeneous system in
equilibrium.
Phase rule is a generalization put forward by Gibbs which explains the equilibrium
existing in heterogeneous systems. It states that the equilibrium between different phases is
influenced only by temperature, pressure and concentration. Then, the number of degrees of
freedom (F) is related to the number of components (C) and phases (P) by the phase rule
equation, i.e.
F=C-P+2
14.2
PHASE
A phase is a homogeneous physically distinct and mechanically separable portion of a system

which is separated from other parts of the system by definite boundaries.
1. Gaseous phase: All gases are completely miscible. Therefore, a gaseous mixture
irrespective of the number of gases present will constitute a single phase. In a gaseoill
mixture, there is no boundary between one gas and the other. Air, which is a mixturf
of N" 0" CO" water vapour, etc., constitutes a single phase.
232
Phase Rule
233
2. Liquid phase:
The number of liquid phases depends upon the number of liquids

present and their mutual solubilities.
Two or more liquids which are miscible with each other constitute a single phase as
there is no bounding surface separating the two different liquids, e.g. alcohol-water
mixture. As there will be vapour in contact with liquid, there will be two phases (liquid
and gas) in miscible liquids.
The two immiscible liquids like benzene and water consist of two distinct liquid phases.
In addition to this there will be one more distinct phase, i.e. vapour phase. It means that
there will be three phases in the case of immiscible liquids.
3. Solid phase:
equilibrium
Every solid constitutes a separate phase, e.g. a heterogeneous
CaC03(s)
CaO(s) + CO2(g)
involves three phases, solid CaC03, solid CaO and gaseous CO2, Thus, there are three
phases-two solids and one gaseous.
Each allotropic form of a solid is regarded as a separate phase, e.g. a mixture of rhombic
sulphur and monoclinic sulphur will constitute two phases because they possess different chemical structures though they are having same chemical formula. A solid solution, irrespective of
the number of solids present is a single phase system.
Mohr's salt [FeS04' (NH4)2S04' 6H 20] constitutes a single phase. The reason is that
FeSOdNH4)2S04 and water form one homogeneous mixture of one colour and it is not possible to separate the crystals of FeS04 from (NH4)2S04'
14.3 COMPONENT
The number of components of a system at equilibrium is the smallest number of independently
variable constituents by means of which the composition of each phase present can be expressed
either directly or in the form of a chemical equation. While expressing the composition of phase
in tenns of the components, zero and negative quantities of the components are permissible. For
example:
I. Consider a water system consisting of three phases.
Ice(s)
Water(l)
Vapour(g)
It is a one component system as each phase is a different physical form of the same
chemical compound represented by H 20.
2. Consider a sulphur system consisting of four phases-rhombic, monoclinic, liquid and

vapour. It is a one component system as the composition of each phase can be
expressed in terms of sulphur only.
3. CaC0 3(s)
CaO(s) + CO2(g)
The system involves three phases. It is a two-component system because the

composition of each of the above phases can be expressed in terms of any two of the
three components present.
234
When CaO and CO2 are considered as components:

Phase
Components
CaC03
CaO
CO 2
CaO + CO 2
CaO + DC02
CO 2 + DCaO
4. MgC03(s) ~ MgO(s) + CO2(g)

It is also a two-component system.
5. An aqueous solution of sodium chloride is a two-component system. The constituents
are NaCI and H 20 and both are necessary to describe the composition of solution
phase.
Unsaturated solution of NaCI in water is a two-phase and two-component system
whereas saturated solution of NaCI in water is a three-phase and two-component
system.
6. In the sodium sulphate-water system, the various phases that may exist are Na2S04,
Na2S047H20, Na2S04'lOH20, solution and vapour. It is a two-component system
because the composition of each phase can be expressed in terms of Na2S04 and H20:
Phase
Components
Na2S04 + DH 20
Na2S04 + 7H20
Na2S04 + IDH 20
Na2S04 + xH 20
DNa2S04 + H 20
Na2S04
Na2S04'7H20
Na2S04'lOH20
Na2S04 solution
H 20 vapour
PCI3(l) + CI2(g)
The system has three phases, but the number of components is only two.
7. PCls(s)
8. CuS04'SH20(S)
CuS04'3H20(S) + 2H20(g)
It is also a two-component system.
9. In the dissociation of ammonium chloride in vacuum, the following equilibrium occurs.

NH4CI(s)
NH3(g) + HCI(g)
The system consists of two phases, viz. solid NH4CI and the homogeneous gaseous
mixture consisting of NH3 and HCl. The system will be one component or two
component depending upon the relative quantities of HCI and NH3 formed. When NHJ
and HCI are present in equivalent quantities the composition of both the phases can be
represented by the same chemical compound NH4CI and the system will be a one
component system.
Phase
Components
Phase Rule
235
Ifa small amount ofNH3 or Hel is added to the equilibrium mixture, then the number
of components will become two.
14.4 DEGREES OF FREEDOM

The number of degrees of freedom of a system is defined as the number of variable factors such
as temperature, pressure and concentration which should be fixed in order to define the system
completely. A system having 1, 2, 3 or 0 degrees of freedom is called univariant, bivariant,
trivariant and nonvariant or invariant respectively.
14.5 PHASE DIAGRAMS

Adiagram which illustrates the conditions of equilibrium between various phases of a substance
a phase diagram. The phase diagram is a graphical representation obtained by plotting
one degree of freedom against another. If the temperature (T) is plotted against pressure (P), the
diagram is called P-T diagram. If the temperature (T) is plotted against composition (C), the
diagram is called T-C diagram. The study of a phase diagram is vital for proper understanding
of the relative stability of equilibrium between phases. From a knowledge of the number of
phases and components of the system, phase rule enables one to predict the conditions under
which a system can remain in equilibrium.
~ called
14.6 APPLICATION OF PHASE RULE TO ONE-COMPONENT SYSTEMS

14.6.1 Water System
Water can exist in three possible phases namely solid, liquid and vapour. Hence, there can be
three forms of equilibria.
solid
liquid, liquid
vapour, solid
vapour
Each equilibrium involves two phases. The phase diagram for the water system is shown
in Figure 14.1.
The diagram contains areas, lines or curves and triple point.
Areas
Area AOC represents the conditions for the water phase system. Area AOB represents the
conditions for the water vapour system. Area BOC represents the conditions for the ice system.
In order to define the system at any point in the areas, it is essential to specifY both the
temperature and pressure. Thus, the areas have two degrees of freedom and are called bivariant
systems. The same conclusion may be arrived by the phase rule also.
F=C-P+2
=1-1+2=2
236
----~----------------------------------------------
C
Water
b,
,
,,
c----- '----- y
'X
,,
,,
z
Ice
4.58 mm
Vapour
B
O.0075C
Temperature
FIGURE 14.1
Phase diagram of water system.
Lines or curves
The curve OA represents the equilibrium between water and vapour at different temperatures.
It is called vaporization curve of water. The curve OB represents the equilibrium between ice
and vapour and it is called sublimation curve of ice. The curve OC represents the equilibrium
between ice and water and it is called melting point curve. To define the system completely only
one of the two variables, viz. temperature or pressure has to be specified since the other variable
can be read from the graph. Thus, the degree of freedom of the system is one and the system
is univariant. It is predicted by the phase rule.
F=C-P+2
=1-2+2=1
Triple point
The three curves OA, OB and OC meet at a point 0 which is known as triple point. At this point
all the three phases namely ice, water and vapour are in equilibrium with one another. Applying
phase rule to this point,
F=C-P+2
=1-3+2=0
Thus, the degree of freedom of this point is zero. It means that three phases can coexist in
equilibrium only at a definite temperature and pressure. The values of pressure and temperature
at point 0 are 4.58 mm and 0.0075C respectively.
Significance of areas between the lines
The state of equilibrium is represented by a point x on the line ~A. The two phases in contact
are liquid and vapour. If the temperature is kept constant and the pressure is increased the
Phase Rule
237
vapour will be compressed into liquid. This change is represented by the dotted line xb in the
figure. Similarly, if pressure is kept constant and temperature is decreased the vapour will
change into liquid. This change is represented by the dotted line xc. Thus, the area above the
curve OA represents exclusively the liquid phase.
If the pressure is maintained constant and the temperature is increased, the liquid will
completely change into vapour. This change is represented by the dotted line xy. Similarly, if
the temperature is kept constant and the pressure is decreased, liquid will be converted into
vapour as represented by the dotted line xz. Thus, the area below the curve OA represents the
vapour phase only.
14.7 TWO-COMPONENT SYSTEMS

The maximum number of degrees of freedom in a two-component system will be three when
the system exists as a single phase, e.g. a mixture of any two gases. There will be two components present in one phase.
F=C-P+2=2-1+2=3
In addition to temperature and pressure, therefore, a third variable namely composition is
be taken into account. In order to represent the conditions of equilibrium graphically, it is
necessary to have three coordinates. This will lead to three dimensional figures which cannot
be conveniently represented on paper. Therefore, any two of the three variables are chosen for
graphical representation, assuming the third to be constant.
A solid-liquid equilibrium of an alloy has practically no gas phase and the effect of
pressure is small on this type of equilibrium. Therefore experiments are usually conducted
under atmospheric pressure. A system in which only the solid and liquid phases are considered and the gas phase is ignored is called a condensed system. Since the pressure is kept
constant, it will reduce the degrees of freedom of the system by one. Now the phase rule
becomes
~so
F=C-P+l
This is known as reduced or condensed phase rule having two variables namely temperature and
concentration or composition of the constituents.
14.8 BINARY ALLOY SYSTEM OR SIMPLE EUTECTIC SYSTEM

Abinary system consisting of two substances which are miscible in all proportions in liquid
phases but which do not react chemically is known as eutectic system, e.g. a mixture of lead
and silver.
14.8.1 Lead-Silver System

The lead-silver system consists of the following four phases taking part in the equilibriumsolid lead, solid silver, solution of silver and lead and vapour.
238
Since the system is studied at constant pressure, the vapour phase can be ignored and the
condensed phase rule is used, i.e.
F=C-P+1
The phase diagram of lead and silver is shown in Figure 14.2.
Liquid
961C A 1 - - - - -_ _
a
I
I
I
I
I
I
832rC
! Solid lead + liquid

303~-------------------------------*----~
Eutectic
Eutectic + Solid silver
100%A
Composition
Solid lead
2.6% Ag
100% B
+
97.4% Pb
FIGURE 14.2
Phase diagram of lead-silver system.
In this diagram, point A represents the melting point of pure silver and point B that of pure
lead. It can be seen from the diagram that addition of Pb to pure Ag lowers the melting point
of Ag. Similarly, addition of Ag to pure Pb lowers the melting point of Pb. All the points on
the curves AO and BO represent the melting points of various mixtures of Ag and Pb. AO
represents the melting point curve of silver and shows the effect of addition of Pb on the melting
point of pure Ag. Similarly, curve BO represents the melting point curve of Pb and shows the
effect of addition of Ag on the melting point of Pb. All along AO, solid Ag and liquid are in
equilibrium while along BO solid Pb and liquid are in equilibrium. Hence, AO and BO both
represent univariant systems.
F=C-P+1=2-2+1=1
In the area above AOB, there is only one phase (liquid solution). Applying reduced phase
rule equation
F=C-P+1=2-1+1=2
Both the temperature and composition have to be specified to define the system
completely.
The area below AO represents the phases solid Ag + solution while that below OB the
phases are solid Pb + solution. All these areas have two phases and one degree of freedom.
F=2-2+1=1
Phase Rule
239
The curves AO and EO intersect at point 0 at a temperature of 303C. The point 0 is called
temperature or eutectic point and it corresponds to the composition 2.6 per cent Ag
+97.4 per cent Pb. This is called the eutectic composition and its melting point is lower than
any alloy of Ag and Pb. The number of phases at this point is 3 (solid silver, solid lead and
~euJectic
solution). Applying the reduced phase rule equation to this point,
F=C-P+I=2-3+1=0
So the system at the point 0 has no degree of freedom. It is invariant. This means that
the system consisting of two solids and liquid solution can exist only at definite temperature and
definite composition.
14.8.2 Applications of the Phase Diagram of Two-Component System or Pattinson's Process

for the Desilverization of Argentiferous Lead
The phase diagram of Pb-Ag system has a special significance in connection with the
desilverization of lead. The argentiferous lead consisting of a very small percentage of silver is
first heated to a temperature above its melting point so that the system consists of only the liquid
phase represented by the point a in Figure 14.2. It is then allowed to cool. The temperature of
the melt will fall along the line abo As soon as the point b is reached lead will begin to
crystallize out and the solution will contain relatively increasing amounts of silver. Further
cooling will shift the system along the line EO. Lead continues to separate out and it is
constantly removed. The melt continues to be richer and richer in silver until the point 0 is
reached where the percentage of silver rises to 2.6. Thus, the original argentiferous lead which
might have contained 0.1 per cent of silver can now contain up to 2.6 per cent of silver. The
process of raising the relative proportion of silver in the alloy is known as Pattinson s process.
This is treated for the recovery of silver profitably.
Characteristics of eutectic point:
The characteristics of the eutectic point are as follows:
I. The eutectic point is an invariant point marked by specific temperature and

composition.
2. It is the lowest melting point of any mixture of silver and lead.
3. If the liquid is cooled below the eutectic point, both the components of the eutectic
simultaneously solidify without any change in the composition or temperature of the
liquid phase.
4. Recent electron microscopic studies show that eutectics are mixtures of the components
but not their compounds.
5. An eutectic system can maintain its temperature constant over long periods.
Uses of eutectic system:
The uses of the eutectic system are as follows:
I. Eutectic systems are used in preparing solders, used for joining two metal pieces
together, e.g. lead-tin solders.
2. Suitable alloy composition can be predicted with the use of eutectic systems.
Differences among melting point, triple point and eutectic point: At the melting point, a
solid and a liquid having the same composition are in equilibri~m. At the triple point, three
240
phases are in equilibrium. At the eutectic point, two solids and a liquid are in equilibrium. By
definition, all eutectic points are melting points, but all melting points need not be eutectic
points. Similarly, all eutectic points are triple points, but all triple points need not be eutectic
points.
14.9
THERMAL ANALYSIS
The construction of phase diagrams from the cooling curves is called thermal analysis. The
phase diagrams are drawn from thermal analysis data, i.e. from temperature-time cooling curves
for the pure metals (silver and lead) and for the various compositions of the two components
(Figure 14.3).
----- ---
I
--------- --- ------r--
\B __________ ~---~---- __________
_~_ ____ _ ____ L __ ~--_-__

_____________
Time
------1--- ... - - - - - - - -
100% A
_ ___ _
Composition
__
I
I
100%8
FIGURE 14.3 Cooling curves for different compositions in a two-component system forming eutectic.
The pure metals Ag (A) and Pb (B) and mixtures of various compositions of the two
components are heated separately to give a homogeneous liquid phase. The liquid solution is
then cooled slowly and the temperature is plotted against time to get the cooling curve. A break
in the curve indicates the appearance of a new phase. The pure metals will freeze at one constant
temperature and the cooling curve will show a horizontal line. For any mixture, it is possible
to obtain its freezing point or melting point and eutectic point. As the mixtures differ in their
composition, their freezing will commence at different temperatures. But the eutectic
temperature remains the same in all mixtures irrespective of their initial composition.
14.10
USES OF PHASE DIAGRAM
The following are the uses of phase diagrams:

1. Phase diagrams are useful in understanding the properties of materials in a heterogeneous equilibrium system.
2. The study of low melting eutectic alloys which are used in soldering can be carried out
using phase diagrams. Similarly, various types of eutectic alloys can be studied for their
various properties with the help of phase diagrams.
3. It is possible to predict from phase diagrams whether an eutectic alloy or solid solution is
formed on cooling a homogeneous liquid mixture of two metals and hence the structural and physical characteristics of any alloy which in tum decide its engineering uses.
Phase Rule
241
14.11 USES OF PHASE RULE

The uses of the phase rule are as follows:
1. The phase rule provides a convenient basis for classification of equilibrium states of
systems with the help of phases, components and degrees of freedom.
2. It applies to macroscopic systems and hence information about molecular structures is
not essential.
3. The phase rule indicates that different systems having the same degrees of freedom
behave in a similar fashion.
4. It helps in deciding whether the given number of substances together would exist in
equilibrium under a given set of conditions.
14.12 LIMITATIONS OF PHASE RULE

The following are the limitations of the phase rule:
1. The phase rule can be applied only for systems in equilibrium. It is not applicable to
the systems which attain the equilibrium state very slowly.
2. All the phases of the system must be present under the same conditions of temperature
and pressure.
3. Only three degrees of freedom are allowed to influence the equilibrium systems.
( SHORT QUESTIONS)
1. State the phase rule. Explain the terms involved in it.
2. In the dissociation of ammonium chloride in vacuum, the following equilibrium occurs.

NH4CI(s)
NH3(g) + HCI(g)
How many number of phases, components and degrees of freedom are available in this
equilibrium?
3.
CaC03(s) ~ CaO(s) + COz(g)
How many number of phases, components and degrees of freedom are available in this
equilibrium?
4. Write a note on triple point.
5. What is the condensed phase rule?
6. What is the eutectic point?
7. What is meant by component with respect to the phase rule?
8. Can a system have more than one triple point? Illustrate your answer with an example.
9. What are the differences among melting, triple and eutectic points?
242
1. What are phase diagrams? How are they drawn? What information do they provide?
2. Draw a neat phase diagram of one component water system and explain the curves, areas
and point with reference to the phase rule.
3. How will you distinguish the eutectic and melting points by thermal analysis?
4. Draw the phase diagram of a two-component system and indicate the phases present in the
various parts of the diagram.
5. Apply the phase rule to the lead-silver system.
6. Discuss the major application of the phase diagram of the lead-silver system.
7. Discuss the application of the phase rule to ice, water and vapour system.
8. How will you experimentally determine the eutectic temperature of a binary alloy system?
9. Write down the number of phases, components and evaluate the number of degrees of
freedom in the following examples.
(a) A solution of sodium chloride in water

(b) Solid carbon and oxygen in equilibrium with gaseous CO and CO2 at
loooe
10. Two metals X and Y form a simple eutectic system. If there are three samples consisting
of (a) the pure component, (b) an alloy with eutectic composition and (c) an alloy of
another composition, what physical measurements would you make to identify the
samples?
11. Explain the salient features involved in the phase diagram of water.
12. What is an eutectic system? What are the characteristics of the eutectic point? Draw the
phase diagram for a two-component alloy system forming a simple eutectic system and
interpret the diagram. Discuss the major application of this diagram.
13. Draw the phase diagram of a simple eutectic A-B system with the following data and
discuss.
Melting point:
Eutectic temperature:
Eutectic composition:
A-961C;
305C
2.6% A
B-327C
ALLOYS
15.1 INTRODUCTION
Generally, metals are insoluble in ordinary solvents such as water and alcohol. But one metal
can be dissolved in another metal in molten state forming a homogeneous liquid mixture. This
material forming a homogeneous liquid on solidification gives an alloy. An alloy can be defined
as a homogeneous mixture of two or more elements out of which at least one is metal.
Alloys find extensive applications in construction, automobiles, heavy machinery,
equipment, etc.
15.2 IMPORTANCE OF ALLOYS

Pure metals, in general, possess some useful properties such as high malleability, ductility, good
electrical conductivity and high density. However, these metals are very soft and highly reactive.
The properties of a given metal can be improved by alloying it with some other metal or non-metal.
The various purposes of making alloys are given as follows:
l. To increase the hardness of metal: Generally, the metals are soft. The hardness of
a metal is enhanced by alloying. For example, soft metals like gold and silver are
hardened by the addition of copper in making jewellery, coinage, etc. In steel, the
presence of carbon imparts hardness. Addition of 0.5% arsenic makes lead hard and it
is used for making bullets.
2. To lower the melting point or to make the metal easily fusible: When an alloying
metal or non-metal is added to a metal, the melting point of metal is lowered. Also
alloying makes the metal easily fusible. For example, Wood's metal, an alloy of
bismuth, lead, cadmium and tin, has the melting point of 70C which is lower than that
of their components (Bi, Pb, Cd and Sn).
3. To increase the corrosion resistance: Metals in pure form are reactive and easily
corroded by surrounding gases, moisture, etc., thereby their .life is reduced. The alloying
243
244
of metal increases the corrosion resistance. For example, pure iron is corroded in moist air
but stainless steel, an alloy of iron with chromium and nickel is more corrosion resistant.
4. To modify colour: The colour of metals can be modified to a desired one by alloying
it with another element. For example, aluminium is silvery white in colour, whereas its
alloy aluminium bronze (copper and aluminium) has a beautiful golden colour.
5. To provide better castability: One of the essential requirements of getting good
castings is expansion of metal on solidification. In general, pure metals undergo con
traction on solidification. Hence, in order to get good castings, metals have to be
alloyed, because alloys expand on solidifcation. And also as alloys are easily fusible,
they also give good castings. For example, type metal an alloy of lead with 5% tin and
2% antimony is used for casting the type for printing purpose.
6. To modify the chemical activity of the metal: Chemical activity of the metal can be
increased or decreased by alloying. For example the more active sodium metal can be
made into less active by alloying with mercury, i.e. sodium amalgam. Similarly, the activi~
of the aluminium metal is enhanced by alloying with mercury, i.e. aluminium amalgam.
15.3
MANUFACTURE OF ALLOYS
Alloys can be prepared by the following processes:

1. Fusion method: In the fusion method, the component metals of the alloy are fused
together in a crucible lined with refractory bricks. The molten metals are stirred well
with graphite rods. The surface of the molten mass is covered with a layer of carbon
powder which prevents the oxidation of component metals. The homogeneous mass on
cooling solidifies to a required alloy. Alloys like brass and bronze are prepared by this metOOd.
2. Powder metallurgy: The metals with a very high melting point and difficult to make
alloy by fusion can be alloyed using the powder metallurgy.
In this technique the finely powdered metals are intimately mixed and subjected to high
pressure and temperature. The tiny particles of the metals get firmly welded to one
another due to melting and diffusion and an alloy is formed (Figure 15.1). Wood's
metal, solder metal, etc. are prepared by this method.
Guide pin
_
Top moulding part
Bottom moulding part

\~""-vi-_ _
Moulded alloy
~>""'>"'>""'>"'",,-,,-",,-,,--'-'--'--'-..>I
FIGURE 15.1
Preparation of an alloy by powder metallurgy.
Alloys
245
3. Electrodeposition method:
The simultaneous electrolytic deposition of alloying

components by passing direct current through a mixture of electrolytes produces alloy
at the cathode. For example, brass an alloy of copper and zinc is obtained by the
electrolysis of a mixed solution of copper and zinc cyanides dissolved in potassium
cyanide.
4. Reduction method: In this method a compound of one metal is reduced as well as

alloyed by another metal. For example, aluminium bronze is prepared by reducing
aluminium oxide with copper in an electric furnace.
15.4 CLASSIFICATION OF ALLOYS

Alloys are generally classified into two classes.
\. Ferrous alloys: The' alloys containing iron as one of the main components are known
as ferrous alloys, e.g. stainless steel and tool steel.
2. Non-ferrous alloys: The alloys which have some element other than iron as the main
constituent are called non-ferrous at:oys, e.g. bronze and duralumin.
15.4.1 Ferrous Alloys

Steel is an alloy of iron and carbon in which carbon content is up to a maximum of 1.5%. The
carbon added to molten iron is converted to iron carbide in steel. Such plain-carbon steel finds
only limited use. Addition of small amount of one or more metals like nickel, chromium and
cobalt etc. imparts special properties to the steel. Such steels are called alloy steels or special
steels. Let us consider the following alloy steels.
\. Nichrome: A steel alloyed with nickel 60% and chromium 12% is called nichrome. It
is resistant to chemicals and heat. It possesses high melting point and high electrical
resistance. It is used for making resistance coils, heating elements in stoves, iron boxes,
toasters and other electrical appliances.
2. Alnico: Aluminium-nickel-cobalt steel has the composition of aluminium 12%, nickel
20%, cobalt 6% and the remaining is iron. It is highly magnetic and used for making
powerful permanent magnets used in generators, motors, microphones, speakers, etc.
3. Stainless steels or corrosion resistant steels:
These are alloy steels which resist

corrosion by atmosphere and chemicals. The property of corrosion resistance is obtained
by adding chromium and nickel together. The protection against corrosion is due to the
formation of dense and tough film of chromium oxide at the surface of metal. Stainless
steels can be classified into the following groups:
(a) Martensitic stainless steels or heat treatable stainless steels: They contain 12-14%
chromium and 0.12--0.35% carbon. Martensitic stainless steels are heat treatable steels
and magnetic. They can be used up to soooe. Such steels find use in making surgical
instruments, scissors, blades, cutlery, etc.
246
(b) Ferritic stainiess steels or magnetic type steels: Ferritic stainless steels contain
chromium 16-18% and carbon 0.12%. They are non-heat treatable and magnetic.
These steels have better corrosion resistance, good ductility and are easily machinable.
They can be easily made into sheets and strips. They are used to make pump shafts,
spindles, valves, etc.
(c) Austenitic stainless steels or non-magnetic type steels: Austenitic stainless stee~
contain at least 24% of chromium and nickel combined and the percentage of each
of them alone is not less than 8%. They exhibit maximum resistance to corrosion. The
most commonly used stainless steel contains chromium 18% and nickel 8% and is
known as 18/8 stainless steel. To increase corrosion resistance further, a little quantity
of molybdenum is added to such steels. They find use in making household utensils,
sinks, dental & surgical instruments.
15.4.2
Non-Ferrous Alloys
1. Solders: The joining of two metal pieces by means of heat and a filler alloy at compara
tively lower temperature (below 400C) is known as soldering. The filler alloy is known
as solder and is generally an alloy of lead and tin. The important solders and their
compositions are as follows:
(a) Soft solder: Its composition is 37-67% lead; 31-61% tin and 0.12-2% antimony. It
melts at low temperature. Soft solder is used for soldering electric connections,
sealing tin cans and joining lead pipes.
(b) Brazing alloy: Its composition is tin 92%; antimony 5.5% and copper 2.5%. Brazing
alloy is used for soldering steel joints.
(c) Tinman s solder: It is an alloy of 66% tin and 34% lead. Tinman's solder is used for
soldering and tinning.
2. Copper alloys:
(a) Brass:
Copper alloys include brass and bronze.
Brass is an alloy of copper and zinc containing more than 5% zinc.
(i) Commercial brass or french gold or guilding metal: It contains 90% copper and
10% zinc. It is stronger and harder than pure copper and used for making rivets,
screws, jewellery, etc.
(ii) Cartridge brass: Cartridge brass contains 70% copper and 30% zinc. It is soft,
has excellent drawing property and is used for making cartridge cases, household
articles, condenser tubes, etc.
(iii) Dutch metal or low brass: It contains 80% copper and 20% zinc. It has golden
colour. It is suitable for all drawing operations. It is used for making musical
instruments, flexible hoses, name-plates, etc.
(iv) Aluminium brass: Aluminium brass contains 76% copper, 22% zinc and 2%
aluminium. It has better corrosion resistance. It is used for marine works.
(v) Special brasses: They contain metals other than copper and zinc.
(a) German silver: German silver contains 25-50% copper, 10--35% zinc and
5-35% tin. It is extremely ductile, malleable and resembles silver. It
Alloys
247
possesses good strength and good corrosion resistance to salt water. German
silver is used in making utensils, bolts, screws, ornaments, coinage, etc.
(b) Admiraly brass or tobin brass: It contains 59-62% copper; 0.5-1.5% tin and
rest is zinc. Admiraly brass possesses high corrosion and abrasion resistance.
It is used in propellers and marine works.
(b) Bronze:
Bronze is a yellowish-brown alloy of copper and tin.
(i) Coinage bronze or common bronze: Coinage bronze contains 89-92% copper and
8-11% tin. It is soft, ductile and durable. Coinage bronze is used for making
pumps, valves, wires, coins, statues, etc.
(ii) Gun metal: Gun metal contains 85% copper, 8% tin, 4% zinc and 3% lead. It
is hard, tough and strong to resist the force of explosion. Gun metal is used for
foundry works, hydraulic fittings, water fittings, marine pump, etc.
(iii) Phosphor bronze: Its composition is 10-13% tin, 0.4-1% phosphorous and rest
is copper. It is hard, brittle and abrasion resistant. Phosphor bronze possesses low
coefficient of friction. It is used for making bearings, gears, taps, bushes, springs
and turbine blades.
(iv) Aluminium bronze: Aluminium bronze contains 90-93% copper and 7-10%
aluminium. It is quite strong, readily fusible and resistant to corrosion. It
possesses good abrasion resistance. Aluminium bronze is used for making
bushes, bearings, jewellery, utensils, etc.
(v) Nickel bronze: Nickel bronze contains 90% copper, 9% nickel and I % iron. It
is hard. It has higher tensile strength and corrosion resistance than copper. Nickel
bronze is used for rolling purposes.
(vi) Beryllium copper: Beryllium copper contains 97.4% copper and 2.6%
beryllium. It is quite hard. It is used for making springs.
15.5 EFFECTS OF ALLOYING ELEMENTS ON PROPERTIES OF STEEL

The effects of alloying elements (nickel, chromium, manganese, molybdenum, etc.) on the
properties of steel are given as follows:
I. Nickel:
It increases toughness, ductility, elasticity, thermal and corrosion resistance.
2. Chromium: It improves hardness and corrosion resistance.

3. Manganese: It increases strength, toughness and brittleness.
4. Molybdenum: It increases strength, corrosion resistance and abrasive resistance.
15.6 HEAT TREATMENT OF ALLOYS

Heat treatment can be defined as heating and cooling operations under controlled conditions
applied to metals or alloys in solid state in order to achieve certain desired properties for
suitable applications.
248
The following are the important objectives of heat treatment:

(a) To relieve internal stresses
(b) To remove imprisoned gases
(c) To improve strength and hardness
(d) To improve machinability
(e) To improve ductility
(f) To improve electrical, mechanical and magnetic properties
The heat treatment generally involves heating the metal or alloy to a specified temperature.
holding it at that elevated temperature for a specified period and cooling according to a
specified process. The heat treatment does not involve any chemical change.
15.7
TYPES OF HEAT TREATMENT PROCESSES
The following are the important heat treatment processes:

1. Annealing: Annealing is a softening process in which steel is heated to and held at a
suitable temperature for sufficient time to allow the dissolution of carbon in iron and then
allowed to cool in a controlled manner. The annealed part is allowed to cool in the furnace
itself. This process removes internal stresses produced during previous treatment. The
process is classified into the following two categories:
(a) Process annealing (low temperature annealing): It involves heating of steel to a
temperature below lower critical point followed by slow cooling. The process
improves machinability by relieving internal stresses. Process annealing increases
ductility and shock resistance but reduces hardness.
(b) Full annealing (high temperature annealing): It involves heating of steel to a temperature about 30-50C above the higher critical temperature, holding for sufficient
time and then cooling gradually to room temperature. During full annealing process
an intimate solution of carbon and other elements present is produced, leading to
increase in ductility and machinability.
2. Normalizing: Normalizing involves heating of steel to a temperature about 30-50C
above the upper critical temperature, holding for about 10-15 minutes and then cooling
gradually in air. By normalizing the homogeneity of the steel structure is recovered. The
internal stresses are removed. This process is usually adopted to convert a soft and ductile
sample into a strong and ductile sample.
3. Hardening or quenching: Hardening is the process of heating steel beyond critical
temperature and then suddenly cooling it either in oil or water bath. The resulting steel will
have higher hardness. The process increases abrasion resistance, resistance to wear and
ability to cut other materials.
4. Age hardening: Age hardening is also called precipitation hardening and is mostly
applicable for non-ferrous alloys. It is a heat treatment that increases the strength of an
alloy due to the presence of precipitate of second phase in a super saturated solution.
The process of age hardening is having two stages. This is having a solution treatment of
the material at high temperature followed by quenching. The second stage is precipitation
Alloys
249
at room or elevated temperature. The age hardening of an alloy of aluminium with 4%

copper can be considered as an example.
(a) Solution treatment: In solution treatment the alloy is heated to a very high
temperature (around 540C) at which all copper dissolves and a single phase exists.
Then the alloy is quenched rapidly using water. Obviously this quenching does not
allow the diffusion necessary to form CuAl2 precipitate. This results in a super
saturated solid solution.
(b) Precipitation: If the super saturated solid solution is allowed to age, very fine
precipitate particles of CuAl 2 will be formed due to diffusion. But at room
temperature, diffusion will be very slow and so it may take a very long time for aging.
Therefore, the super saturated solid solution may be heated to 200C so that aging
is fast. If the aging is at room temperature, it is called natural aging. If aging is at
elevated temperature it is called artificial aging and it is the most common method
of aging.
5. Tempering: Tempering process consists of heating already hardened steel to a

temperature lower than hardening temperature and then allowing to cool slowly.
Tempering removes any stress that might be developed during quenching. The brittleness
and hardness are reduced but toughness and ductility are simultaneously increased.
6. Case hardening or surface hardening: Case hardening is used to prepare steel having
hardened surface resistant to wear and tear and the interior is soft. This process is usually
carried out for low carbon steels (~0.15%), which cannot be hardened by quenching.
In this process the steel is heated to high temperature and carbon or nitrogen or both are
forced into its surface structure by diffusion. After the carbon is absorbed to required
depth, the article is cooled slowly. Then it is treated by a suitable hardening process. It
is also called chemical heat treatment of steel. The following processes are generally
employed for case hardening.
(a) Carburizing: Carburizing is a method of enriching the surface layer of low carbon
content steel with carbon in order to produce a hard case. In this process the material
is heated with 80% charcoal and 20% barium carbonate at 900-950C in cast iron
boxes. The temperature is maintained for sufficient time to enable the carbon to be
absorbed to the required depth. Thereafter the article in the box is subjected to slow cooling.
This method of using solid carbon containing compounds is called solid carburizing.
BaC03 ~ BaO + CO2
CO2 + C~ 2CO
Fe + 2CO ~ FeC + CO2
In gas carburizing the components are heated to about 900C in an atmosphere of
hydrocarbons like methane, propane and coal gas. The carbon in the gas combines with
the surface of the article and makes it hard.
C3Hg
propane
CH4 + Fe
2CH4 + C
methane
Fe(C) + 2H2
250
(b) Nitriding: Nitriding is a process employed effectively for hardening surface of steel
alloys. The material is heated in presence of ammonia at a temperature about 550(,
The atomic nitrogen formed diffuses and combines with surface constituents (iron and
other alloying elements such as aluminium and chromium) to form extremely hard
nitrides.
2NH3
3H2 + 2N
(c) Cyaniding: Cyaniding is also a case hardening for medium carbon alloys, in which
the material is immersed in molten salts like sodium cyanide or potassium cyanide
with little amount of sodium carbonate and sodium chloride at about 870C followed
by quenching in oil or water. The hard surface is produced due to the absorption of
carbon and nitrogen by the metal surface.
7. Flame hardening: In this method, the area to be surface hardened in the steel material
is heated in an oxy-acetylene or oxy-hydrogen flame. The material is then abruptly cooled
by spraying water on it.
8. Induction hardening: In this process, the hardening of steel surface is done by heating
using a high frequency current at about 2000 Hz. Then the heated surface is quenched
immediately by using water spray.
Flame hardening and induction hardening are surface hardening without changing the
composition of the surface, whereas the other surface hardening methods involve the change in
chemical composition of the surface.
( SHORT QUESTIONS)
1.
2.
3.
4.
Explain any two methods of preparation of alloys.

What is meant by annealing of steels?
What are non-ferrous alloys? Give their properties.
Mention any two advantages of alloy making.
5. Give the composition of the following alloys: (a) nichrome, (b) alnico and (c) 18/8 stainless
steel.
1. Write a short note on nickel alloys.
2. Write a note on heat treatment of steel.
3. What are the ~ain purposes of alloying steel?
4. Give the composition of (a) brass and (b) bronze.
5. What happens during carburizing and nitriding of steel?
6. What do you mean by age hardening?
7. What are solders? Explain the different types of solders and their composition.
ANALYTICAL TECHNIQUES
16.1 INTRODUCTION
Spectroscopy is a branch of science dealing with the study of interaction of electromagnetic
radiation with matter. It is one of the most important tools available for the study of atomic and
molecular structure and used in the structural analysis of a wide range of samples.
Electromagnetic radiation is a type of energy that is transmitted through space at enormous
velocities. Gamma rays, X-rays, ultraviolet, visible, infrared, microwaves and radiowaves are all
electromagnetic radiations of different wavelength and energy.
16.2 ELECTROMAGNETIC SPECTRUM

The arrangement of all types of electromagnetic radiations in the order of their increasing
wavelengths or decreasing frequencies is known as complete electromagnetic spectrum
(Figure 16.1). The visible spectrum represents only a small portion of the electromagnetic
spectrum and this portion is perceptive to human eye.
Radiowave
Microwave
Infrared
Visible
Ultraviolet
X-ray
10-2
FIGURE 16.1
Gamma ray'
The electromagnetic spectrum ..

251
252
If all types of electromagnetic radiations are arranged in the order of their increasing
wavelengths (Table 16.1), then the portion above the visible region is called infrared while the
region below it is the ultraviolet region. Infrared radiations have longer wavelengths and are
thus less energetic.
TABLE 16.1
Region
Electromagnetic spectral regions

Frequency (hertz)
Wavelength
10-2-10 nm
X-ray
Ultraviolet
Visible
Infrared
10-400 nm
400-800 nm
0.8-300 Ilm
(800-300,000 nm)
300 Ilm-O.5 m
(3 x 10 5-5 x 108 nm)
0.5 m-300 m
(5 x 108-3 x 10" nm)
Microwave
Radiowaves
3
3
7.5
3.8
x 10 19-3 X lO'6
x 10 16 -7.5 X 10 14
x 10 14 -3.8 XI 10 14
x 10 14 -1 X 10 12
1 x 10 12 -6
8
6 x 10 -1
X
X
10 8
106
The wavelength is usually expressed in millimetres, metres, nanometres, micrometres,

angstrom units, etc.
A = angstrom = 10-8 centimetre

nm = nanometre = 10-9 metre
)lm = micrometre = 10--{) metre
16.3
ELECTROMAGNETIC RADIATIONS
Electromagnetic radiation is characterized by the following parameters.

1. Wavelength: A wavelength is the distance between the two adjacent crests or troughs
in a particular wave (Figure 16.2). It is usually expressed in angstrom units or in
nanometres.
~I
crest
crest
trough
I..
FIGURE 16.2 Wave motion.
~ 1 trough
Analytical Techniques
2. Wave number:
in em-I.
253
The wave number is the reciprocal of wavelength and is expressed

Wave number (v)
= A1 cm-1
3. Frequency: It is defined as the number of waves which can pass through a point in
one second. It is expressed in cycles per second or in hertz.
c
Frequency (v) = A
where c is the velocity of electromagnetic radiation.
The wavelength, the frequency and the wave number are related as follows.
1
v
-=v=-
4. Energy: Energy of a wave of the particular radiation can be calculated by using the
following relation.
E=hv=h~
A
where h is Planck's constant and is equal to 6.626 x 10-27 erg sec.
16.4 ABSORPTION OF RADIATIONS

If a light radiation is passed through a sample of an organic compound, then some of the
wavelengths are absorbed while others belonging to that light source remains unaffected. When
an atom or molecule absorbs energy, it will move to a higher energy state (excited state). In this
way, the electromagnetic energy is transferred to the atoms or molecules in the sample. A simple
energy level diagram is shown in Figure 16.3.
--------------------------E*
A.,,,,pl;oo
Em;..
~o
--------------------~
FIGURE 16.3 A simple energy level diagram.
eo
The two horizontal lines represent two energy levels within the species.
represents
the ground state (lower energy state) and E* the excited state (higher energy state). An
electron is capable of undergoing transition from
to E*, if energy in the form of light or
heat is absorbed. This absorption of radiation causes the molecule or atom to be in the excited
state.
eo
254
Excited atoms or molecules are short lived and tend to return to the ground state. Hence
from the excited level, the electron may return to its normal position either directly or in steps
with the emission of a certain amount of energy. When this emission of light is instantaneous.
the phenomenon is known as fluorescence. When this emission of light is delayed, it is known
as phosphorescence.
16.5
TYPES OF SPECTROSCOPY
The spectroscopy can be divided into two types: atomic spectroscopy and molecular
spectroscopy.
16.5.1
Atomic Spectroscopy: Electronic Transition
Atomic spectroscopy deals with the interaction of electromagnetic radiation with atoms which
are most commonly in their lower energy state known as ground state. This arises from the
transition of an electron between atomic energy levels.
The electrons in any atom occupy the lowest energy level. In a lithium atom two electrons
are normally in the Is orbital and one in the 2s orbital. This arrangement refers to the ground
state of the atom. If some energy is supplied to the atom, the electron in the 2s orbital can move
to a 2p orbital and if further energy is provided it may move to the 3s orbital. Such an atom
in which one or more electrons are present in the higher energy level is said to be in the excited
state. The process of transfer of an electron from one energy level to the other is referred to as
electronic transition.
16.5.2
Molecular Spectroscopy: Vibrational Transition and Rotational Transition
Molecular spectroscopy deals with the interaction of electromagnetic radiation with molecules.
This arises from three types of transition, viz. rotational, vibrational and electronic.
The atoms in the molecule can vibrate and rotate with respect to one another. These
vibrations and rotations have discrete energy states. A number of vibrational and rotational
energy levels are packed on top of each electronic level (Figure 16.4). A molecule can be
excited from one vibrational energy level to the higher energy one by the absorption of required
amount of energy and this transition is called vibrational transition.
Similarly, a molecule can be excited from a lower rotational energy level to a higher
energy level by the absorption of radiation and this transition is called rotational transition.
Transition from vibrational and rotational energy levels within the ground state to the
corresponding vibrational and rotational energy levels within the excited electronic state is also
possible. The resulting spectra is called band spectra and appears to be in broad.
In the case of an atom, the species neither vibrate nor rotate. Thus the atom does not have
vibrational or rotational energy levels. Hence transition between energy levels of an atom results
in a line spectrum (sharp lines).
255
>-
~
c:
W
Q)
FIGURE 16.4
Molecular energy diagram.
16.6 LIGHT ABSORPTION

When light falls upon a homogeneous medium, a portion of the incident light is reflected, a
portion is absorbed within the medium and the remainder is transmitted. If 10 is the intensity of
the incident radiation, 1a that of the absorbed light, 1/ that of the transmitted light, and 1r that
of the reflected light then
10 = 1a + 1/ + 1r
It is observed that only a small portion of the incident light is reflected and so it is
eliminated. Hence
10
= 1a + 1/
The decrease in the intensity of the incident radiation as a result of passage through
transparent media was systematically studied by Lambert and later extended to solutions by Beer.
16.6.1 Lambert's Law

Lambert's law states that when monochromatic light passes through a transparent medium, the
rate of decrease in intensity with the thickness of the medium is proportional to the intensity
of the light. Mathematically this statement may be expressed as
256
_ dl =kl
dl
(16.1)
where 1 is the intensity of the incident light, I is the thickness of the medium and k is a
proportionality constant (absorption coefficient).
If 10 is the intensity of the incident light, then the intensity of the transmitted light I after
passing through a thickness of the medium I can be obtained by integrating Eq. (16.1):
dl
10
=_
k dl
In-=-kl
10
1
-=e
10
-kl
1 =loe- kl
The ratio
.!.-
is the fraction of the incident light transmitted by a thickness I of the
10
medium and is termed the transmittance. Its reciprocal 10 is the opacity and the absorbance
1
A of the medium is given by

1
A=log..l1..
1
16.6.2
Beer's Law
Beer studied the effect of concentration of the coloured constituent in solution upon light
transmission or absorption. He found that if the absorbing substance is present in solution, the
decrease in intensity of the incident radiation is not only dependent on the thickness of the
medium (optical path), but also on the concentration of the absorbing species.
_ dl
=k' cdl
(16.2)
where c is the concentration of the solution in moles/litre, I is the thickness of the medium and
k' is a proportionality constant, the value of which depends upon the nature of the absorbing
substance.
If 10 is the intensity of the incident light, then the intensity of the transmitted light I can
be obtained by integrating Eq. (16.2):
l
10
dl
1
=-
k' cdl
257
1
I
In-=-k d
10
1
-=e
-k'c/
10
1 = loe-k'el
(16.3)
Equation (16.3) can be written as
10 10
g 1
k'd
2.303
1
10g~= A = eel
1
where e is called the molar absorption coefficient or extinction coefficient. The relation is
known as the Lambert-Beer law which is the fundamental equation for colorimetry and
spectrophotometry.
16.7 COLORIMETRIC ANALYSIS

Colorimetric analysis is defined as a technique in which the colour intensity of the unknown
solution is compared with that of the standard solution, Le. a solution of definitely known
concentration. The instrument used for this technique is known as a colorimeter.
This method is suitable for coloured solutions. If the solution is colourless, the colour can
be developed with the help of a suitable complexing agent. The coloured complex can absorb
light in the visible region. For example, in the estimation of cuprous ions, ammonium hydroxide
is used as a complexing agent to get blue-coloured solution.
Colorimetry is concerned with the visible region (400-750 nm) of the spectra.
16.7.1 Working of a Colorimeter

[n a colorimeter, a narrow beam of light of proper wavelength passes through the test solution
towards a sensitive photocell (detector). Generally, a colorimeter is provided with the arrangement of filter to select the light of required wavelength.
The current generated in the photocell is proportional to the amount of light transmitted
by the solution. This in tum depends upon the concentration of the test solution. Thus the
current from the photocell will be more when the light transmitted by the solution is more. This
generalIy happens when the test solution is more dilute. The intensity of current generated is
displayed in a meter (Figure 16.5).
Current
DC
light transmitted DC
1.
concentratIon
258
Narrow
beam
Filter to select
appropriate wavelength
FIGURE 16.5
16.7.2
Test solution
(coloured)
Photocell
Meter
Block diagram of a colorimeter.
Estimation of Concentration of a Solution by Colorimetry
For the determination of concentration of an unknown solution, a calibration curve has to be

first plotted. A series of standard solutions is prepared by dissolving known quantities of the
substance and the colour is developed by adding an appropriate reagent. The same procedure
is followed by developing colours in the case of an unknown sample also. The absorbance of
all these solutions are measured at the optimum wavelength. The absorbance of each of the
standard solution is plotted against the respective concentration. A straight line is obtained if
Beer's law is obeyed. The concentration of the unknown solution can be directly obtained from
the calibration curve (Figure 16.6).
i
c:
e.
~ ~----~------~
.0
Concentration _
FIGURE 16.6
Calibration curve for colorimetric analysis.
The salient features of colorimetric analysis are as follows:

1. It gives more accurate results at low concentration.
2. It is very easy to carry out.
16.7.3
Estimation of Iron by Colorimetry
Principle
Iron present in water as Fe 3+ ions is reduced to Fe 2+ ions by treating with

hydroxylaminehydrochloride. When 1,10 phenanthroline is added, a soluble complex having
orange red colour is produced which can be measured photometrically.
:,vltcai Techniques
259
Procedure
Astandard stock solution of iron is produced by dissolving 0.7022 g of ferrous ammoniumsulphate in water in the presence of 1 ml of concentrated sulphuric acid and made up to 1000 ml
in a standard measuring flask (l ml of this solution == 0.1 mg of iron).
From the stock solution, volumes of 1, 2, 3, 4 and 5 ml are transferred accurately into
100 ml standard measuring flasks using pipette. To each solution, 10 ml of 10% hydroxylamine
hydrochloride, 10 ml of sodium acetate and 8 ml of 1,10 phenanthroline are added and made
up to the mark using distilled water. A blank solution is also prepared by taking 10 ml of 10%
hydroxylamine hydrochloride, 10 ml of sodium acetate and 8 ml of 1,10 phenanthroline and
made up to the mark using distilled water. The cell is filled with the blank solution after rinsing
and the transmittance of the spectrophotometer is set to 100%. The blank solution is then removed
and the absorbances of the standard solutions prepared, are measured at a wavelength 510 nm. A
calibration curve is drawn by plotting various concentrations of iron against absorbance.
The given water sample is transferred into a 100 ml standard measuring flask followed by
addition of 10 ml of hydroxylamine hydrochloride, 10 ml of sodium acetate and 8 ml of 1,10
phenanthroline. This solution is made up to the mark using distilled water and shaken well. The
absorbance of this solution is measured. From the calibration curve, the amount of iron present
in the given water sample can be found out.
16.8 FLAME PHOTOMETRY OR FLAME EMISSION SPECTROSCOPY

It is a well-known fact that a characteristic yellow light is emitted when a small amount of
sodium is introduced into a flame of a Bunsen burner and the brightness of the flame varies with
the amount of sodium introduced. Emission of such characteristic radiation by sodium or other
metal and the correlation of the emission intensity with the concentration of the element form
the basis of flame photometry.
Theory
When the sample solution containing the metal is introduced into a flame, the sequence of
events which occur in flame photometry is charted below.
I. The solvent is evaporated leaving a solid residue.
2. The solid residue is vaporized and dissociates into atoms.
3. By absorbing thermal energy of the flame, some of the atoms from the ground state are
excited to a higher energy state.
4. The excited atoms which are unstable then return to the ground state by emitting
radiations of different wavelengths.
The emitted radiation of different wavelengths is passed through a filter which allows the
characteristic wavelengths of the metal under examination.
The whole process is diagrammatically represented as follows.
+ -
MX
Sample
solution
vaporization
evaporation ..
MX
Solid
"
dissociation
MX :;::=====" M + X
Gas
thermal
. .
excItatIOn)
M*
Gas
hv
emission
260
16.8.1
Instrumentation
The essential components of a flame photometer are as follows:

1. Burner:
The flame produced by the burner should do the following functions.
(a) The flame should evaporate the solvent from the test solution.
(b) It should convert the solid into gas and then dissociate into atoms.
(c) It should excite the atoms and then cause them to emit radiations.
2. Lens:
The emitted light is collected by a lens and then allowed to pass through a filter.
3. Filter: The filter allows the light of particular wavelength to pass through, but
absorbs the light of other wavelengths.
4. Photocell (Detector): The radiation coming through the filter is allowed to fall on the
photocell which measures the intensity of emitted radiations.
Photocell is used as a detector, because it converts the radiations into an electric current.
5. Amplifier and recorder:
amplified and recorded.
As the current coming out of the detector is weak it is
Working
Air at a given pressure is passed into an atomizer. The suction thus produced draws a solution
of the sample into the atomizer where it joins the air stream as a fine mist and passes into the
burner. Here, the air mixes with the fuel gas supplied to the burner at a given pressure and the
mixture is burnt. The resultant radiation from the flame passes through a lens and finally
through an optical filter which permits only the radiation characteristic of the element under
investigation to pass through the photocell. The output from the photocell is amplified and then
recorded (Figure 16.7).
Flame
Lens
Filter
Photocell
Amplifier
and
Recorder
~ Gas
Atomizer
(11
Air
Drain
(constant head)
FIGURE 16.7 Block diagram of a flame photometer.
261
First, a calibration curve has to be plotted using solutions of known concentration. This
~ done by introducing into the flame known concentrations of the element to be determined,
measuring the respective readings and plotting them against the respective concentrations of the
standard solutions used (Figure 16.8).
i
Unknown concentration
Concentration (mg/l) ___
FIGURE 16.8
Calibration curve.
16.8.2 Applications of Flame Photometry

I. Quantitative analysis:
Flame photometry is mainly used for the estimation of alkali

and alkaline earth metals.
For example, sodium is present in most natural water from negligible to appreciable
concentration. Excessive amount of sodium in drinking water is harmful to persons
suffering from cardiac and renal diseases. Water containing sodium ions can cause
boiler corrosion when used in a boiler. Water containing excessive sodium ions is
unsuitable for irrigation purpose because it affects the salinity of the soil. So, even a
small amount of sodium present in natural water, industrial waste water, soil, etc., can
be detected by flame photometry.
2. Glass:
The sodium and potassium contents in glass can be detected by this technique.
3. Gasoline: This technique is also used for the determination of tetraethyl lead in
gasoline.
4. Miscellaneous applications: Flame photometry is applied to the analysis of a wide
variety of materials including biological fluids, cement, etc. The presence of boron in
organic compounds can also be detected by this technique.
16.8.3 Limitations of Flame Photometry

The following are the limitations of flame photometry:
1. Halides and inert gases cannot be directly detected.
2. All metals cannot be analyzed.
262
16.8.4
Estimation of Sodium by Flame Photometry
Preparation of standard sodium solution
2.542 g of analar sodium chloride is dissolved in 1 litre of water in a standard measuring flask.
This solution contains the equivalent of 1 mg of sodium per ml (1 ml == 1 mg Na). This stock
solution is diluted to give four different standard solutions of 10, 5, 2.5 and 1 ppm of sodium
ions.
Construction of calibration curve
The digital display of the instrument is set for zero by using distilled water and then to 100 by
using 10 ppm of sodium solution at sodium wavelength. The standard solutions with different
concentrations are introduced into the flame and the corresponding digital display readings are
noted. When the intensity of the emitted light (digital display reading) is plotted against concentration, a calibration curve is obtained.
Determination of unknown concentration
The given sample is then introduced into the flame and the corresponding intensity of the
emitted light is found out. The amount of sodium in the water sample can be determined by
interpolation.
16.9
VISIBLE AND ULTRAVIOLET SPECTROSCOPY
Visible and ultraviolet spectra arise due to the transition of valence electrons from the lov
energy level to the higher energy level by the absorption of energy. In some cases the requirea
energy can be supplied by radiation of visible wavelengths thus producing an absorption
spectrum in the visible region (400-800 nm). In other cases, the transition occurs due to the
absorption of ultraviolet radiations thus producing an ultraviolet spectrum in the region of
10-400 nm.
The ultraviolet region can be divided into two spectral regions as follows:
Near ultraviolet: 200-400 nm

Far ultraviolet: 10-200 nm
Principle
Ultraviolet absorption spectra occurs due to the transition of electrons from lower electronic
level and higher electronic level. Hence it is also called electronic spectroscopy. For a radiation
to cause electronic excitation, it must be in the ultraviolet region of the electronic spectrum.
16.9.1
Types of Electrons Involved in Organic Molecules
The electrons involved in organic molecules can be classified into different types:
1.
(Y electrons:
They are involved in saturated bonds and they are tightly bound.
Radiation of high energy is required to excite them.
2. 1l'electrons:
easily.
263
They are involved in double or triple bonds and they can be excited very
3 n electrons: Electrons attached to atoms such as chlorine, oxygen or nitrogen as lone

pairs are called n electrons. These non-bonding electrons can be excited at a lower
energy.
16.9.2 Types of Transitions in Organic Molecules

Electronic transitions for organic molecules involve absorption of ultraviolet radiation by electrons in (J, J( or n orbitals and results in their transition to the higher energy antibonding orbital
(excited state). Ultraviolet radiations promote the following electronic transitions:
(Y
0'*, n
0'*, n
Tl* and
1r ~
Tl*
The order of energy level of various molecular orbitals is shown in Figure 16.9.
- - - - - - - - - - a* (Antibonding)
- - - - - - - - - - - 1t" (Antibonding)
(J)
- - - - - - - - - - n (Non-bonding)
c
w
- - - - - - - - - - tr(Bonding)
- - - - - a (Bonding)
FIGURE 16.9
Electronic molecular orbital energies.
The energy needed for (Y ~ 0'* transition is very large. Hence compounds like saturated
hydrocarbons with only (Y bonds and no n electron have absorption bands in the far ultraviolet
region (126-135 run). On the other hand compounds having non-bonding electrons show absorptions due to n ~ Tl* and n ~ 0'* transitions.
16.9.3 Chromophores
The absorption of a given substance is greatly affected if it contains a chromophore. A
chromophore is a functional group which has a characteristic absorption spectrum in the
ultraviolet region. Such groups invariably contain double or triple bonds and include C=C, C=C,
nitro and nitroso groups, azo and carbonyl groups. Chromophores undergo 1r ~ Tl* transitions
in the short wavelength region of ultraviolet radiations.
16.9.4 Auxochromes
The absorption of a given molecule may also be enhanced by the presence of groups called
auxochromes. Important auxochromes include OH, NH 2, CH 3, etc. When conjugated with
264
chromophores, auxochromes modifY the position of absorption band relative to that of the
parent chromophore.
The bathochromic shift is an effect by virtue of which the maximum absorption is shifted
towards longer wavelength due to the presence of an auxochrome. It is also called red shift.
The shifting of maximum absorption to a shorter wavelength due to the presence of
auxochrome is called hypsochromic shift or blue shift.
16.9.5
Instrumentation
The essential parts of a spectrometer are as follows:
Radiation source
Monochromator
Cells
Detectors
Recording system
Radiation source
Generally mercury arc, hydrogen or deuterium lamps are used. The radiation source should meet
the following requirements.
1. It should be stable.
2. The source should provide continuous radiations.
Monochromator
The monochromator consists of an entrance slit, a dispersing element and an exit slit. The
dispersing element is generally a prism or grating. The function of dispersing element is to
isolate a narrow band of wavelength from the radiation source.
Cells
Cells made up of silica or glass are used to contain sample solution as well as reference solution.
The cells should satisfY the following requirements.
1. Cells should have uniform thickness.
2. They should be inert to the solvent.
3. They must transmit the light of wavelength used.
Standard cells of rectangular form with one centimetre path length are generally used.
Solvents which are used in the reference cells are water, ethanol, methanol, chlorofonn, etc.
Detectors
Detectors convert the transmitted radiation into electrical energy. The electrical energy produced
is inversely proportional to the concentration of the solution.
Recording system
The signal from the detector is recorded by this system.
265
16,9,6 Working of Visible and UV Spectrophotometer

The radiation from the source is passed through the monochromator. The monochromator isolates a narrow band of wavelength from the radiation source. The beam of radiation coming out
of the monochromator is split into two identical beams, one of which passes through the
reference cell and the other through the sample cell (Figure 16.10).
()-1_~-\'"*l,\:--m- Source
Monochromator
Sample
r-
r-----
Recorder
Detector
~------
Reference
f---
Beam splitter
FIGURE 16.10
Block diagram of UV-visible spectrophotometer,
If the test solution absorbs light at a particular wavelength, then the intensity of the beam
coming out of the sample cell (l) is less than that of the beam coming out of the reference cell
(10), A graph is recorded by the instrument which is a plot of wavelength versus the absorbance
of the light. This graph is known as an absorption spectrum.
16,9.7 Applications of Visible and Ultraviolet Spectroscopy

Identification of an unknown compound
The absorption spectroscopy is a very useful technique in the identification of chemical substances. An unknown compound can be identified by comparing its spectrum with the spectra
of known compounds. If the two spectra coincide, then the two compounds must be identical.
The rule governing this is known as Hartley 50 rule which states that compounds having similar
structure would have similar absorption spectra.
~antitative
analysis
This technique is also used for the quantitative analysis of organic compounds. This is based
on the Lambert-Beer law:
I
A=log~=ecl
I
where is the extinction coefficient, c is the concentration and I is the length of the cell used
in the spectrometer.
For the quantitative determination of an organic compound, the wavelength of maximum
absorption for the compound is found out. The optical densities are measured for some known
concentrations at the selected wavelength. The values of optical density are plotted against their
respective concentration, to obtain a calibration curve. If Beer's law is obeyed, a straight line
is obtained and from this graph, the unknown concentration can be inferred.
266
Detection of impurities
UV-visible spectroscopy is one of the best methods for detecting impurities in organic
compounds. For example, benzene which is the most common impurity in cyclohexane can be
easily detected by the absorption band of benzene at 255 nm. Similarly, purification of organic
compounds can be continued until the absorption bands characteristic of the impurities
disappear in the spectrum.
Chemical kinetics
The UV-visible spectrophotometer is helpful for studying the kinetics of chemical reactions by
following the changes in concentration of either reactant or product with time during the
reaction.
Tautomeric equilibrium
The UV-visible spectrophotometer can be used to determine the percentage of keto and enol
forms present in compounds such as ethyl acetoacetate by measuring the strength of the respec
tive absorption bands.
"
CH3-C-CH2COOC2H s
keto form
CH 3-C=CHCOOC 2H s
OH
enol form
keto form has

enol form has
16.10
Amax =
Amax =
275 nm
244 nm
INFRARED SPECTROSCOPY
Infrared spectrum is produced by the absorption of energy by a molecule in the infrared region
and the transition occurs between vibrational levels. Hence IR spectroscopy is also known as
vibrational spectroscopy.
The region in the electromagnetic spectrum ranging from 0.8 to 300 Jlm (8003,00,000 nm) is commonly known as the infrared. The IR region can be divided into three
spectral regions as follows:
1. Near infrared: 0.8-2.5 /lm
2. Fundamental infrared: 2.5-50.0 /lm
3. Far infrared: 50-300 /lm
When infrared light is passed through a sample of an organic compound some of the
frequencies are absorbed while other frequencies are transmitted through the sample without
being absorbed. If we plot the per cent absorbance or per cent transmittance against frequency,
the result is an infrared spectrum. This spectrum contains a large number of absorption bands
from which a wealth of information can be derived about the structure of an organic compound.
This technique is quite useful to predict the presence of certain functional groups which
absorb at definite frequencies. For example, the hydroxyl group in a compound absorbs at
267
3200-3600 cm- I and carbonyl group of ketones gives a strong band at 1710 cm- I .
Consequently, IR spectra are often characterized as molecular fingerprints, which detect the
presence of functional groups.
16.10.1 Modes of Vibrations in a Molecule

When energy is absorbed by a molecule, the different bonds of the constituent atoms exhibit the
different modes of vibrations. They are as follows:
Stretching vibrations
Bending or deformation vibrations
Stretching vibrations
In stretching vibrations the atoms move along the bond axis. As a result, the bond length
increases or decreases but bond angle remains unchanged. There are two types of stretching
vibrations.
Symmetric stretching
Asymmetric stretching
1. Symmetric stretching: In this type, the atoms of the molecule move in the same
direction (Figure 16. 11 a).
2. Asymmetric stretching: In this type, the atoms of the molecule move in opposite
direction (Figure 16.11 b).
\/
(a) Symmetric
FIGURE 16.11
(b) Asymmetric
Types of stretching vibrations.
Bending or deformation vibrations
Bending vibrations involve a change in the bond angle whereas the bond length remains
unchanged.
There are four types of bending vibrations.
Scissoring
Rocking
Twisting
Wagging
All are shown in Figure 16.12.
268
Scissoring
Rocking
Twisting
FIGURE 16.12
Wagging
Types of bending vibrations.
I. Scissoring: In this type, the atoms move away and come close to each other in the
same plane just like the blades of a scissor.
2. Rocking:
In this type, the movement of atoms takes place in the same direction.
3. Twisting: In this type one atom moves up and the other moves down the plane with
respect to the central atom.
4. Wagging: In this type two atoms move up and below the plane with respect to the
central atom.
The number of fundamental vibrational modes of a molecule can be calculated as follows.
A non-linear molecule containing N atoms has (3N - 6) fundamental vibrational modes.
For example water is a non-linear triatomic molecule. Therefore,
vibrational degrees of freedom of water = (3N - 6)
=3x3-6
=9-6
=3
So, water is having three fundamental modes of vibration such as symmetric stretching
vibration, asymmetric stretching vibration and bending vibration. All the three vibrations are
said to be IR active as there is a change in dipole moment during the vibration. So, the IR
spectrum of water exhibits three absorption bands.
Thus for a vibration to be IR active, there should be a change in dipole moment of the
molecule. Homonuclear diatomic molecules like O2, N2 and H2 have zero dipole moments and
they are IR inactive.
A linear molecule containing N atoms has (3N - 5) fundamental vibrational modes. For
example, CO2 is a linear molecule. Therefore,
vibrational degrees of freedom of carbon dioxide = (3N - 5)
=3x3-5
=9-5
=L1
269
So, carbon dioxide is having four fundamental modes of vibrations such as symmetric
stretching, asymmetric stretching, in plane bending and out of plane bending. Of the four
nonnal modes, only the asymmetric stretching, in plane bending and out of plane bending
vibrations are IR active as they involve a change in dipole moment. As the symmetric stretching
vibration does not involve any change in dipole moment, it is IR inactive.
16.10.2 Fingerprint Region

In the IR spectrum, the region between 900-1500 cm- I is rich in many absorptions and this area
~ called as fingerprint region. These absorptions are caused by bending vibrations and those
resulting from the stretching vibrations of C-C, c-o and C-N bonds.
The fingerprint region is used for proving the identity of a compound. The matching of
the fingerprint region with the spectrum of a known compound in a library of infrared spectra
is a very powerful tool for confirming the presence of a particular compound.
The essential components of an IR spectrometer (Figure 16.13) are as follows:
Radiation source
Monochromator
Sample holder
Detector
Radiation source
The Nemst glower and globar are the most common sources of radiation. The Nemst glower
consists of a rod of hollow tube about 20 mm long and 1 mm in diameter made by sintering
amixture of oxides of zirconium, thorium and yttrium. Globar is a silicon carbide rod when
heated electrically at 1200-2000C, it glows and produces IR radiation.
IbIochromator
The radiation source emits radiation of various frequencies. As the sample absorbs only at
certain frequencies, it is therefore necessary to select desired frequencies from the radiation
source. This has been achieved by monochromators. Prisms and gratings are commonly used for
this purpose.
Sample holder
The sample holder made up of sodium chloride or potassium bromide is used to contain sample
solutions as well as reference solution because they are transparent to IR radiation.
Detector
jr detectors generally convert thermal radiant energy into electrical energy. Thermocouples
and bolometers are generally used for this purpose.
270
16.10.4 Working of Infrared Spectrometer

The radiation from source is passed through the monochromator. The monochromator isolates
a narrow band of wavelength from the radiation source. The beam of radiation coming out of
the monochromator is split into two identical beams, out of which one passes through the
reference solution and the other through the sample solution.
()--1_---'I---\~i~------~----'
,
Source
Recorder
Detector
Monochromator
'\-------~
Beam splitter
FIGURE 16.13
Block diagram of double beam IR spectrometer.
If the test solution absorbs light at a particular wavelength, then the intensity of the beam
coming out of the sample solution is less than that of the beam coming out of the reference
solution. If I is the intensity of the sample solution and 10 that of the reference solution, then
1110 is called the transmittance. A graph is recorded by the instrument which is a plot of
transmittance versus wave number.
16.10.5 Applications of IR Spectroscopy

Structural diagnosis
The most important application of infrared spectra is its structural diagnosis. Spectra are studied
for the presence or absence of bands which are characteristics of particular molecular groupings
and molecular structure. Thus IR spectra are of great value in checking the synthesis of new
products and in dealing with the unknown structure.
The approximate positions of some infrared absorption bands are given in Table 16.2.
TABLE 16.2
Molecular groups and their wave numbers
Group
Wave number
C-H (aliphatic)
C-H (aromatic)
O-H (phenolic)
2700-3000 cm- i
3000-3100 cm- i
3700 cm- i
-C=O (aldehyde)
1720-1740 cm- i
H
C=O (ketone)
C=O (acid)
1705-1725 cm- i
1700-1750 cm- i
1650 cm- i
N-H
3300-3370 cm- i
C=O (ester)
271
Progress of a chemical reaction
IR spectroscopy can be used for studying the progress of a chemical reaction. For example,
during the oxidation of a secondary alcohol to a ketone, the IR spectra of aliquots withdrawn
from the reaction mixture periodically are recorded. As the reaction proceeds the OH-stretching
band at 3750 cm- i of secondary alcohol slowly disappears and a new band at 1725 cm- i appears
due to the formation of ketone.
Hydrogen bonding
By using IR spectroscopy intermolecular and intramolecular hydrogen bonding can be

distinguished. For example a series of IR spectra of the compound at different dilution are
recorded. As the dilution increases, the absorption band due to intermolecular hydrogen bonding
diminishes whereas that due to intramolecular hydrogen bonding remains unchanged.
Purity of the sample
Generally pure samples show fairly sharp and well resolved absorption bands while the
spectrum of a crude sample may contain several absorption bands which are usually broad and
poorly resolved.
16.11 ATOMIC ABSORPTION SPECTROSCOPY (AAS)

Atomic absorption spectroscopy was introduced by Walsh for the analysis of trace amount of
metallic elements. The advantage of this technique is that 50-60 elements can be determined
without any interference.
16.11.1 Principle
Atomic absorption spectroscopy involves the study of the absorption of radiation usually in the
ultraviolet and visible region by the atoms in the vapour state. Thus in atomic absorption
spectroscopy, the sample is first converted into atomic vapour and then the absorption of the
atomic vapour is measured at a particular wavelength which is the characteristic of individual
element. The measured absorption is proportional to the concentration of the element.
The essential components of atomic absorption spectrophotometer (Figure 16.14) are as follows:
Radiation source
Atomizer
Monochromator
Detector
Amplifier
Recorder
Radiation source
The radiation source should emit stable, intense and characteristic radiation of the element to
be determined. A hollow cathode lamp is used as radiation source. The hollow cathode lamp
272
consists of a glass tube containing noble gas (neon or argon) and hollow cathode made up of
the element to be determined or coated with it. The anode may be made up of tungsten.
Atomizer
Generally burners are used to break the liquid sample into droplets which are then allowed to
enter the flame. This method of formation of small droplets from the liquid sample is called
nebulization. These droplets are then evaporated and the sample element is left in the residue.
The residue is then decomposed in to atoms by flame.
Monochromator
Generally a grating or prism is employed as monochromator. The purpose of monochromator

is to isolate the resonance line from all non-absorbed lines emitted by the radiation source.
Detectors
Generally photomultipliers are used as detectors. When the photon strikes the photomultiplier
tube an electric current is produced.
Amplifier
The electric current from the photomultiplier detector is fed into the amplifier which amplifies
the electric current.
Recorder
The signal coming out of the amplifier is then recorded.

Atomizer
Hollow
cathode lamp
Flame
Prism
(monochromator)
Photomultiplier
(detector)
Amplifier
FIGURE 16.14
Block diagram of atomic absorption spectrophotometer.
16.11.3 Working of Atomic Absorption Spectrophotometer

The process involves two steps:
Atomization of the sample

The absorption of radiation from a light source by the free atom
273
The characteristic light radiation from the hollow cathode lamp is passed through a flame
into which the sample is aspirated. The metallic compounds are decomposed into atoms. A part
of the light from the radiation source is absorbed by the atomic cloud. The unabsorbed radiation
from the flame is allowed to pass through the detector. From the detector, the output is amplified
and recorded using the recorder.
16.11.4 Advantages of Atomic Absorption Spectroscopy

The following are the advantages of AAS:
1. By atomic absorption technique, traces of one element can easily be determined in the
presence of high concentration of other element.
2. Various metals like Ca, Mg, Cr, Cu and Pb can be determined using this technique.
3. The presence of trace elements in contaminated soils and environmental samples can
be determined by this technique.
16.11.5 Quantitative Estimation of Nickel

Preparation of standard nickel solution
Standard nickel solution of 1000 ppm is prepared by dissolving 1.0 g of nickel nitrate in
minimum amount of dilute nitric acid and diluted to 1 litre using distilled water. From the
standard stock solution, a series of standard solutions is prepared by suitable dilution.
Operating parameters
Wavelength
Light source
Flame type
232.0 nm
Hollow cathode lamp (Ni)
Air-acetylene flame
Construction of calibration curve
Now the standard solutions are aspirated one by one into the flame and absorbances are
measured. Now the graph is plotted between absorbance and concentration (Figure 16.15).
1.0
0.8
o 0.6
~
I
I
I
I
0.4
:I unknown
I
I
0.2
I
I
I
I
10
20
30
40
Concentration of Ni solution -
FIGURE 16.15 Calibration curve.
50
274
Determination of unknown concentration
The unknown solution of nickel is aspirated into the flame and absorbance is measured as
performed for the standard calibration. From the absorbance, the concentration of the unknown
sample is determined.
SOLVED EXAMPLE!)_]
Example 16.1: Calculate the frequency of radiations having wavelength 5000A where
c = 2.996 X 1010 cm/s.
Solution:
Frequency (v)
= Ac
2.996 X 1010 cm S-I
=--------::---
5000 x 10-8 cm
= 5.992 x 1014 S-I

Example 16.2:
Calculate the absorbance (optical density) if 10% of incident light is
transmitted.
Solution:
Absorbance (A)
= log 10
1
=log 100
10
= log 10 =1
Example 16.3: A solution of thickness 2 cm transmits 40% incident light. Calculate the
concentration of the solution, if = 6000 litre mol- I cm- I .
Solution:
10 = 100
1= 40
= 6000 litre mol- I cm- I
1=2 cm
c=?
1
log~=cl
1
100
log 40
=6000 x c x 2
275
log 2.5 = c x 12000

0.3979 = c x 12000
0.3979
C=
- - - =3. 316 X 10-5 mo II'Itre -I
12000
txample 16.4: A solution shows a transmittance of 20% when taken in a cell of 2.5 cm
thickness. Calculate its concentration, if the molar absorption coefficient is 12,000 dm3 mol- 1
em-I.
Solution:
10 = 100
1 = 20
e = 12000 dm3 mol- 1 cm- I

1= 2.5 cm
C=?
1
log~= eel
1
100
log -=12000 x C x 2.5
20.
log 5 = C x 30000
0.6989
C
= C
x 30000
= 0.6989 = 2.3296 x 10-5 mol dm-3

30000
( SHORT QUESTIONS)
1. What do you mean by electromagnetic radiation and electromagnetic spectrum?
2. Define and distinguish wavelength and wave number.
3. Define the terms frequency and wave number.
4. Give the energy of an electromagnetic radiation.
5. State the types of spectroscopy.
6. The spectrum arising from electronic transition occurs as a broad band. Justify.
7. Why atomic spectrum appears as sharp line spectrum?
8. State the Beer-Lambert law.
9. State the principle involved in colorimetric analysis.
10. What is flame photometry?

11. Give the different types of electronic transitions that can occur in an organic molecule.
276
12. Define the terms chromophores and auxochromes.

13. Define and distinguish bathochromic shift and hypsochromic shift.
14. Give the basic principle of infrared spectroscopy.
15. How many numbers of fundamental vibrations are available for linear and nonlinear
molecules?
16. IR spectrum is an important tool to study the hydrogen bonding. Justify.
17. What is the function of the following parts in a spectrophotometer:
(a) Monochromator
(b) Filter
1. Explain the parameters that are used to characterize an electromagnetic radiation and its
energy.
2. Derive the expression for the Beer-Lambert law.
3. Write a note on colorimetric analysis with the instrumentation involved in it.
4. Explain various parts of a flame photometer. Write the principle involved in flame pho
tometry and its few applications.
5. Explain the different types of electronic transitions occurring in an organic molecule.
6. Draw the block diagram of a UV-visible spectrophotometer and explain its various parts.
7. Discuss the principle and applications of UV-visible spectroscopy.
8. Explain the different modes of vibration of a molecule with suitable representations.
9. Explain the principle and applications of infrared spectroscopy.
( PROBLEMS )
1. The wavelength of a radiation is 2.5 Ilm. Find (a) wave number, (b) frequency and
(c) energy of the radiation.
(Ans. (a) 4 x 107 m- I (b) 1.2 x 10 14
S-I
(c) 7.95
10-20 1)
2. Calculate the wave number, frequency and energy of a radiation with wavelength 2500 A.
(Ans. 4 x 106 m-I, 1.2 x lOIS s-I, 7.95 X 10-19 1)
3. A monochromatic radiation is incident on a solution of 0.05 M concentration of an absorb
ing substance. The intensity of the radiation is reduced to one-fourth of the initial value
after passing through 10 cm length of the solution. Calculate the molar extinction coefficient and its optical density (absorbance).
(Ans. 120.4 I mol-I m- I ; 0.602)
INDEX
Abrasives
classification, 97
properties, 96
uses, 98
Absorption, 47
Acid number, 113
Acid refractories, 92
Activated carbon, 59
Adsorbate, 47
Adsorbent, 47
Adsorption, 47
applications, 56
chemisorption, 48, 49
ion-exchange, 60
isotherm, 50
physisorption, 49
Adsorption isobar, 55
Alkalinity, 6, 7
Alloys, 243
ferrous, 245
manufacture, 244
non-ferrous, 246
Aniline point, 112
Atom bomb, 71
Atomic absorption spectrophotometer, 272
Atomic absorption spectroscopy, 271
Auxochromes, 263
Basic refractories, 92
Batteries
primary, 77
secondary, 77
Beer's law, 256
Bending vibrations, 267

Bergius process, 198
Binders, 35
Binding energy, 67
Block copolymer, 32
Boiler corrosion, 10
Boiler feed water, 8
Boundary film, 103
Brackish water, 21
Breeder reactor, 74
Buna-S rubber, 43
Butyl rubber, 43
By-product oven method, 196
Calomel electrode, 133

determination of pH, 137
Calorific value, 187
Carbon nanotubes, 120
applications, 121
properties, 121
synthesis, 120
Carbon residue test, 113
Carbonization, 194
types, 194
Catalysts, 36
Caustic embrittlement, 10
Cementation, 172
Cermets,94
Chain reactions, 70
Chemical reactions, 65
Chromophores, 263
Cladding, 172
Cloud point, 112
277
278
Index
Coal
analysis, 191
classification, 189
hydrogenation, 197
varieties, 190
Colorimeter, 257
Colorimetric analysis, 257
Combustion, 214
ignition temperature, 214
spontaneous, 215
Composites
ceramic matrix composites, 45
fibre reinforced polymer composites, 45
metal matrix composites, 44
polymer matrix composites, 45
Compressed natural gas, 210
Concentration cell corrosion, 157
Concentration cells, 138
applications, 139
Conductance, 124, 125
Conductivity, 124
Conductometric titrations, 127
Contact catalysis, 57
Copolymers, 31
Corrosion, 156
control, 164
crevice, 162
erosion, 162
galvanic, 161
pitting, 162
soil, 164
stress, 163
underground, 164
waterline, 163
Corrosion, 155
Cracking, 201
catalytic, 202
thermal, 202
Daniel cell, 130
Deformation vibrations, 267
Degree of polymerization, 30
Degrees of freedom, 235
Deionization, 12, 14
Deionizer, 15
Demineralization process, 12, 14, 15
Desalination, 20
Desalination process, 21
Diesel index, 210
Diesel knock, 209
Differential aeration, 157
Doping, 207
Dyes, 35
Electrochemical series, 144

Electrochemical theory, 156
Electrode concentration cells, 138
Electrode potential, 131, 132
Electrodeposition, 173
Electrodialysis, 21
Electroless copper plating, 177
Electroless nickel plating, 176
Electroless plating, 175
Electrolysis, 123
Electrolyte concentration cells, 138
Electrolytic cells, 130
Electromagnetic radiations, 252
Electromagnetic spectrum, 251
Electromotive force, 131
Electroplating, 173, 174, 175
Emulsions, 104, 109
Engineering plastics, 37
Equivalent conductance, 124, 125, 126
Fillers, 35
Fingerprint region, 269
Fire point, 111
Fischer-tropsch process, 197
Flame emission spectroscopy, 259
Flame photometry, 259, 261, 262
Flash point, 111
Flue gas, 215
Fluid bed catalytic cracking, 203
Foaming, 9
Fossil fuels, 184
Frequency, 253
Freundlich adsorption isotherm, 51
Friction, 101
Fuel
characteristics, 185
classification, 184
gaseous, 186
liquid, 186
solid, 185
Galvanic series, 145
Gaseous fuels, 210
Gasoline, 204
Glass electrode, 136
Graft copolymer, 32
Graphite, 107
Grinding wheels, 99
Gross calorific value, 187
Hard water, 3
Index
Hardness
estimation, 5
units, 4
Heat treatment processes
age hardening, 248
annealing, 248
case hardening, 249
flame hardening, 250
induction hardening, 250
normalizing, 248
quenching, 248
surface hardening, 249
tempering, 249
Helmholtz electrical double layer, l31
Hetero-chain polymer, 31
High polymers, 30
Homo-chain polymer, 31
Homopolymers, 31
Hot dipping, 171
Hydrodynamic lubrication, 102
Hydrogen bomb, 74
Hydrogen electrode, 132
Impurities in water, 2
Indicator electrode, 146
Infrared spectrometer, 270
Infrared spectroscopy, 266
Ion exchange, 12, 14
Ion selective electrodes, 136
Irreversible cells, 141
Isostere, 55
Knocking, 207
Lambert's law, 255

Langmuir adsorption isothenn, 52, 53
Leaded petrol, 207
Light absorption, 255
Light water nuclear power plant, 73
Liquefied petroleum gas, 211
Lubricants, 36, 114
additives, 105
classification, 104
functions, 10 1
liquid, 104
properties, 109
semisolid, 104, 108
solid, 104, 106
synthetic, 106
279
Lubrication, 10 1
extreme pressure, 103
fluid film, 102
hydrodynamic, 102
mechanisms, 102
thin film, 103
~acroD101ecules,
30
Mass defect, 66
Metallic coatings, 171
Mineral oils, 104
Molar conductance, 125
Molybdenum disulphide, 107
Moulding, 40
compression, 40
injection, 41
Nanomaterials
applications, 119
Natural abrasives, 97
Natural gas, 210
Nernst equation, l34, l35
Net calorific value, 187
Neutral refractories, 92
Neutralization number, 113
Nuclear energy, 72
Nuclear fission
characteristics, 69
Nuclear power reactor
components, 72
Nuclear reaction, 65
fission reactions, 68
fusion reactions, 69
projectile capture particle emission reactions, 68
projectile capture reactions, 68
Nucleons, 66
Nylon 6,6, 39
Ohm's law, 124

Oiliness, 103
Oligopolymers, 30
Organic coatings, 178
Otto-Hoffmann's method, 196
Oxidation potential, 131
Phase
gaseous, 232
liquid, 233
solid, 233
280
Index
Phase diagram, 235, 240

Phase rule, 235, 241
Photovoltaic cells, 83
Pigments, 35
Plasticizers, 36
Polycarbonates,38
Polyethyleneterephthalate, 40
Polymerization, 30, 204
addition polymerization, 32, 34
condensation, 33, 34
copolymerization, 32
step polymerization, 33
Polytetrafluoroethylene, 38
Polyurethanes, 38
Polyvinyl chloride, 37
Porosity, 91
Potable water, 17
Potentiometric titrations, 146
Pour point, 112
Primary batteries
alkaline battery, 79
Lechlanche cell, 78
lithium battery, 79
mercury battery, 80
zinc-carbon dry cell, 78
Priming, 8
Producer gas, 211
Protective coatings, 170
Radiations
absorption, 253
Reduction potential, 131
Redwood seconds, 11 0
Reference electrodes, 132
Reforming
dehydrogenation, 208
hydrocracking, 208
isomerization, 208
Refractories, 88
classification, 92
manufacture, 89
properties, 89
Refractory bricks
high alumina bricks, 93
zirconia refractory bricks, 93
Reverse osmosis, 22
Reversible cells, 140
Rubber, 42
Saponification number, 114
Scales, 9
Secondary batteries, 77
acid battery, 81
edison battery, 83
iron-nickel oxide cells, 83
lead-acid accumulator, 81
nicad battery, 82
Sludges, 9
Softening of water, 12
Solar cells, 83
Specific conductance, 124, 125, 126
Spectroscopy
atomic spectroscopy, 254
molecular spectroscopy, 254
Spraying, 172
Standard cell, 141
Subcritical mass, 71
Supercritical mass, 71
Synthetic abrasives, 98
Teflon, 38
Thermocole,39
Treatment processes, 18
coagulation, 18
filtration, 18
screening, 18
sedimentation, 18
sterilization, 19
Vibrational spectroscopy, 266

Vibrations
bending, 267
deformation, 267
stretching, 267
Viscosity, 110
Viscosity index, 110
Visible and ultraviolet spectroscopy, 262, 265
Vulcanization, 42
Water gas, 213

Water treatment, 1
Wave number, 253
Wavelength, 252
Wet corrosion, 156
Wind energy, 86
Zeolite process, 12, 13, 15

Zeolite softener, 13

Engineering Chemistry

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Engineering Chemistry

PHI Learning lfutmGO@ llilW1BO@ctl

Saeed Book Bank

EERING CHEMISTRY, Second Edition

'rinting (Second Edition)

Potable Water (Water for Domestic Supply)

Polymers and Composites

Nuclear Reactor or Atomic Pile

Some Important Refractory Bricks

11 CorroSion and Corrosion Control

Factors Influencing Corrosion

To impart sound concepts of the principles of chemistry, different application-oriented topics

(b) Boiler feed

Should not be alkaline

Soft, free from colour, Fe

Different uses of water

Alkalinity in water tends to neutralize

Scale formed on using untreated water

Produces cracks on the paper.

Free from turbidity,

Causes uneven dyeing, leaves stains on

The impurities present in water may be broadly classified as follows.

The following are the types of suspended impurities:

(a) Inorganic: Clay and sand

They are algae, fungi and bacteria.

Sources of Impurities in Water

The sources of impurities in water are the following:

1.3 HARD WATER

1.3.1 Disadvantages of Hard Water

1.3.2 Hardness of Water

Hardness of water due to the presence of bicarbonates of Ca and Mg is called temporary

The following are the common units used in hardness measurements.

2. Milligram per litre:

It is defined as the number of milligrams of CaC03 present in one i

1 mgll = 1 mg of CaC03 equivalent hardness in one litre of water

Since weight of 1 litre of water = 1 kg

1 mg/l = 1 mg of CaC03 per 106 mg of water

1 part of CaC03 per 106 parts of water

Thus, mathematically both units are equal.

- - - - - - - - - = - - - - - - ' = - - - - x mo ecu ar welg t 0

Multiplication factor for converting various substances into equivalents of CaC03

EDTA is ethylenediaminetetraaceticacid. The structure of EOTA is

[:;.] + Eriochrome B1ack-T - > [:g Eriochrome BlaCk+omPlex

[ ::Eriochrome Black-T].omPlex + EDTA -> [ : :EDTA] complex + Eriochrome Black-T

Let the volume of EDTA consumed be VI ml.

This hardness is present in V ml of hard water.

ppm of CaC03 equivalent

ppm of CaC03 equivalent

Hence, (total hardness) - (permanent hardness) gives the temporary hardness.

1000 ml of 1M EDTA = 100 g of CaC03

The alkalinity of natural water may be taken as an indication of the concentration of

(P = Phenolphthalein alkalinity; M = Methyl orange alkalinity)

1.4.1 Experimental Determination of Alkalinity

Additional volume of acid used up to methyl orange end point

Methyl orange alkalinity (M) in terms of calcium carbonate equivalent

BOILER FEED WATER

Essential Requirements of Boiler Feed Water

Boiler feed water should be free from the following:

1.5.4 Sludge and Scale Formation in Boilers

(a) Sludge in boiler and (b) scale in boiler.

Table 1.4 shows the differences between sludges and scales.

TABLE 1.4 Differences between sludges and scales

1. Scales are hard deposits which stick very

2. Sludges can be removed easily.