Engineering Chemistry by K. Sesha Maheswaramma, Mridula Chugh PDF

Engineering Chemistry
K. Sesha Maheswaramma
Department of Chemistry
Jawaharlal Nehru Technological University, Anantapur
College of Engineering Pulivendula (JNTUACEP)
Andhra Pradesh
Mridula Chugh
Department of Chemistry
Ganga Institute of Technology and Management
Jhajjar, Haryana
A01_ENGINEERING-CHE00_SE_1181_FM.indd 1 5/25/2016 4:11:01 PM

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Dedication
To my in-laws late Smt and Sri Chavva Narayanamma and Eswara Reddy;
my paternal grandparents late Smt and Sri Kalluru Akkayya and Pedda Obula Reddy;
my maternal grandparents late Smt and Sri Rami Reddy Rosamma and Chinna Obula Reddy;
my aunt late Smt Kalluru Nameless
and
my uncle late Sri Kalluru Naga Bhusana Reddy
—K. Sesha Maheswaramma
To my husband Gaurav Chugh for his inspiration.

—Mridula Chugh

This page is intentionally left blank
BRIEF CONTENTS
Forewordxxi
Prefacexxiii
About the Authors xxv
1. Water Technology 1.1
2. Polymers 2.1
3. Fuels and Combustion 3.1
4. Alternate Energy Resources 4.1
5. Electrochemistry and Batteries 5.1
6. Science of Corrosion 6.1
7. Chemistry of Engineering Materials 7.1
8. Phase Rule 8.1
9. Photochemistry 9.1
10. Surface Chemistry 10.1
11. Themodynamics 11.1
12. Metals in Biological System 12.1
13. Organometallic Compounds 13.1
14. Coordination Chemistry 14.1
15. Structure and Reactivity of Organic and Inorganic Molecules 15.1

vi Brief Contents
16. Stereochemistry 16.1
17. Spectroscopy 17.1
18. Thermal Analysis 18.1
19. Chromatography 19.1
20. Solid State and X-Ray Diffraction 20.1
21. Green Chemistry 21.1
Lab Manual Online

Index I.1

CONTENTS
Forewordxxi
Preface xxiii
About the Authors xxv
1. Water Technology 1.1

1.1 Introduction 1.1
1.2 Sources of Water 1.1
1.3 Types of Impurities Present in Water 1.2
1.4 Hard Water and Hardness 1.3
1.5 Determination of Hardness 1.8
1.6 Dissolved Oxygen (DO) 1.15
1.7 Determination of Chlorides in Water 1.16
1.8 Determination of Acidity in Water 1.17
1.9 Alkalinity of Water 1.18
1.10 Disadvantages of Hard Water 1.23
1.11 Quality of Water for Domestic Use 1.24
1.12 Treatment of Water for Domestic Use 1.24
1.13 Break-Point Chlorination 1.31
1.14 Boilers and Boiler Troubles 1.32
1.15 Softening of Water 1.38
1.16 Desalination 1.51
1.17 Review Questions 1.54
Fill in the Blanks 1.54
Multiple-choice Questions 1.56
Short Answer Questions 1.61
Descriptive Questions 1.65
Problems for Practice 1.66
2. Polymers 2.1
2.2 Degree of Polymerisation 2.1
2.3 Classification of Polymers 2.2
2.3.1 Classification Based on Source 2.2
2.3.2 Classification Based on Composition 2.2

viii Contents
2.3.3 Classification Based on Chemical Composition 2.3

2.3.4 Classification Based on Structure 2.3
2.3.5 Classification Based on Mode of Polymerisation 2.4
2.3.6 Classification Based on the Molecular Forces 2.4
2.3.7 Classification Based on Tacticity 2.4
2.4 Types of Polymerization 2.5
2.4.1 Condensation Polymerisation or Step Polymerisation 2.5
2.4.2 Addition/Vinyl/Chain Polymerisation 2.9
2.4.3 Coordination Polymerisation 2.15
2.5 Molecular Mass of a Polymer 2.17
2.6 Plastics 2.18
2.7 Important Polymers—Composition, Preparation, Properties
and Engineering Uses 2.19
2.7.1 Thermoplastics 2.19
2.7.2 Thermosetting Plastics 2.22
2.8 Rubber (Elastomers) 2.25
2.8.1 Processing of Natural Rubber 2.25
2.8.2 Gutta–Percha 2.26
2.8.3 Vulcanisation of Rubber 2.27
2.8.4 Compounding of Rubber 2.28
2.8.5 Synthetic Rubbers or Artificial Rubber 2.29
2.8.6 Important Artificial Rubbers 2.29
2.9 Reinforced or Filled Plastics 2.33
2.9.1 Composition 2.34
2.9.2 Nature of Polymers Used 2.34
2.9.3 Application of Filled Plastics (Reinforced Plastics) 2.34
2.10 Biopolymers 2.35
2.10.1 Major Feed Stocks for Biopolymers 2.35
2.10.2 Preparation Methods 2.35
2.10.3 Important Biodegradable Polymers 2.35
2.10.4 Importance of Biopolymers in Sustainable Development 2.36
2.11 Conducting Polymers 2.37
2.11.1 Intrinsically Conducting Polymer (ICP) or Conjugated π-Electrons
Conducting Polymer 2.37
2.11.2 Conducting Polyaniline 2.39
2.11.3 Extrinsically Conducting Polymers 2.40
2.12 Polyphosphazenes/Phosphonitrilic Polymers 2.40
2.13 Composites 2.42
2.13.1 Constituents of Composites 2.42
2.13.2 Classification of Composites 2.42
2.13.3 Advantages of Composites over Conventional Materials 2.44
2.13.4 Applications of Composites 2.44

Contents ix
3. Fuels and Combustion 3.1

3.2 Classification of Fuels 3.1
3.3 Units of Heat 3.2
3.4 Calorific Value 3.2
3.5 Determination of Calorific Value 3.3
3.5.1 Bomb Calorimeter 3.3
3.5.2 Junker’s Calorimeter 3.4
3.6 Characteristics of Good Fuel 3.7
3.7 Solid Fuels 3.8
3.7.1 Coal 3.8
3.7.2 Analysis of Coal 3.8
3.7.3 Metallurgical Coke 3.16
3.7.4 Manufacture of Metallurgical Coke 3.17
3.8 Liquid Fuels 3.18
3.8.1 Petroleum Refining 3.18
3.8.2 Important Petroleum Products and their Uses 3.20
3.9 Synthetic Petrol 3.21
3.9.1 Cracking 3.21
3.9.2 Fischer–Trapsch Method 3.23
3.9.3 Bergius Method 3.23
3.10 Power Alcohol 3.24
3.10.1 Manufacture of Power Alcohol 3.25
3.11 Knocking 3.26
3.12 Diesel Engine, Cetane and Octane Number 3.26
3.13 Gaseous Fuels 3.28
3.13.1 Natural Gas 3.28
3.13.2 Producer Gas (or) Suction Gas 3.29
3.13.3 Water Gas (or) Blue Gas 3.29
3.13.4 Coal Gas 3.30
3.13.5 Biogas 3.30
3.14 Flue Gas Analysis by Orsats Apparatus 3.31
4. Alternate Energy Resources 4.1

4.1.1 Conventional or Traditional Energy Resources 4.1
4.1.2 Nonconventional Energy Resources or Renewable Energy Sources 4.1
4.1.3 Alternative Energy 4.2
4.2 Non-Conventional Energy Sources and Storage Devices 4.2
4.2.1 Solar Energy 4.2
4.2.2 Wind Energy 4.9
4.2.3 Geothermal Energy 4.10

x Contents
4.2.4 Water Power 4.10

4.2.5 Biomass 4.12
4.2.6 Nuclear Energy 4.13
4.2.7 Nuclear Reactions 4.15
5. Electrochemistry and Batteries 5.1

5.2 Electrolysis 5.1
5.2.1 Laws of Electrolysis 5.2
5.3 Electrolytic Conduction 5.4
5.3.1 Factors Affecting Electrolytic Conduction 5.4
5.3.2 Electrical Resistance and Conductance 5.4
5.3.3 Specific, Equivalent and Molar Conductivities 5.5
5.3.4 Equivalent Conductivity 5.6
5.3.5 Molar Conductivity 5.7
5.3.6 Measurement of Electrolytic Conductance 5.8
5.3.7 Variation of Conductivity with Concentration 5.9
5.3.8 Conductance Behaviour of Strong Electrolyte 5.10
5.3.9 Conductance Behaviour of Weak Electrolyte 5.10
5.4 Kohlrausch’s Law of Independent Migration of Ions 5.11
5.5 Conductometric Titrations 5.15
5.6 Electrochemical Cells 5.21
5.7 Types of Electrodes 5.28
5.8 Reference Electrode 5.31
5.9 Ion Selective Electrodes (ISE) 5.34
5.9.1 Electrochemical Circuit and Working of ISE 5.34
5.9.2 Types of Ion – Selective Membranes 5.35
5.9.3 Applications of Ion Selective Electrodes 5.37
5.10 Glass Electrode 5.38
5.10.1 Construction of Glass Electrode 5.38
5.11 Concentration Cell 5.40
5.12 Potentiometric Titrations 5.42
5.13 Electrochemical Sensors 5.44
5.13.1 Potentiometric Sensor 5.44
5.13.2 Analysis of Glucose in Blood 5.45
5.13.3 Analysis of Urea 5.45
5.14 Voltammetry 5.45
5.14.1 Linear Sweep Voltammetry (LSV) 5.46
5.14.2 Ferric Fe3+/Fe2+ System 5.47
5.14.3 Cyclic Voltammetry 5.49
5.14.4 Applications of Voltammetry 5.50

Contents xi
5.15 Batteries 5.51

5.15.1 Advantages of Batteries 5.51
5.15.2 Disadvantages of Batteries 5.51
Solved Numerical Problems 5.71
Problems for Practice 5.79
6. Science of Corrosion 6.1

6.1.1 Causes of Corrosion 6.1
6.1.2 Types of Corrosion 6.2
6.2 Galvanic Series 6.16
6.2.1 Factors Affecting Corrosion 6.17
6.3 Protection from Corrosion (Preventive Measures for Corrosion Control) 6.19
7. Chemistry of Engineering Materials 7.1

7.1 Semiconducting and Super Conducting Materials 7.1
7.1.1 Semiconductor 7.1
7.1.2 Applications of Semiconductors 7.3
7.1.3 Superconductors 7.3
7.2 Magnetic Materials 7.4
7.2.1 General Properties of Magnetic Materials 7.4
7.2.2 Classification of Magnetic Materials 7.4
7.2.3 Applications of Magnetic Materials 7.6
7.3 Cement 7.6
7.3.1 Classification of Cement 7.7
7.3.2 Raw Materials used in the Manufacture of Portland Cement 7.7
7.3.3 Manufacture of Portland Cement 7.8
7.3.4 Chemical Composition of Portland Cement and its Importance 7.12
7.3.5 Setting and Hardening of Cement 7.13
7.3.6 ISI Specifications of Cement 7.15
7.3.7 Analysis of Cement 7.16
7.3.8 Plaster of Paris/Gypsum Plaster 7.16
7.4 Refractories 7.17
7.4.1 Characteristics of Good Refractory Materials 7.17
7.4.2 Failures of Refractory Materials 7.18
7.4.3 Classification of Refractories 7.18

xii Contents
7.4.4 Properties of Refractories 7.18

7.4.5 Manufacture of High-Alumina Bricks, Magnesite Bricks
and Zirconia Bricks 7.21
7.5 Lubricants 7.22
7.5.1 Important Functions of Lubricants 7.22
7.5.2 Mechanism of Lubrication 7.23
7.5.3 Classification of Lubricants 7.24
7.5.4 Properties of Lubricants 7.27
7.5.5 Redwood Viscometer 7.31
7.5.6 Engler’s Viscometer 7.33
7.5.7 Saybolt Viscometer 7.33
7.5.8 U-Tube Viscometer 7.34
7.5.9 Conversion of Redwood, Engler and Saybolt Viscosities
into Absolute Units 7.35
7.6 Explosives and Propellants 7.36
7.6.1 Some Important Terms about Explosives 7.36
7.6.2 Classification of Explosives 7.37
7.6.3 Precautions during Storage of Explosives 7.39
7.6.4 Blasting Fuses 7.40
7.6.5 Important Explosives and their Preparation 7.40
7.6.6 Rocket Propellants 7.41
7.6.7 Characteristics of a Good Propellant 7.42
7.6.8 Classifications of Propellants 7.43
7.7 Nanomaterials 7.44
7.7.1 Synthesis of Nanomaterials 7.44
7.7.2 Characterisation 7.45
7.7.3 Importance 7.45
7.7.4 Broad Classification of Nanomaterials 7.45
7.7.5 Fullerenes 7.46
7.7.6 Types of Fullerenes 7.46
7.7.7 Properties of Nanomaterials 7.49
7.7.8 Applications of Nanomaterials 7.51
7.8 Liquid Crystals 7.51
7.8.1 Characteristics of Liquid Crystal Phase 7.52
7.8.2 Classification of Liquid Crystals 7.52
7.8.3 Thermotropic Liquid Crystals 7.52
7.8.4 Lyotropic Liquid Crystals 7.57
7.8.5 Chemical Properties of Liquid Crystals 7.57
7.8.6 Applications of Liquid Crystals 7.58
7.9 Abrasives 7.59
7.9.1 Hardness of Abrasive 7.59
7.9.2 Natural Abrasives 7.60
7.9.3 Artificial Abrasives 7.60
Multiple-choice questions 7.64

Contents xiii
8. Phase Rule 8.1

8.2 Explanation of the Terms Involved in Phase Equilibria 8.1
8.2.1 Phase (P) 8.1
8.2.2 Components (C) 8.2
8.2.3 Degree of Freedom (F) 8.4
8.2.4 True and Metastable Equilibrium 8.5
8.2.5 Eutectic Mixture and Eutectic Point 8.5
8.2.6 Triple Point 8.6
8.3 Phase Rule 8.6
8.3.1 Assumptions for the Validation of Phase Rule 8.6
8.3.2 Thermodynamic Derivation of the Phase Rule 8.6
8.3.3 Utility of Phase Rule | Application of Phase Rule 8.8
8.3.4 Limitations of Phase Rule 8.8
8.4 Phase Diagrams 8.9
8.5 One Component System 8.9
8.6 Two Component System 8.14
8.6.1 Eutectic System 8.14
8.6.2 Lead (Pb) – Silver (Ag) System 8.18
8.7 Heat Treatment of Steel 8.21
Solved Numerical Problems 8.32
9. Photochemistry 9.1
9.2 Light Source in Photochemistry 9.1
9.3 Laws of Photochemistry 9.2
9.3.1 Grotthuss–Draper Law or The First Law of Photochemistry 9.2
9.3.2 Stark-Einstein Law or Photochemical Equivalence Law 9.2
9.3.3 Beer-Lambert Law 9.3
9.4 Photophysical and Chemical Processes 9.3
9.4.1 Photophysical Process 9.3
9.4.2 Photochemical Process 9.4
9.5 Quantum Yield and Quantum Efficiency 9.6
9.6 Photosensitisation 9.6
9.7 Photodynamic Therapy 9.6
9.8 Important Photochemical Reactions 9.7

xiv Contents
10. Surface Chemistry 10.1

10.2 Adsorption 10.1
10.2.1 Mechanism of Adsorption 10.2
10.2.2 Adsorption is Exothermic 10.2
10.2.3 Difference between Adsorption and Absorption 10.2
10.2.4 Examples of Adsorption, Absorption, and Sorption 10.3
10.2.5 Positive and Negative Adsorptions 10.3
10.2.6 Classification of Adsorption 10.3
10.2.7 Factors Affecting the Adsorption of Gases by Solids 10.4
10.2.8 Adsorption Isotherms 10.5
10.2.9 Applications of Adsorption 10.16
10.3 Colloidal State 10.17
10.3.1 Types of Solution 10.17
10.3.2 Classification of Colloids 10.18
10.3.3 Properties of Colloidal Solutions 10.21
10.3.4 Applications of Colloids 10.28
Long Answer Questions 10.39
11. Thermodynamics 11.1

11.1.1 Thermodynamic Terms and Basic Concepts 11.1
11.2 Types of Thermodynamic Systems 11.2
11.2.1 Isolated System 11.2
11.2.2 Closed System 11.2
11.2.3 Open System 11.2
11.3 Intensive and Extensive Properties 11.3
11.3.1 Intensive Property 11.3
11.3.2 Extensive Property 11.3
11.3.3 State Variables 11.3
11.4 Reversible and Irreversible Process 11.3
11.4.1 Reversible Process 11.3
11.4.2 Irreversible Process 11.4
11.4.3 Thermodynamic Processes 11.4
11.4.4 Isothermal Process or Isothermal Change 11.5
11.4.5 Indicator Diagram 11.6
11.4.6 Work Done by a System in an Adiabatic Process 11.8
11.4.7 First Law of Thermodynamics and its Application 11.10
11.4.8 Second Law of Thermodynamics 11.13
11.4.9 Carnot’s Engine, Efficiency 11.14
11.4.10 Working of Carnot’s Engine 11.16
11.4.11 Absolute Zero 11.18
11.4.12 Numerical Problems Based on Carnot’s Cycle 11.19

Contents xv
11.4.13 Solved Numerical Problems Based on Isothermal

and Adiabatic Process 11.21
11.5 Thermodynamic Potentials and Maxwell Equations 11.33
11.5.1 Thermodynamic Potential 11.33
11.5.2 Internal Energy (U)11.33
11.5.3 Total Heat Function (H)11.34
11.5.4 Helmholtz Function (F)11.35
11.5.5 Gibb’s Free Energy or Gibb’s Function (G)11.36
11.5.6 Maxwell’s Equations 11.37
11.5.7 Clausius–Clapeyron Equation 11.38
11.5.8 Derivation of the Stefan–Boltzmann Law using Maxwell’s Equations 11.40
11.5.9 Joule–Thomson Effect or Joule–Kelvin Effect 11.44
12. Metals in Biological System 12.1

12.2 Essential Elements 12.1
12.2.1 Bulk Elements 12.2
12.2.2 Macrominerals 12.2
12.2.3 Micro Elements (Trace Elements) 12.2
12.3 Non-Essential Elements 12.4
12.4 Important Metals in Biological Systems 12.4
12.4.1 Haemoglobin 12.4
12.4.2 Myoglobin 12.6
12.4.3 Vitamin B1212.7
12.4.4 Chlorophyll 12.8
12.5 Metals and their Toxicity 12.9
12.5.1 Toxicity of Arsenic 12.9
12.5.2 Toxicity of Lead 12.10
12.5.3 Toxicity of Mercury 12.11
13. Organometallic Compounds 13.1

13.1.1 Organometallic Chemistry Timeline 13.1
13.2 Organolithium Compounds 13.2
13.2.1 Preparation of Organolithium Compounds 13.2
13.2.2 Properties of Organolithium Compounds 13.3

xvi Contents
13.3 Organomagnesium Compounds 13.5

13.3.1 Preparation of Organomagnesium Compounds 13.5
13.3.2 Properties of Organomagnesium Compounds 13.7
13.4 Metal Carbonyls 13.10
13.4.1 Ligand 13.11
13.4.2 Effective Atomic Number 13.11
13.4.3 Preparation of Carbonyls 13.11
13.4.4 Properties of Carbonyls 13.12
13.4.5 Structure of Carbonyls 13.12
14. Coordination Chemistry 14.1

14.2 Basic Requirements to Formation of Coordination Compound 14.1
14.3 Nomenclature of Metal Complexes 14.3
14.3.1 Cationic Complex 14.4
14.3.2 Anionic Complex 14.4
14.3.3 Nonionic Complexes 14.5
14.3.4 Polynuclear Complex 14.6
14.3.5 Complex with Metal-Metal Bond 14.6
14.4 Theories of Coordination Chemistry 14.7
14.4.1 Werner’s Theory 14.7
14.4.2 Sidgwick’s Electronic Concept Theory 14.8
14.4.3 Valance Bond Theory 14.9
14.4.4 Crystal Field Theory 14.11
14.4.5 Common Single Atomic Ligands and their Field Strength 14.14
14.4.6 Molecular Orbital Theory of Coordination Complexes 14.16
14.5 Factors Affecting the Stability of Coordination Compounds 14.17
14.6 Determination of Complex Ion Formation 14.19
14.7 Stability of Coordination Compounds 14.20
14.8 Applications of Coordination Compounds 14.22
15. Structure and Reactivity of Organic and Inorganic Molecules 15.1

15.2 Hybridisation 15.1
15.2.1 Salient Features of Hybridisation 15.1
15.2.2 Important Conditions for Hybridisation 15.2
15.2.3 Types of Hybridisation 15.2

Contents xvii
15.3 Bond Polarisation 15.5

15.3.1 Electron Displacement in Covalent Bonds 15.5
15.4 Reaction Intermediates 15.9
15.4.1 Free Radicals 15.9
15.4.2 Carbocations or Carbonium Ions 15.10
15.4.3 Carbanions 15.12
15.4.4 Carbenes 15.13
15.4.5 Nitrenes or Imidogens 15.13
15.4.6 Benzynes 15.14
15.5 Molecular Orbital Theory 15.19
15.5.1 Important Points on Molecular Orbital Diagrams 15.21
15.5.2 Fundamental Steps for Constructing Molecular Orbitals 15.21
15.5.3 Five Basic Rules of Molecular Orbital Theory 15.22
15.5.4 Linear Combination of Atomic Orbitals and Type of Atomic Orbitals 15.22
15.5.5 Molecular Orbital Energy Level Diagrams of Homo Atomic Molecules15.23
15.5.6 Molecular Energy Level Diagrams of Hetero Atomic Molecules 15.29
16. Stereochemistry 16.1

16.2 Isomerism 16.1
16.2.1 Structural Isomerism 16.1
16.2.2 Space or Stereoisomerism 16.1
16.3 Classification of Structural Isomerism 16.1
16.3.1 Chain or Nuclear Isomerism 16.2
16.3.2 Position Isomerism 16.2
16.3.3 Ring or Chain Isomerism 16.2
16.3.4 Functional Group Isomerism 16.2
16.3.5 Metamerism 16.2
16.3.6 Tautomerism 16.3
16.4 Classification of Stereoisomerism 16.3
16.4.1 Geometrical Isomerism 16.3
16.4.2 Optical Isomerism 16.4
16.4.3 Conformational Isomers 16.10
16.4.4 R–S Nomenclature or CIP Nomenclature 16.10
16.4.5 E–Z Nomenclature 16.12
16.5 Molecular Representation 16.12
16.5.1 Wedge and Dash Projections 16.12
16.5.2 Fisher Projections 16.13
16.5.3 Sawhorse Representation 16.13
16.5.4 Newman Representation 16.14
16.6 Molecular Isomerism 16.14

xviii
Contents

17. Spectroscopy 17.1

17.2 Ultra Violet and Visible Spectroscopy 17.2
17.2.1 Principle 17.2
17.2.2 Instrumentation 17.2
17.2.3 Instrumental Design 17.3
17.2.4 Electronic Transitions 17.5
17.2.5 Chromophores 17.6
17.2.6 Auxochrome 17.6
17.2.7 Woodward–Fieser Rules 17.7
17.2.8 Factors Affecting the Position of the λ Maximum
and Intensity of Radiation 17.10
17.2.9 Franck-Condon Principle 17.11
17.2.10 Solved Problems Based on UV-Vis Spectroscopy 17.12
17.2.11 Applications of UV-Visible Spectroscopy 17.13
17.3 IR-Spectroscopy 17.14
17.3.1 Basic Principle 17.15
17.3.3 Molecular Vibrations 17.17
17.3.4 Factors Affecting Vibrational Frequency 17.22
17.3.5 Degrees of Freedom 17.22
17.3.6 Solved Problems Based on IR Spectra 17.22
17.3.7 Applications of IR Spectroscopy 17.23
17.4 Nuclear Magnetic Resonance Spectroscopy 17.24
17.4.3 Chemical Shift 17.26
17.4.4 Spin-Spin Splitting, Spin-Spin Interaction, Spin–Spin Coupling
or Fine Spectrum 17.28
17.4.5 Magnetic Resonance Imaging 17.29
17.4.6 High Resolution Proton Magnetic Resonance Spectroscopy 17.30
17.4.7 NMR Applications 17.32
17.4.8 Solved Problems Based on Proton NMR 17.33
18. Thermal Analysis 18.1

18.2 Thermogravimetric Analysis 18.1

Contents xix
18.2.1 Principle of TGA 18.2

18.2.2 Applications of TGA 18.3
18.3 Differential Thermal Analysis 18.4
18.3.1 Principle of DTA 18.4
19. Chromatography 19.1

19.1.1 Chromatography Timeline 19.1
19.2 Classification of Chromatography 19.2
19.2.1 Classification Based on Mobile Phase 19.2
19.2.2 Classification Based on Attractive Forces 19.2
19.2.3 Classification Based on Partition of Relative Solubility
of Analyte in Mobile and Stationary Phase 19.2
19.2.4 Chromatographic Techniques on the Type of Support
Material Used in the System 19.2
19.3 Types of Chromatography 19.3
19.3.1 Gas-Liquid-Chromatography 19.3
19.4 Chromatography Theory 19.10
19.4.1 Distribution Coefficient or Partition Coefficient (K)19.10
19.4.2 Retention Time (tR)19.10
19.4.3 Retention Volume (VR)19.11
19.4.4 Plate Theory 19.12
19.5 High Performance Liquid Chromatography 19.14
19.5.2 Theory of High Performance Liquid Chromatography 19.19
20. Solid State and X-Ray Diffraction 20.1

20.1.1 Crystal Structure 20.1
20.2 Crystal Systems 20.1
20.2.1 Laws of Crystallography 20.2
20.3 Crystal Defects 20.3
20.3.1 Stoichiometric Defect 20.3
20.3.2 Non-stoichiometric Defect 20.4
20.4 X-Ray Diffraction 20.6
20.4.1 Introduction 20.6

xx Contents
20.4.3 X-ray Diffraction of Crystals and Bragg’s Equation 20.6

20.4.4 Determination of Crystal Structure with Bragg’s Equation 20.8
20.4.5 X-ray Diffraction Methods 20.8
20.4.6 Instrumentation of X-ray 20.9
20.5 Application of X-ray Diffraction 20.10
21. Green Chemistry 21.1

21.2 Twelve Principles of Green Chemistry 21.1
21.3 Importance of Green Synthesis 21.2
21.3.1 Methods for Green Synthesis 21.3
21.3.2 Applications of Green Synthesis 21.4
21.4 Greenhouse Concepts 21.5
21.4.1 Types of Greenhouse 21.5
21.5 Greenhouse Gases and Greenhouse Effect 21.5
21.5.1 Natural Greenhouse Effect 21.6
21.5.2 Enhanced Greenhouse Effect 21.6
21.5.3 Greenhouse Gas Effect 21.7
21.5.4 Requirements for Greenhouse 21.7
21.6 Carbon Sequestration 21.8
21.6.1 Importance of Carbon Sequestration 21.8
21.7 Why Carbon Dioxide is a Major Problem 21.9
Short answer Questions 21.10
Lab Manual Online

Index I.1

FOREWORD
I feel proud to write these few lines as my student Smt K Sesha Maheswaramma, working as assistant
professor, Department of Chemistry, JNTUACEP, Andhra Pradesh, has brought out this book success-
fully. With a personal note, I wish to place on records that from a remote village Gollala Guduru of
Kadapa District, where the expectation of girl child’s higher education is minimal, she not only became
the assistant professor of an engineering college but also started publishing books! Although the sub-
ject Chemistry is unwelcomed by the students of this region, she has mastered not only the subject but
also the art of writing.
In the recent past, with too much specialization, it was very difficult for anyone to have a com-
prehensive understanding of any subject with broader vision due to limited resources to teaching and
research. To overcome this, recently, ‘Interdisciplinary Approach’ is stressed very much. In this con-
text, Dr K. Sesha Maheswaramma has brought out Engineering Chemistry by integrating Chemistry
with water technology, alternate energy resources, engineering materials, thermodynamics, analytical
methods, green chemistry, etc. This book is most useful to all undergraduate students (both B.Tech.
and B.Sc.) and postgraduate students of M.Sc. Chemistry as well as M.Sc. Physics.
It is true that scientific knowledge is that of empirical—dealing with facts. Reporting of facts
done through the medium of language is marvellous. I sincerely appreciate her hard work and efforts
in bringing out this book.
Rev. Fr. Dr. T. Amala Arockia Raj, SJ

Principal, Loyola Degree College (YSRR)
Pulivendula, Kadapa (Dt.), Andhra Pradesh

PREFACE
Chemistry, as a basic science, plays a vital role in making a foundation for engineering students and
ensuring security by shaping a fruitful superstructure for their entire career.
A comprehensive knowledge of fundamental chemistry is essential for promising and sustain-
able future. Chemistry plays a leading role in shaping the future of research and development with the
integration of multidisciplinary fields such as life sciences, material science, medicine, engineering
and technology.
Engineering Chemistry text book is exclusively designed for the needs of undergraduate students
of all disciplines of science, engineering and technology. This book is designed based on the syllabi of
various universities and autonomous colleges of India. Hence, this book highly recommended for both
graduate and under graduate students of science, engineering and technology. This book introduces
the fundamental concepts in a simple and illustrative manner. This book can also be a useful as self-
learning guide for students as well as teachers to teach in a highly practical way. This book contains 21
theory chapters and 14 lab experiments as an online supplement as per the latest engineering chemistry
syllabi offered in all Indian Universities. Each chapter starts with brief introduction and provides in-
depth information of the relevant topics covered in the syllabus. The textbook covers all the topics and
includes latest information with diagrams, tables and solved numerical problems, and the review zone
contains fill in the blanks, multiple-choice questions, short answer questions and descriptive questions
for examinations. As the book discusses the fundamentals with a practical approach it is suggested for
several nationwide competitive exams such as NET, SET, GATE Groups and Civil Services.
We heartily welcome valuable comments and suggestions from our readers for the improvement
of the future editions of this book, which may be addressed to kallurumahi@rediffmail.com and
mridula.chugh@gmail.com.
ACKNOWLEDGEMENTS
From the bottom of my heart, I give all glory and praises to the Almighty for his everlasting mercy and
abundant compassion to accomplish this work.
Mere words could never express my gratitude to my teachers who provided me all support, guid-
ance and precious life lessons. They activated hunger for knowledge and wisdom, and inspired me to
plan a better future by adding my brick of effort to the world of Chemistry.
I am beholden to the authorities of JNTUA, Anantapur, for their encouragement to sharpen my
skills and contribute same to the development of student community. This effort of ours would not have
been a success but for the contributions made by a lot of people.

xxiv
Preface
I express my heartfelt thanks to the members of editorial and production team of Pearson
Education, especially Mr Sojan Jose, Ms R. Dheepika and Mr M. Balakrishnan, for their unrelenting
efforts in editing the manuscript and their immense contribution has shaped this stupendous work.
I wish to express my sincere thanks to my family members. I owe much to my parents Sri Kalluru
Naga Malla Reddy and Smt. Gangulamma, my brothers Sri Mallikarjuna Reddy and Sri Nagarjuna
Reddy for their cherished, unstinted love and encouragement in all my good activities.
I wish to express my indebted thanks to my husband Dr C. Mallikarjuna Reddy for his unbound-
ing affection and source of constant inspiration throughout my work. I am grateful to my sister-in-law
Smt. T. Chandra Leelavathi and my brother Sri T. Raja Sekhara Reddy, for their perpetual dedication
to carry out my family commitments with all their moral and physical support while I struggled with
my work. My hearty cheers to my beloved children C. Hitesh Reddy and C. Hasya Reddy, whose love
and smile encouraged me in completing this work.
I am thankful to my colleagues, friends and students who helped me a lot to write this book.
K. Sesha Maheswaramma
I express my thanks to all of my family members. First and foremost, I would like to thank my h usband
Gaurav Chugh for standing by me throughout my career and supporting me in writing this book. He is
a continuous source of inspiration. I would like to thank my parents and my siblings for allowing me to
follow my ambitions throughout my childhood. My family, including my in-laws, has always supported
me throughout my career and authoring this book and I really appreciate it. I would also like to thank
Dr Y. Madhveelatha, Principal, MRECW for her encouragement and Dr Pawan Sharma for suggestions
and guidance. I also owe my thanks to my well-wishers Dr Nidhi Dureja, Dr Gaurav Dhingra, Dr Saritha
and Ms Tanuja Safala and Ms Harshitha.
Mridula Chugh

ABOUT THE AUTHORS
K. Sesha Maheswaramma is presently assistant professor in the Department
of Chemistry, JNTUA College of Engineering, Pulivendula, YSR Kadapa
(Dt.), Andhra Pradesh. She has done her M.Sc. in Mineral Chemistry, M.Phil.
in Water treatment and Ph.D. in Solid State Chemistry from Sri Venkateswara
University, Tirupathi, Andhra Pradesh. She won first rank in M.Sc. and was
awarded Justice P. C. Reddy meritorious gold medal in the year 2001 at the
university level.
She has rich privilege of gaining fifteen years of teaching experi-
ence for both graduate and post-graduate students of B.Sc., M.Sc. and
B.Tech. She has zeal for research and established herself as a good guide to encourage stu-
dents for challenging areas of research. Her research interests spread over analytical chemistry,
bio-inorganic medicinal chemistry, solid state spectroscopy and environmental challenges. She has
more than ten research publications in internationally reputed journals and presented more than twenty
research papers in national and international conferences, which are widely acclaimed as the most rel-
evant for addressing the existing societal problems and discussing practical remedies.
Maheswaramma is a coordinator, organizer, speaker, invitee and facilitator for several regional
and national level seminars and training programmes. She is expertise in academic administration,
framing academic guidelines, regulations, syllabi, coordinating various boards like studies, academic,
counseling, career, result analysis and active in chairing debates and discussions.
She visited GFZ Research Centre, Potsdam, Berlin, Germany, and Chinese National Academy
of Science, Beijing, China, and presented research papers. She is a life member of Indian Society
of Technical Education (ISTE) and awarded the IASc–INSA–NASI research fellowship for the years
2013 and 2014.
Mridula Chugh is an assistant professor in Ganga Institute of Technology

and Management, Jhajjar, Haryana. Previously, she worked with Malla Reddy
Engineering College for Women, JNTUH for three years. She has pursued
M.Sc. (Organic Chemistry), M.Phil., and CSIR UGC-NET. She did her master’s
degree in Kurukshetra University, Kurukshetra. She has a teaching experience
of ten years. She has attended various national and international seminars and
conferences and presented papers.

1 WATER TECHNOLOGY
Water is the driving force in nature, we never know the worth of

water till the river is dry.
1.1 INTRODUCTION
Water is a natural wonder and is the most common, important, useful thing for surviving of all the
living beings. Without food, living beings can survive for some days but without water nobody can
survive. Seventy percent of our body contains water, which regulates life processes such as digestion
of food, transportation of nutrients, and excretion of body wastes. It regulates the body temperature by
the process of sweating and evaporation. Water acts as a universal solvent; due to this reason, water is
widely used in laboratories, irrigation, steam generator, industrial purpose, fi re fighting, etc. Besides it
is used for bathing, drinking, sanitary purposes, etc.
From an engineer’s point of view too, very important, without water nothing will happen. It is
required in boilers for production of steam, which acts as a source of energy and a coolant in many
power and chemical plants and many other industries.
1.2 SOURCES OF WATER

Water present on earth passes through a remarkable cycle of changes (as shown in Figure 1.1):
(i) Rain water is the purest form of natural water because it is obtained by evaporation from the sur-
face water. But rain water during its downward path to the earth dissolved considerable amount
of gases (e.g. CO2, NO, NO2, SO2, SO3 etc) and suspended solid particles, which are present in
the atmosphere. So it becomes polluted.
(ii) The water that comes to the surface through rain is in the form of river water and lake water. River
water contains dissolved inorganic salts such as chlorides as well as dissolved impurities from the
soil. In lake water, the main impurities are organic matter.
(iii) A larger amount of rain water is percolated in the soil through permeable rocks, loose sand,
gravel, etc. During its passage downward into the ground, the suspended matter is left behind, and
organic matter is oxidized by bacteria. This water is extremely clear as a result of natural filtration
through the sand bed.
M01_ENGINEERING-CHE00_SE_XXXX_CH01.indd 1 5/12/2016 9:14:16 AM

1.2 Engineering Chemistry
Sources
Sea water Fresh water

(approx 97%) (approx 3%)
Surface water Rain water Underground

water
Flowing water Still water

Streams Ponds Springs
Rivers Lakes Wells
Reservoirs Tubewells
Figure 1.1 Flow diagram of sources of water
(iv) Sea water is the most impure form of natural water. River water joins the sea and thus gives its
impurities to the sea. In addition, due to evaporation of water, sea is having about 3.5% of dis-
solved salts, and the maximum amount (2.6%) is due to sodium chloride. Hence sea water is salty
in taste. This water is not directly useful to man because it is not palatable as it contains 2000
times more dissolved salt than fresh water.
1.3 TYPES OF IMPURITIES PRESENT IN WATER

Water may contain various impurities due to
(i) The ground or soil with which it comes in contact (e.g. garbage, soil particles, etc.)
(ii) Its contact with sewage or industrial wastes
(iii) The decomposition of dead plants and animals
(iv) The growth of bacteria, algae, viruses, etc.
The common impurities present in natural water can be classified into four groups that are as follows
and shown in Figure 1.2:
(i) Dissolved impurities
(a) Dissolved gases – NO2, CO2, SO2, etc., which are soluble in water and make it impure.
(b) Dissolved inorganic salts or ions
(1) Cations: Ca2+, Mg2+, Na+, K+, Fe2+, Al3++, Zn2+, etc.
(2) Anions: CO32− , SO2−
4
, HCO3− , Cl−, etc.
(ii) Suspended impurities
(a) Inorganic – sand, clay, lime, etc.
(b) Organic – Plant and animal materials like discarded vegetables, dry leaves, dead
materials, etc.

Water Technology 1.3
Types of Impurities
Dissolved Suspended Colloidal Microorganism

Inorganic Organic
Gases Inorganic
Figure 1.2 Types of impurities
(iii) Colloidal impurities

Finely divided silica, clay, organic products, colouring matter, etc.
(iv) Microorganism
Various pathogenic microorganisms such as bacteria, fungi, virus, etc.
The various types of impurities present in the water impact certain properties in water.
(a) Presence of different chemicals impart colour, odour and taste to the water.
(b) Presence of dissolved salt makes the water hard.
(c) Excess quantities of metals and dissolved gases make the water corrosive in nature.
(d) Presence of pathogenic bacteria in water makes it unfit for drinking or domestic purposes.
(e) Suspended matter create turbidity to the water.
1.4 HARD WATER AND HARDNESS

Depending on salts presents in water and reaction with soap, water is categorized into hard water
and soft water. Hardness is the characteristic of water by which water does not produce lather with
soap. It is due to presence of chlorides, sulphates and bicarbonates salts of magnesium, calcium and
other heavy metals [CaCl2, CaSO4, MgCl2, MgSO4, Ca(HCO3)2, Mg(HCO3)2, etc]. When hard water is
treated with soap, it does not produce lather, rather it forms a white scum. Soap is the sodium or potas-
sium salt of higher fatty acids like stearic acid [C17H35 COONa – sodium stearate].
2C17 H 35 COONa + MgCl 2 
→ (C1177 H 3355 COO)2 Mg + 2NaCl
Sodium stearate Salt Insoluble magnesium
stearate/white scum
2C17 H 35 COOK + MgSO4 


→ (C17
17 H 3355 COO)2 Mg + K 2SO 4
COO
Pottasium stearate Saallt White scum
2C17 H 35 COONa + CaCl 2 

→ (C1177 H 3355 COO)2 Ca + 2 NaCl
Sodium stearate Salt White scum
2C17 H 35 COONaa + CaS

CaSO
C O 4 
aSO → (C1177 H 35
35 C OO)2 Ca + Na 2SO 4
COO
Soap Salt White scum
Water which can produces lather with soap easily is called soft water.

(i) Types of hardness

Depending on salts present in the water, hardness is of two types, i.e., temporary hardness and
permanent hardness.
(a) Temporary or Carbonate Hardness: This is due to presence of dissolved bicarbonates of
calcium and magnesium. By boiling water, temporary hardness can be removed.
Ca(HCO3 )2 Heat
 →C O3 ↓ + H 2 O + CO
CaCO CO 2 ↑
Calcium
lcium bicarbonate
lciu Calcium
lcium caarbonate
lciu rbonate
(soluble in water) (insoluble in water)
HCO3 )2 Heat
Mg( HCO  →M O3 ↓ + H 2 O + CO
MgCO CO 2 ↑
Magnesium bicarbonate Magnesiium
um carbonate
( soluble in water) (insoluble in water)
(b) Permanent or Non-Carbonate Hardness: This is due to presence of chlorides and sulphates
of calcium and magnesium. Permanent hardness cannot be removed by boiling, therefore,
special methods are followed.
(ii) Hardness is expressed in terms of CaCO3
We know that hardness of water is due to the presence of number of dissolved salts in water but
for comparing the hardness of different samples of water of varying composition, it is necessary
to choose a reference standard. For this purpose, hardness of water is expressed in terms of
equivalents of calcium carbonate only. The following are the reasons for choosing CaCO3 as a
standard for expressing the hardness:
(a) CaCO3 is a complete insoluble salt; thus it can be easily precipitated completely during
water treatment.
(b) Its molecular weight is 100, and equivalent weight is 50, so the calculation becomes easy.
Hence whatever amount of dissolved salts is present in water, it is fi rst converted into calcium
carbonate equivalents by using the formula:
CaCO3 equivalent Equivalent weight of CaCO O3 (550)

0) Weight of hardness producing
= × substance in mg/L
of hardness Equivalent weight of hardness
producing substance
W × 550
=
E
W = Mass of hardness-producing substance in mg/L
E = Equivalent weight of hardness-producing substance
or
Mol. wt. of CaCO3 (100) Wt. of hardness producing

Hardness (CaCO3 equivalent) = × substance in mg //L
L
Mol. wt. ooff the
he substance
W × 100
=
M
Salts responsible for hardness is given in Table 1.1 and method to calculate the hardness.

Table 1.1 Calculation of CaCO3 equivalent

Conversion factor for
Dissolved salt/ calculation of CaCO3
compound/ ion Molar mass Chemical equivalent equivalent
Ca(HCO3)2 162 81 100/162
Mg(HCO3)2 146 73 100/146
CaCO3 100 50 100/100
MgCO3 84 42 100/84
CaSO4 136 68 100/136
CaCl2 111 55.5 100/111
MgSO4 120 60 100/120
MgCl2 95 47.5 100/95
FeSO4·7H2O 278 139 100/278
CO2 44 22 100/44
Mg(NO3)2 148 74 100/148
HCO3− 61 61 100/122
OH− 17 17 100/134
NaAlO2 82 82 100/164
Al2(SO4)3 342 57 100/114
Ca2+ 40 20 100/40
H+ 1 1 100/2
Mg2+ 24 12 100/24
(iii) Units of hardness

Various units used for expressing hardness of water are given below:
(a) Parts per million (ppm)
(b) Milligrams per liter (mg/L)
(c) Degree French (°Fr)
(d) Degree Clark (°Cl)
(1) Parts per million (ppm): It is defined as the number of parts of calcium carbonate equiva-
lent hardness present per 106 parts of water.
1 ppm = 1 part of CaCO3 equivalent hardness in 106 parts of H2O
(2) Milligrams per liter (mg/L): It is defi ned as the number of milligrams of CaCO3 equiva-
lent hardness present per liter of water.
1 mg/L = 1 mg of CaCO3 equivalent per 106 mL of water
= 1 part of CaCO3 equivalent per 106 parts of water
= 1 ppm
(3) Degree French (°Fr): It is defi ned as the number of parts of CaCO3 equivalent hardness
present per 105 parts of water.
1 °Fr = 1 part of CaCO3 equivalent hardness per 105 parts of water.
(4) Degree Clarkes (°Cl): It is defi ned as the number of parts of CaCO3 equivalent hardness
present per 70,000 parts of water.
1 °Cl = 1 part of CaCO3 equivalent hardness per 70,000 parts of water

Relationship between various units of hardness is shown in Table 1.2.
Table 1.2 Relationship between various units of hardness

ppm mg/L Fr °C
ppm 1 1 0.1 0.07
mg/L 1 1 0.1 0.07
°F 10 10 1 0.7
°Cl 14.3 14.3 1.43 1
Solved Numerical Problems Based on Hardness of Water

(i) A water sample contains 204 mg of CaSO4/L. Calculate the hardness in terms of CaCO3
equivalent.
Solution
CaSO 4 ≡ CaCO
CaCO3
136 g mol −1 ≡ 100 g mol −1
∴136 mg CaSO 4 ≡ 100 mg / L of CaCO
mg / L of CaSO O3 eequivalent
100
1 mgg / L of CaSO 4 ≡
136
100
SO 4 ≡
204 mgg / L of CaaS × 204 mg
mg / L of CaCO
CaCO3 eequivalent
136
Hardness of CaSO 4 = 11550 mg
mg / L of CaCO O3 eequivalent.
(ii) Calculate temporary and permanent hardness of a sample of water, which on analysis is found to
contain the following:
Ca(HCO3)2 = 16.2 mg/L, Mg(HCO3)2 = 7.3 mg/L
MgCl2 = 9.5 mg/L, CaSO4 = 13.6 mg/L
Solution
Hardness in terms of CaCO3 equivalent

CaCO3 equivalent
Substance
Mass of substance
(w)
Equivalent mass
of substance (E) (W ×E 50 ) hardness
Ca(HCO3)2 16.2 mg/L 81 10 mg/L
Mg(HCO3)2 7.3 mg/L 73 5 mg/L
MgCl2 9.5 mg/L 47.5 10 mg/L
CaSO4 13.6 mg/L 68 10 mg/L
W × 550
CaCO3 equivalent =
E

16.2 × 50
For (i) Ca(HCO3)2, CaCO3 equivalent = = 10 mg/L
81
7.3 × 50
(ii) Mg(HCO3)2, CaCO3 equivalent = = 5 mg/L
73
9.5 × 50
(iii) MgCl2, CaCO3 equivalent = = 10 mg/L
47.5
13.6 × 50
(iv) CaSO4, CaCO3 equivalent = = 10 mg/L
68
Now
Temporary hardness = Hardness due to bicarbonate ion
= Ca(HCO3 )2 + Mg(HCO3 )2
= 15 mgg / L
Permanent hardness = Hardness due to Cll − , S

SOO24 −
= MgCl2 + CaSO
CaSO 4
= 10 + 10 = 20 mg/L
(iii) A sample of water upon analysis gave the following data:
MgCl2 = 0.143°Fr, MgSO4 = 0.572°Fr, CaSO4 = 0.286°Fr, and Ca(HCO3)2 = 2.316°Fr. Calculate
the hardness in ppm.
Solution Since 1°Fr = 10 ppm
W × 550
CaCO3 equivalent =
E
1.43 × 50
0.143°Fr of MgCl2 = 1.43 ppm = ppm CaCO3 equivalent = 1.51 ppm
47.5
5.72 × 50
0.572°Fr of MgSO4 = 5.72 ppm = ppm CaCO3 equivalent = 4.77 ppm
60
2.86 × 50
0.286°Fr of CaSO4 = 2.86 ppm = ppm CaCO3 equivalent = 2.11 ppm
68
23.16 × 50
2.316°Fr of Ca(HCO3)2 = 23.16 ppm = ppm CaCO3 equivalent = 14.29 ppm
81
∴ Total hardness in ppm scale = 22.68 ppm
(iv) Calculate hardness in terms of CaCO3 equivalent, if 100 ml of a hard water sample neutralizes
exactly 12 ml of 0.12 N HCl by using methyl orange indicator.
Solution
N1V1 = N 2 V2
( Hard water ) ( HCl
HCl)
N1 × 100 = 0.12 × 12
12 × 12
N1 =
100 × 100

Strength of hardness in terms of a CaCO3 equivalent

12 × 12
= × 50 × 1000
100 × 100
Hardness = 720 ppm
(v) Calculate carbonate and non-carbonate hardness of water sample, if analysis of water sample gives
CO2 = 22 ppm, HCO3− = 305 ppm, Ca2+ = 80 ppm, Mg2+ = 48 ppm and total solids = 5000 ppm.
Solution
Equivalent wt. of W × 50
CaCO3 equivalent =
Constituent Mass of substance (W) substance (E) E
CO2 22 ppm 22 50 ppm
HCO3− 305 ppm 61 250 ppm
Ca2+ 80 ppm 20 200 ppm
Mg2+ 48 ppm 12 200 ppm
Carbonate hardness = Due to bicarbonate of Ca and Mg

= 250 ppm
Non-carbonate hardness = (Hardness due to permanent Ca2+ and Mg2++) −
(Hardness due to HCO3− ion)
= (200 + 200) – (250)
Non-carbonate hardness = 150 ppm
1.5 DETERMINATION OF HARDNESS

We know that there are two types of hardness of water, i.e., temporary and permanent hardness.
Temporary hardness is due to bicarbonate of calcium and magnesium, and permanent hardness is due
to chlorides and sulphates of calcium and magnesium.
The hardness of water can be determined by complexometric titration by using ethylenediamine
tetra acetic acid [EDTA] commonly known as EDTA method.
EDTA Method: It is the most important and more accurate method to determine the hardness of water.
EDTA has limited solubility in water, Hence, disodium salt of EDTA is used which is soluble in water.
Principle: EDTA can from complex with salts (Ca2+ and Mg2+) which are present in hard water.
Hence, it is known as complexometric titration. Calcium or magnesium ions present in the water sam-
ple with ammonical buffer solution form an unstable wine red colour complex with Eriochrome Black
T (EBT) indicator. When it is titrated with EDTA solution the metal ions present in water give a stable
deep blue colour (M-EDTA) complex and releases the free indicator.
The formula of EDTA is written as
HOOCH2C CH2COOH
N CH2 CH2 N
HOOCH2C CH2COOH
Ethylene diamine tetra acetic acid

Disodium salt of EDTA is

HOOCH2C CH2COO− Na+
N CH2 CH2 N
Na+ −OOCH2C CH2COOH
It is represented as Na2H2Y. It ionizes in aqueous solution to give 2Na+ ion and a strong chelating ion
represented as H2Y2−.
Na 2 H 2 Y → 2 Na + + H 2 Y 2 −
It is a hexadentate ligand, and it forms complexes with bivalent cations (Mg2+, Ca2+, etc.), and these
complexes are stable in alkaline medium (pH 8-10).
EBT may be represented as:
O OH OH
Na+ −O S N=N
EBT
NO2
{sodium 4-(1-hydroxy-2-napthylazo)-3-hydroxy-7-nitronapthalene-1-sulphonate}
The EBT has two ionisable phenolic hydrogen atoms, and it is represented as Na + H 2 In
In − ; indicator
EBT gives different colours at different pH values.
pH 7.0 pH 12.5
H 2 IInn −

H
pH 5.5
In 2 −
HIn

pH
In
10.0
3−
red blue yellowish orannge

ge
End point: During titration, the colour of the solution changes from wine red to pure blue.
Reactions involved during titration:
M 2+ EBT → [[M-EBT] Complleex +

+ EBT EDTA
→ [M-EDTA] Complex + EBT
(M2 + = Ca2 + /Mgg2 + ) wine red (unstable) (stable) pure blue
present in hardwater
(i) The calcium and magnesium ion present in hard water combines with the indicator EBT at pH
9-10 to form less stable wine red complex.
M 2+ + HIn 2 −
HIn → MInn − + H + M 2+ = C
((M Caa 2 + / M
Mg22++ )
(EBT, Blue) wine red
(ii) When EDTA is added to the water sample, the free M2+ (metal ions) forms a stable complex of
M-EDTA.
Ca 2+ + H 2 Y 2 − → CaY 2 −
CaY + 22H +
(EDTA) (M-EDTA Complex)
2+ 2−
Mg + H2 Y → MgY 2 − + 2H +
(EDTA) (M-EDTA Complex)

(iii) At the end point, when all free metal ions get complexed with EDTA, then further addition of
EDTA sets free the metal ion from metal indicator complex and forms more stable metal EDTA
complex.
CaIn − + H2 Y 2− → aY 2 −
CaY
C + HInn 2 −
HI + H+
MgIn − + H2 Y 2− → MgY 2 −
MgY + HIn 2 − + H+
(wine red) (EDTA) (Metal EDT
EDTA EBT indicator
(M-EBT))
(M-EBT complex) (blue)
(less stab
abble)
able)
le) (more stable)
The metal-EDTA complex may be represented as:

O O
C O O C
H2C N M N CH2
O O
CH2 C O O C H2C
CH2 CH2
[M-EDTA Complex]
M 2+ = C
Caa 2 + //Mg2 +
Procedure
Step I: Standardization of EDTA solution: Rinse and fill the burette with EDTA solution. Pipette out
50 ml of standard hard water (S.H.W)/Standard MgSO4 solution in a conical flask. Add 10–15 ml of
buffer solution and two drops of EBT indicator. Titrate the flask solution against the EDTA solution from
the burette until the colour changes from wine red to pure blue, it is end point. Repeat the procedure to
get two concordant readings. Let the volume of EDTA be consumed as V1 ml.
Step II: Determination of total hardness: Titrate 50 ml of unknown water sample with EDTA solution by
addition of 10–15 ml of buffer solution and two drops of EBT indicator till the wine red colour changes
to pure blue. Let the volume of EDTA be consumed as V2 ml.
Step III: Determination of permanent hardness: Take 250 ml of water sample in a 500 ml beaker and
boil gently for half an hour. Cool, filter, and wash the precipitate with distilled water, collecting filtrate
and washing in a 250 ml measuring flask, and make the volume up to the mark. Now titrate 50 ml of
boiled water sample same as in step I. Let the volume of EDTA be consumed as V3 ml.
Observations and Calculations

1 ml of standard hard water = 1 mg of CaCO3
Step I: Standardization of EDTA solution:
Volume of S.H.W taken for titration = 50 ml
Concordant volume of EDTA used = V1 ml

Now,
V1 ml of EDTA = 50 ml of S.H.W = 50 × 1 mg of CaCO3
50
1 ml of EDTA = mg of CaCO3
V1
Step II: Determination of total hardness:
Volume of unknown water sample taken for titration = 50 ml
Volume of EDTA used = V2 ml
Now, 50
50 ml of unknown water sample = V2 ml of EDTA = V2 × mg of CaCO3
V1
V2 50
1 ml of unknown water sample = × mg of CaCO3
50 V1
V2
1 L (1000 ml) of unknown water sample = × 1000 mg/L or ppm
V1
V2
i.e., total hardness = × 1000 ppm
V1
Step III: Determination of permanent hardness:
Volume of hard water sample taken after boiling and filtering = 50 ml
Let concordant volume of EDTA used = V3 ml
50
50 ml of boiled water = V3 ml of EDTA = V3 × mg of CaCO3
V1
V3 50
1 ml of boiled water = × mg of CaCO3
50 V1
V3
1 L (1000 ml) of boiled water = × 1000 mg/L or ppm
V1
V3
Permanent hardness = × 1000 mg/L
V1
Hence,
V2
Total hardness = × 1000 ppm
V1
V3
Permanent hardness = × 1000 ppm
V1
Temporary hardness = Total hardness – permanent hardness

V2 V
= × 1000 − 3 × 1000
V1 V1
 V − V3 
=  2  1000 ppm
 V1 

Advantages of EDTA Method

(a) EDTA method shows the result with greater accuracy.
(b) This method is more convenient in comparison with other methods.
(c) Procedure of EDTA method is more rapid.
Solved Numerical Problems Based on EDTA Method

(vi) The 1 liter standard hard water (SHW) was prepared by dissolving 1.0 gm of pure and dry CaCO3
in liter distilled water. 50 ml of this SHW required 46 ml of EDTA solution while 50 ml of the
given hard water sample consumed 20 ml of EDTA solution. After boiling, cooling, and filtering,
the hard water sample consumed 10 ml of EDTA solution. Determine the total, permanent, and
temporary hardness in ppm.
Solution
Step-I Standardization of EDTA solution
1L (1000 mL) of SHW = 1 gm (1000 mg) of CaCO3
∴ 1 ml of SHW = 1 mg of CaCO3
46 ml of EDTA solution required = 50 ml of SHW = 50 × 1 mg of CaCO3
50
1 ml of EDTA solution = mg of CaCO3
46
Step-II Determination of total hardness
50 ml of the given hard water sample required = 20 ml EDTA solution
50
= 20 × mg of CaCO3
46
20 50
1 ml of the given hard water sample required = × mg of CaCO3
46 50
20
1L (1000 ml) of the given hard water sample required = ×1000 mg/L
46
= 434.78 mg/L
Step-III Determination of permanent hardness
50 ml of boiled water sample required = 10 ml of EDTA solution
50
= 10 × mg of CaCO3 eq.
46
10
1 ml of boiled water sample required = mg of CaCO3 eq.
46
10
1L (1000 ml) of boiled water sample required = ×1000 mg/L
46
= 217.39 mg/L
Total hardness = 434.78 ppm
Permanent hardness = 217.39 ppm
Temporary hardness = Total hardness − Permanent hardness
= 434.78 − 217.39
= 217.39 ppm

(vii) Calculate carbonate and non-carbonate hardness of water, if 20 mL of standard hard water which
containing 1.5 g CaCO3 per liter, it required 25 mL EDTA solution for end point and 100 mL
of water sample required 18 mL EDTA solution, while the same amount of water after boiling
required 12 mL EDTA solution.
Solution 1000 ml H2O contains 1.5 g of CaCO3
1 ml of SHW = 1.5 mg of CaCO3
Step-I Standardization of EDTA solution
25 ml EDTA required = 20 ml of SHW = 20×1.5 mg of CaCO3
30
1 ml EDTA required = mg of CaCO3
25
Step-II Determination of total hardness
100 ml of hard water sample required = 18 ml EDTA solution
30
= 18 × mg of CaCO3 eq.
25
18 30
1 ml of hard water sample required = × mg of CaCO3 eq.
100 25
18 30
1L (1000 ml) of hard water sample required = × × 1000 mg/L
100 25
Total hardness = 216 mg/L
Step-III Determination of permanent (non-carbonate) hardness
100 ml of boiled water sample required = 12 ml of EDTA
30
100 ml of boiled water sample required = 12 × mg of CaCO3 eq.
25
12 30
1 ml of boiled water sample required = × mg of CaCO3 eq.
100 25
12 30
1L (1000 mL) of boiled water sample required = × × 1000 mg/L
100 25
= 144 mg/L
Total hardness = 216 ppm
Non-carbonate hardness = 144 ppm
Carbonate hardness = Total hardness – Non-carbonate hardness
= 216 – 144
Carbonate hardness = 72 ppm
(viii) Calculate the amount of lime and soda required for the softening of 15000 liters of water, which
is analyzed as follows:
Temporary hardness = 25 ppm
Permanent hardness = 20 ppm
Permanent Mg hardness = 15 ppm
74
Solution Lime requirement = (Temp. hardness + perm. Mg hardness) × Volume of water
100
74
= (25+15) × 15000 = 444000 mg = 444 g
100

106
Soda requirement = (Perm. hardness) × volume of water
100
106
= × 20 × 15000 = 318 g
100
∴ Lime requirement = 444 g
Soda requirement = 318 g
(ix) Calculate the quantity of lime and soda required to soften 20,000 liters of water containing the
following salts:
CaCO3 = 10.0 mg/L MgCO3 = 8.4 mg/L
CaCl2 = 11.1 mg/L MgSO4 = 6.0 mg/L
SiO2 = 1.2 mg/L
assuming the purity of lime as 90% and soda as 95%.
Solution
Conversion to CaCO3 equivalent

Amount
of substance Equivalent wt.
W × 50
Constituent (W) of substance (E) CaCO3 equivalent =
E
CaCO3 10 mg/L 50 10 mg/L
MgCO3 8.4 mg/L 42 10 mg/L
CaCl2 11.1 mg/L 55.5 10 mg/L
MgSO4 6.0 mg/L 60 5 mg/L
SiO2 1.2 mg/L Does not impart hardness
74
Lime requirement = (Temp. Ca2+ + 2 × Temp. Mg2+ + Perm. Mg2++) × Volume of water ×
100 purity factor
74 100
= [10 + 2 × 10 + 5] × 20, 000 ×
100 90
Lime requirement = 0.5755 kg
106
Soda requirement = [Perm.(Ca2+ + Mg2++)] × Volume of water × purity factor
100
106 100
= [10 + 5] × 220, 000 ×
100 95
= 0.3347 kg
(x) Analysis of water gave the following results H2SO4 = 196 mg/L, MgSO4 = 24 mg/L, CaSO4 =
272 mg/L., and NaCl = 25 mg/L. Water is to be supplied to the town with the population of one
lakh only. The daily consumption of water is 50 liter per head. Calculate the cost of lime and soda
required for the softening of the hard water for the town for April 2008, if the cost of lime is Rs.
5 per kg and cost of soda is Rs. 8 per kg.

Solution
Conversion to CaCO3 equivalents
Amount of the Equivalent weight of W × 50

Constituent substance (W) the substance (E) CaCO3 equivalent =
E
H2SO4 196 mg/L 49.5 200 mg/L
MgSO4 24 mg/L 60 20 mg/L
CaSO4 272 mg/L 68 200 mg/L
NaCl 25 mg/L Does not produce hardness
74
Lime requirement = (H SO + MgSO4 as CaCO3 equivalent) × volume of water
100 2 4
50 liter
= 74 (200 + 20) × 1kg
× 1,00,000 × 6
100 head 10 mg
1kg
= 74 (220) × 50 × 105 ×
100 106 mg
= 814 kg
For April 2008, total lime requirement = 814 × 30
= 24420 kg
Given cost of lime = Rs. 5/kg
Rs 5
Total cost of lime = 24420 kg ×
kg
= 1,22,100 Rs.
Similarly, Soda requirement per day
106 1kg
= (H 2SO 4 + MgSO4 + CaCO3 ) mg/L × 50 × 105 × 6
100 10 mg
106 5 1kg
= (200 + 2200 + 200) × 50 × 10 × 6
100 10 mg
= 2226 kg
For April 2008 (30 days), total soda requirement = 2226 × 30 = 66780 kg
Given cost of soda = Rs. 8.00/kg
8
∴ Total cost of soda = 66780 ×
kg
= Rs. 5,34,240
1.6 DISSOLVED OXYGEN (DO)

Amount of oxygen dissolved in water (mg/L) is known as dissolved oxygen. At ambient conditions of tem-
perature and pressure, the solubility of oxygen is about 8 mg/L. The amount of dissolved oxygen measures
the biological activity of the water bodies, and this is most essential for sustaining aquatic life. Estimation

of DO content in a particular water body is of important significance of environmental as well as the

industrial point of view. This serves as an indicator of the extent of pollution of water by oxidizable and
organic impurities. Further, DO is also responsible for corrosion of boilers and requires to be eliminated.
The Winkler test is used to determine the concentration of DO in a water sample. Here the water
sample is treated with a mixture of manganese sulphate and alkaline potassium iodide. Initially formed
manganous hydroxide precipitate traps the dissolved oxygen and oxidizes manganous ion (Mn+2) to a
brown-coloured precipitate of manganic oxide (MnO(OH)2).
Mn 2 + + 2OH
2OH − → M
Mn(OH)2
Mn(OH)2 + 2 O2 → M
1
MnO.(OH)
nO.(OH)2
Brown ppt.
The formed manganic oxide precipitate is allowed to settle down for a few minutes and then 2 to 3 ml
of concentrated H2SO4 is added to dissolved the precipitate. The liberated iodine is proportional to the
dissolved oxygen content of water sample. This is estimated by titrating a standard sodium thiosulphate
solution and using a starch solution as an indicator.
Mn(OH)2 + 4H + + 2I − → Mn 2 + + I 2 + 33H H2O
I 2 + 2S2 O32 − → S4 O62 − + 22I −
From the above equation, we can fi nd that

1 mole of O2 → 2 moles of MnO(OH)2 → 1 mole of I 2
Therefore, after determining the number of moles of iodine produced, we can calculate the number of
moles of oxygen molecule present in the water sample. The oxygen content is usually presented as mg dm−3.
The solubility of oxygen in water at ambient conditions of temperature, and pressure is about 8 mg/L.
1.7 DETERMINATION OF CHLORIDES IN WATER

Acidity is the ability of water to react with bases and certain metals. (or) An acid is a substance which can
act as a proton donor (or) Quantitative capacity of water to neutralise the base. Chlorides are present in
water as salts of calcium, magnesium, sodium and potassium [NaCl, CaCl2, KCl, MgCl2]. The salty taste
of water is due to NaCl present in it. Chlorides are not considered harmful if their concentration is less
than of 250 mg/L. Other salts such as MgCl2 in water undergo hydrolysis and cause problem in boilers.
Principle
When potassium chromate is added as an indicator to the water sample, it dissolves in water and the
chromate ions give yellow colour to the sample. Sodium chloride is present in the dissolved state in
the given sample of water. When this is titrated against silver nitrate, the silver ions react fi rst with the
chloride ions present in the sample and form silver chloride precipitate and sodium nitrate.
AgNO3 + NaCl → AgCl↓ + NaNO3
When all the chloride ions in the sample are precipitated, the excess silver nitrate present reacts with
potassium chromate and forms a pale red precipitate of silver chromate.
2AgNO3 + K 2CrO4 → Ag2CrO4 + 2KNO3

The appearance of the pale red colour indicates that all chloride ions have been precipitated and
indicates the end point of titration. From the titre values, the amount of chloride and salt present in the
sample is calculated.
Indicator: Potassium chromate
End point: Yellow to brick red
Procedure
Take a 50 ml burette and wash it with tap water and distilled water and then rinse it with 0.005 N silver
nitrate solution. Fill the burette with the 0.005 N silver nitrate solution and note down the initial read-
ing. Pipette out 10 ml of the given water sample with a clean 10 ml pipette into a clean and dry coni-
cal flask. Add two to three drops of potassium chromate as the indicator. The solution in the conical
flask turns to yellow colour. Titrate this solution against the 0.005 N silver nitrate solution taken in the
burette. The appearance of a brick red colour is the end point of titration. Note down the fi nal burette
reading. Repeat the titration until consecutive concordant values are obtained. From the titre values,
calculate the amount of chloride and salt present in the given water sample using the given formulae.
Calculations
Pipette solution (water sample) Burette solution (AgNO3)
V1) = 10 ml
Volume of given water sample (V V2) = _____ ml
Volume of silver nitrate solution (V
N1) = ?
Normality of given water sample ((N N2) = 0.005 N
Normality of silver nitrate solution ((N
N1V1 = N2V2
N2V2
Normality of given water sample N1 =
V1
Amount of chloride present in given sample A
= Normality of sample × equivalent weight of chloride = N1 × 35.45 = _____ g/L
Amount of salt present in given sample A
= Normality of the sample × equivalent weight of chloride salt = N1 × 58.45 = _____ g/L.
1.8 DETERMINATION OF ACIDITY IN WATER

Dissolved carbon dioxide (CO2) in water contributes to the acidity of water by formation of carbonic acid.
Water used for drinking purpose should not contain mineral acidity. Highly acidic water, i.e., having
low pH affects aquatic life.
Principle
Acidity of water depends on the end point of indicator used. Hydrolysis or dissociation of acids release
H+ ions which react with standard alkali (NaOH) during titrations.
The colour change of phenolphthalein indicator indicates neutralization of carbonic acid present
in water sample.

Indicators
(i) Phenolphthalein
(ii) Methyl orange
End Point
In case of methyl orange: Orange to yellow
In case of phenolphthalein: Appearance of pink colour
Procedure
Take a 50 ml burette and wash it with tap water and distilled water and then rinse it with sodium hydrox-
ide solution. Fill the burette with 0.02 N sodium hydroxide solution and note down the initial reading.
Take 100 ml of water sample into a conical flask. Add 4 to 5 drops of methyl orange indicator and colour
changes to orange. Titrate the water sample against sodium hydroxide solution until the colour changes
to yellow and note down the volume consumed as A ml. To the same solution, add 3 to 4 drops of phenol-
phthalein indicator and continue the titration until the appearance of pink colour. Note down the volume
of sodium hydroxide consumed as B ml. Repeat the titration to get consecutive concordant readings.
Calculations
Water sample NaOH solution
N1) = ?
Normality of water ((N N2) = 0.02 N
Normality of NaOH solution ((N
V1) = 100 ml
Volume of water (V Volume of NaOH used for methyl orange = A ml
Volume of NaOH used for phenolphthalein = B ml
N1V1 = N2V2 V2) = A + B
Volume of NaOH (V
N1 × 100 = 0.02 × ( A + B)
02 × ( A + B )
0.02
N1 =
100
Acidity of water = Normality × Eq. wt. of CaCO3
02 × ( A + B)
0.02
= × 50 ×1000
× mg/L
100
Volume of NaOHH × N × 550 × 1000
Acidity = mg/L
Volume of water sample
1.9 ALKALINITY OF WATER

The capacity of water for neutralizing an acid solution is known as alkalinity of water (or) the capacity
of a water to accept protons is known as alkalinity of water.

The alkalinity of water is mainly dependent on the following factors:

(i) Due to the presence of ions like HCOO3− , HSi
SiO3− , S
HSiO
HSiO SiO32 − , etc. in water.
(ii) The presence of weak organic acid salts.
Because they consume or have a tendency to take up N+ ions, hence concentration of OH– ions
in water increases.
Classification of Alkalinity
Depending on the ions present, alkalinity of water is broadly classified as
(i) Hydroxide (OH–)
2−
(ii) Carbonate (CO3 ) and
−
(iii) Bicarbonate (HCO3 ) alkalinity
The alkalinity of a water sample may be due to
(i) OH−
(ii) CO32−
(iii) HCO3−
(iv) OH− and CO32−
(v) CO32− and HCO3−
But there is no possibility with OH − andd HCO
HCO3− , because they combine with each other to form
carbonate.
OH − + HCO
HCO3− → C
COO32 − + H 2 O
Units
Alkalinity and hardness are expressed in terms of CaCO3 equivalents, ppm, mg/L, etc.
(i) Alkalinity < total hardness
Carbonate hardness in ppm = Alkalinity in ppm
(ii) Alkalinity ≥ total hardness
Carbonate hardness in ppm = Total hardness in ppm
Non-carbonate hardness = Total hardness – Carbonate hardness
Determination
The type and extent of alkalinity of a water sample can be easily determined by volumetric method.
A known volume of water sample is titrated against standard sulphuric acid by using phenolphthalein
indicator. The end point is disappearance of pink colour. Further the titrated water sample is titrated
against the same standard sulphuric acid by using methyl orange indicator. The end point is appearance
of red colour and the volume of H2SO4 consumed is noted.

H − + H+ → H2O 
(i) OH 
2−− + − P 
(ii) CO3 + H → H HCO
CO3  M
(iii) HCOO3 + H → H 2 O + CO2 
− +
The volume of the standard acid used up to phenolphthalein end point P marks the completion
of reactions (i) and (ii), whereas the total volume of the standard acid used from the beginning up to
methyl orange end point M corresponds to the completion of reactions (i), (ii) and (iii).
Solved Numerical Problems Based on Alkalinity of Water

N
(xi) 100 mL of a water sample required 4 mL of H SO for neutralization to phenolphthalein end
50 2 4
point. Another 16 mL of same acid was needed for further titration to methyl orange end point.
Determine the type and amount of alkalinity in terms of CaCO3 equivalent.
Solution Volume of water sample for titration = 100 mL
Volume used to phenolphthalein end point (A) = 4 mL
Volume used to methyl orange end point (B) = 16 mL
Total volume used to methyl orange end point (A + B) = 20 mL
Phenolphthalein alkalinity (in terms of CaCO3 equivalent)
N1V1 = N 2 V2
( Water ) ( Acid )
N
N1 × 100 = ×4
50
4
N1 =
50 × 100
Strengthh = N1 × Eq. wt of CaCO3

4
× 50
50 × 100
4
nity (P) =
Phenolphthalein alkaliinity × 50 ×1000
× ppm
50 × 100
= 40 ppm
Similarly, for methyl orange alkalinity,
N3V3 = N4V4
Water Acid
N
N3 × 100 = × 20
50
N 20
N3 = ×
50 100
Strength = N3 × Eq. wt. of CaCO3
N 20
= × × 50
50 100

1 20
Methyl orange alkalinity (M) = × × 50 × 1000 ppm
50 100
M = 200 ppm
1
Hence, P< M
2
1
P(40) < M(100)
2
So CO32− and HCO3− ions are present.
Now, alkalinity due to CO32− ions = 2P = 2 × 40 ppm = 80 ppm
alkalinity due to HCO3− ions = M – 2P = 200 – 80 = 120 ppm
(xii) Calculate the alkalinity in CaCO3 equivalents, if 100 mL of a water sample on titration with 0.03
N HCl by using phenolphthalein indicator and end point is at 7.5 mL acid. Another water sample
of same volume require 15 mL of same concentration acid by using methyl orange indicator to
obtain complete neutralization.
Solution Volume of water sample = 100 mL
For Phenolphthalein alkalinity
N1V1 = N 2 V2
( Water ) ( Acid )
N1 × 100 = 0.03 × 7.5
0.03 × 7.5
N1 =
100
Strengthh = N1 × Eq. wt. of CaCO3
0.03 × 7.5
= × 50
100
03 × 7.5
0.03
Phenolphthalein alkalinity (P) = × 50 ×1000
× ppm
100
= 112.5 ppm
For Methyl orange alkalinity,
N3V3 = N4V4
(Water) (Acid)
N3 × 100 = 0.03 × 15
03 × 115
0.03
N3 =
100
Strength = N3 × Eq. wt of CaCO3
03 × 115
0.03
= × 50
100

03 × 115
0.03
Methyl orange alkalinity (M) = × 50 × 100
100
M = 225 ppm
1
Hence P= M
2
1 225 
P(122.5) = M 
2  2 
So alkalinity due to CO32− ions,
Alkalinity due to CO32− ions = 2P or M = 225 ppm
N
(xiii) 50 ml of alkaline water sample required 20 ml of H2SO4 for phenolphthalein end point and
50
another 5 ml for methyl orange indicator, i.e., complete neutralization. Describe the type and
amount of alkalinity.
Solution For Phenolphthalein alkalinity,
N1V1 = N2V2
(Water) (Acid)
1
N1 × 50 = × 20
50
1 20
N1 = ×
50 50
20
= × 50
50 × 50
20
∴ Phenolphthalein alkalinity (P) = × 50 × 1000 ppm
50 × 50
= 400 ppm
For Methyl orange alkalinity,
N3V3 = N4V4
(Water) (Acid)
1
N3 × 50 = × 25
50
25
N3 =
50 × 50
25
= × 50
50 × 50

25
∴ Methyl orange alkalinity (M) = × 50 × 1000
50 × 50
1 = 500 ppm
Hence, P> M
2
1
P(400) > M  500 
2  2 
So OH– and CO32− ions are present.

Now, alkalinity due to OH– = 2P – M = 2(400) – 500
= 300 ppm
2−
alkalinity due to CO3 = 2(M – P) = 2(500 – 400)
= 200 ppm
1.10 DISADVANTAGES OF HARD WATER

Hard water contains large amounts of bicarbonates, sulphates, and chlorides of calcium and magne-
sium salts. It causes number of problems in domestic use, industrial use, and in boilers.
(i) Problems in Domestic Use:
(a) Cooking: Pulses and other vegetables do not cook well in hard water.
Tea, coffee and other drinks prepared with hard water gives an unpleasant taste.
(b) Drinking: Hard water causes bad effect on digestive system.
Due to formation of calcium oxalates, stones are formed in kidneys.
(c) Wastage of soap:
Washing: Hard water does not give much lather with soap, as most of the soap is consumed
for removing calcium and magnesium salts present in water.
Bathing: It produces sticky scum on both tub and body.
(d) Damaging clothes: The Ca2+ and Mg2+ ions present in hard water combine with soap to form
insoluble compounds, which sticks to the clothes. This is difficult to remove, and hence
damages the clothes.
(e) Wastage of fuel: Much fuel is consumed for boiling hard water in kettles because salts form
an incrustation inside the kettle due to formation of carbonates and hydroxides of calcium
and magnesium.
After prolongedusage, kettle also gets damaged due to scale formation.
(ii) Problems in Industrial Use:
(a) Textile industry: Water is used in textile industry for cleaning, washing, and whitening of
yarn. For such purposes, soap is required; if hard water is used, more amount of soap is
wasted.
(b) Paper industry: The water that is used in paper industry should be free from hardness, sus-
pended particles, iron, etc. Because hardness increases the ash contents of paper, suspended
particles produce cracking tendency of paper, and the salt of iron decreases the brightness
of paper.

(c) Iron industry: Hard water makes the iron of low quality. It corrodes the iron and its alloys.
(d) Dyeing industry: The water that is used for dyeing purpose should be free from hardness,
because salts of calcium and magnesium spoil the desired shade.
(e) Sugar industry: Water should be free from hardness-suspended particles as well as patho-
genic microorganisms because hard water causes difficulties in the crystallization of sugar
from molasses.
(iii) Problems in Boilers, Use:
For the generation of steam a huge quantity of water is used in boilers and is known as boiler
feed water. If water used for boilers is hard, it may create number of problems like caustic
embrittlement, corrosion, scale and sludge formation, priming and foaming, etc. This is very
dangerous because at high pressure the same causes explosions. Hence water which is used in
boilers should be softened and should be pure before feeding into the boilers.
Boiler-feed water should satisfy the following requirements:
(a) Hardness < 0.5 ppm
(b) Caustic alkalinity = 0.15 – 0.45 ppm
(c) Soda alkalinity < 1 ppm
(d) Excess soda ash < 0.55 ppm
1.11 QUALITY OF WATER FOR DOMESTIC USE

The potable water or drinking water should satisfy the following essential requirements:
(i) Water should be clear, clean, colourless, and odourless.
(ii) Total dissolved solids (TDS) should be less than 500 ppm.
(iii) It should be free from hardness, suspended particles, and pathogenic bacteria.
(iv) Turbidity should be less than 10 ppm.
(v) Its pH should be about 7–8.
(vi) It should be free from harmful, dissolved solids like arsenic, manganese, chromium, lead, etc.
(vii) It should be free from harmful gases like H2S, SO2, etc.
(viii) It should be neither too hard nor too soft. The recommended hardness is about 300 mg/L as
CaCO3 equivalent.
(ix) Its alkalinity should not exceed 600 mg/L.
(x) It should have an agreeable taste.
(xi) Fluoride should be less than 3 ppm.
(xii) Chloride and sulphate must be less than 250 ppm.
1.12 TREATMENT OF WATER FOR DOMESTIC USE

Purification of water for potable use involves mainly the following steps:
(i) Screening: Removes the floating materials like leaves.
(ii) Sedimentation: Removes suspended impurities like sand, clay, etc.
(iii) Coagulation: Removes finely divided suspended particles.
(iv) Filteration: Removes colloidal impurities and large organisms.
(v) Disinfection: Kills the bacteria.

(i) Screening: The raw water is allowed to pass through screens having large number of holes,
where floating impurities like rags, paper, leaves, etc., are held by them, and water is passed
through the holes.
(ii) Sedimentation: Sedimentation is a process for retention of water for certain period in a deep tank
( ~ 5 meter) or to flow quietly at low velocities. Most of the suspended particles settle down due
to the force of gravity. This process takes two to eight hours. This process removes 70%–75% of
suspended impurities.
(iii) Coagulation: Coagulation is the process by which the fine, suspended, and colloidal impurities
are removed from the water by the addition of suitable chemicals (coagulants). The finely divided
suspended inorganic matters do not settle down so easily, so these smaller particles are converted
into larger ones, which have higher settling velocities.
The commonly used coagulants are the salts of iron and aluminium, e.g., alum (K 2SO4
Al2(SO4)3 . 24H2O), ferrous sulphate (FeSO4 . 7H2O), sodium aluminate (NaAlO2), etc. These
coagulants react with alkaline salts and form a thick gelatinous precipitate known as Flock.
Flock has the property to attract finely suspended particles and form big flock, which settles
down rapidly. This process is called flocculation.
A few commonly used coagulants and their reactions are as follows:
(a) Alum (Al2(SO4)3 K 2SO4 . 24H2O)
(SO 4 )3 + 3Ca(HCO
Al 2 (SO 3Ca(HCO3 )2 → 2Al(OH)3 ↓ + 3CaSO
O 4 + 66CO
CO2
(Flocculant)
Al 2 (S
SOO 4 )3 + Mg(HC
Mg(HCO
M O3 )2 → 2Al(OH)3 ↓ + 3MgSO
g(HCO 3MgSO 4 + 66CO2
(Flocculant)
(b) Sodium aluminate (NaAlO2)
O2 + 2H
NaAlO 2H 2 O → Al(OH)3 ↓ + NaOH
(Floocculant
cculant)
The NaOH produced precipitate of Mg salts as Mg(OH)2

MgSO 4 + 2NaOH
2NaOH → M g(OH)2 + Na 2SO 4
Mg(OH)
(c) Ferrous sulphate (FeSO4 . 7H2O)
FeSO 4 + Mg(HCO3 )2 → Fe(OH)2 ↓ + MgSO 4 + H 2 O + CO2

FeSO 4 + Ca(HCO
Ca(HCO3 )2 → Fe(OH H))2 ↓ + CaSO
CaSO 4 + H 2 O + CO2
4Fe(OH) 2 + 2H 2 O + O2 → 4Fe(OH)3 ↓
(Flocculant)
The precipitates obtained by using suitable coagulants in water get settled down during
sedimentation.
(iv) Filteration: Almost all suspended impurities are removed through filteration process. During
filteration, all types of insoluble colloidal and bacterial impurities are also removed by passing
water through a bed of proper-sized material. Two types of filters are commonly used in domestic
water treatment.
(a) Gravity sand filter
(b) Pressure filter

Fine sand 30-60 cm
sedimented Coarse sand

30-60 cm
water Gravels
(Inlet)
Filtered
water
Under drain (Outlet)
channel
Figure 1.3 Sand filter

(a) Gravity sand filter: It consists of a large, shallow, rectangular tank made of concrete and a
process medium, known as filter medium, which retains solid particles but allows the pas-
sage of water as shown in Figure 1.3.
It consists of three layers. The upper layer consists of fi ne sand (about 50 cm thick) and
is a thick layer. The middle layer consists of coarse sand (about 20 cm thick), and the bottom
layer consists of gravels (about 30 cm thick). It is provided with an inlet for sedimented water
and an under drain channel at the bottom for the exit of filtered water. Sedimented water
enters the sand filter from the top and is uniformly distributed over the fi ne sand layer. As
the water percolates through the sand bed, fi nely suspended particles and most of the germs
and bacteria are retained by the top layer. Clear, filtered water is collected in the under drain
channel, from where it is drawn out.
The rate of filteration becomes slow after some time due to clogging of pores of the top
sand layer by the impurities retained in the pores. Therefore, the portion of the top fine sand
layer is scrapped off and replaced by a new sand layer. The filter is put to use again.
(b) Pressure filter: It consist of a cylindrical as shown in Figure 1.4, vertical steel tank contain-
ing three layers of filtering media, one above the other.
(1) Pebbles layer (10–35 mm grain size)
(2) Coarse sand layer (5–7 mm grain size)
(3) Fine sand layer (1–2 mm grain size)
Impure, sedimented water is mixed with a small amount of alum solution, and then water is
forced through filter bed under pressure. Alum forms the slimy layer on the filter bed, and this
helps in the removal of colloidal and bacteriological impurities. The function of deflector plate,
which is provided at the top, is to distribute the slimy layer of alum uniformly over the top of
the filter bed. Filtered water, as it comes out from the bottom of filter, is under pressure and can
thus be pumped directly. These filters are widely used for industrial purposes.
(v) Disinfection/Sterilization: Sterilization of water means complete destruction of all living
microorganisms (bacteria, virus, etc.) present in water. We know that water after passing through
different processes such as sedimentation, coagulation, and filteration processes still contains
a small percentage of pathogenic bacteria. Therefore, it is necessary to remove these bacteria
and microorganisms from water. The chemicals used for sterilization are known as sterilizers or
disinfectants.

Raw water
Deflector plates
inlet
Wash water
(outlet)
Slimy layer of Al(OH)3
Fine sand
Coarse sand
Pebbles
Compressed air
inlet
Wash water Filtered water

inlet outlet
Figure 1.4 Vertical pressure filter
Several methods have been adopted for sterilization of water. Some of them are given below:
(a) Boiling method
(b) Chlorination method
(c) Ozonolysis method
(d) UV-rays method
(e) Membrane technology method
(a) Boiling method: Water for domestic purposes on a smaller scale may be sterilized by sim-
ple boiling method. In this method, water is boiled for about 20–30 min. This method
kills the harmful disease-causing bacteria and germs. But this method is useful only for
household purposes because this process is very much expensive for municipal supply
of water, and in addition, a large quantity of fuel is required to boil water on a large scale. It
does not provide any protection for further contamination of water.
(b) Chlorination method: It is the most important method for sterilization of water. Chlorination
is done by the following methods:
(1) By using chlorine gas or concentrated aqueous solution.
(2) By using bleaching powder.
(3) By using chloramine.
(1) By using chlorine gas or concentrated aqueous solution
Chlorine is a powerful germicide and most commonly used disinfectant. Chlorine used
for this purpose can be used directly as a gas or as chlorine water.
It reacts with water to form hypochlorous acid and nascent oxygen, both of which
are powerful germicides.

Cl 2 + H 2 O → HCl + HOCl
Hypochlorous aaci
cid
HOCll → HCl
HCl + [O]
(nasceent
nt oxygen)
Germss + [O]
[O] → Germs are oxidised
HOCll + bacteria
bacteria → Deacttivated
ivated bacterias
Apparatus: The apparatus used for disinfection by chlorine is known as chlorinator
(Figure 1.5). It is a large tower containing number of baffle plates. From the top of the
tower, proper dose of chlorine and water is introduced. They get thoroughly mixed
during their passage through the tower, and treated water is taken out from the bottom.
Advantages
(i) It is cheap and is an easily available disinfectant.
(ii) At a low concentration, it is very effective bactericide.
(iii) It can be used at high and low temperatures.
(iv) It is stable and does not deteriorate on keeping.
(v) Chlorine residue can be maintained in treated water, which provides additional
safety for preventing regrowth of bacteria.
Disadvantages
(i) Excess of chlorine produces an unpleasant taste and odour in water.
(ii) It is less effective at higher pH value but more effective at lower pH value (below
pH 6.5).
Raw water Concentrated

inlet chlorine solution
Baffle plates
High tower
Sterilized water
outlet
Figure 1.5 Chlorinator

(2) By using bleaching powder (CaOCl2)

Bleaching powder is a strong oxidizing agent and is having 30 per cent available chlorine.
When water is treated with bleaching powder, hypochlorous acid is formed. It releases
nascent oxygen and the nascent oxygen thus released deactivates the enzymes of micro-
organisms; due to this, metabolic activities will stop and the microorganisms get killed.
CaoCll 2 + H 2 O 
→C OH)2 + C
Caa(OH Cll 2
( Bleaching
Bleaching powder
powder )
Cl 2 + H 2 O 

→ HCl
HCl + H
HOCl
( hypochlorous acid
acid )
HOCll 
→H Cl + [O]
HCl
Nascent oxygen
Germss + [O] → Deactivate the enzyme

↓
Stop metabolic activities
of miicroorganism
croorganisms
↓
Kill
About 1 kg of bleaching powder is sufficient for 1000 kilolitres of water, but allow the
water to stand for several hours.
Disadvantages
(i) Excess of bleaching powder creates bad taste and odour to water.
(ii) It introduces calcium hardness in water due to the formation of Ca(OH)2.
(iii) It is unstable, so its storage is difficult.
(3) By using chloramines (NH2Cl)
By mixing of chlorine and ammonia in 2:1 ratio, chloramine is formed.
Cl 2 + NH 3 

→ NH 2 Cl + HCl
( chloramine
chloramine)
Whenever water is treated with chloramine, hypochlorous acid is formed and with
release of hypochlorous acid it provides greater safeguard from recontamination.
ClNH 2 + H 2 O 

→ HOCl + NH 3
Hypochlorous acid
HOCll  →H Cl + [O]
HCl
Germss + [O] 

→ Kills the germs
So, HOCl + germs → germs are killed.
Advantages
(i) Excess dose of ClNH2 does not create bad odour and taste in water.
(ii) It provides a greater lasting effect than chlorine.

Waste gases
Impure water
(inlet)
Gravel bed
Curved partition
having perforation
Ozone
gas
(inlet)
Sterilized water
(outlet)
Figure 1.6 Ozone sterilizer
(c) Ozonolysis method: Ozone is used for this method. Ozone is a highly unstable and excellent
disinfectant. It breaks down and gives nascent oxygen.
O3 → O2 + [O]
(Nascent oxygen)
The nascent oxygen is very powerful oxidizing agent, which kills all the bacteria and germs
present in water.
Apparatus: The reaction of ozone and water is carried out in ozone sterilizer (Figure 1.6).
During the treatment of water, water is allowed to enter from top to bottom, and ozone is
allowed to enter from bottom to top, which kills the germs when they come in contact with
each other. Sterilized water is collected at the bottom of the tank. The contact time for ozone
and water is about 10–15 minutes.
Advantages
(1) It removes colour and odour from water.
(2) It improves the taste of water.
(3) The excess dose of ozone is not harmful, because it releases O2 on decomposition.
(d) UV-rays method: When water is exposed to UV-rays from electric mercury lamp that is
immersed in water, most of the pathogenic bacteria are destroyed. This method is widely
used for the disinfection of swimming pool water.
Advantages
(1) It does not require any chemicals.
(2) It has not any bad effect during treatment.
(3) It does not produce any odour in water.

Disadvantages
(1) It is very expensive, so it is not widely used on a large scale.
(e) Membrane technology method: Disinfection by this method is generally used for drinking
water. In this method, water purifies most of the contaminant ions, molecules, and small
particles including viruses and bacteria by passing them through a membrane having uni-
form microscopic-size pores. Membrane processes include microfilteration, ultrafilteration,
nanofilteration, and reverse osmosis.
In all these methods, water is forced through membranes made of synthetic polymers,
cellulose acetate, or even ceramics by the application of high pressure in the range of 10
to 50 atm. pressure. Microfilteration and ultrafilteraton membranes with pores of 0.002 to
10 μm in diameter can filter off most bacteria and colloidal particles but not viruses and
ions. Nanofilteration soften water by removing hardness causing metal ions, and reverse
osmosis is used for desalination of sea water.
1.13 BREAK-POINT CHLORINATION

Chlorination of water is done carefully in a controlled manner with the dip or break is called break-
point chlorination. Added chlorine consumed for different reactions such as
(i) Oxidation of reducing substance
(ii) Chlorination of organic substance
(iii) Oxidation of ammonia and disinfection of bacteria
With this method not only living organisms but also organic impurities and free NH3 present in
water are destroyed. The point at which free residual chlorine begins to appear is called break-point
chlorination. It is also known as free residual chlorination.
Break-point chlorination shows four stages of sterilization as shown in Figure 1.7:
Stage-III
Destruction
of chloro
Stage-I
Residual chlorine
organic and Stage-IV

Stage-II
Oxidation chloram- Free residual
of Formating of B ine chlorine D
reducing chloro organic compounds
compounds and
by chloramine
chlorine compounds
C
Break point
Combined chlorine Free chlorine

O A
Applied chlorine dose (mg/L)
Figure 1.7 Break-point chlorination curve

Stage I: Initially, with the lower dosage of Cl2, there is no free residual chlorine since all the added Cl2
gets consumed in complete oxidation of reducing substances present in water.
Stage II: As the amount of Cl2 dose is increased, the amount of residual Cl2 also shows steady increase.
This stage corresponds to the formation of chloro-organic and chloramines compounds without under-
going oxidation.
Stage III: As more amount of Cl2 is applied, the amount of free residual chlorine also decreases, due to
oxidation of chloro-organic and chloramines. When the oxidation destruction is complete, it reaches a
minima.
Stage IV: After minima, the added Cl2 is not used in any reaction. Thus, the residual Cl2 keeps on
increasing in direct proportion to added Cl2.
The point ‘C’ is called break point. It is a point at which free residual chlorine begins to
appear. Thus, break-point chlorination helps in eliminating disagreeable odour and bad taste in
water.
Advantages
(i) It prevents the presence of excess chlorine, which may impart bad odour and taste to water.
(ii) It ensures complete destruction of disease-producing bacteria.
(iii) It prevents the development of any weeds in water.
(iv) It helps to calculate the sufficient amount of chlorine for adding in water.
Dechlorination: Excess of chlorine after the break-point chlorination gives unpleasant taste and
odour in water. The excess of Cl2 may be removed by filtering the treated water over activated carbon.
Over chlorination may also be removed by treating the water with SO2, Na2SO3, and Na2S2O3.
SO2 + Cl 2 + 2H 2 O → H 2SO 4 + 2HCl

Na 2SO3 + Cl 2 + H 2 O → Na 2SO 4 + 2HCl
Na 2S2 O3 + 44C
Cl 2 + 5H
5H 2 O → 2NaHSO4 + 8HCl
Superchlorination: Superchlorination is the addition of excess amount of chlorine for disinfection

of water. It destroys the pathogenic microorganisms as well as organic impurities by oxidation.
Prechlorination: Prechlorination is the treatment of water with chlorine before filtration. In this
process high chlorine is required to satisfy the chlorine demand of filterable matter. With prechlorina-
tion the quality of water is superior because unpleasant tastes and odours due to chlorinated products
may be absorbed during filtration. This process is highly expensive.
Post-chlorination: Post-chlorination is the treatment of chlorine with water after filtration. In this
method treated water may have unpleasant taste and odour, but it is cheaper than prechlorination due
to lower chlorine demand.
1.14 BOILERS AND BOILER TROUBLES

In all the industries, boilers are used for generating steam. Boiler-feed water is the water required for
generation of steam and with the safety, economy and efficiency concerns it should be of very good
quality.

Depending upon the operating pressures, boilers are classified into low-pressure (10–15 kg/cm 2),
medium-pressure (15–35 kg/cm 2), high-pressure (50–140 kg/cm 2), very high-pressure (150–225 kg/
cm2) and supercritical boilers (>225 kg/cm2).
Depends upon the quality of the feed water, so many problems may arise in the boilers. Some of
them are listed hereunder.
(i) Scale and sludge formation
(ii) Priming and foaming or carry over
(iii) Boiler corrosion
(iv) Caustic embrittlement
(i) Scale and Sludge formation
In the boilers, when water is vaporized to steam gradually the concentration of dissolved salts
increases. When the concentration of salts reaches their saturation, they are thrown out in the
form of precipitates. Sludge is the soft, slimy and non-adherent layer of precipitate inside the
boiler and also called mud. Hard adhering coating of precipitate inside the boiler walls is called
scale. Scale and sludge are shown in Figure 1.8.
(a) Sludge: Sludge is a soft, loose, and slimy precipitate formed within the boiler sludge.
It can easily be scrapped off with a wire brush. It is formed at comparatively colder por-
tions of the boiler and collects in areas of the system, where the flow rate is slow or at bends.
Sludges are formed by substances that have greater solubility in hot water than cold water.
Composition: The main composition of sludge includes MgCO3, MgCl2, CaCl2, MgSO4, etc.
Disadvantages
(1) Sludges are poor conductor of heat, so they tend to waste a portion of heat generated.
(2) Sludges decrease the efficiency of the boiler.
(3) Since sludges settle in areas of poor water circulation such as joints, bends, etc., there-
fore choking of pipes takes place.
Removal of Sludge
(1) By taking small precautions, like using of soft water, prevent the formation of sludge
(2) Scrapping of sludge with hard brush
(3) With frequent ‘blow-down operation’
i.e., replacement of concentrated water with fresh water.
Water
∼ ∼∼
∼
∼ ∼∼
Hard,
Boiler adhering
Loose, soft,
wall coating on
slimy ppt
inner walls of
(sludge) Heat Heat boiler (scale)
Figure 1.8 Sludge and scale

(b) Scale: Scale is a hard, adhering and sticky deposit. They stick very fi rmly on the inner walls
of the boilers and very difficult to remove even with a chisel and hammer. These are formed
with CaCO3, Ca(OH)2, Mg(OH)2, CaSO4, CaSiO3, MgSiO3, etc.
Formation of Scales: Due to the following reactions, scales are formed.
(1) Decomposition of calcium bicarbonate
In low pressure boilers, calcium bicarbonate decomposes and gives calcium carbonate.
HCO3 )2 Heatin
Ca( HCO g →C
CaC O3 ↓ H 2 O + CO
aCO CO 2 ↑
( scale
scale)
At high pressure boiler formed CaCO3 is soluble and gives calcium hydroxide, whose
solubility decreases with the temperature and deposit as scale.
High temperature
CaCO3 + H 2 O 


→ Ca(OH)2 ↓ + CO2 ↑
( scale
scale)
(2) Deposition of calcium sulphate as a scale

With increase of temperature the solubility of calcium sulphate decreases, and conse-
quently gets precipitated as hard scale. This scale is quite adherent and difficult to remove.
(3) Hydrolysis of magnesium chloride
At high temperatures, the magnesium salts undergo hydrolysis and give magnesium
hydroxide.
MgCl2 + 2H 2 O 
→ Mg(OH)2 ↓ + 2HCl
( soft scale
scale)
(4) Formation of silicates

Minute amounts of silica present in water form and deposit as calcium or magnesium
silicates and stick very fi rmly to the inner side of the boiler surface.
Disadvantages
(i) Fuel wastage: As scales have a low thermal conductivity to provide a continuous sup-
ply of heat to water, overheating is done, which results in the wastage of fuel.
(ii) Decrease in efficiency: Scales get deposited in the valves and condensers of the boil-
ers, thereby choking them partially. It results in decrease in efficiency of the boiler.
(iii) Danger of explosion: Sometimes at high pressure, the scales crack and water suddenly
comes in contact with overheated iron plates. This results in the sudden formation of
large amount of steam, which may cause explosion.
(iv) Lowering of boiler safety: Super heating of boiler makes the boiler material softer and
weaker, which causes distortion of boiler tube.
Removal
(i) For soft scale: Soft scale is loosely adhering, so it can be removed with the help of
wire brush or blow-down operation.
(ii) For brittle scale: Brittle scale can be removed by giving thermal shocks to the boiler,
i.e., heating and cooling suddenly.
(iii) For hard and adhering scale: They can be removed by adding chemicals.

Example: (i) CaCO3 scale can be dissolved by using 5%–10% HCl.

(ii) CaSO4 scale can be dissolved by adding EDTA since Ca-EDTA complex is
highly soluble in water.
H 2 Y 2 − + Ca 2 + → CaY
Y 2 − + 2H +
(ii) Priming, carry over and foaming

(a) Priming: Priming is the carrying of small droplets of water along with steam while boiling
the water. This is also known as wet steam.
Causes of Priming
(1) Improper design of the boiler
(2) Presence of large amount of fi nely divided particles in the boiling water
(3) Presence of large amount of dissolved solids
(4) Very high level of water in the boiler
(5) High steam generation velocities
(6) Sudden increase in steamproduction rate
(7) Presence of foam on the surface
Precautions to Reducing Priming

(1) Maintaining low level of water
(2) Fitting of mechanical steam purifiers
(3) Ensuring efficient softening and filtration of boiler-feed water
(4) Avoiding of rapid change in steam generation
(5) Removal of scale and sludge frequently
Carryover: Carrying of suspended and dissolved solids along with wet steam is called
carryover.
(b) Foaming: Foaming is the formation of persisted form (or) stable bubbles in the boilers, which
do not break easily. This is due the concentration difference of suspended solid between the
film and the bulk of water. It is also due to the presence of oil and alkalies in boiler-feed
water. Oily substances and alkalies react to form soaps, which reduce the surface tension of
water and thus increase the foaming tendency of water.
Causes of Foaming
The following are the causes of foaming:
(1) Due to the presence of oil or grease in water
(2) Due to the presence of fi nely divided sludge in water
(3) Due to the presence of some chemicals, which reduce the surface tension.
Prevention of Foaming
(1) By the addition of antifoaming agents such as castor oil or polyamides in low-pressure
boilers
(2) By using soft and filtered water

(3) By removing oil from boiler water by adding coagulants like ferrous sulphate or sodium
aluminate, etc.
Disadvantages of Priming and Foaming

(1) Due to the presence of foaming, boiling point of water is increased; hence wastage of
fuel occurs.
(2) It is very difficult to maintain the constant pressure of steam.
(3) Due to the excess formation of foaming, the bubbles entered into the engine along with
the steam, which lowers the efficiency of engine.
(4) Due to priming and foaming, corrosion takes place in the part of the engine.
(5) Due to the presence of foam, water level is not identified.
(iii) Boiler Corrosion

It is the disintegration or decay of boiler material either due to chemical or electrochemical
reaction with its environment.
Factors Causing the Boiler Corrosion

(a) Formation of rust with dissolved oxygen: Dissolved oxygen present in the water attacks the
boiler material and easily forms rust.
2Fe + 2H
2H 2 O + O2 → 2Fe(OH)2 ↓
Ferrous hydroxide
4 Fe(OH)2 + O2 → 2[Fe2 O3 ⋅ 2H
2H 2 O]
Rust
(b) Due to the presence of dissolved CO2: The source of CO2 in water, either dissolved CO2 gas or
bicarbonates, on heating gives CO2 and is also responsible for boiler corrosion.
Mg(HCO3 )2 ∆
→ Mg(OH
Mg(OH)2 + 2C
CO2 ↑
Ca(HCO3 )2 ∆
→C aCO3 ↓ + H 2 O + C
CaC
aCO CO2 ↑
Carbon dioxide (CO2) dissolves in water to form a weak carbonic acid.
CO2 + H 2 O → H 2 CCOO3
CO3 + Fe
H 2 CO Fe → F eCO3 + H 2
FeCO
FeC
eCO
(c) Due to the formation of acids from dissolved salts: Chlorides of some inorganic salts like
MgCl2, CaCl2 etc., which present in water can produce hydrochloric acid and can corrode
the boilers.
MgCl2 + 2H 2 O → Mg(OH)2 ↓ + 2HCl
CaCl 2 + 2H 2 O → Ca(O
Ca(OH
Ca(OHH ) 2 ↓ + 2H
HCl
The liberated HCl reacts with boiler material in chain-like reaction.
Fe + 2HCl
HCl → F FeCll 2 + H 2
FeCl 2 + 2H 2 O → Fe(OH)2 + 2HCl
(d) Due to the presence of oil: Oil undergoes hydrolysis, releasing free fatty acids leading to
corrosion of the boiler.

Prevention of Boiler Corrosion

(a) By removal of DO
(1) Preheating: As solubility of gases decreases with increases in temperature, at approxi-
mate 65°C, complete DO is removed.
(2) Chemical treatment: The DO is removed through the addition of Na2SO3 or Na2S or
hydrazine (N2H4).
2 Na 2SO3 + O2 → 2 Na 2SO 4
Sodium Sulphite Sodium Sulphate
Na 2S + 2O2 → Na 2SO
SO 4
Sodium Sulphide
N 2 H 4 + O 2 → N 2 ↑ + 2H 2 O
Hydrazine
Hydrazine is found to be an ideal compound for removing DO because the prod-

ucts are water and nitrogen gas, which do not form hard products, while due to sodium
sulphite (Na2S) and sodium sulphide (Na2SO3), there is a formation of sodium sulphate
(Na2SO4), which decomposes and gives SO2, and it forms sulphurous acid (H2SO3) in
steam condensate.
(3) Mechanical deaeration: As shown in Figure 1.9, the water passes through the perforated
plates and undergoes deaeration at high temperature and low-pressure dissolved oxygen
and carbon dioxide escapes. The solubility of a gas in water is directly proportional to
pressure and inversely proportional to temperature, hence the water gets deaeration.
Boiler feed water

(inlet)
To vacuum pump
Steel jacket
Perforated plate
T
Tower
Deaerated
water (outlet)
Figure 1.9 Mechanical deaeration of water

(b) By removal of dissolved carbon dioxide (CO2)

(1) Preheating: By increasing the temperature, solubility decreases.
(2) Chemical treatment: By adding calculated quantity of ammonia
2 NH 4 OH + CO2 → ( NH 4 )2 CO3 + H 2 O
(3) Mechanical deaeration: It removes DO as well as CO2 from feed water.
(c) Addition of alkali: Corrosion by acids may be prevented by adding some alkalies from out-
side so that product acid may be neutralized.
(d) By using soft water in the boiler for steam generation.
(iv) Caustic Embrittlement
Caustic embrittlement is the special type of boiler corrosion caused by the use of highly alkaline
water. With this phenomena boiler material becomes brittle with the accumulation of caustic
substances.
During the softening of water by lime soda process, usually small amount of free Na2CO3
is present. In high-pressure boilers, sodium carbonate decomposes and gives sodium hydroxide
and this makes the boiler water ‘caustic.’
Na 2 CO3 + H 2 O 

→ 2 NaOH + CO2 ↑
The concentration of NaOH is increased by evaporation of water, and attacks the boiler
material by giving sodium ferroate (Na2FeO2), which decomposes and forms rust.
FeO2 + 4 H 2 O 
Na 2 FeO → 6NaOH + F
NaOH
NaO
aOH Fee3O 4 + H 2 ↑
Sodium ferroatee Rust
R
This is an electrochemical phenomenon and can be explained on the basis that a concentration
cell is formed due to concentration difference of sodium hydroxide in the boilers particularly at
highly stressed parts like joints, rivets, etc. The dilute NaOH region in the boiler acts as a cath-
ode and the concentrated NaOH region acts as an anode and undergoes corrosion.
(+)
Iron at joint rivets, Concentrated NaOH Dilute NaOH region (−)
Iron at plane surfaces
bends, etc. region
Preventions
(a) By using sodium phosphate as a softening agent instead of sodium carbonate.
(b) By adding certain chemicals such as lignin and tannin to boiler water because they block the
hair cracking inside the boiler.
(c) By adding sodium sulphate to boiler water, which blocks the minute cracks thereby
preventing the entry of sodium hydroxide solution.
1.15 SOFTENING OF WATER

In water, there is a formation of scale-like impurities in the boiler. This scale formation may be mini-
mized by the following treatments:
(i) Internal treatment
(ii) External treatment

(i) Internal treatment: In this method, chemicals are added to the water in the boiler, which is hard
in nature. The added chemicals may function as precipitating agents or sequestering agents to
form more soluble complex compounds with metal ions. In this method, hard deposit scale is
changed into loose deposits, which are easily removed by blow-down operation. Internal treat-
ment of boiler water depends on the nature of feed water and the type of the boiler.
Some important internal treatment methods are:
(a) Colloidal conditioning: In this method, scale formation can be reduced by introducing
organic substances like kerosene, tannin, agar-agar, etc. They surround the minute particles
of scale-forming salts, thereby yielding non-sticky and loose deposits, which can easily be
removed by blow-down operation.
(b) Carbonate conditioning: In low-pressure boilers, scale formation is prevented by adding
sodium carbonate (Na2CO3) to boiler water to prevent the precipitation of scale-forming
calcium sulphate (CaSO4).
When calcium sulphate is converted into calcium carbonate by the addition of sodium
carbonate, CaCO3 acts as a loose sludge, which can be removed by blow-down operation.
CaSO 4 + Na 2 CO3 → CaCO
CaCO3 + Na 2SO 4
loose sludge
Carbonate conditioning is not used in high-pressure boilers because excess of Na 2CO3 might
be converted into NaOH due to hydrolysis, which causes caustic embrittlement.
(c) Phosphate conditioning: Phosphate conditioning involves conversion of scale-forming
calcium and magnesium salts into the most insoluble compound of calcium phosphate
(Ca3(PO4)2) and magnesium phosphate (Mg3(PO4)2), which form easily removable non-
adherent soft sludge, which can be removed by blow-down operation.
3CaCl 2 + 22Na
Na 3 PO 4 → Ca 3 ( PO 4 )2 ↓ + 6 NaCl
3MgCl2 + 2Na
2 Na 3 PO 4 → Mg3 ( PO 4 )2 ↓ + 6 N
NaCl
aCl
The three sodium orthophosphates may be used depending upon the alkalinity of the boiler-
feed water.
(1) In acidic medium, sodium dihydrogen phosphate (NaH2PO4)
(2) In weakly alkaline medium, disodium hydrogen phosphate (Na2HPO4)
(3) In alkaline medium, trisodium phosphate (Na3PO4)
(d) Calgon conditioning: Addition of calgon or sodium hexameta phosphate (NaPO3)6 to boiler
water converts calcium salts into soluble complex compound thereby preventing scale or
sludge formation.
Na 2 [ Na 4 (PO Na + + [Na
(PO3 )6 ] 22Na [Na 4 ( P
POO3 )6 ]2 −
Calgon
O4 + [ N
2CaSO Naa 4 ( P
POO 3 )6 ]2 − → [Ca 2 (PO3 )6 ]2 − + 2Naa 2SO
SO 4
soluble complex ion
(e) Sodium aluminate treatment: When we add sodium aluminate (NaAlO2) in boiler-feed
water, it gets hydrolyzed and form sodium hydroxide (NaOH) and gelatinous precipitate of
aluminium hydroxide Al(OH)3.

O2 + H 2 O → A
NaAlO OH)3 + N
All(OH NaOH
gelatinous ppt
The sodium hydroxide reacts with magnesium salt and converts it into magnesium hydroxide
Mg(OH)2 precipitates.
MgCl2 + 2 NaOH → Mg(OH)2 + 2NaCl

gelatinous ppt
The gelatinous precipitate of Al(OH)3 and Mg(OH)2 entraps colloidal and finely suspended
impurities along with oil drops and silica. The loose slimy precipitate can be easily removed
by blow-down operation.
(f) Complexometric conditioning (EDTA conditioning): When EDTA is added to boiler-feed
water having pH 8.5, then EDTA binds with the scale-forming cations to form stable and
soluble complex. Hence, scale and sludge formation in boiler is prevented.
(g) Electrical conditioning: In this method, sealed glass bulbs, containing mercury connected
to a battery, are set rotating in the boiler. As water boils, mercury bulb emits electrical dis-
charges, which prevent scale-forming particles to adhere together to form scale.
(h) Radioactive conditioning: Radioactive salts containing tablets are placed inside the boiler-
feed water at a few points. Energy radiated from radioactive substances prevents the scale
and sludge formation.
(ii) External treatment: Hard water causes a number of harmful effects when used for domestic,
industrial, and boiler purposes. So we have to remove or reduce hardness-causing impurities pres-
ent in water before using it for any purpose.
The most common methods for softening of water are given below:
(a) Lime soda process
(b) Zeolite process/permutit process/base exchange process
(c) Demineralization/ion-exchange process/de-ionization
(a) Lime Soda Process
It is a very important and popular process for softening of water.
Principle: This method involves the treatment of water sample with calculated quantities of
lime [Ca(OH)2] and soda (Na2CO3), which react with calcium and magnesium salts to form
insoluble precipitates as calcium carbonate (CaCO3) and magnesium hydroxide (Mg(OH)2).
To accelerate the precipitation of CaCO3 and Mg(OH)2, certain substances are added, known
as “coagulants” or “flocculants.”
Functions of lime: For removing temporary hardness, permanent magnesium hardness,
free mineral acids, iron and aluminium salts, dissolved CO2 and H2S in water, lime acts as
a good agent.
(1) Removal of temporary hardness: Here lime converts bicarbonates into carbonates
HCO3 )2 + Ca
Ca( HCO OH)2 
Ca(OH → 2C aCO3 ↓ + 2H 2 O
CaC
aCO
HCO3 )2 + 2Ca
Mg( HCO OH)2 
Ca(OH → 2C aCO3 ↓ + Mg
CaC
aCO OH)2 + 2H 2 O
Mg(OH

(2) Removal of permanent magnesium hardness: Lime can remove the permanent
magnesium hardness and converts the magnesium hydroxide
MgCl2 + Ca(OH)2 

→ Mg(OH)2 ↓ + CaCl
CaCl 2
MgSO4 + Ca(OH)2 
→ Mg(OH)2 ↓ + CaSO 4
In this case, permanent magnesium hardness is converted to permanent calcium
hardness.
(3) Removal of dissolved iron and aluminium salts: Lime can convert iron and aluminium
salts to the corresponding hydrates.
FeSO 4 + Ca(OH)2  
→ Fe(OH)2 ↓ + CaSO
CaSO 4
Al 2 (SO 4 )3 + 3Ca(OH)2 → 2Al(OH)3 ↓ + 3CaSO 4
(4) Removal of dissolved CO2 and H2 S: Lime can remove the carbon dioxide as calcium
carbonate and hydrogen sulphide as calcium sulphide.
CO2 + Ca(OH)2 

→ CaCO
CaCO3 ↓ + H 2 O
H 2S + Ca(OH)2 

→ CaS
CaS + 2H 2 O
Functions of soda: When lime is used to remove the hardness or mineral acids, it has
been found that permanent calcium hardness (CaCl2) and (CaSO4) is introduced in water.
Soda is very effective to remove permanent calcium hardness as follows:
CaCl 2 + Na 2 CO3 → CaCO

CaCO3 ↓ + 2 NaCl
CaSO 4 + Na 2 CO3 → CaCO
CaCO3 ↓ + Na 2SO 4
Important Points about Calculation of Lime and Soda

(i) There is no consideration of substances like NaCl, KCl, Na2SO4, SiO2, Fe2O3, etc., for
calculating lime and soda requirement as they do not impart any hardness.
(ii) Equivalent weight as NaAlO2 is equal to its molar mass.
(iii) When the impurities are given as CaCO3 and/or MgCO3, they should be considered
due to bicarbonates of calcium and/or magnesium, respectively.
(iv) When the impurities are presented in the form of ions such as Ca2+ and/or Mg2+ ion,
they are considered as a permanent hardness.
(v) If there are OH− and CO32− ions present in the treated water, it indicates that excess
of lime and soda, which are added for the treatment, and hence these excess amount
should be added (in terms of CaCO3 equivalent) to the calculation.
Requirement of lime and soda for the constituents responsible for hardness is given in Table 1.4.

Table 1.4 Calculation of lime and soda requirement

Constituents Chemical reaction Requirement
Temporary Hardness
Ca(( HCO
HCO3 )2 HCO3 )2 + Ca
Ca( HCO OH)2 → 2C
Ca(OH aCO3 + 2H 2O
CaCO
CaC
aCO L
Mg(HCO3 )2 + 2C
Ca(OH)
a(OH)2 2L
Mg(( HCO
HCO3 )2
→ 2CaCO3 + Mg(OH)2 + 2H 2O
Permanent Hardness
Ca 2+ Ca 2 + + Na 2CO3 → CaCO3 + 2 Na + S
Mg 2+ Mg 2 + + Ca(OH)2 → Mg(OH)2 + Ca 2 +  L+S

Ca 2 + + Na 2CO3 → CaCO 3 + 2 Na + 
Other Species
HCO3− O3− + Ca
HCO OH) 2 → C
Ca(OH CaCO
CaC O3 + H 2O + C
aCO COO32 − L−S
(e.g.
g. NaHCO
NaHCO3 )
H+ 2H + + Ca(OH)2 → Ca 2 + + 2H 2O  L+S

(Free Acid HCl, H 2SO 4 etc) Ca 2 + + Na 2CO3 → CaCO3 + 2 Na + 
CO2 CO2 + Ca(OH)2 → CaCO3 + H 2O L
Coagulants 2Al3+ + 3Ca

3Ca(OH)2 → 3Ca 2 + + 22Al(OH)3
Al 2 (SO 4 )3 2+ L+S
3Ca + 3Na
3Na 2CO3 → 3CaCO3 + 66NaNa +
3+ 2+
[∵ 2Al = 3CCaa ]
FeSO 4 Fe2 + + Ca(OH)2 → Fe(OH)2 + Ca 2 + L+S

Ca 2 + + Na 2CO3 → CaCO3 + 2 Na +
NaAlO2 O 2 + 2H 2O → A
NaAlO OH)3 + N
All(OH NaOH −L
[∵2 NaOH = Ca(OH)2 ]
Formula for Lime and Soda Requirement

100 parts by mass of CaCO3 are equivalent to
(i) 74 parts of Ca(OH)2
(ii) 106 parts of Na2CO3
74
Lime Requirement = Temp. Ca 2 + + 2 × Temp Mg2 + + per Mgg2 + + Fe2 + + Al3+ )
per( M
100 
+ H + + CO2 + HCO3− − N aAlO2 
NaAlO
all in terms of CaCO3 eq × Voll. oof water
× purity factor (100/% purity)

106
Soda Requirement =  perm(Ca 2 + + Mg2 + + Al3+ + Fe2 + ) + H + − HCO3− 
100 
CO 3 × V
all in terms of CaaC Vol.of water
× purity factor (100/% purity)
Process: Lime soda process is of two types:

(i) Cold lime soda process (at room temperature)
(ii) Hot lime soda process (at 90°C–100°C temperature)
(i) Cold lime soda process
(a) Calculated quantity of lime and soda is mixed with hard water at room
temperature.
(b) At room temperature, the precipitates formed are fi nely divided, so they do not
settle down easily.
(c) So it is essential to add a small amount of coagulant, which hydrolyzes to form
flocculent and gelatinous precipitate of aluminium hydroxide or ferric hydroxide,
which entraps the fi ne precipitates (as shown in Figure 1.10).
Hard water (containing Ca2+, Mg2+, or other heavy metals) + lime + soda
(i) Addition of coagulants or flocculent
(ii) Proper setting time
↓
ppts of CaCO3 + Mg(OH)2 settle out.
FeSO 4 + Ca(OH)
Ca(OH)2 → Fe(OH)2 + CaSO
CaSO 4
(SO 4 )3 + 3Ca(HCO
Al 2 (SO Ca(HCO3 )2 → 22Al(OH)3 ↓ + 33C O 4 + 6CO
CaSO 6CO2 ↑
Aluminium sulphate Gelantinous
(Coagulent) ppts
Motor
Driving belt
Chemicals feed
inlet Raw water (inlet)
(L + S + coagulants)
Filtered softened water
(outlet)
Stirrer
paddles
Outer chamber
Stirrer Inner chamber
Sedimented
sludge
[CaCO3, Mg(OH)2]
Sludge
outlet
Figure 1.10 Cold lime soda softener

(d) Use of sodium aluminate (NaAlO2) as coagulant also helps in the removal of
silica as well as oil, if present in water.
O2 + 2H
NaAlO 2H 2 O → NaOH + Al(OH)3 ↓
Sodium aluminate Aluminium hydroxide
(e) The residual hardness after cold lime soda process is 50 to 60 ppm.
(ii) Hot lime soda process
(a) In this method, softening of water by lime and soda at temperatures close to the
boiling temperature of water (100°C).
(b) The chemical reactions proceed at a faster rate, because the viscosity of water is
low at higher temperature and precipitates sludge settle down easily.
(c) No coagulants are required for hot lime soda process.
(d) The hot L-S plant consists of three parts (as shown below in Figure 1.11):
(1) A ‘reaction tank’ in which feed water, chemicals, and steam are thoroughly
mixed.
(2) A ‘conical sedimentation vessel’ in which sludge settles down.
(3) A ‘sand filter’ that ensures complete removal of sludge from the water.
In the hot process, sodium carbonate (Na2CO3) is used for softening because
it decomposes into sodium hydroxide under high pressure and temperature.
Na 2 CO3 + H 2 O → 2 NaOH + CO2
HCO3 )2 + 2 N
Ca( HCO aOH → C
NaOH
NaO
aOH CaCO
CaC O3 ↓ + N
aCO CO 3 + 2 H 2 O
Naa 2 CO
CaCl 2 + Na 2 CO3 → CaCO3 ↓ + 2 NaCl
HCO3 )2 + 4 NaO
Mg( HCO aOH → M
NaOH OH)2 ↓ + 2 N
Mgg(OH Naa 2 C
COO3 + 2H 2 O
MgCl2 + 2 NaOH → Mg(
Mg(OH)2 + 2NaCl
2 NaCl
(e) The residual hardness after hot lime soda process is 15–30 ppm.
Raw water
(Inlet)
Super
heated steam
(Inlet)
Chemical feed (L + S)
Inlet
Reaction tank
Conical
sedimentation Fine sand layer
tank Coarse sand layer
Precipitated Gravel layer
sludge Filtered softened water
[CaCO3, Mg(OH)2] (Outlet)
Sludge outlet
Figure 1.11 Hot lime soda process

Advantages of Lime Soda Process

(i) It is very economical.
(ii) Hot L-S process is much faster than cold lime soda process.
(iii) During lime soda process, pH value of water is increased; hence corrosion of pipe is
reduced.
(iv) The alkaline nature of treated water controls the amount of pathogenic bacteria in water.
(v) This process also helps to remove Fe and Mn to some extent.
(vi) It removes not only hardness-causing salts but also other minerals.
Disadvantages of Lime Soda Process

(i) Soft water contains 15–30 ppm residual hardness.
(ii) It requires careful operation and skilled supervision for efficient softening.
(iii) Sludge disposal is different and poses a problem.
Difference between cold and hot lime soda process is given in Table 1.5.
Table 1.5 Difference between cold and hot lime soda process
Cold lime soda process Hot lime soda process
1. Less efficient process Very efficient process
2. Reactions are comparatively slow Reactions are fast and complete
3. Low softening capacity High softening capacity
4. Filteration is slow Filteration is fast
5. Coagulants are essential Coagulants are not required
6. Dissolved gases are not removed Dissolved gases such as CO2 and H2S are removed to
some extent
7. Steam is not required Steam is essential
8. Residual hardness is around 60 ppm Residual hardness of about 15–30 ppm
(b) Zeolite or permutit process

Zeolite is known as permutit, i.e., boiling stone. Zeolite process is widely used to soften
water. Zeolites are hydrated alumino silicate minerals. or
Sodium aluminium orthosilicate, and it is represented as Na2O·Al2O3·xSiO2·yH2O
(x = 2 – 10, y = 2 – 6) represented as Na2Z.
Zeolites are of two types:
(1) Natural zeolite: It is non-porous and derived from green sand.
Example: Natrolite (Na2OAl2O3·3SiO2·2H2O)
(2) Synthetic zeolite: It is porous and possesses a gel structure. It is prepared by heating
china clay, feldspar, and soda ash together. They have higher exchange capacity as
compared to natural zeolite. So it is more common in use.
Softening Process
In the zeolite process for softening hard water, the raw water is percolate through a bed of
zeolite (Na2Z), which is packed in a vertical cylindrical tank as shown in the Figure 1.12.
The zeolite bed retains the Ca2+ and Mg2+ ions from hard water by exchanging with Na+
ions thereby the out-flowing water contains sodium salts.

Feed water
+
Zeolite bed
Regeneration
with brine Water softening
Exhausted
zeolite bed
Raw water
(inlet)
Zeolite bed
Gravels
Injector
To sink
Soft water
(outlet)
NaCl solution
storage
Figure 1.12 Zeolite softener
CaSO 4 + Na 2 Z → CCaZ ↓ + Na 2SO 4

MgSO4 + Na 2 Z → M MgZ ↓ + Na 2SO 4
CaCl 2 + Na 2 Z → C
CaZ ↓ + 2 NaCl
HCO3 )2 + Na 2 Z → CaZ ↓ + 2 NaHCO3
Ca( HCO
Na2Z (Zeolite Bed)

Ca(HCO3)2/ Mg(HCO3)2/
Feed Feed
CaCl2/ Water MgCl2/
W r
Wate
CaSO4 MgSO4
MgZ
CaZ
+
+
2NaHCO3/2NaCl/Na2SO4
2NaHCO3/2NaCl/Na2SO4

This process removes both temporary and permanent hardness. After long use, the
zeolite bed gets exhausted. It can be regenerated by using chemicals.
Regeneration: When the zeolite bed is completely converted into calcium and magne-
sium zeolite, it no longer works as softener. It gets exhausted. At this stage, supply of feed
water is stopped, and the exhausted zeolite is regenerated by treating with a concentrated
(10%) brine (NaCl) solution.
Z + 2N
CaZ/MgZ aCll → N
NaCl
NaC Naa 2 Z + CaCl
CaCl 2 /MgCl 2
Exhausted Brine Regenerated Zeollite
ite
Zeolite
The regenerated zeolite bed thus obtained is used again for softening operation.
Zeolite process reduces hardness to 0–15 ppm.
Limitations
(i) Hard water should be turbidity free otherwise impurities will clog the pores.
(ii) Mineral acids must be removed if present because they destroy the zeolites.
(iii) If Mn2+ or Fe2+ ions are present in feed water, it must be removed, otherwise they
form MnZ or FeZ, which cannot be removed easily during regeneration.
Advantages of Zeolite Process

(i) Hardness-causing ions are completely removed with a very low residual hardness of
about 10 ppm in the softened water.
(ii) Zeolite process automatically adjusts for any variation in hardness of incoming water.
(iii) It is a clean process because it does not produce any sludge.
(iv) Zeolite equipment requires less area.
(v) It requires less time for softening the water.
(vi) It requires less skill for operation as well as maintenance.
Disadvantages of Zeolite Process

(i)
Zeolite process cannot tolerate acidity as the zeolite disintegrates.
(ii)
Turbid water cannot be treated satisfactorily.
(iii)
Treated water contains more sodium salts.
This process replaces Ca2+ and Mg2+ ions by Na+ ions, and hence softened water con-
(iv)
tains more sodium and also more dissolved salts.
(v) Anions such as HCO O3− , CO32 − remain in water as sodium salts, which contributing to
the alkalinity causes corrosion and caustic embrittlement of the boiler.
Difference between zeolite and lime soda process is given in Table 1.6.
(c) Demineralization process/Ion exchange process
In this process the cations and anions present in water and which can produce hardness are
removed by ion-exchange resins. Resins are long, cross-linked organic polymers with a
porous structure. Ion-exchange resins are mainly (1) cation-exchange resins and (2) anion-
exchange resins.

Table 1.6 Differences between zeolite and lime soda process

Zeolite process Lime soda process
1. Softened water contains residual hardness about Softened water contains 50–60 ppm in
10 ppm. cold lime soda process and 15–30 ppm
in hot lime soda process.
2. Treated water contains large amount of sodium Treated water contains less amount of
salt than in original raw water. sodium salt.
3. Cost of plant and material is higher. Capital cost is low.
4. This process is not useful for removal of acidic There is no such type of limitations.
impurities, turbidity, etc.
5. The plant occupies less space. The plant occupies more space.
6. Treated water contains more NaHCO3, which cre- Treated water is free from NaHCO3, so it
ates problem in boiler. is used in boiler.
7. The raw water must be free from suspended impuri- This process has no such limitation.
ties. Otherwise the pores of the zeolite get blocked.
8. It automatically sets itself to waters of different Frequent control and adjustment of rea-
hardness. gent is needed.
9. This process removes only Ca2+ and Mg2+ It removes cations and anions from the
ions in solution. It does not remove anions solution.
(HCO3− , Cl
Cl −, SO24 − ) from solution.
10. It is not fit for industrial purposes especially in It is fit for industrial purposes especially
boiler. in boiler.
(1) Cation-exchange resins: These are styrene-divinylbenzene copolymers. These resins

have acidic functional groups such as -COOH, -SO3H, etc., which are capable of exchang-
ing the cation by their hydrogen ions. Hence, they are also called cation exchangers.
They can be represented as R-H, where R is the insoluble polymeric heavy part.
CH2 CH CH2 CH CH2 CH CH2
− + − +
SO3H SO3H
H2C CH CH2
H 2C CH CH CH2
− + − +
SO3H SO3H
Sulphonation form of cation-exchange resin

(2) Anion-exchange resins: These are copolymers of styrene and divinylbenzene contain-
ing basic functional groups such as amine, substituted amine, quaternary ammonium
R′′-OH.
groups, etc. They can be represented as R ′-OH.
CH2 CH CH2 CH CH2 CH CH2
− + −
CH2NMe3+OH CH2NMe3 OH
H2C CH CH2
H2C CH CH CH2
− −
CH2N + Me3 OH CH2N + Me3 OH
Process: Both cation exchanger and anion exchanger are inter-connected with a pipe
as shown in the Figure 1.13. The hard water is fi rst passed through cation-exchange resin
chamber, which removes all the cations (e.g., Ca2++ and Mg2++) from it, and equal amount of
H+ ions are released from its column to water.
2R − H + Ca 2 + /Mg 2 + → R 2 Ca /R 2 Mg + 22H +
Cation-exchange reaction
Water + CO2
Impure
Water
CO2
Cation Anion Steam

exchanger exchanger Jacket
Gravel Gravel
Acid for Alkali for

regeneration regeneration
Demineralized
Pump Degasifier Water
Washing Washing
Figure 1.13 Demineralization by ion exchangers

After passing through cation-exchange chamber, the hard water is now pumped to
‘anion-exchange resin’ chamber where all anions like Cl−, SO2−4 , etc., are removed, and
equal amount of OH− ions are released from this resin bed to water.
R ′OH + Cl − → R ′Cl + OH − 
−
2R ′OH + SO 4 → R 2′ SO
2−
SO 4 + 2OH  Anion exchange reaction
CO3 + 2OH − 
2R ′OH + CO3 → R 2′ CO
2−
H+ and OH– ions released from reactions in equivalent amount get combined to pro-
duce water molecules.
H + + OH
OH − → H 2 O
Thus, the treated water is completely free from cations as well as anions, so it is
known as demineralized or deionized water.
Regeneration of Resins
After some time of usage (depending on water) of cation/anion exchange resins will
exhaust, and it is most important to regenerate.
Regeneration of cation-exchange resins: The cation-exchange resins are regenerated
by addition of dil. HCl or H2SO4:
Caa + 2H + 
R2C → 2R − H + Ca 2 +
( from acid
acid ) ( resin
resin ) ( washing
washing )
+
→ 2R − H + Mg2 +
Mgg + 2H 
R2M
( from acid
acid ) ( resin
resin ) ( washing
washing )
Regenerationof anion-exchange resin: The anion-exchange resins are regenerated by

addition of dil. NaOH:
SO 4 + 2OH − 
R 2′ SO → 2R ′ − OH + SO24 −

( from
from bas
basee) ( resin
resin ) ( washing
washing )
−
R ′Cl + OH  R′′ − OH + Cl −
→ 2R
( from
from bas
basee) ( resin
resin ) ( washing
washing )
After regeneration of both resins, columns are washed with deionized water, and the
washed product is passed to sink.
Advantages
≈22 ppm).
≈
(i) It produces water of very low hardness ((≈
(ii) Highly acidic or highly alkaline water also can be softened.
Disadvantages
(i) The equipment is very costly.
(ii) Expensive chemicals are required for regeneration.
(iii) Turbid water decreases the efficiency of resins.

Mixed-bed deionizer: As shown in Figure 1.14, mixed-bed deionizer contains a single cylindri-
cal vessel with a mixture of a strong cation exchanger and a strong anion exchanger, and is the
most efficient process than separate column exchanger process. Hard water which pass through
the mixed bed contacts number of times with both exchangers and purifies the water. Purified
water is having less than 1 ppm hardness and also this is a most widely used convenient method.
Anion exchanger
Exhausted mixed (Low density
density)
bed ionizer NaOH soln
Raw water (dilute)
Inlet
Mixed H2SO4 soln
ionizer (dilute)
bed Cation exchanger
(High density)
Demineralized Compressed Washing to sink

water Water air
for backwashing
Figure 1.14 Mixed-bed deionizer
Regeneration of resins: When the resins get exhausted, the mixed bed is backwashed with
water. The lighter anion exchangers get displaced to form an upper layer above the heavier
cation exchangers. Then the anion exchangers are regenerated by passing NaOH solution from
the top and then rinsed with deionized water. The lower layer of cation exchangers is generated
by passing H2SO4 solution and is finally rinsed with deionized water. The two beds are then
mixed again by forcing compressed air through it. Now the regenerated bed is ready for use
again.
1.16 DESALINATION
Desalination or desalting involves the removal of dissolved salts (e.g., NaCl) from water. The salinity
of water is due to dissolved NaCl and to a smaller extent of other inorganic salts.
Natural saline water such as sea water contains more than 35,000 ppm while brackish water con-
tains dissolved salts in the range 1000–3500 ppm.
Desalination of saline water may be achieved by any of the two approaches:
(i) Separating water from the saline water
As in
(a) Distillation or evaporation
(b) Freezing
(c) Solvent extraction
(d) Reverse osmosis
(ii) Separating the salt from the saline water
As in
(a) Osmionic process
(b) Electrodialysis

Reverse osmosis and electrodialysis are more important in large-scale operations, and operation
and principle involved in reverse osmosis are discussed.
Reverse Osmosis (RO) (Hyper Filteration)

This technique worksbased on the principle of osmosis. Reverse osmosis is a process by which a sol-
vent such as water is purified of solutes by being forced through a semipermeable membrane through
which the solvent, but not the solute may pass. It is exactly opposite of osmosis and hence it is known
as reverse osmosis.
Generally the tendency of a fluid, i.e., water, to pass through a semipermeable membrane into a
solution where the solvent concentration is higher, thus equalizing the concentrations of materials on
either side of the membrane is known as osmosis. But when pressure is applied on the concentrated side,
the solvent will flow in the reverse direction. Reverse osmosis uses 100–150 micron thick membrane
made from cellulose acetate or polymeric membranes having pores in the range of 0.0001–0.001 μm in
diameter; it allows only water to pass through it and not to the salt. The water molecules diff use through
the membrane while the contaminants get concentrated in the effluent stream and are discharged.
Process: In this process, a high pressure ((≈15–40 kg cm–2) is applied to the sea water or brackish
water, which is to be treated (as shown in Figure 1.15). The semi-permeable membrane allows only the
solvent molecule (pure water) to pass through it. Thus dissolved ionic and non-ionic solvents are left
behind, and water get purified from salt. Generally, we use membrane made up of polymethacrylate
and polyamide polymers for this process.
Advantages
(i) It removes ionic as well as non-ionic salts present in saline water.
(ii) It is economical, compact, and very simple.
Pressure
(≈15−40 kg cm−2)
Piston
Sea water
Semi-permeable
membrane
Pure water
Pure water
(Outlet)
Figure 1.15 Reverse osmosis unit

(iii) It is effective in removing colloidal matters also.

(iv) It is suitable for converting sea water into drinking water.
(v) It has long life and is easy to replace the membrane within two minutes.
(vi) The water obtained from the process can be used in high-pressure boilers.
Electrodialysis
Electrodialysis is another efficient technique used for the desalination of saline water and is a mem-
brane process.
Principle: Under the influence of an electric potential across a salt water solution, charged ions
move towards respective electrodes through ions and selective membrane.
The membranes are cation or anion selective, which basically means that either positive ions or
negative ions will flow through cation-selective membrane consisting of sulphated polystyrene, which
allows only cations to flow through and rejects anions. However, anion-selective membrane consists of
polystyrene with quaternary ammonia, which allows only anions and rejects cations. Multiple mem-
branes alternatively allow cation or anions to flow through. Hence, with this method we can get fresh
water from saline water.
Process: The process is carried out in a special type of the cell called electrodialysis cell (as shown
in Figure 1.16). It consists of two electrodes and ion selective membranes which are permeable to
either cation or anion. The anode is placed near anion-selective membrane while the cathode is placed
near the cation-selective membrane. The anion selective membrane has positively charged functional
groups such as R4N+ and therefore allows negatively charged ions only to pass through them. Similarly,
Sea Water at pressure

5 − 6 Kg/m2
Cation 1 C 2 A 3 C 4 A 5 C 6 A 7 Anion
selective + − + − + − selective
membrane membrane
+ − + − + −
Anode
+
+)
(+)
Cathode + − + − + −
(−)
+ − + − + −
+ − + − + −
+ − + − + −
Pure water
outlet
Concentrated
sea water outlet
Figure 1.16 Electrodialysis of sea water

a cation-selective membrane has negatively charged functional groups such as RCOO− and allows only
positively charged ions to pass through it. Saline water under a pressure of around 5−6 kg/m2 is passed
from the top of the cell and it passes between membrane pairs.
When an emf is applied across two electrodes the cations (Na+) present in salt water move towards
cathode through cation selective membrane and anions (Cl−) move towards the anode through anion
selective membrane. As a result, the concentration of ions in alternate compartments 2, 4, 6 etc.
decreases, while it increases in the alternate compartment 1, 3, 5 etc. Thus water in the even number
compartments becomes pure and is collected from the bottom of the cell. Similarly, water in the odd
number compartment becomes rich in the saline water i.e. it becomes concentrated saline water. It is
collected from a separate outlet at the bottom of the cell.
Advantages
(i) It is economical.
(ii) It is convenient and may be applied at room temperature.
(iii) It is most compact in size and requires only electricity for operation.
1.17 REVIEW QUESTIONS
1.17.1 Fill in the Blanks

1. Hard water prevents lathering of soap due to the presence of the dissolved salts of _______
and _______ .
[
[Ans.: calcium, magnesium]
2. _______ water has high quantity of organic matter.
[
[Ans.: Lake]
3. Hardness is expressed in terms of _______ equivalent.
[
[Ans.: CaCO3]
4. 1 ppm = _______ mg/L = _______ °Fr = _______ °Cl.
[
[Ans.: 1, 0.1, 0.07]
5. _______ indicator is used in EDTA titration.
[
[Ans.: EBT]
6. Caustic alkalinity in water is due to _______ and _______ ions.
[
[Ans.: OH−, CO32− ]
7. Solubility of _______ in water decreases with increase of temperature.
[
[Ans.: CaSO4]
8. The phenomenon of carrying of water along with impurities by steam is called _______ .
[
[Ans.: carry-over]
9. _______ is an ideal chemical for the removal of dissolved oxygen.
[
[Ans.: Hydrazine]

10. The presence of residual _______ in boiler water causes caustic embrittlement.
[
[Ans.: caustic, NaOH]
11. By adding _______ to boiler water, caustic embrittlement can be prevented.
[
[Ans.: sodium sulphate]
12. Sodium aluminated is added as a _______ in purification of water.
[
[Ans.: coagulant]
13. During lime soda process, calcium and magnesium ions impurities precipitate into _______
and _______ .
[
[Ans.: CaCO3, Mg(OH)2]
14. Name of natural zeolite is _______ .
[
[Ans.: natrolite, Na2O . Al2O3 . 4SiO2 . 2H2O]
15. In zeolite process, calcium and magnesium ions are replaced by _______ ions.
[
[Ans.: sodium]
16. Exhausted cation-exchange column is regenerated by passing a solution of _______ .
[
[Ans.: dilute HCl or dilute H2SO4]
17. Cation exchange resin have acidic functional groups like –SO3H, –COOH, –OH capable of
exchanging cation by their _______ ions.
[
[Ans.: hydrogen, H+]
18. Anion-exchange resins are having _______ ions, which are capable of exchanging anions in
water.
[
[Ans.: hydroxide, OH–]
19. _______ process produces least residual hardness in water.
[
[Ans.: Ion-exchange]
20. _______ and _______ are used for colloidal conditioning.
[
[Ans.: Tannin, agar-agar]
21. Water having no ions is called as _______ water.
[
[Ans.: demineralized or deionized]
22. Calgon having chemical name is _______ .
[
[Ans.: sodium hexameta phosphate, Na2[Na4(PO3)6]]
23. For domestic use, pH of water should be in the range of _______ .
[
[Ans.: 7–8]
24. _______ flocculent is precipitated out when Al2(SO4)3 alum is added as a coagulant in water.
[
[Ans.: Al(OH)3]
25. Chemical formula of alum is _______ .
[
[Ans.: K 2SO4 . Al2(SO4)3 . 24H2O]

26. _______ is the best way for disinfection of water in comparison with chlorine or bleaching powder.
[
[Ans.: chloramines, ClNH2]
27. In electrodialysis process, _______ can be separated from brackish water.
[
[Ans.: NaCl]
28. Electrodialysis consists of _______ selective membranes.
[
[Ans.: ions]
29. Cation selective membrane is allowed to pass _______ and move towards cathode, and anion
selective membrane is allowed to pass _______ and move towards anode.
[
[Ans.: cations, anions]
30. Flow of solvent from a region of low concentration to high concentration when two solutions
are separated by semi permeable membrane is called _______ .
[
[Ans.: osmosis]
1.17.2 Multiple-choice Questions

1. The purest form of natural water is
(a) River water (b) Sea water
(c) Underground water (d) Rain water
[
[Ans.: d]
2. The alkaline hardness of water is due to the presence of the following salts of calcium and
magnesium in water.
(a) HCO3− only (b) HCO3− and CO32− only
(c) SO 4 only
2−
(d) HCO3− , CO32− , and OH− only
[
[Ans.: d]
3. A sample of water contains 120 mg of Mg2+ per liter. The hardness of the sample of water in
terms of CaCO3 equivalent is
(a) 120 mg/L (b) 500 mg/L
(c) 250 mg/L (d) 1000 mg/L
[
[Ans.: b]
4. The total hardness of a sample of water is 1.88°Cl eq. CaCO3. Its hardness in ppm would be
(a) 26.88 (b) 18.8
(c) 0.188 (d) 34.65
[
[Ans.: a]
5. The colour obtained by adding EBT indicator to a sample of water containing Ca2+ and Mg2+
at pH = 9–10 is
(a) Blue (b) Wine red
(c) Pink (d) No colour
[
[Ans.: b]

6. On boiling and filtering hard water, water sample contains

(a) Temporary hardness (b) Permanent hardness
(c) Both (d) None of the above
[
[Ans.: b]
7. Blow-down operation causes the removal of
(a) Scales (b) Sludges
(c) Acidity (d) Basicity
[
[Ans.: b]
8. Scale formation in boiler-feed water is due to
(a) Metallic deposition (b) Corrosion in boilers
(c) Deposition of hard water (d) All the above
[
[Ans.: c]
9. Scale formation is mainly due to which of the following salt present in boiler-feed water?
(a) CaSO4 (b) MgCO3
(c) Na2SO4 (d) KCl
[
[Ans.: a]
10. Solubility of CaSO4 salt present in water
(a) Increases with increase in temperature
(b) Decreases with increase in temperature
(c) Remain unchanged with increase in temperature
(d) Not having any defi nite change with increase in temperature.
[
[Ans.: b]
11. EDTA method is used for determining
(a) Temporary hardness (b) Permanent hardness
(c) Temporary and permanent hardness (d) Alkalinity
[
[Ans.: c]
12. When phenolphthalein alkalinity, P = M then alkalinity is due to
(a) OH− (b) CO32−
(c) HCO3− (d) CO32− and HCO3−
[
[Ans.: b]
13. Permanent hardness of water cannot be removed by
(a) Lime soda process (b) Permutit process
(c) Boiling (d) Demineralization process
[
[Ans.: c]
14. Permutit is chemically
(a) Sodium silicate (b) Hydrated sodium alumino silicate
(c) Aluminium silicate (d) All the above
[
[Ans.: b]

15. Hard water is not suitable for use in boilers because

(a) It has a higher boiling point
(b) It leads to scale formation in the boiler
(c) It consumes more fuel in steam generation
(d) The quality of steam generated is not good
[
[Ans.: b]
16. Which of the following substances is capable of removing dissolved oxygen from water?
(a) Cl2 (b) N2H4
(c) Na2SO4 (d) CaOCl2
[
[Ans.: b]
17. Sterilization of water can be done by using
(a) H2O2 (b) O2
(c) Cl2 (d) NaOH
[
[Ans.: c]
18. Coagulants help in settling of
(a) Suspended impurities only
(b) Finely suspended impurities only
(c) Colloidal particles only
(d) Both the suspended and colloidal particles
[
[Ans.: d]
19. 1 ppm of K+ present in a sample of demineralized water is equal to
(a) 4.3478 × 10 –8 mol L –1 (b) 2.564 × 10 –10 mol L –1
(c) 2.564 × 10 mol L
–5 –1
(d) None of the above
[
[Ans.: c]
20. Calgon is a name given to
(a) Sodium silicate
(b) Sodium hexameta phosphate
(c) Sodium meta phosphate
(d) Calcium phosphate
[
[Ans.: b]
21. Permutit exchanges Ca2+ and Mg2+ ions present in hard water with
(a) Zeolite ions (b) H+ ions
+
(c) Na ions (d) None of these
[
[Ans.: c]
22. The exhausted zeolite can be regenerated by treating it with
(a) 10% NaCl solution (b) 50% NaCl solution
(c) 10% HCl solution (d) 50% HCl solution
[
[Ans.: a]

23. Brackish water contains dissolved

(a) CaSO4 (b) MgCl2
(c) NaCl (d) Na2SO4
[
[Ans.: c]
24. Which of the following samples of water cannot be softened by zeolite process?
(a) Water containing temporary hardness
(b) Water containing permanent hardness
(c) Water containing excess of alkalinity
(d) Water containing excess of dissolved salts
[
[Ans.: c]
25. The cation-exchange resins possesses
(a) Acidic groups (b) Basic groups
(c) Amphoteric groups (d) None of these
[
[Ans.: a]
26. Priming and foaming process in boiler-feed water is due to

(a) The formation of air bubbles and production of wet steam
(b) The formation of scales
(c) The formation of sludges
(d) None of these
[
[Ans.: a]
27. The cation and anion resins are made up of the basic polymer unit of
(a) Polyvinyl chloride (b) Poly acrylate
(c) Poly styrene (d) Polybutadiene
[
[Ans.: b]
28. By ion-exchange process the hardness of water can be reduced up to
(a) 0 ppm (b) 5 ppm
(c) 10 ppm (d) 15 ppm
[
[Ans.: a]
29. Boiler corrosion caused by using highly alkaline water in boiler is called
(a) Corrosion (b) Boiler corrosion
(c) Caustic embrittlement (d) Erosion
[
[Ans.: c]
30. Desalination is the process of removing
(a) Common salt from sea water and making it potable
(b) Hard salts from sea water
(c) NaOH from hard water
[
[Ans.: a]

31. An exhausted anion-exchange resin can be regenerated by treating it with

(a) Conc. HCl solution (b) Conc. NaOH solution
(c) Dilute brine solution (c) Conc. brine solution
[
[Ans.: b]
32. Tannins and agar-agar are used for

(a) Phosphate conditioning (b) Colloidal conditioning
(c) Radioactive conditioning (d) Calgon conditioning
[
[Ans.: b]
33. Alum is commonly used in the treatment of municipal water for

(a) Filteration (b) Sedimentation
(c) Coagulation (d) Flocculant
[
[Ans.: d]
34. The chemical formula of alum is
(a) K 2SO4 . Al2 (SO4)3 . 20H2O (b) KNO3 . Al2 (SO4)3 . 24H2O
(c) K 2SO4 . Al2 (SO4)3 . 24H2O (d) K 2SO4 . Al2 (SO4)3 . 21H2O
[
[Ans.: c]
35. Liquid chlorine is most effective
(a) Disinfectant (b) Coagulant
(c) Flocculant (d) Sterilizing agent
[
[Ans.: a]
36. The soft, loose, and slimy precipitate formed within the boiler is called
(a) Scale (b) Sludge
(c) Flocculant (d) Coagulant
[
[Ans.: b]
37. In reverse osmosis (RO) the flow of solvent is due to
(a) Potential gradient (b) Vapour pressure gradient
(c) Concentration gradient (d) None of the above
[
[Ans.: c]
38. In RO process, the membrane used is
(a) Polysulfone (b) Polysulfone amide
(c) Poly amide (d) All above
[
[Ans.: d]
39. Chemical formula of bleaching powder is
(a) Cl2 (b) HOCl
(c) NH2Cl (d) CaOCl2
[
[Ans.: d]

40. The acid responsible for disinfection of germs and bacteria is

(a) HCl (b) HNO3
(c) HOCl (d) H2CO3
[
[Ans.: c]
1.17.3 Short Answer Questions

1. Name the main sources of water.
Ans.: Sea water, rain water, ground water, and surface water.
2. What is the cause for alkalinity of natural water?
Ans.: Due to the presence of dissolved bicarbonates of Ca and Mg in water.
3. Defi ne hardness of water.
Ans.: Hardness is the characteristic property, which produces white scum on treating with soap
solution.
4. Why does not hard water give lather with soap?
Ans.: Because hard water produces insoluble white precipitate on treating with soap.
2C17H35COONa + CaCl2 → (C17H35COO)2 Ca↓ + 2NaCl
Soap Hardness White Scum
5. How is hardness of water expressed?
Ans.: The concentration of hardness-producing salts is expressed in terms of calcium carbonate
(CaCO3) equivalent.
6. How hardness is determined in terms of CaCO3 equivalent.
W × 50
Ans.: Hardness (CaCO3 equivalent) =
E
W = Weight of hardness-producing substance in ppm
E = Equivalent weight of hardness-producing substance
7. Defi ne ppm, mg/L, Clarke’s degree, and French degree.
Ans.: ppm: 1 part of CaCO3 equivalent hardness present in 106 parts of water.
mg/L: Number of mg of CaCO3 equivalent hardness present in 1L of water.
Clarke’s degree: Number of parts of CaCO3 equivalent hardness present in 70,000 parts of
water.
French degree: Number of parts of CaCO3 equivalent hardness present in 105 parts of water.
8. What is the relationship between ppm, mg/L, °Cl, and °Fr.
Ans.: 1 ppm = 1 mg/L = 0.07°Cl = 0.1°Fr
9. Explain why water containing Ca2+ (aq) and HCO3− (aq) ions is said to be hard.
Ans.: The Ca2+ ions give precipitates with soaps. On heating HCO3− ions, they are converted to
CO32− ions, which precipitate in kettles/boilers with Ca2+ ions.
10. Why do we express hardness of water in terms of CaCO3 equivalent?
Ans.: Because addition and subtraction of concentration of hardness-causing constituents are
easy. Its molecular mass is 100.

11. What are the salts responsible for the temporary and permanent hardness of water?
Ans.: Temporary hardness: Mg(HCO3)2 and Ca(HCO3)2
Permanent hardness: CaCl2, MgCl2, CaSO4, MgSO4, FeSO4, etc.
12. Name the gases that dissolve in water and cause corrosion.
Ans.: Oxygen, carbon dioxide, and sulphur dioxide.
13. What happens when hard water is boiled?
Ans.: On boiling, temporary hardness is removed by precipitating as
Ca(HCO3)2 ∆
→ CaCO3↓ + H2O + CO2↑
Mg(HCO3)2 ∆
→ Mg(OH)2↓ + H2O + CO2↑
14. Name any three substances that are used for sterilization of water.
Ans.: (i) Liquid chlorine (ii) Bleaching powder (iii) Chloramine
15. Why is chlorination is better than chlorine or bleaching powder for sterilization of water.
Ans.: Because chloramine
(i) is quite stable
(ii) does not impart bad taste to treated water
(iii) imparts good taste to treated water
16. What is break-point chlorination?
Ans.: It involves addition of sufficient amount of chlorine to water in order to
(i) oxidize organic matter
(ii) reduce substance and
(iii) free ammonia
and leaves behind mainly free chlorine for disinfecting disease-producing bacteria.
17. What are the advantages of break-point chlorination?

Ans.: (i) It oxidizes organic matter, NH3, and reducing substances completely.
(ii) It removes colour in water.
(iii) It destroys all the disease-producing bacteria completely.
(iv) It removes odour from water.
(v) It prevents any growth of weeds in water.
18. Mention the impurities present in natural water.

Ans.: (i) Suspended impurities
(ii) Colloidal impurities
(iii) Dissolved impurities
19. What is standard hard water.

Ans.: Usually it is a solution containing 1 g of CaCO3 equivalent hardness in 1 liter, i.e.,
1000 ppm of hardness water.
20. What is sedimentation with coagulation?

Ans.: The process of removing of fi nely suspended impurities as well as colloidal impurities by
adding requisite amount of coagulant to water before sedimentation.

21. What is colloidal conditioning?

Ans.: Scale formation can be avoided in low-pressure boilers by adding substances like kerosene,
tannin, agar-agar, etc., which get adsorbed over the scale-forming precipitates, thereby
yielding non-sticky and loose deposits, which can be removed by blow-down operation.
22. What is the indicator used in EDTA method? What is the end-point?
Ans.: Indicator: EBT
End point: Wine red to pure blue
23. Why is NH 4 OH-NH4Cl buffer solution added during the determination of hardness of water
by EDTA method?
Ans.: The indicator used in this titration (EBT) shows colour change at a pH value of about 10.
So alkaline buffer (NH 4 OH-NH4Cl) is used.
24. Soft water is not demineralized,whereas demineralized water is soft. Why?
Ans.: Soft water may contain Na+, Cl–, and SO2−4 ions, so it is not demineralized, whereas dem-
ineralized water does not contain any cation and anion.
25. Why is water softened by zeolite process fit for use in boilers?
Ans.: Because zeolite-softened water contains large quantities of sodium salts like NaCl,
Na2SO4, etc., which avoids caustic embrittlement.
26. CO2 should not be present in boiler-feed water. Why?
Ans.: Because CO2 forms carbonic acid (H2CO3) on reacting with water. So boiler’s wall material
can be attacked slowly by carbonic acid and becomes weaker and weaker progressively.
27. What is meant by softening of water?
Ans.: Softening of water means removing hardness-producing salts from water.
28. Why is water softened before using in boilers?
Ans.: Water should be softened before using in boilers otherwise it may cause various boiler
problems like
(i) scale and sludge formation
(ii) priming and foaming
(iii) boiler corrosion.
29. What is meant by disinfection of water by UV method.
Ans.: When water is irradiated by UV radiations, microorganisms and bacteria are killed. This
so-called disinfection of water by UV radiation.
30. What is zeolite?
Ans.: It is hydrated sodium alumino-silicate having formula Na2O . Al2O3 . xSiO2 . yH2O,
where x = 2–10
y = 2–6
It is represented as Na2Z, and Na+ ions are capable of exchanging by M2+ (Ca2+ or Mg2++)
present in water sample.
31. If silica is present in water, what harmful effects it can cause to boilers?
Ans.: If silica is present in water, it causes formation of very fi rmly sticking deposits of calcium
silicate (CaSiO3) and magnesium silicate (MgSiO3) scales in the boilers, which are very
difficult to remove.

32. Why is the presence of NaAlO2 in water equivalent to the presence of equivalent to Ca(OH)2?
Ans.: NaAlO2 + H2O→Al(OH)
→
→Al(OH) 3 + NaOH
1 eq. 1 eq. of Ca(OH)2
33. Alkalinity of water cannot be due to presence of (a) OH −, CO 32− and HCO3 − or (b) OH −, HCO3−
in water. Give reasons.
Ans.: Because, OH− and HCO3− react to form CO32−
OH − + HCO3− → CO32− + H2O.
34. Why does magnesium bicarbonate require double amount of lime for softening?
Ans.: Mg(HCO3)2 + 2Ca(OH)2 → 2CaCO3↓ + Mg(OH)2↓ + 2H2O
Thus from the above equation, mole of Mg(HCO3)2 ≡ 2 mol of Ca(OH)2
35. Are coagulants also used in hot lime soda process? Give reasons.
Ans.: No, because reaction proceeds faster in hot lime soda process, and the precipitate and sludge
formed settle down rapidly. Thus, no coagulants are required in hot lime soda process.
36. Water should not be soft for drinking purposes. Why?
Ans.: Water should not be soft for drinking purposes because soft water is plumbosolvent, i.e.,
it attacks lead used in plumbing.
37. What is the main advantage of reverse osmosis over ion-exchange process?
Ans.: Reverse osmosis removes all ionic, non-ionic, colloidal, and high molecular weight
organic matter.
38. Why does the water softened by lime soda process cause boiler troubles?
Ans.: The treated water still contains some residual hardness.
39. Why can caustic embrittlement be controlled by adding Na2SO4 to boiler-feed water?
Ans.: When Na2SO4 is added to boiler-feed water, it blocks hair cracks, thereby preventing infil-
teration of caustic soda solution in these areas. So by this way, caustic embrittlement is
prevented by using Na2SO4 in boiler-feed water.
40. Why is calgon conditioning better than phosphate conditioning?

Ans.: In calgon conditioning, the added calgon forms soluble complex compound with CaSO4,
thereby it prevents the scale and sludge formation in water.
2Na + [Na4(PO3)6]
+

2–
Na2[Na4(PO3) 6]
calgon
2CaSO4 + [Na4(PO3)6]2– → [Ca2(PO3)6]2– + 2Na2SO4
soluble complex
This soluble complex does not cause any problem in the boilers.
On the other hand, in phosphate conditioning, sodium phosphate is added to boiler
water so that precipitate of calcium phosphate is formed. Although this precipitate is non-
adherent and soft, it has to be removed by frequent blow-down operation.
2Na3PO4 + 3CaSO4 → Ca3(PO4)2↓ + 3Na2SO4
Hence, calgon conditioning is better than phosphate conditioning.

1.17.4 Descriptive Questions

Q.1 Complete the following equations:
a. 1 ppm = ______mg/L = ______°French = ______°Clark
∆
b. Ca(HCO3)2  →
c. Mg(HCO3)2 + 2Ca(OH)2 →
d. Na2[Na4(PO3)6] + 2CaSO4 →
Q.2 Explain the following:
a. Scale and sludge formation and their disadvantages
b. Caustic embrittlement
c. Boiler corrosion
Q.3 What is hardness of water? How is it determined by EDTA method?
Q.4 Describe the continuous lime soda process of softening hard water. Compare continuous cold
lime soda process with hot lime soda process.
Q.5 How is true exhausted zeolite bed regenerated? Give the merits and demerits of zeolite process.
Q.6 What are the requirements of water for domestic use?
Q.7 A water sample contains Ca(HCO3)2 = 32.4 mg/L, Mg(HCO3)2 = 29.2 mg/L, and CaSO4 =
13.5 mg/L. Calculate the temporary and permanent hardness.
[
[Ans.: 40 ppm,10 ppm]
Q.8 Calculate the hardness of water containing the following salts:
CaSO4 = 28 mg/LMg(HCO3)2 = 22 mg/L
MgCl2 = 30 mg/LCaCl2 = 85 mg/L
[
[Ans.: Temporary hardness = 15.07 ppm
Permanent hardness = 128.7 ppm]
Q.9 1 g of CaCO3 was dissolved in dil. HCl, and the solution was diluted to 1 liter. 50 ml of this solu-
tion required 45 ml of EDTA solution. 50 ml of hard water required 18 ml of EDTA solution during
titration in ammonia buffer using EBT indicator. On the other hand, 50 ml of boiled water sample
required 9 ml of EDTA solution under the same condition. Calculate each type of hardness in ppm.
[
[Ans.: Total hardness = 400 ppm
Permanent hardness = 200 ppm
Temporary hardness = 200 ppm]
Q.10 0.28 g of CaCO3 was dissolved in HCl and the solution made up to 1 liter with distilled water.
100 ml of the above solution required 28 ml of EDTA solution on titration. 100 ml of a hard water
sample required 33 ml of same required solution on titration. After 100 ml of this water, cooling
and filtering and then titrated 10 ml of EDTA solution. Calculate the temporary and permanent
hardness.
[
[Ans.: 230 mg/L, 100 mg/L]
Q.11 Explain the ion-exchange method of purifying the water. Discuss their use and regeneration,
giving the reaction involved.

Q.12 Write a short note on break-point chlorination.

Q.13 Pure soft water is not fit for drinking purpose. Why?
Q.14 Write the principle of lime-soda process? Why should we use coagulants along with lime and
soda? Why is water softened by zeolite process that is unfit for use in boilers?
Q.15 Explain reverse osmosis process for desalination of sea water.
Q.16 A water sample contains the following impurities: Ca2+ = 20 ppm, Mg2+ = 18 ppm, HCO3−
= 183 ppm, and SO2−
4 = 24 ppm. Calculate the amount of lime and soda needed for softening.
[
[Ans.: Lime = 185 mg/L
Soda = Zero mg/L]
Q.17 Water sample on analysis gave the following results: Mg(HCO3)2 = 70 mg/L, CaCl2 = 220
mg/L, MgSO4 = 120 mg/L Ca(NO3)2 = 164 mg/L. Calculate the quantity of lime (80% pure) and
soda (90% pure) needed for softening the 10,000 liters of water.
[
[Ans.: Lime = 1.81 kg
Soda = 4.68 kg]
Q.18 A water sample contains the following constituents in ppm: Mg(HCO3)2 = 73, MgCl2 = 95,
MgSO4 = 12, CaSO4 = 68, Ca(HCO3)2 = 81, and NaCl = 4.8. Calculate the cost of chemicals
required for softening 20,000 liters of water, if purity factor for lime is 95% and soda is 90%. The
costs per 100 kg each of lime and soda are Rs. 75 and Rs. 2480, respectively.
[
[Ans.: Lime cost = Rs. 3.03;
Soda cost = Rs. 93.44]
Q.19 What do you mean by pre-chlorination, post-chlorination, and superchlorination. Write the
significance of break-point chlorination.
Q.20 What do you mean by screening, sedimentation, and coagulant sedimentations? How are
colloidal impurities removed from water?
Q.21 What are the factors that cause alkalinity in water? How is alkalinity of water determined by
titrimetric method ?
Q.22 Write a short note on the followings:
a. Phosphate conditioning b. Calgon conditioning
c. Colloidal conditioning d. Carbonate conditioning
e. EDTA conditioning
1.17.5 Problems for Practice

1. 200 ml of water sample require 25 ml of N/50 H2SO4 for neutralization to phenolphthalein
N
end point. After that methyl orange was added to this, and further acid required was 35 ml
H SO . Calculate the type and amount of alkalinity of water as CaCO in ppm. 50
2 4 3
[
[Ans.: CO32− = 250 ppm
HCO3− = 50 ppm]

2. Calculate the amount of lime (88.3% pure) and soda (99% pure) required to soften 24,000 lit-
ers of water per day, which contains the following:
CaCO3 = 1.85 ppm CaSO4 = 0.34 ppm MgCO3 = 0.42 ppm
MgCl2 = 0.76 ppm MgSO4 = 0.90 ppm NaCl = 2.34 ppm
[
Soda = 46.25 kg]
3. Calculate the amount of lime and soda needed for softening 106 liters of water sample, which
contains Mg2+ = 36 ppm, Ca2+ = 20 ppm, and HCO3− = 183 ppm.
[
[Ans.: Lime = 222 kg
Soda = 53 kg]
4. A water sample contains the following: Ca2+ = 120 ppm, Mg2+ = 120 ppm, CO2 = 132 ppm, HCO3− =
122 ppm, and K+ = 40 ppm. Calculate the amount of lime 80% pure and soda 90% pure for sof-
tening 106 liters of water sample.
[
Soda = 824.4 kg]

2 POLYMERS
“Important things for easy life—through polymers”.
2.1 INTRODUCTION
In modern world, polymers are an integral part of an individual’s life. They have the most diverse struc-
ture and applications ranging from domestic articles to highly sophisticated instruments. Polymers are
used in almost all fields such as medicine, industry, agriculture, construction and so on. In recent days,
these materials are used to prepare nanomaterials.
The human body is built up and functions with polymers such as DNA, RNA, hormones, enzymes,
proteins, lipids, phosphonitrilic acids and so on. Most of the food materials that we eat are polymers
such as carbohydrates, starch and so on. In view of their importance, a proper understanding of poly-
meric materials is very essential.
The word polymer is derived from Greek word poly, which means many and meros which means
units (or) parts. Polymers are macromolecules of high molecular masses built up by the linking together
of a large number of small, repeated units by a covalent bond. The repeating unit present in the forma-
tion of a polymer is known as polymerisation.
For example,
Polymer Structure Monomer

1. Polyethylene [ CH2 CH2 ]n H2C CH2 (Ethylene)
2. Polyvinyl chloride
[ CH2 CH ]n H2C CH (Vinyl chloride)
Cl Cl
2.2 DEGREE OF POLYMERISATION

The size of the polymer molecule is decided by the number of repeating units present in it. The number
of repeating units (n) in a chain formed in a polymer is known as the “degree of polymerisation”.
H H H H
nC C [C C ]n
H H H H
Ethene (monomer) Polythene (polymer)
M02_ENGINEERING-CHE00_SE_1181_CH02.indd 1 5/21/2016 9:20:00 AM

In the figure, n is the degree of polymerisation. It is different from polymer and can be 104 or more.
Molecular weight of polymer = Molecular weight of repeating unit × degree of polymerisation
2.3 CLASSIFICATION OF POLYMERS

Polymeric materials can be classified into several ways:
2.3.1 Classification Based on Source

(i) Natural polymers: These polymers are isolated from natural material such as animals and plants.
For example, cotton, silk, wool, nucleic acids, proteins, starch, cellulose, natural rubber, etc.
CH3 CH3
Polymerization
nCH2 C CH CH2 [ CH2 C CH CH2 ]n
2-methyl 1-3 butadiene Poly-isoprene
(isoprene) (rubber)
(ii) Synthetic polymers: Polymers synthesised from low molecular weight compounds are called
synthetic polymers.
For example, polyethylene, polyvinyl chloride, nylon, terylene, etc.
Polymerization
nH2C CH [ H2C CH ]n
Cl Cl
Vinyl chloride Polyvinyl chloride
2.3.2 Classification Based on Composition

(i) Univalent or homopolymers: These are formed with the same monomer units.
For example, polyethylene, polystyrene, polyvinyl chloride, etc.
(ii) Copolymers: These are formed with two or more different monomer units.
For example,
Copolymer Monomer molecules

1. Styrene butadiene rubber Styrene + Butadiene
2. Nitrile rubber Acrylonitrile + Butadiene
Copolymers are classified into four categories depending upon the nature of the distribution of
different monomers in the polymer chain.
(a) Random copolymer: These are formed by the random arrangement of monomer units in the
chain.
A B A A A B B A B B
(b) Alternating copolymers: Monomer units in a copolymer molecule are arranged in an alternate
manner.
A B A B A B

Polymers 2.3
(c) Block copolymer: A block copolymer consists of one in which blocks of repeating units of one
monomer alternate with blocks another monomer.
A A A A B B B B A A A A
(d) Graft copolymer: This copolymer consists of a linear polymer chain of one monomer to which
side chain of different monomer has been grafted.
B
B
B
B
B
A A A A A A A
B B
B
B
B
B B
B
2.3.3 Classification Based on Chemical Composition

(i) Organic polymers: A polymer whose backbone chain is essentially made of carbon atoms is
termed as organic polymer.
For example, polyethylene, polystyrene, polyvinyl chloride, etc.
(ii) Inorganic polymers: Polymers that are formed by non-carbon-carbon bonds are inorganic
polymers.
For example, polysilanes, polygermanes, etc.
2.3.4 Classification Based on Structure

(i) Linear polymers: Here, monomeric units are joined in the form of long, straight chains.
For example, nylons, polyester, polyvinyl chloride, high-density polythene, etc.
(ii) Branched chain polymers: These are mainly linear in nature but also possess some branches
along the chain.
For example, glycogen, amylopectin, low-density polythene, etc.
(iii) Cross-linked polymer: These polymers adjacent chains are joined one to another at various posi-
tions by covalent bonds.
For example, elastomers like rubber.
(iv) Network polymers: Monomer units that have trifunctional groups form three dimensional
networks. The cross-linked polymer is also called network polymer.
For example, Bakelite, urea formaldehyde resin, silicones, etc.

2.3.5 Classification Based on Mode of Polymerisation

(i) Addition polymers: Addition polymerisation takes place in compounds containing reactive dou-
ble bonds. Chain polymerisation is characterised by a self-addition of the monomer molecules to
each other very rapidly through a chain reaction.
For example, polyethylene, polypropylene, polyvinyl chloride, etc.
(ii) Condensation polymers: This type of polymerisation was brought about by monomers contain-
ing two or more reactive functional groups condensing with each other to form a large condensed
polymer and also loss of small molecules such as H2O, NH3, HCL and so on.
For example, polyester, nylon, polyamide, etc.
2.3.6 Classification Based on the Molecular Forces

(i) Thermoplastic polymers: These are linear, long chain polymers, which can be softened on
heating and hardened on cooling reversibly. Thus, they can be processed several times.
For example, polythene, polypropylene, polyvinyl chloride, etc.
(ii) Thermosetting polymers: These polymers get hardened during moulding, and once they have
solidified, they cannot be softened. During moulding, such polymers acquire three-dimensional
cross-linked structure with predominantly strong covalent bonds.
For example, polyester, Bakelite, urea formaldehyde, etc.
(iii) Elastomer: These are rubber-like elastic polymers, which can be stretched to at least thrice its
length, but return to their original shape and dimension as soon as the stretching force is released.
(iv) Fibres: Fibres are polymers whose chains are held by strong intermolecular forces like hydrogen
bonding. They are crystalline in nature and of high tensile strength, due to strong intermolecular
forces.
For example, nylon, polyester, etc.
2.3.7 Classification Based on Tacticity

The stereo chemical arrangement of the monomer units in the main chain of a polymer is known as
tacticity. The orientation of monomeric units in a polymer can take an orderly or disorderly twist
with respect to main chain polymers that are mainly classified into isotactic, syndiotactic and atactic
polymers.
(i) Isotactic polymers: In this polymer, all the side groups lie on the same side of the chain (cis
arrangement), e.g., natural rubber.
H R H R H R H R H
H H H H H H H H H
H R H R H R H R H R H R
C C C C C C
C C C C C C
H H H H H H H H H H

Polymers 2.5
(ii) Syndiotactic polymer: In this polymer, side groups are arranged alternatively (trans arrange-
ment), e.g., Gutta-percha.
H R H H H R H H
H H H R H H H R
H R R H H R R H H R R H
C C C C C C
C C C C C C
H H H H H H H H H H
(iii) Atactic polymer: In this polymer, the monomers randomly arranged to the main chain, e.g.,
polypropylene.
H R R H R H H R R H
H H H H H H H H H H
H R H R H R R H H R R H
C C C C C C
C C C C C C
H H H H H H H H H H
2.4 TYPES OF POLYMERIZATION

Polymerisation is mainly of two types:
(i) Condensation polymerisation (or) step polymerisation
(ii) Vinyl or addition polymerisation (or) chain polymerisation
2.4.1 Condensation Polymerisation or Step Polymerisation

Condensation is brought about by monomers containing two or more reactive functional groups con-
densing with each other to form large condensed polymer and also loss of small molecules such as
H2O, NH3, HCl and so on.
(i) Polyester: Condensation between carboxylic acid and diol gives polyester.
2nH O R OH + nHOOC R COOH
Diol Dicarboxylic acid
O O
O R O C R C O R O + 2(n − 1)H2O
n
Polyester

(ii) Polyethylene terephthalate (PET):
n HO CH2 CH2 OH + nHOOC COOH

Ethylene glycol
Teryphthalic acid
H [O CH2 CH2 OOC CO ]n OH + 2(n − 1)H2O

PET
(iii) Polyamide: Condensation reaction between diamine and dicarboxylic acid gives polyamide.
H H O O
nH2N R NH2 + nHOOC R COOH H [ N R N C R C ]n + 2(n − 1)H2O
Diamine Dicarboxylic acid Polyamide
(iv) Nylon 66: Condensation reaction between hexamethylenediamine and adipic acid gives nylon 66.
nH2N (CH2)6 NH2 + nHOOC (CH2)4 COOH

Hexamethylenediamine Adipic acid
H H O O
2(n − 1)H2O + H [ N (CH2)6 N C (CH2)4 C ]n
Nylon 66
Reaction Mechanism
(i) In polymerisation, the monomers should have a minimum of two reactive functional groups for
polymerisation.
(ii) Polymerisation proceeds in a step-wise reaction between reactive functional groups. In this pro-
cess, the first two monomer units condense to form the dimer. The dimer reacts with another
dimer to form a tetramer or with monomer to form a trimer. In this process, small units such as
NH3, H2O, HCl and so on, are also formed.
(iii) Only one type of reaction between two functional groups is involved in polymer formation.
(iv) The polymer formed still contains both the reactive functional groups at the end of the chain;
hence it is active and not dead as in chain polymerisation.
(v) Reaction between two monomers contains two active functional groups. They will give straight
chain polymers; otherwise, monomers containing more than two functional groups form cross-
linked polymer.
Formation of Polyester
O O
nHO R OH + nHOOC R COOH [O R O C R C ]n + 2(n − 1)H2O
Diol Dicarboxylic acid Polyester

Polymers 2.7
HO R OH + HOOC R COOH
−H2O
HO R OOC R COOH
Ester
HO R OH HOOC R COOH
HO R OOC R COO R OH HOOC R COO R OCO R COOH

Diester HOOC R COOH Diester
HO R OH
HOOC R COO R COO R COO R OH
HOOC R COO R COO R COO R OH
Triester
HO R OH Triester HOOC R COOH
HO R OOC R COO R COO R COO R OH
HOOC R COO R COO R COO R OOC R COOH
The process is continuous and forms polymers.
Formation of Polyethylene Terephthalate
HO CH2 CH2 OH + HOOC COOH
Ethylene glycol Teryphthalic acid

−H2O
HO CH2 CH2 OOC COOH
Ester
HO CH2 CH2 OH
HOOC COOH
HO CH2 CH2 OOC COO CH2 CH2 OH
Diester
HOOC COO CH2 CH2 OOC COOH
HOOC COOH
Diester
Triester
HO CH2 CH2 OOC COO CH2 CH2 OOC COOH HO CH2 CH2 OH
Triester
HOOC COO CH2 CH2 OOC COO CH2 CH2 OH
Triester
The aforementioned reaction is continued and forms a large polymer.

n molecules of ethylene glycol react with n molecules of terephthalic acid.
nHO CH2 CH2 OH + nHOOC COOH
HO [ CH2 CH2 OOC COO ]n H + 2(n − 1)H2O

PET

Formation of Nylon 66
H2N (CH2)6 NH2 + HOOC (CH2)4 COOH
Hexamethylene diamine Adipic acid
−H2O
H2N (CH2)6 NH OC (CH2)4 COOH
Amide
H2N (CH2)6 NH2 HOOC (CH2)4 COOH
H2N (CH2)6 NH OC (CH2)4 CO NH (CH2)6 NH2

Diamide HOOC (CH2)4 CO NH (CH2)6 NH OC (CH2)4 COOH
HOOC (CH2)4 COOH
Diamide H2N (CH2)6 NH2
H2N (CH2)6 NH OC (CH2)4 CO NH (CH2)6 NH OC (CH2)4 COOH
Triamide
(CH2)4 CO NH (CH2)6 NH OC (CH2)4 CO NH (CH2)6 NH2
HOOC
Triamide
The aforementioned reaction proceeds that n molecules of hexamethylenediamine react with n mol-
ecules of adipic acid to form nylon 66.
nH2N (CH2)6 NH2 + nHOOC (CH2)4 COOH
H [ NH (CH2)6 NH OC (CH2)4 CO ]n OH + 2(n − 1)H2O

Nylon 66
Formation of Polyamide
H2N R NH2 + HOOC R COOH
H2N R NH OC R COOH
Amide
H 2N R NH2 HOOC R COOH
H 2N R NH OC R CO HN R NH2
Diamide HOOC R CO NH R NH OC R COOH
Diamide
HOOC R COOH
H2N R NH2
H2N R NH OC R CO HN R NH OC R COOH
Triamide HOOC R CO NH R NH OC R CO NH R N
Triamide
n molecules of diamine and n molecules of dicarboxylic acid react to form polyamide.
nH2N R NH2 + nHOOC R COOH H [ NH R NH OC CO ] n OH + 2(n − 1)H2O

Amide Dicarboxylic acid Polyamide

Polymers 2.9
2.4.2 Addition/Vinyl/Chain Polymerisation

Addition polymerisation takes place in compounds containing reactive double bonds. Chain polymeri-
sation is characterised by a self-addition of the monomer molecules to each other very rapidly through
a chain reaction. No by-product, such as HCl, NH3, H2O and so on, is formed. This polymerisation
occurs in the presence of catalyst, light, or heat.
(i) For example, In the presence of oxygen or Ziegler–Natta catalyst, ethylene gives addition poly-
mer, that is, polythene
O2 (or)
nH2C CH2 Ziegler-natta [ CH2 CH2 ]n
Ethylene catalyst Polythene
(ii) In the presence of azo compounds, vinyl chloride gives polyvinyl chloride.
Azo compounds
nH2C CH [ H2C CH ]n
Cl Cl
Vinyl chloride Polyvinyl chloride
(iii) In the presence of metal, amide styrene gives polystyrene.

Metal amide
nH2C CH [ H2C CH ]n
C6H5 C6H5
Styrene (Polystyrene)
(iv) In the presence of benzoyl peroxide, acrylonitrile gives polyacrylonitrile.

Benzoyl peroxide
nH2C CH [ H2C CH ]n
CN CN
Acrylonitrile Polyacrylonitrile
Reaction Mechanism
In the addition polymerisation, free radical, carbonium ion, or carbanium ions, act as active centres.
Hence, polymerisation may occur in the following:
(i) Free radical
(ii) Ionic (cationic or anionic)
(iii) Coordination mechanisms
In addition, polymerisation, consists of the following steps:
(i) Chain initiation
(ii) Chain propagation
(iii) Chain termination
Free Radical Polymerisation

The initiation of the polymer chain is brought about by free radicals produced by the decomposition of
monomers; thus, this reaction is called free radical polymerisation.

2.10
The decomposition of the initiation to form free radicals can be induced by heat energy, light
energy or catalysts.
Three steps included in free radical polymerisation are as follows:
(i) Chain initiation:
(a) In the presence of catalyst, heat or light, the initiator converts into free radical.
∆/ hv/catalyst •
I 2R
Initiator
Normally, H2O2, benzoyl peroxide, hydroperoxide, tertiary butyl peroxide and azobis-isobutyl
nitriles (AIBN) act as initiators.
(b) Free radicals react with the monomer unit to form a new, active-centred free radical.
• •
R + H2C CH R H2C CH
X X
Free radical Monomer New free radical
(ii) Chain propagation:
(a) In this step, free radical attacks the fresh monomer unit to form another free radical.
• •
R CH2 CH + H2C CH R CH2 CH CH2 CH
X X X X
New free radical
(b) This process continues till the monomer units are present in the reaction mixture. Finally, it
forms a chain propagate free radical.
• •
R CH2 CH + nCH2 CH R CH2 CH [ CH2 CH ]n CH2 CH
X X X X X
Free radical Monomer Chain propagate free radical
Propagation reaction is a very fast reaction; in this reaction, no middle product is formed.
(iii) Chain termination:
In this step, chain propagate polymer radical deactivates with coupling or disproportionation
reaction to stop chain propagation and forms dead polymer.
(a) Coupling: Chain propagation free radicals meet to form polymer and terminate the reaction.
• •
R CH2 CH + CH CH2 R R CH2 CH CH CH2 R
X X X X
Polymer
(b) Disproportionation reaction: Hydrogen atom shifts from one chain propagate free radical to
another chain propagate free radical and ends the reaction.
• •
R CH2 CH + HC CH2 R R CH2 CH2 + HC CH R
X X X X
For example, polymerisation of acrylonitrile in the presence of benzoyl peroxide.

Polymers 2.11
Reaction Mechanism
(a) In this step, benzoyl peroxide dissociates to form phenyl free radicals.
• •
C6H5 CO O O CO C6H5 2C6H5COO 2C6H5 + 2CO2
Benzoyl peroxide Phenyl free radical
(b) Phenyl free radicals react with acrylonitrile and gives chain initiate free radical.
• •
R + H2C CH R CH2 CH
CN CN
Acrylonitrile Chain initiate free radical
(a) In this step, free radicals react with monomer units and give a chain propagate free radical.
This reaction continues till the monomer units are present in reaction mixture.
• •
R CH2 CH + HC CH2 R CH2 CH CH2 CH
CN CN CN CN
nH2C CH
CN
•
R [ CH2 CH ]n CH2 CH
CN CN
Addition polymer radical
(a) The chain terminates with the coupling reaction.
• •
R CH2 CH + HC CH2 R R CH2 CH CH CH2 R
CN CN CN CN
Addition polymer
polyacrylonitrile (PAN)
(or)
(orlon)
For example, polymerisation of methyl methacrylate in the presence of azobis-isobutyl
nitrile.
Reaction Mechanism
(a) In the presence of ultraviolet rays, azobis-isobutyl nitrile homolysis gives cyanopropyl
radical.
U.V •
(CH3)2 C N N C (CH3)2 2 (CH3)2 C + N2
CN CN CN
Azobis-isobutyl nitrile Cyanopropyl radical

2.12
(b) Cyanopropyl radicals react with methyl methacrylate monomer to form chain initiate free
radical.
CH3 CH3
•
(CH3)2 C + H2C C COOCH3 (H3C)2 C CH2 C•
CN CN COOCH3
Cyanopropyl Methyl Chain initiate free radical
radical methacrylate
(a) In this step, the chain initiates free radicals that react with monomer units; finally, it gives
the chain propagate free radical.
CH3 CH3 CH3 CH3
(H3C)2 C CH2 C• + H2C C COOCH3 (H3C)2 C CH2 C CH2 C•
CN COOCH3 CN COOCH3 COOCH3
CH3
nH2C C COOCH3
CH3 CH3
(H3C)2 C [ CH2 C ]n CH2 C•
CN COOCH3 COOCH3
Chain propagate free radical
(a) It terminates with a coupling reaction.
CH3 CH3 CH3 CH3
CH2 C• + • C CH2 H2C C C CH2
COOCH3 COOCH3 COOCH3 COOCH3

Polymethyl methocrylate
(PMMA)
CH3 CH3
ABIN
nH2C C [ H2C C ]n
COOCH3 COOCH3
Methyl methocrylate PMMA
Cationic Addition Polymerisation

The following are the important points in reaction mechanism:
(i) In this polymerisation, carbonium ion acts as the chain initiator.

Polymers 2.13
(ii) BF3, H2SO4 and AlCl3 like Lewis acids act as catalyst, water, carbonic acid, etc., act as co-catalysts.
(iii) In this polymerisation monomer acts as an electron donor and reacts with catalysts (electron
acceptor) to form carbonium ion. The formed carbonium ion reacts with monomer units and
propagates the reaction.
For example, cationic polymerisation of isobutylene in the presence of BF3:
CH3 CH3
BF3
nH2C C H2O
[ H2C C ]n
Isobutylene Polyisobutylene
CH3 CH3
Reaction Mechanism
(a) Carbonium ion is formed due to the following reactions.
−
BF3 + H OH [BF3OH]H [BF3OH] H+
Catalyst Co-catalyst
CH3 CH3
[BF3OH]− + −
H + H2C C H3C C+ [BF3OH]
CH3 CH3
Carbonium ion

(a) Monomer molecules react one by one with carbonium ion and propagate the chain to form
an addition polymer.
CH3 CH3 CH3 CH3
−
H3C C+
−
[BF3OH] + H2C C H3C C CH2 C+ [BF3OH]
CH3 CH3 CH3 CH3
Carbonium ion Isobutylene CH3
nH2C C
CH3
CH3 CH3 CH3
−
H3C C [ CH2 C ]n CH2 C+ [BF3OH]
CH3 CH3 CH3
Addition polymer ion

2.14

(a) Chain termination occurs with disproportionation reaction.
CH3 CH3 CH3 CH3 CH3 CH2
−
H3C C [ CH2 C ]n CH2 C⊕ [BF3OH] H3C C [ CH2 C ]n CH2 C + [BF3OH]H
CH3 CH3 CH3 CH3 CH3 CH3

Polyisobutylene
Anionic Addition Polymerisation

The following are the important points:
(i) Carbanion acts as chain initiator.
(ii) Alkali metal amide, Grignard reagents, etc., act as catalysts and initiate the chain.
(iii) Monomers containing electron-withdrawing groups participate in anionic polymerisation.
(iv) In this polymerisation, there is no chain termination; hence anionic polymers are known as
activated polymers.
Acrylonitrile, styrene and methyl methacrylate participate in anionic polymerisation. For example,
Anionic polymerisation of styrene in the presence of alkali metal amide:
CH CH2
KNH2
n [ CH CH2 ]n
Polystyrene
Styrene
Reaction Mechanism
(a) Carbanion is formed in the chain initiation.
(−)
KNH2 K++ NH2
Catalyst
(−) −
NH2 + H2C CH NH2 CH2 CH
Carbanion
C6H5

(a) Carbanion reacts with styrene monomers and propagates the reaction and forms chain prop-
agate polymer ion.
(b) In this type of polymerisation, chain termination does not occur. Hence, anionic polymer is
active till the monomer units are present in the reaction mixture; therefore, anionic polymers
are also known as active polymers.

Polymers 2.15
− −
NH2 CH2 CH + H2C CH NH2 CH2 CH CH2 CH
C6H5 C6H5 C6H5 C6H5
nH2C CH C6H5
−
H2N [ CH2 CH ]nCH2 CH
C6H5 C6H5
Anionic polymer ion
(c) When impurities are added to the reaction mixture, chain termination occurs. Therefore,
chain termination reagent is added and gets dead polymers.
Differences between addition polymers and condensation polymers

Addition polymer Condensation polymer
1. Generally, vinyl monomers participate in addition Monomers contain minimum two active functional
polymerisation. groups participate in condensation polymerisation
2. Reaction initiates with the help of an initiator. Ini- Here, there is no need of initiator and reaction occurs
tiator reacts with electrons of vinyl monomers and between monomer units.
initiates the reaction.
3. In this process, chain initiation, chain propagation Step-wise reaction occurs in between functional
and chain termination steps are involved. Reactions groups; reaction is slow. Finally, it gives polymer that
are very fast; hence polymer is formed quickly. contains high molecular weight.
4. Here HCl, H2O, NH3, etc., are not formed. Small units like HCl, H2O, NH3, etc., are formed.
5. Monomer units always react with polymer radical Monomer reacts with another monomer units or poly-
or polymer ion. mer molecule.
6. For example, polyethylene, polyvinyl chloride, For example, nylon 66, polyester, etc.,
Teflon, etc.,
2.4.3 Coordination Polymerisation

Coordination polymerisation is invented by two Italian scientists, Ziegler and Natta. They shared the
Nobel Prize for Chemistry in 1963 using the Ziegler–Natta catalyst to polymerise non-polar monomers.
Ziegler–Natta Catalyst
The mixture of titanium halides and trialkyl aluminium is known as Ziegler–Natta catalyst.
(TiCl3 + R3Al)
The reaction between titanium chloride and trialkyl aluminium forms Ziegler–Natta catalyst.
In this process, trialkyl aluminium adsorbs on the surface of titanium chloride, and forms electron
deficient bridge structure.

2.16
R
R Cl
Al Ti
R Cl
Cl
Ziegler-Natta structure
In this structure, titanium chloride acts as catalyst and trialkyl aluminium acts as the co-catalyst.
Coordination polymerisation is a form of addition polymerisation in which monomer adds to a growing
macro molecule through an organometallic active centre.
Reaction Mechanism
(i) Cossee–Arlman mechanism: The formation of C C bonds in the polymerisation of alkenes
are explained by Cossee–Arlman. In this pathway, an intermediate coordination complex con-
tains both growing polymer chain and the monomer.
The coordination polymerisation of alkene can be proceeded by monometallic or bimetallic
mechanism depending on the catalyst. Alkene or substituted alkene is polymerised by Ziegler–
Natta catalyst.
The double bond of alkene will undergo cis addition with the empty orbital of Titanium cata-
lyst to form a four-membered ring coordinate intermediate.
(ii) Monometallic polymerisation mechanism:
R
CH R1
R1 H R1 H
R R CH2
Cl Cl C Cl Cl C Cl Cl
Ti Ti Ti
Cl C Cl C Cl
Cl Cl Cl
H H H H
Four membered ring
coordinate intermediate
(iii) Bimetallic polymerisation mechanism: If the catalyst is made from aluminium and titanium
compounds, the polymerisation proceeds through bimetallic mechanism. In this mechanism, first,
a bridge structure is formed between two metal compounds. Then, the substituted alkene is coor-
dinated with titanium compound to form a six-membered ring.
R R
R′ CH R′ CH R′
δ−
R δ+ R CH2 CH −
δ+ δ CH2 CH2
Ti Al Ti Al Ti R Ti Al Ti Al
R R R Al R R
δ− δ+
H2C CH HC CH
R′ R′

Polymers 2.17
Importance
The Ziegler–Natta catalyst can control the linearity and tacticity of the polymer. Free radical poly-
merisation of ethylene produces a low density branched chain soft, rubbery polymer. However, the
Ziegler–Natta catalyst produces more linear, rigid, high density, high tensile strength, harder and
tougher isotactic polymer.
In the presence of the Ziegler–Natta catalyst, coordination polymerisation occurs and gives iso-
tactic polymer of olefin.
For example, propylene undergoes coordination polymerisation in the presence of Ziegler–Natta
catalyst at 50°C and gives isotactic polymer of polypropylene.
TiCl3 + R3Al
nCH CH2 50°C
H2C CH H2C CH H2C CH H2C CH n
CH3 CH3 CH3 CH3 CH3

Propylene Polypropylene
2.5 MOLECULAR MASS OF A POLYMER

Polymers are a mixture of different monomers with different molecular weights or masses. Hence,
three kinds of molecular masses have been identified, which are as follows:
(i) Number average molecular mass ( M n ) : This is the total mass (w) of all the molecules in a
polymer sample divided by the total number of molecules present. This can be determined by
measuring colligative properties like freezing point depression, boiling point elevation, osmotic
pressure, lowering of vapour pressure, etc.
Mn =
w
=
∑ Ni Mi
∑N ∑ Ni
Where Ni = the number of molecules of mass Mi
The number average molecular mass is a good index for tensile strength, but not for flow.
(ii) Weight average molecular mass ( M w ) : This can be determined from light scattering and ultra-
centrifugation techniques and can measure molecular size as follows:
Mw =
∑ wi M i
∑ wi
where wi = weight fraction of molecules of Mi
Mw =
∑ Ci M i = ∑ Ci M i = ∑ N i M i2
∑ Ci C ∑ Ni Mi
where Ci = weight concentration of Mi molecules
C = total weight concentration of all polymer molecules
Polydispersity index or molecular mass distribution
This is a measure of the distribution of molecular mass of a polymer. This can be calculated
using the weight average molecular weight divided by the number average molecular weight.
Mw
Polydisperity index =
MN

2.18
In a monodisperse system, M w = M N . However, the polydispersity index (PDI) value is always

greater than one, that is, the weight of the average molecular mass is always greater than the
number average molecular mass.
(iii) Viscosity average molecular mass ( M v ) : Viscosity average molecular mass can be determined
by the measuring of viscosity of that particular polymer. This can be explained by the following
formula:
1
 ∑ wi M ia   ∑ N i M ia +1  a
Mv =  = 
 ∑ wi   ∑ wi M i 
where a = constant.
When a = unity, the viscosity and weight average molecular masses are equal. M v is almost less
than M w , a polydispersive polymer is represented as
Mw > Mv > Mn .
2.6 PLASTICS
Plastics are mainly of two types:
(i) Thermoplastics: Thermoplastics are formed with straight chains; hence when heated, they sof-
ten, subsequently melt and when cooled, they become hard. Due to van der walls forces, two
different chains slid over each other and the plasticity of such polymers is reversible. Hence, the
materials can be moulded and remoulded without damage.
For example, PVC, nylon, polystyrene and polyethylene
(ii) Thermosetting plastics: Thermosetting resins do not become soft on heating, and they never
melt once they set. They are normally made from semi-fluid polymers with low molecular masses.
In this case, the polymer chains are entangled with one another and hence cannot slide over each
other. Deformation does not occur on heating, because only the primary covalent bonds are pres-
ent in the entire structure, forming a three dimensional network. They have no scrap value.
For example, Bakelite
Differences Between Thermoplastics and Thermosetting Plastics

Thermoplastics Thermosetting plastics
1. They soften on heating and harden on cooling. They do not soften on heating; on prolong heating,
however, they burn.
2. They consist of long-chain linear macromolecules. These plastics have three dimensional network struc-
ture, joined by strong covalent bonds.
3. They are formed by addition polymerisation. They are formed by condensation polymerisation.
4. By reheating to a suitable temperature, they can be They retain their shape and structure, even on heat-
softened, reshaped and thus reused. ing. Hence, they cannot be reshaped and reused.
5. They are usually soft, weak and less brittle. They are usually hard, strong and more brittle.
6. They can be reclaimed from wastes. They cannot be reclaimed from wastes.
7. They are usually soluble in some organic solvents. Due to strong bonds and cross-linking, they are
insoluble in almost all organic solvents.
8. For example, polyethylene, polyvinyl chloride, poly- For example, Bakelite, novalac resin, resol, resin, etc.
styrene, etc.

Polymers 2.19
2.7 IMPORTANT POLYMERS—COMPOSITION, PREPARATION,

PROPERTIES AND ENGINEERING USES
2.7.1 Thermoplastics
Polythene or Vinyl Resin
Polythene is the most widely used plastic. Polythene is obtained by high-pressure polymerisation of
ethylene, making use of oxygen as initiator. The reaction takes place at 1,500 atmospheric pressure
and 180°C–250°C temperature range. Ethylene polymerised into a waxy solid known as polyethylene.
H H H H
Polymerization
n C C C C
H H H H
n
Ethylene Polyethylene
By using free radical initiator, low density polythene (LDPE) is obtained, while by using ionic cata-
lysts, high density polythene is obtained.
Properties
The properties of polythene are as follows:
(i) Polythene is a rigid, waxy, white, translucent non-polar material, exhibiting considerable chemi-
cal resistance to strong acids, alkalis and salt solutions at room temperature.
(ii) It is a good insulator of electricity. However, it is swollen and permeable to most oils and organic
solvents, particularly kerosene.
(iii) Due to its highly symmetrical chain structure, polythene crystallises very easily. The degree of crys-
tallinity may vary from 40%–95%, depending on the degree of branching in the polythene chain.
(iv) Polyethylene produced by high-pressure process has a branched structure and therefore, is flex-
ible and tough. On the other hand, the low-pressure process results in a completely linear polyeth-
ylene, having higher density and better chemical resistance.
(v) Commercial polythene can be subdivided into three groups:
(a) Low-density polythene (LDPE): It is polymerised under very high pressure of 1,000–5,000
atmospheres and temperature range of 80°C–250°C in the presence of O2 as the initiator. It
has a density of 0.91–0.925 g/cm3 and M.P. 110°C –125°C.
(b) Medium-density polyethylene (MDPE): It is polymerised under medium pressure, having
density 0.925–0.940 g/cm3 and M.P. 130°C–140°C.
(c) High-density polyethylene (HDPE): It is polymerised under atmospheric pressure (6–7
atmospheres) and temperature at 60°C in the presence of Ziegler–Natta catalyst [TiCl3 +
Al(C2H5)3]. The HDPE, which is completely linear, has better chemical resistance and
higher softening point but relatively brittle.
Comparative properties of HDPE and LDPE

Type Density (g-cm−3) Crystallinity Softening point (k) Tensile strength (atm)
LDPE 0.910–0.925 55% 360 85–136
HDPE 0.941–0.965 80% 400 204–313

2.20
Uses
The uses of LDPE are as follows:
(i) LDPE is used in making films and sheets. Pipes made of LDPE are used for agricultural irriga-
tion and domestic water line connections. They are also used for making tubes, coated wires
and cable wires.
(ii) HDPE is used in the manufacture of toys, insulator parts, bottle caps, flexible bottles, kitchen and
domestic articles.
Polyvinyl Chloride (PVC)
It is obtained by heating a water emulsion of vinyl chloride in the presence of a small amount of ben-
zoyl peroxide or hydrogen peroxide in an autoclave under pressure.
H Cl H Cl
Polymerization
n C C C C
H H H H
n
Vinyl chloride PVC
Vinyl chloride so needed is generally prepared by treating acetylene at 1–1.5 atmospheres with hydrogen
chloride at 60–80°C, in the presence of metal chloride as catalyst.
CH CH + HCl CH2 CHCl
Acetylene Vinyl chloride
Properties
PVC is colourless, odourless, non-inflammable and chemically inert powder, resistant to light, atmos-
pheric oxygen, inorganic acids and alkalis but soluble in hot chlorinated hydrocarbons such as ethyl
chloride. Pure resin possesses high softening point and a greater stiffness and rigidity, but is brittle.
Uses
The uses of PVC are as follows:
(i) Rigid PVC or unplasticised PVC has superior chemical resistance and high rigidity but is brittle.
It is used for making sheets, which are employed for tank linings, light fittings, safety helmets,
refrigerator components, tyres, cycles and motor-cycle mudguards. It is also extruded in strip
and tube form for use in place of nonferrous metals.
(ii) Plasticised PVC is used for making continuous sheets, rain coats, table cloths and curtains, elec-
tric cables, toys, radio components, conveyor belts, etc.
Polystyrene (PS)
It is prepared by the polymerisation of styrene in the presence of benzoyl peroxide catalyst.
H H H H
Polymerization
n C C C C
H H
n
Styrene Polystyrene

Polymers 2.21
Properties
Polystyrene is a transparent, light-stable and moisture-resistant material. It is highly electric insulating
and highly resistant to acids, and is a good chemical resistant. However, it has less softening and is
brittle. It has the unique property of transmitting light through curved sections.
Uses
It is used in moulding of articles such as toys, combs, buttons, buckles, radio and television parts,
refrigerator parts, battery cases, high-frequency electric insulators, lenses, indoor lighting panels, food
containers, food packaging, umbrella handles and so on.
Teflon [Polytetrafluoroethylene (PTFE or FLUON)]

The presence of benzoyl peroxide catalyst and high pressure polymerisation of tetrafluoroethylene
gives Teflon.
F F F F
Polymerization
n C C C C
F F F F
n
Tetrafluoroethylene Teflon
Properties
Teflon has a twisted, zigzag structure with fluorine atoms, packed tightly in a spiral around the carbon-
carbon skeleton. Due to the presence of highly electronegative fluorine atoms, there are very strong
attractive forces between different chains. These strong attractive forces give the material extreme
toughness, high softening point, exceptionally high chemical resistance towards all chemicals, high
density, waxy touch, very low coefficient of friction and extremely good electrical and mechanical
properties. It can be machined, punched and drilled. The material cannot be dissolved and cannot exist
in a true molten state. Around 350°C, it sinters to form a very viscous, opaque mass, which can be
moulded by applying high pressure.
Uses
The uses of Teflon are as follows:
(i) It is used as an insulating material (motors, transformers, cables, wires, etc.) and for making
gaskets, pickings, pump parts, tank lining, chemical-carrying pipes, tubings and tanks, etc.
(ii) It is used for coating and impregnating glass fibres, asbestos fibres, cloths, in non-lubricating
bearings, non-sticking stop-clocks, coating of frying pans, etc.
Nylon
These are polyamides. The word nylon is now accepted as a generic term for synthetic polyamides,
which are characterised by a repeating acids linkage ( NHCO ). Nylon is formed with dicarboxylic
acids and diamide under condensation process. It has been named on the basis of number of carbon
atoms present in that two monomer units.

2.22
For example, nylon 6,6, nylon 6,10, nylon 6,11, etc.

Nylon 6,6 is formed with the condensation reaction of hexamethylenediamine and adipic acid.
H H H HO H OH H H
Condensation
nN C N + C C C Polymerization
N C N C C C + 2nH2O
−H2O
H H H O H O H H H O H O
6 4 6 4 n
Hexamethylene Adipic acid Nylon 6,6
diamine
Properties
They are translucent, whitish, horny and high melting polymers. They possess stability up to high
temperature and good abrasion resistance. They are insoluble in common organic solvents and soluble
in phenol and formic acid.
Properties of Nylon Fibres

The properties of nylon fibres are as follows:
(i) They are light, horny and high melting.
(ii) They are insoluble in common solvents.
(iii) They have good strength.
(iv) They absorb little moisture and are thus “drip-dry” in nature.
(v) They are very flexible and retain original shape easily.
(vi) They have resistances to abrasion.
(vii) On blending with wool, the strength and abrasion resistance of the latter increase.
Uses
(i) Nylon 6,6 is primarily used for fibres and tyre cord, which find use in making rocks, ladies
hoses, undergarments, dresses, carpets, ropes, etc.
(ii) Nylon 6,6 and nylon 6,11 are mainly used for moulding purposes for gears, bearings, electrical
mountings, etc. Nylon bearings and gears work quietly without any lubrication.
(iii) They are also used for making filaments for ropes, bristles for tooth brushes, films, etc.
2.7.2 Thermosetting Plastics

Phenol-Formaldehyde Resins or Phenoplasts
These are condensation polymerisation products of phenolic derivatives with aldehydes, prepared by
condensing phenol with formaldehyde in presence of acidic or alkaline catalyst. Depending upon cata-
lyst and reactants mainly three kinds of resins are formed, they are classified as follows:
(i) Novalac resin: The presence of acid, phenol and formaldehyde condense to form novalac resin.
At first, formaldehyde takes proton from acid and forms the carbonium ion.
H
H C + H+ H2C+ OH
O
Formaldehyde Carbonium ion

Polymers 2.23
Phenol react with carbonium ion to form ortho- and para-methylol phenol.
OH OH OH
CH2OH
+
+ H2C OH +
CH2OH
Phenol O-methylol P-methylol
phenol phenol
Ortho-methylol phenol condenses to form novalac resin.

OH OH
H CH2 OH H CH2OH
+
n
OH OH OH OH
CH2 CH2 CH2 CH2
Novalac resin
(ii) Resol resin: Phenol and formaldehyde are refluxed with ammonia at 100°C gives resol resin.
In presence of ammonia, methylol phenol has greater reactivity with formaldehyde than phenol,
hence it gives di- and tri-methylol products.
OH OH OH
HOH2C HOH2C
CH2OH CH2OH CH2OH
HCHO HCHO
CH2OH
Mono-methylol Di-methylol Tri-methylol
phenol phenol phenol
The polymethylol phenol condenses and forms resol resin.

OH OH OH OH
HO H2C CH2 CH2 CH2 CH2OH
n
CH2OH CH2OH CH2OH CH2OH
Resol resin
(iii) Bakelite: Bakelite was first prepared by Baekeland. In the presence of hexamethylenetetramine,
phenol reacts with formaldehyde and forms cross linked resin, that is, Bakelite. It is a hard and
insoluble solid.

2.24
OH OH
H H H C H H H
(CH2)6N4
O H2O
H H
OH OH OH
CH2 CH2
CH2
CH2 CH2 CH2
CH2 CH2
OH OH OH
Bakelite
Properties
Novalac resin is soluble and fusible solid. Resol resin is a hard and brittle solid. Bakelite is a rigid,
hard, infusible, water resistant, and insoluble solid. It resist to non-oxidising acids, salts and organic
solvents, but are attacked by alkali due to presence of free hydroxyl groups. All phenol formaldehyde
resins possess excellent electrical insulating character.
Uses
The uses of resol resin are as follows:
(i) Making electric insulator parts like switches, plugs, switch-boards, heater-handles, etc.
(ii) Preparing moulded articles like telephone parts, cabinets for radio and television.
(iii) Impregnating fabrics, wood and paper.
(iv) As adhesives for grinding wheels.
(v) Making bearings used in propeller shafts for paper industry and rolling mills.
(vi) As hydrogen-exchanger resins in water softening.
Polyurethanes
Diisocyanate and diol give polyurethanes.
For example, a reaction between 1,4-butane diol and 1,6-hexane diisocyanate gives “Perlon - U”,
a crystalline polymer.
Properties
The properties of polyurethanes are as follows:
(i) Polyurethanes are less stable than nylons.
(ii) These have excellent resistance to abrasion and solvents.

Polymers 2.25
Uses
These are used as coatings, films, foams, adhesives and elastomers.
O H O H
nC N C N C + n HO C OH
4
H 6 H
1,6-Hexamethylene 1,4-butane
diisocyanate diol
O H H O H
n C N C N C O C O
H 6 H 4 n
(Perlon-u)
2.8 RUBBER (ELASTOMERS)

Rubbers are high polymers, which have elastic properties. Thus, the rubber band can be stretched to
four to 10 times its original length, and as soon as the stretching force is released, it returns to its origi-
nal length. The elastic deformation in an elastomer arises from the fact that in the unstressed condition,
an elastomer molecule is not straight chained, but in the form of a coil, it can be stretched like a spring
consequently. The unstretched rubber is amorphous.
2.8.1 Processing of Natural Rubber

Isoprene is the basic molecule present in natural rubber. Dispersive form of isoprene units are known
as latex. In the processing of natural rubber isoprene molecules polymerise and form long, coiled
chains of cis-polyisoprene.
HH HH
H2C CH2 C C
n C C C C
H3C H H C H
Isoprene (2-methyl 1,3-butadiene) H H n
Cis-polyisoprene
(Natural rubber)
H H H H
H C H H H C H H H C H H H C H H
H H H H H H H H
C C C C C C C C
C C C C C C C C
H H H H
H H H H
Structure of natural rubber

2.26
By making small incisions on the bark of rubber trees, like having a brasiliensis and guayule, the rub-
ber latex can be collected into small vessels, as it oozes out. It contains 25%–45% of rubber in the form
of milky colloidal emulsion, the remainder of which is made mainly of water and small amounts of
protein and resinous material with time, the flow of latex from the incision made start decreases. Thus,
at regular intervals, tapping is necessary throughout the life of the tree.
Latex is diluted to make 15%–20% of rubber and is filtered to eliminate any dirt present in it. It
is then coagulated in a tank, fitted with irregular partitions by adding about one kg of acetic acid or
formic acid per 200 kg of rubber, to a soft white mass. After washing and drying, the coagulated
residue is treated as follows:
(i) Crepe rubber: It is prepared by adding a little sodium bisulphite to bleach the rubber and is
then passed through a creping machine so that coagulum is rolled out into sheets of about 1 mm
thickness. The sheet possesses an even rough surface resembling crepe paper. The sheet is then
air-dried at 50°C.
(ii) Smoked rubber: It is made by eliminating the bleaching with sodium sulphite and rolling the
coagulum into thicker sheets, having ribbed pattern on its surface. The ribbed surface pattern on
the sheet prevents them from adhering together on stacking. It also facilitates consequent drying
as it exposes greater surface area of the sheet. The sheets are then dried in the smoke obtained
from burning wood or coconut shells at about 50°C. The rubber sheet thus obtained is translucent
and amber in colour.
2.8.2 Gutta–Percha
It is a trans-form of natural rubber. (In natural rubber, isoprene units are linked with cis-form). It is
obtained from the matured leaves of Dichopsis gutta and Palaquium gutta trees, grown mostly in
Malaya and Sumatra. Gutta–percha can be recovered by solvent extraction process, when insoluble
resins and gums are separated. Alternatively, the matured leaves are grounded carefully and is treated
with water at about 70°C for half an hour and then poured into cold water, when Gutta–percha floats
on water surface it is removed.
−H2C H H3C CH2 CH2 H H3C CH2

C C C C C C C
H3C CH2 CH2 H H3C CH2 CH2 H
Rod structure (Gutta percha)
Properties
The properties of gutta percha are as follows:
(i) At room temperature, gutta percha is horny and tough, but softens and becomes tacky at about
100°C.
(ii) It is soluble in aliphatic hydrocarbons, but insoluble in aromatic and chlorinated hydrocarbons.
Uses
It is used in the manufacturing of golf ball covers, submarine cables, adhesives and tissues for surgical
purposes.

Polymers 2.27
2.8.3 Vulcanisation of Rubber

Drawbacks of Raw (Natural) Rubber
The drawbacks of raw (natural) rubber are as follows:
(i) It is plastic in nature. Crude rubber becomes soft and sticky in hot summer, while in cold
weather, it becomes hard and brittle. Its usage is limited to a particular temperature range of
about 10°C–60°C.
(ii) It is weak, due to low tensile strength (200 kg/cm2).
(iii) It has large water absorption capacity.
(iv) It is non-resistant to non-polar solvents such as vegetable and mineral oils, gasoline, benzene and
carbon tetra chloride.
(v) It is attacked by oxidising agents (HNO3, H2SO4, etc.). It perishes due to the oxidisation in air.
(vi) In organic solvents, it undergoes swelling and gradual disintegration.
(vii) It possesses tackiness, which means that under pressure, two fresh raw rubber surfaces coalesce
to form a single piece.
(viii) It possesses very less durability.
(ix) When stretched to a great extent, some molecular chains undergo sliding or slipping over each
other, hence it suffers from permanent deformation.
To improve the properties of rubber, it is compounded with some chemicals such as sulphur, hydrogen
sulphide, benzoyl chloride and the rubber mix is prepared for vulcanisation. The addition of com-
pounding agents is facilitated by the process of mastication. Mastication of rubber means that it is
subjected to severe mechanical working. Oxidative degradation accompanied by a marked decrease in
the molecular weight of the rubber occurs and converts rubber into a soft and gummy mass.
Vulcanisation
Heating of raw rubber with sulphur at around 100°C –140°C is known as vulcanisation. Sulphur com-
bines chemically at the double bonds of rubber chains and forms cross links. With these crosslinks, the
rubber becomes stiff and the percentage of sulphur determines the stiffness of rubber.
For example, a rubber tyre contains 3–5% of sulphur.
CH3 CH3
CH2 C CH CH2 CH2 C CH CH2
+
CH3 CH3
Raw rubber
Vulcanization
addition of sulphur
CH3 CH3
S S S S Sulphur Cross-links

CH3 CH3
Vulcanization of raw rubber

2.28
Advantages of Vulcanisation
The advantages of vulcanisation are as follows:
(i) The tensile strength of vulcanised rubber is very good and has extensibility about 10 times the
tensile strength of raw rubber; when a tensile force is applied, it can bear a load of 2000 kg/cm 2
before it breaks.
(ii) After the removal of deforming force, the articles made from vulcanised rubber regain their origi-
nal shape, so that it has excellent resilience.
(iii) It has broader useful temperature range (−40°C–100°C) compared to raw rubber’s temperature
range (10°C–60°C).
(iv) It has much high resistance to moisture, oxidation and abrasion.
(v) It has much higher resistance to wear and tear as compared to raw rubber.
(vi) It is a better electrical insulator, although it tends to absorb small amounts of water.
or example, ebonite is a better insulator.
(vii) It has resistance to organic solvents like benzene, carbon tetrachloride, petrol, etc., but it swells
in them.
(viii) It is very easy to manipulate vulcanised rubber to produce the desired shapes.
The superior properties of vulcanised rubber compared to raw rubber are summarised in Table 2.1.
Table 2.1 Raw rubber vs. vulcanised rubber

Property Raw rubber Vulcanised rubber
2
Tensile strength 200 kg/cm 2,000 kg/cm2
Resilience Good Very good
Resistance to moisture oxidation and abrasion Poor Good
Useful temperature range 10°C –60°C −40°C –100°C
Resistance to organic solvents Poor Large but limited
Tackiness Marked Slight
Elasticity Very high Low
Per cent elongation at break 1200 800
Manipulability to desired shape Not easy Easy
2.8.4 Compounding of Rubber

Compounding is “mixing of the raw rubber with other chemicals so as to impart the product-specific
properties suitable for particular job”. The following substances are generally mixed with raw rubber:
(i) Antioxidant: Natural rubber has a tendency to “perish” due to oxidation, retarding the deteriorat-
ing of rubber by preventing its oxidation by light and air; about 1% of the antioxidants are used.
These are phenolic substances, phosphites and complex organic amines like phenyl naphthylamine.
(ii) Colouring agents: Colouring agents impart the desired colour to the rubber product.
For example, for white products, titanium dioxide (TiO2) is the usual pigment. For colour prod-
ucts, the following pigments are used:
Colour Pigment
Blue Ultramarine
Green Chromium trioxide
Red Ferric oxide
Crimson Antimony sulfide
Yellow Led chromate

Polymers 2.29
(iii) Vulcanising agents: The main vulcanising agent is sulphur. Among these, sulphur monochloride,
hydrogen sulphide and benzoyl chloride are also used as vulcanisers. Depending on the nature of
the product required, the percentage of S added varies between 0.15% and 32%. The process of
vulcanisation brings about excellent changes in the properties of crude rubber.
(iv) Accelerators: They are positive catalysts for vulcanisation process as they drastically shorten the
time required for vulcanisation. Generally, benzothiazole, 2-mercaptol, zinc alkyl xanthate and
thiocarbamates are used in 0.5%–1% instances as the most usual accelerators.
(v) Reinforcing agents: These agents give rigidity, strength and toughness to the rubber and are
present up to 35% of the rubber compound. Commonly used reinforcers are carbon black, zinc
oxide, CaCO3, MgCO3, etc.
For example, addition of carbon black in the elastomer is used in the manufacture of automobile
tyres.
(vi) Plasticisers and softness: They impart greater tenacity and adhesion to the raw rubber. The
important plasticisers are stearic acid, waxes, vegetable oils, rosin, etc.
(vii) Inert fillers: They lower the cost of the product and alter the physical properties of the mix for
simplifying the subsequent manufacturing operations.
2.8.5 Synthetic Rubbers or Artificial Rubber

The landmark discovery of rubber is the greatest achievement in polymer industry and with the efforts
of scientists and technologists the first useful synthetic rubber Buna-S was prepared.
Advantages of Synthetic Rubbers
Due to better performance properties of synthetic elastomers, natural rubber failed to give stiff
competition.
(i) They are produced from petrochemical raw materials in abundant amounts.
(ii) They are economically beneficial.
(iii) They are not only replacements but are superior to natural rubber in certain cases.
(iv) They are tailor-made elastomers with diverse applications.
(v) They have high abrasion resistance and high tensile strength.
(vi) Certain elastomers like silicones have low temperature (−80°C), flexibility and high temperature
stability.
(vii) Silicones are valuable in surgical prosthetic devices.
2.8.6 Important Artificial Rubbers

Styrene Butadiene Rubber (GR-S or Buna-S)
It is a copolymer of styrene (25% by weight) and butadiene (75% of weight). The monomers are emulsi-
fied in water using soap or detergent. The reaction is initiated by peroxide initiators. Polymerisation is
carried out at 5°C, and therefore, the product is known as cold SBR.
Polymerization
nCH2 CH CH CH2 + nCH2 CH in presence of peroxide
C6H5
Butadiene (75%) Styrene (25%)
( CH2 CH CH CH2 CH2 CH )n
C6H5
Buna-S

2.30
Properties
Styrene rubber is slightly inferior to natural rubber in its physical properties. It possesses high abra-
sion resistance, high load-bearing capacity and resilience. However, it gets readily oxidised, especially
in the presence of traces of ozone present in the atmosphere. It swells in oils and solvents. It can be
vulcanised in the same way as natural rubber, but it requires less sulphur and more accelerators for
vulcanisation.
Uses
The uses of styrene rubber are as follows:
(i) It is mainly used for the manufacture of motor tyres, (passenger car tyres, motor cycle tyres and
scooter and cycle tyres.) but not used for truck tyres.
(ii) It is also used for floor tiles, shoe soles, gaskets, footwear, conveyor belts, wire and cable insula-
tions, carpet backing, adhesives, tank linings, etc.
Buna-N, Nitrile Rubber or GR–A

It is a copolymer of a 1,3-butadiene and acrylonitrile. They are also prepared in emulsion systems.
They are noted for their oil resistance but not suitable for tyres.
Polymerization
n [ H2C CH CH CH2 ] + n (CH2 CH)
CN
1,3-Butadiene Acrylonitrile
( CH2 CH CH CH2 )n ( CH2 CH )n
CN
Nitrilerubber (Buna-N)
Properties
It possesses excellent resistance to heat, sunlight, oils, acids and salts, but it is less resistant to alkalis
than natural rubber because of the presence of cyano groups. As the proportion of acrylonitrile is
increased, the resilience to acids, salts, oils, solvents, etc., increases, but the low temperature resil-
ience suffers. Vulcanised rubber is more resistant to heat and ageing than natural rubbers and may be
exposed to high temperature.
Uses
The uses are as follows:
(i) They are extensively used for fuel tanks, gasoline hoses, creamery equipment, conveyor belts
and high-altitude aircraft components.
(ii) They are also used as adhesives, latex, gaskets, printing rollers, leather and textile.
Poly Sulphide Rubber, Thiokol or GR–P

Thiokols are those elastomers in which sulphur forms a part of the polymer chain. It is a copolymer of
sodium poly sulphide (Na2S4) and ethylene dichloride.

Polymers 2.31
S S S S
heated
Cl CH2 CH2 Cl + Na S S Na −NaCl
CH2 CH2 S S n
Ethylene dichloride Sodium polysulphide Thiokol rubber
Properties
Thiokols have outstanding resistance to swelling and disintegration by organic solvents, mineral oils,
fuels, solvents, oxygen, ozone, gasoline and sunlight. Thiokol films have low permeability to gases.
They have the following limitations:
(i) It tends to flow or lose shaped under continued pressure. As it cannot be vulcanised, it does not
form hard rubber.
(ii) Its tensile strength is lesser than that of natural rubber.
(iii) It cannot be vulcanised.
Uses
The uses of Thiokols are as follows:
(i) Thiokols are used for barrage balloons, life rafts and jackets, which are inflated by CO2.
(ii) It is also used for lining hoses for conveying gasoline and oil, in paints, for gaskets, diaphragm
and seats in contact with solvents, and for printing rolls.
Polyurethanes (Isocyanate Rubber)

These polymers are formed by the reaction between diisocyanates and polyalcohols.
O O
Polymerization
nHO CH2 CH2 OH + nC N CH2 CH2 N C
Ethylene glycol Ethylene diisocyanate
O H H O
n O CH2 CH2 O C N CH2 CH2 N C n

Polyurethane rubber (or) isocyanate rubber
Properties
Polyurethane elastomers have outstanding abrasion resistance and hardness combined with good elas-
ticity and resistance to oils, greases, chemical, weathering and solvents.
Uses
They are used in applications where extreme abrasion resistance is required such as in heel lifts, sur-
face coatings, manufacture of foams, spandex fibres and small industrial wheels.
Silicone Rubbers
Silicones are organic silicone polymers. They have alternate Si-O-bonds.
Preparation: For preparation of silicones, dialkyl-substituted silanes are used as raw materials.

2.32
They undergo hydrolysis and condensation polymerisation to form silicone polymers.

Silicones are of mainly two types:
(i) Straight-chain polymers: Dialkyl-substituted silanes are subjected to hydrolysis and undergo
condensation polymerisation to form straight-chain thermoplastic silicones.
R
hydrolysis condensation
R2SiCl2 R2Si(OH)2 Si O Si O Si O
Dialkyl Dialkyl
dichloro silanol R n
silane
Straight chain thermo
plastic silicone
polymer
(ii) Cross-linked polymers: Mono alkyl-substituted silanes are subjected to hydrolysis and proceeds
condensation reaction gives cross-linked polymers.
R R
hydrolysis
Cl Si Cl HO Si OH
Cl OH
Mono alkyl silanol
R O O
condensation
nHO Si OH R Si O Si R
OH O O
Mono alkyl silanol
R Si O Si R
O O
Cross linked polymer

Alkyl chlorosilanes are prepared by this process.
R Mg X + SiCl4 RSiCl3 + MgXCl
Mono alkyl
trichloro silane
2R Mg X + SiCl4 R2SiCl2 + 2MgXCl

Dialkyl dichloro
silane
Properties
The properties of silicones are as follows:
(i) Silicones have resistance to heat, cold, oxidation, etc.
(ii) They obtain as liquids, resins and elastomers.
(iii) Silicon liquids are having repulsion with water. They have also resistance with chemicals.
(iv) Silicone rubber may form reaction between silicone resins, silica and alumina.

Polymers 2.33
Uses
The uses of silicones are as follows:
(i) Silicones are used as anti-forms in the preparation of food stuff.
(ii) They are used as elastics, insulators, gascatoles and ceiling joints, and also used in medicine.
(iii) They are used as surface-coating agents.
(iv) Silicones are used for lamination.
Reclaimed Rubber
Reclaimed rubber is rubber obtained from waste rubber articles such as worn-out tyres, tables, gaskets,
hoses, foot wear and so on. The process of reclamation of rubber is carried out as follows:
The waste is cut to small pieces and powdered by using a cracker, which exerts powerful grinding
and tearing action. The ferrous impurities, if any are removed by the electromagnetic separator. The
purified waste powdered rubber is then digested with caustic soda solution at about 200°C under pres-
sure for 8–15 hours in a “steam-jacketed autoclave”. By this process, the fibres are hydrolysed. After
the removal of fibres, reclaimed agents (like petroleum and coal tar based oils) and softeners are added
and sulphur gets removed as sodium sulphide and rubber becomes devulcanised. The rubber is then
thoroughly washed with water sprays and dried in hot air driers. Finally, the reclaimed rubber is mixed
with small proportion of reinforcing agents (like clay, carbon black, etc.).
Properties
The reclaimed rubber is of less tensile strength lower in elasticity and possesses lesser wear-resistance
than natural rubber. However, it is much cheaper, uniform in composition and has better ageing proper-
ties. Moreover, it is quite easy for fabrication.
Uses
For manufacturing tyres, tubes, automobile floor mats, belts, hoses, battery containers, mountings,
shoes and heals, etc.
2.9 REINFORCED OR FILLED PLASTICS

Polymers, generally of low strengths and moduli of elasticity, are needed for structural purposes. For
these reasons, polymers are combined with fillers (which are primary silicates) to get better products.
The fillers are solid additives, which modify the physical properties, particularly, the mechanical prop-
erties of basic polymeric materials. For example, they improve: (i) thermal stability, (ii) mechanical
strength, (iii) insulating characteristics, (iv) water resistance, (v) external appearance, (vi) rigidity, (vii)
finish, (viii) hardness, (ix) opacity and (x) workability, besides reducing (xi) cost and (xii) shrinkage
on setting and brittleness.
Usually, specific fillers are added to a polymeric compound to impart special characters to the
final products. Some examples are as follows:
(i) To improve hardness, fillers such as carborundum, quartz and mica are added.
(ii) To make the plastic impervious to x-ray, barium salts are fillers.
(iii) To provide heat and corrosion resistances, asbestos is added.

2.34
The combination of polymeric substance with solid fillers, is called filled or reinforced plastics. The
filler acts as a reinforcing material while the polymer acts as binder, which links the filler particles. The
polymer serves as stress transforming agent from filler to filler particles.
Most commonly used fillers are as follows:
(i) wood flour, (ii) saw dust, (iii) ground cork, (iv) asbestos, (v) marble flour, (vi) china clay, (vii)
paper pulp, (viii) corn husk, (ix) mica, (x) pumice powder, (xi) carbon, (xii) cotton fibres, (xiii) boron
fibres, (xiv) silicon carbide, (xv) silicon nitride, (xvi) graphite, (xvii) alumina, (xviii) glass fibres, (xix)
Kevlar fibres, (xx) cotton fibres, (xxi) metallic oxides such as ZnO, PbO and so on, and (xxii) metallic
powder such as Al, Cu, Pb and so on.
2.9.1 Composition
Fillers are usually employed in a sizable weight percentage. The percentage of filler can be up to 50%
of the total moulding mix.
2.9.2 Nature of Polymers Used

Polymers used are thermoplastics, thermosetting polymers as well as rubber (elastomers) such as poly-
ethylene, polypropylene, nylon-6, PET, polystyrene, melamine, silicone, natural and synthetic rubbers,
epoxy among others.
Some examples of filled plastics are as follows:
(i) Carbon black on addition to natural rubber brings about 40% increase in tensile strength and
such filled plastic is used in automobile tyres.
(ii) The addition of china clay to PVC enhances the electrical insulation characteristics of PVC.
Therefore, this filled plastic is used for electrical insulation purposes.
(iii) PVC and calcium carbonate combination is used for general purposes such as tubings, seat cov-
ers, wires and cable insulations.
(iv) Fibrous fillers such as wood flour, short length of synthetic fibres, cotton flock, macerated paper
and cloth etc., are used in thermosetting polymers, phenol-formaldehyde, melamine, formalde-
hyde, melamine urea, etc., to get filled plastics of higher impact strength.
(v) Asbestos-filled plastics are employed in electrical appliances.
(vi) Fibre-reinforced plastics possess good thermal and shock resistance, good dimensional stability,
good process ability and moulded articles can be repaired easily.
2.9.3 Application of Filled Plastics (Reinforced Plastics)

Filled or reinforced plastics find numerous applications. Some examples are as follows:
(i) In automobiles for making door handles battery cases, engine cooling fans, etc. (using base
polymers polyethylene, polypropylene and nylon-66).
(ii) In defence for making nose cones, pistol grips and riffle bullets (using base polymers polystyrene
and nylon-66).
(iii) In textiles for making shuttle (nylon-66 as base polymer).
(iv) In electrical/electronic industry for making exhaust fan, computer tape, insulators, wire and cable
insulation, switch gear parts, spools, etc., (using polypropylene, PET, nylon and SAN as base
polymers.)

Polymers 2.35
(v) In consumer goods like door handles, and window, hinge, chair shells, camera housing etc. (using
polypropylene and ABS as base polymers).
(vi) Miscellaneous like water meter housings, chemical pump housings, tubings, seat coverings etc.,
(using nylon-66, PVC and polypropylene as polymers).
2.10 BIOPOLYMERS
Biopolymers are macromolecules that occur in nature from plants, trees, bacteria, algae or other
sources that are long chains of molecules linked together through a chemical bond. They are often
degradable through microbial processes such as composting. For example, cellulose, proteins, starch,
collagen, casein, polyesters, etc.
“Sustainable biopolymers” are sourced from sustainably grown and harvested cropland or forests,
manufactured without hazardous inputs and impacts, healthy and safe for the environment during use
and designed to be reutilised at the end of their intended use through recycling or composting. The
potential for using these materials to make synthetic polymers was identified in the early 1900s, but
they have only recently emerged as a viable material for large-scale commercial use.
2.10.1 Major Feed Stocks for Biopolymers

While biopolymers can be made from an almost unlimited range of bio-based materials, most of the
currently marketed biopolymers are made from starch. Corn is currently the primary feedstock, with
potatoes and other starch crops also used in lower amounts.
2.10.2 Preparation Methods

At present, either renewable or synthetic starting materials may be used to produce biodegradable
polymers. Two main strategies may be followed in synthesising a polymer. One strategy is to build
up the polymer structure from a monomer by a process of chemical polymerisation. The alternative is
to take a naturally occurring polymer and chemically modifying it to give it the desired properties. A
disadvantage of chemical modification is that the biodegradability of the polymer may be adversely
affected. Therefore, it is often necessary to seek a compromise between the desired material properties
and biodegradability.
2.10.3 Important Biodegradable Polymers

Biodegradable polymers can be easily degradable by biological activities of decomposers. The natural
raw materials are abundant, renewable and biodegradable, making them attractive feedstock for a new
generation of environmentally friendly bioplastics. Even if only a small percentage of the biopolymers
already being produced were used in the production of plastics, it would significantly decrease our
dependence on non-renewable resources.
(i) Lactic acid is now commercially produced on a large scale through the fermentation of sugar
feedstock obtained from sugarcane, from the conversion of starch from corn, potato peels or
other starch source. It can be polymerised to produce poly (lactic acid).
Poly (lactic acid) has become a significant commercial polymer, useful for recyclable and biode-
gradable packaging, such as bottles, yogurt cups and candy wrappers. It has also been used for food

2.36
service ware, lawn and food waste bags, coatings for paper and cardboard and fibres for clothing,
carpets, sheets and towels and wall coverings. In biomedical applications, it is used for prosthetic
materials, drug encapsulation, biodegradable medical devices and materials for drug delivery.
(ii) Triglycerides is another promising raw material for producing plastics from a large part of the
storage lipids in animal and plant cells such as soybean, flax and rape seed. Triglycerides have
recently become the basis for a new family of composites. With glass fibre reinforcement, they
can be made into long-lasting durable materials with applications in the manufacture of agricul-
tural equipment, the automotive industry, construction and other areas. Fibres other than glass can
also be used in the process, such as fibres from jute, hemp, flax, wood and even straw or hay. If
straw could replace wood in composites now used in the construction industry, it would provide
a new use for an abundant, rapidly renewable agricultural commodity and at the same time con-
serve less rapidly renewable wood fibre.
(iii) Starch is found in corn (maize), potatoes, wheat, tapioca (cassava) and some other plants. Starch-
based bioplastics are important not only because starch is the least expensive biopolymer but
because it can be processed by all of the methods used for synthetic polymers, like film extrusion
and injection moulding. Utensils, plates, cups and other products have been made with starch-
based plastics. The annual world production of starch is well over £70 billion, with much of it
being used for non-food purposes, such as making paper, cardboard, textile sizing and adhesives.
Starch-protein compositions have the interesting characteristic of meeting nutritional require-
ments for farm animals. Hog feed, for example, is recommended to contain 13%–24% protein,
and complemented with starch. If starch-protein plastics were commercialised, used food con-
tainers and service ware collected from fast food restaurants could be pasteurised and turned
into animal feed.
(iv) The interest in soybeans has been revived, recalling Ford’s early efforts. In research laboratories,
it has been shown that soy protein, with and without cellulose extenders, can be processed with
modern extrusion and injection moulding methods and also used for making adhesives and coat-
ings for paper and cardboard.
(v) Many water-soluble biopolymers such as starch, gelatine, soy protein and casein form flexible
films when properly plasticised. Although such films are regarded mainly as food coatings, it is
recognised that they have potential use as non-supported stand-alone sheeting for food packaging
and other purposes.
(vi) Casein, commercially produced mainly from cow’s skimmed milk, is used in adhesives, binders,
protective coatings and other products.
(vii) Polyesters are now produced from natural resources such as starch and sugars, through large-scale
fermentation processes, and are used to manufacture water-resistant bottles, utensils and other
products. Polyesters are produced by bacteria, and can be made commercially on a large scale
through fermentation processes. They are now being used in biomedical applications.
(viii) Collagen is the most abundant protein found in mammals. Gelatine is denatured collagen, and
is used in sausage casings, capsules for drugs and vitamin preparations and other miscellaneous
industrial applications including photography.
2.10.4 Importance of Biopolymers in Sustainable Development

There are enormous societal benefits that result from a shift to bio-based plastics. Bio-based materi-
als have the potential to produce fewer greenhouse gases, require less energy and produce fewer toxic
pollutants over their lifecycle than products made from fossil fuels. They may also be recyclable or

Polymers 2.37
composted (depending on the biomaterial and how it is produced), reducing waste streams to already
crowded landfills or to incinerators.
As the cost of petroleum increases, making products with bio-based materials is increasingly
attractive. Increased demand for agricultural and forest-based feedstock also offers new resource-
based economic development opportunities for farmers, struggling rural communities and manufac-
turing sectors.
However, many of these advantages are not inherent in the material. They depend on ensuring that
bio-based products meet minimal standards for the safe production, use and end-of-life disposition.
Making the transition from a petroleum-based to a bio-based economy also gives us an opportu-
nity to ensure that the impact of product standards on the environment, health and society are included.
The widespread use of these new plastics will depend on developing technologies that can be suc-
cessful in the marketplace. This, in turn, will partly depend on how strongly society is committed to
the concepts of resource conservation, environmental preservation and sustainable technologies. There
are growing signs that people indeed want to live in greater harmony with nature and leave a healthy
planet to the future generation. If so, bioplastics will find a place in the current age of plastics.
2.11 CONDUCTING POLYMERS

Due to non-availability of free electrons, most normal polymers are insulators. Scientists have taken
this property as an advantage, and with their curiosity and challenging nature, they prepared conduct-
ing polymers as promising materials.
“Conducting polymer is an organic polymer having highly delocalised π-electron system and elec-
trical conductance”.
Conducting polymers are broadly classified into two categories as intrinsically conducting poly-
mers and extrinsically conducting polymers.
2.11.1 Intrinsically Conducting Polymer (ICP) or Conjugated π-Electrons

Conducting Polymer
Polymers which contain conjugated π-electron backbone or delocalised electron pairs act as intrinsic
conducting polymers.
For example,
(i) Polyacetylene polymers like Poly-p-phenylene, polyquinolone, etc.
(ii) Condensed aromatic polymers like polyaniline, polyphenanthrylene, etc.
(iii) Heteroaromatic and conjugated aliphatic polymers like polypyrrole, polyazomethine, etc.
If the conductivity of intrinsically conducting polymers is less, they are doped with positive or negative
charges and this process is known as doping.
It is mainly oxidative or p-doping, reductive or n-doping and protonic acid doping.
(i) Oxidative or p-doping: Treating of intrinsically conducting polymers with Lewis acid like I2,
Br2, FeCl3, CCl4, HBF4, etc., is known as p-doping.
(C2 H 2 ) n + 2FeCl3 → (C2 H 2 )+n FeCl 4− + FeCl 2
2(C2 H 2 ) n + 3I 2 → 2[(C2 H 2 )+n I3 ]

2.38
Mechanism of conduction: The removal of an electron from the polymer ∏-back bone using a
suitable oxidising agent leads to the formation of delocalised radical ion called polarion.
A second oxidation of a chain containing polarion, followed by radical recommendation,
yields two charge carriers on each chain. The positive charges sites on the polymer chains are
compensate by anions formed by the oxidising agent.
The delocalised positive charges on the polymer chain are mobile, not the dopant anions.
Thus, these delocalised positive charges are current carriers for conduction. These charges
must move from chain to chain as well as along the chain for bulk conduction.
(ii) Reductive (or) n-doping: Treating of intrinsically conducting polymers with Lewis bases such
as Li, Na, tetrabutyl ammonia, naphthylamine, etc., is known as n-doping.
Reduction
CH CH CH CH + C10H7NH2
Polyacetylene Napthylamine
(Lewis base)
−
CH CH CH CH + C10H8
Naphthalene
+
NH
Mechanism of conduction: The addition of an electron to the polymer ∏-back bone by using a
reducing agent generates a polarion. A second reduction of chain containing polarion, followed
by the recombination of radicals, yields two negative (-ve) carriers on each chain. These charge
sites on the polymer chains are compensated by cations formed by the reducing agent.
(iii) Protonic acid doping: The synthesis of conducting polyaniline is a typical example of this type
of doping technique. In this technique, current-carrying charged species (-ve/+ve) are created by
the protonation of imine nitrogen.
Polyaniline is partially oxidised first, with a suitable oxidising agent, into a base form of
aniline, which contains alternating reduced and oxidised forms of aniline polymer backbone.
This base form of aniline when treated with aqueous HCl (IM) undergoes protonation of imine
nitrogen atom, creating current due to +ve sites in the polymer backbone. These charges are
compensated by the anions (Cl−) of the doping agent, giving the corresponding salt. This doping
results increase conductivity up to 9–10 orders of magnitude.
Applications
Conducting polymers are the most important materials to be used in electric and electronic applica-
tions. Some of the uses are as follows:
(i) As electrode material for commercial rechargeable batteries, for higher power-to-weight ratio.
(ii) As conductive tracks on printed circuit boards.
(iii) As sensors—gas sensor, radiation sensor, humidity sensor, bio sensor for glucose and galactose,
etc.
(iv) As film membranes for gas separations.
(v) As light-emitting diode.
(vi) In electrochemical display windows.
(vii) In fuel cells, as the electro catalytic materials.
(viii) In information storage devices.

Polymers 2.39
2.11.2 Conducting Polyaniline

In 1985, Alan MacDiarmid investigated polyaniline as an electrically conducting polymer.
N N N N
H H H H
n
Properties
The properties of polyaniline are as follows:
(i) Except specific conductivity, all other properties of polyaniline are considered as that of an
organic metal.
(ii) It is transparent in thin layers.
(iii) When heated, it is stable in air.
(iv) It is a highly reactive, redox active material.
(v) In conducting state, it is green and changes its colour in different media.
For example, under reducing condition, it becomes yellow and under oxidising or basic condi-
tion, it becomes blue.
Advantages
The advantages are as follows:
(i) It is the foremost air-stable conducting polymer.
(ii) It has a wide and controllable range of conductivity.
(iii) It shows a number of interesting properties such as multicolour, electrochromism, chemical sen-
sitivity and so on.
(iv) It is considered to be unique among all the conducting polymers as it can be synthesised chemi-
cally or electrochemically as a bulk powder or film.
Disadvantages
The disadvantages are as follows:
(i) It is insoluble in common solvents except strong acids and n-methyl pyrrolidine.
(ii) It has poor mechanical properties.
(iii) It decomposes prior to melting, and hence it is difficult to process.
Uses
The uses of intrinsically conducting polymers are as follows:
(i) Due to its reversible electrochemical response during anodic oxidation and cathodic reduction, it
is useful as a secondary electrode in rechargeable batteries and electrochromic display devices.
(ii) It is used for coating of films and semi-finished articles.
(iii) It is also used for corrosion protection, sensors, smart windows, printed circuit boards, conduc-
tive pipes for explosives, and conductive fabrics.

2.40
2.11.3 Extrinsically Conducting Polymers

Polymers whose conductivity is due to externally added ingredient are known as extrinsically conduct-
ing polymers. They are conductive element filled polymers and blended conducting polymers.
(i) Conductive element-filled polymers: In this kind of polymers, conducting materials like car-
bon black, metal oxides, etc., are added to the polymers.
(ii) Blended conducting polymers: In this kind of polymer, conducting polymers are mixed with
conventional polymer.
Application of Conducting Polymers

Conducting polymers have many uses because they are light weight, easy to process and have good
mechanical properties. They are used in the following:
(i) In chargeable light-weight batteries based on perchlorate-doped polyacetylene lithium systems.
These are approximately 10 times lighter than conventional, lead storage batteries. They have
flexibility to fit into different designs.
(ii) In optical display devices, based on polythiophene and polyaniline. When the structure is electri-
cally biased, the optical density of the film and its colour changes. Such electrochromic systems
produce colour displays with faster switching time and better viewing than conventional liquid
display devices. Due to redox activity in conducting state, polyaniline is green; under reducing
condition, it is in yellow colour, whereas under oxidising condition, it appears blue.
(iii) In telecommunication systems
(iv) In electromagnetic screening materials
(v) In antistatic coatings for clothing
(vi) In electronic devices such as transistors and diodes
(vii) In wiring in aircrafts and aerospace components
(viii) In solar cells and as biosensors in metabolic reactions and drug delivery system for the human body
(ix) In photo voltaic devices
(x) In non-linear optical material
(xi) In molecular wires and molecular switches
2.12 Polyphosphazenes/Phosphonitrilic Polymers

Polyphosphazenes are hybrid inorganic organic polymers with a number of different skeletal structures
that contain a backbone of alternating phosphorous and nitrogen atoms, and are interesting, commer-
cially promising materials. A variety of substituents can substitute the basic backbone and hence we
can get a variety of products. The basic backbone of polyphosphazene is as follows:
Cl
N P
n
Cl
Preparation: The most popularly used method for preparing polyphosphazenes is ring opening and
substitution method. Allcock and co-workers discovered that cyclic trimer (hexachlorocyclo triphosp-
hazene) can be thermally ring opened and can give high molecular weight soluble poly (dichlorophos-
phazene). After the replacement of the chlorine atoms in poly (dichlorophosphazene) by reaction with
organic/organometallic nucleophiles, they give a variety of polyphosphazenes.

Polymers 2.41
Cl Cl
P
N N Cl
Heat
N P
Cl 250°C
n
P P Cl Cl
Cl Cl
N
Hexachlorocyclo triphosphazene Poly (dichlorophosphazene)
Substitution Reactions
(i) Reaction with sodium alkoxide: Poly (dichlorophosphazene) reacts with sodium alkoxide and
gives poly (dialkoxyphosphazene).
Cl OR
RONa
N P N P
–NaCl
n n
Cl OR
Poly (dialkoxyphosphazene)
(ii) Reaction with amine: Poly (dichlorophosphazene) reacts with amine and gives poly
(dialkylaminephasphazene).
Cl NHR
RNH2
N P –HCl
N P
n n
Cl NHR
Poly (dialkylaminephasphazene)
(iii) Reaction with metal alkyd: Poly (dichlorophosphazene) reacts with metal alkyd and gives poly
(dialkylphasphazene).
Cl R
RM
N P –MCl
N P
n n
Cl R
Poly (dialkylphasphazene)
Important Characteristics of Polyphosphazenes

polyphosphazenes have many important properties; biocompatibility, high dipole moment, flexibility,
chemical inertness, broad range of glass transition temperature (Tg), elastomeric property and imper-
meability are the most important of them.
Applications
Based on their wide range of unique properties, polyphosphazenes have countless and advanced appli-
cations. They have potential for formation of new compounds. The applications include in challenging
areas of biomedical research such as tissue generation, macromolecules and so on. These are also used
as ion-conductive membranes for rechargeable lithium batteries and fuel cell membranes. These are

2.42
advanced materials of elastomers for aerospace engineering. Polyphosphazenes are good photonic
materials and fire-resistant polymers.
2.13 COMPOSITES
Composites are multiphase materials that exhibit a significant proportion of the properties of both the
constituent materials.
(or)
Composite materials composed of at least two distinctly dissimilar materials act in harmony. A judi-
cious combination of two or more distinct materials can provide better combination of properties or an
artificially prepared multiphase material in which the chemically dissimilar phases are separated by a
distinct interface.
For example, wood is the composite of cellulose and lignin, bone is the composite of a soft, strong
protein collagen, and brittle, hard apatite material.
Packing paper impregnated with bitumen or wax, rain-proof cloth (cloth impregnated with water-
proof material), insulating tape, reinforced concrete, etc.
2.13.1 Constituents of Composites

Composite material mainly comprises of the following:
(i) Matrix phase: Matrix phase is the continuous body constituent enclosing the composite and
given in its bulk form. Depending upon the matrix phase, composites are known as ceramic
matrix composites, metal matrix composites, polymer matrix composites, etc.
Functions of Matrix Phase
(a) Matrix phase binds the dispersion phase, act as a medium, applied stress is transmitted and
distributed uniformly.
(b) It protects the surface from damage due to chemical reactions, mechanical abrasion, etc.
(c) It prevents the propagation of brittleness, cracking, etc.
Hence, a good matrix phase should be ductile, having corrosion resistant and possess high binding
strength.
(ii) Dispersed phase: Dispersed phase is the structural constituent of composite. Fibres, flakes, whis-
kers, etc., are some important dispersed phases.
2.13.2 Classification of Composites

Composites are broadly classified into three categories:
(i) Particle-reinforced composites: In these composites, the dispersed phase is equiaxed, that is,
the dimensions of the particles are nearly the same in all directions. They are subdivided into
the following:
(a) Large-particle composites
(b) Dispersion-strengthened composites
(ii) Fibre-reinforced composites: In these composites, the dispersed phase is in the form of fibres.
These are subdivided into (a) continuous aligned (b) discontinuous.
Discontinuous composites are further divided into (a) aligned (b) randomly oriented.

Polymers 2.43
(iii) Structural composites: In these composites, the properties depend not only on the constitu-
ent material but also on this geometrical design. These are subdivided into (a) laminates and
(b) sandwich panels.
Among these, fibre-reinforced polymer composites are widely used.
Fibre-reinforced Polymer Composites

These are prepared by reinforcing a plastic matrix with a high-strength fibre material.
Fibre-reinforced composites involve three components, namely filament, a polymer matrix and an
encapsulating agent (which ties fibre filaments to polymer). Glass fibres and metallic fibres are com-
monly employed for this purpose. The fibres can be employed either in the form of continuous lengths,
staples or whiskers. Such composites possess high specific strength (tensile strength/specific gravity)
and high specific modulus (elastic modulus/specific gravity), stiffness and lower overall density.
Characteristics
The fibre-reinforced composites possess superior properties such as higher yield strength, facture
strength and fatigue life. The fibres prevent slip and crack propagation and inhibit it, thereby increas-
ing mechanical properties. When a load is applied, there is a localised plastic flow in the matrix, which
transfers the load to the fibres embedded in it. When a soft phase is present in hard matrix, the shock
resistance of the composite is increased. On the other hand, if hard-reinforcing fibres are present in
a soft matrix, the strength and modulus of the composite are increased. To obtain composites having
the maximum strength and modulus, it is essential that there should be maximum number of fibres
per unit volume, so that each fibre takes its full share of the load. The fibre-reinforced composites are,
generally, anisotropic (i.e., having different directions), and the maximum strength is in the direction
of alignment of fibres. For getting isotropic properties, the fibres are oriented randomly within the
matrix, for example, ordinary fibre glass. It may be pointed here that the cost of laying fibres aligned in
a particular direction is much higher than that for random orientation. For preparing fibre-reinforced
composites, the following are essential:
(i) The coefficient of expansion of the fibre matches closely that of the matrix.
(ii) The fibre and matrix should be chemically compatible with each other and no undesirable reac-
tion takes place between them.
(iii) The fibre should be stable at room temperature and should retain a good percentage of strength
at elevated temperatures.
Some important reinforced composites are described here.
(i) Glass fibre-reinforced polymer composites: For improving the characteristics of nylon, poly-
ester, etc., containing polymer matrices, glass fibres are employed. These have lower densities,
higher tensile strengths and resistance to corrosion and chemicals.
Limitations: The limitations are as follows:
(a) Since the most polymeric matrices start deteriorating or flow or melt at high temperatures,
they find application with limited temperature service conditions.
(b) They cannot be employed as structural components, since these materials do not possess the
desired stiffness and rigidity.

2.44
Applications: They are used in automobile parts, storage tanks, floorings (industrial), transpor-
tation industries, plastic, pipes, etc.
(ii) Carbon fibre-reinforced polymer composites: They are also known as advance polymer matrix
composites or high performance composites and are employed in situations requiring (i) excel-
lent resistance to corrosion, (ii) lighter density and (iii) retention of desired properties, even at
elevated temperatures. However, the general use is limited due to their higher costs.
Applications: They are used as structural components (like wing, body and stabiliser) of air-
crafts (military and commercial) and helicopter’s recreational equipment (fishing rod), sport
materials (golf clubs), etc.
2.13.3 Advantages of Composites over Conventional Materials

Composites have the following advantages over conventional materials such as metals, polymers,
ceramics and so on.
(i) They have higher specific strength and stiffness. They can maintain strength up to higher
temperatures.
(ii) They have lower specific gravity, electrical conductivity and thermal expansion.
(iii) They have better toughness, impact, thermal shock resistance, fatigue strength, corrosion and
oxidation resistance.
2.13.4 Applications of Composites

(i) In automobile industries, transportation industries, turbine engines, wire drawing dies, valves,
pump parts, spray nozzles, storage tanks, fabrication of roof and floors, furniture, sport goods
(lawn, tennis rackets), high-speed machinery, etc.
(ii) Marine applications like propellers, shafts, hulls, spars (for racing boats) and other ship parts.
(iii) Aeronautical applications like components of rockets, aircrafts (business and military), helicop-
ters, missiles, etc.
(iv) Communication antennae and electronic circuit boards
(v) Safety equipment like ballistic protection

1. Repeating units present in polymer is _______.
[Ans.: monomer]
2. When two or more different monomer units participate in polymerisation, _______ polymers
are formed.
[Ans.: copolymers]
3. _______ plastics cannot be remoulded.
[Ans.: thermosetting]

Polymers 2.45
4. Monomer units that participate in the formation of Fluon/Teflon are called _______.
[Ans.: tetrafluoroethylene]
5. Bakelite is _______ plastic.
[Ans.: thermosetting]
6. _______ is the basic unit present natural rubber
[Ans.: Isoprene]
7. _______ monomers are involved in formation of nylon 66.
[Ans.: Hexamethylenediamine and Adipic acid]
8. Monomers possess the double bonds undergo _______ polymerisation mechanism.
[Ans.: addition]
9. An organic polymer with a highly delocalised pi-electron system, having electrical conduct-
ance is called a _______.
[Ans.: conducting polymer]
10. _______ is an organic conducting polymer
[Ans.: Polyaniline]
11. The polymers which occur in nature from plants, bacteria and algae are called _______.
[Ans.: Bio polymer]
12. Triglycerides are produced from _______.
[Ans.: soya bean]

1. High polymers are
(a) Liquids (b) Gases
(c) Solids (d) Colloidal
[Ans.: d]
2. Polymerisation in which two or more chemically different monomers takes part, is called
(a) Addition polymerisation (b) Co polymerisation
(c) Chain polymerisation (d) None of these
[Ans.: b]
3. Structural units of high polymers, are called
(a) Fibres (b) Thermo units
(c) Monomers fabrics (d) Fabrics
[Ans.: c]
4. GR-S rubber is an example of
(a) Condensation polymerisation (b) Co polymerisation
(c) Addition polymerisation (d) Cross-linked polymer
[Ans.: b]

2.46
5. A thermoplastic is formed by the phenomenon of

(a) Chlorination (b) Condensation polymerisation
(c) Nitration (d) Chain polymerisation
[Ans.: d]
6. A copolymer is formed by the union of two or more
(a) A molecules of some monomer by the elimination of small molecules like H2O
(b) Monomer molecules in a chain without the elimination of H2O etc.
(c) Monomer molecules with the elimination of small molecules like H2O
(d) Thermosetting and thermoplastic resins
[Ans.: b]
7. Phenol-formaldehyde resin is commercially known as
(a) PVC (b) Elastomer
(c) Bakelite (d) Nylon
[Ans.: c]
8. Polymer commonly used for making fibre/cloth is
(a) Rubber (b) PVC
(c) Nylon (d) Bakelite
[Ans.: c]
9. Bakelite is prepared by the condensation of
(a) Benzene and formaldehyde (b) Phenol and formaldehyde
(c) Phenol and acetaldehyde (d) Glycerol and phthalic acid
[Ans.: b]
10. A high molecular weight material that can easily be moulded in any desired shape is
(a) Graphite (b) Resin
(c) Jelly (d) Grease
[Ans.: b]
11. A plastic which can be softened on heating and hardened on cooling is called
(a) Thermoelastic (b) Thermoplastic
(c) Thermosetting (d) Thermite
[Ans.: b]
12. Phenol-formaldehyde (Bakelite) is an example of
(a) Thermoelastic (b) Thermoplastic
(c) Thermosetting (d) Thermite
[Ans.: c]
13. Natural rubber is basically a polymer of
(a) Propylene (b) Isoprene
(c) Ethylene (d) Propane
[Ans.: b]
14. Which one of the following is an elastomer?
(a) PVC (b) Bakelite
(c) Natural rubber (d) Nylon
[Ans.: c]

Polymers 2.47
15. Raw rubber on vulcanisation becomes

(a) Plastic (b) Rocky
(c) Soft (d) Less elastic
[Ans.: d]
16. The most commonly used vulcanising agent is
(a) Graphic (b) Carbon black
(c) Sulphur (d) Dry ice
[Ans.: c]
17. Ebonite is
(a) Polyethylene (b) Highly vulcanised rubber
(c) Natural (d) Synthetic rubber
[Ans.: b]
18. One of the important uses of Bakelite is for making
(a) Cables (b) Electrical switches
(c) Cloth (d) Hose pipe
[Ans.: b]
19. The fibre obtained by condensation of hexamethylenediamine and adipic acid is
(a) Decorn (b) Nylon
(c) Rayon (d) Terylene
[Ans.: b]
20. Nylon is
(a) A polythene derivative (b) A polyester fibre
(c) A polyamide fibre (d) None of these
[Ans.: c]
21. Monomer units involved in the formation of Bakelite are
(a) Urea and formaldehyde (b) Phenol and formaldehyde
(c) Urea and phenol (d) Butadiene and ethylene
[Ans.: b]
22. Buna-s is a co polymer of
(a) Vinyl chloride and vinyl alcohol (b) Butadiene and acrylonitrile
(c) Butadiene and styrene (d) Butadiene and ethylene
[Ans.: c]
23. Which one is not a macro molecule?
(a) Protein (b) Insulin
(c) Ice (d) Cellulose
[Ans.: c]
24. Which one is a co polymer?
(a) Nylon-66 (b) Teflon
(c) PVC (d) Polybutadiene
[Ans.: a]

2.48
25. An example of chain-growth polymer is

(a) Nylon-66 (b) Bakelite
(c) Terylene (d) Teflon
[Ans.: d]
26. What is the repeating unit in Teflon?
(a) F2C = CF2 (b) H2C = CH2
(c) H2C = CHCl (d) H2C = CHC6H5
[Ans.: a]
27. Which of the following is not a thermoplastic?
(a) Bakelite (b) Terylene
(c) Polystyrene (d) Polythene
[Ans.: a]
28. Which one is a step-growth polymer?
(a) Teflon (b) PVC
(c) Polybutadiene (d) Bakelite
[Ans.: d]
29. Which of the following is a synthetic polymer?
(a) Cellulose (b) PVC
(c) Proteins (d) Nucleic acids
[Ans.: b]
30. Which of the following is a linear polymer?
(a) Nylons (b) Bakelite
(c) Low density polythene (d) Formaldehyde polymer
[Ans.: a]
31. Which of the following has the largest molecular mass?
(a) Monomer (b) Dimer
(c) Oligomer (d) Polymer
[Ans.: d]
32. Isoprene is monomer of
(a) Starch (b) Synthetic rubber
(c) Natural rubber (d) PVC
[Ans.: c]
33. Which of the following is thermosetting polymer?
(a) Linear (b) Branched chain
(c) Cross-linked (d) Thermoplastic
[Ans.: c]
34. Which of the following is an addition polymer?
(a) Terylene (b) Nylon
(c) Polyethylene (d) All of these
[Ans.: c]

Polymers 2.49
35. Which of the following is thermosetting polymer?

(a) Nylon (b) Polyethylene
(c) Bakelite (d) PVC
[Ans.: c]
36. The monomer of PVC is
(a) Ethylene (b) Vinyl chloride
(c) Tetrafluoroethylene (d) Styrene
[Ans.: b]
37. Chloroprene is the repeating unit in
(a) Polystyrene (b) Neoprene
(c) PVC (d) Polythene
[Ans.: b]
38. The process of vulcanisation makes rubber
(a) Soluble in water (b) Hard
(c) Soft (d) More elastic
[Ans.: b]
39. A common catalyst used in addition polymerisation is
(a) Nickel (b) Y-zeolite
(c) Ziegler–Natta catalyst (d) Platinum
[Ans.: c]
40. Functionality of phenol is
(a) One (b) Two
(c) Three (d) Six
[Ans.: c]
41. _______ polymer is formed from the fermentation of sugar feed stocks obtained from
sugarcane.
(a) Lactic acid (b) Steric acid
(c) Triglycerides (d) None of these
[Ans.: a]
42. Adhesive, binders and protective coating characteristics exhibiting polymers is
(a) Lactose (b) Galactose
(c) Starch (d) Casein
[Ans.: d]
43. Water soluble bio-polymers is/are
(a) Starch (b) Polyester
(c) Both (a) and (b) (d) None of these
[Ans.: a]

1. What is a monomer?
Ans.: The repeating unit present in the formation of a polymer is known as a monomer.

2.50
2. What is a polymer?

Ans.: Polymers are macromolecules of high molecular masses built up by the linking together a
large number of small, repeated units by a covalent bond.
3. What is meant by polymerisation?
Ans.: The chemical process leading to the formation of a polymer is known as polymerisation.
4. What is meant by degree of polymerisation?
Ans.: The number of monomer units in a polymer is known as the degree of polymerisation.
5. Differentiate between homopolymer and copolymer.
Ans.: Homopolymers are formed with same monomer units.
For example, PE, PS, PVC, etc.
Copolymers are formed with two or more different monomers.
For example, styrene butadiene rubber (styrene + butadiene)
6. Differentiate between addition and condensation polymerisation.
Ans.: Addition polymerisation is the process of polymerisation by the addition of monomer units
which have unsaturated double or triple bonds.
For example, polyethylene, polyvinyl chloride, etc.
Condensation polymerisation takes place where the monomer units have two or more reac-
tive functional groups.
For example, polyester, nylon, polyamide, etc.
7. Define thermoplastics.
Ans.: Linear, long chain polymers which can be softened on heating and hardened on cooling
are known as thermoplastics.
For example, polythene, polyvinyl chloride, etc.
8. What are the monomers present on nylon 66?
Ans.: Hexamethylenediamine and adipic acid.
9. What is meant by vulcanisation of rubber?
Ans.: Vulcanisation is heating of the raw rubber at 100–140°C with sulphur.
10. What is natural rubber?
Ans.: Cis-polyisoprene is a natural rubber.
11. What is gutta percha?
Ans.: Trans-polyisoprene is gutta percha.
12. What is crepe rubber?
Ans.: Rubber with sodium bisulphite is passed through a creping machine and the coagulum
is rolled into sheets. The sheet is hence having the surface like crepe paper; hence, it is
known as crepe rubber.
13. What is an elastomer?
Ans.: A n elastomer is vulcanisable rubber like polymer, which can be stretched to at least twice
its length and returned to its original shape and dimensions as soon as stretching force is
released.

Polymers 2.51
14. Why does raw rubber need vulcanisation?

Ans.: In vulcanisation, sulphur combines chemically at the double bonds of different rubber
spring and provides cross-linking between the chains. Hence, for stiffening the rubber
needs vulcanisation.
15. Give examples for natural polymers.
Ans.: Cotton, silk, wool, nucleic acid, proteins, starch, cellulose, etc.
16. Give examples for inorganic polymers.
Ans.: Polyphosphazenes, polysilanes, polygermanes, etc.
17. What are the substances mixed in the compounding of rubber?
Ans.: A ntioxidants, colouring agents, vulcanising agents, accelerators, plasticisers and inert fill-
ers are adding in the compounding of raw rubber.
18. Give note on Bio-polymers?
Ans.: Bio-polymers are macromolecules that occur in nature from plants, tress, bacteria, algae or
others source that are long chains linked together through a chemical bond. They are often
degradable through microbial process such as compositing.
For example, cellulose, proteins, starch, collagen, casein and polyesters
19. Write important bio-degradable polymers?
Ans.: (a) Lactic acids: It is obtained from fermentation of sugar feed stocks conversion of starch
from corn, potato peels, etc.
(b) Triglycerides: It is produced from soya bean, fax and rape seed.
(c) Starch: It is found in corn, potatoes, wheat, tapioca and some other plants.
(d) Collagen: It is found in mammals. It is used in capsules for drug.
20. Explain the importance of bio polymers?
Bio-based materials have the potential to produce fewer greenhouses gases, require less energy
and produce fewer toxic pollutants.
(1) They may also be recyclable or composted.
(2) They reduce waste stream.

Q.1 (a) Write a note on the properties and uses of Teflon.
(b) Differentiate between natural polymer and synthetic polymer.
(c) Write a note on silicone rubbers.
Q.2 (a) Distinguish between addition and condensation polymerisation.
(b) Explain the differences between thermoplastics and thermosetting plastics with examples.
(c) What is meant by degree of polymerisation?
Q.3 Write the structures of four addition polymers and four condensation polymers with their respec-
tive monomers.
Q.4 (a) Describe the preparation, properties and engineering uses of polyethylene.
(b) What is meant by fabrication of plastics? Mention the different fabrication techniques.

2.52
Q.5 (a) What are elastomers? Give examples.

(b) What are the ingredients used in the compounding of plastics? What are their functions?
Q.6 (a) What is a plastic?
(b) Write the merits and demerits of using plastics in the place of metals.
Q.7 (a) Identify the thermosets and thermoplastics among the following:
(i) PVC
(ii) Polyethylene
(iii) Silicone
(iv) Polyester fibre
(v) Bakelite
(b) What is Bakelite? How is it manufactured? Mention its uses.
Q.8 (a) Explain the process of extrusion moulding with a neat diagram.
(b) How are the following polymers prepared? Mention their properties and uses.
(i) PVC
(ii) LDPE
Q.9 (a) What are elastomers? Give the preparation, properties and uses of Buna-S.
(b) Describe a method for moulding of thermoplastic resin.
Q.10 (a) Explain the preparation, properties and uses of Bakelite.
(b) Describe the process of compression moulding with a neat sketch.
Q.11 (a) W hy are silicones called inorganic polymers? Discuss the synthesis of linear chain silicones.
(b) Why can Bakelite not be remoulded? Write its repeating unit.
(c) Describe condensation polymerisation with an example.
Q.12 (a) What is a homochain polymer? Give examples.
(b) What is polymerisation? Explain the different types of polymerisation with examples.
Q.13 (a) How is HDPE prepared? Give its properties and uses.
(b) Explain the injection moulding process with a neat diagram. Mention its advantages.
Q.14 Write informative notes on the following:
(a) Classification of polymers
(b) Mechanism of radical polymerisation
(c) Anionic and cationic polymerisation
(d) Thermodynamics of a polymerisation process
Q.15 What are the common constituents of plastics and what are their functions?
Q.16 Write short notes on the following:
(a) Vulcanisation of rubber
(b) Polyvinyl chloride
(c) Compounding of rubber
(d) Reclaimed rubber
Q.17 Write an essay on the preparation, properties and uses of the following:
(a) Polyvinyl acetate
(b) Cellulose acetate

Polymers 2.53
(c) Phenol formaldehyde resins

(d) Teflon
(e) Polyethylene
(f) Polystyrene
(g) Polymethylmethacrylate
Q.18 Discuss the various polymers related to natural rubber with emphasis on their preparation, prop-
erties and uses.
Q.19 Write an account of application of polymers in bio-medical electronic fields.
Q.20 Write an essay on the various types of synthetic rubber with brief description of the preparation,
properties and uses of any three of them.
Q.21 Write an essay on fibre-reinforced plastics.
Q.22 What type of rubber would you recommend for the following?
(a) For a flexible connection to a steam line
(b) As a gasket for a pipe containing a chlorinated solvent
(c) In a solvent to form an adhesive
(a) Molecular weights of polymers
(b) Conductive polymers
(c) Ionic polymers
(d) Liquid crystal polymers
(e) Engineering polymers
(f) Photo conductive polymers
(g) Polymer structure and properties of polymers
Q.24 Define the following terms and give examples: monomer, polymer, polymerisation and degree
of polymerisation.
Q.25 Distinguish clearly between the following:
(a) Thermoplastic and thermosetting plastic
(b) Natural and synthetic rubber
(c) Addition and condensation polymerisation
Q.26 Discuss the addition polymerisation reaction mechanism.
Q.27 Explain condensation polymerisation with an example.
(a) Vulcanisation of rubber
(b) Compounding of rubber
(c) Gutta percha
(d) Silicone rubber
Q.29 Give the preparation, properties and engineering uses of the following:
(a) Teflon
(b) Polystyrene
(c) Polyethene

2.54
(d) Polyurethane
(e) HDPE
(f) Conductive polymers
Q.30 Discuss the various polymers related to natural rubber with emphasis on their preparation, prop-
erties and uses.
Q.31 Write an essay on the various types of synthetic rubbers.
Q.32 What are elastomers? Write the structure for natural rubber and gutta percha.
Q.33 What is vulcanisation of rubber? Mention its uses. Explain why natural rubber needs vulcanisa-
tion. How is it carried out?
Q.34 How is crepe rubber obtained from latex?
Q.35 What is latex? How is natural rubber isolated from it?
Q.36 Write short notes on silicones. How are they prepared?
Q.37 Write a short note on conducting polymers.
Q.38 Give the structural unit of gutta percha.
Q.39 Give detailed notes bio-polymers and its importance.
Q.40 Explain the preparation methods of bio-polymer and the importance of bio-degradable polymers.

3 Fuels and
Combustion
“A revolution in humanity’s use of fossil fuel-based energy would be necessary

sooner or later to sustain and to extend modern standards of living.”
3.1 INTRODUCTION
‘Fuel is the source of heat energy, it can be stored as potential chemical energy and can be released
through combustion.’
‘Combustible matter having carbon as a major ingredient, produce large amount of heat energy on
burning and can be used for heat generation in industry and domestic applications is known as a fuel.’
‘Any compound or a substance which can produce energy and can be used in the production of
power is termed as a fuel.’
In the combustion process, a fuel reacts with oxygen and releases the energy.
Fuel + O2 → CO2 + H2O + heat
3.2 CLASSIFICATION OF FUELS

Fuels are broadly classified according to their occurrence and state of aggregation. According to the
occurrence they are classified as primary (natural) and secondary (derived) fuels and based on the state
of aggregation solid, liquid and gaseous fuels.
Fuel
(Occurance)
Primary (or) natural Secondary (or) der ive

State of aggregation State of aggregation
Solid Liquid Gaseous Solid Liquid Gaseous

Wood, Peat Petroleum Natural gases Coke, semi Gasoline, Coal gas
Coal, Lignite (or) coke, charcoal, diesel oil, water gas
Crude oil petroleum Kerosene producer
coke, thiokol gas, LPG
M03_ENGINEERING-CHE00_SE_XXXX_CH03.indd 1 5/9/2016 4:35:40 PM

3.3 UNITS OF HEAT

(i) CGS system–calorie: The amount of heat required to raise the temperature of 1 g of water through
1°C at 15 to 16°C.
(ii) MKS system–kilo calorie: The amount of heat required to raise the temperature of 1 kg of water
through 1°C.
1 kcal = 1,000 cal
(iii) British system (FPS system): British thermal unit (BTU): The amount of heat required to raise
the temperature of 1 pound of water through 1°F at 60 to 61°F.
1 BTU = 252 cal = 0.252 kcal
1kcal = 3.968 BTU
(iv) Centigrade heat unit (CHU): The amount of heat required to raise the temperature of 1 pound of
water through 1°C.
1 kcal = 3.968 BTU = 2.2 CHU
3.4 Calorific Value

The total quantity of heat liberated by the complete combustion of one unit mass/volume of fuel in oxygen
is known as calorific value. This is mainly divided into higher calorific value and lower calorific value.
(i) Higher (or) gross calorific value (HCV or GCV): The higher or gross calorific value is the amount
of heat liberated when one unit mass/volume of the fuel is burnt completely and the combustible
products are cooled to room temperature. i.e., 25°C or 77°F.
(ii) Lower or net calorific value (LCV or NCV): Lower calorific value is defined as the amount of heat
liberated when one unit of fuel is burnt completely but the combustible products are allowed to
escape; hence, here lesser amount of heat is available.
LCV = HCV - latent heat of water vapour
LCV = HCV - mass of hydrogen × 9 × latent heat of steam (587 kcal/kg)
This is because one part by mass of hydrogen gives nine parts by mass of water.
LCV = HCV - 0.09HX 587 kcal/kg
(iii) Units of calorific value:
C.G.S-Calories/gram
For Solid and Liquid M.K.S-Kcal/kg

Fuels
F.P.S-B.T.U/lb
C.G.S-Calorie/cubic centimeter (cal/cm3)
Gaseous fuels M.K.S-Kcal/cubic meter (kcal/m3)
F.P.S-B.T.U/cubic feet (B.T.U/ft3)

Fuels and Combustion 3.3
3.5 Determination of calorific value

A calorimeter is used for determining calorific value. For determining calorific value of solid and
liquid fuels a bomb calorimeter is used and for gaseous fuel Junker’s calorimeter is used.
3.5.1 Bomb Calorimeter

Description
Bomb calorimeter consists of strong cylindrical stainless steel bomb with lid. The bomb carries the
fuel, and the lid can be screwed to the body of the bomb and make a perfect gas tight seal. The lid has
two stainless steel electrodes and an oxygen inlet valve, and among these a small ring is attached to
one of the electrodes. A nickel or stainless steel crucible is supported by that right. The bomb is placed
in a copper colorimeter, for preventing heat loss by radiation, it is surrounded by air and water jacket.
Stirrer which can operated electrically and Beckmann’s thermometer, having sensitivity to read up to
0.01°C are provided. The set-up is shown in Figure 3.1.
6V
battery
Beckmann’s Oxygen
thermometer valve
Electrically
operated stirrer
Electrodes
to which a ring
is attached Copper
calorimeter
Mg fuse wire Stainless steel

bomb
Weighted pallet Stainless steel
of given fuel crucible
sample
Air jacket
Water jacket
Figure 3.1 Bomb calorimeter
Working
In the clean crucible, a weighted amount (0.5 to 1.0 g) of the fuel is taken and the crucible is supported
by a ring, a fine magnesium wire touching the fuel sample is stretched across the electrodes. The bomb
lid is tightly screwed, filled with oxygen to 25 atm pressure and then lowered into copper calorimeter,
containing known mass of water, and the initial temperature (t1) is noted. Now, the circuit is completed
by connecting the electrodes with a 6 V battery. The sample burns, liberates heat and absorbed by
water. The water is stirred continuously for maintaining uniform temperature, and hence the final
temperature (t2) is noted.
Observations and Calculation

Weight of fuel = x g
Weight of water in calorimeter = w g

Water equivalent of calorimeter = wt. of apparatus × specific heat = w g

Initial temperature of water = t °C
Final temperature of water = t2 °C
High calorific value of the fuel
(w + w ) (t2 − t1 )
HCV = cal/g
x
Lower calorific value of the fuel
LCV = HCV – 0.09 H × 587 cal/g
Latent of heat of steam = 587 cal/g
Weight of water produced from 1 g of fuel = 9H/100 g = 0.09H g
H = percentage of hydrogen in fuel.
3.5.2 Junker’s Calorimeter

Junker’s gas calorimeter (Figure 3.2) consists of a vertical cylindrical combustion chamber, and the
pressure governor regulates the supply of gaseous fuel. Gasometer measures the volume of gas flowing
in a particular time and combustion of fuel can be carried out by a Bunsen’s burner. The combustion
chamber is surrounded by an annular water space, inside heat exchange coils and outer flues are fitted.
Chromium plated outer jacket which prevent the radiative and convective heat loss from calorimeters
because it contains air and acts as a very good insulator. Openings of annular space can circulate the
water at the appropriate places at constant rate around the combustion chamber. Two thermometers
placed at appropriate place can measure the temperatures of the inlet and outlet water.
Thermometer (T2)
To measuring
vessel
Cylindrical combustion
chamber
Outer jacket
Air
er
Thermometer
t
ome
(T1)
rm
Water from
The
constant
head Exit gases
Condensate
Bunsen burner Gas
Gasometer
Figure 3.2 Junker’s gas calorimeter

In the combustion chamber a known volume of gas is burned at a constant rate in excess of air, produced
heat is absorbed by water. From the temperature difference, heat evolved from the gas can be calculated.
Observations and Calculation

Volume of the gas burnt in ‘t’ at STP = V
Temperature of incoming water = T1
Temperature of outgoing water = T2
Weight of water collected in time t = w
w(T2 − T1 )
High calorific value = kcal/m3 .
V
Mass of steam condensed in time ‘t’ in graduated cylinder from V m3 of gas = m
Latent heat of steam = 587 cal/kg
 m 
Lower calorific value = LCV =  HCV − × 587 kcal/m3
 v 
LCV = HCV − 0.09XHX587 kcal/kg
Calculation of calorific value of a fuel can be made theoretically by using Dulongs formula.
Solved Numerical Problems Based on Calorific Value

(i) Calculate the gross and net calorific value of coal having the following compositions carbon –
85%, hydrogen – 8%, sulphur – 1%, nitrogen – 2%, ash – 4%, latent heat of steam – 587 ca/g.
Solution Gross Calorific Value (GCV)
1   0 
= 8080 × C + 34, 500  H −  + 2, 240 × S k cal/kg
100   8  
1   0 
= 8080 × 85 + 34, 500  8 −  + 2, 240 × 1 k cal/kg
100   8 
1
= [686, 800 + 276, 000 + 2, 240] k cal/kg
100
1
= [965040] k cal/kg = 9650.4 k cal/kg
100
Net Calorific Value (NCV) = (GCV – 0.09H × 587) k cal/kg
= (9650.4 – 0.09 × 8 × 587) k cal/kg = 9227.8 k cal.kg
(ii) A coal has the following composition by weight: C – 90%, O – 3.0%, S – 0.5%, N = 0.5% and ash
= 2.5%. Net calorific value of the coal was found to be 8490.5 k cal/kg. Calculate the percentage
of hydrogen and higher calorific value of coal.
Solution HCV = (HCV + 0.09H × 587) k cal/kg
= (8490.5 + 0.09H × 587) k cal/kg
= (8490.5 + 52.8H) k cal/kg (i)
1   3.0  
Also HCV = 8080 × 90 + 34, 500  H −  + 2, 240 × 0.5 k cal/kg
100   8 
= [7272 + 345H − 129.4 + 11.2] k cal/kg
= [7754.8 + 345H] k cal/kg (ii)

From (i) and (ii), we get

7754.8 + 345H = 8490.5 + 52.8 H
or 292.2H = 8490.5 – 7154.8 = 1335.7
or percentage of H = 1335.7/292.2 = 4.575% (iii)
HCV = (8490.5 + 52.8 × 4.575) k cal/kg [From (i) and (iii)]
= (8490.5 + 241.3) k cal/kg = 8731.8 k cal/kg
(iii) 0.72 gram of a fuel containing 80% carbon, when burnt in a bomb calorimeter, increased the
temperature of water from 27.3° to 29.1°C. If the calorimeter contains 250 gm of water and its
water equivalent is 150 gm, calculate the HCV of the fuel. Give your answer in kJ/kg.
Solution Here x = 0.72 gm, W = 250 gm, w = 150 gm, t1 = 273°C, t2 = 29.1°C
(W + w )(t 2 − t1 )
∴ HCV of fuel (L) = k cal/kg
x
(250 + 150) × (29.1− − 27.3)
= k cal/kg
0.72
= 1000 × 4.2 kJ/kg = 4200 kJ/kg
(iv) On burning 0.83 g of a solid fuel in a bomb calorimeter, the temperature of 3500 g of water
increased from 26.5°C to 29.2°C. Water equivalent of calorimeter and latent heat of steam are
385.0 g and 587.0 cal/g respectively. If the fuel contains 0.7% hydrogen, calculate its gross and
net calorific value.
Solution Here, wt. of fuel (x) = 0.83 g; wt of water (W) = 3500 g; water equivalent of calorim-
eter (w) = 385 g; (t2 – t1) = 2.7°C; percentage of hydrogen (H) = 0.7%; latent heat of steam =
587 cal/g.
( W + w )( t 2 − t1 ) (3500 + 385) × 2.7
\ Gross calorific value = = = 12638 cal/g
x 0.83
Net calorific value = [GCV – 0.09H × 587] = (12683 – 0.09 × 0.7 × 587) cal/g
= (12683 – 37) cal/gm = 12601 cal/gm
(v) Calculate the calorific value of a fuel sample of the coal with the following data.
Mass of the coal = 0.6 g
Water equivalent of calorimeter = 2200 gm
Specific heat of water = 4.187 kJ kg−1 °C−1
Rise in temperature = 6.52 °C
Solution Heat liberated by burning 0.6 g coal
= 3.3 kg × 4.187 kJ kg−1 °C−1 × 6.52 °C = 60.06 kJ
\ Calorific value of coal = 60.06 kJ/0.6 g = 100.1 kJ g−1.
(vi) A sample of coal contains C = 93% H = 6 % and ash = 1%. The following data were obtained
when the above coal was tested in bomb calorimeter.
(a) Wt. of coal burnt – 0.92 gm
(b) Wt. of water taken – 550 gm

(c) Water equivalent of bomb & calorimeter – 2200 g

(d) Rise in temperature – 2.42 °C
(e) Fuse wire correction – 10.0 cal
(f) Acid correction – 50.0 cal
Calculate grass and net calorific values of the coal, assuming the latent heat of condensation of
steam as 580 cal/g.
Solution Wt. of coal sample (x) = 0.92 g: wt. of water (W) = 550 g: water equivalent of calo-
rimeter (w) = 2200 g: temperature rise (t2 – t1) = 2.42 °C; acid correction = 50.0 cal, fuse wire
correction = 10.0 cal; latent heat of steam = 580 cal/g percentage of H = 6%
( W + w )(t2 − t1 ) − [Acid + fuse wire correction ]
∴ GCV =
x
(550 + 2200)(2.42) − (50 + 10)
= cal/g
0.92
= 7168.5 cal/g
NCV = (GCV − 0.09H × Latent heat of steam ) − (7168.5 − 0.09 × 6 × 580) cal/g
= 6855.3 cal/g
3.6 Characteristics of Good Fuel

Important characteristics of a good fuel are listed hereunder.
(i) HCV: The amount of heat released is dependent on high calorific value, hence fuel should
possess more HCV.
(ii) Low moisture content: Moisture content of fuel reduces the calorific value, hence fuel should
possess low moisture content.
(iii) Moderate ignition temperature: Minimum required temperature to preheat the fuel and starts
burning is the ignition temperature. Fuel must have moderate ignition temperature, because low
ignition temperature is dangerous for storage and transport due to fire hazard and for starting a
fire, high ignition temperature is not suitable.
(iv) Moderate velocity of combustion: For continuous supply of heat, fuel must burn with a
moderate velocity.
(v) Low non-combustion matter and ash content: After combustion, non-combustible matter pro-
duces high ash content and also reduces the heating value. With this more heat loss, and loss of
money for over storage, handling, disposal of ash, etc.
(vi) Low cost: Good fuel should be available easily in bulk at low cost.
(vii) High pyrometric effect: Pyrometric effect is the highest temperature obtained with the fuel,
hence fuel should have high pyrometric effect.
(viii) Less pollutants/environmental friendly: By-products of combustion like CO, SO2, NO2, etc.
pollute the environment, so a good fuel should release less pollutants and should be environment
friendly.
(ix) Storage cost: Storage cost of a fuel in bulk should be low
(x) Easy transportation: Fuel should be easy to transport with low cost.
(xi) Uniform particle size: In case of solid fuels, for easy combustion, the particle size should be
uniform.

3.7 Solid Fuels

Coal and coke are main solid fuels.
3.7.1 Coal
Coal is the primary and largest solid fuel used to produce electricity and heat through combustion. Black
or brownish black sedimentary rock usually occur as coal beds, composed primarily of carbon along
with other elements like hydrogen, oxygen, nitrogen and sulphur, also known as pulverised carbon.
Due to biogeological processes, from the dead plant matter and vegetation fossil fuel coal is
formed, and is slowly converted into peat, lignite, bituminous coal and finally to anthracite.
According to carbon and hydrogen ratio, ranking of coal in increasing order is as follows
Peat 
→ Lignite 
→ Semibitumiuous coal 
→ Bituminous coal 
→ Anthracite 
→ Graphite
3.7.2 Analysis of Coal

Proximate and ultimate analysis is carried out to assess and determine the quality of coal.
3.7.2.1 Proximate Analysis of Coal

Practical utility of coal is determined by the proximate analysis. Here, information is obtained regard-
ing moisture, volatile matter, ash and fixed carbon content.
(i) Moisture: In a crucible weighed about 1 g of finely powdered air dried coal sample is placed
inside an electric oven at 105–110°C for 1 h. After that, the crucible is taken out from the oven,
cooled in a desiccator and weighed. Difference in the weight gives information about weight loss
as moisture.
weight loss
% moisture = ×100
weight of coal
(ii) Volatile matter: Dried matter of coal left in crucible (a) is covered with a lid and heated up to
950°C for 7 min in a muffle furnace. The crucible is cooled first in air, next in a desiccator and
then weighed. Loss of weight is due to the volatile matter present.
weight loss
% volatile matter = ×100
weight of coal
(iii) Ash: The residual sample in the crucible (b) is repeatedly heated and cooled (air and desiccator)
up to getting content weight in muffle furnace around 700–750°C and the remaining residue is
responsible for ash.
weight of residue left
% Ash = ×100
weight of coal
(iv) Fixed carbon: Fixed carbon is determined by the following equation

% Carbon = 100 − (% moisture + volatile matter + ash)
Good quality of coal has more fixed carbon.

3.7.2.2 Ultimate Analysis of Coal

Elemental analysis of coal is done by ultimate analysis, and with this analysis carbon, hydrogen, nitro-
gen, oxygen, sulphur and ash content are determined based on the following procedure.
(i) Carbon and hydrogen: In a combustion apparatus, accurately weighed 1–2 g of a coal sample is
burnt in a oxygen current. The coal sample containing carbon and hydrogen is converted into
carbon dioxide and water, and the formed gaseous products are absorbed by known weight of
potassium hydroxide and calcium chloride tubes, respectively. From the weight difference of the
tubes, percentage of carbon and hydrogen is determined as follows.
C + O2 → CO2 (12 parts by mass of carbon gives 44 parts
12 44 by mass of carbon dioxide)
2KOH + CO2 → K 2 CO3 + H 2 O
1
H 2 + O2 → H 2 O (2 parts by mass of hydrogen gives 18 parts by mass of water)
2 2 18
7H 2 O + CaCl 2 
→ CaCl 2 ⋅ 7H 2 O
weight increase in KOH tube × 12 × 100
% carbon =
weight of coal × 44
weight increase in CaCl 2 tube × 2 × 100
% hydrogen =
weight of coal × 18
(ii) Determination of Nitrogen content by Kjeldahl method: In a Kjedahl flask (long-necked flask),
about 1g of accurately weighed powdered coal is heated with concentrated sulphuric acid and
potassium sulphate as a catalyst. After getting a clear solution treated with excess KOH, liber-
ated ammonia is distilled over and absorbed by known volume of standard acid solution. Unused
acid is determined with standard NaOH by back titration. Nitrogen content in coal is calculated
from the volume of acid used by liberated ammonia.
volume of acid used × normality × 14 × 100

% nitrogen =
weight of coal
(iii) Sulphur: Sulphur content in coal is determined from the washings obtained in the determination
of calorific value by the bomb calorimeter. During the determination of calorific value, entire
sulphur present in coal is converted into sulphate. The washings are treated with barium chlo-
ride solution, and the sulphate is precipitated as barium sulphate, then it is filtered, washed and
heated for obtaining a constant weight.
weight of BaSO 4 obtained × 32 × 100
% sulphur =
233 × weight of coal taken in bomb calorimeter
(iv) Ash: Ash content is determined as in proximate analysis.
(v) Oxygen: Oxygen content is determined by using the following equation
% Oxygen = 100 − %(C + H + S + N + ash)

3.10
Solved Numerical Problems Based on Combustion of Fuel

(i) A sample of coal was analysed as follows: Exactly 2.500 g was weighed into a silica crucible.
After heating for one hour at 110 °C, the residue weighed 2.415 g. The crucible next was covered
with a vented lid and strongly heated for exactly seven minutes at 950 ± 20 °C. The residue
weighed 1.528 g. The crucible was then heated without the cover until a constant weight was
obtained. The last residue was found to weight 0.245 g. calculate the percentage results of the
above analysis.
Solution Mass of moisture in coal sample = 2.500 – 2.415
= 0.085 g
Mass of volatile matter = 2.451 – 1.528
= 0.887 g
Mass of ash = 0.245 gm
0.085 × 100
Percentage of moisture = = 3.400%
2.5
0.887 × 100
Percent of volatile matter = = 35.48%
2.500
0.245 × 100
Percent of ash = = 9.8%
2.5
Percent of fixed carbon = (100 – (3.4 + 35.48 – 9.80))
= 51.32%
(ii) Calculate the mass of air needed for complete combustion of 5 kg of coal contain;
C – 80%, H = 15%, O = rest.
Solution 5 kg of coal contains: C = 4 kg; H = 0.75 kg; O = (5 – 4 – 0.75) kg = 0.25 kg
\ Amount of air required for complete combustion of 5 kg coal
= [5 × (32/12) + 0.75 × (16/2) – 0.25] kg × (100/23)
= [13.333 + 6.000 – 0.25] kg × (100/23) = 82.97 kg
(iii) A sample of coal was found to contain; C – 80%, H – 5%, O – 1%, N – 2% remaining being
ash. Calculate the amount of minimum air required for complete combustion of 1 kg of coal
sample.
Combustion reaction Wt. of air required

C + O2 → CO2 800 g (32/12) = 2146 gm
12 32 50 g (16/2) = 400 gm
2H + 0.5O2 → H2O Total = 2546 gm
2 16 Less O in fuel = 10 gm
Net O2 reqd. = 2536 gm
\ wt. of air reqd. = 2536 g (100/23) = 11026 gm = 11.026 kg.


(iv) Calculate the weight and volume of air required for combustion of one kg of Carbon?
Solution Carbon undergoes combustion according to the equation.
C + O2 → CO2
12 32
Thus wt. of O2 required for combustion of 12 gm of C = 32 gm.
32
Hence weight of oxygen required by 1 kg of carbon = × 1 = 2.667 kg
12
100
\ wt. of air (containing 23% oxygen) required = × 2.667 = 11.59 kg
23
Now since 32 gm of oxygen occupies 22.4 litres at NTP
22.4
\ 2.667 × 1000 gm of O2 will occupy =
× 2.667 × 1000 = 1866.9 L
32
So, volume of air (containing 21% oxygen) required
100
= × 1866.9 = 8890 Litres = 8.89 m3
21
(v) A gas has the following composition, by volume: H2 = 30%; CH4 = 5%; CO = 20%; CO2 = 6%;
O2 = 5% and N = 34%. If 50% excess air is used find the weight of air actually supplied per m3
of this gas. [molecular weight of air = 28.97]
Solution In one m3 of the gas
Composition of components Volume of O2 needed

H2 (30%) = 0.3 m 3
0.3 × 0.5 = 0.5 m3
CH4 (5%) = 0.05 m3 0.05 × 2 = 0.1 m3
CO (20%) = 0.2 m3 0.2 × 0.5 = 0.1 m3
O2 (5%) = 0.05 m3 Total = 0.35 m3
Less O2 in fuel gas = −0.05 m3
Net O2 needed = 0.3 m3 = 300 L
100 150
Volume of air required for 1 m3 of gas using 50% excess air = 300 × × = 2142.8 L
21 100
Hence, weight of air actually supplied per m3 of the gas,
 1 mol   28.97 gm 
= 2142.8 L ×  ×
 22.4 L   mol 
= 2771 gm
(vi) A gaseous fuel has the following composition by volume; H2 = 20%; CH4 = 5%; CO = 20%;
CO2 = 5%; N2 = 45%. If 50% excess of air is used find the weight of air actually supplied per m3
of this gas?

3.12
Solution Volume of components in 1 m3 of gaseous fuel and O2 needed for combustion can be
calculated as:
Composition Combustion equation Volume of O2 needed

H2 = 0.20 m 3
H2 + 0.5O2 → H2O 0.20 × 0.5 = 0.1 m3
CH4 = 0.20 m3 CH4 + 2O2 → CO2 + 2H2O 0.05 × 2 = 0.1 m3
CO = 0.20 m3 CO + 0.5O2 → CO2 0.2 × 0.5 = 0.1 m3
Total = 0.3 m3 = 300 L
∴ Volume of air required for 1 m3 of gas using 50% excess air

100 150
= 300 × × = 2142.8 L
21 100
Hence, weight of air actually supplied per m3 of gas

28.94 28.94
= Volume × = 2142.8 × = 2768.4 L
22.4 22.4
(vii) Calculate volume of air required for complete combustion of litres of CO, given percentage of
oxygen in air 21.
Solution Combustion reaction volume of O2 needed
CO + 0.5O2 → CO2 5 L × 0.5 = 2.5 L
Hence, volume of air required
100
= 2.5 × = 11.9 L
21
(viii) A producer gas has following composition by volume: CH4 = 5%; CO = 30%; H2 = 20%; CO2 =
5%; N2 = 40%. Calculate the theoretical quantity of air required per cubic meter of the gas.
Solution volume of component in 1m3 of gaseous fuel and O2 needed for combustion can be
calculated as:
Composition Combustion equation Volume of O2 needed

CH4 = 0.05 m 3
CH4 + 2O2 → CO2 + 2H2O 0.05 × 2 = 0.1 m3
CO = 0.3 m3 CO + 0.5O2 → CO2 0.3 × 0.5 = 0.15 m3
H2 = 0.2 m3 H2 + 0.5O2 → H2O 0.2 × 0.5 = 0.1 m3
Total = 0.35 m3
\ Volume of air required for 1 m3 of gas

100
= 0.35 × = 1.67 m3 .
21
(ix) A coal sample gave the following analysis: C = 66.2%; H = 4.2%; O = 6.1%; N = 1.4%; S = 2.9%;
moisture = 9.7% and ash = 9.5%. If one kg of coal is burnt with 25% excess air, d etermine the
quantity of products of combustion?
Solution One kg of coal sample contains:
C = 662 gm; H2 = 42 gm; S = 29 gm; O = 61 gm; H2O = 97 gm

Weight of oxygen needed for Weight of products

Combustion reaction combustion of combustion
32 44
C + O2 → O2 662 × = 1765.3 gm CO2 = × 662 = 2427.3 gm
12 12
16 18
H2 + 1/2O2 → H2O 42 × = 336 gm H 2O = × 4 L = 378 gm
2 2
32 64
S + O2 → SO2 29 × = 29 gm SO2 = × 29 = 58 gm
32 32
Total = 2130.3 gm
Less O2 in fuel = -61 gm
Net O2 needed = 2069.3 gm
Hence, minimum weight of air required for complete combustion of 1 kg of coal

100
= 2069.3 × = 8996.96 gm (1)
23
(Because the air has 23% (by oxygen weight))
And weight of air supplied for combustion using 25% excess air
125
= 8996.96 ×= 11246.2 gm (2)
100
Since, total weight of products of combustion
= Weight of [excess O2 + N2 + H2O + SO2 + CO2] (3)
\ We should first calculate individual weights of products.
Now, weight of excess O2 = 25% of Net O2 used {equation (1)}
25
= × 2096.3 = 5173 gm
100
Weight of N2 = 77% of weight of air + weight of N2 present in fuel
77
= × 11246.2 + 14 = 8659.6 gm
100
Weight of H2O = 378 + 97 = 475 gm
Weight of SO2 = 58 gm
Weight of CO2 = 2427.3 gm
\ Total weight of products of combustion
= Weight of (excess O2 + N2 + H2O + SO2 + CO2)
= 517.3 + 8659.6 + 475 + 58 + 2427.3 gm = 12137.2 gm
= 12.137 gm
(x) The percentage composition of a sample of bituminous coal was found to be as under: C = 75.4%;
H = 5.3%; O = 12.6%; N = 3.2%; S = 1.3% and Ash = rest. Calculate the minimum weight of air
necessary for complete combustion of 1 kg of coal and percentage composition of dry products
of combustion by weight:

3.14
Solution Total weight O2 needed
 32 16 32 
=  C × + H × + S ×  gm
 12 2 32 
32
= 754 × + 53 × 8 + 13 × 1 = 2447.6 gm
12
Less O2 in coal = 126 gm

\ Net O2 needed = 2321.7 gm
So, minimum weight of air necessary for complete combustion
100
= 2321.7 × = 10094.2 gm = 10.09 kg
23
Dry products of combustion
44 44
CO2 = ×C = × 754 = 2764.7 gm
12 12
64 64
SO2 = ×S = × 13 = 26 gm
32 32
N2 = 77% of weight of air + in fuel
77
= × 10094.2 + 32
100
= 7804.5 gm
Total weight of dry products of combustion = weight of (CO2 + SO2 + N2)
= 2764.7 + 26 + 7804.5 = 10595.2 gm
2764.7
\ Percentage of CO2 = × 100 = 26.09% .
10595.2
26
Percentage of SO2 = × 100 = 0.245%
10505.2
7804.5
Percentage of N 2 = × 100 = 73.66%
10595.2
(xi) The coal has following analysis:
C = 54%; H = 6.5%; O = 3%; N = 1.8%; moisture = 17.3 and remaining is ash. This coal on com-
bustion with excess of air, gave 21.5 kg of dry flue gases per kg of coal burnt. Calculate percent-
age of excess air used for combustion.
Solution 1 kg of coal contains
C = 0.54 kg: H = 0.065 kg; O = 0.03 kg; N = 0.018 kg
Minimum weight of air required for combustion
 32 16  100
=  0.54 × × 0.065 × − 0.03 × = 8.39 kg
 12 2  23

Weight of dry products of combustion

44
CO2 = 0.54 × = 19.8 kg
12
77
N 2 = 0.018 × 8.39 × = 6.478 kg
100
\ Total weight of dry products combustion = 1.98 + 6.478 = 8.458 kg
Given, the actual weight of dry flue gases is 21.5 kg. so balance must have come from excess air
= 21.5 - 8.458 = 13.42 kg
13.042
Hence percentage of excess air = × 100 = 155.45%
8.39
(xii) The percentage composition of a sample of coal by weight was found to be C = 76%; H = 5.2%;
O = 12.8%; N = 2.7%; S = 1.2%. the remaining being ash. Calculate the minimum: (a) weight,
and (b) volume at NTP of air necessary for complete combustion of 1 kg of coal. Also calculate
percentage composition of dry products by weight, if 50% excess air is supplied.
Solution 1 kg of coal contains
C = 760 gm: H = 52 gm; S = 12 gm; O = 128 gm; N = 27 gm
\ Net O2 needed for combustion = (O2 needed for combustion)-(O2 is fuel)
 32 16 32 
=  × 760 + × 52 + × 12 − (128) = 2326.7 gm
 12 2 32 
Now, weight of air necessary for complete combustion of 1 kg of coal
100
= 2326.7 × = 10115.9 gm = 10.116 kg
23
And volume of air necessary for complete combustion of 1 kg of coal
22.4 L 1 m3
= 10115.9 gm × × = 7.83 m3
28.94 gm 1000 L
Weight and percentage of dry products of combustion are calculated below:

44
CO2 = × 760 = 2786.7 gm
12
64
SO2 = × 12 = 24 gm
32
77 150
N 2 = 27 gm (in fuel) + × 10116 × = 11710.9 gm
100 100
50 50
O2 = Minimum weight of O2 × = 2326.7 × = 1163.7 gm
100 100

3.16
Total weight of dry products of combustion = weight of (CO2 + SO2 + N2 + O2)

= 2786.7 + 24 + 11710.9 + 1163.4 = 15684.97 gm
2786.7
\ Percentage of CO2 = × 100 = 17.77%
15684.97
24
Percentage of SO2 = × 100 = 0.153%
15684.97
11710.9
Percentage of N 2 = × 100 = 74.7%
15684.97
1163.4
Percentage of C2 = × 100 = 7.417%
15684.97
3.7.3 Metallurgical Coke

Coke used for metallurgy is called metallurgical coke, and it should have the following good
characteristics.
(i) Purity: Low moisture content keeping down the heating expenses. Ash content hinders the heat-
ing, forms slag and also consumes excess coke for removal of ash. The sulphur and phosphorous
produce undesirable products like SO2, P2O3, P2O5 etc. Which affect the quality of coke, and also
sulphur make the coke brittle. Hence coke should have as low as possible moisture, ash, phos-
phorous and sulphur contents.
(ii) Calorific value: Coke should have a high calorific value.
(iii) Strength: It should be quite compact, strong, hard to withstand abrasion as well as pressure in
furnace.
(iv) Porosity: For complete combustion at high rate, coke should be porus, due to presence of pores
oxygen can easily contact with carbon.
(v) Size: If coke is too big in size, uniformity of heating is not maintained, and if it is too small chok-
ing is observed. Hence, the size of the metallurgical coke should be medium.
(vi) Cost availability and transportation: Coke should be easily available with cheap rate nearer the
metallurgical plant, therefore, with this the transportation cost is also reduced.
(vii) Combustibility: The combustibility of the coke mainly depends on nature of coal, carbonization
temperature, reaction temperature, etc. Further, cokes obtained by high temperature carboni-
zation process are less combustible when compared to coke obtained by low temperature car-
bonization at a given temperature. All cokes have equal reactivity at 800–900°C temperature.
The rate of combustion depends on the rate of oxygen supply about 1000°C. Coke should burn
easily.
(viii) Reactivity of steam: Coke obtained from non-caking coals is more reactive to steam when com-
pared with caking coals. Reactivity to steam of coke is directly proportional to reaction tem-
perature and inversely proportional to carbonization temperature. Especially, the coke used for
manufacture of water gas must be reactive to steam.

3.7.4 Manufacture of Metallurgical Coke

The coke, for metallurgical purposes, is mainly manufactured by two methods. They are (1) Beehive
oven and (2) Otto Hoffman’s by-product oven method.
(i) Beehive oven: Schematic representation of Beehive oven is shown in Figure 3.3. This is the cheap
and earliest method for manufacturing of metallurgical coke. The Beehive oven is the dome-
shaped structure of bricks, with 4 m width and 2.5 m height. It is having two openings, and these
can be opened and closed as desired. Thus, coal is charged from the top opening, and air supply
as well as coke discharge from side opening is used.
Through the top opening, coal is charged about 0.6 m deep layer, air is supplied from the side
opening and the coal ignited. For slow carbonization, combustion is allowed to proceed gradual
diminish supply of air, and it will take to complete 3 to 4 days from the top to bottom layer and
the volatile matter escapes inside the partially closed door. After completing and carbonization,
the hot coke quenched with water and raked out through the side door, leaving the oven hot to
start the next charge batch carbonization. The yield is 80 per cent of the charged coal. Many
such ovens are arranged in series, and with this waste heat is utilized for heating. Hence, it saves
energy, reduces the pollution and is economically beneficial.
Coal charging door
Refractor lining
Zone of combustion
Heat radiated
from the roof to
2.5 m
the coal bed Coal Door for
air supply or
0.6 m coke discharging
4m
Figure 3.3 Beehive coke oven

(ii) Otto Hoffman’s by-product oven: Schematic representation of the modern by-product coke oven,
which is developed by Otto Hoffman is shown in Figure 3.4. It is mainly useful in (i) increased
thermal efficiency of carbonization and (ii) recovery of valuable by-products like ammonia, coal
gas, benzol air, tar etc., It is heated externally by coal gas produced itself or blast furnace gas or
producer gas, and mostly heating is done by heat economy of regenerative system, i.e., utilization
of flue gases for heating.
The oven consists of a number of narrow silica chambers about 10 to 12 m long, 3 to 4 m high
and 0.40 to 0.45 m width. These chambers are erected side by side vertically; further, flues in
between them form a sort of battery. Each chamber is provided at the top with a charging hole,
at the end of chamber a gas off-take and refractory lined cast iron door for discharging coke.
A finely crushed coal is introduced through the charging holes, closed tightly on both the ends to
prevent air access. The oven is heated to 1200°C by employing a regenerative principle, with burning
of producer gas. During combustion, produced flue gases pass towards sensitive checker brick work
until the temperature raises about 1000°C before escaping to chimney. The flow of heating gases is
reversed, to serve in the preheat of inlet gases and the cycle goes on. The heating process is continued
up to 11 to 18 h, till the carbonization and evolution of volatile matter ceases completely. After com-
plete carbonization, a massive ram pushes the red hot coke into a truck and subsequently quenched.

3.18
Chambers loaded with

coal
Coal gas
al
Co Coal bunker
Coal Space between
Coal gas chambers for
charging cars flow of burnt
gases
Tar
Hot
Coke
Gas burns here regenerators
Ram chamber
(Coke Regenerators Outgoing waste
pusher) gases heat
regenerators
before escaping
Coke oven with regenerators
to chimney
Waste gases Air Producer Waste gases
to chimney gas to chimney
Figure 3.4 Otto Hoffman’s by-product coke oven with regenerators
3.8 Liquid Fuels

Liquid fuels are those which are combustible, energy-generating substances and play vital role in
transportation and economy. Most widely used liquid fuels are derived from fossil fuel/petroleum/
crude oil. Some important liquid fuels are petrol, kerosene, diesel, etc.
3.8.1 Petroleum Refining

Petroleum is a complex mixture of organic liquids (hydrocarbons) also known as crude oil or fossill
fuel. It is formed from the fossilized dead plants and animals by exposure to heat and pressure in the
Earth’s crust, and was formed millions of years ago. It is a viscous dark coloured, foul-smelling liquid
along with water and soil particles. Hence, it is necessary to separate these hydrocarbons into useful
products, and this process is known as fractional distillation. In this process, products are separated
depending on boiling points, known as refining of petroleum, and the plant set-up used here are oil
refineries as shown in Figure 3.4.
Refining of petroleum involves the following 3 steps.
Step I: Separation of water by Cottrell’s method: Petrol or crude oil is the emulsion of oil and salt
water, and these colloidal water droplets coalesce to form large drops which can separate out
from oil when the crude oil is sent through two highly charged electrodes.
Step II: Removal of sulphur compounds: crude oil is treated with copper oxide, sulphur reacts with
copper to form copper sulphide precipitate, which is removed by filtration
Doctors sweetening process: The process was described by G. Wendt and S. Diggs. Here,
crude oil is treated with sodium plumbate, i.e., doctors solution, converts mercaptans in sour
gasoline into disulphide.
RSH + Na 2 PbO2 powdered
S in presence of NaOH
→ R − S − S − R + PbS + 2NaOH
Mercaptan from Gardine (sodium plumbate) (alkyl disulphide)

Gases
Petroleum
Tray
ether
Gasoline
Chimney
Down Naphtha
spot
Loose Kerosene
cap
Diesel oil
Lubrication
oil
Steam
Crude
oil Fumace
at 400°C Heavy
oil
Figure 3.5 Fractional distillation of crude petroleum
Step III: F
ractional distillation: In an iron retort, the crude oil is heated to about 400–430°C. Here,
all volatile matter are evaporated, components which are not volatile like tar and asphalt are
settled at the bottom of the column. The hot vapours are then passed through a distillation
column, shown in Figure 3.5.
The distillation chamber is a steel cylindrical tube about 31 m height and 3 m in diameter, and inside,
the chamber trays are fitted at short distances. Every tray is having many holes and an up going short
tube with a bubble cap. At different heights of chamber, the vapours go up, begin to cool and condense
in fractions. Fractions which are having higher boiling point condenses first and lower boiling frac-
tions one after other. Various products obtained in distillation are given in Table 3.1.
Table 3.1 Fractions by distillation of crude

Approx. composition in
terms of hydrocarbon
Name of fraction Boiling range containing C atoms Uses
1. Uncondensed gas. Below 30 °C C1 to C4 As domestic or industrial fuel under
(such as ethane, the name L.P.G. (liquefied petroleum
propane, isobutane) gas).
2. Petroleum ether. 30–70 °C C5–C7 As a solvent.
(Continued )

3.20
Table 3.1 (Continued)
Approx. composition in
terms of hydrocarbon
Name of fraction Boiling range containing C atoms Uses
3. Gasoline or petrol or 40–120 °C C5–C9 As motor fuel, solvent and in dry
motor spirit. (calorific value = 11,250 cleaning.
kcal/kg)
4. Naphtha or solvent spirit. 120–180 °C C9–C10 As solvent and in dry cleaning.
5. Kerosene oil. 180–250 °C C10–C16 As an illuminant, jet engine fuel and

(calorific value = 11,000 for preparing laboratory gas.
kcal/kg)
6. Diesel oil or fuel oil or 250–320 °C C10–C18 Diesel engine fuel.

gas oil. (calorific value = 11,000
kcal/kg)
7. Heavy oil. 320–400 °C C17–C30 For getting gaso-line by cracking

This on refractionation process.
gives: As lubricant
(a) Lubricating oil As lubricant and in cosmetics and
(b) Pertoleum jelly. medicines.
(Vaseline) As lubricant
(c) Grease In candles, boot polishes, wax paper,
(d) Paraffin wax. tarpolin cloth, etc.
8. Residue may be either: Above 400 °C C30 and above Water-proofing of roofs and road
(a) asphalt making.
or As a fuel and in moulding are light
(b) Petroleum coke. rods.
3.8.2 Important Petroleum Products and their Uses

(i) Gasoline (or) petrol (or) motor spirit: In North America, gasoline is often shortened as gas,
while petrol is the common name in the United Kingdom. It is a transparent petroleum derived
oil obtained between 40 to 120°C as mixture of hydrocarbons C5H12–C8H8. Its calorific value
is about 11,250 kcal/kg, with 84 per cent of carbon, 15 per cent of hydrogen and 1 per cent of
nitrogen, sulphur and oxygen as its composition. It is highly volatile inflammable oil, primarily
used as a fuel for internal combustion engines of automobiles.
(ii) Kerosene oil: Kerosene is the fraction obtained between 180 to 250°C, as a mixture of hydro-
carbons C10H22–C16H34 in petroleum distillation. Its calorific value is about 11,000 kcal/kg, with
84 per cent of carbon, 16 per cent of hydrogen and less then 0.1 per cent of sulphur as its composi-
tion. It is widely used fuel for cooking, also used as an jet engine fuel and for making oil gas.
(iii) Diesel oil: In a petroleum distillation, it is a fraction obtained between 250 to 320°C as a mixture
of hydrocarbons of C15H32–C18H38. Its calorific value is about 11,000 kcal/kg, and is mainly used
as a diesel engine fuel.

(iv) Liquefied petroleum gases (LPG): This is obtained from cracking of heavy oils (or) natural gas
and named as bottled gas. It consist of n-butane, isobutene, butylene, propane and less ethane,
and supplied under pressure containers with the trade name of Indane gas, Bharat gas, etc. LPG
is dehydrated, desulphurized and added trace amounts of mercaptans for giving warning of gas
leak, and its calorific value is about 27,800 kcal/m3. It is widely used as a domestic, industrial and
motor fuel.
3.9 Synthetic petrol

Petrol can be synthesized by the following methods.
(i) Cracking
(ii) Fischer–Tropsch method and
(iii) Bergius method
3.9.1 Cracking
The process of breakdown of high molecular weight hydrocarbons of high boiling points into simple,
lower molecular weight hydrocarbons of low boiling points is known as cracking.
cracking
Example: C10 H 22 → C5 H12 + C5 H10
Decane n-pentane pentene
With these we can prepare different fuels having high quality.

Cracking is mainly two types: thermal and catalytic cracking.
3.9.1.1 Thermal Cracking

In this cracking heavy oils are subjected to high temperature and pressure in the absence of catalyst.
In this cracking, the bigger hydrocarbon molecules break down to give smaller paraffins and olefins.
Mechanism of Cracking Process

Cracking processes invoke free radical and carbonium ion intermediates. Thermal cracking mainly
goes through the free radical mechanism. In this mainly of three steps they are as follows: Example:
Thermal cracking of nonane.
Initiation: Nonane undergoes homolytic cleavage at high temperature to give free radicals.
•
High temp
CH 3 − (CH 2 )7 − CH 3 
→ 2CH 3 − (CH 2 )3 − C H 2
Propagation: The formed free radicals undergo further fissions up to thermally more stable radical
is formed.
• •
CH 3 − CH 2 − CH 2 − CH 2 − C H 2 → CH 3 − CH 2 − C H 2 + CH 2 = CH 2
• •
CH 3 − CH 2 − C H 2 → C H 3 + CH 2 = CH 2
•
CH 3 C H 2 → H 2 C = CH 2 + H i

3.22
Termination: Coupling of unstable free radical intermediates gives final products in termination reaction.
• •
C H 3 + C H 3 → CH 3 − CH 3
• •
H 3 C − C H 2 + C H 2 − CH 3 → H 3 C − CH 2 − CH 2 − CH 3
•
H 3 Ci + C H 3 → H 3 C − CH 3
•
H 3 C − C H 2 + H i → H 3 C − CH 3
3.9.1.2 Catalytic Cracking

In catalytic cracking, higher molecular weight hydrocarbons breakdown in the presence of catalyst
like alumina (or) aluminium sulphate via carbonium ion intermediate. Here, quality and quantity of
gasoline can be increased, and it is mainly of two types. They are as follows:
(i) Fixed bed catalytic cracking
(ii) Moving bed catalytic cracking
Mechanism of Catalytic Cracking

This reaction proceeds via carbonium–ion intermediates.
(i) Fixed-bed catalytic cracking: A simple sketch of fixed bed catalytic cracking is shown in Figure
3.6. Here, heavy oil charge is passed through a pre-heater, having a temperature of about 425–
450°C. The formed hot vapours of oil is passed over a fixed bed of catalyst chamber also having
the temperature of about 425–450°C.
Cooler
Cracked Stabilizer
Catalyst vapour Gases
Vapour
Gasoline
Heavy + Heavy
oil charge Heater
− oil
Pre-heater Catalyst Fractionating
(425−450°C) chamber coloumn Gasoline
(425−450°C) +
Some dissolved gas
Figure 3.6 Fixed-bed catalytic cracking
In a catalytic chamber, 40 per cent of oil is converted into petrol and 2–4 per cent of carbon
formed is absorbed on the catalyst bed. Catalyst stops function after 8–10 h, and due to car-
bon deposition it deactivates. This is re-activated by burning off the deposited carbon, During
re-activation, the vapours are directed through another catalyst chamber.
Cracked vapours enter into the fractionating column from the catalyst chamber, and different
gases are cooled and collected.
(ii) Moving-bed catalytic cracking: A schematic representation of a moving bed catalytic cracking
is shown in Figure 3.7. Here, feed oil is passed through a pre-heater, oil vapours formed here

along with very finely powdered catalyst are passed to a reactor, which maintain about 500°C
temperature. The cracked oil vapours are then passed through fractionating column, and heavy
oil is separated. Formed vapours are sent to a cooler, gasoline condenses along with gases, and
is separated from gases as a purified petrol.
Cracked
Flue gases Cooler
vapour Light
Cyclone fraction
Gases
Catalyst
regenerator 600°C 500°C Gases
Regenerator Stabilizer
Catalyst
Reactor Spent Heavy
Feed oil Gasoline
catalyst
oil Fraction Gasoline
matching + gas
Catalyst coloumn
+ oil Air
Blower
Figure 3.7 Moving-bed type catalytic cracking
3.9.2 Fischer–Trapsch Method

Oven-heated coke is mixed with hydrogen and passed steam through it, and water gas (CO + H2) is
formed. It is purified by passing through first Fe2O3, here H2S is removed, next a mixture of Fe2O3 +
Na2CO3, removes organic sulphur compounds. The purified gas is then compressed to 5–25 atm and is
sent through a converter containing catalyst. Catalyst is the mixture of 100 parts of cobalt, 8 parts of
magnesia, 5 parts of thoria and 200 parts of keiselgur at 200–300°C temperature. A mixture of satu-
rated and unsaturated hydrocarbons is formed.
nCO + 2n H 2 
→ Cn H 2n + nH 2 O
unsaturated hydrocarbon
nCO + (2n + 1) H 2 
→ Cn H 2n + 2 + nH 2 O
saturated hydrocarbon
This reaction is highly exothermic. Hence, formed hot gaseous mixture is sent to a cooler. Here,
liquid like crude oil is formed, and passed through a fractionating column. From the column, petrol
and heavy oil are formed. Cracking of heavy oil gives and petrol. Schematic diagram of Fisher-Tropsch
method is shown in Figure 3.8.
3.9.3 Bergius Method

A paste of finely powdered low ash coal, heavy oil and tin or nickel oleate (catalyst) is heated with
hydrogen at 450°C temperature, and 200–250 atm pressure for about 1.5 h. Here, hydrogen reacts with
coal to give saturated hydrocarbons, these are send to condense. Liquid like crude is formed and sent to
fractionating column. From the column petrol, middle oil and heavy oil are formed. Heavy oil is used
further for making paste with fresh coal. The middle oil is hydrogenated in presence of a solid catalyst
in vapour phase to give petrol. The schematic diagram of Bergius process is shown in Figure 3.9.

3.24
Catalyst
(Co + Th + MgO)
+ Keiselguhr)
Cooler
Fe2O3 Fe2O3
+
Na2CO3 Gasoline
Water gas
(CO + H2)
Cracking
Heavy Gasoline
oil
Compressor
Purification (5-25 atm)
Fractionating
H2 of gas column
Figure 3.8 Fischer–Trapsch method
Powedered
coal
Heavy Condenser Gases
oil Catayst Gases
(Sn or Ni
oleate) H2
Gasoline
Paste Middle
oil Gasoline
H2
Heavy
oil
Convertor at Fractionating
Crude
450°C and 200-250 atm coloumn
oil
Figure 3.9 Bergius method
3.10 Power alcohol

Power alcohol is one of the most important non-petroleum fuels. The first four aliphatic alcohols,
methanol, ethanol, propanol and butanol, can be synthesized chemically or biologically and used as a
fuel for internal combustion engines. These are not used as a prime fuel, but used in blends as additives.
Chemical formula of power alcohol is CnH2n+1 OH.

3.10.1 Manufacture of Power Alcohol

Methanol can be prepared from biomass. Ethanol is commonly prepared from various biological
organic substances through fermentation process. However, widely it is manufactured from molasses.
It is a viscous semisolid material, left after crystallization of sugar from sugar cane juice. It is a mixture
of sucrose, glucose and fructose.
The molasses are diluted with water, to reduce sugar concentration from about 50–60 per cent to
10–12 per cent. Nutrients like ammonium sulphate, ammonium phosphate, and some amount of sulphu-
ric acid is added to maintain pH value around 4-5. Right proportions of yeast are added and maintain
the temperature of about 30°C. The invertase enzyme of yeast converts entire sucrose into glucose and
fructose.
C12 H 22 O11 + H 2 O Invertase


30° C
→ C6 H12 O6 + C6 H12 O6
Sucrose Glucose Fructose
The zymase enzyme of yeast converts entire glucose and fructose into ethyl alcohol and releases
carbon dioxide. During this process CO2 produces lot of froth, hence this process is known as fermen-
tation process.
C6 H12 O6 Zymase

30° C

→ 2C2 H 5 OH + 2CO2 (g)
Glucose/fructose Ethyl alcohol
The fermentation process may be completed in about 36–38 h. Depending on the concentration of
alcohol, it is named as wash or rectified spirit or absolute alcohol.
Wash: The fermented liquid containing 18–20 per cent of alcohol is known as wash.
Rectified spirit: Fractional distillated wash contains 90–95 per cent alcohol, and it is known as rectified
spirit.
Absolute alcohol: The rectified spirit is digested with lime for about 2 days and then distilled to get 100
per cent alcohol which is known as absolute alcohol.
Advantages
(i) These are prepared from waste, hence it is a good non petroleum alternative source of energy
and also reduces the pollution.
(ii) It can burn completely, thereby increasing combustion efficiency.
(iii) It has an octane value of about 90, but petrol is having about 60–70. When alcohol mixes with
petrol, it tends to increase the octane rating, and these blended petrol possesses better antiknock
property and reduces the carbon monoxide emission.
(iv) Petrol is blended with alcohol, and it can absorb traces of moisture.
Disadvantages
(i) Alcohol may cause corrosion due to easy oxidation with acids.
(ii) Due to low calorific value of alcohol, more fuel is required for each mile driven.
(iii) Particularly at low temperatures, alcohol is difficult to atomize, due considerable surface
tension.

3.26
3.11 Knocking
Knocking is the metallic sound produced by a spark ignition petrol engine under certain conditions.
The following terms can explain the knocking in better way.
(i) Ignition temperature: It is the minimum temperature at which the combustion is self-supporting.
This is also referred to as spontaneous ignition temperature (SIT).
(ii) Compression ratio (CR): The power output and efficiency of an IC engine depends on a factor
called CR. It is defined as the ratio of gaseous volume (V1) in the cylinder at the end of suction-
stroke to the volume (V2) at the end of compression-stroke of the piston.
V
As V1 > V2 ⇒ CR = 1 > 1
V2
The CR obviously indicates the extent of compression of fuel–air mixture by the piston.
The fuel–air mixture gets heated to a temperature greater than its ignition temperature as a
result of compression. This leads to spontaneous combustion even before sparking.
It is also possible that the last portion of the fuel–air mixture undergoes self-ignition after
sparking. It is due to the heating and compression of the unburned fuel, by the spreading flame-
font sweeping across the cylinder.
The resulting shock wave dissipates its energy by hitting the cylinder walls and the piston. In
view of the characteristic rattling sound emitted, this is called knocking. The CR at which fuel
tends to knock is called critical CR.
To summarise: With the increase in CR, the efficiency of IC engine also increases but after
critical CR, tendency to knock also increases.
Consequences of knocking:
(a) Decreased power output
(b) Mechanical damage by overheating of the cylinder parts.
Probable mechanisms of chemical reactions that lead to knocking are the following:
(c) Free radical chain reaction leading to cracking and oxidation of the hydrocarbons is probably
the mechanism of chemical reactions that lead of knocking.
Factors on which knocking depend are the following
(1) Engine design
(2) Running conditions and
(3) Chemical structure of the fuel hydrocarbons. For instance:
(d) Knocking tendency decreases in the following order: n-alkanes > mono-substituted alkanes
> cycloalkanes > alkenes > poly-substituted alkenes > aromatics. And for straight chain
hydrocarbons, the tendency to knock increases with molecular weight and boiling point.
Example: n-hexane > n-pentane > n-butane.
Aromatic hydrocarbons have higher anti-knocking properties than paraffins and olefins.
3.12 Diesel Engine, Cetane and octane Number

In the diesel engine, air is first drawn into the cylinder and compressed to a pressure of about 500 psi
(3.52 × 105 kg/m2). This compression is accompanied by a rise in temperature to about 500 °C.

Towards the end of the compression, stroke is injected in the form of finely divided spray into air in
the cylinder heated to about 500 °C by compression. The oil absorbs the heat from the air and it ignites
spontaneously as it attains ignition temperature. This raises the temperature and pressure. The piston
is pushed by expanding gases in the power stroke.
In a diesel engine, combustion of fuel is not instantaneous, as the ignition delay is caused. Ignition
delay is the interval between the start of fuel injection and its ignition. This is due to the time taken
for the vaporization fuel droplets and attaining of the vapour to its ignition temperature. It depends
on the (a) engine design; (b) efficiency of mixing of the spray and air; (c) the injector design; and
(d) mostly on the chemical nature of the fuel. Example: Ignition delay is shorter for paraffinic fuel
than that of olefinic, naphthalenic and aromatic fuels.
If the ignition delay is long, it will lead to fuel accumulation in the engine even before the ignition. When
ignited, an explosion results as the combined effect of increased temperature and pressure. This is responsi-
ble for diesel knock. The diesel fuel should have a SIT less than the temperature produced by compression.
As the temperature to which air can be heated by compression is limited by various constraints, it
is desirable to have fuels with short ignition delay but the ignition delay must be long enough for the
compression stroke to be completed. In order to grade the diesel fuels, cetane rating is employed.
Cetane number: It is used for diesel engines to measure the ease of with which a fuel will ignite
under compression
Diesel fuel Cetane no. Remarks

Cetane 100 Very short ignition delay
C16H34 (or CH3 (CH2)14–CH3, n-hexadecane) 0 Longer ignition delay
X-methyl naphthalene
CH3
Cetane number of fuel primarily depends on the nature and composition of its hydrocarbons.
For instance, consider the following series: n-alkanes > cycloalkanes > alkenes > branched alkanes
> aromatics (i.e. cycloalkanes):
(i) ignition delay increases from left to right
(ii) ignition quality increases from right to left
(iii) cetane no. increases from right to left
As straight chain alkanes such as n-cetane have low ignition delay (high ignition quality) and ignite
readily on compression, while aromatics do not ignite readily on compression, so that high cetane
number fuels eliminate diesel knock. The cetane number of diesel fuel may be raised by the addition
of pre-ignition dopes such as alkyl nitrites such as ethyl nitrite, amylnitrite, etc., 2,2,4,4,6,6,8, 8-hepta
methyl nonane (HMN).
CH3 CH3 CH3 CH3

CH3 C CH2 C CH2 C CH2 C CH3
CH3 CH3 CH3 CH3

3.28
With a cetane rating of 15 is now considered as the low-quality diesel in the view of its easy availability
and purity. On the revised scale (HMN reference), the cetane number (CN) represents the % cetane,
in the blend with HMN plus 15/100 of the % HMN. Thus, a blend of 50% cetane and 50% HMN has a
following cetane rating:
15
50 + × 50 = 57.5
100
Octane number: The resistance offered by gasoline to knocking cannot be defined in absolute terms.
It is generally expressed on an arbitrary scale, known as octane rating.
Fuel Octane number Characteristics

n-Heptane 0 Knocks severely
Iso-octane 100 High resistance to knocking
The % of iso-octane in the n-heptane iso-octane blend which has the same knocking characteristics as
the gasoline sample under the same set of conditions is known as octane number.
Additives for improving anti-knock properties: Tetra ethyl lead (TEL) and diethyl telluside
(C2H5)2Te are the most commonly used additives. TEL gives rise to Pb of PbO during combustion.
These particles act as free-radical chain inhibitors as they arrest the propagation of the explosive chain
reactions responsible for knocking.
The efficiency of TEL decreases in the presence of sulphur hence desulphurised gasoline is
preferred. Pb and PbO2 decrease engine life hence they must be removed along with exhaust gases by
adding ethylene dibromide.
Pb, PbO2 + C2H2Br2 → PbBr2
Because PbBr2 formed is volatile its escape into atmosphere. But pollution problem still exists. Another
cause of pollution is incomplete combustion leading to the formation of CO, NO, NO2, SO2, SO3, etc.
Hence, catalytic converters based on Pt are employed which will catalyse combustion reaction to com-
pletion. Example: CO–CO2.
But Pt is poisoned by Pb, so unleaded petrol should be used. Benzene is added for decreasing
knocking. Since benzene is carcinogenic, very low concentration of benzene should be used.
3.13 Gaseous fuels

Important gaseous fuels are natural gas, producer gas, water gas, coal gas, bio gas, etc.
3.13.1 Natural Gas

Natural gas obtained along with petroleum in oil wells is called wet gas. It is purified and removed.
Propane, propene, butane, butene, etc. are used for preparing LPG. If the gas is associated with crude
oil, it is called dry gas. It is having some of the objectionable ingredients like water, H2S, N2, CO2, etc.
and hydrocarbons like propane, butane, propene, butene, etc. are removed.
Composition
Natural gas consists of 70–90 per cent of methane, 5–10 per cent of ethane, 3 per cent of hydrogen and rest
of carbon monoxide and carbon dioxide, approximately. Calorific value is about 12,000–14,000 kcal/m3.

Uses
(i) Used as a domestic fuel, also conveyed over large distances through pipelines.
(ii) Used as a raw material in carbon block manufacture.
(iii) Used for manufacture of different synthetic chemicals.
(iv) Used in the preparation of synthetic products by microbiological fermentation of methane.
(v) Used in the preparation of compressed natural gas.
(vi) Due to less pollution, it is a good substitute for petrol and diesel.
3.13.2 Producer Gas (or) Suction Gas

Composition
Producer gas is the mixture of about 20–22 per cent carbon monoxide (CO), 11–13 per cent carbon
dioxide (CO2), 20–22 per cent hydrogen (H2), 2.5–3.5 per cent methane (CH4) and 40–42 per cent
nitrogen (N2). Hence main composition is CO + N2.
Manufacture
Air is passed through a red hot coal or coke in a gas producer, and maintained temperature is about
1100°C. Producer gas is formed with oxidation and reduction reactions. Initially, oxidation of carbon
gives carbon monoxide and carbon dioxide.
C + O 2  → CO2 + Energy 
 exothermic reaction
C + 1/ 2 O2 → CO + Energy 
Reduction reaction gives producer gas:
CO2 + C  → 2CO + Energy 


C + H 2 O → CO + H 2 + Energy  endothermic reaction
C + 2H 2 O → CO2 + 2H 2 − Energy 
Formed gas is distilled and purified. The calorific value of producer gas is about 1300 kcal/m3.
Uses
(i) Used in the manufacture of steel, glass, etc. for heating of open-hearth furnace.
(ii) Used in the manufacture of coke and coal gas for heating of muffle furnace.
(iii) Used as a reducing agent in metallurgical operations.
3.13.3 Water Gas (or) Blue Gas

Composition
Water gas is the mixture of carbon monoxide (40–42 per cent), hydrogen (50–52 per cent), nitrogen
(3–4 per cent and carbon dioxide (3–4 per cent).

3.30
Manufacture
Steam and little air are passed alternatively through a red hot coal or coke in a reactor maintained at
about 1000°C temperature and water gas is formed in the following reactions.
→ CO2 + Energy 
C + O 2 
 exothermic reaction
2C + O2 → 2CO2 + Energy 
C + H 2 O 
→ CO + H 2 − Energy (endothermic reaction)
The calorific value of water gas is about 2800 kcal/m3.
Uses
(i) Used as an illuminating gas, fuel gas, source of hydrogen gas etc.
Carbonated water gas: It is a mixture of producer gas and hydrocarbons. Calorific value is about
4500 kcal/m3, and used for illuminating and heating purpose.
Semi-water gas: It is a mixture of water gas and producer gas. Calorific value is about 1700 kcal/m3.
Used as a fuel and a source of N2 and H2 in the manufacture of ammonia.
3.13.4 Coal Gas

Coal gas is mainly used as an illuminant in cities and towns; hence, it is known as town gas or illu-
mination gas.
Composition
It is a mixture of carbon monoxide (27–29 per cent), carbon dioxide (2.4 per cent), hydrogen (16–18
per cent), nitrogen (49–51 per cent) and methane (0.5–1 per cent).
Manufacture
It is manufactured by destructive distillation of coal in the absence of air, at about 1300°C temperature.
1300° C
Coal In 
the absence of air
→ Coal gas ↑
The calorific value of coal gas is about 4900 kcal/m3.
Uses
(i) It is used as a fuel and illuminant.
(ii) Used for maintaining reducing atmosphere in metallurgical operations.
3.13.5 Biogas
Composition
Biogas is the mixture of methane (50–60 per cent), carbon dioxide (30–40 per cent), hydrogen (5–10
per cent), nitrogen (2–6 per cent) and trace amount of hydrogen sulphide.

Manufacture
It is produced by the degradation of biological matter like animal dung, poultry waste, vegetable waste,
waste paper, plant waste, human excreta, birds’ excreta, etc. by the anaerobic bacterial action in the
absence of free oxygen.
Uses
(i) Used for cooking food.
(ii) Used as a fuel to run engines.
(iii) Used as an illuminant.
3.14 Flue gas analysis by Orsats apparatus

Flue gas is the mixture of CO2, CO and O2 gases, exhausted from the combustion chamber. Analysis
of flue gas gives an idea about efficiency of combustion. Suppose the flue gas contains considerable
amount of CO, it indicates incomplete combination and short supply of oxygen, and this will lead to
wastage of fuel. If the flue gas contains considerable amount of oxygen, this indicates excess supply of
oxygen and results in loss of heat.
With the help of Orsat’s apparatus flue gas analysis is carried out, as is shown in Figure 3.10. The set-
up consists of a horizontal tube, with a three-way stopcock at one end and another end is connected with a
graduated burette. For maintaining constant temperature during the experiment, the burette is surrounded
by a water jacket. The burette is connected as a set of three absorption bulbs in a series, through a separate
stopcock. The lower end of the burette is further connected to a water reservoir through a rubber tube.
The water level in the burette can be changed by raising or lowering the reservoir water. One end of
the tube, which is connected to a three-way stopcock, is further connected to a U-tube. For drying flue
gas and avoiding the incoming smoke particles, the U-tube is packed with fused CaCl2 and glass wool.
Among the three absorption bulbs, first bulb has potassium hydroxide solution and absorbs only CO2.
The second bulb contains alkaline pyrogallic acid absorbs only O2 and CO2. The third bulb has ammoni-
cal cuprous chloride and can absorb CO2, O2 and CO. For proper analysis of flue gas, first it is passed
Stop cock
Stop cock
Flue Water
gas reservoir
3 2 1
Amm
cyp- Alk
rous pyro- KOH
Fused CaCl2 chlo- gallic Graduated
+ ride acid
burrete
Glass wool
Rubber
Water tubing
Absorption bulbs jocket
Figure 3.10 The orsats apparatus

3.32
through potassium hydroxide containing bulb, and here CO2 is absorbed. Then, it is passed through alka-
line pyrogallic acid containing bulb, and here O2 is absorbed and it can also absorb CO2, but already it
is removed by KOH. Finally, flue gas is passed through the third bulb containing ammoniacal cuprous
chloride, and here CO is absorbed; however, it can absorb CO2 and O2 also but these are already removed.
The entire apparatus is thoroughly cleaned, the steppers are greased, tested for air tightness, the
absorption bulbs are filled with their respective solution and the stopcocks are closed. The water reser-
voir and water jacket are filled with water, and air is excluded from the burette by the raising of reservoir
water level till the burette is completely filled with water. For the exclusion of air, the three-way stopcock
is opened, next the lowering of water level is done and the fuel gas supply is connected to the three-way
stopcock.
Further, 100 ml of the flue gas is carefully sent to the burette with closing of the three-way stopcock.
The fuel gas is forced through the first bulb by opening its stopcock and raising the water level in the
reservoir. Here, potassium hydroxide absorbs the CO2 flue gas is sent repeatedly 2 or 3 times to the first
bulb for complete absorption of CO2. The remaining gas is taken back in the burette and the stopcock
of the first bulb is closed. The levels of water in the reservoir and burette are equalized and decreasing
volume of gas is noted. This decrease in volume gives the volume of CO2 in 100 ml of flue gas. Similarly,
the volumes of O2 and CO are determined by passing the flue gas through the second and third bulbs,
respectively. The remaining gas in the burette after absorption of CO2, O2 and CO is nitrogen.
The decrease in volume of flue gas by first bulb = volume of CO2
The decrease in volume of flue gas by second bulb = volume of O2
The decrease in volume of flue gas by third bulb = volume of CO.

1. _______ is the C.G.S unit of heat.
[Ans.: Calorie]
2. 1 K Cal = 3.968 B.T.H = _______ C.H.U.
[Ans.: 2.2]
3. _______ is used for determining the calorific value of solid and liquid fuels.
[Ans.: Bomb calorie meter]
4. Latent heat of steam is _______.
[Ans.: 588 cal/gm]
5. The lightest temperature obtained with the fuel is known as _______.
[Ans.: Pyrometric effect]
6. KJeldahl method is used for determination of _______.
[Ans.: Nitrogen]
7. Aromatic hydrocarbons have _______ anti knocking properties than paraffins and olefins.
[Ans.: Higher]
8. In flue gas analysis by orsat’s method _______ containing bulb is absorbed by CO2.
[Ans.: KOH reduction]

1. Which of the following fuels possesses the maximum calorific value?
(a) C = 84%, H = 6%, S = 4% and O = 6% (b) C = 84%, H = 12%, S = 1% and O = 1%
(c) C = 90%, H = 5%, S = 2% and O = 3% (d) C = 95%, H = 2%, S = 1% and O = 2%
[Ans.: b]
2. A good fuel should posses
(a) High ignition temperature (b) Moderate ignition temperature
(c) High calorific value (d) Both b and c
[Ans.: d]
3. Ignition temperature of a fuel is the
(a) Temperature at which the fuel can be stored safely
(b) Lowest temperature at which the fuel must be preheated so that it starts burning
(c) Temperature attained with the fuel is burnt
(d) Temperature at which the fuel ignites for a moment, but doesn’t burn after then
[Ans.: b]
4. Which of the following is not an advantage of gaseous fuels over solid and liquid fuels
(a) They can easily be conveyed through pipelines to the actual place of use
(b) They can be lighted at moments notice
(c) They cannot be preheated by the heat of the hot waste gases
(d) Their combustion can readily be controlled
[Ans.: c]
5. Which of the following statements is true
(a) Coke possesses better strength than coal
(b) Coke burns with a long flame
(c) Coke burns with a short flame
(d) Sulphur content of coke is higher than that of coal from which it is obtained
[Ans.: c]
6. Which of the following fuel gases possesses the highest calorific value
(a) Water gas (b) Coal gas
(c) Producer gas (d) Natural gas
[Ans.: b]
7. Petrochemicals can be used to prepare:
(a) PVC plastics (b) Polystyrene plastics
(c) Terylene fibers (d) None of these
[Ans.: d]
8. The maximum temperature reached, when the coal is completely burnt in the theoretical amount
of air is called:
(a) Fusion temperature (b) Calorific intensity
(c) Ignition temperature (d) None of these
[Ans.: b]

3.34
9. The calorific value of a coal sample is higher, if its:

(a) Moisture content is high (b) Ash content is high
(c) Volatile matter is high (d) Fixed carbon is high
[Ans.: d]
10. Which of the following in coal decreases its calorific value:
(a) Carbon (b) Hydrogen
(c) Oxygen (d) Sulphur
[Ans.: c]
11. Which of the following is not a characteristic of progressive transformation of wood to coal
during coalification?
(a) Fixed carbon content increases (b) Moisture content decreases
(c) Volatile matter increases (d) Oxygen content decreases
[Ans.: c]
12. Peat is:
(a) Soft brown coloured (b) Brown jelly like mass
(c) Pitch black coal (d) Last stage of coalification
[Ans.: b]
13. Which of the following contain highest percentage volatile matter?
(a) Peat (b) Lignite
(c) Bituminous coal (d) Anthracite
[Ans.: a]
14. In orsats apparatus, potassium hydroxide is used to absorb:
(a) Oxygen (b) Carbon dioxide
(c) Carbon monoxide (d) Sulphur dioxide
[Ans.: b]
15. Orsats apparatus is used to obtain:
(a) Specific heats of components
(b) Molecular weights of components
(c) Gravimetric analysis of a gas mixture
(d) Volumetric analysis of flue gases
[Ans.: d]
16. Higher calorific value of fuel assumes that is:
(a) Contains H2O in liquid form (b) Contains H2O in vapour form
(c) Ignores the presense of H2O (d) Contain H2O in liquid and vapour forms
[Ans.: d]
17. Stoichiometric quantity of air is the quantity of air required for complete combustion of fuel with
(a) some excess oxygen (b) non oxygen left unused
(c) 50% excess air (d) 100% excess air
[Ans.: b]

18. Analysis of flue gages is done by:

(a) Boy’s gas calorimeter (b) Orsat apparatus
(c) Retort (d) Bomb calorimeter
[Ans.: b]
19. Bomb calorimeter is used for determining the calorific value of
(a) Solid fuel (b) liquid fuel
(c) gaseous fuel (d) both a and b
[Ans.: d]
20. Proximate analysis of fuel is determination of percentage of
(a) C, H, N, S, H2O (b) C, H2O, ash, volatile matter
(c) C only (d) useful heat evolved
[Ans.: b]
21. Ultimate analysis of fuel is determination of percentage of
(a) C, H, N, S, H2O (b) C, H2O, ash, volatile matter
(c) sulphur only (d) fixed carbon only
[Ans.: a]
22. Bomb calorimeter is used to determine:
(a) HCV at constant pressure (b) LCV at constant pressure
(c) HCV at constant volume (d) LCV at constant volume
[Ans.: c]
23. Incomplete combustion can be best judged by
(a) smoky chimney exit (b) excess air in flue gases
(c) measuring CO in flue gases (d) measuring O2 in flue gases
[Ans.: c]
24. Gas with least calorific value is:
(a) coal gas (b) water gas
(c) producer gas (d) natural gas
[Ans.: c]
25. Main constituent of natural gas is
(a) carbon monoxide (b) methane
(c) Hydrogen (d) ethane
[Ans.: b]
26. The process of splitting bigger hydrocarbons into smaller hydrocarbons is called
(a) pyrolysis (b) thermal decomposition
(c) cracking (d) combustion
[Ans.: c]
27. Iso-octane (2,2,4-trimethy pentane) has an octane rating of:
(a) 100 (b) Zero
(c) 50 (d) above 100
[Ans.: a]

3.36
28. Which of the following possess zero octane number:

(a) Iso-octane (b) petrol
(c) n-heptane (d) LPG
[Ans.: c]
29. Suitability of a diesel fuel is determined by:
(a) Octane rating (b) percentage of carbon
(c) length of hydrocarbon chain (d) Cetane number
[Ans.: d]
30. For good performance, the hydrocarbon molecules in a diesel fuel should be
(a) Branch-chained (b) side-chained
(c) straight–chained (d) aromatic
[Ans.: c]
31. The cetane rating of hexadecane is:
(a) 100 (b) 0
(c) 50 (d) none of these
[Ans.: a]
32. Which of the following is used as a jet engine fuel:
(a) LPG (b) Kerosene
(c) Power alcohol (d) coal
[Ans.: b]
33. Main constituent of LPG is
(a) Methane (b) Propane
(c) Benzene (d) Butane
[Ans.: d]
34. Alcohol has an octane number of about
(a) 50 (b) 60–70
(c) 90 (d) 25
[Ans.: c]
35. Alcohol-blended petrol possesses

(a) Better calorific value (b) Better anti knock properties
(c) Poorer-antiknock properties (d) None of these
[Ans.: b]
36. In Bergius process of preparing synthetic petrol by

(a) Passing water gas over heated powdered coke under pressure
(b) Catalytic hydrogenation of coal
(c) Heating coal along under pressure
(d) Cracking of heavy oil
[Ans.: b]

37. A good fuel should possess:

(a) Low calorific value (b) High ignition temperature
(c) High calorific value (d) High ash content
[Ans.: c]
38. Anthracite:
(a) is lowest rank coal
(b) contains high percentage of carbon
(c) contains high percentage of volatile matter
(d) high calorific value and high carbon percentage
[Ans.: d]
39. An example of primary fuel is

(a) Natural gas (b) Petrol
(c) Wood charcoal (d) Coke
[Ans.: a]
40. Lignite is:
(a) Lowest rank coal (b) Highest rank coal
(c) Used in metallurgy of iron (d) Contains no moisture
[Ans.: a]

1. Define fuel and give some examples.
Ans.: Fuel is a combustible substance containing carbon as the major constituent which on
proper burning gives large amount of heat that can be used economically for domestic
and industrial purposes.
Examples are coal, petrol, diesel, etc.
2. Give classification of fuels according to the occurrence.
Ans.: According to the occurrence, the fuels are classified into natural (primary) and secondary
(derived) fuels.
3. What are the units of heat and their inter-conversions?
Ans.: Units of heat are calorie, kilo calorie, British thermal unit and centigrade heat unit.
1 kcal = 1000 cal = 3.968 BTU = 2.2 CHU
4. Define calorific value and give relation between higher and lower calorific values.
Ans.: Calorific value is the total quantity of heat liberated by the complete combustion of one
unit mass/volume of a fuel in oxygen.
LCV = HCV – latent heat of water vapour formed
5. What kinds of calorimeters are used for determining calorific value of solid, liquid and gaseous fuels?
Ans.: Bomb calorimeter is used for determining the calorific value of solid and liquid fuels.
Junker’s calorimeter is used for determining the calorific value of gaseous fuels.

3.38
6. What are the characteristics of a good fuel?

Ans.: High calorific value, moderate ignition temperature, low moisture content, low non-com-
bustible matter content, etc.
7. Name some of the petroleum products.
Ans.: Liquified petroleum gas, gasoline, petrol, kerosene, diesel oil, heavy oil, etc.
8. What are the ovens used for preparation of metallurgical coke?
Ans.: Beehive oven and Otto Hoffman’s by-product oven.
9. Explain cracking with a suitable example.
Ans.: The process of breakdown of high molecular weight hydrocarbons of high boiling points
into simple, lower molecular weight hydrocarbons of low boiling points is known as
cracking.
Cracking
Ex: C10 H 22  → C5 H12 + C5 H10
Decane n-pentane Pentane
10. What is meant by flue gas?

Ans.: The mixture of gases like CO2, CO and O2 exhaust of the combustion chamber is called
flue gas.
11. What is the importance of analysis of flue gas?
Ans.: The analysis of flue gas either from a furnace or from an engine’s exhaust would give an
idea about the efficiency of the combustion process. If the flue gas contains considerable
amount of CO, it indicates that incomplete combustion is occurring and it also indicates
the short supply of O2 for combustion, and this will lead to wastage of fuel.
12. What happens if the flue gas contains considerable amount of O2?
Ans.: It indicates that the O2 supply is very much in excess, and it results in loss of heat.
13. Which apparatus is used in the analysis of flue gas?
Ans.: Orsat’s apparatus.
14. In Orsat’s apparatus, which gases are absorbed by which solutions?
Ans.: Potassium hydroxide solution – only CO2
Alkaline pyrogallic acid – CO2 and O2
Ammonical cuprous chloride – CO, O2 and CO2
Q.1 a. W hat do you understand by the term knocking in IC engines? Explain its relationship with
chemical constituents of fuels.
b. A sample of coal contains 60% carbon, 33% oxygen, 6.0% hydrogen, 0.5% sulphur, 0.2%
nitrogen and 0.3% ash. Calculate GCV and NCV of coal.
Q.2 Distinguish between the followings:
a. Gross and net calorific values
b. Octane number and centane number

Q.3 a. How coal is graded? Explain its calorific value of coal.

b. Give the advantages and disadvantages of coal over gaseous fuels.
Q.4 a. Explain the proximate analysis of coal and its significance.
b. Distinguish between low-temperature carbonisation and high-temperature carbonisation.
Q.5 a. W hat is metallurgical coke? How it is superior than coal? Explain the manufacture of the met-
allurgical coke by Otto Hoffman’s by-product coke oven method. List the various by-products
obtained.
b. Define octane number of gasoline. Why is ethylene dibromide added, when tetra ethyl lead is
used as an anti-knock?
Q.6 A fuel containing 92% C and 4% H2 by mass was burnt in 90% of air of that required for com-
plete combustion. Find out the % of composition of dry product of combustion by mass of H 2 is
burnt completely and no carbon is left behind.
Q.7 Give brief note on the following:
a. Explain how fuels are classified with suitable examples.
b. Give the comparison between solid, liquid and gaseous fuels.
c. What are the characteristics of a good fuel?
Q.8 Explain the significance of the following constituents present in coal:
a. Moisture
b. Volatile matter
c. Ash
d. Fixed carbon
Q.9 a. Discuss the relative merits and demerits of solid, liquid and gaseous fuels.
b. Explain the significance of the following constituents present in coal.
Q.10 a. How a calorific value of a gaseous fuel is determined by Junker’s gas calorimeter? Describe
the experiment with a neat diagram.
b. Calculate gross and net calorific value of a gaseous fuel from the following data. Vol. of gase-
ous fuel burnt at STP -0.09 m3, weight of water used for cooling 25.0 kg, temperature of inlet
water 25 °C, temperature of the outlet water 30.0 °C, weight of water produced by steam con-
densation 0.02 kg latent heat of steam 587 kcal/kg.
Q.11 a. What are the constituents of petroleum? Describe the origin of petroleum.
b. Give an account of production of petrol from crude oil.
Q.12 The analysis of a gas has the following composition: H2 = 14%, CH4 = 2%, CO = 22%, CO2 = 5%,
N2 = 55%, O2 = 2%. Find the air required for the combustion of 1 m3 of the gas. If 45% excess air
is supplied, find the volume analysis of the products.
Q.13 a. Define a fuel? How chemical fuels are classified and give examples for each?
b. What is meant by calorific value of a fuel? Define calorie and kilocalorie.

3.40
Q.14 Explain the significance of the following constituents present in coal:

a. Total carbon
b. Hydrogen
c. Nitrogen
Q.15 a. What are chemical fuels? Give complete classification of chemical fuels with examples.
b. What are different types of fuels? What are the characteristics of a good fuel?
c. Mention the criteria for selecting good fuel.
d. Distinguish between solid, liquid and gaseous fuels.
Q.16 a. What is meant by calorific values of a fuel?
b. Describe how the calorific value of a solid fuel is determined using a bomb calorimeter.
c. What are the fuels used for determination of water equivalent of bomb calorimeter and why?
Q.17 a. Differentiate proximate and ultimate analysis of coal.
b. Discuss the importance of ultimate analysis of coal.
Q.18 a. What a good fuel must have low ash content? Or what is role of ash on coal?
b. How is nitrogen determined in a solid fuel?
c. What is the significance of a volatile matter in coal?
d. How is ranking of coal make based on ultimate analysis?
Q.19 a. What are the advantages of liquid fuels over solid fuels?
b. Differentiate between coal and coke.
c. Explain carbonisation of coal.
d. Why is coke preferred to coal in metallurgical purposes?
e. Why are gaseous fuels more advantageous than solid fuels?
Q.20 a. Write short note on Beehive coke oven.
b. Why is peat not considered as an economical fuel?
Q.21 What is crude oil? Write short note on refining of crude petroleum. What are the various frac-
tions obtained from petroleum? Mention the industrial uses to which they are put.
Q.22 a. W hat are the structural features of hydrocarbons in unlead petrol and diesel? What are the
structural factors that promote its high value?
b. W hat is the significance of octane number and cetane number and for which these are used?
How these can be improved?
c. W hy is C2H4Br2 added, when TEL is used as an anti-knock?
d. W hat types of compounds nowadays are being added to petrol to improve octane rating?
Q.23 a. W hat is meant by cracking of petroleum? Explain? Fluidised-bed catalytic method of obtain-
ing gasoline. Give its mechanism.
b. W hat are the advantages of catalytic cracking process? Describe, with a neat diagram, the
fixed-bed catalytic cracking process.

c. D
ifferentiate between thermal and catalytic cracking.
d. W hat are the advantages of catalytic cracking over thermal cracking?
e. W hat is meant by knocking? How is it related to chemical constitution? Describe the functions
of TEL. Explain octane number and cetane number.
Q.24 a. What is LPG? What are the advantages of LPG over gaseous fuels?
b. Write the approximate compositions and calorific values of water gas and producer gas.
Q.25 a. Define flue gas. How the analysis of flue gas is done by the Orsat apparatus? What conclusion
can be drawn from the experiment? What is the significance of this analysis?
b. H
ow distinction can be made between complete and incomplete combustion of fuel?
c. W hat is leaded petrol?
a. Catalytic converter
b. F
lue analysis and its significance
Q.27 a. What is the principle of bomb colorimeter?
b. How gross calorific value of a solid fuel determined by Bomb Calorimeter? Write Dulong’s
formula for calculating calorific value of fuel from its ultimate combustion data.
c. D iscuss Beehives oven method for the manufacture of coke.
Q.28 a. Describe the fractional distillation of petroleum.
b. W hat do you understand with the knocking of fuel? Report the ways to improve the anti-
knocking characteristic of a fuel.
Q.29 Write short note on metallurgical coke.
Q.30 A coal sample has the following composition: C = 90%; H = 3.5%; O = 3%, S = 0.5%; and
N2 = 1%; the remaining being ash. Calculate the theoretical volume of air required at 27 °C and
1 atm pressure when 100 kg of the coal is burnt.
Q.31 The composition by weight of a coal sample is C = 81%; H = 5%; O = 8.5%; S = 1%; N = 1.5%;
Ash = 3%:
a. Calculate the amount of air required for the complete combustion of 1 kg of the coal.
b. Calculate the gross and net calorific values of the coal sample. Given that the calorific values
of C, H and S are 8,060 kcal/kg; 3,400 kcal/kg and 2,200 kcal/kg, respectively.
Q.32 A producer gas has the following composition by volume: CO = 30%; H 2 = 12%; CO2 = 4%;
CH4 = 2% and N2 = 52%. When 100 m3 of the gas is burnt with 50% excess air used, what will
be the composition of the dry flue gases obtained?
Q.33 A hydrocarbon fuel on combustion gave the flue gas having the following composition by
volume: CO2 = 13%, O2 = 6.5% and N2 = 80.5%. Calculate (a) the composition of fuel by weight
and (b) the percentage of excess air used.
Q.34 Calculate the approximate calorific value of a coal sample having the following ultimate
analysis: C = 80%; H = 3.5%; S = 2.8%; O = 5.0%; N = 1.5% and ash = 7.2%.

4 ALTERNATE ENERGY
RESOURCES
Energy conservation is the foundation of energy independence
4.1 INTRODUCTION
Every day, a lot of carbon dioxide is being released due to different developmental activities that accumu-
lates around the atmosphere. Such release of carbon dioxide is one of the causes of global warming. One
answer to reduce the global warming effect is to replace and retrofit current traditional energy resources
with alternative energy sources which perform comparably better without emitting carbon dioxide.
At the same time, with increasing demand for energy and with fast depleting conventional sources
of energy such as coal, petroleum, natural gas and so on, the non-conventional sources of energy such
as energy the sun, wind, biomass, tidal energy, geo-thermal energy and even energy from waste material
are gaining importance. This energy is abundant, renewable, pollution-free and eco-friendly.
The importance of renewable energy was recognised in the country in the early 1970s. The renew-
able energy programme started with the establishment of the Department of Non-conventional Energy
Sources (DNES) in 1982. The Indian Renewable Energy Development Agency (IREDA) was set up
in 1987. In 1992, the DNES was converted into the Ministry of Non-conventional Energy Sources
(MNES) which has taken several steps to create a suitable atmosphere for harnessing non-conventional
sources of energy. Today, India has one of the largest programmes for renewable energy.
Depending on their usage, energy resources are broadly divided into two categories—conven-
tional and nonconventional energy resources.
4.1.1 Conventional or Traditional Energy Resources

The energy resource that has been used from ancient period is known as conventional or traditional
energy resources. A majority of these energy resources are non-renewable.
For example, coal, fuel wood, crude oil, natural gas, etc.
All conventional sources will become rare, endangered and extinct, as they produce lots of carbon
dioxide that adds to the greenhouse effect in the atmosphere.
4.1.2 Nonconventional Energy Resources or Renewable Energy Sources

The energy sources which will not get exhausted even after continuous and excessive use and are
abundantly available, continuously replenished by nature are nonconventional energy resources. These
energy resources are environmentally and ecologically safe.
For example, solar energy, wind energy, tidal energy, biogas, geothermal energy, nuclear energy, etc.
M04_ENGINEERING-CHE00_SE_1181_CH04.indd 1 5/13/2016 4:53:38 PM

4.1.3 Alternative Energy

Alternative energy is commonly referred to as any energy source that is an alternative to fossil fuel.
According to previous reports, coal as an alternative to wood, petroleum as an alternative to whale
oil, alcohol as an alternative to fossil fuels, coal gasification as an alternative to petroleum etc., were
common; however, this is completely different. Depending on availability, demand and sustainability,
the energy resources which are used as alternative energy source has changed considerably from time
to time.
Alternative energy plays vital role to meet the future demands of energy and environment; hence,
advance research in this area started in a multidisciplinary way. Let us examine the various definitions
of alternative energy.
Oxford Definition
Energy fuelled into ways that does not use up natural resources or harm the environment.
Princeton WordNet
Energy derived from sources that does not use up natural resources or harm the nature.
Natural Resource Defence Council

Energy that is not popularly used and is usually environmental sound such as solar or wind energy.
Material and Management

Fuel source that are other than those derived from fossil fuels typically used inter changeable for
renewable energy.
For example, wind energy, solar energy, biomass, wave and tidal energy.
Torridge District Council

Energy generated from alternatives to fossil fuel, but need not be renewable.
Climate Change 2007

Energy derived from nontraditional sources.
For example, compressed natural gas, solar energy, hydroelectric and wind energy.
Hence, common alternative energy resources are solar energy, water energy (hydroelectric power
and tidal power), wind energy, geothermal energy, biomass energy, nuclear energy, etc.
4.2 NON-CONVENTIONAL ENERGY SOURCES AND STORAGE DEVICES
4.2.1 Solar Energy

The sun is a source of enormous energy. Solar energy originates with thermo-nuclear fusion in the
sun, involving the fusion of hydrogen into helium either through the proton-proton chain or through
the carbon-nitrogen cycle. The Earth receives solar energy as a radiant energy which reaches the top
of the atmosphere at 1,366 watts per square meter. This energy ranges from ultraviolet, visible and
infrared light. About half of this energy actually makes it to the Earth’s surface, 30% is reflected and

Alternate Energy Resources 4.3
20% is absorbed by the atmosphere. Thus, when the sun is directly overhead, full sunlight can deliver
about 700 watt per square meter and at that rate, the sun can deliver 700 MW of power to an area of
390 square miles.
The total amount of solar energy reaching the earth is vast and almost beyond belief. For an exam-
ple, one year’s expenditure of fossil fuel in the USA is equivalent to just 40 minutes of sunlight striking
the particular land surface of the USA.
The solar energy technology broadly comprises thermal conversion and photo conversion. Thermal
conversion takes place through direct heating, ocean waves and currents and wind. Photo conversion
includes photosynthesis, photochemistry, photo electrochemistry, photo galvanism and photovoltaics.
Solar radiation is collected and converted by natural collectors such as the atmosphere, the ocean and
plant life, as well as by man-made collectors of many kinds (Figure 4.1). There are a number of solar
technologies by which it can be harnessed (Figure 4.2).
Solar
radiation
Atmosphere Ocean Structures Man-made collectors Plants
Quantum
Wind OTEC∗ Passive Heat Biomass
process
Useful energy
∗OTEC = Ocean thermal energy conversion
Figure 4.1 Natural and man-made collectors
Process heat
biomass
Heat
Solar thermal
heating & cooling
Photo voltaics
Solar
SUN
radiation Electricity
Solar thermal
OTEC windmills
Mechanical
Windmills
energy
Biochemical
conversion Chemical/fuels
Figure 4.2 Solar technologies

The earliest use of direct solar energy by mankind was drying the body or warming it in the sun during
winters. Indeed, drying of clothes, fodder, timber, agricultural and animal products, salt water (to get
salt) and passive space heating remained the most extensive form of use of direct solar energy in the
history of mankind. All other active solar technologies or devices for harnessing direct solar energy
have fairly recent origins (Figure 4.2). A variety of active solar collectors provide a broad range of
applications as follows:
(i) Solar heating of water
(ii) Solar space heating of buildings
(iii) Solar air-conditioning
(iv) Solar refrigeration
(v) Solar drying
(vi) Solar cooking
(vii) Solar green-houses
(viii) Solar furnaces
(ix) Solar desalination
(x) Salt production
(xi) Solar electricity—thermal
(xii) Solar electricity—photovoltaic
Solar Heating of Water

Solar water heating is very popular in warm, sunny climates. Flat plate collectors for heating water
consists of a thin broad box with a glass or plastic top and a black bottom in which water tubes are
embedded as shown in Figure 4.3. These collectors are faced towards the sun and the black bottom
gets hot when it absorbs sunlight. Thus, water circulating tubes are heated and are conveyed to a tank
where it is stored.
Solar heating system may be active or passive. The heated water is moved by means of pumps in
an active system. However, in a passive system, the collector is lower than the tank. By natural con-
vection, the heated water rises into the tank from the collector and the cool water descends into the
collector from the tank. This is shown in Figure 4.4. The tank will usually have a source of auxiliary
heat (electric or gas) in order to get the temperature to a desired level or to provide heat when solar
energy is insufficient.
Solar Space Heating of Buildings

Flat-plate collectors such as those used in water heating with same concept and less expensive option
can be used for space heating as only air circulation through the collector box is necessary.
In nonfreezing climates, simple water convection systems may suffice.
In freezing climates, an antifreeze fluid is circulated. Solar heat is augmented by an auxiliary heat
source in the hot-water tank.
The efficiency of solar space heating can be enhanced by proper designing of a building to act as
its own collector. Here, the basic principle is to have windows facing the sun. On cool days, it depends
on sun’s angle of incidence and sunlight can heat the interior of the building; however, at nights, insu-
lated drapes or shades can be pulled down to trap the heat inside. Excessive heat in hot days can be
avoided by using an awning or overhang to shield the window from the sun.

Sunlight
Tubes through
which water
circulates
Heat
Black surface Insulation Glass or plastic

window
Figure 4.3 Principle of a flat-plate solar collector
Hot-water
tank
Element
r
ate
t-w
Ho
Hot-water
Collector out
Water
circulates
by convection Auxiliary heat
(electric or gas)
er
at
lw
oo
C
Cold water in
Figure 4.4 Solar water heaters
Solar Air-conditioning
Solar air-conditioning includes solar-powered refrigeration system of ranking cycle system, absorption
refrigerator systems and solar-regenerated desiccant cooling systems. In such type of system, ambient
air is adiabatically cooled, dehumidified, cooled both sensibly and evaporatively and then ducted to
the living area. In the regenerative stage, air is evaporatively cooled, heated as it cools the supply air
stream, heated again by solar collectors and humidified.

Solar Refrigeration
Solar refrigeration is closely related to air-conditioning. It is generally required for food preservation
or for storage of medical and biological materials. Although most of the units/machines fabricated are
simple in design, they are generally too complicated to operate and, therefore, are not usable by the
people.
Solar Drying
Solar drying of agriculture and animal products is the most ancient, traditional and wide-spread
method of utilising direct solar energy. Agricultural products such as grain, hay, copra, fruits, nuts
and vegetables are still-dried with sun drying all over the world, including highly industrialised and
well-developed countries. This method is followed because it is the cheapest and the simplest way to
dry crops and abundant availability of sunlight is also ensured.
Solar Cooking
A solar cooker is a perfectly insulated shallow rectangular metal box, and inner side of this box is
blackened and fitted with a flat glass cover. When this cooker is placed in sunlight, the solar energy
penetrates the glass cover and is absorbed by the inner blackened surface. Thus, temperature will
increase inside the box, and the food gets cooked quickly.
The collector area of such a solar cooker can be increased by providing a plane reflector mirror of
size equal to the size of the box and is hinged on one side of the glass frame. With the help of reflector
mirror, a temperature rise of 15°C–20°C can be achieved inside the solar cooker.
Solar Greenhouses
A greenhouse is a closed structure covered with transparent material (glass or plastic) which acts as a
solar collector and utilises solar radiant energy for the growth of plants.
The incoming shortwave solar radiations can pass through the green house glazing; but the long-
wave thermal radiations emitted by the objects within the greenhouse cannot escape through the
glazed surface. As a result, the radiations get trapped within the greenhouse and result in an increase
in temperature. Further, the air inside the greenhouse gets enriched with carbon dioxide and the mois-
ture loss is reduced due to restricted transpiration. All these factors help the plant growth to sustain
during night and colder months.
Solar Furnaces
Extremely high temperatures with very clean condition of around 3,500°C can provide solar furnaces.
This can be used to melt refractory material.
In a solar furnace, high temperature is obtained by concentrating the solar radiations on to a speci-
men using a number of heliostats (turnable mirrors) arranged on a sloping surface. The biggest advan-
tage of a solar furnace is that heating can be accomplished without any contamination and temperature
can be easily controlled by changing the position of the material in focus. It is anticipated that in future,
solar furnaces can be utilised in the production of nitric acid and fertilisers from air.
Solar Desalination
In this method, solar radiation is admitted through a transparent air-tight cover of sloping sheets of
glass into a shallow blackened pool containing brine. The water evaporates from the brine when solar
radiations pass through the cover. The vapours produced get condensed as purified water on the cooling

Solar
radiation
Potable distilled
water trough
(leads to storage tank)
Brine
Brine Excess brine
inlet to waste
Figure 4.5 Basin type solar-still
glass cover, flow down the sloping roof, collected into a water storage tank (as shown in Figure 4.5).
The excess brine that has not evaporated is run to waste.
The cost of distilled water per litre obtained by this process is cheaper than distilled water obtained
by other electrical energy-based processes.
Salt Production
It is the most widely used method for salt production in many developing countries of the world. The
basic concept is that in areas where evaporation exceeds rainfall, a shallow pool of brine is exposed
which results in evaporation of water, leaving behind the salt.
Solar Electricity—Thermal
Solar energy may be used to heat a fluid, which then generates electricity through a conventional heat
engine. To obtain an adequate working temperature, some form of concentration of solar energy is
required, so that there is little contribution from diffused sunlight for most designs.
Broadly, the systems fall into two categories:
(i) Systems in which individual mirrors track the sun continuously
(ii) Systems in which mirrors are fixed
In continuous tracking systems, a large number of plane or curved mirrors is used. Each mirror is
steered to reflect sunlight onto a single tower mounted boiler and gives a high temperature with high
efficiency. However, mirrors require complex, rugged and accurate mechanisms.
Non-tracking systems consist of assemblies of trough-shaped collector, aligned east to west.
Above each collector, the absorber is fitted in the form of a tube. A general plan of a solar-thermal elec-
tric power plant is shown in Figure 4.6. It is expected that cost-effective and utility scale solar-thermal
power plants might be built in the near future.
Solar Electricity—Photovoltaic
A solar cell—more properly called a photovoltaic, or a PV cell—directly converts incident solar radia-
tion to electrical current. A PV cell looks like a simple wafer of material with one wire attached to the top
and one to the bottom. As sunlight shines on the wafer, it puts out an amount of electric current roughly
equivalent to that emitted by a flashlight battery. Thus, PV cells collect light and convert it to electric
power in one step. However, several cells can be connected together to obtain large amount of power.

Su
n
ra
ys
Thermal
Receiver energy
storage
Solar
thermal Heat
collector exchanger
Steam Feed water
for
process
Electrical power
plant
Electricity
Figure 4.6 General plan of a solar-thermal electric power plant

Working Principle
PV cells consist of two very thin layers of semiconductor materials separated by a junction layer. The
lower layer has atoms with single electrons in their outer orbit which are easily less. The upper layer
has atoms lacking electrons in their outer orbit; these atoms readily gain electrons. When the kinetic
energy of light photons striking the two-layer “sandwich” dislodges electrons from the lower layer, it
creates a current that can flow through a motor or some other electrical device back to the upper side.
The major material used in PV cells is silicon. PV cells consist of a single crystal of p-type silicon
with a surface layer of n-type silicon. When light falls on the junction, the electrons and holes move in
opposite directions across the p-n junction and electric current will flow if an external circuit is con-
nected. This is shown in Figure 4.7.
Cost
The cost of PV power (cents per kilowatt-hour) is the cost of the PV cells divided by the total amount
of power they may be expected to produce over their lifetime currently around 25 cents per kilowatt-
hour while the cost of power from other power alternative is 6–12 cents per kilowatt-hour for residen-
tial electricity. PV power had its first significant application in the 1950s in the solar panels of space
satellites. The cost comes down dramatically if more efficient cells with less expensive production
techniques are evolved.
Uses
The uses of PV cells are as follows:
(i) PV cells are widely used in watches, calculators, toys, etc.

(ii) T
he panels of PV cells provide power for traffic signals, radio transmitters, light houses, irrigation
pumps, earth orbiting satellites, etc.
p-n Junction
Radiation
A B
p n
Current flow Electron flow
Figure 4.7 Semiconductors functioning as solar cells
Future of Solar Energy

Solar electricity is growing at a phenomenal rate due to adverse environmental effects and logging of
non-renewable energy resources. The sun provides power only during the day, but 70% of electrical
demand occurs during the day for industries, offices and stores that are in operation. Thus, remark-
able savings can be achieved by using solar panels for daytime requirements and continuing to rely on
conventional sources at night.
4.2.2 Wind Energy

The research pertaining to wind energy dates back several decade to the 1970s when the NASA devel-
oped an analytical model to predict wind turbine power generation during high winds. Today, both
Sandia laboratory and national renewable energy have programmes dedicated to wind research. The
Field Laboratory Operator is Optimised Wind Energy (FLOWE) at Caltech was established to research
alternative approaches to wind energy.
The sun is the origin of wind energy. Wind is a form of solar energy and is caused by the uneven
heating of the atmosphere by the sun, the irregularities of the earth surface and rotation of the Earth.
Wind flow patterns are modified by the Earth’s terrain bodies of water and vegetation cover. Kinetic
energy in the wind can be used to run wind turbines but the output power depends upon the wind
speed. Turbines generally require a wind in the range of 20 km/h. Wind turbine converts kinetic
energy in the wind into mechanical power. This mechanical power can be used for a specific task or the
generator converts mechanical power into electricity to power homes, businesses, schools and so on.
Figure 4.8 Wind turbines

4.10
Like air draft propeller blades, wind turbines (Figure 4.8) turn in the moving air and power an elec-
tric generator that supplies an electric current. Simply stated, a wind turbine is the opposite of a fan.
Instead of using electricity to make wind, it is using wind to make electricity. The wind turns the
blades, which spin a shaft, which connects to a generator and makes electricity. Wind energy is a free,
renewable resource; the wind turbines set-up is a bit expensive as well.
4.2.3 Geothermal Energy

Geothermal energy is produced by tapping into the thermal energy created and stored within the
Earth’s crust (Figure 4.9). It is considered sustainable because thermal energy is constantly replen-
ished. Several entities such as the National Renewable Energy Laboratory and Sandia National
Laboratories are conducting research towards the goal of establishing a proven science around the
geothermal energy.
Geothermal energy comes from the heat within the earth. The word geothermal comes from the
Greek words geo meaning earth and thermal meaning heat. Geothermal energy has been used for
thousands of years in some countries for cooking and heating. People around the world use geothermal
energy to produce electricity to heat buildings, green houses and for other purposes.
Power plant
Turbine Generator Load

Well
Heat exchanger
Geothermal reservoir
Production Injection
Magma Well Well

Figure 4.9 Geothermal plant
There are four kinds of geothermal sources—hydrothermal, geo pressured, hot dry rock and
magma.
4.2.4 Water Power

The energy of falling or fast-running water can be harnessed and used in the form of motive energy
or temperature difference. Since water is about a thousand times heavier than air, even a slow flowing
stream of water can yield great amount of energy.
Hydroelectric Energy
Hydroelectric energy is a term usually referred to in the context of hydroelectric dams. Hydroelectric
power stations capture the kinetic energy of moving water and give mechanical energy to turbines.
The moving turbines then convert mechanical energy into electrical energy through generators.

This energy has been exploited for centuries. Farmers since the ancient Greeks have used water
wheels to grind wheat into flour. Placed in a river, a water wheel picks up flowing water in buckets
located around the wheel. The kinetic energy of the flowing river turns the wheel and is converted into
mechanical energy that runs the mill (Figure 4.10).
In the late 19th century, hydropower became a source for generating electricity. The first hydro-
electric power plant was built at Niagara Falls in 1879. In 1881, street lamps in Canada were powered
by hydropower. In 1882, the world’s first hydroelectric power plant began operating in Appleton,
Wisconsin.
A typical hydro plant is a system with three parts—an electric plant where the electricity is pro-
duced, a dam that can be opened or closed to control water flow and a reservoir where water can be
stored. The water behind the dam flows through an intake and pushes against blades in a turbine,
causing them to turn. The turbine spins a generator to produce electricity. The amount of electricity
that can be generated depends on how far the water drops and how much water moves through the
system. The electricity can be transported over long-distance electric lines to homes, factories and
businesses.
Generation of electricity from a small-sized hydropower source is a low-cost, environment friendly
and renewable source of energy. Small and mini hydel projects have the potential to provide energy in
remote and hilly areas where extension of grid system is uneconomical.
Sluice gates High pressure water
Water storage Generator

reservior
Dam
Figure 4.10 Hydroelectric power plant
Tidal Energy
Tidal energy is a form of hydropower that converts the energy obtained from tides into useful forms
of power, mainly electricity. Sea water keeps rising and falling alternatively twice a day under the
influence of gravitational pull of moon and sun. This phenomenon is known as tides. Tidal power
refers to capturing energy from the tides in horizontal direction. Tides come in, raise water levels in a
basin and tides roll out. The water is made to pass through turbine to get out of the basin. Therefore,
power generation through this method has a varying degree of success (Figure 4.11).
There are two types of tidal energy systems that can be used to extract energy—kinetic energy, the
moving water of rivers, tides and open ocean currents; and potential energy from the difference in height
between high and low tides. The first method—generating energy from tidal currents—is becoming
more popular because people believe that it does not harm the environment as much as barrages or dams.
Many coastal sites worldwide are being examined for their suitability to produce tidal energy.

4.12
Tidal power

Figure 4.11 Tidal energy
4.2.5 Biomass
Biomass refers to all plant material and animal excreta when considered as an energy source. Some
important kinds of biomass are inferior wood, urban waste, farm animal and human waste. Biomass as
an energy source can be either used directly via combustion to produce heat or indirectly after convert-
ing it into various forms of biofuels. Conversion of biomass to biofuels can be achieved by different
methods such as thermal, chemical and bio chemical methods. Wood remains the largest biomass
energy source.
Since biomass includes plant or animal matter that can be converted into fibers or other indus-
trial chemicals including biofuels, industrial biomass can be grown from numerous types of plants.
Biomass, biofuel and bio gas are burned to produce heat/power and consequently, sulphur oxide,
nitrous oxide and particular matter that pollute the environment are produced from this combustion.
Biogas
Biogas is the gas resulting from an anaerobic digestion process (Figure 4.12). A biogas plant can con-
vert animal manure, green plants, waste from agro industry and slaughterhouses, paper production,
sugarcane production, sewage and so forth into combustible gas.
Biogas is a mixture of methane, carbon dioxide, water and hydrogen.
Biogas power generation flow chart
Organic Oxygen
waste 2O2
Electric
power
Anaerobic Methane Power
digester CH4 generator
Heat
Carbon dioxide
Other
and Water
substances
CO2 + 2H2O
Figure 4.12 Flow chart of biogas power generation

Biofuel
Biofuel is any fuel that derives from biomass; this may be recently living organisms or their metabolic
byproducts, such as manure from cows, buffaloes etc., Typically, biofuel is burnt to release its stored
chemical energy. Biomass can be directly used as fuel or to produce liquid biofuel. Agriculturally pro-
duced biomass fuels such as biodiesel, ethanol and bagasse (byproduct of sugarcane cultivation) can be
burnt in internal combustion engines or boilers.
Algae Fuel
Algae fuel is a biofuel derived from algae. During photosynthesis, algae and other photosynthetic
organisms capture carbon dioxide and sunlight and convert it into oxygen and biomass. This is usually
done by placing the algae between two panes of glass. The algae create three forms of energy fuel—
from its growth cycle, heat can be generate, the oil derived from the algae is used as biofuel and on
maturity, algae can give biomass.
The heat can be used to power building systems such as heating of water or to produce energy.
Biofuel is oil extracted from algae upon maturity and is used to create energy similar to the use of bio-
diesel. Biomass is the matter left over after extracting oil and water and can be harvested to produce
combustible methane for energy production.
Biomass Briquettes
Biomass briquettes are developed as an alternative to charcoal. Almost any kind of plant matter com-
pressed into briquettes has about 70% the calorific value of charcoal.
4.2.6 Nuclear Energy

With growing realisation that the supply of fossil fuels is depleting fast and is very limited, nuclear
energy has gained importance and has become essential as an alternative source of energy. Due to
rapid increase in industry and urbanisation, along with booming increase in population, it is estimated
that the present fossil fuels (coal and petroleum) will not last more than a few decades to cater to the
demand for electric power. Therefore, attention has been focused mainly on nuclear energy, which
seems to offer an infinite source of energy. This field began with the discovery of radioactivity. The
release of tremendous amount of energy through nuclear reaction became possible with the develop-
ment of artificial radioactivity.
Nuclear energy is the energy released when the nuclei of certain atoms undergo induced reac-
tions such as fission and fusion. The materials that make such energy available are called nuclear fuel.
Nuclear fuels release energy by an entirely different mechanism as compared to chemical reactions. In
nuclear fuel, different elements are produced, and some of the binding energy of the nucleus is released,
during bombardment of neutron on radioactive element such as uranium-238, etc. Therefore, a large
amount of energy is released in less than a millionth of a second. For example, complete fission of one
kg of uranium provides the energy equivalent of about 2 × 107 kWh; such amount of energy can be
obtained by burning of about 3,000 tonnes of high grade coal.
Mass Defects and Nuclear Binding Energy

The mass of an atomic nucleus has been found to be always less than the sum of the masses of the
constituent nucleons (i.e., protons, neutrons and electrons). This difference is called mass defect. The
mass thus lost appears in the form of energy in accordance with Einstein’s mass-energy relationship;
the energy emitted is called the binding energy of the nucleus.

4.14
Consider an isotope having atomic number ‘Z’ and mass number ‘A’. Evidently, its atom contains
protons = Z, electrons = Z, Neutrons = (A − Z).
Let mp, me and mn respectively represent the masses of proton, electron and neutron.
Thus, the calculated mass of this isotope is
M′ = Zm p + Zme + ( A − Z )mn
= ZmH + ( A − Z)mn [ mp + me = mH mass of hydrogen atom]
∴
Let M = actual mass of the element

Mass defect = M ′ − Μ = ∆M
∆M = ZmH + (A − Z)mn − M
Thus, the mass defect (∆M) is the loss of mass in the formation of nucleus from its constituents. This
loss of mass represents the amount of energy, which would be released if an atom of mass number A
were synthesised from its constituents. This form of energy is in accordance with Einstein’s mass-
energy relationship.
Thus, the binding energy of the nucleus may be defined as the energy released during the forma-
tion of a nucleus from its constituents nucleons.
Thus, if ∆M is the mass defect,
then, binding energy B.E. = ∆MC2, where C = Velocity of light (3 × 108m/s)
B.E. = [ZmH + (A − Z) mn − M] C2
The binding energy per nucleon is calculated by dividing the binding energy of a nucleus by the
number of nucleons.
The binding energy corresponding to one atomic mass defect is 931.5 MeV (million electron volts)
B.E. 1
Binding energy nucleon, = [ ZmH + ( A − Z)mn − M ]C2
A A
The greater is B.E./nucleon, the greater is the stability of the nucleus.
The energy equivalent to one atomic mass unit (1 amu) is given by,
Mass of 1 atomic unit = 1.6604 × 10 −24
Velocity of light (C) ≈ 2.998 × 1010 cm/sec
Thus E = (1.6604 × 10 −24 )(2.998 × 1010 )2 erg
1..6604 × 10 −24 (2.998 × 1010 )2
= MeV
1.602 × 10 −6
= 931.5 MeV
Example to Calculate the Binding Energy per Nucleon

The formation of helium atom can be written as follows:
2 ⋅ 11 p + 2 ⋅ 01 n → 42 He
Change in mass is given as follows:
∆M = 2m[ 11 p]+2m[ 01 n] − m[ 42 He]
= 2m[ 11 H]+2m[ 01 n] − m[ 42 He]
= 2(1.00782505) + 2(1.0086649) − 4.0026033
= 0.0303766 amu

Since the energy equivalent to 1 amu of mass is 931.5 MeV, the energy change during the formation
4
2 He of atom is
∆E = (0.0303766 amu)(931.5 MeV/amu)
= 28.2956 MeV
Thus binding energy B.E.= 28.2956 MeV
Further, since there are four nucleons in 42 He nucleus, the binding energy per nucleon (EB/A) is
obtained by dividing the total binding energy with the number of nucleons, that is,
E B 28.2956
= = 7.07390 MeV
A 4
The binding energy per nucleon is a direct measure of the stability of the nucleus.
Binding Energies and Stability of Nuclei

Mean binding energies, that is, the binding energies per nucleon, drastically increase with increasing
atomic mass in lighter elements, reach a maximum at mass numbers 55−58, and gradually decrease in the
case of heavier elements. The mass number 55–58 corresponds to iron and nickel, the most stable elements,
and this stability is also reflected in the abundant presence of these elements in the inner core of the earth.
From Figure 4.13, it is seen that the maximum occurs at about mass number 56 (iron). Thus, the
nucleus of iron is thermodynamically most stable. It is also seen that the points for helium (mass number
= 4), carbon (mass number = 12) and oxygen (mass number = 16) lie quite high in the graph. This shows
that the nuclei of these elements are exceptionally stable. The maximum binding energy is seen to be
about 8.7 MeV. This is the energy required to remove a proton or a neutron from the most stable nucleus.
4.2.7 Nuclear Reactions

Nuclear reactions involve changes in the number of nucleons present in the nucleus. Hence, there is a
formation of new atomic species. Thus, nuclear reactions lead to atomic transformations. In addition,
a huge amount of energy is released in nuclear reaction, involving a small but measurable loss in mass.
This mass is transformed into energy in accordance with Einstein’s equation (E = mc2).
9 Fe
Binding energy per nucleon (MeV)
8 16O
12C
7 4He
0
25 50 75 100 125 150 175 200 225 250
Mass number
Figure 4.13 Mean binding energies of various nuclei

4.16
Rutherford carried out the first nuclear reaction by bombarding nitrogen (target nucleus) with a-particles
(projectile) to produce an oxygen isotope.
14 4 17 1
7N + 2 He → 8O + 1H
Nitrogen Helium Oxygen Proton
(a -particle)
Types of Nuclear Reactions
(i) Nuclear fission:

For example,
235
92 U + 01 n → 140 93 1
56 Ba + 36 Kr + 3 0 n + Enormous amount of energy
(ii) Nuclear fusion:

For example,
2
1H + 21 H → 14
2 He + Enormous amount of energy
Nuclear Fission
Very high nuclei have a lower binding energy per nucleon than the nuclei with intermediate mass. Thus,
the former are less stable than the latter. During 1934–1938, Otto Hahn and F. Strassmann observed
that when 235U is bombarded with slow-moving thermal neutrons (energy = 0.025 eV), it undergoes
fission giving barium (z = 56) as one of the products of fission. In order to explain this observation,
L. Meither and O.R. Frisch suggested that after the capture of a neutron, the uranium nucleus gets excited
and then splits into two fragments of approximately equal mass, which is known as nuclear fission.
There is an invariably mass defect during fission, that is, the total mass of products of fission is
less than the total mass of neutron and the 235U atom. The loss of mass appears in the form of energy
according to Einstein’s mass-energy relation, E = mc2.
The fission reaction is represented as follows:
235
92 U + 01 n → ( 235
92 U )→ 140 93 1
56 Ba + 36 Kr + 3 0 n + Huge amount of energy
Excited atom
The splitting of a heavier atom like Uranium-235 into a number of fragments of much smaller mass
by suitable bombardment with sub-atomic particles with liberation of huge amount of energy is called
nuclear fission.
In this reaction, in addition to the release of enormous amount of energy, the most significant
feature of nuclear fission is that more neutrons are produced than those consumed in the reaction. This
process is schematically represented in Figure 4.14.
Mechanism of Nuclear Fission—the Liquid Drop Model

In the fission process, a heavy nucleus splits apart into nearly two equal fragments of more stable nuclei
of intermediate mass. This fission reaction that occurs due to absorption of neutron may be treated as
analogous to the behaviour of a liquid drop as it contracts, elongates and eventually splits apart into two

KO n
Figure 4.14 A schematic diagram representing the uranium fission process
Figure 4.15 Schematic diagram representing the fission process by the Bohr-Wheeler liquid drop model for
heavy nuclei
droplets as shown in Figure 4.15. According to this liquid-drop model, the absorption of neutron by a
nucleus causes the nucleus to oscillate like a liquid drop and then split’s it into two small, stable nuclei.
There are 14 isotopes of uranium, and their mass number ranges from A = 227 to A = 240. The
most important isotopes are 235U and 238U whose natural relative abundance is 0.72% and 99.28%,
respectively. Both 235U and 238U undergo fission upon absorbing a neutron. 238U undergoes fission
with ‘fast’ neutrons while 235U with both ‘fast’ and ‘slow’ neutrons.
Among naturally occurring nuclides, only 235U undergoes fission, but 238U and 232Th are converted
into 239Pu and 233U by neutron capture and two successive b-decay. These two converted nuclides then
undergo fission. Both 235U and 233U can be excited to fissionable state by slow neutrons more easily than
238U as both are less stable.
The division of 235U occurs in different ways and nearly 34 elements were identified in fission
products. Enormous amount of energy is also liberated. In any single reaction, two particular nuclides
are produced along with two or three secondary neutrons. These neutrons have about 200 MeV
of kinetic energy. The daughter nuclei produced in fission reactions have different Z and A values.
Some of many pathways through which 235U undergoes fission with fast neutrons are mentioned
here.

4.18
160 72 1
62 Sm + 30 Zn + 4 0 n + energy
146 87 1
57 La + 35 Br + 3 0 n + energy
235 1 236 140 93 1
92 U+ 0n 92 U 56 Ba + 36 Kr + 3 0 n + energy
144 90 1
55 Cs + 37 Rb + 2 0 n + energy
144 90 1
54 Xe + 38 Sr + 2 n + energy
0
Since emission of more than one neutron occurs in the fission process, there is a possibility of a chain
reaction in which the releases of energy increases in geometric fashion. The neutrons released in one
fission reaction cause a second fission reaction and so on, and a chain reaction continues, which, if
goes unchecked, would quickly lead to the release of enormous amount of energy. A chain reaction
is possible only when the amount of fissionable material exceeds its critical mass (Figure 4.16). The
critical mass is defined as the amount of fissionable material, which is just large enough to recapture
one neutron, on an average, for every fission reaction. If the amount of fissionable material is less than
the critical mass, less than one neutron is recaptured; the rate of fission events does not grow, and the
rate of energy release is low. In addition, if the amount of fissionable matter is more than the critical
mass, the number of fission events increases, and a chain reaction is set up, which quickly grows into
explosive proportions.
Release of Fission Energy

On this basis, nuclear fission reactions may be categorised into two types:
(i) Uncontrolled nuclear fission used for construction of nuclear weapons, the atomic bombs
(ii) Controlled nuclear fission, which is exploited for the controlled generation of energy in nuclear
reactors
133
57 Sm
147 235 U
54 Ba 1 92
n
0
1
n
0
235 U 235 U
101 Nb
1 92 92
n 43
1 0
n
0 235 U 1 150
n Xe
92 0 57
1 235 U
n 92
235 U 0
1
n
0 92 1
n
0
90 Sr 235 U
36 92
Figure 4.16 Self-propagating nuclear chain reactions

(i) Uncontrolled nuclear fission—the atom bomb: In a fission reaction, two or three neutrons are
produced. These neutrons can collide with other fissionable atoms to sustain and multiply the
fission reactions. If the amount of fissionable material exceeds the critical mass, an uncontrolled
explosive chain reaction may result. An enormous amount of energy is produced in the chain
reaction. A nuclear bomb is a frightening example of the enormous amount of energy released
by nuclear fission, which is not controlled.
The central feature of a fission explosion is a growing chain of fission reactions. For this, there
are three requirements as follows:
(a) The fissionable nuclide must be concentrated enough so that it becomes critical.
(b) The sub-critical portions of this fissionable nuclide must be combined into a critical mass.
(c) The critical mass must be held together for a long period so that the chain multiplies to
immense size.
The potential of uncontrolled nuclear fission was first realised in the atomic bomb (Figure 4.17). It
contains two sub-critical portions of fissionable materials.
One portion is propelled into another to form supercritical mass by carefully designed detona-
tion of an ordinary chemical explosive such as trinitrotoluene (TNT). The fission chain multiplies,
and then a nuclear fission explosion occurs. Tremendous amount of heat energy and many other
radio nuclides are also released; their effects are disastrous to life and environment. The radioac-
tive dust and debris are called fall-out.
In 1945, the United States started the nuclear age by dropping two nuclear bombs on Hiroshima
and Nagasaki, Japan. Both these bombs were fission weapons of tremendous power. The bomb,
which was dropped on Hiroshima, contained 235U (Uranium-235) while the Nagasaki bomb had
239
Pu (Plutonium-239) as fissionable materials.
Subcritical235U
Subcritical235U
TNT explosive charge
Figure 4.17 A simple design of atomic bomb

(ii) Controlled nuclear fission—nuclear reactor: For controlled release of fission energy, the chain
reaction is carried out in a device called a nuclear reactor. The fission is controlled in such a man-
ner that on an average, only one neutron is left from each fission; to excite further fission, the
large amount of energy released in nuclear fission can be used to generate electrical power. This
requires a delicate balance between neutron generation and neutron loss, and this is achieved by
proper use of moderator and control rods in the nuclear reactors.

4.20
Two types of nuclear reactors are in common use. They are as follows:
(a) Thermal reactors: Most thermal reactors in the United States are ‘light water reactors’ in
which ordinary water is used as moderator to slow the neutrons. However, heavy water reac-
tors had been developed in Canada in which heavy water, D2O is used as moderator in place
of ordinary water.
Light water reactor (LWR), which is a type of thermal reactor, uses normal water as its
coolant as well as neutron moderator.
There are three varieties of LWRs:
(1) Pressurised water reactor (PWR)
(2) Boiling water reactor (BWR)
(3) Supercritical water reactor (SCWR)
• Reactor design: The LWR produces heat by controlled nuclear fission. The nuclear
reactor core is the major portion of a nuclear reactor where the nuclear reactions
take place (Figure 4.18).
It consists essentially of the following parts:
• Fuel: The fissionable material used in the reactor is called fuel. The fuel used is
enriched uranium-235 (in the form of U3O8). This is obtained from the naturally
occurring U-235. The solid fuel is made into the form of rods or pellets, shielding
by placing them in stainless steel tubes.
• Moderator: The most efficient fission reactions occur with slow neutrons. Thus,
moderators, which are atoms of comparable mass, slow down the fast neutrons
produced in fission and do not absorb them. Light water reactor uses ordinary
water, also called light water, as its neutron moderator (Figure 4.18).
• Control rods: To control the fission process, rods made of cadmium or boron are
suspended between the fuel rods. These rods can be raised or lowered and control
the fission process by absorbing neutrons. Therefore, they are called control rods.
Cadmium and boron are good neutron absorbers.
113
48 Cd + 01 n → 114
48 Cd +g
10
5B + 01 n → 115 B+g
Containment
structure
Steam line
Pressure
vessel Turbine
Isolation
generator
Steam valves
Core Pump
Control rods Condenser

cooling
Water pool water
Figure 4.18 Light water nuclear reactor

• Cooling system: The LWR uses ordinary water to keep the reactor cooled. The light
water is circulated in the reactor core to absorb the heat, which is generated due to
fission reaction. This transfers the heat to a steam generator, which converts water
into steam, and this steam is then taken to turbines, which drive generators to produce
electricity.
• Shielding: To prevent loss of heat and protect the persons operating the reactor from
radiation and heat, the entire reactor core is enclosed in a steel containment vessel.
This vessel is housed in a thick-walled concrete building. The operating people are
protected by a thick layer of organic material made of compressed wood fibres, which
absorb the neutrons, b particles and g-rays.
(b) Breeder reactors: Considering the rate at which U-235 is being used to produce power,
the stocks are likely to exhaust very soon. Therefore, scientists have been actively engaged
in investigating other fissionable materials. They have found plutonium-239 (Pu-239) and
uranium-233 (U-233) to be quite suitable. These are produced by bombardment of more
abundantly available U-238 and Th-232 with neutrons.
A breeder reactor is a nuclear reactor that breeds fuel. It consumes fissile and fertile
material at the same time as it creates new fissile material. In this reactor, neutrons pro-
duced from fission of U-235 are partly used up for carrying on fission of U-235 and partly
to produce Pu-239 or U-233. Such reactors produce more fissionable materials (as Pu-239 or
U-233) than they consume (as U-235).
The sequence of reactions that take place when U-238 and Th-232 are bombarded with fast
neutron producing the fissionable nuclei of Pu-239 and U-233 are represented as follows:
(1) Fissionable Pu-239 by neutron bombardment followed by two successive b-decays.
− −
238
92 U + 01 n → 239
92 U b→ 239 b 239
93 Np → 94 Pu
(2) Fissionable U-233 by neutron bombardment on Th-232 by two successive b-decays.

− −
232
90Th + 01 n → 233
90Th b→ 233 b 233
91 Pa → 92 U
The neutrons produced by fission reactions are absorbed in a blanket of uranium or

thorium. Since higher temperature is required to operate, water cannot be used as a coolant.
Liquid sodium is used as a coolant. This type of reactor uses fast neutrons; therefore, no
moderator is required.
The nuclides such as U-238 and Th-232, which can be converted into fissionable nuclides,
are called fertile nuclides, whereas nuclides such as U-235 and Pu-239, which are fissionable
and are called fissile nuclides.
Nuclear Fusion
Nuclear fusion may be defined as a process of combination of two lighter nuclides to form a heavier
nuclide with the release of energy.
The following reactions have been successfully investigated as fusion reactions:
1 2
1H + 1H → 23 H + γ
2 2
1H + 1H → 42 H + Q(= 3.25 MeV)
2 2
1H + 1H → 31 H + 11 H + Q(= 4.0 MeV)
2 3
1H + 2 H → 42 He + 11 H + Q(=18.3MeV)

4.22
These processes are generally known as thermonuclear reactions, because they require that the collid-
ing nuclei must possess very high kinetic energies before they are initiated. The high kinetic energies
of the reacting nuclei overcome the coulombic repulsion between positive particles of reactants. This is
only possible of extremely high temperature of millions of degrees (≈ 4 × 106 °C), so these processes
generally occur in the sun and other stars because of tremendous high temperatures that are nearly
impossible to achieve and contain on earth. It is, therefore, believed that in the sun, the following pro-
cess takes place:
4 11 H → 42 He +2 +01 e + γ
There is evolution of 26 MeV of energy, and this energy is available to us from the sun and keeps the
sun at extremely high temperature.
The fission reactions take place only with a few rare and extremely heavy nuclides. On the other
hand, fusion reactions are possible for light nuclides such as 1H, which are abundant. Furthermore,
fusion reactions release more energy per unit mass than fission reactions. For example, fission of
U-235 yields 7.9 ×107 KJ/g energy while fusion of two isotopes such as hydrogen, deuterium and
tritium releases 3.4 ×108 KJ/g energy. Another advantage of fusion reaction is that the fusion reac-
tion produces radio nuclides of very short half lives, so there would be no long-term waste disposal
problem.
There are several ways to study fusion reactions as follows:
(i) By using particle accelerators.
(ii) Through stellar nuclear reactions, the process occurs in the sun and other stars.
(iii) By fusion bombs, which use a fission bomb to produce a temperature high enough for fusion.
Fusion Bombs (Uncontrolled Nuclear Fusion Reactions)

A hydrogen bomb uses nuclear fusion. A conventional explosive first triggers a fission bomb, which
then induces the fusion reaction. These bombs are more powerful than fission bombs because they can
incorporate large masses of nuclear fuel to produce unlimited energy.
A hydrogen bomb has an arrangement of nuclear fission in the centre, which is surrounded by a
mixture of deuterium ( 21 H) and lithium 6 isotope ( 63 Li).
Nuclear fission provides heat and neutrons. The neutrons are used up for converting lithium iso-
tope into tritium ( 31 H), and the heat liberated is required for the fusion between 21 H and 31 H to start.
The fusion reactions are then accompanied by the liberation of a large amount of energy.
Thus the reactions taking place in a hydrogen bomb may be represented as follows:
Fission (in the centre) → Heat Neutrons
6
3 Li + 01 n → 31 H + 42 He + 4.78 MeV
2 3
1H + 1H → 42 He + 01 n + 17.6 MeV
2 2
1H + 1H → 23 He + 01 n + 3.3MeV
3 3
1H + 1H → 42 He + 2 01 n + 11MeV
All these processes occur in an extremely short time to release an immense amount of energy, and the
bomb blasts.

Controlled Nuclear Fusion

The major problem in a nuclear fusion reaction is the attainment of high temperature required for the
purpose. So far, attempts to maintain such a high temperature to generate energy on a large scale have
been successful for only a very small fraction of a second, because all known containers would vapour-
ise at such a high temperature. At this temperature, the atoms become fully ionised, and the ions (i.e.,
nuclei and electrons) form the plasma state in which the particles move about independently but in the
form of inter penetrating gases. The plasma is electrically neutral.
Lastly, it can be mentioned that the attempts to make fusion reactors have not met with any suc-
cess so far because of many technical difficulties involved, for example, that of the container material,
which can withstand very high temperatures as required for the fusion to start. However, if a solu-
tion is found, it will place at our disposal a tremendous source of energy at a very cheap rate because
deuterium is present in huge amount in sea water (in the form of D2O).
The differences between nuclear fission and nuclear fusion are listed in Table 4.1.
Table 4.1 Differences between nuclear fission and nuclear fusion

S.No. Nuclear fission Nuclear fusion
1. It involves breaking up of a heavier nucleus into It involves union of two lighter nuclei to form
lighter nuclei. heavier nuclei.
2. It is a chain process. It is not a chain process.
3. It is initiated by neutrons of suitable energy and It is initiated by very high temperature, by a few
does not need high temperature. million degrees.
4. It can be controlled, and the energy release can It is difficult to control this process.
be harnessed for useful purpose.
5. Large number of radio-isotopes is formed, and There is no nuclear waste in this process.
there is nuclear waste.
6. It requires minimum size of fissionable material, There is no limit to the size of the fuel for the reac-
and if the size of the material exceeds the criti- tion to start. However, the fuel does not undergo
cal size, the reaction becomes explosive. fusion until heated to a very high temperature of a
few million degrees.

1. In wind, is converted into mechanical energy or electrical energy.
[Ans.: kinetic energy]
2. is used to produce biofuel.
[Ans.: algae]
3. Geo thermal resources are .
[Ans.: hydrothermal, geopressure, hot dry rocks and magma]
4. Complete the following reactions:
(a) 7 N14 + 01 n → 147 C+
27
(b) 13 Al + → 15 P30 + 01 n
[Ans. : a = 1 H1 ; b = 42 He]

4.24
5. is used as a coolant in nuclear reactor.

[Ans.: light water]
6. Atom bomb is based on .
[Ans.: nuclear fission]
7. isotope of uranium is used in nuclear reactor.
235
[Ans.: U ]
8. Nuclear reaction is produced large quantities of energy according to equation.
[Ans.: Einstein energy mass E = mc2]
9. A fission reactor which produces more fissionable material than its consumed in its operation
is reactor.
[Ans.: breeder]
10. changes alter the number of protons and neutrons in the nuclei of atoms consumed
while simple chemical changes involve in reorganization of only.
[Ans.: nuclear, electrons]
11. Sun’s energy is given by fusion of nuclei.
[Ans.: hydrogen]
12. Photovoltaic cell converts directly incident solar radiations to .
[Ans.: electric current]
13. The major material used in pv cell is .
[Ans.: silicon]

1. Generating mechanical power by using wind is called
(a) Solar energy (b) Tidal energy
(c) Wind energy (d) Biofuels
[Ans.: d]
2. Geothermal energy comes from
(a) Heat from within earth (b) Heat from atmosphere
(c) Heat from organic matter (d) None of the above
[Ans.: a]
3. Bio-fuel producing pollutes are
(a) H2 and O2 (b) Oxides of sulphur and nitrogen
(c) H2O (d) None of the above
[Ans.: b]
4. Energy which is not harm to the environment is
(a) Solar energy (b) Wind energy
(c) Alternative energy (d) None
[Ans.: c]

5. Among the following, which one belongs to alternative energy?

(a) Tidal Energy (b) Wind energy
(c) Solar energy (d) All of the above
[Ans.: c]
6. The source of energy in nuclear fuel is due to
(a) Chemical reaction (b) Nuclear reaction
(c) Nuclear fission (d) Nuclear fusion
[Ans.: c]
7. Binding energy of a nucleus is related with
(a) ∆Mc2 (b) Mc2
(c) ∆Mc (d) hv
[Ans.: a]
8. Fissionable material used in nuclear reactor is
(a) U235 (b) U238
(c) Th232 (d) Pu239
[Ans.: a]
9. 21 H + 21 H → ?
(a) 23 He (b) 42 H
(c) 42 He (d) None of these
[Ans.: c]
10. Control rods used in nuclear reactor is made of
(a) Na (b) B
(c) CO2 (d) U235
[Ans.: b]
11. Atom bomb is based on principle of
(a) Nuclear fusion (b) Nuclear fission
(c) Chemical reaction (d) None of these
[Ans.: b]
12. Uncontrolled nuclear fusion reaction takes place in
(a) Atom bomb (b) H-bomb
(c) Nuclear bomb (d) Radium bomb
[Ans.: b]
13. Solar energy originates from the reaction taking place in the sun
(a) Nuclear fusion (b) Nuclear fission
(c) Chemical reaction (d) Nuclear reaction
[Ans.: a]
14. Photovoltaic cells are commonly known as
(a) Primary cell (b) Solar cell
(c) Secondary cell (d) Fuel cell
[Ans.: b]

4.26
15. Example of indirect solar energy is

(a) Nuclear energy (b) Wind energy
(c) Chemical energy (d) Surface energy
[Ans.: b]

1. Give definitions of alternative energy from different sources.
Ans.: Oxford definition: Energy fueled into ways that do not use up natural resources or harm
the environment.
Princeton WordNet: Energy derived from sources that do not use up natural resources or
harm the nature.
Natural resource defense council: Energy that is not popularly used and is usually envi-
ronmental sound such as solar or wind energy.
Material and management: Fuel source other than those derived from fossil fuels typi-
cally interchangeably used for renewable energy.
For example, wind, solar, biomass, wave and tidal energy.
Torridge District Council: Energy generated from alternatives to fossil fuel; but need not
be renewable.
Climate Change 2007: Energy derived from nontraditional sources.
For example, compressed natural gas, solar, hydroelectric and wind energy
2. Write a short note on wind energy.
Ans.: The term ‘wind energy’ or ‘wind power’ describes the process by which the kinetic energy
of wind is used to generate mechanical power or electricity with turbines.
3. Explain geothermal energy.
Ans.: Geothermal energy comes from the heat within the Earth. Geothermal is a Greek word;
geo–earth and thermal–heat. Geothermal energy is used to produce electricity, green
houses and to heat building for other sources.
4. Write a short note on biofuels.
Ans.: Biofuel is any fuel derived from biomass of recently living organisms or their metabolic
byproducts, such as manure from cows. Algae fuel is a biofuel which is derived from
algae. During photosynthesis, algae and other photosynthetic organisms capture carbon
dioxide and sunlight and convert them into oxygen and biomass. This is usually done by
placing the algae between two panes of glass. The algae create three forms of energy fuel:
they are from its growth cycle heat can generate, the oil derived from the algae used as
biofuel, and on maturity algae can give biomass.

Q.1 Write a brief note on geothermal energy.
Q.2 Write a note on wind energy.
Q.3 Explain the importance of biofuels.

Q.4 Explain any three alternative energy resources.

Q.5 Define alternative energy resources and explain water power.
Q.6 Discuss the theoretical principles involved in the generation of power by nuclear fission and
nuclear fusion.
Q.7 Describe the various components of a nuclear power reactor and their functions.
Q.8 Discuss the environmental aspects of nuclear power generation.
(a) Breeder reactors
(b) Energy from nuclear fusion.
Q.10 Write notes on nuclear fission and fusion.
Q.11 (a) Explain how fission grade U235 is obtained.
(b) Write short note on nuclear binding energy.
Q.12 What are the functions of following in a nuclear reactor?
235
(a) U
(b) Cadmium rods
Q.13 Define nuclear reaction.
Q.14 Calculate the binding energy in Mev of 42 H , if its experimentally determined mass is 4.00390
amu. The masses of a proton, an electron and a neutron are respectively 1.007825, 0.0005852 and
1.008668 amu.
Q.15 Explain how binding energy is useful for the stability of a nucleus.
Q.16 Write the difference between nuclear fusion and nuclear fission.
Q.17 Write the principle involved in atomic bomb and its reactions.
Q.18 Write the reaction taking place in sun and stars.

5 Electrochemistry
and Batteries
5.1 Introduction
Electrochemistry is defined as the branch of chemistry which deals with the relationship between
electrical energy and chemical changes taking place in redox reactions i.e., how chemical energy pro-
duced in a redox reaction can be converted into electrical energy or how electrical energy can be used
to bring about a redox reaction which is otherwise non-spontaneous.
When electricity is passed through the solution of an electrolyte to bring about a redox reaction
known as electrolysis and the arrangement is called an electrolytic cell and when electricity is pro-
duced by redox reactions (which are spontaneous) gives rise to what are known as electrochemical cell
or galvanic cell or voltaic cell.
In an electrolytic cell, the flow of electricity through the solution is due to the flow of ions and in an
electrochemical cell, the flow of current is due to flow of electrons in the external circuit and the flow
of ions through the solution in the inner circuit. The flow of current due to movement of ions through
the solution of an electrolyte is known as electrolytic conduction.
Thus, the three main aspects of study in the branch of electrochemistry are:
(i) Electrolysis
(ii) Electrolytic conduction
(iii) Electrochemical cells
5.2 Electrolysis
Electrolysis is a process of decomposition of an electrolyte by the passage of electricity from an external
source through its aqueous solution or molten state for performing chemical reactions.
Electrolysis requires the use of electrolytic conductors (electrolyte) in the form of an aqueous solu-
tion or in the molten state as well as electronic conductors (electrodes) which are essential components
of an electrolytic cell. Two metal electrodes are dipped in electrolyte and are connected to a source of
electricity i.e. battery. The electrode, which is connected to a positive pole of the battery is called anode
and second electrode is called cathode which is connected to negative pole of the battery. Oxidation
and reduction occur at the electrodes as shown in Figure 5.1.

D.C. Source Ammeter
e− e−
Anode Cathode
− +
− +
− +
− +
− +
− +
Figure 5.1 Electrolytic cell
When an electrolyte is dissolved in water or taken in the molten state is dissociate into charged
ions i.e., cation and anion. On passing electric current, cations move towards the cathode and anions
move towards anode. After reaching at their respective electrodes, reaction takes place.
Oxidation occurs at the anode while reduction takes place at the cathode.
(i) For example electrolysis of molten sodium chloride, it consist of Na+ and Cl− ions.
NaCl(l ) Na + (l ) + Cl − (l )
On passing electricity, ions moves towards their respective electrodes. Sodium metal is liberated
at the cathode and Cl2 is evolved at the anode.
At cathode: 2 Na + + 2e − → 2 Na (reduction)
At anode: 2Cl − → Cl 2 + 2e − (oxidation)
The electrons released at the anode pass through the external circuit and reach the cathode so
that Na+ ions can be reduced. Thus, on oxidation reaction occurs at the anode and a reduction
reaction at the cathode.
(ii) Electrolysis of an aqueous solution of copper sulphate in electrolytic cell using Pt electrodes,
reduction of the cupric ions occurs to copper and is deposited on the cathode, simultaneously
release of oxygen gas at the anode occurs and reaction may be represented as:
At cathode: Cu 2 + + 2e − → Cu (reduction)
− 1 −
At anode: 2OH → H 2 O + O2 + 2e (oxidation)
2
Both SO42- and OH− ions are present near anode. Since the discharge potential of OH− ions is
lower than that of SO42- ions, therefore, OH− ions are discharged with respect to SO42- ions and
SO42- anions are charge carriers in the electrolyte.
5.2.1 Laws of Electrolysis

Faraday in 1833 put forward the relationship between the amount of a substance deposited or dissolved
during the electrolysis of aqueous solutions and the quantity of electricity passed through the electro-
lyte in the form of two laws of electrolysis.

Electrochemistry and Batteries 5.3
Faraday’s First Law of Electrolysis

The first law of electrolysis states that the mass of any substance deposited or liberated at any electrode
due to passage of an electric current is proportional to the quantity of electricity passed.
If W gram of the substance is deposited on passing Q coulombs of electricity, then
W ∝ Q or W = ZQ
Where Z = constant of proportionality and is called as electrochemical equivalent (ECE) of the

substance deposited.
If a current C amperes is passed for t seconds, then
Q=C×t
So that W=Z×Q=Z×C×t
Thus if Q = 1 coulomb or C = 1 ampere or t = 1 second, W = Z.

Hence, electrochemical equivalent (ECE) of a substance may be defined as the mass of the sub-
stance deposited when a current of one ampere is passed for one second i.e., a quantity of electricity
equal to one coulomb is passed.
Electrochemical equivalent can be calculated from the equivalent weight, as one Faraday
(96500 coulombs) deposits one gram equivalent of the substance,
Eq. wt. of the substance
Z=
96500
Faraday’s Second Law of Electrolysis

Faraday’s second law states that when the same quantity of electricity is passed through solutions of
different electrolytes connected in series, the amounts of different substances produced or deposited at
the electrodes are directly proportional to their equivalent weights.
Thus if w1 and w2 are the amounts produced or deposited as the two substances having chemical
equivalent weights of E1 and E2 on passing Q coulombs of electricity.
w1 E1 Z1
= =
w2 E2 Z 2
The charge carried by one mole of electrons can be obtained by multiplying the charge present
on one electron with Avogadro’s number i.e. it is equal to (1.6023 × 10-19 coulombs) × (6.022 × 1023) =
96490 coulombs (∼96, 500 coulombs or 26.8 A.hr). This quantity of electricity is called one Faraday or
Faraday’s constant and is represented by F.
Hence, Faraday’s constant
F = 96490 C mol −1 96500 C mol −1
(i) In terms of electrons:

If n electrons are involved in the electrode reaction, the passage of n Faradays (i.e., n × 96500 C)
of electricity will liberate one mole of the substance.
(ii) In terms of gram equivalents:
One Faraday’s (i.e., 96500 Coulombs) of electricity deposits one gram equivalent of the substance.

Thus by knowing the weight of substance deposited (w gram) on passing a definite quan-
tity of electricity (Q coulombs), the equivalent weight of the substance can be calculated as:
w
Eq. wt. = × 96500
Q
Q = c×t
w
So, E= × 96500.
c×t
So, by knowing the quantity of electricity passed, the amount of substance deposited
can be calculated.
5.3 Electrolytic conDUCTION

(i) The substances which allow electricity to pass through them are known as conductors. For
example metals, graphite, acids, bases, fused salt etc.
(ii) Some substances which do not allow electricity to pass through are known as insulators. For
example: Mica, non-metals, wood, rubber, benzene etc.
(iii) Conductors are further divided into two classes such that one class is for those which conduct elec-
tricity without undergoing any decomposition. These are called electronic conductors e.g., metals,
graphite and other minerals. In such type of substances, conduction is due to the flow of electrons.
(iv) The second class is for those which conduct electricity when current is passed through them or
they undergo decomposition. These are called as electrolytic conductors or electrolytes e.g., solu-
tion of acids, bases and salt in water, fused salt etc. In such type of substances, conduction is due
to the movement of ions.
(v) There are two types of electrolytes such as strong electrolyte and weak electrolyte. Strong electro-
lytes are those which dissociate almost completely in the aqueous solution or in the molten state
and conduct electricity to a large extent e.gs. → NaOH, KOH, HCl, HNO3, H2SO4 etc. and weak
electrolytes are those which have low degree of dissociation and hence conduct electricity to a
small extent e.gs. → NH4OH, CH3COOH, HCN, Ca(OH)2, Al(OH)3 etc.
(vi) The substances which don’t dissociate and donot conduct electricity are known as non-electrolytes
e.gs: Sugar, urea, glucose etc.
5.3.1 Factors Affecting Electrolytic Conduction

(i) Viscosity of the solvent decreases with increase of temperature. Hence electrolytic conduction
increases with increase of temperature.
(ii) Polarity of the solvent affect on electrolytic conduction, greater is the polarity of the solvent,
greater is the ionization and hence greater is the conduction.
(iii) In case of concentrated solution, conduction is less but as the dilution starts, conduction is also increases.
(iv) When temperature increases, dissociation of solution increases and hence the conduction also
increases.
5.3.2 Electrical Resistance and Conductance

Every substance offers resistance to the flow of electricity to a small or large extent. This law is known
as Ohm’s law. This law is applicable to both metallic conductors as well as electrolytic conductors.
Ohm’s law states that if to the ends of a conductor is applied a voltage ‘E’ and a current ‘I’ flows
through it, then resistance ‘R’ of the conductor is given by

E
R=
I
When current is measured in amperes, voltage is measured in volts. If one ampere current flows
through a conductor when a voltage of one volt is applied to it, then resistance of the conductor is taken
as 1 Ohm (written as 1 ‘Ω’ omega)
E Volts
R= or Ohm =
I Amperes
According to Ohm’s law, when a substance offers greater resistance will allow less electricity to
flow through it.
1
I∝
R
The reciprocal of the electrical resistance is called as conductance. It is usually represented as ‘C’.
Thus
1
C=
R
Units
1
C=
Ohm
= Ohm −1 or mho or siemens
i.e., (1 S = 1 Ω−1)
The S.I unit of conductance is Siemens (S).
5.3.3 Specific, Equivalent and Molar Conductivities

Specific Conductivity
Specific conductivity is also known as conductivity. Experimentally, it is observed that resistance R of
a conductor is
(i) Directly proportional to its length (l) and
(ii) Inversely proportional to its area of cross section (a)
i.e.,
l l
R∝ or R= r
a a
Where r is a constant of proportionality, called specific resistance or resistivity. Value of resistivity
depends upon the material of the conductor.
“The reciprocal of resistivity is known as specific conductivity or conductivity or electrolyte con-
ductivity.” It is denoted by k (kappa) or K.
Thus, if K is the conductivity and C is the conductance. Then, we know that
1 1
R= and r=
C K
∴ Formula change into
l
R= r
a
1 1 l
=
C Ka

Now if l = 1 cm and a = 1 cm 2, then K = C.

Hence conductivity of a solution is defined as the conductance of a solution of 1 cm length and
having 1 sq. cm as the area of cross section.
Alternatively, it may be defined as conductance of one centimeter cube of the solution of the elec-
trolyte as represented by the Figure 5.2.
1cm −
+
m
1cm
1c
Figure 5.2 Electrolyte conductivity
“If the volume of the solution is V cm3, then conductivity of such a solution at this dilution V is
written as KV.”
Units
a
Resitivity (r ) = R
l
cm 2
= ohm
cm
= ohm.cm or Ω cm
1
Conductivity (K ) =
r
1
=
ohm.cm
= ohm −1 cm −1 or Ω −1 cm −1 or mho cm −1
C.G.S unit of conductivity = mho cm−1 or S cm−1
S.I unit of conductivity = S m−1
1 S m−1 = 0.01 S cm−1
5.3.4 Equivalent Conductivity

Consider the solutions having equal volumes and containing their corresponding gram equivalent
weights for the comparison of the conductances of the solutions of different electrolytes. Then conduct-
ance of such solution is called its equivalent conductivity or equivalent conductance.
Hence equivalent conductance of a solution is defined as the conductance of all the ions produced
from one gram equivalent of the electrolyte dissolved in V cm3 of the solution when the distance between
the electrodes is one cm and the area of the electrodes is so large that whole of the solution is contained
between them.
Equivalent conductivity or equivalent conductance is represented by Λeq (lambda)
(i) If the volume of solution is V cm3 containing one gram equivalent of the electrolyte,
Then,
Equivalent conductivity = Specific conductivity × V
Λeq = KV × V

(ii) If the solution has concentration of C gram equivalent per litre i.e., C gram equivalents are pres-
ent in 1000 cm3 of the solution, then volume of solution containing one gram equivalent will
1000
be .
C
Hence, Λeq = K v × V can be written as
1000 1000
Λ eq = K c × = Kc ×
Ceq Noramality
Units
Λ eq = K × V
cm3
= ohm −1 cm −1 ×
gram eq
= ohm −1 cm 2 (g eq) −1 or mho cm 2 eq −1
or S cm 2 eq-1
S.I unit is S m 2 eq-1
Hence,
1 S m 2 eq-1 = 104 S cm2 eq-1
5.3.5 Molar Conductivity

The molar conductivity of a solution is defined in a manner similar to that of equivalent conductivity.
The term molar conductivity is sometimes also called as molar conductance or molecular conductivity.
It is usually represented as Λm or m.
The molar conductivity of a solution is defined as the conductance of all the ions produced from
one mole of the electrolyte dissolved in V cm3 of the solution when the electrodes are one cm apart and
the area of the electrodes is so large that whole of the solution is contained between them.
Similar to equivalent conductivity, molar conductivity is given by following expression as follows:
Λm = Kv × V
or
1000 1000
Λ m = Kc × = Kc ×
C Molarity
Where Kc = is specific conductivity
V = Volume of the solution containing one mole of the electrolyte
C = molar concentration
Units
Λ m = Kv × V
cm3
= ohm −1 cm −1 ×
mol
= ohm −1 cm 2 mol −1 or Ω −1 cm 2 mol −1
or mho cm 2 mol −1 or S cm 2 mol −1

5.3.6 Measurement of Electrolytic Conductance

As we know that conductance is the reciprocal of the resistance. Hence conductance can be obtained by the
measurement of the resistance and resistance can be found by the principle of Wheatstone bridge method.
In finding the resistance of the solution of an electrolyte, a special type of cell has to be used such
that the solution is present between the two electrodes. The cell thus used is called as conductivity cell.
It consists of platinised Pt electrodes at a fixed distance apart and resistance is measured using alternat-
ing current to prevent any deposition on the electrodes during electrolysis as represented in Figure 5.3.
In this process, an alternating current of frequency 500-2000 Hz is used. A signal generator such as a
variable frequency oscillator, a null detector-indicator such as ear phone or a sensitive micro ammeter
is used as a detector.
Variable resistance
R Cell
C
A B
J Jockey
Electrolytic
Earphone
solution
Alternation Conductivity Cell

current source
Figure 5.3 Wheatstone bridge circuit
Hence, Wheatstone bridge circuit consists of

(i) Source of alternating current which is either from induction coil or a vacuum tube oscillator.
(ii) An earphone
(iii) Platinised Pt electrodes
(iv) Variable resistance with standard resistance box
In this method, a suitable value of resistance R is introduced from the standard resistance box such
that when the sliding contact i.e., the Jockey J is moved along the stretched wire, the sound in the ear-
phone is reduced to minimum at the point somewhere in the middle of the wire AB, say at the point C.
Then if X is the resistance of the electrolytic solution, then by Wheatstone bridge principle,
Resistance R Resistance of wire AC

=
Resistance X Resistance of wire CB
length AC
=
length BC
length BC
Resistance, X = Resistance R ×
length AC
Thus, knowing the resistance R and the balance point C, resistance X of the electrolytic solution
can be calculated.

Hence,
1 1 length AC
Conductance, C = = ×
Resistance X R length BC
To calculate specific conductivity, which is related with the conductance according to the expression
l
K =C ×
a
Thus specific conductivity of a solution can be determined by measuring its conductance and the
distance (l) between the electrodes and area (a) of cross section of each of the electrodes.
l
For a particular cell, is constant and this constant is called as cell constant.
a
Hence,
Specific conductivity (K) = conductance × cell constant
Thus, the cell constant of any particular cell can be found by measuring the conductance of a solu-
tion whose specific conductivity is known. First of all we have to remove all types of organic as well as
other oily impurities which are sticking to the walls of the cell and electrodes by cleaning with dilute
N
chromic acid. Then we dipped the electrodes of the cell in KCl solution whose specific conductivity
50
is known.
N
By Kohlrausch it is verified that at 25 °C value of specific conductivity of KCl is
50
0.002765 ohm-1 cm−1. Hence by knowing the value of cell constant, the specific conductivity of the given
solution can be determined by measuring its conductance and multiplying the value with the cell constant.
Equivalent conductivity (Λ eq ) can be calculated by using the relation
1000
Λ eq = Specific conductivity ×
Ceq
1000 1000
=K× =K×
Ceq Normality
Molar conductivity (Λm) can be calculated by using the relation
1000
Λ m = Specific conductivity ×
C
1000 1000
=K× =K×
C Molarity
Hence, by knowing the molar concentration, C and specific conductivity K, Λeq (equivalent con-
ductivity) and Λm (molar conductivity) can be calculated.
5.3.7 Variation of Conductivity with Concentration

As we know that, specific conductivity (K) as well as equivalent conductivity (Λeq ) and molar conduc-
tivity (Λm) vary with the concentration of the electrolyte.
The specific conductivity K decreasing with increasing dilution (decrease in concentration) of
the electrolyte solution while equivalent and molar conductance increases with increase in dilution
(decrease in concentration) which is easily understood by the relation.

5.10
1000
Equivalent conductivity Λ eq = K × = K ×V
C
and
1000
Molar conductivity Λ m = K × = K ×V
C
As mentioned above, equivalent conductance increases with increase in dilution and this
value approaches to a limiting value as the dilution of the electrolytic solution increases. This limiting
equivalent conductance value is called the equivalent conductance at zero concentration or infinite
dilution Λ0 or Λa . With increasing dilution, dissociation of the electrolyte increases, hence equivalent
conductance increases but the number of ions per unit volume decreases so specific conductance K
decreases.
On the basis of an empirical relationship between the equivalent conductance and concentration
given as
Λc = Λ0 − b c
Where b is a constant depending upon the nature of the solvent.

Λ0 = specific conductivity at infinite dilution
This equation is called Debyl Huckel-Onsagar equation and is found to hold good at low
concentrations.
5.3.8 Conductance Behaviour of Strong Electrolyte

In case of strong electrolyte, the equivalent conductance does not vary very much with dilution.
A linear graph is obtained for low concentrations but it is not linear for higher concentrations. The
curve shows that there is small increase in conductance with dilution. This is because a strong elec-
trolyte is completely dissociated in solution and so the number of ions remains constant with increase
in dilution, conductance increases and approaches a maximum limiting value at infinite dilution i.e.,
Λ0 or Λ∝.
Examples of strong electrolytes include strong acids and bases (NaOH, HCl, H2SO4, and KOH)
and solutions of ionic solids (NaCl, KNO3, KCl etc).
5.3.9 Conductance Behaviour of Weak Electrolyte

In case of weak electrolyte, equivalent conductance increases rapidly with decrease in concentration.
But conductance of a weak electrolyte is much lower than that of a strong electrolyte at the same con-
centration. Further the curve obtained for a weak electrolyte shows that there is a very large increase
in conductance with dilution especially near infinite dilution as shown in Figure 5.4.
This is because as the concentration of the weak electrolyte is reduced, more of it ionizes. Thus,
increase in conductance with decrease in concentration is due to the increase in the number of ions in
the solution. However, it does not reach a limiting value, So Λ0 or Λ∝ cannot be determined graphically
as in the case of strong electrolyte.
Examples of weak electrolytes include weak acids and bases (acetic acid, other organic acids and
ammonia) and weakly dissociating salts.

Equivalent conductance Λeq.(mho cm2 mol−1)

Λ0
Strong electrolyte (KCI)
Weak electrolyte (CH3COOH)
Concentration( c ) (mol L−1)−½

Figure 5.4 Variation of equivalent conductance of a strong
and weak electrolyte with electrolyte concentration
Variation of equivalent conductance with concentration of strong (KCl) and weak (CH3COOH)
e lectrolytes at 25 °C
Equivalent conductance mho cm2 mol-1
Concentration C mol L-1 Strong electrolyte KCl Weak electrolyte CH3COOH
0.10 128.6 5.2
0.05 133.4 7.4
0.02 138.3 11.6
0.01 141.3 16.2
0.001 146.9 48.6
0.0005 149.86 390.71
5.4 Kohlrausch’s Law Of Independent Migration Of Ions

The equivalent conductance of an electrolyte solution is equal to the sum of the conductivity of the
constituent cations (l +) and anions (l-) and is expressed as
Λeq = l + + l-
The equivalent conductance of an electrolyte solution increases with increasing dilution. At high
concentrations, the greater inter-ionic attraction retard the motion of ions and therefore the conduct-
ance falls with increasing concentrations. But with decrease in concentration (increase in dilution)
the ions are far apart and therefore the interionic attractions decreases due to which the conductance
increases with dilution. So, at infinite dilution, the equivalent conductance reaches its maximum value
as the retarding effects of the ionic atmosphere completely disappear.
Λ 0 = l 0c + l 0a

5.12
Where l 0c and l 0a are called the ionic conductivities at infinite dilution for the cation and anion
respectively and this equation is known as the Kohlrausch’s law of independent conductance of
ions.
The equivalent conductivity of an electrolyte at infinite dilution is the sum of two values one
depending upon the cation and the other upon the anion. This equation stated as at infinite dilution,
each ion makes a definite contribution to the equivalent conductance of the electrolyte whatever be the
nature of the other ion of the electrolyte.
In 1875, Kohlrausch made a series of measurement in which he observed that the differ-
ence between Λ° values for each pair of sodium and potassium salts having a common anion
was same, irrespective of what this anion was. Similarly, the difference in the Λ° values for each
pair of salts having the different anions and a common cation was same, irrespective of what this
cation was.
Λ° values at 25 °C of some pair of electrolytes having common ions

Electrolyte Λ0 Difference Electrolyte Λ0 Difference
KCl 149.86 KBr 151.92
23.41 2.06
NaCl 126.45 KCl 149.86
KBr 151.92 NaBr 128.51
23.41 2.06
NaBr 128.51 NaCl 126.45
KNO3 144.96 LiBr 117.09
23.41 2.06
NaNO3 121.55 LiCl 115.03
The ionic conductivity values of some common ions at 25 °C is presented in Table 5.1.
Table 5.1 Ionic conductivities at infinite dution at 25 °C is in mho cm2

Cations l0c Anions l0a
+ 349.8 - 198.6
H OH
Li+ 38.6 F- 55.4
Na+ 50.1 Cl- 76.4
K+ 73.5 Br- 78.1
Ag+ 61.9 I- 76.8
NH +4 73.3 NO3- 71.5
Mg2+ 53.1 ClO4- 67.4
Ca2+ 59.5 IO 4- 54.5
Ba2+ 63.6 HCOO- 54.6
Cu2+ 53.6 CH3COO- 40.9
Zn2+ 52.8 SO42- 80.0
Sr2+ 59.4 CO32- 69.3

Applications of Kohlrausch’s Law

Conductance measurements have a wide range of numerous applications. A few of them are discussed
below:
(i) Determination of equivalent conductivity at infinite dilution (L0) for weak electrolytes:
As already mentioned, the equivalent conductivity of a weak electrolyte at infinite dilu-
tion cannot be determined experimentally, firstly because the conductance of such a solution
is low and secondly because the dissociation of such an electrolyte is not complete even at
very high dilutions. The equivalent conductivity at infinite dilution can be calculated using
Kohlrausch’s law.
Consider the example of acetic acid (CH3COOH) as the weak electrolyte. By Kohlrausch’s
law
Λ0 (CH3COOH) = l0 (CH3COO-) + l0(H+)
This equation can be arrived at by knowing the molar conductivities at infinite dilution for
the strong electrolytes KCl, CH3COOK and HCl as by Kohlrausch’s law
Λ0 (KCl) = l0 (K+) + l0 (Cl-)
Λ0 (CH3COOK) = l0 (CH3COO-) + l0 (K+)
l0 (HCl) = l0(H+) + l0(Cl-)
Hence, we required
l0 (CH3COO-) + l0(H+) = l0 (CH3COO-) + l0(K+) + l0(H+) + l0(Cl-) - l0(K+) - l0 (Cl-)
i.e. Λ0 (CH3COOH) = Λ0 (CH3COOK) + Λ0(HCl) - Λ0(KCl)
(ii) Determination of the degree of dissociation or ionisation of weak electrolyte:
According to Arrhenius theory of electrolytic dissociation, the increase in the equivalent con-
ductivity with dilution due to the increase in the dissociation of the electrolyte and reaches upto
a limiting value at infinite dilution. Thus if ΛC is the equivalent conductivity of a solution at any
concentration and Λ0 is the equivalent conductivity at infinite dilution (i.e., zero concentration).
So,
ΛC
Degree of dissociation (a ) =
Λ0
The value of Λ0 for the weak electrolyte can be calculated by using Kohlrausch’s law.
(iii) Determination of dissociation constant of a weak electrolyte:
Knowing the degree of dissociation (a), the dissociation constant (K) of the weak electrolyte at
concentration (C) can be calculated using the formula:

CH 3 COOH
−
CH 3 COO + H
+
Initial concn 1 0 0
Equilibrium conc n
1-a a a
When C moles are taken C(1-a) Ca Ca

5.14
[CH 3 COO − ][H + ]

Dissociation constant (K ) =
[CH 3 COOH ]
Ca ⋅ Ca Ca 2
= =
C (1 − a ) 1 − a
Thus by knowing degree of dissociation (a), dissociation constant (K) can be easily
calculated.
(iv) Determination of ionic product of water:
It is found that ionic conductances of H+ and OH- at infinite dilution are
l0(H+) = 349.8 ohm-1 cm2
l0(OH-) = 198.6 ohm-1 cm2
By Kohlrausch’s law
Λ0(H2O) = l0(H+) + l0(OH-)
= 349.8 + 198.6
= 548.4 ohm-1 cm2
Specific conductance of pure water at 25 °C found to be,
K = 5.54 × 10-8 ohm-1 cm-1
Applying the formula,
1000
Λ0 = K ×
C
K × 1000 5.54 × 10 −8 × 1000
C= =
Λ0 548.4
= 1.01 × 10 −7 g ion mool −1
∴ Kw = [H+] [OH-]
= (1.01 × 10-7) × (1.01 × 10-7)
= 1.02 × 10-14
Here, Kw is ionic product of water.
(v) Determination of solubility of sparingly soluble salts:
Salts such as AgCl, BaSO4, PbSO4 etc which dissolve to a very small extent in water are called
sparingly soluble salts. As they dissolve very little, their solutions are considered as infinitely
dilute. Further as their solutions are saturated, their concentration is equal to their solubility.
Thus, by knowing the specific conductance (K) and equivalent conductance (Λ) of such a
solution, we have
1000 1000
Λ0 = K × =K×
C solubility
1000
Λ0 = K ×
S

1000
Hence, Solubility = K ×
Λ0
Since the solutions are extremely dilute, the conductance contribution of water is also con-
sidered. So we have to be subtracted the value of water from the total conductance.
Therefore
( K − K ω ) × 1000
S=
Λ0
Where Kw is the specific conductance of pure water.

And value of Kw is 1.60 × 10-6 S cm-1 at 25 °C.
Ionic Mobility
The ionic mobility is defined as the velocity with which an ion moves under a potential gradient of
1 volt per cm in a solution.
Velocity of the ion
Ionic mobility =
Field strength
Hence,
Units of ionic mobility:
In CGS system: cm 2 s-1 v-1
In S.I system: m 2 s-1 v-1
Ionic mobility at infinite dilution (u0) is related to ion conductance at infinite dilution l0 and it is
obtained by dividing the equivalent conductance of the ion by the Faraday.
l
i.e., Ionic mobility l0 = u0 F ⇒ u0 = 0
F
Hence,
l+0
Ionic mobility of cation (u+ ) =
F
and
l−0
Ionic mobility of anion (u− ) =
F
Where l+0 and l−0 are the equivalent conductance of the cation and anion of the electrolyte.
5.5 Conductometric titrations

Conductometric titration is a simple and accurate technique used in volumetric analysis to determine
the end point of a titration.
Principle
Conductometric titration is based on the fact that the conductance of a solution at a constant tempera-
ture depends upon the following points:

5.16
(i) The number of ions present in solution

(ii) Charge on the ions in solution
(iii) Mobility of the ions present in solution
Conductance change during titration because in titration process one type of ions are replaced
with other kind of ions which differ in their mobilities. At the end point, there is a sharp change in
conductance.
Process
In this process, titrant is added from a burette into a solution taken in a beaker. Conductivity cell is
dipped into this beaker by which conductance is measured after every addition of a titrant.
Conductance of a solution is plotted against volume of titrant added by taking conductance along
y-axis and volume of titrant along x-axis.
Two straight lines are plotted and end point is the point of intersection of two straight lines.
Burette
Titrant solution
Conductivity cell
Solution
Figure 5.5 Arrangement for conductometric titration
Types of conductometric titrations:

(i) Acid-base or neutralization titrations
(ii) Displacement titrations
(iii) Precipitation titrations and complexation titrations
(i) Acid-base titrations:
(a) Titration of a strong acid with a strong base:
Reaction between a strong acid (HCl) with a strong base (NaOH) is written as
+ −
H
+ Cl
+
+
Na + OH

−
→
+
Na+ −
+ H2O
Cl
Strong acid Strong base Strong salt
By taking acid solution (HCl) in a beaker and base (NaOH) into the burette, conduct-
ance of 20 ml of HCl is measured with conductometer on every 1 ml addition of NaOH
solution from the burette. A graph is plotted by taking volume of base along x-axis and
conductance along y-axis.

From the graph, it is clear that conductance first decrease due to replacement of fast
moving H+ ions with slow moving Na+ ions till the end point. After end point, conductance
sharply increases due to presence of fast moving OH- ion in the solution.
A
D
[H
+
g
sin
]d
rea
ec
inc
re
−]
Conductance
a
H
[O
sin
g
C
B
O
End point
Volume of NaOH added
Figure 5.6 Titration curve of strong acid vs strong base
(b)
Titration of a strong acid with a weak base:
The reaction between a strong acid with a weak base is written as
+ −
H
+ Cl
→ NH +4 + Cl − + H 2 O
+ NH 4 OH 
Strong acid Weak base
Strong salt
When a strong acid is titrated against a weak base, a graph as shown below is obtained.
From the graph, it is clear that conductance first decrease sharply due to replacement
of fast moving H+ ions with slow moving NH4+ ions. After the end point, there is very small
increase in conductance because of presence of weak base in the solution.
A
Conductance
End point
Volume of NH4OH added
Figure 5.7 Titration curve for strong acid vs weak base

5.18
(c)
Titration of a weak acid with a strong base:
The reaction between a weak acid with a strong base is written as
+ −
CH 3 COOH +
Na + OH
→ CH 3 COO − + Na + + H 2 O

Weak acid Strong base Strong salt
During titration of a weak acid with a strong base, a graph as shown below is obtained.
From the graph, it is clear that conductance first decrease due to formation of strong
salt (CH3COONa) having a common ion effect (CH3COO –) which suppresses the ionization
of weak acid. There is a small increase in conductance up to end point, due to formation of
strong salt (CN3COO – Na+) which completely ionizes in the solution.
After the end point, conductance sharply increases due to presence of strong base
(Na+OH–) in the solution.
Conductance
End point
Figure 5.8 Titration curve of weak acid vs strong base
(d)
Titration of a weak acid with a weak base:
The reaction between a weak acid (CH3COOH) with a weak base (NH4OH) is written as
→ CH 3 COO − + NH +4 + H 2 O
CH 3 COOH + NH 4 OH 

Weak acid Weak base
Strong salt
From the graph, it is clear that conductance first decreases due to formation of common
ion (CH3COO –), which suppresses the dissociation of weak acid. Further increase in con-
ductance up to end point is observed due to formation of strong salt (CH3COONH4) which
completely dissociates into ions. After the end point, there is small increase in conductance
due to presence of weak base (NH4OH) in the solution.

Conductance
O
End point
Volume of NH4OH added
Figure 5.9 Titration curve of weak acid vs weak base
(e)
Titration of a mixture of strong acid and weak acid with a strong base:
In such titrations of a mixture of strong acid (HCl) and weak acid (CH3COOH) with a strong
base (NaOH), the graph obtained is shown hereunder.
When NaOH solution is added to the mixture of acids, the strong acid (HCl) is neutral-
ized first due to high ionization.
Two end points ‘x’ and ‘y’ are obtained and point ‘x’ corresponds to neutralization of
strong acid (HCl) with a strong base (NaOH).
Point ‘y’ corresponds to neutralization of weak acid (CH3COOH) with a strong base
(NaOH).
After end point ‘y’, there is sharp increase in conductance due to presence of strong
base (Na+OH–) in the solution.
Conductance
OH
HC
Na
lv
OH
vs Na
sN
OOH
CH 3C
aO
y
H
Figure 5.10 Titration curve of strong and weak acid vs strong base
(ii) Displacement titrations:

Upon addition of HCl into sodium acetate (CH3COONa), displacement reaction taken place and
is written as

5.20
CH 3 COO − Na + + H

+
Cl −
→ CH 3 COOH + +
Na+
Cl

−

Strong salt Strong acid Strong salt
From the graph, it is clear that there is small increase in conductance up to end point, which
is due to replacement of highly dissociated CH3COONa with strongly dissociated NaCl and
undissociated CH3COOH.
After the end point, conductance increases due to presence of HCl in the solution.
Conductance
O
End point
Volume of HCl added
Figure 5.11 Displacement reaction of CH3COOH vs HCl
(iii) Precipitation titrations:

Consider a precipitation reaction like AgNO3 vs KCl. The precipitation reaction is written as
Ag + + NO3− + K + + Cl − 
→ AgCl ↓ + K + + NO3−
ppt .
From the figure, it is clear that conductance remains constant up to end point due to same
mobilities of Ag+ and K+ ions. After the end point, there is a sharp increase in conductance due
to presence of free ions (K+ and Cl-) in the solution.
Conductance
O
End point
Volume of KCl added
Figure 5.12 Precipitation reaction of AgNO3 vs KCl

Advantages of Conductometric Titrations

(i) Conductometric titrations are more accurate.
(ii) They can be used for titrating colored solution because the colored solutions cannot be titrated by
ordinary volumetric methods using indicators.
(iii) They can be employed even for titrating very dilute solutions.
(iv) They can be used for titrating weak acids and weak bases.
(v) No observation is required near the end point because end point is detected graphically.
Limitations of Conductometric Titrations

(i) It can be applied only to a limited number of titrations.
(ii) When the total electrolytic concentration is high, the results from conductometric titration become
less accurate, less precision and less satisfactory.
5.6 Electrochemical cells

A device used to convert the chemical energy produced in a redox reaction into electrical energy is
called an electrochemical cell or simply a chemical cell.
Electrochemical cells are also called galvanic cells or voltaic cell after the names of Luigi Galvani
and Alessendro Volta, who were the first to perform experiments on the conversion of chemical energy
into electrical energy. The galvanic cell consists of two half-cells combined in such a way that oxida-
tion takes place in one beaker and reduction takes place in another beaker and both two electrodes are
connected externally by a piece of metal wire and an electric current flows through the external circuit.
The practical application of galvanic cell is Daniel cell as shown in Figure 5.13. It consists of a zinc
rod dipped in zinc sulphate solution taken in a beaker and a copper rod is placed in copper sulphate
solution taken in another beaker. The two portions of the cells are called half cells or redox couples
in which oxidation half reaction in one beaker and reduction half reaction in another beaker. The two
electrodes are connected by a wire and two solutions are connected by a salt bridge.
Voltmeter / Ammeter
Flow of e− e−
electrons
Salt bridge(K2SO4)
2−
Anode (−) SO4 K+ Cathode(+)
Zinc Copper
electrode electrode
Movement of cations
2−
Zn2+ SO4
Movement of anions
ZnSO4 soln. CuSO4 soln.
Figure 5.13 Daniel cell

5.22
Salt bridge is an inverted U-shaped tube containing concentrated solution of an inert electrolyte
like KCl, KNO3, K 2SO4 etc., or solidified solution of such an electrolyte in agar-agar and gelatine. The
inert electrolyte does not take part in the redox reaction. The main functions of the salt bridge are
(i) To complete the electrical circuit by allowing the ions to flow from one solution to the other
without mixing of the two solutions.
(ii) To maintain the electrical neutrality of the solutions in the two half-cells.
The oxidation and reduction reactions that occur at the two electrodes may be represented as:
At the anode:
Zn → Zn 2+ + 2e- (Oxidation half reaction)
At the cathode:
Cu2+ + 2e- → Cu (Reduction half reaction)
The overall cell reaction is:
Zn + Cu2+ → Zn2+ + Cu
or
Zn + CuSO4 → ZnSO4 + Cu
Some important features of the electrochemical cell may be summed up as follows:
(i) The zinc electrode at which oxidation takes place is called the anode. The copper electrode at
which the reduction takes place is called the cathode.
(ii) Due to oxidation of zinc electrode, electrons are produced at the zinc electrode and it pushes the
electrons into the external circuit and hence it is designated as negative pole. The other electrode
required electrons for the reduction of Cu2+ into Cu. Therefore, it acts as the positive pole.
(iii) The electrons flow from the negative pole to the positive pole in the external circuit and conven-
tional current is flowing in opposite direction.
(iv) The oxidation of zinc into ions produces excess of Zn2+ ions in the left beaker. Similarly, reduction
of copper ions to copper leaves the excess of SO42- ions in the solution in the right beaker.
(v) To maintain electrical neutrality of the solution in the two beakers, the cations and anoins move
through the salt bridge which helps to complete the inner circuit.
Representation of a Galvanic Cell

An electrochemical cell is represented in a manner as illustrated below for the Daniel cell:
Zn ZnSO 4 (C1 ) CuSO 4 (C2 ) Cu
or
Zn Zn 2+ (C1 ) Cu 2+ (C2 ) Cu
(i) The electrode on which oxidation takes place is written on the left hand side and other electrode
on which reduction takes place is written on right hand side.
(ii) Anode is written by writting the metal first and then the electrolyte and cathode is written by first
writing the electrolyte and then metal.
(iii) Single vertical lines represent the phase boundaries of the electrodes and double line represents
the salt bridge.

Electrode Potential
Consider a metal rod (M) placed in contact with a 1 M solution of its own ions (M n+) at 25 °C, then there
are possibilities such as
(i) The metal atoms of the metal rod (M) may lose electrons and changed into Mn+ ions, i.e., metal
atoms get oxidized
M → Mn+ + ne- (Oxidation) (1)
(ii) The Mn+ ions, on collision with the metal rod may gain electrons and changed into metal atoms
i.e., Mn+ ions are reduced.
Mn+ + ne- → M (Reduction) (2)
What actually happens depends upon the relative tendency of the metal or its ions. If metal
has relatively higher tendency to get oxidized then reaction (1) will occur. If the metal ions have
relatively higher tendency to reduced, then reaction (2) will occur. During oxidation negative
charge is developed on metal rod and during reduction positive charge develops on metal rod.
Metal rod (M) Metal rod (M)
n+
n+ n+
M
M+ne− M+ne−
M M
Thus in either case, there is a separation of charges between the metal rod and its ions in the
solution. As a result, a potential difference exists between them.
“The electrical potential difference set up between the metal and its ions in the solution is
called electrode potential or the electrode potential may be simply defined as the tendency of an
electrode to lose or gain electrons when it is in contact with solution of its own ions”.
The electrode potential is termed as oxidation potential if oxidation takes place at the elec-
trode with respect to standard hydrogen electrode and is called as reduction potential if r eduction
takes place at the electrode with respect to standard hydrogen electrode. The electrode potential
is called standard electrode potential if metal rod is suspended in a solution of one molar con-
centration and the temperature is kept at 298 K.
Measurement of Electrode Potential

The absolute value of the electrode potential of a single electrode potential cannot be determined
because oxidation half reaction or reduction half reaction cannot take place alone. It can only be meas-
ured by using some electrode as the reference electrode. The reference electrode used is the standard
or normal hydrogen electrode (S.H.E or N.H.E).
It consist of platinum foil or wire coated with platinum black dipped into a molar (1M) solution of H+
ion and hydrogen gas at 1 atmospheric pressure is continuously passed through it at 298 K. This electrode
may serve as anode or cathode depending upon the nature of another electrode to which it is connected.

5.24
Pt Wire
H2 gas
(1 atm. pressure)
Glass tube
Hg
Platinised
pt foil
1M HCl soln.
Standard hydrogen electron
The reaction, when electrode acts as the anode i.e., oxidation takes place
H2(g) → 2H+(aq) + 2e-
When this electrode act as the cathode i.e., reduction takes place
2H+(aq) + 2e- → H2(g)
This electrode is usually represented as

Pt, H2(g), (1 atm)/H+(1M)
The electrode potential of the standard hydrogen electrode is taken as 0.000 at 298 K. The standard
electrode potential of the other electrode can be determined by connecting it with S.H.E and find-
ing EMF of the cell experimentally. As the EMF of the cell is the sum of oxidation potential where
oxidation takes place and reduction potential of the electrode where reduction takes place and as the
electrode potential of S.H.E is zero, so EMF of the cell will directly gives the electrode potential of the
electrode under investigation.
EMF or Cell Potential of a Cell

As we know that electrochemical cell is made up of two electrode i.e., two half cells. One of these
electrodes must have a higher electrode potential than the other. As a result of this, the electrons flow
from an electrode at a higher potential to the electrode at a lower potential.
The difference between the reduction potentials of the two half cells is known as electromotive
force (EMF) of the cell or cell potential or cell voltage.

EMF = Reduction potential of cathode – Reduction potential of anode

EMF = Ecathode – Eanode
Ecell = Eright – Eleft
The EMF of the cell depends on
(i) The nature of the reactions
(ii) Concentration of the solution in the two half cells reactions
(iii) Temperature.
EMF Measurement
EMF of any electrochemical cell is determined by potentiometric method. The measurement becomes
possible when the positive pole of the cell is connected to the end B of the potentiometer wire and the
negative pole to the sliding contact. If the connections are wrong the balance point cannot be deter-
mined and hence the polarity of the electrodes is also indicated by the circuit. The emf of the cell (Ex)
is measured by comparing with the emf of a standard cell (Es), Whose EMF is accurately known and
remains constant at a given temperature.
The sliding contact jockey J is moved along the wire AB till there is no deflection (zero current
flow) in the galvanometer (point C on the wire). The emf of the standard cell (Es) is proportional to the
length AB and emf of the cell (Ex) is proportional to the length AC and the emf of the unknown cell
Ex is calculated by the formula for no deflection in the galvanometer G.
Es length AB
=
Ex length AC
or
length AC
Ex = Es ×
length AB
Standard cell (Es)

− +
A C
B
Jockey
Stretched wire
− +
G
Experimental cell (Ex)

5.26
Electrochemical Series
As we know that emf or cell potential or cell voltage can be calculated as
Ecell = Ecathode - Eanode
or
= Eright - Eleft
If the electrode potential or half - cell potential are measured at 25 °C (298K), then
E°Cell = E°Cathode - E°anode
E°Cell = standard cell potential
In the Daniel cell,

E°Cell = E°Cu 2+
/Cu - E°Zn 2+
/Zn
Where E°Cu /Cu and E°Zn /Zn are the standard reduction potential for copper and zinc ion.
2+ 2+
(Always remember that when no specific mention is made the electrode potential is always the
reduction potential.)
“Electrochemical series is a series in which various electrodes have been arranged in order of their
increasing values of standard reduction potential”. Electrochemical series as shown in Table 5.2.
Table 5.2 Electrochemical series

Standard reduction potentials at 25 °C in aqueous solution
Electrode Electrode reaction E° (Volts)
Li | Li+ Li+ + e → Li -3.045
K | K+ K+ + e- → K -2.925
Ca | Ca2+ Ca+2 + 2e-→ Ca -2.87
Na | Na+ Na+ + e- → Na -2.714
Mg | Mg2+ Mg2+ + 2e- → Mg -2.37
Al | Al3+ Al3+ + 3e-→ Al -1.66
Zn | Zn2+ Zn2+ + 2e-→ Zn -0.763
Fe | Fe2+ Fe2+ + 2e-→ Fe -0.44
Cd | Cd2+ Cd2+ + 2e-→ Cd -0.403
Sn | Sn2+ Sn2+ + 2e → Sn -0.136
Pb | Pb2+ Pb2+ + 2e → Pb -0.126
Fe | Fe3+ Fe3+ + 3e-→ Fe -0.036
Pt | H2 | H+ 2H+ 2e-→ H2 0.000
Pt | Sn2+| Sn4+ Sn4+ + 2e-→ Sn2+ +0.15
Cu | Cu2+ Cu2+ + 2e-→ Cu +0.337
Pt | Fe2+, Fe3+ Fe3+ + e-→ Fe2+ +0.771
Ag | Ag+ Ag+ + e-→ Ag +0.799
7 + 14H + 6e → +1.33
+ -
Pt | Cr3+, Cr2O2-
7 Cr2O2-
2Cr3+ + 7H2O
Pt | Ce3+, Ce4+ Ce4+ + e- → Ce3+ +1.61
Pt | F-, F2 F2 + 2e- → 2F- +2.87

Applications of Electrochemical Series

(i) To compare the relative oxidizing and reducing powers:
In an electrochemical series, the species which are placed above hydrogen are more difficult to
be reduced and their standard reduction potential values are negative. The Li, Li+ electrode has
the least E° Value and therefore, it is reduced with most difficulty. Therefore, Li is the strongest
reducing agent and the species which are placed below hydrogen are easily reduced and their
standard reduction potential values are positive. The F2, 2F- electrode has the highest E°value
and therefore, F2 has the greatest tendency to get reduced, so F2 is the strongest oxidizing agent.
(ii) To compare the relative activities of metals:
Lesser the reduction potential of a metal, more easily it can lose electrons and hence greater is its
reactivity. So, as a result, a metal with less reduction potential can displace metals with higher
reduction potentials from their salt solutions.
For example, Reduction potential of Mg, Zn, Fe, Cu and Ag are in the order: Mg < Zn < Fe
< Cu < Ag.
Hence, each metal can displace metals on its right from the salt solutions.
(iii) To predict whether a metal reacts with acid to give hydrogen gas:
Metal (M) may react with an acid to give hydrogen gas (H2), the following reaction takes place.
1
M + H+ → M + + H2
2
Which can split into two half reactions as:
M → M+ + e− (oxidation half reaction )
1
H+ + e− → H ( reduction half reaction)
2 2
Thus, the metal should have the tendency to lose electrons i.e., undergo oxidation, w.r.t
hydrogen so; the metal should have a negative reduction potential. Thus, all the metals above
hydrogen in electrochemical series react with the acid to give hydrogen gas.
(iv) To predict the spontaneity of any redox reaction:
For a spontaneous reaction, EMF of the cell must be positive and EMF can be calculated by
using the formula.
Ecell = Ecathode - Eanode
(v) To determine the equilibrium constant:
As we know that
∆G° = -RT ln Keq
and
∆G° = − nFE°
RT
E° = ln Keq
nF
2.303RT
E° = log Keq
nF
0.0591
E° = log Keq at 298 K
n
Therefore, by measuring of E° helps us to determine the equilibrium constant for the elec-
trode reaction.

5.28
Nernst Equation for Electrode Potential

Nernst equation tells us the effect of electrolyte concentration and temperature on the electrode
potential.
For this purpose, the electrode reaction is written as reduction reaction.
Mn+ (aq) + ne- → M(s)
Since ∆G: −nFE and ∆G° = −nFE°
Hence
RT [M]
E = E° − 2.303 log
nF [M n+ ]
Where E = electrode potential under given concentration of M n+ ions and temperature T
E° = Standard electrode potential
R = gas constant
T = Temperature in K
F = 1 Faraday
For pure solids or liquids or gases at one atmospheric pressure, the molar concentration is taken
as unity
[M] = 1
RT 1
So, E = E° − 2.303 log
nF [M n + ]
Putting R = 8.314 JK-1 mol-1
F = 96500 coulombs
T = 298 K
0.0591 1
We get E = E° − log
n [M n + ]
In case of an electrochemical cell,
aA + bB ne
−
 → cC + dD
Then applying Nernst equation, we have
0.0591 [C]c [D]d
Ecell = E°cell − log
n [A ]a [B]b
Where n is the number of electrons involved in the cell reaction.
5.7 Types of electrodes

Different types of single electrodes other than the one seen in Daniel cell are also presents in an elec-
trochemical cell. Half cell reactions of such types of electrodes are discussed by using Nernst equation.
Single electrodes may be grouped into the following types:
(i) Metal-metal ion electrode:
Such type of electrode consist of a pure metal (M) is dipped in a solution of its cation (M n+)
The reaction may be represented as
M M n+ + ne −

Thus single electrode potential by Nernst equation is given by
0.0591 [M n + ]
E = E° − log
n [M]
Since [M] = 1 in pure solids or liquids form.

Hence,
0.0591
E = E° − log[ M n + ]
n
or
0.0591
E M/M n+ = E° M/M n+ − log[ M n + ]
n
Ex.: When Zinc rod is dipped in ZnSO4 or copper rod is dipped in CuSO4 soln.
(ii) Metal-amalgam electrode:
Such type of electrode is set up when metal – amalgam (i.e., When metal dissolved in mercury
to form metal – amalgam) is in contact with a solution of metal ion (M n+). Generally, more active
metals such as sodium metal is used for metal – amalgam solution.
The reaction may be represented as:
M(Hg) M n+ + ne −
and electrode potential by Nernst equation
0.0591 [M n + ]
E = E° − log
n [M( Hg)]
or
0.0591 [M n + ]
E M(Hg) / M n+ = E° M/M n+ − log
n [M( Hg)]
Where E°M/M is the standard potential of pure metal, [M(Hg)] is the activity of the metal in
n+
amalgam which is not unity.

(iii) Metal-metal insoluble salt electrode:
Such type of electrode is set up when metal (M) is in contact with sparing soluble salt (MX) and
dipped in a solution containing a common anion (X-).
The reaction is represented as
M(s) | MX | X- (aq)
Electrode reaction as:
M(s) + X − (aq ) MX(s) + e−

5.30
Electrode potential as by Nernst equation

1
E = E° − 0.0591 log
[X − ]
or
1
E M/MX/X − = E° M/MX/X − − 0.0591 log
[X − ]
Ex.: (i) Silver – silver chloride electrode in which silver metal is dipped AgCl solution and then
KCl solution Ag|AgCl|Cl-.
(ii) Calomel electrode in which mercury is in contact with solid mercurous chloride and a
solution of KCl.
Hg|Hg2Cl2|Cl-
(iv) Gas electrode:
Such type of electrode is set up when inert metal (e.g. Pt) dipped in a solution containing ions to
which the gas is reversible and then gas is continuously bubbled through the solution.
Example: Hydrogen electrode consist of a platinum wire coated with platinum black and dipped
in a solution of H+ ions through which hydrogen gas is bubbled.
The hydrogen electrode is represented as
Pt|H2|H+
and electrode reaction is represented as
1
H (g) H + (aq ) + e −
2 2
and electrode potential is given by
[H + ]
E = E° − 0.0591 log
[H 2 ] 12
Since activity of [H2] =1
So E = E° - 0.0591 log[H+]
We know that pH = -log[H ]
+
Hence E = E° + 0.0591 pH
(v) Redox electrode:
Such type of electrode is set up when inert metal (e.g., Pt) dipped in a solution containing com-
mon ions in two oxidation states of the substance.
Example: W hen Pt wire is in contact with common ions in different oxidation state such as Fe2+
and Fe3+
Electrode is represented as
Pt|Fe3+, Fe2+
Electrode reaction is represented as
Fe3+ + e − Fe2 +
Electrode potential is given by
[Fe2 + ]
E = E° − 0.0591 log
[Fe3+ ]

5.8 REFERENCE ELECTRODE

As we know that, each electrochemical cell is made up of two electrodes. It is not possible to determine
experimentally the potential of a single electrode. Electrodes whose potentials are exactly known and
can be used for the construction of the electrochemical cell and by which we can determine the single
electrode potentials are called as reference electrodes.
The common examples of reference electrodes used include the standard hydrogen electrode
(SHE), calomel electrode and silver-silver chloride electrode.
References electrode are broadly classified into two types:
(i) Primary reference electrode
(ii) Secondary reference electrodes
(i) Primary reference electrode:

Standard hydrogen electrode (S.H.E) is used as a primary reference electrode because its stand-
ard potential is taken as zero at all temperature. But it is not always convenient to use standard
hydrogen electrode because it is difficult to maintain the activity of H+ ions in the solution at
unity and also to keep the pressure of the gas uniformly at one atmosphere.
So, for these reason, some secondary reference electrodes like Ag − AgCl, calomel electrode,
Quinhydrone electrode etc. are used.
(ii) Secondary reference electrodes:
They include Ag – AgCl electrode, glass electrode, calomel electrode, Quinhydrone electrode,
their standard potentials are accurately determined and they are generally used in place of stand-
ard hydrogen electrode.
(a)
Standard calomel electrode (SCE):
Calomel electrode is commonly used as a secondary reference electrode for potential meas-
urements Calomel electrode consist of mercury, solid mercurous chloride and a solution of
potassium chloride.
The electrode is represented as Hg, Hg2Cl2(s); KCl solution.
Construction of calomel electrode:
It consist of pure mercury (Hg) placed at the bottom of a glass tube having a side tube on each
side. Mercury (Hg) is covered with a paste of mercurous chloride Hg2Cl2 (Calomel), as shown
in diagram. After that a solution of potassium chloride (KCl) is placed over the paste through the
right side tube and the solution is also filled along the left side also after that a platinum wire is
dipped into glass tube to make electrical contact of the electrode with the circuit as represented
in Figure 5.14.
Working of calomel electrode:
(1) If reduction occurs on calomel electrode then reactions may be represented as follows:
Hg 22 + (aq ) + 2e − 2Hg(l )
Hg 2 Cl 2 (s) Hg 22 + (aq ) + 2Cl − (aq )
It results into increase in the concentration of chloride ions in solution.
(2) If oxidation occurs on calomel electrode then reactions may be represented as follows:
2Hg(l ) Hg 22 + (aq ) + 2e −
Hg 22 + (aq) + 2Cl − (aq ) Hg 2 Cl 2 (s)

5.32
Pt wire
Saturated
KCl solution
Hg2Cl2 paste
Hg
Figure 5.14 Saturated calomel electrode
It result into decrease in the concentration of Cl- ions and increase the Hg 2+
2 ions in the solution.
Thus, in case of the calomel electrode, the electrode reaction is generally represented as
1
Hg Cl (s) + e − Hg(l) + Cl − (aq )
2 2 2
Electrode potential is given by
E = E °Cl-/Hg – 0.0591 log [Cl-]
2Cl 2/pt
Thus, potential of calomel electrode depends upon the concentration of chloride Cl- ions.
The reduction potential of calomel electrode also varies with the concentration of KCl solu-
tion and reduction potential of the calomel electrode at 298 K for various KCl concentrations are
on hydrogen scale are discussed below in Table 5.3:
Table 5.3 Electrode potential of KCl solution at different concentration at 298 K

[KCl] Name Electrode potential (Volt)
0. l N DCE Decinormal calomel electrode 0.3335
l.0 N NCE Normal calomel electrode 0.2810
Saturated SCE saturated calomel electrode 0.2422

To obtain the potential of any other electrode it is combined with the calomel electrode and
the emf of the resulting cell is measured. By which we can easily measure the potential of other
electrode.
Advantages
(i) Calomel electrode is simple to construct.
(ii) It does not vary with temperature.
(iii) It is stable for a long time.
(b)
Quinhydrone Electrode:
This electrode is also used as a reference electrode. This is a redox electrode in which oxida-
tion reduction takes place simultaneously.
It consists of a platinum wire dipped in a solution containing equimolar ratio of
hydroquinone (QH2) and Quinone (Q).
The electrode reaction is represented as:
O O + 2e− + 2H+ HO OH
Quinone (Q) Hydroquinone (QH2)

(C6H4O2) (C6H6O2)
The electron is represented as

Pt, Q, QH2; H+ (aq)
Hydroquinone is reversible with [H+] concn
The electrode potential at 298 K is given by
0.0591 log[QH 2 ]
E = E°pt / Q , H+, QH −
1 1 2 2 [Q][H + ]2
Since, concentration of Quinone and hydroquinone is unity because both are taken in equi-
molar ratio.
0.0591 1
Hence, E = E°PtQ, H+, QH − log + 2
2 2 [H ]
0.0591
E = E° + log[H + ]2
2
0.0591
= E° + 2 × log[H + ]
2
= E° + 0.0591 loog[H + ]
As we know that
pH = −log[H+]

5.34
So, E − E° − 0.0591 pH
Quinhudrome (QH2) is used for the measurement of the pH of the solution. This electrode is not
suitable for alkaline medium
The standard electrode potential of the quinhydrone electrode,
E° = +0.06996 V
Hence,
E = 0.06996 – 0.0591 pH
Thus potential of quinhydrone electrode, depends upon the pH of the solution.
5.9 ION SELECTIVE ELECTRODES (ISE)

An ion selective electrode consists of specially prepared membranes placed between two electrolytes
and having the ability to respond to certain specific ions. So, it is also called as specific ion electrode
(SIE). In such type of electrode the potential developed across the membrane which is related to the
activities of the specific ion dissolved in a solution and this potential is measured by potentiometric
device like a voltmeter or pH meter.
5.9.1 Electrochemical Circuit and Working of ISE

The ISE consist of a tube, in which one end of the tube is fused to an electrically conducting membrane
and the tube contains a gel incorporating the ion to which the electrode is sensitive and inert electro-
lyte such as potassium chloride. A silver wire in contact with the gel together with the inert electrolyte
constitutes the internal silver-silver chloride reference electrode. After that ion selective electrode is
coupled to a SCE and immersed in sample solution. The potential difference developed across the
membrane and this potential difference is related with the activity of ions present in gel as well as in
sample solution as shown in Figure 5.15.
Voltmeter
Standard Ag-AgCl
calomel electrode electrode
(SCE)
External Ion selective

reference electrode
electrode
Membrane
Sample solution
Figure 5.15 Electrochemical circuit

The cell is represented as
Membrane
Reference Sample Internal Reference

electrode 1 solution standard electrode 2
concentration = c1 solution
concentration = c2
External reference electrode Ion-selective electrode
The potential difference developed across the membrane is given by

0.0591 C
EISE = log 2
n C1
and emf of the cell is given by

Ecell = EISE − ∆E ref .
(i) When same reference electrodes are used then ∆Eref = 0

(ii) When different reference electrodes are used then ∆Eref = constant (k)
Suppose in a cell the reference electrode is cathode and so, ISE is cathode.
0.0591 C
Ecell = k − log 2
n C1
Here, k is a constant depends upon the internal and external reference electrode and C1 and C2 are
the concentration of the external and internal solution respectively.
5.9.2 Types of Ion – Selective Membranes

There are four main types of ion – selective membranes used in ion selective electrode
(i) Glass membranes
(ii) Solid state membranes/crystalline membranes
(iii) Gas sensing membranes
(iv) Liquid ion-exchange membranes
(i) Glass membranes:
The electrode which is having glass membrane is very highly selective for some cations such
as Na+, NH4+, Ag+ and Li+ and also selective for some double-charged metal ions, such as Pb2+
and Cd 2+.
Glass membranes are made from ion-exchange type of glass containing Na 2O, CaO and
SiO2 as shown in Figure 5.16(a).
(ii) Solid state membranes/Crystalline membranes:
This type of membrane is selective for both cation and anion of the membrane forming substance.
This type of membrane is made up from lanthanum trifluoride (LaF3) Crystal doped with
europium difluoride (EuF2) is sensitive for Fluoride F- ion and selectivity for other halides,
cyanide, silver, lead, membranes is formed by pressing pellet with pure silver sulphide(Ag2S).

5.36
For example, for chloride (Cl-) ion, pellet of (AgCl & Ag2S) is pressed together within mem-
brane as shown in Figure 5.16(b).
(iii) Gas sensing membranes:
The electrode having gas sensing membrane is used to measure the concentrations of dissolved
gases such as carbon dioxide (CO2), ammonia (NH3), Sulphur dioxide (SO2) Nitrogen oxide
(NO2) and oxygen (O2). Gas molecules diffuse across the membrane until the gas concentration
are the same in the internal electrolyte and the sample solution. Any change in the gas concentra-
tion in internal electrolyte brings about a change in pH of the electrolyte and this pH is measured
by glass electrode.
For example, The CO2 gas sensing electrode has a sodium hydrogen carbonate (NaHCO3)
solution as the internal electrolyte and cell reaction is
CO2 (sample) + 2H2 O H 3 O+ + HCO3− (internal electrolyte)

The concentration of ( HCO3− ) bicarbonate ion is considered as constant in the internal
electrolyte. The pH of the glass electrode is a function of dissolved carbon dioxide in the sample
solution.
(iv) Liquid ion-exchange membranes:
Such type of membrane is usually consisting of a large organic molecule capable of specifically
interacting with an anions or cations.
For cations such as calcium dialkyl phosphoric acid in which calcium chloride is taken as
an internal solution.
For alkali and alkaline earth metal cation, membrane is made up from phosphate diesters
and neutral monocyclic crown ethers.
For anions such as NO3− , ClO 4− , BF4− membrane is made up from tris–1,10-Phenanthroline
Fe (ClO-4)2
2+
Reference electrode
Internal Glass membrane
electrolyte
(a)
Figure 5.16 (a) Ion selective electrode of glass membrane

Reference
electrode
Internal
electrolyte
Solid Liquid
membrane membrane
(b) (c)
Figure 5.16 (b) Ion selective electrode of solid membrane and

(c) Ion selective electrode of liquid membrane
5.9.3 Applications of Ion Selective Electrodes

Ion selective electrodes have become extensively important in recent years, because of the fact that the
potential of these electrodes solves a large number of practical problems. They have been widely used
in clinical, biological, water, air, oceanographic and pharmaceutical research, and in general analytical
determinations. These are commercially available and reliable for H+, NH3, F−, Cl−, Br−, I−, Cd 2+, CN−,
−
BF4, Pb+2, NO3−, ClO 4− , K+, Ag+, S2−, Na+, SCN−, SO2 and a variety of enzymes.
The electrodes have been used for the following individual measurements and titrations:
(i) It is possible to determine lead poisoning in blood and urine samples by atomic absorption or
ashing the sample and using a colourimetric reagent for the lead in the residue. Lead can be
measured directly in blood or in urine samples with a PbS/Ag2S electrode. No pre-treatment or
separation is required.
(ii) Chloride ion can be determined in a variety of industrial and physiological samples by making
use of chloride electrode. Rapid accurate clinical determination of Cl− ion in sweat is an example.
(iii) The distillation and titration procedure in Kjeldahl method may be avoided by using ammonia
electrode. Nitrogen is converted into NH +4 ion and the solution is made basic and the concentra-
tion of NH3 is determined with ammonia electrode.
(iv) Calcium electrode has been used to determine Ca+2 ion in beer, boiler water, soil, milk, minerals,
serum, sea water, sugar, wine, etc. Ca2+ is one of the most important electrolytes in human physi-
ology. The determination of Ca+2 in biological fluids and related samples is, thus, very important.
Successful measurements of this type have been made with calcium ion exchange electrode
and flow through electrode. The latter electrode is ideally suited for serum and other biological
fluids because of increased selectivity of Ca2+ over Na+ and K+.
(v) The electrode has also been used for measuring stability constants of Ca2+ complexes and to fol-
low the kinetics of complex formation.
The potentials of each electrode can be expressed by the Nernst equation. For example, for a
reaction
OX + ne − Red
The Nernst equation may be written as
E = E 0 − [ RT nF ]ln[Red ] [OX ]

5.38
where E0 is the standard potential of the reaction recorded on the scale in which the normal
hydrogen electrode is zero. [OX] and [Red] are molar concentrations of the oxidised and reduced
species, respectively. Actually, activities should be used rather than concentration. However, for
potentiometric titration close to the end point, activity charges are very close to the concentration
charges, and hence, concentrations are used for simplicity.
5.10 GLASS ELECTRODE

Principle: pH of an aqueous solution depends upon the concentration of H+ ions and pH is determined
by using glass electrode. When glass electrode is immersed in solution, whose pH value is to be deter-
mined, the potential difference develops across the membrane and this potential difference is propor-
tional to the concentration of H+ ions.
5.10.1 Construction of Glass Electrode

The glass electrode consists of an electrically conducting glass membrane which is made up from Na2O,
CaO and SiO2. Glass electrode taken in the form of bulb and then sealed to the bottom of a glass tube
as shown in Figure 5.17. The bulb contains 0.1 M HCl solution and internal reference electrode such as
Ag-AgCl electrode or platinum wire is dipped in solution to make electrical contact with the solution.
Electrode is represented as
Ag |AgCl(S) |(0.1M) HCl| glass
Reference
electrode
Ag-AgCl(s)
HCl (0.1 M)
Glass membrane
Figure 5.17 Glass electrode

Theory
The glass membrane of glass electrode undergoes on ion-exchange reaction with the Na+ ions of the
membrane with H+ ions.
M − − Na + + H + M − − H + + Na +
Membrane (M) Membrane (M)
The potential difference developed across the gel layer of glass membrane between the two liquid
and this potential difference developed due to the concentration (C1) of acid solution inside the bulb and
concentration (C2) of acid solution into which glass bulb is dipped.

RT C2
EG = ln
nF C1
As we known that C1 = 0.1M
EG = E°G − 0.0591 log[H + ]
As we know that pH = -log[H+]

EG = E°G + 0.0591 pH
E°G is glass constant
For the measurement of pH of any unknown solution, the glass electrode is immersed in that solu-
tion, and then it is combined with a reference saturated calomel electrode.
The electrochemical cell is represented as
Ag |AgCl|0.1 MHCl| Glass |Solution of unknown pH| saturated calomel electrode
EMF of the cell at 298 K is given as
Ecell = Eright - Eleft
= Eref - EG
= Eref - EG
Ecell = E ref − E°G − 0.0591 pH

E ref − E°G − E cell
pH =
0.0591
EMF of calomel electrode at standard condition is
Eref = 0.2422
0.2422 − E°G − E cell
pH =
0.0591
The value of E°G is obtained by measuring with the solution of known pH and EMF of such a cell is
determined by a potentiometer. So, we can easily determine the pH of unknown solution cell arrange-
ment is represented in Figure 5.18 for unknown solution.
Potentiometer
Pt wire
Glass
electrode
KCl saturated
solution
Solution
of unknown Hg
pH Hg + Hg2Cl2
0.1 M Ag-AgCl(s) Calomel

HCl electrode electrode
Figure 5.18 Glass electrode-calomel electrode cell arrangement for pH determination

5.40
Advantages of Glass Electrode

(i) It can be used even in strong oxidising solutions as well in alkaline solutions.
(ii) The results obtained are quite accurate.
(iii) It is simple to operate and most convenient.
(iv) It is not easily poisoned.
(v) pH is easily determined with few milliliters of solutions.
(vi) It can easily used in the presence of metallic ions.
Limitations of Glass Electrode

The glass electrode is sensitive zeta ions such as Na+ in addition to H+, particularly at pH > 9 which
result into the alternation of the linear relationship between pH and emf of the glass electrode.
5.11 CONCENTRATION CELL

In concentration cell, EMF arises due to transfer of matter from one half-cell to the other because of a
difference in the concentration of the species involved in two half-cell.
Concentration cells may be classified into two types
(i) Electrode – concentration cells
(ii) Electrolyte – concentrations cell
Concentration cells
Electrode concentration Electrolyte concentration

cells cells
With Without
transference transference
(i) Electrode concentration cells:

These cells consist of two like electrodes at different concentration are dipping in the same solu-
tion of the electrolyte. For example, two hydrogen electrodes at different gas pressures immersed
in the same solution of hydrogen ions constitute an electrode – concentration cell.
This cell is represented as
Pt:H2(p1) | Soln of H+ ions (HCl) | H2(p2):Pt
electrode reaction is represented as,
H 2 ( p1 ) 2H + + 2e − (Oxidation )
2H + + 2e − H 2 ( p2 ) ( Reduction )
Overall reaction H 2 (p1 ) H 2 (p2 )
According to nearest equation, emf of the cell is 25 °C is given by

0.0591 p
Ecell = E° − log 2
2 p1
E° for concentration cell is zero

p1
So, Ecell = 0.02955 log at 25°C
p2
The process is spontaneous when expansion of hydrogen gas from pressure p1 at one elec-
trode to pressure p2 at the other electrode it means p2 < p1.
Another example of such type of cell is that of an amalgam with same metal at two different
concentrations.
Hg – Pb (C1), PbSO4 (solution), Hg – Pb (C2)
The electrode reaction is written as:
L.H.E Pb(C1 ) Pb 2 + + 2e − (Oxidation )
R.H.E Pb 2 + + 2e − Pb(C2 ) ( Reduction )
Overall reaction Pb(C1 ) Pb(C2 )
EMF of the cell is given by

E = E right − Eleft
 0.0591   0.0591 
=  E°Pb − log C2  −  E°Pb − log C1 
 2   2 
0.0591 C1 C1
= log = 0.02955 log
2 C2 C2
If C1 > C2, then EMF is positive, it means the whole process is spontaneous.
(ii) Electrolyte-concentration cells:
In these types of cells two identical electrodes are dipped in two metal ions solution at
different concentration.
Such type of cells is represented as
M, M n + (C1 )  M n + (C2 ).M
Example:
Zn, Zn 2 + (C1 )  Ζn 2+ (C2 ), Zn
Here C1 and C2 are the concentration of metal ion (M n+) in the two electrolyte and these two
electrolytes are separated from each other by salt bridge and C2 > C1 for a spontaneous process.
R.H.E M n + (C2 ) + ne − M(S) ( Reduction )
n+ −
L.H.E M(S) M (C1 ) + ne (Oxidation )
n+ n+
Overall reaction M (C2 ) M (C1 )

5.42
EMF of the cell

Ecell = E right − Eleft
 0.0591 1   0.0591 1
=  E° − log  −  E° − log 
 n C2   n C1 
0.0591 C
Ecell = log 2
n C1
If (i) C1 = C2
EMF of the cell, E = 0, it means reaction is at equilibrium
C2 > C1, EMF of the cell comes out to be positive, it means reaction is spontaneous in
(ii)
nature.
For example: Zn  Zn 2 + (C1 )  Zn 2 + (C2 )  Zn
The cell reaction is Zn 2 + (C2 ) Zn 2 + (C1 )

EMF of the cell
C2
Ecell = 0.0591 log
C1
5.12 POTENTIOMETRIC TITRATIONS

Potentiometric titrations are those in which emf of any cell is determined by plotting a graph between
variation of electrode potential versus volume of titrant added.
They are generally are of three types:
(i) Acid-Base titrations
(ii) Oxidation-Reduction titrations
(iii) Precipitation titrations
(i) Acid-Base titrations:
For determining the strength of acid solution, we want to titrate a solution of HCl against NaOH.
Any type of electrode whose electrode potential is depends upon the concentration of H+ ions
(e.gs, quinhydrone electrode, glass electrode) is dipped in the HCl solution and then that elec-
trode is connected with a reference electrode (e.g calomel electrode, Ag–AgCl(S) electrode) to
form a electro chemical cell.
For example, suppose hydrogen electrode is used as H+ indicating electrode and a saturated
calomel electrode is used as the reference electrode and then both electrodes are dipped in acid
solution which is taken in beaker.
The electrochemical cell is represented as
pt , H 2 (1 atm), H + ( unknown concentration C)  KCl Solution; Hg 2 Cl 2 ( s), Hg
EMF is measured by potentiometer which is connected to both the electrodes during the
addition of alkali solution from a burette.

Ecell = E right − Eleft

= Ecalomel − E hydrogen
Ecell = 0.2422 − 0.0591 logg  H + 
Ecell = 0.2422 + 0.0591 pH (1)
By knowing the EMF of the cell, we can determine the pH of the acid solution.
During the titration i.e., when we titrating acid solution (HCl) with titrant (alkali solution
NaOH), concentration of H+ ion goes on decreasing i.e., pH of the solution goes on increasing.
Hence according to equation-1 EMF of the cell goes on increasing. After that a graph is plotted
against electrode potential versus volume of alkali (NaOH) added and we obtained a sigmoid
curve in which end point is analysed. The titration curve is steep near the end point.
End point
E. Volts
Volume of NaOH
Figure 5.19 Potentiometric acid-base titration curve
As it is clear from the Figure 5.19 that for accurate determination of end point, curve should be
steep near the end point, more accurately we can determined the end point by plotting a curve
∆E
between versus volume of NaOH added and end point is determined by drawing a vertical
∆V
line from the peak to the volume axis as shown in Figure 5.20.
End point
∆E
∆V
Volume of NaOH
Figure 5.20 Determination of end-point in acid-base titration curve

(ii) Oxidation-reduction titrations:
The redox titrations are also carried out potentiometrically same as in acid-base titrations. In
redox titrations electrode reversible with respect to H+ ions is replaced by an inert metal, such
as Pt wire, immersed in a solution containing both the oxidized and reduced form of the same
species.

5.44
The electrode acts as an oxidation-reduction electrode and this electrode is combined with a
reference electrode, e.g., a saturated calomel electrode (SCE) to form a galvanic cell.
The cell is represented as
Hg, Hg 2 Cl 2 (s), KCl(sat.soln)  Fe2 + , Fe3+ ; pt
The EMF of the cell is measured potentiometrically at each stage of titration and end point
is obtained near the steep point of the curve as in case of acid-base titration curve.
(iii) Precipitation titrations:
In such type of titrations, potential of the half-cell is measured by connecting it with the calomel
electrode. For example, precipitation reaction of silver nitrate (AgNO3) with potassium chloride
(KCl)
Ag + + NO3− + K + + Cl − → AgCl ↓ + K + + NO3−
Silver electrode is connected with the calomel electrode and silver nitrate (AgNO3) placed
in the micro burette and potassium chloride (KCl) in the beaker and emf of the cell is measured
and plotted against the volume of silver nitrate added. The steep rise in the curve shows the end
point of the titration same as in acid-base titration curve.
5.13 Electrochemical Sensors

Electrochemical sensors are devices which are used to measure electrical parameters such as potential
difference, current, conductance etc., of the sample under analysis.
The sensor which is measure the potential difference is called potentiometric sensor and which
measure current is called amperometric sensor.
Electrochemical sensors produces an electrical signal which is related to the sample under study.
Biological processes such as analysis of glucose in blood and urea are analysed by potentiometric
or amperometric sensor.
5.13.1 Potentiometric Sensor

A potentiometric sensor is a type of chemical sensor which measure potential difference of an electrode
when there is no current flow.
Principle
Potentiometric sensor is used to determine analytical concentration of gas or solution. Working
e lectrode and the reference electrode gives potential difference which is measured by potentiometer.
In the potentiometric sensor the ion-selective electrode (ISE) is coupled with the reference elec-
trode to complete electrical circuit and the sensor measured the potential difference between two elec-
trodes is shown figure.
Ag. Ag Cl Ag. Ag Cl
Internal
solution
Glass membrane Liquid junction
Ion selective Reference

Glass electrode is used to measure pH of the solution taken as ion-selective electrode and connected
with reference electrode.
5.13.2 Analysis of Glucose in Blood

For analysis of glucose in blood glucose sensor which is a potentiometric sensor is used.
Glucose is converted into ions, which is detected by ion-selective electrode (ISE). Glucose is
oxidised into gluconic acid which further undergoes decomposition and gives H+ ions which are
detected by pH electrode.
The reaction can be written as
Glucose + O2 Glucose
 oxidase
→ Gluconic acid + H 2 O2
Formed H2O2 undergoes reaction at the electrode as shown below
H 2 O2 electrode
 → 2H + + O2 + 2e −
H+ ions is measured by pH meter i.e, glass electrode and a potential difference is set-up between glass
electrode and reference electrode which is sense by potentiometric sensor which analyse the glucose
level in blood.
5.13.3 Analysis of Urea

Analysis of urea in serum or urine sample is very common. For this analysis, enzymatic p otentiometric
sensor or urea bio sensors is used.
Urea concentration is determined during enzymatic reaction of urea with urease which release
NH +4 ions and HCO3− ions. By using ammonium ion-selective electrode analyse the ammonium ions
+
( NH 4 ) concentration.
NH 2 CONH 2 + 2H 2 O + H + Urease
→ 2 NH 4+ + HCO3−
Electrode is modified with a gel containing the urease enzyme. The signal is determined by potentio-
metric bio sensor which sense the presence of urea in different sample.
5.14 VOLTAMMETRY
Amperometry is an electrochemical technique in which a current is measured as a function of an
independent variable, that is, time or electrode potential. Voltammetry is a sub-class of amperometry
in which current is measured by varying the potential applied to the electrode. Polarography is a sub-
class of voltammetry that uses a dropping mercury electrode as the working electrode. Coulometry
uses applied current or potential to completely convert an analyte from one oxidation state to another.
In these processes, the total current passed is measured directly or indirectly to determine the number
of electrons passed. Potentiometry measures the potential of a solution between two electrodes. Here,
one electrode is used as a reference electrode; it has the constant potential, and the other is used as an
indicator electrode, whose potential changes depend on the sample.
Electroanalytical methods that depend on the measurement of current as a function of applied poten-
tial are called voltammetric methods. Voltammetry comprises a group of electroanalytical methods that
are based upon the potential current behaviour of a polarizable electrode in the solution being analysed.

5.46
In voltammetry, a measured small potential is impressed across a pair of electrodes one of which is
a non-polarizable reference electrode and the other a polarizable inert electrode. The current, which
flows, depends upon the composition of the solution. In other words, voltammetry and voltammetric
analysis are concerned with the study of current voltage relation at a micro electrode called working
electrode. In order to ensure polarization of the electrode, its dimensions generally are made small.
Therefore, electrode may be of some inert metal, such as platinum or gold. A three-electrode cell is,
however, preferred in general voltammetry. The third electrode can be a simple wire of platinum or
silver or mercury pool. The reference electrode may be of any convenient form since it does not carry
current (Figure 5.21).
Several voltammetric techniques such as Linear sweep voltammetry, Staircase voltammetry,
Square wave voltammetry, Cyclic voltammetry, Anodic stripping voltammetry, Cathodic stripping vol-
tammetry, Adsorptive stripping voltammetry, Alternating current voltammetry, Polarography, Rotated
electrode voltammetry, Normal pulse voltammetry, Differential pulse voltammetry, and Chrono-
amperometry play their own importance roles.
− +
S
R B
A
C
Current
meter
Working Counter
electrode electrode
Reference
Digital volt electrode
meter
Figure 5.21 Voltammetric instrument
5.14.1 Linear Sweep Voltammetry (LSV)

The effectiveness of this technique is based on its capability for observing the redox behaviour rapidly
over a long potential range. Since a rapid linear sweep of the potential is employed, the technique is
commonly termed as linear sweep voltammetry (LSV) or stationary electrode voltammetry (SEV).
Only stationary or quasi-stationary electrode like dropping mercury electrode is employed as the indi-
cator electrode in an unstirred solution.
During the early period, such fast-scan rates could only be monitored over a cathode-ray oscil-
loscope; therefore, the LSV was then known as cathode-ray polarography. Now-a-days, fast-scan rate
X-Y recorders can be used during such experiments. LSV is usually applied at a mercury drop or at
any solid stationary electrode, wherein the potential scan rate can be moderate to fast. When a DME is
used, the entire potential range is covered on a single drop. Since the sweep rate is fast as compared to
drop-time, the recording is made during the end period of the drop’s life. This is done to minimize the
condenser or charging current component. It also ensures that the growth of the mercury drop during
the sweep period remains negligible.

In the single-sweep method, the potential of the working electrode increases linearly to a fixed
value. It may then fall instantaneously to its starting value. The potential sweep has the appearance
of a saw-tooth. The entire i-E curve is recorded during the linear rise of the applied potential. Due to
fast potential sweep, there occurs a depletion of the depolarizer around the electrode surface and a
peak-shaped i-E curve is recorded. The potential of the peak is characteristic of the depolarizer and its
length on the current axis is proportional to concentration of the depolarizer. The following relation
holds good for a reversible system.
0.029
E p = E1/ 2 ±
n
Where Ep is the peak potential, E1/2 is the equivalent de polarographic half-wave potential and n the
number of electrons taking part in the electrode reaction. The positive sign holds for the anodic reac-
tion, whereas the negative sign holds for cathodic reaction.
Linear sweep voltammetry has been employed both for qualitative and quantitative analyses. It has
a reasonably low detection limit, which goes down to 10−5 m. The sensitivity is improved by increasing
the scan rate. LSV, being a transient technique, was earlier known as chronoamperometry with poten-
tial sweep since the potential axis may be taken as time axis.
During periodic polarization (multi-sweep), a saw-tooth voltage is applied with delay. A controlled
drop-time is ensured with a DME.
First Second
cycle cycle
Switching
E
potential
t
Figure 5.22 A triangular excitation signal applied in cyclic voltammetry
5.14.2 Ferric Fe3+/Fe2+ System

Unlike potential step measurements, in LSV measurements, the current response is plotted as a func-
tion of voltage rather than time.
Fe3+ + e − Fe2 +
For the abovementioned system, if an electrolyte solution containing only Fe3+, then the following vol-
tammograms would be seen for a single voltage scan.
Current
V2
Voltage
Time V1 V2
V1
Figure 5.23

5.48
The scan begins from left-hand side of the current/voltage plot where no current flows. As the voltage
swept further to more reductive values, that is, towards right, a current begins to flow and reaches a
peak before dropping.
To justify this behaviour, we need to consider the influence of voltage on the equilibrium estab-
lished at the electrode surface. The rate of electron transfer is fast in comparison to the voltage sweep
rate in electrochemical reduction of Fe3+ to Fe2+.
An equilibrium is established identical to that predicted by thermodynamics at the electrode
surface.
Nernst Equation
RT  Fe 
3+
E=E + 0
ln
nf  Fe2 + 
Nernst equation can explain the relationship between concentration and voltage or potential difference.
Where E = Applied potential difference, E0 = Standard electrode potential.
Hence, when the voltage swept from V1 to V2, the equilibrium position shifts from V1 (no conver-
sion) to V2 (full conversion) of the reactant at the electrode surface. The exact form of the voltammo-
gram can be justified by considering the voltage and mass transport effects.
When the voltage is initially swept from V1, the equilibrium at the electrode surface begins to alter
and the current begins to flow in the following ways:
Fe3+ + e − ← Fe2 +
Fe3+ + e − Fe2 +
Fe3+ + e − Fe2 +
Fe3+ + e − Fe2 +
Fe3+ + e − → Fe2 +
The current rises as the voltage is swept further from its initial value as the equilibrium position is
shifted further to the right due to conversion of more reactant. The peak occurs, and at the same point,
the diffusion layer has grown sufficiently above the electrode so the flux of reactant to the electrode is
not fast enough to satisfy Nernst equation. In this situation, the current begins to drop just as it is in the
potential step measurement. The drop in current follows the same behaviour, which can be explained
by Cottrell equation.
The above voltammogram recorded at a single scan rate. If the scan rate alters the current, then the
response also changes. Figure 5.24 shows a series of linear sweep voltammograms recorded at different
scan rates for an electrolyte solution containing only Fe3+.
Current
V2
Increasing
scan rate
Time
V1
V1 Epc V2 Voltage
Figure 5.24

Each curve has same form except total current. Here, total current increases with increasing scan rate.
This again can be justified by considering the size of the diffusion layer and the time taken to record
the scan. If the scan rate decreases, then LSV voltammogram will take longer time to record. The size
of the diffusion layer above the electrode surface will be different depending on voltage scan rate. The
diffusion layer will grew much further from the electrode in slow voltage scan when compared to fast
scan. Hence, the flux to the electrode surface is smaller at slow scan rate than fast scan rate.
“Current is proportional to the flux towards the electrode and the magnitude of the current will be
lower at slow scan and higher at high scan rate”.
“The position of the current maximum peak occurs at the same voltage; this is the important char-
acteristics of electrode reaction which have rapid electron transfer kinetics and also often referred to as
reversible electron transfer reaction”.
If the electron transfer processes were slow relative to the voltage scan rate, then the reactions are
known as quasi-reversible or irreversible electron transfer reactions. Figure 5.25 represents a series of
voltammograms recorded at a single-voltage sweep rate for different reduction rate constants.
Current Decreasing rate
constants
V1 V2 Voltage
Figure 5.25
In this kind of situations, the voltage applied will not result in the generation of concentrations at the
electrode surface according to the Nernst equation. As the kinetics of the reaction is slow, the equi-
libria are not established rapidly according to voltage scan rate. In this kind of situation, the overall
voltammogram recorded is similar to the graph shown in Figure 5.25, but unlike reversible reaction,
the position of the current maximum shifts depending on the reduction rate constant and the voltage
scan rate. This is due to the reason that current takes more time to respond to the applied voltage than
the reversible case.
5.14.3 Cyclic Voltammetry

Cyclic voltammetry is a very versatile and useful technique and is ideal for studying the mechanism
of redox reactions of diffusion coefficients and half-cell potentials. Actually, it is a logical extension
of LSV. In cyclic voltammetry, a triangular potential wave is impressed on a solid indicator electrode.
Therefore, both forward and reverse reactions are monitored, and complete current-potential charac-
teristics of a redox system are supplied.
On repeating the triangular potential excitation signal during cyclic voltammetry, the potential
of the electrode charges back and forth between two fixed values. These are known as the switching
potentials. During a positive scan, the potential becomes increasingly positive, whereas the reverse is
known as a negative scan. For recording the cyclic voltammogram, the resulting current is plotted dur-
ing the positive and negative potential scans.

5.50
The cyclic voltammogram of a reversible system is shown in Figure 5.26. Here, reduction occurs
during the negative scan and the reduced product is oxidized back during the positive scan. The
cathodic and anodic peak heights appear equal in a reversible system. The nature and shape of a cyclic
voltammetry curve is altered, if the reaction is accompanied by adsorption. Cyclic voltammetry is,
thus, useful in diagnosing the mechanism of the electrode reactions. It also enables one to detect unsta-
ble intermediates of electrode reaction.
Current
Y
ipc
X
V1 V2 Voltage
ipa
Epa Epc
Figure 5.26 A typical cyclic voltammogram
In a reversible system, the difference between anodic and cathodic peak potentials is expressed by the
following expression at 25°C.
0.059
E p = ( E p )anodic − ( E p )cathodic =
n
A reversible redox couple can be identified from its cyclic voltammogram by measuring the potential
difference between the two peaks. The mean between the two peak potentials will correspond to the
formal electrode potential (E°) of the redox couple.
When the potential scan rate (V) is increased, both (ip)anodic and (ip)cathodic increase in proportion to
V1/2 . A plot of (ip)a and (ip)c versus V1/2 is linear for a reversible system.
The ratio of (ip)a/(ip)c remains unity and independent of the scan rate for a reversible couple with
no kinetic complications. This ratio is influenced by coupled chemical reactions and such behav-
ioural study makes cyclic voltammetry a very powerful tool for studying electrode reactions and their
mechanisms.
The spacing between the two peak potentials is larger with irreversible systems as compared to
reversible systems. With increasing irreversibility, the peaks get rounder, and finally, one of them dis-
appears. The difference between the two peak potentials (∆Ep) is used to calculate the heterogeneous
charge transfer rate constant after changes occur in the shape of CV on repeating.
The greatest utility of cyclic voltammetry is its ability to generate a species during a potential scan
and then study its fate in the subsequent scan(s).
5.14.4 Applications of Voltammetry
Modern voltammetric methods continue to be potent tools used by analytical, inorganic, physical and
biological chemists for fundamental studies of oxidation and reduction processes in various media,
adsorption processes on surfaces and electron transfer mechanisms at chemically modified electrode
surfaces.

Several types of voltammetry in current use are as follows:

(i) Voltammetric sensors have lot of importance in the determination of specific species that are of
interest in industry and research; these devices are sometimes called electrodes but are in fact
complete voltammetric cells and are better referred to as sensors.
(ii) Stripping voltammetry is a significant trace analytical method, particularly for the determination
of metals in the environment.
Anodic stripping voltammetry is a quantitative, analytical method for trace analysis of metal cat-
ions. The analyte is deposited (electroplated) onto the working electrode during a deposition step
and then oxidized during the stripping step. The current is measured during the stripping step.
Cathodic stripping voltammetry is a quantitative, analytical method for trace analysis of anions.
A positive potential is applied, oxidizing the mercury electrode and forming insoluble precipi-
tates of the anions. A negative potential then reduces (strips) the deposited film into solution.
(iii) Differential pulse polarography and rapid scan voltammetry are important for the determination
of species of pharmaceutical interest.
(iv) Polarography is a sub-class of voltammetry where the working electrode is a dropping mercury
electrode (DME), useful for its wide cathodic range and renewable surface.
(v) Voltammetry and other electrochemical detectors are frequently employed in high-performance
liquid chromatography and capillary electrophoresis.
(vi) Amperometric techniques are widely used in sensor technology, monitoring titrations and reac-
tions of biological interest.
(vii) Adsorptive stripping voltammetry is a quantitative, analytical method for trace analysis. The ana-
lyte is deposited simply by adsorption on the electrode surface (i.e., no electrolysis) and then
electrolyzed to give the analytical signal. Chemically modified electrodes are often used.
(viii) Rotated electrode voltammetry is a hydrodynamic technique in which the working electrode, usu-
ally a rotating disk electrode (RDE) or rotating ring-disk electrode (RRDE), is rotated at a very
high rate. This technique is useful for studying the kinetics and electrochemical reaction mecha-
nism for a half-reaction.
5.15 BATTERIES
A battery is a device in which numbers of electrochemical cells are connected in series. It converts
chemical energy into electrical energy at a constant voltage.
Batteries are generally used at a commercial level.
5.15.1 Advantages of Batteries

(i) In batteries, there is no need to be connected to an electrical system.
(ii) Batteries act as a portable source of energy.
(iii) Batteries can be easily replaced.
(iv) Different types of batteries have their specific applications e.g. miniature batteries (primary cell)
is generally used in electric watches, calculator, medical devices and secondary cells are generally
used in portable equipments like portable radio and TV, mobile phones, lap–top, computers etc.
5.15.2 Disadvantages of Batteries

(i) Batteries can be used for only a limited time, even rechargeable batteries can be recharged a
certain number of times.

5.52
(ii) Some batteries are dangerous and can lead to fire, explosion, chemical pollution etc.
(iii) Some types of batteries need to be maintained and checked periodically.
Requirements should be Possessed by the Batteries

(i) It should have the compactness, lightness and ruggedness for portability.
(ii) Long life cycle is required.
(iii) Operating voltage is required i.e., voltage should not drop much during use.
(iv) It should be stable with time, temperature, vibration shock etc.
Classification of Various Commercial Cells

(i) Primary cells
(ii) Secondary cells
(iii) Fuel cells
(i) Primary cells: Primary cells are those in which redox reaction occurs only once and cell
becomes dead after some time.
These are non-rechargeable and cell becomes dead after some time.
For example: dry cell, mercury cell and lithium cell etc.
(ii) Secondary cells: Secondary cells are those which can be recharged by passing an electric current
through them and hence can be used over and again.
For example: Lead storage cell, Ni – Cd storage cell etc.
(iii) Fuel cells: Fuel cells are those in which the energy produced from the combustion of fuel such as
H2, O2, CH4 etc. is directly converted into electrical energy.
A Brief Description of Example of Each Type of Cell

(i) Primary Batteries
(a) Dry cell:
Dry cell is a compact form of the Leclanche cell. This is also known as carbon – zinc cells.
It consists of a cylindrical zinc container which acts as the anode. A graphite rod placed
in the center acts as the cathode. Dry cell does not use any liquid that’s why it is called as
dry cell.
It consists of a mixture of NH4Cl, ZnCl2 and MnO2 made into a paste by the addition of
starch which acts as electrolyte. The zinc container is covered with cardboard to protect it
from the atmosphere as shown in Figure 5.27.
(+)
Metal cap Pitch seal
Zinc container
(Anode)
Graphite (Cathode)
Card board
cover
MnO2 + C
Paste of NH4Cl + ZnCl2
Figure 5.27 The dry cell

The reactions of the cell are:

At anode:
Zn(s) → Zn 2+ (aq) + 2e−
At cathode:
2MnO2 (s) + 2 NH 4+ (aq ) + 2e − → Mn 2 O3 (s) + 2 NH 3 (g) + H 2 O
Overall reaction:
Zn(s) + 2 NH +4 (aq ) + 2MnO2 (s) → Zn 2 + (aq ) + Mn 2 O3 (s) + 2 NH 3 (aq ) + H 2 O(l)
The NH3 formed is combined immediately with the Zn 2+ ions and Cl− ions to form the
complex salt [Zn (NH3)2Cl2]
Zn2+ + 2NH3 + 2Cl− → [Zn (NH3)2]Cl2
The dry cell gives a voltage of about 1.5 V. The dry cell is generally used in flash lights,
calculators, toys etc.
(b)
Lithium cells:
Lithium cells are primary (disposable) batteries. Lithium cells have lithium metal as anode
comprising many type of cathodes and electrolytes. Lithium cells are safer, less expensive,
and non-toxic and meet the needs of present as well as future generation.
Due to its high electrode potential, it can produce voltages from 1.5 V to about 3.7 volt,
which is twice the voltage of an ordinary battery.
Lithium cells are generally used in portable consumer electronic devices like radios,
clocks, MP3 players, hearing aids, heart pacemakers etc.
Lithium cells can be classified into three categories:
(1) Lithium cells with solid cathodes
(2) Lithium cells with liquid cathodes
(3) Lithium cells with solid electrolyte
(1) Lithium cells with solid cathodes:
These cells use solid cathode materials such as MnO2, CuO, V2O5 and carbon monofluoride
(CF)n. They cannot be discharged as rapidly as liquid cathode cells. Most commonly lithium
batteries in use are of the Li|MnO2 type. Due to its low discharge characteristic it is generally
suitable for memory backup, watches, calculators, cameras, etc.
The Li|MnO2 cell gives a voltage of about 3.2 V and it is capable to perform at low or
high discharge rates on pulse and perform at wider range of temperature of the cell. It has a
shelf life of around 5–7 years.
Anode: Li metal act as Anode.
Cathode: Mixture of heat – treated electrolytic manages dioxide (MnO2) and
conducting agents.
Electrolyte: Mixture of propylene carbonate and 1, 2-dimethoxy ethane.
Cell reaction
At Anode: Li → Li+ + e−
IV III
At cathode: M nO2 + Li + + e − → MnO2 ( Li + )
IV III
Overall reaction: Li + M nO2 → MnO2 ( Li + )

5.54
Oxidation of lithium metal at the anode takes place which produce positively charged
lithium ions (Li+) and electrons (e−). The Li+ ions go into the solutions and diffuse through
electrolyte and electrons (e−) reach at the cathode where MnO2 is reduced from tetravalent
to trivalent state.
(2) Lithium cells with liquid cathodes:
In these cells, the cathode material is reduced during discharging is present in the liquid
form. Examples are
• SO2 dissolved in a solution of Lithium bromide and acetonitrile
• Liquid thionyl Chloride (SOCl2) as a solvent with lithium aluminium chloride as solute.
It is incompatible with standard batteries, that why they are mostly used for military
applications such as munitions, transceivers and surveillance equipments. This type of
cells gives a voltage of about 2.8 V to 3.5 V for different systems. It has a shelf life about
10 years at normal and cooler temperature.
(i) In Li-SO2 cell
Anode: Lithium metal
Cathode: SO2
Electrolyte: Lithium bromide and small amount of acetonitrile
There is a liquid cathode; it forms a protective layer at the interface of the lithium
and SO2. To maintain the SO2 in a liquid form, Li–SO2 cells internal pressure is 3 bars
at +20 °C temperature and 14 bars at +70 °C temperature.
Overall reaction
2Li + 2SO2 → Li2S2O4
(ii) In Li–SOCl2 cell
Anode: Lithium metal
Cathode: SOCl2
Electrolyte: LiAlCl4 (lithium terachloro aluminate)
In this, porous carbon material acts as a cathode current collector which receives
electrons from the external circuit. It is not sold in the consumer market but having
more application in industrial as well as military level.
Thionyl chloride is a corrosive liquid and reacts with lithium to produce LiCl,
S and SO2. LiCl is precipitated on carbon electrode and SO2 and S are soluble in elec-
trolyte, at lower depth of discharge.
4Li + 2SOCl2 → 4LiCl + SO2 + S
Due to incomplete protective layer at surface of lithium, additives are used. It
provides a voltage of around 3.5 V. It has poor shelf life.
(3) Lithium cells with solid electrolyte:
In such type of cell, solid such as lithium iodide (LiI) ﹛which are electronic insulators but
ionic conductors﹜ can be used as the electrolyte in solid electrolyte batteries. Such batteries
have extremely long shelf life at low drain currents or even at high temperature.
Such types of cells are generally used in heart pacemakers, and for preserving volatile
computer memory.
Anode: Li metal
Cathode: Poly-2-vinyl pyridine (p2vp)
Electrolyte: Solid LiI (In situ)/ I2 (iodine)

There is a solid electrolyte and it provides a voltage of around 2.8 V. LiI is formed in
situ by direct reactions of the electrodes.
Overall reaction
2Li + p2Vp + nI2 → 2LiI + p2vp + (n − 1) I2

It is suitable only for low-current application and its voltage decreases with degree
of discharge due to precipitation of lithium iodide. It has very low self–discharge voltage.
(ii) Secondary batteries:
(a) Lead-acid cells: or (Lead storage cell)
This type of cells is called as storage battery or a storage cell. A storage cell is that which
can work both as voltaic cell as well as electrical cell. During its operation it works as a
voltaic cell i.e., it supplies electrical energy due to a chemical energy and it becomes dis-
charged. Then during its charging, it works as an electrolytic cell i.e., chemical is produced
by supplying of electrical energy. It is also called as lead storage battery.
It consist of
Anode: Lead (Pb) act as anode (or grid of lead filled with spongy lead)
Cathode: Lead dioxide (PbO2) (or grid of lead filled with PbO2)
Electrolyte: Dilute sulphuric acid (H2SO4) (35% by weight)
A lead storage battery consists of 6 cells each producing 2V output. To increase the cur-
rent output of each cell, the cathode plates are joined together and the anode plates are also
joined together and connected in series, we get an output of 12V as shown in Figure 5.28.
Anode (+)
(−) Cathode
Lead (Pb)
Dil H2SO4
Lead
dioxide (PbO2)
Figure 5.28 Lead storage battery
Electrode reactions during discharge

At anode: Lead (Pb) undergoes oxidation
Pb → Pb2+ + 2e−
The Pb2+ ions combine with SO42- (H2SO4) ions to produce PbSO4
Pb2+ + SO42- → PbSO4↓

At cathode:
Lead Oxide (PbO2) undergoes reduction due to flow of electrons from anode to cathode
PbO2 + 4H+ + 2e− → Pb2+ + 2H2O

5.56
and the Pb2+ ions combines with SO42− ions to produce PbSO4
Pb2+ + SO42- → PbSO4↓
Overall reaction
Pb + PbO2 + 4 H + + 2SO24 − → 2PbSO4 + 2H 2 O + Energy
Electrode reaction during charging

The lead storage battery is rechargeable. Now the cell is operated like an electrolytic cell.
The following reactions occur during charging:
At Anode:
PbSO4 + 2e − → Pb + SO24 −
At Cathode:
PbSO4 + 2H 2 O → PbO2 + SO24 − + 4 H + + 2e −
Overall reaction:
2PbSO 4 + 2H 2 O → Pb + PbO2 + 4 H + + 2SO24 −
The PbSO4 formed during discharge is a solid and sticks to the electrodes. So, it is in
position to gain or receive the electrons during electrolysis.
Such type of cell is generally used for electrical vehicles, Automobiles, railway, labo-
ratories, hospitals, power stations, in telephone exchange, UPS system etc.
(b)
Ni-Cd Storage cell (or NiCad cell):
This is also rechargeable cell which is generally used in calculators. It has a longer life than
lead storage cell.
It consist of
Anode: Cadmium (Cd) electrode
Cathode: Nickel (III) oxide-hydroxide [NiO (OH)]
Electrolyte: Alkaline electrolyte (KOH)
Normally Ni-Cd cells have a potential of 1.2V and by using six cells, a voltage of 7.2V
can be produced.
Electrode reactions during discharge
At Anode:
Cd + 2OH− → Cd (OH)2 + 2e−
At Cathode:
2NiO (OH) + 2H2O + 2e− → 2Ni (OH)2 + 2OH−
Overall Reaction:
Cd + 2NiO (OH) + 2H2O → Cd(OH)2 + 2Ni(OH)2
During recharge, the reactions go from right to left. The alkaline electrolyte
(KOH) is not consumed in this reaction.
Such types of cells are used in cordless and wireless telephones, emergency light-
ing, remote controlled electric model airplanes, boats, and cars etc.

(c)
Lithium ion cells:
Lithium ion batteries (sometimes abbreviate as Li-ion batteries) are a type of rechargeable
battery in which the cathode (positive electrode) contains lithium and the anode (negative
electrode) is generally made of a type of porous carbon.
During discharging, the current flows within the battery from the anode to the cathode;
the internal process is the movement of Li+ ions from anode to the cathode, through the
non-aqueous electrolyte.
During charging, an external power source, the current to pass in the reverse direction.
The positive terminal of the charging circuit is connected to the cathode of the battery and
negative terminal is connected to the anode.
Anodes: Hard carbon (LiC6), Graphite (LiC6)
Cathodes: LiCoO2, LiMn 2O4, LiNiO2
Electrolytes: Liquid (non-aqueous) electrolyte which consists of lithium salts such as
LiPF6, LiBF4 in an organic solvent, such as ethylene carbonate.
The cathode half reaction

LiCoO2 ← 
→ Li1− x CoO2 + xLi + + xe −

The Anode half reaction

xLi + + xe − + 6C ← 
→ Li x C6

In Lithium-ion battery the lithium ions are transported to and from the cathode or
anode, with the transition metal, Co in Li1-xCoO2 being oxidized from Co3+ to Co4+ during
charging, and reduced from Co4+ to Co3+ during discharge.
Applications: Used in cell phones, laptops, electric equipments.
Lithium-ion batteries are common in portable consumer electronics because of high
energy-to-weight ratios, lack of memory effect, and slow-discharge when not in use.
Lithium-ion batteries are not to be confused with lithium batteries; the difference is that
lithium batteries, containing metallic lithium acts as primary batteries, while lithium-ion
batteries are secondary batteries, containing an intercalation anode material.
(iii) Fuel cells:
Fuel cell is a device which converts the energy produced during the combustion of fuels directly
into electrical energy.
The process in a fuel cell is:
Fuel + oxygen → oxidation products + Electricity
(oxidant)
Fundamental principles of fuel cell and electrochemical cells are the same, but only differ-
ence between them is that in fuel cell, chemical energy is provided by a fuel and oxidant is stored
outside the cell in which that reactions take place.
Fuel cells have the most important characteristics:
(a) High efficiency
(b) Low emission levels
(c) Low noise levels
(d) Fuel cells are free from vibration, heat transfer and thermal pollution

5.58
Examples of Fuel Cells

(i) Hydrogen-oxygen fuel cell:
A common type of fuel cell based on the combustion of hydrogen gas:
2H2(g) + O2(g) → 2H2O(l)
This is known as Hydrogen–oxygen fuel cell. The design of H2–O2 fuel cell is as shown in
Figure 5.29.
Load
4e−
Anode − + Cathode
Gas chamber
Porous
electrodes
Ion-exchange membrane
Fuel (Hydrogen) Oxidizer (Oxygen)
4e−
4e−
2H2 4H+
4H+ O2
2H2O
H2O
Figure 5.29 H2–O2 fuel cell

It consists of two electrodes made of porous graphite impregnated with a catalyst (platinum,
silver or a metal oxide). The electrodes are placed in an aqueous solution of KOH or NaOH.
Through the anode, H2 gas is bubbled and through the cathode, oxygen gas is bubbled under
pressure of about 50 atm. The gases diffuse into the electrode pores and so does the electrolyte
solution.
The half-cell reactions which occur at the electrodes are as follows:
At Anode:
H2(g) + 2OH− (aq) → 2H2O + 2e− (Oxidation half reaction)
At Cathode:
O2(g) + 2H2O + 4e− → 4OH− (Reduction half reaction)
Overall fuel cell reaction:

2H2(g) + O2(g) → 2H2O(l)
The standard emf of the H2–O2 cell is

E° = E°(cathode) - E°(anode)

= E°(O2/OH-) -E°(H2O/H2)
= 0.401 - (-0.828)
E° = 1.229 V
In actual practice, the emf of the cell is 0.8 to 1.0 V. A fuel cell battery or fuel battery com-
prise of an arrangement of such cells in parallel or series (modules/stack of cells).
Uses of H2-O2 Fuel Cells
(i) H2-O2 fuel cell is generally used in space craft because of their high efficiency, lightness and
product water is a source of fresh water for the astronauts.
(ii) It is also used in submarines or other military vehicles.
(iii) This cell is used as the primary source of electrical energy on the Apollo moon flights.
Approximately 200 kg of fuel is sufficient for 11 days in space.
Types of H2-O2 Fuel Cell

On the basis of the type of electrolyte used in fuel cell, they are of five types:
Fuel cell Electrolyte used

(i) Alkaline fuel cell (AFC) Aqueous KOH (30–40%)
(ii) Molten carbonate fuel cells (MCFC) Mixture of Na2CO3 + WO3
(iii) Phosphoric acid fuel cells (PAFC) Phosphoric acid (H3PO4)
(iv) Solid oxide fuel cells (SOFC) Mixture of yttrium dioxide (Y2O3) + Zirconium dioxide
(ZrO2)
(v) Proton exchange membrane fuel cells (PEMFC) A H-form (cation exchange resin membrane) is used in
place of a fluid electrolyte.
Fuel Cells and their Characteristic Features
Characteristic
features AFC MCFC PAFC SOFC PEMFC
Primary fuel H2 H2, CO, CH4 H2 H2, CO H2
Electrodes Carbon Stainless steel Graphite Ceramic Carbon
Electrolytes Aqueous KOH Molten sodium Phosphoric Yttrium- Polymer mem-
(30–40%) carbonate acid stabilized ZrO2 brane
Catalyst Pt Ni Pt Perovskite Pt
Charge carrier OH− CO32- H+ O2- H+
Operating tem- 50–200 °C 600–700 °C 150–220 °C 700–1000 °C 50–100 °C
perature
Power density 1 1.5–2.6 0.8–1.9 0.1–1.5 4.8–6.5
(kW/m3)
Combined 50-60% 50-70% 55% 55-65% 50-60%
cycle fuel cell
efficiency
Major applica- Space vehicles and Stationary Stationary Auxiliary power Stationary and
tions drinking water power power in vehicles automotive power

5.60
(ii) Methanol-oxygen fuel cell: The Half cell reactions for such cells are:
At anode: CH3OH(l) + H2O(l) → CO2(g) + 6H+(aq) + 6e- (O.H.R)
3
At cathode: O (g) + 6H + (aq ) + 6e − → 3H 2 O(l) (R.H.R)
2 2
3
Overall reaction: CH 3 OH(l) + O2 (g) → CO2 (g) + 2H 2 O(l)
2
Advantages of Fuel Cell
(i) The energy conversion (chemical into electrical) is very high by fuel cells (75-82.8%).
(ii) H2-O2 fuel cell produces H2O, which is used as drinking purpose by astronauts.
(iii) Noise and thermal pollution are low.
(iv) Such type of cells never becomes dead, because of continuous supply of fuel.
(v) Modular and other parts of fuel cells are exchangeable.
(vi) Fuels cells having low maintenance cost.
(vii) Fuels cells saves fossil fuels.
(viii) The regenerative H2–O2 fuel cell is an energy storage system for space application, submarines
and other military vehicles.
Limitations of Fuel Cells
(i) High initial cost.
(ii) Large weight and volume of gas-fuel storage system.
(iii) High cost of pure hydrogen.
(iv) Liquifaction of hydrogen requires 30% of the stored energy.
(v) Life-times of such type of cells are not accurately known.
(vi) Most alkaline cells suffer from CO2 degradation and hence CO2 should be removed from the fuels
and the air.
5.16 Review Questions

1. The electrolyte whose solution conducts electricity to a small extent is called a _______
[Ans.: Weak electrolyte]
2. The electrolytic conductance _______ with temperature.
[Ans.: increases]
3. The unit of specific conductance is _______
[Ans.: ohm−1 cm−1]
4. Specific conductance is the conductance of _______ of the solution
[Ans.: 1 cm3]
5. The equivalent conductance _______ with dilution.
[Ans.: Increase]
6. The L°For a weak electrolyte is calculated by using _______ law.
[Ans.: Kohlrausch]

7. An electrochemical cell converts _______ energy into _______ energy.

[Ans.: Chemical, electrical]
8. The electrode used in the fuel cell is _______.
[Ans.: Concentrated KOH solution]
9. The effect of concentration on the electrode potential is studied by _______ equation.
[Ans.: Nernst]
10. Arrangement of electrodes in order of reducing potential is known as _______.
[Ans.: Electrochemical series]
11. Calmol electrode having _______ solution an electrolyte
[Ans.: saturated KCl]
12. A device which convert the energy of fuel direct into electrical is called as _______ cell.
[Ans.: fuel]
13. The substance which conducts electricity without any decomposition is called as _______
conductor.
[Ans.: electronic]
14. A unit of molar conductivity is _______.
[Ans.: ohm−1 cm2 mol−1]
ΛC
15. Degree of dissociation (α) = .
[Ans.: L0]
16. The tendency of electrode to loss or gain electrode is called as _______ .
[Ans.: Electrode potential]
17. Calomel electrode act as _______ electrode.

[Ans.: reference]
18. Electrode potential of saturated calomel electrode is _______

[Ans.: 0.2422 V]
19. When two like electrodes at different concentrations are dipped in some solution of the electro-
lyte is called as _______ concentration cell.
[Ans.: Electrode]
20. _______ cells are not reversible in nature.

[Ans.: Primary]
21. Lithium ion cell is an example of _______ cell.

[Ans.: Secondary]
22. In Lead-acid cell _______ is act as electrolyte.

[Ans.: Dilute H2SO4]

5.62

1. The effect of temperature increases on concentration is as follows:
(a) Metallic conduction increases, electrolytic conduction decreases
(b) electrolytic conduction increases, metallic conduction decreases
(c) Both metallic and electrolytic conduction decreases
(d) Both metallic and electrolytic conduction increases
[Ans.: b]
2. The units of equivalent conductance are:
(a) Ohm−1 (b) ohm−1 cm−2
(c) Ohm−1 cm2 (d) mho cm 2
[Ans.: c]
3. The cell constant is
l a
(a) (b)
a l
K
(c) a × l (d)
R
[Ans.: a]
4. Effect of dilution on conduction is as follows:
(a) Specific conductance increases, molar conductance decreases
(b) Specific conductance decreases, molar conductance increases
(c) Both increases with dilution
(d) Both decreases with dilution
[Ans.: b]
5. The units of the cell constant is
(a) cm−1 (b) cm 2
(c) cm3 (d) cm−2
[Ans.: a]
6. The potential of a single electrode is a half cell is called as
(a) Reduction potential (b) Half-wave potential
(c) Single electrode potential (d) Cell potential
[Ans.: a]
7. Which of the following constitutes Daniel Cell?
(a) Zn − Ag cell (b) Cu − Ag cell
(c) Zn − Cu cell (d) none of these
[Ans.: c]

8. EMF of a cell in terms of reduction potential of its left and right electrode
(a) E = Eleft + Eright (b) E = Eleft − Eright
(c) E = Eright − Eleft (d) None of these
[Ans.: c]
9. Which of the following is a secondary cell
(a) Dry cell (b) Mercury cell
(c) Ni – Cd cell (d) H2 – O2 cell
[Ans.: c]
10. An electrochemical cell stops working after some time because
(a) One of the electrodes is eaten away
(b) electrode potentials of both electrodes becomes equal in magnitude
(c) electrode potentials of both the electrodes go on decreasing
(d) electrode potentials of both the electrodes go on increasing
[Ans.: b]
11. The standard EMF (E°) for the cell reaction
Zn + Cu 2+ → Zn2+ + Cu is 1.1 volt at 25 °C. The EMF(E) of the cell reaction when 0.1M Cu 2+ and
0.1 M Zn2+ solutions are used, at 25 °C is
(a) 1.10 V (b) 0.10 V
(c) −1.10 V (d) −0.110 V
[Ans.: a]
12. In an electrochemical cell
(a) Potential energy decreases
(b) Kinetic energy decreases
(c) Potential energy changes into electrical energy
(d) Chemical energy changes into electrical energy
[Ans.: d]
13. As lead storage battery is charged
(a) lead dioxide dissolves
(b) sulphuric acid is regenerated
(c) lead electrode becomes coated with lead sulphate
(d) the concentration of sulphuric acid decreases
[Ans.: b]
14. In an electrochemical series electrodes are arranged in the
(a) Increasing order (downwards) of standard reduction potential
(b) Decreasing order of standard reduction potential

5.64
(c) Increasing order of standard oxidation potential

(d) Increasing order of equivalent weight
[Ans.: a]
15. Electrode potential of standard calomel electrode is

(a) 0.2422 V (b) 0.2400 V
(c) 0.2810 V (d) 0.3335 V
[Ans.: a]
16. Silver – Silver chloride electrode is a type of

(a) Redox electrode (b) Metal – Metal Ion electrodes
(c) Metal – Amalgam electrode (d) Gas – ion electrode
[Ans.: b]
17. Calomel electrode consist of calomel with a solution of

(a) Saturated NaCl (b) Saturated Ca (OH)2
(c) Saturated KCl (d) Saturated AgCl
[Ans.: c]
18. Which electrode is used for pH measurement

(a) Silver electrode (b) Redox electrode
(c) Glass electrode (d) Calomel electrode
[Ans.: c]
19. Lechanche cell is an example of
(a) Primary cell (b) Secondary cell
(c) Tertiary cell (d) Fuel cell
[Ans.: a]
20. A fuel cell converts
(a) Chemical energy into electrical energy
(b) Chemical energy into potential energy
(c) Chemical energy into heat
(d) Chemical energy into pressure
[Ans.: a]
21. Which is produced during H2−O2 fuel cell
(a) CH3OH (b) H2O
(c) H2O2 (d) H3O+
[Ans.: b]

22. The cathode of Ni – Cd cell is made up from

(a) NiOH (b) Ni (OH)2
(c) NiO2 (d) NiO (OH)
[Ans.: d]
23. During Charging of lead – acid cell, concentration of H2SO4
(a) Increases (b) Decreases
(c) Remains unchanged (d) First increases then decreases
[Ans.: a]
24. In potentiometric titration, graph is plotted between variations of
(a) Electrode potential with temperature of titrant
(b) Electrode potential with pressure of titrant
(c) Electrode potential with volume of titrant
(d) Electrode potential with concentration of titrant
[Ans.: c]
25. At equilibrium, EMF of the cell is
(a) 0 V (b) 100 V
(c) Less than 0 V (d) More than 0 V
[Ans.: a]
26. In glass electrode, the glass membrane undergoes exchange of Na+ ion with
(a) Ca2+ (b) Mg2+
(c) H+ (d) NH +4
[Ans.: c]
27. Quinhydrone – electrode consist of hydroquinone (QH 2) and quinone (Q) in the ratio of
(a) 1: 2 (b) 1:1
(c) 2:1 (d) 1:15
[Ans.: b]
28. Conductance of an electrode depends upon

(a) Number of free ions present in solution
(b) Number of free ions present in solvent
(c) Concentration of the solution
(d) Temperature of the solution
[Ans.: a]
29. Four metals A, B, C and D are having their reduction potentials as −3.05, −1.66, −0.40 and −0.80 V
respectively. Which one of these will be most reducing agent.
(a) A (b) B
(c) C (d) D
[Ans.: a]

5.66
30. Equivalent conductance of NaCl, HCl and C2H5COONa at infinite dilution are 126.45, 426.16
and 91 ohm−1 cm2 respectively. The equivalent conductance of C2H5COOH at infinite dilution is
(a) 201.28 ohm−1 cm2 (b) 390.71 ohm−1 cm2
−1
(c) 698.28 ohm cm 2
(d) 540.48 ohm−1 cm2
[Ans.: b]
31. Saturated Solution of KNO3 is used to make salt bridge because

(a) Velocity of K+ is greater than that of NO3−
(b) Velocity of NO3− is greater than that of K+
(c) Velocities of both K+ and NO3− are nearly the same
(d) KNO3 is highly soluble in water
[Ans.: c]
N
32. The specific conductance of solution of KCl at 25 °C is 0.002765 ohm−1. If the resistance of
50
the cell is 400 ohms, then what is the value of cell constant
(a) 2 (b) 1.106
(c) 3 (d) 3.2
[Ans.: b]
33. The EMF of the cell Ni | Ni2+ (1.0M) | Au3+(1.0M) | Au
Given that
 E° = − 0.25V for Ni 2 + | Ni
 3+ 
 E° = +1.5V for Au | Au 
V (b) −1.25
(a) 1.25 V (c) 1.75
V (d) 2.00
V
[Ans.: c]
34. The conductivity of a saturated solution of BaSO4 is 3.06 × 10−6 ohm−1 cm 2 and its equivalent
conductance is 1.53 ohm−1 cm2 equiv−1. The Ksp for BaSO4 will be
(a) 4 × 10−12 (b) 2.5 × 10−9
(c) 2.5 × 10−13 (d) 4 × 10−6
[Ans.: d]
35. Which of the following does not conduct electricity

(a) Molten NaCl (b) Aqueous NaCl
(c) Solid NaCl (d) Aqueous NH4Cl
[Ans.: c]

1. How can you test whether the given electrolyte is a strong electrolyte or a weak electrolyte?
Ans.: If the aqueous solution of the electrolyte conducts electricity to a large extent, it is a strong
electrolyte and if to a small extent, it is a weak electrolyte.

2. Define specific conductivity and mention its units.

Ans.: The specific conductance of a solution is defined as the conductance of 1 cm3 of the solu-
tion of the electrolyte. Its unit is ohm−1 cm−1 (or Ω−1 cm−1) (or S cm−1)
3. What is the effect of temperature on the electrical conduction of (i) metallic conductor (ii) elec-
trolytic conductor?
Ans.: With increase of temperature, the electrical conduction of metals decreases whereas that
of electrolyte increases.
4. Define molar conductance and gives its units.
Ans.: It is defined as the conductance of all the ions produced by dissolving 1 mole of the elec-
trolyte in V cm3 of the solution.
Its units is ohm−1 cm2 mol−1 (or S cm 2 mol−1)
5. Why do electrochemical cells stop working after some time?
Ans.: Electrochemical cells produce electrical energy at the cost of chemical energy as sponta-
neous redox reaction takes place in them. When the redox reaction is completed, the cell
stops working.
6. Give the relationship between molar conductivity and specific conductivity.
Ans.:
1000
Λm = K ×
C
Λ m = Molar conductivity
K = Specific conductivity
C = Molar concentration
7. What is the relationship between specific conductance and equivalent conductance.
Ans.: Λeq = K × V
Λeq = Equivalent conductivity
K = Specific conductance
V = Volume of solution containing 1g eq of the substance
8. Give the relationship between equivalent and molar conductance.

Ans.:
Λ m Normality
=
Λ eq Molarity
9. What is cell constant. Give its units.

Ans.: it is the ratio of the distance between the parallel plates of the cell and the area of electrolyte.
l
Cell constant = .
a
Its unit is cm−1

5.68
10. How is cell constant calculated from conductance values.

spcific conductance
Ans.: cell constant =
observed conductance
11. Why voltmeter cannot be used for the precise measurement of EMF of the galvanic cell.
Ans.: Because a part of the cell current is drawn by the voltmeter itself, thereby giving lower
value of EMF than the actual one.
12. What flows in the internal circuit of galvanic cells?

Ans.: Ions flow in the internal circuits of galvanic cells.
13. What is the EMF of the cell when the cell reaction attains equilibrium?
Ans.: At equilibrium, EMF of the cell is zero.
14. Can we use a copper vessel to store 1 M AgNO3 solution, given that E °Cu 2+/Cu = +0.34 V,
E°Ag+/Ag = +0.80 V
Ans.: As the reduction potential of Ag+/ Ag electrode is higher than that of Cu2+/ Cu electrode.
So Cu metal is incapable of displacing silver from silver nitrate solution. Thus, we can use
a copper vessel to store 1 M AgNO3 solution.
15. Why electrode potential of zinc is assigned a negative value; whereas that of copper a positive
value.
Ans.: Because Zn electrode is anodic w.r.t. S.H.E and Cu electrode is cathodic w.r.t. S.H.E.
16. What is the relationship between the standard EMF of the cell and the equilibrium constant of
the cell reaction at 298K?
0.0591
Ans.: E°cell = log Kc
n
Where E °cell = standard EMF of the cell
Kc = Equilibrium constant
n = number of electrons involved in reactions
17. What is the electrolyte used in a dry cell.

Ans.: A paste of NH4Cl, MnO2 and C is used in dry cell.
18. Why the blue colour of the solution gradually fades when CuSO4 solution is electrolyzed using
platinum electrodes.
Ans.: The blue color is due to the presence of Cu2+ ions. During electrolysis these ions are con-
verted into metallic copper hence the blue color fades.
19. Define Kohlrausch’s law?

Ans.: At infinite dilution, equivalent conductance of an electrolyte is equal to the sum of ionic
conductances of cations and anions at infinite dilution.

20. Why D.C current is not used while determining the resistance of an electrolyte?
or
Why only A.C is used and not D.C source in conductometric estimation?
Ans.: If conductometric estimation is carried out by using D.C then the products of electrolysis
collect at the electrodes and set up a back emf, Which apparently increases the resistance
of the electrolyte. So, such estimations are carried out by using AC and detecting the flow
of current.
21. What is the basic reason that a lead storage battery can be recharged?
Ans.: PbSO4 is deposited on the electrodes. So, the electrode reactions can be reversed.
22. Out of zinc and tin which are protects iron better even after cracks and why?
Ans.: Zinc protects better because oxidation potential of zinc is greater but that of tin is less
than that of iron.
23. Why does the equivalent conductivity of a weak electrolyte increase with dilution?
Ans.: Because degree of dissociation of weak electrolyte increases with dilution. As a con-
sequence, the total number of ions present per gram equivalent also increases. Hence,
equivalent conductivity of weak electrolyte increases with dilution.
24. Why equivalent conductivity at infinite dilution for a weak electrolytes solution cannot be deter-
mined experimentally.
Ans.: Equivalent conductivity for a weak electrolyte increases steadily with dilution, and the
curve between Leq and C is not a straight line. The curve does not meet the equivalent
conductivity axis. So, the value of L∞ cannot be obtained by extrapolation. Hence L∞ for
a weak electrolyte is determined indirectly by using kohlrausch’s law.
25. Why, with dilution, equivalent conductance increases but specific conductance decreases.
Ans.: With increase in dilution, two things happen, namely degree of dissociation increases, but
the total volume increases. The number of ions per cm3 decreases, because the effect of
increased volume in decreasing the number of ions per cm3 outweighs the minor increase
in conductance with increase of dilution. On the other hand, equivalent conductance
increases, because the total number of ions per gram equivalent increases with dilution,
due to increased degree of ionization.
26. Why a dry cell becomes dead after a long time even if it has not been used?
Ans.: This is because the acidic NH4Cl corrodes the zinc container even if it has not been used.
27. Solution of two electrolytes A and B each having a concentration of 0.2 M have conductivities
2 × 10−2 and 4 × 10−4 S cm−1 respectively. Which will after greater resistance to the flow of current
and why?
Ans.:
l 1 l
k = c× = ×
a R a

5.70
1
i.e k ∝
R
Conductivity is reciprocal to resistance. Hence, B will offer greater resistance.
28. What is the role of ZnCl2 in dry cell?
Ans.: ZnCl2 combine with NH3 produces to form the complex salt [Zn(NH3)2Cl2] as otherwise
the pressure developed due to NH3 would crack the seal of the cell.
29. Which types of cells are rechargeable?
Ans.: Those cells are rechargeable in which the products formed during discharge are depos-
ited on the electrodes and these can be decomposed to give the original substances when
electrical energy is supplies.
30. The standard reduction potential values of three metallic cations X, Y, Z are 0.52, -3.03, -1.18 V
respectively. What will be the order of reducing power of the corresponding metals?
Ans.: The standard oxidation potential (equal and opposite in sign of standard reduction poten-
tial) of the metals X, Y, Z will be -0.52, 3.03, 1.18 V respectively. Higher the oxidation
potential, more easily metal is oxidized and here greater is the reducing power. Hence, the
reducing power will be in the order Y > Z > X.
31. Why a cell stop working after some time

Ans.: With time, concentration of the electrolytic solutions change. Hence, their electrode
potentials change. When the electrode potentials of two half cells become equal, the cell
stops working.
32. Write any two advantage of H2 – O2 fuel cell over ordinary cell.
Ans.: (i) They do not cause pollution.
(ii) They have high efficiency of 60 – 70%.
33. Write the Nearst’s equation for the electrode reaction:
M n + (aq ) + ne − → M(s)
Ans.:
2.303RT
E M n+ / M = E° M n+ /M + log[ M n + (aq )]
nF
34. Define standard hydrogen electrode.
Ans.: Standard hydrogen electrode (SHE) or Normal hydrogen electrode (NHE) is a reference
electrode which is obtained by dipping platinum foil in 1M HCl solution through which
hydrogen gas is passed at 298 K under 1 atm pressure. Its electrode potential is zero.
35. Glass electrode is preferred to quinhydrone electrode in measuring pH of a solution, Give reason.
Ans.: Glass electrode is simple, not easily oxidized and attain equilibrium rapidly. It can safely
be used upto pH of 10. On the other hand, quinhydrone electrode can be used upto pH of
8 only. It cannot be used in solutions containing redox system. Hence glass electrode is
preferred over quinhydrone electrode in pH measurement of a solution.

36. Alkaline dry cells are considered better than Lechanche cell why?
Ans.: Alkaline dry cell lasts longer, because zinc electrode does not corrode easily.
37. What is the purpose of MnO2 in dry cell?
Ans.: It acts as an oxidizing agent in dry cell.
38. Write the formula for determining the degree of dissociation of weak electrolyte.
Ans.:
equivalent conductivity at any concentration
Degree of dissociation (a ) =
equivalent conductivity at infinite dilutioon
Λ
a = c
Λo
39. What is the emf of H2 – O2 fuel cell?

Ans.: E° = 1.229 V
40. Define fuel cell.
Ans.: Fuel cell is a device which converting energy of a fuel directly into electrical energy.
41. What is Lead - acid accumulator?
Ans.: A secondary cell consisting as lead electrodes, the positive one covered with PbO2,
dipping into H2SO4 solution. Its emf is about 2V.
42. Write major applications of lithium ion cells.

Ans.: Lithium ion cell used in cell phones, laptops, electrical equipment’s etc.
5.16.4 Solved Numerical Problems

N
(i) If specific conductivity of KCl solution at 298 K is 0.002765 ohm−1 cm−1 and resistance of a
50
cell containing this solution is 100 ohm. Calculate cell constant.

Solution As we know that
SP. conductivity K
Cell constant = =
obs. conductance C
Specific conductivity, K = 0.002765 ohm−1 cm−1

1
Conductance, C = ohm −1
100
 l  0.002765
So, cellconstant   =
 a 1
100
= 0.002765 × 100
cellconstant = 0.2765 cm −1

5.72
(ii) Specific conductivity of a 0.12 N solution of an electrolyte is 0.024 ohm−1 cm−1. Determine its
equivalent conductivity.
Solution Equivalent conductivity (Leq )
1000 1000
Λ eq = K c × = Kc ×
Ceq Noramality
Specific conductivity (K) = 0.024 ohm−1 cm−1

1000
Λ eq = K ×
Normality
1000
= 0.024 ×
0.12
Λ eq = 200 ohm −1 cm 2 eq −1
(iii) The resistance of a 0.1 N solution of an electrolyte in a conductivity cell was found to be
245 ohms, calculate the equivalent conductivity of the solution if the electrode in the cell were
2 cm apart and each has an area of 3.5 cm 2.
Solution
l
Specific conductivity K = C ×
a
1 2
= ×
245 3.5
1000
Equivalent conductivity (Λ eq ) = K ×
Normality
1 2 1000
= × ×
245 3.5 0.1
Λ eq = 23.32 ohm −1 cm 2 equ −1
(iv) If the equivalent conductivities at infinite dilution of NaCl, HCl and CH3COONa are 126.4,
426.1 and 91.0 ohm−1 cm 2 equiv−1 respectively, what will be the equivalent conductivity at infi-
nite dilution for acetic acid.
Solution According to Kohlrausch’s law
Λ 0 for CH 3 COOH = l 0 (CH 3 COO − ) + l 0 ( H + )
Given that
Λ 0 ( NaCl) = l 0 ( Na + ) + l 0 (Cl − ) (i)
Λ 0 ( HCl) = l 0 ( H + ) + l 0 (Cl − ) (ii)
Λ 0 (CH 3 COONa) = l 0 (CH 3 COO− ) + l 0 ( Na + ) (iii)

Λ 0 ( NaCl) = 126.4 ohm −1 cm 2 equiv −1

Λ 0 ( HCl) = 426.1 ohm −1 cm 2 equiv −1
Λ 0 (CH 3 COONa ) = 91.0 ohm −1 cm 2 equiv −1
Adding equations, (ii) and (iii) and subtracting (i), we get l0(H+) + l0(Cl−) + l0(CH3COO−) +
l0(Na+) - l0(Na+) - l0(Cl−) = 426.1 + 91.0 – 126.4
l0(CH3COO−1) + l0(H+) = 390.7 ohm−1 cm2 eq−1
i.e., Λ 0 for CH 3 COOH = 390.7 ohm −1 cm 2 eq −1
(v) From the following equivalent conductivities at infinite dilution,
Λ 0 for Ba (OH)2 = 457.6 ohm −1 cm 2 eq −1

Λ 0 for BaCl 2 = 240.6 ohm −1 cm 2 eq −1
Λ 0 for NH 4 Cl = 129.8 ohm −1 cm 2 eq −1
Calculate Λ 0 for NH4OH

Solution
Λ 0 [Ba(OH)2 ] = l 0 ( Ba 2 + ) + 2 l 0 (OH − ) (i)
Λ 0 [Ba(Cl)2 ] = l 0 ( Ba 2 + ) + 2 l 0 (Cl − ) (ii)
Λ 0 [ NH 4 Cl] = l 0 ( NH 4+ ) + l 0 (Cl − ) (iii)
Λ 0 ( NH 4 OH) = l 0 ( NH 4+ ) + l 0 (OH − ) (iv)

1 1
eqn.(i) + eqn.(iii) − equ (ii)
2 2
1 1
= × 457.69 + 129.8 − × 240.6
2 2
Λ 0 ( NH 4 OH) = 238.3 ohm −1 cm 2 eq −1
(vi) The equivalent conductivity at infinite dilution of KCl, HCl and CH3COO K are 130.1, 379.4
and 95.6 ohm−1 cm 2 eq−1 respectively. Calculate equivalent conductivity at infinite dilution for
CH3COOH. If equivalent conductivity of a given acetic acid solution is 48.5 ohm−1 cm 2 eq−1 at
25 °C. Calculate the degree of dissociation of CH3COOH at this temperature.
Solution
Λ 0 for KCl = 130.1 ohm −1 cm 2 equ −1
Λ 0 for HCl = 379.4 ohm −1 cm 2 equ −1
Λ 0 for CH 3 COOK = 95.6 ohm −1 cm 2 equ −1
Λ 0 for CH 3 COOH = l 0 (CH 3 COO − ) + l 0 ( H + )

5.74
Λ 0 ( KCl) = l 0 ( K + ) + l 0 (Cl − ) (i)

+ −
Λ 0 ( HCl) = l 0 ( H ) + l 0 (Cl ) (ii)
− +
Λ 0 (CH 3 COOK ) = l 0 (CH 3 COO ) + l 0 ( K ) (iii)
(ii) + (iii) - (i)
Λ 0 (CH 3 COOK ) + Λ 0 ( HCl) − Λ 0 ( KCl) = Λ 0 (CH 3 COOH )
Λ 0 (CH 3 COOH ) = 379.4 + 95.6 − 130.1

= 344.9 ohm −1 cm 2 mol −1
Give that Λ c = 48.5 ohm −1 cm 2 mol −1
Λ
Degree of dissociation (a ) = c
Λ0
48.5
=
344.9
a = 0.141
(vii) At 291 K the equivalent conductivities at infinite dilution of NH4Cl, NaOH and NaCl are 129.8,
217.4 and 108.9 ohm−1 cm 2 respectively. If the equivalent conductivity of a 0.01N solution of
NH4OH is 9.33 ohm−1 cm 2, what is the percentage dissociation of NH4OH at this dilution? Also
calculate the dissociation constant of NH4OH.
Solution
Here, we are given:
Λ 0 for NH 4 Cl = 129.8 ohm −1cm 2
Λ 0 for NaOH = 217.4 ohm −1cm 2
Λ 0 for NaCl = 108.9 ohm −1cm 2
By Kohlrausch’s law
Λ 0 for NH 4 OH = l 0 ( NH +4 ) + l 0 (Cl − )
= Λ 0 ( NH 4 Cl) + Λ 0 ( NaOH) − Λ 0 ( NaCl)
= 129.8 + 217.4 − 108.9
Λ 0 for NH 4 OH = 238.3 ohm −1cm 2
Given that, Λ 0 for NH 4 OH = 9.33 ohm −1cm 2

Λc
∴ Degree of dissociation (a ) =
Λ0
9.33
=
238.3
= 0.0392
Percentage dissociation = 0.0392 × 100
= 3.92 %


Calculation of dissociation constant
Ca 2
K=
1−a
Here, C = 0.01N
a = 0.0392
0.01 × (0.0392)2
So, K =
1 − 0.0392
0.01 × (0.0392)2
= = 1.599 × 10 −5
0.9608
So, dissociation constant, K = 1.599 × 10−5
(viii) The conductivity of a saturated solution of AgCl at 288 K is found to be 1.382 × 10−6 ohm−1
cm−1. Find it solubility. Given ionic conductances of Ag+ and Cl− at infinite dilution are 61.9
ohm–1 cm2 eq−1 and 76.3 ohm−1 cm2 eq−1 respectively.
Solution
Λ 0 ( AgCl) = l 0 ( Ag + ) + l 0 (Cl − )
= 61.9 + 76.3
= 138.2 ohm −1cm 2 eq −1
1000
Solubility, s = K ×
Λ0
1000
= 1.382 × 10 −6 ×
138.2
= 10 −5 eq L−1
Equivalent weight of CH3 COOH = 143.5g

So, solubility = 143.5 × 10−5 g L−1
Solubility = 1.435 × 10−3 gL−1
(ix) Calculate the standard EMF of a cell which involves the following cell reaction
Zn + 2Ag+→ Zn2+ + 2Ag
Given that E°(Zn2+, Zn) = -0.76 volt
E° (Ag+, Ag) = 0.80 volt
Solution
At L.H.S, Zn → Zn2+ + 2e− (oxidation)
At R.H.S, 2Ag+ + 2e−→ 2Ag (Reduction)
E° = E°right - E°left
= 0.80 – (-0. 76)
E° = 1.56 volts

5.76
(x) Can a solution of 1M CuSO4 be stored in a vessel made of nickel metal? Given that
E°(Nl2+, Ni) = -0.25 volt
E°(Cu2+,Cu) = +0.34 volt
Solution In this problem, we want to see.
Ni + CuSO4→ NiSO4 + Cu
The cell may be represented as
Ni Ni 2+ Cu 2+ Cu
E° = E°right - E°left
= 0.34 – (-0.25)
E° = 0.59 volt
Thus EMF of the cells comes out to be positive. It means CuSO4 reacts with nickel. Hence,
CuSO4 cannot be stored in nickel vessel.
(xi) Calculate the EMF of a Daniel cell at 25 °C, when the concentration of ZnSO4 and CuSO4 are
0.001M and 0.1M respectively. The standard potential of the cell is 1.2 volts.
Solution The cell may be represented as
Zn(s)  Zn 2+ (0.001M )  Cu 2+ (0.1M ) Cu (s)
0.0591 Cu 2 + 
E cell = E°cell − log  2 + 
n  Zn 
E°cell = 1.2
n=2
0.0591 (0.1)
So, E cell = 1.2 − log
2 (0.001)
0.0591
= 1.2 + ×2
2
= 1.2 + 0.0591 = 1.2591 volt
E cell = 1.2591 volt
(xii) Calculate the equilibrium constant for the reaction
Zn + Cd 2 + Zn 2 + + Cd  E° = 0.36 V 
 cell 
Solution
0.0591
E°cell =
log K eq
n
For the given reaction n = 2
E°cell = 0.36 V

0.0591
So, 0.36 = log K eq
2
0.36 × 2
log K eq = = 12.1827
0.0591
K eq = Antilog(12.1827)
K eq = 1.52 × 1012
(xiii) Calculate the emf of a concentration cell at 25 °C consisting of two Zn electrodes immersed in
solutions of Zn 2+ ions of 0.1 M and 0.01 M respectively.

Solution EMF of concentration cell at 25 °C is given by
0.0591 C
Ecell = log 2 [C2 > C1 ]
n C1
Now for Zn 2+/Zn, n = 2

0.0591 0.1
Ecell = log
2 0.01
0.0591
log 10 = 0.0296 × 1
2
Ecell = 0.0296 volt
(xiv) Find the valency of mercurous ions with the help of following cell:
0.002 N mercurous 0.02 N mercurious

Hg Nitrate in 0.1N HNO3 nitrate in 0.1NHNO3 Hg
Anode Cathode
When the emf measured at 18 °C is 0.029 volt.
0.0591 C
Ecell = log 2
n C1
0.0591 0.02
0.029 = log
n 0.002
By solving, n = 2.
(xv) While determining the pH of a solution, the quinhydrone electrode, H+, Q, QH2 was used in
conjunction with a saturated calomel electrode as represented below;
Hg,Hg 2 Cl 2 (s); KCl(Sat. Soln)  Η + ( unknown); Q, QH 2 , Pt
The EMF of the cell was found to be 0.2640 volt at 25 °C. Calculate the pH of the solution at this
temperature given that
Ecalomel = +0.2422 volt at 25 °C and
E°(H+, Q, QH2) = +0.6996 volt

5.78
Solution
The EMF of the cell is given by
E = Eright - Eleft
0.2640 = 0.6996 – 0.0591 pH – 0.2422

0.6996 − 0.2422 − 0.2640
pH =
0.0591
pH = 3.27

Q.1 On the basis of electrolytic condition, how are the electrolytes classified.
Q.2 What is an electrochemical series? Discuss its important applications.
Q.3 Explain Kohlrausch’s law of independent migration of ions. Mention one application of
kohlrausch’s law.
Q.4 What are concentration cells? Explain with example?
Q.5 What is an ion selective electrode? Explain its principle and working.
Q.6 Explain the following terms.
a. Specific conductance
b. Molar conductance
c. Equivalent conductance.
What will be effect of dilution on them?
Q.7 Discuss briefly conductometric titration.
Q.8 a. In conductrometric titration, more concentrated solution is added from burette, why? What
are the advantages of conductrometric titration over ordinary volumetric methods?
b. Draw weak acid – strong base conductometric titration curve and explain it.
Q.9 What is standard electrode potential? Give its importance.
Q.10 a. Why do electrochemical cells stops working after some time?
b. W hy does blue color of copper sulphate solution fade when it is electrolyzed using platinum
electrodes?
Q.11 What are redox electrodes? Indicate the electrode reaction and electrode potential with suitable
example.
Q.12 What is electrochemical series, Give its applications with suitable examples.
Q.13 Describe the following electrodes giving the diagram, electrode notation and electrode reaction
(i) Standard hydrogen electrode
(ii) Calomel electrode.
Q.14 Write short note on fuel cell, how it is different from commercial cell? Mention the advantages of
fuel cells.

Q.15 Write briefly about

(i) Primary cells
(ii) Secondary cells.
Q.16 Explain the working principle of methanol - oxygen fuel cell.
Q.17 Explain the working principle of Ag - AgCl electrode.
Q.18 Describe the construction of lead-acid battery with the reaction occurring during discharge.
Q.19 How does fuel cell differ from battery?
Q.20 What are reference electrodes? Explain the working of quinhydrone electrode.
Q.21 Explain the composition, applications and advantages of the following cells
(i) Ni-Cd Cell
(ii) Lithium ion cell
(iii) Dry cell
Q.22 How are specific conductance and equivalent conductance related to concentration of an
electrolyte?
Q.23 Explain the measurement of pH of solution using glass electrode. Mention the advantages of this
electrode.
Q.24 What is an ion-selective electrode? Explain its working.
Q.25 Explain the construction and functioning of a Daniel cell.
Q.26 Explain the EMF method for determination pH of a solution.
Q.27 What is emf? How is it measured potentiometrically?
Q.28 Derive Nernst equation for the calculation of cell emf.
Q.29 Differentiate primary, secondary and fuel cells with examples.
Q.30 How do you differentiate between EMF series from galvanic series?
5.16.6 Problems for Practice

1. The resistance of 0.01 N NaCl solution at 25 °C is 200 ohms. Cells constant of the conductivity
cell is unity. Calculate the equivalent conductance of the solution.
[Ans.: 500 ohms−1 cm2]
2. Molar conductivity of a 1.5 M solution of an electrolyte is found to be 138.9 S cm2, what would
be the specific conductance of this solution.
[Ans.: 0.208 S cm−1]
3. The measured resistance of a conductance cell containing 7.5 × 10−3 M solution of KCl at 25 °C
was 1005 ohms. Calculated (a) specific conductance and (b) molar conductance of this solution.
Given that cell constant = 1.25 cm−1
[Ans.: (a) = 0.001244 S cm−1
(b) = 165.87 S cm 2 mol−1]

5.80
4. The resistance of a decinormal solution of a salt occupying a volume between two platinum elec-
trodes 1.8 cm apart and 5.4 cm 2 in area was found to be 32 ohms. Calculate equivalent conduct-
ance of this solution
[Ans.: 104.1 ohm−1 cm2 eq−1]
5. The resistance of 0.2N solution of an electrolyte was found to be 250 ohms at 25 °C. Calculate the
equivalent conductivity if the cell constant is 0.75 cm−1
[Ans.: 15 ohm−1 cm2 eq−1]
6. Calculate the equivalent conductance at infinite dilution for CH3COOH, given that
Λ 0 ( HCl) = 425 ohm −1 cm 2 eq −1
Λ 0 ( NaCl) = 188 ohm −1 cm 2 eq −1
Λ 0 (CH 3 COONa ) = 96 ohm −1 cm 2 eq −1
[Ans.: 333 ohm−1 cm2 eq−1]
7. The equivalent conductance of NaOH, NaCl and BaCl2 at infinity dilution are 2.481 × 10−2,
1.265 × 10−2 and 2.800 ×10−2 ohm−1 m 2 eq−1 respectively. Calculate Λ 0 for Ba (OH)2.
[Ans.: 5.232 × 10−2 ohm−1 m 2 eq−1]
8. If the equivalent conductivities at infinity dilution at 293 K for HCl, CH3COO Na and NaCl are
383.5, 78.4 and 102.0 ohm−1 cm 2 respectively. Calculate equivalent conductivity at infinity dilu-
tion. The equivalent conductivity of CH3COOH at other dilution is 100.0 ohm−1 cm 2 at 293 K,
Calculate degree of ionization of acetic acid at this dilution.
[Ans. : Λ 0 = 359.9 ohm −1cm 2 ; a = 0.278]
9. The specific conductivities of a saturated solution of AgCl is 2.30 × 10−6 ohm−1 cm−1 at
25 °C. Calculate the solubility of AgCl at 25 °C, Given that l 0 ( Ag + ) and l0(Cl−) are 61.9 and
76.3 ohm−1 cm 2 eq−1 respectively.
[Ans.: 2.388 × 10−3 gL−1]
10. Calculate the percentage dissociation of AgNO3 at 18 °C, given that ionic conductivity of Ag+ and
NO3− ions are 56.7 and 60.5 ohm−1 cm 2 eq−1. The specific conductance of a decinormal solution of
Ag NO3 at 18 °C is 0.0085 ohm−1 cm−1
[Ans.: 72.52%]
11. The equivalent conductivity of 0.025 N HCOOH acid is 46.1 S cm 2 eq−1. Calculation its degree of
dissociation and dissociation constant. Give that
l0 ( H + ) = 349.65 cm 2 eq −1

l0 ( HCOO − ) = 54.65 cm 2 eq −1
[Ans.: degree of dissociation, 0.114, Dissociation const, k = 3.67 × 10−4]
12. For the cell show below:

Zn(s) ZnSO 4 (aq) CuSO 4 (aq ) Cu (s)

Calculate standard cell potential if standard state reduction electrode potential for Cu2+/Cu and
Zn 2+/Zn is +0.34 V and – 0.76 V respectively.
[Ans.: 1.10 V]
13. Can we use a copper vessel to store 1 M Ag NO3 solution? Given that
E °Cu 2+ | Cu = +0.34 V
E° Ag+ | Ag = +0.80 V
[Ans.: No, we can’t use copper vessel to store Ag NO3]
14. A galvanic cell consist of a metallic zinc plate immensed in 0.1 M Zn(NO3)2 solution and metallic
plate of lead in 0.02 M Pb(NO3)2 solution. Calculate the emf of the cell. Given that standard emf
of the cell is 0.63 volts. Also represents the cell reaction.
[Ans.: EMF = 0.6094 volts, cell reaction Zn | Zn 2+ || Pb2+| Pb]
15. Calculate the EMF of the following cell at 298 K Cd(s) | cd 2+ (0.04M) || Ni2+(2.0M) | Ni (s) given
that standard EMF of the cell is 0.15 volt.
[Ans.: Ecell = 0.20 volt]
16. Calculate the EMF of the following cell

Cr | Cr3+ (0.1M) || Fe2+(0.01M) | Fe
Given that standard EMF of the cell is 0.30 volts
[Ans.: Ecell = 0.2606 volts]
17. Calculate the equilibrium constant for the reaction

Sn 2+ (aq ) + Pb(s) Sn(s) + Pb 2+ (aq) at 298K
Given that E° Sn2+/Sn = -0.14 V
E° Pb2+/Pb = -0.13V
[Ans.: Keq = 0.46]
18. Calculate the standard emf of the H2–O2 fuel cell, given E° values as -0.40 V and 0.83 V for
hydrogen and oxygen half-cell respectively.
[Ans.: 1.23 V]
19. Calculate the EMF of the electrode-concentration cell
Pt; H2(p1), HCl, H2(p2); Pt at 25 °C
If p1 = 600 torr and p2 = 400 torr,
[Ans.: Ecell = 5.19 × 10−3 V]
20. The EMF of the following cell at 25 °C is 0.445 volt. The cell reaction is represented as
pt,H 2 (g) H + ( unknown conc) KCl (sat. soln.) Hg 2 Cl 2 , Hg
Calculate the pH of the unknown solution, give that reduction potential of saturated calomel
electrode is 0.2422 volt.
[Ans.: pH = 3.38]

6 Science of
Corrosion
6.1 Introduction
Corrosion can be defined as the slow degradation or deterioration of a metallic material from the metallic
surface due to unwanted attack by the atmosphere gases, soil, chemical, or electrochemical reaction
with its environment (gaseous or liquid medium).
Degradation or deterioration means reduction in the useful properties of the material which
includes:
(i) Decaying of surfaces of metals
(ii) Weakening of the material due to loss of cross sectional area.
(iii) Loss of properties such as malleability, ductility.
(iv) Cracking of polymer due to sunlight.
6.1.1 Causes of Corrosion

It has been found that most metals (exceptions noble metals like Au, Pt, etc.) exist in nature is combined
forms as their oxides, carbonates, sulphates, sulphides, chlorides etc. Metals are extracted from their
ores by using different extraction processes. Energy is required for the extraction of metals. So, conse-
quently pure metals have higher energy than combined form which has lower energy. For this, metals
easily undergo interaction with their environment either chemically or electrochemically to form a
Stable compound by the process of corrosion.
Corrosion is an oxidation process in which metallic compound having lower energy is formed and
energy liberates.
Corrosion (Oxidation)
Metal
Metallic compound + Energy
Metallurgy(Reduction)
( Higher energy) (L
Lower energy )
or or
 Thermodynamically   Thermodynamically 
 Unstable   Stable 
   
Examples:
(i) Rusting of iron:
When Iron exposed to the atmospheric conditions, a layer of reddish scale and powder of Fe3O4
is formed on the surface.

(ii) Formation of green film on the surface of copper:

A green layer of basic carbonate consisting of [CuCO3 + Cu (OH)2] is formed on the surface of
copper when exposed to moist air.
(iii) Tarnishing of silver:
When silver is exposed to the atmosphere, a black coating of air is formed.
6.1.2 Types of Corrosion

Various types of corrosion processes along with their respective mechanism are given below:
Corrosion
Dry Wet Atmospheric Soil Other

or or forms
chemical Electrochemical
Corrosion Other Liquid Inter Granular Erosion Microbiological

by gases Metal
Oxygen
Galvanic Pitting Stress Crevice Concentration Water line

Cell or
Differential
aeration
Dry or Chemical Corrosion

In such a type, corrosion occurs due to direct chemical action of atmospheric gases such as oxygen,
halogens, sulphur dioxide and hydrogen sulphide with metals resulting into the formation of com-
pounds such as oxides, halides, sulphates and sulphides is known as chemical corrosion. The products
which are formed are insoluble, soluble or liquid in nature.
Dry Corrosion is of types
(i) Oxidation corrosion (Corrosion by oxygen)
(ii) Corrosion by other gases
(iii) Liquid metal corrosion
(i) Oxidation corrosion:
Oxidation corrosion is due to the direct chemical attack of oxygen on the metal in the absence of
moisture at low or high temperature leading to the oxidation of metal.
Alkali metals (Li, Na, K, etc) and alkaline earth metals (Be, Ca, Sr, etc) are oxidized at low
temperatures, whereas all other metals (except Ag, Au, and Pt) are oxidized at high temperatures.

Science of Corrosion 6.3
Mechanism
When a metal is exposed to air, absorption of oxygen takes place even at ordinary temperatures. This
absorption is purely physical in nature and is due to vander Waal’s forces. However, due to climatic
changes, the absorbed oxygen may gradually enter into chemical combination with the metal by elec-
tron transfer between the metal atoms and oxygen as shown below:
2M → 2M n + + 2 ne − (loss of electrons by metal)
(metal ion )
n
O + 2 ne − → nO2 − (gain of electrons by oxygen)
2 2 (oxide ion )
n
overall reaction 2M + O → 2M n+ + nO2 − → M 2 O n
2 2
( metal ion) oxide ion metal oxide
The metal oxide scale is formed at the metal surface. This scale acts as a barrier and tends to
prevent the underlying metal atoms to come in contact with oxygen. The continuation of the oxidation
process depends upon two factors.
(a) The nature of the oxide film formed
(b) The rate of diffusion of the metal ion and oxide ion through the layer formed.
Nature of the Oxide Film Formed on the Surface

hen a metal is placed in atmosphere a thin layer of oxide film is formed at the surface of the metal
W
which can be written as
Metal + Oxygen → Metal oxide
This metal oxide layer can be
(i) Stable: When the oxide film is stable, impervious and highly adhering, such kind of layer forms
a shield for metal surface. The layer consists of fine grain particles which tightly sticks to the
metal surface and does not allow oxygen to diffuse into the metal surface and thus prevents
metal from corrosion e.g. Al, Pb, Cu, Sn etc.
(ii) Unstable: When the oxide film is unstable and has tendency to decompose back to metal and
oxygen, it does not undergo in oxidation corrosion e.g. Au, Ag, Pt, etc.
Metal oxide Metal + Oxygen
(iii) Porous: When the oxide layer having pores or cracks. In such a case, diffusion of cations (Mn+)
and anions (O2-) take place smoothly then oxidation corrosion takes place continuously, till the
entire metal is completely converted into its oxide.
Porous Metal
Oxide
Exposed surface
+O2 Further attack on

Metal Metal metal surface through
(of air)
pores/cracks
The porous nature of oxide film may be explained by pilling-Bedworth rule.

Pilling Bedworth Rule

This rule describes the protective and non-protective nature of the oxide layer which is formed during
corrosion.
According to this rule, the specific volume ratio is calculated as follow:
Volume of metal oxide
Specific volume Ratio =
Volume of metal
(i) If the specific volume ratio is smaller, the oxidation corrosion will take place because the oxide
films will be sufficiently porous for diffusion of M n+ and O2-.
(ii) If volume of metal oxide ≥ volume of parent metal, then it will be non-porous or protective.
(iii) If volume of metal oxide < volume of parent metal, then it will be porous or non-protective.
Examples: Alkali and alkaline earth metals (like Li, Na, K, Mg) form oxides of volume less
than the volume of metal. So, oxide layer faces stress and strains, which result in
development of cracks and pores in its structure. So, further corrosion continues till
the whole metal is destroyed.
But in case of metal like Al forms oxide, whose volume is greater than volume of metal. So, non-
porous, tightly adhering layer is formed, so rate of oxidation rapidly decreases to zero.
Rate of Diffusion of Metal Ion and Oxide Ion Through the Layer Formed
Metal and oxygen combine to form metal oxide which forms a thin film whose thickness is less than
300A°, and it’s called as scale, if its thickness exceeds this value.
This film or scale prevents further oxidation. But for oxidation to continue either the metal ion
must diffuse outwards through the scale to the surface or oxygen ion must diffuse inwards through the
scale to the underlying metal. Both transfers occur, but outward diffusion of metal ion is much easier
because metal ions are smaller than oxide ion and of higher mobility as shown in Figure 6.1.
Reaction at metal-Metal oxide
interface
M → Mn++ ne−(oxidation)
Inward diffusion
of oxide ion through
scale (slow) O2−
Mn+
Atmospheric O2−
Mn+
oxygen (air) Metal (M)
Formation of
e−
metal oxide (M2O)
at the point of
meeting of ions
Reaction at exposed part

1 O + 2e−→O2− (Reduction)
2 2 Direction of electron flow
Outward diffusion of metal ion

through scale (fast process)
Figure 6.1 Oxidation mechanism of metals

(ii) Corrosion by other gases:

Corrosion also occurs by other gases like SO2, Cl2, CO2, H2S, F2 etc. This depends upon the
affinity of metals with these metals. The degree of attack depends on the formation of protective
(non-porous) or non-protective (porous) film on the surface.
The extent of corrosion depends upon the following:
(a) Nature of the environment: The environment plays very important role in corrosion because
it facilitates the affinity between metal and gases.
(b) Chemical affinity between metal and gas: If the affinity between metal and gas is more,
then corrosion will be more and more
(c) Nature of the film formed on the metal surface:
(1) If the film formed is protective or non-porous,then the intensity of attack decreases
Eg: 2Ag + Cl 2 → 2Ag Cl

( protective layer)
(2) If the formed is non–protective or porous, metal is destroyed rapidly
Eg: Sn + 2Cl 2 → SnCl 4
Volatile layer
i.e non-protective layer
It evaporates and metal surface is exposed for corrosion.
(iii) Liquid metal corrosion:
This type of corrosion happens when liquid metal flows over solid metal or alloy at high tem-
perature and solid metal or alloy usually gets weakened. This type of corrosion mainly occurs
in nuclear powers devices.
There are two possibilities of liquid metal corrosion:
(a) Either the liquid dissolves the solid metal surface.
(b) Liquid penetrates into the solid surface and thus weakens the bond.
Wet or Electrochemical Corrosion

It is also known as immersed corrosion. It is more common than dry corrosion. It occurs mostly under
wet or moist conditions through the formation of electrochemical cells, and is therefore, referred to as
electrochemical corrosion.
Wet corrosion can be easily explained by electrochemical theory.
Electrochemical Theory of Corrosion

All metals have tendency to pass into solution. The tendency of metal to pass into solution when
immersed in a solution of its salt is measured in terms of electrode potential. If a metal having lower
reduction potential (higher electropositive) comes into contact with another metal having a higher
electrode potential (higher electro negative) a galvanic cell is set up. The metal having lower electrode
potential becomes anodic and get dissolved as corresponding metallic ions with the liberation of free
electrons.
M → Mn+ + ne- (Oxidation)
The metal with high electrode potential acts as cathode and gets protected during the process.

Mechanism of Electrochemical Corrosion

(i) The existence of separate cathodic and anodic areas between which current flows through the
conducting solution.
(ii) Oxidation (loss of electrons) takes place at the anodic area and the metal is destroyed by
either dissolution or combination with oxygen. Hence, corrosion always takes place at the
anode.
M → Mn+ + ne- (Oxidation)
(iii) Reduction (gain of electrons) takes place at the cathode. The electrons from the anode are a ccepted
by the dissolved oxygen forming ions such as OH- or O2- ions.
1
O + H 2 O + 2e − → 2OH − ( Reduction )
2 2
or
O2 + 2e − → 2O2 − ( Reduction )
(iv) The metallic ions (at anodic area) and non-metallic ions (at cathodic area) diffuse towards each
other through conducting medium and form a corrosion product somewhere between anode and
cathode.
Depending on the nature of corrosive environment, the mechanism of electrochemical cor-
rosion may be explained in terms of
(i) Evolving of hydrogen
(ii) Absorption of oxygen
(i) Evolution of hydrogen:
The process of corrosion in which H2 is liberated is called evolution of hydrogen type corrosion.
This mechanism of corrosion follows usually in acidic environment. Thus, in acidic medium
(absence of oxygen) hydrogen ion acquire electrons with the liberation of H 2 gas in cathodic
reaction and the anode is the metal which undergo oxidation and looses electrons to the environ-
ment and pass into solution. This process is shown in Figure 6.2.
For example:
(a) If iron metal is used, the dissolution of iron as Fe2+
Fe → Fe2+ + 2e- (Oxidation)
(b) These electrons flow through the metal from anode to cathode, Where H+ ions of acidic solu-
tion accept these electrons and get reduced in the form of H2 gas.
2H+ + 2e- → H2 (Reduction)
Overall Reaction
Fe + 2H+ → Fe2+ + H2

Acidic Solution
H+ (Electrolyte)
H+ Cathodic reaction
2H++ 2e− → H2 H+
Fe → Fe2++2e− Anodic Reaction

Fe → Fe2++2e−
Flow of
electrons
Anodic area Small Cathodic Anodic area

(large) area (large)
Iron Metal
Figure 6.2 Mechanism of wet corrosion by hydrogen evolution
It is important to note that in hydrogen evolution type of corrosion, anodic areas are
very large in comparison to cathodic areas. All the metals, above hydrogen in electrochem-
ical series have a tendency to get dissolved in acidic solution with liberation of hydrogen.
(ii) Absorption of oxygen:
This type of corrosion occurs in basic or neutral environment (such as NaCl solution used as
electrolyte). The common example is corrosion of iron occurs by oxygen in the presence of aque-
ous solution of NaCl in the presence of oxygen. This process is shown in Figure 6.3.
Rust Aqueous neutral solution

of electrolyte (NaCl)
Fe → Fe2++2e−
1 O − 1 O + H O + 2e−
+ H O + 2e
2 2 2
− 2
2 2
↓ 2OH ↓ 2OH−
Iron oxide film

Anodic Area
(small) Flow of electrons
Cathodic Cathodic
Area (large) Area (large)
Figure 6.3 Mechanism of wet corrosion of absorption of oxygen
(a) At anode, iron dissolves to form ions as

Fe → Fe2+ + 2e- (Oxidation)
(b) At cathode, the electrons evolved by above reaction are accepted by oxygen in presence of
water.
1
2 2

(c) The Fe2+ ions (at anode) and OH- (at cathode) diffuse and when they combine Fe(OH)2 is
precipitate.
Fe2+ + 2OH- → Fe(OH)2↓
(d) In the presence of sufficient oxygen, Fe(OH)2 can be easily oxidized into ferric hydroxide
[Fe(OH)3]
4 Fe (OH)2 + 2H 2 O + O2 → 4Fe(OH)3 ↓
Yellow rust
(e) If the supply of oxygen is limited then black anhydrous magnetite i.e. ferrousoferic oxide is
formed as
3Fe(OH)3 → Fe3O4·6H2O or Fe2O3·FeO·6H2O(Black rust)
Difference between chemical and electrochemical corrosion

Chemical corrosion Electrochemical corrosion
1. It occurs only in dry conditions. It occurs in wet conditions in the presence of mois-
ture and electrolyte.
2. It involves chemical attack of oxygen or other gases It involves electrochemical attack of corrosive envi-
ronment on the surface of metal.
3. Chemical corrosion products accumulate at the site Corrosion products accumulate some where
of attack i.e. at anode between the area of anode and cathode.
4. It is a self-controlled process. It is a continuous process.
5. In this process, oxidation and reduction sites are In this process, oxidation and reduction takes place
same. at different sites.
6. Chemical corrosion is a slow process taking place It is a fast electrochemical process. It proceeds
by chemical reaction of atmospheric gases. through the cells.
7. In chemical corrosion, product may be unstable, In electrochemical corrosion product is always
volatile or porous in nature. stable e.g. Fe3O4, Zn(OH)2 etc.
8. In chemical corrosion, path for electron flow is not In this process, path for electron flow is always
required. required.
9. It is explained on the basis of absorption. Its mechanism is explained on the basis of electro-
chemical reaction.
Types of Electrochemical Corrosion

Such type of corrosion takes place in following conditions:
(i) When two dissimilar metals or alloys are in contact with each other in the presence of a conduct-
ing medium (aqueous solution, moisture etc.)
(ii) Separate anodic and cathodic areas between which the current flows the conducting medium.
(iii) Oxidation takes place at anode and reduction takes place at cathode e.g. rusting of iron.
(a)
Galvanic corrosion or bimetallic corrosion
The galvanic cell is formed if two different metals (e.g. zinc and copper) are electrically con-
nected and exposed to an electrolyte. As a result, the less noble metal (i.e. the metal having
a lower value of standard reduction potential or placed higher in the electrochemical series)
gets corroded. This type of corrosion is called as galvanic corrosion e.g.: Zn-Cu, Zn-Ag,
Fe-Cu etc.

In Zn-Cu galvanic cell, Zinc (E° = −0.76 V) with lower reduction potential than copper
(E° = + 0.34 V) acts as anode and the electrons flow from anodic metal (Zn) to cathodic metal
(Cu). The anodic metal is corroded, while cathodic metal remains protected. This process is
shown in Figure 6.4.
Zn (anode)
(less noble) Cu(cathode) (More Noble)
e−
Conducting Solution
−
Zn → Zn2++2e
Figure 6.4 Galvanic corrosion (The less noble metal zinc acts as anode and undergoes corrosion,
whereas the most noble metal copper remains protected.)
(1) In acidic solution, the corrosion occurs by evolution of hydrogen
At anode: Zn → Zn 2+ + 2e − (Oxidation )
−
At cathode : 2 H + 2e → H 2
+
( Reduction )
Zn + 2H + → Zn 2+ + H 2
(2) In Neutral or slightly alkaline medium, the corrosion occurs by absorption of oxygen
At anode : Zn → Zn 2 + + 2e − (Oxidation )
1
H 2 O + O2 + 2e − → 2OH − ( Reduction )
At cathode : 2
1
Zn + H 2 O + O2 → Zn(OH)2
2
Examples:
(i) Steel screw’s in a brass marine hardware
(ii) A steel propeller shaft in bronz bearing.
(iii) Steel pipe connected to copper plumbing.
Control
Since Galvanic depends upon the following factors:
(i) Greater the potential difference between two metals, greater is the corrosion.
(ii) Suitable medium for corrosion
(iii) Surface area of the metal
Hence corrosion may be controlled by the following factors:
(i) Avoiding the suitable medium for corrosion.
(ii) Minimizing the potential difference of metals i.e. avoiding the galvanic couples.
(iii) By polishing the metals.

6.10
Concentration Cell Corrosion (Differential Aeration Corrosion)

When a metal is exposed to an electrolyte of varying concentrations or to varying aeration, it under-
goes an electrochemical attack due to formation of miniature concentration cells on its surface and
gets corroded.
Differential aeration corrosion is the most common type of concentration cell corrosion. This type
of cell is formed when the metal is kept in different air concentration i.e. two ends of metal surface are
at different concentration of air. The part of metal which is poorly oxygenated acts as anode and other
part of the metal which is highly oxygenated acts as cathode. This develops electrode potential and
hence the, metal gets corroded.
Let us consider the case of zinc (Zn) rod which is immersed in NaCl solution. A potential differ-
ence is developed between differently aerated areas. The part of the rod which is at greater depth acts
as anode (less oxygenated) and that is which is above the surface acts as cathode (more oxygenated)
and zinc corrodes due to electrode potential. This process is shown in Figure 6.5.
Zn rod
Cathode
Anode
Flow of electrons
e−
Corroding anode
Zn2+ Zn2+
Electrolyte NaCl
Zn → Zn2++2e
Zn2++ 2Cl− → ZnCl2
Figure 6.5 Differential aeration corrosion
At anode: less oxygenated part

Zn → Zn 2+ + 2e- (Oxidation)
At cathode; more oxygenated part
1
2 2
Overall Reaction
Zn 2+ + 2OH- → Zn (OH)2

In a similar way, iron metal corrodes under drop of water (or salt solution). Areas covered by
droplets, having no access of oxygen, it become anodic with respect to the other areas, which are freely
exposed to air become cathodic. This process is shown in Figure 6.6.
Air
Drop of salt solution
Good access of
oxygen Fe → Fe2++2e− Rust ring (Iron hydroxide)
Cathodic Cathodic
area area
(Protected) (Protected)
Anode
(Poor access of
oxygen attacked)
Iron
Figure 6.6 Differential aeration corrosion
At anode: Fe → Fe2+ + 2e- (Oxidation)

1 − −
At cathode: O2 + H 2 O + 2e → 2OH (Reduction)
2
1
Overall reaction Fe + O2 + H 2 O → Fe(OH) 2
2
Iron hydroxide
Important Characteristic about Differential Aeration Corrosion

(i) The metal having low oxygen concentration part act as anode and metal having high oxygen
concentration act as cathode.
(ii) Corrosion may be accelerated in apparently in accessible places, because of deficiency of oxygen
at some part.
(iii) This type of corrosion also accelerated under accumulation of dirt, sand, scale or other contami-
nation, because such covered part act as anode due to difference in air concentration.
(iv) It is a localized attack on some oxygen deficient areas such as metal exposed to aqueous media
corrode under blocks of wood or pieces of glass, which screen that portion of metal from oxygen
access, resulting into localized pitting.
Water-line Corrosion
It is the type of differential aeration corrosion, which occurs when a metal is partly immessed in water.
The corrosion takes place just below the waterline and hence it is known as waterline corrosion.
It is an observed fact that when water is kept stagnant in a steel tank for a long time, corrosion
takes place just below the water level, it is due to the concentration of dissolved oxygen at the water
surface is greater than that under surface.It forms an oxygen concentration cell. The area above the
waterline (highly oxygenated) acts as cathodic and corrosion takes place along a line just beneath the
level of water meniscus (anodic area) as shown in Figure 6.7.

6.12
Cathodic Part
−
H2O + 1 O2 + 2e− → 2OH
2
Anodic part
undergoing Anodic Part undergoing
corrosion corrosion
Fe → Fe2++ 2e−
Water
Steel tank
Figure 6.7 Water-line corrosion
Corrosion takes place at anodic part

At cathode: 1
H 2 O + O2 + 2e − → 2OH − (Reduction)
2
Overall reaction: Fe2 + + 2OH − → Fe (OH)2
↓ oxidation
Fe(OH)3
Corrosion product
This type of corrosion is accelerated when water is acidic in nature and presence of salts like chlo-
rides, bromides, etc. When marine plants attach themselves to side of the ships, this type of corrosion
is increased because of presence of different salts.
Prevention
(i) Water-line corrosion is reduced when the water is free from acidic impurities.
(ii) Usage of special anti foaming paints minimizes such type of corrosion to some extent.
(iii) By using anodic inhibitors like phosphates, carbonates, silicates, water-line corrosion can be
retarded.
This type of corrosion is accelerated when water is acidic in nature and presence of salts like chlo-
rides, bromides, etc. When marine plants attach themselves to side of the ships, this type of corrosion
is increased because of presence of different salts. The use of special antifouling paints minimizes such
type of corrosion to some extent.
Pitting Corrosion
Pitting corrosion is a non-uniform corrosion which is caused by localized accelerated attack on metal
surface and forms pits, cavities and pin holes in the metal.
A pit is formed when the protective coating on the metal surface breaks at specific points. Once the
pit is formed the process of corrosion becomes fast due to differential amount of oxygen in contact with
metal surface. The portion with higher concentration of oxygen become cathode and that with lower oxy-
gen concentration becomes anode. This causes corrosion of metal. This process is shown in Figure 6.8.

Corrosion product
Cathode Cathode
− −
H2O + 1 O2 + 2e− → 2OH H2O + 1 O2 + 2e− → 2OH
2 2
e− e− Flow of electrons
Pit (Anode)
Iron
Fe → Fe2+ + 2e−
Figure 6.8 Pitting corrosion
1
At cathode: H 2 O + O2 + 2e − → 2OH − (Reduction)
2
1
Fe + H 2 O +
O → Fe(OH)2 [
O]
→ Fe(OH)3
Overall Reaction 2 2 Rust
2+ −
Fe + 2OH → Fe(OH)2 → Fe(OH)3
[O]
Pitting corrosion may be caused by

(i) Surface roughness
(ii) Scratches on metal surface
(iii) Local strains of metal due to non-uniform stress
(iv) Presence of extrageneous impurities (like sand, dust or scale)
(v) Presence of drop of salt solution
(vi) Non-uniform polishing of metal etc.
Pitting corrosion may be prevented by

(i) Proper designing of metal
(ii) Proper polishing of metal
(iii) Use of pure metal
Stress Corrosion
Stress corrosion or stress cracking is the type of corrosion which occurs due to combined effect of ten-
sile stresses and the corrosive environment on metal when metal is exposed to corrosive environment.
Pure metal generally does not undergo stress corrosion whereas fabricated metal components or
an article of certain alloys like zinc and nickel brasses undergoes such types of corrosion.

6.14
Favorable Conditions for Stress Corrosion

(i) Tensile stress: The stress developed on metal surface may be internal or external. Internal stress
is caused by manufacturing process (quenching, bending, annealing, etc.) or fabrication process
or heat treatment process. In all such cases, metal under stress becomes more anodic and that
area undergoes corrosion.
(ii) Corrosive environment: The specific and selective environment play very important role in stress
corrosion.
For example
(a) Mild steel undergoes stress corrosion in the presence of caustic alkalies and strong nitrate
solution.
(b) Stainless steel in the presence of acid chloride solution.
(c) Brass in the presence of traces of ammonia.
Mechanism
Stress corrosion is localized electrochemical phenomenon. As we know that, the point or area under
stress as well as grain boundaries act as electrochemical cell which occurs generally due to internal
stresses due to metallurgical operations such as bending, pressing, rolling, quenching, annealing, etc.
Due to presence of stress forms anodic areas in localized zones with respect to more cathodic areas at
the metal surface. Such areas under stress act as anode and they become so chemically active that they
are attacked, even by a mild corrosive environment, which result in the formation of cracks which propa-
gate rapidly resulting in an unexpected failure of the metal surface. This process is shown in Figure 6.9.
Unstressed part
acting as cathode Grain Boundary
(Part under stress acting as anode)
Grain A Grain B
Crack due to
stress corrosion
Figure 6.9 Stress corrosion
In every type of corrosion there is formation of galvanic cells and corrosion takes place at the
anodic part.
At anode: M → Mn+ + ne – (Oxidation)
At cathode: H 2 O + 1 O2 + 2e − → 2OH − (Reduction)

2
Stress corrosion takes place even in mild corrosive environment on the stressed metal part.
Types of Stress Corrosion

(i) Season cracking: This type of cracking is generally refers to the corrosion of copper alloys,
particularly brass. Brasses are binary alloys of Cu and Zn which are electrochemically reactive

in an environment of ammonia. Therefore, when brass is exposed in ammonical medium, both

copper and zinc form complexes by losing electrons in ammonical solution. As a result, dissolu-
tion of brass occurs and forms cracks for stress corrosion.
Zn → Zn 2+ + 2e- and Cu → Cu 2+ + 2e-
Zn 2 + + 4 NH 3 → [Zn( NH 3 ) 4 ]2 + and Cu 2 + + 4 NH 3 → [Cu ( NH 3 ) 4 ]2 +

This reaction is generally referred to a season cracking.
(ii) Caustic Embrittlement: This type of corrosion generally occurs in mild steel, which undergoes
stress corrosion in caustic alkalies at high temperature and pressure. It is very dangerous form of
stress corrosion, generally occurs in steam-boilers and heat-transfer equipments in which water
of high alkalinity attack the mild steel plants, particularly crevices near rivets, bends, joints etc.
The causes and methods of prevention of caustic embrittlement:
For water-softening purpose of Boiler-water, we generally added a certain proportion of sodium
carbonate into it. In high pressure boilers, this breaks up to give sodium hydroxide and carbon
dioxide.
Na2CO3 + H2O → 2NaOH + CO2↑
This makes boiler-water alkaline in nature. This dilute alkaline boiler-water flows into the
minute cracks and crevices by capillary action, where water evaporates and caustic soda con-
centration builds up. The area where metal is stressed and concentration of alkali is much higher
than that in the body of the boiler, alkali dissolve metal as sodium ferrate in crevices, cracks etc.
sodium ferrate is decomposes according to either of the following reactions:
3Na2FeO2 + 4H2O → 6NaOH + Fe3O4 + H2
or
6Na2FeO2 + 6H2O + O2 → 12NaOH + 2Fe3O4
Sodium hydroxide (NaOH) is regenerated and magnetite (Fe3O4) is precipitated, thereby
enhancing further dissolution of iron.
Caustic embrittlement can be explained by considering the following electrochemical cell:
Fe NaOH (Concentrated ) NaOH ( Dilute) Fe
Anode Cathode
The iron surrounded by dilute NaOH is the cathodic area; while iron surrounded by concen-
trated NaOH (e.g. crevices, hair-cracks, rivets etc.) is the anodic area and undergoing corrosion
and is thus dissolved the iron metal from that areas.
Prevention of Caustic Embrittlement

(i) Use of sodium sulphate in boiler-water.
(ii) Use of tannin or lignin as additive boiler-water.
Both these methods prevent caustic cracking by blocking up the cracks and crevices with innocuous
harmless substances, thereby preventing the sodium hydroxide from infiltrating into these areas.
(iii) Corrosion fatigue: This type as corrosion cracking occurs due to repeated stresses caused by shak-
ing, tapping, vibration etc. in the presence of corrosive environment. The repeated stress make same

6.16
metal less elastic which on turn act as anode with respect to other part of metal. The corrosion take
place in these region and cracks occurs. This type of corrosion occurs mostly in alloy steel.
6.2 GALVANIC SERIES

Electrochemical series is very helpful to understand the extent of corrosion on the basis of standard
reduction potential. According to this series a metal placed at top in the series is more anodic and
undergoes corrosion rapidly than the metal below in the series.
The rate and severity of corrosion depends upon the difference in their positions, greater is the dif-
ference, and the faster is the corrosion of metal. For example, Li corrodes faster than Mg; Zn corrodes
faster than Fe, and so on.
However, some exceptions to this generalisation have been noticed. For example, position of tita-
nium (Ti) is higher than silver (Ag) but Ti is less reactive towards corrosion. Similarly, aluminium (Al)
is above zinc (Zn) but zinc corrodes faster. This is only due to formation of strongly adhering oxide
layers on their surfaces, thereby making their effective electrode potential more positive (or less nega-
tive). Hence a new series came into exist which is based on relative oxidation potential in sea water.
This series is known as galvanic series. Galvanic series is shown in Table 6.1.
Table 6.1 Galvanic series

Active 1. Mg
(or Anodic) 2. Mg alloys
3. Zn
4. Al
5. Cd
6. Al Alloys
7. Mild steel
8. Cast iron
9. Stainless steel
10. Pb-Sn alloy (solder)
11. Pb
12. Sn
13. Brass
14. Monel (Ni = 7%, Cu = 30%, Rest Fe)
15. Silver solder
16. Cu
17. Ni
18. Bronze
19. Cu-Ni alloys
20. Ag
21. Chromium stainless steel
22. Graphite
23. Ti
24. Au
25. Pt
Noble
(or Cathodic)

According to this series the metal or alloys higher up the position in the series is more anodic and
undergoes corrosion very rapidly. For example, the position of Zn is higher than Al; hence Zn under-
goes corrosion rapidly not aluminium Al.
6.2.1 Factors Affecting Corrosion

The rate and extent of corrosion of a metal depends upon the following factors:
(i) Nature of the metal and
(ii) Nature of the environment.
(i) Nature of the metal:
The various factors such as its purity, position in galvanic series, physical state, overvoltage etc.
which decide the nature of a metal from the view point of corrosion are as follows.
(a) Purity of the metal: The presences of impurities in a metal accelerate its corrosion. This is
because impurities form minute electrochemical cells with the metal under suitable envi-
ronmental conditions, and the anodic parts get corroded.
For example: Zinc metal containing impurities (such as Pb or Fe) undergoes corrosion
of zinc, due to formation of local electrochemical cells.
(b) Position in galvanic series: The extent of corrosion depends upon the position of metal
in galvanic series. The metal or alloy which is placed at higher up in the series are more
reactive and has greater tendency to undergo corrosion. The rate and severity of corrosion,
depends upon the difference in their positions, and greater is the difference, the faster is the
corrosion of the anodic metal alloy.
(c) Over Voltage: The dissolution of metals in acids may also be considered as a corrosion
reaction. Metals like Zn, Cd, Sn and Pb dissolve rather slowly in acids when they are pure.
However, these metals dissolve rapidly when they contain impurities which are relatively
more noble and also have a low overvoltage.
The difference between the potential of the electrode (voltage) when gas evolution is
actually required and expected theoretical value for the same evolution is called over voltage.
For example, the presence of copper in small amounts as an impurity in zinc increases
the rate of dissolution of zinc by anodic oxidation. This may be explained on the basis of the
hydrogen voltage of the two metals. Pure zinc with higher hydrogen over voltage of 0.70V
dissolves slowly and hydrogen evolution is also slow. Copper with low hydrogen over volt-
age of 0.25V also dissolves but redeposit, on the zinc surface and functions as an efficient
cathode rendering the zinc anodic. Since the hydrogen over voltage is lower at the copper
cathode, the rate of hydrogen evolution increases, since this cathodic reaction is favoured,
the anode reaction, namely, the oxidation (corrosion) of zinc is also favoured.
(d) Physical state of the metal: The rate of corrosion is influenced by physical state of the metal
such as grain size, orientation of crystals, stress etc. The smaller the grain size of the metal
or alloy, the greater will be its solubility in corroding medium and hence greater will be its
corrosion. Moreover, areas under stress, even in a pure metal, tend to be anodic and corro-
sion takes place at these areas.
(e) Relative areas of the anode and cathode:
Rate of corrosion is less when cathodic area is less and anodic area is more.
Cathodic part
Rate of corrosion a
Anodic part

6.18
It is clear that, due to small cathodic part, the demand for electrons will be less and this results
in less dissolution of metal at the anodic part and rate of corrosion is also less.
(f) Reactivity of metals: Some metals are passive in nature, Good examples are Al, Ti, Mg, Ni,
Co, etc. These metals react with oxygen to form non-porous oxide layer that protects the
material from further corrosion. This oxide layer on metal is also self-healing in nature, i.e.,
heals itself if scratched on metal surface.
(g) Nature of oxide film: In aerated atmosphere, particularly all metals get covered with a thin
surface film of metal oxide having a thickness of few Angstromes. Whether the metal oxide
layer is protective or non-protective is decided by pilling-Bedworth rule. This rule decides
the rate of corrosion in a metal.
Greater the specific volume ratio, lesser is the oxidation corrosion rate eg., the specific vol-
ume ratio of Ni,Cr and W are 1.6,2.0 and 3.6 respectively, which indicates that the rate of
oxidation at elevated temperature is least for Tungsten(W).
(h) Solubility of the corrosion product: In electrochemical corrosion, the solubility of the corro-
sion products in the corroding medium is an important factor in deciding the extent and the
rate of corrosion. If the corrosion product is soluble in the corroding medium, corrosion of
metal will take place at a higher rate, But if the corrosion product is insoluble in the corroding
medium (e.g. PbSO4 in case of Pb in a medium of H2SO4) it forms a protective layer on the
metal surface and inhibits further corrosion of the metal.
(i) Volatility of the corrosion product: If corrosive product is volatile in nature, they volatile as
soon as they are formed. Hence, the underlying metal surface is exposed for further attack,
resulting rapid and continuous corrosion.
(ii) Nature of the environment:
(a) Effect of the temperature: The extent and rate of corrosion usually increases with rise in
temperature. This is because an increase in temperature increases the rate of a chemical
reaction as well as the rate of diffusion and decreases polarisation.
(b) Effect of pH: It has been observed that the corrosion takes place more in acidic media
(PH < 7) than neutral or alkaline media (PH ≥ 7). Thus, corrosion of metals can be reduced
by increasing the PH of the environment contrary to it; amphoteric metals like Al, Zn and Pb
are more corroded in alkaline media because they form complex ions in alkaline media and
pass into solution.
(c) Effect of moisture: Moisture or humidity of air is an excellent medium of corrosion. Moisture
present in the atmosphere acts as a solvent for oxygen, other gases (O2, SO2 etc.) and salts
and forms electrochemical cell. Hence, presence of moisture accelerates the rate of corrosion
of a metal. For example, rusting of iron is quite slow in dry air but increases rapidly when the
humidity of air is 60–80%.
Critical humidity is the humidity of the air above which the rate of atmospheric corro-
sion of metal increases sharply and depends on the nature of the metal and the nature of the
corrosion products.
(d) Effect of corrosive gases present in air: The gases like CO2, SO2, H2S etc. present in the
atmosphere or fumes of HCl, HNO3, H2SO4 etc. forms the medium more acidic above the
metal surface because these gases are soluble in water to form acids and make it more con-
ducting. This increases the rate of corrosion due to an increase in the corrosion current flow-
ing in the miniature electrochemical cells on the metal surface.

(e) Effect of corroding medium: Corroding medium plays an important role in deciding the
rate of corrosion. Rate of corrosion is increased in the conductive corroding medium. For
example, the conductance of clay and mineralised soil is much higher than those of dry
sandy soils.
(f) Effect of concentration of oxygen: Differential aeration concentration cell is setup due to
change in the concentration of oxygen. Rate of corrosion increases with increase in con-
centration of oxygen. The region where oxygen concentration is lesser becomes anodic and
oxygen concentration rich portion becomes cathodic. The anodic portion suffers corrosion.
Rate of corrosion increases due to formation of differential aeration cell.
(g) Effect of suspended particles in atmosphere: Two types of suspended particles are present
in atmosphere viz., chemically active and chemically inactive. The chemically active sus-
pended particles like NaCl. (NH4)2 SO4 absorb moisture and thus act as strong electrolytes
thereby enhance corrosion rate. Whereas chemically inactive suspended particles like char-
coal, absorb both moisture as well as sulphur gases and thus slowly enhances corrosion rate.
(h) Effect of the nature of the presence of electrolyte: Electrolyte presence in the medium is also
responsible for deciding rate of corrosion. For example, chloride ions (Cl–) present in the
medium increase the rate of corrosion by destroying the passive film on metal surface; on
2−
the other hand, silicate (SiO3 ) forms an insoluble layer which prevents corrosion of metal.
6.3 P
ROTECTION FROM CORROSION (PREVENTIVE MEASURES
FOR CORROSION CONTROL)
Protection against corrosion means not allowing corrosion reactions to take place. Noble metals do not
corrode but they cannot be used for common purposes, because of their high cost. We have to use other
metals or alloys in the fabrication of many kinds of machinery and equipments and adopt measures to
protect these from corrosion.
(i) Material selection:
(a) The chosen metal should be as pure as possible because the presence of impurities enhances
the rate of corrosion.
(b) The choice of noble metals are preferable because they are highly resistant to corrosion.
(c) Avoid the contact of dissimilar metals in the presence of a corroding environment.
(d) If two dissimilar metals in contact have to be used, they should be as close as possible to
each other in the electrochemical series.
(ii) Proper designing:
(a) W hen anodic and cathodic materials are used together, then the area of anodic material
should be large.
(b) The anodic part should not be painted or coated because any damage in coating would cause
rapid localized corrosion.
(c) Whenever the direct joining of dissimilar metals, is unavoidable, an insulting fitting may be
applied in-between them to avoid direct metal-metal electrical contact.

6.20
(d) Angles, corners, edges etc. should be avoided in construction.For this reason L, T and U
shaped structures should be avoided as far as possible some better shapes of L, T and U
structure are given below:
Poor-L Better-L Poor-T Better-T
Water
Water Tank
Tape Tank
Tape
Poor - U Better - U
(e) The material should not have sharp corners and recesses because they help in accumulation
of impurities. It should be avoided by proper designing as show in figure.
Weld Weld
Recesses
Sharp
Corners
Weld Sharp Weld

Corners
(Poor Design) (Poor Design)
Weld
Smooth
Bend
Weld
(Best Design)

(f) Always prevent the occurrence of in homogeneities in metal and in the corrosive environ-
ment. Thus a proper design should avoid the presence of crevices between adjacent parts
of the structure, even in case of the same metal, since crevices permit concentration differ-
ences. Hence bolts and rivets should be replaced by a butt-weld as shown in figure.
Crevices Weld joint
Bolt joint
(Poor Design) (Good Design)
Weld Joint
Weld joint
(Best Design) (Best Design)
(g) Whenever possible, the equipment should be supported on legs to allow free circulation of
air and prevent the formation of stagnant pools or damp areas.
Air
Poor design because it prevents Best design because it allows

free circulation of air free circulation of air
(h) Uniform flow of corrosion liquid is desirable, since both stagnant areas and highly turbulent
flow and high velocities can cause accelerated corrosion.
(iii) Cathodic protection (Electrical protection):
The principle involved in this method is to force the metal to be protected to behave like a cath-
ode, thereby corrosion does not occur. Cathodic protection is carried out by two methods:
(a) Sacrificial anodic protection (Galvanic protection)
In this method, the metallic structure (to be protected) is connected by a wire to a more
anodic metal, so that corrosion occurs at that anodic metal and metallic structure is pro-
tected. This method is generally used for the protection of underground pipes and tanks.
In this method, the more active metal like Mg is used as anode and this metal used is
called as “sacrificial anode”. A block piece or plate of a more reactive metal (Zn or Mg) is
buried beside the iron pipe and connected to it by a wire as shown in Figure 6.10.

6.22
Soil
Mg
e−
Magnesium
anode
Mg→ Mg2++2e−
iron pipe (Cathode)
O2 + 2H2O + 4e− → 4OH−
O2 + 4H++4e− → 2H2O
Figure 6.10 Sacrifice anodic protection
Since more reactive metal (e.g., Mg) has a greater tendency to get oxidised, it undergoes
oxidation in preference to iron. Thus more active metal acts as anode.
At anode: Mg → Mg2+ + 2e−
The electrons thus released migrate to the iron object which starts acting as cathode. At
cathode released electrons reduce O2 into OH− as:
At cathode:
O2+ 2H2O + 4e− → 4OH−
or
O2+ 4H+ + 4e− → 2H2O
Thus cathode (iron etc.) gets protected. Since the reactive metals (Mg, Zn etc.) scarify
itself during the protection of other metal. The corroded sacrificial metal block is replaced by
a fresh one, when consumed completely. Hence it is termed as sacrificial anode protection.
(b) Impressed current cathodic protection
In this method, an impressed current from an external source is applied in the opposite
direction to neutralize the corrosion current. This is done to convert corroding metal from
anode to cathode. Once the metal becomes cathodic, it is protected from corrosion. Usually,
the impressed current is derived from a DC source (like battery or rectifier on a.c. line)
in which negative terminal of a DC source is connected with the object to be protected
is made the cathode of an electrolytic cell and positive terminal of the DC source is con-
nected to scrap iron, platinum, graphite, nickel or lead anode (insoluble anode) and buried
or immersed in a conducting medium adjacent to the metal to be protected. The anode is,
usually, taken in a backfill (composed of coke, breeze or gypsum) so as to increase the elec-
trical contact with the surrounding soil. This type of cathodic protection has been applied
to protect buried structures, pipes, water-tanks etc. This process is shown in Figure 6.11.

DC sourse
(+) ( −)
Soil
Graphite
de
Anode e catho
Iron pip
Bockfill
Figure 6.11 Impressed current cathodic protection
(iv) Surface coatings: Protecting the surface of an object by the application of coating by different
methods. A brief description of two important protective coatings is given below.
(a) Anodic coatings:
In this process, the base metal (i.e. which is to be protected) is coated with more active metal
(i.e. having lower electrode potential) such as Zn, Al and Cd coating on steel surface. If any
pores, breaks or discontinuities occur in such an anodic coating, a galvanic cell is formed
between the coating metal and the exposed part of the base metal, i.e. steel object. For exam-
ple, in case of galvanized steel, zinc, the coating metal is attacked, leaving the underlying
cathodic metal unattacked. Zinc act as anode with respect to iron, which act as cathode zinc
dissolves anodically and iron metal is protected. Zinc has first corroded in the vicinity of the
exposed iron spot. So, zinc coating protect iron “sacrificially”.
Due to oxidation, zinc layer may be converted to basic zinc carbonate, ZnCO3. Zn
(OH)2 by the action of oxygen, CO2 and moisture. This layer protects the exposed part fur-
ther. This process is shown in Figure 6.12.
Corrosive environment
Exposed part
Zinc Coating (cathode)
Zinc Coating
Zn → Zn2+ + 2e−
Zn → Zn2+ + 2e −
e−
e−
Unexposed Flow of Unexposed
part (anode) electrons part (anode)
Steel
Figure 6.12 Anodic coating i.e. galvanized steel
(b) Cathodic coatings:

In this process, base metal is coated with a more noble metal (i.e. having higher electrode
potential). For example, coating of tin on iron, coating of copper on iron because both Sn,

6.24
Cu having higher electrode potential than iron. This type of coating provides effective pro-
tection to the base metal only when the base metal is completely continuous and free from
pores, cracks or discontinuities. If the coating develops scratches or cracks, iron is not pro-
tected any more; the tin becomes the cathode, while the exposed iron acts as anode. This is
because the standard reduction potential of iron is less than that of tin.
E°Fe2+/Fe = −0.44V
E°Sn2+/Sn = −0.14V
A galvanic cell is set up and an intense localized attack at the small exposed part i.e. iron metal occurs,
which results into severe pitting and perforation of the base metal. In such a case the rusting is much more
rapid as compared to that in case of an unprotected iron piece. This process is shown in Figure 6.13.
Corrosive environment
Exposed part
Sn Coating becomes anodic Sn Coating
Fe → Fe2+ + 2e−
Unexposed Unexposed
part (cathode) Flow of part (cathode)
electrons
Corrosion
product
Figure 6.13 Cathodic coating i.e. Tin – plated steel
Method of Application of Metal Coatings

(i) Hot dipping:
In this process, metal or metal alloys such as iron, copper or steel having a high melting point is
coated with a low melting metals such as tin, zinc, lead or aluminum is known as hot dipping.
This process involves dipping or immersing the base metal article in a molten bath of the coating
metal and covered by a molten flux layer (usually ZnCl2). The flux cleans the base metal surface
and prevents the oxidation of the molten coating-metal.For good adhesion; the base metal sur-
face must be very clean; otherwise it cannot be properly wetted by the molten metal. The most
commonly used hot dipping methods include
(a) Galvanizing
(b) Tinning or Tin plating
(a) Galvanizing:
The process of coating a layer of zinc on iron or steel is called galvanizing. This protects iron
object from rusting. The steel article first pickled with dilute sulphuric acid to remove traces of
rust, dust or any other impurities etc.; at 60–90 °C for about 15 to 20 minutes. Then the metal
is dipped in a molten zinc bath at 430 °C. The surface of the bath is covered with ammonium
chloride flux to prevent oxide formation on the molten zinc. When the article is taken out, it is
found to have been coated with a thick layer of zinc. It is then passed through a pair of hot rollers.

This process removes any excess of zinc and produces a thin film of uniform thickness. The
coated article is annealed at a temperature of 650 °C and cooled to room temperature slowly.
Galvanized articles cannot be used under acidic conditions and galvanized containers cannot
be used to store acidic foods. This process is shown in Figure 6.14.
Drying Ammonium Pair of Galvanized

chamber chloride flux hot rollors sheet
Iron sheet
Hot Annealing
Water Air chamber
Dil. H2SO4 Washing bath Molten zinc Excess zinc

at 60-90°C at 430°C removed
Figure 6.14 Galvanisation of steel sheet

(b) 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. Then tin coated article is passed through a series
of rollers immersed in a palm oil bath to remove the excess tin. The palm oil protects the hot
tin-coated surface against oxidation. This process produces a thin film of uniform thickness
on the steel sheet.
Because of non-toxic nature of tin, tinning is widely used for coating steel, copper and
brass sheets which is used for manufacturing containers for storing food stuffs, ghee, oils,
kerosene’s and packing of food materials. This process is shown in Figure 6.15.
Roller
Tin-placed
et
sheet el she
Pair of Ste
rollers
Palm
oil Acid pickling
Bath of zinc bath
chloride flux
Molten tin
Tank
Figure 6.15 Tinning of steel sheet
(ii) Metal cladding:

In this process, the base metal is protecting from corrosion by coating of a thin uniform homog-
enous layer of a coating metal on the base metal. In this method, base metal sheet is sandwiching
between thin sheets of corrosion resisting metals such as nickel, copper, lead, silver or platinum
and bonded either on one side (e.g. copper clades in cooking vessels) or on both sides (e.g. dura-
lumin is sandwiched between two layers of Pure Aluminium) permanently by the application of

6.26
heat and pressure. Metal cladding is generally practiced in the air craft industry in which a sheet
of duralumin is sandwiched between two layers of pure aluminum to produce a sheet.
The basis requirement for this specification that base metal and the cladding metal should
have similar working characteristics for effective cladding.
In some cases we are also used metal oxide powders in a revolving heating drum in which
base metal is thoroughly immersed. This is known as diffusion or cementation of the base metal
to protect from corrosion, when ZnO is used, it is known as sherardizing. When Al2O3 and Cr2O3
are used, it is known as chromizing and when only Al2O3 is used, it is known as colorizing. In all
this method, we protect the base metal from corrosion by coating of thin film of different metal.
(iii) Electroplating:
In this process, noble metal is coated over more reactive metal. Most commonly used are tin
plating and nickel plating. In electroplating, the object to be plated is made as cathode and sus-
pended in an electroplating bath containing the metal ions to be plated by electro deposition. The
anode may be of the metal to be deposited or it may be an inert electrode (such as graphite) with
good electrical conductivity. During this process, the variables such as voltage, temperature, pH,
current and density are kept constant so that electroplating process remains unchanged (i.e., rate
of deposition of metal on cathode and rate of dissolution on anode).
For example, iron can be protected from corrosion by coating the metal with chromium or
nickel by electroplating process.
(iv) Electro less plating:
In this process, we immersed the base metal article in a bath of a noble metal salt which is used
for coating. The noble metal forms a layer on the base metal article by displacement of base metal
by noble metal. This process is also called as ‘immersion plating’ or ‘displacement plating.’
For example, nickel coating on base metal, In this process, base metal article is dipped in a
bath of nickel sulphate and sodium hypophosphite kept at temperature of 100°C and at pH from
4.5 to 5.0. Nickel ion from solution reduces to nickel and nickel phosphide, which forms a strong
adherent thin film.
(v) Organic surface coatings:
Organic coatings are useful for the protection of metal surface by providing inert barrier on the
surface from corrosion as well as corrosive environment. Organic coating also helpful in decora-
tion of metal surface. Organic coatings commonly used include paints, varnishes, lacquers and
enamels.
Paints
Paint is a term which has been used to signify a uniform dispersion of finally divided solids in a liquid
called “vehicle” or “medium”. The solid comprises of pigments, driers and fillers. Volatile solvent is
mixed with a non-volatile forming a film on metal surface. Example of non-volatile is drying oil and
volatile solvent is thinner.
Constituents of paints and their function
The various constituents of paint include
(a) Pigment
(b) Vehicle or drying oil
(c) Thinner
(d) Drier

(e) Filler or extender

(f) Plasticizers and
(g) Anti-skinning agent
(a) Pigment: It is an essential constituent of paint. It provides color and opacity, in addition of
that imparting strength and aesthetic appeal to the paint. Pigments increase the life of paint
film because they prevent the penetration of UV rays which deteriorate the oil film.
Many properties need to be looked for a pigment. It should be opaque, chemically inert,
non-toxic and miscible with the vehicle. The pigment should have good hiding power i.e., it
should be opaque so that the surface underneath is not visible; otherwise all the dirty spots,
surface defects etc. would be seen. Opacity of the paint is due to the difference between the
refractive indices of the pigment and the vehicle and also on the fine size of the pigment
particles. Pigments commonly used in paints are inorganic solids with high refractive index
either naturally occurring minerals or synthetic chemicals.
Example of pigments Colour
While lead [2PbCO3 ⋅ Pb(OH)2 ] White
Prussian blue K 2 [Fe(CN)6 ] Blue
Carbon black Black
Chromium oxide (Cr2 O3 ) Green
(b) Vehicle or Drying oil: It is a liquid which binds the pigment to the surface and protects pig-
ment from decay. Common example of such oil as linseed oil, dehydrated castor oil, perilla
oil or tung oil or a mixture of drying and semidrying oils. When paint is applied on a metal-
lic surface, the unsaturated fatty acids in oil undergoes oxidation and forming oxides, per-
oxides and hyperoxides at the double bond and further undergo polymerisation and forming
a protective, tough and insoluble film of the polymer on surface.
H2C CH CH CH CH CH2 CH CH CH2 CH2

Conjugated fatty acid residues Non-conjugated fatty acid residues
O2 absorption decomposition followed by rearrangement,
hydrogen abstraction
CH CH HC
O O O
Oxide Peroxide Free radicals
Reactive radicals
Reaction with Fatty acid components of

coupling oil and among radicals
C
C C
O
+ O + C
O
C
C
High cross linked polymeric film

6.28
By adding phenolic and alkyl resin into drying oil, hardness and glossiness of the film
can be improved.
(c) Thinner: Thinner is a volatile solvent, which is often added to paint which helps to adjust
the consistency of the paint. Other functions of thinner area
(1) To increases the penetrating power of the vehicle
(2) To increases the elasticity of the paint film on surface
(3) It helps in retaining the constituent solids into vehicle
Examples of thinness are turpentine, petroleum fractions such as benzene, naphtha, white
spirit, toluol, etc.
(d) Driers: Main function of a drier is to increase the drying power of the vehicle. In addition
to this, driers work as oxygen-carrying catalysts which accelerates the drying of the oil film
by oxidation, polymerization and condensation. Examples of common driers are borates,
tungstates, resinates, linoleates of metals such as Ni, Zn, Co and Mn.
(e) Filler or extender: These are often colourless inorganic substances like aluminium silicate,
barium carbonate, barium sulphate, asbestos, gypsum, calcium carbonate; clay, magnesium
silicate etc. are added to the paints.
The function of addition of filler in paint is that it improves the properties of the paint
and mainly to reduce the cost. It also acts as carriers for the pigment colour, also fill the
voids in the paint film, reduce the cracking of the paint film and improve the durability of the
film.
(f) Plasticizer: They remain permanently in paints and varnishes. They improve the elasticity
of the paint film which prevents cracking of the film. Commonly used plasticizers are tricre-
cyl phosphate, triphenyl phosphate, di butyl phthalate etc.
(g) Anti-skinning agent: Anti-skinning agents like polyhydric phenols are added to the paint so
that getting or skinning of paint can be prevented and can be used for a long period.
(vi) Use of inhibitors:
Inhibitors are chemical substances which on adding in small portion to the corrosive medium
decreases the corrosion rate.
Inhibitors are mainly of following two types
(a) Anodic inhibitors: This type of inhibitors stifles the corrosion reaction, occurring at the
anode by forming a sparingly soluble compound with a newly produced metal ion. Anodic
inhibitors such as chromates, tungstates, phosphates of transition metal react with ions at
the anode and form an insoluble precipitate. These precipitates formed are absorbed on
metal surface by forming a protective film on the metal and prevent corrosion.
This type of control method is effective, but it may be dangerous because if certain
areas are left unprotected by depletion of the inhibitor which causes severe local attack
occur on the metal surface.
(b) Catholic inhibitor: This type of inhibitors slow down the corrosion reaction by consider-
ably decreasing the diffusion of hydrated H+ ion to the cathode and can be used in acidic as
well as in neutral medium.
In acidic solution, the corrosion process involves the following catholic reaction.
2H+ + 2e− → H2(g)
The corrosion of a metal can be reduced by slowing down the rate of diffusion of H+
ions through the cathode. It can be done by using organic compounds such as mercaptans,

amines, substituted ureas, heavy metal soaps, heterocyclic nitrogen compounds, etc. They
adsorb to the metal surface and act as cathodic inhibitors. Antimony and arsenic oxides
deposit adherent film of metals at the cathode and slow down the overvoltage for hydrogen
evolution.
In a neutral solution, cathodic reaction is written as
1
H 2 O + O 2 + 2e −
−
2OH
2
The hydroxide (OH–) ions are formed due to presence of oxygen. The corrosion can be
controlled by either eliminating oxygen from the corroding environment or by retarding its
movement to the cathodic areas. The oxygen is eliminated by adding reducing agents like
Na2SO3 or by dearation and diffusion of oxygen to the catholic areas can be retarded by
the use of Mg, Ni or Zn salts. These salts react with hydroxide ions to form corresponding
insoluble hydroxides which deposit on the cathodic areas and form an almost impermeable
barrier. This method is also helpful for the protection of metal surface by corrosion by slow
down the corrosion process.

1. The gradual loss of a metal by chemical or electrochemical action of environment is called
________.
[Ans.: corrosion]
2. The formula for rust is ________.
[Ans.: Fe2O3 · xH2O]
3. The wet corrosion involves the flow of ________ from anodic area to cathodic area through a
conducting solution.
[Ans.: electrons]
4. When the oxide film is volatile in nature, rate of corrosion of underlying metal is ________.
[Ans.: increases]
5. In galvanic corrosion, the metal having ________ value of reduction potential gets corroded.
[Ans.: lower]
6. Larger the potential difference between two metals, ________ is the extent of corrosion.
[Ans.: greater]
7. In differential aeration corrosion, the poor oxygenated part acts as ________, and undergoes
corrosion.
[Ans.: Anode]
8. ________ and ________ are important factors for stress corrosion.
[Ans.: Tensile stress, corrosive environment]

6.30
9. The rate of corrosion of a metal is inversely proportional to the ________ areas.
[Ans.: anodic]
10. The rate of corrosion is more in presence of oxygen when pH value is ________.
[Ans.: below 7.0]
11. The conductance of clay and mineralised soil is much higher than those of ________ soils.
[Ans.: dry sandy]
12. In tinning, iron is protected with a coating of ________ metal.
[Ans.: tin]
13. ________ is an example of anodic inhibitors.
[Ans.: Chromates]
14. Cathodic inhibitors slow down the corrosion reaction by decreasing the diffusion of ________
ions to the cathode.
[Ans.: H+]
15. In sacrificial anodic protection, the more active metal is used as ________.
[Ans.: anode]
16. An example of anodic coating is ________.
[Ans.: galvanization]
17. An example of cathodic coating is ________.
[Ans.: tinning]
18. In metal cladding, ________ is sandwiched between two layer of pure aluminium.
[Ans.: duralumin]
19. Oxidation corrosion is an example of ________.
[Ans.: dry corrosion]
20. The immersion of base metal article in a bath of a noble metal salt which is used for coating is
called as ________ plating.
[Ans.: Electroless]
21. ________ is used to bind the pigment to the surface and protects pigment from decay.
[Ans.: Vehicle/Drying oil]
22. Commonly used thinner in paint is ________.
[Ans.: turpentine or petroleum]
23. Commonly used plasticizers in paint is ________.
[Ans.: Tricresyl phosphate or Triphenyl phosphate]
24. Brass and copper utensils are usually coated with ________.
[Ans.: Tin(Sn)]

25. ________ are providing desired colour and protection to paint film.
[Ans.: Pigments]
26. In chromizing, the base metal is thoroughly mixed in revolving drum containing metal oxides
of ________ and ________.
[Ans.: Al2O3, Cr2O3]
27. ________ is non-toxic in nature, so it is widely used for coating steel, copper sheets which is used
for storing food stuffs and packing of food materials.
[Ans.: Tinning]
28. In galvanizing, molten zinc bath is covered with ________ flux.
[Ans.: Ammonium chloride]
29. ________ coating is most preferrable than ________ coating.
[Ans.: Anodic, cathodic]
30. In sacrificial anodic protection, commonly ________ metal block is connected with underground
pipes.
[Ans.: Mg]

1. Corrosion is an example of
(a) Oxidation (b) Reduction
(c) Electrolysis (d) Erosion
[Ans.: a]
2. Chemically, the rust is
(a) Fe2O3 (b) FeO · Fe2O3
(c) Fe2O3 · xH2O (d) FeO · xH2O
[Ans.: c]
3. The metal which is protected by a layer of its own oxide
(a) Cu (b) Fe
(c) Au (d) Al
[Ans.: d]
4. The corrosion caused by the direct chemical action of environmental gases or anhydrous liquids
on metal surface is called
(a) Dry corrosion
(b) Wet corrosion
(c) Pitting corrosion
(d) Electrochemical corrosion
[Ans.: a]

6.32
5. Which of the following factors does not govern the rusting of iron?
(a) Presence of air
(b) Presence of moisture
(c) Presence of electrolytes in water
(d) Presence of impurities of more electropositive metals in iron
[Ans.: d]
6. In galvanic corrosion
(a) More metal gets corroded
(b) Less noble metal gets corroded
(c) The metal having a higher standard reduction potential gets corroded
(d) The metal placed lower in the electrochemical series get corroded
[Ans.: b]
7. In electrochemical corrosion
(a) Anode undergoes oxidation (b) Cathode undergoes oxidation
(c) Both undergo oxidation (d) None undergoes oxidation
[Ans.: a]
8. In differential aeration corrosion
(a) Poor oxygenated part acts as anode (b) Rich oxygenated part acts as anode
(c) Poor oxygenated part acts as anode (d) Metal as a whole acts as cathode
[Ans.: a]
9. The localised attack of a corroding environment leading to the formation of holes in an otherwise
relatively unattacked surface of a metal is called
(a) Water-line corrosion (b) Pitting corrosion
(c) Concentration cell corrosion (d) Wet corrosion
[Ans.: b]
10. Water-line corrosion is enhanced by the presence of
(a) Hydroxides (b) Chlorides
(c) Carbonates (d) Silicates
[Ans.: b]
11. Caustic embrittlement is a particular case of
(a) Pitting corrosion (b) Dry corrosion
(c) Stress corrosion (d) Wet corrosion
[Ans.: c]
12. To protect buried pipeline from corrosion is connected to Mg piece through a wire. This process
is called as
(a) Impressed current cathodic protection (b) Galvanic protection
(c) Sacrificial anodic protection (d) Sacrificial cathodic protection
[Ans.: c]

13. In an electrochemical series, the metal at the top is

(a) Most noble (b) Most stable
(c) Most active (d) Most protective
[Ans.: c]
14. Galvanizing is the process of coating iron with
(a) Mg (b) Cu
(c) Zn (d) Ni
[Ans.: c]
15. Corrosion of zinc metal containing an impurity of copper is called
(a) Water line corrosion (b) Moist corrosion
(c) Stress corrosion (d) Galvanic corrosion
[Ans.: d]
16. Anodic coating protects underlined metal
(a) Due to its higher reduction potential
(b) Due to its lower reduction potential
(c) Due to its noble nature
(d) Due to its higher oxidation potential
[Ans.: d]
17. Addition of hydrazine-hydrate to corrosive environment
(a) Retard anodic reaction
(b) Retard cathodic reaction by consuming dissolved oxygen
(c) Prevents diffusion of protons to cathode
(d) Increases hydrogen overvoltage
[Ans.: b]
18. In general, corrosion is maximum when the pH of the corroding medium is
(a) Above 7.0 (b) Equal to 7.0
(c) Below 7.0 (d) Equal to 1.0
[Ans.: c]
19. The process of covering steel with zinc to prevent it from corrosion is called
(a) Galvanizing (b) Tinning
(c) Electroplating (d) Electroless plating
[Ans.: a]
20. Acid pickling of steel is carried out by dipping the steel in
(a) Dilute Hcl (b) Dilute H2SO4
(c) Conc H2SO4 (d) Dil HNO3
[Ans.: b]

6.34
21. During galvanization, the function of flux ammonium chloride is

(a) To prevent oxide formation, on molten zinc
(b) To prevent reduction of molten zinc
(c) To acts as a barrier
(d) None of these
[Ans.: a]
22. In electroplating, the object to be protected from corrosion is made as
(a) Anode (b) Cathode
(c) Both anode and cathode (d) None of the above
[Ans.: b]
23. The oxygen carrier of the paint is called
(a) Drier (b) Pigment
(c) Thinner (d) Extenders
[Ans.: a]
24. In Electroless plating, the base metal article is immersed in a solution of
(a) More active metal salt (b) More noble metal salt
(c) Any one of these (d) None of the above
[Ans.: b]
25. An inhibitor which when added in small quantities to aqueous corrosive environment
(a) Effectively decreases the corrosion of a metal
(b) Increases the corrosion of a metal
(c) No effect on corrosion of metal
(d) Increases the corrosion nature of the environment
[Ans.: a]
26. The cathodic inhibitors slow down the corrosion reaction by decreases
(a) Diffusion of hydrated H+ ion to the cathode
(b) Diffusion of cl- ions to the cathode
(c) Diffusion of hydrated H+ ion to the anode
[Ans.: a]
27. In cathodic coating, base metal is coated with
(a) More noble metal
(b) Less noble metal
(c) More active metal
(d) Having more reduction potential
[Ans.: a]

28. In Impressed current cathodic protection, anode is placed in backfill because

(a) To slow down the rate of corrosion reaction
(b) To increases the rate of reaction
(c) To increase the electrical contact with the surrounding soil
[Ans.: c]
29. The rate of corrosion is more when
(a) Anodic area is large
(b) Anodic area is small
(c) Athodic area is small
[Ans.: b]
30. According to pilling-Bedworth rule, Greater is the specific volume ratio
(a) More is the oxidation corrosion
(b) Lesser is the oxidation corrosion
(c) More is the reduction corrosion
[Ans.: b]

1. Define corrosion.
Ans.: Any process of deterioration and consequent loss of solid metallic materials through an
unwanted chemical or electrochemical attack by its environment, is called as corrosion.
2. What is meant by rusting of iron.
Ans.: The attack of atmospheric gases on iron or steel, formation of a layer of reddish scale of
hydrated ferric oxide fe2O3 · 3H2O on its surface is known as rusting of iron.
3. What is dry corrosion.
Ans.: Dry corrosion takes place due to the direct chemical action of atmospheric gases like CO2,
SO2, O2, H2 etc or anhydrous liquids on the metal surfaces.
4. Formation of which types of metal oxide film cause rapid and continuous corrosion.
Ans.: Volatile oxide film and porous oxide film.
5. Formation of which types of metal oxide film prevents corrosion.
Ans.: Highly unstable oxide film and finely grained tightly adhering, impervious oxide film.
6. State the two conditions for wet corrosion to take place.
Ans.: (i) Immersion or partial dipping of two dissimilar metals or alloy in a solution.
(ii) A metal in contact with the conducting liquid.

6.36
7. Bolt and nut made of the same metal is preferred in practice. Why?
Ans.: Because such a combination will not permit galvanic corrosion to take place.
8. What is wet corrosion.

Ans.: Wet corrosion is due to the flow of electrons from metal surface anodic area towards
cathodic area through a conducting solution. It is also known as electrochemical corrosion.
9. What is galvanic corrosion.

Ans.: W hen two dissimilar metals are electrically connected and exposed to an electrolyte, the
metal higher in electrochemical series undergo corrosion.
10. The rate of metallic corrosion increases with increase in temperature. Give reason.
Ans.: With increase of temperature of the environment, the rate of reaction as well as rate of dif-
fusion increases, thereby corrosion rate increases.
11. Iron corrodes faster than aluminium, even though iron is placed below aluminium in the electro-
chemical series, why?
Ans.: This can be explained by the fact that aluminium forms a non-porous, very thin, highly adher-
ing protective oxide film (Al2O3) on its surface and this film does not permit corrosion to occur.
12. Wire mesh corrodes faster at the joints, why?

Ans.: The joints of wire mesh are stressed due to welding, so that part acts as anode, Hence oxi-
dation takes place easily at such joints leading to faster corrosion at the joints of wire mesh.
13. Impure metal corrodes faster than pure metal under identical conditions. Why?
Ans.: Because presence of impurities in metal cause heterogeneity and form minute electro-
chemical cells at the exposed parts, and anodic parts get easily corroded.
14. How is galvanization different from cathodic protection.

Ans.: In galvanization, the iron object is protected from corrosion by coating it with a layer of
zinc, whereas in cathodic protection, the iron object in made cathodic by connecting it
with a more anodic metal like Al, Mg, etc.
15. Where the electrochemical corrosion takes place.

Ans.: At the anodic area.
16. Rusting of iron is faster in saline water than in ordinary water. Give reason.
Ans.: Due to presence of sodium chloride in saline water, it leads to increased conductivity
of water, so when saline water comes in contact with the iron surface, corrosion current
increases and rusting is speeded up.
17. Why does part of a nail inside the wood undergoes corrosion easily?
Ans.: Corrosion is due to differential aeration, Because part of nail inside the wood is not exposed
to atmospheric conditions, whereas the nail outside is exposed to atmospheric air. Thus nail
inside the wood becomes anodic while remaining part acts as cathodic. So due to differen-
tial aeration, a differential current starts flowing, and the anodic parts gets corroded easily.

18. Why should nickel plated steel articles be free from pores and pin holes.
Ans.: with respect to nickel, steel is anodic and if there are pin holes and pores in nickel plated
steel article, they will expose the anodic steel to atmosphere. A galvanic cell is set up and
an intense localized corrosion at these small exposed parts occur.
19. Corrosion of water filled steel tanks occurs below the water line. Why?
Ans.: This is because, the area above the waterline is highly oxygenated and acts as cathodic, while the
part below the waterline is poorly oxygenated and acts as anodic. So due to differential aeration,
an electrochemical cell is set up which result in corrosion of steel tanks below the waterline.
20. What is meant by the term passivity?
Ans.: It is the phenomenon by which a metal or alloy shows higher corrosion resistance due to
formation of a highly protective, very thin and quite invisible surface film on metal surface.
21. What is effect of pH on corrosion.
Ans.: The lower the pH (or more acidic), greater is the corrosion.
22. Can we use aluminium in place of zinc for cathodic protection of rusting of iron, comment.
Ans.: Standard electrode potential of
Al3+/Al = -1.66V
Zn2+/Zn = -0.76V
In cathodic protection, the metal (iron) to be protected from corrosion is connected by a wire
to a more anodic metal (like Al, Zn etc.), so that all the corrosion occurs at this more active
metal. Thus, the parent metal is protected while the more active metal gets corroded slowly.
As the standard potential of aluminium is more than zinc, so Al is more anodic than Zn, so
we can better use aluminium in place of zinc for cathodic protection of rusting of iron.
23. Why are galvanized utensils not used?
Ans.: Because galvanized articles gets dissolved in dilute food acids and forms highly toxic
compounds. So, galvanized utensils cannot be used for preparation and storing food stuffs.
24. Why are brass utensils usually tinned?
Ans.: Because Tin (Sn) is a noble metal and protects the brass utensils from corrosion, moreover,
tin is non-toxic in nature. Hence, it is widely used for coating copper and brass utensils.
25. Galvanization of iron article is preferred to tinning, why?
Ans.: Galvanization (coating iron with zinc) is preferred to tinning (coating iron with tin) due
to the following reason: zinc(Zn) is more electropositive than iron, so zinc coating acts as
anode; while the exposed iron portions of coating acts as cathode, If by chance, the zinc
coating is broken at some place, the zinc (being more anodic than iron), undergoes corro-
sion, protecting iron from rusting. So, zinc coating protects iron sacrifically.
On the other hand, tin is a noble metal (i.e. having higher reduction potential than iron),
so it protects the iron due to its higher corrosion resistance than iron, If by chance, the tin
coating is broken at some place, much more corrosion of iron takes place because small
exposed part of iron cuts as anode and tin acts as cathode, a galvanic cell is set up, thereby
an intense corrosion at the small exposed iron part occurs.

6.38
26. What is chromizing?

Ans.: The process of heating a mixture of chromium powder, alumina and iron/steel article in a
revolving drum at 1300-1400 °c for 3-4 hours, It increases the corrosion resistance of the article.
27. What are the main constituents of oil varnish.
Ans.: synthetic resin, drying oil and volatile solvent
28. Give two functions of plasticizers.
Ans.: (i) It provides elasticity to the paint film.
(ii) To minimize the cracking of dried paint film.
29. Give three functions of drier in paints.
Ans.: (i) It acts as a carrier of pigments
(ii) It helps in forming a thin, homogeneous and protective film.
(iii) It supplies to paint film adhesion, toughness, durability and water-proofness.
30. Give two functions of extenders or fillers
Ans.: (i) It reduce the cost of paint.
(ii) It reduce the cracking of the paint film.
31. What is an enamel?
Ans.: enamel is an intimate dispersion of pigment in a varnish.
32. Give three function of thinner in a paint.
(i) To suspend pigment particles
(ii) To dissolve film-forming materials.
(iii) To reduce the consistency of paint for getting smooth finish.

Q.1 Define corrosion of metals. Explain the electrochemical theory of wet corrosion with mechanism.
Q.2 Give reasons for the following:
Silver and copper do not undergo much corrosion like iron in moist atmosphere.

(i) Wet corrosion (ii) Dry corrosion (iii) pitting corrosion

Q.4 Explain the mechanism of galvanic corrosion and differential aeration corrosion.
Q.5 What are the factors affecting corrosion? How is it prevented?
Q.6 Explain how can corrosion be controlled by proper designing.
Q.7 What is the role of sacrificial anode in corrosion control.
Q.8 What are the effects of temperature, pH, overvoltage and reactivity of metal influences the
corrosion.


(a) Sacrificial anodic protection (Galvanic protection)
(b) Impressed current cathodic protection
(c) Galvanization
(d) Galvanic series
(e) Caustic embrittlement
Q.10 Discuss the role of nature of oxide formed in oxidation corrosion. State and explain pilling-
Bedworth rule.
Q.11 Explain the mechanism of hydrogen evolution and oxygen absorption in electrochemical
corrosion.
Q.12 Describe the following methods of corrosion control
(i) Tinning (ii) hot dipping (iii) proper designing (iv) electroplating (v) metal clading.
Q.13 What is meant by corrosion inhibitors. Give two examples.
Q.14 Explain the importance of tinning in corrosion control.
Q.15 Give reasons for the following:
(i) corrosion of water filled tank occurs below the waterline.
(ii) A copper equipment should not possess a small steel bolt.
Q.16 Discuss the importance of design and material selection in controlling corrosion.
Q.17 Explain (i) pitting corrosion (ii) Bi-metallic (Galvanic) corrosion.
Q.18 Outline the difference in the use of anodic and cathodic coatings for corrosion prevention.
Q.19 Describe the process of galvanization of iron. How does it prevents the corrosion of iron.
Q.20 (i) Give the requirements of a good paint.
(ii) Write brief account on pigments.
Q.21 Explain the principle involved in
(i) anodic protection (ii) Cathodic protection (iii) galvanization (iv) cementation
Q.22 What happens and why?
(i) Iron sheet riveted with copper rivets.
(ii) An iron pole is partly burried under earth.
(iii) Zinc plate fixed below the ship.
Q.23 Iron corrodes faster than aluminium, even though iron is placed below aluminium in the elec-
trochemical series, why?
Q.24 Explain rusting of iron with the help of electrochemical theory of corrosion.
Q.25 Discuss the differences between varnishes and paints.

6.40
Q.26 What are the constituents of paints and what are their function.
Q.27 What are the important factors that influence the corrosion phenomenon.
Q.28 Write short notes on
(i) Sacrificial anode (ii) Corrosion inhibitors (iii) Electroplating (iv) Electroless Plating
Q.29 How does the nature of metal influence rate of corrosion.
Q.30 How are the metals protected against corrosion by modifying the environment?

Chemistry of
7 Engineering
Materials
7.1 SEMICONDUCTING AND SUPER CONDUCTING MATERIALS

According to conductivity, elements or materials are broadly classified into three categories. They are
as follows:
(i) Conductors
(ii) Semiconductors
(iii) Insulators
Conductors
They allow the maximum portion of the applied thermal or electric field to flow through them.
For example, metals are good conductors.
Insulators
They do not practically allow the heat or electricity to flow through them.
For example, most organic and inorganic solids, except graphite.
Semiconductors
The thermal and electrical conductivity of a semiconductor at normal temperature lies between that of
a conductor and an insulator.
Semiconductors are those solids which are perfect insulators at absolute zero, but conduct electric
current at room temperature. For example, silicon and germanium are two important elements used as
semiconductors.
7.1.1 Semiconductor
At room temperature, semiconductors allow a portion of electric current to flow through them. The
electrical conductivity of a semiconductor at normal temperature lies between that of a good conductor
and an insulator in the range of 10-9 to 102 ohm-1cm-1.

Semiconductors are those solids which are perfect insulators at absolute zero, but conduct electric
current at room temperature. Silicon and germanium are two very important elements used as semi-
conductors. The pure samples (≥99.999% pure) of these elements are obtained by zone refining; some
impurity is added deliberately to these elements by a process called doping. These are of two types—
intrinsic and extrinsic.
Intrinsic Semiconductors (Semiconductors Due to Thermal Defects)

Pure silicon or germanium act as insulators because electrons are fixed in covalent bonds and are not
available for conduction. At high temperatures, electrons are released by breaking of some of the cova-
lent bonds. These electrons move freely in the crystal and can conduct electricity. Without introducing
an external substance, these materials show conduction. Hence, these materials are known as intrinsic
semiconductors.
Extrinsic Semiconductors (Semiconductors Due to Impurity Defects)

Silicon and germanium (group 14 elements) in pure state have very low electrical conductivity.
However, the low electrical conductivity of these elements is greatly enhanced by the addition of even
traces of an element belonging to groups 13 (iii) or group 15 (v) to the crystals of group 14 (iv) elements,
that is, silicon or germanium. The induction of group 15 and group 13 elements to the crystal lattice of
group 14 elements (Si or Ge) produces n-type semiconductors and p-type semiconductors respectively.
n-type Semiconductors ( n Stands for Negative)

This type of semiconductor is produced in any of the following ways:
(i) Due to metal excess defect (explained earlier)
(ii) By the addition of trace amount of group 15 element (P, As) to extremely pure germanium or
silicon by a process called doping.
When an element of group 15(As) is added to germanium (group 14 element) crystal, some atoms of
germanium are replaced by arsenic. In such cases, four electrons of the impurity element (As) are used
in forming bonds to Ge, while the fifth electron remains unused. The additional electrons can move
freely and conduct electricity in the metals.
Hence, arsenic-doped germanium exhibits fairly high electrical conductivity.
p-type Semiconductor ( p Stands for Positive)

This type of semiconductors are formed by the following ways:
(i) Due to metal deficiency defects
(ii) By addition of impurity atoms containing less electrons (i.e., atoms of group 13); in such cases,
the parent insulator to the insulator lattice behaves like a conductor–electron.
When a group 13 element (like B, Ga, In) substitutes for a germanium atom (group 14 element), that is,
when a group 13 element (say B, having only three electrons in the outer shell) is added in small traces
to group 14 elements (say germanium), the atoms of B are not able to complete tetrahedral covalent
structures because they have one electron short of the requirement. Hence, some of the sites normally
occupied by electrons will be left empty. This gives rise to electron vacancies, commonly known as

Chemistry of Engineering Materials 7.3
positive holes because the net charge at these sites is positive. With an electric field, the adjacent elec-
trons move into the positive holes and form other positive holes. The current is passed in the crystal due
to the migration of positive holes. The electrical conductivity of germanium (group 14 element) crystal
increases by the doping trace amount of B (group 13 element). Here, the current is carried by positive
holes; hence, this type of conduction is known as p-type semi conduction.
Unlike metals, the conductivity of semiconductors increases with increase in temperature. This is
due to the fact that an extra electron or a positive hole is weakly bound with the crystal; when energy
is supplied in the form of heat, they (electron or a positive hole) become force from the crystal lattice
for the conduction of electricity.
7.1.2 Applications of Semiconductors

Various semiconductors have been prepared by the following types of combination.
(i) Elements of group 14 (Se, Ge) and group 15 (P, As, Sb)
(ii) Elements of group 13 (B, Ga) and group 14 (Si, Ge)
(iii) Elements of group 13 and group 15 (In Sb, Al, P)
(iv) Elements of group 12 and group 16 (ZnS, CdS, CdSe, Hg, Te)
The properties of a semiconductor are considerably changed depending upon the nature of the impu-
rity. Semiconductors are used in transistors and in exposure metals as photoelectric devices. A combi-
nation of p- and n-type of semiconductors (known as p-n junction) allows electric current from outside
to flow through it in one direction. This type of p-n junction is known as a rectifier and is used for
converting alternating current to direct current.
7.1.3 Superconductors
The electrical resistance of metals depends upon temperature. The electrical resistance decreases with
a decrease in temperature and becomes almost zero near the absolute temperature. Materials in this
state are said to possess super-conductivity. Thus, super-conductivity may be defined as a phenomenon
in which metals, alloys and chemical compounds become perfect conductors with zero resistivity at
temperatures approaching absolute zero. Super-conductors are diamagnetic. The phenomenon was
first discovered by Kamerlingh Onnes in 1913 when he found that mercury becomes super-conductor
at 4K. The temperature at which a substance behaves as super-conductor is called transition tempera-
ture. Most metals exhibit this phenomenon at a temperature range of 2K and 5K.
Efforts are being made to find materials that behave as super-conductors at room temperature
because attaining low temperature with liquid helium is highly expensive. The highest temperature at
which super-conductivity has been observed is 23K for alloys of niobium (Nb3Ge). Since 1987, many
complex metal oxides have been found to possess super-conductivity at fairly high temperatures. Some
examples are given here.
YBa2Cu3O7 90K
Bi2Ca2Sr2Cu3O10 105K
Tl2Ca2Ba2Cu3O10 125K
Super-conductors have many application in electronics, building magnets, aviation transportation
(trains which move in air without rails) and power transmission.

7.2 MAGNETIC MATERIALS

Magnetism is the ability of matter in which there is a force of attraction or repulsion between unlike or
like poles. More than 2,000 years ago, ancient Greeks discovered a mineral that attracts things made of
iron. This mineral was found in Magnesia, a part of Turkey; hence it was named magnetite. Magnets
are commonly used in workplaces and homes.
7.2.1 General Properties of Magnetic Materials

Some of the properties of magnetic materials are as follows:
(i) The Earth acts as a big bar magnet through its core. The north pole of magnets and compass nee-
dles point to the Earth’s magnetic south pole, which is near the Earth’s geographic north pole.
(ii) All magnets have two poles. If a magnet is allowed to rotate freely, the north pole will always
point to the north and the other is called the south pole.
(iii) Opposite magnetic poles attract each other and like magnetic poles repel.
(iv) Every magnet is surrounded by a magnetic field. The magnetic field lines explain the shape of the
field.
(v) According to Becquerel and Faraday, all matter including liquids and gases were affected by
magnetism, but a few respond to a noticeable extent and others do not.
7.2.2 Classification of Magnetic Materials

According to Faraday’s law of magnetic induction, the magnetic forces of material electrons will be
affected when a material is placed within a magnetic field. However, in a magnetic field material, elec-
trons can react quite differently (attract/repel). This mainly depends on the atomic or molecular struc-
ture of the material and the net magnetic field associated with the atom. Depending on the attraction
and repulsion in the magnetic field, materials can be classified into five categories as follows.
(i) Diamagnetic materials—weak repulsion to field
(ii) Paramagnetic materials—weak attraction to field
(iii) Ferromagnetic materials—strong attraction to field
(iv) Ferrimagnetic materials—strong attraction to field
(v) Antiferromagnetic materials—no magnetic moment
Diamagnetic Materials
Diamagnetic materials have weak magnetic susceptibility; hence, they repel slightly in a magnetic
field and the material does not retain the magnetic properties when the external field is removed. Such
materials have no permanent net magnetic movement due to paired electrons. In the external magnetic
field, the electron paths are realigned; hence, the material shows weak repulsion. For example, copper,
silver, gold, etc.
Paramagnetic Materials
Paramagnetic materials have a small positive susceptibility; hence, they attract slightly in a magnetic
field and the material does not retain the magnetic properties when the external field is removed.

Due to the presence of some unpaired electrons and the realignment of the electron path with the exter-
nal magnetic field, the materials show paramagnetism.
For example, magnesium, molybdenum, lithium, tantalum, etc.
Ferromagnetic Materials
Ferromagnetic materials have large positive susceptibility; hence, they exhibit strong attraction to
magnetic field and the materials retain their magnetic properties after the external field has been
removed due to the presence of magnetic domains. Due to the presence of unpaired electrons, ferro-
magnetic materials have net magnetic moment. Here, all the magnetic dipoles are aligned parallel and
are oriented in the same direction. For example, iron, nickel, cobalt, etc.
Curie Temperature
At a particular temperature, the electronic exchange forces in ferromagnets are very large. Hence,
thermal energy eventually overcomes the exchange and produces a randomising effect, and that tem-
perature is known as “Curie temperature”. Below the Curie temperature, the ferromagnet is ordered
and the above is disordered.
Hysteresis
Retaining magnetic properties after the removal of external magnetic field is known as hysteresis.
Magnetic Domain
In ferro and ferrimagnetic materials below Curie temperature, a large number of atom moments is
aligned parallel as small volume regions. This is known as “domain”. The adjacent domains are sepa-
rated by boundaries and are shown in Figure 7.1.
Domain boundary
One Another domain

domain
Figure 7.1 Adjacent domains separated by boundaries
Ferrimagnetic Materials
Ferrimagnetism is similar to ferromagnetism, but is observed in complex crystals and not in atoms in
which the magnetic moments of neighbouring ions are antiparallel and unequal in magnitude.
For example, magnatite was considered a ferromagnet until 1940. In 1940, Neel provided the theo-
retical framework about ferrimagnetism.

Antiferromagnetic Materials
Antiferromagnetism is a phenomenon exhibited by materials in which the complete magnetic movement
is cancelled with the antiparallel coupling of adjacent atoms or ions. Here, the successive magnetic dipoles
are aligned in opposite directions with the same magnitude; hence, it has no net magnetic moment.
For example, manganous oxide, chromium, etc.
Magnetic materials and their spin alignment are shown in Figure 7.2.
Paramagnetism Ferromagnetism
Antiferromagnetism Ferrimagnetism
Figure 7.2 Magnetic materials and spin alignment
7.2.3 Applications of Magnetic Materials

Magnets are used in a vast array of products from loudspeakers to space research. Some applications
are as follows:
(i) Power conversion (electrical to mechanical): In motors (starter motor, power steering motors,
washer pumps), generators and electromagnets.
(ii) Power adaptation and signal transfer: Transformers.
(iii) Permanent magnets: Loudspeaker, sensors, navigation and information systems.
(iv) Data storage analogue: Video and audio tapes.
(v) Data storage digital: Hard disk, floppy disk.
(vi) Quantum devices: Magnetoresisstive random access memory (MRAM), Gaint magnetoresist-
ance (GMR) reading head.
(vii) Instrumentation: Dashboard instruments, nanoscience and technology, medicine, research, etc.
7.3 CEMENT
Concrete is a widely used non-metallic material in construction. Cement is an important bonding
material and can bond sand and rock with water in concrete. It has adhesive and cohesive nature and
can bond with bricks, stones, etc.

7.3.1 Classification of Cement

Cement is broadly classified into natural, puzzolana, slag and Portland cement. These are briefly
discussed here.
Natural Cement
Natural cement is prepared with the calcination and pulverisation of naturally occurring argillaceous
limestone at high temperature. During calcination, calcium silicates and aluminates are formed.
Natural cement is a setting cement and possesses hydraulic qualities and relatively low strength.
The combination of sand with natural cement is known as mortar and is used in laying bricks and
setting stones. Mortar is also used in the construction of dams and as a foundation for bulk masses of
concrete.
Puzzolana Cement
Puzzolana cement is the oldest cement. It is invented by Romans and is used by them for the construc-
tion of walls and domes.
The mixing and grinding of natural puzzolana and slaked lime gives puzzolana cement. Volcanic
ash produced by rapid cooling of lava is known as natural puzzolana. It is a molten mixture of silicates
of calcium, aluminium and iron and has hydraulic properties as well.
Slag Cement
Slag cement is a mixture of lime and blast furnace slag. A mixture of calcium and aluminium silicates
(blast furnace slag) is granulated by pouring into a stream of cold water, dried mixed with hydrated
lime and pulverised to fine powder. The setting of slag cement is too slow, poor in abrasion resistance
and lower in strength. Hence, slag cement has limited applications and is used for making concrete in
bulk construction.
Portland Cement
In 1824, William Aspdin prepared Portland cement by heating limestone and clay by crushing the
resulting product to a fine powder. Hence, he is known as father of Portland cement. On mixing with
water, the cement is set to give a hard stone-like mass and resembles the stone of Portland, England.
Hence, it is known as a magic powder.
7.3.2 Raw Materials used in the Manufacture of Portland Cement

Portland cement primarily consists of lime, silica, alumina and iron.
The following materials are used for manufacture of cement:
(i) Calcareous materials, CaO (such as limestone, chalk, marl, etc.)
(ii) Argillaceous materials, Al2O3 (such as clay, shale, aluminium ore refuse, fly ash and so on)
(iii) Siliceous material, SiO2 (such as clay, shale, sand and so on)
(iv) Powdered coal or fuel oil

(v) Gypsum (CaSO4 · 2H2O) and

(vi) Iron components, Fe2O3 (ferriferous materials such as clay, iron ore and so on)
Importance and the Effects of the Ingredients on Cement

The proportion of the ingredients should be properly maintained; otherwise, the following effects may
be observed on the characteristics of cement.
Strength: Lime, silica, iron oxide and alumina play a vital role on strength of the cement. However,
excess/loss amount of lime and alumina reduces the strength due to expansion and disintegration.
Colour and hardness: Iron oxide provides colour and hardness to cement.
Soundness: A small amount of sulphur trioxide imparts soundness to cement; however, excess amount
reduces the soundness.
Setting: Alumina and lime help in quick setting. Gypsum helps to retard the setting action of cement
and enhances the initial setting time.
Efflorescent: Excess alkali causes the efflorescent.
7.3.3 Manufacture of Portland Cement

The manufacture of Portland cement involves the following steps:
(i) Crushing
(ii) Mixing
(iii) Burning
(iv) Grinding
(v) Packing
Crushing
Crushing of raw materials is done with two crushers. The primary crusher reduces the size of the raw
material to approximately five inches and the secondary crusher further reduces the size to three-
fourth inches. These are then ground to a fine powder (in ball mills or tube mills). Each separate pow-
dered ingredient is stored in separate hoopers (Figure 7.3).
Drilling RIG
Overburden
To crusher
Shale Each raw material
n is stored separately
ee
scr
g
atin
vibr
Limestone
To
Raw materials consists of
combinations of limestone,
cement rock, mart or oyster shells, Primary crusher
and shale, clay, sand, or iron ore Secondary crusher Raw materials conveyed
to grinding mills
Figure 7.3 Stone being reduced to five inches and three-fourths and stored

Mixing
Mixing of raw materials can be done either by a dry or a wet process.
Dry Process
The following proportions of the powdered materials, that is, lime 60–69 per cent, silica 17–25 per
cent, alumina 3–8 per cent, iron oxide 2–4 per cent, magnesium oxide 1–5 per cent, alkali oxides like
Na2O + K 2O 0.3–1.5 per cent and sulphur trioxide 1–3 per cent are then mixed and we get a raw mix.
This is stored in silos (storage bins) and are sent to a rotary kiln for burning. This process is shown in
Figure 7.4 (a) and (b).
To air separator
Raw mix
Cement rock
Limestone
Dust To
Iron ore
Oversize
Clay
Kiln
collector
Hot air
Fines
Dry process
furnace
Raw materials Grinding mill To pneumatic pump Dry mixing and Ground raw
are propertioned blending silos material storage
(a)
Vibrating
Wet process
screen
Water e
Oversiz
Cement rock
added
Limestone
Slurry
Iron ore
Fines
here
Clay
To
Kiln
Raw materials Grinding mill Slurry Slurry is mixed Slurry Storage basins
are propertioned pump and blended pump
Raw materials are ground to power and blended

(b)
Figure 7.4 (a) Dry process: mixing of raw materials; (b) Wet process: mixing of raw materials with water
Wet Process
The calcareous raw material is crushed, powdered, stored and the argillaceous material (clay) is thor-
oughly mixed with water for removing organic material in wash mills stored in basins. These two are
led to grinding mills (tube mill/ball mill) through channels in the right proportions and are mixed to
form a paste called slurry. The chemical composition of slurry may be adjusted with correcting basins,
and it contains about 38–40 per cent of water and is stored in tanks for feeding to a rotary kiln.
Differences between dry and wet process of mixing raw materials shown in Table 7.1.

7.10
Table 7.1 Differences between dry and wet processes

Dry process Wet process
1. It is used only when the raw materials are too hard. It can be used for any kind of raw material.
2. In this method, fine ground powder is formed. Here, slurry is formed.
3. This process is slow and fuel consumption is low. This process is fast and fuel consumption is high.
4. Inferior quality cement is formed. Superior quality cement is formed.
5. The cost of production is low but it is highly eco- Cost of production is little high, but the process is
nomical. cheap.
Burning
The burning process is done in a rotary kiln containing a steel tube, lined inside with refractory bricks,
having 2.5–3m in diameter and 90–120m in length. The kiln is in a slightly inclined position and is
capable of rotating at 1 rpm along its longitudinal axis. Fuel and air are injected at the lower end for
burning, which produce long hot flames that heat the interior of the kiln up to 1,750°C.
From the upper end of the kiln, raw mix or corrected slurry is injected. From the lower end of
the kiln, hot flames are forced with slow rotation and through slope of the kiln, the fed material move
towards the bottom of the kiln and the material descends gradually with temperature.
Depending on the temperature, the kiln is divided into three zones. They are drying zone, calcina-
tion zone and clinkering zone.
Drying zone: It is the upper part of the kiln having temperature around 400°C. Here, water in the slurry
gets evaporated.
Calcination zone: It is the central part of the kiln having temperature around 1,000°C. Here, limestone
of the dry mix or slurry is decomposed to give quick lime as small lumps, also called modules and
carbon dioxide, escape out.
CaCO3 CaO + CO2 ↑

Limestone Quicklime
Clinkering zone: It is the lower part of the kiln having temperature between 1500 and 1700°C. Here,
the chemical interaction of fusion occurs between lime and clay to form calcium aluminates and
silicates.
2Cao + SiO2 → Ca 2SiO 4 (C2S)
Dicalcium silicate
3Cao + SiO 2 → Ca 3SiO5 (C3S)
Tricalcium silicate
3Cao + Al 2 O3 → Ca 3 Al 2 O6 (C3 A)
Tricalcium aluminate
4Cao + Al 2 O3 + Fe2 O3 → Ca 4 Al 2 FeO10 (C 4 AF)
Tetra calciuminoferrite
The silicates and aluminates of calcium fuse to form about 0.5–1cm diameter hard, greyish stones,
known as clinkers. These are hot at about 1,000°C. They are cooled with cool air in another small
rotary kiln at the base of the main kiln and are collected in small trolleys (Figure 7.5).

Materials are
To stored separately
kiln
Dust Raw mix is kiln burned Clinker
Collector To partial fusion at 2700 °F Coal oil or
gas fuel Gypsum
Fan Dust Rotating kiln Clinker

bin cooler Clinker and gypsum conveyed
to grinding mills
Figure 7.5 Burning changes raw mix chemically into cement clinker
Grinding
In ball mills or tube mills, the cooled clinkers are ground to fine powder and 2–3 per cent of gypsum is
added to avoid quick setting and also acts as a retarding agent for early setting of cement, this is shown
in Figure 7.6.
3CaOAl 2 O3 + xCaSO 4 7H 2 O → 3CaO ⋅ Al 2 O3 + xCaSO 4 ⋅ 7H 2 O
Tricalcium aluminate after initial set Gypsum Insoluble tricalcium sulphoalluminate
Air
separator Dust
collector
Gypsum
Clinker
rsize
Ove Fines
Materials are
proportioned
Grinding mill Cement Bulk storage Bulk Bulk Box Packaging Truck
pump truck car car machine
Figure 7.6 Grinding—clinker with gypsum added into Portland cement and shipped
After the initial set, the cement water paste becomes stiff, but gypsum retards the dissolution of C3A by
forming tricalcium sulphoaluminate (3CaO ⋅ Al 2 O3 ⋅ x ⋅ CaSO 4 + H 2 O), which is insoluble (Figure 7.6).
Thus,
3CaOAl 2 O3 + xCaSO 4 ⋅ 7H 2 O → 3CaO ⋅ Al 2 O3 xCaSO 4 ⋅ 7H 2 O
After initial set Gypsum Tricalcium sulpho aluminate (insoluble)
The formation of insoluble C3A prevents very early further reactions of setting and hardening.
Packing
The ground cement is stored in silos, from which it is fed to automatic packing machines. Each bag,
usually contains 50kg of cement.
The flow diagram for the manufacture of Portland cement is shown in Figure 7.7.

7.12
7.3.4 Chemical Composition of Portland Cement and its Importance

Portland cement mainly contains dicalcium silicate (C2S), tricalcium silicate (C3S), tricalcium alu-
minate (C3A) and tetracalcium alumina ferrite (C4AFe). Each component exhibits particular special
behaviour, hence the behaviour of cement can be altered by changing the relative percentages of the
aforementioned compounds.
Dicalcium Silicate (C2S)

Due to slow reaction with water, it gets hardened slowly and strengthens after one week with the for-
mation of tobermonite gel with high surface area. Moist curing continues up to six months.
2CaO ⋅ SiO2 + xH 2 O → 2CaO ⋅ SiO2 ⋅ xH 2 O
Dicalcium silicate Tobermonite gel
Raw-materials
Limestone Clay
1. Crushing Washing
Proportioning Water
Grinding
2. Mixing
(Dry process) (Wet process) Water

Dry powder Slurry
3. Burning
Rotary kiln Pulverised Coal

coal
Clinkers
4. Grinding
Fine clinkers
Gypsum
Portland cement
5. Packaging
Shipment
Figure 7.7 Flow diagram for the manufacture of Portland cement

Tricalcium Silicate (C3S)

This material is responsible for the initial setting and early strength by the formation of hydrolgel; it
has a binding action between the aggregates when rapid reaction occurs with water.
3CaO ⋅ SiO2 + xH 2 O → Ca(OH)2 + 2CaO ⋅ SiO2 ( x − 1)H 2 O + Heat
Tricalcium s ilicate Hydrolgel
Tricalcium Aluminate (C3A)

Due to fast hydration, this compound forms hydrated tricalcium aluminate and is responsible for the
first few days of strength. This reaction is highly exothermic, hence cement is made with less C3A.
At that time, it generates less heat, develops higher strengths and shows greater resistance to sulphate
attacks.
3CaO ⋅ Al 2 O3 + 6H 2 O → 3CaO ⋅ Al 2 O3 + 6H 2 O + Heat
Tricalcium aluminate Hydrated tricalcium aluminate
Due to high heat generation and reactiveness with soil, C3A is the least preferred component in the
cement.
Tetracalcium Aluminferrite (C4AF)

It hydrates very rapidly, reduces clinkering temperature and gives little strength to concrete.
4CaO ⋅ Al 2 O3 ⋅ Fe2 O3 + 7H 2 O → 3CaO ⋅ Al 2 O3 + 6H 2 O + CaO ⋅ Fe2 O3 ⋅ H 2 O
Tetracalcium aluminate Calcium aluminate Calcium ferrite
Importance of Gypsum in Cement

Tricalcium aluminate (C3A) combines with water very rapidly with the evolution of large amount of
heat (exothermic reaction).
C3 A + 6H 2 O → C3 A ⋅ 6H 2 O + Heat
After the initial set, the paste becomes almost stiff. However, in the presence of gypsum, it reacts with
tricalcium aluminate to form insoluble tricalcium sulphoaluminate which helps to retard the speed of
the initial set and does not show any tendency to rapid hydration.
3CaO ⋅ Al 2 O3 → 32CaSO 4 ⋅ 2H 2 O → 3CaO ⋅ Al 2 O3 ⋅ 32CaSO 4 ⋅ 2H 2 O

Tricalcium aluminate Gypsum Tricalcium sulphoaluminate
The aforementioned reaction prevents high concentration of alumina in the cement solution and retards
the early initial set of the cement.
7.3.5 Setting and Hardening of Cement

When water is added and mixed to cement to form cement paste, hydration begins and it is converted
into gel and crystalline material. Solidification, interlocking and binding of the aggregates into a rock-
like matter is two-step process in the form of setting and hardening.

7.14
Setting
It is the stiffening of the cement paste with the formation of gel setting that is divided into initial setting
and final setting.
Initial setting: It refers to the hydration and gel formation from the different constituents of cement.
C3 A + 6H 2 O → C3 A ⋅ 6H 2 O + Heat
Tricalcium aluminate Crystalline hydrated
tricalcium aluminate
C4 AF + 7H 2 O → C3 A ⋅ 6H 2 O + CF ⋅ H 2 O + Heat
Tetracalcium Crystalline gel
alumine ferrite
During the hydration of dicalcium, silicate gives tobermorite gel, which possesses very high surface
area and a high adhesive property.
2C2S+ 4H 2 O → C3S2 ⋅ 6H 2 O + Ca(OH)2 + Heat
Dicalcium silicate Tobermonite gel Crystalline
Final setting: It is the complete formation of tobermorite gel.
Hardening
Hardening is the development of strength with the crystallisation of calcium hydroxide and hydrated
tricalcium aluminate.
2C3S+ 6H 2 O → C3S2 ⋅ 3H 2 O + 3 Ca(OH)2 + Heat
Tricalcium silicate Tobermonite gel Crystalline
calcium hydroxide
3C3 A + 6H 2 O → C3 A ⋅ 6H 2 O + Heat
Tricalcium aluminate Crystalline
hydrated tricalcium aluminate
Two theories are proposed for explaining the hardening of the cement.
Colloidal Theory by Michaels

According to this theory, silicate gels are formed with hydration and are responsible for hardening.
Crystalline Theory by Le Chatelier

According to this theory, crystalline products are formed with hydration, undergo interlocking and are
responsible for hardening.

Hence, setting and hardening of cement is due to the interlocking crystallisation of gels, which are
formed by hydrolysis of constitutional ingredients (Figure 7.8).
Unhydrated cement
+
Water
Hydration
Plastic mass (cement paste)

Colloidal
Crystaline theory
theory
Setting Metastable gel Hydrated crystaline products
Hardening Crystaline products

Stable gel (Coarser dimensions)
Figure 7.8 Schematic diagram of setting and hardening of cement
Ingredients and Reaction Sequence During Setting and Hardening of Cement

When water is added to cement, various ingredients undergo hydration and crystallisation in different
rates (Figure 7.9).
Hydration
Cement 1 day Gelation of
of C3A 7 days Gelation 28 days
+ C2S
and of C3 S
water and C3S
C4AF
Figure 7.9 Sequence of changes during setting and hardening of cement
7.3.6 ISI Specifications of Cement

According to ISI 269–1975, the composition of ordinary Portland cement shall satisfy the following
conditions:
Chemical Requirement of Cement

(i) Ratio of the percentage of lime (CaO) to that of silica (SiO2), alumina (Al2O3) and iron oxide
(Fe2O3) when calculated by the following formula:
CaO − 0.7SO3
shall not be less than 1.02.
2.8SiO 2 +1.2Al 2 O3 + 0.65Fe2 O3
(ii) Ratio of percentage of alumina (Al2O3) to that of iron oxide (Fe2O3) shall not be less than 0.66.
(iii) Weight of insoluble residue shall not exceed 2%.
(iv) Weight of magnesia shall not be more than 6%.

7.16
(v) Total sulphur contents, calculated as sulphuric anhydride (SO3) shall not be more than 2.75%.
(vi) Total loss on ignition shall not exceed 4%.
Physical Requirements of Cement

(i) Setting time:
Initial: not less than 30 minutes; final: not more than 600 minutes.
(ii) Compressive strength (of 1:3 cement mortar cube of cement ampers; Ennore sand):
Three days—not less than 1.6 kg/mm2 (or 16 N/mm 2)
Seven days—not less than 2.2 kg/mm 2 (or 22 N/mm 2)
(iii) Soundness:
By Le Chatelier’s method, it expresses the expansivity of the cement set in 24 hours between
25°C and 100°C.
Unaerated cement—maximum 10 mm
Aerated cement—maximum 5 mm
(iv) Fineness:
Not less than 215 m 2/kg; finer the grinding, the greater is the rate of reactions, thereby hasten-
ing the early development of strength. However, finer cement generates heat quickly, thereby the
cement mortar/concrete is likely to develop cracks.
7.3.7 Analysis of Cement

The quality of cement is maintained by conducting various tests from the raw material stage right up
to the packing stage, at every half an hour to one hour intervals. In fact, various physical and chemical
characteristics are tested. The quality of a sample of cement is determined from a number of measure-
ments as follows.
Soundness: The soundness of cement can analysed by Le Chatelier technique and autoclave method.
According to the ISI specifications, following properties should attain good quality of cement.
Soundness:
By auto clave method: Expansion not more than 0.8%
By Le Chatelier method:
For Aerated cement: maximum 5 mm
For Unaerated cement: maximum 100 mm
Fitness: By Turbidmetic method: 1600 cm2/gm.
By plain permeability method (as specific surface) ≥215 m2/kg.
Compressive strength: As per ISI specifications.
Tensile strength: As per ISI specifications.
Specific gravity: Specific gravity should be 3.1–3.2.
7.3.8 Plaster of Paris/Gypsum Plaster

Gypsum (hydrated calcium sulphateCaSO 4 ⋅ 2H 2 O) is extensively used as a raw material for the manu-
facture of plates, which are almost universally used for coating the inner walls of dwellings.
1
It is the hemihydrate of calcium sulphate 2CaSO 4 ⋅ H 2 O(or CaSO 4 ⋅ H 2 O)
2

Preparation
It is produced by heating pure gypsum to a temperature of about 120°C–160°C. If gypsum is heated
above 200°C, anhydrous sulphate is produced, which loses the power of readily combining with water.
1 °C
CaSO 4 ⋅ 2H 2 O CaSO 4 ⋅ 2H 2 O CaSO 4 ⋅ H 2 O 200
 → CaSO 4
2
Gypsum Orthorhombic Plaster of paris
dihydrate
The preparation of plaster of Paris from gypsum consists of the following operations:
(i) Crushing and grinding of gypsum
(ii) Calcination of ground gypsum in kilns by heating about 150°C
(iii) Pulverising the calcined product
Setting and Hardening

Plaster of Paris forms a plastic mass when it is mixed with water. This plastic mass quickly sets or
hardens, expanding in the process and regains the closely packed crystalline structure of gypsum. The
setting of plaster of Paris can be accelerated by mixing it with alkali sulphates such as K 2SO4, Na2SO4
or alums, which initiate as well as hasten the crystallisation process.
Applications
(i) Its slight expansion on setting renders plaster of Paris suitable for making mould. Therefore, some
details are accurately reproduced.
(ii) It is used in making surgical bandages, structural tiles and castings.
(iii) It is used as plaster for walls and in plaster boards, made up of alternate layers of a fibrous mate-
rial such as felt or paper.
7.4 REFRACTORIES
Refractories are ceramic materials that can withstand high temperatures as well as abrasive and cor-
rosive actions of molten metals, slags and gases, without suffering a deformation in shape. The main
objective of a refractory is to confine heat.
7.4.1 Characteristics of Good Refractory Materials

(i) A good refractory material should have excellent heat, corrosion and abrasion resistance.
(ii) It should possess low thermal coefficient of expansion and should expand and contract uniformly
with increase and decrease of temperature, respectively.
(iii) It should possess high fusion temperature. It should be infusible at operating temperatures.
(iv) It should be able to withstand the overlying load of structure, at operating temperatures.
(v) It should be chemically inert towards corrosive action of molten metal, gases and slags produced
in its immediate contact with furnaces.
(vi) It should not crack at operating temperatures.

7.18
7.4.2 Failures of Refractory Materials

If a given refractory material does not have the aforementioned characteristics, it will fail in service.
Thus, we can easily summarise conditions, which lead to failure of refractory materials as follows:
(i) Refractory material which does not have resistance to required heat, corrosion and abrasion.
(ii) Refractory material which has higher thermal expansion.
(iii) Refractory material which has less refractoriness than the operating temperature.
(iv) Lower quality refractory bricks than the actual load of raw materials in products.
(v) Usage of basic refractory material in a furnace in which acidic reactants and/or products are
being processed and vice versa
(vi) Refractory material that undergoes considerable volume changes during their use at high temp-
eratures.
7.4.3 Classification of Refractories

On the basis of chemical properties, refractories are broadly classified into three main categories.
Acidic Refractories
Refractories which consist of acidic materials are known as acidic refractories.
They are easily attacked by basic materials and not by acidic materials.
For example, alumina, silica and fireclay refractories.
Basic Refractories
Refractories which consist of basic materials are known as basic refractories.There are easily attacked
by acidic materials and not by basic materials.
For example, magnesite and dolomite.
Neutral Refractories
Refractories which consist of weak acidic/basic materials are known as neutral refractories. For exam-
ple, zirconia, graphite, chromite and carborundum.
7.4.4 Properties of Refractories

The important properties of refractories are as follows.
Refractoriness
It is the ability of a material to withstand heat without appreciable deformation. It is commonly meas-
ured as the softening or melting temperature of the material. The softening temperatures of refractory
materials are determined by using “pyrometric cones (seger cones) test” (Figure 7.10). The refractory
should have a softening temperature much higher than the operating temperature of the furnace in
which it is to be used.

Refractoriness is generally determined by comparing the behaviour of heat on the cone of the
material to be tested with that of a series of seger cones of standard dimensions. Refractoriness is
expressed in terms of pyrometric cone equivalent. Cones are 38mm height, 19mm long sides with tri-
angular base pyramids, and at definite temperatures, they can melt or fuse. The temperature at the apex
touching the base is indication of fusion/softening of the test cone. The number of the standard cones
fusing along with the test cone is the pyrometric cone equivalent (PCE) of that particular refractory. If
the test cone fuses later than one standard cone and earlier than the next cone, the PCE is the average
value of the two.
Softened and
deformed apex
37 36 35 joint touching
the base
Plaque
Figure 7.10 Seger cone test
Porosity
Porosity is the property of a solid which contains openings, spaces or minute channels. It can be
expressed as follows:
W −D
P= ×100
W−A
Where W is the weight of saturated specimen

D is the weight of dry specimen
A is the weight of saturated specimen submerged in water
If the refractory has pores, the entry of gases, slags, etc., is easy and can react up to a greater depth.
This can reduce the life of the refractory material. Consequently, it can affect many important proper-
ties of the refractory such as decreasing the strength, resistance to corrosion, resistance to abrasion but
increased resistance to thermal spalling. Hence, a good refractory should have low porosity.
Strength or Refractoriness–under Load

The refractory material must possess high mechanical strength, even at operating temperatures to bear
the maximum possible load, without breaking.
Dimension Stability
It is the resistance of a material to any volume changes, which may occur on its exposure to high
temperature, over prolonged time. It may reversible or irreversible.
Chemical Inertness
A refractory does not easily form fusible products with gases, ash, slags, etc., and hence should be
chemically inert.

7.20
Thermal Expansion
A refractory material should have the least possible thermal expansion due to the following reasons:
(i) Expansion of a refractory decreases the capacity of the furnace.
(ii) Repeated expansion and contraction contribute much towards rapid breakdown and wear and tear
of the material structure.
Thermal Conductivity
Depending upon the type of furnace refractory, materials of high and low thermal conductivity are
required. In most cases, the furnace is lined with refractories of low-heat conductivities to reduce heat
losses externally by radiation; otherwise, maintenance of high temperatures inside the furnace will
become difficult. In muffle furnace walls and coke-oven batteries, a good heat conductivity of refrac-
tory is desirable for effective heat transmission.
Thermal Spalling
The breaking, cracking, peeling off or fracturing of a refractory brick or block under high temperature
is known as thermal spalling.
Thermal spalling may be due to the following:
(i) Rapid change in temperature
(ii) Slag penetration into the refractory brick
Thermal spalling can be decreased by taking the following precautions:
(i) Using high porosity, low coefficient of expansion and good thermal conductivity refractory bricks
(ii) Avoiding sudden temperature changes
(iii) By overfiring the refractories
(iv) By modifying the furnace design
Heat Capacity
It depends on the following:
(i) Thermal conductivity
(ii) Specific heat and
(iii) Specific gravity of refractory
Resistance to Abrasion or Corrosion

Refractoriness is desirable that least abraded by descending hard charge, flue gases escaping at high
speed, particles of carbon or grit, etc.
Electrical Conductivity
Refractories specially used for lining electric furnaces should have low electrical conductivity. Except
graphite, all refractories are poor conductors.

Permeability
The rate of diffusion of gases, liquids and molten solids through a refractory is known as permeability.
It mainly depends on the size and number of connected pores. Permeability increases with temperature.
Texture
Due to large porosity, coarse- or light-textured bricks are less in weight; hence, they are more resist-
ance to sudden temperature changes.
7.4.5 Manufacture of High-Alumina Bricks, Magnesite Bricks

and Zirconia Bricks
High-alumina Bricks
High-alumina bricks are made by mixing calcined bauxite (Al2O3) with clay bind, which contains 50%
or more of Al2O3.
Properties
High-alumina bricks have very low coefficient of expansion, high porosity, great resistance to slags,
very little tendency to spall high temperature, load-bearing capacity, excellent wear-resistance and
stability, both in oxidizing and reducing conditions and are particularly inert to the action of gasses
such as CO2, H2 and natural gas. Thus, they are very good refractories, but very expensive; hence, their
use is limited.
Uses
Medium-duty Bricks
Bricks which contain 50–60% Al2O3 are used for zones of vertical shaft kilns for burning limes, lin-
ings of Portland cement rotary kilns, soaking pits, reheating furnaces, hearths and walls, etc., and are
subject to high abrasion.
High-duty Bricks
Bricks which contain 75% Al2O3 are used in sintering or the hottest zones of cement rotary kilns, lower
parts of soaking pits, brass melting reverberatories, lead dressing reverberatory furnaces, aluminium
melting furnaces, combustion zones of oil-fired furnaces, etc.
Magnesite Bricks
Magnesite bricks are the most widely used basic refractories. Calcined magnesite is powdered to a
proper size, mixed with binding material as caustic magnesia or iron oxide and the mixture is grounded
with water moulded into bricks, then slowly heated to 1,500°C upto eight hours and then slowly cooled.
Properties
Magnesite bricks can be used without load up to 3,000°C and with load of 3.5 kg/cm2 up to 1,500°C.
They possess good crushing strength, good resistance to basic slag and less shrinkage. They have a lot

7.22
of spalling with sudden temperature changes and their resistance to abrasion is poor. They have lot of
tendency to combine with water and CO2.
Uses
These are mainly used in open-hearth furnaces where high temperature required. They are also used in
hot mixer linings, copper converters, reverberatory furnaces for smelting antimony, copper, lead, etc.,
ores, refining furnaces and hot zones of cement rotary kilns.
Zirconia Bricks
These are prepared by heating zirconite mineral (ZrO2) and colloidal zirconite or alumina as bind-
ing material at 1,700°C. This is stabilised by adding of MgO or CaO without undergoing any volume
changes on heating and cooling.
Properties
Zirconia bricks are usually known as neutral refractories, but they have no resistance to acids, slags,
etc. Hence, they are between neutral and basic refractories. Without load, they can withstand up to
2,000°C, but specially prepared bricks can be used up to 2,600°C and with load of 3.5 kg/cm2, up to
1,900°C. They have good resistance to thermal shocks.
Uses
As these bricks are very costly, they are used only in high frequency electric furnaces.
7.5 LUBRICANTS
In all machines, lot of wear and tear is observed due to friction. Therefore, a large amount of energy
is also lost in the form of heat and moving parts get heated and damaged. The ill-effects of frictional
resistance can be minimised by using a suitable substance called lubricant, which can form a thin layer
in between the moving parts and keep the sliding or moving surfaces apart. Hence, frictional resistance
and consequent destruction of material is minimised.
“The process of minimising frictional resistance between moving or sliding surfaces by the intro-
duction of lubricants in between them is called lubrication”.
7.5.1 Important Functions of Lubricants

(i) It avoids direct contact between the rubbing surfaces and reduces surface deformation, wear, tear
and seizure.
(ii) It acts as a coolant by reducing loss of energy in the form of heat.
(iii) It enhances efficiency of a machine by reducing wastage of energy and expansion of metal by
local frictional heat.
(iv) It avoids seizure and relative motion of moving surfaces, such that running cost of the machine
will be reduced.

(v) The lubricant used between piston and the cylinder wall of an internal combustion engine acts as
a seal and can prevent the leakage of gases from the cylinder under high pressure.
7.5.2 Mechanism of Lubrication

There are mainly three types of mechanism by which lubrication is done. These are explained here.
Thick Film, Fluid Film or Hydrodynamic Lubrication

In this mechanism, moving or sliding surfaces are separated by thick film of lubricant fluid; hence, it is
known as thick film or fluid film lubrication. The thick film of lubricant covers entire moving surfaces
and fills irregularities.
Load Thick layer of
Therefore, there is no direct contact between the sur-
lubricant
faces of machine and consequently it reduces the wear. This Velocity
is shown in Figure 7.11. Here, only the internal resistance is
observed between the particles of lubricant; hence, the chosen
lubricant should have minimum viscosity under the working
conditions.
Hydrodynamic friction occurs in the case of shaft run-
ning places like journal bearings, which is shown in Figure
7.12. Thick film lubrication hydrocarbon oils are considered
satisfactory lubricants. Hydrocarbon lubricants are blended
with selected long-chain polymers to maintain viscosity of the
oil throughout the year. Figure 7.11 Fluid-film lubrication
Bearing lining
Boundary or Thin Film Lubrication
Rotating staff in
In this kind of lubrication, moving surfaces are separated floating lubricant
by a thin layer of lubricant, which is absorbed by physi- Thick film of lubricant
cal or chemical forces on the metallic surfaces as shown in
Figure 7.13. Here, the continuous film of lubricant cannot
persist due to any of the following reasons: Figure 7.12 Hydrodynamic lubrications
(i) A shaft starts moving from rest Load

(ii) The speed is very low
(iii) The load is very high Velocity
(iv) The viscosity of the oil is very low
Vegetable oils, animal oils and their soaps possess the property
of adsorption either physically or chemically to the metal sur-
faces and form a thin film of metallic soap, which acts as a good
lubricant. Adsorbed
thin layers of lubricant
Fatty oils possess greater adhesion property than mineral (vegetable or animal oil)
oil, and to improve the oiliness of mineral oils, a small amount of
fatty oils is added. Graphite and molybdenum disulphide are also Figure 7.13 Boundary lubrication
used for boundary lubrication.

7.24
Extreme Pressure Lubrication

In this mechanism, the moving or sliding surfaces are under very high pressure and speed; hence, this
is known as extreme pressure lubrication. Under such conditions, a high local temperature is attained,
and liquid lubricants fail to stick and may decompose or vaporise.
Special additives are added to mineral oils to meet the extreme pressure conditions and are called
extreme pressure additives. Organic compounds having active radicals or groups such as chlorine,
sulphur or phosphorous act as good additives. These compounds react with metallic surfaces to form
metallic chlorides, sulphides or phosphides as more durable films, capable of withstanding very high
loads and temperatures.
7.5.3 Classification of Lubricants

On the basis of their physical state, lubricants can be classified into three categories as listed hereunder.
Liquid Lubricants or Lubricating Oils

Apart from reducing friction and wear, lubricating oil also acts as a cooling medium sealing agent,
corrosion preventer, etc. According to origin, lubricating oils are classified into animal and vegetable
oils, mineral or petroleum oils and blended oils.
Animal and Vegetable Oils

Vegetable and animal oils possess good oiliness but they are costly, undergo oxidation easily, forming
gummy and acidic products, get thickened on coming in contact with air, etc. Hence, they are rarely
used as lubricant, but are used as blending agents.
Mineral or Petroleum Oils

Mineral oils are mainly obtained by the distillation of petroleum.
These are widely used lubricants because they are cheap, abundantly available and quiet stable
under service conditions. The hydrocarbon oil chain length varies between 12 and 50 carbon atoms.
The shorter chain hydrocarbons have lower viscosity than longer chain hydrocarbons.
When compared to animal and vegetable oils, mineral oils possess poor oiliness; therefore, to
increase oiliness, high molecular weight compounds such as oleic and steric acids are added.
Blended Oils
In many modern machinery, no single oil serves as the most satisfactory lubricant. Improving impor-
tant properties by incorporating specific additives is known as blending of oils; such oils give the
desired lubricating properties.
Properties of a Good Lubricating Oil

A good lubricating oil must possess the following qualities:
(i) Low pressure
(ii) High boiling point

(iii) Adequate viscosity to particular service conditions

(iv) Low freezing point
(v) High oxidation resistance
(vi) Heat stability
(vii) Non-corrosive property and
(viii) Stability to decomposition at the operating temperatures.
Greases or Semi-solid Lubricants

Semi-solids consisting of soap dispersed throughout liquid lubricating oil is grease; the liquid lubri-
cant may be a petroleum oil or even a synthetic oil, and may contain any of the additives for specific
requirements.
Preparation
Greases are prepared by the saponification of fat with alkali, followed by adding hot lubricating oil
under agitation. The total amount of mineral oil added determines the consistency of the finished
grease.
The structure of lubricating greases is like that of a gel. Soaps are gelating agents, which give
an interconnected structure by intermolecular forces containing the added oil. The soap dissolves in
the oil at high temperature; hence, inorganic solid, thickening agents are added to improve the heat
resistance of grease. Greases have higher shear or frictional resistance than oils and can support much
heavier loads at lower speeds.
Greases are used in the following situations:
(i) Where oil cannot remain in place due to high load, low speed, intermittent operation, sudden
jerks, etc., for example in-rail axle boxes.
(ii) Bearing and gears that work at high temperatures.
(iii) Where the bearing needs to be sealed against entry of dust, dirt, grit or moisture because greases
are less liable to contamination by these.
(iv) Where dripping or spurting of oil is undesirable, because unlike oils, greases do not splash or
drip over articles being prepared by the machine. For example, paper manufacturing machines,
textiles, edible articles, etc.
The main function of a soap is to acts as a thickening agent; hence, grease sticks firmly to metal sur-
faces. The nature of the soap decides its consistency, resistance to water and oxidation and temperature
up to the grease can be used. Hence greases are classified according to usage soap in their manufacture.
Some of the important greases are as follows:
Calcium-based Greases or Cup-greases

Calcium-based greases are emulsions of petroleum oils with calcium soaps, generally, prepared by
adding required amount of calcium hydroxide to hot oil while under agitation. These are the cheapest
and the most commonly used greases.
They are insoluble in water and are water-resistant. They are satisfactory for use at low tempera-
tures, because above 80°C, oil and soap begin to separate out.

7.26
Soda-base Greases
These are petroleum oils, thickened by mixing sodium soaps. They are not water-resistant, because the
sodium soap content is soluble in water. They can be used up to 175°C and are suitable for use in ball
bearings, where the lubricant gets heated due to friction.
Lithium-based Greases
They are emulsions of petroleum oils with lithium soaps. They have high water resistance and are suit-
able only below 15°C.
Axle Greases
They are cheap resin greases and are prepared by adding lime or heavy metal hydroxide to resin and
fatty oils. The resulting mixture is thoroughly mixed, allowed to stand and tack or mica-like fillers are
finally added. These are water-resistant and are also suitable for less delicate equipment working under
heavy loads at low speed.
Besides these, there are greases prepared by dispersing solids (like graphite, soapstone, etc.,) in
mineral oil.
Solid Lubricants
Graphite and molybdenum disulphide are the important solid lubricants.
These are used in the following conditions.
(i) The operating temperature or load is too high.
(ii) The blended lubricating oil or the mixed grease is unacceptable.
(iiii) There is a need to avoid combustible lubricants.
The layered structure of graphite and the sandwich-like structure of molybdenum disulphide are shown
in Figure 7.14 (a) and (b).
Each carbon
Carbon atoms in a atom is bonded by 3.08 Å
network of only three covalent
hexagons bonds Mo
atom layer
Plates of layers
capable of sliding 3.13 Å
parrellel to each
other S atom layer
3.4 Å 3.13 Å
Mo
atom layer
1.42 Å
(a) (b)
Figure 7.14 (a) Layered structure of graphite (b) Sandwich-like structure of molybdenum disulphide

Hence, the force to shear the crystals parallel to the layers is low and consequently, the parallel layers
slide over one another easily. Usually, some organic substances are mixed with solid lubricants so that
they may stick firmly to the metal surface.
Solid lubricants are used either in the dry powder form or mixed with water or oil. Graphite is
the most widely used lubricant because it is very soapy to touch, non-inflammable and not oxidised in
air below 375°C. Graphite is used in the form of powder or suspension in oil or water with the help of
emulsifying agent tannin. Graphite is dispersed in oil is called oildag and when dispersed in water, it
is called “aquadag”.
In the absence of air, it can be used up to very higher temperature. Graphite is used either in pow-
dered form or as suspension. Graphite greases are used at higher temperature.
7.5.4 Properties of Lubricants

The properties of lubricants are described here.
Neutralisation Number
The acidity or alkalinity of a lubricating oil is determined in terms of its neutralisation number.
Determination of acidity is more common and is expressed as the acid value or acid number. It is
defined as the “number of milligrams of potassium hydroxide required to neutralise all the free acid
present in one gram of the lubricating oil.”
Even the most carefully refined oil may have slight acidity. This is due to the presence of minute
amount of organic constituents that are not completely neutralised during the refining treatment or due
to traces of residues from the refining process. This small intrinsic acidity may not be harmful in itself,
but the degree to which it increases in already used oil is usually taken as a measure of the deterioration
of the oil due to oxidation or contamination. In fact, acid number greater than 0.1 is usually taken as
an indication of oxidation of the oil.
Saponification Number
The saponification value of an oil is defined as the “number of milligrams of potassium hydroxide
required to saponify one gram of the oil”. This is usually determined by refluxing a known quantity of
the oil with a known excess of standard KOH solution and determining the alkali consumed by titrating
the unreacted alkali.
Animal and vegetable oils undergo saponification but mineral oils do not. Further most of the ani-
mal and vegetable oils process their own characteristic saponification values. Hence, the determination
of the saponification value helps in ascertaining the presence of animal and vegetable oils in a lubri-
cant. Conversely, since each of the fined oil has its own specific saponification number, any deviation
from this value in a given sample indicates the probability and extent of adulteration.
Aniline Point
The aniline point of an oil is defined as “the minimum equilibrium solution temperature for equal
volumes of aniline and oil sample”. Aromatic hydrocarbons have high tendency to dissolve natural and
synthetic rubbers; this tendency can be determined on the basis of aniline point of an oil. A higher ani-
line point means lower percentage of hydrocarbons; therefore, having higher aniline point is desirable.

7.28
The aniline point is determined by thoroughly mixing equal volumes of aniline and the oil sample
in a tube and heating the mixture until a homogeneous solution is obtained. This is allowed to cool at a
specified rate until the two phases just separate out. The temperature corresponding to this particular
observation is reported as the aniline point.
Cloud Point and Pour Point

Petroleum oils are complex mixtures of chemical compounds and do not show a fixed freezing point.
When they are sufficiently cooled, they become plastic solids due to the formation of solid crystals or
the congealing of the hydrocarbons present. “The cloud point is the temperature at which this crystal-
lisation of solids in the form of a cloud or haze first becomes noticeable,” when the oil is cooled in a
standard apparatus at a standard rate. The pour point is “the temperature at which the oil just ceases to
flow when cooled at a standard rate in a standard apparatus”.
The pour point has a greater significance for lubricating oil because it determines the suitability of
a hydraulic oil for low temperature installations. Refrigerator plants, air-craft engines, etc., are some
important examples, which may be required to start and operate at sub-zero temperatures.
Flash Point and Fire Point

The flash point of an oil is defined as “the minimum temperature at which the oil gives off sufficient
vapour to ignite momentarily when a flame of standard dimensions” is brought near the surface of the
oil. The fire point of an oil is defined as “the lowest temperature at which the vapours of the oil burn
continuously for at least five seconds” when the standard flame is brought near the surface of the oil.
The lubricating oil should have flash point that is reasonably above its working temperature. This
ensures safety against fire hazards during usage, storage and transport. The flash point of lubricating
oil can be determined by Pensky Marten’s apparatus.
Viscosity and Viscosity Index

Viscosity is one of the most important properties of lubricating oil. The formation of a fluid film of a
lubricant between the friction surfaces and the generation of frictional heat under particular conditions
of load, bearing spread and lubricant supply mostly depend upon the viscosity of the lubricant and, to
some extent, on its oiliness. When large working clearances exist between the friction surfaces, a high
viscosity oil is generally recommended to “cushion” the intermediate application of load. However, it
is often necessary to sacrifice some of the cushioning effect of viscous oil by the partial substitution of
a thinner oil to provide good circulation of oil to dissipate the frictional heat.
If the viscosity of the oil is very low, the fluid lubricant film cannot be maintained between the
moving surfaces as excessive wear may take place. On the other hand, if the viscosity of lubricating
oil is very high, excessive friction would occur due to shearing of oil. Hence, in hydrodynamic lubri-
cation, the lubricant selected must possess sufficiently high viscosity due to adherence to the bearing
and prevent it being squeezed out due to high pressure and yet fluid enough so that the resistance to
the shear is not too high. It is, therefore, essential to have knowledge of the viscosity of lubricating oil.
Viscosity is a measure of the internal resistance to the motion of a fluid and is mainly due to the
forces of cohesion between the fluid molecules. Absolute viscosity can be defined as the tangential
force per unit area required to maintain a unit velocity gradient between two parallel planes in the
fluid unit distance apart. The units of absolute viscosity h (eta) in the centimetre-gram-second (CGS)

system are poise and centipoise (1/100th of a poise). A poise is equal to one dyne per second per square
centimetre. The viscosity of water at 20°C is about a centipoise.
The ratio of absolute viscosity to density for any fluid is known as the absolute kinematic viscos-
ity. It is denoted by h, and in the CGS system, its units are stokes and centistokes (1/100th of a stoke).
h
n=
r
where n = absolute kinematic viscosity

h = absolute dynamic viscosity
r = density of the fluid.
The dimensions of dynamic viscosity are HL −1T−1, and the dimensions of kinematic viscosity are L2T−1.
For academic purposes, viscosity is usually expressed in centistoke, but a more common practical
measure of the viscosity of an oil is the time in seconds for a given quantity of the oil to flow through
a standard orifice under specified set of conditions. Viscosities are usually determined with Redwood
viscometer in commonwealth countries, with Engler’s viscometer in Europe and with Saybolt’s vis-
cometer in the USA. In these commercial viscometers, a fixed volume of the liquid is allowed to flow
through the standard orifice of particular standard apparatus. Redwood (No. 1) seconds at 25°C. The
viscosity of the oil so determined in the time unit is sometimes called relative viscosity. Since the
instruments used are of standard dimensions, the kinematic viscosity of the oil in centistokes can be
calculated from the time taken by the oil to flow through the standard orifice of the instrument, with
the help of the following equations:
m = Ct (for fluids whose kinematic viscosity is more than centistokes) and
m = Ct − b /t (for fluids having kinematic viscosities lesser than or equal to 10 centistokes)
m = Kinematic viscosity in centistokes
t = Time of flow in seconds
C = Viscometer constant
B = Coefficient of kinetic energy, which may be determined experimentally or eliminated by
choosing long flow times
For routine purposes, the test viscometer may be calibrated and the constant C determined by
using solutions of known viscosity. The primary standard used is freshly distilled water whose kin-
ematic viscosity is 1.0008 centistokes. Other standards usually employed are as follows:
40% sucrose solution:
n = 4.390 cs at 25°C, r = 1.17395
60% sucrose solution:
n = 33.66 cs at 25°C, r = 1.28335
For Redwood No. 1 viscometer, the values for the constants are as follows:
Time of flow, t B C
40–85 seconds 190 0.264
85–2,000 seconds 65 0.247
These constants are based on the results of the work carried out at the National Physical Laboratory
at a temperature of 70°F (21.11°C) and with the ranges of viscosity; at that temperature, the results are
accurate to ±1%.

7.30
Redwood No. 2 viscometer is used for every viscous liquids and gives one-tenth the value of
Redwood No. 1 viscometer.
Viscosity Index
The viscosity of an oil decreases with increase in temperature as a result of decrease in intermolecular
attraction due to expansion. Hence, it is always necessary to state the temperature at which the viscos-
ity is determined.
In many applications, the lubricating oil will have to function in a machinery over considerably
wide range of operating temperatures. If this occurs due to seasonal variations in atmospheric tem-
perature, adjustments can be affected by selecting different oils of appropriate viscosity for different
seasons. However, in case of internal combustion engines, aeroplanes, etc., the lubricant used must
function at low starting temperature as well as at very high operating temperature. Since the vis-
cosity of lubricating oils decreases with temperature, it is impossible to select an oil having same
viscosity over such a wide range of operating temperatures. However, one can select an oil whose
variation in viscosity with temperature is minimum. This variation can be indicated either by vis-
cosity temperature curves or by means of the viscosity index. The viscosity index is the numerical
expression of the average slope of the viscosity temperature curve of lubricating oil between 100°F
to 210°F. The oil under examination is compared with two standard oils having the same viscos-
ity at 210°F as the oil under test. Oils of the Pennsylvanian type crudes thin down the least with an
increase in temperature, whereas oils of the Gulf coast origin thin down the most as the temperature is
increased.
Hence, the viscosity index of Pennsylvanian oil is taken as 100 and that of the Gulf oil as zero.
Then, the viscosity of the oil under investigation is deducted as follows:
V − VX
Viscosity index of the oil under test L ×100
VL − VH
where V L = viscosity at 100°F of Gulf oil standard, which has the same viscosity at 210°F as that of
oil under test
VX = viscosity of the oil under test
VH = viscosity at 100°F of Pennsylvanian standard oil, which has the same viscosity at 210°F as
that of oil under test.
Thus, the higher the viscosity index, the lower the rate at which its viscosity decreases with
increase in temperature. Hence, oils of high viscosity index, that is, those having that viscosity tem-
perature curves are demanded for air-cooled internal combustion engines and aircraft engines. In
general, oils of high specific gravity have steeped viscosity temperature curves. However, all oils tend
to attain the same viscosity above 300°C.
By and large, light oils of low viscosity are used in plain bearings for high-speed equipment such
as turbines, spindles and centrifuges, whereas high viscosity oils are used with plain bearings of low-
speed equipment.
Mechanical Stability
Four balls extreme-pressure test is one of the important mechanical tests to judge the suitability of a
lubricant under conditions of very high pressure, as shown in Figure 7.15. In this test, the lubricant

under test is powered in a machine containing four balls. Here, the upper ball is rotated and the lower
three balls are stationary. The load is gradually increased, the ball is withdrawn and examined at spe-
cific intervals for scale formation, etc., and under a given load, the ball bearings after the test comes
out clean if the lubricant desirable. When the load is progressively increased, the liberated heat welds
the ball together. Here, the lubricant is said to have completely failed. Hence, this test enables us to
determine the maximum load that can be carried safely by a lubricant. The four-balls extreme-pressure
lubricant tester is shown in Figure 7.15.
Top ball
rotates
Stationary
balls
Lubricant sample
under-test
Load force
Figure 7.15 Four-balls extreme-pressure lubricant tester
7.5.5 Redwood Viscometer

The Redwood viscometer is made in two sizes. The Redwood No. 1 viscometer is commonly
used for determining viscosities of lubricating oils and has an efflux time of 2,000 seconds or
less. The Redwood No. 2 viscometer is similar to the Redwood No. 1 type but the jet for the out-
flow of the oils is of a larger diameter and hence gives an efflux time of approximately one-tenth
of that obtained with Redwood No. 1 instrument under otherwise identical experimental conditions.
The Redwood No. 2 instrument is therefore used for the oils having higher viscosities such as fuel
oils.
The Redwood viscometer does not give a direct measure of viscosity in absolute units but it ena-
bles the viscosities of oils to be compared by measuring the time of efflux of 50 ml of oil through the
standard orifice of the instrument under standard conditions. The results given by these two viscom-
eters are reported as Redwood No. 1 viscosity or Redwood No. 2 viscosity followed by the efflux time
in seconds of the experimental temperature.
Description
The Redwood No. 1 viscometer as shown in Figure 7.16 essentially consists of a standard cylindrical
oil cup made up of brass and silvered from inside and has 90 mm height and 46.5 mm in diameter.
The cup is open at the upper end. It is fixed with an agate jet in the base. The diameter of the orifice
is 1.62 mm and the internal length is 10 mm. The upper surface of the agate is ground to concave
depression into which a small silver-plated brass ball is attached to a stout wire can be placed in
such a way that the channel is totally closed and no leakage of the oil from the cup through the orifice

7.32
Thermometers
Stirrer blade
Metallic oil Pointer

cup
Water path
Stirrer shield
Oil Valve rod

Heating tube
Water Water
Agate jet of 1.82 mm dia
and 10 mm length
Kohilrausch
flask
50 Levelling
mL screw
Figure 7.16 Redwood viscometer No. 1
can take place. The cup is provided with a pointer, which indicates the level up to which the oil should
be filled in a cup. The lid of the cup is provided with an arrangement to fix a thermometer to indicate
the oil temperature. The oil cup is surrounded by a cylindrical, copper vessel containing water, which
serves as a water bath used for maintaining the desired oil temperature with the help of electrical
heating oils or by means of a gas burner as the case may be. A thermometer is provided to measure
the temperature of water. A stirrer with four blades is provided in a water bath to maintain uniform
temperature in the bath, thus enabling uniform heating of the oil. The stirrer contains a broad, curved
flange at the top to act as a shield for preventing any water from splashing into the oil cylinder. The
entire apparatus rests on a sort of tripod stand provided with levelling screws at the three legs. The
water bath is provided with an outlet for removing water as and when needed. A sprit level is used for
levelling the apparatus and a 50 ml flask for receiving the oil from the jet outlet is also provided.
Working
The instrument is levelled with the help of the levelling screws on the tripod. The water bath is filled
with water to the height corresponding to the tip of the indicator up to which the oil is to be filled in
the cylindrical cup. The orifice is sealed by keeping the brass ball in position. Then the oil under test
is carefully poured into the oil cup up to the tip of the indicator. The 50 ml flask is placed in position
below the jet. The oil and water are kept well-stirred and the respective temperatures are noted. The
ball is raised and suspended from the thermometer bracket. Simultaneously, a stopwatch is started.
When the level of the oil dropping into the flask just reaches the 50 ml mark, the stopwatch is stopped
and the time is noted in seconds. The ball value is replaced in the original position to prevent the over-
flow of the oil. The experiment is repeated, and the mean value of time of flow for 50 ml of the oil is
reported as t seconds, Redwood 1 at T°C. The usual test temperatures stipulated are 21.11°C (70°F),
60°C (140°F) and 93.33°C (200°F).

During the test, the measuring flask should be shielded from draughts with the help of metal shields
usually supplied with the instrument.
7.5.6 Engler’s Viscometer

This instrument is diagrammatically presented in Figure 7.17. The water bath is heated by a gas ring,
and its temperature is kept uniform with the help of the stirrer. The oil cylinder is fitted with three
gauge points, which indicate the amount of oil required and also serve as a means of levelling the
instrument. The loosely fitting cover carrying thermometer can be gently rotated to agitate the oil. The
jet is slightly tapered and is made of platinum for standard work and nickel for general work. The valve
pin, which seats itself in the jet, is lifted at the commencement of a test and is supported in the cover
by a cross pin. As the valve pin is lifted, the stopwatch is started and the time of outflow of 200 ml of
the oil is determined.
The viscosity is expressed in Engler degrees or degree E by using water as standard. The time of
outflow of 200 ml of water at 20°C is taken as 52 seconds. The viscosity in degrees E is calculated by
dividing the time m seconds for the outflow of 200 ml of oil by time of outflow of 200 ml of water at 20°C.
Bath
Valve pin
thermometer
Stirrer
Bath G
liquid G-Gauge points
Oil
(three altogether)
200 ml Gas ring
Figure 7.17 Engler’s viscometer
7.5.7 Saybolt Viscometer

A single unit Saybolt universal viscometer is shown in Figure 7.18. In a multiple-unit viscometer, a
number of oil cups can be accommodated in the same bath, thus enabling tests on a number of oils to
proceed at the same time. Instruments can be fitted with an electric immersion heater, a U-tube for
steam heating or water cooling and a gas ring, which is placed inside the air jacket surrounding the
water bath. The bath liquid is stirred by rotating the cover by means of the two handles as a turn-table
arrangement.

7.34
Bath
thermometer Electric heater
Gallery U-Tube
Stirrer
blade Stirrer
blade
Oil
Air jacket
Cork Gas-ring
60 CC
Oil
Stirrer
handle
Electric
heater
Top view
Figure 7.18 Saybolt viscometer
The temperature can be regulated by running cold or warm water through the U-tube irrespective
of the heating arrangement used. The jet is made of a hard non-corrodible metal such as monel or
stainless steel. The lower end of the jet opens into a larger tube. This tube, when stoppered by a cork,
becomes a closed air chamber preventing the oil flowing out (Figure 7.18).
To start the test, the bath is brought to the test temperature and the oil is heated to the same tem-
perature in a separate vessel. The oil is then poured into the oil cylinder and stirred with the oil ther-
mometer and any excess oil flowing over into the surrounding gallery. When the oil and the bath are at
the same temperature, the oil thermometer is removed, the excess oil drawn off from the gallery with
a pipette, the cork withdrawn and the stopwatch started. The collecting flask is arranged such that the
oil stream will strike its neck, thus avoiding the formation of foam.
For very viscous fuels, a viscometer with a larger jet known as the Saybolt furol viscometer is
used. The Saybolt universal viscometer can be used for oils having flow times of more than 32 sec-
onds. There is no maximum unit; but in general, for liquids having flow times over 1,000 seconds, the
Saybolt furol viscometer is better.
7.5.8 U-Tube Viscometer

The standard U-tube viscometer (Figure 7.19(a) and (b)) is an improved form of the Ostwald viscom-
eters, which is used for the determination of the absolute viscosity of lubricating oils. The determina-
tion of absolute viscosity of lubricating oils by the U-tube viscometer based on Poiseuille’s law.

P πr 4 t
V=
8l η
where V = volume of the liquid flowing through a capillary tube of length l (cm) of uniform radius r
(cm) in a times t (seconds) and h (poise) is the coefficient of viscosity of the liquid at the particular
temperature.
Hand pump
D
C
C
B
B
F
D A
F
(a) (b)
Figure 7.19 U-tube viscometers (a) standard U-tube viscometer (b) Ubbelohde suspende level viscometer
The determination of absolute viscosity by the U-tube viscometer essentially consists of measurement
of the time of passage through the capillary of a fixed volume of liquid under a fixed mean hydrostatic
head ρ of the liquid. If the density of the liquid is d, then P ∝ d and since, for a given viscometer,
h ∝ td.
h = ktd
where k is the proportionality constant; It can be determined for different viscometers from its known
dimensions or by calibration with a standard liquid such as water or any other liquids.
absolute dynamic viscosity ( η)
Absolute kinematic viscosity v = centistokes
density of the liquid (ρ)
7.5.9 C
onversion of Redwood, Engler and Saybolt Viscosities
into Absolute Units
Redwood, Engler and Saybolt instruments are not the ideal methods of determining absolute vis-
cosities. The conversion values are only considered good approximations when only taken at the same
temperature.

7.36
Therefore, the conversion of the aforementioned relative viscosities to absolute viscosities is done
with the help of the following equation:
v = ct − b /t
where v = Kinematic viscosity in centistokes,
t = time flow in seconds,
c and b are constants.
Values of c and b are given in Table 7.2.
Table 7.2 Values of c and a

Instrument Value of c Value of b
Redwood No. 1 0.25 172
Redwood No. 2 2.72 1,120
Saybolt universal 0.22 180
Engler 0.147 374
7.6 EXPLOSIVES AND PROPELLANTS
Explosives
An explosive is a “substance or compound or mixture, which when subjected to thermal and mechani-
cal shock, gets very rapidly oxidised exothermically with a sudden release of potential energy”.
The explosive reaction is exothermic, so the products get heated to a high temperature and a high
pressure is exerted on the surroundings. The amount of power available from a given weight or volume
of explosive, is called “power to weight ratio”.
7.6.1 Some Important Terms about Explosives

Some important terms about explosives are as follows:
Explosive Strength
It is the energy liberated per unit mass of the explosive (cal/g).
Velocity of Detonation
It is the velocity with which the given explosive detonates.
Sensitivity
It can be determine the effect and impact of friction, heat, electric spark or detonator wave etc., on
explosives. Some explosives may detonate by a feather touch, whereas some may not detonate even
with a hammer blow. Sensitivity plays a key role in the selection of explosives for a particular purpose.
Brisance
It indicates the shattering power of an explosive.

7.6.2 Classification of Explosives

Explosives are broadly classified into three groups.
Detonators/Primary Explosives/Initiating Explosives

These are highly sensitive, and explode on receiving a slight-shock or when exposed to fire. Hence,
they should be handled with utmost care. Some of examples are as follows:
Lead Azide (PbN6 )

It is very popular for military uses due to low cost, excellent initiating action and stability in storage.
Mercury Fulminate [Hg(CNO2 )]

It is more sensitive and expensive than lead azide. It is slightly toxic.
Tetracene (C2H7N7O)
It requires low initiating action; ignites easily with high heat of explosion and produces a large volume
of gases.
Diazodinitro Phenol (DDNP)

It is quite sensitive and has high brisance and consequently can initiate explosion even in less sensitive
high explosives.
Propellents or Low Explosives

These are simply burns and do not explode all of a sudden. The chemical reactions taking place in such
explosives are slow and their burning proceeds from the surface inwards in layers at an approximate
rate. The gases evolved disperse readily without building high pressure and consequently, they can be
easily controlled. Some of examples are as follows:
Gun Powder or Black Powder

It is a mixture of 75% potassium nitrate, 15% charcoal and 10% sulphur. The explosive reaction is
10KNO3 + 3S + 8C (3K 2SO4) + 2K 2CO3 + 6CO2 ↑ + 5N2↑
If excess of carbon and sulphur take part in slower processes, it leads to evolution of more gases.
It is an excellent and a cheap explosive for blasting down of coal, as its low velocity gives it a slow
heating action that does not shatter the coal unduly. Hence these are known as time in delay-fuses; used
for blasting in shells, igniters and primer assemblies for propellants, practice bombs and saluting charges.
Nitrocellulose
It is prepared by treating cellulose with nitric and sulphuric acids. Formed nitrocellulose is dissolved
in a mixture of ether and alcohol and the solvent is evaporated, leaving a jelly-like solid behind. It is
study by adding stabiliser like diphenylamine and pressed into cylindrical rods. It is called smokeless
powder as it produces smokeless gases such as CO2, CO, N2 and water vapour.

7.38
High Explosives
Explosives which have high energy content than the primary explosives are called high explosives.
These are quite stable and are insensitive to fire, mechanical shocks, etc. Hence, to start a rapid chemi-
cal reaction, some amount of primary explosives are placed with high explosives.
These are broadly divided into four groups:
Single Compounds Explosives

These contain only one chemical compound. Some of examples are as follows:
(i) Ammonium nitrate: It is very stable, nontoxic and cheap and has low brisance value. It is about
half as powerful as TNT and is mostly employed in making binary explosives. It is dangerous to
store near any inflammable material.
(ii) TNT (Trinitrotoluene): It is high explosive. It is most widely used in shell-firing and under-water
explosions and is well-suited for loading in containers, due to low melting point. It is a safe explo-
sive in manufacture, transportation, storage, non-hydroscopic and violent disruptive explosive,
and does not react with metals. Hence, it is used for military purposes.
(iii) PETN (Pentaerythritol tetra nitrate): It is an extremely powerful, sensitive and standard military
explosive.
(iv) RDX or cyclonite: It is a powerful, sensitive, less toxic, high explosive. RDX came into promi-
nence in military as well as an industrial explosive.
Binary Explosives
Binary explosives are a mixture of TNT and other explosives, and these are more convenient and supe-
rior than single explosives. Due to their low melting point, TNT is one of the ingredients in all binary
explosives.
For example,
(i) TNT + Ammonium nitrate is amatol.
(ii) TNT + PETN is pentolite.
(iii) TNT + Tetryl is tetrytol.
(iv) TNT + RDX + Al powder is tropex.
(v) TNT + Al flakes is titronal.
Plastic Explosive
These are a combination different explosives which are in plastic state. They can be hand moulded and
made into various shapes without any serious risk and are mainly used for industrial applications and
military uses. With high explosive simple combination of plastic explosive can prepare. Due to their
engineering applications, they are available as flexible sheets.
Dynamites
These are explosives containing nitroglycerin as the main ingredient, by pressure or shock detonates.
4C3 H(NO)3 →10H 2 O + 6N ↑ + 12CO ↑ + O ↑

1 Volume up to 10,000 volumes at temperature explosion

The explosion is so sudden that it would shatter the breech of the rifle, before the bullet had time to
move. It also pulverises the rock, instead of breaking it into fragments of immovable size. It is danger-
ous in handling and transporting and is usually mixed with an insert absorbent like wood pulp, starch,
meals, etc. Some examples are as follows:
(i) Straight dynamites: They contain 15–60% nitroglycerine in wood meal with sodium nitrate. The
important uses are blasting of hard rocks, coal and other minerals.
(ii) Blasting gelatin-dynamites: It is the combination of nitroglycerene (91.5%) partly gelatinised by
nitro cotton (8%) or colladion cotton and CaCO3 (0.5%). These are very powerful, water-proof
and stick well in holes into which they have been loaded. They can be used under wet conditions,
where high loading density is desired.
The important uses are submarine blasting, tunnel driving, deep-well shooting and at places
where maximum shattering effects are desired.
(iii) Gun cotton (or cellulose nitrate): Cotton is steeped for half an hour in a cooled mixture of con-
centrated nitric acid and concentrated sulphuric acid.
C6H7O2(OH)3 + 3HNO3(C6H7O2(NO3)3 + 3H2O
(iv) Cordite: It is a form of smokeless powder made by dissolving guncotton (65 parts), nitroglycerine
(30 parts) and petroleum jelly or vaseline (five parts) in acetone. The resulting paste is rolled and
cut into pieces of different dimensions, according to the rate of explosion desired. When acetone
evaporates, the horny cordite remains. The vaseline acts as a stabiliser and a cooling agent on the
powder as it has a tendency to lower the temperature of explosion. The guncotton slows down the
explosive reaction of nitroglycerine and makes cordite an excellent propellant for large calibre
naval guns.
(v) Gelignite: It consists of 65% blasting gelatine and 35% of absorbing powder. It is a powerful
explosive, which can be used under water.
7.6.3 Precautions during Storage of Explosives

The following precautions should be taken while storing explosives:
(i) Explosives should be stored separately, that is, without mixing with others.
(ii) Detonators and explosives should be stored separately.
(iii) Flame lanterns should not be used. In case of power failure, only torches should be used for light-
ing purposes.
(iv) All electric fittings and wirings should be properly insulated and frequently checked.
(v) Only authorised persons should be allowed to the explosive store by wearing magazine shoes.
(vi) One should take care of jerks or drops while handling explosives.
(vii) Smoking/fire should be strictly prohibited around the explosive store.
(viii) The magazine (explosive store) should not be constructed within 500m from any working kiln
or furnace.
(ix) The boundary of the explosive store should be protected by high barbed wire fencing and proper
caution boards should be put up.
(x) The magazine should be provided with heightening conductors as a safeguard.
(xi) During thunder, the magazine should not be opened and no one should be allowed inside.

7.40
7.6.4 Blasting Fuses

A fuse is “a thin water-proof canvas length of tube containing gunpowder (or TNT) arranged to burn
at a given speed for setting off charges of explosives. Fuses are of two types as follows.
Safety Fuse
It is employed in initiating caps, where electrical firing is not used. A safety fuse consists of a small
diameter core of black powder, enclosed in a covering of wrapper of water proofed fabrics. It is made
to have an approximate burning speed of 30–40 seconds per foot (or about 1 cm s-1). When a fuse is
used to fire a shot in blasting, sufficient length is used so that ample time is allowed for the shot firer
to reach a point of safety.
Detonating Fuse
It has a velocity of over 6,000 m/s and consists of a charge of high velocity explosive, such as TNT,
contained in a small diameter bent tube. The line of fuse (called Cordean) is in contact with the charge
throughout its length and this causes practically instantaneous detonation of the whole charge, regard-
less of its velocity. Such fuses are used principally for exploding charges of explosive in deep holes.
7.6.5 Important Explosives and their Preparation

(i) Lead AzidePb(N3)2 is prepared by reacting sodamide (formed by reacting ammonia with sodium)
with nitrous oxide (N2O), followed by treating the sodium azide (NaN3) so-formed with lead
acetate.
Thus;
6NH3 + 2Na (2NaNH2 + 3H2)
NaNH2 + N2O → (NaN3 + H2O)
2NaN3 + Pb(OAc) → Pb(N3)2 + 2AcONa
Sodium azide Lead acetate Lead azide Sodium acetate
(ii) Mercury Fulminate Hg(ONC)2 is prepared by dissolving mercury in excess of HNO3 and then
pouring the resulting solution of ethyl alcohol, when the solution starts boiling and mercury ful-
minate is precipitated.
Decomposition reaction: Hg(ONC)2 Hg(g) + N2 + CO + 117 k Cal
(iii) Diazodinitrophenol (DDNP) is prepared by diazotising picranic acid.
OH OH O H
Diazotization N2Cl
O2N NH2 O2N −HCl O2N N
NO2 NO2 NO2

4,6- dinitro-1,2 -di-
axophenol (DDNP)
(iv) Trinitrotoluene (TNT) is prepared by the nitration of toluene (C6H5CH3) using a nitrating mixture
of concentrated HNO3 and concentrated H2SO4 in 1:1 ratio in a tank reactor, in which contents
are continuously stirred.

CH3 CH3
O2N NO2
(conc)
+ 3HNO3 (conc)
H2SO4
Toluene NO2
TNT
The liquid product (TNT) so formed is taken out, washed with ammoniacal solution of Na2SO3
and then with cold water, when TNT crystallises out. Crystals of TNT are filtered and purified by
melting. The melt is dried (by passing warm air) and poured in containers.
Decomposition reaction: TNT (3.5CO + 3.5C + 2.5H2O + 1.5N2 + 190 K cal
(v)
Nitroglycerine (NG) or glycerol trinitrate (GTN) is prepared by adding glycerol to a cooled mix-
ture of concentrated H2SO4 (60%) and concentrated HNO3 (40%) at 10°C with constant stirring.
CH2OH CH2ONO2
conc
CH2OH + 3HNO3 (conc) CHONO2
H2SO4
CH2OH CH2ONO2
After nitration, the mixture is run into a tank, when the nitroglycerine rises to the top, while
excess acids form the lower layer. The nitroglycerine layer is separated, washed first with water
and then with dilute sodium carbonate solution (2%) to remove traces of acids completely. It is
then converted into different desired types of dynamites by absorbing in specific inert materials.
Decomposition reaction: 4C3H5(NO3)2(12CO2 + 6N2 + 10H2O + O2
(vi) Pentaertythrital Tetranitrate (PETN) is prepared by the cannizaro reaction between formalde-
hyde and acetaldehyde in the molar ratio 4:1.
CH2OH CH2ONO2
Ca(OH)2 3HNO3 (conc)
CH3CHO + 4HCHO HOH2C C CH2OH O2NOH2C C CH2ONO2
H2SO4 (conc)
CH2OH CH2ONO2
PETN
Decomposition reaction: C(CH2ONO2)4(3CO2 + 2CO + 4H2O + 2N2 + 180 K Cal

(vii) RDX or Cyclonite (Cyclomethylene trinitro amine) is prepared by treating hexamethylene tetra
amine with nitric acid.
(CH 2 )6 N 4 + 4HNO3 → (CH 2 NNO2 )3 + NH 4 NO3 + 3HCHO
Hexamethylene tetra amine Formaldehyde
7.6.6 Rocket Propellants

A rocket propellant is a high oxygen-containing fuel plus oxidant whose combustion takes place in a
definite and controlled manner with the evolution of a huge volume of gas. A propellant reacts quickly,
producing a very large volume of hot gases (usually at a temperature of 3,000 °C and a pressure
of 300 kg/cm2), which exits through a small opening (called “jet” or nozzle) at supersonic velocity.
This act of pushing the gas backwards produces an equal and opposite reaction—Newton’s third law of

7.42
motion, which moves the rocket forward. With the increase of exhaust velocity, the rocket performance
increases. Rockets are used for pyrotechnic effect signalling, carrying a life, hurling explosives at an
enemy, putting space capsule into orbit, etc. (Figure 7.20).
Liquid oxygen
Kerosene
(C12H26)
(O2)
Injection
C12H26 + 18.5 O2 Chamber
12CO2 + 13H2O Combustion

Chamber
Figure 7.20 Use of bipropellant in a rocket. Combustion reaction between kerosene and liquid oxygen produces
a huge volume of gaseous CO2 and H2O, the thrust of which forces the rocket upwards with a high speed
7.6.7 Characteristics of a Good Propellant

The characteristics of a good propellant are as follows:
(i) It should have high specific impulse (specific impulse is the thrust delivered divided by the rate
of propellant (fuel plus oxidant) burnt.
(ii) It should produce low molecular weight products (like H2, CO, CO2 and N2) during combustion.
(iii) It should burn at a slow and steady rate.
(iv) It should possess low ignition delay (ignition delay is the time taken by propellant to catch fire in
the presence of an oxidising agent. It is expressed in milliseconds)
(v) It should possess high density.
(vi) It should be stable over wider ranges of temperature.
(vii) It should be safe to handle and store under ordinary condition, that is, it should not detonate
under shock, heat or impact.
(viii) It should be non-corrosive and non-hydroscopic.
(ix) It should be readily ignitable at a predictable burning rate.
(x) It should leave no solid residue after ignition.
(xi) It should not produce toxic products.
(xii) It should produce high temperature on combustion.
Note: Specific impulse is the thrust in kg per second on the fuel burnt. The value of thrust (or propul-
sive force) due to momentum of the exiting gases and is given by the following formula:
m
F= v + ( Pe − Pa )
g
where F = thrust (kg/m/kg)
m = mass flow (kg)
g = acceleration due to gravity (9.81 m 2/s)

v = exhaust velocity (m/s)

Pe = exit pressure (kg/m 2)
Pa = ambient gas pressure (kg/m 2)
and Ae = nozzle exit area (m 2)
7.6.8 Classifications of Propellants

The chemical propellants are classified into solid and liquid categories.
Solid Propellants
These may be “homogeneous” or “composite”. When a solid propellant or a mixture of propellants are
thoroughly mixed in a colloidal state, it is called homogenous solid propellant.
When a single propellant is employed, it is called a single-base propellant. For example, nitro
cellulose, also known as guncotton or smokeless powder. On the other hand, a solid propellant which
contains two materials is called a double-base propellant. For example, ballistite, containing nitro cel-
lulose and nitroglycerine mixture, is a powerful double-base solid propellant. Cordite, composed of
65% nitrocellulose, 30% of nitro cellulose and 40–45% nitroglycerine. Diethyl phthalate, up to 5%, is
also added and this acts as a solvent cum plasticiser, thereby giving a homogenous plastic mass, which
can be worked smoothly. In addition, up to 1% of diphenylamine is added, which acts as a stabiliser.
The propellant gives a flame temperature of about 2,700°C and the volume of gases is about 1,500
times the original volume.
When an oxidising agent is dispersed in a fuel mass, the solid propellant is heterogeneous or com-
posite. Gunpowder is the oldest composite propellant. It gives a flame temperature of 800–1,500°C
and volume of gases is about 400 times the volume of the charge. Other composite solid propellants
are 75% potassium per chlorate plus 25% asphalt oil, 80% ammonium perchlorate plus 20% resin
(rubber) binder, 46% ammonium picrate, 48% sodium nitrate and 8% plastic resin binder. In selecting
the oxidiser, it should be seen that it is non-hygroscopic, stable in contact with fuel and does not form
any corrosive products. The oxidant potassium perchlorate leaves behind a white residue of potassium
chloride particles; while ammonium perchlorate leaves no solid residue, but its combustion products
contain hydrogen chloride and water, which form a toxic and corrosive fog.
Liquid Propellants
They possess many advantages over solid propellants. Thus, liquid propellants are more versatile and
the engine using them can be checked and more easily calibrated. However, unlike solid propellants,
the engine using liquid propellant is quite delicate and cannot withstand any rough handling. Liquid
propellants may be monopropellants or bipropellants.
Monopropellants
It has fuel as well as oxidiser in the same molecule or in a solution containing both these. For example,
hydrogen peroxide, nitromethane, ethylene oxide hydrazine propyl nitrate and a mixture of 21.4%
methanol and 78.6% hydrogen peroxide are some of the common propellants (mono). A monopropel-
lant must be safe to state and at the same time, it should burn smoothly. Due to its reactivity, hydrogen
peroxide is not easy to store and handle. Moreover, metal oxides catalyse decomposition. Therefore,
storage tanks are made of special materials for the same.

7.44
Bipropellants
These are more widely used. Here, liquid fuel and oxidiser, kept separately, are separately injected in the
combustion chamber. The commonly used fuels are liquid hydrogen, hydrazine, ethyl alcohol, aniline
and kerosene oil. Ethyl alcohol admixed with 25% water is a good fuel. Although the addition of water
reduces flame temperature, it reduces the molecular mass of combustion gases, which compensates for
reduction in performance. The common oxidisers employed are liquid oxygen, ozone, hydrogen perox-
ide, fuming nitric acid and liquid flourine. Liquid oxygen is a non-toxic, safe and good oxidising agent,
but it has to be stored under pressure in insulated containers. Ozone is a very powerful oxidising agent,
but it is quite toxic and can explode at high concentration. Liquid flourine is volatile, toxic, corrosive,
very reactive, but is a very good oxidising agent. It is also difficult to store and handle it.
7.7 NANOMATERIALS
Nanoscience and technology are considered one of the most promising fields having huge potential to
bring countless opportunities in many areas of research and development. It is the study of tiny struc-
tures at nanometer scale, which forms a basis for several core technologies.
Definition
“Nanotechnology plays a key role in many areas”.
“One nanometer is one billionth of a meter”.
1 nm = 1/1,00,00,00,000 of a metre, which is close to 1/1,00,00,00,000 of a yard.
For getting easy sense of the nanoscale, it is suffice to know that a human hair has around 50,000
nm and a commonly used microchip has around 150 nm. The normal human eye can see the things
which have the size above 10,000 nm only.
Note on Measures
Almost all nanosciences are discussed by using SI measurements; SI Units and their description shown
in Table 7.3.
Table 7.3 Measuring units and their description

SI unit Description
Meter (m) Approximately three feet or one yard.
Centimeter (cm) 1/100 of a meter, around half an inch (10-2 m)
Millimeter (mm) 1/1,000 of a meter (10-3 m).
Micrometer (μm) 1/100,000 of a meter (10-5 m), also called micron; this is the scale of the most integrated circuits.
Nanometer (nm) 1/1,00,00,00,000 of a meter (10-9 m). The size scale of single, small molecules and nanotechnology.
7.7.1 Synthesis of Nanomaterials

Nanotechnology has sprung into prominence due to the recent development of various synthesis tech-
niques/methodologies and the discovery of modern tools for the characterisation and manipulation
of nanomaterials. Synthesis techniques are broadly categorised as top-up approach and bottom-up
approach. Some of the methods for synthesis of nanomaterials are as follows:
(i) Vapour–liquid–solid growth

(ii) Solution–liquid–solid growth

(iii) Template–mediated growth
(iv) Electron beam lithography
(v) Reverse micellar route, etc.
Preparation of Copper and Nickel Nanooxalates by Reverse Micelle Route

The reverse micellar route is the best method for synthesis of variety of nanoparticles due to the ability
to mix the reactants efficiently and control the size of nanoparticles effectively.
The synthesis of these nanorods have been achieved using two micro-emulsions as described
here:
(i) Microemulsion I is the mixture of cetyl trimethyl ammonium bromide (CTAB) as a surfactant
and n-butanol as the co-surfactant. Here, isooctane or n-octane is used as a hydrocarbon phase
and 0.1 M copper nitrate/nickel nitrate solution is used as the aqueous phase.
(ii) Microemulsion II comprises the same constituents as microemulsion I, except for having 0.1
m ammonium oxalate instead of copper nitrate or nickel nitrate as the aqueous phase. The
weight fractions of various constituents in these microemulsions are 16.76% of CTAB, 13.90%
of n-butanol, 59.29% of isooctane and 10.05% of the aqueous phase. These two microemulsions
were mixed slowly and stirred overnight on a magnetic stirrer, and the resulting precipitate was
separated from the apolar solvents and surfactants by centrifuging and washing it with 1:1 mix-
ture of methanol and chloroform. The precipitate is then dried in air.
7.7.2 Characterisation
The nano materials are characterised by X-ray diffraction, transmission electron microscopy, scanning
electron microscopy, (TEM, SEM and AFM), dynamic light scattering studies (DLS), thermal analy-
sis (TGA/DTA), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy
(XPS), field dependent magnetisation studies, etc.
7.7.3 Importance
(i) The synthesis of nanowires and nano rods has generated a lot of interest in the recent years due
to their importance as objects for understanding microscopic systems.
(ii) Nano-structured wires and rods are expected to have interesting optical, electrical, magnetic and
mechanical properties as compared to micron-sized whiskers and fibres.
(iii) There also find potential use as nanowires in the area of biosensors, where a specific molecule
is attached to the tip of the nanowire, which then identifies a particular molecule in the living
system.
7.7.4 Broad Classification of Nanomaterials

According to the arrangements of atoms or molecules, nanomaterials are broadly classified into three
types as follows:
(i) Materials which have one dimension in the nanoscale.
For example, surface coatings and thin films.

7.46
(ii) Materials which have two dimensions in nanoscale.

For example, nanowires and nanotubes.
(iii) Materials which have three dimensions in nanoscale or quantum dots.
For example, fullerenes, cadmium-selenium quantum dots, gold quantum dots, ZnO quantum
dots, etc.
Some Other Nanomaterials

Super-paramagnetic iron oxide nanoparticle, ZnO nanoparticle, titanium oxide nanoparticle, carbon-
coated silver nanoparticles, gold nanoparticle, NaYF4 nanophosphors, CdS nanowires, ZnS nanorods,
Fe3O4 nanoparticles, etc., are some other nanomaterials.
7.7.5 Fullerenes
A fullerene is a molecule of carbon in the form a hallow sphere, ellipsoid, tube and many other shapes.
A spherical fullerene are also called Buckminsterfullerene (bucky balls); they resemble the balls used
in football. The cylindrical one is called carbon nanotubes or bucky tubes. The fullerene is similar to
structure graphite, which is composed of stacked graph sheets of linked hexagonal or pentagonal rings.
Buckminsterfullerene (C60) was prepared in 1985 by Richard Smalley, Robert curl, James heath,
Sean O’Brien and Harold Kroto. Kroto, Curl and Smalley were awarded the 1996 Nobel Prize in
Chemistry for their roles in the discovery of this class of molecules.
7.7.6. Types of Fullerenes

The types of fullerenes are discussed in this section.
Bucky Ball Cluster

Since the discovery of fullerenes in 1985, many types of fullerenes like Bucky ball clusters, nanotubes,
mega tubes, nano “onions”, linked “ball and chain” dimmers and fullerene rings are prepared.
The most common bucky ball is C60 as shown in Figure 7.21.
Figure 7.21 Common buck ball
Buckminsterfullerene was named after Richard Buckminster Fuller, a noted architectural modeller
who popularised the geodesic dome. As buckminsterfullerenes have a shape similar to that sort of a
dome, the name seemed to be appropriate. As the discovery of the fullerene family came after buck-
minsterfullerene, the shortened name “fullerene” is used to refer to the family of fullerenes. The suffix
“-ene” indicates that each C atom is covalently bonded to three others (instead of the maximum of four),

a situation that classically would correspond to the existence of bonds involving two pairs of electrons.
Buckminsterfullerene is the smallest fullerene molecule containing hexagonal and pentagonal rings, in
which two pentagons share on edge. It is also the most common is terms of natural occurrence, as it can
often be found in soot.
The structure of C60 is a tralancated icosahedron, which resembles an association football of the
type made of 20 hexagons and 12 pentagons with carbon atom at the verities of each polygon and a bond
along each polygon edge. The Van der Waals diameter of a C60 molecule is about 1.1 nm. The nucleolus
to nucleolus diameter of α C60 molecule is about 0.71 nm. The C60 molecule has two bond lengths.
Applications
Fullerenes have been extensively used for several bio-medical applications including the design of high
performance MRI contract agents, X-ray imaging contract agents, photo dynamic therapy and drug
and gene delivery and have been summarised in several comprehensive reviews.
Carbon Nanotubes
Nano tubes are cylindrical fullerenes. These tubes of carbons are usually only a few nanometers wide,
but they can range from less than micrometer to several millimeters in length. They often have closed
ends but can be open-ended as well. Their unique molecular structure results in extraordinary micro-
scopic properties including high tensile strength, high electric conductivity, high ductile, high heat
conductivity and relative chemical in actively.
Hallow tubes of very small dimension with single or multiple walls having potential application
in electronics and industry. Carbon nanotubes have been identified into three structures namely, arm-
chair, zigzag and chiral structure (Figure 7.22 (a), (b) and (c)).
(a) (b)
(c)
Figure 7.22 (a) Armchair (n, n), (b) Zigzag (n, 0), (c) Chiral (n, m)
Due to well-defined geometry, exceptional mechanical properties and extraordinary electrical charac-
teristics of carbon nanotubes (CNTs) are used as nanoelectric circuits, nanoelectrochemical systems,
nonorobots, etc.

7.48
Synthesis of Carbon Nanotubes

Carbon nanotubes, including powder and array types, are generally produced by three main techniques.
(i) Electric arc discharge method
(ii) Laser ablation method
(iii) Thermal or plasma-enhanced chemical vapour deposition method
Laser ablation and arc discharge methods are modified physical vapour deposition techniques and
involve the condensation of hot, gaseous carbon atoms generated from the evaporation of solid carbon.
In arc discharge, vapour is created by an arc discharge between two carbon electrodes with or with-
out a catalyst. The nanotube self-assemble from the resulting carbon vapour laser ablation produces a
small amount of clean nanotubes, whereas arc discharge methods generally produce large quantities
of impure material. Laser ablation and arc discharge techniques produce powder-type nanotubes with
impurities in the form of amorphous carbon and catalyst particles because of the high temperature of
the heat source. The chemical vapour deposition method is a better technique for high yield and low
impurity production of carbon nanotube arrays at moderate temperatures. Plasma-enhanced chemical
vapour deposition can grow individual, free-standing nanofibers with special controlling ability. On
the other hand, high-density aligned nanotubes can be mass-produced using thermal chemical vapour
deposition. The method also provides good control over the size, shape and alignment of the nanotubes.
Recently, Kang et al. have synthesised dense, perfectly aligned arrays of single-walled nanotubes,
and Vijayaraghavan et al. have been able to horizontally align individual nanotubes on a large scale
using dielectrophoretic force. Nanotube materials for analytical applications should be clean with low
impurities from metal catalysts and amorphous carbon. The synthesis of nanotubes with a uniform size
and special density is critical before post-processing and functionalisation.
Applications of Carbon Nanotubes
(i) Carbon nanotubes are used in the preparation of nanoelectric circuits, nanoelectromechanical
systems and nanorobotic systems.
(ii) Multi-walled carbon nanotubes can serve as bearings, switches, gigahertz oscillators, memories,
shuttles, syringes, etc.
(iii) The hollow carbon nanotubes can be used as containers, conduits, pipettes, coaxial cables, etc.
Carbon Nanotubes as Nano Biosensors

Carbon nanotubes have become the forces of intensive research by analytical chemists, as electrodes
to transmit electrical signals or as sensors to detect concentrations of chemicals, biological materials.
Fascinating physical and chemical properties such as electrical conductance, high mechanical stiffness,
light weight, electron-spin resonance, field emission, electrochemical actuation, transistor behaviour,
piezoresistance, contact resistance, coulomb drag power generation, thermal conductivity, lumines-
cence, electrochemical bond expansion, opto-mechanical actuation and the possibilities of function-
alising carbon nanotubes to change their intrinsic properties are the reasons for their use as novel
biosensors.
The structure of nanotubes can be described as a rolled-up tabular shell of graphite sheet with
the carbon atoms covalently bound to their neighbours. The helicity of the shell categorises nanotubes

into metallic or semiconducting types. Based on the capture and promotion of electron transfer reac-
tion from analytics, ballistic conductivity of metallic nanotubes is extremely attractive. Semiconducting
nanotubes can be used as biosensors directly because these are optimised by changing the gate volt-
age. Hence, CNT electrodes have high sensitivity with low detection limit. CNT can be described as
single wall nanotubes (SWNT), double wall nanotubes (DWNT) or multi-wall nanotubes (MWNT).
CNT diameters range from about 1.4 nm to 60 nm and their length varies from microns to above one
centimeter.
To use nanotube electrodes for electro analytic purposes, proper conjugation strategies between
biological molecules such as enzymes, single stand DNA/RNA/PNA, antibodies, receptors and aptam-
ers need to be developed. Appropriate functionalisation methods and immobilisation of biomaterials
on nanotubes are critical since functional groups create defects in the nanotubes that will eventually
alter or degrade the intrinsic electrical properties of the nanotube. Nanotubes also have contact resist-
ance that should be minimised to provide the highest sensitivity when used as a sensor.
Carbon Nanotubes as Nanorobotics

Robots can do all kinds of physical and mechanical work more in various situations instead of man-
power. Nowadays, large-sized robots are used, and shrinking the robot size to nanoscale with carbon
nanotube is a fascinating advantage. Nanorobots can measure mass in femtogram ranges, sensing
forces at piconewton scales, etc., and with a provision for advanced features nanorobots can introduced
in army, intelligence, security, mechanochemical synthesis, etc.
7.7.7 Properties of Nanomaterials

The advent of nanotechnology has resulted in the increased use of nanomaterial-based products in
daily life. A significant increase in the surface-area-to-volume ratio at the nanoscale, giving rise to
novel and enhanced magnetic, mechanical, electronic, catalytic, conducting and optical properties of
nanomaterials, has made nanotechnology the most promising tool of this century.
Size
Nanostructures are the smallest of human-made things but the largest molecules of natural things and
nanometer is the magical point on the scale. Nanoscience and technology provide advanced materials
and systems which are intermediate between isolated atoms and bulk materials, with controlling of
transitional properties. Due to drastically increased surface-to-volume ratio, physical and chemical
properties are quite different from the bulk but tend to dominate at nanoscale.
Optical Properties
Due to large surface area, nanomaterials exhibit better optical properties. Luminescent nanocrystals,
termed as nanophosphors, with unique optical properties make them ideal for a wide spectrum of
applications ranging from flexible displays, lasers to biological imaging and therapeutic agents. For
example, NaYF4 is a highly multifunctional material with promising potential application in IR to
visible up conversion process. Silicon nanowires show strong photoluminescence.

7.50
Mechanical Properties
The mechanical behaviour of nanomaterial are found to be high strength, good ductility, superior
superplasticity, a low-friction coefficient, good thermal stability, high wear resistance, enhanced high-
cycle fatigue life and good corrosion resistance.
For example, tensile strength of carbon nanotube is approximately 20 times greater than the steel.
Magnetic Property
The magnetic property of a nanomaterial is very useful in biological systems. Due to unique proper-
ties and biocompatibility of nanoparticles, they easily combine with biological materials like proteins,
antibodies, enzymes, nucleus acids, etc.
Electrical Properties
Nanomaterials show electrical conductivity from semiconductors to superconductors, depending upon
the diameter and chirality of the molecules. Nano-structured conducting polymers have generated
much interest for their potential use in nanoelectronics.
For example, fullerenes are a class of allotropes of carbon, which are basically graphene sheets rolled
into tubes or spheres. They include the carbon nanotubes because of their mechanical strength and
electrical properties.
Carbon nanotubes have higher electrical conductivity than copper wires. The high electrical conduc-
tivity of nanotubes is mainly negligible amount of defects, so they possess low resistance.
Semiconductors
Most nanomaterials show semi-conductivity.
For example, carbon nanotubes, nanowires, MoS2, etc. They are used mainly as field-effect transistors,
p-n diodes, etc.
Superconductors
Some nanomaterials at low temperature show superconductivity.
For example, at normal temperature, NbS2 is metallic in nature, but at low temperature, it becomes a
superconductor.
Catalytic Activity
Due to the increasing surface area, nanomaterials act as a good catalyst in different homogeneous and
heterogeneous phases.
(i) For example,In 2O3-Ga2O3/Al2O3 nanocomposite used in selective catalytic reduction of nitric
oxide.
(ii) Platinum, a precious transition metal, which has outstanding catalytic and electrical proper-
ties and superior resistant characteristics to corrosion, has been widely applied in chemical,
petrochemical, pharmaceutical, electronic and automotive industries. Both platinum metal and

its alloys possess distinctive ability in catalysing partial oxidation, hydrogenation and dehydro-
genation of a variety of important molecules that are essential in many industrial processes.
7.7.8 Applications of Nanomaterials

Due to the advent of nanotechnology, applications of nanomaterials are quickly increasing by the day.
(i) Conducting polymers are widely employed as coatings conferring electrode systems, antifouling
properties and possibly activating electrocatalytic redox processes, conducting polymers for com-
mercial applications due to their high conductivity, easy preparation and environmental stability
have generated much interest for their potential use in nanoelectronic and organic conductors.
(ii) Aurum nanoparticles have been used for the enhancement of radiation effects on bovine aortic
endothelial cells of superficial X-ray radiation therapy and megavoltage electron radiation ther-
apy beans.
(iii) Nanoparticles are used as important catalysts in different chemical reactions.
(iv) Quantum dots and quantum wires have been used in the design of new super computers.
(v) Magnetic nanoparticles have wide application in medicine as drug transport and biosensor.
(vi) Carbon nanotubes having fascinating physical and chemical properties such as electrical con-
ductance, high mechanical stiffness, light weight, electron spin resonance field emission, elec-
trochemical actuation, transistor behaviour, piezoresistance, contact resistance, coulomb drag
power generation, thermal conductivity, luminescence, electrochemical bond expression, opto-
mechanical actuation,and the possibilities of function-aligned CNTs to change their intrinsic
properties are the reasons for their use in different ways as follows:
(a) They are used as a novel biosensor as enzyme electrodes, immunosensors, DNA, RNA, elec-
trodes, etc.
(b) Due to well-defined geometry, exceptional mechanical properties and extraordinary elec-
tric characteristics, among other outstanding physical properties of CNTs, they are qualified
for potential applications in the preparation of nanoelectronic circuits, nanoelectromechan-
ics systems, nanorobotics systems, structural elements, probes, grippers, tweezers, scissors,
actuators, bearings, syringes, switches, memories, diodes, transistors, logic gates, wires,
cables, position sensors, displacement sensors, circuits, thermal actuators, etc.
(c) They are used in field emission light devices for fluorescent displays.
(d) They act as a storage device in lithium batteries.
(e) From household uses to industries, space, army, medicine, agriculture and other fields, nano-
technology applications are employed.
7.8 LIQUID CRYSTALS

The study of liquid crystals began in 1888 with the observation of two distinct melting points to cho-
lesteryl benzoate by Friedrich Reinitzer.
Liquid crystals constitute a fascinating state of aggregation that is intermediate between the crys-
talline solid and the amorphous liquid. They exhibit rheological behaviour similar to those of liquids
and anisotropic physical properties similar to crystalline solids. Their dual nature and easy response
to electric, magnetic and surface forces have generated innumerable applications, which are extended

7.52
over diverse fields. The explosive growth of application of liquid crystals has generated immense inter-
est amongst the scientists and technologists to synthesise, characterise and understand the substances.
“Liquid crystal is formed in between the temperature of transition point and melting point, the cloudy
liquid shows double refraction. Hence the cloudy liquid is known as liquid crystal or mesomorphic state”.
“The liquid crystals are highly anisotropic fluids that exist between the boundaries of the solid and
conventional, isotropic liquid phase”.
Liquid crystals are made up of liquid and crystals. The term “liquid” is used because the tendency
to take the shape of the container and the word crystals is used because they still contain one or two
dimensional arrays.
7.8.1 Characteristics of Liquid Crystal Phase

The liquid crystalline state is the tendency of the mesogens (molecules) to point along the director
(common axis), which have no intrinsic order. The average alignment of the molecules in solid, liquid
crystal and liquid are shown in Figure 7.23.
Crystalline material possesses long range periodic order in three dimensions, but liquid crystals
do not possess order as a solid, since they have only some degree of alignment order. They show posi-
tional, orientational, bond orientational order, etc.
These are characterised by partial ordering, that is, one or more degrees of freedom, but not all
will have the long-range order.
Solid Liquid crystal Liquid
Figure 7.23 Average alignment of the molecules in solid, liquid crystal and liquid
7.8.2 Classification of Liquid Crystals

Liquid crystals may be divided into two broad categories, according to the principal means of breaking
down the complete order of the solid state.
(i) Thermotropic liquid crystals
(ii) Lyotropic liquid crystals
7.8.3 Thermotropic Liquid Crystals

These crystals are established solely by the adjustment of temperature. There are divided into three
types, namely nematic, cholesteric and smectic. These three classes are distinguished by the different
kinds of molecular order they exhibit.

Nematic Structure
The molecules in the nematic structure maintain a parallel or nearly parallel arrangement to each other
along the long molecular axes. They are mobile in three directions and can rotate about one axis. The
schematic representation of nematic liquid crystals are shown in Figure 7.24.
Properties
The nematic structure is the highest temperature mesophase in thermotropic liquid crystals. In this
structure, the molecules have no particular positional order, but tend to point vertically in same direc-
tion as shown in Figure 7.24. Like liquids, molecules are free to flow, their centre of mass positions are
randomly distributed, but they maintain long range directional or orientational order. The molecular
order of nematics is shown schematically in Figure 7.24.
As in any liquid, the molecules possess no translational order. There exists, however, a significant
degree of long-range orientational order.
^
n
Figure 7.24 Schematic representation of molecular order in nematic liquid crystals
Cholesteric Structure
The cholesteric-mesophase is a nematic type of liquid crystal except that it is made up of optically
active molecules.
The cholesteric liquid crystal phase is typically composed of nematic-mesogenic molecules con-
taining a chiral centre, which produces intermolecular forces that favour alignment between molecules
at a slight angle to one another. Helical structure and pitch of helix of the cholesteric liquid crystal are
shown in Figs. 7.25 (a) and (b) respectively.

7.54
Molecules
Sheets
Figure 7.25 (a) Helical structure of the cholesteric liquid crystal (b) Pitch of a helix of cholesteric liquid crystal
Properties
The cholesteric structure acquires a spontaneous twist about an axis normal to the preferred molecular
directions. The twist may be right-handed or left-handed depending on the molecular conformation.
In the structure of cholesteric phase, the local molecular ordering is identical to that of the nematic
phase. The chiral nematic phase exhibits chirality, hence it is called cholesteric phase. Chiral mol-
ecules those have no internal planes of symmetry can give cholesteric phase. This phase shows a spon-
taneous twisting of the molecular axis parallel to the director. This twist may be right- or left-handed
and depends on the molecular conformation. In the structure of cholesteric phase, the local molecular
ordering is identical to that of the nematic phase. Due to asymmetric packing, the finite twist angle
between adjacent molecules is a long range chiral order.
A cholesteric liquid crystal rotates the direction of linearly polarised light, and it is roughly 1,000 times
stronger than the activity of an ordinary optically active substance such as quartz, hence it is optically active.
The chiral pitch refers to the distance over which the liquid crystal molecule undergoes a full 360-degree twist.
Smectic Structure
The word “smectic” is derived from the Greek word which means soap. The origin is explained by
the fact that the thick, slippery substance often found at the bottom of a soap dish is actually a type of
smectic liquid crystal. Smectic liquid crystal is shown in Figure 7.26.

Properties
Another distinct mesophase of liquid crystal substance is the smectic state. In this phase, the molecules
show a degree of translational order which is not present in the nematic structure. In the smectic state,
molecules maintain the general orientational order of nematics, but also tend to align themselves in
layers or planes; the motion is restricted to within these planes, and separate planes are observed to
flow part each other. The increased order means that the smectic state is more “solid-like” than the
nematic state.
Figure 7.26 Smectic liquid crystal
On the basis of appearance under a polarising microscope, the miscibility with known phases and
X-ray scattering up to nine thermotropic smectic phases has been identified; these phases are labelled
by the chronological order of their discovery and designated as smectic A, B … I.
Some thermotropic liquid crystalline compounds are given in Table 7.4.
Table 7.4 Thermotropic liquid crystalline compounds

Name Formula Liquid
crystalline
range (°C )
1. Nematic Liquid Crystals
(a) P-methoxybenzylideneP1- N 21−47
N-butyl-aniline
H3 C O O C N O C4H9 n
(b) P-n-Hexyl-P1-cyano 14−28

Biphenyl n H13C6 O O CN
(Continued )

7.56
Name Formula Liquid
crystalline
range (°C )
2. Cholesteric Liquid
Crystal: CH3 CH3 145−179
Cholesterylnonanoate
CH3 C (CH2)3 CH
CH3 H CH3
O
H3C (CH2)7 C O
3. Smectic Liquid Crystals:

Smectic A: H 121−131
Ethyl P-(P1-Phenyl
benzalamine) benzoate O O C N O COOC2H5
Smectic B: H 77−116
Ethyl P-ethoxy
benzal- H5C2O O C N O CH CH COOC2H5
P1-aminocinnamate
Smectic C: 108−147
P-n-octyloxy benzoic acid n H17C8 O O COOH
Smectic D: 159−195
P1-n-Octadecyloxy-31-nitro n H37C18 O O O COOH
diphenyl-P-Carbonylic acid
O2N
Smectic E: 173−189
Diethyl p-terphenyl-P, C2H5OOC O O O COOC2H5
P11-Carbenylate
Smectic F: N 103−114
2-(P-Pentyl Phenyl)- n H11C5 O O O O C5H11 n
5-(P-Pentyloxy Phenyl) N
Pyrimidine
Smectic G: N 79−103
2-(P-Pentyl Phenyl)- n H11C5 O O O O C5H11 n
5-(Pentyloxy phenyl) N
Pyrimidine
Smectic H: H 40.5−51
4-Butyloxybenzal-4-
ethyl C4H9 O O C N O C2H5
Aniline

7.8.4 Lyotropic Liquid Crystals

Mixtures of two or more components that change phase with changes of concentration are called lyo-
tropic. These mesophases occur in concentrated solutions of rod-like molecules in an isotropic solvent.
The stability of these mesophases is as readily influenced by concentration of solute as by temperature.
Lyotropic mesophases are important in soaps, gels and colloids and are of great interest in biology.
Lyotropic crystal that has one of the components is an amphiphile (containing polargroup attached
to long hydrocarbon chains) and another is water. When a crystalline amphiphile is added to water,
several mesophases can be observed, ranging from a true solution to the crystal state.
For example, sodium stearate CH3(CH2)16COO –Na
CH2 O CO (CH2)16 CH3
CH O C O (CH2)16 CH3
a-Lecithin- O−
CH2 O P O CH2 CH2 N+(CH3)3
7.8.5 Chemical Properties of Liquid Crystals

According to chemical properties, liquid crystals can be broadly classified into two categories—ther-
motropic liquid crystals and lyotropic liquid crystals. These two are similar in many ways and are
distinguished by the mechanisms that drive their self-organisation.
Thermotropic liquid crystals are formed by increasing the temperature of a solid or by decreas-
ing the temperature of a liquid. Usually, thermotropic liquid crystal occurs with anisotropic disper-
sion forces of the molecules and their packing interactions. Generally, thermotropic liquid crystals
occur because of the presence of anisotropic dispersion forces between the molecules and packing
interactions.
According to their properties, thermotropic liquid crystals can be classified into two types.
Enantiotropic Liquid Crystals

Crystals that can be changed into the liquid crystal state from either lowering the temperature of a
liquid or raising of the temperature of a solid are called enantiotropic crystals.
Monotropic Liquid Crystals

Crystals that can only be changed into the liquid crystal state from any one of these but not both by
either an increase in the temperature of a solid or decrease in the temperature of a liquid are called
monotropic liquid crystals.
Lyotropic liquid crystals are formed with the influence of solvents, and not by changing of tem-
perature. They occur with the results of solvent-induced aggregation of the constituent mesogens into
micellar structures. Such crystals show amphiphilic properties, due to presence of both lyophilic and
lyophobic ends. With this property, in the presence of a solvent form as micellar structures, because
lyophobic ends will stay together and the lyophilic ends stay outward of the solution. By increasing the
concentration of solution and cooling the size of micellar structures increase eventually and separate
the newly formed liquid crystal from the solvent.

7.58
7.8.6 Applications of Liquid Crystals

Liquid crystal science had a major effect in different fields of science and technology. It is widely used
in research, medicine, display, radiation-sensors, thermometers, non-destructive testers, etc.
Displays
These are more desirable for displays than other materials due to lower power consumption and the
clarity of display in the presence of bright lights. The power requirements are low for digital display
and other mechanism to runs the large watches. The two most widely used displays in liquid crystal
displays are dynamic-scattering and field-effect crystals.
Radiation and Sensors

Cholesteric liquid crystals have been used in versatile and inexpensive radiation sensors, where an
impinging invisible radiation is registered as a colour change by local heating and the change of struc-
ture. These devices can be used with UV, infrared, microwave, ultrasonic, ionizing radiation transduc-
ers, etc., where there is a practical absorber in contact with the liquid crystals. Cholesteric liquid-crystal
films have been used as recording media in holograms.
Thermometers
The temperature-dependent variation in the colour of cholesteric liquid crystals has led to the use
of these substances in the measurement of temperature and gradients of temperature. A cholesteric
substance or a mixture of cholesteric substances always exhibits the same colour at the same tem-
perature; the colour is very sensitive to change in the ambient temperature. Cholesteric liquid-crystal
substances, when applied to the surface of the skin, have been used to locate veins, arteries, infections,
tumours and the foetal placenta which are warmer than the surrounding tissue.
Research Field
Nematic liquid crystals are the most useful research tools in the application of magnetic resonance.
Molecules that are dissolved in nematic liquid crystals due to anisotropic environment give a very
highly reduced nuclear magnetic resonance (NMR) spectrum. The analysis of spectra of molecules
in liquid crystal solvents yields information regarding the anisotropy of chemical shifts, chemical
structure, bond angles, bond lengths, direct magnetic dipole-dipole interactions, indirect spin-spin
couplings, molecular order and relaxation processes. Some liquid crystals have been used in chromato-
graphic separations, as solvents to direct the course of chemical reactions and to study molecular rear-
rangements and kinetics and as anisotropic host fluids for visible, UV/IR spectroscopy of molecules.
Non-destructive Testing
Cholesteric-nematic liquid crystals are colour-sensitive with temperature. This property can be used
for non-destructive testing.
Biological Systems and Medicine

Liquid crystals are used in medicine, as optical discs, full colour “electronic slides”, light modulators,
etc. Most biological systems exhibit the properties of liquid crystals. Considerable concentrations of

mesomorphic compounds have been found in many parts of the body, often as steroid or lipid deriva-
tives. A liquid crystal phase has been implicated in degenerative diseases; for example, atherosclerosis,
sickle-cell anaemia, etc. Living tissues such as muscle, tender, ovary, adrenal cortex, nerve etc., show
the optical birefringence properties that are characteristic of liquid crystals.
7.9 ABRASIVES
A material or a mineral that is used to shape, polish or finish a work surfaces through rubbing is an
abrasive. These are substances characterized by their hardness, and they are used to wear down softer
surfaces by cutting, grinding or polishing.
Abrasives are widely and very extensively used in a wide variety of industrial, domestic and
technological applications. This gives rise to a large variation in the physical, chemical composition,
as well as the shape of the abrasive. Common uses for abrasives include grinding, polishing, cut-
ting, drilling, sharpening, sanding, etc.
Examples:
(i) Housewives and farmers use abrasive stones to keep their kitchen knives and agricultural instru-
ments sharp.
(ii) Dentists use an abrasive powder when they clean teeth and to smooth down fillings.
(iii) Abrasives play important roles in various industries such as in grinding of wood into paper pulp,
cutting of stone into carved and surfaced structures, and sharpening of cutting-tools.
Abrasives are broadly divided into natural and artificial abrasives.
Some natural abrasives are calcite, emery, diamond, pumice, sand, corundum, garnet, etc.
Artificial abrasives include ceramic, corundum, glass powder, silicon carbide, zirconia alumina, etc.
7.9.1 Hardness of Abrasive
The most important quality of an abrasive is its hardness; it is measured roughly on Moh’s or Vicker’s
scale as shown in Figure 7.27. Commonly used natural and artificial abrasives in order of increasing
hardness are as follows:
Talc < gypsum or NaCl < calcite < fluorite < apatite < feldspar < quartz < topaz or emery < corun-
dum < diamond
Generally, artificial abrasives are superior in uniformity than natural abrasives, and consequently, they
are preferred in industrial grinding, etc.
Moh’s scale of
Hardness
1 2 3 4 5 6 7 8 9 10
Talc Calcite Apatite Quartz Corundum
Gypsum Fluorite Feldspar Topaz Diamond
Figure 7.27 Moh’s scale of hardness

7.60
7.9.2 Natural Abrasives
Some of the natural abrasives are as follows:
(i) Diamond: It is a crystallised carbon having highest hardness; hence, it can cut into the surface
of any other substances, whereas only another diamond can scratch with a diamond. It is chemi-
cally highly inactive and not attacked by acids, alkalis or fused potassium chlorate. Diamonds
that are off-colour or otherwise faulty are called borts. Black diamond from Brazil is called car-
bonado and has no value for jewellery. Borts and carbonado are used in drill points as saw-teeth
for cutting rocks, stones, or grinding wheels, dressers, and in operations, where great hardness is
required.
(ii) Corundum: It is crystallised aluminium oxide (Al2O3) and comes next to diamond in hardness.
Corundum is not of gem quality but finds use as abrasives for grinding glasses, gems, lenses,
metals and metal-cutting.
(iii) Emery: Emery is fine-grained, opaque, massive mineral and dark grey to black in colour. It is
found mainly in Greece. It has an aggregate of 55%–75% crystalline alumina, 20%–40% mag-
netite (Fe3O4) and about 12% of other minerals of which the chief is tourmaline. Its hardness is
about eight on Moh’s scale. The grinding power of emery almost depends on the proportion of
alumina it contains and on the effects of the other ingredients in determining true hardness of this
mineral. Emery is used as tip bits of cutting, drilling tools, etc. Artificial emery used for buffing
and polishing is a graded combination of alumina and magnetite.
(iv) Garnets: They are trisilicates of alumina, magnesia and ferrous oxide. The common garnet used
as an abrasive is a complex of calcium–aluminium–iron silicates with the approximate formula:
Ca3Al2(SiO4)3.Ca3Fe2(SiO4)3.Fe3Al2(SiO4)3
Hardness of garnets ranges from 6.0 to 7.5 on Moh’s scale. Garnets are too soft for grinding steel
and iron, but when glued to paper or cloth, they are used for finishing hardwoods. They are also
used for bearing pivots in watches, glass grinding, and polishing metals.
(v)
Quartz: Quartz is composed of silica (SiO2), which is impure and grey in colour. Hydrated form
of quartz is the abrasive flint that is used on good quality sand paper. It is almost as hard as garnet;
it is used for grinding, and other sharpening stones are cut from sandstone. This rock consists of
quartz particles cemented together with feldspars, clays, carbonates and other minerals. It is used
for grinding floor, pigments, ores, etc.
7.9.3 Artificial Abrasives
Artificial abrasives are as follows:
(i) Carborundum or Silicon Carbide (SiC): Carborundum is a bluish black crystallised artificial
mineral with hardness between corundum and diamond. It is made by subjecting a mixture of
silica and carbon (coke or coal) to high temperature (1650°C–2200°C) in an electric furnace.
SiO2 + 3C → SiC + 2CO ↑
It is very hard, and in Moh’s scale, the hardness is about 9.3 and chemically inactive and can with-
stand the action of high temperature without damage, but it is not tough and is somewhat brittle.
It is mainly used in cutting-wheels, abrasive papers and cloths. It is extensively used for grinding
of materials of low tensile strength like cast iron, brass, bronze, porcelain, marble, finishing of
leather, glass and optical grinding of lenses.

(ii) Alundum (Al2O3): It is prepared by subjecting a mixture of calcined bauxite, coke and iron to
high temperature, that is, about 4000°C in an electric arc furnace. The iron, titanium and silica
impurities settle down at the bottom of the furnace, and after solidification, the hard crystalline
alumina is separated, crushed and grounded. It is sold under zero number of trade names includ-
ing Aloxite. Alundum or artificial corundum is not as hard as carborundum but is also less brit-
tle and tougher. It is, therefore, used in preference to carborundum for grinding hard steels and
other materials of high tensile strength or abrasive papers and cloths; it is used for finishing wood
works.
(iii) Boron carbide or Norbide (B4C): It is inert and one of the hardest artificial abrasives having
hardness about 9 in Moh’s scale. It is made by heating boron oxide with coke in an electric fur-
nace to approximately 2700°C.
2B2O3 + 7C → B4C + 6CO ↑
It is used on hard materials for making grinding dies and for cutting and sharpening hard, high-speed
tools.

1. are good conductors.
[Ans.: Metals]
2. At absolute zero temperature, solid semiconductors act as perfect .
[Ans.: insulators]
3. are important semiconductors.
[Ans.: Si and Ge]
4. The materials which are used to prevent the loss of electricity through certain parts in an
electrical systems are
[Ans.: dielectrics]
5. Semiconductors that have defects due to impurity are semiconductors.
[Ans.: extrinsic]
6. The addition of Group-15 elements to Group-14 elements gives semiconductors.
[Ans.: n-Type]
7. At absolute temperature, the of metal becomes zero.
[Ans.: electrical resistance]
8. The phenomena of metals that become perfect conductors with zero resistivity at absolute
temperature is known as .
[Ans.: super conductors]
9. is the material possessing adhesive and cohesive properties and capable of bonding
material.
[Ans.: Cement]

7.62
10. Natural cement is made by calcination of a naturally occurring limestone.

[Ans.: argillaceous]
11. , an English mason, invented the cement.
[Ans.: Aspdin Joseph]
12. cement is the oldest cement invented by Romans.
[Ans.: Puzzolana]
13. cement resembled in colour and hardness to Portland stone.
[Ans.: Portland]
14. The formula of gypsum is .
[Ans.: CaSO4 ⋅ 2H2O]
15. acts as a retarding agent for early setting of cement
[Ans.: Gypsum]
16. The process of solidification of cement consists and .
[Ans.: setting, hardening]
17. Calcarious material is rich in .
[Ans.: lime]
Al O
18. According to ISI specifications of cement, the ratio of 2 3 shall not be less than .
Fe2 O3
[Ans.: 0.66]
19. Plaster of Paris setting and hardening can initiate as well as hasten crystallisation.
[Ans.: alums or alkali sulphur]
20. are ceramic materials that can withstand high temperatures.
[Ans.: Refractories]
21. Al2O3 and SiO2 are refractories.
[Ans.: Acidic]
22. are the examples of basic refractories.
[Ans.: CaO, MgO]
23. Introducing the lubricant to reduce frictional resistance between the moving or sliding surfaces
is known as .
[Ans.: lubrication]
24. Fluid film lubrication mechanism is also known as .
[Ans.: Thick-film or Hydrodynamic]
25. oils are considered to be satisfactory lubricants for fluid film lubrication.
[Ans.: Hydrocarbon]
26. Improving the properties of petroleum by incorporating specific additives is called .
[Ans.: blended oils]

27. Calcium-based greases are emulsions of petroleum oils with .

[Ans.: calcium soaps]
28. The most usual solid lubricants are .
[Ans.: graphite and molybdenum disulphide]
29. When graphite is dispersed in oil, it is called V.
[Ans.: oil dag]
30. is the property of a liquid or fluid by virtue of which it offers resistance to its over flow.
[Ans.: viscosity]
31. Primary explosives are also known as .
[Ans.: detonators]
32. Propellants are known as .
[Ans.: low explosives]
33. A mixture of 75% potassium nitrate, 15% charcoal and 10% sulphur is .
[Ans.: gun-powder]
34. Mixture of TNT and ammonium nitrate is .
[Ans.: amatol]
35. Principal ingredient in dynamites are .
[Ans.: nitroglycerine]
36. is a thin, water-proof canvas length tube containing gunpowder or (TNT).
[Ans.: A fuse]
37. A good propellant should have .
[Ans.: high specific impulse]
38. is the energy liberated per unit mass of the explosives.
[Ans.: Explosive strength]
39. explosives have higher energy content than the primary explosives.
[Ans.: High]
40. is an extremely powerful, sensitive and standard military explosive.
[Ans.: PETN]
41. TEM means .
[Ans.: transmission electron microscopy]
42. SEM means .
[Ans.: scanning electron microscopy]
43. XRD means
[Ans.: X-ray diffraction]

7.64
44. crystals are highly anisotropic fluids that exists between the boundaries of the solid
and liquid phase.
[Ans.: Liquid]
45. crystals move in three directions and can rotate about one axis.
[Ans.: Nematic]
46. crystal structure is optically active.
[Ans.: Cholesteric]
47. Lyotropic crystal has and water.
[Ans.: amphiphile]
48. mesophases are important in soaps, gels and colloids.
[Ans.: Lyotropic]
49. are the natural abrasives.
[Ans.: Diamond, corundum, emery and quartz]
50. Carborundum Norbide are abrasives.
[Ans.: Artificial]
51. Hardness of an abrasive is measured roughly on or scales.
[Ans.: Moh’s, Vicker’s]
7.10.2 Multiple-choice questions

1. Which of the following compounds act as super conductors?
(a) YBa2Cu3O7 (b) Bi2Ca2Sr2Cu3O10
(c) Tl2Ca2Ba2Cu3O10 (d) All the above
[Ans.: d]
2. Doping of Germanium with Group-13 elements gives
(a) n-type semiconductors (b) p-type semiconductor
(c) Super conductor (d) Conductor
[Ans.: b]
3. Hydration of cement produces small volume changes known as
(a) Dehydration (b) Soundness
(c) Calcination (d) Hardening
[Ans.: b]
4. The formula for plaster of Paris is
(a) CaSO4 ⋅ H2O (b) CaSO4 ⋅ 3H2O
(c) CaSO4 ⋅ 2H2O (d) CaSO4
[Ans.: c]

5. The formula for tricalcium alumina ferrite

(a) 4CaO ⋅ Al2O3 ⋅ Fe2O3 (b) 4CaO ⋅ Fe2O3
(c) CaO ⋅ Al2O3 (d) Al
[Ans.: a]
6. Which of the following is responsible for high ultimate strength in cement?
(a) C3S (b) C2S
(c) C3A (d) C4AF
[Ans.: a]
7. The major component of Portland cement is
(a) MgO (b) C3A
(c) CaO (d) C2A
[Ans.: c]
8. Tobermonite gel is chemically
(a) Hydrated tricalcium aluminate (b) Hydrated tricalcium silicate
(c) Hydrated dicalcium ferrite (d) Hydrated dicalcium silicate
[Ans.: b]
9. The argillaceous material is rich in
(a) Lime (b) Silica
(c) Stone (d) Ferriferrite
[Ans.: b]
10. According to ISI specification, insoluble residue should not exceed
(a) 5% (b) 3%
(c) 10% (d) 2%
[Ans.: d]
11. Any material that can withstand high temperatures without either breaking or suffering a defor-
mation in shape is called
(a) Dielectric (b) Thermal insulator
(c) Refractory (d) Insulator
[Ans.: c]
12. In acidic environment, refractory should not preferably be
(a) Acidic (b) Basic
(c) Neutral (d) None of these
[Ans.: b]
13. Alumina is an example of
(a) Acidic refractory (b) Basic refractory
(c) Neutral refractory (d) None of these
[Ans.: a]

7.66
14. High resistance to spalling is shown by

(a) Magnesia refractory (b) Dolomite refractory
(c) Alumina refractory (d) Lime refractory
[Ans.: c]
15. Breaking, cracking or peeling off a refractory material under high temperature, is called
(a) Thermal expansion (b) Spalling
(c) Fusion (d) Chemical cracking
[Ans.: b]
16. A refractory material, generally obtained from bauxite
(a) Fire clay (b) Dolomite
(c) Chromite (d) Alumina
[Ans.: d]
17. Which of the following is a neutral refractory?
Dolomite (b) Graphite
(c) Silica (d) Magnesia
[Ans.: b]
18. Porosity in a refractory brick, generally, increases
(a) Density (b) Resistance to spalling
(c) Strength (d) Melting point
[Ans.: b]
19. A good refractory material must
(a) Be chemically inactive in use
(b) Possess low softening temperature
(c) Undergo spalling
(d) Possess high thermal expansion
[Ans.: a]
20. Spalling of refractory material can be reduced by
(a) Rapid changes in temperature
(b) Using porous refractory material
(c) Using high coefficient of expansion refractory material
(d) Using good thermal conductivity refractory material
[Ans.: b]
21. Good thermal conductivity of a refractory material is desirable if it is to be used in the construc-
tion of walls of a
(a) Blast furnace (b) Muffle furnace
(c) Reverberatory furnace (d) All the above
[Ans.: b]
22. The porosity of a refractory brick increases its
(a) Strength (b) Abrasion resistance
(c) Corrosion resistance (d) Resistance to thermal spalling
[Ans.: d]

23. Which one of the following refractories cannot be used in oxidising conditions?
(a) Dolomite bricks (b) Magnesite bricks
(c) Carbon bricks (d) Silica bricks
[Ans.: c]
24. Which one of the following refractories is neutral in character?
(a) Dolomite bricks (b) Silica bricks
(c) Chromite bricks (d) Fire clay bricks
[Ans.: c]
25. Which one of the following refractories is used in nuclear engineering as modulator?
(a) Chromite bricks (b) Carborundum
(c) Beryllia bricks (d) Fire clay bricks
[Ans.: c]
26. An example of acid refractory is
(a) Chromite (b) Dolomite
(c) Silica (d) Magnesite
[Ans.: c]
27. Silica bricks belong to
(a) Acidic refractories (b) Basic refractories
(c) Neutral refractories (d) None of these
[Ans.: a]
28. High resistance to spalling is shown by
(a) Magnesia refractory (b) Dolomite refractory
(c) Alumina refractory (d) Lime refractory
[Ans.: c]
29. How does the porosity of refractory brick affect its mechanical strength?
(a) Increases (b) Decreases
(c) Slightly change (d) No change
[Ans.: b]
30. Refractoriness is measured by using
(a) Refractoriness under load (RUL) test (b) Seger cone test
(c) Conductivity test (d) Spalling test
[Ans.: b]
31. Refractoriness under load is determined by
(a) RUL test (b) Seger cone test
(c) Conductivity test (d) None of these
[Ans.: a]
32. A refractory should be
(a) Chemically active (b) Chemically inactive
(c) Chemically unstable (d) None of these
[Ans.: b]

7.68
33. Formula for porosity

D −W W −D
(a) P = × 100 (b) P = × 100
W−A A −W
D −W W −D
(c) P = × 100 (d) P = × 100
A −W W−A
[Ans.: d]
W −D
34. From the formula P = × 100, W indicates
W−A
(a) Weight of saturated specimen
(b) Weight of dry specimen
(c) Weight of dry specimen in water
(d) Weight of saturated specimen in water
[Ans.: a]
35. Silica bricks are used in
(a) Roofs of open hearth furnaces (b) Coke oven walls
(c) Roofs of electric furnaces (d) All the above
[Ans.: d]
36. Refractory used in the linings of port land cement rotary kilns are
(a) Silica bricks (b) Fire clay bricks
(c) High-alumina bricks (d) Magnesite bricks
[Ans.: c]
37. Magnesite bricks are used in
(a) Acidic refractories (b) Basic refractories
(c) Neutral refractories (d) None of these
[Ans.: b]
38. Refractories used in the construction of electrodes are
(a) Magnesite (b) Alumina
(c) Graphite (d) Chromite
[Ans.: c]
39. Refractories used to separate acidic and basic refractory lining are
(a) Chromite bricks (b) Alumina bricks
(c) Graphite (d) All the above
[Ans.: a]
40. Refractories used in high frequency electric furnaces are
(a) Eryllia bricks (b) Zirconia bricks
(c) Carborundum (d) None of these
[Ans.: b]
41. Higher the porosity of refractory,
(a) Higher the thermal conductivity (b) Higher the refractoriness
(c) Lesser is its thermal conductivity (d) None of these
[Ans.: a]

42. The cause of thermal spalling is

(a) Porosity (b) Rapid change of furnace temperature
(c) Maintaining low temperature (d) None of these
[Ans.: b]
43. Which are the most widely used refractories?
(a) Fire clay bricks (b) Alumina bricks
(c) Chromite bricks (d) None of these
[Ans.: a]
44. High alumina bricks contain about 50–80% Al2O3 and 40–45%
(a) MgO (b) CaO
(c) SiO2 (d) Carbon
[Ans.: c]
45. A refractory lining in a blast furnace should possess
(a) Low thermal conductivity (b) High thermal conductivity
(c) Medium thermal conductivity (d) None of these
[Ans.: a]
46. A lubricant is used with the objective of
(a) Increasing frictional heat
(b) Increasing resistance
(c) Decreasing frictional resistance
(d) Providing direct contact between rubbing surfaces
[Ans.: c]
47. A lubricant should possess high
(a) Volatility (b) Acidity
(c) Oiliness (d) None of these
[Ans.: c]
48. A lubricant is primarily used to prevent
(a) Corrosion of metals (b) Wearing out of rubbing metallic surfaces
(c) Oxidation of metal (d) Reduction of metals
[Ans.: b]
49. A suitable lubricant for watches is
(a) Grease (b) Graphite
(c) Hazel-nut oil (d) Palm oil
[Ans.: c]
50. A good lubricant should have
(a) Low viscosity index (b) High viscosity index
(c) Low fire point (d) High
[Ans.: b]

7.70
51. The lubricant used in a machine working at low temperature should possess
(a) High pour point (b) Low flash point
(c) High cloud point (d) Low pour point
[Ans.: d]
52. The capacity of an oil to stick on to the surfaces of machine parts under conditions of heavy load
is called
(a) Volatility (b) Oiliness
(c) Acid value (d) Flash point
[Ans.: b]
53. Oiliness is the least in case of
(a) Greases (b) Mineral oils
(c) Animal oils (d) Palm oil
[Ans.: b]
54. In case of liquid lubricants, generally
(a) Flash point is higher than the fire point
(b) Fire point is higher than the flash point
(c) Fire point is lower than the flash point
(d) Flash and fire points are identical
[Ans.: b]
55. When the resistance to movement of sliding parts is only due to the internal resistance between
the lubricant itself, the lubrication is called
(a) Fluid film (b) Boundary
(c) Thin film (d) Extreme pressure
[Ans.: a]
56. Mineral oils are
(a) Very costly (b) Poor in oiliness
(c) Unstable (d) Easily oxidised
[Ans.: b]
57. Animal and vegetable oils are
(a) Very cheap (b) Not oxidised easily
(c) Not thickened in use (d) Good in oiliness
[Ans.: d]
58. Greases are not used to lubricate
(a) Rail axle boxes (b) Bearings working at high temperatures
(c) Gears (d) Delicate instruments
[Ans.: d]
59. Machines operating under high temperatures and loads are best lubricated by
(a) Mineral oils (b) Solid lubricants
(c) Greases (d) Animal oils
[Ans.: b]

60. When graphite is dispersed in oil, it is called

(a) Grease (b) Aqua dag
(c) Oil dag (d) Blended oil
[Ans.: c]
61. Pick the odd one out.
(a) Viscosity (b) Carbon residue
(c) Pour-point (d) RUL test
[Ans.: d]
62. The single most important property of lubricating oil is its
(a) Fire point (b) Cloud point
(c) Oiliness (d) Viscosity index
[Ans.: d]
63. What is the type of lubrication involved in delicate machines like watches?
(a) Fluid-film (b) Thin film
(c) Boundary (d) Extreme pressure
[Ans.: a]
64. What are the type of oils suitable for thick film lubrication?
(a) Animal oils (b) Vegetable oils
(c) Blended oils (d) Hydro carbon oils
[Ans.: d]
65. One of the important properties of greases is
(a) Consistency (b) Oiliness
(c) Thermal stability (d) All the above
[Ans.: a]
66. The quality of grease will be measured by using
(a) Refractometer (b) Caliometer
(c) Penetrometer (d) Vaporimeter
[Ans.: c]
67. Precipitation number indicates
(a) Ash content (b) Asphalt
(c) Moisture (d) None of these
[Ans.: b]
68. The aromatic content in the lubricant is determined by
(a) Saponification number (b) Aniline point
(c) Precipitation number (d) Neutralisation number
[Ans.: b]
69. The estimation of carbon residue is generally carried out by
(a) Grease penetrometer (b) Conrodson’s apparatus
(c) Vapourimeter (d) None of these
[Ans.: b]

7.72
70. A good lubricant should deposit

(a) More amount of carbon (b) Least amount of carbon
(c) more amount of ash (d) None of these
[Ans.: b]
71. The oiliness of a lubricant will be increased by the addition of
(a) Mineral (b) Vegetable or animal oil
(c) grease (d) Solid lubricants
[Ans.: b]
72. The diameter of the jet in Redwood No. 1 viscometer is
(a) 1.42 mm (b) 1.62 mm
(c) 3.4 mm (d) 3.6 mm
[Ans.: b]
73. The jet borelength in Redwood No. 2 viscometer is
(a) 5 mm (b) 10 mm
(c) 15 mm (d) 20 mm
[Ans.: b]
74. The formula used to measure the viscosity index is
L −V U −L
(a) VI = ×100 (b) VI = ×100
L −U V −L
L −U L −V
(c) VI = ×100 (d) VI = ×100
L−H H −L
[Ans.: c]
75. Gulf oils are called
(a) L–Oils (b) H – Oils
(c) L and H Oils (d) None of these
[Ans.: a]
76. The unit of viscosity is
(a) Calorie (b) Eta
(c) Poise (d) Seconds
[Ans.: c]
77. The force per unit area F = is
(a) h/d v (b) h ∝ v/ d
(c)h/d/v (d) h ∝ d/v
[Ans.: b]
78. The amount of oil collected during viscosity determination using redwood viscosity is
(a) 50 ml (b) 60 ml
(c) 200 ml (d) 400 ml
[Ans.: a]

79. Absolute viscosity will be calculated by using the formula

(a) Kinematic viscosity × density (b) Commercial viscosity × density
(c) Commercial viscosity/density (d) None of these
[Ans.: a]
80. Abel’s apparatus is used to determine
(a) Carbon residue (b) Consistency
(c) Viscosity (d) Flash point
[Ans.: d]
81. Graphite and molebdenim disulphide are
(a) Synthetic lubricants (b) Antioscidants
(c) Solid lubricants (d) Additives
[Ans.: c]
82. The usual coefficient of friction between solid lubricants is between
(a) 0.001 and 0.01 (b) 0.005 and 0.05
(c) 0.005 and 0.007 (d) 0.005 and 0.01
[Ans.: d]
83. Hexanol is a
(a) Viscosity index improver (b) Thickness
(c) Corrosion prevention (d) Oiliness carrier
[Ans.: a]
84. Lubricants also act as
(a) healing agent (b) Corrosion preventer
(c) Cooling medium (d) All the above
[Ans.: d]
85. The coefficient of friction in fluid film lubrication is
(a) 0.01 to 0.03 (b) 0.01 to 0.3
(c) 0.01 to 0.05 (d) 0.001 to 0.03
[Ans.: d]
86. Tropex is a mixture of
(a) 40% RDX, 40% TNT and 20% Al powder
(b) TNT and PETN
(c) 70% Tetryl and 30% TNT
(d) None
[Ans.: a]
87. Ammonium nitrate is a
(a) Low single compound explosive
(b) High single compound explosive
(a) and (b)
(d) None of these
[Ans.: b]

7.74
88. Lead azide is a

(a) High explosive (b) Low explosive
(c) Primary explosive (d) Propellant
[Ans.: c]
89. Gun powder is
(a) Low explosive (b) High explosive
(c) Blasting fuse (d) All the above
[Ans.: a]
90. A propellant used in rocket engine is
(a) Fuel (b) oxidant
(c) None of these (d) (a) and (b)
[Ans.: d]
91. The term nano means
(a) One billionth of a kilometer (b) One billionth of a meter
(c) One billionth of an inch (d) One billionth of a millimeter
[Ans.: b]
92. Who is the father of nanoscience?
(a) Rutherford (b) Richard Feynmen
(c) Newton (d) Curie
[Ans.: b]
93. Which of the following nanomaterials act as sensors of gases like NO2 and NH3 on the basis of
increase in electrical conductivity?
(a) Carbon nanotubes (b) Thin film
(c) ZnO (d) Palladium
[Ans.: a]
94. The nanotubes of MoS2 and CoS2 are used as
(a) semiconductors (b) Insulators
(c) Storage device (d) Solid lubricants
[Ans.: d]
95. Which of the following nanowires shows photoluminescence?
(a) Zinc oxide (b) Palladium
(c) Silicone (d) MoS2
[Ans.: c]
96. Which nanomaterial effectively catalyses hydrogenation of oil?
(a) Rane CuO (b) Rane pd
(c) Rane Ni (d) Rane ZnO
[Ans.: c]
97. Nanowires and nanotubes are in nanoscale.
(a) One dimensional (b) Two dimensional
(c) Three dimensional (d) None of these
[Ans.: b]

98. type of nanomaterials has a three-dimensional structure.

(a) Thin film (b) Nanowires
(c) Quantum dots (d) All the above
[Ans.: c]
99. According to molecular arrangements, nanomaterials are broadly divided into types.
(a) Two (b) Three
(c) Four (d) Many
[Ans.: b]
100. Thermotropic liquid crystals are
(a) nantiotropic (b) Monotropic
(c) (a) and (b) (d) None of these
[Ans.: c]
101. Crystals which can change into the liquid crystal state from either lowering temperature of a
liquid of raising of the temperature of solid are called
(a) Nantiotropic (b) Monotropic
(c) Nematic (d) All the above
[Ans.: a]
102. Which mesophase is a nematic type of liquid crystal and optically active?
(a) Meiotic (b) Cholesteric
(c) a and b (d) None of these
[Ans.: b]
103. The source of energy in nuclear fuel is due to
(a) Chemical reaction (b) Nuclear reaction
(c) Nuclear fission (d) Nuclear fusion
[Ans.: c]
104. Hardness of an abrasive can be measured with
(a) Rictor scale (b) pH scale
(c) Moh’s scale (d) None of these
[Ans.: c]
105. Diamond is
(a) Natural abrasive (b) Crystallised carbon
(c) Inactive to acids, alkalis (d) All of these
[Ans.: d]
106. The following are natural abrasives
(a) Diamond (b) Emery
(c) Garnet (d) All of these
[Ans.: d]
107. The following are artificial abrasives
(a) Carborundum (b) Alundum
(c) Boron carbide (d) All of these
[Ans.: d]

7.76

1. Define semiconductors.
Ans.: Semiconductors are those solids which are perfect insulators at absolute zero, but con-
duct electric current at room temperature and lies between that of a good conductor and
insulator.
2. What is meant by doping?
Ans.: The addition of some impurities to pure semiconductors to enhance conductivity is known
as doping.
3. Explain intrinsic semiconductors and conduction.
Ans.: At normal temperature and pressure, pure silicon and germanium are insulators, because
no electron is free and all the electrons are fixed in covalent bonds. However, at high tem-
perature, covalent bonds are broken and the electrons so released become free to move in
the crystal and thus conduct electric current. This type of conduction is known as intrinsic
conduction and the conductors are intrinsic semiconductors. It will happen in the crystal
without adding any external substance.
4. Classify extrinsic semiconductors with examples.
Ans.: n-type semiconductors: Upon addition of trace amount of group 15 elements like phos-
phorous and arsenic to pure germanium, n-type semiconductors are formed. Extra elec-
trons come from the impurity and conduct the electricity.
P-type semiconductors: Upon addition of trace amount of group 13 elements like boron
to pure germanium, p-type semiconductors are formed. Formed positive holes by doping
are responsible for conduction.
5. Define superconductors and give examples.
Ans.: Materials which show zero electrical resistance at absolute zero temperature are super
conductors and the state is superconductivity.
Ex: YBe2Cu3O7, Bi2Ca2Sr2Cu3O10.
6. Who invented the magnet and how was it named?
Ans.: More than 2,000 years ago, the ancient Greeks first discovered a mineral that attracts things made
of iron. This mineral was found in Magnesia, a part of Turkey; hence, it was named magnet.
7. Give the classifications of magnetic materials.
Ans.: (i) Diamagnetic
(ii) Paramagnetic
(iii) Ferromagnetic
(iv) Ferrimagnetic
(v) Anti-ferromagnetic materials.
8. Give examples of diamagnetic materials.
Ans.: Copper, silver, gold, etc., are the examples of diamagnetic materials.
9. Define hysteresis.
Ans.: Retaining of magnetic properties after the removal of external magnetic field is known as
hysteresis.

10. What is meant by magnetic domain?

Ans.: In ferro and ferromagnetic materials, below Curie temperature, a large number of atom
moments is aligned parallels as a small volume region. These are known as magnetic domains.
11. Give the broad classifications of cement.
Ans.: Cement is broadly classified into natural, puzzolana, slag and Portland cement.
12. Who invented puzzolana cement and how it can be prepared?
Ans.: Puzzolana cement is the oldest cement invented by Romans. This is prepared by mixing of
natural puzzolana and slaked lime.
13. What is known as the magic powder and what are its main ingredients?
Ans.: Portland cement is also known as magic powder. It primarily consists of lime, silica, alu-
mina and iron.
14. What is the function of iron oxide in cement?
Ans.: Iron oxide provides colour, strength and hardness to the cement.
15. Give the equation for final setting and hardening of the cement.
Ans.: 2C3S + 6H2O → C3S2 ⋅ 3H2O + 3Ca(OH)2 + 500 kj/kg
Tricalcium silicate Tobermonitegel crystalline
calcium hydroxide
16. What are the theories that explain the hardening of the cement?
Ans.: Colloidal theory by Michaels and crystalline theory by Le Chatelier explain the hardening
of the cement.
17. What are the chemical constituents present in Portland cement?
Ans.: Tricalcium silicate (3CaO SiO2), dicalcium silicate (2CaO SiO2), tricalcium aluminate
(3CaOAl2O3) and tetracalcium alumino ferrite (4CaOAl2O3Fe2O3).
18. What is the main function of gypsum in cement?
Ans.: The presence of gypsum in the cement helps to retard the speed of the initial set, due to
the formation of insoluble calcium sulphoaluminate. This does not show tendency to rapid
hydration.
C3A + Gypsum → Tricalcium sulphoaluminate
19. Define a refractory.
Ans.: Refractories are ceramic materials that can withstand high temperatures as well as abra-
sive and corrosive actions of molten metals, slags and gases without deformation.
20. Explain any two important properties of a refractory.
Ans.: Refractoriness: Refractoriness is the ability of a material to withstand heat without appre-
ciable deformation.
Dimension stability: It is the resistance of a material to any volume changes, which may occur on
its exposure to high temperature and load.
21. Give porosity equation.
W −D
Ans.: P = ×100
W−A

7.78
where W = weight of saturated specimen

D = weight of dry specimen
A = weight of saturated specimen submerged in water
A good refractory should have low porosity.
22. Give examples of all types of refractories.
Ans.: Acidic refractories: Alumina, silica
Basic refractories: Magnesite, dolomite
Neutral refractories: Graphite, zirconia
23. What is meant by permeability?
Ans.: Permeability is a measure of rate of diffusion of gases, liquids and molten solids through
a refractory. It depends upon the size and number of connected pores. Permeability will
increase with temperature.
24. What are the uses of magnesite bricks?
Ans.: Magnesite bricks are used in open hearth furnaces, reverberatory furnaces, rotary kilns
and refining furnaces.
25. What is the test used to determine the refractoriness of the refractory?
Ans.: Seger cone test.
26. Define thermal spalling.
Ans.: Breaking, cracking, peeling off or fracturing of a refractory brick under high temperature
is known as thermal spalling.
27. Define lubricants.
Ans.: The process of reducing frictional resistance between moving or sliding surfaces by the
introduction of lubricants in between them is called lubrication.
28. What are the main mechanisms of lubrication?
Ans.: (i) Fluid film or thick film lubrication
(ii) Boundary or thin film lubrication
(iii) Extreme pressure lubrication
29. What are the main types of lubricants?
Ans.: On the basis of physical state, lubricants are classified into liquid lubricants, greases or
semisolid lubricants and solid lubricants.
30. Give some examples of greases.
Ans.: Calcium-based greases, sodium-based greases, lithium-based greases and axle greases.
31. Why does graphite act as a good lubricant?
Ans.: Due to its unique layer structure, graphite acts as a good lubricant.
32. Explain oildag and aquadag.
Ans.: In the presence of tannin, the dispersion of graphite in oil is called oildag and dispersion
of graphite in water is called aquadag.
33. What are the units of absolute viscosity?
Ans.: Eta (h) or poise or centipoise are units for absolute viscosity.

34. Give the equation for viscosity index.

VL × VX
Ans.: Viscosity index = × 100
VL − VH
35. Name the different types of viscometers.

Ans.: Redwood viscometers, Engler’s viscometers, Saybolt viscometers, U-tube viscometers,
etc.
36. How can we measure the mechanical stability of a lubricant?
Ans.: Four-balls extreme pressure is the one of the important mechanical tests to judge the
mechanical stability of a lubricant under load.
37. Give some important properties of explosives.
Ans.: Explosive strength, velocity of detonation, sensitivity, brisance, etc., are some important
properties of explosives.
38. Give some examples for detonators.
Ans.: Lead azide, mercury fulminate, tetracene and diazodinitro phenol.
39. What is the main difference between detonators and propellants?
Ans.: Detonators are highly sensitive and can explode with slight shock or fire, whereas propel-
lants burn simply but do not explode.
40. How are high explosives classified?
Ans.: Depending on the components present on the explosives, they are classified into single
compound explosives, binary explosives, plastic explosives and dynamites.
41. What is the main component present in the binary explosives? Give some examples.
Ans.: T NT is the main component present in binary explosives. Examples are amatol, pentolite,
tetrytol, tropex, etc.
42. Define blasting fuses.
Ans.: A fuse is a thin water-proof canvas length of tube containing gunpowder, arranged to burn
at a given speed for setting of charges of explosives.
43. Define rocket propellants and give their classification.
Ans.: A rocket propellant is high oxygen containing fuel and oxidant, whose combustion takes
place in a definite and controlled manner with the evolution of a huge volume of a gas.
Propellants are mainly classified into solid and liquid propellants.
44. What are the advantages of liquid propellants?
Ans.: Liquid propellants possess many advantages over solid propellants because they are versa-
tile and the engine using them can be checked and calibrated more easily. The engine using
the liquid propellant is quite delicate and cannot withstand any rough handling.
45. Define a nanometre.

Ans.: Nanometre is the one-billionth of a metre, 1 nm = 1/1000000000 metre = 1 × 10 –9 m.
46. Classify nanomaterials according to molecular arrangements.
Ans.: According to atoms/molecular arrangements, nanomaterials are broadly classified into
three types.

7.80
Materials which have one dimension in the nanoscale. For example,, surface coatings, thin
films, etc.
Materials which have two dimensions in the nanoscale. For example, nanowires, nano-
tubes, etc.
Materials which have three dimensions in nanoscale or quantum dots. For example,,
fullerenes.
47. What are the important properties of nanomaterials?
Ans.: A significant increase in surface-area-to-volume ratio at the nanoscale gives rise to novel and
enhanced magnetic, mechanical, electronic, catalytic, conducting and optical properties.
48. Give some examples of semiconducting and superconducting nanomaterials.
Ans.: Semiconductors: Carbon nanotubes, nanowires, MoS2, etc.
Superconductors at high temperature: NbS2.
49. What are the most important applications of carbon nanotubes?

Ans.: Well-defined geometry, exceptional mechanical properties and extraordinary electrical
characteristics of carbon nanotubes are used in nanoelectric circuits, nanoelectro mechan-
ical systems, nanorobotics, nanobiosensors, etc.
50. Give the interconversions of a nanometer.
Ans.: One nanometre is the one-billionth of a meter. 1 nm = 10 – 9 m = 10 – 9 yards approximately.
51. Give the different synthetic routes of nanomaterials.
Ans.: The vapour–liquid–solid growth, solution–liquid, solid growth, template-mediated
growth, electron beam lithography, reverse micellar route, etc.
52. How can we characterise nanomaterials?
Ans.: Nanomaterials are characterised by X-ray diffractions (XRD), transmission elec-
tron microscopy (TEM), scanning electron microscopy (SEM), thermal analysis like
TGA/ DTA, Fourier transform infrared spectroscopy (FITR), etc.
53. Give the broad classification of nanomaterials.
Ans.: (i) Materials which have one dimension in the nanoscale. For example,, surface coatings
or thin films.
(ii) Materials which have two dimension in the nanoscale. For example,, nanowires and
nanotubes.
(iii) Materials which have three dimension in the nanoscale. For example,, quantum dots.
54. Which property plays a vital role in nanomaterials?
Ans.: A significance increase in surface area-to-volume ratio at the nanoscale gives rise to novel
and enhanced magnetic, mechanical, electronic, catalytic, conducting, optical properties, etc.
55. Give a brief note about fullerenes and carbon nanotubes.
Ans.: Fullerenes are a class of allotropes of carbon, which are basically graphene sheets rolled
into tubes or spheres. They include carbon nanotubes because of their mechanical strength
and electrical properties.
56. What are the important uses of carbon nanotubes?
Ans.: Nanoelectronic circuits, nanoelectromechanics, nanorobotics, probes, grippers, nanobio-
sensors, etc., are important uses of carbon nanotubes.

57. Give the broad classification of liquid crystals.

Ans.: Liquid crystals are broadly classified into thermotropic liquid crystals and hydropic liquid
crystals.
58. Name the three kinds of thermotropic liquid crystals.
Ans.: The three types are nematic, cholesteric and smectic liquid crystals.
59. What is the main difference between nematic and cholesteric structure?
Ans.: Cholesteric structure is a nematic type of liquid crystal but it is optically active.
60. Give examples of nematic liquid crystals.
Ans.: P-methoxybenzylidene p1-N-butyl-aniline and P-n-Hexyl-P1-cyanobiphenyl.
61. Why are lyotropic crystals known as amphiphilic?
Ans.: Lyotropic crystals are composed of both lyotropic and lyophobic parts.
62. Define liquid crystals. Why are they named liquid crystals?
Ans.: Liquid crystals are highly anisotropic fluids that exists between the boundaries of the solid
and conventional, isotropic liquid phase.
Liquid crystals are made up of both liquid and crystal. The term “liquid” is used because
the tendency to take the shape of the container and the word crystal is used because they
still contain one- to two-dimensional arrays.
63. Name the different types of thermotropic liquid crystals.
Ans.: Nematic, cholesteric and smectic structures are main types of thermotropic liquid
crystals.
64. Define lyotropic liquid crystal and give an example.
Ans.: Lyotropic liquid crystals are mixtures of two or more components that change phase with
changes of concentration.
For example,, sodium stearate, a -Lecithin.
65. Give some applications of liquid crystals.
Ans.: Liquid crystals are widely used in research, medicine, displays, radiation sensors,
thermometers, non-destructive testers, etc.
66. Give the importance of liquid crystals in medicine.
Ans.: Liquid crystals are widely used in medicine as optical disks, full colour electronic slides,
light modulators, etc., because most biological systems exhibit liquid crystal properties.
67. What is the reason for liquid crystals being used as thermometers?
Ans.: The temperature-dependent variation in the colour of cholesteric liquid crystals has led to
the use of substances in the measurement of temperature and gradients of temperature. A
cholesteric substance or a mixture of cholesterics always exhibits the same colour and the
same temperature. Hence, these are also used to locate veins, arteries, infections, tumours,
etc., which are warmer than surrounding tissues.
68. Give commonly used natural and artificial abrasives in the order of increasing hardness.
Ans.: Talc < Gypsum or NaCl < Calcite < Fluorite < Apatite < Feldspar < Quartz < Topaz or
emery < Corundum < Diamond

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69. Give some common uses of abrasives.

Ans.: (i) Housewives and farmers use abrasive stones to keep their kitchen knives and agricul-
tural instruments sharp.
(ii) Dentists use an abrasive powder when they clean teeth and to smooth down fillings.
(iii) Abrasives play important roles in various industries such as in grinding of wood into
paper pulp, cutting of stone into carved and surfaced structures, and sharpening of
cutting-tools.
70. Give broad classification of abrasives.
Ans.: Abrasives are broadly classified into natural and artificial abrasives.
71. Give brief note about garnet.
Ans.: Garnets are trisilicates of alumina, magnesia and ferrous oxide. The common garnet used as
an abrasive is a complex of calcium–aluminium–iron silicates with the approximate formula:
Ca3Al2(SiO4)3.Ca3Fe2(SiO4)3.Fe3Al2(SiO4)3
Hardness of garnets ranges from 6.0 to 7.5 on Moh’s scale. Garnets are too soft for grind-
ing steel and iron, but when glued to paper or cloth, they are used for finishing hardwoods.
They are also used for bearing pivots in watches, glass grinding, and polishing metals.

Q.1 Define semiconductors and explain intrinsic and extrinsic semiconductors with example.
Q.2 Write a note on n-type and p-type semi-conductors.
Q.3 Give a brief note on the importance and application of semi-conductors.
Q.4 Explain super conductors with examples.
Q.5 Define magnetism and explain dia and paramagnetic materials.
Q.6 Explain the classification of magnetic materials in detail.
Q.7 Give a brief note on the important properties of magnetic materials.
Q.8 Explain the applications of magnetic materials.
Q.9 What is Portland cement? Explain the different ingredients of cement.
Q.10 Give an account of the following:
(a) Chemical composition of cement
(b) Chemical constitution of Portland cement
(c) Naming of Portland cement
Q.11 Explain the setting and hardening of cement with suitable chemical reactions.
Q.12 Write a brief account on the following:
(a) Raw materials and the ingredients of cement
(b) Function of gypsum in cement
(c) Discuss merits and demerits of dry process and wet process.
Q.13 Explain the analysis of cement.

Q.14 Draw a labelled diagram of a rotary kiln used for the manufacture of Portland cement by wet
process and discuss the various reactions taking place in the furnace.
Q.15 What are the microscopic constituents or constitutional compounds present in Portland cement?
How do they contribute towards the properties of the cement?
Q.16 What do you mean by setting and hardening of cement? Discuss the various reactions involved
with the help of equations.
Q.17 “The properties of Portland cement depend upon the relative proportions of its constitutional
compounds”. Justify the statement.
Q.18 What are the different methods of manufacturing cement? Discuss their relative merits and
demerits.
(a) Reactions taking place in the rotary kiln.
(b) Constitutional compounds in cement and its derivatives.
(c) Additives for cement.
(d) Important properties of cement.
(e) How is cement classified?
(f) Define the soundness of cement.
Q.20 (a) W hat is a pyrometric cone equivalent? How is it determined for a refractory? What is its
significance?
(b) Write a short note on the following:
(i) Porosity
(ii) Thermal conductivity
(iii) Dimensional stability
(iv) Strength
Q.21 (a) Define refractories and what are the criteria of a good refractory?
(b) Give the classification of refractories with suitable examples.
Q.22 (a) W hat are refractories? How important are the properties of refractoriness under load and
thermal conductivity for industrial applications?
(b) Compare acidic and basic refractories with examples.
Q.23 (a) How are refractories classified? Give one example for each class.
(b) Write a note on the conditions leading to failure of a refractory material.
Q.24 Discuss any four essential properties of a good refractory in detail.
Q.25 What are the causes leading to failure of a refractory?
Q.26 Write short note on the following:
(a) Refractoriness
(b) Refractoriness under load or strength
(c) Dimensional stability
(d) Thermal conductivity
(e) Porosity

7.84
Q.27 State some important industrial applications of refractories.

Q.28 Discuss the important properties of refractories which have a direct bearing on their industrial
use.
(a) Fire clay refractories
(b) Silica refractories
(c) Magnesite refractories
Q.30 (a) What are the raw materials for refractories?
(b) What are the different steps in the manufacture of refractories?
(c) What do you mean by super refractories?
Q.31 Discuss the various physical and chemical factors which affect the industrial uses of refractories.
Q.32 (a) Give the functions of lubricants.
(b) Describe the mechanism of extreme pressure lubrication.
(c) How is a viscous lubricant converted into grease?
Q.33 Discuss the important properties of lubricating oils, which are useful for their evaluation.
Q.34 (a) Distinguish between hydrodynamic lubrication and boundary lubrication.
(b) Distinguish between hydrodynamic lubrication and extreme pressure lubrication.
Q.35 Explain the following two theories for the mechanism of the lubricants:
(a) Boundary lubrication
(b) Extreme pressure lubrication
Q.36 Write notes on the following:
(a) Blended oils
(b) Petroleum oils
(c) Extreme pressure additives
(d) Antioxidants
Q.37 Explain how the following act as lubricants:
(a) Graphite
(b) Molybdenum disulphide
Q.38 Write a note on lubricants with special reference to their classification, mode of action, examples
and applications.
Q.39 How do we select lubricants for the following?
(a) Cutting tools
(b) I.C. engines
(c) Steam engines
(d) Steam turbines
(e) Gears
Q.40 Explain the various mechanisms of lubrication in detail.
Q.41 Define lubricants. Discuss the important properties of the lubricating oils.

Q.42 Describe the various types of lubrication.

Q.43 Define the flash and fire points.
Q.44 (a) Describe thick-film lubrication.
(b) Write a note on semi-solid lubricants.
Q.45 Write short notes on the following properties of lubricants:
(a) Pour point
(b) Aniline point
Q.46 Explain the hydrodynamic lubrication.
Q.47 Explain the following properties of lubricants and discuss their significance:
(a) Viscosity and viscosity index
(b) Flash point
(c) Aniline point
(d) Saponification value
Q.48 Distinguish between fluid film and boundary lubrication.
Q.49 Lubricating oil has the same viscosity as standard naphthenic and paraffinic type oils at 210°F.
Their viscosities at 100°F are 320 Saybolt universal second (SUS), 430 SUS and 260 SUS respec-
tively. Find the viscosity index of the oil.
Q.50 (a) What do you mean by viscosity index of lubricating oil?
(b) Lubricating oil has a SUS of 58 seconds at 210°F and of 600 seconds at 100°F. The high viscos-
ity index standard (i.e., Pennsylvanian) oil has Saybolt universal viscosity (SUV) of 58 seconds
at 210°F and 400 seconds at 100°F. The low viscosity index standard (i.e., Gulf ) oil has a SUV
of 58 seconds at 210°F and 800 seconds at 100°F. Calculate the viscosity index of oil.
Q.51 Write an essay on solid lubricants with emphasis on their classification, mechanism of action,
examples and applications.
Q.52 How are semi-solid lubricants prepared? In what situations is a semi-solid lubricant preferred?
Mention some important tests for evaluating semi-solid lubrications.
Q.53 How are liquid lubricants classified? Discuss the various methods available for refining mineral
oils.
54. What do you mean by blended or compounded oils? What are the various additives used to
induce or improve the necessary properties of lubricating oil?
Q.55 Discuss the use of lubricating emulsions.
(a) Cup greases
(b) Fixed oils
(c) Gas lubrication
(d) Biodegradable lubricants
(e) Neutralisation number
(f) Extreme pressure lubrication
(g) Oiliness

7.86
(h) Redwood viscometer

(i) Cryogenic bearing lubricants
( j) Lubricants for nuclear reactor systems
(k) Lubricants for food processing
(l) Environmental and health factors in the use of lubricant
Q.57 Justify the following statements:
(a) Flash point determination by the closed-cup apparatus gives a lower value than that deter-
mined by an open-cup apparatus.
(b) Closed-cup apparatus gives more reliable value than the open-cup apparatus for the determi-
nation of flash point.
(c) The relative viscosity determined by Saybolt viscometer or Redwood viscometer can be con-
verted into absolute kinematic viscosity by calculations.
Q.58 Write short notes on saponification and iodine values.
Q.59 Discuss the significance of viscosity in lubricating oil. How is it determined by Redwood
viscometer?
Q.60 (a) Write the structure of graphite. Based on this, suggest why this can be used as a solid lubricant.
(b) Discuss the classification of lubricants.
Q.61 Define lubricants. Discuss the classification of lubricant with suitable examples.
Q.62 (a) Explain the following properties of lubricants and their significance:
(i) Carbon residue
(ii) Aniline point
(b) Write an informative note on synthetic lubricants.
Q.63 Define the term lubricants. Mention their important functions. Explain and discuss the signifi-
cance of any two properties of lubricants.
Q.64 Discuss lubrication, its mechanism and significance in brief. Explain viscosity index of lubricat-
ing oil.
Q.65 (a) Define the terms lubrication and lubricants. What are the different types of lubricants?
Discuss the basic principle of lubrication.
(b) What are the chief functions of lubricants?
(c) What are the different types of lubricants?
(d) Discuss the classification of lubricants with an example.
Q.66 (a) How are lubricating oils produced and refined? Which oil is a better lubricant?
(b) Define dewaxing. What are the characteristic features of synthetic lubricating oils?
Q.67 (a) Write the names of two semi-solid lubricants.
(b) Give brief note on graphite and molybdenum disulphide.
(c) Write a short note on the following:
(i) Semi-solid lubricants
(ii) Synthetic lubricants
(iii) Solid lubricant and its advantage

Q.68 (a) Write a short note on extreme-pressure lubrication?

(b) W hat are the different synthetic lubricants used? How are they superior over petroleum
lubricants?
Q.69 (a) W hat are greases and under what situations are they employed? Discuss the composition and
uses of the following:
(i) Calcium-based greases
(ii) Soda-based greases
(iii) Axle greases
(b) Write a note on extreme-pressure additives to mineral oil.
Q.70 (a) Draw a neat and labelled diagram of the determination viscosity of lubricant by Redwood
viscometer.
(b) Write a short note on aniline point.
Q.71 (a) How does viscosity determine the operating characteristics of the lubricants?
(b) Suggest the suitable properties of lubricating oil used for steam engines and transformers.
Q.72 (a) Cotton seed oil is used as dry oil in paints. Is it true or false?
(b) Write a note on additive for lubricating oils.
Q.73 (a) How are greases made?
(b) What is a lubricant? Discuss the classification and its basic characteristics with examples.
Q.74 (a) What are the characteristic features of synthetic lubricating oils?
(b) Write an explanatory note on solid lubricants.
Q.75 (a) Name any four solid lubricants.
(b) Describe any four desirable properties of lubricant oil.
(c) Write brief note on greases.
Q.76 (a) Explain clearly the importance of the following in selecting lubricating oil for a particular use:
(i) Viscosity
(ii) Flash point
(iii) Acidity
(iv) Carbon residue
(b) How is the viscosity of lubricating oil determined in the laboratory?
Q.77 (a) How will you select a lubricant?
(b) Explain the properties of lubricants such as viscosity and viscosity index.
Q.78 (a) What is meant by lubricant? Explain the mechanism of lubrication.
(b) Write a note on the following:
(i) Lubricating greases
(ii) Lubricant emulsions
(c) Describe a method to manufacture lubricating oils.
(d) Write a note on the lubricating action of greases.
Q.79 (a) How are lubricants classified?
(b) Define flash point. Describe any one method of determining flash point.
(c) With the help of a neat diagram, explain the working of Redwood viscometer.
(d) What is lubrication? Explain any one type of lubrication in detail.

7.88
Q.80 (a) Why are fatty oils no longer used as lubricants?

(b) What do you mean by viscosity of a lubricating fluid? How does it change with temperature?
How do viscosity and viscosity index influence the selection of lubricants for particular
purposes?
(c) W hat are flash point and fire point of a liquid lubricant? Are they directly related to the qual-
ity of lubricants?
(d) Write a short account on solid lubricants.
Q.81 (a) Under what situation greases are used? What are the main functions of soap in grease?
(b) What do you understand by consistency and drop point of grease? Explain their importance.
Q.82 (a) What is meant by “oiliness” of a lubricant? How can this be improved?
(b) Explain boundary and fluid lubrications and mention the conditions therein.
Q.83 (a) What are propellants and explains the characteristics of a good propellants?
(b) Explain the properties of solid and liquid propellants.
Q.84 (a) What are explosives? What are the basic requirement of chemical explosives?
(b) Write short note on Dynamite.
(c) Write short note on TNT.
(d) Distinguish between primary and secondary explosives.
Q.85 Write a short note on the following:
(a) Classification of explosives
(b) Plastic explosives
(c) Rocket fuels
(d) Propellants
(e) Blasting fuses.
Q.86 (a) What is detonation?
(b) What are the requirements of a good propellants?
(c) What are the requirements of a good explosives?
Q.87 (a) What two factors for the selection of a propellant?
(b) Explain Mono and bi propellants with examples.
Q.88 Define nanomaterial. Explain some of the important properties.
Q.89 Give a brief description about the applications of nanomaterials.
Q.90 What are nanomaterials? Explain their characteristics.
Q.91 Give broad classification of nanomaterial with an example.
Q.92 Explain the following properties of nanomaterial:
(a) Catalytic property
(b) Mechanical property
(c) Electrical property
(d) Optical property
Q.93 What are nanoparticles? Give brief description on their properties.
Q.94 Give brief explanation about preparation of nanomaterials and their importance.

Q.95 Give brief explanation about characterisation of nanomaterials.

Q.96 Discuss about carbon nanotubes and their importance.
Q.97 Define liquid crystal and explain the characterising of a liquid crystal phase.
Q.98 Give a brief explanation about thermotropic liquid crystals with example.
Q.99 Write short note on lyotropic liquid crystals.
Q.100 Explain the important applications of liquid crystals.
Q.101 Give brief note on the following:
(a) Smectic structure
(b) Enantiotropic crystal
(c) Monotropic crystals.
Q.102 Define abrasive and explain hardness of abrasive with Moh’s scale.
Q.103 Give brief note on natural and artificial abrasives.
(a) Diamond
(b) Carborundum
(c) Alundum
(d) Hardness of abrasive

8 Phase Rule
8.1 Introduction
In 1875, as a result of mathematical and thermodynamic studies, J. Willard Gibbs put forward a rule
known as Phase Rule; without any exception, the rule is applicable to all heterogeneous system in equi-
librium. By using Phase Rule, the effect of temperature, pressure and concentration can be predicted
qualitatively on a heterogeneous system, which is in equilibrium by the Phase diagrams.
It is assumed that the equilibrium is influenced only by temperature, pressure and concentra-
tion, but not influenced by gravity, electrical or magnetic forces or by surface action. The maximum
number of degree of freedom is taken as three; mathematically, Gibbs’ Phase Rule may be stated
as:
F = C − P + 2 or F + P = C + 2
Where
F = Number of degree of freedom
C = Number of components
P = Number of Phases
8.2 Explanation of the Terms involved in Phase Equilibria
8.2.1 Phase (P)

A heterogeneous system consists of various homogenous parts in contact with each other by distinct
boundaries; any part of a system which is homogeneous, physically distinct and mechanically separa-
ble from other parts of the system is a Phase.
Essential Conditions for a Phase

(i) It should be homogeneous or may be a homogeneous part of a heterogeneous system.
(ii) It should be physically distinct and is separated from other parts of a system by well defined
boundary surface.
(iii) A dynamic equilibrium between different phases of this system should be present to exchange of
chemical species.

Examples
(i) A gas or a gaseous mixture is a single phase because there is no interface between one gas and
another e.g. air which is a mixture of nitrogen, oxygen, carbon dioxide, water vapour, etc is
composed of one phase only.
(ii) Water exists in three forms-ice, water and vapour. It is a three phase system.

solid (Ice)
liquid (water) Gas (water vapour)
(iii) Two or more completely miscible liquids present in a system constitute only one liquid phase as
there will be no surface of separation between them when they are mixed. e.g.: water, alcohol,
acetone etc.
(iv) Two immiscible liquid forms two different phases. e.g.: water and ether, alcohol and ether etc.
Both forms two different phase.
(v) A heterogenous mixture of solid substances consists of as many phases as there are substances
present in that system.
e.g.: decomposition of CaCO3(s)

CaCO3 (s) CaO(s) + CO2 (g)
Here are three phases among those two phases are CaCO3(s) and CaO(s) and third phases is CO2(g)
because all phases are separated by interface.
8.2.2 Components (C)

The smallest number of independently variable constituents by which the composition of each phase
present can be expressed directly or in the form of a chemical equation is the number of components
(C) of a system at equilibrium.
The number of components of a system may be or may not be the same as the actual number of
substances or constituents present in the system; only those constituents of an equilibrium mixture,
which can undergo independent variation, are known as components.
(i) When no reaction takes place, the number of components in equal to the number of
constituents.
(ii) When a reaction occurs, at that time, then the minimum number of species allowing for a reaction
to prepare one species is known as the number of components.
Therefore, the number of components of a system
C=S−R
Where S = number of chemical species present in the system
R = number of independent chemical reactions taking place among the chemical species.
In case of Ionic Reaction
The number of component is calculated as
C = S − (R + 1)
S = Total number of ionic species present in the system.
R = number of relation between ionic species.

Phase Rule 8.3
Examples
(i) Water exists in three phases as

Ice
Water Vapour
(solid) (liquid) (gas)
Each phase can be represented by H2O. Thus, the number of components is one.
(ii) Consider aqueous solution of sugar. Here, the composition of this solution is described by speci-
fying the presence of sugar and water. Thus, the number of components is two.
(iii) Consider the decomposition of Ammonium chloride as

NH 4 Cl(s) NH 3 (g) + HCl(g)
Actually this equilibrium exists as

NH 4 Cl(s)
NH 4 Cl(g) NH 3 (g) + HCl(g)
(a) If the reaction is carried out in a closed vessel or vacuum then number of component is one
because in the gaseous phase both HCl and NH3 are always present in equal amounts and
represents NH4Cl(g).
(b) If the excess of either NH3 or HCl is introduced, the composition of gaseous phase can no
longer be the same and the composition of this phase can no longer be represented by NH4Cl
alone, but one more component is required. Hence, it becomes two component system.
(iv) Consider the thermal decomposition of CaCO3 as

CaCO3 (s) CaO(s) + CO2 ( g )
There are S = 3 ﹛CaCO3(s), CaO(s), CO2(g)﹜
R=1
So, C = S − R
=3−1=2
Hence, the number of component is two.
Here, three different constituents form three different phases, but the composition of each phase
can be expressed in terms of any two of the constituents.
(a) If CaO and CO2 are chosen as the components, then
Phase Composition
CaCO3 → CaO + CO2
CaO → CaO + 0CO2
CO2 → 0CaO + CO2
(b) If CaCO3 and CO2 are chosen as the components, then
Phase Composition
CaCO3 → CaCO3 + 0CO2
CaO → CaCO3 − CO2
CO2 → 0CaCO3 + CO2
(c) If CaCO3 and CaO are chosen as the components, then
Phase Composition
CaCO3 → CaCO3 + 0CaO

CaO → 0CaCO3 + CaO

CO2 → CaCO3 − CaO
Thus, in all these cases the smallest number of constituents which can fix the composition of the
phase present at equilibrium is two; hence, dissociation of CaCO3 by heat is a two component
system.
(v) Consider the system NaBr−KCl−H2O
The number of components is calculated by formula
C = S − (R + 1)
Here number of species, S = 9 (NaBr, NaCl, KCl, KBr, H2O, Na+, Br−, K+, Cl−)
(Dissociation of water is ignored)
Number independent reactions (Relation)
R=4
+ −
NaBr Na + Br
+ −
KCl K + Cl
Na + + Cl −

NaCl
K + + Br −

KBr
∴ Number of components C = S − (R + 1)
= 9 − (4 + 1)
=4
Hence, it is a four compound system.
(vi) Consider the dilute solution of sulphuric acid in water
+ −
H 2SO 4 + H 2 O
H 3O + H SO 4
− + 2−
H SO 4 H + SO 4
+ − 2−
Here, number of species, S = 5( H 2SO 4 , H 2 O, H 3O , HSO 4 , SO 4 )
Number of relation, R = 2
C = S − (R + 1)
= 5 − (2 + 1) = 2
∴ Hence, it is a two component system.
8.2.3 Degree of Freedom (F)

Degree of freedom is defined as the number of intensive variables (temperature, pressure and concen-
tration) that can be changed independently without disturbing the number of phases in equilibrium.
These variables describe the state of the system. On the basis of degree of freedom of the system,
systems are classified as nonvarient(F = 0), monovarient (F = 1), bivarient (F = 2) etc.
Examples
(i) Consider the example of pure gas, the number of degree of freedom is two (F = 2). This
is because a pure gas satisfied the gas equation PV = RT. If the values of pressure (P) and

Phase Rule 8.5
temperature (T) are fixed, then the volume (V) automatically gets fixed. In fact if any two vari-
ables (out of P, V & T) are specified. The third one gets specified by itself. Hence a system con-
sisting of pure gas has two degree of freedom i.e. it is a bivarient system.
(ii) Consider one component having two phase system.

Water
Vapour
This system consists of two phases of one component. The vapour pressure of water is definite at
a definite temperature independent on the concentration. It follows, therefore, that if the tempera-
ture is fixed, the vapour pressure is also fixed and vice-versa. So, we cannot alter both the vari-
ables without disturbing the equilibrium. Hence, we have to mention only one variables without
disturbing the equilibrium i.e. either temperature or pressure. Thus the system has one degree of
freedom (F = 1). System is called as monovarient or univarient (F = 1).
(iii) Consider one component, three phases in equilibrium

Ice
Water Vapour
In this system, there are three phases of one component (H2O). These three phases can co-exist
in equilibrium only at particular temperature (0.0098 °C) and under one particular pressure (4.58
mm of Hg). Any variation of these factors will result into disappearance of one or more of the
phases. Hence this system has zero degree of freedom (F = 0) i.e.nonvariant or invariant.
8.2.4 True and Metastable Equilibrium

Under a given set of conditions, the same state of a system can be attained by approaching from either
direction by any possible procedure; then, that system is said be in the state of true equilibrium.
According to thermodynamics, true equilibrium is attained when the free energy content of the
system is at a minimum for the given values of the variables.
Example: At 1 atm pressure and 0 °C (273 K) ice and liquid water attain true equilibrium because it can
be attained by either partial melting of ice or partial freezing of water.

Ice Water
Under a given set of conditions a state of a system can be attain by only one direction with careful
changing of a system conditions; that system is said to be state of meta stable equilibrium.
Example: At 271 K (−2 °C) or at even lower temperature, it is possible to cool water very slowly
and carefully without appearance of ice; hence, water at −2 °C is said to be in a state of metastable
equilibrium. The metastable equilibrium state of the system may be preserved by not subjecting it to a
sudden shock, stirring or seeding by the solid phase. Solidification sets rapidly as soon as a crystal of
ice is introduced and the temperature rises to 0 °C (273 K).
8.2.5 Eutectic Mixture and Eutectic Point

Mixture of two or more components without reacting chemically in solution state and at a particu-
lar temperature having lowest freezing or melting point among all possible ratio of mixing of that
component is known as eutectic mixture, and such a type of system is called the eutectic system
and the corresponding lowest freezing or melting point of that eutectic mixture is called the eutectic
point.
For example in a eutectic mixture of lead (Pb) and silver(Ag) forms a eutectic point at 303 °C hav-
ing the lowest melting point of eutectic system.

8.2.6 Triple Point

Triple point is a point at which three phases of a system co-exists in equilibrium. The degree of free-
dom of one component system is zero. At triple point, system is in variant i.e. degree of freedom is
zero (F = 0).
For example, consider a system of water having three phases

Ice
Liquid Vapour
All these phase co-exist at a particular temperature (0.0098 °C) and a particular pressure (4.58 mm
of Hg). At triple point F = 0 (invariant or non-variant)
C = 1, P = 3, F=C−P+2=1−3+2=0
F = 0 (Invariant)
8.3 Phase Rule

The phase rule gives relationship between the numbers of phases, components and degree of freedom
of a heterogenous system.
The Gibbs phase rule may be stated as follows:
In a heterogenous system in equilibrium, the number of degree of freedom plus the number of
phases is equal to the number of components plus two.
Mathematically,
F + P = C + 2 or F = C − P + 2
Where
F = number of degree of freedom
C = number of components
P = number of phases
Digit ‘2’ represents the temperature and pressure.
It is assumed that the equilibrium is not influenced by gravity, electrical or magnetic forces or
by surface action and is influenced only by temperature, pressure and concentration. The maximum
number of degree of freedom is taken as three.
8.3.1 Assumptions for the Validation of Phase Rule

(i) The system is in thermal and mechanical equilibrium; consequently, the pressure and tempera-
ture are the same in all the phases of system.
(ii) Surface contribution as well contributions from any electric or magnetic field to the extensive
properties of the system, are negligible.
(iii) Inter phase surfaces are deformable and permeable to components.
8.3.2 Thermodynamic Derivation of the Phase Rule

Let us consider a heterogenous system having C components (C1, C2, C3, …, Cc) distributed between
P phases (P1, P2, P3, …, PP) as shown in Figure 8.1.
As we know that the degree of freedom of a system is equal to the number of independent variables
which must be fixed arbitrarily to define system completely.

Phase Rule 8.7
Degree of freedom = Total number of variables − (Number of variables defined by the system
because of its being in equilibrium)
F=V−E
Phases
P1 P2 P3 Pp
C1 C1 C1 C1 C1
Components
C2 C2 C2 C2 C2
C3 C3 C3 C3 C3
Cc Cc Cc Cc Cc
Figure 8.1 A system showing C components distributed in P phases in equilibrium
(i) Total number of variable can be calculated as follows:

(a) Temperature: Same for all phase (one variable)
(b) Pressure: Same for all phase (one variable)
(c) Concentration: Suppose a phase contains two components (A and B). Then if molar concen-
tration of one component is known, then that of other can be calculated by using formula
x A + x B = 1.
Similarly, if a phase contains three components, only two concentration terms should be known
(xA + xB + xC = 1).
Hence, in general if a phase contains C components, it can be defined completely by (C − 1)
concentration terms or variable.
For a complete system having P phase and C components the total number of variable
required = P(C − 1).
Total number of variables is given by
V = P(C − 1) + 2 (‘2’ stands for temperature and pressure variables)
(ii) The number of variables defined by the system itself i.e. number of relations of equilibrium:
When a heterogenous system is in equilibrium at constant temperature and pressure, the chemical
potential of any component will have the same value in all the P phases.
Thus if a system consist of three phases,
Say a , b and g, then for any component i,
(μi) a = (μi) b = (μi) g
If one of them is taken as standard value, then two equations are written as
(a) (μi) a = (μi) b = (μi) g
(b) (μi) a = (μi)g
Thus for a system of 3 phases, two equations are known for each component.
Similarly, for a system of 4 phases, three equations are known for each components.
In general, for a system of P phases, (P − 1) equations are known for each components.
Hence, for a system having P phases and C components.

Number of equations known will be = C (P − 1)

So, number of variables defined by the system itself = C(P − 1)
E = C(P − 1)
Now, degree of freedom of the system having P Phases and C components will be given by
F=V−E
= [P(C − 1) + 2] − [C(P − 1)]
F=C−P+2
This is the statement of Phase Rule, where only three state variable (Temperature, pressure and
concentration) are taken into consideration.
If one of these two variables (temperature and pressure) does not affect on equilibria then
degree of freedom for such a system will be reduced by one and in this case phase rule is called
as reduced phase rule and it is represented as
F′ = C − P + 1
Reduced phase rule equation.
8.3.3 Utility of Phase Rule | Application of Phase Rule

The following are some of the advantages from the study of phase rule.
(i) Phase rule helps in classifying various equilibrium states of the system in terms of the number
of components, number of phases or the number of degrees of freedom.
(ii) The different systems which are having the same value of degree of freedom according to phase
rule, they would behave in a similar fashion.
(iii) By using phase rule, we can predict the behavior of any system with the changes in the variables
such as temperature, pressure and concentration.
(iv) Phase rule is applicable to physical and chemical equilibria irrespective of the nature or amounts
of the substances.
(v) It finds extensive use in the study of heterogeneous systems. This rule helpful in metallurgy and
provided us useful information about the complex formation among different components.
(vi) By using phase rule, we can predict whether under a given set of conditions, a number of sub-
stances taken together would remain in equilibrium as such or would involve inter-conversion or
elimination of some of them substances.
8.3.4 Limitations of Phase Rule

(i) Phase rule applies only to a single equilibrium state and does not tell us about the number of
other possible equlibria present in the system.
(ii) The phase rule equation (F = C − P + 2) is applicable only to system having three variables. When
the numbers of variables change the equation shall have to be changed accordingly.
(iii) Phase rule deals with macroscopic system only and it does not tell us anything about the molecular
structure.

Phase Rule 8.9
(iv) The phase rule does not give any information regarding the time taken for the system to attain
equilibrium.
(v) The phase rule also does not give any information regarding the amount of any phase under equi-
librium. It only considers the number of phase present in the system at equilibrium.
8.4 Phase Diagrams

Phase diagram is the complete description of behavior of phases in equilibrium. When the system is
in equilibrium, the number of phases that exist together depends upon the conditions of temperature
and pressure concentration kept constant or conditions of temperature and composition, pressure being
kept constant. The diagrams so obtained giving the conditions of equilibria between various phases of
a substance are called as phase diagrams or equilibrium diagrams.
The phase diagram contains a number of lines, areas and point by intersection and by such dia-
grams we are able to know the conditions under which various phases will be present in the system.
Let us consider one component system with different number of phase
(i) Single phase: When a pure substance is in single phase and having one component.
Then according to phase rule equation
F=C−P+2
= 1 − 1 + 2 = 2 (Bivariant)
It means such a system can be completely describe by using two variables
(ii) Two phase: When we are considering one component in two phase are in equilibrium
Then degree of freedom
F=C−P+2
= 1 − 2 + 2 = 1 (Monovariant)
All such type of systems can be completely described by stating only one variables either tem-
perature or pressure.
(iii) Three phase: When we are considering one component in three phase are in equilibrium, then
the system has no degree of freedom
F=C−P+2
= 1 − 3 + 2 = 0 (Invariant)
For all such type of system, all variables must be specified fixed.
8.5 One Component System

For a one component system,
According to phase Rule,
F=C−P+2
C=1
F=3−P
(i) When value of P = 1, then Degree of freedom, F = 2, it means both P and T can be varied inde-
pendently without disturbing the equilibrium.

8.10
(ii) When two phases are in equilibrium, value of P = 2. Degree of freedom (F ) = 1, it means pressure
can be changed freely if temperature is set or vice-versa.
(iii) When three phases are in equilibrium (P = 3). The degree of freedom (F) is equal to zero it means
system can only be non-variant in specific or definite conditions of temperature and pressure.
Water System
Water system is most typical example of one component system, in which the same chemical com-
pound exists in the three phases in equilibrium as
Ice water Vapour
(solid) (liquid) (gas)
These three phases may occur in the three possible combinations of the two phases in equilibrium as
(i) water Vapour vapourisation process
(liquid) (gas)
(ii) Ice Vapour sublimation process

(solid) (gas)
(iii) Ice water Fusion process

(solid) (liquid)
The conditions of temperature and pressure at which the various phases can exist have been deter-
mined experimentally and summed up in Figure 8.2.
These phase diagram of water system is represented as in Figure 8.2.
Critical pressure A
218 atm
Vapour pressure (not to scale)
rve
e
rv
cu
u
on c
Solid phase Liquid phase

n
io
at
Fusi
is
Critical temperature
por
Va
1 atm
4.58 mm O
Triple
A′ rv e point
cu
on
mati Vapour phase
bli
Su
B
T1 BP T2
−273° 0.0023° 0.0098° 100° 374°
Temperature °C (not to scale)
Figure 8.2 Phase diagram of water system

Phase Rule 8.11
The phase diagram consists of:

(i) Three stable curves OA, OB and OC and a meta stable curve OA′
(ii) Three areas AOC, BOC and below AOB
(iii) Definite point, O
(a) Areas
(i) Area below AOB
In this area vapour phase of water exists,
According to phase rule
F=C−P+2
=1−1+2=2
System is bivariant in this area. It means to show the conditions of existence of this phase two
variables temperature as well as pressure are required.
(ii) Area BOC
In this area solid phase (Ice) exists.
Again degree of freedom F = C − P + 2
= 1 −1 + 2 = 2
The system is bivariant and therefore to specify the conditions of as existence of this phase tem-
perature and pressure are to be specified.
(iii) Area AOC
This area consist liquid (water) phase
Degree of freedom F = C − P + 2
=1−1+2=2
Due to bivariant nature of the system in this area both variable (T & P) are to be specified to
explain the conditions of existence of liquid phase of water system.
(b) Curves
(i) Curve OA: It represents liquid-vapour equilibrium
liquid Vapour
This curve is called as vapourization curve or vapour pressure curve. This curve explain with
increase of temperature, the vapour pressure increases.
This curve status from the point O the triple point of water (0.0098 °C at 4.58 mm) and extends
upto critical temperature (374 °C) at critical pressure (218 atm), beyond which the two phases
merge into each other.
Here P = 2 and C = 1
According to phase Rule F = C − P + 2
= 1 − 2 + 2 = 1 (Monovariant)
Since the degree of freedom is one, hence the system is univariant or monovariant. It means, for
any give vapour pressure on curve there is only one value of temperature or vice-versa. At 100
°C, the vapour pressure of water equals the atmospheric pressure (760 mm). This is therefore,
called as boiling point of water. Beyond the point ‘A’ (critical temperature) liquid phase of water
does not exist.
The slope of the curve OA is positive i.e. the vapour pressure of water increases with tempera-
ture. It is also predicted by Clausius-Clapeyron equation as

8.12
dP ∆H v
= = + ve (∵ Vg > Vl )
dT T (Vg − Vl )
Where ∆Hv = Change in molar heat of vaporization

Vg = Molar volume of water vapours
Vl = Molar volume of water liquid
T = boiling point of water
(ii) Curve OB: It is known as sublimation curve or vapour pressure curve of Ice.
It represents equilibrium between solid and vapour phase
solid vapour
It gives various values of temperature and pressure at which ice and vapour can exist together.
This curve starts from point O, the triple point of water and extends upto point B (absolute
zero, −273 °C)
Here P = 2, C = 1
F=C−P+2=1
Since, the degree of freedom is one, hence the system is univariant i.e. for each temperature that
can be one and only one pressure and vice-versa.
Here the slope of the curve OB is positive and this is also predicted by the Clausius-clapeyron
equation
dP ∆H s
= = + ve (∵ Vg > Vs )
dT T (Vg − Vs )
Where ∆H s = Charge in molar heat of sublimation
Vg = Molar volume of gas phase
Vs = Molar volume solid phase.
(iii) Curve OC: It is called as melting point or fusion curve and it represents the equilibrium between
ice and liquid water at various pressure.
solid liquid
Here P = 2, C = 1
F=C−P+2=1
Since, the degree of freedom in one, hence the system is univariant.
The slope of the curve OC is negative i.e. meeting point of ice is lowered by increases of
pressure.
It is also predicted by Clasius-Clapeyron equation
dP ∆H f
= = −ve (∴Vs > Vl)
dT T (Vl − Vs )
Where ∆Hf = change in molar heat of fusion.

Since the density of ice is less than that of water, so Vs > Vl,
dP
Hence should have negative sign. This means that the increase of pressure must lower and
dT
decrease of pressure must increase the freezing point of water.

Phase Rule 8.13
(iv) Metastable Curve OA′: It represents the liquid water and water vapour in metastable equilibrium.
liquid vapour
It is vapour pressure curve of super cooled water, and it is possible to cool liquid water below
its freezing point without the separation of ice and is shown by dotted line curve OA′; this state
is known as metastable state. It is an unstable state because the curve OA′ lies above the curve
OB. It means that at the same temperature, the vapour pressure of the metastable supercooled
water is higher than the vapour pressure of the stable solid phase. If there is any disturbance in
the process equilibrium may disturb and water may suddenly freeze.
P = 2, C = 1
Here
F=C−P+2=1
The degree of freedom is one hence the system is univariant.
(c) Point
The point at which all the three phases of water, that is, ice, water and vapour coexist in equilibrium is
called triple point. Here, the curves OA, OB and OC intersect with each other at point ‘O’. This point is
shown in the phase diagram at point ‘O’. Ice Liquid Vapour
Here P = 3, C = 1
F = C − P + 2
=1−3+2
=0
Since the degree of freedom is zero, hence the system is invariant. The temperature and pressure
corresponding to this equilibrium are 0.0098 °C and 4.58 mm respectively.
The three phases can co-exist in equilibrium under only one set of conditions; even slight changes
in the temperature and pressure will shift the equilibrium and the three phases cannot co-exist.
Salient features of water system

Curve/Area/ No. of phase Degree of freedom
Point Name of the system Phase equilibrium (P) (F)
Curve OA Vaporization curve liquid vapour 02 01 (univariant)
Curve OB Sublimation curve solid vapour 02 01 (univariant)
Curve OC Fusion curve solid liquid 02 01 (univariant)
Curve OA′ Metastable vaporiza- liquid vapour 02 01 (univariant)

tion curve
Area AOC – Liquid 01 02 (bivariant)
Area BOC – Solid 01 02 (bivariant)
Area AOB – Vapour 01 02 (bivariant)
(Below AOB)
Point O – solid liquid vapour 03 Zero (invariant)

8.14
8.6 Two Component System

According to Phase Rule
F=C−P+2
C=2
F=4−P
For a system with two components and one phase degree of freedom will be three.
F=4−1=3
Therefore, three variables would be necessary to describe a system i.e. temperature, pressure and
composition, all of these variables are required, therefore a three dimensional model is required for
presentation which is more complex and difficult to understand we have a 2D planes and therefore we
consider the one variable as constant, only two variables are considered. This reduces the degree of
freedom of the equilibrium system and phase rule is written as
F1 = C − P + 1
This is known as reduced or condensed phase rule. In general, most of experiments are conducted
in open vessel where pressure in constant so, we generally expressed phase diagram of two compo-
nents by using variable temperature and composition.
8.6.1 Eutectic System

Eutectic system is a binary system consisting of two substances that are miscible in all proportions in
the liquid (solution) phase without reacting chemically. (The term eutectic means easy ‘to melt’.)
For example, bismuth–cadmium, lead–silver, KI–water systems, etc.
Eutectic Mixture
Eutectic Mixture is a solid solution of two or more substances having the lowest freezing point of all
the possible mixture of the components, this is taken advantage of in “alloy of low melting point”
which are generally eutectic mixture.
Eutectic Point
Two or more solid substances capable of forming solid solution with each other have the property of
lowering each other’s freezing point, and the minimum freezing point attainable corresponding to
the eutectic mixture is termed as the eutectic point. For example, in Pb-Ag system, eutectic point is
achieved when the composition is 97.4% Pb and 2.6% of Ag.
Systems giving rise to eutectic point are known as eutectic systems. The eutectic composition and
temperature of two metals and salt-water system is given in Table 8.1.
Characteristics of Eutectic Point

(i) Eutectic point represents the lowest or limiting temperature at which a liquid phase can exist in
the system or it is the maximum temperature upto which a solid phase can exist.
(ii) No other mixture containing the two components will have a melting point lower than the eutectic
temperature.

Phase Rule 8.15
Table 8.1 Some eutectic systems

Components and their Eutectic
S. no. melting points Eutectic composition temperature
1. Ag (961 °C); Cu (1083 °C) (71.8% Ag + 29.2 % Cu) 778 °C
2. Ag (961 °C); Pb (327 °C) (2.6% Ag + 97.4 % Pb) 303 °C
3. Zn (419 °C); Cd (323 °C) (67% Zn + 33 % Cd) 270 °C
4. Zn (419 °C); Al (658.7 °C) (95.64% Zn + 4.36 % Al) 380.5 °C
5. Bi (273 °C); Cd (323 °C) (60% Bi + 40 % Cd) 140 °C
6. KCl (773 °C); H2O (0 °C) (20% KCl + 80 % H2O) -11 °C
7. KI (682 °C); H2O (0 °C) (52% KI + 48 % H2O) -22 °C
(i) Eutectic point has precise values of temperature and composition and it represents an invariant
system.
(ii) If the liquid is cooled to just below the eutectic point, both the components of the eutectic simul-
taneously solidify without any change in the composition or temperature of the liquid phase.
(iii) An eutectic system can maintain its temperature constant for long periods.
(iv) When the liquid is cooled below the eutectic point, the components solidify in the form of small
crystal intimately mixed with each other which fill in the spaces between the large crystals of the
pure components which are already separated out.
(v) Eutectic mixtures appreciably contribute towards the strength of the solid structure in case of alloys.
(vi) Eutectic are mixtures of the components but not their compounds.
Applications of Eutectic System

It has wide applications in industries, pharmaceutical science; medical science etc. Some important
applications are the following:
(i) Freeze–drying
(ii) Safety plugs or safety fuses
(iii) Solders and
(iv) Freezing mixture.
(i) Freeze–drying
The freeze–drying is the complete removal of water from the material, such as food. The following are
two advantages of freeze–drying of food materials:
(i) The microorganisms require water to survive. If water is removed from food, then it won’t get
spoiled for a long period of time due to non-survival of microorganisms. Enzymes also require
water to react with food, so dehydrating of food will also stop ripening. Freeze-dried food mate-
rials such as fruits, vegetables etc. can be stored for years and can be completely revitalized with
a little warm water. After the years, the taste and texture will be very much the same.
(ii) Freeze-drying significantly reduce the total weight of the food .Freeze dried food can be easily
transported to the military during war. It is also used by astronauts in a space craft.
Difference between Dehydration and Freeze Drying

Freeze drying is different from ordinary dehydration. In dehydration, water present in the material
is removed by evaporation of water from liquid to vapour state by supplying heat energy. The food

8.16
materials will be decomposed by the heat supplied for evaporation. Moreover the food will lose its
taste, texture and vitality.
But in freeze drying, the liquid water present in the food material is freezed to solid ice, which is
then sublimed under such conditions that the decomposition and volatilization of other constituents is
avoided.
Principle of the Process

Sublimation is the fundamental principle in freeze–drying, that is, the conversion of a solid directly
into a gas. Sublimation occurs when a molecule gains enough energy to break free from the molecules
around it, just like evaporation. Water will sublime from solid form (ice) to gaseous form (vapour)
when the molecules have enough energy to break free but the condition that the solid melting to its
liquid form, which normally happens, does not take place.
(ii) Safety Plugs or Safety Fuse

A safety fuse is a protective device made from a low melting alloy that melts under heat produced
either by excess heating or by an excess current in the circuit.
They are used to ensure the safe working and avoid accidents. Most commonly used low melting
alloys are wood metal, rose metal and fuse wires.
(i) Wood metal contain 50% Bi, 25% Pb, 12.5% Sn and 12.5% Cd. Its melting point is about 70 ° C.
It is used for making safety plugs for cookers, fire alarms and for boilers and electric fuses
etc.
(ii) Rose metal contains 50% Bi, 28% Pb and 22% Sn. Its melting point is 88 ° C. It is used for making
fuse wires, fire arms and automatic sprinklers.
(iii) Fuse wires for small current are made of Pb–Sn alloy and for high current are made of Pb, Sn,
Zn, Sb, Cu, Al etc.
(a) Safety fuses as plugs are installed in building to protect them against any fire hazards. When
a building catches fire, the heat melts fusible alloy plug and water rushes out from the pipe.
This controls the fire automatically.
(b) They are fitted in the form of plug in steam boilers and pressure cookers. Whenever steam
pressure exceeds the limiting value of pressure, safety plug gets over heated and melts,
thereby permitting excessive steam to escape out of the boiler. Thus, accident due to over-
heating can be avoided.
(c) Safety fuse in the form of fuse wire is also used for protection the cable in an electrical cir-
cuit against damage from any excessive current than normal. This is because when current
is exceeded than normal value, fuse wire gets heated upto the melting point of fuse wire
thereby fuse wire gets melted and circuit is broken. As a consequence, wire in the circuit
gets protected from over-heating.
(iii) Solders
A solder is an alloy having lower melting point than that of the individual metals that are joined
together by melting. It works based on the principle of eutectic mixture freezes sharply at its freez-
ing point; hence, solders have somewhat different compositions from the eutectic so that the freezing
occurs over a range of temperatures.

Phase Rule 8.17
Table 8.2 Solders and their compositions and uses

Solder Composition Uses
Soft or Tinner’s solder 50% Pb and 50% Sn or 60% Pb It is commonly used for sealing the tin cans.
and 40% Sn
Half-Half solder 50% Pb and 50% Sn, Pb and Sn It is very common and famous solder in the
are equally shared; hence, it is market. It provides a bright surface in finish
called half-half solder after soldering.
Brazing alloy 92% Sn, 5.5% Pb and 2.5% Cu These are used for soldering of steel joints.
Plumber alloy 67% Pb and 33% Sn It is commonly used for soldering the pipes.
The alloy containing about 60% Pb is used as solders in electrical wiring.
The capacity of solders depends upon the formation of a surface alloy between the solder and the parts
of metals being soldered. Based on desired melting point and the metals to be joined, the solder alloy
can be selected. Solders usually contain Pb and Sn as the main components.
Important solders and their compositions are shown in Table 8.2.
A good solder has the following characteristics
(i) Its melting point should be lower than the soldering metals
(ii) It should spread easily in liquid form and form homogeneous mixture with the soldering metals.
(iii) It should possess good quality of wetting the soldering metals.
(iv) Freezing Mixture

A mixture of ice and salt is known as freezing mixture; it has been observed that the addition of salt to
ice results in considerable lowering of temperature.
A good freezing mixture should satisfy the following conditions:
(i) Salt must be cheap, highly soluble and have a low cryohydric temperature.
(ii) The heat of solution of the salt should be high, that is, solubility of the salt should increase rapidly
on increasing the temperature.
(iii) Components used should form an intimate mixture on cooling.
Normally a mixture of ice and common salt is used as a freezing mixture because common salt is very
cheap and easily available. However, it is not a good component for freezing mixture due to the heat of
solution of the salt is very low and the heat absorbed is almost due to the heat of fusion of ice. Calcium
chloride hexahydrate and ice give an excellent freezing mixture because of very low cryohydric point
and high heat of solution.
Some important freezing mixtures, their eutectic temperatures and percentage composition are
listed in Table 8.3.
Table 8.3 Freezing mixtures

Composition (% of salt Eutectic temperature
System in the mixture) (°C)
NH4Cl and ice 20.1 -16.0
NH4NO3 and ice 43.0 -18.0
NaNO3 and ice 33.3 -18.1
NaCl · 2H2O and ice 23.0 -22.0
KI and Ice 52.0 -23.0
CaCl2 · 6H2O and ice 15.2 -55.9

8.18
8.6.2 Lead (Pb) – Silver (Ag) System

Both lead and silver are completely miscible in liquid state and form homogeneous mixture without
formation of any compound by the mixing of lead and silver.
Melting point of pure lead and pure silver are 327 °C and 961 °C respectively. Melting point of both
components i.e. solvent is lowered by the addition of solute. On addition of silver in lead, melting point
of lead is lowered and vice-versa.
The phase diagram of Pb·Ag system consists of the following points
(a) Curves AO, BO
(b) Areas above AOB, below AO and below OB
(c) Eutectic point (O)
The phase diagram of lead-silver system is shown in Figure 8.3.
X′
Liquid B(961°C)
Y′
Temperature (Not to scale)
Solid Ag
X +
A Liquid
327 °C
Y
Solid Pb
+
Liquid O
C D
303°C
Solid Pb Solid Ag
+ +
Eutectic Eutectic
E
F G
Pb = 100% Pb = 97.4% Pb = 0%
Ag = 0% Ag = 2.6% Ag = 100%
Composition (Not to scale)
Figure 8.3 Phase diagram of lead-silver system
Curves
(i) Curve AO: This curve represents the melting point or freezing point curve of Pb by addition of
small amount of Ag.
Along this curve solid Pb+ liquid melt are in equilibrium. Along this curve, the silver which is
added goes into solution while the separation of solid Pb takes place.
solid Pb liquid (solution of Ag in liquid Pb)

Phase Rule 8.19
C = 2, P = 2
F=C−P+1=2−2+1=1
The system is univariant along this curve. So, to specify the conditions of equilibrium between
two phases only one variable either temperature or composition is to be specified.
(ii) Curve BO: This curve represents the melting point or freezing point curve of Ag by addition of
small amount of Pb. Along this curve the lead which is added goes into solution while separation
of solid Ag takes place.
Along this curve two phases solid silver and liquid melt are in equilibrium.
Solid Ag liquid (Solution of Pb in liquid Ag)
C=2P=2
F=C−P+1=2−2+1=1
The system is univariant along this curve as two phases solid Ag and liquid are in equilibrium.
Only one variable either temperature or composition is to be specified for specify the conditions
of equilibrium between two phases.
Areas
(i) Area above AOB
In this area only one phase i.e. liquid melt (solution of Ag and Pb) co-exists
F=C−P+1
=2−1+1=2
The system is bivariant in this region. So, to show the existence of this phase in this region two
variables temperature as well as composition are required.
(ii) Area below AO or Area enclosed between AOC
In this area AOC, solid Pb and liquid melt co-exist
According to phase rule equation
F=C−P+1
= 2 − 2 + 1 = 1 (Univariant)
The system is univariant in this region. Only one variable either temperature or composition is
required to specify the equilibrium state.
(iii) Area below BO or Area enclosed between BOD
In this area, solid Ag and liquid melt co-exist.
So, according to condensed phase rule equation
F=C−P+1
=2−2+1=1
The system is univariant.
(iv) Area below the line COD
(a) Area enclosed between COEF:
Solid Pb and eutectic phases are co-exist in this region.
F=C−P+1=2−2+1=1
The system is univariant in this region.

8.20
(b) Area enclosed between ODGE:

Solid Ag and Eutectic phases are co-exist in this region.
F=C−P+1=2−2+1=1
The system is univariant in this region.
Points
(i) Point A and Point B: Point A represents the melting point of pure Pb (327 °C) and point B
represents the melting point of pure Ag (961 °C)
At point ‘A’
Solid Pb liquid Pb
P = 2, C = 1
F = C − P + 1 = 1 − 2 + 1 = 0 (Invariant)
At point ‘B’
Solid Ag liquid Ag
P = 2, C = 1
F = C − P + 1 = 1 − 2 + 1 = 0 (Invariant)
(ii) Eutectic Point ‘O’
It is a point where two curve AO and BO meet.
At this point, three phases are in equilibrium
At point ‘O’
Solid Ag Solid Pb liquid meet
(solution of Pb and Ag)
F=C−P+1
=2−3+1=0
Hence, system is invariant. This point ‘O’ represents the lowest possible temperature (303 °C)
below which a liquid phase cannot exist and beyond which the liquid phase cannot be enriched in either
component by freezing out the other component. Such type of liquid mixture of Pb and Ag which has
the lowest freezing point corresponding to all other liquid mixtures is called eutectic mixture and cor-
responding temperature is known as eutectic temperature.
At Eutectic point Pb = 97.4%, Ag = 2.6% and Eutectic temperature = 303 °C.
Cooling of Melt in the Area Above AOB/Pattinson’s Process for Desilverization of Lead
When a liquid melt of certain composition at a point X (or X′) in the area above AOB is allowed to cool,
it follows Newton’s Law of cooling, as follows the path XY(or X′Y′) in the phase diagram. Lead crystals
start separating when point Y is reached and further follows the path YO as we continue the cooling of
liquid melt and correspond silver crystals separate out along the path Y′O and point ‘O’ is reached, this
point is known as eutectic point (low melting) and the solid mixture is called eutectic mixture which
has a characteristic composition for each system.

Phase Rule 8.21
8.7 HEAT TREATMENT OF STEEL

Heat treatment is the combination of heating and cooling of a metal or alloy in one or more temperature
cycles to get desirable physical properties to the metals or alloys. Heat treatment of steel may be carried
out under near equilibrium conditions to enhance the ductility or under non-equilibrium conditions to
enhance the hardness. During heat treatment, the shape and size of the grains or the compositions of
the phase undergoes changes with respect to the microconstituents..
Pure iron is not useful for fabrication of structure component because of its weak mechanical
properties. So a non-metallic element i.e. carbon forms alloys with iron to give various type of steel
and improves the mechanical properties of the base metal. Due to small size of carbon as compared
with iron atom carbon interstitial positions in the lattice formed depends on the crystal structure of
iron which in turn depends on the temperature, as pure iron exist in three allotropic modifications of
a, g and d forms.
The low temperature allotropic form called the α-iron has a body-centered cubic (BCC) struc-
ture which is stable upto 910 °C. In the temperature range between 910 °C 1400 °C, g -iron with a face
centered cubic (FCC) structure is stable and the high temperature allotropic form d -iron has a BCC
structure and it is stable beyond 1400 °C and upto 1535 °C.
Plain carbon steel on heating to temperature more than 723 °C and maintained at this temperature
for a long time allows the formation of the austenite phase and the dissolution of more carbon in the
FCC structure. On slow cooling of the austenite phase transformation of FCC to BCC occurs and the
excess carbon forms cementite.
Hardening
If the steel is quenched by plunging into water or oil to 204°C or a lower temperature, the carbon atom
do not have sufficient time to form cementite but remain trapped in the BCC structure. The excess car-
bon precipitates out in the hot metal and prevents the slipping of the planes. Hence, quenched steel is
quite hard and strong but has lower ductility; this heat treatment is called as transformation hardening.
This involves the transformation of austenite to martensite or the bainite-phase making the steel hard.
Tempering
Due to its brittleness, the quenched steel is not useful for construction purpose; hence, quenching is
always followed by another heat treatment process called tempering. The quenched steel is tempered
by reheating to below the a -iron to g -iron transition temperature. The residual stress and strain are
relieved, and the excess of carbon is rejected in the form of e -carbide (Fe2.4C). By tempering the steel
becomes tougher and ductile. Tempering is carried out at about 200 °C to make hard steel resistant to
abrasion or at higher temperature (~540 °C) to make tough steel capable of withstanding shock loads.
Annealing
This involves heating and holding the steel at a suitable temperature for some time to facilitate the dis-
solution of carbon in g -iron in a furnace; steel is softened and becomes ductile and also machinable.
However, annealing decreases the hardness and strength of the steel. Annealed hypereutectoid steel
contains cementite. It is not soft but can be machined easily. In contrast, annealed hypo-eutectoid steel
contains ferrite and is relatively soft and malleable.

8.22
1000
900 g
g + Fe3C
Temperature (°C)
800 a +g
a
700 Spheroidizing
Process anneal
600
a + Fe3C
500
0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
Carbon (%)
Phase diagram of iron carbon system

1. A homogenous and physically distinct and mechanically separable part of system is called as
____________.
[Ans.: Phase]
2. Number of phases when CaCO3(s) heated is ____________.

[Ans.: 3 (Three)]
3. The smallest number of independent variable constituents by which the composition of each
phase can be expressed in the form of chemical equation is ____________.
[Ans.: Components]
4. The number of component when NH4Cl heated in a closed vessel is ____________.
[Ans.: One]
5. The point at which the gaseous, liquid and solid phases of the system co-exist in equilibrium is
called as ____________.
[Ans.: Triple point]
6. Degree of freedom is zero at triple point is called as ____________.
[Ans.: Invariant system]

Phase Rule 8.23
7. At Invariant system, value of F is ____________.

[Ans.: Zero]
8. In the expression C = S - R, R is number of ____________.
[Ans.: Independent chemical reactions]
9. In case of ionic reaction, the formula for calculating number of component is ____________.
[Ans.: C = S – (R + 1)]
10. The point which refers to the temperature and pressure where a liquid and its vapour become
identical is called as ____________.
[Ans.: Critical Point]
11. The degree of freedom at the triple point of one component system is ____________.
[Ans.: Zero]
12. The existence of a solid substance in more than one crystalline form is called as ____________.
[Ans.: Polymorphism]
13. In a phase diagram, the crossing of a two-phase equilibrium curve is called as ____________.
[Ans.: Transition]
14. The melting point of ice can be lowered by an increase of ____________.
[Ans.: Pressure]
15. Eutectic temperature of Pb-Ag system is ____________.
[Ans.: 303 °C]
16. Phase diagram of Pb-Ag system is plotted between temperature and ____________.
[Ans.: Composition]
17. Mathematical statement of reduced phase rule is ____________.
[Ans.: [F′ = C - P + 1]]
18. At Eutectic point the composition of Pb = ____________ and Ag = ____________.

[Ans.: = 97.4%, 2.6%]
19. Metals essential for solders are ____________ and ____________.
[Ans.: Lead and Tin]
20. In order to get a two metal low melting alloy, ____________ composition is preferred.
[Ans.: Eutectic]
21. The fundamental principle of freeze-drying is ____________.
[Ans.: Sublimation]
22. Iron –Carbon alloys containing 1.7% of carbon are classified as ____________.
[Ans.: Steel]

8.24
23. The percentage of carbon in cast iron is ____________.

[Ans.: 3%]
24. The most important low melting alloys are ____________ and ____________.
[Ans.: Wood metal, Rose metal]
25. A ____________ is a low melting alloy which is used to join two metal pieces together.
[Ans.: Solder]
26. Soft solders mainly contain ____________ and ____________.
[Ans.: Sn, Pb]
27. An ____________ equilibrium diagram indicates the phase changes during heating and cool-
ing and the nature and amount of structural component of steel and cast-iron exist and any
temperature.
[Ans.: Iron-carbon]
28. The solubility or carbon in iron depends on the ____________ of iron.
[Ans.: Crystal structure]
29. The curve above which the system consist of liquid phase only is ____________.
[Ans.: Freezing curve]
30. The curve below which the system consist of solid phase only is ____________.
[Ans.: Melting curve]

1. The Gibb’s phase rule is given as
(a) F = C - P + 2 (b) F = C - P + 1
(c) F = C + P - 2 (d) F = C + P + 2
[Ans.: a]
2. The condensed phase rule is given as

(a) F = C - P + 2 (b) F = C - P + 3
(c) F = C + P + 1 (d) F = C - P + 1
[Ans.: d]
3. Which of the following has higher vapour pressure

(a) super-cooled water at -5 °C (b) Ice at -5 °C
(c) Vapour at -5 °C (d) None of these
[Ans.: a]
4. Dissociation of NH4Cl in a closed vessel is a

(a) one component, one phase system
(b) one component, two phase system

Phase Rule 8.25
(c) Two component, one phase system

(d) Two component, two phase system
[Ans.: b]
5. A system consisting of rhombic sulphur, monoclinic sulphur and vapour in equilibrium is
(a) Non variant (b) univariant
(c) bivariant (d) trivariant
[Ans.: a]
6. In the lead-silver system, the percentage of silver present at the eutectic point is
(a) 0% (b) 2.6%
(c) 97.4% (d) 100%
[Ans.: b]
7. In water system, the three phases exist in equilibrium at

(a) 0 °C, 1 atm (b) 0 °C, 4.58mm
(c) 0.0098 °C, 1 atm (d) 0.0098 °C, 4.58mm
[Ans.: d]
8. Water system is non variant at

(a) Melting point (b) Boiling point
(c) Triple point (d) Critical point
[Ans.: c]
9. Number of phases present in a mixture of N2 and H2 are

(a) 1 (b) 2
(c) 3 (d) 4
[Ans.: a]
10. Number of component present in the following reaction CaCO3(s) → CaO(s) + CO2(g)
(a) 1 (b) 2
(c) 3 (d) 4
[Ans.: b]
11. At the eutectic point, a system has
(a) The lowest melting point (b) The highest melting point
(c) Only two phases (d) Uncertain composition
[Ans.: a]
12. What is degree of freedom at eutectic point
(a) 1 (b) 0
(c) 2 (d) 3
[Ans.: b]

8.26
13. At eutectic point, composition of Pb-Ag system

(a) 100% Pb + 0% Ag
(b) 0% Pb + 100% Ag
(c) 50%Pb + 50% Ag
(d) 97.4%Pb + 2.6% Ag
[Ans.: d]
14. For C = 1 and P = 3, the degree of freedom is
(a) 0 (b) 1
(c) 2 (d) 3
[Ans.: a]
15. For water system, the value of component is
(a) 0 (b) 1
(c) 2 (d) 3
[Ans.: b]
16. Two miscible liquids such as water and alcohol has how many phases
(a) 1 (b) 2
(c) 3 (d) 4
[Ans.: a]
17. Two inmiscible liquids such as water and mercury has how many phases
(a) 1 (b) 2
(c) 3 (d) 4
[Ans.: b]
18. A system of NaCl-KCl-H2O has how many components

(a) 1 (b) 2
(c) 3 (d) 4
[Ans.: c]
19. A binary system consisting of two substances, which are miscible in all proportions in the liquid
phase, but do not react chemically is known as
(a) Invariant system (b) Univariant system
(c) Metastable system (d) Eutectic system
[Ans.: d]
20. The hardest structure that appears on the iron-carbon equilibrium is
(a) Ledeburite (b) Pearlite
(c) Cementite (d) Ferrite
[Ans.: c]

Phase Rule 8.27
21. In Pb-Ag system, the euetectic temperature is

(a) 298 °C (b) 300 °C
(c) 303 °C (d) 310 °C
[Ans.: c]
22. The melting point of pure Pb and pure Ag is
(a) Pb = 100 °C, Ag = 100 °C
(b) Pb = 373 °C, Ag = 298 °C
(c) Pb = 327 °C, Ag = 961 °C
(d) Pb = 961 °C, Ag = 327 °C
[Ans.: c]
23. A system consists of water  vapour, the degree of freedom is
(a) 0 (b) 1
(c) 2 (d) 3
[Ans.: b]
24. With increase of pressure, melting point of ice is
(a) Increase
(b) decreases
(c) remains unchanged
(d) doesn’t show any behaviour
[Ans.: b]
25. For one component system, the maximum number of degree of freedom is
(a) 0 (b) 1
(c) 2 (d) 3
[Ans.: c]
26. A binary alloy system having value of component is
(a) C = 1 (b) C = 2
(c) C = 3 (d) C = 4
[Ans.: b]
27. Soft or Tinner’s solder consists of mainly

(a) Pb and Sn (b) Pb and Ag
(c) Sn and Ag (d) Pb and Bi
[Ans.: a]
28. Wood metal alloy containing metal is

(a) 50% Bi + 20% Pb + 20% Sn + 10% Cd
(b) 20% Bi + 50% Pb + 20% Sn + 10% Cd

8.28
(c) 50% Bi + 25% Pb + 12.5% Sn + 12.5% Cd

(d) 25% Bi + 50% Pb + 12.5% Sn + 12.5% Cd
[Ans.: c]
29. Plumber solder used for soldering consist of
(a) 67% Pb + 33% Sn (b) 50% Pb + 50% Sn
(c) 33% Pb + 67% Sn (d) 25% Pb + 75% Sn
[Ans.: a]
30. The principle of freeze-drying is
(a) Evaporation (b) condensation
(c) sublimation (d) Fusion
[Ans.: c]

1. Define or state phase rule.
Ans.: Phase rule can predict qualitatively the effect of temperature, pressure and concentration
on a heterogenous system which is in equilibrium and it is assumed that equilibrium is not
influence by gravity, electrical or magnetic forces, or by surface action. The degree of free-
dom is related to number of components (C) and of phases (P) by the phase rule equation.
F=C-P+2
2. What is condensed phase rule?
Ans.: When the pressure of the system remains constant, then the phase rule equation becomes.
F=C-P+1
3. Point out the effect of increase of pressure on the melting point of ice.
Ans.: Melting point of ice decreases with rise of pressure as shown in the water system diagram
that curve is inclined towards pressure axis.
4. Define phase

Ans.: A phase may be defined as any part of a system which is homogeneous in itself, physically
distinct, and mechanically separable from other parts of the system.
5. Calculate the, degree of freedom of the following systems

(i) Unsaturated solution of NaCl in equilibrium with its vapour.
(ii) Na2SO4 in water a closed contained at 32.4 °C
Ans.: (i) The system has two phases, solution and vapour and it is a two component system.
Then degree of freedom
F=C-P+2
=2-2+2=2
So, the system is bivariant,

Phase Rule 8.29
(ii) The system has two phases, solution and vapour and it is a two component system.
Since Temperature is fixed at 32.4 °C. So we will apply condensed phase rule equation to
evaluate degree of freedom
F=C-P+1
=2-2+1=1
So, the system is univariant.
6. What is the number of phases when CaCO3(s) is heated,
Ans.:
D
CaCO3(s) → CaO(s) + CO2(g)
Three phases i.e., two solids and one gaseous.
7. How many components are present when NH4Cl is heated in closed vessel.
Ans.: One.
8. Give the number of phases, components and degree of freedom of following
(a) Mixture of N2 and H2 contained in a vessel.
(b) Ice, water and vapour in equilibrium.
(c) An unsaturated sugar solution.
(d) A system consisting of NaCl, KCl, and H2O.
(e) Dissociation of NH4Cl in a closed vessel.
(f) Dissociation of NH4Cl in a closed vessel containing NH3 also.
Ans.:
(a) P = 1 (gaseous phase)
C = 2 (N2, H2)
F=C-P+2=2-1+2=3
(b) P = 3 (ice, water, vapour)
C = 1 (water)
F=C-P+2=1-3+2=0
(c) P = 2 (solid, solution)
C = 2 (sugar, water)
F=C-P+2=2-2+2=2
(d) P = 1 (solution)
C = S - R = 5 - (2 + 1) = 2
F=2-1+2=3
(e) P = 2 (solid, gas)
C = 1 (NH4 Cl)
F=C-P+2=1-2+2=1
(f) P = 2 (solid, gaseous)
C = 2 (NH4 Cl, NH3)
F=C-P+2=2-2+2=2

8.30
9. Classify the following into true and metastable equilibria

(a) Ice and liquid water at atmospheric pressure and 0 °C
(b) water at -3 °C
(c) water and its vapours at 20 °C
(d) SR and monoclinic SM below 95.5 °C
Ans.:
(a) True equilibrium
(b) Metastable equilibrium
(c) True equilibrium
(d) True equilibrium
(e) Metastable equilibrium
10. What is the criterion of multiphase equilibrium?
Ans.: Chemical potential of a component must be same in all phases in equilibrium.
11. What is an invariant system.
Ans.: A system in which degree of freedom is zero i.e., no condition is required to be specified
to define the system.
12. Give an example of invariant system.
Ans.: A system consisting of ice, water and water vapour in equilibrium.
13. Give a mathematical statement of phase rule in the following cases:-
(a) When temperature, pressure and concentration are variables.
(b) When temperature and concentration are variables
(c) When concentration and pressure are variables.
(d) When concentration, pressure, temperature and magnetic force are variables.
Ans.:
(a) F = C - P + 2
(b) F = C - P + 1
(c) F = C - P + 1
(d) F = C - P + 3
14. Give the degree of freedom of one component system in the following cases
(a) When a single phase exists.
(b) When two phases are in equilibrium.
(c) When three phases are in equilibrium.
Ans.:
(a) Two
(b) One
(c) Zero

Phase Rule 8.31
15. What is the minimum number of phases that can co-exist in a one component system.
Ans.: Three
16. What is triple point.

Ans.: A point at which the gaseous, liquid and solid phases of the system co-exist in equilibrium
17. What is the triple point of water system.

Ans.: When system is at 0.0098 °C and 4.58 mm Hg pressure.
18. What is the difference between a phase and a state of matter.

Ans.: There are three states of matter-solid, liquid and gas. A phase is a sample of matter with
definite composition and uniform properties throughout the sample.
19. What is meant by polymorphism.

Ans.: The existence of a solid substance in more than one crystalline form.
20. What is meant by transition?

Ans.: The crossing of a two-phase equilibrium curve in a phase diagram.
21. What is difference between critical point and triple point,

Ans.: Critical point refers to the temperature and pressure where a liquid and its vapour become
identical while triple point is the condition of temperature and pressure under which three
phases of a substance co exit in equilibrium.
22. What is metastable state.

Ans.: The state of super cooled or super saturated solution in which the phase, which is normally
stable under the given conditions, does not form, under normal conditions.
23. What is meant by the term eutectic?

Ans.: A solid solution of two or more substances having the lowest freezing point of all the
possible mixture of the components.
24. What is eutectic composition of Pb-Ag system

Ans.: 97.4%Pb and 2.6% Ag.
25. What is the degree of freedom at eutectic point?
Ans.: zero
26. State the condition in which two substances can form a simple eutectic.
Ans.: The two substance must
(i) Be completely miscible in the liquid state, but immiscible in the solid state
(ii) Not chemically react with each other
27. Justify the statement the eutectic is a mixture and not a compound.
Ans.: Eutectic is a mixture of two solids, which exists at the lowest melting point. Since eutectic
is completely immiscible in the solid state, so it is a mixture and not a compound.

8.32
28. What is the eutectic temperature of Pb-Ag system.

Ans.:Euetctic temperature: 303 °C
29. Name two systems which form eutectic mixtures,

Ans.:
(i) NH4Cl +ice
(ii) KNO3 + ice
30. Which metals form the essential constituents of solders and what is the composition of tinman’s
solder?
Ans.: Lead and Tin are the essential constituents of solders,
Composition of tinman’s solder is
66% Sn + 34% Pb
31. What is a phase diagram
Ans.: Phase diagram is obtained by plotting concentration versus temperature.
32. Why do study phase diagram.
Ans.: To predicts whether a triple point or eutectic alloy or solid solution is formed on cooling a
homogenous liquid mixture containing two metals.
8.8.4 Solved Numerical Problems

(1) Calculate the number of phases, components and degree of freedom in the following systems
(i) CaCO3(s) → CaO(s) + CO2(g)
(ii) H2O(s) → H2O(g) + H2O(l)
(iii) An aqueous solution of NaCl and Na2SO4
Solution
(i) CaCO3 (s) → CaO(s) + CO2(g)
Number of phases = 3 [i.e. CaCO3(s), CaO(s), CO2(g)]
Number of component, C = S - R
S = 3 (number of species)
R = 1 (Number of relation)
C = S - R = 3 - 1 = 2 Component system
So, according to phase rule
F = C - P + 2 = 2 - 3 + 2 = 1 (univariant)
(ii) H2O(s) → H2O(g) + H2O(l)
Number of component = 1 (H2O only)
Number of phases = 3 (solid, liquid, vapour)
So, degree of freedom
F = C - P + 2
= 1 - 3 + 2 = 0 (Invariant)

Phase Rule 8.33
(iii) An aqueous solution of NaCl and Na2SO4

Number of phases, P = 1 (i e solution)
Number of component, C = 3 (i.e NaCl, Na2SO4, H2O)
So, degree of freedom
F=C-P+2=3-1+2=4
(2) Write down the number of component, number of phases and calculate the degree of freedom for
the following equilibria:-
(i) N2(g) + 3H2(g) → 2NH3(g)
(ii) Fe(S) + H2O(g) → FeO(s) + H2(g)
(iii) H2O(g) → H2(g) + ½O2(g)
Solution
(i) Chemical species present are
N2(g), H2(g) and NH3(g)
Number of component C = S - R
S = 3 [Number of species N2, H2 and NH3]
R = 1 [Number of relation]
C = S - R = 3 - 1=2
Number of phases P = 1 (gaseous phase)
Degree of freedom, F = C - P + 2
=2-1+2=3
(ii) Chemical species present are
Fe(s), FeO(s), H2O(g), H2(g)
Number of components, C = S - R
=4-1=3
Number of phases = 3 (Two solids and one gaseous phase)
Degree of freedom, F = C - P + 2
=3-3+2=2
(iii) Number of species present are
H2O(g), H2 (g), and O2 (g)
Number of components C = S - (R + 1)
= 3 - (1 + 1)

=1

Number of phases, P = 1 (gaseous phase)
Degree of freedom, F = C - P - 2
=1-1+2=2
(3) Explain KCl-NaCl-H2O is a three component system while NaBr-KCl-H2O is a four component
system.

8.34
Solution
First system KCl-NaCl-H2O
Total Number of species, S = KCl, NaCl, H2O, K+, Cl−, Na+ (dissociation of water is neglected)
S = 6
Number of independent relations, R = 2
KCl  K+ + Cl−
Nacl  Na+ + Cl−
Thus, C = S - (R + 1) = 6 - (2 + 1) = 3
In the second system,
Total number of species, S = 9
KCl, NaBr, H2O, NaCl, KBr, Na+, K+, Cl−, Br−
The number of independent reactions, R = 4
KCl  K+ + Cl−
NaBr  Na+ + Br−
Na+ + Cl−  NaCl
K+ + Br−  KBr
C = S - (R + 1)
= 9 - (4 + 1) = 4
It is a four component system.

Q.1 State phase rule and explain the significance of the term involved. Illustrate with suitable
examples.
Q.2 Define the terms with suitable example.
(i) Phase
(ii) Component
(iii) Degree of freedom
(iv) Triple point
(v) Eutectic mixture
(vi) Condensed phase rule
Q.3 Draw a phase diagram for one component water system. Label it and discuss the importance of
various points, lines and areas at equilibrium.
Q.4 What is meant by triple point of water?
Why is it different from the normal melting point of ice?

Q.5 Differentiate between True equilibrium and Metastable equilibrium?

Phase Rule 8.35
Q.6 Derive Gibb’s phase Rule equation.

Q.7 Justify the statement ‘The Eutectic is a mixture and not a compound.”
Q.8 What is meant by eutectic point? Explain how can the eutectic point be calculated ? Discuss the
Pb – Ag system.
Q.9 What is the number of phases in the following systems?
(i) Saturated solution of NaCl
(ii) Mixture of rhombic and monoclinic sulphur
(iii) Mixture of O2 and N2
(iv) Mixture of benzene and water
Q.10 Water system is a respresentative system for explaining phase rule and phase equilibria. Explain.
Q.11 Discuss a typical one-component system from the stand point of phase rule.
Q.12 Explain why KCl-NaCl-H2O should be regarded as a three component system: whereas KCl-
NaBr-H2O should be regarded as a four component system.
Q.13 What is condensed phase rule? When is it applied?
Q.14 Define and explain the term components of a system with suitable examples.
Q.15 Discuss the salient feature of Fe-C system.
Q.16 Define the various curves involved in water system with a neat and sketched diagram, why is the
fusion curve in the phase diagram of water system inclined towards the pressure axis? Explain
Q.17 What is a triple point? Explain triple point with reference to water system.
Q.18 Explain the terms
(i) Stable equilibrium,
(ii) Metastable equilibrium,
Q.19 Derive phase rule equation viz. F = C - P + 2, why reduced phase rule is applicable in Pb-Ag
system.
Q.20 Calculate P, C and F in the following cases
(i) NH3(g) at 42 °C
(ii) An emulsion of oil in water at 2 atm and 70 °C
(iii) SR  SM at the transition temperature
(iv) Pure crystal of CuSO4 5H2O
(v) Water system at 4.578 mm of Hg and at 0.0098 °C

9 PHOTOCHEMISTRY
9.1 INTRODUCTION
Photochemistry is the branch of chemistry which deals with the effect of light on chemical systems.
A photochemical reaction is caused by the absorption of electromagnetic radiation, especially ultra-
violet (UV)—visible radiations. Photochemical reactions proceed differently from thermal reactions;
hence they have a lot of importance in organic and inorganic chemistry. The photochemical path offers
advantages over thermal methods of forming thermodynamically disfavoured products by overcom-
ing large activation barriers and the reaction will be completed in a short period of time. Hence, many
thermal reactions have photochemical counterparts.
Some examples are photosynthesis, formation of Vitamin D with sunlight in the body and ozone
formation when oxygen is exposed to sun light.
9.2 LIGHT SOURCE IN PHOTOCHEMISTRY

Photochemists typically work in only a few sections of the electromagnetic spectrum. The most widely
used sections are UV and visible regions. The main source of light is the sun, mercury (high, medium
and low pressure) lamps, sodium lamps, halogen lamps, LASER, etc. Different lamps and their inten-
sity ranges are shown in Table 9.1.
Table 9.1 Different lamps and their intensity ranges

Name of the lamp Wavelength range (nm)
The sun 300–1400
Low-pressure mercury (5–10 atm) 185–254
High pressure Hg lamps (100 atm) (Highly expensive 360–600
and easily damaged)
Low- and high-pressure sodium lamps 600
High power light emitting diodes (Very narrow and 400–650
intensive emission, long life time)
The common types of reactors, vessels and apparatus used for photochemical reactions are irradiated
flasks (used for external irradiation), immersion-well reactors (here, the lamp is surrounded by the
reaction solution), falling film apparatus and photo-microreactors (similar to falling films, but easy to
handle). In all these cases, the lamp usually requires cooling to avoid its overheating.

Solid or liquid optical filters may be used to restrict the irradiation wavelength, the glass acts as a
good solid filter. The different glasses used for irradiation at different wavelengths are as follows:
(i) Quartz glass to irradiate at 254 nm
(ii) Pyrex glass to irradiate at 300 nm
(iii) Normal lab glass to irradiate > 350 nm
9.3 LAWS OF PHOTOCHEMISTRY

Photochemical reaction is initiated by electronically excited molecules or atoms produced by the
absorption of electromagnetic radiation, usually visible or near the UV region.
Photochemical reactions are governed by three basic principles. They are as follows:
(i) Grotthuss–Draper law
(ii) Stark-Einstein law of photochemical equivalence
(iii) Beer-Lambert law
9.3.1 Grotthuss–Draper Law or The First Law of Photochemistry

This law states that light must be absorbed by a chemical substance for a photochemical reaction to
take place. Photoexcitation is the first step in the photochemical process, where the reactant is elevated
to a state to higher energy an excited state. The Grotthuss–Draper law is also known as the first law of
photochemistry.
When light pass through any substance, only a fraction of the incident light which is absorbed by
the substance brings about a chemical change and the reflected and transmitted light do not produced
any such affect. Hence, it is important to remark that in all light radiations, which are absorbed, the
reaction systems do not cause an affect in producing the final product. In some cases, the absorbed light
is reemitted as radiations of the same belong to a different frequency.
The Grotthuss–Draper law is purely qualitative assumption; it does not explain the relation
between the amount of light absorbed by the system and the number of molecules which have reacted
and give a final product.
9.3.2 Stark-Einstein Law or Photochemical Equivalence Law

According to this law, for each photon of light absorbed by a chemical system, only one molecule is
activated for the subsequent reaction. This photoequivalence law was derived by Einstein during his
development of the quantum theory of light; hence it is known as the Stark-Einstein law. No more than
one molecule is activated for the photochemical reaction, as defined by the quantum yield.
According to this law, the part of a light induced on the system the primary process can occur this
is the initial chemical change that results directly from the absorption of light. However, in most pho-
tochemical reactions, the primary processes are usually followed by a secondary process due to normal
interactions between the reactants and they are not required to absorb any light radiation. As a result,
such reactions do not obey the one quantum–one molecule reactant relationship.
The law is further restricted to conventional photochemical processes using the light source of
moderate and high intensity sources; those used in flash photolysis and laser experiments are known as
biphotonic processes—the absorption by a molecule of a substance of two photons of light.

Photochemistry 9.3
9.3.3 Beer-Lambert Law

The Beer-Lambert law proposed that the absorption of light or single wave length is related to the expo-
nential to the thickness of the absorbing compound and the optical path of light thus:
I t = I o e − an (1)
where Io = intensity of incident light
It = intensity of transmitted light
a = constant
n = thickness of absorbing material.
Equation (1) is subsequently modified that thus the Beer-Lambert law of light absorbing is formu-
lated as follows:
I = I o e − ∈cl
I
= e −∈cl
Io
I
log o = ∈ cl (or ) A = ∈ cl
I
9.4 PHOTOPHYSICAL AND CHEMICAL PROCESSES

After absorbing the energy, the excited molecule may undergo different physical and chemical processes.
9.4.1 Photophysical Process

The excited or energised molecule may return to its initial state by any of the following physical
processes:
(i) The molecule can release the excitation energy by emitting radiation through fluorescence or
phosphorescence.
(ii) The absorbed energy may transfer to some other molecule to colloids, without emitting light or
giving product.
(iii) An electron in the atom or molecule may absorb so much energy that it may escape from the atom
or molecule, leaving behind the positive M+ ion by photoionisation.
Jablonski Diagram
The photophysical process can be easily explained by the Jablonski diagram. Once a molecule that has
absorbed energy in the form of electromagnetic radiation goes to excitation state, while coming back
to the ground state, a number of paths may follow.
Quantum mechanics explains internal conversion of energy as a transfer of excess electronic
energy into excess vibrational energy of a lower electronic state, and followed by dissipation of vibra-
tional energy into the surroundings as heat. New jabolonski diagram giving a glance about photo
physical process shown in Figure 9.1.
Internal Conversion
Internal conversion is an intermolecular conversion of molecules which possess to a lower electronic
state without emitting radiation. The higher excited singlet states (S1, S2, S3, … generally denoted as Sn)

and the lowest energy triplet states (T1, T2, T3, …) perform a crossover of two states with the same mul-
tiplicity, that is, singlet to singlet or triplet to triplet state. The internal conversion is more efficient when
two electronic energy levels are close enough that two vibrational energy levels can overlap in between
S1 and S2.
Fluorescence
The internal conversion can also occur in between S1 and S0 (lowest energy or ground state) and is much
slower, allowing time for the molecule to emit a photon or loss of energy from a higher excited state.
This is known as fluorescence.
Inter-system Crossing
The internal conversion from S1 to S0 is due to the vibrational levels of the ground state overlap with
the first excited state for some molecules, which leads to fast deactivation.
Inter-system crossing is a radiation-less process involving a transition between two different
multiplicities—that is S1 (singlet) to T1 (triplet) electronic states. The probability of inter-system cross-
ing is due to the overlapped vibration levels of the two singlet states. This is commonly observed
in molecules containing heavy atoms such as iodine or bromine. The spin and orbital interaction
increases, and the spin becomes more favourable; paramagnetic species also enhance inter-system
crossing, which consequently decreases fluorescence.
Phosphorescence
The emission of photon by internal conversion of electron from T1 to S0 is known as phosphorescence.
The triplet states (with parallel spins) interact more strongly than singlet states (with opposing spins),
the energy difference of T1 − S0 is less than S1 − S2. Hence, phosphorescence occurs at longer wave-
lengths than fluorescence. Important photo physical processes and their transitions shown in Table 9.2.
Table 9.2 Photo physical processes and their transitions

Photophysical process Transition occurs
Light absorption (excitation) S0 − Sn or Tn
Internal conversion Sn − S1 or Tn − T1
Vibrational relaxation Sn* − Sn
Inter-system crossing S1 − T1
Fluorescence S1 − S0
phosphorescence T1 − S0
Non-radiative decay S1 − S0 or T1 − S0
9.4.2 Photochemical Process

A photochemical reaction is a chemical reaction initiated by the absorption of energy in the form of light.
Primary Photochemical Process

If the excited molecule (M*) reacts, it may undergo any of the following chemical processes:
(i) Photodissociation
(ii) Inter-molecular rearrangement
(iii) Reaction with another molecule

Photochemistry 9.5
A = Photon absorption
F = Flourocense
P = Phosphorosence
IC = Internal conversion
ISC = Inter system crossing
Sn
V.R = Vibration relaxation
V.R
S = Singlet state
S2 T = Triplet state
IC ISC
S1 T2
Energy
F IC
P
S0 T1
A
Electronic energy level

diagram
Figure 9.1 Jablonski diagram showing photophysical process
Photodissociation
Dissociation of the molecules of a substance is caused by absorption of radiation energy into atomic
and/or molecular fragments.
M → M * → M + + n+
Photoisomerisation
The conversion of a molecule into its isomer with the same number and types of atoms but a different
structural arrangement is called photoisomerisation.
N−a→N−b
Inter-molecular Rearrangement
By irradiating with light, the molecule will absorb the light energy and will rearrange.
A−B−C→C−B−A
Secondary Photochemical Process

The secondary process may occur upon completion of the primary step.
Several examples of such process are described here:
(i) Ozone formation:
O2 → 2O *
2O * + 2O2 → 2O3
(ii) Destruction of ozone in the upper stratosphere
(iii) Chain reaction

9.5 QUANTUM YIELD AND QUANTUM EFFICIENCY

The efficiency of the photochemical reaction is expressed by the quantum efficiency or quantum yield.
It is a measure of the number of product molecules formed by the quantum of energy absorbed
from each photon.
f is defined as the number of molecules reacted for every number of quanta of light absorbed:
Number of molecule reacted

f =
Number of quantum light absorbed
The concept of quantum efficiency was first introduced by Einstein as each quanta of light absorbed
least formation of product. Though f = 1, in practice, it can be observed from 10−2 to 107.
Low quantum is absorbed in cases where the deviation of the molecules takes place before they
form the product. The deviation may take place by collisions of excited molecules split into other
excited molecules or non-excited molecules in cases where the primary photochemical process gets
reversed. The dissociation of molecule takes place and the dissociated fragments may be recombined
to form the original molecule.
High quantum efficiency is observed in free radical reactions. Photochemical free radical energy
is absorbed only in the chain initiation step to the formation of chain initiation-free radical, but will
propagate the reaction in the propagation step without absorbing any energy. This process is continu-
ous until the product is formed in the termination step.
9.6 PHOTOSENSITISATION
Photosensitisation is a process wherein an electronically excited molecule transfers its energy to another
non-radioactive molecule. After transferring energy, the other molecule gets excited and undergoes pho-
tochemical change. This process is called photosensitisation. Photosensitisation may be inter-molecular or
intra-molecular.
The initially excited molecule D* is designated as donor and the non–radioactive molecule is des-
ignated as the acceptor. This process is represented by this scheme:
D hv→ D * Excited state

A + D* → A * + D (photosensitisation)
There are two types of mechanisms postulated for non-radioactive energy as follows:
(i) Long-range transfer by dipole-dipole interaction
(ii) Short-range transfer by change interaction
9.7 PHOTODYNAMIC THERAPY

Cancer can be defined as a class of disease characterised by uncontrolled growth of a group of cells
beyond their normal limit and invasion to adjacent healthy tissues, which involves dynamic changes in
the genome. Photodynamic therapy (PDT) has emerged as a promising non-invasive chemotherapeutic
technique for the treatment of cancer which uses light to activate the drug molecule (photosensitiser)

Photochemistry 9.7
to produce reactive singlet oxygen species in the presence of molecular oxygen to damage the cancer
cells. Here, cancer cells are selectively targeted and damaged by red light of 600–800 nm wavelength
(photospectral window) by leaving the healthy cells unaffected.
In PDT, the drug is first injected into the patient’s body and sufficient time is given to accumulate
the drug inside the tumour. Subsequently, light is selectively exposed to the tumour to activate the
photosensitiser and to kill the cancer cells. Three essential components for the PDT are photosen-
sitiser, light of a particular wavelength and molecular oxygen. A photosensitiser is a biocompatible
light sensitive molecule which can be photoexcited by a particular wavelength of light. In the excited
state, it can transfer energy to the molecular oxygen to generate reactive oxygen species like singlet
oxygen.
Tissue
Photosensitizer oxygen
(excited state) Photosensitizer
Free radicals
singlet oxygen Cell
Death
Light
Oxygen
source
Photosensitizer Cellular
Light (ground state) toxicity
The photosensitiser used in PDT is mostly the organic molecule. An ideal photosensitiser suitable for
PDT application must fulfil the following criteria. First, the dark toxicity should be as less as possible.
Second, it should have an excited absorption band at visible wavelength, preferably in the range of
600–800 nm which is known as the PDT window. Shorter wavelength has less tissue penetration and
often leads to skin photosensitivity. Longer wavelength of light lowers the quantum yield of triplet
formation which hinders energy transfer to the ground state oxygen molecule to excite it to the sin-
glet state. Third, the photosensitiser should have good aqueous solubility and its excretion from the
patient’s body should be rapid to avoid side effects.
9.8 IMPORTANT PHOTOCHEMICAL REACTIONS

Some examples of photochemical reactions are as follows:
Photosynthesis
(i) Plants use solar energy to convert carbon dioxide and water into glucose and oxygen with the
help of chlorophyll.
(ii) Vitamin D is formed when the human body is exposed to sunlight.
Polymerisation
Many free radical polymerisation reactions start by photoinitiators, which decompose upon absorbing
light to produce the free radicals.

Photodegradation
In many drug bottles, the first precaution is to preserve the drug in a cool and dark place. This is
essential to avoid the drug from photodegradation. For example, poly vinyl chloride medicine bottles.
Photodynamic Therapy
Singlet oxygen is generated by the photosensitised drug when it is exposed to light; it destroys tumours
without affecting normal healthy cells.
Organic Photochemistry
(i) Many organic reactions are initiated by light to give final products with low cost. For example, the
formation of cyclo compounds from alkenes, Zimmerman’s di-pi-methane rearrangement, etc.
(ii) Industrial preparation of benzyl chloride by the gas-phase photochemical reaction of toluene with
+ hv •
chlorine. Cl 2 → 2Cl
C6H5CH3 + Cl• → C6 H 5 CH 2• + HCl
C6 H 5 CH 2• +Cl• →C6 H 5 CH 2 Cl
(iii) Mercaptan can be prepared by the photochemical addition of hydrogen sulphide to alpha olefins.
Inorganic and Organometallic Photochemistry

Many coordination and organometallic compounds are also photoactive and involve cis–trans isomeri-
sation, dissociation of ligands in presence of light.
For example, tetra hydro furan solution of molybdenum hexacarbonyl gives the THF complex in
presence of UV light, which is synthetically useful.
MO(CO) 6 + THF → [MO(CO)5(THF)] + CO
Like this reaction, the photolysis of iron pentacarbonyl affords diiron nonacarbonyl.
Luminescence
Emission of light by a substance, which is not due to heating of the substance, is called luminescence.
Therefore, it is a form of cold body radiation.
Bioluminescence
In fireflies, an enzyme in the abdomen catalyses a reaction that produces light.
Chemical Luminescence
The light produced as a result of chemical reaction is called chemiluminescence.
For example, [A] + [B] → product + light
Luminol + H2O2 (B) → 3-aminophthalate + light
Due to the reaction of luminol with H2O2 in the presence of catalyst, it involves in excitation of
molecule in electronic energy levels and produces 3-aminophthalate and light.

Photochemistry 9.9
Photovoltaic Cell
Photovoltaic (PV) cells (or solar cells produce electricity by photoelectric effect; hence, PV cells are
the building blocks of all PV systems because they are the devices that convert sunlight to electricity.
PV cells are made of semi-conducting materials with different sizes and shapes. They are con-
nected together to form PV molecules that may be up to several feet long and a few feet wide.
Molecules, in turn, can be combined and connected to form PV arrays of different size and power
output; such as electrical connections, mounting hardware, power-conditioning equipment and batter-
ies that use solar energy when the sun is not shining.
When light passes on a PV cell, it may be reflected or absorbed; but only the absorbed light gen-
erates electricity. The energy of the absorbed light is transferred to electrons in the atoms of the PV
cell semiconductor material, and these electrons escape from their normal position in the atoms and
become a part of the electrical flow in an electrical circuit.
Molecular Photochemistry
This is the study of artificial assemblies of two or more molecules to understand the biological process
and the design of artificial systems capable of performing of useful functions.
The main three types of supramolecular systems in the area of co-ordination chemistry are as
follows:
(i) Second-sphere coordination compounds:
For example, hexacyano cobalt (III) anion with poly ammonium macro cyclic receptors.
The complex is associated with other species by electrostatic interaction, hydrogen bonds or
other intra molecular forces.
(ii) Cage-type co-ordination compounds:
This refers to complexes in which the metal ion is encapsulated in a single polydentate ligand.
For example, cage-type cobalt (III) complex.
(iii) Molecular building blocks linked via bridging units by means of covalent or co-ordination
bonds.

1. Crossover of electronically excited molecule two states with same multiplicity is called
___________.
[Ans.: Internal conversion]
2. ________ can prevent the drugs from photodegradation.
[Ans.: Poly vinyl chloride medicine bottles]
3. Vision is initiated by a photochemical reaction of ________.
[Ans.: Rhodopsin]
4. When the excited molecule is breaks into its atomic or molecular fragment, it is called
____________.
[Ans.: Photodissociation]

9.10
5.
Who introduced the quantum efficiency concept?
[Ans.: Einstein]

1. _____________ is concerned with chemical effects of light.
(a) Photochemistry (b) Photolysis
[Ans.: a]
2.
The law that explains thickness of absorbing light and optical path of light is
(a) Bear-Lamberts law (b) Grotthuss–Draper law
(c) Stark-Einstein law (d) None of these
[Ans.: a]
3. Electronically excited molecules that return to ground state with same multiplicity are called
(a) Phosphorescence (b) Fluorescence
(c) Photosensitisation (d) Luminescence
[Ans.: b]
4. Second-sphere co-ordination compounds belongs to
(a) Intra molecular photochemistry
(b) Inter molecular photochemistry
(c) Supramolecular photochemistry
(d) Super molecular photochemistry
[Ans.: c]
5. Light formed from chemical reaction is called
(a) Luminescence (b) Bioluminescence
(c) Chemiluminescence (d) All the above
[Ans.: c]
6. Fire flies are an example of
(a) Bioluminescence (b) Photolysis
(c) Photosynthesis (d) Photoisomerisation
[Ans.: a]

1. What are basic laws of photochemistry?
Ans.: The photochemical reactions are governed by the following two basic principles:
(a) Grotthuss–Draper law
(b) Stark Einstein law of photochemical equivalence.

Photochemistry 9.11
2. Define photochemistry.

Ans.: Photochemistry is a branch of chemistry which is concerned with the effect of chemical
reactions caused by absorption photon from UV-visible and IR radiation.
3. Explain inter-system crossing.
Ans.: Inter-system crossing is a radiation-less process involving transition between two elec-
tronic states with different multiplicities.
4. Describe photosensitisation.
Ans.: It is a process wherein an electronically excited molecule transfers its energy to non-
radioactive molecule to another type of molecule. After excitation, it undergoes a chemical
change called photosensitisation.
5. What is meant by photovoltaic cell?
Ans.: A photovoltaic cell or solar cell is a device in which electricity is produced by photoelectric
effect.
6. Name the types of supramolecular systems.
Ans.: Supramolecular systems are of three types as follows:
(a) Second-sphere co-ordination compounds
(b) Cage-type co-ordination compounds
(c) Molecular building blocks linked via bridging units by means of covalent or co-
ordination bonds.

Q.1 Explain the laws of photochemistry.
Q.2 Describe quantum yield and quantum efficiency of photochemistry.
Q.3 Explain the photochemical process in photochemistry.
Q.4 Explain the photosensitisation process in detail.
Q.5 Give an account of electronically excited states in photochemistry with an energy level
diagram.
Q.6 Explain the photochemical reactions in photochemistry.
Q.7 Give a detailed account of photovoltaic cell.
Q.8 Describe supramolecular photochemistry.

10 Surface chemistry
10.1 INTRODUCTION
“Surface chemistry is the branch of chemistry which deals with the study of the phenomenon occurring at
the surface or interface, that is, at the boundary separating two bulk phases.” We know that number of phe-
nomena occur at the interface, for example, dissolution, crystallization, corrosion, electrode processes, etc.
10.2 ADSORPTION
It is observed that when certain solids like charcoal, silica, etc., are added into a closed vessel contain-
ing some gas or aqueous solution of a solute, the molecules of the gas or the solute are attracted towards
the surface of the solid and then retained on the surface. As a result, the concentration of the gas or the
solute on the surface of the solid increases. This is known as adsorption.
Hence, it may be defined as follows:
(i) Adsorption: The phenomenon of attracting and retaining the molecules of a substance on the
surface of a liquid or a solid resulting into a higher concentration of the molecules on the surface
is called adsorption.
(ii) Adsorbate: The substance (gas or vapour or the solute) that is adsorbed on the surface (liquid or
solid) is called adsorbate.
(iii) Adsorbent: The substance (liquid or solid) that adsorbs either gas or vapour or the solute is
called adsorbent.
(iv) Desorption: The removal of adsorbed substance from the surface is called desorption. It is gen-
erally brought by heating or reducing the pressure.
(v) Occlusion: The adsorption of gases on the surface of metals is called occlusion.
As greater is the surface area of the adsorbent, greater is the adsorption, therefore, finely divided
metals or substances having porous structure, for example charcoal, silica gel, clay, etc act as
excellent adsorbents.
Examples of adsorption:
(i) Adsorption of solute by charcoal: When aqueous solution of raw sugar (which has yellowish
brown colour) is shaken with animal charcoal and then filtered, the filtrate is colourless, which
gives white crystals of sugar on crystallization. This is because the brown colouring substances
are adsorbed by animal charcoal.

10.2
(ii) Adsorption of moisture by silica gel: When silica gel is placed in a closed vessel containing
moist air, the air becomes dry after some time. This is because the water molecules are adsorbed
on the surface of silica gel.
10.2.1 Mechanism of Adsorption

We know that molecules in the interior of a liquid are completely surrounded by other molecules on all
sides, and hence intermolecular forces of attraction are exerted equally in all directions. However, a
molecule at the surface of a liquid is surrounded by large number of molecules (Figure 10.1). Because
the unbalanced, inward forces of attraction on the surface of liquid or solid have the property to attract
and retain the molecules of a gas or solute on their surfaces.
(a) (b)
Figure 10.1 Molecules at the surface experiencing a net inward force of attraction
in case of (a) liquid and (b) solid
10.2.2 Adsorption is Exothermic

During adsorption process, the residual forces on the surface of the adsorbent decreases; it means
surface energy decreases. This decrease that appears in the form of heat is called heat of adsorption.
Hence, adsorption is an exothermic process, that is, ∆Hadsorption is always negative. “The amount of heat
evolved when 1 mole of any gas is adsorbed on a solid adsorbent surface is called “heat of adsorption
or enthalpy of adsorption.”
10.2.3 Difference between Adsorption and Absorption

Adsorption is different from absorption. The former refers to the attraction and retention of the mol-
ecules of a substance on the surface only, while the latter involves distribution of substance that is
uniformly distributed over the liquid or the solid.
When both adsorption and absorption take place simultaneously, the process is called sorption.
Representation of the three processes is shown in Figure 10.2, and the differences between adsorption
and absorption are given in Table 10.1.
Surface concentration Uniform distribution Adsorption and absorption

Adsorbent
Adsorbate (a) (b) (c)
Figure 10.2 (a) Adsorption process (b) Absorption process and (c) Sorption process

Surface Chemistry 10.3
Table 10.1 Differences between adsorption and absorption

Adsorption Absorption
1. It is a process in which molecules of a substance are In this process, molecules of a substance are
assimilated on the surface of a solid (or liquid). uniformly distributed throughout the body of a solid
(or liquid).
2. It is a surface phenomenon, that is, it occurs only at It is a bulk phenomenon, that is, it occurs throughout
the surface of the adsorbent. the body of the material.
3. It is a fast process. It is a slow process.
4. Equilibrium is attained easily. Attainment of equilibrium takes some time.
5. It depends upon surface area of adsorbent. It simply requires the porous structure of the
substance.
10.2.4 Examples of Adsorption, Absorption, and Sorption

(i) When ammonia gas is placed in contact with charcoal, it gets adsorbed on the charcoal, whereas
when ammonia gas is placed in contact with water, it gets absorbed into the water, giving NH4OH
solution of uniform concentration.
(ii) Dyes gets adsorbed as well as absorbed in the cotton fibers, that is, sorption takes place.
10.2.5 Positive and Negative Adsorptions

(i) When the concentration of the adsorbate is more on the surface of the adsorbent than in the bulk,
it is called positive adsorption.
E.g.: When concentrated solution of KCl is shaken with blood charcoal, it shows positive
adsorption.
(ii) When the concentration of the adsorbate is less on the surface of the adsorbent than in the bulk,
it is called negative adsorption.
E.g.: When a dilute solution of KCl is shaken with blood charcoal, it shows negative
adsorption.
10.2.6 Classification of Adsorption

There are two main types of adsorption recognized:
(i) Physical adsorption or physisorption or van der Waal’s adsorption
(ii) Chemical adsorption or chemisorption or Langmuir adsorption or activated adsorption
(i) Physical adsorption: In such type of adsorption, the gas molecules (adsorbed) are held on the
surface of a solid by van der Waal’s forces without resulting into the formation of any chemical
bond between adsorbate and adsorbent. It is called physical adsorption.
(ii) Chemical adsorption: In such type of adsorption, the gas molecules are held on the surface of
a solid by forces similar to those of a chemical bond (ionic or covalent). This type of adsorp-
tion results in the formation of chemical bond between adsorbate and adsorbent; it is called
chemical adsorption. The differences between physical and chemical adsorptions are given in
Table 10.2.

10.4
Table 10.2 Differences between physical and chemical adsorptions

Physical adsorption Chemical adsorption
1. The forces operating in these cases are weak van he forces operating in these cases are similar to those
T
der Waal’s forces. of a chemical bond.
2. The heat of adsorption is low, i.e., about 20–40 The heat of adsorption is high, i.e., 40–400 KJ mol−1.
KJ mol−1.
3. No compound formation takes place. Surface compounds are formed.
4. It occurs at low temperatures. It can occur at high temperatures.
5. This process is reversible in nature, and adsorbate This process is irreversible in nature because
can be recovered from the adsorbent by lowering adsorbate and adsorbent are strongly held by chemical
the pressure. force.
6. It does not require any activation energy. It requires activation energy.
7. It forms multimolecular layer. It forms unimolecular layer.
8. It increases with increase of pressure. It also increases with increase of pressure.
9. It increases with increase in the surface area of It also increases with increase in the surface area of
the adsorbent. the adsorbent.
10. The equilibrium is established rapidly. Establishment of equilibrium requires time.
11. It is not very specific in nature. It is highly specific in nature.
10.2.7 Factors Affecting the Adsorption of Gases by Solids

The amount of gases adsorbed on the surface of solid depends upon the following factors:
(i) Nature and surface area of the adsorbent: It is observed that the extent of adsorption depends
upon the nature of the adsorbent used at the same temperature. Moreover, the greater the surface
area of the adsorbent, the greater is its adsorption capacity. Due to this reason, the substances
like charcoal and silica gel are excellent adsorbent because they have high porous structures and
hence have large surface areas. For the same reason, activated charcoal and finely divided solid
substances are better adsorbents.
(ii) Nature of the gas: Different gases are adsorbed to different extents by the same adsorbent at
the same temperature. The easily liquefiable gases (like HCl, NH3, Cl2, etc.) are adsorbed more
easily than the permanent gases (like H2, N2, O2, etc.). The ease of liquefaction of a gas depends
upon its critical temperature (i.e., the minimum temperature above which a gas cannot be lique-
fied by applying even high pressure). The critical temperature of a gas is related to the intermo-
lecular forces. Hence higher is the critical temperature, the more easily the gas is liquefied and
hence more readily it is adsorbed.
(iii) Temperature: As already discussed, adsorption is an exothermic process and it is accompanied
by evolution of heat. Hence, according to Le Chatelier’s principle, it can be seen that increase of
temperature decreases the rate of adsorption and vice versa.
Condensation

Gas (Adsorbate) + solid (Adsorbent)
Gas Adsorbed on solid + Heat
Evaporation
In case of physisorption, the amount of adsorption decreases with increase of temperature in accord-
ance with Le Chatelier’s principle. But in case of chemisorption, it is observed that the amount
of adsorption initially increases with increase in temperature and then decreases (Figure 10.3).
This is due to the fact that a chemisorption process requires some activation energy and hence the

Physisorption Chemisorption
x x
m m
Temperature Temperature
(a) (b)
Figure 10.3 Adsorption isobars for (a) Physisorption and (b) Chemisorption
initial rise. Once the adsorption process commences, the amount of adsorption decreases due to
its exothermic nature.
(iv) Pressure: At constant temperature, the adsorption of a gas increases with increase of pressure
according to Le Chatelier’s principle; since a dynamic equilibrium exists between the adsorbed
gas and the adsorbent solid.
(v) Activation of adsorbent: In order to increase adsorption, activation of the adsorbing power of
the adsorbent is very necessary.
This is done by increasing the surface area of the adsorbent, which can be achieved by the
following ways:
(a) By making the surface of the adsorbent rough through mechanical rubbing.
(b) By subdividing the adsorbent into smaller pieces or grains.
(c) By removing the gases already adsorbed by strong heating; due to this, its pores are opened,
hence the rate of adsorption activity increases.
10.2.8 Adsorption Isotherms

The extent of adsorption on a given surface increases with increase in pressure (for gases) and concen-
tration (for solution) at constant temperature.
The extent of adsorption is usually expressed as x/m, where m is the mass of the adsorbent and
x is the mass of the adsorbate when adsorption equilibrium is reached.
“A graph between the amount of the gas adsorbed per gram of the adsorbent (x/m) and the equilib-
rium pressure at constant temperature is called adsorption isotherm.”
Freundlich Adsorption Isotherm

To understand the effect of pressure on adsorption of a gas, we consider adsorption as an equilibrium
process. When the adsorbent and adsorbate are enclosed in a closed vessel, after an initial decrease in
the pressure of the gas, gas pressure as well as the amount of gas adsorbed reaches constant values. This
is because when the equilibrium is attained, the rate of adsorption becomes equal to the rate of desorp-
tion (Figure 10.4).
 x
From the graph, it is clear that the extent of adsorption   increases with increasing pressure and
 m
becomes maximum at Ps, called the saturation pressure. At Ps, the rate of adsorption becomes equal to the rate
of desorption (i.e., equilibrium is attained), and further increase in pressure does not alter the equilibrium.

10.6
x
= KP 0
x m
m x 1
= KP n
m
x
= KP 1 Ps (Saturation pressure)
m
Figure 10.4 Freundlich adsorption isotherm
The following observations can be made from graph:

(i) At low pressure, the graph is almost straight line and sloping. This is represented by the follow-
ing equation:
x
∝ P1
m
or
x
= KP1
m (1)
 x
(ii) At high pressure,   is independent of pressure, that is, the graph becomes almost parallel to
 m
x-axis. This is represented by the following equation:
x
∝ P0
m
or
x
= K × P 0 (2)
m
 x
(iii) In the intermediate range of pressure,   will depend on P raised to powers between 1 and 0,
 m
that is, fractions. So, for a small range of pressure values, we can write,
1
x
∝ Pn
m
or
1
x
= KP n (3)
m
Where n = positive integer and n and K are constants depending upon the nature of the adsorbate
and adsorbent at a particular temperature.
This relationship was originally put forward by Freundlich in 1909 and is known as Freundlich
adsorption isotherm.

To test the validity of this equation, taking logarithms on both sides, we get and compare with
straight line equation
x 1
log = log K + log P (4)
m n
y = c + mx → Straight line
x
A graph between log against log P should, therefore, gives a straight line with slope equal to
1 m
and ordinate intercept equal to log K (Figure 10.5).
n
1
m ) = n
p e(
Slo
x
log
m
Intercept (c) = log K
log P
Figure 10.5 Linear graph between log x and log P

m
Limitations of Freundlich adsorption isotherm: When the experiment’s values are plotted, it shows some
deviation from linearity, especially at high pressure. Hence, this relation is suitable only at low pressure.
Langmuir Adsorption Isotherm

In 1916, Irving Langmuir proposed another adsorption isotherm, which explained the variation of
adsorption with pressure. Based on his theory, he derived Langmuir equation, which depicted a rela-
tionship between the number of active sites of the surface undergoing adsorption and pressure.
Assumption of Langmuir Isotherm

(i) Fixed number of vacant or adsorption sites are available on the surface of a solid.
(ii) All the vacant sites are of equal size and shape on the surface of the adsorbent.
(iii) Each site can hold maximum of one gaseous molecule, and a constant amount of heat energy is
released during this process.
(iv) The ability of a molecule to adsorb at a given site is independent of the occupation of the neigh-
boring sites.
(v) Dynamic equilibrium exists between the adsorbed gaseous molecules and the free gaseous
molecules.
Adsorption

A( g ) + B( s)
AB
Desorption

10.8
where A(g) = Unadsorbed gaseous molecule

B(s) = Unoccupied metal surface
AB = Adsorbed gaseous molecule
(vi) Adsorption is monolayer or unilayer.
Derivations of Langmuir Adsorption Equation

(i) Calculation of equilibrium constant: Langmuir proposed the dynamic equilibrium that exists
between adsorbed gaseous molecules and the free gaseous molecules. Using the equilibrium
equation, equilibrium constant can be calculated:
K

A( g ) + B( s)
a
AB
K d
Where Ka = equilibrium constant for forward reaction

Kd = equilibrium constant for backward reaction
According to kinetic theory,
Rate of forward reaction = Ka[A][B]
Rate of backward reaction = Kd[A][B]
At equilibrium,
Rate of forward reaction = Rate of backward reaction
K a [ A][ B ] = K d [ AB]
Ka [ AB ]
K= =
K d [ A][ B ]
where K = adsorption constant or equilibrium constant
(ii) Derivation of Langmuir equation: To derive Langmuir equation, a new parameter ‘θ’ is intro-
duced. Let θ be the number of sites of the surface, which are covered with gaseous molecules.
(1−θ) is the number of vacant sites.
Initially, the rate of adsorption is high because the number of vacant sites is quite large
compared to the filled sites. As adsorption process increases, the number of vacant sites for
adsorption increases. We know that the rate of adsorption depends upon the pressure P and the
number of vacant sites (1−θ).
Rate of adsorption ∝ (1 − θ) ⋅ P
(1)
Rate of adsorption = K a (1 − θ) ⋅ P
Rate of desorption under the same conditions depends on θ, the faction of surface
covered.
Rate of desorption = K d θ (2)
At equilibrium,

Rate of adsorption = Rate of desorption
K a (1 − q ) P = K d ⋅q
Ka P
There q =
Kd + Ka P
Divide numerator and denominator on RHS by Kd .

We get
Ka
⋅P
Kd
θ=
Kd Ka
+ P
Kd Kd
KP
=
1 + KP
K
where K = a
Kd
KP
θ=
1 + KP
This is known as Langmuir adsorption equation.
(iii) Freundlich adsorption equation: A special case of Langmuir equation: We consider
Langmuir Equation
KP
θ=
1 + KP
(a) At low pressure, KP < < 1
Therefore
θ = KP
(1)
or θ ∝ P1
(b) At high pressure,
KP > > 1
KP
θ= =1
KP (2)
θ ∝ P0
Combining the result of equations (1) and (2),
θ = KP 0 −1
1 (3)
or θ = KP n
Equation (3) is in agreement with Freundlich adsorption equation. Hence, we can say
that Freundlich adsorption equation is a special case of Langmuir equation (Figure 10.6).
θ=1
(Zero order)
KP
1 + KP
θ
θ = KP (Ist order)
Pressure, P
Figure 10.6 Langmuir variation of coverage with pressure for molecular adsorption

10.10
(iv) Verification of Langmuir equation: The verification of Langmuir equation can be carried out
as follows:
The amount of gas adsorbed per unit mass of absorbent is x ∝ θ
x = K1θ (4)
By substituting the value of θ,
K1 KP
x=
1 + KP

K2 P
x=
1 + KP
where K 2 = K1K
Dividing both sides by P and then taking reciprocals, it gives
P 1  K
= + P
x K 2  K 2 
Since K and K 2 are constants for a given system. K
Plotting a graph between P/x against P should give a straight line with a slope and inter-
1 K 2
cept . Figure 10.7 shows a linear relationship for same experimental data.
K2
K
)= K2
p e (m
P Slo
x
1
Intercept (c) =
K2
Figure 10.7 Linear graph of P/x versus P
The Langmuir adsorption equation is only valid for unimolecular layer adsorption, not for
multilayer adsorption in several solids.
BET Adsorption Isotherm

The concept of the theory is an extension of the Langmuir theory, which is a theory for monolayer molecu-
lar adsorption to multilayer adsorption. In 1938, Stephen Brunauer, Paul Hugh Emmett, and Edward Teller
proposed this theory (BET theory) after their initials. BET Adsorption Isotherm is shown in Figure 10.8.
The following hypothesis of BET theory:
(i) Gas molecules adsorb on a solid in layer infinitely.
(ii) There is no interaction between each adsorption layer.
(iii) Langmuir theory can be applied to each layer.
The resulting BET equation is expressed as follows:

V/Vm
Figure 10.8 BET adsorption isotherm
1 C −1  P  1
=   + (1)
 P   VmC  P0  VmC
V  0  − 1
 P  
or
1 (C − 1) 1
= ⋅x+ (2)
 1   VmC VmC
V  − 1 
 x  
Here P and P0 = equilibrium and saturation pressure of adsorbates at the temperature of

adsorption
V = Volume of gas adsorbed
Vm = Volume of monolayer absorbed quantity
C = BET constant
 E − EL 
C = exp  1 (3)
 RT 
Where E1 = Heat of adsorption for the first layer

EL = Heat of liquefaction for the second and higher layers
Verification of BET Equation
Equation (1) is an adsorption isotherm and can be plotted as a straight line (Figure 10.9). Plotting of
P
against P/P0 should be a straight line.
V ( P0 − P )
C −1 1
The slope of the line is given as and intercept with the value of . Thus, by knowing the
VmC Vm ⋅ C
value of slope and intercept, both Vm and C can be evaluated by using the following equation:
1
Vm = (4)
A+ I
and

10.12
A
C = 1+ (5)
I
P C−1
Slope =
V(P0−P ) (A) Vm⋅C
1
Intercept =
(I ) V m C
P/P0
Figure 10.9 Linear graph of P/P0 Vs P/V(P0-P)

Derivation of BET Equation
Consider a surface and molecules that are adsorbed on different layers, that is, adsorption on multilayer
(Figure 10.10).
Consider θ0, θ1, θ2 ,……… θn = surface area covered by 0,1, 2,……, n layers of adsorbed molecules.
K

A( g ) + S
1

AS
K−1
A( g ) + AS
K2

A2 S
K −2
K3

A( g ) + A2 S
A3 S and so on.
K −3
4th layer 3rd layer

nd
2 layer
1st layer
Surface
Figure 10.10 Adsorption of gas molecules on the surface of a solid
At equilibrium, θ0 must remain constant.

∴ Rate of evaporation from first layer = Rate of condensation onto base surface
(1)
K −1θ1 = K1 Pθ0
Similarly, at equilibrium, θ1 must remain constant.
 Rate of condensation on the base surface  Rate of condensation on first layer 
∴ + = + 
 Rate of evaporation from the seond layer   Rate of evaporation from first layer 
   
K1 Pθ0 + K −2 θ2 = K 2 Pθ1 + K −1θ1

Substituting in equation (1) gives

K −2 θ2 = K 2 Pθ1
And so on. For other layers,
K − i θi = K i Pθi −1 (2)
According to the definitions, total surface area of the catalyst,
∞
A = ∑ θi (3)
i=0
Total volume of the gas adsorbed on the surface,

∞
V = V0 ∑ iθi (4)
i=0
Where V0 = Volume of the gas adsorbed on one square centimeter of surface when it is covered with a
complete layer.
Then,
∞
V V
∑ iθi
i =0
= = ∞ (5)
AV0 Vm
∑ θi
i =0
Vm = Volume of the gas adsorbed when the entire surface is covered with a complete monolayer
From equation (1),
 K 
θ1 =  1  Pθ0
 K −1 
= Y θ0
 K  
Where Y =  1  P 
 K −1  
By assuming that the properties of 1st, 2nd, and nth layers are equivalent,
K −2 K −3 K − i
= … = g (6)
K2 K3 Ki
Similarly,
 K 
θ2 =  2  Pθ1
 K −2 
= X θ1
 P
Here  X = 
 g
θ3 = X θ2 = X 2 θ1

10.14
Generally,
θi = X θi −1 = X i −1θ1 = X i −1Y θ0 = CX i θ0
Where C = {} Y
X

Substituting in equation (5),

∞ ∞
V
∑ iθi C θ0 ∑ iX i
i=0 i=0
= ∞
=
Vm (θ0 + θ1 + θ2 + ........)
∑ θi
i=0
∞
C θ0 ∑ iX i
i =1
=
 ∞

θ0 1 + C ∑ X i 
 i =1
∞
C ∑ iX i
i =1
=
 ∞

 1 + C ∑ Xi 
 (7)
i =1
On solving,
V CX
=
Vm (1 − X )(1 − X + CX )

At saturation, pressure of gas P0, an infinite number of adsorbate layers must build on the surface.
This means at P0, X must equal 1.
∴ g = P0
P
∴ X =
P0
Substituting in equation (7), we get BET isotherm equation

VmCX
V=
(1 − X ){1 + (C − 1)X }
X 1 X (C − 1)
= +
V (1 − X ) VmC VmC
P 1 C −1 P
= + ×
V (P0 − P ) VmC VmC P0
Where P = Pressure at the absorption equilibrium

P0 = Saturated vapour pressure of the adsorbent at different temperatures

Calculation of Surface Area of Adsorbent by BET Method

BET method is widely used for the calculation of surface areas of solids by physical adsorption of gas
molecules.
The total surface area STotal and a specific surface area S are evaluated by the following equations:
Vm NS
SBET = (1)
V
STotal = SBET × a
V NS
= m a
V
Where N = Avogadro’s number
S = Adsorption cross section
V = Molar volume of adsorbent gas
Vm = Volume of monolayer adsorbed gas
a = Molar weight of adsorbed species
For example, to determine the inner surface of a hardened cement paste, by plotting a
graph between the quantities of adsorbed water at different levels of relative humidity, a BET plot is
obtained.
From the slope A and intercept I, one can calculate Vm and C by using the following equation:
1
Vm =
A+ I
A
C = 1 + , where A = 24.20, I = 0.33
I
1 1
Vm = =
A + I 24.20 + 0.33
= 0.0408 g/g
SBET can be calculated by using the equation,

Vm NS
S BET =
V
The surface covered by one water molecule, S = 0.114 nm 2
So,
1
S BET = 0.0408 × 0.114 × × 6.023 × 10 23
18
= 155.63 × 10 −5 × 10 23 nm 2
= 155.63 × 1018 nm 2 /g
= 155.63 m 2 /g
Surface area of the hardened cement = 155.63 m 2/g

It means the cement paste has inner surface of 155.63 m 2 per g of cement.

10.16
10.2.9 Applications of Adsorption

Adsorption finds extensive applications both in industry and research laboratory. A few applications
are briefly described below:
(i) In preserving vacuum: Adsorption process is used in the production of vacuum by using culti-
vated charcoal in Dewar’s flask.
(ii) In clarification of sugar: Sugar is decolourized by treating sugar solution with charcoal powder.
(iii) In gas masks: All gas masks are devices containing suitable adsorbent so that the poisonous
gases present in the atmosphere are preferentially adsorbed and air for breathing is purified.
(iv) In heterogeneous catalysis: Adsorption is useful in heterogeneous catalysis. This theory is
called adsorption theory. According to this theory, gaseous reactants are adsorbed on the surface
of the solid. As a result, concentration of reactant increases. Hence, the rate of reaction increases.
For example, in the manufacturing of ammonia using iron as catalysts, V2O5 is used as catalyst
in the manufacturing of H2SO4 by contact process.
(v) In softening of hard water: In water-softening process, hard water is passed through zeolite
bed in which Ca2+ and Mg2+ ions of hard water are replaced by equal amount of Na+ ions. So by
this process, water becomes soft.
(vi) In adsorption indicator: Various dyes, which have the property of adsorption, have been
intruded particularly in precipitation titration. For example, by the use of eosin as indicator, KBr
is easily titrated with AgNO3.
(vii) In dehydration process: Silica gel and alumina gel adsorbents are used to remove moisture and
dehumidifies the air from rooms and instruments.
(viii) In chromatographic analysis: The selective adsorption of certain substances from a solution
by a particular solid adsorbent filled in a long and wide vertical tube: column chromatography.
Examples are as follows:
(a) Separation of isomeric aromatic or aliphatic hydrocarbons
(b) Separation of two or more components of mixture
(c) Purification of substances from their contaminants
(d) Identification of biochemicals such as amino acids, neutral lipids, carbohydrates, etc.
(ix) In Froth floatation process: In this process, finely divided sulphide ores (PbS, ZnS, Cu2S, etc.)
are mixed with pine oil and agitated with water containing detergent. Air is then bubbled through
this mixture, and air bubbles stabilized by the detergent adsorb mineral particles, which float to
the surface while the silica impurities settle down.
(x) In medicine: For the treatment of arsenic poisoning, colloidal Fe(OH)3 is administered as an
antidote in which Fe(OH)3 adsorbs arsenic and retains it and thus can be removed from the body
by vomiting.
(xi) In dyeing: During the process of mordant dyeing, the metal ions like Al3+, Fe3+, and Cr6+ adsorb
the dye, which otherwise does not adhere to the fabric.
(xii) Ion exchange adsorption process is used to remove excess of sodium salt from the body fluids
of a patient by providing him/her to a suitable cation exchanger to consume. Similarly, anionic
resin is used to neutralize the excess acid in the stomach.
(xiii) By adsorption, we can easily remove polluting gases and control indoor pollution.
(xiv) By the use of surface active agents in detergents, paints, lubrication, surface cleaner, etc., surface
active agents displace the adhering impurities from all surfaces by the phenomenon of wetting.

(xv) Soil contains small amounts of colloidal fractions in the form of very fine particles of clay, which
adsorb moisture in which essential plant nutrients N, P, and K dissolve and are taken up by the
plants by capillary action.
10.3 COLLOIDAL STATE

The origin of the study of this field lies with Thomas Graham, who in 1861 studied the diffusion of
liquids and solutions across the animal membranes, and as a result, he divided the soluble substances
into two classes:
(i) Crystalloids diffuse readily in solution and those solution that can readily pass through ani-
mal or vegetable membranes, for example, urea, sugar, salts, acids, bases, and other crystalline
substances.
(ii) Colloids (from the Greek words “kola” and “eidos”, which mean glue and like, respectively),
diffuse very slowly in solution and those solution that cannot pass through animal or vegetable
membranes, for example, glue, starch, albumin, proteins, and other amorphous substances.
In recent years, this classification of substances has undergone a great change because distinction
between crystalloids and colloids was not rigid. In fact, any substance, regardless of its nature, could
be converted into a colloid by subdividing it into particles of small size (1–1000 nm).
10.3.1 Types of Solution

On the basis of the size of the particle, the solutions may be of the following three types:
(i) True solution: True solution is a homogeneous solution containing dispersed particles of molec-
ular size (less than 10−9 m or 1 nm), for example, NaCl or glucose solution in water.
(ii) Suspension solution: Suspension is a heterogeneous solution containing mixture of suspended
insoluble particles of size (greater than 10000 A° or 1000 nm).
(iii) Colloidal solution: Colloidal solution is a heterogeneous solution in which a substance is dis-
tributed in colloidal state (1 nm–1000 nm) in an insoluble medium.
The common characteristics among the three solutions are given in Table 10.3.
Table 10.3 Characteristics of true solution, colloidal solution, and suspension

S. no. Property True solutions Colloidal solutions Suspension solutions
1. State Homogeneous Heterogeneous Heterogeneous
2. Particle size Less than 1 nm Between 1 nm and More than 1000 nm
1000 nm
3. Visibility of Invisible Visible under Visible
particle ultramicroscope
4. Diffusion Diffuse quickly Diffuse slowly Do not diffuse
5. Filterability Pass through ordinary Pass through only ordinary Do not pass through
filter paper as well as filter paper, not through ordinary filter paper as well
animal membrane. animal membrane. as animal membrane.
6. Settling Do not settle Do not settle Settle on standing
7. Appearance Clear and transparent Translucent Opaque

10.18
10.3.2 Classification of Colloids

In colloidal system, the terms dispersed phase and dispersion medium are used. Dispersed phase means
the substance distributed in the dispersion medium in the form of colloidal particles, and dispersion
medium means the medium in which the substance is dispersed in the form of colloidal particles. Just
as in solution, where solute and solvent are used, in colloidal system, dispersed phase and dispersion
medium are used.
Colloidal systems are classified in different ways:
(i) Based on the physical state of the dispersed phase and dispersion medium: Depending upon
the physical state of the dispersed phase and dispersion medium, that is, solids, liquids, or gases,
eight types of colloidal systems are possible (Table 10.4).
Table 10.4 Physical states of the dispersed phase and dispersed medium with examples
Dispersed Dispersion Colloidal
S. no. phase medium system Examples
1. Solid Solid Solid Sol Some coloured glasses, gems, stones,
minerals, etc.
2. Solid Liquid Sol Some paints, cell fluids, muddy
water, white of an egg, etc.
3. Solid Gas Solid aerosol Smoke, dust, fume, etc.
4. Liquid Solid Gel Cheese, butter, jellies, curd, boot
polish, etc.
5. Liquid Liquid Emulsion Milk, cream, medicine, etc.
6. Liquid Gas Liquid Aerosol Fog, mist, cloud, spray, etc.
7. Gas Solid Solid foam Biscuit, cake, bread dough, floating
soaps, etc.
8. Gas Liquid Foam or froth Foam, whipped cream, soap lather,
detergent suds, etc.
(ii) Based on the nature of the dispersion medium: Depending upon the nature of the dispersion
medium, the sols (solid in liquid) are given special names as in the following Table 10.5:
Table 10.5 Nature of the dispersed medium and the names of the sols
Dispersion medium Name of the sol
Water Aquasol or Hydrosol
Alcohol Alcosol
Benzene Benzosol
Gases Aerosol
(iii) Based on the nature of interaction between dispersed phase and dispersion medium: On
this basis, colloidal sols are divided into two categories, namely, lyophilic and lyophobic. If water
is the dispersion medium, the terms used are hydrophilic and hydrophobic.
(a) Lyophilic sols are those in which the dispersion medium possesses great affinity (liquid-
loving) for the dispersed phase. Examples are starch, glue, gelatin, agar sols in water, etc.
Characteristics:
(1) Lyophilic sols are directly formed colloidal sols; that is why they are also called intrinsic
colloids.

(2) The dispersion medium is easily separated from the dispersed phase (by evaporation),
and the sol can be made by simply remixing with dispersion medium and shaking. That
is why, these sols are also called reversible sols.
(3) These sols are quite stable and cannot be easily precipitated.
(b) Lyophobic sols are those in which there is no affinity or interaction between the dispersion
medium and the dispersed phase. Examples are gold sol, silver sol, and metal sulphide sol in
water.
Characteristics:
(1) Their colloidal sols are generally prepared by indirect methods; that’s why they are called
extrinsic colloids.
(2) Such types of colloidal sols are not precipitated out once they formed. These sols are also
called irreversible sols.
(3) These sols are easily precipitated (or coagulated), and hence are not stable.
The points of difference between lyophilic sols and lyophobic sols are given below in Table 10.6:
Table 10.6 Differences between lyophilic sols and lyophobic sols

S. no. Property Lyophilic sols Lyophobic sols
1. Ease of preparation Easily prepared by directly Cannot be prepared directly.
mixing with the liquid It can be prepared by special
dispersion medium. methods only.
2. Stability They are quite stable and are notThey are easily precipitated by
easily precipitated or coagulated.
addition of small amount of
electrolyte.
3. Hydration They are highly hydrated. They are not much hydrated.
4. Nature of the particles Particles are solvent-loving and Particles are solvent-hating
in the form of single molecule. and consist of large number of
associated molecules.
5. Viscosity Viscosity is higher than that of Viscosity is almost the same as
the solvent. that of the solvent.
6. Visibility The particles cannot be The particles can be
detected readily, even under readily detected under
ultramicroscope. ultramicroscope.
7. Stability Very stable Poor stability of particle
8. Surface tension Their surface tension is lower Their surface tension is nearly
than that of the dispersion same as that of the dispersion
medium. medium.
9. Reversibility Reversible in nature Irreversible in nature
10. Action of electrolyte Coagulation can be brought about The addition of even small
only by the addition of large quantity of electrolyte can cause
quantities of electrolytes. coagulation.
(iv) Based on the type of particles of the dispersed phase: Depending upon the different size of the
colloids, colloidal dispersion may be divided into the following three categories:
(a)
Multimolecular colloids: Multimolecular colloids are colloidal solutions in which colloidal
particles (or dispersed phase) consist of aggregates of atoms or molecules, each having diam-
eter less than 1 nm. In these aggregates, the atoms or molecules are held together by weak
force of attraction. They are lyophobic in nature. For example,

10.20
(1) A gold sol in water consists of dispersed particles of various sizes made up of several
atoms of gold.
(2) A sulphur sol in water consists of dispersed particles containing a large number of S8
molecules.
(b)
Macromolecular colliods: Macromolecular colloids are colloidal solutions in which the dis-
persed particles are very large molecules of high molecular mass (called macromolecules).
These particles contain a large number of atoms (joined together through covalent bonds),
each having dimensions compared to those of colloidal state. They are lyophilic sols and
possess gold number.
For example,
(1) Naturally occurring macromolecules such as starch, cellulose, proteins, enzymes and
gelatine, etc.
(2) Man-made macromolecules like polyethylene, nylon, polystyrene, synthetic rubber, etc.
(c)
Associated colloids–micelles: Associated colloids are the colloidal solutions in which the
colloidal particles behave as normal, strong electrolytes when dissolved in a medium at
low concentrations, but at higher concentrations, they form aggregated particles of colloidal
dimensions, called micelles.
The formation of micelles takes places only above a particular temperature called Kraft
temperature (Tk) and above a particular concentration called Critical micelle concentration
(CMC).
For example, most common associated colloids are soaps and synthetic detergents. For
soaps, the CMC is 10−4−10−3 mol L−1. Each micelle contains at least 100 molecules.
Mechanism of micelle formation: When soap is dissolved in water, the negative ions
aggregate to form an ionic micelle, which is of colloidal size (Figure 10.11).
We know that soap is sodium salt of higher fatty acid RCOONa; when dissolved in
water, it dissociates into RCOO− and Na+ ions.
− +
RCOONa RCOO + Na
RCOO− ions consist of two parts, that is, non-polar, long hydrocarbon chain R, called
the tail, which is hydrophobic and polar group COO−, called the head, which is hydrophilic.
At higher concentration, ions (RCOO−) forms an aggregate of spherical shape with their
hydrocarbon chains pointing towards the centre and COO − parts outward on the surface of
the sphere.
+ − Free positive (Na+) ions

Water +
−
RCOO− Na+
+ − +
−
+ − Hydrocarbon COO− part

−
−
part
Figure 10.11 A micelle in a soap solution
A few common features among multimolecular, macromolecular, and associated col-

loids are compared in Table 10.7.

Table 10.7 Comparison of multimolecular, macromolecular, and associated colloids

S. no. Multimolecular colloids Macromolecular colloids Associated colloids
1. They are formed by the They are molecules of large They are formed by
aggregation of a large number size having high molecular aggregation of a large
of atoms or molecules, having masses. number of ions in
diameter less than 1 nm. concentrated solution.
2. They are lyophobic sols. They are lyophilic sols. Dispersed particles
containing both lyophilic
and lyophobic parts.
3. They are low conducting. They are poor conducting. They are highly
conducting.
4. Examples are gold and Examples are starch, proteins, Examples are soaps and
sulphur sol in water. enzymes, natural rubber, etc. detergents solution.
10.3.3 Properties of Colloidal Solutions

Colloidal solutions possess some distinct characteristics. Some of them are discussed as follows:
(i) Physical properties:
(a)
Heterogeneous character: Colloidal particles are heterogeneous in nature, having two dis-
tinct phases, that is, dispersed phase and dispersion medium.
(b)
Stability: Colloidal sols are quite stable. Only a few colloidal particles of comparatively
larger size may settle but very slowly.
(c)
Filterability: Colloidal solutions can readily pass through ordinary filter paper, because the
pore size of the filter paper is much larger than that of colloidal particles. But colloidal par-
ticles cannot pass through semi-permeable membrane.
(d)
Visibility and colour: The particles of the colloidal solution are not visible to naked eye or
under ordinary microscope. The colour of the colloidal solution depends upon the wave-
length of light scattered by the colloidal particles.
(ii) Colligative properties: Colloidal particles have a very high molecular weight, so the
number of moles present in a solution is extremely low. Since colligative properties depend
only on the number of effective moles present per litre, the value of any of the colligative
properties—osmotic pressure, elevation in boiling point, depression in freezing point, and lower-
ing of vapour pressure of specific substance—will be quite low, compared to its value, when it is
in the form of a true solution.
(iii) Mechanical properties: When colloidal solution is viewed through an ultramicroscope, colloidal
particles are seen continuously moving in a zigzag way. This phenomenon was first observed by
Robert Brown in 1827, and hence, it is called Brownian movement. Thus, “Brownian movement
is defined as continuous, rapid and random zigzag movement of the colloidal particles in a col-
loidal sol.”
Cause of Brownian movement: The molecules of dispersion medium due to their kinetic motion
strike against the colloidal particles from all sides with different forces, causing them to move.
However, colloidal particles, being comparatively higher, move with a slower speed (Figure 10.12).

10.22
Particles of
dispersion
medium
Colloidal particle

Figure 10.12 Brownian movement is due to the unbalanced imparts
of molecules of the dispersion medium on colloidal particles
(iv) Optical properties: It was observed that when colloidal solution is placed in a dark room and a
strong converging beam of light is passed through it, a path of the beam gets illuminated with a
bluish light when viewed at right angles to the direction of the passage of light. The path of light
becomes visible due to scattering of light by the colloidal particles as shown in Figure 10.13. This
phenomenon was observed by Tyndall in 1869 and is called Tyndall effect. Thus, “Tyndall effect
may be defined as the scattering of light by the colloidal particles present in a colloidal solution.”
Ultramicroscope
Path is Path is
invisible visible
True solution Colloidal solution
Figure 10.13 Tyndall effect exhibited by a colloidal solution, but not by true solution
Causes of Tyndall effect: Tyndall effect is shown by colloidal particles due to scattering
of light by colloidal particles. The colloidal particles absorb the incident light energy, become
self-luminous, and scatter this absorbed light from their surfaces. As the intensity of scatter-
ing is maximum in the plane at right angles to the direction of incident beam, the path becomes
visible. The molecules of true solution do not scatter light, as their size is comparatively
very small.
The importance of Tyndall effect is that it helps to confirm the heterogeneous nature of the
colloidal solutions.
(v) Electrical properties:
(a) S
tability of colloidal sols: The colloidal particles in a colloidal solution carry either
positive or negative charge. So due to electrically charged colloidal particles, colloidal solu-
tion is stable. The particles, due to the same charge, repel one another and do not come
close together to form large, non-colloidal particles. The dispersed phase in a colloidal
solution carries the same charge while the dispersion medium has an equal and opposite
charge.

Table 10.8 Charge on particles of some common sols using water as dispersion medium
S. no. Negatively charged Positively charged
1. Metallic particles(e.g., Cu, Ag, Au Metal hydroxide like Fe(OH)3, Al(OH)3,
sols, etc.) Cr(OH)3, and Ca(OH)2
2. Metal sulphides like As2S3, CdS, Hydrated metallic oxides like Al2O3·xH2O,
etc. Fe2O3·xH2O, Cr2O3·xH2O, etc.
3. Acidic dyes like Congo red and Basic dyes like methylene blue, prussian
eosin sols blue, etc.
4. Starch, gum, gelatin, charcoal, and Hemoglobin
clay
For example, arsenious sulphide particles are negatively charged, whereas the disper-
sion medium (water) is positively charged. Ferric hydroxide particles are positively charged,
whereas the dispersion medium (water) is negatively charged (Table 10.8).
Origin of electrical charge on colloidal particles: The various reasons for the
origin of electrical charge on the colloidal particles are as follows:
(1)
Preferential adsorption of ions from solution: It may be either positive or negative ion
on its surface. For example, if colloidal sol of AgI is prepared by adding KI solution to
AgNO3 solution till KI is in slight excess, iodide ions (I−) will be adsorbed on the surface
of AgI particles, thereby giving them negative charge:
AgI + I− → AgI I −

(from KI) Negative solution
or if AgI is prepared by adding AgNO3 to KI solution, till AgNO3 is in slight excess,

AgI + Ag + → AgI Ag +
(from AgNO 3)
Positive sol
In either case, the left-out ions will remain in the dispersion medium (e.g., K+ ions in
the first case and NO3− ions in the second case), thereby giving equal and opposite charge
to the dispersion medium.
+ −
AgI I
−
K
+ AgI Ag NO3
+ −
AgI I
− + AgI Ag NO3
K −
− + NO3
AgI I K
+ OR AgI Ag
+ −
AgI I
− + AgI Ag NO3
K −
− + + NO3
AgI I K AgI Ag
Mobile/diffused Mobile/diffused
Fixed layer layer Fixed layer layer
Figure 10.14 Formation of electrical double layer
(2)
Dissociation of molecules followed by aggregation of ions: For example, in case of soap,
the RCOO− group gets dissociate from Na+ ions and have a tendency to aggregate into a
cluster, carrying negative charge.

10.24
(3) Dissociation of the molecular electrolytes adsorbed on the surface of particles: For
example, H2S molecules get adsorbed on colloidal particles of As2S3 during precipitation
in which H+ ions are lost, giving negative charge to colloidal particles.
The theory of electrical double layer was proposed by Helmholtz, and he explained
that charge on colloidal particles is due to the preferential adsorption of common ions on
their surface. So when one type of ion of the electrolyte is adsorbed on the surface of the
colloidal particles, it forms a fixed layer; it attracts the counter ions from the medium,
forming a second layer, which is mobile and is called diffused layer. The double layer
of opposite charges thus formed is called Helmholtz electrical double layer. As a result,
a potential difference is set up between the fixed layer and the diffused layer, and this is
known as electro kinetic potential or zeta potential (Figure 10.14).
Electrophoresis or cataphoresis: The colloidal particles are electrically charged either posi-
(b)
tive or negative, and the existence of electrical charge can be shown by the process known as
“electrophoresis,” which is also called “cataphoresis.”
It consists of a U-tube, partly filled with a colloidal solution and rest of the tube is filled
with distilled water. So when electric field is applied, the electrically charged colloidal par-
ticles move towards one or the other electrode, depending on the charge present on colloidal
particles (Figure 10.15). Thus, “The movement of colloidal particles under the influence of
an electric field is called electrophoresis or cataphoresis.”
Cathode
− + − +
Distilled
water
Anode
Colloidal
sol
(a) (b)
Figure 10.15 (a) Before electrophoresis (b) After electrophoresis (for negatively
charged colloidal particles)
On applying potential gradient within a U-tube, which is filled with colloidal solution
and the rest with distilled water, the colloidal particles move towards oppositely charged
electrode. On reaching the electrode, they lose their charge and coagulate. If the movement
of colloidal particles is towards cathode, it is called cataphoresis, as in the case of positively
charged sols like Fe(OH)3.
However, the term electrophoresis is preferred because colloidal particles may migrate
towards anode or cathode depending upon the charge on the colloidal particles.
E
lectro-osmosis: When an electric field is applied on colloidal solution, the particles of
(c)
the dispersion medium (which are also electrically charged) move towards oppositely
charged electrode, provided the colloidal particles are not allowed to move as shown

in Figure 10.16. This phenomenon is called electro-osmosis. Thus, “Electro-osmosis may

be defined as a phenomenon in which molecules of dispersion medium are allowed to
move under the influence of an electric field whereas colloidal particles are not allowed
to move.”
Water Colloidal sol

Water
+ −
Semipermeable membrane
Figure 10.16 Electro-osmosis
C
oagulation or flocculation or precipitation: “Coagulation or precipitation is a process of
(d)
aggregating together the colloidal particles so as to change them into large sized particles
which ultimately settle as precipitate.”
(1)
By addition of electrolyte: Coagulation is generally brought about by the addition of
electrolytes. Because when an electrolyte is added to a colloidal solution, the particles of
the sol take up the ions, which are oppositely charged and thus get neutralized. The ions
responsible for neutralization of charge on the colloidal particles are called the coagulat-
ing ion or flocculating ion. The neutral particles then start accumulating to form parti-
cles of large size, which settle down.
“The minimum amount of an electrolyte (millimoles) that must be added to one liter
of a colloidal solution so as to bring about complete coagulation is called the coagulation
or flocculation or precipitation value of the electrolyte. Thus, smaller is the coagulation
value of an electrolyte, greater is its coagulating or precipitating power.”
The observation about coagulation of colloidal sol was studied by Hardy Schulze
law. The main points of which may be stated as follows:
• The effective ions of the electrolyte in bringing about coagulation are those which
carry charge opposite to that of the colloidal particles. These ions are called coagulat-
ing ions or flocculating ions.
• Greater is the valency of the coagulating or flocculating ion, greater is its power to
bring about coagulation.
Thus, for coagulation of negatively charged As2S3 sol, the flocculating power
decreases in the order.
Al3+ > Ba 2 + > Na +
Similarly, for coagulation of positively charged Fe(OH)3 sol, the coagulating pow-
ers are in the order of
[Fe (CN)6 ]4− > PO34− > SO24 − > Cl −

10.26
The coagulating power is inversely proportional to coagulation/flocculation value.

Comparing the relative coagulating powers of two electrolytes for the same colloidal
sol, we have
Coagulating power of electrolyte 1 Coagulation value of electrolyte 2
=
Coagulating power of elecctrolyte 2 Coagulation value of electrolyte 1
(2) By electrophoresis: Coagulation is also brought about by electrophoresis process, in

which particles of the dispersed phase move towards oppositely charged electrode and
get neutralized. These neutral particles unite and grow in size and then settle down.
(3) By mutual precipitation: In this process, oppositely charged sols are mixed in proper propor-
tions to neutralize the charges of each other, which result in the coagulation of both the sols.
For example, if positively charged Fe(OH)3 and negatively charged As2S3 sols are
mixed, both the sols get coagulated.
(4) By prolonged dialysis: The stability of a colloidal sol is due to the presence of a small
amount of the electrolyte. On prolonged dialysis, the electrolyte is completely removed.
As a result, the colloidal sol becomes unstable and gets coagulated.
(5) By boiling or cooling: In some cases, heating the sols results in coagulation, for example,
coagulation of butter. During boiling, the adsorbed layer is disturbed because the num-
ber of collisions on them by the molecules of dispersion medium increases. As a result,
charge on the particles decreases. Hence the stability decreases, leading to their settling
down as a precipitate.
Similarly, in some cases, cooling the sol results in coagulation, for example, coagula-
tion of milk, that is, on cooling milk, fats start floating on the surface.
Isoelectric point: The charge present on lyophilic colloids like proteins, amino acids, poly-
(e)
peptides, etc., is a function of pH of the medium. They are positively charged in strongly acidic
solution and negatively charged in alkaline medium. However, at a certain pH of the disper-
sion medium, the dispersed particles are neutral, and hence that point is called isoelectric
point. The molecules at the isoelectric point exist as zwitter ions. The dispersed particles are
neutral, and hence they do not migrate when subjected to an electric field. So, at isoelectric
point, coagulation of colloidal particles starts.
+
OH− H3O
R CH COO− R CH COOH R CH COOH
NH2 NH2 NH3

Negative charge
+
Positive charge
(In Basic medium) (In Acidic medium)
Protective action of lyophilic colloids: Lyophobic sols are less stable and hence more easily
(f)
coagulated than lyophilic colloids. This is because the stability of lyophilic sols is due to two
factors:
(1) Same charge on all the colloidal particles
(2) Solvation of the colloidal particles
Thus to bring about coagulation, both these factors have to removed. This is done by
• By adding electrolyte
• By adding suitable electrolyte.

But the stability of lyophobic sol is only due to charge. This factor can be removed by
adding only electrolyte. Hence they can be easily coagulated.
However, it is observed that the addition of certain lyophilic colloids like gums,
soaps, gelatine, etc., to lyophobic colloids (like a metal sol of Ag, Au, etc.) render lyopho-
bic colloids difficult to coagulate by the addition of electrolytes. The process is known as
“protection” and the lyophilic colloids are termed as protective colloids. The protective
action of the lyophilic colloids is due to the covering up of the particles of the lyophobic
colloid by those of the lyophilic colloids as shown in Figure 10.17.
Lyophilic particles
(Protecting particles)
Lyophobic particles
(particles being protected)
Figure 10.17 Protection of colloids
This explanation is not fully correct because the particles of protecting substance
have almost the same size as those of the substance being protected.
To compare the protective action of different lyophilic colloids, Zsigmondy (in 1901)
introduced a term called gold number. It is defined as follows:
“Gold number of a protective colloid is the minimum weight of it in milligrams which
is just sufficient to prevent the coagulation of 1 ml of standard gold sol (i.e., containing
0.0053–0.0058% gold) by the rapid addition of 1 ml of 10% of sodium chloride solution.”
The coagulation of a gold sol is indicated by the change in colour from red to violet. Thus,
the smaller the gold number of a protective colloid, the greater is its protective action. The
gold numbers and reciprocals of few colloids sols are listed in Table 10.9.
Table 10.9 Gold number of a few protective colloids

Colloidal sol Gold number Reciprocal
Gelatin 0.005–0.01 200–100
Casein 0.01–0.02 100–50
Hemoglobin 0.03–0.07 33–14
Gum arabic 0.15–0.25 7–4
Albumen 0.1–0.2 10–5
Starch 20–25 0.5–0.4

10.28
10.3.4 Applications of Colloids

(i) In everyday life
(a) Colloids play an important role in our daily life. Protoplasm and blood are all colloidal in
nature.
(b) A number of food particles that we eat are colloidal in nature, for example, milk, butter, ice
creams, fruit juices, halwa, etc.
(c) The clothes and shoes that we wear are based on colloidal nature. So generally all products in
everyday life that we are using depend on colloids, for example, inks, paints, rubber, cement,
synthetic plastic, etc.
(ii) In analytical chemistry
(a) Traces of noble metals in solution can be detected by microanalysis in which the colour of
colloidal solution formed is analyzed. For example, cassius purple test for gold is due to the
production of colloidal gold.
(b) Silica and alumina gels are used as adsorbent for gases and as drying agent in laboratory.
(c) In quantitative and qualitative analysis technique, colloidal sols are formed during analysis
process.
(iii) In agriculture
(a) Humus acts as protective colloids in good colloidal soils, which retain moisture for emergency.
(b) The soil retains the moisture; this can be reduced by using calcium salts, which results in
coagulation of soil and makes them less hydrophilic.
(iv) In medicine
Medicines in the form of colloids are easily absorbed by the body tissue due to large surface
area and hence are more effective, for example,
(a) Argyrol is a silver sol used as an eye lotion.
(b) Colloidal antimony is used for curing kala azar.
(c) Colloidal gold is used as an intramuscular injection.
(d) Milk of magnesia, which is an emulsion, is used as an antacid for reducing acidity in the stomach.
(e) Blood from minor cuts/wounds is stopped, by coagulation with alum or ferric chloride. The
trivalent Al3+ or Fe3+ ions neutralize the negative charge on the albuminoid particles (which
constitute the blood) and thus coagulate it.
(v) In industry
(a) Sewage disposal: Colloidal particles of dirt, mud, etc., carry electric charge. Hence, when
sewage water is passed through the plates kept at a high potential, the colloidal particles are
coagulated due to electrophoresis, and the suspended matter gets removed.
(b) Purification of water: Impure water containing bacteria or suspended, negatively charged clay
particles can be purified by the removal of these substances by their precipitation with the help of
alum in which Al3+ ions neutralize negatively charged colloidal impurities and settle down, and
pure water can be decanted off.
(c) Smoke precipitation: Smoke particles are actually electrically charged colloidal particles of carbon in
air. Precipitation of smoke particles is carried out by Cottrell precipitator, which is based on the prin-
ciple of electrophoresis. In this process, smoke is allowed to pass through a chamber having a
number of metal plates attached to a metal wire connected to a source of high potential as shown
in Figure 10.18. Charged particles of smoke get attracted by oppositely charged electrode, and
get precipitated after losing their charge and hot air that passes out through the chimney.

The dust particles are also removed in this process. Thus, the nuisance of smoke in big indus-
trial cities can be avoided.
High D.C. voltage Particles-free waste

( 50,000 volts) gases
Plate
electrodes
Chimney
Gases carring
dust or
carbon particles
Carbon or dust particles
Earth
Figure 10.18 Cottrell precipitator
(d)
Electroplating of rubber: Latex is a colloidal solution of negatively charged rubber particles.
From latex, rubber can be obtained by coagulation. Rubber-plated articles are prepared by
depositing negatively charged rubber particles over the articles to be rubber plated, making
that article an anode in a rubber-platting bath.
(e)
Leather tanning: The process of hardening of leather is known as tanning. The tanning of
leather is based on the mutual coagulation of oppositely charged colloids. Tannin, which is
obtained from plants (barks, wood, leaves, etc.) is a mixture of derivatives of polyhydroxy
benzoic acids. It contains negatively charged colloidal particles. Animal hides (raw skin) are
also colloidal in nature and contain positively charged particles. When they are soaked in
tannin, mutual coagulation takes place, and leather becomes hard. Chromium salts are also
used in place of tannin, and it is called chrome tanning.
(f)
In photography: A colloidal solution of silver bromide (AgBr) in gelatine is applied on glass
plates or celluloid films or paper to form sensitive plates in photography.
(g)
Cleansing action of soap: Soap solution is colloidal in nature. It helps in the removal of dirt
or dust sticks on the greasy or oily materials on the cloth. We know that soap is an emulsifier
and soaps are sodium or potassium salts of higher fatty acids, for example, sodium palmitate
(C15H37COONa), sodium sterate (C17H35COONa), etc. It consists of two parts: the hydrocar-
bon part (C15H31-, C17H35-, etc), which is soluble in oil and the polar group (COO− Na+),
which is soluble in water.

10.30
− +
R
: COO
Na
Hydrophobic part Hydrophilic part
(soluble in oil) (soluble in water)
Thus, if a drop of oil is surrounded by soap solution, the R-part of soap remains in the oil
and the COO- Na+ part remains in water as shown in Figure 10.19. Thus soap molecules are
concentrated over the surface of the drop of oil. As a result, the interfacial tension between
oil and water decreases, and hence they are intermixed into each other to form the emulsion.
Thus micelles are formed.
Water
Circle(−) represents polar group
(COO−Na+)
Oil
Wavy line( ) represents
Non-polar group(R−)
Figure 10.19 Role of soap as an emulsifier
(h) Fiber dyeing: The dyeing process means absorption of the colour on fiber. Various dyes are
colloidal in nature. So, there is diffusion of colloidal particles of dye into the fabric.
(i) In warfare: In warfare, smoke screens are used, which are nothing but colloidal dispersion
of certain substances (like titanium oxide) in the air.
(j) Artificial rain: Artificial rain can be caused by spraying charged colloidal dust or sand par-
ticles over a cloud. The colloidal particles (water particles) present in the cloud will get neu-
tralized and coagulate to form bigger water drops, causing artificial rain.
(vi) In nature
(a) Blue colour of the sky: This is due to the scattering of light by colloidal dust particles present
in air (Tyndall effect). Similarly, sea water looks blue due to the scattering of light by the
colloidal impurities present in the sea water.
(b) Tail of comets: Comets are celestial bodies, which fly with very high velocity and leave
behind solid particles in its path, and due to the scattering of light, it is seen as a Tyndall
cone-like structure, which we call the tail of comets.
(c) Fog, mist, and rain: In winters, at night, the moisture of the air condenses on the surface of
dust particles, forming fine droplets. These droplets are colloidal in size and hence continue
to float in the air in the form of fog or mist.
In the upper atmosphere, where the temperature is low, clouds are suspended in air. They
condense together to form bigger drops, which come down in the form of rain. Rain is also
caused when two oppositely charged clouds meet each other.

(d)
Formation of delta: River water contains charged colloidal particles of clay, sand, and many
other materials. Sea water is a very big storehouse of a variety of electrolyte dissolved in
it. As river water reaches the sea water, the electrolytes present in sea water coagulate the
suspended colloidal particles, which ultimately settle down at the point of contact. Thus, the
level of the river bed rises. As a result, the water adopts a different course, and delta is formed
(Figure 10.20), so we can simply say that delta is formed due to silting of estuary (i.e., deposit
of sediments at the mouth of the river).
River River
Coagulated
sand particles
(Delta)
Sea
Figure 10.20 Formation of delta

1. Adsorption is essentially __________ phenomenon.
[Ans.: Surface]
2. The solid on whose surface adsorption takes place is called __________.
[Ans.: Adsorbent]
3. The substance (a gas or a liquid) that is adsorbed on the surface of a solid (adsorbent) is known
as __________.
[Ans.: Adsorbate]
4. The process of removing an adsorbate from the surface of an adsorbent is referred to as __________.
[Ans.: Desorption]
5. When the concentration of the adsorbate becomes more at the surface of an adsorbent than in
bulk phase, the phenomenon is known as __________.
[Ans.: Adsorption]
6. The adsorption of H2 or O2 on charcoal is __________.
[Ans.: Physical adsorption]
7. The heat of adsorption in case of physical adsorption is 20–40 KJ/mole while in case of chemical
adsorption, it is __________ KJ/mole.
[Ans.: 40–400]

10.32
8. At low pressure, the amount of gas adsorbed is __________ proportional to pressure.
[Ans.: Directly]
9. All gas masks contain __________ as adsorbent.
[Ans.: Activated charcoal]
10. A true solution is transparent while a __________ is opaque in nature.
[Ans.: Colloidal solution]
11. A colloidal solution essentially consists of two phases namely (i) __________ and (ii) __________.
[Ans.: (i) Dispersed phase (ii) Dispersion medium]
12. Soap is an example of __________.
[Ans.: Associated colloids]
13. The pH of a lyophilic sol at which the dispersed particles are neutral is called __________.
[Ans.: Isoelectric point]
14. Fe(OH)3 sol is __________ charged while As2S3 sol is __________ charged.
[Ans.: Positively, Negatively]
15. The process of purifying a colloidal solution by placing it in a parchment bag kept in water is
known as __________.
[Ans.: Dialysis]
16. The process of converting a precipitate into colloidal solution on the addition of an electrolyte is
known as __________.
[Ans.: Peptization]
17. Owing to the phenomenon of Tyndall effect, the colloidal particles can be observed as points of
light with the help of __________.
[Ans.: Ultramicroscope]
18. The phenomenon of zigzag motion of colloidal particles is known as __________.
[Ans.: Brownian movement]
19. The migration of colloidal particles under the influence of an electric field is known as __________.
[Ans.: Electrophoresis]
20. The lyophilic colloids that stabilize a lyophobic sol are referred to as __________.
[Ans.: Protective colloids]
21. An aerosol is a colloidal system consisting of __________ dispersed in __________.
[Ans.: Liquid, Air]
22. The size of colloidal particles lies in the range of __________.
[Ans.: 10–1000 A°]
23. The colloidal solution of a solid in a liquid is called __________.
[Ans.: Sol]
24. Process of separating colloids from crystalloids is called __________.
[Ans.: Dialysis]

25. The movement of colloidal particles in a colloidal sol is called __________.

[Ans.: Brownian movement]
26. The movement of colloidal particles under the influence of an electric field is called
__________.
[Ans.: Electrophoresis]
27. The movement of dispersion medium under the influence of an electric field is called
__________.
[Ans.: Electro-osmosis]
28. The addition of an electrolyte to a colloidal sol results in __________.
[Ans.: Coagulation]
29. Smoke is a colloidal solution of __________ in the __________.
[Ans.: Carbon particles, Air]
30. Milk is a colloidal solution of__________ in __________.
[Ans.: Fats, Water]
31. The adhering of the molecules of a gas on the surface of a solid is called __________.
[Ans.: Adsorption]
32. The protective action of different colloids is compared in terms of __________.
[Ans.: Gold number]
33. Liquid–solid dispersions are known as__________.
[Ans.: Gels]
34. A true solution __________ scatter light, whereas a colloidal solution __________ light.
[Ans.: Does not, Scatters]
35. Freundlich adsorption isotherm is a plot of mass versus __________.
[Ans.: Pressure]

1. Adsorption is a phenomenon in which a substance:
(a) Goes into the body of the other substance
(b) Remains close to the other substance
(c) Accumulates on the surface of the other substance
(d) None of these
[Ans.: c]
2. In adsorption of oxalic acid on activated charcoal, the activated charcoal is known as
(a) Adsorbent (b) Adsorbate
(c) Adsorber (d) Absorber
[Ans.: a]

10.34
3. Physical adsorption is essentially quite appreciable

(a) At room temperature (b) At higher temperature
(c) At lower temperature (d) None of these
[Ans.: c]
4. In physical adsorption,
(a) Van der Waal’s forces play a key role.
(b) Chemical bonding plays a key role.
(c) Density of the adsorbing materials plays a key role.
(d) None of these
[Ans.: a]
5. In chemisorption,
(a) Chemical bonding is involved. (b) Physical attractive forces are involved.
(c) Van der Waal’s forces are involved. (d) None of the above
[Ans.: a]
6. Freundlich adsorption isotherm is given by the simple empirical relationship
m x
(a) = KP n (b) = KP1/ n
x m
x m
(c) = KP n −1 (d) = KP1/ n
m x
[Ans.: b]
7. The size of the colloidal particle ranges from
(a) 10 −2 cm to 10 −3 cm (b) 10 −3 cm to 10 −5 cm
−5 −7
(c) 10 cm to 10 cm (d) 10 −7 cm to 10 −8 cm
[Ans.: c]
8. How many phases are present in a colloidal system?
(a) 1 (b) 2
(c) 3 (d) 4
[Ans.: b]
9. The empirical relationship for Langmuir adsorption for moderate pressure is
x K2 P x K1 P
(a) = (b) =
m K1 P + K 2 m K2
x K1 P x K1 P
(c) = (d) =
m K 2 + K1 P m K 2 + K1
[Ans.: c]
10. At high pressure, the Langmuir adsorption relationship is
x x
(a) = 0 (b) = K1
m m
x x K1 P
(c) = 1 (d) =
m m K2 P
[Ans.: b]

11. At low pressure, the Langmuir adsorption relationship is

x
(a) = KP (b) x = K
m m P
x K1 P
(c) = (d) None of the above
m K2 P
[Ans.: a]
12. When a beam of light is passed through a colloidal solution, it

(a) Is reflected (b) Is scattered
(c) Passes through undeviated (d) Is completely absorbed
[Ans.: b]
13. The process of separation of crystalloids by using a semi-permeable membrane is referred

to as
(a) Filtration (b) Dialysis
(c) Ultrafiltration (d) Electrophoresis
[Ans.: b]
14. The amount of heat evolved when 1 mole of any gas is adsorbed on a solid adsorbent surface is
called
(a) Entropy (b) Enthalpy
(c) Heat of reaction (d) Enthalpy of adsorption
[Ans.: d]
15. The random or zigzag motion of the colloidal particles in the dispersion medium is referred
to as
(a) Electro-osmosis (b) Electrophoresis
(c) Brownian movement (d) Tyndall effect
[Ans.: c]
16. Soap essentially forms a colloidal solution in water and removes the greasy matter by
(a) Absorption (b) Emulsification
(c) Coagulation (d) None of the above
[Ans.: b]
17. The presence of electric charge on the colloidal particles is indicated by
(a) Osmosis (b) Dialysis
(c) Electrolysis (d) Electrophoresis
[Ans.: d]
18. The protective action of different colloids is expressed in terms of

(a) Oxidation number (b) Atomic number
(c) Gold number (d) Avogadro’s number
[Ans.: c]

10.36
19. The coagulating power of an electrolyte for arsenious sulphide (As2S3) decreases in the
order
(a) Na + , Al3+ , Ba 2+ (b) Po 43− , So 4 2 − , Cl −
(c) Al3+ , Ba 2+ , Na + (d) Cl − , So 4 2 − , Po 43−
[Ans.: c]
20. The smoke is a colloidal sol of:
(a) Solid dispersed in liquid (b) Gas dispersed in solid
(c) Solid dispersed in gas (d) Gas dispersed in liquid
[Ans.: c]
21. The best coagulant for the precipitation of ferric hydroxide is
(a) Na3PO4 (b) NaNO3
(c) KCl (d) MgSO4
[Ans.: a]
22. Fog is an example of colloidal system of
(a) Liquid dispersed in gas (b) Gas dispersed in gas
(c) Solid dispersed in gas (d) Solid dispersed in liquid
[Ans.: a]
23. The colloidal sols are purified by
(a) Peptization (b) Coagulation
(c) Dialysis (d) Flocculation
[Ans.: c]
24. Crystalloids differ from colloids mainly in respect of
(a) Electrical behavior (b) Particle size
(c) Particle nature (d) Solubility
[Ans.: b]
25. At the critical micelle concentration (cmc), the surface molecules
(a) Decompose (b) Dissociate
(c) Associate (d) Become completely soluble
[Ans.: c]
26. Alum purifies muddy water by
(a) Dialysis (b) Adsorption
(c) Coagulation (d) Forming a true solution
[Ans.: c]
27. Movement of dispersion medium under the influence of electric field is
(a) Electrodialysis (b) Electrophoresis
(c) Electro-osmosis (d) Cataphoresis
[Ans.: c]

28. Colloidal sol is

(a) True solution (b) Suspension
(c) Heterogeneous sol (d) Homogeneous sol
[Ans.: c]
29. Blood may be purified by
(a) Dialysis (b) Electro-osmosis
(c) Coagulation (d) Filtration
[Ans.: a]
30. Blue colour of water in the sea is due to
(a) Refraction of blue light by impurities in sea water
(b) Scattering of light by water
(c) Refraction of blue sky by water
[Ans.: a]
31. Which of the following acts as a protective colloids?
(a) Hydrophilic (b) Hydrophobic
(c) Gold sol (d) Both hydrophilic and hydrophobic
[Ans.: a]
32. Finely divided metal and porous substances provide
(a) Large surface area (b) Small surface area
(c) Moderate surface area (d) No surface area
[Ans.: a]

1. Define adsorption.
Ans.: A process in which molecules of a gas (or liquid) adhere to the surface of solid through
van der Waal’s forces or chemical bond.
2. What is an adsorbent? Give two examples.
Ans.: The solid or liquid surface on which adsorption takes place is called adsorbent. E.g.:
Silica gel and charcoal.
3. What is the effect of increase of temperature on the adsorption of a gas on a solid surface?
Ans.: In case of physical adsorption, rise in temperature decreases the adsorption, but in case of
chemical adsorption, it first increases and then decreases.
4. State one difference between physisorption and chemisorption.
Ans.: Physisorption is non-specific, whereas chemisorption is specific in nature.
5. What is meant by sorption?
Ans.: When adsorption and absorption take place simultaneously, the process is called sorption.
E.g.: Ammonia passed through water in contact with charcoal.

10.38
6. What is meant by desorption?

Ans.: Removal of the adsorbed species from the surface of the adsorbent is called desorption.
7. What is an adsorption isotherm?
Ans.: It is a plot of amount of gas adsorbed per unit mass of adsorbent (x/m) on a solid adsorbent
versus the gas pressure at a constant temperature.
8. What is an adsorption isobar?
Ans.: It is a graph between the magnitude of adsorption and temperature at constant pressure.
9. Give any two examples each for hydrophilic and hydrophobic adsorbents.
Ans.: Hydrophilic adsorbents: Silica gel and zeolites
Hydrophobic adsorbents: Charcoal, polymer adsorbent like polystyrene divinylbenzene
10. Which colloidal system is represented by butter?
Ans.: Butter represents the type, emulsion, that is, liquid fat dispersed in water.
11. Define emulsion.
Ans.: Emulsion is a colloidal suspension of one liquid in another, for example, milk.
12. Give one example for each of the following: (i) solid sol, (ii) solid emulsion and (iii) liquid
aerosol.
Ans.: Solid sol: Ruby glass
Solid emulsion: Cream
Liquid aerosol: Fog
13. What do you understand by electrophoresis?
Ans.: Motion of the colloidal particles of a sol under the influence of an electric field is
electrophoresis.
14. How do you distinguish a colloidal solution from a true solution?
Ans.: When a beam of light is passed through both the solutions, then only colloidal solution
shows Tyndall effect, whereas true solution does not.
15. What substances do the gold numbers possess?
Ans.: Lyophilic sols, which act as protective colloids, possess gold numbers.
16. Why are Brownian movement and Tyndall effects shown by colloidal solutions only?
Ans.: Large-sized particles in a colloidal solution do not settle down, because the molecules of
the dispersion medium bombard them continuously.
17. What happens when a beam of light is passed through a colloidal solution?
Ans.: When a beam of light is passed through a colloidal solution, placed in a dark room, the
path of the beam becomes illuminated and visible when viewed through a microscope
placed at right angle to the path of light. This phenomenon is called Tyndall effect.

18. What is observed when an electrolyte (NaCl) is added to ferric hydroxide sol?
Ans.: When NaCl is added to ferric hydroxide sol, the Cl- ions of NaCl neutralize the positive
charge on ferric hydroxide sol particles and coagulate it. Thus, coagulation of sol occurs.
19. Explain which one of the following electrolysis is most efficient in coagulating a ferric hydroxide
sol: (i) KCl, (ii) FeCl3, (iii) K4 [Fe(CN)6], and (iv) K3 [Fe(CN)6].
Ans.: Ferric hydroxide sol is positively charged, and it is coagulated by negative ions. Since,
negatively charged ion [Fe(CN)6]4- is furnished by K4[Fe(CN)6], it is the most efficient in
coagulating a ferric hydroxide sol.
20. Which one of these will be the most efficient for the precipitation of As2S3 sol and why? (i) NaCl
(ii) BaCl2 (iii) AlCl3
Ans.: Arsenic sulphide (As2S3) sol is negatively charged and is coagulated by positively charged
ions furnished by the added electrolyte. Since the highest positive valency Al3+ is fur-
nished by AlCl3, so, according to Hardy-Schulze law, AlCl3 is the most efficient in the
precipitation of As2S3 sol.
21. Gold number of gelatin and starch are 0.01 and 0.10, respectively. Which of the two possesses a
higher protective power and why?
Ans.: Gelatin, because the smaller the gold number, the greater is the protective power of lyo-
philic colloids.
22. Deltas are formed at a place where the rivers pour their water into sea. Give reason.
Ans.: The negative-charged, fine, sand particles present in the river water are precipitated by the
positive-charged Na+, K+, Mg2+, and Ca2+ ions present in the sea water, thereby leading to
the formation of deltas at the place of their meetings.
23. Potash alum is used for removing impurities from water. Give reason.
Ans.: When alum is added to impure water containing fine, suspended, negatively charged clay
and sand particles, bacteria, etc., the Al3+ ions precipitate them and coagulate them, and
the purified water is left behind.
24. The colloidal particles precipitate on adding electrolyte. Why?
Ans.: Because, when electrolyte is added to a colloidal sol, the charge on the colloidal particles is
neutralized by the oppositely charged ions furnished by the electrolyte. So these particles coag-
ulate and change into bigger particles, which finally settle down under the influence of gravity.
10.4.4 Long Answer Questions

1. Distinguish between physisorption and chemisorption with examples.
2. What are the various factors affecting adsorption of a gas on a solid adsorbent?
3. Derive Langmuir’s adsorption isotherm for monolayer adsorption and show under what condi-
tions it becomes identical to Freundlich adsorption isotherm.
4. Define the terms adsorption, occlusion, adsorption and sorption. How does pressure affect the
adsorption of a gas over activated charcoal at constant temperature?

10.40
5. State and explain BET equation for multilayer adsorption.

6. What is a colloidal sol? How are colloidal sols prepared? Explain the meaning of the following terms:
(a) Tyndall effect
(b) Eletrophoresis
(c) Brownian movement
7. Give a brief account of the optical and electrical properties of colloids.
8. Write a brief account on the following.
(a) Origin of charge on the colloidal particles
(b) Zeta potential and electrical double layer
(c) Gold number
(d) Cataphoresis
9. What is meant by coagulation of colloidal sol? Bring out clearly the role of electrolytes to cause
flocculation of colloidal sols.
10. When a beam of light is passed through a colloidal solution, the path of the beam becomes vis-
ible. Give reasons.
11. Write an account on electro-osmosis and also the significance of electro-osmosis?
12. Explain the natural applications of colloids.
13. Explain the method for determining the surface area of absorbents.
14. Differentiate the following:
(a) Crystalloids from colloids
(b) Lyophilic from lyophobic sols
(c) Chemisorption from physiorption
15. Discuss the various applications of colloid chemistry.
16. Discuss in detail the important applications of colloids in:
(a) Food industry
(b) Chemical industry
(c) Purification of air
(d) Pharmaceutical industry

11 THERMODYNAMICS
11.1 INTRODUCTION
Thermodynamics is the branch of science that deals with the conversion or transformation of heat
energy into other forms of energy such as chemical, electrical, light energy, etc. It is also defi ned as
the study of the flow of heat or any other form of energy into the system as it undergoes a physical or
chemical transformation.
11.1.1 Thermodynamic Terms and Basic Concepts

System
A defi nite quantity of matter bounded by some enclosed surface is known as a system. A system is also
defi ned as that part of the universe which is under thermodynamic study.
Examples: For a scientist, the gas enclosed in a cylinder is a system. For a mechanical engineer,
the machine is a system.
Surrounding
All the matter which can influence the behaviour of the system is known as surroundings. In other
words, except system, rest of the universe is surroundings.
Examples: For an egg placed on the table, the atmosphere around the egg is the surrounding.
Note: The choice of a system and its surrounding is arbitrary.
Boundary
The real or imaginary surface separating the system from its surroundings is called the boundary.
Homogeneous System
When a system is uniform throughout, it is called a homogeneous system.
Example: Pure single solid or liquid or gas system
Phase: Homogeneous, physically distinct and mechanically separable position of a system.

11.2
Heterogeneous System
Heterogeneous system is one which consists of two or more phases.
Examples: Ice in contact with water, ice in contact with water vapour, etc.
11.2 TYPES OF THERMODYNAMIC SYSTEMS

There are three types of thermodynamic systems depending on the nature of the boundary.
11.2.1 Isolated System

If a system may be exchanges neither matter nor energies with the surroundings, then it is known as
an isolated system (Figure 11.1).
Example: A substance, say, boiling water, contained in a thermoflask.
Isolated
system
Insulated
boundary
Figure 11.1 Isolated system
11.2.2 Closed System

If a system exchanges energy but not matter with the surroundings, then it is called a closed system. In
other words, a closed system is one which cannot transfer matter but can transfer energy in the form of
heat, work and radiation to its surroundings.
Example: A specific quantity of hot water contained in a sealed tube is an example of a closed
system while no water vapour can escape from this system; it can transfer heat through the walls of the
tube to the surroundings (Figure 11.2).
Figure 11.2 Closed system
11.2.3 Open System

If a system exchanges both energy and matter with the surroundings, then it is called open system.

Thermodynamics 11.3
Example: Hot water contained in a beaker placed on laboratory table is an open system. The water
vapour (matter) and also heat (energy) is transferred to the surroundings through imaginary boundary
(Figure 11.3).
Figure 11.3 Open system
11.3 INTENSIVE AND EXTENSIVE PROPERTIES
11.3.1 Intensive Property

A property that does not depend on the quantity of matter present in the system is known as intensive
property.
Examples: Pressure, temperature, density, EMF, etc.
11.3.2 Extensive Property

A property that depends on the quantity of matter present in the system is called extensive property.
Examples: Volume, number of moles, enthalpy, entropy and Gibbs free energy
Hence, macroscopic properties are divided as intensive and extensive properties.
11.3.3 State Variables

A thermodynamic system is said to be in a certain state when all its properties are fixed. Fundamental
properties that determine the state of a system are pressure (P), temperature (T), volume (V), mass (M)
and composition. Since a change in the magnitude of such properties alters the state of the system,
these are referred to as state variables.
11.4 REVERSIBLE AND IRREVERSIBLE PROCESS
11.4.1 Reversible Process

The process in which all the changes that occurred in the direct process are repeated in the reverse
direction is called reversible process.
In a thermodynamic system, in the change of the state of absorption of heat energy in the direct
process, the system should release the same amount of heat energy. It changes the state in the reverse
direction. This type of process is called reversible process.

11.4
For example, very slow process done at constant temperature, Carnot cycle process, etc.
If a certain amount of heat is given to ice through it melts and water is formed. If the same amount
of heat is removed from water while the ice is formed.
11.4.2 Irreversible Process

The process in which all the changes that are accepted in the direct process were not repeated in the
reverse direction is called irreversible process.
All the processes that irreversibly occur are examples of an irreversible process.
Examples: conduction, radiation, radioactive decay, electrical heating of a wire, etc.
If an electric current is passed in the wire, the heat is developed in the wire and this cannot be
reversed.
11.4.3 Thermodynamic Processes

When a thermodynamic system changes from one state to another, the operation is called a process.
The various types of thermodynamic processes are as follows:
Isothermal Process
The processes in which the temperature remains constant are termed isothermal processes.
Here dT = 0 dV = 0 PV = Constant
Example: This is often achieved by placing the system in a thermostat.
Adiabatic Process
The processes in which no heat can flow in or out of the system are called adiabatic processes. For an
adiabatic process,
Cp
dQ = 0 where PV g = constant g = C
n
Example: Adiabatic conditions can be approached by carrying the process in an insulated container
such as a thermos bottle.
Isobaric Process
The processes which can take place at constant pressure are called isobaric processes.
Here dP = 0 ∆P = 0
Example: Heating of water to its boiling point and its vapourisation takes place at the same atmos-
pheric pressure.
Isochoric Process
The processes which can take place at constant volume are known as isochoric processes.
Here dV = 0 ∆V = 0
Example: The heating of a substance in a non-expanding chamber is an example of isochoric process.

Thermodynamics 11.5
Cyclic Process
When a system in a given state goes through a number of different processes and finally returns to its
initial state, the overall process is called a cyclic process.
Here ∆E = 0 ∆H = 0
Example: Carnot cycle
In thermodynamics, the state of a system can be represented by pressure, volume and temperature.
These three parameters are known as thermodynamics variables.
Thermal Equilibrium
If there is no heat exchange between two bodies, the bodies are said to be on thermal equilibrium.
11.4.4 Isothermal Process or Isothermal Change

When a thermodynamic process occurs in such a way that its temperature remains constant, the pro-
cess is called isothermal process. In an isothermal process, the heat generated or lost is given or taken
from the surroundings.
Example: When a gas in a cylinder is slowly compressed, heat is generated and conducted to the
surroundings, on other hand, when the gas is allowed to expand slowly a slightly cooled but heat is
taken from the surrounding such that the temperature remains constant.
Heat
Every form of energy has its own method of transmission from one place to another. Heat is one of the
forms of energy that can be transmitted over large distances in vacuum. The specialty of heat energy
is that it can get transmitted by three distinct processes, totally different from one another. They are
conduction, convection and radiation.
Conduction
The transmission of heat from the hotter to the colder part of a body without the transfer of the particles
of the material medium is defined as conduction.
Convection
The transmission of heat from one part to another part of the body or surroundings by the transfer of
particles of matter known as convection.
Radiation
Transmission of heat from a hot body to a cold body without the help of any material or medium.
Conduction and convection are the methods of heat transmission which can be carried out in the
presence of only material medium.

11.6
Work
Force × distance [Joules]
When a force acts on a system such that it produces a displacement in the system, the work is said
to be done.
Equivalence of Heat and Work

It is an established fact that heat is a form of energy; for example, when the brake is applied on a mov-
ing vehicle, the drum becomes hot. In this situation, friction is involved and heat is produced; when
mechanical energy (work) disappears, heat is produced. This shows the equivalence between heat and
work.
Internal Energy or Intrinsic Energy

Every thermodynamic system has a definite amount of energy within itself. The stored energy in a
system which is not apparently shown is called the internal energy or intrinsic energy.
Example: Consider gas enclosed in a cylinder; according to kinetic theory of gases, gas molecules
are in rapid motion and hence they possess kinetic energy. Due to intermolecular forces of attraction,
the system possesses potential energy. The sum of kinetic energy and potential energy is equal to the
internal energy of the system.
Note: The internal energy (U) is independent of the path followed in a cyclic path or process; the
change in internal energy is dU = 0.
If the system can be transferred from the initial state to the final state, the work done by the system
W and the accepted or rejected heat Q but practically the value of Q−W value is a constant. The value
of Q−W can only depend on the initial and the final states of the work.
Q−W = ∆V = Vf − Vi
∆V shows the difference between the initial and final states of the system. This difference is said as
internal energy and is the function of P, V and T.
U in case of functions P, V
 ∂U   ∂U 
dU =   dv +  dP
 ∂V  P  ∂P  V
U in case of functions P, T
 ∂U   ∂U 
dU =  dP +  dT
 ∂P  T  ∂T  P
U in case of functions T, V
 ∂U   ∂U 
dU =  dV +  dT
 ∂V  T  ∂T  V
11.4.5 Indicator Diagram

For an infinite small change in volume between states C, D, the pressure can be treated as almost
constant.
∴ Work done by the gas = PdV

Thermodynamics 11.7
v2
∴ Total work done during expansion = ∫ PdV

v1
It can be shown the area under the curve AB represents the total work done by the gas during
expansions; it is shown with the shaded region in the graph. When the graph is traced from B to A, it
represents the work done on the gas, that is, the gas is said to be compressed.
A graph between pressure and volume of a thermodynamic system is known as indicator diagram.
These diagrams are used to discuss the theory and performance of heat engines (Figure 11.4).
Pi A(Pi, Vi)
CD
B(Pf, Vf)
Pf
Vi dv Vf
Figure 11.4 Indicator diagram
Let us take the initial state (Pi, Vi) of the gas by a point A and the final state (Pf, Vf) by a point B as
shown in the graph. The point A and B indicates to the state of change of gas from A to B and also
called the indicator diagram.
Work Done in Isothermal Process

A process that takes place at constant temperature is known as an isothermal process (Figure 11.5).
F
G B
E H
Vi dv Vf
V
Figure 11.5 Isothermal process
Let one gram mole of an ideal gas expand isothermally. The initial stage A (Pi, Vi) and final stage are
at B (Pf, Vf). In an isothermal process, the pressure and volume are changed but the temperature will
be constant.
Work is done by the gas for a small expansion dW = PdV when it expands from initial value to
final value.

11.8
vf
W= ∫ PdV
vi
RT
Ideal gas equation PV = nRT ⇒ PV = RT (∴n = 1) P=
V
Vf
RT PV = nRT constant
∴W = ∫ dV
Vi
V Vf Vf
 nRT 
W = ∫ PdV = ∫  dV
 V 
Vf
1
W = RT ∫ V dV Vi V i
Vi Where T is constant
W = RT log (V )Vif
V
Vf
or dV
W = RT (log V f − log Vi )
W = nRT ∫
Vi
V
 Vf  = nRT log V V
Vf
W = 2.303 RT log10  
 Vi  i
  Vf 
 Vf  = nRT 2.3026 log10   
W = RT log e     Vi 
 Vi 
The work done in an isothermal process is as follows:
W = nRT loge  f  = 2.303 nRT log10  f 

V V
 V   V 
i i
11.4.6 Work Done by a System in an Adiabatic Process

An adiabatic system is a system with no exchange of heat between the system and its surroundings
(Figure 11.6).
A(Pi, Vi)
C
D
B(Pf, Vf)
P
C′ D′
Vi dv Vf
V
Figure 11.6 Work done in adiabatic process
One gram mole of an ideal gas expands adiabatically from the initial state A (Pi Vi) to a final state
B (Pf Vf) as shown in the graph; during adiabatic expansion, the pressure and the volume change but
the heat is constant.

Thermodynamics 11.9
Let P and V be at intermediate stage C for a small change in volume dV from A to B and C to D.
The work done by the gas during the small expansion is PdV; this is equal to the shaded area CDC′D′
as shown in the graph.
The network done by the gas during the expansion from Vi to Vf is given as follows:
Vf
W= ∫ PdV
Vi
In case of adiabatic process
VfK
dV PV r = K
W= ∫ r
V
Vi
Vf
dV K
= K∫ P=
Vi
Vr Vr
Vf
V − r +1
= K ∫ V − r dV ∴∫ V − r =
Vi
−r + 1
K
= V 1− r − Vi1− r 
1− r  f
K  1 1 
=  − r −1 
1 − r Vf r −1
Vi 

1  K K 
= −
1 − r V fr −1 Vi r −1 
 
1  Pf V f PV
r r

=  − i i
r −1 
1 − r Vf r −1
Vi 

1
W=  P V − PV  ∴ PV r = RT = K
1− r  f f i i
Pf V f = RT f
i i = RTi
PV
If Ti and Tf correspond to the initial and final of the stages,

1
So ⇒ W =  RT − RTi 
1− r  f
R
W= T − Ti  (or)
1− r  f
R
W= T − T f 
r −1  i
Thermodynamics
The study of internal energy of any system is known as thermodynamics.

11.10
Indicator Diagram
A graph between pressure (P) on the Y-axis and volume (V) on the X-axis is the indicator diagram; this
diagram is also called the P–V diagram (Figure 11.7).
Pi A(Pi, Vi)
C
D
Pf B(Pf, Vf)
O Vi dv Vf
Figure 11.7 Graph between pressure and volume
Internal Energy
The ideal gas of internal energy can be dependent on the temperature.
 ∂u   ∂u 
Ideal gas  =0 and  ∂P  = 0
 ∂V  T T
11.4.7 First Law of Thermodynamics and its Applications

The total energy of an isolated system remains constant though it may change from one state to another.
Hence, the absorbed heat of any system is equal to the sum of the increase in internal energy and the
work done by the system. According to this law, if a small amount of heat energy (dQ) is supplied to
the system, then a part of the energy is used to increase the internal energy (dU) of the system and the
remaining energy is used to do external work by the system (dW).
The first law of thermodynamics can be written as dQ = dU + dW(1)
For external work dW = PdV
∴ dQ = dU + PdV
The external work dW = 0, dQ = dU
This law explains the law of conservation energy. It means that thermal energy can be converted
into mechanical energy. Energy can be neither created nor destroyed but it may change from one state
to another. Whenever a quantity of some form of energy disappears, an exactly equivalent amount of
some other form of energy must be produced.
Second Law of Thermodynamics

According to entropy the second law of thermodynamics can be written as
dQ = TdS (2)
Relation between (1) and (2)
TdS = dU + PdV
dU = TdS − PdV

Thermodynamics 11.11
dQ = dU + dW
dW = PdV dQ = dU + PdV
Application of First Law of Thermodynamics

Isothermal Process
In an isothermal process, the temperature of the system remains constant;
that is, dT = 0
Hence, there is no change in the internal energy of the system: dU = mCdT = 0
∴ From the first law, dQ = 0 + dW
dQ = dW
In an isothermal process, the heat supplied a system is used only to do external work.
Adiabatic Process
In an adiabatic process, there is no exchange of heat between the system and the surroundings;
that is, dQ = 0
∴ From the first law of thermodynamics,
dQ = dU + dW
0 = dU + dW
dU = −dW
Therefore, during adiabatic compression, work is done on the gas (dW − Vc) and hence the internal
energy increases (du = +ve).
Cyclic Process
When a system undergoes a cyclic change, the dU = 0.
From the first law of thermodynamics,
dQ = dU + dW ∴ dU = 0
dQ = dW
Isochoric Process
In an isochoric process, there is no change of volume.
For an isochoric process, dV = 0
∴ From the first law of thermodynamics,
dQ = dU + dW
dQ = dU + PdV ∴ dV = 0
dQ = dU
that is, the total heat supplied to the system is equal to the increase in internal energy of the system.

11.12
Isobaric Process
In an isobaric process, the pressure is constant.
Example: phase change process (water to stream)
Heat Capacity
Energy required to raise the temperature of a system is known as heat capacity. If a Q calorie of heat is
absorbed by the system, the temperature of the system raises from T1 to T2.
Heat capacity:
Q
C=
T2 − T1
Thus, the heat capacity of a system is the heat absorbed by unit mass in raising the temperature by 1°C.
For gaseous systems, heat capacity is of two types.
Heat Capacity at Constant Volume (Cv )

In constant volume, the molar heat capacity of a system is defined as the amount of heat required to
raise the temperature of one mole of the substance by 1°C. At constant volume (Qv) when the amount
of heat absorbed by gaseous system (in calories) the temperature raises from T1 to T2.
Heat capacity:
QV
CV =
T2 − T1
According to the first law of thermodynamics,
Q = ∆E + W
Q = ∆E + P ∆V ∴W = P ∆V
⇒ Q = ∆E (∵ ∆V = 0 for isochronic system)
QV ∆E
∴ CV = =
T2 − T1 ∆T
Heat Capacity at Constant Pressure (Cp)

At constant pressure, the molar heat capacity of a system is defined as the amount of heat required to
raise the temperature of one mole of the substance by 1°C. At constant pressure (Qp) when the amount
of heat absorbed by the system (in calories) the temperature raises from T1 to T2.
QP
CP =
T2 − T1

According to the first law of thermodynamics,

Q = ∆E + P ∆V
⇒ Q = ( E2 − E1 ) + P (V2 − V1 )
⇒ Q = ( E2 + PV2 ) − ( E1 + PV1 )
Enthalpy, H = E + PV
∴ QP = H 2 − H1 = ∆H
∴ QP = ∆H
QP ∆H
∴ CP = =
T2 − T1 ∆T
11.4.8 Second Law of Thermodynamics

Clausius Statement
It may be defined as follows:
“It is impossible for any cylindrical machine to transfer heat continuously from a cold body to a
hot body”.
“There is no perfect refrigerator”.
This statement implies that to transfer heat from one body to another body at a higher temperature,
some work must be done by an external agent.
Kelvin–Plank Statement
It is impossible for any reversible heat engine to convert total heat into work.
There is no perfect heat engine
This statement implies that a heat engine should reject a part of heat to a body at lower temperature
(sink) while converting the heat into work.
Importance of Second Law

The first law of thermodynamics says that heat and mechanical work is inter conversable; but it doesn’t
give any limitation and condition for this conversion. The second law of thermodynamics specifies the
direction of the flow of heat engine.
Carnot’s Theorem
In all reversible engines working with the same temperatures, limits will have the same efficiency.
No engine is more efficient than Carnot’s reversible engine working with the same temperature.
Consider two reversible engines A and B working with the temperature T1°C and T2°C. A is more
efficient than B; A works as a heat engine and B as a refrigerator. Engine A observes an amount of heat
energy Q1 from the source at T1°C. It does external work ‘W’. Q2 is rejected to the sink at temperature
at T2°C (Figure 11.8).

11.14
Source
T1° C
Q1 Q1′
A B
Q2 Q2′
Sink
T2° C
Figure 11.8 Working of reversible engines
Engine B observes the amount of heat Q2′ from the sink at temperature T2°C, and ‘W’ work is done on
the work substance and gives the heat Q1′ to the source at the T1°C.
W Q1 − Q2 Q
Efficiency of engine A = h = = = 1− 2
Q1 Q1 Q1
W ′ Q1 ′ − Q2 ′ Q′
Efficiency of engine B = h 1 = = = 1− 2
Q1 ′ Q1 ′ Q1 ′
Let h > h ′
W W
⇒ >
Q1 Q1 ′
⇒ Q1 ′ > Q1
Q1 ′ > Q1
only Q2 ′ > Q2
W = Q1 − Q2 = Q1 ′ − Q2 ′
= Q1 ′ − Q1 = Q2 ′ − Q2
Q2′ – Q2 = The quantity of heat taken from the sink at T2°C

Q1′ – Q1 = The quantity of heat given to the source at T1°C
The heat flows from the sink at the temp T2°C [lower] to the source at temperature T1°C (high
temperature) without any external work
∴ n = n′ its define the second law of thermodynamics
11.4.9 Carnot’s Engine Efficiency

A Carnot’s engine is a heat engine which can transfer heat energy from a body having higher tempera-
ture to lower temperature while transforming the heat energy from one body to another. The Carnot’s
engine loss of heat energy is very minimum.
A Carnot’s engine has mainly four parts:
(i) Source
(ii) Sink
(iii) Working substance
(iv) Insulating stand

Source
A source is the part of the Carnot’s engine which supplies the heat energy with high temperature T1K;
it has infinite thermal capacity. Since it has infinite thermal capacity, its temperature does not change
when some amount of heat energy is drawn from heat.
The source is made up with an adiabatic wall at the bottom and the sides are closed with a diather-
mic wall at the top as shown in Figure 11.10.
Sink
A sink is the part of Carnot’s engine which receives the heat energy, with low temperature T2K.
The sink similar to the source as shown in Figure 11.9.
Working Substance
It is the part of Carnot’s engine which cross heat from the source and is supplied to the sink. The
working substance to heat generally uses ideal gas. The work substance is taken in a cylinder having
movable piston (P) as shown in Figure 11.9. The bottom surface of the cylinder is made with the adi-
abatic wall.
Insulating Stand
It is a part of the Carnot’s engine which can be used for transferring heat from the source to the sink
without loss of heat. This is made with adiabatic material as a block as shown in Figure 11.9.
Thermal wall Piston Adiabatic wall
T1 T2
Adiabatic wall
Ideal gas
Figure 11.9 Carnot’s engine
y
A (P1,V1,T1) Source
B (P2,V2,T1)
Stand Stand
C (P3,V3,T2)
P D (P4,V4,T2)
Sink
O E H F G x
V
Figure 11.10 Working of Carnot’s engine

11.16
11.4.10 Working of Carnot’s Engine

The working of Carnot’s Engine is explained by four cyclic operations; these are shown in Figure 11.10.
Step 1
Let a cylinder having work substance be placed on the source. Let the initial state of gas on the system
be A (P1, V1, T1). It allows the expansion of gasses, slowly moving the piston in the upward direction
whose state reaches B (P2, V2, T1).
∴ The temperature remains constant in this expansion. It is an isothermal expansion.
In this expansion, the working substance can cross heat energy from the source with work done,
W1. The change of state of process is representation in P–V diagram.
The work done in this process is equal to the area of ABCD.
V2
Q1 = W1 = ∫ PdV
V1
PV = nRT If n = 1
V2 dV RT1
P=
= RT1 ∫ V V
V1
V2
= RT1 log e tempp constant
V1
(or)
V 
Q1 = W1 = 2.303 RT1 log10  2  (1)
 V1 
Step 2
Let the cylinder detached from the source be placed on the insulating stand. It allows the adiaba-
tic expansion whose temperature changes to T2. In this adiabatic expansion, the change of state is
observed from B (P2, V2, T1) to from position C (P3, V3, T2). This is shown in the indicator diagram.
Let the work done in this process be W2.
V3
W2 = − ∫ PdV
V2
− R(T1 − T2 )
=
( r − 1)
(or)
−R
W2 = [T − T ]
1− r 2 1
Step 3
Let the cylinder from the stand and place it into the sink to allow the isothermal contract. In this pro-
cess, the change of state is from C (P3, V3, T2) to D (P4, V4, T2). The isothermal contraction is represented
in the indicator diagram as CD.
Let the work done in this process be W3 and the heat supplied to the Q2 be
V4
Q2 = W3 = ∫ PdV
V3
V 
= RT2 log e  4 
 V3 

Step 4
Let the cylinder be detached from the sink and place it on the insulating stand. Allow the adiabatic
contraction until the temperature of the system reaches the T1 element in this process. The change of
state from D (P4, V4, T2) to A (P1, V1, T1) is represented in the indicator diagram DA.
Let the work done in this process be
R
W4 = [T − T ]
1− r 1 2
∴ The total work done W = W1 + W2 + W3 + W4
V  V 
= 2.303 RT1 log10  2  + 2.303 RT2 log10  4  (5)
V
 1  V3 
According to adiabatic relations from the curves A, D

A=D
T1 V1r −1 = T2 V4r −1
T1 V4r −1
= (6)
T2 V1r −1
Adiabatic from BC curves relation

B=C
r −1
T1 V2 = T2V3r −1
T1 V3r −1
=
T2 V2r −1
r −1 r −1
V  V 
 4 =  3 (7)
 V1   V2 
V4 V1
By using equations (6) and (7) = (8)
V3 V2
Substitute equation (8) in equation (5) we get,
V  V 
W = 2.303 RT1 log10  2  + 2.303 RT2 log10  1 
 1
V  V2 
V 
W = 2.303 R loog10  2  [T1 − T2 ] ∴ Q1 = Q2
 V1 
The efficiency of adiabatic Carnot’s engine defines the ratio of work done to the heat energy drawn
from the source.

11.18
T1 − T2
=
T1
V 
2.303 R log10  2  [T1 − T2 ] Q1 − Q2
W  V1  h=
Efficiency = = Q1
Q1 V 
2.303 RT1 log10  2  Q
 V1  = 1− 2
Q1
T
h = 1− 2
T1
The efficiency of the Carnot’s engine depends on the temperature of the sink and the source. The
efficiency of the Carnot’s engine does not depend on the physical properties of the working substance.
11.4.11 Absolute Zero

The efficiency of the Carnot’s engine in terms of the temperatures in Kelvin scale is written as n =
T
1− 2
T1
If T2 = 0°K, then n = 1.
Absolute zero in Kelvin scale is defined as the temperature of the sink for which the efficiency of
Carnot’s engine is equal to unity; it converts total heat into work.
Thermodynamics Scale of Temperature or Kelvin’s Absolute Scale of Temperature

Thermodynamic or Kelvin scale of temperature is based on the efficiency of Carnot’s reversible engine.
Carnot’s engine depends on the temperature of the source (T1) and sink (T2), and it is independent of
the working substance.
Consider a reversible heat engine absorbing an amount of heat Q1 at T1 rejecting heat Q2 at T2.
∴ The efficiency is only the function of two temperatures:
Q1 − Q2 Q T
n= = 1− 2 = 1− 2
Q1 Q1 T1
W Q1 − Q2
n= = = f (T1 , T2 )
Q1 Q1
Q2
1− = f (T1 , T2 )
Q1
Where f (T1, T2) is a function of T1 and T2.
Q2
= 1 − f (T1 , T2 )
Q1
Q1 1
⇒ = = f (T1 , T2 ) (1)
Q2 1 − f (T1 , T2 )
Where F (T1, T2) is another function of T1 and T2.
Now consider another reversible heat engine which absorbs heat Q2 at T2 and rejected Q3 at T3.

Q2
= F (T2 , T3 ) (2)
Q3
Q1
= F (T1 , T3 ) (3)
Q3
Q1
= F (T1 , T2 ) F (T2 , T3 )
Q3
F (T1 , T3 ) = F (T1 , T2 ) F (T2 , T3 ) (4)
We observe that there is no T2 on the left hand side of the equation. This is possible only if
f (T1 )
F (T1 , T2 ) = (5)
(5)
f (T2 )
where f is another function
f (T2 )
F (T2 , T3 ) = ( 6)
(6)
f (T3 )
∴ From equation (1) and (5)
Q1 f (T1 )
=
Q2 f (T2 )
Since Q1 > Q2, f (T1) > f (T2) provided T1 > T2

i.e. f (T) is linear function of a T
∴ Let f (T) = T
Q1 f (T1 ) t 1
∴ = =
Q2 f (T2 ) t 2
where T1, T2 are the temperature in Kelvin scale.

The aforementioned equation defines the Kelvin scale as follows.
“Kelvin scale is that scale in which the ratio of any two temperatures is the same as the ratio of
heat absorbed and heat rejected by a reverse Carnot’s engine working between the two temperatures”.
11.4.12 Numerical Problems Based on Carnot’s Cycle

(i) Calculate the efficiency of a reversible heat engine working between 72°C and 187°C.
T2
∴ Efficiencyn = 1 −
T1
345 Sink T2 = 72 + 273
= 1−
460
= 345° K
= 1 − 0.75
Sink T1 = 187 + 273
n = 0.25 (or ) 25%
= 460 K

11.20
(ii) A refrigerator works under a reversible cycle between the temperature 300°K and 400°K. Calcu-
late the coefficient of performance.
T2 300
K= = =3 T = 300 K
T1 − T2 100 2
T1 = 400 K
K =3
(iii) In a steam turbine, steam heated to 750°C enters the turbine and its temperature is 110°C. What
is the maximum theoretical efficiency of the turbine?
T2 T2 = 110°C
n = 1−
T1
= 110 + 273
383
= 1 − = 1 − 0.374 = 383° K
1023
n = 0.63 (or ) 63% T1 = 750 + 273
= 1028° K
(iv) A Carnot’s engine works between 227°C and 27°C. Its efficiency is 50%. What is the percentage
of actual efficiency of theoretical efficiency?
T
Actual efficiency n = 1 − 2
T1
300
= 1− T2 = 273 + 273
500
3 2 = 300 K
= 1 − =
5 5 T1 = 273 + 227
= 0.4 = 40%
= 500° K
Theoretical efficiency = 50%
40
Percentage = × 100 = 80%
50
(v) A reversible engine works between two temperatures whose difference is 100 K. If it absorbs 746 J
of heat from source and rejects 546 J to sink, calculate the temperatures of source and sink.
We know that
Q2 T
1− = 1− 2
Q1 T1
Q1 − Q2 T1 − T2
= =
Q1 T1
Q1 = 746 J
746 − 546 100
⇒ = Q2 = 546 J
746 T1
T1 − T2 = 100° K
200 100
⇒ = T1 =?
746 T1
T2 =?

100 × 746
⇒ T1 =
200
T1 = 373° K (or )100°C
Actually
T1 − T2 = 100° K
T2 = T1 − 100 K
= 373 − 100
= 273° K (or ) 0°C
11.4.13 S
olved Numerical Problems Based on Isothermal
and Adiabatic Process
(i) A gas at 27°C is compressed to half its volume suddenly calculate the resulting pressure and
temperature (given r = 1.41).
In an adiabatic process,
TV
1 1
r −1
= T2V2r −1 T1 = 273 + 27
T2  V1 
r −1 = 300 K
=
T1  V2  V1 = V
T2  V 
1.41−1 V2 = V / 2
=
300  V /2  r = 1.41
T2 = ?
T2 = 300 × (2)
0.41
p1 = 1 atp
T2 = 300 × 1.33
T2 = 399 K (or )126°C
1 1 r = P2V2 r
PV
r 1.41
P2  V1  P  V 
⇒ P2 = (2)
1.41
= ⇒ 2 =
P1  V2  1  V /2 
p2 = 2.66 atp
1 atp = 1.013 × 105 N/m 2

(ii) The initial temperature of a gas is 27°C; to calculate the rise in temperature when the gas is com-
pressed suddenly to eight times its original pressure (r = 1.5),
P11− r T1r = P21− r T2r T1 = 27 C
1− r r (1−1.5 ) 1.5
−1 T = 300 k
−1 1
 P1   T2   P  T  0.5  1   T 
=  2  ⇒ T2 = 300 × (2 −3 ) 3 P1 = P
3
 P  =  T  ⇒  8 P  = 2 
 300 
=
1.5  8   300 
2 1
P2 = 8 P
= 600 K (or ) 327°C
T2 = ?

11.22
(iii) A quantity of an ideal gas at 17°C is adiabatically compressed to one-tenth of its initial volume.
Calculate the final temperature of the mono atomic and diatomic gas (given r for mono atomic
gas is 1.6, diatomic gas is 1.4)
(a) Monoatomic gas
r −1
TV
1 1 = T2V2r −1
r −1
T2  V1  T1 = 17°C
=
T1  V2  = 17 + 273 = 290
1.61−1
T2  V  V1 = V
=
290  V /10  V
V2 =
T2 10
= (10 )
1.61−1
290 T2 = ?
T2 = 290 × 10 0.61
r = 1.61
= 4.07 × 290
T2 = 1,180 K
(b) Diatomic gas r = 1.4
r −1
T2  V1 
=
T1  V2 
1.4 −1
T2  V 
=
290  V /10 
T2 = (10 ) × 290
0.4

= 2.51 × 290
T2 = 727.9° K (or ) 455 K
(iv) Calculate the work done in if one mole of an ideal gas expands isothermally at 127°C to double
its original volume, given R = 8.314 J/m/K.
Work done in isothermal expansion process:
V  V1 = V
W = 2.303 nRT log  2 
 V1 
V2 = 2V
= 2.303 × 8.314 log10 (2)
n = 1 mole
= 2310 J
log10 (2) = 0.301
(v) Calculate the work done when a gram mole of a perfect gas expands isothermally at 27°C to
double its original volume [R = 8.314 JK−1mole−1]
V  T1 = 27°C
W = 2.303 × nRT log  2 
 V1  = 27 + 273
 2V  = 300 K
= 2.303 × 8.314 × 300 × log  
V  V2 = 2V
= 2.303 × 8.314 × 300 × log10 (2) n =1
W = 1730 J log 2 = 0.301


(vi) Two moles of oxygen (O2) at 0°C are compressed until the volume becomes one-fourth of the
volume at the same temperature. Calculate the work done.
 V /4 
W = 2.303 × 2 × 8.314 × 273 × log  n=2
 V 
T = 273 K
 1
2.303 × 2 × 8.314 × 273 × log   R = 8.314 J
 4
V1 = V
W = − 6294.13 Joules
V
V2 =
4
‘–‘denotes compression
(vii) Deduce the change in the boiling point of water when the pressure changes by 1 cm of Hg. Given
L = 2.268 × 105 J/kg, V1 = 10-3 m3/kg, V2 = 1.674 m3/kg
According to Clausius–Clapeyron, the change in boiling point of water is
dP L
=
dT T (V2 − V1 )
dP × T (V2 − V1 ) am = b n
dT =
L b = mn a
dT = 1K b = am / n
(viii) A tyre pumped to a pressure of 3 atm bursts suddenly. Calculate the fall in temperature due to
adiabatic expansion. The temperature of air before expansion is 27°C and r = 1.4.
P11− r T1r = P21− r T2 r

1− r
 P
T2 r = T1r  
 P2 
P1 = 3 atm
= (300 ) (3)1−1.4
1.4
P2 = 1 atm
−0.4
T21.4 = (300 ) (3) [after burst atmosphere]
1.4
T = 27°C
T2 = (300 )(3)
−0.4 /1.4
1
= 300 K
= (300 )(3)
−0.28
r = 1.4
300 300
T2 = 0.28 = = 220° K T2 = ?
3 1.36
Fall :T1 − T2
= 300 − 220 = 80° K
(a) Entropy
The thermal property of a body which remains constant during an adiabatic process is called
entropy; it remains constant between two adiabatic lines. The entropy denoted by S.
The entropy value is not estimated at a particular point of process. It is calculated between any
two points on adiabatic lines (Figure 11.11).

11.24
L M
A B T1
Q1 C T2
D
Q2 F T3
P E
Q3 G
H T4
Q4
Figure 11.11 Calculation of entropy value
dQ
Change of entropy generally expressed as dS =
T
where dQ is the change in heat energy at the temperature (T) between the two points which are
much closed to each other; thus the total entropy can be written as
dQ
∫ dS = ∫ T
dQ
dS =
T
Explanation
Let a Carnot engine be at working between the temperature T1 and T2 as the Carnot’s cycle of ABCDA.
W
∴ Efficiency n =
Q1
Q1 − Q2 T1 − T2
= =
Q1 T1
Q T
= 1− 2 = 1− 2
Q1 T1

Q2 T2
=
Q1 T1
Q Q2 (1)
⇒ 1 =
T1 T2
If the Carnot engine is working between the temperature T2 and T3 from Carnot cycle of DCEFD,
∴ Efficiency of Carnot engine
Q2 − Q3 T2 − T3
n= =
Q2 T2
Q3 T3
1− = 1−
Q2 T2

Q3 T3
=
Q2 T2
Q3 Q
= 2 (2)
T3 T2

By the Carnot engine’s working, temperature T3 and T4 be:
Q3 Q4
= (3)
T3 T4
Q1 Q2 Q3 Q4
Form equations (1), (2) and (3), we have = = = ...
T1 T2 T3 T4
Q
∴ = constant
T
Q
The quantity of which remains constant between the two adiabatic lines L and M is called
T
entropy.
Q
∴S =
T
(b) Entropy disorder
According to Boltzmann’s theory, the disorder of a material increases from solid to liquid and liquid
to gasses. The disorder of gasses is maximum and the disorder of the solid is minimum. As a result the
change of entropy is maximum for gasses and the change of entropy is minimum for solids.
Hence, entropy is directly proportional to the disorder.
Calculation of entropy
Change in entropy for a reversible process is shown in Figure 11.12.
A Q1
B
D C
Q2
Figure 11.12 Calculation of entropy
Consider a reversible process in the Carnot cycle ABCDA; working with two adiabatic processes
and two isothermal processes, this adiabatic process is shown in the indicator diagram.
Let the total change in entropy reversible process be S.
Total change in entropy = sum of change in entropy of all process Q.
d = d 1 + d 2 + d 3 + d 4 (1)
Here, d 1 is the change in entropy of the system. The state is isothermal and expanded from A to B
with a transformation of heat energy Q1.
Q1
∴ d1 =
T1
d 2 is the change of entropy of the system. This state is adiabatically expanded from B to C without
transformation of heat energy.

11.26
0
∴ d2 = = 0
T1
d 3 is the change of entropy of the system whose isothermal expansion lies between C and D with
transformation of heat energy Q2.
−Q2
∴ d3 =  − ve heat rejected 
T2 
d 4 is the change of entropy of the system whose state is adiabatic contraction between D to A
without transformation of heat energy
0
∴ d4 = =0
T2
All these values are substitute in equation (1)
Q1 Q
d = + 0 − 2 + 0 (2)
T1 T2
Q1 − Q2
From the efficiency of the reversible process, n =
Q1
Q
Entropy change in isothermal expansion dS1 = 1 (positive heat Q2 T
T1 = 1− = 1− 2
observed) Q1 T1
Entropy change in adiabatic expansion dS2 = 0 (entropy constant) Q2 T2
⇒ =
Q Q1 T1
Entropy change in isothermal compression dS3 = 2 (negative (3)
T2 Q1 Q2
heat observed) =
T1 T2
Entropy change in adiabatic compression dS4 = 0
Substitute equation (3) in equation (2) and we get the change of entropy in the reversible process:
Q2 Q2
d =− =0 d = dS
T2 T2
∴d =0 d 1 = dS1
(c) Change in entropy for irreversible process

From the efficiency of irreversible process
Q1 − Q2
h=
Q1
Q T
h = 1 − 2 <1 − 2
Q1 T1

Higher temperature to a body at a lower Q2 T2 Q

< ⇒ 2 ∴ Net increase in entropy
temperature. Consider two bodies A and Q1 T1 T2
B at temperature T1 and T2, respectively Q Q
Q2 T2 Q2 ds = −
Let T1 > T2 < ⇒ T2 T1
Q1 T1 T2
So heat function decrease in entropy of  1 1
Q Q Q = Q − 
A= ⇒ 1> 2 (3)  T2 T1 
T1 T1 T2
Q Is +ve
increase B =
T2

Substitute equation (3) in equation (2) we get the change of entropy in irreversible process
Q1 Q2
d = −
T1 T2
⇒ d = + ve
∴ The change of entropy in irreversible process is positive

(d) Change of entropy of the universe
The change of entropy for reversible process is zero and the irreversible process is positive. However,
in the universe, all the processes are irreversible.
∴ The change of the entropy of the universe should increase with the time.
Let a reversible process in the universe which initially the heat energy Q1 from the source at the
temperature to available of energy in the universe which as reversible process equal to Q1 – Q2.
 Q 
Q1 − Q2 = Q1 1 − 2 
 Q1 
 T 
Q1 − Q2 = Q1 1 − 2 
 T1 
 T 
Available dE = Q1 1 − 2  ∴dE = Q1 − Q2 
 T1 
(The available energy of the universe becomes the maximum as the sink temperatures
becomes T0.)
The maximum available energy at the initial state of the universe is
 T 
Q1 = Q 1 − 0 
 T1 
The maximum available energy at the final state of the universe is
 T 
Q2 = Q 1 − 0 
 T2 
∴ The net available energy dE = Q1 – Q2

11.28
 T   T 
dE = Q 1 − 0  − Q 1 − 0 
 T1   T2 
QT QT
= Q− 0 −Q+ 0
T1 T2
Q Q
dE = T0  − 
 T2 T1 
dE = T0 dS
Here, dS is the change of entropy of the universe. In the universe, the number of irreversible processes
increase and the available energy decreases; so the entropy of the universe increases with the time.
(e) Entropy–temperature diagram
The curves formed by the variation of temperature with the entropy of the system known as T-S
diagram. In the T-S diagram, the change in entropy of the system is taken on the X-axis and the tem-
perature of the system is taken on the Y-axis as shown in Figure 11.13. It is similar to indicator or P-V
diagram.
y y Q1
A Q1 T1 A B
B
W3 W1 W3
W2
D C
P T T D
2 C
Q2
Q2
O E H F G x F E
V S1 S S2
Figure 11.13 Entropy–temperature diagram
In an isothermal process, the temperature is constant but entropy can change. In adiabatic process,
entropy is constant.
W
The efficiency of Carnot engine n =
Q1
Q1 − Q2
n= (1)
Q1
Let a system undergo the change of state isothermally from A→ B. In this process, the change of
entropy is
Q
dS = 1
T1
Q1 = T1dS
From the graph, the change of entropy dS = S2 – S1
∴ Q1 = T1 ( S2 − S1 ) (2)
⇒ Q1 = ABEF (area ) (3)

The system undergoes adiabatic process from B to C with the change of temperature T1 → T2.

∴ Change of entropy = 0
The system undergoes a change from C to D in the isothermal process.
Q
Change of entropy dS = 2
T2
Q2 = T2 dS
From the graph, change of entropy is dS = S2 – S1
⇒ Q2 = T2 ( S2 − S1 ) (4)
Q2 = CDEF (area) (5)

Substitute equation (2) and (4) in equation (1), we get
Q − Q2
h= 1
Q1
T1 ( S2 − S1 ) − T2 ( S2 − S1 )
=
T1 ( S2 − S1 )
(T1 − T2 ) ( S2 − S1 )
=
T1 ( S2 − S1 )
T1 − T2
h=
T1
T2
h = 1−
T1
Substitute equation (3) and (5) in equation (1) we get
ABEF area − CDEF area
h=
ABEF area
ABCD area AD
h= =
ABEF area AF
BE − CB
h=
BEE
T1 − T2 T
h= ⇒ n = 1− 2
T1 T1
Substitute equation (3) and equation (5) in equation (1)
ABEF area − CDEF area
h=
ABEF area
ABCD area AB × BC BC
h= = =
ABEF area AB × BE BE
BE − CE T1 − T2
h= =
BE T1
T2
⇒ h = 1−
T1

11.30
Boyle’s law is valid for isothermal process.

PV = RT (for 1 mole of gas)
(f) Adiabatic process or adiabatic change
When a thermodynamic process occurs in such a way that no change of heat takes places a system and
surroundings, the process is known as adiabatic process. In other words, there is change in temperature
in an adiabatic process.
Example:
Boyle’s law is not valid for adiabatic process.
∴ For an adiabatic process
PV r = Constant
TV r −1 = Constant
p1− r T r = Constant
Adiabatic relations between P, V, T of ideal gas or we show that PVr = constant:
Consider 1 mole of an ideal gas enclosed
Let its thermodynamic coordinates be P, V, T
If the gas under goes adiabatic expansion, work done by the gas dW = PdV
Decrease in internal energy dU = CvdT
∴ From the first law of thermodynamics
dQ = dU +dW
dQ = CvdT + PdV
For an adiabatic process, dQ = 0
0 = CvdT + PdV
CvdT = −PdV(1)
For 1 mole of ideal gas,
PV = RT
RT
P = (2)
V
Substitute equation (2) in equation (1)
− RT
Cv dT = dV
V
Cv dT dV
= −R [∵C p − Cv = R]
T V
Cv dT dV
= −[C p − Cv ]
T V
dT  C p  dV
= − − 1
T  Cv  V
dV
= − ( r − 1)
V
On integration,
T2 V
dT 2
dV
∫ = − ( r − 1) ∫
T1
T V
V
1

T  V 
log  2  = − ( r − 1) log  2 
 T1   V1 
r −1
T  V 
log  2  = log  1 
 T1   V2 
r −1
T2  V1 
=
T1  V2 
r −1
TV
1 1 = T2V2r −1
TV r −1 = Constant (1)
PV
We know that PV = RT ⇒ T =
R
 PV  r −1
 R  V = constant
PV r −1+1
= constant ⇒ PV r = constant (2)
R
RT
We know that PV = RT ⇒ V =
P
r
 RT 
P = constant
 P 
P1− r T r = constant (3)
Equations (1), (2) and (3) are known as adiabatic relations.
(g) Coefficient of performance of a refrigerator
The coefficient of performance of a refrigerator is defined as the ratio of heat taken from sink to the
work needed to run the refrigerator (Figure 11.14).
Source
W = Q1 − Q2 Q1
Q2
Sink
Figure 11.14 Coefficient of performance of a refrigerator

Q Q2 Q
The coefficient of performance K = 2 = = 2 −1
W Q1 − Q2 Q1
1
K=
Q1
−1
Q2
Q1 T1 1 T2
But = ⇒K= ⇒K=
Q2 T2 T1 T1 − T2
−1
T2

11.32
(h) Relationship between the efficiency (n) of a Carnot heat engine and the efficient of perfor-
mance (K) of a refrigerator
Consider a Carnot heat engine’s efficiency is ‘n’ and a Carnot refrigerator’s coefficient of performance
as ‘K’. The working between temperature T1 and T2 is as follows:
T2 T T −T
We know that K= and n = 1 − 2 (or ) 1 2
T1 − T2 T1 T1
T2 1 T1
K +1 = +1 =
T1 − T2 n T1 − T2
T +T −T
⇒ 2 1 2
T1 − T2
T1
⇒
T1 − T2
T1
=
T1 − T2
1 1
K + 1 = (or) n =
n k +1
This is the relation between n and K.
(i) Calculation of change in entropy when ice converted into steam
The process of conversion of m gram of ice at T1°K into steam at T2°K involves three processes.
(1) First, ‘m’ gram of ice converts into water; this is a phase change process occurring at constant
temperature T1.
Heat absorbed during the process dQ = mL1
L1 = Latent heat of fusion
Latent heat of fusion
Change in entropy =
Temperature
mL1  dQ 
∴ Change in entropy dS1 = ∵dS = T 
T1
(2) Second, ‘m’ gram of water at T1°K converts into water at T2°K
Heat absorbed for dT change in temperature = mcdT
where ‘C’ specific heat of water
mcdT
∴ Change in entropy for dT change =
T
T2
mcdT
Change in entropy in entire process dS q = ∫
T1
T
T2
mcdT T 
dS2 = ∫
T1
T
= mc log  2 
 T1 
(3) Finally, ‘m’ gram of water at T2°K is converted into steam at T2°K. This is also a phase at which
the process occurs at constant temperature, T2.
Heat observed during the process dQ = mL2
L2 = Latent heat at vapourisation
mL2
Change in entropy dS3 =
T2

∴ Total change in entropy when ice converts into stream

mL1 T mL2
dS = + mc log 2 +
T1 T1 T2
Solved Numerical Problems Based on Entropy
(i) Find the increase in entropy when 10 g of ice at 0°C is converted into water at the same tempera-
ture given latent heat of fusion of ice = 80 cal/g.
0°C ice −0°C water (phase change)
ML
Change in entropy dS =
T
10 × 80 m = log
= = 2.93 Cal/K
273
L = 80 Cal/g
= 2.93 × 4.2 J/ °K
T = 0°C = 273K
= 12.3 J/ °K
dS = ?
Differences between isothermal and adiabatic processes

Isothermal process Adiabatic process
1. When a thermodynamic system undergoes a physi- 1. When a thermodynamic system undergoes a change
cal change in such way that its temperature remains in such that no exchange of heat takes place between
constant is called isothermal process. it and its surroundings is called an adiabatic process.
2. Exchange of heat takes place between system and 2. No exchange of heat between the system and sur-
surroundings roundings
3. Work done 3. Work done
V  R
W = 2.303RT log10  2 
 V1 
W= [T − T ]
1− r 2 1
4. It obey’s Boyle’s law 4. It does not obey’s Boyle’s law
5. PV = Constant 5. PV r = Constant
11.5 THERMODYNAMIC POTENTIALS AND MAXWELL EQUATIONS
11.5.1 Thermodynamic Potential

The thermo function which gives the energy of thermodynamics systems as defined in P, T, V and S is
called thermodynamic potentials. There are four thermodynamic potentials which represent the energy
of the systems.
These are as follows:
(i) Internal energy (U)
(ii) Helmholtz function (F)
(iii) Total heat energy or Enthalpy (H)
(iv) Gibb’s function or Gibb’s free energy (G)
11.5.2 Internal Energy (U)

It is the thermodynamics potential of the system which represents its total internal energy. The change
in internal energy of the system is derived as follows.

11.34
From first law of thermodynamics,

dQ = dU + dW
dU = dQ – dW
From the second law of thermodynamics, dQ = TdS
External work done: dW = PdV
∴ dU = TdS – PdV(1)
Now equation (1) can be partially differentiated with respect to variables S and V
 ∂U 
 ∂S  = T
V
 ∂U 
 ∂V  = − P
S
Equation (1) can be written as perfect differentiation

∂  ∂U  ∂  ∂U 
=
∂V  ∂S  V ∂S  ∂V  S
 ∂T   ∂( − P ) 
 ∂V  =  ∂S 
S V
 ∂T   ∂P 
 ∂V  = −  ∂S 
S V
This is the first Maxwell thermodynamics equation.

Comparing this equation with dZ = MdX = NdY
M = T, N = −P, X = S, Y = V (dU = TdS - PdV)
∴ This condition for exactness is given by
 ∂M   ∂N 
 ∂Y  =  ∂X 
X Y
 ∂T   ∂P 
 ∂V  = −  ∂S 
S V
11.5.3 Total Heat Function (H)

It is the thermodynamics potential of the system which represents about the total heat energy of the
system. The total heat energy of the system is equal to the sum of internal heat energy and external
energy. Thus, the enthalpy can be written as
Enthalpy H = U + PV
Differentiate the equation
dH = dU + PdV + VdP
dH = TdS − PdV + PdV + VdP

dH = TdS + VdP (2)

Equation (2) is the form of exact differential equation and hence it can be partially differentiated
with respect to P and S.
 ∂H 
 ∂S  = T
P
 ∂H 
 ∂P  = V
S
Equation (2) can be written as exact differential equation as

∂  ∂H  ∂  ∂H 
=
∂S  ∂P  S ∂P  ∂S  P
 ∂V   ∂T 
 ∂S  =  ∂P 
P S
This is the Maxwell third equation.
Comparing this equation with dZ = MdX + NdY
dH = TdS + VdP
M = T; N = V
X = S, Y = P
 ∂M   ∂N 
 ∂Y  =  ∂X 
X Y
 ∂T   ∂V 
 ∂P  =  ∂S 
S P
11.5.4 Helmholtz Function (F)

It is the thermodynamic potential of the system which uses the internal energy of the system of con-
stant temperature. The Helmholtz function in terms of P, V, T and S is derived as follows.
According to the first and second laws of thermodynamics, the equation of change in internal
energy is as follows:
dU = TdS - PdV
If T = constant, TdS = d(TS)
⇒ dU = d(TS) - PdV
dU - d(TS) = -PdV
d(U - TS) = -PdV
dF = -PdV
Here, U – TS = F is called the Helmholtz function; differentiate the above function.
⇒ dF = d(U - TS)
dU - d(TS)
= dU - SdT - TdS
= TdS - PdV - SdT - TdS
dF = -PdV - SdT(2)
Equation (2) is the form of the exact differential form hence it can be partially differentiated as
with respect to V and T.

11.36
 ∂F 
 ∂V  = −P
T
 ∂F 
 ∂T  = −S
V
Equation (2) can be written as perfect differential equation.

∂  ∂F  ∂  ∂F 
=
∂V  ∂T  V ∂T  ∂V  T
 ∂S   ∂ 
⇒  ∂V  =  ∂T ( − P )
T V
 ∂S   ∂P 
⇒ −  = − 
 ∂V  T  ∂T  V
 ∂S   ∂P 
⇒  ∂V  =  ∂T 
T V
This equation is the Maxwell second equation.
11.5.5 Gibb’s Free Energy or Gibb’s Function (G)

It is the T.D potential of the system which gives the total heat of the system at constant temperature
and pressure.
Gibb’s function is mathematically defined as follows:
G = H – TS on differentiation
dG = dH – TdS – SdT
dH = TdS + VdP
dH = d(TS) + VdP
dH – d(TS) = VdP
d[H – TS] = VdP
H – TS = G
∴ H – TS called Gibb’s function
G = H – TS
Differentiate the above Gibb’s function
dG = d(H - TS)
dG = dH - d(TS)
dG = dH - TdS - SdT
dG = TdS + VdP - TdS - SdT [∵dH = TdS + VdP]
dG = VdP - SdT (4)
Equation (4) is the form of exact differential equation and hence it can be partially differentiated with
respect to P, T.
 ∂G 
 ∂P  = V
T
 ∂G 
 ∂T  = − S
P

Equation (4) can be written as an exact differential equation.

∂  ∂G  ∂  ∂G 
=
∂T  ∂p  T ∂P  ∂T  P
 ∂   ∂ 
 ∂T (V ) =  ∂P ( − S )
P T
 ∂V   ∂S 
 ∂T  = −  ∂P  (5)
P T
 ∂S   ∂V 
or  ∂P  = −  ∂T 
T P
This is called Maxwell’s fourth equation.
11.5.6 Maxwell’s Equations

 ∂T   ∂P 
 ∂V  = −  ∂S  (1) Internal energy
S V
 ∂T   ∂V 
 ∂p  =  ∂S  (3) Total heat function or enthalpy
S p
 ∂S   ∂P 
 ∂V  =  ∂T  (2) Helmoheltz function
T V
 ∂S   ∂V 
 ∂p  = −  ∂T  (4) Gibb’s function
T p
Maxwell’s First Equation

(i) dU = TdS - PdV(1)
Equation (1) can be written as dZ = Mdx + Ndy
M → T ; x → S
N → −P; y → V
 ∂M   ∂N 
 ∂Y  =  ∂X  (1)
x y
 ∂T   ∂P 
From (1),   = −  Maxwell’s first equation
 ∂ V S  ∂S  V

(ii) dH = TdS + VdP can be written as dZ = Mdx + Ndy
M → T N→V
x → S y→P
H = U + PV
 ∂T   ∂V 
From (1) ⇒   =  Maxwell’s third equation
 ∂P  S  ∂S  P

11.38
(iii) dF = −SdT - PdV this equation can be written as dz = Mdx + Ndy

M → −S N = −P
x → T y = V
F = U − TS
 ∂S   ∂P 
From (1) ⇒  = Maxwell’s second equation
 ∂V  T  ∂T  V
(iv) dG = −SdT + VdP, this equation can be written as G = H − TS

dz = Mdx + Ndy
M → −S N→V
x → T y → P
 ∂S   ∂V 
From (1) ⇒ −   =  this is Maxwell’s fourth equation.
 ∂P  T  ∂T  P
Specific Heat (C)

The quantity of heat required to raise the temperature of one gram of a substance through 1°C is known
as specific heat.
1 ∂Q
∴ C=
m ∂T
For gases, there are two types of specific heat:
(i) Specific heat at constant pressure (CP):
At constant pressure, the amount of heat required to raise the temperature of a gas at unit mass
through 1°C is known as specific heat at constant pressure.
1  ∂Q 
CP =
m  ∂T  P
(ii) Specific heat at constant volume (CV):
At constant volume, the amount of heat required to raise the temperature of a gas at unit mass
through 1°C is known as specific heat of constant volume.
1  ∂Q 
CV = 
m  ∂T  V
11.5.7 Clausius–Clapeyron Equation

Clausius–Clapeyron’s latent heat equation relates the change in melting and boiling point with change
in pressure.
From Maxwell’s second equation,
 ∂P   ∂S 
 ∂T  =  ∂V 
V T
Multiplying both sides with ‘T’
 ∂P   ∂S 
T  = T 
 ∂T  V  ∂V  T
TdS = dQ
∂P ∂Q
T = (1)
∂T ∂V

Now, assume that the unit mass of a substance undergoes a phase change (from solid to liquid or gas),
the heat observed at constant temperature is given by
∂Q = L, where L = Latent heat
Let V1, V2 be the specific volumes in first state and second state respectively. (Specific volume = volume
per unit mass)
∂P L
∵ T ∂T = V − V (∂V = V2 − V1)
2 1
∂P L
=
∂T
T (V2 − V1 )
which is the latent heat of Clausius–Clapeyron.
Use
Clausius–Clapeyron is used to study the change in melting and boiling point with change in pressure.
Relation between CP and C V

Derivation of CP – C V = R
 ∂Q 
At constant pressure, specific heat is CP =  and (1)
 ∂T  P
 ∂Q 
At constant volume, specific heat is CV =  (2)
 ∂T  V
 ∂Q   ∂Q 
∴ CP – CV =  −
 ∂T  P  ∂T 
V
Clausius equation dQ = TdS
 ∂Q   ∂S 
∴  = T   and
 ∂T  P  ∂T  P
 ∂Q   ∂S 
 =T 
 ∂T  V  ∂T  V
  ∂S   ∂S  
∴ CP – CV = T   −    (3)
  ∂ T  P
 ∂T  V 
If the change in entropy at system is assumed as a function in terms of T, V,
 ∂S   ∂S 
dS =   dT +  dV
∂
 VT  ∂V  T
The above equation divided by ∂T.
 ∂S   ∂S   ∂S   ∂V 
 ∂T  =  ∂T  +  ∂V   ∂T 
P V T
Multiply with T, on both sides
 ∂S   ∂S   ∂S   ∂V 
T  = T   + T 
 ∂T  P  ∂T  V  ∂V  T  ∂T 

11.40
  ∂S   ∂V  
CP = CV + T    
  ∂V  T  ∂T  
  ∂S   ∂V  
CP – CV = T    ∂T  
  ∂V  T 
Ideal gas equation PV = RT
PdV = RdT PV = RT
dV VdP = RdT
= R/P
dT R
dP/dT =
V
 ∂s   ∂P 
From the second equation,   = 
 ∂V  T  ∂T  V
 ∂P   ∂V 
CP – CV = T ⋅   
 ∂T  V  ∂T 
R R
=T⋅ ⋅
V P
R2 R2
=T⋅ =T
PV RT
CP – CV = R
11.5.8 Derivation of the Stefan–Boltzmann Law using Maxwell’s Equations

According to Stefan’s law, the total radiant energy E emitted per second from unit surface area of a
black body is proportional to the fourth power of its absolute temperature T.
Thus, E ∝ T 4
E =s T 4
where s is a constant called Stefan’s constant. In the Meter-Kilogram-Second (MKS) system, its value is
5.672 × 10−8J.sec−1.m−1.k−4.
Consider a block body having volume V, total internal energy U and energy density as E, then
U
internal energy of the system can be written as U = EV ⇒ E = .
V
From the first law of thermodynamics, dQ = dU + dW
From the second law of thermodynamics, dQ = TdS
From Maxwell’s (2) equation
 ∂S   ∂P 
 ∂V  =  ∂T  (1)
T V
dU = TdS – PdV(2)
TdS = dU + PdV
1
dS = [dU + PdV]
T

or
1
∂S =
T
[∂U + PdV ](3)
Substitute equation (2) in equation (3):
1   ∂U    ∂P 

T  ∂V  + P  =  ∂T  (4)
 T  V
(1) According to Maxwell’s electromagnetic theory, the black body radiation in an enclosure
exerts a pressure P on the walls which is equal to one third of energy density E.
E
Thus P = (5)
3
 ∂p  1  ∂E 
⇒
 ∂T  = 3  ∂T 
V V
(2) If V is the volume of the enclosure and E is the energy density of variation, total internal
energy U is expressed as follows:
U = EV
dU = EdV
dU
= E (6)
dV
1   ∂U    ∂P 
(4) ⇒  ∂V  + P  =  ∂T 
T  T  V
 ∂U   ∂P 
 ∂V  = T  ∂T  – P (7)
T V
Equations (5) and (6) are substituted in equation (7).

1  ∂E   ∂P  1  ∂E 
E = T ∙ − P  ∂T  = 3  ∂T 
3  ∂T  V V V
1  ∂E  − E
E=T⋅  
3  ∂T V 3
E T  ∂E  − E
E+ =  
3 3  ∂T V 3
4 E T  ∂E 
⇒ 3 = 3  ∂T  4loge T + logee = logeE
 V
4 E T  ∂E  4 4
⇒ 3 = 3  ∂T  log eT + loge C = logeE ⇒ log e CT = logeE

 V
dT dE
⇒ 4 T = E E = CT4 ⇒ E = s T4

11.42
Integrating on both sides: Here s is the Stefan’s constant

4dT dE
∫ T = ∫ E This is Stefan’s constant.
4 logT4 + logs = log E

log s T4 = log E
E = s T 4
For perfect gas
CP – CV = R
For van der Waals gas:
 a
For van der Waals gas  p + 2  (v − b ) = RT (1)
 v 
 a RT
Where a and b are constants  p + 2  = v − b (2)
v
Differentiating with respect to T at constants ∴ CP – CV =
R ( R /v − b )
Volume: T × ×
V −b   2a  
 RT /(V − b) −  3  
2
 v 
 ∂P  R R
 ∂T  = (v − b) (3) =
 2a  ( v − b)
2
V
1−  3 
 v  RT
Differentiating with respect to ‘T’ at constant pressure since v << b, replace (v – b) by v,
−2a  ∂v  − RT  ∂V  R R R
3 
 ∂ T  = 2 
 ∂ T  + v − b C P − CV = =
2a

v (V − B )  2a  V
2
1−
P P
1−  3  RVT
 V  RT
−1
 ∂v   RT 2a  R  2a   2a 
 ∂T   − 3= = R 1 −  = R 1 + 
P  (V − b)
2
V  v − b  RVT   RVT
R
 ∂v  v − b  2a 
∴  = (4) CP – CV = R 1 +
 ∂T  P  RT 2a   RVT 
−
 (V − b)2 V 3 
 
From equations (3) and (4),
 ∂P   ∂V 
CP – CV = T   
 ∂T  V  ∂T  P
CP
=g
CV
The coefficient of volume elasticity E is defined as
stress −dp
E = strain = dv
v

dp
⇒ E = –V
dv
 ∂p 
Elastic modulus of at constant entropy ES = –V   (1)
 ∂v  S
 ∂P 
Elastic modulus at constant temp ET = –V  (2)
 ∂V  T
 ∂P   ∂P 
−V    ∂V 
(1) ES  ∂ V
= S
= S
(2) ET  ∂P   ∂P 
−V 
 ∂V  T  ∂V  T
3rd
 ∂P   ∂P   ∂T 
 ∂V   ∂T   ∂V 
S
= S S
 ∂P   ∂P   ∂S 
 ∂V   ∂S   ∂V 
T T T
By using Maxwell’s equations, we get
}
 ∂T   ∂V   ∂T   ∂V 
  =   ∂P  =  ∂S 
 ∂P  S  ∂S  P S P

Maxwell second equation
 ∂P   ∂S   ∂P   ∂S 
 ∂T  =  ∂V  ⇒  =
 ∂T  S  ∂V  P
Maxwell third equation
S P
 ∂P   ∂T 
    ∂T   ∂P 
ES  ∂ T  S  ∂ V  S  = −  Maxwell first equation
=
ET  ∂P   ∂S   ∂V  S  ∂S  V
 ∂S   ∂V 
T T
 ∂S   ∂P 
  ⋅− 
ES  ∂ V  p  ∂ S  V
=
ET  ∂T   ∂P 
−
 ∂V  P  ∂T  V
 ∂S   ∂P 
ES  ∂ V   ∂S   ∂S   ∂V   ∂P   ∂T 
=  ∂P  = −  ∂T  ⇒  ∂S  = −  ∂V  Maxwell fourth equation
ET  ∂T   ∂P 
    T P T P
∂V p ∂T  V

11.44
 ∂S   ∂T   ∂S   ∂P  nd
⇒    From 2nd  = 2
 ∂T  P  ∂S  V  ∂V  T  ∂T  V
 ∂S 
 ∂T 
⇒ P
 ∂S 
 ∂T   ∂S   ∂Q 
T 
V  ∂T  P  ∂T  P  ∂Q 
Multiplying numerator and denominator with T, we get = ∴  = CP &
 ∂S   ∂Q   ∂T  P
 ∂Q  T  ∂T   ∂T 
 ∂T  = CV V V
V
ES C P
⇒ =
ET CV
ES
We know that =r
ET
CP
= =r
CV
The ratio of specific heat of the substance at constant pressure and at constant volume is equal to
the ratio of adiabatic and isothermal electricity.
11.5.9 Joule–Thomson Effect or Joule–Kelvin Effect

The phenomena of cooling of gas allowing through the porous plug from high pressure region to low
pressure region at any point of temperature is called the Joule–Thomson effect.
Explanation
Let some amount of the gas on the system pass through the porous plug; enthalpy remains constant.
∴ Enthalpy H = U + PV
Differentiate the function,
dH = dU + PdV + VdP
Here, enthalpy is constant dH = 0
dU + PdV + VdP = 0 (1)
According to second law of thermodynamics, dQ = TdS
According to first law of thermodynamics, dQ = dU + dW
dU + PdV
= (2)
TdS
From equations (1) and (2), we get TdS + VdP = 0 (3)
Let the thermodynamical system whole entropy be a function in terms of temperature and pressure.

∴ The change of entropy can be written as

 ∂S   ∂S 
T   ∂T + T   ∂P + VdP
 ∂T  P  ∂P  T
 ∂S   ∂S 
⇒ T   ∂T + T   ∂P + VdP = 0(4)
∂
 PT  ∂P  T
 ∂S   ∂V 
According to Maxwell’s fourth equation   = − 
 ∂P  T  ∂T  P
Equation (4) can be written as
 ∂S   ∂V 
T   dT − T  dP + VdP = 0
 ∂T  P  ∂T 
or
 ∂Q   ∂V 
 ∂T  dT − T  ∂T  dP + VdP = 0
P P
or
  ∂V  
C P dT − T   − V  dP
  ∂ T P 
or
  ∂V  
C P dT = T   − V  dP = 0
  ∂ T P 
or
 ∂T  1   ∂V  
 ∂P  = C T  ∂T  − V (5)
H P  P 
The above equation is called differential Joule–Thomson or the Joule–Kelvin effect.
 ∂T 
 ∂P  > 0 Positive Joule–Kelvin effect when the cooling effect is observed
H
 ∂T 
 ∂P  < 0 Negative Joule–Thomson effect when the heating effect is observed.
H
 ∂T 
 ∂P  = 0 Joule–Thomson effect where neither cooling nor heating effects are observed.
H
Case I
Joule–Kelvin effect for perfect gas or ideal gas
The ideal gas equation PV = nRT
PV = RT
 ∂V  R
 ∂T  = P (1)
P

11.46
 ∂T  1   ∂V  
 ∂P  = C T  ∂T  − V (2)
H P  P 
1   R 
(1) in (2) = T −V 
C P   P  
1  PV 
=  P − V  = 0
CP
 ∂T 
 ∂P  = 0
H
In case of perfect gas, the Joule–Kelvin effect is zero.

∴ In the Joule–Kelvin expansion for ideal gas, there is no change in heating, cooling and no
change in temperature.
Case II
Joule–Kelvin effect for van der Waals’ gas
Let one gram mole of gas of the state of gas equation be
 a
 P + 2  (V − b) = RT (1)
V
At constant pressure, differentiate the equation (1) with respect to temperature:
 a   ∂V   2 a  ∂V  
 P + 2   ∂T  + (V − b)  − 3  ∂T   = R
V P  V P
 ∂V   a 2a(V − b) 
 ∂T   P + V 2 − V3  = R(2)
P
Equation (2) in (1):
 ∂V   RT 2a(V − b) 
 ∂T  V − b −  = R
P  V3
 ∂V  R
⇒  ∂T  = RT 2 a(V − b)
P −
V −b V3
Multiplying ‘T’ on both sides
 ∂V  RT
⇒  ∂T  T = RT (V − b)
P − 2a
V −b V3
 ∂V  1
⇒ T =
 ∂T  P 1 2a(V − b)
−
V −b RTV 3

(V − b) Multiply N and D
 ∂V  V −b
T =
 ∂T  P 2a(V − b)2
1−
RTV 3
Now V >> b
Here, b2 and 2b are neglected.
 ∂V  V −b
⇒ T =
 ∂T  P 1 − 2aV 2
RTV 3
 ∂V  V −b
T  =
 ∂T  P 2a
1−
RTV
−1
 ∂V   2a 
⇒ T = V − b 1 −
 ∂T  P  RTV 
According to binomial theorem,
(1 − x ) −1 = 1 + x + x 2 + x 3 + − − −
 ∂V   2a 
⇒ T = (V − b)  (1 +
 ∂T  P  RTV 
 ∂V  2aV 2ab
⇒ T = (V − b) + −
 ∂T  P RTV RTV
 ∂V  2a 2ab  2ab 
⇒ T
 ∂T  P
− V = −b + −
RT RTV
∵ RTV = 0 
 ∂V  2a
⇒ T  −V = − b
 ∂T  P RT
Equation (4)
 ∂T  1  2a 
⇒  ∂P  = C  RT − b
H p
 ∂V  2a 2ab
⇒ T − V = −b + −
 ∂T  P RT RTV
 ∂T 
1. S = −  
 ∂P  V
Solution
F = U − TS
∴ dF = dU − TdS − SdT
∴ dF = TdS − PdV − TdS − SdT
= −PdV − SdT

11.48
At constant voltage, dV = 0.
dF = −SdT
 ∂F   ∂F 
∴   = − s ⇒ s = −  
 ∂T   ∂T  V
 ∂G 
2. S = − 
 ∂T  P
Solution
G = H − TS
but H = U + PV
G = U + PV − TS
∴ dG = dU + (PdV + VdP) − (TdS + SdT)
= (dU + PdV) − TdS − SdT + VdP
= TdS − TdS − SdT + VdP
= −SdT + VdP = 0
At constant pressure, dP = 0.
dG = −SdT
 ∂G   ∂G 
− = S (or) S = − 
 ∂T   ∂T  P


1. Energy in transition due to temperature difference is _____________.
[Ans.: Heat]
2. Change in enthalpy is equal to _____________ at constant pressure.
[Ans.: Heat transfer]
3. The specific heat at constant pressure is _____________ than the specific heat at constant volume.
[Ans.: Greater]
4. The difference between two specific heats is _____________.
[Ans.: Gas constant]
5. When two bodies are in thermal equilibrium, then they are at _____________ temperature.
[Ans.: Same]
6. Thermometric property in thermocouple is _____________.
[Ans.: Electro Motive Force]
7. The statement that energy can be neither created nor destroyed but only converted from one form
to another is known as _____________.
[Ans.: Law of conservation of energy]

8. Thermodynamics is the study of the effects of _____________ on a system.

[Ans.: work, heat and energy]
9. Thermodynamics can be expressed in terms of _____________ quantities.
[Ans.: temperature (T), internal energy (U), entropy (S) and heat (Q)]
10. The first law of thermodynamics is an extension of the _____________.
[Ans.: Law of conservation of energy]
11. The change in _____________ of a system is equal to the heat added to the system minus the
work done by the system.
[Ans.: Internal energy]

1. A cycle consisting of one constant pressure, one constant volume and two isentropic processes
is known as
(a) Carnot cycle (b) Stirling cycle
(c) Otto cycle (d) Diesel cycle
[Ans.: d]
2. Which of the following is an extensive property of a thermodynamic system?
(a) Pressure (b) Volume
(c) Temperature (d) Density
[Ans.: b]
3. Which of the following is an intensive property of a thermodynamic system?
(a) Energy (b) Volume
(c) Temperature (d) Enthalpy
[Ans.: c]
4. Closed system is one in which the boundary permits the flow of
(a) Energy (b) Mass
(c) Energy and mass (d) Closed system
[Ans.: a]
5. The science of measuring temperature is
(a) Hydrometry (b) Gravimetry
(c) Volumetry (d) Thermometry
[Ans.: d]
6. Water and vapour are in equilibrium at
(a) Ice point (b) Steam point
(c) Melting point (d) Freezing point
[Ans.: b]

11.50
7. Zeroth law of thermodynamics is concerned with

(a) Internal Energy (b) Enthalpy
(c) Thermal equilibrium (d) Entropy
[Ans.: c]
8. The heat and work are mutually convertible; this statement is known as
(a) Zeroth law of thermodynamics (b) First law of thermodynamics
(c) Second law of thermodynamics (d) Third law of thermodynamics
[Ans.: b]
9. The first law of Thermodynamics is associated with
(a) Entropy (b) Internal energy
(c) Reversibility (d) Irreversibility
[Ans.: b]
10. The direction of heat flow is associated with the statement of
(a) Clausius (b) Joules
(c) Kelvin–Planck (d) Charles
[Ans.: a]
11. The efficiency of engine working on Carnot cycle depends on
(a) Working medium (b) Size of engine
(c) Temperature range (d) None of these
[Ans.: c]
12. At dead state, the available energy of a system is
(a) Zero (b) Maximum
(c) Minimum (d) None of these
[Ans.: a]
13. The process of increasing the moisture content in the air is called
(a) Sensible cooling (b) Humidification
(c) Dehumidification (d) Sensible heating
[Ans.: b]

1. Explain the terms system and surrounding.
Ans.:
System: A definite quantity of matter bounded by some enclosed surface is known as a system.
A system is also defined as that part of the universe which is under thermodynamic
study.
Examples: For a scientist, the gas enclosed in a cylinder is a system. For a mechanical
engineer, the machine is a system.

Surrounding: All the matter which can influence the behaviour of the system is known as sur-
roundings. In other words, except system, rest of the universe is surroundings.
Examples: For an egg placed on the table, the atmosphere around the egg is the surrounding.
Note: The choice of a system and its surrounding is arbitrary.
2. Define reversible and irreversible processes and give examples.
Ans.:
Reversible process: The process in which all the changes that occurred in the direct process
are repeated in the reverse direction is called reversible process. In a ther-
modynamic system, the change of the state of absorption of heat energy is
the direct process, and the system should release the same amount of heat
energy. It changes the state in the reverse direction. This type of process is
called reversible process.
For example, very slow process done at constant temperature, Carnot cycle process, etc.
A certain amount of heat is given to ice through melting and water is formed. If the same amount
of heat is removed from water, then the ice is formed.
Irreversible process: The process in which all the changes that are accepted in the direct process
were not repeated in the reverse direction is called irreversible process. All
the processes that irreversibly occur are examples of an irreversible process.
Examples: Conduction, radiation, radioactive decay, electrical heating of a wire, etc.
If an electric current is passed in the wire, heat is developed in the wire and this cannot be
reversed.
3. Differentiate between isothermal and adiabatic processes.
Ans.:
Differences between isothermal and adiabatic processes
Isothermal process Adiabatic process
1. When a thermodynamic system undergoes a 1. When a thermodynamic system undergoes a
physical change in such way that its tempera- change in such that no exchange of heat takes
ture remains constant is called isothermal place between it and its surroundings is called an
process. adiabatic process.
2. Exchange of heat takes place between system 2. No exchange of heat between the system and
and surroundings surroundings
3. Work done 3. Work done
V  R
W = 2.303RT log10  2 
 V1 
W= [T − T ]
1− r 2 1
4. It obey’s Boyle’s law 4. It does not obey’s Boyle’s law
5. PV = Constant 5. PV r = Constant
4. State first law of thermodynamics.

Ans.: The total energy of an isolated system remains constant though it may change from one
state to another. Hence, the absorbed heat of any system is equal to the sum of the increase
in internal energy and the work done by the system. According to this law, if a small
amount of heat energy (dQ) is supplied to the system, then a part of the energy is used to
increase the internal energy (dU) of the system and the remaining energy is used to do
external work by the system (dW).
The first law of thermodynamics can be written as dQ = dU + dW.

11.52
5. What do you mean by indicator diagram? What is its significance?

Ans.: A graph between pressure (P) on the Y-axis and volume (V) on the X-axis is the indicator
diagram; this diagram is also called the P–V diagram.
6. Define Carnot engine.
Ans.: A Carnot’s engine is a heat engine which can transfer heat energy from a body having
higher temperature to lower temperature while transforming the heat energy from one
body to another. In Carnot’s engine, the loss of heat energy is very minimum.
7. State the importance of second law of thermodynamics.
Ans.: The first law of thermodynamics says that heat and mechanical work is inter conversable,
but it doesn’t give any limitation and condition for this conversion. The second law of ther-
modynamics specifies the direction of the flow of heat engine.
8. What is entropy?
Ans.: The thermal property of a body which remains constant during an adiabatic process is
called entropy; it remains constant between two adiabatic lines.

Q.1 Explain the concept of internal energy of a system. Formulate first law of thermodynamics
and explain its significance.
Q.2 What are reversible and irreversible processes? How does entropy change in each of this
process?
Q.3 State and explain the second law of thermodynamics. Describe Kelvin’s scale of temperature
and give its importance.
Q.4 State and prove Carnot’s theorem. Indicate how it leads to an absolute scale of temperature.
Q.5 Describe the working of Carnot’s engine and derive an expression for its efficiency.
Q.6 Explain Kelvin–Planck and Clausius statement of the second law of thermodynamics and
their importance.
Q.7 Define and explain entropy. Write note on entropy change in reversible and irreversible
processes.
Q.8 Draw the entropy diagram for reversible Carnot cycle and show that what is the area of dia-
gram indicates.

12 METALS IN
BIOLOGICAL SYSTEM
Metal ions play essential roles in biological systems
12.1 INTRODUCTION
Metal ions have been associated with biological systems for billions of years. The metals are important
ingredients in life because some are present in enzymes, in structural features like the Ca in bones, in
transport systems like Fe in haemoglobin, in control systems like Na and K in nervous system, etc. For
instance, the divalent Mg and Ca ions play important regulatory roles in cells. The divalent metals like
Ca2+ and Mg2+ prevent cytotoxicity and in vivo antagonize Cd-induced carcinogenesis. Hence, metal
ions play crucial roles in life processes, and they are also used as inorganic drugs for curing many
diseases because of their biocompatibility.
Examples: The cisplatin (cis-[Pt(NH3)2]Cl2) is the fi rst member of a new class of protein anti-
tumour drug belonging to metal co-ordination complexes that are being introduced in medicines.
Hydroxylapatite [Ca5(PO4)3OH] is used as a substantial material for bone healing and bone grafting.
From the chemical point of view, living organisms have the following twoa types of constituents:
(i) Organic components: 90%, carbohydrates, proteins, etc.
(ii) Inorganic components: 10%, but it has vital activities than organic components.
On the basis of their utility and function in the living system, the elements can be divided into essential
and non-essential elements. Of more than 115 known elements, 29 are known to be essential for the
growth of at least one biological species and only 19 elements are essential to humans.
12.2 ESSENTIAL ELEMENTS

Essential elements have some unique chemical properties that an organism can use to its advantage and
without which it cannot survive. In other words, an essential element is one whose absence results in
abnormal biological function or development or even death, and hence, it must be required for life process.
Elements that are necessary to maintain the functions of a whole body are called essential ele-
ments. On the basis of the absolute amount present in the body, these essential elements are further
divided into bulk elements, macrominerals and micro elements (trace elements).
Essential elements in mammals play vital roles as macrominerals, as structural components (Ca in
bones), in transport system (haemoglobin), in control system (Na & K), as catalysts in group transfer
reactions or redox reactions (enzymes), etc.

12.2
12.2.1 Bulk Elements

Bulk elements are those that are considered primary by most living organisms. They are oxygen, car-
bon, hydrogen, nitrogen, and sulphur. The building blocks of these compounds constitute our organs
and muscles. These five elements also constitute the bulk of our diet, and for instance, more than 10
grams per day of these bulk elements are required for humans.
12.2.2 Macrominerals
Sodium, magnesium, potassium, calcium, chlorine, and phosphorus are referred to as macrominer-
als because they are essential ions in body fluids and form the major structural components of the body.
In addition, phosphorus is a key constituent of both DNA and RNA—the genetic building blocks of
living organisms. The six macrominerals present in the body are required in smaller amounts than the
bulk elements, i.e., lower levels are required in the diet.
12.2.3 Micro Elements (Trace Elements)

Micro elements are those elements that are required in very small amounts, but these are very essen-
tial for maintaining the good health of the organism. These are also known as trace elements or oligo
elements. Iron, copper, zinc, cobalt, manganese, molybdenum, iodine and fluoride are very important
trace elements. Nickel, vanadium, chromium, selenium, tin and silicon are also required by the body
but in very less amount.
Table 12.1 Essential elements

Bulk elements Macrominerals Trace elements
Oxygen (O) Sodium (Na) Manganese (Mn)
Carbon (C) Magnesium (Mg) Iron (Fe)
Hydrogen (H) Potassium (K) Cobalt (Co)
Nitrogen (N) Calcium (Ca) Copper (Cu)
Sulphur (S) Chlorine (Cl) Zinc (Zn)
Phosphorus (P) Iodine (I)
Molybdenum (Mo)
Table 12.2 Essential elements and their importance

Element Dietary source Important functions Insufficiency Excess
Sodium (Na) Table salt, milk, Acts as a systemic electrolyte and is Hyponatremia Hyperna-
sea vegetables and essential in co-regulating ATP with tremia
spinach potassium
Maintains normal hydration and osmotic
pressure
Maintains water balance and transmis-
sion of nerve impulses
Maintains the normal acid–base equilib-
rium
Helps in the transportation of CO2
Maintains proper viscosity of blood
Helps in storage of protein and glycogen

Metals in Biological System 12.3
Potassium Legumes, potato A systemic electrolyte and is essential to Hypokalemia Hyper-

(K) peal, sweet potato, co-regulate ATP with sodium kalemia
tomato, bananas,
papaya, lentils,
dry beans, whole
grains, soybeans,
and spinach
Calcium (Ca) Milk, cheese, Required for the health of muscle, heart Hypocalcemia Hypercal-
egg, fish, leafy and digestive system caemia
green vegetables, It builds and strengthen bone and teeth
nuts and seeds It supports synthesis and function of
blood cells
Magnesium Raw nuts, tomato, Required in the formation of bones and Hypomagne- Hyperma-
(Mg) beans, ginger, soy- teeth and in ATP processing semia and gnesemia
beans, spinach and magnesium
sea vegetables deficiency
Phosphorus Red meat, dairy Main component in bones and cells Hypophos- Hyperphos-
(P) products, fish, In energy processing, in DNA and ATP phatemia phatemia
bread, rice and oats (as phosphate) and many other functions
Chlorine (Cl) Table salt Required for the production of hydro- Hypochlo- Hyperchlo-
chloric acid in the digestive system and remia remia
in cellular pump functions
Iron (Fe) Red meat, fish, Required for many proteins and enzymes Anaemia Iron over-
eggs, dried fruit, In the development of RBC load disorder
grains, dry beans, In the formation of haemoglobin to
spinach, turmeric, prevent anaemia
leafy green veg- Oxygen transfer
etables, soybeans,
tomato and olive
Zinc (Zn) Calf liver, red meat, Essential cofactor for several biochemi- Zinc defi- Zinc toxicity
eggs, beans, mush- cal enzymes such as carboxypeptidase, ciency
rooms, spinach and liver alcohol dehydrogenase and carbonic
green peas anhydrase
Required for growth and healing of
muscles
Manganese Brown rice, beans, Cofactor in enzyme functions Manganese Manganism
(Mn) spinach, pineapple Bones and teeth formation deficiency
and soybeans Intracellular fluid
Copper (Cu) Mushrooms, Required as a cofactor of many redox Copper defi- Copper
spinach, cashews, enzymes, including cytochrome c oxi- ciency toxicity
walnuts and barley dase
Iodine (I) Sea vegetables, Required to synthesis of thyroid hor- Iodine defi- Iodism
iodized salt, egg, mones, thyroxine and triiodothyronine; to ciency
strawberry, cheese, prevent goiter
milk and fish As an antioxidant for extra thyroidal
organs such as mammary and salivary
glands and for gastric mucosa and
immune system (thymus)
(Continued )

12.4
Element Dietary source Important functions Insufficiency Excess
Liver, kidney and Essential constituent in Vitamin B12 Cobalt poi-
bones To maintain the normal bone marrow soning
function in producing erythrocytes
Molybdenum Tomato, onion and In the formation of oxidase enzymes Molybdenum Molybde-
(Mo) carrots deficiency num toxicity
Selenium Brazil nuts, cold Essential to activity of glutathione per- Selenium Selenosis
(Se) water wild fish, oxidase as antioxidant enzymes deficiency
turkey, calf liver,
mustard, mush-
rooms, barley,
cheese and garlic
Sodium, calcium and chlorine are known as extracellular fluids because they are located in blood
plasma. Sodium and potassium play important roles in the maintaining of normal hydration and
osmatic pressure. Potassium, magnesium and phosphate are known as intracellular fluids.
12.3 NON-ESSENTIAL ELEMENTS

These elements are not useful for biological activities. Their functions in biological systems are yet to
be known are non-essential elements.
12.4 IMPORTANT METALS IN BIOLOGICAL SYSTEMS
12.4.1 Haemoglobin
Haemoglobin (Hb) is the red pigment mainly found in erythrocytes, i.e., red blood cells of human
beings. The normal concentration of the Hb in Males is 14–16 g/dl and females 13–15g/dl.
Structure of Haemoglobin
Haemoglobin is a conjugated protein. It consists two parts:
(i) Protein part is known as globin, and it is a polypeptide chain.
(ii) Non-protein part is known as haem, and it contains porphyrin ring chelated with central Fe metal
atom.
Structure of Globin
Globin consists 4 polypeptide chains of two different primary structures. In these four polypeptide
chains, two a -chains and two b -chains. Each a -chain contains 141 amino acids, whereas b -chain
contains 146 amino acids. Therefore, haemoglobin has 574 amino acid residues. The four subunits of
haemoglobin are held together by non-covalent interactions such as hydrophobic, ionic and hydrogen
bonds. Subunits contain a haem group.
Structure of Porphyrin Ring

Porphyrin is a rigid, square planar molecule made of four pyrrole rings. (Pyrrole ring is a five-membered
ring containing N atom.) If a metal atom enters into the ring, then it is called metalloporphyrin. When
metal atom enters into the ring, it displaces two hydrogen atoms from the two nitrogen of 2 pyrrole rings.

The metal forms 2 covalent bonds with the 2 nitrogen atoms and 2 co-ordinate covalent bonds with
another two nitrogen atoms of pyrrole ring.
N
H
N N
H
N
Structure of porphyrin
If central metal atom of porphyrin is Fe, then it is haem, and if the central metal atom is magnesium,
then it is chlorophyll.
Structure of Haem
The haem contains a porphyrin, namely protophyrine with iron as its centre. porphyrin consists of four
pyrrole rings to which four methyl, two propinyl and two vinyl groups are attached. The iron atom is in
ferrous state, it can form six co-ordinate sites. The Fe is centred and bonded by the four nitrogen atoms
of porphyrine ring. The other two bonds are formed on either side of the planar porphyrin ring. On one
side, iron binds with amino acid residue (histidine of the globin). On another side, the co-ordinated posi-
tion of Fe+2 is available to bind oxygen. Haemoglobin contains four haem groups and four polypeptide
chains. In these four groups, two a, and two b. Haemoglobin is used for oxygen transport.
B2 B1
α2 α1
CH2
H3C O
O
N CH3
H3C
N Fe N
HO CH2
O N
N CH3
O
N
H CH2 OH
Structure of haemoglobin

12.6
Physiological importance of haemoglobin is uptake of O2 in the lungs and carries it to the tissues
through blood circulation and takes out CO2 from the tissues and carries it to the lungs.
12.4.2 Myoglobin
The myoglobin (Mb) is one of the metalloproteins. The role of myoglobin is to store the oxygen and
release it for metabolic processes. In addition, it may serve as an oxygen reservoir from which the
organism can draw oxygen during fast metabolic activities.
Myoglobin molecular weight is 17,800 g. The active centre of myoglobin is made of haem unit. It
consists of macrocyclic ligands known as porphyrin, and the iron atom is bound in the cavity of por-
phyrin. The porphyrin macrocycles is made up of four pyrrole rings with conjugated double bonds. The
periphery of macrocyclic ring can have several substituents. These substituents can be used to tune the
stereoelectronic properties of the complex. The inside of porphyrin ring has four nitrogen atoms, two
of which is attached to hydrogen atoms.
These hydrogen atoms can be quite readily deprotonated to generate a dianionic ligand. In this
form the ligand can readily bind to a number of divalent metal ions. The distance from centre of the
porphyrin ring and nitrogen atom is about 2.0 Å, which corresponds to normal M-N distance involving
first row transition metal ion. Because of the delocalization of electron over the entire frame work, the
ring is planar and rigid.
However, it can become non-planar to accommodate certain metal ions, which are either too small
or too large to be fitted exactly in the cavity of the porphyrin ligand. Because of this versatility, in terms
of ligand properties, the porphyrin ligand is present in a variety of biologically important systems.
Myoglobin contains only one haem and one (∝) polypeptide chain. Peptide chain contains 153
amino acids. It is used to store the O2 molecules.
R O O R
N Fe N
R
N
R
N
Mg
Myoglobine structure
tetra phenyl porphyrine
Function of Haemoglobin and Myoglobin

Haemoglobin and myoglobin exists in two forms, i.e., de-oxy form and oxy form.

Haemoglobin
In de-oxy form, four co-ordinates sites of iron are occupied by four nitrogen atoms, fifth co-ordinate
site is occupied by histidine residue. The sixth position is weakly bounded by water molecule. De-oxy
haemoglobin is said to be T-state.
On opposite side of the proximal histidine, there is one more histidine group placed near to the Fe
ion. It forces the binding of di-oxygen in end on bent conformation.
Haemoglobin co-ordinated to oxygen is called oxy haemoglobin. It is also referred to as R-State. In
oxy-haemoglobin state, the sixth co-ordinate site occupied by O2 in end on bent geometry.
Functioning Mechanism of Haemoglobin

In de-oxy haemoglobin, the porphyrin ring is dome shaped; the Fe (II) is in high spin state and para-
magnetic. Its size is 0.78 Å and it occupies above the plane of the porphyrin ring. De-oxy haemoglobin
is formed at muscles and tissues to supply oxygen.
However, oxy haemoglobin iron size is reduced to 0.61 Å and can easily fit into the cavity of planar
porphyrin ring; hence, it moves into the cavity of porphyrin ring with concomitant dragging of proximal
histidine that triggers the conformational changes in other globin subunits and thus by opening other
haem sites. As a result, the binding capacity of other haem irons with O2 is enhanced. This is the best
example for co-operativity interaction. At lungs, oxy haemoglobin structure can bind with oxygen easily.
12.4.3 Vitamin B12

Structure Details
Vitamin B12 is the only known biomolecule with a stable organometallic bond (i.e., carbon-metal bond).
The molecule contains corrin ring that consists of 4 pyrrole subunits with various side groups. The
4 pyrrole subunits are joined on the opposite side by a C CH3 methylene link, on one side by a C H
methylene link and with the two pyrrole subunits joined directly; it is porphyrin but one of the bridg-
ing methylene groups is removed. In each pyrrole, the nitrogen is co-ordinated to the central metal
atom. The sixth ligand is a nitrogen of 5,6 dimethyl benzimidazole, and it is below the ring. The other
nitrogen is linked to a five-carbon sugar, which in turn linked to a phosphate group and then back onto
the corrin ring via one of the seven amide groups attached to the periphery of the corrin ring. The base
ligand forms a ‘strap’ back onto the corrin ring. When compared to the porphyrin the corrin is more
flexible and also less flat. The corrin only has a conjugated chain around the part of the ring system,
whereas a porphyrine is delocalised around the whole four pyrrole rings.
Vitamin B12, common name is cynocobalamine, is a water-soluble vitamin with key role in the
normal functioning of the brain, nervous system and in the formation of red blood cells (RBC). It con-
tains the biochemically rare element cobalt and is one of the eight B-vitamins. It is normally involved
in the metabolism of every cell of the human body, especially affecting DNA synthesis and regulation,
and also fatty acid synthesis and energy production.
Medical Uses of Vitamin B12

(i) It is used to treat vitamin B12 deficiency.
(ii) It is used to treat cyanide poisoning.
(iii) It is used to treat hereditary of transcobalamin II.
(iv) It is used as a part of the Schilling test for detecting pernicious anaemia.

12.8
(v) High vitamin B12 level protects the elderly individuals against shrinkage associated with Alzheim-
er’s disease and impaired cognitive function.
CONH2
CONH2
CONH2
R
H2NOC N N
H CO
N N
H2NOC CONH2
O N
NH N
HO
O O
O P O
O HO
Here, R = 5′ deoxyadenosyl, Me, OH, CN
N N
H Corrin ring
N N
12.4.4 Chlorophyll
Chlorophyll is a green color pigment in cyanobacteria, algae and plants. In plants, the chlorophyll is
found in chloroplasts. Chlorophyll is extremely useful for photosynthesis.
6CO2 + 12H2O → C6H12O6 + 6O2 +6H2O
Structure of Chlorophyll
Chlorophyll structure is similar to other porphyrin pigments such as haemoglobin. It has Mg contain-
ing protoporphyrin in which the Mg metal is placed at the center of the porphyrin ring. Mg metal is
bonded with four nitrogen atoms of porphyrin ring. When the metal enters into the ring, it displaces
two protons and bonds with four nitrogen atoms of pyrrole ring to form the complex. The four nitro-
gen atoms are coordinated with Mg2+ by two normal covalent bonds and two coordinate covalent
bonds. Chlorophyll contains a fused cyclopentanone ring in addition and keto group as substituents.
Chlorophyll contains methyl group at 1, 5, 8 positions, Vinyl group at 2nd position, Ethyl group at 4th
position and a phytol chain at 7th position.
Different types of chlorophylls like chlorophyll-a, chlorophyll-b and chlorophyll-c are found.
Chlorophyll-a and chlorophyll-b differ from each other with respect to the substituents groups

at position three of ring B. Chlorophyll-a contains CH3 group at position 3, whereas chlorophyll-b
contains CHO group at position 3.
CH3
H2C R
4 3
D
CH3 N CH2
5 2
C N Mg N
6
1 CH
3
O N
B
O 7 8 CH
O 3
In chlorophyll-a
CH3O
R CH3
O
In chlorophyll-b
H R CHO
H3C
Phytall chain
H3C
CH3
12.5 METALS AND THEIR TOXICITY

The heavy meals are cumulative and potentially toxic. They cause damages to various organs like kid-
ney and gastrointestinal tract (GIT). The toxic character of metals is either due to:
(a) their combination with sulphydryl (-SH) group’s essential enzymes to form ring compacts and
thus inactivating the enzymes or
(b) complex formation with amino, imidazole, phosphate and carboxyl groups.
Some of the common toxic metals are As, Pb, Hg, Sb, Ag, Au, Cu, Fe, etc.
12.5.1 Toxicity of Arsenic

Arsenic (As) is a well-known poison. As poisoning is mainly due to the following two types:
(i) Inorganic arsenicals: These are mainly used as rodenticides, herbicides and insecticides. These
inorganic arsenicals cause anaemia, leukaemia, nervous, disorders and syphilis.

12.10
(ii) Organic arsenicals: These are mainly used as chemotherapeutic agents. Trivalent arsenicals are
more toxic than the pentavalent arsenicals.
Arsenic Poisoning
Arsenic poisoning is usually homicidal, but it may occur accidently, particularly, in children by inges-
tion of arsenical herbicides or insecticides. It may be either acute or chronic poisoning.
(i) Acute arsenic poisoning: It is characterized by severe gastrointestinal irritation, vomiting, diar-
rhoea and renal failure. The gastrointestinal symptoms usually begin within 1 hour and some-
times it may be delayed up to the severe poisoning, which in turn leads to death within 24 hours.
Treatment
(a) The correction of fluid and electrolyte imbalance.
(b) Administration of dimercaprol, also called British anti-Lewisite or British antilewisite.
(c) Prophylactic antibiotic therapy is advanced to prevent secondary infection.
(d) Hemodialysis may be necessary.
(ii) Chronic arsenic poisoning: It is commonly adopted for homicidal purpose. The symptoms are
weight loss, anorexia and diarrhoea. The later symptoms are loss of hair, finger nails become
brittle, Jaundice, aplastic anaemia and liver cirrhosis.
Treatment
Prolonged administration of dimercaprol. It contains two -SH groups that combine with the metal ions
to form relatively non-toxic and easily water-soluble complexes which are excreted via urine.
CH3 CH3
HS CH S C H
Na OAS O+ Na OAS
HS CH S C CH3
CH2OH H
12.5.2 Toxicity of Lead

Metallic lead (Pb) and its soluble compounds are highly toxic. Lead poisoning is an occupational dis-
ease, which is usually chronic. Occupations involving lead poisoning are ceramic industries, house
painting, copper welding, printing, plumbing and storage battery manufacturing. Flaking, lead-based
paints and toys painted with lead compounds are considered as serious health hazards for children.
Lead poisoning is also caused by chemotherapy.
Lead Poisoning
Lead poisoning is of the following two types:
(i) Acute lead poisoning: It is rare and charaterized by gastrointestinal irritation, muscle cramps
and weakness. Acute haemolytic crisis results in severe anaemia and haemoglobinuria.
Treatment
(a) Prompt gastric lavage.
(b) Use of calcium and phosphate salts and chelating agents for elimination of lead from circulation.
(c) Use to antispasmodics like atropine.

(ii) Chronic lead poisoning: It is commonly observed in young children, due to licking lead paints
or leaded toys, and also found in workers engaged in printing, paint and petroleum industries. The
symptoms are metallic taste in mouth, abdominal pains, appearance of greyish lead line along the
gingiual margin, muscle weakness, paralysis, irritability, headache and mild renal damage.
Treatment
Use of calcium disodium EDTA—the calcium chelate of the disodium salt of EDTA is used for lead
poisoning and is excreted via urine.
Na OOC H2C N CH2 CH2 N CH2 COO Na+
H2C M CH2
C O O C
O O
Dimercaprol is also useful for the treatment of lead poisoning.
12.5.3 Toxicity of Mercury

Inorganic mercurial compounds are used as syphilo therapeutic agents and laxatives. The organic
mercurials are used as antiseptics, preservatives, spermicides and diuretics.
Mercury Poisoning
Mercury poisoning is of the following two types:
(i) Acute poisoning: It is usually due to accidental intake of mercury chloride and other ionizable
mercury salts.
Symptoms
Severe GIT irritation and peripheral circulatory collapse, metalic taste in mouth, excessive salivation
and renal impairment
Treatment
(a) It is treated by the administration of protiens in the form of raw eggs or milk.
(b) By giving medicinal charcoal suspension.
(c) By gastric lavage.
(d) By administration of dimercaprol within one hour of intake.

1. Hb contains __________ number of polypeptide chains.
[Ans.: 2a and 2b]

12.12
2. a-polypeptide chain contains __________ amino acids in Hb.

[Ans.: 141]
3. Hb contains __________ rings.

[Ans.: 4 pyrrole]
4. __________ is the active centre in Hb.
[Ans.: Fe (iron)]
5. Central metal atom in vitamin B12 is __________.

[Ans.: Co]
6. Central metal atom present in chlorophyll is __________.

[Ans.: Mg]
7. In haemoglobin, the protein part is __________ and the non-protein part is __________.
[Ans.: globin, haem]
8. Haem consists of __________ rings.

[Ans.: 4 pyrrole]
9. At __________ co-ordinate site, O2 binds in Hb.

[Ans.: sixth]

1. Elements which required in very small amounts to the body are called
(a) Essential (b) Non-essential
(b) Macroelement (d) Micro element
[Ans.: d]
2. Which of the element involves in electron transfer?

(a) Ca (b) Fe
(c) Mg (d) Both (b) and (c)
[Ans.: d]
3. Number of polypeptide chains present in Hb

(a) 4 (b) 3
(c) 2 (d) 1
[Ans.: a]
4. Number of haem groups present in myoglobin

(a) 4 (b) 3
(c) 2 (d) 1
[Ans.: d]

5. In haemoglobin, the protein part is

(a) Haem (b) Globin
[Ans.: b]
6. Number of amino acid residues present in Hb
(a) 574 (b) 572
(c) 141 (d) 146
[Ans.: a]
7. Oxidiation state of Fe in oxy-Hb is
(a) +2 (b) +3
(c) +1 (d) Both (a) and (b)
[Ans.: a]
8. Which of the following are the toxic metal elements?
(a) As, Pb, Hg (b) Na, K, Cl
(c) H, O, C (d) None of these
[Ans.: a]
9. The types of toxicity are
(a) Chronic (b) Acute
[Ans.: c]
10. The role of chlorophyll is
(a) Oxygen carrier (b) Photosynthesis
(c) Electron transfer (d) Neuromuscular irritability
[Ans.: b]

1. What is the importance of sodium, potasium and chlorine in human body?
Ans.:
(a) Sodium, potassium and chlorine are used to maintain the normal hydration and osmatic pressure.
(b) They are used to maintain the normal acid–base equilibrium.
(c) They are used to maintained neuromuscular irritability.
2. Give an account on physiological importance of haemoglobin?
Ans.:
(a) Haemoglobin uptake O2 from the lungs and carries it to tissues through the blood circulation.
(b) Hb takes out CO2 from the tissues and carries it to lungs.
3. Describe mercury poisoning?
Ans.: Gastrointestinal track irritation, peripheral circulatory collapse and renal impairment.
4. Define metal classification in biological system?
Ans.: The living body contains 29 elements. These can be divided into two main groups:

12.14
(a) Essential elements

(b) Non-essential elements
Essential elements are again classified into two types such as macroelements and micro elements.
5. Draw the structure of haemoglobin?
Ans.:
CH2
H3C
O O
N CH3
H3C
N Fe N
HO CH2
O N
N CH3
O
N
H CH OH
6. Describe the medicinal uses of vitamin B12?

Ans.: Vitamin B12 is used to treat vitamin B12 deficiency, cyanide poisoning and hereditary of
transcobalamin II.

Q.1 Describe haemoglobin with neat sketch.
Q.2 Give detailed explanation about metal toxicity.
Q.3 Explain structure and function of myoglobin.
(a) Vitamin B12
(b) Chloropyhll
Q.5 Explain the biological importance of metals in detail.
Q.6 Give brief note on essential and non-essential elements and their importance in the human
body.

13 ORGANOMETALLIC
COMPOUNDS
13.1 INTRODUCTION
Organometallic chemistry is the study of chemical compounds containing at least one metal–carbon
(M-C) bond, where carbon is part of an organic group. It is also known as organo-inorganics, metallo-
organics and metalorganics. Some examples are organolithium, organo magnesium (Grignard reagent)
compounds, and metal carbonyls. Living systems contain a variety of organometallic compounds such
as haemoglobin, myoglobin and chlorophyll. The specialised field focused on the study of such com-
pounds is known as bioinorganic chemistry.
13.1.1 Organometallic Chemistry Timeline

The timeline of organometallic chemistry is outlined in Table 13.1.
Table 13.1 Timeline of organometallic chemistry

S. no. Year Scientist Investigation
1. 1760 Louis Claude Cadet de Gassicourt Investigated inks based on cobalt salts and isolated
cacodyl from cobalt mineral containing arsenic
2. 1827 Zeise Zeise salt is the first platinum/olefin complex
3. 1863 Charles Friedel and James Crafts Prepared organo chlorosilanes
4. 1890 Ludwig Mond Discovered nickel carbonyl
5. 1899 Grignard Introduced Grignard reaction
6. 1900 Paul Sabatier Worked on hydrogenation organic compounds with
metal catalysts. Hydrogenation of fats kicks off
advances in food industry, such as margarine
7. 1909 Paul Ehrlich Introduced Salvarsan for the treatment of syphilis, an
early arsenic-based organometallic compound
8. 1912 Victor Grignard and Paul Sabatier Won the Nobel Prize in chemistry
9. 1930 Henry Gilman Works on lithium cuprates
10. 1963 Karl Ziegler and Giulio Natta Nobel Prize for Ziegler-Natta catalyst
11. 1968 Heck Heck reaction
12. 1973 Geoffrey Wilkinson and Ernst Nobel Prize for sandwich compounds
Otto Fischer
13. 2005 Yves Chauvin, Robert Grubbs and Nobel Prize for metal-catalysed alkene metathesis
Richard Schrock

13.2
13.2 ORGANOLITHIUM COMPOUNDS

The organolithium compounds characterised by C Li bond are important in organic synthesis.
Organolithium compounds show similar reactivity as Grignard reagent. They are more reactive
than Grignard reagents. Lithium is less electronegative than carbon and the C Li bond is polarised
Cδ- Liδ+. Organolithium compounds behave as a nucleophile and a base.
13.2.1 Preparation of Organolithium Compounds

From Alkyl or Aryl Halides
The reaction of lithium metal at low temperature with an alkyl or aryl halide in a hydrocarbon solvent
in inert atmosphere gives alkyl lithium.
R X + 2Li → R Li + LiX
The yield of alkyl lithium is very low, if very pure lithium is used. It is believed that lithium must con-
tain at least 0.02% of sodium for the reaction to proceed smoothly. In the aforementioned reaction, the
reactivity of the halides is RI > RBr > RCl.
By Halogen–Metal Exchange Method

This method is useful for the preparation of organolithium reagent that cannot be directly obtained
from alkyl halide and metal. In this method, an organic halide is treated with alkyl lithium.
R X + R′ Li → R Li + R′ X
This method is best suited for the preparation of aryl-lithium derivatives. Thus, phenyl lithium is pre-
pared by treating bromobenzene with n-butyl lithium.
Br Li
+n C4H9Li +n C4H9Br
Bromo Benzene Phenyl lithium n-butyl Bromide

Vinyl lithium is obtained as follows:
R H THF R H
C C + n C4H9Li C C + n C4H9Br
R Br −120° R Li
Vinyl Bromide n-Butyl lithium Vinyl lithium n-butyl Bromide
By Metalation
Compounds having acidic hydrogen can be easily converted into organolithium compounds by treat-
ment with suitable organolithium compounds.
Li
+ +
Cyclopenta Phenyl lithium H Li

diene

Organometallic Compounds 13.3
13.2.2 Properties of Organolithium Compounds

Organolithium reagents are very reactive, powerful nucleophiles and strong bases. They find numerous
applications in organic synthesis and are better than the Grignard reagents.
Reaction with Compounds Containing Active Hydrogen

Organolithium reagents react with substrate having active hydrogen such as water, alcohols, amines
and carboxylic acid to give the corresponding hydrocarbons.
R Li + H OH → R H + LiOH
Reaction with Carbonyl Compounds

Organolithium reagent reacts with aldehyde to form secondary alcohol and reacts with ketones to form
tertiary alcohols. Primary alcohols are obtained by treatment with formaldehyde.
H3O+
CH2O + R Li R CH2 O− Li+ R CH2 OH
Formaldehyde 1° alcohol
O
R H3O+ R
R C H +R Li CH O− Li+ C CH OH
R R
Acetaldehyde 2° alcohol
(85%)
R′ R′
R H O+
C O +R Li R′ C O− Li+ 3 R′ C OH
R
Acetone R R
3° alcohol
Grignard reagent cannot react with hindered ketones. However, organolithium reagents are less sus-
ceptible to steric effects and react with hindered ketones, giving the corresponding 3° alcohols.
O O−Li+ OH
− + +
R3C Li H3O
R3C C CR3 R3C C R3C R3C C CR3
R3C CR3
O O−Li+ OH
(CH3)3 C−Li+ H3O+
(CH3)3C C C(CH3)3 (CH3)3C C C (CH3)3 (CH3)3C C C (CH3)3
C (CH3)3 C (CH3)3
O
(CH3)3C Li H3O+
(CH3)3C C C(CH3)3 C(CH3)3C O− Li+ [(CH3)3C]3 COH
−78°C
Reaction with Alkyl Cyanide

Organolithium reagent reacts with alkyl cyanide to give imine slat; when formed imine salt undergoes
hydrolysis first gives the imine, which on acid hydrolysis gives ketone.

13.4
R – Li R′ H2O R H3O+ R
R′ C N C N− Li+ C NH C O
R R R
Alkyl cyanide hydrolysis
Reaction with Epoxide

Epoxide reacts with organolithium reagents to give primary alcohols.
(i) CH3 — Li
CH2 CH2 CH3 CH2 CH2OH
(ii) H3O+
O
Ethyl epoxide 1-Propyl alcohol
Unsaturated organolithium reagent gives unsaturated alcohol.
(i) CH3C C−H+

CH2 CH2 CH3C (CCH2)2OH
(ii) H3O+
O
Reaction with Carbon Dioxide

Organolithium reagent, the formed carboxylate anion, reacts with a second molecule of reagent to give
a ketone.
− +
O O O Li +
+ +R Li − + H3O R
R Li + C O R C O Li R C O Li C O
R
Alkyl lithium carbondioxide R Ketone
This method finds application in the conversion of carboxylic acid into ketones. A special feature of
this reaction is that the original stereo chemistry of the carboxylic acid is maintained in the formed
ketones.
O
H COOH + 2CH3Li+ H C CH3
C6H5 H C6H5 H
trans
2-phenyl cyclo butane 2-phenyl cyclo butyl methyl
carboxylic acid ketone
Reaction with Alkenes

Organolithium reagent reacts with alkenes to give alkyl lithium, which reacts with a second molecule
of alkene to give the corresponding alkyl lithium. This process continues depending on the relative
amount on the alkene.

CH = CH
CH2 CH2 + Li R → R CH2 CH2 Li 
2 2
→
CH = CH
R CH2 CH2 CH2 CH2 Li 
2 2
→ R CH2 CH2 CH2 CH2 CH2 CH2 Li
Electrophilic Displacement
We have already seen the synthesis of vinyl lithium from vinyl bromide in the preparation of vinyl
lithium reagent.
R X + R′ Li → R Li + R′X
Nucleophilic Displacement
The halogen of the alkyl halide can be substituted with the alkyl group of the organolithium reagent to
give hydrocarbon.
R X + R′ Li → R R′ + Li X
Alkyl halide Alkyl lithium
This reaction takes placed by the SN2 mechanism as in the case of Wurtz reaction.
Reaction with α, β-unsaturated Carbonyl Compounds
− +
(i) Ph Li
(ii) H3O+
Ph OH
O
O O
Me2CuLi
H+
He
13.3 ORGANOMAGNESIUM COMPOUNDS

The organomagnesium halides are known as Grignard reagents. These were discovered by Vector
Grignard, and were hence named Grignard reagent. Grignard reagents are represented as R Mg X,
where R = alkyl, aryl, alkenyl, alkynyl and X = Cl, Br, (or) I.
13.3.1 Preparation of Organomagnesium Compounds

Grignard reagents are prepared by the action of magnesium on alkyl halide with anhydrous ether.

13.6
Reflux with
R X + Mg ether RMgX
Reflux with
CH3I + Mg ether CH3 MgI
For the given halogen, the reactivity order of an alkyl group is CH3 > C2H5 > C3H7; hence an increase in
carbon atoms the formation of Grignard reagent becomes difficult.
Reactivity order of alkyl halides is RI > RBr > RCl.
Aryl halide reacts with magnesium to form aryl magnesium halide. For example, phenyl magne-
sium bromide.
Vinyl halides react with magnesium to form vinyl magnesium halide. In aryl and vinyl halides, the
C X bond is stronger than the C X bond of alkyl halide. Therefore, a stronger Lewis base is required
for the formation of aryl or vinyl Grignard reagent requires more basic tetrahydrofuran (THF).
Mechanism
The reaction occurs via free radical mechanism.
2 R X + Mg → R R + MgX2
•
Mg + MgX2 → 2Mg X
• •
R X + Mg X → R + MgX2
•
•
R + Mg X → R Mg X
In addition, the Grignard reagent prepared from subtracts have acidic hydrogen.
Example: alkynes, cyclopentadienes, etc.
R C CH + RMgBr → R C C MgBr + RH
MgBr
Ether
+ RMgBr + RBr
The substrate for the preparation of Grignard reagent should not have groups like COOH, OH,
NH2 and C CH.
Structure
Grignard reagent exists as a coordination complex with ether.
CH3CH2 O CH2CH3
X
C2H5
R Mg X (or) R Mg O
C2H5
C2H5
O
CH3 CH2 O CH2CH3 C2H5

13.3.2 Properties of Organomagnesium Compounds

Grignard reagents may be regarded as polar compounds, and are a source of nucleophile carbon ions.
δ- δ+
R Mg X → R Mg X
Reaction with Compound Containing Active Hydrogen

The Grignard reagent reacts with active hydrogen containing molecules such as H 2O, alcohol, NH3 and
R NH2 and forms hydrocarbons.
CH3 Mg I + H2O → CH4 + Mg(OH)I
CH3 Mg I + NH3 → CH4 + Mg(NH2)I
CH3 Mg I + R OH → CH4 + Mg(OR)I
CH3 Mg I + RNH2 → CH4 + Mg(NHR)I
Reaction with Carbonyl Compounds (Nucleophilic Addition Reaction)

The C Mg bond in the Grignard reagent is polar and generates a nucleophile carbon (Cδ- Mgδ+ Br).
Being nucleophile in nature, the Grignard reagent attacks the carbonyl group of aldehydes, ketones,
esters, anhydrides, acid chlorides and amides. In this reaction, the alkyl group having carbon ionic
character becomes attached to the carbonyl carbon and Mgx to the oxygen of carbonyl group to give
complex. These addition Products in decomposition with water give the hydroxyl compounds.
Reaction with Ketones

O
H3C O− Mg+I H3C OH
H+ + Mg(OH)I
CH3 C CH3 + CH3Mg I C C
H2 O
H3C CH3 H3C CH3
Acetone 3° alcohol
Reaction with Aldehydes
O O− MgI H
H3O+
CH3MgI + CH3 C H CH3 C CH3 CH3 C OH
H CH3
Iso propyl alcohol
Reaction with Formaldehyde

O
C2H5 MgX + H H C2H5 CH2 OMgX C2H5 CH2 OH + Mg(OH)I

13.8
Reaction with Halides

O H H
H3O+
CH3 C H + CH3MgX CH3 C O− Mg+X CH3 C OH Propanol
CH3 CH3
Acetaldehyde
+ Mg(I)(OH)
Reaction with Esters
O O
CH3 O− MgX
CH3MgI + CH3 C OEt C CH3 C CH3 + Mg(OE)t
H3C OEt Acetone
R–MgX
OH
CH3 C CH3
CH3
3° alcohol
Reaction with Acid Chloride

O O
H3C O− Mg+I
− HOH
CH3 C Cl + CH3MgI C CH3 C CH3 + Mg(Cl)I
H3C Cl
(i) CH3MgI (ii) H3O+
Acetyl chloride Acetone
H3C CH3
C
H3C OH
3° alcohol
Reaction with Acid Anhydrides

O
O− MgX O O OH
− + R C RMgX
RMgx + O R C O C R R C R R C R′
H3O+
R C
R R
O 3° alcohol
Reaction with Amines

O
R′ RMgx R O− Mg+X O
RMgx + C O R H + R C C
H2N H3O+ R C R′
NHMgX R′ NHMgX
+
− +

Reaction with Epoxide

Grignard reagent reacts with epoxide to give primary alcohol with the lengthening of carbon chain by
two carbon atoms.
H+
CH3MgBr + CH2 CH2 CH3CH2CH2O−Mg+Br CH3CH2CH2OH
Propyl alcohol
O
Reaction with Carbon Dioxide

Grignard reagent is treated with solid CO2 followed by hydrolysis yield carboxylic acid.
O O O
HCl
RMgX + C O R C O− MgX R C OH + Mg(x)Cl
H2 O
Reaction with Nitriles

When Grignard reagent reacts with nitriles, ketones are formed. If HCN is used instead of alkyl cya-
nide, an aldehyde is obtained.
H H O
− + − H2O H 2O
(1) RMgX + HC N R C N MgX [RC NH] R C H
Acetaldehyde
O
− − + H2O+ H2O
(2) RMgX + RC N RRC N MgX [RR′C NH] R C R
Acetone
Reaction with Oxygen

Oxygen reacts with Grignard reagent of a low temperature to give an adduct, which on acidification
gives the corresponding hydroperoxides.
O2
− + +
(CH3)3C MgX  → (CH3)3 C O O Mg x H→ (CH3)C O OH
Tert-butyl hydroperoxide
Reaction with Sulphur

Grignard reagent reacts with sulphur to give the corresponding thiols.
SR H3O+
RMgX + S Mg RSH + Mg(OH)X
X Thiols
Reaction with Carbon Disulphide

Carbon disulphide reacts with Grignard reagent to give an adduct, which on hydrolysis, gives the cor-
responding di thionic acid.
CH3
H3O+
CH3MgI + S C S S C S−Mg+I CH3CS2H + Mg(OH)I
dithionic acid

13.10
Reaction with Sulphur Dioxide

SO2 adds on to Grignard reagent to give an adduct, which on hydrolysis gives sulfonic acid.
O−Mg+X H3O+
RMgX + SO2 R S R S OH + Mg(OH)X
O
O
Sulfonic acid
Reaction with Sulphur Trioxide

O O O O O
H3O+
CH3MgX + O S S S + Mg(OH)Cl
O H3C OMgX H3C OH
alkane sulphonic acid
Reaction with Iodine

Grignard reagent on reaction with iodine in acetone gives the corresponding alkyl halide.
RMgX + I I R I + MgXI
alkyl iodide
Reaction with Inorganic Halides

Grignard reagent reacts with inorganic halides to gives organometallic compounds.
4 C2H5 Mg Br + PbCl4 → (C2H5)4 Pb + 4Mg (Br)Cl.
Tetraethyl lead
Reaction with Alkyl Halides

CoCl2
C2H5MgBr + C2H5CH2Br  → C2H5CH2 C2H5
13.4 METAL CARBONYLS

Carbonyls are complex compounds in which carbon monoxide is attached to metals by coordinate link-
age. Carbonyls are mainly divided into three types.
(i) Mononuclear carbonyls: Here, only one metal atom is present.
Example: [Ni(CO)4] – Nickel tetracarbonyl
[Fe(CO)5] – Iron pentacarbonyl
[Cr(CO)6] – Chromium hexacarbonyl
[V(CO)6] −Vanadium hexacarbonyl, etc.

(ii) Di or binuclear carbonyls: In these carbonyls, two metal atoms are present.
Example: Fe2(CO)9, CO2(CO)9
(iii) Polynuclear carbonyls: In these carbonyls, more than two metal atoms are present.
Example: Fe3(CO)12
13.4.1 Ligand
Substances which can donate unpaired or non-bonded or a lone pair of electrons are called ligands. The
Lewis dot structure of carbon monoxide is as follows:
Carbon–ground state electronic configuration: – 1s2 2s2 2px1 2py1 2p0z
Excited state electronic configuration: – 1s2 2s1 2px1 2py1 2pz1
Oxygen–ground state electronic configuration: – 1s2 2s2 2px2 2py1 2p1z
C O
C O
Carbon monoxide molecule has a lone pair of electrons of carbon as well as oxygen atoms. In the for-
mation of carbonyls, carbon monoxide donates the lone pair of electrons from carbon to metal atom. As
a result, the two atoms are linked by a coordinate bond. Transition elements have a vacant ‘d’ orbital
which can easily accommodate the donated electrons.
13.4.2 Effective Atomic Number

Effective atomic number (EAN) is the number of electrons present in the metal atom and the number of
electrons gained from the ligand to attain the next inert gas electronic configuration. Some important
carbonyls and their EAN number shown in Table 13.2.
EAN = number of electrons present in the metal atom + number of electrons gained from ligand
Table 13.2 Carbonyls and their EAN number

Carbonyls Number of electrons pre- Number of electrons Next inert gas
sent in metal atom gained from ligand
Cr(CO)6 24 12 24 + 12 = 36 (Kr = 36)
Fe(CO)5 26 10 26 + 10 = 36 (Kr = 36)
Ni(CO)4 28 8 28 + 8 = 36 (Kr = 36)
Mo(CO)6 42 12 42 + 12 = 54 (Xe = 54)
13.4.3 Preparation of Carbonyls

(i) By passing carbon monoxide over reduced nickel at 30–50°C under atmospheric pressure.
30 − 50° C
Ni + 4CO 
→ Ni(CO) 4
(ii) At high temperature and 200–400 atmospheric pressure, iron reacts with carbon monoxide to
form iron pentacarbonyl.

13.12
200 ° C
Fe + 5CO 200
 atm → Fe( CO)5
Penta Carbonyl Nickel
(iii) Metal halides react with carbon monoxide at high temperature and pressure in the presence of
sodium metal and give the concerned metal carbonyl.
CrCl3 + 3Na + 6CO → Cr(CO)6 + 3NaCl
Tri chloro chromium
13.4.4 Properties of Carbonyls

Solubility
In carbonyls, covalent bonds are present. Hence, they dissolve in organic substances.
Reaction with Halogens

Gaseous halogens react with nickel carbonyls and give nickel halides and carbon monoxide.
Ni (CO )4 + X 2 → NiX 2 + 4CO
Reaction with Acids

Among the hydrohalide acids, carbonyls react with hydroiodic acid and give nickel iodide and release
carbon monoxide and hydrogen.
Ni (CO )4 + 2HI → NiI 2 + 4CO ↑ + H 2 ↑
Tetra Carbonyl Nickel
Aqueous halogen acids do not react with carbonyls but aqueous sulphuric acid reacts with nickel car-
bonyl and gives nickel sulphate.
Ni(CO) 4 + H 2SO 4 (aq ) → NiSO 4 + H 2 ↑ + 4CO ↑
13.4.5 Structure of Carbonyls

Nickel Tetracarbonyl
The atomic number of nickel is 28. The outermost electronic configuration is 3d8 4s2 4p0. The energies
of 3d and 4s electrons are not very much different; hence, in the presence of carbon monoxide molecule,
the two 4s electrons shift to 3d orbitals. Thus, four orbitals (one from 4s, three from 4p) undergo sp3
hybridisation and form 4 sp3 hybrid orbitals to form nickel tetracarbonyl complex with carbon mon-
oxide molecules.
The outermost electronic configuration of nickel atom at ground state is as follows:
3d 8 4s 2 4p 0

Shifting of electrons from 4s to 3d orbitals in the presence of CO forms four vacant orbitals and under-
goes sp3 hybridisation to give four equivalent sp3 hybridised orbitals.
3d 10 4s 0 4p 0
sp 3 hybridisation
Electronic configuration of nickel at nickel tetracarbonyl
3d 10 CO COCOCO
CO
Ni
CO CO
CO
Ni(CO)4
Iron Pentacarbonyl
The atomic number of iron is 26. The outermost electronic configuration is 3d6 4s2 4p0.
3d 6 4s 2 4p0
In the presence of ligands, all unpaired d electrons are paired and the 4s electrons shift to the empty
d orbital. Now, one d orbital, one s orbital and three p orbitals are empty. They undergo dsp3 hybridisa-
tion and have a trigonal bipyramidal structure.
In presence of ligands,
3d 8 4s 0 4p0
dsp 3 hybridisation
The electronic configuration of iron in iron pentacarbonyl is as follows.
3d 8 CO CO COCOCO
CO
CO
Fe CO
CO
CO
Fe(CO)5

13.14
Structure of Chromium Hexacarbonyl

The atomic number of chromium is 24. The electronic configuration is 3d5 4s1 4p0.
3d 5 4s1 4p0
In the presence of ligand, all unpaired electrons are paired to form two d orbitals, one s orbitals, three
p empty orbitals and undergo sp3d2 hybridisation and attain octahedral structure.
In presence of ligands,
3d 6 4s 0 4p 0
sp 3d 2 hybridisation
The electronic configuration of chromium in chromium hexacarbonyl is as follows.
CO CO CO COCOCO
CO
CO CO
Cr
CO CO
CO
Cr(CO)6
Structure of Fe2 (CO)9

In this molecule, three carbon monoxide molecules are bonded in between two iron atoms. The remain-
ing six ligands; three are bonded with one iron atom and another three bonded with another iron atom.
CO
CO CO
Fe
CO CO CO
Fe
CO CO
CO
Fe(CO)9
Structure of Fe3(CO)12
In between three iron atoms each, six carbon monoxide molecules are bonded as two bridges.

CO
CO CO
Fe
CO CO CO
Fe
CO CO CO
Fe
CO CO
CO
Fe(CO)12

1. The structure of Grignard reagent is __________.
[Ans.: CH3CH2 O CH2CH3
R Mg X
CH CH3 O CH2CH3]
2
2. R X + Mg Reflux

Ether
→ __________.
[Ans.: R Mg X]
3. Reactivity order for halides in organolithium is __________.
[Ans.: RI > RBr > RCl]
4. The covalent bond between carbon and metal forms __________.
[Ans.: organometallic compounds]
5. The charge carried by carbon in organometallic reagents is __________.
[Ans.: negative]
6. The charge of metal atom in organometallic reagent is __________.
[Ans.: positive]

1. Grignard reagent is
(a) R Li (b) R Mg R
(c) R Mg (d) R Mg X
[Ans.: (d)]

13.16
2. Alkyl lithium reagent structure is

(a) R Li (b) R Li X
[Ans.: (a)]

1. Write any two methods of preparation of organolithium reagents.
Ans.: From alkyl or aryl halides
The reaction of lithium metal at low temperature with an alkyl or aryl halide in a hydro carbon
solvent in inert atmosphere gives alkyl lithium.
R X + 2Li → R Li + Lix
By metalation
Compound having acidic hydrogen can be easily converted into organolithium compound by
treatment with suitable organolithium compound.
Li
+ +
H Li
2. Write any two properties of organomagnesium reagents.

Ans.: Reaction with CO2
R R R
H2O
R Mg X+ C O R C OH MgX R C OH + Mg(X) Cl
Reaction with ketones

O O+ MgX CH
CH3 C CH3 + RMgX CH3 C CH3 CH3 C CH3
R R

Q.1 Give a detailed note on organolithium reagents.
Q.2 Briefly explain organomagnesium reagent.

14 COORDINATION
CHEMISTRY
14.1 INTRODUCTION
Alfred Werner, a Swiss chemist and the founder of coordination chemistry, won the Nobel Prize for
chemistry in 1913 for his research into the structure of coordination compounds. Prior to him, the
concepts of valence bonding and geometry in metal complexes were confusing. He revolutionised
the fields of inorganic chemistry and stereochemistry and found applications in many fields such as
organic chemistry, analytical chemistry, biochemistry, geochemistry and mineralogy. He proved that
stereochemistry is not limited to organic chemistry but is a general phenomenon.
Coordination chemistry is the study of a class of compounds formed by metals. Coordination
compound can be explained by the following example:
K4[Fe(CN)6]—Potassium ferrocyanide complex can prepared by an excess of aqueous potassium
cyanide being added to aqueous ferrous sulphate, formed as a yellow colour solution. The complex
K4[Fe(CN) 6] is called “coordinate compound”. The formation of coordination compound from a metal
is called “complexation”. The complex solution contains [Fe(CN) 6]4- and is called “metal complex
ion”. It can be isolated as the part [Fe(CN) 6]4- in K4 [Fe(CN) 6] and is called “complex species (or)
complex entity”. The formula of the complex species should be represented within brackets—[ ].
14.2 BASIC REQUIREMENTS TO FORMATION OF COORDINATION

COMPOUND
(i) The coordination compound formed by metal and certain number of species is called a ligand.
Ligand means binds or that which is attached, having an electron pair for binding with the posi-
tive metal. It is the prime requirement for complex formation. Ligands may be anions (CN–, Cl–,
SCN–, etc.), neutral molecules (H2O, CO, NH3, etc.) but not positive ions.
(ii) Complex species may be cationic, neutral and anionic.
Examples:
(a) Cationic complex: [Pt(NH3)4]2+ Tetraammineplatinum(II)
(b) Neutral complex: [Pt(NH3)2Cl2] Diamminedichloroplatinum
(c) Anionic complex: [Pt(Cl4)]2– Tetrachloroplatinate(II)
(iii) The stability of the metallic species increases with the complexation of metal ion; hence, complex
of metal is more stable than metal ion itself.
(iv) Complex formation is often accompanied by striking changes in colour.
(v) Depending on the number of ligand bonded to the central metal, the molecule of the complex
attains its characteristic structure such as tetrahedral, square planar, octahedral, etc.

14.2
(vi) Depending on the type of bonding and unpaired electrons present on the metal, the complex may
be diamagnetic or paramagnetic.
(vii) A metal complex differs from an ordinary salt in some respects.
A simple salt is dissolved in water and produce its constituent simple ions.
Example: FeSO4→Fe+2 + SO42–
However, metal complex is dissolved in water and produces complex ion.
Example: K4[Fe(CN)6 ] → [Fe(CN)6]4– + 4K+
(viii) Some metal complexes are soluble in water, but some are insoluble.
Example for water soluble complex: [Ag(NH3)2]+(diamino silver(I)
Example for water insoluble complex: [Ni((CH3)2 C N OH)] Nickel dimethylglyoxime
Some complexes are soluble in organic solvent.
Example: Bis(acetylacetonate)Cu(II)
[Cu(CH3CO CH C O−)2]
CH3
Double Salt and Coordination Compounds

Double salt is the compound formed by combining two stable compounds.
Example: Ferric alum Fe2(SO4)3⋅(NH4)2SO4⋅24H2O
When double salts are dissolved in water, they will completely dissociate into simple ions. For
example, when crystals of ferric alum are dissolved in water, the solution shows properties of NH4+,
SO42– and Fe2+ ions.
Coordination compound is formed with metal and ligands by dative bonds. When it dissolves in water,
it does not break down to simple ion; only the ionic bond breaks and gives metal ion and complex ion.
Example: K4[Fe(CN)6] When dissolved in water the solution, it consists of K+ and [Fe(CN)6]4–; the
complex ion does not break down to Fe+2 and CN–2 ions.
Coordination Number
The total number of monodentate ligands attached to the central metal complex is called coordination
number; this is equal to number of sigma bonds between the metal and ligand. Coordination number
from two to nine is known in complex; four and six are common coordination numbers but three is a
rare coordination number.
Oxidation Number
The number denotes the charge on the central metal atom if all the ligands in the complex were removed
along with their electron pairs; it is represented by Roman numerals.
Eg.:
[NiCl4]2-
In the above complex ion if all four chlorine ligands are removed from complex ion then the central
atom Ni attain a charge of +2. The oxidation number of this metal in this complex is written as II.
[Cr(NH3)6]3+
In the above complex ion if all six ammonia ligands are removed from complex ion then the central
atom Cr attain a charge of +3. The oxidation number of this metal in this complex is written as III.

Coordination Chemistry 14.3
Types of Ligands
A ligand is an ion or a molecule capable of donating an electron pair by participating in the formation
of a coordinate bond. Depending on the bonding formation, ligands are divided into unidentate, poly-
dentate, bridging, ambident, flexident ligands, etc.
Unidentate ligand is bound by only one atom at a time as a donor and fills only one coordination
position of a given cation.
Example: Cl-, Br-, I-, CN-, SCN-, NO3-, NO2-, R3N, pyridine, CO, H2O, etc.
Poly dentate ligand is bonded by more than one atom at a time as a donor and fills more coordina-
tion positions of a given cation. Ligands and their bonding capacity given in Table 14.1.
Table 14.1 Ligands and their bonding capacity

Name of the ligand Bonding capacity
Oxalate Bidentate
Diethylenetriamine Tridentate ligand
Triethylenetetramine Quadrate ligand
EDTA Hexadentate ligand
Bridging ligand binds simultaneously with two metals by forming a bridge between the two metals and
acting as a ligand to both metals.
Cl
Pd Pd
Cl
Ambidentate ligand is capable of bonding through one type of donor atom in one complex but through
a different donor atom in another complex. Such a ligand has potentially two ligating atoms. Some
ambidentate ligands and their names are given in Table 14.2.
Table 14.2 Ambidentate ligands and their names

Ligand Complex Complex name
- M ONO Nitrito
NO2
M NO2 Nitro
CN- M CN Cyano
M NC Isocyano
S2O3- M SSO3 Thiosulphato
M OSSO2 Oxythiosulphate
A flexidentate ligand can bind to a metal with different numbers of coordinate sites.
Example: EDTA is normally a hexadentate ligand but can act as a pentadentate or tetradentate
ligand depends on ligand present at that particular situation; hence, it is called a flexidentate ligand.
14.3 NOMENCLATURE OF METAL COMPLEXES

Metal complexes are named systematically based on certain rules recommended by the International
Union of Pure Applied chemistry (IUPAC).

14.4
14.3.1 Cationic Complex

The cationic complex names begin with the number of ligands, followed by the name of the ligand
bonded to the central metal atom (or) ion. The oxidation number of metal is indicated by Roman numeri-
cal parenthesis.
Example: [Cr(NH3)6]+3 Hexaamminechromium(III)ion.
(a) (b) (c)
The complex name will be written without space between ligand and metal names and the metal name
and the parenthesis in a single entity.
Examples: [Cr(NH3)6]Cl3 - Hexaamminechromium(III)chloride
[Cu(NH3)4]SO4 - Tetraamminecopper(II)sulphate
In normal salts like BaCl2, the salt is named barium chloride and not barium dichloride because the
bivalency of barium is implied. Similarly, [Cr(NH3)6]Cl3 is not named tri chloride; but simply chloride.
The first part of the name of the complex Hexaamminechromium(III) automatically indicates that it is
of three chlorides.
14.3.2 Anionic Complex

The name of the anionic complex will be mentioned by the adding of -ate at the end of the metal ion;
however, complex positive ions or neural molecules do not have such an ending.
Example: [Fe(CN) 6]-4 hexacyanoferrate—here, the suffix “ate” is attached to the name of the metal.
Anionic complexes having simple cations like Na+, K+, etc., where the complex begins with the
name of a cation.
Example: K4[Fe (CN)6] potassium hexacyanoferrate(II)
The complex ion can put in a bracket [ ]. This indicates that the ions are expected to be formed in a
solution when the complex is dissolved in solvent. Some common complex anion shown in Table 14.3.
Table 14.3 Names of complex anions containing metal atoms

Ag – Argentate Fe – Ferrate W – Tungstate
Au – Aurate Pb – Plumbate Zn – Zincate
Al – Aluminate Mn – Magnate Pt – Platinate
Cr – Chromate Ni – Nickelate Mo – Molybdate
Co – Cobaltate Sn – Stannate V – Vanadate
Cu – Cuprate Os – Osmate Ti – Titanate
Naming Ligands
Negative Ligands
The name of a negative ligand ends in O.
Example:
F-- Fluoro O2-- Oxo SCN- - Thiocyanato
Cl- - Chloro O22-- Peroxo C2O42- - oxalato

Neutral Ligand
Neutral ligands are named as such without any special name ending.
Example:
NH3-Ammine NO - Nitrosyl H2O -Aqua
O2- Di oxygen CO - Carbonyl N2 -Di nitrogen
Positive Ligand
Positive ligands end with “ium”.
Example: NH2-NH3+ - hydrazinium
Order of Ligands
(i) When a complex contains different charged ligands, the order is negative ligand, neutral ligand,
positive ligand.
Example: [PtCl2(H2O)(NH2NH3)+] Dichloroaquahydrozoniumplatinum(II)ion
(ii) When a complex contains more than one kind of similar charged ligand, the ligands are listed in
the alphabetical order.
[CrCl3(NO2)3]3- Trichlorotrinitrochromate(III)ion
(iii) The number of the same ligands present in the complex uses prefixes such as di, tri, tetra, penta
and hexa.
[Ag(NH3)2]+ - Diamminesilver(I)ion.
However, when the name of the ligand itself has a prefix such as di, tri, tetra, etc., to avoid confusion,
prefixes such as (di) = bis, (tri) = tris, (tetra) = tetrakis are used to indicate the number of such ligands
present in complex.
[Cu(en) 2]SO4 -bis(ethyldiamine)copper(II)sulphate
Naming Isomeric Ligands

In isomeric complexes, the ligand is attached through different donor atoms to the metal.
Example: M - NO2 nitro (nitro -N-)
M - ONO nitrito (nitrito -O-)
Designating the Ligand Atom in a Polydentate Ligand

A polydentate ligand has more than one donor site, some (or) all of which may be bonded to the metal.
Example:
2− 2−
S O O S
C C
Ni Pt
C C
S O O S
Bis(dithiooxalato -o,o´)Nickelate(II) Bis(dithio -S,S´)Platinate(II)

14.3.3 Nonionic Complexes

Nonionic complexes are represented with a single entity.
Example: [Fe(NH3)3(CO)3] - Triamminetricarbonyliron(0).

14.6
14.3.4 Polynuclear Complex

A complex formed with two or more metal ions per molecule is called a polynuclear complex. The two
metal ions in it are bridged by ligands; such bridging ligands are identified by the prefix µ - if there
are two or more bridging ligands of the same type, this is indicated by tri -µ, di -µ. If there are two or
more bridging ligands of different types, then the prefix µ - is added for each such bridging ligand in
the alphabetical order.
Example:
NH2
(NH3)4Co Co(NH3)4
NH2
Tetraaminocobalt-(III)di-µ-imidotetraaminecobalt-(III) ion.
14.3.5 Complex with Metal-Metal Bond

In a complex having a metal-metal bond, the prefix bis or - di is used before the name of metal which
involves metal-metal bond. Abbreviations for Polydentate ligands their formulas shown in Table 14.4.
(NH3)4Pt Pt(NH3)4 Cl2
Cl Cl
Syndi-chlorooctaaminebi-platinum (II).
[Br4ReReBr4]-2 bis(tetrabromorhenate)(ReRe) (2-)
Table 14.4 Abbreviation for ligand names

Name of the ligand Abbreviation Formula
Ethylene di amine En NH2 CH2 CH2 NH2
Propyl diamine pn CH3 CH (NH2) (CH2 NH2)
Pyridine py C5H5N
Ethylene di amine tetra acetate EDTA CH2 N(CH2COO−)2
CH2 N(CH2COO−)2
Thiourea tu H2N CS NH2
1, 10 - phenathroline o -phen (C12H18N) 2
Oxalato ox COO−
COO−
Some important complexes by Scientist names shown in Table 14.5.
Table 14.5 Scientist names for complexes

Name of the complex Formula
Zeise salt K[Pt(C2H4)Cl3]
Magnus green salt [Pt (NH3)4] [PtCl4]
Ed Mann salt K[Co(NH3)2(NO2)4]
Reinecke’s salt NH4[Cr(NH3)2(NCS)4]
Vaska’s complex [Ir(CO)(PPh3)2Cl2]
Wilkinson catalyst [Rh(PPh3)3Cl]

14.4 THEORIES OF COORDINATION CHEMISTRY

The various theories like Werner’s theory, Sidgwick’s electronic concept theory, valence bond theory
(VBT), crystal field theory (CFT), molecule orbital theory (MOT), etc., have successfully explained the
properties of complexes and the bonding between the metal and ligand.
14.4.1 Werner’s Theory

In 1893, Alfred Werner proposed this theory at the age of 26; it is now referred to as Werner’s coordina-
tion theory. This theory explains the “primary-secondary valence” of metal complexes.
Postulates of Werner’s Theory

(i) Complexes exhibit primary and secondary valance; primary valance is ionisable and secondary
valance is non-ionisable. Primary valance can be satisfied by anions and the secondary valance
by anions and neutral molecule.
(ii) The primary valance represents the oxidation number and the secondary valance represents the
coordination number.
(iii) All elements tend to satisfy both primary and secondary valance; but in every case, the fulfilment
of the secondary valance should be essential.
(iv) Secondary valance is directed towards some fixed positions in structure.
Example: Four coordinated complexes the four valances are arranged in either square planar or
a tetrahedral structure and in six coordinated complexes, six valances are directed towards six
corners of the octahedron.
(v) Werner extensively studied “chloroaminecobalt(III)complexes” with silver salt which is shown in
Table 14.6.
Table 14.6 Werner studied chloroaminecobalt(III)complexes

Complex Number of Cl ions Formula Number of ions Molar
precipitated as AgCl2 in solution conductivity ohm–1
CoCl3⋅6NH3 (A) 3 [Co(NH3)6]Cl3 4 -
404
CoCl3⋅5NH3 (B) 2 [Co(NH3)5Cl]Cl2 3 -
229
CoCl3⋅4NH3 (C) 1 [Co(NH3)4Cl2]Cl 2 -
97
CoCl3⋅3NH3 (D) 0 [Co (NH3)3Cl3] 0 0
In complex (A), primary valence is satisfied by three chloride ions and secondary valence is sat-
isfied by 6 NH3 molecules. According to the complex structure, ammonia molecules are tightly
bound to cobalt, hence they do not dissociate in solution, but chloride ions are far away from co-
balt and are less firmly held by metal. Hence, all the three chloride ions dissociate in the solution,
giving 3Cl- ions and [Co (NH3)6]3- with a total of four ions.
(vi) The bond between metal and ligand is a coordinate covalent bond; it is a type of covalent bond.
Defects of Werner’s Theory

Werner’s theory describes the structure of many coordination compounds successfully; however, it
does not explain the nature of bonding within the coordination sphere.
(i) This theory unable to account for the four coordinated and six coordination among complexes.
(ii) This theory is unable to explain some of the four coordination complexes as square planar, where-
as some others are tetrahedral complexes.

14.8
14.4.2 Sidgwick’s Electronic Concept Theory

According to Sidgwick, the metal and the ligand involve a coordinate bond. Here, the ligand donates
the electrons to the central metal atom to form coordination compounds. These ligands are known as
donors and the metal ions are the acceptors. The bond between the donor and acceptor is called coor-
dinate, or dative or semi-polar bond. The coordinate bond is generally represented by the “→” arrow,
starting from the donor pointing towards the acceptor L→M.
Effective Atomic Number

Effective atomic number (EAN) is also known as 18 electron rule or Nobel gas rule. According to
Sidgwick, the EAN of the central metal ion is the total number of electrons around the central metal
ion, including those gained through coordination by the ligand. The EAN is equal to the atomic num-
ber of the next higher inert gas. Examples of complexes which obey EAN rule and which have excep-
tion from EAN rule are shown in Table 14.7 and 14.8 respectively.
EAN = atomic number of the central metal ± the number of electrons gained or lost
in ion formation + the number of electrons gained through coordination
Table 14.7 Examples of complexes which obey the EAN rule

Complex Central metal Atomic num- Oxidation Electrons EAN Atomic number
(M) ber of metal number of gained through of the next higher
metal coordination inert gas
[Ni(CO)4] Ni 28 0 8 28 + 0 + 8 = 36 36
[Fe(CO)5] Fe 26 0 10 26 + 0 + 0 = 36 36
Table 14.8 Examples of complexes which are exception to the EAN rule
Complex Central Atomic Oxidation Electrons EAN Atomic number
metal (M) number of number of (M) gained through of the next higher
(M) coordination inertgas
(V(CO)6) V 23 0 12 23 + 0 + 12 = 35 36
(Mn(CN)4) M 25 0 8 25 + 0 + 8 = 31 36
Defects of Sidgwick’s Theory

(i) This theory does not explain the stability of metal complexes properly. As the donation of elec-
trons by the ligand to the metal ion would cause accumulation of unfavourble negative charge
over the electro positive charge on the central metal, it will reduce the stability of the metal
complex.
(ii) The electron pair is donated by H2O, NH3, etc., to the central metal ion by 2s2 pair of electron. The
2s2 pair has no bonding characteristics; in order to make them useful for bonding, the electron
should be promoted to a higher energy level. This requires more energy than what is usually avail-
able in the bond formation.
(iii) According to Sidgwick’s theory, coordination compounds must be covalent; but their complexes are
ionic in nature. Here, the force acting in between the metal and ligand is essentially electrostatic.

Later Structural Theories of Coordination Chemistry

Based on modern principle of bonding and overcome to drawbacks of Sidgwick’s and Werner’s theo-
ries, the valence bond theory, crystal field theory and molecule orbital theories are proposed.
14.4.3 Valance Bond Theory

In 1935, Linus Pauling and Slater proposed the valence bond theory (VBT). This theory is primarily
concerned with the structure and magnetic behaviour of metal complexes. It is also called Pauling
theory.
Postulates of Valence Bond Theory

(i) The central metal makes available a number of vacant orbitals equal to its coordination number
for the formation of the covalent bond with the ligand orbital.
(ii) A covalent bond formed by the end of an overlap of a vacant orbital of metal and filled orbital
ligand leads to the formation of M-L s bond.
M L
Vacant Filled
(iii) It is also possible to form a p bond by sideways overlapping of the filled metal orbital with a suit-
able vacant ligand orbital.
M L
(iv) A strong covalent bond is formed when only the orbitals overlap to the maximum extent; this is
possible when the metal vacant orbital undergoes hybridisation.
(v) Numerous combinations of hybridisation are possible with s, p and d orbitals to give different
geometries.
Examples:
Coordination number Type of hybridisation Geometry Example

2 sp Linear [Ag(NH3)2]+
3 sp2 Triganal planar [HgI3] –
4 sp3 Tetrahedral [Ni(CO)4]
4 dsp2 Square planar [Ni(CN)4]2–
5 dsp3 Triganal bi pyramidal [Fe(CO)5]
6 d2sp3 Octahedral [Co(NH3)6]+3
7 sp3d2 Octahedral [CoF6]–4
Spin only Magnetic Moment

A species should have at least one unpaired electron to possess paramagnetic nature. It is attracted by
an external magnetic field; theoretically, the paramagnetic moment of an ion can be calculated by its
number of unpaired electron using the following spin only formula.

14.10
ms = n( n + 2)BM
Where mS = spin only magnetic moment
n = number of unpaired electrons
BM = Bohr magneton
Number of Spin only
unpaired electrons moment (BM)
1 3 = 1.73
2 8 = 2.83
3 15 = 3.87
4 24 = 4.90
5 85 = 5.92
When the species does not contain an unpaired electron, it is diamagnetic.

Depending on the number of d electrons in the metal ion, the VBT can be applied to guess the
structure of the complex.
Number of d electrons = Atomic number of central metal atom - Number of electrons lost in ion
formation - atomic number of previous inert gas.
Examples:
(i) [Ni(NH3)4]2+
Ni atomic number = 28
Number of electrons lost in +2 ion formation = 2
Atomic number of previous inert gas = 18
Number of d electrons in Ni = 28 - 2 - 18 = 8
d8 configuration
28 − 2 − 18 = 8
3d 4s 4p
NH3 NH3 NH3 NH3
sp3 hybridisation
Sp3 hybridisation - Tetrahedral structure

Two lone pair electrons - Paramagnetic
Observed magnetic moment = 2.83 BM.
(ii) [Ni(CN)4]2–
3d 4s 4p
CN CN CN CN
2
dsp
dsp2 hybridisation: square planar

No lone pair of electrons: dia magnetic
Observed magnetic moment = 0 BM.

(iii) [Co(NH3)6]+3
Co-atomic number = 27
Number of electrons lost in +3 ion formation = 3
Atomic number of previous inert gas = 18
Number of d electrons in Co = 27 - 3 - 18 = 6
d6 configuration
NH3
2 3
d sp
d2sp3 hybridisation: Octahedral
No lone pair of electrons: Dia magnetic
Observed magnetic moment = 0 BM.
Defects of Valance Bond Theory

(i) The energy level splitting of metals is not explained by the VBT.
(ii) It is unable to account or predict the relative energies of the different alternative structure for a
complex.
(iii) The reaction and mechanism of the complexes are not explained by this theory.
(iv) It does not explain why certain four coordinated complexes are tetrahedral, whereas others are
square planar.
(v) It does not indicate why certain ligands involved are in the outer orbital complex, whereas some
others form the inner orbital complex.
(vi) This theory does not account for the detailed magnetic properties.
Hybridisation Involving orbital Structure

3
sp Outer orbital Tetrahedral
dsp2 Inner orbital square planar
sp3d2 Outer orbital Octahedral
d2SP3 Inner orbital Octahedral
14.4.4 Crystal Field Theory

The crystal field theory was first proposed by J. H Van Vleck and H. Bethe. This theory involves an
electrostatic approach to bonding in complexes. It was first applied to ionic type crystalline substance.
Therefore, it is called crystal field theory.
(i) This theory is useful in describing the metal-ligand interaction and is especially helpful in
explaining the visible absorption spectra of metal complexes.
(ii) This theory considers the metal ion as being placed in an electrostatic field created by surrounding
molecules or ions.
(iii) This electric field changes the energies of the d electrons in the case transition metal ion. Many
properties of complexes are related to these energy changes. This theory considers the bonding in
complex to be entirely electrostatic.
Assumptions of the Crystal Field Theory

(i) This theory considers a complex as a combination of a central ion surrounded by other ions or mol-
ecules with electrical dipoles called ligands. It regards these ligands as point charges or point poles.

14.12
(ii) The bond between the metal and ligand is purely ionic.
(iii) The interaction between the electron of the metal cation and the ligand is entirely repulsive. These
repulsive forces are responsible for the splitting of the d orbitals of the metal ion.
(iv) In its simplest form, the crystal field theory does not consider the overlapping between the metal
orbital and ligand orbital.
(v) The d-orbital which degenerates in a free metal ion has its degeneracy destroyed by the approach
to the ligands during the formation of the complex.
Crystal Field Splitting of d-orbital in Different Geometrics

The five d-orbitals in isolated gaseous metal ions are degenerated; when a spherically symmetric field
of negative charges is placed around the central metal ion, all the five orbitals will be raised in energy
as a result of the repulsion between the negative field or negative electrons. Although they still remain
degenerated, they will have higher energy than before.
Splitting of d-orbitals in Octahedral Symmetry

(i) Six ligands participate in forming of octahedral complex. They are positioned symmetrically
along the axes of a Cartesian coordinate system with metal ion at the origin.
(ii) In the case of spherically filed, all the d-orbitals will be raised in energy relative to the free ion
due to negative charge repulsion; in these cases, not all the orbitals will be affected to the same
extent. The orbitals laying along the axes (dz2 and dx2 - y2) will be more strongly repelled than
orbital with lobes directed between the axes (dxy, dzx and dyz). The d-orbitals are thus split into
two sets with the dz2 and dx2 − y2 at a higher energy than the other three.
(iii) The orbitals are split into two sets as doubly degenerate (eg) and other is triply degenerated (t2g).
t2g - triply degenerated orbitals are dxy, dyz and dzx.
eg - doubly degenerated orbitals are dz2 and dx2 − y2.
(iv) The splitting of the five d-orbitals into eg and t2g energy levels by approaching the ligand is called
crystal field splitting. This is the major feature of the crystal field theory. The energy difference
between eg and t2g levels is denoted by ∆o or 10Dq and is called crystal field splitting energy.
Crystal Field Stabilisation Energy

The difference between t2g and eg orbitals is the crystal field stabilisation energy; it is denoted by ∆o or
10Dq. The magnitude of ∆o depends on the field strength of the ligand as well as the metal ion. It is
assumed that the sum of the energies of the five d-orbitals in the free state must be equal to the sum of the
energies of five d-orbitals in the octahedral configuration. Splitting occurs in such a way that there is no
net change in energy for the fully occupied orbital. If we consider the energy of the free state as zero, then
Edxy + Edyz + Edzx + Edx2 - y2 + Edz2 = 0 = E(d - free) (1)
∴ 3Edxy + 2Edz2 = 0 (2)
Edz2 - Edxy = 0 (3)
Multiply equation (3) by two and subtract it from equation from (2).
2 Edz2 - 2Edxy = 2∆o
5 Edxy = -2∆o
∴ Edxy = -2/5 ∆o = -0.4 ∆o (or) -4Dq (∵∆o = 10Dq)
Since t2g levels are degenerated,
Edxy = Edxz = Edyz = −0.4∆o (or) −4Dq

On substituting the value of Edxy, namely −0.4∆o in equation (3)

Edz2 - (- 0.4∆o) = ∆o
∴ Edz2 = ∆o - 0.4 ∆o = 0.6 ∆0
Since eg orbitals are degenerate
Edz2 = Edx2 - y2 = 0.6 ∆o (or) 6Dq
This means that presence of an electron in the t2g level will stabilise the complex to the extent ‘0.4 ∆o’.
This stabilisation energyis called “crystal filed stabilisation energy”. The presence of electron in eg
level will destabilise the complex to the extent of 0.6 ∆o.
Splitting of d-orbitals in Tetrahedral Symmetry

The metal ion along with its d-orbitals are arranged in the centre of the cube, the ligands occupy
alternatively in four corners of the cube. Here, two ligands are in the top face of the cube and other
two are in the bottom face but none of the ligand approaches the metal along the Cartesian coordinate
axes. Hence, the orbitals along the axes (dz2, dx2 - y2) will be less strongly repelled than those orbitals
between the axes (dxz, dxy and dyz). With this, the previously degenerate set of five orbitals is now split
into two sets, one at a higher energy and one at lower energy. The higher energy set of orbitals (dxy, dyz
and dzx) is labelled as t2 and the lower energy set (dz2 and dx2 - y2) is labelled as e. (The subscript “g”
disappears here because the tetrahedron lacks the centre of inversion). The energy separation between
the two levels is denoted by ∆t (or) 10 Dq.
The crystal field splitting in the tetrahedral field is intrinsically smaller than the octahedral field because
there are only four ligands surrounded to the metal, but none of them have a direct effect on the d-orbital.
The relationship between the two crystal field separation energies may be represented as ∆t = 4/9∆o.
The tetrahedral geometry can occur with the following reasons:
(i) When ligands are too large, less ligand repulsion occurs.
(ii) When metal ion with zero crystal field stabilisation energy (CFSE), that is, metal atom having the
d0, d5 and d10 electronic configuration or small CFSE—d2 and d7 electronic configuration.
Example: MnO 4− (d0), FeCl 4− (d5 high spin) COCl2 (d7 high spin), ZnCl 2− 10
4 (d )
Splitting of d-orbitals in Square Planarl Symmetry

This is the special case of octahedral symmetry; the removal of two ligands from z-direction completely
in octahedral symmetry leads to square planar geometry. The geometry is favoured by the metal ion
having a d8 configuration in the presence of a strong field. This combination gives low spin complexes
where the first four orbitals are occupied and the high energy dx2 − y2 orbitals are unoccupied.
dx 2−y 2
dxz−y 2 b1g
t2 eg ∆
2/5 ∆t dz 2
dxy
b1g
dz 2
dxy
3/5 ∆t a1g
e t2g
dxz dyz dxy dyz
eg
Tetra hedral Square planar

14.14
dx −y 2
dx 2−y 2
∆
eg
t2
dxy
dz 2
∆0
∆t ∆2
In the pres dxy ∆sp
-ence of sphe dz 2
e -rically symm
-etric negative t2g
feild hypotheti dxz dyz ∆3
-cal one free
isolated dxy dyz
gaseous ion
E A B C D
Tetrahedral complex Octahedral complex Distoraded octa Square planar
∆t = 4/9 ∆0 hedral complex complex
(or) ∆sp≈1.3 ∆0
Tetra hedral
In octahedral symmetry, ligands approach along the axes.

In tetrahedral symmetry, ligands approach in between the axes.
In square planar symmetry, ligands approach towards X and Y axes.
Merits of Crystal Field Theory

(i) This theory predicts the most favourable geometry of complex.
(ii) It also accounts for the fact certain four coordinated complexes are square planar, whereas the
outer ones are tetrahedral.
(iii) It also explains that certain ligands form the outer orbital octahedral complexes, whereas others
form the inner orbital octahedral complexes. They, in turn, correspond to high spin and low spin
complexes.
(iv) This theory is successful in interpreting the magnetic properties taking into orbital contribution
as well.
(v) This theory represents the colour of transition of metal complexes.
(vi) It also explained the spectral properties of metal complexes.
Limitations of Crystal Field Theory

(i) In several complexes, the bonding strength and chemical properties cannot be solely explained
on the basis of electrostatic attraction as emphasised by this theory.
(ii) This theory fails to explain the relative strength of ligand.
14.4.5 Common Single Atomic Ligands and their Field Strength

According to field strength, the single atomic ligands are arranged in Table 14.9 from weak field to
strong field. When weak ligand approaches the metal, outer orbitals of the metal are involved in hybrid-
ization, that is, high spin complexes (6 coordinated complexes –sp3d2, 4 coordinated complexes –sp3).
When strong ligand approaches the metal, inner orbitals of the metal are involved in hybridization, that
is, low spin complexes (6 coordinated complexes –d2sp3, 4 coordinated complexes –dsp2).

Table 14.9 Single atomic ligands and their bonding capacity from weak field to strong field
Ligand Formula of ligand Charge Bonding capacity Remark(s)
Iodide (iodo) I− Monoanionic Monodentate –
Bromide (bromido) Br− Monoanionic Monodentate –
Sulfide (thio or less S2− Dianionic Monodentate –
commonly “bridging (M S), or bidentate
thiolate”) bridging (M−S−M′)
Thiocyanate S CN− Monoanionic Monodentate Ambidentate
(S-thiocyanato)
Chloride (chlorido) Cl− Monoanionic Monodentate Also found in bridging
Nitrate (nitrato) O NO Monoanionic Monodentate –
Azide (azido) N N Monoanionic Monodentate –
Fluoride (fluoro) F− Monoanionic Monodentate –
Hydroxide (hydroxo) O H− Monoanionic Monodentate Often found as a
bridging ligand
Oxalate (oxalato) [O CO CO O]2− Dianionic Bidentate –
Water (aqua) O H2 Neutral Monodentate –
Nitrite (nitrito) O N O− Monoanionic Monodentate Ambidentate
Isothiocyanate N C S− Monoanionic Monodentate Ambidentate
(isothiocyanato)
Acetonitrile CH3CN Neutral Monodentate –
(acetonitrilo)
Pyridine C5H5N Neutral Monodentate –
Ammonia (ammine NH3 Neutral Monodentate –
or less commonly
“ammino”)
Ethylenediamine (en) NH2 CH2 CH2 Neutral Bidentate –
NH2
2,2′-Bipyridine NC5H4 C5H4N Neutral Bidentate Easily reduced to
(bipy) its radical/ anion or
even to its dianion
1,10-Phenanthro- C12H8N2 Neutral Bidentate –
line (phen)
Nitrite (nitro) NO2 Monoanionic Monodentate Ambidentate
Triphenylphosphine P (C6H5)3 Neutral Monodentate –
Cyanide (cyano) C N− Monoanionic Monodentate Can bridge between
N C− metals when both
metals bound to Car-
bon, or one to Carbon
and one to Nitrogen
Carbon monoxide CO Neutral Monodentate Can bridge between
(carbonyl) metals when both
metals bound to
Carbon
The entries in the table are sorted by field strength directly binding through the stated atom, that is,
as a terminal ligand. The ‘strength’ of the ligand may change when the ligand binds in an alternative
binding mode as follows:
(i) When it bridges between metals;
(ii) When a linear ligand that is forced through steric interactions to bind in a nonlinear fashion, the
conformation of the ligand gets distorted.

14.16
14.4.6 Molecular Orbital Theory of Coordination Complexes

Molecular orbital theory was proposed by Pauling; it explains mainly magnetic properties, bond
strength or bond order, bond length and the covalent character of metal and ligand.
For example, [Co(NH3)6]+3 is a complex in which metal and ligand s -bonding are involved.
This complex contains NH3 ligand which can only participate as a s donor to the metal ion. Now,
construct the molecular orbital diagram for octahedral complex.
Let us consider the metal orbitals. The valance orbitals available are 3d, 4s and 4p. A total of nine
orbitals are available and these orbitals are suitable to be used in s bonding. This means that the orbit-
als that we can use should have their lobes pointed along axes. Obviously, 4s orbitals are quite suitable.
This called a1g. All 4p orbitals are also suitable. These are labelled as t1u. Now, let us inspect the 3d
orbitals; only two of them are suitable. The orbitals dx2 − y2 and dz2 are suitable since they have the
lobes along the axes. These are labelled as eg; however, the orbitals dxz, dyz and dxy are not suitable.
Since the ligand orbitals cannot overlap with them to give a positive overlap, this cannot be utilised by
the metal for s bonding. These remain non-bonding and are labelled as t2g.
Thus, a valance orbital of the metal six is suitable for forming s -bonding (a1g, t1u, eg); three are
non-bonding orbitals (t2g).
Let us assume that by linear combination of the ligand orbitals, we are able to generate six orbitals
of symmetry, called ligand group orbital as that of the six metal bonding orbitals. These orbitals on the
metal and the ligand combine.
Salient Features of the Molecular Orbital Diagram can be Summarised as Follows:

(i) The lower energy orbitals a1g, t1u, eg are closer in energy to the ligand orbitals.
(ii) The t2g orbital remains non-bonding. Their energy is not changed after forming the metal orbitals.
(iii) The higher energy orbitals a1g*, t1u*, eg* are closer in energy to the metal orbital.
(iv) The energy separation between non-bonding and the eg* orbitals represent the ∆0 of the crystal
field diagram.
(v) If this separation is large, low spin complexes are formed; if the separation is small, high spin
complexes are formed.
Thus, [CO (NH3)6]3+ [CO has 6 electrons, 6 NH3 ligands have 12 electrons] thus electronic con-
figuration a1g2, t1u6, eg4, t2g6. In contrast, [CO F6]3- has the electronic configuration a1g2 t1u6 eg4,
t2g4, eg*2
z z
y y
x x
4s 4p
3d
z z
y y
x x
z z z
y y y
x x x
z
y t2g set
x
3d
z z
y y
x x
z z z
y y y Coordination Chemistry 14.17

x x x
z
y t2g set
x
eg set z z
y y
x x
dx2–y2 dz2
MO diagram for octahedral complex

Metal complex ligand
∗
t1u
t1u
4p Anti bonding
∗
a1g
a1g
4s
∗
eg LUMO
∗ ∆o Non bonding
eg t2g t2g
3d
Homo
eg eg
t1u
t1u a1g
Bonding
a1g
14.5 F
ACTORS AFFECTING THE STABILITY OF COORDINATION
COMPOUNDS
It is not possible to conclude a particular ligand or particular metal complexes of high or low stability.
No single factor is expected to account for the relative stability of coordination compounds. They are
affected many physical and chemical properties as discussed here.
Charge of the Metal Complex

The complex formation is essential a reaction between cation (metal ion) and ligand. The charge on
metal ion is more important to deciding the stability of metal complex. Greater the positive oxidation
state of the central metal ion greater will be the attraction for the ligand; hence, greater will be the
stability of the complex with same ligand. When metal ion is in a more oxidation state, that complex is
more stable when compared to low oxidation metal complex.

14.18
Size of the Central Metal Ion

Keeping the charge constant as the size of the metal ion decreases, the specific charge per unit surface
area increases. Hence, the metal attraction for the ligand increases. Generally, the size of the metal
decreases and the stability of metal complex increases.
Outer Electronic Configuration

We compare the stability of complexes formed by similarly charged and sized metal ions belong-
ing to two subgroups of the same periodic family. This stability is explained by outer electronic
configuration.
Exmaple: K+ and Cu+ potassium are non-transition elements, whereas copper is a transition
metal. Cations of d-block elements are invariably far more stable complex than non-transition metal
complexes.
Potassium has inert gas configuration (n - 1) s2p6 in the outer shell, whereas copper has pseudo-
inert gas configuration (n - 1) s2p6 d10 in the outermost shell. It is a well-known fact that the latter
configuration is much poorer in shielding the excess positive charge is located on the nucleus then the
formed configuration. Hence effective nuclear charge on copper is more than potassium, that is copper
will behave as a greater nuclear charge. Therefore, Cu+ has greater attraction for electrons offered by
the ligands. Consequently, copper form more stable complex than potassium
Nature of the Ligand Atom

The complexes formed by halide ion have been widely studied for metals the order of stabilities as it
follows the sequence F−>Cl−>Br−>I−. However, this order is reversed for a few metals like Pt+2, Cu+,
Ag+, Hg+2 and Ti+ where back donation occurs from metal to ligand occur in the donation to the transfer
of electron from ligand to the metal. For this back donation from metal to ligand to occur, the ligand
must possess a vacant orbital capable of receiving electrons.
Basicity of Ligand
Basicity is a measure of electron pair donation; greater the basicity of ligand, greater will be the
tendency to donate electron pairs. This means that a more basic ligand will form more stable
complex.
Chelating Ability of the Ligand

The stabilities of complexes are increased by the coordination of the ploy dentate ligand. Coordination
of such ligands produces a ring structure with the metal atom forming a part of the ring system. Such
ring structure complexes are called chelates. This process of chelate formation is called chelation. The
ligand that forms a chelate is called a chelating agent. Due to chelation, extra stability is conferred on
the complex. This extra stability is termed as the chelating effect.
Number of Chelating Rings

Greater the number of chelate rings, greater will be the stability of complex. Some other factors are as
follows:

(i) Size of chelate ring

(ii) Steric effect
(iii) Stereo chemical requirement of ligands
14.6 DETErmination OF COMPLEX ION FORMATION

Many methods are used to confirm the formation of complex compounds in a reaction as discussed
here.
Formation of Precipitate
When a neural covalent complex is formed in a polar medium, it gets precipitated. The formation of the
precipitate on the addition of a ligand indicates the formation of a neural covalent complex.
Example:
Ni+2 + 2HDMG→[Ni(DMG) 2] ↓ + 2H+ (PH > 8]
(Protonated (Dimethyl
dimethyl glyoxime)
glyoxime)
Al+3 + 3CH3 CO CH2 CO CH3 + 3OH−→ [Al(CH3 CO CHCO CH3)3)] ↓ + 3H2O
Change in Chemical Behaviour

The altered reactivity of the metal ions in the presence of the ligands is still a useful indication of
complex formation.
Example: Fe+3 is not precipitated as Fe(OH)3 by NH4OH in the presence of tartaric acid. This indi-
cates the formation of Fe3+ tartrate complex.
Dissolution of an Insoluble Compound in the Presence of Complexing Agents

Many water insoluble substances dissolve readily in the presence of a reagent that forms a soluble
complex.
Example: Dissolution of AgCl in aqueous ammonia indicates the formation of soluble complex
[Ag(NH3)2]Cl.
AgCl + 2NH3→ [Ag(NH3)2]Cl
Insoluble soluble
Colour Change in Solution (Spectral Method)

A colour change of the solution with the addition of another reagent indicates the formation of a new
species. In many cases, the colour of the uncomplex metal ion gets altered and in some cases, a totally
new colour is produced.
Example: Co2+ + 4Cl–→[CoCl4]2–
pink blue
Cu+2 + 4Cl–→[CuCl4]2–
light blue green

14.20
pH Method
The addition of the ligand to metal in solution complex is formed by the releasing of protons.
Example: Cu+2 ion is treated with salicylaldoxime to form the complex [Cu(sal)2] with the release
of protons.
Cu2+ + 2 Hsal→ [Cu(sal) 2] + 2H+
Conductivity Measurement
If the complex formation reaction involves a change in the number of ions, then there would be changes
in the conductivity of the solution. The change in conductance can be used to detect the complex
formation.
14.7 STABILITY OF COORDINATION COMPOUNDS

The subject of stability of metal complexes is important in understanding the properties of complexes.
Many variables associated with the central metal ion and the ligand are greatly complicated. There are
two types of stability—thermodynamic stability and kinetic stability.
Thermodynamic Stability
This measures the extent of the complex formed or transformed into another species by metal ligand
bond energy stability constant when system reached equilibrium.
Kinetic Stability
This refers to the speed of the reaction with transformation, leading to attainment of equilibrium.
Thermodynamic Stability and Kinetic Stability

The thermodynamic stability of a complex depends upon the difference in energy between the reac-
tants and the products; greater the reaction energy, greater the thermodynamic stability.
The kinetic stability of the complex depends on the difference in energy between the reactants and
the activated complex, that is, activation energy. Greater the activation energy, lesser the reaction rate,
implying that the complex is inert.
If the term “stability” is used without any modification, then
y Activated complex it refers to thermodynamic stability.
In thermodynamic point of view, metal-to-ligand bond
energies, stability constant and the thermodynamic variables
Activation energy
derivable from them from being stable or unstable have to be
Energy
Reactant
considered.
Reaction energy
In kinetic stability, the rates and the mechanism of
Product reactions and also with the energies involved in the forma-
tion of the activated complex have to be considered. In the
kinetic point of view, it will be more proper to speak of com-
Reaction co-ordinates x
plex as being inert or labile rather than stable or unstable.

Very often, these two groups of terms are used in correctly. A stable complex may be inert or labile and
an unstable complex may be labile or inert.
Example: CN–ion forms a very stable complex with Ni+2
[Ni(H2O)6]2+ + 4CN–→ [Ni(CN)4]2– + 6H2O
Ni+2 prefers CN– rather than H2O as a ligand. Thus, [Ni(CN)4]2– is thermodynamically more stable than
[Ni(H2O)6]2+. However, when “14C-labelled” CN– (14CN–)is added to the solution, it is almost instanta-
neously incorporated into complex.
[Ni(CN)4]2– + 414CN−→ [Ni(14CN)4]2– + 4CN–
This means that the complex, [Ni(CN)4]2–is kinetically labile. Thus the stability of complex of this does
not ensure inertness.
The Method of Continuous Variation

This method is used for solution where only one complex is formed.
Determination of Composition of Complex by Job’s Method

The sum of the total concentration C of a complexing agent Cx and metal ion CM is held constant and
only their ratio is varied.
CM + Cx= C
A wavelength of light is selected such that where the complex absorbs strongly with metal and ligand
but not individually.
A plot of the mole fraction of the ligand in the mixture x versus y
absorbance gives a triangular curve.
The mole fraction of the ligand in the mixture x = Cx/C
Absorbance
The mole fraction of the metal in the mixture = CM /C

Cx/C + CM /C = C/C ∵CX + CM = C
∴ 1 - x = CM /C
The legs of the triangle are extrapolated until they cross. The mole frac-
tion at the point of this intersection gives the formula of complex, since at Mole fraction x
this point, for the complex Mxn is
n = Cx/CM = x/1 - x
At this point, the ligand and the metal are in the proper relative concentration to give maximum com-
plex formation. Performing the experiment at several different wavelengths at several different values
of C would indicate whether there is more than one complex formed in the solution. In such cases,
n would not be constant.
The curve may be observed to deviate somewhat from the experiment intersecting lines from the
amount of derivation and the stability of constant of the complex can be determined.

14.22
Determination of Stability Constant

For 1:1 complex, the ratio of the true absorbance (A) to the extrapolated absorbance (AExt) is the mole
fraction of the complex actually formed.
A [Mx ]
=
AExt C
Where C = Total concentration of the metal (or) ligand, whichever is the limiting concentration at the
point considered.
Then [Mx] = (A/AExt)C
[M] = CM - [Mx]
= CM - [A/AExt)C
[x] = Cx - [Mx]
= Cx - (A/AExt)C
[MX] ( A/AExt )C
Therefore K = =
[M][X] [C M − (A/AExt )C ][C X − ( A/AExt )C ]
Where K is the stability constant and CM and Cx are the total concentration of metal and ligand
respectively.
14.8 APPLICATIONS OF COORDINATION COMPOUNDS

Coordination compounds are used in several areas of chemistry such as analytical, medicinal, indus-
trial chemistry and agriculture.
Metal Complexes in Analytical Chemistry

Inorganic Qualitative Analysis
Coordination chemistry is used in inorganic qualitative analysis. The formation of metal complex is
employed in the separation and identification of some metals.
Separation
The principle of masking is used in separationof some metals from each other on qualitative analysis.
Example: Cu+2 and Cd 2+ forms insoluble sulphide in the II group. These two metals are separated
by complexing them with CN–. Both form complexes but with a difference.
2CuS + 8 CN–→2 [Cu(CN)4]3– + S22–
Tetra cyano cuprate (III)
CdS + 4CN → [Cd(CN)4]2 + S22–

–
Cadmium Tetra cyano cadmium (II)

Sulphide
The reaction of CN– with CuS is an oxidation reduction reaction coupled with complexation. In both
complexes, Cu complex is stable and Cd complex is unstable. The marked difference in the stabilities
of copper and cadmium cyano complexes is the basis for separating these two metals.

Reductive Complexation
When a ligand reduces a metal of the complexes, the process is called reductive complexation.
Identification of Metals
Complex formation is used to identify several metals in qualitative analysis.
Complexometric Titration
Certain metal ion reacts with certain ligand stoichiometrically and forms stable metal complexes. This
reaction can be used to in volumetric estimation of metal ions.
Example: determination of hardness of water.
Hard water is titrated with EDTA ligand; water containing metals Ca and Mg will form complex
with EDTA. From the end point, hardness giving substances present in water can be determine.
Complex in Calorimeter
Some of the metals can be calorimetrically estimated by the formation of coloured complex species in
solution.
Coordination Compounds in Gravimetry

The formation of coordination compounds serves as an excellent means for gravimetrically estimating
certain metals.
Complexes in Separation of Metals

Some chelating agents are used for separating certain metallic mixtures.

1. The formation of coordination compound from metal ion is called
[Ans.: Complexation]
2. Fe2(SO4)3(NH4)2SO4.24H2O is a
[Ans.: Double salt]
3. The number of mono dentate ligands attached to metal ion indicates
[Ans.: Coordination number]
4. Oxidation number of ‘Ni’ in [NiCl4] −2 complex is
[Ans.: +2]
5. R3N, CO, H2O belongs to ligands.
[Ans.: Unidentate]

14.24
Cl
6. Pt Pt Here, complex Cl belongs to type of ligand.
Cl
[Ans.: Bridging]
7. The suffix “ate” is added to
[Ans.: Complex anion]
8. In Werner’s theory, coordination number represents valence.
[Ans.: Secondary]
9. According to Werner’s theory, the bond between ligand and metal
[Ans.: Coordinate bond or dative bond]
10. The effective atomic number of [V(CO) 6] is
[Ans.: 31]
11. Does [Mn(CN) 4] complex obey the EAN rule?
[Ans.: No]
12. theory proposed EAN.
[Ans.: Sidgwick]
13. Who proposed valence bond theory?
[Ans.: Linus Pauling and Slater]
14. On which basis is the shape of complexes explained in the valence bond theory?
[Ans.: Hybridisation]
15. Square planar complexes exhibiting hybridisation is
[Ans.: dsp2]
16. Sp hybridisation involving complexes geometry is
[Ans.: Linear]
17. Spin only moment is explained by theory
[Ans.: Valence bond]
18. J. H. Van Vleck and Bethe proposed
[Ans.: Crystal field theory]
19. According to crystal field theory, the bond between metal and ligand is
[Ans.: Electrostatic attraction]
20. Splitting of d-orbitals into and egis known as crystal field splitting of d-orbitals.
[Ans.: t2g]
21. Triply degenerate orbitals are and are designated with
[Ans.: dxy, dyz, dzy, t2g]

22. orbitals doubly degenerate orbitals and its representation is eg.

[Ans.: dx −y and dz2]
2 2
23. The energy difference between t2g and eg levels is denoted by and is called
energy.
[Ans.: ∆0 (or) 10Dq, crystal field splitting]
24. In octahedral complexes, orbitals have lesser energy than eg in excited state.
[Ans.: t2g]

1. In coordination complexes which of the following donates the electrons?
(a) Metal (b) Ligand
(c) Both (a) and b (d) None of these
[Ans.: b]
2. The compound formed by addition of two stable compound and on dilution that forms complete
ions is called
(a) Double salt (b) Triple salt
(c) Coordination compound (d) Covalent compounds
[Ans.: a]
3. What is the correct name of the given complex [Cu Cl2(NO2)3]−3?
(a) Trinitrondichlorocopper(III)ion (b) Dichlorotrinitrocuprate(III)ion
(c) Dichlorotrinitrocopper(III)ion (d) Trinitrodichlorocuprate(III)ion
[Ans.: b]
4. Which of the following is a bidentate ligand?
(a) Cl− (b) EDTA
(c) Triethyl triamine (d) Oxalate
[Ans.: d]
5. Which of the following is a neutra ligand?
(a) Cl− (b) NH2 NH3+
(c) CO (d) None of these
[Ans.: c]
6. Which ligand behaves as an isomeric ligand?
(a) M NO2 (b) M Cl
(c) [M EDTA] (d) [M (NH3)6]
[Ans.: a]
7. In Werner’s theory, primary valence represents
(a) Oxidation number
(b) Coordination number
(c) Both a and b
(d) None of these
[Ans.: a]

14.26
8. EAN is explained by

(a) Werner (b) Sidgwick
(c) Linus Pauling and Slater (d) J. H. Van Vleck and Bethe
[Ans.: b]
9. Crystal field theory is proposed by
(a) J.H. Van Vleck and Bethe (b) Werner
(c) Sidgwick (d) Linus Pauling and Slater
[Ans.: a]
10. According to crystal field theory, d-d splitting in octahedral complexes
(a) t2g →eg (b) eg→ t2g
(c) T2 → E (d) E → T2
[Ans.: a]
11. What are the d-orbitals that belong in t2g state?
(a) dxydyzdzx (b) dx2 − y2 (c) dz2
(d) dx2 − y2 and dz2
[Ans.: a]
12. Which orbitals are double degenerated?
(a) dxy, dyz (b) dxz, dz2
(c) dx2 − y2, dz2 (d) dx2 − y2 and dxy
[Ans.: c]
13. Spin only formula µ =
(a) n( n + 2) BM (b) ( n + 2) BM
(c) ( n +1) BM (d) n( n +1) BM
[Ans.: a]
14. Crystal field stabilisation energy for t2g orbital in octahedral complexes is
(a) − 0.4 ∆0 (b) 0.6 ∆0
(c) − 0.6 ∆0 (d) 0.4 ∆0
[Ans.: a]
15. The presence of electrons in t2g (or) eg level will stabilise the complex is called
(a) Crystal field stabilisation energy (b) Crystal field splitting of d-orbital
(c) Crystal field theory (d) None of these
[Ans.: a]
16. The method used to detect the stability of metal complexes is
(a) PH method (b) Job method
(c) Titration method (d) None of these
[Ans.: b]
17. In potassium and copper complexes, a form of stable complex is
(a) Potassium (b) Copper
[Ans.: b]


1. Define coordination compound.
Ans.: Compound of metals with certain number of species called ligands bound to the metal is
called coordination compound.
2. Differentiate double salt and coordination compound.
Ans.: Double salt:
Double salt is formed by the adding of two stable compounds; on dissolution, it breaks
down to its simple component ions.
Coordination compounds:
On dissolution, it does not break down into simple ions.
3. What is meant by coordination number and oxidation state?
Ans.: The total number of ligands attached to metal complex is called coordination number.
The charge on the complex will be denotes the oxidation state.
4. Write the different types of ligands.
Ans.: (i) Monodentate
(ii) Polydentate
(iii) Bridging ligand
(iv) Ambidentate ligand
(v) Flexidentate ligand
5. Give the names of the following complexes:
(i) [Cr(NH3)6]+3
(ii) [PtCl2(H2O)(NH2NH3)]+2
(iii) [CrCl3(NO2)3]3−
(iv) [Cu(en)2]SO4
Ans.: (i) Hexaaminechromium(III)ion.
(ii) Dichloroaquahydrazoniumplatinum(II)ion.
(iii) Trichlorotrinitrochromate(III)ion.
(iv) Biethylenediaminecopper(II)sulphate.
6. Write the different theories of coordination chemistry.
Ans.: (i) Werner’s theory
(ii) Sidgwick theory
(iii) Valence bond theory
(iv) Crystal field theory
(v) Molecular orbital theory
7. Write the postulates and drawbacks on Werner’s theory.
Ans.: It explains the elements exhibit two types of valence as follows:
(i) Primary valence
(ii) Secondary valence
Drawbacks:
It is unable to account the 4-coordinated and 6-coordinated complex in coordination chemistry.
It does not explain the nature of bonding between metal and ligand.

14.28
8. Explain effective atomic number.

Ans.: According to Sidgwick, the total electrons around the metal ion including those gained
through the coordination by the ligand is called effective atomic number (EAN).
EAN is equal to the atomic number of the next inert gas atomic number such that metal
complexes are stable.
9. Explain valence bond theory.
Ans.: In 1935, Pauling and Slater proposed this theory. This theory explains the magnetic prop-
erties and structure of the metal complexes.
10. Explain crystal field theories and their merits and demerits.
Ans.: This theory was explained by J.H. Van Vleck and Bethe. It was first applied by crystalline
substances and on this basis, it was called crystal field theory.
Merits:
(a) It is successful in interpreting the magnetic properties
(b) It explains the colour of complexes.
(c) It gives detailed information about tetrahedral and square planar geometrics of 4 coordinated
complexes.
(d) It is also explains spectral properties of complex.
Demerits:
Bond strength chemical properties cannot be explained.
11. Write any two factors affecting the stability of metal complexes?
Ans.: (i) Charge of the metal complex: Greater the charge on metal greater will be the stability
of complexes.
(ii) Size of the metal ion: Size decreases the stability of metal complexes increases.
12. Write the methods of detection of complexes.
Ans.: (i) Formation of precipitate
(ii) Change in chemical behaviour
(iii) Spectral method
(iv) pH method
(v) Conductivity measurements

Q.1 Write a note on the characteristics of coordination compound.
Q.2 Explain the difference between double salt and coordination compound.
Q.3 Explain the following terms:
(a) Coordination number
(b) Complex ion
(c) Oxidation number
(d) Ligands
Q.4 Define ligand. Explain the types of ligands with examples.
Q.5 Describe the nomenclature of coordination compounds in detail.

Q.6 Write a detailed note on any two theories of coordination chemistry?

Q.7 Write a short note on crystal field stabilisation energy and splitting of d-orbital in crystal field
theory.
Q.8 Explain the factors affecting coordination compounds.
Q.9 Give a brief explanation on the detection of complex ion formation.
Q.10 Explain stability of coordination compounds.
Q.11 Describe Job’s method.
Q.12 Give the application of coordination complexes in analytical chemistry.

STRUCTURE AND
15 REACTIVITY OF
ORGANIC AND
INORGANIC
MOLECULES
15.1 INTRODUCTION
By transferring or sharing electrons, a bond is formed between the atoms. The covalent bond plays a
vital role in the formation of many organic molecules. A covalent bond is formed with the sharing of
electrons between two atoms; it is mainly s-bond
s and p
p- bond.
r -bond
A sigma bond is formed with end-to-end overlap of orbitals.
o -bond
A p bond is formed with a partial or a side-wise overlap of orbitals.
15.2 HYBRIDISATION
Hybridisation is defined as the “hypothetical intermixing of nearly the same energy [of] atomic orbitals
to give [an] entirely new identical equal energy orbitals”.
It is also defi ned as,
“Combining of atomic orbitals have different energies or nearly the same energy and the formation
of a new set of orbitals with equivalent energy and shape”. They are known as hybrid orbital and the
phenomenon is known as hybridisation.
15.2.1 Salient Features of Hybridisation

In hybridisation, only orbitals combine; electrons do not combine. The number of hybrid orbit-
als formed is exactly equal to the number of atomic orbitals that participated in hybridisation.
Only similar energy orbitals can combine and form a hybrid orbital. The formed hybrid orbitals are

15.2
equivalent in energy and shape. Hybrid orbitals can form strong bonds that lead to the formation of
more stable molecules. They are directed in space so as to have minimum repulsion between electron
pairs.
15.2.2 Important Conditions for Hybridisation

The orbitals undergoing hybridisation should have comparable/nearly the same level of energy. The
promotion of an electron is not an essential condition prior to hybridisation. Half-filled or completely
filled orbitals can participate in the process.
15.2.3 Types of Hybridisation

There are various types of hybridisation that occur between s, p and d orbitals. Depending on the type
of atomic orbitals involved in the process, there are sp, sp2, sp3, sp3d and sp3d2 hybridisation. The shape
and bond angles of the molecule depend on the type of hybridisation.
sp Hybridisation
Combining one s and one p orbital and the formation of two equivalent sp hybrid orbitals is known as
sp hybridisation. Each sp hybrid orbital has 50% s character and 50% p character. With sp hybridisa-
tion, the molecule possesses linear geometry.
sp hybridisation is also known as diagonal hybridisation. The two sp hybrid orbitals point in the
opposite direction along the axis with projecting positive lobes and very small negative lobes which
provide more effective overlapping, resulting in the formation of stronger bonds.
Example: Formation of beryllium chloride (BeCl2)
Beryllium: ground state electronic configuration – 1s2 2s2
Excited state electronic configuration – 1s2 2s1 2p1
One 2s and one 2p orbitals of beryllium combine to form two equal sp hybrid orbitals. These
two sp hybrid orbitals are oriented in the opposite direction, forming an angle of 180°. Each sp hybrid
orbital overlaps with the 3p orbital of chlorine axially and forms two Be Cl sigma bonds. The shape
of this molecule is linear, and the bond angle is 180°.
1s 2 2s1 2p1 σ σ
Cl Be Cl
+ + + +
180° Cl Be Cl
sp
sp2 Hybridisation
Combining one s and two p orbitals and the formation of three equivalent sp2 hybrid orbitals is known
as sp2 hybridisation. Each sp2 hybrid orbitals has 33.3% s character and 66.6% p character. With sp2
hybridisation, the molecule possesses trigonal planar geometry. The bond angle between each sp2
hybrid orbital is 120°C.
Example: Formation of boron chloride (BCl3)
Boron – ground state electronic configuration – 1s2 2s2 2p1
Excited state electronic configuration – 1s2 2s1 2px1 2py1 2pz0
One 2s and two 2p orbitals of boron combine to form three equal sp2 hybrid orbitals.

Structure and Reactivity of Organic and Inorganic Molecules 15.3
+
1s 2 2s1 2p 2 F F σ
+
B 120° σ
σ + + +
sp 2 F +
BCl3
sp3 Hybridisation
Combining one s and three p orbitals and the formation of four equivalent sp3 hybrid orbitals is known
as sp3 hybridisation. Each sp3 hybrid orbital has 25% s character and 75% p character. With sp3 hybridi-
sation, the molecule possesses tetrahedron geometry. The bond angle between each sp3 hybrid orbital
is 109°281.
Example: CH4, NH3, H2O.
Formation of Methane (CH4)

Carbon – ground state electronic configuration – 1s2 2s2 2px1 2py1 2pz0
Excited state electronic configuration – 1s2 2s1 2px1 2py1 2pz1
H
H
1s 2 2s1 2p3
109°.281 C
C
H H
sp3 H H
H
H
In NH3 and H2O, the molecules are involved in sp3 hybridisation. However, they cannot exhibit tetra-
hedral structure and the bond angle also varies.
Formation of Ammonia (NH3)

Nitrogen – ground state electronic configuration – 1s2 2s2 2px1 2py1 2pz1
In ground state, nitrogen undergoes sp3 hybridisation with one 2s orbital containing two electrons
and three 2p orbitals containing one electron each. In these four sp3 hybrid orbitals, three hybrid orbit-
als have unpaired electrons and one hybrid orbital has a lone pair of electrons on the central metal
atom. By these lone pair electrons, repulsion occurs between the lone pair and the bond pair. Due to
this repulsion, the geometry of the molecule changes from tetrahedral to pyramidal structure, and the
bond angle also varies from 109° 281 to 107° 51.
N
H H H
107.5°
pyramidal

15.4
Formation of Water (H2O)

Oxygen–ground state electronic configuration – 1s2 2s2 2px2 2py1 2pz1
In ground state, oxygen undergoes sp3 hybridisation with one 2s orbital containing two electrons
and three 2p orbitals; among three p orbitals, one contains a lone pair and another two contain one
electron each. In these four sp3 hybrid orbitals, two hybrid orbitals have unpaired electrons and two
hybrid orbital have a lone pair of electrons on the central atom. In these lone pair of electrons, repulsion
occurs between the lone pair and the bond pair. Due to this repulsion, the geometry of the molecule
changes from tetrahedral to a v-shaped structure, and the bond angle also varies from 109° 281 to 104°.
O
H H
104.5°
V-shaped
Hybridisation Involving d Orbitals

In addition to s and p orbitals, the elements present in the third period contain the d orbital. The energy
of 3d orbitals is comparable to the energy of the 3s, 3p and 4s, 4p orbital. Therefore, hybridisation may
involve 3s, 3p and 3d or 4s, 3d and 4p. Due to energy differences, there is no possibility of hybridisation
involving 4s, 3d and 3p.
sp3d Hybridisation
Combining one s, three p and one d orbital and the formation of five equivalent sp3d hybrid orbitals
is known as sp3d hybridisation. With sp3d hybridisation, the molecule possesses trigonal bipyramidal
geometry. The bond angles are 90° and 120°.
Example: PF5, PCl5.
Formation of Phosphorous Pentachloride

Phosphorous – ground state electronic configuration – 1s2 2s2 2p6 3s2 3px1 3py1 3pz1 3d0
Excited state outer shell electronic configuration – 3s1 3px1 3py1 3pz1 3d1
Cl
Cl
3s1 3p3 3d 1 P Cl
Cl
sp3d Cl
sp3d2 Hybridisation
Combining one s, three p and two d orbital and the formation of six equivalent sp3d2 hybrid orbitals
is known as sp3d2 hybridisation. With sp3d2 hybridisation, the molecule possesses a square pyramidal
(BF6) and octahedral (SF6) geometry.
Formation of Sulphur Hexafluoride

Sulphur – ground state electronic configuration – 1s2 2s2 2p6 3s2 3px2 3py1 3pz1 3d0

Excited state outer shell electronic configuration – 3s1 3px1 3py1 3pz1 3d 2
F
F F
3s1 3p 3 3d 2
S
F F
sp3d 2 F
Its geometry is octahedral and the bond angle is 90°.
dsp2 Hybridisation
Combining one d, one s and two p orbitals and the formation of four equivalent dsp2 hybrid orbit-
als is known as dsp2 hybridisation. With dsp2 hybridisation, the molecule possesses a square planar
geometry.
Example: [Ni(CN)4]−2, [Pt(Cl)4]−2
−2 −2
Cl Cl Cl Cl
Ni Pt
Cl Cl Cl Cl
15.3 BOND POLARISATION

The reaction of organic compounds essentially involves changes in the existing covalent bond present
in their molecules. These changes may involve “electronic displacement in the bonds, breaking of
bonds, energy changes accompanying the cleavage and formation of new bonds”.
To clearly understand the mechanism of various reactions, it is essential to know electron displace-
ment in covalent bonds, cleavage of covalent bonds and the nature of attacking reagents.
15.3.1 Electron Displacement in Covalent Bonds

The electronic displacement in covalent bonds may occur due to the atoms, functional groups or under
the influence of attacking reagents. Due to these electron displacements, the center of different electron
densities are created and there is a chance of attack by the reagent.
The factors which create the center of different electron densities in the substrate is mainly due to the
following:
(i) Inductive effect
(ii) Electromeric effect
(iii) Resonance and mesomeric effect
(iv) Hyperconjugation
Inductive Effect
In a covalent bond between two dissimilar atoms, the electron pair does not remain in the centre but
is attracted towards the more electronegative atoms. Due to unequal sharing of the electron pair, the
bond becomes polar.

15.6
It is defined as follows: “The polarity produced in the molecule as a result of higher electronegativ-
ity of one atom compared to other is termed as inductive effect”.
It is important to note that the electron pair, although permanently displaced or simply shifted, remains
in the same valence shell. The inductive effect is always transmitted along a chain of carbon atoms.
Example: Whenever electron-withdrawing groups are attached to the end of carbon chain, the
sigma electrons of the C X bond are slightly displaced towards the more electronegative atom.
However, the intensity decreases as distance from the source atoms increases.
δδδ+ δδ+ δ+ δ−
C4 C3 C2 C1 Cl
It is a permanent effect in the molecule and can be observed practically in the form of dipole moment.
This type of electron displacement along a carbon chain due to the presence of a source is called
“inductive effect or transmission effect”. This effect is represented by an arrow head in the middle of a
covalent bond pointing to the direction of electron displacement.
There are two types of inductive effects. They are −I effect and +I effect. The carbon and the
hydrogen bond are used as a standard for comparing the tendency of electron attraction and repulsion.
-I Effect
The atom or group which has more power to attract the electron in comparison to hydrogen is said to
be −I effect.
δδδ+ δδ+ δ+ δ−
C4 C3 C2 C1 Cl
The atoms or groups in the decreasing order are as follows:

NR3 > NO2 > SO2R > CN > COOH > F > Cl > Br > I> OR > COOR > OH >
C6H5 > CH CH2 > H
+I Effect
The atom or group which has less power to attract electrons than hydrogen are said to have +I effect.
The s electrons are displaced away from the substituents ‘I’.
δδδ− δδ− δ− δ+
C3 C2 C1 Y
The first group is referred to as attracting or electron withdrawing, while the second group is referred
to as the electron repelling or the electron releasing group.
Groups in the decreasing order are as follows:
(CH3)3C > (CH3)2CH > CH3 > D > H
Salient Features of Inductive Effect

The salient features of inductive effect are as follows:
(i) It is a permanent effect in the molecule or ion. Although the shared pair of electrons are perma-
nently shifted towards the more electronegative atom, they remain in the same valence.
(ii) As a result of the electron pair shifting towards more electronegative atom it acquires a partial
negative charge and other part acquires positive charge.

(iii) The inductive effect is not confined to the polarisation of one bond but is transmitted along a chain
of carbon atom through s bonds. However, the effect is insignificant beyond the second carbon in
the chain.
(iv) Inductive effect brings changes in the physical properties such as dipole moment, solubility, etc.
It affects the rate of reaction.
(v) To explain inductive effect, the carbon and hydrogen bond is taken as a standard, and zero effect
is assumed for the bond. Atoms or groups which have great electron withdrawing capacity than
hydrogen show −I effect, whereas atoms or groups which have greater electron releasing power
show +I effect.
(vi) The phenomenon of inductive effect is very important in organic chemistry as it is helpful in
explaining several facts such as reactivity of alkyl halides, dipole moment, reactivity and strength
of the acids and strength of bases.
Electromeric Effect
The effect involving the complete transfer of a shared pair of electron to one atom of a compound which
is joined by a multiple bond (double (or) triple) at the requirement of attacking reagent is known as
electrometric effect. It is indicated by E and is represented by a curved arrow ( ( showing an electron
pair. It is a temporary effect.
Direction of the Shift of Electron Pair

When the groups linked to multiple bonds are similar, the shift can occur to either direction. For example,
in ethylene, the shift can occur in any one of the carbon atom.
CH2 CH2 CH2 CH2

Both are similar
CH2 CH2 CH2 CH2
When dissimilar groups are linked on two ends of a double bond, the shift is decided by the direction
of the inductive effect.
Example:
CH3 CH CH2 CH3 CH CH2 1
CH3 CH CH2 CH3 CH CH2 2
Due to the electron repelling nature of methyl group, the electron shift occurs according to equation (1)
and not equation (2) path.
1 2 3 4 5
1 2 3 4 5
CH3 CH CH CH2 CH3 CH3 CH CH CH2 CH3 (a)
CH3 CH CH CH2 CH3 CH3 CH CH CH2 CH3 (b)

1 2 3 4 5
The +I effect of CH2CH3 is larger than that of CH3 due to transfer of p -electron from C3 to C2.

15.8
In case of the carbonyl group, the shift is always towards oxygen, that is, more electronegative
atom.
C O C O
This effect is common during the addition of polar reagents on >C C< and >C O bonds.
There are two types of electrometric effects—+E effect and −E effect
(i) The transfer of electron towards the attacking reagent is called +E effect.
Example: Addition of acids to alkene.
+
C C + H+ C C
H
(a) The transfer of electron away from the attacking reagent is called −E effect.
Example:
C O + CN C O
CN
Resonance or Mesomeric Effect

If a molecule has alternate double bonds, it is said to be a conjugated molecule. In such compounds, the
p electrons are delocalised and polarity will develop in the molecule. The same happens when an atom
or a group with a lone pair of electron is in conjugation with a conjugated double bond.
“The development of polarity in a molecule as a result of interaction between two p -bonds
or a p -bond and atom or a group with a lone pair of electrons is known as mesomeric effect or
resonance”.
In a carbonyl group, the oxygen atom is more electronegative than the carbon atom. The p -
electrons of the double bond get displaced towards the oxygen atom. The shifting of the electron is
shown by a curved arrow ( (. This will give an ionic structure. The actual structure seems to lie in
between structures (i) and (ii) which can be best represented as structure (iii) which is p -electrons
drawn preferentially towards oxygen.
C O C O C O C O
(i) (ii) (iii)
Like inductive effect mesomeric effect also +M and −M effect.
+M Effect
Electrons transfer away from the atoms or a group. A group which has the capacity to increase the
electron density of the rest of the molecules is said to be +M effect or groups which donate the electron
to the double or triple bond of the conjugate system are said to be +M effect.
+M effect groups are Cl, Br, I, NH2, NHR, NR 2, OH, OR, SR, SH, OCH3, etc.
The +M effect of a halogen atom in vinyl and allyl halides explains their low reactivity. The +M effect
activates benzene nucleus for electrophilic substitution reaction that occurs at ortho and para position.

-M Effect
The transfer of electrons is directed towards atoms or groups; the group which decreases the electron den-
sity of the rest of the molecules is said to have −M effect or the group which can withdraw electrons from
the double bond or from a conjugated system towards itself due to resonance is said to have −M effect.
O
−M effect groups are NO2, C N, C , CHO, COOH, COOR, etc.
With −M effect, electrophile attacks at the M-position (e.g., benzene). −M effect deactivates for
electrophilic substitution reactions but activates nucleophilic substitution reactions.
Salient Features of Mesomeric Effect

The salient features of mesomeric effect are as follows:
(i) p -electrons and a lone pair of electrons are involved in this effect through conjugative mechanism.
(ii) It is a permanent effect in the molecule in the ground state.
(iii) It affects the physical properties such as dipole moment, solubility and rate of reaction of the
substance.
Hyperconjugation
The kind of delocalisation involving sigma bond orbital is called hyperconjugation.
There should at least one H-atom at a -carbon with respect to sp2 hybrid carbon; greater the num-
ber of C H bonds at a -carbon to the unsaturated system, greater will be the electron release and thus,
greater the hyperconjugation effect.
15.4 REACTION INTERMEDIATES

Short-lived and highly reactive fragments are called reaction intermediate; with the result of reaction
intermediate, either homolytic or heterolytic bond fission occurs. The important reactive intermediates
are free radicals, carbonians, carbanions, carbenes, nitrenes and benzynes.
15.4.1 Free Radicals

A free radical may be defined as an atom or a group of atoms having odd or unpaired electrons. These
results occur due to homolytic fission of a bond and are denoted by putting a dot (.), against the symbol
of atom or a group of atom.
Example: Cl • (chlorine free radical), H • (hydrogen free radical) and CH3 • (methyl free radical).
Formation of Free Radical

The formation of free radical is initiated by heat, light or catalyst; the chemical reaction which takes
place through free radical is known as free radical reaction. Free radicals are highly unstable, gener-
ally neutral and paramagnetic in nature. They are short-lived and highly reactive due to the presence
of odd electron.
Energy
Cl••Cl Sun
 •
light → Cl + Cl
•

15.10
The three types of free radical reactions that are observed are as follows.
(i) Mutual combination of free radical
Cl• + Cl• → Cl 2
(ii) Reaction between free radical and neutral molecule gives a neutral molecule and new free radical.
CH 4 + Cl• → CH 3• + HCl
(iii) A free radical can lose a neutral molecule to form a new free radical.
CH 3COO• → • CH 3 + CO2
Some Important Reactions via Free Radical Formation

(i) Wurtz reaction giving alkanes
(ii) Substitution reactions of alkanes
(iii) Kolbe electrolytic reaction giving alkanes, alkenes and alkynes
(iv) Anti-Markovnikov’s addition or peroxide effect or Kharasch effect
Relative Stability of Free Radicals

(i) Tertiary (3°) > Benzyl > allyl > Secondary (2°) > Primary (1°) > Methyl > Vinyl
• • • • • • •
(ii) (C6 H 5 )3 C > C6 H 5  C H > CH 2  CH  C H 2 > (CH 3 )2 C H > CH 3 C H 2 > C H 3 > HC  C H
(iii)
CH3O CH2 < CH3 CH2 < CH2 < O2N CH2
Structure of Free Radical

The carbon atom of alkyl-free radicals is sp2 hybridised and bonded to only three atoms or groups of
atoms. Hence, free radicals have a planar structure with odd electrons situated in the unused p-orbital
at right angle to the plane of hybrid orbital.
R
R C 120°
R
15.4.2 Carbocations or Carbonium Ions

In a covalent bond, carbon is linked to a more electronegative atom or a group, breaks up by a hetero-
lytic fission. The more an electronegative atom takes the electron pair from carbon; hence carbon loses
its electron and thus acquires a positive charge; known as carbonium ion.
or
Organic substance carrying a positive charge on carbon atom are known as “carbocation” or “car-
bonium ion”,
C X C+ X

Carbocation only differs from free radicals which have an odd electron. Carbocation is very reactive
due to a carbon atom having a vacant p-orbital. A positively charged carbon atom tries to complete
its octet and hence, these ions react readily with those species which can release two electrons for the
formation of fourth bond. They react with the nucleophilic reagent.
Carbocations are named by adding the words carbocation to the parent alkyl group. These are
also termed primary, secondary and tertiary, depending upon the nature of the carbon atom bearing a
positive charge.
H H H R
H C H3C C (CH3)2 C R C
H H R
Methyl carbo Ethyl carbo Isopropyl Tertiary
cation cation (or) Secondary carbocation
carbocation
Primary Carbocation
Formation of Carbocation
(i) By heterolysis of halogen compound:
(CH3)3C Cl (CH3)3C + Cl
(ii) By protonation of alkene or alcohol:
H
H2C CH2 H2C CH3
H −H2O
R O H R OH2 R
(iii) By decomposition of diazo compounds:
−Cl −N2
C6H5 N2 Cl C6H5 N2 C6H5
Some Important Reactions via Carbocation Formation

Some important reactions that take place as a result of carbocation are as follows:
(i) Elimination reaction to form alkenes from alkyl halides and alcohols
(ii) Electrophilic addition reaction of alkenes, alkynes and alkalines
(iii) SN1 reaction of alkyl halides and diazonium salts
(iv) Pinacol–pinacolone molecular rearrangement
Structure of Carbocation
A carbon atom carrying positive charge has six electrons in its valance shell, i.e., two electrons less
than an octet. The positively charged carbon atom in the carbocation is in sp2 hybridisation and has a
planar structure.
R
R C+ 120°
R

15.12
The order of reactivity of carbocation is:

Primary (1°) > Secondary (2°) > Tertiary (3°)
Relative Stability of Carbocation

The stability of alkyl carbocation is influenced by resonance, hyperconjugation and inductive effects.
The stability decreases as +I effect decreases and molecular mass decreases.
+ + + +
CH 2 CH 2 > CH 3CH 2 CH 2 > CH 3 CH 2 > CH 3 CH 2 > CH 3+
If a -hydrogen with respect to carbocation, that is, carbon has one or more than one lone pair of elec-
trons, then the lone pair of electrons strongly stabilise carbocation due to delocalisation.
15.4.3 Carbanions
When a covalent bond in which carbon is attached to a lesser electronegative atom breaks up by het-
erolysis, the atom leaves without taking away the bonding pair of electrons and thus the carbon atom
acquires negative charge due to an extra electron.
Organic ions which contain a negatively charged carbon atom are called carbanions.
C Y C +Y
Structure and Characteristics of Carbanions

(i) In carbanion, the carbon carrying the negative charge contains eight electrons in the valance
shell; it has octet configuration and is diamagnetic.
(ii) They are highly reactive because the carbon carrying the negative charge is electron-rich and
can donate its non-bonding pair of electrons to some other group for sharing. Hence, carbanion
behaves as nucleophiles and is ready to attack electrophiles.
(iii) The negatively charged carbon is in a state of sp3 hybridisation and has a pyramidal structure.
Some Important Reactions via Carbanion Formation

Some important reactions via carbanion formation are as follows:
(i) Aldol condensation of aldehyde having a -H atom
(ii) Cannizzaro’s reaction of aldehyde without a-hydrogen atom
(iii) Perkin reaction
(iv) Knoevenagel reaction
Relative Stability of Carbanions

(i) Aromatic > benzyl > allyl > acetyl > vinyl > alkyl (primary) > secondary > tertiary
− − − − − −
(ii) (C6H5)3 C > (C6H5)2 CH > (C6H5) CH2 > (CH2 CH−)n CH2 > HC C > CH2 CH > CH3 >
− − −
CH3CH2 > (CH3)2CH> (CH3)3C
O2NO CH2 > CH2 > CH3 CH2 > CH3 O CH2

− − − − − −
(C6H5)3 C > (C6H5)2 CH > (C6H5) CH 2 > (CHand
Structure 2 CH−)n CH
Reactivity of 2Organic C >Inorganic
> HC and CH2 CH > CH3 >
Molecules 15.13
− − −
CH3CH2 > (CH3)2CH> (CH3)3C
(iii) O2NO CH2 > CH2 > CH3 CH2 > CH3 O CH2
Stability increases with increase of S-character:

− −
R C C > R2C CH > RCH3 CH2
50% 33% 25% S Character
Groups such as NO2, CN, COOC2H5, > C O, halogen and C6H5 increase the stability of
carbanions.
15.4.4 Carbenes
Carbenes are highly reactive, short-lived, diagonal in geometry and neutral species in which a carbon
atom has six electrons in the outer shell, out of which two constitute a lone pair and two are shared.
Therefore, they are divalent carbon species of carbon containing two unpaired electrons and possess
no charge.
Carbenes are sp2 as well as sp hybridised, neutral, transitory reaction intermediates containing a
carbon atom with two bonds and two electrons.
(i) By the decomposition or pyrolysis of aliphatic diazo compounds or ketones.
u /∆
CH 2 N 2 h → •• CH 2 + N 2
(ii) By action of a base on a suitable polyhalogen.

CHCl3 + C2H5ONa → •• CH 2
sp2 hybrid carbene are two types singlet and triplet.
Some Important Reactions via Carbene Formation

Carbenes undergo several important reactions as follows:
(i) Addition reaction (Carbylamine reaction)
(ii) Insertion reaction (Reimer–Tiemann reaction)
(iii) Ring expansion reaction
15.4.5 Nitrenes or Imidogens

Nitrenes are electron-deficient species in which nitrogen has a sextet of electron. These are similar to
carbenes and the neutral univalent nitrogen intermediate can exist in singlet and triplet forms.
Formation of Nitrenes
Nitrenes are formed in the following manner:
(i) The simplest nitrene is formed when hydrozoic acid is irradiated with UV light in aromatic sol-
vent and forms a small amount of primary aromatic amines.
••
hv C H CH
6 5 3→ P H N
N 3H → N 2 + NH  2 (C6H5)CH2 NH2
••

15.14
(ii) Photolysis of alkyl azide:

••
R N3 hv
→ R N + N2
••
Some Important Reactions Via Nitrenes Formation

Some important reactions in nitrene formation are as follows:
(i) Hofmann rearrangement
(ii) Lossen rearrangement
(iii) Schmidt rearrangement
Reactions
The reactions are discussed here.
Addition Alkenes
Alkenes react with nitrenes to form the corresponding cyclic amine.
CH3CH CH2 + H N CH3 CH CH2

Propene Nitrene N
H
Methyl cyclo propyl amine
Addition to Alkanes
Acetyl nitrene reacts with isobutane to form acetyl tertiary butyl amine.
CH3 O CH3 O
H3C C CH3 + CH3 C N CH3 C NH C CH3
H CH3
Photolysis of phenyl nitrene forms azobenzene.

••
hu
2 C6 H 5 N → C6H5 N N C6 H 5
••
Phenyl nitrene Azobenzene
15.4.6 Benzynes
Benzyne is neutral, highly reactive intermediate; it has a formal C C bond and can be represented as
follows:
(or)
Benzynes are also known as didehydro benzenes.

Stereochemistry
Except for the two hydrogen atoms which are linked a through a bond, the remaining C-atoms are
sp2–hybridised. The C-atoms linked through the bond are sp hybridised. Due to these two sp hybrid-
ised c-atoms, the intermediate is highly strained and is highly reactive. However, the presence of sp
hybridisation does not change its aromatic character. Hence, the intermediate still consists of aromatic
sextet.
There are three possible ground sates of benzyne.

Example:
(i) A triplet state:
(ii) A symmetric singlet state, where the two half-filled sp orbitals are symmetric with respect to C2
axis:
C2 axis +
+
(iii) Anti-symmetric singlet:

+
−
Formation of Benzynes
By Aryl Halides
By heating Aryl halides with amines benzynes are formed.
H − Heat
+ NH2 + NH3 + Cl−
Cl
Chlorobenzene
By Ortho Amino Benzoic Acid

Ortho amino benzoic acid is treated with dilute nitrous acid by losing nitrogen and carbon dioxide
gives benzyne.
+
NH2 N N +
HNO2 −N2 −CO2
H2O
COOH COO− COO+

15.16
Stability of Benzynes
The structure of benzyne can be represented as follows:
(i) (ii) (iii) (iv) (v)
Benzyne is stabilised by resonance between structures (i) and (ii); hence, benzyne can be represented
by structure (iii). The extra p bond (iv) is localised and orthogonal to the other p bond by making up
the aromatic ring. Benzyne can also be drawn as diradical; here, the p bond (v) splits homolytically,
leaving one electron on each of the two atoms that are formally part of that bond. It can be extremely
reactive species due to the nature of its ( ) triple bond. In benzyne, the p-orbitals are distorted to
accommodate the ‘ ’ bond with the ring system, reducing their effective overlapping. A suitable chem-
ical trap for benzyne is a cyclopentadiene.
There are three possible di radical di de hydro benzynes as 1,2 di de hydro benzyne, 1,3 di de
hydro benzyne and 1,4 di de hydro benzyne.
H H H H H
H H H H H
H H
1, 2 didehydro 1, 3 didehydro 1, 4 didehydro
benzyne benzyne benzyne
Reaction with Benzynes

Cyclo Addition
[2 + 2] cyclo addition
+ +
[2 + 3] cyclo addition
+N
N
+ N N
−N
N
Ph Ph
Phenyl azide Benzo triazole
Dimerisation and Trimerisation

Dimerisation of benzyne is a 2+2 cyclo addition reaction, it occurs via a concerted mechanism and
the product is biphenylene. Trimerisation of benzyne is a 2+2 cyclo addition reaction that occurs via
concerted reaction mechanism and the product is triphenylene.

2 Biphenylene
3 Triphenylene
Reaction with Nucleophile

Benzyne reacts with nucleophilic reagent to form different organic compounds.
OH
H2O Phenol
OR
ROH Phenolic ether
RNH2
NHR
Aromatic amine
(C2H5)3 CH
C(C6H5)3
Tri phenyl methyl benzene
Important Organic Reactions

The reactions of organic compounds can be classified into four main types.
(i) Substitution or displacement reaction
(ii) Addition reaction
(iii) Elimination reaction
(iv) Rearrangement reaction
Substitution Reaction
Which an atom or a group attached to a carbon atom in a substrate molecule is replaced by another
atom or a group of atoms, no change occur in the carbon skeleton is observed during the reaction.
Depending on the mechanism, the substitution reactions are further classified into three types as
follows.

15.18
(a) Free radical substitution

(b) Electrophilic substitution
(c) Nucleophilic substitution
Example:
(i) CH4 + Cl2 UV
→ CH3Cl + HCl2 (Free radical substitution)
(ii) CH3CH2Br + NaOH → CH3CH2OH + NaBr (Nucleophilic substitution)
(iii) C6H6 + HNO3 H 2 SO 4
→ C6H5NO2 + H2O (Electrophilic substitution)
(iv) C6H6 + Cl2 FeCl
 3
→C6H5Cl + HCl (Free radical substitution)
Addition Reaction
An attacking reagent adds up to the substrate molecule without elimination of any atom or group. Such
reactions are given by those compounds which possess double or triple bonds. In this process, the triple
bond is converted into a double bond or a single bond and a double bond is converted into a single bond.
For each p bond of the molecule two s bonds are formed and the hybridisation state of carbon atom
changes from sp to sp2 and sp2 to sp.
Addition reactions are also three types.
(a) Free radical Addition
(b) Nucleophilic Addition
(c) Electrophilic Addition
Example:
(i) HC CH + H2 140

NP
o → H 2C
C
CH2 H200
 o → CH 3
2 /Ni
C
CH3 (Free radical addition)
(ii) H2C CH2 + Br2 →CH2Br CH2Br (Electrophilic addition)
O H
OH
(iii) CH3 C H + HCN CH3 C (Nucleophilic addition)
CN
Elimination Reaction
In these reactions, generally, atoms or groups from two adjacent carbon atoms (a, b) in the substrate
molecule are removed and a multiple bond is formed. In the process, two sigma bonds are lost and a
new p -bond is formed, that is, a state of hybridisation of the carbon atom changes from sp3 to sp2 and
sp2 to sp.
This reaction is also known as b -elimination.
Example:
Br Br
Heat
H C C H + Zn H C C H + ZnBr2
(−Br2)
H H H H
Some important elimination reactions are as follows:
(a) Arbylamine
(b) Reimer-Tiemann reaction

Rearrangement Reaction
The reaction which involves the migration of an atom or a group from one site to another within the
molecule, resulting in a new molecular structure is known rearrangement reaction.
Example: Fries rearrangement
O
O C CH3 OH O OH
C CH3
NCl3
+
Phenyl acetate C
C CH3
O ε P hydroxy
acetophenone
Beckmann Rearrangement
N OH O
PCl5
CH3 C CH3 CH3NH C CH3
Acetoxime N-methyl acetamide
15.5 MOLECULAR ORBITAL THEORY

The molecular orbital (MO) theory was proposed by Hund, Jones and Mullikan. This theory treats a
molecule in the same way as an atom. The difference is that in an atom, the electrons rotate around
only one nucleus, whereas in a molecule, the electrons rotate around more than one nuclei, that is, the
molecular orbitals are polycentric.
+
A B
The MO theory has the following rules:

(i) The molecular orbitals are polycentric.
(ii) Electrons are fed into three molecular orbitals one at a time such that each entering electron oc-
cupies the lowest possible quantum state, according to the Aufbau principle.
(iii) The electron also obeys Pauli’s exclusion principle.
(iv) Molecular orbitals can be obtained by linear combination of atomic orbitals.
The molecular orbital theory describes electrons as delocalised moieties over adjacent atoms; it is pow-
erful and has extensive approaches that extend beyond the limitations of the valence shell electron pair
repulsion (VSEPR) and the valence bond theory (VBT). The VSEPR and the VBT accurately predict
bond properties, but they fail to explain structure and magnetic properties of some molecules. The
MO theory incorporates the wave character of electrons in developing the MO diagram; these predict
physical and chemical properties of a molecule such as structure, bond energy, bond length and bond
angle. They also provide information in predicting a molecule’s electronic spectra and para magnetism.

15.20
Atomic and Molecular Orbital

Atomic Orbital
The atomic orbital is the region of space around the nucleus of an atom where an electron is likely to
be found or the electron density is more.
Molecular Orbital
The molecular Orbital is a combination of atomic orbitals where the region of electron density is most
likely to be found in a molecule.
Homo Nuclear Di Atomic Molecules

Molecules consisting of two identical atoms are said to be homo nuclear diatomic.
Example: H2, N2, O2, etc.
Hetero Nuclear Di Atomic Molecules

Molecules consisting of two non-identical atoms are said to be hetero nuclear diatomic.
Example: CO, NO, HF, LiF, etc.
Anti-bonding Molecular Orbitals

Orbitals that are out of phase with each other are called “anti-bonding” orbitals because regions with
dense electron probabilities do not merge and may destabilise the molecule.
Bonding Molecular Orbitals

Bonding orbitals are less energetic than anti-bonding atomic orbitals and are in-phase as shown in
Figure 15.1.
Anti bonding molecular orbitals
−
Energy
+ +
Bonding molecular orbitals
Figure 15.1 Bonding molecular orbitals

Phases and Nodes

Depends on their wave “up” or “down” displacements, phases are designated as (+) or (-). A node
occurs if the phase signs change from (+) to (-) or vice versa. It is important to notice that the phase
signs do not symbolise charges. Nodes are regions where the probability of finding an electron is
zero.
Sigma (r ) and pi (o ) Bond

A sigma-bond is formed as an “end-to-end” overlap of symmetric atomic orbitals.
A pi-bond is formed as a “sideways” overlap of atomic orbitals.
15.5.1 Important Points on Molecular Orbital Diagrams

Some important points on molecular orbital diagrams are as follows:
(i) The Y-axis of a MO diagram represents the total energy of the orbitals.
(ii) Individual atomic orbitals (AO) are arranged on the far left and far right of the diagram.
(iii) Molecular orbitals formed by overlapping of atomic orbitals are located in the middle of the
diagram; they overlap with either a sigma or a pi bond. With respect to their phases, they are
designated as bonding, non-bonding or anti-bonding orbitals.
(iv) According to Pauli’s exclusion principle, lower energy MOs are filled first, followed by consecu-
tively higher energy orbitals.
15.5.2 Fundamental Steps for Constructing Molecular Orbitals

The following are common steps to derive simple homo nuclear and hetero nuclear MOs to construct
more complicated, polyatomic diagrams.
(i) Find the electronic configuration of each atom of the molecule and the place on the atomic orbital
for that atom.
(ii) Determine if the molecule is homo nuclear or hetero nuclear; if the molecule is homo nuclear, the
AOs will be symmetric; hetero nuclear AOs will slightly differ because the more electronegative
atom will be placed lower on the diagram due to lone pairs of electrons being more stable on more
electronegative elements, thus leading them to be lower in energy.
(iii) Keep in mind the energy of the atomic and molecular orbitals; fill molecular orbitals using energy
and bonding properties of the overlapping atomic orbitals. The following factors contribute to the
position of one MO with respect to other MOs:
(a) More nodes = more energetic = higher MOs
(b) Sigma bond orbitals are stronger than pi bond orbitals
(c) Anti-bonding MOs are higher in energy than bonding MOs
(d) Constructive overlap = fewer nodes = more stable (less energetic)
(e) Destructive overlap = more nodes = less stable (more energetic)
(iv) The number of individual atomic orbitals should be equal to the number of molecular orbitals.
Use the MO diagram to predict the properties of the molecule like bond order, bond angle, para-
magnetism, etc.

15.22
15.5.3 Five Basic Rules of Molecular Orbital Theory

The five basic rules of the MO theory are as follows:
(i) The number of molecular orbitals = the number of atomic orbitals combined
(ii) Lower energy orbitals are bonding orbitals; higher energy orbitals are anti-bonding.
(iii) Electrons first enter into the lowest available energy orbital.
(iv) According to Pauli’s exclusion principle, the maximum number of electrons in an orbital is two.
(v) According to Hund’s rule, electrons spread out before pairing up.
Atoms or molecules in which electrons are paired are diamagnetically repelled by both poles of a
magnet. Those that have one or more unpaired electrons are paramagnetically attracted to a magnetic
field.
15.5.4 L
inear Combination of Atomic Orbitals and Type
of Atomic Orbitals
Molecular Orbital
According to Hund and Mullikan, a covalent bond is formed when two half-filled atomic orbitals
(AO) of two atoms come nearer and then overlap each other to form a new bigger orbital known as a
molecular orbital.
The two nuclei may approach each other along a line. When the nuclei come close, the two atomic
orbitals of the two atoms combine to form two molecular orbitals. One is bonding and the other is the
anti-bonding orbital.
Anti-bonding Orbital
The molecular orbital with higher energy gives rise to a repulsive state called anti-bonding orbital.
Bonding Orbital
The molecular orbital with lower energy gives rise to an attractive state called bonding orbital.
Non-bonding Orbital
These do not participate in a chemical bond. They are inner shell orbitals.
The forming of bonding and anti-bonding orbitals may be explained in terms of wave functions.
Let the wave functions of two atoms A and B be YA and YB respectively. These two atomic orbitals
may combine in two ways.
(i) Yb = YA + YB (Bonding)
(ii) Ya = YA − YB (Anti-bonding)
ya = yA − yB
yA yB
yb = yA + yB

From the spectroscopic measurement, the increasing order of energies of molecular orbitals is decided
in the following order.
s 1s < s *1s < s 2s < s *2s < s 2px < p 2py = p 2pz < π*2py = p *2pz < s *2px (For homo nuclear
atoms; atomic number more than seven and hetero nuclear atoms)
s 1s < s *1s < s 2s < s *2s < p 2py = p 2pz < s 2px < p *2py = p *2pz< s *2px (For homo nuclear
atoms; atomic number less than seven)
15.5.5
Molecular Orbital Energy Level Diagrams of Homo Atomic
Molecules
Molecular Energy Level Diagrams of Homo Molecules
Hydrogen Molecule
Atomic number = 1
Electronic configuration = 1s1
Total number of electrons = 1 + 1 = 2
Total number of orbitals = 2(s 1ss *1s)
Molecular electronic configuration = s 1s2
Energy Level Diagram of Hydrogen Molecule
s ∗1s
1s 1s
Atomic orbital Atomic orbital
of hydrogen s 1s of hydrogen
Molecular
orbital of H2
Bond Order
Number of bonding electrons − Number of antibonding electrons
Bond order =
2
Number of bonding electrons = 2
Number of anti-bonding electrons = 0
2−0
∴ Bond order = =1
2
In hydrogen molecule, single bond exists between two atoms.
Magnetic Property
Here, there are no unpaired electrons. Hence, it shows diamagnetic property.
Helium Molecule
Atomic number = 2
Electronic configuration = 1s2

15.24
Total number of orbitals = 2(s 1s and s *1s)

Molecular electronic configuration =s 1s2s *1s2
Energy Level Diagram of Helium Molecule
s ∗1s
1s 1s
A.O. of He A.O. of He
s 1s
M.O. of He2
Bond Order
2−2
Bond order = =0
2
So, Helium molecule does not exist and it is mono atomic.
Magnetic Property
Here, there is no unpaired electron and it is also diamagnetic.
Boron Molecule
Atomic number = 5
Electronic configuration = 1s22s22p1
Total number of atomic orbitals = 5 + 5 = 10
The MO diagram for diboron requires the explanation of the p orbital overlap; three dumbbell-
shaped p-orbitals have equal energy and are oriented mutually perpendicularly or orthogonally. The
p-orbitals oriented in the x-direction (px) can overlap end-on end s bonding (symmetrical) and an
anti-bonding s * molecular orbital. In contrast to the sigma 1s MOs, the s 2p has some non-bonding
electron density at either side of the nuclei and the s * 2p has some electron density between the
nuclei.
The other two p-orbitals, py and pz, can overlap sideways; the resulting bonding orbital has its
electron density above and below the plane of the molecule. The orbital is not symmetric around the
molecular axis and is therefore a p orbital. The anti-bonding p orbital asymmetrical has four lobes
pointing away from the nuclei. Both py and pz orbitals form a pair of p orbitals equal in energy (degen-
erate) and can have higher or lower energies than that of the sigma orbital.
There are 10 electrons and 10 orbitals; out of 10 electrons, four electrons occupy s 1s and s *1s.
These two are non-bonding orbitals. The next four electrons occupy s 2s and s *2s orbitals. Now,
the 2p electrons are to be admitted into the molecular orbitals. According to the order of molecular
orbital energies, the 2p electrons should occupy s 2px. If it is so, the molecule should be diamag-
netic. However, boron is actually paramagnetic. To explain this, it is suggested that p 2py and p 2pz
have to be occupied with single electrons. Hence, the molecular electronic configuration of boron is
s 1s2 s *1s2 s 2s2 s *2s2 p 2 p1y p 2 p1z

Energy Level Diagram of Boron
s ∗2px
2p 2p
p ∗2py p ∗2pz
2px 2py 2pz s 2px 2px 2py 2pz
p 2py1 p 2pz1
Energy
s ∗2s 2
2s 2s
s 2s 2
s ∗1s 2
1s 1s
s 1s 2
A.O’s of B MO’s of B2 A.O’s of B
Bond Order
6−4
Bond order = =1
2
In boron molecule, in between two atoms, a single bond exists.
Magnetic Property
Here, there are two unpaired electrons. Hence, it shows paramagnetic property.
Bond length = 1.59Å, bond dissociation energy = 289 KJ/mole.
Carbon Molecule
Atomic number = 6
Electronic configuration = 1s2 2s2 2p2
Total number of electrons = 12
Total number of orbitals = 10
Molecular orbital electronic configuration
s 1s2s *1s2s 2s2s *2s2p 2 p 2yp 2 pz2

15.26
Energy Level Diagram of Carbon

s ∗2px
2p 2p
p ∗2py p ∗2pz
p 2py2 p 2pz2
Energy
s ∗2s 2
2s 2s
s 2s 2
s ∗1s 2
1s 1s
s 1s 2
A.O’s of C MO’s of C2 A.O’s of C
Bond Order
8−4
Bond order = =2
2
In a carbon molecule, in between two atoms, a double bond exists.
Magnetic Property
Here, there are no un-paired electrons. Hence, it shows diamagnetism.
Bond length = 1.31Å, Bond dissociation energy = 627.9 KJ/mole
Nitrogen Molecule
Atomic number = 7
The molecular electronic configuration is as follows:
s 1s2s *1s2s 2s2s *2s2 p 2 p 2y p 2 pz2s 2 px2
The three s *2px,p *2py,p *2pz anti-bonding orbitals are vacant. Hence, the molecule is highly
stable.

Energy Level Diagram of Nitrogen Molecule

s ∗2px
p ∗2py p ∗2pz
p 2py2 p 2pz2
Energy
s ∗2s 2
2s 2s
s 2s 2
s ∗1s 2
1s 1s
s 1s 2
A.O’s of N MO’s of N2 A.O’s of N
Bond Order
Number of bonding orbitals = 10
Number of anti-bonding orbitals = 4
10 − 4
Bond order = =3
2
Hence, triple bond exists in nitrogen molecule.
Magnetic Property
There are no unpaired electrons. Hence, it shows diamagnetism.
Bond length = 1.1Å, bond dissociation energy = 945.6 KJ/mole.
Oxygen Molecule
Atomic number = 8
Molecular electronic configuration
s 1s2s *1s2s 2s2s *2s2s 2 px2p 2 p 2yp 2 pz2p *2 p1yp *2 p1z

The MO energy level diagram of dioxygen is different from that of the previous diatomic molecules
because the p s MO is lower in energy than the 2p orbitals; this is due to the interaction between the

15.28
2s MO and the 2pz MO. Distributing eight electrons over six molecular orbitals leaves the last two
electrons as a degenerate pair in the 2pp * anti-bonding orbitals, and the resulting bond order is 2.
Energy Level Diagram of Oxygen Molecule

s ∗2px
p ∗2py1 p ∗2pz1
2px 2py 2pz p 2py2 p 2pz2 2px 2py 2pz
s 2px2
Energy
s ∗2s
2s 2s
s 2s
s ∗1s 2
1s 1s
s 1s 2
A.O’s of O MO’s of O2 A.O’s of O
Bond Order
10 − 6
∴ Bond order = =2
2
Hence, the oxygen molecule has double bond.
Magnetic Property
With two unpaired electrons, the oxygen molecule shows para magnetism.
Bond length = 1.21Å, bond dissociation energy = 494.6 KJ/mole
Fluorine Molecule
Atomic number = 9
Electronic configuration is 1s2 2s2 2p5
Molecular electronic configuration
s 1s2s *1s2s 2s2s *2s2s 2 px2p 2 p 2yp 2 pz2p *2 px2p *2 pz2

Energy Level Diagram of Fluorine Molecule

s ∗2px
p ∗2py2 p ∗2pz2
p 2py2 p 2pz2
2px 2py 2pz 2px 2py 2pz
s 2px2
Energy
s ∗2s 2
2s 2s
s 2s 2
s ∗1s 2
1s 1s
s 1s 2
A.O’s of F MO’s of F2 A.O’s of F
Bond Order
10 − 8
Bond order = =1
2
Thus, fluorine molecule contains one covalent single bond.
Magnetic Property
As there are no unpaired electrons, the molecule is diamagnetic.
Bond length = 1.42Å, bond dissociation energy = 155 KJ/mole.
15.5.6 Molecular Energy Level Diagrams of Hetero Atomic Molecules

Carbon Monoxide Molecule
Atomic number of carbon = 6 (1s2 2s2 2p2)
Atomic number of oxygen = 8 (1s2 2s2 2p4)
Molecular orbital configuration is
s 1s2s *1s2s 2s2s *2s2s 2 px2p 2 p 2yp 2 pz2

15.30
Energy Level Diagram of Carbon Monoxide Molecule
s ∗2px
2p 2p
p ∗2py p ∗2pz
p 2py2 p 2pz2
s 2px2
Energy
s ∗2s 2
2s 2s
s 2s 2
s ∗1s 2
1s 1s
s 1s 2
A.O’s of C MO’s of CO A.O’s of O
Bond Order
10 − 4
Bond order = =3
2
In the CO molecule, triple bond is present.
Magnetic Property
No unpaired electrons are available; hence, it is diamagnetic.
Cyanide Ion (CN−)
Atomic number of carbon = 6 (1s2 2s2 2p2)
Atomic number of nitrogen = 7 (1s2 2s2 2p3)
Total number of electrons = 6 + 7 + 1 = 14 (1 is subtracted when there is a +ve charge; 1 is added
when there is a –ve charge.)
Molecular electronic configuration is
s 1s2s *1s2s 2s2s *2s2s 2 px2p 2 p 2yp 2 pz2

Energy Level Diagram of Cyanide Ion
s ∗2px
2p 2p
p ∗2py p ∗2pz
p 2py2 p 2pz2
s 2px2
Energy
s ∗2s 2
2s 2s
s 2s 2
s ∗1s 2
1s 1s
s 1s 2
A.O’s of C MO’s of CN− A.O’s of N
Bond Order
10 − 4
Bond order = =3
2
∴ Triple bond exists in cyanide ion.
Magnetic Property
There are no unpaired electrons; hence, it shows diamagnetism.
Nitric Oxide (NO) Molecule
Atomic number of nitrogen = 7
Atomic number of oxygen = 8
∴ Total number of electrons = 7 + 8 = 15
s 1s2s *1s2s 2s2s *2s2s 2 px2p 2 p 2yp 2 pz2p *2 p1yp *2 pz0

15.32
Energy Level Diagram of Nitric Oxide Molecule

s ∗2px
p ∗2py1 p ∗2pz0
p 2py2 p 2pz2
s 2px
Energy
s ∗2s 2
2s 2s
s 2s 2
s ∗1s 2
1s 1s
s 1s 2
A.O’s of N MO’s of NO A.O’s of O
Bond Order
10 − 5
∴ Bond order = = 2.5
2
In nitric oxide molecule, two bonds—s bond and p bond exist.
Magnetic Property
Here, there are unpaired electrons; hence, it is paramagnetic.
Nitric Oxide Ion (NO−)

Atomic number of nitrogen = 7
Atomic number of oxygen = 8
Total number of electron = 7 + 8 + 1 = 16
s 1s2s *1s2s 2s2s *2s2s 2 px2p 2 p 2yp 2 px2p *2 p1yp *2 p1z

s ∗2px
p ∗2py1 p ∗2pz1
p 2py2 p 2pz2
s 2px
Energy
s ∗2s 2
2s 2s
s 2s2
s ∗1s 2
1s 1s
s 1s 2
A.O’s of N MO’s of NO− A.O’s of O
Bond Order
10 − 6
Bond s order = =2
2
∴ Nitric oxide ion has a double bond.
Magnetic Property
Here, there are two unpaired electrons. Hence, NO− molecules show para magnetism.

1. The mixing of 1s orbital 2p orbitals is __________ hybridisation
[Ans.: sp2]
2. The bond angle observed in sp hybridisation is __________.
[Ans.: 180 °]
3. In sp3 hybridisation, the geometry of the molecules is __________
[Ans.: Tetrahedral]

15.34
4. Structure and hybridisation of NH3 is __________

[Ans.: Pyramidal, sp3]
5. SF6 involving __________ hybridisation and possess __________ geometry
[Ans.: sp3d 2, octahedral]
6. CH4 molecule exhibits __________ hybridisation.
[Ans.: sp3]
7. The polarisation of one bond that is caused by the polarisation of an adjacent atom is called
__________ effect.
[Ans.: inductive]
8. The group or atom which has more power to attract the electron in the comparison of hydrogen
is called __________ effect.
[Ans.: positive inductive]
9. __________ effect is also known as mesomeric effect.
[Ans.: Resonance]
10. Hoffmann reaction involves reaction intermediate __________
[Ans.: nitrene]
11.
Benzene + __________
+ [Ans.: ]
12. Carbanions involving hybridisation are __________

[Ans.: sp3]
13. Molecules having __________ involve addition reaction.
[Ans.: double or triple bonds]

1. The most stable radical is
(a) CH2 CH2 (b) CH2 CHCH
(c) CH2 (d) CH2
[Ans.: d]
2. The number of unshared electrons in carbine is
(a) 1 (b) 2
(c) 3 (d) 4
[Ans.: b]

3. Nitrene is generated as an intermediate in

(a) Hoffmann rearrangement (b) Curtius rearrangement
(c) Insertion (d) All the above
[Ans.: d]
4. Benzyne is generated from
(a) Chlorobenzene in presence of sodamide in liquid NH3
(b) Benzene with sodium in liquid ammonia
(c) Benzene in liquid ammonia
(d) Addition of heat on benzoic acid
[Ans.: c]
5. The nucleophile attack on a carbon-carbon double bond generates
(a) Carbanion (b) carbine
(c) Carbocation (d) free radical
[Ans.: a]
6. The peroxide effect occurs
(a) Free radical mechanism (b) Haemolytic fission of double bond
(c) Heterolytic fission of double bond (d) None of these
[Ans.: a]
7. Benzyne is a
(a) 1,2 di hydro benzene (b) 1,2 de hydro benzene
(c) 1,2,3,4 tetra hydro benzene (d) Tridozenes
[Ans.: b]
8. 2
(a) (b)
(c) (d) None of these
[Ans.: b]
9. CH3CH CH2 + CH3 CH CH2

N
H
(a) H N (b) CCl2
(c) R N (d) CH2
[Ans.: a]

15.36
Br
10. H2C CH2 + Br2 CH2 CH2 involving reaction mechanism
Br
(a) Addition (b) substitution
(c) Elimination (d) rearrangement
[Ans.: a]
11. The structure of benzene is
(a) (b)
(c) (d)
[Ans.: c]

1. What is hybridisation?
Ans.: The hypothetical intermixing of nearly the same energy atomic orbitals to give an entirely
new identical equal energy orbitals is termed hybridisation. The combining of atomic
orbitals which have different energy or nearly the same energy and the formation of new
set of orbitals with equivalent energy and shape is known as hybrid orbital and this phe-
nomenon is known as hybridisation.
2. Write the types of hybridisation and its exhibiting geometrics.
Ans.: 1. SP–linear
2. Sp2 hybridisation–trigonal planar
3. Sp3–tetrahedral
4. Sp3d 2–octahedral or square pyramidal
5. dsp2–square planar
3. Describe inductive effect.
Ans.: The polarisation of one bond caused by the polarisation of an adjacent atom is called
inductive effect. It is two types:
1. Negative effect (-I effect)
2. Positive effect (+I effect)
4. Write note on electrometric effect.
Ans.: The effect involving the complete transfer of a shared pair of electron to one atom of a
compound which is joined by a multiple bond (double (or) triple) at the requirement of
attacking reagent is known as electrometric effect. It is indicated by E and js represented
by a curved arrow ( ( showing the electron pair. It is a temporary effect.

C O C O
It is two types:
1 +E effect
2. -E effect
5. Explain resonance or mesomeric effect.
Ans.: The development of polarity in a molecule as a result of interaction between two p -bonds
or a p -bond and an atom or a group with a lone pair electrons is known as mesomeric effect
or resonance.
6. What do you mean by reactive intermediates? What are the types of intermediate?
Ans.: Short-lived and highly reactive fragments are called reactive intermediate. They are of the
following types:
1. Free radical
2. Carbocation or cabonium ion
3. Calbanion
4. Calbene
5. Nitrene
6. Benzyne
7. Write the reactions involving free radical intermediate.
Ans.: 1. Wurtz reaction
2. Anti-Markovnikov’s addition
3. Kolbe electrolysis
4. Substitution
8. Write the formation of carbocation.
Ans.:
By Heterolysis process:
+
(CH3)C Cl (CH3)3C
By protonation of alkenes or alcohol:
H+ +
CH2 CH2 CH3 CH2
H+ + +
R OH R OH2 R H2O
By decomposition of diazo compounds:
−Cl + −N2 +
C6H5 N2 Cl C6H5 N2 C6H5
9. Give different types of reactions?

Ans.: The types of reactions are as follows:
1. Addition reaction
2. Elimination
3. Substitution
4. Rearrangement

15.38
10. Write a short note on substitute reaction.

Ans.: W hen an atom or a group attached to a carbon atom in substrate molecule is replaced by
another atom or a group of atoms during the reaction and there is no change occur in car-
bon skeleton, it is called substation. It is of three types:
1. Free radical substitution
2. Nucleophilic substitution
3. Electrophilic substitution
11. Describe elimination reaction?
Ans.: In these reactions, generally, atoms or groups from two adjacent carbon atoms (a, b) in
the substrate molecule are removed and a multiple bond is formed. This is called elimina-
tion reaction.
12. Write the types addition reaction.
Ans.: Based on the involving reactive intermediates, the addition reaction is classified into three
types.
1. Free radical
2. Nucleophilic addition
3. Electrophilic addition
13. Define bonding and anti-bonding molecular orbitals.
Ans.: Anti-bonding orbital: The molecular orbital with higher energy gives rise to a repulsive
state called anti-bonding orbital.
Bonding orbital: The molecular orbital with lower energy gives rise to an attractive state
called bonding orbital.
14. Give the increasing energy order of molecular orbitals.
Ans.: s 1s < s *1s < s 2s < s *2s < s 2px < p 2py = p 2pz < π*2py = p *2pz < s *2px (For homo
nuclear atoms; the atomic number is more than seven)
s 1s < s *1s < s 2s < s *2s < p 2py = p 2pz < s 2px < p *2py = p *2pz < s *2px (For homo
nuclear atoms; the atomic number is less than seven)
15. What is the bond order present in B2, C2 and N2?
Ans.: Boron molecule (B2) - 1
Carbon molecule (C2) -2
Nitrogen molecule (N2) -3

Q.1 Give a detailed note on hybridisation and its salient features, important conditions and types.
Q.2 Explain the inductive effect with suitable examples.
Q.3 Describe electrometric effect and resonance effect with suitable examples.
Q.4 Describe the reactive intermediate in detail.

Q.5 Write a note on the types of reactions. Explain all reactions with examples.
Q.6 Give a brief note on molecular orbital theory and its importance.
Q.7 Explain molecular orbital diagrams of N2 and O2 molecules. What is the difference in their
molecular energy levels?
Q.8 Explain the molecular energy diagrams of CO and NO.

16 STEREOCHEMISTRY
16.1 INTRODUCTION
The properties of molecules depend on the arrangement of atoms in a molecule. The arrangement of
atoms or groups in a molecule is explained by stereochemistry. In Greek, “stereo” means solid/volume/
space; hence, stereochemistry means chemistry in space.
Stereochemistry is the branch of chemistry which deals with three-dimensional (3D) structure of
molecules and studies the physical, chemical and biological properties of organic molecules.
16.2 ISOMERISM
Organic compounds having the same molecular formula but differing from each other by some of physi-
cal or chemical properties or both are known as isomers and the phenomenon is known as isomerism. The
term “isomer” was first introduced by Berzelius. In Greek, “iso” means equal and “meros” means parts.
The difference in the properties of isomers is due to the difference in the relative arrangement of
various atoms or groups present in their molecules. There are two main types of isomerism as follows:
(i) Structural or constitutional
(ii) Space or stereoisomerism
16.2.1 Structural Isomerism

The constituent atoms or groups are linked to one another within the molecule without any reference
to space. Structural isomers are compounds that have the same molecular formula but have different
structural formulae.
16.2.2 Space or Stereoisomerism

Stereoisomers have the same molecular and structural formulae but different spatial arrangement of
atoms or groups. The spatial arrangement of atoms or groups is also referred to as configuration of the
molecule.
16.3 CLASSIFICATION OF STRUCTURAL ISOMERISM

Structural isomerism is further classified into chain or nuclear isomerism, positional isomerism, ring
or chain isomerism and functional group isomerism.

16.2
16.3.1 Chain or Nuclear Isomerism

This type of isomerism is due to the difference in the arrangement of carbon atoms constituting the
chain, that is, straight or branched chain of carbon atom.
Example:
CH3
CH3 CH2 CH2 CH3 ; CH3 CH CH3
CH3
CH3 CH2CH CH2 ; CH3 C CH2
But-1-ene 2-Methyl propene
16.3.2 Position Isomerism

This is due to the difference in the position occupied by the particular atom or groups in the same car-
bon chain or due to different positions of (or) bonds in alkene and alkynes.
CH3 CH2CH CH2 ; CH3CH CH CH3
But-1-ene But-2-ene
16.3.3 Ring or Chain Isomerism

This type of isomerism is due to different modes of linking of carbon atoms, that is, the isomers possess
either open chain or closed chain structures.
Example:
CH2
C3H6 CH3 CH CH2 CH2 CH2
Propene Cyclopropane
16.3.4 Functional Group Isomerism

Compounds having the same molecular formulae but different functional group in their molecule show
functional isomerism known as functional group isomerism.
Example:
C2H6O CH3 CH2OH ; CH3 O CH3 C3H6O
ethanol dimethyl Saturated alcohol, ethers
ether O
CH3 CH2 C H
propenaldehyde
O
CH3 C CH3
acetone
CH2 CH CH2 OH
prop–2–en–1–ol
16.3.5 Metamerism
The different alkyl groups attached to the same polyvalent functional group or atom so that com-
pounds having the same molecular formulae but different structural formulae due to different

Stereochemistry 16.3
alkyl group on either side of the functional groups are called metamers and the phenomenon is known
as metamerism.
Example: C4H10O C2H5O C2H5 C3H4 O CH3
16.3.6 Tautomerism
Isomers simultaneously exist in equilibrium with each other; this is a special type of functional isom-
erism. The term “tautomerism” comes from the Greek word “tauto” which means same, and “meros”,
which means parts.
Tautomerism is a type of isomerism in which a substance exists in two readily interconvertible to
different structures, leading to dynamic equilibrium.
It is caused by the wandering nature of the mobile hydrogen atom between two polyvalent atoms
within the same molecule; it is also known as desmotropism (“desmos” means bond, and “tropos”
means turn). If the hydrogen atom oscillates between two polyvalent atoms linked together, that sys-
tem is a “dyad” and if the hydrogen atom moves from the first to the third in a chain, the system is a
triad.
Dyad System
Example: Hydrocyanic acid; here, the hydrogen atom oscillates between carbon and nitrogen atoms.
H C N C N H
Triad System
Example: Keto–enol system.
R′ R′
a b a b
d b b d
R″ R″
Erythro Threo
16.4 CLASSIFICATION OF STEREOISOMERISM

Stereoisomerism is further classified into three types—geometrical, optical and conformational
isomerism.
16.4.1 Geometrical Isomerism

The phenomenon exhibited by isomers having the same molecular formula and a double bond in their
special arrangements of atoms or groups with respect to the double bond is known as geometrical
isomerism. The isomers are called geometrical isomers.
Example: Maleic acid and fumaric acid with the molecular formula C4H4OH.
H COOH H COOH
H COOH HOOC H

16.4
Geometrical isomerism is also known as “cis-trans” isomerism. If two carboxylic acid (same groups)
groups are present on same side of the double bond, it is called “cis-isomers”. If they are present on the
opposite side, it is called “trans-isomers”.
CH3 CH3
CH3 H3C
When geometrical isomerism is caused due to the presence of one double bond and if the two groups
are identical, it is easy to name the geometrical isomers.
When a geometrical isomer contains more than one double bond, the compound is considered a
derivative of the longest chain which contains the maximum number of double bonds. The prefix “cis”
and “trans” being placed before the numbers indicate the position of the double bonds to describe the
relative positions of the carbon atoms in the main chain.
CH3
CH3
CH3
3-isopropyl hexa 2,4,-cis-diene
Geometrical isomerism is also exhibited by the cumulenes provided the number of adjacent double
bonds is in odd number.
Ph Ph Ph C6H4NO2
C C C C C
O2NH4C6 C6H4NO2 NO2H4C6 Ph
cis Trans
16.4.2 Optical Isomerism

Optical isomerism is a type of stereoisomerism in which the isomers are identical in molecular weight,
molecular formula; physical and chemical properties but differ in the arrangement of substituents about
an asymmetric carbon atom and their effect on the rotation of beam of plane polarized light.
Optical Activity
Ordinary light consists of rays of varying wave length vibrating in all directions perpendicular to
the direction of propagation. When ordinary light is passed through a Nicol prism, the vibration are
adjusted in a single plane only. The light whose vibrations occur only in one plane is termed as plane
polarised light. The devise that brings polarisation in the light is called a polariser.
Substances have the ability to rotate the plane polarised light either towards right (clockwise) (or) left
(anticlockwise); such substances are termed optically active substances and the property is called optical
activity. The apparatus which measures the extent rotation of the plane polarised light is called a polarimeter.
The angle of rotation depends on the following factors:
(i) Nature of substance
(ii) Wave length of light used (l)
(iii) Concentration of the solution (C) in g cm−3

(iv) Nature of the solvent

(v) Length of the path through which polarised light possess.
(vi) Temperature at which the measurements are made
The measurement of optical activity is done in terms of specific rotation which is defined as the rotation pro-
duced by a solution of 10 cm and unit concentration for the given wavelength of light at a given temperature.
°c a
specific rotation [a ]twavelength = obs
l×C
where a obs = rotation observed
l = length of solution in decimetres
C = number of grams in 1 ml solution.
Compound having the same physical and chemical properties but differing only in behaviour towards
polarised light is called optical isomers. This phenomenon is known as optical isomerism.
Optical isomers which rotate the plane polarised light to the right are known as “dextrorotatory”,
“d-form” or +ve sign.
The optical isomer which rotates the plane polarised light to the left (anticlockwise) is known as
“laevorotatory”, “l-form” or is indicated by -ve sign.
The optical power of the two aforementioned isomers is equal in magnitude but opposite in sign.
An equimolar mixture of the two forms, therefore, will be optically inactive. This mixture is termed
“racemic mixture”, dl-form or (t) mixture.
Molecular Symmetry and Chirality

Stereochemistry is primarily concerned with molecular geometry and is best described in terms of
molecular symmetry. In order to study the symmetry of a molecule, certain operations such as rotation,
reflection, etc., are required. By doing so if indistinguishable arrangement from original is obtained;
the operation is called “symmetry operation” and the molecule said to possess an element of symmetry.
A symmetry element is a mathematical entity present in a molecule. It may be point, an axis or a
plane. A symmetry element is a label given to a molecule that transforms in a given way. A symmetry
operation is a way of interchanging the molecule to form two geometrically equivalent parts.
There are four symmetry operations namely, rotation, reflection and inversion and a combination
of the first two. The symmetry of a molecule can be generally attained by four symmetry operations
and four corresponding elements of symmetry. Any organic molecule can be described by four sym-
metry elements as follows:
(i) Axis of symmetry, rotational axis of symmetry or simple axis of symmetry (Cn)
(ii) Plane of symmetry or reflection of symmetry (s)
(iii) Centre of symmetry (i)
(iv) Rotational and reflection axis of symmetry (Sn)
Axis of Symmetry (Cn )

Cn = 360/n, C2 = 180, C3 = 120, C4 = 90, C5 = 72, etc.
If an imaginary line can be drawn through the centre of the molecule by rotation about that axis by an
angle of 360/n, it gives a structure indistinguishable from the original. Then, the molecule is said to
possess the simple axis of symmetry (Cn). The axis is called n-fold or proper axis of symmetry and the
operation is called a Cn operation.

16.6
H H H H
⇒ 360 = 2 (Two fold axis of symmetry)
180°
180
Cl Cl Cl Cl
C2-axis
Plane of Symmetry (r )
Plane of symmetry can divide the molecule into two halves which are mirror images of each other or a
reflection of two halves of molecules across the plane; this makes it indistinguishable from the original.
The plane is called s and the operation is called s operation.
COOH COOH
O
H H
H H
Centre of Symmetry (i)

If a line is drawn from any part of the molecule to that point and is extended on equal distance beyond
it, an analogous part will be encountered and the molecule shows the centre of symmetry
(i) This symmetry element is sometimes called the “point of inversion”.
Cl H
F H F
H
H Cl
Rotational–Reflection Axis of Symmetry (Sn )

It is a combination of rotation axis and reflection symmetry. The Sn operation can be achieved by rota-
tion, followed by reflection—identical ⊥ C2 = Sn.
H1 Cl 180° Cl H2 H2 Cl
C C C C C C
Cl H2 H1 Cl Cl H1
Chirality
Organic molecules are classified into two types. Based on the chirality of a molecule, they are classified
into chiral molecules and achiral molecules.
Chiral Molecule
A molecule containing an asymmetric carbon is called “chiral”. It can also be defined as a molecule that lacks
reflection symmetry or exhibits optical rotation. It may also be a molecule that lacks Sn-axis of symmetry.

Achiral Molecule
A molecule may contain any kind of symmetry operation, that is, plane of symmetry, axis of symme-
try, rotational axis of symmetry and reflexion axis of symmetry.
Molecule Containing an Asymmetric Carbon

A tetragonal carbon containing four different atoms/groups are called asymmetric carbon (or) chiral carbon.
H
C COOH
HO
OH
Lacks Reflection Symmetry

If a molecule is superimposable on its images, it is said to possess reflection symmetry. On the other
hand, if it is not superimposable, the molecule lacks reflection symmetry. The molecule that possesses
reflection symmetry is achiral.
Molecule with One Chiral Centre

Molecule with tetra coordinate centre
H
H
C COOH OH
Cl
OH
Molecule with two chiral centres

Dissimilar chiral centre
Cl Br
CO2H
Cl Br
Number of isomers = 2n
n = Number of dissimilar chiral centre
Similar chiral centre
Cl
Cl
∴ Number of isomers = 2n − 1
n = Number of similar chiral centres
Stereochemical Terms
(i) Homomers: Molecules which have the same molecular formulae and are superimposable on
each other are called homomers.

16.8
(ii) Isomers: Molecules which have the same molecular formulae and are not superimposable on
each other are called isomers.
(iii) Superimposability: When one molecule is placed on another molecule, and if all the atoms,
groups, bond length and connectivity coincide with the corresponding ones in each other, they
are said to be superimposable.
(iv) Constitutional isomers: Isomers which have different molecular connectivity are called consti-
tutional isomers.
Example: chain, positional, functional, metamers, tautomers and ring chain isomers.
(v) Stereoisomers: Those isomers which have the same molecular connectivity are called stereoiso-
mers.
(vi) Enantiomers: Stereoisomers which are non-superimposable mirror images are represented by
(+ & −). Compounds which have asymmetric carbon show optical isomerism, but, sometimes, it
may not exhibit due to the presence of meso compound.
(vii) Diastereomers: Stereoisomers which are neither non-superimposable nor mirror images are
called diastereomers.
Example:
CH3 CH3 COOH COOH

H C OH HO C H HO C H HO C H
H C OH HO C H HO C H H C OH
CH2OH CH2OH CH2OH CH2OH
I II III IV
I and II; III and IV are enantiomers and I and III; I and IV; II and III; and II and IV are diastereomers.
Properties of Enantiomers and Diastereomers

The properties of enantiomers and diastereomers are as follows:
(i) A molecule can have only one mirror image and hence exists only in one enantiomeric pair; on
the other hand, structural conditions permitting a molecule can have many diastereomers.
(ii) No two stereoisomers can be enantiomers and diastereomers at the same time, that is, two enan-
tiomeric and diastereomeric relationships are mutually exclusive.
(iii) Enantiomers have identical physical and chemical properties such as boiling point, densities, re-
fractive index, etc. They differ only in their action on plane polarised light. One of the enantiomers
rotates the plane polarised light to the right or the clockwise direction and is known as dextroro-
tatory (d) and the other to the left or the anti-clockwise direction is known as laevorotatory (l).
A mixture of two equal amounts of dextro and laevo enantiomers is called racemic mixture; it is
optically inactive due to equal and opposite direction rotation of the plane polarised light.
(iv) Diastereomers have different physical and chemical properties.
Meso Compounds
A meso compound possesses a plane of symmetry even though it contains chiral centres. A meso com-
pound is “optically inactive as it contains an internal plane of symmetry; whatever relation is caused
by one chiral carbon is compensated by the rotation caused in the opposite direction but to the same
magnitude by the second chiral carbon.

Example: Two isomers of tartaric acid are optically active, due to the presence of a plane of symmetry
as shown in Figure 16.1. However, on mono esterification of tartaric acid, similar chiral centres become
dissimilar. Therefore, there is no plane of symmetry and it is optically active and will give four isomers.
CO2H CO2CH3
H OH Esterification H OH Absence of
plane of
H OH H OH symmetry
CO2H CO2H
Figure 16.1 Meso compounds

Racemic Mixture
A mixture of two equal amounts of dextro and laevo enantiomers is called racemic mixture; it is opti-
cally inactive due to equal and opposite direction rotation of the plane polarised light.
Resolution of Racemic Mixture

The synthesis of an optically active compound produces a mixture of both (+) and (−) isomers in equal
amounts. Such mixtures are called racemic mixture or racemate. The separation of a racemic mixture
into its two optical active components is known as resolution.
The following methods are used in racemic mixtures.
Chemical Resolution
Optically active isomers of the same compound resemble one another so closely in all properties except
optical isomers that are not possible to separate them by ordinary laboratory. If, however, the racemic
mixture is made to combine with another optically active compound, the difference is set up which can
be exploited for separation.
Example: Racemic lactic acid is allowed to combine with the optically active base (−) strychnine.
The salt formed will be as follows:
(−) strychnine (+) lactate and
(−) strychnine (-) lactate
These salts are not true enantiomers. They differ considerably in properties and, in particular, in solu-
bility in various solvent. By fractional crystallisation from a suitable solvent, they can be separated.
The treatment with dilute mineral acid removes optically active base and leaves two separate samples
of (+) lactic acid and (-) lactic acid.
Biochemical Resolution
When certain bacteria or moulds are added to a solution of racemic mixture, they bring about the
decomposition of the optically active forms more rapidly than others.
Example: Penicillium glaucum decomposes (+) tartaric acid more readily than (-) isomers.
Racemisation
Conversion of an optically active compound into a racemic mixture is called racemisation.
Thus, racemisation can be accomplished by heat and light.
Example: The conversion of either the optically active lactic acid into a racemic mixture by heat-
ing its aqueous solution may proceed through an end intermediate.

16.10
CH3 CH3 CH3 CH3

H C OH ∝C OH H C
OH HO C H
+
O C OH HO C OH O C OH O C OH
(+)-Acid Enol (+)-Acid (−)-Acid
(2 molecules) (unstable)
Racemic mixture
When the proton migrates back to the carbon atom, the process can involve the opening of either of two
linkages of the double bond that can produce either the original configuration or in it.
Molecule with Helical Shape

The helical, propeller or screw-shaped molecular entity shows chirality. A right-hand side helix is
described as a plus or p, a left hand side one as m or minus.
Erythro and Threo System

This nomenclature is used only for two adjacent chiral carbon compounds and has the following
structure:
R-Cab-Cbd-R″
Out of six substituents, the two substituents on two chiral centres should be the same.
When fisher projection are drawn for stereoisomers with two adjacent chirality centres, the pair of
enantiomers with similar groups on the side of carbon vertical chain is called erythro form. The pair of
enantiomers with similar groups on the opposite side is called threo form.
R′ R′
a b a b
d b b d
R″ R″
Erythro Threo
16.4.3 Conformational Isomers

Stereoisomers whose energy barrier for interconversion is less than 40 kJ/mole are called conforma-
tional isomers.
Configurational Isomers
Stereoisomers whose energy barrier for interconversion is more than 60 kJ/mole are called configura-
tion isomers.
16.4.4 R–S Nomenclature or CIP Nomenclature

The R–S nomenclature system is based on a 3D structure of molecule. It was first introduced by Chan
and Ingold and was subsequently developed by Chan, Ingold and Prelog, and hence the system is
known as CIP nomenclature. The assignment of configuration is done by applying two rules; the first
is the sequence rule and the second is the chirality rule.

The sequence rule arranges four ligands of chiral centre with priority sequences as 1 > 2 > 3 > 4
(or) a > b > c > d.
The chiral centre is then viewed from the side remote from the lowest ranking group 4 or d and the
assigned name to the chiral centre as ‘R’ or ‘S’.
Sequence Rule
(i) The ligand with a higher atomic number will get higher priority and is numbered from 1 to 4; the
decrease in the priority is 1 > 2 > 3 > 4.
Example: Br > Cl> F > H
(ii) When two atoms attached to the chiral centre is the same, take the next atoms in the group and so on.
Example: C2H5> CH3
(iii) If group has multiple bond, do duplication and triplication.
Example:
C
O O CN C N
C
O C NN
(iv) Heavier isotopes will have more priority over lighter isotopes.
Example: 13C > 12C, D > H
(v) When the chiral centre atom is a part of the ring system, the sequence rule is exactly the same.
Each branch of the ring is followed until a difference can be detected.
(vi) Give more priority to R configuration than S. Once the priority order of the ligand is identified,
the configuration assignment is made by chirality rule. According this rule, put these least priority
group, (4 (or) d) away from the viewer and determine order of 1 → 2 → 3 from this point of view
of the arrangement. 1 → 2 → 3 appears in clockwise direction the configuration is R, and the ar-
rangement appears in the anti-clockwise direction the configuration is ‘S’.
Example: lactic acid
3 3
CH4 CH4
H4 4H
2
HO2C OH HO CO2H
1 1 2
R S
The priority sequence for the most common groups and atoms is given as follows.
O O
(High priority) I, Br, Cl, SH, F, O C R, OR, OH, NO2, NH C R, NR2,

O O O O O O
NHR, NH2, CCl3, C Cl, C OR, C OH, C NH2, C R, C H, CN,

CH2OH, C6H5 , CR3, CH2R, CH3, H (Low priority).
Axial Chirality
The term used to refer to stereoisomerism resulting from the non-planar arrangement of four groups
in pair about a chirality axis is exemplified by allenes, abc c c d and by the atropisomerism

16.12
of ortho-substituted biphenyls. The configuration in molecular entities possessing axial chirality is

specified by the stereo descriptors, Ra and Sa (or by P or M).
Example: Spiro compounds biphenyls
a d (a)
b c (b)
16.4.5 E–Z Nomenclature

The configurational stereoisomers of the kind shown above need an additional nomenclature in order
to specify the spatial orientations of the group attached to the double bond. But description of cis-trans
configuration is ambiguous when all the four substituents attached to the double bond are different.
This is explained by E–Z nomenclature. Here, Z stands for “zusammen”, which means together and
E stands for “entagegen”, which means opposite in German.
This system also follows the sequence rules of R–S nomenclature, to assign the configuration of
geometrical isomers.
Select the atom or group with higher priority on each carbon if the atoms or group of the higher
priority on each carbon come on the same side of the double bond, the isomer is assigned ‘Z’ configura-
tion. On the other hand, if the atoms are groups of higher priority are present on each carbon atoms on
the opposite side of the double bond, the isomer is assigned the configuration ‘E’.
Example:
2 Br F 2 Br Cl 1
1 l Cl 1 l F
Z E
16.5 MOLECULAR REPRESENTATION

In 1871, van’t Hoff suggested that carbon has tetrahedral geometry. Since then, stereochemistry gained
importance. Originally, organic molecules were 3D, but 3D structures cannot be represented in the
original form on two-dimensional (2D) planes like board or paper. Stereochemistry can explain the
conversion of 3D molecular structure into 2D molecular structure on plane or paper.
In stereochemistry, four kinds of representation are available to represent the 3D structure into 2D
structure. They are as follows:
(i) Wedge and Dash projections
(ii) Fisher projections
(iii) Sawhorse projections
(iv) Newman projections
16.5.1 Wedge and Dash Projections

In this representation, the bonds are represented with three types of lines. One is with wedge shaped
thick line ( ), another is the dashed line (||||) and the remaining are normal solid lines ( ). The wedge-
shaped thick line indicates that the corresponding group is projecting towards the viewer, or above the

plane or in front of the viewer. The dashed line indicates that the corresponding group is projecting
away from the viewer or below the plane and the normal solid line indicates that the corresponding
group is in the plane of the black board or paper. If stereochemistry is unknown, this can be indicated
explicitly by the away line ( ).
These wedge formulae will give complete information, including the basic molecular formula,
geometry and bond angles as well.
Example: lactic acid
H COOH HOOC H
C C
HO CH3 H3C OH
16.5.2 Fisher Projections

(i) In Fisher representation, each asymmetric carbon (chiral centre) is represented with cross (+).
CHO
H OH
CH3
(ii) Fisher representation can have only one vertical line and one or more horizontal lines ( ).
(iii) The maximum number of carbons should be on the vertical line or select the longest carbon chain
as a vertical line and one or more horizontal lines, depending on the number of asymmetric car-
bon in the molecules.
(iv) Put the highly oxidised group at the top of the vertical line.
(v) (a) If any of the Fisher representation may rotate 180° in plane it produces initial representation only.
(b) If any of the Fisher representation may rotate 90° in plane it produces mirror image of initial
representation.
(vi) Each Fisher representation is eclipsed.
(vii) In the Fisher representation,
(a) The groups on the vertical line are below the plane.
(b) The groups on the horizontal line are in front of the plane.
(viii) The Fisher representation gives easier way to represent the molecule having more number of carbons.
Example: n-pentane
CH3 C2H5
H C H H C H
H C H H C H
C2H5 CH3
Wrong form Correct form
16.5.3 Sawhorse Representation

(i) In sawhorse representation, the molecule must be see in side way. Therefore, the observer can
see both front and back carbon.
(ii) In this projection, draw the C C bond as a diagonal line.

16.14
(iii) At the termini of the diagonal axis, place the three bonds with 120° representation each.
(iv) In the Sawhorse representation, the groups must be with the eclipse.
d d d
f
f f
e
Eclipsed e e gauche
c (or) a c
a a
c
b b b
CH3
H
H
H
H
H3C
H H
H H
H3C H3C
Eclipsed Staggered stable
un stable
16.5.4 Newman Representation

In Newman projection formulae, the molecules are seen along the C C bond.
(i) The front carbon is represented by the dot and the three other bonds are attached with 120° .
(ii) The back carbon is represented as a circle and the three other bonds are attached with 120°
O O .
(iii) The C C bond cannot be represented on the plane of the paper.
(iv) It is good for easy observation of groups present on two adjacent carbons; as the C C bond
allows rotating to change orientation of groups in space. Therefore, this representation is very
useful for conformational analysis.
Example: CH3 CH3
HH H H
H
H H H H
60°
(or)
H H U
H H H H
HH
H
Eclipsed Staggered
16.6 MOLECULAR ISOMERISM

Molecules with the same molecular formulae but with different arrangement of atoms in space are
called isomers. The criterion for determining isomeric relation is shown in Figure 16.2.

Do the molecules have same No They are not isomers.

molecular formulae?
Yes
Are they super imposable Yes They are called homomers.

on each other?
No
They are called isomers. Is the No They are called constitutional

molecular connectivity isomers.
(or) bonding same eg: (a) Chain (b) Position
(c) Functional (d) Metamerism
Yes (e)Tautomerism
No
They are called stereo isomers They are called diastereomers.
Do they have non-super imposable
mirror image relationship.
Yes
They are called enantiomers.
Are they are interconvertible at room temperature.

No Yes
Required energy 40-60 kJ/mole energised Required Energy

is >60 kcalJ/mole molecule are border line is < 40 kJ/mole
case depending on conditions
they act as both isomers
Configurational Conformational (or) dynamic

stereomers stereoisomers
Configurational Configurational Conformational Conformational

enantiomers diastereomers enantiomers diastereomers
Figure 16.2 Determination of molecular isomerism

1. Organic compounds having the same molecular formula but differ in some physical or chemical
properties are called .
[Ans.: Isomer]
2. Non-superimposable mirror images are .
[Ans.: enantiomers]
3. The stereoisomers which are interconvertible at room temperature >60 kJ mole are called
.
[Ans.: configurational isomers]

16.16

1. is a staggered form.
(a) H CH3 (b) H
H3C CH3
H3C CH3
H H H H
CH3
[Ans.: b]
2. Which of the following is an achiral carbon?
(a) b (b) a
c c a b c b
d a
(c) a (d) b
c c b a c c
d b
[Ans.: a]
3. Alcohol and ethers exhibit isomerism.
(a) Metamerism (b) Tauto isomerism
(c) Functional group (d) Chain isomerism
[Ans.: c]
4. Which substance is optically active?
(a) b (b) a
c c a a c a
d a
(c) b (d) b
a c a a c a
b c
[Ans.: a]
5. The same molecular formula and superimposable are used in .
(a) Stereoisomers (b) Homomers
(c) Optical isomers (d) All of these
[Ans.: b]
6. Detect the isomer.
(a) a a (b) a b
b b b a
(c) a a (d) a b
a a b c
[Ans.: a]

7. CH3 CH2 CH2 and CH3CH CH3 is an example of .

(a) Chain isomerism (b) Position isomerism
(c) Metamerism (d) Tautomerism
[Ans.: b]
8. Isomers with the same molecular formula but different structural formula are called .
(a) Structural isomers (b) Stereoisomers
(c) Optical isomers (d) None of thesew
[Ans.: a]
9. The different alkyl groups attached to the same polyvalent functional group are called (b)
(a) Tautomerism (b) Metamerism
(c) Mesomerism (d) Ring chain isomerism
[Ans.: b]
10. A tetragonal carbon containing four different groups are called .
(a) Symmetric carbon (b) Asymmetric carbon
[Ans.: b]
11. A molecule containing an asymmetric carbon is called .
(a) Achiral (b) Chiral
(c) Enantiomer (d) Diastereomer
[Ans.: b]
12. Cis-tran isomerism belongs to .
(a) Optical isomerism (b) Conformational isomerism
(c) Geometrical isomerism (d) Structural isomerism
[Ans.: c]
13. Eclipsed and staggered representations are observed in .
(a) Newman molecular representation
(b) Fisher representation
(c) Sawhorse representations
(d) Wedge and Dash representation
[Ans.: a]
14. The ability of a substance which rotates the plane polarised light is called .
(a) Optical activity (b) Optical inactive
[Ans.: a] CH3
15. CH3 CH2 CH2 CH3 and CH3 CH CH3 are .
(a) Structural isomers (b) Geometrical isomers
(c) Optical isomers (d) Stereoisomers
[Ans.: a]
16. Keto–enols are isomers.
(a) Meta isomers (b) Geometrical
(c) Stereoisomers (d) Tauto isomers
[Ans.: d]

16.18
17. Erythro and threo isomers belong to .

(a) Optical isomers (b) Stereoisomers
(c) Structural isomers (d) Configuration isomers
[Ans.: a]

1. Define isomerism.
Ans.: Organic compounds having the same molecular formula but differing from each other at
least in some physical properties or chemical properties or both are known as isomers and
the phenomenon is called isomerism.
2. Write a note on structural isomerism.
Ans.: The constituent atoms or groups are linked to one another within the molecule without any
reference to space structural isomers. These are compounds that have the same molecular
formula but different structural formulae.
3. Write the types of structural isomers.
Ans.:
1. Chain isomerism
2. Position isomerism
3. Ring chain isomerism
4. Functional group isomerism
5. Metamerism
6. Tautomerism
4. Explain stereoisomerism.
Ans.: Stereo means space, “iso” means equal and “mers” means parts.
It has the same chemical formula but differs with spatial arrangement of atoms or groups
and are called stereoisomers and the phenomenon is called stereoisomerism.
5. Describe optical activity and optional isomerism.
Ans.: Substance that has the ability to rotate the plane polarised light either to the right or left are
termed as optical active compounds and that property is called optical activity.
Compound having the same physical and chemical properties but differs only in the behav-
iour towards plane polarised light is called optical isomerism.
6. Write the types of molecular representations.
Ans.:
1. Wedge and Dash representation
2. Fisher representation
3. Sawhorse representation
4. Newman representation

7. Differentiate between enantiomers and diastereomers.

Ans.:
Enantiomers Diastereomers
hose stereoisomers which have non-
T hose stereoisomers which have neither
T
superimposable mirror images are called non-superimposable nor mirror images are
enantiomers. called diastereomers.
nantiomers have identical physical and
E iastereomers have different chemical
D
chemical properties. properties.

Q.1 Give a detailed sketch on molecular representations and the types of molecular representation.
Q.2 Write a note on stereochemical terms and the properties of enantiomers and diastereomers.
Q.3 Describe configuration isomerism.
Q.4 Write a brief note on geometrical isomerism.
Q.5 Explain the E–Z nomenclature with a neat sketch.
Q.6 Write about isomerism and its significance.

17 SPECTROSCOPY
17.1 INTRODUCTION
All integral laws of spectral lines and of atomic theory spring originally from the quantum theory. It
is the mysterious organ on which Nature plays her music of the spectra, and the rhythm to which she
regulates the structure of the atoms and nuclei.
Spectroscopy is the study of the interaction of electromagnetic radiation in all its forms with matter.
Electromagnetic spectrum is the range of all types of electromagnetic radiation. The interaction might
give rise to electronic excitations (UV), molecular vibrations (IR) and nuclear spin orientation (NMR).
Electromagnetic energy is used while listening to the radio, watching television, sending a mes-
sage or popping popcorn in a microwave oven.
Examples: Radio waves, microwaves, infrared light, UV-visible light, X-rays, etc.
The sun is a source of energy across the entire spectrum; the electromagnetic radiation bombards
the atmosphere and protects us from high energy waves that can be harmful to life. Electromagnetic
energy travels in the form of waves and spans a broad spectrum from very long radio waves to very
short gamma rays and shown in Figure 17.1. The human eye can only detect a small portion of this
spectrum called visible light.
Electromagnetic radiation can be described in terms of a stream of mass-less particles, called
photons, each travelling in a wave-like pattern at the speed of light. Each photon contains a certain
amount of energy. Different types of radiation are defined by the amount of energy formed in photons.
The frequency is measured in cycle per second or Hertz. Wavelength is measured in metres and energy
is measured in electron volts.
Electromagnetic spectrum 400nm BOYGBIV 700nm

Electronic transition
Electronic transition
Molecular vibration
d-d &, f-f transition

Molecular rotation
in valance shell
Electron spin
Nuclear spin
in inner shell
transition
transition
NMR ESR Micro wave Infra red Visible UV X-Ray
Longer wave length Shoter wave length

Lower frequency higher frequency
Lower energy higher energy
Figure 17.1 Electromagnetic spectrum

17.2
17.2 ULTRA VIOLET AND VISIBLE SPECTROSCOPY
17.2.1 Principle
On passing electromagnetic radiation in the UV and visible region through a compound, a part of the
radiation is absorbed by the compound. After the absorption of energy, the electrons in the orbital of
lower energy are excited into the orbital of higher energy.
The energy absorbed by the molecule will be equal to the difference between the two energy levels
like lower and higher energy. During this stage, spectra electronic excitations occur. Hence, some-
times, it is also called “electronic spectroscopy”.
UV-Vis Electronic
Radiation Sample transitions
Electronic transitions are observed in the electronic vibrational and rotation level and they produce
broad UV-Vis bands. When a graph is drawn by taking absorbance on Y-axis and wave length on X-axis,
we get a curve structure; it is shown in Figure 17.2. This is different for different types of excitations. By
using this graph, we can analyse the compound. In the graph, 100% absorbance occurs at λ max value.
y
A 100
b
s
o 80
r
b
a 60
n 50
c
e 40
20
x
O l l l l l l l l l
Wave length (l)
Figure 17.2 Graph showing electronic transition

The UV region is further divided into two regions:
(i) Vacuum region 100–190 (200 nm)
(ii) Near UV region 190–400 nm
17.2.2 Instrumentation
A beam of light from a visible and/or UV light source is separated into its component wavelength
by a prism or diffraction grating. Each monochromatic beam is split into two equal intensity beams
by a half-mirrored device; one is the sample beam that passes through a small transparent container
(cuvette) containing a solution of the compound being studied in a transparent solvent and other beam
is the reference that passes through an identical cuvette containing only the solvent. The intensity of
these beams is measured by an electronic detector and compared. The intensity of the reference beam
which should have absorbed little or no light absorption is indicated as “Io” and the intensity of the

Spectroscopy 17.3
sample beam is indicated as ”I”. Over a short period of time, the spectrometer automatically scans
all the component wave length in the described manner. The UV region is scanned as normally from
200–400 nm. The visible region is scanned from 400–800 nm. The UV-Vis spectrometer block dia-
gram is shown in Figure 17.3.
Mirror
Reference
Duterium Tungston
or
lamp lamp M
irr Photo diode
Data
Filter read out
Absorbance
Data
processing
Photo diode
Beam spliter
Mono chromator
Sample
Figure 17.3 UV-Vis spectrometer block diagram
17.2.3 Instrumental Design

A spectrometer is an instrument for measuring the transmittance or absorbance of a sample as a func-
tion of the wave length of electromagnetic radiation. The key components of a spectrophotometer are
as follows:
(i) Source (UV-Vis)
(ii) Wave length selector (monochromator)
(iii) Sample cell/reference cell
(iv) Detector
Source
The source generates a broad band of electromagnetic radiation. The commonly used sources in the
UV-Vis spectrophotometers are deuterium arc lamp and tungsten-halogen lamp.
Deuterium Arc Lamp

The first source, the “deuterium arc lamp”, yields a good intensity continuum in the UV region and
provides useful intensity in the UV region. Modern deuterium lamps have low noise; noise from the
lamp is often the limiting factor in overall instrument noise performance. Over time, the intensity of
light from a deuterium arc lamp steadily decreases. The half-life of such typical lamps is 1,000 hours.

17.4
Tungsten-halogen Lamp
The second source, the tungsten-halogen lamp, yields good intensity over the part of the UV spectrum
and the entire visible range. This type of lamp has very low noise and low drift and has a half-life of
10,000 hours. Most spectrophotometers used to measure UV-Vis range contain both types of lamps.
In such instruments, either a source selector is used to switch between the lamps as appropriate or the
light from the two sources is mixed to yield a single broad band source. Sometimes, xenon lamp is used
as an alternate light source, but it is highly expensive.
Wave Length Selector (Dispersion Device)

A dispersion device gives a different wavelength of light to be scattered at different angles. When com-
bined with an appropriate exist slit, these devices can be used to select a particular wavelength of light
from a continuous source. Prism and holographic grating are commonly used as wavelength selectors
in a UV-Visible spectrophotometer.
Prism
A prism generates a rainbow from sunlight—the same principle is used in spectrophotometers. Prisms
are simple and inexpensive. The resulting dispersion is angularly non-linear. The angle of dispersion is
temperature-sensitive; hence, holographic gratings are used instead of the prism.
Holographic Grating
The light falling on the grating is reflected at different angles, depending on the wavelength. Holographic
grating yields a linear angular dispersion at wavelength and is temperature-insensitive. However, it
reflects light in different orders. As they overlap, a filter must be used to ensure that only light from the
desired reflection order reaches the detectors.
A monochromator consists of an entrance slit, a dispersion device and an exist slit. Ideally, the
output from monochromator is a monochromatic light.
Optics
These are used to relay and focus light through the instrument. These are carefully designed with the
chromatic aberration of individual lenses in an optical system and can be used to cancel each other out.
An effective optical system can be constructed with the following simple and inexpensive components.
Cuvettes
The most commonly used cell is the open-topped rectangular cell. These cells are available in path
length from 1 to 100 mm. The normally used cuvettes having path length of 10 mm. The external width
of a rectangular cell is 12.5 mm. When the sample volume is limited, narrow opening cells are often
used. When sample volume is extremely limited, micro cells can be used that reduce the aperture of
the sample area to a very small cross section. Only approximately 60 µl of sample is required for meas-
urement. Ultra microcells, sample volumes down to 5 µl can be measured. The flow through cells are
used for automated application. Modern cells are connected to sample transferring through tubing with

Spectroscopy 17.5
screw fitting. With aperture cells and microcells, parts of the light beam are blocked, throughput is
reduced and sensitivity is compromised to an extent. The loss of sensitivity depends on the degree of
aperturing and on the optical geometry. The single beam instrument, the cuvette containing the solvent
is placed in the spectrometer and the blank is measured after the sample solution is then measured in
the same cuvette. All modern instruments automatically store the reference IO values which calculate
absorbance values for the sample.
Dual and split beam instruments require two cuvettes. Initially, both cuvettes are filled with a pure
solvent and a so-called balance measurement is performed. This measurement reflects the difference in
absorbance between the two optical paths in use. The sample cuvette is then filled with a sample solu-
tion for measurement, and IO and I are measured. The resulting spectrum is corrected by subtracting
the balance spectrum.
Detector
A detector converts a light signal into an electrical signal. Spectrophotometers normally contain either
photomultiplier tube or a photodiode detector. In UV-Vis spectroscopy, the photo multiplier is a com-
monly used detector; it consists of a photo emissive cathode, several dynodes and an anode. A pho-
ton of radiation entering the tube strikes the cathode causing the emission of several electrons; these
electrons are accelerated towards the first dynode. The electrons strike the first dynode, causing the
emission of several electrons from the incident electron. These electrons are then accelerated towards
the second dynode and produce more electrons which are accelerated towards the third dynode and
so on. Eventually, the electrons are collected at the anode. Each original photon has produces 106 –107
electrons; the resulting current is amplified and measured. Photo multiplier is very sensitive to UV and
visible radiation and has fast response time. Intense light damages photo multiplier and are limited to
measuring low power radiation.
17.2.4 Electronic Transitions

The range of UV- Visible spectroscopy is 200–800 nm. The range for UV is specifically 200–400 nm
and for visible ranges at 400–800 nm. Such type of UV-Vis radiation gets exposed with molecules.
At that time, the electrons which are present at bonding molecular orbital and non-bonding molecular
orbital enter into anti-bonding molecular orbital such as s * and p *.
Here, s and p are bonding molecular orbital, n stands for non-bonding orbital and s * and p *
stand for anti-bonding molecular orbital. Molecule exposed to UV-Visible radiation bonding molecular
orbital as well non-bonding molecular orbital electrons will absorb energy and get transfer from the
ground state to the excited state, that is, antibonding molecular orbital.
The following different types of electronic transitions are observed in UV-Visible spectra:
(i) s — s * (iii) n — s*
(ii) p — p * (iv) n — p *
r -r * Electronic Transitions
Very high energy is required for the s -s * transition. Such type of transition is observed below 200 nm,
that is, vacuum ultra-violet region
Example: Saturated hydro carbon.

17.6
n-r * Electronic Transition

Saturated molecule which contains hetero atoms like oxygen, nitrogen, etc., having a lone pair of
electrons involves these types of electronic transitions. These transitions are comparatively less energy
transitions than s –s * transitions.
Example: Alcohols, amines and ethers.
o –o * Transition
Unsaturated compounds involve these types of electronic transitions.
Example: Alkene, alkynes and aromatic compounds.
n–o * Electronic Transition

In these transitions, an electron from a lone pair on a hetero atom is exited to anti-bonding p * orbital.
Example: Carbonyl compounds.
17.2.5 Chromophores
It is a group of molecule, which is responsible for the absorption of light by molecules. It is conju-
gated dienes. It is the minimum structural requirement for the absorption of radiation in UV-range. By
having functional groups or some other structural features, its presence gives a colour to a compound.
Nowadays, the term chromophore is used in much boarder sense which may be defined as any group
which exhibits absorption of Electromagnetic Radiation (EMR) in the visible or UV region. It may or
may not import the any colour to the compound.
Two types of chromophore are as follows:
Chromophores in which the group has p electrons undergo p → p * transitions.
Example: Ethylene, acetylene.
Chromophores having both p -electrons and nonbonding electrons undergo two types of transi-
tions—p → p * and n → p *
Example: carbonyls, nitriles, azo compounds, acids.
17.2.6 Auxochrome
In isolated chromophore groups such as >c c< and c c , absorption takes place in far ultraviolet
region which cannot be easily studied. However, the position of absorption is maximum and the intensity
of absorption can be modified in different ways by some structural changes or change of solvent as follows.
“In auxochrome, it is a group which itself does not act as a group chromophore but when it is attached
to a chromophore, it shifts the absorption maximum towards longer wave length along with an increase in
the intensity of absorption”.
Some commonly known auxochromic groups are OH, NH2, OR, NHR and NR 2
Example: When auxochrome NH2 group is attached to benzene ring, it absorption changes from
λmax 255 to λmax280.
All auxochromes have one or more non-bonding pair of electrons.
If auxochrome is attached to a chromophore, it helps in extending the conjugation by sharing of
non-bonding pair of electrons.
⊕ ⊕
CH2 CH NR2 CH2 CH NR2

Spectroscopy 17.7
17.2.7 Woodward–Fieser Rules

In 1945, Robert Burns Woodward proposed rules for correlating of λmax values with molecular
structure; but in 1959, Louis Frederick Fieser modified these rules with more experimental data, and
the modified rule is known as Woodward-Fieser Rules. These are used to calculate the position and
λmax for a given molecular structure by relating the position and degree of substitution of chromophore.
According to Woodward and Fieser, each type of diene or triene system has a certain fixed λmax
value; this is known as base value or parent value. The contribution made by various alkyl substituent,
ring residue, double bond extending conjugation, polar groups such as Cl, Br, etc., are added to the
base value to obtain λmax for a particular compound.
Conjugated Dienes
Different types of conjugated dienes are as follows:
(i) Homoannular diene Cyclic diene having conjugated double bonds in same ring.
(ii) Heteroannular diene Cyclic diene having conjugated double bonds in different rings.
(iii) Endocyclic double bond Double bond present in a ring.
(iv) Exocyclic double bond Double bond in which one of the doubly bonded atoms is a part of a ring
system.
A B
Here, ring A has one exocyclic and endocyclic double bond. Ring B has only one endocyclic double
bond.
Base Values of Different Organic Functional Groups and Increments for Substituent/
Groups are Shown in Tables 17.1–17.4
Table 17.1 Conjugated diene correlations

S. no. Diene/substituent/group Base value (nm) Substituent/group (nm)
1. Homoannular diene 253 –
2. Heteroannular diene 214 –
3. Alkyl substituent or Ring residue – 5
4. Double bond extending conjugation – 30
5. Exocyclic double bonds – 5
6. OAc(Oxy acetyl) – 0
7. OA (Oxy alkyl) – 6
8. Cl/Br – 5

17.8
Example:
For Heteroannular base value = 214 nm

Ring residue = 3 × 5 = 15 nm
Exocyclic double bond = 1 × 5 = 5 nm
λmax = 214 + 15 + 5 = 234 nm
Table 17.2 a , b unsaturated carbonyl compounds or ketones

S. no. a, b unsaturated carbonyl compounds or ketones/ Base value Substituent/
substituent/group (nm) group (nm)
1. Acyclic a, b unsaturated ketones 214 –
2. 6 membered cyclic a, b unsaturated ketones 215 –
3. 5 membered cyclic a, b unsaturated ketones 202 –
4. a, b unsaturated aldehydes 210 –
5. a, b unsaturated carboxylic acids & esters 195 –
6. Alkyl substituent or ring residue in a position – 10
7. Alkyl substituent or ring residue in b position – 12
8. Alkyl substituent or ring residue in g and higher positions – 18
9. Double bond extending conjugation – 30
10. Exocyclic double bonds – 5
11. Homodiene compound – 39
12. OH in a position – 15
13. OH in b position – 30
14. OH in d position – 50
15. OAc in a, b, g, d positions – 6
16. OMe in a position – 35
17. OMe in b position – 30
18 OMe in g position – 17
19. OMe in δ position – 31
20. Cl in a position – 15
21. Cl in b position – 12
22. Br in a position – 25
23. Br in b position – 30
24. NR2 in b position – 95
Example:
O
Base value = 214 nm
b - Substituents = 1 × 12 = 12 nm
d - Substituents = 1 × 18 = 18 nm
Double bond extending conjugation =1 × 30 = 30 nm
Exocyclic double bond = 5 nm
l max = 214 + 12 + 18 + 30 + 5 = 279 nm

Spectroscopy 17.9
Table 17.3 Aromatic compounds

S. no. Aromatic compounds/substituent/group Base value (nm) Substituent/
group (nm)
1. ArCOR 246 –
2. ArCHO 250 –
3. ArCO2H 230 –
4. ArCO2R 230 –
5. Alkyl group or ring residue in ortho and meta position – 3
6. Alkyl group or ring residue in para position – 10
7. OH, OCH3, OAlkyl in ortho/meta position – 7
8. OH, OCH3, OAlkyl para position – 25
9. O (oxonium) in ortho position – 11
10. O (oxonium) in meta position – 20
11. O (oxonium) in para position – 78
12. Cl in ortho/meta position – 0
13. Cl in para position – 10
14. Br in ortho/meta position – 2
15. Br in para position – 15
16. NH2 in ortho/meta position – 13
17. NH2 in para position – 58
18. NHCOCH3 in ortho/meta position – 20
19. NHCOCH3 in para position – 45
20. NHCH3 in para position – 73
21. N(CH3)2 in o, m position – 20
22. N(CH3)2 in p position – 85
Example:
MeO
O
Base value = 246 nm
Ring residue in o- position = 1 × 3 = 3 nm
Polar group OCH3 in p- position = 25 nm
λmax = 246 + 3 + 25 = 274 nm
Table 17.4 Absorptions wave length of typical organic functional groups
Chromophore System Wave length of absorption maximum
Vm
Amine NH2 195
Bromide Br 208
Iodide I 260
Thioketone >C S 205
Ester O 205
R C
OR
(Continued )

17.10
Chromophore System Wave length of absorption maximum
Vm
Aldehyde O 210
R C
H
Carboxylic acid O 200–210
R C
H
Nitro NO2 210
Nitrite ONO 220–230
A3O N N 285–400
Conjugated olefins (C C)2 210–230
(C C)3 260
( C C)5 330
Benzene (1) 198
(2) 255
Naphthalene (1) 220
(2) 275
(3) 314
actors Affecting the Position of the λ Maximum

17.2.8 F
and Intensity of Radiation
The absorption spectra is the graph between the light absorption and the frequency. It is characterised
by the following:
(i) λmax: Position of spectra.
(ii) Intensity: The amount of radiation absorbed by the molecule.
Factors Affecting the Position of Spectra (k max)

The position of the spectra mainly depends on the following several structural and non-structural
features:
Structural Factors
Substitution
λmax may affect by substituent on a chromophore by two mechanisms—by changing of transition or
shifting the wavelength of existing transitions.
Example: Each alkyl substituent produces 5 nm bathochromic shift.
Solvent
The solvent effect arises due to different salvation for the ground and exited states; if the ground state is
more solvated strongly than the exited state, the energy difference is increased. The increased energy
difference shift the absorbance towards shorter wave lengths.

Spectroscopy 17.11
Geometry
Due to steric effects, trans-stilbene absorbs at a longer wavelength than cis-stilbene. Co-planarity is
required for the most effective overlap of the p - orbitals. Due to steric effects, the cis-isomer is forced into
a non-planar conformation and twisted slightly out of plane by steric interactions so that the degree of con-
jugation in the p -system is slightly less than trans isomers, resulting in greater energy for the transition.
Non-structural Factors
(i) PH
(ii) Temperature: Temperature gives more energy to the ground state; as a result energy required for
excitation will be less.
Factors Affecting the Intensity of Absorption of Radiation

Thickness of the Medium
Lambert’s law: When a beam of monochromic light is allowed to pass through a transparent medium,
the rate of decrease of intensity with the thickness of medium is directly proportional to the intensity
of incident light.
Concentration
Beer's law: When a beam of monochromatic light is allowed to pass through a transparent medium, the
rate of decrease of intensity with the concentration of absorbing solute is directly proportional to the
intensity of incident radiation.
A = e cl
Where A = Absorbance
e = Extinction coefficient
C = Concentration of solution
I = Wave length
17.2.9 Franck-Condon Principle

Kasha’s Rule
In the electronic excited state, molecules quickly relax to the lowest vibrational level of the lowest
electronic excitation state and they can come back to the electronic ground state via photon emission.
Stokes’ Shift
The displacement of fluorescence bands towards the longer wavelengths (lower energy) can be com-
pared to the absorption bands. This was a long-established experimental fact before the Franck-Condon
principle provided its interpretation.
Franck–Condon Principle
The Franck–Condon principle is applied to both absorption and fluorescence; it has a classical and
quantum application that explains the intensity of vibronic transitions.

17.12
The classical formulation, of the Franck–Condon principle is an electronic transition occurs

without changing in the positions of the nuclei in the molecular entity and its environment; the result-
ing state is Franck–Condon state, and the transition involved is a vertical transition.
The quantum mechanical formulation of the Franck–Condon principle is that the intensity of a
vibronic transition is proportional to the square of the overlap integral between the vibrational wave
functions of the two states that are involved in the transition.
The Franck-Condon Principle explains in detail the intensities of vibronic transitions, or the absorp-
tion or emission of a photon. The nuclear configuration of the molecule experiences no significant change
when a molecule undergoes an electronic transition, such as ionisation. This is because the nuclei are much
more massive than electrons and the electronic transition takes place faster than the nuclei can respond.
The theory states that it must undergo a vibration when the nucleus realigns itself with the new
electronic configuration. The nucleus in a molecule has Coulombic forces acting on it from the elec-
trons and other nuclei of the system. Once a molecule undergoes the electronic transition, the resulting
Coulombic forces serve to change the energy of the molecule. This change brings it from the ground
state to an excited state and the results in the nuclei change its vibrational state. This vibrational struc-
ture of an electronic transition shows that the absorption spectrum consists of many lines instead of a
single sharp electronic absorption line.
Consider a diatomic molecule with atoms A and B that oscillate back and front along the axis of
bond linking them. The potential energy of such system is related to interatomic distance (g AB), plot
between potential energy and inter atomic distance shown in Figure 17.4.
The area within the potential energy curve is populated with different vibrational levels of the
molecule. These levels are quantised and the energy separation between the levels decreases with
increasing value of g AB.
The electronic excitation of such a system by light absorption in a change in the overall electronic
distribution within the molecule forms a different potential curve. The Franck-Condon principle states
that the inter-nuclei distance in a molecule is fixed during the electronic transition. This indicates the
electronic transition of the exited states has the same geometry and interatomic bond distances as same
as the ground state of the molecule.
y
Potential energy (E)
γe (equillibrium
distance)
x
γAB (interatomic distance)
Figure 17.4 Graph between potential energy and inter atomic distance
17.2.10 Solved Problems Based on UV-VIS Spectroscopy

(i) Find the name and λ maximum values of the following compounds in the UV-Vis Region
(a)


Spectroscopy 17.13
Name of the Compound - 2,4-dimethylpenta-1,3-diene

λ maximum value – 234 nm
(b)

Name of the compound - 1-methylcyclohexa-1,3-diene
O
(c)

Name of the compound - 3,4-dimethylpenta-3-en-2-one
17.2.11 Applications of UV-Visible Spectroscopy

Ultra-violet spectroscopy is used more extensively in assaying (quantitative measurements) than in
identification. UV spectroscopy is usually applied for predicting the conjugated double bonds a , b
unsaturated carbonyl compounds, organic and inorganic complexes in a solution. UV-Visible spectros-
copy is used to characterise the absorption, transmission and reflectivity of various important materi-
als such as pigments, coatings, etc.
Quantitative Analysis
This quantitative determination of compounds is based on Beer’s law which is as follows:
A = log I0/It = log 1/T = −logT = abc = ¨bc
where ¨ = Extinction co-efficient
c = concentration
b = length of the cell
Example: The trace metal content of an alloy such as manganese in steel can be determined.
Qualitative Analysis
UV absorption spectroscopy can be characterised by comparing the absorption spectrum with the
spectra of known compounds.
Example: Characterisation of aromatic compounds and aromatic olefins.
Chemical Kinetics
Kinetics of reaction rates can be determined by using UV-Visible spectroscopy. If a reagent or a prod-
uct of the reaction absorbs radiation at a particular frequency, the spectrometer can be set to measure
the absorption at that frequency as a function of time.
Example: The rate of hydrolysis of an ester.

17.14
Detection of Impurities
Due to the presence of impurities in a substance that give it additional peaks, it can be compared
with standard materials. The impurities can also be detected by measuring the absorbance at specific
wavelength.
Example: Benzene appears as a common impurity in cyclohexane; its presence can be easily
detected by its absorption at 255 nm.
Structure Elucidation of Organic Compound

The structure elucidation of an organic compound and a hetero atom can conclude by location and
combination of peaks; whether the compound is saturated or unsaturated, hetero atoms are present or
not.
Dissociation Constants of Acids and Bases
pH = Pka + log[A-]/[HA]
If the ratio of particular pH and the ratio of [H-]/[HA] can be determined spectrophotometrically from
the graph plotted in between absorbance and wave length of different pH values, the Pka value can be
calculated from the above equation.
Molecular Weight Determination

By preparing the suitable derivatives of the particular compounds, the molecular weight of compound
can be measured spectrophotometrically.
Example: To calculate the molecular weight of amine, it is converted into amine picrate. The
known concentration of amine picrate is dissolved in one litre solution and its optical density is meas-
ured at λmax 380 nm. After this, the concentration of the solution in gram mole per litre can be calcu-
lated by using the following equation:
log I 0 / I t
c=
ε max × q
As HPLC Detector
The UV-Visible spectrophotometer may also use as a detector for HPLC.
17.3 IR-SPECTROSCOPY
Infrared (IR) spectroscopy is applied to a broad range of organic and inorganic materials in solid, liq-
uid and gaseous forms. The crystal, molecular vibrational modes absorb electromagnetic radiation. In
general, functional groups that have strong dipoles give rise to strong absorptions in the infrared spec-
trum. The infrared spectral range is roughly 1 to 100µ (10,000 to 100 cm-1). The IR technique is quick,
simple and relatively inexpensive and serves as a useful supplementary technique in the identification
of natural inorganic species such as minerals and natural compounds. Oxygen and nitrogen do not

Spectroscopy 17.15
absorb infrared light. Their molecular symmetry does not possess dipole moment of vibrational excita-
tion. Solids such as NaCl, KBr, CaF2, LiF, CaBr and CsI are used as transparent windows and prism
materials for IR spectroscopy because of their vibrational absorptions are in different spectral regions.
17.3.1 Basic Principle

The absorption of IR transitions occur in vibrational or rotational energy level, but does not have
enough energy to induce electronic transitions as seen with UV. Molecule absorb IR radiation, the
vibrations or rotations within the molecules must cause a net change in the dipole moment of the mol-
ecule; but do not require any permanent dipole moment.
The electric field of the radiation interacts with fluctuations in the dipole moment of the molecule;
if the frequency of the radiation matches the vibrational frequency of the molecule, then radiation
will be absorbed, causing a change in the molecular vibrations. The interpretation of an IR spectrum
provides information about the functional group present in molecule. An IR spectrum is a plot of wave-
length versus absorption. Specific absorption bands indicate the presence of the particular functional
group. By itself, an IR spectrum does not provide enough information about the complete chemi-
cal structure of the compound. However, it is very helpful when combined with other spectroscopic
technique.
Generally, molecules are always in motion. The bond between atoms involve in stretching, bend-
ing, wagging, twisting and rocking. These are called molecular vibrations. Organic compounds absorb
IR radiation in different types of bonds (in different functional groups) and absorb IR radiation at dif-
ferent characteristic frequencies, causing an increase in amplitude of that bond vibration.
The IR radiation range is between 2.5µ and 25µ or 4000–400 cm−1. The IR is placed in between
UV-Vis and microwave.
The IR spectrum is further divided into four regions.
(i) Photographic region: This is the visible region range of 1.2µ
(ii) Very Near–IR region: This is known as over tone region; its range is 1.2 to 2.5µ.
(iii) Near IR region: This is known as vibration region; its range is 2.5 to 25µ.
(iv) For IR region: This is known as rotation region; its range is 25µ to 300–400µ.
The IR spectrum broadly divided into two regions as follows and shown in Figure 17.5
(i) Functional group region
(ii) Finger print region.
4000 3000 2500 2000 1500 1000 625 cm−1
-OH C H (C H) (Stretching) C C Over- C O C C C X (Stretching)

-COOH Ar H C H C N tone C N C N Bending region
-NH2 H C C C O H
O Fermi O C S
-NH resonance N Stretching. freq
C
-C C H O very low.
Functional group-region Finger print region

(Stretching region)
Figure 17.5 Infrared spectrum

17.16
A standard IR runs a single spectrum; it is a dispersive or a scanning monochromator method. In the
Fourier transform infrared spectroscopy (FTIR), a moving mirror inside the apparatus alters the distri-
bution of infrared light that passes through the interferometer; the signal directly records an “interfero-
gram” and it represents light output as a function of mirror position. This data-processing technique is
called Fourier transformation and turns this raw data into the desired result as a spectrum. The light
output is a function of infrared wavelength or wavenumber.
Introduction
A source provides radiation over the entire range of the IR spectrum. A monochromator disperses the
light and then selects a narrow wave number range. The detector measures the energy and transforms
it into an electrical signal. This signal is further amplified and registered by the recorder. The FTIR
spectra of most of the samples were recorded in the mid and far IR regions and are used for the present
investigation. Standard IR spectroscopy block diagram shown in Figure 17.6.
Standard IR Spectroscopy Block Diagram

Radiation source
Sampling area Mono chromator
considering optics
Recoder Amplifier Detector
Figure 17.6 IR Spectroscopy block diagram
Source
The IR radiation is produced by electrically heating source, usually Nernst filament or a Globar to
1000–1800°c. The Nernst filament is fabricated from a binder and oxides of thorium, cerium, zirco-
nium and yttrium. The Globar is a small rod of silicon carbide is 5 cm in length and 0.5 cm in diameter.
The maximum radiation for Globar occurs in the 5000–5500 cm−1 region. Nichrome wire, carbon arc,
rhodium wire and tungsten filament lamp are also used as a light source. In a commercial IR spectrom-
eter, either a nichrome wire or a platinum filament contained in a ceramic tube is commonly used as
IR source for the range 4000–400 cm−1
Monochromator
A monochromator separates the poly chromatic source radiation into suitable wavelength. This is
achieved by a prism or diffraction grating. An ideal prism instrument would contain a large number of
prisms made from different optical materials. A high resolution prism instrument contains combina-
tion of SiO2, NaCl and KBr prisms. Low-cost instrument uses a NaCl prism over the entire range. They
give the highest resolution in the vital finger print region.
Functions of Monochromator
The functions of a monochromator are as follows:
(i) It disperses the radiation according to its wave number components.

Spectroscopy 17.17
(ii) It restricts the radiation falling on the detector into a narrow wave number range.
(iii) It maintains the incident energy on the detector to an approximately constant entire wave number
range of the instrument when no sample is present.
Some instrument are used as double monochromator.
Detectors
A detector usually converts the thermal radiant energy into electrical energy which can be subse-
quently being plotted on chart recorder. Two types of the detectors are commonly used.
Thermal Detectors
Here, the IR radiation produces a heating effect that alters some physical property of the detector.
The detector mostly produces an electrical signal which is proportional to the intensity of the incident
radiation over the whole spectral range of the instrument.
The thermal detectors are selective and non-selective.
Selective Detectors Selective detectors are directly dependent upon the wavelength of incident radiation.
Example: Photographic plates, photo cells, photo conductive cells and infrared phosphors.
Non-selective Detectors Non-selective detector directly depends on incident energy but is independ-
ent of the wave length.
Example: Thermo couples, bolometers, pneumatic cells.
Pyro electrics are the most advance detectors being used recently.
Photon Detectors
Photon detectors use the quantum effects of the IR radiation to change the electrical properties of a sem-
iconductor. The result is producing electrons and holes; this is the internal photo effect. A sufficiently
energetic photon that strikes an electron in the detector can raise those electrons from as non-conducting
state into a conducting state. As conductors, electrons can contribute the current flow depending on the
configuration of the semiconductor. These are referred to as ‘photo voltaic’ or ‘photo conductive cell’.
Amplifiers and Recorders

The radiant energy received by the detectors is converted into measurable electrical signal and is
amplified by the amplifiers. The amplified signals are registered by a recorder or plotter.
17.3.3 Molecular Vibrations

For a molecule to absorb infrared radiation, it must undergo a net change in the dipole moment as a result
of vibrational or rotational motion. The energies associated with rotational transitions are generally
much smaller than that for vibrational transitions and the peaks are found below 300 cm−1. Typically,
vibrational spectra are measured between 4000 cm−1 to 650 cm−1 for NaCl optics or 4,000 cm−1 to
450 cm−1 for KBr optics.
All atoms in a molecule are constantly in motion. A diatomic molecule contains only a sin-
gle motion; polyatomic molecules have more than one type of vibration motion, known as normal
modes. Vibrations can be subdivided into two classes, depending on whether the bond length or angle
change—they are stretching and bending vibrations. IR vibrational frequency range for different func-
tional groups shown in Table 17.5.

17.18
Table 17.5 IR vibrational frequency range for functional groups

S. no. Functional group IR frequency range in cm−1
1. Alkanes C H Stretching – <3000
C O Stretching – 1000 − 1300
C H Bending – <1000
2. Cyclo-alkanes Δ C H Stretching – >3000
3. Alkenes C C Stretching – 1550 – 1680
CH2 CH2 1640
C C C C 1620
1600 – 1580
1620 – 1640
4. Cyclo alkenes – 1974
– 1565
5. Alkynes C H Stretching -3300

C C Stretching – 2100 – 2300
C H Bending –<900 (900 – 750).
6. Aromatic H
3000 cm−1
C H Stretching-3000
C C Skeletal- 1600 –1400
Maximum –4 (vibrations)
Minimum –2 (vibrations)
a) ≈ 1600 sharp (variable)
≈ 1580 sharp (very weak)
≈ 1500 sharp (very intense)
≈ 1450 sharp (very weak)
X
730–770 Two bands
690–710 (strong)
X
735–770
Y
X
860–900
750–810
Y
X
800–860

Spectroscopy 17.19

7. Ethers C O C stretching – 1000 – 1300
dialkyl ether – 1060 – 1150
Alkyl-Aryl ether - 1240 – 1285
Vinyl ether - 1200 – 1275
Cyclic ether – 1170 – 1250
O
≈ 1250
8. Alcohols O H stretching - 3500–3600

O H H-Bonding - 3200–3400
C O stretching 1100–1250
Primary (1°) C O ≈ 1050
Secondary (2°)C O ≈ 1050
Tertiary (3°) C O ≈ 1150
ph O stretching ≈1250
9. Carbonyl compounds R C H Streching ≈ 2800
O
R C O Streching ≈ 1600–1750
H
10. ketones C O stretching -1600–1830
O
1820–1825
O
1775
O
1751
1715
11. Carboxylic acid C H stretching - 3600 – 3700
C O stretching - 1100 – 1250

12. Esters O
R C OR
C O stretching -1750–1790
C O C stretching -1150 –1300
(Continued )

17.20
13. Acid halides O
R C Cl 1815–1825 C O
(asymmetric)
C O (symmetric) -1745−1755
C O C - 1180−1220
14. Anhydrides O O
R C C R
O
C O −1780−1825
15. Cyclic anhydrides C O (Asymmetric)1840−1870
C O (symmetric )1700−1800
C O C-1200−1300
16. Amides 3200−3400
17. Amines 3250−3400
18. Nitrile R C N-2200−2300
Ar C N -2100−2200
R N C -2100−2150
19. Nitro compounds O
R N Symmertic 1370–1390
O
O
AR N Symmertic 1330–1370
O
O
R N Assymertic 1530–1560
O
O
AR N Assymertic 1500–1540
O
20. Allene Stretching-1900 – 2000
Note:
(i) In cycloalkenes, the ring strain increases and the IR frequency also increases.
(ii) In carbonyls, an increase in conjugation leads to decreased IR frequency of carbonyls.
Symmetrical (homolytic) diatomic molecules are observed in the Raman spectra but not in the
IR spectra. This is due to the fact that diatomic molecules have one band and no permanent dipole
movement change and therefore only one single vibration occurs, and IR is inactive.
Example: O2 or N2
Unsymmetrical diatomic molecules absorb in the IR spectra, due to change in dipole moment and
IR is active.
Example: CN

Spectroscopy 17.21
Polyatomic molecules undergo more complex vibrations that can be resolved into normal modes
of vibration. The normal modes of vibration are stretching (symmetric and asymmetric) and bending
(scissoring, rocking, wagging and twisting).
Stretching
Vibration is a rhythmic movement along the bond axis such that the inter-atomic distance increases or
decreases and alters the length of a bond, such as C H or C C. The vibrations of a molecule contain-
ing three atoms are more complex; there are symmetric and asymmetric stretches.
Bending
A bending vibration may consist of a change in bond angle between bonds and it does not occur
along the line of the bond. If we alter the angle between two bonds, such as the HCH angle in a
methylene group, the bond lengths remain unchanged. A diatomic molecule such as HCl can only
undergo stretching vibrations.
H–Cl
Streching
Bending vibrations can be either in plane (d ) or out plane (g ) modes.
Rocking
A change in the angle between a group of atoms, such as a methylene group and the rest of the molecule
is called rocking.
Wagging
A change in the angle between the plane of a group of atoms, such as a methylene group and a plane
through the rest of the molecule is called wagging.
Twisting
A change in the angle between the planes of two groups of atoms, such as a change in the angle
between the two methylene groups is called twisting.
Out-of-plane
This is a change in the angle between any one of the C H bonds and the plane defined by the remain-
ing atoms of the ethylene molecule. Another example is in BF3 when the boron atom moves in and out
of the plane of the three fluorine atoms.
In a rocking, wagging or twisting coordinate, the bond lengths within the groups involved do not
change but the angles change. Rocking is distinguished from wagging by the fact that the atoms in the
group stay in the same plane.

17.22
17.3.4 Factors Affecting Vibrational Frequency

Isotope Effect
When an atom is replaced by an isotope, the effect on force constant (k) is negligible but due to reduced
or increased mass, it has an effect on the rotational and vibrational behaviour. Hence, a change in the
mass has an effect on frequency (ν).
Solvent Effect
The polar solvent has an influence on the IR spectra of organic compounds due to the interaction
between solvent and compounds, and is called solvent effects.
Compounds which contain n, p and p * orbitals are placed into a polar solvent, and the solvent
will stabilise with these three orbitals to a different extent. The order of stabilisation effects of the polar
solvent is n orbital > p * orbital > p orbital. The spectra of n→p * transition will shift to shorter wave-
lengths and higher energies due to the polar solvent causes the energy difference between n orbital and
p * orbital to become bigger. The spectra of p→p * transition will shift longer wavelength and lower
energies due to the polar solvent that causes energy difference between p and p * orbitals to become
smaller.
17.3.5 Degrees of Freedom

The number of variables required to explain the motion of a particle is known as the degree of free-
dom. In an atom moving in a three-dimensional space, three coordinates are adequate; so its degree
of freedom is three but its motion is purely translational. If a molecule is made of N atoms or ions, the
degree of freedom becomes 3N, because each atom has three degrees of freedom; but these atoms are
bonded together, all motions are not translational; some become rotational and others vibrational. For
non-linear molecules, all rotational motions can be described in terms of rotations around three axes,
hence, it possesses 3N − 6 degrees of freedom for normal vibrational motion. For a linear molecule,
there is no rotation around its own axis because it leaves the molecule unchanged. Therefore, there
are only two rotational degrees of freedom for any linear molecule that possesses 3N − 5 degrees of
freedom for vibration.
(i) Number of fundamental vibrational modes for a linear molecule = 3N − 5
(ii) Number of fundamental vibrational modes for a non-linear molecule = 3N − 6
where N = number of atoms in a molecule.
17.3.6 Solved Problems Based on IR Spectra

(i) Find the number of vibrational modes for the following molecules:
NH3, C6H6, C10H8, CH4, C2H2, CO, HCl.
For a non-linear molecule, the number of fundamental vibrational modes = 3N − 6
NH3 − 6 (3 × 4 − 6 = 6)
C6H6 − 30 (3 × 12 − 6 = 30)
C10H8 − 48 (3 × 18 – 6 = 46)
CH4 − 9 (3 × 5 − 6 = 9)
For a linear molecule, the number of fundamental vibrational modes = 3N − 5

Spectroscopy 17.23
C2H2 − 7 (3 × 4 − 5 = 7)
CO-1 (3 × 2 − 5 = 1)
HCl-1 (3 × 2 − 5 = 1)
(ii) State which of the following molecules are IR active. Why?
N2, CO, CO2, HCl, H2, O2.
N2, CO2, H2 and O2 – IR inactive
CO and HCl – active
All molecules cannot interact with IR radiation; only those molecules which exhibit change in
dipole moment during a vibration can exhibit IR spectra. Hence, homonuclear diatomic molecules
like H2, O2, N2, Cl2, etc., do not show change in dipole moment during vibration; consequently,
they do not exhibit IR spectra. The heteronuclear diatomic/polyatomic molecules like HCl, BeCl2,
NH3, CH4, C6H6, etc., show a change in the dipole moment and can exhibit IR spectra.
17.3.7 Applications of IR Spectroscopy

IR spectroscopy is a simple and reliable technique and is widely used in industry as well as in research,
for analysis, quality control and dynamic measurement. It is also used in forensic analysis in civil and
criminal analysis.
(i) Identification of functional group and structural elucidation
IR region broadly divided into functional group region (4000–1600 cm−1) and finger print region
(1600–400 cm−1).
In functional group frequency region, the peaks corresponding to different functional groups
can be observed; according to corresponding peaks, functional group can be determined.
In finger print region, each atom of the molecules is connected by a bond and each bond gives
different characteristic peaks at the IR region; this region of IR spectrum is called finger print
region of the molecule.
(ii) Identification of substance
IR spectroscopy is used to distinguish whether a given sample of an organic substance is identical
with another or not because the probability of any two compounds will produce identical spectra
is almost zero. Hence, if two compounds have an identical IR spectra, then both of them must be
samples of the same substance.
IR spectra of two enantiomeric compounds are identical; hence IR spectroscopy fails to distin-
guish enantiomers.
Example: IR spectrum of benzaldehyde is observed as follows:
C H stretching of aromatic ring 3080 cm−1
C H stretching of aldehyde 2775–2860 cm−1
C O stretching of aromatic aldehyde 1700 cm−1
C C stretching of aromatic ring 1595 cm−1
C H bending 685–745 cm−1
As shown above, no other compound can produce same IR spectra other than benzaldehyde.
(iii) Study of the chemical reaction progress
By examining a small amount of the reaction mixture withdrawn from time to time, the progress
of chemical reaction can be determined. The rate of disappearance of a characteristic absorption

17.24
band of the reactant group and/or the rate of appearance of the characteristic absorption band of
the product group due to formation of new product is determined.
(iv) Detection of impurities in the compound
IR spectrum of the test sample to be determined is compared with the standard compound; if any
additional peaks are observed, it is due to impurities present in the compound.
(v) Quantitative analysis
The quantity of the substance can be determined either in pure form or as a mixture of two or
more compounds; here, the characteristic peak corresponding to the substance is chosen and log
I0/It of peaks for standard and test sample is compared. This is called base line technique for quan-
titative analysis of the substance.
(vi) Qualitative analysis
IR spectroscopy is a highly important method for identification of compounds and functional group.
Structural analysis can be done by using group frequencies; group frequencies are vibrations that
are associated with certain functional groups. It is possible to identify a functional group of a mol-
ecule by comparing its vibrational frequency on an IR spectrum with an IR stored data bank.
17.4 NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY
17.4.1 Principle
The analytical field involved with the interaction between radiofrequency radiation and nuclei of the
molecule is called nuclear magnetic resonance spectroscopy (NMR). NMR is a powerful tool for the
investigation of nuclear structure. In NMR, the energy source is radio waves; they are the lowest
energy form of NMR. Radio frequency waves lie between 107–108 cycles per seconds. This frequency
energy is not sufficient to vibrate, rotate o) exit the molecule or an atom. However, this energy is suf-
ficient to affect the nuclear spin of the atoms of a molecule.
The NMR technique enables us to study the shape and structure of a molecule. It reveals only the
different chemical environment of the various forms of nuclei present in molecule, from which we can
ascertain the structure of the molecule with which we deal. By using this method, we can determine
both quantitative and qualitative analysis of organic compounds in particular.
When the spins of protons and neutrons comprising nuclei are not paired, the nuclei of all these
elements carry a charge; the overall spin of the charged nucleolus generates a magnetic dipole along
the spin axes. The intrinsic magnitude of the dipole is a fundamental nuclear property and is called the
nuclear magnetic moment (m).
Depending on protons and neutrons present in the nucleolus, the spin orientation I will be changed.
(i) I = 0 for 10B, 12C, 14N, 16O, 32S etc., No spin, NMR inactive (Even number of protons and neutrons)
(ii) I = ½ for 1H, 13C, 15N, 19F, 31P etc., Dipolar nuclei, NMR active (Odd number of protons and even
number neutrons)
(iii) I ≥ 1 for 2H, 10B, 14N etc., quadrupolar nuclei, NMR active (Odd number of protons and neutrons)
According to quantum mechanical terms, the nuclear magnetic moment of the nucleolus can align
with an externally applied magnetic field strength (B0) in only 2I + 1 ways, either reinforcing or by
opposing B0.
The energetically preferred orientation has the magnetic moment aligned parallel with the applied
field (S = 1/2) and is often given the notation a, whereas higher energy anti-parallel orientation
(S = −1/2) is referred to as b . The rotational axis of the spinning nucleolus cannot be oriented exactly

Spectroscopy 17.25
parallel to the direction of the applied field B0 but must process about this field at angle with an angular
velocity (w 0) given by the expression.
w 0 = g B0 (1)
The constant g is the magnetic gyroscopic ratio and the related magnetic moment m and the spin num-
ber I for any specific molecule.
The basic requirements for NMR spectrometer are as follows and shown in Figure 17.7.
(i) Very strong static and homogeneous magnetic field
(ii) Sampling tube and sample preparation
(iii) Stable radio frequency generator
(iv) Radio frequency receiver/detector
(v) Recorder
Radio frequency Radio frequency

Detector
transmitter amplifier
Sweep Sweep
coil coil
Audio
Magnetic pole Magnetic pole
amplifier
Spinning
sample tube Recorder
Sweep
genarats
Figure 17.7 NMR Block diagram
Very Strong Static and Homogeneous Magnetic Field

The magnetic field is the most commercial NMR spectrometer and may be either an electromagnetic or
a permanent magnet; both must have the capability of producing a very strong static and homogeneous
magnetic field. The produced field must be homogeneous to 1 part in 108 within the sample area and
must be stable to similar degree for short period of time. The magnetic size is 15 inches in diameter
and capable of producing strong fields up to 23,500 gauss for 100 mHz.
Sampling Tube and Sample Preparation

An NMR tube is a cylindrical tube made of special glass 18–20 cm in length and 5 mm in external
diameter. The solution of sample should be to a height of 4–5 cm.
The ideal solvent should contain no protons or the solvent proton to have to be replaced by deute-
rium. The solvent used must be inert, low boiling and inexpensive. The sample size for proton magnetic

17.26
resonance (PMR) on a continuous wave–nuclear magnetic resonance (CW–NMR) instrument should

be around 30–50 mg in about 0.5 ml of solvent. However, for pulse transmission–NMR (PT–NMR)
spectra, 1 mg of sample in 0.5 ml would be a strong solution.
Stable Radio Frequency Generator

Perpendicular to magnetic field, the radio frequency oscillator is installed to transmit radio waves of
some mixed frequency such as 60, 100, 220 and 300 MHz. A sweep generator is installed to supply to the
secondary magnet for high resolution work, and the frequency must be constant to about one part in 108.
Radio Frequency Detector/Receiver

It is installed perpendicular to both the magnetic field and the oscillator coil and is tuned to the same
frequency as transmitter. When resonance occurs, the detector coil detects radio frequency signal and
this signal is amplified and sent to the recorder.
Recorder
The recorder gives a spectrum a plot of strength of resonance signal on the y-axis and strength of
magnetic field on the x-axis. The strength of resonance signal is directly proportional to the number of
nuclei resonating at that particular field strength.
Therefore, the magnetic field increases linearly and the recorder pen travels from left to right, thus
protons achieve resonance faster; the de-shielded proton appears on the left side—down field, whereas
the shielded proton appears on the right side—up field of chart in the form of peaks. Tetramethylsilane
(TMS) is shown at a peak value of d = 0 ppm, hence, it is using as reference compound.
17.4.3 Chemical Shift

The difference in absolute precessional frequency of a particular set of protons of molecule and abso-
lute n r of reference compound proton is called chemical shift.
(or) The difference between the absorption positions of a particular set of proton from the absorp-
tion position of a reference proton is called chemical shift of the particular set of protons.
Chemical shift = (absolute n s of particular set of proton) – (absolute n r of reference protons)
This formula gives the chemical shift values in Hz (cycle/sec). Chemically non-equivalent proton
gives different chemical shift values. Chemical shift values for different types of proton are shown in
Table 17.6.
Table 17.6 Chemical shift values
Type of proton Approximate chemical shift (ppm)
(CH3)4Si 0
CH3 0.9
CH2 1.3
1.4
CH
C C CH3 1.7

Spectroscopy 17.27
Type of proton Approximate chemical shift (ppm)

O 2.1
C CH3
2.3
CH3
C C H 2.4
R O CH3 3.3
R C CH2 4.7
R
R C C H 5.3
R R
6.5-8
H
O 9.0-10
C H
2.5-4
I C H
2.5-4
Br C H
3-4
Cl C H
4-4.5
F C H
RNH2 Variable, 1.5-4
ROH Variable, 2-5
ArOH Variable, 4-7
O Variable, 10-12
C OH
Conversion of Chemical Shifts in Hz into Field Independent Chemical Shift

In proton NMR spectroscopy, two measurement scales have been used to convert chemical shifts val-
ues from Hz to field independent chemical shifts and are measured in ppm. They are delta units, scale
(d ) and tau units or scale (t)
Delta Units or Scale (c )

This scale is recent and advanced units, which set 15e reference (TMS) at arbitral 0.0 ppm for both
1
H and 13C– NMR spectroscopy. Since the TMS reference is the extreme right, the d values increases
from right to left, that is, in the direction of weaker shielding.

17.28
n sample ( Hz) − n reference ( Hz)

d = .
n Instrument ( MHz)
(or)
n sample ( Hz) − n reference ( Hz)
d = × 106 (or )
Instrumental frequency
Chemical shift (Hz) away from reference
d = ppm
Instrumental frequency(M MHz)
All chemical shift values in d units must be mentioned in ppm. The instrumental frequency is always
equal to the precessional frequency of protons of reference compound.
vInstrument = vReference
Tau Scale (s )

It is an old technique. In this scale, arbitrary put the reference of TMS at 10 ppm with scale number
decreasing to the left. This is no longer used. For the sake of convenience, the t scale values are taken
in d scale.
t = 10 − d
The commonly used units for chemical shift is d values. The chemical shift in Hz depends on the
strength of external magnetic field but in d units are independent.
17.4.4 S
pin-Spin Splitting, Spin-Spin Interaction,
Spin–Spin Coupling or Fine Spectrum
In proton NMR, the signal due to a particular set of proton may not be a signal sharp peak but instead
appears as a collection of peaks. The signal may be split into two or more peaks. The splitting occurs
only between nuclei with different chemically or magnetically non-equivalent protons.
Splitting of signals occurs due to small interaction/coupling between two chemically non-
equivalent protons, neighbouring proton or group of protons and is related to the number of possible spin
orientation of neighbouring group proton. This is known as “spin-spin interaction/spin-spin splitting”.
Theory of Spin-spin Splitting

Splitting of signals in proton NMR is due to indirect spin-spin interaction. Spin-spin coupling of nuclei
is transmitted through the intervening bonds but not through space. The number of lines in the multiple
of particular set of protons of a molecule is equal to the total number of different precessional frequen-
cies associated with those protons.
Example: Ha and H b proton shows two precessional frequencies due to upward and downward
orientation of Ha and H b proton and gives a doublet.
Ha Hb
Hb proton Ha proton
X Y possible possible
X C C Y spin spin
orientation orientation
Ha Hb

Spectroscopy 17.29
Upward orientation of the neighbouring proton increases with the precessional frequency of reference
proton but downward spin orientation of the neighbourhood proton describes the precessional fre-
quency of reference proton. The number of lines in the NMR spectra is equal to the number of possible
spin orientations of neighbourhood protons.
Example:
Neighbour hood
X Y
proton
X C C Hb
Ha Hb
Reference
proton
In the Ha peak split into triplet Ha, there should be three different precessional frequency coupling
interactions and the neighbourhood proton should have three possible spin orientation and Ha appears
as a triplet.
Possible spin orientations of H b proton are as follows:
1) 25%
2) 25%
50%
3) 25%
4) 25%
Out of the four, three are possible with 25%, 50% and 25%.
These three different possible spin orientations of H b nuclei influence on Ha nuclei and coupling
interaction is observed and the splitting of Ha nucleolus signal occurs in its PMR spectra as a tri-
plet. Ha will have two possible spin orientations. Therefore, H b proton split into two signals, that is,
doublet.
Ha Hb
Hb Proton Ha Proton
possible possible
spin orientation spin orientation
Multiplicity by (n + 1) Rule
The number of peaks in 1H-NMR is referred as the multiplicity explained by (n + 1) rule. This rule
gives multiplicity of signals of reference protons in the molecule; where n is the number of neighbour-
ing protons of reference protons.
17.4.5 Magnetic Resonance Imaging

Magnetic resonance imaging, nuclear magnetic resonance imaging or magnetic resonance tomography
is a medical imaging technique used in radiology to investigate the anatomy and physiology of the
body in both healthy and sick conditions. It is commonly used in medical and nuclear physics. These
techniques are explained by the basic concept of nuclear magnetic resonance spectroscopy.

17.30
Working Process of Magnetic Resonance Imaging

In nuclei having proton and neutron,
mg
one way to model a proton is to think of it as a sphere composed of positive current loops that create
magnetic dipole moment given by mp = 2.7928 mB. Actually, there are two ways that positively charged
proton spins.
Spin up Spin down
In these two ways, there is no presence of any magnetic field of the two states are same. When a proton
is placed into an external magnetic field, it feels a torque that will tend to orient the magnetic dipole
moment along the same axis as the magnetic field lines. However, angular momentum of the proton
keeps it from aligning exactly and the magnetic dipole moment will process about an axis.
If we now direct an electromagnetic wave just the right frequency at proton, the precession of the
m of the proton will flatten out since it will tend to align with the magnetic field lines of the wave. By
sending the em pulse, we give spin up protons enough energy to transition to the spin down state.
The human body consists mostly of water which contain hydrogen nuclei. Hydrogen nuclei have the
strongest NMR signals. The MRI machine contains a large magnetic coil that can create a very large
magnetic field. It also contains a second set of coils that create the electromagnetic pulse (RF pulse).
When the RF pulse is emitted, the spin up transitions to spin down state when we turn off the mag-
netic fields. The nuclei return to the magnetic fields. The nuclei return to the ground state and release
energy. This energy that has varying intensity can be used to construct on image by a computer. The
higher density, the brighter it will appear on the screen
17.4.6 High Resolution Proton Magnetic Resonance Spectroscopy

High resolution PMR spectrum gives the total number of peaks instead of a single peak in low resolu-
tion NMR. Here, the spectrum is split into a cluster of peaks; the possibilities are as follows:
(i) Peak a singlet
(ii) Peaks in the cluster a doublet
(iii) Peaks in the cluster a triplet
(iv) Peaks in the cluster a quartet

Spectroscopy 17.31
The same information get from a high resolution spectrum as well as low resolution spectrum; but in
high resolution spectrum gives cluster of peaks instead of single peak as in low resolution spectrum.
In addition, the amount of splitting of peaks gives important extra information in interpreting a high
resolution spectrum.
Interpreting a High Resolution Spectrum

The n + 1 Rule
The amount of splitting gives information about the number of hydrogen atoms attached to the carbon
atom or the next carbon atom. The number of sub peaks in the cluster is one more than the number of
hydrogen attached to the next carbon atom.
Singlet Next to carbon with no hydrogen attached
Doublet Next to a CH group
Triplet Next to a CH2 group
Quartet Next to a CH3 group
Using the n + 1 Rule

Example: C4H8O2
High resolution Low resolution

(3)
(2) (3)
4.0 3.0 2.0 1.0 0 4.0 2.0 1.0
In a low resolution spectrum, there are three clusters of peaks observed with three different environ-
ments for hydrogen; in the three environments, the hydrogen ratio is 2:3:3. Here, there are eight hydro-
gen atoms altogether and represent a CH2 group and two CH3 groups.
Splitting Pattern
CH2 group at 4.1 ppm: Quartet gives information that next carbon is attached with the three hydrogen,
that is, CH3 group.
CH3 group at 1.3 ppm: Triplet gives information that the next carbon is attached with the two
hydrogen atoms, that is, CH2 group.
The combination of these two clusters of peaks one a quartet and other is triplet. It is a common
ethyl group CH3CH2.
CH3 group at about 2.0 ppm: Singlet means the next carbon does not have any hydrogens attached.
The compound is as follows:
O
(3 hydrogens singlet) CH3 C O CH2 CH3 (3 hydrogens triplet)
(2 hydrogens quartet)
By using chemical shift data, it can identify the environment of each group.

17.32
17.4.7 NMR Applications

NMR has become an advanced and a powerful analytical technique that has found a variety of applica-
tions in many disciplines of scientific research, medicine and various industries.
Some applications of NMR are discussed here.
Solution Structure
This is the only method for atomic resolution structure determination of bio-molecules in aqueous
solution under near physiological conditions.
Molecular Dynamic
It is used for quantifying motional properties of bio-molecules.
Protein Folding
It is the most powerful tool for determining the residual structure of unfolded proteins and structuring
of folding proteins.
Ionisation State
It is used to determine the chemical properties of functional groups, bio macro molecules, such as the
ionisation states of ionisable groups at the active sites of enzymes.
Drug Screening and Designing

It is used for drug leads and conformation compounds bound to enzymes, receptors and other proteins.
Hydrogen Bonding
It is used in direct detection of hydrogen bonding interactions.
Metabolite Analysis
It is a very powerful technology for metabolite analysis.
Protein Hydration
It is used in the detection of interior water and its interaction with bio macro molecules.
Chemical Analysis
It is used in chemical identification and conformational analysis of synthetic or natural chemicals.
Material Science
It is a powerful tool in research of polymer chemistry and physics.
Weak Inter-Molecular Interaction

Allowing weak functional interactions between macro bio molecules is yet to be studied.

Spectroscopy 17.33
17.4.8 Solved Problems Based on Proton NMR

(i) Explain the chemical shift values and draw the structure of a given compound.
C3H7Cl
3H
2H
2H
4 3 2 1 0
PPM
Structure and chemical shift values:

Functional group Splitting pattern Chemical shift value
Methyl (CH3) 2+1 0.94
Methylene (CH2) 5+1 1.61
Methylene Chloride 2+1 3.68
(CH2-Cl)
1.61
Cl
0.94 3.68
(ii)
C5H10O
3H
6H
1H
3 2 1 0
PPM

2 Methyl (CH3) 1+1 1.04
CH 6+1 2.56
Methyl (CH3) 0+1 1.98

17.34
1.04
2.56
1.98
1.04
O
(iii)
C4H10Cl
6H
2H
1H
1H
5 4 3 2 1 0
PPM
2 Methyl (CH3) 2+1 0.91
CH 8+1 1.32
Hydroxyl (OH) 2+1 4.24
3.45
0.91
OH
1.32 4.24
0.91
(iv)
C6H4F2
1H
8 7 6 5 4 3 2 1 0
PPM

Spectroscopy 17.35

4 CH 1+1 7.14
F
7.14 7.14
7.14 7.14
F
(v)
C6H14O
6H
1H
4 3 2 1 0
PPM

4 Methyl (CH3) 1+1 1.13
2 Methylene (CH2) 6+1 3.65
1.13 1.13
3.65 3.65
O
1.13 1.13
(vi)
C6H12O2
3H
2H 2H
2H 3H
4 3 2 1 0
PPM

17.36

Methyl (CH3) 2+1 0.93
Methyl (CH3) 0+1 3.61
O
1.75
0.93 3.61
O
1.38 2.32

1. What is the range of UV _____________ and visible _____________.
[Ans.: 200–400 and 400–800]
2. UV-visible spectroscopy is also called _____________.
[Ans.: Electronic spectroscopy]
3. UV-visible spectroscopy predicts the _____________.
[Ans.: Unsaturation of organic and inorganic molecule]
4. In UV-visible spectroscopy commonly used sources _____________ and _____________.
[Ans.: Deuterium arc and tungsten–halogen lamp]
5. Carbonyl compounds involve _____________ electronic transitions.
[Ans.: n - p *]
6. We observe the s - s * electronic transitions _____________.
[Ans.: Below 200 nm]
7. The molecular vibration at which we observe change in bond length is _____________
[Ans.: Stretching vibrations]
8. We observe electronic transitions in IR spectroscopy at the _____________
[Ans.: Vibration level]
9. IR active molecules are called _____________
[Ans.: Permanent dipole moment molecule]
10. The region that occurs at 4,000–1,600 cm−1 range is _____________
[Ans.: Functional group region]
11. An IR instrument which converts thermal radiant energy to electrical energy is _____________
[Ans.: Detectors]

Spectroscopy 17.37
12. _____________ and _____________ detectors are used in IR instrumentation.

[Ans.: Thermal and photon]
13. _____________ is the energy source for NMR spectroscopy.
[Ans.: Radio waves]
14. NMR is _____________.
[Ans.: Nuclear magnetic resonance spectroscopy]
15. _____________ and _____________ scales are used to measure the chemical shift values in
NMR spectroscopy.
[Ans.: Delta and Tau (t)]
16. Interaction between two chemically non-equivalent protons is called _____________.
[Ans.: Spin-spin interaction]
17. t = _____________.
[Ans.: 10 − d]

1. How many electronic transitions we observe in UV-visible spectroscopy
(a) 4 (b) 2
(c) 3 (d) 5
[Ans.: a]
2. UV-visible spectroscopy is also called
(a) Electronic spectroscopy (b) Vibrational spectroscopy
(c) Rotational spectroscopy (d) Vibration- rotational spectroscopy
[Ans.: a]
3. The range of UV-visible spectroscopy is
(a) 200–800 nm (b) 400–800 nm
(c) 200–400 nm (d) None of these
[Ans.: a]
4. Which of the following is responsible to absorb the UV-visible light by a molecule?
(a) Auxochrome (b) Chromophore
[Ans.: b]
5. Which is an auxochromic group?
O O
(a) R C R (b) R C H
(c) CN (d) NHR
[Ans.: d]

17.38
6. IR spectroscopy is called

(a) Rotational spectroscopy (b) Vibrational spectroscopy
(c) Electronic spectroscopy (d) None of these
[Ans.: b]
7. IR active molecules are
(a) Electronegative elements (b) Non-polar molecule
(c) Di–pole moment exhibiting molecule (d) All the above
[Ans.: c]
8. IR spectra detects
(a) Functional group (b) Unsaturation
(c) Number of protons (d) Nature of nuclei
[Ans.: a]
9. In IR, what is the range of IR in cm-1?
(a) 200–800 cm-1 (b) 400–800 cm-1
(c) 200–400 cm-1 (d) 400–4,000 cm-1
[Ans.: d]
10. What is the finger print region range in IR
(a) 4,000–400 cm-1 (b) 4,000–1,600 cm-1
(c) 1,600–400 cm-1 (d) No range
[Ans.: c]
11. What is functional group range
(a) 4,000–1,600 cm-1 (b) 1,600–400 cm-1
[Ans.: a]
12. What is reference compound in NMR spectroscopy
(a) Tri methyl silane (TMS) (b) Di methyl silane (DMS)
(c) Mono methyl silane (MMS) (d) None of these
[Ans.: a]
13. Radio frequency range in NMR
(a) 105 − 102 (b) 107 − 108
(c) 1010 − 1012 (d) All the above
[Ans.: b]
14. By absorbing radio wave frequency in NMR, changes are involved in
(a) Vibrational energy level (b) Rotational energy level
(c) Nuclear spin orientation (d) None of these
[Ans.: c]

Spectroscopy 17.39
15. Multiplicity rule is

(a) n + 2 (b) n + 3
(c) n + 1 (d) n + 5
[Ans.: c]
16. At _____________ spectrum observe clusters of peaks.
(a) Low resolution spectrum (b) High resolution spectrum
(c) Medium resolution spectrum (d) a & b
[Ans.: b]
17. In NMR spectroscopy, we study
(a) Shape and structure of the molecule (b) Chemical environment of nuclei.
(c) Mass of the molecule (d) None of these
[Ans.: b]
18. What are the units for δ scale?
(a) 4 m sec-1 (b) PPM
(c) Neuton (d) Hertz
[Ans.: b]

1. Write a short note on electronic transitions.
Ans.: By the absorbing of electromagnetic radiation in the range of 200–800 nm, the electrons
are involved in transitions in electronic energy levels.
In UV–visible spectroscopy, different types of electronic transitions such as
s - s *, p - p *, n - s * and n - p * are present.
2. Explain auxochrome.
Ans.: It is a group which does not act as a chromophore but when it is attached to a chromophore,
it shifts the absorption maximum towards the longer wavelength along with an increase in
the intensity of absorption.
3. Give an account of chromophore.
Ans.: It is group of molecules, which is responsible for the absorption of light by molecules. It is
conjugated dienes.
4. Write the factors affecting on the λ maximum and intensity of radiation?
Ans.: Factors affecting the λ maximum are as follows:
Structural factors are substitution, solvent and geometry.
1.
Non – structural factors are pH and temperature.
Factors affecting the intensity of absorption of radiation are Thickness of the medium and
concentration.

17.40
5. What do are determine by using UV–visible spectroscopy?

Ans.: U V– spectroscopy is usually applied to predict the conjugated double bonds, a, b unsatu-
rated carbonyl compounds and organic complexes in a solution.
6. What do we determine using IR spectroscopy?
Ans.: By the using IR, we detect the functional groups based on their bonds.
7. Write the range of IR radiation.
Ans.: The IR radiation range is between 2.5m and 25m.
8. How many regions do we observe in the graphical representation of IR spectroscopy?
Ans.: In the IR spectrum, we observe two regions:
(a) Finger print region
(b) Functional group region
9. Write the applications of IR.

Ans.:
(a) Identification of functional groups
(b) Studying the progress of chemical reaction
(c) Detection of impurities
(d) Qualitative and quantitative analysis
10. Explain the molecular vibrations in IR spectroscopy.
Ans.: Molecular vibrations in IR
(a) Stretching
(a) Symetrical
(b) Assymetrical
(b) Bending
Scissoring
Inplane
Roclcing
Twistting
Outplane
Wagging
11. Explain stretching vibrations.

Ans.: The bond angle remain the same but the bond length changes during vibrations.
Stretching is of two types:
(a) Symmetrical
(b) Asymmetrical
12. Explain bending vibrations.
Ans.: Bond length remains the same but the bond angle changes during vibrations.
Bending is classified as follows:
(a) Inplane
(b) Outplane

Spectroscopy 17.41
13. Write the factors affecting vibrational frequency in IR spectroscopy.

Ans.:
(a) Isotope effect
(b) Solvent effect
14. What is the aim of NMR spectroscopy?
Ans.: NMR is a powerful tool for to investigate the structure of nuclei by using radio waves.
15. What is the energy source in NMR and its frequency?
Ans.: The energy source for NMR is radio waves; its range is in between 107 and 108.
16. Write a note on chemical shift.
Ans.: The difference between absolute precessional frequency of a particular set of protons of
molecules and the absolute precessional frequency of reference compound proton is called
chemical shift.
17. What are the scales for chemical shift values in NMR?
Ans.: In proton NMR spectroscopy, two measurement scales have been used to convert the
chemical shift in the Hz into field independent chemical shift.
(a) Delta (d )
(b) Tau scale (t)
d sample(Hz) − d reference (Hz)
d =
d instrument (MHz)
t = 10 − d.
18. Explain spin–spin interaction.
Ans.: Splitting of signals occurs due small interaction between the two chemically non-equivalent
protons and is related to the number of spin orientations possible of neighbouring group of
protons. This is called spin-spin coupling or spin-spin interaction.
19. Explain spin multiplicity rule.
Ans.: number of peaks in NMR is referred to as the multiplicity explained by (n + 1) rule, where
n is the number of neighbouring protons of reference.
20. What is high resolution spectrum in NMR spectroscopy?
Ans.: High resolution NMR spectrum form many of what looked like single peak in lower reso-
lution spectrum are split into cluster peaks.

Q.1 Describe the principle of UV–visible spectroscopy.
Q.2 Give detailed notes on instrumentation of UV–visible spectroscopy.
Q.3 Explain the electronic transitions in UV–visible spectroscopy.
Q.4 Write notes on applications of UV–visible spectroscopy.

17.42
Q.5 Define the following one with suitable examples.

(a) Auxochrome (b) Chromophore
Q.6 Give an account on factors affecting the position of the λ maximum and intensity of radiation.
Q.7 Write the basic principle of IR spectroscopy.
Q.8 Give an account on instrumentation of IR spectroscopy.
Q.9 Explain the molecular vibrations in IR spectroscopy.
Q.10 Write the application in IR spectroscopy.
Q.11 Give a detailed note on the basic principle of NMR spectroscopy.
Q.12 Explain the instrumentation of NMR with a neat sketch.
Q.13 Describe chemical shift. How do we measure chemical shift values in NMR spectroscopy?
Q.14 Give a brief note on spin-spin splitting and the theory of spin-spin interaction with examples.
Q.15 Write a note on magnetic resonance imaging.
Q.16 Explain the difference between low resolution spectrum and high resolution spectrum.

18 THERMAL ANALYSIS
18.1 INTRODUCTION
Thermal analysis is a branch of materials science where the properties of materials are studied as
they change with temperature. Thermometric methods are distinct analytical tools; several commonly
used methods are distinguished from one another by the property which is measured as mentioned in
Table 18.1. Data are obtained in the form of continuously recorded curves; these may be regarded as
thermal data.
Table 18.1 Common thermal methods and the property measured

S. no. Method Property measured
1. Thermogravimetric analysis (TGA) Change in weight/mass
2. Derivative thermogravimetric analysis (DTG) Rate of exchange of weight
3. Differential thermal analysis (DTA) Heat evolved or absorbed/temperature difference
4. Thermometric titrations Change of temperature
5. Dielectric thermal analysis (DETA) Dielectric permittivity and loss factor
6. Differential scanning calorimetry (DSC) Heat difference
7. Dilatometry (DIL) Volume
8. Dynamic mechanical analysis (DMA) Mechanical stiffness and damping
9. Evolved gas analysis (EGA) Gaseous decomposition products
10. Laser ﬂash analysis (LFA) Thermal diffusivity and thermal conductivity
11. Thermomechanical analysis (TMA) Dimension
12. Thermo-optical analysis (TOA) Optical properties
13. Derivatography A complex method in thermal analysis
18.2 THERMOGRAVIMETRIC ANALYSIS

Thermogravimetric analysis (TGA) is a method of thermal analysis in which changes in physical and
chemical properties of materials are measured as a function of increasing temperature (with constant

18.2
heating rate), or as a function of time (with constant temperature and/or constant mass loss). TGA
can provide information about physical phenomena, such as second-order phase transitions, includ-
ing vaporisation, sublimation, absorption, adsorption and desorption. Similarly, TGA can also provide
information about chemical phenomena, including chemisorptions, desolvation (dehydration), decom-
position and solid-gas reactions (oxidation or reduction).
The technique of TGA is concerned with an analysis of sample weight change curve. The tech-
nique involves change in weight of system under examination as the temperature is increased at a
predetermined and preferably at a linear rate. Automatic recording thermo balance can give the data
manual recording as well as curve of weight change of the sample versus sample temperature. TGA
has been widely used in recent years due to the easy availability of automatic, continuously recording
sophisticated thermobalances. These are reliable, rugged and very accurate.
TGA is usually two types—dynamic TGA and isothermal or static TGA.
Dynamic TGA
In this type of analysis, the sample undergoes continuous increase in temperature, usually linear with
time.
Isothermal TGA
In this type of analysis, the sample is maintained at a constant temperature for a certain period of time,
during which any changes in weights are noted.
18.2.1 Principle of TGA

The principle of the technique can be illustrated by the weight loss curve of a hypothetical compound
MCO3.2H2O as shown in Figure 18.1.
Y MCO3·2H2O
A MCO3·H2O
B MCO3
Weight loss
C D
MO
E F
Temperature (°C) X
Figure 18.1 Weight loss curve of a hypothetical compound MCO3.2H2O
In the curve, at point ‘A’, one water molecule is evolved, and the temperature at A is called “minimum
weight loss temperature”. A break is obtained in the curve ‘B’ due to the stoichiometry approaching
of MCO3 ⋅ H 2 O. Further heating results in the formation of anhydrous MCO3 weight levels from C
to D. The drying temperature of MCO3 is somewhere between C and D the values of C and D depend
upon the heating rate of the furnace. A slower heating rate will shift this temperature to lower values.

Thermal Analysis 18.3
At point D, the MCO3 starts decomposition and evolves CO2 and forms MO; the weight level from E
to F is the same due to the thermal stabilities of the original sample. The intermediate compounds and
the final product can be ascertained by an examination of the various regions in the curve. The curve
is quantitative in that the calculation can be made to determine the stoichiometry of the compound at
any given temperature.
Example: Thermogravimetric determination of copper and silver alloys are based on relative stabili-
ties of nitrates are shown in Figure 18.2.
Silver nitrate (AgNO3) is stable up to 473°C, where it starts decomposing into NO3 and O2 and
finally metallic silver is left at 608°C.
Cupric nitrate (Cu(NO3)2), however, decomposes into CuO in two steps. CuO remains stable up
to 950°C.
1. AgNO3
100 mg
15°K
2. Cupric 608°C
nitrate
278°C
3. Mixture
400°C 700°C
Figure 18.2 Thermogravimetric curve of copper and silver alloys based on relative stabilities of nitrates
In a thermogravimetric curve, it should be noted that the decomposition temperature is a function

of method apparatus and procedure. Moreover, the balance must be calibrated preferably each time
it is used by placing a known weight on the pan to give reference mark. This is done so that in the
upper right corner, correction must also be applied for the apparent weight change of the empty sam-
ple pan to get the actual weight change taking place in the specimen, the apparent weight changes
is usually caused by the inter play of a complex combination of various factors, such as contained
geometry, radiation effect, the atmosphere in the furnace, air buoyancy, conduction effects in the
furnace, etc.
18.2.2 Applications of TGA

TGA is commonly used to determine the selected characteristics of materials that exhibit either mass
loss or gain due to decomposition, oxidation or loss of volatiles such as moisture. Common applications
of TGA are as follows:
(i) Materials characterisation through analysis of characteristic decomposition patterns.
(ii) Studies of degradation mechanisms and reaction kinetics.
(iii) Determination of organic content in a sample.

18.4
(iv) Determination of inorganic content in a sample like ash, which may be useful for corroborat-
ing predicted material structures or simply used as a chemical analysis. It is an especially useful
technique for the study of polymeric materials, including thermoplastics, thermosets, elastomers,
composites, plastic films, fibres, coatings and paints.
(v) Determination of the composition of complex mixtures.
(a) Determines the purity and thermal stability of analytical reagents, including primary strands.
(b) Determines correction of error in gravimetric analysis
(c) New weighing composition in gravimetric analysis and determination of their thermal sta-
bility ranges.
(d) Weighing substances which are unstable at ambient temperatures such as that those which
absorb CO2 and H2O from air.
(e) The study of properties of materials in relation to the methods useful for their preparation.
(f) For evaluation of various filtration techniques, such as ignition of filler paper and so on.
(g) Discovery of new methods of separation.
(h) Studying the sublimation behaviour of various substances.
18.3 DIFFERENTIAL THERMAL ANALYSIS

Differential thermal analysis (DTA) is a technique in analytical chemistry for identifying and quantita-
tively analysing the chemical composition of substances by observing the thermal behaviour of sample
as it is heated. The technique is based on the fact that as a substance is heated, it undergoes reaction and
phase changes that involve absorption or emission of heat. In DTA, the temperature of the test material
is measured relative to that of an adjacent inert material. A thermocouple imbedded in the test piece
and another in the inert material are connected so that any differential temperatures generated during
the heating cycle are graphically recorded as a series of peaks on moving chart. The amount of heat
involved and temperature at which these changes take place are characteristics of individual element or
compounds. The identification of substance compound, therefore, is accomplished by comparing DTA
curves obtained from unknown with those of known elements or compounds. Moreover, the amount of
substance present in a composite sample will be related to the area under the peaks in the graph, and
this amount can be determined by comparing the area of characteristic peak under identical conditions.
18.3.1 Principle of DTA

The thermal effects associated with the physical and chemical changes described above are measured
by a differential method in which the sample temperature is continuously compared against the tem-
perature of the thermally inert reference material. The difference in temperature, called the differential
temperature (DT), is recorded as a function of reference material temperature or time, assuring that the
furnace temperature rise is linear with time.
In a typical experiment, a furnace is used which contains a sample holder. The latter has two
identical and symmetrically located chambers. One set of thermocouple junctions is inserted into the
inert material such as aluminium oxide and the other set of thermocouple junction is placed in another
chamber containing the sample. Other temperature detecting devices, which also have been employed,
are thermistor, resistance and thermometer. The furnace and the sample block temperature are then
increased at a linear rate and the temperature difference between the sample and reference material is
continuously measured against the reference material temperature.

Thermal Analysis 18.5
∆T h
TS–Tta
a c d f g i
0 b
e
120 270 580 980

Temperature of central wall
Figure 18.3 Differential thermal curve
The differential thermal curve is shown in Figure 18.3. At point A, it has been assumed that the sample
undergoes some type of endothermic reaction. It is also evident from the sample temperature curve
that the sample temperature is no longer linear with respect to time but logs the furnace temperature as
a result of absorption heat. The reaction becomes complete at B and the sample temperature increases
and after some time, it becomes equal to the furnace temperature again at C. During the actual transi-
tion which begins at A, the sample and reference material temperature differ ideally in the case of dif-
ferential temperature curve. A peak ABC, with maximum at B is thus obtained in the curve. Beyond B,
the curve retains to base the ∆T = 0 due to equalisation of sample and reference temperatures. Only an
endothermic transition is illustrated here. Hence, each substance will, in general, give a curve whose
number, shape and position of various endothermic and exothermic peaks act as a means of qualitative
identification of the substance. This technique can also be used to quantitatively evaluate the amount of
substance present by making use of the fact that the reaction is proportionally to the amount of reacting
substance.

1. The measuring unit in DTA is .
[Ans.: Rate of exchange weight]
2. The condition at which we measure the change of weight in TGA is .
[Ans.: Temperature]

1. What is the apparatus used in TGA?
(a) Thermobalance (b) Calorimeter
(c) DTA Apparatus (d) All the above
[Ans.: a]

18.6
2. What is the parameter used to examine the change in weight in thermometric method?
(a) Temperature (b) Light
(c) Pressure (d) None of these
[Ans.: a]

1. Explain any two applications in thermogravimetric analysis.
Ans.: 1. Determines the purity and thermal stability of analytical chemistry
2. Determines the composition of complex structure.
2. Write the types of thermogravimetric analysis.
Ans.: The types of thermogravimetric analysis are as follows:
1. Dynamic TGA
2. ISO thermal
3. What is the apparatus used in DTA?
Ans.: Thermobalance is the apparatus used in DTA.
4. How many types of thermal methods are observed?
Ans.: There are four methods:
1. Thermogravimetric analysis
2. Differential thermal analysis
3. Derivative thermogravimetric analysis
4. Thermometric titrations

Q.1 Give a detailed note on thermogravimetric analysis.
Q.2 Explain differential thermal analysis with a detailed sketch.

19 CHROMATOGRAPHY
19.1 INTRODUCTION
The separation of a mixture by the distribution of its components between a mobile and a stationary
phase is known as chromatography. Here, the mobile phase is solvent and stationary phase is column
packing material.
Chromatography is a valuable analytical tool as it can separate mixture components. It is also a
useful technique to obtain qualitative and quantitative information about each component.
The term “chromatography” is applied to a process in which mixture components are separated by
differential migration. The differential migration is caused by flow of mobile phase.
It may also be defi ned as follows:
Chromatography comprises a group of techniques that are used to separate mixture components
by the relative attraction of each component to the stationary phase. After the sample is added to the
stationary phase, the mixture (sample) spends some of its time on the stationary phase and the remain-
der of its time in the mobile phase. It depends on the abilities of the sample components to be adsorbed
on the stationary phase or to remain in the mobile phase. For example, a strongly adsorbed component
spends more time on the stationary phase than a weakly adsorbed component.
Adsorption on the stationary phase is caused by the attraction between a polar or changed group
on the stationary phase and a group of opposite polarity on the sample component.
Generally, the amount of adsorption on the stationary phase increases linearly until the adsorption
sites on the stationary phase are completely occupied.
In other words, the amount of adsorption of a chemical species on the stationary phase usually
increases as the concentration of the species on the mobile phase increases.
The amount of adsorption is also temperature dependent. Based on the adsorption, the mixture is
partitioned or divided between the stationary and mobile phase and moves along the mobile phase at a
controlled rate. As the mobile phase over use the sample and moves down the column, the components
of the sample mixture are subjected to series of distributions between the phases. Individual compo-
nents tend to migrate down the column at different rates and leave the column at different times.
19.1.1 Chromatography Timeline

S. no. Year Milestones
1. 1903 Tsvet separated plant pigments on chalk columns
2. 1931 Lederer and Kuhn separated carotenoids by liquid chromatography
(Continued )

19.2
(Continued)
S. no. Year Milestones
3. 1938 Thin layer and ion exchange chromatography started
4. 1950 Reverse phase liquid chromatography started
5. 1954 Martin and Synge got the Nobel Prize for gas liquid chromatography
6. 1959 Gel permeation
7. 1965 Instrumental liquid chromatography (water) started
19.2 CLASSIFICATION OF CHROMATOGRAPHY

Depending on the mobile phase and the attractive forces, chromatography is classified into the follow-
ing categories:
19.2.1 Classification Based on Mobile Phase

(i) Depending on mobile phase, chromatography is mainly divided into liquid chromatography and
gas chromatography.
(ii) Liquid chromatography is further divided, depending on the liquid used and by applying condi-
tions as follows:
(a) Classification based on type of liquid using aqueous, organic and super critical fluid chroma-
tography (SCFC).
(b) Classification based on liquid condition—column (gravity flow), high performance (pres-
sure flow) and thin layer (adsorption) chromatography.
(iii) Gas chromatography is further divided into gas-solid and gas-liquid chromatography, depending
on the stationary phase.
19.2.2 Classification Based on Attractive Forces

(i) Adsorption chromatography (for polar non-ionic compounds) and ion exchange chromatography
(for ionic compounds)
If the analyte is an anion, the bonded phase has positive charge.
If the analyte is a cation, the bonded phase has negative charge.
19.2.3 C
lassification Based on Partition of Relative Solubility
of Analyte in Mobile and Stationary Phase
(i) Normal chromatography—if the analyte is non-polar, polar organic stationary phase is used than
mobile phase.
(ii) Reverse chromatography—if the analyte is not polar, polar organic stationary phase is used than
mobile phase.
19.2.4 C
hromatographic Techniques on the Type of Support
Material Used in the System
(i) Packed bed (column) chromatography, open tubular (capillary) chromatography and open bed
(planar) chromatography

Chromatography 19.3
19.3 TYPES OF CHROMATOGRAPHY

Chromatography is divided into different categories, depending upon the nature of the stationary phase
and mobile phase. Different types of techniques are listed in Table 19.1.
Table 19.1 Types of chromatography

S. no. Type of chromatography Mobile phase Stationary phase
1. Gas–liquid Gas Liquid
2. Gas–solid Gas Solid
3. Ion-pair Liquid Liquid
4. Ion-exchange Liquid Gel
5. Liquid–Liquid Liquid Liquid
6. Liquid–Solid Liquid Solid
7. Thin-layer Liquid Flat-plate
8. Paper Liquid Liquid on paper
9. Size exclusion Liquid Gel
10. Adsorption Liquid Solid
11. Partition Liquid Liquid-coated
19.3.1 Gas-Liquid-Chromatography
The concept of gas-liquid-chromatography (GLC) was first enunciated by Martin and Synge in 1914. It
is the most elegant and useful of all the chromatographic techniques. GLC is also called as vapour phase
chromatography, gas-liquid partition chromatography, gas partition chromatography and vapour fractom-
etry chromatography. GLC is preferred for the separation of species other than low boiling point materials.
In GLC, a solid porous support (diatomaceous earth or crushed fire brick) is coated with a thin film
of liquid phase. The coatings are normally non-volatile and chemically inert. While passing the sample
solution through the column, the components of the mixture are separated by differential migration.
Instrumentation
The main components of GLC can be divided into four sections as follows:
(i) Carrier gas
(ii) The column and packing materials
(iii) Sample introduction
(iv) Detectors
Carrier Gas
Carrier gas functions as a mobile gas phase, which progresses the sample down the column. In order
to perform this function, the flow of carrier gas should be controlled. The carrier gas supply system
comprises a needle valve, a flow meter, a pressure gauge and a few feet of metal capillary restrictors.
A high pressure gas cylinder is used as a carrier gas reservoir; usually, N2, H2, He, Ar and CO2
gases are used as carrier gas. The choice of the carrier gas depends partly on the composition of the
sample. For example, H2 and He are used when thermal detectors are employed since the thermal

19.4
conductivity of H2 and He is much higher than other carrier gases. The carrier gas normally used is
helium since it is more easily removed by differential pumping than any other gas and it is a high ioni-
sation potential (22 eV).
Flow Rate
The flow of carrier gas is caused due to the pressure difference between the inlet and outlet of the
column. The rate of gas flow in particular analysis depends on the diameter of the column. For every
separation procedure, there is an optimum carrier gas flow rate which has to be determined experimen-
tally. Normally, the gas flow rate is around 10–400 mL/min. The flow rate should be maintained below
1% in order to reduce analytical errors. The rate of gas flow is constant when the inlet pressure remains
constant. Generally, the rate can be measured by using rotameter or a sample soap bubble flow meter
which gives an accuracy of about 1%.
Column and Packing Materials

Several techniques are employed for coating support particles with stationary liquid phase. In one
method, a known weight of support is mixed with three or four times of solvent. The solvent is then
evaporated often in a rotatory stripper, to give a dry, free flowing solid. The flowing solid is slowly
poured into the column with gentle tapping.
There are two types of columns which are commonly used. They are packed columns and capil-
lary columns or open tubular columns.
Packed Columns
The packed column is a tube, packed with a suitable material like tubing glass, stainless steel or
copper materials. The internal diameter of the column is usually between 4 and 8 mm. The length of
the column may be between one and five m; very long columns are best constructed by coupling shoot
(less than 3 m) sections, to any desired length.
Open Tubular Columns

Open tubular columns vary in length between 10 and 100 m. The inner diameter of open tubular columns
is often between 0.2 and 0.5 mm. Most open tubular columns are constructed with glass or fused silica
rather than metal because metals can catalyse several chemical reactions within the column temperature.
Types of Solid Support

The solid support serves to hold in liquid stationary phase when exposed to mobile gas phase; it should
not possess adsorption properties towards the components of the sample. It serves as a mechanical
matrix for the liquid phase.
The most common solid support is derived from diatomaceous earths and are the skeletal remains
of the unicellular algae known as diatoms. They are also known as kieselguhr. Diatomaceous earths
primarily consist of hydrated silica groups, represented as follows.
OH OH OH OH
OH OH
O O O
Si Si Si Si
Si O Si (or)

Chromatography 19.5
If the diatomaceous earths is heated to about 900°C and crushed to particle of uniform size, the result-
ant pink substance is known as chromosorb-p; it possesses polar functional groups which make it a
good adsorbent. If chromosorb-p is not coated with a liquid base, it can be used as the stationary phase
in GSC. The polar sample components can be adsorbed on chromosorb-p as well as dissolved in the
stationary liquid coated on the support.
If the diatomaceous earth is heated in the presence of Na2CO3, a white solid called chromosorb-w
is obtained. In addition to the products of the diatomaceous earths, several other substances such as
powdered Teflon, graphitised carbon black, volcanic bacteria, armeenan neomberian deposits, acti-
vated carbon, many organic polymers, alumina, silica gel, aluminium, silicon, MgO, MgCO3, ver-
miculite and glass are also used. Beads have been used as solid support; if the solid support is more
polar, then it can be deactivated (made with a paper) by coating of dimethyl chlorosilane (DMCS) or
by rinsing the support within a solution of a strong acid (usually, HCl). Acid washing retains metallic
impurities on the support and coats some of the polar sites.
CH3 CH3
Si OH + Cl Si Cl Si O Si Cl
CH3 CH3
Upon washing with alcohol, the second chloride is also replaced by a methoxy group.
CH3 CH3
Si O Si Cl + HO CH3 Si O Si OCH3
CH3 CH3
The adsorption effects can also be minimised if the celite is treated with silating agent, such as hexa-
methyl disilane or dimethyl dichlorosilane.
Stationary Liquid Phase

The stationary phase should be a liquid that is virtually non-volatile at column temperature. The choice
of liquid phase (stationary phase) depends on the composition of the sample.
The mobile phase competes with sample components for adsorptive sites on the stationary phase.
If the polarity of the mobile phase increases, it results in greater adsorption of mobile phase molecules
on the stationary phase and a decrease in the number of adsorptive sites which are available for the
sample components. Consequently, increasing the polarity of the mobile phase decreases the retention
time of the sample components. Alternatively, the sample components can be thought of as partition-
ing themselves between the stationary phase and mobile phases. The polarity of the mobile phase
increases the concentrations of the components in the mobile phase increase and the retention time
decreases.
Generally, it is found that the polar substance is most satisfactorily analysed on a polar stationary
phase. Similarly, a non-polar compound will show the best results on a non-polar phase.
Example: For separation of polar components like alcohols, amines, etc., it is preferable to choose
a polar liquid like polyethylene glycol.

19.6
The general requirements for a good liquid phase are as follows:

(i) It should be essentially non-volatile at the temperatures to be used.
(ii) It must be thermally stable.
(iii) It should yield the appropriate value for the components to be studied. It should be neither too
small nor too long.
(iv) It should be readily available in a reproducible form.
(v) It should be chemically inert towards solid or if it reacts, it should be fast and reversible.
(vi) The liquid should have a very low vapour pressure.
(vii) It should be a good solvent for a component of the sample.
A single liquid does not melt a requirement for all possible solutes. Some are needed for low tempera-
ture, others for high pressures. For some studies, a non-selective liquid is desirable; for others, a highly
selective phase is needed. The choice of the liquid is often based on the availability and habit.
Column Preparation
Several techniques are employed for coating support particles with a stationary liquid phase. In one
method, a known weight of support is mixed with three to four times of volatile solvent. The solvent is
then evaporated, often in a rotatory stripper, to give a dry, free following solid. The following solid is
slowly poured into the column with gentle tapping. Usually, two types of columns—packed and open
tabular columns— are encountered in GLC.
Sample Introduction
In this technique, the sample must be introduced into the column in the form of a compact “plug”. For
this purpose, the following methods are used.
Syringe Method
In this method, the samples are directly injected at the inlet part within a short period with the help of
micro syringe. In commercial instruments, a rubber septum is used.
Liquid samples are also introduced with syringes (0.1–100 mL capacity) as neat liquids or solution.
The sample is drawn into the syringe without any air bubbles.
Gaseous samples are introduced into the column by the gas light syringe, by pass loop system or
by the use of valves.
Solid samples can be introduced into two ways; the solid sample is dissolved in a suitable solvent
and injected as a solution or the solid is packed into the end of the syringe by “tapping”. In some meth-
ods, the sample is injected directly into the instrument through a septum by a plunger (Figure 19.1).
Carrier gas of
Substrate
controlled pressure
Sample injected
into gas stream
Syringe
Figure 19.1 Syringe method

Chromatography 19.7
Valve Method
This method is especially convenient for sample gas stream or shown in Figure 19.2.
Sample gas Carrier gas
Vent To column
Sample reservoir
Figure 19.2 Valve method
As shown in Figure 19.2, when the No. 1 valve is turned at 90°C, the sample reservoir is filled with
sample gas. After returning to its original position, No. 2 valve is turned at 90°C, so that the measured
carrier gas is filled into the column. Many ingenious modifications have been constructed by fusing a
single stop lock with multiple openings.
Ampule Method
It is a precise method to introduce the sample, but the least convenient. The sample is sealed in a fragile
glass ampule and weighed. The sample is then inserted into a special, heated chamber at the head of
the column, where it is surrounded by following carrier gas. When the temperature reaches a certain
range, the sample is vaporised almost in simultaneously and is swept on to the column (Figure 19.3).
Column
Recorder
injector
Reducing volve
Flow meter
Pressure
regulator Detector
Carrier gas
reservoir
Figure 19.3 Gas-liquid-chromatography
Detectors
The function of the detector is to detect and measure the difference of the sample as they immerse from
the column. The choice of the detector depends on the type of analysis being performed. High sensitiv-
ity can be achieved by using a flame detector and the sample is destroyed in the process. High selectiv-
ity can be achieved with electron–couple detectors. Other detectors such as the thermal conductivity
detectors are non-selective and non-destructive.
According to Haler, detectors can be classified into two major families; they are detectors can
respond to the concentration (in mole fraction) of the solute in the carrier and those that respond to the
mass flow rate of the solute (in moles per unit time).

19.8
First Family Detectors

Thermal Conductivity Detector
Thermal conductivity detector (TCD) is a simple and most widely used type of detector. TCD intro-
duced by ray in 1914 the and is also known as katharometer. It is based on the principle that all gases
have the ability to conduct heat, but in varying degrees. The difference in heat conduction can be used
to quantitatively determine the composition of a mixture of gases.
The schematic diagram of TCD is shown in Figure 19.4.
To resistance
measuring device
Column
Exhaust
Gas flow from gas
chromatogram
Hot wire
Figure 19.4 Thermal conductivity detector

As shown in Figure 19.4, the detector consists of a hallow tube with a wire situated in the central
axis. The wire is electrically heated when only the carrier gas flows over it; a thermal balance can be
obtained at a certain temperature under the condition of steady temperature and the electrical resist-
ance of the wire is steady. When a different gas (e.g., a sample component) flows over the wire, there is
a change in the thermal conductivity of the surrounding gas. Heat is conducted away from the wire at
a different rate. The temperature of the wire changes by using resistance for detection and estimation
of the unknown sample components.
a -ray Argon Ionisation Detection

The electron capture (or electron affinity) detector operates on the basis of electron by compounds that
have an affinity for electrons. Thus, the compound must have an electro negative group or element.
The detector consists of two electrodes (as shown in Figure 19.5) across which a potential differ-
ence of 10–100 V can be applied. The source of electron or b -rays is tritium rather than Sr90. Tritium is
a radioactive gas that emits b -rays. It is usually installed in the form of a tantalum wire saturated with
tritium. The b -rays or electrons traverse the effluent from the gas chromatogram. Many compounds
such as paraffin and simple hydrocarbons, are virtually transparent to electrons, but organic halides,
phosphorous or nitrogen compounds are not transparent to the electrons and the latter are captured by
such compounds.
Electrodes setup at
different potential
Column
Sr90 Exhaust
Gas flow from
gas chromatogram
column
Figure 19.5 Cross section of detector

Chromatography 19.9
As the carrier gas (nitrogen) flows through the detector, b particles from the tritium source ionise the
nitrogen molecules and form slow electrons. These slow electrons are create a fixed voltage to the
anode. When these electrons are collected at the collector electrode, they produce a steady current
which provides a base line on the recorder.
When the organic compounds which contain halogen, nitrogen and phosphorus pass through the
column, there is some variation in the number of electrons reaching the collector electrode and thus
provides the detection signal.
Argon Ionisation Detectors

In the argon ionisation detector, argon must be used as the carrier gas in the chromatography separa-
tion. The detector contains two electrodes placed parallel to each other and a potential difference is
applied across them.
Under normal conditions, the carrier gas (argon) acts as an insulator and no current flows between
the electrodes. A radioactive source (tritium) is placed in the approach region to the electrodes so that
the rays emitted by it excite the argon atoms and the electrons are produced by a thin bombardment
action.
When the carrier gas electrodes emerge out of the column, no current passes across the electrodes
under normal condition as the gas is a non-conductor. When it is subject to ionising radiation (b rays),
the carrier gas produces a steady supply of positive ions and free electrons which can be measured as
a standing current between two changed electrodes. The reactions which take place in the detector can
be represented as follows.
Ar electron
 → Ar * (excited )
→ Ar + RH* + e −
Ar * + RH 
When the sample components pass through the detector, the standing current may be perturbed com-
ponents containing highly electronegative atoms that capture free electrons very efficiently. They are
detected by the decrease in the standing current. This occurs because of the increased rate of recom-
bination of positive and negative ions, compared with positive ions and electrons. Other species have a
little effect on the ion current, thus, electron the capture detector is highly selective and very sensitive
for compounds containing halogens, phosphorus, peroxides, amines, quinones, alcohols, nitro com-
pounds and poly nuclear aromatic ring systems. They do not detect H2O, CH4, O2, CO2, N2, CO, C2H6 or
fluorinated compounds (CXFX). The sensitivity of the detector is 0.08 mg/ml and the linear dyanionic
range is 105. The detector is suitable for measurement or organic molecules present over a wide range
of concentrations.
Second Family Detectors

Flame Ionisation Detector
The flame ionisation detector is the most widely used detector in gas chromatography. Its linear
dynamic range is approximately 107. It was introduced by William and Dewar. These detectors are
based on the electrical conductivity of the gases. At normal temperatures and pressures, gases act as
insulators, but if electrons are present, they will become conductive ions.
Hydrogen flame detector is one of the simplest detectors; in this detector, hydrogen must be used
as a carrier gas. In this detector, the effluent from the columns is led into an oxy-hydrogen flame. As
shown in Figure 19.6, two wire electrodes are placed in a flame. An electrical potential is applied across
the electrodes.

19.10
Collector electrode
polarizing electrode
Flame
Air
Sample from
H2 GC column
Figure 19.6 Flame ionisation detector
When only the inert carrier gas enters the flame, the current across the electrons is constant. When an
organic compound from the end of the chromatography columns enters the flame, it is broken up into
fragments that are highly conducting. These ions result in ionisation current and there would be con-
sequent change in the current flowing across the electrodes. The magnitude of the variation in current
would be directly proportional to the number of ions or the electrons formed in the flame gases, which
in turn, would be proportional to the carbon content of the organic molecules in the vapour.
Thus, the detector is capable of detecting 10−12 g of organic material. It has secured disadvantages
such as it is not sensitive to many inorganic compounds (O2, H2O, CO2, NH3). The change in conduc-
tivity depends on the particular molecules; hence, its response to organic compounds depends on the
particular molecules.
19.4 CHROMATOGRAPHY THEORY
19.4.1 Distribution Coefficient or Partition Coefficient (K)

The distribution coefficient is defined as the ratio of the concentration of the species in the stationary
phase CS to the concentration of the species in the mobile phase Cm.
Cs
K= (1)
Cm
The distribution coefficient (K) is related to the velocity of a comparent which moves along the station-
ary phase during development. As K increases, the average velocity of motion decreases. As different
components have different distribution coefficients for a particular set of experimental conditions, the
distribution coefficient of a component could be compared to the coefficients of known species for
quantitative analysis.
19.4.2 Retention Time (tR)

A more easily measured parameter, which can also be used for quantitative analysis, is the retention
time (tr) of a chemical species.

Chromatography 19.11
The retention time is the time required to elute a sample component from the station any phase,
that is, it is the time required for the mobile phase to sweep the component from the stationary phase.
From this definition, we can write the following equation rate.
 1 
R = u
 1 + K 1 
length L L
tR = = = (1 + k 1 ) = tm (1 + k 1 )(2)
rate  1  U
u
 1 + k1 
where
tm is the time required for a carrier molecule to transverse the column.
u is the carrier gas flow rate.
L is the length of the column.
k1 is the capacity factor.
19.4.3 Retention Volume (VR)

The retention volume is the volume of the mobile phase required to elute the sample component from
the stationary phase. The retention volume, VR, is proportional to the retention time and to the flow
rate. The flow rate (F) is normally measured at the end of the column; hence the true flow of rate (FC)
at the column temperature TC, is
Fc = F × Tc (at room temperature)
The retention volume at the column temperature and atmosphere pressure is then;
VR = tR + FC(3)
However, a pressure gradient exits down any column, and it is necessary to introduce and additional
correction factor, J, to correct the gas volume for compressibility in the column.
The corrected absolute retention volume VR is thus:
VR + tR Fc J
This can be seen from Figure 19.7.
tR
2
Detector response
tR
1
Air
Time (or) Volume
Figure 19.7 Chromatography retention times or volumes against to detector response
As shown in Figure 19.7, an air peak after appears in a chromatogram from the unretained air injected
with the sample, and the time for this to appear is taken as tm. Relative retention values (a) are obtained
by comparing the specific retention volumes (Vg) of the solute under consideration with some standard
solute whole behaviour on the particular column in use being precisely known.

19.12
t − tm V − Vm
a = = (4)
tret − tm Vret − Vm
This is the ratio of the retention time or volume of the substance, after correction for t m and Vm to the
corrected retention time of volume of a reference compound.
As the retention volume at a constant flow rate is proportional to the retention time, the two defini-
tions of relative retention are equivalent. The direct proportionality between the distribution coefficient
‘K’ for a substance and the corrected retention time or retention volume of the substance makes it pos-
sible to express the relative retention in terms of distribution coefficient.
K
a = (5)
K ref
Where a = relative retention.
In ion-exchange chromatography, the relative retention (Equation 5) is sometimes called the sepa-
ration factor.
19.4.4 Plate theory

The plate theory was first introduced by Martin and Synge from the distillation theory of columns. A
theoretical plate can be thought of as a single equilibrium of the sample component between the sta-
tionary and mobile phases or a theoretical plate is the portion of column in which an equilibrium exists.
This equilibrium indicates the existence of a single component between a stationary phase and a
mobile phase.
The column efficiency can be explained based on the number of theoretical plates, N. As the num-
ber of theoretical plates increases, the column efficiency also increases. Thus the number of theoretical
plates N, is used as measure of column efficiency. Clearly, the product of these two terms is the column
length L,
That is, L = N++
L L
The height equivalent to one theoretical plate is defined by H = (or) N = .
N H
“H” decreases as the efficiency of a column becomes greater, that is, as “H” becomes smaller, the
number of equilibrations that occur in a given length of column become larger.
Resolution
Resolution is a measure of the degree of separation of adjacent peaks. Two general factors will deter-
mine the effectiveness of the separation distance between the zone centres as they migrate and compact-
ness (overlap) of zones. As the distance between the zone centres increases, the degree of separation
increases and a measure of the difference is termed resolution.
As the zones travel, they tend to spread and broaden and even though the zone centres are well
separated, overlapping of the bonds can occur. This is illustrated as shown in Figure 19.8.

(a) Qs = 0.5
(b) Qs = 0.75
4
Signal
(c) Qs = 1.00
(d)
Qs = 1.5
Time (or) volume
Figure 19.8 Resolution and the measure of the degree of separation

∆tr ∆Vr
The resolution of two peaks from each other is defined as resolution RS = = (1)
w w
where ∆tr or ∆Vr is the separation between peaks (in units of time or volume) and w is the width of each
peaks, in corresponding units (w = 4s). For simplicity, we assume that w is same for both peaks. Figure
19.8 shows how two peaks are separated at various values of resolution. When resolution = 0.5, the
overlap of the two peaks is 16%; when resolution is = 1.0, the overlap is 2.3% and overlap is reduced to
0.1 at a resolution of 1.5. It can be shown that the resolution is given by
N  a − 1
Resolution =  a  t z(2)
4
Factors Affecting Separation
In GLC, the following parameters are of practical interest and can be altered to improve the efficiency
of the separation.
Particle Size and Surface Area

An increase in the surface area or a decrease in particle size tends to increase the number of theoretical
plates. In general, a 60/80 mesh particle size is usual into a quarter- inch column.

19.14
Carrier Gas Flow Rate

There is an optimum flow rate which gives the maximum efficiency. This parameter can be experimen-
tally determined. If the gas flow rate is very slow, the eluted peaks will tend to be broad while if the
flow is too fast, the peaks will not resolved.
Type and Amount of Stationary Phase

It is a key factor in determining the efficiency of the column. Therefore, considerable care must be
exercised in choosing the correct stationary phase. If the wrong liquid is chosen, separation will not
be obtained.
The amount of stationary phase will affect the column performance in several ways. As the con-
centration of the liquid phase increases, the number of the orbital plates for the column will also
increase. Excessive liquid support can also cause tailing in the chromatogram. In general, light broad-
ening is preferred and most columns contain from 1–5% liquid phase.
Column Length
As the length of the column increases, the number of theoretical plates will increase. There is a practi-
cal limit to the length because problems relating to the gas flow are encountered with long columns.
Most columns are between 1 and 10 m (excluding capillary columns).
Column Diameter
As the diameter of the column decreases, the number of theoretical plates will increase.
Column Temperature
The maximum temperature for the column is determined by the vapour pressure of the liquid phase—
the vapour pressure of the sample and the efficiency of separation. The temperature should not be high
enough to vapourise the stationary phase. As this will destroy the uniformity of the column, on the
other hand, the temperature has to be high enough to maintain the sample in the vapour state. Hence,
adjustment of the temperature is made to give high numbers of theoretical plates, which leads to opti-
mum resolution, while maintaining reasonable elution times for the components of the sample.
19.5 HIGH PERFORMANCE LIQUID CHROMATOGRAPHY

Liquid chromatography is a slow separating technique and is performed in vertical columns under
gravitational force.
High performance liquid chromatography (HPLC) is a high resolution and high speed liquid chro-
matography since it makes use of high pressure to force liquid through a column, and is packed with
very efficient particles of a very small diameter. This arrangement provides a high inlet pressure up to
10,000 psi and gives reasonable flow rate. Therefore, the versatility has been achieved by using smaller
diameter and large surface area particles and by using suitable packing structure. Therefore, the HPLC
has seven times more resolving power than liquid chromatography.
Apart from flow changes, HPLC is analogous to liquid chromatography in many ways as follows.
(i) The low pressure pumps are replaced by high pressure pumps is which can produce pulse free
inlet pressure of 600-1000 psi.

(ii) HPLC provides great reduction time in comparison with conventional liquid chromatography.
Furthermore, this reduction is accomplished over a wide range of unknown sample concentra-
tions, including trace levels with a high degree of precision and accuracy.
(iii) HPLC is capable of generating high column efficiencies. That is, plate heights are extremely
small in comparison with conventional liquid chromatography. Therefore, a very low number of
plates are possible given column lengths.
(iv) HPLC is applicable not only to the separation of lower molecular weights, but also to macro-
molecular compounds. Furthermore, separations based on adsorption, partition, ion-exchange
and size exclusion are possible. For these reasons, HPLC may be significantly greater than other
chromatographic techniques.
The various components of HPLC are described as follows and shown in Figure 19.10.
Column Packing Materials

The size and diameter of the particle influence the efficiency of the column. Usually, 30–50 µm diam-
eter porous type material is coated as a thin layer in the column. This liquid thin layer is chemically or
covalently bonded to the solid support so that it is not washed away by the mobile liquid phases under
high pressures.
The esterified silicon packing is not very suitable, since it gets hydrolysed and also gets exchange-
able with lower alcohols. To avoid this, generally, silicon polymers are used as packing material as
these polymers have three-dimensional cross-linked structure and are very stable.
The stationary liquid phase is covalently bonded to the silica surface by the reaction as follows
(Figure 19.9):
OCH2CH3
CH3 CH2 OH
Particle Si OH + (CH3 CH2O)3 Si R Particle Si O Si R
OCH2CH3
R = C8H17 and C18H37 (Octadenyl group C18H37)

H H H
OH H H H
O
Si O C C C H
Si C C C
O H H H
O OH H H H
Silica substrate
O
Si O
O
O
O
Si O
O
Figure 19.9 Diagram of C8H17 groups bonded to silica

19.16
Column polar phases Non-polar phases

R = (CH2)3NH2 R = (CH2)17CH3
R = (CH2)3CN R = (CH2)2
The efficiency of the column is increased as the particle size is decreased. This can be observed by
plotting plate height versus linear velocity.
As shown in Figure 19.10, the reduction of particle size from 45 to 6 µm results in a ten-fold or
more decrease on plate height.
Y
5 44.7 µm
Plate height (µm)
4 34.9 µm
22.6 µm
3
13.2 µm
2 8.8 µm
1 6.1 µm
X
0
1 2 3 4 5
Linear velocity (cm/sec)
Figure 19.10 Plate height versus linear velocity
Column Parameters
Column Length
Column length is an important experimental parameter that controls the number of available plates.
This, in turn, influences the resolution and retention time. The actual length of the column used in
HPLC is usually determined by the resolution required, inlet pressures and type of analysis. The col-
umn length should be around one to five metres. In some cases, longer columns are used in order to
detect large samples. These can be made by connecting a series of short columns with dead volume
connections.
Column Diameter
The inner diameter of HPLC columns range from two to five mm since the sample capacity varies with
the diameter. Larger diameter columns are only used for preparative HPLC. If short columns are used,
they are usually used as linear columns.
Sample Introduction
Sample can be introduced by any one of the following methods:
(i) Syringe septum injection
(ii) Stop-flow injection
(iii) Sample valve injection

Syringe Septum Injection

In this type of system, the sample can be introduced directly into the column through a self-sealing
electrostatic system. For this reason, micro syringes are designed to withstand pressures up to 1,500 psi.
Stop-Flow Injection
Stop-flow injection is the second type of syringe injection in which no septum is used. Hence, the sol-
vent flow is momentarily stopped.
Sample Valve Injection

The most widely used sampling devices are now sampling valves or loops. Sampling loops permit the
introduction of samples at pressures up to 7,000 psi.
Pumping Systems
In HPLC, two or more suitable pump systems are connected to several reservoirs (Figure 19.11). The
pumping system must have the following requirements:
(i) Generations of pressure up to 10,000 psi (Ibx/in 2)
(ii) Pulse-free output
(iii) Flow rates ranging from 0.1 to 10 mL/min
(iv) Flow control and flow reproducibility of 0.5% or better
(v) Corrosion-resistant components (seals of stainless steel or Teflon)
There are three types of pumps, namely reciprocating pumps, syringe or displacement type pumps and
pneumatic or constant pumps. These are explained as follows.
Reciprocating Pumps
Reciprocating pumps usually consist of a small chamber in which the solvent is froth pumps by the
back and motion of a motor driven piston. These kinds of pumps contain about 2–3 µm filter to prevent
dust from getting into the pump heads. Excessive dust will clog the filter and lead to poor performance.
The advantage of reciprocating pumps include their small internal volume (35–400 µL), high
output pressures (up to 10,000 psi), ready adoptability to gradient elution and their contact flow rates,
which are largely independent of column back-pressure and solvent viscosity.
Displacement Pumps
Displacement pump usually consists of large, syringe-like chambers equipped with a plunger that is
activated by a screwdriver mechanism, powered by a stepping motor.
The liquid displacement pump is capable of producing the highest pressures available for HPLC
(>75,000 psi). Normally, inlet column pressures of this type should not be encountered in HPLC if this
kind of pressures is required to achieve a reasonable flow. The availability of those pressures are useful
in HPLC for packing micro-sized stationary phase particles.

19.18
Pump
Injection head
Buffer
volume Column
Heater jacket
Multiport
volve Cappillary
connecting table
Detector Recorder
Solvent
reservoir
Figure 19.11 Block diagram of HPLC
Flow Control and Programming System

Most commercial HPLC instruments are equipped with computer-controlled devices for measuring
the flow rate. Many instruments have some devices for varying the compositor of the solvent either
simultaneously or in a step-wise fashion.
Solvent Treatment
The solvent used in HPLC must be of high quality. Therefore, solvents should be filtered before injec-
tion. In order to remove dust particles, the solvent is passed through a pre-column in which impurities
will be collected.
In liquid chromatography, the sample is more like the solvent; then, it is necessary to make the
solvent less like the sample by changing the solvent property.
Detectors
The detectors used in HPLC can be classified in general terms as bulk property detectors and solute
property detectors. The bulk type detector functions by measuring a bulk physical property of column
eluent, while the solute type detector functions by measuring a physical under chemical property of a
solute. The bulk property detector will have a sensitivity of about 10-6 g/mL and the solute property
detector about 10-9 g/mL.
Detectors used in HPLC are as follows:
(i) Refractive index
(ii) Dielectric constant

(iii) Electrical conductivity

(iv) Thermal conductivity
(v) UV and visible
(vi) Fluorescence
(vii) Radioactivity
(viii) Electron capture
Of all these detectors, the most commonly and widely used detectors are refractometer detectors
and UV detectors. The differential refractometer detector is often called a “universal detector”.
Refractive Index Detector

The refractive index detector is a differential refractometer and measures the refraction of a light beam.
It arises due to the difference in refractive index between the sample and the reference channel. The
sample channel contains mobile phase plus solute from the column while only the mobile phase passes
through the refractive channel.
In the operation of the refractive index detector, the lens are adjusted to the light beam, and the
parallel beam passes to the mirror through the sample and reference cells. The mirror reflects the beam
back through the cells and lens which focuses the reflected light into a photo cell. The angle of deflec-
tion arising from the difference between the two cells causes the angle changes. Finally, the photo cell
measures the change in the beam intensity. The signal is then amplified and recorded (Figure 19.12).
Mark
Sample
Lens Light source
Reference Detector Amplifier and Recorder

Mirror Photo cell power supply
Figure 19.12 Refractive index detector of HPLC
19.5.2 Theory of High Performance Liquid Chromatography

Equilibrium Constant
If the chromatographic system attains equilibrium, the ratio of the concentrations of the solute in the
two phases is constant and can be expressed as equilibrium constant. Thus, for a two component mix-
ture of solute 1 and 2 are as follows:
KD1 = C 1 s / C 1m
KD2 = C 2 s / C 2 m

19.20
where KD1 and KD2 are the equilibrium constants for solutes 1 and 2. C is the concentration of solutes
in stationary phase(s) and mobile phase (m).
Desorption
Desorption of 1 and 2 in the columns at a given time is shown in Figure 19.13, assuming the system is
at equilibrium.
tR2
Detector response
tR1
w1 w2
tm tR1 tR2
Time (or) Volume
Figure 19.13 Chromatographic retention time or volume versus detector response
Directive of Mobile Phase Flow

Concentration of solute in mobile phone
Fraction of bed
length
Concentration of solute in stationary

illustration of sorption - desorption in the
phase chromatographic system
Retention Time and Volume

The appearance of peaks in the effluent can be expressed in terms of retention volumes. They charac-
terise the particular components and are described on the basis of a chromatogram. The chromatogram
is obtained by plotting detector response on y-axis and time or volume on x-axis.
As shown in Figure 19.13, tR1 and tR2 are the retention times for components 1 and 2 and tm is
the relation time for a solute which does not participate in the sorption–desorption process. It passes
through the column at the same rate of the mobile phase. This volume (occupied by a solute or air) is
often referred to as the dead volume of the column.

In order to find out the variable components in the chromatography method, it is essential to
calculate the corrected retention times, tR or net retention time tN given as follows:
t R1 = t R1 − tm
t R2 = t R2 − tm
When the chromatographic experiment is performed at a constant known flow rate, the position of each
peak can be expressed as a retention volume:
VR1 = t R1 × flow rate
VR2 = t R2 × flow rate
Vm = tm × flow rate
where VR1 ,VR2 and Vm are the retention volumes for peak 1, peak 2 and a solute that is not sorted respectively.
Separation Ratio
The ratio of the distribution coefficients for each of the two components is called the separation ratio,
a and is given by
K D2
a =
K D1
By definition, the component having the larger K D value is designated as K D . Therefore, the numbered
2
value for a must be greater than or equal to one if both components have the same K D value.
If chromatographic peaks are defined in terms of retention times as shown in Figure 19.13, the
separation ratio is given by
t R2 − tm t R2 K D2
a = = =
t R1 − tm t R1 K D1
The actual values of the distribution coefficients for the components 1 and 2 are also important
in determining the case of separation. For example, both of the following provide the same a values.
2 20
a =
= 2; a = =2
1 10
As shown in the above mentioned values, the latter separation valid required a much larger analysis
time.
Capacity Ratio or Capacity Factor (K′)

Capacity ratio is defined as the ratio of concentration of the solute in the two phases. It is also referred
to as the capacity factor (K′).
qs C A dx
Thus, K ′ = = s s
qm Cm Am dx
where dx = length or distance (a small section of the bond)
Q = number of moles of solute in the two phases
A = cross sectional area of the two phases
V = volume of two phases

19.22
s and m indicate the stationary and mobile phases respectively. It is an important equation in chro-
matography since it relates the equilibrium distribution of the solute within the column to the thermo-
dynamic properties of the column; graphical representation is shown in Figure 19.14.
Concentration
Detector response in mobile
phase
Concentration
in stationary
phase
Time (or) Volume
Figure 19.14 Equilibrium distribution of the solute between mobile and stationary phase
If one solute molecule were to be followed through the column, it would spend a fraction of its time in
the stationary phase and a fraction of its time in the mobile phase. The average fraction of time in the
stationary phase is given byQ5 Q5 + Qm and the average fraction of time in the mobile phase is given
Qm
by .
Q5 + Qm
Q5 1 Qm 1
= ; =
Q5 + Qm (1 + K ′ ) Q5 + Qm (1 + K ′ )
When the mobile phase moves down the column at constant velocity V, the solute molecule in the
mobile phase moves at the velocity V, but remains static in the stationary phase.
Therefore, the average velocity of the band will depend on the velocity V, of the mobile phase, and
the fraction of time, the solute is in the mobile phase. The band velocity Vband is given by
Vband = V ( 1
1+ K ′ )
Isotherms (Peak Shapes)
If the distribution coefficient (K D) is independent of concentration, a plot of the concentration of the sol-
ute in the stationary phase versus the concentration in the mobile phase provides a linear distribution
isotherm. A graph of this type is called linear distribution isotherm. The slope of the linear isotherm
gives the distribution coefficient.
C
K = s (or ) Cs = KCm
Cm
Non-linear isotherms are also formed when the distribution coefficient is dependent upon the concen-
tration, which causes the elution peak to be skewed and the retention or volume to change with sample
concentration.

Conc. in stationary phase

Linear Convex Concave
Conc. in mobile phase

Detector response
Retention time
Retention time
Sample size
Figure 19.15 Graph showing isotherms
As shown in Figure 19.15, the isotherm has been used to describe a non-ideal inter molecular attraction.
For example, convex isotherms are usually encountered in column chromatography due to the forma-
tion of hydrogen bonding between the solute and stationary phase.
The concave isotherm is often characteristic of an end-on orientation of the solute molecule towards
the stationary phase surface. These peaks will arise due to over loading of the column with excessive sam-
ple. Due to variation in the activity of the available adsorption sites, most systems depart from linearity.
Resolution
Resolution is defined as the degree of separation of two chromatographic peaks. By definition, it is the
distance between the peaks centres divided by the average bandwidths which are expressed in the same
units. It can be explained for the two component system based on Figure 19.16.
tR2 − tR1 2 ∆t
Rs = =
w1 + w2 w1 + w2
2

19.24
where w is expressed in the same volume units as v. Where the two peaks are close together,
∆t ∆v
w2 approaches w1 andRs = = .
w2 w2
It is important to note that resolution depends not only on the distance between the peaks, but also
on the narrowness of the peaks. The former is determined by the column which is subject to the nature
of the stationary and mobile phases. The latter is determined by the column efficiency, which, in turn,
is a function of column parameters such as flow rate, particle size, particle diameter and packing of
the column.
Factors Influencing Resolution

Resolution is related to the efficiency, selectivity and capacity factor; hence, control of resolution is
possible by controlling these three fundamental parameters. The influence of the three are illustrated
in Figure 19.16.
A B
A B
(a) (b)
Detector response
A B
(c)
A B
(d)
Time (or) volume
Figure 19.16 Efficiency, selectivity and capacity factor affect the resolution
As shown in Figure 19.16, an increase in efficiency (narrowing of peaks) increases resolution as shown
in (b) in Figure 19.16. An increase in resolution, through the separation of the bands (d) is achieved by
altering column selectivity, so that peak 2 is sorbed to greater extent. In (a), poor resolution is obtained
because of low capacity factor in that neither peak is appreciably sorbed.

Efficiency
Column efficiency is quantitatively expressed by the number of theoretical plates N in the chromato-
graphic bed.
When a solute band passes through the column, several factors will contribute to the broadening
of the zone. The efficiency of the column numerically describes the extent to which the band is broad-
ened and is dependent on a variety of column and kinetic parameters.
tR
Detector response
w = 4s
Time (or) volume
Figure 19.17 Calculation of N
As shown in Figure 19.17, the number of theoretical plates is given by

2 2 (1)
N =  R  = 16  R 
t t

s  w 
where σ is the variance of the peaks in time units, tR is the retention time for the peak and w is the
2
width of the peak at its base in time units. In units of volume equation (1) is
2 2
N = R = R
V V
s   w 
where VR is the retention volume, and w and σ are measured in volume units.
Column efficiency can also be expressed in terms of the plate height, H (HETP) or height equiva-
lent to a theoretical plate. Thus,
L
H=
N
where L is the length of the column bed. Since N is dimensionless L and H must be expressed in the
same units.
Applications
GLC and HPLC are applicable to every applied area of science. It is a routine technique in pharma-
ceutical, biochemical, food and beverage, agricultural, petroleum, environmental polymer, industrial
organic and inorganic and organometallic analysis.
HPLC is identical trace analysis technique. For example, it is useful for the detection of air force
(air pollutants) and water pollutants, pesticide residues in plants and food stuff, impurities in all sorts
of commercial, pharmaceutical and drugs and their metabolites in body fluids.

19.26
Analytical HPLC (Qualitative)

Qualitative analysis in GLC and HPLC is done by comparing retention times or retention volumes of
sample components with retention times or retention volumes of reference compounds. Direct com-
parison of the results obtained with the sample and the results obtained with the standards is generally
not possible as these are developed on different days, under different experimental conditions or by a
different laboratory.
Therefore, the relative retention, specific retention volume or Kovats retention indices are compared.
The Kovats retention index relates the retention of the sample component to the retention of
straight chain saturated hydrocarbons which elute before and after the sample component. The Kovats
retention index is defined in one of the following equivalent ways.
 log(t − tm ) − log(tn − tm ) 
I = 100  + 100 n(1)
 log(tn +1 − tm ) − log(tn − tm ) 
 log(v − vm ) − log(tn − tm ) 
I = 100  + 100 n (2)
 log( vn +1 − vm ) − log(vn − vm ) 
 log a s n  (3)
I = 100   + 100 n
 log a n+1n 
where I = retention time of the sample component.

tm = retention time for mobile phase.
tn = retention time of the saturated hydrocarbon containing n carbons which elutes before the
sample compartment.
Sample size is held constant and the area under the component peak is proportional to the concen-
tration of the component in the sample.
The area under peak can be measured by following any one of the following methods.
(i) Peak height
(ii) Triangulation
(iii) Counting
(iv) Planimeter
(v) Cut and weight
(vi) Disc integration
(vii) Electronic integration

1. and columns are used in GLC.
[Ans.: Packed, open tubular]
2. Carrier gas acts as phase in GLC.
[Ans.: Mobile]

3. In GLC, column packing methods are and

[Ans.: Syringe, valve]
4. is used to defect and measures the sample as they immerse from column.
[Ans.: Detectors]
5. and are first family detectors in GLC.
[Ans.: Thermal conductivity viva, B-ray Aragon ionisation]

1. Carrier gas in gas-liquid chromatography
(a) CO2 (b) CO
(c) CO32− (d) none of these
[Ans.: a]
2. The time required for mobile phase to elute the component from stationary phase is called
(a) Retention volume (b) Retention co-efficient
(c) Both (a) and (b) (d) Retention time
[Ans.: d]
3. High pressure pumps producing pressure in HPLC are
(a) 600–1,000 psi (b) 1,000–1,500 psi
(c) 200–300 psi (d) All of these
[Ans.: a]
4. analytical technique is used to separate the component by using stationary and mobile
phase.
(a) Spectroscopy (b) Chromatography
(c) Electro analytical technique (d) None of these
[Ans.: b]
5. In paper chromatography, the stationary phase is
(a) Solid (b) Gas
(c) Liquid (d) Both (a) and (b)
[Ans.: c]
6. Which of the following acts as an absorbent in chromatography?
(a) Mobile phase (b) Stationary phase
(c) (a) and (b) (d) Stationary phase
[Ans.: b]

1. What is meant by chromatography?
Ans.: It is a valuable analytical tool since it can separate mixture components. It is also useful
technique to obtain qualitative and quantitative information about each component.

19.28
2. Explain the different types of chromatographic techniques.

Ans.: Chromatography is divided into different categories, dependent upon the nature of the
stationary and mobile phase.
1. Gas liquid
2. Gas solid
3. Ion exchange
4. Ion-pair
5. Liquid–liquid
6. Paper
7. Thin-layer
8. Liquid solid
9. Size exclusion
3. Write a note on gas liquid chromatography.
Ans.: Gas-liquid chromatography was first discovered by Martin and Synge in 1914.
Gas liquid chromatography is a stationary phase; the mobile phase is gas.
It is also called vapour phase chromatography.
4. Explain retention time.
Ans.: The time required to sweep the component from stationary phase for mobile phase is
called retention time.
5. Write a note on retention volume.
Ans.: The volume of mobile phase required to elute the sample component from the stationary
phase is called retention volume.
6. Write the factors affecting on separation of component in GLC.
Ans.: Factors affecting separation component in GLC are as follows:
1. Particle size and surface area
2. Carrier gas flow rate
3. Type and amount of stationary phase
4. Column diameter
5. Column temperature
7. Write the sample introduction methods in HPLC.
Ans.: A sample can be introduced by the following methods:
1. Syringe septum method
2. Stop-flow injection
3. Sample valve injection
8. Explain the types of detectors used in HPLC.
Ans.: The types of detectors used in HPLC are as follows:
1. Refractive index
2. Dielectric constant
3. Electrical conductivity
4. Thermal conductivity
5. UV and visible
6. Fluorescence
7. Radio activity
8. Electron capture


Q.1 Explain the instrumentation of gas-liquid chromatography.
Q.2 Write short notes+ on the following:
(a) Partition coefficient
(b) Retention time
(c) Retention volume
(d) Plate theory
Q.3 Write a note on HPLC and the instrumentation of HPLC.
Q.4 Describe the theories of HPLC and its application.

20 SOLID STATE AND
X-RAY DIFFRACTION
20.1 INTRODUCTION
X-ray diff raction on inorganic and organic solids is an increasingly important technique for char-
acterisation, the interpretation of the physical and chemical properties of materials in terms of their
ideal or defective atomic structure and the transfer of the acquired crystal chemical knowledge to the
engineering of solid-state compounds with novel technological properties in qualitative and quantita-
tive analysis.
Determination of crystal structure was started by Max von Laue and was followed by William
Henry Bragg with his son, Lawrence. In 1915, Henry Bragg and Lawrence Bragg were awarded the
Nobel Prize for their work; Lawrence remains the youngest winner ever.
Since the discovery of Bragg-type X-ray diff raction from periodic crystal lattices, this technique
has become the most essential tool in crystallography in different fields, ranging from the identification
of crystalline compounds to get a complete crystal structure.
20.1.1 Crystal Structure

Crystalline solid is a solid in which the constituent structural units are arranged in a defi nite geometri-
cal configuration. A crystal is a three-dimensional natural grating in which the atoms or molecules are
arranged in a defi nite geometrical shape with flat faces and sharp edges.
The identical units present in a crystal are called unit cell and contain the same number of mole-
cules arranged in exactly the same manner. The shape of the unit cell is explained by three axes (a, b, c)
and three angles (a, b,b g ). The dimensions of the unit cells of most crystals are roughly of the same
order of magnitude as the wavelength of the X-ray.
20.2 CRYSTAL SYSTEMS

Crystal systems can probably be imagined unit cells of many different shapes. However, one of the
requirements of a unit cell is that it can be stacked to fill a three-dimensional space; seven unit cell
shapes meet this requirement and are known as the seven crystal systems. Crystals can be classified
into these seven categories. A list of the these systems in the order of increasing symmetry is shown
in Table 20.1.

20.2
Table 20.1 Seven crystal systems and their lattice parameters

Crystal system Relationship among lattice parameters
Triclinic a ≠ b ≠ c; a ≠ b ≠ g ≠ 90°
Monoclinic a ≠ b ≠ c; a = g = 90° ; b ≠ 90°
Orthorhombic a ≠ b ≠ c; a = b = g = 90°
Tetragonal a = b ≠ c; a = b = g = 90°
Hexagonal a = b ≠ c; a = b = 90°, g =120°
Rhombohedral or trigonal a = b = c; a = b = g ≠ 90°
Cubic a = b = c; a = b = g = 90°
20.2.1 Laws of Crystallography

There are three laws of crystallography as follows:
Law of Constancy of Interfacial Angles

Under the same physical condition, the substance of the various crystals possess a constant angle
between the corresponding phases.
Law of Constancy of Symmetry

In the substance, all crystals are the same and have the same symmetry.
Elements of Symmetry or Symmetrical Elements

There are three types of symmetry.
Plane of Symmetry
It is possible to divide the crystal into two equal parts, one being the mirror image of the other by an
imaginary plane. The crystal is said to have a plane of symmetry.
For example, a cubic crystal has two types of symmetry as follows:
(i) Three rectangular planes of symmetry
(ii) Six diagonal planes of symmetry
Axis of Symmetry
The axis of symmetry means a line is imagined around which the crystal may be rotated such that
it appears unchanged parts in its shape during the complete rotation/revolution. For example, if the
crystal having the same appearance n times in one complete rotation, the axis is said to be n fold sym-
metry. If the values of n can be 2, 3, 4 and 6, the symmetry is known as di, tri, tetra and hexagonal
symmetry.

Solid State and X-Ray Diffraction 20.3
Centre of Symmetry
The centre of symmetry of a crystal is such a point that a line is drawn through it. It intersects the
surface of the crystal at equal distances in all directions.
Law of Rational Indices or Rationality of Indices

The indices of any phase of the crystal along the crystallography axis either equal to unit indices or
some simple whole number multiplies of it or parallel to it.
For example, OX, OY, OZ, are three crystallographic axis, ABC = a unit crystal, DEF = another
crystal, O = centre of crystal.
z
F
D A B E
x y
20.3 CRYSTAL DEFECTS

An ideal crystal of a crystalline solid has all unit cells with the same lattice points in the entire crystal.
If the same atoms may not occupy on their position, the crystal shows defects and is known as crystal
defect. The crystal defects can be mainly classified into two types. They are stoichiometric defect and
non-stoichiometric defects.
A B A B
B A B A
A B A B
B A B A
Ideal crystal
20.3.1 Stoichiometric Defect

In this type of crystal, the number of positive ions and negative ions is equal and the crystal is neutral.
These defects are further classified into two types—Schottky defect and Frenkel defect.
Schottky Defect
In this type of defected crystals, positive ions and negative ions may be missed in some places but the
number of missing positive and negative ions are equal. This type of defect is also known as point
defect.
Example: NaCl(sodium chloride) and CsCl (cesium chloride)

20.4
A+ B− A+ B−
B− B− A+
A+ B− A+
B− A+ B− A+
Frenkel Defect
In this type of defect, the hole is created in the crystal lattice when any one of the ion (positive or nega-
tive) occupies an interstitial position between lattice points. Frenkel defect is generally observed in
ionic crystals in which negative and positive ions differ largely in their ionic radii.
A+ B− A+ B−
B− B− A+
A+
A+ B− A+ B−
B− A+ B− A+
20.3.2 Non-stoichiometric Defect

Non-stoichiometric crystals are those in which positive and negative ions are in a different ratio. These
crystals do not obey the law of definite proportions of charges. Hence, there will be excess of either
positive or negative ions in a crystal. However, the crystal will be neutral with the equal number of
positive and negative charges. Non-stoichiometric defects are further divided into metal excess and
metal deficiency defects.
Metal Excess Defects

Metal excess defects may be caused due to loss of negative ions or extra positive ions.
Loss of Negative Ions

If the positive ions are in excess due to missing of negative ions from the lattice, this will be compen-
sated by the presence of extra electron with this the electrical charge is balanced.

A+ B− A+ B−
B− A+ e− A+
A+ B− A+ B−
B− A+ B− A+
Extra Positive Ions

Sometimes, metal excess defect appears due to the presence of extra positive ion in interstitial position
of a lattice. To maintain electrical neutrality, an electron also occupies the interstitial position.
A+ B− A+ B−
A+
B− A+ B− A+
e−
A+ B− A+ B−
B− A+ B− A+
Crystals with metal excess defects act as semiconductors; due to the presence of free electrons in
the interstitial position of crystal. They can easily flow from one place to another and act as n-type
semi-conductors.
Metal Deficiency Defect

Metal deficiency defects may be due to missing of positive ion or extra negative ion.
Missing of Positive Ions

Sometimes, a positive ion is missed from its lattice site and the electrical neutrality is maintained by
acquiring two charges on the nearby metal ion instead of one charge. It is necessary to exhibit the metal
variable valence to show this defect.
A+ B− A+ B−
B− A+ B−
A2+ B− A+ B−
B− A+ B− A+

20.6
Extra Negative Ion

Sometimes, an extra negative ion may occupy the interstitial position and the extra negative charge
is balanced by having an extra positive charge on one of the nearest positive ion. Here also, the metal
must be capable of showing variable valence.
A+ B− A+ B−
B−
B− A2+ B− A+
A+ B− A+ B−
B− A+ B− A+
20.4 X-RAY DIFFRACTION
20.4.1 Introduction
X-radiation is an electromagnetic radiation with a rough wavelength between 0.1Å and 100Å; similar
to inter-atomic distance of a crystal. It allows crystal structures to conveniently diffract X-rays.
X-ray diffraction is used to identify phases by comparison with data from known structures, to
quantify changes of cell parameters orientation, crystallise size and other structural parameters. It is
also used to determine the crystallographic structure—cell parameters, space group and atomic coor-
dinates of known or unknown crystals.
In crystallography, angstroms (Å) are the units, equal to 10-8 cm or 10-10 m. One angstrom is equal
to 0.1 nm.
20.4.2 Principle
When crystalline structures exposed to X-Rays diffraction, it results in an influence structure with
geometrical variations, which correspond in the electromagnetic spectrum with wave length X-rays
having photon energy between 3 and 8 kev.
20.4.3 X-ray Diffraction of Crystals and Bragg’s Equation

In order to decide the chemical composition of various crystal planes or the mode of distribution of
various atoms composing the crystal, X-rays could be used. Bragg pointed out that unlike reflection
of monochromatic light, the reflection of X-ray can takes place only at certain angles which are deter-
mined by the wavelength of X-rays and the distance between the planes in the crystal. He followed the
method of passing a beam of X-rays through a crystal and examining the diffraction spectra produced.
The reason for this suggestion was that X-rays possess the same wavelength as interatomic distances
in a crystal. The inter-planar distance in the crystal and the angle of reflection is known as Bragg’s
equation.
When a beam of X-rays is passed through a crystal, the emergent radiation is allowed to fall on a
photographic plate which was placed a few centimeters away from a crystal. The photograph obtained

consisted of a central spot surrounded by spots from different diffracted beams. These photographic
spots were arranged in a pattern which indicates the symmetry of the crystal. X-ray diffraction of
crystal shown in Figure 20.1.
D F
G I
E
A q q
Plane-l
J K d
B Plane-ll
H
C Plane-lll
Figure 20.1 X-ray Diffraction of crystals
Consider a set of parallel planes of inter-planar placing d having miller indices (h, k, l). Let a beam of
X-rays of wavelength l be directed towards the crystal at an angle q to the atomic planes. The inter-
action between X-rays and electrons of the atoms is visualised as a process of reflection of X-rays by
atomic planes. Let a parallel beam of X-rays DE and GH incident on the plane-I and plane-II reflected
and the reflected beams are EF and HI.
The atomic phases are considered to be transparent; they allow a part of the wavelength of the rays
and reflect the other part, the incident angle q called Bragg angle is equal to the reflected.
There is a plane angle difference between the X-rays reflected from plane-I and adjacent plane-II
in the crystal. The reflected from X-rays EF and HI interfere constructively only when these path dif-
ference is equal to an integrated multiple of the wavelength (l), if d is the inter-planar species, the path
difference is JH and HK.
Derivation of Bragg’s Equation

ABC = parallel planes of crystal
DE, GH = incident rays
EF, HI = reflected rays
EJ = perpendicular line at E point for DE ray
EK = perpendicular line at E point for EF ray
The horizontal lines represent the parallel planes in the crystal situated at distance d. The crystal may
be imagined as a layer containing cells. The reflection of X-rays can take place only at certain angles
determined by the wavelengths of X-rays and the distance between the planes in the crystal. He derived
an expression known as Bragg’s equation which gives a simple relation between the wave length of
X-ray (l), the inter planar distance in the crystal (d) and the angle of reflectionq. A beam of X-rays is
incident on the crystal at angle q.
The DE beam is reflected at point E from the upper surface. The GH beam is reflected at point H
from the second lower surface. Let us draw the perpendiculars EJ and EK to the incident and reflected
beam at the point of incidence respectively. The difference in the path lengths of the waves reflected
from the first two planes is given by JH + HK.
From ∆EJH, JH
sinq =
EH
EH = d

20.8
JH
sin q =
d
JH = d sin q
From ∆EHK,
HK
sin q =
EH
EH = d
HK
sin q =
d
HK = d sin q
JH + HK = 2d sin q
When reflected rays are in same phase, 2d sin q = nl .

This equation is known as Bragg’s equation, where n is an integer; When n = 1, first order reflec-
tion is obtained. When n = 2, 3, second and third order reflection are obtained.
20.4.4 Determination of Crystal Structure with Bragg’s Equation

A beam of X-rays are passed through a crystal X-rays reflected from different layers. Incident and
reflected rays are determined with the help of Bragg’s X-ray spectrometer and also to determine
angle q.
Values are substituted in the equation 2d sinq = nl and the crystal structure is determined.
20.4.5 X-ray Diffraction Methods

Powder Method
The powder method is the most widely used method for crystals with simple structures. The powder
impact consists of many small crystals, which are oriented with possible directions. As a result, X-rays
are scattered from all sets of planes.
The scattered X-rays are detected using on X-ray-sensitive film. Substances to be examined are
finely powdered and kept in the form of a cylinder inside the glass tube. A narrow beam of X-rays are
allowed to fall on the powder. The diffracted X-rays strike a strip of photographic film arranged in the
form of a circular.
In this method, no rotation is necessary, since the powder sample already contains micro crystals
arranged in all possible orientation. Hence, a large number of crystal lattice planes are available with
the correct position for maximum X-rays to be reflected. As a result lighted areas form a lines with
different distances from the incident beam. These distances can be converted into the scattering angles
to be used in the Bragg’s equation for different planes of the crystals.
Single Crystal X-ray Diffraction

Single crystal X-ray diffraction can provide detailed information about the internal lattice of crystalline
substances, including bond length, bond angles, unit cell dimensions; it is a non-destructive analytical
technique.

Principle
This is a constructive interference of monochromatic X-rays and a crystalline sample. The cathode
ray tube generates X-rays; the formed rays are filtered to produce monochromatic radiation, colli-
mated to concentrate and directed towards the sample to produce constructive interference. When
conditions satisfy the Braggs law nl = 2d sinq; that is, the wave length of electromagnetic radiation
to the diffraction angle and the lattice spacing in a crystalline sample, these diffracted X-rays are
then detected, processed and counted. By changing the geometry of the incident rays, the orientation
of the centered crystal and the detectors, all possible diffraction directions of the lattice should be
obtained.
All diffraction methods are based on generation of X-rays in an X-ray tube. These X-rays are detected
at the sample, and the diffracted rays powder and single-crystal diffraction vary in instrumentation.
20.4.6 Instrumentation of X-ray

When X-Rays are passed through the crystal, the light is diffracted and pattern according to the crystal
structure. Regarding electron density map, this pattern can be mapped and analysed; it shows the exact
arrangement of atoms in the crystals.
To get a good result, the crystal should be of small size less than one millimeter, perfect without
cracks and air bubbles. If the crystals are not perfect gives random patterns and other problems also
occurs at the time of end image formation.
Different substances crystallise differently.
(i) Small molecules generally crystallise easily.
(ii) Protein or nucleic acids are much harder to crystallise.
Mounting Crystals
The X-ray beam can be passed through the sample; by rotating capillary (or) a tube which contain
sample crystals are mounted. Crystals required to be positioned within ∼25 micrometers accuracy of
the beam.
Exposing X-rays
Once the crystals are properly mounted, they are exposed to X-ray beams. X-ray sources are synchro-
tron, X-ray generator, etc.
Reflection
When the X-rays pass through the crystals, the beam is reflected in a space behind the crystal; the
reflected pattern can be collected by using regular photographic film and then analysed according to
the relative intensity of the spots. By using a goniometer, the diffraction pattern at different angles is
obtained for 3D pattern, to obtain correct crystal structure.
Electron Density Map

The 3D structure obtained above is the electron density map. With this map, we get the final structure
as given in Figure 20.2.

20.10
Crystal
X-Rays
Diffraction
pattern
Phase
Refinement
Electron
density map
Fitting
Atomic
model
Figure 20.2 Electron density map
20.5 APPLICATION OF X-RAY DIFFRACTION

X-ray powder diffraction is used to detect and analyse unknown crystalline material in geology, envi-
ronmental science, material science, engineering, biology, etc. Some applications are as follows:
To characterise crystalline material.
To identify fine grained material such as clays, mixed layers clays which are difficult to determine
optically.
To determination unit cell dimensions.
To check sample purity in qualitative analysis.
In quantitative analysis of polyphase mixtures
To determine lattice mismatch between film and substrate and to interfering stress and strain.
To determine dislocation density and quality of the film by rocking curve measurement.
To measure super lattice in multilayered epitaxial structure.
To determine the thickness, roughness and density of the film by using glancing inside X-ray reflec-
tivity measurements.
To make textural measurements, such as the orientation of grains, in a ploy crystalline sample.
To undertake in charge density studies
To physically analyse crystalline aggregates such as orientation, texture, crystallite size distribu-
tion, and lattice micro strain effects, etc.

1. X-ray crystallography is used to detect the .
[Ans.: Crystalline structure]

2. X-rays having photon energy are .

[Ans.: 3 to 8 keV]
3. The size of crystal in instrumentation of X-rays is .
[Ans.: 1mm]

1. Units used in crystallography is
(a) Angstrome (b) m/s
(c) Nanometer (d) None of these
[Ans.: a]
2. 1 Å = nm.
(a) 0.01 nm (b) 1 nm
(c) 0.1 nm (d) All the above
[Ans.: c]
3. Wave length of X-rays in between
(a) 0.1 to 100 Å (b) 1 to 200 Å
(c) 0.1 to 0.01 Å (d) No range
[Ans.: a]
4. Bragg equation nl =
(a) 2d sinq (b) 3d sinq
(c) 4d sinq (d) nd sinq
[Ans.: a]
5. The method used to detect simple crystal structures is
(a) Crystal method (b) Solid method
(c) Liquid method (d) Powder method
[Ans.: d]

1. Give a short note on X-ray crystallography.
Ans.: X-ray radiation of electromagnetic radiation wavelength in between 0.1Å to 100Å is used
to detect the structure of crystals.
2. Explain the important tools in X-ray diffraction.
Ans.: It is an important tool used to detect the following:
(a) Structure of the crystals
(b) Quantity change of cell parameter and orientation
(c) Size of the crystallite
(d) Cell parameters, space group, atomic co-ordinates.

20.12
3. Explain the Bragg’s equation.

Ans.: The inter-planar distance in the crystals and the angle of reflection is known as Bragg’s
equation; it is represented by nl = 2d sinq.
4. Give a note on powder method.
Ans.: The powder method is most widely used particularly for crystals with sample structure.
5. Write the source for X-ray diffraction.
Ans.: (a) X-ray beam
(b) Synchrotron
(c) X-ray generator

Q.1 Describe the principle of X-ray diffraction.
Q.2 Give a detailed note on Bragg’s equation for X-ray diffraction.
Q.3 Write a note on powder method and its importance.
Q.4 Give a brief account of single crystal X-ray diffraction.
Q.5 Explain the instrumentation of X-ray diffraction.

21 GREEN CHEMISTRY
Sustainable development meets the needs of present generations

without compromising the possibility of future generation
to attend their needs and aspirations.
21.1 INTRODUCTION
Green chemistry or sustainable chemistry or environmentally benign chemistry is the frontiers of
science with the utilisation of set of principles that attempts to reduce or eliminates the use or gen-
eration of hazardous substances in the design and manufacture of environmentally and economically
sustainable products. The growing attention to sustainable development includes the reduction of envi-
ronmental impact and the effective utilization of renewable resources. It can help to solve large global
problems such as climate change, energy consumption of effective utilization of natural resources,
especially renewable resources.
The terms ‘green chemistry’ and ‘sustainable chemistry’ have been often used in several areas to
introduce the efforts of academics, scientists and industrialists towards the development of new effi-
cient chemical processes accounting for their environmental impact. Green chemistry may be consid-
ered as a modern scientific platform where the common efforts of academia, industry and government
converge to develop a sustainable civilization, and in this context, it is certainly clear that fundamental
chemistry has an important role to play.
Probably one of the most important steps in the evolution of green chemistry is closely related to
U.S. Environmental Protection Agency (USEPA). In the 1980s, a significant change began in the execu-
tion of environmental regulations, and pollution became the priority instead of end-of-pipeline control.
In 1990, the pollution Prevention Act, approved by the American Congress in the United States, initiated
to create a modus operandi for dealing with pollution in an innovative and sustainable way and paved
the way to green chemistry concept. Green chemistry takes advantage for technological advancement
chemical processing to achieve environmental efficiency.
21.2 TWELVE PRINCIPLES OF GREEN CHEMISTRY

Paul Anastas and John Warner of the U.S. Environmental Protection Agency coined the two-letter
word “green chemistry” and formulated 12 principles of green chemistry. They are as follows:

21.2
(i) Waste prevention instead of remediation: Waste prevention is better than treating or cleaning
up after it is formed.
(ii) Atom economy (or) efficiency: Safer synthetic methods should be designed to give a good yield
of the final product.
(iii) Use of less hazardous and toxic chemical synthesis: Synthetic methodologies should be de-
signed to use and generate environmentally benign, which possess little or no toxicity.
(iv) Designing of safer chemicals/products: Chemical products should be designed to preserve ef-
ficacy of function while reducing toxicity.
(v) Innocuous solvents and auxiliaries: The use of auxiliary substances, such as solvent and sepa-
rating agents, should be made unnecessary wherever possible and innocuous when used.
(vi) Design for energy efficiency: Energy requirements of chemical processes should be recognised
for their environmental and economic impacts and should be minimised. Preferably, synthetic
methods should be conducted at ambient temperature and pressure.
(vii) Use of renewable feedstock or raw material: A raw material or feedstock should be renewable,
rather than depleting the environment, whenever used technically, and economically possible.
(viii) Reduce derivatives (or) shorten synthetic routes: Unnecessary derivatization, such as use of
blocking groups, protection/deprotection, temporary modification of physical or chemical pro-
cesses, should be minimised or avoided because such steps require additional reagents and can
also generate waste.
(ix) Catalysis rather than stoichiometric reagents: Catalytic reagents are superior to stoichiometric
reagents.
(x) Design for degradation: Chemical products should be designed to degrade, so that at the end of their
function, they break down into innocuous degradation products and do not remain in the environment.
(xi) Real-time analysis for pollution prevention: Analytical methodologies are required to be fur-
ther developed to allow for real-time, in-process monitoring and control prior to the formation of
pollution.
(xii) Inherently safer processes for accident prevention: Substances, derivatives and products in
chemical process should be chosen to minimise the potential for chemical accidents including
releases, explosions and fires.
21.3 IMPORTANCE OF GREEN SYNTHESIS

Green chemistry addresses many challenges by opening a wide and multifaceted research scope and
allowing the invention of novel reacting chemicals that can maximise the desired products and mini-
mise the waste products, as well as the design of new synthetic schemes that are inherently, environ-
mentally and ecologically benign.
The following are the importance of green synthesis:
(i) This prevents pollution at the molecular level by atom economy.
(ii) It gives innovative scientific solutions to real-world environmental problems.
(iii) It provides alternative synthetic routes for feedstock and starting material.
(iv) Biocatalysis and bioleaching are prominent applications in green chemistry.
(v) Utilisation of carbon dioxide as a green solvent.
(vi) Biosorption is one of the important phenomena based on 12 principles of green chemistry. In bio-
sorption process, number of agricultural materials such as wool, palm kernel husk, apple residues,
banana husk and sawdust are being used to remove toxic metals from waste water.

Green Chemistry 21.3
(vii) Effective utilisation of renewable resources as alternate energy sources such as solar energy,
wind energy, hydro energy, etc.
21.3.1 Methods for Green Synthesis

Over the past decades, green chemistry has convincingly demonstrated how fundamental scientific
methodologies can be devised and applied to protect human health and the environment in an eco-
friendly and economically beneficial manner.
Alternative Synthetic Route for Feedstocks and Starting Materials

Example: Production of dimethyl carbonate (DMC)
Dimethyl carbonate is a versatile and environmentally friendly material for chemical industry.
Due to high oxygen content and blending properties, it is used as a good component of fuel.
Traditional Method
In this method, phosgene (COCl2) and methanol (CH3OH) are used to produce DMC.
COCl2 + 2CH 3 OH → CH 3 OCOOCH 3 + 2HCl
phosgene methanol DMC
Here phosgene (reactant) and hydrochloride acid (by-product) are environmentally harmful.
Greener Method (Alternative Method)

This method makes use of copper chloride, methanol, oxygen and carbon monoxide.
2CuCl + 2CH 3 OH + 1 2 O2 → 2Cu(OCH3 )Cl + H 2 O

2Cu(OCH3 )Cl + CO → 2CuCl + CH 3 OCOOCH 3
DMC
Here copper chloride further comes as a by-product, and usage of CO in this method is cheap and
indirectly decreases the pollution.
Biocatalysis or Bioleaching
Bioleaching is the extraction of specific metals from their ores by using microorganisms such as
bacteria.
Example: Extraction of gold
Traditional Method
Heap leaching method is the traditional method employed for the extraction of gold using cyanide.
Here, cyanide is hazardous to health and environment.
Greener Method
In this method, Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans bacteria are used to
oxidise ferrous and sulphur. The gold will be easily separated from the ore and solution. This method
is much cleaner than the traditional heap leaching method.

21.4
Catalysis
Catalytic methods are superior than stoichiometric methods.
Example: Synthesis of adipic acid
Adipic acid is a monomer for nylon and starting material for cathode.
Traditional Method
In the past, for the production of adipic acid, benzene is used as a starting material. However, it is highly
carcinogenic and causes leukaemia. Afterwards, the starting material became cyclohexanone or a mix-
ture of cyclohexanone and cyclohexanol. In oxidation with nitric acid, it produces toxic fumes of nitric
oxides, which are contributors to the greenhouse effect, acid rain and the destruction of ozone layer.
Greener Method
In this method, cyclohexane is oxidised by 30 per cent of hydrogen peroxide in the presence of a catalyst.
The catalyst used is a salt of the metal wolfram and dissolved in an organic solvent such as aliquot 336.
O OH
HNO3
and/or
Trasitional route
HOOC (CH2)4 COOH
Adipic acid
Na2CuO4, H2O2
KHSO4, Aliqcuat 336
Greener route
Oxidation with H2O2 is very effective and environmentally benign. Scientists improved the reaction
with other metal catalysts such as tungsten and molybdenum. The process also promoted towards
biocatalytic method by using genetically transgenic bacteria like Klebsiella pneumoniae, a non-toxic
strain of E. coli. Dr Karen M. Draths and Professor John W. Frost were awarded the “Presidential
Green Chemistry Challenge Award” in 1998 in the USA for this achievement.
21.3.2 Applications of Green Synthesis

Green synthesis has wide applications in many fields. Few of them are as follows:
(i) Preparation of antibacterial products that are alternative for traditional chlorine or tin containing
antibacterial agents such as bandages, sutures, hospital gowns, acne medication, toothpastes, air
filters, antiviral agents, etc.
(ii) Used for cleaning clothes such as the following:
(a) Tetraamidomacrocyclic ligand (TAML) catalyst activates hydrogen peroxide that inhibits
dye transfer and is good for washing machines which use less water.
(b) Total Impact Programme (TIP) as laundry formulation incorporates neutral pH, detergents,
enzymes, surfactants, oxygen bleach and biodegradable softness.
(c) Dry cleaning with liquid carbon dioxide, which is non-flammable, non-toxic and a renewable
substance.

(d) Use of sodium iminodisuccinate for cleaning clothes, which is a biodegradable and environ-
ment friendly chelating agent.
(i) Used for cleaning water by using the following:
(a) Chlorine disinfection which is toxic to aquatic life but important for preventing diseases.
(b) Polymer technology for manufacture of high molecular weight, water-soluble polymers in
aqueous salt solution.
(ii) Used for industrial cleaning by using simple green, non-toxic, biodegradable surfactants, thereby
replacing traditional organic solvents.
(iii) Use of carbon dioxide blowing agent for polystyrene foam production; polystyrene foam is used
in packing and food transportation.
(iv) The conversion of waste glycerine from biodiesel production to propylene glycol.
(v) Synthesis of nanoparticles of metals. The stabilization of small particles is done by using poly-
mers, ligands, solid matrix and surfactants. The preparation of nanoparticles in green solvent such
as water and other non-toxic solvents is very popular nowadays.
21.4 GREENHOUSE CONCEPTS

A greenhouse is also known as a glasshouse. In the greenhouse, plants are grown in a building or other
complexes. Building of the greenhouse is made up of either glass or plastic material. In a greenhouse,
the incoming UV light is absorbed consequently the temperature of air inside the greenhouse increases
and retained in the building by the roof and wall, and air is warmed near the ground and flowing within
the complex.
21.4.1 Types of Greenhouse

A greenhouse is divided into two types:
(i) Glass greenhouse
(ii) Plastic greenhouse
In both types of greenhouses, the plastics used are polyethylene, polycarbonate or PMMA glass.
Uses of Glasshouse
(i) In a greenhouse, temperature, level of light and shade are maintained.
(ii) In a greenhouse, growth of plants is controlled by controlling temperature and lighting of the house.
(iii) It is also used to improve the qualities of the land and also to improve food production by provid-
ing good environment.
(iv) It is also used for growing flowers, vegetables, fruits and transplantation of specific plants.
(v) In addition to all of these, the greenhouse is also used to produce solar fields which produce steam
for solar-enhanced oil.
21.5 GREENHOUSE GASES AND GREENHOUSE EFFECT

In greenhouse effect, UV radiations from sun of short wavelength are absorbed through a transparent
medium, but IR radiations of longer wavelength are unable to pass back from that medium. As a result,
inside temperature increases. Such effect is called the greenhouse effect. This effect is shown due to
absorption of excess heat by carbon dioxide present in it.

21.6
The greenhouse effect is a natural process that produces a relatively warm environment near the
earth’s surface conducive to life on earth; this is broadly of two types: natural and enhanced green-
house effects.
21.5.1 Natural Greenhouse Effect

The natural greenhouse effect occurs naturally by greenhouse gases present in the earth’s atmosphere;
the main natural greenhouse gases are carbon dioxide, methane, nitrous oxide and water vapour.
21.5.2 Enhanced Greenhouse Effect

The enhanced greenhouse effect occurs by human activities which release greenhouse gases into the
atmosphere. The main anthropogenic or human-induced greenhouse gases are carbon dioxide, nitrous
oxide, hydrofluorocarbons (HFCs), perfluorocarbons (PFCs), methane and sulphur hexafluoride.
The enhanced greenhouse effect is responsible for the increase in global temperature, that is, global
warming.
Sources of greenhouse gases, properties and their impacts are shown in Table 21.1.
Table 21.1 Greenhouse gases their sources, properties and impacts

S. no. Greenhouse Source Sink Emission (%) Atmospheric life
gas time in years
1. Carbon diox- Combustion of fossil Photosynthesis and 60 5–200
ide (CO2) fuels, deforestation, gas ocean surface
flaring, cement produc-
tion, different industrial
activities, etc.
2. Methane Landfills, produc- Reaction with 20 12
(CH4) tion and distribution tropospheric hydroxyl
of natural gas and (OH) and removal by
petroleum, fermenta- soils
tion from digestive
system of livestock,
rice cultivation, natural
wetlands, combustion
of fossil fuels, etc.
3. Nitrous oxide Combustion of fos- Removal by soils 6 114
(N2O) sil fuels, fertilizers, and stratospheric
manure, nylon produc- photolysis
tion, biological sources
in oceans and soils, etc.
4. Hydro- Aerosol, propellants, CFCs and HFCs are 50,000 Depends on the
fluorocarbons refrigeration gases, removed by strato- compound and
(HFCs) foam-blowing agents, spheric photolysis the minimum life
solvents, fire retard- and reaction with span is 2 years
ants, aluminium smelt- tropospheric hydroxyl
ing, semiconductor (OH)
production, etc.

5. Perfluorocar- Aluminium production <1% >10,000

bons (PFCs) and semiconductor
production
6. Sulphur hex- Electrical transmission <1% 3,200
afluoride (SF6) and distribution sys-
tems, circuit breakers,
magnesium produc-
tion, etc.
21.5.3 Greenhouse Gas Effect

Greenhouse gases in the earth’s atmosphere absorb infrared radiation from the ground. This radiation
is re-emitted in all directions and radiated back towards the earth’s surface, thereby leading to the
warming of the earth’s surface. Scientists have been able to determine carbon dioxide concentrations
on earth over time and the temperature variation by using data from ice cores and other sources.
Since middle of 20th century, temperature variations and climate changes have been observed due to
manmade sources of greenhouse gases but not on the basis of the presence of natural greenhouse gases.
During the 21st century, the earth is likely to experience the following greenhouse effects:
(i) Higher maximum temperatures and more hot days
(ii) Higher minimum temperatures and fewer cold days
(iii) More intense precipitation events like rain over many areas
(iv) Melting of polar ice caps resulting in rising sea levels
(v) Unseasonal rains, flowering and shedding of trees
(vi) Unexpected floods and droughts
Suggestions for Combating Global Warming

(i) Reduction of fossil fuel combustion and sourcing new fuel alternatives
(ii) Reducing deforestation, replanting of destroyed forests and afforestation
(iii) Reducing or eliminating the use of HFCs, CFCs, perfluorocarbons, and sulphur hexafluoride
(iv) Carbon dioxide sequestration
Finding alternatives to these greenhouse gases in chemical and industrial processes have led to the
development of a new branch of chemistry called green chemistry.
Example of Greenhouse Effect

(i) Bright sun light warms a car on a cold, clear day by the greenhouse effect
(ii) Global warming
(iii) Increasing atmospheric carbon dioxide level
21.5.4 Requirements for Greenhouse

(i) Greenhouse carbon dioxide: The presence of carbon dioxide in greenhouse is responsible for
absorption of radiations by it. Carbon dioxide in greenhouse is also responsible for enhanced
plant growth.
(ii) Greenhouse heating: Heating is most important in colder climates. For good heating, the heat
lost by solid opaque wall is prevented by providing greenhouse design.

21.8
(iii) Greenhouse ventilation: For a good greenhouse, and for a good plant, proper ventilation is an
important factor. The main aims of ventilation are to regulate the temperature and humidity in a
greenhouse. This also ensures a fresh air supply for photosynthesis and plant respiration. Ventila-
tion in a greenhouse is controlled either automatically via a computer or recirculation fans.
(iv) Green synthesis: Green chemistry is also called sustainable chemistry. Main aim of Green Syn-
thesis is minimize the usage of hazard material and maximizing the efficiency of chemical for the
synthesis of particular product.Green synthesis is identified as development in the following fields:
(a) Use of supercritical carbon dioxide as a solvent called green solvent
(b) Oxidant used as an aqueous hydrogen peroxide
(c) Use of hydrogen in asymmetric synthesis
Green synthesis methods have a good impact on the environment.
In these processes, there is less exposure to pollutants, waste reduction and less energy consump-
tion. In research, green synthesis methods include the use of microwave reactors to minimize energy
needs and use of microfluidic reactors to minimize solvent waste.
Main aim of Green chemistry the design of chemical products and processes that reduce or mini-
mize the hazardous effects to living beings and the environment.
21.6 Carbon Sequestration

Carbon sequestration is the process of carbon capture from burning fossil fuels and the long term stor-
age of CO2 safely before releasing into the atmosphere.
Terrestrial or biologic sequestration is the storage of carbon via agricultural and forestry prac-
tices. Geologic sequestration involves injecting carbon dioxide to deep underground where it stays
permanently.
Carbon dioxide capture and sequestration (CCS) is a set of three step processes that can greatly
reduce CO2 emissions from new and existing coal- and gas-fired power plants and large industrial
sources. The processes are as follows:
(i) Capture of CO2 from power plants or industrial processes.
(ii) Transport of the captured and compressed CO2 commonly through pipeline but can also be trans-
ported by train, truck, ship, etc.
(iii) Underground injection and geologic sequestration of the CO2 into deep underground rock
formations of depleted oil or gas fields, deep coal seams, etc.
21.6.1 Importance of Carbon Sequestration

Carbon dioxide (CO2) capture and sequestration (CCS) can significantly reduce emissions from large
stationary sources of CO2, which include power plants using coal and natural gas, as well as industries
such as ethanol processing plants, natural gas processing plants and cement industries.
Carbon dioxide capture and sequestration play an important role in reducing greenhouse gas emis-
sions dramatically and enabling low-carbon electricity generation from power plants and industries
that burn fossil fuels. With this process, about 80–90% CO2 emission may reduce from the power
plants and is equal to:
(i) Planting more than 62 million trees and waiting at least 10 years for them to grow.
(ii) Avoiding annual electricity-related emissions from more than 300,000 homes.

21.7 WHY CARBON DIOXIDE IS A MAJOR PROBLEM

In pre-industrial age, every million molecules of air contained about 280 molecules of carbon dioxide,
and now, that proportion exceeds 380 molecules per million and it continues to increase. Evidence is
mounting that carbon dioxide’s heat-trapping power has already started to boost average global tem-
peratures. If carbon dioxide levels continue to increase, then further atmospheric warming occurs and
its consequences result in rising of sea levels, agriculture disruptions, stronger storms (e.g., hurricanes)
striking more often, etc.
However, reducing carbon dioxide emission does not have a simple solution. Fossil fuels, which
provide about 85 per cent of the world’s energy, are made of hydrocarbons, and burning them releases
huge quantities of carbon dioxide. Fossil-fuel burning will remain substantial, even renewable energy
sources emerge. In fossil fuels, coal is the worst carbon dioxide emitter per unit of energy produced. A
grand challenge for the 21st century’s engineers will be developing systems for capturing the carbon
dioxide produced by burning fossil fuels and sequestering it safely away from the atmosphere.

1. In 1990, the Pollution Prevention Act was approved by the __________ in the United States.
[Ans.: American congress]
2. __________ of the U.S. Environmental Protection Agency coined the two-letter word “green
chemistry”.
[Ans.: Paul Anastas and John Warner]
3. Waste __________ is better than treating or cleaning up after it is formed.
[Ans.: prevention]
4. A raw material or feedstock should be __________ rather than depleting the environment when-
ever technically and economically possible.
[Ans.: renewable]
5. The __________ occurs by human activities which release greenhouse gases into the atmosphere.
[Ans.: enhanced greenhouse effect]
6. Higher maximum temperatures and more hot days can be observes due to __________.
[Ans.: Greenhouse effect]

1. Who framed 12 principles of green chemistry
(a) Paul Anastas (b) John Warner
(c) PPA (d) Both (a) and (b)
[Ans.: d]

21.10
2. The enhanced greenhouse effect is caused by

(a) N2O (b) SF6
(c) PFCs (d) All of these
[Ans.: d]

1. Define green chemistry.
Ans.: Green chemistry is the frontier of science with the utilization of set of principles that
attempts to reduce or eliminate the use or generation of hazardous substances in the design
and manufacture of environmentally and economically sustainable products.
2. Define biocatalysis or bioleaching, Explain with one example.
Ans.: Bioleaching is the extraction of specific metals from their ores by using microorganisms
such as bacteria.
Example: Extraction of gold
Traditional method: Heap leaching method by using cyanide.
Greener method: Acidithiobacillus ferocious and Acidithiobacillus thiooxidans bacteria are used.
3. Explain greener route for synthesis of adipic acid.
Ans.: In greener route, cyclohexane is oxidized by 30 per cent of hydrogen peroxide in presence
of catalyst.
Na2CuO4, H2O2
HOOC (CH2)4 COOH
KHSO4, Aliqcuat 336 Adipic acid
Greener route

Q.1 Give brief note on Carbon sequestration and its importance.
Q.2 Explain Greenhouse effects and its impacts.
Q.3 Give brief note on types of greenhouses.
Q.4 Discuss the use of solar energy for space heating, water heating and production of electricity.
Q.5 Discuss the use of indirect solar energy for generation of electrical power.
(a) Solar greenhouse
(b) Solar production of electricity
Q.7 Explain the solar desalination process and solar cooking process.
Q.8 Write informative note on wind power with its merits and limitations.
Q.9 Define green chemistry and explain 12 principles of green chemistry.
Q.10 Explain any two greener methods with examples.
Q.11 Give a brief note on greenhouse concept.
Q.12 What is the importance of green synthesis?

lab manual
M01_ENGINEERING-CHEMISTRY-LAB-MANUAL_1181_CH01.indd 1 5/23/2016 5:11:03 PM

Estimation of
1 Magnesium by
EDTA Method
AIM
To estimate the amount of magnesium present in 100 ml of the given solution using approximately 0.01 M
ethylenediamine tetraacetic acid (EDTA) solution.
Principle
The estimation of magnesium is based on complexometric titration. Magnesium ions in ammonia solution
form a wine red colour complex with Eriochrome Black T (EBT) indicator. When the EDTA
solution is added, it reacts with the magnesium ions and releases the free indicator. The colour of the
solution changes from wine red to blue, which indicates the end point of titration.
Mg2+ + EBT → Mg − EBT

(unstable wine red colour complex)
Mg - EBT + EDTA → Mg − EDTA + EBT
(stable blue colour complex)
EDTA metal ion complex is stable at pH = 10.
PROCEDURE
Part A: Preparation of Standard Magnesium Sulphate Solution
Take approximately 0.25 g of magnesium sulphate crystals in a clean and dry weighing bottle. Weigh
the bottle along with the magnesium sulphate crystals accurately up to the fourth decimal place using
the rider in an analytical balance. Then, carefully transfer the chemical substance into a clean 100 ml
standard flask with the help of a glass funnel. After the transfer, weigh the empty bottle accurately. The
difference between these two values gives the weight of magnesium sulphate. Dissolve the magnesium
sulphate crystals in a minimum quantity of distilled water and make it up to the mark. Shake the standard
flask well to obtain uniform concentration and keep aside the solution for further use.

L.4 Engineering Chemistry
Weight Rider Total

S. no. Substance g mg Main Sub weight (g)
1 Weighing bottle + MgSO4 (W1)
2 Empty weighing bottle (W2)
Weight of magnesium sulphate + weighing bottle (W1) = _____ g

Weight of empty weighing bottle (W2) = _____ g
Weight of magnesium sulphate (W) = (W1 − W2) = _____ g
Gram molecular weight (GMW) of MgSO4 ⋅ 7H2O = 246.47
Weight of MgSO 4 1000
Molarity of magnesium sulphate solution (M1) = ×
G.M.W of MgSO 4 100
Part B: Standardisation of EDTA Solution

Clean a burette with tap water and then rinse it with distilled water as well as the EDTA solution.
Then, fill it with the EDTA solution and note down the initial reading. Pipette out 20 ml of the standard
magnesium sulphate solution into a clean conical flask. Add 8 to 10 ml of ammonical buffer solution
and two to three drops of the EBT indicator. The solution turns to wine red colour. Titrate this solution
mixture against the EDTA solution taken in the burette until the colour changes from wine red to blue,
which indicates the end point of titration. Note down the volume of EDTA run down. Repeat the titra-
tion until two consecutive concordant values are obtained. Note down the values in a tabular column.
From the titre values, calculate the strength of EDTA.
Volume of MgSO4 Burette readings (ml) Volume of EDTA

S. no. solution (ml) Initial Final run down (ml)
1
2
3
Pipette solution (MgSO4) Burette solution (EDTA)

Volume of magnesium sulphate (V1) = 20 ml Volume of EDTA (V2) = _____ ml
Molarity of magnesium sulphate (M1) = _____ Molarity of EDTA (M2) = ?
No. of moles of magnesium sulphate (n1) = 1 No. of moles of EDTA (n1) = 1
M1V1 M 2V2
=
n1 n2
M1V1 n2
Molarity of EDTA solution (M2) = ×
n1 V2

Estimation of Magnesium by EDTA Method L.5
Part C: Estimation of Magnesium

Make up to the mark the given unknown magnesium ion solution by adding distilled water and shake
the resulting solution well to get uniform concentration. Fill the burette with the EDTA solution
and note down the initial reading. Pipette out 20 ml of the unknown magnesium sulphate solution
into a clean conical flask. Then, add 8 to 10 ml of ammonical buffer solution and two to three drops
of the EBT indicator. The solution turns to wine red colour. Titrate the solution against the EDTA
solution until the colour changes from wine red to blue, which indicates the end point of titration.
Repeat the titration until two consecutive concordant values are obtained. Calculate the molarity of
the magnesium ion solution and the amount of magnesium present in the whole of the given 100 ml
solution from the titre values.
Volume of unknown MgSO4 Burette readings (ml) Volume of EDTA

1
2
Pipette solution (unknown MgSO4 solution) Burette solution (EDTA)

Molarity of magnesium sulphate (M3) = ? Molarity of EDTA (M4) = M2
M 3V3 M 4V4
=
n3 n4
M 4V4 n3
Molarity of given unknown magnesium sulphate solution (M3) = ×
n4 V3
GMW of magnesium = 24
Amount of magnesium present in 100 ml of given solution
Molarity of MgSO 4 ( M 3 ) × GMW of Mg × V (100)
(W) =
1000
RESULT
Molarity of the magnesium sulphate solution (M1) = _____ M
Molarity of the EDTA solution (M2) = _____ M
Molarity of the unknown magnesium sulphate solution (M3) = _____ M
Amount of magnesium present in 100 ml of the given solution (W) = _____ g
VIVA QUESTIONS
1. What is complexometric titration?
2. What is the role of the EBT indicator?
3. Expand EDTA.

4. Give the structure of EDTA.

5. What is the end point of titration in this experiment?
6. What is the basic principle involved in this experiment?
7. Define molarity.
8. What is the GMW of MgSO4 ⋅ 7H2O?

Estimation of
2 Total Hardness
of Water by
EDTA Method
AIM
To estimate the total hardness present in the given water sample using approximately 0.01 M ethylen-
ediamine tetraacetic acid (EDTA) solution.
PRINCIPLE
The estimation of hardness is based on complexometric titration. These titrations are particularly use-
ful to determination of a mixture of different metal ions in solution. Calcium or magnesium ions present
in the water sample in the presence of ammonical buffer solution form an unstable wine red colour
complex with Eriochrome Black T (EBT) indicator. When the EDTA solution is added, it reacts with
the calcium or magnesium ions present in water to form a stable deep blue colour (M–EDTA) complex
and releases the free indicator.
Ca2+ + EBT → Ca − EBT (unstable wine red colour complex)
Ca − EBT + EDTA → Ca − EDTA + EBT
(stable deep blue colour complex)
(or)
Mg + EBT → Mg − EBT (unstable wine red colour complex)
2+
Mg − EBT + EDTA → Mg − EDTA + EBT

(stable deep blue colour complex)
EDTA metal ion complex is stable at pH = 10.
Part A: Preparation of Standard Magnesium Sulphate Solution
Take approximately 0.25 g of magnesium sulphate crystals in a clean and dry weighing bottle. Weigh
the bottle along with the crystals accurately up to the fourth decimal place using the rider in a simple
balance. Then, transfer the chemical substance into a clean 100 ml standard flask with the help of
a glass funnel. After the transfer, weigh the empty bottle accurately. The difference between these
two values gives the weight of magnesium sulphate. Dissolve the magnesium sulphate crystals in a

minimum quantity of distilled water and make it up to the mark. Shake the standard flask well to obtain
uniform concentration and keep aside the solution for further use.
Weight Rider Total weight

S. no. Substance g mg Main Sub (g)
1 Weighing bottle + MgSO4 (W1)
Weight of magnesium sulphate + weighing bottle (W1) = _____ g

Weight of magnesium sulphate (W) = (W1 − W2) = _____ g
Gram molecular weight (GMW) of MgSO4 ⋅ 7H2O = 246.47
Weight of MgSO 4 1000
Molarity of magnesium sulphate solution (M1) = ×
GMW of MgSO 4 100

Clean a burette with tap water and then rinse it with distilled water as well as the EDTA solution. Then,
fill it with the EDTA solution and note down the initial reading. Pipette out 20 ml of the standard magne-
sium sulphate solution into a clean conical flask. Add 20 ml of distilled water, 5 ml of ammonical buffer
solution and two to three drops of the EBT indicator. The solution turns to wine red colour. Titrate this
solution mixture against the EDTA solution taken in the burette until the colour changes from wine red
to blue. Note down the volume of EDTA run down. Repeat the titration until two consecutive concord-
ant values are obtained. Note down the values in a tabular column. Calculate the strength of EDTA based
on the titre values.

1
2
3
Pipette solution (MgSO4) Burette solution (EDTA)

Molarity of magnesium sulphate (M1) = _____ Molarity of EDTA (M2) = ?
M1V1 M 2V2
=
n1 n2
Molarity of EDTA solution (M2) = M1V1 × n2

n1 V2

Estimation of Total Hardness of Water by EDTA Method L.9
Part C: Estimation of Total Hardness of Given Water Sample

Pipette out 40 ml of hard water into a clean conical flask and add 20 ml of ammonical buffer solution to
maintain the pH as 10. Then, add two to three drops of the EBT indicator and titrate the solution mix-
ture against the EDTA solution taken in the burette. The end point of titration is the change of colour
from wine red to deep blue. Repeat the titration for two consecutive concordant values. Note down the
values in a tabular column. Calculate the molarity of the given hard water and its total hardness from
the titre values.

1
2
3
Pipette solution (hard water) Burette solution (EDTA)

Volume of given water sample (V3) = 40 ml Volume of EDTA (V4) = _____ ml
Molarity of given water sample (M3) = ? Molarity of EDTA (M4) = M2
No. of moles of given water sample (n3) = 1 No. of moles of EDTA (n4) = 1
M 3V3 M 4V4
=
n3 n4
Molarity of given water sample (M3) = M 4V4 × n3

n4 V3
GMW of CaCO3 = 100
Total hardness of given water sample = M3 × GMW of CaCO3 × 100
RESULT
Molarity of the magnesium sulphate solution (M1) = _____ M
Molarity of the given water sample (M3) = _____ M
Total hardness of the given water sample (W) = _____ g
VIVA QUESTIONS
1. What is hardness?
2. Define temporary hardness.
3. In this experiment, which solution maintains the pH?
4. What is the importance of pH balance in this experiment?
5. What are the units of hardness?
6. What does the wine red colour indicate?

7. What is the relation between temporary and permanent hardness?

8. How can you remove temporary hardness?
9. What is buffer?
10. What is the colour of the EBT indicator?

Estimation of
3 Copper by
EDTA Method
AIM
To estimate the amount of copper present in 100 ml of the given solution using approximately 0.01 M
ethylenediamine tetraacetic acid (EDTA) solution.
PRINCIPLE
The estimation is based on complexometric titration. Copper ions in ammonia solution form a blue
colour complex with Fast Sulphon Black-F (FSB-F) indicator. EDTA reacts with the copper ions and
releases the free indicator; hence, the colour of the solution changes from blue to dark green.
Cu2+ + FSB-F → Cu − FSB-F (unstable blue colour complex)
Cu − FSB-F + EDTA → Cu − EDTA + FSB-F
(stable dark green colour complex)
PROCEDURE
Part A: Preparation of Standard Copper Sulphate Solution
Take approximately 0.25 g of copper sulphate crystals in a clean and dry weighing bottle. Weigh the
bottle along with the crystals accurately up to the fourth decimal place by using the rider in a simple
balance. Then, transfer the chemical substance completely into a clean 100 ml standard flask with the
help of a glass funnel. Then, weigh the empty weighing bottle accurately and carefully. The difference
between these two values gives the weight of copper sulphate. Dissolve the copper sulphate crystals in
a minimum quantity of distilled water and then make it up to the mark. Shake the standard flask well
to obtain uniform concentration and keep aside the solution for further use.
Weight Rider Total

1 Weighing bottle + CuSO4 (W1)
M03_ENGINEERING-CHEMISTRY-LAB-MANUAL_4519_XXXX_M03.indd 11 5/23/2016 5:16:39 PM

Weight of copper sulphate + weighing bottle (W1) = _____ g

Weight of copper sulphate (W) = (W1 − W2) = _____ g
Gram molecular weight (GMW) of CuSO4 ⋅ 5H2O = 249.69
Weight of CuSO 4 1000
Molarity of copper sulphate solution (M1) = ×
GMW of CuSO 4 100

Clean a burette initially with tap water and then rinse it with distilled water as well as the EDTA solu-
tion. Then, fill it with the EDTA solution and note down the initial reading. Pipette out 20 ml of the
standard copper sulphate solution into a clean conical flask. Add 20 ml of ammonia solution and two
to three drops of the FSB-F indicator. Titrate this solution mixture against the EDTA solution taken
in the burette. The end point is the change of colour from blue to dark green. Repeat the titration until
two consecutive concordant values are obtained. Note down the titration values in a tabular column
and calculate the strength of EDTA from the titre values.
Volume of CuSO4 Burette readings (ml) Volume of EDTA

1
2
3
Pipette solution (CuSO4) Burette solution (EDTA)

Volume of copper sulphate solution (V1) = 20 ml Volume of EDTA (V2) = _____ ml
Molarity of copper sulphate solution (M1) = _____ Molarity of EDTA (M2) = ?
No. of moles of copper sulphate solution (n1) = 1 No. of moles of EDTA (n1) = 1
M1V1 M 2V2
=
n1 n2
M1V1 n2
Molarity of EDTA solution (M2) = ×
n1 V2
Part C: Estimation of Copper
Make up to the mark the given unknown copper ion solution by adding distilled water. Shake the
resulting solution well to get uniform concentration. Fill the burette with the EDTA solution and note
down the initial reading. Pipette out 20 ml of the unknown copper sulphate solution into a clean conical
flask. Then, add 20 ml of distilled water, 5 ml of liquor ammonia and two to three drops of the FSB-F
indicator. The solution turns to blue colour immediately. Titrate this against the EDTA solution until
the colour changes from blue to dark green, which indicates the end point of titration. Repeat the titra-
tion to get two consecutive concordant values. Calculate the molarity of the copper ion solution and the
amount of copper present in 100 ml of the given solution from the titre values.

Estimation of Copper by EDTA Method L.13
Volume of unknown Burette readings (ml) Volume of EDTA

S. no. CuSO4 solution (ml) Initial Final run down (ml)
1
2
3
Pipette solution (unknown CuSO4 solution) Burette solution (EDTA)

Volume of copper sulphate solution (V3) = 20 ml Volume of EDTA (V4) = _____ ml
Molarity of copper sulphate solution (M3) = _____ Molarity of EDTA (M4) = M2
No. of moles of copper sulphate solution (n3) = 1 No. of moles of EDTA (n4) = 1
M 3V3 M 4V4
=
n3 n4
M 4V4 n3
Molarity of given unknown copper sulphate solution (M3) = ×
n4 V3
GMW of copper = 63.5
Amount of copper present in 100 ml of given solution
Molarity of CuSO 4 (M 3 ) × GMW of Cu ×V (100)
(W) =
1000
RESULT
Molarity of the copper sulphate solution (M1) = _____ M
Molarity of the unknown copper sulphate solution (M3) = _____ M
Amount of copper present in 100 ml of the given solution (W) = _____ g
VIVA QUESTIONS
1. What is the role of the indicator in this experiment?
2. Why does the colour change at the end point?
3. What is GMW?
4. What is the unit of molarity?
5. Why does EDTA act as a good chelating agent?
6. What is the GMW of CuSO4 ⋅ 5H2O?

Estimation of
4 Copper by
Iodometery
Aim
To estimate the amount of copper present in 100 ml of the given solution by using approximately 0.05N
sodium thiosulphate (hypo) solution.
Principle
The estimation is based on iodometric titration. Hypo is standardised by titrating with standard
potassium dichromate solution, which liberates iodine from potassium iodide in an acidic medium.
K 2Cr2O7 + 7H2SO4 + 6KI → 4K 2SO4 + Cr2(SO4)3 + 7H2O + 3I2
Copper sulphate reacts with potassium iodide liberating iodine.
2CuSO4 + 4KI → 2K 2SO4 + 2Cu + 2I2
The liberated iodine is titrated against hypo using starch as the indicator.
2Na2S2O3 + I2 → Na2S4O6 + 2NaI
The starch indicator forms a violet blue colour with iodine. The disappearance of the violet blue colour
and the appearance of a light green colour indicate the end point of titration.
Procedure
Part A: Preparation of Standard Potassium Dichromate Solution
Take approximately 0.245 g of potassium dichromate in a clean and dry weighing bottle. Weigh the
bottle accurately up to the fourth decimal place using the rider in a simple balance. Then, transfer the
substance into a clean 100 ml standard flask with the help of a glass funnel. Then, weigh the empty
bottle accurately. The difference between the two values gives the weight of potassium dichromate.
Dissolve the substance in a minimum quantity of distilled water and make it up to the mark. Shake
thoroughly to obtain uniform concentration and keep aside for further use.
M04_ENGINEERING-CHEMISTRY-LAB-MANUAL_XXXX_CH04.indd 14 5/23/2016 5:18:44 PM

Estimation of Copper by Iodometery L.15
Weight Rider Total

1 Weighing bottle + K2Cr2O7 (W1)
Weight of potassium dichromate + weighting bottle (W1) = _____ g

Weight of potassium dichromate W = (W1 − W2) = _____ g
Gram molecular weight (GMW) of potassium dichromate = 294.16
Gram equivalent weight (GEW) of potassium dichromate = 49
Weight of K 2 Cr2 O7 1000
Normality of potassium dichromate (N1) = ×
GEW of K 2 Cr2 O7 100
Part B: Standardisation of Hypo Solution

Clean a burette initially with tap water and then rinse it with distilled water as well as the hypo solution.
Then, fill it with the hypo solution and note down the initial reading. Pipette out 20 ml of the standard
potassium dichromate solution into a clean conical flask. Add 20 ml of dilute sulphuric acid and 10
ml of 10% potassium iodide solution. The solution turns to a deep brown colour. Titrate this solution
mixture against the hypo solution taken in the burette. When the solution forms a light brown colour,
add 1 ml of 1% starch solution and continue the titration until the colour changes from brown to green.
The end point of titration is the change of colour from violet brown to light green. Repeat the titration
to get two consecutive concordant values. Calculate the normality of hypo from the titre values.
Volume of Burette reading (ml) Volume of

S. no. K2Cr2O7 solution (ml) Initial Final hypo run down (ml)
1
2
3
Pipette solution (K 2Cr2O7) Burette solution (hypo)

Volume of potassium dichromate (V1) = 20 ml Volume of hypo (V2) = _____ ml
Normality of potassium dichromate (N1) = _____ Normality of hypo (N2) = ?
N1V1 = N2V2
N1V1
Normality of hypo solution (N2) = N 2 =
V2
Part C: Estimation of Copper
Make up to the mark the given unknown copper ion solution by adding distilled water. Shake the
resulting solution well to get uniform concentration. Pipette out 20 ml of the made-up copper sulphate

solution into a clean conical flask. Add a few drops of ammonium hydroxide solution to get a blue
colour precipitate, and then add a few drops of acetic acid to dissolve the formed precipitate. Add 10 ml
of 10% potassium iodide solution and titrate against hypo taken in a burette. When the solution turns
to a light brown colour, add 1 ml of 1% starch solution and continue the titration. The end point of titra-
tion is the change in colour from violet blue to dirty white or off-white. Repeat the titration to get two
consecutive concordant values. Calculate the normality of the copper sulphate solution and the amount
of copper present in 100 ml of the given solution from the titre values.
Volume of unknown Burette readings (ml) Volume of

S. no. CuSO4 solution (ml) Initial Final hypo run down (ml)
1
2
3
Pipette solution (unknown CuSO4 solution) Burette solution (hypo)

Volume of copper sulphate solution (V3) = 20 ml Volume of hypo (V4) = _____
Normality of copper sulphate solution (N3) = _____ Normality of hypo (N4) = N2
N3V3 = N4V4
N 4V4
Normality of given unknown copper sulphate solution N 3 =
V3
GMW of copper = 63.5
Normality of CuSO 4 × GMW of Cu ×V
Amount of copper present in 100 ml of given solution (W) =
1000
Result
Normality of the potassium dichromate solution (N1) = _____ N
Normality of the hypo solution (N2) = _____ N
Normality of the copper sulphate solution (N3) = _____ N
Amount of copper present in 100 ml of the given solution (W) = _____ g
Viva questions
1. What is the principle involved in this experiment?
2. What is the indicator used in this experiment?
3. What are the main differences between complexometry and iodometry?
4. What is normality?
6. What is the importance of the addition of sulphuric acid in this experiment?
7. What is the chemical name of hypo?
8. Give the formula of hypo.
9. What is the oxidation state of chromium in potassium dichromate?
10. What is the importance of iodometry?

Estimation of
5 Dissolved Oxygen
in the Given
Water Sample
AIM
To estimate the amount of dissolved oxygen present in the given water sample.
METHOD
Winkler’s method.
PRINCIPLE
The given sample is treated with manganous sulphate followed by alkaline iodide. First, manganous
sulphate reacts with potassium hydroxide resulting in potassium sulphate and manganous hydroxide.
MnSO4 + 2KOH → K 2SO4 + Mn(OH)2↓
Manganous hydroxide thus formed reacts with the dissolved oxygen present in the sample and forms
manganic hydroxide.
2Mn(OH)2 + H2O + (O) → 2Mn (OH)3↓
Manganic hydroxide thus formed reacts with potassium iodide in the presence of concentrated
sulphuric acid; as a result, potassium sulphate and manganous sulphate are formed liberating free
iodine. This liberated iodine is equivalent to the amount of oxygen dissolved in the given water
sample.
2Mn(OH)3 + 2KI + 3H2SO4 → K 2SO4 + 2MnSO4 + 6H2O + I2
The liberated iodine is titrated against 0.025 N sodium thiosulphate (hypo) solution by using 1% starch
solution as the indicator. The disappearance of the blue colour is the end point of titration.

Sample Volume of water Burette reading (ml) Volume of hypo

S. no. temperature ( °C) sample (ml) Initial Final run down (ml)
1
2
3
4
PROCEDURE
1. Clean the reagent bottle with water, rinse it with distilled water and then fill it with the given water
sample.
2. To this bottle, add 1 ml of manganous sulphate and 1 ml of alkaline iodine solution.
3. Close the bottle tightly, shake thoroughly and keep in a dark place for about five minutes to avoid
photochemical reaction.
4. After five minutes, take out the bottle from the dark place and add 1 ml of concentrated sulphuric
acid along the inner side of the bottle.
5. Shake the bottle well until the precipitate is completely dissolved.
6. Take a clean 50 ml burette, and rinse and fill it with 0.025 N sodium thiosulphate solution.
7. Transfer 50 ml of the sample from the reagent bottle into a clean conical flask with the help of a
measuring jar.
8. Then, add one or two drops of 1% starch solution as indicator. The solution turns into a blue colour.
9. Titrate this against the 0.025 N sodium thiosulphate solution until the disappearance of the blue
colour, which is the end point of titration.
10. Repeat the titration until consecutive concordant values are obtained. From the titre values, calcu-
late the dissolved oxygen content in the given samples.
11. Repeat the same experiment by increasing the temperature of the water sample up to 70°C and
calculate the dissolved oxygen content.
The dissolved oxygen content is calculated using the following formula:
K × normality of hypo (0.025) × 0.698 × 1000 × volume of hypo used

Oxygen content =
volume of sample
= _____ CC or ml/L
volume of reagent bottle

where K =
volume of reagent bottle − volume of reagent added
250
= = 1.005
250 − 2
(At normal temperature and pressure, 8 g of oxygen is present in 1 litre of water; 1 mg = 1.43 ml and
1 ml = 0.698 mg.)

Estimation of Dissolved Oxygen in the Given Water Sample L.19
RESULT
Amount of oxygen dissolved in the given sample at room temperature = _____ cc or ml/L.
Amount of oxygen dissolved in the given sample at 70° C = _____ cc or ml/L.
DISCUSSION
Oxygen is one of the most limiting abiotic factors and is essential for living organisms. Living cells
require energy to perform metabolic activities. This energy is liberated or generated by the oxidation
of food stuff within the cells in the presence of oxygen.
The actual quantity of oxygen present in water under the most favourable conditions is much less
than that present in the atmosphere. The amount of oxygen present in the atmosphere is 210 cc or ml/L,
whereas that present in 1 L of water does not exceed 10 cc or ml/L. Hence, dissolved oxygen acts as a
limiting factor in the distribution of aquatic animals because most living organisms require oxygen for
respiration. The oxygen supply in water comes chiefly from the following sources:
1. By diffusion from air
2. From photosynthesis of aquatic plants and phytoplankton
It depends on temperature, salinity, pressure, humidity, pollution etc., which greatly affect the capacity
of water to retain oxygen for organisms. For example, as the temperature of the water increases, its
oxygen-retaining capacity decreases, irrespective of whether it is fresh or marine water. The surface of
water, which is in contact with air, will have greater amount of oxygen when compared to lower parts.
It is evident from the experiment that the amount of oxygen present in the sample at room tempera-
ture (28°C) is greater than that at 70°C. This is because as the temperature increases, the water gets
heated up; its capacity to retain oxygen is reduced and oxygen may be released into the atmosphere.
VIVA QUESTIONS
1. What is the basic principle involved here?
2. Why do you keep the reagent bottle in a dark place?
3. Which kind of water has high dissolved oxygen?
4. What is the difference between oxygen and nascent oxygen?
5. What is the unit of dissolved oxygen?
6. Which indicator is used in this experiment?
7. What are the factors influencing dissolved oxygen capacity in water?
8. What is the effect of temperature on the dissolved oxygen content?

Estimation of
6 Ferrous Iron by
Dichrometry
Aim
To estimate the amount of ferrous iron present in 100 ml of the given solution by using approximately
0.05N potassium dichromate solution.
Principle
The estimation is based on redox titration. Ferrous iron is estimated by dichrometry using diphe-
nylamine indicator. Potassium dichromate oxidises ferrous iron to ferric iron in an acidic medium.
K 2Cr2O7 + 4 H2SO4 → K 2SO4 + Cr2(SO4)3 + 4H2O + 3(O)
[2FeSO4 + H2SO4 + (O) → Fe2 (SO4)3 + (H2O)] × 3
K 2Cr2O7 + 6FeSO4 + 7H2SO4 → K 2SO4 + Cr2(SO4)3 + 3 Fe2 (SO4)3 + 7H2O
The addition of orthophosphoric acid is to reduce the redox potential of the ferrous to ferric iron and
to obtain the sharp change of the end point of titration from a colourless to a permanent violet blue
colour solution.
Procedure
Part A: Preparation of Standard Mohr’s Salt Solution
Take approximately 2 g of crystalline ferrous ammonium sulphate (Mohr’s salt) in a clean and dry
weighing bottle and weigh the substance. Transfer the chemical substance into a clean 100 ml standard
flask with the help of a glass funnel. After transferring the substance, weigh the empty bot-
tle accurately. The difference between the two values gives the weight of Mohr’s salt. First add
5 ml of dilute sulphuric acid to Mohr’s salt to avoid the oxidation of ferrous iron to ferric iron. Then,
dissolve it in a minimum quantity of distilled water and finally make it up to the mark. Shake the
standard flask well to obtain a standard solution of uniform concentration and keep it aside for
further use.

Estimation of Ferrous Iron by Dichrometry L.21
Weight Rider Total weight

S. no. Substance g mg Main Sub (g)
1 Weighing bottle + Mohr’s salt (W1)
Weight of weighing bottle + Mohr’s salt (W1) = _____ g

Weight of Mohr’s salt W = (W1 − W2) = _____ g
Gram equivalent weight (GEW) of Mohr’s salt = 392.13
Gram molecular weight (GMW) of Mohr’s salt = 392.13
,
Weight of Mohr s salt 1000
Normality of Mohr’s salt N1 = , ×
GEW of Mohr s salt 100
Part B: Standardisation of Potassium Dichromate Solution

Clean a burette with tap water and then rinse it with distilled water as well as the potassium dichromate
solution. Fill it with the potassium dichromate solution and note down the initial reading. Pipette out
20 ml of the standard Mohr’s salt solution into a clean conical flask. Add 20 ml of dilute sulphuric acid,
5 ml of phosphoric acid and two to three drops of diphenylamine indicator. Titrate the solution mixture
against the potassium dichromate solution. The end point of titration is the appearance of a permanent
violet blue colour. Repeat the titration until two consecutive concordant values are obtained. Note down
the titration values. Calculate the normality of the potassium dichromate solution from the titre values.
Volume of Mohr’s salt Burette reading (ml) Volume of K2Cr2O7

1
2
3
Pipette solution (Mohr’s salt) Burette solution (K 2Cr2O7)

Volume of Mohr’s salt (V1) = _____ 20ml Volume of K 2Cr2O7 (V2) = _____
Normality of Mohr’s salt (N1) = _____ Normality of K 2Cr2O7 (N2) = ?
N1V1 = N2V2
N1V1
Normality of potassium dichromate N 2 =
V2
Part C: Estimation of Ferrous Iron

The given unknown ferrous iron solution is make up to the mark by adding distilled water and shake
well to get uniform concentration. Pipette out 20 ml of the made-up ferrous iron solution in a clean
conical flask. Add 20 ml of dilute sulphuric acid, 5 ml of orthophosphoric acid and three drops of
diphenylamine indicator. Titrate this solution mixture against the potassium dichromate solution.

The end point of titration is the appearance of a permanent violet blue colour. Repeat the titration until
two consecutive concordant values are obtained. Calculate the normality of the ferrous iron solution
and the amount of ferrous iron present in 100 ml of the given solution from the titre values.
Volume of unknown ferrous Burette reading (ml) Volume of K2Cr2O7

S. no. iron solution (ml) Initial Final run down (ml)
1
2
Pipette solution (unknown ferrous iron solution) Burette solution (K 2Cr2O7)

Volume of ferrous iron solution (V3) = 20ml Volume of K 2Cr2O7 (V4) = _____ ml
Normality of ferrous iron solution (N3) = ? Normality of K 2Cr2O7 (N4) = N2
N3V3 = N4V4
NV
Normality of given unknown ferrous iron solution N 3 = 4 4
V3
GMW of iron = 55.85
Amount of ferrous iron present in 100 ml of given solution
Normality of unknown ferrous iron solution ( N 3 ) × GMW of Fe × V
(W) =
1000
Result
Normality of the Mohr’s salt solution (N1) = _____ N
Normality of the potassium dichromate solution (N2) = _____ N
Normality of the unknown ferrous iron solution (N3) = _____ N
Amount of ferrous iron present in 100 ml of the given solution (W) = _____ g
Viva questions
1. What is the difference between ferrous and ferric iron?
2. What is redox titration?
4. What is Mohr’s salt?
5. What is the oxidation number of chromium in potassium dichromate?
6. Which indicator is used in this experiment?
7. What is the unit of Mohr’s salt concentration?

7 Conductometry
Aim
To determine the strength of a strong acid by titrating against a strong base conductometrically.
Apparatus
Conductivity bridge, conductivity cell, 100 ml beaker, 100 ml standard flask, microburette.
Principle
Conductometric titrations are based on changes in the electrical conductance of a solution. A solution
containing hydrochloric acid dissociates into H+ and Cl− ions, in which H+ ions have greater mobility.
With addition of sodium hydroxide solution, H+ ions are replaced by Na+ ions. This decreases
the conductivity of the solution as Na+ ions possess lesser mobility. At the neutralization point, the
solution contains Na + and Cl− ions and will show minimum conductivity. On further addition of
sodium hydroxide solution, conductivity increases because of the higher mobility of the OH- ions.
H+Cl− + Na+OH− → Na+Cl− + H2O
Procedure
Take standard solutions of 1N sodium hydroxide and 0.1 N hydrochloric acid. Transfer 20 ml of
the given hydrochloric acid solution into a 100 ml beaker and add 20 ml of water. Keep the beaker
in thermostat. Wash the conductivity cell with the conductivity water and rinse with the acid
solution. Keep the cell in an acid-containing beaker and connect to the conductivity bridge.
Measure the conductivity of the solution using a digital conductometer. Add 0.2 ml of the sodium
hydroxide solution into the beaker, stir well and measure the conductivity. Continue the addition
of the solution (0.2 ml each time), stir well and measure the conductivity for every instance.
Repeat the addition until the number of values taken on either side of the point of minimum con-
ductivity is equal. Calculate the corrected conductance by applying volume correction, which is
given by
V + U 
C1 =  C
 V 

where C = observed conductance

C1 = corrected conductance
V = volume of water and acid
U = volume of base
Precautions
1. The conductivity cell should never be kept dry.
2. The electrode must be washed.
S. no. Volume of NaOH (ml) Observed conductance (C) Corrected conductance (C1)
1
2
3
4
5
6
7
Calculations
NaOH HCl
Normality of sodium hydroxide (N1) = _____ Normality of hydrochloric acid (N2) = _____
Volume of sodium hydroxide (V1) = _____ Volume of hydrochloric acid (V2) = _____
N1V1 = N2V2
N1V1
Normality of hydrochloric acid N 2 =
V2
Graph
Corrected conductance
Neutralization point (or)

End point
Volume of sodium
hydroxide (ml)

Conductometry L.25
Result
The strength of hydrochloric acid is determined experimentally and is found to be _____ N.
Viva questions
1. What is conductometric titration?
2. What is the difference between conductometric and volumetric titrations?
3. What is the unit of conductance?
4. What is conductivity?
5. What are the factors influencing conductivity?
6. When we increase the concentration, what will happen to the conductance?
7. How can you identify the end point of titration?
8. HCl + NaOH → _____.
9. Which medium shows high conductance values?
10. What are the advantages and disadvantages of conductometric titration?
11. What is the importance of conductometric titrations?

Redwood
8 Viscometer No. 1
Aim
To determine the kinematic viscosity and absolute viscosity of the given thin sample of oil at various
temperatures and to study the variations of viscosities with temperature using Redwood viscometer
No. 1.
Principle
Viscosity is the property of a liquid by virtue of which it offers resistance to its own flow. The viscosity
of liquids decreases with increasing temperature. The rate at which the viscosity changes with tem-
perature is known as viscosity index.
L −U
VI = × 100
L−H
where VI = viscosity index
U = viscosity at 100°F of the oil under test
L =viscosity at 100°F of the low-viscosity standard oil (Gulf oil) having a VI of 0 and also
having the same viscosity as the oil under test at 210°F
H =viscosity at 100°F of the high-viscosity standard oil (Pennsylvanian oil) having a VI of 100
and also having the same viscosity as the oil under test at 210°F.
Apparatus
Redwood viscometer No. 1, two thermometers (0–100°C), a narrow-necked flask (50 cc), a stop watch.
Description
Oil Cup
It is a silver plated brass cylinder (90 mm in height and 46.5 mm in diameter). The upper end of the
cup is open. The bottom of the cylinder is fitted with an agate jet (with a bore diameter of 1.62 mm
and a length of 10 mm). The jet is opened or closed by a valve rod, which is a small silver-plated brass
ball fixed to a stout wire. The level to which the cylinder is to be filled with oil is indicated by a point-
ing wire fixed on the inner side of the cylinder. The lid of the cup is fitted with a thermometer, which
indicates the temperature of the oil.
M08_ENGINEERING-CHEMISTRY-LAB-MANUAL_XXXX_CH08.indd 26 5/4/2016 11:59:47 AM

Redwood Viscometer No. 1 L.27
Heating Bath
The oil cup is surrounded by a cylindrical copper bath containing water. It is provided with a tap for
water outlet and an electric heating coil is fixed at the bottom. A thermometer fixed in the water jacket
indicates the temperature of the water.
Stirrer
Outside the cylinder, there is a stirrer, carrying blades, for stirring the water in the bath for maintaining
a uniform desired temperature. The stirrer is provided with a cylinder shield at the top to prevent the
water from splashing into the oil cylinder.
Levelling Screws
The entire apparatus rests on the three keys provided at the bottom with levelling screws.
Kohlrausch Flask
It is a specially shaped small-mouth flask for receiving oil from the jet outlet. Its capacity is 50 ml up
to the mark in its neck.
Procedure
1. Clean the cup and make sure the cup and the jet are free from dust.
2. Close the cup with the help of the ball valve. Fill the cup with the given oil sample up to the tip
of the hook gauge.
3. Insert thermometers in the holders, one in the oil cup and the other in the water jacket, and read
the room temperature of the oil.
4. Place the clean standard receiver flask of 50 ml capacity just below the jet. Note down the time
required to fill 50 cc of oil into the flask at room temperature.
5. Start the heating process and wait until the temperature of the bath is raised by 12 to 15°C.
6. Cut off the heating process when the temperature of the bath is raised by 12 to 15°C.
7. Stir the water continuously until the temperature of the water and the oil becomes the same.
8. Lift the ball valve and start the stop watch. Simultaneously, note down the time required to collect
50 cc of oil into the flask. Note down the temperature.
9. Repeat the experiment at various temperatures and tabulate the observed readings.
10. Find the kinematic viscosity and the absolute viscosity as explained in the following section using
the given formulae.
Theory
1. Viscosity is the property of a liquid or fluid by virtue of which it offers resistance to its own flow.
B
Kinematic viscosity of oil = At − centistokes (centipoise)
t
Here, t is the time taken for collecting 50 cc of oil, A and B are viscometer constants. A = 0.26 and
B = 171.5.
2. Absolute viscosity = Kinematic viscosity × density
Density of oil at different temperatures = T - Tr

Here, T = Density of oil at tested temperature

Tr = Density of oil at room temperature
Model graphs
1. Temperature Vs Redwood seconds
(redwood seconds)
Time
x
Temperature
2. Temperature Vs kinematic viscosity
y
Kinematic viscosity
x
Temperature
3. Temperature Vs absolute viscosity
y
Absolute viscosity
x
Temperature
Result
It is observed from the graphs that as the temperature increases, the Redwood seconds, kinematic
viscosity and absolute viscosity decrease.

Viva questions
1. What are the oils used in Redwood viscometer No. 1 and No. 2?
2. What are the differences between Redwood viscometer No. 1 and No. 2?
3. Define viscosity?
4. What are the units of viscosity?
5. What is viscosity index?
6. What is the necessity of using the water bath?
7. How much oil is collected each time?
8. How to regulate the temperature?
9. What is the effect of temperature on the lubricants?
10. What are the differences between absolute viscosity and kinematic viscosity?

Redwood
Viscometer No. 2
Aim
To determine the kinematic viscosity and absolute viscosity of the given thick sample of oil (highly
viscous) at various temperatures and to study the variations of viscosity with temperature by using
Redwood viscometer No. 2.
Principle
Viscosity is the property of a liquid by virtue of which it offers resistance to its own flow. The viscosity
of liquids decreases with increasing temperature. The rate at which the viscosity changes with tem-
perature is known as viscosity index.
L −U
VI = × 100
L−H
where VI = viscosity index
U = viscosity at 100°F of the oil under test
L =viscosity at 100°F of the low-viscosity standard oil (Gulf oil) having a VI of 0 and also
having the same viscosity as the oil under test at 210°F
H =viscosity at 100°F of the high-viscosity standard oil (Pennsylvanian oil) having a VI of 100
and also having the same viscosity as the oil under test at 210°F.
Apparatus
Redwood viscometer No. 2, two thermometers (0–100°C), a narrow-necked flask (50 cc), a stop watch.
Description
Oil Cup
It is a silver plated brass cylinder. The upper end of the cup is open. The bottom of the cylinder
is fitted with an agate jet (with a diameter of 3.8 mm and a length of 15 mm). The jet is opened
or closed by a valve rod, which is a small silver-plated brass ball fixed to a stout wire. The level
to which the cylinder is to be filled with oil is indicated by a pointing wire fixed on the inner side
of the cylinder. The lid of the cup is fitted with a thermometer, which indicates the temperature of
the oil.

Heating Bath
The oil cup is surrounded by a cylindrical copper bath containing water. It is provided with a tap for
water outlet and an electric heating coil is fixed at the bottom. A thermometer fixed in the water jacket
indicates the temperature of the water.
Stirrer
Outside the cylinder, there is a stirrer, carrying blades, for stirring the water in the bath for maintaining
a uniform desired temperature. The stirrer is provided with a cylinder shield at the top to prevent the
water from splashing into the oil cylinder.
Levelling Screws
The entire apparatus rests on the three keys provided at the bottom with levelling screws.
Flask
It is a specially shaped flask for receiving oil from the jet outlet. Its capacity is 50 ml up to the mark
in its neck.
Procedure
1. Clean the cup and make sure the cup and the jet are free from dust.
2. Close the cup with the help of a ball valve. Fill the cup with the given oil sample up to the tip of
the hook gauge.
3. Insert thermometers in the holders, one in the oil cup and the other in the water jacket, and read
the room temperature of the oil.
4. Place the clean standard receiver flask of 50 ml capacity just below the jet. Note down the time
required to fill 50 cc of oil into the flask at room temperature.
5. Start the heating process and wait until the temperature of the bath is raised by 12 to 15°C.
6. Cut off the heating process when the temperature of the bath is raised by 12 to 15°C.
7. Stir the water continuously until the temperature of the water and the oil becomes the same.
8. Lift the ball valve and start the stop watch. Simultaneously, note down the time required to collect
50 cc of oil into the flask. Note down the temperature.
9. Repeat the experiment at various temperatures and tabulate the observed readings.
10. Find the kinematic viscosity and absolute viscosity as explained in the following section using the
given formulae.
Theory
1. Viscosity is the property of a liquid or fluid by virtue of which it offers resistance to its own flow.
B
Kinematic viscosity of oil = At − centistokes (centipoise).
t
Here, t = time taken for collecting 50 cc of oil, A and B are viscometer constants. A = 0.26 and B = 171.5.
2. Absolute viscosity = Kinematic viscosity × density
Density of oil at different temperatures = T - Tr

Here, T = Density of oil at tested temperature

Tr = Density of oil at room temperature
Model graphs
1. Temperature Vs Redwood seconds
y
(redwood seconds)
Time
x
Temperature
2. Temperature Vs kinematic viscosity

y
Kinetic viscosity
x
Temperature
3. Temperature Vs absolute viscosity

y
Absolute viscosity
x
Temperature
Result
It is observed from the graphs that as the temperature increases, the Redwood seconds, kinematic
viscosity and absolute viscosity decrease.

Phase Diagram:
9 Urea Vs
Benzoic Acid
Aim
To construct a phase diagram for a binary system consisting of urea and benzoic acid and find the
eutectic composition and temperature.
Principle
The number of phases that exist together when the system is in equilibrium depend upon the conditions
of temperature and composition. These conditions are determined experimentally and then plotted on
a graph. The diagram so obtained giving the conditions of equilibria between various phases of sub-
stance is called phase diagram.
Eutectic point is where two curves AO and BO meet together. At this point three phases (solid
urea, solid benzoic acid and their liquid solution) co-exist. Eutectic point ‘O’ represents the lowest pos-
sible temperature (70–75°C) at which liquid phase cannot be enriched in either component by freezing
out the other component. The temperature (70–75°C) and composition of the components (50% urea,
50% benzoic acid) corresponding to the eutectic point are called the eutectic temperature and eutectic
composition. According to reduced phase equation eutectic point has no degree of freedom. So it is
invariant.
F′ = C - P + 1 (2 – 3 + 1 = 0)
where F′ = no of degrees of freedom = 0
C = no of components = 2
P = no of phases = 3.
Procedure
Fit a boiling test tube with a two-holed cork, and insert a stirrer and a thermometer into the holes.
Take approximately 4 g of urea in the test tube. Heat this in a dry glycerine bath. The temperature
remains constant for a range of time at the melting point. After complete melting, cool it and note the
temperature at which it solidifies (freezing point). In a similar way, repeat the experiment with vary-
ing compositions of urea and benzoic acid from 0 to 100%. Note the freezing points. Similar way
determine the freezing point of unknown composition. Plot them against the percentage composition.
Calculate the eutectic composition, unknown composition, and temperature from the graph.

Weight of Weight of benzoic Freezing

S. no. urea (g) acid (g) % of urea % of benzoic acid point °C
1 4 0 100 0
2 4 1 80 20
3 4 2 66.6 33.3
4 4 3 57.19 42.85
5 4 4 50 50
6 0 4 0 100
7 1 4 20 80
8 2 4 33.3 66.6
9 3 4 42.85 57.19
10 Unknown x Unknown y
Graph
Eutectic point
Eutectic temperature
A B
Freezing point
Freezing point
Urea: 100% Benzoic acid: 100%

Benzoic acid: 0% Urea: 0%
Eutectic composition
Result
The phase diagram is constructed for urea and benzoic acid.
From the graph
Eutectic temperature = _____ °C.
Eutectic composition = _____% of urea, _____% benzoic acid.
Unknown mixture composition = _____% of urea, _____% of benzoic acid.
Viva questions
1. Define eutectic point.
2. What is the melting point of urea?
3. What is the melting point of benzoic acid?

Phase Diagram: Urea Vs Benzoic Acid L.35
4. What is the necessity of using the glycerine bath?

5. What is the principle involved in the phase rule?
6. How many components are involved in this phase rule experiment?
7. Define freezing point.
8. What is the importance of eutectic mixtures?
9. Give the phase rule equation.
10. Give the phase rule equation for condensed systems.

10 Bomb Calorimeter
Aim
To determine the calorific value of solid and liquid fuels using a bomb calorimeter.
APPARATUS
Bomb calorimeter, Thermometer.
PRINCIPLE
Calorific value of the fuel is the total quantity of heat liberated, when a unit mass (or volume) of
the fuel is burnt completely. Calorific value of solid and liquid fuels can be determine with bomb
calorimeter.
Gross (or) Higher Calorific Value (HCV) of the fuel is the total amount of heat produced, when
unit mass/volume of the fuel has been burnt completely and the products of combustion have been
cooled to room temperature.
Net (or) Lower Calorific Value (LCV) of the fuel is the net heat produced, when unit mass/volume
of the fuel is burnt completely and the products are permitted to escape.
Description of equipment
Bomb calorimeter consists of a strong cylindrical stainless steel bomb in which the combustion of fuel
is made to take place. The bomb has a lid, which can be screwed to the body of bomb so as to make a
perfect gas-tight seal. The lid is provided with two stainless steel electrodes and an oxygen inlet valve.
To one of the electrodes, a small ring is attached. In this ring, a nickel or stainless steel crucible can be
supported. The bomb is placed in a copper calorimeter, which is surrounded by an air-jacket and water
jacket to prevent heat losses due to radiation. The calorimeter is provided with an electrically operated
stirrer and thermometer.
PROCEDURE
Take a known mass (1.0 g) of the given fuel in clean crucible. The crucible then supported over the
ring. A fine magnesium wire, touching the fuel sample, is then stretched across the electrodes. The
bomb lid is tightly screwed and bomb filled with oxygen to 25 atmospheric pressure. The bomb is then
lowered into copper calorimeter, containing a known mass of water. Note down the initial temperature

Bomb Calorimeter L.37
of the water. Connect the electrodes to 6-volt battery. When the sample is burns and heat is liberated,
continue the stirring of water for maintaining uniform temperature and record the maximum tempera-
ture attained.
Calculations
( w + w )(t2 + t1 )
High calorific value of the fuel = cal/g.
x
where w = weight of water
w = water equivalent in g of calorimeter
t2 = Final temperature of water in calorimeter
t1 = Initial temperature of water in calorimeter
x = Weight of the fuel
Low calorific value of the fuel = HCV − Latent heat of water formed.
HCV − 0.09H × 587 cal/g
Mass of H2O from 1 g of fuel = 0.09H
Latent heat of stream = 587 cal/g.
Precautions
1. Oxygen should be filled very slowly in the bomb. Afterwards the pressure of O2 may flow the fuel
in the crucible.
2. The fuse wire should remain in contact with the fuel.
Result
High calorific value of the given fuel = _____ cal/g.
Low calorific value of the given fuel = _____ cal/g.
Viva questions
1. What is the principle of a bomb calorimeter?
2. Which state of fuel calorific value can be determined with bomb calorimeter?
3. What is combustion?
4. What is the formula for calculating high calorific value?
5. Which substances are liberated in combustion?
6. What is the relation between high calorific value and low calorific value?

DETERMINATION
11 OF IRON IN STEEL
Aim
To determine the amount of iron present in steel.
Reagents required
Standard oxalic acid solution (0.1N), potassium permanganate solution (0.1N) and dilute sulphuric acid
(2N).
Principle
The steel sample is dissolved in dilute sulphuric acid, which converts the iron present in it to ferrous
sulphate with the liberation of hydrogen gas.
Fe2+ + H2SO4 → FeSO4 + H2↑
The amount of Fe2+ present in a solution can be determined by titrating against a standard potassium
permanganate solution.
2KMnO4 + 8H2SO4 + 10FeSO4 → K 2SO4 + 2MnSO4 + 5Fe2(SO4) + 8H2O
Procedure
Part A: Standardisation of Potassium Permanganate Solution
Clean a burette initially with tap water and then rinse it with distilled water as well as potassium per-
manganate solution. Then, fill it with the potassium permanganate solution and note down the initial
reading. Pipette out 10 ml of the standard oxalic acid solution into a 250 ml conical flask. Add 10 ml of
dilute sulphuric and heat the solution to about 70°C. Then, titrate this solution slowly against the potas-
sium permanganate solution from the burette until a faint but permanent pink colour persists in the
solution. Repeat the titration until consecutive concordant values are obtained. Note down the values in
a tabular column and calculate the normality of the potassium permanganate solution.
Volume of oxalic Burette readings (ml) Volume of KMnO4

S. no. acid (ml) Initial Final solution (ml)
1 10
2 10

Determination of Iron in Steel L.39
Pipette solution (oxalic acid) Burette solution (KMnO4)

Volume of oxalic acid (V1) = 10 ml Volume of potassium permanganate solution (V2) = _____ ml
Normality of oxalic acid (N1) = 0.1N Normality of potassium permanganate solution (N2) = _____
N1V1 = N2V2
N1V1
Normality of potassium permanganate solution N 2 =
V2
Part B: Determination of Iron in the Steel Sample

Dissolve 1 g of steel completely in 100 ml of dilute sulphuric acid and transfer the solution quanti-
tatively into a 250 ml standard flask. Make up the volume to 250 ml by adding distilled water and
shake the solution thoroughly. Pipette out 25 ml of the solution into a clean conical flask. Add 10 ml of
dilute sulphuric acid and titrate against the potassium permanganate solution taken in the burette. The
appearance of a permanent pink colour is the end point of titration. Repeat the titration until concurrent
readings are obtained.
1 ml of 0.1N potassium permanganate = 5.585 mg of iron.
Volume of steel Burette readings (ml) Volume of KMnO4

S. no. solution (ml) Initial Final solution (ml)
1
2
x × 10 × 5.585 × N2 × 10 × 1000
Percentage of iron in steel sample =
1000 × 1
where 10x = volume of potassium permanganate
N2 = normality of potassium permanganate
Result
Amount of iron present in 250 ml of the solution prepared from 1 g of steel = _____ g.
Viva questions
1. What is the basic principal involved in this experiment.
2. What is the oxidation state of Mn in potassium permanganate.
3. What is the end point in this experiment.
4. In this experiment which substance act as indicator.
5. In this experiment what is the role of H2SO4.

Estimation of
12 Chloride and
Salt in Given
Water Samples
Aim
To estimate the amount of chloride and salt content in the given water samples A and B.
Reagents
0.005N silver nitrate solution and 10% potassium chromate.
Principle
When potassium chromate is added as an indicator to the water sample, it dissolves in water and the
chromate ions give yellow colour to the sample. Sodium chloride is present in the dissolved state in
the given sample of water. When this is titrated against silver nitrate, the silver ions react first with the
chloride ions present in the sample and form silver chloride precipitate and sodium nitrate.
AgNO3 + NaCl → AgCl↓ + NaNO3
When all the chloride ions in the sample are precipitated, the excess silver nitrate present reacts with
potassium chromate and forms a pale red precipitate of silver chromate.
2AgNO3 + K 2CrO4 → Ag2CrO4 + 2KNO3
The appearance of the pale red colour indicates that all chloride ions have been precipitated and indi-
cates the end point of titration. From the titre values, the amount of chloride and salt present in the
sample is calculated.
Procedure
Take a 50 ml burette and wash it with tap water and distilled water and then rinse it with 0.005 N silver
nitrate solution. Fill the burette with the 0.005 N silver nitrate solution and note down the initial reading.
Pipette out 10 ml of the given water sample with a clean 10 ml pipette into a clean and dry conical flask.

Estimation of Chloride and Salt in Given Water Samples L.41
Add two to three drops of potassium chromate as the indicator. The solution in the conical flask turns
to yellow colour. Titrate this solution against the 0.005 N silver nitrate solution taken in the burette.
The appearance of a pale red colour is the end point of titration. Note down the final burette reading.
Repeat the titration until consecutive concordant values are obtained. From the titre values, calculate
the amount of chloride and salt present in the given water sample using the given formulae.
Burette reading (ml)

Volume of Volume of AgNO3
S. no. Sample sample (ml) Initial Final solution (ml)
1 A 10 ml
2 A 10 ml
3 B 10 ml
4 B 10 ml
Calculations
Sample A
Volume of given water sample (V1) = 10 ml Volume of silver nitrate solution (V2) = _____ ml
Normality of given water sample (N1) = ? Normality of silver nitrate solution (N2) = 0.005N
N1V1 = N2V2
Normality of given water sample N = N2V2

1
V1
Amount of chloride present in given sample A
Amount of salt present in given sample A
Sample B
Volume of given water sample (V1) = 10 ml Volume of silver nitrate solution (V2) = _____ ml
Normality of given water sample (N1) = ? Normality of silver nitrate solution (N2) = 0.005N
N1V1 = N2V2
N2V2
Normality of given water sample N1 =
V1
Amount of chloride present in given sample B
Amount of salt present in given sample B

Result
Amount of chloride present in sample A = _____ g/L
Amount of salt present in sample A = _____ g/L
Amount of chloride present in sample B = _____ g/L
Amount of salt present in sample B = _____ g/L.
Discussion
All types of natural water contain various amounts of salts such as potassium, sodium, magnesium,
calcium, sulphates, phosphates, nitrates, and chlorides. Among these salts, sodium chloride occurs in
larger quantities. All these salts are responsible for the salinity of water. Salinity has been defined as the
total amount of dissolved salts in 1L of water and is denoted by ‘S’. Salinity is higher in sea water than
in fresh water. The average salt content of sea water is known to be approximately 35 %, whereas that
of fresh water normally may not exceed 0.5 %. Salt content of various water resources has significance
in understanding better the regulatory mechanism of various aquatic animals.
Sea derives salts from the fresh water. During rain, water percolates into the soil where salts get
dissolved in the water. The excess rain water run down into the rivers and from there it reaches the
sea. The river water is non-salty, whereas the sea water is salty. This is mainly because of the various
animals living in the sea water. These animals require calcium carbonate (CaCO3) to form their
protective covering. As a result, the percentage of calcium carbonate in the sea water becomes reduced,
whereas that of sodium chloride increases. Moreover, the rate of evaporation is also greater in sea
water, which results in the accumulation of salts in it.
Viva Questions
1. What is the colour of chromate ions?
2. What is the chemical reaction between silver nitrate and sodium chloride?
3. Sea water is more salty. Explain the reason.
4. Give the equivalent weight of chloride.
5. What is the end point here?

13 pH METRIC TITRATION
OF ACID vs BASE
AIM
To determine the concentration of a strong acid by a pH-metric titration against a strong base.
pH METRIC TITRATION
The determination of the concentration of acid or a base by titrating against a standard base or acid by
monitoring the pH of the titrated solution is called a pH-metric titration. The solution from burette is
added to the beaker, the concentration of the titrand in the cell varies linear to the volume of the titrant
added. Since the cell potential Ecell, has a logarithmic relationship to the concentration of H+, the plot
of Ecell versus volume of the titrant added is a sigmoid curve. As a pH in the cell is linear to Ecell gets a
similar sigmoid curve for the plot of pH versus volume of the titrant added. The abscissa (volume point)
corresponding to the intersection point on the sigmoid is the end point of the titration.
APPARATUS
pH meter with glass electrode and standard calomel electrode (SCE), pipette, micro burette, beaker.
CHEMICALS/SOLUTIONS
Standard sodium hydroxide (0.1 N), hydroxide acid (0.01 N), potassium hydrogen phthalate 0.10 M (pH
4.02), borax 20.00 M (pH 9.15)
PROCEDURE
Step A: Calibration of the pH Meter
Pour about 40 ml of acid buffer (potassium hydrogen phthalate) in a 100 ml beaker. Immerse the glass
electrode and SCE in the buffer (a combined glass electrode is a combination of a glass electrode and
an Ag/AgCl reference electrode). Gently stir the solution and read the pH of the solution by the pH
meter, if it does not show the pH of potassium hydrogen phthalate (4.02), turn on the calibration knob
till the display shows 4.02. Clean the beaker and pour about 40 ml the basic borax buffer. Gently stir

the solution and read the pH of the solution by the pH meter. If the reading is 9.15 or very close to it,
the pH meter is well calibrated.
Step B: pH Metric Titration (Pilot Titration)
Pipette out 40 ml of the acid in a 100 ml beaker. Fill the burette with the standard NaOH solution.
Immerse the glass electrode and SCE or the combined electrode in the solution. Note the pH value
in the Table against zero volume of the NaOH added. Run 1 ml from the burette into the cell, stir the
contents and read the stable pH and continue to add 1 ml each time, read the corresponding pH up to
observing the variation in pH. Stop further addition of the NaOH if you observe an abrupt change in
pH. Note down the burette readings between which the pH has abruptly changed.
Precautions
(i) Do not disturb the calibration knob of the pH meter once it is calibrated.
(ii) Stir the contents in the beaker gently.
S. no. Volume of NaOH (ml) pH Measured

1
2
3
4
Calculations and Graph

(i) Plot pH on y-axis and volume of NaOH on x-axis. A Sigmoid graph as shown below is derived.
(ii) Read the end point from the graph and calculate the concentration of the acid by V1N1 = V2N2.
pH
Volume of NaOH (ml)

PROCEDURE FOR
14 SYSTEMATIC
QUALITATIVE
ANALYSIS
OF ORGANIC
SUBSTANCES
Experiment Observation Inference

Physical property
I. 1. Colour Light brown or red Phenol or aniline
Dark brown May be amine
Pale yellow Nitro benzene
2. State Solid May be benzoic acid, salicylic
acid, glucose, fructose etc.
Liquid May be ethanoic acid, propanone,
phenol, aniline, benzaldehyde,
formaldehyde etc.
3. Odour (a) Phenolic odour Phenol
(b) Pungent odour Aliphatic aldehyde or aliphatic
carboxylic acid
(c) Bitter almond smell Benzaldehyde
(d) Sweet smell Ketone
(e)
Fishy odour or ammonical Amine
smell
II. Nature of compound by ignition test (combustion test)
A little quantity of the substance (a) Burns with a sooty flame May be an aromatic compound
is ignited on a nickel spatula (b) Burns with a non-sooty flame May be an aliphatic compound
(Continued)


Physical property
III. Physical constant Boiling Point /Melting Point
IV. Solubility
1. Water and Litmus Test (a) Soluble and the solution turns May be an acidic compound (phe-
blue litmus to red litmus nol or Carboxylic acid)
(b) Soluble and the solution turns May be aliphatic amine/ Basic com
red litmus to blue litmus pounds
(c) Soluble but neutral May be aliphatic aldehyde, ketone,
amide or carbohydrate
2.
Saturated aqueous sodium Soluble with effervescence and May be carboxylic acid
bicarbonate solution regenerated by the addition of
dilute hydrochloric acid
3.
Dilute sodium hydroxide Soluble and regenerated by the Acidic compound (phenol or car-
solution addition of dilute hydrochloric acid boxylic acid)
4. Dilute hydrochloric acid Soluble and regenerated by the addi- May be amine
tion of sodium hydroxide solution
5. Ether Insoluble May be carbohydrate or amide
V. Action of heat Substance changes into a black May be carbohydrate
mass
VI. Detection of nitrogen/halogens/sulphur by Lassaigne’s test:
Preparation of sodium fusion extract:
Dry a small piece of sodium metal between the folds of a filter paper. Take it in a dry ignition tube and heat
till the metal melts. Add a few crystals or one or two drops of the given organic substance and heat the tube
slowly until it becomes red hot. Drop the hot ignition tube along with the contents into 5ml of distilled
water present in a mortar. Grind the tube with a pestle and filter the solution. The filtrate so obtained is
called the sodium fusion extract, which is used for the determination of elements present in a compound.
1. Take a small quantity of the Prussian blue coloured solution or Nitrogen is present.
sodium fusion extract in a precipitate is formed.
test tube. To this, add ferrous
sulphate crystals or ferrous
ammonium sulphate crystals
and heat up to boiling. Then,
add one drop of concentrated
sulphuric acid.
2. Take a small quantity of the White precipitate is formed and eas- Presence of chlorine.
sodium fusion extract in a test ily soluble in ammonium hydroxide.
tube. Add dilute HNO3, heat White precipitate is formed and Presence of bromine.
to half of its volume and then soluble in excess amount of
add aqueous silver nitrate. ammonium hydroxide.
White precipitate is formed and Presence of iodine.
insoluble in ammonium hydroxide.

Procedure for Systematic Qualitative Analysis of Organic Substances L.47

Physical property
3. Take a small quantity of the Pink or violet colour solution Presence of sulphur.
sodium fusion extract in a test appears.
tube. Add sodium nitro prus-
side solution.
VII. Tests for functional groups:
1. Azo dye test: Red azo is formed. May be amine.
Dissolve the compound in
dilute hydrochloric acid and
add a saturated solution of
sodium nitrite and cool. In
another test tube, dissolve
b-naphthol in sodium hydrox-
ide solution and cool. Mix the
two solutions.
2. Action with 30% hot aqueous Ammonium gas is evolved. May be amide.
sodium hydroxide solution:
Take the substance in a test
tube, add sodium hydroxide
and heat the test tube in a
water bath.
Test with Borsche’s reagent Yellow or orange coloured pre- May be ketone or aldehyde.
3.
(Brady’s reagent): cipitate is formed.
Add 2ml of the Borsche’s rea-
gent to about four drops of
the compound and heat the
test tube in a water bath. Add
concentrated HCl.
4. Test with Schiff’s reagent: (a) Pink colour is restored. Aldehyde
Add Schiff’s reagent to the (b) Pink colour is not restored. ketone
organic compound.
5. Test with neutral ferric chlo- Violet, green or blue-coloured May be phenol.
ride solution: solution is formed.
Add two drops of neutral fer-
ric chloride solution to the
aqueous solution of the com-
pound
6.
Test with saturated sodium Soluble with effervescence with May be carboxylic acid.
bicarbonate: the liberation of carbon dioxide,
Add saturated bicarbonate which changes lime water milky,
solution to the compound puts off burning candle.
taken in a test tube.
(Continued)


Physical property
7. Test with dilute hydrochloric Soluble and regenerated with the May be amine.
acid: addition of dilute sodium hydrox-
Add dilute hydrochloric acid ide solution.
to the substance taken in a
test tube.
8. Molisch’s test: A violet or red ring is formed at May be a carbohydrate.
Dissolve very small amount the junction of the two layers.
of the substance in distilled
water taken in a test tube. Add
two drops of a solution of
a-naphthol in alcohol to the
side of the test tube.
VIII. Additional tests (confirmatory tests for functional group):
1. Primary amines:
(a) Carbylamine reaction: Add Offensive odour of isocyanide is Primary amine is confirmed.
alcoholic potassium hydrox- observed.
ide and chloroform to the
compound and heat.
(b) Bromination: Dissolve the White or pale yellow precipitate is Primary amine is confirmed.
substance in water or alco- formed.
hol and add bromine water
drop by drop until pale yel-
low colour persists.
(c) Reaction with nitric acid: Yellow oil drops appear. Secondary amine is confirmed.
Dissolve the compound in
dilute HCl and then add
cooled sodium nitrate.
If Yellow oil drops are not
appeared. The solution is
divided into two parts.
Test with b Napthol in NaOH Red azo dye is formed. Primary amine is confirmed.
solution:
Test with NaOH solution: Grass green precipitate is formed. Tertiary amine is confirmed.
2. Amides:
(a) Hydrolysis with 10% aque- Carboxylic acid is generated. Amide is confirmed.
ous sodium hydroxide solu-
tion: Reflux 1 gm of the sub-
stance with 10 ml of 10%
sodium hydroxide solution
until no more ammonia is
evolved. Cool and acidify
with concentrated hydro-
chloric acid.


Physical property
3. Aldehydes or ketones:
(a) Test with Fehling’s solution: (a)

Red precipitate of cuprous Aldehyde is confirmed.
Add a few drops of the com- oxide is obtained.
pound to 2 ml of Fehling’s (b) Cuprous oxide is not formed. Ketone is confirmed.
solution A and B, and heat in
a water bath.
Test with Tollen’s reagent: (a) Silver mirror or black precipi- Aldehyde is confirmed.
(b)
Add a few drops of the given tate of silver is formed.
compound to 20 ml of Tol- (b) No silver mirror is formed. Ketone is confirmed.
len’s reagent, and heat in a
water bath.
(Preparation of Tollen’s
reagent: Add two drops of
sodium hydroxide solu-
tion to silver nitrate solu-
tion. Then add ammonium
hydroxide solution drop by
drop with shaking until the
formation of a brown pre-
cipitate.)
4. Phenols:
(a) Test with sodium metal: Add Hydrogen gas is evolved. It shows the presence of the
a dry piece of sodium metal hydroxyl group.
to the given compound in a
dry test tube.
(b) Diazo coupling reaction Scarlet red coloured azo dye is Phenol is present.
(Azo dye test): Dissolve the formed.
given compound in sodium
hydroxide solution. In
another test tube, dissolve
aniline in dilute hydrochlo-
ric acid and add 0.5 g of
sodium nitrite and cool. Mix
the two solutions.
(c) Bromination: Dissolve the White or pale yellow precipitate is Phenolis confirmed.
compound in water or alco- formed.
hol. To this, add bromine
water until pale yellow col-
our persists.
(Continued)


Physical property
5. Carboxylic acids:
(a) Esterification test: To one Fruity smell is observed due to the Carboxylic acid is confirmed.
part of the given compound, formation of ester.
add two parts of alcohol and
one part of concentrated sul-
phuric acid. Heat and pour
the contents into a beaker
containing excess of sodium
carbonate solution.
(b) Phenolphthalein test: Add one The pink colour of the solution Carboxylic acid is confirmed.
drop of phenolphthalein to a disappears.
very dilute solution of sodium
hydroxide. To this pink col-
oured solution, add aqueous
or alcoholic solution of the
compound drop by drop.
6. Carbohydrates:
(a) Action of concentrated sul- Chars with the smell of burnt Carbohydrate is confirmed.
phuric acid: Add concen- sugar.
trated sulphuric acid to the
substance.
(b) Test with Fehling’s solution: Red cuprous oxide is formed. It is a reducing sugar.
Add Fehling’s solution to
the aqueous solution of the
compound and heat the test
tube in water bath.
(c) Test with Tollen’s reagent: Silver mirror is formed. It is a reducing a sugar.
Add Tollen’s reagent to the
aqueous solution of the com-
pound, and heat the test tube
in a water bath.
IX. Report: Aliphatic/aromatic
X. Preparation of derivatives:
1. Primary amine:
(a) Acetyl derivative: Mix 1ml of the amine with 3ml of water in a test tube and shake well to get an emul-
sion. To this, add 1ml of acetic anhydride and shake the mixture well again. Separate the crystalline
acetyl derivative obtained by filtration.
(b) Bromo derivative: Add bromine water to the amine drop by drop and shake well until the colour of the
bromine water persists. Separate the white or pale yellow precipitate formed by filtration.
2. Amides:
Acid by hydrolysis: Take 1g of the amide in a boiling test tube. To this, add 15ml of 10% sodium hydroxide
and heat in a water bath until no more ammonia is evolved. Cool and acidify with concentrated hydrochlo-
ric acid. Then, carboxylic acid is formed.


Physical property
3. Aldehydes and ketones:
(a) Phenylhydrozone: Dissolve 1g phenyl hydrazine hydrochloride in excess of strong solution of sodium acetate
in a test tube. Dissolve the carbonyl compound in water or alcohol in another test tube. Mix the two solutions
and heat on a water bath. Separate the white or yellow precipitate of phenylhydrazone obtained by filtration.
(b) 2.4-Dinitrophenylhydrazone: Add Borsche’s reagent to the aldehyde or ketone and boil for about three
minutes. Dilute it with water until turbidity or precipitate appears and warm again until a clear solution
is formed. Separate the yellow crystals of dinitro phenyl hydrazone obtained on cooling by filtration.
4. Phenols:
(a) Benzoate derivative: Dissolve the phenol in excess of 10% sodium hydroxide solution in a boiling test
tube. To this, add 2ml of benzoyl chloride drop by drop, with constant shaking. Cork the mouth of the
test tube and shake vigorously for 10 minutes and cool. Pour the formed oily product into plenty of water.
Rub the walls of the beaker with a glass rod to induce crystallisation and separate the solid by filtration.
(b) Bromo derivative: Dissolve the phenol in water or alcohol and then add bromine water with shaking.
Filter the formed precipitate.
5. Carboxylic acids:
(a) Ester formation: Take carboxylic acid, alcohol and sulphuric acid in a boiling test tube in 1:2:1 ratio.
Heat the contents and pour into a beaker containing sodium carbonate solution. Extract the ester with
ether and then evaporate the solvent.
(b) Anilide: Mix a small quantity of carboxylic acid with a few drops of thionyl chloride and reflux for
20 minutes using air condenser. Acid chloride is formed. Then, add 1 ml of aniline and shake well.
Separate the white crystalline anilide compound formed.
6. Carbohydrates:
Osazone: Mix the sugar, phenyl hydrazine hydrochloride, sodium acetate crystals and distilled water in a
test tube. Heat on a water bath for 10 minutes and cool. Filter the formed osazone.
Report:
Name of the Compound:
Structural formula of the Compound:
Name of the prepared derivative:
SOME PRACTICAL EQUATIONS WITH DETAILED EXPLANATION

Solubility
Water
Phenol and formaldehyde can soluble in water due to formation hydrogen bonds.
Sodium hydroxide (NaOH)
Organic acids which are insoluble in water normally dissolved in NaOH solution due to the formation
of respective conjugate base.
HCl
C6 H 5 OH + NaOH → C6 H 5 ONa + H 2 O 
→ C6 H 5 OH + NaCl
Phenol Sodium phenate
HCl
CH 3COOH + NaOH → CH 3COONa + H 2 O 
→ CH 3COOH + NaCl
Acetic acid Sodium acetate
HCl
C6 H 5 COOH + NaOH → C6 H 5 COONa + H 2 O 
→ C6 H 5 COOH + NaCl
Benzoic acid Sodium benzoate

Dilute hydrochloric acid (HCl)
C6H5NH2 + HCl→ C6H5N+H3Cl− NaOH

→ C6H5NH2 + NaCl + H2O
Aniline Aniline hydrochloride (or) Anilinium chloride
Sodium bicarbonate (NaHCO3)
C6 H 5 COOH 
Benzoic acid  C6 H 5 COONa  C6 H 5 COOH 
  Conc HCl 
(or)  + NaHCO 3 → (or) +H
 2 O + CO 2 ↑   → (or)  + NaCl
CH 3COOH  CH 3COONa  CH 3COOH 
Sodium bi
Acetic acid 
 Carbonate
With dilute HCl, acetic acid does not regenerate.

Lassaigne’s test
Preparation of sodium fusion extract
(i)
NH2
+ Na NaCN

(ii) Na + C + N → NaCN
(iii) 2Na + S → Na2S
(iv) Na + X → NaX (Where X = Cl, Br, I)
N, S, Cl, Br are bonded with organic substances by covalent bonds; in the preparation of sodium fusion
extract covalent bonds are converted into ionic bonds. Covalent bond is less reactive than ionic.
Test for nitrogen

6NaCN + FeSO4(s) → Na4[Fe(CN) 6] + Na2SO4
In the presence of H2SO4. ferrous sulphate is converted into ferric sulphate.
3Na4[Fe(CN) 6] + 2Fe2(SO4)3→ Fe4[Fe(CN) 6] + 6Na2SO4
Ferric ferro cyanide complex (Prussian blue colour)
6NaCN + Fe(NH 4 )2SO 4 → Na 4 [Fe(NH 4 )2 (CN)6 ]+ Na 2SO 4
3Na 4 [Fe(NH 4 )2 (CN)6 ]+ 4Fe+3 → Fe 4 [Fe(NH 4 )2 (CN)6 ]3 + Na 2SO 4

Halogen
NaX + AgNO3 → AgX↓ + NaNO3
Sulphur
Na2S + Na2[Fe(CN)5(NO)] → Na4[Fe(CN)5NOS]
Sodium Sulpho Nitro Prusside

Esterification
CH3COOH + HOC2H5 ConH

 2SO 4
→ CH3COOC2H5 + H2O
Acetic acid Ethanol Ethyl acetate
C6H5COOH + HOC2H5 H→ C6H5COOC2H5 + H2O

+
Benzoic acid Ethanol Ethyl benzoate
Borsche’s reagent
2, 4 Dinitro phenyl hydrazine (or) 2, 4 DNP
H2C (O + H2)N NH H2C N NH
NO2 NO2
NO2 NO2
2,4 DNP Formaldehyde
phenyl hydrazone
H C O H2N NH
NO2
+ CH N NH
H NO2
Benzaldehyde NO2
NO2
Benzal 2,4 DNP
hydrazone
(CH3)2C O + H 2N NH (CH3)2 C N NH
NO2 NO2
NO2 NO2
Acetone 2,4 DNP
Tollen’s reagent
Ammonical solution of silver nitrate is known as Tollen’s reagent.
+
R—CHO + 2 Ag(NH3)2OH → RCOO− N H4 + 2Ag ↓ + H2O + 3NH3
Tollen’s reagent Silver mirror
R—CHO + Ag2O → RCOOH + 2Ag↓

Fehling’s solution
Fehling’s solution is a blue coloured alkaline solution of cupric ion complexed with sodium potassium
tartrate ions.
R—CHO + 2 Cu (OH) 2 + NaOH→ RCOONa + Cu2O ↓ + 3H2O
Blue colour Red
R—CHO + 2CuO → RCOOH + Cu 2O ↓
Red
Benzaldehyde reduces only Tollen’s reagent.
Schiff’s reagent
A diluted solution of rosaniline hydrochloride,
COOH
H C OH (Na or K)
H C OH (Na or K)
Phenols azodye test

NaNO2 + HCl→NaCl + HNO2
C6H5NH2 + HCl→ C6H5NH2 ⋅ HCl
Aniline hydrochloride
(or)
+ H HO +
C6H5 N H + N C6H5 N N + 2H2O N N OH + NaCl
Phenol
H O NaOH
Cl− Cl−
Benzene diazonium p-hydroxy azobenzene
chloride (red dye)
Bromination
OH OH
Br Br
+ 3Br2 (aq) + 3HBr
Br
2,4,6 tribromophenol
white ppt
Amines
Carbylamine reaction
C6H5NH2 + CHCl3 + 3KOH → C6H5NC + 3KCl + 3H2O
Phenyl iso cyanide

Diazotisation
NaNO2 + HCl→ HNO2 + NaCl
C6H5 NH2 + HCl→ C6H5NH2⋅HCl
+ H HO +
C6H5 N H + N C6H5 N N + 2H2O
H O
Cl− Cl−
Benzene diazonium
chloride
OH
+ NaOH
α–naphthol
OH
N N
+ HCl
Azobenzene (red dye)
Amides
O
Urea or carbamide H2N C NH2 10% NaOH
O
Aqueous NaOH
∆ HCl
H2N C NH2 2NH3 + CO2 HCOOH + NaCl
H O H Formic acid
Derivatives
Amines
Bromo derivative
NH2 NH2
Br Br
+ Br2(water) + 3HBr
Aniline
Br
2,4,6 tribromoaniline

Acetyl derivative
NH2 O NH C CH3
C CH3
H2O
+ O + CH3COOH
C CH3
O
Acetic anhydride Acetanilide
Molisch’s test
Glucose CH2—OH—(CHOH)4—CHO
CHO
H C OH
HO CH CH OH Conc H2SO4 CH CH
HO C H
−3H2O
H C C H C C
H C OH
HOH2C OH HO CHO H2C O CHO
H C OH OH
5-hydroxy methyl furfural
CH2OH
Reduction of Fehling solution
CHO COOH
∆
(CHOH)4 + 2CuO (CHOH)4 + Cu2O
Red ppt
CH2OH CH2OH
Gluconic acid
Reduction of Tollen’s reagent
CHO COOH
∆
(CHOH)4 + Ag2O (CHOH)4 + 2Ag
CH2OH CH2OH

2,4 dinitro phenyl hydrazine
CHO CH N NH C6H5(NO2)2
CHOH C N NH C6H5(NO2)2
+ 3H2N⋅NH C6H5(NO2)2
(CHOH)3 2,N, D.N.P (CHOH)3
CH2OH NO2 CH2OH

or
CH N NH NO2 Glucose 2,4 DNP
or
NO2 Glucosazone
C N NH NO2
(CHOH)3
CH2OH
Phenols derivatives
Benzoate derivative
OH Cl C O O C O
+ −HCl
Benzoyl chloride Phenyl benzoate
Reaction with benzyl chloride is known as schottan Baumann reaction.

Carboxylic acids
Anilide derivative
O
CH3COOH + SOCl2 CH3 C Cl + SO2 + HCl

O H O
CH3 C Cl + H2N C6H5 C6H5 N COCH3 + HCl

Acetanilide
C6H5COOH + SOCl2 C6H5COCl + SO2 + HCl
Benzoyl chloride
O
C6H5COCl + C6H5NH2 C6H5 NH C C6H5 + HCl

Benzanilide
CH O H2 N NH C6H5 CH N NH C6H5 CH N NH C6H5
CHOH CHO(H + NH2)NH C6H5 C O + C6H5NH2 + NH3

+
(CHOH)3 (CHOH)3 (CHOH)3
CH2OH CH2OH CH2OH

Glucose phenylhydrazone
Phenylhydrazone
of Glucose
CH N NH C6H5
C N.NH C6H5
(CHOH)3
Glucosazone
CH2OH

INDEX
A Applications of
Adsorption 10.16
Absolute zero 11.18
Carbon nanotubes 7.48
Absorption of oxygen 6.7
Colloids 10.28
Achiral molecule 16.7
Composites 2.44
Acid-Base titrations 5.42
Coordination compounds 14.22
Addition reaction 15.18
Electrochemical series 5.27
Addition/Vinyl/Chain polymerisation 2.9
Eutectic system 8.15
Adiabatic process or adiabatic change 11.30
Green synthesis 21.4
Adsorption is 10.1
Ion selective electrodes 5.37
Exothermic 10.2
IR spectroscopy 17.23
Isotherms 10.5
Liquid crystals 7.58
Advantages of
Magnetic materials 7.6
Batteries 5.51
Nanomaterials 7.51
Composites over conventional materials 2.44
Semiconductors 7.3
Glass electrode 5.40
TGA 18.3
Alkalinity of water 1.18
b -ray argon ionisation detection 19.8
Alternative energy 4.2
Argon ionisation detectors 19.9
Ampule method 19.7
Assumptions for the validation of phase rule 8.6
Analysis of
Atomic and molecular orbital 15.20
Cement 7.16
Auxochrome 17.6
Coal 3.8
Axis of symmetry (Cn ) 16.5
Glucose in blood 5.45
Urea 5.45
Anionic addition polymerisation 2.14 B
Annealing 8.21 Basic principle 17.15
Anodic Basic requirements to formation of coordination
Coatings 6.23 compound 14.1
Inhibitors 6.28 Batteries 5.51
Antiferromagnetic materials 7.6 Beer-Lambert law 9.3
Application of Benzynes 15.14
Filled plastics (Reinforced plastics) 2.34 Bergius method 3.23
First law of thermodynamics 11.11 BET adsorption isotherm 10.10
X-Ray diffraction 20.10 Binary explosives 7.38
Applications 19.25 Biochemical resolution 16.9
Z01_ENGINEERING-CHE00_SE_1181_Index.indd 1 5/17/2016 7:20:10 PM

I.2 Index
Biogas 3.30 Good fuel 3.7

Biomass 4.12 Good refractory materials 7.17
Biopolymers 2.35 Liquid crystal phase 7.52
Bipropellants 7.44 Chemical
Blasting fuses 7.40 Composition of portland cement and its
Boiler corrosion 1.36 importance 7.12
Boilers and boiler troubles 1.32 Properties of liquid crystals 7.57
Boiling method 1.27 Resolution 16.9
Bomb calorimeter 3.3 Chemical shift 17.26
Bond polarisation 15.5 Chirality 16.6
Boron molecule 15.24 Chiral molecule 16.6
Boundary or thin film lubrication 7.23 Chlorination method 1.27
Break-point chlorination 1.31 Chlorophyll 12.8
Broad classification of nanomaterials 7.45 Chromatography
Bucky ball cluster 7.46 Theory 19.10
Bulk elements 12.2 Timeline 19.1
Chromophores 17.6
C Classification based on
Calorific value 3.2 Attractive forces 19.2
Carbanions 15.12 Chemical composition 2.3
Carbenes 15.13 Composition 2.2
Carbocations or Carbonium ions 15.10 Mobile phase 19.2
Carbon Mode of polymerisation 2.4
Molecule 15.25 Source 2.2
Monoxide molecule 15.29 Structure 2.3
Nanotubes 7.47 Tacticity 2.4
Sequestration 21.8 The molecular forces 2.4
Carnot’s engine efficiency 11.14 Classification of
Carrier gas 19.3 Adsorption 10.3
Catalytic cracking 3.22 Cement 7.7
Cathodic Chromatography 19.2
Coatings 6.23 Colloids 10.18
Protection 6.21 Composites 2.42
Catholic inhibitor 6.28 Explosives 7.37
Cationic addition polymerisation 2.12 Fuels 3.1
Causes of corrosion 6.1 Liquid crystals 7.52
Caustic embrittlement 1.38 Lubricants 7.24
Cement 7.6 Magnetic materials 7.4
Centre of symmetry 16.6 Polymers 2.2
Chain or nuclear isomerism 16.2 Refractories 7.18
Change Stereoisomerism 16.3
In entropy for irreversible process 11.26 Structural isomerism 16.1
Of entropy of the universe 11.27 Propellants 7.43
Characterisation 7.45 Clausius–Clapeyron equation 11.38
Characteristics of Closed system 11.2
A good propellant 7.42 Coagulation or flocculation or precipitation 10.25

Index I.3
Coal 3.8 Derivation of
Coal gas 3.30 Bragg’s equation 20.7
Coefficient of performance of a refrigerator 11.31 The Stefan–Boltzmann law using Maxwell’s
Colligative properties 10.21 equations 11.40
Colloidal state 10.17 Desalination 1.51
Column Descriptive questions 1.65, 2.51, 5.78, 6.38, 7.82,
And packing materials 19.4 8.34, 9.11, 12.14, 13.16, 14.28, 15.38, 16.19, 17.41,
Packing materials 19.15 18.6, 19.29, 20.12, 21.10
Parameters 19.16 Determination of complex ion formation 14.19
Preparation 19.6 Detectors 19.7
Components (C) 8.2 Determination of
Composites 2.42 Acidity in water 1.17
Composition 2.34 Calorific value 3.3
Compounding of rubber 2.28 Chlorides in water 1.16
Concentration cell 5.40 Crystal structure with Bragg’s equation 20.8
Corrosion 6.10 Hardness 1.8
Detonators/Primary explosives/Initiating
Condensation polymerisation or step
explosives 7.37
polymerisation 2.5
Diamagnetic materials 7.4
Conductance behaviour of
Diesel engine, cetane and octane number 3.26
Strong electrolyte 5.10
Difference between adsorption and absorption 10.2
Weak electrolyte 5.10
Differential thermal analysis 18.4
Conducting
Directive of mobile phase flow 19.20
Polyaniline 2.39
Disadvantages of
Polymers 2.37
Batteries 5.51
Conductometric titrations 5.15
Hard water 1.23
Configurational isomers 16.10 Displacement pumps 19.17
Conformational isomers 16.10 Dissolved oxygen (DO) 1.15
Constituents of composites 2.42 Distribution coefficient or partition
Construction of glass electrode 5.38 coefficient (K) 19.10
Conventional or traditional energy resources 4.1 Dry or chemical corrosion 6.2
Coordination polymerisation 2.15 Dry process 7.9
Cracking 3.21 dsp2 hybridisation 15.5
Crystal Dynamites 7.38
Defects 20.3
Field theory 14.11 E
Structure 20.1
Edta method 1.8
Systems 20.1
Effective atomic number 13.11
Cyclic voltammetry 5.49
Electrical
Properties 10.22
Resistance and conductance 5.4
D Electrochemical
Degree of Cells 5.21
Freedom 8.4 Circuit and working of ISE 5.34
Polymerisation 2.1 Sensors 5.44
Freedom 17.22 Series 5.26
Demineralization process/Ion exchange process 1.47 Theory of corrosion 6.5

I.4 Index
Electrode Separation 19.13
Concentration cells 5.40 The adsorption of gases by solids 10.4
Potential 5.23 The intensity of absorption of radiation 17.11
Electrodialysis 1.53 The position of spectra (l max) 17.10
Electro less plating 6.26 The position of the K maximum and intensity
Electrolysis 5.1 of radiation 17.10
Electrolyte-concentration cells 5.41 The stability of coordination compounds 14.17
Electrolytic conduction 5.4 Vibrational frequency 17.22
Electromeric effect 15.7 Failures of refractory materials 7.18
Electron displacement in covalent bonds 15.5 Faraday’s
Electronic transitions 17.5 First law of electrolysis 5.3
Electro-osmosis 10.24 Second law of electrolysis 5.3
Electrophoresis or cataphoresis 10.24 Favorable conditions for stress corrosion 6.14
Electroplating 6.26 Ferric Fe3+/Fe2+ System 5.47
Elements of symmetry or symmetrical Ferrimagnetic materials 7.5
elements 20.2
Ferromagnetic materials 7.5
Elimination reaction 15.18
Fill in the blanks 1.54, 2.44, 5.60, 6.29, 7.61, 9.9,
EMF
10.31, 13.15, 14.23, 15.33, 16.15, 17.36, 18.5,
Measurement 5.25
19.26, 20.10, 21.9
Or cell potential of a cell 5.24 First
Engler’s viscometer 7.33 Family detectors 19.8
Enhanced greenhouse effect 21.6 Law of thermodynamics 11.10
Entropy 11.23 Fischer–Trapsch method 3.23
Entropy disorder 11.25 Fisher projections 16.13
Entropy–temperature diagram 11.28 Five basic rules of molecular orbital theory 15.22
Equivalent conductivity 5.6 Flame ionisation detector 19.9
Essential elements 12.1 Flow
Eutectic
Control and programming system 19.18
Mixture and Eutectic point 8.5
Rate 19.4
System 8.14
Flue gas analysis by orsats apparatus 3.31
Evolution of hydrogen 6.6
Fluorescence 9.4
Examples of adsorption, absorption,
Fluorine molecule 15.28
and sorption 10.3
Franck–Condon principle 17.11
Explosives and propellants 7.36
Free
External treatment 1.40
Radical polymerisation 2.9
Extreme pressure lubrication 7.24
Radicals 15.9
Extrinsically conducting polymers 2.40
Extrinsic semiconductors (semiconductors Freeze–drying 8.15
due to impurity defects) 7.2 Freezing mixture 8.17
E–Z Nomenclature 16.12 Freundlich adsorption isotherm 10.5
Fuel cells 5.57
Fullerenes 7.46
F Functional group isomerism 16.2
Factors affecting corrosion 6.17 Fundamental steps for constructing molecular
Electrolytic conduction 5.4 orbitals 15.21

Index I.5
G Important
Artificial rubbers 2.29
Galvanic
Biodegradable polymers 2.35
Corrosion or bimetallic corrosion 6.8
Conditions for hybridisation 15.2
Series 6.16
Galvanizing 6.24 Explosives and their preparation 7.40
Gas electrode 5.30 Functions of lubricants 7.22
Gaseous fuels 3.28 Metals in biological systems 12.4
Gas-Liquid-Chromatography 19.3 Petroleum products and their uses 3.20
General properties of magnetic materials 7.4 Photochemical reactions 9.7
Geometrical isomerism 16.3 Points on molecular orbital diagrams 15.21
Geothermal energy 4.10 Polymers—Composition, preparation,
Gibb’s free energy or Gibb’s function (G) 11.36 properties and engineering uses 2.19
Glass electrode 5.38 Impressed current cathodic protection 6.22
Greases or semi-solid lubricants 7.25 Indicator diagram 11.6
Greenhouse Inductive effect 15.5
Concepts 21.5 Inorganic and organometallic photochemistry 9.8
Gas effect 21.7 Instrumental design 17.3
Gases and greenhouse effect 21.5 Instrumentation 19.3, 17.16, 19.15, 17.25
Grotthuss–Draper law or the first law of of X-ray 20.9
photochemistry 9.2 Intensive and extensive properties 11.3
Gutta–Percha 2.26 Internal
Conversion 9.3
H Energy or Intrinsic energy 11.6
Haemoglobin 12.4 Energy (U) 11.33
Hardness is expressed in terms of CaCO3 1.4 Treatment 1.39
Hard water and hardness 1.3 Inter-system crossing 9.4
Heat treatment of steel 8.21 Intrinsically conducting polymer (ICP) or conjugated
Helium molecule 15.23 p -electrons conducting polymer 2.37
Helmholtz function (F) 11.35 Intrinsic semiconductors (semiconductors due to
High thermal defects) 7.2
Explosives 7.38 Introduction 1.1, 5.1, 6.1, 8.1, 20.6, 2.1, 3.1, 4.1, 9.1,
Performance liquid chromatography 19.14 10.1, 11.1, 12.1, 13.1, 14.1, 15.1, 17.1, 18.1, 19.1,
Resolution 17.30 20.1, 21.1
Hot dipping 6.24 Ion selective electrodes 5.34
Hybridisation 15.1 Irreversible process 11.4
Hydrogen molecule 15.23 Isoelectric point 10.26
Hyperconjugation 15.9 Isolated system 11.2
Isomerism 16.1
I Isothermal process or isothermal change 11.5
Importance 7.45 Isotherms 19.22
Importance of
Biopolymers in sustainable development 2.36
Carbon sequestration 21.8 J
Green synthesis 21.2 Jablonski diagram 9.3
Second law 11.13 Joule–Kelvin effect for perfect gas or ideal gas 11.45

I.6 Index
Joule– Power alcohol 3.25

Kelvin effect for van der Waals’ gas 11.46 Material selection 6.19
Thomson Effect or Joule–Kelvin effect 11.44 Measurement of
Junker’s calorimeter 3.4 Electrode potential 5.23
Electrolytic conductance 5.8
K Mechanical properties 10.21
Mechanism of
Kasha’s rule 17.11
Adsorption 10.2
Knocking 3.26
Electrochemical corrosion 6.6
Kohlrausch’s law of independent migration
Mechanism of lubrication 7.23
of ions 5.11
Membrane technology method 1.31
Meso compounds 16.8
L Metal-amalgam electrode 5.29
Langmuir adsorption isotherm 10.7 Metal
Laws of Carbonyls 13.10
Crystallography 20.2 Cladding 6.25
Electrolysis 5.2 Deficiency defect 20.5
Photochemistry 9.2 Excess defects 20.4
Lead (Pb) – Silver (Ag) system 8.18 Metallurgical coke 3.16
Ligand 13.11 Metal-metal
Light source in photochemistry 9.1 Insoluble salt electrode 5.29
Lime soda process 1.40 Ion electrode 5.28
Limitations of phase rule 8.8 Metals and their toxicity 12.9
Linear Metamerism 16.2
Combination of atomic orbitals and type Method of application of metal coatings 6.24
of atomic orbitals 15.22 Methods for green synthesis 21.3
Sweep voltammetry (LSV) 5.46 Micro elements (Trace elements) 12.2
Liquid Molar conductivity 5.7
Crystals 7.51 Molecular energy level diagrams of
Fuels 3.18 Hetero molecules 15.29
Propellants 7.43 Homo molecules 15.23
Long answer questions 10.39 Molecular
Lubricants 7.22 Isomerism 16.14
Lyotropic liquid crystals 7.57 Mass of a polymer 2.17
Orbital energy level diagrams 15.23
Orbital theory 15.19
M Orbital theory of coordination complexes 14.16
Macrominerals 12.2 Representation 16.12
Magnetic Symmetry and chirality 16.5
Materials 7.4 Vibrations 17.17
Resonance 17.30 Molecule containing an asymmetric carbon 16.7
Resonance imaging 17.29 Monopropellants 7.43
Major feed stocks for biopolymers 2.35 Mounting crystals 20.9
Manufacture of Multiple-choice questions 7.64, 1.56, 2.45, 5.62,
High-alumina bricks, magnesite bricks 7.21 6.31, 8.24, 9.10, 10.33, 12.12, 13.15, 15.34, 16.16,
Metallurgical coke 3.17 17.37, 18.5, 19.27, 20.11, 21.9, 14.25
Portland cement 7.8 Myoglobin 12.6

Index I.7
N P
Nanomaterials 7.44 Paints 6.26
Natural Paramagnetic materials 7.4
Cement 7.7 Petroleum refining 3.18
Gas 3.28 Phase
Greenhouse effect 21.6 Diagrams 8.9
Nature of polymers used 2.34 Rule 8.6
Nernst equation for electrode potential 5.28 Phase (P) 8.1
Newman representation 16.14 Phosphorescence 9.4
Nitrenes or Imidogens 15.13 Photochemical process 9.4
Nitric oxide Photodynamic therapy 9.6
Ion (NO −) 15.32 Photophysical
(NO) molecule 15.31 And chemical processes 9.3
Nitrogen molecule 15.26 Process 9.3
NMR applications 17.32 Photosensitisation 9.6
Nomenclature of metal complexes 14.3
Photovoltaic cell 9.9
Non-conventional energy
Physical properties 10.21
Resources or renewable energy sources 4.1
Pilling Bedworth rule 6.4
Sources and storage devices 4.2
Pitting corrosion 6.12
Non-essential elements 12.4
Plaster of Paris/Gypsum plaster 7.16
Non-stoichiometric defect 20.4
Plastic explosive 7.38
n-type semiconductors ( n stands for negative) 7.2
Plastics 2.18
Nuclear
Plate theory 19.12
Energy 4.13
Polyphosphazenes/Phosphonitrilic polymers 2.40
Fission 4.16
Portland cement 7.7
Fusion 4.21
Magnetic resonance spectroscopy 17.24 Position isomerism 16.2
Reactions 4.15 Positive and negative adsorptions 10.3
Numerical problems based on Carnot’s cycle 11.19 Potentiometric
Sensor 5.44
O Titrations 5.42
Powder method 20.8
One component system 8.9
Power alcohol 3.24
Open system 11.2
Optical Precautions
Activity 16.4 During storage of explosives 7.39
Isomerism 16.4 Titrations 5.44
properties 10.22 Preparation methods 2.35
Organic surface coatings 6.26 Preparation of
Organolithium compounds 13.2 Carbonyls 13.11
Organomagnesium compounds 13.5 Organolithium compounds 13.2
Organometallic chemistry timeline 13.1 Organomagnesium compounds 13.5
Oxidation Primary
Corrosion 6.2 Batteries 5.52
Reduction titrations 5.43 Photochemical process 9.4
Oxygen molecule 15.27 Priming, carry over and foaming 1.35
Ozonolysis method 1.30 Principle 17.2, 17.24, 20.6

I.8 Index
Principle of Requirements for greenhouse 21.7

DTA 18.4 Resolution 19.12
TGA 18.2 Resolution of racemic mixture 16.9
Processing of natural rubber 2.25 Resonance or mesomeric effect 15.8
Producer gas (or) Suction gas 3.29 Retention
Propellents or low explosives 7.37 Time 19.10
Proper designing 6.19 Time and volume 19.20
Properties of Volume 19.11
Carbonyls 13.12 Reverse osmosis (RO) (Hyper filteration) 1.52
Colloidal solutions 10.21 Reversible and irreversible process 11.3
Enantiomers and diastereomers 16.8 Reversible process 11.3
Lubricants 7.27 Review questions 1.54, 5.60, 6.29, 7.61, 12.11, 2.44,
Nanomaterials 7.49 3.32, 4.23, 8.22, 9.9, 10.31, 13.15, 14.23, 15.33,
Organolithium compounds 13.3 16.15, 17.36, 18.5, 19.26, 20.10, 21.9
Organomagnesium compounds 13.7 Ring or chain isomerism 16.2
Refractories 7.18 Rocket propellants 7.41
Protection from corrosion (preventive measures Rotational–Reflection axis of symmetry (Sn) 16.6
for corrosion control) 6.19 R–S nomenclature or CIP nomenclature 16.10
Protective action of lyophilic colloids 10.26 Rubber (Elastomers) 2.25
Proximate analysis of coal 3.8
p-type semiconductor ( p stands for positive) 7.2 S
Pumping systems 19.17 Sacrificial anodic protection
Puzzolana cement 7.7 (Galvanic protection) 6.21
Safety plugs or safety fuse 8.16
Q Salient features of hybridisation 15.1
Quality of water for domestic use 1.24 Sample 19.6
Quantum yield and quantum efficiency 9.6 Sample introduction 19.16
Quinhydrone electrode 5.33 Sawhorse representation 16.13
Saybolt viscometer 7.33
R Scale and sludge formation 1.33
Secondary
Racemic mixture 16.9
Batteries 5.55
Racemisation 16.9
Photochemical process 9.5
Raw materials used in the manufacture of portland
Second
cement 7.7 Family detectors 19.9
Reaction intermediates 15.9 Law of thermodynamics 11.13
Rearrangement reaction 15.19 Semiconducting and super
Reciprocating pumps 19.17 conducting materials 7.1
Redox electrode 5.30 Semiconductor 7.1
Redwood viscometer 7.31 Setting and hardening of cement 7.13
Reference electrode 5.31 Short answer questions 1.61, 2.49, 5.66, 6.35, 7.76,
Refractive index detector 19.19 9.10, 10.37, 12.13, 13.16, 14.27, 15.36, 16.18,
Refractories 7.17 17.39, 18.6, 19.27, 20.11, 21.10
Reinforced or filled plastics 2.33 Sidgwick’s electronic concept theory 14.8
Relationship between the efficiency (n) of a Carnot Single
heat engine and the efficient of performance (K) Compounds explosives 7.38
of a refrigerator 11.32 Crystal x-ray diffraction 20.8

Index I.9
Slag cement 7.7 Synthesis of

Softening of water 1.38 Carbon nanotubes 7.48
Solar energy 4.2 Nanomaterials 7.44
Solders 8.16 Synthetic
Solid Petrol 3.21
Fuels 3.8 Rubbers or artificial rubber 2.29
Lubricants 7.26 Syringe method 19.6
Propellants 7.43
Solved numerical problems 5.71, 8.32
Solved numerical problems based on T
Alkalinity of water 1.20 Tautomerism 16.3
Combustion of fuel 3.10 Tempering 8.21
EDTA method 1.12 Theories of coordination chemistry 14.7
Entropy 11.33 Theory of high performance liquid
Hardness of water 1.6 chromatography 19.19
Isothermal and adiabatic process 11.21 Thermal
IR spectra 17.22 Conductivity detector 19.8
Proton NMR 17.33 Cracking 3.21
UV-Vis Spectroscopy 17.12 Thermodynamic
Some important terms about explosives 7.36 Derivation of the phase rule 8.6
Sources of water 1.1 Potential 11.33
sp2 hybridisation 15.2 Potentials and maxwell equations 11.33
sp3 d 2 hybridisation 15.4 Processes 11.4
sp3 d hybridisation 15.4 Terms and basic concepts 11.1
sp3 hybridisation 15.3 Thermogravimetric analysis 18.1
Space or stereoisomerism 16.1 Thermoplastics 2.19
Specific, equivalent and molar conductivities 5.5 Thermosetting plastics 2.22
Spectroscopy 17.14 Thermotropic liquid crystals 7.52
sp Hybridisation 15.2 Thick film, fluid film or hydrodynamic
Spin-spin splitting, spin-spin interaction, lubrication 7.23
spin–spin coupling or fine spectrum 17.28 Tinning 6.25
Stability of Total heat function (H) 11.34
Colloidal sols 10.22 Toxicity of
Coordination compounds 14.20 Arsenic 12.9
Standard calomel electrode (SCE) 5.31 Lead 12.10
Stark-Einstein law or photochemical equivalence Mercury 12.11
law 9.2 Tralancated 7.47
Stationary liquid phase 19.5 Treatment of water for domestic use 1.24
Stereochemical terms 16.7 Triple point 8.6
Stoichiometric defect 20.3 True and metastable equilibrium 8.5
Stokes’ shift 17.11 Twelve principles of green chemistry 21.1
Stress corrosion 6.13 Two component system 8.14
Structural isomerism 16.1 Types of
Structure of carbonyls 13.12 Chromatography 19.3
Substitution reaction 15.17 Corrosion 6.2
Superconductors 7.3 Electrochemical corrosion 6.8
Surface coatings 6.23 Electrodes 5.28

I.10 Index
Fullerenes 7.46 Voltammetry 5.45
hardness 1.4 Vulcanisation of rubber 2.27
Hybridisation 15.2
impurities present in water 1.2 W
Ion – Selective membranes 5.35
Water
Polymerization 2.5
Gas (or) Blue gas 3.29
Solid support 19.4
line corrosion 6.11
Solution 10.17
Power 4.10
Stress corrosion 6.14
System 8.10
Thermodynamic systems 11.2
Wedge and dash projections 16.12
Werner’s theory 14.7
U Wet or electrochemical corrosion 6.5
Ultimate analysis of coal 3.9 Wet process 7.9
Ultra violet and visible spectroscopy 17.2 Why carbon dioxide is a major problem 21.9
Units of Wind energy 4.9
Hardness 1.5 Woodward–Fieser rules 17.7
Heat 3.2 Work done by a system in an adiabatic
Use of inhibitors 6.28 process 11.8
Utility of phase rule | Application Working of Carnot’s engine 11.16
of phase rule 8.8
U-Tube viscometer 7.34 X
UV-rays method 1.30 X-Ray diffraction 20.6
Diffraction methods 20.8
V Diffraction of crystals and
Bragg’s equation 20.6
Valance bond theory 14.9
Valve method 19.7
Variation of conductivity with concentration 5.9 Z
Vitamin B12 12.7 Zeolite or permutit process 1.45

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Engineering Chemistry

A01_ENGINEERING-CHE00_SE_1181_FM.indd 1 5/25/2016 4:11:01 PM

Published by Pearson India Education Services Pvt. Ltd, CIN: U72200TN2005PTC057128,

A01_ENGINEERING-CHE00_SE_1181_FM.indd 2 5/25/2016 4:11:01 PM

To my husband Gaurav Chugh for his inspiration.

A01_ENGINEERING-CHE00_SE_1181_FM.indd 3 5/25/2016 4:11:02 PM

1. Water Technology 1.1

2. Polymers 2.1

3. Fuels and Combustion 3.1

4. Alternate Energy Resources 4.1

5. Electrochemistry and Batteries 5.1

6. Science of Corrosion 6.1

7. Chemistry of Engineering Materials 7.1

8. Phase Rule 8.1

9. Photochemistry 9.1

10. Surface Chemistry 10.1

11. Themodynamics 11.1

12. Metals in Biological System 12.1

13. Organometallic Compounds 13.1

14. Coordination Chemistry 14.1

15. Structure and Reactivity of Organic and Inorganic Molecules 15.1

A01_ENGINEERING-CHE00_SE_1181_FM.indd 5 5/25/2016 4:11:02 PM

16. Stereochemistry 16.1

17. Spectroscopy 17.1

18. Thermal Analysis 18.1

19. Chromatography 19.1

20. Solid State and X-Ray Diffraction 20.1

21. Green Chemistry 21.1

Lab Manual Online

A01_ENGINEERING-CHE00_SE_1181_FM.indd 6 5/25/2016 4:11:02 PM

1. Water Technology 1.1

A01_ENGINEERING-CHE00_SE_1181_FM.indd 7 5/25/2016 4:11:02 PM

2.3.3 Classification Based on Chemical Composition 2.3

A01_ENGINEERING-CHE00_SE_1181_FM.indd 8 5/25/2016 4:11:02 PM

3. Fuels and Combustion 3.1

4. Alternate Energy Resources 4.1

A01_ENGINEERING-CHE00_SE_1181_FM.indd 9 5/25/2016 4:11:02 PM

4.2.4 Water Power 4.10

5. Electrochemistry and Batteries 5.1

A01_ENGINEERING-CHE00_SE_1181_FM.indd 10 5/25/2016 4:11:02 PM

5.15 Batteries 5.51

6. Science of Corrosion 6.1

7. Chemistry of Engineering Materials 7.1

A01_ENGINEERING-CHE00_SE_1181_FM.indd 11 5/25/2016 4:11:02 PM

7.4.4 Properties of Refractories 7.18

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8. Phase Rule 8.1

A01_ENGINEERING-CHE00_SE_1181_FM.indd 13 5/25/2016 4:11:02 PM

10. Surface Chemistry 10.1

11. Thermodynamics 11.1

A01_ENGINEERING-CHE00_SE_1181_FM.indd 14 5/25/2016 4:11:02 PM

11.4.13 Solved Numerical Problems Based on Isothermal

12. Metals in Biological System 12.1

13. Organometallic Compounds 13.1

A01_ENGINEERING-CHE00_SE_1181_FM.indd 15 5/25/2016 4:11:03 PM

13.3 Organomagnesium Compounds 13.5

14. Coordination Chemistry 14.1

15. Structure and Reactivity of Organic and Inorganic Molecules 15.1

A01_ENGINEERING-CHE00_SE_1181_FM.indd 16 5/25/2016 4:11:03 PM

15.3 Bond Polarisation 15.5

16. Stereochemistry 16.1

A01_ENGINEERING-CHE00_SE_1181_FM.indd 17 5/25/2016 4:11:03 PM

Fill in the Blanks 16.15

16. Stereochemistry 16.1

17. Spectroscopy 17.1

18. Thermal Analysis 18.1

19. Chromatography 19.1

20. Solid State and X-Ray Diffraction 20.1

21. Green Chemistry 21.1

Lab Manual Online

11.4.13 Solved Numerical Problems Based on Isothermal

18.2.1 Principle of TGA 18.2

20.4.3 X-ray Diffraction of Crystals and Bragg’s Equation 20.6

Lab Manual Online

Rev. Fr. Dr. T. Amala Arockia Raj, SJ