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Engineering Chemistry

Book · June 2012

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3 authors, including:

Baskar Chinnappan Ranjit Dhillon


THDC Institute of Hydropower Engineering and Technology Tehri, Uttarakhand Te… Punjab Agricultural University
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Contents

Foreword v
Preface vii
1.  General Chemistry 1
Learning Objectives 1
1.1  Valence Bond Theory 1
1.2  Hybridization and Shapes of Molecules 2
sp Hybridization 3
sp2 Hybridization 5
sp3 Hybridization 5
Lone Pair in Hybrid Orbitals 7
1.3  Molecular Orbital Theory 8
Linear Combination of Atomic Orbitals (LCAO) 9
MO Diagram of Homodiatomic Molecules 11
MO Diagram of Heteronuclear Diatomic Molecules 14
1.4  Metallic Bond 17
Theories of Metallic Bond 17
1.5  Hydrogen Bond 20
Types of Hydrogen Bond 21
Consequences of Hydrogen Bonding 22
1.6  van der Waals Forces 24
1.7  Solid State 25
Crystalline Solids 26
Amorphous Solids 26
Differences between Amorphous and Crystalline Solids 26
1.8  Space Lattice and Unit Cell 27
1.9  Types of Unit Cell 28
1.10  Cubic Lattice 30
Calculation of Number of Particles per Unit Cel 31
Density Computation  31
1.11  Crystal Structure 34
Packing Efficiency 36
Radius Ratio Rule 38
Relation between Void Radius and Atom Radius in Close Packing 39
1.12  Bragg’s Law – X-Ray Structure of Crystals 42
X-Ray Structure of Crystals 42
1.13  Liquid Crystals and Their Applications 45
Classification of Liquid Crystals 46
Types of Mesophases 47
Liquid Crystalline Behavior in Homologous Series 50
Applications of Liquid Crystals 51

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x  • Contents

1.14  Fullerenes – Structure and Applications 53


Applications 54
Key Terms 54
Objective-Type Questions 55
Review Questions 59
Numerical Problems 61
Answers 62

2.  Organic Reaction Mechanisms 65


Learning Objectives 65
2.1  Bonding in Organic Molecules 65
Homolytic Fission 65
Heterolytic Fission 66
2.2  Electronic Displacement Effects in Organic Molecules 66
Inductive Effect 66
Inductometric Effect 69
Electromeric Effect 69
Mesomeric or Resonance Effect 69
Hyperconjugative Effect: Baker–Nathan Effect 72
2.3  Reactive Intermediates 73
Free Radicals 74
Carbocations 76
Carbanions 78
Carbene 80
2.4  Attacking Reagents in an Organic Reaction 81
Electrophiles 81
Nucleophiles 81
2.5  Types of Organic Reactions 82
2.6  Addition Reactions 82
Nucleophilic Addition 83
Electrophilic Addition 86
Free Radical Addition 88
2.7  Substitution Reactions 89
Nucleophilic Substitution (SN) 89
Electrophilic Substitution 92
Nucleophilic Aromatic Substitution 96
Free Radical Substitution 98
2.8  Elimination Reactions 99
Bimolecular Elimination Reactions (E2) 99
Unimolecular Elimination Reactions (E1) 100
Elimination versus Substitution 101
2.9  Rearrangement Reactions 101
2.10  Some Name Reactions 102
Aldol Condensation 102

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Contents •  xi

Cannizzaro Reaction 104


Pinacol–Pinacolone Rearrangement 106
Beckmann Rearrangement 108
Hofmann Rearrangement or Degradation 109
Key Terms 111
Objective-Type Questions 111
Review Questions 114
Answers 116

3.  Stereochemistry 119


Learning Objectives 119
3.1  Stereoisomerism 119
Types of Stereoisomers 120
3.2  Chirality and Optical Activity 120
Concept of Chirality 120
Chirality and Symmetry Elements 121
Fischer Projections 123
Concept of Optical Activity 125
Measurement of Optical Activity 125
Relation between Chirality and Optical Activity 126
3.3  Optical Isomerism 130
Enantiomers and Optical Activity 130
Diastereomers and Optical Activity 131
Relation between Number of Optical Isomers and Stereogenic Carbons 132
3.4  Configuration 133
Relative Configuration (D and L System) 134
Absolute Configuration (R and S System) 136
3.5  Geometrical Isomerism 140
cis and trans Nomenclature 140
E and Z Nomenclature 142
Geometrical Isomerism in Cyclic Structures 143
3.6  Conformational Isomerism 144
Newman Projections 144
Conformations 144
Conformations of Ethane 145
Conformations of n-Butane 146
Conformations of Cyclohexane 146
Key Terms 148
Objective-Type Questions 149
Review Questions 152
Numerical Problems 155
Answers 156

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xii  • Contents

4.  Chemical Kinetics 157


Learning Objectives 157
4.1  Rate of Reaction 158
Measurement of Rate of Reaction 158
Factors Influencing Rate of Reaction 159
Rate Laws 159
4.2  Order and Molecularity 160
Order 160
Molecularity 162
4.3  Integrated Rate Equations and Half Lives 163
Zero-Order Reactions 163
First-Order Reactions 163
Second-Order Reactions 164
Third-Order Reactions 167
Higher nth Order Reactions 168
4.4  Pseudo-First-Order 176
4.5  Temperature Dependence of Rate of Reactions 177
Temperature Coefficient 177
Activation Energy 177
Arrhenius Equation 178
4.6  Theories of Reaction Rates 183
Collision Theory 183
Transition State Theory (Absolute Reaction Rate Theory or Activated Complex Theory) 185
4.7  Catalysts 187
Types of Catalysts 187
Types of Catalytic Reactions 187
Mechanism of Catalysis 188
Key Terms 189
Objective-Type Questions 189
Review Questions 193
Numerical Problems 196
Answers 198

5  Electrochemistry 199
Learning Objectives 199
5.1  Electrical Conductance 200
Types of Electrolytes 200
Conductivity of Solutions of Electrolytes 200
Specific Conductance 201
Equivalent Conductance 202
Molar Conductance 202
Ionic Conductance 202
Factors Affecting Conductance 204

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Contents •  xiii

Transport (Transference) Number 204


Interionic Attraction Theory of Conductance 205
Hydration of Ions 205
5.2  Electrochemical Cells 208
Redox Reactions 208
5.3  Electrode Potential 209
Origin of Electrode Potential 209
Oxidation Potential 210
Reduction Potential 210
Standard Electrode Potential (E0) 210
5.4  Galvanic Cells 211
Construction and Working 211
Salt Bridge 212
EMF of the Cell and Free Energy Change 212
Electrochemical Conventions and Notations 213
5.5  Nernst Equation 214
Derivation 214
5.6  Measurement of EMF of a Cell 221
EMF and Potential Difference 221
Potentiometric Measurement 221
5.7  Reference Electrodes 222
Standard Hydrogen Electrode (Normal Hydrogen Electrode) 223
Calomel Electrode 223
Silver–Silver Chloride Electrode 224
5.8  Single Electrode Potential 225
Measurement of Single Electrode Potential 226
Applications 226
Electrochemical Series 227
5.9  Types of Electrodes 230
5.10  Glass Electrode 233
Construction 233
Glass Electrode Potential 234
Advantages and Limitations 235
Determination of pH using Glass Electrode 236
5.11  Concentration Cells 239
Electrode Concentration Cells  239
Electrolyte Concentration Cells 239
Applications of Concentration Cells 242
5.12  Batteries 244
Discharging and Charging of a Battery 244
Characteristics of a Battery 245
5.13  Classical Batteries 247
Primary Cells 247
Secondary (Storage) Cells 249
5.14  Modern Batteries 251

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xiv  • Contents

Metal–Air Batteries 251


Nickel–Metal Hydride Batteries 252
Lithium Batteries 253
5.15  Fuel Cells 254
Comparison with Conventional Galvanic Cells 254
Advantages and Limitations 255
Cell Representation 255
Hydrogen–Oxygen Fuel Cell 255
Types of Fuel Cells 257
5.16  Corrosion 259
5.17  Corrosion in Metals and Alloys 259
Causes of Corrosion 259
Effects of Corrosion 260
5.18  Corrosion Cell 260
5.19  Types of Corrosion 261
Dry Corrosion (Direct Chemical Attack) 261
Wet Corrosion (Electrochemical Theory of Corrosion) 262
Differences between Dry Corrosion and Wet Corrosion 263
5.20  Types of Electrochemical Corrosion 264
Differential Metal Corrosion (Galvanic Corrosion) 264
Differential Aeration Corrosion (Concentration Cell Corrosion) 265
Waterline Corrosion 266
Crevice Corrosion 266
Pitting Corrosion 267
5.21  Other Types of Corrosion 268
5.22  Factors Influencing Rate of Corrosion 271
Primary Factors 271
Secondary Factors 272
5.23  Corrosion Control Methods 274
5.24  Protective Coatings 276
Key Terms 278
Objective-Type Questions 279
Review Questions 284
Numerical Problems 288
Answers 290

6.  Water and Its Treatment 293


Learning Objectives 293
6.1  Sources of Water 293
6.2  Impurities in Water 294
6.3  Hardness of Water 294
Formation of Hard Water 294
Types of Hardness 295
Degree of Hardness 295
Units of Hardness 296

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Contents •  xv

6.4  Determination of Hardness of Water 299


Soap Solution Method 299
Complexometric Titration Method Using EDTA 301
6.5  Alkalinity of Water 304
Types of Alkalinity 304
Estimation of Alkalinity 304
6.6  Analysis of Water 308
Determination of Chlorides by Argentometric Method 308
Determination of Fluoride by SPADNS Method 309
Determination of Nitrate by Phenol Disulphonic Method 309
Determination of Sulphate by Gravimetric Method 310
Determination of Dissolved Oxygen by Winkler’s Method 311
6.7  Disadvantages of Hard Water 312
Domestic Purposes 312
Industrial Purposes 312
6.8  Potable Water 313
Pretreatment 313
Removal of Suspended Impurities 313
Disinfection 314
Desalination of Brackish Water 315
6.9  Boiler Feed Water 317
Characteristics of Boiler Feed Water 318
Boiler Troubles/Problems 318
6.10  Techniques for Water Softening 322
External Treatment for Softening Water 322
Internal Treatment for Softening Water 327
6.11  Sewage 333
Characteristics of Wastewater 333
Sewage Treatment 334
Key Terms 338
Objective-Type Questions 338
Review Questions 342
Numerical Problems 346
Answers 350

7.  Chemistry of Engineering Materials 353


Learning Objectives 353
7.1  Some Important Terms and Definitions 354
7.2  Classification of Polymers 355
7.3  Types of Polymerization 358
Addition Polymerization or Chain-Growth Polymerization 358
Condensation Polymerization or Step-Growth Polymerization 358
Copolymerization 360
7.4  Mechanism of Addition Polymerization 361

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xvi  • Contents

Free Radical Mechanism 361


Ionic Polymerization 362
7.5  Polymerization Techniques 366
Bulk Polymerization 366
Solution Polymerization 366
Suspension (Pearl) Polymerization 367
Emulsion Polymerization 368
7.6  Molecular Weights of Polymers 369
7.7  Structure–Property Relationship of Polymers 372
Glass Transition Temperature (Tg) 374
7.8  Plastics 376
Properties and Uses of Plastics as Engineering Materials 376
Classification of Plastics 377
Compounding of Plastics 377
Casting of Plastics 379
Spinning of Plastics 379
Plastic Molding Methods 381
7.9  Some Important Commercial Thermoplastics 387
Polyethylene (PE) 387
Polypropylene 389
Polystyrene 389
Polyvinylchloride 390
Polyvinyl Acetate 391
Polytetrafluoroethylene/Teflon 391
Polymethyl Methacrylate/Plexiglass 392
Polyurethanes 392
7.10  Some Important Commercial Thermosetting Resins 393
Phenol–Formaldehyde Resins 393
Amino Resins 395
Silicone Resins 397
7.11  Elastomers (Rubbers) 398
Natural Rubber (NR) 398
Processing of Latex 398
Processes for Improvement of Properties of Natural Rubber 399
Synthetic Rubbers 401
7.12  Some Important Synthetic Rubbers 401
Butyl Rubber (GR-I Rubber) 401
Polychloroprene (Neoprene or GR-M Rubber) 402
Styrene–Butadiene Rubber (SBR) (Buna-S or GR-S Rubber) 402
Nitrile Rubber (NBR) (Buna-N or GR-A Rubber) 403
Polysulphide Rubber 403
Silicone Rubber 404
7.13  Fibers 404
Physical Properties 404
Types of Fibers 405
Spinning Processes 405

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Contents •  xvii

7.14  Some Important Synthetic and Semisynthetic Fibers 406


Nylons (Polyamides) 406
Polyethylene Terephthalate (Polyester) 408
Acrylic Fibers (Polyacrylonitriles) 409
7.15  Composites 410
Classification of Composites 411
Fiber Reinforced Plastics (FRPs) 412
7.16  Adhesives 413
Types of Adhesives 413
Epoxy Resins (Araldite) 413
7.17  Conducting Polymers 414
Conducting Polymers with Conjugated p-Electrons 415
Applications of Conducting Polymers 418
7.18  Semiconducting Polymers 419
7.19  Natural Polymers (Biopolymers) 419
Starch 419
Cellulose 420
Proteins 421
Nucleic Acids 421
Natural Rubber 421
7.20  Ion Exchange Resins 421
7.21  Biodegradable Polymers 422
Classification of Biodegradable Polymers 423
Applications of Biodegradable Polymers 423
7.22  Refractories 424
Classification of Refractories 424
Characteristics of Refractories 424
Manufacture of Refractory Materials 427
Some Common Refractories 428
Causes for Failure of Refractory Material 429
7.23  Alloys 430
Purpose of Making Alloys 430
Manufacture of Alloys 431
Classification of Alloys 431
7.24  Nanotechnology 434
General Methods of Synthesis and Characterization 435
Applications of Nanomaterials 438
Carbon Nanotubes 439
Key Terms 442
Objective-Type Questions 443
Review Questions 448
Numerical Problems 453
Answers 454

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xviii  • Contents

8.  Fuels and Combustion 455


Learning Objectives 455
8.1  Classifications of Fuels 456
Classification Based on Physical State 456
Classification Based on Occurrence 457
Characteristics of a Good Fuel 458
8.2  Calorific Value 458
Units 458
Gross and Net Calorific Values 459
8.3  Determination of Calorific Value 459
Theoretical Determination 459
Experimental Determination 461
8.4  Combustion 466
Concepts 466
Calculations 467
8.5  Solid Fuels – Coal 472
Types of Coal 473
Uses of Coal 473
Pulverized Coal 473
8.6  Proximate and Ultimate Analyses of Coal 474
Proximate Analysis 474
Ultimate Analysis 476
8.7  Coke 479
Coke as Metallurgical Fuel 480
Caking and Coking Coals 480
Coking Processes 480
8.8   Biofuels 483
Biomass 484
Biodiesel 485
Mechanism for acid-catalyzed transesterification (Figure 11): 487
Mechanism for base-catalyzed transesterification (Figure 12): 488
Biogas 489
8.9  Liquid Fuels – Petroleum 490
Origin 490
Composition 490
Production from Refining of Crude Oil 490
Fractional Distillation 491
Cracking 492
Catalytic Reforming 494
Compounds Isolated from Crude Oil 496
Knocking 496
8.10  Power Alcohol and Synthetic Petrol 498
Power Alcohol 498
Synthetic Petrol 499
8.11  Gaseous Fuels 501

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Contents •  xix

Liquefied Petroleum Gas 502


Natural Gas 502
Coal Gas 503
Producer Gas 504
Water Gas 505
Flue Gas Analysis 506
8.12  Lubricants 507
Principle of Lubrication 508
Mechanism of Lubrication 510
Classification of Lubricants 511
Additives for Lubricants 513
Properties of Lubricants and their Measurement 514
8.13  Rocket Propellants 521
8.14  Explosives 523
Classification of Chemical Explosives 523
Characteristics of Chemical Explosives 525
Preparation of Explosives 526
Key Terms 529
Objective-Type Questions 529
Review Questions 532
Numerical Problems 537
Answers 541

9.  Chemical Methods of Analysis 543


Learning Objectives 543
9.1  Physical Analysis 543
9.2  Chemical Analysis 544
9.3  Volumetric (Titrimetric) Analysis 545
Some Terms Used in Volumetric Analysis 545
Different Types of Volumetric Titrations 547
9.4  Neutralization Titrations (Acid–Base Titrations) 547
Selection of Indicators and Their Action 547
Acid–Base Titration Curves 548
Estimation of Alkalinity of Water 548
9.5  Redox Titrations 549
Redox Indicators 549
Potassium Permanganate Titrations 550
Potassium Dichromate Titrations 550
Iodine Titrations 550
9.6  Complexometric Titrations 551
Selection of Indicators 551
Estimation of Hardness of Water by EDTA Method 551
9.7  Precipitation Titrations 552
Argentometric Titration 552

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xx  • Contents

9.8  Gravimetric Analysis 553


Precipitation Method 553
Volatilization Method 554
Key Terms 554
Objective-Type Questions 554
Review Questions 556
Answers 557

10.   Instrumental Methods of Analysis 559


Learning Objectives 559
10.1  Electroanalytical Methods 559
Conductometry 559
Potentiometry 566
10.2  Electromagnetic Radiation 569
Characteristics of Electromagnetic Radiation 569
Electromagnetic Spectrum 569
10.3  Molecular Spectroscopy 570
Types of Energy Changes in a Molecule 570
Interaction of Electromagnetic Radiation with Molecule and Origin of Electronic Spectra 571
Laws of Absorbance of Radiation 572
10.4  Basic Spectroscopy Instrumentation 574
Essential Components 574
Block Diagrams for Standard Emission and Absorption Spectrometers 574
Resolving Power and Signal-to-Noise Ratio 575
Width and Intensity of Spectral Lines 576
10.5  Infrared Spectroscopy 576
Interaction between Infrared Radiations and Molecular Vibrations 577
Modes of Vibration 577
Analysis of IR Spectra 579
Recording of IR Spectrum (Instrumentation for IR Spectroscopy) 582
Applications of IR Spectroscopy 583
Fourier Transform (FT) 584
10.6  NMR Spectroscopy 586
Concepts and Theory 586
Interaction between Nuclear Spin and Magnetic Field 587
Instrumentation of NMR Spectroscopy 590
Chemical Shift 590
Spin–Spin Interaction 594
Interpretation of NMR Spectra 596
Representative NMR Spectra of Some Organic Molecules and Their Interpretation 598
Simplification of Complex Spectra 600
13
C NMR 601
10.7  UV–Visible Spectroscopy 604
Chromophore and Auxochrome 604

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Contents •  xxi

Electronic Transitions 604


Representation of UV–Visible Spectra 605
Applications of UV Absorption Spectroscopy 605
Woodward–Fisher Rules for Calculating Absorption Maximum in Conjugated Dienes 606
10.8  Mass Spectrometry (MS) 609
Theory 609
Representation of Mass Spectra 609
Instrumentation 613
Mass Spectra of Some Simple Organic Compounds 617
10.9  Chromatography 621
Types of Chromatography 621
Key Terms 624
Objective-Type Questions 624
Review Questions 628
Numerical Problems 634
Answers 635

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