Principles of Chemical Kinetics: James E. House

Principles of Chemical Kinetics
Second Edition
James E. House
Illinois State University
and
Illinois Wesleyan University
AMSTERDAM • BOSTON • HEIDELBERG • LONDON

NEW YORK • OXFORD • PARIS • SAN DIEGO
SAN FRANCISCO • SINGAPORE • SYDNEY • TOKYO
ELSEVIER Academic Press is an imprint of Elsevier
Contents
1 Fundamental Concepts of Kinetics 1

1.1 Rates of Reactions 2
1.2 Dependence of Rates on Concentration 4
1.2.1 First-Order 5
1.2.2 Second-Order 8
1.2.3 Zero-Order 10
1.2.4 Nth-Order Reactions 13
1.3 Cautions on Treating Kinetic Data 13
1.4 Effect of Temperature 16
1.5 Some Common Reaction Mechanisms 20
1.5.1 Direct Combination 21
1.5.2 Chain Mechanisms 22
1.5.3 Substitution Reactions 23
1.6 Catalysis 27
References for Further Reading 30
Problems 31
2 Kinetics of More Complex Systems 37
2.1 Second-Order Reaction, First-Order in Two Components 37

2.2 Third-Order Reactions 43
2.3 Parallel Reactions 45
2.4 Series First-Order Reactions 47
2.5 Series Reactions with Two Intermediates 53
2.6 Reversible Reactions 58
2.7 Autocatalysis 64
2.8 Effect of Temperature 69
Problems 75
vii
viii Contents
3 Techniques and Methods 79
3.1 Calculating Rate Constants 79

3.2 The Method of Half-Lives 81
3.3 Initial Rates 83
3.4 Using Large Excess of a Reactant (Flooding) 86
3.5 The Logarithmic Method 87
3.6 Effects of Pressure 89
3.7 Flow Techniques 94
3.8 Relaxation Techniques 95
3.9 Tracer Methods 98
3.10 Kinetic Isotope Effects 102
Problems 108
4 Reactions in the Gas Phase 111
4.1 Collision Theory 111

4.2 The Potential Energy Surface 116
4.3 Transition State Theory 119
4.4 Unimolecular Decomposition of Gases 124
4.5 Free Radical or Chain Mechanisms 131
4.6 Adsorption of Gases on Solids 136
4.6.1 Langmuir Adsorption Isotherm 138
4.6.2 B—E—T Isotherm 142
4.6.3 Poisons and Inhibitors 143
4.7 Catalysis 145
Problems 148
5 Reactions in Solutions 153
5.1 The Nature of Liquids 153

5.1.1 Intermolecular Forces 154
5.1.2 The Solubility Parameter 159
5.1.3 Solvation of Ions and Molecules 163
5.1.4 The Hard-Soft Interaction Principle (HSIP) 165
5.2 Effects of Solvent Polarity on Rates 167
5.3 Ideal Solutions 169
5.4 Cohesion Energies of Ideal Solutions 172
5.5 Effects of Solvent Cohesion Energy on Rates 175
5.6 Solvation and Its Effects on Rates 177
5.7 Effects of Ionic Strength 182
Contents ix
5.8 Linear Free Energy Relationships 185

5.9 The Compensation Effect 189
5.10 Some Correlations of Rates with Solubility Parameter 191
Problems 199
6 Enzyme Catalysis 205

6.1 Enzyme Action 205
6.2 Kinetics of Reactions Catalyzed by Enzymes 208
6.2.1 Michaelis—Menten Analysis 208
6.2.2 Lineweaver—Burk and Eadie Analyses 213
6.3 Inhibition of Enzyme Action 215
6.3.1 Competitive Inhibition 216
6.3.2 Noncompetitive Inhibition 218
6.3.3 Uncompetitive Inhibition 219
6.4 The Effect of pH 220
6.5 Enzyme Activation by Metal Ions 223
6.6 Regulatory Enzymes 224
Problems 227
7 Kinetics of Reactions in the Solid State 229
7.1 Some General Considerations 229

7.2 Factors Affecting Reactions in Solids 234
7.3 Rate Laws for Reactions in Solids 235
7.3.1 The Parabolic Rate Law 236
7.3.2 The First-Order Rate Law 237
7.3.3 The Contracting Sphere Rate Law 238
7.3.4 The Contracting Area Rate Law 240
7.4 The Prout—Tompkins Equation 243
7.5 Rate Laws Based an Nucleation 246
7.6 Applying Rate Laws 249
7.7 Results of Some Kinetic Studies 252
7.7.1 The Deaquation-Anation of [Co(NH 3 ) 5 H 2 0]C13252
7.7.2 The Deaquation-Anation of [Cr(NH 3 ) 5 H 2 0]3r3255
7.7.3 The Dehydration of Trans-[Co(NH3) 4 C12]I03 • 2H20 256
7.7.4 Two Reacting Solids 259
Problems 262
x Contents
8 Nonisothermal Methods in Kinetics 267
8.1 TGA and DSC Methods 268

8.2 Kinetic Analysis by the Coats and Redfern Method 271
8.3 The Reich and Stivala Method 275
8.4 A Method Based on Three (a,T) Data Pairs 276
8.5 A Method Based on Four (a,T) Data Pairs 279
8.6 A Differential Method 280
8.7 A Comprehensive Nonisothermal Kinetic Method 280
8.8 The General Rate Law and a Comprehensive Method 281
Problems 288
9 Additional Applications of Kinetics 289
9.1 Radioactive Decay 289

9.1.1 Independent Isotopes 290
9.1.2 Parent-Daughter Cases 291
9.2 Mechanistic Implications of Orbital Symrnetry 297
9.3 A Further Look at Solvent Properties and Rates 303
Problems 314
Index 317

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Principles of Chemical Kinetics

AMSTERDAM • BOSTON • HEIDELBERG • LONDON

1 Fundamental Concepts of Kinetics 1

2 Kinetics of More Complex Systems 37

2.1 Second-Order Reaction, First-Order in Two Components 37

3 Techniques and Methods 79

3.1 Calculating Rate Constants 79

4 Reactions in the Gas Phase 111

4.1 Collision Theory 111

5 Reactions in Solutions 153

5.1 The Nature of Liquids 153

5.8 Linear Free Energy Relationships 185

6 Enzyme Catalysis 205

7 Kinetics of Reactions in the Solid State 229

7.1 Some General Considerations 229

8 Nonisothermal Methods in Kinetics 267

8.1 TGA and DSC Methods 268

9 Additional Applications of Kinetics 289

9.1 Radioactive Decay 289

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