Chemical Kinetics (eBook)

Cover 1
Copyright page 5
Contents 6
Preface 12
Chapter 1. Introduction 14
1.1 Initial Difficulties in the Development of Chemical Kinetics in the Twentieth Century 15
1.2 Chemical Kinetics: The Current View 17
References 27
Chapter 2. Reaction Rate Laws 28
2.1 Reaction Rates 28
2.2 Factors that Influence the Velocities of Reactions 30
References 45
Chapter 3. Experimental Methods 46
3.1 Application of Conventional Techniques to Study Reactions 47
3.2 Application of Special Techniques for Fast Reactions 63
References 88
Chapter 4. Reaction Order and Rate Constants 90
4.1 Rates of Elementary Reactions 90
4.2 Rates of Complex Reactions 97
4.3 Methods for Solving Kinetic Equations 102
4.4 Simplification of Kinetic Schemes 119
References 126
Chapter 5. Collisions and Molecular Dynamics 128
5.1 Simple Collision Theory 130
5.2 Collision Cross Section 135
5.3 Calculation of Classical Trajectories 141
5.4 PES Crossings 148
5.5 Molecular Dynamics 150
References 155
Chapter 6. Reactivity in Thermalised Systems 156
6.1 Transition-State Theory 156
6.2 Semi-Classical Treatments 169
6.3 Intersecting-State Model 180
References 200
Chapter 7. Relationships between Structure and Reactivity 202
7.1 Quadratic Free-Energy Relationships (QFER) 202
7.2 Linear Free-Energy Relationships (LFER) 206
7.3 Other Kinds of Relationships between Structure and Reactivity 215
References 220
Chapter 8. Unimolecular Reactions 222
8.1 Lindemann–Christiansen Mechanism 222
8.2 Hinshelwood’s Treatment 225
8.3 Rice–Rampsberger–Kassel–Marcus (RRKM) Treatment 228
8.4 Local Random Matrix Theory (LRMT) 231
8.5 Energy Barriers in the Isomerisation of Cyclopropane 233
References 235
Chapter 9. Elementary Reactions in Solution 236
9.1 Solvent Effects on Reaction Rates 236
9.2 Effect of Diffusion 238
9.3 Diffusion Constants 242
9.4 Reaction Control 248
References 262
Chapter 10. Reactions on Surfaces 264
10.1 Adsorption 264
10.2 Adsorption Isotherms 269
10.3 Kinetics on Surfaces 272
10.4 Transition-State Theory for Reactions on Surfaces 276
10.5 Model Systems 281
References 284
Chapter 11. Substitution Reactions 286
11.1 Mechanisms of Substitution Reactions 286
11.2 SN2 and SN1 Reactions 287
11.3 Langford–Gray Classification 289
11.4 Symmetrical Methyl Group Transfers in the Gas-Phase 293
11.5 State Correlation Diagrams of Pross and Shaik 295
11.6 Intersecting-State Model 298
11.7 Cross-Reactions in Methyl Group Transfers in the Gas Phase 301
11.8 Solvent Effects in Methyl Group Transfers 302
References 307
Chapter 12. Chain Reactions 308
12.1 Hydrogen–Bromine Reaction 308
12.2 Reaction between Molecular Hydrogen and Chlorine 311
12.3 Reaction between Molecular Hydrogen and Iodine 313
12.4 Calculation of Energy Barriers for Elementary Steps in Hydrogen–Halogens Reactions 314
12.5 Comparison of the Mechanisms of the Hydrogen–Halogen Reactions 316
12.6 Pyrolysis of Hydrocarbons 318
12.7 Explosive Reactions 323
12.8 Polymerisation Reactions 330
References 333
Chapter 13. Acid–Base Catalysis and Proton-Transfer Reactions 334
13.1 General Catalytic Mechanisms 334
13.2 General and Specific Acid–Base Catalysis 339
13.3 Mechanistic Interpretation of the pH Dependence of the Rates 342
13.4 Catalytic Activity and Acid–Base Strength 351
13.5 Salt Effects 355
13.6 Acidity Functions 356
13.7 Hydrated Proton Mobility in Water 358
13.8 Proton-Transfer Rates in Solution 363
References 371
Chapter 14. Enzymatic Catalysis 374
14.1 Terminology 374
14.2 Michaelis–Menten Equation 376
14.3 Mechanisms with Two Enzyme–Substrate Complexes 381
14.4 Inhibition of Enzymes 383
14.5 Effects of pH 386
14.6 Temperature Effects 388
14.7 Molecular Models for Enzyme Catalysis 389
14.8 Isomerisation of Dihydroxyacetone Phosphate to Glyceraldehyde 3-Phosphate Catalysed by Triose-Phosphate 392
14.9 Hydroperoxidation of Linoleic Acid Catalysed by Soybean Lipoxygenase-1 394
References 396
Chapter 15. Transitions between Electronic States 398
15.1 Mechanisms of Energy Transfer 398
15.2 The “Golden Rule” of Quantum Mechanics 404
15.3 Radiative and Radiationless Rates 408
15.4 Franck–Condon Factors 413
15.5 Radiationless Transitions within a Molecule 420
15.6 Triplet-Energy (or Electron) Transfer between Molecules 423
15.7 Electronic Coupling 434
15.8 Triplet-Energy (and Electron) Transfer Rates 443
References 447
Chapter 16. Electron Transfer Reactions 450
16.1 Rate Laws for Outer-Sphere Electron Exchanges 450
16.2 Theories of Electron-Transfer Reactions 453
16.3 ISM and Electron-Transfer Reactions 465
16.4 Non-Adiabatic Self-Exchanges of Transition-Metal Complexes 471
16.5 Electron Self-Exchanges of Organic Molecules 473
16.6 Inverted Regions 475
16.7 Electron Transfer at Electrodes 482
References 495
Appendix I: General Data 498
Appendix II: Statistical Thermodynamics 500
Appendix III: Parameters Employed in ISM Calculations 508
Appendix IV: Semi-classical Interacting State Model 512
IV.1 Vibrationally Adiabatic Path 512
IV.2 Tunnelling Corrections 515
IV.3 Semi-classical Rate Constants 516
References 517
Appendix V: The Lippincott–Schroeder Potential 518
V.1 Lippincott—Schroeder (LS) Potential 518
V.2 The LS–ISM Reaction Path 521
V.3 Rate Constants for Proton Transfer along an H-bond 521
References 522
Appendix VI: Problems 524
Subject Index 556