Chemical kinectics : from molecular structure to chemical reactivity / 1st ed.
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作 者：Luis Arnaut, Sebasti鋋o Formosinho, Hugh Burrows.
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ISBN：9780444521866
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简介
Chemical Kinetics bridges the gap between beginner and specialist with a path that leads the reader from the phenomenological approach to the rates of chemical reactions to the state-of-the-art calculation of the rate constants of the most prevalent reactions: atom transfers,catalysis, proton transfers, substitution reactions, energy transfers and electron transfers. For the beginner provides the basics: the simplest concepts, the fundamental experiments, and the underlying theories. For the specialist shows where sophisticated experimental and theoretical methods combine to offer a panorama of time-dependent molecular phenomena connected by a new rational.Chemical Kinetics goes far beyond the qualitative description: with the guidance of theory, the path becomesa reaction path that can actually be inspected and calculated. But Chemical Kinetics is more about structure and reactivity than numbers and calculations. A great emphasis in the clarity of the concepts is achieved by illustrating all the theories and mechanisms with recent examples, some of them described with sufficient detail and simplicity to be used in general chemistry and lab courses. * Looking at atoms and molecules, and how molecular structures change with time. * Providing practical examples and detailed theoretical calculations *Of special interest to Industrial Chemistry and Biochemistry.
目录
Table Of Contents:
Preface xi
1 Introdcution
1.1 Initial Difficulties in the Development of Chemical Kinetics in the Twentieth Century 2
1.2 Chemical Kinetics: The Current View 4
References 14
2 Reaction Rate Laws 15
2.1 Reaction Rates 15
2.2 Factors that Influence the Velocities of Reactions 17
2.2.1 Nature of the reagents 17
2.2.2 Reactant concentration 19
2.2.3 Temperature 25
2.2.4 Light 26
2.2.5 Catalysts 29
2.2.6 Reaction medium 30
References 32
3 Experimental Methods 33
3.1 Application of Conventional Techniques to Study Reactions 34
3.1.1 First-order reactions 34
3.1.2 Second-order reactions 36
3.1.3 Complex reactions 39
3.1.4 Activation energy 41
3.1.5 Dependence of light intensity 43
3.1.6 Enzyme catalysis 46
3.1.7 Dependence on ionic strength 47
3.2 Application of Special Techniques for Fast Reactions 50
3.2.1 Flow methods 51
3.2.2 Relaxation methods 52
3.2.3 Competition methods 56
3.2.4 Methods with enhanced time resolution 61
References 75
4 Reaction Order and Rate Constants 77
4.1 Rates of Elementary Reactions 77
4.1.1 First-order reactions 77
4.1.2 Second-order reactions 80
4.1.3 Zero-order reactions 82
4.1.4 Third-order reactions 83
4.2 Rates of Complex Reactions 84
4.2.1 Parallel first-order reactions 85
4.2.2 Consecutive first-order reactions 86
4.2.3 Reversible first-order reactions 88
4.3 Methods for Solving Kinetic Equations 89
4.3.1 Laplace transforms 89
4.3.2 Matrix method 94
4.3.3 Runge鈥揔utta method 97
4.3.4 Markov chains 99
4.3.5 Monte Carlo method 103
4.4 Simplification of Kinetic Schemes 106
4.4.1 Isolation method 106
4.4.2 Pre-equilibrium approximation 107
4.4.3 Steady-state approximation 108
4.4.4 Rate-determining step of a reaction 111
References 113
5 Collisions and Molecular Dynamics 115
5.1 Simple Collision Theory 117
5.2 Collision Cross Section 122
5.3 Calculation of Classical Trajectories 128
5.4 PES Crossings 135
5.5 Molecular Dynamics 137
References 142
6 Reactivity in Thermalised Systems 143
6.1 Transition-State Theory 143
6.1.1 Classical formulation 144
6.1.2 Partition functions 147
6.1.3 Absolute rate calculations 149
6.1.4 Statistical factors 151
6.1.5 Beyond the classical formulation 154
6.2 Semi-Classical Treatments 156
6.2.1 Kinetic isotope effects 156
6.2.2 Tunnel effect 160
6.3 Intersecting-State Model 167
6.3.1 Activation energies 170
6.3.2 Classical rate constants 176
6.3.3 Absolute semi-classical rates 180
6.3.4 Relative rates 183
References 187
7 Relationships between Structure and Reactivity 189
7.1 Quadratic Free-Energy Relationships (QFER) 189
7.2 Linear Free-Energy Relationships (LEER) 193
7.2.1 Br枚nsted equation 194
7.2.2 Bell鈥揈vans鈥揚olanyi equation 196
7.2.3 Hammett and Taft relationships 196
7.3 Other Kinds of Relationships between Structure and Reactivity 202
7.3.1 The Hammond postulate 202
7.3.2 The reactivity鈥搒electivity principle (RSP) 203
7.3.3 Relationships of the electronic effect: equation of Ritchie 205
7.3.4 An empirical extension of the Bell鈥揈vans鈥揚olanyi relationship 205
References 207
8 Unimolecular Reactions 209
8.1 Lindemann鈥揅hristiansen Mechanism 209
8.2 Hinshelwood's Treatment 212
8.3 Rice鈥揜ampsberger鈥揔assel鈥揗arcus (RRKM) Treatment 215
8.4 Local Random Matrix Theory (LRMT) 218
8.5 Energy Barriers in the Isomerisation of Cyclopropane 220
References 222
9 Elementary Reactions in Solution 223
9.1 Solvent Effects on Reaction Rates 223
9.2 Effect of Diffusion 225
9.3 Diffusion Constants 229
9.4 Reaction Control 235
9.4.1 Internal pressure 237
9.4.2 Reactions between ions 240
9.4.3 Effect of ionic strength 244
9.4.4 Effect of hydrostatic pressure 246
References 249
10 Reactions on Surfaces 251
10.1 Adsorption 251
10.2 Adsorption Isotherms 256
10.2.1 Langmuir isotherm 256
10.2.2 Adsorption with dissociation 257
10.2.3 Competitive adsorption 258
10.3 Kinetics on Surfaces 259
10.3.1 Unimolecular surface reactions 259
10.3.2 Activation energies of unimolecular surface reactions 260
10.3.3 Reaction between two adsorbed molecules 261
10.3.4 Reaction between a molecule in the gas phase and an adsorbed molecule 263
10.4 Transition-State Theory for Reactions on Surfaces 263
10.4.1 Unimolecular reactions 263
10.4.2 Bimolecular reactions 265
10.5 Model Systems 268
10.5.1 Langmuir鈥揌inshelwood mechanism 268
10.5.2 Eley鈥揜ideal mechanism 270
References 271
11 Substitution Reactions 273
11.1 Mechanisms of Substitution Reactions 273
11.2 SN2 and SN1 Reactions 274
11.3 Langford鈥揋ray Classification 276
11.4 Symmetrical Methyl Group Transfers in the Gas-Phase 280
11.5 State Correlation Diagrams of Pross and Shaik 282
11.6 Intersecting-State Model 285
11.7 Cross-Reactions in Methyl Group Transfers in the Gas Phase 288
11.8 Solvent Effects in Methyl Group Transfers 289
References 294
12 Chain Reactions 295
12.1 Hydrogen鈥揃romine Reaction 295
12.2 Reaction between Molecular Hydrogen and Chlorine 298
12.3 Reaction between Molecular Hydrogen and Iodine 300
12.4 Calculation of Energy Barriers for Elementary Steps in Hydrogen鈥揌alogens Reactions 301
12.5 Comparison of the Mechanisms of the Hydrogen鈥揌alogen Reactions 303
12.6 Pyrolysis of Hydrocarbons 305
12.6.1 Pyrolysis of ethane 306
12.6.2 Pyrolysis of acetic aldehyde 308
12.6.3 Goldfinger鈥揕etort鈥揘iclause rules 309
12.7 Explosive Reactions 310
12.7.1 Combustion between hydrogen and oxygen 310
12.7.2 Thermal explosions 314
12.7.3 Combustion of hydrocarbons 316
12.8 Polymerisation Reactions 317
References 320
13 Acid鈥揃ase Catalysis and Proton-Transfer Reactions 321
13.1 General Catalytic Mechanisms 321
13.1.1 Fast pre-equilibrium: Arrhenius intermediates 322
13.1.2 Steady-state conditions: van't Hoff intermediates 324
13.2 General and Specific Acid鈥揃ase Catalysis 326
13.3 Mechanistic Interpretation of the pH Dependence of the Rates 329
13.4 Catalytic Activity and Acid鈥揃ase Strength 338
13.5 Salt Effects 342
13.6 Acidity Functions 343
13.7 Hydrated Proton Mobility in Water 345
13.8 Proton-Transfer Rates in Solution 350
13.8.1 Classical PT rates 351
13.8.2 Semiclassical absolute rates 356
References 358
14 Enzymatic Catalysis 361
14.1 Terminology 361
14.2 Michaelis鈥揗enten Equation 363
14.3 Mechanisms with Two Enzyme鈥揝ubstrate Complexes 368
14.4 Inhibition of Enzymes 370
14.5 Effects of pH 373
14.6 Temperature Effects 375
14.7 Molecular Models for Enzyme Catalysis 376
14.8 Isomerisation of Dihydroxyacetone Phosphate to Glyceraldehyde 3-Phosphate Catalysed by Triose-Phosphate 379
14.9 Hydroperoxidation of Linoleic Acid Catalysed by Soybean Lipoxygenase-1 381
References 383
15 Transitions between Electronic States 385
15.1 Mechanisms of Energy Transfer 385
15.2 The "Golden Rule" of Quantum Mechanics 391
15.3 Radiative and Radiationless Rates 395
15.4 Franck鈥揅ondon Factors 400
15.5 Radiationless Transitions within a Molecule 407
15.6 Triplet-Energy (or Electron) Transfer between Molecules 410
15.7 Electronic Coupling 421
15.8 Triplet-Energy (and Electron) Transfer Rates 430
References 434
16 Electron Transfer Reactions 437
16.1 Rate Laws for Outer-Sphere Electron Exchanges 437
16.2 Theories of Electron-Transfer Reactions 440
16.2.1 The classical theory of Marcus 440
16.2.2 Solute-driven and solvent-driven processes 443
16.2.3 Critique of the theory of Marcus 445
16.2.4 ISM as a criterion for solute-driven electron transfers 449
16.3 ISM and Electron-Transfer Reactions 452
16.3.1 Representing ET reactions by the crossing of two potential-energy curves 452
16.3.2 Adiabatic self-exchanges of transition-metal complexes 454
16.3.3 Outer-sphere electron transfers with characteristics of an inner-sphere mechanism 456
16.4 Non-Adiabatic Self-Exchanges of Transition-Metal Complexes 458
16.4.1 A source of non-adiabaticity: orbital symmetry 458
16.4.2 Electron tunnelling at a distance 458
16.4.3 Non-adiabaticity due to spin forbidden processes 459
16.5 Electron Self-Exchanges of Organic Molecules 460
16.6 Inverted Regions 462
16.7 Electron Transfer at Electrodes 469
16.7.1 The Tafel equation 469
16.7.2 Calculations of rate constants 475
16.7.3 Asymmetry in Tafel plots 478
16.7.4 Electron transfer at surfaces through a blocking layer 479
References 482
Appendix I: General Data 485
Appendix II: Statistical Thermodynamics 487
Appendix III: Parameters Employed in ISM Calculations 495
Appendix IV: Semi-classical Interacting State Model 499
IV.1 Vibrationally Adiabatic Path 499
IV.2 Tunnelling Corrections 502
IV.3 Semi-classical Rate Constants 503
References 504
Appendix V: The Lippincott鈥揝chroeder Potential 505
V.1 Lippincott鈥擲chroeder (LS) Potential 505
V.2 The LS鈥揑SM Reaction Path 508
V.3 Rate Constants for Proton Transfer along an H-bond 508
References 509
Appendix VI: Problems 511
Subject Index 543
Preface xi
1 Introdcution
1.1 Initial Difficulties in the Development of Chemical Kinetics in the Twentieth Century 2
1.2 Chemical Kinetics: The Current View 4
References 14
2 Reaction Rate Laws 15
2.1 Reaction Rates 15
2.2 Factors that Influence the Velocities of Reactions 17
2.2.1 Nature of the reagents 17
2.2.2 Reactant concentration 19
2.2.3 Temperature 25
2.2.4 Light 26
2.2.5 Catalysts 29
2.2.6 Reaction medium 30
References 32
3 Experimental Methods 33
3.1 Application of Conventional Techniques to Study Reactions 34
3.1.1 First-order reactions 34
3.1.2 Second-order reactions 36
3.1.3 Complex reactions 39
3.1.4 Activation energy 41
3.1.5 Dependence of light intensity 43
3.1.6 Enzyme catalysis 46
3.1.7 Dependence on ionic strength 47
3.2 Application of Special Techniques for Fast Reactions 50
3.2.1 Flow methods 51
3.2.2 Relaxation methods 52
3.2.3 Competition methods 56
3.2.4 Methods with enhanced time resolution 61
References 75
4 Reaction Order and Rate Constants 77
4.1 Rates of Elementary Reactions 77
4.1.1 First-order reactions 77
4.1.2 Second-order reactions 80
4.1.3 Zero-order reactions 82
4.1.4 Third-order reactions 83
4.2 Rates of Complex Reactions 84
4.2.1 Parallel first-order reactions 85
4.2.2 Consecutive first-order reactions 86
4.2.3 Reversible first-order reactions 88
4.3 Methods for Solving Kinetic Equations 89
4.3.1 Laplace transforms 89
4.3.2 Matrix method 94
4.3.3 Runge鈥揔utta method 97
4.3.4 Markov chains 99
4.3.5 Monte Carlo method 103
4.4 Simplification of Kinetic Schemes 106
4.4.1 Isolation method 106
4.4.2 Pre-equilibrium approximation 107
4.4.3 Steady-state approximation 108
4.4.4 Rate-determining step of a reaction 111
References 113
5 Collisions and Molecular Dynamics 115
5.1 Simple Collision Theory 117
5.2 Collision Cross Section 122
5.3 Calculation of Classical Trajectories 128
5.4 PES Crossings 135
5.5 Molecular Dynamics 137
References 142
6 Reactivity in Thermalised Systems 143
6.1 Transition-State Theory 143
6.1.1 Classical formulation 144
6.1.2 Partition functions 147
6.1.3 Absolute rate calculations 149
6.1.4 Statistical factors 151
6.1.5 Beyond the classical formulation 154
6.2 Semi-Classical Treatments 156
6.2.1 Kinetic isotope effects 156
6.2.2 Tunnel effect 160
6.3 Intersecting-State Model 167
6.3.1 Activation energies 170
6.3.2 Classical rate constants 176
6.3.3 Absolute semi-classical rates 180
6.3.4 Relative rates 183
References 187
7 Relationships between Structure and Reactivity 189
7.1 Quadratic Free-Energy Relationships (QFER) 189
7.2 Linear Free-Energy Relationships (LEER) 193
7.2.1 Br枚nsted equation 194
7.2.2 Bell鈥揈vans鈥揚olanyi equation 196
7.2.3 Hammett and Taft relationships 196
7.3 Other Kinds of Relationships between Structure and Reactivity 202
7.3.1 The Hammond postulate 202
7.3.2 The reactivity鈥搒electivity principle (RSP) 203
7.3.3 Relationships of the electronic effect: equation of Ritchie 205
7.3.4 An empirical extension of the Bell鈥揈vans鈥揚olanyi relationship 205
References 207
8 Unimolecular Reactions 209
8.1 Lindemann鈥揅hristiansen Mechanism 209
8.2 Hinshelwood's Treatment 212
8.3 Rice鈥揜ampsberger鈥揔assel鈥揗arcus (RRKM) Treatment 215
8.4 Local Random Matrix Theory (LRMT) 218
8.5 Energy Barriers in the Isomerisation of Cyclopropane 220
References 222
9 Elementary Reactions in Solution 223
9.1 Solvent Effects on Reaction Rates 223
9.2 Effect of Diffusion 225
9.3 Diffusion Constants 229
9.4 Reaction Control 235
9.4.1 Internal pressure 237
9.4.2 Reactions between ions 240
9.4.3 Effect of ionic strength 244
9.4.4 Effect of hydrostatic pressure 246
References 249
10 Reactions on Surfaces 251
10.1 Adsorption 251
10.2 Adsorption Isotherms 256
10.2.1 Langmuir isotherm 256
10.2.2 Adsorption with dissociation 257
10.2.3 Competitive adsorption 258
10.3 Kinetics on Surfaces 259
10.3.1 Unimolecular surface reactions 259
10.3.2 Activation energies of unimolecular surface reactions 260
10.3.3 Reaction between two adsorbed molecules 261
10.3.4 Reaction between a molecule in the gas phase and an adsorbed molecule 263
10.4 Transition-State Theory for Reactions on Surfaces 263
10.4.1 Unimolecular reactions 263
10.4.2 Bimolecular reactions 265
10.5 Model Systems 268
10.5.1 Langmuir鈥揌inshelwood mechanism 268
10.5.2 Eley鈥揜ideal mechanism 270
References 271
11 Substitution Reactions 273
11.1 Mechanisms of Substitution Reactions 273
11.2 SN2 and SN1 Reactions 274
11.3 Langford鈥揋ray Classification 276
11.4 Symmetrical Methyl Group Transfers in the Gas-Phase 280
11.5 State Correlation Diagrams of Pross and Shaik 282
11.6 Intersecting-State Model 285
11.7 Cross-Reactions in Methyl Group Transfers in the Gas Phase 288
11.8 Solvent Effects in Methyl Group Transfers 289
References 294
12 Chain Reactions 295
12.1 Hydrogen鈥揃romine Reaction 295
12.2 Reaction between Molecular Hydrogen and Chlorine 298
12.3 Reaction between Molecular Hydrogen and Iodine 300
12.4 Calculation of Energy Barriers for Elementary Steps in Hydrogen鈥揌alogens Reactions 301
12.5 Comparison of the Mechanisms of the Hydrogen鈥揌alogen Reactions 303
12.6 Pyrolysis of Hydrocarbons 305
12.6.1 Pyrolysis of ethane 306
12.6.2 Pyrolysis of acetic aldehyde 308
12.6.3 Goldfinger鈥揕etort鈥揘iclause rules 309
12.7 Explosive Reactions 310
12.7.1 Combustion between hydrogen and oxygen 310
12.7.2 Thermal explosions 314
12.7.3 Combustion of hydrocarbons 316
12.8 Polymerisation Reactions 317
References 320
13 Acid鈥揃ase Catalysis and Proton-Transfer Reactions 321
13.1 General Catalytic Mechanisms 321
13.1.1 Fast pre-equilibrium: Arrhenius intermediates 322
13.1.2 Steady-state conditions: van't Hoff intermediates 324
13.2 General and Specific Acid鈥揃ase Catalysis 326
13.3 Mechanistic Interpretation of the pH Dependence of the Rates 329
13.4 Catalytic Activity and Acid鈥揃ase Strength 338
13.5 Salt Effects 342
13.6 Acidity Functions 343
13.7 Hydrated Proton Mobility in Water 345
13.8 Proton-Transfer Rates in Solution 350
13.8.1 Classical PT rates 351
13.8.2 Semiclassical absolute rates 356
References 358
14 Enzymatic Catalysis 361
14.1 Terminology 361
14.2 Michaelis鈥揗enten Equation 363
14.3 Mechanisms with Two Enzyme鈥揝ubstrate Complexes 368
14.4 Inhibition of Enzymes 370
14.5 Effects of pH 373
14.6 Temperature Effects 375
14.7 Molecular Models for Enzyme Catalysis 376
14.8 Isomerisation of Dihydroxyacetone Phosphate to Glyceraldehyde 3-Phosphate Catalysed by Triose-Phosphate 379
14.9 Hydroperoxidation of Linoleic Acid Catalysed by Soybean Lipoxygenase-1 381
References 383
15 Transitions between Electronic States 385
15.1 Mechanisms of Energy Transfer 385
15.2 The "Golden Rule" of Quantum Mechanics 391
15.3 Radiative and Radiationless Rates 395
15.4 Franck鈥揅ondon Factors 400
15.5 Radiationless Transitions within a Molecule 407
15.6 Triplet-Energy (or Electron) Transfer between Molecules 410
15.7 Electronic Coupling 421
15.8 Triplet-Energy (and Electron) Transfer Rates 430
References 434
16 Electron Transfer Reactions 437
16.1 Rate Laws for Outer-Sphere Electron Exchanges 437
16.2 Theories of Electron-Transfer Reactions 440
16.2.1 The classical theory of Marcus 440
16.2.2 Solute-driven and solvent-driven processes 443
16.2.3 Critique of the theory of Marcus 445
16.2.4 ISM as a criterion for solute-driven electron transfers 449
16.3 ISM and Electron-Transfer Reactions 452
16.3.1 Representing ET reactions by the crossing of two potential-energy curves 452
16.3.2 Adiabatic self-exchanges of transition-metal complexes 454
16.3.3 Outer-sphere electron transfers with characteristics of an inner-sphere mechanism 456
16.4 Non-Adiabatic Self-Exchanges of Transition-Metal Complexes 458
16.4.1 A source of non-adiabaticity: orbital symmetry 458
16.4.2 Electron tunnelling at a distance 458
16.4.3 Non-adiabaticity due to spin forbidden processes 459
16.5 Electron Self-Exchanges of Organic Molecules 460
16.6 Inverted Regions 462
16.7 Electron Transfer at Electrodes 469
16.7.1 The Tafel equation 469
16.7.2 Calculations of rate constants 475
16.7.3 Asymmetry in Tafel plots 478
16.7.4 Electron transfer at surfaces through a blocking layer 479
References 482
Appendix I: General Data 485
Appendix II: Statistical Thermodynamics 487
Appendix III: Parameters Employed in ISM Calculations 495
Appendix IV: Semi-classical Interacting State Model 499
IV.1 Vibrationally Adiabatic Path 499
IV.2 Tunnelling Corrections 502
IV.3 Semi-classical Rate Constants 503
References 504
Appendix V: The Lippincott鈥揝chroeder Potential 505
V.1 Lippincott鈥擲chroeder (LS) Potential 505
V.2 The LS鈥揑SM Reaction Path 508
V.3 Rate Constants for Proton Transfer along an H-bond 508
References 509
Appendix VI: Problems 511
Subject Index 543
Chemical kinectics : from molecular structure to chemical reactivity / 1st ed.
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