1 Introduction 1
Historical and general introduction 1
Classification of methods 4
Reaction half-times accessible by the various methods 6
The energetics of very fast reactions 7
Theory of rate constants for diffusion-controlled reactions 10
2 The Simpler Methods 14
Use of low concentrations 14
Measurement of equilibrium constant and rate of reverse reaction 16
Competition methods 17
Low-temperature methods 18
The thermal-maximum method 23
Quenching methods 24
The capacity-flow method 26
Electrolytic addition of reagent 28
3 Flow Methods 29
General introduction 29
The continuous-flow method 29
The accelerated-flow method 41
The stopped-flow method 43
The baffle method 48
Reactions investigated by flow methods 49
4 Relaxation Methods(Ⅰ):Temperature-jump,Pressure-jump,and Electric-impulse Methods 59
Introduction 59
Relaxation time and its relation to rate constants 60
Temperature-jump method 64
Pressure-jump method 69
Electric-impulse method 71
Comparison of aingle-displacement relaxation methods 76
Some general characteristics of relaxation methods 77
Mathe-matical theory of damped oscillatory impulses 78
5 Relaxation Methods(Ⅱ):Ultrasonic-absorption and Related Methods 81
General principles 81
Ultrasonic-absorption or acoustic methods:principles 84
techniques 90
some general features 94
applications 94
High-frequency alternating-field methods 102
6 Flash and Related Methods 104
General principles 104
Experimental arrangements 105
General comments 107
Applications:relaxation studies 108
studies of the triplet state 111
photochemically-initiated irreversible reactions 116
Pulse radiolysis 119
7 Photochemical and Related Methods 121
Introduction:the mechanism of photochemical free-radical polymerization reactions 122
determination of k？/kt by conventional photochemical methods 123
Determination of the rate constants of polymerization 125
The rate constants of polymerization reactions 135
The recombination of iodine atoms 137
8 Fluorescence Methods 142
General principles:introduction 142
fluorescence quenching 142
Experimental investigation of fluorescence:fluorescence intensity 149
determination of mean life-time 152
General comments on fluorescence methods 153
Kinetic applications of fluorescence measurements 153
9 Electrochemical Methods 164
General principles 164
Theory of electrochemical methods:coulometry at constant voltage 166
voltammetry at controlled current 177
Techniques 181
General comments 184
Applications 184
10 Electron-spin Resonance(paramagnetie resonance) 193
General principles:introduction 193
determination of the lifetimes of free radicals 198
Experimental study 204
Applications 207
General comments on e.s.r.methods 213
11 Nuclear Magnetic Resonance 214
General principles:introduction 214
experimental determination of n.m.r.spectra 221
the structure of proton magnetic resonance spectra 223
nuclear-spin relaxation and line-widths in absence of reaction 228
the determination of reaction rates from n.m.r.spectra 231
General comments 237
Kinetic applications of n.m.r.methods 239
12 Some General Topics in the Mechanisms and Energetics of Reactions in Solution 262
Rates and mechanisms of fast proton-transfer reactions 262
Replacement of solvent molecules in the coordination shells of metal cations 275
Diffusion control of rates of reaction 279
Interpretation of Arrhenius energies of activation 285
Appendix 293
Index 294