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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