《FAST REACTIONS IN SOLUTION》求取 ⇩

1Introduction1

Historical and general introduction1

Classification of methods4

Reaction half-times accessible by the various methods6

The energetics of very fast reactions7

Theory of rate constants for diffusion-controlled reactions10

2The Simpler Methods14

Use of low concentrations14

Measurement of equilibrium constant and rate of reverse reaction16

Competition methods17

Low-temperature methods18

The thermal-maximum method23

Quenching methods24

The capacity-flow method26

Electrolytic addition of reagent28

3Flow Methods29

General introduction29

The continuous-flow method29

The accelerated-flow method41

The stopped-flow method43

The baffle method48

Reactions investigated by flow methods49

4Relaxation Methods(Ⅰ):Temperature-jump,Pressure-jump,and Electric-impulse Methods59

Introduction59

Relaxation time and its relation to rate constants60

Temperature-jump method64

Pressure-jump method69

Electric-impulse method71

Comparison of aingle-displacement relaxation methods76

Some general characteristics of relaxation methods77

Mathe-matical theory of damped oscillatory impulses78

5Relaxation Methods(Ⅱ):Ultrasonic-absorption and Related Methods81

General principles81

Ultrasonic-absorption or acoustic methods:principles84

techniques90

some general features94

applications94

High-frequency alternating-field methods102

6Flash and Related Methods104

General principles104

Experimental arrangements105

General comments107

Applications:relaxation studies108

studies of the triplet state111

photochemically-initiated irreversible reactions116

Pulse radiolysis119

7Photochemical and Related Methods121

Introduction:the mechanism of photochemical free-radical polymerization reactions122

determination of k？/kt by conventional photochemical methods123

Determination of the rate constants of polymerization125

The rate constants of polymerization reactions135

The recombination of iodine atoms137

8Fluorescence Methods142

General principles:introduction142

fluorescence quenching142

Experimental investigation of fluorescence:fluorescence intensity149

determination of mean life-time152

General comments on fluorescence methods153

Kinetic applications of fluorescence measurements153

9Electrochemical Methods164

General principles164

Theory of electrochemical methods:coulometry at constant voltage166

voltammetry at controlled current177

Techniques181

General comments184

Applications184

10Electron-spin Resonance(paramagnetie resonance)193

General principles:introduction193

determination of the lifetimes of free radicals198

Experimental study204

Applications207

General comments on e.s.r.methods213

11Nuclear Magnetic Resonance214

General principles:introduction214

experimental determination of n.m.r.spectra221

the structure of proton magnetic resonance spectra223

nuclear-spin relaxation and line-widths in absence of reaction228

the determination of reaction rates from n.m.r.spectra231

General comments237

Kinetic applications of n.m.r.methods239

12Some General Topics in the Mechanisms and Energetics of Reactions in Solution262

Rates and mechanisms of fast proton-transfer reactions262

Replacement of solvent molecules in the coordination shells of metal cations275

Diffusion control of rates of reaction279

Interpretation of Arrhenius energies of activation285

Appendix293

Index294