Fundamentals of Chemistry Kinetics基础化学动力学

Contents Preface x1 Acknowledgements xiii 1 THE EMPIRICAL FRAMEWORK OF CHEMICAL KINETICS 1.1 Introduction 1.2 The rate equation 1.3 Integrated rate equations 1.4 Reaction half-life and mean lifetime 1.5 The determination of reaction order 1.6 Effect of temperature on reaction rates Suggested reading Problems 2 THE EXPERIMENTAL STUDY OF REACTION KINETICS 2.1 Minimum requirements for the study of chemical kinetics 2.2 The evolution of techniques for monitoring reaction progress 2.3 The application of spectrophotometry to chemical kinetics 2.4 Electrical conductivity and dilatometry 2.5 Techniques for the gas phase 2.6 Modern experimental techniques 2.7 The evaluation of the rate constant Suggested reading Problems 3 REACTION MECHAMSM AND REACTION ORDER 3.1 An elementary reaction and the molecularity 3.2 Consecutive reaction processes 3.3 Formation of an intermediate complex 3.4 The "third body" effect in atom recombination 3.5 Parallel reactions 3.6 Reactant participating in equilibria 3.7 Opposing reactions 3.8 Isotopic exchange reactions Suggested reading Problems 4. THEORIES OF BIMOLECULAR REACTIONS 4.1 The Collision Theory 4.2 Transition State Theory 4.3 The theory of diffusion-controlled reactions in solution Suggested reading Problems 5 THE INTERPRETATION OF BIMOLECULAR REACTIONS IN SOLUTION 5.1 Solvent effects on reaction rates 5.2 Applied hydrostatic pressure 5.3 Dielectric permittivity 5.4 lonic strength 5.5 Linear free energy relationships 5.6 Kinetic isotope effects 5.7 Electron transfer reactions in solution Suggested reading Problems 6 UNIMOLECULAR GAS PHASE REACTIONS 6.1 The kinetic results 6.2 The Lindemann mechanism 6.3 The RRK (or Kassel) theory 6.4 The RRKM theory Suggested reading Problems 7 CHAIN REACTIONS 7.1 Linear chain reactions 7.2 Pyrolysis reactions involving chain mechanisms 7.3 Chain polymerisation: free radical processes 7.4 Chain polymerisation: ionic processes 7.5 Less simple linear chain reactions 7.6 Branching chains and explosion phenomena Suggested reading Problems 8 HETEROGENEOUS CATALYSIS 8.1 Introduction 8.2 Chemisorption and the chemisorbed state 8.3 The Langmuir adsorption isotherm 8.4 Reactions on a catalyst surface 8.5 Catalytic exchange of alkanes with deuterium 8.6 The catalytic oxidation ofcarbon monoxide 8.7 Catalytic synthesis and decomposition of ammonia 8.8 The criterion for a good catalyst 8.9 Catalysis in industry Suggested reading Problems 9 HOMOGENEOUS CATALYSIS 9.1 Gas phase catalysis 9.2 Catalysis in solution 9.3 Catalysis by acids 9.4 Catalysis by bases 9.5 Autocatalysis 9.6 Oscillating reactions 9.7 Catalysis by enzymes 9.8 Enzyme inhibitors Suggested reading Problems 10 RELAXATION AND OTHER ADVANCED TECHNIQUES 10.1 Introduction 10.2 Relaxation techniques: experimental aspects 10.3 More complex reaction systems 10.4 NMR spectroscopy 10.5 Electrochemical methods Suggested reading Problems 11 PHOTOCHEMISTRV AND RADIATION CHEMISTRY 11.1 Initial effects of light absorption 11.2 Photochemical kinetics 11.3 Flash photolysis 11.4 Primary effects of ionising radiations 11.5 Radiation chemistry of aqueous solutions 11.6 Pulse radiolysis Suggested reading Problems 12 REACTION DYNAMICS 12.1 Introduction 12.2 Studies using crossed molecular beams 12.3 Energy distribution within the reaction products 12.4 lon-molecule reactions 12.5 Dynamics of ion-molecule reactions Suggested reading X Cwtenls APPENDIXA APPENDIX B ANSWERS TO THE PROBLEMS INDEX INDEX OF CHEMICAL BEACTIONS