INORGANIC REACTION MECHANISMS AN INTRODUCTIONPDF电子书下载

Chapter 1 INTRODUCTION 1

1-1 The Subject of this Book 1

1-2 Stoichiometry 2

1-3 Equilibria 3

1-4 Reaction Rate 5

1-5 Transition-State Theory 8

1-6 Order and Reaction Mechanism 10

1-7 Symbols 11

Chapter 2 BINDING STRENGTH AND REACTION RATES:ACIDS,BASES,AND SOLVENTS 14

2-1 Bronsted Theory 14

2-2 Specific-Acid Catalysis 15

2-3 General-Acid Catalysis 17

2-4 Bronsted Equation 18

2-5 Statistical Corrections 20

2-6 Lewis Theory 22

2-7 Other Definitions 24

2-8 General Influence of Solvents 25

2-9 Physical Properties of Solvents 26

2-10 Chemical Nature of Solvents 28

Chapter 3 BINDING STRENGTH AND REACTION RATES:LINEAR FREE-ENERGY RELA-TIONS 31

3-1 Linear Free-Energy Relations 32

3-2 Assumptions 36

3-3 Mathematical Form 37

3-4 Examples of LFER 37

3-5 Problems with LFER 40

3-6 Intermediates 45

3-7 Kinetic Isotope Effects 46

Chapter 4 NUCLEOPHILIC DISPLACEMENTS 51

4-1 Types of Mechanism 51

4-2 Rate Scales 53

4-3 Rate Factors 54

4-4 Orders of Nucleophilic Character 57

4-5 Displacements on Phosphorus 59

4-6 Displacements in Planar Complexes 63

4-7 Discussion 68

Chapter 5 NONRADICAL MECHANISMS FOR PEROXIDE REACTIONS 73

5-1 Nucleophilic Displacements 73

5-2 Peroxyanions as Nucleophiles 81

5-3 Peroxyanions as Leaving Groups 82

5-4 Peroxide Decomposition 84

5-5 Hypohalite Reactions 88

Chapter 6 REPLACEMENTS IN OCTAHEDRAL COMPLEXES 90

6-1 Labile and Inert Complexes 90

6-2 Crystal-Field Stabilization 92

6-3 General Aspects 95

6-4 Dissociation vs．Displacement 100

6-5 Base Hydrolysis 103

6-6 Chromium(Ⅲ)Compounds 107

6-7 Complexes of Divalent Cations 112

Chapter 7 ELECTRON-TRANSFER REACTIONS OF COMPLEXES 115

7-1 Electron-Transfer Theory 115

7-2 Outer-Sphere Exchange Reactions 118

7-3 Bridge Mechanism 120

7-4 Iron(Ⅱ)—Iron(Ⅲ)Exchange 125

7-5 Two-Electron Transfers 127

7-6 Noncomplementary Reactions 128

7-7 Replacement through Redox Mechanism 132

Chapter 8 REACTIONS OF OXYANIONS 137

8-1 Factors Affecting Rates 137

8-2 Oxygen Exchange 142

8-3 Exchange between Phosphate and Water 145

8-4 Induced Reactions 146

8-5 Chromate-Arsenite Reaction 149

8-6 Urea-Formation Reaction 151

Chapter 9 FREE RADICAL REACTIONS 154

9-1 Steady-State Approximation 155

9-2 Decomposition of Persulfate 155

9-3 Dinitrogen Pentoxide Decomposition 158

9-4 Chain Reactions 160

9-5 Hydrogen-Bromine Reaction 163

9-6 Other Hydrogen-Halogen Reactions 166

9-7 Persulfate-Peroxide Reaction 170

Chapter 10 SOME UNSOLVED PROBLEMS 174

10-1 General Problems 174

10-2 Constituents of a Rate Law 175

10-3 Trace-Metal Catalysis 176

10-4 Problems in Phosphorus Displacements 177

10-5 Replacements in Coordination Compounds 180

10-6 Nitrosation Reactions 181

10-7 Some Reactions to Study 183

Index 185