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