| Preface vii |
| Part I General Theory |
| 1 The Nature of Chemical Kinetics 3 |
| 1.1 What Is Chemical Kinetics? 3 |
| 1.2 How to Describe Chemical Reaction Rates? 4 |
| 1.3 Can the Rate Equation Be Predicted from the Chemical Equation? 5 |
| 1.4 Rate Equation of Reverse Reaction 7 |
| References 9 |
| 2 Thermodynamics of Chemical Reactions 11 |
| 2.1 The Chemical Equation of Reaction Is the Law of Conservation of Mass 11 |
| 2.2 Thermodynamic Definition of Reactions 11 |
| 2.3 Chemical Affinity: Thermodynamic Force of Reaction 12 |
| 2.4 Gibbs Energy of Chemical Reaction 15 |
| 2.5 Chemical Affinity in 1806 16 |
| 2.6 Applications of Chemical Affinity: Direction of Chemical Changes 18 |
| References 19 |
| 3 Experimental Methods and Treatment of Data 21 |
| 3.1 Principle of Rate Measurements 21 |
| 3.2 Treatment of Rate Data 22 |
| 3.3 A Kinetic Measurement of Ethene Hydrogenation with H4Ru4(CO)12 24 |
| 3.3.1 Apparatus and Procedure 25 |
| 3.3.2 Reaction between H4Ru4(CO)12 and Ethene 26 |
| 3.3.3 Catalytic Hydrogenation 27 |
| References 33 |
| 4 Theory of Complex Reactions: Reaction Path 35 |
| 4.1 Complex Reactions and Elementary Reactions 35 |
| 4.2 Theory of Reaction Path 36 |
| 4.3 Quasi-stationary State Approximation 38 |
| References 39 |
| 5 Theory of Elementary Reactions 41 |
| 5.1 Starting Point of the Theory of Elementary Reactions: The Arrhenius Equation Is an Approximation of the van't Hoff Equation 41 |
| 5.2 Kinetic Data 46 |
| 5.3 McC. Lewis' Collision Theory of Active Molecules 48 |
| 5.4 Active Molecule and Critical Colliding State 49 |
| 5.5 Potential Energy Surfaces 52 |
| 5.6 Eyring's Theory of Activated Complex 56 |
| 5.7 Activation Free Energy and Entropy 59 |
| References 62 |
| 6 Coordination Equilibrium and Kinetics 63 |
| 6.1 Horiuti's Theory 63 |
| 6.1.1 Definition and Theorems 63 |
| 6.1.2 Rates of Elementary Reactions 64 |
| 6.2 Coordination Equilibrium 68 |
| 6.2.1 Ideal Coordination 68 |
| 6.2.2 Induced Coordination 70 |
| 6.2.3 Coordination on Cluster of Sites 71 |
| 6.2.4 Coordination on Nonuniform Surface Sites 75 |
| 6.2.5 Relation between Two Models of Coordination on Uniform and Nonuniform Sites 76 |
| 6.2.6 Theory of Coordination on Nonuniform Sites 78 |
| 6.3 Coordination Reactions 81 |
| 6.3.1 Turnover Frequency 81 |
| 6.3.2 Michaelis-Menten Equatlon 83 |
| 6.3.3 Relation between Energies of Coordination and Activation 85 |
| References 85 |
| Part II Kinetics of Ziegler-Natta-Kaminsky Polymerization |
| 7 Traditional Kinetics of Ziegler-Natta-Kaminsky Polymerization 89 |
| 7.1 Historical Introduction 89 |
| 7.2 Kinetic Observables and Variables 91 |
| 7.2.1 Rate of Polymerization 91 |
| 7.2.2 Molecular Weight Distribution 92 |
| 7.2.3 Polymerization Time 94 |
| 7.3 Traditional Kinetics 97 |
| 7.3.1 Ideal Kinetic Model: Stationary Rate and MWD 97 |
| 7.3.2 Extension of the Ideal Model 102 |
| 7.3.3 Plausibility and Uncertainty of Traditional Kinetics 108 |
| References 111 |
| 8 Coordination Kinetics of Ziegler-Natta-Kaminsky Polymerization 113 |
| 8.1 Critical State and Its Initial States 113 |
| 8.2 Monomer Concentration in Solution or Partial Pressure in Gas Phase: Which Is Better as a Kinetic Variable? 116 |
| 8.3 Coordination Kinetics of Elementary Reactions of Growing Polymers: Which Is the Rate-determining Step, Coordination or Insertion? 118 |
| 8.4 Transfer Reaction by Monomer and the First Monomer Insertion 121 |
| 8.5 Solvent Effect 124 |
| 8.6 Coordination Kinetics of Copolymerization 127 |
| References 129 |
| 9 Homogeneous Polymerization 131 |
| 9.1 Living Polymerization of Propene with V(acac)3/AIR2X Catalysts 131 |
| 9.1.1 Principal Kinetics of Living Polymerization with V(acac)3/Al(C2H5)2Cl 133 |
| 9.1.2 Further Analysis in Accordance with Coordination Kinetics 136 |
| 9.1.3 Reactions of Living Polypropylene with Additive 140 |
| 9.2 Pseudo-living Polymerization of Propene with Soluble Catalysts 145 |
| 9.2.1 Ethene Polymerization with Cp2Ti(C2H5)Cl/Al(C2H5)Cl2 145 |
| 9.2.2 MMA Polymerization with Me2C(Cp)(Ind)Zr(Me)(thf)+BPh4- 146 |
| 9.3 Stationary Propene Polymerization with Vanadium-based Catalysts 151 |
| 9.3.1 Molecular Weight Distribution at Elevated Temperatures 155 |
| 9.4 Kinetics of Polymerization with Metallocene/MAO Catalysts－Trigger, Single-site Two-state or Slow-initiation Model 156 |
| 9.4.1 Kinetic Features and Topics of Kaminsky Polymerization 157 |
| 9.4,2 Trigger Model and Slow-initiation Model 159 |
| 9.4.3 Single-site Two-state Model 160 |
| References 161 |
| 10 Propene Polymerization with Heterogeneous Ziegler-Natta Catalysts: TiCl3-and MgCl2-supported TiCl4 Catalysts 163 |
| 10.1 Transitional Analysis of Mass Transfer 163 |
| 10.1.1 Pure Polymerization Rate Free from Mass Transfer Effect 167 |
| 10.2 Kinetic Behavior of TiCl3/Al(C2H5)2Y(Y=C2H5, H, Cl, Br, I) 168 |
| 10.2.1 Polymerization Rate during Polymerization 169 |
| 10.2.2 Temperature Dependence of the Stationary Rate 178 |
| 10.2,3 Effect of Hydrogen Addition 179 |
| 10.3 Elimination and Substitution of Cocatalyst during Polymerization: Kinetic Relaxation Method 179 |
| 10.3.1 Rate of Polymerization after Elimination of Cocatalyst 180 |
| 10.3.2 Reversible Changes in the Kinetic Curve with Cocatalyst Substitutions 183 |
| 10.3.3 Pretreatment of TiC13 with Various Halide Compounds 187 |
| 10.3.4 MWDs during Polymerization 188 |
| 10.3.5 Effects of Temperature, Hydrogen Pressure, Monomer Pressure and Cocatalyst Concentration 190 |
| 10.4 MgCl2-supported TiCl4/Al(C2H5)3 Catalyst 192 |
| 10.4.1 Dependence of Polymerization Rate on Time 193 |
| 10.4.2 Kinetic Behavior during Polymerization 195 |
| 10.4.3 Effect of External Electron Donor 202 |
| 10.4,4 Elimination of Cocatalyst during Polymerization 203 |
| 10.4.5 Quasi-living Stages 203 |
| 10.5 Radio-CO Tagging Method and CO Quenching Method 205 |
| References 213 |
| 11 Kinetic Mechanism of Molecular Weight Distribution and Isotacticity 215 |
| 11.1 Kinetic Features of Molecular Weight Distribution and Isotacticity 215 |
| 11.2 Rival Theories of Broad MWDS 216 |
| 11.2.1 Broad MWDS in the Stationary State 216 |
| 11.2.2 Experimental Test of Rival Theories for Stationary Broad MWDs 223 |
| 11.2.3 MWDs during Quasi-living Polymerization 226 |
| 11.2.4 Possible Kinetic Models of Broadening MWDs 230 |
| 11.3 Kinetic Model of Isotacticity 233 |
| 11.3.1 Characterization of Stereoregularity 233 |
| 11.3.2 Kinetic Models of Stereospecificity 240 |
| References 243 |
| Index 245 |
| Preface vii |
| Part I General Theory |
| 1 The Nature of Chemical Kinetics 3 |
| 1.1 What Is Chemical Kinetics? 3 |
| 1.2 How to Describe Chemical Reaction Rates? 4 |
| 1.3 Can the Rate Equation Be Predicted from the Chemical Equation? 5 |
