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東工大
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東工大
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1. 反応速度論. 第3版
慶伊富長著
出版情報: 東京 : 東京化学同人, 2001.2  vii, 126p ; 22cm
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1.反応速度論の性格 1
   1・1 反応速度論は 1
   1・2 反応速度をどう表わすか 3
   1・3 反応式から速度式を予測できるか 6
   1・4 逆反応の速度式 9
2.反応系の熱力学 12
   2・1 反応式は質量不変則である 12
   2・2 反応の熱力学的定義 13
   2・3 反応の駆動力:化学親和力 15
3.速度の測定 20
   3・1 速度の定義と測定原理 20
   3・2 速度測定と精度 24
   3・3 速度式の決め方 26
   3・4 活性化エネルギーの決め方 32
4.反応経路の理論 34
   4・1 単純反応と複合反応 34
   4・2 複合反応の速度:定常状態近似 36
   4・3 定常状態近似 39
   4・4 反応経路と素反応 43
   4・5 反応経路の水槽モデル 48
   4・6 可逆反応(平衡付近の反応)の理論 50
5.素反応の理論 54
   5・1 素反応と分子数 54
   5・2 素反応の速度定数 55
   5・3 素反応の衝突理論 58
6.絶対反応速度論(遷移状態法) 63
   6・1 アレニウスの速度理論 63
   6・2 臨界衝突状態とアレニウスの活性分子 66
   6・3 平衡定数の統計熱学表示 68
   6・4 絶対反応速度論 75
   6・5 活性錯合体と臨界系 79
   6・6 活性化エネルギーと活性化エントロピー 81
   6・7 絶対反応速度論の有効性と理論的地位 84
   6・8 反応ポテンシャル曲面 92
7.気相反応 96
   7・1 単分子反応 96
   7・2 分子線による反応の研究(分子線交差法) 98
   7・3 連鎖反応と爆発反応 99
   7・4 衝撃波による反応研究 103
   8.溶液反応 105
   8・1 溶液反応の拡散衝突説 105
   8・2 T-ジャンプ法 109
   8・3 溶液反応の速度論 110
9.不均一系触媒反応,酵素反応 111
   9・1 触媒反応 111
   9・2 固体触媒反応 112
   9・3 不均一系反応の速度理論 119
   9・4 酵素反応 120
10.重合反応 126
   10・1 重合反応 126
   10・2 重合反応の速度論 129
   10・3 共重合反応の速度 135
   10・4 ラジカル重合の素反応速度定数 138
11.反応機構 140
   11・1 トレーサー法 141
   11・2 経験則LFER 141
参考書 147
索引 149
1.反応速度論の性格 1
   1・1 反応速度論は 1
   1・2 反応速度をどう表わすか 3
2.

図書

東工大
目次DB
図書
東工大
目次DB
2. Heterogeneous kinetics : theory of Ziegler-Natta-Kaminsky polymerization (Kodansha ; Springer)
Tominaga Keii
出版情報: Tokyo : Kodansha , Berlin : Springer, c2004  xiii, 249 p. ; 25 cm
シリーズ名: Springer series in chemical physics ; 77
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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
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