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)i2 ........................................ 24
3.3.1. Apparatus and Procedure ......................... 25
3.3.2. Reaction between H4Ru4(CO)i2 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 Equation ....................... 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 ................................................. 1ll
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/A1R2X Catalysts .............................. 131
9.1.1. Principal Kinetics of Living Polymerization
with V(acac)3/A1(C2H5)2C1 ....................... 133
9.1.2. Further Analysis in Accordance with
Coordination Kinetics .......................... 136
9.1.3. Reactions of Living Polypropylene with
Additives ...................................... 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
xii. Contents
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: TiCb-and MgCb-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 Т1С13/А1(С2Н5)2Y
(Y= C2H5, H, CI, 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 TiCb 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.MgCb-supported ТЮ4/А1(С2Н5)з 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-C*0 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
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