Page 13 - Introduction to chemical reaction engineering and kinetics

Contents xiii

5.6 Complexities Combined 106
56.1 Concept of Rate-Determining Step (rds) 106
56.2 Determination of Reaction Network 106
5.7 Problems for Chapter 5 108

6 . FUNDAMENTALS OF REACTION RATES 115
6.1 Prelhninary Considerations 115
6.1.1 Relating to Reaction-Rate Theories 115
6.1.2 Relating to Reaction Mechanisms and Elementary Reactions 116
6.2 Description of Elementary Chemical Reactions 117
6.2.1 Types of Elementary Reactions 117
6.2.2 General Requirements for Elementary Chemical Reactions 120
6.3 Energy in Molecules 120
6.3.1 Potential Energy in Molecules-Requirements for Reaction 120
6.3.2 Kinetic Energy in Molecules 126
6.4 Simple Collision Theory of Reaction Rates 128
6.4.1 Simple Collision Theory (XT) of Bimolecular Gas-Phase Reactions 129
6.4.2 Collision Theory of Unimolecular Reactions 134
6.4.3 Collision Theory of Bimolecular Combination Reactions; Termolecular
Reactions 137
6.5 Transition State Theory (TST) 139
6.5.1 General Features of the TST 139
6.5.2 Thermodynamic Formulation 141
6.5.3 Quantitative Estimates of Rate Constants Using TST with Statistical Mechanics 143
6.5.4 Comparison of TST with SCT 145
6.6 Elementary Reactions Involving Other Than Gas-Phase Neutral Species 146
6.6.1 Reactions in Condensed Phases 146
6.6.2 Surface Phenomena 147
6.6.3 Photochemical Elementary Reactions 149
6.6.4 Reactions in Plasmas 150
6.7 Summary 151
6.8 Problems for Chapter 6 152

7 . HOMOGENEOUS REACTION MECHANISMS AND RATE LAWS 154
7.1 Simple Homogeneous Reactions 155
7.1.1 Types of Mechanisms 155
7.1.2 Open-Sequence Mechanisms: Derivation of Rate Law from Mechanism 155
7.1.3 Closed-Sequence Mechanisms; Chain Reactions 157
7.1.4 Photochemical Reactions 163
7.2 Complex Reactions 164
7.2.1 Derivation of Rate Laws 164
7.2.2 Computer Modeling of Complex Reaction Kinetics 165
7.3 Polymerization Reactions 165
7.3.1 Chain-Reaction Polymerization 166
7.3.2 Step-Change Polymerization 168
7.4 Problems for Chapter 7 170

8 . CATALYSIS AND CATALYTIC REACTIONS 176
8.1 Catalysis and Catalysts 176
81.1 Nature and Concept 176
81.2 Types of Catalysis 178
81.3 General Aspects of Catalysis 179
~ 8.2 Molecular Catalysis 182
8.2.1 Gas-Phase Reactions 182
8.2.2 Acid-Base Catalysis 183