njit-etd2003-111 - New Jersey Institute of Technology

TABLE OF CONTENTS
Chapter
1 INTRODUCTION
1.1 Background
1.2 Previous Studies
2 THERMOCHEMICAL KINETICS
Page
1
1
3
7
2.1 Overview 7
2.2 Computational Chemistry 8
2.3 Kinetics 10
2.3.1 Lindemann-Hinshelwood Mechanism for Unimolecular Reactions 10
2.3.2 Slater Theory 14
2.3.3 RRK Theory of Unimolecular Reactions 15
2.3.4 RRKM Theory of Unimolecular Reactions 17
2.3.5 Chemical Activation Reactions 17
2.3.6 QRRK Analysis for Unimolecular and Chemical Activation
Reactions 21
3 THERMOCHEMICAL AND KINETIC ANALYSYS OF THE ACETYL
RADICAL + 02 REACTION SYSTEM 24
3.1 Background 24
3.2 Calculation Methods 26
3.2.1 Determination of Enthalpy of Formation 27
3.2.2 Determination of Entropy and Heat Capacity 29
3.2.3 High-Pressure Limit A Factor (Ace) and Rate Constant (1(0.0)
Determination 30
3.2.4 Kinetic Analysis 31
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