njit-etd2003-111 - New Jersey Institute of Technology

TABLE OF CONTENTS
(Continued)
Chapter
Page
4.2.3
4.2.4
High-Pressure Limit A Factors (Ace) and Rate Constants (k.0)
Determination 73
Kinetic Analysis 74
4.3 Results and Discussion 75
4.3.1 Geometries of Parent Hydroperoxide Aldehyde, Two Intermediate
Radicals and Transition States 75
4.3.2 Enthalpy of Formation (AHe298) using Calculated Total Energies
and Isodesmic Reactions 77
4.3.3 Entropy (V(298)) and Heat Capacity (Cp(T), 300 __ T/K 5 1500) 82
4.3.4 Energy Diagram for C•1-12CHO + 02 Reaction System 82
4.3.5 Comparison of C•l-12CH° + 02, CH3Co0 + 02 and C2H5 + 02 86
4.3.6 Analysis of the C•1-12CHO + 02 Chemical Activation Reaction 86
4.3.7 Abstraction of a Hydrogen from the —CHO Group of
C•1-12CHO by 02 90
4.3.8 Unimolecular Dissociation of Formyl Methyl Peroxy and
Acetyl Hydroperoxide Radicals 94
4.3.9 Formyl Methyl Radical Unimolecular Dissociation 95
4.3.10 Detailed Mechanism of Formyl Methyl Radical Oxidation
Reactions 96
4.3.11 Comparison of C•l-12CH° + 02 with Unimolecular Dissociation of
C•l-12CH° 101
4.4 Summary 104
5 REACTION OF H + KETENE TO FORMYL METHYL RADICAL AND
ACETYL RADICALS AND REVERSE DISSOCIATIONS 106
5.1 Background 106