Kinetic Studies of the Reactions of Alkyl and Silyl Hydrides Page: IV
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TABLE OF CONTENTS
Page
LIST OF TABLES ......................................................v
LIST OF ILLUSTRATIONS.............................................viii
Chapter
1. INTRODUCTION.................................................1
A. Basic Properties of Silicon and Carbon..............................1
B. Major Methods to Determine R-H Bond Dissociation Enthalpies..........2
Radical Kinetics /Equilibria....................................3
Association / Dissociation Equilibria.............................4
Photoionization Mass Spectrometry..............................7
C. Background to the Research ......................................9
2. EXPERIMENTAL METHOD.......................................13
A. Flash Photolysis / Resonance Fluorescence (FP-RF) Technique..........13
B. Kinetic Experimental Procedure ..................................15
C. HBr UV Absorption Experiments..................................17
D. Laser-Photolysis / Resonance Fluorescence (LP-RF) Technique..........17
E. Materials.....................................................18
F. Data Analysis .................................................20
3. KINETICS AND THERMOCHEMISTRY OF ALKYL AND SILYL
RADICALS .....................................................28
A. HBr Absorption Cross Section (e) Determination ..................28
B. Kinetic Study Results And Discussion..............................31
Comparison of Alkyl + HBr Rate Constants with Prior
Determinations.......................................32
Study of the Trimethylsilyl + HBr Reaction ......................35
Study of the Br + Si2H6 Reaction. For the reaction .................36
C. Thermochemical Calculations ....................................38
Theoretical Background......................................38
Calculations of C-H Bond Energies.............................42
Comparison of C-H Bond Strength of Alkanes with Values Obtained in
Previous Studies......................................46
IV
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Yuan, Jessie (Jessie Win-Jae). Kinetic Studies of the Reactions of Alkyl and Silyl Hydrides, dissertation, August 1996; Denton, Texas. (https://digital.library.unt.edu/ark:/67531/metadc277864/m1/6/: accessed July 18, 2024), University of North Texas Libraries, UNT Digital Library, https://digital.library.unt.edu; .