Investigations of Thermochemistry and the Kinetics of H Atom Radical Reactions

The thermochemistry of several species, and the kinetics of various H atom radical reactions relevant to atmospheric and combustion chemistry were investigated using ab initio theoretical techniques and the flash photolysis / resonance fluorescence technique. Using ab initio quantum mechanical calculations up to the G3 level of theory, the C-H bond strengths of several alkanes were calculated. The bond strengths were calculated using two working reactions. From the results, it is apparent that the bond strengths decrease as methyl groups are added to the central carbon. The results are in good agreement with recent experimental halogenation kinetic studies. Hydrogen bond strengths with sulfur and oxygen were studied via CCSD(T) theory, together with extrapolation to the complete basis set limit. The results for the bond dissociation energies (ground state at 0 K, units: kJ mol-1) are: S-H = 349.9, S-D = 354.7, HS-H = 376.2, DS-D = 383.4, and HO-H = 492.6. These data compare well with experimental literature. The rate constants for the isotopic reactions of H + H2S, D + H2S, H + D2S, and D + D2S are studied at the QCISD(T)/6-311+G(3df,2p) level of theory. The contributions of the exchange reaction versus abstraction are examined through transition state theory. The energy of NS was computed via CCSD(T) theory, together with extrapolation to the complete basis set limit. The results were employed with three working reactions to find ΔfH0(NS) = 277.3 ± 2 kJ mol-1 and ΔfH298(NS) = 278.0 ± 2 kJ mol-1. This thermochemistry is consistent with, but much more precise than, earlier literature values. A kinetic study of the reaction of H + CH2CCl2 was conducted over the temperature range of 298 - 680 K. The reaction was found to be pressure dependent and results of the rate constants and their interpretation via unimolecular rate theory are presented.

Grantor dc:publisher

University of North Texas

Year dc:date

2002

Author dc:creator

• Peebles, Lynda Renee

Contributors dc:contributor

• Marshall, Paul, 1960-
• Desiderato, Robert
• Braterman, Paul S.
• Thomas, Ruthanne D.

• Thermochemistry.
• Chemical kinetics.
• Chemical bonds.
• Chemical reactions.
• CCSD(T) theory
• thermochemistry
• bond strength
• kinetics

Statement dc:rights

• Use restricted to UNT Community
• Copyright
• Peebles, Lynda Renee
• Copyright is held by the author, unless otherwise noted. All rights reserved.

Language dc:language

English

Identifier

oclc: 52061458
https://digital.library.unt.edu/ark:/67531/metadc3275/
ark: ark:/67531/metadc3275

OAI identifier oai:identifier

info:ark/67531/metadc3275