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Title:	Thermochemical properties of fluorinated hydrocarbons, hydroperoxides, and fluorinated hydroperoxides; thermochemistry and kinetics on dissociation and association reactions of oxiranyl radical
Author:	Wang, Heng
View Online:	njit-etd2016-042 (xx, 217 pages ~ 7.8 MB pdf)
Department:	Department of Chemistry and Environmental Science
Degree:	Doctor of Philosophy
Program:	Chemistry
Document Type:	Dissertation
Advisory Committee:	Bozzelli, Joseph W. (Committee chair) Krasnoperov, Lev N. (Committee member) Gund, Tamara M. (Committee member) Khalizov, Alexei (Committee member) Chen, Chiung-chu (Committee member)
Date:	2016-05
Keywords:	Computational chemistry Combustion chemistry Quantum chemistry Environmental science Atmosphere chemistry Physical chemistry
Availability:	Unrestricted
Abstract:	Thermochemical properties on fluorinated hydrocarbons, alcohol, hydroperoxides, and alkyl hydroperoxides are determined. Reaction kinetics and modeling on the three member ring cyclic ether radical, oxiranyl radical, are studied under atmospheric and combustion environments. Molecular geometries, vibration frequencies, internal rotor potentials, and thermo-chemical properties (ΔfHº298, S°(T) and C°p(T)) for fluorinated-hydrocarbons, thermochemical properties and bond energies, for alkyl and fluoro hydroperoxides and fluoro alcohols are determined with comparison of data from a number of different ab initio, density functional theory (DFT) and composite calculation methods, and basis sets. Kinetic parameters for unimolecular decomposition and isomerization reactions of the oxiranyl radical are determined versus pressure and temperature. Kinetic parameters for chemically activated bimolecular oxidation reaction of the oxiranyl radical with 3O2 are determined for the formation and unimolecular dissociation of the formed peroxy radical. Kinetic calculations use multi-frequency quantum RRK analysis for the energy dependent rate constant with Master Equation analysis for fall-off. Computer modeling for simulation and identification of the primary products, important reaction paths and thermal characteristics under atmospheric and combustion conditions are evaluated. Thermochemical and kinetic properties developed during this work illustrate the effects of fluorine substitution on structures and bonding in C1 to C4 normal hydrocarbons, fluoro-alcohols, fluoro-hydroperoxides based on standard enthalpies of formation and bond dissociation energies. Thermochemical kinetic calculations for the unimolecular dissociation (ring opening) and molecular oxygen oxidation association reactions of oxiranyl radical show important reaction paths and their changes as function of temperature and pressure.