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Title:	Reaction mechanisms of hydrocarbon and mercury systems in the atmosphere and in combustion: A theoretical study of thermochemical and kinetic properties
Author:	Auzmendi Murua, Itsaso
View Online:	njit-etd2013-064 (xxxvii, 544 pages ~ 12.6 MB pdf)
Department:	Department of Chemical, Biological and Pharmaceutical Engineering
Degree:	Doctor of Philosophy
Program:	Chemical Engineering
Document Type:	Dissertation
Advisory Committee:	Bozzelli, Joseph W. (Committee chair) Wang, Xianqin (Committee member) Barat, Robert Benedict (Committee member) Simon, Laurent (Committee member) Raman, Sumathy (Committee member)
Date:	2013-05
Keywords:	Thermochemistry Combustion modeling Mercury oxidation Kinetics Hydrocarbon oxidation Halogens
Availability:	Unrestricted
Abstract:	The continuing increase in the world population and the rapidly changing lifestyle and education of this population projects significant increases in energy requirements. Global warming is a worldwide major concern with a very serious potential stress on our climate threatening major changes to the environment. It is, without question, of major importance to improve the efficiency and optimize the current available combustion processes and fuel sources, to develop alternative fuels and to reduce the emissions of toxic pollutants. The objective of this dissertation is to present thermochemical, kinetic and modeling results on two reference fuels (the land vehicle fuel isooctane and the jet fuel JP-10), on smaller cyclic alkanes and ethers, and on the oxidation of mercury by the addition of halogens, in atmospheric and combustion environments. As illustrated in the combustion models developed, a fundamental understanding of the processes can enable optimization, and lead to reductions in pollutant emissions. Molecular geometries, vibration frequencies, internal rotor potentials and thermochemical properties (ΔfHº298, S°(T) and COp(T)) are presented at different ab-initio, density functional theory (DFT) and composite calculation methods, with the use of several basis sets. Kinetic parameters are determined versus pressure and temperature for the chemically activated formation and unimolecular dissociation of the adducts, calculated via the use of multi-frequency quantum RRK analysis for the energy dependent rate constant with Master Equation analysis for fall off. The simulations for the determination of the important reaction paths, identification of main products and determination of combustion characteristics at different process conditions are evaluated. The thermochemical and kinetic properties developed during this work will aid in the optimization of the hydrocarbon fueled engine performance and other applications of the target fuels isooctane and JP-10. Thermochemical properties are developed for use in kinetics on oxidation and unimolecular dissociation of small cyclic alkanes and ethers for use in atmospheric and in combustion reaction mechanisms. Separately the understanding and developed kinetic and thermochemical parameters for mercury halides, and oxyhalides and the interactions of Hg and halides with NOx and SOx will help lead to a reduction of mercury emissions from power generating plants.