NJIT eTD::njit-etd1999-072::Lee, Jongwoo::"Thermodynamic and kinetic analysis on CI.+RCI -- CI2+R.reactions, CH3CjO+O2= products and CjCHO+O2= products"

Thermodynamic Parameters, ΔH^o_f(298),S^o₍₂₉₈₎ and Cp(T) are evaluated for C₁ and C₂ chlorocarbon molecules and radicals. These thermodynamic properties are used in evaluation and comparison of R.+ Cl₂ => R-Cl + Cl. (defined forward direction) reaction rate constants from the kinetics literature. Data from some 20 reactions in the literature show linearity on a plot of Ea_fwd vs. ΔH_rxn,fwd, yielding a slope of (0.38 ± 0.04) and intercept of (10.10 ± 0.77) kcal/mole. Thermodynamic properties (ΔH^o₍₂₉₈₎, S^o₍₂₉₈₎ and Cp(T) from 300 to 1500 K) for reactants, adducts, transition states, and products in reactions of CH₃ and C₂H₅ with Cl₂ are calculated using CBSQ//MP2/6-311G(d,p). Evaluated thermodynamic property data are presented for all isomers of the stable molecules CH₃Cl, CH₂Cl₂, CHCl₃, CC1₄, C₂H₅Cl, C₂H₄Cl₂, C₂H₃Cl₃, C₂H₂CI₄, C₂HCl₅, C₂Cl₆, C₂H₃Cl, C₂H₂C2₂, C₂HCl₃, and C₂Cl₄. Evaluated thermodynamic property data are also presented for the alkyl radicals, (including isomers) C·H₂CL·, C·HCl₂, C·Cl₃, C₂H₄Cl·, C₂H₃Cl₂·, C₂H₂Cl₃·, C₂HCl₄·, and C₂Cl₅·, for the olefin radicals (including isomers) C₂H₂Cl·, C₂HCl₂·, and C₂Cl₃·.

Thermodynamic property and chemical kinetic analysis are performed on reactants, intermediates, transition states and products from reactions of the two radicals resulting via H atom abstraction from acetaldehyde: CH₃CjO and CjCHO with molecular oxygen.Density functional and ab initio calculations are utilized to estimate thermodynamic properties: ΔH _f^o₂₉₈ , and Cp^o(T) 300 - 1500K. Rate constants are estimated as a function of temperature and pressure using QRRK analysis for k(E) and modified strong collision analysis for fall-off for application to atmospheric and combustion kinetic modeling.

The important reaction paths are determined as:

CH₃CjO + O₂ ---> CH 2CO + HO₂ via HO₂ Elimination

CH₃CjO + O₂ ---> CyCOCO=O + OH via OH Elimination

CH₃CjO + O₂ ---> CCOQj (Stabilization)

CjCHO + O₂ ---> CO + C.H₂OOH via H shift (C.H₂OOH rapidly decays to CH₂O + OH)

CjCHO + O₂ ---> CQjCHO (Stabilization)

Title:	Thermodynamic and kinetic analysis on Cl.+RCl -- Cl₂+R.reactions, CH₃CjO+O₂= products and CjCHO+O₂= products
Author:	Lee, Jongwoo
Document Type:	Thesis
Department:	Department of Chemical Engineering, Chemistry and Environmental Science
Degree:	Master of Science
Major:	Chemical Engineering
Advisory Committee:	Bozzelli, Joseph W. Pfeffer, Robert Barat, Robert Benedict
Thesis Date:	1999, May
Keywords:	Molecular orbitals. Chemical kinetics. Thermochemistry.
Availability:	Unrestricted
Abstract:	Thermodynamic Parameters, ΔH^o_f(298),S^o₍₂₉₈₎ and Cp(T) are evaluated for C₁ and C₂ chlorocarbon molecules and radicals. These thermodynamic properties are used in evaluation and comparison of R.+ Cl₂ => R-Cl + Cl. (defined forward direction) reaction rate constants from the kinetics literature. Data from some 20 reactions in the literature show linearity on a plot of Ea_fwd vs. ΔH_rxn,fwd, yielding a slope of (0.38 ± 0.04) and intercept of (10.10 ± 0.77) kcal/mole. Thermodynamic properties (ΔH^o₍₂₉₈₎, S^o₍₂₉₈₎ and Cp(T) from 300 to 1500 K) for reactants, adducts, transition states, and products in reactions of CH₃ and C₂H₅ with Cl₂ are calculated using CBSQ//MP2/6-311G(d,p). Evaluated thermodynamic property data are presented for all isomers of the stable molecules CH₃Cl, CH₂Cl₂, CHCl₃, CC1₄, C₂H₅Cl, C₂H₄Cl₂, C₂H₃Cl₃, C₂H₂CI₄, C₂HCl₅, C₂Cl₆, C₂H₃Cl, C₂H₂C2₂, C₂HCl₃, and C₂Cl₄. Evaluated thermodynamic property data are also presented for the alkyl radicals, (including isomers) C·H₂CL·, C·HCl₂, C·Cl₃, C₂H₄Cl·, C₂H₃Cl₂·, C₂H₂Cl₃·, C₂HCl₄·, and C₂Cl₅·, for the olefin radicals (including isomers) C₂H₂Cl·, C₂HCl₂·, and C₂Cl₃·. Thermodynamic property and chemical kinetic analysis are performed on reactants, intermediates, transition states and products from reactions of the two radicals resulting via H atom abstraction from acetaldehyde: CH₃CjO and CjCHO with molecular oxygen.Density functional and ab initio calculations are utilized to estimate thermodynamic properties: ΔH _f^o₂₉₈ , and Cp^o(T) 300 - 1500K. Rate constants are estimated as a function of temperature and pressure using QRRK analysis for k(E) and modified strong collision analysis for fall-off for application to atmospheric and combustion kinetic modeling. The important reaction paths are determined as: CH₃CjO + O₂ ---> CH 2CO + HO₂ via HO₂ Elimination CH₃CjO + O₂ ---> CyCOCO=O + OH via OH Elimination CH₃CjO + O₂ ---> CCOQj (Stabilization) CjCHO + O₂ ---> CO + C.H₂OOH via H shift (C.H₂OOH rapidly decays to CH₂O + OH) CjCHO + O₂ ---> CQjCHO (Stabilization)
Complete Thesis:	njit-etd1999-072 (222 pages ~ 13,021 KB pdf)
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