Thermochemistry and kinetics of the 2-butanone-4-yl CH3C(=O)CH2CH2• + O2 reaction system |
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Authors: | N Sebbar J W Bozzelli D Trimis H Bockhorn |
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Institution: | 1. KIT- Karlsruhe Institute of Technology, Engler-Bunte-Institut, Karlsruhe, Germany;2. Department of Chemical Engineering, Chemistry and Environmental Science, New Jersey Institute of Technology, Newark, New Jersey |
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Abstract: | Thermochemistry and kinetic pathways on the 2-butanone-4-yl (CH3C(=O)CH2CH2•) + O2 reaction system are determined. Standard enthalpies, entropies, and heat capacities are evaluated using the G3MP2B3, G3, G3MP3, CBS-QB3 ab initio methods, and the B3LYP/6-311g(d,p) density functional calculation method. The CH3C(=O)CH2CH2• radical + O2 association reaction forms a chemically activated peroxy radical with 35 kcal mol−1 excess of energy. The chemically activated adduct can undergo RO−O bond dissociation, rearrangement via intramolecular hydrogen transfer reactions to form hydroperoxide-alkyl radicals, or eliminate HO2 and OH. The hydroperoxide-alkyl radical intermediates can undergo further reactions forming ketones, cyclic ethers, OH radicals, ketene, formaldehyde, or oxiranes. A relatively new path showing a low barrier and resulting in reactive product sets involves peroxy radical attack on a carbonyl carbon atom in a cyclic transition state structure. It is shown to be important in ketones when the cyclic transition state has five or more central atoms. |
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Keywords: | ab initio butanone oxidation reaction pathways thermochemistry |
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