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Thermochemistry and kinetics of the 2‐butanone‐4‐yl CH 3 C(=O)CH 2 CH 2 • + O 2 reaction system
Author(s) -
Sebbar N.,
Bozzelli J. W.,
Trimis D.,
Bockhorn H.
Publication year - 2019
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.21276
Subject(s) - chemistry , thermochemistry , radical , ketene , intramolecular force , isodesmic reaction , transition state , standard enthalpy of formation , bond dissociation energy , hydrogen atom abstraction , hydrogen atom , alkyl , arrhenius equation , medicinal chemistry , photochemistry , dissociation (chemistry) , activation energy , organic chemistry , catalysis
Thermochemistry and kinetic pathways on the 2‐butanone‐4‐yl (CH 3 C(=O)CH 2 CH 2 •) + O 2 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 CH 3 C(=O)CH 2 CH 2 • radical + O 2 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 HO 2 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.