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Kinetics of the Reactions of Methyl Radical with Hydrogen, Methyl and Ethyl Peroxides
Author(s) -
Cao Fei,
Shi Gai,
Song Jinou,
Tian Pengzhen,
Li Zhijun
Publication year - 2021
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.202100193
Subject(s) - chemistry , hydrogen atom abstraction , formaldehyde , reaction rate constant , aldehyde , kinetics , medicinal chemistry , methyl group , reaction mechanism , computational chemistry , transition state , ab initio , radical , methyl radical , photochemistry , group (periodic table) , organic chemistry , catalysis , physics , quantum mechanics
Abstract The HOOH+CH 3 , CH 3 OOH+CH 3 and CH 3 CH 2 OOH+CH 3 reactions were characterized using accurate ab initio methods with reliable basis sets. The reaction rate constants were calculated by canonical variational transition state theory as applied to a complex mechanism involving the formation of reactant complexes. The formation of aldehyde or formaldehyde was observed when the CH 3 radical attacks on the CH 2 group in CH 3 CH 2 OOH or on the CH 3 group in CH 3 OOH. The results showed that the channels of H‐abstraction from OH group are dominant channels at low temperature, while the channels of OH‐transfer to CH 3 become predominant with increasing temperature. For the CH 3 OOH+CH 3 reaction, the channel producing CH 2 O+OH and the OH‐transfer channel have a similar rate coefficient.