Kinetics of the Reactions of Methyl Radical with Hydrogen, Methyl and Ethyl Peroxides. Issue 7 (15th February 2021)

• Record Type: Journal Article
• Authors: Cao, Fei; Shi, Gai; Song, Jinou; Tian, Pengzhen; Li, Zhijun
• Is Part Of: ChemistrySelect. Volume 6:Issue 7(2021)
• Page Start: 1548
• Page End: 1554
• Publication Date: 2021-02-15
• Subjects: Keyword: ethyl hydroperoxide -- hydrogen -- methyl hydroperoxide -- methyl radical -- reaction mechanisms; Chemistry -- Periodicals; 540.5
• DOI: 10.1002/slct.202100193
• Languages: English
• ISSNs: 2365-6549

Abstract

Abstract: The HOOH+CH3, CH3 OOH+CH3 and CH3 CH2 OOH+CH3 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 CH3 radical attacks on the CH2 group in CH3 CH2 OOH or on the CH3 group in CH3 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 CH3 become predominant with increasing temperature. For the CH3 OOH+CH3 reaction, the channel producing CH2 O+OH and the OH‐transfer channel have a similar rate coefficient. Abstract : or the CH3 +CH3 OOH reaction, the H‐abstraction from CH3 in CH3 OOH leads to the formation of CH2 O+OH, indicating that the nascent hydroxide radical leaves the product complexes without interaction with the formaldehyde. It is dominant channel at the temperature greater than 600 K. Similar channel to produce CH3 CHO+OH is also founded in the CH3 +C2 H5 OOH reaction, but it is not such important as in the CH3 +C2 H5 OOH reaction.