NDLI: Thermochemistry and kinetics of acetonylperoxy radical isomerisation and decomposition : a quantum chemistry and CVT/SCT approach

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	El-Nahas, Ahmed M. Simmie, John M. Navarro, Maria V. Bozzelli, Joseph W. Black, Gráinne Curran, Henry J.
Description	Country affiliation: Egypt Author Affiliation: El-Nahas AM ( Faculty of Science, El-Menoufia University, Shebin El-Kom, Egypt.)
Abstract	CBS-QB3 calculations have been used to determine thermochemical and kinetic parameters of the isomerisation and decomposition reactions of the acetonylperoxy radical, $CH_{3}C(O)CH_{2}OO˙,$ which has been formed via the reaction of acetonyl radical with $O_{2}$ leading to the formation of an energised peroxy adduct with a calculated well depth of near 111 kJ $mol^{−1}.$ This species can undergo subsequent 1,5 and 1,3 H-shifts to give the primary and secondary radicals: $C˙H_{2}C(O)CH_{2}OOH$ and $CH_{3}C(O)C˙HOOH,$ respectively, or rearrange to give a 3-methyl-1,2-dioxetan-3-yloxy radical. Rate constants for isomerisation and subsequent decomposition have been estimated using canonical variational transition state theory with small curvature tunneling CVT/SCT. The variational effect for the isomerisation channels is only moderate but the tunneling correction is significant at temperatures up to 1000 K; the formation of a primary radical by a 1,5-shift is the main reaction channel and the competition with the secondary one starts only at around 1500 K. The fate of the primary acetonylhydroperoxy radical is predominantly to form oxetan-3-one while the ketene and 1-oxy-3-hydroxyacetonyl radical channels only compete with the formation of oxetan-3-one at temperatures >1200 K. In addition, consistent and reliable enthalpies of formation have been computed for the molecules acetonylhydroperoxide, 1,3-dihydroxyacetone , methylglyoxal and cyclobutanone , and for some related radicals.
File Format	HTM / HTML
ISSN	14639076
Issue Number	47
Journal	Physical Chemistry Chemical Physics
Volume Number	10
e-ISSN	14639084
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2008-12-21
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Discipline Physics Discipline Biophysics Discipline Chemistry
Alternative Title	Thermochemistry and kinetics of acetonylperoxy radical isomerisation and decomposition: a quantum chemistry and CVT/SCT approach
Content Type	Text
Resource Type	Article
Subject	Physics and Astronomy Physical and Theoretical Chemistry

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