Unimolecular decomposition of ethyl hydroperoxide: Ab initio/Rice- Ramsperger-Kassel-Marcus theoretical prediction of rate constants

Dongna Chen, Hanfeng Jin, Zhandong Wang, Lidong Zhang*, Fei Qi

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

18 Scopus citations

Abstract

Alkyl hydroperoxides are found to be important intermediates in the combustion and oxidation processes of hydrocarbons. However, studies of ethyl hydroperoxide (CH3CH2OOH) are limited. In this work, kinetics and mechanisms for unimolecular decomposition of CH3CH 2OOH have been investigated. The potential energy surface of decomposition reactions have first been predicted at the CCSD(T)/6-311+G(3df,2p) //B3LYP/6-311G(d, p) level. The results show that the formation of CH 3CH2O + OH via O-O direct bond dissociation is dominant, the branching ratio of which is over 99% in the whole temperature range from 300 to 1000 K, and its rate constant can be expressed as k1 = 9.26 × 10 52 T-11.91 exp(-26879/T) s-1 at 1 atm. The rate constants of the reaction CH3CH2OOH → CH 3CH2O + OH at different temperatures and pressures have been calculated, which can help us to comprehend the reactions of CH 3CH2OOH at experimental conditions.

Original languageEnglish (US)
Pages (from-to)602-611
Number of pages10
JournalJournal of Physical Chemistry A
Volume115
Issue number5
DOIs
StatePublished - Feb 10 2011
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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