New Insight into Competition between Decomposition Pathways of Hydroperoxymethyl Formate in Low Temperature DME Oxidation

Li Li Xing, Xiao Yuan Zhang, Zhandong Wang, Shuang Li, Li Dong Zhang*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

8 Scopus citations

Abstract

Hydroperoxymethyl formate is a crucial intermediate formed during the low-temperature oxidation of dimethyl ether. The decomposition pathways of HOOCH2OCHO were calculated at QCISD(T)/CBS//B3LYP/6-311++G(d,p) level. The temperature- and pressure-dependent rate constants are computed using microcanonical variational transition state theory coupled with the RRKM/master equation calculations. The calculations show that a pathway leads to the formation of formic acid and a Criegee intermediate does exist, besides the direct dissociation channel to OH and OCH2OCHO radicals. However, formation of the Criegee intermediate has never been considered as an intermediate in dimethyl ether combustion before. The computed rate constants indicate that the newly confirmed pathway is competitive to the direct dissociation route and it is promising to reduce the low-temperature oxidation reactivity. Also electronic effect of groups, e.g. -CHO and O atom, is taken into account. Moreover, Hirshfeld atomic charge and natural bond order analysis are performed to explain this phenomenon from a perspective of chemical nature.

Original languageEnglish (US)
Pages (from-to)563-572
Number of pages10
JournalChinese Journal of Chemical Physics
Volume28
Issue number5
DOIs
StatePublished - Oct 27 2015

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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