Kinetics of the high-temperature combustion reactions of dibutylether using composite computational methods

Mariam El Rachidi, Alexander C. Davis, Mani Sarathy

Research output: Contribution to journalArticlepeer-review

14 Scopus citations

Abstract

This paper investigates the high-temperature combustion kinetics of n-dibutyl ether (n-DBE), including unimolecular decomposition, H-abstraction by H, H-migration, and C{single bond}C/C{single bond}O β-scission reactions of the DBE radicals. The energetics of H-abstraction by OH radicals is also studied. All rates are determined computationally using the CBS-QB3 and G4 composite methods in conjunction with conventional transition state theory. The B3LYP/6-311++G(2df,2pd) method is used to optimize the geometries and calculate the frequencies of all reactive species and transition states for use in ChemRate. Some of the rates calculated in this study vary markedly from those obtained for similar reactions of alcohols or alkanes, particularly those pertaining to unimolecular decomposition and β-scission at the α-β C{single bond}C bond. These variations show that analogies to alkanes and alcohols are, in some cases, inappropriate means of estimating the reaction rates of ethers. This emphasizes the need to establish valid rates through computation or experimentation. Such studies are especially important given that ethers exhibit promising biofuel and fuel additive characteristics. © 2014.
Original languageEnglish (US)
Pages (from-to)385-392
Number of pages8
JournalProceedings of the Combustion Institute
Volume35
Issue number1
DOIs
StatePublished - 2015

ASJC Scopus subject areas

  • Chemical Engineering(all)
  • Mechanical Engineering
  • Physical and Theoretical Chemistry

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