A theoretical kinetics study of the reactions of methylbutanoate with hydrogen and hydroxyl radicals

Lidong Zhang, Qinxue Chen, Peng Zhang

Research output: Journal article publicationJournal articleAcademic researchpeer-review

33 Citations (Scopus)

Abstract

The chemical kinetics for the reactions of methylbutanoate (MB) with hydrogen and hydroxyl radicals were studied theoretically with the ab initio transition state theory. In addition to the hydrogen abstraction reactions of MB by the radicals, the potential energy surfaces of MB + H and MB + OH were further investigated to search for additional significant hydrogen addition channels, which are followed by β-scission reactions to produce non-hydrogen and non-water products, respectively. Stationary points on the potential energy surfaces were calculated at the QCISD(T)/CBS//B3LYP/6-311++G(d,p) level. Phenomenological rate coefficients for temperature- and pressure-dependent reactions were calculated over broad ranges of temperature (200-2500 K) and pressure (1.3 × 10-3-102atm) by solving the time-dependent multiple-well master equation. The theoretical rate coefficients were compared with the available experimental and theoretical data and observed discrepancies were analyzed. The predicted rate coefficients are represented in the forms that may readily be used in combustion modeling of MB.
Original languageEnglish
Pages (from-to)481-489
Number of pages9
JournalProceedings of the Combustion Institute
Volume35
Issue number1
DOIs
Publication statusPublished - 1 Jan 2015

Keywords

  • Chemical kinetics
  • Hydrogen radical
  • Hydroxyl radical
  • Methylbutanoate
  • Transition state theory

ASJC Scopus subject areas

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

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