Rate constants for hydrogen abstraction reactions by the hydroperoxyl radical from methanol, ethenol, acetaldehyde, toluene, and phenol

Mohammednoor Altarawneh, Ala'A H. Al-Muhtaseb, Bogdan Z. Dlugogorski, Eric M. Kennedy, John C. MacKie

Research output: Contribution to journalArticle

29 Citations (Scopus)

Abstract

An important step in the initial oxidation of hydrocarbons at low to intermediate temperatures is the abstraction of H by hydroperoxyl radical (HO2). In this study, we calculate energy profiles for the sequence: reactant + HO2 → [complex of reactants] → transition state → [complex of products] → product + H2O2 for methanol, ethenol (i.e., C2H3OH), acetaldehyde, toluene, and phenol. Rate constants are provided in the simple Arrhenius form. Reasonable agreement was obtained with the limited literature data available for acetaldehyde and toluene. Addition of HO2 to the various distinct sites in phenol is investigated. Direct abstraction of the hydroxyl H was found to dominate over HO2 addition to the ring. The results presented herein should be useful in modeling the lower temperature oxidation of the five compounds considered, especially at low temperature where the HO2 is expected to exist at reactive levels.

Original languageEnglish
Pages (from-to)1725-1733
Number of pages9
JournalJournal of Computational Chemistry
Volume32
Issue number8
DOIs
Publication statusPublished - Jun 2011

Fingerprint

Phenol
Acetaldehyde
Toluene
Rate Constant
Oxidation
Hydrogen
Phenols
Methanol
Rate constants
Transition State
Hydrocarbons
Distinct
Ring
Calculate
Hydroxyl Radical
Temperature
Energy
Modeling
Abstraction
Profile

Keywords

  • acetaldehyde
  • ethenol
  • HO radical
  • methanol
  • phenol
  • toluene
  • TST

ASJC Scopus subject areas

  • Chemistry(all)
  • Computational Mathematics

Cite this

Rate constants for hydrogen abstraction reactions by the hydroperoxyl radical from methanol, ethenol, acetaldehyde, toluene, and phenol. / Altarawneh, Mohammednoor; Al-Muhtaseb, Ala'A H.; Dlugogorski, Bogdan Z.; Kennedy, Eric M.; MacKie, John C.

In: Journal of Computational Chemistry, Vol. 32, No. 8, 06.2011, p. 1725-1733.

Research output: Contribution to journalArticle

Altarawneh, Mohammednoor ; Al-Muhtaseb, Ala'A H. ; Dlugogorski, Bogdan Z. ; Kennedy, Eric M. ; MacKie, John C. / Rate constants for hydrogen abstraction reactions by the hydroperoxyl radical from methanol, ethenol, acetaldehyde, toluene, and phenol. In: Journal of Computational Chemistry. 2011 ; Vol. 32, No. 8. pp. 1725-1733.
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AU - Kennedy, Eric M.

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