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Rate constants for hydrogen abstraction reactions by the hydroperoxyl radical from methanol, ethenol, acetaldehyde, toluene, and phenol
Author(s) -
Altarawneh Mohammednoor,
AlMuhtaseb Ala'A H.,
Dlugogorski Bogdan Z.,
Kennedy Eric M.,
Mackie John C.
Publication year - 2011
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.21756
Subject(s) - hydroperoxyl , chemistry , toluene , acetaldehyde , reaction rate constant , arrhenius equation , methanol , hydrogen atom abstraction , phenol , photochemistry , activation energy , computational chemistry , hydrogen , radical , organic chemistry , ethanol , kinetics , physics , quantum mechanics
Abstract An important step in the initial oxidation of hydrocarbons at low to intermediate temperatures is the abstraction of H by hydroperoxyl radical (HO 2 ). In this study, we calculate energy profiles for the sequence: reactant + HO 2 → [complex of reactants] → transition state → [complex of products] → product + H 2 O 2 for methanol, ethenol (i.e., C 2 H 3 OH), 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 HO 2 to the various distinct sites in phenol is investigated. Direct abstraction of the hydroxyl H was found to dominate over HO 2 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 HO 2 is expected to exist at reactive levels. © 2011 Wiley Periodicals, Inc. J Comput Chem 2011