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Measurements of the kinetics of the OH‐initiated oxidation of β‐pinene: Radical propagation in the OH + β‐pinene + O 2 + NO reaction system
Author(s) -
Davis Maxine E.,
Tapscott Craig,
Stevens Philip S.
Publication year - 2005
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.20105
Subject(s) - chemistry , pinene , radical , kinetics , isomerization , reaction rate constant , reaction mechanism , hydroxyl radical , photochemistry , chemical kinetics , torr , analytical chemistry (journal) , organic chemistry , thermodynamics , catalysis , physics , quantum mechanics
The mechanism of the OH‐initiated oxidation of β‐pinene in the presence of NO has been investigated using a discharge‐flow system at 5 Torr and 300 K. OH radical concentrations were measured as a function of reaction time by laser‐induced fluorescence (LIF). The rate constant for the OH +β‐pinene reaction was measured to be (7.68 ± 0.72) ×10 −11 cm 3 molecule −1 s −1 . OH radical propagation was observed after the addition of O 2 and NO, and the measured OH concentration profiles were compared to simulations based on both the Master Chemical Mechanism and the Regional Atmospheric Chemistry Mechanism for β‐pinene oxidation in order to determine the ability of these mechanisms to describe the observed efficiency of radical propagation. Both models are able to reproduce the observed OH concentrations profiles to within 15%. Expanding the MCM to include isomerization of the β‐hydroxy alkoxy radicals improves the agreement with the experimental observations. © 2005 Wiley Periodicals, Inc. Int J Chem Kinet 37: 522–531, 2005