First-Principles Chemical Kinetic Modeling of Methyl trans-3-Hexenoate Epoxidation by HO2

The design of innovative combustion processes relies on a comprehensive understanding of biodiesel oxidation kinetics. The present study aims at unraveling the reaction mechanism involved in the epoxidation of a realistic biodiesel surrogate, methyl trans-3-hexenoate, by hydroperoxy radicals using a...

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Bibliographic Details
Published in:The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2017-03, Vol.121 (9), p.1909-1915
Main Authors: Cagnina, S, Nicolle, A, de Bruin, T, Georgievskii, Y, Klippenstein, S. J
Format: Article
Language:English
Subjects:
ab initio
combustion
Ester
INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
phenomenological kinetics
TST
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Summary:The design of innovative combustion processes relies on a comprehensive understanding of biodiesel oxidation kinetics. The present study aims at unraveling the reaction mechanism involved in the epoxidation of a realistic biodiesel surrogate, methyl trans-3-hexenoate, by hydroperoxy radicals using a bottom-up theoretical kinetics methodology. The obtained rate constants are in good agreement with experimental data for alkene epoxidation by HO2. The impact of temperature and pressure on epoxidation pathways involving H-bonded and non-H-bonded conformers was assessed. The obtained rate constant was finally implemented into a state-of-the-art detailed combustion mechanism, resulting in fairly good agreement with engine experiments.
ISSN:1089-5639
1520-5215
DOI:10.1021/acs.jpca.7b00519