title: First-Principles Chemical Kinetic Modeling of Methyl trans-3-Hexenoate Epoxidation by HO2.
abstract: 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.
authors.affiliation: IFP Energies Nouvelles , Engine and Vehicle Modeling Department, 1 et 4 avenue de Bois-Préau, 92852 Rueil-Malmaison Cedex, France.|Institut Carnot IFPEN Transports Energie , 1 et 4 avenue de Bois-Préau, 92852 Rueil-Malmaison Cedex, France.
authors.forename: S
authors.initials: S
authors.lastname: Cagnina
authors.affiliation: IFP Energies Nouvelles , Engine and Vehicle Modeling Department, 1 et 4 avenue de Bois-Préau, 92852 Rueil-Malmaison Cedex, France.|Institut Carnot IFPEN Transports Energie , 1 et 4 avenue de Bois-Préau, 92852 Rueil-Malmaison Cedex, France.
authors.forename: A
authors.identifier: http://orcid.org/0000-0002-9234-3101
authors.initials: A
authors.lastname: Nicolle
authors.affiliation: IFP Energies Nouvelles , Thermodynamics and Molecular Modeling Department, 1 et 4 avenue de Bois-Préau, 92852 Rueil-Malmaison Cedex, France.
authors.forename: T
authors.initials: T
authors.lastname: de Bruin
authors.affiliation: Argonne National Laboratory , Chemical Sciences and Engineering Division, Argonne, Illinois 60439, United States.
authors.forename: Y
authors.initials: Y
authors.lastname: Georgievskii
authors.affiliation: Argonne National Laboratory , Chemical Sciences and Engineering Division, Argonne, Illinois 60439, United States.
authors.forename: S J
authors.initials: SJ
authors.lastname: Klippenstein