First-Principles Chemical Kinetic Modeling of Methyl trans -3-Hexenoate Epoxidation by HO 2

Stefania Cagnina; André Nicolle; Theodorus de Bruin; Youri Georgievskii; Stephen Klippenstein

First-Principles Chemical Kinetic Modeling of Methyl trans -3-Hexenoate Epoxidation by HO 2

Stefania Cagnina ^{1, 2} André Nicolle ^{1, 2} Theodorus de Bruin ¹ Youri Georgievskii ³ Stephen Klippenstein ³

2 Institut Carnot IFPEN Transports Energie

3 ANL - Argonne National Laboratory [Lemont]

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.

Document type :

Journal articles

Domain :

Chemical Sciences

Complete list of metadatas

https://hal-ifp.archives-ouvertes.fr/hal-01760363
Contributor : Françoise Bertrand <>
Submitted on : Friday, April 6, 2018 - 11:27:37 AM
Last modification on : Thursday, February 7, 2019 - 4:43:40 PM

First-Principles Chemical Kinetic Modeling of Methyl trans -3-Hexenoate Epoxidation by HO 2

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First-Principles Chemical Kinetic Modeling of Methyl trans -3-Hexenoate Epoxidation by HO 2

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