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Title: First-principles chemical kinetic modeling of methyl trans-3-hexenoate epoxidation by HO 2

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 HO 2. The impact of temperature and pressure on epoxidation pathways involving H-bonded and non-H-bonded conformers was assessed. As a result, 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:
 [1] ; ORCiD logo [1] ;  [2] ;  [3] ;  [3]
  1. IFP Energies Nouvelles, Rueil-Malmaison Cedex (France); Institut Carnot IFPEN Transports Energie, Rueil-Malmaison Cedex (France)
  2. IFP Energies Nouvelles, Rueil-Malmaison Cedex (France)
  3. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Grant/Contract Number:
AC02-06CH11357
Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 121; Journal Issue: 9; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Ester; TST; ab initio; combustion; phenomenological kinetics
OSTI Identifier:
1365818