skip to main content

DOE PAGESDOE PAGES

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

Cagnina, S., Nicolle, Andre, de Bruin, T., Georgievskii, Y., and Klippenstein, S. J.. First-principles chemical kinetic modeling of methyl trans-3-hexenoate epoxidation by HO2. United States: N. p., Web. doi:10.1021/acs.jpca.7b00519.
Cagnina, S., Nicolle, Andre, de Bruin, T., Georgievskii, Y., & Klippenstein, S. J.. First-principles chemical kinetic modeling of methyl trans-3-hexenoate epoxidation by HO2. United States. doi:10.1021/acs.jpca.7b00519.
Cagnina, S., Nicolle, Andre, de Bruin, T., Georgievskii, Y., and Klippenstein, S. J.. 2017. "First-principles chemical kinetic modeling of methyl trans-3-hexenoate epoxidation by HO2". United States. doi:10.1021/acs.jpca.7b00519. https://www.osti.gov/servlets/purl/1365818.
@article{osti_1365818,
title = {First-principles chemical kinetic modeling of methyl trans-3-hexenoate epoxidation by HO2},
author = {Cagnina, S. and Nicolle, Andre and de Bruin, T. and Georgievskii, Y. and Klippenstein, S. J.},
abstractNote = {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. 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.},
doi = {10.1021/acs.jpca.7b00519},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 9,
volume = 121,
place = {United States},
year = {2017},
month = {2}
}