First-principles chemical kinetic modeling of methyl trans-3-hexenoate epoxidation by HO2

Cagnina, S.; Nicolle, Andre; de Bruin, T.; Georgievskii, Y.; Klippenstein, S. J.

doi:10.1021/acs.jpca.7b00519

Title: First-principles chemical kinetic modeling of methyl trans-3-hexenoate epoxidation by HO₂

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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. 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:

Cagnina, S. ^[1];

^[1]; de Bruin, T. ^[2]; Georgievskii, Y. ^[3]; Klippenstein, S. J. ^[3]

IFP Energies Nouvelles, Rueil-Malmaison Cedex (France); Institut Carnot IFPEN Transports Energie, Rueil-Malmaison Cedex (France)
IFP Energies Nouvelles, Rueil-Malmaison Cedex (France)
Argonne National Lab. (ANL), Argonne, IL (United States)

Publication Date:: Thu Feb 16 00:00:00 EST 2017

Research Org.:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1365818

Grant/Contract Number:: AC02-06CH11357

Resource 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

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Ester; TST; ab initio; combustion; phenomenological kinetics

Citation Formats


                    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., 2017. 
Web.  doi:10.1021/acs.jpca.7b00519.

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                    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.  https://doi.org/10.1021/acs.jpca.7b00519

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                    Cagnina, S., Nicolle, Andre, de Bruin, T., Georgievskii, Y., and Klippenstein, S. J. Thu .  
"First-principles chemical kinetic modeling of methyl trans-3-hexenoate epoxidation by HO2".  United States.  https://doi.org/10.1021/acs.jpca.7b00519.  https://www.osti.gov/servlets/purl/1365818.

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@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         = {Thu Feb 16 00:00:00 EST 2017},

  month        = {Thu Feb 16 00:00:00 EST 2017}

}

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Title: First-principles chemical kinetic modeling of methyl trans-3-hexenoate epoxidation by HO2

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Title: First-principles chemical kinetic modeling of methyl trans-3-hexenoate epoxidation by HO₂