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.
Cagnina, S., et al. "First-principles chemical kinetic modeling of methyl <i>trans</i>-3-hexenoate epoxidation by HO<sub>2</sub>." Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, vol. 121, no. 9, Feb. 2017. https://doi.org/10.1021/acs.jpca.7b00519
Cagnina, S., Nicolle, Andre, de Bruin, T., Georgievskii, Y., & Klippenstein, S. J. (2017). First-principles chemical kinetic modeling of methyl <i>trans</i>-3-hexenoate epoxidation by HO<sub>2</sub>. Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, 121(9). https://doi.org/10.1021/acs.jpca.7b00519
Cagnina, S., Nicolle, Andre, de Bruin, T., et al., "First-principles chemical kinetic modeling of methyl <i>trans</i>-3-hexenoate epoxidation by HO<sub>2</sub>," Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory 121, no. 9 (2017), https://doi.org/10.1021/acs.jpca.7b00519
@article{osti_1365818,
author = {Cagnina, S. and Nicolle, Andre and de Bruin, T. and Georgievskii, Y. and Klippenstein, S. J.},
title = {First-principles chemical kinetic modeling of methyl <i>trans</i>-3-hexenoate epoxidation by HO<sub>2</sub>},
annote = {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},
url = {https://www.osti.gov/biblio/1365818},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
issn = {ISSN 1089-5639},
number = {9},
volume = {121},
place = {United States},
publisher = {American Chemical Society},
year = {2017},
month = {02}}
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1365818
Journal Information:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 9 Vol. 121; ISSN 1089-5639