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Title: Molecular Dynamics Study of Combustion Reactions in a Supercritical Environment. Part 2: Boxed MD Study of CO + OH → CO 2 + H Reaction Kinetics

Abstract

Oxy-fuel combustion technology holds a great promise in both increasing the efficiency of the energy conversion and reducing environmental impact. However, effects of the higher pressures and replacement of the nitrogen with carbon dioxide diluent are not well understood at present. The title reaction is one of the most important processes in combustion. Despite numerous studies, the effects of supercritical carbon dioxide environment did not receive much attention in the past. Here we report the results of boxed molecular dynamics simulations of these effects at QM/MM theory level with periodical boundary conditions. The free energy barriers for HOCO intermediate formation and decomposition were tabulated in a wide range of pressures (1–1000 atm) and temperatures (400–1600 K). Pressure dependence of calculated rate constants for these reaction steps and overall reaction were analyzed. We found that the CO2 environment may increase these rate constants up to a factor of 25, at near critical conditions. At higher temperatures, this effect weakens significantly. Numerical values for parameters of extended Arrhenius equation, suitable for combustion kinetic modeling are reported.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]
  1. NanoScienece Technology Center, University of Central Florida, 12424 Research Parkway, Suite 400, Orlando, Florida 32826, United States; N. I. Lobachevsky State University of Nizhny Novgorod, Gagarin Av. 23, Nizhny Novgorod 603950, Russia
  2. NanoScienece Technology Center, University of Central Florida, 12424 Research Parkway, Suite 400, Orlando, Florida 32826, United States; Department of Chemistry, and Department of Physics, University of Central Florida, 4111 Libra Drive, Orlando, Florida 32816, United States; South Ural State University, Lenin pr. 76, Chelyabinsk 454080, Russia; National Research Nuclear University MEPhI, Kashirskoye shosse 31, Moscow, 115409, Russia
  3. Center for Advanced Turbomachinery and Energy Research (CATER), Mechanical and Aerospace Engineering, University of Central Florida, Orlando, Florida 32816, United States
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory-National Energy Research Scientific Computing Center
Sponsoring Org.:
USDOE Office of Fossil Energy (FE)
OSTI Identifier:
1480272
Grant/Contract Number:  
FE0025260
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 122; Journal Issue: 4; Journal ID: ISSN 1089-5639
Country of Publication:
United States
Language:
English

Citation Formats

Panteleev, Sergey V., Masunov, Artëm E., and Vasu, Subith S. Molecular Dynamics Study of Combustion Reactions in a Supercritical Environment. Part 2: Boxed MD Study of CO + OH → CO 2 + H Reaction Kinetics. United States: N. p., 2018. Web. doi:10.1021/acs.jpca.7b09774.
Panteleev, Sergey V., Masunov, Artëm E., & Vasu, Subith S. Molecular Dynamics Study of Combustion Reactions in a Supercritical Environment. Part 2: Boxed MD Study of CO + OH → CO 2 + H Reaction Kinetics. United States. doi:10.1021/acs.jpca.7b09774.
Panteleev, Sergey V., Masunov, Artëm E., and Vasu, Subith S. Mon . "Molecular Dynamics Study of Combustion Reactions in a Supercritical Environment. Part 2: Boxed MD Study of CO + OH → CO 2 + H Reaction Kinetics". United States. doi:10.1021/acs.jpca.7b09774. https://www.osti.gov/servlets/purl/1480272.
@article{osti_1480272,
title = {Molecular Dynamics Study of Combustion Reactions in a Supercritical Environment. Part 2: Boxed MD Study of CO + OH → CO 2 + H Reaction Kinetics},
author = {Panteleev, Sergey V. and Masunov, Artëm E. and Vasu, Subith S.},
abstractNote = {Oxy-fuel combustion technology holds a great promise in both increasing the efficiency of the energy conversion and reducing environmental impact. However, effects of the higher pressures and replacement of the nitrogen with carbon dioxide diluent are not well understood at present. The title reaction is one of the most important processes in combustion. Despite numerous studies, the effects of supercritical carbon dioxide environment did not receive much attention in the past. Here we report the results of boxed molecular dynamics simulations of these effects at QM/MM theory level with periodical boundary conditions. The free energy barriers for HOCO intermediate formation and decomposition were tabulated in a wide range of pressures (1–1000 atm) and temperatures (400–1600 K). Pressure dependence of calculated rate constants for these reaction steps and overall reaction were analyzed. We found that the CO2 environment may increase these rate constants up to a factor of 25, at near critical conditions. At higher temperatures, this effect weakens significantly. Numerical values for parameters of extended Arrhenius equation, suitable for combustion kinetic modeling are reported.},
doi = {10.1021/acs.jpca.7b09774},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
issn = {1089-5639},
number = 4,
volume = 122,
place = {United States},
year = {2018},
month = {1}
}

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