Molecular Dynamics Study of Combustion Reactions in a Supercritical Environment. Part 2: Boxed MD Study of CO + OH → CO2 + H Reaction Kinetics

Panteleev, Sergey V.; Masunov, Artëm E.; Vasu, Subith S.

doi:10.1021/acs.jpca.7b09774

Title: Molecular Dynamics Study of Combustion Reactions in a Supercritical Environment. Part 2: Boxed MD Study of CO + OH → CO₂ + H Reaction Kinetics

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Abstract

Oxy-fuel combustion technology holds a great promise in both increasing the efficiency of the energy conversion and reducing environmental impact. Yet, 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. In this work, 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 discovered 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:

^[1];

^[2];

^[3]

Univ. of Central Florida, Orlando, FL (United States); N. I. Lobachevsky State Univ. of Nizhny Novgorod (Russia)
Univ. of Central Florida, Orlando, FL (United States); South Ural State Univ., Chelyabinsk (Russia); National Research Nuclear Univ. MEPhI, Moscow (Russia)
Univ. of Central Florida, Orlando, FL (United States)

Publication Date:: Tue Jan 23 00:00:00 EST 2018

Research Org.:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

Sponsoring Org.:: USDOE Office of Fossil Energy (FE)

OSTI Identifier:: 1480272

Grant/Contract Number:: FE0025260

Resource Type:: 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

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS

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 → CO2 + H Reaction Kinetics.  United States: N. p., 2018. 
Web.  doi:10.1021/acs.jpca.7b09774.

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                    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 → CO2 + H Reaction Kinetics.  United States.  https://doi.org/10.1021/acs.jpca.7b09774

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                    Panteleev, Sergey V., Masunov, Artëm E., and Vasu, Subith S. Tue .  
"Molecular Dynamics Study of Combustion Reactions in a Supercritical Environment. Part 2: Boxed MD Study of CO + OH → CO2 + H Reaction Kinetics".  United States.  https://doi.org/10.1021/acs.jpca.7b09774.  https://www.osti.gov/servlets/purl/1480272.

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@article{osti_1480272,

  title        = {Molecular Dynamics Study of Combustion Reactions in a Supercritical Environment. Part 2: Boxed MD Study of CO + OH → CO2 + 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. Yet, 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. In this work, 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 discovered 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},

  number       = 4,

  volume       = 122,

  place        = {United States},

  year         = {Tue Jan 23 00:00:00 EST 2018},

  month        = {Tue Jan 23 00:00:00 EST 2018}

}

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Title: Molecular Dynamics Study of Combustion Reactions in a Supercritical Environment. Part 2: Boxed MD Study of CO + OH → CO2 + H Reaction Kinetics

Abstract

Citation Formats

Title: Molecular Dynamics Study of Combustion Reactions in a Supercritical Environment. Part 2: Boxed MD Study of CO + OH → CO₂ + H Reaction Kinetics