Molecular Dynamics of Combustion Reactions in Supercritical Carbon Dioxide. Part 5: Computational Study of Ethane Dissociation and Recombination Reactions C2H6 ⇌ CH3 + CH3

Wang, Chun-Hung; Panteleev, Sergey V.; Masunov, Artëm E.; Allison, Timothy C.; Chang, Sungho; Lim, Chansun; Jin, Yuin; Vasu, Subith S.

doi:10.1021/acs.jpca.9b02302

Title: Molecular Dynamics of Combustion Reactions in Supercritical Carbon Dioxide. Part 5: Computational Study of Ethane Dissociation and Recombination Reactions C₂H₆ ⇌ CH₃ + CH₃

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Abstract

Fossil fuel oxy-combustion is an emerging technology where the habitual nitrogen diluent is replaced by high-pressure supercritical CO₂ (sCO₂), which increases the efficiency of energy conversion. In this study, the chemical kinetics of the combustion reaction C₂H₆ ⇌ CH₃ + CH₃ in the sCO₂ environment is predicted at 30–1000 atm and 1000–2000 K. We adopt a multiscale approach, where the reactive complex is treated quantum mechanically in rigid rotor/harmonic oscillator approximation, while environment effects at different densities are taken into account by the potential of mean force, produced with classical molecular dynamics (MD). Here, we used boxed MD, where enhanced sampling of infrequent events of barrier crossing is accomplished without application of the bias potential. The multistate empirical valence bond model is applied to describe free radical formation accurately at the cost of the classical force field. Predicted rates at low densities agree well with the literature data. In conclusion, rate constants at 300 atm are 2.41 × 10¹⁴T^–0.20 exp(–77.03 kcal/mol/RT) 1/s for ethane dissociation and 8.44 × 10^–19T^1.42 exp(19.89 kcal/mol/RT) cm³/molecule/s for methyl–methyl recombination.

Authors:

Wang, Chun-Hung ^[1];

^[2];

^[3]; Allison, Timothy C. ^[4]; Chang, Sungho ^[5]; Lim, Chansun ^[6]; Jin, Yuin ^[6];

^[1]

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); N. I. Lobachevsky State Univ. of Nizhny Novgorod (Russia); South Ural State Univ., Chelyabinsk (Russia); National Research Nuclear Univ. MEPhI, Moscow (Russia)
Southwest Research Inst., San Antonio, TX (United States)
KEPCO Research Inst., Daejeon (Korea)
Hanwha Power Systems, Gyeonggi (Korea)

Publication Date:: Mon Apr 29 00:00:00 EDT 2019

Research Org.:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Sponsoring Org.:: USDOE Office of Science (SC); Russian Federation

OSTI Identifier:: 1577496

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

Additional Journal Information:: Journal Volume: 123; Journal Issue: 22; Journal ID: ISSN 1089-5639

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry; Physics; redox reactions; chemical reactions; solvents; kinetic parameters; molecules

Citation Formats


                    Wang, Chun-Hung, Panteleev, Sergey V., Masunov, Artëm E., Allison, Timothy C., Chang, Sungho, Lim, Chansun, Jin, Yuin, and Vasu, Subith S. Molecular Dynamics of Combustion Reactions in Supercritical Carbon Dioxide. Part 5: Computational Study of Ethane Dissociation and Recombination Reactions C2H6 ⇌ CH3 + CH3.  United States: N. p., 2019. 
Web.  doi:10.1021/acs.jpca.9b02302.

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                    Wang, Chun-Hung, Panteleev, Sergey V., Masunov, Artëm E., Allison, Timothy C., Chang, Sungho, Lim, Chansun, Jin, Yuin, & Vasu, Subith S. Molecular Dynamics of Combustion Reactions in Supercritical Carbon Dioxide. Part 5: Computational Study of Ethane Dissociation and Recombination Reactions C2H6 ⇌ CH3 + CH3.  United States.  https://doi.org/10.1021/acs.jpca.9b02302

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                    Wang, Chun-Hung, Panteleev, Sergey V., Masunov, Artëm E., Allison, Timothy C., Chang, Sungho, Lim, Chansun, Jin, Yuin, and Vasu, Subith S. Mon .  
"Molecular Dynamics of Combustion Reactions in Supercritical Carbon Dioxide. Part 5: Computational Study of Ethane Dissociation and Recombination Reactions C2H6 ⇌ CH3 + CH3".  United States.  https://doi.org/10.1021/acs.jpca.9b02302.  https://www.osti.gov/servlets/purl/1577496.

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@article{osti_1577496,

  title        = {Molecular Dynamics of Combustion Reactions in Supercritical Carbon Dioxide. Part 5: Computational Study of Ethane Dissociation and Recombination Reactions C2H6 ⇌ CH3 + CH3},

  author       = {Wang, Chun-Hung and Panteleev, Sergey V. and Masunov, Artëm E. and Allison, Timothy C. and Chang, Sungho and Lim, Chansun and Jin, Yuin and Vasu, Subith S.},

  abstractNote = {Fossil fuel oxy-combustion is an emerging technology where the habitual nitrogen diluent is replaced by high-pressure supercritical CO2 (sCO2), which increases the efficiency of energy conversion. In this study, the chemical kinetics of the combustion reaction C2H6 ⇌ CH3 + CH3 in the sCO2 environment is predicted at 30–1000 atm and 1000–2000 K. We adopt a multiscale approach, where the reactive complex is treated quantum mechanically in rigid rotor/harmonic oscillator approximation, while environment effects at different densities are taken into account by the potential of mean force, produced with classical molecular dynamics (MD). Here, we used boxed MD, where enhanced sampling of infrequent events of barrier crossing is accomplished without application of the bias potential. The multistate empirical valence bond model is applied to describe free radical formation accurately at the cost of the classical force field. Predicted rates at low densities agree well with the literature data. In conclusion, rate constants at 300 atm are 2.41 × 1014T–0.20 exp(–77.03 kcal/mol/RT) 1/s for ethane dissociation and 8.44 × 10–19T1.42 exp(19.89 kcal/mol/RT) cm3/molecule/s for methyl–methyl recombination.},

  doi          = {10.1021/acs.jpca.9b02302},

  journal      = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},

  number       = 22,

  volume       = 123,

  place        = {United States},

  year         = {Mon Apr 29 00:00:00 EDT 2019},

  month        = {Mon Apr 29 00:00:00 EDT 2019}

}

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Title: Molecular Dynamics of Combustion Reactions in Supercritical Carbon Dioxide. Part 5: Computational Study of Ethane Dissociation and Recombination Reactions C2H6 ⇌ CH3 + CH3

Abstract

Citation Formats

Title: Molecular Dynamics of Combustion Reactions in Supercritical Carbon Dioxide. Part 5: Computational Study of Ethane Dissociation and Recombination Reactions C₂H₆ ⇌ CH₃ + CH₃