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Title: Molecular Dynamics Study of Combustion Reactions in Supercritical Environment. Part 3: Boxed MD Study of CH 3 + HO 2 → CH 3O + OH Reaction Kinetics

Abstract

The kinetics of reaction CH 3 + HO 2 → CH 3O + OH in supercritical carbon dioxide media at pressures from 0.3 to 1000 atm in the temperature range (600–1600) K was studied using boxed molecular dynamics simulations at QM/MM theory level with periodical boundary conditions. The mechanism of this process includes two consecutive steps: formation and decomposition of CH 3OOH intermediate. We calculated the activation free energies and rate constants of each step, then used Bodenstein’s quasistationary concentrations approximation to estimate the rate constants of the reaction. On the basis of the temperature dependence of the rate constants, parameters in the extended Arrhenius equation were determined. Furthermore, we found that reaction rate of each step, as well as overall reaction, increases with increasing CO 2 pressure in the system. The most capable zone for the process is T = 1000–1200 K, and the CO 2 pressure is about 100 atm.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]
  1. Univ. of Central Florida, Orlando, FL (United States); N. I. Lobachevsky State Univ. of Nizhny Novgorod (Russia)
  2. Univ. of Central Florida, Orlando, FL (United States); South Ural State Univ., Chelyabinsk (Russia); National Research Nuclear Univ. MEPhI, Moscow (Russia)
  3. Univ. of Central Florida, Orlando, FL (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Fossil Energy (FE)
OSTI Identifier:
1480274
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: 13; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
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 Supercritical Environment. Part 3: Boxed MD Study of CH3 + HO2 → CH3O + OH Reaction Kinetics. United States: N. p., 2018. Web. doi:10.1021/acs.jpca.7b12233.
Panteleev, Sergey V., Masunov, Artëm E., & Vasu, Subith S. Molecular Dynamics Study of Combustion Reactions in Supercritical Environment. Part 3: Boxed MD Study of CH3 + HO2 → CH3O + OH Reaction Kinetics. United States. doi:10.1021/acs.jpca.7b12233.
Panteleev, Sergey V., Masunov, Artëm E., and Vasu, Subith S. Mon . "Molecular Dynamics Study of Combustion Reactions in Supercritical Environment. Part 3: Boxed MD Study of CH3 + HO2 → CH3O + OH Reaction Kinetics". United States. doi:10.1021/acs.jpca.7b12233. https://www.osti.gov/servlets/purl/1480274.
@article{osti_1480274,
title = {Molecular Dynamics Study of Combustion Reactions in Supercritical Environment. Part 3: Boxed MD Study of CH3 + HO2 → CH3O + OH Reaction Kinetics},
author = {Panteleev, Sergey V. and Masunov, Artëm E. and Vasu, Subith S.},
abstractNote = {The kinetics of reaction CH3 + HO2 → CH3O + OH in supercritical carbon dioxide media at pressures from 0.3 to 1000 atm in the temperature range (600–1600) K was studied using boxed molecular dynamics simulations at QM/MM theory level with periodical boundary conditions. The mechanism of this process includes two consecutive steps: formation and decomposition of CH3OOH intermediate. We calculated the activation free energies and rate constants of each step, then used Bodenstein’s quasistationary concentrations approximation to estimate the rate constants of the reaction. On the basis of the temperature dependence of the rate constants, parameters in the extended Arrhenius equation were determined. Furthermore, we found that reaction rate of each step, as well as overall reaction, increases with increasing CO2 pressure in the system. The most capable zone for the process is T = 1000–1200 K, and the CO2 pressure is about 100 atm.},
doi = {10.1021/acs.jpca.7b12233},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 13,
volume = 122,
place = {United States},
year = {2018},
month = {3}
}

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