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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 3 O + OH Reaction Kinetics

Abstract

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. We found that reaction rate of each step, as well as overall reaction, increases with increasing CO2 pressure in the system. The most effective zone for the process is T = 1000–1200 K, and the CO2 pressure is about 100 atm.

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 Dr., 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:
1480274
DOE Contract Number:  
FE0025260
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory; Journal Volume: 122; Journal Issue: 13
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 CH 3 + HO 2 → CH 3 O + 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 CH 3 + HO 2 → CH 3 O + 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 CH 3 + HO 2 → CH 3 O + OH Reaction Kinetics". United States. doi:10.1021/acs.jpca.7b12233.
@article{osti_1480274,
title = {Molecular Dynamics Study of Combustion Reactions in Supercritical Environment. Part 3: Boxed MD Study of CH 3 + HO 2 → CH 3 O + 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. We found that reaction rate of each step, as well as overall reaction, increases with increasing CO2 pressure in the system. The most effective 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 = {Mon Mar 05 00:00:00 EST 2018},
month = {Mon Mar 05 00:00:00 EST 2018}
}