Molecular Dynamics Study of Combustion Reactions in Supercritical Environment. Part 3: Boxed MD Study of CH3 + HO2 → CH3O + OH Reaction Kinetics
[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)
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.
- Research Organization:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
- Sponsoring Organization:
- USDOE Office of Fossil Energy (FE)
- Grant/Contract Number:
- FE0025260
- OSTI ID:
- 1480274
- Journal Information:
- Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Vol. 122, Issue 13; ISSN 1089-5639
- Publisher:
- American Chemical SocietyCopyright Statement
- Country of Publication:
- United States
- Language:
- English
Web of Science
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