Molecular Dynamics Study Of Combustion Reactions In Supercritical Environment. Part 3: Boxed Md Study Of Ch3 + Ho2 → Ch3O + 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.

Publication Date

4-5-2018

Publication Title

Journal of Physical Chemistry A

Volume

122

Issue

13

Number of Pages

3337-3345

Document Type

Article

Personal Identifier

scopus

DOI Link

https://doi.org/10.1021/acs.jpca.7b12233

Socpus ID

85045066803 (Scopus)

Source API URL

https://api.elsevier.com/content/abstract/scopus_id/85045066803

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