Article
Catalytic Effect of Carbon Dioxide on Reaction OH + CO → H + CO2 in Supercritical Environment: Master Equation Study
Journal of Physical Chemistry A
(2018)
Abstract
We investigated the reaction rates of OH + CO → H + CO2 in supercritical CO2 environment with and without additional CO2 molecule included in reactive complex. Ab initio potential energy surfaces previously reported a lower activation barrier and hence a catalytic effect of additional CO2 molecule. Here we solve the steady-state unimolecular master equations based on the Rice–Ramsperger–Kassel–Marcus theory (RRKM) and compare the rates for the two mechanisms. We found that the alternative reaction mechanism becomes faster at high pressure and low temperature, when the concentration of prereactive complex with additional CO2 molecule becomes appreciable. Therefore, this catalytic effect may be important for the chemical processes in CO2 solvent but is unlikely to play a role during combustion.
Disciplines
Publication Date
Summer July 31, 2018
DOI
10.1021/acs.jpca.8b04501
Citation Information
Artem Masunov, Elizabeth Wait and Subith Vasu. "Catalytic Effect of Carbon Dioxide on Reaction OH + CO → H + CO2 in Supercritical Environment: Master Equation Study" Journal of Physical Chemistry A Vol. 122 Iss. 31 (2018) p. 6355 - 6359 Available at: http://works.bepress.com/elizabeth-wait/6/