Catalytic Effect of Carbon Dioxide on Reaction OH
+ CO → H + CO<sub>2</sub> in Supercritical Environment: Master
Equation Study
Artëm E. Masunov
Elizabeth E. Wait
Subith S. Vasu
10.1021/acs.jpca.8b04501.s001
https://acs.figshare.com/articles/journal_contribution/Catalytic_Effect_of_Carbon_Dioxide_on_Reaction_OH_CO_H_CO_sub_2_sub_in_Supercritical_Environment_Master_Equation_Study/6879785
We investigated the reaction rates
of OH + CO → H + CO<sub>2</sub> in supercritical CO<sub>2</sub> environment with and without
additional CO<sub>2</sub> molecule included in reactive complex. Ab
initio potential energy surfaces previously reported a lower activation
barrier and hence a catalytic effect of additional CO<sub>2</sub> 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 CO<sub>2</sub> molecule becomes appreciable. Therefore, this catalytic effect
may be important for the chemical processes in CO<sub>2</sub> solvent
but is unlikely to play a role during combustion.
2018-07-30 21:15:17
CO 2 molecule
Master Equation Study
CO 2 environment
CO 2
OH
unimolecular master equations
alternative reaction mechanism
RRKM