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Catalytic Effect of Carbon Dioxide on Reaction OH + CO → H + CO2 in Supercritical Environment: Master Equation Study
journal contribution
posted on 2018-07-30, 21:15 authored by Artëm E. Masunov, Elizabeth E. Wait, Subith S. VasuWe 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.