Abstract
(CO2) and (CO3) structures were proposed as the activated complex of the rate determining and isotope fractionation governing step in the catalytic oxidation of CO over NiO catalyst. Following Bigeleisen’s formalism, the theoretical rate constant ratios for 13C and 14C substitution were calculated and compared with the experimental values. Computational analysis confirmed the (CO2) activated complex and pointed out that the (CO3) activated complex could not explain the experimetal results.