Abstract The kinetics for the oxidation of carbon monoxide in the presence of excess oxygen over Pt–Rh alloy catalysts were studied by using the reversed-flow gas chromatography technique. Suitable mathematical analysis equations were derived by means of which the rate constants for the oxidation reaction of carbon monoxide, as well as for the adsorption and desorption of the reactant CO on the catalysts pure Pt, 75 atom% Pt+25 atom% Rh, 50 atom% Pt+50 atom% Rh, 25 atom% Pt+75 atom% Rh and pure Rh supported on SiO 2 were determined. All the catalysts show a maximum rate constant for the production of CO 2 at a characteristic temperature close to that found in the literature. The rate constants for the adsorption of CO increase generally with increasing temperature, while those for the desorption decrease with increasing temperature. From the variation of the rate constants with temperature activation energies for the oxidation reaction and adsorption of CO were determined, which are sensitive to the composition of the catalytic surface. The appearance of CO 2 and carbon, when introducing pure CO into the column with the catalysts, verified a partial dissociative adsorption (e.g., disproportionation) of CO on the catalysts used. The latter indicates a mechanism for the CO oxidation through a partial dissociative adsorption of CO followed by the reaction of adsorbed CO molecules with adsorbed O atoms.