Abstract
The kinetics and mechanism of the oxygen exchange between C18O2 and MoO3 have been examined in the temperature range 673–793 K and in the pressure range 24–146 Pa. The rate of oxygen exchange was proportional to the pressure of CO2 with an activation energy of 94.5 kJ mol–1, which was smaller than that for the catalytic oxidation of CO with O2 on MoO3 by 22.1 kJ mol–1. The rate constant of oxygen exchange between CO2 and MoO3, Rco2, was 51–25 times larger than that for the catalytic oxidation of CO with O2 on MoO3, kco2, at 673–793 K; both had similar frequency factors and fractions of effective collisions were estimated to be almost the same. The difference between Rco2 and kco2 originated from the difference in the activation energies between the two reactions. An active complex with a unidentate carbonate was proposed in the oxygen exchange mechanism.
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