Temperature dependence of isotopic fractionation in the CO(2)‐O(2) isotope exchange reaction

RATIONALE: Oxygen isotope exchange between O(2) and CO(2) in the presence of heated platinum (Pt) is an established technique for determining the δ (17)O value of CO(2). However, there is not yet a consensus on the associated fractionation factors at the steady state. METHODS: We determined experimentally the steady‐state α (17) and α (18) fractionation factors for Pt‐catalyzed CO(2)‐O(2) oxygen isotope exchange at temperatures ranging from 500 to 1200°C. For comparison, the theoretical α (18) equilibrium exchange values reported by Richet et al. (1997) have been updated using the direct sum method for CO(2) and the corresponding α (17) values were determined. Finally, we examined whether the steady‐state fractionation factors depend on the isotopic composition of the reactants, by using CO(2) and O(2) differing in δ(18)O value from −66 ‰ to +4 ‰. RESULTS: The experimentally determined steady‐state fractionation factors α (17) and α (18) are lower than those obtained from the updated theoretical calculations (of CO(2)‐O(2) isotope exchange under equilibrium conditions) by 0.0024 ± 0.0001 and 0.0048 ± 0.0002, respectively. The offset is not due to scale incompatibilities between isotope measurements of O(2) and CO(2) nor to the neglect of non‐Born‐Oppenheimer effects in the calculations. There is a crossover temperature at which enrichment in the minor isotopes switches from CO(2) to O(2). The direct sum evaluation yields a θ value of ~0.54, i.e. higher than the canonical range maximum for a mass‐dependent fractionation process. CONCLUSIONS: Updated theoretical values of α (18) for equilibrium isotope exchange are lower than those derived from previous work by Richet et al. (1997). The direct sum evaluation for CO(2) yields θ values higher than the canonical range maximum for mass‐dependent fractionation processes. This demonstrates the need to include anharmonic effects in the calculation and definition of mass‐dependent fractionation processes for poly‐atomic molecules. The discrepancy between the theory and the experimental α (17) and α (18) values may be due to thermal diffusion associated with the temperature gradient in the reactor.