A non-mass-dependent isotopic fractionation effect

Isotopic fractionation is discussed in terms of collision cross sections. Under thermal equilibrium conditions, isotopically non-reactive collisions and collisions involving indistinguishable isotopes have no effect on the concentration of isotopic species: isotopic exchange reactions give rise to the well known mass-dependent isotopic fractionation (MDF). Under non-thermal equilibrium conditions, the non-reactive and indistinguishable cross sections must be taken into account since they participate in the loss of energy (thermalisation) of the hot species. If an isotope exchange between hot and cold species occurs during the thermalisation, the relative isotopic abundances contribute to the reaction rates and the MDF rule is not valid anymore. A general formulation of the isotopic fractionation, accounting for thermal and non-thermal situations, is proposed. The experimental results obtained during the synthesis of ozone 1] are well explained by the present treatment, which could be extended to other isotopic anomalies observed in meteorites.