Kinetic origin of the ozone isotope effect: a critical analysis of enrichments and rate coefficients

Abstract

The oxygen isotope anomaly in ozone was first identified in isotopomers ⁴⁹O₃ and ⁵⁰O₃ with enrichments of over 10%. Recent rate coefficient measurements imply a new interpretation of the anomaly. The large variability of the rate coefficients of ozone formation O + O₂ → O₃ of about 50% characterizes the ozone isotope effect and demonstrates its kinetic origin. Surprisingly, the rate coefficients correlate with the zero-point energy change of the oxygen molecules participating in the isotope exchange reactions but not with the mass of the ozone molecules. Rate coefficients of symmetric molecules depart from this linear relationship by about 20%.