Reactions of CF3O− core ions with ClONO2 and H2O

Abstract

The reactions of CF₃O⁻, CF₃OHF⁻ and CF₃OH₂O⁻ with ClONO₂ have been studied in the temperature range 225–325 K. The reactions of CF₃O⁻ and CF₃OH₂O⁻ with ClONO₂ proceed at the collision rate whereas the reaction of CF₃OHF⁻ with ClONO₂ is slower. No significant temperature dependence of the rate constant has been found for each reaction. The mechanistic study has shown that the reaction of CF₃O⁻ with ClONO₂ proceeds by fluoride transfer and the product of the reaction between CF₃OH₂O⁻ and ClONO₂ is the cluster ion CF₃OClONO₂⁻. The equilibrium reaction of CF₃O⁻ with H₂O has been also studied between 262 and 295 K. Values of − 63.2 ± 6.7 kJ mol⁻¹ and − 114.6 ± 23.9 J mol⁻¹ K⁻¹ were derived for the standard reaction enthalpy and entropy, respectively.