The Gas-Phase Decomposition of CF3OH with Water: A Radical-Catalyzed Mechanism

Abstract

CF₃OH is an atmospheric sink for hydrofluorocarbons (HFCs) and hydrofluoroethers (HFEs). Several new mechanisms, including catalyzation via H₂O and OH radical, for the decomposition of CF₃OH into HF and CF₂O are studied using ab inito methods. The present work demonstrates that the OH radical has a strong catalytic effect on the transition state for the decomposition of CF₃OH. The barrier is found to be reduced from 45.9 kcal mol⁻¹ for the unimolecular decomposition to 11.0 kcal mol⁻¹ for decomposition including H₂O and OH.