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The atmospheric degradation of HFC-134a (CF₃CFH₂) proceeds via the formation of CF₃CFHO radicals. Long path length FTIR environmental chamber techniques were used to study the atmospheric fate of CF₃CFHO radicals. Two competing reaction pathways were identified for CF₃CFHO radicals:  reaction with O₂, CF₃CFHO + O₂ → CF₃C(O)F + HO₂, and decomposition via C−C bond scission, CF₃CFHO + M → CF₃ + HC(O)F + M. CF₃CFHO radicals were produced by two different reactions:  either via the self-reaction of CF₃CFHO₂ radicals or via the CF₃CFHO₂ + NO reaction. It was found that decomposition was much more important when CF₃CFHO radicals were produced via the CF₃CFHO₂ + NO reaction than when they were produced via the self-reaction of CF₃CFHO₂ radicals. We ascribe this observation to the formation of vibrationally excited CF₃CFHO* radicals in the CF₃CFHO₂ + NO reaction …