Evidence for the unimolecular decomposition of CF3OCF3 to COF2 and CF4 by high energy irradiation

The electron beam irradiation of CF3OCF3 produces COF2 and CF4 in a nearly 1:1 stoichiometric ratio. •The electron beam induced decomposition of CF3OCF3 produces COF2 and CF4.•The CF3OCF3 decomposition and COF2 and CF4 evolution occurs in a nearly 1:1 stoichiometric ratio.•Unimolecular decomposition is consistent with the observed stoichiometry of the radiation-induced degradation. The decomposition of CF3OCF3 via electron beam irradiation in the gas phase and isolated in an argon matrix at T=10K is investigated via infrared spectroscopy. CF3OCF3 produces only COF2 and CF4. In the gas phase irradiation, the G value for CF3OCF3 decomposition is 5.9, and the G values for formation of COF2 and CF4 are 5.0 and 4.9, respectively. In the low temperature matrix isolated irradiation, CF3OCF3 decomposition and COF2 evolution occur in a 1:1 ratio. The results strongly suggest that a unimolecular mechanism for the formation of COF2 is operative because the product yields in the gas phase and matrix exposures are similar.