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

The decomposition of CF3OCF3 via electron beam irradiation in the gas phase and isolated in an argon matrix at T = 10 K 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.