Atmospheric degradation mechanism of CF3OCH3

A smog chamber/FTIR technique was used to study the Cl atom initiated oxida tion of CF3OCH3 in 700 Torr of N-2/O-2 at 296 K. Using relative rate techni ques it was determined that k(Cl + CF3OCH3) = (1.4 +/- 0.2) x 10(-13) and k (Cl + CF3OC(O)H) = (9.8 +/- 1.2) x 10(-15) cm(3) molecule(-1) s(-1). At 700 Torr of N-2/O-2 diluent at 296 K reaction with O-2 is the only loss mechan ism of the CF3OCH2O. radical. The infrared spectra of the peroxy nitrates C F3OCH2O2NO2 and CF3OC(O)O2NO2 were recorded and compared to the nonfluorina ted analogues CH3OCH2O2NO2 and CH3OC(O)O2NO2. The thermal decomposition rat e of CF3OC(O)O2NO2 is (2.3 +/- 0.1) x 10(-4) s(-1) in 700 Torr of N-2 at 29 5.8 K. The reaction of CF3OC(O)O-2 radicals with HO2 radicals gives CF3OC(O )H in a yield of (80 +/- 11)%. The results are discussed with respect to th e atmospheric degradation mechanism of CF3OCH3 and other ethers.