Atmospheric chemistry of CF3C(O)OCH2CF3: UV spectra and kinetic data for CF3C(O)OCH(center dot)CF3 and CF3C(O)OCH(OO center dot)CF3 radicals, and atmospheric fate of CF3C(O)OCH(O center dot)CF3 radicals

Pulse radiolysis transient UV absorption spectroscopy was used to study the ultraviolet absorption spectra (230-330 nm) and kinetics of CF3C(O)OCH(.)C F, and CF3C(O)OCH(OO .)CF3 radicals at 296 K. At 280 nm sigma(CF3C(O)OCH(.) CF3) = (1.08 +/- 0.13) x 10(-18) cm(2) molecule(-1), at 240 nm sigma(CF3C(O )OCH(OO .)CF3) (2.06 +/- 0.24) x 10(-18) cm(2) molecule(-1). Rate constants for the reaction of F atoms with CF3C(O)OCH2CF3, the self-reactions of CF3 C(O)OCH(.)CF3 and CF3C(O)OCH(OO)CF3 radicals, and the reactions of CF3C (O) OCH(OO)CF3 radicals with NO and NO2 were (1.8 +/- 0.2) x 10(-12), (1.5 +/- 0.2) x 10(-11), (7.6 +/- 0.9) x 10-12, (1.5 +/- 0.2) x 10(-11) and (8.5 +/- 0.9) x 10(-12) cm(3) molecule(-1) s(-1), respectively. The atmospheric fat e of CF3C(O)OCH(O .)CF3 radicals was investigated in a FTIR smog chamber. T hree loss processes for the CF3C(O)OCH(O .)CF3 radicals were identified at 296 K and 700 Torr total pressure, reaction with O-2 to form CF3C(O)OC(O)CF 3, alpha-rearrangement to form CF3C(O). radicals and CSC(O)OH, and decompos ition via a mechanism which is unclear. In 760 Torr of air at 296 K, 65% of the CF3C(O)OCH(O .)CF3 radicals react with oxygen, 18% undergo alpha-rearr angement, while the fate of the remaining 17% is unclear.