Product distribution in the Cl-initiated photooxidation of CF3C(O)OCH2CF3

M. B. BLANCO, I. BARNES AND MARIANO A. TERUEL

JOHN WILEY & SONS LTD

Año: 2010 vol. 23 p. 950 - 950

he product distribution and the mechanism of the reaction of Cl atoms with 2,2,2- trifluoroethyl 2,2,2-trifluoroacetate (CF3C(O)OCH2CF3) were investigated using a 1080 L environmental chamber with in situ FTIR spectroscopy detection. The experiments were performed at (296 ± 2) K and atmospheric pressure (760 ± 10) Torr of synthetic air free of NOx. A yield of (45 ± 3) % was obtained for the CF3C(O)OC(O)CF3 formation. CF2O and CO were found to be secondary products with estimated yields of 35 and 28 %, respectively. No trifluoroacetic acid (CF3C(O)OH) was observed. The yields determined are rationalized in terms of the competitive reaction channels for the fluoroalcoxy radicals formed in the H-abstraction process: a) reaction with O2, b) C-C, C-O, C-H decomposition and c) a possible α-ester rearrangement pathway. The negligible importance of the α-ester channel, to produce trifluoroacetic acid, was explained by the reduction of the stability of the five-membered tr