QUANTUM YIELD IN THE GAS-PHASE PHOTOLYSIS OF PERFLUOROACETYL CHLORIDE- A COMPARISON WITH RELATED-COMPOUNDS

The photolysis of perfluoroacetyl chloride vapour was studied in the p ressure range 4.6-59.9 Torr and with addition of inert gas up to 535.2 Torr using light of 254 and 280 nm. The quantum yield for the decompo sition of CF3COCl taken as Phi[CF3Cl + 2C(2)F(6)] = 0.98 +/- 0.13 was not affected by the total pressure, the intensity and the wavelength o f the light within the studied range of conditions. In the presence of c-C6H12 a clear hydrogen abstraction reaction took place indicating t he presence of CF3 radicals. An upper limit for the rate of hydrogen a bstraction of log k(H)(cm(3) mol(-1) s(-1)) = 7.9 at 298 K was obtaine d. Light emission was not observed over the range 330-600 nm. Mechanis ms for the decomposition of perfluoroacyl halides are discussed.