THE PHOTOLYSIS OF TRIFLUOROACETIC ACID VAPOR

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Abstract
The photolysis of CF3COOH vapor has been studied at temperatures between about 90 and 190 °C, using light of wavelengths between 2000 and 2200 Å. The major products were CO2 and C2F6, with smaller amounts of CO, H2, and CF3H. A marked reduction in the yields of CO2, CO, and H2 with increasing pressure of added isobutane or 1-butene has been interpreted to imply the presence of free COOH radicals in the system, which is supported by the tentative identification of formic and oxalic acids as products of the photolysis. It is thought that the reaction[Formula: see text]represents the main primary photolytic process, with the minor processes[Formula: see text]and[Formula: see text]accounting for no more than 27 and 7% respectively of the total at 165 °C.Some tentative conclusions have been drawn about the reactions of COOH radicals. In the present system, the disproportionation reaction,[Formula: see text]appears to predominate, with the decomposition reaction,[Formula: see text]apparently of minor importance at 165 °C.

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