Photochemistry of anhydrides. Part 1.—Photolysis of perfluoroacetic anhydride vapour: a new source of CF3 radicals
- 1 January 1972
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases
- Vol. 68, 88-95
- https://doi.org/10.1039/f19726800088
Abstract
The photolysis of perfluoroacetic anhydride was studied in the temperature range 19–177°C using wavelengths in the range 254–265 nm. The photolysis is exceptionally simple and is quantitatively described by the reactions (CF3CO)2O +hν→ 2CF3+ CO + CO2, CF3+ CF3 [graphic omitted] C2F6, The anhydride was tested as a source of CF3 radicals by photolyzing it in the presence of CH4 and of cyclohexane. For the reactions CF3+ CH4→ CF3H + CH3(7), CF3+ c-C6H12→ CF3H + c-C6H11, (12), we obtain log(k7/k1 c)/(cm3/2 mol–1/2 s–1/2)=(5.93 ± 0.32)–(12500 ± 700)/θ, (logk12/k1/2 c)/(cm3/2 mol–1/2 s–1/2)=(5.18 ± 0.15)–(5560 ± 220)/θ, where θ= 2.303 RT/cal mol–1. These results agree with previous ones obtained using conventional sources of CF3 radicals. We conclude that perfluoroacetic anhydride is a convenient new source of CF3 radicals.Keywords
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