Abstract
The photolysis of the vapour of perfluoro-n-butyric anhydride was studied at 20 and 227°C. The effective primary process is (n-C3F7CO)2O +hν→ 2 n-C3F7+ CO + CO2 and the overall decomposition is quantitatively described by the equation (n-C3F7CO)2O +hν→ n-C6F14+ CO + CO2 The quantum yields of products increase with temperature but are independent of pressure. (n-C3F7CO)2O was photolysed in the presence of cyclohexane vapour. For the reactions n-C3F7+ c-C6H12→ n-C3F7H + c-C6H11kH 2 n-C3F7→ C6F14kc we obtain, logkH/kc½=(4.99 ± 0.12)–(23910 ± 750)/θ where θ= 2.303RTJ mol–1 and kH/k½ c is in cm mol–½ s–½.

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