Several fluorine‐containing ethanes (monofluoro, 1,1‐difluoro, 1,1,1‐trifluoro, 1,1,2‐trifluoro, 1,1,2,2‐tetrafluoro, and pentafluoro) and ethenes (1,1‐difluoro and trifluoro) form hydrogen fluoride when irradiated with gamma rays in the gas phase at 25°C. Hydrogen fluoride is apparently formed from fluoroethanes by a mechanism which involves formation of an intermediate semiion pair. We observed identical HF yields both in the absence and presence of molecular oxygen, except for monofluoroethane. A reduction of G(HF) with increasing sample pressure, for example, of 1,1,2,2‐tetrafluoroethane, indicates that collisional stabilization of excited fluoroethane molecules competes with the process of HF elimination. High G values for HF and CO2 in mixtures of CF2CFH and O2 reveal the occurrence of a chain reaction.
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