Mercury-Photosensitized Oxidation of Tetrafluoroethylene

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Abstract
The mercury‐photosensitized reactions of C2F4 were studied in the absence and the presence of oxygen at room temperature. In the absence of oxygen, the only product was cyclo‐C3F6, whereas CF2O and another unidentified product were also formed in the presence of oxygen. The cyclo‐C3F6 formation rate was unaffected by oxygen or nitrogen and was proportional to the C2F4 pressure and the square root of the incident intensity. The results are explained. The oxidation apparently does not involve the CF2 radical. Two processes are introduced to explain the oxygenated products. One of these is attack of C2F4 by oxygen atoms produced from the mercury‐photosensitized decomposition of oxygen. The other involves the reaction of molecular oxygen with an electronically excited C2F4 molecule. The first oxidation process can be suppressed by the addition of nitrogen, whereas the second cannot. The oxidation mechanism presented is not complete but does explain the major trends.