Mercury-Sensitized Photolysis of C2F4

Tetrafluoroethylene was decomposed by mercury photosensitization at temperatures from 21° to 224°C. At pressures below 60 mm, the only product was c‐C₃F₆ and its production was linear with the C₂F₄ pressure and enhanced by raising the temperature. The CF₂ radicals produced during photolysis can either recombine or add to the substrate: $$\begin{array}{c}2{\mathrm{CF}}_2\to {\displaystyle {lim}_{k_6}}{\mathrm{C}}_2{\mathrm{F}}_4,\\ {\mathrm{CF}}_2+{\mathrm{C}}_2{\mathrm{F}}_4\to {\displaystyle {lim}_{k_7}}c{\mathrm{-C}}_3{\mathrm{F}}_6.\end{array}$$ The rate constant ratio k₇/k₆^½ was found to be 395 exp (−6700/RT) (liter/mole·sec)^½.