Biradical Intermediates in Tetrafluoroethylene Dissociation and Difluorocarbene Recombination

Tetrafluoroethylene pyrolysis has been studied under the strictly homogeneous conditions of a free-piston monopulse adiabatic compression set-up, and biradical intermediate C˙F2−C˙F2 is shown to precede CF₂ formation. The rate constant for biradical decomposition into two CF₂ species is estimated to be K₄=10^13.5±0.1exp(–201 ± 8 kJ mol⁻¹/RT) s⁻¹. Based on the detailed equilibrium principle CF₂ recombination is proposed to take place through biradical formation.