Chlorine abstraction reactions of fluorine. Part 1.—Reaction of fluorine with trichlorofluoromethane

Abstract

The kinetics and mechanism of the reaction of fluorine with CCl₃F have been investigated in a static system over the temperature range 491–598 K. The reaction was at least partly heterogeneous, independent of surface area to volume ratio, independent of diluent and uninhibited by either oxygen or chlorine monofluoride. The rate equation had the form : –d[CCl₃F]/dt=k[F₂]^½[CCl₃F]. The rate constants were reproducible using different Pyrex reaction vessels and fitted the Arrhenius equation : log k(l.^½ mol^–½ s^–1)=(6.77 ± 0.10)–(19 250 ± 240)/2.303 RT. A full mechanism is presented which, by using steady-state assumptions, agrees with the experimentally derived rate equation.