Practical Aspects of Thermal Dissociation and Recombination Reactions: the Reaction Systems CF ₃ X(+M)↔CF ₃ +X (+M) with X=F, Cl, Br, and I

Abstract The thermal dissociation/recombination reactions of the perfluoromethyl halides CF 4 ↔CF 3 +F, CF 3 Cl ↔ CF 3 +Cl, CF 3 Br ↔ CF 3 +Br, and CF 3 I ↔ CF 3 +I are analyzed with respect to their transition (for increasing pressures) from second‐order to first‐order dissociation (or from third‐order to second‐order recombination). The dependence of this transition on the temperature is documented. Practical aspects of the modelling of falloff curves are discussed.