Pyrolysis of 1-chloro-1,1-difluoroethane: Considerations about its molecular nature

Abstract

A new insight into the contested origin of the absence of radical reaction in the pyrolysis of CF 2 ClCH 3 is given. This chain reaction would be too slow compared with the molecular reaction because of a too slow homogeneous initiation leading to a too fast wall recombination of the Cl atom chain carriers.

Pyrolysis of 1,1-dichloro-1-fluoroethane in the absence and presence of added propene or CCl4: A computer-aided kinetic study

“…Kinetic and mechanistic studies in our laboratory have shown that the thermal dehydrochlorination of CCl 3 CH 3 is mainly a radical reaction [1], while that of CClF 2 CH 3 is molecular [2,3]. This work deals with the intermediate case of CCl 2 FCH 3 (Freon 141b), which completes the series CCl 3Ϫn F n CH 3 , with n ϭ 0 -2.…”

“…l Experimental value from [13]. Cl and CClF 2 CH 3 , calculated from data given in [1] and [3], respectively.…”

“…The model consisted of the reactions fromTable I, the isomerization, the decomposition of the produced radicals, their reactions with HCl and Cl 2 , and all possible reverse reactions and chain terminations 3. Calculated for experimental conditions from Sianesi et al[4] (200 torr of CCl 2 FCH 3 at 803 K and a reaction time of 2 s) using the rate constant measured by these authors.…”