Pyrolysis of branched-chain perfluoroalkanes in the presence of halogens

Article abstract of DOI:10.1016/0022-1139(93)02945-B

The thermal decomposition of some highly branched perfluoroalkanes in the presence of molecular halogens (Cl2, Br2, I2) has been studied.The clear-cut cleavage of the most hindered carbon-carbon bond and the trapping by halogens of the intermediate radicals so formed account for the product distribution.Kinetic measurements support a mechanism based on homolytic rupture of the perfluoroalkanes as the rate-determining step, followed by the fast reaction of the intermediates with halogens.