Methods and materials are provided for the production of essentially isomerically pure perhalogenated and partially halogenated compounds. One embodiment of the present invention provides a process for the production of essentially isomerically pure CFC-216aa. Other embodiments include processes for the production of CFC-217ba and HFC-227ea. Particular embodiments of the present invention provide separation techniques for the separation of chlorofluorocarbons from HF, from other chlorofluorocarbons, and the separation of isomers of halogenated compounds. Still other embodiments of the present invention provide catalytic synthetic techniques that demonstrate extended catalyst lifetime. In other embodiments, the present invention provides catalytic techniques for the purification of isomeric mixtures.