Simultaneous separation of perfluorocarbons and oxyfluorocarbons using capillary gas chromatography: analysis of the products of hexafluoropropene oxidation

Capillary gas chromatography was investigated as a method of analyzing and quantifying the products of the high-temperature gas-phase oxidation of hexafluoropropene. Standard polysiloxane polymer stationary phases were found to be ineffective in separating the aggressive mixture of oxyfluorocarbons and perfluorocarbons. Adsorbent type stationary phases provided better retention and separation for the exceedingly volatile components than polar/non-polar liquid phases. The tested silica-based porous-layer phase was found to be susceptible to degradation through interaction with acid fluoride species. The analysis was ultimately performed in two stages. Authentic oxidation product gas samples were first analyzed, then treated with aqueous potassium hydroxide to remove carbonyl compounds and resampled to determine oxygen content on the same system. Detector response factor ratios for a number of different perfluorocarbons were obtained, the information which is useful for chromatographic method development but is conspicuously absent in the open literature. The system was found to have good long-term stability with calibration deviations of less than 3% over a period of two years.