Temperature-dependent electron capture detector response to common alternative fluorocarbons

The relative electron capture detector (ECD) response to alternative fluorocarbons (AFCs) using gas chromatography are found to be at least 1 order of magnitude lower than that for CFC-12. Detection limits for the chlorofluorocarbons CFC-12, HCFC-22, HCFC-123, and HCFC-124 are found to be 2.5, 90, 30, and 90 pg, respectively. Those for the hydrofluorocarbons are significantly poorer; 14 and 45 ng for HFC-125 and HFC-134a, respectively. HFC-152a was not detected using ECD. Since atmospheric concentrations of these compounds are in the low part-per-trillion level, GC-ECD is apparently not sensitive enough to be used for AFC analysis without substantial preconcentration. Two columns are evaluated for the AFC separation. The Poraplot Q WPLOT column showed good separation ability, though column bleed limits detection performance. A Carboxen 1004 packed column exhibits much lower interference. But separations are time consuming and peak broadening adversely affects limits of detection. Mechanisms for the ECD response are proposed based on thermodynamics and temperature-dependent ECD responses. CFC-12, HCFC-123, and HFC-125 apparently undergo ion-forming dissociative electron capture. The electron capture process for HCFC-22 and HFC-134a appear to form molecular ions. Both mechanisms appear to be operative for HCFC-124 electron capture. Dissociative electron capture rate constants for HCFC-123, HCFC-124, and HFC-125 are estimated to be 3.5 × 10(-)(10), 1.0 × 10(-)(10), and 5.6 × 10(-)(13) cm(3) s(-)(1), respectively at 300 °C.