Flameless Operating Mode for Improved Multiple Flame Photometric Detection in Gas Chromatography

Abstract

A novel flameless operating mode is introduced, which improves the response of a multiple flame photometric detector (mFPD). The mFPD normally has analyte travel through 4 ‘worker’ flames in series before entering a final ‘analytical’ flame where its emission is monitored. Here, it is found that when the analytical flame is not ignited, background luminescence is reduced over 30 times and the strong analyte chemiluminescence of the worker flames can be made to extend a large distance (~ 10 flame widths) into the analytical flame region where it is detected. This occurs for phosphorous (HPO*), quadratic sulfur (S₂*), and linear sulfur (HSO*) emission. Conversely, carbon emission resides inside the worker flames and yields a small negative signal. As a result, very good selectivity over carbon is observed, and improved minimum detectable limits (MDL) of 4 pg S/s (S₂*) and 0.3 pg P/s (HPO*) are obtained, which are up to 20 times lower than previous values reported for the mFPD. Further, linear sulfur (HSO*) yields an MDL of 6 pg S/s, which is over 3 times lower than values reported for other FPDs. Due to the worker flames present in this mode, other benefits of regular mFPD operation are maintained, like uniform analyte response and large quenching resistance. In application, a trace benzothiophene analyte is readily detected within a concentrated diesel fuel matrix in the flameless mFPD mode, while no response is observed in the conventional FPD mode. Results indicate that this flameless operating mode is advantageous for sulfur and phosphorous analysis.

Graphical Abstract