Chemiluminescent photon yields measured in the flame photometric detector on chromatographic peaks containing sulfur, phosphorus, manganese, ruthenium, iron or selenium

Photon yields — the number of photons generated per analyte atom — are of obvious analytical and mechanistic importance in flame chemiluminescence. However, such numbers are unavailable for spectral detectors in gas chromatography (as well as for most conventional spectroscopic systems). In this study, photon yields have been determined for the chemiluminescence of several elements in the flame photometric detector (FPD). The number of photons generated per atom of FPD-active element was 2×10−3 for sulfur (emitter S2*, test compound thianaphthene), 3×10−3 for phosphorus [HPO*, tris(pentafluorophenyl)phosphine], 8×10−3 for manganese (Mn*, methylcyclopentadienyl manganese tricarbonyl), 3×10−3 for ruthenium (emitter unknown, ruthenocene), 4×10−5 for iron (Fe*, ferrocene) and 2×10−4 for selenium (Se2*, dimethylbenzselenazole). Total flows, maximum thermocouple temperatures, and visible flame volumes have also been estimated for each element under signal/noise-optimized conditions in order to provide a database for kinetic calculations.