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

Photon yields - the number of photons generated per analyte atom - are of o bvious analytical and mechanistic importance in flame chemiluminescence. Ho wever, such numbers are unavailable for spectral detectors in gas chromatog raphy las well as for most conventional spectroscopic systems). In this stu dy, photon yields have been determined for the chemiluminescence of several elements in the flame photometric detector (FPD). The number of photons ge nerated per atom of FPD-active element was 2 X 10(-3) for sulfur (emitter S *(2), test compound thianaphthene), 3 x 10(-3) for phosphorus [HPO*, tris(p entafluorophenyl)phosphine], 8 x 10(-3) for manganese (Mn*, methylcyclopent adienyl manganese tricarbonyl), 3 x 10-3 for ruthenium (emitter unknown, ru thenocene), 4 x 10(-5) for iron (Fe*, ferrocene) and 2 x 10(-4) for seleniu m (Se*(2), dimethylbenzselenazole). Total flows, maximum thermocouple tempe ratures, and visible flame volumes have also been estimated for each elemen t under signal/noise-optimized conditions in order to provide a database fo r kinetic calculations. (C) 2001 Elsevier Science B.V. All rights reserved.