(1) now at Department of Chemistry, Sam Houston State University, Huntsville, Texas USA,
(2) Cooperative Institute for Research in Environmental Sciences and Department of Chemistry and Biochemistry, University of Colorado, Boulder, CO, USA,and
(3) Department of Chemistry and the Center for the Management, Utilization, and Protection of Water Resources, Tennessee Technological University, Cookeville, Temnnessee, USA
Phosphine, alkylated phosphines and monophosphinate esters are detected with high sensitivity in capillary gas chromatography (GC) by their chemiluminescent reactions with molecular fluorine. Detection limits for these oxygen-sensitive compounds are estimated to be 1.3 pg, 0.5 pg, 8 pg, and 17 pg for phosphine, trimethyl phosphine, trimethyl phosphinate ester, and triethyl phosphine, respectively. As found in earlier work with alkylated sulfur, selenium and tellurium compounds, the detector exhibits a linear response. For triethyl phosphine, a linear range of greater than three orders of magnitude was demonstrated. Emission spectra were obtained for the trimethyl phosphine and triethyl phosphine systems. Chemiluminescence emitters include electronically excited HCF, vibrationally excited HF, and an unknown species in the trimethyl phosphine system. Mostly excited HF was detected in the triethyl phosphine system. Under the reaction conditions employed in the GC detector, the principal emitter is HCF for trimethyl phosphine and HF for triethyl phosphine. This detector may have important applications in investigations of the biogeochemical cycling of phosphorous.