The goal of this work was to investigate the properties of existing atomic emission systems which are useful for element-selective detection of chromatographic effluent. A microwave induced plasma (MIP) system has been optimized for the selective detection of boron in the effluent of a gas chromatograph. A method was developed for the analysis of total boron present in several lubrication oil additives and in several formulated lubrication oils. Values obtained by this method compare favorably with those obtained by other atomic emission spectroscopic (AES) methods. A direct current plasma (DCP) system has been optimized for the selective detection of boron in flowing organic liquid streams. A method was developed for the analysis of total boron present in several lubrication oil additives by flow injection analysis (FIA). A method was also developed for the qualitative separation "speciation" of these additives by size exclusion chromatography-DCP. Values obtained through this method compare favorably with values obtained through other AES methods. The MIP system was optimized for the selective detection of titanium in the effluent of the gas chromatograph. This system was used to analyze a group of reaction mixtures containing novel titanium chelates and organo-metallic compounds, as well as several organo-titanium-boron compounds. The MIP system was optimized for the selective detection of several of the group VA and group VIA elements in the effluent of the gas chromatograph. This system was used to characterize a series of coal standards (the Argonne Premium Coal Standards) by pyrolysis-GC-AES. Volatile compounds containing nitrogen, oxygen and sulfur were detected. The Py-GC-AES method was used to characterize several other coal, sedimentary and kerogen samples. Volatile phosphorous, arsenic, and selenium compounds were detected, as were compounds of nitrogen, oxygen and sulfur. The MIP system was evaluated as a detector suitable for on-line elemental analysis by simultaneous multi-element detection. Several anomalies were observed in the detector response to hydrogen, non-linear response being observed within a large set of model compounds examined. Chlorinated molecules demonstrated enhanced hydrogen response. The anomalies do not greatly affect the empirical formulae calculated for compounds, provided that the analyte mass delivered to the plasma is above $1\times10\sp{-10}$ g. Empirical formulae for a variety of model compounds, as well as for a mixture of sixteen chlorinated pesticides are presented. (Abstract shortened by UMI.)
| Identifer | oai:union.ndltd.org:UMASS/oai:scholarworks.umass.edu:dissertations-8349 |
| Date | 01 January 1992 |
| Creators | Seeley, Jeffrey Anderson |
| Publisher | ScholarWorks@UMass Amherst |
| Source Sets | University of Massachusetts, Amherst |
| Language | English |
| Detected Language | English |
| Type | text |
| Source | Doctoral Dissertations Available from Proquest |
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