Title page for ETD etd-452222539751141

Type of Document Dissertation
Author Shi, Heng
Author's Email Address heng.shi@vt.edu
URN etd-452222539751141
Title Supercritical Fluid Chromatography with Chemiluminescent Nitrogen and Sulfur Detection
Degree PhD
Department Chemistry
Advisory Committee
Advisor Name Title
Bell, Harold M.
Glanville, James O.
McNair, Harold M.
Viers, Jimmy W.
Taylor, Larry T. Committee Chair
  • supercritical fluid chromatography
  • chemiluminescence detection
  • CLND
  • SCLD
  • pharmaceuticals
  • pesticides
  • food flavor
Date of Defense 1997-04-21
Availability unrestricted
The need for sensitive and selective detectors in supercritical fluid chromatography (SFC) is particularly evident since SFC can be used to analyze classes of compounds that are not readily amenable to either gas chromatography (GC) or liquid chromatography (LC). These compounds include species that are nonvolatile or thermally labile and , in addition, contain no chromophore that can be used for spectrophoto detection. The objective of this research is therefore to interface selective chemilumninescent detectors with SFC in the sensitive detection of nitrogen- and/or sulfur containing compounds.

The chemiluminecent nitrogen detector (CLND), a gas-phase detector which is specific for nitrogen-containing compounds, was first evaluated as a detector for use with capillary SFC. The potential use of the CLND for food flavor and petroleum samples was demonstrated. In addition to equimolar nitrogen response, the CLND showed good sensitivity and large linear dynamic range. Minimum detectable quantity (MDQ) was 60 pg of nitrogen with a linear range of over 3 orders of magnitude. Nitrogen to carbon selectivity of 105 was obtained. Capillary SFC with simultaneous flame ionization and chemiluminescent detection was also demonstrated.

The second portion of the research investigated the CLND for packed column SFC with methanol modified CO2. The only modification made in the CLND for packed column SFC is the pyrolysis furnace. The CLND and UV were used to interface with SFC via a post-column split. Methanol-modified CO2 was also demonstrated to be compatible with the CLND even with a high mobile phase flow rate. The use of pressure and modifier programs appears to be feasible as is evidenced by the baseline studies which have been performed, as well as by the applications demonstrated.

The last portion of the research focused on the evaluation of a new generation sulfur chemiluminescent detector (SCLD), which is also a gas-phase detector, with packed column SFC using both pure and methanol modified CO2. The minimum detectable quantities were determined to be 2.6 pg or 14 pg sulfur for mobile phase employing pure CO2 or 8% methanol modified CO2 respectively. The evaluation study also showed excellent selectivity and linearity, as well as day-to-day repeatability. The capabilities of the SFC-SCLD system for sulfur speciation and detection of thermally labile pesticides and polar sulfonamides, as well as petrochemical samples were presented.

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