Derivatizations for Improved Detection of Alcohols by Gas Chromatography and Photoionization Detection (GC-PID)

Authors: I. S. Kruil a; M. Swartz a; J. N. Driscoll b Affiliations: a The Barnett Institute and Department of Chemistry, Northeastern University, Boston, Massachusetts, USA b HNU Systems, Inc., Highlands, Massachusetts, USA DOI: 10.1080/00032718408059851 Publication Frequency: 18 issues per year Published in: Analytical Letters, Volume 17, Issue 20 1984 , pages 2369 - 2384 Subjects: Analytical Chemistry; Chemical Spectroscopy; Forensic Chemistry; Formats available: PDF (English)

Abstract
Pentafluorophenyldimethylsilyl chloride (flophemesyl chloride, F1) is a well known derivatization reagent for improved electron capture detection (ECD) in gas chromatography (GC)(GC-ECD), but it has never been utilized for improved detectability and sensitivity in GCphotoionization detection (GC-PID). We have now utilized a wide variety of flophemesyl alcohol derivatives in order to show a new approach for realizing greatly reduced minimum detection limits (MDL) of virtually all alcohol derivatives in GC-PID analysis. This particular derivatization approach is inexpensive and easy to apply, leading to quantitative or near 100% conversion of the starting alcohols to the expected flophemesyl ethers (silyl ethers). Detection limits can be lowered by 2-3 orders of magnitude for such derivatives when compared with the starting alcohols, along with calibration plots that are linear over 5-7 orders of magnitude. Specific GC conditions have been developed for many flophemesyl derivatives, in all cases using packed columns. Both ECD and PID relative response factors (RRFs) and normalized RRFs have been determined, and such ratios can now be used for improved analyte identification from complex sample matrices, where appropriate. We have attempted to describe in this preliminary report some interesting results and approaches for improved GC-PID detection of a large number of alcohols and alcohol analogs. The method of derivatization is extremely simple to perform, and appears to lead to a single, well-defined product of known structure in 100% yield or thereabouts. Chromatography for typical flophemesylalcohol analytes can be excellent, as in Figure 1, with symmetrical peak shape, little or no tailing, and overall excellent MDLs. With GC-detector-computer interfacing, we are able to obtain both chromatograms and preliminary as well as calculated data within a single 5-10 minute time span27 The total amount of time per analysis will obviously depend on the particular analyte derivative and the chromatography obtained. RRFs and normalized RRFs are quite easy to determine, they are fully reproducible, and can serve as good markers for a particular alcohol and its flophemesyl derivative. In view of the calibration plots possible and MDLs, these overall

analytical methods for GC-ECD-PID using flophemesyl derivatization should, we hope, find widespread and ready acceptance and utility by the analytical community. Keywords: GC-PID; gas chromatography; photoionization detection; derivatization; trace organic analysis

First HNU PI 51 1975

Replacement PID PI52-C 2008

Max. T (oC) Ion chamb. Material Dead Volume (uL) Det. Limit ppb Lamp lifetime (hrs.)

225 Teflon 350 20.0 5,000

275 Ceramic & gold 50 0.5 5,000

The early work (1976-78) was done with an HNU PI51 shown above. The replacement instrument (with improved specs) is a P I52-01C manufactured by:

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