A Rapid Analytical Method for the Selective Quenching-Free Determination of Thiols by GC-FPD

A rapid method is introduced, which facilitates the selective gas chromatography–flame photometric detection (GC–FPD) analysis of thiols. The method uses lead oxide particles or plumbite solution to complex thiols into a solid lead thiolate moiety that can be physically separated from complex sample matrices and then reconstituted as the original thiol in a simple replacement solvent for analysis. While both red or yellow forms of lead oxide are found to remove thiols from sample solutions, the latter does so about 10 times faster than the former. Comparatively, though, plumbite solution is most rapid in this regard and is still 10 fold faster than solid yellow lead oxide. For example, 98 ± 1% ( n = 3) of a 1-butanethiol standard in hexane (600 ng µL − 1 ) was extracted after only 2 min of contact with a 0.06 M plumbite solution. The method allows thiols to be selectively isolated from co-eluting peaks and other sulfur species, which can simplify their determination. It also allows thiols to be removed from complex hydrocarbon matrices for analysis, which can greatly reduce interference from signal quenching when using a conventional FPD. For instance, analysis of a thiol standard in a commercial gasoline by this method showed that the FPD sulfur signal increased from 16 to 97% of its expected value by removing the quenching hydrocarbon interference. Accordingly, results indicate that this method could be a useful alternative approach for the selective analysis of such thiol-containing samples. Graphical Abstract