Novel Strategies for Organosulfur Analysis in Gas Chromatography with Flame Photometric Detection

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dc.contributor.advisorThurbide, Kevin B.
dc.contributor.authorMcKelvie, Kaylan Halcyon
dc.contributor.committeememberGailer, Jürgen G.
dc.contributor.committeememberMarriott, Robert A.
dc.contributor.committeememberLing, Changchun
dc.contributor.committeememberNorman, Ann-Lise
dc.contributor.committeememberHarynuk, James J.
dc.date2020-06
dc.date.accessioned2020-04-16T16:31:54Z
dc.date.available2020-04-16T16:31:54Z
dc.date.issued2020-04-09
dc.description.abstractThis thesis describes the development of novel methods to analyze organosulfur compounds using gas chromatography (GC) with flame photometric detection (FPD). The first area of exploration utilizes a water stationary phase for sulfur separations. Several organosulfur compounds are retained to varying degrees on this phase, while non-polar hydrocarbons are unretained. This prevents the co-elution of sulfur analytes with hydrocarbons and the response quenching that is often observed in GC-FPD. Overall, the water stationary phase is shown to be a useful alternative for the analysis of organosulfur compounds in complex matrices. Next, a sample preparation method using lead oxide particles or plumbite solution is demonstrated 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. The method allows thiols to be selectively isolated from co-eluting peaks, which can simplify their determination and greatly reduce interference from signal quenching when using an FPD. As an extension of this technique, a selective chromatographic system is also demonstrated. This uses PbO or plumbite as a pre-column trap for thiols, which allows non-thiols to separate as normal while thiols are not eluted until in situ reconstitution. This illustrates the potential for their controlled GC analysis. Accordingly, results indicate that these methods could be useful alternative approaches for the selective analysis of such thiol-containing samples. Lastly, a novel miniaturized GC-FPD device built within a titanium platform (Ti µGC-FPD) is presented. The monolithic Ti device contains both a separation column and a shielded cavity to house the detector flame. The FPD employs a micro counter-current flame that is stabilized by opposing relatively low flows of oxygen and hydrogen, with minimum detectable limits of about 70 pg S/s for sulfur and 8 pg P/s for phosphorous. Overall, good separations with stable and sensitive detector performance are obtained with the device, and its sturdy Ti structure supports robust operation. Results indicate that this Ti µGC-FPD device may be a useful alternative approach for incorporating selective FPD sensing in µGC analyses.en_US
dc.identifier.citationMcKelvie, K. H. (2020). Novel Strategies for Organosulfur Analysis in Gas Chromatography with Flame Photometric Detection (Doctoral thesis, University of Calgary, Calgary, Canada). Retrieved from https://prism.ucalgary.ca.en_US
dc.identifier.doihttp://dx.doi.org/10.11575/PRISM/37681
dc.identifier.urihttp://hdl.handle.net/1880/111802
dc.language.isoengen_US
dc.publisher.facultyScienceen_US
dc.publisher.institutionUniversity of Calgaryen
dc.rightsUniversity of Calgary graduate students retain copyright ownership and moral rights for their thesis. You may use this material in any way that is permitted by the Copyright Act or through licensing that has been assigned to the document. For uses that are not allowable under copyright legislation or licensing, you are required to seek permission.en_US
dc.subjectgas chromatographyen_US
dc.subjectflame photometric detectionen_US
dc.subjectthiolsen_US
dc.subjectquenchingen_US
dc.subjectsulfuren_US
dc.subjectstationary phaseen_US
dc.subjectwateren_US
dc.subjectminiatureen_US
dc.subjecttitaniumen_US
dc.subject.classificationChemistry--Analyticalen_US
dc.titleNovel Strategies for Organosulfur Analysis in Gas Chromatography with Flame Photometric Detectionen_US
dc.typedoctoral thesisen_US
thesis.degree.disciplineChemistryen_US
thesis.degree.grantorUniversity of Calgaryen_US
thesis.degree.nameDoctor of Philosophy (PhD)en_US
ucalgary.item.requestcopytrueen_US
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