SIFT-MS: development of instrumentation and applications.

dc.contributor.authorFrancis, Gregory Jamesen
dc.date.accessioned2010-03-31T22:41:07Z
dc.date.available2010-03-31T22:41:07Z
dc.date.issued2007en
dc.description.abstractData is presented for a range of experiments that have been performed using a selected ion flow tube (SIFT) instrument operated at room temperature (~ 298K) with carrier gas pressures typically in the range of 0.3 – 0.6 Torr. The majority of the experiments discussed are performed on a Voice100 instrument that has not been described in detail previously. The Voice100 is a novel instrument that has been designed particularly for quantitative trace gas analysis using the SIFT-MS technique. A mixture of helium and argon carrier gases are employed in the Voice100 flow tube. By mixing carrier gases, the flow dynamics and diffusion characteristics of a flow tube are altered when compared to classic single carrier gas models. Therefore firstly, optimal flow conditions for the operation of a Voice100 are characterised. The diffusion of an ion in a mixture of carrier gases is then characterised using theoretical models and experimental techniques. This research requires that a new parameter Mp be defined regarding the mass discrimination of an ion in the non-field-free region near the downstream ion sampling orifice. Furthermore, a new method is described for the simultaneous measurement of rate coefficients for the reactions of H₃O⁺.(H₂O)n (n = 1, 2, 3) ions with analytes. Rate coefficients and branching ratios for the reactions of SIFT-MS precursor ions with specific analytes related to four individual applications are presented. For each application, the kinetic parameters are determined so as to facilitate the quantitative detection of the analytes relevant to that application. The GeoVOC application involves the measurement of hydrocarbon concentrations in the headspace of soil and water across a range of humidities. Alkyl esters are investigated to allow for the quantitative detection of each compound in fruits and vegetables. Chemical warfare agents, their surrogates and precursor compounds are studied which allows for the quantitative or semi-quantitative detection of a range of highly toxic compounds. Finally, 17 compounds classified by the US-EPA as hazardous air pollutants are studied that enables SIFT-MS instruments to replicate sections of the TO-14A and TO-15 methods.en
dc.identifier.urihttp://hdl.handle.net/10092/3676
dc.identifier.urihttp://dx.doi.org/10.26021/8088
dc.language.isoen
dc.publisherUniversity of Canterbury. Chemistryen
dc.relation.isreferencedbyNZCUen
dc.rightsCopyright Gregory James Francisen
dc.rights.urihttps://canterbury.libguides.com/rights/thesesen
dc.subjectSelected Ion Flow Tubeen
dc.subjectSIFT-MSen
dc.subjectIon-molecule kineticsen
dc.subjectComputational Chemistryen
dc.titleSIFT-MS: development of instrumentation and applications.en
dc.typeTheses / Dissertations
thesis.degree.disciplineChemistryen
thesis.degree.grantorUniversity of Canterburyen
thesis.degree.levelDoctoralen
thesis.degree.nameDoctor of Philosophyen
uc.bibnumber1079621en
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