Fundamental Studies of Reactions between NO3 Radicals and Organic Surfaces

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dc.contributor.authorZhang, Yafenen
dc.contributor.committeechairMorris, John R.en
dc.contributor.committeememberTroya, Diegoen
dc.contributor.committeememberTanko, James M.en
dc.contributor.committeememberTissue, Brian M.en
dc.contributor.departmentChemistryen
dc.date.accessioned2014-03-14T21:35:07Zen
dc.date.adate2012-05-14en
dc.date.available2014-03-14T21:35:07Zen
dc.date.issued2012-04-19en
dc.date.rdate2012-05-14en
dc.date.sdate2012-04-30en
dc.description.abstractUltrahigh vacuum (UHV) surface science experiments were designed to study reaction kinetics and mechanisms of gas-phase NO₃ radicals with well-organized, highly characterized, organic thin films. The surface reactions were monitored in situ with reflection-absorption infrared spectroscopy (RAIRS). The oxidation states of surface-bound molecules were identified with X-ray photoelectron spectroscopy (XPS). Consumption of vinyl groups was observed concurrently with formation of organic nitrates in RAIRS. XPS spectra showed little oxidation of sulfur head groups. The observed rate constant was determined based on the consumption of carbon-carbon double bonds and the formation of organic nitrates. Using this rate constant, the initial reaction probability was determined to be (3 ± 1) X 10⁻³. This reaction probability is approximately two orders of magnitude higher than that for the reactions between the same surface and pure O₃, which is due to the higher electron affinity of NO₃ relative to O₃. These results led to the development of a proposed mechanism that involves electrophilic addition of NO₃ to the double bonds. Reactions between NO₃ and a methyl-terminated SAM were also monitored in situ with RAIRS. In the CH3-SAM studies, hydrogen abstraction was observed during NO3 exposure. The results presented in this thesis should help develop an understanding of the fundamental interfacial reaction dynamics of NO₃ radicals with organic surfaces.en
dc.description.degreeMaster of Scienceen
dc.identifier.otheretd-04302012-132828en
dc.identifier.sourceurlhttp://scholar.lib.vt.edu/theses/available/etd-04302012-132828/en
dc.identifier.urihttp://hdl.handle.net/10919/42372en
dc.publisherVirginia Techen
dc.relation.haspartThesis_Yafen_Zhang_ETD.pdfen
dc.rightsIn Copyrighten
dc.rights.urihttp://rightsstatements.org/vocab/InC/1.0/en
dc.subjectnitrate radicalsen
dc.subjectself-assembled monolayersen
dc.subjectultrahigh vacuumen
dc.subjectelectrophilic additionen
dc.subjecthydrogen abstractionen
dc.titleFundamental Studies of Reactions between NO3 Radicals and Organic Surfacesen
dc.typeThesisen
thesis.degree.disciplineChemistryen
thesis.degree.grantorVirginia Polytechnic Institute and State Universityen
thesis.degree.levelmastersen
thesis.degree.nameMaster of Scienceen

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