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ESR investigation of some free-radical adducts

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dc.contributor.authorKozloski, Richard Peteren
dc.contributor.committeechairDessy, Raymond E.en
dc.contributor.committeememberClifford, Alan F.en
dc.contributor.committeememberField, Paul E.en
dc.contributor.committeememberGibbs, Gerald V.en
dc.contributor.committeememberOgliaruso, Michael A.en
dc.contributor.departmentChemistryen
dc.date.accessioned2014-03-14T21:16:12Zen
dc.date.adate2010-07-15en
dc.date.available2014-03-14T21:16:12Zen
dc.date.issued1977-01-15en
dc.date.rdate2010-07-15en
dc.date.sdate2010-07-15en
dc.description.abstractThe effect of steric strain on the esr hyperfine coupling constants of several free-radical adducts of perfluoropropene and perfluoro-2-butene were investigated. Silyl, hydroxyalkyl, thiyl and alkoxy free radicals, which were generated by photo-irradiation, reacted with these olefins to form free-radical adducts. Trends in the esr hfs were then looked for in each class of adducts. The thiyl and alkoxy radicals were found to be unsuitable for this type of study due to the low degree of steric strain produced by these species in the adducts. Trends toward higher a-Fβ/CF₃ hfs and lower a<sup>Fα</sup> hfs were observed for the silyl and hydroxyalkyl radical adducts as the steric strain in the adduct was increased. The ratio of the <sup>Fα</sup> to a-Fβ/CF₃ hfs was shown to be a good measure of the degree of steric strain in these radical adducts. The possibility that the (Me₃Si)₂CHC(SiMe₃)₂ free radical, which has been reported to contain an "esr invisible" β-H, might be misidentified was investigated. Our conclusion was that the β-H is present and has not been replaced by a t-butoxy group.en
dc.description.degreePh. D.en
dc.format.extent101 leavesen
dc.format.mediumBTDen
dc.format.mimetypeapplication/pdfen
dc.identifier.otheretd-07152010-020336en
dc.identifier.sourceurlhttp://scholar.lib.vt.edu/theses/available/etd-07152010-020336/en
dc.identifier.urihttp://hdl.handle.net/10919/38813en
dc.language.isoenen
dc.publisherVirginia Techen
dc.relation.haspartLD5655.V856_1977.K695.pdfen
dc.relation.isformatofOCLC# 21257701en
dc.rightsIn Copyrighten
dc.rights.urihttp://rightsstatements.org/vocab/InC/1.0/en
dc.subject.lccLD5655.V856 1977.K695en
dc.subject.lcshBlood -- Sedimentationen
dc.subject.lcshFree radicals (Chemistry)en
dc.titleESR investigation of some free-radical adductsen
dc.typeDissertationen
dc.type.dcmitypeTexten
thesis.degree.disciplineChemistryen
thesis.degree.grantorVirginia Polytechnic Institute and State Universityen
thesis.degree.leveldoctoralen
thesis.degree.namePh. D.en

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