Internal pressure's role in the selectivity of the bromine radical

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dc.contributor.authorHulvey, Glenn A.en
dc.contributor.committeechairTanko, James M.en
dc.contributor.committeememberMerola, Joseph S.en
dc.contributor.committeememberMarand, Hervé L.en
dc.contributor.departmentChemistryen
dc.date.accessioned2014-03-14T21:37:23Zen
dc.date.adate2009-06-10en
dc.date.available2014-03-14T21:37:23Zen
dc.date.issued1993-01-05en
dc.date.rdate2009-06-10en
dc.date.sdate2009-06-10en
dc.description.abstractThe results of our studies demonstrate a link between selectivity in free radical brominations and the internal pressure of solvent. The study encompassed l8 solvents and/or mixtures over which the rate constant ratio for SH2 ring opening of cyclopropylbenzene (kC) vs hydrogen abstraction from toluene (kH) by bromine atom was found to vary by nearly a factor of twenty as a function of solvent. The observed rate constant ratios correlate with the cohesive energy density of the solvent, which is approximately equal to the internal pressure (kC/kH is found to increase with increasing solvent pressure) for the solvents used in this study. A similar competition pitting cyclopropylbenzene against p-chlorotoluene shows the same solvent effect. It is suggested that the observed variation in selectivity "with solvent pressure occurs because the volume of activation with kC is more negative than for kH by about 20 cm3/mol.en
dc.description.degreeMaster of Scienceen
dc.format.extentix, 54 leavesen
dc.format.mediumBTDen
dc.format.mimetypeapplication/pdfen
dc.identifier.otheretd-06102009-063106en
dc.identifier.sourceurlhttp://scholar.lib.vt.edu/theses/available/etd-06102009-063106/en
dc.identifier.urihttp://hdl.handle.net/10919/42980en
dc.language.isoenen
dc.publisherVirginia Techen
dc.relation.haspartLD5655.V855_1993.H848.pdfen
dc.relation.isformatofOCLC# 29151924en
dc.rightsIn Copyrighten
dc.rights.urihttp://rightsstatements.org/vocab/InC/1.0/en
dc.subject.lccLD5655.V855 1993.H848en
dc.subject.lcshBromineen
dc.subject.lcshCyclopropylbenzeneen
dc.subject.lcshFree radicals (Chemistry)en
dc.subject.lcshTolueneen
dc.titleInternal pressure's role in the selectivity of the bromine radicalen
dc.typeThesisen
dc.type.dcmitypeTexten
thesis.degree.disciplineChemistryen
thesis.degree.grantorVirginia Polytechnic Institute and State Universityen
thesis.degree.levelmastersen
thesis.degree.nameMaster of Scienceen

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