Construction of a rapid-scanning stopped-flow instrument and applications in the area of mercury porphyrins

dc.contributor.advisorKadish, Karl M.
dc.contributor.committeeMemberBear, John L.
dc.contributor.committeeMemberDeming, Stanley N.
dc.contributor.committeeMemberKimball, Aubrey P.
dc.creatorRiffard, Serge
dc.description.abstractThe first part of the research presented in this thesis describes the construction of a Rapid-Scanning Stopped-Flow spectrometer from available instrumentation. Very extensive descriptions and comments on the construction and use of the instrument are presented in order to allow an uninitiated person to use the instrumentation with some degree of success. Two applications of the instrument are then presented. The first involves a kinetic study of the demetalation reaction of (5,10,15,20-tetraphenylporphinato)mercury(II) in the presence of imidazole. The reaction is found to be first order in both imidazole and the mono-imidazole mercury-porphyrin complex and, based on analysis of the data, a mechanism involving the transient formation of a cis bis-ligated mercury porphyrin is postulated. A second study in this thesis involves demetalation of the same mercury porphyrin in the presence of acidic impurities. In this qualitative study, a mechanism is postulated which involves the instantaneous formation of a porphyrin dication and its slow deprotonation into the free base porphyrin.
dc.description.departmentChemistry, Department of
dc.format.digitalOriginreformatted digital
dc.rightsThis item is protected by copyright but is made available here under a claim of fair use (17 U.S.C. Section 107) for non-profit research and educational purposes. Users of this work assume the responsibility for determining copyright status prior to reusing, publishing, or reproducing this item for purposes other than what is allowed by fair use or other copyright exemptions. Any reuse of this item in excess of fair use or other copyright exemptions requires express permission of the copyright holder.
dc.titleConstruction of a rapid-scanning stopped-flow instrument and applications in the area of mercury porphyrins
dc.type.genreThesis of Natural Sciences and Mathematics, Department of of Houston of Science


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