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dc.rights.licenseRestricted to current Rensselaer faculty, staff and students. Access inquiries may be directed to the Rensselaer Libraries.
dc.contributorAikens, David A.
dc.contributorHollinger, Henry B.
dc.contributorKapner, Robert S.
dc.contributorRichtol, H.H.
dc.contributorWiedemeier, Heribert A.
dc.contributor.authorGrant, George C.
dc.date.accessioned2021-11-03T08:51:31Z
dc.date.available2021-11-03T08:51:31Z
dc.date.created2017-07-27T09:53:50Z
dc.date.issued1968-01
dc.identifier.urihttps://hdl.handle.net/20.500.13015/2016
dc.descriptionJanuary 1968
dc.descriptionSchool of Science
dc.description.abstractEven though halide ion is known to function as a ligand bridge in the oxidation of Cr(II) at mercury electrodes, strong evidence has been presented to show that halide ion does not function as a ligand bridge in the electrooxidation of Co(II)EDTAat either a platinum or a mercury electrode, although there are manychemical similarities between the two systems. The character of the electrode surface has been shown not to be responsible for the differences in the effect of halide ions for these two reactions.
dc.description.abstractIn addition, the time-dependent current for constant potential oxidation of Co(II)EDTAindicates a rate of adsorption orders of magnitude slower than known systems of inorganic complexes. Because of the time dependent inhibition of the electrooxidation, the effects of halide ion in this reaction have been shown to depend markedly on the choice of experimental method. In contrast, polarograms for reduction of Co(III)EDTA complexes at a platinum electrode at negative potentials where adsorption is weaker have been shown to have typical, although irreversible, shapes and limiting currents near the theoretical value.
dc.description.abstractThe currents which were observed polarographically for oxidation of Co(II)EDTA at a platinum rotated disk electrode are markedly hindered by adsorption and are not more than 15% of the theoretical value. In contrast, currents observed at a mercury electrode were in agreement with theoretical predictions.
dc.description.abstractSeveral chemical species which could cause interference with determination of the electrode reaction mechanismshave been investigated. It has been demonstrated that presence of certain Hg(II) species in the working electrode compartmentcan lead to strong interference, while certain platinum compounds,if present at the electrode surface, would lead to moderate interference. Mercury and platinum compounds catalyze the otherwise slow conversion of thermodynamically unstable CoYCl and CoYBr to the more stable CoY. The catalyzed conversion of the halide capture product to the thermodynamically stable, non-capture product is sufficiently fast to result in erroneous conclusions concerning the importance of ligand capture.
dc.language.isoENG
dc.publisherRensselaer Polytechnic Institute, Troy, NY
dc.relation.ispartofRensselaer Theses and Dissertations Online Collection
dc.subjectAnalytical chemistry
dc.titleLigand bridging in electrode reactions : the oxidation/reduction of cobalt/EDTA complex
dc.typeElectronic thesis
dc.typeThesis
dc.digitool.pid178457
dc.digitool.pid178458
dc.digitool.pid178459
dc.rights.holderThis electronic version is a licensed copy owned by Rensselaer Polytechnic Institute, Troy, NY. Copyright of original work retained by author.
dc.description.degreePhD
dc.relation.departmentDept. of Chemistry


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