Show simple item record

dc.contributor.advisorFernando, Quintusen_US
dc.contributor.authorBrown, Frank Reber.
dc.creatorBrown, Frank Reber.en_US
dc.date.accessioned2011-10-31T17:03:12Z
dc.date.available2011-10-31T17:03:12Z
dc.date.issued1987en_US
dc.identifier.urihttp://hdl.handle.net/10150/184254
dc.description.abstractThe rate of oxidation of copper metal to copper (I) by copper (II) in the presence of organic ligands has been determined for a variety of ligands using a flow injection analysis system to sample the reaction. The results obtained using the FIA sampling method compare favorably with those obtained in eariler work when allyl alcohol was used as the ligand. The mechanism proposed in that earlier work has been shown to be a general mechanism for the oxidation of copper metal in the presence of complexing ligands. It was found that some ligands increase the rate of the reaction beyond the ability of conventional FIA to sample many data points before the reaction reaches equilibrium. A method has been developed that allows for more rapid sampling of the reaction mixture by the FIA system, resulting in overlapping FIA peaks. These overlapping peaks can then be deconvolved by an iterative curve fitting/digital subtraction technique in which each peak in the FIA output is fitted to a model function and subtracted from the output, thus removing its effect on the peak height of subsequent peaks. The iodination of acetylacetone in acidic solution was also studied by the fast injection FIA technique. Iodine was generated coulometrically in the solution containing acetylacetone and hydrochloric acid. By this method, the keto-enol equilibrium constant of acetylacetone was determined over a range of pH's. They ranged from 2.3 x 10⁻⁵ at a pH of 2.63 to 1.8 x 10⁻⁴ at a pH of 4.03. It was also found that the reaction was first order with respect to the acetylacetone concentration.
dc.language.isoenen_US
dc.publisherThe University of Arizona.en_US
dc.rightsCopyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author.en_US
dc.subjectChemistry, Analytic -- Technique.en_US
dc.subjectChemical apparatus.en_US
dc.titleAnalytical applications of flow injection analysis.en_US
dc.typetexten_US
dc.typeDissertation-Reproduction (electronic)en_US
dc.identifier.oclc700054663en_US
thesis.degree.grantorUniversity of Arizonaen_US
thesis.degree.leveldoctoralen_US
dc.identifier.proquest8804165en_US
thesis.degree.disciplineChemistryen_US
thesis.degree.disciplineGraduate Collegeen_US
thesis.degree.namePh.D.en_US
refterms.dateFOA2018-08-22T17:04:51Z
html.description.abstractThe rate of oxidation of copper metal to copper (I) by copper (II) in the presence of organic ligands has been determined for a variety of ligands using a flow injection analysis system to sample the reaction. The results obtained using the FIA sampling method compare favorably with those obtained in eariler work when allyl alcohol was used as the ligand. The mechanism proposed in that earlier work has been shown to be a general mechanism for the oxidation of copper metal in the presence of complexing ligands. It was found that some ligands increase the rate of the reaction beyond the ability of conventional FIA to sample many data points before the reaction reaches equilibrium. A method has been developed that allows for more rapid sampling of the reaction mixture by the FIA system, resulting in overlapping FIA peaks. These overlapping peaks can then be deconvolved by an iterative curve fitting/digital subtraction technique in which each peak in the FIA output is fitted to a model function and subtracted from the output, thus removing its effect on the peak height of subsequent peaks. The iodination of acetylacetone in acidic solution was also studied by the fast injection FIA technique. Iodine was generated coulometrically in the solution containing acetylacetone and hydrochloric acid. By this method, the keto-enol equilibrium constant of acetylacetone was determined over a range of pH's. They ranged from 2.3 x 10⁻⁵ at a pH of 2.63 to 1.8 x 10⁻⁴ at a pH of 4.03. It was also found that the reaction was first order with respect to the acetylacetone concentration.


Files in this item

Thumbnail
Name:
azu_td_8804165_sip1_m.pdf
Size:
4.005Mb
Format:
PDF
Description:
azu_td_8804165_sip1_m.pdf

This item appears in the following Collection(s)

Show simple item record