Thermodynamic and kinetic studies of galena in the presence and absence of potassium ethyl xanthate

dc.contributor.authorPritzker, Mark Daviden
dc.contributor.committeechairYoon, Roe-Hoanen
dc.contributor.committeememberGibbs, Geralden
dc.contributor.committeememberReifsnider, Kenneth L.en
dc.contributor.committeememberRichardson, P.E.en
dc.contributor.committeememberSanzone, Georgeen
dc.contributor.committeememberWard, Thomas C.en
dc.contributor.committeememberWightman, James P.en
dc.contributor.departmentMaterials Engineering Scienceen
dc.date.accessioned2017-03-10T21:54:25Zen
dc.date.available2017-03-10T21:54:25Zen
dc.date.issued1985en
dc.description.abstractA study of the electrochemistry of the PbS-H₂O and PbS-KEX-H₂O systems has been made by carrying out thermodynamic calculations, electrochemical experiments and microflotation tests. Particular attention has been paid to how well this system can be described by equilibrium thermodynamics. The thermodynamic calculations are more comprehensive than previous ones of this type since they are based on a mass balance which includes both insoluble and soluble species. The data they provide include equilibrium concentrations of all dissolved species at any E<sub>h</sub> and pH and an E<sub>h</sub>-pH stability diagram for each collector addition. Also, two- and three-dimensional plots showing the effect of E<sub>h</sub> and pH on xanthate uptake by the galena surface have been presented for the first time. These are particularly useful because they can be directly compared to observed flotation data. The results of voltammetry, IGP and potential-step experiments suggest that the oxidation of galena at pH 6.8 and 9.2 begins at a potential below the value predicted by bulk thermodynamics with the electrosorption of OH⁻ and the formation of a metal-deficient sulfide and a surface lead oxide. When oxidation becomes extensive enough, bulk products, Sº and PbO, begin to nucleate. Thiosulfate is detected at pH 9.2, but only becomes significant at high potentials. The electrochemical experiments indicate that xanthate adsorbs onto galena via a one-electron transfer chemisorption reaction in the first monolayer and via the formation of PbX₂ in subsequent layers. It also appears that galena oxidation and xanthate adsorption are competitive processes that tend to inhibit each other. Ground galena exhibits natural floatability at pH 9.2 as long as oxidation extends to the formation of a metal-deficient sulfide, but not to bulk PbO. When 10⁻⁵ M xanthate is added, the upper potential limit for flotation agrees well with the value predicted from thermodynamics for the decomposition of PbX₂. The lower limit, on the other hand, is at least 200 mv lower than any of the predicted values. PbS dissolves anodically at pH 1.1 and 4.6 to form Pb²⁺ and Sº first by a random surface process and then by a nucleation and growth mechanism once oxidation becomes extensive enough. At pH 0, the relation between the open-circuit potential and mineral solubility, as predicted by the thermodynamic calculations, agrees quantitatively with that determined experimentally. However, as the pH is increased to 1.1 and 4.6, the system becomes increasingly less reversible.en
dc.description.degreePh. D.en
dc.format.extentxxix, 493 leavesen
dc.format.mimetypeapplication/pdfen
dc.identifier.urihttp://hdl.handle.net/10919/76476en
dc.language.isoen_USen
dc.publisherVirginia Polytechnic Institute and State Universityen
dc.relation.isformatofOCLC# 12832905en
dc.rightsIn Copyrighten
dc.rights.urihttp://rightsstatements.org/vocab/InC/1.0/en
dc.subject.lccLD5655.V856 1985.P747en
dc.subject.lcshFlotation -- Experimentsen
dc.subject.lcshElectrochemical analysisen
dc.subject.lcshGalena -- Reactivityen
dc.subject.lcshPotassium ethylxanthate -- Absorption and adsorptionen
dc.titleThermodynamic and kinetic studies of galena in the presence and absence of potassium ethyl xanthateen
dc.typeDissertationen
dc.type.dcmitypeTexten
thesis.degree.disciplineMaterials Engineering Scienceen
thesis.degree.grantorVirginia Polytechnic Institute and State Universityen
thesis.degree.leveldoctoralen
thesis.degree.namePh. D.en

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