A survey of the chemical literature revealed a lack of agreement in the values reported by various investigators for the solubility product constants of the metallic sulfides. The object of this thesis was to obtain a reliable set of solubility product constant values for the metallic sulfides by means of thermodynamic calculations. Of considerable importance in calculating the values of the solubility product constants of the metallic sulfides is the value of the standard free energy of formation of the sulfide ion. A critical review of the values that have been reported by various investigators for this constant , including a value determined electrochemically by the writer, was made in order to select the most reliable value. The value of 20.64 kcal. at 25° C., calculated by the writer from data given by Konopik and Leberl, was selected as the most accurate value. The solubility product constants were obtained by combining this figure with free energy data of the metallic sulfides and the metallic ions, obtained when possible from values currently accepted by the National Bureau ot Standards. When no direct measurements of free energy values were available, standard enthalpy data in combination with estimates of entropies obtained by a method recently introduced by W. M. Latimer were used to obtain these values. The results of the calculations or the solubility product constants of the metallic sulfides are summarized in the table given below.

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Probing the surface chemistry of thiol ligand binding to cadmium chalcogenide nanoparticles is important to clarify factors involved in quantum dot stability and surface functionalisation. This research is a spectroscopic investigation aimed at gaining a better understanding of the interaction/bonding of various ligands to CdS, with respect to the use of CdS in biological imaging. The findings of this research are important to the more general field of cadmium chalcogenide materials as biological imaging agents. Deposited CdS nanoparticle films were used in this work as model quantum dot surfaces for ligand adsorption studies. The adsorption of the monothiol-containing ligands, mercaptoacetic acid, mercaptopropionic acid, and mercaptoethanol, to CdS thin films were studied in situ using attenuated total reflectance infrared spectroscopy. The absence of an S-H stretch absorption for the adsorbed species showed that adsorption occurred via the deprotonated thiol group. The adsorption of the dithiol-containing ligands α-lipoic acid, dihydrolipoic acid, and dithiothreitol to CdS nanoparticle films was investigated. The adsorption of dihydrolipoic acid and dithiothreitol was found to occur via both thiol functional groups and an additional interaction between the carboxylate group and the CdS surface. The adsorption of α-lipoic acid to CdS in the presence of light proceeded with photo-oxidation of the CdS surface and reductive cleavage of the disulfide bond of α-lipoic acid to produce some adsorbed dihydrolipoic acid and thiosulfate. The adsorption of α-lipoic acid to CdS in the absence of visible light showed no photo-oxidation, and suggested adsorption occurred via retention of the disulfide bond. The kinetics of adsorption and desorption of oxalic acid on deposited anatase TiO₂ films were studied to investigate the feasibility of extracting molecular information from attenuated total reflectance infrared spectroscopic kinetic data of ligand processes on deposited particle films. Oxalic acid adsorbed on anatase TiO₂ is a well-studied example and is reported to result in three different surface species. The profile of the desorption data indicated contributions from three different components. Different component contributions were unable to be obtained from the adsorption data which is attributed to adsorption occurring much faster than desorption and thus being relatively insensitive to the presence of different adsorbed species. The kinetics of adsorption and desorption of mercaptoacetic acid on CdS were investigated. The desorption data profile indicated the presence of two adsorbed species with different affinities for the CdS surface, the exact chemical nature of which can only be speculated upon given the absence of distinguishing IR spectral features. Ligand exchange reactions at the surface of oleate and trioctylphosphine oxide-capped CdS quantum dot films were investigated. Adsorbed oleate was coordinated to the CdS in a chelating bidentate manner through the carboxylate functional group, while adsorbed trioctylphosphine oxide was coordinated though the P=O functional group. Ligand exchange reactions on the oleate and trioctylphosphine-capped CdS films were studied, and exchange with monothiol-containing ligands was observed only at solution pH where the exchanging ligand was uncharged. Avidin-biotin bioconjugation reactions were carried out on CdS films, which involved the sequential adsorption of mercaptoacetic acid, the protein avidin, and the subsequent binding of the ligand biotin. The spectral data suggested that avidin underwent a conformational change upon adsorption to the CdS surface. This conformation appeared to be perturbed again upon binding of biotin, and it is speculated that the conformation partially reverted back to the native solution conformation.

Thesis (B.S.)--University of Missouri, School of Mines and Metallurgy, 1899. / Year of thesis publication determined from "Forty-First Annual Catalogue, School of Mines and Metallurgy, University of Missouri". The entire thesis text is included in file. Typescript. Illustrated by author. Title from title screen of thesis/dissertation PDF file (viewed March 3, 2010)

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