The oxygen and oxalate exchange reactions of the bisoxalatoplatinate (II) ion in aqueous solution
Teggins, John Edward
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This dissertation reports on experiments conducted to investigate properties of the bisoxalatonplatinate (II) ion in weakly acidic and essentially neutral aqueous media. In particular, the following kinetic effects have been studied: a) The exchange between free oxalate and the complex ion. b) The exchange between solvent and ligand oxygen. c) The dependence of the above reactions on temperature, ionic strength, and hydrogen ion concentration. In order to elucidate the mechanism of these reactions, a limited study of the exchange reaction between free oxalate species and water is also reported and discussed. The oxalate exchange reaction(a) was performed by allowing aqueous solutions containing sodium bisoxalatonplatinate (II) and free oxalate labelled with carbon-14 to react in the dark at constant temperature. Where necessary, the ionic strengths of reaction solutions were adjusted by the addition of sodium nitrate solution, and pH values were maintained with suitable phosphate buffers. Quenching of the reaction was achieved by precipitating potassium bisoxalatonplatinate (II) by the addition of potassium chloride solution. Measurement of the beta-activity of a given precipitate enabled the amount of exchange to be calculated. [TRUNCATED]
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