Abstract

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.

Degree

College and Department

Physical and Mathematical Sciences; Chemistry and Biochemistry

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