Publisher's Synopsis
Excerpt from A Lead Standard Cell and a Determination of the Potential of the Lead Electrode: Dissertation, Presented in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy in the Graduate School of the Ohio State University
This method first suggested by Callender and Barnes,1 and later de veloped by Geiger,2 depends upon the change in slope of the solubility curve of a salt accompanying the change from one hydrate to another. Since the electromotive force of a cell in which the hydrated salt com prises a part is a function of the solubility of the salt, any change in the solubility curve of that salt will have a noticeable effect upon the electro motive force. If the electromotive force of such a cell is plotted against the temperature, the slope of the curve obtained will undergo a change at the transition temperature of the salt, and by measuring the electro motive force at difierent temperatures the transition temperature of the salt may be determined. For example, in the Clark cell, the salt which is stable up to is zinc sulfate heptahydrate This salt changes to the hexahydrate (zhso4.6h20) at and since at this temperature both salts have the same solubility, the voltages of two cells containing, respectively, the heptahydrate and the hexahydrate would be identical. At no other temperature would this condition pre vail. The fact that salts frequently remain in a metastable condition beyond the transition temperature does not affect the accuracy of the method, since by plotting the electromotive force against the tempera ture two curves are obtained depending upon which salt is present in the cell, and the point of intersection of the two curves, representing the point of equal solubility will be the transition temperature.
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