Papers - Measurement of Irreversible Potentials as a Metallurgical Research Tool (T.P. 1234, with discussion)

Early workers attempted to study the structure of alloys by measurement of equilibrium electrode potentials in aqueous solutions containing ions of the metals from which the alloy was made.' The method was subject to such limitations (e.g., the difficulty in attaining electrochemical equilibrium at low temperatures) that it has not been widely used by metallurgists. Recently, Seltz and co-workers have introduced a greatly improved method for studying alloys by measurement of equilibrium electrode potentials in molten salts.2"4 The mathematical treatment is the same, of course, as for equilibrium potentials of amalgams in aqueous solutions.5 This method will probably find extensive use, since it makes possible not only the determination of phase fields of equilibrium diagrams but also the determination of certain thermodynamic quantities which can be used advantageously in metallurgical calculations. However, the method presents difficulties. With many metallic and alloy electrodes, reversibility is not readily obtainable. Also, the difficulty of obtaining suitable material from which to make the cells is increased as the temperature is increased. Moreover, the necessity of carrying out measurements in a vacuum requires additional apparatus and introduces considerable difficulty, especially at the higher temperatures. Apparently, no consideration has been given heretofore to the metallurgical use of irreversible electrode potentials that exist when a specimen is immersed in a suitable aqueous solution at room temperature. The apparatus and the method required for such measurements are very simple, and if the results of such measurements could be demonstrated to be reproducible they might be very valuable in studying the structure of alloys. The method would not have the scope of that developed by Seltz and his co-workers because no thermodynamic quantities could be calculated from the data. However, the utility and the simplicity of the method might warrant extensive use for the determination of phase fields and similar applications. Theory of Irreversible Potentials A brief review of the theory of irreversible potentials will be given before showing how to interpret the potential readings in terms of alloy structure. It is known that heterogeneity of a metal surface in an electrolyte will produce points of different potentials, with the result that current flows between these points and electrochemical reactions occur. The points at which oxidation reactions are localized are known as anodes, and those at which reduction reactions are localized are known as cathodes.6, 7, 8 For the benefit of those who are not familiar with the terms anode and cathode as applied to a primary cell, the potential difference between anode and cathode of such a cell can be measured when