Measurement of Irreversible Potentials as a Metallurgical Research Tool

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.1 The method was subject to such limitations (e.g., the difficulty in attaining electro-chemical 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 equilib-rium 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 deter-mination of phase fields of equilibrium diagrams but also the determination of certain thermodynamic quantities which can be used advantageously in metal-lurgical 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 temper-ature is increased. Moreover, the necessity of carrying out measurements in a vacuum requires additional apparatus and intro-duces considerable difficulty, especially at the higher temperatures.