Extractive Metallurgy Division - Thermodynamic Properties for the Zn-Cd System from Electromotive Force Measurement

Precise electromotive force measurements have been made on the zinc-cadmium system over the temperature range 700° to 900°C. Activity coefficients, partial free energies, enthalpies, and entropies have been determined .for the entire composition range. The integral heat of mixing is positive and compares favorably with calorimetrically determined values. Vapor-liquid equilibrium compositions were determined .for a total pressure of 1 atm and these agree well with previous values determined in other ways. The use of electromotive force measurements to obtain thermodynamic data for liquid metal systems is a simple and well-known method. Several reviews of the various experimental methods and results have been published.2,3,11 However, most of the past work using this technique was carried out at temperatures slightly above the melting point of the alloy system where alloy composition changes due to vapor transport and increased metal solubility in the electrolyte are not important factors. One advantage of extending the electromotive force measurements up to and including the normal boiling point of the alloy is that it is then possible to evaluate the vapor-liquid equilibrium of the alloy at various pressure levels up to 1 atm. A detailed discussion of the thermodynamics of reversible electromotive force cells can be found in most advanced physical chemistry or chemical thermodynamic textbooks. The expression stating the inter-relation of the electromotive force and the thermodynamic functions is the Gibbs-Helmholtz equation.