Ammonia Pressure Hydrometallurgy: Estimation of High Temperature Stability Constants for Metal Ammine Complexes

The thermodynamic data necessary for the quantitative treatment of Metal-NH3- H2O systems at elevated temperatures are lacking in the literature. As a result discussions of the chemical basis of high temperature processes, such as leaching and hydrogen reduction, have tended to rely on low temperature thermodynamic data. In this paper a critical review is presented of the available high temperature data for metal ammine formation in aqueous systems, and methods are suggested to enable extrapolation of elevated temperature stability constants from low temperature thermodynamic data. Predictions of the Van't Hoff Lsobar, the simple cation Correspondence Principle (whereby metal ammine complexes are treated as simple cations) and Helgeson's Electrostatic-Nonelectrostatic Model are compared with the available high temperature stability constants for nickel ammines. Up to 80 °C all three estimation methods yield results which are in agreement with experimental data. However, serious deviations occur at higher temperatures; the various models overestimate the stability constants in the order Van't Hoff Isobar > electrostatic-nonelectrostatic model > simple cation Correspondence Principle. Using the experimental nickel data as a basis, a method is presented which permits reasonable estimates to be made of the stability constants of metal ammine complexes for temperatures above 80 °C.