The Mechanism of Dissolution of Sparingly Soluble Salts—Application of a Novel Electrochemical Theory

Although the dissolution of sparingly soluble salts is of interest to many fields, such as material science, dentistry, and geochemistry, the simplicity of these reactions provides its own motivation for study. Three features of these reactions are examined in this paper: (i) the unusual forms of the kinetic expression that have been used to describe their rates of reaction, (ii) the observation that the rate of dissolution is correlated with the potential difference across the solid-solution interface, and (iii) the observation of non-stoichiometric dissolution. Mechanistic descriptions of the kinetics of dissolution in current use do not account for all these factors, while the surface vacancy model does. In this paper, it is shown that linear kinetics arise from a symmetry of the rates of removal and deposition of anions and cations. On the other hand, non-linear kinetics arise from an asymmetry in the rates of removal and deposition of anions and cations. Because the surface vacancy model is an electrochemical model, the influence of potential difference on the rate of reaction is inherent to the model. A transient, or non-stationary state, version of the model is used to explain how non-stoichiometric dissolution arises.