The Solubilities and Thermodynamic Equilibrium of Anhydrite and Gypsum

Anhydritic claystones consist of a clay matrix with finely distributed anhydrite. Their swelling has led to severe damage and high repair costs in several tunnels. Gypsum growth combined with water uptake by the clay minerals is the main cause of the swelling process. Identifying the conditions under which gypsum rather than anhydrite represents the stable phase is crucial for understanding rock swelling. As existing studies on the anhydrite–gypsum–water equilibrium appear to be contradictory and do not provide all of the information required, we revisit this classic problem here by formulating and studying a thermodynamic model. In contrast to earlier research, our model is not limited to the anhydrite–gypsum equilibrium, but allows for the determination of the equilibrium concentrations of the individual anhydrite dissolution and gypsum precipitation reactions that underlie the sulphate transformation. The results of the paper are, therefore, also valuable for the formulation of comprehensive sulphate–water interaction models that consider diffusive and advective ion transport simultaneously with the chemical dissolution and precipitation reactions. Furthermore, in addition to the influencing factors that have been considered by previous studies (i.e., fluid and solid pressures, concentration of foreign ions, temperature), we consistently incorporate the effect of the surface energy of the sulphate crystals into the thermodynamic equations and discuss the effect of the clay minerals on the equilibrium conditions. The surface energy effects, which are important particularly in the case of claystones with extremely small pores, increase the solubility of gypsum, thus shifting the thermodynamic equilibrium in favour of anhydrite. Clay minerals also favour anhydrite because they lower the activity of the water. The predictions from the model are compared with experimental results and with predictions from other models in the literature. Finally, a comprehensive equilibrium diagram is presented in terms of pore water pressure, solid pressure, temperature, water activity and pore size.