Determination of Epsomite-Hexahydrite Equilibria by the Humidity-Buffer Technique at 0.1 MPa with Implications for Phase Equilibria in the System MgSO 4 -H 2 O

Abstract

Epsomite (MgSO₄·7H₂O) and hexahydrite (MgSO₄·6H₂O) are common minerals found in marine evaporite deposits, in saline lakes as precipitates, in weathering zones of coal and metallic deposits, in some soils and their efflorescences, and possibly on the surface of Europa as evaporite deposits. Thermodynamic properties of these two minerals reported in the literature are in poor agreement. In this study, epsomite-hexahydrite equilibria were determined along four humidity-buffer curves at 0.1 MPa and between 25 and 45°C. Results obtained for the reaction epsomite= hexahydrite + H₂O, as demonstrated by very tight reversals along each humidity buffer, can be represented by ln K(± 0.012) = 20.001 - 7182.07/T, where K is the equilibrium constant, and T is temperature in Kelvin. The derived standard Gibbs free energy of reaction is 10.13 ± 0.07 kJ/mol, which is essentially the same value as that calculated from vapor pressure measurements reported in the literature. However, this value is at least 0.8 kJ/mol lower than those calculated from the data derived mostly from calorimetric measurements.