Thermodynamic Model for the Solubility of Ba(SeO 4 , SO 4 ) Precipitates
The solubility of Ba(SeO 4 , SO 4 ) precipitates was determined as a function of the BaSeO 4 mole fractions, ranging from 0.0015 to 0.3830, and time with an equilibration period extending to as long as 302 days. Equilibrium/steady state conditions in this system are reached in ≤ 65 days. Pitzer’s ion interaction model was used to calculate solid and aqueous phase activity coefficients. Thermodynamic analyses showed that the data do not satisfy Gibbs-Duhem equation, thereby demonstrating that a single-solid solution phase does not control both the selenate and sulfate concentrations. Our extensive data with log 10 [Ba] ranging from -3.6 to -5.9 mol kg -1 , log 10 [SeO 4 ] rangingfrom-3.6 to -5.2 mol kg -1 , and log 10 [SO 4 ] ranging from-4.0 to -5.3 mol kg -1 can be explained with the formation of an ideal BaSeO 4 solid solution phase that controls the selenium concentrations and a slightly disordered/less-crystalline BaSO 4 (s) (log 10 Κ° sp = -9.5 instead of -10.05 for barite) that controls the sulfate concentrations. In these experiments the BaSO 4 component of the solid solution phase never reaches thermodynamic equilibrium with the aqueous phase. Thermodynamic interpretations of the data show that both the ideal BaSeO 4 solid solution phase and less-crystalline BaSO 4 (s) phase are in equilibrium with each other in the entire range of BaSeO 4 mole fractions investigated in this study.