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Thermodynamic model for the solubility of Ba(SeO$$_{4}$$, SO$$_{4}$$) precipitates

Rai, D.*; Felmy, A. R.*; Moore, D. A.*; Kitamura, Akira  ; Yoshikawa, Hideki; Doi, Reisuke ; Yoshida, Yasushi*

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 $$leq$$ 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 [Ba], [SeO$$_{4}$$], and [SO$$_{4}$$] 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) 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.

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Category:Chemistry, Inorganic & Nuclear

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