Thermodynamics of the Eu( iii )–Mg–SO₄ –H₂O and Eu( iii )–Na–SO₄ –H₂O systems. Part I: solubility experiments and the full dissociation Pitzer model

The solubility of Eu(III) was investigated under undersaturated conditions in acidic, dilute to concentrated MgSO4 and Na2 SO4 solutions at T = (22 ± 2) °C. After attaining equilibrium conditions, solid phases were characterized by a multi-method approach, including X-ray diffraction (XRD), Raman and infrared (IR) spectroscopy, quantitative chemical analysis (ICP-OES) and thermogravimetric analysis (TG-DTA). A total of 45 solubility samples were investigated for the systems Eu2 (SO4) 3–MgSO4–H 2O (19 samples) and Eu2 (SO4) 3–Na2SO 4–H2 O (26 samples). Eu2 (SO4) 3·8H2 O(cr) was found to control the solubility of Eu(III) in all investigated MgSO4 solutions, as well as in dilute Na 2SO 4 systems. The transformation of Eu 2(SO4 ) 3·8H2 O(cr) into the double salt Na 2Eu2 (SO4) 4 ·2H2O(cr) was observed at mNa2 SO4 > 0.01 mol kg−1. The latter phase is characterized by significantly lower solubility. Based on these experimental solubility measurements, thermodynamic and activity models were proposed based on the Pitzer equations considering the full dissociation of the Eu(III) species in MgSO4 and Na2 SO4 aqueous solutions, i.e. deliberately excluding Eu(III)-sulfate complex formation. ... mehrA combination of the geochemical calculation code PhreeSCALE and the parameter estimation code PEST was used to determine the values of solubility products ðK°s;0Þ and binary and ternary specific interaction parameters (βð0Þij , βð1Þij , Cϕij , θik, Ψijk).