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 Na2SO4 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...

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Published in:Dalton transactions : an international journal of inorganic chemistry 2024-04, Vol.53 (14), p.6289-6299
Main Authors: dos Santos, P F, A Lassin, Gaona, X, Garbev, K, Altmaier, M, Madé, B
Format: Article
Language:English
Subjects:
Aqueous solutions
Chemical analysis
Complex formation
Differential thermal analysis
Dilution
Earth Sciences
Equilibrium conditions
Infrared analysis
Infrared spectroscopy
Interaction parameters
Magnesium sulfate
Mathematical models
Parameter estimation
Sciences of the Universe
Solid phases
Solubility
Thermodynamics
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Summary:The solubility of Eu(iii) was investigated under undersaturated conditions in acidic, dilute to concentrated MgSO4 and Na2SO4 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–H2O (19 samples) and Eu2(SO4)3–Na2SO4–H2O (26 samples). Eu2(SO4)3·8H2O(cr) was found to control the solubility of Eu(iii) in all investigated MgSO4 solutions, as well as in dilute Na2SO4 systems. The transformation of Eu2(SO4)3·8H2O(cr) into the double salt Na2Eu2(SO4)4·2H2O(cr) was observed at mNa2SO4 > 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 Na2SO4 aqueous solutions, i.e. deliberately excluding Eu(iii)-sulfate complex formation. A combination of the geochemical calculation code PhreeSCALE and the parameter estimation code PEST was used to determine the values of solubility products [Formula Omitted] and binary and ternary specific interaction parameters (βij(0), βij(1), Cijφ, θik, Ψijk).
ISSN:1477-9226
1477-9234
DOI:10.1039/d3dt04322c