In this study we developed thermodynamic models for solid-liquid equilibrium for mixed systems HF-NaF-H2O and HF-KF-H2O up to 2 m HF at T = 25oC. Models are developed on the basis of Pitzer ion interactions approach. The recommendations on mean activity coefficients (γ ±) have been used to construct the model for HF-H2O system. The models for binary systems NaF-H2O and KF-H2O are taken from our previous study in the same journal [Donchev et al. ASN (2021) 8(2), 1-15]. To parameterize models for ternary systems we used the available solubility data, i.e. on the basis of solubility approach. The thermodynamic solubility products (as ln Ko sp) of precipitating in mixed systems double salts [NaF.HF(cr), and KF.HF(cr)] have been determined on the basis of evaluated model ion interaction parameters and using experimental m(sat) solubility data. The model is in a good agreement with experimewnt solubility data in the systems HF–NaF–H2O and HF–NaF–H2O up to maximum HF molality of 2 mol·kg−1. At higher acid molality the model predicts much higher solubility of double salts (NaF.HF(cr) and KF.HF(cr) for both mixed systems. It was concluded that not a correct raw data for binary HF–H2O system used in parameterization are the main reason for concentration restriction of mixed HF models presented here.

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In this study we developed well validated thermodynamic models for solution behavior and solid-liquid equilibrium for all fluoride binary systems, for which activity data are available. The subject of modeling study are 5 fluoride systems of the type 1-1 (HF-H2O, NaF-H2O, KF-H2O, RbF-H2O, and CsF-H2O) and one of 1-2 type (H2SiF6-H2O) from low to very high concentration at 298.15 K. Models are developed on the basis of Pitzer ion interactions approach. The recommendations on mean activity coefficients (γ±) have been used to construct the model for HF-H2O system. To parameterize models for all other 5 binary systems we used all available raw experimental osmotic coefficients data (φ) for whole concentration range of solutions, and up to saturation point. The predictions of new developed here models are in excellent agreement with experimental osmotic coefficients data, and with recommendations on activity coefficients in binary solutions from low to very high concentration: up to 20 mol. kg−1 in HF-H2O, and up to 35.6 mol.kg−1 in CsF-H2O. The Deliquescence Relative Humidity (DRH (%)) and thermodynamic solubility products (as ln Ko sp) of 4 solid phases [NaF(s), KF.2H2O(s), RbF(s), and CsF(s)] have been determined on the basis of evaluated model parameters and using experimental m(sat) solubility data.

The models described in this study are of high importance in the development of thermodynamic database needed for nuclear waste geochemical storage as well as for technology for extracting cesium resources from saline waters. In this study we developed new not concentration restricted thermodynamic models for solution behavior and solid-liquid equilibrium in CsF-H2O CsOH-H2O and Cs2SO4-H2O systems at 25 °C. To parameterize models we used all available experimental osmotic coefficients data for whole concentration range of solutions and up to saturation point. The new models are developed on the basis of Pitzer ion interactions approach. The predictions of new developed here models are in excellent agreement with experimental osmotic coefficients data (ϕ) in binary solutions from low to extremely high concentration (up to 21.8 mol.kg-1 for CsOH-H2O and up to 35.6 mol.kg-1 for CsF-H2O). The previously developed by Christov by Christov and co-authors and by other authors Pitzer approach based thermodynamic models for five (5) cesium binary systems (CsCl-H2O CsBr- H2O CsI-H2O CsNO3-H2O and Cs2SeO4- H2O) are tested by comparison with experimental osmotic coefficients data and with recommendations on activity coefficients (γ±) in binary solutions. The models which give the best agreement with (ϕ)- and (γ±) -data from low to high concentration up to m(sat) are accepted as correct models which can be used for solubility calculations in binary and mixed systems and determination of thermodynamic properties of precipitating cesium solid phases. The thermodynamic solubility products (ln Kosp) and the Deliquescence Relative Humidity (DRH) of solid phases precipitating from saturated cesium binary solutions (CsF(cr) CsCl(cr) CsBr(cr) CsI(cr) CsOH(cr) CsNO3(cr) Cs2SO4(cr) and Cs2SeO4(cr)) have been determined on the basis of evaluated and accepted binary parameters and using experimental solubility data. The reported mixing parameters [θ(Cs M2+) and ψ(Cs M2+ X)] evaluated by solubility approach for 15 cesium mixed ternary systems (CsCl-MgCl2-H2O CsBr-MgBr2-H2O CsCl-NiCl2-H2O CsBr-NiBr2-H2O CsCl-MnCl2-H2O CsCl-CoCl2-H2O CsCl-CuCl2-H2O CsCl-CsBr-H2O CsCl-RbCl-H2O Cs2SO4-CoSO4-H2O Cs2SeO4-CoSeO4-H2O Cs2SO4-NiSO4-H2O Cs2SeO4-NiSeO4-H2O Cs2SO4-ZnSO4-H2O and Cs2SeO4-ZnSeO4-H2O) are tabulated.

The main purpose of this study is to develop new thermodynamic models for solution behavior and solid-liquid equilibrium in 10 nitrate binary systems of the type 2–1 (Mg(NO3)2-H2O, Ca(NO3)2-H2O, Ba(NO3)2-H2O, Sr(NO3)2-H2O, and UO2(NO3)2-H2O), 3–1 (Cr(NO3)3-H2O, Al(NO3)3-H2O, La(NO3)3-H2O, Lu(NO3)3-H2O), and 4–1 (Th(NO3)4-H2O) from low to very high concentration at 25 °C. To construct models, we used different versions of standard molality-based Pitzer approach. To parameterize models, we used all available raw experimental osmotic coefficients data (φ) for whole concentration range of solutions, and up to supersaturation zone. The predictions of developed models are in excellent agreement with φ-data, and with recommendations on activity coefficients (γ±) in binary solutions from low to very high concentration. The Deliquescence Relative Humidity (DRH), and thermodynamic solubility product (as ln K°sp) of 12 nitrate solid phases, precipitating from saturated binary solutions have been calculated. The concentration-independent models for nitrate systems described in this study are of high importance for development of strategies and programs for nuclear waste geochemical storage.