Development of accurate chemical thermodynamic database for geochemical storage of nuclear waste. Part II: Models for predicting solution properties and solid-liquid equilibrium in binary nitrate systems

Abstract

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.