Thermodynamic Modeling of Aqueous Aluminum Chemistry and Solid-Liquid Equilibria to High Solution Concentration and Temperature. I. The Acidic H-Al-Na-K-Cl-H2O System from 0 to 100 °C

摘要

In this paper, we describe the development of a thermodynamic model that calculates solute/solvent activities and solid-liquid equilibria in the acidic aluminum system, H-Al3+-Na-K-Cl-H2O, to high molality from 0 ° to ≈100 °C. The model incorporates the concentration-dependent, specific interaction equations for aqueous solutions of Pitzer (Activity Coefficients in Electrolyte Solutions, 2nd edn., pp. 75–153, CRC Press, Boca Raton, 1991). Parameterization of this model adds Al3+ specific interactions in the binary Al-Cl-H2O and ternary Al-H-Cl-H2O, Al-Na-Cl-H2O and Al-K-Cl-H2O systems as well as the standard chemical potentials of AlCl3?6H2O(s) and Al(OH)3(s) (gibbsite) in the 0 ° to 100 °C range to our variable temperature (0–250 °C) model of acid-base reactions in the H-Na-K-OH-Cl-HSO4-SO4-H2O system (Christov and Moller in Geochim. Cosmochim. Acta 68:1309, 2004). In constructing our aluminum model, we used Emf, osmotic, equilibrium constant and solubility data. New Emf measurements using the cell Pt|H2(g, 101.325 kPa)|HCl(m 1), AlCl3(m 2)|AgCl(s)|Ag|Pt at temperatures ranging from 0 to 45 °C and at total ionic strength ranging from 0.1 to 3 mol?kg?1 are presented. Gibbsite and boehmite, AlOOH(s), solubility data are used in testing the model. Limitations of the model due to data insufficiencies are discussed.