Experimental determination of the solubility constant for magnesium chloride hydroxide hydrate (Mg3Cl(OH)5•4H2O, phase 5) at room temperature, and its importance to nuclear waste isolation in geological repositories in salt formations

In this study, the solubility constant of magnesium chloride hydroxide hydrate, Mg3Cl(OH)(5)center dot 4H(2)O, termed as phase 5, is determined from a series of solubility experiments in MgCl2-NaCl solutions. The solubility constant in logarithmic units at 25 degrees C for the following reaction, Mg3Cl(OH)(5) center dot 4H(2)O + 5H(+) = 3Mg(2+) + 9H(2)O(I) + Cl- is calculated as 43.21 +/- 0.33 (2 sigma) based on the specific interaction theory (SIT) model for extrapolation to infinite dilution. The Gibbs free energy and enthalpy of formation for phase 5 at 25 degrees C are derived as -3384 +/- 2 (2 sigma) kJ mol(-1) and -3896 +/- 6 (2 sigma) kJ mol(-1), respectively. MgO (bulk, pure MgO corresponding to the mineral periclase) is the only engineered barrier certified by the Environmental Protection Agency (EPA) for emplacement in the Waste Isolation Pilot Plant (WIPP) in the US, and an Mg(OH)(2)-based engineered barrier (bulk, pure Mg(OH)(2) corresponding to brucite) is to be employed in the Asse repository in Germany. Phase 5, and its similar phase, phase 3 (Mg2Cl(OH)(3)center dot 4H(2)O), could have a significant role in influencing the geochemical conditions in geological repositories for nuclear waste in salt formations where MgO or brucite is employed as engineered barriers. Based on our solubility constant for phase 5 in combination with the literature value for phase 3, we predict that the composition for the invariant point of phase 5 and phase 3 would be m(Mg) = 1.70 and pmH = 8.94 in the Mg-Cl binary system. The recent WIPP Compliance Recertification Application Performance Assessment Baseline Calculations indicate that phase 5, instead of phase 3, is indeed a stable phase when the WIPP Generic Weep Brine (GWB), a Na-Mg-Cl-dominated brine associated with the Salado Formation, equilibrates with actinide-source-term phases, brucite, magnesium carbonates, halite and anhydrite. Therefore, phase 5 is important to the WIPP, and potentially important to other repositories in salt formations. (C) 2010 Elsevier Ltd. All rights reserved.