Thermodynamic models for highly charged aqueous species: Solubility of Th(IV) hydrous oxide in concentrated NaHCO3 and Na2CO3 solutions

Abstract

An aqueous thermodynamic model is proposed to describe the solubility ofTh(IV) hydrous oxide in the aqueous Na+-HCO3--CO32--OH--ClO4--H2O system extending to high concentration at 25‡C. This model is relatively simple in that only two aqueous species are included: Th(OH)3CO3- and Th(CO3)56-. Pitzer ion interaction parameters, Β(0) and Β(l) for Na+ with Th(CO3)56-, are also determined (1.31 and 30, respectively). Reconciliation of all of the experimental solubility data for Th(IV) hydrous oxide in NaClO4 media required the introduction of a large mixing parameter for the highly charged Th(CO3)4-. The relatively large values required for the ion interaction parameters Β(0) and Β(l), together with commensurately large mixing terms with the bulk anionic species, resulted in considerable uncertainty in determining standard state equilibrium constants for the formation of the highly charged Th(CO3)56- species. This uncertainty is a result of the large contributions from Β(0) and Β(l) to the excess solution free energy at the concentrations (0.1m) where this species becomes important. The magnitude of the mixing term implies that formation of this species depends strongly upon the bulk ionic media. X-ray absorption results, confirming the presence of the thorium pentacarbonate species in concentrated bicarbonate and carbonate solutions, are also included.