Interlink between solubility, structure, surface and thermodynamics in the ThO2(s, hyd)-H2O(l) system

Christian Kiefer; Thomas Neill; Nese Cevirim-Papaioannou; Dieter Schild; Xavier Gaona; Tonya Vitova; Kathy Dardenne; Jörg Rothe; Marcus Altmaier; Horst Geckeis

doi:10.3389/fchem.2022.1042709

Interlink between solubility, structure, surface and thermodynamics in the ThO₂(s, hyd)-H₂O(l) system

Front Chem. 2022 Nov 15:10:1042709. doi: 10.3389/fchem.2022.1042709. eCollection 2022.

Authors

Affiliations

¹ Institute for Nuclear Waste Disposal, Karlsruhe Institute of Technology, Karlsruhe, Germany.
² Research Centre for Radwaste Disposal and Williamson Research Centre for Molecular Environmental Science, Department of Earth and Environmental Sciences, The University of Manchester, Manchester, United Kingdom.

Abstract

The impact of temperature on a freshly precipitated ThO₂(am, hyd) solid phase was investigated using a combination of undersaturation solubility experiments and a multi-method approach for the characterization of the solid phase. XRD and EXAFS confirm that ageing of ThO₂(am, hyd) at T = 80°C promotes a significant increase of the particle size and crystallinity. TG-DTA and XPS support that the ageing process is accompanied by an important decrease in the number of hydration waters/hydroxide groups in the original amorphous Th(IV) hydrous oxide. However, while clear differences between the structure of freshly precipitated ThO₂(am, hyd) and aged samples were observed, the characterization methods used in this work are unable to resolve clear differences between solid phases aged for different time periods or at different pH values. Solubility experiments conducted at T = 22°C with fresh and aged Th(IV) solid phases show a systematic decrease in the solubility of the solid phases aged at T = 80°C. In contrast to the observations gained by solid phase characterization, the ageing time and ageing pH significantly affect the solubility measured at T = 22°C. These observations can be consistently explained considering a solubility control by the outermost surface of the ThO₂(s, hyd) solid, which cannot be properly probed by any of the techniques considered in this work. Solubility data are used to derive the thermodynamic properties (log *K°_s,0, Δ_f G°_m) of the investigated solid phases, and discussed in terms of particle size using the Schindler equation. These results provide new insights on the interlink between solubility, structure, surface and thermodynamics in the ThO₂(s, hyd)-H₂O(l) system, with special emphasis on the transformation of the amorphous hydrous/hydroxide solid phases into the thermodynamically stable crystalline oxides.

Keywords: solubility; structure; surface; temperature; thermodynamics; thorium.