Zirconium Dioxide Solubility in High Temperature Aqueous Solutions

Abstract

The heat transport purification system of CANDU nuclear reactors is used to remove particulates and dissolved impurities from the heat transport coolant. Zirconium dioxide shows some potential as a high-temperature ion-exchange medium for cationic and anionic impurities found in the CANDU heat transport system (HTS). Zirconium in the reactor core can be neutron activated, and potentially can be dissolved and transported to out-of-core locations in the HTS. However, the solubility of zirconium dioxide in high-temperature aqueous solutions has rarely been reported. This paper reports the solubility of zirconium dioxide in 10−4 mol⋅kg−1 LiOH solution, determined between 298 and 573 K, using a static autoclave. Over this temperature range, the measured solubility of zirconium dioxide is between 0.9 and 12×10−8 mol⋅kg−1, with a minimum solubility around 523 K. This low solubility suggests that its use as a high-temperature ion-exchanger would not introduce significant concentrations of contaminants into the system. A thermodynamic analysis of the solubility data suggests that Zr(OH)40 likely is the dominant species over a wide pH region at elevated temperatures. The calculated Gibbs energies of formation of Zr(OH)40(aq) and Zr(OH)4(am) at 298.15 K are −1472.6 kJ⋅mol−1 and −1514.2 kJ⋅mol−1, respectively. The enthalpy of formation of Zr(OH)40 has a value of −1695±11 kJ⋅mol−1 at 298.15 K.