Solubilities and solubility products of thorium hydroxide under moderate temperature conditions

Abstract

AbstractThe Th solubilities of the sample solutions that initially contained Th(OH)4(am) prepared by undersaturation and oversaturation methods in the pHcrange of 2.0–8.0 in a 0.5 M ionic strength solution of NaClO4and HClO4and stored at aging temperatures (Ta) of 298, 313 and 333 K were investigated in this study. After a certain period of time up to 40 weeks depending onTa, supernatants of the sample solutions were ultrafiltrated through 3 kDa membranes under the measurement temperature (Tm) of 298, 313 and 333 K. Size distributions of the colloidal species were investigated by ultrafiltration using membranes with different pore sizes ranging from 3 to 100 kDa, and the solid phases were examined by X-ray diffraction (XRD). The solubility of the sample solutions obtained after aging atTa=298 K using undersaturation method with continuous shaking was similar to those of dried precipitate of Th hydroxide. The solubilities obtained after aging atTa=313 and 333 K were lower than those atTa=298 K. The XRD spectra suggested that the crystallization of the solid phase proceeded under these elevated temperatures. The solubility of the sample solutions obtained after aging atTa=333 K using the oversaturation technique were similar to those prepared by undersaturation method and aged at the sameTa. A slight temperature dependence of the apparent solubilities on theTmwas observed in the sample solutions prepared by both methods. The solubility products$({K_{{\text{sp,}}{T_{\text{a}}}}}({T_{\text{m}}}))$after differentTaandTmwere determined from the solubility analysis. The observed increase in the formation constant$({K_{{\text{s,}}{T_{\text{a}}}}}({T_{\text{m}}}))$of Th4++(4+x)H2O(1)⇌Th(OH)4·xH2O(s,Ta)+4H+with increasingTmindicated that the reaction was endothermic. The enthalpy change$(\Delta_{r}H_{m\_ T_{\text{a}} \to {\text{cr}}}^{\circ} )$between the solid phases of Th(OH)4·xH2O(s,Ta) and ThO2(cr) suggested that the solid phase transformation from Th(OH)4·xH2O(s,Ta) to ThO2(cr) contains an endothermic process.