Experimental and modeling studies of PR and ND oxalate solubility to high ionic strengths: Insight into actinide(III) oxalates

Abstract

Actinide oxalates are chemical compounds important to nuclear industry, ranging from actinide separation in waste reprocessing, to production of specialty actinides, and to disposal of high level nuclear waste (HLW) and spent nuclear fuel (SNF). In this study, the solubility constants for Pr2(C2O4)3·10H2O and Nd2(C2O4)3·10H2O by performing solubility experiments in HNO3 and mixtures of HNO3 and H2C2O4 at 23.0 ± 0.2 °C have been determined. The targeted starting materials, Pr2(C2O4)3·10H2O and Nd2(C2O4)3·10H2O, were successfully synthesized at room temperature using PrCl3, NdCl3 and oxalic acid as the source metrials. Then, we utilized the targeted solubility-controlling phases to conduct solubility measurements. There was no phase change over the entire periods of experiments, demonstrating that Pr2(C2O4)3·10H2O and Nd2(C2O4)3·10H2O were the solubility-controlling phases in our respective experiments.Based on our experimental data, we have developed a thermodynamic model for Pr2(C2O4)3·10H2O and Nd2(C2O4)3·10H2O in the mixtures of HNO3 and H2C2O4 to high ionic strengths. The model for Pr2(C2O4)3·10H2O reproduces well the reported experimental data for Pu2(C2O4)3·10H2O, which are not utilized for the model development, demonstrating that Pr(III) is an excellent analog for Pu(III). Similarly, the model for Nd2(C2O4)3·10H2O reproduces the solubility of Am2(C2O4)3·10H2O and Cm2(C2O4)3·10H2O. The Pitzer model was used for the calculation of activity coefficients. Based on the published, well established model for dissociation constants for oxalic acid and stability constants for actinide-oxalate complexes [i.e., AmC2O4+, and Am(C2O4)2−] to high ionic strengths, we have obtained the solubility constants (log10K0) for the following reactions at 25 °C,Pr2(C2O4)3·10H2O ⇌ 2Pr3+ + 3C2O42− + 10H2O(l)Nd2(C2O4)3·10H2O ⇌ 2Nd3+ + 3C2O42− + 10H2O(l) to be −30.82 ± 0.30 (2σ), and −31.14 ± 0.35 (2σ), respectively. These values can be directly applied to Pu2(C2O4)3·10H2O, Am2(C2O4)3·10H2O and Cm2(C2O4)3·10H2O.The model established for actinide oxalates by this study provides the needed knowledge with regard to solubilities of actinide/REE oxalates at various ionic strengths, and is expected to find applications in many fields, including the geological disposal of nuclear waste and the mobility of REE under the surface conditions, as Pr2(C2O4)3·10H2O and Nd2(C2O4)3·10H2O can be regarded as the pure Pr and Nd end-members of deveroite, a recently discovered natural REE oxalate with the following stoichiometry, (Ce1.01Nd0.33La0.32Pr0.11Y0.11Sm0.01Pb0.04U0.03Th0.01Ca0.04)2.01(C2O4)2.99·9.99H2O. Regarding its importance in the geological disposal of nuclear waste, Am2(C2O4)3·10H2O/Pu2(C2O4)3·10H2O/Cm2(C2O4)3·10H2O can be the source-term phase for actinides, as demonstrated by the instance in the disposal in clay/shale formations. This is exemplified by the stability of Am2(C2O4)3·10H2O in comparison with Am(OH)3(am), Am(OH)3(s) and AmCO3(OH)(s) under the relevant geological repository conditions.