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

Xiong, Yongliang; Wang, Yifeng

doi:10.1016/j.chemgeo.2021.120200

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

Journal Article · Mon Jul 05 00:00:00 EDT 2021 · Chemical Geology

DOI:https://doi.org/10.1016/j.chemgeo.2021.120200· OSTI ID:1773287

Xiong, Yongliang ^[1]; Wang, Yifeng ^[1]

Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

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⁺ + 3C₂O₄^2- + 10H₂O(l). Nd₂(C₂O₄)₃•10H₂O ⇌ 2Nd³⁺ + 3C₂O₄^2- + 10H₂O(l). to be -30.82 ± 0.30 (2σ), and - 31.14 ± 0.35 (2σ), respectively. These values for 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, (Ce_1.01Nd_0.33La_0.32Pr_0.11Y_0.11Sm_0.01Pb_0.04U_0.03Th_0.01Ca_0.04)_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.

View Accepted Manuscript (DOE)

Research Organization:: Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA); USDOE Office of Nuclear Energy (NE)

Grant/Contract Number:: AC04-94AL85000; NA0003525

OSTI ID:: 1773287

Alternate ID(s):: OSTI ID: 1815143

Report Number(s):: SAND2021-3458J; 694981

Journal Information:: Chemical Geology, Journal Name: Chemical Geology Vol. 573; ISSN 0009-2541

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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

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