A spectrophotometric study of the impact of pH and metal-to-ligand ratio on the speciation of the Pu(vi)-oxalate system

Sockwell, Ashleigh Kirstin; DiBlasi, Nicole Ann; Hixon, Amy E.

doi:10.1039/d3cp04010k

A spectrophotometric study of the impact of pH and metal-to-ligand ratio on the speciation of the Pu(vi)-oxalate system

Journal Article · Tue Nov 21 00:00:00 EST 2023 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/d3cp04010k· OSTI ID:2281495

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University of Notre Dame, IN (United States)
University of Notre Dame, IN (United States); Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

The oxalate ligand is prevalent throughout the nuclear fuel cycle. While the Pu(III)- and Pu(IV)-oxalate systems are well studied due to their use in plutonium metal and PuO₂ production, the effect of oxalate on Pu(VI) remains understudied. Absorption spectroscopy was employed to probe the solution behavior of the Pu(VI)-oxalate system as a function of pH (1, 3, 7) and metal-to-ligand ratio (M/L; 10 : 1–1 : 10). Peak changes in the UV-vis-NIR spectra were associated with the formation of multiple Pu(VI)-oxalate species with increasing oxalate concentration. Some insight into identification of species present in solution was gained from the limited Pu(VI)-oxalate literature and comparisons with the assumed isostructural U(VI)-oxalate system. A peak in the UV-vis-NIR spectrum at 839 nm, which corresponds to the formation of a 1 : 1 PuO₂(C₂O₄)(aq) complex, was observed and used to determine the formation constant (log β° = 4.64 ± 0.06). A higher coordinated Pu(VI)-oxalate peak at 846 nm was tentatively assigned as the 1 : 2 complex PuO₂(C₂O₄)₂^2₋ and a preliminary formation constant was determined (log β° = 9.30 ± 0.08). In conclusion, the predominance of both complexes was shown in speciation diagrams calculated from the formation constants, illustrating the importance of considering the Pu(VI)-oxalate system in the nuclear fuel cycle.

View Accepted Manuscript (DOE)

Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States); Oak Ridge Institute for Science and Education (ORISE), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: 89233218CNA000001; SC0018231

OSTI ID:: 2281495

Alternate ID(s):: OSTI ID: 2222826

Report Number(s):: LA-UR--24-20293

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 48 Vol. 25; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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