An improved thermodynamic model for the complexation of trivalent actinides and lanthanide with oxalic acid valid to high ionic strength.

Xiong, Yongliang; Thakur, Punam; Borkowski, Marian

doi:10.1016/j.chemgeo.2015.07.029

An improved thermodynamic model for the complexation of trivalent actinides and lanthanide with oxalic acid valid to high ionic strength.

Journal Article · Thu Jul 30 00:00:00 EDT 2015 · Chemical Geology

DOI:https://doi.org/10.1016/j.chemgeo.2015.07.029· OSTI ID:1236228

Xiong, Yongliang ^[1]; Thakur, Punam ^[2]; Borkowski, Marian ^[3]

Sandia National Lab. (SNL-NM), Carlsbad, NM (United States)
Florida State Univ., Tallahassee, FL (United States)
Los Alamos National Lab. (LANL), Carlsbad, NM (United States)

The dissociation constants of oxalic acid (Ox), and the stability constants of Am³⁺, Cm³⁺ and Eu³⁺ with Ox^2– have been determined at 25 °C, over a range of concentration varying from 0.1 to 6.60 m NaClO4 using potentiometric titration and extraction techniques, respectively. The experimental data support the formation of complexes, M(Ox)_n^{3 – 2n}, where (M = Am³⁺, Cm³⁺ and Eu³⁺ and n = 1 and 2). The dissociation constant and the stability constant values measured as a function of NaClO₄ concentration were used to estimate the Pitzer parameters for the respective interactions of Am³⁺, Cm³⁺ and Eu³⁺ with Ox. Furthermore, the stability constants data of Am³⁺ –Ox measured in NaClO₄ and in NaCl solutions from the literature were simultaneously fitted in order to refine the existing actinide–oxalate complexation model that can be used universally in the safety assessment of radioactive waste disposal. The thermodynamic stability constant: log β⁰₁₀₁ = 6.30 ± 0.06 and log β⁰₁₀₂ = 10.84 ± 0.06 for Am³⁺ was obtained by simultaneously fitting data in NaCl and NaClO₄ media. Additionally, log β⁰₁₀₁ = 6.72 ± 0.08 and log β⁰₁₀₂ = 11.05 ± 0.09 for the Cm³⁺ and log β⁰₁₀₁ = 6.67 ± 0.08 and log β⁰₁₀₂ = 11.15 ± 0.09 for the Eu³⁺ were calculated by extrapolation of data to zero ionic strength in NaClO₄ medium only. For all stability constants, the Pitzer model gives an excellent representation of the data using interaction parameters β⁽⁰⁾, β⁽¹⁾, and CΦ determined in this work. The thermodynamic model developed in this work will be useful in accurately modeling the potential solubility of trivalent actinides and early lanthanides to ionic strength of 6.60 m in low temperature environments in the presence of Ox. Furthermore, the work is also applicable to the accurate modeling transport of rare earth elements in various environments under the surface conditions.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC04-94AL85000

OSTI ID:: 1236228

Alternate ID(s):: OSTI ID: 1246575

Report Number(s):: SAND--2015-6902J; 599092

Journal Information:: Chemical Geology, Journal Name: Chemical Geology Journal Issue: C Vol. 413; ISSN 0009-2541

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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An improved thermodynamic model for the complexation of trivalent actinides and lanthanide with oxalic acid valid to high ionic strength.

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References (45)

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