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A spectrophotometric study of the impact of pH and metal-to-ligand ratio on the speciation of the Pu(vi)-oxalate system
Abstract
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)22₋ 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 themore »
- Authors:
-
[1];
[2];
[1]
- University of Notre Dame, IN (United States)
- University of Notre Dame, IN (United States); Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
- Publication Date:
- Research Org.:
- Los Alamos National Laboratory (LANL), Los Alamos, NM (United States); Oak Ridge Institute for Science and Education (ORISE), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 2281495
- Alternate Identifier(s):
- OSTI ID: 2222826
- Report Number(s):
- LA-UR-24-20293
Journal ID: ISSN 1463-9076
- Grant/Contract Number:
- 89233218CNA000001; SC0018231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Physical Chemistry Chemical Physics. PCCP
- Additional Journal Information:
- Journal Volume: 25; Journal Issue: 48; Journal ID: ISSN 1463-9076
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Sockwell, Ashleigh Kirstin, DiBlasi, Nicole Ann, and Hixon, Amy E. A spectrophotometric study of the impact of pH and metal-to-ligand ratio on the speciation of the Pu(vi)-oxalate system. United States: N. p., 2023.
Web. doi:10.1039/d3cp04010k.
Sockwell, Ashleigh Kirstin, DiBlasi, Nicole Ann, & Hixon, Amy E. A spectrophotometric study of the impact of pH and metal-to-ligand ratio on the speciation of the Pu(vi)-oxalate system. United States. https://doi.org/10.1039/d3cp04010k
Sockwell, Ashleigh Kirstin, DiBlasi, Nicole Ann, and Hixon, Amy E. Tue .
"A spectrophotometric study of the impact of pH and metal-to-ligand ratio on the speciation of the Pu(vi)-oxalate system". United States. https://doi.org/10.1039/d3cp04010k.
@article{osti_2281495,
title = {A spectrophotometric study of the impact of pH and metal-to-ligand ratio on the speciation of the Pu(vi)-oxalate system},
author = {Sockwell, Ashleigh Kirstin and DiBlasi, Nicole Ann and Hixon, Amy E.},
abstractNote = {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)22₋ 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.},
doi = {10.1039/d3cp04010k},
journal = {Physical Chemistry Chemical Physics. PCCP},
number = 48,
volume = 25,
place = {United States},
year = {Tue Nov 21 00:00:00 EST 2023},
month = {Tue Nov 21 00:00:00 EST 2023}
}
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Works referenced in this record:
Reduction of Np(VI) and Pu(VI) by Organic Chelating Agents
journal, January 1998
- Reed, D. T.; Wygmans, D. G.; Aase, S. B.
- Radiochimica Acta, Vol. 82, Issue s1
Actinide oxalates, solid state structures and applications
journal, May 2014
- Abraham, Francis; Arab-Chapelet, Bénédicte; Rivenet, Murielle
- Coordination Chemistry Reviews, Vol. 266-267
Spectroscopic investigation of the formation of PuO2Cl+ and PuO2Cl2 in NaCl solutions and application for natural brine solutions
journal, October 1999
- Runde, W.; Reilly, S. D.; Neu, M. P.
- Geochimica et Cosmochimica Acta, Vol. 63, Issue 19-20
Electronic absorption spectra of crystalline Pu(V) compounds
journal, December 2007
- Bessonov, A. A.; Krot, N. N.
- Radiochemistry, Vol. 49, Issue 6
Dioxouranium(VI) oxalate complexes †
journal, January 2000
- Ferri, Diego; Iuliano, Mauro; Manfredi, Carla
- Journal of the Chemical Society, Dalton Transactions, Issue 19
On the Hydrolysis of the Dioxouranium(VI) Ion in Oxalate Solutions
journal, May 2005
- Manfredi, Carla; Ferri, Diego; Vasca, Ermanno
- Annali di Chimica, Vol. 95, Issue 5
Crystal Growth and First Crystallographic Characterization of Mixed Uranium(IV)–Plutonium(III) Oxalates
journal, April 2013
- Tamain, Christelle; Arab Chapelet, Bénédicte; Rivenet, Murielle
- Inorganic Chemistry, Vol. 52, Issue 9
Effect of reduction on the stability of Pu(VI) hydrolysis species
journal, November 2010
- Cho, Hye-Ryun; Jung, E. C.; Park, K. K.
- ract, Vol. 98, Issue 9-11
Quantitative Microstructural Characterization of Plutonium Oxalate Auto‐Degradation and Evidence for PuO
2
Nanocrystal Formation
journal, July 2021
- Corbey, Jordan F.; Sweet, Lucas E.; Sinkov, Sergey I.
- European Journal of Inorganic Chemistry, Vol. 2021, Issue 32
Multiscale structural characterizations of mixed U( iv )–An( iii ) oxalates (An( iii ) = Pu or Am) combining XAS and XRD measurements
journal, January 2016
- Arab-Chapelet, B.; Martin, P. M.; Costenoble, S.
- Dalton Transactions, Vol. 45, Issue 16
Spectroscopic Study of the Hydrolysis of PuO2+2 in Aqueous Solution
journal, January 1995
- Pashalidis, I.; Kim, J. I.; Ashida, T.
- Radiochimica Acta, Vol. 68, Issue 2
Synthesis and study of Np(V) sesquioxalates
journal, April 2007
- Krot, N. N.; Bessonov, A. A.; Charushnikova, I. A.
- Radiochemistry, Vol. 49, Issue 2
Dioxouranium(VI)–carboxylate complexesA calorimetric and potentiometric investigation of interaction with oxalate at infinite dilution and in NaCl aqueous solution at I=1.0molL−1 and T=25°C
journal, February 2007
- Crea, F.; Derobertis, A.; Destefano, C.
- Talanta, Vol. 71, Issue 2
Reactivity of nitrate and organic acids at the concrete–bitumen interface of a nuclear waste repository cell
journal, March 2014
- Bertron, A.; Jacquemet, N.; Erable, B.
- Nuclear Engineering and Design, Vol. 268
Hydrolysis of Plutonium(VI) at Variable Temperatures (283-343 K)
journal, August 2011
- Rao, Linfeng; Tian, Guoxin; Di Bernardo, Plinio
- Chemistry - A European Journal, Vol. 17, Issue 39
Initial Hydrolysis of Plutonium(VI)
journal, March 1993
- Okajima, S.; Reed, D. T.
- ract, Vol. 60, Issue 4
Thermodynamics of the complexation of uranium(vi) with oxalate in aqueous solution at 10–70 °C
journal, January 2009
- Di Bernardo, Plinio; Zanonato, Pier Luigi; Tian, Guoxin
- Dalton Transactions, Issue 23
Literature Review for Oxalate Oxidation Processes and Plutonium Oxalate Solubility
report, February 2012
- Nash, C.
A review of plutonium oxalate decomposition reactions and effects of decomposition temperature on the surface area of the plutonium dioxide product
journal, October 2015
- Orr, R. M.; Sims, H. E.; Taylor, R. J.
- Journal of Nuclear Materials, Vol. 465
Reaction mechanisms of the thermal conversion of Pu(IV) oxalate into plutonium oxide
journal, October 2007
- Vigier, N.; Grandjean, S.; Arab-Chapelet, B.
- Journal of Alloys and Compounds, Vol. 444-445
Ligand rigidity and electronic effect on the complexation of hexavalent plutonyl with three dicarboxylic acids: a combined spectrophotometric and computational study
journal, January 2020
- Xu, Lei; Pu, Ning; Yuan, Jianhua
- New Journal of Chemistry, Vol. 44, Issue 10
The thermal decomposition of hydrated plutonium(IV) oxalates
journal, January 1964
- Jenkins, I. L.; Waterman, M. J.
- Journal of Inorganic and Nuclear Chemistry, Vol. 26, Issue 1
Solubility of plutonium(VI) carbonate in saline solutions
journal, June 2007
- Reilly, Sean D.; Runde, Wolfgang; Neu, Mary P.
- Geochimica et Cosmochimica Acta, Vol. 71, Issue 11
Raman spectral titration method: an informative technique for studying the complexation of uranyl with uranyl( vi )–DPA/oxalate systems as examples
journal, January 2017
- Liu, Qian; Zhang, Qianci; Yang, Suliang
- Dalton Transactions, Vol. 46, Issue 39
Actinide oxalate complexes formation as a function of temperature by capillary electrophoresis coupled with inductively coupled plasma mass spectrometry
journal, January 2015
- Brunel, Benoit; Philippini, Violaine; Mendes, Mickaël
- Radiochimica Acta, Vol. 103, Issue 1
X-ray powder crystallographic data on plutonium and other oxalates—II
journal, January 1965
- Jenkins, I. L.; Moore, F. H.; Waterman, M. J.
- Journal of Inorganic and Nuclear Chemistry, Vol. 27, Issue 1
Spectrophotometric study of uranyl–oxalate complexation in solution
journal, June 2002
- Havel, Josef; Soto-Guerrero, Julio; Lubal, Přemysl
- Polyhedron, Vol. 21, Issue 14-15
The Photochemical Behavior of the Uranyl Ion (UO$\rm{{_{2}^{2+}}}$): a Dimer Perspective and Outlook
journal, November 2009
- Görller‐Walrand, Christiane; Servaes, Kelly
- Helvetica Chimica Acta, Vol. 92, Issue 11
Thermodynamic and Structural Trends in Hexavalent Actinyl Cations: Complexation of Dipicolinic Acid with NpO 2 2+ and PuO 2 2+ in Comparison with UO 2 2+
journal, October 2013
- Xu, Chao; Tian, Guoxin; Teat, Simon J.
- Chemistry – A European Journal, Vol. 19, Issue 49
EPR and ENDOR studies of self(α)-irradiation effects in Pu(VI) oxalate: evidence for participation of 5f electrons of 239Pu in chemical bonding with CO2−
journal, December 2000
- Bhide, M. K.; Kadam, R. M.; Babu, Y.
- Chemical Physics Letters, Vol. 332, Issue 1-2
Pu(VI) Hydrolysis: Further Evidence for a Dimeric Plutonyl Hydroxide and Contrasts with U(VI) Chemistry
journal, February 2006
- Reilly, Sean D.; Neu, Mary P.
- Inorganic Chemistry, Vol. 45, Issue 4
X-ray powder crystallographic data on plutonium and other oxalates—I
journal, January 1965
- Jenkins, I. L.; Moore, F. H.; Waterman, M. J.
- Journal of Inorganic and Nuclear Chemistry, Vol. 27, Issue 1
Thermodynamic study on the U(VI) complexation with dicarboxylates by calorimetry
journal, November 2008
- Kirishima, Akira; Onishi, Yuko; Sato, Nobuaki
- Radiochimica Acta, Vol. 96, Issue 9-11
Visible-NIR absorption spectroscopy study of the formation of ternary plutonyl(vi ) carbonate complexes
journal, January 2020
- Jo, Yongheum; Cho, Hye-Ryun; Yun, Jong-Il
- Dalton Transactions, Vol. 49, Issue 33
Raman and infrared spectra of plutonium (IV) oxalate and its thermal degradation products
journal, April 2022
- Christian, Jonathan H.; Foley, Bryan J.; Ciprian, Elodia
- Journal of Nuclear Materials, Vol. 562