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Speciation and Bioavailability Measurements of Environmental Plutonium Using Diffusion in Thin Films
Published on: November 9, 2015
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Homoleptic An(IV) Dimethyl Sulfoxide Complexes of Th-Pu Enable Insight into Solution Speciation and Redox
Emily R Mikeska1, Kayleigh R Autry2, David A Dixon2
1Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States.
Inorganic Chemistry
|November 4, 2025
Summary
Tetravalent actinide ions show different solvation in dimethyl sulfoxide (DMSO) compared to water. DMSO stabilizes these ions more than water, influencing their reactivity and speciation.
Area of Science:
- Inorganic Chemistry
- Actinide Chemistry
- Coordination Chemistry
Background:
- Understanding solvation properties of tetravalent actinide ions is crucial for nuclear fuel reprocessing and waste management.
- Dimethyl sulfoxide (DMSO) is a potential alternative solvent to aqueous media for actinide chemistry.
Purpose of the Study:
- To evaluate the solvation properties of tetravalent actinide ions in DMSO versus aqueous media.
- To investigate the speciation and thermodynamics of actinide complexes in DMSO.
- To assess the electrochemical behavior of Np and Pu in DMSO.
Main Methods:
- Synthesis of 8- and 9-coordinate homoleptic dimethyl sulfoxide An(IV) complexes.
- Comparison of solid-state and solution-phase electronic absorption spectra.
- Experimental and computational determination of thermodynamic equilibria.
- Cyclic voltammetry of Np and Pu in DMSO electrolyte.
Main Results:
- Actinide complexes were successfully synthesized and characterized.
- Solution speciation was inferred by comparing solid-state and solution spectra.
- Thermodynamics of 8- and 9-coordinate equilibria correlate with ionic radius.
- Tetravalent Np and Pu ions are stabilized in DMSO compared to aqueous media.
- DMSO exhibits a more donating character than water.
Conclusions:
- DMSO offers enhanced stabilization for tetravalent actinide ions compared to water.
- The observed stabilization is attributed to the donating nature of DMSO.
- Further reactivity is anticipated upon reduction to the +III oxidation state.
- These findings have implications for actinide separation and processing in non-aqueous media.
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