Third phase inversion, red oil formation, and multinuclear speciation of tetravalent cerium in the tri-n-butyl phosphate–n-dodecane solvent extraction system

ABSTRACT

The extraction of tetravalent cerium, Ce(IV), from aqueous nitric acid with tri-n-butyl phosphate (TBP) in n-dodecane was studied by varying the aqueous, initial cerium(IV) concentration, [Ce⁴⁺]_aq,init, up to and beyond the point of third phase formation, defined by the critical aqueous concentration (or CAC) and the limiting organic concentration (or LOC). The new chemistry, elaborated here for the nearly-century-old Ce(IV)–20% TBP system, focuses on the phenomena of third phase inversion and the distribution of four solutes—Ce(IV), HNO₃, H₂O, and TBP—between the aqueous and organic phases, which are of direct relevance to the PUREX process. We demonstrate that multinuclear Ce(IV) entities are present in the organic phases.

KEYWORDS:

• Bulk electrolysis
• Ce(IV) dimer
• distribution ratio
• FT-IR spectroscopy
• solute isotherm
• XANES

Acknowledgments

We thank Renato Chiarizia for assistance during the initial stages of this work, which is supported by the U. S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, under contract No DE-AC02-06CH11357.