Chemistry of extractable nitrosyl ruthenium species in the system nitric acid-tributyl phosphate-dodecane

Abstract

Fission product ruthenium is present in solutions resulting from the dissolution of spent nuclear fuel in the form of nitro and nitrato complexes of nitrosyl ruthenium. A fraction of the ruthenium, mostly higher nitrato complexes, is extracted into the organic solvent phase in the Purex process. Stripping tests reveal a component in the solvent phase that cannot be readily transferred to the aqueous phase. Experiments were performed to determine whether the retained fraction is a highly extractable species originally present in the aqueous phase or if it is the product of a reaction between the extracted species and the solvent. A chromatographic procedure was developed to separate the species in the aqueous phase. This revealed a species more extractable than the tetranitrato complex; however, since the separation process involved TBP, the ambiguity regarding the origin of this species could not be resolved. On the other hand, in a separate series of experiments evidence was found showing that the retained species result from a reversible reaction in the solvent phase. The equilibrium concentration of this species is dependent on the temperature and the tributyl phosphate activity. This complex apparently results from the substitution of aquo ligands in the extracted species by tributyl phosphate.