The redox potential of Pu containing acidic solutions and the fate of "Pu(IV)-colloids": Direct measurement versus optical absorption spectroscopy

Redox potentials were measured in acidic aqueous solutions (-log(10)[H+]=0.7) containing different fractions of tri- and tetravalent plutonium. Eh values measured directly by a Pt electrode vs Ag/AgCl reference electrode agree very well with the redox potential calculated from the oxidation state distribution Pu(III)/Pu(IV). By monitoring the solutions over 120 days the kinetics of redox state distribution and dissolution of initially present Pu(IV)-colloids were studied. In solutions of Eh>950mV colloids dissolve and form Pu(VI), whereas at lower Eh the dissolution of colloids leads to formation of Pu(III). These findings corroborate the assumption that colloids are an integral part of the aqueous Pu redox chemistry and that formation and dissolution can be fully understood by means of Eh / pH stability calculations.