Electrochemical Description of Redox Equilibria in Nuclear Glass

Glass matrices were selected to immobilize fission products because glass is capable of chemically incorporating a wide spectrum of elements within a single matrix. Some of these elements can be found at different oxidation states. The redox equilibrium constants of multivalent species can be used to develop thermodynamic models for a better description of nuclear glasses. Some of the multivalent species loaded in nuclear glass, such as iron and sulfur, have already been a subject of investigation by conventional glassmakers or geochemists in the earth sciences. Other redox species more specifically related to nuclear glass, including cerium and ruthenium, have also been investigated. These studies have demonstrated the advantages of using electrochemical techniques, voltammetry and potentiometry, to determine the equilibrium constants. Oxygen potential measurements are also particularly suitable for characterizing the redox state of the multivalent dissolved species in molten glass.