Nuclear fuel reprocessing schemes such as PUREX and UREX utilise HNO3 media. An understanding of the corrosion of process engineering materials such as stainless steel in such media is a major concern for the nuclear industry. Two key species are cerium and chromium which, as Ce(IV), Cr(VI), may act as corrosion accelerants. An on-line analytical technique for these quantities would be useful for determining the relationship between corrosion rate and [Ce(IV)] and [Cr(VI)]. Consequently, a strategy for simultaneous quantification of Ce(IV), Cr(VI) and Cr(III) in the presence of other ions found in average burn-up Magnox / PWR fuel reprocessing stream (Fe, Mg, Nd, Al) is being developed.

This involves simultaneous UV-vis absorbance measurement at 620, 540, 450 nm, wavelengths where Ce and Cr absorb but other ions do not. Mixed solutions of Cr(VI) and Ce(IV) are found to present higher absorbance values at 540 nm than those predicted from absorbances recorded from single component solutions of those ions. This is attributed to the formation of a 3: 1 Cr(VI)-Ce(IV) complex and we report on the complexation and UV-visible spectrophotometric characteristics of this species. To the best of our knowledge this is the first experimental study of this complex in aqueous nitric acid solution systems.