Abstract
Monoamides extractants are being studied in recent years as alternate extractants to TBP for irradiated nuclear fuels reprocessing. Their extracting strength and selectivity toward Pu(IV) can be tuned depending on the nature of their alkyl chain and the nitric acid concentration. Like TBP, monoamides can extract water and nitric acid while in contact. However, nitric acid is unstable in both aqueous and organic phases. Due to radiolysis, it can be disproportionate in nitrous acid (HNO2) which is known to possess redox properties. It could lead to the formation of the HNO3/HNO2 redox couple which may cause several parasitic redox reactions and affect the recycling process. Meaningful the redox speciation of actinides (An) in an organic phase is important for acute control of the recycling processes. The electrochemical behavior of the Ce(IV)/Ce(III) couple have been studied at 25 and 40°C by cyclic voltammetry at a vitreous carbon working electrode in three N,N-dialkylamides solvents (DEHBA (N,N-di-(2-ethylhexyl)-n-butanamide), DEHiBA (N,N-di-(2-ethylhexyl)-iso-butanamide) and DEHDMBA (N,N-di-(2-ethylhexyl-)3,3-dimethylbutanamide)) pre-equilibrated with aqueous nitric acid solutions (HNO3 5M). Results showed that the Ce(IV)/Ce(III) redox process exhibits a well-defined reversible couple with a diffusion-controlled electrochemical behavior. This initial study on the Ce(IV)/Ce(III) couple, a "non-radioactive model" of the Pu(IV)/Pu(III) couple has been an entry to the direct electrochemical characterization of plutonium in these extractants aiming to identify the nature of the electrochemical process of the Ce(IV)/Ce(III) couple and the difficulties associated with carrying out electrochemical measurements in these viscous and low conductive media. The Pu(IV)/Pu(III) couple has been studied at 40°C in DEHBA at a vitreous carbon working electrode at different concentrations of nitric acid (0,6 M < [HNO3]org < 3,7 M). The study of the speciation of plutonium (IV) in the organic DEHBA phase after extraction showed the presence of two types of plutonium(IV) complexes with variable predominance due to the nitric acid concentration. Cyclic voltammetry measurements showed an significant effect of the speciation of plutonium in the organic phase on the electroactivity of the Pu(IV)/Pu(III) couple. At low nitric acid concentrations, the Pu(IV)/Pu(III) redox process exhibits a well-defined reversible couple with a diffusion-controlled electrochemical behavior. At higher nitric acid concentrations, no electrochemical response of the Pu(IV)/Pu(III) couple is observed. This study enabled the determination of physic and chemical characteristics of the Ce(IV)/Ce(III) and Pu(IV)/Pu(III) couples in N,N-dialkylamides media as the redox potential and the diffusion coefficient that were not previously studied. This study validates the implementation of electrochemical method for the quantification of tetravalent metallic cation in organic phases.