抄録
A photochemically-induced valency adjustment method has been studied to remove Np from the mixed nitric acid solutions of Pu and Np in connection with the Purex reprocessing. The valencies of Pu and Np ions were adjusted to be Pu(III) and Np(V) under the initial conditions and their concentrations were 1 × 10-4 and 1× 10-3' mol•dm-3, respectively. The experiments were carried out under the various conditions changing the irradiation intensities of the Hg lamp in the various concentrations of HNO3. It was found that the rates of the redox reactions of the Pu ions were significantly affected by the irradiated light as well as the acid strength. Under the irradiation of the 0.015 W Hg lamp in 3 HNO3 solution containing a tenfold excess of a hydroxylamine and hydrazine, more than 95% Pu(III) was oxidized rapidly to Pu(IV) within 10 min irradiation and it remained at the same valency even after the continuous further irradiation.
On the other hand, the irradiation did not change the valency of Np(V) under the conditions studied. These valency conditions, i.e. Pu(IV) and Np( V), are appropriate for separating Np from Pu by the solvent extraction with TBP-n-dodecane.
The present results lead to the conclusion that the photochemical method has a high potential for removing Np from the mixed solution of Pu and Np. The photochemical redox reaction mechanisms of Pu and Np in the nitric acid solution were discussed from the stand-points of the thermodynamic and kinetic considerations related to the variation in their standard electrode potentials of the photo-excited ion species by the light irradiation.
