REDOX BEHAVIOUR OF NEPTUNIUM IN PUREX EXTRACTION PROCESSES

点击翻译按钮获取中文摘要

In order to clarify the distribution behavior of neptunium in the Purex extraction processes, the equilibrium and rate of the extraction of neptunium into 30% TBP-dodecane were examined as a function of nitrous acid (3-6 M) and nitrous acid (10^<-4>-10^<-2> M) concentrations. It was shown that the rapid equilibrium between nitric and nitrous acids controlls the redox potential of the aqueous phase, which in turn controlls the ratio of the concentrations of extractable Np(VI) to unextractable Np(V). The redox potential can be quantitatively described with using the activities of nitric acid, nitrous acid and water in nitric acid solutions:E/V = 0.951 + 0.058・log<@D7{HNO<@D23@>D2}<@D12@>D1(/){HNO<@D22@>D2}<@D11/2@>D1{H<@D22@>D2O}<@D11/2@>D1@>D7 By examining also the rate of the extraction of neptunium into TOPO-dodecane, the ratedetermining step was confirmed to be the oxidation of Np(V) to Np(VI) in the aqueous phase. The rate of the reaction was obtained to be:k/h = 5.44 x {HNO_3}^<1.02>{HNO_2}^<0.56>