Chemistry of neptunium and of other actinides in carbonate medium

This work is a contribution to the establishment of a thermodynamic data base in order to forecast the behaviour of Np and other actinides in natural waters that might come into contact with a nuclear waste repository. Redox potentials and complexation constants in acidic and carbonate media are measured in aqueous solutions, in the presence of an inert salt (sodium perchlorate) of variable concentrations. The activity coefficients are calculated, from the variation of thermodynamic measurements with the ionic strength, with the Specific Interaction Theory (S.I.T.). The electrochemical data, obtained by polarography and voltamperometry, are interpreted, for irreversible systems, with numerical and graphical methods based on the Koutecky-Weber's and S.I.T. equations. The equilibrium constants in carbonate medium are measured by absorption spectrophotometry and a graphical method is proposed to determine the stoichiometries of polynuclear species. In this work are proposed numerical data relative to: - the redox potentials of the systems: M(VI/V) and M(IV/III) in acidic medium where M = U, Np, Pu; U(VI/V) in carbonate medium; Np(VI/V) in bicarbonate medium of ionic strength 3 M. - the formation constants of the hexakis (carbonato) tris [dioxoneptunate (VI)] complex in 3 M medium - the formation constants of the mono, di and tri (carbonato) dioxoneptunate (V) complexes - the influence of the ionic strength on some of the studied chemical equilibria by using, when necessary, literature results. All specific interaction coefficients (activity coefficients) of these species are also measured or calculated.