Abstract

Titrations of Pu(IV) with HNO3 in a series of aqueous HClO4 solutions ranging in ionic strength from 2 to 19 molal were followed using visible and near-infrared absorption spectrophotometry. The Pu 5f-5f spectra in the visible and near IR range change with complex formation. At each ionic strength, a series of spectra were obtained by varying nitrate concentration. Each series was deconvoluted into spectra of Pu4+ (aq), Pu(NO3)3− and Pu(NO3)22+ complexes, and simultaneously their formation constants were determined. When corrected for the incomplete dissociation of nitric acid, the ionic strength dependence of each formation constant can be described by two parameters, β0 and Δe using the formulae of specific ion interaction theory.

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