Redox Behavior of Neptunium(V) in Tributyl Phosphate and N,N-Dihexyl Octanamide Extractants Dissolved in n-Dodecane |
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Authors: | P. N. Pathak Neelam Kumari D. R. Prabhu V. K. Manchanda |
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Affiliation: | (1) Radiochemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai, 400 085, India;(2) Department of Energy Science, Sungkyunkwan University, Suwon, 440746, Korea |
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Abstract: | Spectrophotometric investigations have been carried out on the disproportionation of Np(V) to form Np(IV) and Np(VI) in 1.1 mol⋅L−1 solutions of tributyl phosphate (TBP) and in N,N-dihexyl octanamide (DHOA) in n-dodecane medium. The Np(V) was found to coordinate with Np(IV) in 1.1 mol⋅L−1 TBP solution in n-dodecane to form a mixed valence “cation–cation” complex by bonding through an axial oxo group on Np(V). By contrast, this interaction was less prominent in the case of 1.1 mol⋅L−1 DHOA solutions. The effect of 1-octanol, added as phase modifier, on the disproportionation behavior of Np(V) was also investigated. An attempt was made to calculate the disproportionation/reduction rate constants for Np(V) under the conditions of these studies. Absorbance measurements on the Np stripped from organic phases revealed the occurrence of Np(V) in the aqueous phase. |
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