Abstract
Complexation of NpO2 + and NpO2 2 + with unsaturated K n P2W17O61 n - 1 0 (L x-) heteropolyanion and disproportionation of Np(V) in the presence of L x- were studied spectrophotometrically. The logarithms (logK) of the formation constants of NpO2 VL and NpO2 V IL are ∼3 and 7, respectively. The K+ and Na+ cations bind the L x- anions, thus decreasing the yield of the complexes. Neptunium(V) disproportionation in K10P2W17O61 solutions containing 1 M (HClO4 + NaClO4) (pH from 0 to 4) and free from NaClO4 (pH 2-6.5) was studied. The disproportionation rate is described by the equation -d[Np(V)]/dt = k[Np(V)][L x-]. The pH dependence of the rate constant passes through a maximum at pH 1. The rate constant decreases with increasing [Na+]. The reaction is inhibited by its product, Np(IV). The Np(V) complex is not involved in disproportionation; the reactive species is NpO2 + aqua ion, which is probably converted into NpO3 +L x-. Then NpO3 +L x- rapidly reacts with NpO2 +, which occurs simultaneously with, or is preceded by release of the second oxygen atom.
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