Raman spectroscopy of neptunyl and plutonyl ions in aqueous solution: hydrolysis of neptunium(VI) and plutonium(VI) and disproportionation of plutonium(V)

Author’s reply to “Comment on ‘Plutonium chemistry: a synthesis of experimental data and a quantitative model for plutonium oxide solubility’ by J.M. Haschke and V.M. Oversby”

“…The pHdependent second-order rate constants (k V and k VI ) derived from the available data for Pu(V) and Pu(VI) [7][8][9][10]13,14] in non-complexing solutions (Fig. 2) are in close agreement and validate Eq.…”

“…The method is adopted because ln(rate)-ln[Pu] data show that behavior of Pu(VI) is indistinguishable from that of Pu(V) [2]. Regression analysis of rate data for Pu(VI) at pH 1.5 [8], pH 6.0 [10], and pH 7.1 [14] gives respective orders of 1.5, 2.6, and 1.9 that center on 2 and lead to Àd([Pu(VI)]/dt) = k VI [Pu(VI)] 2 . The k VI of 4 · 10 À5 mol À1 s À1 derived by Newton and Hobart [1] for n = 2 accurately describes the data at pH 1.5.…”

On the performance of the intermediate Hamiltonian Fock-space coupled-cluster method on linear triatomic molecules: The electronic spectra of NpO2+, NpO22+, and PuO22+

“…Comparison to experimental data is difficult as it is well known that solvation and complexation lower the vibrational frequencies of actinyls considerably. 44 Madic et al 45 gave Raman data for these ions in aqueous solution. The difference in values for the symmetric stretch of NpO 2 + and PuO 2 2+ ͑767 and 833 cm −1 , respectively͒ of 66 cm −1 is remarkably similar to our computed gas phase difference of 71 cm −1 .…”

The redox potential of Pu containing acidic solutions and the fate of "Pu(IV)-colloids": Direct measurement versus optical absorption spectroscopy

“…Strong deviations of steady state distributions from the expected equilibria were reported by Romanovski et al [19] and Nitsche et al [20] over a wide range of acidity and Pu concentration. On the other hand, acceleration of redox reactions by Pu(IV) polymers was suggested [21,22] and Newton et al [23] assumed that Pu(V) disproportionation cannot proceed at all in the absence of Pu(IV) polymers.…”