Estimation of parameters in plutonium solutions

Silver, G. L.

doi:10.1007/s10967-010-0501-0

Cited by 10 publications

(5 citation statements)

References 14 publications

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“…The p K a obtained for [Pu(H 2 O) 8 ] 4+ from the metadynamics simulations is vastly different from a value of −0.60 obtained from older experimental data sets and the NEA-TDB, suggesting spontaneous hydrolysis. This value is however in good agreement with the values of 0.59 obtained by Yusov et al and 0.00 ± 0.20 obtained by Yun et al It also agrees with the estimated values obtained by Silver. ,, We note that as a result of the discrepancies between the various experimental studies on Pu 4+ hydrolysis, Lemire et al have previously suggested a rather large value of 0.78 ± 0.60. The reaction Δ F obtained from our simulations indicates the hydrolysis of Pu 4+ is not spontaneous, a situation suggested by the older experimental data .…”

Section: Resultssupporting

confidence: 92%

“…This value is however in good agreement with the values of 0.59 obtained by Yusov et al 12 and 0.00 ± 0.20 obtained by Yun et al 8f It also agrees with the estimated values obtained by Silver. 8d,e, 57 We note that as a result of the discrepancies between the various experimental studies on Pu 4+ 3+ . The raw and corrected ΔF values were found to be 10.37 and 9.13 kcal/mol, respectively.…”

Section: ■ Results and Discussionmentioning

confidence: 75%

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Coordination and Hydrolysis of Plutonium Ions in Aqueous Solution Using Car–Parrinello Molecular Dynamics Free Energy Simulations

2013

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Car-Parrinello molecular dynamics (CPMD) simulations have been used to examine the hydration structures, coordination energetics, and the first hydrolysis constants of Pu(3+), Pu(4+), PuO2(+), and PuO2(2+) ions in aqueous solution at 300 K. The coordination numbers and structural properties of the first shell of these ions are in good agreement with available experimental estimates. The hexavalent PuO2(2+) species is coordinated to five aquo ligands while the pentavalent PuO2(+) complex is coordinated to four aquo ligands. The Pu(3+) and Pu(4+) ions are both coordinated to eight water molecules. The first hydrolysis constants obtained for Pu(3+) and PuO2(2+) are 6.65 and 5.70, respectively, all within 0.3 pH unit of the experimental values (6.90 and 5.50, respectively). The hydrolysis constant of Pu(4+), 0.17, disagrees with the value of -0.60 in the most recent update of the Nuclear Energy Agency Thermochemical Database (NEA-TDB) but supports recent experimental findings. The hydrolysis constant of PuO2(+), 9.51, supports the experimental results of Bennett et al. [Radiochim. Acta 1992, 56, 15]. A correlation between the pKa of the first hydrolysis reaction and the effective charge of the plutonium center was found.

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Section: Resultssupporting

confidence: 92%

Section: ■ Results and Discussionmentioning

confidence: 75%

Coordination and Hydrolysis of Plutonium Ions in Aqueous Solution Using Car–Parrinello Molecular Dynamics Free Energy Simulations

2013

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“…There is more enthusiasm for semi-empirical, ad hoc methods than there is for the comparatively simple conservation principles. The expressed preferences lead to questions not adequately addressed[8]. History may decide that contemporary preferences have more to do with tribal solidarity than with science.The new approach for estimating the pH of a plutonium solution does not rely on electrodes, buffer solutions, or curve fitting.…”

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confidence: 99%

What is the acidity of a plutonium solution?

Silver

2010

J Radioanal Nucl Chem

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“…In other words, the estimate KH-0.355 as the equilibrium constant for Eq. (l) is not supported by the results of two tests that compare estimated to measured acid concentrations [7,8,11]. The tests herein and in [7] are related but they are not identical.…”

Section: Comparisons Between Measurements Of [H+] and The Six Estimatmentioning

confidence: 74%

Plutonium hydrolysis and the double double-point

Silver

2010

J Radioanal Nucl Chem

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There is uncertainty about the numerical value of the first hydrolysis constant of the tetravalent plutonium ion. A new method for discriminating between the claims is illustrated. It suggests the traditional estimates of that constant are closer to its true value than a singular result based on a few solvent extraction experiments. A previously unnoticed multiple point in aqueous Pu chemistry is illustrated.

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Estimation of parameters in plutonium solutions

Cited by 10 publications

References 14 publications

Coordination and Hydrolysis of Plutonium Ions in Aqueous Solution Using Car–Parrinello Molecular Dynamics Free Energy Simulations

Coordination and Hydrolysis of Plutonium Ions in Aqueous Solution Using Car–Parrinello Molecular Dynamics Free Energy Simulations

What is the acidity of a plutonium solution?

Plutonium hydrolysis and the double double-point

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