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Title: Complexation of Plutonium (IV) with Sulfate at VariableTemperatures

Authors:
; ; ; ;
Publication Date:
Research Org.:
COLLABORATION - Pacific Northwest NationalLaboratory
Sponsoring Org.:
USDOE
OSTI Identifier:
917311
Report Number(s):
LBNL-63454
DOE Contract Number:
DE-AC02-05CH11231
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Radioanalytical Nuclear Chemistry; Journal Volume: 274; Journal Issue: 1; Related Information: Journal Publication Date: 2007
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Xia, Y., Friese, J.I., Moore, D.A., Bachelor, P.P., and Rao, L. Complexation of Plutonium (IV) with Sulfate at VariableTemperatures. United States: N. p., 2007. Web. doi:10.1007/s10967-006-6907-z.
Xia, Y., Friese, J.I., Moore, D.A., Bachelor, P.P., & Rao, L. Complexation of Plutonium (IV) with Sulfate at VariableTemperatures. United States. doi:10.1007/s10967-006-6907-z.
Xia, Y., Friese, J.I., Moore, D.A., Bachelor, P.P., and Rao, L. Thu . "Complexation of Plutonium (IV) with Sulfate at VariableTemperatures". United States. doi:10.1007/s10967-006-6907-z.
@article{osti_917311,
title = {Complexation of Plutonium (IV) with Sulfate at VariableTemperatures},
author = {Xia, Y. and Friese, J.I. and Moore, D.A. and Bachelor, P.P. and Rao, L.},
abstractNote = {},
doi = {10.1007/s10967-006-6907-z},
journal = {Journal of Radioanalytical Nuclear Chemistry},
number = 1,
volume = 274,
place = {United States},
year = {Thu Feb 01 00:00:00 EST 2007},
month = {Thu Feb 01 00:00:00 EST 2007}
}
  • The complexation of plutonium(IV) with sulfate at variable temperatures has been investigated by solvent extraction method. A NaBrO{sub 3} solution was used as holding oxidant to maintain the plutonium(IV) oxidation state throughout the experiments. The distribution ratio of Pu(IV) between the organic and aqueous phases was found to decrease as the concentrations of sulfate were increased. Stability constants of the 1:1 and 1:2 Pu(IV)-HSO{sub 4}{sup -} complexes, dominant in the aqueous phase, were calculated from the effect of [HSO{sub 4}{sup -}] on the distribution ratio. The enthalpy and entropy of complexation were calculated from the stability constants at different temperaturesmore » using the Van't Hoff equation.« less
  • The complexation of plutonium(IV) with sulfate at variable temperatures from 25o C to 55o C has been investigated by solvent extraction method. A NaBrO3 as holding oxidant was used to maintain plutonium in the Pu(IV) oxidation state throughout the experiments. The distribution ratio of Pu(IV) between the organic and aqueous phases was found to decrease as the concentrations of sulfate were increased. Stability constants of the 1:1 and 1:2 Pu(IV)-HSO4- complexes, dominant in the aqueous phase under the experimental conditions, were calculated from the effect of [HSO4-] on the distribution ratio. The enthalpy and entropy of complexation were calculated frommore » the stability constants at different temperatures by using the Van’t Hoff equation.« less
  • Complexation of Pu(IV) with fluoride was studied by solvent extraction at 25, 40 and 55 C in 2.2 mol {center_dot} kg{sup -1} HClO{sub 4}. The distribution ratio of Pu(IV) between the organic and aqueous phases decreased as the concentration of fluoride was increased due to the formation of Pu(IV)-F complexes in the aqueous phase. Two complexes, PuF{sup 3+} and PuF{sub 2}{sup 2+}, were identified under the conditions in this work and their stability constants at 25, 40 and 55 C and I = 2.2 mol {center_dot} kg{sup -1} HClO{sub 4} were determined from the distribution data. The Specific Ion Interactionmore » approach (SIT) was used to extrapolate the constants to the state of infinite dilution. Data from this work indicate that the complexation of Pu(IV) with fluoride is endothermic and entropy-driven. The complexation becomes stronger at higher temperatures.« less
  • The complexation of Pu(IV) with fluoride at elevated temperatures was studied by solvent extraction technique. A solution of NaBrO3 was used as holding oxidant to maintain the oxidation state of plutonium throughout the experiments. The distribution ratio of Pu(IV) between the organic and aqueous phases was found to decrease as the concentrations of fluoride were increased. Stability constants of the 1:1 and 1:2 Pu(IV)-F- complexes, dominant in the aqueous phase under the experimental conditions, were calculated from the effect of fluoride ions on the distribution ratio. The thermodynamic parameters, including enthalpy and entropy of complexation between Pu(IV) and fluoride atmore » 25 degrees C - 55 degrees C were calculated from the stability constants at different temperatures by using the Van’t Hoff equation.« less
  • The effect of the concentration of nitric acid and tetravalent uranium and the effect of sulfonate and sulfate ions on the reduction reextraction of plutonium from organic phases containing 30% TBP in kerosene, 0.33M UO/sub 2/(NO/ sub 3/)/sub 2/, 0.4M HNO/sub 3/, and approximately 10/sup -5/M Pu were investigated. The effectiveness of the reextraction increases with decreasing concentration of nitric acid and with increasing concentration of tetravalent uranium. Sulfonic acid exents only a small effect on the stability of trivalent plutonium, but with the addition of uranium(IV) sulfate solutions even 0.02M H2SO/ sub 4/ prevents the reverse oxidation of plutoniummore » for 22 hr. (tr-auth)« less