Abstract
Complexation of uranyl (UO2 2+) and neptunyl (NpO2 +) with citrate at high ionic strengths I(m) has been investigated by solvent extraction with HDEHP. β1 app values were obtained for I(m) between 0.3 m and 5.0 m NaCl. For NpO2 +, at pHm = 4.7–6.4 only the 1:0:1 complex was formed while for UO2 2+ at pHm 3.0 the 1:1:1 and 1:0:1 complexes were detected with the latter species more dominant. Values obtained for β1 app ranged from 2.62 ± 0.05 to 2.56 ± 0.03 for neptunyl and from 7.30 ± 0.04 to 7.03 ± 0.08 for uranyl as 1 increased from 0.3m to 5.0m NaCl. The β1 app values were used to estimate the concentration of citrate required in a neutral brine to provide a 10% competition with hydrolysis.
This is a preview of subscription content, log in via an institution to check access.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Preview
Unable to display preview. Download preview PDF.
References
Lappin, A.R., Garber, D.P., Hunter, R.L., Davies, P.B., System analysis, long-term radionuclide transport, and dose assessment, waste isolation pilot plant (WIPP), southeastern New Mexico. Report SAND89-0462, Sandia National Laboratories (1989).
Moskvin, A.I., Marov, I.N., Zolotov, Y.A., Neptunium (V) complexes with citric and tartaric acids. Russ. J. Inorg. Chem., 6:926–929 (1961).
Sevost’yanova, E.P., Complex formation by neptunium(V) with citric acid. Radiokhimiya, 27:24–27 (1985).
Rees, T.F., Daniel, S.R., Complexation of neptunium(V) by salicylate, pthalate and citrate ligands in a pH 7.5 phosphate buffered system. Polyhedron, 3:667–673 (1984).
Inoue, Y., Tochiyama, O., Takahashi, T., Study of the carboxylate complexing of Np(V) by solvent extraction with TTA and capriquat. Radiochimica Acta, 31:197–199 (1982).
Rizkalla, F.N., Nectoux, F., Dabos-Seignon, S., Pages, M., Complexation of neptunium(V)by halo-and hydroxycarboxylate ligands. Radiochimica Acta, 51:113–118 (1990).
Rajan, K.S., Martell, A.E., Equilibrium studies of uranyl complexes III. Interaction of uranyl ion with citric acid. Inorg.Chem., 4:462–469 (1964).
Vaňura, P., Kuča, L., Citrate complexes of uranyl in solutions with high citrate concentrations. Collect. Czech. Chem. Comm. 45:41–53 (1980).
Gustafson, R., Martell, A., Ultracentrifugation of uranyl citrate chelates J. Am. Chem. Soc., 85:2571–2574 (1963).
Feldman, I., Havill, J., Newman, W., The uranyl-citrate system. II. Polarographic studies of the 1:1 complex. J. Am. Chem, Soc., 73:3593–3595 (1951).
Feldman, I., North, C.A., Hunter, H.B., Equilibrium constants for the formation of polynuclear tridentate 1:1 chelates in uranyl-malate,-citrate, and-tartarate systems. J. Phys.Chem., 64:1224–1230 (1960).
Adin, A., Klotz, P., Newman, L., Mixed-metal complexes between In(III) and U(VI) with malic, citric and tataric acids. Inorg.Chem., 9:2499–2505 (1970).
Markovits, G., Klotz, P., Newman, L., Formation constants for the mixed metal complexes between In(III) and U(VI) with malic, citric and tataric acids. Inorg. Chem., 11:2405–2408 (1972).
Ohyoshi, E., Oda, J., Ohyoshi, A., Complex formation between the uranyl ion and citric acid. Bull. Chem. Soc. Jap., 48:227–229 (1975).
Borkowski, M., Lis, S., Choppin, G.R., Complexation study of NpO2 + and UO2 2+ ions with several organic ligands in aqueous solutions of high ionic strength. Radiochimica Acta 74:117–121 (1996).
Feldman, I., Newman, W., The uranyl-citrate system. I. Spectrophotometric studies in acid solution. ai]J._Am. Chem. Soc., 73:2312–2315 (1951).
Li, N. C., Lindenbaum, A., White, J. M., Some metal complexes of citric and tricarballylicacids. J. Inorg. Nucl. Chem. 12:122–128 (1959).
Peppard, D.F., Mason, G. W., Maier, J. L., Driscoll, W.J. Fractional extraction of the lanthanides as their dialkyl orthophoshates. J. Inorg. Nucl. Chem. 4:334 (1954).
Erten, H.N., Mohammed, A.K., and Choppin, G.R., Variation of stability constants of thorium and uranium oxalate complexes with ionic strength. Radiochimica Acta 66/67:123–128 (1994).
Mizera, J., Bond, A.H., Choppin, G.R., Dissociation constants of carboxylic acids at high ionic strengths. Radionuclide Speciation in Real Systems, eds. Reed, D.T., Clark, S., Rao, L., Plenum (1998).
Choppin, G.R., Rao L.F., Complexation of pentavalent and hexavalent actinides by fluoride. Raiochimica Acta 37:143–146 (1984).
Grenthe, I., Fulger. J., Konings, R.J.M. et al. OECD-Chemical Thermodynamics Vol.1, Chemical Thermodynamics of Uranium. Elsevier Publishers B.V., 683, (1992).
Labonne-Wall, N., Choppin, G.R., Lopez, C., Monsallier, J-M., Interaction of uranyl with humic and fulvic acids at high ionic strength, Radionuclide Speciation in Real Systems, eds. Reed, D.T., Clark, S., Rao, L., Plenum (1998).
Allen, P., Shuh, D., Bucher, J., Edelstein, N., Reich, T., Denecke, M., Nitsche, H., EXAFS Determinations of uranium structures: the uranyl ion complexed with tartaric, citric, and malic acids. Inorg.Chem., 35:784–787 (1996).
Author information
Authors and Affiliations
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 1999 Kluwer Academic / Plenum Publishers, New York
About this chapter
Cite this chapter
Bronikowski, M., Pokrovsky, O.S., Borkowski, M., Choppin, G.R. (1999). UO2 2+ and NpO2 + Complexation with Citrate in Brine Solutions. In: Reed, D.T., Clark, S.B., Rao, L. (eds) Actinide Speciation in High Ionic Strength Media. Springer, Boston, MA. https://doi.org/10.1007/978-1-4419-8690-0_11
Download citation
DOI: https://doi.org/10.1007/978-1-4419-8690-0_11
Publisher Name: Springer, Boston, MA
Print ISBN: 978-1-4613-4666-1
Online ISBN: 978-1-4419-8690-0
eBook Packages: Springer Book Archive