Abstract
Interaction of actinides(IV) with hydroxyisobutyric acid (HHIB) in aqueous solutions and in the course of crystallization of solid compounds was studied. The complexes ML (4-n)+ n (M = U, Np, Pu; L− is hydroxyisobutyrate anion; n = 1, 2, 3) exist in solution. Their apparent stepwise stability constants K′ i were measured, and the overall concentration stability constants β3 of the complexes ML +3 were calculated. For U(IV) and Np(IV), logβ3 is close to 13.3–13.4, and for Pu(IV), logβ3 = 14.5 ± 0.9 (ionic strength I = 0.1–0.3). In the course of crystallization in air, complexes of U(IV) with hydroxyisobutyric acid, as well as those with citric acid, undergo oxidative degradation, which can be accompanied by complete oxidation of U(IV). The crystalline compounds formed in the process are oxalates of U(IV) or U(VI). The complexation of Np(V) with HHIB was studied. NpO +2 forms with HHIB the complexes NpO2L and NpO2L −2 . Their concentration stability constants are logK 1 = 2.04 ± 0.15 and logK 2 = 0.71 ± 0.10 (I = 0.4), i.e., logβ2 = 2.75 ± 0.25.
Similar content being viewed by others
References
Deelstra, H. and Verbeek, F., J. Chromatogr. A, 1965, vol. 17, pp. 558–566.
Choppin, G.R. and Chopoorian, J.A., J. Inorg. Nucl. Chem., 1961, vol. 22, nos. 1–2, pp. 97–113.
Deelstra, H. and Verbeek, F., Anal. Chim. Acta, 1964, vol. 31, pp. 251–257.
Dedov, V.B., Levedev, I.A., Ryzhov, M.N., et al., Radiokhimiya, 1961, vol. 3, no. 6, pp. 701–705.
Lebedev, I.A. and Shalinets, A.B., in Khimiya transuranovykh i oskolochnykh elementov (Chemistry of Transuranium and Fission Elements), Leningrad: Nauka, 1967, pp. 140–144.
Moskvin, A.I., Radiokhimiya, 1971, vol. 13, no. 4, pp. 582–588.
Szabó, Z. and Grenthe, I., Inorg. Chem., 2000, vol. 39, no. 22, pp. 5036–5043.
Borkowski, M., Lis, S., and Choppin, G.R., Complexation Study of NpO +2 and UO 2+2 Ions with Several Organic Ligands in Aqueous Solutions of High Ionic Strength, DOE Report CONF 950946, http://www.osti.gov/bridge/purl.cover.jsp;jsessionid=80BDA3C524C15EA7C3D31D5D30263B09?purl=/102411-iNDrAQ/webviewable/.
Moll, H., Geipel, G., Reich, T., et al., Radiochim. Acta, 2003, vol. 91, no. 1, pp. 11–20.
Moll, H., Geipel, G., Bernhard, G., et al., Complex Formation in the System Uranium(VI)-Alpha-Substituted Carboxylic Acids Studied by UV-vis Spectroscopy. Part II: α-Hydroxyisobutyric Acid, Annual Report of the Inst. of Radiochemistry, 2000, p. 3.
Rizkalla, E.N., Nectoux, F., Dabos-Seignon, S., and Pagès, M., Radiochim. Acta, 1990, vol. 51, no. 3, pp. 113–117.
Stout, B.E., Caceci, M.S., Nectoux, F., and Pagès, M., Radiochim. Acta, 1989, vol. 46, no. 4, pp. 181–184.
Yusov, A.B., Sokolova, M.N., Grigor’ev, M.S., et al., Radiokhimiya, 2012, vol. 54, no. 2, pp. 97–106.
Shilov, V.P., Yusov, A.B., and Fedoseev, A.M., Radiokhimiya, 2007, vol. 49, no. 5, pp. 412–416.
APEX2, Madison, Wisconsin (USA): Bruker AXS Inc., 2007.
SAINT-Plus, Version 6.01, Madison, Wisconsin (USA): Bruker AXS Inc., 1998.
Sheldrick, G.M., SADABS, Madison, Wisconsin (USA): Bruker AXS Inc., 2004.
Sheldrick, G.M., Acta Crystallogr., Sect. A, 2008, vol. 64, no. 1, pp. 112–122.
Martel, A.E., Smith, R.M., and Motekaitis, R.J., NIST Critically Selected Stability Constants of Metal Complexes: Version 8.0, College Station, TX.
Yusov, A.B., Fedosseev, A.M., and Delegard, C.H., Radiochim. Acta, 2004, vol. 92, no. 12, pp. 869–881.
Inoue, Y., Tochiyama, O., and Takahashi, T., Radiochim. Acta, 1982, vol. 31, nos. 3/4, pp. 197–199.
Inoue, Y. and Tochiyama, O., Polyhedron, 1983, vol. 2, no. 7, pp. 627–630.
Bailey, H., Mosselmans, J.F., and Schofield, P.F., Chem. Geol., 2005, vol. 216, nos. 1–2, pp. 1–16.
Thuéry, P., Inorg. Chem., 2007, vol. 46, no. 6, pp. 2307–2315.
Thuéry, P., Chem. Commun., 2006, no. 8, pp. 853–855.
Budantseva, N.A., Grigor’ev, M.S., Mishkevich, V.I., et al., Koord. Khim., 2011, vol. 37, no. 9, pp. 703–709.
Rodriguez-Dieguez, A., Mota, A.J., Seco, J.M., et al., Dalton Trans., 2009, pp. 9578–9586.
Thuéry, P., Cryst. Growth Design, 2008, vol. 8, no. 5, pp. 4132–4143.
Grigoriev, M.S., Den Auwer, C., Meyer, D., and Moisy, P., Acta Crystallogr., Sect. E, 2006, vol. 62, no. 8, pp. m1725–m1727.
Author information
Authors and Affiliations
Corresponding author
Additional information
Original Russian Text © A.M. Fedoseev, M.S. Grigor’ev, A.B. Yusov, 2012, published in Radiokhimiya, 2012, Vol. 54, No. 5, pp. 408–415.
Rights and permissions
About this article
Cite this article
Fedoseev, A.M., Grigor’ev, M.S. & Yusov, A.B. Interaction of tetravalent actinides and Np(V) with some hydroxy carboxylic acids. Radiochemistry 54, 443–451 (2012). https://doi.org/10.1134/S1066362212050049
Received:
Published:
Issue Date:
DOI: https://doi.org/10.1134/S1066362212050049