Tetravalent uranium readily undergoes hydrolysis even in highly acidic aqueous solutions. In the present work, solutions ranging from 0.4 to 19?mM (total U) concentration ( ) are carefully investigated by light scattering technique with special emphasis on polymerization leading to colloid formation. The results clearly indicate that the concentration has significant effect on particle size as well as stability of colloids. With increasing concentration the size of colloids formed is smaller due to more crystalline nature of the colloids. Stability of colloids formed at lower concentration is greater than that of colloids formed at higher concentration. Weight average molecular weight of the freshly prepared and colloidal polymers aged for 3 days is determined from the Debye plot. It increases from 1,800 to 13,000?Da. 40–50 atoms of U are considered to be present in the polymer. Positive value of second virial coefficient shows that solute-solvent interaction is high leading to stable suspension. The results of this work are a clear indication that U(IV) hydrolysis does not differ from hydrolysis of Pu(IV). 1. Introduction Due to high electric charge, tetravalent actinides have an inordinate tendency to undergo hydrolysis leading to formation of polynuclear species of colloidal dimensions even under very acidic conditions [1–4]. Such processes are observed for tetravalent ions such as Th(IV), Pu(IV), U(IV), Np(IV), and Pa(IV), and to a lesser extent for the hexavalent actinyl ions U(VI) and Pu(VI) [5–7]. The initial step in hydrolysis is the formation of mononuclear species. But further hydrolysis may lead to a variety of polynuclear species [8, 9]. Consider, for example, above millimolar concentration and close to the solubility limit, Pu(IV) form polynuclear species [10]. The consequences of formation of polynuclear species include excessive foaming in evaporation operation, clog in transfer lines, interference in ion exchange operations, and emulsification in solvent extraction operations, and mainly it can lead to criticality hazard due to increase in local concentration of Pu [11]. Colloids can also facilitate the transport of actinide elements in the environment. The transport of plutonium from repository to surrounding may increase when the stable colloidal Pu(IV) formed in ground water comes in contact with spent nuclear fuel [12]. Rate of mobility depends on the size of colloids. For instance, colloids of smaller size less than 50?nm have high mobility and surface to volume ratio [13, 14]. Similarly the nature of colloidal polymers also plays a
References
[1]
R. Knopp, V. Neck, and J. I. Kim, “Solubility, hydrolysis and colloid formation of plutonium(IV),” Radiochimica Acta, vol. 86, pp. 101–108, 1999.
[2]
V. Neck, J. I. Kim, B. S. Seidel et al., “A spectroscopic study of the hydrolysis, colloid formation and solubility of Np(IV),” Radiochimica Acta, vol. 89, no. 7, pp. 439–446, 2001.
[3]
C. Walther, H. R. Cho, C. M. Marquardt et al., “Hydrolysis of plutonium(IV) in acidic solutions: no effect of hydrolysis on absorption-spectra of mononuclear hydroxide complexes,” Radiochimica Acta, vol. 95, no. 1, pp. 7–16, 2007.
[4]
C. F. Baes Jr. and R. E. Mesmer, The Hydrolysis of Cations, Wiley-Interscience, New York, NY, USA, 1976.
[5]
C. Walther, M. Fuss, and S. Büchner, “Formation and hydrolysis of polynuclear Th(IV) complexes—a nano-electrospray mass-spectrometry study,” Radiochimica Acta, vol. 96, no. 7, pp. 411–425, 2008.
[6]
K. Fujiwara and Y. Kohara, “Hydrolysis constants of tetravalent neptunium by using solvent extraction method,” Radiochimica Acta, vol. 96, no. 9–11, pp. 613–616, 2008.
[7]
M. Altmaier, X. Gaona, and T. Fanghanel, “Recent advances in aqueous actinide chemistry and thermodynamics,” Chemical Reviews, vol. 113, no. 2, pp. 901–943, 2013.
[8]
N. Torapava, I. Persson, L. Eriksson, and D. Lundberg, “Hydration and hydrolysis of thorium(IV) in aqueous solution and the structures of two crystalline thorium(IV) hydrates,” Inorganic Chemistry, vol. 48, no. 24, pp. 11712–11723, 2009.
[9]
C. Ekberg, Y. Albinsson, M. J. Comarmand, and P. L. Brown, “Studies on the complexation behaviour of thorium(IV)—1. Hydrolysis equilibria,” Journal of Solution Chemistry, vol. 29, no. 1, pp. 63–86, 2000.
[10]
J.-I. Yun, H.-R. Cho, V. Neck et al., “Investigation of the hydrolysis of plutonium(IV) by a combination of spectroscopy and redox potential measurements,” Radiochimica Acta, vol. 95, no. 2, pp. 89–95, 2007.
[11]
D. J. Chaiko, “Partitioning of polymeric plutonium(IV) in Winsor II microemulsion systems,” Separation Science and Technology, vol. 27, no. 11, pp. 1389–1405, 1992.
[12]
C. Ekberg, K. Larsson, G. Skarnemark, A. Odegaard-Jensen, and I. Persson, “The structure of plutonium(IV) oxide as hydrolysed clusters in aqueous suspensions,” Dalton Transactions, vol. 42, no. 6, pp. 2035–2040, 2013.
[13]
C. Walther, C. Bitea, W. Hauser, J. I. Kim, and F. J. Scherbaum, “Laser induced breakdown detection for the assessment of colloid mediated radionuclide migration,” Nuclear Instruments and Methods in Physics Research B, vol. 195, no. 3-4, pp. 374–388, 2002.
[14]
R. Kretzschmar, K. Barmettler, D. Grolimund, Y.-D. Yan, M. Borkovec, and H. Sticher, “Experimental determination of colloid deposition rates and collision efficiencies in natural porous media,” Water Resources Research, vol. 33, no. 5, pp. 1129–1137, 1997.
[15]
V. M. Ermolaev, E. V. Zakharova, and V. P. Shilov, “Depolymerization of Pu(IV) polymer in 0.5–3 M HNO3 in the presence of reductants and oxidants,” Radiochemistry, vol. 43, no. 4, pp. 424–428, 2001.
[16]
H.-R. Cho, C. Walther, J. Rothe et al., “Combined LIBD and XAFS investigation of the formation and structure of Zr(IV) colloids,” Analytical and Bioanalytical Chemistry, vol. 383, no. 1, pp. 28–40, 2005.
[17]
R. Atta-Fynn, D. F. Johnson, E. J. Bylaska, E. S. Ilton, G. K. Schenter, and W. A. de Jong, “Structure and hydrolysis of the U(IV), U(V), and U(VI) aqua ions from Ab initio molecular simulations,” Inorganic Chemistry, vol. 51, no. 5, pp. 3016–3024, 2012.
[18]
C. Manfredi, V. Caruso, E. Vasca et al., “On the hydrolysis of the tetravalent uranium ion U4+,” Journal of Solution Chemistry, vol. 35, no. 7, pp. 927–937, 2006.
[19]
C. Walther and M. A. Denecke, “Actinide colloids and particles of environmental concern,” Chemical Reviews, vol. 113, no. 2, pp. 995–1015, 2013.
[20]
I. Grenthe, J. Fuger, R. J. M. Konnings et al., Chemical Thermodynamics of Uranium, vol. 1 of Chemical Thermodynamics, North-Holland, Amsterdam, The Netherlands, 1992.
[21]
K. Opel, S. Wei?, S. Hübener, H. Z?nker, and G. Bernhard, “Study of the solubility of amorphous and crystalline uranium dioxide by combined spectroscopic methods,” Radiochimica Acta, vol. 95, no. 3, pp. 143–149, 2007.
[22]
C. Walther, “Comparison of colloid investigations by single particle analytical techniques—a case study on thorium-oxyhydroxides,” Colloids and Surfaces A, vol. 217, no. 1–3, pp. 81–92, 2003.
[23]
C. Walther, J. Rothe, M. Fuss, S. Büchner, S. Koltsov, and T. Bergmann, “Investigation of polynuclear Zr(IV) hydroxide complexes by nanoelectrospray mass-spectrometry combined with XAFS,” Analytical and Bioanalytical Chemistry, vol. 388, no. 2, pp. 409–431, 2007.
[24]
A. E. Stebbens and L. L. Shreir, “Refractive index of uranium oxide produced by anodic oxidation,” Nature, vol. 183, no. 4668, pp. 1113–1114, 1959.
[25]
J. Rothe, C. Walther, M. A. Denecke, and T. Fangh?nel, “XAFS and LIBD investigation of the formation and structure of colloidal Pu(IV) hydrolysis products,” Inorganic Chemistry, vol. 43, no. 15, pp. 4708–4718, 2004.
[26]
J. Selbin and M. Schober, “The chemistry of uranium(IV)—I. Uranium-oxygen bonds in some products derived from the hydrolysis of UCl4,” Journal of Inorganic and Nuclear Chemistry, vol. 28, no. 3, pp. 817–823, 1966.
[27]
P. Thiyagarajan, H. Diamond, L. Soderholm, E. P. Horwitz, L. M. Toth, and L. K. Felker, “Plutonium(IV) polymers in aqueous and organic media,” Inorganic Chemistry, vol. 29, no. 10, pp. 1902–1907, 1990.
[28]
S. W. Rabideau, “Equilibria and reaction rates in the disproportionation of Pu(IV),” Journal of the American Chemical Society, vol. 75, no. 4, pp. 798–801, 1953.
[29]
D. W. Ockenden and G. A. Welch, “The preparation and properties of some plutonium compounds—part V. Colloidal quadrivalent plutonium,” Journal of the Chemical Society, pp. 3358–3363, 1956.
[30]
G. L. Johnson and L. M. Toth, “Plutonium(IV) and thorium(IV) hydrous polymer chemistry,” Tech. Rep. ORNL/TM-6365, Oak Ridge National Laboratory, Oak Ridge, Tenn, USA, 1978.
[31]
N. Priyadarshini, M. Sampath, S. Kumar, U. K. Mudali, and R. Natarajan, “Light scattering studies to determine molecular weight of freshly prepared Zr(IV) hydrous polymer,” Journal of Radioanalytical and Nuclear Chemistry, vol. 295, no. 2, pp. 1093–1096, 2013.
[32]
N. Priyadarshini, M. Sampath, S. Kumar, U. Kamachi Mudali, and R. Natarajan, “A combined spectroscopic and light scattering study of hydrolysis of uranium(VI) leading to colloid formatin in aqueous solutions,” Journal of Radioanalytical and Nuclear Chemistry, vol. 298, no. 3, pp. 1923–1931, 2013.