The behavior of U(IV) octahedral complexes [cation]2[UCl6], where the [cation]+ is [BuMeIm]+ and [MeBu3N]+, is studied using UV/visible spectroscopy, cyclic staircase voltammetry, and rotating disk electrode voltammetry in hydrophobic room-temperature ionic liquids (RTILs) [BuMeIm][Tf2N] and [MeBu3N][Tf2N], where BuMeIm+ and MeBu3N+ are 1-butyl-3-methylimidazolium and tri-n-butylmethylammonium cations, respectively, and Tf2N- is the bis(trifluoromethylsulfonyl)imide anion. The absorption spectra of [cation]2[UCl6] complexes in the RTIL solutions are similar to the diffuse solid-state reflectance spectra of the corresponding solid species, indicating that the octahedral complex UCl6(2-) is the predominant chemical form of U(IV) in Tf2N--based hydrophobic ionic liquids. Hexachloro complexes of U(IV) are stable to hydrolysis in the studied RTILs. Voltammograms of UCl(6)2- at the glassy carbon electrode in both RTILs and at the potential range of -2.5 to +1.0 V versus Ag/Ag(I) reveal the following electrochemical couples: UCl6-/UCl6(2-) (quasi-reversible system), UCl(6)2-/UCl6(3-) (quasi-reversible system), and UCl(6)2-/UCl6(Tf2N)x-3+x (irreversible reduction). The voltammetric half-wave potential, Ep/2, of the U(V)/U(IV) couple in [BuMeIm][Tf2N] is positively shifted by 80 mV compared with that in [MeBu3N][Tf2N]. The positive shift in the Ep/2 value for the quasi-reversible U(IV)/U(III) couple is much greater (250 mV) in [BuMeIm][Tf2N]. Presumably, the potential shift is due to the specific interaction of BuMeIm+ with the uranium-hexachloro complex in ionic liquid. Scanning the negative potential to -3.5 V in [MeBu3N][Tf2N] solutions of UCl6(2-) reveals the presence of an irreversible cathodic process at the peak potential equal to -3.12 V (at 100 mV/s and 60 degrees C), which could be attributed to the reduction of U(III) to U(0).

The present work describes the first structural studies of protactinium(V) in sulfuric and hydrofluoric acid media using X-ray absorption spectroscopy. The results show unambiguously the absence of the trans-dioxo bond that characterizes the other early actinide elements such as U and Np. In concentrated sulfuric acid (13 M), Pa(V) is proved to exhibit a single oxo bond as postulated in the literature for species in more dilute media. In a 0.5 M HF medium, XANES and EXAFS spectra indicate the absence of any oxo bond: Pa(V) exists in the form of a pure fluoro complex.

Element 104 / Hydrolysis / Complex formation / Relativistic molecular calculationsSummary. Fully relativistic molecular density-functional calculations of the electronic structures of hydrated, hydrolyzed and fluoride/chloride complexes have been performed for group-4 elements Zr, Hf, and element 104, Rf. Using the electronic density distribution data, relative values of the free energy change for hydrolysis and complex formation reactions were defined. The results show the following trend for the first hydrolysis step of the cationic species: Zr > Hf > Rf in agreement with experiments. For the complex formation in HF solutions, the trend to a decrease from Zr to Hf is continued with Rf, provided no hydrolysis takes place. At pH > 0, further fluorination of hydrolyzed species or fluorocomplexes has an inversed trend in the group Rf ≥ Zr > Hf, with the difference between the elements being very small. For the complex formation in HCl solutions, the trend is continued with Rf, so that Zr > Hf > Rf independently of pH. A decisive energetic factor in hydrolysis or complex formation processes proved to be a predominant electrostatic metal-ligand interaction. Trends in the K d (distribution coefficient) values for the group-4 elements are expected to follow those of the complex formation.

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A high-resolution measurement of the neutron-induced fission cross section of 234 U and 237 Np has been performed at the CERN Neutron Time-of-Flight facility. The cross sections have been determined in a wide energy range from 1 eV to 1 GeV using the evaluated 235 U cross section as reference. In these measurements the energy determination for the 234 U resonances could be improved, whereas previous discrepancies for the 237 Np resonances were confirmed. New cross-section data are provided for high neutron energies that go beyond the limits of prior evaluations, obtaining important differences in the case of 237 Np.

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We summarize here the results of the TARC experiment whose main purpose is to demonstrate the possibility of using Adiabatic Resonance Crossing (ARC) to destroy efficiently Long-Lived Fission Fragments (LLFFs) in accelerator-driven systems and to validate a new simulation developed in the framework of the Energy Amplifier programme. An experimental set-up was installed in a CERN PS proton beam line to study how neutrons produced by spallation at relatively high energy ( E n ≥ 1 MeV) slow down quasi adiabatically with almost flat isolethargic energy distribution and reach the capture resonance energy of an element to be transmuted where they will have a high probability of being captured. Precision measurements of energy and space distributions of spallation neutrons (using 2.5 GeV/ c and 3.5 GeV/ c protons) slowing down in a 3.3 m × 3.3 m × 3 m lead volume and of neutron capture rates on LLFFs 99 Tc, 129 I, and several other elements were performed. An appropriate formalism and appropriate computational tools necessary for the analysis and understanding of the data were developed and validated in detail. Our direct experimental observation of ARC demonstrates the possibility to destroy, in a parasitic mode, outside the Energy Amplifier core, large amounts of 99 Tc or 129 I at a rate exceeding the production rate, thereby making it practical to reduce correspondingly the existing stockpile of LLFFs. In addition, TARC opens up new possibilities for radioactive isotope production as an alternative to nuclear reactors, in particular for medical applications, as well as new possibilities for neutron research and industrial applications.

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