Determination of weight distribution ratios of Pa(V) and Np(V) with some extraction chromatography resins and the AG1-X8 resin

Literature data on distribution ratios (D_w) of Np(V) and Pa(V) for the AG1-X8 resin are scarce whereas those related on resin capacity factors (k′) values for TEVA, TRU and U/TEVA resins are absent. Therefore, batch extraction experiments for Pa(V) and Np(V) from HCl and HNO₃ media were realized, at tracer scale, with AG1-X8 and EIChroM resins (TEVA, TRU and U/TEVA). Based on the new D_w and k′ values obtained in this study, a new protocol for Pa/Np separation has been developed leading to a better separation factor of 10⁵ and a chemical yield of 97 ± 3% and 99 ± 1% for Pa and Np, respectively. A separation of ²³¹Pa from uranium matrix was successfully tested.     

High-pressure study of neptunium and plutonium compounds

Abstract

Neptunium and plutonium monopnictides and monochalcogenides were studied by x-ray diffraction at pressures up to 57 GPa. All of them exhibit structural phase transitions under pressure. The arsenides and tellurides have a CsCl (B2) type high-pressure structure. Sb as an anion favours a tetragonal high-pressure structure. The compressibilities were determined for all of the compounds studied. The results are compared to those obtained for the corresponding thorium and uranium compounds.     

Spatially resolved micro-X-ray fluorescence and micro-X-ray absorption fine structure study of a fractured granite bore core following a radiotracer experiment

Spatially resolved X-ray absorption and fluorescence investigation with a micrometer-scale resolution on actinide-containing samples provide information necessary for safety assessment of nuclear waste disposal. In this paper one example of such an experiment is presented. This example entails neptunium speciation in a fractured granite bore core from the Swedish Äspö Hard Rock Laboratory following a radiotracer experiment using µ-XAFS and µ-XRF. In order to probe micro-volumes below the surface in the granite samples and thereby avoid potential changes in the Np speciation during cutting of the bore core, a confocal irradiation–detection geometry is employed. µ-XAFS results for a selected granite bore core cross section with ~ 3 nmol Np/g reveal that Np, originally introduced as Np(V) in the tracer cocktail, is present in the granite in its reduced Np(IV) form. The Np(IV) is often present as particles, tens of µm in size. Elemental distribution maps show the tracer Np to be located in fissures and permeable channels not larger than 100 µm. The Np distribution appears often correlated with Zn also present in some fissures. We observe small granite fissures containing Fe (presumably Fe(II)), where we do not detect any Np. It is feasible that inflowing Np(V) has a shorter residence time in large fractures, while in the smaller fissures migration is slower, leading to longer residence times, i.e., reaction times, where it is reduced to less soluble Np(IV) and becomes thereby immobilized.     

The Synthesis and Crystal Structure of NpSe3

Neptunium triselenide, NpSe₃, was synthesized in high yield by the reaction of the elements in a Sb₂Se₃ flux at 1223 K. Its structure has been determined by single‐crystal X‐ray diffraction methods. Thecompound crystallizes with two formula units in space group C$\rm^{2}_{2h}$ –P2₁/mof the monoclinic system in the TiS₃ structure type with cell constants at 100 K of a = 5.592(3) Å, b = 4.002(2) Å, c = 9.422(5) Å,β = 97.40(1) °. The asymmetric unit comprises one neptunium and three selenium atoms, each with site symmetry m. Np–Se interatomic distances range from 2.859(2) to 2.927(3) Å; the Se–Se bond length of 2.340(3) Å is typical of a single bond. The compound may thus be charge‐balanced and formulated as Np⁴⁺Se^2–Se₂^2–.     

Chemistry of tetravalent actinide phosphates—Part II

The chemistry and crystal structure of tetravalent cation phosphates, including that of actinides was reviewed several times until 1985. Later, new compounds were synthesized and characterized. In more recent studies it was found that some of previously reported phases, especially those of thorium, uranium, and neptunium, were wrongly identified. In the light of these new facts, an update review and classification of tetravalent actinides phosphates is proposed in this two-part paper. Their crystal structure and some chemical properties are compared to non-actinide cation phosphates.     

分光光度法在镎的光化学研究中的应用

以工业汞灯为光源,在硝酸体系中采用光化学方法控制镎(Np)价态的研究中,应用分光光度法对Np的价态及Np的定量测定分析,探讨了Np的光化学机理,得出了Np(Ⅵ)的光化还原速率方程,为光化学分离和提纯Np提供了必要的信息。     

Ab initio study of bonding trends for f0 actinide oxyfluoride species

 Fully relativistic, four-component Dirac–Fock calculations and quasirelativistic pseudopotential calculations at different ab initio levels are used to study the bonding trends among the naked, triatomic [OAnO] ^q+ groups or the oxyfluorides [AnO _n F _m ] ^q with f ⁰ configurations. The triatomic f ⁰ series is suggested to range from the bent ThO₂ via the linear OPaO⁺ to at least NpO₂ ³⁺, a possible new gas-phase species. The neutral oxyfluoride molecules include the experimentally unknown NpO₂F₃ and PuO₂F₄. The latter is a candidate for the so far unknown oxidation state Pu(VIII), which is found to lie considerably above Pu(VI), but to be locally stable. Their all-oxygen isoelectronic analogues are NpO₅ ³⁻, known in the solid state, and the unknown PuO₆ ⁴⁻. Further possible candidates for Pu(VIII) are PuO₄(D _4h ) and the cube-shaped PuF₈(O _h ). Isoelectronic UF₈ ²⁻ is calculated to be D _4d , in agreement with experiment. Received: 18 May 2001 / Accepted: 21 June 2001 / Published online: 11 October 2001     

Divergent Stabilities of Tetravalent Cerium,Uranium, and Neptunium Imidophosphorane Complexes**

The study of the redox chemistry of mid-actinides (U−Pu) has historically relied on cerium as a model, due to the accessibility of trivalent and tetravalent oxidation states for these ions. Recently, dramatic shifts of lanthanide 4+/3+ non-aqueous redox couples have been established within a homoleptic imidophosphorane ligand framework. Herein we extend the chemistry of the imidophosphorane ligand (NPC=[N=P^tBu(pyrr)₂]⁻; pyrr=pyrrolidinyl) to tetrahomoleptic NPC complexes of neptunium and cerium ( 1-M , 2-M , M=Np, Ce) and present comparative structural, electrochemical, and theoretical studies of these complexes. Large cathodic shifts in the M^4+/3+ (M=Ce, U, Np) couples underpin the stabilization of higher metal oxidation states owing to the strongly donating nature of the NPC ligands, providing access to the U^5+/4+, U^6+/5+, and to an unprecedented, well-behaved Np^5+/4+ redox couple. The differences in the chemical redox properties of the U vs. Ce and Np complexes are rationalized based on their redox potentials, degree of structural rearrangement upon reduction/oxidation, relative molecular orbital energies, and orbital composition analyses employing density functional theory.     

核燃料后处理中锕系元素的声化学调价研究进展

硝酸水溶液在超声波辐照下产生自由基及活性分子,通过加入辅助试剂或控制硝酸浓度可以选择性地利用这些活性组分氧化或还原铀、镎、钚等锕系元素。在核燃料后处理流程中可利用上述反应对锕系元素进行声化学调价,实现锕系元素调价的无盐化,在某些调价过程中甚至无需额外加入任何试剂。由于上述优点,声化学方法有望在后处理流程的钚、镎调价方面得到应用。     

Synthesis, structure determination, and infrared spectroscopy of (NpO2)2(SO4)(H2O)4: Prevalence of cation-cation interactions and cationic nets in neptunyl sulfate compounds

The compound (NpO₂)₂(SO₄)(H₂O)₄ was synthesized by evaporation of a Np⁵⁺ sulfate solution. The crystal structure was determined using single crystal X-ray diffraction and refined to an R₁=0.0310. (NpO₂)₂(SO₄)(H₂O)₄ crystallizes in triclinic space group P-1, a=8.1102(7) Å, b=8.7506(7) Å, c=16.234(1) Å, α=90.242(2)°, β=92.855(2)°, γ=113.067(2)°, V=1058.3(2) Å³, and Z=2. The structure contains neptunyl pentagonal bipyramids that share vertices through cation-cation interactions to form a sheet or cationic net. The sheet is decorated on each side by vertex sharing with sulfate tetrahedra, and adjacent sheets are linked together through hydrogen bonding. A graphical representation of (NpO₂)₂(SO₄)(H₂O)₄ was constructed to facilitate the structural comparison to similar Np⁵⁺ compounds. The prevalence of the cationic nets in neptunyl sulfate compounds related to the overall stability of the structure is also discussed.