Chemistry Of Neptunium Research Articles

Neptunium Alkoxide Chemistry: Expanding Alkoxides to the Transuranium Elements.

Two oxo-containing neptunium(IV) tert-butoxides, [Np3O(OtBu)10] (1) and [K4Np2O(OtBu)10] (2), were synthesized using the ligand substitution between neptunium(IV) silylamides and HOtBu, whereas the salt metathesis between [NpCl4(DME)2] (DME = dimethoxyethane) and various amounts of LiOtBu resulted in the formation of oxo-free alkoxides [Np(OtBu)4(py)2] (3; py = pyridine) and [Li(THF)]2[Np(OtBu)6] (4; THF = tetrahydrofuran). These complexes are the first structurally characterized neptunium(IV) alkoxides using single-crystal X-ray diffraction and solid-state absorption spectroscopy, which provide data for the development of anhydrous metal-organic neptunium chemistry.

A terminal neptunium(V)-mono(oxo) complex.

Neptunium was the first actinide element to be artificially synthesized, yet, compared with its more famous neighbours uranium and plutonium, is less conspicuously studied. Most neptunium chemistry involves the neptunyl di(oxo)-motif, and transuranic compounds with one metal-ligand multiple bond are rare, being found only in extended-structure oxide, fluoride or oxyhalide materials. These combinations stabilize the required high oxidation states, which are otherwise challenging to realize for transuranic ions. Here we report the synthesis, isolation and characterization of a stable molecular neptunium(V)-mono(oxo) triamidoamine complex. We describe a strong Np≡O triple bond with dominant 5f-orbital contributions and σu > πu energy ordering, akin to terminal uranium-nitrides and di(oxo)-actinyls, but not the uranium-mono(oxo) triple bonds or other actinide multiple bonds reported so far. This work demonstrates that molecular high-oxidation-state transuranic complexes with a single metal-ligand bond can be stabilized and studied in isolation.

X-ray absorption spectroscopy and actinide electrochemistry: a setup dedicated to radioactive samples applied to neptunium chemistry.

A spectroelectrochemical setup has been developed to investigate radioactive elements in small volumes (0.7 to 2 ml) under oxidation-reduction (redox) controlled conditions by X-ray absorption spectroscopy (XAS). The cell design is presented together with in situ XAS measurements performed during neptunium redox reactions. Cycling experiments on the NpO22+/NpO2+ redox couple were applied to qualify the cell electrodynamics using XANES measurements and its ability to probe modifications in the neptunyl hydration shell in a 1 mol l-1 HNO3 solution. The XAS results are in agreement with previous structural studies and the NpO22+/NpO2+ standard potential, determined using Nernst methods, is consistent with measurements based on other techniques. Subsequently, the NpO2+, NpO22+ and Np4+ ion structures in solution were stabilized and measured using EXAFS. The resulting fit parameters are again compared with other results from the literature and with theoretical models in order to evaluate how this spectroelectrochemistry experiment succeeds or fails to stabilize the oxidation states of actinides. The experiment succeeded in: (i) implementing a robust and safe XAS device to investigate unstable radioactive species, (ii) evaluate in a reproducible manner the NpO22+/NpO2+ standard potential under dilute conditions and (iii) clarify mechanistic aspects of the actinyl hydration sphere in solution. In contrast, a detailed comparison of EXAFS fit parameters shows that this method is less appropriate than the majority of the previously reported chemical methods for the stabilization of the Np4+ ion.

The crystal and coordination chemistry of neptunium in all its oxidation states: An expanded structural hierarchy of neptunium compounds

Structures of 388 neptunium-bearing crystal structures are sorted into an expanded structural hierarchy and examined. The majority of structures contain Np(V) (149), Np(VI) (99), or Np(IV) (91) whereas structures containing Np(II), Np(III), Np(VII), or more than one oxidation state are rare. Coordination geometry of Np(V) and Np(VI) compounds is dominated by the approximately linear neptunyl cation. Actinyl–actinyl interactions (AAIs) are most prevalent in Np(V) compounds and are observed in 48% of these extended structures. Prismatic coordination geometries are commonly observed in Np(IV) compounds. Np(III) organometallic complexes display a variety of coordination modes. Coordination chemistry of Np(VII) compounds is dominated by the tetra-oxido core. Updated average bond length values are provided for Np(IV), Np(V), Np(VI), and Np(VII) compounds and updated bond valence parameters for Np(IV) are reported. A graphical notation system for neptunyl structures coordinated by organic ligands was developed to facilitate discussion and identify similarities between neptunyl compounds coordinated by oxyanions and neptunyl compounds coordinated by organic ligands.

Complexation and redox chemistry of neptunium, plutonium and americium with a hydroxylaminato ligand.

There is significant interest in ligands that can stabilize actinide ions in oxidation states that can be exploited to chemically differentiate 5f and 4f elements. Applications range from developing large-scale actinide separation strategies for nuclear industry processing to carrying out analytical studies that support environmental monitoring and remediation efforts. Here, we report syntheses and characterization of Np(iv), Pu(iv) and Am(iii) complexes with N-tert-butyl-N-(pyridin-2-yl)hydroxylaminato, [2-(tBuNO)py]−(interchangeable hereafter with [(tBuNO)py]−), a ligand which was previously found to impart remarkable stability to cerium in the +4 oxidation state. An[(tBuNO)py]4 (An = Pu, 1; Np, 2) have been synthesized, characterized by X-ray diffraction, X-ray absorption, 1H NMR and UV-vis-NIR spectroscopies, and cyclic voltammetry, along with computational modeling and analysis. In the case of Pu, oxidation of Pu(iii) to Pu(iv) was observed upon complexation with the [(tBuNO)py]− ligand. The Pu complex 1 and Np complex 2 were also isolated directly from Pu(iv) and Np(iv) precursors. Electrochemical measurements indicate that a Pu(iii) species can be accessed upon one-electron reduction of 1 with a large negative reduction potential (E1/2 = −2.26 V vs. Fc+/0). Applying oxidation potentials to 1 and 2 resulted in ligand-centered electron transfer reactions, which is different from the previously reported redox chemistry of UIV[(tBuNO)py]4 that revealed a stable U(v) product. Treatment of an anhydrous Am(iii) precursor with the [(tBuNO)py]− ligand did not result in oxidation to Am(iv). Instead, the dimeric complex [AmIII(μ2-(tBuNO)py)((tBuNO)py)2]2 (3) was isolated. Complex 3 is a rare example of a structurally characterized non-aqueous Am-containing molecular complex prepared using inert atmosphere techniques. Predicted redox potentials from density functional theory calculations show a trivalent accessibility trend of U(iii) < Np(iii) < Pu(iii) and that the higher oxidation states of actinides (i.e., +5 for Np and Pu and +4 for Am) are not stabilized by [2-(tBuNO)py]−, in good agreement with experimental observations.

Organometallic Neptunium Chemistry

Fifty years have passed since the foundation of organometallic neptunium chemistry, and yet only a handful of complexes have been reported, and even fewer have been fully characterized. Yet, increasingly, combined synthetic/spectroscopic/computational studies are demonstrating how covalently bonding, soft, carbocyclic organometallic ligands provide an excellent platform for advancing the fundamental understanding of the differences in orbital contributions and covalency in f-block metal-ligand bonding. Understanding the subtleties is the key to the safe handling and separations of the highly radioactive nuclei. This review describes the complexes that have been synthesized to date and presents a critical assessment of the successes and difficulties in their analysis and the bonding information they have provided. Because of increasing recent efforts to start new Np-capable air-sensitive inorganic chemistry laboratories, the importance of radioactivity, the basics of Np decay and its ramifications (including the radiochemical synthesis of one organometallic compound), and the available anhydrous starting materials are also surveyed. The review also highlights a range of instances in which important differences in the chemical behavior between Np and its closest neighbors, uranium and plutonium, are found.

Reevaluation of Neptunium-Nitric Acid Radiation Chemistry by Multiscale Modeling.

Multiscale modeling has been used to quantitatively reevaluate the radiation chemistry of neptunium in a range of aerated nitric acid solutions (0.1-6.0 mol dm-3). Exact calculation of initial radiolytic yields accounting for changes in radiation track chemistry was found to be crucial for reproducing experimental data. The γ irradiation induces changes in the Np(VI)/Np(V) oxidation-state distribution, predominantly driven by reactions involving HNO2, H2O2, NO2•, and NO3• from the radiolysis of aqueous nitric acid. Oxidation of Np(V) by NO3• (k = 8.1 × 108 dm3 mol-1 s-1) provides the initial increase in Np(VI) concentration, while also delaying net reduction of Np(VI) by consuming HNO2. Reduction of Np(VI) is dominated by thermal reactions with HNO2 (k = 0.7-73 dm3 mol-1 s-1) and H2O2 (k = 1.9 dm3 mol-1 s-1). A steady state is eventually established once the concentration of Np(V) is sufficiently high to be oxidized by NO2• (k = 2.4 × 102-3.1 × 104dm3mol-1 s-1). An additional thermal oxidation reaction between Np(V) and HNO3 (k = 2.0 × 103 dm3 mol-1 s-1) is required for nitric acid concentrations >4.0 mol dm-3. For 0.1 mol dm-3 HNO3, the rate of Np(VI) reduction is in excess of that which can be accounted for by radiolytic product mass balance, suggesting the existence of a catalytic-acid-dependent reduction process.

New oxidation states for neptunium complexes

Understanding actinide chemistry is critical for nuclear waste treatment as well as for illuminating the role of f orbitals in bonding and reactivity. Researchers have made a leap forward in neptunium chemistry, preparing the first NpII and NpIII organometallic complexes (Nat. Chem. 2016, DOI: 10.1038/nchem.2520). Working at the Institute for Transuranium Elements, a team led by Polly L. Arnold of the University of Edinburgh combined radioactive NpCl4 and a macrocyclic ligand, trans-calix[2]benzene[2]pyrrole, to form a mononuclear NpIII complex with the Np bound to the nitrogens of the pyrrole groups and sandwiched between the aryl rings; a fifth bond goes to Cl. The researchers reduced the complex to form a similar NpII structure in which the Cl is replaced by a neutral molecule of the solvent, dimethoxyethane, bound through its oxygens via a bidentate linkage. The NpII complex decays to a binuclear NpIII complex. Analysis of the mononuclear NpIII complex indicates

The redox chemistry of neptunium in γ-irradiated aqueous nitric acid in the presence of an organic phase

The radiolytic changes in oxidation state for solutions of initially Np(V) and/or Np(VI) were investigated by gamma-irradiation in conjunction with UV/Vis spectroscopy of the aqueous phase. Samples were irradiated in varying concentrations of nitric acid, and with or without the presence of 30 % TBP in dodecane. At short irradiation times Np(V) was oxidized to Np(VI), even in the presence of the organic phase. Upon the radiolytic production of sufficient amounts of nitrous acid, reduction of Np(VI) to Np(V) occurred in both phases. This was accompanied by stripping of the previously extracted Np(VI). Nitric acid concentrations of 6 M mitigated this reduction.

The redox chemistry of neptunium inγ-irradiated aqueous nitric acid

AbstractThe redox chemistry of neptunium in irradiated 4 M nitric acid was investigated usingγ-ray irradiation and UV/Vis spectroscopic measurements. Irradiation caused changes in the abundances of Np(V) and Np(VI) regardless of the initial fractional components of these oxidation states. At low absorbed doses Np(V) was oxidized to Np(VI) in irradiated solution, due to its reaction with oxidizing, radiolytically-produced, free radicals. However, when sufficient radiolytically-produced nitrous acid accumulated, the reduction of Np(VI) to Np(V) occurred, even at this high nitric acid concentration. Neptunium(IV) was not produced. A kinetic model which incorporates the standard water radiolysis reactions, estimated radical yields for 4 M HNO3, and rate constants for neptunium reactions available from the literature was used to successfully reproduce the experimental results.

R&D Activities on Actinide Separation in China

A brief status of the development of actinide separation in china is presented. The activities on actinide separation include:1) Neptunium chemistry and its separation in Purex Process;2) actinide separation from HLLW;3) separation of actinides from rare earth; and4) preliminary studies on uranium cathode deposit by pyrochemical process.

Chemical Effects at the Reaction Front in Corroding Spent Nuclear Fuel

AbstractPerformance assessment models of the U. S. repository at Yucca Mountain, Nevada suggest that neptunium from spent nuclear fuel is a potentially important dose contributor. A scientific understanding of how the UO2 matrix of spent nuclear fuel impacts the oxidative dissolution and reductive precipitation of Np is needed to predict the behavior of Np at the fuel surface during aqueous corrosion. Neptunium would most likely be transported as aqueous Np(V) species, but for this to occur it must first be oxidized from the Np(IV) state found within the parent spent nuclear fuel. In this paper we present synchrotron x-ray absorption spectroscopy and microscopy findings that illuminate the resultant local chemistry of neptunium and plutonium within uranium oxide spent nuclear fuel before and after corrosive alteration in an air-saturated aqueous environment. We find the Pu and Np in unaltered spent fuel to have a +4 oxidation state and an environment consistent with solid-solution in the UO2 matrix. During corrosion in an air-saturated aqueous environment, the uranium matrix is converted to uranyl (UO22+) mineral assemblage that is depleted in Np and Pu relative to the parent fuel. The transition from U(IV) in the fuel to a fully U(VI) character across the corrosion front is not sharp, but occurs over a transition zone of ∼ 50 micrometers. We find evidence of a thin (∼ 20 micrometer) layer that is enriched in Pu and Np within a predominantly U(IV) environment on the fuel side of the transition zone. These experimental observations are consistent with available data for the standard reduction potentials for NpO2+/Np4+ and UO22+/U4+ couples, which indicate that Np(IV) may not be effectively oxidized to Np(V) at the corrosion potential of uranium dioxide spent nuclear fuel in air-saturated aqueous solutions.

Structural Chemistry of the Neptunium–Germanium Binary System

The structural chemistry of the complete binary neptunium–germanide system has been investigated by means of X-ray diffraction. In addition to the well-known NpGe3 (AuCu3 type), at least five new binary phases have been found. The crystal structure of NpGe2−x (defect ThSi2 type), NpGe2−x (defect AlB2 type), NpGe (USi type), Np5Ge4 (Ti5Ga4 type), and Np5Ge3 (W5Si3 type) have been refined from single-crystal and powder X-ray diffraction data. X-ray powder analyses by Rietveld-type profile refinement revealed a small homogeneity range of the three first phases, as usually observed with the rare-earth or uranium isotypic compounds, whereas Np5Ge4 and Np5Ge3 seem to be line compounds as the unit cell parameters were independent of the starting composition. The formation and the homogeneity range of these new phases are discussed, and the structural evolution is compared with the analogous uranium binary system.

Modelling of uranium and neptunium chemistry in a deep rock environment

According to the present concept for final storage of spent nuclear fuel in Sweden, the spent fuel, encapsulated in copper or copper/steel canisters, will be placed in tunnels in a deep rock formation. The canisters will be surrounded by compacted bentonite clay acting as a buffer material. In connection with a safety analysis of such a storage facility, the total solubility of certain elements (e.g., uranium) as well as the transport properties (e.g., retardation due to sorption on mineral surfaces) of the long-lived radionuclides released from the canister have to be predicted or measured. The chemical conditions, governing the solubility and speciation of trace elements encountered in and around the repository depend on interactions between the ground water and the engineering materials in the repository and a production of oxidants due to radiolysis in the spent fuel. In the present study the speciation and solubility of uranium and neptunium in a bentonite-ground water system and in ground waters with compositions measured at a site at aspo, SE Sweden, have been calculated. The calculations have been carried out using a recent version of the geochemical computer code PHREEQE and the database HATCHES 5.0. Predictions of the uranium and neptunium concentrations in the ground water in the vicinity of a damaged high level waste repository have also been performed. The uranium concentration in the water in the bentonite barrier is predicted to be of the same order of magnitude or lower than that found in some granitic ground waters. For neptunium the calculations are uncertain due to the small amount of experimentally determined thermodynamic data and few verifications under the conditions (pH - Eh - carbonate concentration) considered. The predicted concentrations (ca 10−12 m, corresponds to ca 0.006 Bq/l) may be regarded as high, considering the high toxicity of neptunium and its long half-life.

Chemistry of Neptunium in Solution

The discovery and the chemistry of neptunium is described. Improvements in redox reactions, analytical determinations and environmental research work are discussed.

Recent progress in the extraction chemistry of actinide ions

For over 40 years now, actinide scientists worldwide have maintained and sustained a high level of activity and interest in the chemistry and technology of actinide element liquid-liquid extraction systems, but the thrust and scope of this activity has changed. Two to three decades ago large teams of chemists and chemical engineers in a few countries strove to develop the essential elements of processes ( e. g. PUREX, THOREX, BUTEX etc.) for reprocessing irradiated nuclear fuel. Today, much smaller groups of investigators scattered around the globe are pursuing challenging actinide element extraction chemistry and systems of particular interest to them. Examples of these latter activities include 1. (a) continued studies of selected PUREX process features ( e.g., neptunium chemistry, modeling of plutonium and uranium extraction and separation, etc.); 2. (b) consideration of certain aliphatic amides as a replacement for TBP in PUREX-type processes; 3. (c) investigation of nitrogen and sulfur-based compounds to effect liquidliquid extraction separation of trivalent actinides and lanthanides, synthesis and application of bifunctional organophosphorus reagents for removal of all TRU elements from nuclear waste solutions; various synergistic extraction systems etc. This paper highlights the objectives and status of these modernday actinide extraction studies and also attempts to project the near-future thrust and direction of investigations of actinide liquid-liquid extraction systems.

Electrochemical and spectroscopic studies of neptunium in the aluminum chloride-1-n-butylpyridinium chloride melt at 40.degree.C

The chemistry of neptunium in acidic and basic AlCl/sub 3/-1-n-butylpyridinium chloride melts at 40/sup 0/C has been investigated by means of electrochemical and spectral techniques. In acidic as well as in basic melts, the reduction of Np(IV) to Np(III) at glassy-carbon electrodes is quasi-reversible. Indirect measurements of the formal potential and spectroscopic results on the Np(IV)-Np(III) system as a function of the acidity indicate that Np(III) and Np(IV) exist as NpCl/sub 6//sup 3 -/ and NpCl/sub 6//sup 2 -/ and solvated Np/sup 3 +/ and NpCl/sub x//sup (4-x)+/ (with 3 greater than or equal to x greater than or equal to 1), respectively, in basic and acidic melts. The apparent rate constant K/sup 0/' has been measured on the basic and acidic sites. It depends on the melt acidity only in the latter melts. The Nugent linearization method has been applied to the standard potentials of Np(IV)-Np(III) and U(IV)-U(III) in 2:1 melts. A comparison with the results obtained from other room-temperature solvents shows, as already found with lanthanides, that the acidic melt is a very weak solvating medium.

All-Union Conference on the Chemistry of Neptunium and Plutonium

All-Union Conference on the Chemistry of Neptunium and Plutonium

Some observations on the chemistry of neptunium in basic solution

Some observations on the chemistry of neptunium in basic solution