Depleted uranium hexafluoride—The fluorine source for production of the inorganic and organic compounds

The methods of the transfer of depleted uranium hexafluoride into the safer chemical forms have been analyzed. The depleted uranium hexafluoride is the very valuable source of the high-purity fluorine that it may be used for the production of the pure fluorine-containing compounds. The need for processing of hydrogen fluoride obtained as a result of depleted uranium hexafluoride (DUF₆) conversion, as a result of its high chemical and toxicological hazard. The methods and ways of fluorine application in different fields of science and technology are contained in DUF₆. Basic direction of fluorine application, contained in DUF₆, is nuclear fuel cycle.     

Nitrogen Oxide Fluorides

Oxyfluorides of nitrogen, i.e. compounds containing the grouping F? N? O, have been known for many years in the form of simple compounds, such as NOF and NO₂F. Detailed studies of physical, structural, and chemical aspects of this class of compounds have been conducted only in recent years, after the potential of N? F compounds as rocket propellants had been recognized. Several novel types of oxyfluorides of nitrogen, such as difluorohydroxyl amines, RO? NF₂, or trifluoroamine oxide, F₃NO, have been discovered recently. A further major development in O? N? F chemistry is indicated by the discovery that compounds of great chemical potential are formed between HF and NOF or NO₂F, respectively. The compound O₂NOF, although not an oxyfluoride of nitrogen, will also be discussed in this review, because of its particular chemical relationship to NO₂F.     

Stereochemistry of nitrogen E lone pair in NH3E,NOFE, N2O3E2, AgNO2E,and NCl3E

We revisit nitrogen based simple fundamental molecules in their solid state structures, with the purpose of casting new light on the stereoactivity of valence lone pairs (LPs)—formally N(2s²)—in different crystal geometries. Based on coupled investigations of crystal chemistry and ab initio DFT calculations providing the electron localization function (ELF), LP behavior is analyzed precisely by finding its position E, orientation and “volume of influence” which consists in an electronic cloud generated around the so-called ‘centroïd’ Ec of the electronic doublet. The results show the paramount importance of the role of N(2s²) LP in the crystal network architecture through the different case studies pertaining to ammonia (NH₃), nitrosyl fluoride (NOF), nitrosyl nitrite (N₂O₃), silver nitrite (AgNO₂), and nitrogen trichloride (NCl₃). An unexpected direct ionic interaction between [NO]⁺ or Ag⁺ and the centroïd Ec of the [NO₂Ec]⁻ nitrite group has been evidenced in N₂O₃E₂ and AgNO₂, respectively.     

Nitridfluoride des Urans

Nitridefluorides of Uranium Uranium nitridefluorides with compositions between UNF and UN_0.98F_1.20 were prepared by heating uranium nitride with uranium tetrafluoride. The oxidation state of uranium in these compounds is variing between 4 and 4.14. In the whole area there exists a tetragonal high-temperature phase and an orthorhombic low-temperature phase. The temperature of the transformation between these two phases depends upon the composition of the nitridefluoride. Structure investigations based on single-crystals of the tetragonal phase showed that there is some similarity to the tetragonal lanthanium oxide fluoride.     

Determination of uranium and thorium in phosphate rocks by a combined ion-exchange — Spectrophotometric method

Summary Determination of Uranium and Thorium in Phosphate Rocks by a Combined Ion-Exchange — Spectrophotometric Method A selective anion-exchange separation and Spectrophotometric method has been developed for the determination of uranium and thorium in phosphate rocks. About 0.2 g of rock sample is decomposed with nitric acid. Uranium and thorium are adsorbed by anion-exchange on an Amberlite CG 400 (NO₃ ^–) column from the sample solution adjusted to 2.5M in magnesium nitrate and 0.1M in nitric acid. Uranium and thorium are eluted consecutively with 6.6M nitric acid and 0.1M nitric acid, respectively. Uranium and thorium in the respective effluents are determined spectrophotometrically with Arsenazo III. Results are quoted on uranium and thorium in NBS standard phosphate rock and others.     

Extraction-photometric determination of uranium(IV) with chlorophosphonazo-III

A sensitive spectrophotometric method has been developed for the determination of uranium. The uranium(IV)-chlorophosphonazo-III complex is extracted into 3-methyl-1-butanol from 1.5–3.0 M hydrochloric acid solution. Maximal absorbance occurs at 673 nm and Beer's law is obeyed over the range of 0–15 μg per 10 ml of the organic phase. The molar absorptivity is 12.1·10⁴ 1 mole^?1 cm^?1. Uranium can be determined in the presence of fluoride. sulfate and phosphate. Nitrate ion and elements (chromium, copper, iron) which affect the reduction of uranium(VI) or stability of uranium(IV) interfere.     

Electrode processes of uranium ions and electrodeposition of uranium in molten LiCl-KCl

In the first part, LiCl-KCl-UCl₃ and LiCl-KCl-UCl₃-UCl₄ molten salts were prepared, which were studied employing cyclic voltammetry and chronopotentiometry techniques, respectively. It was determined that the reduction of U(IV) to uranium metal takes two steps. Firstly, U(IV) is reduced to U(III). Then, the reduction of U(III) to uranium metal occurs in a step with a global exchange of three electrons. Cyclic voltammetry studies indicated that at low sweep rates, the reduction of U(III) to uranium is reversible. However, a mixed control of both diffusion and electrontransfer is observed as the sweep rate increases. The diffusion coefficient of U(III) and the formal potential of U(III)/U versus Ag/AgCl reference electrode in these two salt systems were calculated respectively. In second part, based on the data of the electrode processes of uranium ions, electrodeposition of uranium metal was carried out. Uranium deposits were prepared adopting a 304 stainless steel electrode in the molten LiCl-KCl-UCl₃ and LiCl-KCl-UCl₃-UCl₄, respectively by employing suitable electrolytic techniques. The morphology of the deposits and the cross-section of the cathode were investigated by SEM. It was determined that at the beginning of the deposition process, uranium product alloys with stainless steel and forms a thin layer, and then uranium begins to grow adhering to the layer.     

UF6 and UF4 in Liquid Ammonia: [UF7(NH3)]3− and [UF4(NH3)4]

From the reaction of uranium hexafluoride UF₆ with dry liquid ammonia, the [UF₇(NH₃)]^3? anion and the [UF₄(NH₃)₄] molecule were isolated and identified for the first time. They are found in signal‐green crystals of trisammonium monoammine heptafluorouranate(IV) ammonia (1:1; [NH₄]₃[UF₇(NH₃)] ? NH₃) and emerald‐green crystals of tetraammine tetrafluorouranium(IV) ammonia (1:1; [UF₄(NH₃)₄] ? NH₃). [NH₄]₃[UF₇(NH₃)] ? NH₃ features discrete [UF₇(NH₃)]^3? anions with a coordination geometry similar to a bicapped trigonal prism, hitherto unknown for U^IV compounds. The emerald‐green [UF₄(NH₃)₄] ? NH₃ contains discrete tetraammine tetrafluorouranium(IV) [UF₄(NH₃)₄] molecules. [UF₄(NH₃)₄] ? NH₃ is not stable at room temperature and forms pastel‐green [UF₄(NH₃)₄] as a powder that is surprisingly stable up to 147 °C. The compounds are the first structurally characterized ammonia complexes of uranium fluorides.     

Investigation of Uranium(VI) Extraction Mechanisms from Phosphoric and Sulfuric Media by 31P-NMR

Uranium extraction using DEHCNPB (butyl-1-[N,N-bis(2-ethylhexyl)carbamoyl]nonyl phosphonic acid, a bifunctional cationic extractant) has been studied to better understand mechanism differences depending on the original acidic solution (phosphoric or sulfuric). Solvent extraction batch experiments were carried out and the organic phases were probed using ³¹P-NMR. This technique enabled to demonstrate that phosphoric acid is poorly extracted by DEHCNPB ([H₃PO₄]_org < 2mM), using direct quantification in the organic phase by ³¹P-NMR spectra integration. Moreover, in the presence of uranium in the initial phosphoric acid solution, uranyl extraction by DEHCNPB competes with H₃PO₄ extraction.Average stoichiometries of U(VI)-DEHCNPB complexes in organic phases were also determined using slope analysis on uranium distribution data. Uranium seems to be extracted from a phosphoric medium by two extractant molecules, whereas more than three DEHCNPB on average would be necessary to extract uranium from a sulfuric medium. Thus, uranium is extracted according to different mechanisms depending on the nature of the initial solution.     

Reaction between rare earth elements and HFNO2 solution

Rare earth elements react with HFNO₂ solution to produce nitrosylium fluorometallates (NO)_xLnF_x+3. The value of x is 1.0 or 1.5 for light rare earth elements and 0.5 or 1.0 for heavy rare earths. Nitrosylium fluorometallates of rare earth elements can be decomposed into the simple fluoride and nitrosyl fluoride at low temperatures (46–68°C).     

Oxidation of molecular bromine by uranium hexafluoride in acetonitrile. Preparation and properties of hexafluorouranates(V) containing positive bromine

Molecular bromine is oxidized by uranium hexafluoride in acetonitrile at ambient temperature. The product is formulated on the basis of its spectra, and its brominating an oxidizing abilities as [Br(C₆H₉N₃)][UF₆] in which bromine is bound to an acetonitrile trimer containing C=N bonds.     

Determination of ultratrace quantities of uranium by laser-induced fluorescence spectrometry

Uranium (1.5–12 ng l^?1) is co-precipitated with calcium fluoride, the precipitate is ignited in air, and the uranium fluorescence induced by a pulsed nitrogen laser is measured. The detection limit is 0.5 ng l^?1 uranium. Iron(III) and lead interfere seriously.     

Constant-current coulometric determination of uranium in the pure metal

A new method is proposed for the highly precise and accurate constant-current coulometry of uranium in high-purity uranium. Precisely weighed amounts of uranium and pure iron are dissolved in 7 M sulfuric acid containing some hydrogen peroxide (40% $\text{v}\text{v}$). The solution is quantitatively transferred to the coulometric cell by rinsing with 1 M H₂SO₄, saturated with cerium(III) sulfate. The first step is the quantitative electro-chemical reduction to U(IV), Fe(II) and Ce(III) on a gold gauze electrode at constant current (100 mA) until evolution of hydrogen is observed. The hydrogen is then removed by flushing the solution with very pure nitrogen until the potential of a platinum gauze electrode reaches a constant value. Oxidation on the gold gauze electrode is carried out under precisely controlled constant current; after the quantitative oxidation of U(IV) to U(VI) and Fe(II) to Fe(III), and crossing the end-point, this end-point is determined very precisely potentiometrically through back-titration by successive current injections of 10 mA during 1 s. The method was tested on a NBS reference material, uranium (NBS 960).     

Breaking Local Charge Symmetry of Iron Single Atoms for Efficient Electrocatalytic Nitrate Reduction to Ammonia

The electrochemical conversion of nitrate pollutants into value-added ammonia is a feasible way to achieve artificial nitrogen cycle. However, the development of electrocatalytic nitrate-to-ammonia reduction reaction (NO₃⁻RR) has been hampered by high overpotential and low Faradaic efficiency. Here we develop an iron single-atom catalyst coordinated with nitrogen and phosphorus on hollow carbon polyhedron (denoted as Fe−N/P−C) as a NO₃⁻RR electrocatalyst. Owing to the tuning effect of phosphorus atoms on breaking local charge symmetry of the single-Fe-atom catalyst, it facilitates the adsorption of nitrate ions and enrichment of some key reaction intermediates during the NO₃⁻RR process. The Fe−N/P−C catalyst exhibits 90.3 % ammonia Faradaic efficiency with a yield rate of 17980 μg h⁻¹ mg_cat⁻¹, greatly outperforming the reported Fe-based catalysts. Furthermore, operando SR-FTIR spectroscopy measurements reveal the reaction pathway based on key intermediates observed under different applied potentials and reaction durations. Density functional theory calculations demonstrate that the optimized free energy of NO₃⁻RR intermediates is ascribed to the asymmetric atomic interface configuration, which achieves the optimal electron density distribution. This work demonstrates the critical role of atomic-level precision modulation by heteroatom doping for the NO₃⁻RR, providing an effective strategy for improving the catalytic performance of single atom catalysts in different electrochemical reactions.     

Treatment of off-gas evolved from thermal decomposition of sludge waste

Korea Atomic Energy Research Institute (KAERI) started a decommissioning program of a uranium conversion plant. The treatment of the sludge waste, which was generated during the operation of the plant, is one of the most important tasks in the decommissioning program of the plant. The major compounds of sludge waste are nitrate salts and uranium. The sludge waste is denitrated by thermal decomposition. The treatment of off-gas evolved from the thermal decomposition of nitrate salts in the sludge waste is investigated. The nitrate salts in the sludge were decomposed in two steps: the first decomposition is due to the ammonium nitrate, and the second is due to the sodium and calcium nitrate and calcium carbonate. The components of off-gas from the decomposition of ammonium nitrate at low temperature are NH₃, N₂O, NO₂, and NO. In addition, the components from the decomposition of sodium and calcium nitrate at high temperature are NO₂ and NO. Off-gas from the thermal decomposition is treated by the catalytic oxidation of ammonia and selective catalytic reduction (SCR). Ammonia is converted into nitrogen oxides through the oxidation catalyst and all nitrogen oxides are removed by SCR treatment besides nitrous oxide, which is greenhouse gas. An additional process is needed to remove nitrous oxide, and the feeding rate of ammonia in SCR should be controlled properly for evolved nitrogen oxides.     

Optimization of a radioanalytical procedure for the determination of uranium isotopes in environmental samples

A radiochemical procedure is described for the fast and sensitive measurement of uranium isotopes in gaseous and liquid effluents of nuclear facilities. Equally, this procedure is suitable to measure uranium isotopes in all kinds of environmental samples. Uranium is leached from ashed sample materials with HNO₃, HF, and Al(NO₃)₃ solution and separated from matrix elements by extraction with trioctylphosphinic oxide and backextraction with NH₄F. After radiochemical cleaning by coprecipitation with LaF₃ and anion exchange, uranium isotopes are electroplated on stainless steel discs from HCl/oxalate solution. The preparation is measured by alpha-spectrometry using surface barrier detectors. The detection limit for 1000 minutes of counting time is 2 mBq per sample and nuclide, the chemical yield is in the range of 50 to 80%.     

Reduction of nitric oxide,nitrous acid and nitrogen dioxide at platinum electrodes in acidic solutions: Review and new voltammetric results

The literature concerning the chemical and electrochemical reactions of nitric oxide, nitrous acid and nitrogen dioxide in aqueous solutions is reviewed briefly, with emphasis on electrochemical reductions at platinum electrodes in acidic solutions. The voltammetric behavior of NO and NO₂ at a Pt electrode in perchloric acid is virtually identical to that for HNO₂ and this is explained on the basis of a common electroactive precursor concluded to be NO⁺. Three cathodic waves are obtained for acidic solutions of NO, HNO₂ and NO₂. The first two waves correspond to reduction of NO⁺ to NO and N₂O₃ to NO, respectively. The presence of N₂O₃ results from decomposition of the parent compounds. The presence of Br^- or Cl^- in acidic solutions of the title compounds promotes the voltammetric reductions at lower H⁺ concentrations. This probably results from formation of electroactive nitrosyl halides.     

Determination of uranium(VI) in seawater by means of automated flow constant-current cathodic stripping at carbon fibre electrodes

Uranium(VI) is determined in an automated flow system by means of constant-current reductive stripping with a mercury film-coated carbon fibre electrode and catechol as adsorptive reagent at pH 8.6 Interference from iron(III) is eliminated by addition of sulphite. Increased linear range between stripping signal and sample uranium(VI) concentration can be obtained by adding, in the computer, several stripping curves, each obtained after a short period of adsorptive accumulation. It is shown that the hanging mercury drop electrode can be used for the determination of uranium(VI) by means of computerized constant current stripping without the need for inert gas bubbling. The results obtained for uranium(VI) in two reference seawater samples, NASS-1 and CASS-1, were 2.90 and 2.68 μg l^?1 with standard deviations (n = 8) of 0.57 and 0.75 μg l^?1, respectively.     

Determination of uranium isotopes in environmental samples by alpha-spectrometry

A new and accurate method for the determination of uranium isotopes (²³⁸U, ²³⁴U and ²³⁵U) in environmental samples by alpha-spectrometry has been developed. Uranium is preconcentrated from filtered water samples by coprecipitation with iron(III) hydroxide at pH 9-10 using an ammonia solution and the precipitate is dissolved in HNO₃ and mineralized with H₂O₂ and HF; uranium in biological samples is ashed at 600 °C, leached with Na₂CO₃ solution and mineralised with HNO₃, HF and H₂O₂; uranium in soil samples is fused with Na₂CO₃ and Na₂O₂ at 600 °C and leached with HCl, HNO₃ and HF. The mineralized or leaching solution in 2M HNO₃ is passed through a Microthene-TOPO (tri-octyl-phosphine oxide) column; after washing, uranium is directly eluted into a cell with ammonium oxalate solution, electrodeposited on a stainless steel disk and measured by alpha-spectrometry. The lower limits of detection of the method is 0.37 Bq^.kg^-1 (soil) and 0.22 mBq^.l^-1 (water) for ²³⁸U and ²³⁴U and 0.038 Bq^.kg^-1 (soil) and 0.022 mBq^.l^-1 (water) for ²³⁵U if 0.5 g of soil and 1 litre of water are analyzed. Five reference materials supplied by the IAEA have been analyzed and reliable results are obtained. Sample analyses show that, the ²³⁸U, ²³⁴U and ²³⁵U concentrations are in the ranges of 0.30-103, 0.49-135 and 0.02-4.82 mBq^.l^-1 in waters, of 1.01-7.14, 0.85-7.69 and 0.04-0.32 Bq^.kg^-1 in mosses and lichens, and of 25.6-53.1, 26.4-53.8 and 1.18-2.48 Bq^.kg^-1 in sediments. The average uranium yields for waters, mosses, lichens and sediments are 74.5±9.0%, 80.5±8.3%, 77.8±4.9% and 89.4±9.7%, respectively.     

Metallboranate und Boranatometallate. 13 [1]. Darstellung und Molekülstruktur von Uran(III)-tetrahydridoborat-3-Tetrahydrofuran

Metal Boranates and Boranatometallates. 13. Preparation and Molecular Structure of Uranium(III) Tetrahydridoborate-3-Tetrahydrofuran U(BH₄)₃ · 3 THF is slowly formed from UH₃ and diborane in the presence of tetrahydrofuran as a solvent. The compound crystallizes in the triclinic system, space group P1 , with distinct molecules in the unit cell. Its uranium atom is surrounded by three BH₄ and three tetrahydrofuran ligands in a distorted facial-octahedral arrangement. Uranium boron bond distances indicate that the BH₄ groups act as μ₃-H ligands.