The determination of bound nitrogen in uranium hexafluoride with an ammonia electrode

Uranium hexafluoride reacts with nitrosyl fluoride (NOF), nitryl fluoride (NO₂F), and nitrogen oxides to form solid compounds such as nitrosyl heptafluorouranate (NOUF₇) and nitryl heptafluorouranate (NO₂UF₇). Since these compounds are undesirable impurities in uranium hexafluoride, a method has been developed for the determination of these nitrogen oxyfluorides in uranium hexafluoride. Uranium hexafluoride is hydrolyzed in a potassium permanganate solution which converts the uranium hexafluoride to uranyl fluoride and the nitrogen oxyfluorides to nitric acid. The nitrate is reduced with aluminum powder to ammonia, which is then measured with an ammonia electrode in a basic solution. The method is relatively interference-free because the electrode is a gas-sensing device. The detection limit is 0.8 μg bound N/g U, and the precision at 3 μg bound N/g U is ± 16%.     

Anion exchange separation and determination of yttrium in uranium oxide — Yttrium oxide mixture

A procedure has been developed for quantitative separation of yttrium from uranium by anion exchange from nearly saturated NH₄Cl solution in 0–2N HCl medium. Apparently no organic matter is leached out during the separation as yttrium could be determined by EDTA titration without resorting to fuming with perchloric acid before titration. The precision obtained in the analysis of yttrium in a mixture containing about 12 mg of yttrium and about 300 mg of uranium was ±0.3% (27 determinations).     

The gravimetric determination of uranium in uranyl nitrate

A study of the factors which affect the gravimetric determination of uranium in uranyl nitrate is described. In the gravimetry of uranium, the U₃O₈ (weighing form) produced by ignition is usually assumed to deviate <0.02% from theoretical composition; and elemental impurities are assumed to form common oxides within the U₃0₈ matrix. It is shown that these assumptions are incorrect. Ignition temperature and time affect U₃O₈ stoichiometry. Ignitions of uranyl nitrate for 1–3 h at 850° produce U₃O₈ that deviates as much as 0.15% from stoichiometric U₃O₈; deviations are negligible when uranyl nitrate is ignited at 1000° for 2 h. Elemental impurities, particularly calcium and phosphorus, affect the composition of U₃O₈ formed in the ignition of uranyl nitrate. A variety of impurity complexes such as uranates and phosphates are found within the U₃O₈ matrix. Formation of these impurity complexes depends on the elements present, their concentration, and ignition temperature. Therefore, in the gravimetric determination of uranium in uranyl nitrate, the effects of ignition parameters and nonvolatile impurities must be considered in order to obtain accurate uranium determinations.     

Detection of uranium with a wireless sensing method by using salophen as receptor and magnetic nanoparticles as signal-amplifying tags

A new wireless sensing method for the detection of uranium in water samples has been reported in this paper. The method is based on a sandwich-type detection strategy. Salophen, a tetradentate ligand of uranyl ion, was immobilized on the surface of the polyurethane-protected magnetoelastic sensor as receptor for the capture of uranyl ion. The phosphorylated polyvinyl alcohol coated magnetic Fe₃O₄ nanoparticles were used as signal-amplifying tags of uranyl ion. In a procedure of determining uranium, firstly uranyl ion in sample solution was captured on the sensor surface. Then the captured uranyl bound the nanoparticle through its coordination with the phosphate group. The amount of uranium was detected through the measure of the resonance frequency shift caused by the enhanced mass loading on the sensor surface. A linear range was found to be 0.2–20.0 μg/L under optimal conditions with a detection limit of 0.11 μg/L. The method has been applied to determine uranium in environmental water samples with the relative standard deviations of 2.1–3.6 % and the recoveries of 98.0–101.5 %. The present technique is one of the most suitable techniques for assay of uranium at trace level in environmental water samples collected from different sources.     

Ion exchange/adsorption properties of crystalline compound of anatase and rutile

The crystallinely hydrous titanium dioxide, H₄Ti₃O₈, was synthesized by heating amorphous titanium hydroxide at 80°C for 12 hours. XRD, TGA and pH titration were employed to characterize the prepared crystal. The studies on acid, base and radiation stabilities of the crystal demonstrate the reliability of this type of ion exchange material for treating radioactive nuclear wastes. The uranyl ions are so much preferred by the crystal that the complexation of uranyl and chloride ions in solution phase is completely destructed. The uptake of uranium on the crystal is remarkably sensitive to the solution pH. Plot of log/K_D of the uranium on the crystal vs. equilibrium pH generates a series of lines with the mean slope of 0.40, which is the verification of sophisticated loading mechanisms in H/UO ₂ ²⁺ reaction.     

Studies in bivalent chromium salts

Summary The above estimations show that stannous chloride and uranyl acetate can be estimated with the help of chromous sulphate. In the case of tin, excess of ferric iron is added and its excess found by titration with chromous sulphate, using neutral red or phenosafranine as indicator. In the case of uranyl acetate chromous salt titration, the above two indicators work satisfactorily in the absence of excess of sulphuric acid, whereas methyl red and p-ethoxycrysodine give good end points even in the presence of excess acid. In the alternative procedure for estimation of uranium, chromous sulphate serves the purpose of a Jone's reductor.Ammonium metavanadate solution can be titrated directly against chromous sulphate. N-phenylanthranilic acid, diphenylamine, diphenylbenzidine and diphenylamine sulphonic acid serve satisfactorily as internal indicators for the VO_3– to VO²⁺ change. It has been shown that ferric and cupric salts do not interfere in the above titrations. Mixtures of vanadate and dichromate or vanadate and ceric sulphate can also be titrated in the same manner using the same indicators.Part VI: cf. Z. analyt. Chem. 162, 33 (1958).     

低浓缩铀靶辐照后溶液中铀的化学种态及主要裂变元素的影响

利用化学种态分析软件CHEMSPEC计算了低浓缩铀靶辐照后溶液中铀(U)的化学种态分布及其主要裂变元素对U化学种态的影响。结果表明,在单组分体系中,pH值和铀酰浓度都会显著影响U的化学种态分布。随着铀酰浓度的增大,溶液中将会生成多核配合物;在较高的NO₃^-浓度下,U在溶液中主要以UO₂²⁺和UO₂NO³⁺的形式存在。CO₂对不同浓度铀的种态分布影响结果表明,当铀酰浓度较低时,铀的化学种态多以碳酸铀酰的形式存在;当铀酰浓度较高时,铀的化学种态多以氢氧铀酰或柱铀矿沉淀的形式存在。计算发现,当裂片元素Tc、I、Mo的浓度小于0.01mol·L^-1并分别以TcO₄^-、I^-、MoO₄^2-的种态存在时,这些裂片元素不改变铀的各化学种态的分布。     

Single step conversion of UO2 and U3U8 into uranyl sulphate solution

A direct and simple method for the conversion of UO₂ and U₃O₈ powder into uranyl sulphate solution is described, eliminating many tedious chemical steps. UO₂ and U₃O₈ are not soluble in concentrated or dilute sulphuric acid, as uranium in lower oxidation state does not react with sulphuric acid. However, nitric acid oxidizes uranium from lower valency to higher valency state, i.e., tetravalent to the hexavalent uranyl ion in solution. Sufficient amount of sulphuric acid present in the reaction mixture makes it possible for uranyl ions, formed by oxidation of nitric acid, to react with sulphuric acid forming uranyl sulphate.     

A universal solvent extraction-titration method for the rapid and accurate determination of uranium in complex solutions

A rapid and accurate method has been developed for the determination of uranium in complex solutions produced in the recovery of uranium from nuclear fuels. These solutions usually contain 0.1–20 g U l^-1 and high concentrations of aluminum nitrate in addition to a variety of cations and anions associated with fuel-element constituents and dissolution media. The method involves the solvent extraction of uranium from an acid-deficient aluminum nitrate-tetrapropylammonium nitrate solution into 2% tributy1 phosphate in n-amy1 acetate. The uranium is then backextracted with a concentrated phosphoric acid solution, and titrated by the method of Davies and Gray. The uranium extraction efficiency for sample solutions weighing up to 50 g is 99.9% or better, and the limit of error per analysis with 95% confidence is ±0.6%. No prior sample preparation is necessary, no expensive equipment is required, and even unskilled personnel can do duplicate analyses in 1.5 h.     

Uranium association with corroding carbon steel surfaces

We investigated the association of uranium with clean and corroded surfaces of 1010 carbon steel. Studying steel contaminated by uranium species will have an important effect on the development of methods used to clean radioactively contaminated metal waste. X‐ray photoelectron spectroscopy, synchrotron infrared microspectroscopy and laboratory‐based Fourier transform infrared analysis of steel surfaces exposed to uranyl nitrate showed the presence of crystallized hydrated uranyl oxides, uranyl hydroxides, iron oxyhydroxides and iron oxides. In general, heavily corroded areas physically shield the uranium species, which tended to associate spatially with hydroxyl groups and lepidocrocite. Lightly corroded areas contained uranium species with stronger axial U–O bonding. Infrared spectroscopy, Rutherford backscattering spectroscopy and energy‐dispersive spectroscopy mapping analysis revealed that the uranium species are well distributed within the upper micron of the thick corrosion layer and associated more with areas of high hydroxide content. Parameters such as the concentration of uranyl nitrate solution used to expose the carbon steel coupons, the method of contamination (dipped or sprayed with dilute uranyl nitrate solution) and the degree of corrosion (accelerated corrosion before and/or after contamination) played significant roles in the distribution and nature of the uranyl hydroxide/iron oxyhydroxide corrosion products found on the surface of all coupons. These factors must be considered in the development and optimization of decontamination processes for metal waste. Copyright © 2003 John Wiley & Sons, Ltd.     

Colorimetric determination of boron in nitrate solutions

A method has been developed for the determination of microgram amounts of boron in nitrate solutions. Nitrate is destroyed with formic acid and sulphuric acid under reflux conditions. As much as 3 millimoles of nitrate are reduced completely by refluxing 1 ml of the nitrate solution with 1 ml of 88% formic acid for 15 minutes. Boron is determined by the carminic acid method after forming the colored complex in situ. This method has been applied to the determination of boron in uranyl nitrate solutions after extraction of uranium with tri-n-octylphosphine oxide dissolved in cyclohexane.     

Synergistic extraction of uranium(VI) with tri-n-butyl phosphate and i-butyldodecylsulfoxide

Summary The synergistic extraction of uranium(VI) from aqueous nitric acid solution with a mixture of tri-n-butyl phosphate (TBP) and i-butyldodecylsulfoxide (BDSO) in toluene was investigated. The effects of the concentrations of extractant, nitric acid, sodium nitrate and sodium oxalate on the distribution ratios of uranium(VI) have been studied. The values of enthalpy change for the extraction reactions with BDSO, TBP and a mixture of TBP and BDSO in toluene were -23.2±0.8 kJ/mol, -29.2±1.4 kJ/mol and -30.6±0.6 kJ/mol, respectively. It has been found that the maximum synergistic extraction effect occurs when the molar ratio of TBP to BDSO is close to 1. The composition of the complex of the synergistic extraction is UO₂(NO₃)₂ ^. BDSO ^. TBP.     

低浓缩铀靶辐照后溶液中铀的化学种态及主要裂变元素的影响

利用化学种态分析软件CHEMSPEC计算了低浓缩铀靶辐照后溶液中铀(U)的化学种态分布及其主要裂变元素对U化学种态的影响。结果表明,在单组分体系中,pH值和铀酰浓度都会显著影响U的化学种态分布。随着铀酰浓度的增大,溶液中将会生成多核配合物;在较高的NO₃^-浓度下,U在溶液中主要以UO₂²⁺和UO₂NO₃⁺的形式存在。CO₂对不同浓度铀的种态分布影响结果表明,当铀酰浓度较低时,铀的化学种态多以碳酸铀酰的形式存在;当铀酰浓度较高时,铀的化学种态多以氢氧铀酰或柱铀矿沉淀的形式存在。计算发现,当裂片元素Tc、I、Mo的浓度小于0.01 mol·L^-1并分别以TcO₄^-、I^-、MoO₄^2-的种态存在时,这些裂片元素不改变铀的各化学种态的分布。     

Uranium electrodeposition for alpha spectrometric source preparation

In this paper a simple method was used to design and set up an electrodeposition device for uranium source preparation for alpha spectrometry measurements. The aim of this work is to find the optimal parameters to be used to achieve uranium alpha sources with good spectral properties and maximum yield of the electrodeposition process. Samples with specific uranium activity were prepared from aqueous solution of uranyl nitrate hexahydrate (UO₂ (NO₃)₂·6H₂O). A series of preliminary experiments was conducted to establish the main parameters that have a significant influence on the deposition efficiency. Among these, the electrodeposition time was studied and the optimum time was found to be 1 h, in the case of our home-made deposition cell. It was also shown that a current of 1,500 mA, plating time of 60 min and pH range of 2–2.2 are the best conditions for deposition of uranium. The alpha spectrometry results show a good spectral resolution for the uranium sources obtained by the electrodeposition using the optimal parameters.     

A titrimetric method for the sequential determination of thorium and uranium

A method for the sequential determination of thorium and uranium has been developed. In the sample solution containing thorium and uranium, thorium is first determined by complexometric titration with ethylenediaminetetraacetic acid (EDTA) and then in the same solution uranium is determined by redox titration employing potentiometry. As EDTA interferes in uranium determination giving positive bias, it is destroyed by fuming with HClO₄ prior to the determination of uranium. A precision and accuracy of better than ±0.15% is obtained for thorium at 10mg level and uranium ranging from 5 mg to 20 mg in the aliquot.     

Surface modification in natural fluorapatite after uranyl solution treatment

Natural fluorapatite samples were contacted with uranyl nitrate solutions (from 10⁻² to 10⁻⁶M), adjusted to pH 6.0, then, shaken for times varying between 15 minutes to 72 hours, at room temperature. After that, the solid and liquid phases were separated by centrifugation and the solid was dried at 80°C overnight. The uranium analysis of the solid samples and solutions revealed that uranium was incorporated over fluorapatite. Selected solid samples produced by contacting treatments were analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques. XRD patterns showed the growth of uranyl species in the fluorapatite. Imaging by SEM at 20000x showed the location of uranyl compounds in a crystalline layer in the surface of fluorapatite grains. This layer was well defined for the 10⁻² M of U-contacting solution, but a saturation value was attained at 64% of uranium uptake yield. In the case of 10⁻⁴ M and lower U-contacting solution, the uranium uptake yield was near of 90% after 45 minutes. This fact suggests that natural fluorapatite has excellent properties to immobilize uranium compounds in a solution. Afterwards, the pregnant fluorapatite mineral was regenerated using an alkaline-leaching process. The uranium separated in this way is concentrated and can be handled to a final disposition.     

Estimation of distribution coefficient of uranium around a uranium mining site

Distribution coefficient (K _d) of uranium and its daughter products are very important for migration study around uranium mining sites. Since the distribution coefficient depends very much on the soil and groundwater chemistry, generation of site specific K _d is very important. In the literature there is a large variation of K _d values of uranium. For realistic prediction of contaminant migration, literature K _d value is not very effective. So site specific experimental K _d values are required. The present study emphasizes on the estimation of site specific distribution coefficient for uranium around a uranium mining site. The soil and groundwater parameters which affect the K _d value of uranium have also been estimated. Soil and groundwater samples from nine locations around Turamdih uranium mining site were collected and chemically characterized for various parameters. The distribution coefficient of uranium in top and one meter depth soil samples from above locations were estimated using laboratory batch method. The distribution coefficient of uranium varies from 69 ± 4 to 5524 ± 285 l/kg. No significant difference in uranium K _d values was observed for top and one meter depth soil samples. In the top and one meter depth soil samples uranium K _d values vary from 129 ± 8 to 5524 ± 285 and 69 ± 4 to 3862 ± 195 l/kg respectively. For the estimation of distribution coefficient of uranium different parameters like equilibration time, solid to solution ratio, method of tracer addition to solution, solid-solution separation method etc. have been optimized. The distribution coefficient of uranium determined in the present study will be used for the migration study of uranium around uranium mining sites.     

Speciation of the uranyl nitrate system via spectrophotometric titrations

The speciation of the uranyl nitrate system has been studied previously with limited success producing a wide range of stability constant values. The current literature has values for the mononitrate species, with scattered data for higher nitrate species. Furthermore, the reported values vary with experimental method. The work presented here examines the stability of the uranyl/nitrate/perchlorate/water system via spectrophotometric titrations with a focus on the predominance of the uranyl dinitrate species at low nitrate concentrations. Stability constants were determined at ionic strengths ranging from 1 to 6 molal followed by refinement with the specific ion interaction theory. The zero ionic strength stability constant of the uranyl dinitrate species was refined as log β (2,1)º = 3.37 ± 0.02 when including the stability constant for the uranyl mononitrate from Ahrland and 2.66 ± 0.02 without. These values are considerably higher than previous studies, which is attributed to the alternate speciation model used. The values generated in this work produce speciation diagrams that are consistent with published solvent extraction data of the uranyl nitrate system.     

Nitrate ion transport across TBP-kerosene oil supported liquid membranes coupled with uranyl ions

The role of nitrate ions in uranyl ions transport across TBP-kerosene oil supported liquid membranes (SLM) at varied concentrations of HNO₃ and NaNO₃ has been studied. It has been found that nitrate ions move faster compared to uranyl ions at the uranium feed solution concentrations studied. The nitrate to uranyl ions flux ratio vary from 355 to 2636 under different chemical conditions. At low uranium concentration the nitrate ions transport as HNO₃ · TBP, in addition to as UO₂(NO₃)₂ · 2TBP type complex species. The flux of nitrate ions is of the order of 12.10 · 10^–3 mol · m^–2 · s^–1 compared to that of uranium ions (4.56 · 10^–6 mol · m^–2 · s^–1). The permeability coefficient of the membrane for nitrate ions varies with chemical composition of the feed solution and is in the order of 2.5 · 10^–10 m^–2 · s^–1. The data is useful to estimate the nitrate ions required to move a given amount of uranyl ions across such an SLM and in simple solvent extraction.     

Fluorescence and absorbance spectroscopy of the uranyl ion in nitric acid for process monitoring applications

Near real time process monitoring of the uranium content in an aqueous fuel recycling plant is a desired component of an advanced safeguards suite; Ultraviolet–Visible spectroscopy and Time Resolved Laser induced Fluorescence Spectroscopy can contribute to this technology gap. This work presents the observation of the spectroscopic parameters (molar absorptivities, fluorescent response) of the uranyl ion across the range of conditions expected in reprocessing chemistry. From this data, a monitor using the ratio of the absorbance of the uranyl ion at 403 and 426 nm has been developed. This technique can determine the nitrate solution concentration and can be coupled with a condition appropriate molar absorptivity to determine the uranyl concentration. This method provides a reliable technique for online, real time process monitoring of the uranyl and nitrate concentration under a wide range of solution compositions.