Simultaneous determination of lead and nickel in uranium by square-wave polarography

A sensitive method for the simultaneous determination of trace lead and nickel in uranium is described. These elements are separated from uranium by anion exchange and then determined by square-wave polarography using the alkaline cyanide solution as supporting electrolyte. The procedure is applicable to uranium metal and its compounds containing as little as 1 p.p.m. of lead and nickel.     

Indirect determination of uranium by the on-line reduction and fluorimetric detection of cerium(III).

A novel flow injection method has been developed for the indirect determination of uranium by the on-line reduction and subsequent fluorimetric detection of cerium(III). A sample solution containing uranium(VI), prepared as a sulfuric acid solution, was injected into a sulfuric acid carrier solution and passed through a column packed with metal bismuth to reduce uranium(VI) to uranium(IV). The sample solution was merged with a cerium(IV) solution to oxidize uranium(IV) to uranium(VI) and the cerium(III) generated was then monitored fluorimetricaly. The present method is free from interference from zirconium, lanthanides, and thorium, and has been successfully applied to the determination of uranium in monazite coupled with an anion-exchange separation in a sulfuric acid medium to eliminate iron(III). The sample throughput was 25 per hour and the lowest detectable concentration was 0.0042 mg l(-1).     

Spectrophotometric determination of uranium using ascorbic acid as a chromogenic reagent

A spectrophotometric method has been developed for the determination of uranium(VI) using ascorbic acid. Uranium in the hexavalent state forms a reddish-brown coloured complex with ascorbic acid. The colour intensity of the complex is maximum at pH 4.2-4.5 and is stable for 24 hr. The absorbances of uranium(VI)-ascorbic acid complex at 360 and 450 nm are used for its quantification. Uranium in the range 8-200 microg/ml has been determined with good precision. The method allows the determination of uranium in the presence of many metal ions present as impurities. The described method is simple, accurate and applicable to uranium concentration relevant to the PUREX process and thus can be used for analytical control purposes.     

Complexation of uranium by 2-(2-thiazolylazo)-4-methoxyphenol and 2-(2-thiazolylazo)-5-methoxyphenol

A comparative study has been made of the complexation of uranium(VI) by 2-(2-thiazolyl)-4-methoxyphenol (TAMH) and 2-(2-thiazolylazo)-5-methoxyphenol(TAMR). The complexes are less stable and have lower molar absorptivities than the PAR and TAR complexes but are still useful for determination of uranium. The TAMH chelate can be extracted into isobutyl methyl ketone. Both complexes are 1:1 metal :ligand. For the TAMH complex log beta(1) = 8.8, = 1.4 x 10(4) at 610 mmu; for the TAMR complex log beta(1) = 8.1, = 2.0 x 10(4) at 530 mmu.     

Determination of small amounts of uranium in hafnium,zirconium and zircaloy-2

To meet specification requirements, selected methods for determining uranium have been examined and two satisfactory procedures have been developed for application to the analysis of reactor-grades of hafnium, zirconium and Zircaloy-2.These procedures are based on extraction of uranyl ions from a solution of the sample with a tri-n-butyl phosphate-iso-octane mixture. Following this extraction, uranium over the range 10–150 p.p.m. is determined by a spectrophotometric method, using dibenzoylmethane. For smaller amounts of uranium, down to about 0.5 p.p.m., the determination is completed by squarewave polarography.     

Determination of trace elements in manganese metal and compounds by ion-exchange chromatography and atomic absorption spectrometry : part 2. Determination of Bi,Cd, In,Zn, Pb,Fe(III), Ga,Cu(II), Co and U(VI)

Traces of the specified elements are separated from 1 g of manganese (II), using a 30- g column of AG50W-X8 cation-exchange resin and mixtures of hydrochloric acid and acetone as eluents. The trace elements are separated into three groups and are determined by atomic absorption spectrometry, except uranium for which spectrophotometry is used. Recoveries for 10 μg amounts (20 μg for gallium) vary between 94% (for gallium) and 103% (for uranium). A combined elution curve, results for the analysis of synthetic mixtures and for the determination of ten trace elements in samples of manganese metal, chloride and dioxide are presented.     

Acetylacetone as chelating reagent, extracting solvent, and electrolysis medium: Polarographic determination of uranium(VI) and iron(III)

The chelating reagent acetylacetone has been examined as a polarographic medium; a method for its purification has been developed and it is found that the specific conductance is 4.2 x 10(-8) mho/cm, the accessible potential ranges are from -0.16 to -2.26 V vs. Ag/0.1M AgClO(4) for the pure solvent and from -0.35 to -2.20 V in the solvent after extraction. In pure solvent ferric acetylacetonate exhibits one wave and the uranyl complex gives two waves. After extraction from aqueous solution at pH 6.8-7.0, both metal acetylacetonates are reduced more reversibly and at more positive potential than in the pure solvent. Calibration curves are linear in the range 10(-5) -10(-3)M metal ion in the extract. The direct polarographic determination of uranium and iron in acetylacetone after extraction of the chelate from aqueous solution has been developed.     

Dosage de l'oxygene dans l'uranium et ses composes par la methode au monochlorure de soufre

A sulfur monochloride method is proposed for the determination of oxygen in uranium compounds. Sulfur monochloride reacts with oxygenated compounds at temperatures depending upon their nature; the sulfur dioxide produced is titrated by iodometry, after the excess reagent has been eliminated by a selective adsorption-desorption process using activated charcoal. This method has been successfully applied to uranium oxides (UO₂, U₃O₈), to mixtures of uranium dioxide with uranium, uranium nitride, and uranium carbide, and to substituted carbides (UC_1-xO_x). The results are generally satisfactory for oxygen contents higher than 500 p.p.m. However, in the presence of free or combined carbon, this limit is considerably higher. A loss of oxygen as carbon monoxide is also possible, and a simultaneous determination of carbon monoxide must be carried out. The relative error is of the order of a few per cent.     

Determination of micro amounts of uranium by a molybdenum blue method

A new and highly sensitive spectrophotometric method has been developed for the determination of micro amounts of uranium by a molybdenum blue method. The method is based on the observation that at low acidities uranium(IV) reduces ammonium molybdate to molybdenum blue, the absorbance of which is proportional to the amount of uranium present. The variables affecting development of the colour have been investigated and the conditions optimized. Beer's law is found to hold good for uranium concentrations between 1 and 20 ppm, with a precision of 2%. The effect of diverse ions has been studied. The method is useful for the determination of uranium present as an impurity (down to 0.1%) in plutonium, neptunium or thorium.     

Determination of uranium in plutonium by differential linear sweep oscillographic polarography

The polarographic behavior of uranium in hydroxylamine hydrochloride was investigated by differential oscillographic polarography. A procedure is presented for the determination of uranium in plutonium for concentrations of uranium greater than 10 p.p.m. Analyses of solutions containing 22 common impurities found in plutonium metal revealed that antimony, copper, and titanium cause significant interference. A reversible peak corresponding to a one-electron reduction was obtained with a peak potential of -0.167 V vs. Hg pool electrode. The diffusion coefficient is 0.51·10^-5 cm²/sec and the diffusion current constant is 1.59 with an average relative standard deviation of 2.28%. The peak current of uranium can be affected by hydrochloric, nitric, perchloric, and sulfuric acids, depending on the acid concentration.     

Fluorometric determination of uranium and tungsten with o-hydroxyhydroquinonephthalein in the presence of non-ionic surfactant

Complex formation between uranium or tungsten and o-hydroxyhydroquinonephthalein (Qnph) in various micellar surfactant media has been investigated fluorometrically, and determination of uranium and tungsten based on the difference between the relative fluorescence intensities of Qnph and the metal complex at 535 nm, with excitation at 400 nm in the presence of poly(vinyl) alcohol as a non-ionic surfactant. The calibration curves were linear up to 1.0 mu/ml uranium and 0.9, mu/ml tungsten. The relative standard deviations (5 replicates) were 2.6% for tungsten and 3.0% for uranium, and recovery tests gave relatively good results (97-104%).     

Spectrophotometric determination of uranium(VI) with 2-(3,5-dibromo-2-pyridylazo)-5-diethylaminophenol in the presence of anionic surfactant

A highly sensitive method for spectrophotometric determination of uranium has been devised. The method is based on formation of a red-violet 1:2 (metal:ligand) complex from the reaction of uranium(VI) with 2-(3,5-dibromo-2-pyridylazo)-5-diethylaminophenol (3,5-diBr-PADAP) in the presence of an anionic surfactant, sodium lauryl sulphate. Its molar absorptivity is found to be 9.1 x 10(4)l.mole(-1).cm(-1). The absorbance is constant in the range pH 8.4-9.9 Beer's law is obeyed for 0-1.4 mug/ml concentrations of uranium. In the presence of DCTA the method is selective for uranium, and can be used for the determination of trace amounts of uranium in water samples.     

Extraction of uranium, thorium and lanthanides using Cyanex-923: Their separations and recovery from monazite

The extraction behavior of uranium, thorium and lanthanides, represented by cerium and ytterbium, by Cyanex-923 has been investigated. The effect of different variables like the concentration of acids, metal ion and extractant, nature of diluent and temperature has been studied. A composition for the extracted U(VI) and Th(IV) species has been proposed. Based on the partition data some important binary and ternary separations involving the aforesaid metal ions have been achieved. The proposed procedure has been applied for the recovery of uranium, thorium and lanthanide fraction from monazite sand. The stability and regeneration capacity of the extractant have been evaluated.     

Coulometric determination of uranium with a platinum working electrode

Experimental conditions have been established which enable uranium to be determined coulometrically by the reduction of uranium(VI) to uranium(IV) at a platinum working electrode, by controlled-potential or controlled-potential-limit techniques. The procedure has been used successfully as a subsidiary method in the routine determination of uranium in pure uranyl nitrate solutions. The platinum electrode has several important practical advantages over the well established mercury-pool electrode for the coulometric determination of uranium. The consecutive determination of iron(III) and uranium(VI), or plutonium(IV) and uranium(VI) can be carried out with the same working electrode in the same solution and the coulometric oxidation of uranium(IV) to uranium(VT) is practicable. The rate of stirring of the cell liquor is much less critical in the case of the platinum electrode. Two main problems had to be overcome before a practical procedure could be achieved; hydrogen evolution during the uranium(VI)-(IV) reduction had to be eliminated so that 100% current efficiency could be obtained for the desired reaction and electrode-surface poisoning phenomena had to be controlled so that reaction times could be kept reasonably short. It was found that selection of a hydrochloric acid base solution containing a small amount of bismuth(III) enabled hydrogen evolution to be avoided: also electrode-surface poisoning with this base solution was not particularly serious and could be maintained at a satisfactorily low level by occasionally anodizing the electrode in dilute sulphuric acid. Bismuth(III) forms a complex with chloride ions and its presence increases the hydrogen overvoltage at the working electrode: no visible deposit of bismuth metal forms on the electrode during the uranium reduction. Samples containing nitrate can be analysed provided sulphamic acid is added to this hydrochoric acid base solution.     

Separation of uranium from other metals by partition chromatography

Uranium(VI) can be separated quantitatively from most other metal ions by partition chromatography on a silica-gel column. The column is treated with aqueous 6M nitric acid; after sorption of the sample, uranium(VI) is selectively and rapidly eluted by methyl isobutyl ketone. In addition to the separation of macro quantities of metal ions, the method has been used successfully for the isolation of trace amounts of metal ions from uranium(VI).     

Simultaneous determination of thorium and uranium in ores and SRMs by instrumental neutron activation analysis

A procedure has been developed for the determination of thoirum and uranium in ores and geological materials. The technique is relatively simple, accurate and adaptable routinely. Gamma-ray peak interferences are discussed in detail and the usefulness of the multiple gamma-ray peak ratios in the determination of the purity of peaks has been explained. The precision and accuracy of the method have been determined by analysing IAEA and NBL Standard thorium/uranium ores.     

Determination of cadmium in uranium by ion exchange and square-wave polarography

Traces of cadmium in uranium and its compounds can be determined by ion-exchange separation and square-wave polarography. With a small column of anion-exchange resin, cadmium can be separated from uranium and recovered quantitatively from hydrochloric acid solution, Separations of cadmium from uranium are not perfect but are sufficient for the determination of traces of cadmium by square-wave polarography. The lower limit of the method is 0.01 p.p.m. of cadmium.     

Determination of uranium(VI) in natural waters after preconcentration on adsorbent containing m-aminophenol fragments

Sorption and complexing properties of a modified adsorbent based on a maleic anhydride-styrene copolymer towards uranium(VI) are studied and the main quantitative characteristics of the metal ion sorption are determined. An adsorbent containing m-aminophenol fragments is proposed for the selective sorption of uranium(VI) from solutions. The optimal sorption conditions have been found. The recovery of uranium(VI) under the optimal conditions exceeds 95%. A procedure of the sorption photometric determination of uranium(VI) in sea water is developed.     

A modified method for the determination of uranium in Nb/Ta minerals by LED fluorimetry

A modified LED fluorimetry determination of uranium in Nb/Ta minerals has been developed. The mineral is brought into solution by fusion with mixed phosphate flux (NaH₂PO₄, H₂O and Na₂HPO₄). Iron quenches uranium fluorescence when it is present above the ratio of (iron to uranium) 100. Uranium is separated in ethyl acetate by solvent extraction and then stripped back into pyrophosphate buffer (pH ~ 7) prior to its LED fluorimetry determination. This modified method has been applied for the determination of uranium in synthetic mixtures and Nb/Ta minerals including Certified Reference Materials (X1807) with high degree of accuracy and precision.

     

Further study of extraction equilibrium of uranium(VI) with dicyclohexano-18-crown-6 and its application to separating uranium and thorium

In our publication (1), the extraction of uranium with dicyclohexano-18-crown-6 (mixed isomers) has been described. The extraction equilibrium of uranium(VI) from aqueous hydrochloric acid solution with dicyclohexano-18-crown-6 isomer A (Ia) and isomer B (Ib) in 1,2-dichloroethane is presented in this paper. The extracted species are found to be 1:2 (metal/crown) for Ia and 2:3 for Ib from slope analysis and direct determination of extracted complexes. The extraction equilibrium constants (Kex) have been determined at 25°C, and equal 29.5 for the former and 0.208 for the latter. It is concluded that Ia has stronger coordinate ability for uranium than Ib. The different orientation of the lone pairs of the oxygen atoms in both isomers will be taken into account for interpreting above results. The extraction of uranium(VI) with dicyclohexano-18-crown-6 (mixed isomers) or Ia from aqueous hydrochloric acid solution is effective and selective. In 0.1M crown ether-1,2-dichloroethane-6N HCl system, the separation factor U(VI)/Th(IV) exceeds 1000. The result can be taken in separating uranium and thorium.