Extraction and separation studies of uranium/VI/with tris-/2-ethyl hexyl/phosphate

A solvent extraction method is proposed for the extraction and separation of uranium from salicylate media using tris-/2-ethyl hexyl/ phosphate dissolved in xylene as an extractant. The optimum conditions were evaluated from a critical study of pH, salicylate concentration, extractant concentration, period of equilibration and diluent. The method permits the separation of uranium from thorium, cerium, titanium, zirconium, hafnium, copper, vanadium and chromium from binary mixtures and is applicable to the analysis of uranium in synthetic samples. The method is precise, accurate, fast and selective.     

Cation-exchange separation of hafnium and zirconium from accompanying ions

Hafnium and zirconium are not retained on the strongly acidic cation-exchange resin Dowex 50 from a mixture consisting of methanol and 12M nitric acid (19:1) which is 0.1M in trioctylphosphine oxide. On the other hand most other elements investigated are strongly adsorbed on the resin from this medium so that they are readily separated from hafnium and zirconium. These elements include titanium, rare earths, alkali metals, alkaline earth metals, iron, cobalt, manganese and zinc. This separation technique has been found to be suitable for the separation of tracer and milligram amounts of hafnium and zirconium from accompanying metal ions. If in place of methanol other organic solvents such as acetone, tetrahydrofuran and methyl glycol are used the selectivity of the separation of zirconium and hafnium from the other elements is decreased. The same effect is observed when hydrochloric acid is used in the mixtures instead of nitric acid.     

Extraction of lanthanoids and some associated elements by mono-(2-ethylhexyl)phosphoric acid and their separations

Mono-(2-ethylhexyl)phosphoric acid (H₂MEHP) has been used to study the extraction of some lanthanoids and other associated elements from nitric acid medium. Effect of various variables like kind of diluent, concentration of metal ion, nitric acid and extractant has been investigated. Based on distribution data, it was possible to achieve some separations of lighter lanthanoids from metals like titanium, zirconium, thorium and uranium with high separation factors.     

Solvent extraction separations with bpha. applications to the microanalysis of niobium and zirconium in uranium

A detailed study of the benzoylphenylhydroxylamine (BPHA)-chloroform-hydrochloric acid solvent extraction system with 52 elements is described with emphasis placed on extraction of the easily hydrolyzed transition metals from strong hydrochloric acid. From this study, a separation procedure for hafnium, niobium, tantalum, titanium, vanadium, and zirconium from uranium was developed, and procedures are given for the microanalysis of niobium and zirconium in uranium. Niobium and zirconium are separated from uranium by extraction into BPHA-chloroform from 10-N HCl.The separated elements are then measured colorimetrically as the niobium-4-(2-pyridylazo)resorcinol and zirconium-arsenazo III complexes. The limit of detection is 1 μg/g U.     

Simple spectrophotometric method for determination of zirconium or hafnium in selected molybdenum-base alloys

A simple analytical procedure is described for determining zirconium or hafnium in molybdenum-base alloys by formation of the Arsenazo III complex of zirconium or hafnium in 9 M hydrochloric acid medium. The absorbance is measured at 670 nm. Molybdenum (10 mg), titanium (1 mg), and rhenium (10 mg) have no adverse effect. No prior separation is needed. The relative standard deviation is 1.3-2.7%.     

Solvent extraction separation of hafnium with 4-methyl-3-pentene-2-one

A new method for the extractive separation of hafnium from zirconium is presented. Zirconium is extracted with pure mesityl oxide from 4M nitric acid/4M sodium nitrate medium, followed by extraction of hafnium with mesityl oxide from 0.4M hydrochloric acid/2M ammonium thiocyanate medium. It is possible to accomplish clean separations of Hf from Zr in ratios from 1:20 to 1:200. The separation of hafnium from commonly associated elements such as scandium, yttrium, uranium, thorium, alkali and alkaline earth metals in 500:1 weight ratio to hafnium is also possible.     

A simple method for the preparation of pure hafnium

The separation of zirconium and hafnium by fractional precipitation as pyrophosphate¹ has been extended for the preparation of pure hafnium. The favourable uptake of hafnium, in spite of the decreasing tendency of partition factor when hafnium concentration is high, is maintained for all concentration of hafnium (relative to zirconium). Particularly significant is the fact that at very high concentrations of hafnium (at≈84%) the uptake of zirconium sharply falls. So pure hafnium can be prepared from natural zirconium by a simple process of eight or nine stages of fractional precipitations as pyrophosphate. This process yields reactor grade zirconium on the one side and pure hafnium on the other side.     

Analysis of niobium alloys

An ion-exchange method was applied to the analysis of synthetic mixtures representing various niobium-base alloys. The alloying elements which were separated and determined include vanadium, zirconium, hafnium, titanium, molybdenum, tungsten and tantalum. Mixtures containing zirconium or hafnium, tungsten, tantalum and niobium were separated by means of a single short column. Coupled columns were employed for the resolution of mixtures containing vanadium, zirconium or titanium, molybdenum, tungsten and niobium. The separation procedures and the methods employed for the determination of the alloying elements in their separate fractions are described.     

Separation of zirconium and hafnium from early actinides and rare earth elements with eichrom’s pb resin in HCl

The separation of zirconium and hafnium isotopes from the early actinides and rare earth elements (REE) with Eichrom’s Pb resin has been studied. Batch studies were performed to characterize the behavior of actinium, thorium, zirconium, hafnium, lutetium, and yttrium on Pb resin from HCl solutions (0.001 M to 11 M). The early actinides and REE had no affinity for the resin at any concentration of HCl, but zirconium and hafnium showed a moderate uptake at high concentrations of HCl with a maximum extraction at 11 M HCl. Several column separations were tested, including with only tracer isotopes and with mass. Rapid, simple separations of zirconium from actinium, thorium, protactinium, and the REE with high yields and low elution volumes are presented with applications for tracer isotope production and fission product separations. The resin is less suitable for hafnium separations as hafnium tends to bleed off the resin even at high concentrations of HCl.

     

Extraction and separation of zirconium from hafnium using a new solvent microextraction technique

A simple method based on the dispersive liquid?Cliquid microextraction and a solidification of floating organic drop followed by an inductively coupled plasma-optical emission spectrometry (ICP-OES) was developed for the extraction and separation of zirconium from hafnium. In this extraction method, an appropriate mixture of acetone (disperser solvent) and 1-undecanol (extraction solvent) was injected rapidly, into the sample solution containing 2.0?mol?L^?1 nitric acid and metal ions in their complex form with cyanex272 and a cloudy solution was formed. After centrifugation, the test tube was cooled by inserting it into an ice bath for 5?min. The solidified 1-undecanol on the top of the solution was transferred into suitable vial and immediately melted, then, 100.0???L of it was dissolved in 100.0???L of 1-propanol and finally, was injected into an ICP-OES by a flow injection system for analysis. Some effective parameters on the extraction and separation of zirconium and hafnium such as type of extraction and disperser solvents and their volumes, type and concentration of ligands, and the type and concentration of acids have been evaluated and optimized. Under the optimum conditions, the selectivity factor of about 13 was obtained.     

金属有机化合物的分析(Ⅴ)——双(烷基环戊二烯基)二卤化钛、锆、铪的纸色谱与核磁共振谱关系的研究

文献报导,仅Subbotina,A.I.等用纸色谱法研究了Cp₂TiCl₂与CpTiCl₅二化合物的分离。我们试图用薄层色谱法分离双(烷基环戊二烯基)二卤化钛、锆、铪化合物,未获成功。改用纸色谱法,取得良好的效果,并对各类化合物所得R_f值与它们的核磁共振谱的δ值之间的变化关系作了研究。     

Diantipyrilmethane as complex-forming reagents in the thin-layer chromatographic determination of metals

Summary The efficiency of diantipyrilmethane used as a reagent for the chromatographic separation of metals, including titanium, zirconium and hafnium, rare earth elements, transition and platinum metals is shown. The peculiarities of the chromatographic behaviour of metal diantipyrilmethanates and the mechanism of their retention in TLC are discussed. Methods were developed for the determination of metals based on complex formation directly in the sorbent layer or by liquid extraction. The chromatographic separation takes place in silica gel thin layers with elution by organic solvent-mineral acid mixtures. The metals are determined by densitometric or spectrophotometric methods. After the complexes are isolated from the layer. The procedures are characterized by simplicity, efficiency, and a rather high selectivity. They were used to analyze steels, alloys, industrial solutions and other samples.     

Extraction and separation studies of tellurium(IV) with tris-(2-ethyl hexyl) phosphate

A method is proposed for the extraction of microgram levels of tellurium(IV) from halide media with tris-(2-ethyl hexyl) phosphate dissolved in toluene as extractant. The optimum conditions have been evaluated from a critical study of acid concentration, extractant concentration, period of equilibration and effect of solvent. Tellurium ion from the organic phase is stripped with water and determined spectrophotometrically with stannous chloride. The method affords binary separation of tellurium from copper, bismuth, gold and selenium and is applicable to the analysis of alloy samples and synthetic mixtures. The method is fast, accurate and precise.     

Determination of zirconium and hafnium with xylenol orange and methylthymol blue

Both Xylenol Orange and Methylthymol Blue are highly selective and sensitive reagents for zirconium and hafnium forming intensely red complexes in an acidic medium. The factors affecting the color formation have been studied. The properties of the complexes have been determined and compared. In general, zirconium forms a more stable complex with the two dyes than hafnium, and Xylenol Orange forms a stronger complex with either zirconium or hafnium than Methylthymol Blue. Hydrogen peroxide can completely mask the zirconium complexes of either dye but only slightly affects the hafnium complex of Xylenol Orange. Zirconium and hafnium can both be determined without separation using peroxide as a masking agent and sulfate as a demasking agent. A bleaching reaction was observed when small amounts of hafnium were added to the red zirconium complex of Methylthymol Blue in 2.4 N perchloric acid or a small amount of zirconium was added to the red hafnium complex of Methylthymol Blue solution at pH 2 to 3.     

Polarographic determination of traces of zirconium in ores by use of complex-forming compounds adsorbable at the dropping mercury electrode

A polarographic method is proposed for the determination of trace zirconium down to the 5 x 10(-9)M level, based on the adsorption of the complex of zirconium with oxalic acid + cupferron + diphenylguanidine at the dropping mercury electrode in sodium acetate-acetic acid solution (pH 5.7). Under optimum conditions the wave-height is proportional to the concentration of zirconium in the range from 0 to 0.4 mug ml . The serious interference from titanium(IV) can be effectively eliminated by solvent extraction with 3% tri-n-octylamine from lN sulphuric acid and stripping with 0.1 M perchloric acid-lM hydrochloric acid-2M nitric acid mixture. The mechanism giving rise to the wave for the zirconium complex has been investigated. The method has been applied to the determination of trace zirconium in ores and ceramics.     

Extraction separation of thallium (III) from thallium (I) with n-octylaniline

A novel method is developed for the extraction separation of thallium(III) from salicylate medium with n-octylaniline dissolved in toluene as an extractant. The optimum conditions have been determined by making a critical study of weak acid concentration, extractant concentration, period of equilibration and effect of solvent on the equilibria. The thallium (III) from the pregnant organic phase is stripped with acetate buffer solution (pH 4.7) and determined complexometrically with EDTA. The method affords the sequential separation of thallium(III) from thallium(I) and also commonly associated metal ions such as Al(III), Ga(III), In(III), Fe(III), Bi(III), Sb(III) and Pb(II). It is used for analysis of synthetic mixtures of associated metal ions and alloys. The method is highly selective, simple and reproducible. The reaction takes place at room temperature and requires 15-20 min for extraction and determination of thallium(III).     

Separation studies of molybdenum(VI) and rhenium(VII) using TPPO as an extractant

A simple, rapid and reproducible method for the extractive separation of molybdenum(VI) and rhenium(VII) is proposed using triphenylphosphine oxide (TPPO) dissolved in toluene as an extractant. The extractions are carried out from the hydrochloric and hydrobromic acid medium. The extraction of molybdenum is quantitative from 2.54-3.10 M hydrochloric acid and from 3.76-3.98 M hydrobromic acid, and that of rhenium is from 6.78-7.91 M hydrochloric acid. The probable nature of the extractable species is established using log distribution ratio-log concentration plots. The method permits mutual separation of molybdenum(VI) and rhenium(VII) and is applicable for the analysis of alloys and pharmaceutical sample. The detection limits for molybdenum(VI) and rhenium(VII) are 0.8 ppm and 4 ppm respectively.     

Adsorption behavior of Zr, Hf, Nb, Ta and Pa on macroporous anion exchanger in NH4SCN/HClO4 and NH4SCN/HF media

The possible use of thiocyanate and ammonium thiocyanate-hydrofluoric acid mixtures for quantitative anion exchange separation of zirconium from hafnium and niobium from tantalum and protactinium has been investigated. Distribution coefficients of zirconium(IV), hafnium(IV), niobium(V), tantalum(V) and protactinium(V) on macroporous BIO-RAD AGMP1 resin over a wide range of SCN and SCN/HF concentrations have been determined. The simultaneous presence of these two complexing agents causes a strong decrease of the adsorption phenomena.     

The differentiation of submicrogram amounts of inorganic and organomercury in water by flameless atomic absorption spectrometry

The basic conditions for the determination of niobium, titanium and zirconium with an argon plasma and a Hitachi UHF Plasma Spectrascan operated at 2450 MHz and 450 W maximum output, have been established. The niobium 405.89-nm, titanium 365.35-nm and zirconium 339.19-nm lines gave detection limits of 0.5, 0.1 and 2.0 p.p.m., respectively, when pure solutions were used. Effects of gas flow rates, high-frequency output and concentration of acids were examined. In applications to steel, titanium was determined without prior chemical separation from iron at the 499.95-nm line, whereas niobium and zirconium could not be determined in the presence of large amounts of iron. When a cupferron precipitation method followed by extraction of iron with methyl isobutyl ketone was applied, satisfactory results were obtained.     

Determination of niobium, titanium and zirconium by high-frequency plasma torch emission spectrometry and its application to steel

The basic conditions for the determination of niobium, titanium and zirconium with an argon plasma and a Hitachi UHF Plasma Spectrascan operated at 2450 MHz and 450 W maximum output, have been established. The niobium 405.89-nm, titanium 365.35-nm and zirconium 339.19-nm lines gave detection limits of 0.5, 0.1 and 2.0 p.p.m., respectively, when pure solutions were used. Effects of gas flow rates, high-frequency output and concentration of acids were examined. In applications to steel, titanium was determined without prior chemical separation from iron at the 499.95-nm line, whereas niobium and zirconium could not be determined in the presence of large amounts of iron. When a cupferron precipitation method followed by extraction of iron with methyl isobutyl ketone was applied, satisfactory results were obtained.