Separation of rhenium(vii) from molybdenum(vi) and many other elements by anion exchange

A method is described for the selective separation of μg and mg amounts of rhenium(VII) from molybdenum (VI) and many other metal ions by means of the strongly basic anion-exchange resin Dowex 1-X8. The separation is based on the preferential elution of molybdenum by a 90% (v/v) methanol-10% 6 M nitric acid mixture; rhenium and a few other elements are retained while molybdenum and most other metal ions including Fe(III), Ca, Mg, Mn, U, Cu, V, etc., are practically unadsorbed. After elution of the adsorbed rhenium with 70% (v/v) tetrahydrofuran-30% 9 M hydrochloric acid, the rhenium is determined spectrophotometrically by a modified thiocyanate method.     

Extraction of rhenium(VII) and molybdenum(VI) with hexabutyltriamide of phosphoric acid from acid media

Extraction of rhenium(VII) and molybdenum(VI) from sulfuric, hydrochloric, and nitric acid solutions with hexabutyltriamide of phosphoric acid was studied. The influence exerted on the extraction of Re(VII) and Mo(VI) by the nature and concentration of an acid in the aqueous phase, temperature, time of contact between phases, and concentration of the extracting agent in the organic phase was analyzed. Isotherms of extraction of rhenium(VII) and molybdenum(VI) with solutions of hexabutyltriamide phosphoric acid in kerosene were obtained, the composition of the complexes being extracted was determined, the enthalpies and entropies were evaluated, and the concentration constants of extraction of the metals were found.     

Column chromatographic separation of molybdenum (VI) from alloys with poly-(dibenzo-18-crown-6) from a hydrochloric acid medium

A very simple column chromatographic separation method has been developed for molybdenum (VI) using poly-(dibenzo-18-crown-6). The separations are carried out from hydrochloric acid medium. The adsorption of molybdenum (VI) on a poly-(DB-18-C-6) was quantitative from 2.5 to 10.0M HCl. Amongst the various eluents tested, 0.5M ammonium hydroxide was found to be an efficient eluent. Molybdenum (VI) was separated from a large number of elements in binary form, as well as from multicomponent mixtures. The method was applied for the analysis of molybdenum from various alloy samples. The method is very simple, rapid, selective and reproducible. The reproducibility of the procedure is +/-2%.     

Extractive separation of molybdenum as Mo(V) xanthate from Iron, vanadium, Tungsten, copper, uranium and other elements

A simple and selective extraction of molybdenum is described. Tungsten is masked with tartaric acid and molybdenum(VI) is reduced in 2M hydrochloric acid by boiling with hydrazine sulphate. Iron, copper and vanadium are then masked with ascorbic acid, thiourea and potassium hydrogen fluoride respectively. The molybdenum(V) is extracted as its xanthate complex into chloroform, from 1M hydrochloric acid that is 0.4M potassium ethyl xanthate. The complex is decomposed by excess of liquid bromine, and the molybdenum is stripped into alkaline hydrogen peroxide solution. The molybdenum is then determined by standard methods. Large amounts of Cu(II), Mn(II), Fe(III), Ti(IV), Zr, Ce(IV), V(V), Nb, Cr(VI), W(VI), U(VI), Re(VII) and Os(VIII) do not interfere. Several synthetic samples and ferromolybdenum have been rapidly and satisfactorily analysed by the method.     

Anion-exchange separation of plutonium in hydrochloric-hydrobromic acid media

Plutonium can be rapidly and selectively separated from the elements that interfere in its radiochemical determination, by the use of hydrobromic acid in a hydrohalic acid anion-exchange separation procedure. Plutonium(IV) and (VI) are adsorbed onto the resin column from 9M hydrochloric acid, interfering elements such as americium and thorium are washed from the column with 9M hydrochloric acid, and the plutonium is reduced to plutoniurn(III) and washed from the column with 11M hydrobromic acid. Interfering elements such as uranium and neptunium, which are adsorbed onto the column from 9M hydrochloric acid, are retained there during the hydrochloric and hydrobromic acid washes. This system would also appear to provide the means for effectively separating plutonium from those elements that commonly interfere in such chemical methods of analysis as redox titration.     

Re(VII) extraction and separation from Mo(VI) by levextrel resins containing trialkyl amine

A synthetic method of novel trialkyl amine (N235, R₃N, R = C₈–C₁₀) Levextrel resin was described in this paper. The extraction behavior of rhenium(VII) and molybdenum(VI) with this N235 Levextrel resin has been studied. The mechanism of extraction of Re(VII) with the N235 Levextrel resin has been discussed briefly through equi-molar series method and the conventional slope analysis method. The optimal conditions of extraction and separation Mo(VI) and Re(VII) with the N235 Levextrel resin were determined. Also, its excellent extraction characteristics for Re(VII) were confirmed by extraction and stripping tests in a analog liquid solution containing Mo(VI) and Re(VII).     

Separation and concentration of molybdenum(VI) and tungsten(VI) with chelating ion-exchange resins containing sulphur ligands

Three chelating ion-exchange resins based on macroreticular polyacrylonitrile-divinylbenzene copolymers with thioglycollic acid and cysteine as functional groups have been tested for separation of molybdenum(VI) and tungsten(VI). On a short column of the thioglycollic acid resin, molybdenum(VI) and tungsten(VI) can be selectively sorbed from pH-4.3 acetate buffer and eluted with 2M hydrochloric acid and a mixture of 0.1M sodium hydroxide and 0.1M sodium chloride, respectively, with quantitative recovery even at very low concentrations. Simulated sea-water samples have been analysed.     

Chromatographic separation of uranium(VI) from other elements using L-valine and poly[dibenzo-18-crown-6]

A selective and effective column chromatographic separation method has been developed for uranium(VI) using poly[dibenzo-18-crown-6]. The separation was carried out in L-valine medium. The adsorption of uranium(VI) was quantitative from 1.0 × 10⁻⁴ to 1 × 10⁻¹ M of L-valine. Amongst various eluents 2.0–8.0 M hydrochloric acid, 1.0–4.0 M sulfuric acid, 1.0–5.0 M perchloric acid, 6.0–8.0 M hydrobromic acid and 5.0–6.0 M acetic acid were found to be efficient eluents for uranium(Vl). The capacity of poly[dibenzo-18-crown-6] for uranium(VI) was 0.25 ± 0.01 mmol/g of crown polymer. Uranium(VI) was separated from number of cations and anions in binary mixtures in which most of the cations and anions show a very high tolerance limit. The selective separation of uranium(VI) was carried out from multicomponent mixtures. The method was extended to determination of uranium(VI) in geological samples. The method is simple, rapid and selective with good reproducibility (approximately ∼2%).     

Separation of molybdenum(VI) from other elements by solvent extraction with dibenzo-18-crown-6 from hydrochloric acid medium

DB-18-C6 was used for the extractive separation analysis of molybdenum(VI) from a range of other elements. Molybdenum(VI) was quantitatively extracted from 8M hydrochloric acid with 0.01M DB-18-C6 in nitrobenzene. It was stripped from the organic phase with 2M nitric acid and determined spectrophotometrically with Tiron at 390 nm. Molybdenum was separated from a large number of elements in binary mixtures, the tolerance limit for most elements being very high. Selective extraction of molybdenum permits its separation from barium, thorium, cesium, rubidium, strontium, lanthanum, chromium(III) and cerium(III). The method was extended for the analysis of molybdenum in a soil sample.     

Separation of molybdenum (VI) by extraction withn-octylaniline from hydrochloric acid medium

n-Octylaniline in bezene was used for the extractive separation of molybdenum (VI) from hydrochloric acid medium. Molybdenum(VI) was extracted quantitatively from 10 ml aqueous solution 1.5M in hydrochloric acid and 10M in lithium chloride into 10 ml of 10%n-octylaninline in benzene. It was stripped from the organic phase with 5% aqueous ammonia solution and estimated spectrophotometrically with thiocyanate at 465 nm. The interference of various ions has been studied in detail and conditions have been established for the determination of molybdenum(VI) in synthetic mixtures and alloy samples.     

Liquid-liquid extraction of molybdenum thiocyanate with hexamethyl phosphortriamide and direct spectrophotometric determination in the organic phase

A sensitive and selective method for estimation of trace molybdenum with fairly common reagents has been developed. The Mo-thiocyanate complex is extracted with hexamethyl phosphortriamide and chloroform from 0.75-1.5M hydrochloric acid. The molar absorptivity is 1.76 x 10(4) 1.mole(-1).cm(-1). The system obeys Beer's law at 460nm over the molybdenum concentration range 0.75-5ppm. The method is simple, rapid, and requires no additional reducing agent. It is generally free from interference by most of the metals commonly associated with molybdenum, including rhenium. Molybdenum in alloy steel has been successfully determined.     

Spectrophotometric determination of molybdenum(VI)

Molybdenum(IV) gives a red colour with ammonium thiocyanate in 5-8M hydrochloric acid medium, the Sandell sensitivity index being 0.018 ppm Mo(VI)/cm(2). Molybdenum(VI) in 4-7M hydrochloric acid medium forms a red complex with ethyl xanthate and ammonium thiocyanate and this can be extracted into acetophenone. Beer's law is obeyed over the range of 1.2-13.8 ppm, and the Sandell indices at 370 and 470 nm are 0.0016 and 0.0068 ppm/cm(2) respectively. The colour is stable for 40 hr. Most cations do not interfere.     

Liquid-liquid extraction separation of uranium(VI) from associated elements using dibenzo-24-crown-8 from hydrobromic acid medium

Liquid-liquid extraction of uranium (VI) from hydrobromic acid solutions with dibenzo-24-crown-8 in nitrobenzene have been investigated. Uranium(VI) was quantitatively extracted from 6.0–8.0M hydrobromic acid with 0.001–0.01M dibenzo-24-crown-8 and was quantitatively stripped from the organic phase with 0.1–1.0M hydrochloric acid, 0.5–10M nitric acid, 2–10M perchloric acid, 3.0–10M sulfuric acid or 3.0–10M acetic acid. It was possible to separate uranium(VI) from a number of elements in binary mixtures. Most of the elements showed very high tolerance limit Uranium(VI) was also separated from a number of associated elements in multicomponent mixtures. The method is very simple, selective, rapid and highly reproducible (approximately±2%) and was applied to the analysis of uranium in geological samples.     

Separation of rhenium from molybdenum and other heavy metals by solvent extraction

Summary Two methods are presented for the extractive separation of rhenium from molybdenum and other heavy metals in hydrochloric acid solution. In the first method, Mo(VI) and Re(VII) are reduced by hydrazine in strong hydrochloric acid solution to Mo(V) and Re(IV). The former is then extracted intoiso-amyl acetate. The Re(IV) remaining in the aqueous phase is oxidised to Re(VII) and determined by known procedures. In the second method, Re(VII) and other ions in 1–1.3N HCl are boiled with hydrazine sulphate for 5 minutes. After adding EDTA to complex Mo(V) and adjusting the solution to 0.33N HCl, rhenium is extracted into chloroform containing 1% tribenzylamine, and is recovered by shaking with water having sufficient ammonia to neutralise the acid and a little hydrogen peroxide.

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Zusammenfassung Zwei Arbeitsweisen für die extraktive Trennung des Rheniums von Molybdän und anderen Schwermetallen in salzsaurer Lösung wurden angegeben. Bei dem ersten Verfahren werden Mo(VI) und Re(VII) mit Hydrazin in stark salzsaurer Lösung zu Mo(V) und Re(IV) reduziert. Ersteres wird dann mit Isoamylacetat extrahiert. Re(IV) verbleibt in der wäßrigen Phase, wird zu Re(VII) oxydiert und auf bekannte Art bestimmt. Beim zweiten Verfahren werden Re(VII) und die anderen Ionen in 1- bis 1,3-n Salzsäure 5 Minuten mit Hydrazinsulfat gekocht. Nachdem man ÄDTA zur Komplexierung des Mo(V) zugesetzt und die Lösung auf 0,33-n an Salzsäure eingestellt hat, wird Rhenium mit einer 1%igen Lösung von Tribenzylamin in Chloroform extrahiert. Die Rückextraktion erfolgt mit Wasser, worin Ammoniak (zur Neutralisation der Säure) und etwas Wasserstoffperoxid gelöst sind.

     

A new volumetric method for the determination of molybdenum(VI)

Summary A new volumetric method has been developed for the determination of molybdenum(VI). The method consists in the reduction of molybdenum(VI) by heating with a slight excess of hydrazine sulphate in 1 to 2 M hydrochloric acid medium for ten minutes on a water bath. The mixture is cooled and the molybdenum(V) obtained determined by titration with a standard solution of ceric sulphate at an overall acidity of 4 N hydrochloric acid, using diphenyl benzidine as indicator and adding 5 ml of syrupy phosphoric acid for 50 ml of the mixture. Alternately the molybdenum(V) can be titrated with a standard solution of ceric sulphate at an overall acidity of 3 N hydrochloric acid using ferroin as indicator and adding 5 ml of syrupy phosphoric acid for 50 ml of the titration mixture. The molybdenum(V) can also be titrated with a standard solution of sodium vanadate in 8 N sulphuric acid medium, using N-phenyl anthranilic acid as indicator. Alternately, the titration with sodium vanadate can be made with diphenyl benzidine as indicator in 4 N acid medium, adding 5 ml of syrupy phosphoric acid and 1 ml of 1.0 M oxalic acid to catalyse the indicator action. The method now proposed is much more convenient than the methods currently available. It is simple because it does not require any costly chemicals or complicated apparatus. Furthermore, it has the advantages of great rapidity and excellent precision.     

Methods for the separation of rhenium, osmium and molybdenum applicable to isotope geochemistry

Effective methods are described for the chemical separation of rhenium, osmium and molybdenum. The methods are based on distillation and anion-exchange chromatography, and have been the basis for rhenium-osmium isotope studies of ore deposits and meteorites. Successful anion-exchange separation of osmium requires both recognition and careful control of the osmium species in solution; thus, distillation of osmium tetroxide from a mixture of sulfuric acid and hydrogen peroxide is preferred to anion-exchange. Distribution coefficients measured for perrhenate in sulfuric acid media are sufficiently high (K(d) > 500) for rhenium to be directly loaded onto an ion-exchange column from a distillation residue and subsequently eluted with nitric acid. Polymerization of molybdenum species during elution is prevented by use of a solution that is 1M in hydrochloric acid and 1M in sodium chloride.     

Radiochemical separation of rhenium(VII) from tungsten(VI)

The absorption of rhenium(VII) and tungsten(VI) ions on Al₂O₃ from HCl, HClO₄, HNO₃, H₂SO₄, H₃PO₄, NaOH, NH₄OH, NaCl, NaF, and Na-tartarate solutions by batch equilibration, as well as by passage through a chromatographic column, has been studied. The results show that rhenium(VII) can be effectively separated from tungsten(VI) using any of the acid or salt solutions investigated. The experimental data allowed to develop a simple procedure for the radiochemical separation of rhenium isotopes from an irradiated WO₃ sample.     

Column chromatographic separation of uranium(VI) and other elements using poly(dibenzo-18-crown-6) and ascorbic acid medium

A selective and very effective separation method for uranium(VI) has been developed by using poly(dibenzo-18-crown-6) and column chromatography. The separations are carried out from ascorbic acid medium. The adsorption of uranium(VI) was quantitative from 0.00002 to 0.006 M ascorbic acid. The elution of uranium(VI) was quantitative with 2.0-8.0 M HCl and 2.0-5.0 M H2SO4. The capacity of poly(dibenzo-18-crown-6) for uranium(VI) was found to be 0.92 +/- 0.01 mmol g(-1) of crown polymer. Uranium(VI) was separated from a number of cations in binary as well as in multicomponent mixtures. The method was extended to the determination of uranium in geological samples. It is possible to separate and determine 5 ppm of uranium(VI) by this method. The method is very simple, rapid, selective and has good reproducibility (approximately +/- 2%).     

Sorptive separation of molybdenum(VI) from rhenium-containing solutions

It is shown that Purolite S957 cation-exchange resin containing phosphonic-acid and sulfonic groups is capable of selectively sorbing molybdenum(VI) in the presence of rhenium(VII) in solution.     

Liquid anion exchanger study of gold (III) from aqueous halide media with N-n-octylaniline

N-n-octylaniline in xylene is used for the extractive separation of gold(III) from halide media. Gold(III) was extracted quantitatively with 10 ml of 2% reagent in xylene from 0.5-10 M and 0.5-8 M hydrochloric acid and hydrobromic acid, respectively. It was stripped from the organic phase with ammonia buffer solution (pH 10.1) and estimated spectrophotometrically with stannous chloride. The effect of metal ion, acids, reagent concentration and of various foreign ions has been investigated. Method is applicable to the analysis of synthetic mixtures containing platinum metals and alloy samples. The method is fast, accurate and precise.