Precipitation of molybdenum(V) as the hydroxide and its separation from rhenium

A study of the conditions for precipitation of molybdenum(V) hydroxide shows that for Mo concentration 1 mg ml about 97.5% of the Mo can be precipitated between pH 5 and 5.8. Lower concentrations of molybdenum(V) or molybdenum(VI) can be precipitated quantitatively by using 20 times the amount of zirconium as collector, at the same pH. On this basis, a simple method is given for quantitative separation of rhenium from large amounts of molybdenum and is attested by analysis of synthetic and molybdenite samples.     

6-Methyl-2-pyridinecarboxamide oxime, a reagent for copper

6-Methyl-2-pyridinecarboxamide oxime (R) forms a yellow compound with copper(I), the molar absorptivity being 7.2 x 10(3) at the wavelength of maximum absorption, 405 nm. The copper compound, CuR(2), forms completely over the pH range 4.5-7 and is easily extracted into isoamyl alcohol. R is highly specific for copper, the methyl group neighbouring the ring nitrogen atom preventing reaction with iron and other metals.     

N-hydroxy-N,N'-diphenylcinnamamidine (HDPCA) as a new reagent for extractive separation and photometric determination of vanadium(V)

N-hydroxy-N,N′-diphenylcinnamamidine (HDPCA) forms a blue-violet coloured 1:2 complex (metal:ligand) with vanadium(V), which can be quantitatively extracted into chloroform from 1.0–9.5M acetic acid medium. Based on this colour reaction, a sensitive and highly selective method for the spectrophotometric determination of microgram quantities of vanadium(V) has been developed. The complex shows maximum absorption at 570 nm and obeys Beer's law in the vanadium concentration range 0.6–12.5 μg/ml. The method has been applied to alloy steels.     

2,5-Dihydroxyacetophenone oxime as an analytical reagent for the amperometric determination of copper,palladium, and nickel

Summary Copper, palladium and nickel can be titrated amperometrically with 2,5-dihydroxyacetophenone oxime at –0.15, –0.4 and, –1.2 V vs. S. C. E. respectively, the optimum p_H values being 4.6, 4.0, and 9.0. Alkali and alkaline earth metals, Al, Bi, Cd, Co, Cr. Fe(II), Hg, Mn, Ni, Pb, Th, Zn, UO, W, and Zr do not interfere with the estimation of copper and palladium. The interferences due to the presence of silver and iron(III) can be eliminated by adding excess of KCl and KF respectively. Most heavy metals interfere with the estimation of nickel and should be eliminated before titration.

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Zusammenfassung Kupfer, Palladium und Nickel können mit 2,5-Dihydroxyaeetophenonoxim bei –0,15, –0,4 bzw. –1,2 V gegen eine gesättigte Kalomelelektrode amperometrisch titriert werden, wobei man das p_H am besten auf 4,6, 4,0 bzw. 9,0 hält. Alkalimetalle, Erdalkalien, Al, Bi, Cd, Co, Cr, Fe(II), Hg, Mn, Ni, Pb, Th, Zn, UO₂, W und Zr stören die Bestimmung des Kupfers und des Palladiums. Silber und Eisen können mit Kaliumchlorid gefällt bzw. mit Kaliumfluorid maskiert werden. Die meisten Schwermetalle stören die Nickelbestimmung und müssen daher vor der Titration entfernt werden.

     

NMR structural aspects of the chemistry of V, Mo, W polyoxometalates

The results of structural investigations of vanadium, molybdenum, and tungsten polyoxoanions (PA) by ¹⁷O, ⁵¹V, ⁹⁵Mo, ¹⁸³W, and heteroatom NMR are generalized in this review. NMR spectroscopy possibilities to determine the structure of PA are discussed. NMR data on PA of different structures compositions nuclei are demonstrated.     

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.     

Oximidobenzotetronic acid as a reagent for the separation and gravimetric determination of palladium and cobalt

Oximidobenzotetronic acid is recommended for the separation and gravimetric determination of palladium and cobalt An ethanolic solution of the reagent quantitatively precipitates palladium(II) from solutions which are 0.75 N in acid up to pH 5.1, the complex is weighed as Pd(C₉H₅NO₄)₂. Cobalt(II) can be determined in the filtrate after the precipitation of palladium. With 0.5 N acid solutions, no interference was found from Pt(IV), Ir(IV), Rh(III), Ru(III), Os(IV), Au(III), Ag(I), Cu(II), Fe(III), Ni(II), Hg(II). Pb(II), Bi(III), Cd(II), As(V), Se(VI), Te(IV), Mo(VI), Sb(III), Al(III), Cr(III), Zn(II), Ti(IV), Zr(IV). acetate, oxalate, citrate, tartrate, phosphate and fluoride.     

Tropoloae as a specific reagent for the determination of vanadium(V)

The blue colour developed on interaction of vanadium(V) with tropolone m 5.5-7.0N acid can be extracted into chloroform. The complex has an absorption maximum at 590 nm. Colour development is instantaneous and the extracted species is stable for 72 hr. Beer's law is followed in the range 1.02-14.25 ppm of vanadium. The molar absorptivity is 4.63 x 10(3)l.mole(-1).cm(-1). Most anions do not interfere. Of the 37 cations examined, only Ti(III), Ru(III), Pt(IV), Ir(IV), Mn(II), Ta(V) and Ce(III) were found to interfere. The interference due to these cations has been removed by masking them with EDTA.     

Group separation by solvent extraction from silicate rock matrix of Nb, Mo, Ta, and W at low levels for ICP-MS

Summary The extraction efficiency from silicate rock solutions in HF of Nb, Mo, Ta, and W as a function of fluoride activity in HCl solution, 3 mol/l, was investigated. At pF 3.5, N-benzoyl N-phenylhydroxylamine (BPHA) dissolved in CHCl₃ proved to be an ideal system for the separation of the four analyte elements from the rock matrix after HF dissolution. All major rock constituents except for titanium are left behind in the aqueous phase. Values for the distribution ratios are 500±100 for all four elements allowing cross calibration in ICP-MS between enriched isotopes of Mo and W added to the samples before dissolution (isotope dilution) and the neighbouring monoisotopic elements Nb and Ta. Previously such high distribution ratios have been reported for Mo only because Nb, Ta, and W are not normally available as reactive ions due to hydrolysis unless directly released from fluoride complexes by downwards adjustment of fluoride activity of the solution in the presence of BPHA. Analytical data from 20 geochemical reference standards document the practical value of the described analytical procedure. Using ICP-MS and BPHA-pentanol solutions standards, superior detection limits are demonstrated by Nb, Ta, and W values in the sub ppm range obtained for some ultrabasic rock standards for which reference values are not yet available. Using ICP-MS and BPHA-pentanol solutions, superior detection limits are demonstrated by concentration values in the sub ppm range obtained for some ultrabasic rock standards for which reference values are not yet available.     

Substituted ethan phosphonic acid esters as reagents for the separation of molybdenum from rhenium by solvent extraction

New esters of the ethan phosphonic acids have been synthesized and their extraction properties studied with respect to Mo(VI), Re(VII), Fe(III),Au(III),Tl(III) and Sb(V). A possibility is shown for the analytical separation of molybdenum from rhenium (beta = 700). The state of these new extraction agents in carbon tetrachloride solution, and the mechanism of the extraction processes, have been investigated by means of infrared spectra.     

Extraction chromatographic separation of99Mo and187W with trioctylamine

⁹⁹Mo and¹⁸⁷W have been separated by reversed phase extraction chromatographic technique, using 1M TOA impregnated on kieselguhr in a column and 4N HCl, respectively, as stationary and mobile phase.     

On line ion exchange separation of short-lived Zr, Hf, Mo, Ta and W isotopes as homologs of transactinide elements

The short-lived isotopes of W and their descendants have been separated from nuclear reaction products arising in the bombardment of samarium target with²⁴Mg ions at the U-400 cyclotron of JINR-Dubna. Chemical separations were performed using previously elaborated fast and continuous ion exchange. In similar way products of²³⁵U fission, obtained at the microtron MT-25 during irradiation of²³⁵U target with photoneutrons were separated.     

Vibrational spectra of hexachloromolybdates and hexachlorotungstates: hexachloro-anions of Mo(III), Mo(IV), Mo(V), W(IV) and W(V)

Raman and far-i.r. measurements are reported for salts of the ions [MoCl₆]ⁿ⁻ (n = 1, 2, 3) and [WCl₆]ⁿ⁻ (n = 1, 2). The frequencies v₁, v₃, v₄, and v₅ for these ions, many of which have not been measured previously, were thus mostly identified, but v₂ was not observed for any of these ions.     

EPR study of dithiophosphate,dithiocarbamate, and xanthate complexes of Cr(V), Mo(V), and W(V)

Liquid and frozen solutions of diethyl dithiophosphate, diethyl dithiocarbamate, and butyl xanthate complexes of Cr(V), Mo(V) and W(V) were studied by the EPR method in the temperature range from 293–77dg K. The spin-Hamiltonian parameters were determined. Conclusions were drawn about the structure of these complexes and about the bond character within the complexes. A multiplicity of the hyperfine splitting constants from Cr⁵³, Mo^95,97, and W¹⁸³ to the constant of additional hyperfine splitting from the p³¹ isotope is observed in diethyl phosphate complexes.     

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.     

Thin-layer chromatographic separation of Se(IV), Te(IV), V(V), and Mo(VI) as ternary mixtures and their identification with potassium thiocarbonate (PTC) reagent

Summary Thin-layer chromatography of Se(IV), Te(IV), V(V), and Mo(VI) as ternary mixtures has been described. The separation was effected on a silica gel G layer by employing two different solvent systems: diethyl oxalate-HCl (601v/v) andn-butyl acetate-HCl (400.6v/v). The chromatograms were visualized with 0.1M potassium thiocarbonate (PTC) spray and the limits of identification as determined, lie between 1.27 and 2.04g.

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Zusammenfassung Die Dünnschichtchromatographie ternärer Gemische von Se(IV), Te(IV), V(V) und Mo(VI) wurde beschrieben. Die Trennung wurde auf Schichten von Kieselgel G mit zwei verschiedenen Lösungsmittelsystemen durchgeführt: Diäthyloxalat—Salzsäure (601) und n-Butylacetat—Salzsäure (400,6). Die Chromatogramme wurden mit 0,1-m Kaliumthiocarbonat gesprüht. Die Nachweisgrenze liegt zwischen 1,27 und 2,04g.

     

氧化钪中Ti,Mo,W,V,Zr等难熔杂质光谱分析

本用提高样品蒸发速率的方法提高氧化钪中难熔杂质光谱分析灵敏度。采用一种特殊的阴极设计，配合使用Ｎ２＋Ａｒ气氛控制，在旋流气室中放电激发，取样仅５ｍｇ的条件下，光谱测定氧化钪中难烷质Ｔｉ，Ｚｒ，Ｍｏ，Ｗ，Ｖ灵敏度可达（１－３）×１０＾－４％。测定的相对标准偏差为９％－２７％。     

Haematein as a reagent for thorium, zirconium and uranium

Summary Haematein gives violet colored complexes with thorium and uranium and an orange colored complex with zirconium of the stoichiometric ratios 16, 13, and 11 respectively of the metal and the reagent (Job's method). The reagent and the complexes of thorium, uranium and zirconium show absorption maxima at 520–540 m, 520–540 m 500–520 m respectively. In observations at 540 m in 60 percent aqueous acetone 0.05 mg of thoria (a 12 fold excess of cerite earths has no influence), 0.029 mg U₃O₈ and 0.025 mg of zirconia may be determined. The spectral characteristics of the complexes indicate a similarity in character in spite of differences in stoichiometric composition.     

Preparation of Al,Cr, Nb,Mo, and W Monophosphides from a Lithium Metaphosphate Melt

Synthesis of a series of phosphides (AlP, CrP, NbP, MoP, and WP) by reactions of powdered metals with a melt of lithium metaphosphate LiPO₃ was studied. Thermodynamic parameters (H ⁰ _{2 9 8}, S ⁰ _{2 9 8}, G ⁰ _{2 9 8}, and G ⁰ _{1 2 7 3}) of the reactions were calculated and their temperature modes were optimized on the basis of the standard thermodynamic characteristics of the initial substances and the reaction products. X-ray patterns of the powders of the obtained compounds are presented.