Extractive-spectrophotometric determination of molybdenum with 4-unsubstituted-5-pyrazolones

A fairly sensitive and selective method for rapid determination of tracer amounts of molybdenum(V) as mixed-ligand complexes with thiocyanate and 4-unsubstituted-5-pyrazolones is described. The red complexes are extractable into chloroform from 1-5M hydrochloric or perchloric acid or 1-3M sulphuric arid media. The molar absorptivities are in the range 1.72-2.15 x 10(4)l.mole(-1).cm(-1) at 455 nm (lambda(max)). The method has been applied to the estimation of molybdenum in various synthetic and alloy-steel samples. In presence of excess of the reagent, Cu(II), Co(II), Mn(II), Fe(II), Fe(III), Al(III), Cr(III), Cr(VI), Ti(III), Ti(IV), Zr(IV), Hf(IV), V(III), V(IV), V(V), Nb(V), Ta(V), W(VI) and U(VI) do not interfere.     

Polarographische Bestimmung von Molybd?n neben anderen Metallen

Zusammenfassung Es wird eine polarographische Bestimmungsmethode für Molybdän in Gegenwart anderer Metalle beschrieben. Molybdän(VI) gibt in Anwesenheit einer 0,25 M Ammoniumtartratlösung eine gut reproduzierbare Reduktionsstufe bei E _1/2= – 1,27 V (GKE). Die Methode wurde mit guten Ergebnissen bei der Molybdänbestimmung in Legierungen (Fehler ±1%) und mineralischem Gestein (Fehler –2%) angewandt. Der störende Einfluß von größeren Mengen Chrom(VI) wird durch ein beschriebenes säulen-chromatographisches Trennverfahren mit Hilfe des Anionenaustauschers Wofatit SBW beseitigt. Ein zehnfacher Überschuß an W(VI), Mn(II), Ni(II), Cu(II) und Tl(I) sowie gleiche Mengen an Fe(II), Fe(III), Cd(II), Co(II), V(V) und Bi(III) stören nicht.

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Summary A polarographic method for the determination of molybdenum in presence of other metals is described. Molybdenum (VI) yields a well-defined cathodic wave in ammonium tartrate medium (0.25 M) at E _1/2= –1.27 V vs. S.C.E. The results obtained have been applied to the determination of molybdenum in ores (error ±1%) and alloys (error –2%). The interfering influence of greater amounts of chromium(VI) is eliminated by ion-exchange with the strongly basic anion-exchanger Wofatit SBW. A ten-fold excess of W(VI), Mn(II), Ni(II), Cu(II) and Tl(I) as well as equal amounts of Fe(II), Fe(III), Cd(II), Co(II), V(V) and Bi(III) do not interfere.

     

Preparation, characterization and application of an cellulose ion-exchanger with acetoacetamide functional groups

Summary A method is described for functionalizing acetoacetamide chelating groups onto microcrystalline cellulose (Cell-AcAc). This material shows a significant affinity for Fe(III), Cu(II) and U(VI) and no or very less affinity for the M(I) ions (M=Na, K), M(II) ions (M= Mg, Ca; Fe, Co, Ni, Zn), La(III) and Y(III) including Th(IV). The obtained K _d values offer a column separation method for U(VI) ions from the rest of above-mentioned metal ions except Fe(III). Cell-AcAc and its Cu(II) complexes are characterized by means of FT-IR spectra.

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Darstellung, Charakterisierung und Anwendung von Ionenaustauschmaterial aus Cellulose mit chemisch gebundener Acetoacetamid-Gruppe

Zusammenfassung Die Darstellung von immobilisiertem Acetoacetamid auf mikrokristallinem Cellulosepulver (Cell-AcAc) wird beschrieben. Der Ionenaustauscher Cell-AcAc hat eine ausgeprägte Affinität für Fe(III), Cu(II) and U(VI), aber nahezu keine für die M(I)-Ionen (M=Na, K) M(II)-Ionen (M=Mg, Ca; Fe, Co, Ni, Zn), La(III), Y(III) sowie Th(IV). Die erhaltenen K _d-Werte ermöglichen für U(VI)-Ionen eine quantitative säulen-chromatographische Trennung von den anderen genannten Kationen mit Ausnahme von Fe(III). Das Ionenaustauschmaterial Cell-AcAc und sein Cu(II)-Komplex wurden durch FT-IR-Spektren charakterisiert.

     

Synthesis and analytical properties of 3,4-dihydroxybenzaldehyde guanylhydrazone (3,4-DBGH)

Synthesis and analytical properties of 3,4-dihydroxy-benzaldehyde guanylhydrazone are described. The reagent was tested with 43 cations but only Co(II), Fe(II), Fe(III), Mo(VI), W(VI) and V(V) gave colored complexes. Spectral characteristics of the reagent are presented. Procedure for a selective a determination of Co(II), a sensitive determination of Fe(III) and determination of Mo(VI), W(VI) and V(V) in presence of large amounts of Fe(III) are reported. The method was applied for the determination (a) of Co(II) in presence of other cations at excess (b) of Fe(III) in a city drinking water sample without preconcentration and (c) of Mo(VI) in a standard steel sample.     

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.     

Voltamperometric determination of uranium and plutonium in alkaline solutions

The simultaneous determination of U(VI), Pu(VI), Pu(V) in 0.5–4.0 M NaOH has been elaborated by means of classical and differential pulse voltamperometry. U(VI) is determined with a dropping mercury electrode (DME) at the half-wave potential of E_1/2=–0.89 V vs. Ag/AgCl reference electrode due to reduction to U(V). The limiting current or peak heights are proportional to uranium(VI) concentration in the range of 1.3.10^–7–3·10^–4 M U(VI). Deviation from proportionality is observed for higher concentrations due to polymerization of uranates. Pu(VI) and Pu(V) are determined with a platinum rotating electrode at E_1/2=–0.02 V due to the reaction Pu(VI)+e^–»Pu(V) and with DME at E_1/2=–1.1 V due to the reduction to Pu(III). The limiting currents of both Pu(VI) and Pu(V) are proportional to their concentrations in the range of 4·10^–6–1.2·10^–3 M Pu. The determination of U(VI), Pu(VI), Pu(V) is not interfered by the presence of the following salts: 2M NaNO₃, 2M NaNO₂, 1.5M NaAlO₂, 0.5M NaF and ions of Mo(VI), W(VI), V(V), Cu(II). The presence of CrO ₄ ^2– and FeO ₂ ^– ions disturbs the determination of U(VI) in 1–4M NaOH, however, contribution of the reaction Fe(III)+e^–»Fe(II) to uranium reduction peak can be calculated from the height of the second peak Fe(II)+2 e^–»Fe(0).     

Bestimmung von Wolfram durch amperometrische Redoxtitration mit Dichromat

Zusammenfassung Wolfram wird in etwa 10 M salzsaurer Lösung durch überschüssiges Cr(II) reduziert. Dies ist experimentell einfacher als die Verwendung von Reduktorsäulen oder flüssigen Amalgamen. Die Titration mit Fe(III) oder Cr(VI) erfaßt zunächst den Reagensüberschuß; danach wird W(V) zu W(VI) oxidiert. Die potentiometrische Indikation ist gehemmt. Geeignet ist die Biamperometrie bei E _pol= 0,2 V. In einer Folgetitration können außer W auch Fe und Mo oder V bestimmt werden. Nur Ti stört. Gegenüber der reduktometrischen Titration von W(VI) mit Cr(II) ergeben sich als Vorteile, daß ein titerkonstantes Reagens benutzt werden kann und die Lösung nicht entlüftet werden muß. Probenvorbereitungen für Ferrowolfram, Stahl, Hartmetall-Vorlegierung und Wolframerz werden beschrieben.

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Determination of tungsten by amperometric redox titration with dichromate

Summary Tungsten is reduced by an excess of Cr(II) in about 10 M HCl. This is technically simpler than the use of reductor columns or liquid amalgams. Titration with Fe(III) or Cr(VI) first consumes the excess of Cr(II) and then oxidizes W(V) to W(VI). The potentiometric response of metal electrodes to W(V) is slow but biamperometric indication at E_pol=0.2 V applies well. A mixture of W, Fe and Mo can be analyzed in a consecutive titration. Only Ti interferes. As compared to the reductometric titration of W(VI) with Cr(II) the method uses a stable titrant and avoids deairating of the sample solution. Sample preparations for ferrotungsten, steel and wolframite ore are described.

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Die Publikation beruht auf den Diplomarbeiten von R. Kranich [8] und R. Aupers [1].

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Wir danken dem Fonds der Chemischen Industrie für finanzielle Unterstützung sowie J. Becker, U. Görs und G. Schrovenwever für ihre Mitarbeit.     

Liquid – liquid extraction behavior of V(IV) using phosphinic acids as extractants

The extraction behavior of V(IV) in the presence of Mo(VI), W(VI), U(VI), V(V), Ti(IV), Al(III), Cr(III), Fe(III), Mn(II), Zn(II) and Pb(II) has been studied using two alkylphosphinic acid extractants, Cyanex 272 and 301. The effect of various parameters, such as the nature of diluent, the type of mineral acid and the concentration of the acid, and metal ions has been investigated. The loading and recycling capacity of the extractants has been assessed. Based on the distribution data some binary separations from V(IV) were achieved. Received: 24 October 1996 / Revised: 2 July 1997 / Accepted: 5 July 1997     

Liquid – liquid extraction behavior of V(IV) using phosphinic acids as extractants

The extraction behavior of V(IV) in the presence of Mo(VI), W(VI), U(VI), V(V), Ti(IV), Al(III), Cr(III), Fe(III), Mn(II), Zn(II) and Pb(II) has been studied using two alkylphosphinic acid extractants, Cyanex 272 and 301. The effect of various parameters, such as the nature of diluent, the type of mineral acid and the concentration of the acid, and metal ions has been investigated. The loading and recycling capacity of the extractants has been assessed. Based on the distribution data some binary separations from V(IV) were achieved. Received: 24 October 1996 / Revised: 2 July 1997 / Accepted: 5 July 1997     

Selective separation of indium from zinc, lead, gallium and many other elements by cation-exchange chromatography in hydrohalic acid-acetone medium

Indium can be separated from Zn, Pb(II), Ga, Ca, Be, Mg, Ti(IV), Mn(II), Fe(III), Al, U(VI), Na, Ni(II) and Co(II) by selective elution with 0.50M hydrochloric acid in 30% aqueous acetone from a column of AG50W-X8 cation-exchange resin, all the other elements being retained by the column. Lithium is included in the elements retained by the column when 0.35M hydrochloric acid in 45% aqueous acetone is used for eluting indium, but the elution of indium is slightly retarded. Ba, Sr, Zr, Hf, Th, Sc, Y, La and the lanthanides, Rb and Cs should also be retained according to their distribution coefficients. Cd, Bi(III), Au(III), Pt(IV), Pd(II), Rh(III), Mo(VI) and W(VI) can be eluted with 0.20M hydrobromic acid in 50% aqueous acetone before the elution of indium, and Ir(III), Ir(IV), As(III), As(V), Se(IV), Tl(III), Hg(II), Ge(IV), Sb(III) and Sb(V), though not investigated in detail, should accompany these elements. Relevant distribution coefficients and elution curves and results for analyses of synthetic mixtures of indium with other elements are presented.     

The spectrophotometric determination of vanadium after extraction as vanadium(III) ferronate by tribenzylamine

Vanadium(III) obtained by dithionite reduction of vanadium(V) can be extracted as its ferron complex with tribenzylamine in chloroform from 0.05 M sulphuric acid. Vanadium (0–5 μg ml^-1) is determined spectrophotometrically at 430 nm with a sensitivity of 0.0028 μg V cm^-2. Al(III), Co(II), Ni(II), Fe(II, III), Hg(II), Si(IV), Be(II), Mg(II), Ca(II), Sr(II), Ba(II), Cr(VI, III), W(VI), Zn(II), U(VI), Mn(II). Pb(II), Cu(II), Cd(II) and Th(IV) do not interfere; only Mo(VI), Ti(IV), Zr(IV). Bi(V) and Sn(II) interfere. A single determination takes only 7 min. The extracted complex is V^III (R-3H.TBA)₃ where R = C₉H₄O₄NSI. The method is satisfactory for the determination of vanadium in steels, alum and other samples without preliminary separations.     

Selective and quantitative separation of zinc and lead from other elements by cation-exchange chromatography in hydrohalic acid-acetone solutions

Zinc and lead can be separated from Cd, Bi(III), In and V(V) by eluting these elements with 0.2M hydrochloric acid in 60% acetone from a column of AG50W-X8 cation-exchange resin, zinc and lead being retained. Mercury(II), Tl(III), As(III), Au(III), Sn(IV), Mo(VI), W(VI) and the platinum metals have not been investigated quantitatively, but from their distribution coefficients, should also be eluted. Vanadium(V), Mo(VI) and W(VI) require the presence of hydrogen peroxide. Zinc and lead can be eluted with 0.5M hydrochloric acid in 60% acetone or 0.5M hydrobromic acid in 65% acetone and determined by AAS; the alkali and alkaline-earth metal ions, Mn(II), Co, Ni, Cu(II), Fe(III), Al, Ga, Cr(III), Ti(IV), Zr, Hf, Th, Sc, Y, La and the lanthanides are retained on the column, except for a small fraction of copper eluted with zinc and lead. Separations are sharp and quantitative. The method has successfully been applied to determination of zinc and lead in three silicate rocks and a sediment.     

Extractive separation and spectrophotometric determination of tungsten as phosphotungsten blue

Phosphotungsten blue is produced by tin(II) reduction of tungstate solution complexed with phosphate at a w/w ratio of W/P = 5, in 4M hydrochloric acid medium, and extracted with isoamyl alcohol; thus tungsten is separated from Fe(III), Ni, Co, Cr(III), V(V), As(V), Sb(III), Bi, Si, U(VI), Ca and Cu(II). In presence of bismuth (0.5 mg/ml), 99.7% W is separated in a single extraction. After alkaline back-extraction, tungsten is determined spectrophotometrically as phosphotungsten blue; it is measured at 930 nm in aqueous solution or at 900-960 nm after isoamyl alcohol extraction, the Beer's law ranges being 0.08-0.6 and 0.16-0.72 mg/ml respectively. The methods are shown to give satisfactory results in the analysis of practical samples containing some milligrams of tungsten.     

Voltammetry and controlled-potential coulometry with boron carbide electrodes

With the boron carbide electrode, E_{p$\text{p}\text{2}$} values were determined for the reduction of the following ions: Cd(II), Co(II), Cu(II), Fe(III), Ni(II), Pb(II), Ru(IV), Sb(V), and U(VI). The linear dependence of peak current on concentration is demonstrated for the U(VI) → U(IV) and Fe(III) → Fe(II) reductions at the boron carbide electrode. The suitability of the electrode for the controlled-potential coulometric ti trations of Fe(II) → Fe(III), Fe(III) → Fe(II), and U(VI) → U(IV) was studied; the results were inconclusive because of the small surface area that could be used conveniently and the possibility of oxygen leaks in the cell.     

Extraction of molybdenum(V) as its ferron complex with trioctylamine in chloroform from a sulphuric acid medium

A simple, rapid, and highly selective method for the separation of molybdenum from a large number of elements of analytical importance has been developed. The method is based on the extraction of a Mo(V)-ferron (7-iodo-8-hydroxyquinoline-5-sulphonic acid) complex into trioctylamine-chloroform in a sulphuric acid medium using ascorbic acid as a reductant. Many elements such as Re(VII), W(VI), U(VI), Th(IV), Cr(III), Cr(VI), V(V), Ce(IV), Ru(III), Co(II), Ni(II), Mn(II), Fe(II), Fe(III), Cd(II), Mg(II), Cu(II), Al(III), Zn(II), Pb(II), Ag(I), and As(V) are not extracted under the conditions proposed and, thus, molybdenum can be easily separated without any interference. Sulphate, chloride, nitrate, phosphate, and oxalate anions have no effect on the extraction of molybdenum. However, zirconium and palladium interfere seriously. The ratio of Mo: ferron: TOA in the extracted species is found to be 1: 1: 3 using Job’s method of continuous variations. This value has been further confirmed by the mole-ratio method. The text was submitted by the authors in English.     

Solvent extraction and spectrophotometric determination of palladium(II) with 7-iodo-8-hydroxyquinoline-5-sulphonic acid

An extractive spectrophotometric procedure has been developed for the determination of palladium (II) at microgram levels. The palladium(II) chelate of 7-iodo-8-hydroxyquinoline-5-sulphonic acid is extracted into n-butanol. Extraction is maximal (95%) from 0.2M perchloric acid. Beer's law is valid at 430 nm over a wide range of palladium concentration from 2.5 ppm. The molar absorptivity is 958 1.mole(-1).mm(-1). The system can tolerate a large excess of Co(II), Ni(II), Rh(III), Pt(IV), Cr(III), W(VI), chloride, phosphate, citrate and tartrate. Small quantities of Ru(III), IR(III) and EDTA do not interfere, but serious interference is caused by Fe(III), V(V), Mo(VI) and Os(VIII).     

Sorption-spectroscopy and test determination of uranium(VI) and iron(III) from a single sample on the solid phase of fiber materials filled with an AB-17 ion exchanger

Diffuse reflectance spectroscopy has been used for the study of the sorption of malonate and glycolate complexes of uranium(VI) and iron(III), present simultaneously in solution, onto the solid phase of fiber materials filled with an AB-17 anion exchanger. In the form of malonate complexes uranium(VI) is determined in 0.5 M HCl on substrate discs with immobilized Arsenazo III, while iron(III) is determined on substrate discs with potassium thiocyanate in 0.5 M HCl. The dependence of the analytical signals on the concentrations of U(VI) and Fe(III) is linear in the ranges 0.02–0.16 μg/mL; the detection limit is 0.01 μg/mL. The possibility of analysis of U(VI) and Fe(III) mixtures in ratio from 1: 5 to 5: 1 in the presence of 2-fold concentrations of Zr(IV), Th(IV), and Ti(IV), 5-fold concentrations of Bi(III), 10-fold concentrations of Cu(II), 20-fold concentrations of La(III), 100-fold concentrations of Ni(II) and Zn(II), and 200-fold concentrations of Co(II) and Ca(II) has been demonstrated. Standard color scales in the concentration range from 0.02 to 0.2 μg/mL have been used for the visual determination of uranium(VI) and iron(III).     

Electrometric titrations of Cr(VI), Mn(IV), V(V), Co(III) and U(VI) with a standard iron(II) solution in alkaline media containing hexitols

Direct and indirect potentiometric, bipotentiometric and biamperometric titrations with a standard iron(II) solution are described for some inorganic compounds in alkaline media containing hexitols (mannitol, dulcitol and sorbitol). The optimal conditions for titrations based on the Cr(VI) → Cr(III), Mn(IV) → Mn(III) → Mn(II), V(V) → V(IV), Co(III) → Co(II) and U(VI) → U(IV) systems are discussed. Of the hexitols studied, sorbitol has the greatest effect on the value of the redox potential of the Fe(III)/Fe(II) system; the E_f° value is about —1.10 V vs. SCE.     

Extraction and separation of bismuth(III) from steel and bismuth-base alloys

Summary Separation of bismuth(III) from iron(III), molybdenum(VI), vanadium(V), chromium(VI), titanium(IV), antimony(III), lead(II), beryllium(II), uranium(VI), hafnium(IV), indium(III) and zirconium (IV) is achieved by solvent extraction with high molecular weight amines from sodium succinate solution adjusted to suitable pH. Bismuth(III) is stripped from the organic phase and determined spectrophotometrically. The method is shown to be applicable to bismuth alloys.

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Extraktion und Trennung von Wismut(III) aus Stahl und wismuthältigen Legierungen

Zusammenfassung Wismut(III) läßt sich von Fe(III), Mo(VI), V(V), Cr(VI), Ti(IV), Sb(III), Pb(II), Be(II), U(VI), Hf(IV), In(III) und Zr(IV) durch Extraktion mit hochmolekularen Aminen aus Natriumsuccinat bei geeignetem pH trennen. Bi(III) wird dann von der organischen Phase getrennt und spektralphotometrisch bestimmt. Das Verfahren eignet sich für Wismutlegierungen.

     

Combination collectors in adsorption colloid flotation for multielement determination in waters by neutron activation

A method is described for the collection of small amounts of both anions and cations in water samples by adsorption colloid flotation with a combination collector, prior to quantitation by neutron activation. In the presence of 20 mg of iron(III) and 2 ml of 0.1 M ammonium pyrrolidinedithiocarbamate, As(V), Cd(II), Co(II), Cu(II), Hg(II), Mo(VI), Sn(IV), Sb(III), Te(VI), Ti(IV), U(VI), V(V) and W(VI) are quantitatively collected from 1 -l samples at a pH 5.8 ± 0.1; sodium dodecyl sulfate and sodium oleate are used as surfactant. Recoveries for all the elements tested are greater than 90%. Results for a number of elements in sea waer and an NBS water standard, SRM 1643a, are given.