Individual and sequential flow injection spectrophotometric determination of vanadium(V) and titanium(IV)

Summary Methods for the individual and sequential flow injection spectrophotometric determination of vanadium(V) and titanium(IV) are proposed, based on the formation of peroxo complexes. The detection limits are 1.0 × 10^–5 mol/l V (120 l) and 2.5 × 10^–6 mol/l Ti (80 l). A cation exchange resin mini-column is incorporated on-line into the vanadium manifold to remove the titanium complex and allow the vanadium to be determined selectively. A normal injection valve is used for the individual determinations, but it is modified for determination of V(V)/–Ti(IV) mixtures in order to introduce two samples sequentially into the reagent stream. One passes through a cation exchanger minicolumn, the other through an empty column, before reaching the detector. The former allows V alone to be measured, the latter V+Ti.

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Individuelle und sequentielle spektralphotometrische Fließinjektionsbestimmung von Vanadium(V) und Titan(IV)

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Dedicated to Prof. Dr. G. Tölg on the occasion of his 60th birthday     

Adsorptive stripping voltammetric measurements of trace amounts of platinum(II) and ruthenium(III) in the presence of 1-(2-pyridylazo)-2-naphthol

An extremely sensitive stripping voltammetric procedure for low level measurements of platinum (II, IV) or ruthenium (III, IV) is reported. The method is based on the interfacial accumulation of the platinum (II) or ruthenium (III)-1-(2-pyridylazo)-2-naphthol complex on the surface of a hanging mercury drop electrode, followed by the reduction of the adsorbed complex during the cathodic scan. The peak potential was found to be –0.8 V vs. Ag/AgCl electrode and the reduction current of the adsorbed complex ions of platinum (II) or ruthenium (III) was measured by differential pulse cathodic stripping voltammetry. The optimum experimental conditions were: 1.5×10^–7 mol/l of 1-(2-pyridylazo)-2-naphthol solution of pH 9.3, preconcentration potential of –0.2 V, accumulation time of 3 min and pulse amplitude of 50 mV with 4 mV s^–1 scan rate in the presence of ethanol-water (30% v/v) — sodium sulphate (0.5 mol/l). Linear response up to 6.4 × 10^–8 and 5.1 × 10^–8 mol/l and a relative standard deviation (at 1.2×10^–8 mol/l) of 2.4 and 1.6% (n=5) for platinum (II) and ruthenium (III) respectively were obtained. The detection limits of platinum and ruthenium were 3.2×10^–10 and 4.1×10^–10 mol/l, respectively. The electronic spectra of the Pt(II) — PAN and Ru(III) — PAN complexes were measured at pH 9.3 and the stoichiometric ratios of the complexes formed were obtained by the molar ratio method. The effects of some interfering ions on the proposed procedure were critically investigated. The method was found suitable for the sub-microdetermination of ruthenium (IV) and platinum (IV) after their reduction to ruthenium (III) and platinum (II) with sulphur dioxide in acid media. The applicability of the method for the analysis of binary mixtures of ruthenium (III) and (IV) or platinum (II) and (IV) has also been carried out successfully. The method is simple, rapid, precise, and promising for the determination of the tested metal ions at micro-molar concentration level.     

Spectrophotometric extractive determination of Ti in mineral samples and aluminium alloys as a mixed-ligand Ti(IV)-salicylhydroxamic acid-thiocyanate complex

A sensitive method for the determination of titanium, based on the formation of a mixed-ligand Ti (IV)-salicylhydroxamic acid-thiocyanate complex and extraction of this into a liquid ion-exchanger phase has been developed. The extract has maximum absorbance at 400–460 nm and the apparent molar absorptivity is 1.8 × 10⁴l · mole^–1 · cm^–1 at 420 nm. The system obeys Beer's law at 420 nm in the range 0.16–3.20 mg/1 Ti, the detection limit being 0.1 mg/1. The method is found suitable for determination of titanium in aluminium alloys and silicate rocks.     

2-(2-Thiazolylazo)-pcresol (TAC) as a reagent for the spectrophotometric determination of titanium (IV)

The reaction between titanium(IV) and 2-(2-thiazolylazo)-p-cresol-(TAC) in aqueous methanol media at apparent pH 4.0–5.6 results in a intensely coloured complex that is stable for at least 2 h. The combining ratio is 1 1 cation TAC. Beer's law is obeyed up to 5.0 g/ml titanium(IV) at 580 nm. The apparent molar absorptivity at 580 nm is 9.82.10³ l.mole^–1.cm^–1 and the detection limit obtained was 5 ng/ml titanium (IV). A spectrophotometric method for the simultaneous determination of titanium and iron with TAC is proposed.     

Simultaneous determination of sodium dodecyl sulphate and sodium linear-dodecylbenzenesulphonate with 1-stearyl-4-(4-aminonaphthylazo)-pyridinium bromide by spectrophotometry

A rapid and sensitive spectrophotometric method for the simultaneous determination of sodium dodecyl sulphate (SDS) and sodium linear-dodecylbenzenesulphonate (DBS) with 1-stearyl-4-(4-aminonaphthylazo)-pyridinium bromide (SAPB) is described using the difference at the maximum absorption wavelength of the SDS- and the DBS-ion associate. SDS and DBS have been determined independently by measuring their respective absorbances at the maximum absorption wavelength. The apparent molar absorptivities of the SDS- and the DBS-ion associate are 8.0×10⁴ l mol^–1 cm^–1 at 445 nm and 4.5×10⁴ l mol^–1 cm^–1 at 424 nm, respectively. The calibration graph for SDS is linear in the range from 0.1 to 1.0×10^–6 mol/l in the presence of 1.2×10^–6 mol/l DBS and for DBS from 0.8 to 2.0×10^–6 mol/l in the presence of 8.0×10^–7 mol/l SDS. The relative standard deviation (n=15) for 8.0×10^–7 mol/l SDS is 3.4% and for 1.6×10^–6 mol/l DBS 2.1%. The proposed method has been applied to the simulatenous determination of SDS and DBS in river water samples.     

Extraction and spectrophotometric determination of titanium(iv) with 3-hydroxy-2-methyl-1-(4-tolyl)-4-pyridone

Titanium(IV) in sulphuric, perchloric and hydrochloric acid media reacts with 3-hydroxy-2-methyl-1-(4-tolyl)-4-pyridone (HY) to give a complex which is extractable into chloroform. The composition of the extractable complex depends on the acidity of the aqueous phase and on which mineral acid is used. The mixed titanium-perchlorate-HY complex which is formed in the presence of excess of perchlorate is the most suitable for the spectrophotometric determination of titanium. The molar absorptivity of the complex is 1.6×10⁴1·mole^–1·cm^–1 at 355 nm. The optimum titanium concentration range is 0.5–6,g/ml. The method has been successfully applied to the determination of titanium in samples of bauxite and alumina refractory.     

Spectrophotometric determination of anionic surfactants in tap and river waters with 1-(10-bromodecyl)-4-(4-aminonaphthylazo)-pyrimidinium bromide

Summary A new cationic dye, 1-(10-bromodecyl)-4-(4-aminonaphthylazo)-pyridinium bromide, was synthesized and evaluated as a new reagent for the determination of anionic surfactants. The reagent reacts with anionic surfactants, such as sodium dodecylsulphate and sodium dodecylbenzenesulphonate, to produce an ion associate in an aqueous medium. The colour change occurs simultaneously, and the colour development is very stable. This makes it possible to determine anionic surfactants directly by spectrophotometry without solvent extraction. The stoichiometric ratio of the ion associate was found to be 1:1 by the mole ratio method. The calibration graph was linear up to 2.5×10^–6 mol/l. The apparent molar absorptivity of the ion associate was 5.3×10⁴ l mol^–1 cm^–1 (at 595 nm). The relative standard deviation (n=10) for 1.2×10^–6 mol/l sodium dodecylsulphate was 4.9%. The proposed method was applied to the determination of anionic surfactants in tap and river waters.     

Determination of cobalt in the presence of high concentrations of zinc by differential pulse polarography

Summary Cobalt(II) can be determined in 0.1 mol/l Na₃citrate + 0.1 mol/l NH₄Cl + 0.08% dimethylglyoxime as supporting electrolyte in the presence of a 50 000-fold excess of zinc by differential pulse polarography. The limit of determination is 4.2×10^–5 mol/l Co (2.5 mg/l). Linear calibration curves are obtained within the range of 1×10^–7 to 5×10^–6 mol/l cobalt without zinc and in the presence of 5×10^–3 mol/l Zn. The analytical method developed is suitable for the determination of cobalt in zinc plant solutions.

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Cobaltbestimmung in Gegenwart hoher Zinkkonzentrationen mit Hilfe der Differential-Puls-Polarographie

     

Spectrophotometric determination of iron in alloys and ores with 1-(2-pyridylmethylideneamine)-5-(salicylideneamine)thiourea

Summary A spectrophotometric method for the determination of iron is described. The green Fe(II) complex is formed at pH 4.8 in a medium containing 40% dimethylformamide and 0.8 g/l ascorbic acid, and the absorbance is measured at 635 nm. The molar absorptivity is 5.7×10³lo·mole^–1·cm^–1. The method has been applied with good results to the determination of iron in six alloys and ores.

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Spektrophotometrische Bestimmung von Eisen in Legierungen und Erzen mit 1-(2-Pyridylmethylidenamin)-5-(salicylidenamin)-thioharnstoff

Zusammenfassung Ein spektrophotometrisches Verfahren zur Eisenbestimmung wurde beschrieben. Der grüne Fe(II)-Komplex bildet sich bei pH 4,8 in einem Medium aus 40% Dimethylformamid und 0,8 g/l Askorbinsäure. Die Absorbanz wird bei 635 nm gemessen. Die molare Absorptivität beträgt 5,7× 10³l·mol^–1·cm^–1. Die Methode gab gute Resultate bei der Bestimmung von Eisen in sechs Legierungen und Erzen.

     

Solvent extraction and spectrophotometric determination of titanium (IV) with 3-phenyl-3-methyl-2-mercaptopropenoic acid by use of the synergistic effect of pyridine

Summary The distribution equilibria of 3-phenyl-3-methyl-2-mercaptopropenoic acid (PhMMP), pyridine and the titanium (IV)-PhMMP complex in the presence of pyridine have been studied in the chloroform-water system. An extraction-photometric method for the determination of micro amounts of titanium has been developed. The synergistic effect of pyridine, and the influence of pH, the reagent concentration and the presence of electrolytes and masking agents on the equilibrium have been determined. From slope analysis of the distribution curves, the composition of the extracted species has been found to be Ti(OH)₂(HR)₂·py. The complex is extracted quantitatively. Beer's law is obeyed over the range 0.09–4.30g/ml titanium (IV) and the molar absorptivity is 1.30×10⁴1·mole^–1·cm^–1 at 447 nm. The method has been applied to the determination of titanium in ceramics.

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Über die Extraktion und spektrophotometrische Bestimmung von Titan(IV) mit 3-Phenyl-3-methyl-2-mercaptopropensäure mit Hilfe der synergistischen Wirkung des Pyridins

Zusammmenfassung Das Verteilungsgleichgewicht von 3-Phenyl-3-methyl-2-mercaptopropensäure (PhMMP), Pyridin und Titan-PhMMP-Komplex in Gegenwart von Pyridin wurde in einem Wasser-Chloroform-System untersucht. Eine extraktionsphotometrische Methode für die Bestimmung von Mikromengen Titan(IV) wurde ausgearbeitet. Die synergistische Wirkung des Pyridins sowie der Einfluß des pH, des Reagens und der Gegenwart von Elektrolyten und maskierenden Reagenzien in der wäßrigen Phase auf das Gleichgewicht wurden bestimmt. Aus der Richtung der Verteilungskurven wurde für den extrahierten Komplex die Zusammensetzung Ti(OH)₂(HR)₂·py ermittelt. Der Komplex wird quantitativ extrahiert. Das Beersche Gesetz ist von 0,09–4,30g·ml^–1 Ti(IV) erfüllt, der molare Absorptionskoeffizient ist 1,13·10⁴1·mol^–1·cm^–1; die Sandell-Empfindlichkeit beträgt 3,7ng·cm^–2 bei 447 nm. Diese Methode wurde für die Bestimmung von Titan in keramischem Material verwendet.

     

Determination of Mo(VI) with 2-benzylideneiminobenzohydroxamic acid (2-BIBH) in urine by cathodic stripping voltammetry

Summary Controlled adsorptive accumulation of Mo(VI)-2-BIBH at the hanging mercury drop electrode (HMDE) provides the basis for the direct stripping measurement of Mo(VI) in nanomolar concentration. The cathodic stripping response is evaluated with respect to experimental parameters such as preconcentration time, preconcentration potential and others. A differential pulse cathodic stripping voltammetric method for the determination of Mo(VI) with 2-BIBH in urine is proposed. The detection limit is 10^–9 mol/l Mo(VI), standard deviation for 5×10^–8 mol/l is ±1.58×10^–9 mol/l.

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Bestimmung von MolybdÄn(VI) mit 2-BenzylideniminobenzohydroxamsÄure (2-BIBH) in Harn durch kathodische Stripping-Voltammetrie

     

2-(5-Nitro-2-Pyridylazo)-5-(N-Propyl-N-Sulfopropylamino)Phenol as a new analytical reagent for flow-injection spectrophotometric determination of trace vanadium(V)

A flow injection method using 2-(5-nitro-2-pyridylazo)-5-(N-propyl-N-sulfopropylamino)phenol-(Nitro-PAPS) as a new chromogenic reagent is presented for sensitive and rapid determination of vanadium. Nitro-PAPS reacts with vanadium(V) in weakly acidic medium to form a water soluble complex of molar absorptivity of 8.0 × 10⁴L mol^–1 cm^–1 at 592 nm (maximum absorption wavelength), which permits the straightforward application of a flow injection system to the sensitive determination of vanadium. Under the optimum conditions established, a linear calibration graph was obtained in the range 1–120 ng mL^–1. The relative standard deviation for 60 ng mL^–1 vanadium was 2.2% (n = 5) and the limit of detection was 1 ng mL^–1. The sample throughput is about 40 h^–1. Most inorganic and organic anions examined did not interfere even at concentrations of 3000–6000 times of vanadium. Interference from cobalt(II), copper(II) and nickel(II) at 200ng mL^–1 levels can be overcome by the addition of N-(dithio-carboxy)sarcosine. The recoveries for each 20 and 10 ng mL^–1 vanadium added to the river water were 98 and 97%, respectively.The authors express their thanks to Miss Miho Suzuki and Miss Hiroyo Yamada for their experimental assistance in part.     

2,2′-Dichinoxalyl — ein neues Reagens zur spektrophotometrischen Bestimmung von Titan(III)

Zusammenfassung 2,2-Dichinoxalyl ist ein geeignetes Reagens zur spektrophotometrischen Bestimmung von Titan(III) in salzsaurem Medium. Das molare Verhältnis der Reaktionspartner 2,2-DChx: Ti(III) beträgt 1 2. Die bei der Redoxreaktion entstehende blaue Verbindung weist ein Absorptionsmaximum bei 680 nm auf. Der molare Extinktionskoeffizient beträgt =2,9·10⁴. Im Ti (III)-Konzentrationsbereich von 2,09 · 10^–6 bis 1,04 · 10^–4 erhält man eine geradlinige Eichkurve. Die beschriebene Methode eignet sich zur Bestimmung von Titan in Ilmeniten und Titanlegierungen. 2,2-DChx kann auch zur extraktions-kolorimetrischen Bestimmung von Ti(III) verwendet werden.

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2,2-Diquinoxalyl — A new reagent for spectrophotometric determination of titanium(III)

Summary 2,2-Diquinoxalyl (DQux) is a suitable reagent for spectrophotometric determination of titanium (III) in HCl medium. The molar relationship of the reaction partners DQux Ti(III) is 12. The blue compound arising in the redox reaction exhibits an absorption maximum at 680 nm. The absorptivity is =2.9×10⁴. In the Ti(III) concentration range from 2.9×10^–6 to 1.04×10^–4 a straight-line calibration curve is obtained. The method described is suitable for determination of titanium in ilmenites and titanium alloys. DQux can also be used for extraction colorimetric determination of Ti(III).

     

Spectrophotometric determination of manganese with derivatives of 1,3,3-trimethyl-2-[3-(1,3,3-trimethyl-1,3- H-indol-2-ylidene)propenyl]-3 H-indolium

A new, simple, rapid, and sensitive spectrophotometric method has been developed for the determination of manganese in sewage. The method is based on the reaction of manganese with derivatives of 1,3,3-trimethyl-2-[3-(1,3,3-trimethyl-1,3-H-indol-2-ylidene)propenyl]-3H-indolium to form a colored ion associate with a sensitive absorption maximum at 560 nm. The appropriate reaction conditions have been established: pH 8.5–10.0, 1.25–2.3×10^–3 mol L^–1 1-nitroso-2-naphthol, and 1.6–2.4×10^–4 mol L^–1 dye reagent. Beer's law is obeyed for manganese concentrations up to 4.2 mg L^–1. The limit of detection is 0.01 mg L^–1 Mn²⁺; the molar absorptivity of the ion associate was 7.5×10⁴ L mol^–1 cm^–1. The effect of various foreign ions was examined. A reaction mechanism is suggested. The developed procedure was tested for determination of manganese in sewage with satisfactory precision and accuracy.     

Determination of Selenium(IV) by Stripping Voltammetry at a Mercury-Film Electrode

A procedure was proposed for the determination of selenium(IV) by stripping voltammetry on a mercury-film electrode at an electrolysis potential of +0.4 V versus the saturated silver–silver chloride reference electrode in a 1 M H₂SO₄ solution. The current of the cathodic peak is a linear function of the selenium(IV) concentration in the range from 5 × 10^–3 to 3 × 10^–1 mg/L (6.3 × 10^–8 to 3.8 × 10^–6 M) at a time of electrolysis of 30 s (t _el). The detection limit for selenium is 1 × 10^–4 mg/L (1.3 × 10^–9 M) at t _el = 300 s. It was shown that selenium(IV) can be determined in the presence of 10 mg/L Zn(II), 1 mg/L Cd(II), 0.5 mg/L Pb(II), and 0.2 mg/L Cu(II). A procedure for the determination of selenium in natural, mineral, and potable water was proposed.     

Spectrophotometric determination of palladium(II) with phenylfluorone in the presence of hexadecylpyridinium bromide

Phenylfluorone reacts with palladium(II) in the presence of hexadecylpyridinium bromide to form a water-soluble chelate with an absorption maximum at 630 nm, the absorbance being constant in the pH-range of 9.0–10.2. At this wavelength Beer's law is obeyed up to 7.25 × 10^–5 mol/L palladium(II). The sensitivity is very high and the molar absorptivity is 8.5 × 10⁴ L mol^–1 cm^–1, permitting the determination of palladium(II) at µg level. The ratio of palladium to phenylfluorone in the complex is 1:1. The method has successfully been applied to the determination of palladium in titanium alloys.     

Extraction-spectrophotometric determination of trace iron (II) in sea water with 2-[2-(3,5-dibromopyridyl)azo]-5-diethylaminobenzoic acid

An extraction-spectrophotometric method is described for the determination of traces of iron(II) with 2-[2-(3,5-dibromopyridyl)azo]-5-diethyl-aminobenzoic acid. The reagent forms a stable and blue 12 iron/reagent complex that can be extracted into chloroform. The apparent molar absorptivity of the iron(II) complex is 1.09 × 10⁵ 1 mol^–1 cm^–1 at 624 nm in chloroform. The reagent is relatively selective; interferences from cobalt, copper, nickel and vanadium can be removed by using dimethylglyoxime and EDTA. The method is applied to the determination of iron (II) in sea water and aluminium alloys with good precision and accuracy.     

Determination of oxytetracycline in urine and human serum by differential pulse polarography

Summary A differential pulse polarographic method for the determination of oxytetracycline in urine and human serum in acid media (HClO₄ of pH 2) is proposed. The effects of the amount of sample taken and the concentration of HClO₄ present were investigated. The detection limit was 5.5×10^–6 mol/l. The standard deviation of the determination of 5.5×10^–5 mol/l of oxytetracycline in 2 ml of urine was 1.7×10^–6 mol/l and that of the determination of 5.5×10^–5 mol/l of oxytetracycline in 2 ml of human serum was 1.9×10^–6 mol/l.

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Bestimmung von Oxytetracyclin in Urin und Humanserum durch Differential-Pulspolarography

     

Analytical separation of antimony(III) from bismuth(III), lead(II), gallium(III), thallium(III), tellurium(IV) and tin(IV) with cyanex 302

A method is proposed for the separation of antimony(III) (100–400 g) from bismuth(III), lead(II), gallium(III), thallium(III), tellurium(IV) and tin(IV) from an aqueous solution of pH 0.5–1.5 using 8×10^–3–1×10^–2 mol dm^–3 cyanex 302 dissolved in toluene as an extractant. The antimony is stripped from the cyanex phase with water and determined spectrophotometrically with iodide. Various experimental parameters are optimized and the probable 13 stoichiometry of the extracted species is evaluated. The method is applicable to the analysis of alloys and pharmaceutical samples. The separation and determination take only 20 min.     

Voltammetric determination of traces of cobalt(II) with a chemically modified carbon paste electrode

Summary A new preconcentration and voltammetric determination method for cobalt(II) in aqueous solution with a chemically modified electrode is proposed. The accumulation behaviour and voltammetry of cobalt(II) has been investigated with a carbon paste electrode modified with cationexchanger and 1,10-phenanthroline. The electrochemical response is characterized with respect to carbon paste composition, pH, preconcentration time, cobalt(II) concentration and other variables. For a 3-min preconcentration time, the electrode gives good linearity for 1×10^–7 to 4×10^–6 mol/l Co(II), a detection limit of 8×10^–8 mol/l. The response can be reproduced with a 4.0% relative standard deviation. The method is fairly free from many coexisting ions interferences. A rapid and convenient renewal procedure allows the use of a single electrode in multiple analytical determinations over several days. Satisfactory results are obtained for the determination of cobalt in a variety of certified standard reference materials.