Spectrophotometric methods for the determination of osmium-I Extraction and ultraviolet spectrophotometric determination of osmium tetroxide

An ultraviolet spectrophotometric method is presented for the détermination of milligram quantities of osmium in solutions of uranyl sulphate. Osmium is first oxidised to the octovalent state and the osmium tetroxide which is formed, is selectively extracted with chloroform. The ultraviolet absorption spectrum'of osmium tetroxide in chloroform has a series of absorption bands with peak absorbancies at 282, 289, 297, 304 and 312 mμ and molar absorbancy indexes of 1870, 1760,1640, 1400 and 1000, respectively. For each wavelength, the optimum concentration range for the determination of osmium was evaluated. From 0.4 to 3.3 mg of osmium can be determined with a coefficient of variation of 3%. Of the elements tested only chloride and octovalent ruthenium interfere; however, both of these interferences can be eliminated.     

Spectrophotometric methods for the determination of osmium-III Reaction of osmium tetroxide with 1:5-diphenylcarbo- hydrazide in aqueous solutions followed by extraction of the complex

-A spectrophotometric method has been developed which is applicable to the determination of extremely small quantities of osmium. Osmium is oxidised to the octovalent state, then added to an acidic aqueous solution containing 1:5-diphenylcarbohydrazide (DPC). After heating the aqueous solution to 65°, the osmium-DPC complex is extracted with chloroform. A molar absorbancy index of about 150,000 is obtained. From 7 to 25 μg of osmium can be determined with a coefficient of variation of 6%. It was established that Fe^III, Cu^II, Ru^III and Au^III seriously interfere in the determination of osmium by this method, while Cr^VI, Ni^II, Mo^VI, Ir^III and chloride interfere only when present in relatively high concentrations.     

Determination of Osmium(VIII) by Flow Injection-Kinetic Methods Using Bromopyrogallol Red and Hydrogen Peroxide

A new flow injection-kinetic method has been developed for the determination of trace amount of osmium(WI), based on its catalytic effect on the bromopyrogallol red and hydrogen peroxide reaction. The reaction is followed spectrophotometrically by measuring the decrease in absorbance at 559 nm. The calibration graph for osmium(VIII) is linear over the range from 0.0040 to 0.10 μg/ml and the detection limit and sampling frequency are 0.0030 μg/ml and 47 per hour, respectively. The proposed method was applied to the determination of trace amounts of osmium in refined ores and chlorination residues with satisfactory results.     

Spectrophotometric determination of osmium with quinisatin oxime

A spectrophotometric determination of osmium has been developed, based on the purple color (absorption maximum at 515 mμ) formed by reaction of osmium with quinisatin oxime in buffered solution of dimethyl formamide and methanol. The absorbances are reproducible, and the system conforms to Beer's law. The method compares favorably in sensitivity with existing methods for osmium. The optimum concentration range (for 1 cm optical path) is about 2 to 10 p.p.m. of osmium. Although the maximum color develops slowly, it is stable for 7 days or longer. Several elements, notably iron, cobalt, and ruthenium, interfere, so that separation, is necessary. A reaction ratio of 1:2 for osmium and quinisatin oxime was clearly indicated; some evidence was also obtained for the presence of higher complexes.     

Spectrophotometric determination of rhodium using acenaphthenequinone monoxime (AQM)

A water-soluble dark-brown complex formed by osmium with acenaphthenequinonemonoxime exhibits an absorption maximum at 430 nm. The composition of the complex comes out to 1:2 (metal:ligand) as revealed by Job's method of continuous variations, logarithmic method, and Gerade method of Asmus. The pH range for complete formation of the complex is 6.5–8.5. Its sensitvitiy has been found to be 0.0323 μg/cm². The effect of diverse ions has also been investigated.     

The determination of traces of osmium in ruthenium sponge by neutron activation analysis

Tracer techniques confirmed that a quantitative separation of osmium and ruthenium is possible by distillation from a hydrogen peroxide-sulphuric acid solution. Osmium distils quantitatively as OsO₄ at a temperature of 105 ± 5° in about 30 min. The ruthenium contamination is approximately 0.01 %.In the present work a neutron activation analysis is described for the determination of traces of osmium in ruthenium sponge. When quantities of osmium below 30 p.p.m. are determined, the ruthenium contamination of the distillate must be taken into account, when the measurement is made with a 3” x 3” NaI(Tl) crystal. This can easily be achieved by measurement in two energy regions with a γ-spectrometer or with a multichannel pulse-height analyzer. With a NaI(T1) wafer as detector, the correction for ruthenium can be omitted for osmium concentrations above 10 p.p.m.With the addition method of analysis, 10–2000 p.p.m. in 10-mg samples of ruthenium sponge can be determined by neutron activation analysis. Chemical separation is necessary but no carriers are required. The lowest limit of determination is about 3 p.p.m. for a 3” x 3” crystal; for the wafer, about 1 p.p.m. can be determined.     

Spectrophotometric determination of osmium with p-(morpholino)-n-(4'-hydroxy-3'-methoxy)benzylidineaniline

A sensitive spectrophotometric determination of osmium is based on the blue color (absorption maximum at 615 mμ formed by reaction of osmium with p-(morpholino)-N-(4'-hydroxy-3'-methoxy)benzylidineaniline (“anil”) in acetate-buffered solution containing ethanol to prevent formation of a precipitate, Full color development is attained in I h at room temperature, and the color is stable for several hours. The absorbance is reproducible. The optimum concentration range for I-cm optical path is about I to 4 p.p.m. of osmium. Several transition elements interfere ; osmium can be separated as its tetroxide by the usual distillation method. The blue product is a cationic complex formed by reaction of anil with osmium in a 2 : I mole ratio. When osmium is in excess a red cationic complex (absorption maximum at 466 mμ) is formed by a I : I reaction between osmium and the reagent. The I : I complex is slowly converted to the 2 : I complex by excess reagent.     

Spectrophotometric determination of osmium with ammonium thiocyanate

Summary A spectrophotometric method for the determination of osmium using ammonium thiocyanate is described. A stable reddish brown colour with an absorption maximum at 440 nm is produced when osmium tetroxide is heated for 30 min at a p_H between 1 to 4 over a boiling water bath with excess reagent. The recommended concentration range is from 3 to 15 ppm of osmium in aqueous medium and from 0.6 to 1.5 ppm when the brown colour (which turns blue) is extracted into isoamyl alcohol. Errors are about ± 1.5%.

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Zusammenfassung Zur spektrophotometrischen Bestimmung von Osmium wird als Reagens Ammoniumthiocyanat empfohlen. Bei Erwärmung von Osmiumtetroxid bei p_H 1–4 mit überschüssigem Reagens (30 min) wird eine beständige rötlich-braune Färbung mit einem Absorptionsmaximum bei 440 nm gebildet. Der günstigste Konzentrationsbereich ist 3–15 ppm in wä\rigem Medium bzw. 0,6–1,5 ppm, wenn mit Isoamylalkohol extrahiert wird (wobei die Farbe nach Blau umschlägt). Die Fehler betragen etwa ± 1,5%.

     

Sorption-colorimetric and test determination of osmium in alloys and concentrates

A test is proposed for the evaluation of the concentration of osmium in solutions based on the direct proportionality between the concentrations of osmium(IV) or osmium(VI) and the length of the colored zone on the indicator paper; the latter is covered by a polymer film and is in contact with the test solution along one edge. The paper is impregnated by 3-methyl-2,6-dimercapto-1,4-thiopyrone, which reacts with osmium ions in the solid phase and forms poorly soluble products. The effectiveness of the dynamic preconcentration of osmium(IV) from solutions, obtained upon the reduction of its volatile tetroxide for the subsequent visual test and colorimetric determination on paper filters in the total concentration range 4–400 μg in samples for a sample volume of 100 mL, is demonstrated. The procedures developed are utilized for the determination of osmium in ore processing wastes from Dzhezkazgan’s mines and in its alloys.     

Spectrophotometric determination of osmium

Summary m-Amino benzoic acid in large excess reacts with tetra-, hexa- and octavalent osmium at theph range 4.5–6 to give a purple complex having absorption maximum at 500 nm. Beer's law is obeyed for 0.5 to 8 ppm of osmium(VI) and osmium(VIII) with optimum concentration range of 2 to 8 ppm of osmium(VI) and 3 to 8 ppm for osmium(VIII). The per cent relative error per 1% absolute photometric error is 2.8 for both osmium(VI) and osmium(VIII). Ions such as Pd²⁺, Rh³⁺, Ir⁴⁺, W⁶⁺, U⁶⁺, Co²⁺, Hg²⁺, Mg²⁺, Ca²⁺, Ba²⁺, Sr²⁺, Th⁴⁺ and Zr⁴⁺ do not interfere in the determination.Molar ratio method indicates that the reagent first reduces osmium (VIII) and osmium(VI) to osmium(IV), which then probably forms a 11 complex with the excess unoxidised reagent.Part III.: Anal. chim. Acta 22, 306 (1960); cf. Z. analyt. Chem. 177, 291 (1960).     

Gravimetric determination of osmium with 1:2:3-benzotriazole

A method for the direct gravimetric determination of osmium with 1:2:3-benzotriazole in acetic acid-sodium acetate buffer is presented. The method is accurate and reproducible, and the conditions used in the determination are not critical. The precipitate is a stoichiometric compound which is stable from room temperature up to 200°. It appears that 1:2:3-benzotriazole is probably the first organic reagent to be used successfully in the direct gravimetric determination of osmium.     

Photometric determination of osmium with thiourea after extraction of the tetroxide

A general method for the determination of 5–1000 γ of osmium involves extraction of osmium tetroxide with chloroform or carbon tetrachloride, followed by shaking the organic solvent with a sulfuric acid solution, of thiourea to form red Os(NH₂CSNH₂)₆⁺³, whose color intensity is measured photometrically. A sharp separation of osmium from ruthenium can be obtained by reducing Os(VIII) and Ru(VIII) with ferrous sulfate and then oxidizing Os(IV) to Os(VIII) with nitric acid; ruthenium remains reduced and is not extracted by chloroform or carbon tetrachloride.     

Colorimetric determination of osmium (VI) with 1-naphthylamine-3,5,7-trisulfonic acid

An investigation has been made of the organic compound, 1-naphthylamine-3,5,7-trisulfonic acid, for use as a colorimetric reagent for the determination of trace quantities of osniiun(Vl). When this compound is added to an osmium (OsO₄^-2) solution, a violet colored organo-osmium complex is formed which has highest sensitivity at wavelength 560 mμ. The complex reaches maximum color intensity after four hours. The solution should be brought to pH 1.5 and maintained at tins pH with a buffer, after maximum color development. The colored complex conforms to Beer's law over an osmium concentration range of 0 to 6 p.p.m. Its absorbance is not affected by either excess reagent (up to a 7 : 1 ratio) or by temperature variation over the range 15° to 35° C. Many metallic ions interfere with the color reaction and hence require a separation, of osmium from these ions.The nature of the complex in solution was studied by the following three methods: (1) mole ratio, (2) continuous variations and (3) slope ratio. All three methods indicate a ratio of reagent to osmium of 2 to 1.A procedure for the colorimetric determination of osmium(VI) has been developed; it has a sensitivity of 1 part osmium in 15,000,000 parts of solution, with good precision.     

Spectrophotometric determination of pyrrole derivatives

A simple, reliable and rapid method for the spectrophotometric determination of some pyrrole derivatives with concentrated sulphuric acid has been developed. The results show a maximum deviation of about 0.2 μg.     

Study of the system Os(IV)-chloride-brilliant green: Extraction-spectrophotometric determination of osmium

A sensitive extraction-spectrophotometric method of the determination of osmium, taking advantage of the ion-associate of the chloride osmium anion with brilliant green has been developed. The complex is extracted from aqueous phase with a mixture of C₆H₅Cl + CCl₄ (3 + 1). Molar absorptivity () at 640 nm is 1.95 × 10⁵ liters mol⁻¹cm⁻¹ (specific ABSORPTIVITY = 1.03). The relative standard deviation is 1–3%. The mole ratio of Os:BG in the complex is 1:3. Platinum metals interfere with the determination of osmium. The determination can be highly selective after preliminary separation of osmium by distillation as OsO₄.     

Spectrophotometric determination of osmium with 1-naphthylamine-4,6,8-trisulfonic acid

This investigation was undertaken to determine if the naphthylamine sulfonic acid-osmate (OsVI) reaction is suitable for a spectrophotometric determination of osmium. The 1-naphthylamine- 4, 6,8-trisulfonic acid osmate complex is water-soluble and forms a stable violet-colored system at PH 1 to 1.5 that is independent of reagent concentration. At 555 mμ the colored complex obeys Beer's law over a concentration range of 0.1 to 6.5 p.p.m. osmium and remains stable with respect to time and temperature. The effects of pH, temperature, reagent concentration, and diverse ions were studied. The nature of the organo-osmate complex in solution was studied by three techniques and the effect of temperature and pH on the rate of complex formation was determined. A procedure for the removal of osmium from all interfering ions was developed based on well known distillation techniques.A convenient, sensitive, reproducible and accurate method for the spectrophotometric determination of osmium has been developed.     

Flow-through fluorescence immunosensor for atrazine determination

A new flow-through fluoroimmunosensor for atrazine determination based on the use of protein A immobilized on controlled pore glass as immunoreactor is reported. The support, placed in the optical path of the flow cell, allows the ‘in situ’ quantification of atrazine by on-line antigen–antibody binding upon successive injections of both substances. The immunosensor has a detection limit of 2.1 μg l⁻¹, a sample speed of about 10 samples per hour, and provides high reproducibility both within-day (3.2% for 5 μg l⁻¹ and 2.2% for 30 μg l⁻¹) and between days. The optimum working concentration range was 2.1–50 μg l⁻¹. Possible interferences of other triazines like simazine, desethylatrazine (DEA) and desisopropylatrazine (DIA) were evaluated. Simazine and DIA were not cross-reactive; however, the cross-reactivity for DEA was CR=7.7%. The proposed immunosensor was successfully applied to the determination of atrazine in drinking water and citrus fruits.     

Spectrophotometric determination of osmium with the use of 3-methyl-2,6-dimercapto-1,4-thiopyrone in concentrates and alloys

Taking into account the specific features of the complexation of osmium(VI) and osmium(IV) with 3-methyl-2,6-dimercapto-1,4-thiopyrone without a change in the oxidation number of the given element and properties of complexes formed in aqueous and organic solutions, schemes were proposed for the instrumental (including spectrophotometric) determination of osmium with the preconcentration and separation from concomitant components without distillation of its tetroxide from technological solutions or solutions of an alkalioxidizing sample decomposition. A procedure was proposed for the direct spectrophotometric determination of osmium(VI) in solutions; the accuracy of the procedure was verified with a standard reference sample of a platinum concentrate. The developed procedure was used for the determination of osmium in the flotation slime of ores from Dzhezkazgan deposits and in alloys.     

Flotation—spectrophotometric determination of osmium with thiocyanate and methylene blue

A sensitive flotation—spectrophotometric method, based on the ion associate formed by the anionic thiocyanate complex of osmium with the basic dye methylene blue (MB) is described. The ion associate precipitates when the aqueous solution is shaken with toluene, and the separated and washed compound is dissolved in acetone. The molar absorptivity is 2.2 × 10⁵ l mol^-1 cm^-1 at 655 nm. Beer's law is obeyed. The molar ratio of Os:SCN:MB in the separated and washed ion associate is 1:6:3. Ruthenium reacts similarly. The method is applied to the determination of traces of osmium in crucible platinum after separation of osmium by distillation as tetroxide.     

Flotation-spectrophotometric determination of osmium (ruthenium) with thiocyanate and Capri blue

A sensitive flotation-spectrophotometric method for the determination of osmium, based on the ion associate formed by the anionic thiocyanate osmium complex with oxazine basic dye, Capri blue (CB), has been developed. The ion associate is separated by shaking the aqueous solution (pH 2–3) with diisopropyl ether, washing the precipitate with water, and dissolving it in methanol. Molar absorptivity in this method amounts to 2.7 × 10⁵ liters mol⁻¹ cm⁻¹ at 630 nm. The molar ratio Os:SCN:CB in the separated associate is 1:8:5. Under the conditions of the determination of osmium, ruthenium can be determined as well. Metals that form anionic thiocyanate complexes, including other platinum metals, interfere. The method becomes highly selective for osmium and ruthenium after their separation by distillation as tetroxides. Osmium and ruthenium were determined with Capri blue after their extractive separation as thiocyanate complexes.