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Extraction of Ruthenium and Its Separation from Rhodium and Palladium with 4-Pyridone Derivatives

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Extraction of Ruthenium and Its Separation from Rhodium and Palladium with 4-Pyridone Derivatives CROATICA CHEMICA ACTA CCACAA 78 (4) 617¿626 (2005) ISSN-0011-1643 CCA-3055 Original Scientific Paper Extraction of Ruthenium and Its Separation from Rhodium and Palladium with 4-Pyridone Derivatives Vinka Dru{kovi},a Vlasta Vojkovi},b,* and Tatjana Antoni}c aResearch & Development, Belupo Ltd. Pharmaceuticals & Cosmetics, Radni~ka cesta, 10000 Zagreb, Croatia bLaboratory of Analytical Chemistry, Faculty of Science, University of Zagreb, Strossmayerov trg 14, 10000 Zagreb, Croatia cLaboratory for the Synthesis of New Materials, Ru|er Bo{kovi} Institute, Bijeni~ka 54, 10000 Zagreb, Croatia RECEIVED MARCH 2, 2004; REVISED MAY 3, 2005; ACCEPTED MAY 3, 2005 Formation of a yellow chelate complex of ruthenium(III) with 3-hydroxy-2-methyl-1-phenyl- -4-pyridone or 3-hydroxy-2-methyl-1-(4-tolyl)-4-pyridone in the aqueous phase and extraction Keywords of the chelates in dichloromethane were used for spectrophotometric determination of ruthe- extraction nium. Beer's law was obeyed over the concentration range of 0.1–20.0 mgcm–3 ruthenium. gama-pyridone Molar absorptivity was 1.35 ´ 104 mol–1 dm3 cm–1 (organic phase, at 393 nm) and 1.29 ´ 104 palladium mol–1 dm3 cm–1 (aqueous phase, at 367 nm), irrespective of the reagent used. The method was rhodium successfully applied to the determination of ruthenium in synthetic mixtures. Extraction of a ruthenium chelate complex of ruthenium(III) with 3-hydroxy-2-methyl-1-phenyl-4-pyridone proved to be separation a simple and efficacious method for the separation of ruthenium(III) from large amounts of spectrophotometry palladium(II) and rhodium(III). INTRODUCTION chlorocomplexes, have been much used in the catalytic oxidation of some organic compounds. Ruthenium and its Ruthenium is a scarce element that is found in about alloys also have a widespread application in jewellery.1 –8 10 % of the earth's crust. It is present in much larger In radiochemistry, the interest lies in the separation amounts in chondrite and, especially, in iron meteorites of rhodium from ruthenium since rhodium is a daughter ((1-6) ´ 10–4 %). It usually occurs in association with of ruthenium by beta decay.2 1 other platinum group metals. The growing use of ruthenium in widely different As one of the most effective hardeners in high-den- fields has made it necessary to develop simple, inexpen- sity alloys, ruthenium is widely used in the electronic in- sive and sensitive methods for its determination. When dustry. Alloyed with other platinum metals it serves to ruthenium is present in various matrices in extremely make electrical contacts for heavy wear resistance. Re- low concentrations, direct determination is not success- cently, platinum metals, especially ruthenium and its ful without previous preconcentration and separation. * Author to whom correspondence should be addressed. (E-mail: [email protected]) 618 V. DRU[KOVI] et al. Separation procedures (volatilization, coprecipitation, tive extracting spectrophotometric reagents to determine solvent extraction, sorption and chromatography) can be palladium(II),32 and spectrophotometric or fluorimetric used to isolate and preconcentrate ruthenium from multi- reagents to determine iridium(IV).33,34 component samples containing noble and base metals.3 In the present paper, we report the results of studies A conventional method for the separation of ruthe- of the reaction between ruthenium(III) and HX(HY) nium from the platinum metals is based on the distilla- with the intention to elucidate the spectrophotometric tion of volatile ruthenium tetroxide.3,4 Different oxidants determination of ruthenium in the aqueous phase or in (HClO4+H2SO4, NaBiO3,K2Cr2O7 and KMnO4) for ru- the organic phase after extraction with some organic sol- thenium have been used. This, however, is not an appro- vents, and to use the data to open new possibilities for priate method for producing ruthenium on an industrial the separation of ruthenium from other platinum metals. scale because it requires complicated manipulation and O because of the explosive property of tetroxide at temper- O OH atures above 180 °C. Therefore, solvent extraction is OH 1 N CH preferred to distillation. For metal preconcentration, the 3 N CH tetroxide can be extracted into carbon tetrachloride,5-7 3 chloroform,5 or mephasine.8 CH Precipitation methods are rarely used to isolate ru- 3 thenium from multi-component mixtures due to lack of 3-Hydroxy-2-Methyl-1-Phenyl- 3-Hydroxy-2-Methyl-1-(4-Tolyl)- selective precipitants.3 However, ruthenium concentra- 4-Pyridone (HX) 4-Pyridone (HY) tion can be achieved by the solvent flotation method.9 The method is based on the ion associate formed by the 2– anionic chloride complex of ruthenium RuCl6 with the EXPERIMENTAL basic dye Rhodamine 6G. It precipitates when the aque- ous solution is shaken with toluene. The separated com- Reagents pound is soluble in acetone. A stock solution of ruthenium(III) (1 ´ 10–2 mol dm–3) was e.g., Various complexing agents ( di(2-ethylhexyl)- prepared by dissolving (NH ) RuCl × H O (Johnson 10 3 3 4 2 5 2 phosphonic acid, carbamates, dithizone, and thiourea Matthey, New York, USA) in 1 mol dm–3 HCl. The solution 3 derivatives ) can be used in separation procedures to was standardized spectrophotometrically with thiourea35 convert ruthenium into stable extractable species. and checked with the ruthenium atomic absorption standard The chlorocomplexes of ruthenium are extractable by solution (Johnson Matthey). 11 means of various organophosphorus compounds and Rhodium(III) and palladium(II) stock solutions (0.02 and high-molecular-weight amines.11,12 Amine, dissolved in –3 0.01 mol dm ) were prepared from RhCl3 or PdCl2 (Fluka, an organic diluent, is transformed into organic cation Buchs, Switzerland) in 0.05 mol dm–3 HCl. The solutions + (RxNH ) by reacting with the acid present in aqueous were standardized gravimetrically36 with the dimethylglyo- solution. The cation reacts with the anionic complex of xime (palladium) and zinc (rhodium). Working solutions were the analyte in solution by forming an ion-pair, dissolved obtained by appropriate dilution of the stock solution with in the organic solvent used as diluent. deionized water. Ruthenium can be separated from platinum metals 3-Hydroxy-2-methyl-1-phenyl-4-pyridone (HX), and 3- after its conversion into a thiocyanate complex.13–17 A hydroxy-2-methyl-1-(4-tolyl)-4-pyridone (HY) were synthe- high distribution coefficient is achieved when polyure- sized as described previously.37 Solutions were prepared by thane foam is applied in ruthenium extraction from dissolving weighed amounts of HX in water (heating time thiocyanate media.16 Surfactant extraction of ruthenium 15 minutes at about 80 °C) and of HY in 96 % (v/v) ethanol. from thiocyanate media into Triton X-100 phase in the Thiourea, 10 %, w/v aqueous solution. 17 presence of Zephiramine has been investigated. A solution of alkali metal salts and a solution of differ- Solvent-extraction processes are well established and ent metals were used to study ion interference. efficient techniques for the separation of ruthenium from All the chemicals used were of analytical-reagent grade. platinum and palladium,12,18 rhodium,14,18 osmium, and iridium.18,19 UV-VIS spectrophotometry is widely applied for the Apparatus determination of microgram amounts of ruthenium. Ex- A Varian double-beam spectrophotometer, model Cary 3, traction is the first step to be taken before spectrophoto- equipped with 1-cm quartz cells, was used for absorption 12, 20–31 metric determination of ruthenium. measurements. Determination of palladium, ruthenium and Recently, gamma-pyridone derivatives, 3-hydroxy-2- rhodium in the aqueous phase after extraction was performed methyl-1-phenyl-4-pyridone (HX) or 3-hydroxy-2-methyl- on a Perkin Elmer atomic absorption spectrometer, model -1-(4-tolyl)-4-pyridone (HY), have been used as effec- 3030B. Operating conditions are given in Table I. Croat. Chem. Acta 78 (4) 617¿626 (2005) EXTRACTION OF RUTHENIUM 619 TABLE I. Operating conditions for ruthenium, rhodium and palla- and a given amount of HX were mixed and diluted to about dium determination by AAS 15 cm3. The pH was adjusted to 6.5 by addition of NaOH. The solution was transferred quantitatively to a 25-cm3 R.f. generator 50/60 Hz, operating power 500 W standard flask, heated at 75 °C for 15 minutes, cooled to 3 3 Gas flow air: 45 dm /min; acetylene: 20 dm /min room temperature in ice water and finally diluted to vol- –3 –3 Ruthenium 0.57 mol dm HCl; 0.15 mol dm HNO3; ume. The final ruthenium(III) and HX concentrations were 0.5 % LaCl3; 349.9 nm 5 × 10–5 mol dm–3 and 4.5 × 10–3 mol dm–3. –3 –3 Rhodium 2.7 mol dm HCl; 0.07 mol dm Na2SO4; An aliquot (10 cm3) was shaken with an equal volume 343.5 nm of dichloromethane in a 50-cm3 conical flask with a me- Palladium 0.5 mol dm–3 HCl; 244.8 nm chanical shaker for 20 min. Concentrations of the metals that remained in the aqueous phase were determined by atomic absorption spectrometry (AAS) after dilution, as de- A Griffin flask shaker with a time switch served for ex- scribed above. The experiments were carried out in dupli- traction. The pH of the aqueous phase was measured with a cate. Radiometer PHM 85 precision pH-meter. Synthetic Mixtures General Extraction Procedure Different amounts of metal salts, including those of ruthe- A known volume of the working ruthenium solution and a nium, were mixed. A mixture (about 0.5 g) was dissolved given amount of HX(HY) were mixed and diluted to about in1cm3 concentrated hydrochloric acid by heating. After 3 III III 6cm. The pH was adjusted to 6.5 (Ru -HX) or 7.0 (Ru - cooling to room temperature, it was diluted with deionized -HY) with the addition of NaOH.
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