Sorption Preconcentration of Platinum-Group Metals with Filled Fibrous POLYORGS Sorbents

The sorption of platinum, palladium, and rhodium with fibrous filled POLYORGS sorbents was studied depending on the concentration of hydrochloric acid and the time of contact of the solution with the sorbent in the batch mode. The equilibrium and kinetic characteristics of the sorption of platinum with the POLYORGS 17-n sorbent were determined, on the basis of these data the conditions for the dynamic preconcentration of platinum from a 1 M HCl solution were calculated. Conditions were selected for the group preconcentration of palladium, platinum, and gold in the dynamic mode and for their subsequent determination in the sorbent. It was demonstrated that rhodium can be preconcentrated with the POLYORGS 17-n sorbent in the dynamic mode in the presence of tin chloride.     

Studies on the extraction of platinum metals with tri-iso-octylamine from hydrochloric and hydrobromic acid: separation and determination of gold, palladium and platinum

The extraction of Pd(II), Rh(III), Ir(III), Au(III) and Pt(IV) from hydrochloric and hydrobromic acid with 5% tri-iso-octylamine solution in carbon tetrachloride has been studied. The gold extract from hydrochloric acid is yellow and absorbs at 325 nm, the palladium compound is red and absorbs at 290 nm and 467 nm, and the platinum compound is blood-red and shows absorption at 268 nm. The gold, palladium and platinum extracts from hydrobromic acid are crimson. reddish brown and blood-red, with maximum absorption at 260, 345 and 300 nm respectively. Methods have been devised for the separation of gold from platinum and for its determination and also for the simultaneous determination of palladium and platinum.     

Catalytic amperometric and catalytic constant-current potentiometric titrations of silver(I), palladium(II) and mercury(II)

Amperometry and constant-current potentiometry were used to follow the course of catalytic titrations of silver(I), palladium(II), and mercury(II) with potassium iodide. The Ce(IV)As(III) and Ce(IV)Sb(III) systems in the presence of sulphuric acid were used as indicator reactions. The possibilities of application of platinum, palladium, gold, graphite, and glassy-carbon indicator electrodes were investigated. Graphite appeared to be somewhat more advantageous than the other electrode materials. The effect of concentration of the components of the indicator reactions, the presence of organic solvents and acids on the shape of the catalytic titration curves was studied. Amounts of 30-3000 mug of silver(I) nitrate, 90-900 mug of palladium(II) chloride, 130-1300 mug of mercury(II) chloride, and 150-1500 mug of mercury(II) nitrate were determined with a relative standard deviation less than 1.0%. The results obtained were in good agreement with those of comparable methods. The catalytic titration method developed was applied to determination of mercury in Unguentum Hydrargyri.     

Flow-Injection Study and Analytical Applications of the Reactions of Palladium(II) and Platinum(IV) with Tin(II) Chloride in Hydrochloric Acid Solutions

The interaction of palladium(II) and platinum(II) with tin(II) chloride in hydrochloric acid solutions was studied by flow-injection (FI) spectrophotometry. It was found using kinetic measurements in the stopped flow mode that the composition of detected products and the rate of their formation depend on the concentrations of tin(II) and chloride ions in the reaction zone and on the acidity of the solution. Optimal FI conditions were found, and the selectivity of interaction of palladium(II) with tin(II) chloride was estimated for the detection of the signal at 407 nm (yellow form) and 646 nm (green form). It was demonstrated that the reaction of the formation of yellow platinum(IV) complexes is slower than that for palladium(II), especially at rather low concentrations of hydrochloric acid in the reaction flow. Based on the detection of green complexes of palladium(II) with tin(II) chloride, a flow injection method was proposed for the selective spectrophotometric determination of palladium(II) in the presence of other platinum-group metals. The height of the recorded peak is directly proportional to the concentration of palladium(II) in the injected solution in the range of 0.028–0.300 mM. The method was used for the analysis of pharmaceuticals and industrial catalysts.     

Tri-n-octylphosphine sulfide: : A selective organic extractant

Tri-n-octylphosphine sulfide (TOPS) has been investigated as the stationary phase in reversed-phase partition paper Chromatographie separations using nitric or hydrochloric acids as the mobile phase. TOPS has also been studied as an extractant for metal ions. Silver, mercury (II), and palladium (II) were found to have RF values of zero when nitric acid was used as the mobile phase. These same ions were also selectively extracted from aqueous nitric acid solutions. Gold(III), mercury(II), palladium (II), and platinum (IV) were found to have RF values of zero when hydrochloric acid was used as the mobile phase. However, only gold(III) and mercury(II) were extracted from aqueous hydrochloric acid solutions in liquid-liquid extraction systems. Several separations were successfully performed from 1 M nitric acid.     

A fire-assay and wet chemical method for the determination of palladium, platinum, gold, and silver in ores and concentrates

A method is presented for the determination of palladium, platinum, gold and silver in ores and concentrates by a fire-assay and wet chemical technique. After parting of the lead assay button with dilute nitric acid, and separation of the solution from the residue, the palladium and platinum in the solution are precipitated by the addition of stannous chloride, with tellurium as collector. The resulting precipitate is combined with the gold residue and dissolved in aqua regia, then the solution is analysed for palladium, platinum and gold by atomic-absorption spectrophotometry (AAS). Silver is determined in the original solution by AAS before the reduction step.     

Solvent extraction and spectrophotometric determination of palladium(II) with some nitrogen-containing heterocyclic hydrazones in the presence of chloride ions

Three terdentate hydrazones, all containing the 1-phthalazino grouping in the hydrazine moiety but differing in the heterocyclic substituent in the aldehyde moiety, have been used as analytical reagents for palladium(II), the optimal conditions for the extractive spectrophotometric determination of palladium(II) in the presence of chloride ions being deduced. These compounds are highly selective and sensitive reagents for palladium(II), since they are not extracted into chloroform from sulfuric acid solutions and do not react with other platinum group metals. The desirable spectral properties of the palladium(II) complex of benzothiazole-2-aldehyde-1-phthalazinohydrazone (BAPhH) have also been discussed with respect to preference of the C  N structural form in the heterocyclic ring on the aldehyde moiety of the ligand.     

Stability constants of some metal dithizonates

The overall stability constants of electroneutral dithizonates of bismuth, cadmium, cobalt(II), copper(II), iron(II), lead(II), manganese(II), mercury(II), nickel, palladium(II), silver, tin(II) and zinc were determined by means of stoichiometric dilution in aqueous solution stabilized by hydroxylamine hydrochloride, at pH 5.50-10.02. Stability constants of complexes ML of bivalent metals were determined under similar conditions but with an excess of metal.     

A new solvent extraction scheme for the separation of platinum,palladium, rhodium and iridium

A new scheme is proposed for the separation of platinum, palladium, rhodium and iridium in hydrochloric acid solutions, by solvent extraction. Platinum and palladium are complexed with 2-mercaptobenzothiazole and potassium iodide and simultaneously extracted into chloroform, thus separating them from rhodium and iridium. Palladium is separated from platinum by extracting its dimethylglyoxime complex into chloroform, while rhodium is separated from iridium by extracting its 2-mercaptobenzothiazole complex into chloroform after reduction with tin(II) chloride.     

Determination of arsenic in ores, concentrates and related materials by graphite-furnace atomic-absorption spectrometry after separation by xanthate extraction

A method for determining approximately 0.2 mug/g or more of arsenic in ores, concentrates and related materials is described. After sample decomposition arsenic(V) is reduced to arsenic(III) with titanium(III) and separated from iron, lead, zinc, copper, uranium, tin, antimony, bismuth and other elements by cyclohexane extraction of its xanthate complex from approximately 8-10M hydrochloric acid. After washing with 10M hydrochloric acid-2% thiourea solution to remove residual iron and co-extracted copper, followed by water to remove chloride, arsenic is stripped from the extract with 16M nitric acid and ultimately determined in a 2% nitric acid medium by graphite-furnace atomic-absorption spectrometry, at 193.7 nm, in the presence of thiourea (which eliminates interference from sulphate) and palladium as matrix modifiers. Small amounts of gold, platinum and palladium, which are partly co-extracted as xanthates under the proposed conditions, do not interfere.     

Application of Silica Chemically Modified by Sulfur-Containing Groups to the Separation and Determination of Platinum and Rhenium in Catalysts Based on Aluminum Oxide

Adsorbents based on silica chemically modified by sulfur-containing groups (dithiocarbamate, thiodiazolethiol, mercaptophenyl, and aminobenzothiazole) quantitatively extract (recovery ≥99%) platinum( IV) from solutions ranging from 4 M HCl to pH 6. Under the conditions of the adsorption separation of platinum(IV), rhenium(VII) is not extracted and remains in the solution. The subsequent quantitative (98–99%) adsorption of rhenium(VII) is achieved in the presence of a 1000-fold excess of tin(II) chloride. Adsorption on the surface of adsorbents leads to the formation of platinum(II) complexes with sulfur-containing groups, luminescent at 77 K on irradiation with UV light. The luminescence spectra of surface platinum( II) complexes are located in the region of 550–700 nm. In the adsorption of rhenium(III) in the presence of tin(II) chloride, intensely colored brown complexes of rhenium formed on the surface of adsorbents. Electron paramagnetic resonance showed that, in the surface complexes, rhenium is in the oxidation state 2+. Silicas chemically modified by sulfur-containing groups were used in the development of procedures for the sequential isolation and determination of platinum and rhenium in solutions after the decomposition of aluminum–platinum–rhenium catalysts.     

Amperometric titration of palladium, silver and copper with benzimidazol-2-ylmethanethiol, and its application to non-ferrous materials

A method is described for the determination of mg amounts of palladium, silver and copper by amperometric titration with benzimidazol-2-ylmethanethiol in acetate buifer medium (pH 4-5) at an applied potential of -0.2 V vs. the saturated calomel electrode. Direct titrations are possible in the presence of a number of foreign ions. Copper and palladium interfere mutually and in the determination of silver. Mercury(I), mercury(II) and platinum(IV) also interfere. Silver does not interfere in the determination of copper and palladium if it is first precipitated as chloride. The method has been successfully applied to the analysis of non-ferrous materials.     

Spectrophotometric determination of noble metals with tin(II) in bromide solutions

In presence of tin(II) bromide, noble metals give coloured products which are suitable for spcctrophotometric determinations. The colours are red (platinum), yellow-orange (rhodium), yellow-brown (palladium), yellow (iridium) and violet (gold) They are extracted, except for gold, with isoamyl alcohol Platinum, rhodium and palladium can be separated from irdium, and rhodium and platinum from palladium. Rhodium and platinum can be determined simultaneously.     

Cation-exchange behaviour of the platinum group and some other rare elements in hydrobromic acid-thiourea-acetone media

Ion-exchange distribution coefficients and elution curves are presented for copper(I), silver, gold(I), palladium, platinum(II), rhodium(III), iridium(III), ruthenium(III), osmium(III), mercury(II), thallium(I), tellurium(II), lead and bismuth in mixtures of thiourea, hydrobromic acid, acetone and water, with the cation-exchange resin AGW50W-X4. The system affords excellent separations of rhodium, mercury, silver (or copper), tellurium, gold, and palladium (or platinum) from each other.     

Effect of citric acid and hydrochloric acid on the polarographic behaviour of tin: Application to the determination of tin(II) in presence of tin(IV) in the activating solutions of the electroless plating of polymers

A new method for the determination of tin(II) in presence of tin(IV) is described. The method is based on differential pulse polarography on the hanging mercury drop electrode (HMDE). The effect of citric acid and hydrochloric acid concentrations on the polarographic peaks of tin(II) and tin(IV) has been studied. In 1 M HCl, the total quantity of tin can be determined, as under these conditions, in the absence of complexing agents, eventual variations in the oxidation states, in any concentration ratio, do not affect the peak height and the peak potential. In 0.2 M HCl and 0.2 M citric acid, tin(II) can be determined selectively in presence of tin(IV), as under these conditions, tin(IV) does not present polarographic response, while a well-defined peak is observed for tin(II). The method is applied to determine tin(II) and total tin in the activating solutions of the electroless plating of polymers.     

Determination of platinum and iridium in reforming catalysts by second derivative and absorptiometric spectrophotometry

Summary Investigations on the spectrophotometric determination of platinum as a complex formed by tin(II)chloride in hydrochloric acid are reported. The determination of platinum was found to be interfered with by iridium, because it also forms a complex with tin(II) chloride. The features of the derivative absorption spectrophotometry for the quantitative determination of platinum and iridium was also studied. The analytical application of the method for the determination of platinum and iridium in catalysts was investigated.     

Simultaneous Potentiostatic Coulometric Determination of Platinum and Palladium

Based on a voltammetric study of the electrochemical behavior of Pt(IV) and Pd(II) in a 1 M HCl + 0.1 M ethylenediamine hydrochloride solution at a carbon–graphite electrode, we have found the optimum conditions for the simultaneous determination of 0.2 to 3 mg of platinum and palladium with a relative standard deviation of less than 0.5%.The oxidation reactions were Pd(0) Pd(II) and Pt(II) Pt(IV). Mass excesses of analytes of 3.5- to 4.5-fold with respect to each other did not interfere with the determination of individual elements. With alternate cathodic and anodic polarization of the electrode, these elements can be multiply determined in a single portion of solution. The procedure was used for the simultaneous determination of platinum and palladium in process solutions of KP-1 platinum concentrate after the separation of gold and silver and also in platinum- and palladium-based alloys.     

Extractive separation of platinum from macroamounts of palladium using triphenylphosphine oxide and its successive spectrophotometric determination by the stannous chloride method

Trialkylphosphine oxides extract more effectively chloride complexes of platinum than of palladium(II). Of the examined tributylphosphine (TBPO), trioctylphosphine (TOPO), and triphenylphosphine (TPPO) oxides the latter one makes possible best separation of these metals.The extraction of platinum with TPPO from solutions containing platinum and palladium unfavorably decreases with increasing palladium concentration. Using 0.1 M TPPO solution in dichloroethane, at HCl concentration 7.5 M, it is possible to separate 2–200 μg Pt/ml at a palladium concentration not higher than 10 mg/ml.Separation of platinum from macroamounts of palladium has been combined with spectrophotometric determination of platinum by means of stannous chloride. The method has been applied to the analysis of palladium for platinum content.     

Simultaneous determination of tin and lead by a.c. anodic stripping voltammetry at a hanging mercury drop electrode sensitized by cetyltrimethylammoniu

The influence of cetyltrimethylammonium bromide (CTAB) on the simultaneous determination of tin(IV) and lead(II) by anodic stripping voltammetry at a hanging mercury drop electrode (HMDE) in a 0.1 M hydrochloric acid—0.1 M oxalic acid medium was studied using d.c. and a.c. stripping. In the presence of CTAB, tin and lead show voltammetric peaks separated by 100 mV, the sensitivity depending on the concentration of CTAB. The best conditions for the simultaneous determination of both elements (2 × 10^-3 M) were found. A method is proposed for the determination of tin in the presence of lead and three procedures are given for the determination of lead in the presence of tin.     

Extraction of gold, palladium and platinum from chloride, bromide and iodide solution with di-n-octyl sulphide (DOS) in cyclohexane

The extraction of gold, palladium and platinum from hydrochloric acid, hydrobromic acid and iodide media by solutions of di-n-octyl sulphide in cyclohexane was examined. From distribution data it was concluded that the monosolvates AuX(3).DOS and disolvates PdX(2).2DOS are extracted. Extraction of platinum was efficient only from iodide solutions; a disolvate PtI(4).2DOS was formed. The possibility of separation of gold and palladium from platinum by extraction from bromide or chloride solutions and simultaneous extraction of palladium and platinum from an iodide medium was demonstrated.