Iridium(IV) extraction with petroleum sulfoxides from hydrochloric acid solutions

Iridium(IV) extraction with petroleum sulfoxides (PSO) from hydrochloric acid solutions is studied. Optimum conditions of extraction are chosen. It is shown that in the investigated extraction systems for a phase contact time of 30 min, iridium(IV) is extracted by the ion-associative mechanism. Electronic, ¹H NMR, and IR-spectroscopy, and elemental analysis are used to establish the structure of the extracted compound.     

Extraction of Iridium(IV) by 1-(2-(2,4-Dichlorophenyl)-4-propyl-1,3-dioxolan-2-yl-methyl)-1H-1,2,4-triazole from Hydrochloric Solutions

Extraction of iridium(IV) by 1-(2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-yl-methyl)-¹H-1,2,4-triazole from hydrochloric solutions was studied. Optimal extraction parameters were determined. The mechanism of iridium(IV) extraction in this system is ion exchange (3.0 mol/L HCl and τ_cont = 5 min). Electronic, ¹H NMR, ¹³C NMR, and IR spectroscopy and elemental analysis were used to determine the composition of the extracted compound.     

Evaluation of plutonium(IV) extraction rate between nitric acid and tri‐n‐butylphosphate solution using a glass chip microchannel

Extraction of Pu(IV) with tri‐n‐butylphosphate is performed using a glass chip microchannel to evaluate the extraction rate. Two‐phase flow forms in the microchannel by introducing a solution of Pu(IV) and tri‐n‐butylphosphate with flow rates above 5 μL/min. The Pu(IV) extraction reaction proceeds at the interface between the two phases. To evaluate the extraction rate, the contact time between the two phases is varied from 0.48 to 4.8 s by changing the confluent length of the microchannel and the flow rate. The Pu concentration of each phase collected from the microchannel is measured with an alpha liquid scintillation counter, and the contact time dependence of Pu(IV) extraction is obtained. An extraction model based on diffusion in the microchannel and the reaction at the interface is proposed and applied to determine the extraction rate. The extraction process is assumed to follow pseudo‐first‐order kinetics, and the extraction rate constant of Pu(IV) is determined to be 1.5 × 10^?2 cm/s. The investigation demonstrates that a microfluidic device can be a new tool to determine Pu(IV) extraction rates.     

Extraction of Iridium(IV) from Hydrochloric Acid Solution with Bis(piperidinoethylthioethyl)-1-phenyl-1-ethanone

A bidentate organic compound containing nitrogen and sulfur donor atoms was tested as a reagent for extraction of iridium(IV) from aqueous solutions. The composition of the extractable Ir(IV) complex was determined by ¹H NMR, UV, and IR spectroscopy and elemental analysis.     

Polyurethane foam for the extraction of rhodium and its separation from iridium

The rate of reaction of rhodium with thiocyanate at 90 degrees in the presence of lithium chloride or sufficient hydrochloric acid and the subsequent extraction of the metal from hydrochloric acid medium by polyether-type polyurethane foam was investigated. The effect of the chloride salts of different cations decreased in the order Li(+) > Na(+) > K(+) indicating that Rh(SCN)(6)(3-) is extracted through a simple solvent-extraction mechanism rather than the "cation-chelation" mechanism. The separation of rhodium and iridium was also examined and the results indicated that in the presence of 5-fold excess of iridium, an average of 95 +/- 2% iridium remained in the aqueous phase while an average of 93 +/- 2% rhodium was retained by the foam.     

Separation of rhodium and iridium by multiple fractional extraction

Mixtures of the chloro complexes of rhodium(III) and iridium(IV) were resolved by a nine stage multiple extraction technique. The solutes are partitioned in a hydrochloric acid-tributyl phosphate system. Rhodium is concentrated in the raffinate while iridium is concentrated in the extractant. 99% of the rhodium and 94% of the iridium are recovered free of the other metal. Experimental results agree reasonably well with the results predicted by a theoretical treatment of the distribution data.     

Solvent Extraction Separation of Iridium(III) from Rhodium(III) by N-n-Octylaniline

The use ofN-n-octylaniline for the extraction of iridium(III) from malonate media is studied at pH 8.5. Iridium(III) extracted in the organic phase was stripped with 2.0 M hydrochloric acid and was determined spectrophotometrically by the stannous chloride–hydrobromic acid method at 385 nm. The extraction system is studied as a function of the equilibration time, diluent, reagent concentration and diverse ions. Experimental data have been analyzed graphically to determine the stoichiometry of the extracted species. It was found that the extraction of iridium(III) proceeds by an anion exchange mechanism and transforms into the extracted species [RR"NH₂ ⁺Ir(C₃H₂O₄)₂ ^–]_org. The method is simple, rapid, and selective and has been devised for the sequential separation of iridium(III) from rhodium(III), not only from each other, but also from other accompanying Platinum Group Metals (PGMs), Au(III), and base metals.     

Reactivities of osmium(VIII), iridium(IV) and platinum(IV) towards glycolaldehyde

Oxidations of glycolaldehyde (GA) to glyoxal by osmium(VIII), iridium(IV) and platinum(IV) have been investigated in aqueous solution, and the orders with respect to each [reactant] determined. The reaction involving iridium(IV) takes place through intermediate formation of free radicals in a MeCO₂Na-MeCO₂H buffer medium, whereas a one-step two-electron transfer process occurs in the oxidations by Os^VIII and Pt^IV in an alkaline medium. Mechanisms consistent with the experimental findings are proposed. This revised version was published online in June 2006 with corrections to the Cover Date.     

Bestimmung von iridiumspuren mit thiodibenzoylmethan mittels substöchiometrischer isotopenverdünnungs-analyse: Determination of traces of iridium with thiodibenzoylmethane by substoichiometric isotope dilution analysis

Determination of traces of iridium with thiodibenzoylmethane by substoichiometric isotope dilution analysisIridium(III or IV) reacts with thiodibenzoylmethane on heating at pH 6 to form a 1:3 complex, which can be concentrated by extraction into chloroform. Based on this reaction, a reproducible, selective determination of iridium is achieved by means of substoichiometric isotope dilution analysis, based on ¹⁹²Ir. The linear range is 1–11 nmol of iridium.     

Kinetic-spectrofluorimetric determination of trace amounts of iridium

A simple and sensitive kinetic-spectrofluorimetric method is described for the determination of iridium(IV) and the possible mechanism of catalytic reaction is proposed. The method is based on the fluorescent quenching reaction of salicylaldehyde p-nitro-benzoylhydrazone (SAP-NBH) with potassium periodate, inhibited by Ir(IV) in a water-ethanol (7.3+2.7, v/v) medium at pH 10.70 and 55 degrees C. Cetyltrimethyl ammonium bromide sensitized the determination obviously. SAP-NBH was newly synthesized and its ionization constants were established spectrophotometrically. The reaction was monitored by measuring the change rate of fluorescence (lambda ex/em=252/310 nm) after a fixed time of 5 min. The proposed method allowed the determination of iridium in the range of 0.11-18 ng ml(-1) with a RSD of 2.5% at a concentration of 10 ng ml(-1) and the detection limit was down to 0.09 ng ml(-1). The method was found to be relatively selective and was applied successfully to determine iridium in synthetic mixtures and mineral sample with the results consistent well with the ref. values.     

Liquid-liquid extraction of rhodium(III) from hydrochloric acid solutions with 1,2,4-triazole derivative

Liquid-liquid extraction of rhodium(III) from hydrochloric acid solutions with a 1,2,4-triazole derivative was studied. Optimal conditions for its recovery were found. Rhodium(III) was shown to be recovered in extraction system by ion-exchange reaction at the time of phase contact not longer than 5 min. When phase contact time increased, rhodium(III) is extracted by a mixed mechanism with simultaneous insertion of two extractant molecules into the inner coordination sphere of rhodium(III) ion. Composition of coordination species of recovered compounds was established by electronic, IR, ¹H and ¹³C NMR spectroscopy and functional analysis, the structure of the coordination species is proposed.     

Sorption recovery of sulfate complexes of iridium on hydrated zirconium dioxide

The sorption on a hydrated zirconium(IV) dioxide from solutions of trinuclear iridium(IV,IV,IV) and iridium(III,III,IV) oxosulfates was studied. The effect of temperature, sorbent grain size, concentration of sulfate complexes of iridium in solution, and acidity of the medium on the sorption recovery was considered.     

Liquid–liquid extraction of thorium(IV) by fatty acids: a comparative study

In this paper, extractants that have the potential to be sustainably regenerated, are proposed for thorium(IV) removal from nitrate aqueous phases. These extractants are oleic (OA), palmitic (PA) and lauric (LA) acids. The advantages of using these acids are their sustainability, their biocompatibility and their non-toxicity, this makes these simpler and greener compared to other extractants (organophosphorus, azote derivatives, macrocyclic crown, etc…) used for metal extraction. These acids were applied as chelating agent for Th(IV) liquid–liquid extraction. The extractions were carried out in chloroform as an organic phase through the formation of thorium–OA, thorium–PA and thorium–LA complexes. The synergistic extraction of Th(IV) with these extractants in the presence of tributhylphosphine (TBP) has been investigated. The effect of different variables, such as time contact, pH of the aqueous phase, concentration of fatty acid, TBP addition on fatty acids, ionic strength and temperature, is reported. The results showed that the extraction kinetics using LA and OA were fast than with PA. The KNO₃ addition does not seem to highly influence the extraction yield, and no important synergy effect was noticed in the presence of TPB. Thermodynamic data for Th(IV) solvent extraction are also reported in this paper.     

EPR spectroscopy of transformations of iridium(III) and iridium(IV) hydroxo complexes in alkaline media

Processes that occur in strong alkaline solutions of iridium(III) and iridium(IV) hydroxo complexes have been studied by EPR and electronic absorption spectroscopy. It has been demonstrated that dissolution of iridium compounds in alkaline solutions should be accompanied by a series of complicated transformations involving oxygen, which lead to the formation of several binuclear iridium(III, III), (III, IV), and (IV, IV) dioxygen complexes.     

Theoretical studies of iridium-mediated tautomerization of substituted pyridines

Room temperature reaction of [Ir(COD)₂]BF₄ (COD = 1,5-cyclooctadiene) and amide-tethered or simple 2,3′-bipyridyls gave iridium(I) complexes bearing chelating protic pyridylidenes. This protic pyridylidene tautomer is stabilized by both chelation effect and by hydrogen bonding. The mechanistic details of this tautomerization of N-heterocycles to N-heterocyclic carbenes (NHCs) were investigated using the density functional theory (DFT). DFT studies suggested that cyclometalation of 2,3′-bipyridyls took place to give an iridium(III) hydride, which subsequently undergoes formal 1,3-hydrogen shift from the iridium to the pyridyl nitrogen atom. Two possible mechanisms of this formal 1,3-hydrogen shift process have been examined: the β-insertion of the hydride into an olefin followed by proton abstraction and the water-assisted proton transfer via a cyclic transition state. The latter mechanism is strongly favored in the presence of a catalytic amount of water, and this mechanism is applicable to the tautomerization of both amide-tethered and amide-free 2,3′-bipyridyls.     

Spectrofluorimetric determination of iridium(IV) traces using 4-pyridone derivatives

A new spectrofluorimetric determination of iridium(IV) with 3-hydroxy-2-methyl-1-phenyl-4-pyridone (HX) or 3-hydroxy-2-methyl-1-(4-tolyl)-4-pyridone (HY) is reported. Iridium(IV) react with HX or HY and chelates were extracted into chloroform or dichloromethane. The organic phase showed fluorescence. The fluorescence measurements to quantify iridium were carried out in its fluorescent band centred at λ_ex=373 nm and λ_em=480 nm. Under optimal conditions, the calibration graphs were linear over the concentration range of 0.1-7.6 μg ml⁻¹ of iridium for Ir(IV)-HX and 0.1-5.8 μg ml⁻¹ for Ir(IV)-HY with a correlation coefficients of 0.999 and 0.992 and relative standard deviation of ±1.1%.The method is free from interference by Rh(III) and Pt(IV), which normally interfere with other methods. Iridium can be determined in the presence of 300-fold excess of rhodium(III) and 10-fold excess of platinum(IV).The method was applied successfully to the determination of iridium in some synthetic mixtures and mineral sample gave satisfactory results.     

Mechanism of uranium(IV) extraction with CYANEX 302 in kerosene from nitrate medium

The extraction of U(IV) by bis(2,4,4-trimethylpentyl) monothiophosphinic acid (CYANEX 302) in kerosene from nitric acid solution has been investigated under equilibrium conditions. The effects of the different parameters affecting the extraction process were studied and the stoichiometry of the extracted species was elucidated. The kinetics of this extraction was also investigated using a stirred Lewis cell. The effects of the different parameters affecting the extraction rate as well as the temperature were separately investigated. The results are interpreted by a reaction mechanism where the extraction process of U(IV) is controlled by a chemical reaction at the interface rather than in the bulk phase.     

Extraction of Vanadium (IV) with DI-2-Ethylhexylphosphoric Acid

Abstract

It was established with the use of electron and ESR spectroscopic methods that in the presence of sodium sulfate, the extraction of vanadium (IV) with di-2-ethylhexylphosphoric acid takes place by a cation-exchange mechanism giving rise to two complex compounds of vanadium (IV) oxocation with sulfuric and di-2-ethylhexylphosphoric acid anions. The vanadium (IV) oxocation sulfate complex extracted in the solid state was examined with X-ray structural analysis. It was shown that the vanadium (IV) oxocation sulfate complex trihydrate crystallizes in the centrosymmetrical space group to form dimers with bridging sulfate groups.     

Bestimmung von Iridiumspuren mit Dithizon mittels substöchiometrischer Isotopenverdünnungsanalyse

Iridium(III or IV) reacts with dithizone on heating at pH 6 to form a 1∶2 complex, which can be concentrated by extraction into chloroform. Based on this reaction, a reproducible, selective determination of iridium (1 ppb) is achieved by means of substoichiometric isotope dilution analysis based on¹⁹²Ir.     

Extraction of iridium (IV) from hydrochloric acid media with crown ether in chloroform, and its determination by ICP-AES

A new method for the quantitative extraction and determination of trace amounts of iridium from hydrochloric acid media has been established based on the formation of an ion-association complex of iridium hexachloro anion IrCl6(2-) with dicyclohexyl-18-crown-6 (DC18C6) oxonium cation in chloroform, then determination by inductively coupled plasma atomic emission spectrometry (ICP-AES). The effect of various factors (solvent, acid concentration, crown ether, reagent concentration, shaking time, composition of the extracted species, foreign ions, etc.) on the extraction and back-extraction of iridium has been investigated. The procedure was used to determine traces of iridium in palladium chloride and rhodium chloride.