Liquid-liquid extraction and recovery of indium using Cyanex 923

The extraction of In(III) from HCl, H₂SO₄, and HNO₃ media using a 0.20 mol l⁻¹ Cyanex 923 solution in toluene is investigated. In(III) is quantitatively extracted over a fairly wide range of HCl molarity while from H₂SO₄ and HNO₃ media the extraction is quantitative at low acid concentration. The extracted metal ion has been recovered by stripping with 1.0 mol l⁻¹ H₂SO₄. The stoichiometry of the In(III): Cyanex 923 complex is observed to be 1:2. The extraction of In(III) is insignificantly changed in diluents namely toluene, n-hexane, kerosene (160-200 °C), cyclohexane, and xylene having more or less the same dielectric constants, whereas, it decreases with increasing polarity of diluents such as cyclohexanone and chloroform. The extractant is stable towards prolonged acid contact and there is a negligible loss in its extraction efficiency even after recycling for 20 times. The extraction behavior of some commonly associated metal ions namely V(IV), Ti(IV), Al(III), Cr(III), Fe(III), Ga(III), Sb(III), Tl(III), Mn(II), Fe(II), Cu(II), Zn(II), Cd(II), Pb(II), and Tl(I) has also been investigated. Based on the partition data the conditions have been identified for attaining some binary separations of In(III). These conditions are extended for the recovery of pure indium from zinc blend, zinc plating mud, and galena. The recovery of the metal ions is around 95% with purity approximately 99%.     

Synthesis and efficiency of poly(acrylamidrazonehydrazide) chelating fiber for preconcentrating and separating trace gold and palladium from solution

A new poly(acrylamidrazone-hydrazide) chelating fiber has been synthesized using polyacrylonitrile fiber as a starting material. An ICP-OES method for applying the fiber to preconcentrate and separate trace Au(III) and Pd(IV) ions in solution has been established. The experiments show that 8 ng/ml Au(III) and 6 ng/ml Pd(IV) in 1000 ml of solution can be enriched quantitatively by the fiber column at a flow rate of 12 ml/min at pH 2. These ions can be desorbed quantitatively with 10 ml of 2.5% CS(NH₂)₂ + 6% H₂SO₄ containing 0.2% Fe(II) from the column at an elution rate of 6 ml/min. A fiber treated with 12M HCl or 15M HNO₃ can be re-used 10 times with above 95% recoveries of Au(III) and Pd(IV), and 120–800-fold excesses of Cu(II), Mn(II), Fe(III), Al(III), Ni(II), Mg(II) and Ca(II) ions cause little interference. The RSDs are 2.0% for 8 ng/ml Au and 3.5% for 6 ng/ml Pd. The recovery of added standard in a solution sample from a metal smelter is 96.2% for Au and 100% for Pd, and the content of each ion in the sample determined by the method is in agreement with the analysed value from the smelter laboratory.     

Synthesis and Efficiency of an Epoxy-Urea Chelating Resin for Preconcentrating and Separating Trace Bi,In, Sn,Zr, V And Ti From Solution Samples

Abstract

A new epoxy-urea chelating resin was synthesized from epoxy resin and used for the preconcentration and separation of trace Bi(III), In(III), Sn(IV), Zr(IV), V(V) and Ti(IV) ions from solution samples. The analyzed ions can be enriched at pH 5 at a flow rate of 1–4 ml/min, and can be also desorbed with 10 mL of 2 M HCl +0.1g NH₄F solution from the resin column, with recoveries over 97%. The chelating resin reused 6 times can still adsorb quantitatively the Bi, In, Sn, Zr, V and Ti ions, and eighty to thousand-fold excesses of Ca(II), Mg(II), Cu(II), Zn(II), Al(III), Sb(III), Ni(II), Mn(II) and Fe(III) cause little interference with the enrichment and determination of these ions. The RSDs of the proposed method for the determination of 500–50 ng/ml Bi, In and Sn, 50–5.0 ng/ml Zr, V and Ti were in the range of 0.4 ～ 4.0%, the enrichment factor of the resin for the ions is in the range of 10–100. The recoveries of added standard in waste water are between 96% and 100%, and the concentration of each ion in alloy steel sample determined by the method is in good agreement with the reference value analyzed by a steel plant with average error <2.8%.     

ICP-OES determination of traces of Ru, Au, V and Ti preconcentrated and separated by a new poly(epoxy-melamine) chelating resin from solutions

A new poly(epoxy-melamine) chelating resin is synthesized from epoxy resin and used for the preconcentration and separation of traces of Ru(III), Au(III), V(V) and Ti(IV) ions from sample solutions. The ions analyzed can be quantitatively enriched by the resin at a flow-rate of 2 mL/min at pH 4, and quantitatively desorbed with 10 mL of 1 mol/L HCl + 0.2 g CS(NH₂)₂ at a flow-rate of 1 mL/min with recoveries of over 97%. The chelating resin can be reused 7 times without obvious loss of efficiency. Thousand-fold excesses of coexistent ions caused little interference during the enrichment and determination steps. The RSDs for the determination of 50 ng/mL Ru(III) and Au(III), 5.0 ng/mL V(V) and Ti(IV) were in the range of 1.5–4.5%. The recoveries of added standards in a real sample solution are between 96% and 100%, and the results for the ions analyzed in a nickel alloy sample are in good agreement with their reported values.     

Consecutive thin-layer chromatographic separation of Au(III), Pt(IV), Pd(II) and large amounts of associated base metals

Summary The TLC system composed of ECTEOLA-cellulose and 2.5 mol/l HCl–2.5 mol/l NaCl–0.6% (w/v) H₂O₂ solution allows consecutive separations of Au(III), Pt(IV), Pd(II) and a number of associated base metals such as Cr(III), Mn(II), Fe(III), Co(II) Ni(II), Cu(II), Mg, Ca, Ba, Al, Bi(III), Pb(II), Zn(II) and Ag(I) coexisting in an extremely wide range of amounts and ratios, to be conducted completely in a single run. The effectiveness of the present system is verified by applying it to various synthesized samples containing the three noble metals and one of the base metals, Pt-metal powder and two kinds of Au-alloys.     

Polarographic analytical determination of Hg(II), Cu(II), Cd(II), As(III), Sb(III), Ti(IV) and U(VI) in the presence of Fe(III)

The analytical determination of Hg(II), Cu(II), Cd(II), As(III), Sb(III), Ti(IV) and U(VI) in the presence of Fe(III) and 1 M H₂SO₄ are investigated using the polarographic technique. The wave corresponding to the reduction of Fe(III) to Fe(II) was found to be completely suppressed by the addition of 1% pyrogallol. Thus, different mixtures of these elements, viz. Hg(II), Cu(II), Cd(II), As(III) and Fe(III)-mixture (A), Cu(II), Cd(II), Sb(III), As(III) and Fe(III)-mixture (B), and Cu(II), Cd(II), Ti(IV), U(VI) and Fe(III)-mixture (C), were quantitatively determined using 1% pyrogallol and 1 M H₂SO₄ as supporting electrolyte. The i₁/c results give excellent correlations in each case, as indicated from the results of leastsquares regression analysis.     

Sulfonylcalix[4]arenetetrasulfonate as pre-column chelating reagent for selective determination of aluminum(III), iron(III), and titanium(IV) by ion-pair reversed-phase high-performance liquid chromatography with spectrophotometric detection

Sulfonylcalix[4]arenetetrasulfonate (SO₂CAS) has been examined as a pre-column chelating reagent for ultratrace determination of metal ions by ion-pair reversed-phase high-performance liquid chromatography with spectrophotometric detection. Metal ions were converted into the SO₂CAS chelates in an acetic buffer solution (pH 4.7). The chelates were injected onto a n-octadecylsilanized silica-type Chromolith™ Performance RP-18e column and were eluted using a methanol (50 wt.%)-water eluent (pH 5.6) containing tetra-n-butylammonium bromide (7.0 mmol kg⁻¹), acetate buffer (5.0 mmol kg⁻¹), and disodium ethylendiamine-N,N,N′,N′-tetraacetate (0.10 mmol kg⁻¹). Under the conditions used, Al(III), Fe(III), and Ti(IV) were selectively detected among 21 kinds of metal ions [Al(III), Ba(II), Be(II), Ca(II), Cd(II), Co(II), Cr(III), Cu(II), Fe(III), Ga(III), Hf(IV), In(III), Mg(II), Mn(II), Mo(VI), Ni(II), Pb(II), Ti(IV), V(V), Zn(II), and Zr(IV)]. The detection limits on a 3σ blank basis were 8.8 nmol dm⁻³ (0.24 ng cm⁻³) for Al(III), 7.6 nmol dm⁻³ (0.42 ng cm⁻³) for Fe(III), and 17 nmol dm⁻³ (0.80 ng cm⁻³) for Ti(IV). The practical applicability of the proposed method was checked using river and tap water samples.     

Preparation, characterization and metal sorption studies of a Chrome-Azurol-S-loaded anion-exchange resin

Chrome Azurol S (CS) was mobilized on an strongly basic anion-exchange resin (Dowex 2 x 4, in Cl(-) form) by batch equilibration. The modified resin was stable in acetate buffer solution and in 0.1 M HCl and H(2)SO(4), but it was readily degraded with 2-6 M HCl and HNO(3). Retention of Ba(II), Sr(II), Ca(II), Mg(II), Al(III), Cr(III), Zn(II), Fe(III), Ti(IV), Mn(II), Co(II), Ni(II), Cu(II), Cd(II) and Pb(II) was studied using the batch equilibration method. The uptake and recovery yields were determined by using inductively-coupled plasma atomic emission spectroscopy (for Mg, Al, Cr, Ti, Fe, Mn, Ni, Zn, Cu, Cd and Pb) and atomic absorption spectrophotometry (for Ba, Sr, Ca and Co). The optimum pH value was established for performing a selective separation of Al(III) from the other metal ions. The sorption capacities of the CS-loaded resing for Al(III), Cr(III), Mg(II) (at pH 6), Fe(III) (at pH 5) and Ti(IV) (at pH 4) were 14, 2.9, 0.3, 3 and 3.9 mumoles g(-1) respectively. On this basis a method for separating Al(III) from other cations was established.     

ICP-OES determination of traces of Ru, Au, V and Ti preconcentrated and separated by a new poly(epoxy-melamine) chelating resin from solutions

A new poly(epoxy-melamine) chelating resin is synthesized from epoxy resin and used for the preconcentration and separation of traces of Ru(III), Au(III), V(V) and Ti(IV) ions from sample solutions. The ions analyzed can be quantitatively enriched by the resin at a flow-rate of 2 mL/min at pH 4, and quantitatively desorbed with 10 mL of 1 mol/L HCl + 0.2 g CS(NH₂)₂ at a flow-rate of 1 mL/min with recoveries of over 97%. The chelating resin can be reused 7 times without obvious loss of efficiency. Thousand-fold excesses of coexistent ions caused little interference during the enrichment and determination steps. The RSDs for the determination of 50 ng/mL Ru(III) and Au(III), 5.0 ng/mL V(V) and Ti(IV) were in the range of 1.5–4.5%. The recoveries of added standards in a real sample solution are between 96% and 100%, and the results for the ions analyzed in a nickel alloy sample are in good agreement with their reported values. Received: 12 May 1997 / Revised: 1 September 1997 / Accepted: 9 October 1997     

Influence of hydrolyzed and nonhydrolyzed Ti,Cr, and Al ions on the formation of beta-FeOOH particles

Beta-FeOOH particles were synthesized in the presence of Ti(IV), Al(III), and Cr(III) at metal/Fe atomic ratios of 0-0.1 by the following two methods: hydrolysis of aqueous FeCl3 solutions added to the hydrolysis products of these metal ions (subsequent hydrolysis, SH) and hydrolysis of aqueous FeCl3 solutions dissolving these metal ions (combined hydrolysis, CH). On increasing Al/Fe the particle size of the products with AlCl3 by SH method steeply rose at a low Al/Fe and then fell. The similar increase of particle size was seen in SH method with Ti(SO4)2 though the addition of TiCl4 decreased the particle size. In CH method, Ti(IV) markedly impeded the beta-FeOOH formation but Al(III) and Cr(III) showed no influence. The particles prepared by CH and SH methods contained a large amount of Ti(IV) but a few Al(III) and Cr(III). The large spindle-shaped and rod-shaped particles produced by SH method with AlCl3 and Ti(SO4)2 were highly microporous and poorly crystallized, indicating that the particles consist of fine primary particles and the aggregation of fine particles would be promoted by SO4(2-). The different influences of the metal ions on the beta-FeOOH formation were explained by their hydrolysis characteristics.     

Properties and applications of polyacrylacylisothiourea chelating fiber for preconcentration and separation of trace titanium, vanadium and bismuth

An ICP-OES method using a new poly-acrylacylisothiourea chelating fiber to preconcentrate and separate trace Ti(IV), V(V) and Bi(III) ions from solution samples is established. The results show that 5–25 ng/ml of Ti or V and 50–250 ng/ml of Bi ions in 200–1000 ml of solution can be enriched quantitatively by 0.05 g of the fiber at pH 3 with recoveries over 97%. These ions can be desorbed quantitatively with 10 ml of 4M HC1O₄. 100- to 1000-fold excesses of Fe(III), Al(III), Ca(II), Mg(II), Cu(II), Ni(II) and Mn(II) ions cause little interference. The chelating fiber stored for about 2 years can still be used repeatedly for preconcentration and separation of trace Ti, V and Bi ions from solution with above 95% recovery. The RSDs for enrichment and determination of 5 ng/ml of Ti or V and 50 ng/ml of Bi are in the range 2.5–2.8%. The recoveries of added standard in real waste waters and mineral samples are between 96 and 100%, and the concentration found for each ion in the mineral sample was in good agreement with that measured by ETAAS.     

Potentiometric determination of uranium in the presence of plutonium in H2SO4 medium

The potentiometric determination of uranium is widely carried out in phosphoric acid medium to suppress the interferences of plutonium by complexation. Owing to the complexity of the recycling plutonium from the phosphate based waste involving manifold stages of separation, a method has been proposed in the present paper which does not use phosphoric acid. Uranium and plutonium are reduced to U/IV/ and Pu/III/ in 1M H₂SO₄ by Ti/III/, and NaNO₂ is chosen to selectively oxidize Pu/III/ and the excess of Ti/III/. The unreacted NaNO₂ is destroyed by sulphamic acid and excess Fe/III/ is added following dilution. The equivalent amount of Fe/II/ thus liberated is titrated against standard K₂Cr₂O₇. R.S.D. obtained for the determination of uranium /1–2 mg/ is 0.3% with plutonium being present upto 4.0 mg.     

Hydrogen chemical ionization mass spectrometry of metalloporphyrins

The hydrogen chemical ionization (H₂ CI) mass spectra of a range of metal(II) (Ni, Cu, Co, Pt), metal (III) (Al, Mn, Ga, Fe (bearing a single axial ligand)) and metal(IV) (Si, Ge, Sn (bearing two axial ligands) and V (as V?O²⁺)) porphyrins have been determined, The spectra are highly dependent on the coordinated metal, rather than the axial ligand(s) (where present). Ni(II), Cu(II), Mn(II or III), Ga(III), Ge(IV), Fe(III) and Sn(IV) porphyrins fragment via hydrogenation and demetallation, followed by cleavage of the resulting porphyrinogens at the meso(bridge) positions to give mono- and di-pyrrolic fragments. Tripyrrolic fragments are also observed in the case of Ni(II), Cu(II) and Sn(IV). Fragmentations of this type are similar to those observed for free-base porphyrins. In the case of Pt(II), Co(II), Al(III), Si(IV) and V(IV) (as vanadyl), the dipyrrolic fragment ions are either very weak or completely absent; hence their H₂CI spectra contain limited structural information. This variable CI behaviour may be related to the relative stabilities of the metalloporphyrins together with the multiple stable valency states exhibited by several metals.     

Oximidobenzotetronic acid as a reagent for the separation and gravimetric determination of palladium and cobalt

Oximidobenzotetronic acid is recommended for the separation and gravimetric determination of palladium and cobalt An ethanolic solution of the reagent quantitatively precipitates palladium(II) from solutions which are 0.75 N in acid up to pH 5.1, the complex is weighed as Pd(C₉H₅NO₄)₂. Cobalt(II) can be determined in the filtrate after the precipitation of palladium. With 0.5 N acid solutions, no interference was found from Pt(IV), Ir(IV), Rh(III), Ru(III), Os(IV), Au(III), Ag(I), Cu(II), Fe(III), Ni(II), Hg(II). Pb(II), Bi(III), Cd(II), As(V), Se(VI), Te(IV), Mo(VI), Sb(III), Al(III), Cr(III), Zn(II), Ti(IV), Zr(IV). acetate, oxalate, citrate, tartrate, phosphate and fluoride.     

Application of the Weisz Ring oven technique to the separation and identification of micro-quantities of some less familiar cations

Summary Use of the ring oven in separation and identification of mixtures of less familiar metal ions has been described. Separation of metal ions from the following mixtures has successfully been carried out: 1. UO₂(II) and Th(IV), 2. Th(IV) and Ce(IV), 3. Pd(II) and Au(III), 4. Pt(IV) and Au(III), 5. Ce(III) and Ce(IV), 6. UO₂(II), Th(IV) and Ti(IV), 7. Th(IV), Ti(IV) and Ce(IV), 8. Th(IV), Ce(IV) and Zr(IV), 9. Ti(IV), V(V) and Zr(IV), 10. Mo(VI), V(V) and W(VI) and 11. Be(II), Al(III) and Mg(II). In the case of binary mixtures, the separation was in the form of a central spot and a concentric ring; in ternary mixtures the metals were precipitated in a central spot and two concentric rings.

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Zusammenfassung Zur Trennung und Identifizierung folgender Gemische seltenerer Metallionen wurde der Ringofen mit Erfolg verwendet: 1. UO₂(II) und Th(IV), 2. Th(IV) und Ce(IV), 3. Pd(II) und Au(III), 4. Pt(IV) und Au(III), 5. Ce(III) und Ce(IV), 6. UO₂(II), Th(IV) und Ti(IV), 7. Th(IV), Ti(IV) und Ce(IV). 8. Th(IV), Ce(IV) und Zr(IV), 9. Ti(IV), V(V) und Zr(IV), 10. Mo(VI), V(V) und W(VI) und 11. Be(II), Al(III) und Mg(II). Bei binären Gemischen erfolgt die Trennung in einen zentralen Fleck und einen Ring, bei ternären Mischungen in einen Fleck und zwei konzentrische Ringe.

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Résumé On a décrit l'utilisation du four annulaire pour la séparation et l'identification de mélanges d'ions métalliques moins courants. On a effectué la séparation des ions métalliques à partir des mélanges suivants: 1. UO₂(II) et Th(IV), 2. Th(IV) et Ce(IV), 3. Pd(II) et Au(III), 4. Pt(IV) et Au(III), 5. Ce(III) et Ce(IV), 6. UO₂(II), Th(IV) et Ti(IV), 7. Th(IV), Ti(IV) et Ce(IV), 8. Th(IV), Ce(IV) et Zr(IV), 9. Ti(IV), V(V) et Zr(IV), 10. Mo(VI), V(V) et W(VI) et 11. Be(II), Al(III) et Mg(II). Dans le cas des mélanges binaires, la séparation se présentait sous forme d'une tache centrale et d'un anneau concentrique; chez les mélanges ternaires, les métaux étaient précipités en une tache centrale et deux anneaux concentriques.

     

The ion chromatographic separation of high valence metal cations using a neutral polystyrene resin dynamically modified with dipicolinic acid

A neutral polystyrene resin column, dynamically loaded with dipicolinic acid at a concentration of 0.1 mM in 1 M potassium nitrate eluent, was investigated for the separation characteristics of a number of high valence metal cations over the pH range 0-3. The metal species studied were Th(IV), U(VI), Zr(IV), Hf(IV), Ti(IV), Sn(IV), V(IV) and V(V), Fe(III) and Bi(III), of which Ti(IV), Sn(IV), V(IV) and Fe(III) did not show any retention. For the remaining metal ions, significant retention was obtained with good peak shapes, except for Th(IV), which moved only slightly from the solvent front with some tailing. The retention order at pH 0.3 was Th(IV) < V(V) < Bi(III) < U(VI) < Hf(IV) < Zr(IV). A notable feature of this separation system was the high selectivity shown for uranium, zirconium and hafnium, the last two being nearly resolved in 15 min on the relatively short 10 cm column.     

Some New Reagents in Inorganic Paper Chromatography

Abstract

Sensitive colour reactions given by 2-Hydroxy-4-methoxyacetophenone; 4-Benzyloxyresacetophenone; 2′, 4′, 4-Trihydroxychalkone; 2-Hyaroxy-4′, 6′-dimethoxychalkone and 2-Methyl-5,7-dihydroxychromone are reported as chromatographic spray reagents for the detection of a number of metal ions on paper chromatograms. Sensitivity limits for detection of Be(II), Al(III), V(IV), Fe(II), Fe(III) and Th(IV) in relation to 2-Hydroxy-4-methoxyacetophenone; 2′-Hydroxy-4′, 6′-dimethoxychalkone; 2′, 4′, 4-Trihydroxychalkone and 2-Methyl-5, 7-dihydroxychromone are also reported alongwith separation of groups of metal ions by using three new solvent systems.     

Electrochemical amination of benzene in aqueous-acetic solutions of sulfuric acid

Indirect cathodic amination of benzene with hydroxylamine in the presence of Ti(IV)/Ti(III) mediator system in aqueous media containing 4–11 mol/L H₂SO₄ and 13–5.5 mol/L AcOH has been studied. Aniline, diphenyl, and isomeric phenylenediamines are the electrolysis products at 25–60°C. The increase in temperature favors the formation of the monoamino compound. Aniline yield with respect to hydroxylamine at complete conversion of the latter has reached 78.7%, mass fraction of aniline being 97.1%.     

Electrochemical amination. Ti(IV)/Ti(III) mediator system in aqueous solutions of sulfuric acid

As a result of polarographic and spectrophotometric studies, and mathematical modeling, the dependence of electrochemical properties of the Ti(IV)/Ti(III) pair on the composition of the Ti(IV) complexes is established in sulfuric acid solutions. It is found that Ti(IV) in 1–17 M H₂SO₄ at the metal ion concentrations used in the process of amination of aromatic compounds can exist in the form of twelve basic complex forms, of which seven, including the binuclear and two tetranuclear ones, are observed for the first time. Ten forms are electrochemically active. An increase in the overall amount of reversibly reducing cationic mononuclear hydrosulfate complexes of Ti(IV) among these at a growing H₂SO₄ concentration results in an increase in the redox potential of the Ti(IV)/Ti(III) mediator system and therefore in an increase in the yield of the electrochemical amination products.     

Interaction of Aluminium (III) with the f-Family Ions Np(VI), Pu(VI), Np(V), Np(IV), Pu(IV), Nd(III), and Am(III) in the Course of Simultaneous Hydrolysis

The interaction of Np(VI), Pu(VI), Np(V), Np(IV), Pu(IV), Nd(III), and Am(III) with Al(III) in solutions at pH 0–4 was studied by the spectrophotometric method. It was shown that, in the range of pH 3–4, the hydrolyzed forms of neptunyl and plutonyl react with the hydrolyzed forms of aluminium. In the case of Pu(VI), the mixed hydroxoaqua complexes (H₂O)₃PuO₂(-OH)₂Al(OH)(H₂O)₃ ²⁺ or (H₂O)₄PuO₂OAl(OH)(H₂O)₄ ²⁺ are formed at the first stage of hydrolysis. Np(VI) also forms similar hydroxoaqua complexes with Al(III). The formation of the mixed hydroxoaqua complexes was also observed when Np(IV) or Pu(IV) was simultaneously hydrolyzed with Al(III) at pH 1.5–2.5. The Np(IV) complex with Al(III) has, most likely, the formula (H₂O) _n (OH)Np(-OH)₂Al(OH)(H₂O)₃ ³⁺. At pH from 2 to 4.1 (when aluminium hydroxide precipitates), the Np(V) or Nd(III) ions exist in solutions with or without Al(III) in similar forms. When pH is increased to 5–5.5, these ions are almost not captured by the aluminium hydroxide precipitate.