Anion exchange studies of indium(III) in malonate and ascorbate solutions separation from mixtures

Summary Systematic studies are presented on the anion-exchange behaviour of indium on Dowex 21K in malonic acid and ascorbic acid solutions. Hydrochloric, sulphuric, nitric and perchloric acids, also sodium and ammonium nitrate at different concentrations were tested as eluants in the two systems. Their efficiency was evaluated in terms of elution constants. Methods have been developed for the separation of indium from several elements in malonate as well as ascorbate media with the technique of selective sorption, selective elution or by gradient elution.     

Anion exchange studies of lead in chloride and malonate solutions separation from mixtures

Summary Lead forms anionic chloride complexes in 4 M hydrochloric acid and a malonate complex at pH 4.8 with malonic acid. The behaviour of these complexes has been studied on Dowex 21-K resin with various eluants and methods have been developed for the separation of lead from several elements. The technique has been extended to the analysis of lead-based alloys. Satisfactory results are obtained.

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Zusammenfassung Die anionischen Chlorid- und Malonatkomplexe des Bleis wurden in ihrem Verhalten am Ionenaustauscher Dowex 21-K untersucht und Methoden zur Abtrennung des Bleis von mehreren anderen Elementen ausgearbeitet. An einem Beispiel wird die Analyse einer Bleilegierung beschrieben. Es werden zufriedenstellende Ergebnisse erhalten.

     

Anion exchange studies of zirconium(iv) in citrate solution separation from mixtures

The anion exchange behaviour of zirconium(IV) in a citrate system is described. Nitric acid, hydrochloric acid, perchloric acid and ammonium chloride were tested as eluants on Dowex ₂₁K column. Zirconium is separated from fission product elements e.g., barium, strontium, cadmium, caesium, molybdate and also from lead.     

Separation and analysis of aluminium(III) by cation exchange ion chromatography

A method for the determination of aluminium(III) ions based on separation by cation exchange column chromatography and detection by conductivity detector has been developed. It is fast and reliable, and can be used for the separation and analysis of aluminium(III) ions from other metal ions like Mg(II), Mn(II), Zn(II), Co(II), Ca(II), Sr(II), rare earth elements like Lu(III), Tm(III), and Gd(III), which are eluted at different times and so do not interfere. Effect of p-phenylene diamine concentration present in the eluent, presence of other metal ions and effect of various anions present in the injection sample on the separation and analysis of aluminium(III) ions have also been studied.     

Conductance of iron(III) laurate solutions in binary liquid mixtures

Summary The specific conductivity of iron(III) laurate solutions in binary liquid mixtures shows that the soap aggregates into micelles and CMC is found to be independent of temperature and concentration of benzene, acetone and tetrachloromethane in 1-butanol. The variation of molecular conductance,, with soap concentration, C, is expressed by the equation: = 10^AC^B. Both constants A and B vary with solvent composition but B remains constant with increase in temperature. Several parameters such as molecular conductance at infinite dilution, , dissociation constant, K, heat of dissociation, H, entropy, S and free energy, G of dissociation of soap have been evaluated and the effect of the nature of solvents has been discussed.     

Iron (II) and iron (III) isotope exchange in water–dimethyl sulfoxide mixtures

The rate of the isotope exchange reaction between iron(II) and iron(III) perchlorates has been measured in a solvent mixture containing a 3:2 mole ratio of water to dimethyl sulfoxide over the temperature range from 25° to ?98°C. In this temperature range, the reactants can diffuse together faster than they can undergo isotope exchange. The activation enthalpy and entropy for the acid-independent reaction were 6.0 ± 1.2 kcal/mole and ?38 ± 17 cal/deg mole, respectively. Below ?22°C, the acid-dependent exchange reaction did not contribute significantly to the exchange. In liquid media at ?112° and ?117°C and in a solid glass at ?136°C, no isotope exchange was observed over the period of a calculated half-life for the reaction. At these temperatures, the rate at which the reactants diffuse together is slower than the calculated rate of isotope exchange. In a solid glass at ?196°C, no isotope exchange was observed over the period of one week.     

Cation exchange studies of vanadium(V) on Dowex 50W-X8. Separation from mixtures

Summary The cation exchange behaviour of milligram amounts of vanadium on Dowex 50W-X8 has been studied using different eluants. Quantitative elution can be achieved by 200 ml of 0.5N hydrochloric acid, 1–2N sulphuric acid, 2–3N phosphoric acid or 0.5–1N ammonium chloride solution. The relative efficiency of eluants is discussed in terms of their elution constants and bed distribution coefficients. Vanadium has been separated from copper(II), iron(III), cobalt(II), nickel, zinc, zirconium (IV), aluminium, cerium(IV), uranium(VI), thorium(IV), manganese(II), titanium(IV), and from phosphate.

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Zusammenfassung Das Verhalten von Milligramm-Mengen Vanadium am Kationenaustauscher Dowex 50W-X8 wurde mit verschiedenen Eluierungsmitteln untersucht. Mit 200ml 0,5 n Salzsäure, 1–2 n Schwefelsäure, 2–3 n Phosphorsäure oder 0,5–1 n Ammoniumchloridlösung konnte das Vanadium quantitativ eluiert werden. Die Wirksamkeit dieser Eluierungslösungen wurde an Hand der Elutionskonstanten und der Verteilungskoeffizienten erörtert. Von folgenden Ionen konnte das Vanadium getrennt werden: Kupfer(II), Eisen(III), Kobalt(II), Nickel, Zink, Zirkonium(IV), Aluminium, Cer(IV), Uran(VI), Thorium(IV), Mangan(II), Titan(IV) und Phosphat.

     

Solvent extraction separation of iron(III) and aluminium(III) from other elements with Cyanex 302

A rapid method was developed for the solvent extraction separation of iron(III) and aluminium(III) from other elements with Cyanex 302 in chloroform as the diluent. Iron(III) was quantitatively extracted at pH 2.0-2.5 with 5 x 10(-3) M Cyanex 302 in chloroform whereas the extraction of aluminium(III) was quantitative in the pH range 3.0-4.0 with 10 x 10(-3) M Cyanex 302 in chloroform. Iron(III) was stripped from the organic phase with 1.0 M and aluminium(III) with 2.0 M hydrochloric acid. Both metals were separated from multicomponent mixtures. The method was applied to the separation of iron and aluminium from real samples.     

Kojic acid derivatives as powerful chelators for iron(III) and aluminium(III)

Proceeding from a ligand constituted by two units of kojic acid linked by a methylene group, which proved a very promising chelator for excess iron(III) and aluminium(III) pathologies, two new ligands have been designed and synthesized: one by adding a vanillin molecule in the linker and the second by adding an o-vanillin molecule. Both these ligands, on the basis of complex formation studies presented here, show significant potential as therapeutic agents for iron and aluminium overload. Protonation constants of the pure ligands have been determined by potentiometry, and standard reaction heats by calorimetry. Hydrogen bonding plays an important role in the protonation reactions. The crystal structures of both ligands have furthermore been resolved. Complex formation equilibria for the iron complexes have been studied by combined potentiometry-spectrophotometry and those of aluminium by potentiometry alone. All complexes were found to contain two metal ions. NMR diffusion measurements hardly applied to complex formation equilibria and the results of density functional theory (DFT) calculations were powerful tools in confirming the proposed reaction model and in evaluating the relative stabilities of the products. Further support was given by NMR chemical shift measurements and electrospray mass spectrometry.     

Separation and preconcentration of iron(II) and iron(III) from natural water on a melamine-formaldehyde resin

A combined method for the preconcentration and selective spectrophotometric determination of both valencies of iron, i.e., Fe(II) and Fe(III), down to 0.4 mug l(-1) has been developed. Iron(III) from synthetic and natural water samples has been concentrated on a melamine-formaldehyde resin at pH 5; iron(II) was not retained under identical conditions. The oxidized iron was concentrated on a second resin column. The iron in both columns was eluted with 1 M HCl solution and separately analyzed by the 1,10-phenanthroline-citrate spectrophotometric method. The effect of pH, adsorption and elution rates, and interferences on the developed procedure were investigated. Metal ions that can be retained by the resin at moderate concentrations, e.g., Al(3+), do not cause interference in more dilute solutions encountered in natural water samples. At least 160-fold volume enrichment can be easily obtained using an adsorption flowrate of 50 ml min(-1). A hydrothermal water sample was analyzed by the recommended procedure and by a literature method, and the results were statistically compared by t- and F-tests.     

Synthesis,crystal structures and spectroscopic studies of praseodymium(III) malonate complexes

Reactions of malonic acid (H₂mal) with PrCl₃·6H₂O afforded the known complex [Pr₂(mal)₃(H₂O)₆]_n (1), and compounds [Pr₂(mal)₃(H₂O)₆]_n·2nH₂O (2·2nH₂O), [PrCl(mal)(H₂O)₃]_n·0.5nH₂O (3·0.5nH₂O) and [Pr(mal)(Hmal)(H₂O)₃]_n·nH₂O (4·nH₂O) using various reaction ratios, reaction media (H₂O, MeOH) and pH values. Analogous reactions with CeCl₃·7H₂O afforded compounds [Ce₂(mal)₃(H₂O)₆]_n (5), [CeCl(mal)(H₂O)₃]_n·nH₂O (6·nH₂O) and [Ce(mal)(Hmal)(H₂O)₃]_n·nH₂O (7·nH₂O). Compounds 2·2nH₂O and 3·0.5nH₂O were characterized by X-ray crystallography, and 4–7 by microanalytical and spectroscopic data. The malonate(-2) ligand adopts three different coordination modes in the structures of 1–3, i.e., the μ₂-κO:κO′:κO″ and the μ₄-κ²O:κO′:κ²O″:κO? in 1 and 2 leading to a 3D network structure, and the μ₃-κ²O:κO′:κ²O″:κO? in 3 promoting an 1D structure. The thermal decomposition of 1 and 3·0.5nH₂O was monitored by TG/DTA and TG/DTG measurements. The structural features of 1–3 are discussed in terms of known malonato(-2) Ln^III and Ca^II complexes. The bioinorganic chemistry relevance of our results is discussed.     

Separation of microgram quantities of aluminum and iron(III)

The separation of microgram quantities of ferric iron and aluminum can be effected by passage of an acidic thiocyanate solution through the anion exchange resin Amberlite IRA-400A. The anionic complex of iron and thiocyanate remains on the column whereas aluminum passes through with the eluate. This method has been utilized in the separation of up to 200 μg of iron from comparable amounts of aluminum thus permitting the spectrophotometric determination of the latter in caustic liquors and other alkali products.