Reversed Phase Extraction Chromatographic Separation Of Scandium With Amberlite LA-1 From Malonate Solutions

Abstract

Scandium was extracted at pH 5.0 from 0.01 M malonic acid on silica gel column impregnated with Amberlite LA-1. Nickel, zinc, cadmium, mercury, lead, tin, aluminium, and lanthanum in binary mixtures because they could not form malonato complexes. It was separated by the process of selective elution from elements such as zirconium, thorium, uranium, iron(III), gallium, indium, cerium(III), litanium by exploiting difference in stability of malonato complexes. Scandium was separated from multicomponent mixture containing yttrium, titanium, zironium, thorium, uranium and aluminium by a process of selective sorbtion and selective elution.     

Separation of thorium as ascorbato complex by extraction with Aliquat 336S

Thorium was quantitatively extracted with 0.1M Aliquat 336S at pH 4.5 from 0.01M ascorbic acid. It was then stripped with 2M hydrochloric acid. Thorium arsenazo III complex was determined spectrophotometrically at 655 nm. It was separated from binary and tertiary mixtures by exploiting the difference in distribution ratios of various elements from ascorbic acid media. Some separations were accomplished by selective stripping of thorium from nitric and hydrochloric acid. The method was extended for the analysis of thorium in monazite and gas mantles.     

Extraction chromatographic separation of thorium (IV) with tri-n-octylphosphine oxide (TOPO)

Thorium was extracted from a mixture of nitric acid and NaNO₃ of 0.01M each at pH 2.2 on a column of silica gel coated with TOPO. Thorium was separated from alkalis, alkaline earths, chromium, iron, cobalt, nickel, zinc, cadmium, mercury, lead, trivalent rare earths, platinum group metals, chloride, phosphate and acetate in binary mixtures by selective extraction of thorium. Thorium was separated from cerium (IV), zirconium, uranium and molybdenum by selective elution of thorium with 0.01M H₂SO₄. The method was extended for the analysis of thorium in monozite ore.     

Solvent extraction separation of thorium as picrate complex with 18-crown-6

Thorium was quantitatively extracted from 0.04M picric acid with 0.065M of 18-crown-6 at pH 2.0–3.5. It was stripped from organic phase with 0.5M nitric acid and was determined spectrophotometrically at 655 nm as its Arsenazo-III complex. Thorium was separated from mixture containing cerium, uranium, zirconium, hafnium, yttrium and lead in complex mixtures. The method was extended for the analysis of thorium in monazite.     

Separation and gravimetric determination of thorium and cerium(IV) with vanillin

Vanillin forms insoluble complexes with thorium and cerium(IV) at pH 4.0–6.2 and 2.5–7.0 respectively. Thorium and cerium can be determined gravimetrically and separated from each other as well as from uranium(VI) and typical trivalent rare earths. The precipitates obtained are ignited to the corresponding oxide and weighed; as little as 4.4 mg of ThO₂ and 4.9 mg of CeO₂ can be determined.     

Determination of zirconium,thorium and scandium with 2,5-dihydroxy-1,4-benzoquinone

Zirconium is quantitatively precipitated by 2,5-dihydroxy-1,4-benzoquinone and is separated from scandium in 1 N hydrochloric acid solution. Thorium is separated at pH 0.5 from uranium(VI), cerium(IV), lanthanum, yttrium and scandium. Scandium is quantitatively precipitated by this reagent in the pH range 1.4–2.0 and at pH 1.5 equivalent amounts of lanthanum do not interfere; small amounts of yttrium cause interference.     

Liquid anion-exchange separation of vanadium from malonate media

Summary Vanadium(IV) and (V) can be quantitatively extracted with 0.2 mol/l Amberlite LA-2 in xylene at pH 3.0 from 0.02 mol/l malonic acid, stripped with 0.5 mol/l hydrochloric acid, and determined spectrophotometrically. Five other liquid anion exchangers (Amberlite LA-1, Primene JM-T, Aliquat 336S, TOA and TIOA) were examined as possible extractants. The extraction of vanadium(IV) was found to be quantitative only with Amberlite LA-2, while that of vanadium(V) was quantitative with Amberlite LA-1 and LA-2, Primene JM-T and Aliquat 336S. Eight common solvents were tested as diluents; of these hexane, cyclohexane, benzene, and xylene were found to be satisfactory. Vanadium was separated from elements that do not form anionic complexes with malonic acid by selective extraction, from those that form weak complexes by washing the organic extract with water, and from metals that form strong malonato complexes by selective stripping with hydrochloric, nitric, or sulphuric acid. The method has been applied to the determination of vanadium in steel, coal fly ash and fuel oil. The precision of measurement is within ±5% and the detection limit of the method for vanadium is 0.5 mg/kg.     

Liquid-liquid extraction of thorium (IV) with hexaacetato calix(6)arene

Thorium(IV) was quantitatively extracted at pH 7.5 with 0.0001M of hexaacetato calix(6)arene in toluene and after stripping with 0.05M nitric acid, it was determined spectrophotometrically at 545 nm with thoron. Thorium(IV) was separated from commonly associated elements in fission products like uranium(VI), cesium(I), lead(II), strontium(II) and cerium(IV) in varying proportions. The method is simple, rapid, selective and applicable for the microgram concentrations of thorium(IV).     

Complexometric titration of submicromole amounts of thorium(IV) with photometric end-point detection

Summary Thorium(IV) can be determined in the microgram range by photometric titration with EDTA in the presence of an approximately equivalent amount of the indicator Semi-Xylenol Orange at pH 2 (HClO₄). Most other elements do not interfere. Interfering metal ions can be separated from thorium(IV) by electrolysis at a mercury pool cathode.

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Zusammenfassung Mikrogrammengen Thorium(IV) lassen sich durch photometrische Titration mit EDTA in Anwesenheit einer äquivalenten Menge des Indikators Semixylenol-Orange bei pH 2 (HClO₄) bestimmen. Die meisten anderen Metalle stören die Bestimmung nicht. Störende Metallionen können durch elektrolytische Abscheidung an einer Quecksilberkathode von Thorium (IV) abgetrennt werden.

     

Liquid-liquid extraction of thorium from malonate solution with liquid anion-exchangers

Thorium is quantitatively extracted with 4% Amberlite LA-1 or LA-2 in xylene, from 0.01M malonic acid medium at pH 3.0 and stripped from the organic phase with 1M hydrochloric acid, then determined spectrophotometrically at 545 nm as its complex with thoron. It is separated from other elements by selective extraction and stripping.     

Palladium(II) malonato complexes with some heterocyclic ligands

Palladium(II) malonato complexes with heterocyclic ligands have been synthesized and characterized by spectroscopic and biological studies. The compoun     

Spectrophotometric determination of scandium with arsenazo

Arsenazo is used for the spectrophotometric determination of scandium in the range 10 to 50 μg. The absorbance is measured at 570 mμ and pH 6.1. A method is proposed for the successive determination of scandium and thorium. Scandium is separated from magnesium, calcium, rare earths, zirconium, fluoride, phosphate, and some other metals by extraction with TTA in xylene. Copper, aluminum, and iron(III) are removed by 8-quinolinol-chloroform extraction. Uranium(VI) is removed by anion exchange using hydrochloric acid. Thorium is separated from scandium by anion exchange using nitric acid.     

Enantioselective Michael reaction catalyzed by well-defined chiral ru amido complexes: isolation and characterization of the catalyst intermediate,ru malonato complex having a metal-carbon bond

Chiral Ru amido complexes promote asymmetric Michael addition of malonates to cyclic enones, leading to Michael adducts with excellent ee's, in which the chiral Ru amido complexes react with malonates to give isolable catalyst intermediates, chiral Ru malonato complexes bearing a metal bound C-nucleophile.     

Determination of thorium in zirconium-hafnium mixtures by aromatic polycarboxylic acids

Summary Results are presented for 1,3,5-benzenetricarboxylic (trimesic), 1,2,4-benzenetricarboxylic (trimellitic) and 1,2,4,5-benzenetetracarboxylic (pyromellitic) acids as precipitants for thorium. Trimesic and pyromellitic acids have been found to be better reagents than trimellitic acid. Thorium and zirconium-hafnium mixtures can be separated by precipitating zirconium-hafnium first in 0.5–0.8 N acid solution and then precipitating thorium in the filtrate at 3–4 pH. The separations are quite reproducible. The precipitates in all cases are ignited to the respective oxides. 5–10 mg samples of thorium can be estimated and separated from 10–50 mg samples of zirconium and/or hafnium. Results of investigations on interferences of cations and anions and pyrolysis curves for the decomposition of precipitates are presented.

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Zusammenfassung Als Fällungsmittel fÜr Thorium wurden 1,3,5-Benzoltricarbonsäure (Trimesinsäure), 1,2,4,5-Benzoltetracarbonsäure (Pyromellitsäure) und 1,2,4-Benzoltricarbonsäure (Trimellitsäure) untersucht, wobei die beiden ersten sich als gÜnstiger erwiesen haben. Gemische von Thorium und Zirkonium/Hafnium kÖnnen getrennt werden, indem man zuerst Zr/Hf in 0,5–0,8 n saurer LÖsung fällt und anschlie\end Thorium aus dem Filtrat bei pH 3–4 niederschlägt. Die Trennung ist gut reproduzierbar. Die Niederschläge werden jeweils zu den entsprechenden Oxiden verglÜht. 5–10 mg Th kÖnnen von 10–50 mg Zr und/oder Hf getrennt werden. StÖrungen durch andere Kationen und Anionen wurden untersucht und Pyrolysekurven fÜr die Zersetzung der Niederschläge aufgestellt.

     

Liquid–liquid extraction of thorium(IV) with N-n-heptylaniline from acid media

The extraction behavior of thorium(IV) from sulphuric acid medium with N-n-heptylaniline in xylene. Various parameters like reagent concentration, acid concentration, equilibration time, diverse ions and effect of diluents were studied. Thorium(IV) was selectively extracted and separated from many metal ions. The nature of the extracted species was determined. Thorium(IV) was analyzed from monazite ore and gas mantle.

     

Studies on extraction of thorium from nitrate solutions with quaternary ammonium halides

Thorium can be quantitatively extracted with 0.1 M Hyamine 1622 in dichloroethane from 0.25M nitric acid/2M sodium nitrate and stripped from the organic phase with 0.1M sulphuric acid. The equilibration takes 20 min. Thorium can thus be separated from a large number of elements which are usually associated with it in monazite and in fission products of nuclear fuel.     

The analysis of zirconium-thorium binary alloys

Thorium-zirconium binary alloys are analysed by complexometric procedures. For alloys containing more than 20% thorium or 5% zirconium by weight, the sum of the constituents is obtained by a back titration procedure at pH 2.6–2.8 with bismuth nitrate using xylenol orange as indicator. Thorium is then masked with sulphate and the liberated EDTA is titrated with bismuth at pH 1.2–1.3. For alloys containing less than 20% of thorium, thorium fluoride is precipitated on lanthanum fluoride to effect its separation before titration. For alloys containing less than 5% of zirconium, the zirconium is separated by precipitation with p-bromo-mandelic acid.     

Extractive-chromatographic separation of bismuth with aliquat 336S from citrate solutions

Bismuth is extracted from O.O1M citric acid at pH 3.0 with Aliquat 336S coated on a silica gel column, by extraction chromatography. It was then stripped with 0.1M sulphuric acid and determined spectrophotometrically at 460 nm as the iodide complex. Bismuth was effectively separated from binary as well as ternary mixtures by taking advantage of the difference in the stability of the citrate complexes with metal ions in mineral acids. The method was extended to the analysis of bismuth from low fusible alloys.     

Thorium(IV) and uranium(VI) complexes with some heterocyclic azo dyes in absolute ethanol

Thorium(IV) and uranium(VI) chelate complexes with PAN, PAR, TAN and TAR have been studied in absolute ethanol. The uranyl ion forms complexes with PAN, PAR, TAN and TAR in the metal to ligand molar ratio of 1:1. Thorium(IV) forms complexes with PAR, TAR and TAN in the molar ratio of 1:2. In case of Th(IV)-PAN complexes the molar ratio is 1:2.4. The stability constants for all the above complexes have been worked out using the mole ratio method. The kinetics of aquation of Th(IV)-PAN complexes indicate that PAN acts as a tridentate ligand.     

Determination of thorium isotopes in bastnaesite ores

A procedure for the determination of alpha-emitting thorium isotopes in bastnaesite ores has been developed. The refractory sample was completely decomposed by potassium fluoride fusion in a platinum crucible followed by transposition to a pyrosulfate fusion. The pyrosulfate cake was dissolved in HCl and the resulting precipitate dissolved in DTPA solution; thorium was coprecipitated as hydroxide using cerium present in bastnaesite as natural carrier. Thorium was then extracted into a TOPO solution, separated by using Dowex 1-X8 for anionic exchange, electrodeposited and finally analyzed by alpha-spectrometry. Thorium was also determined spectrophotometrically using Arsenazo as a colorimetric reagent. The thorium yield of the above discussed chemical procedure is more than 85%.