Spectrophotometric study of reactions of scandium,ytrium and lanthanum ions with some triphenylmethane dyes in the presence of cationic surfactants

Optimum conditions for the formation of ternary complexes of scandium, ytrium and lanthanum ions with chrome azurol S, eriochrome cyanine R and pyrocatechol violet in the presence of cetyltrimethylammonium, cetypyridinium and tetradecyldimethylbenzyl-ammonium (zephiramine) ions are described. The spectrophotometric determination of scandium with chrome azurol S and zephiramine exhibits the greatest sensitivity (? = 1.50 × 10⁵ l mol^?1 cm^?1 at 610 nm). In the spectrophotometric determination of scandium with eriochrome cyanine R and cetylpyridinium ion (? = 9.2 × 10⁴ at 600 nm), the interference caused by yttrium is the least. In the best method for yttrium (with pyrocatechol violet and zephiramine), the molar absorptivity is 3.3 × 10⁴ at 660 nm. Lanthanum does not form ternary complexes of analytical interest in these systems. Some aspects of the formation of ternary complexes with cationic surfactants are discussed.     

Spectrophotometric determination of scandium with anthrarufin-2,6-disulfonic acid (disodium salt)

A new spectrophotometric method for the determination of scandium, is described using anthraru-fin-2, 6-disulfonic acid (disodium salt) as a reagent. The color reaction has a sensitivity of 0.004 μg Sc per cm² for log $\text{I}{}_0\text{1}$ = 0.001 and obeys Beer's law up to 2 p.p.m. The effects of ph, time, order of addition of the reagents, temperature, and diverse ions were investigated. A separation procedure was developed and applied to six salt solutions containing scandium plus a variety of foreign ions.     

Chlorophosphonazo-p-Cl,a new reagent for the spectrophotometric determination of scandium

Summary Chlorophosphonazo-p-Cl, A New Reagent for the Spectrophotometric Determination of Scandium The synthesis of chlorophosphonazo-p-Cl (CPApC) and a highly sensitive method with CPApC as a new reagent for the spectrophotometric determination of scandium are described. Scandium reacts with CPApC in nitric acid medium at pH 2 to form a 11-type complex which has a maximum absorption at 762 nm. Under the experimental conditions employed, the apparent molar absorptivity is 1.54×10⁵ l·mol^–1·cm^–1 and the relative standard deviation for 2.0g of scandium is 0.92%. The determination range is 0–6g of scandium in 25 ml of solution by using standard addition-deduction method. Scandium can be determined in the presence of reasonable amounts of rare earths.This work was supported by the Science Fund of the Chinese Academy of Sciences.     

Spectrophotometric determination of scandium with bromopyrogallol red

A highly sensitive spectrophotometnc method for scandium with Bromopyrogallolo Red is described;) mierogram amounts of scandium can be determined by measurement 'at 610 mmu and pH 6-1. The molar-absorptivity is 2.4 x 10(4) at 610 mmu. Formation of a 1:1 complex of scandium with Bromopyrogallol Red is confirmed, Common cations interfere, but can be separated completely by three successive ioń-exchange (Steps, so the method can be applied to the determmation of traces of scandium in silicate rocks. Results are quoted for scandiumn in several types of igneous rocks.     

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.     

On-line spectrophotometric determination of scandium after preconcentration on XAD-4 resin impregnated with nalidixic acid

An on-line scandium preconcentration and determination method was developed with spectrophotometer associated with flow injection. Scandium from aqueous sample solution of pH 4.5 was selectively retained in the minicolumn containing XAD-4 resin impregnated with nalidixic acid at a flow rate of 11.8 mL min^?1 as scandium–nalidixic acid complex. The scandium complex was desorbed from the resin by 0.1 mol L^?1 HCl at a flow rate of 3.2 mL min^?1 and mixed with arsenazo-III solution (0.05 % solution in 0.1 mol L^?1 HCl, 3.2 mL min^?1) and taken to the flow through cell of spectrophotometer where its absorbance was measured at 640 nm. The preconcentration factors obtained were 35 and 155; detection limits of 1.4 and 0.32 μg L^?1 and sample throughputs of 40 and 11 were obtained for preconcentration time of 60 and 300 s, respectively. The tolerance limits of many interfering cations like Th(IV), U (VI), rare-earths and anions like tartrate, citrate, oxalate and fluoride were improved. The method was successfully applied to the determination of scandium from mock seawater samples and good recovery was obtained. The method was also validated on certified reference material IAEA-SL-1 (lake sediment) and the result was in good agreement with the reported value.     

Neutron activation analysis of scandium

A neutron activation method is proposed for the determination of trace quantities of scandium, down to submicrogram level, in rocks, ores and meteorites. The sample and standard are irradiated intermittently for a total of 30 h, at a neutron flux of 5·10¹¹ n/cm²/sec; the radiochemical separation consists essentially of a one-step anion exchange. The induced γ-activity of ⁴⁰Sc, 85 days, isolated from the sample is measured and compared with that of a standard. The chemical yield averages 85% and there is a considerable saving of time in the radiochemical work. Results are quoted for the scandium contents of 2 standard rocks, cassiterite and several stony meteorites. Details of conflicting nuclear reactions are also given.     

Determination of trace scandium by ion-exchanger phase spectrophotometry withp-nitrochlorophosphonazo

Ion-exchanger phase Spectrophotometry withp-nitrochlorophosphonazo (CPApN) has been developed for the determination of scandium. The linear range is 1–8 g of scandium in 50 ml of solution, using 0.8 g of resin, with an apparent molar absorptivity of 2.76 × 10⁵ 1 mol^–1 cm^–1. Aluminum and rare earth elements in reasonable amounts do not interfere. The method has been applied successfully to the determination of scandium in alloys, with relative standard deviations of 2–4%.     

The determination of stable scandium in plants,animals, sediments,sands, soils,rocks and minerals by neutron-activation analysis

A method is described for the determination of stable scandium in samples of plants, animals, sediments, soils, rocks and minerals. The samples and comparator standards were irradiated in a neutron flux of 5·10¹² n/cm²/sec for 4 h and dissolved and the scandium quantitatively precipitated from 2N nitric acid as scandium phytate; contaminants were rinsed from the precipitate with nitric and hydrochloric acids. The limit of detection was 0.005μg(±10% at the 95% confidence level). The activated ⁴⁶Sc was counted by γ-spectrometry.     

A highly sensitive spectrophotometric determination of palladium with chromal blue g and cetyltrimethylammonium chloride

A new spectrophotometric method for the determination of palladium with chromal blue G (Color Index 43835) and cetyltrimethylammonium chloride is described. The sensitivity of the color reaction between palladium and chromal blue G is greatly increased in the presence of cetyltrimethylammonium chloride. The palladium complex has maximal absorbance at pH 3.2–3.8 and at 670 nm. Beer's law is obeyed over the range 0.08–1.4 p.p.m. palladium; the molar absorptivity is 1.01 · 10⁵ l mol^-1 cm^-1 at 670 nm and the sensitivity is 1·10^-3 μg Pd cm^-2. The mole ratio of palladium and chromal blue G in the complex in the presence of cetyltrimethylammonium chloride is 1:3. Only scandium interferes when sodium fluoride is used as masking agent.     

Determination of trace quantities of scandium in silicate rocks by a combined ion exchange-spectrophotometric method

A spectrophotometric determination of scandium in silicate rocks has been developed with arsenazo as the color reagent. After the decomposition of samples with a hydrofluoric-perchloric acid mixture, traces of scandium are separated from interferences by cation- and anion-exchange in acid sulfate media and anion exchange in hydrochloric acid solution. The successive 3 steps, with an intermediate concentration step, yield scandium in a sufficiently pure state for spectrophotometric determination.     

A radiochemical method of separation of carrier-free vanadium from scandium and bulk amount of titanium

A method for the separation of carrier-free vanadium from scandium and bulk amount of titanium has been developed. Vanadium has been produced through the reaction^natTi(d,n)^48,49V with 8 MeV deuterons from the Variable Energy Cyclotron, Calcutta. The separation is performed with Dowex 1×8, 50–100 mesh fluoride from anion exchange resin which retains all the scandium and titanium with 4.5M hydrofluoric acid as eluent, while vanadium(V) is easily eluted. The chemical yield of vanadium was >85%.     

Analytical application and spectrophotometric study of the scandium-indoferron complex

A new spectrophotometric method for microgram amounts of scandium with indoferron is described. The molar absorptivity is 960 l.mole⁻¹.mm⁻¹ at 600 nm. Uranium and the rare earths do not interfere, if present in amounts less than 50 μg. Scandium in silicate rocks can be determined by the procedure after separation of the scandium by a three-stage ion-exchange Chromatographic technique. The acid dissociation constants of indoferron and conditional formation constants of the 1:2 complex have been determined spectrophotometrically.     

Trace element determination in high-purity scandium by neutron activation analysis and pre-irradiation matrix separation

A pre-irradiation separation procedure has been developed for the determination of trace elements in high-purity scandium by neutron activation analysis. The sample is dissolved in high-purity concentrated hydrochloric acid and scandium is extracted with the same volume of a solution of 50 vol.% bis(2-ethyl hexyl)-orthophosphoric acid (HDEHP) in toluene. The scandium matrix is removed from the most important trace impurities and the residual amount of Sc is in the range of 0.001%. The separation is carried out in the vial to be used in irradiation to prevent sample contamination. Detection limits in the ppb range were achieved with a sample of 10 mg, a thermal neutron flux of 2 · 10¹³ n · cm^–2 · s^–1 and an irradiation time of 48 hours. Most of the elements sought in two samples of high-purity scandium were below the detection limits.     

The spectrophotometric determination of scandium with disodium 3-hydroxy-4-[(6-methyl-2-pyridyl)azo]-2,7-naphthalenedisulfonate N-oxide

Summary The application of the named compound for the spectrophotometric determination of scandium is described. The effects due to pH, reagent concentration, time and diverse ions are reported. Beer's law is obeyed and the molar absorbance coefficient at 555 nm is 1.55×10⁴. By using a cupferron extraction prior to analysis, the procedure is quite selective.

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Spektrophotometrische Bestimmung von Scandium mit Dinatrium-3-hydroxy- 4-[(6-methyl-2-pyridyl)azo]-2,7-naphthalindisulfonat-N-oxid

Zusammenfassung Die Anwendung der genannten Verbindung für die spektrophotometrische Bestimmung von Scandium wurde beschrieben. Der Einfluß des pH, der Reagenskonzentration, der Zeit und verschiedener Ionen wurde untersucht. Das Beersche Gesetz wird befolgt, der molare Absorptionskoeffizient bei 555 nm beträgt 1,55×10⁴. Nach vorhergehender Cupferron-Extraktion ist das Verfahren selektiv.

     

Spectrophotometric determination of microamounts of scandium with o-chlorophenylfluorone and cetyltrimethylammonium bromide

The reaction of scandium(III) with o-chlorophenylfluorone (o-CIPF) in the presence of cetyltrimethylammonium bromide (CTMAB) has been studied. In an acetate buffer at pH 4.4, a red-purple complex is obtained, with maximum absorption at 569 nm and a molar absorptivity of 1.31 x 10(5)1.mole(-1).cm(-1). The composition of the complex is found to be 1:2:2 Sc-o-CIPF-CTMAB. Beer's law is obeyed over the range 0-12 mug/25 ml scandium. The proposed method has been used for determination of trace scandium in tungsten ores after its prior separation by solvent extraction.     

Spectrophotometric determination of scandium based on the cocoloration effect in scandium-cerium-p-acetylchlorophosphonazo (CPApA) system

Scandium in the presence of cerium(III) forms, with p-acetylchlorophosphonazo (CPApA), a heteropolynuclei ternary β-complex of scandium-cerium-CPApA. The complex gives a very sensitive reaction for scandium with a molar absorptivity of _Sc = 2.29 × 10⁵ l mol⁻¹ cm⁻¹ due to the cocoloration effect. Most foreign ions can be tolerated in considerable amounts. The optimum conditions and the mechanism of the complex formation reaction are discussed. A simple method is proposed for the determination of scandium in alloys, with satisfactory results.     

Thermodynamic calculations of the interaction of scandium halides with aluminum

The fundamental characteristics of the reduction of scandium trifluoride and trichloride with aluminum were studied by thermodynamic modeling over wide temperature and pressure ranges (1100–1400 K and 1–10⁶ Pa for ScF₃ and 800–1200 K and 1–10⁵ Pa for ScCl₃). Calculations of the equilibrium compositions of the systems were performed to draw conclusions about the contents of condensed and gaseous components and determine the temperatures of the complete reduction of trihalides with the formation of a two-phase alloy containing a saturated solution of scandium in aluminum and the Al₃Sc intermetallic compound. The results of modeling were in agreement with the available experimental data.     

Studies on the scandium distribution in organs of fattened chicken by neutron activation analysis

Tissues samples of chicken /blood, liver, spleen, fat, pancreas, kidney, lung, breast muscle, brain, femur, faeces, egg yolk, white of egg/, were analyzed for scandium concentration. ScCl₃ was applied intravenously /1 mg kg^–1 body weight/. High scandium concentrations were found in the liver /34. 35 ppm/, spleen /15.46 ppm/, and lung /15.52 ppm/ three days after application. This experiment shows that accumulation of scandium occurs in the yolk of egg but not in the white of the egg.     

Dehydrocoupling of boranes with amines using a scandium catalyst

The scandocene alkyl complex (C₅Me₅)₂ScCH₂SiMe₃ was found to be an efficient catalyst for the dehydrocoupling of the non-cyclic boranes, dicyclohexylborane and thexylborane, with amines under mild conditions. The reactions afforded the corresponding aminoboranes in high yields with good functional group tolerance. The stoichiometric reaction of scandium alkyl with amine led to the isolation of a scandium amide complex, which was shown to be an active species during the catalysis. Although a borane-coordinated scandium hydride was also obtained from the stoichiometric experiment, it was not involved in the catalytic cycle. In addition, kinetic studies provided insight into this intermolecular dehydrogenation reaction.