Non-aqueous fluorimetric determination of scandium in silicate rocks

A method for the fluorimetric determination of scandium with 1,2,7-trihydroxyanthraquinone in dimethylformamide medium is described. The calibration graphs obtained by the normal, synchronous, and synchronous first and second derivative techniques are linear between 12 and 225 ng/ml, and the detection limit is 2 ng/ml. The method is applied to the determination of Sc(III) in two simulated and two naturally occurring rocks.     

Extraction fluorimetric determination of uranium by conventional spectrophotometry

The determination of uranium by a fluorimetric method using a conventional spectrophotometer has been elaborated. The quenching effect of the matrix was reduced by separation with liquid-liquid extraction and emulsion liquid membrane extraction methods using D2EHPA as a selective extraction reagent. The method was employed for uranium determination in radioactive waste solutions and proved to be very fast and easy to perform. It was found that it is possible to determinate as low as 0.2 ppm of uranium in a 10 ml sample.     

Substoichiometric determination of mercury with cetyltrimethylammonium bromide

A radiometric method based on substoichiometric isotope dilution analysis has been developed for the determination of mercury using cetyltrimethylammonium bromide (CTAB) as the substoichiometric reagent. The method is based on the extraction of mercury as an ionassociation complex of tetraiodomercurate(II) ion with a substoichiometric amount of CTAB in benzene. The calibration graph was found to be linear in the range 0–10 μg Hg (II) in the aqueous phase of 10 ml volume. A detection limit of 0.06 μg·ml⁻¹ could be achieved by the proposed method. The relative standard deviation of the method was found to be 3.0% and the method has been successfully applied to study the determination of mercury in various synthetic mixtures.     

Spectrophotometric determination of germanium with Catechol Violet and cetyltrimethylammonium bromide

A ternary complex between germanium, Catechol Violet (CV) and cetyltrimethylanunoniuni bromide is proposed for the determination of germanium. The stoichiometric ratio Ge:CV is 1:2. Beer's law is obeyed from 0.1 to 1.0 ppm of Ge. The method is highly selective. Interference from Sn(IV), Fe(III), Bi(III), Cr(VI), Mo(VI), V(V) and Sb(III) in mg amounts is eliminated by extracting the germanium into carbon tetrachloride from 9M HC1 and then stripping into water before the photometric determination.     

Spectrophotometric determination of thorium with Xylenol Orange and cetyltrimethylammonium bromide

The thorium-Xylenol Orange reaction sensitized by cetyltrimethylammonium bromide ( = 5.51 x 10(4) l.mole(-1).cm(-1)) is accompanied by a bathochromic shift from 570 to 600 nm. The system is more selective than the binary system, because the reaction pH is lowered from 4.0 to 2.5; Beer's law is obeyed for 0.04-4.00 ppm of thorium.     

Spectrophotometric determination of molybdenum in steels with o-nitrophenylfluorone and cetyltrimethylammonium bromide

A method has been developed for determining microamounts of molybdenum(VI) in aqueous solution by means of the Mo-o-nitrophenylfluorone—cetyltrimethylammonium bromide system, in which micellar solubilization is applied. A red complex is formed in 0.2–0.6M hydrochloric acid medium. The sensitivity of the method is high, and the apparent molar absorptivity is 1.55 × 10⁵ l.mole⁻¹. cm⁻¹. The absorption peak of the complex appears at 530 nm. The colour of the complex develops quickly and is stable for more than 24 hr. The composition of the complex is Mo: o-NPF = 1:1, and the system obeys Beer's law in the range 0–10 μg of Mo per 25 ml. The method has been used for the rapid determination of molybdenum in alloy steels with satisfactory results.     

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.     

Polarographic behavior of nicotinamide in surfactant media and its determination in cetyltrimethylammonium bromide surfactant system

The behavior of nicotinamide has been studied by differential pulse polarography and cyclic voltammetry in the presence of certain ionic and nonionic surfactants, viz. cetyltrimethylammonium bromide (CTAB), sodium dodecylsulfate (SDS) and Triton X-100 (TX-100). The cathodic peak potential (E(p(c))) and peak current (I(p(c))) of nicotinamide were found to be remarkably dependent on the charge and concentration of the surfactant. The presence of SDS and that of TX-100 cause a shift in peak potential and a change in peak current of nicotinamide. In the presence of the cationic surfactant, CTAB, an enhancement in the sensitivity of nicotinamide was observed. A sharp peak with more than two-fold increase in current was used to determine the limit of detection and linear working range using the differential pulse polarographic technique. The present method was successfully used for the simultaneous determination of nicotinamide and pyridoxine hydrochloride, and for the determination of nicotinamide in multivitamin pharmaceutical preparations.     

Extraction by reversed micelles of triton N-42 for the spectrophotometric determination of cetyltrimethylammonium bromide

Micellar preconcentration of 1 : 2 associates of Bromophenol Blue with cetyltrimethylammonium bromide is proposed to improve the procedure for the spectrophotometric determination of cationic surfactants. The preconcentration procedure involves quantitative extraction by reversed micelles of Triton N-42 in decane followed by the decomposition of the micellar solution with chloroform. The loss of 10^–7–10^–5 M cetyltrimethylammonium bromide in 5–100-fold preconcentration was not supported by the added-found method (RSD = 3–5%). The determination limit for cetyltrimethylammonium bromide is 2 × 10^–7 M.Translated from Zhurnal Analiticheskoi Khimii, Vol. 60, No. 1, 2005, pp. 17–21.Original Russian Text Copyright © 2005 by Demidova, Bulavchenko.     

Spectrophtometric determination of tungsten(VI) with rutin and cetyltrimethylammonium bromide

Tungsten-(VI) reacts with rutin in the presence of cetyltrimethylammonium bromide to form a soluble yellow complex having maximum absorbance at 416 nm. The molar ratio of tungsten to rutin in the complex is 1:2. The molar absorptivity is 5.01 x 10(4) 1.mole(-1).cm(-1). Beer's law is obeyed over the range 1 x 10(-7)(-1) x 10(-5)M tungsten (VI). Optimum solution conditions for the determination of tungsten in various sample matrices have been found and the interference of diverse ions has been examined.     

Spectrophotometric determination of molybdenum with 7,8-dihydroxy-4-methylcoumarin and cetyltrimethylammonium bromide

The 1:2 complexes formed between molybdenum and 7,8-dihydroxy-4-methylcoumarin in the presence and absence of cetyltrimethylammonium bromide (CTAB) have been studied. The binary complex formed at pH 5.6-6.0 in the absence of CTAB exhibits an absortion maximum at 360 nm with a molar absorptivity of 5.1 x 10(4) 1.mole(-1).cm(-1). The complex formed at pH 4.8-6.0 in the presence of CTAB has a molar absorptivity of 1.32 x 10(5) 1.mole(-1).cm (-1) at 400 nm, the wavelength of maximum absorption. Optimum conditions for complex formation were investigated and a rapid, sensitive and relatively selective method for the determination of up to approximately 70% of Mo in diverse alloys and steels is described. Small amounts of zirconium and tungsten interfere.     

Spectrofluorimetric determination of niobium with morin enhanced by cetyltrimethylammonium bromide micelles

The effect of surfactants on the fluorescence of the niobium—morin system is described. Cationic surfactants strongly enhanced the intensity (e.g., cetyltrimethylammonium bromide (CTAB) gives an 80-fold increase), while anionic and non-ionic surfactants are without effect. The formation of 1:1 and 1:3 (Nb:morin) complexes is demonstrated spectrophotometrically. The conditional stability constants for these complexes in CTAB micelles are β₁ = (1.14 ± 0.01) × 10⁴ l mol^?1 amd β₃ = (5.66 ± 0.02 × 10¹⁰ l³ mol^?3. The micellar-enhanced fluorimetric method has a 1 μg l^?1 detection limit, and is highly selective. The r.s.d. for the determination of 50 μg l^?1 Nb is 3.5%.     

Micelle mediated extraction of titanium and its ultra-trace determination in silicate rocks

A highly sensitive method for extractive spectrophotometric determination of titanium in silicate rocks is described. Titanium in the range 0-10 microg as TiO2 is extracted into benzene or toluene by the formation of a ternary complex of the metal with thiocyanate (SCN-) and cetyltrimethylammonium bromide (CTA) in the ratio 1:2:2. A deep yellowish-orange ternary complex thus formed is suitable for the determination of titanium at wavelength 421 nm. The optimum colour intensity of this ternary complex was attained when the complex was extracted from an aqueous solution having concentrations of thiocyanate and HCl, in the range, 1.5-2.5 and 1-5 mol L(-1), respectively. The molar absorptivity and Sandell's sensitivity of the extracted species were found to be 1.1-1.0x10(5) L mol(-1) cm(-1) and 0.47 ng cm(-2) (referred to titanium), respectively, at lambda(max) of 421 nm. Except Fe3+, Nb5+ and V5+, no interference was encountered in the estimation of titanium. While up to 10 mg L(-1) Nb and V did not interfere in the determination of titanium, the interference of Fe(3+) was eliminated by reducing it to Fe2+ using SnCl2 solution. The method is highly sensitive and selective. The results obtained for titanium estimation in a host of silicate rock samples have been found to be highly reproducible, accurate and favourably comparable with certified values of reference materials and those obtained from standard methods.     

Simultaneous electrochemical determination of three sunscreens using cetyltrimethylammonium bromide

This paper proposes a methodology based on electrochemical reduction for the simultaneous determination of three sunscreen agents, namely 4-methylbenzylidene camphor (MBC), benzophenone-3 (BENZO) and 2-ethylhexyl-4-methoxycinnamate (EHMC) by differential-pulse polarography (DPP). The highest peak currents and optimal separation of reduction peaks were obtained by using a supporting electrolyte consisted of Britton-Robinson buffer-methanol (8:2) solution at pH 4.0 and cationic surfactant 3.0 x 10(-4)mol L(-1) cetyltrimethylammonium bromide (CTAB). The methodology was validated using four commercial sunscreen preparation as a sample and the results showed high recovery rates. The efficiency of the proposed methodology was demonstrated by comparing the results obtained by DPP with those obtained by the high-performance liquid chromatography (HPLC) method.     

Photometric determination of phosphorus in silicate rocks

Phosphorus in silicate rocks may bedeterminedaccurately by the photometric molybdovanadophosphoric acid method following decomposition of the sample with nitric-hydrofluoric acid.     

Photometric determination of arsenic in silicate rocks

Summary The method described consists in decomposing the silicate rock sample by fusion with sodium hydroxide or sodium hydroxide-peroxide, leaching the melt with water, evolving arsine from the filtrate, and finally determining arsenic by photometric evaluation of molybdenum blue. Satisfactory accuracy has been demonstrated for the range 0.0 to 20 p. p. m. As, for which the method is particularly intended.

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Zusammenfassung Zur Bestimmung des Arsengehaltes in Silikatgesteinen wird die Probe durch Schmelzen mit Natriumhydroxyd und gegebenenfalls Natriumperoxyd aufgeschlossen. Aus dem Filtrat der wäßrigen Lösung dieser Schmelze wird Arsenwasserstoff entwickelt und in natriumhydrogenkarbonathältiger Jodlösung aufgefangen. Das hierbei entstehende Arsenat wird nach Zugabe von Molybdatreagens und Bisulfit photometrisch bestimmt. Für Arsengehalte unter 0,02% werden nach dieser Methode Resultate von zufriedenstellender Genauigkeit erhalten.

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Résumé La méthode décrite consiste en la décomposition de l'échantillon de roche silicatée par fusion avec la soude ou le peroxyde de sodium, reprenant la partie fondue par l'eau, libérant l'hydrogène arsénié du filtrat et finalement dosant l'arsenic par colorimétrie du bleu de molybdène. Une précision suffisante a été mise en évidence dans le domaine de 0,0 à 20 p. p. m. d'arsenic pour lequel la méthode convient particulièrement bien.

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Fulbright Scholar.     

Determination of uranium in silicate rocks using laser induced fluorescence

A rapid method for fluorimetric estimation of uranium in silicate rocks is described. The fluorescence of uranyl complex is induced by laser beam in the ultraviolet region provided by nitrogen laser tube. The emission spectrum is quite intense and relatively persistent. For direct estimation of uranium in geological silicate materials without prior extraction, the interference of certain cations and anions that might be present in silicate rocks on uranium determination was studied. The limit of detection is 0.5 ppb.     

Spectrophotometric determination of traces of lead with bromopyrogallol red and cetyltrimethylammonium or cetylpyridinium bromide

A method is described based on the sensitizing effect of cetyltrimethylammonium or cetylpyridinium bromide on the lead-Bromopyrogallol Red colour reaction. The reaction is instantaneous and the colour remains stable for over 120 hr in the presence of Triton X-100. Both colour systems obey Beer's law up to 5.5 ppm of lead. Methods are described for dealing with interferences.     

Spectrofluorometric determination of trace amounts of terbium with 4-chlorosalicylic acid, EDTA, and cetyltrimethylammonium bromide.

The quadruple complex formed by terbium with 4-chlorosalicylic acid (CSA), EDTA and cetyltrimethylammonium bromide (CTMAB) has been used for the sensitive spectrofluorometric determination of terbium in mixed rare earths. The effect of the experimental conditions on the fluorescence intensity was defined. Under the optimum conditions selected, the fluorescence intensity was linear with the terbium concentration in the range of 3.0 x 10(-8)-1.0 x 10(-5) mol/L with a detection limit of 8.0 x 10(-9) mol/L (S/N = 3). It has been satisfactory for the determination of terbium in mixed rare earths with good recovery.     

Potentiometric microtitration of anions with cetyltrimethylammonium bromide

Summary A new titrant, cetyltrimethylammonium bromide, has been evaluated for the potentiometric precipitation titration of small amounts of some large inorganic anions. Emf's were monitored with a fluoroborate ion-selective electrode and a double-junction reference electrode. The perchlorate, nitrate, and calcium electrodes also respond to the various anions. Sharp endpoint breaks were obtained for permanganate, hexafluoroarsenate, hexafluorophosphate, persulfate, tetrachloroplatinite, hexachloroplatinate, tetrachlorostannite, tetrachloroaurate, ferricyanide, tetrachloromercurate, tetrachlorothallate, hexachloroosmiate, and bismuth(III) in hydrochloric acid. Medium breaks were obtained for perrhenate, perchlorate, tetrafluoroborate, dichromate, hexafluoroantimonate, ferrocyanide, hexachlorostannate, and hexachloroiridate. Shallow breaks were obtained for iodide, periodate, and tetrachloropalladate. Because of the limited solubility of the titrant in water it cannot be used at concentrations higher than 0.01 N.

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Potentiometrische Mikrotitration von Anionen mit Cetyltrimethyl-ammoniumbromid. I

Zusammenfassung Cetyltrimethylammoniumbromid wurde als neues Titrationsmittel für die potentiometrische Fällungstitration kleiner Mengen großer anorganischer Anionen eingesetzt. Die EMK wurde mit einer ionenspezifischen Fluorboratelektrode und einer doppelt verbundenen Bezugselektrode gemessen. Perchlorat-, Nitrat- und Calciumelektroden eignen sich ebenfalls für die entsprechenden Anionen. Scharfe Endpunkte wurden erhalten für Permanganat, Hexafluoroarseniat, Hexafluorophosphat, Persulfat, Tetrachloroplatinit, Hexachloroplatinat, Tetrachlorostannit, Tetrachloroaurat, Eisen(Ill)cyanid, Tetrachloromercurat, Tetrachlorothallat, Hexachloroosmiat und Wismuth(III) in Salzsäure. Mittelscharfe Umschlagpunkte erhielt man für Perrhenat, Perchlorat, Tetrafluoroborat, Dichromat, Hexafluoroantimonat, Eisen(II)cyanid, Hexachlorostannat und Hexachloroiridat. Unscharfe Umschlagpunkte ergaben Jodid, Perjodat und Tetrachloropalladat. Wegen der begrenzten Löslichkeit des Titrationsmittels in Wasser kann es maximal in 0,01 N Lösung angewendet werden.

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Work performed under the auspices of the U. S. Department of Energy by the Lawrence Livermore Laboratory under contract number W-7405-ENG-48.

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This paper is dedicated to the memory of my mother, Flora Selig, who died in June 1979.