Preconcentration of trace cobalt with the ion pair of 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol and tetraphenylborate onto microcrystalline naphthalene or column method and its determination by derivative spectrophotometry

Cobalt-2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (5-Br-PADAP)-tetraphenylborate ion associated complex is quantitatively adsorbed on microcrystalline naphthalene in the pH range 3.5-9.5 from a fairly large volume of the aqueous samples (preconcentration factor ~30). After filtration, the solid mass consisting of the cobalt complex and naphthalene was dissolved with 5 ml of dimethylformamide (DMF) and the metal determined by first-derivative spectrophotometry. The cobalt-5-Br-PADAP complex can alternatively be quantitatively retained on ammonium tetraphenylborate-naphthalene adsorbent filled in a column (preconcentration factor 120) in the same pH range and determined similarly. The detection limit is 30 ppb (signal-to-noise ratio=2) and the calibration curve is linear over 0.3-8.0 mug of cobalt in 5 ml of the final DMF solution. Eight replicate determinations of 1.0 mug of cobalt gave a mean peak height of 0.208 (at 611.5 nm) with a relative standard deviation of 1.2%. The sensitivity of the method is 1.04 (dA/dnm) ml mug(-1) found from the slope of the calibration curve. The interference of a large number of anions and cations on the determination of cobalt has been studied and the optimized conditions developed were utilized for its trace determination in various standard alloys and biological samples.     

Preconcentration of trace nickel with the ion pair of disodium 1-nitroso-2-naphthol-3,6-disulfonate and tetradecyldimethylbenzylammonium chloride on microcrystalline naphthalene or by the column method and determination by third derivative spectrophotometry

Nickel is quantitatively retained by disodium 1-nitroso-2-naphthol-3,6-disulfonate (nitroso-R salt) and tetradecyldimethylbenzylammonium chloride (TDBA(+)Cl(-)) on microcrystalline naphthalene in the pH range 5.4-12.1 from large volumes of aqueous solutions of various alloys and biological samples. After filtration, the solid mass consisting of the nickel complex and naphthalene was dissolved with 5 ml of dimethylformamide (DMF) and the metal was determined by third derivative spectrophotometry. Nickel complex can alternatively be quantitatively adsorbed on tetradecyldimethylbenzylammonium-naphthalene adsorbent packed in a column and determined similarly. The detection limit is 10 ppb (signal to noise ratio 2) and the calibration curve is linear from 30 to 5.4x10(3) ppb in dimethylformamide solution with a correlation coefficient of 0.9997 by measuring the distance d(3)A/dlambda(3) between lambda(1) (537 nm) and lambda(2) (507 nm). Eight replicated determinations of 2.5 mug of nickel in 5 ml of dimethylformamide solution gave a mean intensity (peak-to-peak signal between lambda(1) and lambda(2)) of 0.339 with a relative standard deviation of +/-0.87%. The sensitivity of the method is 0.677 ml/mug found from the slope (d(3)A/dnm(3)) of the calibration curve. Various parameters such as the effect of pH, volume of aqueous phase and interference of a number of metal ions on the determination of nickel has been studied in detail to optimize the conditions for nickel determination in various alloys and biological samples.     

Derivative spectrophotometric determination of iridium after preconcentration of its 1-(2-pyridylazo)-2-naphthol complex on microcrystalline naphthalene

Iridium is preconcentrated from the large volume of its aqueous solution using 1-(2-pyridylazo-2-naphthol) (PAN) on microcrystalline naphthalene in the pH range of 4.5-6.0. The solid mass after filtration is dissolved with 5 ml of dimethylformamide (DMF) and the metal determined by first derivative spectrophotometry. The detection limit is 20 ppb (signal to noise ratio = 2) and the calibration curve is linear over the concentration range 0.25-75.0 mug in 5 ml of the final DMF solution with a correlation coefficient of 0.9996 and relative standard deviation of +/- 1.1%. Various parameters such as the effect of pH, volume of aqueous phase, choice of solvent, reagent and naphthalene concentration, shaking time and interference of a number of metal ions on the determination of trace amount of iridium have been studied in detail to optimize the conditions for its determination in synthetic samples corresponding to various standard alloys and environmental samples.     

Trace determination of zinc in standard alloys, environmental and pharmaceutical samples by fourth derivative spectrophotometry using 1-2-(thiazolylazo)-2-naphthol as reagent and ammonium tetraphenylborate supported on naphthalene as adsorbent

A highly sensitive, selective, economical and rapid method for the trace determination of zinc using fourth derivative spectrophotometry has been proposed with 1-2-(thiazolylazo)-2-naphthol (TAN) as an analytical reagent and ammonium tetraphenylborate (ATPB)-naphthalene as an adsorbent. Zn-TAN is quantitatively retained on ATPB naphthalene in the pH range 6.5-9.5. The calibration plot is linear in the concentration range 0.02-1.4 mug ml(-1) Zn of DMF solution. The sensitivity of the method as determined from the slope of the calibration plot is 2.640 (d(4)A/dlambda(4))/(mug ml(-1)). Nine replicate determinations of 5.0 mug of zinc in 5 ml of DMF give a mean signal height of 2.660 (peak to peak height between lambda(1)=597 nm and lambda(2)=585 nm) with a relative standard deviation of 1.1%. The various conditions have been optimized and the developed method has been used for the determination of zinc in standard alloys, environmental and pharmaceutical samples.     

Column preconcentration of trace manganese with the ion pair of 2-nitroso-1-naphthol-4-sulfonic acid tetradecyldimethylbenzyl-ammonium chloride supported on naphthalene and determination by derivative spectrophotometry

A column preconcentration method has been developed for the determination of trace amounts of manganese by preconcentration on 2-nitroso-1-naphthol-4-sulfonic acid (nitroso-S)-tetradecyldimethylbenzylammonium (TDBA) naphthalene as an adsorbent using a simple funnel tipped glass tube. Manganese reacts with nitroso-S to form a water soluble brown colored chelate anion. The chelate anion forms a water insoluble Mn-Nitroso-S-TDBA ion pair on naphthalene packed in a column in the pH range 9.6-10.5 at a flow rate of 1-2 ml/min. The solid mass consisting of manganese complex and naphthalene is dissolved in 5 ml of dimethylformamide (DMF) and the metal determined by second derivative spectrophotometry. The calibration curve is linear in the concentration range 0.25-35.0 micrograms of Mn in 5 ml of the final DMF solution. Eight replicate determinations of 25 micrograms of standard manganese solution give a mean peak height of 4.0 with a correlation coefficient of 0.9995 and relative standard deviation of +/- 1.1%. The sensitivity was calculated to be 0.502(d2 A/d lambda 2)/microgram ml-1 from the slope of the calibration curve. The detection limit was 0.020 microgram ml-1 for manganese at the minimum instrumental settings (signal to noise ratio = 2). Various parameters effecting the method such as the effect of pH, volume of aqueous phase and interference of a number of metal ions on the determination of manganese have been evaluated to optimize the conditions for its determination in standard alloys and biological samples.     

Ammonium tetraphenylborate-naphthalene adsorbent for the preconcentration and trace determination of uranium in standard alloys and synthetic samples using 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol by fourth-derivative spectrophotometry

A solid ion-pair material produced from ammonium tetraphenylborate (ATPB) and naphthalene has been used for the preconcentration of uranium from the large volume of its aqueous complex samples. Uranium reacts with 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (5-Br-PADAP) to form a water insoluble, coloured complex. This complex is quantitatively retained on the ATPB-naphthalene adsorbent filled in a column in the pH range 7.0–9.5 and at a flow rate of 2 ml/min. The solid mass from the column is dissolved with 5 ml of dimethylformamide (DMF) and uranium is determined by fourth-derivative spectrophotometry. The calibration curve is linear over the concentration range of 0.13–15.0 g of uranium in 5 ml of the final DMF solution. Seven replicate determinations of 6 g of uranium gave a mean peak height (peak-to-peak signal between 592 nm and 582 nm) of 1.02 with a relative standard deviation of 0.95%. The sensitivity is 0.8419 (d⁴A/d⁴)/(g ml^–1) found from the slope of the calibration curve. The interference of a large number of anions and cations on the estimation of uranium has been studied and the method applied for the determination of uranium in coal fly ash, Zr-base alloy and some synthetic samples corresponding to standard alloys.     

Column preconcentration of titanium in aluminium and zinc alloys with oxalic acid-ascorbic acid and the ion-pair of sodium 1,2-dihydroxybenzene-3,5-disulphonic acid and tetradecyldimethylbenzylammonium chloride supported on naphthalene using spectrometry

A solid ion-pair compound produced from sodium 1,2-dihydroxybenzene-3,5-disulphonic acid (Tiron) and tetradecyldimethylbenzylammonium chloride(TDBA) supported on naphthalene in a simple glass-tipped funnel tube provides a simple adsorbent system for preconcentrating titanium from some alloys. Titanium reacts with Tiron to form a water-soluble coloured chelate anion which in turn forms a water-insoluble stable titanium/Tiron/TDBA complex with the ion-pair on the surface of naphthalene packed in a column. Titanium is quantitatively retained on the naphthalene in the presence of L-ascorbic acid and oxalic acid in the pH range 3.0-4.5 and at a flow-rate of 1 mil/min. The metal complex and naphthalene were dissolved from the column with 5 ml of dimethylformamide(DMF), and the absorbance of the solution was measured at 398 nm. A calibration graph was linear over the range 1-18 mug of titanium in 5 ml of the final DMF solution. The complex has a molar absorptivity of 1.39 x 10(4) l.mole(-1).cm(-1) and a sensitivity of 3.44 x 10(-3) mug/cm(2) for 0.001 absorbance. Eight replicate determinations for a sample containing 12 mug of titanium gave a mean absorbance of 0.697 with a relative standard deviation of 0.82%. The interference of various ions was studied and optimum conditions were developed for the determination of titanium in various aluminium and zinc alloys.     

Column chromatographic pre-concentration of iron(III) in alloys and biological samples with 1-nitroso-2-naphthol-3,6-disulphonate and benzyldimethyltetradecylammonium-perchlorate adsorbent supported on naphthalene using atomic absorption spectrometry

The solid ion-pair material produced from the reaction between benzyldimethyltetradecylammonium chloride (BDTA) and sodium perchlorate on naphthalene provides the basis for a simple, rapid and selective technique for pre-concentrating iron from up to 500 ml of aqueous solution. Iron reacts with disodium 1-nitroso-2-naphthol-3,6-disulphonate (Nitroso-R salt) to form a water-soluble coloured chelate anion. The iron chelate anion forms a water-insoluble, stable iron-Nitroso-R-BDTA complex on naphthalene packed in a column. Trace amounts of iron are quantitatively retained on naphthalene in the pH range 3.5-7.5 and at a flow-rate of 1-2 ml min-1. The solid mass is dissolved out from the column with 5 ml of N,N-dimethylformamide and iron is determined by means of an atomic absorption spectrometer at 248 nm. The calibration graph is linear for concentrations of iron over the range of 0.5-20 micrograms in 5 ml of final solution. The standard deviation and relative standard deviation were calculated. The detection limit of the method was 0.0196 micrograms ml-1 of iron. The sensitivity for 1% absorption was 0.072 microgram ml-1 (0.165 microgram ml-1 by direct atomic absorption spectrometry of aqueous solution). The proposed method was applied to the determination of iron in standard alloys and biological samples.     

Preconcentration of 1-(2-pyridylazo)-2-naphthol-iron(III)-capriquat on a membrane filter, and third-derivative spectrophotometric determination of iron(III)

Iron(III) was preconcentrated by collection on an organic solvent-soluble membrane filter (nitrocellulose (NC)) of the iron(III)-1-(2-pyridylazo)-2-naphthol (PAN) complex in the presence of capriquat as an oily quaternary ammonium salt. Third-derivative spectrophotometry was used for measurement of the third-derivative distance (d(3)A/dlambda(3)) between lambda(1) = 520 nm and lambda(2) = 590 nm or lambda(3) = 660 nm and lambda(4) = 724 nm of the iron(III)-PAN-capriquat complex or PAN-capriquat in dimethylsulfoxide (DMSO) following preconcentration. The calibration curve was linear in the range of 1-10 mug iron(III)/5.0 ml DMSO solution. The proposed method was about five-fold more sensitive and more selective than using zero-order spectrophotometry.     

Preconcentration of iron (III), cobalt (II) and copper (II) nitroso-R complexes on tetradecyldimethylbenzylammonium iodide-naphthalene adsorbent

Iron, cobalt and copper form coloured water soluble anionic complexes with disodium 1-nitroso-2-naphthol-3-6-disulphonate (nitroso R-salt). The anionic complex is retained quantitatively as a water insoluble neutral ion associated complex (M-nitroso R-TDBA) on tetradecyldimethylbenzylammonium iodide on naphthalene (TDBA(+)I(-)-naphthalene) packed column in the pH range of: Fe(III): 3.1-6.5, Co: 3.4-8.5 and Cu 5.9-8.0 when their solutions are passed individually over this adsorbent at a flow rate of 0.5-5.0 ml/min. The solid mass consisting of an ion associated metal complex along with naphthalene is dissolved out of the column with 5 ml dimethylformamide/chloroform and metals are determined spectrophotometrically. The absorbance is measured at 710 nm for iron, 425 nm for cobalt and 480 nm for copper. Beers law is obeyed in the concentration range 9.2-82 mug of iron, 425 nm for cobalt cobalt and 3.0-62 mug of copper in 5 ml of final DMF/CHCl(3) solution. The molar absorptivities are calculated to be Fe: 7.58 x 10(3), Co: 1.33 x 10(4) and Cu: 4.92 x 10(4)M(-1)cm(-1). Ten replicate determinations containing 25 mug of iron, 9.96 mug of cobalt and 3.17 mug of copper gave mean absorbances 0.677, 0.450 and 0.490 with relative standard deviations of 0.88, 0.98 and 0.92%, respectively. The interference of large number of metals and anions on the estimations of these metals has been studied. The optimized conditions so developed have been employed for the trace determination of these metals in standard alloys, waste water and fly ash samples.     

Atomic absorption spectrometric determination of trace zinc in alloys and biological samples after preconcentration with [1-(2-pyridylazo)-2-naphthol] on microcrystalline naphthalene

An atomic absorption spectrometric method for the determination of trace amounts of zinc after adsorption of its [1-(2-pyridylazo)-2-naphthol] complex on microcrystalline naphthalene has been developed. This complex is adsorbed on microcrystalline naphthalene in the pH range 3.5-7.5 from large volumes of aqueous solutions of various alloys and biological samples with a preconcentration factor of 40. After filtration, the solid mass consisting of the zinc complex and naphthalene was dissolved with 5 ml of dimethylformamide and the metal was determined by flame atomic absorption spectrometry. Zinc can alternatively be quantitatively adsorbed on [1-(2-pyridylazo)-2-naphthol]-naphthalene adsorbent packed in a column and determined similarly. About 0.5 ng of zinc can be concentrated in a column from 200 ml of aqueous sample, where its concentration is as low as 2.5 pg ml-1. The calibration curve is linear in the range 0.1-6.5 ng ml-1 in dimethylformamide solution. Eight replicate determinations of 2 ng ml-1 of zinc gave a mean absorbance of 0.145 with a relative standard deviation of 1.5%. The sensitivity for 1% absorption was 0.061 ng ml-1. Various parameters, such as the effect of pH and the interference of a number of metal ions on the determination of zinc, have been studied in detail to optimize the conditions for the determination of zinc in various standard complex materials.     

Atomic absorption spectrometric determination of ultra trace amounts of zinc after preconcentration with the ion pair of 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol and ammonium tetraphenylborate on microcrystalline naphthalene or by column method

Zinc is quantitatively retained on 2-(5-bromo-2-pyridylazo)-5-diethylamminophenol (5-BrPADAP)-ammonium tetraphenylborate with microcrystalline naphthalene or by a column method in the pH range 7.5-9.0 from a large volume of aqueous solutions of various samples. After filtration, the solid mass consisting of the zinc complex and naphthalene was dissolved with 5 ml of dimethylflarmamide and the metal was determined by atomic absorption spectrometry. Zinc complex can alternatively be quantitatively adsorbed on ammonium tetrphenylborate-naphthalene adsorbent packed in a column and determined similarly. The calibration curve is linear 0.05-4.0 ppb in dimethylformamide solution. Eight replicate detenninations of 1.0 ppb of zinc gave a mean absorbance of 0.124 with a relative standard deviation of 1.3%. The sensitivity for 1% absorption was 0.035 ppb. The interference of a large number of anions and cations has been studied and the optimized conditions developed were utilized for the trace determination of zinc in various standard samples.     

Tetradecyldimethylbenzylammonium thiocyanate adsorbent supported on naphthalene for the preconcentration and determination of cobalt in aluminium alloys and steels using atomic absorption spectrometry

A solid ion-pair material produced from tetradecyldimethylbenzylammonium chloride (TDBA) and ammonium thiocyanate on naphthalene provides a simple, rapid and selective technique of preconcentrating cobalt from up to 200 ml of aqueous solution. Cobalt reacts with sodium 1-nitroso-2-naphthol-3,6-disulphonate (nitroso-R salt) to form a brown, water-soluble chelate anion. The chelate anion forms a water-insoluble Co-nitroso-R salt-TDBA complex on naphthalene packed in a column and trace cobalt is quantitatively retained on the naphthalene in the pH range 2.7–11.0 at a flow-rate of 2 ml min^?1. The solid mass is stripped from the column with 5 ml of dimethylformamide (DMF) and cobalt is measured by atomic absorption spectrometry (AAS) at 241 nm. The calibration graph is linear over the concentration range 0.5–15μg Co in 5 ml of dimethylformamide solution. Seven replicate determinations of 9 μg of cobalt gave a mean absorbance of 0.095 with a relative standard deviation of 1.7%. The sensitivity for 1% absorption was 0.0834μg ml^?1 (0.240 μg ml^?1 for direct AAS on the aqueous solution). The proposed method was utilized for the determination of cobalt in standard aluminium alloys and steel samples.     

Preconcentration of copper with the ion-pair of 1,10- phenanthroline and tetraphenylborate on naphthalene

A solid ion-pair material produced from 1,10-phenanthroline and tetraphenylborate on naphthalene provides a simple, rapid and fairly selective means of preconcentrating copper from up to 1000 ml of aqueous samples (about 200-fold concentration is possible). Copper is quantitatively adsorbed in the pH range 1.6–10.4 at a flow rate of 3 ml min^?1. The solid mass (0.2 g) is dissolved from the column with 5 ml of dimethylformamide (DMF) and copper is measured by atomic absorption spectrometry at 324.7 nm. Linear calibration is obtained for 2–28 μg of copper in 5 ml of DMF solution. Replicate determination of 14 μg of copper gave a mean absorbance of 0.220 (n = 7) with a relative standard deviation of 1.5%. The sensitivity for 1% absorption was 0.093 μg ml^?1. After optimization, the method was applied to determine trace copper in standard reference materials, natural waters, beverages and hair.     

Column preconcentration and FAAS determination of copper,iron, nickel and zinc using 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol-tetraphenylborate-naphthalene adsorbent

A solid co-precipitated material obtained from an ion-pair of 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (5-Br-PADAP) and tetraphenylborate (TPB), and microcrystals of naphthalene has been tried as an adsorbent for the column preconcentration of copper(I), iron(II), nickel(II) and Zn(II). The retention of the metal ions was found to be maximum and constant in the pH range 3.0-8.0 for Cu, 3.8-7.5 for Fe, 4.5-7.5 for Ni and 8.5-11.0 for Zn. The elements were determined by FAAS after dissolving the metal along with the adsorbent in an organic solvent (10 mL of DMF). The characteristic concentration for 1% absorption was found to be 0.0332, 0.0536, 0.0537 and 0.0142 (aqueous medium 0.0512, 0.0638, 0.1294 and 0.0216) microg mL(-1) for Cu, Fe, Ni and Zn, respectively. The calibration plot was linear in the range 1.5-20.0, 2.0-38.0, 2.5-25.0 and 0.5-15.0 micro g in the final 10 mL of DMF solution for Cu, Fe, Ni and Zn, respectively. Various parameters such as pH, volume of buffer, amount of adsorbent, flow rate, preconcentration factor and effect of diverse salts and cations were studied. The optimised conditions were utilized for the determination of Cu, Fe, Ni and Zn in various water, beverage and human hair samples.     

Atomic absorption spectrometric determination of trace amounts of nickel after preconcentration with [1-(2-Pyridylazo)-2-Naphthol]-Naphthalene adsorbent or after adsorption of its complex on microcrystalline naphthalene

An atomic absorption spectrometric method for the determination of trace amounts of nickel after adsorption of its 1 -(2-pyridylazo)-2-naphthol complex on microcrystalline naphthalene has been developed. This complex is adsorbed on microcrystalline naphthalene in the pH range 4.5-7.8 from large volumes of aque ous solutions of various alloys and biological and environmental samples containing nickel. After filtration, the solid mass consisting of nickel complex and naphthalene was dissolved in 5 mL of dimethylformamide, and the metal was determined using a flame atomic absorption spectrometer at a wavelength of 232 nm. Alternatively, nickel can be quantitatively adsorbed on [l-(2-pyridylazo)-2-naphthol]-naphthalene adsorbent packed in a column and determined similarly. The calibration curve is linear over the concentration range 2.0-100 Μg of nickel in 5 mL of the final dimethylformamide solution. Eight replicate determinations of 20 Μg of nickel give a mean absorbance of 0.072 with a relative standard deviation of 1.3%. The sensitivity for 1% absorption is 0.24 Μg/mL. Various parameters such as the effect of pH, the volume of the aqueous phase, and the interference of a large number of metal ions with the determination of nickel have been studied in detail to optimize the conditions for its determination in various standard alloys and biological and environmental samples. This article was submitted by the authors in English.     

Flame atomic absorption spectrometric determination of trace chromium in various standard samples after preconcentration with 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol

Chromium can be quantitatively retained as 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (5-Br-PADAP)-tetra-phenylborate(TPB) complex onto microcrystalline naphthalene in the pH range 4.8-5.9 from a large volume of aqueous solutions of various standard samples. After filtration, the solid mass consisting of the chromium complex and naphthalene was dissolved with 5 mL of dimethylformamide and the metal was determined by air-acetylene FAAS. A detection limit of 4 ng/mL for chromium was established. The interference of a large number of anions and cations has been studied and the optimized conditions developed were utilized for the trace determination of chromium in various standard alloys and biological samples.     

Flame atomic absorption spectrometric determination of trace chromium in various standard samples after preconcentration with 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol

Chromium can be quantitatively retained as 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (5-Br-PADAP)-tetraphenylborate(TPB) complex onto microcrystalline naphthalene in the pH range 4.8–5.9 from a large volume of aqueous solutions of various standard samples. After filtration, the solid mass consisting of the chromium complex and naphthalene was dissolved with 5 mL of dimethylformamide and the metal was determined by air-acetylene FAAS. A detection limit of ¶4 ng/mL for chromium was established. The interference of a large number of anions and cations has been studied and the optimized conditions developed were utilized for the trace determination of chromium in various standard alloys and biological samples.     

Differential pulse polarographic determination of trace amounts of vanadium and molybdenum in various standard alloys and environmental samples after preconcentration of their morpholine-4-carbodithioates on microcrystalline naphthalene or morpholine-4-dithiocarbamate cetyltrimethyl-ammonium bromide-naphthalene adsorbent

A highly selective, sensitive, and fairly rapid and economical differential pulse polarographic (DPP) method has been reported for the determination of trace amounts of vanadium and molybdenum in standard alloys and various environmental samples. The morpholine-4-carbodithioates of these metals were retained (>99% recovery) quantitatively on microcrystalline naphthalene in the pH range 4.5-6.9 for vanadium and 1.5-4.5 for molybdenum. These metals were determined by DPP after desorption with 10 ml of 1 M HCl. Vanadium and molybdenum may also be preconcentrated by passing their aqueous solutions under similar conditions on morpholine-4-dithiocarbamate CTMAB-naphthalene adsorbent packed in a column at a flow rate of 1-5 ml min(-1) and determined similarly. The detection limits are 0.20 ppm for vanadium and 0.04 ppm for molybdenum at minimum instrumental settings (signal to noise ratio=2). The linearity is maintained in the following concentration ranges, vanadium 0.50-10.0 and molybdenum 0.10-9.0 ppm, with a correlation factor of 0.9996 (confidence interval of 95%, slopes 0.0196 and 0.01497 muA mug(-1), intercepts 3.65x10(-3) and -1.92x10(-3) respectively) and relative standard deviation of 1.1% in the microcrystalline method, while in the column method, the linearity is maintained in the concentration ranges, 0.50-6.5 for vanadium and 0.10-5.5 ppm for molybdenum with correlation factor of 0.9994 (with confidence interval of 95%, slopes 0.0194, 0.015 muA mug(-1), intercepts 3.60x10(-3) and -1.90x10(-3) respectively) and relative standard deviation of 1.4%. Various parameters such as the effect of pH, reagent, naphthalene and CTMAB concentrations, volume of aqueous phase and interference of a large number of metal ions on the estimation of vanadium and molybdenum have been studied in detail to optimize the conditions for their voltammetric determination at trace level in various standard alloys and environmental samples.     

Determination of ruthenium and osmium in each other's presence in chloride solutions by direct and third-order derivative spectrophotometry

Ruthenium and osmium (up to 20 mug Ru(Os) ml(-1)) can be determined in chloride solutions directly after absorption of RuO(4) and OsO(4) in hydrochloric acid. In 9 M HCl, RuO(4) and OsO(4) are quantitatively converted into RuCl(6)(2-) (lambda(max) = 480.0 nm, epsilon = 4.8 x 10(3) l mol(-1) cm(-1)) and OsCl(6)(2-) (lambda(max) = 334.8 nm, epsilon = 8.4 x 10(3) l mol(-1) cm(-1)) respectively. Osmium does not interfere with the determination of ruthenium in the form of the RuCl(6)(2-) complex by direct spectrophotometry. The absorbance of the obtained solution at lambda(max) = 480.0 nm corresponds only to the concentration of ruthenium. A derivative spectrophotometric method using numerical calculation of absorption spectra of the RuCl(6)(2-) and OsCl(6)(2-) complexes has been developed for the determination of osmium in a mixture with ruthenium. The interfering effect of ruthenium on the determination of osmium can be eliminated by measuring the value of a third-order derivative spectrum of the OsCl(6)(2-) complex at 350.0 nm ("zero-crossing point" of ruthenium). Simple and rapid determination of ruthenium and osmium in a calibration standard solution of the noble metals (Ru, Rh, Pd, Os, Ir, Pt and Au) for plasma spectroscopy using the proposed methods has been achieved.