Determination of transition metal ions in tobacco as their 2-(2-quinolinylazo)-5-dimethylaminophenol derivatives using reversed-phase liquid chromatography with UV-VIS detection

This paper reports the utilization of solid-phase extraction and the reversed-phase high-performance liquid chromatography for the determination of six important transition metal ions: iron, cobalt, nickel, copper, zinc and manganese in tobacco with 2-(2-quinolinylazo)-5-dimethylaminophenol (QADMAP) as chelating reagent. Iron, cobalt, nickel, copper, zinc and manganese ions react with QADMAP to form colored chelates in the medium of acetic acid-sodium acetate buffer solution (pH 4.0). These chelates can be enriched by solid-phase extraction with Waters Sep-Pak-C18 cartridge, and eluted the retained chelates from cartridge with tetrahydrofuran. The chelates were separated on a Waters Nova-Pak-C18 column (150x3.9 mm, 5 microm) by gradient elution with methanol (containing 0.5% of acetic acid) and 0.05 mol/l pH 4.0 acetic acid-sodium acetate buffer solution as mobile phase at a flow-rate of 0.5 ml/min. The detection limits of iron, cobalt, nickel, copper, zinc and manganese are 10, 12, 8, 13, 17 and 22 ng/l, respectively. This method had been applied to the determination of iron, cobalt, nickel, copper, zinc and manganese in tobacco with good results.     

Malachite green as a reagent for detection and spectrophotometric determination of chromium(VI)

A sensitive and inexpensive method of spectrophotometric determination of chromium(VI), based on the absorbance of its complex with malachite green and acetic acid at pH 2.5 is reported. The complex shows a molar absorptivity of 8 x 10(4) l.mole(-1) cm(-1) at 560 nm, using malachite green and acetic acid as reference solution. The effect of time, temperature, pH and reagent concentration is studied and optimum operating conditions are established. Beer's law is applicable in the concentration range 2.0-22.8 mug/ml chromium(VI). The resin beads act as a catalyst and as little as 1.6 mug of chromium(VI) is detected in the resin phase as compared to 4.1 mug in the solution phase. The standard deviation in the determinations is +/-0.40 mug/ml for a 10.35 mug/ml solution.     

Solid phase extraction and spectrophotometric determination of silver with 2-(2-quinolylazo)-5-diethylaminophenol as chromogenic reagent.

A new chromogenic reagent, 2-(2-quinolylazo)-5-diethylaminophenol (QADEAP), was synthesized. A sensitive, selective and rapid method has been developed for the determination of microg/L level silver ion based on the rapid reaction of silver(l) with QADEAP and the solid phase extraction of the colored chelate with C18 cartridge. The QADEAP reacts with Ag(l) to form a violet chelate of a molar ratio 1:2 (silver to QADEAP) in pH 3.5-8.0. This chelate was prconcentrated by solid phase extraction with C18 cartridge. An enrichment factor of 100 was achieved. The molar absorptivity of the chelate is 1.30 x 10(5) L mol(-1) cm(-1) at 590 nm in measured solution. Beer's law is obeyed in the range of 0.01-0.6 microg/ml. The relative standard deviation for eleven replicate samples of 0.01 microg/ml is 1.15%. The detection limit is 0.02 microg/L in the original samples. This method was applied to the determination of microg/L level silver ion in water with good results.     

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.     

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 cobalt with N-(dithiocarboxy)sarcosine and amberlite xad-4 resin

Cobalt reacts with N-(dithiocarboxy)sarcosine (DTCS) to form a 1:3 Co:DTCS complex which is so stable that after its formation no decomposition occurs even in 4M hydrochloric acid. The complex is sorbed on a column of Amberlite XAD-4 copolymer from an acidic solution and eluted with 10 ml of a 1:1:3 v v mixture of 1.0M ammonia solution (pH = 9), 0.1M EDTA and methanol. The absorbance of the eluted chelate is measured at 320 nm against water ( = 2.15 x 10(4) l.mole(-1).cm(-1)). The recovery of cobalt from 1 litre of tap-water or sea-water is quantitative. The effect of diverse ions can be eliminated by the addition of EDTA after chelation of the cobalt. The copper complex with DTCS is partly sorbed on the column because of its slow rate of decomposition by EDTA, but most of the copper chelate sorbed can be eluted with hydrochloric acid and any co-eluted with the cobalt chelate can be completely decomposed by heating the eluate. Cobalt enrichment factors of at least 100 are obtained, so the method is applicable to the determination of cobalt at the ng ml level.     

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.     

A highly sensitive spectrophotometric method for determination of micro amounts of arsenic

A highly sensitive spectrophotometric method for determination of arsenic, based on the formation of an ion-association complex between arsenoantimonomolybdenum blue and Malachite Green, has been developed. The ion-association complex is soluble in the presence of Triton X-305, so arsenic can be determined directly in aqueous solution. The apparent molar absorptivity for arsenic is 1.13 x 10(5) l.mole(-1).cm(-1) at 640 nm. Beer's law is obeyed for 0-5 mug of arsenic. The lower limit of determination (absorbance = 0.01) is 4 ng ml in the final solution.     

Solid Phase Extraction and Spectrophotometric Determination of Silver with 2-(2-Quinolylazo)-5-Dimethylaminophenol

A new chromogenic reagent, 2-(2-quinolylazo)-5-Dimethylaminophenol (QADMAP) was synthesized, and a sensitive, selective, and rapid method was developed for the determination of the μg/L level of silver ions. The method is based on the rapid reaction of silver(I) with QADMAP and the solid phase extraction of the colored chelate using a C₁₈ cartridge. The QADMAP reacts with Ag(I) in the presence of a citric acid-sodium hydroxide buffer solution (pH 5.0) and a sodium dodecyl sulfonate (SDS) medium to form a violet chelate of molar ratio 1 : 2 (silver to QADMAP). This chelate was enriched by solid phase extraction with C₁₈ cartridge, and the retained chelate was eluted from the cartridge using ethanol (with 1% acetic acid). In the ethanol medium (with 1% acetic acid), the molar absorptivity of the chelate was 1.25 × 10⁵ L mol⁻¹ cm⁻¹ at 584 nm. Beer’s law was obeyed in the range 0.01–0.6 μg/mL. The relative standard deviation for eleven replicate samples of 0.01 μg/mL was 1.86%. The detection limit is 0.02 μg/L in the original samples. The method was applied to the determination of μg/L levels of silver ions in water with good results.__________From Zhurnal Analiticheskoi Khimii, Vol. 60, No. 6, 2005, pp. 566–570.Original English Text Copyright © 2005 by Huang, Yang, Hu, Yin.This article was submitted by the authors in English.     

Spectrophotometric determination of gallium(III) with phenylfluorone in the presence of hexadecylpyridinium bromide and pyridine

Phenylfluorone reacts with gallium in the presence of hexadecylpyridinium bromide and pyridine to form a water-soluble chelate with an absorption maximum at 570 nm and constant absorbance in the pH range 4.0-5.5. At this wavelength, Beer's law is obeyed up to 4.3 x 10(-6)M gallium. The sensitivity is very high and the molar absorptivity is 1.48 x 10(5) 1.mole(-1).cm(-1). The chelate has been utilized in the determination of gallium at the mug level. The ratio of gallium to phenylfluorone in the complex is 1:2.     

Analytical application of a new thiazolylazo reagent, 2-(2-benzothiazolylazo)-5-dimethylamino-4-tolylarsonic acid Spectrophotometric determination of palladium

A new thiazolylazo reagent, 2-(2-benzothiazolylazo)-5-dimethylamino-4-tolylarsonic acid, has been synthesized and found to be a good chromogenic reagent for palladium. A 1:1 blue chelate (lambda(max) = 718 nm) is formed in a sulphuric or nitric acid medium. The molar absorptivity is 6.65 x 10(4) l. mole(-1).cm(-1). Beer's law is obeyed in the range 0-1.6 mug/ml Pd. Relatively large amounts of co-existing elements, including noble metals, can be tolerated.     

Water-soluble polymers for spectrophotometric and flow injection determination of cobalt with nitroso-R-salt

The water-soluble polymers poly(ethylenimine), quaternized poly(ethylenimine), and poly-4-vinyl-(N-benzyltrimethyl) ammonium chloride were found to be able to change the kinetics of the reaction of cobalt with nitroso-R-salt and the optical density of the cobalt complex formed. The optimum pH range for the complex formation was a wide range from 1 to 10 and at pH 2 the reaction developed instantly. The calibration graph was linear in the range 0.005-2 mug ml(-1). The effective molar absorptivity coefficient of the complex was equal to (2.8+/-0.08)10(3). A spectrophotometric determination method for cobalt with nitroso-R-salt in the presence of water-soluble polymers (before and after membrane preconcentration) and a colorimetric flow injection method were developed. For the flow injection-based spectrophotometric determination, the calibration graph was linear in the concentration range of 0-4.0 mug ml(-1) cobalt with a regression coefficient of 0.9992. The relative standard deviation (R.S.D.) for the determination of 1.0 mug ml(-1) cobalt was 0.9% (ten replicate injections), and at all concentration measured, the R.S.D. of the data was below 5.0%. The proposed FI procedure was applied to river water samples after membrane preconcentration of cobalt. The limit of detection was 4 ng ml(-1).     

Study on the Solid Phase Extraction of Hg(II)‐ABR Chelate with C18 Disks and its Application to the Determination of Mercury in Tobacco and Tobacco Additives

A highly sensitive, selective and rapid method for the determination of mercury based on the rapid reaction of mercury(II) with 5‐(p‐aminobenzylidene)‐rhodanine (ABR) and the solid phase extraction of the colored chelate with C₁₈ disks has been developed. In the presence of pH = 3.5 sodium acetate‐acetic acid buffer solution and Emulsifier‐OP medium, ABR reacts with mercury(II) to form a red chelate of a molar ratio 1:2 (mercury to ABR). This chelate was enriched by the solid phase extraction with C₁₈ disks and eluted the retained chelate from the disks with dimethyl formamide (DMF). The enrichment factor of 50 was achieved. In the DMF medium, the molar absorptivity of the chelate is 1.16 × 10⁵ L.mol^?1.cm^?1 at 540 nm. Beer's law is obeyed in the range of 0.01?3 μg/mL in the measured solution. The relative standard deviation for eleven replicated samples of 0.01 μg/mL level is 1.83%. This method was applied to the determination of mercury in tobacco and tobacco additives with good results.     

Extractive spectrophotometric determination of trace amounts of iron(III) with benzyltriethylammonium chloride

The ion-association complex formed between a thiocyanato-iron(III) ion and a benzyltriethylammonium ion is extracted into 1,2-dichloroethane, and its absorbance at 476 nm is used for determination of the iron. Beer's law is obeyed up to about 4 mug/ml iron concentration in the final solution. The molar absorptivity is 2.79 x 10(4) l.mole(-1).cm(-1).     

Determination of trace lead, cadmium and mercury by on-line column enrichment followed by RP-HPLC as metal-tetra-(4-bromophenyl)-porphyrin chelates

This paper reports the utilization of tetra-(4-bromophenyl)-porphyrin (T(4)BPP) as a chelating reagent using Waters Xterratrade mark RP(18) column for the on-line column enrichment and the separation of trace lead, cadmium and mercury ions by reversed-phase high-performance liquid chromatography (RP-HPLC) with photodiode array detector. When the Hg-T(4)BPP, Pb-T(4)BPP and Cd-T(4)BPP chelates were injected into the injector and sent to the enrichment column with 0.05 mol l(-1) of pH 10.0 pyrrolidine-phosphoric acid buffer solution (containing 10% of tetrahydrofuran (THF)) as mobile phase. The chelates were retained on the top of the enrichment column. After the enrichment is finished, by switching the valve of six-ports switching valve, the retained metal-T(4)BPP chelates will be eluted by mobile phase in reverse direction and will travel towards analytical column. With THF (containing 0.05 mol l(-1), pH 10.0 pyrrolidine-phosphoric acid buffer salt) and 0.05 mol l(-1), pH 10.0 pyrrolidine-phosphoric acid buffer solution (containinging 10% THF) gradient elution as mobile phase, the chelates separation on the analytical column was satisfactory. The linearity ranges are 0.01-120 mug l(-1) for each metal ion. The detection limits (S/N=3) of lead, cadmium and mercury are 1.0, 0.5 and 1.0 ng l(-1), respectively. This method can be applied to the determination (mug l(-1)) level of lead, cadmium and mercury in drinking water with satisfactory results.     

Spectrophotometric determination of cobalt with 1-(2-pyridylazo)-2-naphthol and surfactants

A simple and highly selective spectrophotometric method for the determination of cobalt based upon the rapid reaction with PAN in the presence of surfactants and minute amounts of ammonium persulphate at pH 5.0 is described. The cobalt(III) chelate is made water-soluble by a neutral surfactant. Triton X-100, combined with sodium dodecylbenzene sulphonate (DBS). Iron(III), bismuth, tin(IV) and aluminium are masked with oxalate or citrate. Iron(II) must be absent. The other metal-PAN chelates, except that of nickel, are readily decomposed by EDTA. Up to 150 microg of nickel does not interfere. When larger amounts up to 625 microg are present, the absorbance can be corrected by measurements at two wavelengths. In a strongly acid medium (below pH 0.5) the nickel and other metal chelates are completely and instantaneously decomposed, while the cobalt(III) chelate remains unchanged. When, in place of EDTA, several ml of 6M hydrochloric acid are added after the colour development, nickel in quantities up to 1250 microg can be tolerated. A several hundredfold excess of zinc and manganese does not interfere. At 620 nm Beer's law is obeyed over the cobalt concentration range 0.4-3.2 microg/ml. The precision (95% confidence) is +/- 1.0 microg for 100 microg of cobalt. The molar absorptivity is 1.90 x 10(4) l. mole(-1) .cm(-1).     

Colour reaction of platinum(II) with 5-(4-nitrophenylazo)-8-(p-toluenesulphonamido)-quinoline and its analytical applications

A simple, rapid and sensitive spectrophotometric method has been developed for the determination of platinum. 5-(4-Nitrophenylazo)-8-(p-toluenesulphonamido)quinoline (NPTSQ) reacts with platinum(II) almost instantaneously in alkaline solution to form a violet-red 1:2 complex with an absorption maximum at 640 nm. Beer's law is obeyed over the concentration range 0-1 mug/ml platinum. The molar absorptivity is 1.37 x 10(5) 1.mole(-1).cm(-1). The method has been used for the determination of microamounts of platinum in catalysts and anode slime.     

Extraction and spectrophotometric determination of lead(II) with pyridine-2-acetaldehyde salicyloylhydrazone

Lead(II) reacts with pyridine-2-acetaldehyde salicyloylhydrazone (PASH) in the pH range 8.6-9.3 to form a yellow-green, 1:2 chelate which can be extracted into chloroform. Beer's law is obeyed in the concentration range 1.5-6.2 mug ml(-1) of lead(II). The molar absorptivity of the extracted species is 1.93 x 10(4) l mol(-1) cm(-1) at 380 nm. The proposed method is sensitive, simple, rapid, accurate and has been satisfactorily applied for the determination of lead in synthetic mixtures, alloys, water and soil samples.     

Spectrophotometric determination of aluminium by morin

A direct spectrophotometric method for the determination of aluminium with morin has been developed. Morin reacts in slightly acidic 50% ethanolic media (0.0001-0.0015 M H(2)SO(4)) with Al to give a deep-yellow chelate which has an absorption maximum at 421 nm. The average molar absorptivity and Sandell's sensitivity were found to be 5.3 x 10(3) l mol(-1) cm(-1) and 5 ng of Al cm(-2), respectively. The reaction is instantaneous and absorbance remains stable for 48 h. The colour system obeys Beer's law from 10 ng ml(-1) to 5.0 mug ml(-1) of Al; the stoichiometric composition of the chelate is 2:3 (Al:morin). The interference from over 50 cations, anions and complexing agents has been studied at 0.1 mug ml(-1) of Al. The method was applied successfully to some certified reference material samples (alloys and steels), environmental waters (inland and surface), biological samples (human blood, urine and gallstone), soils and complex synthetic mixtures.     

Photometric determination of cobalt with nitroso-R-salt

The chelate is quantitatively formed only in the pH range 6.5-7.5. Despite the large stability constant, a large excess of reagent is required to suppress interferences. The most suitable wavelength for the photometric measurement is 500 nm, where the molar absorptivity is 1.607 x 10(4) 1.mole(-1). cm(-1). The procedure given allows determination of 8 x 10(-4)% Co in a l-g sample. The standard deviation for cobalt is 2.1 mug/100 ml (f = 19). Applications to analysis of iron and steel, nickel, copper, ores and silicates are given.