Spectrophotometric and derivative spectrophotometric determination of iron by extraction of the iron(II)-TPYZ-picrate ion-association complex

A solvent extraction-spectrophotometric determination of microamounts of iron has been developed, based on the formation of an ion-association complex of iron(II) with 2,4,6-tris(2'-pyridyl)-1,3,5-triazine as primary ligand and picrate as counter-ion, which is extracted into 1,2-dichloroethane. The complex is formed at pH 4.0-7.0 and the iron concentration can be determined by measuring the absorbance directly in the organic phase. The apparent molar absorptivity is 2.2 x 10(5) l.mole(-1).cm(-1). As the method is practically free from interferences it was applied to the determination of iron in different biological and inorganic samples. Although the proposed method is very sensitive it can be further sensitized by employing the derivative spectrophotometric technique.     

Extraction-spectrophotometric determination of iron(II) by ternary complex formation with pyrocatechol violet and cetyltrimethylammonium bromide

A method for iron(II) determination based on reaction with Pyrocatechol Violet to form a 1:2 binary complex at pH 5-7 is described and has been extended to an extraction-spectrophotometric procedure for the determination of iron(II) by formation of the 1:2:2 iron(II)-Pyrocatechol Violet-cetyltrimethylammonium bromide ternary complex. The molar absorptivities of the binary and ternary complexes at 595 and 605 nm are 6.55 x 10(4) and 1.35 x 10(5)1.mole(-1).cm(-1), respectively. The method has been successfully applied to the determination of iron in felspar, Portland cement and sodium hydroxide.     

Simultaneous determination of iron and zinc by pH gradient construction in a flow-injection system

A flow-injection method for the simultaneous determination of iron and zinc in the human hair with 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (5-Br-PADAP) using a pH gradient technique has been developed. The linear range for the determination of iron is 0.1 approximately 1.8 mug ml(-1) and for zinc is 0.2 approximately 5.0 mug ml(-1). About 20 approximately 30 samples can be determined in 1 h. The proposed method is simple, rapid and accurate. It has been applied to the simultaneous determination of trace amounts of iron and zinc in the human hair with satisfactory results.     

Ammonium tetraphenylborate-naphthalene adsorbent for the preconcentration and trace determination of iron in alloys and biological samples using 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol by third derivative spectrophotometry

A solid ion-pair material produced from ammonium tetraphenylborate on naphthalene (ATPB-naphthalene) provides a simple, rapid, economical and selective technique for preconcentrating iron from approximately 500 ml of aqueous solution of standard alloys and biological samples. Iron reacts with 2-(5-bromo-2-pryidlazo)-5-diethylaminophenol (5-Br-PADAP) to form a water-soluble cationic complex. When the aqueous solution of this cationic species in the pH range 3.2-8.5 is passed over the adsorbent ATPB-naphthalene at a flow rate of 1 ml min(-1), it is quantitatively retained on naphthalene as an uncharged ion-associated complex. The solid mass from the column was dissolved out with 5 ml of dimethylformamide (DMF) and iron is determined by third derivative spectrophotometry by measuring the signal d(3)A/ dlambda(3) between lambda(2)(773 nm) and lambda(3)(737 nm). The calibration curve is linear over the concentration range 0.10-25.0 mug of iron in 5 ml of DMF solution. Eight replicate determinations of 5 mug of iron gave a mean intensity (peak-to-peak signal between lambda(2) and lambda(3)) of 1.534 with a relative standard deviation of 0.90%. The sensitivity of the method is 0.307 (d(3)A/dnm(3) )/mug found from the slope of the calibration curve. 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 iron in various standard alloys and biological samples.     

Extractive-spectrophotometric determination of trace iron(II) with di-2-pyridylmethanone 2-(5-nitro)pyridylhydrazone

The optimum conditions for the extractive-spectrophotometric determination of trace iron(II) with di-2-pyridylmethanone 2-(5-nitro)pyridylhydrazone have been established. Iron(II) reacts with this reagent at pH 2.0-7.5 to form an uncharged 1:2 (metal-to-ligand) complex, which can be extracted with toluene. Beer's law is obeyed over the range up to 0.84 mug/ml of iron(II) at 505 nm. The molar absorptivity of the extracted species is 5.83 x 10(4) 1.mole(-1).cm(-1). The proposed method is extremely sensitive and reproducible, and has been satisfactorily applied to the determination of total iron in freshwater samples by adding ascorbic acid to reduce iron(III).     

Simultaneous determination of copper and iron by second derivative spectrophotometry using mixtures of ligands

A highly sensitive and selective second derivative spectrophotometric method has been developed for the determination of copper and iron in mixtures. The method is based on the separation of the analytes by liquid-liquid extraction as picrate ion pairs. Iron-picrate, reacts in the organic phase of DCE with 5-phenyl-3-(4-phenyl-2-pyridinyl)-1,2,4-triazine (PPT). Similarly the copper-picrate reacts with 2,9-dimethyl-4,7-diphenyl-1,10-phenantroline (bathocuproine). The extracts were evaluated directly by derivative spectrophotometric measurement, using the zero-crossing approach for determination of copper and graphic method for iron. Iron and copper were thus determined in the ranges 8-120 ng ml(-1) and 8-125 ng ml(-1), respectively, in the presence of one another. The detection limits achieved (3sigma) were 2.9 ng ml(-1) of iron and 2.8 ng ml(-1) of copper. The relative standard deviations were in all instances less than 2.1%. The proposed method was applied to the determination of both analytes in river and tap water and the results were consistent with those provided by the AAS standard method.     

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.     

A flow-through fluorescent sensor to determine Fe(III) and total inorganic iron

A flow-through fluorescent sensor for the consecutive determination of Fe(III) and total iron is described. The reactive phase of the proposed sensor, which has a high affinity for complexed Fe(III), consists of pyoverdin immobilized on controlled pore glass (CPG) by covalent bonding. This pigment selectively reacts with Fe(III) decreasing its fluorescence emission. Total inorganic iron is determined as Fe(III) after on-line oxidation in a mini-column containing persulphate immobilized on an ion exchange resin. The developed method allows the determination of Fe(III) in the 3-200 (g l(-1) range. The relative standard deviations of 10 determinations of 60 (g l(-1) of Fe(III) and 20 (g l(-1) of Fe(III)+Fe(II) are 3 and 5%, respectively. The sensor has been satisfactorily applied to speciate iron in synthetic, tap and well waters and wines. There were no significant differences for total inorganic iron determination between this new method and the atomic absorption spectroscopy reference method at the 95% confidence level. The sensor allows the concentration of Fe(II) to be calculated as the difference between total inorganic iron and Fe(III). The lifetime of the sensor is at least 3 months in continuous use or the equivalent of 1000 determinations.     

Surfactant-mediated extraction of iron and its spectrophotometric determination in rocks, minerals, soils, stream sediments and water samples

An extraction spectrophotometric method for iron determination in rocks, minerals, soils, stream sediments and water samples has been developed. At pH 3-4, iron (III) forms a 1:2:1 ternary complex with thiocyanate and cetyltrimethylammonium bromide (Fe/SCN/CTAB) which is extracted into ethyl acetate. The readily formed purple complex is suitable for extraction spectrophotometric determination of iron in rocks and related materials from submicrogram to milligram levels. The method is free from any interference due to commonly associated ions present in the matrices of rock samples. The present method is at least fourfold more sensitive (ε=3.2×10⁴ l mol⁻¹ cm⁻¹) than the conventional thiocyanate method and, in addition to the enhanced sensitivity and selectivity, it has got definite advantages over the corresponding binary thiocyanate system in terms of substantial improvement in the stability of the complex formed and broadening of Beer's law adherence range (0-6.0 mg/l). The method has been applied to a number of geological and hydrogeochemical samples for the determination of iron and the results obtained have been found to be favourably comparable with those obtained from the standard methods.     

Flow injection determination of iron by its catalytic effect on the oxidation of 3,3',5,5'-tetramethylbenzidine by hydrogen peroxide

A flow injection-photometric method has been developed for the determination of iron(II+III). The method is based on the catalytic effect of iron(III) on the hydrogen peroxide oxidation of 3,3',5,5'-tetramethylbenzidine to form a blue compound (lambda(max)=650 nm). In this catalyzed reaction, 1,10-phenanthroline acted as an effective activator. Iron(II) is also determined, being oxidized by hydrogen peroxide. Calibration graphs for iron(II) and iron(III) obtained under the optimized conditions were identical with each other and linear in the range 0.2-200 ng ml(-1) with a detection limit of 0.05 ng ml(-1) iron. The reproducibility was satisfactory with a relative S.D. of 1.0% for ten determinations of 5 ng ml(-1) iron(III). The proposed method was successfully applied to the determination of iron in river and lake water samples and can be determined free iron species.     

Utility of solid-phase spectrophotometry for determination of dissolved iron(II) and iron(III) using 2,3-dichloro-6-(3-carboxy-2-hydroxy-1-naphthylazo)quinoxaline

A new simple, very sensitive, selective and accurate procedure for the determination of trace amounts of iron(II) by solid-phase spectrophotometry (SPS) has been developed. The procedure is based on fixation of iron(II) as 2,3-dichloro-6-(3-carboxy-2-hydroxy-1-naphthylazo)quinoxaline on a styrene-divinylbenzene anion-exchange resin. The absorbance of resin sorbed iron(II) complex is measured directly at 743 and 830nm. Iron(III) was determined by difference measurements after reduction of iron(III) to iron(II) with hydroxylamine hydrochloride. Calibration is linear over the range 1.0-20 microgL(-1) of Fe(II) with relative standard deviation (R.S.D.) of 1.65% (n=10.0). The detection and quantification limits for 100mL sample system are 280 and 950 ngL(-1) using 0.5 g of the exchanger. The molar absorptivity and Sandell sensitivity are also calculated and found to be 2.86 x 10(6)Lmol(-1)cm(-1) and 0.0196 ngcm(-2), respectively. The proposed procedure has been successfully applied to determine iron(II) and iron(III) in tap, mineral and well water samples.     

Catalytic flow-injection determination of sub-ppb copper(II) using the redox reaction of cysteine with iron(III) in the presence of 2,4,6-tris(2-pyridyl)-1,3,5-triazine.

A kinetic-catalytic spectrophotometric flow-injection method was developed for the rapid and sensitive determination of trace amounts of copper(II). The method is based on the catalytic effect of copper(II) on the redox reaction of cysteine with iron(III). Iron(II) produced by the catalytic reaction reacts with 2,4,6-tris(2-pyridyl)-1,3,5-triazine (TPTZ) to form the iron(II)-TPTZ complex (lambda(max) = 593 nm). By measuring an absorbance of the complex, one could determine 0.05-8 ppb copper(II) with the relative standard deviations (n = 10) of 1.6%, 1.3%, and 0.8% for 0.5 ppb, 1 ppb, and 2 ppb copper(II), respectively. The limit of detection (S/N = 3) was 0.005 ppb. The sample throughput was 30 h(-1). The proposed method was successfully applied to the determination of copper in natural water and serum samples.     

A new spectrophotometric method for the determination of total and ferric iron in rain water at the ppb level

A new, simple, selective and sensitive spectrophotometric procedure for the on-site quantification of iron at nano-gram levels in atmospheric precipitations, i.e. rain as sample source is described. It is based on the color reaction of Fe3+ with SCN- ions in the presence of a cationic surfactant, i.e. cetylpyridinium chloride (CPC), in strong HCl solution, and subsequent extraction of the complex with N-octylacetamide into toluene or chloroform. The apparent molar absorptivity of the complex is 2.60 x 10(5) L mol(-1) cm(-1) at lambdamax = 480 nm at an enrichment factor (EF) of 10. The detection limit (causing higher absorbance than the sum of the blank absorbance (0.009) and 3 SD) is 5 ng mL(-1) Fe. Ions commonly associated with iron did not interfere in the present method. The effect of analytical variables, i.e. amount and type of the reagents, acidity, solvent, temperature, dilution, etc., in the determination of iron are discussed. The validity of the present method is checked with GF-AAS. The method has been applied to the determination of iron at the ppb level in rain water samples.     

A highly sensitive colour reaction for Se(IV) with the iodide-rhodamine B-PVA system Spectrophotometric determination of trace amounts of selenium in water

A highly sensitive spectrophotometric method for determination of selenium(IV) has been developed, based on Se(IV) oxidation of I(-) to I(-)(3) in a weak-acid medium, then formation of the 1:1 ion-association complex of I(-)(3) with Rhodamine B in the presence of poly(vinyl alcohol). The molar absorptivity is 1.97 x 10(5)l.mole(-1).cm(-1). Preconcentration of Se(IV) and elimination of interfering ions is achieved by an improved thiol cotton method, so the determination has very good selectivity. Se(IV) at mug/l. levels in tap water, hot-spring water and river water has been satisfactorily determined by the method.     

新显色剂2-(2-噻唑偶氮)-5-二乙氨基苯甲酸分光光度法测定微量钴

近年来,杂环偶氮苯甲酸类显色剂取得了较快的发展。由于氨基取代结构对试剂性能有较大的影响^[1],因此本文合成了新显色剂2-(2-噻唑偶氮)-5-二乙氨基苯甲酸,(TAEB)并研究了它与钴的显色反应。     

Spectrophotometric determination of iron with ferrozine by flow-injection analysis

Two methods for the determination of iron by normal FIA and reversed FIA were developed using sodium 3-(2-pyridyl)-5,6-diphenyl-1,2,4-triazine-4',4'-disulphonate (ferrozine). The reagent formed a chelate with Fe(II) in hexamethylentetramine buffered medium at pH 5.5. In one previous reaction coil Fe(III) was reduced to Fe(II) by ascorbic acid and in the other reaction coil the complexation reaction was developed. The linear range of the determination was 0.5-6 and 0.1-5 mug ml(-1) of iron for normal FIA and reversed FIA respectively. The proposed method was sensitive (detection limit 0.012 and 0.010 mug ml(-1)), rapid and reproducible (RSD 0.3 and 0.28%). The method was satisfactorily applied to the determination of iron in waste water, toadstool tissue, potato leaves, human hair and bauxites at a sampling rate of 90 and 50 samples h(-1) for normal FIA and reversed FIA respectively.     

Spectrophotometric determination of chloride in mineral and drinking waters using sequential injection analysis

An on-line sequential injection system has been developed for spectrophotometric determination of chloride in drinking mineral, natural, and ground waters. Samples containing different concentrations of chloride were analyzed. The analysis is based on detection of the red iron(III) thiocyanate complex. The complex was monitored spectrophotometrically at 480 nm using de-ionized water as the carrier stream at a flow rate of 3.21 mL min(-1). The method was found to be linear within the range 0-50 mg L(-1) chloride; the detection limit was 3.01 mg L(-1). The fully automated method can be used to analyze 37 samples per hour with a relative standard deviation (RSD) better than 2.50%.     

Spectrophotometry Determination of Iron(II) Separated by Means of Adsorption of Its 3-(2-Pyridyl)-5, 6-Diphenyl-1, 2, 4-Triazine Complex with Tetraphenyl-Borate on Microcrystalline Naphthalene

A procedure is describe for the adsorption of ion-associated complex of iron(II) 3-(2-pyridyl)-5, 6-diphenyl-1, 2, 4-triazine (abbreviated as PDT) cation with tetra phenylborate (TPB) anion on macrocrystalline naphthalene. A water-insoluble ion-associated complex formed with PDT and TPB is quantitatively adsorbed on micro-crystalline naphthalene. The solid mixture containing the colored complex is dissolved in acetonitrile and the absorbance was measured at 553 nm. The other factors such as pH, amounts of reagents and naphthalene, shaking and standing times, diverse ions are studied. The method has been applied for the determination of iron in alloys and water samples.     

Simultaneous spectrophotometric determination of nickel and iron in copper-base alloy with bromo-PADAP

The reaction of nickel (II) with Br-PADAP, in the presence of tergitol NPX surfactant, forms a complex with absorption peaks at 520 and 560 nm. The iron(II)-Br-PADAP system at the same conditions forms a chelate with absorption peaks at 560 and 748 nm. This allows the simultaneous spectrophotometric determination of nickel and iron by measuring the absorbance at 560 and 748 nm. The proposed method, at ph 4.0-5.7, shows a molar absorptivity of 1.22 x 10(5)l . mole(-1) . cm(-1) for nickel at 560 nm and 8.20 x 10(4)l . mole(-1) . cm(-1) at 560 nm and 3.35 x 10(4)l . mole(-1) . cm(-1) at 748 nm for iron(II). Beer's law is obeyed up to 0.40 mu/ml of nickel(II) and up to 0.65 mu/ml of iron(II). Thiosulphate as masking agent allows the simultaneous determination of iron and nickel in the presence of high concentrations of copper. The ethylene glycol 2-(2-amino-ethyl) tetracetic acid provides the elimination of many other interferences. The method has been applied successfully to the simultaneous determination of nickel and iron in reference samples.     

Solid-phase spectrophotometric microdetermination of iron with ascorbic acid and ferrozine

 A very sensitive and selective method for the determination of trace amounts of iron has been developed, based on the reduction of Fe(III) to Fe(II) by ascorbic acid, followed by chromogenic chelation of Fe(II) with ferrozine. The complex Fe(II)-ferrozine is easily sorbed on a dextran-type anion-exchange gel packed in a 1 mm cell, and the absorbance of the gel is measured directly at 569 and 800 nm. The extended linear range of the determination is 0.5–10 ng ml^-1 of iron (apparent molar absorptivity=4.4×10⁷ l mol^-1 cm^-1) and the precision (RSD) 1.3% for a concentration of 5 ng ml^-1 of iron (n=10). The detection limit for a sample volume of 1000 ml, using 0.040 g of anion-exchanger, corresponds to 0.12 ng ml^-1. The method has been successfully applied to the determination of iron in natural and waste waters, wine, soil extract and previously digested vegetal tissues, drugs and human hair. Received: 20 November 1995/Revised: 23 January 1996/Accepted: 26 January 1996