Determination of trace molybdenum in vegetable and food samples by spectrophotometry with p-carboxyphenylfluorone

A new highly sensitive and selective chromogenic reagent, p-carboxyphenylfluorone (p-CPF), was studied for spectrophotometric determination of trace molybdenum. In 0.36 mol L(-1)phosphoric acid medium, p-CPF reacts with molybdenum(VI) to form a 1:3 red complex, which has a sensitive absorption peak at 531 nm. Under optimal conditions, the reaction of molybdenum(VI) with p-CPF completed rapidly and absorbance remains almost constant for at least 24 h. Molybdenum(VI) obeyed Beer's law in the range 0-2.0 microg mL(-1); the apparent molar absorption coefficient, Sandell's sensitivity and the limit of detection were found to be 1.03 x 10(5) L mol(-1) cm(-1), 1.028 ng cm(-2)and 0.73 ng mL(-1) respectively; the effect of various foreign ions were examined in detail. It was found that most coexisting ions can be tolerated in considerable amounts, especially 800 mg of Mn(II), 200 mg of Mg(II), Fe(II), Co(III), Ni(II) and Cd(II), 50 mg of Ca(II) and Al(III), 25 mg of Cu(II) and Fe(III), 10 mg of Hg (II), La(III), Bi(III), Pb(II) and Zn(II) don't interfere with the determination of molybdenum(VI). The proposed method is very simple, sensitive and selective, it has been applied to determine molybdenum in vegetable and food samples with a very high precision and accuracy. Moreover, the synthesis of the reagent and the conditions of the colour reaction were also studied in detail.     

In-situ separation of chromium(III) and chromium(VI) and sequential ETV-ICP-AES determination using acetylacetone and PTFE as chemical modifiers

Electrothermal vaporization-inductively coupled plasma-atomic emission spectrometry (ETV-ICP-ES) has been used for the sequential determination of Cr(III) and Cr(VI). The method is based on the difference between the chelate reactions of the two Cr species and acetylacetone. Cr(III) chelate was separated from Cr(VI) and determined with use of acetylacetone as chemical modifier. The retained Cr(VI) in graphite tube was analyzed subsequently, after addition of polytetrafluoroethylene (PTFE) as chemical modifier. The different factors affecting the vaporization behavior of Cr(III) acetylacetonate were investigated in detail. The detection limits for Cr (III) and Cr(VI) were 0.56 and 1.4 ng mL(-1), respectively, and relative standard deviations for 0.1 microg mL(-1) Cr(III) and 0.1 microg mL(-1) Cr(VI) were 2.5% (n = 6) and 4.8% (n = 6), respectively. The linear ranges of the calibration curve for both Cr(IIl) and Cr(VI) covered three orders of magnitude. The proposed method was used to analyze water samples with satisfactory results.     

6-Chloro-3-hydroxy-2-(5'-methylfuryl)-4H-chromene-4-one as an analytical reagent for micro determination of molybdenum(VI).

6-Chloro-3-hydroxy-2-(5'-methylfuryl)-4H-chromene-4-one (CHMFC) has been used as an analytical reagent for the spectrophotometric determination of molybdenum. Molybdenum(VI) in the presence of several cations, anions and complexing agents forms a yellow 1:2 complex with CHMFC. The complex is quantitatively extractable into 1,2-dichloroethane from 1 mol dm(-3) acetic acid medium and is stable for more than 6 h. The complex shows an absorption maximum at 438 nm with a molar absorptivity of 5.36 x 10(4) dm3 mol(-1) cm(-1) and Sandell's sensitivity equal to 0.0017 microg Mo cm(-2). The method obeys Beer's law up to 1.9 microg Mo ml(-1). The relative standard deviations are 0.2% for solutions and 0.5-1.5% for solid samples. The method is simple, selective, precise and rapid, and has been satisfactorily applied to the micro determination of molybdenum in various synthetic and standard samples.     

A simple spectrophotometric method for the determination of copper in industrial, environmental, biological and soil samples using 2,5-dimercapto-1,3,4-thiadiazole.

A simple spectrophotometric method is presented for the rapid determination of copper at a trace level using 2,5-dimercapto-1,3,4-thiadiazole (DMTD) as a new spectrophotometric reagent. The method is based on the reaction of non-absorbent DMTD in a slightly acidic (0.002-0.014 mol dm(-3) sulfuric acid) aqueous solution with copper(II) to produce a highly absorbent greenish-yellow chelate product that has an absorption maximum at 390 nm. The reaction is instantaneous and the absorbance remains stable for 24 h. The average molar absorption coefficient and Sandell's sensitivity were found to be 5.65 x 10(4) dm3 mol(-1) cm(-1) and 10 ng cm(-2) of CuII, respectively. Linear calibration graphs were obtained for 0.1-20 microg cm(-3) of CuII; the stoichiometric composition of the chelate is 1:2 (Cu:DMTD). A large excess of over 50 cations, anions and complexing agents (e.g. tartrate, oxalate, citrate, phosphate, thiourea, SCN-) do not interfere in the determination. The method was successfully used for the determination of copper in several Standard Reference Materials as well as in some environmental water samples, biological samples, soil samples and solutions containing both copper(I) and copper(II) and complex synthetic mixtures. The method has high precision and accuracy (s = +/-0.01 for 0.5 microg cm(-1)).     

The spectrophotometric determination of trace molybdenum (VI) after collection and elution as molybdate ion on protonated chitin

Collection and elution method for inorganic anion on protonated chitin has been applied to the spectrophotometric determination of molybdenum (VI). The molybdenum (VI) is collected as molybdate ion on a column of chitin in weak acidic medium which is easily eluted with a small volume of 0.1 M ammonia buffer solution (pH 10). The molybdenum (VI) in the eluent is determined by bromopyrogallol red-Zephiramine method spectrophotometrically. Beer's law is obeyed over the concentration range of 0.1-0.8 mug of molybdenum (VI) in 1 ml of eluent at 634 nm. The apparent molar absorptivity is 6x10(4) dm(3) mol(-1) cm(-1). The tolerance limits for WO(4)(2-), VO(3)(-), CrO(4)(2-) and Fe (III) is low, that is, 1-100 times that of molybdenum (VI), but some metal ions and common inorganic anions do not interfere in concentration range of 1000-5000 times that of molybdenum (VI). The present method can be applied to the determination of molybdenum (VI) in natural water samples.     

Square wave adsorptive stripping voltammetry of molybdenum(VI) in continuous flow at a wall-jet mercury film electrode sensor

An adsorptive stripping voltammetry method for the determination of traces of molybdenum(VI) in flowing solution at a wall-jet electrode sensor has been developed. After adsorption of a molybdenum complex on a wall-jet mercury film electrode, the complex is reduced by a square wave scan. More satisfactory results were obtained using 8-hydroxyquinoline as a complexing agent in nitrate medium than using Toluidine Blue in oxalic acid. Enhanced sensitivity was achieved by optimizing adsorption time and square wave parameter values. The detection limit of Mo(VI) was found to be at the nanomolar level. Interference of some other metallic species in the determination of nanomolar Mo(VI) was also investigated: Cu(II), Zn(II), Mn(II) do not interfere at 10 muM, whereas 1 muM FeEDTA(-) causes an increase in peak current. This iron interference was removed effectively with citric acid.     

Novel spectrophotometric method for the determination of molybdenum in a PVA medium.

A novel spectrophotometric method for the determination of trace molybdenum in the presence of a large amount of tungsten was developed. This proposed method was based on the formation of a green charge-transfer polyoxometalate, molybdo-11-tungstophosphate-3,3',5,5'-tetramethylbenzidine-N-propanesulfonic, which was solubilized and stabilized in a PVA medium; the wavelength of the maximum absorption was at 660 nm. Beer's law was obeyed in the Mo concentration range of 0.04-1.6 microg ml(-1). The molar absorptivity was 1.35 x 10(4) l mol(-1) cm(-1). The developed method avoided the interference of W(VI), and was conveniently applied to analyses of some tungsten ores containing Mo(VI) with satisfactory results.     

Spectrophotometric determination of trace molybdenum in plants and seeds with 3,5-dibromo-4-hydroxyphenylflurone

A novel spectrophotometric method based on a new reagent, 3,5-dibromo-4-hydroxyphenylflurone, was developed for the determination of molybdenum in plants and seeds. 3,5-Dibromo-4-hydroxyphenylflurone showed outstanding analytical characteristics for spectrophotometric determination of molybdenum. The reaction conditions are simple and stable. In 0.2 mol l(-1) phosphoric acid medium (which can combine with iron and other metal ions and greatly improves the selectivity of the color system), molybdenum(VI) reacts with 3,5-dibromo-4-hydroxyphenylflurone to form a 1:2 red complex with an absorption maximum at 530 nm, the color reaction can completed in 2 min and the absorbance of the molybdenum complex remains stable for at least 72 h at room temperature. Its stability constant is 1.21 x 10(28) at 25 degrees C. Beer's law is obeyed over the range 0-0.6 microg ml(-1) Mo(VI). The reagent has very high sensitivity and selectivity; the molar absorptivity of the complex is 1.35 x 10(5) 1 mol(-1) cm(-1) and the limit of quantification, the limit of detection and relative standard deviation (n = 10) were found to be 6.7 ng ml(-1), 2.2 ng ml(-1) and 1.01%, respectively. Cu (50000-fold), Fe (20000-fold), K (20000-fold), NH4+ (20000-fold), Mg (15000-fold), Zn (10000-fold), Na (10000-fold), Al (4000-fold), Ca (25000-fold), Mn (2000-fold), Ce (500-fold), Cr (400-fold) and Bi (200-fold) do not interfere with the determination of trace levels of molybdenum up to the excesses indicated. The selectivity is much superior to that of other published methods. The proposed method was applied to the direct determination of molybdenum in plants and seeds with satisfactory results. The synthesis of the reagent and conditions of color reaction were studied in detail.     

Rapid spectrophotometric determination of chromium(III)

A spectrophotometric procedure is suggested for the determination of Cr(III). The reaction between Cr(III) and 2-(5-bromo-2-pyridylazo)-5-dimethylaminophenol is accelerated by sodium dodecyl sulphate(SDS), sodium benzoate causes a further increase in the absorbance of the chelate. The optimum pH range for the reaction is 5-5.8(benzoate buffer). The chelate exhibits maximum absorbance at 590 nm, obeys Beer's law over the concentration range 0.02-0.56 microg/ml of Cr(III), has molar absorptivity of 7.8 x 10(4) 1. mol(-1) cm(-1) and a Sandell sensitivity of 0.66 ng/cm. The metal to ligand ratio is 1:2 in the absence of SDS and 1:1 in its presence. A procedure for the determination of Cr(III) and Cr(VI), when present together, is described. The method has been applied to the analysis of Cr(III) in tap water.     

Spectrophotometric determination of lead in industrial, environmental, biological and soil samples using 2,5-dimercapto-1,3,4-thiadiazole

A very simple, ultra-sensitive and fairly selective non-extractive spectrophotometric method for the determination of trace amounts of lead with 2,5-dimercapto-1,3,4-thiadiazole (DMTD) has been developed. DMTD reacts in slightly acidic (0.0015-0.01 M HCl) aquatic media with lead(II) to give a greenish-yellow chelate, which has an absorption maximum at 375 nm. The reaction is instantaneous and absorbance remains stable for 24 h. The average molar absorption coefficient and Sandell's sensitivity were found to be 4.93x10(4) lmol(-1)cm(-1) and 15 ngcm(-2) of Pb, respectively. Linear calibration graphs were obtained for 0.1-40 mugml(-1) of Pb; the stoichiometric composition of the chelate is 1:2 (Pb-DMTD). The interference from over 50 cations, anions and complexing agents has been studied at 1 mugml(-1) of Pb. The method developed was used successfully in the determination of lead in several standard reference materials (alloys and steels), environmental waters (potable and polluted), biological samples (human blood and urine), soil samples, solutions containing both lead(II) and lead(IV) and complex synthetic mixtures. The method has high precision and accuracy (S=+/-0.01 for 0.5 mugml(-1)).     

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.     

Utility of 5-Diazo-1,2,4- Triazol-3-Carboxylic Acid for Colorimetric Determination of Certain 8-Hydroxyquinolines

Abstract

A colorimetric method for the determination of certain 8-hydroxyquinolines has been developed. The method is based on the coupling of 8-quinolinols with diazotriazole carboxylic acid in the presence of sodium carbonate (0.5% w/v) at ambient temperature (around 30°C). The resulting azo dyes are stable and give intense absorption in the range of 486–540 nm. Beer's law is valid in the concentration ranges of 1 – 8, 2.5 – 17.5, 5 – 35, 2 – 20, and 2 – 20 mcg/ml for 8-hydroxyquinoline (HQ), 5,7-diiodo-8-hydroxyquinoline (DIQ), 5,7-dibromo-8-hydroxyquinoline (DBQ), 5-chloro-7-iodo-8-hydroxyquinoline (CIQ) and 8-hydroxy-7-iodo-5-quinoline sulfonic acid (SIQ), respectively. The proposed method has been successfully applied for the determination of the studied compounds in pure form and in commercial formulations. The obtained results are in good agreement with those obtained from reported methods.     

Determination of trace cadmium in waters by flame atomic absorption spectrophotometry after preconcentration with 1-nitroso-2-naphthol-3,6-disulfonic acid on Ambersorb 572

A procedure for the determination of trace amount of cadmium after adsorption of its 1-nitroso-2-naphthol-3,6-disulfonic acid chelate on Ambersorb 572 has been proposed. This chelate is adsorbed on the adsorbent in the pH range 3-8 from large volumes of aqueous solution of water samples with a preconcentration factor of 200. After being sorbed, cadmium was eluted by 5 mL of 2.0 mol L(-1) nitric acid solution and determined directly by flame atomic absorption spectrophotometery (FAAS). The detection limit (3sigma) of cadmium was 0.32 microg L(-1). The precision of the proposed procedure, calculated as the relative standard deviation of recovery in sample solution (100 mL) containing 5 microg of cadmium was satisfactory (1.9%). The adsorption of cadmium onto adsorbent can formally be described by a Langmuir equation with a maximum adsorption capacity of 19.6 mg g(-1) and a binding constant of 6.5 x 10(-3) L mg(-1). Various parameters, such as the effect of pH and the interference of a number of metal ions on the determination of cadmium, have been studied in detail to optimize the conditions for the preconcentration and determination of cadmium in water samples. This procedure was applied to the determination of cadmium in tap and river water samples.     

Flow injection atomic absorption spectrometric determination of iodide using an on-line preconcentration technique

A continuous flow atomic absorption spectrometric system was used to develop an efficient on-line preconcentration-elution procedure for the determination of iodide traces. Chromium (VI) is introduced into the flow system and is reduced to chromium (III) in acid medium proportionally to the iodide present in the sample. The Cr(III) reduced by iodide is retained on a minicolumn packed with a poly(aminophosphonic acid) chelating resin, while unreduced Cr(VI) is not retained. Reduced Cr(III) is preconcentrated by passing the sample containing iodide through the system during 3 min, and is then eluted with 0.5 mol L(-1) hydrochloric acid and determined by flame atomic absorption spectrometry (FAAS). The detection limit (3sigma) obtained is 2.5 microg L(-1). Other ions typically present in waters do not interfere. The proposed method allows the determination of iodide in the range 6-220 microg L(-1) with a relative standard deviation of 2.7% at a rate of 17 samples h(-1). The method has been applied to the determination of iodide in tap and sea waters.     

Spectrophotometric determination of zirconium with 5,7-dibromo-8-hydroxyquinoline in presence of thiocyanate

The characteristics of the ternary complex formed between zirconium(IV) and 5,7-dibromo-8-hydroxyquinoline in presence of thiocyanate have been studied with an analytical point of view. The resulting colored species is extractable into chloroform with absorption maximum at 416 nm, which leads to the determination of the trace amounts of the metal ion. The method obeys Beer’s law in the range 0.2–9.0 μg Zr/mL having molar absorbitivity and Sandell’s sensitivity values of 1.05 × 10⁴ L/mol cm and 0.0087 μg Zr/cm², respectively. The ratio of zirconium(IV), 5,7-dibromo-8-hydroxyquinoline and thiocyanate in the extracted species is found to be 1: 2: 2. A large number of foreign ions do not interfere in the proposed method. The applicability of the procedure is tested by carrying out satisfactorily the analysis of a wide variety of 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.     

Studies and application of catalytic kinetic spectrophotometric determination of trace chromium(VI) sensitized by microemulsion medium

A new catalytic kinetic spectrophotometric method for the determination of trace amount of chromium (VI) in microemulsion medium has been developed. The method is based on the catalytic effect of chromium (VI) on the oxidation of nuclear fast red in the presence of Tween-80 microemulsion and HAc-NaAc buffer solution (pH = 5.2). The linear ranges are in the range of 0 approximately 0.0480 microg mL(-1) of Cr (VI) at 528 nm and the detection limit is 1.56x10(-9)g mL(-1). The method has been applied in determination of Cr (VI) in water and food samples with satisfactory results. The relative standard deviation is less than 4.6 % and the recovery is 93.5 approximately 104 %.     

Separation and preconcentration of chromium species by selective absorption on Lemna minor and determination by slurry atomisation electrothermal atomic absorption spectrometry

A novel method for the separation and preconcentration of Cr(III)/Cr(VI) with Lemna minor and determination by slurry atomization electrothermal atomic absorption spectrometry (ETAAS) was developed. A sample solution was added to a polyethylene beaker containing 10 mg of 160 mesh pre-treated Lemna minor, adjusted to pH 1.0, stirred for 8 min for selective absorption of Cr(III) and then centrifuged. The upper layer of solution was transferred into another polyethylene beaker containing 10 mg of 160 mesh pre-treated Lemna minor, adjusted to pH 5.0, stirred for 12 min for adsorption of the residual Cr(VI) and centrifuged. The two residues in two centrifuge tubes were washed twice with water, 2 ml of agar solution added, stirred for 2 min, then two slurries were prepared and used for the determination of Cr(III) and Cr(VI) by ETAAS. Detection limits (3sigma) of 0.01 microg L(-1) for Cr(III) and 0.03 microg L(-1) for Cr(VI) were obtained. The relative standard deviation was 2.8% for Cr(III) and 3.3% for Cr(VI) at the 1 microg L(-1) level. The method was applied to the determination of Cr(III)/Cr(VI) in water samples. The analytical recoveries of Cr(III) and Cr(VI) added to samples were 97-102 and 96-103%, respectively.     

Simultaneous determination of titanium and molybdenum in steel samples using derivative spectrophotometry in neutral micellar medium

A simple, selective and sensitive spectrophotometric method has been developed for the individual and simultaneous determination of Ti(IV) and Mo(VI) using resacetophenone p-hydroxybenzoylhydrazone (RAPHBH) in presence of Triton X-100, without any prior separation. Beer's law is obeyed between 0.13-1.2 microg mL-1 and 0.18-1.90 microg mL-1 concentration of Ti(IV) and Mo(VI) at 455 nm and 405 nm, respectively. The molar absorptivity and Sandell's sensitivity of the coloured complexes at pH 3.0 are 3.1x10(4) L mol-1 cm-1, 4.2x10(4) L mol-1 cm-1, and 1.6 ng cm-2, 2.3 ng cm-2 for Ti(IV) and Mo(VI), respectively. The stoichiometry of the complexes were found to be 1:2 and 1:1 (metal:ligand) for Ti(IV) and Mo(VI), respectively. These metal ions interfere with the determination of each other in zero-order spectrophotometry. The first derivative spectra of these complexes permitted a simultaneous determination of Ti(IV) and Mo(VI) at zero crossing wavelengths of 500.0 nm and 455.0 nm, respectively. The effect of foreign ions in the determination of Ti(IV) and Mo(VI) were investigated. The proposed method has been successfully applied for the determination of titanium and molybdenum in standard alloy steel, mineral and soil samples.     

Preparation of fluorescent polyvinyl alcohol keto-derivatives nanoparticles and selective determination of chromium(VI)

A novel fluorescent polyvinyl alcohol keto-derivatives nanoparticle (PVAK) has been prepared in one-step method. The nanoparticles has excitation and emission maxima at 349 and 462 nm, respectively. Based on the fluorescence quenching of PVAK by Cr(VI), we established a simple and selective fluorimetric method for the determination of Cr(VI) without separation of Cr(III) in water. The reaction conditions between Cr(VI) and PVAK were investigated in detail. Furthermore, the reaction mechanism between PVAK and Cr(VI) was also discussed. Under optimal experimental conditions, a limit of detection of 0.02 microg mL(-1) was achieved. The calibration curve was linear over the concentration range 0.1-13.2 microg mL(-1) with a correlation coefficient of 0.9987. The proposed method has been applied to the selective quantification of Cr(VI) in synthetic samples and waste-water samples with the satisfactory results.