Catalytic flow injection determination of vanadium by oxidation of N-(3-sulfopropyl)-3,3',5,5'-tetramethylbenzidine using bromate

A catalytic flow-injection (FI) method was developed for the determination of 10⁻⁹ mol l⁻¹ levels of vanadium(IV, V). The method is based on the catalytic effect of vanadium(V) on oxidation of N-(3-sulfopropyl)-3,3′,5,5′-tetramethylbenzidine (TMBZ·PS) using bromate as oxidant to form a yellow dye (λ_max=460 nm). The use of 5-sulfosalicylic acid (SSA) as an activator enhanced the sensitivity of the method. The calibration graphs with a working range 0.05–8.0 ng ml⁻¹ were obtained for vanadium(V). Vanadium(IV) was also determined, being oxidized by bromate. The detection limit (signal/noise, S/N=3) was 0.01 ng ml⁻¹ (ca. 2×10⁻¹⁰ mol l⁻¹) vanadium. The relative standard deviations (R.S.D.) for 15 determinations of 0.5 ng ml⁻¹ vanadium, and for ten determinations of 0.1 and 1.0 ng ml⁻¹ vanadium were 0.41, 2.6 and 0.25%, respectively, with a sampling rate of 15 samples h⁻¹. The proposed method was successfully applied to the determination of vanadium in natural waters.     

溴酸钾氧化酸性铬深蓝催化动力学极谱法测定痕量钒

在0.15mol·L~(-1)H_2SO_4介质中,以酒石酸作活化剂,Ⅴ(Ⅴ)对溴酸钾氧化酸性铬深蓝的反应具有强烈的催化作用,以极谱法监测催化反应过程中酸性铬深蓝浓度的变化,建立了测定痕量钒的催化动力学新方法。钒的线性范围为0.10～7.0ng·ml~(-1),检出限为0.05ng·ml~(-1),应用于人发中痕量钒的测定,结果满意。并对酸性铬深蓝的极谱特性进行了初步的探讨。     

Flow-injection spectrophotometric determination of trace vanadium based on catalysis of the gallic acid bromate reaction

High sensitivity is obtained by using high concentrations of gallic acid and bromate, although the uncatalyzed reaction is significant. Various reactant concentrations, reaction temperature, pH and residence times can be used to alter the linear calibration ranges and sensitivity for vanadium. With reagent streams of 1.76 M bromate and 0.06 M gallic acid at pH 3.8 (each at 1 ml min^?1), 0.2–20 ng of vanadium (20-μl injections) can be determined at 30°C. Oxidized gallic acid is detected at 380 nm. When the bromate concentration is decreased to 0.5 M and the temperature is 65°C, 0.05–4 ng of vanadium can be determined; the relative standard deviation is ca. 5% for 0.6 ng of vanadium. The toleranes for Al(III), Fe(III), Mo(VI) and iodide are 10 ng, 10 ng, 50 ng and 200 ng, respectively, for the determination of 1 ng of vanadium. About 12 samples can be injected per hour.     

Kinetic-catalytic determination of vanadium(IV) using methyl orange-bromate redox reaction.

Determination of V(IV) based on its catalytic effect on the reaction between Methyl Orange and bromate in thepresence of citric acid was studied. The calibration curve obtained by fixed-time method was linear in the range of 2.5-300 ng ml(-1). By use of slope method, a calibration curve containing two linear portions were obtained. Using fixed-time and slope methods, we obtained detection limits of 0.8 and 1.5 ng ml(-1), respectively. Fe2+, As(III), V(V) and Hg2+ interfered. The method was successful for analysis of water samples.     

Flow-injection spectrophotometry of vanadium by catalysis of the bromate oxidation of N,N'-bis(2-hydroxyl-3-sulfopropyl)-tolidine

A highly sensitive flow-injection method is proposed for the catalytic determination of vanadium(V) at sub-nanogram per milliliter levels using a new indicator reaction. The method is based on the catalytic effect of vanadium(V) on the bromate oxidation of N,N′-bis(2-hydroxyl-3-sulfopropyl)-tolidine. 1,2-Dihydroxybenzene-3,5-disulfonate was used as an activator in the vanadium(V)-catalyzed reaction and significantly enhanced the sensitivity of the method. Vanadium(V) in the range 0.01-3.0 ng ml⁻¹ was easily determined with sampling rate of about 30 h⁻¹. Vanadium(IV) could be also determined. The limit of detection (S/N=3) was 0.008 ng ml⁻¹ and the relative standard deviations were 1.4 and 1.6% for ten determinations of 0.2 ng ml⁻¹ vanadium(IV) and vanadium(V), respectively. Interferences from metal ions could be suppressed by the addition of ethylenediamine-N,N,N′,N′-tetrakis(methylenephosphonic acid) as a masking agent. The proposed method was successfully applied to the determination of vanadium in water samples.     

Catalytic determination of ultra trace amounts of vanadium with detection by linear sweep voltammetry

Vanadium has a very strong catalytic effect on the bromate oxidation of gallocyanine at pH of 4.0. The oxidation product of gallocyanine exhibit a voltammetric wave at + 0.10 V vs. Ag/AgCl reference electrode in 0.10 mol/l KNO₃ medium. The linear scan voltammetric behaviour of the reaction products at HMDE has been studied and selected as the indicator component for the reaction. A detection limit of 0.05 ng/ml and calibration graph from 0.30–200.00 ng/ml vanadium were obtained. Vanadium in water and gasoline samples was determined by this method, with satisfactory results.     

溴酸钾-二甲酚橙体系-顺序注射-催化光度法测定痕量钒

在酸性介质条件下,钒(Ⅳ)能显著催化溴酸钾对二甲酚橙的氧化褪色反应。据此建立了测定痕量钒(Ⅳ)的顺序注射催化光度法。方法的线性范围为0.5~50ng/mL、检出限为0.4ng/mL。对10ng/mL的钒(Ⅳ)连续11次测定的相对标准偏差为1.1%。用于环境水样中痕量钒(Ⅳ)的测定,加标回收率为91%~108%。     

溴酸钾二甲酚橙体系-顺序注射-催化光度法测定痕量钒

在酸性介质条件下,钒(Ⅳ)能显著催化溴酸钾对二甲酚橙的氧化褪色反应。据此建立了测定痕量钒(Ⅳ)的顺序注射催化光度法。方法的线性范围为0.5⁵0ng/mL、检出限为0.4ng/mL。对10ng/mL的钒(Ⅳ)连续11次测定的相对标准偏差为1.1%。用于环境水样中痕量钒(Ⅳ)的测定,加标回收率为91%50ng/mL、检出限为0.4ng/mL。对10ng/mL的钒(Ⅳ)连续11次测定的相对标准偏差为1.1%。用于环境水样中痕量钒(Ⅳ)的测定,加标回收率为91%¹08%。     

Highly sensitive spectrophotometric kinetic determination of vanadium by catalysis of the gallic acid-bromate reaction

Conditions are described for improving the speed and sensitivity of this catalytic determination of vanadium. The reaction of 0.018 M gallic acid with 0.96 M sodium bromate at pH 3.8 and double-beam spectrophotometric measurement at 380 nm are recommended. The calibration curves are obtained by the tangent (2-point) and fixed-time (single-point) method. The highest practical sensitivity at 22–30°C was ca. 40 pg for an absorbance change of 0.0005, 50 times better than previously. The detection limit was ca. 0.5 ng of vanadium. Reaction at 50°C gave even better sensitivity.     

Catalytic Determination of Vanadium Based on the Bromate Oxidative-C oupling Reaction of Metol with Phloroglucinol

 A selective, sensitive and simple catalytic method is developed for the determination of vanadium in natural and highly polluted waste waters. The method is based on the catalytic effect of V^V and/or V^IV on the bromate oxidative-coupling reaction of metol with phloroglucinol (PG). The reaction is followed spectrophotometrically by tracing the oxidation product at 464 nm after 10 minutes of mixing the reagents. The optimum reaction conditions are metol (8.0×10⁻³ M), PG (4.0×10⁻³ M) and bromate (2×10⁻² M) at 35°C and in presence of an activator-b uffer mixture of 5×10⁻² M of each of citric and monochloroacetic acids (pH 2.40). Following the recommended procedure, vanadium can be determined with a linear calibration graph up to 8.0 ng mL⁻¹ and a detection limit, based on the 3s_b criterion, of 0.1 ng mL⁻¹. Spectrophotometric determination of as little as 1.0 ng mL⁻¹ of V^V or V^IV in aqueous solutions gave an average recovery of 98% with relative standard deviations of ?1.8% (n = 5). The proposed method was directly applied to the determination of vanadium in Nile river water and highly polluted industrial wastes. Statistical treatments of analytical results could not detect any systematic error and showed the high accuracy and precision of the developed method. Received November 25, 1999. Revision March 10, 2000.     

Trace analysis of vanadium as pentavalent vanadium using differential pulse polarography with a coupled catalytic homogeneous reaction

The differential pulse polarographic determination of the vanadium (V) ion coupled with a catalytic homogeneous reaction was carried out in a system containing the vanadium (V)-PAR complex and an oxidant in acetic/acetate buffer. On addition of the powerful oxidant, sodium bromate, the peak current for the reduction of the vanadium (V) complex was increased significantly by about 21 times. A calibration plot was found to be linear in the concentration range 0.05–0.25 g/ml and the detection limit was 5 ng/ml.     

Kinetic spectrophotometric determination of trace amounts of selenium and vanadium

A sensitive kinetic spectrophotometric method has been developed for the determination of Se(IV) over the range of 45 to 4000 ng in 10 mL of solution. The method is based on the catalytic effect of Se(IV) on the reduction reaction of bromate by hydrazinium dichloride, with subsequent reaction of Ponceau S with products of the above reaction (chlorine and bromine), causing color changing of Ponceau S. Method development includes optimization of time interval for measurement of slope, pH, reagents concentration, and temperature. The optimized conditions yielded a theoretical detection limit of 33 ng/¶10 mL of solution of Se(IV). The interfering effects were studied and removed. The method was applied to the determination of selenium in spiked water, Kjeldahl tablet, selenium tablet, and shampoo. Vanadium(V) has an inhibition effect on the catalyzed reaction of bromate and hydrazine by selenium. Using this effect, V(V) can be determined in the range of 70 to 2500 ng in 10 mL of solution. The optimization procedure includes pH and selenium concentration. An extraction method was used for interference removal. The method was applied to the determination of vanadium in petroleum.     

Catalytic determination of ultra trace amounts of vanadium with detection by linear sweep voltammetry

Vanadium has a very strong catalytic effect on the bromate oxidation of gallocyanine at pH of 4.0. The oxidation product of gallocyanine exhibit a voltammetric wave at + 0.10 V vs. Ag/AgCl reference electrode in 0.10 mol/l KNO₃ medium. The linear scan voltammetric behaviour of the reaction products at HMDE has been studied and selected as the indicator component for the reaction. A detection limit of 0.05 ng/ml and calibration graph from 0.30–200.00 ng/ml vanadium were obtained. Vanadium in water and gasoline samples was determined by this method, with satisfactory results. Received: 26 September 1996 / Revised: 6 November 1996 / Accepted: 15 November 1996     

Kinetic spectrophotometric determination of trace amounts of selenium and vanadium

A sensitive kinetic spectrophotometric method has been developed for the determination of Se(IV) over the range of 45 to 4000 ng in 10 mL of solution. The method is based on the catalytic effect of Se(IV) on the reduction reaction of bromate by hydrazinium dichloride, with subsequent reaction of Ponceau S with products of the above reaction (chlorine and bromine), causing color changing of Ponceau S. Method development includes optimization of time interval for measurement of slope, pH, reagents concentration, and temperature. The optimized conditions yielded a theoretical detection limit of 33 ng/?10 mL of solution of Se(IV). The interfering effects were studied and removed. The method was applied to the determination of selenium in spiked water, Kjeldahl tablet, selenium tablet, and shampoo. Vanadium(V) has an inhibition effect on the catalyzed reaction of bromate and hydrazine by selenium. Using this effect, V(V) can be determined in the range of 70 to 2500 ng in 10 mL of solution. The optimization procedure includes pH and selenium concentration. An extraction method was used for interference removal. The method was applied to the determination of vanadium in petroleum. Received: 20 October 1998 / Revised: 17 April 1999 / Accepted: 3 June 1999     

邻氨基酚萃取催化光度法测定痕量钒及其催化反应机理

研究了在ｐＨ３．５的弱酸性介质中，痕量钒（Ｖ）能催化溴酸钾氧化邻氨基酚的指示反应，用萃取平衡控制反应时间和水相中邻氨基酚的浓度及反应程度，通过测量４２４ｎｍ下有机相的吸光度，建立了萃取催化光度法测定钒的新方法，方法的线性范围为０．００１０～０．３０ｍｇ／Ｌ检出限为１．０×１０＾－６ｇ／Ｌ用于人发，煤和岩石中痕量钒的测定，结果满意，此外，还探讨了反应机理，建立了动力方程。     

Kinetic-spectrophotometric determination of trace amounts of vanadium

A simple and sensitive kinetic-spectrophotometric method is described for the determination of vanadium and the possible mechanism of catalytic reaction is proposed. The method is based on the vanadium(V)-catalyzed oxidation of 1,8-diaminonaphthalene (DNA) by potassium bromate (Tiron as activator) at pH 3.8 and 40 degrees C. The reaction was monitored spectrophotometrically by measuring the increase in absorbance of oxidation products at 505 nm after a fixed time (6 min). The proposed method allowed the determination of vanadium in the range 0.025-15 ng ml(-1) with good precision and accuracy and the detection limit was down to 0.01 ng ml(-1). The method was found to be relatively selective and was applied successfully to the determination of vanadium in food and hair samples without previous separations. Recovery experiments have also been performed; excellent results were obtained.     

Determination of Trace Amounts of Vanadium by Kinetic-Catalytic Spectrophotometric Methods

Kinetic-catalytic spectrophotometric methods were proposed for the determination of trace amounts of vanadium element as vanadium（Ⅳ） and/or V（Ⅴ） ions. The vanadium（Ⅳ） as VO^2＋ ion and/or vanadium（Ⅴ） as VO3^- ion showed a catalytic effect on the kinetic reactions between a color reagent such as methylthymol blue （MTB） or SPADNS and bromate in acidic media. The rate of decrease in the absorbance of the reagent MTB at 440 nm or SPADNS at 510 nm was proportional to concentration of V（Ⅳ） and/or V（Ⅴ） ions in the solution. The linear ranges for determination of vanadium were obtained in the range of 1.0-150 and 5.0-100.0 μg/L by the fixed-time and slope methods, respectively, with using MTB as reagent. In the presence of SPADNS as reagent, the calibration curves were made in the amplitude 1.0-200.0 and 5.0-150 μg/L of vanadium ion by the fixed-time and slope methods, respectively. Using fixed-time method, the limits of detection were obtained to be 0.5 and 0.7 μg/L of vanadium in the presence of MTB and SPADNS as reagents, respectively. Detection limits of vanadium by slope method and reagents of SPADNS and MTB were obtained to be 3.5 and 3.8 μg/L of vanadium, respectively. The proposed methods were applied successfully to determination of vanadium in synthetic and real samples.     

An adsorption-catalytic test method for determining vanadium

The promoting effect of vanadium(V, IV) in the reaction of gallic acid oxidation with bromate ions in aqueous solutions was studied, and the dependence of the rates of catalytic and noncatalytic reactions on the concentration of components was found. A catalytic mechanism was proposed based on the experimental results and data of quantum-mechanical calculations. The linear dependence of the rate of the catalytic reaction on the concentration of vanadium(V)/vanadium(IV) was used to determine these ions in solutions by catalytic photometry. The detection limit was 0.01 μg in an aliquot portion of the test solution; the determination error was less than 20%. The conditions were found for stabilizing the properties of paper supports for more than 30 days, since the interaction of filter and chromatographic papers with bromate ions was found. An adsorption- catalytic test method was proposed for the semiquantitative visual determination of vanadium ions in water and aqueous solutions by the color of the pretreated paper strip immersed in the test solution. The detection limit for vanadium ions was 0.1 mg/L. The 100-fold amounts of Ni(II), Mn(II), Cr(III), and Co(II) do not interfere with the determination. The method was tested on river and sea water samples from different sources.     

Separation via flotation, spectrophotometric speciation, and determination of vanadium(IV) in wastes of power stations.

1-(2-Hydroxy-4-methoxybenzophenone)-4-phenylthiosemicarbazone (HMBPT) was investigated as a new reagent for the flotation of vanadium(IV). At pH approximately 1.5, vanadium(IV) forms a 1:1 pale-violet complex with HMBPT in aqueous solution. An intense clear violet layer was formed after flotation, by adding an oleic acid (HOL) surfactant. The composition of the float was 1:1 [V(IV)]:[HMBPT]. A highly selective and sensitive spectrophotometric procedure was proposed for the determination of microamounts of V(IV) as its floated complex. The molar absorptivities of the V(IV)-HMBPT and V(IV)-HMBPT-HOL systems were 0.4 x 10(4) and 0.12 x 10(5) L mol(-1) cm(-1) at 560 nm, respectively. The formation constants of the species formed in the presence and absence of HOL were 4.6 x 10(7) and 8.7 x 10(5) L mol(-1), respectively. Beer's law was obeyed up to 1 x 10(-4) mol L(-1) in the aqueous layer as well as in the oleic acid layer. The HMBPT-V(IV) complexes formed in the aqueous solution and scum layer were characterized by elemental analysis, infrared and UV spectrophotometric studies. The mode of chelation between V(IV) and HMBPT is proposed to be due to a reaction between the protonated bidentate HMBPT ligand and V(IV) through the S=C and N=C groups. Interferences from various foreign ions were avoided by adding excess HMBPT and/or Na2S2O3 as a masking agent. The proposed flotation method was successfully applied to the analysis of V(IV) in synthetic mixtures, wastes of power stations, simulated samples and in real ores. The separation mechanism is discussed.     

催化动力学极谱法测定痕量钒

在硫酸介质中,以酒石酸为活化剂,痕量钒对溴酸钾氧化甲基橙的反应有极强的催化作用,以极谱法监测催化反应过程中甲基橙及其氧化产物浓度的变化,建立了双峰指示催化动力学极谱法制定痕量钒的新方法,方法的线性范围为0.23-3.70μg/L,检出限为0.17μg/L。方法已用于食品及水样中痕量钒的测定。