Adsorption voltammetry of the vanadium-2-(5′-bromo-2′-pyridylazo)-5-diethylaminophenol (5-Br-PADAP) system

The behaviour of the vanadium(V) complex with 5-Br-PADAP at a mercury electrode was investigated in HOAcNaOAc. The adsorption phenomena were observed by linear-sweep voltammetry. The mechanism of the electrode reaction was found to be the irreversible reduction of the V(V) in the complex adsorbed on the surface of the electrode to the V(IV) complex with 5-Br-PADAP. In 0.02 mol l^?1 HOAc-0.012 mol l^?1 NaOAc (pH 4.5) and 1 × 10^?6 mol l^?1 5-Br-PADAP, the detection limits of linear-sweep adsorption voltammetry and 1.5th-order derivative adsorption voltammetry are 5 × 10^?10 and 2.5 × 10^?11 mol l^?1 , respectively. The method was applied to samples of ore (Geological Deposit).     

铌(V)-酒石酸-2-(5'-溴-2'-吡啶偶氮)-5-二乙氨基苯酚三元配便物的汞电极上的吸附

本文用线性变势吸附伏安法研究了铌(V)-酒石酸-2-(5'-溴-2'-吡啶偶氮)-5-二乙氨基苯酚三元配合物在汞电极上的电吸附性质, 测定了表面浓度, 讨论了吸附浓度的表达式及其与吸附时间、金属离子浓度、配位体浓度的关系, 验证了吸附量与电极面积及还原峰电流的关系。证明了配合物在电极上的还原是一个可逆吸附的还原过程。     

Spectrophotometric determination of gadolinium(III) with 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (5-Br-PADAP)

Reaction between gadolinium(III) and 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (5- Br-PADAP) was studied for delineating optimal conditions for complexation. This reagent can be used for the spectrophotometric determination of Gd(III) in concentrations ranging from 0.04 to 1.2 ppm (a = 1.76(+/- 0.03) x 10(5) (1.(-1) mole(-1). cm). The reaction takes place at a pH between 9.2 and 11.6. In the presence of Triton X-100 this complex is soluble in water. In order to overcome difficulties caused by the presence of other lanthanides, an ion exchange chromatographic technique was used.     

Adsorption voltammetry of the copper(II) 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol complex

The voltammetric determination of copper(II), based on adsorptive accumulation of the Cu(II)-2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (S-Br-PADAP) complex on a hanging mercury drop electrode, is reported. The complex can be accumulated at the electrode at constant potential in 0.1M ammonium nitrate/ammonia buffer solution, and its reduction wave observed by scanning the potential in the negative direction, in the differential pulse mode. The calibration graph for copper is linear over the range 0.05-0.5muM, with accumulation for 5 min at -0.20 V. The adsorption of the complex is discussed and compared with that of copper complexes with several other pyridylazo derivatives.     

Adsorptive cathodic stripping voltammetry determination of ultra trace levels of cobalt

The complexation of Co(II) with 4-(2-pyridylazo)resorcinol (PAR) was studied by spectroscopy and voltammetry. In addition, an adsorptive stripping voltammetric method was developed for the determination of ultra trace levels of Co(II) using a hanging mercury drop electrode. The method is based on accumulation of Co(II) on a mercury electrode using PAR as the complexing agent. The effects of instrumental and chemical parameters on the sensitivity of the method were investigated. The detection limit of the method is 0.003 ng/mL. Most foreign species do not interfere with the determination. The high sensitivity and selectivity of this method were demonstrated by determination of cobalt in blood and water samples.     

Adsorptive stripping voltammetric measurements of trace amounts of platinum(II) and ruthenium(III) in the presence of 1-(2-pyridylazo)-2-naphthol

An extremely sensitive stripping voltammetric procedure for low level measurements of platinum (II, IV) or ruthenium (III, IV) is reported. The method is based on the interfacial accumulation of the platinum (II) or ruthenium (III)-1-(2-pyridylazo)-2-naphthol complex on the surface of a hanging mercury drop electrode, followed by the reduction of the adsorbed complex during the cathodic scan. The peak potential was found to be –0.8 V vs. Ag/AgCl electrode and the reduction current of the adsorbed complex ions of platinum (II) or ruthenium (III) was measured by differential pulse cathodic stripping voltammetry. The optimum experimental conditions were: 1.5×10^–7 mol/l of 1-(2-pyridylazo)-2-naphthol solution of pH 9.3, preconcentration potential of –0.2 V, accumulation time of 3 min and pulse amplitude of 50 mV with 4 mV s^–1 scan rate in the presence of ethanol-water (30% v/v) — sodium sulphate (0.5 mol/l). Linear response up to 6.4 × 10^–8 and 5.1 × 10^–8 mol/l and a relative standard deviation (at 1.2×10^–8 mol/l) of 2.4 and 1.6% (n=5) for platinum (II) and ruthenium (III) respectively were obtained. The detection limits of platinum and ruthenium were 3.2×10^–10 and 4.1×10^–10 mol/l, respectively. The electronic spectra of the Pt(II) — PAN and Ru(III) — PAN complexes were measured at pH 9.3 and the stoichiometric ratios of the complexes formed were obtained by the molar ratio method. The effects of some interfering ions on the proposed procedure were critically investigated. The method was found suitable for the sub-microdetermination of ruthenium (IV) and platinum (IV) after their reduction to ruthenium (III) and platinum (II) with sulphur dioxide in acid media. The applicability of the method for the analysis of binary mixtures of ruthenium (III) and (IV) or platinum (II) and (IV) has also been carried out successfully. The method is simple, rapid, precise, and promising for the determination of the tested metal ions at micro-molar concentration level.     

Adsorptive stripping measurements of trace aluminum in the presence of cupferron

The adsorptive collection of the aluminum complex with cupferron is exploited for developing a highly sensitive stripping procedure for trace aluminum. Optimal experimental conditions include the use of 2 x 10(-4)M cupferron in PIPES buffer (pH 7.0), an accumulation potential of -0.40 V and a linear potential scan. With controlled accumulation for 2 min, a detection limit near 30 ng/l. aluminum is obtained. The relative standard deviation (at 5 microg/l.) is 2.9%. Possible interferences are evaluated. The analytical performance compares favourably with that of early adsorptive stripping schemes for aluminum.     

Determination of molybdenum in the presence of 2-(2-benzothiazolylazo)-p-cresol by catalytic-adsorptive stripping voltammetry

The adsorptive collection of the molybdenum (VI) complexed with 2-(2-benzothiazolylazo)-p-cresol (BTAC) coupled with the catalytic current of the adsorbed complex at a static mercury drop electrode yields an ultrasensitive voltammetric procedure for the determination of molybdenum. Optimal experimental conditions were: a stirred acetate buffer 0.2 M (pH 3.5) as supporting electrolyte, a BTAC concentration of 1.0 x 10(-6) M as ligand, and a concentration of 0.1 M potassium nitrate as the oxidizing agent. In addition, a preconcentration potential of -0.080 V vs Ag/AgCl (3 M KCl), equilibration time of 15 s, a frequency of 30 Hz, a scan increment of 2 mV, a pulse amplitude of 0.050 mV, and a drop area of 0.032 cm2 were used. The cyclic voltammogram was recorded using a staircase wave with a scan rate of 100 mV/s. The forward scan starts at the initial potential of -0.080 V and is reversed at -0.90 V. Using the catalytic current at approximately -0.55 V the response to the Mo(VI) was found to be linear over a concentration range of 1.0-10.0 microg/L. The limit of detection is as low as 6.2 x 10(-10) M with 4 min of preconcentration time. The possible interference of other trace ions was investigated. The merits of this procedure are demonstrated using of reference samples.     

Determination of molybdenum in the presence of 2-(2-benzothiazolylazo)-p-cresol by catalytic-adsorptive stripping voltammetry

The adsorptive collection of the molybdenum (VI) complexed with 2-(2-benzothiazolylazo)-p-cresol (BTAC) coupled with the catalytic current of the adsorbed complex at a static mercury drop electrode yields an ultrasensitive voltammetric procedure for the determination of molybdenum. Optimal experimental conditions were: a stirred acetate buffer ¶0.2 M (pH 3.5) as supporting electrolyte, a BTAC concentration of 1.0 × 10^–6 M as ligand, and a concentration of 0.1 M potassium nitrate as the oxidizing agent. In addition, a preconcentration potential of –0.080 V vs Ag/AgCl (3 M KCl), equilibration time of 15 s, a frequency of 30 Hz, a scan increment of 2 mV, a pulse amplitude of 0.050 mV, and a drop area of 0.032 cm² were used. The cyclic voltammogram was recorded using a staircase wave with a scan rate of 100 mV/s. The forward scan starts at the initial potential of –0.080 V and is reversed at –0.90 V. Using the catalytic current at ～–0.55 V the response to the Mo(VI) was found to be linear over a concentration range of 1.0–10.0 μg/L. The limit of detection is as low as 6.2 × 10^–10 M with 4 min of preconcentration time. The possible interference of other trace ions was investigated. The merits of this procedure are demonstrated using of reference samples.     

Adsorptive stripping voltammetry following solid-phase extraction for the trace analysis of fenchlorazol-ethyl in tap water

A very sensitive procedure is presented for quantifying fenchlorazol-ethyl by adsorptive stripping voltammetry using disposable Carbopack solid-phase extraction columns for isolating the phytopharmacon from tap water. The stripping response was evaluated with respect to pH-value, accumulation time, potential and mercury drop size. In consideration of the recovery rate the detectable level for fenchlorazol-ethyl after 10 min accumulation at –0.1 V was found to be 0.2 g·l^–1 in 1 l of water. The procedure was applied to spiked tap water.Lecture presented at the First Conference on Electroanalytical Chemistry (ELACH I), Feldberg, Mecklenburg, 2–4 June 1993     

Adsorptive stripping voltammetry of Ni(II) using fast linear sweeps

Summary Nickel was determined as bis-(dimethylglyoximato)-nickel(II) by fast cathodic linear sweep voltammetry with a rate of 10 V s^–1 after adsorption on a static mercury electrode. The peak width at half-height was 60 mV. For determinations down to 1 ppb of Ni(II), only 40 s accumulation time were required without accelerating measures like stirring or potential application. Resolution and sensitivity were thus similar to differential pulse voltammetry but the duration of a measuring cycle was only 45 s (40 s accumulation, 80 ms for sweep and 5 s for readout). The method was tested with 2 industrial waste water samples and urine. The direct determination of Ni(II) in urine failed, whereas it was possible in the waste water. Concurrent adsorption was the main interference.

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Adsorptive Stripping-Voltammetrie von Nickel(II) mit schnellem linearem Spannungsvorschub

     

Adsorptive stripping voltammetry determination of molybdenum(VI) in water and soil

A differential pulse stripping voltammetry method for the trace determination of molybdenum(VI) in water and soil has been developed. In 0.048M oxalic acid and 6 x 10(-5)M Toluidine Blue (pH 1.8) solution, Mo(V), the reduction product of Mo(VI) in the sample solution, can form a ternary complex, which can be concentrated by adsorption on a static mercury drop electrode at -0.1 V (vs. Ag/AgCl). The adsorbed complex gives a well-defined cathodic stripping current peak at -0.30 V, which can be used for determining Mo(VI) in the range 5 x 10(-10)-7 x 10(-9)M, with a detection limit of 1 x 10(-10)M (4 min accumulation). The method is also selective. Most of the common ions do not interfere but Sn(IV) and large amounts of Cu(2+), Ag(+) and Au(3+) affect the determination.     

Spectrophotometric determination of zinc with 2-(3,5-dibromo-2-pyridylazo)-5-diethylaminophenol in the presence of anionic surfactant

A sensitive spectrophotometric method for zinc has been established by reacting zinc with 2-(3,5-dibromo-2-pyridylazo)-5-diethylaminophenol (3,5-diBr-PADAP) in the presence of an anionic surfactant, sodium lauryl sulphate. The molar absorptivity is 1.3 x 10(5) l.mole(-1).cm(-1) at 570 nm. The molar ratio of zinc to 3,5-diBr-PADAP is 1:2. Beer's law is obeyed up to 0.7 ppm of zinc. With preseparation of zinc by extraction of its thiocyanate complex, the method has been applied to the determination of zinc in waste water.     

Adsorptive stripping measurements of germanium(IV) in the presence of pyrogallol

The adsorptive stripping voltammetric determination of germanium(IV) based on the adsorptive accumulation of the germanium(IV)-pyrogallol complex on a hanging mercury drop electrode is reported. The reduction current of the adsorbed germanium complex is measured by differential-pulse cathodic stripping voltammetry. The peak potential is at -0.42 V vs. Ag AgCl (saturated KCL). The effects of various parameters (ligand concentration, supporting electrolytic composition and concentration, accumulation potential and collection time) on the response are discussed. With controlled accumulation for 3 min, the detection limit is 1.2 x 10(-9) M germanium. The relative standard deviation (at 1.2 x 10(-8) M germanium) is 3.6%. Possible interferences are evaluated. The applicability of the method to the determination of germanium(IV) in ore samples was also successfully carried out.     

Spectrophotometric determination of uranium(VI) with 2-(3,5-dibromo-2-pyridylazo)-5-diethylaminophenol in the presence of anionic surfactant

A highly sensitive method for spectrophotometric determination of uranium has been devised. The method is based on formation of a red-violet 1:2 (metal:ligand) complex from the reaction of uranium(VI) with 2-(3,5-dibromo-2-pyridylazo)-5-diethylaminophenol (3,5-diBr-PADAP) in the presence of an anionic surfactant, sodium lauryl sulphate. Its molar absorptivity is found to be 9.1 x 10(4)l.mole(-1).cm(-1). The absorbance is constant in the range pH 8.4-9.9 Beer's law is obeyed for 0-1.4 mug/ml concentrations of uranium. In the presence of DCTA the method is selective for uranium, and can be used for the determination of trace amounts of uranium in water samples.     

Adsorptive stripping voltammetry of some trace elements in biological samples. I. Cadmium and zinc

A study of the adsorptive stripping voltammetry of cadmium and zinc is reported in which ligands containing sulphur donor atoms were examined. This type of ligand showed good adsorptive behaviour and strong metal complexation. It was found that the ligand 2,5-dimer-capto-1,3,4-thiadiazole (DMTD) was very suitable for the determination of cadmium and zinc using this technique.The method was applied to the direct determination of these metals in biological samples using benzyl trimethylammonium methoxide as digesting solvent for the samples.     

Spectrophotometric determination of cadmium(II) using 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol

The complex of cadmium with the reagent 2-(-5-bromo-2-pyridylazo)-5-diethylaminophenol (5-Br-PADAP) has been studied. The composition, stability constant, and free energy change of formation of the complex have been determined. A sensitive spectrophotometric method for the determination of cadmium has been developed and applied for a range of concentration of 0.4–4.0 μg/ml cadmium using the complex Cd-5-Br-PADAP. The optimum conditions for maximum sensitivity of determination such as standing time, pH, wavelength, and order of addition have been determined. The effect of foreign ions on this method has been also studied.     

Spectrophotometric Determination of Mercury Using 2-(5-Bromo-2-pyridylazo)-5-diethylaminophenol

Abstract

Mercuric ion with 5-Br-PADAP forms a 1:2 complex at pH 8.0–10, which, with the addition of Triton X-100, has a molar absorptivity of 1.10 × 10⁵ at 565 nm. A method is described for the determination of mercury in industrial waste water and sludge.