Stripping voltammetry of manganese based on chelate adsorption at the hanging mercury drop electrode

A novel electrochemical stripping approach for the trace measurement of manganese is presented. The metal chelate with erichrome black T is adsorbed on a hanging mercury drop electrode, and the subsequent reduction current of the accumulated chelate is measured by voltammetry. Adsorptive preconcentration for 5 min results in a detection limit of 6 × 10^?10 M (32 l^?1). Cyclic voltammetry is used to characterize the redox and interfacial processes. Optimal experimental conditions include a 0.02 M piperazine-N,N′-bis(2-ethanesulfonic acid) solution (pH 12) containing 1 × 10^?6 M eriochrome black T, a preconcentration potential of ?0.80 V, and a linear potential scan. The response is linear up to 2.9 × 10^?7 M, and the relative standard deviation at 1.8 × 10^?7 M is 1.5%. The effects of possible interferences from metal ions or organic surfactants are evaluated.     

Voltammetric study of the copper-1,10-phenanthroline complex

The behaviour of the complex of copper with 1,10-phenanthroline at a mercury electrode was investigated in acidic chloride media. Adsorption phenomena were observed by both differential-pulse and normal-pulse polarography. These properties were used in developing a sensitive stripping voltammetric procedurefor the determination of traces of copper. The effects of various operational parameters (pH, ligand concentration, potential and accumulation time) on the reduction current of the adsorbed chelate are discussed. Interferences by other trace metals and organic matter were investigated. A linear current-concentration relationship was observed up to about 1.5 × 10^?7 M. The detection limit is 1.2 × 10^?10 M copper after a 10-min accumulation time with a stirred solution.     

Analytical application of poly [dibenzo-18-crown-6] for chromatographic separation of thorium(IV) from uranium(VI) and other elements in glycine medium

A selective and effective chromatographic separation method for thorium(IV) has been developed by using poly [dibenzo-18-crown-6] as stationary phase. The separations are carried out from glycine medium. The sorption of thorium(IV) was quantitative from 1 × 10^?2 to 1 × 10^?4 M glycine. The elution of thorium(IV) was quantitative with 2.0–8.0 M HCl, 4.0–7.0 M HBr, 1.0–2.0 M HClO₄ and 5.0 M H₂SO₄. The capacity of poly [dibenzo-18-crown-6] for thorium(IV) was found to be 0.215 ± 0.01 mmol/g of crown polymer. The effect of concentration of glycine, metal ion, foreign ion and eluents has been studied. Thorium(IV) was separated from a number of cations in ternary as well as in multicomponent mixtures. The applicability of the proposed method was checked for the determination of thorium(IV) in real as well as geological sample. The method is simple, rapid, and selective with good reproducibility (approximately ±2 %).     

An optical-fibre sensor for fluoride

The optical sensor is based on the formation of a fluoride ternary complex from an immobilized fluorescent binary zirconium-calcein blue chelate at pH 2.2. The enhanced fluorescence enables fluoride to be determined in the range 2.63 × 10^?5 ?4.21 × 10^?4 M (0.5–8.00 mg l^?1) with a limit of detection of 2.63 × 10^?5 M. The response of the sensor to fluoride is affected by ionic strength and temperature. The response time depends on the particle size and the packing density of the polymer (XAD-4) substrate used.     

Adsorptive stripping voltammetry of sex hormones at the static mercury drop electrode

Controlled adsorptive accumulation of testosterone, methyltestosterone and progesterone on the static mercury drop electrode provides the basis for direct stripping measurement of these compounds ar nanomolar concentrations. The adsorptive stripping behavior is evaluated with respect to preconcentration time and potential, stripping mode, concentration dependence, drop size and other variables. With 5-min accumulation, peak current enhancements of 45, 18 anal 12 are observed for 5 × 10^?8 M testosterone, progesterone and methyltestosterone, respectively, relative to direct pulse voltammetry. Detection limits are 1.6 × 10^?10 M for testosterone, 2 × 10^?10 M for progesterone and 3.3 × 10^?10 M for methyltestosterone with 15-min preconcentration. The relative standard deviation for 8 × 10^?8 M progesterone is 3.4% (n=8). Applicability to direct measurements of methyltestosterone in pharmaceutical formulations is assessed.     

Adsorptive Cathodic Stripping Voltammetry Determination of Ultra Trace of Lead in Different Real Samples

Abstract

In the present work, an adsorptive cathodic stripping voltammetric method using a hanging mercury drop electrode (HMDE) was described in order to determine the ultra trace of lead ions with carbidopa in different real samples. The method is based on accumulation of lead metal ion on mercury electrode using carbidopa as a suitable complexing agent. The potential was scanned to the negative direction and the differential pulse stripping voltammograms were recorded. The instrumental and chemical parameters were optimized. The optimized conditions were obtained in pH of 8.4, carbidopa amount of 1.0×10^?6 M, accumulation potential of 0. 0 V, accumulation time of 100 s, scan rate of 100 mV/s and pulse height of 50 mV. The relationship between the peak current versus concentration was linear over the range of 2.4×10^?10–4.8×10^?7 M. The limits of detection were 5.8×10^?11 M and the relative standard deviation at 4.8×10^?10, 2.1×10^?8, and 2.4×10^?7 M of lead ion were obtained 3.2, 2.9, and 2.7%, respectively (n=7).     

Electrochemical study of thorium in dimethylsulfoxide and propylene carbonate

Solutions of ThCl₄ in anhydrous dimethylsulfoxide or propylene carbonate have been investigated by dc polarography and controlled potential chronoamperometry on a hanging mercury drop electrode. The results are interpreted by assuming that the cathodic reduction of thorium on mercury proceeds through one step Th(IV)+4 e→Th(0) (E^1/2??1.65V vs. SCE in DMSO); however, the results obtained indicate that the reduction gives rise to the the formation of an autoinhibiting monoatomic layer of thorium; further reduction of thorium on this requires an overpotential (E^1/2??2.15 V vs. SCE in DMSO).The mean value for the maximal superficial concentration of thorium in the film deduced from these experiments equals 1.25×10^?9 mol cm^?2, whereas the value for a hexagonal close-packed layer is 1.5×10^?9 mol cm^?2.     

Voltammetric determination of selenosulfate ions at a mercury-film electrode

A procedure is proposed for the voltammetric determination of selenium as selenosulfate (SO₃Se^2?) ions at a mercury-film electrode (MFE). Selenosulfate ions are determined in the range from 2 × 10^?4 to 1.0 × 10^?3 M without analyte accumulation, using peak current at ?0.92 ± 0.02 V and in the range from 1 × 10^?7 to 2 × 10^?4 M after analyte accumulation with the open circuit, using peak current at ?1.18 ± 0.03 V as the analytical signal. The mechanisms of SO₃Se^2? reduction at an MFE under the conditions of direct voltammetry and stripping voltammetry with accumulation are proposed and discussed.     

Determination of some quinoxaline-N-dioxide derivatives by adsorptive stripping voltammetry

Some derivatives of quinoxaline-N-dioxides, which are used as growth promoters in animals (Carbadox, Cyadox, Olaquindox), can be determined at nanomolar concentrations by stripping volatammetry from a static mercury drop electrode after adsorptive accumulation on the electrode surface. With differential pulse voltammetry, in 0.1 M sodium perchlorate with 5% (v/v) dimethylformamide, the detection limit for Cyadox is 3 × 10^?10 mol 1^?1 after accumulation for 300 s in stirred solution; detection limits are 2 × 10^?9 mol 1^?1 (180 s accumulation) for Carbadox and 7 × 10 mol 1^?1 (60 s accumulation) for Olaquindox. The relative standard deviations are 0.85% for Cyadox (4 × 10^?9 mol 1^?1), 0.54% for Carbadox (2 × 10^?8 mol 1^?1) and 0.95% for Olaquindox (2 × 10^?8 mol 1^?1). Surfactants interfere.     

Trace determination of lanthanum,cerium, and praseodymium based on adsorptive stripping voltammetry

A sensitive stripping procedure is described for quantifying lanthanum, cerium and praseodymium ions, based on the controlled adsorptive accumulation of the lanthanide/o- cresolphthalexon complex onto the static mercury drop electrode. The effect of various operational parameters on the stripping response is discussed. A 20-min accumulation period coupled with differential pulse measurement of the current resulting from the adsorbed complex permits quantitation down to the 1 × 10^?10 M level. For concentrations ranging from 2.5 × 10^?8 M to 2.5 × 10^?9 M, a 0.5- to 4-min accumulation period is sufficient. The relative standard deviation ar the 7 × 10^?8 M level ranges from 1 to 6%.     

Determination of traces of palladium by adsorptive stripping voltammetry of the dimethylglyoxime complex

Preconcentration is achieved by adsorption of a palladium-dimethylglyoxime complex on a hanging mercury drop electrode. Optimal conditions area stirred acetate buffer solution (pH 5.15) containing 2 × 10^?4 M dimethylglyoxime and an accumulation potential of —0.20 V. The height of the stripping peak in a negative-going linear scan is linearly dependent on palladium concentration and preconcentration time (over the ranges 0–16 μg l^?1 and 0–300 s, respectively). For a 10-min preconcentration time, the detection limit is 20 ng l^?1 (2.1 × 10^?10 M). Possible interferences by other trace metals are investigated. Palladium added to seawater samples was easily quantified.     

Determination of trace amounts of nickel by differential pulse adsorptive cathodic stripping voltammetry using calconcarboxylic acid as a chelating agent

A method for the determination of nickel(II) by stripping voltammetry is described. The method is based on the adsorptive accumulation of nickel(II) calconcarboxylic acid complex onto a hanging mercury drop electrode (HMDE), followed by the reduction of the adsorbed complex using differential pulse voltammetry. The optimum operating conditions and parameters were found to be 0.05 M NH₃/NH₄Cl buffer (pH = 9.5) as the supporting electrolyte, a ligand concentration of 1 × 10^?6 M, accumulation potential of ?0.5 V (vs. Ag/AgCl) and accumulation time of 60 s. At the optimized conditions, the peak current is proportional to the concentration of nickel in the range of 1.7 × 10^?9 to 4.7 × 10^?7 M (0.1–28 ng ml^?1) with a detection limit of 0.05 ng ml^?1. The relative standard deviation (n = 10) at nickel concentrations of 2, 10 and 15 ng ml^?1 varies in the range 0.76 to 2.1%. Possible interferences by metal ions, which are of great significance in real matrices, have been studied. The method was successfully applied to the determination of nickel content in a chocolate sample.     

A Coated Graphite Thorium‐Ion Selective Potentiometric Sensor Based on a Calix[4]arene Bearing Phosphoryl Groups

5,11,17,23‐Tetra‐tert‐butyl‐25,26,27,28‐tetrakis(diphenylphosphinoylmethoxy)calix[4]arene ( 1 )has been used for the preparation of a graphite coated thorium ion‐selective electrode (Th⁴⁺‐ISE). The plasticized PVC membrane containing 30% PVC, 58% ortho‐nitrophenyloctylether (NPOE), 4% sodium tetraphenylborate (NaTPB) and 8% ionophore was directly coated on a graphite rod. This sensor gave good Nernstian responses with a slope of 15.5 ± 0.1 mV/decade over a concentration range of 1 × 10^?5 ?1 × 10^?3 M of thorium ions with a limit of detection of 7.9 × 10^?6 M. The dynamic response time of the electrode to achieve a steady potential was found to be about 15 seconds. The potential of the prepared sensor was independent of the pH variation in the range 2.3–4.0. The selectivity relative to several mono‐, di‐ and tri‐valent metal ions, i.e. Li⁺, Na⁺, K⁺, Ag⁺, NH₄⁺, Sr²⁺, Mn²⁺, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺, La³⁺, Sm³⁺, Dy³⁺, Er³⁺ and Y³⁺ was examined. This electrode can be used for 6 months without any considerable divergences in the potential response. The sensor was successfully used as an indicator electrode for the potentiometric titration of a thorium solution using a standard solution of EDTA.     

Adsorptive stripping voltammetry of chlordiazepoxide at the hanging mercury drop electrode

Controlled adsorptive accumulation at the hanging mercury drop electrode enables 0.8–11 × 10^?5 M chlordiazepoxide to be quantified by differential-pulse stripping voltammetry with accumulation times of 1–3 min. With 3-min accumulation, the peak current is enhanced 12-fold for 1.0 × 10^?7 M chlordiazepoxide compared to the current from differential pulse polarography. The detection limit is 0.9 × 10^?9 M for 4-min accumulation. The procedure is applied to spiked human serum after preseparation of the drug on a Sep-Pak C₁₈ cartridge.     

Kinetic determination of some inorganic and organic compounds by oxidation with iodate

Sulphite (5.0 × 10^?1?5.0 × 10^?3 M), ascorbic acid and other compounds are oxidized by potassium iodate in dilute sulphuric acid; the production of iodide is monitored by an iodide-selective electrode. The time needed for a 40-mV potential change is inversely proportional to concentration. For sulphite (1.0 × 10^?5?1.0 × 10^?4 M), selectivity is improved by sweeping the sulphur dioxide formed in acidic EDTA-containing solution into the iodate solution.     

Highly Ordered TiO2 Nanotubes for Electrochemical Sensing of Hair Dye Basic Brown 17

Self‐organized Ti/TiO₂ nanotubular array electrodes were prepared by electrochemical anodization and used to monitor the reduction of the hair dye basic brown 17 (BB17) at a potential of ?0.60 V vs. Ag/AgCl. Analytical curves were obtained from 1.0×10^?6 to 8.0×10^?5 mol L^?1 with a detection limit of 1.3×10^?7 mol L^?1 by using the best experimental conditions, linear scan voltammetry at pH 6, scan rate=60 mV s^?1, and accumulation time=5 min. The detection system performance was not interfered by other hair dyes and successfully used to determine the dye in tap water samples.     

Determination of cadmium(II) using glassy carbon electrodes modified with cupferron, ß-naphthol, and multiwalled carbon nanotubes

We report on a simple and reliable method for the determination of trace cadmium ion using a glassy carbon electrode (GCE) modified with cupferron, ß-naphthol and MWCNTs. The operational mechanism consists of several steps: first, the ligand cupferron on the modified electrode reacts with Cd²⁺ ion to form a chelate compound. Next, this chelate is adsorbed by the carrier ß-naphthol following the principle of organic co-precipitation. Finally, the coprecipitated complex is detected by the GCE. This scheme is interesting because it combines preconcentration and electrochemical detection. Two linear responses are obtained, one in the concentration range of 5.0?×?10^?11 to 1.6?×?10^?8 M, the other in the range of 1.6?×?10^?8 to 1.42?×?10^?6 M, with a lower detection limit of 1.6?×?10^?11 M. This modified GCE does not suffer from significant interferences by Cu(II), Hg(II), Ag(I), Fe(III), Pb(II), Cr(III), Zn(II), NO^3?, Cl^?, SO ₄ ^2? ions and EDTA. The response of the electrode remained constant for at least 3 weeks of successive operation. The method presented here provides a new way for the simultaneous separation, enrichment, and electrochemical detection of trace cadmium ion.

A nafion/crown ether film electrode and its application in the anodic stripping voltammetric determination of traces of silver

Glassy carbon electrodes are modified by coating with dicyclohexyl-18-crown-6 in Nafion-117. The electrode is used for a very sensitive anodic stripping voltammetric determination of silver. High sensitivity is obtained owing to the release of crown molecules from the silver-crown complex during the deposition. The detection limit is 2×10^?12 M after electrodeposition for 30 min. The recommended supporting electrolyte is 4×10^?3–7×10^?3 M potassium chloride in 0.01 M nitric acid with a deposition potential of ?0.30 V vs. SCE and a linear potential scan. Three typical calibration graphs were linear over the range 2×10^?11–1×10^?8 M for deposition times of 30, 20 and 8 min, respectively. The silver content of reagent-grade ammonium nitrate was found to be 0.48×10^?4% with a relative standard deviation of 3.7% (n=7) for parallel determinations.     

Subnanomolar Determination of Indium by Adsorptive Stripping Differential Pulse Voltammetry Using Factorial Design for Optimization

Abstract

A highly sensitive method to determine of indium is proposed by adsorption stripping differential pulse cathodic voltammetry (AdSDPCV) method. The complex of indium ions with xylenol orange is analyzed based on the adsorption collection onto a hanging mercury drop electrode (HMDE). After accumulation of the complex at ?0.20 V vs. Ag/AgCl reference electrode, the potential is scanned in a negative direction from ?0.40 to ?0.75 V with the differential pulse method. Then, the reduction peak current of In(III)–XO complex is measured. The influence of chemical and instrumental variables was studied by factorial design analysis. Under optimum conditions and accumulation time of 60 s, linear dynamic range was 0.1–10 ng/ml (8.7 × 10^?10 to 8.7 × 10^?8 M) with a limit of detection of 0.03 ng/ml (2.6 × 10^?10 M); at accumulation time of 5 min, linear dynamic range was 0.04–10 ng/ml (3.4 × 10^?10 to 8.7 × 10^?8 M) with a limit of detection of 0.013 ng/ml (1.1 × 10^?10 M). The applicability of the method to analysis of real samples was assessed by the determination of indium in water, alloy, and jarosite (zinc ore) samples.     

Adsorptive stripping voltammetry of bovine serum albumin

The behaviour of bovine serum albumin in cyclic voltammetry and differential-pulse adsorptive stripping voltammetry is described. Under the optimized conditions, with an accumulation potential of +0.15 V (vs. Ag/AgCl) and accumulation times of 50 s or 120 s, linear calibration graphs were obtained for 1.0–4.0×10^?8 M BSA and 0.2–1.5×10^?8 M BSA, respectively.