Anodic stripping voltammetric determination of bismuth(III) using a Tosflex-coated mercury film electrode

A Tosflex-mercury film electrode (TMFE) was prepared by spin-coating a solution of the perfluorinated anion exchange polymer Tosflex onto a glassy carbon electrode surface followed by electrodeposition of mercury film on this electrode. This electrode was used for the determination of trace bismuth(III) which was preconcentrated onto the TMFE as anionic bismuth(III) complexes with chloride in a chloride medium. The preconcentration was carried out at a potential of-0.2 V, and the preconcentration of the bismuth(III) was enhanced significantly by the anion-exchange feature of Tosflex. The accumulated bismuth(III) was then determined by anodic square-wave stripping voltammetry (SWSV). Various parameters influencing the determination of bismuth(III) were examined in detail. With 2 min accumulation, the analytical signal versus concentration dependence was linear up to 50 ppb, and the detection limit was 0.58 ppb. This modified electrode showed good resistance to the interferences from surface-active compounds and common ions.     

Anodic stripping voltammetric determination of mercury using multi-walled carbon nanotubes film coated glassy carbon electrode

An electrochemical method for the determination of trace levels of mercury based on a multi-walled carbon nanotubes (MWNT) film coated glassy carbon electrode (GCE) is described. In 0.1 mol L^–1 HCl solution containing 0.02 mol L^–1 KI, Hg²⁺ was firstly preconcentrated at the MWNT film and then reduced at –0.60 V. During the anodic potential sweep, reduced mercury was oxidized, and then a sensitive and well-defined stripping peak at about –0.20 V appeared. Under identical conditions, a MWNT film coated GCE greatly enhances the stripping peak current of mercury in contrast to a bare GCE. Low concentrations of I^– remarkably improve the determining sensitivity, since this increases the accumulation efficiency of Hg²⁺ at the MWNT film coated GCE. The stripping peak current is proportional to the concentration of Hg²⁺ over the range 8×10^–10–5×10^–7 mol L^–1. The lowest detectable concentration of Hg²⁺ is 2×10^–10 mol L^–1 at 5 min accumulation. The relative standard deviation (RSD) at 1×10^–8 mol L^–1 Hg²⁺ was about 6% (n=10). By using this proposed method, Hg²⁺ in some water samples was determined, and the results were compared with those obtained by atomic absorption spectrometry (AAS). The two results are similar, suggesting that the MWNT-film coated GCE has great potential in practical analysis.     

Anodic stripping voltammetric determination of vardenafil hydrochloride at pencil graphite electrode

In this paper, we present a very popular and low-cost sensor material as disposable pencil graphite electrode (PGE) system for the trace-level determination of vardenafil hydrochloride (VRL). Electrochemical behavior and determination of VRL was carried out by cyclic and square-wave adsorptive anodic stripping (SW-AdAS) voltammetry. The proposed method was highly sensitive and had a linear calibration range from 3 × 10^?10 to 1 × 10^?7 M with a correlation coefficient of 0.997. The limit of detection and limit of quantitation values were calculated as 1 × 10^?10 and 3 × 10^?10 M, respectively. Developed method with disposable PGE shows high sensitivity, selectivity and stability in a wide concentration range for VRL determination without the necessity of any modification. Additionally, this system was successfully applied in Levitra^® tablets and spiked human serum in trace level of VRL. Some kinetic parameters of VRL’s were represented for the first time. The results showed that the proposed method is highly sensitive, easy and low cost for trace-level determination of VRL.     

Adsorptive stripping voltammetric determination of dimenhydrinate at a hanging mercury drop electrode

Dimenhydrinate exhibits a single adsorptive stripping peak at a hanging mercury drop electrode after accumulation at 0.0V vs Ag/AgCl electrode at pH 3.8 (acetate buffer). The addition of trace amounts of copper ions enhanced the dimenhydrinate peak and its height depends on the concentration of each dimenhydrinate and Cu²⁺. The adsorptive stripping response was evaluated with respect to accumulation time and potential, concentration dependence, electrolyte, the presence of other purines, surfactants and other metal ions, and some variables. The calibration graph for dimenhydrinate determination is linear over the range 2.0×10^–8–2.0×10^–7 M (pre-concentration for 60s). The correlation factor is found to be 0.985 and RSD is 3.2% at 1.0×10^–7 M. Detection limit is 1.0×10^–8 M after 5 min accumulation. The determination of dimenhydrinate in pharmaceutical formulations by the proposed method is also reported.     

Anodic stripping determination of mercury in air with a glassy carbon electrode

A technique for stripping determination of mercury traces in air employing a glassy carbon electrode is described. The sample is passed at 2 liters min^?1 for 2 hr through an absorber containing 0.2 M potassium permanganate and 10% $\text{w}\text{v}$ sulfuric acid (1:1). After reduction with hydroxylamine hydrochloride, the determination is carried out in 0.12 M potassium thiocyanate at pH 2.0 ± 0.2 in the presence of 0.2 ppm of cupric ions. Calibration curves were found to be linear in the range 20 ppb-1 ppm Hg(II) in the cell. The accuracy of the method was tested over simulated samples and it was found to be better than 95%; the relative standard deviation was 5% or less. The limit of detection of mercury in air was approximately 10 μg m^?3.     

Anodic stripping coulometry at a thin-film mercury electrode

Primary coulometric versions of d.c. anodic stripping voltammetry, performed in a microcell at a mercury-plated rotating glassy carbon electrode, are applied to the determination of cadmium and lead. With exhaustive preelectrolysis of the sample solution, 5–100 ng of the metal can be determined from the charge contained in the stripping signal; precision and accuracy are in the 5% range. An extrapolation procedure that requires only partial metal deposition is evaluated.     

Anodic stripping voltammetric determination of trace lead with a nafion/crown-ether film electrode

An electrode for the anodic stripping voltammetric determination of trace lead has been made by coating glassy carbon with a film of Naflon in which a crown ether is incorporated. The sensitivity is increased because of continuous transfer of lead from solution to the electrode surface by complexation with the crown ether and reduction during the deposition period. A detection limit of 5 x 10(-10)M has been obtained by electrodeposition for 3 min. The method is sensitive, simple and relatively rapid, with a relative standard deviation of 8% at the 2 x 10(-9)M level.     

Preconcentration and voltammetric measurement of mercury with a crown-ether modified carbon-paste electrode

Carbon-paste electrodes modified with crown-ethers were constructed by mixing the crown-ethers into a graphite powder/Nujol oil matrix. The electrodes so formed were able to bind mercuric ions chemically, and gave greater voltammetric response to mercury than that of ordinary carbon-paste electrodes. The response was characterized with respect to paste composition, crown-ether, preconcentration period, mercury concentration, reproducibility, possible interferences, and other variables. Best results were obtained with 18-crown-6 and an acetate buffer (pH 4.0). The electrode gave good linearity for 1 x 10(-5)-6 x 10(-6)M mercury, a detection limit of 2 x 10(-6)M, and a relative standard deviation of 11%. The investigation may lead to a new class of modified (complexing) electrodes, with different patterns of reactivity.     

Anodic stripping voltammetry at a nickel-based mercury film electrode

The electrochemical properties of the nickel-based mercury film electrode (Ni-MFE) were investigated with respect to application of the electrode in the anodic stripping voltammetry (a.s.v.) of heavy metal ions. The hydrogen overpotential at the Ni-MFE is higher than those at MFEs based on other metals, and high enough to get quantitative a.s.v. peaks of lead and cadmium. The mercury film of the Ni-MFE is stable both mechanically and chemically; a.s.v. peaks at a Ni-MFE which had been used fifty times within 300 h after its preparation were identical with those at the freshly prepared electrode. With the Ni-MFE, 5 × 10^?10–10^?7 M lead(II) and 2 × 10^?10–10^?7 M cadmium(II) in the solution can be determined with relative standard deviations of 11 and 12%, respectively. These results are comparable to those obtained by a.s.v. at an in situ mercury-plated g]assy carbon electrode.     

Pulsed voltammetric stripping at the thin-film mercury electrode

A computer-controlled data acquisition system was used to generate comparative data for thin-film anodic stripping voltammetry with staircase, differential pulse and squarewave waveforms. Each waveform was tested for its sensitivity and speed of analysis. The square-wave form is the most sensitive, whether square wave or differential pulse measurements are used. This waveform offers the advantages of fast analysis time and discrimination against charging currents.     

Anodic stripping voltammetric determination of silver ion at a carbon paste electrode modified with carbon nanotubes

A carbon paste electrode (CPE) was modified with multi-wall carbon nanotubes and successfully applied to the determination of silver ion by differential pulse anodic stripping voltammetry. Compared to a conventional CPE, a remarkably improved peak current response and sensitivity is observed. The analytical procedure consisted of an open circuit accumulation step for 2?min in ?0.4?V, this followed by an anodic potential scan between +0.2 and?+?0.6?V to obtain the voltammetric peak. The oxidation peak current is proportional to the concentration of silver ion in the range from 1.0?×?10^?8 to 1.0?×?10^?5?mol?L^?1, with a detection limit of 1.8?×?10^?9?mol?L^?1 after an accumulation time of 120?s. The relative standard deviation for 7 successive determinations of Ag(I) at 0.1???M concentration is 1.99%. The procedure was validated by determining Ag(I) in natural waters.

Copper film electrode for anodic stripping voltammetric determination of trace mercury and lead

A novel in-situ prepared copper film electrode (CuFE) for anodic stripping voltammetric measurement of trace levels of Hg(II) and Pb(II) is presented. The optimal electroanalytical performance of the CuFE was achieved in electrolyte solution comprising 0.1 M HCl and 0.4 M NaCl. The CuFE exhibited excellent operation in the presence of dissolved oxygen with calculated LoD of 0.1 μg L^− 1 Hg(II) and 0.06 μg L^− 1 Pb(II) in combination with 300 s accumulation time, repeatability with RSD of 4.5% for Hg(II) and 0.9% for Pb(II) (n = 12), and favourable linear response in the examined concentration range of 10–100 μg L^− 1 (R² = 0.997) for Hg and 5–70 μg L^− 1 (R² = 0.999) for Pb after 120 s accumulation. The electrode enabled also simultaneous detection of both investigated metal ions and revealed promising electroanalytical characteristics similar to or in certain cases surpassing those of commonly used gold electrodes.     

Anodic stripping voltammetric determination of antimony in gunshot residue

Anodic stripping voltammetry (a.s.v.) ata mercury film on a glassy carbon working electrode was utilized to determine the amount of antimony from hand swabs. The procedure described is useful for determining 10–120 ng of antimony found in the residue ou the hands of an individual suspected of discharging or handling a firearm. The voltammogram provides an elemental pattern recognizable as gunshot residue containing small amounts of antimony and much larger amounts of copper and lead. The amount of antimony in a variety of gunshot-residue samples was determined by both anodic stripping voltammetry and graphite-furnace atomic absorptiou spectrometry for comparison purposes. Anodic stripping voltammetry is excellent for observation of the multielement pattern which proves to be very useful for gunshot-residue samples.     

Anodic stripping voltammetric determination of copper (II) ions at a graphene quantum dot-modified pencil graphite electrode

A simple and sensitive electrochemical sensor based on graphene quantum dot-modified pencil graphite electrode (GQD/PGE) was fabricated and used for highly selective and sensitive determination of copper (II) ions in nanomolar concentration by square wave adsorptive stripping voltammetric method. The sensing mechanism could be attributed to the formation of a complex between Cu²⁺ ions and oxygen-containing groups in GQDs which result in an increased SWV signal in comparison with the bare electrode. Optimization of various experimental parameters such as pre-concentration time, pre-concentration potential, pH, and buffer type which influence the performance of the sensor, was investigated. Under optimized condition, GQD-modified electrode has been used for the analysis of Cu²⁺ in the concentration range from 50 pM to 4 nM and a lower detection limit of 12 pM with good stability, repeatability, and selectivity. Finally, the practical applicability of GQD-PGE was confirmed via measuring trace amount of Cu (II) in water samples. The GQD/PGE surface could be regenerated by exerting more positive potentials than the stripping potential of the Cu (II) ion and then used for another deposition.     

Anodic stripping voltammetric determination of titanium(IV) using a carbon paste electrode modified with cetyltrimethylammonium bromide

A method is described for the voltammetric determination of titanium(IV) using a carbon paste electrode modified in situ with cetyltrimethylammonium bromide. The cationic micellar surfactant adsorbs onto the electrode particularly at negative potentials, simultaneously preconcentrating titanium(IV) as the oxalate complex with reduction to titanium(III). Anodic stripping voltammetry exploiting reoxidation can be used for the determination of trace levels of titanium(IV). Linearity between current and concentration exists between 5 and 160 mug l(-1) Ti(IV) (preconcentration time 2 min). The limit of detection (calculated as 3sigma) is 0.1 mug l(-1), with a preconcentration time of 10 min.     

Cathodic stripping voltammetric determination of selenium(IV) at a thin-film mercury electrode in a thiocyanate-containing electrolyte

The well-known method for the determination of selenium(IV), which is based on the cathodic stripping voltammetry of copper(I) selenide, has been adapted for application at the thin-film mercury electrode on glassy carbon (TFME). Insufficient reproducibility and sensitivity have been overcome by using a 0.1 mol/L HClO₄ electrolyte solution containing 0.02 mol/L thiocyanate ions. Thiocyanate ions have been found to increase the peak height of the selenium response and shift it to more positive potentials. This behaviour is explained by an adsorption of SCN^– at the interface glassy carbon/Cu₂Se and its action as an electron transfer catalyst between glassy carbon and copper(I) selenide. A 3σ-detection limit of 75 ng/L Se^(IV) has been achieved. The relative standard deviation is 5.2% at 5 μg/L selenium(IV). The influence of cadmium(II), arsenic(III), zinc(II), iron(III) and lead(II) ions on the selenium response has been studied. In case of lead ions, a new signal occurred at more negative potentials than the reduction of Cu₂Se. This signal, which is probably due to the reduction of PbSe, can also be used for the determination of selenium(IV).     

Cathodic stripping voltammetric determination of selenium(IV) at a thin-film mercury electrode in a thiocyanate-containing electrolyte

The well-known method for the determination of selenium(IV), which is based on the cathodic stripping voltammetry of copper(I) selenide, has been adapted for application at the thin-film mercury electrode on glassy carbon (TFME). Insufficient reproducibility and sensitivity have been overcome by using a 0.1 mol/L HClO₄ electrolyte solution containing 0.02 mol/L thiocyanate ions. Thiocyanate ions have been found to increase the peak height of the selenium response and shift it to more positive potentials. This behaviour is explained by an adsorption of SCN^– at the interface glassy carbon/Cu₂Se and its action as an electron transfer catalyst between glassy carbon and copper(I) selenide. A 3σ-detection limit of 75 ng/L Se^(IV) has been achieved. The relative standard deviation is 5.2% at 5 μg/L selenium(IV). The influence of cadmium(II), arsenic(III), zinc(II), iron(III) and lead(II) ions on the selenium response has been studied. In case of lead ions, a new signal occurred at more negative potentials than the reduction of Cu₂Se. This signal, which is probably due to the reduction of PbSe, can also be used for the determination of selenium(IV). Received: 13 November 1996 / Revised: 19 December 1996 / Accepted: 24 December 1996     

依诺沙星在碳糊电极上的阳极吸附伏安法研究

在0.40 mol/L的NaAc-HAc(pH 4.5)缓冲液中,使用JP-303极谱分析仪,依诺沙星在碳糊电极(CPE)上有一灵敏的吸附伏安氧化峰,峰电位为1.17 V(vs.SCE).该氧化峰的二阶导数峰电流与依诺沙星的浓度在4.0×10-9～4.0×10-7 mol/L(富集90 s)范围内呈良好的线性关系,相关系数为0.995,检出限为2.0×10-9 mol/L(S/N=3,富集110 s).探讨了依诺沙星在碳糊电极上的伏安性质和电极反应机理,并且用于诺佳胶囊中依诺沙星的测定.     

Anodic stripping voltammetry with mercury electrode potential-step and current-step methods

Prof. N. Tanaka (Sendai): (1) What is the difference of this method and the method proposed by Dr. Hickling? (2) How can this method be applied when two substances are present in the solution?Prof.P. Delahay: (1) If I recall correctly hickling in his work recently published [Anal. Chim. Acta, 14 (1956) 297] carries out the anodic oxidation with a stirred amalgam 1 would say that method is quite different from that of hickling. (2) The situation is similar to that in polarography. Both metals are deposited, and the potential first switched at a value at which only the nobler metal is oxidized. A second current-time curve is recorded at a potential at which both metals are oxidized. The concentration of the less noble metal is obtained by difference.Prof. H.A. Laitinen (Urbana): (1) What are the relative sensitivity limits of the potential step and current step methods? (2) Would Prof. Delahay care to comment on the application of these methods with solid microelectrodes? Here no diffusion can occur within the electrode and diffusion in the solution is ill-defined.Prof. P. Delahay: (i) Sensitivities are quite comparable although the potential-step method is more sensitive than the current-step method. (2) These methods can be applied to solid electrodes but a coulometric determination must then be made. Direct evaluation of the concentration from the current-time caracterstics (potential-time curves in the current-step method) is only possible when less than a monolayer is involved (or perhaps a few layers for a non-uniform deposit). See the recent work of nicholson published in J.Am.Chem.Soc.Dr. H. Gerischer (Stuttgart): (t) Wenn ich Sie recht verstanden habe, beruht die grosse Empfindlichkeit der Methode darauf, days eine elektrolitische Trennung und Anerkennung der Untersuchungssubstanz in dem kleinen Hg-Tropfen Erfolgt. (2) Wie wird die Auswertung des anodischen Stromstosses vorgenommen; durch einfache graphische Integration? (3) Glauben Sie nicht, dass die starke Konvektion in der Lösung auch eine Konvektion im Amalgam zur Folge hat, was zu einem weitgehenden Konzentrationsausgleich im Amalgam führen sollte wenn t relativ gross ist?Prof. P. Delahay: (1) The gain in sensitivity is indeed due to the extraction of the metal from the solution into a thin layer of mercury. The metal is deposited into mercury at a rate larger than that at which it can diffuse away. (2) There was no current integration but only direct measurement on the recorded current-time curve. (3) Convection obviously interferes but reproducible conditions can be achieved in analytical applications.Dr. Mechelynck (Mol, Belgique):Dans le cas ou les temps d'électrolyse sont longs, le gain expérimental est supérieur an gain théorique. Je pense qu'au point de vue analytique c'est un avantage, puisque ce phénomène, qui est dû à la sph$\text{'}\text{?}$ericité; de 1'électrode, est parfaitement reproductible si les électrolyses sont effectuées pendant (des temps identiques. Est-ce effectivement le cas?Prof. P. Delahay; Tout à fait d'accord. On est toutefois limité par la solubilité du métal dans le mercure.Prof. W. Kemula (Warsaw): Which substances have you studied? Have you met difficulties with purification of basic electrolytes?Prof. P. Delahay :Our study was limited to the development of some fundamental ideas and their verification and not with the details of application. We studied primarily cadmium. I might add that other metals were studied by nikei.ly and cooke in the work they reported at the Lisbon IUPAC meeting (see recent publication in Anal. Chem.).The purification of the supporting electrolyte is a serious problem. Another problem is the necessity of equilibrating the solution with its container. However, these difficulties are often common to many trace analysis methods.     

Simple and rapid determination of iodide in table salt by stripping potentiometry at a carbon-paste electrode

A simple and rapid procedure, utilising constant-current stripping analysis (CCSA) at a carbon-paste electrode containing tricresyl phosphate as a pasting liquid (TCP-CPE), has been developed for the determination of iodide in table salt. Because of a synergistic accumulation mechanism based on ion-pairing and extraction of iodide in combination with electrolytic pretreatment of the TCP-CPE, the method is selective for iodide and enables direct determination of iodide in samples of table salt containing anti-caking agents such as K(4)[Fe(CN)(6)] (food additive "E 536") or MgO. The iodide content (calculated as KI) can be determined in a concentration range of 2 to 100 mg kg(-1) salt, with a detection limit (S/N=3) of 1 mg kg(-1), and a recovery from 90 to 115%. The proposed method has been used to determine iodide in several types of artificially iodised table salt and in one sample of natural sea salt. The results obtained agreed well with those obtained by use of three independent reference methods (titration, spectrophotometry, and ICP-MS) used to validate the CCSA method, indicating that the developed method is applicable as a routine procedure for rapid testing in salt production process control and in the analysis of marketed table salts.