Silver based mercury film electrode: Part IV. Comparison of theoretical and experimental voltammetric results obtained for cadmium

Using the silver based mercury film electrode (SBMFE) and cyclic and stripping voltammetric techniques the behaviour of cadmium has been compared with the behaviour of lead as well as with the predictions of the theory of de Vries and van Dalen. At the SBMFE with film thickness between 0.1 and 2 μm lead behaves with good agreement with theoretical predictions and only at thicknesses higher than 2 μm some deviations occur due to collecting of the excess mercury at the bottom of the wire electrode. On the other hand even at thin film electrodes the behaviour of cadmium deviates significantly from the predictions of the theory. The height of the anodic peak decreases and its width increases; also the displacement of the potentials of both cathodic and anodic peaks is smaller than the values predicted theoretically. The deviations are caused neither by the formation of intermetallic compounds in the bulk of mercury phase nor by the formation of heterogenous cadmium amalgam; they reflect the interaction between cadmium dissolved in mercury and the solid silver amalgam which is the substrate of the mercury film. Owing to the effect discussed the stripping determination of cadmium at SBMFE is characterized by a lower sensitivity and reproducibility.     

The dependence of the kinetics of some simple outer-sphere electrode reactions on the nature of the electrode material

The kinetics of a number of simple inorganic electrode reactions that are known or expected to follow outer-sphere pathways have been examined at mercury, silver, platinum, and gold-aqueous interfaces in order to explore the effects of varying the electrode material on outer-sphere reactivity. The electroreduction kinetics of Co(III) ammine complexes exhibited only mild dependences on the nature of the electrode material which were compatible with the expected variations in double-layer effects. However, the electrooxidation of Cr²⁺ proceeded at strikingly higher overpotentials on the solid surfaces compared with mercury electrodes. Similar effects were also seen for the electrooxidation of V²⁺, Eu²⁺ and Ru²⁺ in the presence of Cr²⁺. Much larger rate constants were observed for these aquo reactions at solid surfaces in the absence of Cr²⁺, although Cr²⁺ had no influence on Co(NH₃)₆³⁺ electroreduction, or any reaction at mercury electrodes. It is speculated that the very large substrate effects upon the electrode kinetics of aquo couples arise from the influence of the inner-layer water structure on the reactant-solvent interactions experienced by these “structure-making” reactants at their plane of closest approach. The inhibiting influence of Cr²⁺ may be due to its ability to efficiently remove adsorbed catalytic contaminants by incorporation into a substitutionally inert Cr(III) electrooxidation product by means of a ligand-bridge mechanism.     

Graphite multi-micro-disc based mercury film electrode: Comparison of experimental and theoretical anodic stripping results

an ensemble of properly distanced micro mercury film electrodes (MMFE) was used in cyclic and anodic stripping voltammetry. the experimental results were compared with the anodic stripping theory, and the agreement was found to be satisfactory. The MMFE peaks (calculated per unit area) were higher, thinner and shifted towards more negative potentials compared with the large area mercury film electrode (LAMFE) peaks.The initial graphite electrode consisted of 65 independent micro-discs forming a circle, and was prepared from carbon fibres 4.66 μm in radius. The graphite multi-micro-disc electrode was quantitatively checked in a Fe(CN)₆^3? solution under both chronoamperometric and voltammetric conditions. The deposition and oxidation of mercury is discussed also.     

Development of cysteine-modified screen-printed electrode for the chronopotentiometric stripping analysis of cadmium(II) in wastewater and soil extracts

Screen-printed carbon electrodes were fabricated with amino acid functionality by using in situ co-deposition of mercury and cysteine. The three-electrode configuration (graphite carbon working electrode, carbon counter electrode and silver/silver chloride reference electrode) incorporating a cysteine-modified working electrode exhibited good sensitivity towards cadmium(II). Several experimental variables affecting the sensor stripping response were characterised and optimised. These include cysteine and mercury concentrations, deposition time, deposition potential and stripping current. Surface analysis was also conducted using scanning electron microscopy (SEM) in order to characterize the electrode surface during cadmium analysis. The stripping chronopotentiometric response for cadmium(II) was linear in the concentration range 0.4–800 g L^–1 when a deposition time of 2 min was used. A detection limit of 0.4 g L^–1 was obtained using 0.025 M Tris–HCl buffer containing 0.1 M KCl (pH 7.4) as the supporting electrolyte. The analytical utility of the cysteine-modified sensor was demonstrated by applying it to cadmium analysis in various wastewater and soil samples collected from a contaminated site and extracted using acetic acid. The results obtained using the developed electrodes agreed satisfactorily with the values achieved using atomic absorption spectrometry and inductively coupled plasma mass spectrometry analysis. These results demonstrate the feasibility of using this type of sensor for cadmium analysis.     

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.     

Voltammetric behavior and trace determination of Pb at a mercury-free screen-printed silver electrode

Screen-printed silver electrodes (AgSPEs), without chemical modification, has been investigated as disposable sensors for the measurement of trace levels of Pb²⁺. Potential segment analysis indicates that the formation of underpotential and bulk depositions of Pb is not strongly coupled on the AgSPE. The possibility of determining Pb²⁺ at trace levels using the reversible underpotential deposition peak was examined by square-wave anodic stripping voltammetry without removal of oxygen. Under the optimized analytical conditions, the obtained sensitivity, linearity, and detection limit are 0.355 μA/ppb, 5-80 ppb (r=0.9992), and 0.46 ppb (S/N=3), respectively. The electrode is quite stable for repetitive measurements. The interference effect was thoroughly studied with various metals and no significant change in current was found in the determination of 5 ppb Pb²⁺. The practical applications were demonstrated to measure trace Pb²⁺ in natural waters.     

Direct determination of traces of silver in mercury by voltammetry at the hanging mercury drop electrode in acetonitrile medium

A direct method for the determination of silver in mercury is described. The sample of mercury is introduced into the container of the hanging mercury drop electrode and the anodic voltammograms are recorded in a 0.1 M lithium perchlorate solution in acetonitrile. The anodic peak of silver obtained under these conditions is well separated from the mercury dissolution current. The peak height is proportional to silver concentration over the wide range 2 × 10^?6 mol dm^?3 (1.6 × 10^?6%) to at least 2.0 × 10^?2 mol dm^?3. No prior separation is needed; the procedure requires less than 20 min. The diffusion coefficient of silver in mercury was determined at several temperatures. It was found that silver in mercury does not form intermetallic compounds with copper, lead, thallium, cadmium, tin and bismuth.     

Optimisation of mercury film deposition on glassy carbon electrodes: evaluation of the combined effects of pH, thiocyanate ion and deposition potential

The combined effects of pH, thiocyanate ion and deposition potential in the characteristics of thin mercury film electrodes plated on glassy carbon surfaces are evaluated. Charges of deposited mercury are used as an experimental parameter for the estimation of the effectiveness of the mercury deposition procedure. The sensitivity of the anodic stripping voltammetry (ASV) method for the determination of lead at in situ and at ex situ formed thin mercury films are also examined. It was concluded that, in acidic solutions (pH 2.5-5.7) and fairly negative deposition potentials, e.g. −1.3 to −1.5 V, thiocyanate ion promotes the formation of the mercury film, in respect both to the amount of deposited mercury and to the mercury deposition rate. Also, the mercury coatings produced in thiocyanate solutions are more homogeneous, as depicted by microscopic examinations. In the presence of thiocyanate there is no obvious advantage of using high concentrations of mercury and/or high deposition times for the in situ and ex situ preparation of the mercury film electrodes. The optimised thin mercury film electrode ex situ prepared in a 5.0 mM thiocyanate solution of pH 3.4 was successfully applied to the ASV determination of lead and copper in acidified seawater (pH 2). The limit of detection (3σ) was 6×10⁻¹¹ M for lead and 2×10⁻¹⁰ M for copper for a deposition time of 5 min. Relative standard deviations (R.S.D.s) of <1.2% were obtained for determinations at the nanomolar of concentration level.     

Gold electrodes from recordable CDs for mercury quantification by flow injection analysis

The development of a new methodology for the construction of very efficient flow cells for mercury detection by potentiometric stripping analysis, employing the thin gold layer of recordable CDs as working ¶electrode is reported. This new source of electrodes (CDtrodes) show very attractive performance, similar to that obtained with commercial gold electrodes, with superior versatility. The low cost of this new source of “gold electrodes” allows a frequent replacement of the electrode, avoiding cumbersome clean-up treatments. Various experimental parameters have been optimized to yield low detection limits (0.25 ng/mL of mercury for 5 min deposition at 0.3 V) and good precision (standard deviation of 1.9% was obtained for 15 repetitive measurements using 10 ng/mL of mercury). Standard curves were found to be linear over the range of 0.5–100 μg L^–1 of mercury. The flow cells developed were used for the quantification of mercury in oceanic and tap water.     

Voltammetry at the mercury film electrodes: Comparison of theoretical and experimental results obtained for indium in thiocyanate medium

The voltammetric behaviour of the In(III)-In(Hg) system was studied at the silver-, graphite-, and glassy carbon-based mercury film electrodes under cyclic and stripping conditions in thiocyanate media. The reversible curves obtained at high thiocyanate ion concentration showed a good agreement with theoretical predictions, particularly for the cathodic process. The anodic curves obtained at thin silver-based mercury film electrodes deviated from theoretical predictions due to the interactions between indium, dissolved in mercury, and the silver substrate of the film electrode. At low thiocyanate ion concentrations, where the current was controlled partly by the rate of the preceding chemical step and partly by diffusion, the variations in the film thickness affected the position of the curve as predicted theoretically for the reversible diffusion controlled case.     

Anodic behaviour of the (222) macrobicyclic ligand on mercury electrode in propylenecarbonate

The anodic behaviour of the free macrobicyclic ligand (222) was examined by various electrochemical techniques on mercury and on platinum electrodes. From results on platinum electrode using cyclic voltammetry it appears that the anodic oxidation of (222) proceeds irreversibly at potentials more positive than +0.7 V (aq. SCE), however, its mechanism could not be determined because the anodic signal was not well developed. Under polarographic conditions a reversible anodic diffusion controlled wave at E_1/2=+0.08 V (aq. SCE) was observed, corresponding to a complex formation of the ligand (222) with the ions of mercury formed by anodic polarization of mercury electrode. In excess of mercuric cations a cathodic wave at slightly more positive potentals was found.     

Anodic stripping voltammetry at a micro-disc mercury film electrode: Theory of the reversible case

For p=(ar²/D_O)^1/2<0.12 and H=al²/D_R<0.14, simple theoretical equations are proposed to characterize the reversible anodic stripping voltammetric peaks of amalgams obtained with a micro-disc mercury film electrode. The calculated, normalized peaks were higher, thinner and shifted towards more negative potentials compared with the peaks described for the regular size mercury film electrodes. The ADI method was used in calculations.     

Electrodeposition and anodic stripping of silver on single carbon fibers

Silver is deposited electrolytically on carbon fibers from acetate buffer at pH 4.6 in the potential range from ?0.3 to ?0.8 V vs. SCE. Chronoamperometric and cyclic voltammetric measurements confirm that the mecanism of deposition is nucleation; the rate is higher than that at large circular glassy carbon electrodes. The silver deposits are more stable, especially with respect to oxidation by air, than are similar deposits of mercury. Preliminary results on codeposition of silver and mercury are reported.     

Nickel pentacyanonitrosylferrate film modified aluminum electrode for electrocatalytic oxidation of hydrazine

The electrocatalytic oxidation of hydrazine at the aluminum electrode, modified by electroless deposition of nickel pentacyanonitrosylferrate (NiPCNF) on the surface of the electrode has been studied by cyclic voltammetry, chronoamperometry and rotating disk electrode voltammetry and the kinetics of the catalytic reaction were investigated. The results were explained using the theory of electrocatalytic reactions at chemically modified electrodes. It was found that a one-electron charge-transfer process is rate limiting and that the average values of the rate constant for the catalytic reaction and the diffusion coefficient, evaluated by different approaches, are 5.2×10³ M^–1s^–1 and 8.5×10^–6 cm²s^–1, respectively. Further examinations of the modified electrodes show that the modifying layers (NiPCNF) on the aluminum substrate have reproducible behavior and a high level of stability, after exposing them in air and hydrazine solutions for a long time. Electronic Publication     

Determination of low levels of cyanide with a silver/silver sulphide wire electrode

A silver/silver sulphide electrode is prepred quickly by holding a cleaned silver wire in vapours from molten sulphur. In 1000–10 mg l^?1 cyanide solutions, the electrode exhibits a linear E/log C_CN function which becomes slightly sinusoidal for 10–0.1 mg l^–1 cyanide. The average slope is slightl super-Nerstian (10 mV/decade concentration). The applicability of the electrode is demonstrated for the determinations of microgram quantities of water-soluble cyanide from the Prussian blue pigments which are constituents of externally applied cosmetics. The home-made electrode provides results agreing with those obtained with commercially available electrodes.     

Voltammetric and chronoamperometric investigation of germanium amalgams: Part I. Properties of the homogenous amalgam

Using cyclic voltammetry and chronoamperometry with several anodic steps the deposition and particularly the oxidation of germanium from a HMDE was investigated within pH range 4–12 at Ge (IV) concentrations ranging from 4×10^?7M to 1×10^?4M in the absence of ligands capable to form the complex compounds with Ge(IV) in a solution. It was found that the initially formed product of electrodeposition is a homogeneous, usually supersaturated amalgam. Germanium from this amalgam oxidizes at about 1 V (vs. mercury sulphate reference electrode) or after some induction period, the length of which depends on concentration of Ge(0) in mercury, it begins to crystallize forming heterogenous germanium amalgam. Germanium from this heterogenous amalgam oxidizes in a separate voltammetric peak at more positive potentials. The solubility of germanium in mercury was evaluated on the basis of the oxidation current of homogenous amalgam and the value obtained is equal to (2±0.5)×10^?7M i.e. (1.1±0.3)×10^?7 wt. %. Applying the Stevens and Shain method the diffusion coefficient of germanium in mercury was found to be (1.32±0.1)×10^?5 cm² s^?1.     

Anodic behaviour of 2-mercaptoethanol at a mercury electrode

The anodic processes which occur at the mercury electrode in 2-mercaptoethanol solutions are studied by various polarographic techniques (d.c., a.c. and differential pulse), controlled-potential coulometry, cyclic voltammetry and differential capacity curves. Two steps are distinguished in the process: a one-electron charge transfer and a dismutation step leading to the formation of a mercury(II) mercaptide. The final product is isolated and analyzed. Differential-pulse polarography can be used to determine ?10^?4 M 2-mercaptoethanol with a limit of M.     

Reaction mechanism of the benzoquinone/hydroquinone couple at platinum electrodes in aqueous solutions: Retardation and enhancement of electrode kinetics by single chemisorbed layers

The electrochemical kinetics of the benzoquinone (Q)/hydroquinone (H₂Q) redox couple at platinum electrodes in aqueous solutions has been found to be extremely sensitive to the nature of species adsorbed on the electrode surface at monolayer coverages. Experimental measurements were based on thin-layer cyclic voltammetry; the use of thin-layer electrodes was dictated by the need to minimize surface contamination. Bulky neutral or anionic aromatic adsorbates led to the familiar U-shaped rate-vs.-pH curves; the rate minimum occurred near pH 4. Kinetic effects due to oriental changes of chemisorbed species were noted only when the rate was low. Adsorbed 1 atoms led to comparatively rapid reactivity (rate constant k° > 10^?3 cm s^?1) and virtual independence of pH. Profound retardation resulted from pretreatment ofthe surface with CN^? and SCN^?; total irreversibility (k° < 10^?6 cm s^?1) was observed at pH 4, with a further decrease in rate at pH 7. In contrast, when the surface contained n layer of chemisorbed phenyltriethylammonium cations, the electrode rate increased with increasing pH. The results indicate that different reaction pathways predominate when different absorbates are present.     

Crystallic silver amalgam--a novel electrode material

A crystallic silver amalgam was found to be a suitable working electrode material for voltammetric determination of electrochemically reducible organic nitro-compounds. Optimum conditions for crystal growth were found, the crystal surface was investigated by atomic force microscopy in tapping mode and single crystals were used for the preparation of quasi-cylindrical single crystal silver amalgam electrode (CAgAE). An electrochemical behavior of this alternative electrode material was investigated in aqueous media by direct current voltammetry, cyclic voltammetry (CV), differential pulse voltammetry (DPV) and adsorptive stripping voltammetry (AdSV) using 4-nitrophenol as a model compound. Applicable potential windows of the CAgAE were found comparable with those obtained at a hanging mercury drop electrode, providing high hydrogen overpotential, and polished silver solid amalgam electrode. Thanks to the smooth single crystal electrode surface, the effect of the passivation is not too pronounced, direct DPV determination of 100 μmol l(-1) of 4-nitrophenol at CAgAEs in 0.2 mol l(-1) acetate buffer pH 4.8 provides a RSD around 1.5% (n = 15). DPV calibration curves of 4-nitrophenol are linear in the whole concentration range 1-100 μmol l(-1) with a limit of quantification of 1.5 μmol l(-1). The attempt to increase sensitivity by application of AdSV was not successful. The mechanism of 4-nitrophenol reduction at CAgAE was investigated by CV.     

Influence of chemical composition of electrode material on the differential capacitance characteristics of the ionic liquid | electrode interface

The electrical double layer structure at polycrystalline metal | ionic liquid interface has been studied using cyclic voltammetry, electrochemical impedance spectroscopy and in situ infrared methods. Polycrystalline Bi(PC), Pb(PC), Au(PC) and Pt(PC) electrodes have been prepared using ultra-high vacuum magnetron sputtering method. Noticeable dependence of differential capacitance on the electrode potential has been observed. For all electrodes, a wide well-expressed minimum in capacitance, potential (C, E) curve has been shown. For graphene, C(0001), carbide-derived carbon and Bi(PC) U-shaped curves and for Pb(PC), Au(PC) and Pt(PC) M-shaped C, E curves have been measured. Dependence of the C, E curve shape on the electrode chemical composition has been explained by the different position of the image plane of surface charge, dependent on the electronic characteristics of the electrodes under study.