Cyclic voltammetry and chronoamperometry of lead ions at carbon fibre electrodes

Cyclic voltammetry of reversible redox couples. e.g., hexacyanoferrate (III)/(II), at carbon fibre electrodes yields sigmoidal anodic and cathodic scans that are almost superimposed. However, the cyclic voltammogram of lead (II) ions was markedly different. The voltammogram, and results from chronoamperometric measurements, can be interpreted on the basis of lead nucleation.     

Cyclic staircase voltammetry

The use of cyclic staircase voltammetry was investigated in order to study kinetic mechanisms at low concentration levels. The reversible case for c.s.c.v. was studied along with two common kinetic cases: e.c. and catalytic mechanism. For both the e.c. and catalytic case, it was possible to correlate the peak current ratio with the rate constant with one working curve regardless of the step size, the step time or the time in the step in which the current was measured. For the catalytic mechanism, the increase in the peak current of the forward peak can also be correlated with the rate constant, once again regardless of the experimental parameters. Using this technique, high sensitivity can be obtained at low concentrations and fast scan rates as was shown by comparing c.s.c.v. with cyclic voltammetry for micromolar cadmium solutions. The use of staircase voltammetry for the study of the catalytic reaction between iron (III)-triethanolamine and hydroxylamine was demonstrated and a rate constant of 180 M^?1 s^?1 was obtained, which is consistent with previous work.     

Cyclic voltammetry of phenol

The possibility of phenol determination by cyclic voltammetry (CVA) on electrochemically modified glassy-carbon electrodes (GCE) was studied. The effect of the rate of linear potential sweep on the sensitivity of phenol determination was investigated. The adsorption nature of the analytical signal of phenol was revealed. The formation of the hydroquinone-quinone couple by the electrochemical oxidation of phenol was proved by CVA.     

Cyclic voltammetry and differential pulse voltammetry of rescinnamine

Two redox processes can be4 observed for rescinnamine by cyclic voltammetry. The electroactive group is identified as the 3,4,5-trimethoxycinnamic. A mechanism including a homogenous dimerization reacyion following the electron transfer is proposed for the redoz process which occurs at less negative potentials, and the rate constant for the homogenous reactions is calculated. Differential pulse voltammetry is proved to be a suitable method for quantitative determination of the alkaloid.     

Cyclic voltammetry and voltabsorptometry studies of redox proteins immobilised on nanocrystalline tin dioxide electrodes

Protein film cyclic voltammetry is a well-established technique for the study of redox proteins immobilised on electrode surfaces. In this paper, we use nanostructured SnO(2) electrodes to demonstrate that cyclic voltabsorptometry is an effective, complimentary approach to such studies of protein redox function. We exemplify this approach using two different redox systems: microperoxidase-11 (MP-11) and flavodoxin Desulfovibrio vulgaris Hildenborough (Fld). Both systems were immobilised on nanocrystalline SnO(2) electrodes and the resulting films investigated by simultaneous cyclic voltammetry and voltabsorptometry. We demonstrate that cyclic voltabsorptometry allows the unambiguous and background free observation of redox reactions for both systems studied.     

Cyclic voltammetry at microstructured electrodes

We present the theoretical treatment of cyclic voltammograms at microstructured electrodes. Calculations of voltammograms permit the determination of electrochemical parameters of redox systems in a single cell in parallel with the determinations of the spectroscopic parameters. The structural parameters of the electrode can be determined using the theoretical treatment presented if the electrochemical parameters of the redox system are known. Furthermore, lithographic-galvanic (LIGA) structures can be used as a model for microporous electrodes. Regression analysis was used to compare experimental and calculated cyclic voltammograms as well as to determine the electrochemical and spectroscopic parameters. A modified Randles-Sevčik equation has been derived to described the peak current dependence of cyclic voltammograms at micro-structured electrodes for both reversible and quasi-reversible charge transfer.     

Cyclic voltammetry of copper in sodium hydroxide solutions

The cyclic voltammograms of the Cu electrode were, obtained in NaOH solution as a function of the voltage scanning rate, electrolyte concentration and voltage range. A correlation was made between three well-defined anodic peaks and their corresponding cathodic ones. The anodic peaks were found to correspond successively to the formation of a monolayer of Cu₂O, formation of a thick multilayer film of CuO and finally Cu₂O₃ upon which O₂ is evolved. It is suggested that CuO is formed from the oxidation of Cu₂O and/or direct oxidation of metallic copper.Below 0.1 M NaOH the ratio of anodic to cathodic charges was found to be about unity, indicating the quantitative reduction of solid oxidation products, while at higher alkali concentrations higher charge ratios were obtained due to increasing proportions of soluble reaction products.The behaviour of the copper electrode in NaOH was found to be quite complicated. Thus, no simple relations were found between the voltage scanning rate and both the peak current and peak potential or between the peak current and the alkali, concentration. Further work is needed to obtain a definitive explanation of this behaviour.     

Cyclic voltammetry of silyl- and stannyl-tricobalt cluster compounds

The electrochemical behavior of the clusters PhM′Co₃(CO)_n (M′ = Si, n = 11 and M′ = Sn, n = 12) has been examined via cyclic voltammetry in CH₂Cl₂ solution. In both cases the radical anions PhM′Co₃(CO)_n? are unstable, rearranging to Co(CO)₄ and other products. However, for the silicon compound, where there is one formal cobalt—cobalt bond, the radical anion is sufficiently stable to allow for detection of anion reoxidation at medium scan speeds. The half-life of PhSiCo₃(CO)₁₁? has been calculated as 2.3 s at 25°C.     

Cyclic voltammetry of iron dimine complexes in acetonitrile

The electrochemical behavior of iron diimine complexes, (H₃C?N=C(R)?C(R′)=N?CH₃)₃Fe(II) (R, R′=H,H;H, CH₃; CH₃, CH₃), and (C₅H₄N?C(R₁)=N(R₂))₃Fe(II) (R₁, R₂=H, CH₃; CH₃, CH₃) on a platinum working electrode in acetonitrile is described, and compared to that of the parent aromatic complex, tris-(2,2′-bipyridine)Fe(II). One-electron reversible oxidations were found for all the compounds studied. The electrochemical reductions show 2–3 reduction waves in the potential range studied. Only for the complexes of mixed diimine ligands or 2,2′-bipyridine, a pre-adsorption wave is also observed. It is possible to stabilize low valence states with all ligands studied. A formal iron(I) state is described for the first time for all aliphatic diimine complexes, thus showing that the acceptor properties of the diimine complexes do not depend on the presence of the aromatic rings, but on the iron-diimine chromophore.     

Simultaneous determination of lead,copper, cadmium and zinc in pure zirconium metal by differential-pulse anodic stripping voltammetry

Zirconium metal (ca. I g) was dissolved in hydrofluoric acid, excess of which was removed by fuming with sulphuric acid. An aliquot of this solution was treated with sodium citrate and adjusted to pH 4.5. Lead, copper and cadmium were deposited on the hanging mercury drop electrode by applying a potential of ?0.8 V vs. Ag/AgCl for 1 min and anodic stripping voltammograms were recorded; the anodic peaks appeared at ?0.51, ?0.14 and ?0.67 V, respectively. In a separate run, zinc was deposited at ?1.2 V and the stripping peak appeared at ?1.1 V. Standard additions were used to quantify these impurities at levels in the low mg kg^?1 range, with relative standard deviations of 5–11%.     

Spectroelectrochemistry on electroactive self-assembled monolayers: Cyclic voltammetry coupled to spectrophotometry

We present a spectroelectrochemical bench involving an electrochemical/spectrophotometric coupling dedicated to probe electroactive self-assembled monolayers (SAMs). This bench is validated by the study of the oxidation of a 5,5′-disubstituted-2,2′-bithiophene immobilized on Au substrate, producing a reversible dimerization of the radical cation (i.e. EC_Dim process) leading to a dimer. A direct comparison between thin layer spectroelectrochemistry in solution and spectroelectrochemistry on SAMs shows that a SAM could be viewed as a highly concentrated solution.     

Cyclic voltammetry and electrochemical quartz crystal microbalance studies of a rhodized platinum electrode in sulfuric acid solution

The adsorption properties of a rhodized platinum electrode in sulfuric acid were studied through simultaneous cyclic voltammetry (CV) and electrochemical quartz crystal microbalance (EQCM) measurements. The processes occurring at the Rh surface during the potential scan between 0.04 and 1.3 V were analyzed in terms of the changes in mass and charge. The apparent molar masses of the species adsorbed on Rh in different potential regions were determined from the mass–charge correlation. The results obtained suggest that the desorption of hydrogen UPD initially occurs in conjunction with the incorporation of mass due to the adsorption of bisulfate/sulfate ions between 0.04 V and 0.12 V; the apparent molar mass (M ₁) in this potential region is consistent with that of bisulfate ion, assuming that one sulfate species occupies the site originally occupied by five H atoms. Between 0.12 V and 0.20 V, the apparent molar mass, M ₂, is less than M ₁. This result may be associated with a structural rearrangement of the adsorbed sulfate species. The apparent molar mass, M ₃, was determined in the potential region of 0.20–0.56 V; the value obtained for M ₃ suggests that the adsorbed species are hydrated bisulfate ions (HSO₄⁻·4H₂O). Additionally, it was found that Rh oxides formed at the surface between 0.56 V and 1.3 V could not be directly identified from the correlation between charge and mass.     

Cyclic voltammetry and theoretical calculations of silyl-substituted 1,4-benzoquinones

Cyclic voltammograms of 2,3,5,6-tetrakis(trimethylsilyl)-1,4-benzoquinone (1a), 2,3,5,6-tetrakis(dimethylvinylsilyl)-1,4-benzoquinone (1b), 2,3,5,6-tetrakis(dimethylsilyl)-1,4-benzoquinone (1c), 4,4,6,6,10,10,12,12-octamethyl-4,6,10,12-tetrasilatricyclo[7.3.0.0^3,7]dodeca-1(9),3(7)-diene-2,8-dione (1d), and 5-t-butyl-2-(pentamethyldisilanyl)-1,4-benzoquinone (5h) showed that the first reduction step was reversible and that the second step was irreversible. The first half-wave reduction potentials of 1a, 1b, 1c, and 1d shifted negatively relative to 1,4-benzoquinone by −0.31, −0.24, −0.03, and −0.18 V, respectively. These results demonstrated that the electron-accepting ability of the chair-form quinones 1a and 1b was lower than that of the planar quinones 1c and 1d. The of 5h (−0.93 V vs. Ag/Ag⁺) was quite similar to that of 5-t-butyl-2-trimethylsilyl-1,4-benzoquinone (5a, −0.94 V). A cyclic voltammogram of dimethylsilylene-bridged 1,4-benzoquinone dimer 7 showed two kinds of (−0.76 and −0.94 V). The electrochemical behavior of 7 would be interpreted in terms of near-neighbor interactions between reduced and non-reduced quinone units. Theoretical calculations of the silyl-1,4-benzoquinones reproduced well the solid state structures of the compounds. Also, the computed vibrational frequencies of the silyl-1,4-benzoquinones were in good agreement with the IR absorption frequencies of the CO units in the compounds. The LUMO energy levels of the silyl-1,4-benzoquinones were quantitatively proportional to the .     

循环伏安法研究金属铅在硫酸溶液中形成PbO~2的过程

测取了硫酸浓度为0.5～5.1mol.dm^-^3、扫描速度为1～70mV/s的铅的循环伏安曲线.得到两个PbO~2形成峰I和II,相应地假设为PbO和PbSO~4的氧化.在较低的扫描速度下以及稀硫酸溶液中,峰值电位ψpI与扫描速度S几乎无关,峰值电流ipI近似地与(S)^1/2呈直线关系,并与PbSO~4在硫酸溶液中的溶解度相应,所以过程可能受Pb^2+离子在表面膜孔隙内的扩散所控制.在较高的扫描速度下,δψpi/δlogS=50mV,属于不可逆过程,对于峰II PbSO~4的氧化过程也进行了初步讨论.     

In-situ FT-IR studies on cyclic voltammetry of polythiophene

In-situ FT-IR spectra were taken during a cyclic voltammetric study of polythiophene in 1M LiClO₄ in propylene carbonate. The external reflection technique was used in the spectroscopic measurements. A broad band extending from 1500 cm^–1 to higher wave numbers appeared during oxidation of polythiophene with a potential scan from 2.8 V to 4.2 V. Bands due to doping of the polymer at 1330 and 1020 cm^–1 were also found to increase during the same potential scan. The appearance of spectral changes above 3.3 V supports the model of two types of doping processes occurring in the polymer. The observed changes almost disappeared during the reverse scan.     

Cyclic voltammetry responses of metastable gold electrodes in aqueous media

Ohne Zusammenfassung     

Cyclic voltammetry determination of epinephrine with a carbon fiber ultramicroelectrode

A carbon fiber ultramicroelectrode was used for the electroanalytical determination of epinephrine in biological fluids (urine) by cyclic voltammetry. The ultramicroelectrode was subjected to an electrochemical pretreatment in order to improve the epinephrine adsorption on the electrode surface. With this preconcetration step, detection limits of 7.8 ng ml(-1) and determination limits of 27.6 ng ml(-1) can be reached. The method was contrasted with native fluorescence determination-similar results were obtained.     

Cyclic voltammetry of biopolymer heparin at PVC plasticized liquid membrane

Cyclic voltammetry is used to study the charge transfer reaction of the biopolymer heparin at the PVC plasticized 1,6-dichlorohexane membrane–solution interface. Several unique feature of the reaction are demonstrated including the apparent diffusion control and the specific interaction of heparin with the cation of the membrane phase, which probably acts as the heparin carrier (ionophore). Voltammetric behaviour corresponds to the interfacial transfer of a mixture of polyanions with a relatively high content of polyanions carrying a low charge. Amperometry appears to be a suitable method for the quantification of heparin in various preparations with the sensitivity of ca. 1 U mL⁻¹ (S/N=3).