Catalytic effects of metal submonolayers formed by faradaic adsorption on the anodic oxidation of ascorbic acid at a platinum electrode

The catalytic effects of metal ions on the anodic oxidation of ascorbic acid on a Pt electrode in 1 M HClO₄ were studied by linear sweep voltammetry. The anodic peak due to a two-electron oxidation of ascorbic acid shifts to the negative potential side on the addition of Bi³⁺. This indicates the accelerating effect of Bi³⁺ on the oxidation of ascorbic acid. The presence of other metal ions, such as Pb²⁺, Hg²⁺, Tl⁺, Ag⁺ and Sb³⁺, also exerts similar effects. These metal ions were adsorbed on a Pt electrode at underpotentials and the adsorbed metals (denoted as M_ad) still remain on the electrode surface until the electrode potential goes up to and beyond the peak potential of the oxidation of ascorbic acid. On the other hand, metal ions forming no adsorbed layer on Pt, such as Co²⁺, Zn²⁺, Fe³⁺ and Ni²⁺, exhibit no catalytic effect. These facts suggest that the presence of a M_ad on Pt is essential for the promotion of the anodic oxidation of ascorbic acid. However, there is a difference in the catalytic action among the M_ad, for example, Cu_ad, Cd_ad, In_ad, Sn_ad and Mo_ad display no catalytic action.The catalytic activity depends on the degree of surface coverage by the M_ad. The maximal effect of the M_ad is attained in the submonolayer region. The effects of metal ions were discussed on the basis that the M_ad plays its major role in the removal of the adsorbed ascorbic acid occupying active sites on the electrode surface, and provides effective sites for the activation of adjacent water molecules. Furthermore, from the ¹³C NMR spectra for the oxidation products, the adsorbed water on the M_ad appears to function by promoting the subsequent hydration steps, following the electron-transfer step of ascorbic acid.     

Ring-disk electrode studies of the open-circuit dissolution of iodine films formed during the anodic oxidation of iodide on platinum

The open-circuit behavior of iodine films formed on platinum by electrooxidation of iodide was studied at rotating disk and rotating ring-disk electrodes. The potential transient and ring current transient at open circuit for c_I^?>0.012 M can be explained by assuming: (1) convective-diffusion controlled dissolution of the film; (2) establishment of the I₂+I^?→ I₃^? equilibrium; (3) establishment of the I₂ (solid) →I₂ (solution) equilibrium. The behavior at lower concentrations of c_I^? suggests that convective-diffusion control is absent.     

The anodic oxidation of fluorene and some of its derivatives: Conditions for the formation of a new conducting polymer

Quinones undergo a one-step two-electron reduction in molten acetamide at the mercury and platinum electrodes. The reversibility of reduction increases in the order benzoquinone < napthaquinone = phenanthrquinone < anthraquinone.     

Influence of ph on the reduction of thick anodic oxide films on gold

The reduction of thick oxide films, produced anodically on gold under constant potential conditions in the oxygen gas evolution region, was examined as a function of sweep-rate in both acid and base. Although peak maxima potential values for the reduction reactions were not totally independent of sweep-rate, even at very low values of the latter, the earlier assumption that the film is composed of at least two (and in some cases, according to the present results, as many as five) different oxygold species was shown to be a reasonable one. The other assumption, namely that the hydrous film in the case of gold is anionic (due to excess hydroxide-ion incorporation) was also shown to be a reasonable one by comparison with recent work with hydrous nickel oxide films for which structural data is available. In these systems counterbalancing cations (H⁺, Na⁺, etc.) are assumed to be present in water contained in pores or layers in the structure. Furthermore, the unusual potential-pH dependence of the hydrous film reduction process can easily be explained in terms of the excess hydroxide incorporation model.     

Structurally heterogeneous electrode films of polyacrylamide and acrylamide/vinylpyridine copolymeric gels: Mediation of ascorbic acid oxidation

The surface chemistry, i.e. adsorption and surface phase formation, on Rh, Ir, Pt and Au single-crystal electrodes in 0.5 M H₂SO₄ has been studied in the potential range between 0 and 4 V vs. a standard hydrogen electrode by X-ray photoelectron spectroscopy and cyclic voltammetry. Both methods gave complementary results which were interpreted as potential-dependent changes from physisorption of water to adsorption of hydroxyl groups, hydroxide film formation, and eventual growth of thick adlayers of oxyhydroxide (Rh, Ir and Au) or hydroxide (Pt) with increasing applied voltage.     

The formation and reduction of anodic films on electrodeposited ruthenium

The formation and reduction of anodic films on bright ruthenium was investigated using substrates prepared by electrodeposition onto gold-plated platinum from a commercial ruthenium bath operated at 70°C. Anodic films formed on the ruthenium may be reduced by maintaining the electrode at potentials below 0.2 V. The reduction behaviour was markedly affected by the anodization potential and, at short times, by the period of anodization. The bell-shaped cathodic current-time curves observed with films produced at potentials in the region of 1.2 V, suggest that the process in this case involves nucleation of reduction centres on a relatively stable surface layer. The influence of potential, time, and both the concentration and nature of the electrolyte on the extent of anodic film formation was investigated. The results are discussed in terms of the formation of stable phase oxides in the relatively thick anodic film produced on the ruthenium surface.     

Synergistic effect in the electrocatalytic oxidation of methanol on platinum+palladium alloy electrodes

The electrocatalytic oxidation of methanol has been investigated on platinium+palladium alloy electrodes of different compositions in acid, neutral and alkaline aqueous solutions.The surface characteristics (composition and roughness factor) of the alloys and the stability of the electrodes in contact with different electrolytic solutions have been studied using cyclic voltammetry. In particular, a surface enrichment in platinum due to a preferential dissolution of palladium and an increase of the roughness factor with an increase of the palladium content has been shown.The electrocatalytic activity of different alloys for methanol oxidation has been characterized by exchange current densities obtained from extrapolation of Tafel lines of calculated equilibrium potential. The plot of these current densities vs. the surface composition leads to a synergistic effect, particularly important in alkaline medium. A reasonable explanation of this enhanced electroactivity at about 15 at.% in Pd is given on the basis of a decrease of electrode poisoning.     

Supramolecular phenomena in organic redox films at electrodes: Part I. The methylene blue/leucomethylene blue redox couple at the platinum electrode

It is possible to generate conductive multilayer structures by reduction of methylene blue cations at the interface: clean surface of a platinum electrode/1 M aqueous electrolyte solution.The characteristics of the multilayer ordered phase generated in fluoride and nitrate solutions are presented and the mechanism of a fast charge transfer between electrode/organic film and organic film/aqueous solution interfaces is discussed. The conductivity of the film is interpreted by postulating formation of a mixed valence structure with the generation of a cation radical intermediate which is favoured in the solid state at characteristic potentials.     

Direct potentiometric titration of thiosulfate,thiourea, and ascorbic acid with lodate using an iodide ion-selective electrode

A potentiometric method has been developed for the semi-automatic direct titration of thiourea, thiosulfate, and ascorbic acid with potassium iodate in strongly acidic solutions using an iodide ion-selective electrode to monitor the reaction and locate the endpoint. The method is simple, fast, precise, and accurate. Amounts ranging from 0.15–1.5 mg of thiourea (3.9 × 10^?4–3.9 × 10^?3, M), 0.3–3.0 mg of thiosulfate (5.4 × 10^?4–5.4 × 10^?3, M), and 0.5–5.0 mg of ascorbic acid (5.7 × 10^?4–5.7 × 10^?3, M) have been determined with an average error of about 1%. The method has been applied to the determination of ascorbic acid in tablets. Results checked closely with those obtained with a standard titrimetric method.     

Voltammetric,chronoamperometric and chronoabsorptometric studies of the nucleation of n-heptyl viologen films on SnO2, silane-modified SnO2 and ion-beam-treated ito-metallized polymer films

Nucleation of the first monolayers of the n-heptyl viologen-bromide or-biphthalate films on SnO₂ electrodes was found to be accelerated by the addition of one molecular layer of dimethyldiethoxy (dmde)-silane to the SnO₂ surface. Partitioning of the reactant viologen into the non-polar surface layer and lowering of the surface tension against nucleation site growth in the silane layer may both be responsible for the enhanced nucleation rates. Similar acceleration of the nucleation of n-HV⁺ was found on ion-beam-etched indium-tin oxide-metallized polymer electrodes (MPOTE). A second nucleation site with a much lower, and distinguishable rate of nucleation, was produced on this type of electrode surface. Chronoamperometry and chronoabsorptometry were used to confirm that the nucleation of n-heptyl viologen cation-radical salts follows an instantaneous rather than progressive nucleation mechanism, on any of the surfaces studied.     

Electrochemical formation of stable ferrocene anion and the formal rate constant of the ferrocene0/− electrode

A reversible cyclic voltammogram for the one-electron reduction of ferrocene in 1,2-dimethoxyethane is recorded under experimental conditions that enable the ferrocene anion to exist for a few minutes. The formal rate constant of the ferrocene^0/? electrode, determined by cyclic voltammetry at ?45°C, ca. 10^?3 cm s^?1, is in striking contrast with that of ferrocene^+/0, > 10^?1 cm s^?1. The distortion of the ferrocene molecule caused by reduction may be a reason for this difference in electron-transfer rate.     

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.     

Polymer films on electrodes: Part III. Digital simulation model for cyclic voltammetry of electroactive polymer film and electrochemistry of poly(vinylferrocene) on platinum

The electrochemistry of electrodeposited poly(vinylferrocene) (PVF) and poly(vinylferrocene acrylonitrile) (PVFAN) films on platinum electrodes was studied in acetonitrile solutions using perchlorate or p-toluenesulfonate as the counter ion by cyclic voltammetry. A model is proposed for the cyclic voltammetric behavior of polymeric films on electrode surfaces. The model incorporates non-equivalent redox sites with interconversion between such sites, electron-transfer kinetics at substrate/film interface and diffusion within the film. Parameters are obtained which yield a good fit to the experimental results.     

Differential double-layer capacitance of a mercury-drop electrode attached to a platinum wire: Frequency dispersion due to the measuring bridge and to the geometry at pendant and sessile electrodes

The frequency dependence of the double-layer capacitance has been studied at the interface Hg/0.116 M KCl in water at ?1.200 V vs. a reversible calomel electrode at 25°C. Two drop electrodes attached to 0.1-mm platinum wire have been used, one sessile with a narrow wedge, the other pendant with a widely open wedge between drop surface and support. The operation of the a.c. resistor-ratio arms bridge has been analysed in a manner generally applicable to series-R, C measurements. On that basis the effect of stray capacitances could be compensated and the frequency dispersion due to the measuring system reduced to a minimum. Both electrodes show a low-frequency dispersion of the measured series capacitance C(ω) and resistance R(ω), ω being the angular frequency. This dispersion has been analysed with a simple R, C network. In series with the bulk resistance R₃ this network has two mutually parallel series R, C's: R₁, C₁ of the drop itself and R₂, C₂ of its edge (neck). From the actual C(ω), R(ω) data follow correct capacitance data C₁, while R₂ and C₂ show a relatively stronger dependence on frequency and kind of electrode (pendant or sessile). Moreover, a sessile electrode exhibits a wedge or shielding effect above a much smaller ω (=ω_h >ω₁, the frequency above which the edge effect becomes insignificant) than a pendant electrode. Conclusions drawn from this information are: in the frequency domain (ω_h?ω₁) diffusive mass transport may be studied without interference from any geometric effect, which is probably also true at small electrolyte concentrations. This study should be performed with a pendant electrode, since it has the largest (ω_h?ω₁) domain.     

Polarographic studies on the electrode kinetics of the nickel(II) complexes with glycine and some of its derivatives: I. glycine complexes

D.C. polarograms of the Ni(II)-glycine complexes were measured with varying pH values at constant total glycine concentration (0.05 M) and conversely with varying total glycine concentration at constant pH values (3.5, 4.5, 7.5 and 9.5). The current—voltage curves obtained were analysed to determine the limiting currents, the transfer coefficients, and the half-wave potentials, by using the non-linear least squares method. From the dependence of the half-wave potentials on the free glycine concentration, the mechanism of the electrode processes was elucidated. It was shown that the first wave corresponded to the reduction of the Ni²⁺ aquo-complex, the second to the NiG⁺ complex, the third to the NiG₂ complex and the fourth to the NiG^?₃ complex. The kinetic parameters for the four charge transfer processes were determined.The second and third waves were kinetic in character and the rate constants of the dissociation and association reactions between NiG⁺ and NiG₂ and between NiG₂ and NiG^?₃ were determined by analysing the dependence of the kinetic limiting currents on the free glycine concentration.     

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.