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1.
p-Phenylenediamine oxidation at platinum electrodes in acetonitrile solutions has been studied under a very wide range of experimental conditions. Chronopotentiometry, rotating disc electrode and cyclic voltammetry were used as electrochemical techniques. Coulometry at constant potential and product analysis were also performed.The electrochemical reaction appears as a fast and reversible one electron exchange per molecule of PPD. The electrode reaction is further complicated by follow-up chemical reactions giving unknown products in the bulk of the solution.The whole polarization curve under steady state conditions shows two waves, while under non-steady state conditions a small wave at intermediate potentials is also apparent.The reaction pathway for the first wave was interpreted as a non-conventional e.c.e. mechanism where the parent molecule acts as a base in the chemical step.These assumptions were confirmed through experiments performed with pyridine or water addition.  相似文献   

2.
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.  相似文献   

3.
The time evolution of a self-sustained potential oscillation under constant current oxidation of formaldehyde was observed on the rotating ring disk electrode assemble. Under the condition when the potential was controlled, the laser deflection voltammogram as well as the conventional cyclic voltammogram were measured. The mechanism of the multi-electron oxidationof formaldhyde on a platinum electode is discussed.  相似文献   

4.
6 and 7-substituted 2-amino-4-hydroxy-5,6,7,8-tetrahydropteridines are oxidized at a platinum electrode in several waves in the potential range between hydrogen and oxygen evolution potentials. The electrode process in the first (main) anodic wave was investigated in more detail using a stationary and rotating disc platinum electrode. The process in this wave is “semireversible” with an exchange of two electrons. The standard rate constants of this reaction were determined. The oxidation product is deactivated by an irreversible chemical reaction. Some of the products block the surface of the electrode.  相似文献   

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The electrochemical formation of a Ni(III)-EDTA (EDTA=ethylenediaminetetra-acetate) precipitate on a Pt electrode is observed. This precipitate can be reduced without dissolution. The electrochemical properties of this precipitate are analysed and compared with those of other tervalent nickel complexes.  相似文献   

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<正>The electrocatalytic oxidation of methanol at the platinum electrode modified with Eu-Fe cyanide-bridged binuclear complexes (Eu-Fe film) was investigated for the first time by cyclic voltammetry.Compared with the bare platinum electrode,the results showed that the modified electrode had excellent electrocatalytic activity for the oxidation of methanol;the oxidation peak potential shifted more negatively and the peak current increased about twenty times.The electrooxidation of methanol at the modified electrode with Eu-Fe cyanide-bridged binuclear complexes material exhibited the better tolerance capacity to poison of intermediate species;the peak current was proportional to the concentration of methanol in the range of 0.5-2.0mol/L (R~2 = 0.9991,n =7),which was a comparatively wider linear range.Moreover,based on the linear relationship between the peak current and the square root of scan rate,electrocatalytic oxidation process of methanol was confirmed to be a diffusion control process.Furthermore,according to the counting of electron transfer number(n_α) in the rate-limiting step and the slope of linear equation between acidity of electrolyte and the oxidation peak potential(E_p),the possible mechanism of the electrooxidation of methanol at the modified electrode was primarily discussed.  相似文献   

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The oxidation processes of cyanide and cyanate ions on a Pt electrode in aqueous and methanol solutions were studied by infrared spectroscopy. In aqueous solution, the cyanide ion was oxidized to cyanate and successively to carbon dioxide. The reaction proceeded on an oxidized platinum surface. In methanol solution, HNCO is the main product during anodization.  相似文献   

12.
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 Mad) 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 Mad 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 Mad, for example, Cuad, Cdad, Inad, Snad and Moad display no catalytic action.The catalytic activity depends on the degree of surface coverage by the Mad. The maximal effect of the Mad is attained in the submonolayer region. The effects of metal ions were discussed on the basis that the Mad 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 Mad appears to function by promoting the subsequent hydration steps, following the electron-transfer step of ascorbic acid.  相似文献   

13.
The influence of adsorbed tin and tin(IV) ions on the oxidation of methanol chemisorbed species as well as the methanol from the bulk of the solution was studied on a Pt electrode by voltammetric and radiometric methods. It was found that tin is not adsorbed as an ad-atom but rather as a divalent ion. Enhancement of the electrocatalytic oxidation of chemisorbed species derived from methanol was observed only in the potential range from 0.4 to 0.8 V. The influence of some factors on the electrocatalytic properties of platinum is discussed.  相似文献   

14.
Both platinum(II) and the total amount of platinum were determined in the 5-μmole range with a precision of 0.3%. First, platinum(II) was determined dy oxidation with electrogenerated bromine,the equivalent quantity of electricity being measured. After reduction to platinum(II) with electrogenarated tin(II), the total amount of platinum was determined by a second oxidation with electrogenerated bromine.The reduction with tin(II) was too slow for manual control, and an electronic coulometric titrator was used.The construction of the tritator is described. The underlying coulometric principle, called controlled-reagent coulometry, and its adventages are discussed. A number of other substances were also tested.  相似文献   

15.
Ferrocene attached to the surface of a platinum electrode catalyses the electrochemical oxidation of ascorbic acid in acidic buffer solutions. The overpotential for ascorbic acid oxidation is decreased by 150 mV at pH 2.2 compared with reaction at bare platinum; and an increase in anodic current and decrease in cathodic current for the redox reaction of ferrocene occurs on addition of ascorbic acid to the solution. The ferrocene-modified electrode is useful for the voltammetric determination of ascorbic acid in natural fruit juices. The advantages result from the electrocatalytic effect and from the prevention of adsorption of inhibitory substances from solution.  相似文献   

16.
The electrocatalytic oxidation of isoniazid (INH) by (ferrocenylmethyl)trimethylammonium [(FcM)TMA] at the platinum electrode in 0.10 M Na2SO4 aqueous solution was studied by cyclic voltammetry (CV). Although INH itself showed a very poor electrochemical response at the platinum electrode, the response could be greatly enhanced by using (FcM)TMA as a mediator, which enables a sensitive electrochemical determination of the substrate INH. The reaction rate constant for catalytic oxidation reaction was evaluated as (3.98±0.10)×103 M−1 s−1 by using chronoamperometry (CA). Experimental conditions such as supporting electrolyte and its concentration, solution pH, and the concentrations of the catalyst (FcM)TMA and the substrate INH were investigated to maximize the current efficiency of the electrocatalytic oxidation. The method can be used for the sensitive practical determination of INH, and also opens an avenue for using (FcM)TMA as a mediator in electroanalytical determination which is very simple, cheap, and rapid. Furthermore, no sample pretreatment or time-consuming extraction steps are required prior to the analysis.  相似文献   

17.
The considerations which determine the success of controlled-potential coulometric analyses on the submicrogram level are discussed, and it is shown that the ultimate sensitivity of the method is governed by the accuracy with which the requisite background corrections, especially that for the charging quantity of electricity, can be determined. A method for the coulometric determination of zinc based on these considerations is shown to contain a limiting uncertainty of ± 0.2 mμFy, so that as little as 0.07 μg of zinc can be determined within about ± 10%, while quantities of zinc exceeding about 10 μg can be determined with an accuracy and precision of ± 0.1% or better. Possible techniques for the further extension of controlled-potential coulometric analysis into the millimicrogram range are briefly discussed.  相似文献   

18.
A glassy carbon electrode modified with platinum nanoparticle-decorated carbon nanotubes (Pt-CNT/GCE) was prepared. The electrochemical behaviors for the catalysis oxidations of hydrogen peroxide and cysteine were studied. The Pt-CNT/GCE showed catalytic activity for electro-oxidation of hydrogen peroxide at 0.6 V in PBS (pH = 7.0) and for that of cysteine at 0.55 V in sulfuric acid medium (pH 相似文献   

19.
The use of hydrogenated platinum electrodes allows observation of the electroreduction of some oxygenated ions, which is otherwise masked by the reduction of the hydrogen ion. The present paper deals with the reduction of molybdenum(VI) at a prehydrogenated platinum electrode in acid solutions. The experimental conditions for the electrode hydrogenation process are the following: 90 min at a cathodic current density of about 7 A/cm(2) for microelectrodes with an area of 0.02-0.03 cm(2); about 120 min at a current density of 1.5-2 A/cm(2) for microelectrodes with an area of 0.25-0.35 cm(2). The reduction of molybdenum(VI) in 0.8-1.6M H(2)SO(4) occurs in two consecutive steps: the more cathodic wave [Mo(V) to Mo(III)] is for the most part masked by the reduction of the solvent; the less cathodic wave [Mo(VI) to Mo(V)] takes place at E(1 2 ) values of about +0.07 V, is well shaped, diffusion-controlled and usable for the determination of molybdenum down to 4 x 10(-5)M or 6 x 10(-5)M if a rotating disk electrode is used. Interferences from diverse ions have been studied. A generalization of the effect of electrode hydrogenation on the reduction of those oxygenated ions so far studied [i.e., vanadium(IV), uranium(VI) and molybdenum(VI)] is presented.  相似文献   

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