Linear Potential Sweep Voltammetry Research Articles

Adsorption of methylene blue on a mercury electrode

The adsorption of methylene blue cation has been studied on the mercury electrode by linear potential-sweep voltammetry and by interfacial tension measurement. The amount of methylene blue cation adsorbed at different concentrations has been determined by extrapolation from plots of the integrals of the current/potential curves versus the reciprocal of the square root of the potential-sweep rate. The surface coverage thus derived is in very good agreement with the surface excess obtained from equilibrium mercury/solution interfacial tension measurements, which have been treated taking into account the self-association of methylene blue cation. The results obtained are consistent with the hypothesis of the formation, on average, of a bimolecular layer of methylene blue cation with flat orientation of the molecule with respect to the electrode surface.

The electrochemical reduction of nitrosonium ion in concentrated sulphuric acid: The NO +/NO redox couple

The electrochemical reduction of NO + ion in concentrated sulphuric acid has been studied on gold and platinum electrodes in the temperature range from 4·5 to 55·5°C with the rotating disk electrode, linear potential-sweep voltammetry and chronopotentiometry. On gold, NO + is reduced to NO, the reaction being a reversible one-electron transfer reaction. The experimental diffusion coefficients of the NO + ion and NO molecule are evaluated. On platinum, in the potential region where reduction of NO + ion and oxidation of NO occur, oxides formed on the metal interfere, thus making the interpretation of the process difficult.

Theoretical study of a reversible reaction followed by a chemical reaction in thin layer linear potential sweep voltammetry

Summary A theoretical study of current-potential curves in thin layer linear potential sweep voltammetry is presented for a reversible electrochemical reaction O+ ne R coupled with an irreversible chemical reaction. The following schemes are considered: 2R→Z (dimerization); O+R→Z (coupling reaction); R→Z (first order reaction). Different possible dimerization paths (purely radical, radical ionic, and purely ionic dimerization) are studied in detail. Criteria are given which allow a distinction to be made between the different schemes. The theory allows the determination of the rate constant of the chemical reaction; the limiting attainable values are determined, and a comparison is made with diffusion voltammetry.

Theoretical study of a reversible reaction followed by a chemical reaction in thin layer linear potential sweep voltammetry

Theoretical study of a reversible reaction followed by a chemical reaction in thin layer linear potential sweep voltammetry

Influence of the adsorption of the depolarizer or of a product of the electrochemical reaction on polarographic currents: XVII. Theoretical study of a reversible surface reaction followed by a first order chemical reaction in linear potential sweep voltammetry

A theoretical study of the peaks appearing in linear potential sweep voltammetry is presented under the following conditions: (a) the electrochemical reaction is reversible; (b) the depolarizer and the products of the electrochemical reaction are strongly adsorbed; (c) the product of the electrochemical reaction undergoes a first-order reaction according to the scheme: O + n e ⇄ R R → k Z The equations for the reduction and oxidation peaks have been calculated, and their characteristics are described. The rate constant of the chemical reaction can be determined on the basis of this theory. The results of this theoretical study can be directly applied to the same reaction scheme in thin layer voltammetry.

Influence of the adsorption of the depolarizer or of a product of the electrochemical reaction on polarographic currents XVII. Theoretical study of a reversible surface reaction followed by a first order chemical reaction in linear potential sweep voltammetry

Influence of the adsorption of the depolarizer or of a product of the electrochemical reaction on polarographic currents XVII. Theoretical study of a reversible surface reaction followed by a first order chemical reaction in linear potential sweep voltammetry

The Elucidation and Study of the Mechanism of Chemical Surface Reactions Using Linear Potential Sweep Voltammetry

AbstractA theoretical study of adsorption peaks in linear potential sweep voltammetry is presented for a reversible electrochemical reaction 0 + ne ⇄ R, followed by one of the chemical reactions 2R → Z (I); 0 + R → Z (II); R → Z (III). Criteria are given which allow a distinction to be made among diverse dimerization mechanisms. The rate constant of the chemical reaction can be determined on the basis of the theory.

Influence de l'adsorption du dépolarisant ou d'un produit de la réaction électrochimique sur les courants polarographiques—X. Étude théorique, en voltammétrie a variation linéaire de tension, d'une réaction en surface réversible suivie d'une dimérisation

A theoretical study of the peaks appearing in linear potential-sweep voltammetry is presented for the following case: the electrochemical reaction is reversible, the depolarizer and the product of the electrochemical reaction are both strongly adsorbed at the surface of the electrode, and the product of the electrochemical reaction dimerizes. The equation for the reduction and oxidation peaks has been calculated and their characteristics are described. The rate constant of the dimerizaton reaction can be determined on the basis of the theory.

Study of the kinetics of electrochemical reactions by thin-layer voltammetry

Linear potential sweep voltammetry in thin layers of solution offers numerous advantages for the study of irreversible reactions. The experimental equations, derived here for representative reaction types, are simpler than their counterparts in ordinary voltammetry, and may in some cases be solved directly for the electrochemical rate parameters, k0 and αn0. Rate measurements in thin layers do not require that both members of the reactant couple be present initially in solution. The physical and mathematical simplicity of thin layer voltammetry may allow the otherwise impossible study of irreversible systems involving multiple reactants, multiple charge-transfer steps or complicated stoichiometry. Experiments in which the theory is verified and exploited for studies of fundamental interest will be described in subsequent communications.

Study of the kinetics of electrochemical reactions by thin-layer voltammetry: I. theory

Linear potential sweep voltammetry in thin layers of solution offers numerous advantages for the study of irreversible reactions. The experimental equations, derived here for representative reaction types, are simpler than their counterparts in ordinary voltammetry, and may in some cases be solved directly for the electrochemical rate parameters, k0 and αn0. Rate measurements in thin layers do not require that both members of the reactant couple be present initially in solution. The physical and mathematical simplicity of thin layer voltammetry may allow the otherwise impossible study of irreversible systems involving multiple reactants, multiple charge-transfer steps or complicated stoichiometry. Experiments in which the theory is verified and exploited for studies of fundamental interest will be described in subsequent communications.

A Controlled-Potential and Controlled-Current Cyclic Voltammeter†

SUMMARY An instrument has been designed and constructed to be used primarily for electrochemical investigations in molten salt systems. It operates in either a controlled-potential or controlled-current mode. In the controlled-potential mode it may be used for linear potential sweep voltammetry or chronoamperometry; in the controlled-current mode, for chronopotentiometry with control of the initial potential. Fast electronic switching circuitry permits reversal of the sweep direction or current polarity, or termination of the experiment at preselected electrode potentials. Easily implemented extensions of the basic operating modes are discussed. The potentiostat is designed to deliver 100 mA at ±10 V, but larger transient currents can be accommodated. Accurate, calibrated sweep rates of 0.005 to 500 V/sec make the instrument suitable for kinetics studies. The rapid sweep rates also are used to advantage to minimize the effects of convective mass transport.

On the Separation of Half-Wave Potentials Required for Resolution of Simple, Reversible, Overlapping Waves in Stationary Electrode Voltammetry

SUMMARY Linear potential sweep voltammetry at stationary or quasi-stationary electrodes has become a widely accepted analytical technique. In contrast with the well-known dc polarographic current-voltage curve which reaches a limiting current (i1) at potentials sufficiently removed from the half-wave potential (E1/2), the voltammetric curve at a stationary electrode in unstirred solution reaches a maximum value (ip) after which the current decreases rather slowly as the potential is increased further. This “tail” is a matter of concern in the analysis of multicomponent systems if two or more species react during a single sweep of the electrode potential. This communication presents the results of calculations made to determine the separation of half-wave potentials required to permit the quantitative determination of each species in multicomponent systems. Regular, first-, and second-derivative techniques are considered.

Potential-step electrolysis followed by linear-sweep voltammetry at a plane mercury-film electrode

A theoretical treatment is given of constant-potential electrolysis followed by linear potential-sweep voltammetry at a mercury-film electrode. The case of an oxidizing potential step followed by reduction with a linear sweep is considered, as well as that of a reducing potential step followed by oxidation with a linear sweep. The analytical aspects of the results are discussed. The effect of initial and boundary conditions on the continuity of the current-potential curve at the start of the potential sweep is considered.

Linear potential-sweep voltammetry at a plane mercury- film electrode

A general treatment is given of linear potential-sweep voltammetry with a mercury-film electrode. The current-potential equations for both oxidizing and reducing potential-sweeps are considered. A mathematical approximation, useful for very thin mercury-films, is discussed, while the limiting case of zero film thickness is also considered. The effect of ohmic drop on the current-potential curves is given. The bearing of the results on experiment is pointed out.

Potential-step electrolysis followed by linear-sweep voltammetry

The method of potential-step electrolysis followed by linear potential-sweep voltammetry is considered theoretically. It is shown that, for a reversible electrode reaction without kinetic complications, the current—potential curve obtained during the linear potential-sweep is closely connected with the Ševčik—Randies P-function of normal linear-sweep voltammetry. Analytical implications are pointed out, while the presence of kinetic complications and the effect of finite electrode volume are briefly discussed.

Potential-sweep voltammetry—adsorption of chloranilic acid on a mercury electrode

The behaviour of chloranilic acid on mercury electrodes has been investigated by linear potential-sweep voltammetry. In very dilute solutions, a single adsorption peak appears. In more concentrated solutions, a second peak is observed which is diffusion-controlled. The amount of chloranilic acid adsorbed at the different concentrations has been determined by extrapolation, from the plots of the integrals of the current-potential curves versus the reciprocal of the square-root of potential-sweep rate. The maximum surface coverage thus derived is in very good agreement with the surface excess obtained from measurement of the mercury-solution interface tension using the drop-weight method. The results are consistent with the hypothesis of the formation of a monolayer of chloranilic acid with a flat orientation of the molecule with respect to the electrode surface.

Linear Potential Sweep Voltammetry in Thin Layers of Solution.

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTLinear Potential Sweep Voltammetry in Thin Layers of Solution.A. T. Hubbard and F. C. AnsonCite this: Anal. Chem. 1966, 38, 1, 58–61Publication Date (Print):January 1, 1966Publication History Published online1 May 2002Published inissue 1 January 1966https://doi.org/10.1021/ac60233a015RIGHTS & PERMISSIONSArticle Views491Altmetric-Citations149LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (407 KB) Get e-Alerts Get e-Alerts