Diffusion-affected charge transfer: demonstration experiment for the linear relationship between current and its semiintegral

Diffusion-affected charge transfer is a basic situation of electrochemical kinetics; the rate coefficients are often estimated by analyzing cyclic voltammograms. Provided that a couple of conditions hold, decoupling of diffusion and charge transfer is possible by using a recent theory leading to a l...

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Main Author: Tamás Pajkossy
Format: Article
Language:English
Published: Elsevier 2025-09-01
Series:Electrochemistry Communications
Subjects:
Online Access:http://www.sciencedirect.com/science/article/pii/S1388248125001080
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author Tamás Pajkossy
author_facet Tamás Pajkossy
author_sort Tamás Pajkossy
collection DOAJ
description Diffusion-affected charge transfer is a basic situation of electrochemical kinetics; the rate coefficients are often estimated by analyzing cyclic voltammograms. Provided that a couple of conditions hold, decoupling of diffusion and charge transfer is possible by using a recent theory leading to a linear relation of the current and its so-called semiintegral. Accordingly, a set of voltammograms of such reactions, measured with varied scan rates, can be transformed into two functions characteristic of charge transfer and diffusion separately, yielding charge transfer rate coefficients. We present here voltammograms measured on a well-known electrochemical system (gold electrode in a ferrocyanide/ferricyanide containing aqueous solution) and demonstrate the applicability of the above-mentioned linear relation; finally, we calculate the charge transfer rate coefficients as a function of the electrode potential. The main advantages and disadvantages of the analysis method are discussed, along with the limitations of the practical applicability.
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spelling doaj-art-98d1ffce4a4d4f8c965da803ddfb84a62025-08-20T03:44:06ZengElsevierElectrochemistry Communications1388-24812025-09-0117810796910.1016/j.elecom.2025.107969Diffusion-affected charge transfer: demonstration experiment for the linear relationship between current and its semiintegralTamás Pajkossy0Corresponding author.; Institute of Materials and Environmental Chemistry, Research Centre for Natural Sciences, Magyar tudósok körútja 2, Budapest H-1117, HungaryDiffusion-affected charge transfer is a basic situation of electrochemical kinetics; the rate coefficients are often estimated by analyzing cyclic voltammograms. Provided that a couple of conditions hold, decoupling of diffusion and charge transfer is possible by using a recent theory leading to a linear relation of the current and its so-called semiintegral. Accordingly, a set of voltammograms of such reactions, measured with varied scan rates, can be transformed into two functions characteristic of charge transfer and diffusion separately, yielding charge transfer rate coefficients. We present here voltammograms measured on a well-known electrochemical system (gold electrode in a ferrocyanide/ferricyanide containing aqueous solution) and demonstrate the applicability of the above-mentioned linear relation; finally, we calculate the charge transfer rate coefficients as a function of the electrode potential. The main advantages and disadvantages of the analysis method are discussed, along with the limitations of the practical applicability.http://www.sciencedirect.com/science/article/pii/S1388248125001080InterfaceDiffusionVoltammetryCharge transfer
spellingShingle Tamás Pajkossy
Diffusion-affected charge transfer: demonstration experiment for the linear relationship between current and its semiintegral
Electrochemistry Communications
Interface
Diffusion
Voltammetry
Charge transfer
title Diffusion-affected charge transfer: demonstration experiment for the linear relationship between current and its semiintegral
title_full Diffusion-affected charge transfer: demonstration experiment for the linear relationship between current and its semiintegral
title_fullStr Diffusion-affected charge transfer: demonstration experiment for the linear relationship between current and its semiintegral
title_full_unstemmed Diffusion-affected charge transfer: demonstration experiment for the linear relationship between current and its semiintegral
title_short Diffusion-affected charge transfer: demonstration experiment for the linear relationship between current and its semiintegral
title_sort diffusion affected charge transfer demonstration experiment for the linear relationship between current and its semiintegral
topic Interface
Diffusion
Voltammetry
Charge transfer
url http://www.sciencedirect.com/science/article/pii/S1388248125001080
work_keys_str_mv AT tamaspajkossy diffusionaffectedchargetransferdemonstrationexperimentforthelinearrelationshipbetweencurrentanditssemiintegral