, Volume 9, Issue 3, pp 409–415 | Cite as

A Simple Method to Establish the Relationship Between the Equilibrium Polarization Resistance and the Elementary Kinetic Parameters of an Electrocatalysed Reaction

  • María A. Montero
  • Carlos A. Marozzi
  • María R. Gennero de Chialvo
  • Abel C. Chialvo
Original Research


A simple and rigorous methodology to establish the relationship between the faradaic equilibrium polarization resistance of an electrocatalytic reaction with the elementary kinetic parameters involved in the reaction mechanism is proposed. It was derived through an alternative method, which avoided the differentiation of the corresponding current-overpotential dependence. This formalism includes the cases where both, reactants and products, exhibit diffusion contributions. It is demonstrated that the equilibrium polarization resistance is the sum of both, faradaic and diffusion, contributions. Each diffusion term has a linear variation with the inverse of the limiting diffusion current density of the species involved. This behavior was exemplified with two different experimental data sets for the hydrogen electrode reaction, obtained on a rotating disc and microelectrodes, respectively.

Graphical Abstract

Experimental equilibrium polarization resistance is the sum of faradaic (\( {R}_p^o \)) and diffusion (\( {R}_p^d \)) contributions. A simple and novel methodology is presented for the derivation of the relationship between \( {R}_p^o \) and the equilibrium reaction rates of the elementary steps (\( {v}_i^e \)). It is also demonstrated the linear variation of \( {R}_p^d \) with the inverse of the limiting diffusion current density.


Equilibrium polarization resistance Faradaic and diffusion contributions Equilibrium reaction rate of elementary steps Exchange current density 



The authors wish to acknowledge the financial support received from Agencia Nacional de Promoción Científica y Tecnológica (ANPCyT, PICT 2014-2001); Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET, PIP 0311); and Universidad Nacional del Litoral (UNL, CAI+D 2016 PIC 018LI).


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Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2017

Authors and Affiliations

  • María A. Montero
    • 1
  • Carlos A. Marozzi
    • 1
  • María R. Gennero de Chialvo
    • 1
  • Abel C. Chialvo
    • 1
  1. 1.Instituto de Química Aplicada del Litoral, IQAL (UNL-CONICET), Programa de Electroquímica Aplicada e Ingeniería Electroquímica, PRELINE (FIQ-UNL)Santa FeArgentina

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