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Strategies for the determination of the convective-diffusion limiting current from steady state linear sweep voltammetry

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Abstract

The limiting current is an important parameter for the characterization of mass transport in electrochemical systems operating under convective-diffusion control. Four methods to determine the limiting current from current (I) vs. potential (E) plots are considered. Strategies to determine the limiting current values include: (1) direct measurement from I vs. E curves, (2) estimation from the current value at E L = ΔE/2 where ΔE is the length of the limiting current plateau, (3) evaluation of the first derivative dI/dE in the I vs. E curve and (4) from plots of E/I vs. I −1. The electrode reactions chosen to demonstrate the different strategies are: Cu(II) → Cu(I) and Cu(I) → Cu(0) in 1.5 mol dm−3 NaCl (pH 2) at a platinum rotating disc electrode and \( {\text{Fe}}({\text{CN}})^{{3 - }}_{6} \to {\text{Fe}}({\text{CN}})^{{4 - }}_{6} \) in 1 mol dm−3 NaOH at a 60 ppi reticulated vitreous carbon electrode (RVC).

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Abbreviations

A :

Electrode area (cm2)

c b :

Concentration of reactant ions in the bulk solution (mol dm−3)

E 1/2 :

Half-wave potential, corresponding to I L/2 (V)

E L :

Potential at which the limiting current value is taken (V)

E max :

Maximum potential value on the plateau region (V)

E min :

Minimum potential value on the plateau region (V)

F :

Faraday constant, 96,485 (C mol−1)

D :

Diffusion coefficient of electroactive species (cm2 s−1)

I :

Current (mA)

I L :

Limiting current (mA)

j L :

Limiting current density (mA cm−2)

k m :

Mass transport coefficient (cm s−1)

z :

Number of electrons transferred in the reaction (Dimensionless)

v :

Mean linear velocity of the electrolyte (cm s−1)

ω :

Rotation rate of disc electrode (rad s−1)

ν :

Kinematic viscosity of the electrolyte (cm2 s−1)

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Author notes

  1. G. Kear

    Present address: Electrochemical Engineering Laboratory, Energy Technology, Research Group, School of Engineering Sciences, University of Southampton, Highfield, Southampton, SO17 1BJ, UK

Authors and Affiliations

  1. Electrochemical Engineering Laboratory, Energy Technology Research Group, School of Engineering Sciences, University of Southampton, Highfield, Southampton, SO17 1BJ, UK

    C. Ponce-de-León, C. T. J. Low & F. C. Walsh

  2. Building Research Association of New Zealand (BRANZ) Ltd, Private Bag 50 908, Porirua City, 6220, New Zealand

    G. Kear

Authors
  1. C. Ponce-de-León
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  2. C. T. J. Low
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  3. G. Kear
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  4. F. C. Walsh
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Correspondence to C. Ponce-de-León.

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Ponce-de-León, C., Low, C.T.J., Kear, G. et al. Strategies for the determination of the convective-diffusion limiting current from steady state linear sweep voltammetry. J Appl Electrochem 37, 1261–1270 (2007). https://doi.org/10.1007/s10800-007-9392-3

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  • DOI: https://doi.org/10.1007/s10800-007-9392-3

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