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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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