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

By C. Ponce de León, C.T.J. Low, G. Kear and F.C. Walsh


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 EL =DE/2 where DE 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 K3Fe(CN)6 ? K4Fe(CN)6 in 1 mol dm-3 NaOH at a 60 ppi reticulated vitreous carbon electrode (RVC)

Topics: TP, QD
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