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ChemElectroChem
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Supporting Information
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Mass-Transport-Corrected Transfer Coefficients: A Fully
20 General Approach
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22 Christopher Batchelor-McAuley,* Danlei Li, and Richard G. Compton
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Table of Content

Section 1: Accuracy of applying (a) the Koutecký-Levich method and (b) the analytical mass-transport

corrected method to microdisc voltammetry ............................................... 2

Section 2: Accuracy of applying Koutecký-Levich method and the normal mass-transport corrected method

at electrodes under a very ‘near’ steady-state regime ........................................ 7

Section 3: Schematics of the procedures for Tafel analysis .................................. 10

Section 4: Voltammetric response on a carbon microdisc electrode ............................ 13

Section 5: Comparison of the measured electrochemical rate constant for Fe2+/3+ redox couple ...... 14

1
Section 1: Accuracy of applying (a) the Koutecký-Levich method and (b) the analytical mass-
transport corrected method to microdisc voltammetry

In this section we investigate the accuracy of applying the Koutecký-Levich method and the normal mass-

transport corrected method in analysing steady-state voltammograms measured at a microdisc electrode for an

irreversible one electron transfer process. First we obtain the expected fully steady-state voltammograms for

microdisc electrodes with various radii (a=1, 5, 25 and 125 μm) using a previously reported analytically

approximate equation for the steady-state flux to a microsdic electrode as developed by Oldham et al.[1].

Although this equation for the steady-state flux is empirical it is highly accurate with a reported error of less

than 0.3%. The theoretical current-voltage profile is then analysed using both the Koutecký-Levich (K-L)

method and the normal mass-transport corrected method so as to assess the ‘best case scenario’ for the error

incurred by using these approximate analysis methods. Note that the expression for the current presented by

Oldham accounts, to a high degree of accuracy, for the non-uniform accessibility of the microdisc electrode.

a) Koutecký-Levich method on a microdisc electrode For an irreversible one electrode transfer oxidative

process

A ⇄ B + 𝑒 − , the inverse of the total current density is assumed to be expressed as Equation (1)[2]:
1 1 1 1 𝑒 −𝛼a𝜃
𝑗
=𝑗 + 𝑗 = 𝐹𝑚 𝑐 + 𝐹𝑘 0 𝑐
(1)
mt et 0

where 𝑗mt is the mass-transport limiting current, 𝑗et is the limiting current for heterogeneous kinetics at the

electrode surface calculated using Butler-Volmer model with the assumption of a uniformly accessible electrode,

F is the Faraday constant, 𝑚0 is the mass transfer coefficient (𝑚0 = 4𝐷𝑎/π for a microdisc electrode), D is

the diffusion coefficient of species A, 𝜃 is the dimensionless potential where 𝜃 = 𝐹(𝐸 − 𝐸0 )/(𝑅𝑇), 𝑐 is the

bulk concentration of species A in solution, 𝑘0 is the electrochemical rate constant, 𝛼a is the anodic transfer

coefficient, E is the applied potential at the working electrode, R is the gas constant and T is the temperature in

K.
1 1 𝑒 −𝛼a 𝜃
Plotting versus at different potentials should give a series of straight lines with an intercept of .
𝑗 𝑚0 𝑐 𝐹𝑘 0 𝑐

From the magnitude of the intercept the anodic transfer coefficient and electrochemical rate constant can be

calculated. It is very common at this stage for either the transfer coefficient or alternatively the rate of electron

transfer to be assumed to be independently known so as to allow the assessment of either k0 or 𝛼a respectively,

this artificially improves the apparent accuracy of the analysis method. In reality neither of these parameters are

2
experimentally known, and need to be determined from the data. Consequently, if we wish to independently

determine the magnitude of the transfer coefficient then a plot of the natural log of the K-L intercepts against
𝛼a 𝐹
the applied potential should yield a slope of − 𝑅𝑇
. Further, determination of the conditional or standard

electrochemical rate constant requires knowledge of the formal or standard potential. Assuming the formal or

standard potential is known the intercept of this plot will yield a measure of the conditional or standard

electrochemical rate constant.

Figure 1 a) depicts a series of four theoretical voltammograms predicted for four different sized microelectrodes,

as calculated from the expression provided by Oldham assuming 𝛼a = 0.5 and k0 = 1×10-7 m s-1. Here in Figure

1 a) the current has been normalised against the steady-state current and the position of the voltammetric wave

varies as a function of the size of the electrode. All other parameters used for the construction of the theoretical

current-voltage profiles are shown in the caption of Figure 1. From these four theoretical voltammograms the
1 1
set of plots of 𝑗
versus 𝑚0 𝑐
as determined at four different potentials (0.290, 0.360, 0.407 and 0.485 V) is given

in Figure 1 (b). As predicted by Equation 1 this K-L analysis yields a series of straight lines which have a

gradient of 1/F. Table 1 gives the intercepts of the four different potentials, where Figure 2 plots the natural

logarithm of these intercepts as a function of the analysis potential. From this plot the transfer coefficient is

determined to be 0.476±0.005; however, the ‘true’ transfer coefficient used to construct the idealised data was

0.5. This error is not due to any error in the description of the electrochemical flux from use of the Oldham

equation. Moreover, even for this ideal case the transfer coefficient does not lie within the uncertainty of the

value determined from K-L analysis. The inability of the K-L analysis to precisely determine the transfer

coefficient, even in this ‘best case scenario’ originates from the systematic error made in assuming that Equation

1 is able to accurately describe the voltammetric waveshape. Here for a microdisc electrode this is not the case

due to the surface being non-uniformly accessible. Furthermore, this systematic error also creates an issue when

estimating the conditional electrochemical rate constant, the intercept of Figure 2 yields an estimate of the

electrochemical rate constant to be 1.34±0.1×10-7 m s-1, a ~30% error from the actual value of 1×10-7 m s-1.

Again the true value does not even lie within the expected uncertainty of the parameter as determined from K-

L analysis.

It is worth noting that this error is sensitive electrode potentials used for the analysis; however, the values used

have been chosen to be reflective of what may reasonably be employed in the analysis of an actual experimental

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situation. The work by Bard and Kim use relatively high potentials towards the steady-state part of the

voltammetric wave, this is where the errors in the analysis will be greatest.

Figure 1 (a) Voltammograms at microdisc electrodes with various radii of 1 μm (black), 5 μm (red), 25 μm (blue) and 125 μm (green).
All the currents are normalised to their respective steady-state current calculated using the Oldham equation. The parameters used in the

equation: E0 = 0 V; c =1 mM; k0 = 1×10-7 m s-1; D = 1×10-9 m2 s-1; αa = αc = 0.5. (b) Plots of 1/j vs. 1/(m0c) obtained from voltammograms
in (a) at different potentials E-E0=0.290, 0.360, 0.407, 0.485 V.

Table 1 The intercepts of the K-L plots for the four different potentials plotted in Figure 1 b).

Sets of data E-E0 / V Intercept

1) 0.290 0.3670
2) 0.360 0.0961
3) 0.407 0.0402
4) 0.485 0.00989

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Figure 2 Plot of the natural log of the K-L intercepts as a function of the measurement potential (raw data given in Table 1). From linear
fitting of the data an intercept of 4.35±0.08 and a slope of -18.52±0.21 are determined.

b) Mass transport corrected method on a microdisc electrode In contrast to the above outlined K-L method the

mass-transport correction is applied to the analysis of a single voltammogram. Figure 3 depicts the voltammetric

response expected for a microdisc electrode with radius of 5 μm. The corresponding mass-transport corrected

anodic transfer coefficient plot is obtained using Equation 2[3]:

1 1
d ln| − |
𝐼a 𝐼lim
= −𝛼a ′ (2)
d 𝜃

where 𝐼a is the anodic current, 𝐼lim is the steady-state current, D is the diffusion coefficient of species A, 𝛼a ′

is the mass-transport corrected anodic transfer coefficient. As before this analysis and the use of Equation 2 is

predicted on the assumption that the current is uniform across the whole electrode surface.

Figure 3 presents the analytical mass-transport corrected anodic transfer coefficient plot where the 𝛼a ′ deviates

from its true value 0.5 at high overpotentials. The errors in estimated transfer coefficient at different fractions

of the wave (relative to the steady-state flux) are tabulated in Table 2. It is shown that if the transfer coefficient

is estimated by using the Tafel region of 10%-30% of steady state current, the averaged 𝛼a ′ is calculated to be

0.492 with only 1.6% error compared to its true value.

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Figure 3 Mass transport corrected anodic transfer coefficient on a microdisc electrode with radius of 5 μm. The black solid curve is the
normalised voltammogram simulated using Oldham equation where E0 = 0 V; c=1 mM; k0 = 1×10-7 m s-1; D = 1×10-9 m2 s-1; αa = αc =
0.5. The dotted line stands for different fractions of the wave (10%, 30%, 50% and 80% of Is.s). The blue solid curve is the mass-transport
corrected cathodic transfer coefficient plot as a function of potential. The current range analysed is 1-99% of Is.s.
Table 2 Error in αa at different fraction of the voltammetric wave.
Fraction of the wave 10% of Is.s 30% 50% 80%

Error in αc <1 % 2.8% 6.0% 12%

According to the results obtained above, it is shown that the estimated transfer coefficient using both methods

have comparable errors in the analysis of voltammograms at microdisc electrode. However, it is worthwhile

pointing out that both methods only hold with the assumption of a uniformly accessible electrode. Futhermore,

in both of the above analysis we have assumed that the physical parameters of the system are known with perfect

accuracy. If for instance there is an uncertainty in the size of the used electrodes this will significantly influence

the accuracy of these procedures. A further issue, and as will be explored in the next SI section, both analysis

methods are restricted to the true steady-state regime. Neither is able to account for any degree of contribution

of linear diffusion to the voltammetric response, a larger error is obtained when the system deviates away from

being at true steady-state (i.e. at higher scan rates or for larger electrodes).[3]

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Section 2: Accuracy of applying Koutecký-Levich method and the normal mass-transport
corrected method at electrodes under a very ‘near’ steady-state regime

This section presents an investigation into how accurate the application of the K-L method on a microdisc

electrode under a ‘near’ steady-state regime is as compared to the normal mass-transport corrected method. The

voltammograms for microdisc electrodes with various radii (a= 5, 10 and 20 μm) are simulated using a home-

written programme by Dr Oleksiy Klymenko [4] and these idealised ‘near’ steady-state voltammograms are

shown in Figure 4 a) where the current has been normalised against the expected steady-state flux. Note for the

larger electrodes the flux is significantly above that expected under steady-state conditions and reflects the

contribution of linear diffusion to the voltammetric response. The simulation program is based on the conformal

mapping of the spatial coordinates and uses an exponentially expanding time grid.[4]

Figure 4 a) depicts a series of theoretical voltammograms predicted for three different sized microelectrodes

(radii a=5, 10 and 20 μm), as numerically calculated by the Klymenko program using 𝛼a = 0.5 and k0 = 1×10-7
1 1
m s-1. Figure 4 b) presents the K-L analysis for these three electrodes where a set of plots of versus at
𝑗 𝑚0 𝑐

different potentials (0.256, 0.324, 0.368, 0.440 V) are presented. Again linear relationship is obtained as
𝑒 −𝛼a𝜃
expected with a gradient of (approximately) 1/F and intercept of . Table 3 presents the values of intercepts
𝐹𝑘 0 𝑐

as measured for these four potentials and Figure 5 further gives the plots of the natural log of the intercepts as
𝛼a 𝐹
a function of potential of which the slope yields − . From Figure 5 the anodic transfer coefficient is
𝑅𝑇

estimated to be 0.46±0.01. The conditional electrochemical rate constant is calculated to be 1.48±0.2×10-7 m s-

1
from the intercept of Figure 5. Hence, for these ‘near’ steady-state voltammogram the calculated αa,K-L is in

error by 8% from its true value 0.5 and calculated k0 is wrong by nearly 50%(!) compared to its true value (1×10-
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m s-1). This additional decrease in accuracy from the situation in Section 1 purely reflects the inability of the

K-L analysis to account for any linear contribution to the voltamemtric response of the electrode.

For completeness the results analysed using normal mass-transport corrected method are shown in Figure 6 and

Table 4. Figure 6 gives the mass-transport corrected anodic transfer coefficient on a microdisc electrode with

radius of 20 μm, where the αa’ deviates from its true value at higher overpotentials. Moreover, the behaviour of

transfer coefficient as a function of potential tends to be more like the behaviour under linear regime[3] as the

radius of electrode increases. We can see that the accuracy in analysing a very ‘near’ steady-state voltammogram

decreases for both K-L and normal mass-transport corrected methods. The difference in the values estimated

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from these two methods does not reflect any under lying change in the assumptions made but purely reflects the

slight difference in how the analysis is performed. Notably the K-L analysis tends to only use a limited range

of potentials whereas the mass-transport correction uses more of the available voltammetric information.

Figure 4 (a) Voltammograms at microdisc electrodes with various radii of 5 μm (red), 10 μm (blue) and 20 μm (green). All the currents
are normalised to their respective steady state current calculated using Is.s=4FDca. The parameters used in the equation: E0 = 0.0 V; c =1
mM; k0 = 1×10-7 m s-1; D = 1×10-9 m2 s-1; αa = αc =0.5, scan rate = 0.025 V s-1. (b) Plots of 1/j vs. 1/(m0c) obtained from voltammograms
in (a) at different potentials E-E0=0.256, 0.324, 0.368, 0.440 V.

Table 3 The intercepts of the K-L plots for the four different potentials in Figure 4(b).

Sets of data E-E0 / V Intercept

1) 0.256 0.73210
2) 0.324 0.20150
3) 0.368 0.09001
4) 0.440 0.02697

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Figure 5 Plot of the natural log of the K-L intercepts as a function of the measurement potential (raw data given in Table 1). From linear
fitting of the data an intercept of 4.25±0.15 and a slope of -17.95±0.42 are determined.

Figure 6 Mass-transport corrected anodic transfer coefficient on a microdisc electrode with radius of 20 μm. The black solid curve is the
oxidative voltammetric wave simulated normalised to its steady-state current (Is.s=4FDca) where E0 = 0 V; c = 1 mM; k0 = 1×10-7 m s-1;
D = 1×10-9 m2 s-1; αa = αc = 0.5; scan rate = 0.025 V s-1. The dotted line stands for different fractions of the wave (10%, 30%, 50% and
80% of Is.s). The blue solid curve is the mass-transport corrected anodic transfer coefficient plot as a function of potential.

Table 4 Error in αa at different fraction of the voltammetric wave in Figure 6.

Fraction of the wave 10% of Is.s 30% 50% 80%

Error in αa 1.4% 4.6% 9.0% 26.5%

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Section 3: Schematics of the procedures for Tafel analysis

This section presents schematics of the suggested procedures for Tafel analysis. How to choose the mass-

transport correction method for different electrode geometries is shown in Scheme 1. The procedures for the

normal mass-transport correction is presented in Scheme 2 where the Tafel region is chosen on the basis of a

microdisc electrode whereas the Tafel region varies for other electrode geometries [3]. The procedures for the

proposed new extraction method in this work is shown in Scheme 3.

Scheme 1 General procedures for the choice of transfer coefficient analysis under different electrode geometries.

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Scheme 2 Procedures for the normal mass-transport correction on a microdisc electrode.

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Scheme 3 Procedures for proposed new extraction method.

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Section 4: Voltammetric response on a carbon microdisc electrode

This section provides the experimental voltammograms on a carbon microdisc electrode (calibrated radius of

3.64 μm) without background correction in a solution containing 5 mM (NH4)2Fe(SO4)2 and 2.5 mM (NH4)2SO4

in 0.2 M HClO4 at 0.05 V s-1. The background current obtained from blank solution (2.5 mM (NH4)2SO4 in 0.2

M HClO4) is shown as the blue curve in Figure 7.

Figure 7 Cyclic voltammogram on a carbon microdisc electrode (radius of 3.64μm) without background correction (red). Solution
composition: (a) 5 mM (NH4)2Fe(SO4)2, 2.5 (NH4)2SO4 in 0.2 M HClO4; (b) 10 mM (NH4)2Fe(SO4)2, 2.5 mM (NH4)2SO4 in 0.2 M
HClO4; (c) 20 mM (NH4)2Fe(SO4)2, 2.5 (NH4)2SO4 in 0.2 M HClO4. Blue curve represents the voltammogram obtained in blank solution
with 2.5 (NH4)2SO4 in 0.2 M HClO4. Scan rate used is 0.05 V s-1.

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Section 5: Comparison of the measured electrochemical rate constant for the Fe2+/3+(aq) redox
couple with literature reported values

In this work the electrochemical rate constant of Fe2+/3+ redox couple of the experimental voltammogram is

extracted to be 1.1-2.3×10-6 m s-1 using data in the potential range of 0.7-1.1 V. The uncertainty predominantly

reflects the uncertainty in the measured anodic transfer coefficient which is found to vary from 0.3 to 0.26. A

small variation in the transfer coefficient causes a significant (exponential) change in the measured conditional

electrochemical rate constant. In our previous work a value of 5×10-7 m s-1 for the electrochemical rate constant

was used to fit the experimental voltammogram for Fe2+ oxidation; this lower value was chosen based on a

relatively large anodic transfer coefficient of 0.35 being used. In addition, the values of extracted conditional

electrochemical rate constant are comparable to those in the literature in which carbon-related electrodes were

used. Zhang et al. measured the value of electrochemical rate constant of Fe2+/3+ redox couple to be 3.8-5.8×10-

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m s-1 on a highly oriented pyrolytic graphite (HOPG) macroelectrode assuming the transfer coefficient is 0.5.[5]

References:
[1] aK. B. Oldham, C. G. Zoski, J. Electroanal. Chem. Interfacial Electrochem. 1991,
313, 17-28; bA. Molina, J. Gonzalez, E. O. Barnes, R. G. Compton, J. Phys. Chem. C
2013, 118, 346-356.
[2] J. Kim, A. J. Bard, Analytical Chemistry 2016, 88, 1742-1747.
[3] D. Li, C. Lin, C. Batchelor-McAuley, L. Chen, R. G. Compton, J. Electroanal. Chem.
2018, 826, 117-124.
[4] O. V. Klymenko, R. G. Evans, C. Hardacre, I. B. Svir, R. G. Compton, J. Electroanal.
Chem. 2004, 571, 211-221.
[5] G. Zhang, S. Y. Tan, A. N. Patel, P. R. Unwin, Phys. Chem. Chem. Phys. 2016, 18,
32387-32395.

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