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Electrochemistry Communications 2 (2000) 85–89

Electrochemical nucleation with diffusion-limited growth. Properties and

analysis of transients
Luc Heerman *, Anthony Tarallo
¨
Departement Scheikunde, Afdeling Coordinatiechemie, Katholieke Universiteit Leuven, Celestijnenlaan 200G, B-3001 Heverlee, Belgium

Received 11 October 1999; received in revised form 28 October 1999; accepted 29 October 1999

Abstract

A general equation for the potentiostatic transient for the case of electrochemical nucleation with diffusion-controlled growth has been
published recently [L. Heerman, A. Tarallo, J. Electroanal. Chem. 470 (1999) 70]. This equation essentially is a correction to the model of
Scharifker and Mostany [J. Electroanal. Chem. 177 (1984) 13] but leads to quite different predictions. This paper discusses the differences
between these two models with special emphasis on the analysis of experimental transients. Numerical data are presented which allow the
determination of the nucleation parameters (nucleation rate constant A and site density N0). Finally, it is shown that plots of I/Imax versus
t/tmax, which are widely used in the literature for the graphical representation of experimental results, are not very sensitive and can easily
lead to misinterpretation of experimental results. q2000 Elsevier Science S.A. All rights reserved.

Keywords: Nucleation; Diffusion-controlled growth; Potentiostatic transients; Chronoamperometry

1. Introduction

The theoretical description of the potentiostatic transient

for multiple nucleation with diffusion-controlled growth has
been controversial for many years. Scharifker et al. [1]
recently reviewed the subject and compared the fitting of
experimental transients with the theoretical equations pro-
posed by different groups [2–4]. The analytical expression
most widely used until now in the literature for the current
transient is the equation derived by Scharifker and Mostany
[2]:
I(t)szFDc(pDt)y1/2[1yexp(ypkN 0 DtQ)] (1)
1/2
where ks(8pMc/r) and Q'Q[At] (Fig. 1(a)) is given
by
Qs1y[1yexp(yAt)]/At (2)
Methods for the estimation of the nucleation parameters,
the nucleation rate constant A and the site density N0, from Fig. 1. Graphical representation of the functions (a) Q (Eq. (2)), (b) F
experimental transients with Eq. (1) have been discussed by (Eq. (4)) and (c) (F/Q); (F/Q)™4/3 as At™0; (F/Q)™1 as At™`.
Scharifker et al. [2,5,6] and others [7,8]. However, we have
shown recently [9] that the model of Scharifker and Mostany N0 and low values of A (it must be noted also that Eq. (1)
[2] is not correct and that Eq. (1) cannot be used to describe
does not reduce to the correct expression for the limit of very
properly experimental transients obtained at high values of
short times when there is no overlap of the diffusion fields).
* Corresponding author. Tel.: q32-16-327-337; fax: q32-16-327-992; In fact we have shown that the correct expression for the
e-mail: luc.heerman@chem.kuleuven.ac.be current transient is given by

1388-2481/00/$ - see front matter q2000 Elsevier Science S.A. All rights reserved.
PII S 1 3 8 8 - 2 4 8 1 ( 9 9 ) 0 0 1 4 4 - 7

Tuesday Jan 11 02:24 PM StyleTag -- Journal: ELECOM (Electrochemistry Communications) Article: 154
86 L. Heerman, A. Tarallo / Electrochemistry Communications 2 (2000) 85–89
I(t)szFDc(pDt)y1/2(F/Q)[1yexp(ypkN 0 DtQ)] (3)
where F'F[(At)1/2] (Fig. 1(b)), related to Dawson’s
integral, is given by
(At)1/2
exp(yAt)
Fs1y | exp l2 dl (4)
(At)1/2
0 the Scharifker–Mostany treatment the reduced current den-
The main difference between Eq. (3) (which has been
deduced previously by Mirkin and Nilov ([4], Eq. (32))
using rather dubious arguments) and the Scharifker–Mostany
formula can be summarized briefly as follows. Scharifker and
Mostany [2] calculate the fraction of the electrode surface
covered by diffusion zones u(t) and obtain the expression
for the current density as the planar diffusion flux (Cottrell
equation) to this fractional area, i.e. I(t)szFDc(pDt)y1/2
=u(t), so that the thickness of the diffusion layer in the case
of overlap is a function only of time variable t. We have
argued that this is physically incorrect because such a pro-
cedure allows the diffusion layer to expand always at the
same rate, whether all the nuclei are born or not. The thickness
of the diffusion layer must be a function not only of time
variable t but also of the nucleation rate constant A, except of
course in the case of instantaneous nucleation (all the nuclei
are born immediately after application of the nucleation
pulse). It follows from the boundary conditions that the thick-
¯ Q/F)(pDt)1/2 and
ness of the diffusion layer is given by ≠s(
Eq. (3) is obtained by introducing this expression in the
general equation, I(t)szFDc(u(t)/≠(t)) ¯ . Eq. (3) reduces to
the correct expressions for both the limits of very short and
very long times (as t™0, I(t)™zFDCaN0t1/2F, the current
density for an ensemble of independent growing nuclei [3];
as t™`, I(t)™zFD1/2c(pt)y1/2, the Cottrell limit). Eq. (3)
essentially must be considered as a ‘correction’ to the equa-
tion of Scharifker and Mostany [2] since the same model is
used for the calculation of overlap. However, both equations
lead to quite different results which are discussed in this paper
with special emphasis on the analysis of experimental tran-
sients. Before doing so it might be useful to remember that
both Eqs. (1) and (3) make use of the nucleation law
N(t)sN0[1yexp(yAt)], which has been criticized
recently by Deutscher and Fletcher [10]. Use of this equation
implies that the number of nucleation sites on the electrode
is instantaneously fixed after applying a potential step and
thus assumes a ‘frozen’ energetic state of the surface. Then,
two limiting cases can be considered: A<1, NsN0At (pro-
gressive nucleation) and A41, NsN0 (instantaneous
nucleation). A model which takes into account the dynamics
of the appearance and disappearance of active sites on the
surface has been discussed by Milchev [11,12] but is beyond
the scope of this paper.
2. Results
It has been shown by Scharifker and Mostany [2] that it
is advantageous for the analysis of transients to define the
Tuesday Jan 11 02:24 PM StyleTag -- Journal: ELECOM (Electrochemistry Communications)
following quantities bspkN0D, asb/A (a™` for progres-
sive nucleation and a™0 for instantaneous nucleation) and
xsbtmax where tmax is the time corresponding to the current
maximum in the transient. It is also useful to define a ‘reduced
current density’ as the current density divided by the Cottrell
current at the same time, IR(t)sI(t)(pt)1/2/zFD1/2c. For
sity can be written as
IR(t)s1yexp(ya AtQ) (5)
while for Eq. (3) the reduced current density takes the form:
IR(t)s(F/Q)[1yexp(ya AtQ )] (6)
Inspection of these equations shows immediately the basic
difference between the two approaches. In the case of the
Scharifker–Mostany formula, the reduced current density
IR(t) is simply equal to u(t), the fractional area covered by
diffusion zones. According to Eq. (6), however, the reduced
¯ , and thus
current density reflects the retardation of u(t)/≠(t)
also the slow expansion of the diffusion layer, as the result
of slow nucleation. In the case of instantaneous nucleation,
F/Qs1 and both equations become identical; as At™0 (pro-
gressive nucleation), F/Q™4/3 so that the ratio of the
values predicted by Eqs. (5) and (6) is a constant factor. A
typical set of calculated I(t)–IR(t) pairs for the general case
is shown in Fig. 2.
According to Eq. (5), IR(t) always increases smoothly
from zero to unity at a rate which depends on the nucleation
parameters. Eq. (6) however predicts a maximum (with a
value always greater than unity) in the IR(t) versus time
curve which is a certain indication of slow nucleation and
which is indeed observed experimentally. After this maxi-
mum the reduced current decreases slowly, IR™1 as t™`.
There are several effects of all this on the experimental tran-
sients which can be deduced directly from Fig. 2. First, Imax
(the current density at tmax) is higher than the Cottrell current
which is impossible according to the Scharifker–Mostany
model. Second, for t)tmax the current according to Eq. (3)
will decrease only very slowly to the Cottrell value (which
is the limit for t™`), while the Scharifker–Mostany model
predicts that the current will fall to the diffusion-limited value
almost immediately after the maximum. This means that
according to Eq. (3) all points of the transient carry infor-
mation on the nucleation parameters, and not only the rising
part of the transient and the region around the maximum. If
this is the good news (for example for the fitting of tran-
sients), then the bad news is that it not possible to determine
diffusion coefficients from the falling part of the transient.
Finally, it is easily seen that the current maximum according
to Eq. (3) should occur at shorter times than predicted by the
Scharifker–Mostany model. However, for both limiting cases
this difference should disappear, so that a plot of tmax/
tmax(SM) (the ratio of tmax according to Eq. (3) and the value
according to Eq. (2)) is expected to pass through a minimum.
Scharifker and Mostany [2] have shown that analysis of
experimental transients is possible by constructing a pair of
Article: 154
 L. Heerman, A. Tarallo / Electrochemistry Communications 2 (2000) 85–89 87

Eq. (3) is much more sensitive to a change of the nucleation

parameters, as could be anticipated from the theory. The plot
of btmax versus log(a) according to Eq. (3) is shown in
Fig. 4.
On the scale of this graph the difference between the values
predicted by Eq. (3) and the Scharifker–Mostany model are
hardly visible. However, the plot of tmax/tmax(SM) shown in
Fig. 5 passes through a minimum as predicted by theory (this
minimum with a value of 0.884 is found at log(a); y0.5).
The pair of plots in Figs. 3 and 4 can be used for the analysis
of experimental transients according to Eq. (3) in the same
way that was customary for the analysis of transients accord-
ing to the theory of Scharifker and Mostany [2]. Numerical

Fig. 2. Reduced current (A) and nucleation transients (B) according to (a)
the Scharifker–Mostany model and (b) Eq. (3). The dashed line is the
Cottrell current for a planar macro-electrode. Arrows indicate the position
of the current maximum. Fig. 3. Plot of Imaxtmax1/2/a vs. log(a) according to (a) Scharifker and
Mostany [2] and (b) Eq. (3). Values for the limiting cases of instantaneous
working curves, i.e. a plot of Imaxtmax1/2/a versus log(a) and progressive nucleation are indicated.
(where aszFD1/2c/p1/2; thus, Imaxtmax1/2/a is the value of
the reduced current at the maximum of the transient) and a
plot of btmax versus log(a). We have calculated numerically
these plots for both models to make a direct comparison. The
plot of Imaxtmax1/2/a versus log(a) is shown in Fig. 3.
For small values of a (instantaneous nucleation) Imaxtmax1/2
/a tends to the limiting value 0.7153 calculated previously
by Scharifker and Mostany [2]. For large values of a the
Scharifker–Mostany model predicts that Imaxtmax1/2/
a™0.9034 as log(a)™` while Eq. (3) gives this limit as
(4/3)P0.9034s1.2045 (this higher value results from the
fact that the current density at the maximum is higher than
the Cottrell value). The plot of Imaxtmax1/2/a versus log(a)
according to Eq. (3) approaches the limit of progressive
nucleation more slowly than predicted by the Scharifker–
Mostany model which imposes a Cottrell current immediately
after the maximum. Here it must be reminded that ‘progres-
sive nucleation’ is just a mathematical limit; nucleation will
be observed as ‘progressive’ for AtF0.2 [3] but as t™` this
condition will fail and at long times the current will always Fig. 4. Plot of btmax vs. log(a) according to Eq. (3). See text for a compar-
tend to the Cottrell limit. It follows that the plot according to ison with the Scharifker–Mostany model.

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88 L. Heerman, A. Tarallo / Electrochemistry Communications 2 (2000) 85–89

values of both Imaxtmax1/2/a and btmax versus log(a) are given

in Table 1.
Finally, it is interesting to look at plots of (I/Imax)2 versus
t/tmax which have been widely used in the literature for the
representation of experimental results. These plots do not
require an a priori knowledge of the diffusion coefficient and
hide the fact that the current density can have values higher
than the Cottrell current (perhaps explaining why this kind
of plot seems so popular). In our previous paper [9] we have
stated that such plots are the same for the limiting cases of
instantaneous and progressive nucleation and can still be used
for a qualitative analysis of the transients. This conclusion
was based on the fact that Eqs. (1) and (3) give same the
lines for the limiting cases of instantaneous and progressive
nucleation in this kind of plot. The numerical calculations
however show that important differences exist between the
predictions of both theoretical models. As can be expected,
Fig. 5. Plot of tmax/tmax(SM) vs. log(a); tmax is the position of the current there are no important differences in plots of (I/Imax)2 versus
maximum according to Eq. (3) and tmax(SM) is the same quantity according t/tmax for small enough values of a, up to log(a); y0.6 (this
to the Scharifker–Mostany expression.
could be inferred directly from the plot in Fig. 3). However,
for larger values of log(a) there are important differences
Table 1 for values of t/tmax)1 (there is never much difference for
Numerical values of Imaxtmax1/2/a and btmax versus log(a) according to
the rising part of the transient). The values of I/Imax according
Eq. (3)
to Eq. (3) are lower than the ones predicted by the Scharif-
Log(a) Imaxtmax1/2/a btmax ker–Mostany model, especially for t/tmax)2. Eventually, for
values in the range 0-log(a)-1, the plot according to Eq.
y3.00 0.7156 1.257 (3) will cross the line for the limiting case of progressive
y2.50 0.7163 1.260 nucleation and then approach this limit for very large values
y2.00 0.7182 1.266
y1.75 0.7206 1.275 of t/tmax from below. However, for values of log(a))1 there
y1.50 0.7243 1.288 is an inversion in the relative position of the plots with respect
y1.40 0.7264 1.296 to that theoretical limit, i.e. the plots move up again. The
y1.30 0.7299 1.309
y1.20 0.7331 1.321 series of plots of (I/Imax)2 versus t/tmax according to Eq. (3)
y1.10 0.7386 1.341 shown in Fig. 6 clearly demonstrate this behaviour.
y1.00 0.7444 1.363
y0.90 0.7526 1.395
y0.80 0.7621 1.433
y0.70 0.7754 1.488
y0.60 0.7922 1.562
y0.50 0.8117 1.655
y0.40 0.8347 1.776
y0.30 0.8587 1.916
y0.20 0.8851 2.090
y0.10 0.9110 2.288
0.00 0.9359 2.512
0.10 0.9602 2.770
0.20 0.9833 3.062
0.30 1.0049 3.392
0.40 1.0244 3.760
0.50 1.0426 4.177
0.60 1.0584 4.638
0.70 1.0734 5.162
0.80 1.0873 5.754
0.90 1.1012 6.434
1.00 1.1116 7.170
1.25 1.1340 9.443
1.50 1.1520 12.494
1.75 1.1645 16.532
2.00 1.1747 21.950
2.25 1.1822 29.164
2.50 1.1881 38.801 Fig. 6. Plot of (I/Imax)2 vs. t/tmax for different values of log(a) according
2.75 1.1935 51.735 to Eq. (3). The plots for the range 0-log(a)-1 are not shown in this
3.00 1.1951 68.700 figure because they fall in the same narrow band as the plots for the range
1-log(a)-`.

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 L. Heerman, A. Tarallo / Electrochemistry Communications 2 (2000) 85–89
From an experimental viewpoint this means that plots of
(I/Imax)2 versus t/tmax for the whole range 0-log(a)-`
will ‘appear’ as progressive, if no other analysis is done on
the transients. Therefore, we think that the use of such plots,
although widely used in the literature for the representation
of experimental data, is of very limited value for the analysis
of transients and must be strongly discouraged.
3. Conclusions
The properties of the potentiostatic transient for electro-
chemical nucleation with diffusion-controlled growth have
been discussed. The model of Scharifker and Mostany [2]
and the correction to it, which we have proposed recently
[9], lead to quite different theoretical predictions. Working
curves for the analysis of experimental transients according
to this new equation have been constructed. Finally, it is
shown that plots of (I/Imax)2 versus t/tmax, although widely
used in the literature, have a very limited value for the analysis
of experimental transients.
Acknowledgements
The authors are indebted to Professor A. Milchev (Acad-
emy of Sciences, Sofia, Bulgaria) for his stimulating interest
in this work. The authors also thank the IWT (Vlaams Insti-
Tuesday Jan 11 02:24 PM
89
tuut voor de Bevordering van het Wetenschappelijk Onder-
zoek in de Industrie, Brussels) for financial support and the
award of a research grant to one of us (A.T.).
References
[1] B.R. Scharifker, J. Mostany, M. Palomar-Pardave, ´ I. Gonzalez, J.
Electrochem. Soc. 146 (1999) 1005.
[2] B.R. Scharifker, J. Mostany, J. Electroanal. Chem. 177 (1984) 13.
[3] M. Sluyters-Rehbach, J.H.O.J. Wijenberg, E. Bosco, J. Sluyters, J.
Electroanal. Chem. 236 (1987) 1.
[4] M.V. Mirkin, A.P. Nilov, J. Electroanal. Chem. 283 (1990) 35.
[5] J. Mostany, J. Mozota, B.R. Scharifker, J. Electroanal. Chem. 177
(1984) 25.
[6] M.T. Palomar-Pardave, M.T. Ramirez, I. Gonzalez, A. Serruya, B.R.
Scharifker, J. Electrochem. Soc. 143 (1996) 1551.
[7] M.T. Palomar-Pardave, I. Gonzalez, A.B. Soto, E.M. Arce, J. Elec-
troanal. Chem. 443 (1998) 125.
[8] J. Yu, H. Cao, Y. Chen, L. Kang, H. Yang, J. Electroanal. Chem. 474
(1999) 69.
[9] L. Heerman, A. Tarallo, J. Electroanal. Chem. 470 (1999) 70.
[10] R.L. Deutscher, S. Fletcher, J. Chem. Soc., Faraday Trans. 94 (1998)
3527.
[11] A. Milchev, J. Electroanal. Chem. 457 (1998) 35.
[12] A. Milchev, J. Electroanal. Chem. 457 (1998) 47.
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