J. Efectroanal. Chem.

, 177 (1984) 13-23 13

Elsevier Sequoia S.A., Lausanne - Printed in The Netherlands

THREE-DIMENSIONAL NUCLEATION WITH DIFFUSION CONTROLLED

GROWTH

PART I. NUMBER DENSITY OF ACTIVE SITES AND NUCLEATION RATES

PER SITE

B.R. SCHARIFKER and J. MOSTANY

Departamento de Quimica, Universidad Simbn Bolioar, Apartado 80659, Caracas 1080 -A (Venezuela)
(Received 3rd March 1984)

ABSTRACT

The current transient for three-dimensional nucleation on a finite number of active sites, followed by
diffusion controlled growth, has been analysed. Both the number density of active sites and the true
nucleation rate per site can be obtained from the current maximum of single-step potentiostatic
experiments. Instantaneous and progressive nucleation are shown to be special cases of the more general
situation described.

LIST OF SYMBOLS

A nucleation rate per active site (s-t)

= zFD’/~~/~‘/’ (A s’12 cm-*)
z = &rkD (s-l)
c bulk concentration (mol cme3)
c(r, t) instantaneous concentration at a radial distance r from hemispherical centre (mol cm-‘)
c(z, t) instantaneous concentration at a distance z from the planar surface (mol cm-3)
D diffusion coefficient (cm* s-t)
E expectation number
F the Faraday constant (C mol-‘)
I current density (A cm-*)
IIn maximum of current (A cmm2)
J, flux density at the surface of hemispherical centre (mol cmm2 s-‘)
JP flux density at the surface of planar electrode (mol cmm2 s-t)
k = (In&/p) ‘I2 dimensionless constant affecting growth rate of diffusion zones
M molar mass of the deposit (g mol-‘)
N number density of growing centres (cmm2)
N, number density of active sites (cme2)
N 0.1 number density of active sites not converted into growth centres at time t (cmm2)
P probability
R radial distance from a representative point (cm)

0022-0728/84/$03.00 0 1984 Elsevier Sequoia S.A.

14

r radial distance from hemispherical centre (cm)

‘d radius of diffusion zone (cm)
t time (s)
u age of diffusion zone (s)
W Jacobian matrix
x = bt, dimensionless time of the maximum
,? distance normal to the plane (cm)
a = b/A dimensionless parameter
density of the deposit (g cmm3)
z fractional area covered by diffusion zones

INTRODUCTION

The experimental study of electrochemical three-dimensional nucleation processes

usually relies upon the determination of the number of crystallites on an electrode
surface, either from the direct microscopic observation of the surface or by correlat-
ing the measured electrical variable, most commonly the current, to the number of
crystallites. The result has invariably been the product of the nucleation rate per
active site on the surface, A, and the number density of active sites for nucleation, NO
[1,2]. Both quantities, however, vary with overpotential and in order to establish the
exact relationship between the overpotential and the kinetics of nucleation, it is
necessary to determine separately NOand A. In particular, the value deduced for the
free energy change of nucleation from experimental data on the variation of the
product AN, with overpotential would be in gross error if N,, itself varied signifi-
cantly with overpotential.
The fact that the number of active sites for nucleation may not be constant
throughout the overpotential range has been recognised already [3] and even a
distribution of activities of the sites has been proposed [4] but, to the knowledge of
the present authors, the number of active sites has been assumed to be constant in
all experimental investigations of three-dimensional nucleation to date, and thus the
variation of the apparent nucleation rate, AN,, with overpotential, has been equated
to the variation of true nucleation rate A with overpotential, notwithstanding the
fact that it is the latter quantity which is needed for a knowledge of the energetics of
nucleation. Thus it is important to be able to determine NO and A separately if
meaningful comparisons are to be made with the different theories of nucleation
[5,61.
In this paper, we will develop the method of calculating current transients for
three-dimensional nucleation with diffusion controlled growth described in previous
communications [7,8], in order to determine NO and A simultaneously from single
step potentiostatic current transients. The second paper of this series will present the
basic results of the experimental investigation of the number density of active sites
and the nucleation rates per site for the nucleation of lead on vitreous carbon.
Further aspects, such as the modification of the number density of sites and of the
true nucleation rates by adsorption of ions from solution, will be reported in later
communications.
 15

Projection of hemispherical diffusional fields onto the plane of the electrodes

In order to calculate the current transient, we will consider the equivalent area of
plane surface towards which diffuses, by linear diffusion, the same amount of
material that would be transferred, through spherical diffusion, to a hemispherical
growing centre [7]. The total amount of material that diffuses to a hemispherical
electrode of radius rO is

2ar,2J,(t) = -2 sr,2D(ac(r, t)/ar).=., (1)

where J,(t) is the flux at the surface of the hemisphere. Under conditions of
semi-infinite diffusion and with zero surface concentration of electroactive species,
the mass transport equation (1) results in the well known expression [9]

(ac( r, t)/ar).=,, = c/( 7rDt)1’2 + c/r0 (2)

but, because of the small size of the nuclei in the early stages of their growth, the
second term in eqn. (2) dominates at all times and, to a good approximation, mass
transport may be considered to proceed in a steady state, i.e.

(a+, t)/a+ro = c/r0 (3)

Hence,

2rrtJF(t) = -2ar,,Dc (4
The equivalent area of plane surface, rr:, towards which the same amount of of
material diffuses as that given by eqn. (1) can be defined through eqn. (5)

‘rrrd2Jp(t) = -nriD(ac(z, t)/&),_, (5)

where Jr< t) is the flux at the surface of the planar electrode and z is the direction
normal to the plane. For semi-infinite linear diffusion and complete diffusion
control eqn. (5) results in

7rrd2Jp(t) = -~ar~~D’/~c/~~/~t’/~ (6)

Now, since we have defined r, in such a way as to equate the amount of material (i.e.
flux x area) diffusing either to the hemisphere or to the segment of the plane of area
mr2, then

2rriJ,( t) = mriJ,,( t) (7)

and from eqns. (4), (6) and (7) it follows that

2mr0 Dc = vr’/2riD1/2c/t’/2

form which the radius of the diffusion zone is given by

rd = (2rO)1’2( nDt)1’4 (8)

This result applies to a stationary hemisphere sitting on the plane. For a growing
16

hemispherical nucleus, its radius can be expressed as [2,10]

‘a ( t ) = (2DcMt/p)“* (9)
and eqn. (8) becomes

Id(t) = (kDt)“2 (10)

where

k = (8m~M/‘p)~‘” (11)
The earlier conjecture [7] that the diffusion zones radii grew with t’/2 is thus
justified by eqns. (10) and (11).

Calculation of coverage probabilities and of the current transients

Having reduced the mass transport from spherical coordinates around each
growing centre to linear, the overlap of hemispherical diffusion fields of individ-
ual nuclei is also reduced from overlap in “2:” dimensions [11,12] to overlap in two
dimensions, for which the calculation of the true coverage of the electrode by the
projection of the diffusional fields onto the plane is exact [13-161. We will consider
that nucleation occurs randomly on a limited number density N, of active sites on
the surface, initially available for nucleation. If their probability of conversion into
growing nuclei is uniform with time, then the decay rate of the number of, sites
available due to their conversion into nuclei is proportional to the number of sites,
i.e.

- dN,,,/dt = AN,,, (12)

where N, f is the number density of active sites remaining available for nucleation at
time t. Integrating eqn. (12) and given the initial condition that N,,a = N,, then

N,,, = N, exp( -At) (13)

thus the rate of formation of nuclei on the electrode becomes

dN/dt = AN,,, = AN, exp( -At) (14)

This equation only takes into account the reduction of the rate of formation of
growing nuclei due to the decay of the number of active sites because of their
conversion into growing nuclei. The further decay of the number of active sites due
to their ingestion either by the growing nuclei themselves or by exclusion zones for
nucleation associated with the diffusion zones discussed above is taken into account
by the statistical treatment of collision and overlap of diffusion zones that follows.
Since the growth rate of diffusion zones is always larger than the growth rate of the
nuclei that originate them, cf. eqns. (9) and (lo), then ingestion by diffusion zones
will necessarily precede ingestion by growing nuclei, and thus the latter need not be
considered. Furthermore, it is not even necessary to identify diffusion zones with
exclusion zones, for any nucleus actually growing inside a diffusion zone will not
 17

contribute to the observed current and will therefore behave just as a “phantom”
nucleus [14].
Given the rate of formation of nuclei by eqn. (14) and the growth rate of diffusion
zones by eqn. (lo), the true coverage of the electrode by them can be calculated by a
number of methods, all leading to the same result. We will follow here the method of
Evans [15-171 but we wish to point out that that of Avrami [14] produced the same
final expression for the true coverage. The probability that a representative point,
chosen at random at the surface of the electrode, shall be crossed by exactly m
diffusion zones can be found from the Poisson equation

P,=E”exp(-E)/m! (15)

where E is the expectation number. The probability that no diffusion field will cover
the representative point is then

Po=exp(-E) (16)

P, is the fractional area of the electrode that remains uncovered and, since the
expectation number varies with time, is also a function of t. The radius of the
projection onto the plane of the diffusion field of a growing nucleus, the diffusion
zone, is given by eqn. (lo), and it follows that any diffusion zone of age u > R*/kD
developed within an annulus of width dR and radial distance R from the representa-
tive point will pass it and that the longest distance from which a diffusion zone
originated at time t can reach the representative point is (kDt)‘/*. It then follows
[17] that the expectation number of diffusion zones that can cover a representative
point is

E = (W’0”2 (’
2mRAN,,_ expl
__ -A(t- . u)]dudR
Jo JR2/kD

=N,nkD[f+(l -e-“‘)/A] (17)

and hence that the fractional area covered by diffusion zones, 8 = 1 - exp( - E), is

B=l-exp{-NomkD[t-(l-e-A’)]} (18)

The radial flux density of electroactive material through the boundaries of the
diffusion fields will be given by the equivalent planar diffusive flux to an electrode
of fractional area 0 [7]. Thus the current density to the whole electrode surface is

1= ( ,SD1’*c/7r1’*t’/*)(1 - exp{ - NomkD [ t - (1 - ebA’)/A] }) (19)

This expression can be presented in non-dimensional form [8] by plotting Z’/Zi vs.
t/t,, Fig. 1, for different values of the dimensionless parameter (Y = N,rkD/A.

Parameters of the current maximum

The current described by eqn. (19) passes through a maximum and therefore the
current Z, and the time t, corresponding to the maximum can be evaluated by
18

equating the first derivative of eqn. (19) to zero. t, is thus given by

ln(1 + 2bt, - 2btmeeA’m) - bt, + (b/A)(l - eCA’m) = 0 (20)

where
b = NgrkD (21)
Making the substitutions
x = bt m (22)

a=b/A (23)
we obtain from eqn. (20)

ln(1 + 2x - 2xeCxla) -x + a(1 - eeX’,) = 0 (24)

Equation (19) can now be written in terms of x and a for the current maximum, i.e.

Im=(a/t~2){1-exp[-x+a(l-e-“/“)]} (25)
where

a = ~FD’/~c/,rr’/~ (26)
and thus knowledge of I,,, and t, from experimental current transients allows the
simultaneous determination of x and a by solving the system of transcendental
(non-linear) equations

ln( 1 - I,ty’/a) + x - a(1 - eCxlrr) = 0 (27.1)

ln[l + 2x(1 - eCXILI)] -x + a(1 - e-X’u) = 0 (27.2)

from which N, and A are obtained, simultaneously, from single-step potentiostatic
experiments.
In order to solve the system of equations (27), we first note that eqn. (27.2) can be
solved numerically to obtain x as an function of a. A plot of values of x that satisfy
eqn. (27.2) for different values of a, found using Newton’s method, is shown in Fig.
2. On the other hand, adding eqn. (27.1) to eqn. (27.2) one finds that

-ln(l - I,ty’/a) = ln[l + 2x(1 - e-x/a)] (28)

from which

I,tz’/a = 2x(1 - e- "'")/[l + 2x(1 - e-x/a)] (29)

We can then use the appropriate values of x and a found above, cf. Fig. 2, to
construct a plot of Z,,,t~‘/a vs. log a from eqn. (29), which is shown in Fig. 3. From
these two plots and through the definitions of b, x, a and a given in eqns. (21)-(23)
and (26), it is possible to find both N, and A from the experimental values of Z, and
t In’
We will now examine the two limiting cases of small a, or “instantaneous”
 19

IO’1 /Aem-*
i

( I/Im)’

I.C

0.5

t /tm
I

0 1 2 3 4

Fig. 1. (a) Calculated current transients for D = 1 X10-s cm’ s-l, c = 1 X10-s mol cmm3, M = 207.2 g
mol-‘, p=11.3 g cmm3, z = 2 and AN, =109 cm-’ s-‘. (1) a = 0.16, (2) LY= 0.50, (3) (Y = 2.0. (b)
Non-dimensional plots of the transients in (a) together with the corresponding plots for instantaneous
nucleation (upper continuous curve) and progressive nucleation (lower continuous curve).
20

Fig. 2. Solution of eqn. (27.2). (0) Numerical solution using Newton’s method; (-- -) asymptotic
solution for low values of a, eqn. (32); (- ) asymptotic solution for large values of a, eqn. (35).

0.95 - l/2
Imtm
a

0.90 -

0.70 - to9 a

-3 -2 -I 0 I 2 3

Fig. 3. Plot of I,,,f~,/‘/u vs. log a, eqn. (29), using values of x corresponding to OLfound by the numerical
solution of eqn. (27.2).
 21

nucleation, and large (Y,or “progressive” nucleation. They correspond to the extreme
situations of fast nucleation on a small number of active sites and slow nucleation on
a large number of active sites, respectively, and have been discussed in previous
communications [7,8].
For instantaneous nucleation (LX-+ 0) it has been shown that [7]

1= (~~/t’/‘)[l -exp(-bt)] (30)

and that t, = 1.2564/b. Introducing this value into eqn. (30) and rearranging one
obtains
I,,,t’,‘/a = 1 - exp( - 1.2564) = 0.7153 (31)
which is the limiting value for a + 0 of I,ty’/a obtained from the solution of eqn.
(27), shown in Fig. 3. Furthermore, the asymptotic solution of eqn. (27.2) for small
values of (Yis
x = 1.2564 lx-+0 (32)
and is shown as a broken line in Fig. 2.
For progressive nucleation (CY+ cc), similarly [7],

I = (a/~‘/~)[ 1 - exp( -Abt2/2)] (33)

and t, = (4.6733/Ab)‘j2. Thus
I,t~‘/u = 1 - exp( - 2.3367) = 0.9034 (34)
which is the limiting value for cy -+ cc found from the solution of eqn. (27), Fig. 3.
Then “instantaneous” and “progressive” nucleation can be considered as special,
extreme cases of a more general phenomenon of heterogeneous nucleation on a finite
number of active sites on the surface, as recently pointed out by Abyaneh and
Fleischmann [17]. Now, from eqns. (22) and (23), Abti/2 in the exponential term in
eqn. (33) can be equated to x2/2~ and then

lim ( x2/2cr) = 2.3367

a-a,
thus

x = (4.6733~~)~‘~ = 2.1618~~“~ (r-cc (35)

gives the asymptotic solution of eqn. (27.2) for large values of (Ywhich is shown by
the continuous line in Fig. 2.
The set of equations (27) can be solved graphically, by the procedure outlined
above, using the plots presented ‘in Figs. 2 and 3 as working curves. It is a simple
matter, however, to find its solution by means of numerical analysis [18]. Given a set
of continuous and differentiable equations in the vicinity of the roots x,(Y:

(36)

the Jacobian matrix of the set can be constructed as the derivatives off, and f2 with
22

respect to their variables,

w(x, a) =
afox af,m
(37)
[ afox afdaa 1
Having an approximation to the roots of the set, xp and (Ye, a better approximation
Xptl7ap+1 can be found from the expression

(38)

The solution of the set of equations (27) is thus found iteratively by successive
approximations of x and (Yuntil the residuals fi( x, a) and f2(x, a) are smaller than a
preestablished convergence criterion. The experimental determinations of N, and A
for the nucleation of lead on vitreous carbon described in Part II of this series were
accomplished with this numerical method.

SUMMARY

Three-dimensional nucleation on a finite number of active sites followed by

diffusion controlled growth of nuclei has been analysed, and an expression for the
current transient was obtained by consideration of the two-dimensional projections
of three-dimensional diffusional fields of individual nuclei onto the plane of the
electrode. The current maximum is shown to provide the information needed for the
simultaneous evaluation of the number density of active sites on the surface and of
the rate of nucleation per active site. A procedure is described whereby working
curves allow the determination of both quantities from single-step potentiostatic
experiments. Finally, instantaneous and progressive nucleation are shown to be
special cases of the more general situation described here, and they were recovered
through the asymptotic solutions for small and large values of the dimensionless
parameter (Y, respectively.

ACKNOWLEDGEMENT

One of us (B.S.) gratefully acknowledges the Consejo National de Investigaciones

Cientificas y Tecnologicas (CONICIT) of Venezuela for financial support through
grant number Sl-1227.

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