Pergamon Chemical Emginrering S&me, Vol. 49, No. 10. pp. 1493-1572.

1994
Copyright Q 1994 Eisevier Science Ltd
Printed in Gnat Britain. All rights rcscrvcd
ooo9-2509P4 $24.00 + 0.00

REVIEW ARTICLE NUMBER 44

ELECTROCHEMICAL REACTION DYNAMICS: A REVIEW

J. L. HUDSON
Department of Chemical Engineering, School of Engineering and Applied Science, Thornton Hall,
University of Virginia, Charlottesville, VA 22903-2442, U.S.A.

and

T. T. TSOTSIS’
Department of Chemical Engineering, School of Engineering, HEDCO Building, University of Southern
California, Los Angeles, CA 90089-1211, U.S.A.

Abstract-We review here the status of research on the dynamics of electrochemical reactions. The
electrodissolution of metals, cathodic deposition, and electrocatalytic reactions are discussed. We treat
dynamic behavior such as periodic oscillations, bifurcations, chaos, and spatial patterns and also the status
of mechanisms and mathematical models, which explain the dynamics.

CONTENTS
INTRODUCTION ............................. . . . * *. . * . . 1493
ELECTROCHEMICAL EXPERIMENTS ........... .... . 1494
Experimental techniques ........................ ........ 1494
Techniques for data analysis ..................... ........ 1495
ELECTRODISSOLUTION OF METALS ........... 7 ........ 1499
Iron electrodissolution ......................... ........ lSo0
Anodic dissolution of copper .................... ........ . 1514
Nickel electrodissolution ........................ ........ 1523
Other metals ................................. .. ........ 1528
Other elements ............................... ........ . 1533
CATHODIC PROCESSES ....................... .... . . 1534
ELECTROCATALYTIC REACTIONS ........ 1546
Oxidation of small organic molecules .............. ........ 1546
Hydrogen oxidation ........................... ........ 1554
Hydrogen peroxide reduction .................... 1.556
Other electrocatalytic reactions ................... ...... 1559
SEMICONDUCTOR ELECTRODES .............. 1559
MEMBRANES ................................ .. .... . . 1561
CONCLUDING REMARKS ..................... .. .. ....... 1.561
REFERENCES ................................ ..... . 1561

INTRODUCTION two-phase gas-liquid reactors, and in heterogeneous

Chemically reacting systems can exhibit interesting surface catalyzed reactions.
steady-state and dynamic behavior, such as simple Oscillations and surface patterns can also arise in
and complex periodic oscillations, quasiperiodicity, electrochemical reactions. In potentiostatic (constant
and chaos; furthermore, both surface waves and time- potential) systems the current can oscillate and in
varying spatial structures have been observed. Non- galvanostatic (constant current) systems the potential
steady behavior can occur even when all external can oscillate. Both the current and potential can oscil-
conditions, such as feed rate and concentrations, cool- late in less restricted systems. Nonsteady behavior of
ing temperature, etc., are held constant. Oscillations electrochemical systems was observed as early as 1828
have been observed in continuous stirred reactors, (Fechner, 1828), and has been the subject of numerous
investigations since then. Much of the earlier work
has been reviewed by Wojtowicz (1972) and Poncet et
‘Author to whom correspondence should he addressed. al. (1977). In fact, there are probably more examples of

1493
1494 J. L. HUDSON and T. T. TSOTSIS
oscillating systems in electrochemistry than in any and concepts. For further details standard textbooks
other area of chemistry. in electrochemical engineering should be consulted.
We review and discuss some of the most important Some of the quantitative methods of data analysis are
experimental and theoretical studies dealing with the presented in the subsection “Techniques for data ana-
topic of electrochemical reaction dynamics. Our pri- lysis”. We show how periodic, quasiperiodic, and cha-
mary emphasis is on the most recent studies. The otic time series from electrochemical experiments can
reader is referred back to the classical review paper by be analyzed. We note that, with variation of a para-
Wojtowicz (1972) and to the paper of Poncet et al. meter, such as voltage or current, the behavior can
(1977) for detailed discussions of research done before change from steady to oscillatory; with further vari-
the early 1970s. Three recent reviews have also been ation a simple periodic oscillation can change to one
written on specific aspects of electrochemical dy- with twice the period (a period-doubling bifurcation)
namics. The dynamics of metal electrodissolution has or can change to an oscillation with two fundamental
been considered by Hudson and Bassett (1991) and incommensurate frequencies, i.e. quasiperiodicity. We
chaotic behavior in electrochemical systems has been also give examples of transitions to chaos from both
reviewed by Hudson (1993). The application of fractal periodic and quasiperiodic behavior. Several
theory to the analysis of the complex behavior ob- examples of different types of low-order chaos are
served in many electrochemical reaction systems has discussed. In addition, we show that higher-order,
been reviewed by Costa (1991). more complicated chaos can arise in electrochemical
Electrochemical reactions have several features, systems and that this increase in complexity can be
which make their use in dynamic studies interesting. produced with variation of a parameter; transitions
The first, of course, is that many types of dynamic have been observed from periodic to low-order cha-
behavior have been observed, as will be seen below. otic to higher-order chaotic behavior.
Secondly, the measurement of current or voltage is The emphasis of this review, however, is on
relatively straightforward. Furthermore, noise is often examples of oscillatory behavior, which have been
at a sufficiently low level such that the data can be seen in a variety of types of systems. We discuss such
interpreted without ambiguity. Finally, the time scale behavior in the electrodissolution of metals, in cath-
of the oscillations, under some conditions, is short odic processes, and in electrocatalytic reactions. We
both relative to the time scale of changes in the surface also give a few examples of studies of nonuniform
conditions, so that data are taken under stationary electrodes. Interesting dynamics have also been ob-
conditions, and absolutely so that large amounts of served with solid electrolyte type electrochemical sys-
data can be obtained to use in data analysis. tems [see e.g. Enoki et al. (1977), Hetrick and
The majority of electrochemical systems, for which Logothetis (1979), Okamoto et al. (1983) and Yen-
interesting dynamic behavior has been reported, in- tekakis and Vayenas (19SS)l. These will not be dealt
volve the anodic dissolution of various metals. Since with further here.
some of the oscillations observed are associated with
pitting metal corrosion, it is only natural that such
anodic dynamic phenomena have attracted significant ELECTROCHEMICAL EXPERIMENTS
attention and interest. Oscillations and other dy- Experimental techniques
namics are, however, not associated with anodic pro- All of the experiments discussed here were carried
cesses only. Intricate dynamics have also been ob- out using either stationary wire, rod and disk elec-
served with several cathodic systems, especially those trodes or rotating disk electrodes. Rotating disk elec-
involved with the electrodeposition of various metals, trodes are often utilized to eliminate or reduce the
an area of great technical significance. Fuel cells have, mass transport limitations associated with fast elec-
in recent years, attracted a growing interest. These trochemical kinetics.
systems involve the direct electrochemical oxidation A schematic of a rotating disk electrode is shown in
of various electroorganic compounds. Several of these Fig. 1. The electrode is simply a metal rod embedded
electrochemical reaction systems have also shown in a Teflon cylinder. Only the end of the metal rod is
some very interesting dynamic behavior. More exotic exposed to the electrolyte. The potential of the work-
examples of electrochemical systems, that exhibit os- ing electrode is measured relative to a reference elec-
cillations and other dynamics, involve semiconductor trode; a saturated calomel electrode (SCE) is shown in
electrodes and photoelectrochemical processes and Fig. 1. Several other reference. electrodes also exist.
systems in which biological/organic membranes are The type of electrode used depends on the particular
present. experiment being carried out. Current flows between
In the section below entitled “Electrochemical Ex- the working and the counterelectrodes. The arrange-
periments” we give an overview of some of the types of ment of the three electrodes varies depending on the
behavior which have been observed in electrochemi- nature of the experiment. The reference electrode
cal reactions. In the subsection “Experimental tech- might be in a side chamber or might be close to the
niques” we briefly discuss some of the methods used in surface of the working electrode. The counterelec-
experimental studies of electrochemical reaction dy- trode can also be in a side chamber or might be
namics. We do so only to familiarize those of our located below the surface of the rotating disk. The
readers unfamiliar with the area of basic terminology makeup of the electrolyte, of course, depends on the
 Electrochemical reaction dynamics 1495

/ Fig. 2. Current density vs potential curves at various acid

Working concentrations: thick lines denote potentiostatic run, solid
elcctrodc
and broken thick lines denote, respectively, galvanostatically
stable and unstable states. Thin lines show end points of
Fig. 1. Rotating disk electrode apparatus
galvanostatic conditions. From Lev et al. (1988b).

reaction being investigated. The rotating disk is

a standard electrochemical apparatus. With it the
mass transfer resistance between the metal surface and
the bulk fluid can be controlled by fixing the rate of
rotation of the disk. In studies concerned with the
investigation of the spatial structures during nickel
dissolution, the cell contained two parallel nickel
wires (one working, one counter) and a reference elec-
trode. In addition, 15 microreference electrodes were
placed along the nickel working electrode to measure
local current distributions. These were referenced to
another reference electrode, which was placed in the
vicinity of the cell’s reference electrode.
Experiments are carried out either potentiostati-
tally, i.e. at constant potential while the current is
monitored as a function of time so that analysis of the
oscillations can be performed, or galvanostatically, i.e.
at constant current while the potential is being meas-
ured. In a number of the studies discussed, the experi-
ments were carried out under dynamic conditions, i.e.
while the potential or current is constantly ramped up
and down. It is sometimes difficult to say, under these
conditions, whether the oscillations observed are sus-
tained or an artifact of the experimental method.
A number of papers by &hell and coworkers, to be
discussed later, have focused on these exact issues.
Techniquesfor data analysis
In this section we give a description of the methods,
which have proven to be useful in the analysis of
oscillatory or other dynamic data from electrochemi-
cal experiments. The data are typically available in the
form of a time series, either of current or of potential
as a function of time, often after all transients have
died out. In experiments done potentiostatically, for
example, the current is measured. After some time the
current becomes steady or settles down into a station-
ary pattern, such as a periodic oscillation or a chaotic
behavior. One then analyzes the system after it has
become stationary. In many cases (as specifically
noted) the system never really becomes stationary.
Instead, it undergoes a slow transient on which faster
dynamics are sometimes superimposed; often, one
then analyzes the faster dynamics using a section of
the time series. The transient approach to some final
state sometimes also contains interesting dynamic be-
havior, which helps in the identification of the various
mechanistic steps responsible for oscillations.
The most common technique of data analysis (espe-
cially in the earlier studies) involved simple observa-
tion and discussion of the oscillatory and other dy-
namic time series. The time-series behavior is often
studied as a function of a system parameter. Such
a plot, for example, is shown in Fig. 2 for nickel
electrodissolution in sulfuric acid solutions. The cur-
rent is the parameter held constant. The potential is
the measured variable. For low current values the
potential is constant. For larger current values the
potential oscillates and the maxima and the minima of
the oscillations are then indicated in the figure.
A more useful plot, when the data are available
(which is not often), is a diagram showing the behav-
ior of a system as a function of two parameters. Such
diagrams can be found, for example, in Lev et al.
(1988b) and Albahadily et al. (1989) and an example is
shown in Fig. 3. The two parameters in this case are
the potential and the rotational speed of a rotating
disk elecrtrode. Regions of steady-state and oscilla-
tory behavior are shown. In addition, different types
of oscillatory behavior are indicated (these studies will
be discussed in more detail below). A means for deal-
ing with oscillatory (dynamic) data is taking its
Fourier transform. Such transforms can often identify
underlying periodicities in data. They can also help
distinguish between quasiperiodic and chaotic signals
(Eckmann and Ruelle, 1985). A quasiperiodic time
signal and its Fourier transform are shown in Fig. 4.
An example of simple chaos is shown in Fig. 5. The
time series is shown in Fig. 5(a) and has no apparent
periodicity. Without the tools of nonlinear dynamics
the experimenter would not be able to say much more
about this behavior. A power spectrum of the time
series shown in Fig. 4(a) is given in Fig. 4(b). Often the
power spectrum cannot distinguish conclusively be-
tween chaotic behavior and a periodic or
quasiperiodic signal with noise because all have
power spectra with broad peaks at many frequencies
or no peaks at all, just a broad continuum. Other
techniques must then be used to be able to say
whether the behavior is periodic, quasiperiodic or
chaotic.
1496 J. L. HUDSON
420 460
Potential (mV)
Fig. 3. The parameter plane (rotation speed vs the potential
of the working electrode) divided into regions where different
dynamical behavior was observed. The largest variety was
found in the thin banana-shaped region, whose. various parts
are labeled in the lower right inset which is an enlamement of
the rectangle indicated by the arrow. Parameter ranges in
this rectangle: 424.0-429.5 mV. 1450-1600 rum. P = peri-
odic oscilla%ons with small amplitudes. QP =-quasiperiodic
oscillations. x = chaotic oscillations. MM0 = mixed-mode
oscillations. 1’ = a periodic mixed-mode state with one
large-amplitude oscillation and one small amplitude oscilla-
tion per cycle. lo = a periodicstate with one large-amplitude
oscillation per cycle. Note that at lower potentials we ob-
servedP to deformsmoothly into lo as the rotation rate was
increased. SS = stationary-state behavior. The inset in the
upper-leftcorner is an enlargementof the lower tip of the
banana. Parameter ranges for this enlargement:
405.5-408.0 mV, 1280-1310 rpm. Reproduced by per-
mission of the Electrochemical Society from Albahadily er
nl., J. them. Phys. (1989).
Another very useful tool for dynamic data analysis
is the reconstruction of the attractor. An attractor is
a subset of phase space to which nearby trajectories
are attracted. This method can transform a very com-
plicated time series into an attractor with a relatively
simple form, which is much easier to visualize than the
time series. The most commonly used method to re-
construct an attractor is the method of time delays.
Additional variables are created by using the values of
a variable at previous times. Let us say, for example,
that some variable Z(t) is recorded as a function of
time. A three-dimensional state space plot, for
example, can be created by plotting the values of
Z(t), Z(t - 22), Z(r - 42), where 7 is some time con-
stant. For higher-dimensional reconstructions one
just uses more time-delayed variables. This method
has been proven by Takens (1981) to be a valid tech-
nique for the reconstruction of an attractor from
a time series. This technique had been suggested pre-
viously by Packard et al. (1980). For steady-state
behavior, the attractor is a point. Periodic behavior
has an attractor which is a closed line, which can
either be very simple or complex. Quasiperiodic be-
havior has an attractor which is a torus, and low-
order, chaotic behavior has a “sheet-like” attractor.
The reconstructed attractor from Fig. 5(a) is shown in
and T. T. TSOTSIS
Fig. 5(b). It has a relatively simple and well-structured
form.
It is often useful to take a transverse cut through the
attractor. This cut is called a Poincari: section, and is
represented in a dimension less than the original state
space. For example, a plane is typically used to make
a Poincar6 section of an attractor in three-dimen-
sional space. For periodic attrators, whose dimension
is one, the Poincark section yields a set of points, the
number of which is the periodicity of the attractor.
For example, one, two, and four peak periodic attrac-
tors have Poincare sections with one, two, and four
points, respectively. The simplest quasiperiodic be-
havior is a two-dimensional torus and has a Poincark
section which is a closed line. For low-dimensional
chaotic attractors with a single positive Lyapunov
exponent (defined below), where the dissipation is
sufficiently strong, the Poincar6 section has a simple
shape. An example is given in Fig. 5(c); it looks like
a simple line. In fact, it is a more complicated struc-
ture, which is locally the product of a line and
a Cantor set.
A sequence of Poincark sections is shown in Fig.
5(e) to explain the flow of trajectories around the
attractor. The PoincarC sections were made with
planes at constant Z(t - 2t) = 17.5 mA and
Z(t - 47) = 17.5 mA, and were constructed by using
all the intersections of the attractor of Fig. 5(b) with
the above-mentioned planes. In Fig. 5(e) only a few
orbits around the attractor are shown so that the
location and orientation of the sections can be seen.
The arrow on each section is used to mark the points
that started on the edge of the attractor in section 1.
This sequence shows the stretching, folding, mixing,
and contraction processes common to these types of
simple chaotic attractors (Rossler, 1976a, b, 1977).
Since this behavior is chaotic, it has one positive
Lyapunov exponent and, thus, trajectories diverge
exponentially in one direction. However, since the
trajectories are bound in space, the flow must undergo
a repeated stretching, folding, and contracting process
to merge separating trajectories. As a result of this
process, nearby states on the attractor become decor-
related (Wolf ef al., 1985). Thus, there is an extreme
sensitivity to initial conditions with such systems.
Consequently, no long-range predictions are possible.
In going from section 1 to 2, one observes the stretch-
ing of the trajectories. In going from section 2 to 3, the
trajectories continue to stretch but the folding process
is also observed. In addition, the points that were on
the outside of the attractor are now on the inside. In
going from section 3 to 4, one sees the contraction of
the fold onto itself. This process continues as trajecto-
ries proceed around the attractor mixing the trajecto-
ries to give back the result seen in section 1.
For such low-dimensional chaotic attractors it is
often useful to make return maps from their Poincari
sections. Such a map is seen in Fig. 5(d). The return
map is just the plot of some coordinate value of the
(N + 1)th crossing of the Poincari: plane vs the coor-
dinate value of the Nth crossing of the Poincark
 Electrochemical reaction dynamics 1497

Cd)

..
t
. -

F-4 s--31

19
Time

(4

I J
18
Frequency (Hz)

21.0 25.0
Fig. 4. Quasiperiodicity: (a) time series; (b) power spectrum& = 0.78 Hz& = 4.14 Hq (c) attractor (spline
fit); (d) Poincark section taken at I(t - 21) = 23 mA, increasing f(r - 2~); (e) return map (next angle) of(d),
center point used for the calculation was (24.6,21.3). Reprinted with permission from Bassett and Hudson,
J. phys. Chem. Copyright 1989a American Chemical Society.

plane. For Poincark sections, which appear one-di- are related to the expanding or contracting nature of
mensional, the return map will also appear one-di- different directions in phase space. There are as many
mensional. exponents as there are phase space dimensions. Posit-
Certain types of chaos have very characteristic re- ive exponents give the average rate of exponential
turn maps. For example, chaos which arises via the divergence of nearby trajectories within the attractor.
period-doubling route has a quadratic shape. The Negative exponents, on the other hand, measure the
chaos described in this section arose via the period- average rate of exponential convergence of trajecto-
doubling route and has only a very weak cubic term. ries onto the attractor. In addition, any attractor
Type I intermittency chaos, which arises via an in- other than a fixed point will have at least one zero
verse tangent bifurcation [see Eckmann and Ruelle exponent (Wolf et al., 1985). Since the volume of an
(1985) and Thompson and Stewart (1986)], has a map attractor in a dissipative system is zero, the sum of the
which is tangent to the 45” line. Shil’nikov chaos, exponents must be negative. In three-dimensional
which will be described later, also has a very charac- space, steady states have three negative exponents,
teristic return map. periodic states have two negative exponents and one
An important measure of chaos is the Lyapunov zero exponent, quasiperiodic states have one negative
characteristic exponent (LCE). Lyapunov exponents and two zero exponents, and chaotic states have one
1498 J. L. HUDSON and’T. T. TSOTSIS

Cd)
25
1

5
Time 17 25
10 - 4r1, - ]

17 25
I(t - 27)
Fig. 5. One band chaos: (a) time series: (b) attractor (spline fit); (c) Poincare section taken at I(t) = 17.5 mA,
increasing I(t - 4~); (d) return map constructed from the Poincare section taken at I(t - 25) = 17.5 mA
with increasing I(r - 4~); using variable I(t - 4r); (e) series of Poincark sections showing the flow of
trajectories around the attractor. Sections 1 and 3 were taken at I(t - 2~) = 17.5 mA and sections 2 and
4 were taken at I(r - 45) = 17.5 mA. Reprinted with permission from Bassett and Hudson, J. phys. Chem.
Copyright 1989a American Chemical Society.

negative, one zero, and one positive exponent. It is where 1dy/dx Ii is the slope of the map at the ith iterate
this positive exponent which makes chaos “chaotic”. and n is the number of points making up the return
Techniques have been developed to calculate map. For example, a value for the largest exponent of
Lyapunov characteristic exponents from expezi- 0.6 has been obtained for the map of
mental data. One such method, which was developed Fig. 5(d).
to calculate the largest such exponent, is due to Wolf An important technique for the analysis of appar-
et al. (1985), as already discussed. Other methods are ently chaotic experimental data will now be discussed.
still under development; they clearly offer the best In it, the fractal or Hausdorff dimension of the attrac-
possibility of obtaining reasonable values for expo- tor is estimated. The Hausdorff dimension (D) is the
nents. In addition, approximate values for the measure of the local structure of an attractor. To
Lyapunov exponents from experimental data can define this quantity, one first covers the attractor
sometimes be obtained from a return map constructed (represented in F-dimensional state space) with F-
from the data; such approximate methods have been dimensional hypercubes of side length I and considers
used before the development of the newer algorithms. the limit I + 0. If the minimal number of cubes needed
One uses the expression to cover the attractor M(Z) grows like

I = lim (l/n) i log, I dy/dx 1, (1) lim M(I) cc ImD (2)

n-m i=1 I-10
 Electrochemical reaction dynamics 1499

then the exponent D is called the Hausdorffdimension Reasons for this are discussed, for example, in Ebeling
of the attractor (Grassberger and Procaccia, 1983a, b). et al. (1990) and Mayer-Kress (1986). In this case,
This quantity is especially useful for several reasons. a generalized dimension can be calculated. Before the
The first is that it allows one to differentiate between mean is taken above, the value ni(l) is raised to the
noise and chaos. Secondly, the calculation gives (q - 1) power. The mean is then taken and the result
a lower bound on how many degrees of freedom of raised to the (l/q - 1) power. The result is the gener-
the system need to be defined, in other words how alized dimension dq, for which the correlation dimen-
many equations are needed to model the system. For sion D2 is a special case.
chaotic attractors, the minimum number of degrees of Another method has been recently developed and
freedom needed to define a state is the next largest has been shown to be very useful in calculating the
integer greater than its fractal dimension. Thus, if an dimension of nonuniform attractors [see e.g. Wang et
attractor has a dimension of 2.1, at least three equa- al. (1990) for an application]. This “nearest-neighbor”
tions are needed to model the system [the actual method was developed by Badii and Politi (1985) and
number may be greater than three (Takens, 1981)]. an algorithm based on it was developed by Kostelich
A method used to estimate an attractor’s fractal and Swinney (1987). It yields an estimate for the
dimension was developed by Grassberger and information dimension Dl. In this method, the dis-
Procaccia (1983a, bk it determines an attractor’s cor- tance between a reference point on the attractor and
relation dimension, which is a lower bound on its its kth nearest neighbor is calculated. For a large
fractal dimension. The first step is to represent the enough data set this distance scales as the number of
data in a d-dimensional space using the time delay points raised (0 the ( - l/Dl) power.
method. Thus, some variable Xi has the coordinates The calculation of attractor dimensions is a power-
ful tool in the analysis of chaotic data. It can furnish
Xi = (x(ti)T X(ti -t 5)~ * e9X[tf + (d - l)T]}. (3)
a verification that the data are indeed chaotic and it
Consider first a single attractor point and calculate indicates how chaotic the data set is. For example,
the relative number of neighbors from that point a dimension of say 2.1 would point to a simple chaotic
which have a distance from it less than 1. This relative attractor with a single positive Lyapunov exponent.
number is given by A dimension of say 3.1 would indicate that the time
series is more complicated and that the attractor has
ni(l) = lim (l/N) F @(I - IXi - X,1) (4) two positive exponents or directions of expansion.
N-CC ,=1 However, the methods can easily yield spurious re-
where 0 is the Heaviside function and 1 is some sults if great care is not taken. This is particularly true
distance. One then calculates the correlation integral in the case of high-dimensional attractors or those
by taking the mean of the above equation over all with a high degree of nonuniformity. The book by
points of the attractor: Mayer-Kress (1986) contains some interesting
examples.
C(I) = lim (l/N) 5 ni(l). The above constitute the most commonly used
(5)
N-m i=l methods of analyzing dynamic data. Other possibil-
C(l) is proportional to the relative number of dis- ities exist. For example, artificial neural networks
tances between all attractor points, which are smaller have recently been used in the analysis of a period-
than the given distance 1. This taking of the mean doubling route to chaos (Hudson et al., 1990; Rico-
results in Martinez et ol., 1992).

C(I) = lim (l/N’) C @(I- IXi - Xii). (6)

N-CC i,j=l
ELECTRODISSOLUTION OF METALS
It has been shown by Grassberger and Procaccia In this section we discuss some of the dynamics
(1983a) that which have been observed during the electrodissol-
C(l) x I’ ution of metals. This category of reactions has re-
(7)
ceived more attention than the other types of electro-
where v is the correlation dimension (often called D2) chemical reactions (Hudson, 1989,199l) and has been
for smaller values of 1. Thus, to calculate Y, one deter- the subject of a recent review (Hudson and Bassett,
mines the slope of the linear portion of the plot of 1991). Through the years, several different metals have
log {C(Z)} vs log {I}. Practically, one repeats these been shown to produce oscillatory dissolution. Fur-
calculations for increasing values of the embedding thermo-e, many interesting types of temporal and
dimension until a saturation value of v is reached, in spatial behavior have been produced.
other words until v does not increase with increasing In the past few years several of the tools of nonlin-
d. For the behavior in Fig. 5, the correlation dimen- ear dynamics have been applied to time series ob-
sion was found to be 2.2, thus indicating chaos and the tained from electrodissolution of metals (Albahadily
fractal nature of the attractor. For nonhomogeneous and Schell, 1988; Albahadily et nl., 1989; Bassett and
attractors, i.e. those whose trajectories are not spread Hudson, 1987, 1988a, b, 1989, 1990a,b; Diem and
“nicely” uniformly over the entire attractor, the above Hudson, 1987; Kawczynski et al, 1988; Lev et al,,
method often fails to converge to a correct value. 1988a, 1989). Diem and Hudson (1987) and Wang and
1500 J. L. HUDSON and T. T. Tsorsrs

Hudson (1991) have used methods such as the calcu- electrodissolution in HLSOL solutions. Bartlett (1945)
lation of a correlation dimension (Grassberger and reported on the various acidic transients observed for
Procaccia, 1983a, b) to show the existence of simple the Fe/H,S04/Pt system. He observed overshoot
and higher-order chaotic structures during the elec- phenomena, and various relaxation-type oscillations.
trodissolution of iron in H,SO, at the limiting-cur- In a follow-up study Bartlett and Stephenson (1952)
rent plateau. Copper electrodissolution in HJPO* has used an optical microscope together with poten-
been studied by Albahadily and Schell (1988) and tiodynamic and potentiostatic experiments in order to
&hell and Albahadily (1989) and has been found to study in situ the electrode surface during the various
undergo Hopf bifurcations to oscillatory behavior transients and oscillations observed with this reac-
and period-doubling bifurcations to simple chaos. tion.
This system was also found to give both periodic and The potentiostatic polarization curve as reported
chaotic mixed-mode oscillations. Lev et al. (1988a, by Bartlett and Stephenson is shown in Fig. 6. This
1989) have studied the galvanostatic electrodissol- curve was made starting from a potential of - 0.65 V
ution of nickel in HzS04; they have observed Hopf (vs SCE), raising the potential in steps of 0.05 V, and
bifurcations, saddle-loop bifurcations, period-doub- allowing at least 1 min for the current to assume its
ling bifurcations, chaos, and quasiperiodicity. In addi- steady-state value. Note in Fig. 6 the Hz and O2
tion, Lev et al. (1988b) have observed spatial struc- evolution regions, the passivation region and the re-
tures during nickel dissolution. Bassett and Hudson gion, where oscillations are observed, just prior to
have shown that copper electrodissolution in NaCl passivation on the current plateau. In traversing curve
and HISO gives a plethora of interesting behavior, A the authors report that they observe through their
including a variety of periodic oscillations, period microscope, in the lower voltages, where H, evolution
doubling to simple chaos, type III intermittency, win- occurs, that the anode surface is “metallic gray, badly
dows of period three oscillations within chaotic re- pitted, with a jagged appearance and with gas bubbles
gions (Bassett and Hudson, 1987), Shil’nikov chaos streaming profusely from the pits”. Close to the peak
(Bassett and Hudson, 1988a), quasiperiodicity, chaos the anode begins to turn black and the gas evolution
on a broken torus (Bassett and Hudson, 1989), and decreases. In the beginning of the current plateau the
period doubling of tori (Bassett and Hudson, 1988b). anode loses its jagged appearance, becoming smooth,
The first example to be discussed in detail is the and the black film gives way to a brownish coat. This
electrodissolution of iron in sulfuric acid. The oscilla- brownish coat first forms a thin film covering the
tions in this system have probably received more whole anodic surface. Soon, however, under the ac-
attention than any other case. The next two sections tion of convective currents and occasional gas bubbles
of this review deal with copper electrodissolution and the film ruptures in several places, exposing the
nickel electrodissolution, which also have produced anodic surface. While the film is rupturing, its parts
a large set of fascinating dynamic behavior. We then which remain intact seem to increase in thickness and
discuss briefly other metals that have shown interest- irregularity. Trapped bubbles occasionally break
ing dynamics. loose, carrying with them pieces of the film. Ever)t-
ually, as one keeps traversing slowly curve A, a mech-
Iron electrodissolution anical equilibrium is established in the film.
One of the earliest and most widely studied oscillat- Bartlett and Stephenson (1952) report that when-
ing electrochemical reactions is Fe dissolution in vari- ever the “anode surface can be viewed through the
ous acidic media, with reports on this reaction dating brownish coat it appears to have a swarming motion?,
back to the early 1800s (Fechner, 1828; Joule, 1844). looking like “a gray table top swarming with ants and
Most of the published work on oscillations is for Fe viewed from a great distance”. In the passive region

Hydrogen

cv01uti0n

Anode-calomcl potential (V)

Fig. 6. Typical dependence of steady-state current upon &ode-calomel voltage. Anode area = 2.0 mm’.
Reproduced by permission of the Electrochemical Society from Bartlett and Stephenson, J. electrochem.
Sot. (1952).
 Electrochemical
the brownish coat is removed and the anode surface is
“relatively clear except for scattered black spots”. In
the region of oscillations the anode looks similar to its
appearance in the current plateau region prior to
oscillations, except for an additional effect associated
with the periodic activity. To each drop of current in
the oscillatory cycle corresponds a “twitch”. This
“twitch” was described by Bartlett and Stephenson as
a “brief change or discontinuity in the swarming
motion characteristic of voltages in the active region”.
This twitch appeared to be propagated across the face
of the anode, “starting from the bottom in the case of
a vertical anode”.The authors also report that “co-
incident with each current pulse, small flakes of the
black material previously formed on the anode are
observed to fall away from the face of the anode”. We
report Bartlett and Stephenson’s optical observations
here, in some detail, to make our reader aware that
some of the physical observations associated with
electrochemical oscillations are rather spectacular.
Other transient phenomena observed by Bartlett
and Stephenson are also worth mentioning in the
context of the reproducibility of the various dynamic
phenomena observed with electrochemical reaction
systems. Bartlett and Stephenson carried out a series
of experiments, in which the cell current is interrupted
briefly, by opening and closing a switch, and the
current is monitored, after the circuit is restored. They
observed that the current, after dropping to zero for
the period of interruption, jumps to an initial value
substantially higher than its final steady-state value. It
then decays rapidly to a minimum, and then again
rises slowly to the original steady-state value, before
interruption. Bartlett and Stephenson observed that
in order to obtain reproducible successive transients,
the immediate history of the anode must be faithfully
reproduced for each transient. For example, they
found that transients resulting from circuit off-times
greater than 0.03 s cannot be reproduced with a great
degree of accuracy. Furthermore, although individual
transients in a series produced by short off-times
(C 0.03 s) were exact reproductions of each other, they
are not very accurate reproductions of transients re-
corded several minutes earlier or later.
Reproducibility of the experimentally observed dy-
namic behavior is not a problem unique to the
Fe/H,SO, system or to Bartlett and Stephenson’s
experiments. Similar dificulties are encountered
throughout the published literature on the dynamic
behavior of electrochemical systems. Bartlett and
Stephenson’s microscopic observations offer, how-
ever, some insight into the problems of reproducibil-
ity. They observed that gas evolution began immedi-
ately after the circuit was broken, at the beginning of
off-time, and ceased after the circuit was closed, at the
end of off-time. During the off-time Bartlett and
Stephenson note that “gas bubbles play havoc with
the brownish anode coat, tearing it, shifting it and
even removing it entirely, if the off-time is great
enough”. In fact, the brown surface layer never returns
exactly to the configuration it had before current
reaction dynamics 1501
interruption. To no one’s surprise they also found that
long off-time transients are not reproducible. As the
off-time length decreases, the disruptive effects of gas
evolution also decrease and for sufficiently short off-
times no gas evolution is observed at all, and the
surface layer is unaffected.
Although the gas bubble evolution problem and its
effect on the surface structure and dynamic behavior
is probably unique to the experiments described by
Bartlett and Stephenson, the genera1 pattern is not.
Electrochemical systems are dynamic entities and the
surface of electrodes and even the electrolyte solutions
themselves change as a function of experimental time.
As a result, one often observes changes in the dynamic
behavior, sometimes gradual, sometimes abrupt,
sometimes reproducible and sometimes not. This is
a problem prevalent in the more broad area of hetero-
geneous reaction dynamics.
Franck (1958) and Franck and FitzHugh (1961)
also observed oscillations during Fe electrodissol-
ution in HzS04. Large current fluctuations were ob-
served, in which the current swings between the active
and passive states (for the latter the current is close to
zero). Franck and FitzHugh (1961) developed a math-
ematical model to explain these oscillations. This
model is one of the earliest quantitative models aimed
at understanding the dynamics of this electrochemical
reaction. It also has broader implications, since it is
generally applicable to a variety of other metal elec-
trodissolution systems, which exhibit oscillations and
other interesting dynamic behavior in the so-called
“active-passive transition” range.
The model of Franck and FitzHugh was developed
to explain the large-amplitude oscillations observed
with the Fe/H2S04 system under potentiostatic con-
ditions. It is a two-variable model. The two variables
are the coverage of the electrode surface by a passivat-
ing film, 0, and an overpotential, E, defined as
E- E,-EE, (8)
where E, is the constant applied potential and E, is
the Flade potential. E, is defined as the equilibrium
potential of the passivating reaction (10) to follow. At
this potential Franck and FitzHugh assume that an
abrupt transition occurs between the active and pass-
ive states of the electrode surface. As a two-variable
model, it is unable to predict some of the complex
oscillations observed with the Fe/H,SO, system, to
be discussed later in this section. It also contains
a number of questionable assumptions (see the dis-
cussions that follow). The model of Franck and
FitzHugh is important, however, because of its his-
toric significance as one of the first quantitative
models in this field. The fact, furthermore, that it is
still attracting attention is indicative that, although
oversimplified, it still captures many of the important
features of the phenomenon. Franck and FitzHugh
assumed that the mechanism of metal dissolution is
described as
Fe + Fe’+ + 2e- (9)
1502 J. L. HUDSON
and T. T. TSOTSIS
while the formation of the passivating film can be
written as
Fe + 2H20-t Fe(OH), + 2Hf + 2e-. (10)
The Flade potential, E,, is assumed to depend on H+
concentration, shifted negatively with decreasing H+
concentration, i.e. with increasing pH. The simplest
functional dependence one can think of is a linear one.
Logarithmic dependences were also tried by Franck
and FitzHugh. Franck and FitzHugh further simpli-
fied their model equations by linearizing the cur-
rent/potential curve, They assumed that the rate of
H+ production is negligible, when compared to its
rate of transport, and that its concentration profile in
the diffusion layer is linear. The basic feature of the
model is the discontinuity in the kinetics at the Flade
potential, i.e. at E = 0. A passivating film is formed
when E > 0, and dissolves when E c 0. For E > 0 the
rate of formation is proportional to 1 - 0, and for
E -c 0 the rate of dissolution is proportional to 0.
Metallic dissolution occurs at the active sites when
E e 0. We will proceed by presenting the develop-
ment of the model equations, following the paper of
Talbot et al. (1985). Before we do so, however, we note
that qualitatively the Franck-FitzHugh model de-
scribes a mechanism of sequential steps, which appear
to be a very plausible cause for the oscillations. First,
at the beginning of an oscillatory cycle, the Fe elec-
trode is assumed to bc in an active state with local
current densities of the order of a few A/cm’. Because
of the increase in Fe’+ concentration at the elec-
trode/electrolyte interface, H+ ions electromigrate
away and the local pH increases. The net result of this
pH increase is a decrease in the Flade potential, E,,
and a corresponding increase in the overpotential, E,
which at some point becomes positive. At this point
the electrode passivates, Fez+ production stops, H+
ions migrate back to the electrode/electrolyte inter-
face, the Flade potential increases again, the over-
potential decreases, the electrode again becomes ac-
tive, and the cycle repeats itself. That such a plausible
mechanism will predict oscillations for only a rather
restricted set of conditions, as will be explained below,
should serve as a note of caution against putting too
much faith into the many other more qualitative
mechanisms for oscillations proposed for several elec-
trochemical systems (a number of which will be dis-
cussed in this paper). Until and when a quantitative
analysis of any given mechanism is performed, one
cannot be certain whether or not such a model truly
predicts oscillations.
To proceed with the model, after algebraic manip-
ulation of the original equations, based on the as-
sumptions described above, one ends up with a system
of two differential equations in terms of the over-
potential E and the surface coverage 8:
dE
- = k, - k2E - k3B + k,E W(E, e) (11)
dt
d0
- = k,EW(E,Q) (12)
dt
where W(E, f3) = 8-C (1 - 28)U(E) (U being the
Heaviside step function) is a potential-dependent
function of surface coverage indicative of the discon-
tinuity of the electrode kinetics at E = 0. Note that
l-8 for E>O
w(E,e) = e (13)
{ for E<O.
The definition of the five parameters ki, i = 1, . . . ,5,
which are dependent on reaction and transport coef-
ficients, can be found in the original publications
(Franck and FitzHugh, 1961; Gougerot and
Petitclerc, 1975; Talbot et al., 1985). Pearlstein and
Johnson (1989) made the above system of equations
dimensionless by introducing a dimensionless over-
potential V and a dimensionless time T:
v=y, r=kzt
2
giving
dV
-=bh-V-bf?+ VG(V,I:)/c (15)
dz
b = k3k,/k;, c = k2/k4, h = k,/k,
G(V,0) = [tJ + (1 - 20)U(V)]. (17)
The above system of equations has a unique steady-
state solution (V,, 0,) given as follows:
tracing out a single continuous locus in the (V, 0)
parameter space. Franck and FitzHugh proved the
existence of oscillations by integrating the differential
equations using an analog computer. Talbot et al.
(1985) and Pearlstein and Johnson (1989) sub-
sequently showed this integration to be qualitatively
wrong. Talbot et al. (1985) and Pearlstein and
Johnson (1989), furthermore, used linear stability ana-
lysis, topological arguments, and numerical integra-
tion in order to determine the regions in the para-
meter space where oscillations are possible.
The stability boundary for the above system of
equations is shown in Fig. 7. For all other values of
h and c the above system of equations has a unique
steady state, which is globally stable. A unique glo-
bally stable steady state also exists in region VII of
Fig. 7. In region VIII the unique steady state is un-
stable and is surrounded by a globally stable limit
cycle. Finally, in regions IXA and lXB both a stable
steady state and a stable limit cycle exist. This, in turn,
implies the existence of an unstable limit cycle U sur-
rounding the stable state and lying completely within
the stable limit cycle S. Any trajectory starting within
U will wind up at the steady state, while any trajectory
starting outside U will wind up at the limit cycle S.
 Electrochemical reaction dynamics 1503

Pagitsas and Sazou (1991) analyzed the Franck-

I.07 FitzHugh mode1 using the smoothed Heaviside func-

tion of Wang et al. (1990), but also assuming logarith-
mic dependence of E, on H+. In the Nernst-Planck
equation for the transport of H’ between the electro-
lyte bulk and the electrode, they introduced a correct-
I K ing factor. This factor accounts for the effect of Fe’+

D
c 0.5

E F and SO:+ on the transport of H+ ions and is related

to the transference number of H+ ions.
IXA I% Koper and Sluyters (1993a) have recently recon-
sidered the Franck-FitzHugh model without making
VIII
the assumption of a discontinuous change in the reac-
L R tion kinetics at the Flade potential. They also present
0 0.5 1.0 a new model which incorporates the role of the un-
compensated ohmic cell resistance and the dissolving
metal ions. The bifurcation structure of this new

l.OI VII
model is studied numerically in detail.
Large-period relaxation-type current oscillations
were also observed by Podesta er al. (1979a). These
oscillations were only clearly visible when the poten-
tial was within k 0.05 V of the passivity potential

kTr.zl
c 0.5
range, i.e. within the potential range associated with
J K
the negative resistance in the polarization curve.
E F
Podesta et al. made a very careful study of the charac-
VIII teristics of these oscillations; see Fig. 8 for definitions.
m.4 %
For example, they noted that for H,SO, concentra-
tion, C < 1.2 N, the I,/I, ratio is small, in the range
L R
of 34.6. For C > 1.2 N the ratio increases abruptly to
0 0.5 1.0
values in the range of 85-120. For C - 1.2 N a sharp
h
increase is also observed in the ratio of charges
Fig. 7. The entire stability boundary in the h-c half-plane:
(Q./Qp) associated with the active and passive regions
(top) b = 0.1 and (bottom) b = 1. Reproduced by permission
of the Electrochemical Society from Pearlstein and Johnson, during an oscillation. For H,SO, concentrations lar-
J. electrochem. sot. (1989). ger than 2.0 N, stirring made the oscillations cease.
For C < 2.0 N oscillations do not disappear upon
stirring, but instead a linear dependence of frequency
The Franck-Fitz/Hugh model shows interesting dy- on the square root of the rotational speed was ob-
namic behavior. Urifortunately, the model is not gen- served. Adding Fe ‘+ into the electrolyte did not affect
eric, i.e. any smoothing in the discontinuity around the oscillations. A net corrosion of the metal is ob-
E = 0, regardless of how small, completely changes served after recording the oscillations for a period of
the dynamic behavior. For example, Wang et al.
(1990) changed the function G( V, 0) in eq. (17) by
replacing the Heaviside step function V(V) by
a smoothed Heaviside function x(V), defined as
1
x(V = 1 --withu *O. (19)
(eav + 1)
For large values of a, x(V) is a very sharp smoothed
Heaviside step function, changing abruptly from 0 to
2
1 at V = 0. Despite this, Wang et al. (1990) found that e
the modified system of equations has a different dy- a
v
namic behavior from the original Franck-FitzHugh
model. There are now only two regions in the para-
meter space, one in which only a unique, globally
stable steady state exists, and one where this state
becomes unstable and is surrounded by a unique,
globally stable limit cycle. Only regular supercritical 0
Hopf bifurcations are now observed. Previously, Time
Pearlstein and Johnson had shown that the original
Fig. 8. Definition of parameters in the presentation of the
Franck-FitzHugh model not only exhibited super- current-time relationship. Reproduced by permission of the
critical and subcritical Hopf bifurcations but also Electrochemical Society from Podesta ef ol., J. electrochem.
bifurcations from a homoclinic orbit, More recently, Sac. (1979a).
1504 J. L. HUDSON
and T.T.TSOTSIS
time. This corrosion is macroscopically nonuniform the Fe polarization curve as observed by Russell and
especially at the lower acid concentrations, appar- Newman. Note the region of oscillations AIJ,c in the
ently due to the fact that the electrode behaves as limiting-current plateau. To observe the oscillations
a nonequipotential surface. Podesta et al. (1979a) ex- the potential was swept in the positive direction,
plain their observed behavior by postulating two dif- stopped about 30 mV negative to V,_, (the passiva-
ferent mechanisms, one for the lower and another for tion potential observed under potentiodynamic con-
the higher H,SO, concentrations. The transition, ditions), and then reversed in the negative direction to
however, between the two regions is not abrupt and is a voltage V, in the midst of the AVosc region. In the
placed at about 1.5 N. In the beginning of the active positive voltage sweep one observes overshoot/under-
part of the cycle, Podesta et al. (1979a) suggest that the shoot phenomena, not observed in the negative volt-
high initial rate of Fe electrodissolution results in the age sweep; see Fig. 10. If the electrode is allowed to
accumulation of Fe’+ in the vicinity of the metal
surface and the simultaneous migration of H + away
from that region at an amount equivalent to the Fez+ A
produced. This exchange of H + by Fe’* results in
a local pH increase and in the precipitation of
Fe(OH)r as the initial surface blocking species. This
film represents a resistive contribution and, therefore,
&
results in a decrease in the current density. The cur-
rent continues to decrease because of an increase in A
G-4C
the film resistance caused by a thickening of the film
and also because of possible structural changes. 7
Eventually, the acidic current and, correspondingly, B
the H + migration decreases so much that the H + G
composition at the interface approaches that of the
bulk solution. This promotes the chemical dissolution
of the oxyhydrated passivating films and a repeat of
the cycle.
As already mentioned, the current oscillations be-
came progressively different as the acid concentration I L
V DE
increased beyond 1.5 N. Podesta et al. (1979a) at- VPVP-A VA-P
tribute these changes to the high sulfate conqentra- Voltage v - maa
tions at the electrode interface, which result in local
Fig. 9. Schematic diagram illustrating potential region
precipitation of FeSO,. It is this FeSO, film then,
where current oscillations are observed. Reproduced by per-
which causes the passivation of the surface and the mission of the Electrochemical Society from Russell and
decrease in the current. A decrease in the current Newman, J. electrochem.Sot. (1986a).
results in conditions favorable for film dissolution and
the cycle repeats itself. For this case then the oscilla-
tions are due to a precipitation-dissolution mechan-
ism without the active participation of the H + ions.
Podesta et al. (1979a) provided no additional
quantitative information to verify the existence of
either the Fe(OH)2 or the FeS04 films. The mechan-
ism of oscillations for the lower HzSOI con-
centrations is, of course, similar to the mechanism
of Frank and FitzHugh, already discussed. No w

quantitative mathematical models were presented to z

verify the so-called “dissolution/precipitation” mech-
z
;
u
anism. In subsequent publications Podesta et al.
(1981, 1982a) examined the morphology of Fe elec-
trodes using SEM after potentiostatic polarization in
the HsSO.+ solutions. They verified the presence of
anodic surface films, both in the oscillatory and pas-
sivating regions, but offered no additional insight into
their chemical composition.
V oc VP4 VA-P
Current oscillations within the limiting-current
plateau were also observed by Russell and Newman Voltage v - a,
(1983, 1986a, b, 1987). They studied three rotating Fe
Fig. 10. Potentiodyhamic sweep results for a typical experi-
disk electrodes and a rotating hemispherical electrode ment. Reproduced by permission of the Electrochemical
in electrolytes containing varying amounts of Society from Russell and Newman, J. electrochem. Sot.
H,SO,/Na,SO,. Figure 9 is a qualitative sketch of (1986a).
 Electrochemical reaction dynamics 1505

passivate, no current oscillations are observed; in- density, ibY, and the observed superficial current
stead the path followed is indicated by the dotted line density, i:
in Fig. 10. When a positive slope load line was used as
iby = i/c,. (20)
suggested initially by Epelboin et al. (1972Fsee also
the discussion below-random current fluctuations The potential required to maintain this iby is given by
were also observed in region B and on the ac- a Butler-Volmer relationship of the form [this is eq.
tive/passive transition line CD (see Fig. V), but these (28) of the original paper by Russell and Newman
fluctuations were strongly dependent on the poten- (1986b), if one neglects the cathodic term]
tiostatic capacitative constants.
A current oscillation is shown in Fig. 11. The oscil- I/- a0 = RT,n’bv
a.F nFK.
lation is irregular, characterized by significant noise at
the bottom of the cycle. Another oscillation, which where Q0 is the potential just outside the diffusive
seemed to have resulted from a period-doubling bifur- double layer, a, is the anodic transfer coefficient, and
cation of a single-peak regular oscillation, was also K, is the anodic rate constant. This equation is
observed (Russell and Newman, 1986a). Russell and plotted in part A of Fig. 13. If one, for example, looks
Newman (1987) have also presented a model, which at Fig. 14, which shows one of the experimental poten-
provides a qualitative description of the various phys- tiodynamic curves of Russell and Newman (19873, for
ical processes they propose as leading to the sustained a rotation speed of 167.6 rad/s the electrode is at the
current oscillations. As with the other models dis- verge of passivation when V - Ip,, = 0.765 V (Olle
cussed so far, the fundamental basis for their model is being the potential of the reference electrode). Figure
the continuous cycling between the active and the 13 then gives the surface pH that exists at the elec-
passive states of the electrode. Their model includes trode/salt interface at the verge of passivation, once
the formation of a porous sulfate salt film, which has the overpotential is specified. This curve is shown in
been shown by Alkire and coworkers (1978, 1983) to part B of Fig. 13. For a given pH the electrode is
be a necessary precursor to passivation due to oxide passive (i.e. covered by an oxide film) when Y - Q0 is
formation. In fact, Beck (1982), who also observed above the line in part B. An approximate potential
oscillations near the passive potentials during Fe balance between the electrode surface and a hemi-
anodization in H,SOd and HC104 electrolytes, also spherical counterelectrode located at infinity is given
implicated porous prepassivation salt films in the gen- as
eration of such oscillations. Of importance to this
model are the conditions which allow the electrode to
be either in the active or the passive state. Figure 12
shows the passivation potential vs pH as determined
by Pourbaix (1974). Russell and Newman assume that +A@,,,+i*.
%,so.
the electrode is covered by a salt film at all potentials
at the limiting-current plateau. Of interest then is to The second term on the right-hand side is the dif-
develop the relationship between the salt film thick- fusion potential in the pores of the salt film, the third
ness, its porosity and the fraction of the electrode term represents the ohmic potential drop in the film,
surface covered by it, before one considers its role in the fourth term is the diffusion potential in the solu-
the generation of sustained oscillations. Russell and tion, and the fifth term is the ohmic potential drop
Newman define the fraction of the electrode surface between the salt film/solution interface and the hemi-
not covered by film as E,. The following relationship spherical counterelectrode at infinity. (More details
then holds between the Butler-Volmer current about the development of this equation can be found

2t; 0 ’ I I I 0
0 50 100 LSO

Time (ms)
Fig. 11. Sustained oscillations observed for electrode M in electrolyte at Cl = 167.6 rad/s. Electrode is
polarized in point b in Fig. 14. Reproduced by permission of the Electrochemical Society from Russell and
Newman, J. electrochem. Sot. (1986a).

CES 49: 10-B

1506 J. L. HUDSONand T. T. TSOTSIS
0.4

0.2 E 0.15-
0.10 -

G 0.05 -

* o-
-0.05 -
0
-0.10 -
Z
G -7 -6 -5 -4 -3 -2 -1 0

; log,0 (%I
-0.2
(B)
,
. 0.25
\
\ 0.20
-0.4 \
FWezOg . 0.1s
equilibrium \ E
\ 0.10
8 0.05
\ I
-0.6 I I I . I I > 0
0 2 4 6 8 10 12 -0.05
-0.10
PH
-0.15
Fig. 12. Experimentally determined potential-pH passiva- 1 2 3 4 5 6
tion conditions and the theoretical equilibrium between Fe
and Fe,O, (dashed line) taken from Pourbaix (1974). Repro- (PH&
duced by permission of the Electrochemical Society from
Russell and Newman, J. electrochem. Sm. (1987).

in the original publications, The uncompensated

ohmic electrolyte resistance plays an important role in
the prediction of oscillations in the model of Russell
and Newman, while it is totally absent from the model
of Franck and FitzHugh. The importance of such
resistances in cathodic type oscillation will be dis-
cussed later.) Values of the ratio of film thickness (6~)
to its porosity E, (note that Ed # E, in general) can be
calculated, for example, by fixing V- (DRE= 0.765, 0 100 zoo 300 4oa 500

varying E, (i.e. varying V - ao), and calculating 6y/zr 6/e, MO

from the above equation. These calculations are
Fig. 13. Steady-state limiting current analysis. Part A, value
shown as line a in part C in Fig. 13. Figure 13 allows
of (V- Cp,) required to produce iL at various values of E,.
one to calculate 6y/e, for various values of cr and to Part B, value of the surface pH which will result in passiva-
understand the various physical phenomena that oc- tion at a given value of( V - 0,) based on the experimentally
cur both under steady-state and oscillatory condi- determined passivation curve in Fig. 12. Part C, values of
tions. For example, Fig. 15 shows the changes that a,,/~~ for various cell potentials as a function of the over-
potential (V - a,,). Reproduced by permission of the Elec-
occur in the overpotential and pH at the elec- trochemical Society from Russeli and Newman, J. elec-
trode/salt interface during an oscillatory cycle, like, trochem. Sot. (1987).
for example, the one shown in Fig. 11. The passive
state (according to Russell and Newman, shown sche-
matically in Fig. 15) involves the formation on the the electrode/salt interface. V - a0 increases and all
electrode surface, under the salt film, of an Fe,O, these processes are represented by line AB,in Fig. 15.
oxide film, several monolayers thick. Eventually, as pH and Y - Do keep increasing, this
What happens during an oscillation can be visual- line will cross the passivation line at point B. As the
ized based on Fig. 15. The electrode starts in the active electrode passivates there is a sharp decrease in the
state, point A, and the high current density in the current density, which results in a sharp decrease in
pores associated with active dissolution results in ohmic potential drop between the electrode and the
a large potential gradient, which in turn causes H + to reference electrode, which in turn results in an instan-
migrate out of the pores of the film and results in a pH taneous increase of V - fDo to point C in Fig. 15. The
increase. A transient increase in the Fe2+ concentra- low passivation current generates only a small poten-
tion in the pores also occurs, which results in in- tial gradient in the salt film and H + ions back-diffuse
creased rates of FeSO, precipitation, especially near into the salt film (line CD in Fig. 15) until at a point
 Electrochemical reaction dynamics 1507

tial distributions and partially passivated electrode

i? 2000 1 I--- surfaces were shown to exist in models by Law and
AV
0%. Newman (1986) and Orazem and Miller (1987). These
- Q = 261.8 I
models were developed to explain nonuniform cor-
rosion patterns observed with rotating Fe disks
(Russell and Newman, 1983; Orazem and Miller,
1987; Epelboin et al., 1972) and to account (Law and
Newman, 1979) for the Z-shaped polarization curves
originally observed by Epelboin et al. (1972) and sub-
sequently by Russell and Newman (1983) using a de-
vice known as the negative impedance converter,
which produces a positive slope load line.
The oscillations were modeled using the mathemat-
0.2 0.4 0.6 0.8 1.0 - ical equations previously developed to account for the
v - $,,E WI
formation and growth of a porous salt film during
anodic dissolution of Fe in acidic sulfate electrolytes
Fig. 14. Potentiodynamic sweep curves for a rotating disk (Russell and Newman, 1986b). The principal change is
electrode with radius = 0.149 cm, in a 1 M H2S04 electro-
lyte. Regions in which oscillations are observed are in-
in the boundary condition at the electrode, where the
dicated. Electrode rotation speeds are given in rad/s. Repro- surface porosity was assumed to be an exponentially
duced by permission of the Electrochemical Society from decreasing function of the surface Fe++ concentra-
Russell and Newman, J. electrochem. Sot. (1987). tion, i.e.
E, = $exp{ - p(looo)[c~: (?j = 0) - C&J}.
(23)
D the electrode reactivates, i.e. the oxide film dis- Furthermore, since the original model is one-dimen-
solves. At this point, i increases sharply, the ohmic sional in order to account for the fact that a perpet-
drop also increases, and V - a0 sharply decreases ually active central region remains at the electrode, in
down to the original point A. The cycle then begins the oscillation model, Russell and Newman (1987)
again. retain a residual ohmic drop when in the passive state.
The current density at the minimum of the cycle This is in order to simulate the ohmic potential that
(see Fig. 11) is too large to correspond to a completely the active central core imposes on the surrounding
passivated state. It instead corresponds to a partly- passive electrode region. It is necessary to do so be-
active-partly-passive state. The proposed potential cause otherwise the ohmic drop would become so
distributions on the electrode surface for the low and small and I/- a0 so large, that for reactivation one
high current states during an oscillation are shown in would require a pH smaller than the bulk value.
Fig. 16. 0. in this figure is the potential at the salt- The model simulations of an oscillatory cycle are
film/electrolyte interface. Similar nonuniform poten- shown in Fig. 15 as points l-17. These simulations are

0.30

Oxide film
0.25
(a)
Sal1 film

0.20
Bulk solurion

5‘ 0.15

e”
’ 0.10 - Electrode
>

0.05 - Salt film i ’ 5

/
; ;4
Bulk solution : a,
0 : 0’2
(17) G’,

-0.05 -
0.50 0.75 1.00 1.25 I so 3.00 3.25 3.50

pll (q = 0)

Fig. 15. Calculated potential-pH conditions at theelectrode surface. Part (a), cases (i) and (ii). Part(b), case
(iii). Reproducedby permissionof the ElectrochemicalSociety from Russelland Newman, 4. electtochem.
SW (1987).
 J. L. HUDSONand T. T. Tsors~s

(a) (b)
L--L4 IA

Fig. 16. Potential distributions in the high-current (a) and low-current (b) oscillatory states. Reproduced
by permission of the Electrochemical Society from Russell and Newman, J. elecrrochem. Sot. (1987).

for a rotational speed of 167.6 and V - mRE = 0.565 V dZ

-= - KJZ + K2 Y.
(point /I in Fig. 14). The simulated current-time curves dt
show a fair agreement with the experimental results of Kado and Kumitomi (1991) then introduce pair inter-
Russell and Newman but a better qualitative match actions among the various adsorbed intermediates
with the observations of Podesta et al. (1979a, 1981, (analogous to the classical lattice gas model) but in-
1982b). Despite the fair agreement between theoretical clude the pair interaction factors only in K,, the
and experimental observations, the model of Russell reaction constant for reaction (26). They write for K2
and Newman represents a valuable modeling effort
aimed at understanding the general phenomenon of K, = KL, exp [4X, Y, Z)lK, Tl (32)
electrochemical transients and oscillations. In our where
opinion it captures all the important physical pro- e(X, Y, 2) = 2(e,,X* + eyy Y* + e,,Z’ + e,,XY
cesses occurring during an oscillatory cycle. Its inabil-
ity to quantitatively match the data results from the + eYLYZ + e,,ZX) (33)
fact that it is a one-dimensional model attempting to where exx, e,,, e.., exy,eyr, erx are the interaction
model what essentially is a two-dimensional phenom-
parameters. Linear stability and numerical analysis of
enon. the model shows it capable of predicting a variety of
A model to explain the current oscillations of Fe in oscillatory waveforms. An electrochemical model to
H2S04 has also been recently published by Kado and predict oscillations of general interest to electrochemi-
Kumitomi (1991). Their model assumes the following cal systems involving active/passive film transitions,
mechanism for iron dissolution: which also assumed that the adsorption/desorption
Fe + Hz0 4 Fe(OH)(ads) + H l + e- (24) constants depended exponentially on surface cover-
age, had been previously presented by Talbot and
Fe(OH)(ads) + Hz0 + [Fe(OH)J (ads) + H* + e- Oriani (1985, 1987).
(25) Teschke et al. (1989) recently published a paper, in
which they claim that they were able to study only the
Fe + [ Fe(OH),](ads) 4 (Fe [Fe(OH),]}(ads) processes associated with the working electrode by
(26) using a specially designed polarization device. They
coupled their studies with in situ microscopic observa-
(Fe [Fe(OH),]}(ads) --+ Fe(OH)+
tions. Figure 17 is a voltammogram obtained with
+ (FeOH)(ads) + e- (27) their polarization device. In Fig. 17 the Fe electrodes
were initially polarized in 1 M H,SO, solution for
Fe(OH)+ + H l + Fezi (aq) + H20. C3
30 min at - 650 mV. Increasing the voltage at a rate
This mechanism had been previously proposed by of 3.5 mV/s from - 650 mV, one first observes the
Schweickert et al. (1980) to describe Fe dissolution in surface to be metallic gray and covered by Hz
the prepassive region. Kado and Kumitomi (1991) bubbles. At - 225 mV a black film starts covering the
neglect the effect of reactions (24) and (28) and write surface. A minimum current is observed at - 60 mV
three differential equations in terms of the surface and subsequently one observes a region of oscilla-
coverages of Fe(OH).d. ‘(X), [Fe(OH)&, ( Y) and tions, which stops at + 100 mV. In the current
{FeCWOWJL W: plateau region the surface is covered by a gelatinous
viscous layer, which covers the electrode surface and
dX
-= - KIX •t K,Z (29) which appeared to have a “swarming appearance”
dt
due to a turbulent motion introduced by convection.
dY This swarming appearance persists until the electrode
-= -KKrY+ KIX (30)
dt passivates at about 200 mV, following a small current
 Electrochemical reaction dynamics 1.509

spike. In SEM micrographs of electrodes polarized in

600 the oscillatory region, Teschke et al. (1989) observed
a low-reflectivity ring, separating two high-reflectivity
t regions, presumably made of thick FeS04 deposits.
%
-2
u
I 400
If the previous procedure is now reversed, starting
at 600 mV and decreasing the voltage at a rate of

m
E
3.5 mV/s, one observes that at 275 mV periodic activ-
ity sets in, in the region coincident with the ac-
tive/passive transition, which continues until about
125 mV. At about - 50 mV a new periodic activity
sets in, which continues until - 160 mV, and which
1. 1 1 I \ , corresponds to the periodic activity observed in the
-500 A00 -300 -200 -100 100 200 300 400 anodic scan. This region of oscillations disappears
mV vs SCE when the system is operated without the special polar-
ization device. Both regions of oscillations also disap-
pear for electrodes polarized in H,SO, solutions
saturated with FeS04. Teschke et al. (1989) attribute
their oscillations to the formation and destruction of
a colloidal salt film, which pi-ecipitates adjacent to the
electrode surface.
Teschke et al. (1985a, b) had previously reported
periodic capillary current phenomena associated with
current oscillations with the Fe/H2S04 system..The
electrochemical cell used in their experiment is shown
in Fig. 18. It consists of a Pyrex glass cylinder,
a (2.5 cm diameter, 15 cm long), twisted into U-shape
and fitted with a lateral tubing, b, 4 mm in diameter.
The level in this tubing can be adjusted by raising or
lowering the level in the main deposit c. Iron tips, cut
normal to the axis of a 0.3 mm thick, 99.99% iron
400 -500 -400 -300 -200 -100 100 200 300 400 wire, were used as the anode. Figure 19 shows the
mV VI SCE potentiodynamic curve observed with this system
with oscillations observed in the active/passive
Fig. 17. Voltammogram obtained by the polarization device transition. In the same figure, the results of an experi-
shown in Fig. 1 of the original paper: (a, top) anodic scan; (b,
ment are shown, in which a square-wave voltage was
bottom) cathodic scan. Reprinted with permission from
Teschke et al., Langmuir. Copyright 1989 American applied to the anode and the electrical current and the
Chemical Society. liquid level around the wire electrode were monitored.

Fig. 18. Experimental setup for observing the electrical and mechanical oscillations: The projection system
formed by lamp (d), lenses (e), and screen (f); the U-shaped Pyrex glass cylinder (a) and the micromanip-
ulator (g). The insert (lower right) shows the electrode tip touching the liquid. Reprinted with permission
from Teschke et al., Langmuir. Copyright 1985 American Chemical Society.
 1510 I. L. HUDSON and T. T. TSOTSIS

3- (a) the wettability of the reaction products deposited on

the wire surface, (ii) the various electrochemical pro-
cesses occurring at the tip and (iii) the gravity. The
corrosion products deposited on the wire up to the
triple-phase boundary at the meniscus make the elec-
trode surface more hydrophilic, resulting in the rise of
the viscous meniscus up the wire. Gravity, on the
\r other hand, is responsible for the fall of the liquid
-300 -7.00 -100 O(SCE)lOO 200 300
when the adhesion forces between the Fe corrosion
V (mW products and liquid are not sufficient to hold the
2 400 liquid column. Surface tension forces play an im-
r(
portant role in the phenomenon, since they are re-
S 200
sponsible for the ascent and the fall, which lead to the
,z
> renewal of the exposed corroding surface.
0 20 40 Oscillations have also been observed during Fe
T (min) electrodissolution in electrolytes other than aqueous
HzSO,/sulfate solutions. Current oscillations during
A
Fe electrodissolution in HzS04 solutions in CH,OH
have been reported by Tousek (1975) and Kalusic et
6.0.. nl. (1982). Oscillations have been reported by Cooper
-z et al. (1980) during Fe electrodissolution in NaClOs.
c
8 Oscillations during Fe electrodissolution in HN03
2 solutions have been reported by Gabrielli et al. (1976).
Oscillations have also been reported for the dissolu-
5.5,. tion of Fe in chloride solutions. The earlier reports
date back to the early 1970s. They were part of studies
aimed at a better understanding of the phenomena
0 20 40 occurring during the electromachining of Fe. The
T (min) oscillations observed were attributed to the presence
of porous nonprotective films (Chin, 1971;
Cd) Postlethwaite and Kell, 1972), which are formed dur-
1200 ing Fe dissolution in NaCl solutions. A more exten-
sive investigation was published recently (Li et al.,
?
800 1990b). In this study the authors used a rotating Fe
t
disk electrode in neutral NaCl solutions together with
400 a ring electrode made of Ti coated with RuO, ,Figure
21 is the anodic polarization curve of Fe as reported
by Li et al. (1990b). One can identify four regions, i.e.
40
the Tafel region I; the current peak region II; the
T (min)
diffusion-limited current region III; and region IV
Fig. 19. Forced capillary oscillations: (a) polarization curve following region III. The diffusion-limited current iD
of Fe in 1 M H,SO,, aqueous solution at 25°C showing the was found to decrease with increasing NaCl concen-
passive-active transition, scanning starting + 350 mV (vs tration and this was attributed to changes in the
SCE) with a sweeping rate of 1.5 mV/s; (b) electrode applied F&l, solubility. The line indicated as iR(0.8 V) in Fig.
voltage as a function of time: (c) liquid level variation as
a function of time; (d) current-time dependence. Reprinted 21 is proportional to the mass flux of the ferrous
with permission from Teschke et al., Langmuir. Copyright species and the line &(O.l V) to the flux of the ferric
1985 American Chemical Society.. species.
The lines iR(0.1 V) and iR (0.8 V) are revealing of the
phenomena occurring in the various regions of the
Note that both the current and the liquid level are polarization curve. In the Tafel region, as the poten-
oscillating in response to the voltage oscillations im- tial is increased, Fe is oxidized only to Fez*, as
posed on the electrode, with maximum height ob- indicated by the increase in i,(O.8 V). As the peak in
served at the maximum current. Potentiostatic cur- the disk current was approached, the formation of
rent oscillations are shown in Fig. 20. These oscilla- a black film, previously shown to be FeCI, (Kuo and
tions are accompanied by simultaneous oscillations in Landolt, 1976), was observed. Above this peak poten-
the liquid level in contact with the Fe electrode tip. tial the i,(O.8 V) remained constant as the potential
A mechanism is presented by Teschke et al. (1985a, b) increased, indicative of the fact that the Fez+ flux was
to explain the mechanical liquid-level oscillations as- due to the dissolution rate of the FeCI, film, in this
sociated with the electrochemical periodic variations. region a diffusion-limited process. At higher poten-
According to them the capillary oscillations are in- tials (> 1.5 V) Fe’+ species are detected, and above
duced by the action of three factors, which include (i) 2.0 V the limiting current for Fe3+ indicates again the
 Electrochemical reaction dynamics 1.511

60

50

40
<
I
30

Fig. 20. Current-time

20

10

0 I
0
f f

1
f- /

profile for an iron electrode in 1 M H,SO, aqueous solution at constant anode

potential ( + 300 mv YS SCE). Reprinted with permission from Teschke et al., Langmuir.Copyright 1985
2
Minutes
f r-

3 4

American Chemical Society.

Ring current density (mA/cm’) formation is higher than the rate of its dissolution the
-40 -20 0 20 40 60 film thickens and, as a result, the resistance and there-
fore the potential increases. At some point, as the
potential increases, Fe’+ itself begins to oxidize to
G lIV
2
Fe3+. Part of the Fe’+ is dissolved in the solution and
; part is incorporated into the surface film. The authors
L claim that the solubility of Fe” + is higher than that of
111
3 1.5 - Fe’+. As a result, the more Fe3+ that is formed, the
5 1.0 - ; higher the dissolution rate of the film, until it over-
x 0.5 - )” takes the growth rate. At this point the film begins to
4
a
0.0 - thin and finally disappears, at which point the poten-
11 tial drops sharply. Fe continues to oxidize to Fe2+ but
-1.0
I I production of Fe3+ stops and the cycle repeats itself.
-5 -3 -I 1
A mathematical model based on this mechanism was
Log disk currenl dcnsily (Alcm2)
subsequently presented by Li et al. (1990a). The model
Fig. 21. Anodic polarization characteristics of Fe in 4 M consists of three ordinary differentials in terms of the
NaCI; 200 rpm, and 20 mV/s sweep rate. (I) Tafel region, (II) fraction of the porous film volume JIZ(X, t) occupied
peak current and current minimum, (III) limiting current by FeCl, , at position X, and $J(X, t). the fraction of
region, and (IV) postlimiting current region. Reproduced by
permission of the Electrochemical Society from Li er al.,
film volume occupied by FeC13 and the film thickness
J. &ctrochem. Sot. (199Ob). L(t). Linear stability analysis of the model predicted
a region of conditions in the parameter space, for
formation of a Fe 3* film (the film was observed to which a unique unstable state exists from which the
have a yellow color), and the decrease in the ix (0.8 V) fastest growing mode is oscillatory. The authors
indicates a rapid oxidation of Fe’* species into Fe3* theorized that, in this region, the film might neither
species. grow nor dissolve monotonically, but, rather, oscilla-
Oscillations were observed in the diffusion-limited tions might occur. They did not present, however, any
current region III as well as in region IV under both further evidence of such oscillations. In a more recent
galvanostatic and potentiostatic conditions, and in paper, Li et al. (1993) analyzed the complex oscilla-
the presence and/or absence of rotation. The oscilla- tions observed by Li et al. (1990b) and showed them to
tions had various waveforms ranging from the single be deterministic chaos. They also estimated the cor-
peak and relaxation type to the very complex type. No relation dimensions and the Lyapunov exponents of
mathematical model for the oscillations was presented the chaotic attractors. The power spectra of the po-
in this paper, but instead a mechanism for the oscilla- tential oscillations observed in 2 M NaCl solutions
tions was proposed, which is as follows: for galvano- exhibited two distinct dominant frequencies at 0.1 and
static oscillations, when an anodic current is first 4 Hz. Li et al. (1993) associated the high-frequency
applied Fe is oxidized to Fe’+. The Fe’+ concentra- oscillations with the growth and dissolution of a non-
tion at the Fe/solution interface rapidly increases porous inner layer, which forms under an external
until conditions of saturation are reached, at which porous salt film. The low-frequency, larger-amplitude
point FeC1, begins to precipitate on the Fe surface oscillations were in turn attributed to the dissolution
forming a black porous film. As long as the rate of film and growth phenomena associated with this external
 1512 J. L. HUDSONand T. T. TSOTSIS

film. Li et al. (1992) and Li and Nobe (1993) have also part of the cycle before the electrode is completely
investigated the effect of two organic inhibitors repassivated. This can be observed visually because
(benzotriazole and hexynol) on the dynamics during the electrode becomes clear to pale green from a dark
iron electrodissolution in concentrated chloride solu- green color. Once the electrode is repassivated the
tions. Simple and complex oscillations were also ob- polyaniline is reoxidized by the O2 in the system.
served in the presence of these inhibitors. Complex potential oscillations during the corrosion
Several other papers have reported oscillations dur- of Fe, Ni and Fe-Ni alloys have been observed by
ing Fe electrodissolution in various acidic media Shen et al. (1992), who report that the oscillations are
(Karsulin et al., 1977; Torigoe, 1970; Moina and associated with the instability of the anodic film and
Posadas, 1989; Strehblow and Wenners, 1977). Unfor- their complex waveforms are due to the surface het-
tunately, in a number of these papers, the oscillations erogeneity related to pitting corrosion. Shen et al.
are not well documented. In some instances, while the (1992b) also reported on the effect of benzotriazole on
authors are claiming to have observed oscillations, the the oscillatory behavior of Fe-Ni and Cu-Ni alloys
data presented only indicate oscillatory transients. during their electrodissolution in concentrated NaCl
Moina and Posadas (1989), for example, present an solutions. Chaotic oscillations were observed both in
oscillatory transient they observed during electrodis- the absence and in the presence of benzotriazole. The
solution of Fe in acidic (pH = 2) (NH4)zS04 solu- presence of the inhibitor seemed to result in decreas-
tions. Although the authors claim to have observed ing oscillatory frequencies for the Fe-Ni alloy, while
oscillations, no such sustained oscillations are pres- for the Cu-Ni alloy the addition of benzotriazole
ented. A similar oscillatory transient during galvano- resulted in potential oscillations of smaller amplitude.
static experiments with Fe in 4 M HCl has been pres- High-frequency current (and more recently voltage)
ented by Strehblow and Wenners (1977). A number of noise has been observed and its power density meas-
papers, which deal with the corrosion of Fe, various ured with passive Fe electrodes by Heusler and
steels and Fe alloys in acidic media, report large. coworkers (Nachstedt and Heusler, 1988a, b, Heusler
current fluctuations (Szklavska-Smialowska and et al., 1992) during the incubation time after the addi-
Janik-Czachor, 1969; Shiobara and Marioka, 1972; tion of halide ions, and before the appearance of the
Williams et al., 1974; Tong, 1981; Abd El Wahab et al., first corrosion pit. A number of elaborate stochastic
1982; Podesta et al., 1982a; Bertocci and Yang- models have also been developed to explain this elec-
Xiang, 1984; DeBerry, 1985; Bertocci et al., 1986; trochemical noise [see e.g. Williams et al. (1985) and
Bershadskaya et al., 1988; Champagnie et al., 1989; Okada (1984, 1985, 1986, 1988, 1990, 1991a,b, 19921.
Matsuhashi et al., 1990; D’Alba et al., 1989, 1991; Okada, in particular, has advanced a two-stage initi-
Shen et al., 1992; Tingjiang and Naixin, 1993) as- ation process hypothesis leading to pitting corrosion.
sociated with nucleation and growth of pits. In each stage, random processes occur, leading to
For example, Abd El Wahab et al. (1982) report high-frequency current fluctuations. Other recent
large current oscillations during the galvanostatic works dealing with electrochemical noise include
polarization of various Fe-Cr alloys in H,SO, those by Dawson et al. (1989), Rothwell and Eden
electrolytes containing various amounts of Cl- (1992), Sharland et al. (1990). Cano et al. (1990), Pride
ions. These oscillations were attributed to the et al. (1992) and Hudson (1992b). The topic appears to
alternate breakdown and repair of the passive films. be attracting increasing interest.
Breakdown is caused by the aggressive Cl- ions, while As already discussed, Fe electrodissolution in acidic
film repair is caused by oxygen and SOi- ions. These media has been shown to exhibit some very complex
ideas are consistent with views on the pitting cor- types of oscillatory behavior. One of the earliest sys-
rosion behavior of Fe-Cr alloys originally proposed tematic investigations of the complex dynamic behav-
by Uhlig and coworkers (Leckie and Uhlig, 1966; ior is due to Beni and Hackwood (1984), who ob-
Horvath and Uhlig, 1968). The dynamic behavior of served intermittent turbulence, period doubling and
Fe electrodissolution in H2S04 solutions has also other periodic and aperiodic oscillations in the ac-
been investigated by Sazou et al. (1992). In the pres- tive/passive transition region. They also developed
ence of Cl- ions for a stationary electrode, the relax- a model, which involves the gradual transformation of
ation-type oscillations normally observed with the an anodic film, to try to explain the sequence of
Fe/HzSO., system become aperiodic and finally dis- oscillations they observed. Hudson and coworkers
appear. For rotating electrodes, upon increasing the have used nonlinear dynamic data analysis techniques
Cl- ion concentration, quasiperiodic and chaotic os- in order to better characterize the observed complex
cillations are observed. Large-period current fluctu- oscillatory behavior. In one of the earlier papers Diem
ations during open-circuit exposure of polyaniline- and Hudson (1987) reported on the chaotic behavior
modified type 430 stainless steel in a 0.2 M observed with Fe electrodissolution in H2S04. They
HzS04 + 0.2 M NaCl solution have been reported by carried out potentiostatic and potentiodynamic in-
DeBerry (1985). The current fluctuations observed vestigations using rotating Fe disk electrodes, but also
with the polyaniline-covered electrode are interpreted used an Fe wire. A summary of their potentiostatic
in terms of a passive film undergoing a partial break- experiments with the rotating disk is shown in Fig. 22.
down in the acid chloride solution and then being For E c 0.04 they observed a single steady state.
repaired with the aid of the polyaniline. The polyani- Beyond that voltage and up to 0.23 V they only ob-
line film is partially reduced during the more negative served oscillatory behavior. At E = 0.24 the electrode
 Electrochemical reaction dynamics 1513

.i
1 :
350 - ..+---_, .* :
,,_._.A@ l-.*. :

Oscillating
:Y
i.t
Q 300 -Steady \ . .D

l
9 I\ ;c
- 250 - 6. t

200 - , ,‘._.,. ;
0.2 IO - 7’) (A)
I I + I I
150
0 0.05 0.10 0.15 0.20 0.25

E 0’ YS Hg/Hg,SO,)

Fig. 22. Potentiostatic experiments. Upper and lower curves

are absolute maxima and minima, respectively, of the oscilla-
tions. From Diem and Hudson (1987). Reproduced by per-
mission of the American Institute of Chemical Engineers.
0 1987 AICbE. All rights reserved

Fig. 23. Three-dimensional state space plots using splined

passivates. The upper and lower curves in Fig. 22
indicate the maxima and minima of the current oscil-
lations. In order to fully characterize the nature of the
oscillatory behavior observed, Diem and Hudson cal-
culated the dimensions of the attractors correspond-
ing to the time series. Depending on the voltage, the
attractors were shown to be chaotic and to have
dimensions between 2.4 and 6.0, the correlation
mension u being the largest for low values of voltage
and the smallest for higher values of voltage. For
0.2 V -C E c 0.22 V u was less than three. As already
discussed, u is a lower bound for the Hausdorff dimen-
sion. When the latter is less than three the chaotic
attractor should be embeddable in a three-dimen-
sional state space. The attractor for E = 0.21, for
which u = 2.4, is shown in Fig. 23 and it appears to be
simple. The authors could not say with certainty
whether or not it was embeddable in the three-dimen-
sional space because they had no evidence that the
trajectory did not cross itself. In contrast, in the same
figure, one can observe the attractor for E = 0.08 V
for which u = 5.4. This attractor is considerably
complicated and clearly not embeddable in three di-
mensions.
In a subsequent study, Wang and Hudson (1991)
studied the effect of changing the area of the electrode
or the dynamics of the Fe/H2S04 system in the limit-
ing-current plateau. They varied systematically
diameter of the rotating disk electrode from 2.0 mm to
6.35 mm. What they observed was that the complexity
of the oscillatory behavior exhibited by the electrodes
increased as the diameter of the electrode increased.
For the smaller electrodes used they observed regular
oscillations. As the electrode diameter increased, the
regular oscillations gave way to low-order chaos, and
then to higher-order chaos. Wang and Hudson at-
tributed this behavior to the coupling between the
various active sites on the electrode surface. In their
most recent study, Wang and Hudson (1992) carried
out experiments on interacting electrochemical
lators using Fe in H2S04. One, two, or three elec-
trodes were embedded in the end of a rotating
disk. Examples were shown in which the coupling of
points: (a) E = 0.21 v (u “I 2.4; 4000 points); (b) E = 0.08 V
(v = 5.4; 2OC0 points). Direction of flow is indicated. From
Diem and Hudson (1987). Reproduced by permission of the
American Institute of Chemical Engineers. @ 1987 AICbE.
All rights reserved.
periodic oscillators resulted in chaos and in which the
di- coupling of chaotic oscillators led to higher chaos.
As was noted above, the surface of a metal anode
may not be uniform. This nonuniformity has been
investigated during the active-passive oscillations
which occur with Fe in H2S04 near the Flade poten-
tial. During the oscillations, there occurs the forma-
tion and removal of a film on the surface of the
electrode. The film, however, does not grow uni-
formly, but rather does so by forming first at the outer
radius (in the case of a circular electrode) and then
growing radially inward. Pigeaud and Kirkpatrick
(1969) showed that a zone of higher reflectance grows
radially inward as the current relaxes downward from
its maximum value (active state) to its minimum value
more (passive state). The film then gradually disappears and
then the cycle is repeated. Hudson et al. (1993) studied
the spatiotemporal dynamics of this reaction as
a function of the applied potential in the region near
the Flade potential. While the current was measured,
the surface patterns (the growth of the film) were
the monitored with a video camera. It was shown that as
the potential was changed in the cathodic direction
(during a series of potentiostatic experiments) a
spatiotemporal period doubling took place.
The effect of forced periodic oscillations in the po-
tential in the passive/active transition region, where
the Fe/H2S04 system exhibits autonomous poten-
tiostatic current oscillations and bistability, has been
studied by Pagitsas et al. (1992a). Their applied elec-
trode potential is described as E = E, + E,cos (m,r),
where E. is a potential, for which the unperturbed
system exhibits single-peak relaxation oscillations
oscil- with frequency wO_ The dynamic response of the elec-
trochemical system was studied as a function of the
frequency ratio (wJwo ). The response of the system
(see Fig. 24) shows wide regions of quasiperiodicity
1514 J. L. HUDSON and T. T. TSOTSIS

ically forced Franck-FitzHugh system again exhib-

ited entrainment bands and regions of quasiperiod-
icity. Square-pulsed oscillating potentials have been
utilized by Fukumoto et al. (1992) for the treatment of
steels of high Cr content. The fractal nature of cor-
rosion pit profiles resulting when stainless-steel rods
are oxidized anodically in synthetic ocean water has
been analyzed by Costa et al. (1991). Further details
about the application of fractal theory to electro-
chemical systems can be found in the review paper by
I I I I Costa (1991).
112
--- 1 3 2 5 3
3 23 F 1 Anodic dissolution of copper
mp’% Cu electrodissolution has also shown some interest-
ing dynamic behavior. Oscillations for this system
Fig. 24. Phase diagram representing the various types of have been reported by Hedges (1926,1929), as early as
response of the system Fe/2M HLS04 to a periodic per-
turbation of the Fe electrode potential. This is constructed
in 1926. Figure 25 shows the potential oscillations
by plotting the perturbation amplitude vs op/wO, where w,is reported by Hedges in his original paper for Cu elec-
the sinusoidal perturbation frequency and w0 is the auton- trodissolution in HCI. The experiments were neither
omous frequency of the periodic oscillations for potentiostatic nor galvanostatic, so the current den-
E. = 274 mV. The numbers in the graph are equal to k, i.e. sity also oscillated in phase with the potential oscilla-
the periodicrty of the entrained response.The shaded regions
represent the quasiperiodic domains. Reproduced by per- tions. Several large-period (by electrochemical stan-
mission of Elsevier Sequoia S.A. from Pagitsas et al., J. dards) regular or relaxation-type oscillations are re-
electroanal. Chem. 327, 98 (lYY2a). ported in this figure. Hedges also reported some vis-
ible periodic changes of the anodic Cu surface. Simul-
(shaded areas in Fig. 24), separated by entrainment taneously, for example, with the rise AB in the poten-
bands, which are either harmonic (0, = wr,, where w, tial (see Fig. 25) a thin dark gray film formed and
is the frequency of the response) or subharmonic propagated up the anode surface. The voltage then
(w, = w,,/2). The authors did not observe any period- slowly decreased down to a point C (the current
doubling cascades or other routes leading to chaos. correspondingly increased), where the potential rap-
The experimental study was coupled with a modeling idly decreased to its initial value. Almost simultan-
study (Pagitsas et al., 1992b; Karantonis et al., 1993) eously (with a delay of a fraction of a second) a white
using the Franck-FitzHugh model, as previously film formed and propagated down the surface. The
modified by Pagitsas and Sazou (1991). The period- smooth dark gray film was observed to break into

2
I
2 0
6
4
2
6
4
2
8
6
4

Fig. 25. The amplitude in graphs 37-41 is about half of that indicated in graph 58. This is because half the
number of cells was used in these experiments. When the highly resistant film forms, the voltmeter records
aImost the total EMF of the battery, the resistance of the rest of the circuit being relatively small. Reprinted
with permission from Hedges, J. them. Sm. Copyright 1926 American Chemical Society.
 Electrochemical reaction dynamics
a rough red-brown one, which transformed immedi-
ately into the white film. The series of events was
repeated cycle after cycle. While the white film was
thought to be cuprous chloride, the nature of the
other two films was not clear, probably some form of
an oxide film.
A number of interesting transient experiments were
also reported by Hedges. If the circuit was broken,
while at the high potential part of the cycle, one
observed the cuprous chloride film to form immedi-
ately, uniformly over the whole anode surface. Upon
closing the circuit, the oxide films were reinstated
immediately, while the potential was rising. If one
waited for 1 or 2 s to close the circuit, there was a lag
in the formation of the oxide films. By interrupting
and closing the circuit several times, one observed
that the white film (cuprous chloride) did not form
upon interrupting the circuit. Instead, the smooth
dark gray film turned into the red-colored one. The
white film now appeared upon closing the circuit
followed by the gray oxide film.
Hedges attempted to explain the transient and the
oscillatory behavior by postulating that the smooth
gray oxide film of high resistance is metastable in the
region of oscillations and that it changes in the oxide
film of low resistance (the red film), which reacts with
the chloride ions to form the CuCl film. For example,
when the circuit is broken, Hedges claims that the
smooth gray oxide film, stable only at high voltages,
reacts with the available chloride ions. When the
circuit is reinstated, the available chloride ions are
consumed and the oxide film is again formed. By
repeating the circuit closing/opening process in rapid
succession, the solution in the immediate vicinity of
the anode becomes so depleted of Cl ~, that breaking
the circuit only converts the gray film into the red
stable film, which persists in the absence of Cl-, but
converts immediately into CuCl once the circuit is
reinstated. According to Hedges, this mechanism for
oscillations, which involves a metastable oxide film
converting into a stable oxide film, which in turn
converts into a CuCl film, is supported by the effect
that the various experimental parameters have on
oscillations. For example, increasing current density
was found to increase the period of oscillations, which
according to Hedges is because higher currents de-
plete more rapidly the solution of Cl- and stabilize
the gray oxide film. Increasing the temperature was
found to decrease the time the anode spends in the
cycle at high voltages, which according to Hedges is
due to the fact that the gray oxide is more unstable at
higher temperatures.
Additional experiments with rotating anodes re-
ported a few years later by Hedges himself (1929)
seemed to discredit the mechanism involving a meta-
stable oxide film. Instead, this time Hedges attributed
the oscillations to a dissolution process of the oxide
film, which, according to him, only happens when the
local Cl- concentration reaches a threshold value.
Whether the mechanism for oscillations suggested by
Hedges is valid or not is debatable. His papers, how-
1515
ever, still remain some of the most detailed and careful
accounts of experimental work with the Cu electrodis-
solution reaction system.
Hedges also reported oscillations for Cu in other
Cl--containing electrolyte solutions. For example,
graph 40 in Fig. 25 is for Cu in 5% NH&I solution,
and graph 41 for Cu in 5% NaCl solution. Oscilla-
tions with very long periods were reported for Cu in
5% CuCl, solution.
Interesting oscillations were also observed with Cu
in KCN solutions (graphs 53, 54 in Fig. 25) also ac-
companied by visible changes on the Cu anode sur-
face. For example, for Cu in 10% KCN solutions,
Hedges observed that at low current densities no film
is formed on the surface and Cu dissolves presumably
as potassium cuprocyanide. When the current density
was raised to 59 mA/cm’, a gray oxide formed on the
metal and the potential difference between anode and
cathode rose from 1.6 to 2.7 V. This film, after a few
seconds, gives place to white film (of CuCN according
to Hedges) and the potential returns to its original
value. Thereafter, the anode oscillates between these
two states in a regular manner. On further increasing
the current density to 86mA/cm2 a pale green film
permanently covers the anode, followed by a rise in
the potential from 3.6 to 6.2 V and the onset of a sec-
ond series of oscillations. These oscillations are more
diverse in character and, in many instances, highly
irregular. No changes in the nature of the surface
film are observed during this second series of oscil-
lations.
A similar mechanism for oseillafions involving cyc-
lic transitions between a CuCl and a Cu,O film was
suggested in 1948 by Bonhoefler and Gerischer (1948)
to explain the oscillatory behavior of Cu in HCI.
A porous CuCl layer first precipitates on the electrode
surface. This increases the local current density, there-
by increasing the alkalinity of the electrolyte in the
pores, due to H + migration, creating conditions fa-
vorable for Cu20 precipitation. This precipitation
further increases local current density, thereby accel-
erating Cu,O precipitation. Eventually, conditions in
the pores become favorable for Cu2 + production. In
the meantime, CuCl production has substantially de-
creased and it gradually disappears. Thus, the condi-
tions which brought about the Ccl20 production
cease to exist, and the Cu20 film begins to dissolve at
an accelerating rate. This continues until conditions
are once again favorable for CuCl production and the
cycle begins again.
Oscillations during Cu anodization in neutral NaCl
solutions were reported by La1 and Thirsk (1953). La1
and Thirsk, furthermore, dispute Hedge’s (and
Bonhoeffer and Gerischer’s) mechanisms for oscilla-
tions involving a cyclic transition between a Cu20
and a CuCl film. According to them, the oscillations
may be due to a compact CuCl film, the discontinuity
provided by cupric ions formed, when the chloride
deposit reaches a certain thickness. These ions may
disrupt or modify the film of CuCI. Since, simultan-
eously, the film is being dissolved, conditions are
1516 J. L. HUDSON and T. T. TSOTSIS

eventually brought about in which cuprous ions are X-ray diffraction and were shown to correspond to
produced and the film is being formed again. Cu20. Physical changes occurring on the anode sur-
Cooper (1956) and Cooper and Bartlett (1958) have face during a cycle were recorded with a motion
studied Cu electrodissolution in HCl in the presence picture camera and a sequence of four pictures is
of natural convection. They observed two steady-state reported in Fig. 27. During the low potential, active
plateaus; see Fig. 26. In the first plateau they found phase of the cycle, the Cu surface became etched and
that Cu metal dissolves only in the form of Cu+, while pitted, while a red-orange layer, identified as CulO,
in the second plateau 30% of Cu is dissolved as Cu’“. accumulated on the surface [Fig. 27(a)]. Beginning
They have found no direct evidence for Cut0 forma- with the onset of transpassive dissolution (coinciding
tion. Only CuCl is deposited on the Cu surface in both with the onset of potential increase) the anode surface
plateaus. They have observed oscillations in the re- becomes smoothed and polished, attaining a nearly
gion below Cu2 + or O2 formation at the beginning of specular appearance as the peak potential is ap-
the first current plateau with periods from 10s to proached. The surface now is covered by two films,
1 min. They explain these oscillations in terms of the a thin (submicron) film of Cu20 and a thick
formation and dissolution of a CuCl film. After the (1~100 /rm) loosely adherent film of Cu20 and water-
film is formed, the decrease of total current causes an soluble copper oxychlorides. The thin film starts
increase in anolyte concentration. This drags up the forming at the periphery, spreads progressively in-
concentration at the base of the pores and results in wards, dislodging the film formed during the active
lower electrode potentials there. Below a critical phase. Immediately before the fall from the peak po-
value, layer formation will cease, and the existing tential, the electrode surface loses its polished appear-
layer will continue to dissolve until the surface is bare ance, becoming dull under intense field illumination
enough for the cycle to begin again. [Fig. 27(c)], while, at the beginning of the active phase
The dynamic behavior of Cu electrodissolution in of a new cycle, the thin Cu20 film peels away and the
Cl--containing electrolyte solutions has also been crystals of a new thick phase of Cu,O are beginning to
studied by Tobias and coworkers (Cooper et al., 1980; form [Fig. 27(d)].
Landoldt et al., 1970; Kinoshita et al., 1970). Sus- Cooper et al. (1980) present a model to explain the
tained potential oscillations were observed under gal- observed oscillatory behavior, which involves the al-
vanostatic conditions during Cu electrodissolution in ternation between periods of film growth by high field
NaClO, solution. For this electrolyte, Cooper et al. ionic conduction and field breakdown resulting from
report oscillations for a current density range between resistive switching transitions. During the potential
0.3 and 150 A/cm’, with a frequency in the range growth phase of the cycle, charge is passed through
between 0.003 Hz to over 1000 Hz. The period of the growing nonporous film by ionic conduction.
oscillations was found to decrease with increasing Above a critical voltaT, resistive switching
current density and to increase with increasing elec- transitions begin to occur simultaneously with film
trolyte flow rate and temperature. The apparent val- growth resulting in the formation of channels of low
ence density of dissolution remained constant during electronic resistivity. These provide alternate paths for
an oscillatory cycle. It was found to increase with the current and result in the reduction of voltage and
current density and to approach a constant value in the flow of ionic current and the growth of the film.
(1.2 f 0.04) above 10 A/cm2. Solid reaction products The continued flow of electronic current results in the
adhering to the surface of the anode were analyzed by removal of the channels and adjacent Cu10 by anodic
reactions like

Cu20 + HZ0 + 4C1-=2CuCI, + 2e- + 20H-

(34)
2H,O=O, + 4H+ + 4e- (35)
Cu,O+:ClO; f4HC=2Cu”+ ++Cl- +2H,O.
2
S
._ (36)
Once the channels are removed (all channels must be
removed to polarize the film of a given thickness to
the field strengths required for ionic conduction), the
film repair/growth process can resume. At low current
-0.4 -0.2 0 0.5 1.o 1.5
densities the removal of the Cu10 film is complete,
V (V/O-I N calomel) but at high current densities (> lOA/cm’) the re-
Fig. 26. Characteristic curves for an unshielded anode moval of the film is partial and the lowest potentials in
(0.02 cm) with exposed face vertical, in 2 N HCI, showing the cycle are about 10 V above the active dissolution
locus of initial current and voltage (iO, V,) of stationary potential. The widely different field strengths required
values of current and voltage for the first plateau (i,, K), for
the second plateau (i,,, y,), and for the steady state (ix, V,).
for the two modes of current flow preclude the possib-
Reproduced by permission of the Electrochemical Society ility that they will occur simultaneously for extended
from Cooper and Bartlett, J. electrochem. Sot. (1958). periods of time. According to Cooper et al., electronic
 Electrochemical reaction dynamics 1517

Fig. 27. Sequence of changes of surface morphology during a potential cycle. Rotating disk electrode,
i = 0.32 A/cm*, 360rpm: (a) appearance of active phase electrode showing thick Cu20 layer (x) and
roughened substrate (bright field illumination); (b) progression (right lo left) of transpassive film; thick film
has been removed; dark field illumination; (c)electrode surface at peak potential (bright field); (d) beginning
of active phase of second cycle (dark field). Reproduced by permission of the Electrochemical Society from
Cooper et al., J. rlectrochem. Sot. (1980).

current through the Cu,O can only occur through ported by the same group (Landolt et al., 1970;
mechanisms that destroy the film and no stable film Kinoshita et al., 1970) almost 10 years earlier and
can be produced through ionic conduction since the attributed to the formation and dissolution of solid
growth rate is higher than the film dissolution. Cl - anodic products.
ions seem to play an important role in the mechanism Nobe and coworkers (Lee et al., 1985; Lee and
of high field ionic conduction/field breakdown and Nobe, 1986; Pearlstein et al., 1985) have presented
Cooper et al. report several other common electrolyte a detailed experimental and theoretical study of the
systems, which in the presence of Cl- exhibit large- dynamics of Cu electrodissolution in acidic Cl- me-
amplitude oscillations. dia. Experiments have been carried out with a rotat-
Oscillations during the anodic dissolution of Cu in ing ring/disk electrode assembly. The region of oscil-
KC1 and NaClO, electrolyte solutions had been re- lations observed during potentiodynamic experiments
 1518 J. L. HUDSON and T. T. TSOTSIS

500 j-

CuCl film
i
z = h(t)
I
i I-WW

Fig. 29. One-dimensional idealization of the Cu rotating

disk electrode and CuCl film. Reproduced by permission of
the Electrochemical Society from Pearlstein et al., J. elec-
rrochem. sot. (1985).
1 10 100

Current density (mA/cm2) flux of Cl- is related to the rate of reaction (37)

Fig. 28. Anodic polarization of Cu in 0.1 M NaCl + 1N

H3S04, 0.2 M NaCl + 1N HISO,, 0.5 M NaCl + 1 N
H,SOI, and 1 M HCI. Sweep rate, 0.5 mV/s. Reproduced by
permission of the Electrochemical Society from Lee er al., J.
electrochem. Sot. (1985).
while at h(t) C is related to C,, the bulk electrolyte
concentration of Cl-, by C = K,C, . To account for
the change in g(t) one writes a mass balance equation

in electrolytes containing varying amounts of Cl- is PC~

---=&CT.
dg
shown in Fig. 28. Both regular and chaotic oscilla- MWcu dt
tions were observed. To account for the change in h(t) one writes a mass
A one-dimensional model for oscillations has also balance for CuCl production in the film:
been developed by the same group (Pearlstein et al.,
1985). The model describes Cu electrodissolution in
acidic chloride media with the following reaction
mechanism:
= --&=&((aC,+K,) (44)
C”
Cu(s) f Cl-(aq)=CuCl(s) f e- (37)
with aC, being the rate for the electrochemical reac-
CuCl(s) + Cl- (aq)*CuCl; (surface) (38) tion (38) and K3 being the rate for reaction (39). u is
CuCl; (surface)*CuCl; (aq) (39) dependent on the rotational speed ( z W1”) and
CuCl=Cu*+(aq) + Cl-(aq) + em. (40)
Ki = Kio exp (45)
According to this kinetic scheme, if the CuCl (s) prod-
uct is not removed fast enough, a porous film will The above set of differential equations was analyzed
form and, for process (37) to occur, Cl- must diffuse by linear stability analysis and a region of conditions
through the porous film. Reaction (38) is a nonelec- was found in the parameter space where a unique
trochemical process [reaction (38) is much faster than unstable steady state exists [by steady state implying
reaction (39)] and reaction (40) only occurs at high a state in which the film thickness A0 = h(t) - g(t)
potentials. Pearlstein et al. (1985) model an idealized and the reaction rate do not change with time]. One
one-dimensional analog of their rotating disk elec- would possibly expect, in the same region, that oscilla-
trode; see Fig. 29. They write the diffusion equation as tions in the film thickness and current density also
exist. Pearlstein et al. (1985). however, did not present
dC any numerical integrations of their model, indicating
- =
at
D,$, g(t) < 2 < h(t) (41) the existence of such oscillatory states.
Current oscillations during Cu electrodissolution in
C being the concentration of Cl- in the film and D, NaCl solutions containing thiocyanate ions were re-
the Fickian diffusivity of Cl- (all non-Fickian trans- ported by Gu et al. (1990). It was observed that in the
port effects are neglected). Pearlstein et al. (1985) as- presence of externally imposed magnetic fields and by
sume that film porosity and pore size distribution properly controlling the electric potential, one could
remain constant and uniform across the film and that alter the period and amplitude of the oscillations and
reaction (37) only occurs at the g(t) interface and could even suppress them under certain conditions
reactions (38) and (39) at the h(t) interface. At g(t) the (Gu and Fahidy, 1992). Direct visual observations
 Electrochemical reaction dynamics 1519

showed that the thiocyanate ions first cause a precipi- region II (400 mV < E < 1300), were observed. In re-
tation in the vincinity of the anode followed by the gion I the anode was completely covered (within
appearance of a black film on the surface, followed by 2 min) with a white CuCl film. The observed oscilla-
oscillations. No oscillations were observed in the ab- tions are chaotic and the chaotic attractor was cal-
sence of that film. In subsequent papers, Fricoteaux et culated to have a correlation dimension of 2.6. This
al. (1992) and Gu et nl. (1992a, b, 1993) used concepts chaotic behavior subsequently became less complic-
from the fractional Brownian motion theory [see ated, giving rise to a two-peak oscillation, a one-peak
Mandelbrot and van Ness (1968)] to analyze the oscillation, and finally becoming a steady state.
long-term behavior of the oscillatory behavior ob- In region II a visible strip of a thick CuCl film forms
served in anodic copper dissolution. Using surface at the perimeter of the electrode, while a more com-
enhanced Raman spectroscopy, they were able to pact thin CuCl film forms at the center. As the experi-
show that, during oscillations, the electrode surface is ment progresses, the visible film moves inwards,
covered by a Cu20 and a CuSCN film. eventually covering the whole anode surface. In this
Extensive investigations of the dynamic behavior of region oscillations of much higher frequency are ob-
Cu electrodissolution in acidic chloride media have served. The attractor shown in Fig. 31 appears to be
been performed by Bassett and Hudson (1987, Shil’nikov chaos. Shil’nikov chaos (or homoclinic
1988a, b, 1989, 1990a, b). Bassett and Hudson in a re- chaos: Shil’nikov, 1965) has also been observed in the
cent paper (Bassett and Hudson, 1990b), for example, copper/chloride ion system with 0.1 M NaCl. Accord-
have described the dynamic behavior of Cu electrodis- ing to the theory developed by Shil’nikov, there are
solution in 0.3 and 0.5 M NaCl in 1 N HzSO, electro- infinitely many nonperiodic trajectories in systems
lytes. Potentiostatic experiments with an electrolyte which display a homoclinic orbit by being asymptotic
containing 0.5 M NaCl and a Cu electrode rotating at to a saddle-focus at t 4 a~ and t 4 - m provided
1000 rpm are shown in Fig. 30. Oscillations occur in that 1P/p 1 < 1, where (P k iR, p) are the eigenvalues
the range 275 mV < E < 1000 mV. In the experiment of the saddle-focus (Argoul et al., 1987).
there is first a transient, followed by oscillations. In the time series and attractor shown in Fig. 31,
Eventually, the oscillations cease and current drops to trajectories spiral out from that point, make a large
the steady-state value shown in Fig. 30. Two distinct
regions of behavior, region I (275 < E < 400 mV) and 80

420 ,-

0 f
-100 500
I I
900 1300
I I
1700
Time

E (rnV “S SCE) 80

r .
6000 1200

800

400

--lo
100 2.50 400 400 900 1400
E(mV) 40 80

Fig. 30. (a, top) I vs E, 0.5 M NaCI; 2OOOrpm. (b, bottom)
Time at which oscillations start (bottom of vertical line) and
stop (top of line); OSM NaCI; 1OOOrpm. Reproduced by
permission of the Electrochemical Society from Bassett and
Hudson, J. electrochem. SK (1990b).
Fig. 31. (a, top) Chaos as oscillations end: time series; 0.5 M
NaCI; 400 mV. (b, bottom) Chaos as oscillations end: attrac-
tor; 0.5 M NaCI; 400 mV; r = l/120 s. Reproduced by per-
mission of the Electrochemical Society from Bassett and
Hudson, J. electrochem. Sot. (1990b).
1520 J. L. HUDSON and T. T. TSOTSLS

circuit around the attractor, and are then reinjected For Cu electrodissolution in 0.1 M NaCl + 1 N
in its vicinity. Since the point of reinjection varies H2HS04 electrolytes the observed behavior is differ-
slightly each time, the number of small-amplitude ent (Bassett and Hudson, 199Oa). The results of poten-
oscillations around the saddle-focus can also vary. tiostatic experiments with a Cu anode rotating at
The fact that the trajectories are reinjected in 1000 rpm are shown in Fig. 32. Oscillations are ob-
a nonoscillatory manner near the supposed saddle- served in the region 300 mV < E -c 1050 mV. In the
focus and leave the area of the supposed saddle-focus region 300 mV < E < 315 mV the oscillations are
by oscillating away from it indicates that the saddle- first single-peak, making the transition during a
focus has eigenvalues p and P + iR, where fi is neg- period-doubling bifurcation to a two-peak and to
ative and P is positive. This then is a “spiral”-type a four-peak oscillation, and finally to chaotic behav-
strange attractor as described by Riissler (1976a, b, ior. The Cu surface is covered by a red/brown film
1977). Shil’nikov chaos for strongly contracting flows, (which Bassett and Hudson report to consist of
which exhibit the “spiral”-type attractor, has an inter- CuCl/Cu,O), which first forms at the perimeter and
esting feature: the return map of a Poincari section subsequently moves to cover the whole electrode sur-
taken transverse to the trajectories as they leave or face. In the 315 mV < E -c 1050mV region the oscil-
return to the area of the saddle-focus is multi- latory behavior observed is Shil’nikov chaos as in
branched, i.e. it consists of a set of one-dimensional region II above.
curves, each of which is associated, with some non- Intricate dynamic behavior has also been reported
negative integer. This integer represents the number of by &hell and coworkers (Albahadily and Schell, 1988;
small-amplitude oscillations a trajectory completes Albahadily et al., 1989; Schell and Albahadily, 1989)
around the saddle-focus between two successive for Cu electrodissolution in H,POI solutions. For
crossings of the Poincare plane (Argoul et al., 1987). a rotating Cu electrode in a HJPO, electrolyte
Such a return map can be found in the paper by thermostated at a temperature of - 175°C the re-
Bassett and Hudson (1988b). gions of different dynamic behavior in the rotational
Eventually the attractor gives way to the nonoscil- speed vs potential parameter space are shown in Fig.
latory behavior. The behavior with 0.3 M NaCl was 33. The left (solid line) boundary in this figure involves
generally similar to that observed with 0.5 M NaCl an ordinary, supercritical Hopf bifurcation, where by
except in region I, where the chaos for 0.3 M NaCl slowly varying the potential or the rotational speed
disappeared through three different routes. In the first one observes a small-amplitude oscillation upon
route the chaos gave way to a three-peak periodic crossing this boundary, the amplitude of the oscilla-
behavior, then to two-peak, then to one-peak oscilla- tions increasing as one moves away from the bound-
tion and finally to a nonoscillatory behavior. In the ary. Things are not that simple on the right boundary
second route the chaos gave way to a simpler chaos however. Large-amplitude oscillations were observed
with a sheet-like structure to be followed by a series of when one crossed the right (dashed) boundary into the
period-doubling transitions to four-peak, two-peak SO region and 1 mV away from the boundary. These
and one-peak oscillations. In the third route reverse large-amplitude oscillations, close to the boundary,
period doubling of tori from chaos was observed. In were mixed with small-amplitude oscillations. Along
this dynamic behavior (Bassett and Hudson, 1989), as line AB of Fig. 33 at the lower potentials, only large
the experimental time and the film thickness in- single-peak oscillations were observed. As the poten-
creased, the chaotic attractor first changed into a two- tial increased, the system was moved through a range
band chaotic attractor, then to a quasiperiodic of mixed-mode oscillations (the number of small-am-
motion on a double torus, followed by a period- plitude oscillations increasing with increasing poten-
having bifurcation to a torus with a next maximum tial) until a point where only small-amplitude single-
map consisting of a single loop followed by peak oscillations were observed, which themselves
a transition to a limit cycle and finally to a steady disappeared through a Hopf bifurcation, when the
state. A similar-type bifurcation, i.e. period doubling right boundary of Fig. 33 was crossed. Both periodic
of tori to chaos, had previously been seen in fluid and aperiodic MMOs were observed, the latter imply-
mechanics (Haucke et al., 1984) and predicted theoret- ing the presence of Shil’nikov chaos, Several MMOs
ically by Franceschini (1983) from the analysis of were also observed within the region labeled SO in
differential equations resulting from the truncation of Fig. 33, apparently not being a continuation of the
Navier-Stokes equations and by Argoul and Arneodo MMOs just described. Period-doubling bifurcations
(1984) who studied an external oscillation coupled to leading to chaos were also observed in the same
an oscillatory system, which then, as a result, under- region.
goes period-doubling bifurcations to chaos. Albahadily et al. (1989) have also reported observ-
Interesting behavior was also observed for Cu in ing Farey sequences of mixed-mode oscillations
0.3 M NaCl + 1 N H2S04 solution for lower rota- (MMOs) with the Cu in H,PO, system. Farey se-
tional speeds of 400 rpm (Bassett and Hudson, 1988a). quences are defined as periodic sequences, for which
This behavior involved a two-band chaos, which then a one-to-one correspondence can be established with
gave rise to a one-band chaos to chaos on a broken ordered sequences of rational numbers. They have
toroidal structure, and finally to quasiperiodic behav- been typically observed in systems for which there is
ior and nonoscillatory behavior. a locking relation between an intrinsic frequency of
 Electrochemical reaction dynamics 1521

350
r
300 -

zoo - Oscillalions

Steady orate

50
I”I / _*,~-.-._*_._.-w-~-~_.~.-.-~
*.d-.‘*
0’ I
100 300 500 700 900 1100

No oscillations

I T

E (mV vs SCE)
Fig. 32. (a, top) I YS E; 1OOOrpm. (b, bottom) Time at which the oscillations start (bottom of vertical line)
and stop (top ofline); 1000 rpm. Reproduced by permission of the Electrochemical Society from Bassett and
Hudson, J. electrochem. Sot. (1990a).

the system with an externally driven oscillation or
with another internal frequency, the combined system
trajectories lying on a torus. The Farey sequence of
MMOs reported for the Cu/HsPO., system is, how-
ever, not associated with phase locking on a torus.
The analysis of the data shows that the basic structure
in the phase space that supports MMOs is found in
the region of chaotic oscillations and a map with two
extrema [for a further discussion of the two extrema
maps, see Ringland et al. (1990) and Ringland and
Schell (1991)] is the strongly constraining limit rep-
resentation of this structure. MMOs associated with
phase locking on a torus will have an underlying
one-dimensional map possessing no dual extrema.
Typical measured MMOs with a rotating Cu disk
electrode thermostated at - 20°C in HsP04 are
shown in Fig. 34. The Farey tree constructed from the
observed states is shown in Fig. 35. The potential is
thought to increase to the right of this figure (the
vertical dimension used solely for diagrammatic con-
venience). Note in Fig. 35 that each pattern of each
state is the concatenation of the patterns of the pair of
states above it, on either side. The Farey tree arises in
number theory as a scheme for the progressive genera-
tion of all rational numbers between a given pair of
rationals p/r and q/s, which proceeds by writing the
Farey sum (p + q)/(r + s) between the two starting
rationals. The rational number corresponding to
a given MM0 (called the firing number) is repres-
ented as F = S/(L + S), i.e. the fraction of small oscil-
lations in the given MMO. A plot of the firing number
of the MMOs vs the potential, as reported by
Albahadily et al. (1989), has a structure similar to that
of the “devil’s staircase” seen in models of phase
locking. In the experiments with the Cu/H,PO, sys-
tem, Albahadily et al. (1989) report that for the most
part the region of MMOs is separated from
quasiperiodicity by a region of chaotic states, al-
though at higher rotational rates only small distances
separate the region of MMOs from quasiperiodicity,
making it difficult to even determine whether an inter-
mediate chaotic region even existed. Nevertheless, the
authors claim that the evidence indicates that no
stable torus is present in the region of MMOs leading
to the conclusion, as already discussed, that the Farey
sequence observed does not arise due to phase locking
on a torus.
In a recent paper, Schell and Albahadily (1989)
have reported bands of alternating periodic and cha-
otic states for the Cu/H1P04 system, each state pos-
sessing an MM0 structure with a different combina-
tion of large- and small-amplitude oscillations. The

CES 49: 10-C

 J. L. HUDSON and T. T. TSOTSIS

sz Potential (V)
0.80

Fig. 33. Measured boundaries in the parameter plane, rota-

tion speed vs the potential set for the working electrode that
separate the region for which sustained oscillations were
observed (labeled SO) from the region for which only stable
stationary states were found (labeled SS). Solid lines consist
of points at which Hopf bifurcations occurred; dashed lines
consist of points at which mixed-mode oscillations appeared.
Temperature = - 17S”C. The small-amplitude oscillations
shown in the insert were observed just inside the solid por-
tion of the boundary: rotation speed= 2200rpm, poten-
tial = 427 mV, maximum absolute value of the
current = 1.4mA, minimum value = 1.2 mA. The waveform
consisting of large and small-amplitude oscillations was le)
measured just inside the dashed portion of the boundary: 150
rotation speed = 7000 rpm, potential = 567mV, maximum
absolute value of the current = 5.8 mA, minimum Time (9)
value = 1.4mA. The dynamic behavior observed when the
system was moved along the line labelled A-E is describedin Fig. 34. A continuation of the sequence shown in Fig. I of
Section IIB of the original paper. Reproduced by permission the original paper. Rotation rate and the scale of the current
of the American Institute of Physics from Albahadily and are the same as Fig. I of the original paper: (a) 1’ state,
Schell, J. them. Phys. (1988). I’= 430.15mV; (b) a 1’ state, Y= 430.30mV; (c)a l4 state,
V = 430.4OmV; (d) a l5 state, V = 430.45 mV; (e) a mixed-
mode state near to the end of the sequence, V = 430.49 mV.
chaotic regimes in this sequence were shown to be Reproduced by permission of the American Institute of
linked to the periodic regimes through tangent and Physics from Albahadily et al., J. them. Phys. (1989).
period-doubling bifurcation with the waveforms of
the chaotic MMOs appearing to be mixtures of the
waveforms of the adjacent periodic states. They have
also observed a transition from small-amplitude cha-
otic oscillations to chaotic MMOs. Similar peri-
odic-chaotic sequences of MMOs had previously
been observed with the Belousov-Zhabotinski reac-
tion (Hudson et al., 1979; Hudson and Mankin, 1981;
Coffman et al., 1987).
Artificial neural network (ANN) analysis was ap-
plied to current vs time dynamic data for the
Cu/H,PO, system by Hudson et al.. (1990) and Rico-
Martinez et al. (1993). Both discrete- as well as con-
tinuous-time nonlinear signal processing of Cu elec- Fig. 35. A portion of the Farey tree constructed of observed
trodissolution data were utilized. The discrete states. States marked with a star were observed for only four
approach, although performing well in terms of to six cycles. Most other states were observed for many more
cycles. Reproduced by permission of the American Institute
predicting the experimental time series, is incapable of
of Physics from Albahadily et nl., J. them. Phys. (1989).
correctly reproducing the observed bifurcation se-
quences. The continuous approach, on the other
hand, seemed to be successful in predicting both the 1961; Pointu, 1969a, b; Galushko et al., 1972a; Poncet
time series and the overall bifurcation behavior. et al., 1978; Vuchkov and Rashkov, 1981; Al-Kharafi
The dynamics of the Cu/HJPO, system have at- and El Tantawy, 1981; Glarum and Marshall,
tracted a lot of attention through the years, with 1985a, b; Novak and SzBcs, 1986; Tsitsopoulos, 1988;
oscillations for this system reported for the first time Tsitsopoulos et al., 1987, 1989; Champagnie et al.,
back in 1936 by Jacquet (1936) and by several investi- 1991). The oscillations have been attributed to
gators since then (Hoar and Farthing, 1952; Lorking, changes occurring within surface or near-surface
1962; Williams and Barrett, 1956; Giles and Bartlett, films. Glarum and Marshall (1985a) have attributed
 Electrochemical reaction dynamics 1523

the oscillations to phenomena occurring within a vis- ions and increased current densities. The cycle would
cous interface layer formed close to the anodic sur- then repeat itself. The concentration polarization of
face, which was shown to have negative impedance the Cu2+ ions would again cause an increase in the
characteristics. Other investigators have attributed local pH, which would trigger the formation of
the oscillations to various surface films formed on the CUE , which would then block the surface, and so
anodic surface. Williams and Barrett (1956) claim that on. Although the mechanism sounds reasonable,
the surface film is CU~(PO~)~. 3H20, but others be- Tsotsis and coworkers (1989) in their original paper
lieve that the surface films responsible for the oscilla- cautioned against putting much faith into it. The
tions are oxides or hydroxides of Cu. Tsotsis and complex experimental results of Schell and coworkers
coworkers (Tsitsopoulos, 1988; Tsitsopoulos et al., provide ample support and evidence for their state-
1987.1989; Champagnie et al., 1991) have made exten- ment. Before a quantitative mechanism for oscilla-
sive investigations of the dynamics of the Cu/H,PO, tions emerges, important factors, such as the effect of
system using an array of in siru (like ellipsometry and local pH changes, changes in solution viscosity, the
video microscopy) and ex situ (like XPS and SEM) ever present boundary layer effects, the possible pres-
techniques. Ellipsometry and video microscopy ence of space charge effects, the surface and bulk
showed the anodic surface to be changing in phase distribution, and the thickness of the Cu,O and
with the current oscillations. XPS- and X-ray-induced CUE films formed and dissolved during the oscil-
Auger spectra of the surface showed that, during oscil- lations, still need to be investigated in detail.
lations, the surface is covered by both CuZO and Oscillations during anodization of Cu in neutral
Cu(OH),, but in the passive state of the oscillatory and acidic sulfate and nitrate solutions have also been
cycle (i.e. the minimum in current) the presence of reported by a number of investigators. Landolt et al.
CUE is more profound (compared to Cu20) than (1969, 1970) and Kinoshita et al. (1970), for example,
in the active state. SEM and in situ video microscopy have reported voltage fluctuations in the transpassive
showed that the Cu(OH)* formed does not com- Cu dissolution region for Cu in KNOs and KrSO.,
pletely fill the pores of the Cur0 film, consistent with solutions. Kawczynski et al. (1984, 1988) have ob-
the fact that the anodic surface does not completely served both regular multipeak and chaotic oscilla-
passivate during the oscillations. Tsotsis and tions during Cu anodization in a CuS04 + HLS04
coworkers proposed a qualitatively simple mechan- solution. They have analyzed the chaotic attractor in
ism (similar to the one proposed for Cu anodization in terms of one-dimensional Poincare maps. Oscillations
acidic chloride media) for oscillations. According to during Cu anodic oxidation in acidified Cu sulfate
them the metal enters the oscillatory region when the solutions have been reported by Garneau et al. (199 1).
current density reaches values corresponding to its Oscillations only occur when a sufficiently thick sur-
active state. The anodic potential at this point is in the face film is formed. Current oscillations during the
range 40@440mV and the electrolyte interphase anodization of Cu in H2S04 were also studied by
is saturated with Cu’+ ions due to the active dissolu- Minotas et al. (1989) as a function of the verti-
tion process. In contrast, the hydrogen ions, due to cal/horizontal position of the electrode. Gravity was
their high mobility, are forced out of the boundary found to affect both the amplitude and frequency of
layer, thus causing an increase in the local pH (prob- the oscillations. XRD showed the presence of
ably enhanced by the accumulation of OH- and CuSO, xH,O on the anodic surface and SEM
[H,PO,] - ions due to electrostatic forces). This local showed the existence of white products on a darker
pH increase will then trigger the formation of Cu or Cu oxide background. Both periodic and cha-
Cu(OH), through electrochemical reactions involving otic oscillations during Cu dissolution in an acetate
the Cu surface of the CuaO film or by precipitation buffer solution have been reported by Dewald et al.
reactions involving Cu ‘+, The Cu(OH)* formed will (1991, 1993). The oscillations appeared after the elec-
tend to hinder and decrease the rates of formation and trode surface had been covered by a red-brown film
diffusion of CL?+ ions from the metal to the electro- (probably Cu20). SEM and XRD were used to study
lyte and will result in a decrease of the current density. the electrode surface. The chaotic oscillations were
The oxide films formed are porous and the Cu(OH)r shown to be low-dimensional deterministic chaos. Us-
formed does not completely fill the pores; therefore, ing a recursive proportional feedback control scheme
the metal does not passivate completely and the cur- they were able to stabilize the chaotic oscillation into
rent density does not drop to zero. Once the current a period-l orbit (Parmananda et al., 1993).
density and the rate of Cu dissolution decrease, the Potential oscillations during open-circuit immer-
excess of Cu2+ ions at the electrolyte interphase is sion of Cu-AI and Cu-Ag-Al alloys in NaOH solu-
depleted, resulting in an increased buildup of the H+ tions have been reported by Hurtado et al. (1993). The
ion concentration. The net result of this process could authors explain the oscillations in terms of the Al
then be a decrease of the local pH and an increase in dissolution process, which affects the Cu dissolution
the rate of the Cu(OH), dissolution (probably en- process, which involves the formation and dissolution
hanced by the high potential fields across the film). of a Cur0 film. The accumulation of aluminate ions
The partial dissolution of this CUE film would at the electrode interphase and their diffusion to the
then result in the unblocking of the Cu surface, and in bulk solution provide the driving force for the oscilla-
turn in increased rates of Cu dissolution into Cu2+ tions.
1524 J. L. HUDSON and T. T. Tsorsrs

Nickel electrodissolution cause Ni ions to leave the metal and enter the film.
The earliest account of oscillatory behavior with There they will form a nonstoichiometric Ni ion ex-
this electrochemical system is due to Hoar and cess region (see Fig. 36) at the metal/film interface.
Mowat (1950). For Ni anodization in H,SO, they Simultaneously, some Ni ions in the oxide film will
observed regular potential oscillations under gal- enter the solution forming a Ni ion deficient region at
vanostatic conditions. They proposed the following the film/electrolyte interface. Due to the positive po-
qualitative mechanism to explain the observed oscilla- tential one expects the Ni ions to move toward the
tions. The rise in potential is due to the formation of film/electrolyte interface and the cation vacancies to
a thin passivating film, the rate of formation of which, move toward the film/metal interface. Where they
under these conditions, is greater than its rate of meet, a stoichiometric region (SR) is expected to be
dissolution. As this happens, oxygen can be dis- formed. Stoichiometric Ni oxide films are bad
charged at its surface as an alternative anodic reac- ionic/electronic conductors. The SR, being a poorly
tion. As a result, the amount of current available for conducting region, is therefore expected to cause
film formation diminishes and the rate of film forma- a large field potential drop (see Fig. 36). This would
tion then becomes less than its constant rate of dis- then lead to a tunneling of electrons from the valence
solution. The film finally disappears and the potential band of the Ni oxide on the solution side of the SR to
returns to values corresponding to active metal dis- the conduction band of the oxide on the metal side of
solution. Oxygen discharge ceases, the film building the SR. These electrons neutralize the excess Ni ca-
process starts again, and the cycle repeats itself. In tions and the holes generated by the tunneling process
a later report, Hoar (1952) also implicated changes in neutralize the negative charges of the cation va-
the pH at the electrode/electrolyte interface in the cancies. Thus, the SR builds further in thickness.
formation of the passive oxide layer. A stage is thus reached, where electronic tunneling
Regular oscillations in the potential were also re- becomes difficult and further passage of current
ported by Osterwald and Feller (1960). A model con- causes more Ni cations on the metal side of the SR
sisting of two ordinary differential equations was and Ni cation vacancies on the solution side to build,
presented later by Osterwald (1962) to explain the thus increasing the field potential drop along the SR.
oscillations. In view of the complex behavior that has This then results in the increase in the potential ob-
been reported with the Ni electrodissolution sys- served during the oscillation. When the field potential
tem-see below-the validity of Osterwald’s model is drop reaches a high value then internal field emission
questionable. occurs from the valence band of the Ni oxide on the
Doss and coworkers (Indira et al., 1969; Doss, 1974) solution side to the conduction band on the metal side
have also reported galvanostatic oscillations with the across the SR. This results in the breakdown of the SR
Ni/H,SO, system and have proposed an interesting through the formation of highly conducting filaments.
mechanism to explain these oscillations. According to This then brings down the potential drop in the SR.
them, the anodic dissolution of Ni involves three The SR then begins to form again. According to
steps: (i) the entry of Ni ions into a solid oxide film, Indira et al. (1969), this repeated formation/break-
that has been reported to cover the surface of the down of the SR is the cause for the oscillations. They
metal even in the absence of anodic current; (ii) migra- claim, furthermore, that their SR breakdown/forma-
tion through the oxide film; (iii) transfer into the tion mechanism is of more general validity. For
solution and formation of the aqueous or other com- example, it has been observed that the transition from
plexes. In the absence of electronic conduction [Indira the active to the passive state of the metal is caused by
et al. (1969) claim that the films formed are nonporous passing only a small amount of current. In most
and charge transfer occurs only through solid-state instances this current would not even be sufficient to
conduction] a positive potential on the metal would cover the apparent electrode surface by one mono-

,
H G
Fig 36. Schematic diagram for potential drop in the nickelLsulphuric-acid system: (AB), potential in metal;
(BC) potential drop at the metal-oxide interface; (CD) potential drop in nickel ion excess region; (DE)
potential drop in SR; (EF) potential drop in the nickel ion deficit region; (FG) potential drop in electric
double layer at the film-solution interface; (GH) potential in solution. Reproduced by permission of
Elsevier Sequoia S.A. from Indira et al., J. electroanal. Chem. 21, 61 (1969).
 Electrochemical reaction dynamics 1525

layer of oxygen. Doss et al. theorize instead that the 1989, 1990) the existence of propagating waves
active state of the metal is caused by a few conducting and antiphase oscillations (Figs 37 and 38). They
filaments across the SR, their cross-sectional area used a rectangular shallow electrochemical cell
being only a small fraction of the total surface. Their (200 x 200 x 40 mm) holding two thin Ni wires. The
buildup would only require a small amount of current. current distribution along the working anode was
A mechanism of oscillations involving the forma- recorded using 15 Ag/AgCl microelectrodes equally
tion of Ni oxides has also been suggested by Ohashi spread along the wire. The antiphase oscillations (see
and coworkers (Ohashi and Adachi, 1983; Ohashi and Fig. 38) during galvanostatic operation are due to the
Hirai, 1985). Oscillations observed during the electro- condition of constant space-averaged current in the
dissolution of Ni in solutions containing chloride and presence of local current oscillations. There is a 180
iodide ions have been reported by Li and Vittori phase shift between the current oscillations at the wire
(1988). These oscillations were observed for a broad edges, so that the sum of all oscillations results in
range of conditions (i.e. potential), when the iodide a constant space-averaged current. Analogous anti-
concentration was kept low. Increasing the iodide phase oscillations have been reported with catalytic
concentration or adding surfactants like sodium-p- wires operated in the constant-resistance mode
octylbenzenesulfonate, even in the presence of low (Sheintuch and Schmidt, 1986; Sheintuch, 1990). The
iodide concentrations, suppresses the oscillations. pattern observed in the “almost potentiostatic mode”
Changes in the color of the Ni surface during the shows good global synchronization (the “almost po-
oscillations (a black color alternating with a metallic tentiostatic mode” of operation results by incorporat-
appearance) are due, according to Li and Vittori, ing a resistance between the reference and the working
to a preferential dissolution at the grain boundaries. electrode; both the current and the true electrode
Oscillations during electrodissolution of Ni in H2S04 potential oscillate in this case because they relate to
containing iodide ions were reported by Champagnie each other by Ohm’s law).
et al. (1989). The authors used SEM, XPS, optical Based on their observations, Sheintuch, Pismen,
microscopy, and computerized video image analysis and coworkers have constructed a detailed bifurca-
to identify the chemical nature of the anode metal tion map of the dynamics of Ni electrodissolution in
surface films during the oscillations. sulfuric acid (Lev et al., 1988b; Lev et al., 1989; Haim
Sheintuch, Pismen, and coworkers have made an et al., 1992b). The current vs potential curve is shown in
extensive investigation of the dynamics of the Fig. 39. When the potential is the only variable deter-
Ni/H,SO, system. They reported (Lev et nl., 1988a, b, mining the current in the potentiostatic mode, the

(b)

Fig. 37. Traveling waves during almost potentiostatic oseiIlations: (a) three-dimensional representation of
local current distribution; (b) enlarged section. Operating conditions: 20-em nickel wire in 6 N sulfuric acid.
1.67V relative to saturated Calomel electrode, current normalized relative to 65mA/cm2, distributed
homogeneously. Time scale in scans (50 scans s-‘k length scale covers the whole wire. Reproduced with
permission from Nnture (Lev et al., 1988a). Copyright 1988 Macmillan Magazines Limited.
 1526 J. L. HUDSON and T. T. T~~TSIS

Fig. 38. Local current distribution of antiphase oscillations during galvanostatic operation. Operating
conditions: 20-cm nickel wire in 2N sulfuric acid, current is 16.25mA/cmZ; local current normalized
relative to the current density at 15.5mA/cm* as measured under potentiostatic conditions
[I = (0, - v,,)/(u, - uO), where u,,, uIIand u,are the microelectrode potential at rest, under galvanostatic and
under potentiostatic conditions, respectively]. Time and length scales are the same as in Fig. 37. Repro-
duced with permission from Nature (Lev et al., 1988a). Copyright 1988 Macmillan Magazines Limited.

lo2
r Unique __ USN

Electrode potential (mV)

Fig. 39. Current density vs potential curve for dissolutionof

nickelin 0.5 N H2S04. The regions shown are active dissoiu-
tion (I), primary passivity (2), transpassivity (3), secondary
11 I I I I
0 1 2 3 4
passivity(4) and oxygen evolution (5). From Lev et al.
(1988b). Sulfuric acid concentration (N)

Fig. 40. Bifurcation map of nickel dissolution in the vicinity

states lying in the ascending branches are stable, while
those lying in the descending branches are unstable.
In the galvanostatic operation, the number of states
changes at the extrema of the curve. Interesting dy-
namics are observed during galvanostatic operation
in the transpassive region. For HISO_, concentrations
below 0.38 N, only stationary states are observed.
A unique oscillatory state is possible for concentra-
tions below 4.5 N. Multiple limit cycles and other
complex dynamic behavior are observed at higher
concentrations. A continuous oscillatory region,
bounded by two Hopf bifurcations, exists [see Fig.
2(a)] in the concentration range 0.384.95 N. The
oscillatory region becomes discontinuous in the range
0.95-2.5 N [Fig. 2(b)]. At higher concentrations, the
upper oscillatory branch disappears. The bifurcation
map for the Ni/H,SO, system for concentrations
below 4 N is shown in Fig. 40. Note the Hopf, saddle-
node, saddle-loop lines and the existence of a cusp (C)
and a double-zero eigenvalue (DZ). Regions of
biorhythmicity and other complex dynamic behavior
appear for concentrations above 4.5 N (see Fig. 41).
The region of complex behavior is also shown sche-
matically in Fig. 41. The lower boundary of that
region was observed to be a transition from simple
periodicity to quasiperiodicity, while in the upper
of a double-zero-eigenvalue singularity: lines denote stable
or unstable saddle-node (i.e. SN or USN).., (- . 4,,. Houf
(------- ) and saddle-loop (SL) (- -) bifurcations.
Dotted region indicates existence of oscillatory state. Cusp
(C) and double-zero-eigenvalue (DZ) are also marked. Froh
Lev et al. (1988b).
boundary the chaotic motion turns into periodic
motion. No hysteresis is observed upon crossing these
boundaries. Figure 42 shows the sequence of ampli-
tudes, winding numbers, and computed correlation
dimensions of oscillatory states observed at 8.2 N
H,S04 concentration. Note the existence of a band of
quasiperiodic states (denoted by T) between regions
of single-peak and four-peak oscillations and two
regions with chaotic oscillations. The first region has
a relatively high correlation dimension, while the sec-
ond region is only mildly chaotic. The sequence
of states (Pl-T-PQ-P3-C-PS-P7-P&P&P8-PlC&
C-P2) is reported to be a robust property of the
Ni/H2S04 system, observed with decreasing current
and other Ni wires. Similar bifurcation diagrams with
increasing current, i.e. simple periodic, quasiperiodic,
chaotic, complex periodic, chaotic, and periodic, were
also observed for other H,SO, concentrations.
Haim et al. (1992b) have developed a mathematical
model to describe the experiments of Lev et al. Ac-
 Electrochemical reaction dynamics 1521

100 NiO formation: NiOH + NiO + H + + e -

90 - Unique (U) Saddle ,- -
(46c)
2 80
5 70
Double zero NiO dissolution: NiO + 2H+ + Ni2+ + H,O.
< 60
(46f)
5 50
2 40 In their model, Haim et al. (1992b) identify four sur-
r 30 face species, i.e. nickel atoms, adsorbed bisulfate, sur-
s 20 face oxide, and surface hydroxide. Their mechanism
10 includes four variables: the electrode potential and the
coverages of three of the four species, 6,, for the bisul-
Sulfuric acid concentration (N) fate, n for the NiO and 0 for the total (oxide + hy-
droxide) coverage. Haim et al. (1992b) eliminate the 0,,
Fig. 41. Grand bifurcation map of Ni dissolution: typical coverage by assuming bisulfate adsorption to be in
phase planes ace unique(U), globallystable(U,) and oscilla-
tory states (0), multiplicity of oscillatory and stable states adsorption equilibrium, i.e.
(OS), bistability (near cusp), and bichythmicity (MO). The
Hopf, saddle-node and saddle-loop bifurcations ace identi- (474
fied in the figure; the generalized Hopf is denoted by the
dotted line. The domain of complex motions is detailed in
Fig. 7 of the original paper. Reprinted with permission from where Ch is the activity of hydrogen ions in solution.
Lev et al. Copyright 1989 American Chemical Society. For the rest of the reactions (46b)-(46f) they assume
that they follow the Tafel law, i.e. r m exp (aF$/RT),
4 representing the electrode potential and a the trans-
fer coefficient. In particular, they assume
for reaction (46b):

rb= kbCh(l -@-&)exp WW

o” 0.9 C for reaction (46~):
0.5
r (47c)

for reaction (46d):

r,,=k,,(l-0-t&)exp (47d)

for reaction (46e):

(47e)

for reaction (46f):

11 7
66 72 78 84 (47f)
Cucrenr (mAlcm*)
Haim et al. (1992) write surface balances for 0 and n
Fig. 42. Bifurcation diagram observed at 8N showing the
amplitude, nature, winding number and dimension of the
attractor (return maps of states marked by arrows ace shown
in Fig. 5 of the original paper). Reprinted with permission
from Lev er al. Copyright 1989 American Chemical Society.
c d”=, e
Mdt
-_I
J
cording to them, nickel anodization is described by
and for the electrode potential
the following reactions:
bisulfate adsorption: Ni + HSO; SNiHSO; (ads) 2-I-r
C ldt- b
-r. f

Ni dissolution: Ni + Ni2+ + 2e-
O2 evolution: Hz0 + 2H’ + )O,
NiOH formation: Ni + H,O + NiOH
Wa)
CM is the surface molar capacity, C1 the double-layer
(46b) capacity and I the imposed current. They first analyze
a two-dimensional problem by assuming dn/dt N 0.
+ 2e- 146c)
Parameter estimation in this two-variable model is
+ H+ + e- based on the fitting of the experimentally observed
(46d) bifurcation boundaries and singularities, The result of
 1528 J. L. HUDSONand T. T. Tsonrs
DZ
Ch (acid concentration)
10
stable
state
1 I I I
0 1 2 3
Sulfuric acid concentration (N)
Fig. 43. Comparison of observed (lower diagram after Lev
et al., 1988b, Chem. Engng Sci., 43, 1339) and simulated
(upper) bifurcation maps showing Hopf, saddle loop (SL),
saddle node (SN), and saddle unstable node (USN) bifurca-
tions and cusp (C) and double-zero (DZ) singularities. The
nature of motion in the simulated diagram is identical with
that marked in the corresponding experimental domain.
Reprinted with permission from Haim et al. (1992a). Copy-
right 1989 American Chemical Society.
this process is shown in Fig. 43. The model qualitat-
ively predicts the experimental behavior. The full
three-dimensional problem [eqs (48a)-(48c)] was then
numerically analyzed and shown to exhibit intricate
dynamic behavior. Haim et al. (1992) have also ex-
tended their model to describe the antiphase oscil-
lations under galvanostatic conditions and the travel-
ling waves, when a small external resistor is incorpor-
ated in the circuit, observed previously with the
Ni/H,SO, system by the same group (see the dis-
cussion above). Several other studies (Sternberg, 1989;
Vaiiliu et al., 1990) have also reported oscillations
during Ni electrodissolution in HzS04.
Oscillations and other interesting dynamic behav-
ior have also been reported during the anodization of
a number of other metals. A rather concise discussion
of some of these studies follows.
Other metals
Silver anodization. One of the earliest reports of
anodic oscillations during Ag electrodissolution is by
Gilbertson and Fertner (1942). They attributed the
oscillations to the dissolution of anodic films, either
AgCN or Ag,O, depending on the current density.
Anodic oscillations during Ag electrodissolution, un-
der potentiostatic conditions, in a plating bath con-
taining AgCN, KCN, and K2C03 were later reported
by Francis and Coiner (1950). They proposed a mech-
anism for oscillations similar to that of Gilbertson
and Fertner. At the beginning of the oscillatory cycle,
the current density is high and this results in consider-
able concentration polarization, i.e. decrease in CN-
and increase in Ag + concentrations. Subsequently,
the current decreases rapidly until a point is reached
where AgCN precipitates and forms a film. The oscil-
lations which follow are caused by cyclic precipitation
and formation of this film.
Oscillations during anodization of Ag in KC1 solu-
tions were reported by La1 et al. (1951). The oscil-
lations were attributed to the rearrangement and re-
crystallization of various anodic solid films. Large-
period oscillations under galvanostatic conditions
during the anodic oxidation of electropolished Ag
electrodes were reported by Dignam et al. (1969).
Oscillations were again attributed to the formation
and dissolution of Ag10 films.
Oscillations during the anodization of Ag in dense
HCl solutions were also reported by Indira et al.
J (1969). They proposed, however, a different mechan-
4 ism to explain the oscillations. According to them, the
anodic AgCl film consists of three regions. Near the
metal-film interface, a region exists with an excess of
Ag ions. Near the film-electrolyte interface, an Ag
ion-deficient region is found. A stoichiometric region
(SR) is formed in between. According to Indira et al.
(1969), during their experiments the Ag ion excess
region behaves as an N-type conductor. The asso-
ciated holes in the Ag ion-deficient region make it
a P-type conductor. The film in between acts as
a poorly conducting PN junction (PNJ). Consider-
able potential drop exists across the PNJ domain.
When the field exceeds a certain limit, the PNJ breaks
through an avalanche-type breakdown process and
highly conducting filaments form. This in turn brings
down the potential. Subsequently, the PNJ builds
again. The repeated formation and breakdown of the
PNJ thus causes the high-frequency oscillations ob-
served.
Current oscillations during the anodic dissolution
of Ag in a 1 M HCIO., electrolyte from a one-dimen-
sional artificial pit electrode have been reported by
Corcoran and Sieradzki (1992). The oscillations were
found to be chaotic (the fractal dimension was cal-
culated to be - 2.8) and are thought to result from
transitions between a bare and a salt-covered surface
or instabilities in local regions of a salt-film-covered
surface. Both types of oscillations were shown to re-
sult in porous electrode surfaces. This surface porosity
might lead to a stress corrosion cracking (Corcoran
and Sieradzki, 1992).
Aluminum and aluminum alloys. Several studies
have reported oscillations during the electrodissol-
ution and corrosion of Al and Al alloys. In one of the
earlier studies, current oscillations were reported by
Kassyura and Zaretskii (1971) during the anodic PO-
larization of Al alloys containing O&6.25% Mg in
NaN03 + NaCl electrolytes. The amplitude and per-
iod of oscillations were found to increase with increas-
ing NO; concentration.
 Electrochemical reaction dynamics 1529

Potential oscillations during the anodization of Cu tration to increase again, the deposited hy-
(3-8.5%) containing Al alloys in 3% NaCl solutions droxides/oxides to dissolve, and the cycle to repeat
containing NH.,OH were reported by Aeschbacher itself.
and Pagetti-Aimone (1974). The oscillations were cor-
related with the pitting corrosion observed under Gold anodization. Oscillations during Au anodiza-
these conditions. The electrochemistry, surface chem- tion in acidic electrolytes were first reported by
istry and morphology of Cu containing Al alloys, Franck (1958) and later by Vetter (1967). The electro-
immersed in sulfuric acid/chromic acid etching solu- chemical behavior of Au in acidic solutions contain-
tions, were also studied by Pocius (1983). The electro- ing chloride ions has been studied extensively by
chemical measurements showed the presence of ‘an Arvia and coworkers (Herrera Gallego et al., 1975;
oscillatory chemical reaction involving the dissolution Podesta et al., 1979b; Podesta et al., 1981, 1982b).
and deposition of Cu within the alloy. Current oscillations, for example, have been reported
Current density oscillations during the anodization for the Au/H,SO, system containing Cl- ions.
of Al in a NaV03 .2H,O electrolyte in the presence of Figure 44 shows a typical oscillation as reported by
formic acid and simultaneous formation of a porous Podesta et al. (1979b) for this system. Oscillations
alumina film were reported by Ragalevicius and appear both in the presence and in the absence of
Stakenas (1981). The oscillations were attributed to stirring. In the presence of stirring, oscillations are
a mechanism whereby the formic acid concentration observed within a potential range, for which a limiting
in the pores of the growing film decreases as the film current is observed. The oscillations were associated
thickness increases. This then results in lower current with a localized type. of corrosion. The electrodissol-
densities and increasing formic acid concentrations ution of the metal, according to Podesta et al. (1979b),
through replenishment from the electrolyte bulk. The occurs through the following two reactions:
cycle thus repeats. Denser films form at lower formic
Au + 2Cl- + AuCl; + e- (50)
acid concentrations.
Oscillations during the growth of anodic alumina 3AuC1, $ AuCI, + 2Au + 2Cl-. (51)
films in the presence of various supporting electrolytes
Reaction (50) is fast and reaction (51) is at equilibrium.
have also been studied by Cocke et al. (1985) and
The whole electrodissolution process is under dif-
Nourbakhsh et al. (1987). These oscillations result in
fusion control, in the absence of stirring or under
the oscillatory incorporation of various anions
limiting-current conditions. This results in the de-
(WOI-, MOOS-, Mn04- and CrOa-) in the growing
pletion of Cl- ions at the electrode interface, which
anodic alumina film. Rapid corrosion potential oscil-
then results in oxide layer formation (through the
lations during Al immersion in a brightening solution
discharge of HZ0 molecules). When this happens, the
were reported by Chatterjee (1984). The oscillations
current decreases because the surface passivates, the
were attributed to a passivationdissolution etching
HCl then diffuses back, dissolves the oxide film, and
mechanism. Potential oscillations under galvanostatic
the cycle repeats itself. The dissolution of the passivat-
conditions, during the anodization of Al in alkaline
ing film is thought to occur in a nonuniform manner;
solutions containing H202, were reported by Verba
and Koshel(1986). The oscillations were attributed to
Cobalt electrodissolution. The dynamic behavior of
a mechanism involving the formation and dissolution
Co anodization in various acidic electrolytes has at-
of passivating films at the anode (oxides, hydroxides).
tracted considerable attention. In one of the earliest
Potential oscillations on a single Al crystal exposed to
studies, Franck and Meunier (1953) studied the poten-
a NaOH solution were reported by Miadokova and
tial oscillations during Co anodization in hydro-
Siska (1987) and Halasa and Miadokova (1990).
chloric acid + chromic acid solutions. Hudson et al.
Finally, current oscillations (under potentio-
static/potentiodynamic conditions) and potential os-
cillations (under galvanostatic/current sweep condi-
tions) during the anodization of In containing Al
alloys in KOH solutions have been reported by
Wilhelmsen et al. (1991). They also proposed a mech-
anistic model to explain the oscillations. In particles
are deposited on the alloy surface after polarizing the
electrode at negative potentials (vs Hg/HgO). These
particles represent the active sites on the anodic sur-
face. Oxidation of Al proceeds via OH- consumption
at the active sites according to the following reaction:
Al + 40H $Al(OH): + 3e-. (49)
When the current density exceeds a critical value,
aluminum oxide or hydroxide will deposit on the
active sites, causing the current density to drop. The Fig. 44. Current-time display 2N HCI, Ed: 1.712V, 25°C.
low current density will then cause the OH- concen- From Podesta et al. (1979b).
1530 J. L. HUDSON
and T. T. TS~TSIS
(1988) studied the same system under potentiostatic
conditions using a rotating Co electrode. They at-
tributed the observed oscillations to a film formed
during the reduction of chromic acid.
In a more recent study, Bell et 01. (1992) have
studied the dynamic phenomena resulting from the
interaction of two Co disk electrodes (one rotating,
the other stationary) immersed in the same hydro-
chloric + chromic acid electrolyte. Figure 45 shows
the current vs potential for the upper and lower disks,
investigated individually opposite to blank disks.
Both disks show a region of oscillations, although for
the bottom disk the region is smaller. When both
disks are used, one can adjust their potentials inde-
pendently. By doing so, one observes many interesting
dynamic phenomena. For example, each electrode can
drive the other to oscillations, for conditions for
which the other electrode would not oscillate. Coup-
ling can, in some instances, drive both electrodes to
oscillations, for conditions for which neither electrode
would exhibit oscillations. Coupling, under condi-
tions for which both electrodes would oscillate, has
been shown to lead to chaotic oscillations but also,
under some conditions, to complete extinction of such
oscillations.
The anodization of Co electrodes in phosphate
solutions, at potentials where secondary passivity is
observed, was studied by Jaeger et al. (1985). The Co
electrode was shown to exhibi; current oscillations
-60 -40 -20 0 20 40 60
(b)
-60 -40 -20 0 20 40 60
Potential (mV)
Fig. 45. Current vs potential for each electrode with oppo-
site electrode blank: (X) steady state; (0) minimum and
maximum of current oscillations; 0.6M CrO,/l.ON HCl,
75rpm, 4mm gap. (a) Top electrode; (b) bottom electrode.
Reprinted with permission from Bell et al. (1992). Copyright
1992 American Chemical Society.
under potentiostatic conditions. As the potential in-
creased, a number of oscillatory states were observed
resulting from period doubling. Regular single-peak
and relaxation-type oscillations jump phenomena and
hysteresis behavior during Co anodization in H,PO,
solutions have been recently reported by Sazou and
Pagitsas (1992). The oscillations were attributed to the
formation and dissolution of various passive films.
A simple mathematical model involving two ordinary
differential equations, following the analysis of Degn
(1968), was also presented to explain the relaxation-
type oscillations (Pagitsas and Sazou, 1992).
The dynamic behavior of Co anodization in sulfuric
acid electrolytes containing nitrate ions has been in-
vestigated by Sazou et al. (1990). In acidic electrolytes,
in the absence of nitrate ions, they did not observe any
oscillations. Figure 46 shows the potentiodynamic
curve in the absence of nitrate ions. Sazou et al. (1990)
distinguish the following regions: (i) the active dissolu-
tion region (ab), where metal ions are formed and
oxide formation begins; (ii) region bc, produced by
blockage of the surface by a thin oxide film; (iii) the
reactivation regions (cc’and c’d), where oxide dissolu-
tion occurs by sulfate ions; (iv) a passivation section
(de), attributed to Co oxides of higher valency; (v) the
complete passivation region (ee’); and (vi) the oxygen
evolution region. Section bc disappears for poten-
tiodynamic runs with low scan rates or under poten-
tiostatic conditions. On reversing the potential scan,
a hysteresis appears in the transition from the passive
to the active state. Activation occurs in two steps, first
a sharp current rise to a peak followed by a decrease
in current and then, again, an increase to a limiting
value. In the presence of nitrate ions, above a certain
threshold concentration, in the current plateau re-
gion, one observes oscillations. The region of oscil-
lations in the w (rotational speed)-E parameter space
is shown in Fig. 47. Since, under potentiostatic condi-
tions, the surface is continuously changing, the ob-
served oscillatory behavior is also changing, varying
from simple periodic to what appears to be an aperi-
odic state. Sazou et al. (1990) attribute the oscillations
to a breakdown of the passive film, which results from
the action of NO; according to the following two
reactions:
Co + 3NO; + 3H+ + Co(NOJ)z + HNOZ + HZ0
(52)
HNOz + HZ0 *NO; + 3H+ + 2e-. (53)
The autocatalytic character of step (53) appears to
play a key role in the generation of sustained oscil-
lations.
The dynamic nature of Co anodization in sulfuric
acid electrolytes, containing chloride ions, was studied
in subsequent papers by Sazou and Pagitsas
(1991a, b). In the presence of chloride ions, following
an initial induction period, one observes a variety of
oscillatory behavior. Current oscillations are again
associated with localized pitting corrosion, due to the
attack of chloride ions on the passive surface. During
 Electrochemical reaction dynamics

Fig. 46. Potentiodynamic sweep curves for a rotating disk Co electrode in 1.58 M H2S04 aqueoussolution
at two different rotation speeds. dE/dt = 20 mV/s. Reproduced by permission of Else&r SequoiaS.A. from
Sazou et al., ;I. electroanal. Chem. 289, 220 (1990).

Fig. 47. Correlation between the rotation speed of the Co disk electrode and the potential region where
oscillations are observed. Composite of data from the hydrodynamic system 1.58 M HISO, + 0.15 M
NO;. In the inset a sample of current oscillations observed under two different sets of conditions are
shown. The points at which these oscillations appear are indicatedin the main figure by the numbers 1 and
2. Reproduced by permission of Elsevier Sequoia S.A. from Sazou et al., J. electroonol.Chem. 289, 228
( 1990).

oscillations, the active and passive states coexist
on the electrode surface. More recently, Sazou and
Pagitsas (1993a, b) reported oscillations in the pres-
ence of iodide ions. Under potentiostatic conditions,
oscillations were observed in the current plateau re-
gion. For higher iodide concentrations, one observes
two distinct potential regions where oscillations oc-
cur. Potential oscillations under galvanostatic condi-
tions and current oscillations under potentiostatic
conditions involving the redox Co(II)/Co(III) system
have been reported by Pastor and coworkers
(1992a,b). The oscillations were observed when two
Pt electrodes were immersed in a sodium perchlorate
solution in acetic acid containing l-3% H20. The
mechanism responsible for the oscillations (i.e. elec-
trochemical vs chemical) is unclear at this point.
Lead electrodissolution. A number of studies have
reported oscillations during Pb anodization.
Bhaskara Rao (1967) has reported potential oscil-
lations under galvanostatic conditions during the
anodization.of Pb and Pb alloy (Ag or Sn) electrodes
in an electrolyte containing LiAlCl.+ in propylene car-
bonate. l%e same author was unable to observe oscil-
lations during Pb anodization in an electrolyte con-
taining LiCl in y-butyrolactone. X-ray diffraction
1532 J. L. HUDSON and
studies of the Pb anode anodized in the LiAl&/
propylene carbonate electrolyte showed the forma-
tion of a PbCI, film. Bhaskara Rao attributed the
oscillations observed with this electrolyte to the
formation and dissolution of this film. No insoluble
PbC12 film was observed during the anodization of Pb
in the LiCVy-butyrolactone electrolyte. This explains,
according to Bhaskara Rao, why no oscillations were
observed in this system.
Current oscillations during the anodization of Pb
in H,S04 solutions were reported by Grauer et al.
(1969). The oscillations were observed in the region
prior to passivation. Oscillations during the galvano-
static polarization of Pb in NaOH solutions contain-
ing various concentrations of ClO; or C10, ions
have been reported by Abd El Aal (1992). The oscil-
lations were found to occur within the oxygen evolu-
tion region, indicating an effect of the aggressive
CIO; or ClO, ions on the oxygen formation/evolu-
tion process.
Tin anodization. The Sn/alkaline solutions system
is one of a number of electrochemical systems for
which both cathodic and anodic oscillations have
been observed. Potential oscillations under galvano-
static conditions during the anodization of Sn and Sn
amalgams in NaOH solutions, for example, have been
reported by Shams El Din and Abd El Wahab (1964)
and Shams El Din and Kamel (1972). The oscillations
were attributed to the competition between the anodic
formation and dissolution of Sn(OH),. The potential
of the Sn electrode oscillated between its Sn/Sn(OH)z
and Sn(OH)2/Sn(OH), potential values.
The competition between the formation and dis-
solution of Sn(OH), has also been implicated to ex-
plain the potential oscillations observed for the
Sn/NaOH system by Wu and Hao (1984). In an
earlier study, Hampson and Spencer (1968) observed
potential oscillations during the anodization of Sn in
dense alkaline (KOH) solutions. Oscillations were ob-
served with horizontal but not with vertical elec-
trodes, and were attributed to the formation and
dissolution of a SnO, film.
In a later study, Stirrup and Hampson (1976) re-
ported current oscillations during Sn anodization in
NaOH solutions for electrodes rotating at high rota-
tional speeds. The oscillations were observed in a re-
gion of potentials corresponding to the transition
between primary and secondary passivity. Primary
passivity is caused by deposition of a SnO or Sn(OH)z
film, which forms when the solubility limit of stannite
ion (HSnO;) is exceeded. Secondary passivation is
caused by the formation of SnOz. Stirrup and
Hampson suggest a mechanism for oscillations
similar to that of Shams El Din and Abd El
Wahab, except that the surfaces, between which the
electrode oscillates, are Sn/SnO(SnOH)2 and
SnO[Sn(OH),]/SnO,. The formation of a permanent
film of SnO, causes the oscillations to cease.
Muralidharan et al. (1983) have also observed cur-
rent oscillations under potentiodynamic conditions
T. T. TSOTSIS
for the Sn/NaOH system. They dispute the mechan-
ism of Hampson and coworkers, and instead attribute
the oscillations to the formation of a nonstoichio-
metric passive film, but provide little further evidence
to support their mechanism.
Finally, current oscillations were observed by
Drogowska et al. (1991) on preoxidized Sn electrodes
immersed in bicarbonate of phosphate solutions in
the presence of chloride ions. The oscillations, which
were very regular, were only observed as long as
a passive film covered the Sn surface and were at-
tributed to the alternating corrosion (by the chloride
ions) and repair of this film.
Anodic zinc oscillations, The Zn in alkaline electro-
lytes system is another electrochemical system for
which both cathodic and anodic oscillations have
been observed. Reports on anodic oscillations date
back to the late 1950s (Franck, 1958). The dynamics of
this system have been studied in some detail by Hull et
al. (1970) and Hull and Toni (1971). A number of
visual changes were observed on the Zn anode during
the anodization as the electrolyte potential was swept
between two predetermined limits (see Fig. 48). At
potentials less anodic than point B, the electrode
surface was bright and each patterns were visible. At
B a white film formed. In the absence of stirring in the
region CD, this film flaked from the surface. At D, the
current started to increase and the surface beneath
the white film started growing dark. After passing
through the oscillatory region, the passivated surface
had turned black. In the region FGH, the black film
underwent a rapid lightening to leave the surface
covered by a white crystalline passivating layer. This
color change appeared to be reversible. In the reverse
sweep, in the region JK, the light-colored film began
to darken again just prior to complete reactivation. At
K, where the surface was a mixture of light and dark
areas, the current was observed to oscillate again
between the active and passive states. A stable current
was eventually attained at L, and the electrode was
then covered by a black film, which, however, per-
mitted active dissolution of the electrode to proceed.
The film in the region LM lightened again gradually
to leave the electrode surface with a similar appear-
ance as in the forward sweep. Hull et al. attributed the
oscillations to the formation of a ZnO film, the forma-
tion and dissolution of which depends strongly on the
electrolyte pH at the electrode/electrolyte interface.
A similar mechanism for oscillations was proposed by
Kano et al. (1970).
Relaxation-type current oscillations during the
anodization of Zn in alkaline solutions have also been
reported by Podesta et al. (Podesta et al., 1979a, b;
Piatti et al., 1980). The oscillations disappear when the
electrode is rotated even at moderate rotational
speeds, while during the oscillations a net localized
corrosion of Zn is observed. The oscillations
w&q attributed to the formation and dissolution
of surface films, which passivate the Zn electrode
surface.
 Electrochemical reaction dynamics 1533

- Black lllm

IlZk Light gray

I

Film darkens
7” T
Milky film
I
Thick silver
colored film
Scan rate = 1.1 mV/s
5 N KOH (unstimd)

- ._800
-0.92 -1.04 -1.16 -1.28
Electrode potential vs Hg-HgO (V)
Fig. 48. Current-voltage curve of a zinc wire electrode in unstirred 5 N KOH recorded at a scan rate of
1.1 mV/s. Reproduced by permission of the Electrochemical Society from Hull et al., J. elecrrochem. Sm.
(1970).

The surface of Zn electrodes immersed in NaOH 700

containing electrolytes in the active, oscillatory and
600
passive regions were examined by SEM in a later
study by Podesta et al. (1982b). Again, the oscillations 7 500
were related to the formation and dissolution of a pas- .!. 400
sivating film. Current oscillations under potentio- a
static/potentiodynamic conditions for the Zn/NaOH rS 300
system have also been reported by McKubre and w 200
Macdonald (1981). The oscillations have been at-
tributed to the formation and dissolution of a com- 100
pact passivating surface film. Initially, as voltage in- 0
creases (see Fig. 49) metal dissolution proceeds as -1400 -1200 -1000 -800 -600

Zn+40H-f Zn(OH):- + 2e-. (54) Potential (mV vs Hg/HgO)

Fig. 49. Current oscillations of zinc during anodic poten-
At potentials corresponding to the onset of the linear tiodynamic sweep at 5 mV/s: 28 w/o NaOH, 8O”C, 600 rpm
current/voltage region the Zn/ZnO reversible poten- Reproduced by permission of the Electrochemical Society
tial is exceeded and the predominant reaction be- from McKubre and Macdonald, J. electrochem. Sot. (1981).

comes
Other elements
Zn+ 20H- =ZnO + Hz0 + 2e- (55) Two studies have reported oscillations during Ti
coupled with a ZnO dissolution reaction anodization. Vicentini et al. (1975) have reported peri-
odic oscillations during the electrochemical polariza-
ZnO + Hz0 + 20H- +Zn(OH):-. (56) tion of Ti in H2S04 solutions of varying molarity.
When the electrolyte in the immediate vicinity of the Current oscillations during the anodic polarization of
electrode is saturated with Zn(OH):-, Zn(OH), pre- Ti in bromide solutions have been reported by Okada
cipitates, forming a porous film (type I). The forma- (1981).
tion of this film continues through the two reactions Potential oscillations during the anodization of
above until the pH within the porous film is reduced both polycrystalline and single crystal Bi in NaCl
to the point that ZnO becomes insoluble, forming solutions with or without HCI have been discussed in
a compact passivating-type film (type II). This results an early study by Petrov (1971). The electrochemical
in reduced dissolution currents, the concentration of anodization of Bi in a variety of electrolytes like
Zn(OH)i- decreases, pH increases and both films phosphate, borate, benzoate, and tartarate was
redissolve, reactivation results, and the cycle repeats studied by Ammar and Khalil (1971). Oscillations
itself with the precipitation of a new Zn(OH), were observed with all electrolytes and attributed to
More recently, current oscillations during the the dielectric breakdown of the anodic passivating
anodic dissolution of Zn in concentrated KOH solu- films.
tions containing polyethylene glycol have been re- Potential oscillations under galvanostatic condi-
ported by Frackowiak and Kiciak (1988). tions for Cd anodization in KOH solutions have been
1534 J. L. HUDSON and
reported by Galushko et al. (1972a, b). The oscil-
lations have been attributed to the formation and
destruction of a passive surface film, which was identi-
fied to be either Cd(OH)r or Cd0 finely dispersed in
Cd(OH), .
Potential oscillations during the corrosion of duc-
tile chromium alloyed with small amounts
(0.1-0.4 wt%) of a number of Pt group metals
(Ru, OS, Ir, Pt, Pd) have been reported by Tomashov
and coworkers (1980). The oscillations have been at-
tributed to a cyclic passivation/activation process of
the Cr surface accompanied by cyclic changes in the
pH at the electrode/electrolyte interface.
A number of studies have reported interesting dy-
namics during Nb electropolishing. Kadaner et al.
(198 l), for example, have observed low-frequency
(0.01-0.3 Hz) potential oscillations during the electro-
chemical dissolution of Nb in an HBFI electrolyte by
imposing a 50 Hz alternating current (AC) equal to or
larger than the passivation current of the metal under
these conditions. Potential oscillations during the
electropolishing of Nb in HF/HrSO, solutions have
been reported by Anisimov and Kovarskii (1983),
Sandulov et al. (1988), and Eidel’berg et al.
(1990, 1991). A technique for electropolishing Nb has
been reported by Diepers and coworkes (Diepers and
Schmidt, 1971; Diepers et al., 1971). It involves the
superimposition of a potential oscillation on the top
of the electropolishing voltage corresponding to cur-
rent-limiting conditions.
Potential oscillations under galvanostatic (or gal-
vanodynamic) conditions during W electrodissolution
in NaOH solutions have been reported by Dikusar
and coworkers (Dikusar et al., 1985; Englegardt and
Dikusar, 1986 and references therein). The oscillations
have been attributed to thermokinetic instabilities
caused by the electrochemical reaction heat released
on the electrode surface and the resulting large tem-
perature gradients between the electrode surface and
the electrolyte bulk. Dikusar and coworkers have also
presented an extensive theoretical analysis of the phe-
nomena, which are similar to the thermokinetic in-
stabilities observed in chemical reactors.
Recently, a study was published (Schlegel and
Paretti, 1992) which reports open-circuit potential
oscillations on a hanging mercury drop electrode
(HMDE), which appear to be driven by anodic- rather
than cathodic-type processes (see the section to
follow). The oscillations in open-circuit potential are
observed in aqueous solutions containing complex
ions of cobalt and arise because of cyclic pH changes
in the electrode/electrolyte interfacial region, which
are due to reactions that take place on the electrode
surface and the interfacial region. An earlier study by
Opekar and Holub (1980) has reported potential os-
cillations during the electrodissolution of Hg from the
surface of glassy carbon electrodes under galvano-
static conditions into solutions containing SCN-
ions.
Potential oscillations during the galvanostatic oxi-
dation of highly oriented pyrographite (HOPG) inter-
T. T. TSOTSIS
calated with HzS04 have been reported by Harrach et
al. (1992). The electrochemical cell allows for in situ
measurement of the electrode’s in-plane conductivity
and X-ray diffractometry. The potential oscillations
were shown to be accompanied by in-phase changes
in the conductivity and the XRD spectrum of the
electrode. The authors attribute the oscillations to
a complex mechanism involving an overcharging
stage (i.e. increase in the charge of the graphene layers
with simultaneous expulsion of H*), during which the
potential increases linearly with charge; this stage, at
high potentials, is followed by the overoxidation of
graphite, an autocatalytic, irreversible reaction de-
scribed schematically as
OH OH
I I
>C=C< +2HsO-+ >C C< +2H++2e-.
This process results in a rapid decrease of the HrO
molecules at the reaction front, which then slows
down the reaction; near the front, graphene layers
collapse, preventing the further arrival of new Hz0
molecules and preventing the overoxidation reaction
from occurring. According to Harrach et al. (1992),
this mechanism explains the reproducible potential
oscillations and is consistent with their conductivity
and XRD data.
CATHODIC PROCESSES
Although anodic oscillations are more common,
quite a few cases exist of oscillating cathodic reac-
tions. One such example occurs during tin plating.
Clarke and Bernie (1967) reported some interesting
dynamic behavior during the bright acid tin plating
process studied in a Haring-Blum cell used to
measure the plating throwing efficiency. The cell, 6 in.
long, contained a perforated sheet of pure tin as the
anode placed in between two parallel thick brass bar
cathodes. The plating bath contained various
amounts of brightener prepared by an elaborate tech-
nique described in the original publication. In solu-
tions containing various amounts of brightener each
cathode seemed to undergo regular relaxation-type
oscillations. The two cathodes, which were placed in
different distances from the anode, seemed to oscillate
simultaneously, but their oscillations looked different.
The near cathode spent most of the period in the
lower potentials, i.e. passive state with a short “flash”
into the active higher-potential branch (a puff of hy-
drogen was also observed), from which it soon re-
turned. On the other hand, the far cathode spent most
of the period in the higher potentials with brief excur-
sions into the lower passive potentials, coincident
with the times the other cathode moved into the
higher potentials. The result of this behavior was that
most tin deposited onto the far cathode, resulting in
throwing efficiencies of over 100%. Clarke and Bernie
attribute the oscillations to a cathodic passivity mech-
anism resulting from the adsorption of brightener
molecules, similar to the mechanism proposed for the
 Electrochemical reaction dynamics 1535

(1991). The surface morphology of the Sn deposits was

monitored in situ by a video camera. Figure 50 shows
-1400
the potential oscillations observed under a cathodic
5
current of 800 A/mz. The amplitude of oscillations
u -1600
increases during the first eight cycles. It remains con-
B -1800
stant up to 20 s, subsequently decreasing up to 70 s, at
E which point the oscillations cease. During the 65 s of
m
-2000 oscillations Piron et a/. (1991) recorded changes of the
electrode surface with the video camera. They report
I I I I I I
-2200 that “the surface appearance blurred after 3 s”, point
0 10 20 30 40 50 60 70
c in Fig. 50. “Later, after 10 and 60 s, the surface
Time (5) roughened, resulting in an increase in the surface
Fig. 50. Potential oscillation of the tin electrode in the solu- area.” Figure 51 shows SEM micrographs of samples
tion of 0.23 M SnO + 6.25 M KOH, at a cathodic density of taken at various times during the oscillations. At the
800 A/m’. Reproduced by permission of the Electrodhemkl first peak (point b in Fig. 50) the surface is covered by
Society from Piron et al., J. elmtrochem. Sot. (1991). small crystals. At points c and d (as the oscillations
proceed) dendritic growth prevails. After 70 s, when
oscillations cease, whisker-like structures appear,
which provide a large surface area.
oscillations for the anodic electrodissolution pro- The oscillations ceased upon mechanical stirring
cesses. and were observed for current densities higher than
Cathodic oscillations in Sn electrodes immersed in the limiting current density. The oscillations were
electrolytes containing Sn(II) ions in the absence of attributed to a depletion of Sn(II) ions near the elec-
any organic compounds were reported by Piron et al. trode, which decreases the potential. The potential

Fig. 51. Scanning electron micrographs of the tin electrode surfaces at different moments during the
potential oscillation at 800A/mZ. (a, top left) At the time (b) in Fig. I of the original paper (1500 times); (b,
top right), at the time (c) in Fig. 1 of the original paper (200 times); (c, bottom left), at the time (d) in Fig. 1 of
the original paper (200 times); (d, bottom right). at the time (e) in Fig. 1 of the original paper (1500 times).
Reproduced by permission of the Electrochemical Society from Piron et af., J. efectrochem. Sot. (1991).
1536 J. L. HUDSON and T. T. TSOTSIS
subsequently increases due to the natural convection
induced by the density difference between the elec-
trode interface and the solution bulk. Hydrogen
evolution was not implicated because it was only
observed to occur in the first cycle of the oscillations
(see the discussion of the mechanism for oscillations
for the Zn in alkaline solution system, which follows).
Oscillations during Sn electrocrystallization from
a stannous sulfate solution containing various organic
substances have also been reported by Nezu et al.
(1986a, b). Oscillations result from periodic changes in
the surface concentration of these compounds.
Cathodic oscillations during Zn deposition have
been reported by a number of investigators. One of
the earliest complete investigations of the dynamics of
the cathodic processes leading to the oscillations ob-
served in this system was by St. Pierre and Piron
(19871, who studied the dynamic behavior of Zn an-
odes and cathodes immersed in a ZnO + KOH solu-
tion. Regular relaxation-type oscillations were ob-
served under galvanostatic conditions for current
densities below a threshold value. Above this value
the current density increased with increasing current
density. Agitation seemed to eliminate the ossil-
lations. St. Pierre and Piron suggested the following
mechanism to explain the voltage oscillations.
When a cathodic constant current is imposed on
the Zn electrode immersed in an alkaline solution
containing Zn ions, the metal at first is reduced with
a 100% current efficiency according to the following
reaction:
Zn(OH):-(aq) + 2e- + Zn(s) + 40H-(aq). (57)
For high current densities the consumption of Zn ions
in the electrode’s vicinity is larger than the flux of
these ions from the solution bulk towards the elec-
trode’s interface. This results in a decrease in the Zn
ion concentration near the electrode and in an in-
creasing cathodic concentration overvoltage. The
!&a
-2.0 - Zn dspoaitionand
hydmgenevolntion
3OlIc,-0.a4.4/cmZ
0 10 20
Fig. 52. Oscillation phenomenon potential wave and charactenstlc pomts used to define variables. Repro-
duced by permission of the Electrochemical Society from St. Pierre and Piron, J. electrocbem. Sot. (1990).
electrode becomes progressively more active and this
results in an increasing hydrogen evolution according
to the reaction
2HrO •C2e- + Hz(g) + 20H-(aq). (58)
The hydrogen thus evolved creates bubbling and in-
creasing convection currents near the electrode sur-
face, which helps to replenish the Zn in the vicinity of
the electrode. The cathodic overvoltage then de-
creases, the hydrogen evolution slows down and the
cycle repeats. A more quantitative investigation of the
mechanism for oscillations was reported in a more
recent paper by St. Pierre and Piron (1990). They
divide the oscillatory cycle into three parts (see Fig.
52): a recovery region, which is defined as the region
between t,,, and tmin(the width of this region is given
by r, = r,,, - t,in); a depletion region between
t maxand ti, which is the inflection point on the de-
creasing part of the cycle (the width defined as
td = ti - t,,,); and a supersaturation region between
ti and the next minimum t&. Generally, t, < tdr but
this is not true for lower Zn concentrations. They
concluded, as before, that the driving force for the
oscillations is a high enough current density, which
during the transition and depletion periods produces
a depletion of Zn ions at the interface. During this
time Zn is deposited at a rate higher than that sup-
plied by diffusion and natural convection. St. Pierre
and Piron observed that td decreases, as current den-
sity increases or the Zn concentration decreases, con-
sistent with this mechanism. At the end of the de-
pletion period the potential is low enough to make the
hydrogen reaction possible. Bubbles begin to form on
the electrode surface after the hydrogen concentration
has reached a level in the solution several times its
saturation value. The growth, detachment and move-
ment of bubbles, as already mentioned, cause a mass
transfer enhancement and replenishment of Zn in the
@min~%dJ
30 40 50 60
 Electrochemical reaction dynamics
diffusion layer. Bubbles appear at the end of the
supersaturation region at the potential minimum.
A general characteristic of the Zn system, which
might aid in the search for other systems that might
exhibit similar phenomena, is the occurrence of the
hydrogen evolution reaction at potentials signi-
ficantly more active than the reduction of the metal.
A limiting-current density for metal deposition is ob-
served before the hydrogen evolution reaction be-
comes significant. When current densities higher than
the limiting current are imposed, Zn depletion occurs,
which decreases the potential, allowing the hydrogen
reaction to occur, bubbles to form, etc. The formation
of powdery deposits during the oscillations increases
the surface area with time and the real current density
falls below the limiting-current density. As a result,
oscillations finally cease to exist after a few cycles.
Suter and Wong (1989) made extensive investiga-
tions of the oscillations observed during Zn depos-
ition from a ZnS04 electrolyte. Their primary interest
was to understand how the different noise power
spectra are related to the different morphologies of
deposits grown. They found that, whenever dendrites
are formed, the cell current exhibits oscillations under
both potentiostatic and galvanostatic conditions. The
more orderly the resulting dendrites, the larger the
amplitude of the oscillations. The frequency of oscil-
lations varied from below 1 Hz up to 50 Hz and it was
found to be proportional to the product of concentra-
tion and applied voltage. Suter and Wong attribute
the oscillations to large current densities on the cath-
ode (resulting from the fact that the anode to cathode
surface area ratio is very large in their cell), which
result in a dielectric breakdown in the double layer
and charge depletion. The repeated charging and dis-
charging of the interfacial capacitor thus leads to
current oscillations. Since the resistance between the
various growing dendrites is very small, their oscil-
lations are phase locked to give an observable effect.
Wang and Ming (1992), using in siru transmission
interference contrast microscopy, have studied oscilla-
tions in the local concentration field around a grow-
ing single dendrite tip for a ZnS04 electrolyfe solu-
tion. They attributed the local concentration field
oscillations (and the simultaneous oscillations in the
current density) to a competition between the faceted
dendritic growth and the diffusion of the electrolyte
toward the growing dendrite.
Cathodic potential oscillations have recently been
reported by Weber (1990) for zinc cathodes immersed
in ZnCl,/KCl solutions containing H,BO,. Two dis-
tinctly different types of oscillations were reported.
Two mechanisms responsible for these oscillations
were proposed.
Electrochemical metal deposition also exhibits dif-
fusion-limited aggregation (DLA) phenomena. In fact,
by varying the concentration of the metal ions, the
conductivity of the electrolyte and the applied con-
stant current and voltage, one can observe a number
of different deposit morphologies like dense radial
(Grier et al., 1987), dendritic (Sawada et al., 1986;
CES 49: 10-D
1537
Sawada, 1986) and DLA-like fractal patterns (Grier et
al., 1986; Brady and Ball, 1984; Matsushita et al., 1984,
1985; Argoul et al., 1987, 1988, 1990; Argoul and
Ameodo, 1990; Sagues et al., 1990; Costa et al.,
199lb). Argoul and Arneodo (1990) have studied Zn
deposition from an aqueous ZnSO_+ electrolyte solu-
tion using two thin parallel Zn electrodes contained
between two rectangular glass plates. The elec- .
trode position reaction was studied under galvano-
static conditions and the structure of formed deposits
was studied using an in situ 35 mm camera. Regular
and relaxation-type single-peak oscillations and also
deterministic chaos were observed and were related to
the growth phenomena of the Zn deposits on the
cathode. Argoul et al. (1993) recently reported a more
extensive investigation of the same system. The per-
iod-doubling transition leading from the relaxation-
type oscillations to the deterministic chaos was shown
to be a precursor of alternating sequences of peri-
odic/chaotic states and to be associated with the pres-
ence of Shil’nikov homoclinic chaos.
The effect of various metal impurities (Ni, Co, Cu,
Cd, Sb, Ge, As, Bi) on Zn electrodeposition has been
studied by Maja and coworkers (1982). All metal
impurities were reported to lead to oscillatory in-
stabilities and significant changes in the morphology
of the resulting deposits. Oscillations reported by
Nezu et al. (1985) during the electrocrystallization of
Zn from alkaline solutions were attributed to the
periodic changes of the surface concentration of zin-
cate ions.
One of the most carefully studied systems exhi-
biting cathodic oscillations is the In(III) reduction in
thiocyanate ion containing electrolytes over dropping
mercury (DME) or hanging drop mercury electrodes
(HDME) (Jakuszewski and Turowska, 1969; De Levie
and Husovsky, 1969; De Levie and Pospisil, 1969;
Pospisil and De Levie, 1970; De Levie, 1970; Moreira
and De Levie, 1971; Saito, 1992). De Levie and co-
workers have developed a model to explain the oscil-
lations based on an electrical circuit equivalent rep-
resentation of the various electrochemical processes
occurring on the mercury electrode. The two re-
quirements for oscillations as listed by De Levie are
a negative charge transfer resistance, which results in
a negative diffusion impedance and a sufficiently large
external circuit resistance. For further discussions on
the effect of negative charge transfer resistance in the
generation of electrochemical oscillations, see
Tamamushi and Matsuda (1966), Pamfilov er al.
(1970), Jakuszewski and Turowska (1973), Salie (1980)
and Koper and Sluyters (1993b).
A model of electrochemical oscillations of relevance
to the In3+/SCN- system has been presented by
Keizer and Scherson (1980). The model deals with an
electrocatalytic reaction, which involves a reducible
cation X’ + m . solution reacting with two anions Y -,
which are adsorbed on the cathode. The resulting
product XY:‘-“+ forms a surface film. This surface
film is subsequently regenerated to produce 2Y ~. The
switching mechanism is the cathodic desorption of
1538 J. L. HUDSON and T. T. TSOTSIS

Y -, which in the model of Keizer and Scherson is lower than the charge transfer and double-layer
governed by an equation suggested by the pH de- relaxation of the voltage.
pendence of the Flade potential. An important feature Detailed studies of the In(III)/SCN- oscillator at
of the model is the existence of two distinct forms of the HMDE were recently undertaken by Koper and
the electrode surface, a covered surface, which is ca- Sluyters (1991a, b) and Koper et al. (1992). The experi-
pable of reduction, and an uncovered surface, which is mental bifurcation diagram for this reaction, in the
unreactive. Keizer and Scherson have developed a set R, (external resistance)-V (potential) plane, as re-
of detailed transport equations close to the electrode ported by Koper and Sluyters, shows either a single
surface, which they apply to the electrochemical steady state or an oscillatory state. Regular and
mechanism mentioned above, modeled after a mech- relaxation-type single-peak oscillations and mixed-
anism suggested by De Levie: mode and even chaotic-type oscillations were ob-
served. The presence of nearly homoclinic-type oscil-
X2+ + 2Y-(ads)~XY~P2’+(film) (59) lations was also reported.
ze- + XY:“-2’+(film)~Xo + 2Y-(ads). (60) Koper and Sluyters have also developed a math-
ematical model to describe the oscillations for the
The film formation process is assumed rapid and at In(III)/SCN- system. Their model is based on the
equilibrium. For the fractional surface coverage of equivalent cell circuit of Fig. 53. For the cell potential,
Y -, 0 they write an equation they write the following equation:
dE V-E jF
O(V)=
1, vav, (63)
x=--- R.ACd Cci
i 0, v* < v
where j, is the Faradaic current density and A the
where V, is the desorption potential, which is not electrode surface. (The rest of the symbols are defined
fixed. It is instead assumed to be a function of p, the in Fig. 53.) For the average concentration of the In’+
concentration of X2+ close to the electrode surface. species, in the boundary layer near the electrode, they
Keizer and Scherson write an equation, similar to the write an equation
one giving the dependence of the Flade potential on
dCo - 2K,Co
pH, namely -ZZ + g (Cbulk - CO) WI
dt 6
V, = a + b ln (P/PB) (62)
which is based on the assumption of a linear diffusion
where pB is the value of p in the bulk. The above layer of constant thickness S. They define the follow-
electrocatalytic mechanism leads to a negative differ- ing dimensionless variables:
ential resistance in the current-voltage curve, since at
more cathodic voltages Y- desorbs, which then pre- u = (F/RT) V, e = (F/RT)E, x = Co/C,,,,
vents the film formation and metal reduction from and define k, = (1/2)kk’, where k’ accounts for the
occurring. Keizer and Scherson analyzed their model reaction rate units and k (dimensionless) depends on
by graphical and numerical techniques. Using, as they the electrochemical reaction mechanism of the
claim, realistic values of the transport/equilibrium In(III)/SCN- mechanism. For this mechanism,
parameters, they find limit cycle oscillations in the
electrode voltage and in the surface concentration of
X2+ ions. The existence and amplitude and period of
these oscillations were found to depend on the resist-
ance in the external electrical circuit. In fact, as it was
also observed experimentally by De Levie and co- IV7 F
L
workers, the model showed that there is a region of
resistances, within which oscillations are observed.
-i f
Within this region the model shows, in agreement
with the experiments, that the period and amplitude
of oscillations decreases as the external resistance is A
increased. The predicted current-voltage curve shows, -i
-ip
as already mentioned, a region of negative differential
resistances. The oscillations are, however, observed
prior to this region. The oscillations are characterized zp
by a rapid decrease in voltage, when the reduction of
the XY’Z-2)+ film occurs, followed by a sequence of
rapidly, and then slowly, increasing voltages. Im- Fig. 53. General equivalent cell circuit of an electrochemical
portant for the generation of oscillations is the switch- cell with double-layer capacitance Cd and Faradaic impe-
ing on and off by the voltage and the concentration- dance ZF, in series with an external resistance R. (ohmic cell
resistance is either neglected or comprised in R,). E is the cell
dependent Y- adsorption of the film reduction pro-
or electrode potential; Y is the (controllable) circuit poten-
cess. This leads to oscillations because the electrodif- tial. Reproduced by permission of Elsevier Sequoia S.A. from
fusional transport of X2+ in solution is significantly Koper and Sluyters, J. electroanaL Chem. 303, 74 (1991b).
 Electrochemical reaction dynamics 1539

Koper and Sluyters follow the mechanism of Pospisil Koper and Sluyters also presented a modified model
and De Levie: to account for the In(III)/SCN- oscillations observed
.at a DME. They also presented a model to account for
In3+ + ZSCN- (ads) 5 In(SCN); (ads) (65) oscillations observed during the cathodic reduction of
various metals in the presence of various organic
In(SCN): (ads) + 3e- z In’ + 2SCN-(ads) inhibitors @ike, for example, Cu’+ reduction in the
presence of tribenzylamine; see Jehring and
(66) Kuerschner (1977)]. In this model, they assume that
the Faradaic current is proportional to the unoc-
but also allow for the uncatalyzed reaction of In(W)
cupied (by inhibitors) area of the mercury electrode
with a rate with an exponential dependence on e.
and the rate of reduction to conform to an exponen-
Dimensionalizing time as t = (k’tji3) the dimensionless
tial dependence on the electrolyte potential. The equa-
forms of eqs (63) and (64) are
tions describing the model are given as
de v---e
de
Z=r-cX - 7 - cx(1 - 0) exp [na(e -e’)] (70)
Xt-
dx
-= -kkx+d(l -x) (68) dx
dt -=-kkx(l-@exp[na(e-e’)]+d(l -x)
dt
with
(71)
ACdk’R, nFZ &,kdk
, d=g where 0 = [inhaas]/[inhaa~,ma,] and B depends on
Y=fi* == 2R TC.,
e through a relationship similar to eq. (65):
k = k, O2 + k, exp [nn(e - e’)]

where 0 is the average dimensionless concentration 6,mar9 e 2 ed

8= (72)
(SCN - )ASCN- ),a, of SCN- in the boundary layer { drnsx exp [- h(e - ed)‘], e c ed_
and n the number of electrons transferred. Koper and
Sluyters assume 13to have the following dependence By choosing emaX# 1 one takes into account the fact
on e (see also the discussion on the model of Keizer that even at maximum inhibitor coverage there will
and Scherson): still be some Faradaic current as it has been experi-
mentally observed.
4 eG ed
O= (69) More recently, Koper (1992) has reexamined in
exp C- b(e - edY], e > ed
great detail the system of equations (67) and (68). as
where ed is considered a constant. Computed oscilla- a special case, in the more general context of oscillat-
tory profiles based on this model are shown in Fig. 54. ing electrochemical systems, which exhibit a negative

Fig. 54. Computed oscillation profiles for i for model eqs (20) and (21) of original paper with parameter
values c1 = 12, cZ = 0.48, k, = 0.1, kz = 0.004, d = 0.02, e” = 34, e_, = 35, b = 0.5 and (from top to
bottom): u = 37/r = 0.5, v = 38/r = 1.1, u = 38/r = 1.3. Reproduced by permission of Elsevier Sequoia S.A.
from Koper and Sluyters, J. electroanal. Gem. 303, 84 (1991 b).
1540 J. L. HUDSON
Faradaic resistance. Under potentiostatic conditions
he showed that in the (r, u) parameter space this sys-
tem of equations exhibits a cross-shaped phase dia-
gram, which has the universal structure of the dia-
gram that was previously described by Guckenheimer
(1986). Under galvanostatic conditions the system ex-
hibits multiple steady states, but no oscillations.
A three-variable model to describe the mixed-mode
oscillations of the In(III)/SCN- system on a HMDE
was presented in a recent paper by Koper and
Gaspard (1991). They start by writing an ordinary
differential equation for the electrode potential E
[similar to eq. (63) of Koper and Sluyters (1991b)l:
dE V-E
C.iz= - R - AnFK,(E)C,,.
(73)
is
where C,=, is the concentration of In(II1) at the
HMDE surface and K,(E) is the potential-dependent
rate. They also write the diffusion equation for the
concentration of In(II1) in the electrolyte around the
HMDE:
g=D[$+S$] (74a)
with boundary conditions
oat
= k,-hW,=,@), Cm, = C,,u~k.t-b)
ar r=(I
Koper and Gaspard do not attempt to solve the
above system of equations. Instead, they simplify it to
a system of three ordinary differential equations,
which they believe capture the basic dynamic features
of the more complex system. They do so by assuming
a boundary layer around the HMDE of thickness a,
which they divide into two fictive spherical diffusive
layers of thickness a/2. In the layer closer to the
HMDE, they assume the concentration to be uniform
equal to Cbulru and in the next layer to be CbYILw.
Based on these assumptions, they write three differen-
tial equations in terms of e [the dimensionless elec-
trode potential; see also the model of Koper and
Sluyters (1991b)], u, and w:
de v-e
_-- mk(e)u (75)
dt- I for the possibility of a curvature in the In(III) concen-
$ =- +
k(e)u d(w -u)
dw
- ‘9d(16 -225~ +9u). (77) boundary layer.
dt - 333
The numerical coefficients in eq. (77) stem from the
spherical geometry and from the assumption about
the thickness of the various layers. As Koper and
Sluyters also did, they assume that
k(e) = kl O* + k* exp [na(e -e’)]. (78) a partially chaotic region, which is bounded by a cas-
The first term again accounts for the catalyzed In(II1)
reduction and the second for the uncatalyzed rate
component. 0 is assumed to follow the sigmoidal
dependence [eq. (69)] on e, which results in a negative
and T. T. TSOTSIS
dk(e)/de for a region of e. The typical oscillatory time
series, predicted by this model, are shown in Fig. 55.
FOT low r values, a small stable node is observed,
which is changed into a stable focus at r = 0.015763
and then undergoes a Hopf bifurcation at
r = 0.017155 [a typical small-amplitude oscillation is
shown in Fig. 55(a)]. Shortly thereafter the small-
amplitude oscillation is destroyed (as one increases r)
and a mixed-mode oscillation (MMO) is observed; see
Fig. 55(b) and (c). With increasing r they observed the
sequence
with n going from 1 to 8 or 10. In the sequence on the
right-hand side two neighboring states show inter-
jacent periodic states, which are concatenations of the
two principal states. The above sequence is similar to
the Farey sequences observed by Schell and co-
workers in their studies of electrochemical reaction
dynamics (see previous discussions) typically shown
to occur near homoclinic tangencies.
At higher r the model again. predicts MMOs, but
between two neighboring states one can now find
both chaotic and periodic states (see Fig. 56). Periodic
states turn into chaotic states through subharmonic
bifurcations, while the chaotic states disappear
through either tangent bifurcations or period
halvings. The behavior of the model seems typical of
the dynamics resulting from iterative maps, which
possess two extrema; see the relevant discussion in the
work of Ringland et al. (1990) and Ringland and
Schell(l991). The highest observed MM0 is 1’. For
r beyond the region, where this MM0 is observed
(r = 0.026843), this state disappears, giving rise to
a subharmonic (period four) oscillation, which is sub-
sequently period halved and disappears through
a Hopf bifurcation at r = 0.027. After the last Hopf
bifurcation the system remains in a stationary state of
low potential and high current, reaching its diffusion-
limited regime.
The model of Koper and Gaspard, although over-
simplified, represents a significant improvement over
the model of Koper and Sluyters because it accounts
tration profile in the boundary layer. Koper and
Gaspard report that their model’s results are generic
in the sense that they observed similar behavior with
a many-box description of mass transport through the
In a more recent paper, Koper and Gaspard (1992)
have completely analyzed the dynamic behavior of the
system of equations (75)-(77) in the (u, r) parameter
space. Again, two types of bifurcation sequences were
observed: (i) periodic/chaotic sequences of MMOs, in
which neighboring periodic states are separated by
cade of subharmonic bifurcations on one side and
a tangent bifurcation on the other; and (ii) Farey
sequences of MMOs, in which two neighboring prin-
cipal MMOs are connected by MMOs, which are
 Electrochemical reaction dynamics 1541

r = 0.01717 r = 0.0171732
150

i i

r = 0.01724
150 150

i i

0 40 0 40
t t
Fig. 55. Typical oscillatory time series for the current i obtained for eqs (4)-(6) of the original paper.
Depicted are, for the indicated values of r, a small-amplitude oscillation, a MM0 state 119, and a typical
“Farey” state l’l*. Note the small I domain in which these transitions take place. All other parameter
values were fixed at u = 37, d = 1, m = 120, k, = 2.5, k, = 0.01, e,, = 35, b = 0.5, non = 0.5, and e0 = 30.
Reprinted with permission from Koper and Gaspard (1991). Copyright 1991 American Chemical Society.

r = 0.0265 r = 0.0267

‘5oI
lSOl

i i

r = 0.02683 r = 0.026637

lrolr t501

i i

Fig. 56. Typical oscillatory profiles of the flow defined by eqs (4)-(6) of the original paper for higher values
of the resistance r. Depicted arc, for the indicated values of r, the MM0 states l’, l*, and 1’ and a chaotic
state situated between the periodic states 1’and 1’. All other parameter values as in Fig. 55. Reprinted with
permission from Koper and Gaspard (1991). Copyright 1991 American Chemical Society.
1542 J. L. HUDSON and
concatenations of the two principal states, obeying an
incomplete Farey arithmetic sequence. Koper and
Gaspard have also extended their analysis to the
rotating disk electrode (RDE). For the In(III)/SCN-
system, the RDE gave behavior very similar to the
HMDE system. The dynamic behavior for the
In(III)/SCN- system, as reported by Koper and Gas-
pard (1992) is very similar to that reported by Ring-
land et al. (1990) and Ringland and Schell (1991).
Additional results on this system have been published
by Koper et al. (1992). The mixed-mode and chaotic
oscillations were studied in experimental detail in the
parameter plane. Using their earlier model, the
authors discuss the relationship of the experimentally
observed sequences with those predicted by the
Shil’nikov theory for homoclinic orbits.
Relaxation-type oscillations which arise in the po-
larographic reduction of anions like Fe(CN):-,
Pt(Cl,)*-, Pt(Cl,)*-, S,Og-, and CrO:- have been
investigated by Gokhstein, Frumkin and coworkers
(Gokhstein and Frumkin, 1960, 1962; Frumkin er al.,
1961; Gokhstein, 1961, 1963). The presence of an
external resistance, in series with the electrochemical
cell, was necessary for the generation of these
oscillations and they appear in a region where the
current-voltage curves exhibit a regime of negative
resistances. Several other studies have also been
devoted to the dynamic behavior of the reduction
reaction of such ions. Wolf et al. (1992), for example,
have recently developed a dynamic model for the
reduction of SZOi-_ The results of the model are
compared to experiments carried out under poten-
tiostatic conditions. The most important feature of the
mechanism underlying the model is a region of
negative differential resistance in the cathodic cur-
rent/overvoltage curve. According to Wolf et al., it is
caused by the repulsive electrostatic interaction be-
tween the anions and the negative charged electrode,
which opposes the effect of increasing overvoltage.
Chaotic oscillations during Fe(CN)a- reduction on
a glassy carbon electrode were observed by Varma
and Upadhyay (1989). The system was forced to
undergo chaotic oscillations by applying a low-ampli-
tude (40 mV peak to peak) sine potential wave. Regu-
lar oscillations were observed in the absence of forc-
ing.
One of the cathodic systems that has attracted
considerable attention is Cu electrodeposition. Poten-
tial oscillations during Cu electrodeposition from
a (CuS04 + H&O.+) solution in the presence of o-
phenanthrolin were reported in an early study by
Schlitter et al. (1968). The oscillations were attributed
to the presence of two distinct surface species resulting
from o-phenanthrolin, which act as inhibitors, and
whose rate of formation and reduction is potential-
dependent.
Oscillations during the polarographic reduction of
CL?+ (and Bi’+) in the presence of tribenzylamine in
acidic solutions, in the current-voltage region exhi-
biting negative resistance characteristics, and in the
presence of a suitable external resistance were re-
T. T. Tsoms
ported by Jehring and Kuerschner (1977). The oscil-
lations were accompanied by periodic adsorption and
desorption of the inhibitor coupled with periodic con-
centration changes of the reactant in the neighbor-
hood of the electrode.
Current oscillations during the polarographic re-
duction of Cu2+ 9Cd’+, and Tl+ on a dropping mer-
cury electrode (DME) in the presence of various in-
hibitors (alcohols, phosphonium perchlorates and
bromides, phosphine oxides and phospholipids) were
observed by Diirfler and Miiller (1982). Only the
systems that exhibited a negative dZ/de region and
a current maximum in the presence of an external
resistance exhibited oscillations. The oscillations were
explained in terms of an electrode mechanism, involv-
ing electrosorption and inhibition, and its interaction
with the overall external circuit.
Potential oscillations during Cu deposition in an
electroless bath containing CuS04, glycerin and
HCHO were reported by Panumis et al. (1989). The
oscillations were attributed to a competition between
the electrocatalytic reduction either to CuZO or Cu.
Potential oscillations during the galvanostatic elec-
trodeposition of Cu were reported by Maksimovic
and coworkers (1979). The oscillations were shown to
lead to the deposition of a powdery deposit. Potential
oscillations during the deposition of CuCd alloy in
the presence of HCHO were reported by Vaskelis et
al. (1977). The oscillations were explained in terms of
the passivating effect of Cd during the alloy elec-
trodeposition process.
Cathodic potential oscillations under galvanostatic
conditions during the electrodeposition of NiiP
alloys on a variety of cathodes (Fe, Cu and Cd) were
reported by Vakhidov et al. (1972, 1977). The ampli-
tude of the oscillations and the current efficiency of
deposition seemed to depend on the nature of the
cathode. The nature of the Ni-P alloy thus formed
was also studied in detail. The alloy was shown to
have a layered structure with alternating layers of
Ni-P alloy and pure Ni. This layered structure was
correlated to the potential oscillations observed dur-
ing cathodic electrodeposition. The following mech-
anism was postulated. At first, hydrogen is evolved at
the cathode, resulting in an increase in the pH near
the electrode surface, causing an increase in the elec-
trode potential to a point where Ni2+ is reduced
simultaneously with the reduction of P from the
HsP02 electrolyte. As a result, P is then occluded in
the deposit and thus the Ni-P alloy layer is formed.
The reduction of hypophosphite is retarded owing to
the limited solubility of P in Ni and the decrease of the
electric field energy at the cathode due to depolar-
ization. As a result, a pure Ni layer is formed. This
then causes an increase in the potential to conditions
at which H3P02 is reduced to form a Ni-P alloy and
the cycle repeats itself. Current oscillations under po-
tentiostatic conditions and hysteresis phenomena un-
der potentiodynamic conditions during the elec-
trodeposition of Ni from chloride and sulfate solu-
tions were reported by Selskis et al. (1991).
 Electrochemical reaction dynamics
Oscillations during cathodic reactions involving
chromium have been reported by various invest-
igators (see also the studies of Frumkin, Gokhstein
and coworkers mentioned above). Oscillations during
the electrolytic deposition of chromium have been
reported by Kimura and Hayashi (1971). The oscil-
lations were observed in the potential region corres-
ponding to the partial reduction of Cr6+ to Cr3+.
They were attributed to the formation of a cathodic
film of chromate. Current oscillations during the elec-
trolytic reduction of dichromates in acetic solutions
have been reported by Franczak et al. (1980). The
oscillations occur within a range of Cr,O$- concen-
trations and their amplitude decreases with increasing
temperature. Oscillations during the reduction of
CrO:- on a DME have been reported by Fleszar et
al. (197.3).
During chromium electrodeposition on vitreous
carbon electrodes, Jiang and Pletcher (1983) observed
oscillatory behavior during potential sweeps at poten-
tials just prior to the deposition potential. The oscil-
lations were attributed to passivating films formed.
Potential oscillations during CrO, reduction under
galvanostatic conditions in electrolyte solutions con-
taining F- or TiFa- were reported by Karnaukhov et
al. (1990). A model was also presented, which con-
siders consecutive+reduction steps of the Cr6+ in the
electrolyte region adjacent to the electrode. The
model predicts a critical current density, beyond
which oscillations are observed. It is capable, further-
more, of predicting the qualitative effect of the CrOJ
concentration on the oscillations.
Cd electrodeposition has also shown interesting
behavior and it was one of the earliest systems studied
(Hedges, 1927). Potential oscillations during the
electrodeposition of Cd or Pb under galvanostatic
conditions from dilute melts of CdClz (or
PbCl,) + NaCl + KC1 were reported by Polyakov et
al. (1979). Current oscillations during PbC12 reduc-
tion on a liquid Pb drop electrode were reported by
De Almeidi Lima et al. (1992). The current perturba-
tions were attributed to motions of the electrode sur-
face. Potential oscillations during electrochemical re-
duction of Cd0 films in alkaline solutions under gal-
vanostatic conditions were reported by Hamdani et
al. (1984). The oscillations were attributed to a mech-
anism which involved the reduction of CdO, its hy-
dration into Cd(OH)2 and the reduction and dissolu-
tion of Cd(OH)2.
Oscillations during the electrocrystallization of
cadmium from alkaline cyanide solutions
(NaCN + CdO) were reported by Kaneko et al.
(1988). The oscillations were observed under gal-
vanostatic conditions for a current density above the
limiting-current densities (limiting currents were ob-
served only in the absence of stirring, they disap-
peared upon stirring) observed for the current-poten-
tial curve under potentiostatic conditions. Concur-
rently with the oscillations, they observed hydrogen
bubbles evolved periodically from the cathodic sur-
face. The following mechanism was suggested to ex-
1543
plain the oscillations. After the beginning of the gal-
vanostatic electrolysis, the surface concentration of
cadmium ions is decreased. When the concentration
becomes approximately zero the potential shifts rap-
idly from a positive to a negative value, where hydro-
gen evolution on the cadmium metal occurs. The
hydrogen bubbles, thus evolved, help to restore the
surface concentration of cadmium by forced convec-
tion, the potential shifts again to a positive value and
the cycle repeats itself. This mechanism for oscil-
lations is, of course, very similar to the mechanism for
oscillations suggested by St. Pierre and Piron for Zn
electrodeposition. Current oscillations during Cd
electrodeposition from H2S04 solutions in the pres-
ence of N.JV-bis(monooxyethylene) octadecylamine
(POOA) were studied by Shinohara et al. (1991).
Depending on the experimental conditions, they
observed both small-amplitude/high-frequency but
also large-amplitude/small-frequency oscillations.
They attributed these two distinctly different types of
oscillations to two different mechanisms. The large-
amplitude oscillations were attributed to the inhibi-
tion effects of POOA. On the other hand, the small-
amplitude oscillations were attributed to the
synchronization and amplification of local currents
generated at the tips of the protrusions of the irregular
cathodic surface.
Current and voltage oscillations during the
electrQdeposition of Ag-Sb alloys from a ferrocyan-
ide/thiocyanate bath have been reported by Krustev
et al. (1989, 1992). These oscillations were associated
with the deposition of sandwich-type deposits with
alternating phases, which were rich and poor in Sb.
Current oscillations during the polarographic re-
duction of Bi3+ on a dropping mercury electrode in
aqueous HCl + HClO& solutions, in the presence of
sodium dodecyl sulfate as an inhibitor, were reported
by Gonzalez et al. (1982)-see also the study of
Jehring and Kuerschner (1977).
Current oscillations during the electroreduction of
H2SeOJ or Se(IV) in HClO., electrolytes on Hg elec-
trodes have been reported by Mattson et al. (1993).
The oscillations were found to occur at potentials
where HzSe forms and were accompanied by the
precipitation of red Se(O) close to the electrode. They
were attributed to the modulation of the mass transfer
of Se(IV) to the electrode surface by a chemical reac-
tion between H2Se and Se(IV) close to the electrode.
The electrocatalytic reduction of HNOJ over
a platinized Pt electrode in the presence of various
supporting electrolytes was studied by Horanyi and
Rizmayer (1982). In the presence of strongly adsorbed
chloride ions, large-period galvanostatic and poten-
tiostatic oscillations were observed. Horanyi and
Rizmayer also used radioactively labeled chloride
ions in order to investigate in situ the various surface
phenomena occurring during the oscillations. The
oscillatory phenomena observed correlated nicely
with periodical changes in the adsorption of chloride
ions. The oscillations were attributed to the inhibitory
effects of the choride ions. A series of experiments
1544 J. L. HUDSON and T. T. TSOTSIS

under open-circuit conditions were carried out by

Horanyi and Rizmayer (1983) in the presence of
a Hz atmosphere. In the reduction of HNOB, hydro-
gen can act as its redox partner. Oscillations are again
observed in the presence of chloride ions. A simple
model involving three differential equations in the
surface coverage of HNOJ (e,,,,) of chloride ions
(Qc,) and potential E was presented. It was shown to
be capable of predicting the oscillations, but it was not
analyzed numerically. Current oscillations under po-
tentiostatic conditions and potential oscillations un-
der galvanostatic conditions were observed during the
reduction ofnitrate ions on In electrodes by Hampson
and Piercy (1973).
Current oscillations during bromate ions reduction
4@:
System A
in HzS04 solutions over a DME in the presence of
phenol and over a stationary Hg electrode in H2S04
and HNOB solution in the presence of bromine have
been reported by Olexova and Treindl (Treindl and
Olexova, 1983; Olexova and Treindl, 1984, 1988, 1990).
The oscillations were attributed to the formation and
destruction of passive films on the Hg surface. A simple
model to explain the oscillations has also been recently
reported (Olexova et al., 1992) in which the anodic
oxidation of Hg plays an important role.
Potential oscillations were observed in a strongly
alkaline iodide + iodate solution (Radkov and
Ljutov, 1988). The oscillations were shown to be due
to the cathodic processes and were accompanied by
weak hydrogen evolution. Hydrogen evolution was
not, however, necessary for the oscillations. Current
oscillations were observed by Aravamuthan et al. System B
(1984) during cyclic voltammograms over an HMDE
during the electrochemical reduction of 2-nitro- Fig. 57. The apparatus in which oscillations are studied. In
this geometry the mercury meniscus is convex and the center
benzidine in N,N-dimethylformamide solutions. They of the meniscus is initially set even with the top of the tube, In
were attributed either to the tangential motion of the A, the corroding electrode (Al) is in the same vessel as the
mercury surface, which causes uneven polarization, of mercury. In B, the corroding metal is located in a separate
the drop, or the inhibition of the reaction caused by container connected to the solution above the mercury by
a l.OM NaCl salt bridge (SB). The polarity of the oscillo-
coverage of the electrode surface by various products. scope (OSC) is as indicated. For the iron wire-acidic-dichro-
A number of other papers have also reported current mate-mercury system, the setup is the same except that Fe
oscillations during cyclic voltammetric studies of the replaces Al and the tungsten tip is placed near the perimeter
electroreduction of various organic compounds over of the mercury surface. Reprinted with permission from
a DME or an HMDE electrode (Ginzburg et ol., 1981; Keizer et al. (1979). Copyright 1979 American Chemical
Society.
Yamaguchi et al., 1981; Pragst and Loewis, 1982;
Ershler and Levinson, 1981). Violent current/voltage
oscillations and sparking were observed during the
electrolysis of Cryolite (NaJAlF6) and other melts and the oscillations in the voltage difference between
with different NaF/AlF, ratids by Nordmo and Hg and W, u = & - &,e,pl(W,, are shown in Fig. 59.
Thonstad (1984). Keizer et al. define the duration of the flat portion of
An interesting class of oscillating electrochemical the cycle (Fig. 59) as “flat-line time” and the time it
systems, the so-called “Beating Mercury Heart” sys- takes to go from the end of the flat portion of the cycle
tems, have been investigated by Keizer and coworkers to the cycle peak as the “rise time”. There are two
(Lin et al., 1979; Keizer et al., 1979; Anvir, 1989). The types of “Beating Mercury Heart” systems: those for
original observation was made by Kiihne and was which oscillations are triggered by placing a W tip in
reported over 100 years ago by Lippmann (1873). The the center of the Hg surface. and those for which
apparatus used by Keizer et al. is shown in Fig. 57. Hg oscillations are triggered by placing the W tip at the
in a glass tube is covered by an acidic or basic solu- perimeter. The latter are associated with the forma-
tion. A metal electrode (Al, Mg or Fe) is connected to tion of a film on the Hg surface.
a W tip, which is in contact with the Hg surface. This The flat portion of the cycle in Fig. 59 corresponds
results in a rapid motion of the Hg surface, which to the negative separations in Fig. 58. The voltage
Keizer et al. monitored with a high-speed camera. The begins to rise when contact is broken. Separation
oscillations of the Hg surface are shown in Fig. 58, achieves its maximum value before the voltage does,
 Electrochemical reaction dynamics 1545

-1

-2

-3
I I I
0 20 40 60 80
Time (min)
Fig. 58. Separation of W tip and the mercury surface as
a function of time for the Al(W)IOH-(aq), O,(aq)lHg(I)
oscillator. The experimental data is designated by vertical
error bars. Analysis of the film data was carried out with the
aid of a Photo Optical Data Analyzer (L. W. Van Nuys,
Model 224A). The solid line comes from the limit cycle
oscillation for model I with y,, = 391, Y= 280, D = 45,
i0 = 1.35 x 10e3, L = 0.17, and other parameters listedin ref.
27 of the original paper. Reprinted with permission from
Keizer et al. (1979). Copyright 1979 American Chemical
Society.
Fig. 59. Typical oscilloscope traces of spontaneous oscilla-
tions for the oscillators: (a) AI(W)INaCl(aq), NaOH(aq),
O~lHg(l) and (b) Fe(W)tK2CrZO,(aq)H2SOL(aq)t Hg(1).
and then decreases until contact between W and Hg is The vertical axis is the Hg to M(W) voltage difference, U,
which is always positive [one large division is 50mV in (a)
again established. sudden decrease in voltage is
The
and 200mV in (b)]; the horizontal axis is time (one large
complete within 10e6 -lo-’ s. The changes ob- division 2Oms). On the portion of the curve where the volt-
served in Figs 58 and 59 are due to the chem- age is constant, the flat line, v = 0.1 mV. The period is the
ical/physical processes occurring on the corroding time between two voltage peaks, and the duration of the
rising voltage is the rise time. The difference between the
metal and Hg surfaces. The driving force for oscil-
highest voltage during a period and the flat line is the peak
lations is the corrosion of the metal. For Fe or Al, the height. Reprinted with permission from Keizer er al. (1979).
processes, according to Keizer et al., are described by Copyright 1979 American Chemical Society.
the following reactions:
Fe + 2H+(aq)e Fe’+(aq) + H,(g) (79)
2Al+ 20H-(aq) + 6H20 *2Al(OH), + 3H,(g). The role of the corroding metal electrode (Fe) is to
provide the electrons for reaction (82). Similar oscil-
(80) lations can result by applying a voltage between the
Oscillations, which are triggered from near the per- Hg surface and the W tip in the absence of the Fe
imeter, occur in aqueous acid solutions (H2S04. electrode.
HCl, HN03), which contain strong oxidants like The center-triggered oscillations involve no film
CrlO:-, MnO;, and S20Q-. They involve the formation. For the system studied in most detail
formation of a surface film on the Hg surface, which by Keizer et al. [Al(W)/NaOH(aq), NaCl(aq),
proceeds spontaneously at these conditions. For the O,(aq)/Hg(l)], during the short circuit of the W tip
H2S04/Cr20$- system, for example, the surface film and the Hg, the following process occurs on the Hg
is formed by the following reaction: surface:
14Hf(aq) + Cr,O$-(aq) + 6Hg(l) + 3SO$-(aq) O,(aq) + 2H,O(l) + 4e- + 40H-(aq). (83)
-, 2Cr3+(aq) + 3Hg2S0,(s) + 7H,O(l). (81) The source of electrons is the Al electrode through the
Due to the film formation, the surface tension of the following overall reaction:
Hg changes and, under the action of the W-Hg volt-
age, the shape of the Hg surface changes (i.e. flattens). Al(s) + 40H-(aq) 4 Al(OH), + 3e-. (84)
As the surface flattens, the film is reduced according to Again, oscillations can be observed in the absence of
the following reaction: Al by applying an appropriate voltage between W and
Hg,SO,(s) + 2e- + 2Hg(l) + SO:-(aq). (82) Hg.
1546 J. L. HUDSONand T. T. TWIXIS
At equilibrium, the shape of the Hg surface depends Center triggered
on its surface tension y. When y is large, the surface
flattens, and when y is small the surface becomes more
3
rounded. In turn, y depends on the voltage and the 1
nature of the Hg-electrolyte interface. This is called
the electrocapillary effect and Fig. 60 shows how the Y
shape of the y vs V curve is affected by the formation 2 Hg4Mi-
of surface films and the adsorption of anions or inert q H.3
species. Figure 61 shows schematically how the elec- 02(q) + 2A20 + 4c - 40K(Surf)
trocapillary effect results in oscillations. For the I
+
center-triggered oscillations, for example, the path
V
2 to 3 corresponds to the reduction of the Hg surface
by reaction (83) during short circuit. This in turn
Side triggered
results in the reduction of y, flattening of the surface,
2
and breaking of the short circuit.
Keizer et al. (1979) have developed a model for the 1
center-triggered oscillations. They write three differ-
ential equations in terms of the separation distance Rg
Y 3
between the W tip and the Hg surface, the concentra-
tion of OH- on the Hg surface and D = (bHx - @AICwI. * Hg-.H2
They have investigated the model numerically and the 1
fi+<aqj + e- - ~H2(Sarf)
agreement between theory and experiments is very
good. Further details can be found in the original +
publications. v
A general diffusion/reaction model of relevance to
Side triggered
electroreduction systems has been presented by Jome
(1983). The model predicts oscillations, propagating
waves and patterns found on the electrode surface.
A generalized nucleation/growth model applicable to
electrocrystallization systems has been presented by
Bosco and Rangarajan (1982). The model predicts
interesting oscillatory transients.
The effect of sinusoidal cell-voltage control during
electrodeposition in a parallel-plate reactor has been
I Iig2X(surf) + ze- - 2Hs + x2-

+ -
studied theoretically by Smeltzer and Fedkiw (1991).
V
At high cycle-averaged current densities representing
a large fraction of the mass transfer limiting-current Fig. 61. A representation of the cycle of surface tension
sinusoidal cell-voltage oscillations can result in more changes for three different reduction processes on mercury.
Step 1 - 2 represents the rapid short circuit; step 2 -+ 3
uniform deposits than under steady-state control, the represents reduction occurring at the short-circuited voltage
uniformity of the deposit increasing with frequency. of the W tip; step 3 + 1 occurs after short circuit is broken.
At lower current densities, however, sinusoidal volt- See text for explanation. Reprinted with permission from
age control causes a more nonuniform deposition. Keizer et al. (1979). Copyright 1979 American Chemical
Society.

ELECTROCATALYTIC REACTIONS
Oxidation of small organic compounds
Formaldehyde, formate ions, formic acid. The elec-
trocatalytic oxidation of formaldehyde, formate ions,
and formic acid has been the subject of numerous
research studies. Several review papers on the electro-
chemical oxidation of these and other small organic
compounds have appeared; see, for example, Parsons
and VanderNoot (1988) for a recent review (and refer-
ences therein for other reviews on the same subject).
The dynamic behavior observed during the elec-
+
V trocatalytic oxidation of these compounds has also
attracted interest, starting with the investigations of
Fig. 60. Schematic graphs of the surface tension as a func- Mueller and coworkers (Mueller, 1923; Mueller and
tion of voltage for mercury and for mercury with Hz. OH-, Hindemith, 1927; Mueller and Tanaka, 1928), who
or Hg,X adsorbed on the surface. Reprinted with permission
from Keizer et al. (1979). Copyright 1979 American studied the oxidation of formic acid and observed
Chemical Society. oscillatory behavior under galvanostatic and
 Electrochemical reaction dynamics
quasipotentiostatic conditions. In a most recent
study, Albahadily and &hell (1991) reported on the
occurrence of potential oscillations during the electro-
chemical oxidation of formic acid under galvanostatic
conditions, and have discussed possible mechanisms
for oscillations. Several other studies (Wojtowicz et
al., 1968; Conway and Dziecuch, 1963; Schell et al.,
1989; Parida and Schell, 1991; Raspel et al., 1990;
Anastasijevic et al., 1989; Beden and Bewick, 1980;
Beden et al., 1981; Lamy and Hahn, 1985; Horanyi et
al., 1977, 1978; Guenther et al., 1982) have also re-
ported interesting dynamic behavior with this reac-
tion.
The formic acid oxidation involves both reactive
intermediates [formed by what Albahadily and Schell
(1991) define as the direct path] and other intermedi-
ates, which at low potential values are virtually in-
active and help to deactivate the electrode surface.
Several reactions that have been mentioned in the
literature would qualify for the direct path.
Albahadily and Schell (1991), for example, write the
following four reactions:
HCOOH + COOH + H (85)
COOH+CO, + H+ + em (86)
H-tH+ +e (87)
HCOOH + H 4 COOH + H2 (88)
where the underbar stands for an adsorbed reactive
intermediate. Furthermore, these steps themselves can
be decomposed into several other partial steps. Sev-
eral strongly adsorbed intermediates have been sug-
gested in the literature. Albahadily and Schell (1991)
consider only adsorbed CO as the intermediate and
postulate that it is formed by two reactions:
COOH+IJ-tCO+HzO (89)
2cOOH + CO + Hz0 + COZ. (90)
To complete the mechanism for oscillations requires
an additional feedback step between the poisoning
and direct path steps. Albahadily and Schell consider
this feedback step to be the reaction between
chemisorbed hydroxyl radicals and adsorbed co, i.e.
QH + CO+ H* + CO2 + e-. (91)
Hydroxyl radicals are assumed to chemisorb on the
electrode surface at high potentials in a process that
eventually might lead to oxide formation:
H,O+QH+H+ +e-. (92)
A similar feedback mechanism was proposed by
Wojtowicz et al. (1968), who also postulated that eq.
(91) is an autocatalytic reaction by assuming that its
rate is proportional to the density of vacant sites.
As with the several other mechanisms for oscil-
lations involving the formation/removal of poisons
from the electrode surface, the physical explanation
for oscillations based on the above mechanism is
rather simple. Reactions (89) and (90) lead to the
formation of co, which by covering the surface re-
1547
sults in an increase in the potentiaI in order to main-
tain constant current. At high enough potentials -OH
are formed, which through reaction (91) remove the
adsorbed co, the potential drops and the cycle
repeats itself. Although such a mechanism is adequate
to describe many of the oscillations observed,
Albahadily and Schell presented intricate experi-
mental dynamic behavior, which would tend to
indicate that other feedback mechanisms, coupled to
the main reaction, also exist.
Their experiments were performed with a rotating
Pt electrode in a 2.0 M solution of sodium formate in
1.0 M H,SO,. Figure 62 shows the potential (E) vs
current (I) curve. Their experiments indicate a broad
range of I values, for which the system shows oscil-
lations, and an equally broad range of conditions for
which it supports bistability, as was also previously
reported by Conway and Dzieciuch (1963). An ex-
planation for the observed bistability involves oxide
formation, which in the direction of increasing current
drives the system to a high-potential steady state. In
the opposite direction the decreasing current results in
small decreases of the potential until a critical current
density value is reached, below which the high-poten-
tial oxidation reactions cannot take place due to the
small current and the oxide breakup [a general model
predicting multiple steady states for electroor-
ganic reactions has been presented by Sakel-
laropoulos and Vohntine (NSO)]. The mechanism for
oscillations obviously remains valid in the presence of
the mechanism supporting bistability.
Albahadily and Schell report three distinct se-
quences of complex oscillatory behavior plus a range
of conditions in which simple large-period/large-am-
plitude oscillations were observed, The first sequence,
at the low-current end, consisted of oscillations with
a combination of small and large peaks, the ratio of
1.4 ,
. -1 01
. . -
E
w
1
-0.2
0 0.24
1 (ma)
Fig. 62. (a) Measured potential response [E vs SCE
(50.0°C)] at different values of the applied current (I). Open
squares represent data recorded after changing the current in
the positive direction. Two open squares for one value of the
current represent maximal and minimal values of an oscillat-
ing potential. Closed squares represent data recorded after
changing the current in the negative direction. Inset: An
enlargementof the low-current region. Reproducedby per-
missionof ElsevierSequoiaS.A. from Albahadilyand Schell,
J. electroanal. Chem. 308, 156 (1991).
1548 J. L. HUDSONand T. T.
the number of small peaks to that of large peaks
increasing as the current density increased. This se-
quence was followed by simple large-peak oscillations
with very large periods of up to 7 h, indicative of the
presence of a nearly homoclinic orbit. The large-per-
iod oscillations were then followed by a sequence of
oscillations with an ordering reversed to that of the
first sequence to be followed by a set of oscillatory
states, whose members could be identified as elements
from a Farey sequence. A sequence of Farey states
had been previously reported for formic acid oxida-
tion, under different experimental conditions by
Schell et al. (1989).
Using the mechanistic ideas previously discussed
Albahadily and Schell have developed two mathemat-
ical models to describe the oscillations. The first
model consists of six coupled differential equations in
terms of the surface coverages 0r2 (for COOH),
Oco (CO), @OH (OH), 6.1 (W and 00 (0) and the
potential. Reactions (85)-(88) represent the direct
path and reactions (89) and (90) the formation of C&l,
while reactions (91) and (92) the reaction between QH
and CO and the chemisorption of OH, correspond-
ingly. For the autocatalytic step (91) Albahadily and
Schell write the rate as
r7 = k,(.y + k72)&oQoH (93)
where s is the concentration of empty sites.
(Wojtowicz et al. assumed the same expression
but with k72 = 0.) To the above set of reactions,
Albahadily and Schell add two additional reactions to
account for the formation of oxides and for the evolu-
tion of oxygen:
QH+H++Q+e- (94)
H10+Q+$02+2Hf+2e-+Q. (95)
Numerical integrations of the differential equations to
simulate a small-amplitude oscillation are shown in
Fig. 63(a).
Model 2, for which simulations are shown in Fig.
63(b) and (c), couples reaction (85) with an additional
chemisorption step for HCOOH, namely
HCOOH-+COOH+H++e- (96)
considers the poison CO to be formed only by reac-
tion (90) and couples the oxidation of formic acid to
later stages of oxide formation through the reaction
Q + HCOOH -+ HZ0 + CO*. (97
For the latter, evidence is provided by the occurrence
of mixed-mode oscillations at the higher currents. For
the mixed-mode oscillations observed at the lower
currents, Albahadily and Schell postulate the exist-
ence of two forms of strongly bonded CO participat-
ing in the same reaction but with slightly different
potential dependence.
The effect that the nonlinear electrochemical dy-
namics of the oxidation process of formate/formic
acid has on the cyclic voltammetric behavior of the
process has been studied by Parida and Schell(l991).
Parida and Schell think of a stable cyclic voltam-
TSOTSIS
(4
0.7
0.4
z
Y
0. I
-0.2 1
(b)
0.7
9 0.4
w 0.1
1.0
a 0.5
0
Time (s)
Fig. 63. Calculations of potential and surface concen-
trations as a function of time. The formulation of the models
and the parameter values used in the calculation are given in
the appendix of the original paper: (a) potential calculated
from model 1, see the appendix of the original paper; (b)
potential calculated from model 2; (c) dimensionless surface
concentrations of CO (upper waveform) and OH calculated
using model 2. The time series for the concentration of OH is
terminated so that the shape of an oscillation in the upper
waveform is seen clearly. Reproduced by permission of
Elsevier Sequoia S.A. from Albahadily and Schell,
J. electroanak Chem. 308, 167 (1991).
mogram that repeats itself as a limit cycle projected
from the state space onto the current-potential plane.
They view the formic acid/formate oxidation process,
subjected to a cyclic sweeping potential, as a paramet-
rically, periodically forced nonlinear dynamic system.
For a range of values of the lower potential limit (LPL)
in the sweeping potential they found two types of
stable cyclic voltammograms (CV) coexisting a large-
amplitude CV (see Fig. 64) and a small-amplitude CV
(see Fig. 65), suggesting that the electrochemical sys-
tem subjected to a cyclic potential is a bistable system.
In the large-amplitude CV beginning at low potentials
the current first increases, due to the oxidation of
formate/formic acid, passes through a maximum and
then descends at larger values of the potential to
considerably smaller values of current due to the
formation of oxides on the working electrode surface.
On the reverse sweep, the current remains low (but
still finite due to the reduction of the oxides and the
oxidation of forrnate/formic acid that still occurs on
the electrode surface) until a point where a sharp rise
in the current occurs. This coincides with the last
value of the potential, where the last oxide is reduced.
 //f
.(a)
Electrochemical reaction dynamics
oxide formation [reaction (94)] reaches a stage that
1549

4
can be removed in the reverse sweep. For initial con-
ditions, for which the surface has a high hydroxyl
coverage, the oxide layer develops to a stage that
cannot be completely removed in the reverse sweep.
Bistability in the cyclic voltammetric behavior was
also reported for a number of primary alcohols
I (ethanol, propanol, butanol) by Cai and Schell(l992).
For ethanol and propanol, besides the bistable re-
sponse, other more complicated behavior was also
reported; see the discussion to follow.
A mechanism for the oscillations during formic acid
0 500 1000 oxidation on Pt has been recently discussed by
Potentiat (mV) Okamoto (1992). Okamoto implicates two poisoning
intermediates formed on the Pt surface, one being
Fig. 64. Set of cyclic voltammograms recorded at different
adsorbed CO and the other HZ0 molecules adsorbed
values of the lower potential limit (LPL). Current is plotted
against potential (SCE). Sweep rate = SO.OmV/s, upper po- on Pt sites adjacent to the CO-covered Pt sites. At the
tential limit = lOOO.OmV (SCE). (a) LPL = 20.0mV. At this high-voltage part of the potential cycle HZ0 reacts
value for the LPL, the system relaxes to the large-amplitude with CO and both poisons are then removed.
CV from all starting points. Reprinted with permission from Okamoto and Tanaka (1993) report that the same
Parida and Schell (1991). Copyright 1991 American
Chemical Society.
mechanism prevails during oscillations with formal-
dehyde oxidation.
One of the earlier and most complete investigations

r
20 of oscillations during the oxidation of formate ions
(a) over Pt or Pd electrodes is by Wojtowicz and cowor-
kers (1968), already referred to in the discussion of the
paper by Albahadily and Schell. Large oscillations
were observed under galvanostatic and potentiostatic
conditions and an extensive discussion was devoted to
the mechanistic causes for oscillations. As already
discussed, Wojtowicz and coworkers were the first to
include in the mechanism for oscillations an
autocatalytic step involving the removal from the
surface of inert reaction intermediates by an oxygen-
containing surface species.
Sustained current oscillations during HCOOH oxi-
dation in a HC104 supporting electrolyte over a
Pt (10 0) crystal were reported by Raspel et al. (1990).
Polcntial (mV) The authors report a reaction scheme for oscillations,
which involves reactions (85) and (86) describing the
Fig. 65. Sequence of small-amplitude cyclic voltammograms
shown at successively smaller values of the LPL. All other oxidation of formic acid to COZ, reaction (89) describ-
conditions the same as in Fig. 64. (a) LPL = 26OmV. Shown ing the poisoning of the surface by CO, and reactions
on the same scale as used in Fig. 64. (b) The same as (a), but (91) and (92) for the removal of the CO poison from
on a larger scale. Reprinted with permission from Parida and the surface. Based on this reaction scheme, they have
Schell (1991). Copyright 1991 American Chemical Society.
given in qualitative terms an explanation for the ob-
served oscillations. If one starts from the more neg-
The small-amplitude CVs are observed when the LPL ative potentials, where the surface is covered by CO,
is increased above a critical value, for which the moving into the potential region, where oscillations
oxides are permanently maintained on the electrode are observed, adsorbed CO is removed by surface
surface. Parida and &hell explain the b&ability in the hydroxyls. This frees sites for HCOOH oxidation
CV behavior in the context of the mechanism for [reactions (85) and (86)] and thus the current rises.
oscillations suggested by Albahadily and Schell This, in turn, produces adsorbed CO and also
(1991), i.e. reactions (85)-(97). Reactions (85)-(88), the protons, which would lead to a change in the pH in
direct path, cause the current increase in the first part the vicinity of the surface and in a reduction in the
of the forward sweep. CO is also formed [reactions surface hydroxyl groups and a reduced ability to
(89) and (90)]. At larger potentials, ~OH is chemi- remove CO. Thus, the current drops again, the pH
sorbed [reaction (92)], which in turn reacts with CO increases by diffusion of protons into the bulk solu-
[reaction (91)]. If the initial LPL conditions are such tion, the OH coverage increases, depoisoning of the
that enough CO is formed on the surface, for condi- surface occurs and the cycle repeats itself. The role of
tions that bistability occurs, reaction (91) will domin- pH aside, their mechanism is similar to that of
ate the forward sweep portion of the cycle and the Albahadily and Schell.
1550 J. L. HUDSON and T. T. TSOTSIS

The kinetics of formic acid oxidation over single- creasing part of the current oscillation is related to an
crystal Pt electrodes of various crystallographic ori- increasing oxidation current of formate ions on
entations have been studied by Tripkovic et al. (1991). a growing area of Rh, the deposition resulting from
The reaction rate and mechanism were shown to be the following reactions:
strongly dependent on the structure of the electrode
surface. The oscillatory behavior which was observed Rh’+ + 3Rh - COO- + 4Rh(s) + 3C02(g) (98)
during potentiodynamic experiments with the or
Pt(1 00), Pt(1 1 1 1) and Pt(6 10) simple crystal elec-
trode surfaces was not observed with the Pt(3 1 1) and 2Rh’ + + 3HCOO-(aq)
Pt(3 10) surfaces, which are characterized by in- + 2Rh(s) + 3COl(g) + 3H+(aq). (99)
creased step density. A detailed investigation of the
various factors (including the effect of adsorbing The decreasing part of the cycle may be due to an
anions) affecting oscillations during the formic acid inhibiting effect of RhOH formed according to the
oxidation on Pt(1 0 0) single crystal electrodes has electrochemical reaction
been reported by Markovic and Ross (1993). In agree- Rh + Hz0 + Rh - OH + H+(aq) + e-. (100)
ment with the results of Raspel et al. (1990) they were
unable to observe oscillations on Pt(l 1 1) crystals. The electrochemical oxidation of formate ions accord-
They were unable however to reproduce the strong ing to Beden et al. (1981) is described by three steps:
pH effects on oscillations reported by Raspel er nl. Rh + HCOO-(aq)+ Rh - COO- + H+(aq) + e-
(1990).
Anastasijevic et al. (1989) used differential electro- (101)
chemical mass spectrometry (DEMS) to in situ moni- Rh - COO- + Rh(s) + COa(g) + e- (102)
tor the CO2 produced during oscillations observed
with the HCOOH oxidation system. Potential oscil- Rh-COO-+Rh-OH
lations in phase with the CO2 mass spectral oscil- + 2Rh(s) + COl(g) + OH-(aq). (103)
lations were observed. Sun and Lin (1992) have re-
ported high-frequency current oscillations during the Strongly adsorbed intermediates may be formed and
oxidation of HCOOH over a Sb modified Pt elec- removed by a reaction with adsorbed OH:
trode. In situ, FTIR together with electrochemical Rh
techniques was used to study the oscillations. Rh-COO-+Rh-H+ Rh CO + OH-(aq)
>
Beden, Lamy and coworkers (Beden and Bewick,
1980; Beden et al., 1981; Lamy and Hahn, 1985) have (W
made an extensive investigation of oscillations ob- Rh
served under potentiodynamic/potentiostatic condi- Rh CO + 2Rh - OH 4 4Rh(s) + CO2 + HzO.
>
tions during the oxidation of formate ions (0.25 M
HCOONa in 0.2 M NaCIO, as supporting electro- (105)
lyte) in neutral media on in situ deposited Rh elec- According to Beden and coworkers, the electrode
trodes. Oscillations were observed as long as there state oscillates between a partially blocked and a free
was rhodium nitrate salt present in the electrolyte. Rh surface. The above mechanism is obviously not
Beden and coworkers utilized infrared spectroscopy distinctly different from the mechanism of Albahadily
to monitor the evolving gas and in situ reflectance and Schell already discussed.
studies of the Rh electrodes. It was thus verified that A variety of dynamic phenomena were also re-
CO2 is the only gas emitted during the oscillations ported by Xu and Schell(l990) and Schell et al. (1989)
and that the reflectance curve shows large perturba- for the electrochemical oxidation of formaldehyde at
tions synchronous with the oscillations. These large a rotating Pt electrode under galvanostatic conditions
changes were attributed to light scattering by the gas (interesting dynamics for this reaction have been re-
bubbles emitted in bursts, with each oscillation, but ported by a number of other investigators, e.g. Buck
also indicate an appreciable perturbation of the oxide and Griffith, 1962; Shropshire, 1967; Hunger, 1968,
layer during the oscillations. IR spectroscopy of elec- 1969; Breiter, 1969; Vielstich, 1970; Horanyi et al.,
trochemically modulated reflection signals (SIREM) 1978; Horanyi and Inzelt, 1978; Sidheswaram, 1978;
produced evidence for dissociative chemisorption of Novak and Visy, 1979, 1980; Avramov-Ivic et al.,
the formate species. Two CO-type species were identi- 1988; Hachkar et al., 1990, 1991; Nakabayashi and
fied (2050 and 1920 cm-‘), which presumably play the Kira, 1992). The reaction exhibited bistability with
role of electrocatalytic poisons. Studies using the vis- both high and low potential states coexisting within
ible UV spectrum of the electroreflection signal the same range of current density values. Sustained
(SUVER) have shown the presence of three oxygen- oscillations were realized over a broad range of the
ated species on the Rh electrode, out of which the applied current density values. Period-doubling bifur-
RhOH, appearing in acid and neutral solutions, was cations leading to chaos were observed by decreasing
implicated by Beden and coworkers in the oscilla- the current from a value at which a regular, one-peak
tions. oscillation was observed. Through a further decrease
A qualitative mechanism for oscillations has been in the current, a periodicchaotic bifurcation se-
suggested. According to Beden et al. (1981) the in- quence was observed, i.e. intervals of periodicity sep-
 Electrochemical reaction dynamics
arated by intervals of chaotic behavior. Periodic
states appear through tangent bifurcations from
chaotic states. Upon decreasing the current, one ob-
serves a limited number of subhatmonics and the
eventual return to a chaotic state. Within the periodic
interval principal states, labeled as lM (1 representing
one large oscillation and M representing M small
oscillations), and their subharmonics were observed.
Nonprincipal states were also observed. Although
such states appear to be similar to states observed
during formic acid oxidations, careful examination of
their symbolic patterns, obtained through one-dimen-
sional mapping, reveals them to be different.
Increasing the current beyond the value for which
the regular one-peak oscillation was observed, led to
the appearance of oscillations like those of Fig. 66.
The value of the potential peak in Fig. 66 is well
within the region, in which surface oxides are formed
on the electrode surface. Xu and &hell explain the
dynamic behavior of formaldehyde oxidation by
again postulating a mechanism, which involves a dir-
ect path, poison formation and removal coupled with
oxide formation on the electrode surface. Only the
initial steps of the direct path are different from those
of the formic acid/formate oxidation process already
discussed. They involve the hydration of HCHO to
form CH,(OH), and oxidation of CH2(0H)2 to form
HCOOH through the following two steps:
CHI(OH)L -+ HC(QH), + H+ + e- (106)
HC(QH), + HCOOH + H+ + e-. (107)
Other investigators, who had observed very similar
dynamic behavior during HCHO/HCOOH oxida-
tion, assumed these steps to be very fast and the
overall mechanism of the HCHO oxidation to be
similar to that of HCOOH oxidation. The results of
Xu and Schell seem to contradict these studies.
In a recent study, Beden and coworkers (Hachkar
er al., 1990,199l) reported on the dynamic behavior of
a variety of small electroactive organic compounds
(4
710
(b)
0 302 604
Time (s)
Fig. 66. Measured waveforms of dynamical states that were
found at values of the current that were larger than the value
at which the 1’ state. Fin. Z(a). was found to exist: (al
Id = 30 fi/cm2; (b) -I,, ~45‘&crn2. Reprinted wi&
permission from Xu and Sehell (1990). Copyright 1990
American Chemical Society.
1551
WCHO, (CH0)2, HCOOH, CH,OH, C,H,(OH),]
on various electrodes, focusing particular attention on
HCHO oxidation. Oscillations were observed during
cyclic voltammetric studies of HCHO oxidation in 0.1
NaOH electrolyte over a Rh wire. The oscillations
were observed in the positive portion of the sweep
cycle in the region, where the presence of Rh hydrox-
ide species has been reported. Oscillations were also
observed with Rh and Pt electrodes. The region in the
CV where oscillations are observed appear to be de-
pendent on the low and upper potential limits of the
sweep cycle. Beden and coworkers also carried out an
in situ investigation of the electrode surface, during
oscillations, for the electrocatalytic oxidation of
HCHO over Rh electrodes in alkaline solutions using
UV-visible reflectance spectroscopy. By observing the
Rh surface during the oscillations they were able to
show that the current oscillations were accompanied
by in-phase significant periodic reflectivity changes.
By comparing the UV spectra observed with those of
various oxides grown under different sets of experi-
mental pH and potential conditions and by observing
the dependence of the amplitude of reflectivity oscil-
lations on wavelength, they concluded that the peri-
odic buildup and removal of superficial oxide films is
involved in the mechanism for oscillations.
Regular one-peak oscillations during formaldehyde
oxidation over a rotating Pt electrode in a H2S04
solution were reported by Novak and Visy (1979,
1980).
Hunger (1969) also studied oscillations during for-
maldehyde oxidation over Pt electrodes in H,SO,
solutions. He subdivides the region of oscillations into
three subregions. In the first subregion (characterized
by galvanostatic oscillations for which the upper po-
tential stayed below + 0.92V vs SHE), Hunger at-
tributes the oscillation to a “valve” mechanism:
CH~(OH)Z,.I + CHz(OH)z,a, (108)
CH2(OH)2sda + A + H* + e- (109)
A+B+H++e- (110)
B+C+H++e- (111)
C+CO,fH++e-. (112)
Species A, B, C were not identified and the above
mechanism presumably represents the stepwise
anodic oxidation of formaldehyde. Step (112) is fol-
lowed by the readsorption step (108) and according to
Hunger this coupling mechanism in combination with
the fact that above 0.6 V vs SHE adsorption of
HCHO is negligible is sufficient to explain the ob-
served oscillations in this region.
Above current densities of 100pA/cm2 upper po-
tentials above 0.92 V vs SHE but lower potentials
below 0.6V are observed. According to Hunger, in
this region the oscillations are explained by a mixed
mechanism, i.e. “valve” plus anodic oxidation/reduc-
tion of Pt. The anodic oxidation of Pt is thought to
occur by direct adsorption of Hz0 and further dis-
charge.of adsorbed OH groups. Oxidation is followed
by reduction of the Pt oxide (represented by Pt/O) by
1552 J. L. HUDSONand T. T. TSOTSIS
HCHO:
Pt/O + +_CH20 ---t!COz + tHz0 + Pt (113)
which then prepares the electrode surface for re-
adsorption of HCHO on the Pt free sites. In the third
region for current densities above 400 pA/cm2 the
lower potential limit is above 0.6V vs SHE, which
according to Hunger precludes the adsorption of
CH,O on Pt. The oscillations in this region are due to
an oxidation/reduction mechanism of the Pt surface
as described above. They are mass transport con-
trolled. Turbulence in the layer adjacent to the
electrode surface is created through the evolution of
CO,. This leads to periodic changes in the thickness
of the boundary layer.
A number of interesting studies have been per-
formed by Horanyi and coworkers (Horanyi et a!.,
1977, 1978a). They have shown that under appropri-
ate experimental conditions, it is possible to observe
oscillations in the rest potential of a Pt electrode
immersed in a solution of Ce4+ or Fe3+ ions and
a variety of fuel compounds like formaldehyde, formic
acid, methanol, ethylene glycol, glyoxal, glycoal-
dehyde, and 2-propanol. These oscillations are very
similar to the oscillations observed by the same group
under galvanostatic conditions, lending credibility to
the argument that the galvanostatic oscillations ob-
served are due to the electrocatalytic kinetics and not
to the external circuit.
Horanyi and coworkers (Horanyi and Inzelt, 1978;
Horanyi et al., l978b) also reported galvanostatic
oscillations during the oxidation of ethylene glycol,
glyoxal, and glyoxylic acid over a platinized elec-
trode. In order to gain information on the state of the
electrode surface during oscillations, Horanyi and In-
zelt carried out their experiments in the presence of
36Cl-labeled chloride ions and monitored the concen-
tration of the radioactive species on the electrode
surface. The potential and the WI count rate oscil-
lated in phase, leading Horanyi and Inzelt to postu-
late that the potential oscillations involve adsorption
and desorption of chemisorbed species, which occupy
the same surface sites with the chloride ions and
which inhibit the main reaction.
A rotating ring-disk electrode cell was used by
Nakabayashi and Kira (1992) to study the electro-
chemical oxidation of formaldehyde in 2.0 M HzS04.
The potential/current of the disk and ring parts of the
electrode were independently adjusted. The ring elec-
trode was first operated in a galvanostatic mode un-
der conditions for which the ring potential exhibited
autonomous oscillations. The disk potential was then
simultaneously deliberately oscillated between the
voltage for Hz evolution (- 0.4 V) and the voltage
corresponding to zero current (0.1 V) vs SCE.
A wealth of various forced electrochemical potential
oscillations of the ring electrode resulted and were
studied by Nakabayashi and Kira (1992). The interac-
tion between the disk/ring electrodes is due to the
hydrogen evolved on the disk electrode, during the
forced potential oscillations, which transports to the
ring electrode and interferes with the electrochemical
formaldehyde oxidation reaction.
Alcohols and other organic compounds. Oscillations
during the galvanostatic oxidation of methanol have
been reported by several investigators. One of the
earliest studies of oscillations during CHJOH oxida-
tion is by Parela (1958) and later by Koch (1965).
Parela also provided a qualitative explanation for
these oscillations. At the low potential in the cycle, the
quantity of CHJOH adsorbed on the electrode is
small and, as it is readily oxidized, the potential rises
to a value at which the initial stage (PtOH) of surface
oxidation of Pt occurs. This oxide then reacts with
methanol to give HCHO and HCOOH which then
themselves oxidize on the electrode surface providing
time for the CH,OH to diffuse to the electrode sur-
face. Only a minor part of the surface seems to be
changing during the oscillation. The charge trans-
ferred in one cycle corresponded to 1% of the charge
associated with full monolayer coverage of the elec-
trode by CH,OH. Potential oscillations under poten-
tiodynamic conditions for CHjOH oxidation in
HISOQ electrolytes have been reported by Innocencio
and Innocencio (1991). The authors also present
a mechanism for oscillations, which they claim is
consistent with their experimental observations.
Novak and Visy (1979) report oscillations during
CH,OH oxidation in HClO, solutions over a rotat-
ing Pt electrode. The same authors have reported
oscillations with ethanol oxidation in both sulfuric
acid and HClO,. Oscillations during EtOH oxidation
in sulfuric acid solution over Pt electrodes were also
reported to occur by Venkateswara Rao and Roy
(1977) and Korchinskii (1975).
Oscillations with the oxidation of 2-propanol, s-
butanol and cyclohexanol were reported by Horanyi
et al. (1971, 1972, 1973). Potential oscillations were
reported by Takahashi and Miyake (1972) and Izumi
and Ohnishi (1982) during the galvanostatic oxidation
of various lower fatty alcohols over a Pt electrode in
acid aqueous solutions. They were attributed to two
competing processes, the accumulation on the surface
of the electrode of intermediates formed by the partial
oxidation of alcohols, which causes a decrease in the
oxidation rates, and an increase in the polarization.
Recently, Inzelt et al. (1993) reported that the poten-
tial oscillations observed during 2-propanol oxidation
over a platinized electrode can be associated with the
accumulation and consumption of chemisorbed spe-
cies. In their studies, they used an electrochemical
quartz crystal microbalance, which allows for con-
tinuous monitoring of the changes of the mass of
species adsorbed on the electrode surface. The same
technique has been recently applied to the study of
potential oscillations during galvanostatic oxidation
of formic acid on platinum (Inzelt and KertCsz, 1993)
and to the study of oscillations observed during open-
circuit copper electrodissolution in H2S04 and
CuSO, solutions (Inzelt, 1993). Interesting cyclic vol-
tammetric behavior has been reported by Schell and
 Electrochemical reaction dynamics 1553

-500 -200 100 -500 -200 100

E(mV)

Fig. 67. (a) A period-one cyclic voltammogram. Sweep rate = SOmV/s; lower potential limit = - 500 mV
vs SCE, UPL = 40.0 mV YS SCE, rotation rate = 5OOrpm, T = 25°C. (b) A period-two cyclic voltammo-
gram. UPL = 84.0 mV. The number 1 labels the point at which the curve is initiated at the beginning of the
first cycle of the potential; 2 denotes the point on the curve at the end of the first cycle and the beginning of
the second cycle in the potential. At the end of the second cycle the system returns to the point labelled 1. (c)
A Deriod-two cvclic voltammoaram measured close to the bifurcation point. UPL = 50.1 mV. (d) A Deriod-
two cyclic voltammogram. IJfi = 50.2 mV. Reproduced by permissidn of the Royal Society Gf’Chemistry
from Schell and Cai, J. Chem. Sot. Faraday Trans. (1991).

Cai (1991) during the ethanol oxidation over a rotat-
ing Pt electrode in an alkaline solution. Cyclic
voltammograms (CV) with periods 2, 3, 4, 5 and 7
times longer than the period of the potential cycle
were reported as well as aperiodic cyclic voltammo-
grams. The various types of voltammetric behavior
were found by systematically varying the upper
potential limit (UPL) during cycling. Period-one and
two CVs are shown in Fig. 67. The oxidation of
ethanol occurs during the rise in current in Fig. 67(a)
in the forward sweep. The decrease in current is at-
tributed to the formation of various oxide species and
the increase in current occurs after the final reduction
of the oxide layer. The period-two CV is shown in Fig.
67(b). The complete curve in Fig. 67(b) is traced out
every two cycles in the potential. The behavior in Fig.
67(b) is attributed to the formation of a resinous film
through aldol condensation. Upon increasing the
UP1 beyond the values in Fig. 67, aperiodic CVs were
observed. Many windows were found within the re-
gion of chaos, in which higher-order periodic CVs
were observed. Similar complex behavior was most
recently reported with methanol and 1-propanol by
t,he same authors (Schell and Cai, 1993).
Oscillations during the reduction of 2-butanone on
Pt in H2S04 have been reported by Feyaerts and
Wemptinne (1978).
Oscillations during the electroreduction of benzo-
triazole on a Cu amalgalm electrode in H,SOL have
been reported by Rysakov et al. (1974). They were
correlated with the alternating reduction of benzo-
triazole and hydrogen evolution.
Oscillations during the oxidation of dextrose over
a platinized Pt electrode in a phosphate buffer solu-
tion at a pH of 7.4 have been reported by Rao and
Drake (1969). The oscillatory behavior under gal-
vanostatic conditions is attributed to kinetic effects
(i.e. inhibition of the dextrose oxidation reaction) by
the main product of the reaction, i.e. gluconic acid and
the potential dependence of its adsorption.
Potentiostatic current oscillations during ethylene
oxidation over a rotating Pt electrode in 1 M aqueous
HCIOL electrqlyte have been reported by Wojtowicz
et al. (1968). The oscillations have been shown to cease
above a critical rotational speed depending on the
temperature and potential, indicating that the oscil-
lations are more diffusion controlled. Wojtowicz and
Conway (1969) presented a coupled diffusion-electro-
chemical oxidation mechanism to explain the occur-
rence of oscillations in qualitative terms. According to
them, as C2H4 reacts and depletes at the electrode
surface, a surface oxide builds on the electrode.
A point is reached when a rapid autocatalytic reaction
removes the oxide from the electrode surface and the
cycle repeats itself.
Oscillations during the partial oxidation of CH4 on
Cu, Au, glassy carbon and Hg-plated Cu electrodes in
aqueous media have been reported by Freser (1991).
The use of periodic voltage/current control to im-
prove the selectivity ‘of electroorganic synthesis reac-

CES49:10-E
1554 J. L. HUDSON and T. T. TSOTW

tions has been studied experimentally and theoret- .

ically by Fedkiw and coworkers (Fedkiw and Scott, I
I
1984; Nolen and Fedkiw, 1990; Smeltzer and Fedkiw, I
1992a, b) and a number of other investigators [for I
I
further details see Fedkiw and Scott (1984) and I
Smeltzer and Fedkiw (1992a, b)]. Fedkiw and cowor- I

kers studied the electroreduction of nitrobenzene DJ

*
(NB) to produce the intermediate compound phenyl- I
hydroxylamine (PHA), which subsequently undergoes I I
either a further electrochemical reduction to produce
aniline (an undesired product) or rearranges chemic-
ally to form the desired product p-aminophenol
(PAP). Under some conditions, the periodic voltage
operation seemed to give better PRP selectivities than
the steady-state operation for the same cycle averaged
PAP production rate. Autonomous current oscilla-
tions over a DME with the same reactions have been
reported by Jakuszewski and Turowska (1973). A sim-
ilar concept has recently been applied by Schell and
Albahadily (1993) to the electrocatalyzed oxidation of
formic acid.
Hjelmfelt et al. (1991) have studied power produc-
tion in electrochemical cells. They have looked at Fig. 68. Overview of the dynamic behavior in a broad para-
three different electrochemical systems: one contain- meter region. In regions A and B, stationary state and
ing two electrode reactions, another containing an small-amplitude harmonic oscillations were observed, re-
additional autocatalytic pathway between the elec- spectively. In region C the system exhibited mixed-mode
oscillations, whereas in region D single periodic large-ampli-
trode reactions and a third containing both compet-
tude relaxation oscillations were found. As the current values
ing autocatalytic and linear pathways between the at which the transition from stationary state to small oscilla-
electrode reactions. For both systems containing the tions occurred could vary up to 100yA/cm2 at different days,
autocatalytic pathways, Hjelmfelt et al. (1991) found no scale is shown in the current axis. Reproduced by per-
bistability in the power output, i.e. a high-efficiency, mission of Elsevier Science Publishers BV from Krischer e?
al., Physica D (1993).
high-power output branch coexisting with a low-efii-
ciency, low-power branch. The third system exhibits
damped or unstable oscillations, which eventually The transition from the chaotic attractor to the
lead to the low-efficiency branch. No autonomous MMOs was attributed to an interior crisis-type bifur-
oscillations were observed. cation, during which the small chaotic attractor is
destroyed by collision with the stable manifold of
Hydrogen oxidation a saddle-type limit set. At lower Cuzf the transition
The dynamic behavior of the electrocatalytic to MMOs occurs through the period-doubling cas-
H2 oxidation on Pt electrodes in the presence of cade. Most recently, the same group (Eiswirth et al.,
various cations has been studied by a number of 1992) have investigated the oxidation of hydrogen on
investigators (Eiswirth et al., 1992; Krischer et al., single-crystal platinum surfaces. They found that the
1991a, b, 1993; Horanyi and Visy, 1979; Armstrong dynamic behavior was different on the three types of
and Butler, 1947; Kodera et aI., 1986, 1988; Deibert surfaces: Pt(l lo), no oscillations; Pt(1 1 I), only
and Williams, 1969; Yamazaki and Kodera, 1989, simple oscillations; Pt(1 00), a variety of oscillation
1991; Yamazaki et al., 1990; Conway and Novak, types including simple periodic oscillations, period-
1977; Butler and Armstrong, 1932; Sawyer and Seo, doubling, chaos, and mixed-mode oscillations.
1963). Krischer et al. (1991, 1993) have studied this One of the earliest reports of oscillations during the
reaction in the presence of Cuz + and Cl - by carefully electrocatalytic H2 oxidation on Pt electrodes in the
varying two control parameters, i.e. current density presence of various ions is due to Horanyi and Visy
and CuZ+ concentration. In the parameter space (see (1979). About 30 years earlier Armstrong and Butler
Fig. 68) they observed four different regions of dy- (1947) had discussed the possible role of metal cation
namic behavior. In region A stationary states and in impurities on the observed galvanostatic oscillations
region B small-amplitude harmonic oscillations were but had made no effort to experimentally verify their
observed. In region C mixed-mode oscillations and in ideas. According to Horanyi and Visy the following
region D large-amplitude relaxation oscillations were mechanism explains the role of various cations in the
found. Depending on the concentration of Cu’+ the generation of the observed of oscillations. Electro-
transition from the harmonic small-amplitude oscil- sorbed cations presumably inhibit the oxidation of
lations to the MM0 regime would occur from HZ by blocking the sites on the surface that are avail-
a simple periodic, period doubled or chaotic attractor able for H2 adsorption and reaction. As a result of this
arising from a Feigenbaum route (Feigenbaum, 1983). inhibition under galvanostatic conditions the poten-
 Electrochemical reaction dynamics 1555

written as the sum of the oxidation current of H2, IH.

- 470
the cathodic current of Ag deposition, I,, the anodic
current of deposited Ag electrodissolution, I,, and the
- 460
charging/discharging current of the double layer, I,,,.
1200
I = I” - I, + I. + I*,_ (114)
Since the rate of H2 oxidation on Ag is two to three
\ \\
__ 0mu - +,@w
orders of magitude less than that on Pt they assumed
that the oxidation current on Ag is negligible. They
- 440 also assumed that an attractive interaction occurs
between Ag* adatoms on Pt. IdI is given as
-
- 430
(115)

C,, being the double-layer capacity and Cg the elec-

400 - 420
trode potential. Combining eqs (114) and (115)

- 410 g=(I--I,+I,--I.)lC,. (116)

/
The surface coverage of Ag, 0, is expressed as
-
0 20 40 60 80
(117)
t (9)

Fig. 69. Typical curve of potential oscillation (without Q being the quantity of electricity required to com-
multilayer deposition of Ag). Solution: 0.70 M plete a monolayer of adsorbed Ag. The overall rate of
HCIO,.+ 5.2 x iO_” M AgCIOI,-’ H2 bubbling rate: H, oxidation can be represented by the following
2OOc&/min, constant anodic current: 6.0mA. From three reaction steps:
Kodera et al. (1986).
H,(b) -+ Hz(s); HZ(s) + 2Hta); H(a)+H+ +e
tial should shift to more positive values, where de- (118)
sorption of the various metal cations would be occur- where b, s, and a stand for solution bulk, vicinity of
ring at the expense of adsorption. As a result the electrode and its surface correspondingly. The first
number of free-surface sites available for reaction step in the above mechanism represents diffusion, the
would increase, resulting in a decrease in the poten- second step adsorption, and the third step surface
tial. Thus, the sequence of blocking (due to adsorp- reaction. Based on the above scheme, IH was given as
tion) and unblocking of the metal surface by metal
ions is thought to result in the potential oscillations I = IO0 + K)(l -0)
H
under galvanostatic conditions. Horanyi and Visy re- 1 + KB pexP(%)
ported potential oscillations during H2 oxidation in
the presence of Cd”+, Cu2+, Bi3+, Sn2+, and Ag+ (119)
ions.
Kodera et a!. (Kodera et al., 1986, 1988; Yamazaki where
and Kodera, 1989, 1990) studied the oscillations dur- K:+K
ing electrocatalytic Hz oxidation in the presence of IO = ~
l+K
Ag+ ions using an Ag+ monitor electrode to directly
observe the deposition/dissolution phenomena during Ii; being the forward rate constant of the third reac-
the oscillations. (They also studied oscillations during tion above,
electrocatalytic H2 oxidation in the presence of CuZt K = {K: [H2(b)]/K;}“2 (120)
and Pb2+ ions.) Figure 69 shows the oscillations in
the electrode potential (CD)and the potential of the K: , KY being the forward/reverse reaction rate con-
AgC electrode (QDI). It is clear from this figure that the stants of the adsorption reaction, and
potential oscillations are directly related to the depos- B = [l - 1,/{1,(1 - 8)}]“2 (121)
ition/electrodissolution of Ag+. Kodera et al. (1988)
presented a mathematical model to explain the oscil- I, being the rate-limiting current.
lations. According to them the anodic current I can be For the cathodic current of Ag deposition I, and for
the anodic current of Ag dissolution they write

IL.AgKcLAg+(b)lU -~~~v(~)ew[ -(l&?QF]

(122)
I, =
1L,AI + K,[Ag+(b)l exp (s) exp [ -(lL_)@F]
1556 J. L. HUDSON and T. T. TSOTSIS

dation can occur in a kinetically periodic way when

,=K.,exp[T]exp($
where K, or K. are the rate constants for the cathodic
or anodic processes, IL,*. is the limiting current of
Ag+ diffusion, u the interaction energy between Ag+
adatoms, 6 a symmetry factor and y the anodic Tafel
constant both taken as 0.5. The above equations were
analyzed by linear stability analysis and were shown
to predict oscillations only when u < 0, i.e. in the
presence of attractive interaction between Ag(a)
adatoms. By assigning values to all constants except
K,, K, and u and by adjusting the values of K,, K,
and u, they were able to predict potential oscillations
(i.e. a, QM oscillations under galvanostatic condi-
tions).
Sustained potential oscillations have also been re-
ported during the electrocatalytic Hz oxidation on Pt
in the presence of CO (Deibert and Williams, 1969;
Yamazaki and Kodera, 1991). For example,
Yamazaki and Kodera (1991) reported large, regular
sustained oscillations, which they attributed to inhibi-
tion of the Hz reaction by CO. A mechanism involv-
ing adsorption/desorption of CO (conceptually sim-
ilar to the mechanism for oscillations during elec-
trocatalytic HZ oxidation in the presence of metal ions
presented by the same groupsee the discussion
above) was also presented, which seemed to give oscil-
lations for a region of parameter values and to predict
the qualitative influence of parameters, such as the
HI/CO bubbling rates and current density on the
oscillations. Again it was necessary to assume an
attractive interaction between the CO adatoms for the
model to predict the oscillations.
Novak and Conway (1977) have reported sustained
potentiostatic/potentiodynamic oscillations during
the electrocatalytic oxidation of H2 over a Pt elec-
trode in trifluoroacetic acid (TFA) containing con-
trolled traces of water. No oscillations arise in com-
pletely anhydrous TFA or when excess Hz0 is pres-
ent. Under these conditions they report that Hz oxi-
(123) potentials are reached at which the oxide layer begins
to reduce and ttifluoroacetate anion readsorption can
occur. The oscillatory behavior was found to depend
(a) on the degree of dryness of the solution, (b) on the
extent the Pt surface was oxidized at appropriate
positive potentials, and (c) stirring. Novak and
Conway also used in situ observations of the periodic
changes of the relative reflectance of the surface, in
phase with the current oscillations, to indirectly
deduce the participation of the surface oxide and
anion adsorption/desorption phenomena during the
oscillations. During oscillations observed under
potentiodynamic conditions the amplitude of success-
ive oscillations is a linear function of (At)“‘, At being
the time between successive pulses, which according
to them is a key indication that the oscillations arise
because of coupling between the kinetics of the elec-
trocatalytic oxidation reaction and diffusional mass
transfer of HZ. This is also indicated by the fact that
stirring completely eliminates the oscillations. The
proposed mechanism for oscillations is shown in Fig.
70. Several studies have also reported oscillations
during the electrocatalytic oxidation of H, in various
aqueous electrolytes in the absence of any gaseous or
metal impurities. Thalinger and Volmer in 1930
observed current oscillations during H2 oxidation
when a resistance in series with the cell was suitably
adjusted. Armstrong and Butler (1932, 1947) observed
potential oscillations during H2 oxidation on Pt in
a dilute H2S04 solution. They attributed the oscil-
lations to the presence of two unspecified processes
occurring on the electrode surface. According to them,
oscillations in the potential are the result of cycling
between these two surface processes the process of
diffusion providing the driving force for cycling.
Sawyer and Seo (1963) also observed very regular
potential oscillations during H2 oxidation on Pt.
They proposed as the mechanism responsible for
oscillations a cyclic formation and reduction of Pt

Scheme 1

Ha concentration in diffusion Reactivation due Reactivated surface due to oxide

layer approaches bulk c reduction by H2 andfor dcrorption
value (inhibited state; to increase of H2 of adaorbed anions by reaction
HZ-flux minimized; concentration at electrode H+ + AGs + HA from H+ produced
current minimum) surface-positive by Hz oxidation at surface
feedback step
H2 flux HZ consumption
diminishes facilitated
t I
+A-+&0
Inactivated surface;
H2 concentration in diffusion Diffusion layer depleted in Hz: flux
Surface inactivated
layer reco”crs to due to anion readsorption of Hz maximized (active stam, Hz-
larger values oxidation current maximized)
and/or surface
oxidation (hysteresis
with respect to
desorptioa directions
of these processes)

Fig. 70. Reprinted with permission from Conway and Novak (1977). Copyright 1977 American Chemical
Society.
 Electrochemical reaction dynamics 1557
Hydrogen peroxide reduction electrode. The mechanism of surface synchronization
Oscillations during electrochemical H202 reduc- was also investigated. The rise time in the oscillations
tion on a number of Cutontaining electrodes (see Fig. 71) was plotted as a function of the electrode
(CusFeS,, &Fe&, Cu,S, CuS, CuInS,, and CuInSe,) crystal’s diameter and it was found to have a linear
have been reported by Tributsch and coworkers dependence with a slope of 10 m/s, which approxim-
(Tributsch, 1975a, b, 1989; Tributsch and Bennett, ately also reflects the velocity of the propagating
1976; Cattarin and Tributsch, 1988a,b, 1990, 1992, chemical wave on the surface.
1993; Cattarin et al, 1990). Experiments by the same The oscillations on the Cu5FeS, electrode were also
group with FeS, Fe&, PbS, MO&, and CdS elec- shown to depend on the electrochemical pretreatment
trodes did not produce any oscillations, which, ac- of the surface, in a wide range of pH (2-13) although
cording to them, proves that the monovalent Cu+ ion the more alkaline pHs are more favorable (8-10).
tnust play an important role in the generation of Mass transport, as measured by the electrode rota-
oscillations. Neither were oscillations produced with tional rate, seemed to have an important effect on the
p-conducting Cu20 crystals or metallic Cu. Oscil- frequency, amplitude, and nature of the oscillations.
lations were observed under potentiodynamic, poten- In their search for a mechanism for the oscillations,
tiostatic, and galvanostatic conditions. The type of Tributsch and coworkers focused their attention on
oscillations ranged from simple, single-peak oscilla- the electronic structure of the Cu(I) ions, which are in
tions to the multipeak, complex types. electronic contact with a well-conducting sulfide
With all copper-containing sulfides, and in particu- matrix. The investigated sulfides are polar crystals, in
lar Cu2S, visible light clearly changed the amplitude which charge is transferred from the metal [copper is
and frequency of oscillations. In certain cases, a light thus losing its 4s electron to result in a monovalent
pulse was capable of switching ofI the oscillations. Cu(I)-ion] to sulfur to establish polar bonding. These
According to Tributsch and coworkers, this cathodic Cu(1) ions have further bonding capabilities by means
photoeffect is an indication of the participation of of their 3d orbitals, which engage in covalent bonding.
a Cu(I)-oxide species in the mechanism of oscillations. These covalent bonds are not expected to depend on
Measurement of the average electric charge turnover potential, but on the other hand cathodic polarization
during one oscillation on Cu5FeS4 (Bornite) electrode will affect the positive character of the Cu(1) ions and
showed that it corresponds to that of a mono- their polar bonding. It seems from the experiments of
layer-assuming one electron charge per 5 A* of sur- Tributsch and coworkers that the oscillatory behavior
face partaking in the reaction. This is indicative of the appears as soon as the positive character of the Cu(1)
fact that the entire Bornite electrode surface is parti- ions on the sulfide surface is reduced below a certain
cipating in the oscillation. These experiments were minimum. That a minimum cathodic electrode poten-
performed with a pyramidal Bornite crystal electrode, tial is required for the oscillations to occur is under-
which was gradually cut down. It was shown during stood in the following manner: At low cathodic poten-
these experiments that the average charge during an tials. ordinary catalytic decomposition of Hz02 will
oscillation varied linearly with the surface area of the
CU =o
CU =o c
CU =o a
CU -OH Hl”+02 cu
CU CU OcI21
c:
-OH =
CU -OH CU
OH
CU -OH C”

CU -OH CU -OH H20+ O2

CU -OH CU -OH

CU -OH CU -OH CU -OH

Sulfide Elecuolyre Sulfide Electrolyte

Sulfide Electrolyte

I I I
1 IV 100
Time
Surface arca (mm*)
Fig. 72. Scheme for the explanation of the periodicity of
Fig. 71. Dependence of oscillating charge on surface area of catalysis and proposed relation between partial reactions
Cu,FeS, electrode; electrolyte: 10-l M H,OZ, 10-l M KCl. and current oscillations (Me = metal ion = Cut). Reprinted
Reprinted with permission from Tributsch (1975~1). with permission from Tributsch and Bennett (1976).
1558 J. L. HUDKIN and T. T. TSOTSIS

occur on the &-containing electrode through altem- to the presence of iron oxides, which interfere with the
ate direct reduction/oxidation of the Cu ions. This is a characterization of the chemical environment of cop-
widely accepted mechanism for homogeneous Hz02 per. Since CuS was found to be generated during the
reduction. Reducing the positive character of the first stages of the oxidation of CuFe!$ and has also
Cu(I) ions by means of the cathodic potential will been shown to produce oscillations (see above)
eventually result in ceasing the electron transfer to the Cattarin et al. use this species to discuss the oscilla-
Cu(1) ion, thus stopping the catalytic decomposition tory phenomena. They represent the formation of the
of H202. At this point, the less efficient, but still active species Cu(lI)* as
energetically possible, electrochemical reduction of
CuS + 4H,O, + Cu(II)* + 4H20 + Sod. (127)
H202 will occur. This is described by the following
reaction steps (Tributsch and Bennett, 1976): On this active species it is assumed that Hz02 reduc-
tion requires less overpotential to occur, and happens
H,Oz + Me + Me0 + H,O (124) there until the bound species is converted into an inert
Me + Me-OH + HO1 -+ 2Me + O2 + Hz0 (125) CuO oxide. This interpretation is consistent with their
experimental observation that the process is deac-
Me0 f Me-OH + HO1 -P 2Me-OH + Oz. (126) tivated under polarization negative enough to reduce
The mechanistic scheme resulting in oscillations is as Cu(II)* in the presence of a nucleophilic ligand like
follows (according to Tributsch and coworkers-see NHS. This removes the active complex from the sur-
also Fig. 72): The copper sites on the copper sulfide face impeding its accumulation and results in conver-
are first oxidized through reaction (124). Then reac- sion of the copper complex into CuO. It is not clear
tion (126) [reaction (126) is autocatalytic since one how this mechanism of oscillations relates to the one
Me-OH results in two Me-OHS] involving a HOa previously suggested by the group. Cattarin ef al.
radical leads to the covering of the surface with OH (199Oa, b) themselves do not discuss the similarities
groups. Reaction (125) then cleans the surface of OH and/or differences. In a most recent paper, Cattarin
groups so that oxidation of Cu by H202 can occur and Tributsch (1993) discuss the existence of oscilla-
again. During the oscillations, an oxide layer is peri- tions in terms of the electrical model of Degn (1968)
odically formed and destroyed, but it is not directly that we have already discussed.
responsible for the oscillations. It is rather the pres- Oscillatory behavior during H,Oz reduction on Ag
ence of surface hydroxyl groups that are formed and in 02-free acidic solutions has been reported by
cathodically reduced that cause the oscillations. The Honda et al. (1986). Large-period and large-amplitude
mechanism, therefore, differs from the passive layer potential oscillations were observed. Honda et al.
concepts applied to oscillating electrode surfaces. No describe the cathodic reactions as
resistant cathodic passivation layer has been found H202 + e- -. OH(a) + OH- (128)
with sulfides exposed to HzOz-containing electro-
lytes. As already mentioned, the oscillations occur in OH(a) + e- + OH- (129)
terms of a propagating wave rather than a spatially 20H- + 2H+ + 2H20 (130)
uniform oscillation. Figure 73 incorporates the above
mechanism into a scheme for explaining the propaga- (a) designating the adsorption state. Reaction (128) is
tion of the oscillatory wave. considered to be rate limiting. The anodic reactions
Tn a recent study, Cattarin et al. (199Oa, b) investig- are represented as
ated the oscillatory kinetics of Hz02 reduction on Ag=+ Ag+(s) + e- (131)
CuFe$ by cyclic voltametry, ex situ analysis of the
Ag+(s)+Ag+(b) (132)
corrosion products, XPS, and EDX. They have im-
plicated the formation of an active Cu(II)* species, S, b representing the surface and bulk states, re-
which they were unfortunately unable to identify due spectively. An open-circuit (i.e. purely chemical) oxi-

“2%
L H20
cue culcuo

Fig. 73. Scheme for the explanation of the diffuse boundary regions of a propagating oscillation wave.
Reprinted with permission from Tributsch and Bennett (1976).
 Electrochemical
dation of Ag by HZO1 was also assumed to occur:
2Ag + 2H+(s) + H202(s) + 2Hz0 + 2Ag+(s).
According to Honda et al., the following mechanism
explains the oscillations. In the decreasing potential
part of the cycle, H20z reduction occurs according to
reactions (128)-(130). Simultaneously, the surface of
the electrode changes and becomes more active to-
wards H,O, reduction until, at a critical value, reac-
tion (133) commences. Ag+(s) formation by reactions
(131) and (132) causes an abrupt change of the poten-
tial to a positive value, since reaction (133) was as-
sumed to be very fast. In the potential-increasing part
of the cycle, the formation of AgC by reaction (133)
and its reduction to Ag by eqs (131) and (132) will
occur. During this process, the electrode once more
deactivates with respect to reaction (133) and finally
reaction (133) ceases, The inactive Ag species is
thought to involve O(a) and OH(a), but Honda et al.
presented no direct experimental evidence. Obviously,
additional experimentation is needed to verify this
mechanism for oscillations.
Fetner and Hudson (1990) also pbserved oscilla-
tions during the galvanostatic reduction of H202 on
a rotating Pt disk electrode in acidic solutions. They
observed oscillations ranging from the simple, single-
peak type to the very complex, albeit regular,
type-see Fig. 74. The data indicate the presence of
a saddle focus, which influences the flow on the oscil-
latory attractor. The oscillatory dynamics seemed to
be influenced by the rotational rate of the electrode,
(a) 1OOOrpm
640 I
6
is 340
2
Lu
401
0 1.75 5.25
Time (s)
(b) 400 rpm
640 I
401
50.0 51.75
Time (a)
Fig. 74. Effect of rotation rate (O.OSM H202.
H$O,, IOmA): (a) KKlOrpm, (b) 4OOrpm. Reprinted
permission from Fetner and Hudson (1990). Copyright
American Chemical Society.
reaction dynamics 1559
signifying that mass transfer is one of the processes
that affects the electrocatalytic reaction. The dy-
namics of the time series obtained with this reaction
(133) were investigated in more detail by Kube et al. (1993).
They analyzed the time series using a local method
and were able to calculate the eigenvalues of a fixed
point of the attractor constructed from the data. It
was shown how the system characteristics change as
a slow temporal variation of the oscillations occurs.
Current oscillations during H,O, and O2 electro-
chemical reduction in alkaline solutions over single
crystal Au electrodes have been reported by Strbac
and Adzic (1992). Oscillations were observed on the
Au( 1, 0,O) surface, but not on the two other low index
planes. Hydroxide ion adsorption was implicated in
the generation of these oscillations.
Other electrocutalytic reactions
Oscillations under potentiostatic conditions during
CH,OH synthesis from CO on Pt electrodes modified
with K*Fe,(CN), have been reported by Ogura and
Yamasaki (1985). The reaction was activated by the
addition of primary alcohols and complexes of
Fe(H), Fe(III), and Cr(III). The period/amplitude/in-
duction time for the current oscillations were shown
to be sensitive to the temperature and to the concen-
tration and nature of alcohols and metal complexes
added.
Oscillations in the rest potential during N,H, reac-
tion on Pt electrodes in KOH electrolytes were re-
ported in an early paper by Szpak (1968). A simple
model involving two differential equations in terms of
the concentration of an unidentified reaction inter-
mediate and the concentration of “free” sites on the
electrode was also presented. It was shown to be
capable of predicting single-peak regular and relax-
ation-type oscillations.
SEMICONDUCTOR ELECTRODES
A number of studies have reported oscillations and
other interesting behavior during electrochemical re-
actions on semiconductor electrode surfaces (see also
7.0 the discussion of the work ofTributsch and coworkers
in the preceding section). In one of the earliest studies,
van Meirhaeghe ef al. (1979) reported current oscilla-
tions observed under potentiostatic conditions on an
illuminated n-type GaAs electrode immersed in borax
solutions (KC1 + NaZB~07. pH = 10). Oscillations
were observed in a region of the current-voltage para-
meter space, where the system exhibits a negative
differential resistance. Oscillations were observed for
values of the light intensity and of the external resist-
ance exceeding minimum values. The oscillations dis-
57.0
appeared when the borax concentration exceeded
a maximum value. They were not observed in acetate
or pthalate buffer solutions, although various regions
of negative differential resistance were also observed
O.lOM
with for these systems. The oscillations reported ranged
1990 from the regular single-peak to the relaxation type at
high values of the external resistance.
1560 J. L. HUDSON
Van Meirhaeghe et al. (1979) refer to a theory of
electrochemical oscillations developed by Degn (1968)
to explain the oscillations. According to Degn (1968),
three conditions must be fulfilled for oscillations to
occur: (i) a region of negative differential resistance in
the current/voltage curve; (ii) an external resistance;
(iii) the occurrence of concentration polarization near
the electrode surface due to the electrochemical reac-
tion. The first two conditions are fulfilled for the GaAs
system. Concentration polarization of OH- occurs
during anodic GaAs dissolution due to the following
reaction:
GaAs + 6h+ + SOH- + GaO; + AsO;
+ 4H20. (134)
Van Meirhaeghe et al. (1979) explain the oscillations
in the following manner. Starting from the passive
state of the electrode and decreasing the semiconduc-
tor electrode’s potential, one reaches the region of
negative differential resistances. There, the GaAs sur-
face dissolves faster, causing depletion of OH- near
the electrode surface according to reaction (134). As
a result, the photocurrent decreases and so does the
voltage drop over the external resistance. The elec-
trode potential (vs SCE) shifts in the positive direction
into the passivation region. There the GaAs dissolu-
tion rate decreases, the OH- concentration polariza-
tion decreases, and the current and the voltage drop
over the external resistance increase. The potential (vs
SCE) again decreases, the system once more reaches
the active state, and the cycle closes. Current and
potential oscillation during H202 reduction on
n-GaAs and illuminated p-GaAs single crystal elec-
trodes have been reported by Koper et al. (1993).
Single-peak regular and relaxation type oscillations,
MMOs and deterministic chaos were reported. For
GaAs the current oscillations were accompanied by
oscillations in the electroluminescence.
Oscillations in the current and electrode reflectivity
and surface propagating waves were observed by
Tributsch et al. (1981) during iodide oxidation over
illuminated n-type MoSea semiconductor electrodes.
Similar phenomena in the absence of light were re-
ported for p-type MoSea and on metallic MbSes and
Pt surfaces. The interesting dynamic behavior was
attributed to the formation of a metastable iodine film
on the electrode surface, which undergoes various
phase transitions.
Damped photocurrent oscillations under poten-
tiostatic conditions with CdS electrodes immersed in
basic aqueous solutions have been reported by
Josseaux et al. (1985). The oscillations were attributed
to the formation and dissolution of a Cd(OH)z film.
Current oscillations with CdS electrodes immersed in
an 0.1 M K,F(CN),/O.l M K,F(CN), aqueous elec-
trolyte have been reported by Vainas (1985). The
oscillations were attributed to the formation and de-
tachment of gas bubbles formed on metallic Cd
patches found on the CdS.
Photocurrent oscillations, observed on an n-type
CdTe semiconductor electrode immersed in cesium
and T. T. TSOTSIS
sulfide solutions, have been reported by Marcu and
Tenne (1988). The oscillations were attributed to the
formation of free Te on the surface due to the reaction
CdTe + 2hf z Cd’+ + Te’. (135)
This surface Te dissolves according to the reaction
Tea + 30H- + h+ + TeO:- + !H2 (136)
the rate of which increases as the amount of free Te on
the electrode surface increases. As a result of reaction
(136) the local pH decreases, which results in a reduc-
tion of the flat-band potential of CdTe. This in turn
results in the reduction of the photocurrent of reac-
tion (135), which results in less Te produced, a de-
crease in the rate of reaction (136), an increase in the
pH, and a repeat of the cycle. The oscillations finally
disappear when the electrode surface is covered by
CdS, which is produced according to the reaction
Cd’+ + S”- + CdS. (137)
Current oscillations were also observed by Marcu and
Strehblow (1991) during anodization of Cd,Hg,_,Te
electrodes in basic solutions containing Cs+ and
ST ions. The surface concentrations of OH and Cs
were shown to oscillate synchronously with the cur-
rent oscillations. The oscillations were again at-
tributed to the formation and dissolution of a mono-
layer film of Te on the electrode surface as in the case
of oscillations observed with CdTe electrodes.
Current oscillations have been reported during the
dissolution of p- and n-Si electrodes in fluoride-con-
taining electrolytes (Gerischer and Liibke, 1988;
Lewerenz and Schlichthorl, 1992; Blackwood et al.,
1992; Chazalviel et al., 1988; Oszanam et al., 1991;
Stumper et al., 1991; Lewerenz, 1992). One of the
earliest studies is by Gerischer and Liibke (1988) who
reported current oscillations observed with a p-type Si
electrode immersed in an NHIF electrolyte solution.
Current oscillations under potentiodynamic condi-
tions with p-Si electrodes in NH4F electrolytes have
been reported by Chazalviel et al. (1991). The oscil-
lations disappeared under potentiostatic conditions
or for low speeds of the voltammetric sweep.
Oszanam et a!. (1992) and Chazalviel and Oszanam
(1992) subsequently reported that they were able to
observe current oscillations with this system upon
applying a small oscillatory perturbation in the po-
tential. The authors present a model to account for
this resonant behavior. They view the electrode as
consisting of small domains, which individually ex-
hibit autonomous current oscillations. These oscil-
lations consist of a succession of nonoverlapping cur-
rent pulses whose spacing was taken to be propor-
tional to the integrated change in the preceding pulse.
The authors explain this assumption by saying that
each current pulse results in the creation of a SiOl
film in the small domain. For a pulse to occur again,
one must wait for the chemical dissolution process to
dissolve this film. For a constant applied potential,
these domains are uncorrelated and, macroscopically,
a stable current is observed. In the presence of an
 Electrochemical reaction dynamics 1561

lations observed during p-Si or n-Si electrode dissolu-

tion is still not well understood.

MEMBRANES
There is a large body of information on oscillations
(and spatial patterns) which occur in membranes. Sus-
0 M~crowmve ripnd 0.20 - tained oscillations have been studied in both living
’ ’ ’ 1 ’ ’ ’ 0 and non-living systems. These studies are related to
those described above. However, the volume of in-
formation makes it impossible to discuss the area in
any detail in this review. Fortunately, an excellent and
complete review on oscillations and spatial non-
niformities in membranes has recently been published
by Larter (1990). The review cites over 310 references
and is recommended to readers interested in the sub-
ject.
01 ‘m--T ’ ’ ’ ’ ’ 1
0 10 20 30 40 SO 60 70 *o” CONCLUDING REMARKS
Time ($1 As can be seen from the above discussion, there are
numerous examples of oscillatory behavior in electro-
Fig. 75. Simultaneous photocurrent and excess microwave
reflectivity transients of n-Si (1 1 1) in 0.2M NH&F and chemical reacting systems. These examples appear
evaluation for surface recombination and charge transfer during the anodic dissolution and cathodic deposition
velocities; light mtensity 1.2 mW/cm’; wavelength of metals, and during electrocatalytic reactions. Such
I = 830 nm; electrode potential + 3 V (SCE). Reproduced oscillations are found in a wide variety of conditions
by pcrrnissron of Elsevier Sequoia S.A. from Lewerenz and
and over large parameter ranges.
Schlichthijrl, J. electroanal. Cheat. 327, 88 (1992).
Electrochemical reactions have furnished confirma-
tion of the existence of many types of interesting
dynamic behavior. For example, period-doubling bi-
imposed small sinusoidal potential, the behavior of furcations to chaos, several types of low-order chaos
these domains becomes synchronized and a resonant and transitions to higher-order chaos, quasiperiod-
oscillatory current behavior is observed. Chazlaviel icity, mixed-mode oscillations, etc., have been ob-
and Oszaman (1992) suggest that their model might served and analyzed. Surface patterns and wave
be more generally applicable to other oscillating elec- propagation have also been observed. Such studies
trochemical systems where other forms of coupling have been possible since well-defined dynamic behav-
between the various microdomains might exist, for ior occurs in several electrochemical reacting systems,
example, through an external resistance. Blackwood the signal-to-noise ratio is often relatively high, the
et al. (1992) have used a p-Si disk-Pt ring assembly to dynamic behavior is stationary for long times relative
monitor the processes occurring during the oscil- to the oscillation period, parameters (potential, cur-
lations as well as in situ ellipsometric measurements. rent) are easy to control and hold constant, etc.
The Pt ring current and the two main ellipsometric Although progress has been made in interpreting
parameters A and 1(1were shown to oscillate simultan- the origin of the oscillations and spatial patterns, this
eously with the p-Si disk current. Blackwood et al. is one area which needs further investigation. One
(1992), however, claim that the magnitudes of the would like to be able to explain the nature and cause
A oscillations are too small to correspond to any of the oscillatory behavior. Furthermore, an under-
periodic buildup and dissolution of surface oxide standing of oscillations will add to the understanding
layers. They attribute, instead, the ellipsometric of the electrochemical reactions themselves since
changes to periodic changes in the electrical field in models based on oscillatory phenomena are more
the interfacial region. Oscillations for n-type Si elec- sensitive to the assumed mechanism than those which
trodes have been reported in a number of papers. rely only on steady-state comparisons to experiment.
Figure 75 from Lewerenz and Schlichthiirl(1992), for This is also true with regard to surface patterns. In-
example, shows simultaneous photocurrent and ex- vestigations of such patterns. will aid in understanding
cess microwave reflectivity oscillations of n-Si (1 1 1) the role of surface nonuniformities in electrochemical
in 0.2 M NHLF solutions. Recently, Lewerenz (1992) reactions.
has used ex situ XPS measurements to monitor the
surface of n-Si (1 1 1) electrodes immersed in NH4F Acknowledgements-This work was supported in part by the
solutions. The samples prior to immersion were oxi- National S&mm Foundation (JLH), the University of
dized up to a thickness of 354OA. During oscil- Southern California (TTT) and by the Virginia Center for
Innovative Technology (JLH). A portion of this review was
lations the oxide thickness changed by less than 10% written while JLH was at the Fritz Haber Institut of the Max
although it appeared to oscillate simultaneously with Planck Gesellschaft with Professor G. Ertl, under the aus-
the current oscillations. The mechanism of oscil- pices of the Humboldt Foundation. We thank Mark Bassett,
1562 J. L. HUDSON and T. T. TSOTSIS

Ying Wang, Katharina Krischer for their technical contribu- Argoul, F., Huth, J., Merzeau, P., Arneodo, A. and Swinney,
tions. The authors would also like to thank Dr Bruce H. L., 1993, Experimental evidence for homoclinic chaos
Bennion for his assistance in locating many of the references in an electrochemical growth process. Physicu D 62, 170.
used in this paper, and Gamward Quan for his assistance in Armstrong, G. and Butler, J. A. V., 1947, Electrochemical
preparing the manuscript. periodicities in the anodic polarization of platinum elec-
trodes in the presence of hydrogen and their significance.
Disc. Faraday Sot. 1, 122.
Avramov-Ivic, M. L., Adzic, R. R., Bewick, A. and Razeg, M.,
1988, An investigation of the oxidation of formaldehyde
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