
B IFURCATIONS
☞ L AB V ISIT 11
Iron + Sulfuric Acid −→ Hopf Bifurcation
T
HIS EXAMPLE of electric current oscillations in an electrochemical reac-
tion exhibits a subcritical Hopf bifurcation and hysteresis. These dynamical ideas
are fairly new compared to the long history of electrochemistry. The first elec-
trochemical system showing periodic orbits dates from G. Fechner in 1828, who
found an oscillating current caused by the competing forces of depositing and
dissolving of silver on an iron electrode placed in a silver nitrate solution.
The experiment shown here was designed to explore oscillatory phenomena
in the dissolving of iron in a sulfuric acid solution. A 99.99% iron rod with a
diameter of 3 mm is lowered into 200 ml of the acid. When a potential difference
is applied, the current of the electrochemical system is a measure of the overall
reaction rate between the electrode surface and the electrolytic solution. The
behavior of the current as a function of time shows considerable complication at
certain parameter settings. The so-called electrodissolution problem is far from
completely understood, due to the large number of coupled chemical reactions
involved.
The electrical potential applied to the electrode is used as a bifurcation
parameter in this experiment. Figure 11.27 shows a small sample of the interest-
ing dynamical phenomena in this reaction. Parts (a)–(d) of the figure show the
measured current (in milliamperes) as a function of time (in seconds), for four
different settings of the potential. The potential increases from (a) to (d). Figure
11.27(a) shows a short transient followed by a constant current, which continues
for the slightly higher potential in (b). In Figure 11.27(c), small irregular oscilla-
tions have developed, which seem aperiodic. Another small change in potential
leads to clear periodic oscillations of larger amplitude in (d). Apparently, a Hopf
bifurcation has occurred.
The time series in Figure 11.28 are from the same electrochemical experi-
ment, except that in this case, the voltage parameter is decreased from part (a)
to (d). Viewed together, the behaviors shown in Figures 11.27 and 11.28 can be
Sazou, D., Karantonis, A., and Pagitsas, M. 1993. Generalized Hopf, saddle-node infinite
period bifurcations and excitability during the electrodissolution and passivation of iron
in a sulfuric acid solution. Int. J. Bifurcations and Chaos 3: 981–997.
496