
L AB V ISIT 3
☞ L AB V ISIT 3
Periodicity and Chaos in a Chemical Reaction
I
N ELEMENTARY chemistry classes, a great deal of emphasis is placed on
finding the equilibrium state of a reaction. It turns out that equilibria present only
one facet of possible behavior in a chemical reaction. Periodic oscillations and
even more erratic behaviors are routinely observed in particular systems.
Studies on oscillating reactions originally focused on the Belousov-
Zhabotinskii reaction, in which bromate ions are reduced by malonic acid
in the presence of a catalyst. The mechanism of the reaction is complicated.
More than 20 species can be identified at various stages of the reaction. Experi-
ments on this reaction by a group of researchers at the University of Texas were
conducted in a continuous-flow stirred tank reactor (CSTR), shown schemati-
cally in Figure 3.17. The solution is stirred at 1800 rpm by the impeller. There is
a constant flow in and out of the tank, perfectly balanced so that the total fluid
volume does not change as the reaction proceeds. The feed chemicals are fixed
concentrations of malonic acid, potassium bromate, cerous sulfate, and sulfuric
acid. The flow rate is maintained as a constant throughout the reaction, and the
bromide concentration is measured with electrodes immersed in the reactor. The
output of the experiment is monitored solely through the bromide measurement.
The constant flow rate can be treated as a system parameter, which can be
changed from time to time to look for qualitative changes in system dynamics,
or bifurcations. Figure 3.18 shows several different periodic behaviors of the
bromide concentration, for different settings of the flow rate. The progression
of flow rate values shown here is decreasing in the direction of the arrows and
results in periodic behavior of periods 6, 5, 3, 5, 4, 6, and 5. Each oscillation (an
up and down movement of the bromide concentration) takes around 2 minutes.
Approximately one hour was allowed to pass between changes of the flow rate to
allow the system to settle into its asymptotic behavior.
Roux, J.-C., Simoyi, R.H., Swinney, H.L., “Observation of a strange attractor”. Physica
D 8, 257-266 (1983).
Coffman, K.G., McCormick, W.D., Noszticzius, Z., Simoyi, R.H., Swinney, H.L., “Uni-
versality, multiplicity, and the effect of iron impurities in the Belousov-Zhabotinskii
reaction.” J. Chemical Physics 86, 119-129 (1987).
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