Dynamical response of the sinusoidally perturbed electrodissolution/passivation of iron in sulfuric acid solutions: Entrainment, spike generation, and quasiperiodicity.
The iron/sulfuric acid (Fe/2 M H(2)SO(4)) system exhibits periodic current oscillations of relaxation type within the potential transition region formed between the active and passive states of the iron electrode when it is polarized in the 2 M sulfuric acid solution. In the present work the dynamical response of the Fe/2 M H(2)SO(4) electrochemical oscillator is investigated when the applied potential at the iron electrode is sinusoidally perturbed. The behavior of the periodically perturbed Fe/2 M H(2)SO(4) oscillator differs significantly from the response of other forced oscillators, as the potential amplitude E(p) and the frequency ratio omega(p)/omega(0) vary. The omega(p) and omega(0) are the angular frequencies of the perturbed applied potential and the unperturbed oscillator, respectively. A special feature of its response is the appearance of a number of spikes, generated within the passive section of a periodic oscillatory cycle for omega(p)/omega(0)<2.9, for periods of the autonomous oscillator T(0) greater, similar 3 s. The number of the generated spikes depends on the amplitude and frequency of the perturbed applied potential as well as on the period of the autonomous oscillator. Spikes are not generated for omega(p)/omega(0)=1 and the system is harmonically entrained by the forcing frequency. However, when the system is subharmonically entrained for omega(p)/omega(0) close to 2, spike generation does occur. By increasing the perturbation frequency for omega(p)/omega(0) greater, similar 2.9 and T(0) greater, similar 3 s, or by decreasing the autonomous period for T(0)<3 s and all the omega(p)/omega(0)<2.9 ratios, the spike generation pattern, is replaced by a quasiperiodic pattern. The dynamical response of the perturbed Fe/2 M H(2)SO(4) electrochemical oscillator is characterized by using time-delay reconstructions of the attractors, Poincare maps, and Fourier power spectra.
Karantonis
Antonis
A
Laboratory of Physical Chemistry, Department of Chemistry, Aristotle University of Thessaloniki, 54 006 Thessaloniki, Greece.
Pagitsas
Michael
M
Sazou
Dimitra
D