Quantitative dynamical relationships for the effect of rotation rate on frequency and waveform of electrochemical oscillations

Mónika Urvölgyi, V. Gáspár, Timea Nagy, István Z. Kiss

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

We investigate the effect of changing mass transfer conditions through variation of rotation rate of a rotating disk electrode on features of oscillatory dynamics of negative differential resistance electrochemical systems. The theoretical analysis and numerical simulation of a prototype two-variable electrochemical model show that for oscillations close to a Hopf bifurcation the frequency (ω) increases with increase in rotation rate (d) following an approximate square root formula ω∞d 1/2. For relaxation oscillations, the oscillations maxima, minima, and transition points between the high- and low-current states do not depend on rotation rate; the oscillation waveform invariance is explained using nullcline analysis by showing that the rotation does not affect the nullcline of the fast variable (electrode potential) along which the oscillations occur. The numerical and theoretical predictions are confirmed in experiments with copper electrodissolution in phosphoric acid electrolyte using a rotating electrode setup. The results thus indicate that simplifying concepts related to invariant manifolds and parameter dependence of bifurcation points (principle of critical simplification) are efficient approaches to obtaining quantitative dynamical relationships for decoding complexity in electrochemical reaction systems.

Original languageEnglish
Pages (from-to)56-65
Number of pages10
JournalChemical Engineering Science
Volume83
DOIs
Publication statusPublished - Dec 3 2012

Fingerprint

Waveform
Oscillation
Electrode
Electrodes
Relaxation Oscillations
Rotating Disk
Hopf bifurcation
Invariant Manifolds
Rotating disks
Mass Transfer
Phosphoric acid
Bifurcation Point
Electrolyte
Invariance
Square root
Copper
Hopf Bifurcation
Simplification
Electrolytes
Decoding

Keywords

  • Electrochemistry
  • Mathematical modeling
  • Model reduction
  • Nonlinear dynamics
  • Nullclines
  • Oscillations

ASJC Scopus subject areas

  • Chemical Engineering(all)
  • Chemistry(all)
  • Applied Mathematics
  • Industrial and Manufacturing Engineering

Cite this

Quantitative dynamical relationships for the effect of rotation rate on frequency and waveform of electrochemical oscillations. / Urvölgyi, Mónika; Gáspár, V.; Nagy, Timea; Kiss, István Z.

In: Chemical Engineering Science, Vol. 83, 03.12.2012, p. 56-65.

Research output: Contribution to journalArticle

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