On Discrete Thermodynamics of Electrochemical Systems and Electrochemical Oscillations

TL;DR

This paper applies discrete thermodynamics to electrochemical systems, revealing how feedback mechanisms lead to oscillations and bifurcations, with spectra exhibiting multifractal characteristics, and compares theoretical results with experiments.

Contribution

It introduces a discrete thermodynamics framework for electrochemical systems, explaining oscillations and bifurcations through a ln-logistic map with non-unity charge transfer coefficient.

Findings

Electrochemical oscillations arise beyond bifurcation points.

Spectra of oscillations are multifractal.

Graphical solutions align qualitatively with experimental data.

Abstract

The article presents results of discrete thermodynamics (DTD) basic application to electrochemical systems. Consistent treatment of the electrochemical system as comprising two interacting subsystems - the chemical and the electrical (electrochemical) - leads to ln-logistic map of states of the electrochemical system with non-unity coefficient of the electrical charge transfer. This factor provides for a feedback and causes dynamic behavior of electrochemical systems, including bifurcations and electrochemical oscillations. The latter occur beyond bifurcation point at essential deviation of the chemical subsystem from true thermodynamic equilibrium. If the charge transfer coefficient takes on unity, the map turns into classical equation of electrochemical equilibrium. Spectra of electrochemical oscillations, resulted from the DTD formalism, are multifractals. Graphical solutions of this work are qualitatively compared to some experimental results.