Thermodynamically predicted oscillations in closed chemical systems

TL;DR

This paper introduces a thermodynamic framework for understanding chemical oscillations in closed systems, challenging the traditional kinetic models and highlighting new features like spontaneity and fractality.

Contribution

It presents a thermodynamic approach to chemical oscillations, demonstrating their occurrence without kinetic assumptions and revealing new characteristics such as spontaneity and fractality.

Findings

Chemical oscillations can be predicted thermodynamically.

Oscillations occur in bistable bifurcation areas.

New features like spontaneity and fractality are identified.

Abstract

All known up to now models of chemical oscillations are based exclusively on kinetic considerations. The chemical gross-process equation is split usually by elementary steps, each step is supplied by an arrow and a differential equation, joint solution to such a construction under certain, often ad hoc chosen conditions and with ad hoc numerical coefficients leads to chemical oscillations. Kinetic perception of chemical oscillations reigns without exclusions. However, as it was recently shown by the author for the laser and for the electrochemical systems, chemical oscillations follow also from solutions to the basic expressions of discrete thermodynamics of chemical equilibria. Graphically those solutions are various fork bifurcation diagrams, and, in certain types of chemical systems, oscillations are well pronounced in the bistable bifurcation areas. In this work we describe a general thermodynamic approach to chemical oscillations as opposite to kinetic models, and depict some of their new features like spontaneity and fractality. The paper doubts exclusivity of the kinetic approach to chemical oscillations, and its aim is to discuss and exemplify thermodynamically predicted chemical oscillations in closed chemical systems.