Damped physical oscillators, temperature and chemical clocks

TL;DR

This paper explores the analogy between physical and chemical oscillators, showing that chemical clocks can be represented by equations similar to those of damped physical oscillators, revealing underlying reversible entropy oscillations.

Contribution

It introduces a formalism that unifies chemical and physical oscillations by relaxing Onsager's reciprocal relations, highlighting reversible entropy oscillations in chemical clocks.

Findings

Chemical oscillations can be modeled by equations analogous to physical damped oscillators.

Reversible temperature and entropy oscillations are present in chemical clocks like the Belousov-Zhabotinsky reaction.

Physical and chemical clocks share underlying reversible entropy-conserving mechanisms.

Abstract

The metaphor of a clock in physics describes near-equilibrium reversible phenomena such as an oscillating spring. It is surprising that for chemical and biological clocks the focus has been exclusively on the far-from-equilibrium dissipative processes. We show here that one can represent chemical oscillations (the Lotka-Volterra system and the Brusselator) by equations analogous to Onsager's phenomenological equations when the condition of the reciprocal relations, i.e. the symmetry in the coupling of thermodynamic forces to fluxes is relaxed and antisymmetric contributions are permitted. We compare these oscillations to damped oscillators in physics (e.g., springs, coupled springs and electrical circuits) which are represented by similar equations. Onsager's equations and harmonic Hamiltonian systems are shown to be limiting cases of a more general formalism. The central element of un-damped physical oscillations is the conservation of entropy which unavoidably results in reversible temperature oscillations. Such temperature oscillations exist in springs and electrical LC-circuits, but have among others also been found in the oscillating Belousov-Zhabotinsky reaction, in oscillations of yeast cells, and during the nervous impulse. This suggests that such oscillations contain reversible entropy-conserving elements, and that physical and chemical clocks may be more similar than expected.