Thermodynamic stability of elementary chemical reactions proceeding at finite rates revisited using Lyapunov function analysis

Abstract

The thermodynamic stability of a few representative elementary chemical reactions proceeding at finite rates has been investigated using the recently proposed thermodynamic Lyapunov function and following the steps of Lyapunov’s second method (also termed as the direct method) of stability of motion. The thermodynamic Lyapunov function; L s , used herein is the excess rate of entropy production in the thermodynamic perturbation space, which thereby inherits the dictates of the second law of thermodynamics. This Lyapunov function is not the same as the excess entropy rate that one encounters in thermodynamic (irreversible) literature. The model chemical conversions studied in this presentation are A+B→ v xX and A+B⇌ ν xX. For the sake of simplicity, the thermal effects of chemical reactions have been considered as not adding to the perturbation as our main aim was to demonstrate how one should use systematically the proposed thermodynamic Lyapunov function following the steps of Lyapunov’s second method of stability of motion. The domains of thermodynamic stability under the constantly acting small disturbances, thermodynamic asymptotic stability and thermodynamic instability in these model systems get established.