Nonequilibrium Thermodynamic Formalism of Nonlinear Chemical Reaction Systems with Waage-Guldberg's Law of Mass Action

Abstract: Macroscopic entropy production $\sigma^{(tot)}$ in the general nonlinear isothermal chemical reaction system with mass action kinetics is decomposed into a free energy dissipation and a house-keeping heat: $\sigma^{(tot)}=\sigma^{(fd)}+\sigma^{(hk)}$; $\sigma^{(fd)}=-\rd A/\rd t$, where $A$ is a generalized free energy function. This yields a novel nonequilibrium free energy balance equation $\rd A/\rd t=-\sigma^{(tot)}+\sigma^{(hk)}$, which is on a par with celebrated entropy balance equation $\rd S/\rd t=\sigma^{(tot)}+\eta^{(ex)}$ where $\eta^{(ex)}$ is the rate of entropy exchange with the environment.For kinetic systems with complex balance, $\sigma^{(fd)}$ and $\sigma^{(hk)}$ are the macroscopic limits of stochastic free energy dissipation and house-keeping heat, which are both nonnegative, in the Delbr\"uck-Gillespie description of the stochastic chemical kinetics.Therefore, we show that a full kinetic and thermodynamic theory of chemical reaction systems that transcends mesoscopic and macroscopic levels emerges.