Variational principles in chemical equilibria: Complex chemical systems with interacting subsystems

Abstract

The goal of the paper is to derive a revised condition of global equilibrium in complex chemical systems as variational principle in formalism of recently developed discrete thermodynamics (DTD) of chemical equilibria. In classical approach the problem of complex equilibrium is solved by minimization of the system Gibbs' free energy subject to logistic constraints. DTD demands any isolated system to comprise smaller subentities, which individual equilibria are based on the balance of internal and external thermodynamic forces, acting against them. The internal forces are equal to the subsystems thermodynamic affinities, while external forces originate from subsystems mutual interactions. Those interactions impose additional constraints on the mother system Gibbs' free energy minimum. Basic expression of discrete thermodynamics, being multiplied by subsystems deviations from their "true" thermodynamic equilibria, is naturally identical to d'Alembert's principle. A thermodynamic version of d'Alembert's principle in combination with derived from it thermodynamic version of the principle of virtual work, allowed us to express the interactive constraints as a condition, that the sum of all subsystems thermodynamic affinities, multiplied by their deviations from their "true" equilibria, must be equal to zero. The revised formula of global equilibrium condition in complex chemical systems contains three terms - system Gibbs' free energy, logistic constraints, identical to their classical version, and interactive constraints, originated from the subsystems mutual interactions.