Physicochemical Mechanics and Nonequilibrium Chemical Thermodynamics.

Abstract

Equilibrium thermodynamics answers the question, "by how much?" Nonequilibrium thermodynamics answers the question "how fast?" The physicochemical mechanics approach presented in this article answers both of these questions. It also gives equilibrium laws and expressions for all major transport coefficients and their relations, which was previously impossible. For example, Onsager's reciprocal relations only tell us that symmetric transport coefficients are equal, and even for these, the value is often not known. Our new approach, applicable to non-isolated systems, leads to a new formulation of the second law of thermodynamics and agrees with entropy increase in spontaneous processes for isolated systems. Instead of entropy, it is based on a modified Lagrangian formulation which always increases during system evolution, even in the presence of external fields. This article will present numerous examples of physicochemical mechanics can be applied to various transport processes and their equilibriums, including thermodiffusion and different surface processes. It has been proven that the efficiency of a transport process with an actual steady-state flux (as opposed to a reversible process near equilibrium) is 50%. Finally, an analogy between physicochemical mechanics and some social processes is mentioned.