On the thermodynamics of elementary chemical reactions in homogeneous systems

Abstract

The authors intend to contribute to the solution of the problems posed by the inconsistency of thermodynamics with the classical theory of chemical kinetics. It is, however, mainly intended only to clarify the basic question of linear theory, i.e., trivial and real satisfaction of the Onsager reciprocity relations (ORR). To this end, the thermodynamic basic equations of homogeneous closed chemically reacting systems are presented and direct transformation of a stoichiometrically equivalent independent system is given. Nonlinear constitutive equations of reaction kinetics equivalent to the Guldberg–Waage equations are presented and a method is given for their derivation. It has been proven that in stoichiometrically independent systems the ORR’s are always trivially satisfied in a linear approximation. A real satisfaction of the ORR’s occurs only in the case of independent fluxes and affinities that equivalently represent dependent systems.