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On the thermodynamics of elementary chemical reactions in homogeneous systems

On the thermodynamics of elementary chemical reactions in homogeneous systems

Authors :
I. Gyarmati
S. Lengyel
Source :
The Journal of Chemical Physics. 75:2384-2389
Publication Year :
1981
Publisher :
AIP Publishing, 1981.

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.

Details

ISSN :
10897690 and 00219606
Volume :
75
Database :
OpenAIRE
Journal :
The Journal of Chemical Physics
Accession number :
edsair.doi...........7ed237de736c7b1603f3f941ba5705d9
Full Text :
https://doi.org/10.1063/1.442301