Abstract
Nonlinear systems can not be totally determined by the conjugate pairs of through and across variables routinely used in nonequilibrium thermodynamics and physical systems theory [1,2] . Once a reference state is specified, this problem is solved, but the constitutive relations now are reference state dependent. In this work, network thermodynamics, as developed by Peusner [3,4], is applied to nonlinear kinetic networks. The unification with the Hill, King-Altman approaches is further refined using the reference state idea of Sauer [ 1,2]. This results in a new, formal “thermokinetic” coordinate system which preserves both linearity and reciprocity far from equilibrium. This work also identifies two distinct classes of networks, namely “mechanistic” and “thermodynamic”. It will be shown that Peusner's approach [3–8, 24–28] provides a smooth transition between them as the mechanistic model approaches the near equilibrium (Onsager) domain.
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Mikulecky, D.C., Sauer, F. The role of the reference state in nonlinear kinetic models: Network thermodynamics leads to a linear and reciprocal coordinate system far from equilibrium. J Math Chem 2, 171–196 (1988). https://doi.org/10.1007/BF01165927
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DOI: https://doi.org/10.1007/BF01165927