Mathematical Formalism of Nonequilibrium Thermodynamics for Nonlinear Chemical Reaction Systems with General Rate Law

被引：0
作者：
Hao Ge
Hong Qian
机构：
[1] Peking University,Beijing International Center for Mathematical Research (BICMR) and Biodynamic Optical Imaging Center (BIOPIC)
[2] University of Washington,Department of Applied Mathematics
来源：
Journal of Statistical Physics | 2017年 / 166卷
关键词：
Chemical reaction models; Large deviation principle; Stochastic thermodynamics;
D O I：
暂无
中图分类号：
学科分类号：
摘要：
This paper studies a mathematical formalism of nonequilibrium thermodynamics for chemical reaction models with N species, M reactions, and general rate law. We establish a mathematical basis for J. W. Gibbs’ macroscopic chemical thermodynamics under G. N. Lewis’ kinetic law of entire equilibrium (detailed balance in nonlinear chemical kinetics). In doing so, the equilibrium thermodynamics is then naturally generalized to nonequilibrium settings without detailed balance. The kinetic models are represented by a Markovian jumping process. A generalized macroscopic chemical free energy function and its associated balance equation with nonnegative source and sink are the major discoveries. The proof is based on the large deviation principle of this type of Markov processes. A general fluctuation dissipation theorem for stochastic reaction kinetics is also proved. The mathematical theory illustrates how a novel macroscopic dynamic law can emerges from the mesoscopic kinetics in a multi-scale system.
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页码：190 / 209
页数：19
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