Nonequilibrium thermodynamic formalism of nonlinear chemical reaction systems with Waage-Guldberg’s law of mass action

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• 作者：Hao Ge^a ; ^{haoge@pku.edu.cn" class="auth_mail" title="E-mail the corresponding author} ; Hong Qian^b ; ^{hqian@u.washington.edu" class="auth_mail" title="E-mail the corresponding author}
• 关键词：Chemical nonequilibrium ; Entropy production ; Complex balance ; Macroscopic limit
• 刊名：Chemical Physics
• 出版年：2016
• 出版时间：15 June 2016
• 年：2016
• 卷：472
• 期：Complete
• 页码：241-248
• 全文大小：388 K

文摘

Macroscopic entropy production rate ed0e" title="Click to view the MathML source">σ^(tot)${\sigma }^{(\mathit{tot})}$ in the general nonlinear isothermal chemical reaction system with mass action kinetics is decomposed into a free energy dissipation rate and a house-keeping heat dissipation rate: σ^(tot)=σ^(fd)+σ^(hk)${\sigma }^{(\mathit{tot})}={\sigma }^{(\mathit{fd})}+{\sigma }^{(\mathit{hk})}$; ed5229b2a5f26f43c06f16" title="Click to view the MathML source">σ^(fd)=-dA/dt${\sigma }^{(\mathit{fd})}=-\text{d}A/\text{d}t$, where A   is a generalized free energy function. This yields a novel nonequilibrium free energy balance equation dA/dt=-σ^(tot)+σ^(hk)$\text{d}A/\text{d}t=-{\sigma }^{(\mathit{tot})}+{\sigma }^{(\mathit{hk})}$, which is on a par with celebrated entropy balance equation e97ff489c5bdab7d060e" title="Click to view the MathML source">dS/dt=σ^(tot)+η^(ex)$\text{d}S/\text{d}t={\sigma }^{(\mathit{tot})}+{\eta }^{(\mathit{ex})}$ where η^(ex)${\eta }^{(\mathit{ex})}$ is the rate of entropy exchange with the environment. For kinetic systems with complex balance, σ^(fd)${\sigma }^{(\mathit{fd})}$ and σ^(hk)${\sigma }^{(\mathit{hk})}$ are the macroscopic limits of stochastic free energy dissipation rate and house-keeping heat dissipation rate, which are both nonnegative, in the Delbrück–Gillespie description of the stochastic chemical kinetics. A full kinetic and thermodynamic theory of chemical reaction systems that transcends mesoscopic and macroscopic levels emerges.