On the Validity of the Assumption of Local Equilibrium in Non-Equilibrium Thermodynamics

Validity of path thermodynamics in reactive systems

Path thermodynamic formulation of non-equilibrium reactive systems is considered. It is shown through simple practical examples that this approach can lead to results that contradict well established thermodynamic properties of such systems. Rigorous mathematical analysis confirming this fact is presented.

Diffusion approximations to the chemical master equation only have a consistent stochastic thermodynamics at chemical equilibrium

The stochastic thermodynamics of a dilute, well-stirred mixture of chemically-reacting species is built on the stochastic trajectories of reaction events obtained from the Chemical Master Equation. However, when the molecular populations are large, the discrete Chemical Master Equation can be approximated with a continuous diffusion process, like the Chemical Langevin Equation or Low Noise Approximation. In this paper, we investigate to what extent these diffusion approximations inherit the stochastic thermodynamics of the Chemical Master Equation. We find that a stochastic-thermodynamic descr…

非平衡区中的经典与量子热力学：应用于 Stirling 热机

Classical and quantum thermodynamics in a non-equilibrium regime: Application to Stirling engine

本文提出基于无量纲极小功原理的非平衡热力学理论，通过引入熵产生率定义非平衡热力学势，无需因子化初始条件假设且适用于完全量子区，并经 Stirling 热机数值模拟验证，为开发非平衡高效热机提供理论基础。

化学平衡作为热力学力的平衡

Chemical Equilibrium as Balance of the Thermodynamic Forces

本文阐述了作为热力学力平衡的化学平衡热力学的综合基础。基于不可逆热力学的线性方程、De Donder热力学力的定义和Le Chatelier原理，新的化学平衡热力学为系统内的多种化学相互作用提供了明确的解释。化学转变的能量特征与反应程度之间的基本关系是基于化学平衡作为内部和外部热力学力之间的平衡的思想，其以仅包含一个新参数的逻辑斯谛方程的形式呈现。基本方程的解定义了化学系统的状态域，从真正的平衡到真正的混沌。新的理论完全来自目前公认的思想，并涵盖了平衡态热力学以及非平衡态热力学在一个独特的概念。

Marcus交叉交换电子转移反应速率的非平衡热力学形式

Non-Equilibrium Thermodynamics formalism for Marcus cross-exchange electron transfer reaction rates

利用Onsager非平衡态热力学理论推导了Marcus理论中的交叉交换电子转移公式。

开放化学体系的热力学平衡

Thermodynamic Equilibrium in Open Chemical Systems

本文提出了一种新的开放化学体系平衡模型，提出了在热力学外力作用下反应偏离平衡的线性关系。该模型的基本方程包含传统的对数项和一个非传统的抛物线项。在孤立平衡时，非传统项等于零，使整个方程变为传统形式的常数方程。这一项与过量热力学函数相吻合，揭示了热力学活度系数的对数与开放平衡时反应程度之间的线性关系。发现的关系促使我们在许多系统中使用线性系数和反应偏离真实平衡的组合，而不是活度系数。线性系数可以通过热力学计算机模拟找到，而位移是定义开放平衡态的自变量。通过各种模拟技术获得的数值数据证明了化学动力学方法的前提。

用南部热力学表述的涨落非线性非平衡系统

Fluctuating Non-linear Non-equilibrium System in Terms of Nambu Thermodynamics

本文提出用广义南部动力学刻画远离平衡且含涨落的非平衡热力学系统，通过三角反应、BZ反应和H-R模型展示南部括号的适用性，并揭示熵演化的周期性及哈密顿量对熵增的抑制作用。

Braun-Le Chatelier principle in dissipative thermodynamics

Braun-Le Chatelier principle is a fundamental result of equilibrium thermodynamics, showing how stable equilibrium states shift when external conditions are varied. The principle follows from convexity of thermodynamic potential. Analogously, from convexity of dissipation potential it follows how steady non-equilibrium states shift when thermodynamic forces are varied, which is the extension of the principle to dissipative thermodynamics.