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物理化学力学与非平衡化学热力学

Physicochemical Mechanics and Nonequilibrium Chemical Thermodynamics.

作者信息

Kocherginsky Nikolai Meerovich

机构信息

Next-ChemX, University of Illinois at Urbana-Champaign, Hazelwood Dr., Champaign, IL 61820-7460, USA.

出版信息

Entropy (Basel). 2023 Sep 14;25(9):1332. doi: 10.3390/e25091332.

Abstract

Equilibrium thermodynamics answers the question, "by how much?" Nonequilibrium thermodynamics answers the question "how fast?" The physicochemical mechanics approach presented in this article answers both of these questions. It also gives equilibrium laws and expressions for all major transport coefficients and their relations, which was previously impossible. For example, Onsager's reciprocal relations only tell us that symmetric transport coefficients are equal, and even for these, the value is often not known. Our new approach, applicable to non-isolated systems, leads to a new formulation of the second law of thermodynamics and agrees with entropy increase in spontaneous processes for isolated systems. Instead of entropy, it is based on a modified Lagrangian formulation which always increases during system evolution, even in the presence of external fields. This article will present numerous examples of physicochemical mechanics can be applied to various transport processes and their equilibriums, including thermodiffusion and different surface processes. It has been proven that the efficiency of a transport process with an actual steady-state flux (as opposed to a reversible process near equilibrium) is 50%. Finally, an analogy between physicochemical mechanics and some social processes is mentioned.

摘要

平衡热力学回答的问题是“多少?”非平衡热力学回答的问题是“多快?”本文所介绍的物理化学力学方法能回答这两个问题。它还给出了所有主要输运系数的平衡定律和表达式以及它们之间的关系,这在以前是不可能的。例如,昂萨格互易关系只告诉我们对称输运系数相等,即便如此,其数值通常也未知。我们适用于非孤立系统的新方法,引出了热力学第二定律的新表述,并且与孤立系统自发过程中的熵增加相一致。它不是基于熵,而是基于一种修正的拉格朗日表述,这种表述在系统演化过程中总是增加的,即使存在外场时也是如此。本文将给出物理化学力学可应用于各种输运过程及其平衡的大量例子,包括热扩散和不同的表面过程。已经证明,具有实际稳态通量的输运过程(与接近平衡的可逆过程相对)的效率为50%。最后,提到了物理化学力学与一些社会过程之间的类比。

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