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Analysis of open system Carnot cycle and state functions

机译：开放系统卡诺循环和状态函数分析

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摘要

A first principle analysis of an open system thermodynamical Carnot cycle is provided and the results are compared to those proposed by Gibbs for open systems. The Kelvin-Clausius statement concerning heat transfer for reversible cycles is taken as an axiom, from which several rigorous theorems are proven. An equation is derived that resembles a Gibbs-Duhern relation equating convected entropies, from which two distinguishable forms of entropy are proven to exist for such systems; this questions prevailing developments which presume a singular or characteristic entropic form that couple all work and heat flows, such as in Onsager first-order thermodynamics. In particular, a closed path undergone by the system does not return the environment to the initial state for one of these entropic forms. The Biot assertion that the entropy contribution due to diathermal heat transfer does not form a state function is therefore contradicted and a local entropy is shown to exist. Several other new composite state functions for work and heat flow are shown to exist for open systems. From Gibbs' results, it is suggested that the ensuing chemical potentials used routinely may possibly ignore heat effects. The functions developed here are suitable for application since the functions are proven to exist, rather than presumed to exist. (C) 2004 Elsevier Ltd. All rights reserved.
机译：提供了一个开放系统热力学卡诺循环的第一原理分析，并将结果与​​Gibbs提出的用于开放系统的结果进行了比较。关于可逆循环传热的开尔文-克劳修斯（Kelvin-Clausius）陈述被视为一个公理，据此证明了几个严格的定理。推导出一个方程，该方程类似于对流熵的Gibbs-Duhern关系，从中证明了这种系统存在两种可区分的熵形式。这就质疑了目前的发展趋势，这些发展趋势假定一种将所有功和热流耦合在一起的奇异或特性熵形式，例如在Onsager一阶热力学中。特别地，对于这些熵形式之一，系统所经历的闭合路径不会使环境返回到初始状态。 Biot断言，由于热传热引起的熵贡献没有形成状态函数，因此这是矛盾的，并且表明存在局部熵。对于开放系统，还存在用于工作和热流的其他几个新的复合状态函数。根据吉布斯的结果，建议常规使用的随后化学势可能会忽略热效应。此处开发的功能适合于应用，因为这些功能已被证明存在，而不是假定存在。 （C）2004 Elsevier Ltd.保留所有权利。

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