Van Lith Janneke
Department of Philosophy and Religious Studies, Utrecht University, Janskerkhof 13, 3512 BL Utrecht, The Netherlands.
Entropy (Basel). 2018 Apr 30;20(5):328. doi: 10.3390/e20050328.
The Gibbs paradox in statistical mechanics is often taken to indicate that already in the classical domain particles should be treated as fundamentally indistinguishable. This paper shows, on the contrary, how one can recover the thermodynamical account of the entropy of mixing, while treating states that only differ by permutations of similar particles as distinct. By reference to the orthodox theory of thermodynamics, it is argued that entropy differences are only meaningful if they are related to reversible processes connecting the initial and final state. For mixing processes, this means that processes should be considered in which particle number is allowed to vary. Within the context of statistical mechanics, the Gibbsian grandcanonical ensemble is a suitable device for describing such processes. It is shown how the grandcanonical entropy relates in the appropriate way to changes of other thermodynamical quantities in reversible processes, and how the thermodynamical account of the entropy of mixing is recovered even when treating the particles as distinguishable.
统计力学中的吉布斯佯谬常被认为表明,即使在经典领域,粒子也应被视为本质上不可区分的。相反,本文展示了如何在将仅通过相似粒子排列而不同的状态视为不同状态的同时,恢复混合熵的热力学解释。通过参考正统的热力学理论,有人认为,只有当熵差与连接初始态和终态的可逆过程相关时,它们才有意义。对于混合过程,这意味着应考虑粒子数允许变化的过程。在统计力学的背景下,吉布斯巨正则系综是描述此类过程的合适工具。本文展示了巨正则熵如何以适当方式与可逆过程中其他热力学量的变化相关,以及即使将粒子视为可区分的,如何恢复混合熵的热力学解释。