关于玻尔兹曼熵的广泛性的评论

Rol, Riek, Alex, E. Sobol'
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引用次数: 5

摘要

在热力学中,熵是一个广义的状态函数。它由统计力学根据玻尔兹曼和吉布斯用著名的公式S=kBlnW推导出的N个粒子的微正则系综,kB为玻尔兹曼常数,W为可达的微态数,但通常不广泛,除非由lnN!—“NlnN + N”。此外,在恒定密度下粒子数N→∞的热力学极限下,由于limN→∞(lnN!—NlnN + N)=∞。因此,这里所示的理想气体的玻尔兹曼熵S既不适用于有N个粒子的小系统,也不适用于热力学极限。因此,如果要求熵的严格延展性,那么统计力学关于玻尔兹曼熵是其热力学类似物的微观描述的说法就受到了挑战。
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Comments on the Extensivity of the Boltzmann Entropy
In thermodynamics entropy Std is an extensive state function. Its derivation by statistical mechanics following Boltzmann and Gibbs with the famous formula S=kBlnW for a micro-canonical ensemble with N particles, kB the Boltzmann constant, and W the number of accessible micro-states is however in general not extensive unless the Stirling approximation given by lnN! – NlnN + N is used. Furthermore, at the thermodynamic limit with the number of particles N→∞ at constant density the Stirling approximation can not be used to show extensivity because limN→∞ (lnN! – NlnN + N)=∞. Hence, the Boltzmann entropy S as shown here for the ideal gas is neither for a small system with N particles nor at the thermodynamic limit extensive. Thus, if strict extensivity for the entropy is requested the claim of statistical mechanics that the Boltzmann entropy is a microscopic description of its thermodynamic analog is challenged.
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