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arXiv 1407.0128cond-mat.stat-mech
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多分散体系统计力学中组成熵的作用

On the role of composition entropies in the statistical mechanics of polydisperse systems

Fabien Paillusson, Ignacio Pagonabarraga

摘要:

多分散体系通常在处理一般软物质或任何非简单流体时遇到。然而,在统计热力学的框架内处理它们是一项微妙的任务,因为后者基本上是为简单的-非完全多分散-系统设计的。在本文中,我们解决的问题,为这些系统定义一个非模糊的组合熵。我们这样做的热力学势的扩展性的一般属性,并讨论一个具体的混合实验。这使我们引入新的概念,组成熵的单相系统,我们不同化的混合熵。然后,我们表明,他们没有贡献的热力学系统在固定的组合物,并规定substantial $\ln N!$从自由能表征一个系统,但多分散它可以。然后,我们重新推导任何两个多分散系统之间的混合熵的一般表达式,并解释它们的概率分布之间的距离,并表明,这些指标之一自然涉及到最近的扩展兰道尔的原则。然后,我们提出了限制表达式的混合熵的情况下,混合与原始组成的比例相等,并最终解决化学反应的挑战性问题。

英文摘要:

Polydisperse systems are commonly encountered when dealing with soft matter in general or any non simple fluid. Yet their treatment within the framework of statistical thermodynamics is a delicate task as the latter has been essentially devised for simple --- non fully polydisperse --- systems. In this paper, we address the issue of defining a non ambiguous combinatorial entropy for these systems. We do so by focusing on the general property of extensivity of the thermodynamic potentials and discussing a specific mixing experiment. This leads us to introduce the new concept of composition entropy for single phase systems that we do not assimilate to a mixing entropy. We then show that they do not contribute to the thermodynamics of the system at fixed composition and prescribe to substract $\ln N!$ from the free energy characterizing a system however polydisperse it can be. We then re-derive general expressions for the mixing entropy between any two polydisperse systems and interpret them in term of distances between probability distributions and show that one of these metrics relates naturally to a recent extension of Landauer's principle. We then propose limiting expressions for the mixing entropy in the case of mixing with equal proportion in the original compositions and finally address the challenging problem of chemical reactions.

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