Nonextensive Approach to Thermodynamics: Analysis and Suggestions, and Application to Chemical Reactivity
Nonextensive Approach to Thermodynamics: Analysis and Suggestions, and Application to Chemical Reactivity
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热力学非广延方法：分析和建议以及在化学反应中的应用
DOI：
10.1021/jp046849
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发表时间：
2004
影响因子：
3.3
通讯作者：
P. Letellier
中科院分区：
文献类型：
--
作者：
M. Turmine;A. Mayaffre;P. Letellier
在微观异质反应介质中，例如液滴、雾、多孔基质、胶束溶液、互穿相，化学反应性在某些情况下不仅取决于反应物的性质和比例，还取决于系统的形状、尺寸和结构。这种行为无法在经典热力学的严格框架中使用广泛的状态函数来描述。物理学家已经证明，通过使用非广延状态函数，可以将热力学的应用领域扩展到此类问题。因此，通过统计方法，C. Tsallis 提出了一种涉及分形维数的非广延形式的熵。尽管从基本角度来看，所建议的功能很有趣，但化学家通常很难利用它们。因此，我们尝试以另一种方式解决这个问题，并提出经典热力学规则的概括，以便它们能够适应描述......
In microscopic heterogeneous reaction media, such as drops, fogs, porous substrates, micellar solutions, interpenetrated phases, chemical reactivity depends, in some cases, not only on the nature and the proportion of reactants but also on the shape, the size, and the structure of the system. This kind of behavior cannot be described in the strict framework of classical thermodynamics using extensive state functions. Physicists have shown that it is possible to extend the application field of thermodynamics to this kind of problem by using nonextensive state functions. Thus, by a statistical approach, C. Tsallis proposed a nonextensive form of the entropy which involves a fractal dimension. Although the suggested functions are interesting from a fundamental point of view, they are often difficult for the chemist to exploit. Therefore, we have attempted to tackle this problem in another way and propose a generalization of the rules of classical thermodynamics so that they can be adapted to the description ...