Size Dependence of Transfer Free Energies. 2. Hard Sphere Models
Size Dependence of Transfer Free Energies. 2. Hard Sphere Models
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DOI：
10.1021/jp960668t
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发表时间：
1996-08
期刊：
影响因子：
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通讯作者：
K. Sharp;Sanat K. Kumar;P. Rossky;R. Friedman;B. Honig
中科院分区：
文献类型：
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作者：
K. Sharp;Sanat K. Kumar;P. Rossky;R. Friedman;B. Honig
本文和以前的论文1的主要目标是确定摩尔体积是否对溶质分子在不同相之间的分配有重要贡献。前一篇论文考虑了链状溶剂分子的混合熵，其中发现链连接性引起的体积效应会提高溶解溶质的化学势。在本文中，我们考虑的情况下，球形溶剂分子。导出了在可加体积条件下硬球混合熵的表达式。除了建议如何体积效应可能与分子的形状，我们的研究结果使我们能够考虑各种理论之间的关系，有相关的混合熵摩尔体积。结果表明，体积依赖的贡献溶剂化熵可以解释在涉及硬球或理想压力，而不是环境压力的压力-体积效应。熵效应直接来自于自由体积r的变化。
The primary goal of this and a previous paper1 is to determine whether molar volume makes significant contributions to the partitioning of solute molecules between different phases. The previous paper considered the entropies of mixing of chainlike solvent molecules where volume effects arising from chain connectivity were found to raise the chemical potential of dissolved solutes. In this paper we consider the case of spherical solvent molecules. An expression is derived for the entropy of mixing of hard spheres under additive volume conditions. In addition to suggesting how volume effects may be related to molecular shape, our results allow us to consider the relationship between various theories which have related mixing entropies to molar volume. It is shown that volume-dependent contributions to solvation entropies can be interpreted in terms of pressure−volume effects involving hard sphere or ideal pressure rather than ambient pressures. Entropic effects result directly from changes in free volume r...