Icebergs or no Icebergs in aqueous alcohols?: Composition-dependent mixing schemes
Icebergs or no Icebergs in aqueous alcohols?: Composition-dependent mixing schemes
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DOI：
10.1021/jp0312722
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发表时间：
2004-04
影响因子：
2.9
通讯作者：
Y. Koga;K. Nishikawa;P. Westh
中科院分区：
文献类型：
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作者：
Y. Koga;K. Nishikawa;P. Westh
我们最近的热力学研究修正了“冰山形成”的经典概念。H2O的氢键网络在小的非电解质溶质附近的局部增强（即，“冰山形成”）仍然是正确的。然而，大量的H2O远离溶质的氢键的概率逐渐减少，作为溶质组合物的增加。当大量的H2O的氢键概率减少到键渗流阈值的六边形冰连接，氢键渗流失去了一个定性不同的混合方案集，从而解决方案由两种集群。在富含溶质的区域，溶质分子形成自己的簇。因此，“冰山的形成”基本上是正确的，在一个狭窄的范围内，在H2O丰富的区域为小的非电解质溶质。因此，对近年来文献中提到的“冰山”概念，应根据溶质的浓度范围和大小加以澄清。
The classical concept of “iceberg formation” is modified by our recent thermodynamic studies. The local enhancement of the hydrogen-bond network of H2O in the immediate vicinity of small nonelectrolyte solutes (i.e., the “iceberg formation”) is still correct. However, the hydrogen-bond probability of bulk H2O away from solutes is reduced progressively, as the solute composition increases. When the hydrogen-bond probability of bulk H2O is reduced to the bond percolation threshold of the hexagonal ice connectivity, the hydrogen-bond percolation is lost and a qualitatively different mixing scheme sets in, whereby the solution consists of two kinds of clusters. In the solute-rich region, solute molecules form clusters of its own kind. Thus, the “iceberg formation” is basically correct within a narrow range in the H2O-rich region for small nonelectrolyte solutes. Thus, reference made to the “iceberg” concept in recent literatures should be clarified in terms of the concentration range and the size of solute in...