水在其双结点上的惊人性质反映了分子间相互作用的特异性
Surprising properties of water on its binodal as the reflection of the specificity of intermolecular interactions
摘要：
本文讨论了正常水和重水的密度（或比容）、蒸发热和分子熵在它们共存曲线上的行为。特别注意水和氩以及最近的水同系物$H_{2} S$的密度和蒸发热行为的相似性的物理本质。它示出，这种相似性的外观是水分子的旋转运动的结果，其平均在水中的粒子间的潜力，并导致它的氩样的形式。为了描述水和氩的双节点行为的细微差别，考虑了适当的分子体积对压力的依赖性。根据这一点，对常用的范德瓦尔斯和卡纳汉-斯塔林状态方程进行了修正。分析了水的熵直径的非常令人惊讶的行为。它示出的熵直径的温度依赖性的非平凡的细节是直接连接到水中的分子的旋转运动的特性。详细研究了水分子在临界点附近涨落区的强二聚效应。发现在临界点附近形成二聚体$(D_{2} O)_{2} $的单体发生内旋转。
英文摘要：
In the paper the behavior of density (or specific volume), the heat of evaporation and entropy per molecule for normal and heavy water on their coexistence curves is discussed. The special attention is paid on the physical nature of the similarity in the behavior of density and the heat of evaporation for water and argon as well as the nearest water homolog $H_{2} S$. It is shown that the appearance of this similarity is a consequence of the rotational motion of water molecules, which averages the inter-particle potential in water and leads it to the argon-like form. To describe the fine distinctions in the behavior of the binodals for water and argon the dependence of the proper molecular volume on pressure is taken into account. In accordance with this often used the van der Waals and Carnahan-Starling equations of states are modified. The very surprising behavior of the entropy diameter for water is analyzed. It is shown that the nontrivial details of the temperature dependence for the entropy diameter is directly connected with the peculiarities of the rotational motion of molecules in water. The effect of strong dimerization of water molecules in the fluctuation region near the critical point is studied in details. The inner rotation of monomers forming the dimer $(D_{2} O)_{2} $ near the critical point is discovered.
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