A temperature programmed desorption study of interactions between water and hydrophobes at cryogenic temperatures

结晶 解吸 氢键 结晶水 无定形固体 热脱附光谱法 化学 化学物理 结晶学 疏水效应 化学工程 分子 物理化学 吸附 有机化学 工程类
作者
R. Souda,Tadaaki Nagao
出处
期刊:Physical Chemistry Chemical Physics [Royal Society of Chemistry]
卷期号:24 (27): 16900-16907 被引量:1
标识
DOI:10.1039/d2cp01580c
摘要

It is considered that hydrophobic solutes dissolve in water via the formation of icelike cages in the first hydration shell. However, this conventional picture is currently under debate. We have investigated how hydrophobic species, such as D2, Ne, Ar, Xe, CH4, and C3H8, interact with water in composite films of amorphous solid water (ASW) based on temperature programmed desorption (TPD). The D2 and Ne species tend to be incorporated in ASW without being caged, whereas two distinct peaks assignable to the caged species are identifiable for the other solutes examined here. The low-temperature peak is observed preferentially for Ar and CH4 prior to crystallization. The hydrophobes are thought to be encapsulated in porous ASW films via reorganization of the hydrogen bond network up to 100 K; most of them are released in a liquidlike phase that occurs immediately before crystallization at ca. 160 K. The nature of hydrophobic hydration at cryogenic temperature appears to differ from that in normal water at room temperature because the former resembles crystalline ices in the local hydrogen-bond structure rather than the latter. No ordered structures assignable to clathrate hydrates were identified before and after crystallization.
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