Souda Ryutaro
Nanoscale Materials Center, National Institute for Materials Science, 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan.
J Phys Chem B. 2007 Sep 27;111(38):11209-13. doi: 10.1021/jp0725580. Epub 2007 Aug 31.
Interactions of sodium chloride with amorphous and crystalline water films, leading to the possible formation of a dilute NaCl solution, were investigated using time-of-flight secondary ion mass spectrometry as a function of temperature. A monolayer of NaCl tends to remain on the surface or in subsurface sites of thick amorphous solid water films (200 monolayers); the Na+ ion is hydrated preferentially, whereas the Cl- ion is segregated at the surface. The hydration structure of NaCl is fundamentally unchanged for viscous liquid water that appears at temperatures higher than 136 K. The solubility of NaCl increases abruptly at 160 K because of the evolution of supercooled liquid water, which can hydrate the Cl- ion efficiently. However, the diffusion of the ions toward the bulk of supercooled liquid water is interrupted by crystallization; therefore, the dilute NaCl solution that is characterized by completely separated Na+-Cl- pairs may not be formed. When NaCl is deposited on the crystalline ice film, hydration of NaCl is enhanced above 160 K as well, indicating that a liquidlike phase coexists with crystals.
利用飞行时间二次离子质谱法研究了氯化钠与非晶态和晶态水膜的相互作用,这种相互作用可能导致稀氯化钠溶液的形成,并考察了其随温度的变化情况。单层氯化钠倾向于保留在厚非晶态固体水膜(200个单层)的表面或次表面位置;Na⁺离子优先被水合,而Cl⁻离子则在表面偏析。对于温度高于136K时出现的粘性液态水,氯化钠的水合结构基本不变。由于过冷液态水的形成,氯化钠的溶解度在160K时突然增加,过冷液态水能够有效地水合Cl⁻离子。然而,离子向大量过冷液态水的扩散被结晶中断;因此,可能无法形成以完全分离的Na⁺-Cl⁻对为特征的稀氯化钠溶液。当氯化钠沉积在结晶冰膜上时,氯化钠的水合作用在160K以上也会增强,这表明类液相与晶体共存。