Polyamorphism Group, Surface Physics and Structure Unit, National Institute for Materials Science, 1-1 Namiki, Tsukuba, 305-0044, Japan.
J Phys Chem B. 2011 Dec 8;115(48):14064-7. doi: 10.1021/jp203669p. Epub 2011 Jul 7.
Melting of the precipitated ice IV in supercooled LiCl-H(2)O solution was studied in the range of 0-0.6 MPa and 160-270 K. Emulsified solution was used to detect this metastable transition. Ice IV was precipitated from the aqueous solution of 2.0 mol % LiCl (or 4.8 mol % LiCl) in each emulsion particle at low-temperature and high-pressure conditions, and the emulsion was decompressed at different temperatures. The melting of ice IV was detected from the temperature change of the emulsified sample during the decompression. There was an apparently sudden change in the slope of the ice IV melting curve (liquidus) in the pressure-temperature diagram. At the high-pressure and high-temperature side of the change, the solute-induced freezing point depression was observed. At the low-pressure and low-temperature side, ice IV transformed into ice Ih on the decompression, and the transition was almost unrelated to the concentration of LiCl. These experimental results were roughly explained by the presumed existence of two kinds of liquid water (low-density liquid water and high-density liquid water), or polyamorphism in water, and by the simple assumption that LiCl dissolved maily in high-density liquid water.
在 0-0.6 MPa 和 160-270 K 的范围内研究了过冷 LiCl-H(2)O 溶液中沉淀冰 IV 的熔融。使用乳化溶液来检测这种亚稳转变。在低温高压条件下,在每个乳液颗粒中的 2.0 mol% LiCl(或 4.8 mol% LiCl)的水溶液中沉淀出冰 IV,然后在不同温度下对乳液进行减压。通过在减压过程中乳化样品的温度变化来检测冰 IV 的熔融。在压力-温度图中,冰 IV 熔融曲线(液相线)的斜率明显突然发生变化。在变化的高压高温侧,观察到溶质诱导的冰点降低。在低压低温侧,冰 IV 在减压下转变为冰 Ih,该转变几乎与 LiCl 的浓度无关。这些实验结果大致可以通过假定存在两种类型的液态水(低密度液态水和高密度液态水)或水的多形性,以及 LiCl 主要溶解在高密度液态水中的简单假设来解释。