Ruiz Guadalupe N, Amann-Winkel Katrin, Bove Livia E, Corti Horacio R, Loerting Thomas
Institute of Physical Chemistry, University of Innsbruck, Innrain 52c, 6020 Innsbruck, Austria.
Phys Chem Chem Phys. 2018 Feb 28;20(9):6401-6408. doi: 10.1039/c7cp08677f.
A DSC study of dilute glassy LiCl aqueous solutions in the water-dominated regime provides direct evidence of a glass-to-liquid transition in expanded high density amorphous (eHDA)-type solutions. Similarly, low density amorphous ice (LDA) exhibits a glass transition prior to crystallization to ice I. Both glass transition temperatures are independent of the salt concentration, whereas the magnitude of the heat capacity increase differs. By contrast to pure water, the glass transition endpoint for LDA can be accessed in LiCl aqueous solutions above 0.01 mole fraction. Furthermore, we also reveal the endpoint for HDA's glass transition, solving the question on the width of both glass transitions. This suggests that both equilibrated HDL and LDL can be accessed in dilute LiCl solutions, supporting the liquid-liquid transition scenario to understand water's anomalies.
对水占主导区域的稀玻璃态LiCl水溶液进行的差示扫描量热(DSC)研究,为膨胀高密度无定形(eHDA)型溶液中的玻璃态到液态转变提供了直接证据。同样,低密度无定形冰(LDA)在结晶为冰I之前表现出玻璃化转变。两个玻璃化转变温度均与盐浓度无关,而热容增加的幅度有所不同。与纯水相比,在摩尔分数高于0.01的LiCl水溶液中可以达到LDA的玻璃化转变终点。此外,我们还揭示了HDA玻璃化转变的终点,解决了两个玻璃化转变宽度的问题。这表明在稀LiCl溶液中可以达到平衡的高密度液体(HDL)和低密度液体(LDL),支持了液-液转变的设想来理解水的异常现象。