Isocompositional liquid-liquid transition in dilute aqueous LiCl solutions

Abstract

We here demonstrate that small amounts of LiCl dissolved in water extend the existence window of deeply supercooled liquid water. This shift allows us to observe the isocompositional, sharp liquid-liquid transition (LLT), while this is not possible in pure water. Upon heating at ambient pressure, the hyperquenched and densified glass first turns into the high-density liquid (HDL) and then experiences the LLT to the low-density liquid (LDL) at 137–141 K and ambient pressure. At the LLT the viscosity suddenly jumps up by an order of magnitude, from ∼4.3×109Pas in HDL to ∼3.7×1010Pas in LDL for the 3.1 mol % solution based on our calorimetric analysis. That is, the LLT takes place clearly in the ultraviscous liquid domain at ambient pressure. By contrast, the viscosity of the emerging LDL at the LLT is still in the domain of the soft glass for pure water and for solutions exceeding 5 mol % LiCl that were studied in the past. This is owing to our observation that, first, the LDL's glass transition is lowered by about 8 K to 126 K in the presence of small amounts LiCl, whereas the HDL's glass transition remains at 118 K. Second, the stability of HDL at ambient pressure is increased by high-pressure annealing, shifting the LLT to higher temperatures. Published by the American Physical Society 2024