Apparent First-Order Liquid-Liquid Transition with Pre-transition Density Anomaly, in Water-Rich Ideal Solutions

The striking increases in response functions observed during supercooling of pure water have been the source of much interest and controversy. Imminent divergences of compressibility etc. unfortunately cannot be confirmed due to pre-emption by ice crystallization. Crystallization can be repressed by addition of second components, but these usually destroy the anomalies of interest. Here we study systems in which protic ionic liquid second components dissolve ideally in water, and ice formation is avoided without destroying the anomalies. We observe a major heat capacity spike during cooling, which is reversed during heating, and is apparently of first order. It occurs just before the glassy state is reached and is preceded by water-like density anomalies. We propose that it is the much-discussed liquid-liquid transition previously hidden by crystallization. Fast cooling should allow the important fluctuations/structures to be preserved in the glassy state for leisurely investigation. Heat capacities of an aqueous non-ideal salt solution (11.4 mol % LiCl) and an ideal salt solution (14.4 mol % hydrazinium trifluoroacetate) were measured and compared in the temperature range of water anomalies.