Absence of the liquid-liquid phase transition in aqueous ionic liquids

The anomalies of supercooled water may be explained by an underlying liquid-liquid phase transition (LLPT) between high- and low-density states. Recently, its observation at 185 K was inferred using solutions containing aqueous ionic liquids at a solute mole fraction of x = 0.156 [Woutersen et al., Science 359, 1127 (2018)]. We employ x-ray diffraction, calorimetry, and dilatometry on these hydrazinium trifluoroacetate solutions at x = 0.00-0.40 to show that the transition at 185 K is not related to a genuine LLPT of water. Continuous densification upon compression, continuous changes of halo position, and absence of thermal signatures for a high- to low-density transition rule out the possibility of an LLPT for x >= 0.13. The data show that employing sophisticated solutions adds a layer of complexity that hampers extrapolation of the LLPT concept from one- to two-component systems. The possibility of an LLPT can only be probed for pure water or sufficiently dilute aqueous solutions.