First-Order Liquid–Liquid Transition without Density Discontinuity in Molten Sodium Acetate Trihydrate and Its Influence on Crystallization

Liquid–liquid transition (LLT) refers to the phase transition among thermodynamically distinct liquid states with identical composition in analogy to the polymorphic transition in solid. The growing awareness of its significance to understanding the nature of liquid also provokes curiosity about its potential impact on crystallization. Here, we report a first-order liquid–liquid transition above liquidus temperature in the melt of sodium acetate trihydrate using nuclear magnetic resonance, differential scanning calorimetry, and high-precision density measurements, which show negligible change in density associated with the observed LLT. Further, the kinetics and products of crystallization are significantly influenced by LLT, providing a new way for the controlling crystallization pathway and realizing crystal polymorph selection.