Nucleation in aqueous NaCl solutions shifts from 1-step to 2-step mechanism on crossing the spinodal

Abstract

In this work, we use large-scale molecular dynamics simulations coupled to free energy calculations to identify for the first time a limit of stability (spinodal) and a change in the nucleation mechanism in aqueous NaCl solutions. This is a system of considerable atmospheric, geological and technical significance. We find that the supersaturated metastable NaCl solution reaches its limit of stability at sufficiently high salt concentrations, as indicated by the composition dependence of the salt chemical potential, indicating the transition to a phase separation by spinodal decomposition. However, the metastability limit of the NaCl solution does not correspond to spinodal decomposition with respect to crystallization. We find that beyond this spinodal, a liquid/amorphous separation occurs in the aqueous solution, whereby the ions first form disordered clusters. We term these clusters as "amorphous salt". We also identify a transition from one- to two-step crystallization mechanism driven by a spinodal. In particular, crystallization from aqueous NaCl solution beyond the spinodal is a two-step process, in which the ions first phase-separate into disordered amorphous salt clusters, followed by the crystallization of ions in the amorphous salt phase. In contrast, in the aqueous NaCl solution at concentrations lower than the spinodal, crystallization occurs via a one-step process, as the ions aggregate directly into crystalline nuclei. The change of mechanism with increasing supersaturation underscores the importance of an accurate determination of the driving force for phase separation. The study has broader implications on the mechanism for nucleation of crystals from solutions at high supersaturations.

References in corpus (10)

• Crystal Nucleation in Liquids: Open Questions and Future Challenges in Molecular Dynamics Simulations
• Direct Calculation of Ice Homogeneous Nucleation Rate for a Molecular Model of Water
• Recent Progress in Molecular Simulation of Aqueous Electrolytes: Force Fields, Chemical Potentials and Solubility
• Microscopic Mechanism and Kinetics of Ice Formation at Complex Interfaces: Zooming in on Kaolinite
• Forward Flux Sampling Calculation of Homogeneous Nucleation Rates from Aqueous NaCl Solutions
• A simulation study of homogeneous ice nucleation in supercooled salty water
• Phase transitions in fluctuations and their role in two-step nucleation
• Nucleation barriers in tetrahedral liquids spanning glassy and crystallizing regimes
• Crystallization of Lennard-Jones nanodroplets: from near melting to deeply supercooled
• Amorphous Precursors of Crystallization during Spinodal Decomposition

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