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

Abstract

Here, 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. By contrast, in the aqueous NaCl solution at concentrations lower than the spinodal, crystallization occurs via a one-step processmore » 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.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]
  1. Univ. of Pennsylvania, Philadelphia, PA (United States)
  2. Princeton Univ., NJ (United States)
Publication Date:
Research Org.:
Princeton Univ., NJ (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1610630
Alternate Identifier(s):
OSTI ID: 1503939
Grant/Contract Number:  
SC0002128
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 150; Journal Issue: 12; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; chemistry; physics

Citation Formats

Jiang, Hao, Debenedetti, Pablo G., and Panagiotopoulos, Athanassios Z. Nucleation in aqueous NaCl solutions shifts from 1-step to 2-step mechanism on crossing the spinodal. United States: N. p., 2019. Web. doi:10.1063/1.5084248.
Jiang, Hao, Debenedetti, Pablo G., & Panagiotopoulos, Athanassios Z. Nucleation in aqueous NaCl solutions shifts from 1-step to 2-step mechanism on crossing the spinodal. United States. https://doi.org/10.1063/1.5084248
Jiang, Hao, Debenedetti, Pablo G., and Panagiotopoulos, Athanassios Z. Fri . "Nucleation in aqueous NaCl solutions shifts from 1-step to 2-step mechanism on crossing the spinodal". United States. https://doi.org/10.1063/1.5084248. https://www.osti.gov/servlets/purl/1610630.
@article{osti_1610630,
title = {Nucleation in aqueous NaCl solutions shifts from 1-step to 2-step mechanism on crossing the spinodal},
author = {Jiang, Hao and Debenedetti, Pablo G. and Panagiotopoulos, Athanassios Z.},
abstractNote = {Here, 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. By 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.},
doi = {10.1063/1.5084248},
journal = {Journal of Chemical Physics},
number = 12,
volume = 150,
place = {United States},
year = {Fri Mar 22 00:00:00 EDT 2019},
month = {Fri Mar 22 00:00:00 EDT 2019}
}

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