Countercations Control Local Specific Bonding Interactions and Nucleation Mechanisms in Concentrated Water-in-Salt Solutions

Wang, Hsiu-Wen; Graham, Trent R.; Mamontov, Eugene; Page, Katharine; Stack, Andrew G.; Pearce, Carolyn I.

doi:10.1021/acs.jpclett.9b01416

Title: Countercations Control Local Specific Bonding Interactions and Nucleation Mechanisms in Concentrated Water-in-Salt Solutions

Journal Article · 29 May 2019 · Journal of Physical Chemistry Letters

DOI: https://doi.org/10.1021/acs.jpclett.9b01416 · OSTI ID:1524854

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Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

One of the continuing difficulties presented in salt solutions is understanding ion association reactions driving dynamic demixing from solvation, complexation, and solute clustering. The problems understanding this phenomenon are exacerbated in the highly concentrated water-in-salt solutions, where the deficiency of water leads to a dramatic retardation of water solvent and formation of extended solvent–solute clustering networks. By probing microscopic dynamics of water and prenucleation clusters using quasi-elastic neutron scattering and proton nuclear magnetic resonance spectroscopy, we observed contrasting mechanistic specifics of ion–water mobilities in highly concentrated Na⁺- versus K⁺-based aluminate solutions (diffusion coefficients of 0.2 vs 2.6 × 10^–10 m² s^–1 at 293 K, respectively). The magnitude of the differences is far beyond countercations acting as simple innocent charge-balancing species or water solvents functioning as a simple medium for ion diffusion. The distinct crystallization mechanisms studied further imply that different prenucleation cluster dynamics can either frustrate or promote crystallization, as described by nonclassical nucleation theory.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Interfacial Dynamics in Radioactive Environments and Materials (IDREAM); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1524854

Alternate ID(s):: OSTI ID: 1567252

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: n/a Vol. 10; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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