Discriminative ionic polarizability of alkali halide solutions: Hydration cells, bond distortion, surface stress, and viscosity
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Sun, Wei
Tong, Zhibo
Bo, Maolin
Ostrikov, Kostya Ken
Huang, Yongli
Sun, Chang Q
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Abstract
Understanding the performance of individual ions in salt solutions and the consequence of ionic hydration on hydrogen bonding network distortion, surface stress, and solution viscosity remains great challenge. We show herein findings pertained to alkali halide YX solutions using differential phonon spectroscopy (X = Cl, Br, I; Y = Li, Na, K, Rb, Cs): (i) an ion occupies eccentrically the tetrahedrally-coordinated interstitial of water to form a (±:4H2O:6H2O) hydration cell without bonding to H2O molecules; (ii) ionic polarization shortens and stiffens the H-O bond while does the O:H nonbond contrastingly; (iii) the screening of the hydrating water dipoles limits the cation hydration cell to be size invariant while the inter-anion repulsion reduces its hydration volume by weakening the anionic long-range electric field when the ionic separation shrinks; and (iv) the polarization of cation and anion dictates respectively the linear and the nonlinear part of Jones-Dale's viscosity and surface stress. Findings would provide profound impact to the understanding and deep engineering of water, ice, and aqueous solutions.
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Journal of Molecular Liquids
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348
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Science & Technology
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Chemistry, Physical
Physics, Atomic, Molecular & Chemical
Chemistry
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Li, L; Sun, W; Tong, Z; Bo, M; Ostrikov, KK; Huang, Y; Sun, CQ, Discriminative ionic polarizability of alkali halide solutions: Hydration cells, bond distortion, surface stress, and viscosity, Journal of Molecular Liquids, 2022, 348, pp. 118062