Local molecular environment drives speciation and reactivity of ion complexes in concentrated salt solution

N Rampal and HW Wang and D Biriukov and AB Brady and JC Neuefeind and M Predota and AG Stack, JOURNAL OF MOLECULAR LIQUIDS, 340, 116898 (2021).

DOI: 10.1016/j.molliq.2021.116898

The speciation and reactivity of aqueous salt solutions are important for a wide variety of applications. However, application of this information is inhibited by broad disagreement about composition, mechanisms, and structure in concentrated solutions especially. Here, neutron diffraction with isotopic substitution measurements on aqueous zinc chloride solutions are used to calibrate molecular dynamics simulations that include effective electronic polarization. This allows us to probe the origin of speciation and reactivity of zinc chloride- water ion complexes, ZnClx(H2O)(y)(2-x) (x <= 4 and y <= 6), by comparing the reactivity of species in concentrated (4.5 m) and dilute (0.01 m) conditions. Within the concentrated solution, it is found that the extended solvation environment is dominated by solvent-separated ion complexes whose presence increases the free energy of activation for interconversion of species while simultaneously enhancing their thermodynamic stability. This concentration-dependent reactivity and stability suggests that other reactions, such as the nucleation of solid phases, will also be affected. (C) 2021 The Authors. Published by Elsevier B.V.

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