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Keywords = Kirkwood–Buff formalism

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30 pages, 2113 KiB  
Review
Linking Solution Microstructure and Solvation Thermodynamics of Mixed-Solvent Systems: Formal Results, Critical Observations, and Modeling Pitfalls
by Ariel A. Chialvo
Thermo 2024, 4(3), 407-432; https://doi.org/10.3390/thermo4030022 - 22 Sep 2024
Cited by 1 | Viewed by 1510
Abstract
This review provides a critical assessment of the current state of affairs regarding the solvation thermodynamics involving mixed-solvent systems. It focuses specifically on (i) its rigorous molecular-based foundations, (ii) the underlying connections between the microstructural behavior of the mixed-solvent [...] Read more.
This review provides a critical assessment of the current state of affairs regarding the solvation thermodynamics involving mixed-solvent systems. It focuses specifically on (i) its rigorous molecular-based foundations, (ii) the underlying connections between the microstructural behavior of the mixed-solvent environment and its thermodynamic responses, (iii) the microstructural characterization of the behavior of the mixed-solvent environment around the dilute solute via unique fundamental structure-making/-breaking functions and the universal preferential solvation function, (iv) the discussion of potential drawbacks associated with the molecular simulation-based determination of thermodynamic preferential interaction parameters, and (v) the forensic examination of frequent modeling pitfalls behind the interpretation of preferential solvation from experimental data of Gibbs free energy of solute transfer. Full article
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