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Keywords = Kirkwood-Buff fluctuation theory

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30 pages, 2721 KiB  
Article
Solvent and H/D Isotopic Substitution Effects on the Krichevskii Parameter of Solutes: A Novel Approach to Their Accurate Determination
by Ariel A. Chialvo and Oscar D. Crisalle
Liquids 2022, 2(4), 474-503; https://doi.org/10.3390/liquids2040028 - 15 Dec 2022
Cited by 8 | Viewed by 4462
Abstract
We establish a direct route for the accurate determination of the solvent effect on the Krichevskii parameter of a solute, based solely on the contrasting solvation behavior of the solute in the desired solvent relative to that of the reference solvent, i.e., in [...] Read more.
We establish a direct route for the accurate determination of the solvent effect on the Krichevskii parameter of a solute, based solely on the contrasting solvation behavior of the solute in the desired solvent relative to that of the reference solvent, i.e., in terms of the distinct solvation Gibbs free energies of the solute and the corresponding Krichevskii parameters of an ideal gas solute in the pair of solvents. First, we illustrate the proposed approach in the determination of the H/Dsolvent effect on the Krichevskii parameter of gaseous solutes in aqueous solutions, when the solvents are different isotopic forms (isotopomers) of water, and then, by generalizing the approach to any pair of solvents. For that purpose, we (a) identify the links between the standard solvation Gibbs free energy of the isolute in the two involved solvent environments and the resulting Krichevskii parameters, (b) discuss the fundamentally based linear behavior between the Krichevskii parameter and the standard solvation Gibbs free energy of the isolute in an αsolvent, and interpret two emblematic cases of solutions involving either an ideal gas solute or an isolute behaving identically as the solvating species, as well as (c) provide a novel microstructural interpretation of the solvent effect on the Krichevskii parameter according to a rigorous characterization of the critical solvation as described by a finite unambiguous structure making/breaking parameter Siα(SR) of the isolute in the pair of αsolvents. Full article
(This article belongs to the Section Chemical Physics of Liquids)
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