Theory of effective interactions between identical and different non-ionic solutes in a binary solvent

Ryuichi Okamoto

Physica A: Statistical Mechanics and its Applications, 2024, vol. 651, issue C

Abstract: The introduction of cosolvents and other additives significantly has a profound impact on the physicochemical properties and phases of solutions. This study develops a thermodynamic theory to investigate the effective interactions between identical and different non-ionic solutes in a binary solvent. We derive the rigorous thermodynamic identity for the osmotic second virial coefficients among two solute species, which includes an adsorption contribution unique to multi-component solvents. Numerical analyses based on a model free energy show that co-nonsolvency and depletion effects between the identical solute species emerge from this adsorption contribution. On the other hand, the adsorption contribution intensifies the repulsion between different solute species that exhibit opposite preferences to the solvent components. These findings unify seemingly disparate phenomena under a common framework, providing insights into solute–solute and intra-molecular interactions in mixed solvents.

Keywords: Osmotic second virial coefficient; Co-nonsolvency; Depletion interaction; Kirkwood–Buff integral (search for similar items in EconPapers)
Date: 2024
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Persistent link: https://EconPapers.repec.org/RePEc:eee:phsmap:v:651:y:2024:i:c:s0378437124005429

DOI: 10.1016/j.physa.2024.130033

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