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Precipitation in aqueous mixtures with addition of a strongly hydrophilic or hydrophobic solute
1Department of Physics, Kyoto University, Kyoto 606-8502, Japan.
Abstract:
We examine phase separation in aqueous mixtures due to preferential solvation with a low-density solute (hydrophilic ions or hydrophobic particles). For hydrophilic ions, preferential solvation can stabilize water domains enriched with ions. This precipitation occurs above a critical solute density n(p) in wide ranges of the temperature and the average composition, where the mixture solvent would be in a one-phase state without solute. The volume fraction of precipitated domains tends to zero as the average solute density n is decreased to np or as the interaction parameter χ is decreased to a critical value χ(p). If we start with one-phase states with n>n(p) or χ>χ(p), precipitation proceeds via homogeneous nucleation or via heterogeneous nucleation, for example, around suspended colloids. In the latter case, colloid particles are wrapped by thick wetting layers. We also predict a first-order prewetting transition for n or χ slightly below np or χ(p) for neutral colloids.
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