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Hydrotropy and scattering: Pre-ouzo as extended near-spinodal region

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JournalPhysical Chemistry Chemical Physics
DateSubmitted - 24 Jul 2017
DateAccepted/In press - 4 Sep 2017
DateE-pub ahead of print - 26 Sep 2017
DatePublished (current) - 21 Oct 2017
Issue number39
Volume19
Number of pages9
Pages (from-to)26734-26742
Early online date26/09/17
Original languageEnglish

Abstract

Solubilization or mixing in the presence of hydrotropes are often accompanied by the increase of scattering intensity. When the scattering corresponding to mesoscale structuring grows, the mixed state is called “pre-ouzo” aggregate, which appears often and is distinct from critical density fluctuation, yet its precise mechanism of appearance is still obscure. Combining the results from the theories of scattering and thermodynamic phase stability with differential geometry, we constructed a theory which can account for hydrotrope mixing thermodynamics and the pre-ouzo effect in a unified manner. In addition, another well-known signature of hydrotropy, the minimum hydrotrope concentration (MHC) at which solubility of sparingly soluble hydrophobic solutes suddenly increase, has also been linked to the scattering increase. The thermodynamic signatures of the pre-ouzo effect and MHC reveal a mechanistic difference between them, which manifests in the thermodynamic order of derivatives.

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