Shimizu, Seishi orcid.org/0000-0002-7853-1683 and Matubayasi, Nobuyuki (2017) Unifying hydrotropy under Gibbs phase rule. Physical Chemistry Chemical Physics. pp. 23597-23605. ISSN 1463-9084
Abstract
The task of elucidating the mechanism of solubility enhancement using hydrotropes has been hampered by the wide variety of phase behaviour that hydrotropes can exhibit, encompassing near-ideal aqueous solution, self-association, micelle formation, and micro-emulsions. Instead of taking a field guide or encyclopedic approach to classify hydrotropes into different molecular classes, we take a rational approach aiming at constructing a unified theory of hydrotropy based upon the first principles of statistical thermodynamics. Achieving this aim can be facilitated by the two key concepts: (1) the Gibbs phase rule as the basis of classifying the hydrotropes in terms of the degrees of freedom and the number of variables to modulate the solvation free energy; (2) the Kirkwood-Buff integrals to quantify the interactions between the species and their relative contributions to the process of solubilization. We demonstrate that the application of the two key concepts can in principle be used to distinguish the different molecular scenarios at work under apparently similar solubility curves observed from experiments. In addition, a generalization of our previous approach to solutes beyond dilution reveals the unified mechanism of hydrotropy, driven by a strong solute-hydrotrope interaction which overcomes the apparent per-hydrotrope inefficiency due to hydrotrope self-clustering.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | This journal is © the Owner Societies 2017. .This is an author-produced version of the published paper. Uploaded in accordance with the publisher’s self-archiving policy. Further copying may not be permitted; contact the publisher for details. |
Dates: |
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Institution: | The University of York |
Academic Units: | The University of York > Faculty of Sciences (York) > Chemistry (York) |
Depositing User: | Pure (York) |
Date Deposited: | 23 May 2017 14:30 |
Last Modified: | 25 Dec 2024 00:15 |
Published Version: | https://doi.org/10.1039/c7cp02132a |
Status: | Published |
Refereed: | Yes |
Identification Number: | 10.1039/c7cp02132a |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:116832 |
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