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Linear similarity relationships were discovered for these data over the full range of solvent compositions studied. Kinetic data for the pH-independent hydrolysis of (4-methoxyphenyl)-2,2-dichloroacetate measured in this work and solubility data for naphthalene, and other substrates of low polarity, in aqueous binary mixtures of methanol, ethanol, acetonitrile, dimethyl sulfoxide (DMSO), and 1,4-dioxane were used.

The solvation effects observed in water-organic solutions were studied by combining data for reaction kinetics and dissolution equilibria by means of a linear free-energy (similarity) analysis. Many of the conclusions reviewed in this article make a contribution to the chemistry of solutions and physical organic chemistry. On the contrary, if sonication perturbs the stabilization of encounter complexes between reagents, it hinders the reaction. When ultrasound suppresses this hydrophobic stabilization of reagents, it accelerates the reaction. Correlation of kinetic sonication effects with substrate hydrophobicity has revealed that independent of the reaction mechanism the decrease in reaction rate with the increasing content of different hydrophobic co-solvents can be explained by the reaction ground-state stabilization, which is largely of hydrophobic origin.

In this mini-review we summarize these experimental data, showing that the application of classical quantitative methods, such as reaction kinetics and correlation analysis, if combined with sonication of the reaction medium, can reveal subtle hydrophobic interactions that remain hidden in the conventional experiments. Besides the well-known role of ultrasound in initiation and acceleration of radical reactions, this low-energy acoustic field has recently become a valuable tool for physico-chemical investigations of solvation phenomena in homogeneous ionic reactions in aqueous and aqueous-organic solutions.

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