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Ultrasonic detection of hydrophobic interactions: a quantitative approach
Author(s) -
Tuulmets Ants,
Järv Jaak,
Salmar Siim,
Cravotto Giancarlo
Publication year - 2008
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.1415
Subject(s) - chemistry , solvolysis , sonication , reagent , solvent , hydrophobic effect , hydrolysis , ethanol , chloride , methanol , organic chemistry , chromatography
Abstract Kinetic effects of sonication on ester hydrolysis and tert ‐butyl chloride solvolysis, studied in ethanol–water binary solvent, are discussed in terms of quantitative relationships between their magnitude and the hydrophobicity of reagents. A number of conclusions were drawn from the observed linear free‐energy (LFE) relationships. Independent of reaction mechanism, the decrease in reaction rates with increasing ethanol content in the solvent is mainly due to hydrophobic stabilization of the ground state. While hydrophobic species can be hidden in the ethanol clusters present in the region X EtOH > 0.15, at lower ethanol contents hydrophobic reagents are weakly solvated and the hydrophobic stabilization can be easily overcome by sonication. Copyright © 2008 John Wiley & Sons, Ltd.