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Reaction kinetics and solubility in water-organic binary solutions are governed by similar solvation equilibria
- Source :
- Journal of Physical Organic Chemistry. 29:118-126
- Publication Year :
- 2015
- Publisher :
- Wiley, 2015.
-
Abstract
- 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. 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. Linear similarity relationships were discovered for these data over the full range of solvent compositions studied. To gain insight into the similarities observed between these different phenomena, molecular dynamics simulations were carried out for naphthalene and an ester in water–acetonitrile solutions. The results revealed considerable preferential solvation of these substrates by the co-solvent. Linear relationships between the experimental data and the mole fractions of acetonitrile in the solvation shells of substrates were found. Surprisingly, a linear relationship was found between the mole fractions of acetonitrile in the solvation shells of the ester and naphthalene. This linearity indicated that a similar solvation mechanism governs even such different phenomena as dissolution and reaction kinetics. The relationships between the experimental data and the results of the molecular dynamics calculations found in this work explained the solvent effect observed in water-organic solutions on the molecular level. Copyright © 2015 John Wiley & Sons, Ltd.
- Subjects :
- Aqueous solution
010304 chemical physics
Chemistry
Implicit solvation
Organic Chemistry
Solvation
010402 general chemistry
Mole fraction
01 natural sciences
0104 chemical sciences
Solvation shell
Computational chemistry
0103 physical sciences
Organic chemistry
Physical and Theoretical Chemistry
Solvent effects
Solubility
Dissolution
Subjects
Details
- ISSN :
- 08943230
- Volume :
- 29
- Database :
- OpenAIRE
- Journal :
- Journal of Physical Organic Chemistry
- Accession number :
- edsair.doi...........f66b2afb00996fd8546d5438b5816b88