Effect of solvent composition on the acidity of phenols in dimethyl sulfoxide - water mixtures

Richard M. Tarkka; Ik Hwan Um; Hai Qi Xie; Alan Pierre Chatrouse; Francois Terrier; Shmaryahu Hoz; Erwin Buncel

doi:10.1002/(SICI)1099-1395(199812)11:12<847::AID-POC42>3.0.CO;2-5

Effect of solvent composition on the acidity of phenols in dimethyl sulfoxide - water mixtures

Richard M. Tarkka, Ik Hwan Um, Hai Qi Xie, Alan Pierre Chatrouse, Francois Terrier, Shmaryahu Hoz, Erwin Buncel

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

9 Scopus citations

Abstract

The effect of solvent composition on the acidity of substituted phenols in DMSO-H₂O systems was examined. It is shown that in DMSO-H₂O mixtures with up to 35 mol% DMSO there is a linear relationship between the pK_a values of monosubstituted phenols in the binary solvent mixtures of different compositions and the corresponding pK_a values in water. This leads to an equation relating the slope and intercept terms, pK_a(DMSO-H₂O) = slope[pK_a(H₂O)] + intercept. The basis of this relationship in the Kirkwood-Westheimer equation is examined. The significance of a possible 'supersolvent' is discussed. The applicability of the relationships derived herein to other rate-equilibria relationships and solvent mixtures is considered.

Original language	English
Pages (from-to)	847-852
Number of pages	6
Journal	Journal of Physical Organic Chemistry
Volume	11
Issue number	12
DOIs	https://doi.org/10.1002/(SICI)1099-1395(199812)11:12<847::AID-POC42>3.0.CO;2-5
State	Published - Dec 1998

Keywords

Acidity
Phenols
Solvent composition
Supersolvent

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10.1002/(SICI)1099-1395(199812)11:12<847::AID-POC42>3.0.CO;2-5

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title = "Effect of solvent composition on the acidity of phenols in dimethyl sulfoxide - water mixtures",

abstract = "The effect of solvent composition on the acidity of substituted phenols in DMSO-H2O systems was examined. It is shown that in DMSO-H2O mixtures with up to 35 mol% DMSO there is a linear relationship between the pKa values of monosubstituted phenols in the binary solvent mixtures of different compositions and the corresponding pKa values in water. This leads to an equation relating the slope and intercept terms, pKa(DMSO-H2O) = slope[pKa(H2O)] + intercept. The basis of this relationship in the Kirkwood-Westheimer equation is examined. The significance of a possible 'supersolvent' is discussed. The applicability of the relationships derived herein to other rate-equilibria relationships and solvent mixtures is considered.",

keywords = "Acidity, Phenols, Solvent composition, Supersolvent",

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AU - Tarkka, Richard M.

AU - Um, Ik Hwan

AU - Xie, Hai Qi

AU - Chatrouse, Alan Pierre

AU - Terrier, Francois

AU - Hoz, Shmaryahu

AU - Buncel, Erwin

PY - 1998/12

Y1 - 1998/12

N2 - The effect of solvent composition on the acidity of substituted phenols in DMSO-H2O systems was examined. It is shown that in DMSO-H2O mixtures with up to 35 mol% DMSO there is a linear relationship between the pKa values of monosubstituted phenols in the binary solvent mixtures of different compositions and the corresponding pKa values in water. This leads to an equation relating the slope and intercept terms, pKa(DMSO-H2O) = slope[pKa(H2O)] + intercept. The basis of this relationship in the Kirkwood-Westheimer equation is examined. The significance of a possible 'supersolvent' is discussed. The applicability of the relationships derived herein to other rate-equilibria relationships and solvent mixtures is considered.

AB - The effect of solvent composition on the acidity of substituted phenols in DMSO-H2O systems was examined. It is shown that in DMSO-H2O mixtures with up to 35 mol% DMSO there is a linear relationship between the pKa values of monosubstituted phenols in the binary solvent mixtures of different compositions and the corresponding pKa values in water. This leads to an equation relating the slope and intercept terms, pKa(DMSO-H2O) = slope[pKa(H2O)] + intercept. The basis of this relationship in the Kirkwood-Westheimer equation is examined. The significance of a possible 'supersolvent' is discussed. The applicability of the relationships derived herein to other rate-equilibria relationships and solvent mixtures is considered.

KW - Acidity

KW - Phenols

KW - Solvent composition

KW - Supersolvent

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JO - Journal of Physical Organic Chemistry

JF - Journal of Physical Organic Chemistry

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Effect of solvent composition on the acidity of phenols in dimethyl sulfoxide - water mixtures

Abstract

Keywords

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