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Grunwald–Winstein equation

The linear free energy relation:
log 10 ( k s k 0 ) = m Y
expressing the dependence of the rate of solvolysis of a substrate on ionizing power of the solvent. The rate constant k 0 applies to the reference solvent (ethanol–water, 80:20, v/v) and k s to the solvent s, both at 25 °C. The parameter m is characteristic of the substrate and is assigned the value unity for tert-butyl chloride. The value Y is intended to be a quantitative measure of the ionizing power of the solvents. The equation was later extended to the form:
log 10 ( k s k 0 ) = m Y + l N
where N is the nucleophilicity of the solvent and l its susceptibility parameter. The equation has also been applied to reactions other than solvolysis.
Source:
PAC, 1994, 66, 1077 (Glossary of terms used in physical organic chemistry (IUPAC Recommendations 1994)) on page 1118
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IUPAC. Compendium of Chemical Terminology, 2nd ed. (the "Gold Book"). Compiled by A. D. McNaught and A. Wilkinson. Blackwell Scientific Publications, Oxford (1997). XML on-line corrected version: http://goldbook.iupac.org (2006-) created by M. Nic, J. Jirat, B. Kosata; updates compiled by A. Jenkins. ISBN 0-9678550-9-8. doi:10.1351/goldbook.
Last update: 2014-02-24; version: 2.3.3.
DOI of this term: doi:10.1351/goldbook.G02710.
Original PDF version: http://www.iupac.org/goldbook/G02710.pdf. The PDF version is out of date and is provided for reference purposes only. For some entries, the PDF version may be unavailable.
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