A SURVEY OF THERMODYNAMIC PARAMETERS FOR SOLVOLYSIS IN WATER

A method is suggested for determining the standard state entropies of the transition state for the neutral hydrolysis of esters in water. This has required the development of methods for approximating initial state parameters where experimental data are lacking.Characteristic linear correlations bet...

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Bibliographic Details
Published in:Canadian journal of chemistry 1959-04, Vol.37 (4), p.803-824
Main Authors: Robertson, R. E, Heppolette, R. L, Scott, J. M. W
Format: Article
Language:English
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Summary:A method is suggested for determining the standard state entropies of the transition state for the neutral hydrolysis of esters in water. This has required the development of methods for approximating initial state parameters where experimental data are lacking.Characteristic linear correlations between the entropy and enthalpy of activation are observed for hydrolysis in water, as well as for the bimolecular halide exchange reaction in acetone and for acid-base equilibria. Explanations are advanced to explain the observed trends.From the derived standard state entropies, a method for estimating the charge development in the transition state for the methyl and isopropyl halides is proposed. With this further detailed knowledge of the transition state in the methyl halide series, reasonable values of the activation enthalpy can be calculated from available thermochemical data.
ISSN:0008-4042
1480-3291
DOI:10.1139/v59-108