Abstract
Kinetic equations, applicable to A-1, A-SE2, and A-2 reactions in concentrated aqueous acids, are derived. The variation in reaction rate with varying acid concentration is treated in terms of the "excess acidity" of the medium (X-function), rather than in terms of Hammett-type acidity functions or the water activity. The parameters obtained are the medium-independent rate constant k0, in the aqueous standard state, as an intercept, and a slope parameter m≠ hydration parameters (r-values) are also obtained, for A-2 reactions. The equations derived are shown to apply to A-1 acetal hydrolyses, A-SE2 electrophilic aromatic substitutions, and mixed A-2/A-1 ester hydrolyses. In a general discussion of available methods for analyzing rate data in these media, it is shown that the X-function method encompasses most, if not all, of the others, and that classical acidity functions are no longer necessary.
Publisher
Canadian Science Publishing
Subject
Organic Chemistry,General Chemistry,Catalysis
Cited by
101 articles.
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