Conclusions
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1.
The following rule was formulated for the establishment of the mechanism of the limiting step of hydrolysis: in reactions of hydrolysis in aqueous solutions of strong acids, the activity of the activated complex should be expressed in terms of the concentrations of various forms of the reagents in such a way that the factor with the activity coefficients obtained in the kinetic equation would not vary or would depend little on the acid concentration, which reflects the stoichiometric equation of the limiting step.
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2.
The reactions of hydrolysis in aqueous solutions of strong acids are divided into four groups. In reactions of groups I and II the activated state of the process is formed from a nonionized form of the reagent, hydroxonium ions, and a nucleophile—a water molecule (group I) and anions (group II). Group II also includes reactions with the simultaneous appearance of a nucleophilic action of water and anions. In reactions of other groups, the activated state is formed from a protonated form of the reagent with or without the participation of water molecules (group III) and with the participation of anions (group IV).
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Report at the General Meeting at the Division of General and Theoretical Chemistry of the Academy of Sciences of the USSR, April 26, 1972.
Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 998–1006, May, 1973.
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Vinnik, M.I. Some elementary reactions of acid-base processes in the liquid phase. Russ Chem Bull 22, 963–969 (1973). https://doi.org/10.1007/BF00854232
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DOI: https://doi.org/10.1007/BF00854232