D. N. Tarasov, R. P. Tiger, S. G. Entelis, A. V. Gorshkov, and M. A. Levina
Semenov Institute of Chemical Physics, Russian Academy of Sciences, Moscow, 117977 Russia
Received December 26, 1997
Abstract—A new approach to the quantitative description of the effect of medium on the kinetics of the molec-
ular reactions of aliphatic alcohols is developed. This approach is based on analogies in the behavior of linear-
chain associates of alcohols formed via hydrogen bonding and flexible-chain polymers in solutions. In the same
reaction, the reaction order with respect to the alcohol may differ depending on the ability of the solvent to sta-
bilize or deteriorate the polymer-like structure of the solution. The classification of solvents is proposed based
on their effects on the structure of associated solutions. Based on the kinetic data on the model reaction of
n-butanol addition to aryl isocyanate, the kinetic parameters are found that quantitatively characterize the
degree to which a solvent affects the reaction.
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