Molecular organization of reagents in the kinetics and catalysis of liquid-phase reactions: VIII. A new approach to solvent effect on the reaction kinetics in associated media

A new approach to the quantitative description of the effect of medium on t he kinetics of the molecular reactions of aliphatic alcohols is developed. This approach is based on analogies in the behavior of linear-chain associa tes of alcohols formed via hydrogen bonding and flexible-chain polymers in solutions. In the same reaction, the reaction order with respect to the alc ohol may differ depending on the ability of the solvent to stabilize or det eriorate 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 add ition to aryl isocyanate, the kinetic parameters are found that quantitativ ely characterize the degree to which a solvent affects the reaction.