ASSOCIATION AND DISSOCIATION EFFECT OF AL COHOLS ON RATE CONSTANTS OFTHE REACTION WITH ACETIC-ANHYDRIDE

Kinetic study of the equimolar reactions of acetic anhydride with vari ous alcohols was investigated under varying dilution of the reactants. The second order reaction rate constants k2 varied according to the c hange of the initial concentrations of the reactants. The rate constan ts k(infinity) obtained at an infinite dilution of the reactants were considered to be the real intrinsic rates of alcohol monomers, and var ied according to the class of alcohols as follows. p-Alcohols>Methanol , s-Alcohols>t-Alcohols The correlations of the rate constants k(infin ity) with Taft's substituents constant sigma, and the electron densit y on the oxygen atom of the alcohol were fairly good in each class of the alkyl substituents of the alcohols. Those correlations show the fa ct that the electron donating substituents on the alcohols accelerate the esterification reaction, and the in teraction of the oxygen atom o f the alcohol with the carbonyl carbon of anhydride plays an important role in this reaction.