Group Interactions in Polyelectrolytes. II. Kinetics of Alkaline Hydrolysis of Polymethyl Acrylate

Abstract The second-order rate constant of the alkaline hydrolysis of polymethyl acrylate in an aqueous acetone solution decreases as the reaction proceeds. The plot of the logarithmic term of the second-order rate equation against the reaction time is divided into four lines; this suggests that the reaction proceeds in four steps. The rate equation of the reaction can be derived by assuming that the reactivity of ester groups is electrically affected mainly by a few neighboring hydrolyzed groups. The kinetic behavior is compared with the titration data of polyacrylic acid; the sets of data can be correlated through a simple equation containg two constants, k0, the intrinsic rate constant, and pK0, the intrinsic ionization constant.