Abstract
The oxidative chemical polymerization kinetics of aniline (AN) with ammonium peroxydisulfate (APS) in aqueous acid solutions with and without the presence of initial substrates is reported. A semi-empirical kinetic equation, − d[ AN] dt = k 1[ AN][ APS] + k 2′[ AN][ P] , where [P] = equivalent concentration of polymer, is proposed for this autoaccelerated reaction. The value obtained for k 2′ depends primarily on acid concentration and the presence of substrate surfaces; k 1 is affected by the presence of catalyst and the initial reactant concentrations. In general, k 2′ has a value about two to three orders of magnitude higher than k 1. A mechanism similar to the electrochemical polymerization is proposed for the autoacceleration reaction which involves the oxidation of aniline by highly oxidized polyaniline with the incorporation of acid.
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