J. Yano et al., KINETIC-STUDY OF THE ELECTROPOLYMERIZATION OF ANILINE USING CHRONOAMPEROMETRIC TECHNIQUES, Analytical sciences, 13(5), 1997, pp. 741-746
Aniline was electropolymerized using constant-potential electrolysis.
The chronoamperograms during the electropolymerization definitely had
two different time dependences on the electrolytic current. During the
initial stage, the current increased with the square root of the elec
trolysis time, and then increased linearly with the time. Those result
s were intrinsically the same as those of the electrodeposition of met
al ions. To determine the kinetic parameters, the electrolytic current
during the polymerization was analyzed on the basis of metal electrod
eposition models developed by Fleishmann and Thirsk. The rate constant
of the polymerization reaction was found to be directly proportional
to the concentration of protons, to the concentration of anions and to
the square of the concentration of aniline; also, the rate constant w
as formulated using the concentrations as well as the electrolysis pot
ential and temperature. The concentration dependence of the rate const
ant led to the belief that the rate-determining reaction in the polyme
rization was the electro-oxidation of the dimer of aniline, p-aminodip
henylamine.