The utilization of electropolymerized electronically conducting polyme
rs as amperometric chemical sensors and electrocatalysts is described,
with specific emphasis on poly(pyrrole) based materials. A theoretica
l model describing the operational principles of the polymer sensor is
also described. The processes of substrate transport to the sensor su
rface, and subsequent substrate reaction at the latter, were analysed
in the context of rotating disc voltammetry. Two distinct situations w
ere considered. In the first, the substrate does not partition into th
e layer, but simply reacts, via Butler-Volmer kinetics, at the polymer
/solution interface. The second situation arises when the substrate pa
rtitions into the polymer layer. In this instance, substrate diffusion
and reaction within the film was analysed. The porous nature of the p
olymer film is specifically taken into account. The redox chemistry of
poly(pyrrole) films doped with Cl- and DBS- ions was examined using c
yclic voltammetry and complex impedance spectroscopy and the mechanism
of redox switching in these materials was investigated. The electrode
kinetics of the quinone-hydroquinone redox couple at the doped poly(p
yrrole) films was also examined using cyclic voltammetry and rotating
disc electrode voltammetry, and the mechanistic pathway was elucidated
.