Thermokinetic studies of poly(<Emphasis Type="Italic">o</Emphasis>-toluidine) doped with perchloric acid

Thermokinetic parameters of the solid-state of poly(o-toluidine) (POT) doped with perchloric (HClO₄) acid was studied by thermogravimetric analysis (TG) and differential thermal analysis (DTA) under non-isothermal conditions. Molecular mechanics (MM) calculations suggest that the optimal geometric structure (OMG) of the HClO₄-doped POT is at least four orders of magnitude more stable than the molecular geometric (MG) structure. These calculations indicate that the potential energy (PE/kJ mol⁻¹) of the OMG is about four (1.09·10⁴) orders of magnitude lower than the MG structure of the same matrix. The empirical formula of the doped polymer is best represented by POT-2HClO₄·2H₂O]_n as substantiate by elemental analysis and MM calculations. The full polymer decomposition and degradation were found to occur in three stages during the temperature increase. The decomposition activation energy (E _d) of HClO₄-doped POT matrix was calculated by employing different approximations. The heating rate (α) of the decomposition and the frequency factor (K _o) were calculated. A number of equations were used to evaluate the kinetic parameters. The mechanism of the degradation of the conducting polymer is explained on the basis of their kinetic parameters. A remarkable heating rate dependence of the decomposition rate was observed.