The authors present some theoretical considerations concerning the influence of the form of the conversion functionf(α) on the values of the degree of conversion corresponding to the maximum value of the reaction rate (αmax) as well as on the inflexion points (αinf) of the DTG curve. The obtained equations are characterized by a general validity no matter the form off(α).
The results of an attempt to derive correct nonisothermal kinetic equations from isothermal ones through the classical nonisothermal change (CNC) of the postulated primary kinetic equations are presented. An alternative possibility through use of the model of infinitesimal isothermal portions (MIIP) is discussed.
The paper deals with the influence of the deviation of the true heating rate with respect to the programmed one on the values
of non-isothermal kinetic parameters for the solid-gas thermal decompositions of CaC2O4.H2O and [Ni(NH3)6]Br2. An original method, based on integration over small ranges of the variables and making use of local heating rates, was applied
in order to determine the non-isothermal kinetic parameter values. The results show significant differences between values
of non-isothermal kinetic parameters obtained by using true local heating rates and those obtained by using the programmed
An improved version of the Coats-Redfern method of evaluating non-isothermal kinetic parameters is presented. The Coats-Redfern approximation of the temperature integral is replaced by a third-degree rational approximation, which is much more accurate. The kinetic parameters are evaluated iteratively by linear regression and, besides the correlation coefficient, the F test is suggested as a supplementary statistical criterion for selecting the most probable mechanism function. For applications, both non-isothermal data obtained by theoretical simulation and experimental data taken from the literature for the non-isothermal dehydration of Mg(OH)2 have been processed.
and the steady-state approximation are used to present a demonstration of the fact that the evolution of the reaction rates
under non-isothermal conditions depends on the ratio of the activation energies and on the heating rate. At the same time,
it is shown that, under isothermal conditions, the ratio of the activation energies plays no role.
The paper investigates the validity of steady-state approximation for the case of constant rate thermal analysis experiments. It is shown that the approximation holds for the experiments run with a controlled rate of either the decomposition of the compound, or the production of gas.