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.
A differential method is proposed which uses local heating rates to evaluate non-isothermal kinetic parameters. The method
allows to study the influence of the deviation of the true heating rate with respect to the programmed one on the values of
the kinetic parameters. For application, the kinetic parameters of the following solid-gas decomposition reaction were evaluated:
[Ni(NH3)6]Br2(s)→[Ni(NH3)2]Br2(s)+4NH3(g). The results obtained revealed significant differences between the values of the non-isothermal kinetic parameters obtained
by using local heating rates and those obtained by using the programmed heating rate. It was also demonstrated that the kinetic
equation which makes use of the local heating rates permits a better description of the experimental (α, t) data than the
kinetic equation which uses the programmed constant heating rate.
The authors continue their considerations concerning the validity of the steady-state approximation in non-isothermal kinetics.
A sequence of two first-order consecutive reactions with an active intermediate was subjected to kinetic analysis by numerical
solution of the corresponding differential kinetic equations for a number of particular cases. The results demonstrated that
the rate of change of concentration of the active intermediate is negligibly small if the assumption made in the isothermal
case is also accepted for the non-isothermal case, i.e. k2(T(t))>>
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.
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.
The integral methods proposed to compute the kinetic parameters of heterogeneous reactions under non-isothermal conditions are usually worked by the help of the least squares method and the obtained correlation coefficient is taken as a criterion to choose the best integral method.
Authors:C. Popescu, R. Alexandrescu, I. Morjan, and E. Segal
Several experiments have shown that inorganic salts may be decomposed to oxides by irradiating them with a continuous-wave
CO2 laser. The process is characterized by an extremely high heating rate which develops within the impact region of the laser
beam with the substance. For comparison, salts were also decomposed under controlled heating conditions. Knowledge of the
intermediate steps stresses the importance of the positive and negative feedback mechanisms which control the laser-induced
reactions. The present paper reviews results obtained by us for more complete descriptions of laser-induced reactions.