Evaluation of activation energy of thermally stimulated solid-state reactions under arbitrary variation of temperature

TLDR

The thermal effect of a reaction causes the temperature inside the system to deviate from a prescribed heating program. To account for such temperature deviations in kinetic evaluations, a computational method applicable to arbitrary temperature variations has been developed. The method integrates the isoconversional principle with numerical integration of dα/dt = k[T(t)]f(α) over the actual temperature profile, details a robust algorithm, and tolerates temperature noise. Model simulations demonstrate that incorporating temperature deviations yields more reliable activation energy estimates than methods that ignore these deviations. © 1997 John Wiley & Sons, Inc.

Abstract

The thermal effect of a reaction makes the temperature inside the reaction system deviate from a prescribed heating program. To take into account the effect of such temperature deviations on kinetic evaluations, a computational method applicable to an arbitrary variation in temperature has been developed. The method combines the isoconversional principle of evaluating the activation energy with numerical integration of the equation, dα/dt = k[T(t)]f(α), over the actual variation of the temperature with the time, T(t). Details of the numerical algorithm are reported. A model example has been used to verify the reliability of this method as compared to an analogous method which does not account for the deviations of the temperature from a prescribed program. The method has been tested for tolerance for noise in the temperature. © 1997 by John Wiley & Sons, Inc.