Authors:J. Criado, P. Sánchez-Jiménez, and L. Pérez-Maqueda
A critical study of the use of isoconversional methods for the kinetic analysis of non-isothermal data corresponding to processes
with either a real or an apparent variation of the activation energy, E, with the reacted fraction, α, has been carried out using for the first time simulated curves. It has been shown that the
activation energies obtained from model-free methods are independent of the heating rate. However, the activation energy shows
a very strong dependence of the range of heating rates used for simulating the curves if the apparent change of E with α is caused by overlapping processes with different individual activation energies. This criterion perhaps could be
used for determining if a real dependence between E and α is really occurring.
A nonlinear algorithm has been suggested to increase the accuracy of evaluating the activation energy by the integral isoconversional method. A minor modification of the algorithm has made it possible to adapt the isoconversional method for an arbitrary variation of the temperature. This advanced isoconversional method allows for trustworthy estimates of the activation energy when the thermal effect of a reaction makes the temperature of a sample deviate from a prescribed heating program.
Authors:P. Budrugeac, D. Homentcovschi, and E. Segal
The differential and integral isoconversional methods for evaluation the activation energy, described in the first note of
this series, were applied for:
a) simulated data for two successive reactions;
b) dehydration of calcium oxalate monohydrate.
It was shown that for these systems the activation energy depends on the conversion degree as well as on the method of evaluation.
Authors:D. Válková, J. Kislinger, M. Pekař, and J. Kučerík
Humic acids represent a complicated mixture of miscellaneous molecules formed as a product of mostly microbial degradation
of dead plant tissues and animal bodies. In this work, lignite humic acids were enriched by model compounds and the model-free
method suggested by Šimon was used to evaluate their stability over the whole range of conversions during the first thermooxidative
degradation step. The kinetic parameters obtained were used to predict the stability at 20 and 180�C, respectively, which
served for the recognition of processes induced by heat and those naturally occurring at lower temperatures. Comparison of
the conversion times brought a partial insight into the kinetics and consequently into the role of individual compounds in
the thermooxidative degradation/stability of the secondary structure of humic acids. It has been demonstrated that aromatic
compounds added to humic acids, except pyridine, increased stability of humic acids and intermediate chars. The same conclusion
can be drawn for acetic and palmitic acids. Addition of glucose or ethanol decreased the overall humic stability; however,
the char of the former showed the highest stability after 40% of degradation.
The pyrolysis of wheat straw has been carried out by means of thermogravimetric analysis in inert atmosphere. The samples
were heated over a range of temperatures that includes the entire range of pyrolysis with three different heating rates of
5, 10 and 20 K min−1. The activation energy values as a function of the extent of conversion for the pyrolysis process of wheat straw have been
calculated by means of the Flynn–Wall–Ozawa isoconversional method, the Vyazovkin–Sbirrazzuoli isoconversional method and
an iterative isoconversional method presented in this article. The results have showed that there are small differences between
the activation energy values obtained from the three methods, and the pyrolysis process reveals a dependence of the activation
energy on conversion and have indicated the validity of the iterative integral isoconversional method. The effective activation
energy for the pyrolysis of wheat straw is 130–175 kJ mol−1 in the conversion range of 0.15–0.85. Furthermore, the prediction of the pyrolysis process under isothermal conditions from
the dependence of the activation energy on the extent of conversion has been presented.
Authors:P Budrugeac, D. Homentcovschi, and E. Segal
An analysis is presented of the consequences of the use of a one term equation containing apparent activation parameters,
instead of the true rate equation to describe two successive decomposition reactions undergone by a solid compound. It is
demonstrated that the apparent activation energy, obtained by means of isoconversional differential and integral methods,
varies with the conversion degree for a relatively narrow temperature range and with temperature at a given value of the conversion
degree. The activation energy values obtained with the isoconversional differential method are higher than the corresponding
values obtained with the isoconversional integral method.
(activation energy, pre-exponential factor, and conversion function) of each degradation step is one important target of kinetic investigations. Many kinetic analysis methods have been developed, among which isoconversionalmethods have been widely used [ 1