Three model-free methods for calculation of activation energy in TG

Two well-known isoconversion methods, the first one developed by Ozawa-Flynn-Wall and the second one developed by Friedman, are confronted with calculations made using modulated thermogravimetry (MTG). The latter variant is free from a number of assumptions and restrictions made in the isoconversion computations. In particular, it allows the use of a single decomposition curve and it remains in force even in the case of multistage decomposition with conjugated processes. To obtain the model-fitting methods from the model-free methods one should replace some functions averaged over isoconversion levels by the functions calculated on the basis of kinetic models. In the Ozawa-Flynn-Wall method it is the averaged reduced time (integral of Arrhenius exponential over time). In the method of Friedman it is the averaged differential conversion function. In MTG, the perturbations caused by the sinusoidal temperature modulation are connected with derivatives of mass loss by simple scaling, where activation energy plays a role of a scaling parameter. The ratio of the experimentally measured perturbations to the experimental derivative is used for the model-free computation of activation energy. If a theoretical derivative replaces the experimental one, this procedure leads to the model-fitting method. Even a rough approximation of the experimental derivative should not lead to an excessive error in activation energy. If in a vicinity of peaks' maxima in derivatives of mass loss the decomposition is controlled by single rate-limiting processes, modulated thermogravimetry should give realistic activation energies for these processes. Inasmuch as the results of MTG are weakly sensitive to selection of kinetic models, this method should have a high predictive force.