Impact of Thermodynamic Constraints on the Lability of Activation Energy as a Function of Conversion Degree

The subject concerns the determination of activation energy under dynamic conditions using two theoretical isothermal models, and subsequently experimental data, with reference to the α–T relationship matrix. In recent years, the Vyazovkin method, classified as one of the isoconversional variants, has gained the greatest recognition. Comparison was made between two isothermal models of the thermal dissociation of calcite, which in chronological terms are associated with a kinetic–nucleation reaction/process (the H-CL, as a kinetic model) and a kinetic–desorption reaction/process (the V, as a thermodynamic model). A comparison of numerical values, understood as the logarithm of the reaction/process rate with respect to temperature, shows correspondence in the temperature range up to the equilibrium temperature. The H-CL model is characterized by a strong dominance of the nucleation process relative to the chemical reaction, whereas the V model exhibits a certain type of balance resulting from the course of the chemical decomposition reaction combined with the transformation of a metastable oxide into a crystalline form. It was confirmed that both models describe the same phenomenon within the transformation process, which implies that for a constant conversion degree, the proportions of the chemical reaction and the physical process vary. Pointwise with increasing temperature, the H-CL model leads to a minimum activation energy E → 0, whereas the V model reaches a negative activation energy E < 0. In both cases, the apparent activation energy summed over the process is constant, and the assigned conversion degree, treated as isoconversional, remains fixed and corresponds to the assumed activation energy of the completed reaction/process. Several simple methods for its determination under dynamic/isoconversion conditions are used.