Role of isoconversional methods in varying activation energies of solid-state kinetics: I. isothermal kinetic studies

Solid-state kinetics was developed from kinetic concepts for reactions in homogeneous phase systems, which has created considerable debate over issues such as variable activation energy. This behavior has been viewed by some as a violation of basic chemical kinetic principles. Variation in activation energy has been detected by isoconversional or ‘model-free’ calculation methods. The relationship between different calculation methods and the occurrence of variable activation energy was investigated in this work by employing model-fitting and isoconversional methods to analyze simulated isothermal data. In addition, these approaches were applied for sulfameter–dioxolane solvate desolvation data. We showed that variable activation energy is of two types—a true variation that results from the complex nature of the solid-state process and an artifactual one resulting from the use of some isoconversional methods.