An alternative approach to kinetic analysis of temperature-programmed reaction data

To date, kinetic computations have been carried out efficiently for a great variety of physico-chemical processes including crystallization, melting and solid-solid transitions. However, appropriate methods for the kinetic analysis of chemical reactions, especially multi-staged reactions, are currently lacking. Here we report on an alternative way of treating temperature-programmed reaction data using the reduction of iron(iii) oxide as an example. The main principle in the suggested approach is to take into account every stage of the studied process, resulting in a system of kinetic differential equations. Kinetic parameters (activation energy and preexponential factors) are optimized for each of the stages, and cubic splines are used to approximate the conversion functions that reflect changes in reaction-specific surface area throughout the process. The applicability of the suggested method has been tested on temperature-programmed reduction (TPR) data for iron(iii) oxide samples produced from the original Fe₂O₃ powder by annealing it at 600, 700 and 800 °C. Results of kinetic analysis obtained at different temperature regimes demonstrate the good stability and performance of the method. Peculiarities of iron(iii) oxide reduction have been revealed, depending on the stage and heating rate. The influence of material morphology on the reduction kinetics has been assessed by comparing preexponential factors corresponding to the first reduction stage. This approach allows a comparison of the structural characteristics of the materials based on the kinetic analysis of the TPR data. Using optimized conversion functions, the initial particle size distribution has been reproduced. Theoretically found particle size distribution was found to correlate well with the experimental distribution obtained via laser diffraction.