A kinetic study of the thermal decomposition process of potassium metabisulfite: Estimation of distributed reactivity model

Abstract

The thermal decomposition kinetics of potassium metabisulfite was studied by thermogravimetric (TG) and differential thermogravimetric (DTG) techniques using non-isothermal experiments. The apparent activation energy (Ea) is determined using the differential (Friedman) isoconversional method. The results of the Friedman's isoconversional analysis of the TG data suggests that the investigated decomposition process follows a single-step reaction and the observed apparent activation energy was determined as 122.4±2.1 kJ mol-1. A kinetic rate equation was derived for the decomposition process of potassium metabisulfite with contracting area model, f(α)=2(1-α)1/2, which is established using the Malek's kinetic procedure. The value of pre-exponential factor (A) is also evaluated and was found to be A=1.37×1012 min-1. By applying the Miura's procedure the distributed reactivity model (DRM) for investigated decomposition process was established. From the dependence α versus Ea, the experimental distribution curve of apparent activation energies, f(Ea), was estimated. By applying the non-linear least-squares analysis, it was found that the Gaussian distribution model (with distribution parameters E0=121.3 kJ mol-1 and σ=1.5 kJ mol-1) represents the best reactivity model for describing the investigated process. Using the Miura's method, the A values were estimated at five different heating rates and the average A values are plotted against Ea. The linear relationship between the A and Ea values was established (compensation effect). Also, it was concluded that the Ea values calculated by the Friedman's method and estimated distribution curve, f(Ea), are correct even in the case when the investigated decomposition process occurs through the single-step reaction mechanism. © 2008 Elsevier Ltd. All rights reserved.