Application of Non‐Arrhenius Equations in Interpreting Calcium Carbonate Decomposition Kinetics: Revisited

Abstract

Thermal decomposition kinetics of calcium carbonate was studied by non‐isothermal thermogravimetric analysis at different heating rates. The reaction mechanism was found to follow a two‐dimensional phase boundary‐controlled model by model‐free and model‐fitting methods. Two non‐Arrhenius equations (Harcourt–Esson equation and Berthelot–Hood equation) were used to interpret the decomposition kinetics and the results were correlated with those by using the Arrhenius equation. The ambiguous operations in kinetic analysis in the literature, including the determination of reaction mechanism by the shape of thermogravimetry/DTG curves and the correlation of the kinetic parameters of non‐Arrhenius and Arrhenius equations, were discussed. Some suggestions were proposed when using non‐Arrhenius equations in interpreting solid decomposition kinetics.

A Multifaceted Kinetic Model for the Thermal Decomposition of Calcium Carbonate

“…According to Figure 5, the theoretical values calculated from the interface model (R) agree well with the experimental data obtained for the thermal decomposition of calcium carbonate. The relative error data in Table 1 also indicates the accuracy of the interface model in describing the thermal decomposition behavior of calcium carbonate, which is also consistent with the literature [22,42,43]. Although the calculated data in Table 1 indicate a relatively larger value for the relative error between the theoretical and experimental values of the diffusion model, it is seen from Figure 5 that the diffusion model partly describes the thermal decomposition process of calcium carbonate with consistency [17].…”

“…This method was used to obtain the activation energy (by slash of ln dα/dT f (α) against 1 T ) and pre-exponential factor (by intercept of ln dα/dT f (α) against 1 T ) as well. Due to the formation of pores as a result of carbon dioxide liberation during the thermal decomposition of calcium carbonate, the random pore model, interface reaction model, and diffusion model were introduced for combinatorial optimization [4,22,30,33]. Based on the theory of Šesták for the kinetic model of accommodation function [34][35][36], the following multifaceted model function was established.…”

“…There have been several studies on calcium carbonate among which the kinetic studies on the thermal decomposition of calcium carbonate are extensively reported. Some model functions were selected from the literature to compare with the multifaceted model function [4,15,17,22,24,39,40]. The experiments mentioned in the previous section were repeated in the comparative studies of the different models for the thermal decomposition of calcium carbonate.…”

“…Chen et al determined the decomposition reaction model of calcium carbonate using the model-free and model fitting methods. The model for the thermal decomposition of calcium carbonate was proposed to be R 2 [22] which can be expressed as:…”

Non-isothermal depolymerisation kinetics of poly(ethylene oxide)

“…The non-isothermal pyrolysis and TG analysis of plastic waste material in the search to produce new fuels [25] is one such example appearing in the polymer literature and the non-isothermal decomposition of inorganic salts [26,27] is representative of fundamental NIK studies that appear elsewhere in the literature. Data derived from non-isothermal pyrolysis techniques such as these, however, can in some cases produce seemingly high values of activation energies compared with other techniques [28].…”