RESUMO
Several inorganic hydrates exhibit reversible reactions of thermal dehydration and rehydration, which is potentially applicable to thermochemical energy storage. Detailed kinetic information on both forward and reverse reactions is essential for refining energy storage systems. In this study, factors determining the reaction pathway and kinetics of the multistep thermal dehydration of inorganic hydrates to form anhydride via intermediate hydrates were investigated as exemplified by the thermal dehydration of CaCl2·2H2O (CC-DH) in a stream of dry N2. The formation of CaCl2·H2O (CC-MH) as the intermediate hydrate is known during the thermal dehydration of CC-DH to form its anhydride (CC-AH). However, the two-step kinetic modeling based on the chemical reaction pathway considering the formation of the CC-MH intermediate failed in terms of the reaction stoichiometry and kinetic behavior of the component reaction steps. The kinetic modeling was refined by considering the physico-geometrical reaction mechanism and the self-generated reaction conditions to be a three-step reaction. The multistep reaction was explained as comprising the surface reaction of the thermal dehydration of CC-DH to CC-AH and subsequent contracting geometry-type reactions from CC-DH to CC-MH and from CC-MH to CC-AH occurring consecutively in the core of the reacting particles surrounded by the surface product layer of CC-AH. The acceleration of the linear advancement rate of the reaction interface during both contracting geometry-type reactions was revealed through multistep kinetic analysis and was described by a decrease in the water vapor pressure at the reaction interface as the previous reaction step proceeded and terminated.
RESUMO
This study investigated how water vapor influences the reaction pathway and kinetics of the multistep thermal dehydration of inorganic hydrates, focusing on CaCl2·2H2O (CC-DH) transforming into its anhydride (CC-AH) via an intermediate of its monohydrate (CC-MH). In the presence of atmospheric water vapor, the thermal dehydration of CC-DH stoichiometrically proceeded through two distinct steps, resulting in the formation of CC-AH via CC-MH under isothermal conditions and linear nonisothermal conditions at a lower heating rate (ß). Irrespective of atmospheric water vapor pressure (p(H2O)), these reaction steps were kinetically characterized by a physico-geometrical consecutive process involving the surface reaction and phase boundary-controlled reaction, which was accompanied by three-dimensional shrinkage of the reaction interface. In addition, a significant induction period was observed for the second reaction step, that is, the thermal dehydration of CC-MH intermediate to form CC-AH. With increasing p(H2O), a systematic increase in the apparent Arrhenius parameters was observed for the first reaction step, that is, the thermal dehydration of CC-DH to form CC-MH, whereas the second reaction step exhibited unsystematic variations of the Arrhenius parameters. At a larger ß in the presence of atmospheric water vapor, the first and second reaction steps partially overlapped; moreover, an alternative reaction step of the thermal dehydration of CC-MH to form CaCl2·0.3H2O was observed between these reaction steps. The physico-geometrical phenomena influencing the reaction pathway and kinetics of the multistep thermal dehydration were elucidated by considering the effects of atmospheric and self-generated water vapor in a geometrically constrained reaction scheme.