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  • Author or Editor: N. Koga x
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Summary Two different processes of the thermal decomposition of synthetic bayerite, i.e., the non-isothermal decomposition of mechanically ground sample in flowing N2 and the controlled rate thermal decomposition of crystalline bayerite under vacuum, were investigated comparatively. In comparison with the conventional non-isothermal decomposition of crystalline bayerite in flowing N2, the reaction temperature of the thermal decomposition was lowered by the individual effects of mechanical grinding of the sample and the reaction rate control. These decomposition processes indicated similar behavior characterized by the restricted changes of the specific surface area during the course of decomposition reaction and the formation of an amorphous alumina as the decomposition product. Different thermal behaviors were observed for those amorphous Al2O3 produced by the respective decomposition processes.

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Abstract  

The physico-geometric kinetics for the solid-state reactions by thermoanalytical (TA) measurements were reexamined by focusing some fundamental aspects: (1) the fundamental kinetic equation, (2) the kinetic model function, (3) the fractional reaction α, and (4) the apparent kinetic parameters. It was pointed out that some pitfalls in the practical kinetic study are originated by the disagreement between the kinetic information from the TA measurements and the theory of the physico-geometric kinetics. In order to increase the degree of coordination between the theory and practice, several attempts were made from both the theoretical and experimental points of views. The significance of the apparent kinetic parameters was discussed with a possible orientation for obtaining the reliable kinetic parameters.

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Two different samples of amorphous calcium carbonate (ACC) hydrates were prepared respectively by mixing aqueous solutions of CaCl2 and Na2CO3-NaOH and by allowing the diffusion of (NH4)2CO3 sublimate into ethanol solution of CaCl2. Thermal behaviors of the synthetic ACCs were investigated comparatively by means of thermoanalytical techniques complimented by powder X-ray diffraction, FTIR spectrometry and microscopic observations. The anhydrous ACCs produced by the thermal dehydration of the respective samples were crystallized to calcite in different ways. The sample prepared in aqueous medium was crystallized at around 600 K in a single step. Crystallization in two separated steps at around 600 and 825 K was observed for the sample prepared in ethanol medium. Characteristics of the crystallization processes were discussed from thermodynamic and kinetic points of view.

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Effect of mechanical grinding of hydromagnesite on the reaction pathway and kinetic behaviors of the thermal decomposition process was investigated by means of thermoanalytical techniques, together with crystallographic and morphological measurements. A crystalline hydromagnesite, the as-received sample, was decomposed in two distinguished mass loss steps of overlapped dehydration-dehydroxylation and dehydroxylation-decarbonation via an amorphous intermediate of carbonate compound. Thermal decomposition of an amorphous hydromagnesite, obtained by mechanical grinding of the as-received sample, was characterized by three well-separated decomposition processes of dehydration, dehydroxylation and decarbonation. The kinetic behaviors of the respective decomposition steps were estimated separately using a mathematical deconvolution of the partially overlapped reaction steps. From the formal kinetic analyses of the respective reaction processes, it was revealed that the dehydration and dehydroxylation processes indicate the decelerate rate behaviors controlled by diffusion, while the rate behavior of nucleation limited type is predominant for the decarbonation process.

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For the quantitative analyses of evolved CO2and H2O during the thermal decomposition of solids, calibration curves, i.e. the amounts of evolved gases vs. the corresponding peak areas of mass chromatograms measured by TG-MS, were plotted as referenced by the reaction stoichiometry of the thermal decomposition of sodium hydrogencarbonate NaHCO3. The accuracy and reliability of the quantitative analyses of the evolved CO2and H2O based on the calibration curves were evaluated by applying the calibration curves to the mass chromatograms for the thermal decompositions of copper(II) and zinc carbonate hydroxides. It was indicated from the observed ratio of evolved CO2and H2O that the compositions of copper(II) and zinc carbonate hydroxides examined in this study correspond to mineral malachite, Cu2CO3(OH)2, and hydrozincate, Zn5(CO3)2(OH)6, respectively. Reliability of the present analytical procedure was confirmed by the fairly good agreement of the mass fraction of the evolved gases calculated from the analytical values with the total mass-loss during the thermal decompositions measured by TG.

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The degree of coordination between the kinetic information from the thermonalytical measurements and the kinetic theory of the solid-state reactions was investigated through the microscopic study of the thermal dehydration of several inorganic salt hydrates. An accommodation function was applied to the conventional kinetic model functionsf(α), in an attempt to reduce the disagreement between the actual process and the idealized one assumed in formulatingf(α). The significance of the non-integral kinetic exponent in the kinetic model function was discussed with its physico-chemical meanings.

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Thermoanalytical (TA) and hot-stage microscopic techniques were employed to investigate the complicated behaviour of the non-isothermal dehydration of single crystals of α-NiSO4·6H2O. Non-isothermal dehydration to the tetrahydrate proceeds in two stages: (1) surface nucleation and growth of nuclei, followed by advancement of reaction fronts inward; (2) random nucleation and growth near the reaction front as well as in the bulk. Corresponding TA curves were interpreted to represent diffusional removal of evolved water vapour through the surface layer created in stage (1). The dehydration process of the tetrahydrate to the monohydrate is explained on the basis of textural structures produced in the previous step. Crack formation in the surface layer and rapid escape of the water vapour were observed in this step.

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Abstract  

Effects of sample mass on the kinetics of isothermal dehydration of crushed crystals of Li2SO4·H2O were investigated using conventional TG. The process was characterized by a combination of Avrami-Erofeyev and contracting geometry models. Distribution of the fractional reaction, α, in particles within the sample assembly as well as the change in the rate of gross diffusion of the evolved water vapour appear responsible for the sample-mass-dependent kinetic parameters obtained for the system.

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