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Thermal dehydration of d-glucose monohydrate in solid and liquid states

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PHYSICAL CHEMISTRY CHEMICAL PHYSICS
卷 25, 期 24, 页码 16643-16656

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ROYAL SOC CHEMISTRY
DOI: 10.1039/d3cp02059b

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The physico-geometrical reaction pathway and kinetics of the thermal dehydration of d-glucose monohydrate (DG-MH) are significantly influenced by the melting of the reactant. By controlling the reaction conditions, three different reaction modes were observed: solid-state reaction, switching from a solid- to liquid-state reaction, and liquid-state reaction. The reaction pathway and kinetics of the thermal dehydration of DG-MH vary depending on the sample and reaction conditions.
The physico-geometrical reaction pathway and kinetics of the thermal dehydration of d-glucose monohydrate (DG-MH) dramatically alter by the melting of the reactant midway through the reaction. By controlling the reaction conditions, the thermal dehydration of DG-MH was systematically traced by thermoanalytical techniques in three different reaction modes: (1) solid-state reaction, (2) switching from a solid- to liquid-state reaction, and (3) liquid-state reaction. Solid-state thermal dehydration occurred under isothermal conditions and linear nonisothermal conditions at a small heating rate (beta <= 1 K min(-1)) in a stream of dry N-2. The kinetic behavior comprised the presence of an induction period and a sigmoidal mass loss process characterized by a derivative mass loss curve with a symmetrical shape under isothermal conditions, resembling the autocatalytic reaction in homogeneous kinetic processes. When DG-MH was heated at a larger beta (>= 2 K min(-1)), the melting of DG-MH occurred midway through the thermal dehydration process, by which a core-shell structure of molten DG-MH and surface product layer of crystalline anhydride was produced. Subsequently, thermal dehydration proceeded as a complex multistep process. Furthermore, the thermal dehydration initiated at approximately the melting point of DG-MH upon the application of a certain water vapor pressure to the reaction atmosphere, and proceeded in the liquid-state, exhibiting a smooth mass loss process to form crystalline anhydride. The reaction pathway and kinetics of the thermal dehydration of DG-MH and the corresponding changes with the sample and reaction conditions are discussed on the basis of the detailed kinetic analysis.

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