Okazaki Takahiro, Hara Masami, Muravyev Nikita V, Koga Nobuyoshi
Department of Science Education, Division of Educational Sciences, Graduate School of Education, Hiroshima University, 1-1-1 Kagamiyama, Higashi-Hiroshima 739-8524, Japan.
Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences, 4 Kosygin Str., 119991, Moscow, Russia.
Phys Chem Chem Phys. 2021 Dec 22;24(1):129-141. doi: 10.1039/d1cp04734e.
In this study, we investigated the mechanistic features and kinetics of the thermal decomposition of solids accompanied by liquefaction as exemplified by the thermal dehydration reactions of monosodium L-glutamate monohydrate (MSG-MH). The thermal dehydration of MSG-MH occurs two mass-loss processes comprising the elimination of crystalline water and intramolecular dehydration. Multistep kinetic behaviors and the liquefaction during both thermal dehydration processes were evidenced by systematic thermoanalytical measurements and microscopic observations. During the thermal dehydration of crystalline water, the liquefaction of the surface product layer occurred midway through the reaction, and the subsequent reaction proceeded with a geometrical constraint, where the solid reactant was covered by a liquid surface layer, affording a solid anhydride. The intramolecular dehydration of the solid anhydride yielded a liquid product on the surface of the reacting particles, and the internal solid reactant dissolved in the liquid product. Subsequently, the intramolecular dehydration proceeded in the liquid phase to afford liquid sodium pyroglutamate. The net kinetic behavior of the physico-geometrical reaction steps in each thermal dehydration process was revealed using kinetic approaches based on cumulative and conjunct kinetic equations. The advanced kinetic approaches employed to reveal the specific kinetic features of the heterogeneous reaction processes in solid-liquid-gas systems are described in this article.
在本研究中,我们以L-谷氨酸单钠一水合物(MSG-MH)的热脱水反应为例,研究了伴随液化的固体热分解的机理特征和动力学。MSG-MH的热脱水发生两个质量损失过程,包括结晶水的消除和分子内脱水。系统的热分析测量和微观观察证明了两个热脱水过程中的多步动力学行为和液化现象。在结晶水的热脱水过程中,表面产物层的液化在反应进行到一半时发生,随后的反应在几何约束下进行,其中固体反应物被液体表面层覆盖,生成固体酸酐。固体酸酐的分子内脱水在反应颗粒表面产生液体产物,内部固体反应物溶解在液体产物中。随后,分子内脱水在液相中进行,生成液体焦谷氨酸钠。使用基于累积和联合动力学方程的动力学方法揭示了每个热脱水过程中物理几何反应步骤的净动力学行为。本文描述了用于揭示固-液-气系统中非均相反应过程特定动力学特征的先进动力学方法。