Zushi Yuto, Iwasaki Shun, Koga Nobuyoshi
Department of Science Education, Division of Educational Sciences, Graduate School of Humanities and Social Sciences, Hiroshima University, 1-1-1 Kagamiyama, Higashi-Hiroshima 739-8524, Japan.
Phys Chem Chem Phys. 2022 Jul 6;24(26):15736-15748. doi: 10.1039/d2cp01948e.
The kinetics of the thermal dehydration of compacted composite grains of NaCO·HO (SC-MH) comprising columnar SC-MH crystalline particles and an SC-MH matrix were investigated as a model system for composites of the same compound with a porphyritic texture. The presence of an induction period was confirmed as a novel finding for the thermal dehydration of SC-MH. The subsequent mass loss process was characterized as a partially overlapping two-step process attributed to the consecutive reactions of SC-MH matrix and columnar SC-MH crystalline particles. The overlapping nature of two reaction steps was revealed by determining the contributions and kinetic parameters of the individual reaction steps a kinetic deconvolution analysis. Furthermore, the initial mass loss process caused by the thermal dehydration of the SC-MH matrix was characterized as a physico-geometrical consecutive process comprising a surface reaction and a subsequent three-dimensional (3D)-phase boundary-controlled reaction. The subsequent thermal dehydration of the columnar SC-MH crystalline particles compacted in the grains was characterized as being geometrically constrained by 3D-interface shrinkage, forming two reaction interfaces during the overlapping stage of the two reaction steps. It was expected from the kinetic results that the linear advancement rate of the second reaction interface was influenced by the water vapor produced at the reaction interface of the first reaction step. This caused the linear advancement rate of the second reaction interface to accelerate as the reaction proceeded due to contraction of the first reaction interface and completion of the first reaction step.
以具有斑状结构的相同化合物复合材料的模型系统,研究了由柱状SC-MH晶体颗粒和SC-MH基质组成的压实复合颗粒NaCO·HO(SC-MH)的热脱水动力学。确认存在诱导期是SC-MH热脱水的一个新发现。随后的质量损失过程被表征为一个部分重叠的两步过程,这归因于SC-MH基质和柱状SC-MH晶体颗粒的连续反应。通过确定各个反应步骤的贡献和动力学参数(动力学反褶积分析)揭示了两个反应步骤的重叠性质。此外,由SC-MH基质的热脱水引起的初始质量损失过程被表征为一个物理几何连续过程,包括表面反应和随后的三维(3D)相边界控制反应。颗粒中压实的柱状SC-MH晶体颗粒的随后热脱水被表征为受到3D界面收缩的几何约束,在两个反应步骤的重叠阶段形成两个反应界面。从动力学结果可以预期,第二个反应界面的线性推进速率受到第一个反应步骤的反应界面处产生的水蒸气的影响。这导致第二个反应界面的线性推进速率随着反应的进行而加速,这是由于第一个反应界面的收缩和第一个反应步骤的完成。