Reactive crystallization in supercritical water.

超临界水中的反应结晶。

• 批准号: 07405036
• 负责人: ARAI Kunio
• 金额: $ 20.48万
• 依托单位: Tohoku University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1996
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07405036/
• 关键词: Supercritical water; Reaction Crystallization; Metal oxide fine particle; molecular dynamics simulation; Dielectric Spectra Analysis; Solvent structure; MD計算; MO計算; 溶媒和構造; noシミュレーション

The objective of our work was to examine supercritical water as a reaction solvent. We made both molecular simulations and experimental measurements in our studies. For the simulations, we used SPC model that was modified to have flexibility and to have cHarge located at the center of mass. We grafted a new intramolecular potential function to give the model applicability at high temperature. The new model could provide superior predictions of IR-spectra, pressure-volume-temperature, relations, saturation conditions, self diffusion coefficients, and other properties compared with current literature models for water. We also examined the dielectric behavior experimentally and theoretically. For the experiments, a new cell was constructed and used to study the behavior of hydrogen bonds as temperature and concentration of the system was varied up to about 373K.Alcohols were used as the solutes. We found that there were several regions of hydrogen bonding but that there was a continuous change in the time constants, in contrary to that reported in the literature. The three regions disappeared as the temperature was elevated indicating a weakening of the hydrogen bonding. However, simulation shows that hydrogen bonding still exists since bifurcated structure was found.

我们工作的目的是将超临界水作为一种反应溶剂。在研究中，我们进行了分子模拟和实验测量。对于模拟，我们使用了经过修改以具有灵活性并在质量中心充电的SPC模型。我们嫁接了新的分子内电势功能，以在高温下给予模型适用性。与当前的水文献模型相比，新模型可以提供IR-Spectra，压力量 - 温度，关系，饱和条件，自扩散系数和其他特性的卓越预测。我们还从实验和理论上检查了介电行为。对于实验，构建了一个新的细胞，并用于研究氢键的行为，因为该系统的温度和浓度变化为约373K。将其用作溶质。我们发现有几个区域的氢键区域，但与文献中报道的相反，时间常数发生了不断变化。由于温度升高，这三个区域消失了，表明氢键的衰弱。然而，模拟表明，由于发现分叉结构以来，氢键仍然存在。

项目成果

Tadafumi Adschiri, Yakima Hakuta, Kunio Arai: ""Reactive crystallization in supercritical water"" Symposium Series of Chemical Engineering. 49. 194 (1995)

Tadafumi Adschiri、Yakima Hakuta、Kunio Arai：““超临界水中的反应结晶””化学工程研讨会系列。

阿尻雅文: "超臨界水中での反応晶析" 化学工学シンポジウムシリーズ. 49. 194-199 (1995)

Masafumi Asiri：“超临界水中的反应结晶”化学工程研讨会系列。49. 194-199 (1995)