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Solid-Liquid Phase Equilibria of Organic Compounds Under High Pressures

高压下有机化合物的固液相平衡

基本信息

批准号：
62550697
负责人：
MAKITA Tadashi
金额：
$ 1.22万
依托单位：
Kobe University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (C)
财政年份：
1987
资助国家：
日本
起止时间：
1987 至 1988
项目状态：
已结题

项目摘要

Solid-liquid phase equilibria of the binary mixtures of organic compounds have been investigated at temperatures from 278 to 343 K and pressures up to 500 MPa using a high-pressure optical vessel newly designed. The uncertainties in the measurements of temperature, pressure and composition are within 0.1 K, 0.5 MPa and 0.001 mole fraction, respectively.1 Systems investigated(1) simple eutectic systems : benzene + cyclohexane, benzene + 2-methyl-2-propanol(2) systems with formation of intermolecular compounds : carbon tetrachloride + benzene, carbon tetrachloride + p-xylene(3) partial solid solution system : -methylnaphthalene + -methylnaphthalene(4) complete solid solution system : chlorobenzene + bromobenzene2 Apparatus and experimental proceduresThe measurements were performed in a high-pressure vessel with a couple of optical windows. The sample liquid of a known composition was introduced in the equilibrium vessel, which was immersed in a liquid bath thermostatically controlled within 0.05 K, and was compressed gradually. The phase transition and solid-liquid coexistence were observed visually.3 Experimental results and discussionThe freezing temperature at a constant composition increases monotonously with increasing pressure in all cases of phase diagrams. The eutectic temperature shifts to higher temperature, and the eutectic composition shifts to richer composition of the component whose pressure coefficient of freezing temperature is larger. In the systems forming intermolecular compounds, it is found that the congruent melting point turns to the incongruent melting point, and that one compound disappears under high pressure. The solid-liquid coexistence curve can be correlated satisfactorily by an equation newly proposed for all systems.

本文用新设计的高压光学容器研究了有机化合物二元混合物在278 ~ 343 K和500 MPa压力下的固液相平衡。温度、压力和组成测量的不确定度分别在0.1 K、0.5 MPa和0.001摩尔分数以内。1研究的体系（1）简单低共熔体系：苯+环己烷、苯+ 2-甲基-2-丙醇（2）形成分子间化合物的体系：四氯化碳+苯、四氯化碳+对二甲苯（3）部分固溶体体系：-甲基萘+ -甲基萘（4）完全固溶体体系：氯苯+溴苯2装置和实验步骤在具有一对光学窗口的高压容器中进行测量。将已知组成的样品液体引入平衡容器中，将其浸入恒温控制在0.05K内的液浴中，并逐渐压缩。的相变和固-液共存进行了可视化观察。3实验结果和讨论的凝固温度在一个恒定的组成单调增加，在所有情况下的相图的压力增加。凝固温度压力系数大的组分，其共晶温度向高温方向移动，共晶成分向富成分方向移动。在形成分子间化合物的体系中，发现在高压下，一种化合物的熔点由一致熔点变为不一致熔点。用新提出的适用于所有体系的固-液共存曲线关联式，可以得到满意的关联结果。