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Thermodynamic Properties of Organized Solutions

有序溶液的热力学性质

基本信息

批准号：
60470006
负责人：
SHINODA Kozo
金额：
$ 3.39万
依托单位：
Yokohama National University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (B)
财政年份：
1985
资助国家：
日本
起止时间：
1985 至 1987
项目状态：
已结题

项目摘要

Head investigator has pointed out a significance of the so-called "organized solutions(systems)" (Kozo Shinoda, J. Phys. Chem., 89, 2429 (1985)). Representatives of these systems are micellar solutions, liquid crystals, solubilized solutions, microemulsions, host-guest (inclusion and enclathration) systems. In this program, as typical host-guest systems, thermodynamic properties of aqueous solutions of a series of quaternary ammonium salts and the formation of clathrate-like hydrates of these salts were mainly investigated. Main results are summarized as follows:(1) The formation of clathrate-like hydrates of tetrabutylammonium alkanesulfonates, amino carboxylates, and halogenated carboxylates was confirmed and their thermodynamic properties were examined.(2) The formation of tetrabutylammonium (or tetraisopentylammonium) polyacrylate hydrate was confirmed by a thermal analytic method using a differential scanning calorimeter. The clathratelike hydrates of quaternary ammonium salts having polymeric anions have never been known before. The melting points and hydration numbers of these hydrates were 11.2゜C, 30<plus-minus>1, and 19.5゜C, 42<plus-minus>2 for tetrabutylammonium polyacrylate and for tetraisopentylammonium polyacrylate, respectivthes(3) Solubilities of a series of quaternary ammonium salts R_4NX (R=CH_3 - n-C_8H_<17> ; X=Cl, Br, I, and c10_4) in water were measured and these results were systematically interpreted by an iceberg formation of water around the R_4N cation and by a steric affect caused by the anion on the stability of the iceberg.(4) Intercalation of alcohols within a clathrate-like gydrate solid was examined and the different behaviors were found between methyl alcohol and ethyl alchohol.(5) Viscosity and density measurements on aqueous solutions of R_4N-polyacrylate were made. These results were similarly interpreted by the existence of an ordered structure of water around both R_4N cation and polyacrylate anion.

首席研究员指出了所谓的“有组织的解决方案（系统）”的重要性（Kozo Shinoda，J. Phys. Chem.，89，2429（1985））。这些系统的代表是胶束溶液，液晶，增溶溶液，微乳液，主-客体（包合和包合）系统。本项目主要研究了一系列季铵盐水溶液作为典型的主-客体体系的热力学性质及其笼形水合物的形成过程。主要研究结果如下：（1）证实了四丁基烷基磺酸铵、氨基羧酸铵和卤代羧酸铵的笼形水合物的形成，并考察了它们的热力学性质。(2)通过使用差示扫描量热计的热分析方法确认了四丁基铵（或四异戊基铵）聚丙烯酸酯水合物的形成。具有聚合阴离子的季铵盐的笼形水合物以前从未被发现。四丁基聚丙烯酸铵和四异戊基聚丙烯酸铵的熔点和水合数分别为11.2 ℃和<plus-minus>30.1;四丁基聚丙烯酸铵和四异戊基聚丙烯酸铵分别为19.5 ℃和42.2<plus-minus><17>。X=Cl、Br、I，和c10_4），并用R_1附近水的冰山形成对这些结果进行了系统的解释。4 N阳离子和由空间位阻效应引起的阴离子对冰山稳定性的影响。(4)研究了醇类化合物在笼形固体中的插层行为，发现甲醇和乙醇的插层行为不同。(5)对R_4 N-聚丙烯酸酯水溶液的粘度和密度进行了测定。这一结果也可以用水在R_4N阳离子和聚丙烯酸酯阴离子周围的有序结构来解释。