Thermodynamic Properties of Organized Solutions

Head investigator has pointed out a significance of the so-called "organized solutions（systems）" （Kozo Shinoda， J. Phys. Chem.，第2429号（1985年）这些系统的表现形式包括微解决方案、液体晶体、溶解性解决方案、微模拟、主机-来宾（包容性和融合）系统。在这个程序中，作为一个典型的主机-来宾系统，一系列四氢氨盐的类解决方案的热动力学特性和类似梯度的化合物主要被调查。主要结果概括如下：（1）四氨硫代硫酸盐、氨基羧基和卤化碳化物的类类clathrate氢化物的形成得到确认，并对其热调动力学特性进行了测试。（2）四戊二胺（或四戊二戊二胺）聚丙烯酸水合物的形成是通过使用不同扫描热量计的热分析方法证实的。“四氢氨盐的氢化物以前从未被人知道过聚合物动物。”这些氢化物的熔化点和氢化数为11.2 ° C、30&lt;加-minus&gt;1和19.5 ° C、42&lt;加-minus&gt;2，用于四氮opentylamonium polyacrylate，相关性（3）四氮胺盐系列R_4NX的溶剂（R=CH_3 -n-C_8H_<17>; X=Cl， Br， I， and c10_4）在水被测量后，这些结果被R_4N疗法周围水的冰伯格形成系统地解释，并被一种对冰伯格稳定性的强烈影响引起。（4）在类似于乳糖的胶状固体中对酒精进行了分析，并且在甲基酒精和乙基酒精之间发现了不同的行为。（5）对R_4N-聚丙烯酸酯制成的各种解决方案的可见度和密度测量。这些结果与R_4N cation和聚丙烯酸阴离子的有序结构的存在类似地解释。

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.