Thermodynamic Properties of Organized Solutions

Head investigator has pointed out a significance of the so-called“organized solutions(Systems)”(Kozo Shinoda，J.Phys.Chem.，#china_person0#，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&lt；plus-minus&gt；1，and 19.5°C，42&lt；plus-minus&gt；2for tetrabutylammonium polyacrylate and for tetraisopentylammonium polyacrylate，respectivthes(3)Solubilities of a series of quaternary ammonium salts R_4NX(R=CH_3-n-C_8H_&lt；17&gt；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 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 densulate polasures。These results were similarly interpreted by the existence of an ordered structure of water around both R_4N cation and polyacrylate anion。

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.