Hydrates of Organic Compounds. IV. Clathrate Hydrates of Various Bolaform Salts

The solid-liquid phase diagrams are presented for binary mixtures of water with various polymethylene-bis(tributylammonium) difluorides, [(n-C4H9)3N(CH2)nN(n-C4H9)3]F2 (n=4, 5, 6, 8, and 10); and with hexamethylenebis(tributylammonium) dihydroxide and its salts, [(n-C4H9)3N(CH2)6N(n-C4H9)3](X2 or Y) (X=OH, Cl, and Br; Y=OOC–COO and OOC–(CH2)3–COO). It has been found that all the compounds form congruently melting hydrates which have large hydration numbers. The hydrates appear to be clathrate-like hydrates essentially similar to those formed by many tetrabutyl(or isopentyl) ammonium salts. The most stable hydrate found in this study is [(n-C4H9)3N(CH2)6N(n-C4H9)3]F2 hydrate (mp 20.4 °C). The melting points of hexamethylenebis(tributylammonium) hydrates have been compared with those of the corresponding tetrabutylammonium hydrates.

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