화학공학소재연구정보센터
Journal of the American Chemical Society, Vol.119, No.47, 11481-11486, 1997
Structure, stoichiometry, and morphology of bromine hydrate
The hydrate of bromine was one of the first clathrate hydrates discovered. It has played a significant role in the development of the solid solution theory of clathrate hydrates, yet its detailed structure remains unknown. This hydrate again has become a test case for two different views of clathrates: the solid solution model, after van der Waals and Platteeuw, that sees clathrates as unstable lattices which derive stability from a minimum degree of cage filling and thus are nonstoichiometric, and a view promoted by Dyadin and Aladko that all large cages in a hydrate structure need to be filled. In light of the latter view, existing data obtained over the last similar to 160-year period on the composition and morphology of bromine hydrate would require the existence of four different hydrate structures. Our single crystal diffraction study of 16 different crystals of distinct compositions (Br-2 . 8.62H(2)O to Br-2 . 10.68H(2)O) and morphologies showed that there is just a single structure (tetragonal, P4(2)/mnm, a = 23.04 Angstrom, c = 12.07 Angstrom, the structure originally proposed by Alien and Jeffrey) with considerable variation in the degree of occupancy of the large cages. The results favor the solid solution model for clathrates, and settle the question of long standing regarding the structure(s) of bromine hydrate. The bromine atoms occupy the large 14- and 15-hedral cages with up to 15 different crystallographically independent sites per cage and fractional occupancies from 0.19 to