Reactions of intermetallic compounds in liquid ammonia. I, Bismuthides

Moore, Thomas Edwin, 1918-
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In view of the limited available information concerning reactions of intermetalllc compounds, this study was undertaken to initiate an extensive program of work on the chemistry of these compounds in liquid ammonia. It is hoped that the results of such a program will supplement and extend present knowledge so as to permit generalizations regarding the reactions of this important class of substances. The bismuthides were selected for study initially because less is known about their chemistry than about the corresponding plumbides, tellurides, and selenides and also because of the ease with which compounds of definite composition can be prepared in liquid ammonia. The normal or trisodium monobismuthide was chosen for the most complete investigation for the following reasons: (1) it has the simplest anion; (2) it is the least soluble bismuthide; (3) it is the only bismuthide having an atomic ratio of sodium to bismuth that would be expected from ordinary valence considerations. Since the behaviour of the tellurides, selenides, and sulfides toward oxidation had already been investigated by McCleary and Fernelius, it seemed advisable to extend the study of oxidation to include the bismuthides. By analogy to the formation of the salts of the oxygen acids of tellurium, selenium, and sulfur, it was hoped that emphasis on oxidation might provide a means of producing bismuthates. An important objective of this work also has been the development of more satisfactory experimental methods for carrying out studies on intermetallic compounds and their reactions