The Supposed High-temperature Polymorphism of Tin

TIN has long been cited as offering a classic example of polymorphism, second in repute only to the allotropy of sulphur. The notorious "tin disease," which Cohen1 has studied so exhaustively in terms of the enantiotropic transformation of tetragonal white 0 tin to cubic gray a tin, has apparently encouraged the expectation that one or more addi-tional polymorphic modifications might exist. The search for confirma-tion of this idea has, as might be anticipated, led to the accumulation of a body of miscellaneous evidence, much of which would probably never have been sought, or taken seriously even by its discoverers, but for previous assumptions. The ball apparently was started rolling in 1880 by Trechmann,' who reported a new modification of tin (y tin), which was brittle and found in "hard head," a highly arsenical, slaggy material produced in a certain stage of tin smelting. A mixture of two kinds of crystals was obtained from a Cornish tin furnace, and those thought to be y tin were studied crystallographically. The results indicated that these crystals were rhombic and of different density from the tetragonal tin prepared electrolytically by Miller.3 Their analysis was given as 98.7 per cent Sn, 1.3 per cent Fe, and traces of As, Sb, Bi and S. In 1881 von Foullon4 obtained similar crystals from a Bohemian tin furnace. Headden5 examined crystals similar to those of Trechmann and von Foullon and reported them to be monoclinic, but of analysis corresponding to stannous sulphide. Later, Stevanovic,6 by goniometric measurements, proved that these crystals of SnS were really rhombic. Groth7 pictures and describes both "rhombic tin" (Fig. 9, vol. 1) and stannous sulphide (Fig. 84, vol. 1); their faces and angles correspond within the accuracy of measurement. Spencer3 in 1921 examined the above evidence critically; he found similar crystals from Cornish tin furnaces, proved them to be SnS, and even was able to analyze some of Trechmann's original specimens, finding high sulphur content. (Apparently Trechmann's analysis had been based on a second lot of crystals, not described crystallographically.)