Phase diagrams of arsenic, antimony, and bismuth at pressures up to 70 kbars

Klement Jr, W. ; Jayaraman, A. ; Kennedy, G. C. (1963) Phase diagrams of arsenic, antimony, and bismuth at pressures up to 70 kbars Physical Review, 131 (2). pp. 632-637. ISSN 0031-899X

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The meltings under pressure of arsenic, antimony, and bismuth have been determined up to nearly 70 kbar by means of differential thermal analysis (DTA). Arsenic initially melts with a positive dT/dP, the fusion curve flattening out near 940°C at the highest pressures attained. The fusion curve of antimony exhibits practically no change with pressure initially, but takes on a slightly negative slope at higher pressures until a triple point is encountered near 57 kbar and 567°C; the high-pressure polymorph melts with a positive slope of 4.3°C/kbar. For bismuth, a triple point between the liquid and polymorphs IV and V occurs near 38.0 kbar and 296°C, in addition to the well-studied liquid-I-II and liquid-II-IV triple points at lower pressures. DTA was also used to determine the solid-solid phase boundaries in bismuth, triple points occurring between II, III, and IV near 24.0 kbar and 180°C and between III, IV, and V near 53 kbar and 174°C. The III-IV transition occurs at different temperatures upon heating and cooling and this hysteresis interval increases with pressure. No hystereses were observed for the IV-V and III-V transitions. At room temperature and at pressures beyond the well-known I-II and II-III transitions, the III-V transition is next encountered near ~78-82 kbar (as estimated by extrapolation). Suggestions are made for the structures of the high-pressure Bi polymorphs and analogies are drawn between Bi, Sb, and As for the melting and distortion under pressure of the normal rhombohedral structure.

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