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The system K2Mg2(SO4)3 (langbeinite)-K2Ca2(SO4)3 (calcium-langbeinite)

G.W. Morey·J.J. Rowe·R.O. Fournier
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Abstract

The join between the compositions K 2 Mg 2 (SO 4 ) 3 and K 2 Ca 2 (SO 4 ) 3 was studied by means of high-temperature equilibrium quenching techniques and by means of a heating stage mounted on an X-ray diffractometer. Complete solid solution exists in the system, but at 25°C members of the solid solution series are isometric only in the composition range 0–73·5 wt. per cent K 2 Ca 2 (SO 4 ) 3 . At compositions richer in K 2 Ca 2 (SO 4 ) 3 than 73·5 wt. per cent, members of the series are optically biaxial. At higher temperatures members of the solid solution series are isometric at successively more calcium-rich compositions and pure K 2 Ca 2 (SO 4 ) 3 is isometric above about 200 ± 2°C. The system is not binary, as mixtures richer in K 2 Ca 2 (SO 4 ) 3 than 42 wt. per cent decompose with the formation of liquid and CaSO 4 .

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G.W. Morey, J.J. Rowe, R.O. Fournier. 1964. The system K2Mg2(SO4)3 (langbeinite)-K2Ca2(SO4)3 (calcium-langbeinite). https://doi.org/10.1016/0022-1902(64)80232-3

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USGS1967

The ternary system K2SO4 MgSO4 CaSO4

Melting and subsolidus relations in the system K 2 SO 4 MgSO 4 CaSO 4 were studied using heating-cooling curves, differential thermal analysis, optics, X-ray diffraction at room and high temperatures and by quenching techniques. Previous investigators were unable to study the binary MgSO 4 CaSO 4 system and the adjacent area in the ternary system because of the decomposition of MgSO 4 and CaSO 4 at high temperatures. This problem was partly overcome by a novel sealed-tube quenching method, by hydrothermal synthesis, and by long-time heating in the solidus. As a result of this study, we found: (1) a new compound, CaSO 4 ·3MgSO 4 (m.p. 1201°C) with a field extending into the ternary system; (2) a high temperature form of MgSO 4 with a sluggishly reversible inversion. An X-ray diffraction pattern for this polymorphic form is given; (3) the inversion of β-CaSO 4 (anhydrite) to α-CaSO 4 at 1195°C, in agreement with grahmann ; (1) (4) the melting point of MgSO 4 is 1136°C and that of CaSO 4 is 1462°C (using sealed tube methods to prevent decomposition of the sulphates); (5) calcium langbeinite (K 2 SO 4 ·2CaSO 4 ) is the only compound in the K 2 SO 4 CaSO 4 binary system. This resolved discrepancies in the results of previous investigators; (6) a continuous solid solution series between congruently melting K 2 SOP 4 ·2MgSO 4 (langbeinite) and incongruently melting K 2 SO 4 ·2CaSO 4 (calcium langbeinite); (7) the liquidus in the ternary system consists of primary phase fields of K 2 SO 4 , MgSO 4 , CaSO 4 , langbeinite-calcium langbeinite solid solution, and CaSO 4 ·3MgSO 4 . The CaSO 4 field extends over a large portion of the system. Previously reported fields for the compounds (K 2 SO 4 ·MgSO 4 ·nCaSO 4 ), K 2 SO 4 ·3CaSO 4 and K 2 SO 4 ·CaSO 4 were not found; (8) a minimum in the ternary system at: 740°C, 25% MgSO 4 , 6% CaSO 4 , 69% K 2 SO 4 ; and ternary eutectics at 882°C, 49% MgSO 4 , 19% CaSO 4 , 32% K 2 SO 4 ; and 880°, 67·5% MgSO 4 , 5% CaSO 4 , 27·5% K 2 SO 4 .

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