Phase relations in the system PbS-PbSe-PbTe were investigated in the temperature range between 1150 and 300°C. There is a complete solid solution series along the join PbS-PbSe, whereas miscibility gaps exist below ∼ 350°C and 805°C along joins PbSe-PbTe and PbS-PbTe, respectively. Both gaps extend into the ternary system, and the range of the gap between PbS and PbTe reduces in size with temperature as well as Se-content.

By using the subregular model of mixing (Ganguly and Saxena, 1987), mixing energetics and activity composition relations of PbX were derived. The temperature-dependence of the interaction parameters was calculated to be 5057.6 − 1.7T, 9605.2 − 4.4T, 3933.2 − 3.1T (T < 500°C), 6410.3 − 6.35T (T < 500°C) 1649 − 0.26T, 1594.6 − 0.2T, and 12906.3 − 17.3T for WW_Ste, W_TeS, W_SeTe, W_TeSe, W_SSe, W_SeS, and W_SSeTe, respectively. A critical temperature along the join PbS-PbSe at ∼ 100°C was obtained from interaction parameter calculation, which suggests the separation of the PbS-PbSe series.

Correlation of solid-solution ranges established in this study with natural occurrences was made.