Ag-Cu exchange equilibria between α-miargyrite AgSbS2 and pyrargyrite Ag3SbS3 and between chalcostibite CuSbS2 and both pyrargyrite and high-skinnerite Cu3SbS3 are reported for the temperature range 150–350°C. All of these features are constrained by Ag-Cu exchange experiments (evacuated silica tubes; variable mass ratio) over the temperature range 120–400°C. Chalcostibite is found to take very little Ag into its structure. Utilizing Ag-Cu data from this study as well as the Ag-Cu solution models for pyrargyrite and high-skinnerite, a two-site Ag-Cu non-convergent ordered solution model for α-miargyrite () and a one-site Ag-Cu mixing model for chalcostibite ( = 25.0 kJ/gfw) are formulated. These results are constrained by a miscibility gap between α-miargyrite and chalcostibite from 225 to 325°C. The mixing model for α-miargyrite is expanded to include As for which α-miargyrite has a limited solubility along the Sb-As join with smithite AgAsS2.

Sulphosalts in the system CuSbS2-CuBiS2 (chalcostibite-emplectite) form a complete solid solution series. Seven compositions with the general formula Cu(SbxBi1–x)S2 have been synthesized using dry methods at 310°C. All members of the series are orthorhombic (space group Pnma) and show smoothly increasing a and b cell parameters with substitution of Bi for Sb; the c cell parameter increases up to 50% CuBiS2 substitution and then becomes constant. DSC experiments on CuBiS2 show an endothermic heat effect (2.45 kJ/mol.) at 472°C due to the breakdown reaction to Cu3BiS3 (wittichenite) plus Bi2S3 (bismuthinite). With the addition of 10% CuSbS2 to CuBiS2, the decomposition temperature increases and the endothermic peak is broadened but the energy remains essentially the same (2.53 kJ/mol.). No evidence of this decomposition was observed when the amount of the CuSbS2 component was >30%. The local structure and co-ordination of Cu in the samples were studied by EXAFS analysis of the Cu-K edge but no significant variation occurs in the local Cu environment. The Debye-Waller factor for the first shell of S atoms surrounding Cu in end member CuSbS2 tends to be slightly smaller than for the intermediate solid solutions, suggesting that the tetrahedral Cu environments in the intermediate composition samples is somewhat more disordered than in the end-member. The low expansion characteristics along c appear to be controlled by the linkages between the (CuS3 + BiS2) sheets perpendicular to c being relatively inflexible.