The data of Rau (1967) on the H 2 S/H 2 ratios of gas in equilibrium with high digenite solid solutions permit the calculation of the activity of Cu 2 S as a function of temperature and composition. The activity of Cu 2 S falls to 0.5 when the mole fraction (in the system Cu 2 S-S) drops only to 0.87. These calculations also permit the estimation of the activity of S 2 -temperature curve for the hexagonal chalcocite-high digenite reaction and a revised standard free energy for covellite.New data on the variation of the activity of S 2 in equilibrium with various metal/sulfur ratios for Cu = Fe in the intermediate solid solution permit the calculation of the activity of CuFeS 2 and show that it may drop as low as 0.2 at a mole fraction of 0.90 (system CuFeS 2 -Cu 2 Fe 2 S 2 ). The behavior of the copper-bearing solid solutions closely parallels that of pyrrhotite (Toulmin and Barton, 1964) in which the activity of FeS falls to 0.4 at a mole fraction of 0.9. A phase diagram is given for the CuFe-S join between 400 degrees and 700 degrees C.