Fe-Zn mixing energetics of the Iss phase in the system Cu-Fe-Zn-S

A thermodynamic analysis of the intermediate solid solution (Iss) of near-cubanite composition has been attempted by considering an Fe–Zn exchange equilibrium between Iss and sphalerite. The interchange free-energy parameter of Fe–Zn mixing in Iss (W^Iss) and the free energy of the exchange equilibrium (G_1,T ) have been deduced at 500, 600, 700 and 723° C using the compositional data of sphalerite and Iss from phase equilibrium experiments and by the standard method of linear regression analysis. For sphalerite, two independent activity-composition models have been chosen. The extracted values of G_1,T and W^Iss, using both models, are compared. Although the values match, the errors in the extracted parameters are relatively larger when Hutcheon's model is used. Both G_1,T and W^Iss show linear variations with temperature, as given by the following relations: G^1,T = –35.41 + 0.033 T in kcal (SE=0.229)W^ISS= 48.451 – 0.041 T in kcal (SE=0.565) Activity-composition relations and different mixing parameters have been calculated for the Iss phase. A large positive deviation from ideality is observed in Iss on the join CuFe₂S₃–CuZn₂S₃. No geothermometric application has been attempted in this study, even though Iss of cubanite composition (isocubanite) in association with sphalerite, pyrite and pyrrhotite is reported from seafloor hydrothermal deposits. This is due to the fact that: (a) the temperatures of formation of these deposits are significantly lower than 500° C, the lower limit of appropriate experimental data base; (b) microprobe data of the coexisting isocubanite and sphalerite in the relevant natural assemblages are not available.Symbols a _J ⁱ activity of component i in phase J - G_{1, T} standard free energy change of reaction (cal) - G^IM free energy of ideal mixing (cal) - G^EM free energy of excess mixing (cal) - G _M ^ex free energy of mixing (cal) - G _i excess free energy of mixing at infinite dilution (cal) - _i ^J activity coefficient of component i in phase J - _i ^{J, 0} standard chemical potential of component i in phase J (cal) - ; _i ^J chemical potential of component i in phase J (cal) - R universal gas constant (1.98717 cal/K·mol) - T temperature in degree (K) - W^J interchange free energy of phase J in (cal) - X _J ⁱ mole fraction of component i in phase J