RI 8301 Electrochemical Determination of the Gibbs Energy of Formation of Sphalerite (ZnS)

As part of the Bureau of Mines, U.S. Department of the Interior, effort to provide thermodynamic data for the advancement of minerals technology, the Gibbs energy of formation of sphalerite (zinc sulfide) was investigated with a high-temperature galvanic cell employing stabilized zirconia as the electrolyte. In the temperature range 948 to 1,210 K, potential measurements were obtained for the cell Pt, ZnS + ZnO, S02 = 1 atm // Zr02 // Cu20 + Cu, Pt, with the overall cell reaction ZnS(c) + 3 Cu20(c) = ZnO(c) + 6 Cu(c) + S02(g). (1) These results, combined with the best available values of ?Gf° for ZnO, S02, and Cu20 from the literature, give the Gibbs energy of formation of zinc sulfide for the reaction Zn(l,v) + 1/2 S2(g) = ZnS© (2) ?Gf° = -64.223 + 24.02 X 10-3T ± 0.650 kcal/mole (3) (948-1,180 K; standard states - pure liquid zinc and S2 gas at 1 atm), and ?Gf° = -92.720 + 48.17 X 10-3 ± 0.650 kcal/mole (1,180-1,210 K; standard states - pure zinc vapor and S2 gas at 1 atm). A third law analysis yields for the formation reaction Zn(1) + 1/2 S2(g) = ZnS(c), (5) a standard enthalpy of formation as follows: ?Hf298.15 = -63.64 ± 0.700 kcal/mole.