RI 8588 Electrochemical Determination of Gibbs Energies of Formation of Cobalt and Nickel Sulfides

The Bureau of Mines has determined the standard Gibbs energies (AGf°) of CoS1.035 (cobalt sulfide) and Ni2.515S2 (nickel sulfide) with high-temperature galvanic cells using stabilized Zr02 (zirconia) as the electrolyte. Potential measurements were obtained for the cell Pt, CoS1.035, CoO, S02(g, 1 atm)//Zr02//02(g, 0.0114 atm), Pt, with the overall cell reaction C0S1.035(c) + 1.535 02(g, 0.0114 atm) = CoO(c) + 1.035 S02(g)¬ These results, combined with the best available data for ?Gf° of CoO and S02 from the literature, give the standard Gibbs energy of formation of CoS1.035 for the reaction Co(c) + 0 5175 S2(g) = CoS1.035(c) ?Gf° = -38.890 + 18.87 x 10-3T ± 0.185 kcal/mole (866.0 - 1,104.9 K), where temperature (T) is expressed in kelvins. Similar measurements were obtained for the cell Pt, N12.515S2, NiO, S02(g, 1 atm)//Zr02//02(g, 0.0122 atm), Pt, with the overall cell reaction Ni2.515S2(c) + 3.2575 02(g, 0.0122 atm) = 2.515 NiO(c) + 2 S02(g). Combination of these results with data for ?Gfo of NiO and S02 from the literature yields the standard Gibbs energy of formation of Ni2.515S2 for the reaction 2.515 Ni(c) + S2(g) = Ni2.S1SS2(c) ?Gf° -65.377 + 24.67 x 10-3T ± 0.541 kcal/mole (968.6 -1,053.7 K).