RI 8486 Electrochemical Determination of Gibbs Energies of Formation of MnS and Fe0.9S

[As part of the Bureau of Mines effort to provide thermodynamic data for advancement of mineral resources technology, the standard Gibbs energies of formation (?G°f) of MnS (manganese sulfide) and Fe0.9 S (pyrrhotite) were investigated with a high-temperature galvanic cell employing stabilized Zr02 (zirconia) as the electrolyte. Potential measurements were obtained for the cell Pt, MnS, MnO, S02 (g, 1 atm)//Zr02//02(g, 0.0114 atm), Pt with the overall cell reaction MnS (s) + 1.5 02 (g, 0.0114 atm) = MnO (s) + S02 (g) . (1) These results give the standard Gibbs energy of formation of MnS for the reaction Mn (s) + 0.552 (g) = MnS (s) (2) ?G°f = -66.487 + 15.19 x 10-3T±0.207 kcal/mole (896.4 - 1,208.1 K) (3) where temperature (T) is expressed in kelvins. Similar measurements were obtained for the cell Pt, FeO .9S, Fe304 , S02 (g, 1 atm) //Zr02//02 (g, 0.0114 atm) , Pt with the overall cell reaction 10/3 FeO .9 S (s) + 16/3 02 (g, 0.0114 atm) = Fe.,04 (s) +10/3 S02 (g). (4) These results yield the standard Gibbs energy of formation for the reaction 0.9 Fe (s) + 0.5 S2 (g) = Fe0.9 S (s) (5) ?G°f = -35.229 + 12.67 x 1073T+-0.104 kcal/mole (839.5 - 1,086.6 K). (6) A third-law analysis of MnS data yields a standard enthalpy of formation (AH°f) for the reaction Mn (s) + S (rh) = MnS (s) (7) ?H°f298 = -51.16±0.21 kcal/mole (8) A similar third-law analysis for Fe0.9S data yields a ?29°f298 for the reaction 0.9 Fe(s) + S(rh) = FeO .9S(s) (9) ?HO\°f298 = -24.01±_0.15 kcal/mole. (10) ]