RI 8405 Electrochemical Determination of Gibbs Energies of Formation of MoS2 and WS2_Redacted

"As part of the Bureau of Mines effort to provide thermodynamic data for the advancement of mineral technology, the Gibbs energies of formation of MoS2 (molybdenite) and WS2 (tungsten disulfide) were determined with high-temperature galvanic cells employing stabilized Zr02 (zirconia) as the electro¬lyte. In the temperature range from 867 to 1,209 K, potential measurements were obtained for the cellPt, MoS2 , Mo02 , SO2 = 1 atm // Zr02 // 02 = 0.0112 atm, Pt, with the overall cell reactionMoS2(c) + 3 02(g, 0.0112 atm) = Mo02 (c) + 2 S02(g). (1)These results, combined with the best available values for Gibbs energies of formation (?G°f) of Mo02 (molybdenum dioxide) and SO2 (sulfur dioxide) from the literature, give the standard Gibbs energy of formation of MoS2, ?G°f, for the reactionMo(c) + S2(g) = MoS2(c) (2)?G°f = -96.681 + 43.76 x 10-3T±0.538 kcal/mole, (3)where temperature (T) is expressed in Kelvins.Similar measurements in the temperature range from 872 to 1,210 K were obtained for the cellPt, WS2 , W03 , SO2 = 1 atm // Zr02 // 02 = 0.0114 atm, Pt, with the overall cell reactionWS2(c) + 3.5 02(g, 0.0114 atm) = W03 (c)+ 2 S02(g). (4) Combination of these results with the best available data of ?G°f for W03 (tungsten trioxide) and SO2 from the literature gives the Gibbs energy of formation of WS2 in the temperature range from 872 to 1,210 K for the reactionW(c) + S2(g) = WS2 (c)(5)?G°f = -92.429 + 43.88 x 10-3T ± 0.280 kcal/mole. (6)A third-law analysis yields a standard enthalpy (?H°f) for the reaction298Mo(c) + 2 S(rh) = MoS2(c), (7)?H°f = -67.36±0.60 kcal/mole, (8)298where the standard states are pure crystalline MoS2 / and rhombic sulfur."