Abstract
Abstract The e.m.f. of the galvanic cells Pt, Ru, RuO2¦15 YSZ¦O2 (PO2 = 0.21 atm), Pt (I) and Pt, Cu, Cu2O¦8 YSZ¦RuO2, Ru, Pt (II) (YSZ is Y2O3-stabilized ZrO2) were measured over the ranges 1005–1106 K and 751–1200 K respectively, yielding the least-squares expressions E(I) = 813.57 − 0.50242T ± 2.52 mV (1) and E(II) = 80.27 + 0.07035T ± 1.33 mV (2) From these results, the standard Gibbs energy of formation of RuO2 was determined to be ΔG° f(RuO2(s)) = −305464 + 172.70T ± 1245 J mol−1 (3) A third-law analysis yielded a value of −313.9 ± 0.7 kJ mol−1 for ΔH°f (RuO2(s), 298.15 K). A partial phase diagram of the La-Ru-O system was determined, based on which the e.m.f. of the cell Pt, LaRuO 3 , La 2 O 3 , Ru ¦15 YSZ ¦ O 2 (P O 2 = 0.21 atm ) , Pt (III) was measured over the range 1032–1256 K yielding the expression E(III) = 844.14 − 0.49906T ± 2.40 mV (4) From this ΔG°f (LaRuO3(s)) = −1175350 + 274.57T J mol−1 was derived. The consistency of ΔG°f (LaRuO3(s)) was verified by e.m.f. measurements on the cell Pt, Cu, Cu2O¦8 YSZ¦LaRuO3, RuO2, La2O3, Pt (IV) at two temperatures.
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