ZrO_2・CaO を用いた酸素濃淡電池による硫化物および硫酸塩の標準生成自由エネルギーの測定

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The following cells were constructed with ZrO_2・CaO as an electrolyte and pure SO_2 gas was supplied to the testing electrode chamber. pure SO_2, MnO, MnS, Pt/ZrO_2・CaO/Pt, Air……(1) pure SO_2, Cu, Cu_2S, Pt/ZrO_2・CaO/Pt, Air……(2) pure SO_2, NiO, NiSO_4, Pt/ZrO_2・CaO/Pt, Air……(3) pure SO_2, CoO, CoSO_4, Pt/ZrO_2・CaO/Pt, Air……(4) pure SO_2, Fe_2O_3, Fe_2(SO_4)_3, Pt/ZrO_2・CaO/Pt, Air……(5) The electromotive forces of those cells in the temperature range from 800 to 1400K were generally very stable and very reproducible except for the cell of equation (3). Reversibility of the electromotive forces was proved sufficiently good by supplying a small external current to the cells. From the electromotive forces and the standard free energies of formation of the relevant oxides, those of MnS, Cu_2S, NiSO_4, CoSO_4 and Fe_2(SO_4)_3 were determined as follows. (1) Mn(s)+1/2S_2(g)=MnS(s) ⊿G_<MnS>=-65390±510+(16.13±0.83)T 1013 to 1350K (2) 2Cu(s)+1/2S_2(g)=Cu_2S(s) ⊿G_<Cu_2S>=-31110±350+(7.38±0.65)T 963 to 1286K (3) Ni(s)+1/2S_2(g)+2O_2(g)=NiSO_4(s) ⊿G_<NiSO_4>=-216300±800+(100.3±1.9)T 903 to 1069K (4) Co(s)+1/2S_2(g)+2O_2(g)=CoSO_4(s) ⊿G_<CoSO_4>=-221200±500+(96.98±1.02)T 921 to 1121K (5) 2Fe(s)+3/2S_2(g)+6O_2=Fe_2(SO_4)_3(s) ⊿_<Fe_2(SO_4)_3>=-626100±1900+(274.4±6.4)T 823 to 904K The above free energy changes showed good agreements with the previous data by other investigators except for iron sulfate. However, all of the standard deviations of the present data were much smaller than those of the data by other investigators.
社団法人日本鉄鋼協会の論文
1977-03-01

ZrO_2・CaO を用いた酸素濃淡電池による硫化物および硫酸塩の標準生成自由エネルギーの測定

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