Fundamental Researches on Metallurgical Treatment of Manganese Ores. I : On the Equilibrium in the Reduction of Mn_3O_4 with CO.

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The present report is the first part of a series of studies dealing with how to produce metallic manganese by electrolysis from low grade ores. In this part, the equilibrium in the reduction, Mn_3O_4+CO=3MnO+CO_2, was studied by means of a flow method in order to get thermodynamical data required in analysing pyrometallurgical treatment of manganese ores. The effects of temperature on the equilibrium constant and the free energy change in the reaction within the range of 500°〜800℃ were determined. The experimental data obtained may be summarized as follows : logK_ρ=318/T+0.373, 〓H=-2, 410+14.87 T-27.9・10^<-3>T^2+12.57・10^<-6>T^3, 〓F°=-2, 410+34.3 TlogT+27.9・10^<-3>T^2-6.29・10^<-6>T^3+80.5T. The present writers have also obtained the following results for dissociation equilibrium of Mn_3O_4 by combining the equation with the known one for CO and CO_2 : logPo_2=-28, 800/T+9.76, 〓H=65, 500+15.26T-28.6・10^<-3>T^2+12.57.10^<-6>T^3, 〓F°=65, 500-35.2Tlog T+28.6・10^<-3>T^2-6.29・10^<-6>T^3-50, 800・T^<-1>+61.3T.
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