PHASE RELATIONS AND ACTIVITIES IN THE Cu-Fe-S-As AND Cu-Fe-S-Sb SYSTEMS AT 1473K

摘要

To analyze the behavior of minor elements in the copper smelting process, the phase relations and the activities of arsenic and antimony in the miscibility gap of Cu-Fe-S-X (X = As or Sb) system have been determined at 1473K by the quenching method and the double Knudsen cell-mass spectrometric method, respectively. The experiments have been conducted for the charges in the miscibility gap with different mass%Fe/mass%Cu ratios with varying arsenic or antimony content. The activity measurements indicate that the arsenic activities in both the metal and matte phases show extremely negative deviation from the ideal behavior. The Raoultian activity coefficients at infinite dilution in the metal and matte phases are found to be almost constant against the charges in the miscibility gap, and they are 4.3 X 10~(-3) and 5.5 X 10~(-2) for the metal and matte phases, respectively. Moreover, the activity measurements of antimony show an activity value larger than that of arsenic but it still deviates negatively from Raoult's law. The activity coefficients of antimony at infinite dilution are found to be 1.2 X 10~(-2) and 2.2 X 10~(-1) for the metal and matte phases, respectively. The vapor pressures of the predominant As, As_2, AsS, Sb, Sb_2, and SbS species in the gas phases of arsenic and antimony, respectively, equilibrated with the immiscible solutions have been calculated on the basis of the determined activity coefficients and they are very small at less than 1 Pa, even when their contents in the metal phase are increased up to 10 mass%.