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Ionic equilibrium in silicate slags Toop, Gerald Wesley

Abstract

The problem of determining the total number of discrete anions in both acid and basic silicate melts has been investigated in order to apply ionic theory and 'Temkin's rule' to binary and ternary silicate slags. With an examination of structure and equilibria in silicate melts, a method was developed for determining the most probable number of anions in any basic or acid slag in terms of an equilibrium constant involving singly bonded oxygen, doubly bonded oxygen, and free oxygen ions in the melt. It was found that for an appropriate value of the equilibrium constant, values of Temkin's ionic fraction of oxygen ions may be obtained that are close to, or equal to the activities of various metal oxides in binary silicate melts. This observation was consistent with the thermodynamics of the systems studied and was verified mathematically by the application of the Gibbs-Duhem relationship to ionic silicate melts. Some ionic forms of the Gibbs-Duhem equation were derived and applied successfully to the CaO-FeO-SiO₂ system containing divalent cations, and to the Cu₂O-PbO-SiO₂ system containing both divalent and monovalent cations. Some ternary activity values of Cu₂O and PbO were determined experimentally in the Cu₂O-PbO-SiO₂ system by equilibrating silica saturated melts of Cu₂O and PbO with copper-lead alloys at 1100°C.

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