A thermodynamic study of pyrite and pyrrhotite

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Through the use of the electrum-tarnish method the following equation has been found to interrelate the composition of pyrrhotite, fugacity of sulfur, and temperature: In this equation f s 2 is the fugacity of sulfur relative to the ideal diatomic gas at 1 atm, N is the mol fraction of FeS in pyrrhotite (in the system FeS-S 2 ), and T the absolute temperature. The experimental uncertainty in the equation is 0-003 in N . The activity of FeS ( a FeS ) in pyrrhotite relative to the pure substance at the temperature of consideration follows from the above equation by virtue of the Gibbs-Duhem relation; it is given by: The electrum-tarnish method has permitted us to determine the f s 2 vs. T curve for the univariant assemblage pyrrhotite-pyrite-vapor from 743 to 325°C. Our determinations of the composition of pyrrhotite are in excellent agreement with the results of Arnold. The activity of FeS in pyrite-saturated pyrrhotite is very different from unity, a fact that greatly influences the interpretation of some other phase equilibrium studies involving pyrrhotite and their application to sulfide mineral assemblages, but has little effect on the more general calculations of composition of hydrothermal or magmatic fluids. Pressure effects calculated from available volumetric data on the phases are small.

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