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A new method for the determination of the fugacity of sulfur in laboratory systems consists of visual observation of the development and decomposition of a sulfide tarnish phase on silver-gold alloy (electrum) of precisely known composition. The alloy system is calibrated against pure sulfur. The method has the following advantages: simple apparatus; ability to cover a large range of fugacity of S2; ability to cover a large temperature range by permitting runs of long duration; ability to tolerate other components in the gas phase; and ease of recovery of the quenched charges for determinations of phases and compositions. Results obtained by the electrum-tarnish method are in satisfactory agreement with those obtained by other workers for the fs2 vs. T curves for the assemblage Ni(1-x)S + NiS2. The electrum-tarnish method shows promise for investigating many other reactions. Univariant reactions studied by this method can be represented as lines forming a genetic grid in terms of the environmental parameters fs2 and T, The slopes of such lines can yield valuable thermodynamic data for the phases involved, but activity coefficients must be known for phases of variable composition. ?? 1964.
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The electrum-tarnish method for the determination of the fugacity of sulfur in laboratory sulfide systems