Thermodynamic properties in liquid Ag–Sn alloys have been determined for
NSn=0.27–0.80 over the temperature range of 636–983 K, by the following emf method by means of a galvanic cell using fused salt electrolytes:
\ominus W/Sn(1)/SnCl
2 in KCl+LiCl/Ag–Sn(l)/W ⊕.
Activities of tin at 973 K exhibit negative deviations for silver-rich regions and positive for tin-rich regions from Raoult’s law, and
aSn values agree well with the determinations of Chowdhury
et al. Activities of silver exhibit negative deviations from Raoult’s law over the whole concentration range.
It has been observed that the activities of both components have intimate relations with the phase diagram of this system, suggesting that the strongly concentration dependence is connected with the existence of ζ, ε compound clusters in the melt, and with the physical properties of the liquid alloys.
It can be clearly seen that the anomalous fluctuations in the values of Δ\bar
HSn and Δ\bar
SSn at approximately
NSn=0.65–0.70, and possibly also at
NSn=0.55 by the determinations of Laurie
et al. are difficult to rationalize.
The thermodynamic properties of liquid alloys composed of IB metals (Cu, Ag and Au) and tin have been discussed in terms of the alloy solution theory of Engel. Namely, the activities and the heats of mixing for liquid alloys seem to be consistently explained on the assumption that the filling of d shell is incomplete for the IB metals as well as the transition metals, whereas it is complete for tin.
The activities and the heats of mixing of liquid Cu–Sn and Ag–Sn alloys are quite different from those of the liquid Au–Sn system, in which the activities show considerably negative deviations and the heats of mixing are exothermic, in the whole concentration range, owing to larger differences of electronegativity factor in the gold alloys.
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