Abstract
The thermodynamic properties of the palladium-tin system have been investigated over the entire composition range. Reversible galvanic cells employing a thoria-yttria solid electrolyte and a Ni-NiO reference electrode have been used between 900 and 1200°K for measurements on solid alloys containing 0–55 at.% tin. The results have been combined with similar molten salt electrolyte studies on the more tin-rich (liquid) alloys to provide complete data for the free energies of the system at 1050°K. An isoperibol tin-solution calorimeter has been used to measure the heats of formation at 320°K of the α-solid solution alloys and the intermediate phases Pd 3Sn, Pd 2Sn, Pd 3Sn 2, PdSn, PdSn 2, PdSn 3 and PdSn 4. Entropies of formation have been estimated by combination of the free energy and enthalpy measurements. The thermodynamic properties of the alloys are discussed in relation to the electronic and structural characteristics of the phases; it is hypothesised that the thermodynamic properties are strongly influenced by effects arising from electron transfer.
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