Abstract
Enthalpies of formation of (Pd + In) alloys have been obtained by direct reaction calorimetry using a very high temperature calorimeter between 1,425 and 1,679 K in the concentration range 0 < x{sub Pd} < 0.66. They are very negative with a minimum {Delta}{sub mix}H{sub m}{degree} = {minus}59.6 {+-} 2.5 kJ mol at x{sub PD} = 0.59 and independent of temperature within the experimental error. The integral molar enthalpy of mixing is given by {Delta}{sub mix}H{sub m}{degree}/{l_brace}kJ/mol{r_brace} = x(1 {minus} x) ({minus}126.94 {minus} 92.653x {minus} 83.231x{sup 2} {minus} 734.49x{sup 3} + 949.07x{sup 4}), where x = x{sub PD}. The limiting partial molar enthalpy of palladium in indium was calculated as {Delta}h{sub m} (Pd liquid in {infinity} liquid In) = {minus}127 {+-} 5 kJ/mol. The results are discussed and compared with the enthalpies of formation of solid alloys. The anomalous behavior of the partial enthalpy of Pd is assumed to be due to the charge transfer of, at most, two electrons of In to Pd.
Published Version
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