Thermochemistry of alloys of transition metals: Part III. Copper-silver, -titanium, -zirconium,and -hafnium at 1373 K

The enthalpies of mixing of liquid copper with liquid silver and with solid titanium, zirconium, and hafnium have been measured by high temperature reaction calorimetry at 1371 to 1373 K. A least squares treatment of the data for copper-silver alloys yields the following expression for the molar enthalpy of mixing: δH_mix = x_Agx_Cu(17.66-5.46 x_Ag) kJ mol^-1. The enthalpies of solution of solid titanium, zirconium, and hafnium in dilute solutions in liquid copper are all exothermic; the following values were found: -2.0 kJ mol^-1 for Ti, -52.5 kJ mol^-1 for Zr, and -46.3 kJ mol^-1 for Hf. These values are all significantly less exothermic than predicted by the semiempirical theory of Miedema. The enthalpies of formation of congruent melting intermetallic phases in the systems Cu-Ti, Cu-Zr, and Cu-Hf were measured by drop calorimetry or by solution calorimetry in liquid copper. The enthalpies of formation of the solid alloys have been compared with corresponding data for the liquid alloys.