Non-monotonic systematic variation of the thermodynamic properties of lanthanide metals in liquid bismuth

In a system consisting of molten eutectic mixture of LiCl, KCl, and liquid bismuth, the excess enthalpy changes of Ce, Pr, Nd and Ho in liquid bismuth were evaluated in a temperature range from 850 K to 1100 K by electromotive force measurement. The newly determined values were compared with those previously determined for La, Gd, Tb, and Dy, and the systematic variation of these values along the lanthanide series was discussed. As a result, it was found that the excess enthalpy changes of lanthanides show non-monotonic variation as a function of 2/3 power of molar volumes, which does not agree with the linear trend of variation which is anticipated by the semi-empirical rule. Instead of the conventional definition of the excess enthalpy changes standardized to the metallic states, those standardized to the hypothetical metallic vapor states were adapted and their systematics were discussed.