Systematics and anomalies in rare earth/aluminum bromide vapor complexes: thermodynamic properties of the vapor complexes LnAl3Br12 from Ln = Sc to Ln = Lu.

Systematics and anomalies in the rare earth/aluminum bromide vapor complexes have been investigated by the phase equilibrium-quenching experiments. The measurements suggest that the LnAl3Br12 complexes are the predominant vapor complexes for the 16 rare earth elements Ln = Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu in the temperature range 601-833 K and pressure range 0.01-0.22 MPa, which is different from the rare earth/aluminum chloride systems, where the predominant vapor complexes are LnAl3Cl12 from Ln = La to Ln = Lu, but LnAl2Cl9 for Ln = Sc and Y are roughly in the same ranges, which indicates the importance of the halogen anion radius on the rare earth vapor complex formation. In the temperature and pressure ranges, gaseous Al2Br6 and AlBr3 are dominant species and the molar fraction of LnAl3Br12 is normally less than 0.01. Thermodynamic functions of the reactions LnBr3(s) + (3/2)Al2Br6(g) = LnAl3Br12(g) were calculated from the measurements for the 16 rare earth elements and then smoothly interpolated for the radioelement Ln = Pm. The standard molar enthalpies and standard molar entropies show significant Gd divergences from LaAl3Br12 to LuAl3Br12 when plotted as functions of the rare earth atomic number. They also suggest nearly linear manner for ScAl3Br12, LuAl3Br12, YAl3Br12, and LaAl3Br12 when plotted as functions of the rare earth ionic radius.