Lanthanide Contraction in Ln F3 (Ln = Ce-Lu) and Its Chemical and Structural Consequences: Part 1: Location of YF3 in the Ln F3 Series According to Its Chemical and Structural Characteristics

Abstract

A lanthanide contraction(LC) of 14 lanthanides (Ln) from ₅₈Ce to ₇₁Lu consists of the interaction of Ln nucleus with 4f-electrons. Rare earth elements (REEs-R) include Sc, Y, La, and 14 Ln. They are located in 4-6th periods of the subgroup of group III. The electronic structure divides R into short (d- Sc, Y, La) and long (14 f-elements Ce-Lu) homologous series. The most important chemical consequence of LC is the creation of a new conglomerate of 16 RF₃ by mixing fluorides of d- (Y, La) and f-elements. This determines the location of YF₃ among LnF₃. The location of YF₃ depends on the structural (formula volumes-V_form) and thermochemical (temperatures and heats of phase transformations, phase diagrams) properties. The location of YF₃ between HoF₃ and ErF₃ was determined by V_form at a standard pressure (P_st) and temperature (T_st). The location of YF₃ according to heats of phase transformations ΔH_fus and ΔH_trans is in a dimorphic structural subgroup (SSGr) D (Ln = Er-Lu), but without the exact "pseudo Z_Y". According to the temperatures of phase transformations (T_trans) in LnF₃ (Ln = Dy-Lu), YF₃ is located in the SSGr D between ErF₃ and TmF₃. The ErF₃-YF₃ and YF₃-TmF₃ phase diagrams show it to be between ErF₃ and TmF₃. The crystals of five β-LnF₃ (Ln = Ho-Lu) and β-YF₃ were obtained in identical conditions and their crystal structures were studied. V_form (at P_st and T_st) with "pseudo" atomic numberZ_Y = 67.42 was calculated from the unit cell parameters, which were defined with ±5 × 10^-4 Å accuracy. It determines the location of YF₃ between HoF₃ and ErF₃.

Keywords: heats of phase transformations; lanthanide contraction; lanthanides; phase diagrams; polymorphism; rare earth elements; yttrium trifluoride.