Studies in the chemical metallurgy of the titanium group metals

Synthesis and nonstoichiometry of the zirconium trihalides

“…The recent restudy of the tribromide structure utilizing single-crystal data yielded small anisotropic thermal parameters for all atoms and these were plausibly interpreted in terms of the absence of local metal displacements (pairing etc.) and in support of the choice of the space group.7 Comparison of both the lattice parameters reported in the last study, a = 6.7275 (20) Á and c = 6.2992 (14) Á, with those in Table I and the dark brown color for the ZrBr3 product reported earlier8 with that cited above at first thought suggests that the actual ZrBr3 crystal utilized may have been significantly superstoichiometric through oxidation by the excess of solvated zirconium(IV) in the eutectic melt from which it was grown. Flowever, analytical data have consistently supported a stoichiometry quite near Br:Zr = 3.0:1,21 in which case another less obvious explanation will be necessary.…”

Synthesis, Structure, and Magnetism of La15.9(2)Cr5.4(2)S32: A Cr(III) Sulfide Containing d3-d3Cr2S912-Bioctahedra with Large Antiferromagnetic Coupling

“…The metal halide structures are defined by an octahedron of metal atoms in which 12 halide ions bridge each octahedral edge. These units are found in some binary metal halides, such as PtCl 2 and ZrI 2 , but the clusters in La 15.9(2) Cr 5.4(2) S 32 differ from the prototypical M 6 X 12 clusters in several important aspects. The differences are best illustrated in cluster O.…”

Thermodynamics of Vaporization of ZrI4 from Substoichiometric Solid Zirconium Iodides

“…Shelton and co-workers (2)(3)(4)(5)(6) have used this method with effusion mass loss measurements in studies of zirconium halide systems. In our measurements the pressure of ZrI4 was observed by a torsion-effusion method in which ZrI4 slowly escaped from the system so that the over-all composition changed with time and the change in composition was evaluated from the mass loss, which was continuously determined with a Cahn RH-10 recording microbalance.…”