Synthesis and nonstoichiometry of the zirconium trihalides
The synthesis of ZrX/sub 3/ (X = Cl, Br, I) by reaction of the corresponding tetrahalides with ZrCl, ZrBr, or ZrI/sub 1.8/ in sealed tantalum tubing gives high-purity, single-phase products, thereby avoiding problems of the relatively low reactivity of and contamination by zirconium powder reductant used previously. Phase limits for the three trihalides established by isopiestic equilibration with the adjoining phases are 2.94 (2) less than or equal to Cl:Zr less than or equal to 3.03 (2) (440/sup 0/C), 2.87 (2) less than or equal to Br:Zr less than or equal to 3.23 (2) (435/sup 0/C), and 2.83 (5) (775/sup 0/C) less than or equal to I:Zr less than or equal to 3.43 (5) (475/sup 0/C). The hexagonal lattice constants for the bromide phase (Guinier techniques) decrease linearly with increasing bromide content across the entire range without the development of any additional lines. The variation of the c dimension for ZrI/sub 3/ (and HfI/sub 3/) on oxidation is in the opposite direction, and in this case extra lines from a presumed superlattice structure developed toward the upper limit. The structural implications of these results are considered. The reported structure for ..cap alpha..-ZrCl/sub 3/, an unusual BiI/sub 3/-type variant, was based on a misassigned ZrCl powder pattern and therefore appears to be in error. 25 references.
- Research Organization:
- Ames Lab., IA
- OSTI ID:
- 6760413
- Journal Information:
- Inorg. Chem.; (United States), Vol. 17:5
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ZIRCONIUM BROMIDES
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
STRUCTURAL CHEMICAL ANALYSIS
ZIRCONIUM CHLORIDES
ZIRCONIUM IODIDES
ASYMMETRY
EQUILIBRIUM
HEXAGONAL LATTICES
HIGH TEMPERATURE
PRESSURE DEPENDENCE
STOICHIOMETRY
SYNTHESIS
TEMPERATURE DEPENDENCE
X-RAY DIFFRACTION
BROMIDES
BROMINE COMPOUNDS
CHLORIDES
CHLORINE COMPOUNDS
COHERENT SCATTERING
CRYSTAL LATTICES
CRYSTAL STRUCTURE
DIFFRACTION
HALIDES
HALOGEN COMPOUNDS
IODIDES
IODINE COMPOUNDS
SCATTERING
TRANSITION ELEMENT COMPOUNDS
YIELDS
ZIRCONIUM COMPOUNDS
400201* - Chemical & Physicochemical Properties