Low-temperature routes to new structures for yttrium, holmium, erbium, and thulium oxychlorides

Journal Article · Wed Feb 13 04:00:00 EST 1985 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic00198a013· OSTI ID:5740668

Garcia, E; Corbett, J D; Ford, J E; Vary, W J

The pyrohydrolysis of (NH/sub 4/)/sub 3/RCl/sub 6/ (R = Y, Dy, Ho, Er, Tm, Yb) has been studied at 270-550/sup 0/C. This produces in part the YOF form of YOCl near 500/sup 0/C and R anti 3m (disordered SmSI + YOF) phases for YOCl, HoOCl, ErOCl, TmOCl and YbOCl at 270-400/sup 0/C. Fluxed transformations of the disordered materials yield the new SmSI form of HoOCl (from LiCl-KCl) and YOF-type TmOCl, ErOCl (LiCl-KCl or RCl/sub 3/), YOCl, and HoOCl(KCl). No new structures are found for Dy and Yb. Reactions with LiCl-KCl or KCl melts also produce R/sub 3/O/sub 4/Cl phases for R = Y, Yb, Dy, and Ho, the last two being new. The R anti 3m oxychlorides of Y, Ho, Er, and Yb are intercalated by sodium in liquid ammonia at room temperature to yield 3R-Na/sub x/ROCl. The relationship of these new structure types to the previously known (PbFCl or SmSI) forms of the rare-earth-metal oxychlorides are considered. Different preparative routes are observed to exercise some kinetic control over the structures of the ROCl products even for reactions run at the same temperature. ScOCl has the FeOCl-type layered structure. 18 references, 1 figure, 5 tables.

• Research Organization: Iowa State Univ., Ames
• DOE Contract Number: W-7405-ENG-82
• OSTI ID: 5740668
• Journal Information: Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 24:4; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
360202* -- Ceramics
Cermets
& Refractories-- Structure & Phase Studies
ALKALI METALS
AMMONIA
AMMONIUM COMPOUNDS
CHEMICAL PREPARATION
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHLORINE COMPOUNDS
DATA
DECOMPOSITION
DYSPROSIUM COMPOUNDS
ELEMENTS
ERBIUM COMPOUNDS
EXPERIMENTAL DATA
HALOGEN COMPOUNDS
HIGH TEMPERATURE
HOLMIUM COMPOUNDS
HYDRIDES
HYDROGEN COMPOUNDS
HYDROLYSIS
INFORMATION
KINETICS
LYSIS
METALS
NITROGEN COMPOUNDS
NITROGEN HYDRIDES
NUMERICAL DATA
OXYCHLORIDES
OXYGEN COMPOUNDS
PYROLYSIS
RARE EARTH COMPOUNDS
REACTION KINETICS
SODIUM
SOLVOLYSIS
STRUCTURAL CHEMICAL ANALYSIS
SYNTHESIS
THERMOCHEMICAL PROCESSES
THULIUM COMPOUNDS
TRANSITION ELEMENT COMPOUNDS
YTTERBIUM COMPOUNDS
YTTRIUM COMPOUNDS