Vapor complexes of samarium(III) and samarium(II) chlorides with aluminium(III) chloride

Journal Article · Thu Feb 01 04:00:00 EST 1979 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic50192a038· OSTI ID:6479438

Papatheodorou, G N; Kucera, G H

The electron absorption spectra of vapor-phase compounds formed by reacting SmCl/sub 3/(s) and SmCl/sub 2/(s) with gaseous Al/sub 2/Cl/sub 6/ have been measured at temperatures up to 800/sup 0/K and total pressures up to 13 atm. The spectra of the pale yellow Sm/sup III/-Al-Cl gaseous complex(es) were characteristic of the f ..-->.. f electronic transitions of Sm(III). The spectra of the red-brown Sm/sup II/-Al-Cl gaseous complex(es) showed high-intensity, broad bands which are attributed to 4f ..-->.. 5d transitions of Sm(II). Spectrophotometric measurements have been used to investigate the partial pressures of the vapor complexes at different Al/sub 2/Cl/sub 6/ pressures. Thermodynamic considerations suggest that the SmAl/sub 3/Cl/sub 12/ is the predominant vapor species formed by the trivalent samarium. For the reaction SmCl/sub 3/(s) + 3/2Al/sub 2/Cl/sub 6/(g) ..-->.. SmAl/sub 3/Cl/sub 12/(g) the values of ..delta..H = 6.7 k/cal and ..delta..s = -1.0 eu have been derived. At 650/sup 0/K the volatility enhancement of Sm(II) has been estimated to be approx.10/sup 10/. Rare earth oxides have been halogenated and vapor transported using Al/sub 2/Cl/sub 6/ or Al/sub 2/Br/sub 6/. 5 figures, 5 tables.

• Research Organization: Argonne National Lab., IL
• OSTI ID: 6479438
• Journal Information: Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 18:2; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ABSORPTION SPECTRA
ALUMINIUM CHLORIDES
ALUMINIUM COMPLEXES
ALUMINIUM COMPOUNDS
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
CHLORIDES
CHLORINE COMPOUNDS
COMPLEXES
DISSOCIATION
FLUIDS
GASES
HALIDES
HALOGEN COMPOUNDS
HIGH TEMPERATURE
HOLMIUM COMPLEXES
MEDIUM PRESSURE
NEODYMIUM COMPLEXES
PHYSICAL PROPERTIES
PRESSURE DEPENDENCE
RARE EARTH COMPLEXES
RARE EARTH COMPOUNDS
SAMARIUM CHLORIDES
SAMARIUM COMPLEXES
SAMARIUM COMPOUNDS
SPECTRA
SYNTHESIS
TEMPERATURE DEPENDENCE
THERMODYNAMIC PROPERTIES
VAPORS
YIELDS