The Nature of the Addition Compounds of Zirconium and Hafnium Tetrachloride with Phosphorus Oxychloride

摘要

Cryoscopic measurements were made in nitrobenzene on the (Zr,Hf)Cl4:2POCl3.and (Zr, Hf):POCl3 addition compounds. The 1:1 com pounds are monomers, and the 1:2 compounds dissociate presumably to the 1:1 compound and POCl3. The zirconium compound is slightly more dissociated than the hafnium compound. X-ray powder patterns of the tetrahalides, and the addition compounds, show the hafnium tetrachloride to be the same as the zirconium tetrachloride. The patterns of the addition compounds are of lower symmetry than those of the tetrahalides.