The Raman Spectrum of Mercury (II) Iodide in High Temperature Solvents

Abstract

The Raman spectrum of mercury(II) iodide was observed in cesium nitrate at 430°C and in meta- and para-terphenyl at 235 and 240°C, respectively. A single strong polarized line was found at 148. 5 cm^?1, width at half height 15 cm^?1 in cesium nitrate, and a single line at 154. 0 cm^?1 width at half height 7 cm^?1 in the terphenyls. The observed spectra are not consistent with interactions of the solute and the solvents involving bonds of highly covalent character, but do not exclude other interactions.

In the course of an investigation on the nature of mercury (II) iodide species in solution in molten alkali metal nitrates, by its distribution between the salt melts and terphenyl melts^{1, 2}, it became of interest to study by means of Raman spectroscopy the mercury (II) iodide species formed. Several such studies at lower temperatures have already been made: in the gas phase³, in a krypton matrix⁴, in alcohols⁵, tributy phosphate⁶ and dioxame⁷, and in molten mercury(II) iodide⁸, chloride⁹, and bromide⁹. The reason for looking at the Raman spectrum in yetfurther media was the suggestion made on the basis of thermodynamic and kinetic data^2,10 that the mercury(II) iodide species in the alkali mitrate melts are solvated by nitrate anions, and that possiby the mixed anion terrahedral species HgI₂(NO₃)₂ is formed. Recent Ranan sepctrophotometric data on mixed halide anionic complexes of mercury₁₁ identified prominent lines of the spectrum of the species HgBr_nI^2– _4–n, including HGBr₂I₂ ^2–, so that a comparison could be made. The solubility of mercury (II) iodide in molten alkali metal nitrates is rather small, expect for cesium nitrate¹², Where the solubility should be sufficent for the Raman spectrum to be recorded. Also, it was comcluded from vapor pressure osmometric data in aromatic solvents that demiric species of mercury(II) halides (even a trimeric species of the iodide) are found, in which the mercury has a distorted octahedral coordination, with three halogen atoms bonded to a mercury atom in the dimer¹³. In terphenyl melts, the solubility