The structure of nonaqueous iron(III) chloride solutions was studied using Móssbauer spectroscopy. It has been established that the iron(III) chloride is in dimeric or polymeric forms in benzene and nitrobenzene, and partially in acetone, acetonitrile, pyridine, and dimethylformamide, while it is monomeric in ethanol. The stability of dimeric solvates increases with the increase of the donicity of the solvent. The stability of the iron-pyridine dimeric solvate is much higher than that of the others. The ability of the monomer formation depends on the donicity and dielectric constant of the solvent. The order of this ability is ethanol, dimethylformamide, pyridine, acetone, acetonitrile, nitrobenzene, and benzene.
The solvation of tin tetrahalides by donor solvents was studied using Móssbauer spectroscopy. The rate constants of the process SnX4 + 2D ^SnX4D2 for Snl4 and tetrahydrofuran at 5 °C were found to be k\ = 1.1 ± 0.3 min-1 [mol(kg of benzene)-1]-2 and = 0.06 ± 0.02 min-1; the heat of this reaction was , = -4.0 ± 1.0 kcal/mol. Using Bjerrum's formation function the solvation could be shown to proceed in two steps. The successive equilibrium constants of the formation of the solvate complexes in the system SnI4-THF at 5 °C were: K\ = 0.9 ± 0.2 [mol(kg of benzene)-1]-1 and K2 = 13.1 ± 1.6 [mol(kg of benzene)-1]-1 and for the system SnBr4-acetic anhydride: K\ = 0.8 ± 0.2 [mol(kg of benzene)-1]-1 and K2 = 4.0 ± 0.6 [mol(kg of benzene)-1]-1.
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