The coordination slates of Ni(II) and Cu(II) in aqueous magnesium chloride solutions have been studied spectrophotometrkally at temperatures up to 320° and concentrations up to 8 M in magnesium chloride. For Ni(II), increase in the MgCl2 concentration results in the replacement of H2O in the first coordination sphere of Ni(H2O)62+ by Cl- to give NiCl64− groups. With increasing temperature, transformation to NiCl42− groups occurs through a two-species octahedral-tetrahedral equilibrium. Thermodynamic data are presented for this equilibrium. For Cu(II), at similar temperatures and MgCl2 concentrations, the coordination state is the CuCl42− configuration, but in this case the transition from Cu(H2O)62+ cannot be described in terms of a two-species equilibrium but seems to occur by means of a continuous ligand exchang0e and distortion mechanism. In the MgCl2-H2O system, H2O coordinates strongly with Mg(II). For compositions near H2O/Mg = 6, the Mg(H2O)62+ species appears to exist as an independent entity. It is pointed out that changes in the Ni(II) coordination states can serve as indicators for the determination of Mg(II) hydration, numbers as well as hydration numbers of other noble gas configuration cations in molten hydrate systems.
ASJC Scopus subject areas
- General Chemistry
- Colloid and Surface Chemistry