Thermochimica Acta, Vol.354, No.1-2, 153-160, 2000
Phase relationships in cobalt iodate hydrates - thermal analyses, X-ray, IR, and Raman spectroscopic studies
The phase relationships of the cobalt iodate-water system have been examined using thermal analyses (DSC, TG), X-ray, LR and Raman spectroscopic methods. The compounds established are Co(IO3)(2). 4H(2)O, alpha-Co(IO3)(2). 2H(2)O, beta-Co(IO3)(2). 2H(2)O. Co(IO3)(2) as well as the novel compounds Co(IO3)(2). xH(2)O and Co(IO3)(2). H2O. beta-Co(IO3)(2). 2H(2)O is isostructural to the respective nickel compound. Co(IO3)(2). H2O crystallises orthorhombic with a=827.18(6) pm, b=1104.52(8) pm, and c=772.26(4) pm. The vibrational spectra display acentric space groups (violation of the mutual exclusion principle) for Co(IO3)(2). H2O and Co(IO3)(2).beta-Co(IO3)(2). 2H(2)O dehydrates to Co(IO3)(2), Co(IO3)(2). xH(2)O at similar to 300 K (TG) to Co(IO3)(2). H2O, and Co(IO3)(2). H2O at 519 K (DSC) to Co(IO3)(2). Both the strength of the hydrogen bonds and the colour of the various cobalt iodate hydrates differ strongly. This is caused by the different ligand field splitting of the respective Co(IO3)(x)(H2O)(y) polyhedra. The former is shown from the average wave numbers of the uncoupled OD stretching modes (isotopically dilute samples), which decrease in the range Co(IO3)(2). H2O (pale-pink, nu(OD): 2302 and 2248 cm(-1), 90 K)
Keywords:cobalt iodate hydrates;phase relationships;Raman and infrared spectra;x-ray powder data;colour;strength of hydrogen bonds