Cobalt(II)–halide association equilibria in ammonium nitrate–dimethyl sulfoxide melts

Add time:07/23/2019    Source:sciencedirect.com

The cobalt(II)–chloride association equilibria in ammonium nitrate–dimethyl sulfoxide (DMSO) melts of the type NH4NO3·xDMSO at five different compositions in the range 1.0 ≤ x ≤ 5.0 have been investigated by the spectrophotometric method. Absorption spectra of cobalt(II) chloride solutions containing variable amounts of ammonium chloride at different temperatures from 35 to 65 °C have been recorded in the wavelength range of 400–800 nm. In the absence of chloride, the solutions show spectra typical for octahedral coordination of cobalt(II). Addition of chloride changed the absorption spectra to a tetrahedral or severely distorted octahedral coordination. Stability constants for the complexes [Co(NO3)2(DMSO)2], [Co(NO3)2X2]2− and [CoCl4]2−, and the species spectra for all complexes are reported. The effect of varying the DMSO/NH4NO3 mole ratio is discussed. A sharp increase of the stability constants around x = 2 is correlated to the competition between the solvent molecules or ions and the cobalt(II) ions for the ligand and to the solvation of NH4+ with two DMSO.

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