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Chloro complexes of cobalt(II) in acetone

Affiliation:	1. Department of Chemistry, Washington State University, USA;2. Department of Radiology and Biomedical Imaging, University of CA, San Francisco, USA;3. Institute of Biotechnology, CR, Prague;4. Cancer Targeted Technology, USA

Abstract:	Equilibria of cobalt(II) perchlorate with lithium chloride in 0.1 M LiClO₄ acetone solution have been investigated by means of potentiometry and spectrophotometry at 25.0°C. By the addition of a large excess of medium salt (LiClO₄), the ionic dissociation of electrolytes are surpressed and the ion-pairs predominate in this medium. It was confirmed that AgAgCl electrode gives rise to the Nernstian response in this medium. The potentiometry reveals the formation of following chloro complexes of cobalt (II): $Co(ClO_{4})_{2} +LiCl ⇌ K_{1} CoCl(ClO_{4})+LiClO_{4}$ $Co(ClO_{4})+LiCl ⇌ K_{2} CoCl_{2} +LiClO_{4}$ $CoCl_{2} +LiCl ⇌ K_{3} LiCoCl_{3}$ Successive formation constants were determined as log K₁ = 5.0 ± 0.3, log K₂ = 6.2 ± 0.3 (log β₂ = log K₁K₂ = 11.15 ± 0.03) and log K₃ = 5.97 ± 0.03. By the spectrophotometric titration at higher concentration of lithium chloride, we have the following equilibrium: $LiCoCl_{3} +LiCl ⇌ K_{4} LiCoCl_{3}$ with formation constant of log K₄ = 2.64 ± 0.05. Absorption spectra of these complexes are presented.

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