Abstract
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 AgAgCl 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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