Investigation of complexation and solubility equilibria in the copper(I)/cyanide system at 25 °C

The complexation of copper(I) by cyanide ions (CN−) in aqueous solution has been studied by glass electrode potentiometry at 25 °C and ionic strengths (I) of 1, 3 and 5 M in NaCl media. Overall formation constants, βn, for the equilibria: Cu+(aq) + nCN−(aq) ⇌ Cu(CN)n(n − 1)−(aq) with n = 2, 3 and 4, were quantified, along with the ionization constant (Kw) of water and the acid dissociation constant (Ka) of HCN(aq). The solubility constants *Ksn for the equilibria: CuCN(s) + (n − 1)HCN0(aq) ⇌ Cu(CN)n(n − 1)−(aq) + (n − 1)H+(aq) were also determined from a re-analysis of published solubility data for CuCN(s) in acidic cyanide solutions at I = 1 M(NaCl) and 25 °C. Because of the instability of uncomplexed Cu+(aq) and parameter correlations in the data, neither β1 nor the solubility product Ks0 (CuCN(s) ⇌ Cu+(aq) + CN−(aq)) could be reliably determined from the present data although estimates are presented.