Preferential solvation of ions in mixed solvents. 6: Univalent anions in aqueous organic solvents according to the inverse Kirkwood–Buff integral (IKBI) approach

Abstract: The inverse Kirkwood–Buff integral (IKBI) approach is applied to the preferential solvation of F−, Cl−, Br−, I−, and in aqueous mixtures of the co-solvents (S) methanol (MeOH), ethanol (EtOH), t-butanol (t-BuOH), 1,2-ethanediol (EG), glycerol (Gly), acetone (Me2CO), acetonitrile (MeCN), formamide (FA), N,N-dimethylformamide (DMF), N,N,N′,N′,N″,N″-hexamethyl phosphoric triamide (HMPT), and dimethylsulfoxide (DMSO), as far as the relevant data exist in the literature. Fluoride anions are selectively solvated by the water up to large mole fractions (x S ⩾0.4) of S=EtOH, t-BuOH, Me2CO, MeCN, and DMF, and up to lower contents (x S ∼0.1) of MeOH, EG, FA, and DMSO. The other anions are preferentially solvated by water to diminishing extent as their sizes become larger, and the largest ones show some preference for S in water-rich mixtures of MeOH and FA, whereas in aqueous Gly even chloride is preferentially solvated by the Gly. The competition between the co-solvent and the anion for the hydrogen bonds that water molecules donate is the main cause for the observed preferential solvation behaviour. [Copyright &y& Elsevier]