Solubilities of salts and kinetics of reactions involving inorganic complex ions in aqueous acetone mixtures. Derivation of transfer chemical potentials for ions in these aqueous mixtures at ambient pressure and 298.2 K

Gibbs Energies of Transfer of Cations from Water to Mixed Aqueous Organic Solvents

“… a Using Δ t G °(MCl) data from ref combined with Δ t G °(Cl - ) data based on the TATB scale, ref . b Recommended value from ref based on the TATB scale.…”

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

“…The unconfirmed data [13] for the transfer of CN À into aqueous ethanol lead to preferential hydration ( figure 13), with dx CN,EtOH similar in magnitude to the corresponding values for perchlorate. Contrarily, for cyanide transfer into aqueous acetone the D t G data [17] lead to selective hydration up to x Me 2 CO $ 0:45, whereas for perchlorate this limit is x Me 2 CO $ 0:25 (figure 6), beyond which limits both anions are preferentially hydrated but do not exclude the acetone from the first solvation shell. Finally, the transfer of cyanide into aqueous dimethylsulfoxide [31] shows (figure 11) preferential hydration of a magnitude between that of chloride and bromide.…”

“…In the presence of water, however, this ability is swamped by the electron pair donation (EPD) ability of the carbonyl group of acetone, so that in water-rich mixtures it cannot exert its HBD properties towards anions. Beyond x S = 0.60 there are no D t G data [2], and the data for ClO À 4 are from [17], there being no confirmatory data available. The selected V X;Me 2 CO values [12] are problematic, in that they were derived from unconfirmed data, they show poor ionic additivity, and the difference between the values for bromide and chloride is $33 cm 3 AE mol À1 rather than $8 cm 3 AE mol À1 as for all the other solvents.…”