AbstractIsobaric vapor‐liquid equilibrium data at atmospheric pressure are reported for seven systems, each consisting of water, an alcohol (methanol or ethanol), and an anhydrous acetate salt (of sodium, potassium, barium, or calcium) dissolved to saturation in the boiling liquid phase. These systems are intended to complete a matrix about the single system ethanol‐water‐potassium acetate for which data were reported previously.Solubility data are reported in terms of saturation salt concentration as a function of alcohol‐water proportionality in the liquid. Sodium acetate as well as potassium acetate was found capable of eliminating completely the ethanol‐water azeotrope.Major differences in the effects of these salts as compared to those reproted for other salts in the salt‐effect literature were observed. Systems were discovered in which the salt appeared to cause both salting out and salting in of the alcohol in differing composition regions of the same system, the predominating effect depending on the relative proportions of alcohol and water. Systems were also discovered in which the salt salted‐in the component in which it was less soluble. Both observed effects are in contradiction with previously accepted theories of salt effect in vapor‐liq