The salt effect of four inorganic salts, namely; zinc nitrate, calcium nitrate, magnesium nitrate and magnesium chloride on the vapor liquid equilibria of the binary methyl acetate-methanol system was investigated using a modified Othmer still at 1atm. The salting out effect of methyl acetate was studied at different salt concentrations. For a salt concentration of 5wt%, it was found that zinc nitrate gives better salting out effect than calcium and magnesium nitrate. Magnesium chloride also shows a salting out effect, but could not eliminate the azeotrope completely, even at higher salt concentrations. It is observed that the bivalent cation salts (ZnNO3, CaNO3, MgNO3 and MgCl2) had greater salting out effect than univalent cation salts (LiNO3,LiCl) reported earlier. Further, salting out coefficients were calculated using the scaled particle theory. The experimental vapor-liquid equilibrium data with the salts was compared with that calculated using the scaled particle theory, but only qualitative agreement was observed. © 2014 Elsevier B.V.