To obtain further experimental evidence for the mechanisms of the salting effect produced by the addition of saltingout or sating-in inducing electrolytes to aqueous solutions of watersoluble polymers, systematic studies on the vapor−liquid equilibria and liquid−liquid equilibria of aqueous solutions of several polymers are performed in the presence of a large series of electrolytes. Polymers are polyethylene glycol 400 (PEG400), polyethylene glycol dimethyl ether 250 (PEGDME250), polyethylene glycol dimethyl ether 2000 (PEGDME2000), and polypropylene glycol 400 (PPG400), and the investigated electrolytes are KCl, NH4Cl, MgCl2, (CH3)4NCl, NaCl, NaNO3, Na2 CO3, Na2 SO4, and Na3Cit (tri-sodium citrate). Aqueous solutions of PPG400 form aqueous two-phase systems with all the investigated salts; however, other investigated polymers form aqueous two-phase systems only with Na2CO3, Na2SO4, and Na3Cit. A relation was found between the salting-out or sating-in effects of electrolyte on the polymer aqueous solutions and the slopes of the constant water activity lines of ternary polymer−salt aqueous solutions, so that, in the case of the salting-out effect, the constant water activity lines had a concave slope, but in the case of the salting-in effects, the constant water activity lines had a convex slope. The effect of temperature, anion of electrolyte, cation of electrolyte, and type and molar mass of polymers were studied and the results interpreted in terms of the solute−water and solute−solute interactions. The salting-out effect results from the formation of ion (specially anion)−water hydration complexes, which, in turn, decreases hydration, and hence, the solubility of the polymer and the salting-in effect results from a direct binding of the cations to the ether oxygens of the polymers.
