The aim of this work is to obtain further evidence about the salting-out effect produced by the addition of tri-sodium citrate to aqueous solutions of water miscible ionic liquid 1-butyl-3-methylimidazolium bromide ([C4mim][Br]) by evaluating the effect of tri-sodium citrate on the thermodynamic properties of aqueous solutions of this ionic liquid. Experimental measurements of density and sound velocity at different temperatures ranging from (288.15 to 308.15) K, the refractive index at 308.15 K and the liquid– liquid phase diagram at different temperatures ranging from (288.15 to 338.15) K for aqueous solutions containing 1-butyl-3-methylimidazolium bromide ([C4mim][Br]) and tri-sodium citrate (Na3Cit) are taken. The apparent molar volume of transfer of [C4mim][Br] from water to aqueous solutions of Na3Cit have positive values and it increases by increasing salt molality. Although at high IL molality, the apparent molar isentropic compressibility shows similar behaviour with that of the apparent molar volume. However at low concentrations of IL, the apparent molar isentropic compressibility of transfer of [C4mim][Br] from water to aqueous solutions of Na3Cit have negative values. The effects of temperature and the addition of Na3Cit and [C4mim][Br] on the liquid–liquid phase diagram of the investigated system have been studied. It was found that an increase in temperature caused the expansion of the one-phase region. The presence of Na3Cit triggers a salting-out effect, leading to significant upward shifts of the liquid–liquid de-mixing temperatures of the system. The effect of temperature on the phase-forming ability in the system investigated has been studied based on a salting-out coefficient obtained from fitting the binodal values to a Setschenow-type equation for each temperature. Based on cloud point values, the energetics of the clouding process have been estimated and it was found that both of entropy and enthalpy are the driving forces for biphasic format
