Abstract
This work provides a comprehensive evaluation of the effect of the cation alkyl side chain length of the 1-alkyl-3-methylimidazolium chloride series ([C (n) C(1)im]Cl, n = 2-14) of ionic liquids (ILs) on their capability to form aqueous biphasic systems (ABSs) with salts and self-aggregation derived properties. The liquid-liquid phase behavior of ternary systems composed of [C (n) C(1)im]Cl, water, and K(3)PO(4) or K(2)CO(3) and the respective Setschenow salting-out coefficients (k(s) ), a quantitative measure of the two-phase formation ability, were determined. An odd-even effect in the k(s) values along the number of methylene groups of the longest IL cation alkyl side chain was identified for the ABS formed by K(2)CO(3), a weaker salting-out agent where the phenomenon is clearly identified. In general, cations with even alkyl side chains, being likely to display higher molar volumes, are more easily salted-out and thus more prone to undergo phase separation. The odd-even effect in the k(s) values is, however, more significant in ILs up to n = 6, where the nanostructuration/nanosegregation of ILs plays a less relevant role. Still, with the [C (n) C(1)im]Cl (n = 7-14) series of ILs, an odd-even effect was also identified in the ILs' ionization degree, molar conductivity, and conductivity at infinite dilution. In summary, it is shown here that the ILs' odd-even effect occurs in IL aqueous solutions and not just in neat ILs, an already well-established phenomenon occurring in a series of ILs' properties described as a result of the orientation of the terminal methyl groups to the imidazolium ring cation and consequent effect in the ILs' cohesive energy.