Ionic association of the ionic liquids [C4mim][BF4], [C4mim][PF6], and [Cnmim]Br in molecular solvents

Considering the ionic nature of ionic liquids (ILs), ionic association is expected to be essential in solutions of ILs and to have an important influence on their applications. Although numerous studies have been reported for the ionic association behavior of ILs in solution, quantitative results are quite scarce. Herein, the conductivities of the ILs [Cnmim]Br (n=4, 6, 8, 10, 12), [C4mim][BF4], and [C4mim][PF6] in various molecular solvents (water, methanol, 1-propanol, 1-pentanol, acetonitrile, and acetone) are determined at 298.15 K as a function of IL concentration. The conductance data are analyzed by the Lee-Wheaton conductivity equation in terms of the ionic association constant (KA) and the limiting molar conductance (Lambda(m)(0)). Combined with the values for the Br- anion reported in the literature, the limiting molar conductivities and the transference numbers of the cations and [BF4]- and [PF6]- anions are calculated in the molecular solvents. It is shown that the alkyl chain length of the cations and type of anion affect the ionic association constants and limiting molar conductivities of the ILs. For a given anion (Br-), the Lambda(m)(0) values decrease with increasing alkyl chain length of the cations in all the molecular solvents, whereas the KA values of the ILs decrease in organic solvents but increase in water as the alkyl chain length of the cations increases. For the [C4mim]+ cation, the limiting molar conductivities of the ILs decrease in the order Br- > [BF4]- > [PF6]-, and their ionic association constants follow the order [BF4]- > [PF6]- > Br- in water, acetone, and acetonitrile. Furthermore, and similar to the classical electrolytes, a linear relationship is observed between ln KA of the ILs and the reciprocal of the dielectric constants of the molecular solvents. The ILs are solvated to a different extent by the molecular solvents, and ionic association is affected significantly by ionic solvation. This information is expected to be useful for the modulation of the IL conductance by the alkyl chain length of the cations, type of anion, and physical properties of the molecular solvents.