Industrial & Engineering Chemistry Research, Vol.47, No.6, 2056-2062, 2008
Activity coefficients of LiCl in ethanol-water mixtures at 298.15K
The electromotive force, E, of the cell containing two ion-selective electrodes (ISE) Na-ISE vertical bar LiCl(m), ethanol (Y), H2O(100-Y) vertical bar Cl-ISE has been measured at a temperature of 298.15 K as a function of the weight percentage Y of ethanol in a mixed solvent. Y was varied between 0 and 80% in 20-unit steps, and the molality of the electrolyte (m) was between 0.02 and 4 mol kg(-1), approximately. This electrode system was previously checked and calibrated by measuring the activity coefficients of LiCl in 0, 20, and 40% methanol-water and comparing them with literature values. The values of the standard electromotive force, El (molal scale), were determined using routine methods of extrapolation (Debye-Huckel and Pitzer equations). The results obtained produced good internal consistency within the normal limits of experimental error encountered in these types of measurements. Once El was determined, the mean ionic activity coefficients for LiCl, the free energy of transfer from the water to the alcohol-water mixture, and the primary LICI hydration number were calculated. The variation of these magnitudes with the composition of the mixture is discussed in terms of the ionsolvent and ion-ion interactions and their changes with the properties of the medium.