Electric conductivities of 1:1 electrolytes in liquid methanol along the liquid–vapor coexistence curve up to the critical temperature. I. NaCl, KCl, and CsCl solutions

The molar conductivities Lambda of NaCl, KCl, and CsCl in liquid methanol were measured in the concentration range of (0.3-2.0) x 10(-3) mol dm(-3) and the temperature range of 60-240 degrees C along the liquid-vapor coexistence curve. The temperature range corresponds to the solvent density range of (2.78-1.55)rhoc, where rhoc = 0.2756 g cm(-3) is the critical density of methanol. The concentration dependence of Lambda at each temperature and density (pressure) has been analyzed by the Fuoss-Chen-Justice equation to obtain the limiting molar conductivity Lambda0 and the molar association constant KA. For all the electrolytes studied, Lambda0 increased almost linearly with decreasing density at densities above 2.0rhoc, while the opposite tendency was observed at lower densities. The relative contribution of the nonhydrodynamic effect on the translational friction coefficient zeta was estimated in terms of Deltazeta/zeta, where the residual friction coefficient Deltazeta is the difference between zeta and the Stokes friction coefficient zetaS. At densities above 2.0rhoc, Deltazeta/zeta increased with decreasing density though zeta and Deltazeta decrease, and the tendencies are common for all the ions studied. The density dependences of zeta and Deltazeta/zeta were explained well by the Hubbard-Onsager (HO) dielectric friction theory based on the sphere-in-continuum model. At densities below 2.0rhoc, however, the experimental results cannot be explained by the HO theory.