Theoretical interpretation of the limiting electric conductivity in ionic solution

The physical essence of the limiting equivalent ionic conductivity in solution, λ0i, has been a continuing challenge over almost a century. Here I briefly present an ab initio theoretical treatment providing (1) a new insight into the nature of λ0i, and (2) a mathematical formula for computing λ0i. In the new treatment, one assumes that any chosen ion i is surrounded by a spherical body of oriented solvent dipoles carrying the charge of the counterion, and the bulk solvent is a continuum with no molecular detail. λ0i is thus the result of the tandem operation, at hydrodynamic equilibrium, of the dipole body's electrophoretic and relaxation forces exerted on the drifting ion. λ0i is found to be proportional to the radius of ion i, and independent of the ionic charge. From experimental λ0i's, the ion radius can be computed as ‘electric radius.’ An electric ion-radius scale so derived compares well with other ion-size scales. The current theory expresses λ0i using only universal constants and unitary factors of the ionic solution, and it sheds new light on the fundamental nature of ion and charge transport in a polar liquid medium.