Interconversion of Specific and Equivalent Conductivity of Ions in Electrolyte Solution: Effects of High Ionic Valence and Temperature

In a recent article (Fraenkel, D. Chem. Phys. Lett.2021, 781, 138957), an argument was made and advanced that the derivation of the equivalent conductivity of ionic solutions, Λ, directly from the specific conductivity, S, is correct only for symmetric strong electrolytes; for asymmetric electrolytes, a scientifically more sound way of deriving Λ from S is through the ionic conductivities, i.e., converting the specific ionic conductivity, σi─after being redefined to include the effect of the counterion─to the equivalent ionic conductivity, λi. That article, as a Letter, was limited to ions of valence 1 and 2 at 25 °C. Here, the study is extended to electrolytes with ions of higher valence (3, 4) and temperatures other than 25 °C. The proposed method of indirect S-to-Λ conversion is shown to be broader, and it is further elaborated upon and discussed.