LIMITING CONDUCTANCE OF LYONIUM AND LYATE IONS
The problem of proton mobility has been considered in H2O–CH3OH, H2O–D2O, and H2O–H2O2 solvents from the current viewpoint of the mechanism of proton mobility for aqueous solutions. Mixed solvents are more complicated in that one must consider the relative basicity and acidity of the species competing for the protons. It is concluded that for dilute solutions of HClO4, where water is replaced by hydrogen peroxide, the decrease in equivalent conductance relative to that of KCl in the same solvent mixture is due to the partial elimination of the proton transfer process.For highly acidic non-aqueous solvents of high dielectric constants such as HF, HCN, and HCOOH, the problem of the weakness of the usual "strong" acids of aqueous solution makes a direct determination of the limiting equivalent conductances difficult. In the case of anhydrous hydrogen fluoride the available experimental evidence indicates that the limiting conductance of the lyonium ion is approximately the same as that of the potassium ion but the lyate ion has a higher limiting conductance than other stable anions.The higher proton mobility in ice leads one to expect that hydrogen-bonded systems may be found where the conductivity may approach that of electronic semiconductors.