Anomalous Behavior of Internal Mobilities for Ag(I) and 11(1) Ions in Molten Nitrates

The data on internal cation mobilities, it, in the molten binary nitrate systems (Ag, M)N03 and (Ti, M)N03 (M = alka-li metal ion) previously obtained by us have been re-examined. In binary alkali nitrates it is known to be well expressed by an empirical equation u = {A/(Vm — 17)} exp (-E/RT), where V,,, is the molar volume; while A, V6, and E are constants nearly independent of the cations with which they are mixed. It is found that in melts containing U for the M devi-ates negatively from this equation, and that with TF, UM deviates positively. Thus, Ag and TV both with relatively high polarizabilities, have opposite effects on UM, that is a tranquilization effect and an agitation effect, respectively. The rea-son has been interpreted in terms of the high polarizabilities and the difference in the sizes of Ag and TV