Abstract
The data on internal cation mobilities, u, in the molten binary nitrate systems (M, Ag)NO3 and (M, Tl)NO3 (M=alkali metal ion) determined by Klemm's countercurrent electromigration method are reexamined. In binary alkali nitrates u is well expressed by an empirical equation u={A/(Vm – Vo)}exp(-E/RT), where Vm is the molar volume; A, Vo and E are constants nearly independent of coexisting cations. If Ag+ is contained, the uM of coexisting cations M negatively deviates from such an equation, and, on the contrary, if Tl+ is contained, the uM positively deviates. Thus, Ag+ and Tl+ having relatively high polarizabilities have the opposite effects on uM, that is tranquilization effect and agitation effect, respectively. The reason has been interpreted in terms of the high polarizabilities and the difference in the sizes of Ag+ and Tl+.
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