Journal of the Electrochemical Society, Vol.144, No.4, 1332-1339, 1997
Anomalous Behavior of Internal Mobilities for Ag(I) and Tl(I) Ions in Molten Nitrates
The data on internal cation mobilities, u, in the molten binary nitrate systems (Ag, M)NO3 and (Tl, M)NO3 (M=alkali metal ion) previously obtained by us have been re-examined. In binary alkali nitrates Ir is known to be well expressed by an empirical equation u={A/(V-m-V-0)} exp (-E/RT), where V-m is the molar volume; while A, V-0, and E are constants nearly independent of the cations with which they are mixed, It is found that in melts containing Ag+, u(M), for the M deviates negatively from this Equation, and that with Tl+, u(M) deviates positively. Thus, Ag+ and Tl+ both with relatively high polarizabilities, have opposite effects on u(M), that is a tranquilization effect and an agitation effect, respectively The reason has been interpreted in terms of the high polarizabilities and the difference in the sizes of Ag+ and Tl+.
Keywords:SELF-EXCHANGE VELOCITIES;CATION MOBILITIES;BINARY-SYSTEM;EUTECTIC COMPOSITION;MD SIMULATIONS;KLEMM METHOD;LI-ISOTOPES;MIXTURES