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Advances in Molten Salts

ISSN:
1-56700-142-4 (Print)

Effet of high polarizability on mobilities in ionic melts

Pao-Hwa Chou
Department of Electronic Chemistry, Tokyo Institute of Technology, Nagatsuta 4259, Midori-ku, Yokohama 226-8502, Japan

Shingo Kawase
Department of Electronic Chemistry, Tokyo Institute of Technology, Nagatsuta 4259, Midori-ku, Yokohama 226-8502, Japan

Isao Okada
Department of Chemistry, Faculty of Science and Engineering, Sophia University, Kioi-cho 7-1, Chiyoda-ku, Tokyo 102-8554, Japan

Abstract

The effect of cations having high polarizability on the mobilities of coexisting cations as well as of the cations themselves has been studied for Ag+, Tl+ and Cs+ ions. We have previously found that the internal mobilities, u, of alkali ions in molten salts such as nitrates are well expressed by an empirical equation:u = [A/(Vm-V0)] sxp(-E/RT), where Vm- is the molar volume, and A, V0 and E are parameters nearly independent of coexisting cations. In binary melts (M, Ag)NO3, uM except for M=Li+ becomes smaller than expressed by this equation; Ag+ ion has a tranquilization effect on uM. On the contrary, in (M, Tl)NO3, uM becomes higher than according to the equation, which means that Tl+ has an agitation effect on uM. It is found that Cs+, having a high polarizability, also has an appreciable agitation effect.