A new interpretation of the original data of chemla's group on the mobilities of binary molten system (Li, K)Br

摘要

For the molten binary system (Li, K)Br where the Chemla effect was discovered, the data on the external Mobilities presented by Chemla's group about 40 years ago are newly analyzed. It is found that these data including those in a trace amount of Na+ excellently fit the empirical equation for internal mobilities of cation M+ except for K+ in pure LiBr at a high temperature (1023 K): u(M)(i) = [A(M)/(V-m - V-oM)] exp(-E-M/RT), where V-m is the molar volume of the mixture, T the temperature, and R the gas constant; A(M), V-oM and E-M are parameters peculiar to cation M+ (Li+, Na+ and K+). These findings including the Chemla crossing point of the isotherms of u(M)(i) of two cations are discussed mainly from the standpoint of concentration and temperature dependence. The present system is found to be a conspicuous example for supporting the dynamic dissociation model previously presented, and the original data, which were obtained using a modified Hittorf method and cover a wide range of concentrations and temperatures (633 K-1023 K), are proven to be highly accurate.