Abstract:
Diffusion coefficients of the ions Ag+, Cl– and Br– in molten KNO3+ Ca(NO3)2 of molar ratio 62 : 38 have been determined by chronopotentiometry. In the range 400–550 K the results fit a modified Fulcher equation, Di=AiT½ exp [(–ki)/(T–T0)], where T0= 316 K. The values of the Fulcher coefficients, ki, are all close to that previously found for electrical conductivity. The measured values of DBr– depart from the Fulcher equation below 400 K, and there are signs of a return to Arrhenius behaviour. It is suggested that in the Fulcher region the transport mechanism for diffusion and conductivity involves cooperative translations of both cations and anions, but that at lower temperatures there is a transition to a “glass-like” transport mechanism in which only certain ions are regarded as mobile.
