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The electromotive force (EMF) method was described and some characteristic examples from the past and recent literatures were reviewed. The important experimental procedures for a successful measurement of an EMF of different galvanic cells at a certain temperature and determination of the thermodynamic properties of chemical compounds from the obtained EMF values were described. A typical galvanic cell arrangement in a furnace was presented. The two most common types of AgI-based solid electrolytes, AgI and RbAg4I5, were discussed in detail. The ionic conduction mechanisms and the application of the solid electrolytes in the EMF cells were described. In this work, we have also conducted EMF measurements using the fast Ag ion conducting solid-state electrolyte. The solid-state electrolyte Ag3GeS3I glass and the cathode material Ag4HgSe2I2 were synthesized and electrochemical cell ( )graphite|Ag|Ag3GeS3I glass|Ag4HgSe2I2|graphite(+) was assembled to measure the activity of Ag in the quaternary phase. The extremely low values of activity of silver in Ag4HgSe2I2 in the temperature range 412–482 K indicate that Ag4HgSe2I2 has superionic property. The obtained results and the determined thermodynamic values are presented and discussed.

The Fast Silver Ion Conducting Solid-State Electrolytes for Deriving Thermodynamic Data