| Summary: | A problem often encountered in polarization studies at water (w)/organic solvent (o) interfaces is the poor stability of the potential of the reference electrode connected to the organic solvent phase (o). The potential of this reference electrode is usually based on the partition of a highly hydrophobic cation between the reference water (wʹ) and the organic solvent phase (o). The deterioration in stability is associated with the spontaneous extraction of a salt containing a common cation from the phase (wʹ) to the phase (o), which leads to a significant shift in the reference potential. In the present study, the novel concept of a polarizable reference electrode is introduced, which makes it possible to resolve this problem in a sophisticated way. The solution makes use of a polarizable metal electrode, the potential of which is adjusted by a battery-operated three-electrode potentiostat, and which then serves as a reference organic solvent electrode in a four-electrode system for the polarization of the water/organic solvent interface.
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