Electrolysis with electrolyte dropping electrode: II. Basic properties of the system

In a theoretical discussion the conditions have been pointed out where an interface of two immiscible electrolyte solution behaves as an equilibrium system metal ion-metallic electrode, as an ideally polarized electrode and as an electrode under faradaic current flow. The basic equations for current-electrical potential difference across the interface have been deduced for the cases of ion as well as electron transfer.Experimentally, various base electrolyte systems were studied, the most advantageous among these are LiCl in water+tetrabutylammonium tetraphenylborate in nitrobenzene and MgCl₂ in water+tetrabutylammonium dicarbollyl cobaltate in nitrobenzene. S-shaped polarographic curves were observed with the tetramethylammonium ion. The limiting current is directly proportional to concentration. The limiting currents are somewhat higher than those predicted by the Ilkovi? equation which has been ascribed to the tangential movement of the interface.