Ion Transfer Energies and Galvani Potentials

Data on the distribution coefficients and transfer energies of electrolytes for water-nitrobenzene systems mainly originate from the works by Davies [126] and Rais [115]. Although the results of the first of the cited works have been used to test Eq. (35), the publication itself [126] has been somewhat forgotten. In practice, however, data by 

Rais are widely used and applicable to many ions. It should be noted that Rais, on the basis of Eq. (34), divided the quantities into Gf ionic components. These data are cited almost completely in numerous review articles and publications [6, 9, 12, 97, 128] More recently they have been supplemented with the results of electroanalytical determinations obtained by other authors [6-15, 60, 65, 66, 129-137]. 

The values of A Gf and A cpf, obtained with the use of electrochemical methods for the water-1,2-dichloroethane [65-66,134,138], water-dichloromethane [139], water-acetophenone [140] and water-methyhsobutyl ketone [67] systems are shown in Tables 2 to 5. In the case of the systems with 1,2-dichloroethane the data obtained from 

The interface between an aqueous solution containing a strongly hydrophilic electrolyte (e.g. LiCl) and a nitrobenzene solution containing a strongly hydrophobic salt [e.g. tetrabutylammonium tetraphenylborate (TBATPhB)], schematically shown below  

At the present time the electrochemistry of immiscible electrolyte solutions is developing mainly on the basis of the studies of the water-nitrobenzene and water-1,2-dichloroethane interfaces. The polarizability ranges of these interfaces in the presence of typical electrolytes (system XV) are about 0.30 V. Extension of these ranges towards negative currents has been achieved by substitution of TBA ions by tetraphenyl-arsonium ions [145], and by crystal violet cations [133,134]. But the substitution of TPhB ions by dicarboUyl cobaltate (III) anions leads to an extension of the above range towards positive currents [127]. 

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