Results for the Mercury-Aqueous Solution Interface

The shape of the electrocapillary curve is easily calculated if it is assumed that the double layer acts as a condenser of constant capacity C. In this case, double integration of Eq. V-50 gives 

Incidentally, a quantity called the rational potential is defined as E for the mercury-water interface (no added electrolyte) so, in general, = E + 0.480 V if a normal calomel reference electrode is used. 

Equation V-64 is that of a parabola, and electrocapillary curves are indeed approximately parabolic in shape. Because E ax tmd 7 max very nearly the same for certain electrolytes, such as sodium sulfate and sodium carbonate, it is generally assumed that specific adsorption effects are absent, and Emax is taken as a constant (-0.480 V) characteristic of the mercury-water interface. For most other electrolytes there is a shift in the maximum voltage, and is then taken to be Emax 0.480. Some values for the quantities are given in Table V-5 [113]. Much information of this type is due to Gouy [125], although additional results are to be found in most of the other references cited in this section. 

Properties of the Electrical Double Layer at the Electrocapillary Maximum 

Note Some of Grahame s values for and included in this table. For a common cation, the sequence of anions in order of increasing adsorption is similar to that of the Hofmeister series in coagulation studies, and it is evident that specific adsorption properties are involved. 

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Interfacial tension against electrode potential curves have a parabolic shape with a maximum value which depends on the nature and concentration of the electrolyte (see fig. 10.1). Detailed results for the mercury aqueous solution interface were initially reported by Gouy [7, G5]. Examination of these data for the alkali metal halides shows that the interfacial tension depends markedly on the nature of the electrolyte at positive potentials. On the other hand, the variation with electrolyte at negative potentials is rather small. It follows that the anions in the electrolyte strongly affect the interfacial tension when they predominate in the double layer. 

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