A practical approach to modeling the electrical double layer in the presence of specific adsorption of ions

1997 ◽  
Vol 75 (11) ◽  
pp. 1710-1720 ◽  
Author(s):  
Bruno Pettinger ◽  
Karl Doblhofer

Model calculations are presented that yield in a straightforward manner the quantitative dependence of the specific adsorption of ions at electrode surfaces on the applied electrode potential (electrode charge). Furthermore, the double-layer capacitance and the potential at the outer Helmholtz plane (ø2) are obtained. The derivation is based on Devanathan's three-capacitor model for the interfacial electric-potential distribution. A convenient correction function for the ø1 potential accounting for the discreteness-of-charge effect is derived, largely on the basis of recent work by Conway et al. The results are shown to be in very good agreement with published work by Lawrence and Parsons on the double layer between Br− electrolyte and the mercury electrode. Keywords: electrochemistry, specific adsorption, electric double layer, discreteness-of-charge effect.

Author(s):  
W. Ronald Fawcett

In examining the properties of the metal | solution interface, two limiting types of behavior are found, namely, the ideal polarizable interface and the ideally nonpolarizable interface. In the former case, the interface behaves as a capacitor so that charge can be placed on the metal using an external voltage source. This leads to the establishment of an equal and opposite charge on the solution side. The total system in which charge is separated in space is called the electrical double layer and its properties are characterized by electrostatic equilibrium. An electrical double layer exists in general at any interface at which there is a change in dielectric properties. It has an important influence on the structure of the interface and on the kinetics of processes occurring there. The classical example of an ideally polarizable interface is a mercury electrode in an electrolyte solution which does not contain mercury ions, for example, aqueous KCl. The charge on the mercury surface is altered using an external voltage source placed between the polarizable electrode and non-polarizable electrode, for example, a silver | silver chloride electrode in contact with the same solution. Within well-defined limits, the charge can be changed in both the negative and positive directions. When the mercury electrode is positively charged, there is an excess of anions in the solution close to the electrode. The opposite situation occurs when the electrode is negatively charged. An important point of reference is the point of zero charge (PZC), which occurs when the charge on the electrode is exactly zero. The properties of the electrical double layer in solution depend on the nature of the electrolyte and its concentration. In many electrolytes, one or more of the constituent ions are specifically adsorbed at the interface. Specific adsorption implies that the local ionic concentration is determined not just by electrostatic forces but also by specific chemical forces. For example, the larger halide ions are chemisorbed on mercury due to the covalent nature of the interaction between a mercury atom and the anion. Specific adsorption can also result from the hydrophobic nature of an ion.


1981 ◽  
Vol 46 (9) ◽  
pp. 2158-2165
Author(s):  
U. Palm ◽  
M. Väärtnŏu ◽  
M. Salve

A procedure for the calculation of the characteristics of the inner part of the electrical double layer has been elaborated on the basis of the capacity data obtained in the conditions of specific adsorption of ions, accompanied by an increase of the inner layer dimensions. The formulae derived have been verified by studying the specific adsorption of tetraalkylammonium cations from aliphatic alcohols.


1979 ◽  
Vol 100 (1-2) ◽  
pp. 365-377 ◽  
Author(s):  
B. Damaskin ◽  
L. Kuznetsova ◽  
U. Palm ◽  
M. Väärtnu ◽  
M. Salve

1966 ◽  
Vol 19 (8) ◽  
pp. 1343 ◽  
Author(s):  
TM Florence

In concentrated chloride media, nickel is reduced at far more positive potentials than in dilute solutions. The positive shift in half-wave potential increases as the ionic strength is raised, and is also greater when the cation of the supporting electrolyte has a high hydration number. Evidence is presented to show that the reduction in overpotential is due to the formation of a nickel chloride complex, [Ni(H2O)5Cl]+, which has a stoicheiometric stability constant of 0.094 � 0.009 at an ionic strength of 10.0. Spectrophotometric results show that this nickel species is not formed in low ionic strength solutions. In anhydrous methanol saturated with lithium chloride, nickel is present as the tetrachloro complex, [NiCl,]2-, which has similar polarographic behaviour to the monochloro complex. Current-potential curves recorded at a rotated pyrolytic graphite electrode enabled the behaviour of nickel to be studied in the absence of specific adsorption of the chloride ion. Nickel is reduced at more positive potentials at a dropping mercury electrode than at the pyrolytic graphite electrode, and the results indicate that this difference is due to specific adsorption of chloride on the mercury electrode.


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