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The thermodynamic theory of electrocapillarity considered above is simultaneously the thermodynamic theory of the electrical double layer and yields, in its framework, quantitative data on the double layer. However, further clarification of the properties of the double layer must be based on a consideration of its structure. At present it is impossible to formulate an exact theory of the structure of the electrical double layer, even in the simple case where no specific adsorption occurs. This is partly because of the lack of experimental data (e.g. on the permittivity in electric fields of up to 109 V m"1) and partly because even the largest computers are incapable of carrying out such a task. The analysis of a system where an electrically charged metal in which the positions of the ions in the lattice are known (the situation is more complicated with liquid metals) is in contact with an electrolyte solution should include the effect of the electrical field on the permittivity of the solvent, its structure and electrolyte ion concentrations in the vicinity of the interface, and, at the same time, the effect of varying ion concentrations on the structure and the permittivity of the solvent. Because of the unsolved difficulties in the solution of this problem, simplifying models must be employed: the electrical double layer is divided into three regions that interact only electrostatically, i.e. the electrode itself, the compact layer and the diffuse layer. On the basis of this model, the overall differential capacity C for a system without specific adsorption, i.e. if the compact layer does not contain ions, is divided into two capacities in series, one corresponding to the compact layer Cc and the other to the diffuse layer Cd:



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It is assumed that the quantity Cc is not a function of the electrolyte concentration c, and changes only with the charge a, while Cd depends both on a and on c, according to the diffuse layer theory (see below). The validity of this relationship is a necessary condition for the case where the adsorption of ions in the double layer is purely electrostatic in nature. Experiments have demonstrated that the concept of the electrical double layer without specific adsorption is applicable to a very limited number of systems. Specific adsorption apparently does not occur in LiF, NaF and KF solutions (except at high concentrations, where anomalous phenomena occur). At potentials that are appropriately more negative than Epzc, where adsorption of anions is absent, no specific adsorption occurs for the salts of

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214 Li + , Na + and K+ and the ions of some alkaline earths (cf. Fig. 4.3). 4.3.1 Diffuse electrical layer

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The diffuse layer is formed, as mentioned above, through the interaction of the electrostatic field produced by the charge of the electrode, or, for specific adsorption, by the charge of the ions in the compact layer. In rigorous formulation of the problem, the theory of the diffuse layer should consider: (a) The individual ion dimensions (b) The effect of the electric field in the diffuse layer on the dielectric properties of the solvent (c) The effect of the ions on the dielectric properties of the solvent A rigorous solution of this problem was attempted, for example, in the 'hard sphere approximation' by D. Henderson, L. Blum, and others. Here the discussion will be limited to the classical Gouy-Chapman theory, describing conditions between the bulk of the solution and the outer Helmholtz plane and considering the ions as point charges and the solvent as a structureless dielectric of permittivity e. The inner electrical potential 0(1) of the bulk of the solution will be taken as zero and the potential in the outer Helmholtz plane will be denoted as 0 2 - The space charge in the diffuse layer is given by the Poisson equation divD=-/9 (4.3.2) where D is the electrical displacement given by the product of the permittivity of the solution and of the electric field grad 0. If e is not a function of the coordinates and a linear problem is involved (i.e. if in the diffuse layer the potential 0, charge density p and ion concentrations c, are functions only of the coordinate x perpendicular to the outer Helmholtz plane), then Eq. (4.3.2) becomes d2d> p div grad 0 = *f = - ax e (4.3.3)

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The space charge density is given by the sum of the charges of all the ions present: P = i(d)<t>ZiF (4.3.4)

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