Mathematical models double-layer capacitance

The second meaning of the word circuit is related to electrochemical impedance spectroscopy. A key point in this spectroscopy is the fact that any -> electrochemical cell can be represented by an equivalent electrical circuit that consists of electronic (resistances, capacitances, and inductances) and mathematical components. The equivalent circuit is a model that more or less correctly reflects the reality of the cell examined. At minimum, the equivalent circuit should contain a capacitor of - capacity Ca representing the -> double layer, the - impedance of the faradaic process Zf, and the uncompensated - resistance Ru (see -> IRU potential drop). The electronic components in the equivalent circuit can be arranged in series (series circuit) and parallel (parallel circuit). An equivalent circuit representing an electrochemical - half-cell or an -> electrode and an uncomplicated electrode process (-> Randles circuit) is shown below. Ic and If in the figure are the -> capacitive current and the -+ faradaic current, respectively. 

The method is based on the chemical equilibrium program MINEQL (2), modified to include the coulombic energy of adsorption caused by the charged surface. First the principles of MINEQL are presented through a short example from solution chemistry and then the extension of the method to the constant-capacitance double-layer model of the surface/solution interface used by Stumm, Schindler, and co-workers (3,4) is demonstrated. Finally, the use of the method in the triple-layer site-binding model introduced by Yates, Levine, and Healy (5), and used by Davis, James, and Leckie (6), is shown. In each case the mathematics are described in suflBcient detail to be reproducible. 

The method developed here for the description of chemical equilibria including adsorption on charged surfaces was applied to interpret phosphate adsorption on iron oxide (9), and to study electrical double-layer properties in simple electrolytes (6), and adsorption of metal ions on iron oxide (10). The mathematical formulation was combined with a procedure for determining constants from experimental data in a comparison of four different models for the surface/solution interface a constant-capacitance double-layer model, a diffuse double-layer model, the triplelayer model described here, and the Stem model (11). The reader is referred to the Literature Cited for an elaboration on the applications. 

The problem when trying to make an electrical model of the physical or chemical processes in tissue is often that it is not possible to mimic the electrical behavior with ordinary lumped, physically realisable components such as resistors (R), capacitors (C), inductors, semiconductor components, and batteries. Let us mention three examples 1) The constant phase element (CPE), not realizable with a finite number of ideal resistors and capacitors. 2) The double layer in the electrolyte in contact with a metal surface. Such a layer has capacitive properties, but perhaps with a capacitance that is voltage or frequency dependent. 3) Diffusion-controlled processes (see Section 2.4). Distributed components such as a CPE can be considered composed of an infinite number of lumped components, even if the mathematical expression for a CPE is simple. 

Any electrochemical cell can be represented in terms of an equivalent electrical circuit that comprises a combination of resistances, capacitances or inductances as well as mathematical components. At least the circuit should contain the double-layer capacity, the impedance of the faradaic or non-faradaic process and the high-frequency resistance. The equivalent circuit has the character of a model, which more or less precisely reflects the reality. The equivalent circuit should not involve too many elements because then the standard errors of the corresponding parameters become too large (see Sect. II.5.7), and the model considered has to be assessed as not determined, i.e. it is not valid. 

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