Metal-solution interphase model

The simplest model of the structure of the metal-solution interphase is the Helmholtz compact double-layer model (1879). According to this model, all the excess charge... 

The simplest model of the structure of the metal-solution interphase is the Helmholtz compact double-layer model (1879). According to this model, all the excess charge on the solution side of the interphase, qs. is lined up in the same plane at a fixed distance away from the electrode, the Helmholtz plane (Fig. 4.4). This fixed distance xH is determined by the hydration sphere of the ions. It is defined as the plane of the centers of the hydrated ions. All excess charge on the metal, qM, is located at the metal surface. 

The rigoroiis analysis of the effect of temperature variations on interfacial properties is a key tool to provide new and valuable information on the structure and reactivity of the metal solution interphase. The entropy of the components that form the interphase is a unique probe of their stmctural properties. Therefore, this experimental data is particularly useful for the validation of molecular models of electrified interphases. In addition, the use of fast temperature perturbations is especially suitable for the selective characterization of different inter-facial components, based on their different response time towards the temperature change. In this way, the entropic properties of doublelayer phenomena and charge-transfer adsorption processes can be evaluated separately. It will be shown in this chapter that the combina-... 

First let us turn our attention to the metal surface and understand the simplifications which we usually make when considering it as part of the electrode-solution interphase then we shall present a model for the structure of the solution at the interphase and discuss the expected behaviour of this model when the potential of the electrode varies. We shall continue to discuss the influence that the interphase may have on electrode reactions and conclude this section by enumerating the different variables which are important in the study of the interphase. 

Against simplistic views of the FIAM, it is necessary to stress that the model does not imply that the free metal ion is the only species available to the microorganism [2,14], Indeed, the internalisation flux (i.e. the rate of acquisition) depends on the free metal ion concentration at the biological interphase (which in the FIAM is practically cj ), but metal bound to a ligand in the solution can dissociate, can diffuse (under a negligible gradient according to the FIAM), and can eventually be taken up. 

The next question concerns how these excess charges are distributed on the metal and solution sides of the interphase. We discuss these topics in the next four sections. Four models of charge distribution in the solution side of the interphase are discussed the Helmholtz, Gouy-Chapman, Stern, and Grahame models. 

Thus, according to this model, the interphase consists of two equal and opposite layers of charges, one on the metal ( m) the other in solution (q ). This pair of charged layers, called the double layer, is equivalent to a parallel-plate capacitor (Fig. 4.5). The variation of potential in the double layer with distance from the electrode is linear (Fig. 4.4). A parallel-plate condenser has capacitance per unit area given by the equation... 

Thus, according to these theories, all univalent (1 1) electrolytes should behave the same way. However, this is not what was observed experimentally. Solutions of different 1 1 electrolytes (e.g., NaCl, NaBr, Nal, KI) show species-specific behavior. In order to interpret this specific behavior, Grahame (5) proposed a new model of the interphase the triple-layer model. The basic idea in the interpretation of the ion-specific behavior is that anions, when attracted into the interphase, may become dehydrated and thus get closer to the electrode. Each anion undergoes this to a different extent. This difference in the degree of dehydration and the difference in the size of ions results in the specific behavior of the anions. Ions that are partially or fully dehydrated are in contact with the electrode. This contact adsorption of ions allows short-range forces (e.g., electric image forces) to act between the metal elec-... 

The first attempt to explain the capacitive nature of the interphase is credited to Helmholtz, in the middle of the nineteenth century. In his model, the interphase is viewed as a parallel-plate capacitor - a layer of ions on its solution side and a corresponding excess of charge on the surface of the metal. It should be noted here that electroneutrality must be maintained in the bulk of all phases, but not at the... 

The surface films discussed in this section reach a steady state when they are thick enough to stop electron transport. Hence, as the surface films become electrically insulating, the active electrodes reach passivation. In the case of monovalent ions such as lithium, the surface films formed in Li salt solutions (or on Li metal) can conduct Li-ions, and hence, behave in general as a solid electrolyte interphase (the SEI model ). See the basic equations 1-7 related to ion transport through surface films in section la above. The potentiodynamics of SEI electrodes such as Li or Li-C may be characterized by a Tafel-like behavior at a high electrical field and by an Ohmic behavior at the low electrical field. The non-uniform structure of the surface films leads to a non-uniform current distribution, and thereby, Li dissolution from Li electrodes may be characterized by cracks, and Li deposition may be dendritic. The morphology of these processes, directed by the surface films, is dealt with later in this chapter. When bivalent active metals are involved, their surface films cannot conduct the bivalent ions. Thereby, Mg or Ca deposition is impossible in most of the commonly used polar aprotic electrolyte solutions. Mg or Ca dissolution occurs at very high over potentials in which the surface films are broken. Hence, dissolution of multivalent active metals occurs via a breakdown and repair of the surface films. 

Figure 7-17. Impedance model of iron corrosion in neutral aerated solution with inhomogeneous diffusion of oxygen and reaction control of the anodic metal dissolution (Zmc) (a) metal/electro-lyte interphase, (b) elements of the transfer function.

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