Interface Gibbs energy

The open cell discussed was considered as an equilibrium cell since equilibrium was established across each individual interface. However, the cell as a whole is not in equilibrium the overall Gibbs energy of the full reaction is not zero, and when the circuit is closed, an electric current flows that is attended by chemical changes (i.e., a spontaneous process sets in). 

This dependence is fundamental for electrochemistry, but its key role for liquid-liquid interfaces was first recognized by Koryta [1-5,35]. The standard transfer energy of an ion from the aqueous phase to the nonaqueous phase, AGf J, denoted in abbreviated form by the symbol A"G is the difference of standard chemical potential of standard chemical potentials of the ions, i.e., of the standard Gibbs energies of solvation in both phases. 

For symmetrical electrolytes, of, e.g., type 1 1, such a liquid-liquid interface, in equilibrium, is described by the standard Galvani potential, usually called the distribution potential. This very important quantity can be expressed in the three equivalent forms, i.e., using the ionic standard potentials, or standard Gibbs energies of transfer, and employing the limiting ionic partition coefficients [3] ... 

The voltammetric information given here suggests that the transfer of an objective cation from Wl to LM can be achieved under a smaller membrane potential when an anion for which the Gibbs transfer energy at the LM/W2 interface is smaller is added into W2. In the case of the above-mentioned membrane system, the transfer of K+ from Wl to LM in the presence of 0.01 M MgBr2 in W2 is expected to be attained even at the membrane potential 0.19 V (which corresponds to the Gibbs energy of transfer of 18.3... 

Kulik, D. A., 2002, Gibbs energy minimization approach to model sorption equilibria at the mineral-water interface Thermodynamic relations for multi-site-surface complexation. American Journal of Science 302,227-279. ... 

There are other ways of estimating inner potential differences. Gi rault and Schiffrin [4] assume that the difference in the inner potential is negligible at the pzc, because the interface consists of an extended layer where both solvents mix, so that any dipole potentials will be small. The resulting scale of Gibbs energies of transfer agrees reasonably well with the TPAs+/TPB scale, if the small difference in the radii of these ions is accounted for. 

The determination of the Gibbs energy of adsorption at zero surface coverage AGg=o nd of the interaction parameter A as a function of an electrical variable, may become a valuable source of information on the interactions at the interface. The value of AG°can be considered as the energy required to replace n monomolecularly adsorbed solvent molecules from a fully solvent-covered electrode surface by one monomeric molecule of the solute... 

As mentioned earlier, the Gibbs energy of adsorption can be analyzed using one of two independent electrical variables potential or charge density. The problem was discussed by Parsons and others, but it was not unequivocally solved because both variables are interconnected. Recent studies of the phase transition occurring at charged interfaces, performed at a controlled potential, show that if the potential is... 

The AG° values of acetone adsorption decrease slightly in the sequence H2O,Me0H, NM. They are indicative of a weak physical adsorption at the Hg/solution interface. It is also evident that the Gibbs energy of adsorption is enhanced by the electric field, particularly at the point of adsorption maximum. Small values of AG , similar to those determined at the solution/air interface, attest to the absence of specific interactions cf acetone with the mercury surface (which is opposite to the TU adsorption case). Hence, the solute-solvent interaction in the solution is an important factor in the adsorption of acetone, as shown for the zero charge on the Hg electrode in Fig. 11. 

What are the differences when we deal with internal surfaces i.e., interfaces) instead of free surfaces Although more complex in detail, wrong bonds are again responsible for internal surface Gibbs energies. Therefore, we normally expect cusps to occur in Eb vs. 0 (y vs. 0) plots (Fig. 3-9). 

In heterogeneous solid state reactions, the phase boundaries move under the action of chemical (electrochemical) potential gradients. If the Gibbs energy of reaction is dissipated mainly at the interface, the reaction is named an interface controlled chemical reaction. Sometimes a thermodynamic pressure (AG/AK) is invoked to formalize the movement of the phase boundaries during heterogeneous reactions. This force, however, is a virtual thermodynamic force and must not be confused with mechanical (electrical) forces. 

These g values are defined per unit volume. Let us now put in the interface energy previously left out. If V = 4/3-7rr3 is the volume of the nucleus, the net Gibbs energy change is (neglecting elastic misfit energies)... 

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