Ivey 1 wel


Oscillations are found in this model iffi <5 = 1 +A.  [c.1114]

The model of the inner layer suggests that the interaction energy of water molecules with the metal will be at a minimum somewhere close to the PZC, a result strongly supported by the fact that adsorption of less polar organic molecules often shows a maximum at this same pomt [18]. Flowever, particularly at anodic potentials, there is now strong evidence that simple anions may lose part of their hydration or solvation sheath and migrate from the OFIP to the IFIP. There is also evidence that some larger cations, such as [R N], Tl and Cs also undergo specific adsorption at sufiBciently negative potentials. The evidence for specific adsorption comes not only from classical experiments in which the surface tension of mercury is studied as a ftmction of the potential (electrocapillarity), and the coverage derived from rather indirect reasoning [28], but also more direct methods, such as the measurement of the amount of material removed from solution, using radioactive tracers and ellipsometry. A critical problem is much of this work, particularly in those data derived from electrocapillarity, is that the validity of the Gotiy-Chapman model must be assumed, an assumption that has been queried. The calculation of the free energy change associated witii this process is not simple, and the following efiects need to be considered.  [c.594]

The energy gained on moving from the OFIP to the IFIP. The electrostatic part of this will have the fomi  [c.594]

The matrix elements l "l/ l " are multidimensional integrals J 4> Uf )iiUf )4>n U/)[c.1062]


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