Chemical Equilibrium. A Chem1 Reference Text(en)(28s) by Lower S. K.

By Lower S. K.

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Ii) Examples of the Standard-State Selection The Gibbs energy of adsorption is a measure of adsorbate–metal interactions. Its values depend, however, on the choice of standard states for the chemical potentials of the components involved in the process. Therefore values determined for different systems can only be compared if they refer to the same standard-state conditions. values of adsorption of thiourea (TU) on several metallic electrodes, calculated for the most often used standard states, are presented in Table 1.

It was concluded that at a potential of zero charge, the water structure near the electrode surface is the same as in the bulk. The polymeric structure of water is disrupted at high surface field strength, and small clusters are formed. Using a similar technique, Bockris and Habib82 studied water adsorption on a smooth platinum electrode in 50% solution. , with the increase of the water–platinum bond energy. According to one of the surface selection rules, the amplitude of the observed band shifts from zero to a maximum when the adsorbed water molecules change their orientation from parallel to perpendicular to the surface (only dipoles perpendicularly oriented to the surface interact with the incident light).

Two different methods are usually used. The first one, described in detail by Wieckowski,104 is used to measure the surface concentration on rough electrodes. Solute is labeled with a low-energy emitter in order to decrease, owing to self-absorption, the counting coming from the bulk of the solution. , in the glass scintillator placed directly under the electrode surface. The counting rate is proportional to the amount of adsorbed species, which can easily be converted into the surface concentration provided that the roughness factor of the electrode is known.

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