Counter-ions, adsorption

Formation of the t2g band with a binding energy of 0.8 eV below the Fermi level in Fig. 21 indicates a change in Ru coordination for potentials above 0.4 V. The increased O/Ru ratio in Fig. 20 is therefore not only a consequence of enhanced counter ion adsorption, but rather a result of oxide/hydroxide formation. 

Figure 2. Representation of the possible site forms in the site-binding model which includes the effect of counter-ion adsorption, combined with a diagram of charges and potentials at the insulator/electrolyte interface. Reproduced with permission from Ref. (14). Copyright 1983, North Holland.

Procedure. The solid used is a Merck alumina gel. The product is predominantly amorphous but its X-ray diffraction pattern exhibits small peaks characteristics of gibbsite. Its surface charge determined by counter-ions adsorption is reported in Fig. 4. Batch experiments were performed using 5 g/L solid contacted with ltr4 m uranyl carbonated solutions at pH 7... 

Surfaces which are already charged (e.g. by ionisation) usually show a preferential tendency to adsorb counter-ions, especially those with a high charge number. It is possible for counter-ion adsorption to cause a reversal of charge. 

Jang, H. M., The nature of counter-ion adsorption at the oxide/water interface, Ph. D. Thesis, University of California, Berkeley, 1986. 

Copper electrodeposition on Au(111) Copper is an interesting metal and has been widely investigated in electrodeposition studies from aqueous solutions. There are numerous publications in the literature on this topic. Furthermore, technical processes to produce Cu interconnects on microchips have been established in aqueous solutions. In general, the quality of the deposits is strongly influenced by the bath composition. On the nanometer scale, one finds different superstmctures in the underpotential deposition regime if different counter-ions are used in the solutions. A co-adsorption between the metal atoms and the anions has been reported. In the underpotential regime, before the bulk deposition begins, one Cu mono-layer forms on Au(lll) [66]. 

The physical meaning of the g (ion) potential depends on the accepted model of an ionic double layer. The proposed models correspond to the Gouy-Chapman diffuse layer, with or without allowance for the Stem modification and/or the penetration of small counter-ions above the plane of the ionic heads of the adsorbed large ions. " The experimental data obtained for the adsorption of dodecyl trimethylammonium bromide and sodium dodecyl sulfate strongly support the Haydon and Taylor mode According to this model, there is a considerable space between the ionic heads and the surface boundary between, for instance, water and heptane. The presence in this space of small inorganic ions forms an additional diffuse layer that partly compensates for the diffuse layer potential between the ionic heads and the bulk solution. Thus, the Eq. (31) may be considered as a linear combination of two linear functions, one of which [A% - g (dip)] crosses the zero point of the coordinates (A% and 1/A are equal to zero), and the other has an intercept on the potential axis. This, of course, implies that the orientation of the apparent dipole moments of the long-chain ions is independent of A. 

Ionic compounds such as halides, carboxylates or polyoxoanions, dissolved in (generally aqueous) solution can generate electrostatic stabilization. The adsorption of these compounds and their related counter ions on the metallic surface will generate an electrical double-layer around the particles (Fig. 1). The result is a coulombic repulsion between the particles. If the electric potential associated with the double layer is high enough, then the electrostatic repulsion will prevent particle aggregation [27,30]. 

While in previous ab initio smdies the reconstructed surface was mostly simulated as Au(lll), Feng et al. [2005] have recently performed periodic density functional theory (DFT) calculations on a realistic system in which they used a (5 x 1) unit cell and added an additional atom to the first surface layer. In their calculations, the electrode potential was included by charging the slab and placing a reference electrode (with the counter charge) in the middle of the vacuum region. From the surface free energy curves, which were evaluated on the basis of experimentally measured capacities, they concluded that there is no necessity for specific ion adsorption [Bohnen and Kolb, 1998] and that the positive surface charge alone would be sufficient to lift the reconstmction. 

Electrochemical reactions are driven by the potential difference at the solid liquid interface, which is established by the electrochemical double layer composed, in a simple case, of water and two types of counter ions. Thus, provided the electrochemical interface is preserved upon emersion and transfer, one always has to deal with a complex coadsorption experiment. In contrast to the solid/vacuum interface, where for instance metal adsorption can be studied by evaporating a metal onto the surface, electrochemical metal deposition is always a coadsorption of metal ions, counter ions, and probably water dipols, which together cause the potential difference at the surface. This complex situation has to be taken into account when interpreting XPS data of emersed electrode surfaces in terms of chemical shifts or binding energies. 

The ionic strength of the solution also significantly influences polyelectrolyte adsorption. In general, the higher the ionic strength of the medium, the less extended and the more coiled the polymer conformation becomes (due to preferential interaction with counter ions in solution rather than with other segments of the polymer chain). The coiled polymer becomes more accessible to the internal porous structure and adsorption is increased. However, for the same reason, it is less influential on the surface charge. 

Figure 6.16 Reconformation of adsorbed cationic polyacrylamide (MW 4 x 106) on cellulose fibres as shown by the kinetics of adsorption and adsorption stoichiometry (measured by counter ion release).

The total energy of this adsorption reaction can be found experimentally from the microscopic activity quotient, and separated theoretically into the following components (1) transfer of the ion to be adsorbed from the bulk of solution to the oxide surface plane, at which the mean electrostatic potential is t/>q with respect to the bulk of solution (2) reaction of the adsorbate in the surface plane with a functional group at the surface (3) transfer of a fraction of the counter charge from solution into the solution part of the double layer by attraction of counter ions and (4) transfer of the remainder of the counter charge by expulsion of co-ions from the solution part of the double layer to the solution. 

Two mechanisms for retention in reversed-phase ion-pair liquid chromatography have been considered. One is the adsorption of the hydrophobic paired ion on the hydrophobic surface of stationary phase material. In the second mechanism, the hydrophobic counter-ion is held on the surface of the hydro-phobic stationary phase, and the analyte ion is retained by ion-ion interactions, as shown in Figure 4.16. In the latter case, of a dynamic ion-exchange... 

It is also noteworthy that the surface tension of mixed solutions of anionic and cationic surfactants is controlled by the activity of the salt (38). These results indicate that, in adsorption of an ionic surfactant at the solution surface, the accompanying adsorption of the counter ion also plays an important role. 

In addition to proton adsorption, interactions between the ions of the inert electrolyte (counter ions, section 10.3) and the oxide surface lead to ion pair formation which influences the electrochemical properties of the oxides and the determination of pKa values. Ion pair formation involves outer sphere surface complexes (see Chap. 11), e.g. 

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