Chemisorption, anionic

In the presence of mineral phases containing anions that would form sparingly soluble compounds (e.g. POt - and F for the lower oxidation states) an enhanced plutonium uptake due to chemisorption can be expected (57). For plutonium in the higher oxidation states the formation of anionic carbonate complexes would drastically reduce the sorption on e.g oxide and silicate surfaces. 

Adsorption of ions from the solution. There are two types of ionic adsorption from solutions onto electrode surfaces an electrostatic (physical) adsorption under the effect of the charge on the metal surface, and a specific adsorption (chemisorption) under the effect of chemical (nonelectrostatic) forces. Specifically adsorbing ions are called surface active. Specific adsorption is more pronounced with anions. 

Whenever the concentration of a species at the interface is greater than can be accounted for by electrostatic interactions, we speak of specific adsorption. It is usually caused by chemical interactions between the adsorbate and the electrode, and is then denoted as chemisorption. In some cases adsorption is caused by weaker interactions such as van der Waals forces we then speak of physisorption. Of course, the solvent is always present at the interface so the interaction of a species with the electrode has to be greater than that of the solvent if it is to be adsorbed on the electrode surface. Adsorption involves a partial desolvation. Cations tend to have a firmer solvation sheath than anions, and are therefore less likely to be adsorbed. 

In addition to phosphine ligands, a variety of other monodentate and chelating ligands have been introduced to functionalized polymers [1-5]. For example, cyclo-pentadiene was immobilized to Merrifield resins to obtain titanocene complexes (Fig. 42.13) [102]. The immobilization of anionic cyclopentadiene ligands represents a transition between chemisorption and the presently discussed coordinative attachment of ligands. The depicted immobilization method can also be adopted for other metallocenes. The titanocene derivatives are mostly known for their high hydrogenation and isomerization activity (see also Section 42.3.6.1) [103]. 

At this point, we have reached the stage where we can describe the adatom-substrate system in terms of the ANG Hamiltonian (Muscat and Newns 1978, Grimley 1983). We consider the case of anionic chemisorption ( 1.2.2), where a j-spin electron in the substrate level e, below the Fermi level (FL) eF, hops over into the affinity level (A) of the adatom, whose j-spin electron resides in the lower ionization level (I), as in Fig. 4.1. Thus, the intra-atomic electron Coulomb repulsion energy on the adatom (a) is... 

Fig. 4.1. Anionic chemisorption energy-level diagram showing transfer of j-spin electron from substrate level ek to affinity level A on adatom, while experiencing Coulomb repulsion U from j-spin electron in ionization level I.

Both cationic adsorption and anionic adsorption belong to what is called ionic adsorption. Covalent adsorption is due to the localized covalent bonding, and metallic adsorption is due to the delocalized covalent bonding. The distinction among these three modes of chemisorption, however, is not so definite that the transition from the covalent through the metallic to the ionic adsorption may not be discontinuous, but rather continuous, in the same way as the transition of the three-dimensional solid compounds between the covalent, metallic, and ionic bonding. 

Chemisorption of anions at the electrode interface involves dehydration of hydrated anions followed by adsorption of dehydrated anions which, then, penetrate into the compact double layer to contact the interface directly, this result is called the contact adsorption or specific adsorption. The plane of the contact adsorption of dehydrated anions is occasionally called the inner Helmholtz plane... 

Hg/OH on which the standard electrochemical free enthalpy of anion adsorption is positive AGli > 0), only the ph3 ical adsorption of hydrated anions occurs at the OHP whereas, the chemisorption of anions takes place at the IHP on those electrodes whose standard electrochemical free enthalpy of anion adsorption is negative < 0). 

Such anion adsorption can be prevented by chemisorbing a mono-layer of a strongly adherent thiol molecule to the Au surfaces [97,98]. 1-Propanethiol (PT) was used here because the gold nanotubules can still be wetted with water after chemisorption of the PT monolayer [97].t The Em versus applied potential curves for an untreated and PT-treated gold nanotubule membrane, with KBr solutions present on either side of the membrane, are shown in Fig. 13. The untreated membrane shows only cation permselectivity, but the permselectivity of the PT-treated membrane can be switched, exactly as was the case with the nonadsorbing electrolyte (Fig. 12). 

In cathodic area, the Tafel slope in the presence of DDTC is bigger than that in the absence of DDTC, and the cathodic curves imder the conditions of different DDTC concentration are almost parallel and their Tafel slopes only change a little. These demonstrate that the chemisorption of DDTC on the surface of jamesonite electrode also inhibits the cathodic reaction, but the chemisorption amoimt of DDTC is a little and almost not affected by the DDTC concentration due to their negatively electric properties of DDTC anion and the electrode surface. This reveals that there is a little DDTC chemisorption on the mineral even if the potential is lower (i.e., negative potential). 

The spectra obtained from the chemisorption of methanol onto catalyst above 100°C indicated the progressive oxidation of methoxy species to formate via dioxymethylene/HCHO and finally to CO, CO2, and H2. Phenol adsorbed on the surface Lewis acid-base pair site and dissociated to phenolate anion and proton. The formation of phenolate anion and proton were discerned from the strong intense C-0 stretching vibration and the disappearence of phenolic 0-H stretching vibration, respectively. Importantly, there were series of definite low intensity bands between 2050 and 1780 cm" that were identified as the out-of-plane aromatic C-H bending vibrations [79, 84-85]. These bending vibrations are possible only if the phenyl ring of phenol is perpendicular to the catalyst surface. 

Certain regions where anionic chemisorption occurs on p-type semicon-... 

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