Surface complexation limit

Naturally, the number of surface sites limits the amount of Pt complexes that can be adsorbed. Typically, the.se catalysts contain up to 1 wt% Pt. Adsorption is a fast process and in general an eggshell catalyst will be formed. Figure 3.29 shows the processes that occur. 

Integrating equations (2.37) and (2.39) under assumption that in case of direct reaction of surface complex formation (Me C ) the reaction of interaction of oxygen with surface metal atoms is the limiting stage rather than formation of physadsorbed oxygen (i.e. assuming that [02( )J = const and it does not change in time) we arrive to the respective expression for kinetics of direct and inverse reactions ... 

In the surface complex formation model the amount of surface charge that can be developed on an oxide surface is restricted by the number of surface sites. (This limitation is inherently not a part of the Gouy-Chapman theory.)... 

The surface characteristics of kaolinite was discussed in Chapter 3.4 and in Fig. 3.9. While the siloxane layer may - to a limited extent - participate in ion exchange reactions. The functional OH-groups at the gibbsite and edge surfaces are able to surface complex heavy metal ions. (Schindler et al., 1987). 

Adsorption and Precipitation vs heterogeneous Nucleation and Surface Precipitation. There is not only a continuum between surface complexation (adsorption) and precipitation, but there is also obiously a continuum from heterogeneous nucleation to surface precipitation. The two models are two limiting cases for the initiation of precipitation. In the heterogeneous nucleation model, the interface is fixed and no mixing of ions occurs across the interface. As a consequence precipi-... 

Pathway (d) in Fig. 9.3 provides a possible explanation for the efficiency of a combination of a reductant and a complex former in promoting fast dissolution of Fe(III) (hydr)oxydes. In this pathway, Fe(II) is the reductant. In the absence of a complex former, however, Fe2+ does not transfer electrons to the surface Fe(III) of a Fe(III) (hydr)oxide to any measurable apparent extent. The electron transfer occurs only in the presence of a suitable bridging ligand (e.g., oxalate). As illustrated in Fig. 9.3d, a ternary surface complex is formed and an electron transfer, presumably inner-sphere, occurs between the adsorbed Fe(II) and the surface Fe(III). This is followed by the rate-limiting detachment of the reduced surface iron. In this pathway, the concentration of Fe(U)aq remains constant while the concentration of dissolved Fe(III) increases thus, Fe(II)aq acts as a catalyst to produce Fe(II)(aq) from the dissolution of Fe(III)(hydr)oxides. 

In an interesting analysis of the effects of reduction of dimensionality on rates of adsorption/desorption reactions (26), the bimolecular rate of 10 M- s- has been reported as the lower limit of diffusion control. Based on this value, the rates given in Table III indicate the desorption step is chemical-reaction-controlled, likely controlled by the chemical activation energy of breaking the surface complex bond. On the other hand, the coupled adsorption step is probably diffusion controlled. 

Similar photo-induced reductive dissolution to that reported for lepidocrocite in the presence of citric acid has been observed for hematite (a-Fe203) in the presence of S(IV) oxyanions (42) (see Figure 3). As shown in the conceptual model of Faust and Hoffmann (42) in Figure 4, two major pathways may lead to the production of Fe(II)ag i) surface redox reactions, both photochemical and thermal (dark), involving Fe(III)-S(IV) surface complexes (reactions 3 and 4 in Figure 4), and ii) aqueous phase photochemical and thermal redox reactions (reactions 11 and 12 in Figure 4). However, the rate of hematite dissolution (reaction 5) limits the rate at which Fe(II)aq may be produced by aqueous phase pathways (reactions 11 and 12) by limiting the availability of Fe(III)aq for such reactions. The rate of total aqueous iron production (d[Fe(aq)]T/dt = d [Fe(III)aq] +... 

Few studies have systematically examined how chemical characteristics of organic reductants influence rates of reductive dissolution. Oxidation of aliphatic alcohols and amines by iron, cobalt, and nickel oxide-coated electrodes was examined by Fleischman et al. (38). Experiments revealed that reductant molecules adsorb to the oxide surface, and that electron transfer within the surface complex is the rate-limiting step. It was also found that (i) amines are oxidized more quickly than corresponding alcohols, (ii) primary alcohols and amines are oxidized more quickly than secondary and tertiary analogs, and (iii) increased chain length and branching inhibit the reaction (38). The three different transition metal oxide surfaces exhibited different behavior as well. Rates of amine oxidation by the oxides considered decreased in the order Ni > Co >... 

Reductive dissolution occurs via (i) surface precursor complex formation between reductant molecules and oxide surface sites, (ii) electron transfer within this surface complex, and (iii) breakdown of the successor complex and release of dissolved metal ions. Surface speciation is important in determining rates of each of these contributing steps. Limited available evidence concerning rates and mechanism of surface chemical reactions and analogy to similar reactions in homogeneous solution both support this conclusion. 

This scheme disregards mass transfer limitations and represents only a simplified model. Formation of A S may involve specific interactions, such as hydrogen bonds, coordination, or ir-complex formation, or non-specific interactions, such as van der Waals or hydrophobic bonds. Non-specific interactions are insignificant for small polar molecules, but may contribute significantly to the surface complex formation if the hydrophobic moiety is large ( 5, 6) ... 

The adsorption data is often fitted to an adsorption isotherm equation. Two of the most widely used are the Langmuir and the Freundlich equations. These are useful for summarizing adsorption data and for comparison purposes. They may enable limited predictions of adsorption behaviour under conditions other than those of the actual experiment to be made, but they provide no information about the mechanism of adsorption nor the speciation of the surface complexes. More information is available from the various surface complexation models that have been developed in recent years. These models represent adsorption in terms of interaction of the adsorbate with the surface OH groups of the adsorbent oxide (see Chap. 10) and can describe the location of the adsorbed species in the electrical double layer. 

The similarity between the measured activation energies for the reaction-limited production of acrolein over Cu20(100) from allyl alcohol in UHV or propene following a 1 atm. exposure gives a clear indication that these reactions involve the same surface intermediate, an allyloxy. This similarity also suggests that the surface intermediates formed by these two routes behave in a chemically similar fashion. For the (100) surface, the Cu -alkoxide surface complex is similar regardless of whether oxygen from... 

Figure 11.1. Schematic views of various ways in which an organic chemical, i, may sorb to natural inorganic solids (a) adsorption from air to surfaces with limited water presence, (b) partitioning from aqueous solutions to the layer of vicinal water adjacent to surfaces that serves as an absorbent liquid, (c) adsorption from aqueous solution to specific surface sites due to electron donor-acceptor interactions, (d) adsorption of charged molecules from aqueous solution to complementarily charged surfaces due to electrostatic attractions, and (e) chemisorption due to surface bonding or inner sphere complex formation.

Adequacy of Thermodynamic Data. Data on several important aluminosilicates appear to be insufficient for a detailed discussion of all equilibria. Information on the influence of solid solutions or coprecipitated phases on thermodynamic properties appears to be rather limited, as is that for metastable non-stoichiometric oxides (e.g., of manganese) and surface complexes. 

There is no simple, comprehensive theory and steric forces are complex and difficult to describe. Different components contribute to the force, and depending upon the situation, dominate the total force. The most important interaction is repulsive and of entropic origin. It is caused by the reduced configuration entropy of the polymer chains. If the thermal movement of a polymer chain at a surface is limited by the approach of another surface, then the entropy of the individual polymer chain decreases. In addition, the concentration of monomers in the gap increases. This leads to an increased osmotic pressure. 

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