Competitive adsorption, mixtures

When one of the two acids is used in excess and the pk -values of the two acids differ strongly, the salt deficit method should be used with caution. Formic add, acetic acid, propionic acid, and trifluoroacetic acid have been electrolyzed competitively in mixtures of pairs. Formic acid and trifluoroacetic acid are comparable in case of electrolysis, both are more readily electrolyzed than acetic and propionic adds. Deviations are rationalized on the basis of differences in ionization [147]. It might 1 useful in such cases to neutralize both acids completely. Sometimes one of the two acids, although being the minor component, is more favorably oxidized possibly due to preferential adsorption or its higher acidity [148]. In this case the continuous addition of the more acidic add to an excess of the weaker acid may lead to successful cross-coupling [149], The chain length of the two acids should be chosen in such a... 

If this is not the case, the adsorption behavior can be described by competitive adsorption. The extent of adsorption depends not only on the individual adsorption constants but also on the intrinsic kinetics of adsorption of the individual adsorbates and thus, the adsorption layer formed is influenced by the qualitative and quantitative composition of the complex mixture of adsorbable solutes full equilibrium is often not attained (Cosovic, 1990). 

Fig. 5 FTIR spectra of ssDNA films adsorbed onto gold surfaces from aqueous solutions. Reference spectra for films of individual 5-mer homo-ONDs are shown along with spectra following competitive adsorption from their equimolar mixtures. The corresponding surface density, n, is indicated for each of the homo-ONDs (lO OND cm ) [23]...

The adsorption of the solutes by discrete one-to-one complexes was discussed by Soczewinski (77, 78). In this simple model equations for k value are derived by the application of the law of mass action to the competitive adsorption equilibria between solute and solvent molecules for the active sites of the adsorbent. It follows then that with an eluent mixture containing a polar solvent in an inert" nonpolar diluent, a linear relationship holds so that... 

In water-DMSO mixtures in the presence of C104 and 1 anions, the electroreduction of Cd(II) ions was influenced by competitive adsorption of DM SO molecules and anions [224] and the rate of the Cd(II)/Cd process changed nonmonotonically with solvent composition. In water-rich mixtures, the electrode process was accelerated by the formation of activated complex Cd(II)-anion (ClO, —, I ). At higher DM SO concentration, the rate of the Cd(II)/Cd process was found to decrease and reach minimum at DM SO concentration equal to 9M. At cdmso > 9 M, the rate of the process increased again. 

It was found that the competitive adsorption of 1 and AN molecules on the Cd electrode affected the kinetics of the Cd(II) electroreduction [226]. The physicochemical properties of coatings and effects of organic additives on cadmium deposition from iodide-water-AN mixtures were also studied by Kuznetsov et al. [225]. 

The same authors have found that the inhibition effect of crown ethers [230] and crown esters [229] on cadmium electrodeposition from water-AN mixtures was caused by the competitive adsorption of macrocycles and organic solvents molecules. The effect of structure and concentration of crown ethers on the cadmium electrodeposition from aqueous sulfate solutions was also studied [231]. 

Figure 4 shows an example of the adsorbed amount of NP-EO q and SDS from a surfactant mixture as a function of the total surfactant concentration. The figure shows that the adsorbed amount reaches a limiting value, which is close to the cmc of the solution mixture. In this example the initial NP-EO- q/SDS ratio is 30/70 (w/w), i.e. the SDS is present in excess. The figure reveals, however, that NP-EO g is present in excess on the surface, i.e. a strong competitive adsorption is taking place. 

A situation that commonly occurs with food foams and emulsions is that there is a mixture of protein and low-molecular-weight surfactant available for adsorption at the interface. The composition and structure of the developing adsorbed layer are therefore strongly influenced by dynamic aspects of the competitive adsorption between protein and surfactant. This competitive adsorption in turn is influenced by the nature of the interfacial protein-protein and protein-surfactant interactions. At the most basic level, what drives this competition is that the surfactant-surface interaction is stronger than the interaction of the surface with the protein (or protein-surfactant complex) (Dickinson, 1998 Goff, 1997 Rodriguez Patino et al., 2007 Miller et al., 2008 Kotsmar et al., 2009). 

However, about three times more of propanal than of acetone was obtained from an equimolecular mixture of 1 and 2-propanol this difference might arise from competitive adsorptions it seems to indicate that free radicals are not involved under these conditions. 

In studies of competitive adsorption, the usually measured quantity is the overall composition of the adsorbed phase for a given composition of the bulk phase in equilibrium with it. It has been found that chemical shifts can provide a more detailed description. In a mixture of Xe and Kr in N 4 zeolite it was possible to observe the individual signals from XenKr mixed clusters as well as the Xen clusters under magic angle spinning (28). The absolute 129Xe chemical shifts of the XenKr mixed clusters and the increments between XenKr and the Xen+1 in various Xe-Kr mixtures in Na4 zeolite, are shown in Table I. 

The high molar mass species reside mostly in the aqueous phase with a number of peptide groups residing in the oil/water interface [293]. Although these latter surfactants are less effective at reducing interfacial tension, they can form a viscoelastic membrane-like film around oil droplets or air bubbles. These tend to be used in the preparation of, for example, O/W emulsions. These trends are by no means exclusive, mixtures are the norm and competitive adsorption is prevalent. Caseinate, one of the most commonly used surfactants in the food industry, is itself a mixture of interacting proteins of varying surface activity [814],... 

Although the multicomponent Langmuir equations account qualitatively for competitive adsorption of the mixture components, few real systems conform quantitatively to this simple model. For example, in real systems the separation factor is generally concentration dependent, and azeotrope formation (a = 1.0) and selectivity reversal (a varying from less than 1.0 to more than 1.0 over the composition range) are relatively common. Such behavior may limit the product purity attainable in a particular adsorption separation. It is sometimes possible to avoid such problems by introducing an additional component into the system which will modify the equilibrium behavior and eliminate the selectivity reversal. 

Optimal operating conditions and catalysts Acetylation of phenyl ethers was generally carried out in the absence of solvents, which makes easier the recovery of the acetylated product from the reaction mixture. On the other hand, because of the high melting point of substrate and acetylated products, solvents were always used in the acetylation of 2-methoxynaphthalene. Flow reactors (e.g. fixed bed tubular reactors), in which the detrimental effect of competitive adsorption of substrate and products on the acetylation yield is lower than in the batch reactors, should be preferred. However although the set up of fixed bed reactors for liquid phase reactions is relatively simple, their substitution to the batch reactors, which are the only system used in academic organic chemistry, remains essentially limited to commercial units. 

The occurrence of competitive adsorption may complicate matters, and the conclusions stated previously may no longer pertain. A compound that is intrinsically more reactive than another may react more slowly than the other when both are present in a mixture because of stronger adsorption of the other compound. Such inhibition effects may be caused not only by the reacting molecules but also by the hydrotreating products, such as intermediates and end products including H2S and NH3. 

A Langmuir-Hinshelwood type of rate expression is often used to describe the effect of the competitive adsorption of components m in the reaction mixture on the rate of hydrotreating of compound i ... 

Prins summarizes advances in understanding of the reactions in catalytic hydrodenitrogenation (HDN), which is important in hydroprocessing of fossil fuels. Hydroprocessing is the largest application in industrial catalysis based on the amount of material processed. The chapter addresses the structures of the oxide precursors and the active sulfided forms of catalysts such as Ni-promoted Mo or W on alumina as well as the catalytically active sites. Reaction networks, kinetics, and mechanisms (particularly of C-N bond rupture) in HDN of aliphatic, aromatic, and polycyclic compounds are considered, with an evaluation of the effects of competitive adsorption in mixtures. Phosphate and fluorine promotion enhance the HDN activity of catalysts explanations for the effect of phosphate are summarized, but the function of fluorine remains to be understood. An account of HDN on various metal sulfides and on metals, metal carbides, and metal nitrides concludes this chapter. 

As trial system to test the application of the proposed model the ability of encapsulated XAD-7 was evaluated for the selective separation of berberine from dilute aqueous mixtures of berberine and dopamine, the target secondary metabolite, and an undesirable intermediate metabolite of Thalictrum rugosum plant cell culture [18]. Competitive adsorption experiments were performed in dilute aqueous mixtures of berberine and dopamine, both at initial concentrations of 60 mg l-1, which is representative of actual plant cell culture. Experimental and theoretical results for normalized bulk concentration profiles of berberine and dopamine are shown in Fig. 10. The bulk berberine concentration was reduced to approximately 4.6% of the initial concentration, which indicates that 95.4% of the berberine in the initial mixed solution was adsorbed. Encapsulated XAD-7, therefore, selectively concentrated the berberine from dilute aqueous mixtures of berberine and dopamine. 

Using SFS, Davies and co-workers [77-79] reported enhanced adsorption and competitive adsorption at the hydrophobic surface, reminiscent of that seen at the air-solution interface. For the SDS/PEO mixture [79], competitive adsorption was observed at low concentrations, whereas at higher SDS concentrations, PEO was depleted from the surface. Similar observations were made from IR-ATR measurements by Poirier et al. [80] on CieTAB/PSS mixtures at the silica-solution interface. However, the technique could not distinguish between depletion or surface complex formation. Similar trends were also reported by Fielden et al. [76] for SDS/AM-MAPTC mixtures on mica. For the PEI/SDS mixture at the hydrophobic interface [76], the SFS measurements indicated a higher degree of order and hence adsorption due to complexation at the interface. This was also shown to be strongly pH dependent [81],... 

Figure 5.10. Concentrations in a liquid-solid adsorption system (competitive adsorption from binary mixture or solution).

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