Adsorption driving forces

Three main mechanisms have been proposed to explain this behavior the TT-TT dispersion interaction mechanism, the H-bonding formation mechanism, and the electron donor—acceptor complex mechanism. The first two mechanisms were proposed by Coughlin and Ezra [16] in 1968, and the third mechanism was proposed by Mattson and coworkers [20] in 1969. At that time, phenol was known to be adsorbed in a flat position on the graphene layers, and in this situation the adsorption driving forces would be due to tt-tt dispersion interactions between the aromatic ring of phenol and the aromatic structure of the graphene layers. 

The concentradon of Species A on the surface is governed be the adsorption of A and B from the gas phase when the adsorption driving force is the product of the gas phase partial pressure and the concentration of vacant sites, Cy... 

This leads to the expectation that the eomponent that will be adsorbed in a given element of adsorption space will be the component with the highest adsorption driving force. Thus in a multicomponent system the kth component will displace the jth if... 

Chapter 3, there is often a region immediately preceding the lower closure point, in which increased adsorption is brought about by reversible capillary condensation. The meniscus now tends to be somewhat ill defined owing to its small dimensions (p. 153), but the mechanism can still be thought of in Kelvin terms, where the driving force is the pressure difference across an interface. 

All of these relations are brought together in the fundamental form (kinetic term)(driving force) adsorption term... 

Reaction Special condition Basic rate equation Driving force Adsorption term... 

Figure 16-9 depicts porous adsorbent particles in an adsorption bed with sufficient generality to illustrate the nature and location of individual transport and dispersion mechanisms. Each mechanism involves a different driving force and, in general, gives rise to a different form of mathematical result. 

This expression can be used to describe both pore and solid diffusion so long as the driving force is expressed in terms of the appropriate concentrations. Although the driving force should be more correctly expressed in terms of chemical potentials, Eq. (16-63) provides a qualitatively and quantitatively correct representation of adsorption systems so long as the diffusivity is allowed to be a function of the adsorbate concentration. The diffusivity will be constant only for a thermodynamically ideal system, which is only an adequate approximation for a limited number of adsorption systems. 

Linear Driving Force Approximation Simplified expressions can also be used for an approximate description of adsorption in terms of rate coefficients for both extrapai ticle and intraparticle mass transfer controlling. As an approximation, the rate of adsorption on a particle can be written as ... 

Axial Dispersion Effects In adsorption bed calculations, axial dispersion effects are typically accounted for by the axial diffusionhke term in the bed conservation equations [Eqs. (16-51) and (16-52)]. For nearly linear isotherms (0.5 < R < 1.5), the combined effects of axial dispersion and mass-transfer resistances on the adsorption behavior of packed beds can be expressed approximately in terms of an apparent rate coefficient for use with a fluid-phase driving force (column 1, Table 16-12) ... 

FIG. 16-27 Constant pattern solutions for R = 0.5. Ordinant is cfor nfexcept for axial dispersion for which individual curves are labeled a, axial dispersion h, external mass transfer c, pore diffusion (spherical particles) d, surface diffusion (spherical particles) e, linear driving force approximation f, reaction kinetics. [from LeVan in Rodrigues et al. (eds.), Adsorption Science and Technology, Kluwer Academic Publishers, Dor drecht, The Nether lands, 1989 r eprinted with permission.]... 

Gas Phase Adsorption - This is a condensation process where the adsorption forces condense the molecules from the bulk phase within the pores of the activated carbon. The driving force for adsorption is the ratio of the partial pressure and the vapour pressure of the compound. 

We have covered a body of material in this chapter that deals with movement of mass along gradients and between phases. We have examined the commonalities and differences between linear driving forces, net rates of adsorption, and permeation. Each has the common feature that reaction is not involved but does involve transport between apparently well-defined regions. We move now to chemically reactive systems in anticipation of eventually analyzing problems that involve mass transfer and reaction. 

Part (a) is the driving force for the adsorption. If only (a) were present, adsorbed chains would lie flat on the surface. Parts (b) and (c) are the opposing forces (b) accounts for the entropy loss of a bond on the surface as compared to the solution, (c) represents the separation into a concentrated surface phase and a dilute solution. Part (d) arises from polymer-polymer, solvent-solvent and polymer-solvent interactions, which usually favour accumulation of segments. At equili-... 

We have modelled the [CDopen - methyl pyruvate] complex. The result is shown in Figure 2. In this complex there is no steric hindrance to prevent the free rotation of the substrate around the quinuclidine nitrogen. Thus, in complex shown in Figure 2. there is no preferential stabilization of the substrate. In earlier computer modeling it was suggested that Pt is involved in the stabilization of the [CDopew-a-lfeto ester] complex, i.e. the Pt surface prevent the free rotation of the substrate, however the driving force for enantio-differentiation, i.e. for preferential adsorption of the substrate, was not discussed [14]. 

In the first step the solution enters the pores. The driving forces for the flow are capillary forces. During the flow, adsorption by ion exchange occurs. Due to the high rate of adsorption an uneven distribution of Pt ions results. Subsequently, a situation exists in which the diffusion through the pore mouth becomes rate determining. The active phase is pre.sent as a shell, which moves towards the interior of the particle as shown in Fig. 3.30. 

Hence, the question arose whether the lifting of reconstruction is due to surface charging (as a result of the electrode potential), adsorption of electrolyte ions (or molecules), or both. Although various experimental and theoretical investigations have been carried out, the driving force for the lifting of reconstruction is not yet clear. 

Wu S, Lipkowski J, Magnussen OM, Ocko BM, Wandlowski T. 1998. The driving force for (p X - 3) <->(1x1) phase transition of Au(lll) in the presence of organic adsorption A combined chronocoulometric and surface X-ray scattering study. J Electroanal Chem 446 67-77. 

Although the correlation between ket and the driving force determined by Eq. (14) has been confirmed by various experimental approaches, the effect of the Galvani potential difference remains to be fully understood. The elegant theoretical description by Schmickler seems to be in conflict with a great deal of experimental results. Even clearer evidence of the k t dependence on A 0 has been presented by Fermin et al. for photo-induced electron-transfer processes involving water-soluble porphyrins [50,83]. As discussed in the next section, the rationalization of the potential dependence of ket iti these systems is complicated by perturbations of the interfacial potential associated with the specific adsorption of the ionic dye. 

Another important type of physical chemical interaction that may alter absorption is that of drug binding or adsorption onto the surface of another material. As with complexation and micellarization, adsorption will reduce the effective concentration gradient between gut fluids and the bloodstream, which is the driving force for passive absorption. While adsorption frequently reduces the rate of absorption, the interaction is often readily reversible and will not affect the extent of absorption. A major exception is adsorption onto charcoal, which in many cases appears to be irreversible, at least during the time of residence within the GIT. As a result, charcoal often reduces the extent of drug absorption. Indeed, this fact... 

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