Desorption, explanation

There are numerous references in the literature to irreversible adsorption from solution. Irreversible adsorption is defined as the lack of desotption from an adsoibed layer equilibrated with pure solvent. Often there is no evidence of strong surface-adsorbate bond formation, either in terms of the chemistry of the system or from direct calorimetric measurements of the heat of adsorption. It is also typical that if a better solvent is used, or a strongly competitive adsorbate, then desorption is rapid and complete. Adsorption irreversibility occurs quite frequently in polymers [4] and proteins [121-123] but has also been observed in small molecules and surfactants [124-128]. Each of these cases has a different explanation and discussion. 

Irreversible adsorption discussed in Section XI-3 poses a paradox. Consider, for example, curve 1 of Fig. XI-8, and for a particular system let the equilibrium concentration be 0.025 g/lOO cm, corresponding to a coverage, 6 of about 0.5. If the adsorption is irreversible, no desorption would occur on a small dilution on the other hand, more adsorption would occur if the concentration were increased. If adsorption is possible but not desorption, why does the adsorption stop at 6 = 0.5 instead of continuing up to 0 = 1 Comment on this paradox and on possible explanations. 

One might expect the frequency factor A for desorption to be around 10 sec (note Eq. XVII-2). Much smaller values are sometimes found, as in the case of the desorption of Cs from Ni surfaces [133], for which the adsorption lifetime obeyed the equation r = 1.7x 10 exp(3300// r) sec R in calories per mole per degree Kelvin). A suggested explanation was that surface diffusion must occur to desorption sites for desorption to occur. Conversely, A factors in the range of lO sec have been observed and can be accounted for in terms of strong surface orientational forces [134]. 

Type V isotherms of water on carbon display a considerable variety of detail, as may be gathered from the representative examples collected in Fig. 5.14. Hysteresis is invariably present, but in some cases there are well defined loops (Fig. 5.14(b). (t ), (capillary-condensed water. Extreme low-pressure hysteresis, as in Fig. 5.14(c) is very probably due to penetration effects of the kind discussed in Chapter 4. 

The solid product, BaO, was apparently amorphous and porous. Decomposition rate measurements were made between the phase transformation at 1422 K and 1550 K (the salt melts at 1620 K). The enthalpy and entropy of activation at 1500 K (575 13 kJ mole-1 and 200 8 J K"1 mole-1) are very similar to the standard enthalpy and entropy of decomposition at the same temperature (588 7 kJ and 257 5 J K-1, respectively, referred to 1 mole of BaS04). The simplest mechanistic explanation of the observations is that all steps in the reaction are in equilibrium except for desorption of the gaseous products, S02 and 02. Desorption occurs over an area equivalent to about 1.4% of the total exposed crystal surface. Other possible models are discussed. 

Figure 7.12. Dissociation of NO N + O in a temperature-programmed desorption and static SIMS experiment, along with Monte Carlo simulations, showing the effect of lateral interactions (see text for explanation). The bottom part shows representative arrangements of NO molecules (grey), and...

The observation of negative apparent activation energy can most simply be interpreted in terms of the competition between the adsorption and desorption of methylacetylene on the surface. This qualitative explanation is illustrated in Figure 3, where the steady-state production of trimethylbenzene is compared with the TPD trace of methylacetylene. The fall off in steady state cyclotrimerization rate matches the tail of the desorption spectrum and illustrates the role of reactant desorption at higher temperatiu-es controlling the availability of alkyne monomers and thus the overall cyclotrimerization rate in this temperatime/pressure regime. 

Krishnaswami S, Graustein WC, Turekian KK, Dowd F (1982) Radium, thorium, and radioactive lead isotopes in groundwaters application to the in-situ determination of adsorption-desorption rate constants and retardation factors. Water Resour Res 6 1663-1675 Krishnaswami S, Bhushan R, Baskaran M (1991) Radium isotopes and Rn in shallow brines, Kharaghoda (India). Chem Geol (Isot Geosci) 87 125-136 Kronfeld J, Vogel JC, Talma AS (1994) A new explanation for extreme " U/ U disequilibria in a dolomitic aquifer. Earth Planet Sci Lett 123 81-93... 

The presence of fine solid particles or a finely dispersed second liquid phase in the continuous absorbent phase can have a very strong effect on the mass transfer rate between the gas and the continuous phases. The mass transport into the solid particles or liquid drops can essentially alter the concentration gradient and, consequently, the absorption rate [27-36]. The qualitative explanation of this phenomenon is that the particle absorbs oxygen in the oxygen-rich hydro-dynamic mass transfer film, after which, desorption of oxygen takes place in the oxygen-poor bulk of the liquid. 

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