Langmuir isotherm theory

Brunauer-Emmett-Teller (BET) [20], Langmuir isotherm theory is applied when a monolayer of molecules is sorbed on a homogeneous surface where each site requires the same energy to adsorb molecules. The Freundlich isotherm also assumes a monolayer, but allows for an exponential distribution of adsorption energies. BET isotherms provide for multilayer adsorption. 

For indoor organic gases (VOCs and SVOCs) Langmuir isotherm theory is commonly used to describe indoor sink behavior at equilibrium [20] ... 

Stahlberg has presented models for ion-exchange chromatography combining the Gouy-Chapman theory for the electrical double layer (see Section V-2) with the Langmuir isotherm (. XI-4) [193] and with a specific adsorption model [194]. 

Consider a binary adsorbed mixture for which each pure component obeys the Langmuir equation, Eq. (16-13). Let n = 4 mol/kg, nl =. 3 mol/kg, Kipi = K2P2 = 1. Use the ideal adsorbed-solution theory to determine ni and n. Substituting the pure component Langmuir isotherm... 

For nonlinear systems, however, the evaluation of the flow rates is not straightforward. Morbidelli and co-workers developed a complete design of the binary separation by SMB chromatography in the frame of Equilibrium Theory for various adsorption equilibrium isotherms the constant selectivity stoichiometric model [21, 22], the constant selectivity Langmuir adsorption isotherm [23], the variable selectivity modified Langmuir isotherm [24], and the bi-Langmuir isotherm [25]. The region for complete separation was defined in terms of the flow rate ratios in the four sections of the equivalent TMB unit ... 

In this chapter, we consider several simple models of ion sorption and exchange that can be applied within the context of a geochemical model. These models include distribution coefficients, Freundlich and Langmuir isotherms, and ion exchange theory. In the following chapter (Chapter 10), we consider surface com-plexation theory, which is more complicated but in some ways more robust than the models presented here. 

When the functional form of the correlation is suggested by theory, there is a great deal more confidence that the correlation can be extrapolated into regions of P that have no experimental data, and can be used for other families of compounds other than the training set S. Examples of theory-suggested functional forms include the van der Waals equation of state for gases, the Langmuir isotherm for adsorption and catalysis, and the Clausius-Clapeyron equation for the vapor pressure of liquids. 

The deviations from the Szyszkowski-Langmuir adsorption theory have led to the proposal of a munber of models for the equihbrium adsorption of surfactants at the gas-Uquid interface. The aim of this paper is to critically analyze the theories and assess their applicabihty to the adsorption of both ionic and nonionic surfactants at the gas-hquid interface. The thermodynamic approach of Butler [14] and the Lucassen-Reynders dividing surface [15] will be used to describe the adsorption layer state and adsorption isotherm as a function of partial molecular area for adsorbed nonionic surfactants. The traditional approach with the Gibbs dividing surface and Gibbs adsorption isotherm, and the Gouy-Chapman electrical double layer electrostatics will be used to describe the adsorption of ionic surfactants and ionic-nonionic surfactant mixtures. The fimdamental modeling of the adsorption processes and the molecular interactions in the adsorption layers will be developed to predict the parameters of the proposed models and improve the adsorption models for ionic surfactants. Finally, experimental data for surface tension will be used to validate the proposed adsorption models. 

EXAMPLE 9.4 Kinetic-Theory-Based Description of Binary Adsorption. Assume that two gases A and B individually follow the Langmuir isotherm in their adsorption on a particular solid. Use the logic that results in Equation (46) to derive an expression for the fraction of surface sites covered by one of the species when a mixture of the two gases is allowed to come to adsorption equilibrium with that solid. 

The exponent 1/n of isotherm (1) is linearly dependent on the temperature. At sufficiently high temperatures when, by (18), 1/n > 1, the theory gives simply a linear course of the isotherm at the beginning an isotherm of the form q = Cp1/", 1/n > 1, cannot be obtained by superposition of the Langmuir isotherm. Indeed, in this case a(b) still has the form of equation (9) with 1/n > 1, but we may no longer seek the asymptotic form of the beginning of the isotherm by formulas (11) and (12) since... 

Because the Langmuir isotherm is not an adequate description of most systems, Equation (2.9) is not used much for area measurement. A number of other isotherm formulations utilize adsorption in surface area measurements, however (cf. Young Crowell, 1962, for example). The best known and most widely used is the BET (Brunauer, Emmett Teller, 1938) theory, a generalization of the Langmuir model to multilayer absorption. Assuming that for the second and succeeding molecular... 

D. Basmadjian and P. Coroyannakis, Equilibrium-theory revisited -Isothermal fixed-bed sorption of binary systems. 1. Solutes obeying the Langmuir isotherm. Chem. 

By introducing a number of simplifying assumptions, Brunauer, Emmett and Teller (1938) were able to extend the Langmuir mechanism to multilayer adsorption and obtain an isotherm equation (the BET equation), which has Type II character. The original BET treatment involved an extension of the Langmuir kinetic theory of monomolecular adsorption to the formation of an infinite number of adsorbed layers. 

Stahlberg, J. The Gouy-Chapman theory in combination with a modified Langmuir isotherm as a theoretical model for ion-pair chromatography. J. Chromatogr. 1986, 356, 231-245. 

Obstacles to practical application of the Langmuir and Freundlich isotherm theories include the following (1) These isotherms do not effectively address adsorption versus degradation and competitive adsorption (2) the conclusions are not all inclusive i.e., adsorption constants and coefficients do not hold true in all cases within similar oil types let alone across different oil types (3) the process has so many variables that the additive variance is commonly too great to prove any subtle difference between clays other than a vastly different level of activity (this problem is especially true when using log vs. log plots with incremental changes on the order of 0.1%) and (4) the adsorption constants and coefficients have limited use for the refiner. 

For multicomponent adsorption the most commonly used isotherm is the extended Langmuir isotherm (Eq. 18). Another, frequently used approach is the Ideal Adsorption Solution theory (IAS theory), which was developed by Prausnitz [53] and applied to mixtures of gases by, for example, Kaul [54] and Rees [52,55]. 

Derylo-Marczewska and Jaroniec [28] have reviewed the adsorption of organic solutes from dilute solutions and have provided a useful compilation of published experimental data for both single- and multisolute adsorption isotherms on carbonaceous adsorbents. They also presented a survey of theoretical approaches used to describe the solute adsorption equilibria, including the Polanyi adsorption model, the solvophobic interaction model, the Langmuir adsorption theory, the vacancy solution model, as well as considerations based on the energetic heterogeneity of the adsorbent. In particular, these authors emphasize the... 

One can even go so far as to derive the isotherm from dynamic measurements. Note that this does not mean that a dynamic Langmuir isotherm is derived the theory is based on diffusion-limited adsorption, so the surface is taken to be fully relaxed with respect to the sub-surface concentration. In other words, the isotherm is taken to be identical to that in the static case. This is probably correct, unless under dynamic conditions the surfactant assumes a different conformation. 

It is easy to see that adsorption energies are dependent on the curvature of the interface. Consider first adsorption on a planar interface. At low pressures, p, a sub-monolayer, gas-like, and eventually a two-dimensional liquid described by a Langmuir isotherm (or decorations thereof) forms. At higher pressures still (p/ps>0.35, where ps is the saturated vapour pressure) multilayer adsorption isotherms can occur depending on adsorbate, molecular size and adsorbate-substrate interactions. This regime is usually described by the theory of Brxmauer-Emmet-Teller (BET). In this domain, ln(p/pg) = 1/t, where t is the thickness of the film. 

The ideal model should be applied to get information about the thermodynamic behavior of a chromatographic column. Through work by Lapidus and Amundson (1952) and van Deemter et al. (1956) in the case of linear isotherms and by Glueckauf (1947, 1949) for nonlinear isotherms, considerable progress was made in understanding the influences of the isotherm shape on the elution profile. This work was later expanded to a comprehensive theory due to improved mathematics. Major contributions come from the application of nonlinear wave theory and the method of characteristics by Helfferich et al. (1970, 1996) and Rhee et al. (1970, 1986, 1989), who made analytical solutions available for Eqs. 6.41 and 6.42 for multi-component Langmuir isotherms. 

Figure 6.28 compares measured and simulated profiles for the batch separation of EMD53986. Very good agreement between theory (solid lines) and experiment (symbols) is achieved using the multi-component modified-Langmuir isotherm (Fig. 6.21). Also shown are the simulation results neglecting component interaction by using only the single-component isotherms (dashed line), which deviate strongly from the observed mixture behavior. Typical for competitive adsorption is the displacement of the weaker retained R-enantiomer and the peak expansion of the stronger adsorbed S-enantiomer.

Figure 6.29 shows a comparison between two different isotherm models (Fig. 6.21) used for validation agreement between theory and experiment is good using the modified multi-component Langmuir model (Fig. 6.21), while the symmetrical Langmuir isotherm leads to profiles shifted to earlier retention times. The structural... 

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