Adsorption isotherm models

Numerous mathematical models attempt to characterize the adsorpbon process. The three most widely accepted isotherm models are the Freundlich, the Langmuir, and the 

BET models. The Freundlich isotherm is an empirical relationship, while the Langmuir and BET isotherms are based on theoretical developments. The Langmuir isotherm is based on the concept of monolayer adsorption, while the BET isotherm assumes multilayer adsorption. 

The BET model (8) assumes that layers of molecules are adsorbed on top of previously adsorbed molecules. Each layer adsorbs according to the Langmuir adsorption model. The four basic assumptions for the BET multilayer adsorption model are (a) adsorbed molecules do not migrate on the surface (b) the enthalpy of adsorption is constant for all molecules in a given layer (c) all molecules in layers beyond the first have equal energies of adsorption and (d) layers need not be completed for adsorption before the next one starts. The BET equation has the following formula for adsorption from a liquid solution  

A plot of x/m vs C results in a curve of the form shown in Fig. 3. Theoretically, when C approaches the saturation value C, the moles of adsorbate adsorbed become very large because the BET model does not constrain the number of layers adsorbed. In practice, because the saturation concentration of can only be estimated, an iterative process should be used in solving BET equation. 

The Langmuir isotherm (10) assumes adsorption is reversible and occurs only for the monolayer on the adsorbent surface. The equation is shown below  

The function f(r) can be considered as the activity of the 2D Meads phase in the UPD range compared to the Me activity (aue = 1) of a 3D Me bulk phase (cf. eq. (1.2)). The explicit form of f(r) depends on the Meads-S and Meads-Meads interactions and the crystallographic structure of S, and can be derived using appropriate adsorption isotherm models. 

Generally, monolayer formation can be caused either by non-localized or localized adsorption. TTie first case can be described by 2D ideal or real gas models [3.253, 3.254] which apply to systems with solid substrates at relatively high temperatures or 

In many physically important cases of localized adsorption, each adatom of the compact monolayer covers effectively n 1 adsorption sites [3.87-3.89, 3.98, 3.122, 3.191, 3.214, 3.261]. Such a multisite or 1/n adsorption can be caused by a crystallographic Me-S misfit, i.e., the adatom diameter exceeds the distance between two neighboring adsorption sites, and/or by a partial charge of adatoms (A 1 in eq. (3.2)), i.e., a partly ionic character of the Meads-S bond. The theoretical treatment of a /n adsorption differs from the description of the 1/1 adsorption by a simple Ising model. It implies the so-called hard-core lattice gas models with different approximations [3.214, 3.262-3.266]. Generally, these theoretical approaches can only be applied far away from the critical conditions for a first order phase transition. In addition, Monte Carlo simulations are a reliable tool for obtaining valuable information on both the shape of isotherms and the critical conditions of a 1/n adsorption [3.214, 3.265-3.267]. 

As an example of a 1/1 adsorption in Me UPD systems, the Fowler-Frumkin isotherm, which is derived using the so-called mean field approximation (Section 8.3), is given by [3.257, 3.258, 3.268]  

TTie degree of coverage, 6, is related to the surface excess concentration, F, by 6= /yrwL where /ml denotes the surface excess concentration of a Meads monolayer. The parameter c represents the number of first nearest neighbors in the compact Meads monolayer. The lateral interaction parameter, a, is related to the lateral interaction energy, i Meads-Meads. by = l Meads-Meads electrode potentials E 

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In this chapter, we are going to show that using the one- and the two-component multilayer adsorption isotherm models or the models taking into the account lateral interactions among the molecules in the monolayer (discussed in Section 2.1), the overload peak profiles presented in Section 2.4 can be qualitatively modeled. 

Electrochemical impedance spectroscopy was used to determine the effect of isomers of 2,5-bis( -pyridyl)-l,3,4-thiadiazole 36 (n 2 or 3) on the corrosion of mild steel in perchloric acid solution <2002MI197>. The inhibition efficiency was structure dependent and the 3-pyridyl gave better inhibition than the 2-pyridyl. X-ray photoelectron spectroscopy helped establish the 3-pyridyl thiadiazoles mode of action toward corrosion. Adsorption of the 3-pyridyl on the mild steel surface in 1M HCIO4 follows the Langmuir adsorption isotherm model and the surface analysis showed corrosion inhibition by the 3-pyridyl derivative is due to the formation of chemisorbed film on the steel surface. 

Mixture phase equilibrium calculations, types of, 24 680-681 Mixture-process design type, 8 399 commercial experimental design software compared, 8 398t Mixtures. See also Multicomponent mixtures Nonideal liquid mixtures acetylene containing, 2 186 adsorption, 2 593-594 adsorption isotherm models,... 

According to the equilibrium dispersive model and adsorption isotherm models the equilibrium data and isotherm model parameters can be calculated and compared with experimental data. It was found that frontal analysis is an effective technique for the study of multicomponent adsorption equilibria [92], As has been previously mentioned, pure pigments and dyes are generally not necessary, therefore, frontal analysis and preparative RP-HPLC techniques have not been frequently applied in their analysis. 

Empirical determination of collection windows - Adsorption isotherm modeling... 

A final area of difficulty is in the application of data analysis to specific models of adsorption isotherms. This difficulty results from the fact that different models for adsorption isotherms generate plots of surface versus dissolved concentration that have characteristic shapes. If a plot of observational data results in a curve with a shape similar to that generated by a model, this result is often taken as proof that the particular model applies. Unfortunately, this assumption has been made for situations where many of the basic requirements of the model are violated in the system under study. The Langmuir adsorption isotherm model has suffered considerable abuse by geochemists in this regard. It should be remembered that "shapes" of adsorption isotherms are far from proof that a specific model applies. 

In literature the existing experimental data base of supercritical adsorption equilibria is limited and most of the data have been modelled with one of three common adsorption isotherm models - the Langmuir, the Freundlich and the Toth. The models define adsorption isotherms with a similar shape and they have 2 or 3 adjustable parameters which allow an accurate correlation. 

In this paper we present a new characterisation method for porous carbonaceous materials. It is based on a theoretical treatment of adsorption isotherms measured in wide temperature (303 to 383 K) and pressure ranges (0 to 10000 kPa) and for different adsorbates (N2, CH4, Ar, C3H8 and n-C4Hio). The theoretical treatment relies on the Integral Adsorption Equation concept. We developed a local adsorption isotherm model based on the extension of the Redlich-Kwong equation of state to surface phenomena and we improved it to take into account the multilayer formation. The pore size distribution fimction is assumed to be a bi-modal gaussian. By a minimisation procedure, it is possible to determine the bi-modal pore size distribution function witch can be used for purely characterisation purposes or to predict adsorption isotherms. 

The concentration-dependent binding of Ru(dcb)-based sensitizers is well described by the Langmuir adsorption isotherm model from which adduct formation constants of 10 have typically been abstracted [123, 132]. While it is often stated that monolayer coverage of the sensitizers is achieved, this is difficult to prove. The colloidal nature of the films makes absolute surface area determinations almost impossible. There is no evidence for multilayer formation, so the surface coverage is at most monolayer and probably sub-monolayer in most cases. The surface coverage for sensitzers in a 1 cm geometric area is typically 10 mol, where 10 mol cm would be expected for a close-packed monolayer of 14 A diameter sensitizers on a flat surface. 

Properties of Activated Carbon Adsorption Isotherm Models Design Consideration of PAC Systems Regeneration... 

Validation issues are especially important in the analytical field when quantifications are made. However, it is also important to validate the adsorption isotherm model and its estimated parameters used in preparative chromatography. In contrast to the situation for the bioanalytical area in the pharmaceutical industry, there are few published reports on validation in the analytical biotechnological and in the isotherm parameter determination field, and there exists no detailed validation guidelines [16, 17], This is why much effort in this thesis is focused on the development of validated methods in both these fields. 

After the adsorption isotherm experiments have been completed, an isotherm equation must be chosen. This equation should fit the experimental data. Often are the experimental data (the experimental adsorption data acquired by the FA method or the perturbation retention times acquired by the PP method) only compared with the ones calculated using the adsorption isotherm parameters acquired from some adsorption isotherm models [131], This is sometimes the only validation done in this field [131], However, the adsorption isotherm parameters should preferably be validated in two step (1) the different isotherm models should be compared using statistical calculations, e.g., an F-test, and (2) by using the parameters to computer simulate elution profiles and then compare them with experimental ones. 

Figure 4.2 illustrates the best competitive adsorption isotherm model for benzyl alcohol and 2-phenylethanol [16]. The whole set of competitive adsorption data obtained using Frontal Analysis was fitted to obtain the Langmuir parameters column saturation capacity qs =146 g/1), equilibrium constant for benzyl alcohol bsA = 0.0143) and the equilibrium constant for 2-phenylethanol (bpE = 0.0254 1/g). The quality of the fit obtained with this simple model is in part explained by the small variation of the activity coefficients of the two solutes in the mobile phase when the solute concentrations increased from 0 to 50 g/1. The Langmuir competitive adsorption isotherm simplifies also in the case where activity coefficients are of constant value in both phases over the whole concentration range [17]. 

The separation area in Figure 17.17 that was calculated using the three-layer adsorption isotherm model was determined in two different ways. The data points... 

Given in Table 10.7 are the surface reactions and corresponding activity adsorption isotherm model equations used in MINTEQA2 as presented by Allison et al. (1991). In these expressions SOH and SOH M represent unoccupied surface sites and surface sites occupied by species M. Because the and Freundlich isotherm models assume an infinite number of available sorption sites, the con-... 

To evaluate the adsorption of chelates and organic ligands, such as surfactants, a simple adsorption isotherm model may be used. The perhaps most straightforward model has been developed by Langmuir. Assuming that the surface is basic and the adsorbate is acidic in the Bronsted or the Lewis sense, we obtain for the displacement of the solvent liquid (L) molecules by the adsorbate (A) ... 

Fit experimental data to the Langmuir and Freundlich adsorption isotherm models. 

To illustrate the use of nonlinear models, we study an adsorption experiment. The system studied was the adsorption of Ha on a Pd catalyst with SiOa support (25,24], The adsorption is assumed dissociative. Both the catalyst and the support adsorb Ha so the adsorption isotherm model is... 

Acidity, external surface 13-P-09 Adsorption isotherms, modelling 16-P-lO... 

Experimental data can be often fitted more precisely to an adsorption isotherm model when an additional linear term is introduced that covers the nonspecific adsorption of the solute to the adsorbent. This modifies the single-component Langmuir isotherm (Equation 2.53) (Seidel-Morgenstern and Nicoud, 1996) ... 

Only for a small number of relatively simple single-component adsorption isotherm models analytical solutions of the set of IAS theory equations can be derived. This is possible, for example, for the Langmuir model. If the saturation capacities of all components in the corresponding single-component isotherm equations (Equation 2.51) are identical, the IAS theory generates the same competitive isotherm model as given by Equation 2.57. 

After specifying the c9, it remains again just solving the explicit equations (2.67). The described algorithm can be efficiently applied to solve the set of IAS equations for arbitrary increasing single-component adsorption isotherm models and any component number n. 

Ilic, M., Flockerzi, D., and Seidel-Morgenstern, A. (2010) A thermodynamically consistent explicit competitive adsorption isotherm model based on second-order single component behaviour. /. Chromatogr. A, 1217, 2132-2137. 

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