Adsorption energy distribution

Several numerical procedures for EADF evaluation have also been proposed. Morrison and Ross [19] developed the so-called CAEDMON (Computed Adsorption Energy Distribution in the Monolayer) method. Adamson and Ling [20] proposed an iterative approximation that needs no a priori assumptions. Later, House and Jaycock [21] improved that method and proposed the so-called HILDA (Heterogeneity Investigation at Loughborough by a Distribution Analysis) algorithm. Stanley et al. [22,23] presented two regularization methods as well as the method of expectation maximalization. 

This model is directly derived from the Langmuir isotherm. It assumes that the adsorbent surface consists of two different types of independent adsorption sites. Under this assumption, the adsorption energy distribution can be modeled by a bimodal discrete probability density function, where two spikes (delta-Dirac functions) are located at the average adsorption energy of the two kinds of sites, respectively. The equation of the Bilangmuir isotherm is... 

As many other models, even the Toth isotherm was originally derived for the study of gas-solid equilibria. However, it has been extended to the description of liquid-solid system. This isotherm assumes a continuous and wide adsorption energy distribution. The equation of the Toth isotherm is... 

Figure 5. Adsorption energy distributions for the MCM-41 and CeMCM-41 samples calculated from submonolayer nitrogen adsorption data.

Specific surface areas of the materials under study were calculated using the BET method [22, 23]. Their pore size distributions were evaluated from adsorption branches of nitrogen isotherms using the BJH method [24] with the corrected form of the Kelvin equation for capillary condensation in cylindrical pores [25, 26]. In addition, adsorption energy distributions (AED) were evaluated from submonolayer parts of nitrogen adsorption isotherms using the algorithm reported in Ref. [27],... 

Very recently, Kruk et al. (1997a) have analysed their detailed nitrogen isotherms determined on a series of siliceous MCM-41 samples of different pore size. The low-pressure data were used to calculate the adsorption energy distribution, which in general appeared to show little variation from one sample to another. However, it was found that the adsorption at the lowest accessible pressures (5 x 10"7 < p/pa < 1CT3) was significantly enhanced by the decrease in pore size. This may have been due to either corrugations in the pore walls or an overall increased curvature of the pore wall. 

Inverse Gas Chromatography at finite concentration conditions (IGC-FC) offers another possibility to perform such determinations. Furthermore, IGC readily provides the data required for the calculation of adsorption energy distribution functions. The aim of the present study was to... 

The first domain is used to determine the specific surface area (5 bet(H20)) and the BET constant values. Moreover, the large number of available experimental points allows the calculation of the corresponding adsorption energy distribution function of water on silica. 

Fig. 4. Adsorption energy distribution function (AEDF) of water on silica at 40 °C.

The last point concerns the water adsorption energy distribution functions that give a fingerprint of the surface energetic heterogeneity of the examined solids [3]. The adsorption energy distribution functions (AEDF) of water on the silica are displayed in Fig. 4. 

This study demonstrates the ability of IGC, at finite concentration conditions, to determine quickly (within one or two days depending on the desired accuracy) water adsorption isotherms, with relative pressures ranging from 0 to 0.85. Moreover, IGC provides isotherms made up of several hundreds of experimental points. This permits the computation of meaningful adsorption energy distribution functions. 

The samples were conditioned following the D160 protocol (conditioning at 160 °C, under dry carrier gas stream). The methylene chloride adsorption isotherms were determined on each sample and used to compute the BET surface area (5bet(CH2C12)), the corresponding BET constant (Cbet), and the adsorption energy distribution functions (AEDF). 

The surface energetic heterogeneity determination constitutes an additional aspect of the present study. This was performed by means of the methylene chloride adsorption energy distribution functions (AEDF) computation, relating the number of interactive surface sites to the desorption energy of each individual site. The latter are displayed in Fig. 1. 

Local adsorption energies, e, local adsorption isotherms, dip, T, e), local monolayer capacities, c ax, and adsorption energy distribution functions, /(e), for... 

In the above, the heterogeneity parameters nt and m characterize the shape (width and asymmetry) of adsorption energy distribution function, and the equilibrium constant, ATi , describes the position of distribution function on energy axis... 

Fig. 3. Adsorption energy distribution of ethane and propane in Norit activated carbon ----- MPSD model---------Energy distribution model...

Analysis of Heterogeneity. The monolayer analysis consists of three elements an adsorption isotherm equation, a model for heterogeneous surfaces, and an algorithm such as CAEDMON, which uses the first two elements to extract the adsorptive energy distribution and the specific surface from isotherm data. Morrison and Ross developed a virial isotherm equation for a mobile film of adsorbed gas at submonolayer coverage (6) ... 

Boudreau and Cooper showed that adsorptive energy distributions can be computed directly from chromatograms (38)- Their method is similar in principle to the present analysis, except for the use of an adsorption isotherm equation that provides an analytical solution for Equation 15. This simplification, which describes all adsorption isotherms as if they occur below the two-dimensional critical temperature 7 c = 0.60 (6), speeds computation of the histogram. Its practical effect is to broaden the energy scale artificially, however, particularly when light vapors are used to characterize low energy, homogeneous substrates. 

Fig. 5.25 Adsorption energy distributions for CH4, N2, and Ar on a relaxed simulated silica surface [44].

Actual surfaces are heterogeneous and the adsorption data on real adsorbents are usually not well accounted for by one of the two models discussed in the section above. The distribution of the adsorption energy (AED) on a homogeneous surface is a Dirac distribution. On an actual surface, the adsorption energy distribution has a finite width. It can be unimodal or multi-modal. The isotherm models discussed in this section correspond to such surfaces. Each of them can be related to a different AED. In all cases, however, there are no adsorbate-adsorbate interactions. In this group, the most useful models are the bi-Langmuir and multi-Langmuir isotherms, the Toth isotherm, and the Freundlich isotherm. 

Originally derived for the study of gas-solid equilibria, the T6th isotherm [64] accounts for adsorption on a heterogeneous surface, with no adsorbate-adsorbate interactions. It has three parameters. The heterogeneous surface has a unimodal adsorption energy distribution with a width related to the value of the parameter t. Like the Langmuir isotherm, it can be extended to the case of liquid-solid equilibrium. Its equation is... 

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