Isotherms Dubinin-Astakhov

Erdem-Senatalar, A., Tatller, M. and Sirkecioglu, A. (2000). The relationship of the geometric factor in the Dubinin-Astakhov isotherm equation with the fractal dimension. Colloids Sur. A, 173, 51-59. 

In the same way, the Dubinin-Astakhov isotherm has been extended to the adsorption of gas mixtures [176] ... 

The Dubinin-Astakhov isotherm (18) has also been extended to adsorption from solution [200,206] moreover, the equations obtained for the values7=1 and j = 2 have been applied to... 

Semiernpirical Isotherm Models. Some of these models have been shown to have some thermodynamic inconsistencies and should be used with due care. They include models based on the Polanyi adsorption potential (Dubinin-Radushkevich, Dubinin-Astakhov, Radke-Prausnitz, Toth, UNI LAN. and BET). 

On the other hand, for the microporous carbons with pore size distribution (PSD) with pore fractality, the pore fractal dimensions56,59,62 which represent the size distribution irregularity can be theoretically calculated by non-linear fitting of experimental adsorption isotherm with Dubinin-Astakhov (D-A) equation in consideration of PSD with pore fractality.143"149 The image analysis method54,151"153 has proven to be also effective for the estimation of the surface fractal dimension of the porous materials using perimeter-area method.154"159... 

Figure 4.6 shows the PSDs obtained from the high-resolution N2 adsorption isotherms at 77 K (Figure 4.5) by applying the Horvath-Kawazoe method (Figure 4.6a), Dubinin-Astakhov method...

FIGU RE 4.9 Comparison of the PSD obtained for different samples by applying different methods (a) Sample ACF1, (b) sample AC2, and (c) sample AC1. DR-C02 is the PSD obtained by applying the Dubinin-based method proposed by Cazorla-Amoros et al. [10] to C02 at 273 K. HK, DFT, and DA are the PSDs obtained by applying Horvath-Kawazoe, DFT, and Dubinin-Astakhov methods to the N2 adsorption isotherm at 77 K, respectively. 

Stoeckli (1993) has pointed out that the Dubinin-Astakhov equation (Equation (4.45)) can be derived from Equation (4.52), but McEnaney (1988) and others (e.g. Jaroniec et al. 1997) have drawn attention to the difficulty in arriving at an unambiguous interpretation of the energy distribution function. Indeed, Stoeckli et al. (1998) have now pointed out that Equation (4.45) can be usefully applied to a number of adsorption isotherms on non-porous solids. A comprehensive review of the significance and application of Equation (4.52) is given by Rudzinski and Everett (1992). 

Over the past 30 years many organic molecules of different size, shape and polarity have been used as molecular probes. A high proportion of the experimental isotherms on porous carbons have been analysed by application of the Dubinin-Radushkevich (DR) equation or, in a few cases, by the Dubinin-Astakhov (DA) equation. So far, the more sophisticated Dubinin-Stoeckli (DS) treatment (Stoeckli, 1993) has been applied by very few other investigators. 

Various attempts were made by Dubinin and his co-workers to apply the fractional volume filling principle and thereby obtain a characteristic curve for the correlation of a series of physisorption isotherms on a zeolite (Dubinin, 1975). As was noted in Chapter 4, the original Dubinin-Radushkevich (DR) equation (i.e. Equation (4.39)) was found to be inadequate and in its place the more general Dubinin-Astakhov (DA) equation was applied (i.e. Equation (4.45)). 

The methods depend on the theoretical treatment which is used. A majority of them are based on the Generalised Adsorption Isotherm (GAI) also called the Integral Adsorption Equation (LAE). The more recent approaches use the Monte Carlo simulations or the density functional theory to calculate the local adsorption isotherm. The analytical form of the pore size distribution function (PSD) is not a priori assumed. It is determined using the regularization method [1,2,3]. Older methods use the Dubinin-Radushkevich or the Dubinin-Astakhov models as kernel with a gaussian or a gamma-type function for the pore size distribution. In some cases, the generalised adsorption equation can be solved analytically and the parameters of the PSD appear directly in the isotherm equation [4,5,6]. Other methods which do not rely on the GAI concept are sometimes used the MP and the Horvath-Kawazoe (H-K) methods are the most well known [7,8]. 

Textural characterisation of the samples was carried out by measuring apparent density (mercury at 0.1 MPa), mercury porosimetry and N2 and CO2 adsorption isotherms, at -196 and 0 °C, respectively. The apparent surface areas of the samples were obtained by using the BET equation [5]. The micropore size analysis was performed by means of the t-plot and the Dubinin-Astakhov methods [6]. 

The Dubinin-Astakhov (D-A) [6] equation was applied to the N2 adsorption isotherms. The accessible pore width, L, was calculated fi om the expression proposed by Stoeckli and Ballerini [9]. 

Several methods have been proposed for the characterisation of the Micropore Size Distribution (MPSD) that take into account the energetic heterogeneity of solid surfaces [9,10]. The Dubinin-Radushkevich (DR) and Dubinin-Astakhov (DA) equations have been used to describe the adsorption process on structurally heterogeneous solids [11,12]. From these equations, the adsorption isotherm can be expressed as follows ... 

The pore volumes of the obtained hard carbons were measured using the molecular probe method [3]. Adsorption isotherms of the probe molecules were measured at 298 K using an adsorption apparatus (Bel Japan, Belsorp 28). The employed probe molecules were CO2, C2H6> n-C4H o and (-C4H10 (minimum molecular dimensions 0.33, 0.40, 0.43 and 0.50 nm, respectively). By applying the Dubinin-Astakhov equation (n=2) [1] to the measured isotherms, the limiting micropore volumes corresponding to the minimum size of the adsorbed molecules were determined. 

Chen, S.G. and Yang, R.T. (1994). Theoretical basis for the potential theory adsorption isotherms. The Dubinin-Radushkevich and Dubinin-Astakhov equations. Langmuir, 10, 4244-9. 

The study of a particular adsorption process requires the knowledge of equilibrium data and adsorption kinetics [4]. Equilibrium data are obtained firom adsorption isotherms and are used to evaluate the capacity of activated carbons to adsorb a particular molecule. They constitute the first experimental information that is generally used as a tool to discriminate among different activated carbons and thereby choose the most appropriate one for a particular application. Statistically, adsorption from dilute solutions is simple because the solvent can be interpreted as primitive, that is to say as a structureless continuum [3]. Therefore, all equations derived firom monolayer gas adsorption remain vafid. Some of these equations, such as the Langmuir and Dubinin—Astakhov, are widely used to determine the adsorption capacity of activated carbons. Batch equilibrium tests are often complemented by kinetics studies, to determine the external mass transfer resistance and the effective diffusion coefficient, and by dynamic column studies. These column studies are used to determine system size requirements, contact time, and carbon usage rates. These parameters can be obtained from the breakthrough curves. In this chapter, I shall deal mainly with equilibrium data in the adsorption of organic solutes. 

The adsorption isotherm of microporous adsorbents have often been modeled by the Dubinin-Astakhov model. In this approach, which is based on a so-called pore-filling of an adsorbent by a subcritical gas (T < T ), the total adsorbed density is expressed as ... 

Adsorption equilibrium data of SO2, NH3 and CO2 were analyzed by the linearized forms of the Langmuir and Freundlich equations (see Eqns. 2 and 4). The water vapour isotherm was analyzed by the linearized forms of the Dubinin-Astakhov equation (6), because of the above mentioned condensation phenomena. 

Langmuir model is an excellent fit for the adsorption of SO2 and NH3 on Pentalofos tuff and a fairly good representation in the case of CO2. In the latter case, the Freundlich model appears, however, to be more suitable. On the contrary, as expected, in the fitting of the water vapour adsorption isotherm, best results are obtained using the Dubinin-Astakhov equation. 

Figure 18 (a) N2 adsorption isotherm of a nanoporous zirconia membrane, (b) Corresponding Dubinin-Astakhov differential pore volume plot. 

Fractal Analogue of the Dubinin-Astakhov Adsorption Isotherm... 

The DR isotherm describing adsorption in a single pore is a special case of a more general isotherm known in the literature as the Dubinin-Astakhov (DA) isotherm [35, 62] ... 

The following table 5.3-3 shows the various formula for the spreading pressure and the pure component hypothetical pressure for various commonly used isotherms. Some isotherms such as Langmuir, Freundlich, LRC have analytical expressions for the spreading pressure as well as the pure component hypothetical pressure. Other isotherms, such as O Brien Myers, Ruthven, Toth and Nitta have analytical expression for the spreading pressure, but the pure component hypothetical pressure expressed in terms of the reduced pressure must be determined from a numerical method. For other general isotherms, such as Unilan, Aranovich, Dubinin-Radushkevich, Dubinin-Astakhov, Dubinin-Stoeckli, Dubinin-Jaroniec, one must resort to a numerical method to obtain the spreading pressure as well as the pure component hypothetical pressure. 

The potential theory of adsorption was introduced by Polanyi in 1914. Dubinin [48,49] and Stoeckli et al. [50] improved the theory and termed it the theory of volume filling of micropores (TVFM). This theory has been widely used in correlating the effect of temperature on the adsorption isotherms of pure gases. The modern formulationof TVFM is the Dubinin-Astakhov (DA) equation, which is expressed as... 

The difficulty in the case of microporous materials stems from the porefilling mechanism. For this reason, the surface area of such materials is often determined by other methods than BET, which is based on layer formation. From the Dubinin equation the micropore volume Wo can be converted to the surface area. The as isotherm comparison method is an independent method for estimating the micropore volume and the surface area (20). The reference isotherm is a plot of the measured isotherm normalized by the amount of gas adsorbed at a fixed relative pressure, typically at p/po = 0.4. High resolution as analysis (21) yields more information about the characteristic texture of the adsorbent. Further methods (MP (22), -plot (23), Dubinin-Astakhov (11), Dubinin-Stockli (12), and so on) are also available for more reliable estimates of the micropore volume and surface area. 

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