Adsorption isotherms Toth equation

More about Adsorption The Toth Equation Applied to Air Purification The Langmuir isotherm, while adequate for many purposes, has since its inception been superseded by more refined equations with a broader range of applications. One such equation is that due to Toth, which is given by... 

The best results to describe the adsorption isotherm by the selected isotherm equations were achieved by the Toth model. The Freundlich model showed in some cases a lack of flexibility in describing the region were the linear behaviour changed to saturation behaviour (22 MPa) and the Langmuir-model in some cases had difficulties in describing the region were the adsorbate is saturated (16 MPa). 

Equations (1) and (2) are applicable when the alumina is energetically homogeneous (isosteric heat of adsorption, q, is independent of water loading, n). The Toth equation can be used when the alumina is energetically heterogeneous (q decreases with increasing n) and the isotherm shape is Type I [7] ... 

Being the three-parameter model, the Toth equation can describe well many adsorption data. We apply this isotherm equation to fit the isotherm data of propane on activated carbon. For example taking the isotherm data at 303 K in Table 3.2-1, the extracted optimal parameters are (using the ISO FITl routine) ... 

Like the Sips and Toth equation, the Unilan equation is a three-parameter isotherm equation, and they are commonly used to correlate adsorption equilibrium data of many solids, such as activated carbon and zeolite. 

Various practical isotherm equations have been presented and they are useful in describing adsorption data of many adsorption systems. Among the many equations presented, the Toth equation is the attractive equation because of its correct behaviour at low and high loading. If the Henry behaviour is not critical then the Sips equation is also popular. For sub-critical vapours, multilayer isotherm equations are also presented in this chapter. Despite the many equations proposed in the literature, the BET equation still remains the most popular equation for the determination of surface area. When condensation occurs in the reduced pressure range of aroimd 0.4 to 0.995, the theory of condensation put forward by Kelvin is useful in the determination of the pore size as well as the pore size distribution. 

In this theory of Ideal Adsorption Solution, adsorption isotherm equation for pure components can take any form which fits the data best (Richter et al., 1989). Two isotherms commonly used are Toth and Unilan equations (Chapter 3), although Toth equation is the preferable equation from the computational point of view because it usually gives faster convergence than the Unilan equation does. When DR equation is used to describe pure component data, the application of the LAST in this case has some special features (Richter et al., 1989) and it was used by Lavanchy et al. (1996) in the description of equilibria of chlorobenzene and tetrachloride on activated carbon. 

In nonlinear adsorption systems where parallel diffusion mechanisms hold, the mass balance equation given in eq. (9.2-lb) is still valid. The difference is in the functional relationship between the concentrations of the two phases, that is the local adsorption isotherm. In general, this relationship can take any form that can describe well equilibrium data. Adsorption isotherm such as Langmuir, Unilan, Toth, Sips can be used. In this section we present the mathematical model for a general isotherm and then perform simulations with a Langmuir isotherm as it is adequate to show the effect of isotherm nonlinearity on the dynamics behaviour. The adsorption isotherm takes the following functional form ... 

We finish this section by considering another isotherm equation the Toth equation, which is a popular equation in describing adsorption isotherm of numerous practical systems. It has the form ... 

As was proven earlier in this chapter, if an isotherm of Type I has both a monolayer and a multilayer domain, then there are two possibilities for calculating the specific surface area. The modified BET equation to the multilayer domain and one of the monolayer equations to the monolayer domain can be applied. The appropriate monolayer equation and the value of (the relative equilibrium pressure where the multilayer adsorption begins) can be calculated from the function Py). In most cases, the Toth equation is the simplest monolayer relationship because it can be applied instead of the FT, VT, and BT equations (see Section IVF). However, if the isotherm of Type I does not have a multilayer plateau, then the approximation... 

P = 0.0405 (i.e., to this relative pressure dominantly monolayer adsorption takes place) therefore, the Toth equation can be applied to this part of the isotherm. Because the saturation pressure of oxygen at 85 K is a known value and is equal to 57.33 kPa, the pressures can be expressed as relative ones. This means that Eq. (389) can be directly fitted to the measured data in the domain of 0 < P,. < 0.0405. So, we obtain that... 

In spite of the faets mentioned in points 1, every deviation shown in Table 2 is less than the errors of measuring of an adsorption isotherm ( 2%). This means that every Toth equation with aU of the parameters tabulated in Table 2 can describe the carbon dioxide isotherm with good accuracy. 

The three-parameter Toth equation is considered particularly successful in representing adsorption data over extensive ranges (from zero to full mono-layer coverage). For using LAST it is thus necessary to have a very good fit of single-component adsorption isotherms for all the gases involved. This in turn requires experimental data at each temperature/gas considered. 

In Section V.A it has been shown that a monolayer isotherm measured on a heterogeneous surface has always an increasing function y(p. ) which, in most cases, can be described by the Toth equation. It was also shown that in the case of multilayer adsorption the function ) always has a decreasing domain which may begin at a rel-... 

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... 

At this point, it is feasible to correlate the liquid-phase adsorption equilibrium single component data, with the help of isotherm equations developed for gas-phase adsorption, since, in principle, it is feasible to extend these isotherms to liquid-phase adsorption by the simple replacement of adsorbate pressure by concentration [92], These equations are the Langmuir, Freundlich, Sips, Toth, and Dubinin-Radushkevich equations [91-93], Nevertheless, the Langmuir and Freudlich equations are the most extensively applied to correlate liquid-phase adsorption data. [2,87],... 

Both adsorption from a supercritical fluid to an adsorbent and desorption from an adsorbent find applications in supercritical fluid processing. The extrapolation of classical sorption theory to supercritical conditions has merits. The supercritical conditions are believed to necessitate monolayer coverage and density dependent isotherms. Considerable success has been observed by the authors in working with an equation of state based upon the Toth isoterm. It is also important to note that the retrograde behavior observed for vapor-liquid phase equilibrium is experimentally observed and predicted for sorptive systems. 

Describing the measured data and extrapolation of those to the geostatic pressure is possible on condition that we suppose an equivalent adsorption, i.e., we suppose as if the sorbed amount were adsorbed on a heterogeneous surface. This is an unavoidable supposition because all known isotherm equations describe physical or chemical adsorption taking place on surfaces and does not do it for the bulk phases. One of the widely-used isotherm equation is the Toth [16] equation also applied by Valanzuela and Myers in their handbook where are collected more than 100 simple gas isotherms [17]. The explicit form of this equation is the following ... 

Though the suggestions of Sips were received well, by Sips himself who proposed a generalized Freundlich isotherm, by Misra who considered a kind of generalized DR equation, by Rudzinski and co-workers who extended the method to multilayer adsorption, and by Toth et who... 

From the derived Toth isotherms, the isosteric heat of adsorption as a fiinction of coverage can be calculated by the following equation [11] ... 

The BET model has been generalized by using of various monolayer isotherms for heterogeneous surfaces Langmuir-Freundlich [94], Toth [95], generalized Freundheh (GF) [94], Dubinin-Radushkevich [67,95,96], and others [5]. These equations have been apphed to the interpretation of experimental data [5,6]. The above-discussed procedure has also extended to the adsorption with lateral interactions on randomly heterogeneous surfaces also [5]. 

Usually, the above equations hold fine in restricted pressure ranges, say for p Pm (with pj and p two temperature-dependent characteristic pressures depending on the considered adsorption system) for the Temkin and Toth isotherm, pi is allowed to vanish. 

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