Adsorption isotherms integral equation

The integral free energy is determined from an adsorption isotherm by Equation 1-6. In practice it is sometimes simpler to determine the partial molal... 

As done in the case of Langmuir adsorption isotherm, integration of Equation (25) is performed with the condition that at f = 0 the substrate concentration in the liquid phase is that in equilibrium with the initial photoadsorbed amoimt, Cl,o this initial concentration is imknown, but it may be determined... 

Equation (3.15) forms the basis for the derivation of adsorption isotherms from equations of state. Alternatively, it can also be used to obtain equations of state from adsorption isotherms. For example, for a linear isotherm, n/p is constant and the integration of Eq. (3.15) gives... 

One may choose 6(Q,P,T) such that the integral equation can be inverted to give f Q) from the observed isotherm. Hobson [150] chose a local isotherm function that was essentially a stylized van der Waals form with a linear low-pressure region followed by a vertical step tod = 1. Sips [151] showed that Eq. XVII-127 could be converted to a standard transform if the Langmuir adsorption model was used. One writes... 

The equation, when integrated, allows one to calculate q from adsorption isotherms obtained experimentally at two or more temperatures, provided the range of temperature is small enough to justify the assumption that (f is independent of temperature. If isotherms are available for only two temperatures, the value of q is given by the expression... 

Determination of the equilibrium spreading pressure generally requires measurement and integration of the adsorption isotherm for the adhesive vapors on the adherend from zero coverage to saturation, in accord with the Gibbs adsorption equation [20] ... 

Finally, let us discuss the adsorption isotherms. The chemical potential is more difficult to evaluate adequately from integral equations than the structural properties. It appears, however, that the ROZ-PY theory reflects trends observed in simulation perfectly well. The results for the adsorption isotherms for a hard sphere fluid in permeable multiple membranes, following from the ROZ-PY theory and simulations for a matrix at p = 0.6, are shown in Fig. 4. The agreement between the theoretical results and compu-... 

Equation (4.3.37) can be used to determine the function = T1(c1), which is the adsorption isotherm for the given surface-active substance. Substitution for c1 in the Gibbs adsorption isotherm and integration of the differential equation obtained yields the equation of state for a monomole-cular film = T jt). 

For the case of nonlinear adsorption isotherms, no analytical solutions exist the mass balance equations must be integrated numerically to obtain the band profiles. Approximate analytical solutions are only possible for the cases where the solute concentration is low and accordingly, the deviation from linear isotherm is only minor. All the approximate analytical solutions utilize a parabolic adsorption isotherm q = aC( -bC). This constraint prevents us from drawing general conclusions regarding most of the important consequences of nonlinearity. 

As described earlier, one of the first methods used to obtain PSD from the Dubinin equation is the so-called Dubinin-Stoeckli method [38-43], For strongly activated carbons with a heterogeneous collection of micropores, the overall adsorption isotherm is considered as a convolution of contributions from individual pore groups. Integrating the summation and assuming a normal Gaussian equation for the distribution of MPV with respect to the K parameter (Equation 4.19), Stoeckli obtained an equation useful to estimate the micro-PSD. 

If adsorption is fast but not sufficiently strong to justify the assumption C0 0, then C0 will, at any instant, be determined by the adsorption isotherm (2.103). This boundary condition leads to mathematical problems the integral equation resulting from (2.110) then becomes a Volterra equation. This has been solved for only some very simple isotherms. Delahay and Trachtenberg [203] solved it for the Henry isotherm (2.104), the solution being... 

If we assume that the adsorption isotherm for the chemisorbate is of the Temkin form, then i k" cMcoh exp(-a/0ads), where a is the transfer coefficient, with a value usually close to 0.5, and / is the inhomogeneity factor of the Pt surface, with a value of 10-11. Integrating this equation assuming that cMeoH and E are constant, we obtain... 

Probably the most significant comparisons which can be made are of values of properties determined from calorimetric measurements with values calculated from adsorption isotherms. Two general methods are available for the comparison of values of enthalpies determined from experiments of the two types. One involves two differentiations The change in the partial molal enthalpy, AH2, of X2, for Process 4, is determined from the differentiation with respect to n2/n1 of the integral heat of adsorption measured in a series of calorimetric experiments of the type represented by Equation 1. The values of the differential heats of adsorption (heats corresponding to the differential Process 4) are compared with values determined from the temperature variation of AG2/T for a series of values of n2/n in Process 4. This type of comparison has been made successfully by several groups of authors (3, 5, 10). 

Enthalpy Change. The enthalpy change measured by the heats of immersion (smooth curve) and calculated with Equation 7 (plotted points) is compared in Figure 6. The agreement is satisfactory, since the integration of the Gibbs adsorption equation depends so strongly upon the extrapolation of the adsorption isotherm to x = 0. 

The Davies and Jones derivation makes some fundamental assumptions concerning the surface concentrations of the lattice ions and the BCF theory is only applicable to very small supersaturations. Thus, both theories have limitations which affect the interpretation of the results of growth experiments. Nielsen [27] has attempted to examine in detail how the parabolic dependence can be explained in terms of the density of kinks on a growth spiral and the adsorption and integration of lattice ions. One of the factors, a = S — 1, comes from the density of kinks on the spiral [eqns. (4) and (68)] and the other factor is proportional to the net flux per kink of ions from the solution into the lattice. Nielsen found it necessary to assume that the adsorption of equivalent amounts of constituent ions occurred and that the surface adsorption layer is in equilibrium with the solution. Rather than eqn. (145), Nielsen expresses the concentration in the adsorption layer in the form of a simple adsorption isotherm equation... 

Equation (2.34) is often referred to as the Gibbs adsorption equation where the interdependence of r and p is given by the adsorption isotherm. TTie Gibbs adsorption equation is a surface equation of state which indicates that, for any equilibrium pressure and temperature, the spreading pressure II is dependent on the surface excess concentration r. The value of spreading pressure, for any surface excess concentration, may be calculated from the adsorption isotherm drawn with the coordinates n/p and p, by integration between the initial state (n = 0, p = 0) and an equilibrium state represented by one point on the isotherm. 

Stoeckli (1981), McEnaney and Mays (1991), Hutson and Yang (1997) and others (see Rudzinski and Everett, 1992) have attempted to provide a theoretical basis for the DR and DA equations in terms of an integral transform or a generalized adsorption isotherm, which may be expressed in the form of Equation (4.52). However, in practice the DR and DA equations are usually applied empirically and consequently the derived quantities (micropore volume, characteristic energy and structural constant) are not always easy to interpret. 

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 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]. 

Tabulated data for experimental adsorption isotherms are fitted with analytical equations for the calculation of thermodynamic properties by integration or differentiation. These thermodynaunic properties expressed as a function of temperature, pressure, and composition are input to process simulators of atdsorption columns. In addition, anaJytical equations for isotherms are useful for interpolation and cautious extrapolation. Obviously, it is desirable that the Isotherm equations agree with experiment within the estimated experimental error. The same points apply to theoretical isotherms obtained by molecular simulation, with the requirement that the analytical equations should fit the isotherms within the estimated statistical error of the molecular simulation. 

A novel approach is reported for the accurate evaluation of pore size distributions for mesoporous and microporous silicas from nitrogen adsorption data. The model used is a hybrid combination of statistical mechanical calculations and experimental observations for macroporous silicas and for MCM-41 ordered mesoporous silicas, which are regarded as the best model mesoporous solids currently available. Thus, an accurate reference isotherm has been developed from extensive experimental observations and surface heterogeneity analysis by density functional theory the critical pore filling pressures have been determined as a function of the pore size from adsorption isotherms on MCM-41 materials well characterized by independent X-ray techniques and finally, the important variation of the pore fluid density with pressure and pore size has been accounted for by density functional theory calculations. The pore size distribution for an unknown sample is extracted from its experimental nitrogen isotherm by inversion of the integral equation of adsorption using the hybrid models as the kernel matrix. The approach reported in the current study opens new opportunities in characterization of mesoporous and microporous-mesoporous materials. 

The integral equation of isothermal adsorption for the case of pore size distribution can be written as the convolution ... 

---