Multilayer equations

The following table (Table 3.8-1) summarises all the multilayer equations dealt with in this chapter. The parameter x in some of the equations is the reduced pressure (P/Pq)-... 

Reactor sources also produce appreciable background (e.g. fast neutrons, y-rays), which can also be recorded by area detectors. By introducing some curvature into the guides, it is possible to separate out this component, which is not reflected as efficiently as are cold (A 5-30 A) neutrons. Alternatively, the beam may be deflected by supermirrors, which operate on the basis of the discrete ttiin-film multilayer equations of Hayter and Mook [85], and such mirrors may be designed to reflect up to three or four times the critical angle for internal reflection that can be achieved by natural Ni guide coatings (9c 0.1 A (A)). 

This is fortunately offered by the calorimetric experiments which suggest that the BET monolayer content physically corresponds to an energetically strong retention. This quantity, provided by the BET equation, could therefore be called safely the BET strong retention capacity This quantity includes two parts, which are the micropore capacity and the monolayer content on the non-microporous portions of the surface. The latter, which provides the external (/.e. non-microporous) surface area is easily assessed by means of the as or t methods, without even requesting the very low part of the adsorption isotherm. The as method is to be preferred when one wishes to carry out a more detailed analysis of the micropores and when the low pressure range of the adsorption isotherm is available. Conversely, if one only wishes to assess a reliable external surface area, he will probably find it simpler to use the t method this can indeed easily be done in a software, after introducing the appropriate multilayer equation, like the Harkins and Jura t-curve equation [13]. The recommended succession of calculations is therefore ... 

Because of their prevalence in physical adsorption studies on high-energy, powdered solids, type II isotherms are of considerable practical importance. Bmnauer, Emmett, and Teller (BET) [39] showed how to extent Langmuir s approach to multilayer adsorption, and their equation has come to be known as the BET equation. The derivation that follows is the traditional one, based on a detailed balancing of forward and reverse rates. 

The very considerable success of the BET equation stimulated various investigators to consider modifications of it that would correct certain approximations and give a better fit to type II isotherms. Thus if it is assumed that multilayer formation is limited to n layers, perhaps because of the opposing walls of a capillary being involved, one... 

The first term on the right is the common inverse cube law, the second is taken to be the empirically more important form for moderate film thickness (and also conforms to the polarization model, Section XVII-7C), and the last term allows for structural perturbation in the adsorbed film relative to bulk liquid adsorbate. In effect, the vapor pressure of a thin multilayer film is taken to be P and to relax toward P as the film thickens. The equation has been useful in relating adsorption isotherms to contact angle behavior (see Section X-7). Roy and Halsey [73] have used a similar equation earlier, Halsey [74] allowed for surface heterogeneity by assuming a distribution of Uq values in Eq. XVII-79. Dubinin s equation (Eq. XVII-75) has been mentioned another variant has been used by Bonnetain and co-workers [7S]. 

The multilayer isotherms illustrated thus far have all been of a continuous appearance—it was such isotherms that the BET, FHH, and other equations treated. About 30 years ago, however, multilayer adsorption on smooth sur-... 

As pointed out in Section XVII-8, agreement of a theoretical isotherm equation with data at one temperature is a necessary but quite insufficient test of the validity of the premises on which it was derived. Quite differently based models may yield equations that are experimentally indistinguishable and even algebraically identical. In the multilayer region, it turns out that in a number of cases the isotherm shape is relatively independent of the nature of the solid and that any equation fitting it can be used to obtain essentially the same relative surface areas for different solids, so that consistency of surface area determination does not provide a sensitive criterion either. 

Brunauer (see Refs. 136-138) defended these defects as deliberate approximations needed to obtain a practical two-constant equation. The assumption of a constant heat of adsorption in the first layer represents a balance between the effects of surface heterogeneity and of lateral interaction, and the assumption of a constant instead of a decreasing heat of adsorption for the succeeding layers balances the overestimate of the entropy of adsorption. These comments do help to explain why the model works as well as it does. However, since these approximations are inherent in the treatment, one can see why the BET model does not lend itself readily to any detailed insight into the real physical nature of multilayers. In summary, the BET equation will undoubtedly maintain its usefulness in surface area determinations, and it does provide some physical information about the nature of the adsorbed film, but only at the level of approximation inherent in the model. Mainly, the c value provides an estimate of the first layer heat of adsorption, averaged over the region of fit. 

There is little doubt that, at least with type II isotherms, we can tell the approximate point at which multilayer adsorption sets in. The concept of a two-dimensional phase seems relatively sterile as applied to multilayer adsorption, except insofar as such isotherm equations may be used as empirically convenient, since the thickness of the adsorbed film is not easily allowed to become variable. 

The adsorption isotherms are often Langmuirian in type (under conditions such that multilayer formation is not likely), and in the case of zeolites, both n and b vary with the cation present. At higher pressures, capillary condensation typically occurs, as discussed in the next section. Some N2 isotherms for M41S materials are shown in Fig. XVII-27 they are Langmuirian below P/P of about 0.2. In the case of a microporous carbon (prepared by carbonizing olive pits), the isotherms for He at 4.2 K and for N2 at 77 K were similar and Langmuirlike up to P/P near unity, but were fit to a modified Dubninin-Radushkevich (DR) equation (see Eq. XVII-75) to estimate micropore sizes around 40 A [186]. 

In the present study we try to obtain the isotherm equation in the form of a sum of the three terms Langmuir s, Henry s and multilayer adsorption, because it is the most convenient and is easily physically interpreted but, using more a realistic assumption. Namely, we take the partition functions as in the case of the isotherm of d Arcy and Watt [20], but assume that the value of V for the multilayer adsorption appearing in the (5) is equal to the sum of the number of adsorbed water molecules on the Langmuir s and Henry s sites ... 

Langmuir referred to the possibility that the evaporation-condensation mechanism could also apply to second and higher molecular layers, but the equation he derived for the isotherm was complex and has been little used. By adopting the Langmuir mechanism but introducing a number of simplifying assumptions Brunauer, Emmett and Teller in 1938 were able to arrive at their well known equation for multilayer adsorption, which has enjoyed widespread use ever since. 

A number of attempts have been made to modify the BET equation so as to obtain better agreement with the experimental isotherm data in the multilayer region. One of the most recent is that of Brunauer and his co-workers ... 

The multilayer region. The Frenkel-Halsey-Hiil (FHH) equation... 

When the film thickens beyond two or three molecular layers, the effect of surface structure is largely smoothed out. It should therefore be possible, as Hill and Halsey have argued, to analyse the isotherm in the multilayer region by reference to surface forces (Chapter 1), the partial molar entropy of the adsorbed film being taken as equal to that of the liquid adsorptive. By application of the 6-12 relation of Chapter 1 (with omission of the r" term as being negligible except at short distances) Hill was able to arrive at the isotherm equation... 

The validity of Equation (2.30) may be tested by plotting log log (p°/p) against log ( / ) (or, if more convenient, against log n) when a straight line of slope -s should be obtained for the multilayer region of the isotherm. In... 

Equation (3.52) is applied in succession to all steps from step 1 onwards, commencing from the uptake n, where all pores are deemed full (often at p/p° = 0-95 cf. p. 132), to obtain the values of 5 4, 6A2 etc. If no correction is made for the thinning of the multilayer as the emptying process continues, the core volumes will be given by Svf = ( — and the uncorrected... 

In order to allow for the thinning of the multilayer, it is necessary to assume a pore model so as to be able to apply a correction to Uj, etc., in turn for re-insertion into Equation (3.52). Unfortunately, with the cylindrical model the correction becomes increasingly complicated as desorption proceeds, since the wall area of each group of cores changes progressively as the multilayer thins down. With the slit model, on the other hand, <5/l for a... 

Layered Structures. Whenever a barrier polymer lacks the necessary mechanical properties for an appHcation or the barrier would be adequate with only a small amount of the more expensive barrier polymer, a multilayer stmcture via coextmsion or lamination is appropriate. Whenever the barrier polymer is difficult to melt process or a particular traditional substrate such as paper or cellophane [9005-81-6] is necessary, a coating either from latex or a solvent is appropriate. A layered stmcture uses the barrier polymer most efficiently since permeation must occur through the barrier polymer and not around the barrier polymer. No short cuts are allowed for a permeant. The barrier properties of these stmctures are described by the permeance which is described in equation 16 where and L are the permeabiUties and thicknesses of the layers. 

Equations la and lb are for a simple two-phase system such as the air-bulk solid interface. Real materials aren t so simple. They have natural oxides and surface roughness, and consist of deposited or grown multilayered structures in many cases. In these cases each layer and interface can be represented by a 2 x 2 matrix (for isotropic materials), and the overall reflection properties can be calculated by matrix multiplication. The resulting algebraic equations are too complex to invert, and a major consequence is that regression analysis must be used to determine the system s physical parameters. ... 

The stress-strain relations in arbitrary in-plane coordinates, namely Equation (4.5), are useful in the definition of the laminate stiffnesses because of the arbitrary orientation of the constituent laminae. Both Equations (4.4) and (4.5) can be thought of as stress-strain relations for the k layer of a multilayered laminate. Thus, Equation (4.5) can be written as... 

This review is structured as follows. In the next section we present the theory for adsorbates that remain in quasi-equilibrium throughout the desorption process, in which case a few macroscopic variables, namely the partial coverages 0, and their rate equations are needed. We introduce the lattice gas model and discuss results ranging from non-interacting adsorbates to systems with multiple interactions, treated essentially exactly with the transfer matrix method, in Sec. II. Examples of the accuracy possible in the modehng of experimental data using this theory, from our own work, are presented for such diverse systems as multilayers of alkali metals on metals, competitive desorption of tellurium from tungsten, and dissociative... 

The principle underlying surface area measurements is simple physisorb an inert gas such as argon or nitrogen and determine how many molecules are needed to form a complete monolayer. As, for example, the N2 molecule occupies 0.162 nm at 77 K, the total surface area follows directly. Although this sounds straightforward, in practice molecules may adsorb beyond the monolayer to form multilayers. In addition, the molecules may condense in small pores. In fact, the narrower the pores, the easier N2 will condense in them. This phenomenon of capillary pore condensation, as described by the Kelvin equation, can be used to determine the types of pores and their size distribution inside a system. But first we need to know more about adsorption isotherms of physisorbed species. Thus, we will derive the isotherm of Brunauer Emmett and Teller, usually called BET isotherm. 

BET method. The most commonly used method for determining the specific surface area is the so-called BET method, which obtained its name from three Nobel prize winners Brunauer, Emmett and Teller (1938). It is a modification of the Langmuir theory, which, besides monolayer adsorption, also considers multilayer adsorption. The equation allows easy calculation of the surface area, commonly referred to as the BET surface area ( bet). From the isotherms also pore-radii and pore-volumes can be calculated (from classical equation for condensation in the pores). 

For microporous materials the 5bet values obtained are usually much higher than the real surface area, because in the region where the BET equation is applied (this equation assumes multilayer adsorption but not condensation) conden.sation already takes place. 

The most spectacular peak profiles, which suggest self-associative interactions, were obtained for 5-phenyl-1-pentanol on the Whatman No. 1 and No. 3 chromatographic papers (see Figure 2.15 and Figure 2.16). Very similar band profiles can be obtained using the mass-transfer model (Eqnation 2.21), coupled with the Fowler-Guggenheim isotherm of adsorption (Equation 2.4), or with the multilayer isotherm (Equation 2.7). 

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