Multi-layer, adsorption

Brunauer-Emmett-Teller (BET) adsorption describes multi-layer Langmuir adsorption. Multi-layer adsorption occurs in physical or van der Waals bonding of gases or vapors to solid phases. The BET model, originally used to describe this adsorption, has been applied to the description of adsorption from solid solutions. The adsorption of molecules to the surface of particles forms a new surface layer to which additional molecules can adsorb. If it is assumed that the energy of adsorption on all successive layers is equal, the BET adsorption model [36] is expressed as Eq. (6) ... 

From the point of view of solute interaction with the structure of the surface, it is now very complex indeed. In contrast to the less polar or dispersive solvents, the character of the interactive surface will be modified dramatically as the concentration of the polar solvent ranges from 0 to l%w/v. However, above l%w/v, the surface will be modified more subtly, allowing a more controlled adjustment of the interactive nature of the surface It would appear that multi-layer adsorption would also be feasible. For example, the second layer of ethyl acetate might have an absorbed layer of the dispersive solvent n-heptane on it. However, any subsequent solvent layers that may be generated will be situated further and further from the silica surface and are likely to be very weakly held and sparse in nature. Under such circumstances their presence, if in fact real, may have little impact on solute retention. 

In this review article we have tried to show that an analytical approach to the thermodynamics and the kinetics of adsorbates is not restricted to simple systems but can deal with rather complicated situations in a systematic approach, such as multi-site and multi-component systems with or without precursor-mediated adsorption and surface reconstruction, including multi-layers/subsurface species. This approach automatically ensures that such fundamental principles as detailed balance are implemented properly. 

The basic technique involves physical adsorption of N2, which has a cross-sectional area of 0.162 nm, on the surface. The problem is that multi-layers of gas start to build up on the catalyst surface before a monolayer is completely formed. The BET equation describes these phenomena ... 

Fabrication processing of these materials is highly complex, particularly for materials created to have interfaces in morphology or a microstructure [4—5], for example in co-fired multi-layer ceramics. In addition, there is both a scientific and a practical interest in studying the influence of a particular pore microstructure on the motional behavior of fluids imbibed into these materials [6-9]. This is due to the fact that the actual use of functionalized ceramics in industrial and biomedical applications often involves the movement of one or more fluids through the material. Research in this area is therefore bi-directional one must characterize both how the spatial microstructure (e.g., pore size, surface chemistry, surface area, connectivity) of the material evolves during processing, and how this microstructure affects the motional properties (e.g., molecular diffusion, adsorption coefficients, thermodynamic constants) of fluids contained within it. 

This isotherm finds use mainly in the study of the adsorption of gases on solids however, it can be useful in the study of adsorption of pollutants from aqueous systems, particularly onto solid phases. The heterogeneous nature of a solid surface (i. e., soils, sediments, suspended solids) would obviously invalidate the first assumption (i.e., a, above) used in developing the relationship. The third assumption (i. e., c, above) also would be invalid in a situation where one is dealing with multi-layer adsorption. 

Following mono-layer uptake, further increase in pressure results in multi-layer adsorption of N2. For this part of the isotherm, condensation-evaporation equilibrium is assumed to take place, instead of adsorption-desorption equilibrium for each individual layer other than the first layer. This dynamic equiUbria for the first and higher layers and some simplifying assumptions form the basis for the B ET treatment of the multi-layer adsorption isotherm. A lengthy derivation leads to the BET relation between adsorbed volume of N2 and relative pressure. Here relative pressure is defined as the ratio of the equilibrium pressure to the... 

Fig. 20.1. MAC Mode AFM three-dimensional images in air of (A) clean HOPG electrode (B) thin-film dsDNA-biosensor surface, prepared onto HOPG by 3 min free adsorption from 60 pg/mL dsDNA in pH 4.5 0.1 M acetate buffer (C) multi-layer film dsDNA biosensor, prepared onto HOPG by evaporation of three consecutive drops each containing 5pL of 50 pg/mL dsDNA in pH 4.5 0.1 M acetate buffer (D) thick-film dsDNA biosensor, prepared onto HOPG by evaporation from 37.5mg/mL dsDNA in pH 4.5 0.1M acetate buffer. With permission from Refs. [28,29].

GCE surface. Such kinds of devices have been shown to be inappropriate since they do not ensure a complete coverage of the GCE surface allowing the non-specific adsorption of the compound. However, a new type of biosensor-multi-layer dsDNA-electrochemical biosensor obtained by successive additions of small quantities of dsDNA on the GCE surface has been developed (see Procedure 29 in CD accompanying this book) and further used to study the interaction between dsDNA and the quercetin-Cu(II) complex. 

For an evaluation of the local model isotherm 6(p,T,Q) with constant interaction energy Q, the effects of multi-layer adsorption and lateral interactions between neighboring adsorbed molecules are considered by applying two modifications to the Langmuir isotherm (i) a multi-layer correction according to the well known BET-concept and (ii) a correction due to lateral interactions with neighboring gas molecules introduced by Fowler and Guggenheim (FG) [105] ... 

Atomic force microscopy has been up to now only scarcely used by the plasma processing community. Results mainly concern low-resolution measurements, that is modification of the surface roughness induced by the plasma [43,44], Micro masking effects have been observed when processing Si with a SF6 plasma beam at low temperature (Fig. 11) and correlated to the multi-layer adsorption of plasma species as observed by XPS [45], Further development of vacuum techniques should allow high resolution surface probe microscopy measurements on plasma-treated samples, and possibly lead to complementary information on adsorption kinetics, surface density of states. 

The type II isotherm is associated with solids with no apparent porosity or macropores (pore size > 50 nm). The adsorption phenomenon involved is interpreted in terms of single-layer adsorption up to an inversion point B, followed by a multi-layer type adsorption. The type IV isotherm is characteristic of solids with mesopores (2 nm < pore size < 50 nm). It has a hysteresis loop reflecting a capillary condensation type phenomenon. A phase transition occurs during which, under the eflcct of interactions with the surface of the solid, the gas phase abruptly condenses in the pore, accompanied by the formation of a meniscus at the liquid-gas interface. Modelling of this phenomenon, in the form of semi-empirical equations (BJH, Kelvin), can be used to ascertain the pore size distribution (cf. Paragr. 1.1.3.2). 

Langmuir monolayers play some part in the preparation of multi-layer systems, now mostly referred to as self-assembled monolayers or multilayers (SAM s). However, this role is modest because it is difficult to make Langmuir-Blodgett layers sufficiently perfect and stable to function in new materials, such as electronic and bio-mimetic devices. One approach of stabilizing LB films is by working with molecules having double bonds that, after deposition, are polymerized. Such layers are stable enough to serve as a substrate for protein adsorption ). 

Wang, C.-H. Hwang, B.J. A general adsorption isotherm considering multi-layer adsorption and heterogeneity of adsorbent. Chem. Eng. Sci. 2000, 55, 4311-4321. 

Since IGC is able to generate adsorption isotherms and to evaluate acid/base interactions for specified adsorbate-adsorbent pairs, it follows that the technique is able to develop a detailed picture of surface properties for non-volatile stationary phases. This is illustrated, again for carbon fibers, by Vukov and Gray (48). They combine IGC information at essentially zero coverage of the injected probes with finite concentration data to obtain heat of adsorption values ranging from zero to multi-layer coverage. Their meticulous study shows the effects of thermal pretreatment on fiber surface characteristics, and underscores the convenience and power of IGC to generate information otherwise far more difficult to obtain. 

Vapor Adsorption. Ethanol and heptane vapor adsorption isotherms on cellulose are illustrated in Figure 6 for temperatures of 24.3 C and 26.5°C. The isotherms indicate multi-layer adsorption, which is typical for vapor adsorption on polymeric materials (16). Adsorption is sensitive to the temperature of both vapors and is decreased significantly by increasing the temperature from 24.3°C to 26.5 C. 

The resulting isotherms are illustrated as lines in Fig. 6.25b. The stronger adsorbing S-enantiomer isotherm exhibits an inflection point and is assumed to be independent of the R-enantiomer concentration. The R-enantiomer isotherm shows typical Langmuir behavior and minor interaction with the S-enantiomers. The rather uncommon case of higher loadings of the R-enantiomer in mixtures can be explained with multi-layer adsorption processes (Mihlbachler et al., 2001). 

The two processes are known as SILAR (successive ion layer adsorption and reaction) and ILGAR (ion layer gas reaction). Both methods work best when a metal salt is chosen in which the metal ion has the same valence state as in the desired final compound. Depending on concentration, temperature and duration, the thickness of the deposited metal can be varied from approximately monolayer thickness to more continuous single- or multi-layer coverage. 

Wang, C.H. and Hwang, B.J. (2000). Characterizing the adsorption behaviors of various adsorbates on activated carbons via the multi-layer theory. J. Chin. Inst. Chem. Eng., 31, 333-8. 

The nitrogen adsorption isotherms are characteristic of microporous solids. The aging treatments cause a clear decrease in the micropore volume and in the microporous surface. The decreases are nevertheless smaller for the Cu-ZSM-5 solid (variation A = 0.04 after aging at 1173 K) than for the parent zeolite (A= 0.07) (Table 2). An apparent BET surface area has been reported though the BET theory is not applicable to microporous materials since the pore condensation isotherm is interfering with the multi-layer adsorption isotherm. 

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