Isotherms activity-dispersion

Pig. 2. Activity-dispersion isotherms at constant lattice parameter a. 

Lee, C. K., Morbidelli, M., and Varma, A. Steady state multiplicity behavior of an isothermal axial dispersion fixed-bed reactor with nonuniformly active catalyst. Chem. Eng. Sci. 42, 1595-1608, 1987. 

Adsorption. Adsorption (qv) is an effective means of lowering the concentration of dissolved organics in effluent. Activated carbon is the most widely used and effective adsorbent for dyes (4) and, it has been extensively studied in the waste treatment of the different classes of dyes, ie, acid, direct, basic, reactive, disperse, etc (5—22). Commercial activated carbon can be prepared from lignite and bituminous coal, wood, pulp mill residue, coconut shell, and blood and have a surface area ranging from 500—1400 m /g (23). The feasibiUty of adsorption on carbon for the removal of dissolved organic pollutants has been demonstrated by adsorption isotherms (24) (see Carbon, activated carbon). Several pilot-plant and commercial-scale systems using activated carbon adsorption columns have been developed (25—27). 

Nitrogen adsorption experiments showed a typical t)q5e I isotherm for activated carbon catalysts. For iron impregnated catalysts the specific surface area decreased fix>m 1088 m /g (0.5 wt% Fe ) to 1020 m /g (5.0 wt% Fe). No agglomerization of metal tin or tin oxide was observed from the SEM image of 5Fe-0.5Sn/AC catalyst (Fig. 1). In Fig. 2 iron oxides on the catalyst surface can be seen from the X-Ray diffractions. The peaks of tin or tin oxide cannot be investigated because the quantity of loaded tin is very small and the dispersion of tin particle is high on the support surface. 

The performance of demulsifiers can be predicted by the relationship between the film pressure of the demulsifier and the normalized area and the solvent properties of the demulsifier [1632]. The surfactant activity of the demulsifier is dependent on the bulk phase behavior of the chemical when dispersed in the crude oil emulsions. This behavior can be monitored by determining the demulsifier pressure-area isotherms for adsorption at the crude oil-water interface. 

Of special interest in liquid dispersions are the surface-active agents that tend to accumulate at air/ liquid, liquid/liquid, and/or solid/liquid interfaces. Surfactants can arrange themselves to form a coherent film surrounding the dispersed droplets (in emulsions) or suspended particles (in suspensions). This process is an oriented physical adsorption. Adsorption at the interface tends to increase with increasing thermodynamic activity of the surfactant in solution until a complete monolayer is formed at the interface or until the active sites are saturated with surfactant molecules. Also, a multilayer of adsorbed surfactant molecules may occur, resulting in more complex adsorption isotherms. 

Potential pitfalls exist in ranking catalysts based solely on correlations of laboratory tests (MAT or FFB) to riser performance when catalysts decay at significantly different rates. Weekman first pointed out the erroneous conversion ranking of decaying catalysts in fixed bed and moving bed isothermal reactors (1-3). Phenomena such as axial dispersion in the FFB reactor, the nonisothermal nature of the MAT test, and feedstock differences further complicate the catalyst characterization. In addition, differences between REY, USY and RE-USY catalyst types exist due to differences in coke deactivation rates, heats of reaction, activation energies and intrinsic activities. 

Fig. 3. Activity-lattice parameter isotherms at a constant dispersion of 28 5 A.

Heat capacity between that of ice and liquid water ACpi - - 0.2 cal K-1 g 1 Normalization of pK at 0.05 gg-1. Knee in adsorption isotherm. Native state very stable At 0.07 gg-1 transition in surface water, from disordered to ordered and/or from dispersed to clustered state seen in IR and EPR spectroscopic and thermodynamic properties associated with completion of charged group hydration Water mobility ca. 100 x less than for bulk water increased motion with increased hydration. Bound ligand mobility r constant from 0-0.2gg-1 t = 4x10-9s. Enzymatic activity negligible. 

Fumed silica acts as a highly reinforcing filler in silicone elastomers. Its activity results fi-om its highly dispersed particle structure, high surface area and surface energy. To better understand the interplay of these properties first studies on gas adsorption of hexamethylsiloxane on hydrophilic and silylated silica have been conducted. The shape of the adsorption isotherm revels the existence of low- and high-energy adsorption sites, the latter qualitatively seem to be related to reinforcement of the silicone elastomer. Further quantitative studies in this field are needed. 

The distinguishing feature of dehydrated zeolites as microporous aluminosilicate adsorbents lies in the presence in their voids—i.e., micropores—of cations. These cations compensate excess negative charges of their aluminosilicate skeletons. The cations form, in the zeolite micropores, centers for the adsorption of molecules with a nonuniform distribution of the electron density (dipole, quadrupole, or multiple-bond molecules) or of polarizable molecules. These interactions, which will be called, somewhat conventionally, electrostatic interactions, combine with dispersion interactions and cause a considerable increase in the adsorption energy. As a result, the adsorption isotherms of vapors on zeolites, as a rule, become much steeper in the initial regions of equilibrium pressures as compared with isotherms for active carbons. 

We compare in Figure 6.20 two profiles that were calculated as numerical solutions of the equilibrium-dispersive model, using a linear isotherm. The first profile (solid line) is calculated with a single-site isotherm q = 26.4C) and an infinitely fast A/D kinetics (but a finite axial dispersion coefficient). The second profile (dashed line) uses a two-site isotherm model q — 24C - - 2.4C), which is identical to the single-site isotherm, and assumes infinitely fast A/D kinetics on the ordinary sites but slow A/D kinetics on the active sites. In both cases, the inverse Laplace transform of the general rate model given by Lenhoff [38] (Eqs. 6.65a to h) is used for the simulation. In the case of a surface with two t5q>es of adsorption sites, Eq. 6.65a is modified to take into accoimt the kinetics of adsorption-desorption on these two site types. 

Inverse gas chromatographic measurements may be carried out both at infinite dilution and at finite solute concentrations [1]. In the first case vapours of testing solutes are injected onto the colurtm and their concentrations in the adsorbed layer proceed to zero. Testing substances interact with strong active sites on the examined surface. The retention data are then converted into, e.g. dispersive component of the surface free energy and specific component of free energy of adsorption. In the second case, i.e. at finite solute concentrations, the appropriate adsorption isotherms are used to describe the surface properties of polymer or filler. The differential isosteric heat of adsorption is also calculated under the assumption that the isotherms were obtained at small temperature intervals. 

More recently, Terzyk [32] also suggested that the irreversibility of phenol adsorption is due to the creation of strong complexes between phenol and surface carbonyl and lactone groups and to phenol polymerization. Salame and Bandosz [33] studied phenol adsorption at 30 and 60°C on oxidized and nonoxidized activated carbons. They concluded, from analyses of the isotherms by the FreundUch equation and the surface acidity of the carbons, that phenol was physisorbed by tt—tt dispersion interactions, whereas it was chemisorbed via ester formation between the OH group of phenol and surface carboxyl groups. 

Ahn. P.K. et al.. Effect of alkaline earth added to platinum-supporting oxides on platinum dispersion and dehydrogenation activity, Appl. Catal. A, 101. 207, 1993. Tamiu a. H.. Katayama. N.. and Furuichi. R., The Co+ adsorption properties of ALO,. Fe,O,. Fe,O4. TiO,. and MnOj evaluated by modeling with the Frumkin isotherm., 7 Colloid Interf. Sci.. 195. 192, 1997. 

Dispersion is defined as the fraction of active atoms in surface positions. Higher dispersions are achieved either as monolayers of atomically dispersed material or as very small crystallites. Both exist in practice. In either case, measurement of surface concentration is most easily performed by quantitative probing with selective molecules. There are three common approaches measurement of (I) chemisorption isotherms. (2) reaction titration, and (3) poison titration. 

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