Adsorbate phases

In general, one should allow for nonideality in the adsorbed phase (as well as in solution), and various authors have developed this topic [5,137,145-149]. Also, the adsorbent surface may be heterogeneous, and Sircar [150] has pointed out that a given set of data may equally well be represented by nonideality of the adsorbed layer on a uniform surface or by an ideal adsorbed layer on a heterogeneous surface. 

Fig. XVII-13. Variation of the density with the adsorbed phase according to the potential theory.

We assume for simplicity that the adsorbed phase has the same entropy as the solid so that only an energy change is associated with the transfer of material from the bnlk to the adsorbed phase, then ... 

To characterize the state of the adsorbed phase, it is useful to evaluate its molar entropy, s , defined as the mean molar value for all the molecules adsorbed over the complete range of surface coverage up to the given amount adsorbed. The molar integral entropy of adsorption. As, is then defined as... 

The problem has been discussed in terms of chemical potential by Everett and Haynes, who emphasize that the condition of diffusional equilibrium throughout the adsorbed phase requires that the chemical potential shall be the same at all points within the phase and since, as already noted, the interaction energy varies wtih distance from the wall, the internal pressure must vary in sympathy, so as to enable the chemical potential to remain constant. 

Density of adsorbed phase/(gcm ) nonane, 0-72 nitrogen, 0-81 carbon dioxide, 110. 

In very small pores the molecules never escape from the force field of the pore wall even at the center of the pore. In this situation the concepts of monolayer and multilayer sorption become blurred and it is more useful to consider adsorption simply as pore filling. The molecular volume in the adsorbed phase is similar to that of the saturated Hquid sorbate, so a rough estimate of the saturation capacity can be obtained simply from the quotient of the specific micropore volume and the molar volume of the saturated Hquid. 

Henry s law corresponds physically to the situation in which the adsorbed phase is so dilute that there is neither competition for surface sites nor any significant interaction between adsorbed molecules. At higher concentrations both of these effects become important and the form of the isotherm becomes more complex. The isotherms have been classified into five different types (9) (Eig. 4). Isotherms for a microporous adsorbent are generally of type I the more complex forms are associated with multilayer adsorption and capillary condensation. 

Fig. 5. Variation of isosteric heat of adsorption with adsorbed phase concentration. Reprinted from ref. 10, courtesy of Marcel Dekker, Inc. To convert kj...

Ideal Adsorbed Solution Theory. Perhaps the most successful approach to the prediction of multicomponent equiUbria from single-component isotherm data is ideal adsorbed solution theory (14). In essence, the theory is based on the assumption that the adsorbed phase is thermodynamically ideal in the sense that the equiUbrium pressure for each component is simply the product of its mole fraction in the adsorbed phase and the equihbrium pressure for the pure component at the same spreadingpressure. The theoretical basis for this assumption and the details of the calculations required to predict the mixture isotherm are given in standard texts on adsorption (7) as well as in the original paper (14). Whereas the theory has been shown to work well for several systems, notably for mixtures of hydrocarbons on carbon adsorbents, there are a number of systems which do not obey this model. Azeotrope formation and selectivity reversal, which are observed quite commonly in real systems, ate not consistent with an ideal adsorbed... 

Thermodynamically Consistent Isotherm Models. These models include both the statistical thermodynamic models and the models that can be derived from an assumed equation of state for the adsorbed phase plus the thermodynamics of the adsorbed phase, ie, the Gibbs adsorption isotherm,... 

A the adsorbed phase mole fraction of component i. These equations are solved simultaneously to determine P , P, and A, and the following equations... 

Haeany Solution Model The initial model (37) considered the adsorbed phase to be a mixture of adsorbed molecules and vacancies (a vacancy solution) and assumed that nonideaUties of the solution can be described by the two-parameter Wilson activity coefficient equation. Subsequendy, it was found that the use of the three-parameter Flory-Huggins activity coefficient equation provided improved prediction of binary isotherms (38). 

Eijuillbrium. Among the aspects of adsorption, equiUbtium is the most studied and pubUshed. Many different adsorption equiUbtium equations are used for the gas phase the more important have been presented (see section on Isotherm Models). Equally important is the adsorbed phase mixing rule that is used with these other models to predict multicomponent behavior. 

The desorptive process may be analyzed before boiling. The key assumption is that the vapor and adsorbed phases are ia equiUbrium ia the bulk of the bed. This assumption eliminates iatraparticle resistances from further consideration and is reasonable for rotary kiln appHcations. The two remaining resistances are associated with hydrocarbon diffusion out of the bed and with convection from the bed surface to the bulk gases. The flux of species Fi from the desorbiag bed becomes... 

D5 adsorbed-phase (sohd, surface, particle, or micropore) diffusion... 

The quantity of a solute adsorbed can be given conveniently in terms of moles or volume (for adsorption) or ion-equivalents (for ion exchange) per unit mass or volume (dry or wet) of sorbent. Common units for adsorption are moV(m of fluid) for the fluid-phase concentration Cj and moV(kg of clean adsorbent) for adsorbed-phase concentration /ij. For gases, partial pressure may replace concentration. 

The enthalpy of the adsorbed phase is evaluated along a path for which the gas-phase components undergo temperature change from Tref to T and then are adsorbed isothermaUy, giving... 

Numerical values for solid diffusivities D,j in adsorbents are sparse and disperse. Moreover, they may be strongly dependent on the adsorbed phase concentration of solute. Hence, locally conducted experiments and interpretation must be used to a great extent. Summaries of available data for surface diffusivities in activated carbon and other adsorbent materials and for micropore diffusivities in zeolites are given in Ruthven, Yang, Suzuki, and Karger and Ruthven (gen. refs.). 

Combined Pore and Solid Diffusion In porous adsorbents and ion-exchange resins, intraparticle transport can occur with pore and solid diffusion in parallel. The dominant transport process is the faster one, and this depends on the relative diffusivities and concentrations in the pore fluid and in the adsorbed phase. Often, equilibrium between the pore fluid and the solid phase can be assumed to exist locally at each point within a particle. In this case, the mass-transfer flux is expressed by ... 

In the irreversible limit R < 0.1), the adsorption front within the particle approaches a shock transition separating an inner core into which the adsorbate has not yet penetrated from an outer layer in which the adsorbed phase concentration is uniform at the saturation value. The dynamics of this process is described approximately by the shrinldng-core model [Yagi and Kunii, Chem. Eng. (Japan), 19, 500 (1955)]. For an infinite fluid volume, the solution is ... 

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