Adsorption energy balance

Material balances, often an energy balance, and occasionally a momentum balance are needed to describe an adsorption process. These are written in various forms depending on the specific application and desire for simplicity or rigor. Reasonably general material balances for various processes are given below. An energy balance is developed for a fixea bed for gas-phase application and simphfied for liquid-phase application. Momentum balances for pressure drop in packed beds are given in Sec. 6. 

Many different forms of the energy balance have been used in fixed-bed adsorption studies. The form chosen for a particular study depends on the process considered (e.g., temperature swing adsorption or pressure swing adsorption) and on the degree of approximation that is appropriate. 

The isoteric heat of adsorption qf is composition-dependent, and the sum of integrals Eq. (16-60) is difficult to evaluate for multicomponent adsorption if the isosteric heats indeed depend on loading. Because each isosteric heat depends on the loadings of all components, the sum must be evaluated for a path beginning with clean adsorbent and ending with the proper loadings of all components, if the isosteric heat of adsorption is constant, as is commonly assumed, then the energy balance (Eq. 16-55) becomes... 

Nonisothermal hquid-phase processes may be driven by changes in feed temperature or heat addition or withdrawal through a column wall. For these, heats of adsorption and pressure effects are generally of less concern. For this case a suitable energy balance is... 

Adsorption The design of gas-adsorption equipment is in many ways analogous to the design of gas-absorption equipment, with a solid adsorbent replacing the liqiiid solvent (see Secs. 16 and 19). Similarity is evident in the material- and energy-balance equations as well as in the methods employed to determine the column height. The final choice, as one would expect, rests with the overall process economics. 

Because of this heat generation, when adsorption takes place in a fixed bed with a gas phase flowing through the bed, the adsorption becomes a non-isothermal, non-adiabatic, non-equilibrium time and position dependent process. The following set of equations defines the mass and energy balances for this dynamic adsorption system [30,31] ... 

The adsorption of hydrocarbons by activated carbon is characterized by the development of adsorption isotherms, adsorption mass and energy balances, and dynamic adsorption zone flow through a fixed bed. 

A volcano plot correlates a kinetic parameter, such as the activation energy, with a thermodynamic parameter, such as the adsorption energy. The maximum in the volcano plot corresponds to the Sabatier principle maximum, where the rate of activation of reactant molecules and the desorption of product molecules balance. 

With high concentrations, heat effects in the chromatographic column may be important. This would require the simultaneous application of an energy balance and the introduction of a term reflecting the influence of temperature on the adsorption equilibrium. 

The coverage under reaction conditions is high and differences in adsorbate-adsorbate interactions balance the differences in adsorption energy. 

The energy balance (3.301) is applicable for catalysis, adsorption, and ion exchange. More specifically, in catalysis, where the steady-state condition exists, frequently the accumulation term is zero. In contrast, adsorption and ion exchange operate under unsteady-state condition. The analysis of the energy balance equation for catalytic fixed beds is presented in detail in Section 5.3.4. 

Some components in a gas or liquid interact with sites, termed adsorption sites, on a solid surface by virtue of van der Waals forces, electrostatic interactions, or chemical binding forces. The interaction may be selective to specific components in the fluids, depending on the characteristics of both the solid and the components, and thus the specific components are concentrated on the solid surface. It is assumed that adsorbates are reversibly adsorbed at adsorption sites with homogeneous adsorption energy, and that adsorption is under equilibrium at the fluid- adsorbent interface. Let (m" ) be the number of adsorption sites and (m 2) the number of molecules of A adsorbed at equilibrium, both per unit surface area of the adsorbent. Then, the rate of adsorption r (kmol m s ) should be proportional to the concentration of adsorbate A in the fluid phase and the number of unoccupied adsorption sites. Moreover, the rate of desorption should be proportional to the number of occupied sites per unit surface area. Here, we need not consider the effects of mass transfer, as we are discussing equilibrium conditions at the interface. At equilibrium, these two rates should balance. Thus,... 

The energy balance within the particle includes the heat of adsorption, Qp per unit volume of particle that is,... 

If the free energy of adsorption is taken as equal to the net energy of interaction between the layers, then the energy balance yields ... 

As a molecule approaches the solid surface, a balance is established between the intermolecular attractive and repulsive forces. If other molecules are already adsorbed, both adsorbent-adsorbate and adsorbate-adsorbate interactions come into play. It is at once evident that assessment of the adsorption energy is likely to become exceedingly complicated in the case of a multicomponent system - especially if the adsorption is taking place from solution at a liquid-solid interface. For this reason, in the numerous attempts made to calculate energies of adsorption, most attention has been given to the adsorption of a single component at the gas-solid interface. 

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