Adsorption processes thermodynamics

Systems involving an interface are often metastable, that is, essentially in equilibrium in some aspects although in principle evolving slowly to a final state of global equilibrium. The solid-vapor interface is a good example of this. We can have adsorption equilibrium and calculate various thermodynamic quantities for the adsorption process yet the particles of a solid are unstable toward a drift to the final equilibrium condition of a single, perfect crystal. Much of Chapters IX and XVII are thus thermodynamic in content. 

The performance of adsorption processes results in general from the combined effects of thermodynamic and rate factors. It is convenient to consider first thermodynamic factors. These determine the process performance in a limit where the system behaves ideally i.e. without mass transfer and Idnetic limitations and with the fluid phase in perfect... 

Cyclic voltammetry is the most widely used technique for acquiring qualitative information about electrochemical reactions. The power of cyclic voltammetry results from its ability to rapidly provide considerable information on the thermodynamics of redox processes, on the kinetics of heterogeneous electron-transfer reactions, and on coupled chemical reactions or adsorption processes. Cyclic voltammetry is often the first experiment performed in an electroanalytical study. In particular, it offers a rapid location of redox potentials of the electroactive species, and convenient evaluation of the effect of media upon the redox process. 

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. 

True differential heats of adsorption may be determined from equilibrium data when adsorption is thermodynamically reversible. However, when this process is not reversible, a calorimeter must be employed, and the so-called differential heats, which are then measured, refer actually to the average heats evolved during the adsorption of small doses of gas ... 

The term parametric pumping was coined by Wilhelm et al. [Wilhelm, Rice, and Bendelius, Ind. Eng. Chem. Fundam., 5,141-144 (1966)] to describe a liquid-phase adsorption process in which separation is achieved by periodically reversing not only flow but also an intensive thermodynamic property such as temperature, which influences adsorptivity. Moreover, they considered the concurrent cycling of pressure, pH, and electrical and magnetic fields. A lot of research and development has been conducted on thermal, pressure, and pH driven cycles, but to date only gas-phase pressure-swing parametric pumping has found much commercial acceptance. 

By the use of other assumptions, the thermodynamic treatment can be simplified and more progress can be made. In particular. Hill has shown that a system of considerable utility can be obtained by considering the adsorption process as a pseudo one-component system. Only the adsorbate is considered as taking an active part. The adsorbent is assumed inert and the only effect of its presence is that its surface provides an attractive force field for the adsorbate molecules. 

In conclusion, the enthalpic partition processes in the columns for polymer HPLC substantially differ from the adsorption processes. Enthalpic partition can be employed for the separation of polymers of the low-to-medium polarity in combination with the alkyl bonded phases on silica gels. The extent of the enthalpic partition and consequently also of the polymer retention is controlled primarily by the thermodynamic quality of eluent toward separated species and by the extent of the bonded phase solvation. 

The deviations from the Szyszkowski-Langmuir adsorption theory have led to the proposal of a munber of models for the equihbrium adsorption of surfactants at the gas-Uquid interface. The aim of this paper is to critically analyze the theories and assess their applicabihty to the adsorption of both ionic and nonionic surfactants at the gas-hquid interface. The thermodynamic approach of Butler [14] and the Lucassen-Reynders dividing surface [15] will be used to describe the adsorption layer state and adsorption isotherm as a function of partial molecular area for adsorbed nonionic surfactants. The traditional approach with the Gibbs dividing surface and Gibbs adsorption isotherm, and the Gouy-Chapman electrical double layer electrostatics will be used to describe the adsorption of ionic surfactants and ionic-nonionic surfactant mixtures. The fimdamental modeling of the adsorption processes and the molecular interactions in the adsorption layers will be developed to predict the parameters of the proposed models and improve the adsorption models for ionic surfactants. Finally, experimental data for surface tension will be used to validate the proposed adsorption models. 

On the other hand, the values for g13 or g23 are positive, with a few exceptions. In other words, the adsorption processes of water and of protein onto polymer surfaces are for the most part thermodynamically unfavorable. The negative values of gs are the result of a remarkable decrease in free energy when adsorptive water molecules are driven back to the bulk water system, as seen... 

Also, in Section 6.83 we talked about the importance of thermodynamic parameters involved in the adsorption process. Thus, the next step is to connect these two sections and find the corresponding AG°, AH0 and AS0 of the adsorption process using the developed isotherm. How can this be done ... 

As we have seen, an adsorption isotherm is one way of describing the thermodynamics of gas adsorption. However, it is by no means the only way. Calorimetric measurements can be made for the process of adsorption, and thermodynamic parameters may be evaluated from the results. To discuss all of these in detail would require another chapter. Rather than develop all the theoretical and experimental aspects of this subject, therefore, it seems preferable to continue focusing on adsorption isotherms, extracting as much thermodynamic insight from this topic as possible. Within this context, results from adsorption calorimetry may be cited for comparison without a full development of this latter topic. 

For an adsorption process to be thermodynamically favorable (proceed spontaneously), the entropy loss has to be compensated by a net decrease in enthalpy A Hr. 

Gas Separation by Adsorption Processes Ralph T. Yang Heterogeneous Reactor Design Hong H. Lee Molecular Thermodynamics of Nonideal Fluids Lloyd L. Lee Phase Equilibria in Chemical Engineering Stanley M. Walas Transport Processes in Chemically Reacting Flow Systems Darnel E. Rosner... 

The practical characteristic of a dyestuff is that when a textile is immersed in a solution containing a dye. the dye preferentially adsorbs onto and diffuses into the texiile. The thermodynamic equations defining this process have been reviewed in detail. The driving force for this adsorption process is the difference in chemical potential between the dye In the solution phase and the dye in the fiber phase. In practice it is only necessary to consider changes in chemical potential and to understand that the driving force is the reduction in free energy associated with the dye molecule moving from one phase to the other, as the molecule always moves to the siate of lowest chemical potential. 

What is the driving force for protein adsorption Is the adsorption driven by overall energetic (enthalpic) interactions or does the entropic contribution prevail Do both entropic and enthalpic contributions play a major part in the adsorption process, the extent of each depending on the particular protein and surface in question An illuminating thermodynamic analysis given by Norde and Lyklema 62,66) for the adsorption of two different globular proteins (human serum albumin, HSA, and bovine pancreatic ribonuclease, RNase) on polystyrene latices will be presented. We believe this analysis has general validity. 

When molecules adsorb to a flat substrate, their conformation is modified due to the geometric confinement between the two interfaces and the direct interaction to the substrate. This state can be far from equilibrium if the adsorption process has been fast and irreversible. In this case, the molecules do not have time to sample the whole assembly of thermodynamic states and get trapped kinetically at contact sites. The reversibility is difficult to achieve because of the great size of the molecules and strong adhesion which might exceeds kBT by far. In order to approach an equilibrium state, the sample has to be pre-... 

When adsorption takes place, the gas molecules are restricted to two-dimensional motion. Gas adsorption processes are, therefore, accompanied by a decrease in entropy. Since adsorption also involves a decrease in free energy, then, from the thermodynamic relationship,... 

In this work we utilized FTIR methods to examine the SA monolayers on flat, polar solid surfaces prepared from nonpolar solutions. We used ATR and GI FTIR measurements to characterize the material and bonding of the S A monolayers, and used transmission and ATR FTIR to monitor the dynamics of the SA adsorption process. With reference to measurements on standard Langmuir-Blodgett monolayer samples, we were able to quantify the S A kinetic results. We also used fluorescence spectroscopy of incorporated pyrene probes in S A mixed monolayer films as a simple method for the determination of the relative adsorption and thermodynamic constants. 

The thermodynamic parameters for the adsorption process of the IC and PEO were also determined using the classical equation [31]. The thermodynamic parameters for the adsorption process of IC are listed in Table 4.3. 

The analysis of these experimental data, taken from reference [28], shows that the thermodynamic parameter values of IC and PEO are completely different. A large positive AH0 and also a large positive AS° are found for the adsorption process of PEO, suggesting that the driving force for this process is of an entropic nature and then AG° is more negative when the temperature increases. 

By the use of various transient methods, electrochemistry has found extensive new applications for the study of chemical reactions and adsorption phenomena. Thus a combination of thermodynamic and kinetic measurements can be utilized to characterize the chemistry of heterogeneous electron-transfer reactions. Furthermore, heterogeneous adsorption processes (liquid-solid) have been the subject of intense investigations. The mechanisms of metal ion com-plexation reactions also have been ascertained through the use of various electrochemical impulse techniques. 

When an outgassed solid (the adsorbent) is confined to a closed space and exposed to a gas or vapor (the adsorptive) at a given pressure and temperature, an adsorption process takes place. The adsorptive molecules are transferred to, and accumulate in, the interfacial layer, as a consequence of an attractive force between the surface of the solid and the adsorptive (the adsorptive actually adsorbed by the adsorbent is named adsorbate). After some time, the pressure becomes constant and the thermodynamic equilibrium of adsorption is achieved. 

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