Transport model irreversible thermodynamics

Transport models fall into three basic classifications models based on solution/diffusion of solvents (nonporous transport models), models based on irreversible thermodynamics, and models based on porous membranes. Highlights of some of these models are discussed below. 

As with the finely-porous model, (Chapter 4.1.3), the mathematical representation of solvent and solute fluxes for the irreversible thermodynamic model is quite complex and beyond the scope of this work. However, it is recommended that readers consider references1 and8 for details on this transport model. 

A variety of RO membrane models exist that describe the transport properties of the skin layer. The solution-diffusion model( ) is widely accepted in desalination where the feed solution is relatively dilute on a mole-fraction basis. However, models based on irreversible thermodynamics usually describe membrane behavior more accurately where concentrated solutions are involved.( ) Since high concentrations will be encountered in ethanol enrichment, our present treatment adopts the irreversible thermodynamics model introduced by Kedem and Katchalsky.(7.)... 

Cation, anion, and water transport in ion-exchange membranes have been described by several phenomenological solution-diffusion models and electrokinetic pore-flow theories. Phenomenological models based on irreversible thermodynamics have been applied to cation-exchange membranes, including DuPont s Nafion perfluorosulfonic acid membranes [147, 148]. These models view the membrane as a black box and membrane properties such as ionic fluxes, water transport, and electric potential are related to one another without specifying the membrane structure and molecular-level mechanism for ion and solvent permeation. For a four-component system (one mobile cation, one mobile anion, water, and membrane fixed-charge sites), there are three independent flux equations (for cations, anions, and solvent species) of the form... 

Reverse osmosis is simply the application of pressure on a solution in excess of the osmotic pressure to create a driving force that reverses the direction of osmotic transfer of the solvent, usually water. The transport behavior can be analyzed elegantly by using general theories of irreversible thermodynamics however, a simplified solution-diffusion model accounts quite well for the actual details and mechanism in most reverse osmosis systems. Most successful membranes for this purpose sorb approximately 5 to 15% water at equilibrium. A thermodynamic analysis shows that the application of a pressure difference, Ap, to the water on the two sides of the membrane induces a differential concentration of water within the membrane at its two faces in accordance with the following (31) ... 

For membrane processes involving liquids the mass transport mechanisms can be more involved. This is because the nature of liquid mixtures currently separated by membranes is also significantly more complex they include emulsions, suspensions of solid particles, proteins, and microorganisms, and multi-component solutions of polymers, salts, acids or bases. The interactions between the species present in such liquid mixtures and the membrane materials could include not only adsorption phenomena but also electric, electrostatic, polarization, and Donnan effects. When an aqueous solution/suspension phase is treated by a MF or UF process it is generally accepted, for example, that convection and particle sieving phenomena are coupled with one or more of the phenomena noted previously. In nanofiltration processes, which typically utilize microporous membranes, the interactions with the membrane surfaces are more prevalent, and the importance of electrostatic and other effects is more significant. The conventional models utilized until now to describe liquid phase filtration are based on irreversible thermodynamics good reviews about such models have been reported in the technical literature [1.1, 1.3, 1.4]. 

In addition to the approach using phenomenological equations for modelling ion transport in soils, the theory of irreversible thermodynamics may be adapted to soils [26], as for the case of ion-exchange membranes. Spiegler [251 and Kedem and Katchalsky [27,28] are the prime examples of this approach to transport models. The detailed review by Verbrugge and Pintauro contains a number of other references to mathematical approaches for modelling the fundamental electrokinetic phenomena. 

The Irreversible Thermodynamics Model (Kedem and Katchalsky (1958)) is founded on coupled transport between solute and solvent and between the different driving forces. The entropy of the system increases and free energy is dissipated, where the free energy dissipation function may be written as a sum of solute and solvent fluxes multiplied by drivir forces. Lv is the hydrodynamic permeability of the membrane, AII v the osmotic pressure difference between membrane wall and permeate, Ls the solute permeability and cms the average solute concentration across the membrane. 

Thus, from the point of view of modem phenomenological thermodynamics, the current outputs of classical equilibrium thermodynamics (e.g. the description of thermochemistry of mixtures) and the tasks of irreversible thermodynamics, like the description of linear transport phenomena and nonlinear chemical kinetics, are valid much more generally, e.g. even when all these processes mn simultaneously. As we noted above, these properties are not expected to be valid in any material models in some models the local equilibrium may not be valid, reaction rates may depend not only on concentrations and temperature, etc. 

Marcotte et al. improved Toupin s model by giving a closer thermodynamic description of forces involved in the osmotic dehydration process [41]. The transmembrane transport is modeled on the basis of irreversible thermodynamics whereas transport in the intercellular space is modeled by relations derived from the second Pick s equation. 

Transport in OSN membranes occurs by mechanisms similar to those in membranes used for aqueous separations. Most theoretical analyses rely on either irreversible thermodynamics, the pore-flow model and the extended Nemst-Planck equation, or the solution-diffusion model [135]. To account for coupling between solute and solvent transport (i.e., convective mass transfer effects), the Stefan-Maxwell equations commonly are used. The solution-diffusion model appears to provide a better description of mixed-solvent transport and allow prediction of mixture transport rates from pure component measurements [136]. Experimental transport measurements may depend significantly on membrane preconditioning due to strong solvent-membrane interactions that lead to swelling or solvent phase separation in the membrane pore structure [137]. 

Several approaches have been followed to understand the transport phenomena occurring in perfluoropolymeric membranes, and these include irreversible thermodynamics, use of the Nemst-Planck transport equation (Eq.l3), and various descriptions (e.g., free-volume model, lattice model, quasi-crystalline model) coupling the morphological and chemical properties of the membranes. The reader is referred to the references and citations in the reviews [81-87] for more details related to these models. 

The thermodynamics of irreversible processes are very useful for understanding and quantifying coupling phenomena. However, structure-related membrane models are more useful than the irreversible thermodynamic approach for developing specific membranes. A number of such transport models have been developed, partly based on the principles of the thermodynamics of irreversible processes, both for porous and nonporous membranes. Again, two types of structure will be considered here porous membranes, as found in microfUtration/uItrafiltration, and nonporous membranes of the type used in pervaporation/gas separation. 

In the second chapter of this book, we shall represent and discuss a few examples of physical or chemical models for biological phenomena like transport across membranes, membrane excitation, control of metabolism, and population dynamic interaction between different species. All these models will be of the type of a reaction kinetic model, i.e., the model processes are chemical reactions and diffusion of molecules or may at least be interpreted like that. Thus, the physical background of the various models is irreversible thermodynamics of reactions and diffusion. 

In this Section, it is implicitly assumed that the mass transport resistance at the fluid-membrane interface on either side of the membrane is negligible. Also the following is information that is made available publicly by the membrane manufacturers, when not otherwise noted. As in technical processes, mass transport across semipermeable medical membranes is conveniently related to the concentration and pressme driving forces according to irreversible thermodynamics. Hence, for a two-component mixture the solute and solvent capacity to permeate a semipermeable membrane under an applied pressure and concentration gradient across the membrane can be expressed in terms of the following three parameters Lp, hydraulic permeability Pm, diffusive permeability and a, Staverman reflection coefficient (Kedem and Katchalski, 1958). All of them are more accurately measured experimentally because a limited knowledge of membrane stmcture means that theoretical models provide rather inaccurate predictions. 

Modeling an electrochemical interface by the equivalent circuit (EC) representation approach has been exceptionally popular in studies of electrodes modified with polymer membranes, although an analytical approach based on transport equations derived from irreversible thermodynamics was also attempted [6,7]. ECs are typically composed of numerous ideal electrical components, which attempt to represent the redox electrochemistry of the polymer itself, its highly developed morphology, the interpenetration of the electrolyte solution and the polymer matrix, and the extended electrochemical double layer established between the solution and the polymer with variable localized properties (degree of oxidation, porosity, conductivity, etc.). 

An optimized mechanism for homogeneous combustion of C1-C3 species by Qin et al. (70 species, 14 irreversible and 449 reversible reactions) [2] was employed for modeling gas-phase chemistry. Thermodynamic data were included in the provided scheme. Surface and gas-phase reaction rates were evaluated with Surface-CHEMKIN [3] and CHEMKIN [4] respectively. Mixture-average difihi-sion was the transport model, using the CHEMKIN transport database [5]. 

Figure 10. Kleitz s reaction pathway model for solid-state gas-diffusion electrodes. Traditionally, losses in reversible work at an electrochemical interface can be described as a series of contiguous drops in electrical state along a current pathway, for example. A—E—B. However, if charge transfer at point E is limited by the availability of a neutral electroactive intermediate (in this case ad (b) sorbed oxygen at the interface), a thermodynamic (Nernstian) step in electrical state [d/j) develops, related to the displacement in concentration of that intermediate from equilibrium. In this way it is possible for irreversibilities along a current-independent pathway (in this case formation and transport of electroactive oxygen) to manifest themselves as electrical resistance. This type of chemical valve , as Kleitz calls it, may also involve a significant reservoir of intermediates that appears as a capacitance in transient measurements such as impedance. Portions of this image are adapted from ref 46. (Adapted with permission from ref 46. Copyright 1993 Rise National Laboratory, Denmark.)...

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