Membrane-liquid interactions

The fabrication of membranes to work in MC operations has to meet some important structural and chemical requirements, including controlled pore size and narrow pore distribution, along with high porosity and controlled mutual membrane-liquid interactions. The achievement of these targets is often reliant on the combination of suitable materials with well-addressed tailoring procedures. 

There is a need to be able to describe both types of behavior, diffusive and hydraulic, in a consistent manner, which also agrees with experimental data. For example, a membrane with a low water content is expected to be controlled by diffusion, and an uptake isotherm needs to be used (see Figure 7). The reasons for this are that there is not a continuous liquid pathway across the medium and that the membrane matrix interacts significantly with the water due to binding and solvating the sulfonic acid sites. A hydraulic pressure in this system may not be defined. 

Efficient extraction of proteins has been reported with reverse micellar liquid membrane systems, where the pores of the membrane are filled with the reverse micellar phase and the enzyme is extracted from the aqueous phase on one side of membrane while the back extraction into a second aqueous phase takes place at the other side. By this, both the forward and back extractions can be performed using one membrane module [132,208]. Armstrong and Li [209] confirmed the general trends observed in phase transfer using a glass diffusion cell with a reverse micellar liquid membrane. Electrostatic interactions and surfactant concentration affected the protein transfer into the organic membrane and... 

Example 4.9 Entropy production in separation process Distillation Distillation columns generally operate far from their thermodynamically optimum conditions. In absorption, desorption, membrane separation, and rectification, the major irreversibility is due to mass transfer. The analysis of a sieve tray distillation column reveals that the irreversibility on the tray is mostly due to bubble-liquid interaction on the tray, and mass transfer is the largest contributor to the irreversibility. 

These relations can be used as rough estimates of steric rejection, if the solute and membrane pore dimensions are known. The derivation is based on a strictly model situation (see Figure 1) and a long list of necessary assumptions can be written. Apart from the simplified geometry (hard sphere in a cylindrical pore), it was also assumed that the solute travels at the same velocity as the surrounding liquid, that the solute concentration in the accessible parts of the pore is uniform and equal to the concentration in the feed, that the flow pattern is laminar, the liquid is Newtonian, diffusional contribution to solute transport is negligible (pore Peclet number is sufficiently high), concentration polarization and membrane-solute interactions are absent, etc. 

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]. 

These other mechanisms of retaining particles within the depth of membranes may be mechanical or physicochemical. Mechanical means of entrapment apply equally to liquid and gas filtration they include inenial impaction to the walls or surfaces of the pores and lodgement in crevices and dead ends." Theoretical models and other illustrations of membrane filters often portray pores as being cylindrical in shape and as passing directly from the top surface of the membrane to the bottom surface by the shortest siraightesl route. In fact pores are rarely cylindrical, they do not have smooth walls, and their passage may be extremely convoluted even through very thin (typically 0.015 cm) depths of membrane. Physicochemical interactions with the filler medium can be very... 

Proton diffusion can occur via two mechanisms, structural diffusion and vehicle diffusion [37]. It is the combination of these two diffusion mechanisms that confers protonic defects exceptional conductivity in liquid water. The conductivity of protons in aqueous systems of bulk water can be viewed as the limiting case for conductivity in PFSA membranes. When aqueous systems interact with the environment, such as in an acidic polymer membrane, the interaction reduces the conductivity of protons compared to that in bulk water [37]. In addition to the mechanisms described above, transport properties and conductivity of the aqueous phase of an acidic polymer membrane will also be effected by interactions with the sulfonate heads, and by restriction of the size of the aqueous phase that forms within acidic polymer membranes [32]. The effects of the introduction of the membrane can be considered on the molecular scale and on a longer-range scale, see Refs. [16, 32]. Of particular relevance to macroscopic models are the diffusion coefficients. As the amount of water sorbed by the membrane increases and the molecular scale effects are reduced, the properties approach those of bulk water on the molecular scale [32]. 

Other interactions in a membrane internal nanospace. The first is evaporation through a nonporous membrane (pervaporation). Interaction of separating components with a polymer in a membrane internal nanospace, in some cases, moves liquid-vapor equilibrium and removes azeotropic points. 

Biological membranes provide the essential barrier between cells and the organelles of which cells are composed. Cellular membranes are complicated extensive biomolecular sheetlike structures, mostly fonned by lipid molecules held together by cooperative nonco-valent interactions. A membrane is not a static structure, but rather a complex dynamical two-dimensional liquid crystalline fluid mosaic of oriented proteins and lipids. A number of experimental approaches can be used to investigate and characterize biological membranes. However, the complexity of membranes is such that experimental data remain very difficult to interpret at the microscopic level. In recent years, computational studies of membranes based on detailed atomic models, as summarized in Chapter 21, have greatly increased the ability to interpret experimental data, yielding a much-improved picture of the structure and dynamics of lipid bilayers and the relationship of those properties to membrane function [21]. 

The only feasible procedure at the moment is molecular dynamics computer simulation, which can be used since most systems are currently essentially controlled by classical dynamics even though the intermolecular potentials are often quantum mechanical in origin. There are indeed many intermolecular potentials available which are remarkably reliable for most liquids, and even for liquid mixtures, of scientific and technical importance. However potentials for the design of membranes and of the interaction of fluid molecules with membranes on the atomic scale are less well developed. 

In the short term, we do not expect chiral membranes to find large-scale application. Therefore, membrane-assisted enantioselective processes are more likely to be applied. The two processes described in more detail (liquid-membrane fractionation and micellar-enhanced ultrafiltration) rely on established membrane processes and make use of chiral interactions outside the membrane. The major advantages of these... 

In this review, recent development of active transport of ions accross the liquid membranes using the synthetic ionophores such as crown ethers and other acyclic ligands, which selectively complex with cations based on the ion-dipole interaction, was surveyed,... 

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