Concentration polarization cause

A phenomenon that is particularly important in the design of reverse osmosis units is that of concentration polarization. This occurs on the feed-side (concentrated side) of the reverse osmosis membrane. Because the solute cannot permeate through the membrane, the concentration of the solute in the liquid adjacent to the surface of the membrane is greater than that in the bulk of the fluid. This difference causes mass transfer of solute by diffusion from the membrane surface back to the bulk liquid. The rate of diffusion back into the bulk fluid depends on the mass transfer coefficient for the boundary layer on feed-side. Concentration polarization is the ratio of the solute concentration at the membrane surface to the solute concentration in the bulk stream. Concentration polarization causes the flux of solvent to decrease since the osmotic pressure increases as the boundary layer concentration increases and the overall driving force (AP - An) decreases. 

This deviation may be attributable to concentration polarization caused by a decrease in the flow velocity of the feed water in the above conditions. 

In a pressure-driven membrane process the molecules are generally rejected by the membrane and therefore their concentrations in the permeate are lower than those in the feed solution. However, an accumulation of excess particles can occur at the membrane surface with the creation of a boundary layer. This phenomenon, called concentration polarization, causes a different membrane performance. In particular, with low molecular weight solutes the observed rejection will be lower than the real retention or, sometimes, it could be negative. 

Concentration polarization caused by macromolecules, which may induce a reversible osmotic pressure that disappears after the filtration pressure is released, and the adsorption on the membrane pores of solid materials or inside the membrane pores of solid materials, which are rid of by rinsing the membrane after the filtration process, are occurrences that both contribute to the reversible resistance to permeation, 7 rev On the other hand, the solids that are deposited on the membrane surface or inside the pores, which are removed only by chemical cleaning of the membrane, constitute the irreversible fouling, Rmev-... 

Both kinetic and concentration polarization cause the potential of an electrode to be more negative than the thermodynamic value. Concentration polarization results from the slow rate at which reactants or products are transported to or away from the electrode surfaces. Kinetic polarization arises from the slow rate of the electrochemical reactions at the electrode surfaces. 

An effect not considered in the above models is the added resistance, caused by fouling, to solute back-diffusion from the boundary layer. Fouling thus increases concentration polarization effects and raises the osmotic pressure of the feed adjacent to the membrane surface, so reducing the driving force for permeation. This factor was explored experimentally by Sheppard and Thomas (31) by covering reverse osmosis membranes with uniform, permeable plastic films. These authors also developed a predictive model to correlate their results. Carter et al. (32) have studied the concentration polarization caused by the build-up of rust fouling layers on reverse osmosis membranes but assumed (and confirmed by experiment) that the rust layer had negligible hydraulic resistance. 

It seems therefore, that the established procedures involving high feed velocity across the membrane surface, additional turbulence promotion, etc., need to be applied and optimized. There is a need for a model for fouling in reverse osmosis which incorporates such factors as the added concentration polarization caused by the fouling layer, and Donnan exclusion effects due to charged foulants. Clearly there is scope for more detailed experimental work in this area. 

The analysis procedure developed in the previous section for gas permeation forms the basis for analyzing RO. However, the RO analysis is more complicated because of 1) osmotic pressure, which is included in Eq. fl7-12T and 2) mass transfer rates are much lower in liquid systems. Since the mass transfer rates are relatively low, the wt frac of solute at the membrane wall x will be greater than the wt frac of solute in the bulk of the retentate x, . This buildup of solute at the membrane surface occurs because the movement of solvent through the membrane carries solute with it to the membrane wall. Since the solute does not pass through the semipermeable membrane, its concentration will build up at the wall and it must back diffuse from the wall to the bulk solution. This phenomenon, concentration polarization, is illustrated in Figure 17-10. Concentration polarization has a major effect on the separations obtained in RO and UF (see next section). Since concentration polarization causes x > Xp the osmotic pressure becomes higher on the retentate side and, following Eq. fl7-12). the flux declines. Concentration polarization will also increase Ax in Eq. tl7-13 and flux of solute may increase, which is also undesirable. In addition, since concentration polarization increases solute concentration, precipitation becomes more likely. 

Major problems inherent in general applications of RO systems have to do with (1) the presence of particulate and colloidal matter in feed water, (2) precipitation of soluble salts, and (3) physical and chemical makeup of the feed water. All RO membranes can become clogged, some more readily than others. This problem is most severe for spiral-wound and hollow-fiber modules, especially when submicron and colloidal particles enter the unit (larger particulate matter can be easily removed by standard filtration methods). A similar problem is the occurrence of concentration-polarization, previously discussed for ED processes. Concentration-polarization is caused by an accumulation of solute on or near the membrane surface and results in lower flux and reduced salt rejection. 

Molecular Rotational Diffusion. Rotational diffusion is the dominant intrinsic cause of depolarization under conditions of low solution viscosity and low fluorophore concentration. Polarization measurements are accurate indicators of molecular size. Two types of measurements are used steady-state depolarization and time-dependent (dynamic) depolarization. 

In an electrochemical system, gas supersaturation of the solution layer next to the electrode will produce a shift of equilibrium potential (as in diffusional concentration polarization). In the cathodic evolution of hydrogen, the shift is in the negative direction, in the anodic evolution of chlorine it is in the positive direction. When this step is rate determining and other causes of polarization do not exist, the value of electrode polarization will be related to solution supersaturation by... 

The dead-end setup is by far the easiest apparatus both in construction and use. Reactor and separation unit can be combined and only one pump is needed to pump in the feed. A cross-flow setup, on the other hand, needs a separation unit next to the actual reactor and an additional pump to provide a rapid circulation across the membrane. The major disadvantage of the dead-end filtration is the possibility of concentration polarization, which is defined as an accumulation of retained material on the feed side of the membrane. This effect causes non-optimal membrane performance since losses through membrane defects, which are of course always present, will be amplified by a high surface concentration. In extreme cases concentration polarization can also lead to precipitation of material and membrane fouling. A membrane installed in a cross-flow setup, preferably applied with a turbulent flow, will suffer much less from this... 

A lithium ion transference number significantly less than 1 is certainly an undesired property, because the resultant overwhelming anion movement and enrichment near electrode surfaces would cause concentration polarization during battery operation, especially when the local viscosity is high (such as in polymer electrolytes), and extra impedance to the ion transport would occur as a consequence at the interfaces. Fortunately, in liquid electrolytes, this polarization factor is not seriously pronounced. 

Problems encountered with filtration ate that membrane fouhng can occur, which causes a decline in flux with time under constant operating conditions. Furthermore, concentration polarization, the effect that the increased concentration of components on the membrane surface reduces the flux due to the additional hydrodynamic resistance, is observed. This effect can be minimized in cross-flow filtration, by applying high flux rates across the membrane surface (Wang et al, 1979 Lee, 1989). 

Since in cathodic reactions is always smaller than c°, the concentration polarization has a negative sign, which adds to the activation overpotential in causing the electrode to depart from the equilibrium potential in the negative direction for an electronation reaction. 

In 4.4 the theory of 4.2 will be applied to study electro-diffusion of ions through a unipolar ion-exchange membrane, separating two electrolyte solutions. This will include the classical treatment of concentration polarization in a solution layer adjacent to an ion-exchange membrane under an electric current. The validity limits of this theory, set by the violations of local electro-neutrality and caused by the development of a macroscopic nonequilibrium space charge, will be indicated. (The effects of the nonequilibrium space charge are to be discussed at some length in Chapter 5.)... 

When the fluid layer mass-transfer coefficient (kM) is large, the resistance Vkbe of this layer is small, and the overall resistance is determined only by the membrane. When the fluid layer mass-transfer coefficient is small, the resistance term 1 /kbb is large, and becomes a significant fraction of the total resistance to permeation. The overall mass transfer coefficient (kov) then becomes smaller, and the flux decreases. The boundary layer mass transfer coefficient is thus an arithmetical fix used to correct the membrane permeation rate for the effect of concentration polarization. Nothing is revealed about the causes of concentration polarization. 

As described above, the initial cause of membrane fouling is concentration polarization, which results in deposition of a layer of material on the membrane surface. The phenomenon of concentration polarization is described in detail in Chapter 4. In ultrafiltration, solvent and macromolecular or colloidal solutes are carried towards the membrane surface by the solution permeating the membrane. Solvent molecules permeate the membrane, but the larger solutes accumulate at the membrane surface. Because of their size, the rate at which the rejected solute molecules can diffuse from the membrane surface back to the bulk solution is relatively low. Thus their concentration at the membrane surface is typically 20-50 times higher than the feed solution concentration. These solutes become so concentrated at the membrane surface that a gel layer is formed and becomes a secondary barrier to flow through the membrane. The formation of this gel layer on the membrane surface is illustrated in Figure 6.6. The gel layer model was developed at the Amicon Corporation in the 1960s [8],... 

The effect of the gel layer on the flux through an ultrafiltration membrane at different feed pressures is illustrated in Figure 6.7. At a very low pressure p, the flux Jv is low, so the effect of concentration polarization is small, and a gel layer does not form on the membrane surface. The flux is close to the pure water flux of the membrane at the same pressure. As the applied pressure is increased to pressure p2, the higher flux causes increased concentration polarization, and the concentration of retained material at the membrane surface increases. If the pressure is increased further to p3, concentration polarization becomes enough for the retained solutes at the membrane surface to reach the gel concentration cgel and form the secondary barrier layer. This is the limiting flux for the membrane. Further increases in pressure only increase the thickness of the gel layer, not the flux. 

The formation of concentration gradients caused by the flow of ions through a single cationic membrane is shown in Figure 10.8. As in the treatment of concentration polarization in other membrane processes, the resistance of the aqueous solution is modeled as a thin boundary layer of unstirred solution separating the... 

Most inefficiencies in electrodialysis systems are related to the difficulty in controlling concentration polarization. The second cause is current utilization losses, arising from the following factors [10] ... 

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