Transport model preferential sorption - capillary flow

Another concept of water and salt transport in reverse osmosis is the preferential sorption-capillary flow mechanism. In this model, the surface of a membrane is microporous and heterogeneous at all levels of solute separation. It is hypothesized that, due to the chemical nature of the membrane skin layer in contact with the aqueous solution, a preferential sorption for the water causes a sorbed water layer to be formed at the skin. This layer of purified water is then forced through the capillary pores by pressure. 

The Preferential Sorption/Capillary Flow Model (Sourirajan and Matsuufa (1985)) is based on the assumption that a layer of water sorbs at the membrane surface, creating a deficit of solute at the surface. The membrane is viewed as a microporous medium, and transport is controlled by the surface chemistry of the membrane and water transport through the membrane. Ions with large hydrated radii are retained better, since they also have to overcome more energy to strip off the water. Ions diffuse through the laj et of strucmred water at the membrane surface and through water cluster channels in the membrane (Staude (1992)), where B is the pure water permeability of the membrane. 

Several mechanisms have been proposed to explain reverse osmosis. According to the preferential sorption-capillary flow mechanism of Sourirajan [114], reverse osmosis separation is the combined result of an interfacial phenomenon and fluid transport under pressure through capillary pores. Figure 5.58a is a conceptual model of this mechanism for recovery of fresh water from aqueous salt solutions. The surface of the membrane in contact with the solution has a preferential sorption for water and/or preferential repulsion for the solute, while a continuous removal of the preferentially sorbed interfacial water, which is of a monomolecular nature, is effected by flow under pressure through the membrane capillaries. According to this model, the critical pore diameter for a maximum separation and permeability is equal to twice the thickness of the preferentially sorbed interfacial layer (Figure 5.58b). 

Good quality RO membranes can reject >95-99% of the NaCl from aqueous feed streams (Baker, Cussler, Eykamp et al., 1991 Scott, 1981). The morphologies of these membranes are typically asymmetric with a thin highly selective polymer layer on top of an open support structure. Two rather different approaches have been used to describe the transport processes in such membranes the solution-diffusion (Merten, 1966) and surface force capillary flow model (Matsuura and Sourirajan, 1981). In the solution-diffusion model, the solute moves within the essentially homogeneously solvent swollen polymer matrix. The solute has a mobility that is dependent upon the free volume of the solvent, solute, and polymer. In the capillary pore diffusion model, it is assumed that separation occurs due to surface and fluid transport phenomena within an actual nanopore. The pore surface is seen as promoting preferential sorption of the solvent and repulsion of the solutes. The model envisions a more or less pure solvent layer on the pore walls that is forced through the membrane capillary pores under pressure. 

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