Membrane materials solubility selectivity

DJD is the ratio of the diffusion coefficients of the two molecules and can be viewed as the mobil-ity or diffusivity selectivity, reflecting the different sizes of the two molecules is the ratio of the Henry s law sorption coefficients of the two molecules and can be viewed as the sorption or solubility selectivity of the two molecules. The balance between the solubility selectivity and the diffusivity selectivity determines whether a membrane material is selective for molecule A or molecule B in a feed mixture. Either the diffusivity or the solubility needs to be enhanced to increase membrane selectivity however, polymers that are more permeable are generally less selective and vice versa [19]. The schematic diagram of polymer membrane is given in Figure 6.1. The driving force behind the transport process which involves sorption, diffusion and permeation is the concentration difference between the two phases [21]. 

Approaches to make a polymeric membrane selective to C02 attempt to enhance the solubility selectivity of the polymer material for C02 and reduce the diffusivity selectivity of the polymer that favors smaller hydrogen molecule. The permeability of a polymer membrane for species A, PA, is often expressed as (Ghosal and Freeman, 1994)... 

These incorporate membranes fabricated from insoluble crystalline materials. They can be in the form of a single crystal, a compressed disc of micro-crystalline material or an agglomerate of micro-crystals embedded in a silicone rubber or paraffin matrix which is moulded in the form of a thin disc. The materials used are highly insoluble salts such as lanthanum fluoride, barium sulphate, silver halides and metal sulphides. These types of membrane show a selective and Nemstian response to solutions containing either the cation or the anion of the salt used. Factors to be considered in the fabrication of a suitable membrane include solubility, mechanical strength, conductivity and resistance to abrasion or corrosion. 

Permeabilities measured for pure gases can serve as a rough guide for selection of membrane materials. For design, data must be obtained on gas mixtures, where selectivities are often found to be much lower than those calculated from pure-component measurements. This effect is often due to plasticisation of the membrane by sorption of the most soluble component of the gas. This allows easier penetration by the less-permeable components. The problem of concentration polarisation, which is often encountered in small-scale flow tests, may also be responsible. Concentration polarisation results when the retention time of the gas in contact with the membrane is long. This allows substantial depletion of the most permeable component on the feed side of the membrane. The membrane-surface concentration of that component, and therefore its flux through the membrane, decreases. 

Glasses exist that fnnction as selective electrodes for many different monovalent and some divalent cations. Alternatively, a hydrophobic membrane can be made semiper-meable if a hydrophobic molecnle called an ionophore that selectively binds an ion is dissolved in it. The selectivity of the membrane is determined by the structnre of the ionophore. Some ionophores are natnral products, such as gramicidin, which is highly specific for K+, whereas others such as crown ethers and cryptands are synthetic. Ions such as, 1, Br, and N03 can be detected using quaternary ammonium cationic surfactants as a lipid-soluble counterion. ISEs are generally sensitive in the 10 to 10 M range, but are not perfectly selective. The most typical membrane material used in ISEs is polyvinyl chloride plasticized with dialkylsebacate or other hydrophobic chemicals. 

Traditionally, potentiometric sensors are distinguished by the membrane material. Glass electrodes are very well established especially in the detection of H+. However, fine-tuning of the potentiometric response of this type of membrane is chemically difficult. Solid-state membranes such as silver halides or metal sulphides are also well established for a number of cations and anions [25,26]. Their LOD is ideally a direct function of the solubility product of the materials [27], but it is often limited by dissolution of impurities [28-30]. Polymeric membrane-based ISEs are a group of the most versatile and widespread potentiometric sensors. Their versatility is based on the possibility of chemical tuning because the selectivity is based on the extraction of an ion into a polymer and its complexation with a receptor that can be chemically designed. Most research has been done on polymer-based ISEs and the remainder of this work will focus on this sensor type. 

Various analytical techniques make use of both porous and nonporous (semipermeable) membranes. For porous membranes, components are separated as a result of a sieving effect (size exclusion), that is, the membrane is permeable to molecules with diameters smaller than the membrane pore diameter. The selectivity of such a membrane is thus dependent on its pore diameter. The operation of nonporous membranes is based on differences in solubility and the diffusion coefficients of individual analytes in the membrane material. A porous membrane impregnated with a liquid or a membrane made of a monolithic material, such as silicone rubber, can be used as nonporous membranes. 

Membrane Processes Membrane processes are also used diafiltration is convenient for the removal of small contaminating species such as salts and smaller proteins, and can be combined with subsequent steps to concentrate the protein. Provided that proper membrane materials have been selected to avoid protein-membrane interactions, diafiltration using ultrafiltration membranes is typically straightforward, high-yielding and capital-sparing. These operations can often tolerate the concentration of the desired protein to its solubility limit, maximizing process efficiency. 

Selectivity and productivity depend on sorption and diffusion. Sorption is dictated by thermodynamic properties, namely, the solubility parameter of the solute(s)/membrane material system. On the other hand, the size, shape, molecular weight of the solute, and the availability of inter/intra molecular free space of the polymer largely govern the second property, the diffusion coefficient. For an ideal membrane, both the sorption and diffusion processes should favor the chosen solute. If one step becomes unfavorable for a given solute the overall selectivity will be poor [28]. 

The composite membrane gave 4—5 times larger flux than commercial membrane without appreciable loss in selectivity. Downstream pressure of -6.67 KPa had little effect on the total flux Methanol selectivity PVA > CA > CTA > B1 > B2. The influence of the membrane material with varying solubility parameter is investigated... 

Separation from mixtures is achieved because the membrane transports one component more readily than the others, even if the driving forces are equal. The effectiveness of pervaporation is measured by two parameters, namely flux, which determines the rate of permeation and selectivity, which measures the separation efficiency of the membrane (controlled by the intrinsic properties of the polymer used to construct it). The coupling of fluxes affecting the permeability of a mixture component can be divided into two parts, namely a thermodynamic part expressed as solubility, and a kinetic part expressed as diffusivity. In the thermodynamic part, the concentration change of one component in the membrane due to the presence of another is caused by mutual interactions between the permeates in the membrane in addition to interactions between the individual components and the membrane material. On the other hand, kinetic coupling arises from the dependence of the concentration on the diffusion coefficients of the permeates in the polymers [155]. 

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