Polymer membrane diffusivity-selective

Although microporous membranes are a topic of research interest, all current commercial gas separations are based on the fourth type of mechanism shown in Figure 36, namely diffusion through dense polymer films. Gas transport through dense polymer membranes is governed by equation 8 where is the flux of component /,andare the partial pressure of the component i on either side of the membrane, /is the membrane thickness, and is a constant called the membrane permeability, which is a measure of the membrane s ability to permeate gas. The ability of a membrane to separate two gases, i and is the ratio of their permeabilities,a, called the membrane selectivity (eq. 9). 

Plasticization Gas solubility in the membrane is one of the factors governing its permeation, but the other factor, diffusivity, is not always independent of solubility. If the solubility of a gas in a polymer is too high, plasticization and swelhng result, and the critical structure that controls diffusion selectivity is disrupted. These effects are particularly troublesome with condensable gases, and are most often noticed when the partial pressure of CO9 or H9S is high. H9 and He do not show this effect This problem is well known, but its manifestation is not always immediate. 

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)... 

It follows from Equation 8.13 that aA/B can be expressed as the product of the diffusivity selectivity, DA/DB, and the solubility selectivity, SA/SB. Diffusion (or mobility) selectivity is governed primarily by the size difference between gas molecules and always favors smaller gas molecules. Solubility selectivity is controlled by the relative condensability of the gases in the polymer and their relative affinity for the polymer. Solubility selectivity typically favors larger, more condensable molecules. From Equation 8.13, it is seen that the product of gas mobility and solubility selectivity determines the overall membrane selectivity. It is clear that for a membrane to be C02 selective, it must have high diffusivity selectivity based on the affinity for C02 but it should be flexible enough to permeate larger molecules such... 

Figure 5.7 shows a typical application of gas-diffusion membranes isolation of the circulating sample from a voltammetric or potentiometric electrode for the electrochemical determination of gaseous species. The ion-selective electrode depicted in this Figure includes a polymer membrane containing nonactin that is used for the potentiometric determination of ammonia produced in biocatalytic reactions. Interferences from alkali metal ions are overcome by covering the nonactin membrane with an outer hydro-... 

The factors affecting the selectivity and permeability of polymer membranes to different gases are best discussed on the basis of Eqs. (12) and (14). As noted in Eq. (12), the permeability coefficient, P, of a penetrant gas in a polymer membrane is the product of a (concentration-averaged) diffusion coefficient, D, and of a solubility coefficient,... 

Robeson [4] showed that there exists a trade-off relationship between selectivity and permeability for dense polymer membranes. This plot was later updated by Singh and Koros [9] (see Figure 4.1). Molecular transport of light gases in such membranes typically occurs by a solution diffusion mechanism (as discussed in Section 4.2.1). For a polymer membrane to be commercially considered for the removal of CO2 from H2, CH4, or air, both the CO2 permeability and selectivity must be competitively high. Since the gases in the mixture with CO2 often are smaller (H2) or about the same size as CO2, they may diffuse more rapidly through the polymers, and it follows that the diffusion selectivity will be <1. The only way... 

The permselectivity of hydrocarbon vapors, p, is dominated by the sorption component, and sorption of hydrocarbon vapors by rubbery polymers is determined by the condensability of their vapors. It can be seen from Table 9.3, that in organosilicon polymers the propane/methane sorption selectivity, is 10.5-16.2, whereas diffusion selectivity, is only 0.16-0.41. Refs. [39 3] report values of permselectivity of hydrocarbon mixtures with nitrogen for organosilicon membranes produced by GKSS (see Figure 9.10). It can be seen that separation selectivity increases with rising boiling temperature of the hydrocarbon, which points to domination of the sorption component of selectivity. 

An important factor that determines diffusion selectivity of the membrane is the rigidity and regularity of the polymer strucmre and stability of the membrane to the mixture being separated. The rigidity of the polymer structure is determined... 

Although these two expressions have the same form, the coefficients are different. In particular, the solubility constant varies much more between various gas solutes than does the diffusion coefficient D. This implies that polymer membranes tend to be much more selective in separation various gas species than porous membranes. Unfortunately, diffusion coefficients in solids and liquids are much smaller than for gases so this increase in selectivity is often traded off with lower permeation rates. 

Figure 19.4). For the three gases given above, the selective electrodes include a glass electrode in contact with a bicarbonate solution of low concentration (0.01 M). The bicarbonate solution is separated from the sample solution by a polymer membrane that allows diffusion of the gas analyte towards the inner electrode compartment. 

One of the first zeolite based membranes were composite membranes, obtained by dispersion of zeolite crystals in dense polymeric films in order to make zeolite filled polymeric membranes [59,60,61], These membranes have been developed at the end of the 80 s for both gas separation and pervaporation. The clogging of zeolite pores by the matrix and the quality of the interface between the zeolite crystals and the polymer matrix (non-selective diffusion pathways) were key points. 

Permselectivity is the ability of a membrane to allow a high flux of one chemical species (typically the analyte) while reducing or eliminating the flux of other species (chemical or sensor interferences). An extreme example of permselectivity is the liquid polymer membranes used in ion selective electrodes. The ionophores contained in these membranes bind selectively to a specific ion. However, this binding is often so strong that the diffusion constant for these ions through the membrane is vanishingly small [15]. 

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