Small molecule separation pore size distributions

For the optimal application of GPC to the separation of discrete small molecules, three factors should be considered. Solvent effects are minimal, but may contribute selectivity when solvent-solute interactions occur. The resolving power in SMGPC increases as the square root of the column efficiency (plate count). New, efficient GPC columns exist which make the separation of small molecules affordable and practical, as indicated by applications to polymer, pesticide, pharmaceutical, and food samples. Finally, the slope and range of the calibration curve are indicative of the distribution of pores available within a column. Transformation of the calibration curve data for individual columns yields pore size distributions from which useful predictions can be made regarding the characteristics of column sets. 

Ksec = 0 when the molecule hydrodynamic radius is higher than the mean pore diameter. KSEC is 1 with small molecules, which can easily penetrate into the pores. The most important parameters influencing resolution are the pore volume, pore size distribution, and particle size. The separation domain is between the exclusion volume Va and the inclusion volume ( V0 + Vp). 

Molecular sieving Fig. 4(e) where, due to steric hindrance, only small molecules will diffuse through the membrane, seems to be a useful principle for achieving good separations. To ensure this molecular sieving effect, ultramicroporous membranes have to be prepared. Moreover, such membranes should not only be defect free but must also present a very narrow pore size distribution to avoid any other (less selective) permeation mechanisms defect-free zeolite membranes appear to be good candidates for this type of separation. 

The column packing in SEC comprises porous, spherical gel beads with a defined pore size distribution. Most often, these beads are made from poly(styr-ene-divinylbenzene). (For GFC, cross-linked dextran and agarose gels are often used. ) The sample is dissolved in a suitable solvent that is often used as the mobile phase as well. Separation occurs as a result of differences in accessibility of pore volume. Small molecules can freely access the whole pore volume as a result, the column retards these molecules the greatest. As molecular volume increases, less and less pore volume is accessible for molecules to sample, and elution times decrease. For all molecules with hydrodynamic volumes that are too large to penetrate into the pores of the packing, elution occurs at the (interstitial) void volume of the column. The retention volume for each solute can be described mathematically as ... 

Carbon molecular sieves (CMS) are highly microporous materials having a preponderance of pores of < 1 nm. Among the various types of carbon, CMS materials represent one member of the family of activated carbons. CMS differ from activated carbons in the actual surface composition and the pore size distribution. Unlike CMS, activated carbons display far better detectable surface functionalities. CMS are finding a number of possible uses for the separation of air or other gases and in catalysis. CMS for use as air separation sorbents are usually made from activated carbons by a post-treatment that narrows the pore-size distribution to produce a material with a biomodal pore distribution having a predominance of pores < 0.6 nm [38]. Key to the performance of these materials is their size specific selectivity. CMS are similar to zeolites in that their porous structures have dimensions sized close to the critical dimensions of small to medium sized molecules, that is, the range between 0.3 and 1 nm. As a result, separations can be made on the basis of differences in molecular sizes and... 

CMS have substantially uniform micropores (3 to 12 A) while ordinary activated carbons have a wide pore size distribution (2 to 2000 A). Narrow pores of CMS favor the diffusion of small molecules, and inhibit penetration of large ones, thus providing a sharp separation as compared to ordinary activated carbons. Another important property of CMS is the slit shaped pore structure which makes them useful for kinetic separation and adsorption equilibrium studies. 

CMS are amorphous materials. Their pore structure below 5 A can not be studied by X-ray diffraction, in contrast to most mineral molecular sieves. Transmission electron microscopy has also not been found suitable for determining such small pore dimensions. The most effective method for characterization is the analysis of adsorption isotherms of small probe molecules with different critical dimensions, viz. O2, N2, CO2, CH4. These adsorption isotherms are useful in determining the pore size distribution, surface area, pore volumes and separation capacity of CMS. In addition, these isotherms give information on the potential industrial applications of these materials, e.g. for the separation of nitrogen from air or of carbon dioxide and methane from flue gases. 

Gas mixture separation processes are based on the specific pore size distribution of CMS, which permits diffusion of different gasses at different rates. These processes aim to either recover and recycle valuable constituents from industrial waste gases, or to separate small gas molecules by preferential adsorption. The latter is at present the most important large scale application of CMS. Separations that have been accomplished include oxygen from nitrogen in air, carbon dioxide from methane in natural gas, ethylene from ethane, linear from branched hydrocarbons (such as n-butane from isobutane), and hydrogen from flue gases [6]. 

Sample molecules that are too large to enter the pores of the support material, which is commercially available in various pore dimensions, are not retained and leave the column first. The required elution volume Ve is correspondingly small. Small molecules are retained most strongly because they can enter all the pores of the support material. Sample molecules of medium size can partly penetrate into the stationary phase and elute according to their depth of penetration into the pores (Fig. 7.3). No specific interactions should take place between the molecules of the dendrimer sample and the stationary phase in GPC since this can impair the efficiency of separation by the exclusion principal. After separation the eluate flows through a concentration-dependent detector (e.g. a UV/VIS detector) interfaced with a computer. One obtains a chromatogram which, to a first approximation, reflects the relative contents of molecules of molar mass M. If macromolecules of suitable molar mass and narrow molar mass distribution are available for calibration of the column, the relative GPC molar mass of the investigated dendrimer can be determined via the calibration function log(M) =f( Vc). 

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