Pore size determination chromatography

Molecular probes have already been used to characterize nanoporous materials, in term of pore size determination (gas adsorption) or surface chemistry investigation (use of polar probe molecules) [5]. In this paper, we describe a new methodology based on liquid chromatography in order to characterize the two kinds of mesopores discussed above. The results obtained so far on a highly dealuminated (Y, Zeolyst CBV780) and non-dealuminated (Y, Zeolyst CBV300) zeolites are reported. 

Gel filtration chromatography has been extensively used to determine pore-size distributions of polymeric gels (in particle form). These models generally do not consider details of the shape of the pores, but rather they may consider a distribution of effective average pore sizes. Rodbard [326,327] reviews the various models for pore-size distributions. These include the uniform-pore models of Porath, Squire, and Ostrowski discussed earlier, the Gaussian pore distribution and its approximation developed by Ackers and Henn [3,155,156], the log-normal distribution, and the logistic distribution. 

The effects of various pore-size distributions, including Gaussian, rectangular distributions, and continuous power-law, coupled with an assumption of cylindrical pores and mass transfer resistance on chromatographic behavior, have been developed by Goto and McCoy [139]. This study utilized the method of moments to determine the effects of the various distributions on mean retention and band spreading in size exclusion chromatography. 

At end, it is important to mention that calcium pectate gel beads were compared with calcium alginates gel beads for all entrapment uses [65, 66] in this work, the authors determined the pore size of the beads by size exclusion chromatography using dextran standards and other solutes. 

The ideal packing should be relatively large in diameter, 80-100 nm, and be available with a pore size range from 500 to 10,000 A. The ores should be uniform in size distribution and shallow to reduce diffusion times. Improvements of this type will lead to the use of size exclusion chromatography for particle size determinations in the routine manner in which it is now employed for molecular weight determinations. 

Molecular sieves (zeolites) are artificially prepared aluminosilicates of alXali metals. The most common types for gas chromatography are molecular sieve 5A, a calcium aluminosilicate with an effective pore diameter of 0.5 nm, and molecular sieve 13X, a sodium aluminosilicate with an effective pore diameter of 1 nm. The molecular sieves have a tunnel-liXe pore structure with the pore size being dependent on the geometrical structure of the zeolite and the size of the cation. The pores are essentially microporous as the cross-sectional diameter of the channels is of similar dimensions to those of small molecules. This also contrilsutes to the enormous surface area of these materials. Two features primarily govern retention on molecular sieves. The size of the analyte idiich determines whether it can enter the porous... 

The size-exclusion chromatography (or gel-chromatography) is a means of separation which is exclusively dependent on the exchange of solute molecules between the solvent of the mobile-phase and the same solvent within the pores of the column-packing material. In reality, it is the pore-size-range of the packing material that solely determines the molecular-size-range within which a particular separation can take place effectively. 

The efficiency of fractionation by gel chromatography not only depends on the type of gel but also on the dimensions of the column. The internal volume V, of the gel pores is determined by the amount of dry resin used and by its swellability, which in turn depends upon the eluting agent. The total volume of the gel bed V, is thus made up of the volume of the gel framework, the internal volume V, of the gel, and the external volume Vq between the gel particles. The external volume Vq is identical with the elution volume of a substance with a molecular weight above the exclusion limit. Macromolecules of this size cannot penetrate the network but pass through the column unimpeded. Vq can thus be readily determined. 

ISEC, which was introduced by Halasz and Martin in 1978 [119], represents a simple and fast method for the determination of the pore volnme, the pore size distribution profile, and the spe-cihc snrface area of porous solids. Generally, ISEC is based on the principle of SEC. SEC, also referred to as gel permeation or gel filtration chromatography, is a noninteractive chromatographic method that separates analytes according to their size by employing a stationary phase that exhibits a well-dehned pore distribution. 

The factors that control separation and dispersion are quite different. The relative separation of two solutes is solely dependent on the nature and magnitude of the Interactions between each solute and the two phases. Thus, the relative movement of each solute band would appear to be Independent of column dimensions or particle geometry and be determined only by the choice of the stationary phase and the mobile phase. However, there is a caveat to this statement. It assumes that any exclusion properties of the stationary phase are not included in the term particle geometry. The pore size of the packing material can control retention directly and exclusively, as in exclusion chromatography or, indirectly, by controlling the access of the solute to the stationary phase in normal and reverse phase chromatography. As all stationary phases based on silica gel exhibit some exclusion properties, the ideal situation where the selective retention of two solutes is solely controlled by phase interactions is rarely met in practice. If the molecular size of the solutes differ, then the exclusion properties of the silica gel will always play some part in solute retention. 

We have tried to explain the general principles of the chromatography at critical conditions applicable not only to functionality determination. In order to analyse the herterogeneities in macromolecules, it is necessary to take into account not only the relationships between the macromolecule size and the pore size of the stationary phase, but also the energy of the interaction of the molecule with the adsorbent. 

A more modern method to determine the MMD is GPC, gel permeation chromatography, also named size-exclusion chromatography, SEC. A polymer solution is passed over a column with a porous structure. The residence time of the chains on the column depends on the diameter of the coiled chain smaller chains can migrate through more pores (they can also enter into the smaller ones), and it takes a longer time for them to pass along the column. The bigger ones cannot enter into any of the side-pores and pass in the shortest time. 

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