Preferential sorption

Reverse osmosis models can be divided into three types irreversible thermodynamics models, such as Kedem-Katchalsky and Spiegler-Kedem models nonporous or homogeneous membrane models, such as the solution—diffusion (SD), solution—diffusion—imperfection, and extended solution—diffusion models and pore models, such as the finely porous, preferential sorption—capillary flow, and surface force—pore flow models. Charged RO membrane theories can be used to describe nanofiltration membranes, which are often negatively charged. Models such as Dorman exclusion and the... 

This assumption is implicitly present not only in the traditional theory of the free-radical copolymerization [41,43,44], but in its subsequent extensions based on more complicated models than the ideal one. The best known are two types of such models. To the first of them the models belong wherein the reactivity of the active center of a macroradical is controlled not only by the type of its ultimate unit but also by the types of penultimate [45] and even penpenultimate [46] monomeric units. The kinetic models of the second type describe systems in which the formation of complexes occurs between the components of a reaction system that results in the alteration of their reactivity [47-50]. Essentially, all the refinements of the theory of radical copolymerization connected with the models mentioned above are used to reduce exclusively to a more sophisticated account of the kinetics and mechanism of a macroradical propagation, leaving out of consideration accompanying physical factors. The most important among them is the phenomenon of preferential sorption of monomers to the active center of a growing polymer chain. A quantitative theory taking into consideration this physical factor was advanced in paper [51]. 

It was in article [52] where the main reason responsible for the above-mentioned peculiarities was explicitly formulated and substantiated. Its authors related these peculiarities with partitioning of monomer molecules between the bulk of a reaction mixture and the domain of a growing polymer radical. This phenomenon induced by preferential sorption of one of the monomers in such a domain is known as the bootstrap effect. This term was introduced by Harwood [53], because when growing a polymer radical can control under certain conditions its own microenvironment. This original concept enabled him to interpret many interesting features peculiar to this phenomenon. Particularly, he managed to qualitatively explain the similarity of the sequence distribution in copolymerization products of the same composition prepared in different solvents under noticeable discrepancies in composition of monomer mixtures. 

The main peculiarities of the preferential sorption phenomenon have been experimentally examined in detail in a series of papers by Semchikov, Smirnova et al. [61-76]. Investigating the free-radical copolymerization in bulk of about 30 concrete pairs of the most commonly encountered vinyl monomers, they revealed the following characteristic features of this phenomenon ... 

The n-PrOH concentration in the permeate and the normalized permeation rate increased with the increasing CD content in the CD/PVA membrane. The addition of CD in the PVA membrane determined the increasing of the swelling degree and preferential sorption of n-PrOH and p-xylene, due to the fact that the affinity of CD for these isomers was stronger than that for i-PrOH and o-xylene respectively [84],... 

Tharayil, N., Bhowmik, P.C., and Xing, B. Preferential sorption of phenolic phytotoxins to soil implications for altering the availability of allelochemicals, J. Agric. Food Chem., 54(8) 3033-3040, 2006. 

Figure 1. Schematic of preferential sorption-capillary flow mechanism for reverse-osmosis separations of sodium chloride from aqueous solutions...

According to the above mechanism, reverse osmosis separation is governed by two distinct factors, namely (i) an equilibrium effect which is concerned with the details of preferential sorption in the vicinity of the membrane surface, and (ii) a kinetic effect which is concerned with the mobilities of solute and solvent through membrane pores. While the former (equilibrium effect) is governed by repulsive and attractive potential gradients in the vicinity of the membrane surface, the latter (mobility effect) is governed both by the potential gradients (equilibrium effect) and the steric effects associated with the structure and size of molecules relative to those of pores on the membrane surface. 

The preferential sorption-capillary flow mechanism of reverse osmosis does that. In the NaCl-H20-cellulose acetate membrane system, water is preferentially sorbed at the membrane-solution Interface due to electrostatic repulsion of ions in the vicinity of materials of low dielectric constant (13) and also due to the polar character of the cellulose acetate membrane material. In the p-chlorophenol-water-cellulose acetate membrane system, solute is preferentially sorbed at the interface due to higher acidity (proton donating ability) of p-chlorophenol compared to that of water and the net proton acceptor (basic) character of the polar part of cellulose acetate membrane material. In the benzene-water-cellulose acetate membrane, and cumene-water-cellulose acetate membrane systems, again solute is preferentially sorbed at the interface due to nonpolar... 

Preferential Sorption at Membrane-Solution Interfaces and Solute Separation In Reverse Osmosis... 

While details of preferential sorption represent mainly the... 

With particular reference to reverse osmosis systems involving cellulose acetate membranes and aqueous solutions, the membrane material has both polar and nonpolar character, and the solvent, of course, is polar. When these two components of the reverse osmosis system are kept constant, preferential sorption at the membrane-solution interface, and, in turn, solute separation in reverse osmosis, may be expected to be controlled by the chemical nature of the solute. If the latter can be expressed by appropriate quantitative physicochemical parameters representing polar-, steric-, nonpolar-, and/or ionic-character of the solutes, then one can expect unique correlations to exist between such parameters and reverse osmosis data on solute separations for each membrane. Experimental results confirm that such is indeed the case (18). 

Gibbs adsorption equation is an expression of the natural phenomenon that surface forces can give rise to concentration gradients at Interfaces. Such concentration gradient at a membrane-solution Interface constitutes preferential sorption of one of the constituents of the solution at the interface. By letting the preferentially sorbed Interfacial fluid under the Influence of surface forces, flow out under pressure through suitably created pores in an appropriate membrane material, a new and versatile physicochemical separation process unfolds itself. That was how "reverse osmosis" was conceived in 1956. 

Certain SEC applications solicit specific experimental conditions. The most common reason is the limited sample solubility. In this case, special solvents or increased temperature are inavoid-able. A possibility to improve sample solubility and quality of eluent offer multicomponent solvents (Sections 16.2.2 and 16.8.2). The selectivity of polymer separation by SEC drops with the deteriorating eluent quality due to decreasing differences in the hydrodynamic volume of macromolecules with different molar masses. The system peaks appear on the chromatograms obtained with mixed eluents due to preferential solvation of sample molecules (Sections 16.3.2 and 16.3.3). The multicomponent eluents may create system peaks also as a result of the (preferential) sorption of their components within column packing [144,145]. The extent of preferential sorption is often sensitive toward pressure variations [69,70,146-149]. Even if the specific detectors are used, which do not see the eluent composition changes, it is necessary to discriminate the bulk sample solvent from the SEC separated macromolecules otherwise the determined molecular characteristics can be affected. This is especially important if the analyzed polymer contains a tail of fractions possessing lower molar masses (Sections 16.4.4 and 16.4.5). 

Both radial and axial temperature gradients may appear. As shown is Section 16.3.5, adsorption of polymers depends on temperature. Given the temperature and pressure dependence of the preferential sorption of the mixed eluent components within column packing [146-149], one can expect also considerable changes in the column interactivity with the temperature and pressure variations that may result in a possible gradual departure from the critical conditions. 

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