Solute retention displacement model

Consequences of the Snyder and Soczewinski model are manifold, and their praetieal importance is very signifieant. The most speetaeular conclusions of this model are (1) a possibility to quantify adsorbents ehromatographic activity and (2) a possibility to dehne and quantify chromatographic polarity of solvents (known as the solvents elution strength). These two conclusions could only be drawn on the assumption as to the displacement mechanism of solute retention. An obvious necessity was to quantify the effect of displacement, which resulted in the following relationship for the thermodynamic equilibrium constant of adsorption, K,, in the case of an active chromatographic adsorbent and of the monocomponent eluent ... 

Retention on these supports is adaquetely described by the adsorption displacement model. Nevertheless, the adsorption sites are delocalized due to the flexible moiety of the ligand, and secondary solvent effects play a significant role. The cyano phase behaves much like a deactivated silica toward nonpolar and moderately polar solutes and solvents. Cyano propyl columns appear to have basic tendencies in chloroform and acidic tendencies in methyl tertiobutyl ether (MTBE)... 

Second, previous tests of the displacement model have focused mainly on its ability to correlate and predict retention data in terms of derived correlational equations. Such correlations are based on various free energy relationships, and it is often found that comparisons of this kind can be insensitive to differences in the underlying physical model. That is, correlations of experimental retention data with theory may appear acceptable, in spite of marked deficiencies of the model. In some cases (e.g.. Ref. 12, sorption versus displacement models), radically different models can even yield the same or similar correlational equations. Here we will further test the proposed model for LSC retention in the following ways (1) application of the model to a wide range of LSC systems, involving major variations in solute, solvent, and adsorbent (2) examination of the various free energy terms that individually contribute to overall retention. 

On balance, the plots of Fig. 21 suggest that calculated values of 0b from the present approach are reasonably close to actual isotherm values. Thus, these isotherm data can be regarded as supporting the present displacement model (and related equations), or at the least, not disproving the model. Whether the present approach can be extended to predict isotherm data with an acceptable accuracy for other purposes (e.g., preparative separations with column overload) remains to be seen. This will require careful studies of the same adsorbent sample, measuring both solvent isotherm data and appropriate solute retention values, with use of the solute retention data to derive solvent parameters for calculations of 6b ... 

Models for the interactions of solutes in adsorption chromatography have been discussed extensively in the literature [7-9]. Only the interactions with silica and alumina will be considered here. However, various modifications to the models for the previous two adsorbents have been applied to modern high-performance columns (e.g., amino-silica and cyano-silica). The interactions in adsorption chromatography can be very complex. The model that has emerged which describes many of the interactions is the displacement model developed by Snyder [1,3,4,7,8], Generally, retention is assumed to occur by a displacement process. For ex-... 

The semiempirical model of adsorption chromatography, analogous to that of Martin and Synge, was established only in the late 1960s by Snyder [3] and Soczewinski [4] independently, and it is often referred to as the displacement model of solute retention. The crucial assumption of this model is that the mechanism of retention consists in competition among the solute and solvent molecules for the active sites of the adsorbent and, hence, in a virtually... 

Retention mechanisms of adsorption chromatography have been extensively studied. There are two popular models for this process. The displacement model, originally proposed by Snyder, treats the distribution of solute between a surface phase, usually assumed to be a monolayer, and a mobile phase as a result of a competitive solute and solvent adsorption. A treatment of this model, including the significance of predictions of solvent strength and selectivity in terms of mobile-phase optimization strategies, has been published by Snyder (81). 

The partition and displacement model considers retention to result from a two step process. The first involves formation of a mixed stationary phase by intercalation of solvent molecules from the mobile phase. The composition of the solvents in the stationary phase is established according to thermodynamic equilibrium and is usually different to the bulk mobile phase composition. Competitive sorption of solvents is modeled as a displacement process and is complete before the solute is introduced into the two-phase system. Solute retention is then modeled as a partition process between the solvent modified stationary phase and the mobile phase by taking into account all solute-solvent interactions in both phases. The phenomenological model of solvent effects attempts to model retention as a combination of solute-solvent interactions (the solvation effect) and solvent-solvent interactions (the general medium... 

Fig. 6.1. Schematic illustration of the displacement model. Retention is determined by the displacement of a mobile phase molecule (M), by a solute molecule (S), from a binding site on the stationary phase ( ). Adapted from Snyder and Poppe (1980), with...

Both of these models attempt to explain the relationship between solute retention and the polarity of the mobile phase. An independent study of mixed solvent theory has supported the sorption model (McCann et al., 1982) whereas another study on the effects of solvent composition on the chromatography of alkylphenols and naphthols shows evidence in favour of the displacement model (Hurtubise et al.,... 

Polar-bonded stationary phases, such as cyanopropyl, diol, or aminopropyl, bonded to a silica matrix, have moderate polarity and can be used in normal- and reversed-phase (RP) systems. The retention behavior of heterocyclic bases was also examined using these adsorbents by determination of Rm (log k) values of solutes by the use of eluents with various modifier concentrations.It was statistically found that the Snyder-Soczewihski equation and Scott theory describe the retention of quinolines on polar-bonded stationary phases in normal-phase systems sufficiently well. It seems that results are consistent with a displacement model. The dispersive interactions between solute molecules and the polar component of an eluent seem also to have an important role. Similarly, the retention—... 

In its simplest form the competition model assumes the entire adsorbent surface is covered by a monolayer of solute and mobile phase molecules. Under normal chromatographic conditions, the concentration of sample molecules will be small and the adsorbed monolayer will consist mainly of mobile phase molecules. Retention of a solute molecule occurs by displacing a roughly equivalent volume of mobile phase molecules from the monolayer to make the surface accessible to the adsorbed solute aiolecule. For elution of the solute to occur -the above process must be reversible, and can be represented by the equilibrium depicted by equation (4.6)... 

The competition model and solvent interaction model were at one time heatedly debated but current thinking maintains that under defined r iitions the two theories are equivalent, however, it is impossible to distinguish between then on the basis of experimental retention data alone [231,249]. Based on the measurement of solute and solvent activity coefficients it was concluded that both models operate alternately. At higher solvent B concentrations, the competition effect diminishes, since under these conditions the solute molecule can enter the Interfacial layer without displacing solvent molecules. The competition model, in its expanded form, is more general, and can be used to derive the principal results of the solvent interaction model as a special case. In essence, it seems that the end result is the same, only the tenet that surface adsorption or solvent association are the dominant retention interactions remain at variance. 

The competition model of Snyder assumes that the adso tion surface is completely covered by adsorbed eluent molecules forming a mono-layer. When solute molecules are adsorbed they displace olvent molecules. Due to the size differences one or more eluent mofecules are displaced by the solute molecules. The adsorbent surface is ijissumed to be homogeneous and each molecule tends to interact totally wRh the surface, i.e., it is adsorbed flatwise. Thus, the adsorbent surface area that the molecules require can be calculated from their molecular dimensions. Neglecting the interactions between solute and eluent molecules in the liquid and the adsorbed phase, the retention of an adsorbed molecule (expressed as net retention volume per unit weight of adsorbent K) can be related to the properties of the stationary phase, the eluent, and the sample by... 

From the Snyder-Soczewinski model (12, 13), the entire adsorbent surface is covered by an adsorbate monolayer that consists of mobile phase. Retention is assumed to occur as a displacement process in which an adsorbing solute molecule X displaces some number n of previously adsorbed mobile-phase molecules S... 

Snyder [350] has given an early description and interpretation of the behaviour of LSC systems. He explained retention on the basis of the so-called competition model . In this model it is assumed that the solid surface is covered with mobile phase molecules and that solute molecules will have to compete with the molecules in this adsorbed layer to (temporarily) occupy an adsorption site. Solvents which show a strong adsorption to the surface are hard to displace and hence are strong solvents , which give rise to low retention times. On the other hand, solvents that show weak interactions with the stationary surface can easily be replaced and act as weak solvents . Clearly, it is the difference between the affinity of the mobile phase and that of the solute for the stationary phase that determines retention in LSC according to the competition model. 

In an effort to describe effluent results obtained from the different soil layers, we utilized various versions of the multireaction model described above. In principle, we based our efforts on the assumption of the miscible displacement approach that describes retention reactions of solutes during transport in porous media (Selim, 1992). Several simplifying assumptions were necessary in order to describe the S04 experimental data based on these models. Briefly, we tested the capability of the convection-dispersion (CD) equation to describe the mobility of applied sulfates in individual soil layers where steady-state conditions were assumed. 

The various aspects of displacement and localization are now well understood, and predictions of their effects on retention in LSC can be made with some confidence. Hydrogen bonding between solute and solvent molecules requires further investigation, and it is likely that such studies will contribute to our understanding of hydrogen bonding in solution as well. On the basis of the present model it should prove possible to systematically explore new stationary phase compositions for unique separation potential. However, this subject falls outside the area of mobile-phase effects per se, and will be reserved for another time. 

In contrast, the Scott-Kucera model considers a solvent system composed of an apolar solvent A and a polar solvent B (Scott and Kucera, 1975). When this mixture is pumped through a column, a monolayer of the most polar solvent B is formed by adsorption of B on the adsorbent. Sample molecules are adsorbed on this monolayer instead of on the adsorbent surface. In other words, there is no displacement of adsorbed solvent molecules, and interaction between the molecules of the monolayer and the sample molecules determines the retention of the component. This theory has been adapted by saying that the model is only valid for medium polar mobile phases and solutes with a polarity lower than the most polar solvent in the eluent. These medium polar solvents are called hydrogen-bonding solvents (esters, ethers, ketones). A monolayer of these solvents behaves as a hydrogen-bonding phase. Inter-... 

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