Thin-layer adsorption chromatography with mixed mobile phases. 4. Extension of Ościk's equation to heterogeneous adsorbents

In this paper the equation for thin-layer adsorption chromatography with multicomponent mobile phases, proposed by O?cik in 1965 is extended to energetically heterogeneous solid surfaces. Other forms of this equation, more convenient in practical applications, are presented. Model calculations are made for TLC with binary mobile phases according to the modified form of O?cik's equation. Finally, this equation is compared with that of Snyder.     

Effects of solute-solvent and solvent-solvent association in liquid adsorption chromatography with binary mobile phase

Analytical equations for the capacity ratio in liquid adsorption chromatography with a binary mobile phase, involving solute-solvent and solvent-solvent association in the mobile and surface phases, have been derived. Very simple equations have been obtained for higher values of mole fraction of the more efficient eluting solvent.     

Thin-layer adsorption chromatography with mixed mobile phases. 1. Characterization of chromatographic systems showing energetic heterogeneity of adsorbent surfaces with regard to admolecules of solvents and solutes

Thin-layer adsorption chromatography with a multicomponent mobile phase is discussed. A new equation for predicting R_M-values in TLC with mixed mobile phases using the R_M-ValUeS obtained for pure solvents is proposed. This equation takes into account effects of energetic heterogeneity of the adsorbent surface with regard to adsorbed molecules of solvents and solutes. Experimental verification of this equation is presented for R_M-data obtained by TLC using a binary mobile phase.     

Thin-layer adsorption chromatography with mixed mobile phases. 3. Correlation between parameters characterizing the chromatographic systems with binary and ternary mobile phases

TLC experimental data have been measured for polycyclic hydrocarbons in binary and ternary mobile phases on silica gel. These data have been interpretated using the equation discussed by us in Part 1 of this series [HRC & CC 2 (1979) 236]. The heterogeneity parameter appearing in this equation has been evaluated and compared for different ternary and binary mobile phases.     

Molecular interactions in adsorption liquid chromatography with mixed mobile phase

Summary The equation of Jaroniec was used to describe the molecular interactions in liquid adsorption chromatography with mixed mobile phases. The main object of the investigation was to demonstrate that the type of association in the bulk phase is independent of the nature of the stationary phase, and to examine the influence of the nature and number of components in the mobile phase upon the specific interactions in the system. The relationship between the type of association and the structure of the chromatographed substance was also taken into account.     

Thin-layer adsorption chromatography with mixed mobile phases. 2. Effects of solute-solvent interactions and energetic heterogeneity of surfaces with regard to admolecules in TLC

In the Part 1 of this series a new equation for determining the R_m values in TLC with mixed mobile phases was proposed and examined by using the parameter m, which is a measure of energetic heterogeneity of the adsorbent surface with regard to the adsorbing molecules (admolecules). The numerical values of m, evaluated for 13 chromatographic systems, have been compared with that of the O?cik's parameter A, which characterizes solute-solvent interactions.     

New description of heterogeneity effects in adsorption from multicomponent solutions and liquid adsorption chromatography

General equations describing adsorption from solutions on solids and liquid adsorption chromatography with mixed mobile phases are formulated in terms of the bulk and surface activity coefficeints. Definition of the surface activity coefficients is extended; they describe nonideality of surface solution due to difference in molecular interactions of the components as well as nonideality of this solution generated by the adsorbent heterogeneity. It is shown that the above general equations predict simpler expressions known already in the literature.     

A simple procedure for evaluating the heterogeneity parameter and the ratio of molecular sizes of solute and solvent by using HPLC data

Based on the relationship defining the dependence of the capacity ratio upon the composition of the mobile phase, a simple numerical procedure is proposed for evaluating the heterogeneity parameter and the ratio of molecular sizes of solute and solvent. This procedure is examined by using HPLC data for pesticides chromatographed in isooctane/dichloromethane eluent on Lichrosorb at 291 K.     

Adsorption effects in gel permeation chromatography: The application of binary mobile phases

Summary The influence of the adsorption properties of the column packing on the elution mechanism of macromolecules was investigated. Experimentally determined elution volumes of polystyrene standards in different mobile phases were compared with computed theoretical plots assuming (a) the pure steric exclusion mechanism; (b) mixed steric exclusion and adsorption mechanism.     

Polyacrylate liquid crystalline stationary phases in supercritical fluid chromatography with carbon dioxide mobile phase

Summary New polyacrylate liquid crystalline compounds were coated onto glass or fused-silica capillary columns as stationary phases and applied to supercritical fluid chromatography. These stationary phases, were very stable: no bleeding was observed at 200°C and up to 200kg/cm² pressures of carbon dioxide mobile phase. The wide working range of the capillary column was extended below the g-n transition temperature. Isomeric compounds such as - and -methoxynaphthalene, anthracene and phenanthrene and several phenolic compounds were separated.     

A linear relationship between partition ratio and composition of a binary mobile phase in reversed-phase liquid chromatography using chemically bonded stationary phases

A simple linear relationship which enables the effect of the composition of a binary mobile phase on the retention of a solute to be assessed in reverse phase liquid chromatography using a bonded stationary phase has been derived. The equations have been tested using published experimental data.     

Retention of functional polymers in liquid adsorption chromatography: Effect of the end groups in PEGs and their methyl ethers in different mobile phases

It is shown that the end group parameter, which describes the influence of the end group on retention, can be determined in RP chromatography from two chromatograms of a nonfunctional and a monofunctional sample, if a sufficient number of peaks with the same number of repeat units in each sample can be reasonably resolved and identified. The same procedure can also be applied for pairs of di‐ and monofunctional polymers. End group parameters have been determined in three different mobile phases: acetonitrile–water, acetone–water and methanol–water of different compositions. The temperature dependence of the interaction parameter of the repeat unit and the end group parameter has been found to be different, which allows a fine‐tuning of retention.     

Retention in liquid chromatography with multicomponent mobile phases: Relationship with binary systems

Summary Using the concept of an effective concentration a method is proposed for predicting retention in liquid chromatography with multicomponent mobile phases based on experiments with corresponding binary ones. The method is verified for normal and reversed-phase systems with ternary mobile phases and agrees closely with experimental data.     

Dependence of selectivity and resolution upon composition of the binary mobile phase in LSC

The recently derived general equation for the capacity ratio has been utilized to study the dependence of selectivity and resolution upon mobile phase composition. This equation accounts for differences in molecular size of solutes and solvents, and for the energetic heterogeneity of the adscrbent surface. Model calculations illustrating the influence of these factors on the selectivity and resolution are presented and discussed.     

Fluorocarbon stationary phases for liquid chromatography applications

This article presents an overview on fluorocarbon stationary phases for liquid chromatography (LC) applications. Fluorocarbons developed as alternative reverse phases have revealed previously unknown separation mechanisms and special utilities. Solvophobicity and fluorophilicity of the fluorinated phases provide enhanced selectivity for organofluorine compounds. The dual normal- and reverse-phase characteristics make fluorinated phases suitable for analysis of polar pharmaceutical and biological samples such as proteins, peptides, nucleotides, steroids, and alkaloids. Fluorinated phases for other applications including supercritical fluid chromatography (SFC), micellar electrokinetic liquid chromatography (MEKC), ion chromatography (IC), open tubular electrochromatography (OTEC), and liquid chromatography-mass spectrometry (LC-MS) are also highlighted.     

Influence of solvent strength in possible optimization of adsorption thin-layer chromatography

Considerations of TLC process optimization have been based on the thermodynamic theory of adsorption from multicomponent solvents using experimental and theoretical R_{M1, 2} = f (Φ₁) relationships. It was found that a relationship exists between the A_z parameter (log k where k is the partition coefficient of the substance chromatographed) of the above theory and pK_a values of substances as well as the solubility parameter δ of the mobile phase components. Analysis of the A_z values of substances shows that a slight variation therein is associated with lower selectivity of chromatographic separation.     

Adsorption TLC with binary mobile phases

Summary An equation describing R_M values in TLC with a binary mobile phase has been derived and examined by using TLC data. Two different methods have been proposed to determine the chromatographic parameters characterizing energetic heterogeneity of the adsorption system and solute-solvent interactions. These methods differ in the estimation of the mole fractions of solvents in the surface phase. In method I an analytical equation for evaluating these mole fractions is assumeda priori. Method II utilized the excess adsorption isotherm measured for the mobile phae-adsorbent system.     

Separation of imidacloprid and its degradation products using reversed phase liquid chromatography with water rich mobile phases

Water rich mobile phases in RPLC are not generally used because of the longer retention times involved when organic modifiers such as methanol or acetonitrile are used. The problem of longer retention times can be addressed using hydrophobic alcohols such as pentanol in low quantities (less than 1%) as organic modifiers. The advantages of using these mobile phases in RPLC for the separation of water soluble and weakly retained congeners is demonstrated through the separation of imidacloprid and its degradation products using a 0.4% pentanol in water mobile phase with 0.2% acetic acid.     

Bonded stationary phases for reversed phase liquid chromatography with a water mobile phase: application to subcritical water extraction

Reversed phase high-performance liquid chromatography (RP-HPLC) is demonstrated for hydrophobic analytes such as aromatic hydrocarbons on a chemically bonded stationary phase and a mobile phase consisting of only water. Reversed phase liquid chromatography separations using a water-only mobile phase has been termed WRP-LC for water-only reversed phase LC. Reasonable capacity factors are achieved through the use of a non-porous silica substrate resulting in a chromatographic phase volume ratio much lower than usually found in RP-HPLC. Two types of bonded WRP-LC columns have been developed and applied. A brush phase was synthesized from an organochlorosilane. The other phase, synthesized from an organodichlorosilane, is termed a branch phase and results in a polymeric structure of greater thickness than the brush phase. A baseline separation of a mixture containing benzaldehyde, benzene, toluene, and ethyl benzene in less than 5 min is demonstrated using a water mobile phase with 12 000 plates generated for the unretained benzaldehyde peak. The theoretically predicted minimum reduced plate height is also shown to be approached for the unretained analyte using the brush phase. As an application, subcritical water extraction (SWE) at 200°C is combined with WRP-LC. This combination allows for the extraction of organic compounds from solid matrices immediately followed by liquid chromatographic separation of those extracted compounds all using a solvent of 100% water. We demonstrate SWE/WRP-LC by spiking benzene, ethyl benzene, and naphthalene onto sand then extracting the analytes with SWE followed by chromatographic separation on a WRP column. A sand sample contaminated with gasoline was also analyzed using SWE/WRP-LC. This extraction process also provides kinetic information about the rate of analyte extraction from the sand matrix. Under the conditions employed, analytes were extracted at different rates, providing additional selectivity in addition to the WRP-LC separation.