Novel inverse liquid chromatography detector configuration for studying solid-liquid adsorption

Inverse liquid chromatography (ILC) is a physicochemical chromatographic technique for studying solid-liquid interactions and surface properties of unknown solid materials. However, such studies are dependent on the ability to self pack the sample powder into a LC column in a reliable and robust manner. In practise, this is often difficult and anomalous chromatograms can be encountered quite frequently. Results obtained with a novel LC system configuration utilising both pre and post-column UV-vis detectors for ILC studies are reported here which greatly assist in our attempts to interpret such chromatograms. The operational issues for using a two detector system are discussed including the use of both detectors in the linear concentration regime; with the choice of an optimal detector wavelength being the most critical factor. The two detector system was demonstrated to be capable of verifying reversible adsorption processes, as well as assisting in the interpretation of complex or problematic chromatograms. This paper demonstrates that the two detector ILC system can offer a number of practical benefits in the study of complex chromatographic phenomena.     

Accurate and rapid estimation of adsorption isotherms in liquid chromatography using the inverse method on plateaus

The inverse method (IM) is an attractive approach for estimating adsorption isotherm parameters in liquid chromatography (LC), mainly due to its experimental simplicity and low sample consumption. This article presents a new experimental approach, the inverse method on plateaus (IMP), which uses elution profiles on concentration plateaus together with IM. This approach enabled us to obtain very accurate adsorption isotherms that agreed well with those estimated by means of frontal analysis over the entire concentration range under consideration. IMP is recommended when accurate adsorption isotherm estimates are required, and standard IM is insufficient.     

Experimental adsorption isotherms based on inverse gas chromatography

A new chromatographic perturbation method is used for studying the adsorption-desorption equilibrium in various gas-solid heterogeneous systems. It is the reversed-flow method giving accurate and precise values of many physicochemical constants including the basic and necessary adsorption isotherm values. For four inorganic oxides, namely, Cr2O3, Fe2O3, TiO2 and PbO, and two aromatic hydrocarbons (benzene, toluene) these adsorption isotherms have been determined through a non-linear model.     

Fitting adsorption isotherms to the distribution data determined using packed micro-columns for high-performance liquid chromatography

Knowing the adsorption isotherms of the components of a mixture on the chromatographic system used to separate them is necessary for a better understanding of the separation process and for the optimization of the production rate and costs in preparative high-performance liquid chromatography (HPLC). Currently, adsorption isotherms are usually measured by frontal analysis, using conventional analytical columns. Unfortunately, this approach requires relatively large quantities of pure compounds, and hence is expensive, especially in the case of pure enantiomers. In this work, we investigated the possible use of packed micro-bore and capillary HPLC columns for the determination of adsorption isotherms of benzophenone, o-cresol and phenol in reversed-phase systems and of the enantiomers of mandelic acid on a Teicoplanin chiral stationary phase. We found a reasonable agreement between the isotherm coefficients of the model compounds determined on micro-columns and on conventional analytical columns packed with the same material. Both frontal analysis and perturbation techniques could be used for this determination. The consumption of pure compounds needed to determine the isotherms decreases proportionally to the second power of the decrease in the column inner diameter, i.e. 10 times for a micro-bore column (1 mm I.D.) and 100 times for capillary columns (0.32 mm I.D.) with respect to 3.3 mm I.D. conventional columns.     

Improved method for determining binary adsorption isotherms by using concentration pulse chromatography: adsorption of CO2 and N2 by silicalite at different pressures

Adsorption separation of carbon dioxide from nitrogen at different system total pressures with silicalite as the adsorbent was studied by using concentration pulse chromatography. Improving the methodology for determining binary adsorption isotherms by concentration pulse method (CPM) was also the goal of this study. Binary adsorption isotherms, x–y phase diagrams and separation factor plots have been determined at 26 °C to look at the influence of pressure on the separation using concentration pulse chromatography. Available methods for determining binary adsorption isotherms using CPM have been reviewed and shown to be incapable of interpreting this particular binary system. An improved novel model has been proposed to interpret the data in this study. It has been referred to as the Kennedy-Tezel concentration pulse method (KT-CPM) and has been shown to be superior to other methods used in the literature. Results using this data were found to be consistent with the previous results in the literature. The binary isotherms for the CO₂–N₂ system show a decrease in CO₂ selectivity as total system pressure increases. The optimal separation factor for silicalite was found to increase with decreasing system pressure and decreasing mole fraction of CO₂ in the feed mixture.     

Penetration isotherms of binary mobile phases for liquid chromatography

Penetration isotherms ψ of eight binary solvent systems used as mobile phases in liquid chromatography are calculated. Dependences of penetrability coefficients of binary mixtures on the volume fraction of the more active solvent are described using modified polynomial functions, in which some empirical coefficients are changed for penetrability coefficients of pure solvents.     

Density isotherms of binary solvents hexane-modifier for liquid chromatography

Isothermic dependences of density of binary mobile phases on volume fraction of modifiers for normal-phase liquid chromatography are studied by the example of hexane-modifier systems (dioxane, diethyl ester, ethyl acetate). The influence of temperature on density and deviations of density of mobile phases from additivity are discussed.     

Optimisation and comparison of several microextraction/methylation methods for determining haloacetic acids in water using gas chromatography

This article presents the different modes and configurations of liquid-phase microextraction (LPME) through comparison with headspace solid-phase microextraction (HS-SPME) for the simultaneous extraction/methylation of the nine haloacetic acids (HAAs) found in water. This is the first analytical case reported of solvent bar extraction–preconcentration–derivatisation assisted by an ion-pairing transfer for HAAs. In this method, 5 μL of the organic extractant, decane, was confined within a hollow-fibre membrane that was placed in a stirred aqueous sample containing the derivatising reagents (dimethylsulphate with a tetrabutylammonium salt). With heating at 45 °C in the HS-SPME method, some organic solvents (extractant, excess of derivatising reagent) are also volatilised and compete with the esters on the fibre (the fibre is damaged and it can be reused only 50−60 times). In addition, the HS-SPME method provides inadequate sensitivity (limits of detections between 0.3 and 5 μg/L) to quantify HAAs at the level usually found in drinking waters. Alternative headspace LPME methods for HAAs require heating (45 °C, 25 min) to derivatise and volatilise the esters but, by using solvent bar microextraction (SBME), the extraction/methylation takes place at room temperature without degradation of HAAs to trihalomethanes. Adequate precision (relative standard deviation of approximately 8%), linearity (0.1–500 μg/L) and sensitivity (10 times higher than the HS-SPME alternative) indicate that the SBME method can be a candidate for routine determination of HAAs in tap water. Finally, the SBME method was applied for the analysis of HAAs in tap and swimming pool water and the results were compared with those of a previous validated headspace gas chromatography–mass spectrometry method.      

Study of adsorption from solutions by frontal chromatography

Summary The automatic frontal chromatography installation was described. By this chromatographic method the adsorption isotherm of benzene from n-heptane solutions on hydroxylated surface of silica with various porosity has been determined. This investigation was performed at different flow rates of eluent and in a wide range of concentrations. The isotherm of adsorption obtained by this chromatographic method has been compared with the results of the static measurements. The coincidence of adsorption isotherms measured at the various flow rates are shown to be a criterion of proximity the chromatographic process to the equilibrium.     

Effectiveness of the H-root method for determining adsorption isotherms of protein-salt systems in open micro-channels

The application of the H-root method (HRM) for predicting isotherm data for protein-salt systems in open-channel chromatographs is presented. HRM mainly consists of performing a regression of the chromatographic response of a system in order to predict the isotherms of the solutes. The method is applicable to proteins with Type I (Langmuir) isotherms. HRM enables a quick determination of the effects of salt on protein isotherms, to facilitate the development of preparative separation protocols of trace proteins in open micro-channel systems. Two configurations were investigated: micro open parallel plate system (microOPPS) and micro open tubular system (microOTS). The effectiveness of HRM was evaluated by simulating the behavior of these open-channel systems with mass-transfer effects included. The influence of operating and geometrical parameters was determined with a detailed parametric study. It was found that HRM can give good estimates of the adsorption isotherms in both micro-channel systems. This is primarily attributed to efficient mass transfer, which ensured correspondence to the equilibrium assumption of HRM. In general, the microOTS was found to give more accurate predictions than the microOPPS. This is attributed to the smooth circular perimeter of flow. Nevertheless, the difference in accuracy is generally insignificant, and with the proper selection of operating conditions, both systems are well suited for HRM.     

Effect of column material on sorption isotherms obtained by inverse gas chromatography

The dependence of sucrose sorption isotherm data obtained by inverse gas chromatography on column material was studied. Columns made of polyamide glass, copper and stainless steel were used. The results obtained indicate that the interaction between water vapour and the column wall cannot be ignored when products with very low equilibrium moisture content are considered.     

吸附等温线的插值方法的研究

关于用函数形式确切地描述吸附等温线已有不少研究.沈中和等认为,难于找到适合各种形状吸附等温线的理想函数形式,建议采用线性插值.但线性插值显然会使计算结果带来额外偏差.Buchner等和Zingales等曾提出用函数平滑或拟合整个吸附等温线,但此法受所选函数形式的限制并存在拟合误差,无法如实描绘某些吸附等     

Enthalpy of adsorption for hydrocarbons on concrete by inverse gas chromatography

Enthalpies of adsorption, ΔH(a), are reported for several light hydrocarbons on normal construction concrete. ΔH(a), which are a measure of the adhesion strength of a molecule on a surface, were determined by gas-solid chromatography with a packed column containing 60-80 mesh concrete particles. With this approach, the specific retention volume for a compound is measured as a function of temperature, and these data are used to calculate ΔH(a). For the hydrocarbons studied, we found that ΔH(a) was relatively large for unsaturated hydrocarbons. These are the first determinations of ΔH(a) of hydrocarbons on construction concrete, but useful comparisons with other ionic solids such as clays can be made.     

Characterization of soil particle surfaces using adsorption excess isotherms

Measurement of adsorption excess isotherms of methanol-benzene mixtures was applied to the characterization of soil particle surfaces. The sorption capacity and Gibbs energy of sorption of the solid-liquid interface were determined for montmorillonite, three types of soil, and their humin fractions. The soils were found to be less polar or less hydrophilic than the clay, and the humin fraction of soils was found to be less hydrophilic than the whole soils. The soil and humin samples have heterogeneous surfaces which can be divided in two regions on the basis of their relative polarity. The x-axis intersection of the straight section of isotherm assigns the relative proportions of the hydrophilic and hydrophobic regions of the surface.     

A comparison of two test methods for determining elastomer physical properties

Accurate values of Poisson's ratio for elastomers are necessary, for example, in the stress analysis of rubber components. Poisson's ratio may be expressed in terms of the elastic and bulk moduli of the elastomer. It is shown that errors in Poisson's ratio are small even though errors in experimental values of these moduli can be large.Two methods of measuring the moduli of elastiomers are described. Samples of nominally the same compounding formulation were tested by both methods and the results compared. Sources of error are discussed and comments made regarding the handling of the two experimental facilities.