Determination of single component isotherms and affinity energy distribution by chromatography

Adsorption isotherm data were acquired by frontal analysis (FA) and large sample-size band profiles were recorded for phenol and caffeine. For both compounds, the isotherm data fit well to the Langmuir, Toth, and Bi-Langmuir models of adsorption. The Langmuir model must be dismissed because it does not predict accurately the overloaded band profiles. However, profiles calculated using the unimodal Toth and the bimodal Bi-Langmuir models are indistinguishable. The expectation-maximization procedure was used to calculate directly the affinity energy distribution (AED) from the raw FA data points. For both compounds, the AED converges to a bimodal distribution at high numbers of iterations. This result, which shows the high sensitivity of the EM method, suggest that the Bi-Langmuir model makes better physical sense than the Toth model. This model also permits a detailed investigation of the properties of active sites, a feature often evoked in chromatography but so far rarely the topic of a quantitative investigation.     

Sol-gel multicapillary columns for gas-solid chromatography

In this work, we report the method for the preparation of multicapillary columns (MCCs) for gas-solid chromatography. The porous layer adsorbent is formed on capillary walls by the hydrolysis of aluminum alkoxide in the presence of polypropylene glycol (PPG) and HCl. Porosity and selectivity of the adsorbent depend on reaction conditions and the concentration of PPG. Sol-gel MCCs are well suited for high-speed chromatographic analysis of light hydrocarbons by gas-solid chromatography. Nine-component mixtures of C1-C4 hydrocarbons are separated within 8-12 s. The efficiency of 25-30 cm long alumina sol-gel MCCs consisting of approximately 1400 capillaries of 40 microm diameter is up to 2500-3000 theoretical plates.     

Preparative gas-solid adsorption chromatography. Part II. Selection of optimal conditions for separation in preparative chromatography

Summary The paper discusses the effects of the flow rate and the nature of the carrier gas, and the value of the Henry temperature coefficient on the capacity and effciency of preparative gas-solid adsorption columns.The theoretical relationship between the height equivalent of a theoretical plate (HETP) and the experimental parameters under overloaded conditions was obtained byDe Wet andPretorius [1] and somewhat modified by us [2]. Although it was derived under the assumption that the sorption isotherm is linear, the equation was shown to be in qualitative agreement with the experimental results when the separation took place in a partition column.Consequently we investigated the applicability of this equation for separation on gas-solid adsorption columns containing modified silica, further the optimum characteristics of the adsorbents and the optimal separation conditions. The dependence of the capacity on the separation conditions, theoretically derived by us in an earlier paper [3] has also been studied.

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Präparative Adsorptions-Fest-Gas-Chromatographie. Teil II: Wahl der optimalen Trennbedingungen in der präparativen Chromatographie

Zusammenfassung Die Arbeit befaßt sich mit der Wirkung von Strömungsgeschwindigkeit und Art des Trägergases, sowie mit dem Wert des Temperatur-Koeffizienten nach Henry auf die Kapazität und Wirksamkeit von Adsorptionssäulen für die präparative Fest-Gas-Chromatographie. Die theoretische Beziehung zwischen Bodenzahl (HETP) und Versuchsbedingungen bei Überladung wurde vonDe Wet undPretorius [1] emittelt und von uns etwas abgewandelt [2]. Obwohl sie unter der Voraussetzung einer linearen Adsorptionsisotherme abgeleitet wurde, zeigte die Gleichung gute Übereinstimmungmit den experimentell erhaltenen Ergebnissen bei der Trennung in einer Verteilungssäule. Daraufhin untersuchten wir die Anwendbarkeit dieser Gleichung für Trennungen auf Adsorptionssäulen für die Gas-Fest-Chromatographie, die mit modifiziertem Silicagel gefüllt waren; weiterhin versuchten wir die optimalen Eigenschaften der Adsorbentien und die optimalen Trennbedingungen zu ermitteln. Die Abhängigkeit der Belastbarkeit von den Trennbedingungen, die in einer früheren Arbeit [3] von uns schon theoretisch abgeleitet worden war, wurde ebenfalls untersucht.

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Chromatographie d'adsorption gaz-solide prépartive. 2ème Partie: Sélection des conditions optimales de séparation en chromatographie préparative

Résumé Dans ce travail on étudie les effets de la vitesse, de la nature du gaz vecteur, ainsi que de la valeur du coefficient de température selon Henry, sur la capacité et l'efficacité de colonnes adsorbantes en chromatographie préparative gaz-solide. La relation théorique entre la hauteur équivalente d'un plateau théorique (HETP) et les paramètres expérimentaux, dans des conditions de surcharge, a été établie parDe Wet etPretorius [1] et légèrement modifiée par nous [2]. Bien que cette relation füt obtenue en supposant que l'isotherme d'adsorption est linéaire, on trouve une bonne concordance qualitative avec les résultats expérimentaux de la chromatographie de partage. Par conséquent nous avons étudié la validité de cette équation pour des séparations sur colonnes adsorbantes en chromatographie gaz-solide (silice modifié); en outre nous avons essayé d'établir les caractéristiques optimales des adsorbants et les conditions de séparation optimales. On a étudié la relation existant entre la capacité et les conditions de séparation, en tenant compte des équations théoriques établies par nous dans un travail antérieur [3].

     

Preparative gas-solid adsorption chromatography. Part I. Peak shape and application fields

Summary Modified silica gel is a promising adsorbent for preparative chromatography. The deviation of actual peaks from the theoretical Gaussian peaks have been investigated. The symmetry of the peaks is discussed as a function of the carrier gas velocity. The isolation of a number of hydrocarbons by preparative gas solid adsorption chromatography is described.

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Präparative Adsorptions-Fest-Gas-Chromatographie. Teil I. Peak-Formen und Anwendungsgebiete

Zusammenfassung Modifiziertes Silicagel ist ein vielversprechendes Adsorbens für die präparative Gas-Chromatographie. Die Abweichungen der tatsächlich erhaltenen Peaks von den theoretischen Gauß-Peaks wurden untersucht. Die Symmetrie der Peaks als Funktion der Trägergas-Strömungsgeschwindigkeit wird diskutiert. Die Isolierung einer Anzahl von Kohlenwasserstoffen durch die präparative Adsorptions-Fest-Gas-Chromatographie wird beschrieben.

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Chromatographie d'adsorption gaz-solide préparative. 1ère partie. Forme des pics et champs d'application

Résumé Le gel de silice modifié est un adsorbant prometteur pour la chromatographie préparative. Les différences entre la forme des pics et la courbe théorique de Gauss ont été étudiées. La symétrie des pics est étudiée en fonction de la vitesse du gaz vecteur. On décrit l'isolement d'un certain nombre d'hydrocarbures par chromatographie d'adsorption gaz-solide préparative.

     

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.     

Determination of erythromycin ethylsuccinate by liquid chromatography.

A method is described for the determination of erythromycin ethylsuccinate by liquid chromatography. A C18 reversed-phase column (25 cm x 4.6 mm I.D.) was used with acetonitrile-0.2 M tetrabutylammonium sulphate (pH 6.5)-0.2 M phosphate buffer (pH 6.5)-water [x:5:5:(90-x)] as mobile phase. The proportion of acetonitrile (x) has to be adapted to the type of stationary phase used. For RSil C18 LL, 42.5% was used. The column was heated at 35 degrees C, the flow-rate was 1.5 ml/min and UV detection was performed at 215 nm. The main component, erythromycin A ethylsuccinate, was separated from all other components which were present in commercial samples. The main impurities were erythromycin A and the ethylsuccinate esters of erythromycin B and C. The amide N-ethylsuccinyl-N-demethylerythromycin A was shown to be present in all the samples examined. The method was successfully applied to the analysis of specialities.     

Adsorption isotherms of nonionic surfactants in SBA-15 measured by micro-column chromatography

In this work, micro-column liquid chromatography has been employed for the study of the adsorption of ethylene glucol monoether (C8E4) and pentaethylene glucol monoether (C10E5) nonionic surfactants into the nanopores of SBA-15 silica at two temperatures. The adsorption process for both the surfactants has been investigated in the range of concentration from very dilute solution to "just above" critical micelle concentration (CMC). The adsorption data for both the surfactants are characterized as typical LC-shaped isotherms with plateau near the CMC. A simple two-step adsorption model has been applied to represent an experimental data. An attempt to estimate the thickness of the surfactant layer in the pores, from the experimental data, has been made.     

Heats of adsorption of some organic compounds on beta-cyclodextrin determined by gas-solid chromatography

Isosteric adsorptive enthalpies have been derived from the temperature dependence of retention volumes determined by eluted pulse gas-solid chromatography. The heat data were obtained for systems using more than 20 organic liquids as adsorbates, and beta-cyclodextrin as adsorbent. The experimental results have been discussed in the light of intermolecular force between molecules of adsorbate and adsorbent.     

Analysis of permanent gases by gas-solid chromatography using an ionisation method for detection

A method is described for the analysis of hydrogen, oxygen, nitrogen, methane and carbon monoxide by gas-solid chromatography, using an ionisation method for detection. Accuracies of determination comparable with those of the best katharometers are: attainable, without the need for the high accuracy of flow control or careful thermostatic control associated with katharometers. An ultimate detection level of 0.1 μ1 of s.t.p. gas can be obtained.     

Structure-retention correlations of hydrocarbons in gas-liquid and gas-solid chromatography. Cycloalkenes and cycloalkadienes

Summary The retention indices of cycloalkenes and cycloalkadienes with C₆–C₁₃ rings are determined by gas-liquid chromatography (GLC) on glass capillary columns coated with OV-1 and Ucon LB 550X and by gas-solid chromatography (GSC) on a microcolumn packed with uncoated graphitized thermal carbon black (GTCB). Structure — retention correlations are derived on using index differences such as H^OV, H^GTCB and ΔI values, considering the differences in the stereochemistry of these compounds. It is shown that the combined application of index increments obtained in GLC and GSC provides more detailed structure informations. The value of the retention index units agree with the most stable conformations of the alicyclic compounds. The high value for the energy equivalent to an index unit (ΔG_I.U.=4.18kJ/mol) confirmes that graphitized thermal carbon black causes much stronger dispersive interactions than any nonpolar liquid phase. Dedicated to Prof. Dr. E. sz. Kováts (Ecola Polytechnique Fédérale de Lausanne) on the occasion of his sixtieth birthday.     

Use of high-efficiency packed columns for gas-solid chromatography : V. Micropacked columns

Micropacked columns are constructed using graphitized carbon black as a support for gas-liquid-solid chromatography. Their effectiveness is evaluated in terms of Van Deemter plots, flow-rates, inlet pressure and column capacity. It is shown that such columns, by choosing an appropriate liquid phase, can be used for a wide range of temperatures and types of compound. Analytical applications connected with the analysis of complex organic mixtures in water are discussed. The problems of the analysis of air pollutants are also considered.     

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.