The efficiency of open tubular gas chromatographic columns

Summary A new parameter, the mean specific plate number, is proposed for assessing the efficiency of support coated open tubular (SCOT) and wall coated open tubular (WCOT) columns and for comparing the efficiency of different open tubular columns. It has the advantage over most previously used parameters in that it has only a small dependence on the partition ratio and it allows for the column diameter.A graphical presentation is given of the maximum theoretical mean specific plate number as a function of the partition ratio for SCOT columns having a range of relative porous layer thicknesses and for WCOT columns with a range of phase ratios.This presentation permits ready visual comparison of the potential efficiency of different columns and enables a simple evaluation of the percentage utilization of theoretical efficiency from experimentally determined values of the maximum mean specific plate number. For a given column the percentage utilization of theoretical efficiency at optimum average gas velocity and that at optimum practical gas velocity or at a higher average gas velocity are shown to be equal provided that corrections for column pressure drop are made.     

The study of catalysis by novel gas chromatographic techniques

Summary Studies of catalytic reactions have been made using differential (sample-vacancy) and stopped-flow gas chromatography. Reactions are often very sensitive to trace materials and in particular it has been necessary to devise a technique for removing oxygen from carrier-gas streams down to very low levels. The techniques and the results are often relevant to the more normal analytical applications of gas chromatography.Presented at Table Ronde sur les mesures physicochimiques par chromatographie en phase gazeuse (Lyons, November 13–14th, 1973), organized by Dr.robin (INSA, Villeurbanne)     

Large diameter open tubular columns in gas chromatographic analysis

Large diameter open tubular columns provide the packed column chromatographer with a simple route to higher resolution gas chromatography. They can be operated in a high-flow (lower resolution) mode that permits their direct substitution for a packed column, or they can be operated in a low-flow (higher resolution) mode that maximizes separation at the cost of longer analysis times. Inlet design and column installation can influence both the chromatographic results and quantiative reliability. Make-up gas is not required in the high-flow mode, and its benefits in the low-flow mode are restricted to enhanced detector sensitivity, provided the outlet end of the column resides in the detector jet (FID). The columns seem fully compatible with all common modes of detection.     

Prediction of gas chromatographic retention indices of polychlorinated dibenzothiophenes on non-polar columns

Polychlorodibenzothiophenes (PCDTs) have been found in several kinds of environmental samples. The lack of reference compounds has meant that very little is known about their gas chromatographic behavior. Here we discuss the retention of 19 authentic PCDTs and their sulfones on the widely used gas chromatographic stationary phases DB-5 and DB-5ms. The retention order is different from that of the polychlorodibenzofurans. The data generated allowed us to carry out a multiple linear regression to generate parameters for predicting the retention indices of unknown congeners based only on their structural features.     

Determination of ion adsorption by radioactive tracer technique

Summary The slight linear decrease of the “per mole of AgI adsorbed amount” (ˉC) of the coagulating ion with the increasing pI at a constant concentration of the coagulating ion was proved and explained by the linear decrease of the specific surface. The adsorbed amount of the coagulating ions at a constant concentration and at a given pI decreases with the increasing concentration in which the AgI precipitate was formed. Ions of different valencies are adsorbed in equivalent amounts which are independent of their concentrations which were higher than their coagulation values. The correctness of the desorption-adsorption formula logc″/c′=(z′−z″ a+ logx/(−x) respectivelyS=c″ (1−x)/c′x= 10(z′−z″)a was confirmed (x the fraction of the adsorbed amount of the ion of valencyz″ and concentrationc″, 1−x the fraction of the adsorbed amount of the ion of valencyz′ and concentration c′,S the selectivity coefficient of ion exchangers). Therefore the coagulated AgI can be considered as an ideal ion exchanger. The constanta in the above formula is equal to the slope of the line “log coagulation value-valency” of theSchulze-Hardy rule.

---

Zusammenfassung Die leicht lineare Abnahme des pro Mol AgJ adsorbierten Betrages (ˉC) der koagulierenden Ionen mit steigendem p^J bei konstanter Konzentration des koagulierenden Ions wurde gezeigt und durch die lineare Abnahme der spez. Oberfl?che erkl?rt. Der adsorbierte Betrag an koagulierenden Ionen bei konstanter Konzentration und gegebenem p^J sinkt mit steigender Konzentration, mit der die AgJ-F?llung erzeugt wird. Ionen verschiedener Wertigkeiten werden in ?quivalenten Betr?gen unabh?ngig von ihren Konzentrationen adsorbiert und sind h?her als ihre Koagulationswerte. Die Richtigkeit der Desorption-Adsorptions-Formel logc″/c′=(z′−z″ a+logx/(−x) bzw.S=c″ (1−x)/c′x= 10(z′−z″)a wurde sichergestellt (x= Bruchteil des adsorbierten Betrages des Ions der Valenzz″ und dessen Konzentrationc″, 1 −x=Bruchteil des adsorbierten Betrages des Ions der Valenzz′ und der Konzentration c′,S=Selektivit?tskoeffizient des Ionenaustauschers). Deshalb kann das koagulierte AgJ als ein idealer Ionenaustauscher betrachtet werden. Die Konstantea in der obigen Formel ist gleich der Neigung der Kurve “log Koagulationswert/Valenz” in derSchulze-Hardy-Regel (2).

---

---

Contribution number 95 from the Department of Physical Chemistry, Faculty of Sciences, University of Zagreb. Partially reported at the I. Yugoslav Congress for Pure and Applied Chemistry, Zagreb, June 1960.     

Thermoanalytical and gas chromatographic properties of the copper(II) complexes of alkyl-substituted Schiff's bases

Summary A study is presented of the thermoanalytical and gas chromatographic (GC) properties of the copper(II) complexes of twenty four tetradenate Schiff's bases. Variations in thermal stability, volatility and GC retention of the complexes are discussed in terms of stereo-electronic effects of the substituents. Although some complexes decomposed extensively during vaporization above 250°C all, apparently, survive chromatography intact at 200°C. Certain complexes were separated as distinct regio-isomers by GC. Fluorinated ligands still appear to be the most suitable derivatizing reagents for Cu(II).     

On-line testing of gas chromatographic columns with a programmable computing integrator

Summary A program is described which calculates the number of effective plates and the coating efficiency over the entire range of a test chromatogram. The peak widths at half height are derived by assuming a Gaussian peak shape. The interpolated peak width at k=4 is used for computing a standardized number of effective plates. Plate height, column permeability, overall performance and a novel parameter called sampling efficiency are calculated from 5 other figures — i. e. carrier gas code, pressure drop, column length, column temperature and particle size.Dedicated to Dr. Leslie S. Ettre for his 60th birthday.     

Prediction of theoretical plate number in isothermal gas chromatographic analysis on capillary columns

A method for the prediction of the efficiency of gas chromatographic analysis in isothermal conditions by using experimental data of 1-alcohols and n-alkanes measured on capillary columns filled with polar and non-polar stationary phases in isothermal and isobaric conditions is described. The theoretical plate height trend indicates the change of separation efficiency as a function of inlet pressure and column temperature. By evaluating the variation of the diffusion coefficients of the analysed compounds into the mobile and stationary phase it is possible to predict the column efficiency and the number of theoretical plates at any temperature.     

Characteristics and performance of gas chromatographic detectors with glass capillary columns

A comparison of the characteristics and Performance of the flame ionization, electron capture, and flame photometric detectors with capillary columns is described. Factors which may affect the limits of detection, linearity, chromatographic peak shape, and other detector performance characteristics are discussed and compared with the results of a model derived for the behavior of concentration and mass flow-rate dependent chromatographic detectors used with capillary GC systems. Examples are given of highly complex and labile mixtures such as pesticide residues and products from coal hydrogenation.     

Preparation and use of packed capillary columns in chromatographic and related techniques

In this paper general considerations related to the various approaches and parameters influencing the preparation of highly efficient and stable capillary columns for use in liquid chromatography and related techniques are presented and the column production process is discussed in some detail. The different packing methods available for delivering a packing material into a capillary column are discussed from a practical viewpoint. Packing with a gas (dry packing), packing with a liquid solvent or a mixture of solvents (slurry packing), packing with supercritical carbon dioxide, electrokinetic packing, and sol-gel packing technologies are introduced and discussed throughout the paper. Practical recommendations for obtaining highly efficient (high plate numbers) and stable capillary packed columns are also addressed and discussed.     

样品前处理技术在气相色谱分析中的应用进展

气相色谱法是当前应用最广泛的分析技术之一。使用气相色谱对复杂基体进行分析时的样品前处理步骤往往繁琐耗时,易引起误差,已成为制约分析效率和准确度提升的关键环节。本文综述了2009-2013年几种主要的样品前处理技术,包括吹扫捕集、固相萃取、固相微萃取、液相微萃取技术以及微波辅助萃取、超声波辅助萃取等场辅助萃取技术在气相色谱分析中的应用研究进展。