An analysis of coating-efficiency as a measure for capillary column performance

Summary An expression is proposed for the value of the Coating-Efficiency C. E. starting from the Golay-equation, extended to situations of appreciable pressure drop by Giddings. A comparison is made between the coating-efficiency following this theory and the simplified expression for coating-efficiency as generally used in the literature, that neglects the effects of resistance to mass transfer in the liquid phase and the pressure drop. It is shown that the complete equation from the coating-efficiency explains the observations made in practice. Application of the theory described will lead to a better check on film formation in capillary columns.     

Sample introduction in high speed capillary gas chromatography; input band width and detection limits

The speed of analysis in capillary gas chromatography can be substantially increased by reduction of the column inner diameter. However, special demands are then posed upon instrumental design. In particular, the sampling system is highly critical because it has to be capable of delivering extremely small injection band widths which must be compatible with the column inside diameter. This study focuses on the evaluation of two potentially suitable sample introduction systems with respect to input band width and detection limits and their compatibility with small bore (≦ 100 μm) columns in capillary gas chromatography. One of them allows liquid on-column injection, based on liquid splitting, of only a few nl onto small bore (≦ 100 ?m) fused silica columns. For gases, input band widths as low as 1 ms are obtained with this system. The other one is part of a miniaturized gas chromatograph with extremely low dead volume interfaces and detector volumes. It allows input band widths for gases of a few ms. Without any preconcentration ppm concentrations are measured in gaseous samples with a 80 ?m thick film capillary column. It will be shown that a further reduction of the minimum detectable amount and analysis time is possible with this equipment.     

The influence of surface treatments on the electroosmotic flow in micellar electrokinetic capillary chromatography

Summary An investigation was carried out to study the electroosmotic flow (EOF) in micellar electrokinetic capillary chromatography (MECC). Fused silica capillaries were treated with various reagents to investigate the parameters influencing the magnitude and reproducibility of the EOF. The results for untreated and treated columns were collected and compared under the same experimental conditions. Furthermore, experiments with and without sodium dodecylsulfate (SDS) addition to the buffer were carried out to elucidate the influence of this surfactant on the EOF. The mechanisms behind the effects of these modifications on the EOF and the stability of the coatings on the column wall are discussed.     

The effect of column characteristics on the minimum analyte concentration and the minimum detectable amount in capillary gas chromatography

The need for faster and more efficient separations of complex mixtures of organic compounds by gas chromatography has led to the development of small inner diameter open tubular columns. Owing to their decreased plate height, extremely narrow peaks are obtained. When differently sized columns with equal plate numbers are compared, injection of a fixed amount of a solute will give the highest detector signals for the smallest bore columns. When P is defined as the ratio of the column inlet and outlet pressures, it can be seen from theory that under normalized chromatographic conditions the minimum detectable amount (Q_º) for a mass flow sensitive detector increases proportionally to the square of the column diameter for P = 1. In the situation of greater interest in the practice of open tubular gas chromatography where P is large, a linear relationship is derived between Q_º and the column diameter. It is a widespread misunderstanding, however, that narrow bore capillary columns should be used for this reason in trace analysis. If a fixed relative contribution of the injection band width to the overall peak variance is allowed, a decreased plate height drastically restricts the maximum sample volume to be injected. It is shown that the minimum analyte concentration in the injected sample (C_º) is inversely proportional to the column inner diameter when a mass flow sensitive detector is used. For actual concentrations less than C_º, sample preconcentration is required. The effect of peak resolution and selectivity of the stationary phase in relation to C_º and Q_º will be discussed as well. The validity of the given theory is experimentally investigated. Minimum analyte concentrations and minimum detectable amounts are compared using columns with different inner diameter.     

Temperature programmed retention indices: Calculation from isothermal data. Part 1: Theory

Direct conversion of isothermal to temperature programmed indices is not possible. In this work it is shown that linear temperature programmed retention indices can only be calculated from isothermal retention data if the temperature dependence of both the distribution coefficients and the column dead time are taken into account. Procedures are described which allow calculation of retention temperatures and from these, accurate programmed retention indices. Within certain limits the initial oven temperature and programming rate can be chosen freely. The prerequisite for this calculation is the availability of reliable isothermal retention data (retention times, retention factors, relative retention times, or retention indices) at two different temperatures for one column. The use of compiled isothermal retention indices at two different temperatures for the calculation of retention temperatures and thus temperature programmed indices is demonstrated. For the column for which programmed retention indices have to be determined, the isothermal retention times of the n-alkanes and the column dead time as a function of temperature have to be known in addition to the compiled data for a given stationary phase. Once the programmed retention indices have been calculated for a given column the concept allows the calculation of temperature programmed indices for columns with different specifications. The characteristics which can be varied are: column length, column inner diameter, phase-ratio, initial oven temperature, and programming rate.     

Capillary GC Determination of Amines in Aqueous Samples Using Sorptive Preconcentration on Polydimethylsiloxane and Polyacrylate Phases

The use of sorptive extraction/thermal desorption (SE/TD) for the enrichment of amines from aqueous samples was investigated. The amines were derivatized in situ in the water sample by pentafluorobenzoyl chloride and subsequently enriched onto the SE cartridge. Two SE/TD cartridges were used, a commercially available polydimethylsiloxane (PDMS) packed cartridge and a similar cartridge prepared with newly synthesized poly(butyl acrylate) (PBA). Blank profiles of PBA were not as good as those obtained from the PDMS phase. A complex chromatogram was obtained using mass spectrometric detection. Fortunately, the use of a nitrogen-phosphorus detector (NPD) resulted in clean blanks. The PBA phase showed superior performance for the enrichment of the polar amine derivatives from water samples compared to the PDMS material. Using a CGC-NPD set-up and only 1 mL samples, detection limits are in the sub-ppb range.     

On-line coupling of equilibrium-sorptive enrichment to gas chromatography to determine low-molecular-mass pollutants in environmental water samples

On-line combination of equilibrium sorptive enrichment and gas chromatography is used for the analysis of a group of pollutants varying widely in polarity and volatility in aqueous samples at trace levels. For the ESE process open-tubular traps were used. The newly developed hyphenated method shows a high sensitivity for all the compounds under study. The detection limits were typically between 0.1 and 1 microg/l. The sample volumes required for the compounds to reach equilibrium with the stationary phase are in the range of 20 ml for the aromatic hydrocarbons included in the study (benzene, toluene and p-xylene), to 200 ml for epichlorohydrin and dichlorohydrin. Within- and between-day precision of the absolute peak areas varied between 3 and 16%. The performance of the new method was tested by the analysis of different environmental water samples.     

Selective removal of water in purge and cold-trap capmary gas chromatographic analysis of volatile organic traces in aqueous samples

The design and features of an on-line purge and cold-trap pre-concentration device for rapid analysis of volatile organic compounds in aqueous samples are discussed. Excessive water is removed from the purge gas by a condenser or a water permeable membrane in order to avoid blocking of the capillary cold-trap. Synthetic mixtures covering concentrations ranging from tenths to tens of ppb's and different chemical classes are used to study the effect of various process factors on the efficiency and selectivity of water removal as well as on the purging recovery. The importance of the concentration of the solutes, the flow rate in conjunction with the volume of the purge gas, and the temperature of the condenser, the cold-trap and the sample is emphasized. Theoretical models describing the purge process and the blocking of the cold-trap agree fairly well with the highly reproducible experimental results (σ = 2–4%). Both the condenser and the Nafion membrane successfully remove water, although some compounds, dependent on volatility and polarity, are partly or completely lost. It is shown that non-polar volatile organic compounds are efficiently enriched so that recoveries between 80–100% and a detection limit of 1 ppt can be obtained. The applicability of the system is illustrated on some examples.