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  • 1
    Publication Date: 1988-12-01
    Print ISSN: 0009-5893
    Electronic ISSN: 1612-1112
    Topics: Chemistry and Pharmacology
    Published by Springer
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  • 2
    Publication Date: 1988-12-01
    Print ISSN: 0009-5893
    Electronic ISSN: 1612-1112
    Topics: Chemistry and Pharmacology
    Published by Springer
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  • 3
    ISSN: 1612-1112
    Keywords: Capillary gas chromatography ; Al2O3-PLOT columns ; Catalytic activity ; Halocarbons
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Al2O3-PLOT columns are used with great advantage for the analysis of volatiles, because of the increased capacity ratio and selectivity compared to WCOT-columns. Their applicability is limited to relatively non-polar components with relatively low boiling points i. e. eluting before n-decane. In the analysis of the halocarbons in stratospheric air, the decomposition of certain compounds was observed. In this study the stability of a number of volatile organic compounds was determined in function dependence of the column temperature using a two-dimensional GC-system. A possible reaction mechanism for the decomposition is proposed and confirmed for several chlorinated ethanes.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 1612-1112
    Keywords: Capillary gas chromatography ; ECD calibration ; Permeation system ; Halocarbons in stratosphere
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary In part I of this work an analytical procedure was presented for the capillary gas chromatographic determination of volatile hydrocarbons in gases. Here, various quantitative aspects of GC analysis and Electron Capture Detection are emphasized. The performance of several types of capillary columns is studied and a compromise is suggested between column inner diameter, film thickness, stationary phase and oven temperature. The influence of several experimental parameters like pulse voltage, standing current and the detector temperature on the quantitative results of EC detection are discussed. ECD calibration by coulometric detection in the Constant Frequency mode is compared to Constant Current EC detection using gas standards. The gas standards were prepared either by static or dynamic dilution procedures. Accurate and highly reproducible concentrations between ppm's and ppb's were obtained by a newly designed permeation gas system, of which a detailed description is given. The applicability of the total procedure is demonstrated by the quantitative analysis of a series of stratospheric air samples collected at altitudes between 10 and 30 km.
    Type of Medium: Electronic Resource
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  • 5
    ISSN: 0935-6304
    Keywords: Open tubular liquid chromatography ; Instrument band broadening ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In comparison with conventionally packed HPLC columns, from a theoretical point of view, open capillary liquid chromatography (OTLC) systems offer a number of advantages like high plate numbers and short analysis times. On the other hand, drastic changes have to be made to the instrumentation. In particular, the contribution to band broadening by the chromatographic equipment must be considerably reduced. In the present study an OTLC system was developed and evaluated, which yields satisfactory results for 26 μm i. d. columns. The determination of the contribution of the chromatographic equipment to the total band broadening is discussed.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 6
    ISSN: 0935-6304
    Keywords: Capillary gas chromatography ; Detectability ; Thick films ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: For a typical narrow bore (50 μm) and wide bore (320 μm) capillary column the effects of increased stationary phase film thickness (df) on the minimum detectable amount, Qo, as well as on the minimum analyte concentration, Co, are described. In treating the effect of an increased film thickness, two approaches can be followed; either the separation temperature is kept constant, resulting in larger values of the capacity ratio, k, or the column temperature is increased such as to keep k constant. For normalized chromatographic conditions the effects of both approaches on the minimum plate height, optimum carrier gas velocity, and required plate number are described, finally yielding expressions for Qo and Co for both mass flow and concentration sensitive detectors. At constant temperature, Co always increases with the film thickness for mass flow sensitive detectors (e.g. FID). Wide bore thin film columns offer the lowest value of Co attainable. For concentration sensitive detectors (e.g. TCD), Co is affected neither by column diameter nor by film thickness. The Qo-df plot for constant temperature shows a minimum, suggesting an optimum film thickness for mass flow sensitive as well as concentration sensitive detectors. The corresponding capacity ratio has a value between 0.5 and 1.5. At elevated temperatures (k constant) in combination with mass flow sensitive detectors, again an optimum film thickness exists, corresponding to a minimum value of Co. For constant capacity ratio Qo always increases with the film thickness for both types of detectors. As indicated above, in some situations the lowest values of Co and Qo are obtained at an increased film thickness, the effect being marginal. As an initial guideline, for the daily practice of capillary gas chromatography with respect to minimum values of Co and Qo, the use of thin film columns is to be preferred.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 7
    ISSN: 0935-6304
    Keywords: Capillary GC ; Deactivation ; 29Si-NMR ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A high degree of deactivation of glass and fused-silica capillary column walls is attainable by means of high temperature silylation (HTS) with or without a preceding leaching process. HTS with a phenyl containing disilazane, diphenyltetramethyldisilazane (DPTMDS), and polydimethylsiloxane (PDMS) are studied on Cab-O-Sil, a fumed silica, as a model substrate. Using 29Si CP-MAS NMR, it was shown that no dimethylsiloxane chains were formed upon silylation with DPTMDS under different conditions of humidity and stoichiometry at 377°C. With DPTMDS deactivation it is possible that amino trisiloxy silane groups are formed, these groups add extra activity to the surface. Silylation with a PDMS, OV 101, at various temperatures between 300°-420°C did show that dimethylsiloxane chains were bonded at the surface. Using the 29Si CP-MAS NMR technique with variable contact times to reveal siloxy group mobility, the degradation of dimethylsiloxane chains at the surface was studied. PDMS degradation at an optimal temperature gives a more effective diminuation of the silane activity caused by chemical reaction with the silanol groups and the effective screening of the remaining silanol groups with anchored polydimethylsiloxane chains and small cyclodimethylsiloxane ring structures at the surface.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 11 (1988), S. 845-848 
    ISSN: 0935-6304
    Keywords: Capillary gas chromatography ; GC/MS ; Theory ; Ceparation speed ; Detection limits ; Identification limits ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 11 (1988), S. 862-869 
    ISSN: 0935-6304
    Keywords: Capillary gas chromatography ; Column-detector systems ; Detectability ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Expressions for the minimum detectable amount Qo and the minimum analyte concentration Co as functions of the chromatographic parameters are derived for both mass and concentration sensitive detectors. The effects of pressure drop, column inner diameter, and film thickness are given.The minimum analyte concentration for mass flow sensitive detectors, Com, can be reduced considerably by selecting the carrier gas velocity well above its optimum value (related to Hmin), however, at the cost of long columns and long analysis times. For Qo the improvements can be neglected, and so the analysis can best be performed at uopt.When the flow rate in the detector, Fd, is equal to the column flow rate Fc, the maximum permissible detector volume of concentration sensitive detectors is proportional to dc2 up to dc3, and so narrow bore columns require detectors of extremely small volume. Make-up gas has to be added when the actual volume is too large, thus worsening the detectability. Another approach, vacuum operation of the detector cell, appears to be very attractive. On the other hand, when wide bore columns are used in combination with small volume concentration sensitive detectors, very small values of Qoc and Coc are obtainable when the abundant carrier gas can be removed before entering the detector cell.Digital noise filtering can further reduce the obtainable Qo and Co values, especially for broad peaks and thus for wide bore columns.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 11 (1988), S. 852-857 
    ISSN: 0935-6304
    Keywords: High speed capillary GC ; Narrow bore columns ; Enrichment ; Cold trapping ; Flash thermodesorption ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reduction of the column diameter has proved to be a highly efficient tool to increase the speed of analysis. Unfortunately, the requirements for instrumental design with respect to sample input band width, low dead volume interfacing, and time constants of detection and registration systems are the more critical the smaller the inside diameter.Recently we reported input band widths as low as 1 ms [1] for gaseous samples at ppm concentration levels, without any preconcentration, in a study with narrow bore columns and thermal conductivity detection.In this study a simple versatile micro on-column cold trap/thermodesorption enrichment system for narrow bore columns is introduced and evaluated. The combination of considerable sample enrichment and preservation of the compatibility of the required input band width with column dimensions is critically examined. The process of thermodesorption (reinjection) which is the most critical step, is particularly emphasized.The system consists of a short aluminum coated fused silica or metal capillary with a low mass and a low cost electrical heating. Input band widths down to 1 ms are obtained without extreme demands on electrical power (300 watt). The potential of the system is illustrated with some extremely fast separations.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
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