Analysis of trace components in gases by gas chromatography

Summary Relationships are derived describing how the detection limit of a chromatographic system depends on the minimum detectable limit of the detector and the chromatographic parameters such as column length, efficiency, carrier gas flow rate and the capacity factor. Performance data of detectors developed in the last 25 years at the Dalian Institute of Chemical Physics of the Chinese Academy of Sciences are given and a few selected application examples are listed. These include trace analysis by preconcentration and by direct analysis and the utilization of multidimensional gas chromatography with two columns, two detectors, a 12-port valve, and a catalytic conversion reactor.     

Study of the responses of a gas chromatography—reduction gas detector system to gaseous hydrocarbons under different conditions

The response of a reduction gas detector (RGD) to C₂-C₆ alkenes, C₂-C₆ alkanes, isoprene and benzene has been investigated using gas chromatography (GC) with a packed column. The RGD is considerably more sensitive to alkenes than is the flame ionization detector. The detection limit of this present GC/RGD system for alkenes is about 0.01 ng. It has much greater sensitivity to alkenes than to alkanes. Its sensitivity increases with increasing HgO bed temperature, but its selectivity towards alkenes decreases at the same time. The selectivity of the RGD may not be significant for much heavier molecules. The sensitivity of the RGD is inversely proportional to the carrier gas flow rate through the HgO bed. The baseline of the system increases significantly with increasing oven temperature.     

Rapid on-line analysis of low molecular weight hydrocarbons using glass capillary gas chromatography

Rapid analysis is important for on-line chromatography. Gaseous or vaporized samples have been injected via heated gas sampling valves of less than 500 μl dead volume. The critical sampling and split problems could be solved by temperature programming. The general analysis described could be successfully used inter alia in scouting reactions.     

Viscosities of carrier gases at gas chromatograph temperatures and pressures

Summary Equations are derived for viscosities of H₂, He, N₂ and Ar for use at chromatographic temperatures which are accurate to within 0.3% for H₂, and 0.1% for the other gases. The effect of pressure is usually negligible but may increase the viscosity of N₂ or Ar by as much as 0.5% at 25°C or lower and 5 atm or higher.     

On-line multidimensional supercritical fluid chromatography/capillary gas chromatography

A new analytical technique combining on-line supercritical fluid chromatography with capillary gas chromatography has been developed. The supercritical fluid sample effluent is decompressed through a restrictor directly into a conventional capillary gas chromatographic injection port. This technique allows for not only direct (100%) sample transfer from the supercritical fluid chromatograph to the gas chromatograph but also for selective or multi-step heartcutting of various sample peaks as they elute from the supercritical fluid chromatograph. Heartcut times are determined by monitoring the responses from the flame ionization or ultraviolet absorbance detectors on the supercritical fluid chromatograph. This report describes the operational setup and provides the results of heartcut reproducibility experiments using normal hydrocarbon and aromatic test mixtures. Results from studies where operational parameters were varied, such as GC injector temperature, will also be provided. The potential usefulness of this new technique for selective heartcutting will also be demonstrated using complex hydrocarbon streams.     

Hydrocarbon type analysis by gas chromatograph using a single capillary column and a multi-column valve system

Summary Two different gas chromatographic methods are used for the determination of hydrocarbon type distribution in naphtha and gasoline samples with final boiling points up to 275 °C. The methods are based either on a single capillary column or on a valve-switched packed column system. Both methods give extensive information on paraffins, olefins, naphthenes and aromatics in total as well as by carbon-number. In each case the analysis is fully automated with a computer controlling the entire analysis from injection to results presentation. The advantages and limitations of both methods are discussed.Presented at the 14th International Symposium on Chromatography London, September, 1982     

固相萃取-毛细管气相色谱法检测淫羊霍等药用植物有机氯农药残留

建立了淫羊霍等药用植物中六六六及滴滴涕异构体残留量的毛细管气相色谱检测方法。样品采用微量化学法进行提取,固相萃取法净化,以不分流方式进样,用HP 5弹性石英毛细管柱程序升温分离样品,微电子捕获检测器检测,外标法计算其质量分数。结果表明,最小检测量为1.4×10-14～1.2×10-12g,加样平均回收率为92.16%～100.59%,相对标准偏差为0.5%～4.2%。该法各项技术指标均满足农药残留检测的要求。     

Application of capillary gas chromatography to automated on-line quantitative analysis of solvent vapors

Solvent vapors in air may be measured with capillary gas chromatographic columns. By using large diameter columns and sample loops of approximately the same internal diameter, the column may be connected directly to the gas sampling valve. This approach eliminates the use of a splitter or cryogenic trapping and allows low levels to be measured. By operating the column at high velocity, column efficiency is sacrificed for increase in speed.     

鸦片的气相色谱快速分析

采用大口径毛细管柱,建立了一种气相色谱测定鸦片中生物碱的快速分析方法。样品经超声提取,ＨＰ－１（５ｍ×０．５３ｍｍ×２．６５μｍ）毛细管色谱柱,ＦＩＤ测定。回收率为９６．８％￣１０１．１％,相对标准偏差均小于３％。方法简便,快速,准确,灵敏。     

Real-time control of column switching in multidimensional gas chromatography

In chromatography the separation power expressed in terms of peak capacity can be greatly enhanced by multidimensional techniques. The most important aspect of multidimensional chromatography is the precise location of the heart-cut window. Very often the reliability of this positioning is ensured by applying relatively large heart-cuts; this reduces the intrinsic selectivity offered by the technique. The best way of locating peaks in chromatography is by means of retention indices. This technique can also be used in multidimensional chromatography. A method is described whereby the heartcut window in multidimensional gas chromatography (MDGC) can be defined precisely.     

Construction of an all-glass/fused silica,zero dead volume multidimensional gas chromatographic system using press-fit connectors: Preliminary results

A multidimensional gas chromatographic system has been constructed using commercially available press-fit connectors, glass splitters, and fused silica lines. In this new design all the lines are continuously purged with carrier gas, ensuring no dead volumes in the chromatographic path. Some preliminary results and practical considerations are presented.     

High resolution gas chromatographic determination of permanent gases with a helium ionization detector

The capability of the helium ionization detector (HID) to operate in connection with capillary columns for trace gas analyses has been evaluated. Two different capillary columns were considered: a PLOT fused silica column with molecular sleve and a thick film WCOT glass column with PS-255. The determination of trace impurities in gases can be achieved with evident advantages over classical adsorption columns, even using a split injection system. Direct on-column injections also have been investigated with promising results.     

Operating the pulsed discharged detector in both the electron-capture and photoionization modes within the same GC analysis

Summary Since the electron-capture detector (ECD) is highly selective, it is imperative to use a more universal ionization detector in conjunction with the ECD in order to detect non-capturing or weakly capturing compounds. Also in an EC study of weakly or moderately strong electron-capturing compounds, it is necessary to identify the EC peak of the compound by identifying the major component with an ionization detector. In this paper we have shown that the pulsed discharge detector can be interchanged between the EC and the helium ionization modes within 4–6 s. The application of this procedure has been illustrated with a mixture of alkane/alkene chlorocompounds. The interchange between EC and argon photoionization modes has also been investigated. The change from EC to argon photoionization also occurs in 4–6 s but the reverse process requires 9 s.     

Fast analysis by gas chromatography

Summary The efficiency of fast GC columns depends largely on the quality of the chromatograph. A theoretical and experimental study shows the relative importance of the various phenomena involved and permits the optimization of a GC System. Extremely good performances, exceeding 2,500 plates per second have been routinely obtained.Ezzel a tanulmánnyal Halász István Professzor Urat köszöntjük 60. születésnapja alkalmából.     

Improvements in preconcentration methods for determining trace impurities in ultra-pure gases by gas chromatography

Summary The blanks in preconcentration methods for determining trace amounts of impurities in ultra-pure gases, which include the preconcentration volume of sample gases, carrier gas impurities and atmospheric contamination are discussed and three concentration methods for eliminating blank errors are proposed. These are, the differential volume method by concentrating at the same flow-rate but different times (DVMSF), the differential time method by concentrating the same volumes at different flow-rates (DTMSV) and the differential volume method by concentrating for the same times but different flow-rates (DVMST). DVMST is proposed as the best method for its ability to eliminate all blank errors described. The methods are used to determine trace amounts of Ar+O₂ and N₂ in ultra-pure hydrogen. Calculations demonstrate that the methods can effectively improve analytical accuracy.