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Some aroma compounds found in alcoholic beverages are characteristic of a certain beverage (i.e. 2,4-decadienoic acid ethyl ester is characteristic of pear spirit and 5-butyltetrahydro-4-methylfuran-2-on “whiskey lactone” is characteristic of aged spirits like whiskey). These substances were detectable in beverages but not in blood samples. The aim of this investigation was to find a sensitive sampling technique for aroma compounds in whole blood samples. This technique may be used in forensic toxicology for examination of drinking claims. The method comprises dynamic headspace sampling using a purge and trap concentrator, followed by quantitative gas chromatography–mass spectrometry (dynamic HS–GC–MS). The influence of sample preparation, trap adsorbents and sample temperature as well as desorption time and purge time on the quality of the analytical results were investigated. The following optimal parameters were determined: stirred and diluted whole blood sample without salt addition, use of Carbotrap C as trap material, sample temperature at 80 °C, desorption time 20 min and purge time 30 min. These optimal parameters were used for the determination of detection limits (LOD). The LOD of aroma compounds by means of dynamic headspace sampling were compared with the results of conventional sampling: the static headspace technique. Limits of detection for the aroma compounds with conventional static headspace GC are in the range 400–10,000 μg L−1. Dynamic headspace–GC was found to be a more sensitive sampling technique for most of the aroma compounds investigated (e.g. C4–C8 ethyl esters, benzoic acid ethyl ester, linalool oxide and 4-ethylguaiacol) with detection limits between 1 and 50 μg L−1, but there were also limits to the sampling of substances with lower volatility like decanoic acid ethyl ester, 2,4-decadienoic acid ethyl ester, eugenol and whiskey lactone with detection limits of about 1,000 μg L−1.

In the area of former ammunition plants, contaminations caused by explosives and their degradation products are of great environmental relevance because of the immediate vicinity of ground- and drinking water reservoirs. Beside the determination of selected explosive-related compounds by means of HPLC with UV detection, a LC-MS-MS coupling utilizing electrospray ionisation was developed, which is particularly suited for the determination of highly polar compounds. Therewith, 12 different explosive-related compounds were identified and quantified on the basis of specific precursor-/ product-ion traces using the high selectivity and sensitivity of multiple reaction monitoring mode (MRM) of a triple quadrupole mass spectrometer. The LC-MS-MS-technique was applied to water samples from the area of a former ammunition plant. In addition to dinitrophenols and aminodinitrotoluenes which could be determined also by HPLC-UV, some highly polar compounds were found in the contaminated water, for example 3,5-dinitrobenzoic acid and 2-amino-4,6-dinitrobenzoic acid. The highest concentrations (14–40 µg L−1) were found for two isomers of dinitrotoluenesulfonic acids. In order to assure the quantitative determination of polar substances in real samples with different composition, external calibration and standard addition method were compared. The presented LC-MS-MS-method is suited for screening and quantification of polar and hydrophilic explosive-related compounds from different classes of substances in a single analytical protocol.

A novel system for sample introduction into a Gas Chromatograph (GC) using an automated in-column pyrolysis device has been developed. The in-column pyrolysis device is suitable for use with any GC or GC-MS system. Solid samples are dissolved or emulsions can be diluted and injected into the system. Because the system is designed for introducing liquid samples, a better control of the injected sample amounts is achieved. This leads to high reproducibility of the peak areas, offering new opportunities for quantitation of polymers or other high molecular weight materials. In addition, a better statistical representation of the material to be analyzed is given if the samples are dissolved in a solvent. The system can be operated both in a normal GC injection mode, and in the pyrolysis mode. As a conventional GC injector working in on-column or Programmed Temperature Vaporization (PTV) injection mode, (without the pyrolysis function), information on the volatile fraction of a sample can be obtained. Once the volatile materials in the sample have been separated, a second analysis on the non-volatile matrix can be performed by initiating the pyrolysis sequence, yielding information on the non-volatile fraction of the sample. Both features, on column or PTV injection mode and in-column pyrolysis can be used separately or in combination. This new technology is expected to be useful for the determination of additives, monomers, solvents and other volatile components in a non volatile matrix, such as polymers, as well as in the characterization of the non-volatile matrix itself, in a single run.

A new system has been developed for rapid on-line SPE-LC-MS-MS analysis of a wide spectrum of trace level pesticides in drinking and surface water. The system employs a serial arrangement of two different turbulent flow columns (TFC; polymer based column in front, carbon based column back) for rapid extraction (Turbulent flow solid phase extraction; TFSPE) from small sample volumes (10 mL) at high flow rates (5 mL min−1). Purely organic eluent is used for TFC elution, and the effluent is re-mixed with water in a mixing chamber in front of the HPLC column to provide efficient analyte focusing. This methodology allows to use a short monolithic LC column for the following fast on-line LC-APCI-MS-MS analysis. This approach gives quantitative results for nearly 30 pesticide species (triazines, phenyl ureas, organophosphorous pesticides and others) in less than 14 min and, thus, allows considerably increased sample throughput. The method is well reproducible, robust and extremely sensitive achieving detection limits between 0.1 and 1 ng L−1. As the comparison of internal and external calibration methods showed, potential matrix effects on the quality of the results are managed by the method in a very effective manner. Real pesticide concentrations determined in drinking water and surface water samples showed significant temporal variations but were constantly below the concentration limit for individual pollutants of 100 ng L−1.

This review summarizes a presentation on ambient air analysis of volatile organic compounds given at the “Trace enrichment for GC and HPLC analysis” workshop at the ISC'02. Adsorptive enrichment of volatile organic compounds has become an important technique in ambient air analysis. The paper focuses on the use of adsorptive enrichment for sampling volatile organic compounds. Different techniques for sampling and desorption are reviewed and an overview of commonly used adsorbent materials is given. Furthermore, strategies for managing interferences, such as moisture, are discussed.

A rapid and simple method, pyrolysis gas chromatography coupled with mass spectrometric detection (Py-GC-MS), is introduced for qualitative determination of banned aromatic amines released from azo dyes on textiles. Use of Py-GC-MS can reduce absolute analysis time from three hours to thirty minutes, because no sample preparation is necessary. Qualitative determination of banned amines by Py-GC-MS was investigated for three pure azo dyes and six contaminated textile samples consisting of different matrices. Pyrolysates of pure azo dyes were identified as aromatic amines. Banned aromatic amines released from azo dyes could be qualitatively determined for four of six contaminated textile samples by Py-GC-MS.

This work deals with the investigation of the possibilities and limitations using a commercially available software package Drylab for the fast optimisation of running conditions and the prediction of separation and retention times of a mixture consisting of fourteen neutral (nitramines, aminonitroaromatics and nitroaromatics) and six acidic (nitrophenols) explosive-related compounds.

Headspace solid-phase microextraction (HS-SPME) has been successfully applied to the determination of perfume components in scented candle wax, liquid laundry detergent, and fabric softener. Different fiber coatings (100 μm polydimethylsiloxane, 50/30 μm divinylbenzene/Carboxen/polydimethylsiloxane, 70 μm Carbowax/divinylbenzene, and 85 μm polyacrylate) were tested and the extraction conditions were optimized. For most compounds extraction efficiency, reproducibility, and long-term stability were highest for polydimethylsiloxane. The compatibility of SPME with fast gas chromatographic separation was investigated. The speed of conventional gas chromatography was increased by a factor of 2.5, without loss of separation efficiency, simply by reducing the column length and inner diameter and adjusting the separation conditions by use of method translation software. It was demonstrated that SPME is a suitable sample-introduction technique for fast GC if split injection is used.

This work describes methodical studies of thermally assisted hydrolysis and methylation (THM) of fatty acids (FA) and triglycerides comparing different derivatization reagents, such as tetramethylammonium hydroxide (TMAH), tetramethylammonium acetate (TMAAc), trimethylsulfonium hydroxide (TMSH), trimethylphenylamine hydroxide (TMPAH), and (m-trifluoromethylphenyl) trimethylammonium hydroxide (MethPrep 2). The performance of these reagents using different injection techniques, such as pyrolysis, hot split injection, and programmed temperature vaporization (PTV) has been investigated.

A review is given dealing with commonly used adsorbent materials in ambient air analysis of volatile organic compounds (VOCs). The adsorbents covered in the paper are selected in consideration of their compatibility with thermal desorption. Initially, we discuss the requirements that an adsorbent should fulfill, and useful parameters for the selection and evaluation of an appropriate material. Then, the most important materials are presented considering their properties, advantages, and drawbacks. A few applications are given, but a complete review of sampling techniques and applications dealing with adsorptive enrichment and thermal desorption is beyond the scope of this paper.

AGC method has been developed for the analysis of tricholoroacetic acid (TCA) in water samples. It entails large-volume injection (LVI) and programmed-temperature vaporization (PTV) of water samples, thermal decarboxylation of TCA to chloroform in the injector, and GC-ECD analysis of the decarboxylation product. Conditions such as final injector temperature, splitless time, and injection volume were optimized. The limit of detection is approximately 0.1 μg L−1 Several real samples were analyzed. The method presented is an easy means of determination of TCA and eliminates sample-preparation steps such as extraction and derivatization.

Laboratory experiments have been performed to examine the potential of adsorptive enrichment thermal desorption and gas chromatography for the analysis of low molecular-weight oxygenated compounds in gaseous samples. The experiments were conducted with test atmospheres containing, for example, acetaldehyde, propionaldehyde, acrolein, methacrolein, and acetone. The suitability of the graphitized carbon blacks Carbotrap X and Carbograph 5 for sampling these compounds was tested. In this context the influence of humidity on the recovery of the analytes and on the storage stability of the loaded adsorbent tubes over a period of seven days under different storage conditions was investigated. Losses of up to 60% propionaldehyde and acrolein were observed for Carbotrap X, even immediately after sampling. In contrast Carbograph 5 seems promising for the sampling of low molecular-weight oxygenated compounds, although with some limitations. The laboratory investigations were proved by use of an interlaboratory experiment.

In the context of evaluating air sampling methods, laboratory experiments were performed to investigate the stability of eleven selected low boiling hydrocarbons (e.g. 1,3-butadiene, isoprene) adsorbed on four different carbon based adsorbents. The carbon molecular sieves Carboxen 569, Carboxen 1003, Carbosieve SIII and the graphitized carbon black Carbotrap X were tested. The influence of storage duration on the recovery of the analytes was examined by loading the adsorbent tubes with the test compounds via a sample loop under inert gas. Furthermore, the influence of sampling the hydrocarbons continuously from air on the recovery of the analytes was investigated using a simple experimental set-up providing a flow of synthetic air spiked with the hydrocarbons. Analysis of the loaded adsorbent tubes was performed by thermal desorption and capillary gas chromatography. Losses up to 80% of 1,3-butadiene and isoprene were observed for the carbon molecular sieves, occurring even immediately after the sampling step. In contrast, no significant losses of these reactive constituents were detected for Carbotrap X over a storage time of seven days. The laboratory investigations were confirmed in a field experiment.

A new PLOT column (CP-LOWOX) designed specifically for the analysis of oxygenated compounds has been used for the gas chromatographic determination of semi-volatile carbonyl compounds. The separation behavior of the new column was investigated by comparing it with the widely used non-polar polydimethylsiloxane and polar poly(ethylene glycol) columns. The CP-LOWOX column has unique selectivity for aldehydes and ketones enabling a selective separation of these analytes from predominating hydrocarbon matrices. Application of the CP-LOWOX column for the analysis of polar compounds in ambient air is demonstrated. Sampling was performed by adsorptive enrichment coupled with thermal desorption. The suitability of Tenax TA and a multi-bed adsorbent trap Carbotrap C and Carbotrap) was tested for the sampling of semivolatile carbonyl compounds.

The use of Solid Phase Microextraction (SPME) for the qualitative and quantitative determination of Linear Alkylbenzenesulfonates (LAS) in waste water samples was investigated. A Carbowax/Templated Resin (CW/¶TPR) coated fiber was directly immersed into influent and effluent samples of a sewage treatment plant (STP). Extraction conditions such as time, pH, ion strength were investigated. The extracted LAS were desorbed with a solvent in a specially designed SPME-LC interface for analysis with HPLC-FLD and Electrospray Ionization Mass Spectrometry (ESI-MS). The combination of SPME with ESI-MS proved to be an alternative technique for the LAS determination in waste water. Linear ranges of the external calibration were found from 0.5–100 ng/mL, with detection limits of 0.5 ng/mL for each individual LAS homologue. The reproducibility of the method is 15% (relative standard deviation).

The potential of large-volume PTV injection was studied for the analysis of triazine herbicides in water samples. Direct water injection and in-vial extraction were described and compared. Detection limits were between 0.01–0.02 μg L−1 and relative standard deviations were

For the comprehensive characterization of ambient air concentrations of a broad spectrum of volatile organic compounds (VOCs) an analytical method is described, consisting of adsorptive enrichment, thermal desorption without cryofocusing, and capillary gas chromatographic separation. The method was applied during two-week measuring campaigns in winter and summer 1995, and in the winter of 1996. Long-term sampling was carried out at sampling points in residential areas in the suburbs and near the city center of Leipzig. About 70 VOCs – mainly hydrocarbons from propene to hexadecane – were identified both by GC-MS and chromatographic retention data and quantified after external calibration. Mean values of VOC concentrations obtained during the sampling periods are reported and discussed with regard to the topographical location of the sampling points in the Leipzig area, seasonal variations, and possible emission sources.

The combination of headspace solid-phase microextraction with atomic-emission detection enables highly selective and sensitive determination of itro musk compounds in cosmetic products. Sample preparation is considerably simplified; there is no solvent extraction step. Enrichment is influenced by the type and amount of cosmetic product investigated. The lowest amount giving well detectable peaks is 1 mg musk compound per kg sample. Calibration curves obtained from spiked solutions of selected reference cosmetics in water show very good linearity. Relative standard deviations of peak areas from repeated measurements are usually

A method was developed for the determination of nitrobenzoic acids and nitrophenols as well as of diaminoaromatics and was applied to the analysis of water samples from the former ammunition plant at Elsnig (Saxony, Germany).

The capillary gas chromatographic retention behavior of α-pinene and tricyclene has been investigated on stationary phases of different polarities. On all but one of the columns employed, tricyclene eluted before α-pinene; only permethylated β-cyclodextrins dissolved in moderately polar polisiloxanes gave a reversed elution order. The intermolecular interactions which caused the unexpected retention behavior were investigated in detail, applying methods of computer simulation. To achieve this, we have developed a calculation algorithm on the basis of molecular mechanical optimizations and programmed it in a macro. This makes it possible to systematically investigate a given configuration space in which all the possible interactions can take place. It was shown that permethylated β-cyclodextrin as host molecule for both guest molecules offers an optimum cavity size. As a result the number of energetically favorable contacts between host and guest molecules as well as the strength of the interactions in this stationary phase were larger. As a consequence the elution order, normally only influenced by the vapor pressure of the compounds at a given temperature, was changed. Nonspecific interactions played an especially important role for these kinds of substances.

A method for the gas chromatographic trace analysis of underivatized nitrophenols in ground-water is presented. Using a highly de-activated separation system a satisfactory precision for their quantitative GC analysis could be achieved by avoiding condensation of the solvent and by fast injection of the sample. The reproducibility of the peak areas of eleven nitrophenols in ethylacetate was 0.992.

The separation of racemic side-chain fluorinated alkylbenzenes and bromofluorinated analogues by capillary gas chromatography using permethylated α, β and γ-cyclodextrins dissolved in polysiloxanes of different polarity as stationary phases is described. The influence of the achiral polysiloxane matrices on the separation of enantiomers is discussed in the light of the results obtained with the different phases. For a part of the tested compounds thermodynamic data are determined which describe the interaction of enantiomers with the stationary phase. The mechanism of separation is discussed on this basis and by comparison with data for structurally similar compounds.

A GC method is described for the determination of pollutants in aqueous samples by direct enrichment out of large sample volumes in a PTV injector. The vaporized water is eliminated through the split vent and the analytes are concentrated on an adsorbent inside the insert of the PTV. For the selection of suitable adsorbents, breakthrough volumes of selected pesticides and nitroaromatics on Tenax TA, Tenax GR, Chemipack C18 and graphitized carbon blacks have been determined by experiment. The determination of the breakthrough volumes was carried out directly in the PTV insert. Tenax TA proved to be the best sorbent with regard to the breakthrough volumes and its inertness to the analytes to be determined. As the result of the investigations, 500 μl of aqueous standard solutions of pesticides and nitroaromatics (concn.=0.02 ... 2 μg/l) were analyzed with an average relative standard deviation of 10%. The procedure was successfully applied for the analysis of real samples.

Needles of the Macedonian Pine,Pinus peuce Griseb., a conifer growing in the Balkan mountains, were extracted by a Likens-Nickerson simultaneous distillation-solvent extraction device. The components of this essential oil were identified by the retention times obtained on two columns differing in polarity and by GC-MS. Because of the complex nature of such plant extracts, a multidimensional GC method for enantiomer analysis, using a non-chiral pre-column and a chiral main column has been developed. The enantiomeric ratios of five monoterpene hydrocarbons were estimated by GC-GC and GC-GC-MS.

Retention indices of 6 selected hydroxy compounds (aliphatic and bicyclic alcohols, phenols) were determined on 2 HP-5 fused-silica, capillary columns with different film thicknesses (0.11 μm and 0.33 μm) at 8 different oven temperatures between 80 and 150°C. For some substances the I-T plot was found to show a minimum which cannot be explained by the common retention-index temperature-dependence in gas-liquid chromatography. This result is discussed in terms of adsorption at the liquid-solid interface of the capillary column.

Mittels adsorptiver Anreicherung an hydrophoben Adsorbentien, Thermodesorption und kapillargaschromatographischer Analyse wurden fluchtige organische Verbindungen in den Rauchgasen aus dem Hausbrand von Braunkohlebriketts aus dem Lausitzer Revier bestimmt. 152 Verbindungen konnten sicher identifiziert und quantitativ erfast werden. Die auf die Menge des eingesetzten Brennmaterials bezogenen Emissionsfaktoren der nachgewiesenen Einzelverbindungen wurden ermittelt und gestatten erstmals eine auf konkreten Meswerten basierende Abschatzung der aus dem Hausbrand heimischer Braunkohle resultierenden Belastung der Stadt Leipzig mt fluchtigen organischen Verbindungen.

An indirect GC method is described for the determination of Ethephon in drinking water on the basis of the headspace analysis of the ethylene formed from Ethephon. In order to reach the necessary detection limit, the entire volume of the static headspace distribution is transferred into a cold injection system (CIS). There, the ethylene is adsorbed on Carbosieve SIII at 10°C and, subsequently, desorbed at 300 °C. The water vapour included in the headspace is completely eliminated through the splitting system. By means of this technique, a detection limit of 0.05 μg/l water was reached.

Using achiral stationary phases of different polarity in capillary gas chromatography it is demonstrated that the hydration of 1,2–5,6-dibenzocycloocta-1,5-diene yields five isomers of the tricyclo[10.4.0.04,9]hexadecanes. With highly polar stationary phases all isomers of the tricyclic hexadecanes and the semihydrated products in the mixture were also separated from each other. The chiral isomers were separated on cyclodextrin stationary phase. Moreover, with columns of achiral and chiral phases coupled in series, in a double oven gas chromatograph, it was possible to estimate the configuration of the isomers. The separation of diastereomers on chiral stationary phases is a useful means for structural assignment of isomeric compounds.

A high-resolution gas-chromatographic (HRGC) method with electron capture detection is described for the sensitive determination of PCBs and toxaphene in water in the lower ng/l range. The required low detection limits are guaranteed by isolation of the target compounds and concentration from the filtered water sample by solid phase extraction with specific C18 silica gel (200–250 μm) alone or combined with the injection of larger extract volumes into a programmed temperature vaporizer (PTV) operating in the solvent venting mode. The bonded silica gel was prepared by reaction of the surface silanol groups with octadecyltrichlorosilane. A C18 silica of reproducible coverage was received. Practical aspects of the use of the solid phase extraction in combination with the PTV injection technique are discussed. The recoveries for toxaphene and PCBs were 85 and 78%.

The adsorption of moelcules on the nonspecific and nonporous adsorbent graphitized thermal carbon black (GTCB) is mainly determined by their intermolecular dispersion interaction with the flat graphite surface. Since the retention values strongly depend on the geometrical configuration and shape of the investigated molecules and their arrangement on the graphite plane, it is possible to separate compounds with only small differences in their molecular shape on short columns packed with particles of pure or modified GTCB.

In a series-coupled system of two capillary columns with different polarity, a controlled overlapping of sulphur-containing and sulphur-free compounds can be achieved by means of different mid-point pressure settings. By means of this selectivity tuning it is possible to measure exactly the quenching of the flame photometric detector signal for a sulphur compound coeluted with an excess of a sulphur-free compound. With the example of a complex sample it is shown that, with a suitable system of columns, selectivity tuning can give quench-free FPD chromatograms or chromatograms with quench-free regions.

The large-volume sampling of aqueous samples in a programmed temperature vaporizer (PTV) injector was used successfully for the target and non-target analysis of real samples. In this still rarely applied method, e.g., 1 mL of the water sample to be analyzed is slowly injected direct into the PTV. The vaporized water is eliminated through the split vent. The analytes are concentrated onto an adsorbent inside the insert and subsequently thermally desorbed. The capability of the method is demonstrated using a sample from the river Elbe. By means of coupling this method with a mass selective detector in SIM mode (target analysis) the method allows the determination of pollutants in the concentration range up to 0.01 μg/L. Furthermore, PTV enrichment is an effective and time-saving method for non-target analysis in SCAN mode. In a sample from the river Elbe over 20 compounds were identified.

Selectivity tuning is used in a system of series-coupled GC-columns of different polarity in order to improve the analysis of complex samples of essential oils. It is shown that selectivity tuning by changing the flow-rates in the single columns can be used for improving both the resolution and the reliability of identification. Furthermore, by combining this method with column switching techniques (multidimensional GC) a reduction of sample complexity could be reached. Isothermal retention indices of 35 terpenoid compounds were ascertained using a non-polar and a polar capillary column serving as the input-values of a computer program which enables the prediction of system retention times at any adjusted flow-rate. Therefore, promising chromatographic conditions for the separation of interesting compounds could be selected without great experimental effort and some of these compounds could be identified with a high degree of reliability.

The fundamental suitability of solid-phase microextraction (SPME) has been investigated for the enrichment of partially well water-soluble and differently substituted polar nitrophenols. Two commercially available fibers coated with 100 μm polydimethylsiloxane or 85 μm polyacrylate, respectively, were compared with regard to the efficiency of the enrichment of these compounds. For all the compounds investigated, polyacrylate fiber showed a better affinity when the exposure time was longer in comparison with polydimethylsiloxane fiber. The ‘salting-out’ and the enrichment at low pH-values increased the sensitivity of the process significantly.

For the study of relationships between retention behaviour and molecular structure in GLC and GSC the retention indices of alkenylbenzenes with 2–6 carbon atoms in a straight or branched side chain and of isotopological alkylbenzenes were determined on capillary columns coated with OV-1 and Ucon LB and on a micropacked column filled with graphitized thermal carbon black. From the values obtained index differences corresponding to the increments of the double bond in the side chain were derived. These differences depend significantly on the structure of the side chain and of the position of the double bond.

Die Retentionsindices von Alkylbenzolen der C-Zahlen 9 bis 14 wurden bei der GAC an einer mit graphitiertem thermischem Rus gepackten Saule gemessen. Die daraus abgeleiteten Homomorphiefaktoren sind fur Benzolderivate mit mehreren Methylgruppen positiv, fur die ubrigen Alkyl-und Dialkylbenzole negativ. Es werden Zusammenhange zwischen Molekulstruktur und Retention diskutiert und die Ergebnisse mit entsprechenden Resultaten in der GVC verglichen. Die Vorteile dieses Adsorbens zur Trennung von Alkylbenzolen mit verzweigten Seitenketten werden demonstriert.

Using n-heptane as eluent a direct linear correlation was found between the logk’ values of various polar test compounds and the silanol content determined by the methyllithium method. The peak asymmetries pass through a maximum at a medium silanol content. Peak asymmetries and logk’ values depend also on the chain length of the bonded alkyl group. A computer program was used to classify 25 home-made RP materials, 7 commercial products and the starting silica to achieve a hierarchical classification of them. The arrangement provides some detailed information about the presence and the effect of silanol groups.

High silica molecular sieves (silicalite, ZSM-5) were tested as adsorbents for gas chromatographic trace analysis. Therefore the retention behaviour of low-boiling organic compounds (hydrocarbons, halogenated hydrocarbons, amines, alcohols and ethers) on these materials was investigated. The specific retention volumes at different temperatures have been determined and elution orders and peak shapes were studied. The retention data allow a simple calculation of the breakthrough volumes (dynamic adsorption capacity) and the chromatographic characterisation of the adsorbents. Both nitrogen and oxygen containing compounds could not—or at least unreproducibely—be eluated up to 300°. The elution order and the peak shape of compounds with the same number of carbon atoms but different geometric and electronic structure (e.g.n-butenes;n-hexane, cyclohexane, benzene) can be explained by the action of exclusion effects and different diffusion barriers.

In der vorliegenden Arbeit wurden fur einige durch thermischen Umlagerung von cyclododecatrien-(1.5.9) erhaltene Kohlenwasserstoffe und ihre Hydrierungs-produkte Retentionsdaten an graphitiertem thermischen Rus bestimmt. In Verbindung mit semiempirischen Berechnungen und durch Vergleich mit Retentionsdaten, die an Squalan-bzw. Ucon 50 HB 280×polar-Trennkapillaren gemesen wurden, konnte aus diesen, Werten eine konfigurative Zuordnung getroffen werden.

Reaction products of the pyrolysis of n-dodecylpentane and n-hexylcyclohexane had been separated and identified on a glass capillary column coated with Polydimethylsiloxane OV-1.

Die Retentionsindices von Alkylbenzolen der C-Zahlen 9 bis 14 wurden an Glaskapillaren, welche mit Squalan, Ucon LB 550 X, Ucon 50 HB 280 X polar und Carbowax 20 M impragniert waren, gemessen. Anhand der aus den Retentionsindices abgeleiteten Homorphiefaktoren (HS), Index-differenzen zwischen unterschiedlich polaren Trennflussigkeiten (ΔI), und der Indexzunahme pro CH2-Gruppe (ICH2) werden Zusammenhange zwischen gas-chromatographischem Retentionsverhalten und Molekulstruktur am Beispiel homologer Reihen geradkettiger Mono- und p-Dialkylbenzole, isomerer unverzweigter p-Dialkylbenzole mit unterschiedlich langen Seitenketten, isomerer verzweigter Butyl- und p-Dibutylbenzole sowie der Polymethylbenzole diskutiert.

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 HOV, HGTCB 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 (ΔGI.U.=4.18kJ/mol) confirmes that graphitized thermal carbon black causes much stronger dispersive interactions than any nonpolar liquid phase.

Die Desaktivierung von Glaskapillaren duch Silanisierung mit verschiedenen Reagenzien bei unterschiedlichen Reaktionsbedingungen wurde untersucht. Es zeigte sich, das die Wirksamkeit der Silanisierung wesentlich verbessert werden kann, wenn die Behandlung der Glaskapillaren mit reinem Hexamethyldisilazan etwa 20 Stunden lang bei 300°C erfolgt.