Comparison of correlation equations for the prediction of gas chromatographic separation of alkylbenzenes

Summary A detailed statistical analysis, comparing the validity of the best literature recommended equations for prediction of retention indices of alkylbenzenes on squalane and methylsilicone stationary phases with the unified retention index concept, is presented. A comparison with literature sources shows that the unified retention index provides the smallest residual error. Hence, it can be applied for prediction purposes.     

Single fiber-in-capillary annular column for gas chromatographic separation

A method for preparation of a stationary phase-adjustable column with in-column stationary phase-coated fused-silica fiber annular column was successfully developed. The surface of a 0.12 mm o.d. bare optical fiber was first coated with a stationary phase and then inserted into a fused-silica capillary (non-coated or coated) as an annular column for gas chromatographic study. The optical fiber and capillary were coated with polydimethylsiloxane (SE-30) and polyethylene glycol 20M (PEG-20M) as nonpolar and polar stationary phases, respectively. Among the investigated annular and open tubular columns, the PEG-20M-coated fiber-in-PEG-20M-coated capillary annular column showed the highest column efficiency with a minimum plate height of 0.35 mm and an optimum gas velocity of 25 cm/s. When a SE-30/PEG-20M-coated fiber-in-uncoated capillary annular column was applied to separate a 9-component complex mixture, the total analysis time was 5.3 min and the column length was 12 m. By contrast, when a SE-30-coated fiber-in-PEG-20M-coated capillary annular column was used to separate the same 9-component mixture, the analysis time was reduced to 3.5 min and the column length was shortened by half to 6 m. Our results show that the stationary phase-coated fiber-in-stationary phase-coated capillary annular column is a better choice for gas chromatographic separation as it is more efficient and flexible. In addition, the proposed annular column design provides flexibility in using two or even more types of stationary phases to achieve optimal analytical separation.     

Generalized equations to evaluate the gas hold-up time of chromatographic systems

Summary The two approaches used for the calculation of the gas hold-up time and thus, the adjusted retention time are outlined, first for the restricted case when the carbon numbers of the three homologues used for the calculation are evenly spaced (c₃–c₂=c₂–c₁) and then, for the general case when (c₃–c₂) differs from (c₂–c₁). The basic difference in the philosophy of the two approaches is shown.     

Monte-carlo simulation of gas chromatographic separation for the prediction of retention times and peak half widths

Summary A new method for prediction of gas chromatographic retention times and peak half widths is based on the renewal theory. The only requirements are the heats of vaporization of the compounds to be separated and one calibration measurement. With this data, retention times and peak half widths can be predicted for isothermal as well as temperature-programmed gas chromatography. For the separation of non-polar substances on non-polar stationary phases the prediction error for retention times is approx. 1–2%. First simulations of polar molecules and polar stationary phases indicate that this method is also applicable in these cases but some extension will be required.     

Correlation equations for prediction of gas chromatographic separation of hydrocarbons on squalane

Summary The retention index of several hydrocarbon classes on squalane was found to be predictable (within two index units) with help of a physico-chemical index and a correction-structural number. A large number of structural elements were examined by means of correlation analysis and regression equations were obtained for calculation of the structural number. The multinomial regression equations were simplified by combining in one factor the important structural elements. A set of a limited number of selected representatives for every hydrocarbon class was found to give reliable estimations for the regression coefficient equations.     

Liquid and gas chromatographic separation of isomeric methylated dibenzothiophenes

Trace amounts of a dibenzothiophene (DBT) series in complex matrices were detected by gas chromatography with flame photometric detection (FPD) after purification and isolation by normal-phase high performance liquid chromatography. The gas chromatographic behavior of eleven methylated DBTs was studied on six common stationary phases. Complete resolution of the four monomethyl DBT isomers was only achieved on a capillary column coated with a methylphenylsilicone phase gummified in situ by heat-curing. The determination of the relative distribution of the four monomethylated isomers is proposed as a powerful method for monitoring oil pollution in marine environment.     

Enantiomer separation of side-chain fluorinated alkylbenzenes by capillary gas chromatography on cyclodextrin phases

Summary The separation of racemic side-chain fluorinated alkylbenzenes and bromofluorinated analogues by capillary gas chromatography using permethylated , and -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.     

Determination of the gas chromatographic gas hold-up time

Summary New versions are suggested for the gas hold-up time calculation in gas chromatography. The results are compared with those obtained by using other methods. The advantages of the suggested ways of calculation are pointed out.     

Improved gas chromatographic separation of C6 epoxides

Summary The separation of C₆ epoxides on a fused-silica capillary column coated with Permaphase DMS (dimethylsilicone) was investigated. Retention indices were determined at 50 and 60°C.We demonstrate that this stationary phase provides a better resolving power than OV-101.     

Comparison of sample concentration methods and correlation chromatography for polymer dynamic head-space studies

Summary Gas chromatography has been used to study the kinetics of evolution of volatiles from polypropylene samples (at 70°C). Correlation chromatography (CC) and the trapping of volatiles on Tenax sorbents and activated charcoal were employed to improve the detector signal. As a reference, the kinetics of gas evolution was studied by making a series of direct single injections of polymer head-space gas on a GC column. The results of trapping differed from those obtained by single injection. However, the data from single injections and CC were in good agreement. The CC method was found to offer far more operator convenience for dynamic head-space analysis than sample trapping, being less subject to operator errors.     

Headspace gas chromatographic separation of toxic organic impurities from air

Summary To determine toxic organic compounds (methanol, ethanol, n-propanol, acetone, methyl ethyl ketone, methyl isobutyl ketone) in air a method was developed for their headspace gas chromatographic analysis with preconcentration in n-butanol (alcohols) and in n-pentanol (ketones). The distribution coefficients of analytes in the air-absorbent system have been measured: 1051 (MeOH), 5630 (EtOH), 6773 (n-PrOH), 307 (Me₂CO), 580 (MeCOEt), 1035 (MeCOBu-i). The minimum detectable level (mg m⁻³) was determined as low as 0.9 (MeOH), 4.0 (EtOH), 0.9 (n-PrOH), 0.2 (Me₂CO), 0.1 (MeCOEt), 0.4 (MeCOBu-i). The method was effectively used for gas effluent air control in the workplace and in the atmosphere. Presented at the 21^st ISC held in Stuttgart, Germany, 15^th–20^th September, 1996     

A spark modulator for correlation chromatography

Summary A spark modulator has been tested as an injection system for correlation gas chromatography. An air/hydrocarbon vapour mixture was used as the carrier gas. Single negative sample injections were performed using a single spark period. The experiments resulted in negative sample peaks and a positive product peak. The intensity of all peaks showed a characteristic dependence on the spark frequency and power used. Ghostpeaks were absent when a correlation experiment was performed with a high concentration of a test compound in pure air. The signal to noise ratio enhancement however, was lower than the theoretical value. More experiments are necessary to expalain this phenomenon.     

Influence of carrier gas on the prediction of gas chromatographic retention times based on thermodynamic parameters

We present an investigation into the influence of carrier gas on the thermodynamics governing a capillary gas chromatographic separation. Thermodynamic parameters are estimated for a series of alkanes and alcohols on three common stationary phases using helium, hydrogen, and nitrogen carrier gases. It is shown that the substitution of carrier gases for one another results in a change in the thermodynamic parameters governing the separation. The effect of the carrier gas on the thermodynamic parameters is large enough to compromise the accuracy of the retention time calculations based on thermodynamic parameters collected in a carrier gas other than the one actually in use in a specific gas chromatographic system. A possible kinetic explanation for these observations is also investigated.     

An improved gas chromatographic assay for spectinomycin hydrochloride

Summary A gas chromatographic assay for spectinomycin hydrochloride is described. The method is based on that prescribed by the United States Pharmacopeia (USP XXII). The method involves silylation of spectinomycin hydrochloride; phenazone is used as an internal standard. Spectinomycin and phenazone have adequate stability under the prescribed conditions. The stationary phase is 3% OV-17 on Gaschrom Q 100–120 mesh. The selectivity of the proposed method is better than that of the GLC method described in the USP XXII.     

Design and evaluation of a mixed-phase capillary column for the gas chromatographic separation of the volatile components of cheese

Summary A mixed-phase capillary GC column has been designed for the separation of the compounds commonly present in the volatile fraction of cheeses. The design includes the calculation of the optimum phase concentration and the operating conditions. The evaluation of the resulting column indicates that its performance in the qualitative and quantitative analysis of cheese volatile compounds is better than those of other columns coated with a single stationary phase.     

Evaluation of 3,5-stigmastadiene content of edible oils: Comparison between the traditional capillary gas chromatographic method and the on-line high performance liquid chromatography-capillary gas chromatographic analysis

Summary The quantitation of 3,5-stigmastadiene and other steroidal hydrocarbons, commonly known as steradienes, is a valid tool for the recognition of refining (in particular bleaching) of edible oils; the evidence of this process is nowadays of a great interest due to growing market for virgin, cold-pressed, natural oils. Due to the long time required (about 4 hours) and the amount of solvents employed (about 650 mL) to perform the official analysis, other methods have been recently proposed, the most important of which involves high performance liquid chromatography coupled with capillary gas chromatography (HPLC-GC). In this study the results of ten oil samples, analysed by both the official method and HPLC-GC, are reported and the two methods compared and discussed, for routine use, in terms of sample preparation, time of analysis and setting up, difficulty and reproducibility.     

Comparison of gas chromatographic hyphenated techniques for mercury speciation analysis

In this study, we evaluate advantages and disadvantages of three hyphenated techniques for mercury speciation analysis in different sample matrices using gas chromatography (GC) with mass spectrometry (GC-MS), inductively coupled plasma mass spectrometry (GC-ICP-MS) and pyrolysis atomic fluorescence (GC-pyro-AFS) detection. Aqueous ethylation with NaBEt(4) was required in all cases. All systems were validated with respect to precision, with repeatability and reproducibility <5% RSD, confirmed by the Snedecor F-test. All methods proved to be robust according to a Plackett-Burnham design for 7 factors and 15 experiments, and calculations were carried out using the procedures described by Youden and Steiner. In order to evaluate accuracy, certified reference materials (DORM-2 and DOLT-3) were analyzed after closed-vessel microwave extraction with tetramethylammonium hydroxide (TMAH). No statistically significant differences were found to the certified values (p=0.05). The suitability for water samples analysis with different organic matter and chloride contents was evaluated by recovery experiments in synthetic spiked waters. Absolute detection and quantification limits were in the range of 2-6 pg for GC-pyro-AFS, 1-4 pg for GC-MS, with 0.05-0.21 pg for GC-ICP-MS showing the best limits of detection for the three systems employed. However, all systems are sufficiently sensitive for mercury speciation in environmental samples, with GC-MS and GC-ICP-MS offering isotope analysis capabilities for the use of species-specific isotope dilution analysis, and GC-pyro-AFS being the most cost effective alternative.     

Single-walled carbon nanotubes as stationary phase in gas chromatographic separation and determination of argon, carbon dioxide and hydrogen

A chromatographic technique is introduced based on single-walled carbon nanotubes (SWCNTs) as stationary phase for separation of Ar, CO₂ and H₂ at parts per million (ppm) levels. The efficiency of SWCNTs was compared with solid materials such as molecular sieve, charcoal, multi-walled carbon nanotubes and carbon nanofibers. The morphology of SWCNTs was optimized for maximum adsorption of H₂, CO₂ and Ar and minimum adsorption of gases such as N₂, O₂, CO and H₂O vapour. To control temperature of the gas chromatography column, peltier cooler was used. Mixtures of Ar, CO₂ and H₂ were separated according to column temperature program. Relative standard deviation for nine replicate analyses of 0.2 mL H₂ containing 10 μL of each Ar or CO₂ was 2.5% for Ar, 2.8% for CO₂ and 3.6% for H₂. The interfering effects of CO, and O₂ were investigated. Working ranges were evaluated as 40-600 ppm for Ar, 30-850 ppm for CO₂ and 10-1200 ppm for H₂. Significant sensitivity, small relative standard deviation (RSD) and acceptable limit of detection (LOD) were obtained for each analyte, showing capability of SWCNTs for gas separation and determination processes. Finally, the method was used to evaluate the contents of CO₂ in air sample.