Comparison of two-stage retention index monitoring capillary gas chromatography and selected ion monitoring capillary gas chromatography – mass spectrometry as analytical tools

Two-stage capillary GC with two-stage retention index monitoring is an efficient analytical technique which can be used for detection and determination of small amounts of volatile compounds in complex mixtures of hundreds or thousands of other compounds. The system employs two capillary columns, coated with different stationary phases, connected on-line with the aid of a micro valve; the first column acts as a pre-separating unit from which unresolved fractions of interest are cut (transferred) into another column for final, interference-free separation of the compounds to be determined. This technique has been compared with selected ion monitoring capillary GC-MS using a hydrocarbon mixture as a test sample for comparing resolution, repeatability, and the practical usefulness of the techniques. Results indicate that two-stage capillary GC is very useful for mixtures containing compounds which produce mostly non-specific ions in the MS ion source whereas compounds producing specific ions can be easily analyzed by capillary GC – single ion monitoring MS even if they are not perfectly separated by a single capillary column.     

On-line multidimensional chromatography using packed capillary liquid chromatography and capillary gas chromatography

The introduction of selected fractions from a liquid chromatograph into a gas chromatograph has been described; however, analyses were performed by off-line experiments requiring collection and reinjection of the separate fractions or by on-line procedures where disadvantageously, only a fraction of the separated peak or a well resolved component in a mixture could be introduced into a gas chromatograph. This disadvantage is overcome by the apparatus and method described in this paper, which utilizes a multidimensional chromatography system employing a high efficiency, packed capillary LC column coupled on-line to a capillary gas chromatograph. The liquid chromatograph (so designed) can act as a highly efficient clean-up or chemical class fractionation step prior to introduction into the gas chromatograph, significantly reducing sample preparation times in many applications. Thus minor components in a complex matrix can be determined without prior sample clean-up, an example of which is the determination of polychlorinated biphenyls in a complex hydrocarbon matrix.     

Dicholorbenzyl alkyl ether homologs as retention index markers and internal standards for the analysis of environmental samples using capillary gas chromatography

A homologous series of 2,4-dichlorobenzyl alkyl ethers (DCBEs) have been synthesized and purified for use as retention index calibrants and internal standards. They are stable, sensitive to ECD and FID and ideal for GC-MS, with base peaks at m/z 159/161. The retention index calibration against the n-alkanes for a linear temperature program (LTP) series is given and recommendations made for the most suitable members of the DCBE series for use as internal standards in organochlorine (OC) residue analysis.     

Influence of the carrier gas on retention factors of gaseous hydrocarbons on polytrimethylsilylpropyne using capillary gas chromatography

The retention factor and height equivalent of a theoretical plate for gaseous hydrocarbons C₁—C₄ were studied on capillary columns with the layer of the new polymeric adsorbent polytrimethylsilylpropyne (PTMSP) as functions of the nature and pressure of the carrier gas. The retention factor k increases in the series helium < nitrogen < carbon dioxide. The k values depend linearly on the average pressure of the carrier gas in a capillary column with the adsorption PTMSP layer.     

Identification of unknown compounds on the basis of retention index data in comprehensive two-dimensional gas chromatography

The identification of unknown compounds in complex samples is very difficult. Comprehensive two-dimensional gas chromatography (GC x GC) provides very good resolution and improved identification reliability. Mass spectrometry is a powerful identification tool and retention index data are another good approach to this end. In this study, a second-order polynomial was used to calculate retention index data based on n-alkanes beyond the region of the 'isovolatile' curve in GC x GC, and the results in the 2nd dimension were validated by using the same stationary phase column in one-dimensional GC. To test the usefulness of the method, volatile compounds in a tobacco leaf extract fraction were analyzed using GC x GC, and 60 compounds were identified on the basis of their retention indices.     

The influence of the carrier gas on retention in capillary gas-solid chromatography

In capillary gas-solid chromatography where interactions between solute and carrier gas and adsorption of the solute on the surface of the adsorbent are considered to be imperfect, it has been shown that chromatographic retention is determined largely by adsorption processes. It has been established that correlation relationships k(P₂)=A k(P₁) + B, where k is the retention factor, and A and B are equation constants, was valid for use of different carrier gases P₁ and P₂. Column efficiency could be improved by use of carbon dioxide. The advantages of using carbon dioxide as the carrier gas were investigated.     

Capillary gas chromatography of esters correlations between structure and retention index

Summary The retention index of twenty different homologous series of esters have been determined experimentally on polar (Carbowax 1540) and non-polar (squalane) columns. General equations to calculate retention index have been established by statistical methods. The influence of the length and inductive effect of acid and alcohol chains and the relative position of the carboxylic group are discussed.     

Uncoated capillary column inlets (retention gaps) in gas chromatography

Uncoated but deactivated pre-columns have become a widely used tool in capillary gas chromatography (GC), serving strongly differing purposes. Pre-columns are often used as guard columns, reducing the effects of involatile sample by-products on chromatographic performance and rendering exchange of contaminated column inlets simple. Wide-bore pre-columns facilitate introduction of the syringe needle and open the way for a relatively robust on-column autosampler. Other pre-columns are used for re-concentrating solute bands that are broadened due to the flow of sample liquid in the column inlet (retention gap). Long pre-columns allow on-column injection of large sample volumes (e.g., 50-80 microliter when a 15 m X 0.32 mm I.D. pre-column is used). The background of the various uses of pre-columns is discussed, concluding with an evaluation of different deactivation methods for the internal wall of the pre-columns. Critical parameters are inertness, wettability and retention power. Press-fit connections are recommended for coupling pre-columns to the coated columns.     

Identification of oxygenated polycyclic aromatic hydrocarbons in diesel particulate matter by capillary gas chromatography and capillary gas chromatography/mass spectrometry

Summary Using a two-step liquid chromatographic separation on normalphase cartridges, crude extracts of diesel particulate matter can be separated without time-consuming sample handling into special fractions which mainly contain slightly-polar oxygenated polycyclic aromatic hydrocarbons (oxy-PAH) and nitrated polycyclic aromatic hydrocarbons (nitro-PAH). Subsequent analysis was by fused-silica capillary gas chromatography on a SE54 column along with flame-ionisation (GC/FID) and positive-ion electron-impact mass spectrometric detection (GC/MS) respectively. A number of individual oxy-PAH belonging to four different chemical classes (ketones, quinones, anhydrides and aldehydes) and several individual nitro-PAH were characterized by their retention times and mass spectra. Presented at the 15th International Symposium on Chromatography, Nürnberg, October 1984     

A comparison of different retention index systems with unsaturated and aromatic hydrocarbons in capillary gas chromatography on PEG 20M

Summary The correction of the reproducibility of retention indices on polar capillary columns with different film thickness, using more polar reference standards instead ofn-alkanes, was investigated. It was found that the replacement ofn-alkanes by 1-alkenes, 3-alkynes and n-alkylbenzenes as standards significantly improves the reproducibility of retention indices and diminishes their temperature increments forn-alkanes,n-alkynes and arenes on PEG 20M columns.     

An homologous series of benzodiazepine retention index standards for gas chromatography

An homologous series of benzodiazepine retention index standards (the R-series) has been synthesized and the gas chromatographic behavior of the series investigated on NB-54 and NB-1701 capillary columns. The compounds were stable, exhibited symmetrical peak shapes, and fairly linear retention behavior was observed on both columns. The series can be coinjected with every sample to enable the high precision analysis of toxicological samples; screening for 20 benzodiazepine drugs was possible in 23 minutes (including cooling). The R-series method was compared with a retention index method based on a series of benzodiazepine drugs as standards and with a method employing relative retention times. The precision of the R-series method was found to be generally better than that of the two other methods in both long- and short-term studies.     

Rapid gas analyses for the investigation of spontaneous combustion using capillary gas chromatography

A simple and fast but sensitive and precise gas chromatographic method is described for the quantitative determination of O(2), N(2), CO, CO(2), C1 and C2-hydrocarbons for coal research. Gas analyses are necessary to obtain parameters for modelling spontaneous combustion and to predict long term coal behaviour. The method is based on a single PLOT-type capillary column in a single channel gas chromatograph. Using a micro-volume TCD coupled in series with a FID detector containing a capillary methanizer it is possible to determine high and trace level gases simultaneously. Trace quantities of CO and CO(2) can be determined with a single analysis and the detection limits are improved significantly using the capillary methanizer. The detection limit of the described method is approximately ten parts per million CO(2) and one part per million CO. Using the same instrument configuration the O(2)/N(2) ratios (major components), as parameter for coal reactivity, are also determined. The proposed approach is restricted to the determination of gases evolved during coal studies and the application to other gas mixtures is not considered.     

Dependence of the width of the chromatographic zone on retention time in capillary gas chromatography

The dependence of the width of the chromatographic zone on retention time for capillary columns was studied theoretically and experimentally. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 320–322, February, 1997.     

New applications of the retention index concept in gas and high performance liquid chromatography

New methods for the precalculation of GC retention indices (RIs) are discussed. The first is based on a new modification of the correlation equation log RI = a logT_b + bA + c and is recommended for low boiling compounds of the general type R-X with known boiling points (T_b) analyzed on polymer sorbent Porapack Q. The second method permits one to predict RIs of products of organic reactions A + B → C +… with the correlation ΔRI = a ΔE + b (a < 0,|ρ| > 0.9), where ΔRI = RI_C– RI_A– RI_B and ΔE = E_C– E_A– E_B– are the differences in the internal molecular energies of reagents and products of organic reactions which are estimated by molecular dynamics methods. In the final section new possibilities of the use of RIs in reversed phase HPLC, namely for the determination of the number of hydroxyl groups in phenols, are illustrated.     

New applications of the retention index concept in gas and high performance liquid chromatography

New methods for the precalculation of GC retention indices (RIs) are discussed. The first is based on a new modification of the correlation equation log RI = a logT_b + bA + c and is recommended for low boiling compounds of the general type R-X with known boiling points (T_b) analyzed on polymer sorbent Porapack Q. The second method permits one to predict RIs of products of organic reactions A + B → C +… with the correlation ΔRI = a ΔE + b (a < 0,|ρ| > 0.9), where ΔRI = RI_C– RI_A– RI_B and ΔE = E_C– E_A– E_B– are the differences in the internal molecular energies of reagents and products of organic reactions which are estimated by molecular dynamics methods. In the final section new possibilities of the use of RIs in reversed phase HPLC, namely for the determination of the number of hydroxyl groups in phenols, are illustrated. Received: 9 November 1998 / Revised: 15 April 1999 / Accepted: 30 April 1999     

Analysis of pyrethrins using capillary supercritical fluid chromatography and capillary gas chromatography with fourier transform infrared detection

The six insecticidally active components in a commercial preparation of pyrethrin extract are separated by capillary gas chromatography (GC) and by capillary supercritical fluid chromatography (SFC). Thermal degradation of pyrethrin I and II are observed under the GC conditions required to separate the pyrethrin components. The use of shorter columns and thinner stationary phase coatings reduce the amount of degradation but cannot eliminate degradation of pyrethrin II. The SFC chromatograms, obtained under thermally mild conditions, show that all components including pyrethrin II elute without degradation. Infrared spectra of cinerin I & II, jasmolin I & II, and pyrethrin I & II are obtained using a flow through SFC/IR detection cell. Spectra clearly reveal the structural differences needed to distinguish and identify the components in the extract.