Capillary gas chromatography of amines with ammonia as carrier gas

The use of ammonia as a carrier gas for the chromatography of aliphatic and aromatic amines has been investigated. As compared to nitrogen, ammonia gave drastically improved peak symmetry and lower capacity factors (k′) for primary and secondary amines on polar (Polyethylene glycol) and medium Polar (methylphenylcyanopropylsilicone) stationary Phases. The effect of ammonia was more Pronounced at low column temperatures. Considerably better detection limits of primary and secondary amines were obtained with ammonia as carrier gas than with nitrogen. No detrimental effects of using ammonia were observed on the gas chromatograph or on the columns over a period of about one year.     

Reaction gas chromatography: Study of the photodecomposition of selected substances

Summary A simple apparatus that permits to carry out photolytic reactions in direct connection with a gas chromatograph has been designed. The photodecomposition of C₅–C₇ aliphatic alkanes, C₁–C₅ primary, secondary and tertiary aliphatic alcohols and of some other substances was studied using this apparatus. The degradation products are characteristic of the individual types of alcohols. The identification of the individual types of alcohols. The identification of the degradation products confirms the proposed schemes for the photodegradation reactions. The apparatus described can also be used for the study of photolysis kinetics, as it permits the easy and rapid variation of the reaction conditions.     

Effect of ammonia on the response of the electron capture detector (ECD)

The effect of ammonia on the electron capture detector (ECD) response has been investigated. Nitrogen with different ammonia concentrations (5–20%) was used as make-up gas. Compared to pure nitrogen, the ECD response decreased when the ammonia concentration in the make-up gas was 5%. However, the response increased when the ammonia concentration was 20%. The response factor of 4-chlorophenol increased 4 fold when ammonia was 20%. Also, di- and tri-chlorophenols increased by 30–50%. The nitroaromatic compounds responses increased by about 2–3.7 times with 20% ammonia in the make-up gas. The signal-to-noise (S/N) increased when 20% ammonia in nitrogen was used as make-up gas compared to pure nitrogen. Also, the detector linearity increased by 50% with ammonia.     

Study of the surface ionization detector for gas chromatography

The structure of the surface ionization detector (SID) and the operation parameters of GC-SID were investigated to reduce peak tailing and to enhance sensitivity. The performances of the GC-SID, including its repeatability, linearity, sensitivity, selectivity, and tolerance towards water vapor, were evaluated systematically. Compared with nitrogen-phosphorus detector (NPD), the SID was able to detect fg level triethylamine, and selectively respond to alkylamines, some anilines, and some nitrogen heterocyclic compounds. Among alkylamines, the SID sensitivity to diisobutylamine was rather small. Even so, it was also still 10 times higher than that on NPD. The SID selectivity, defined as the sensitivity ratio between triethylamine and various tested non-nitrogen compounds, was higher than 10(6). It was found that the SID is highly tolerant towards water vapor, allowing direct injection of water sample. Finally, the GC-SID was applied to directly measure trace amines in headspace gases of rotted meat and trace simazine in tap water. The SID sensitivity to simazine was proven to be 5 times higher than that on flame ionization detector (FID). This study suggests that the SID is a promising GC detector.     

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.     

Flow of the carrier gas in open-tubular capillary columns in temperature-programmed gas chromatography

A second-order non-linear partial different equation was derived to describe the dependence of carrier gas pressure in the column on the column distance and the time under temperature programmed conditions. This equation was solved numerically by the modified finite difference method for various column parameters. Constant inlet and outlet pressures were used as boundary conditions. The retention times calculated on assumption of a constant pressure profile along the column. Significant differences between retention times of corresponding solutes calculated by the two methods were found, especially when relatively long columns(L>50m) with small internal diameter(d<0.3mm)and high temperature program rates (r>5°/min)are used.     

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.     

Characterization of a microelectromechanical systems-based counter-current flame ionization detector

This work is concerned with the influence of different operating parameters on the response of a counter-current micro flame ionization detector (cc-μFID) with low gas consumption for mobile applications. At cc-μFID flow rates (<10ml/min hydrogen), the response depends mainly on the oxygen flow. At 7.5ml/min hydrogen flow, highest sensitivity (13.7mC/gC) is obtained with the smallest flame chamber and nozzle size, moderate sample gas flow (2.0ml/min), and an oxygen flow above stoichiometry (9.4ml/min, λ=2.5). The largest absolute signal is obtained at increased sample gas flow (8.0ml/min). However, to prevent parting of the micro-flame by the sample gas stream, largest nozzles (smallest outflow velocity) give the best result (4.37nA). Whereas cc-μFID sensitivity is comparable with conventional FID sensitivity, peak-to-peak noise of 1pA is relatively large. Therefore, the minimum detectable carbon mass flow of 1.46×10(-10)gC/s and the minimum detectable methane concentration of 3.43ppm are larger than typical FID detection limits. μGC-μFID experiments show the difference between premixing the sample with the hydrogen or with the oxygen with respect to sensitivity and response factors. Sensitivity is decreased considerably when the column effluent is added to the oxygen instead of to the hydrogen. For hydrogen premixed samples the response factor to butane can be increased up to 0.81 (methane=1), whereas for oxygen premixed samples it is maximally 0.31. This smaller sensitivity to oxygen premixed samples and the larger variation of response factors shows the importance of the hydrogen atom during breakdown of organic molecules to single-carbon fragments before ionization.     

Investigating the performance characteristics of the barrier discharge ionization detector and comparison to the flame ionization detector for the gas chromatographic analysis of volatile and semivolatile organic compounds

Abstract

The response behavior and performance characteristics of the recently introduced barrier discharge ionization detector (BID) for gas chromatography (GC-BID) were investigated by analyzing different classes of organic compounds such as alcohols, alkanes, cycloaliphatic compounds, polycyclic aromatic hydrocarbons (PAHs), and others. The results obtained by GC-BID were compared with those of gas chromatography with flame ionization detection (GC-FID), aiming to demonstrate the particular merits of the new BID detector over the well-established FID. The response of the BID not only was found to be strongly dependent on the detector settings, but also shows a high dependence on the analyte class and the individual analyte. The sensitivity of the BID detector compared to the FID was higher by a factor of ca. 4 on average when considering all compounds analyzed. The relative standard deviation (RSD) was better than 5% for the majority of the cases. The BID detector showed better precision (lower RSD) in comparison with the FID for the investigated compounds. Linear calibrations were obtained for the analytes over more than four orders of magnitude with coefficients of determination typically higher than 0.999 and the limits of detection varied from 0.04 to 1.48?ng/s for the GC-BID.     

The effect of molecular structure upon the response of the flame ionization detector

Summary It is known that the response of the FID is proportional to the number of carbon atoms in hydrocarbon molecules. If there is a heteroatom in the molecule, the response of the FID decreases. It is possible to calculate the sensitivity to any organic molecule if the signal-decreasing effect of a heteroatom or functional group is known. The sensitivity of a detector to an organic molecule containing heteroatoms is referenced to normal hydrocarbons by means of the effective carbon-atom number (ECN). Several authors have dealt with the determination ofECN values of different molecules and the effective carbon-atom number increment (ECN _inc) values for different functional groups and heteroatoms. In our previous work [1]ECN _inc values of several components were studied for homologous series. In this study we have investigated the effects of molecule structure upon ECN values by comparing theECN _inc of functional groups which are attached to molecules of different structure.     

Selectivity enhancement of a metal-sensitive flame ionization detector for capillary gas chromatography

A novel modification of a hydrogen-atmosphere flamo ionization detector (HAFID) is presented which attenuates response to hydrocarbon compounds, significantly enhancing selectivity towards organometallic compounds by more than an order of magnitude. Chromatograms of an organometallic compound test mixture and regular leaded gasoline are presented to depict the specificity of the response.     

Possible amounts of oxygen in the carrier gas as compared to sample amounts

Summary The amount of oxygen which may be present in the gas volume corresponding to a peak is investigated and compared to the sample amounts. It is shown that even with high purity carrier gases one may have a significant excess of oxygen present at low sample amounts. Attention is drawn to the possibility of impurity build-up by diffusion e.g. through the septum.     

Analysis of amine compounds by capillary gas chromatography using ammonia–helium carrier gas

The use of 10%, 1%, and 0.1% ammonia in helium as carrier gas was investigated as a means of improving poor chromatographic peak shape often associated with low level determinations of amine compounds using thin film capillary columns. The 1% ammonia in helium was found suitable for improving the peak shape of sterically unhindered amine compounds, such as urethane and certain aliphatic primary amines, during gas chromatographic analysis on thin film columns. There was a negligible effect on the peak tailing arising on thick film columns. The 0.1% ammonia in helium was suitable, but not as efficient as the 1% ammonia in helium, in eliminating the peak tailing associated with low level analysis of amine compounds. The signal-to-noise (S/N) ratio improved from < 1 using helium carrier gas to 20–25 (for certain test amine compounds) using 1% ammonia in carrier gas. The 10% ammonia in helium carrier gas had an effect on the chromatographic performance similar to that of the 1% ammonia in helium, but the baseline level was very high and this mixture was not used in further studies.     

The variation of carrier gas viscosities with temperature

After describing simplified equations exspressing the temparature dependency of the viscosity of carrier gases (helium, nitrogen and hydrogen ) relative to a base value, absolute relationships based on the kinetic theory of gases are discussed. Comparative data obtained using various calculation methods are given and are compared to measured values. Based on the kinetic relationshipsm, of viscosity. Finally, the influence of pressure on the viscosity is also briefly discussed. As a supplement, Viscosity data are tabulated for the three gases in the range of 0°C to 400°C in increments of 2 K, calculated using the kinetic relationships.     

Determination of volatile aliphatic amines in air by solid-phase microextraction coupled with gas chromatography with flame ionization detection

Practical aspects of the application of solid-phase microextraction (SPME) to the determination of volatile aliphatic amines in air are described. Analytes included methylamine (MA), ethylamine (EA), dimethylamine (DMA), diethylamine (DEA), trimethylamine (TMA) and triethylamine (TEA). New SPME stationary phases were examined. The effects of relative humidity and temperature on analytes uptake were taken into account in analysis. Gas chromatography (GC) with flame ionization detector (FID) was used for the final analysis.     

Selection of carrier gas velocity in the analysis of a multicomponent sample

Summary The selection of the average linear carrier gas velocity in the analysis of a multicomponent mixture under isothermal and programmed-temperature conditions is discussed. It is shown that one shouls always select a velocity which is at least equal but preferably higher than the optimum average gas velocity of the earliest peak at the initial column temperature.These symbols essentially correspond to those specified by the British Standard [6], ASTM [7] and IUPAC [8] GC nomenclastures.     

Use of hydrogen as a carrier gas for the analysis of steroids with anabolic activity by gas chromatography-mass spectrometry

Due to the impact in the media and the requirements of sensitivity and robustness, the detection of the misuse of forbidden substances in sports is a really challenging area for analytical chemistry, where any study focused on enhancing the performance of the analytical methods will be of great interest. The aim of the present study was to evaluate the usefulness of using hydrogen instead of helium as a carrier gas for the analysis of anabolic steroids by gas chromatography-mass spectrometry with electron ionization. There are several drawbacks related with the use of helium as a carrier gas: it is expensive, is a non-renewable resource, and has limited availability in many parts of the world. In contrast, hydrogen is readily available using a hydrogen generator or high-pressure bottled gas, and allows a faster analysis without loss of efficiency; nevertheless it should not be forgotten that due to its explosiveness hydrogen must be handled with caution. Throughout the study the impact of the change of the carrier gas will be evaluated in terms of: performance of the chromatographic system, saving of time and money, impact on the high vacuum in the analyzer, changes in the fragmentation behaviour of the analytes, and finally consequences for the limits of detection achieved with the method.     

Comparison of methods to enhance flame ionization detector (FID) signals in gas chromatography

The performances of some numerical methods to improve the signal to noise ratio are compared and applied to enhance noisy signals obtained in gas chromatography with capillary columns and a flame Ionization detector. Several methods have been considered: cutoffs In the Fourier transform of the recorded signal; real time numerical filtering; theoretical model curve fitting; and the correlation of a chromatogram recorded from a pseudorandomly injected sample with the pseudorandom injection function. Numerical real time filtering is shown to be the most convenient method when the main periodic component of the noise has been determined by Fourier analysis.