Highly accurate gas chromatographic analysis of reference gases for use in vehicle emission measurements

 A highly accurate gas chromatographic analytical method has been developed for the determination of the composition of gas mixtures. It was tested using a reference gas as an example consisting of 3.5% of CO, 14% of CO₂, 0.2% of propane and residual N₂ intended for the use in vehicle emission measurements. The method is based on comparison measurements with samples of a calibration gas, whose composition is iteratively adapted to that of the sample investigated using a gravimetric gas mixing method. For the gas chromatographic measurement, a molecular sieve column and a polymer column are used in parallel and in isothermal operation. All gas components can be determined by a single gas chromatographic measurement, and the relative uncertainty of measurement achievable is ?0.4%. Received: 6 March 1996/Revised: 30 May 1996/Accepted: 6 June 1996     

Gas chromatography analysis: method validation and measurement uncertainty evaluation for volume fraction measurements of gases in simulated reformate gas stream

It is important to understand each analytical system and its limitations when performing any chromatographic measurements. In the present paper, a methodology for method validation and measurement uncertainty evaluation for the measurement of volume fractions of selected gases (CO₂, CO, CH₄, H₂) in simulated reformate gas streams by using gas chromatography was developed. A detailed procedure for in-house method validation based on a simple experimental design and consistent statistics is presented. The analytical protocol allowed us to quantify gases in volume fractions from 2.00 to 100.0 mL/(100 mL) with satisfactory recoveries. We proved that the method was selective for the measurement of gases in simulated reformate gas stream. In addition, a step-by-step illustration of modelling approach for measurement uncertainty evaluation of each component is also provided. Uncertainty arising from repeatability and trueness is relatively low, while the contribution from reproducibility is of higher level for all the analytes tested. The main reason for this is changes in atmospheric pressure that affect gas chromatographic measurements. Solution of this problem could be more frequent calibration of apparatus, yielding to higher costs and more time-consuming process, or by measuring the atmospheric pressure and using it to correct the response of the gas chromatograph for resulting variations in sample size. The obtained results confirm that it is imperative to fully characterize the analytical system before proceeding with an analysis.     

Validated Stability-Indicating Chromatographic Methods for the Determination of Veralipride in Presence of Its Degradation Products

Two sensitive and selective chromatographic methods were developed and validated for determination of veralipride in presence of its degradation products. Forced degradation studies were performed, using HCl, NaOH and 3% H₂O₂. The first method is based on thin-layer chromatographic separation of the intact drug spot from its degradation, followed by densitometric measurements. The second method is based on isocratic liquid chromatographic separation of the studied drug from its degradation on a reversed phase C₁₈ column. The proposed LC method was utilized to investigate the kinetics of alkaline degradation process of the selected drug at different temperatures.     

Comparison of different methods to estimate the uncertainty in composition measurement by chromatography

Natural gas is a mixture that contains hydrocarbons and other compounds, such as CO₂ and N₂. Natural gas composition is commonly measured by gas chromatography, and this measurement is important for the calculation of some thermodynamic properties that determine its commercial value. The estimation of uncertainty in chromatographic measurement is essential for an adequate presentation of the results and a necessary tool for supporting decision making. Various approaches have been proposed for the uncertainty estimation in chromatographic measurement. The present work is an evaluation of three approaches of uncertainty estimation, where two of them (guide to the expression of uncertainty in measurement method and prediction method) were compared with the Monte Carlo method, which has a wider scope of application. The aforementioned methods for uncertainty estimation were applied to gas chromatography assays of three different samples of natural gas. The results indicated that the prediction method and the guide to the expression of uncertainty in measurement method (in the simple version used) are not adequate to calculate the uncertainty in chromatography measurement, because uncertainty estimations obtained by those approaches are in general lower than those given by the Monte Carlo method.     

Capillary gas chromatographic analysis of highly brominated fire retardant compounds

We report the development of a capillary gas chromatographic method, superior to existing packed column methods, for the analysis of highly brominated additive fire-retardants, including decabromodiphenyl ether (1) and decabromodiphenoxyethane (II). Neither compound has been analyzed previously by capillary GC, and there are no published methods for (II). For (I), the new method is 5–10 times faster than an analogous packed column method, and it has 100 times lower detection limits and twice the precision of a gas chromatographic/mass spectrometric method. For (II), the capillary method is 30–50% faster than an unpublished liquid chromatographic method. The greater efficiency of the capillary method makes possible the complete resolution (R ≥ 1.25) of structurally very similar compounds (e.g. compound (II) and its Br₉Cl₁ and Br₈Cl₂ analogues). With the new method, commercial preparations of (I) and (II) can be rapidly analyzed, and samples from combustion and pyrolysis experiments can be evaluated for compositional changes.     

Analysis of small carbohydrates in several bioactive botanicals by gas chromatography with mass spectrometry and liquid chromatography with tandem mass spectrometry

Bioactive botanicals contain natural compounds with specific biological activity, such as antibacterial, antioxidant, immune stimulating, and taste improving. A full characterization of the chemical composition of these botanicals is frequently necessary. A study of small carbohydrates from the plant materials of 18 bioactive botanicals is further described. The study presents the identification of the carbohydrate using a gas chromatographic‐mass spectrometric analysis that allows detection of molecules as large as maltotetraose, after changing them into trimethylsilyl derivatives. A number of carbohydrates in the plant (fructose, glucose, mannose, sucrose, maltose, xylose, sorbitol, and myo‐, chiro‐, and scyllo‐inositols) were quantitated using a novel liquid chromatography with tandem mass spectrometric technique. Both techniques involved new method developments. The gas chromatography with mass spectrometric analysis involved derivatization and separation on a Rxi^®‐5Sil MS column with H₂ as a carrier gas. The liquid chromatographic separation was obtained using a hydrophilic interaction type column, YMC‐PAC Polyamine II. The tandem mass spectrometer used an electrospray ionization source in multiple reaction monitoring positive ion mode with the detection of the adducts of the carbohydrates with Cs⁺ ions. The validated quantitative procedure showed excellent precision and accuracy allowing the analysis in a wide range of concentrations of the analytes.     

Multidimensional Gas Chromatography–Mass Spectrometry Method for Fingerprinting Polycyclic Aromatic Hydrocarbons and Their Alkyl-Homologs in Crude Oil

The composition of polycyclic aromatic hydrocarbons in crude oil is usually too complex to use standard capillary gas chromatography to separate all of the components. In this study, a multidimensional gas chromatography–mass spectrometry (GC-MS) technique was used to analyze polycyclic aromatic hydrocarbon fractions of crude oil collected from the Dongying oil field in the Bohai Sea. A DB-17MS column (30?m?×?0.25?mm?×?0.25?µm) was used as a prefractionating column and only selected heart-cuts were transferred to the second chromatographic dimension (HP-5MS, 15?m?×?0.25?mm?×?0.25?µm) by a pressure-adjusted continual flow-type switching device for quantification of the polycyclic aromatic hydrocarbons. The chromatographic elements and parameters, such as detector selection and column combinations, were optimized. Naphthalene, phenanthrene, fluorene, dibenzothiophene, chrysene, and their C₁–C₄ alkyl homologs were identified. The profile of the polycyclic aromatic hydrocarbons obtained using the multidimensional GC-MS method was compared with the results obtained by traditional one-dimensional GC-MS.     

Peak parking method for measurement of molecular diffusivity in liquid phase systems

The combination of series of measurements of band broadening made with the peak parking (PP) method, using successively an open capillary tube and a HPLC column, gives a convenient procedure for the measurement of the molecular diffusivity (D_m) of compounds in solutions, of their axial dispersion coefficient (D_ax,m) in chromatographic columns, and of the tortuosity or obstructive factor of the column bed. The molecular diffusivity measured for benzene in methanol was in excellent agreement with literature data. The ratio of the axial dispersion coefficient to this diffusivity gives the obstructive factor (γ_m) of the packed bed, which was 0.74 for the column used. The values of D_m in other solutions were obtained from the D_ax,m values measured by the PP method, by correcting the D_ax,m values with the γ_m value. The D_m values determined by this method were in good agreement with those previously reported or estimated using literature correlations. These results showed that the PP method is effective for the experimental measurement of D_m.     

Gas chromatographic determination of inorganic gases in high purity ethylene

Summary A simple and sensitive gas chromatographic method using the single column technique without an extreme working temperature range for the separation of O₂, N₂, CO and CO₂ was developed. The analysis was performed on micropacked columns filled with active charcoal with particle size distribution smaller than 20 m, using a microthermal conductivity detector. The results obtained show that such a column is capable of good separation of O₂, N₂ and CO at room temperature. To shorten the elution time of CO₂ the temperature has to be elevated above ambient temperature by about 100°C. Employing for ethylene removal the subtraction method introduced in gas chromatography very early by Ray, the achieved separation of inorganic gases was usefully applied for the determination of inorganic gases traces in high purity ethylene.     

Gas Chromatographic Determination of Cinoxacin

A gas Chromatographic method has been established for analysis of Cinoxacin in crystalline powder. The method is based on chemicaI derivatization of Cinoxacin as its methyl ester, and n-octacosane is used as an internal standard. Gas chromatographic analysis was proceeded on a glass column packed with 2% OV-1 on Chromosorb W. Quantitation is feasible by measurements of peak area ratios. The method proves to be simple, rapid and accurate.     

Determination of volatile halogenated hydrocarbons in tap water,seawater and industrial effluents by glass capillary gas chromatography and electron capture detection

A rapid and sensitive method to determine volatile organohalides in different types of waters has been developed. The chromatographic system is based on the resolving power of the glass capillary column and the high sensitivity of the electron capture detector. The capillary columns were connected to the detector so that the eluate from the column is mixed with thermostatted purge gas to minimize band broadening due to dead volumes. The low column bleeding and decreased band spreading from capillary columns enhance the sensitivity to very low levels: 1 fg (10^?15g) for carbon tetrachloride, despite dilution of the column eluate by the purge gas. The water samples of 100 ml were extracted with 1 to 10 ml n-pentane which is the most practical alkane with respect to purity. When using high water to pentane ratios corrections had to be made, due to low extraction yield, to get accurate quantifications. A column with Carbowax 400 stationary phase permits direct tap water injection. The water peak concealed the substances eluated after CHCl₃ and CHBrCl₂. The gas chromatographic separation of haloforms in tap water could be shortened to 30 seconds using a 10 m SE–52 column with an increased film thickness. Besides tap water and seawater, industrial waste water from a pulp mill was analyzed. Ten different halogenated organic compounds, ranging from 1 ng/I to 760 μg/I, were quantified in the different waters. Bromoform, which had not previously been found in seawater, was detected. Chromatogram of a standard mixture containing 11 organohalides. Stationary phase, SE-52; 33 m × 0.3 mm i.d. inj. temp. 200°, column temp. 50°, interface 250°, detector temp. 250°. Helium carrier gas flow rate, 36 cm/s, scavenger'gas flow 30 ml/min. Split ratio 1:20, 1 = CH₂CI₂, 2 = CHC1₃, 3 = CH₃CC1₃, 4 = CC1₄, 5 = CHCICCI₂, 6 = CHBrCI₂, 7 = CBrC1₃, 8 = CHBr₂Cl, 9 = CCl₂CC1₂, 10 = CHCl₂l, 11 = CHBr₃.     

Measurements of dissolved nonmethane hydrocarbons in sea water

Summary An automated stripping technique for the measurement of dissolved hydrocarbons in sea water is presented together with some results obtained during a ship cruise from Europe to Brazil. The sea water concentrations of NMHC were determined in a three step process: degassing, preconcentration, and gas chromatographic analysis. In a stripping chamber the dissolved gases were purged from sea water with helium. The stripped hydrocarbons were cryogenically concentrated, and after thermal desorption they were injected into the gas chromatograph. The light fraction (C₂–C₄) was separated on a packed and the heavy fraction (C₅–C₁₀) on a capillary column. All valves were microprocessor controlled in order to achieve an automated process. For the C₂–C₄ hydrocarbons the stripping efficiencies exceeded 90% except for acetylene (80%), the lower limit of detection was 1 to 4.5 pmol hydrocarbon per liter of sea water and the accuracy of the method was better than 25%, depending on the individual hydrocarbons. Typical oceanic concentrations were in the 10 and 100 pmol/l range. Alkenes were generally more abundant than the corresponding alkanes and within the homologous series the concentrations decreased with increasing number of carbon atoms.     

Beiträge zur Chemie des Phosphors. 43. Gaschromatographische Trennung von Phosphanen

Monophosphane (PH₃), diphosphane (P₂H₄), and triphosphane-5 (P₃H₅) could be separated in mixtures by isothermal gas chromatography. On the basis of the experiences hereby obtained, further gas chromatographic separations were carried out with a programmed temperature mode. For the identification of the chromatographic peaks a mass spectrometer as a second detector was applied. In the temperature range from ?60°C to +60°C, it was possible for the first time to separate mixtures of diphosphane and higher phosphanes without any decomposition in the gas chromatographic column. Besides monophosphane and diphosphane, triphosphane-3 (P₃H₃), triphosphane-5 (P₃H₅), and tetraphosphane-6 (P₄H₆) could be eluated as undecomposed components. By this, a fundamental basis for the application of gas chromatography to the quantitative analysis of mixtures of phosphanes and to the development of a gas chromatographic method for the preparative isolation of individual higher phosphanes has been established.     

Separation of Methylated Purines by High Pressure Liquid Chromatography

Abstract

This paper reports a method for the separation and measurement of methylated purines of interest to carcinogenesis studies by high-pressure liquid chromatography (HPLC) following their column chromatographic isolation from collected urine samples. HPLC was evaluated on three different cation-exchange columns, with optimum conditions obtained on a Partisil 10-SCX column employing isocratic elution with 0.25M (NH₄)H₂PO₄ at pH 4.0. This column was also found to be useful for the separation of mono-methylguanine isomers. Application is shown to the analysis of rat urine following animal treatment with methyl methanesulfonate.     

Analysis of trace levels of impurities and hydrogen isotopes in helium purge gas using gas chromatography for tritium extraction system of an Indian lead lithium ceramic breeder test blanket module

In the fusion fuel cycle, the accurate analysis and understanding of the chemical composition of any gas mixture is of great importance for the efficient design of a tritium extraction and purification system or any tritium handling system. Methods like laser Raman spectroscopy and gas chromatography with thermal conductivity detector have been considered for hydrogen isotopes analyses in fuel cycles. Gas chromatography with a cryogenic separation column has been used for the analysis of hydrogen isotopes gas mixtures in general due to its high reliability and ease of operation. Hydrogen isotopes gas mixture analysis with cryogenic columns has been reported earlier using different column materials for percentage level composition. In the present work, trace levels of hydrogen isotopes (∼100 ppm of H₂ and D₂) have been analyzed with a Zeolite 5A and a modified γ‐Al₂O₃ column. Impurities in He gas (∼10 ppm of H₂, O₂, and N₂) have been analyzed using a Zeolite 13‐X column. Gas chromatography with discharge ionization detection has been utilized for this purpose. The results of these experiments suggest that the columns developed were able to separate ppm levels of the desired components with a small response time (<6 min) and good resolution in both cases.     

Stabilization of gas chromatographic stationary phases with nanosized particles

Summary Stabilization of polar and apolar stationary phases with nanosized particles has been demonstrated for gas chromatographic capillary columns. Mixtures of small amounts of (2–10%) of solid particles and liquids form gels, which preserve the stability of the films of stationary phases on the column walls. The stabilization effect of polar and apolar particles has been studied by determining some rheological properties of gels (flow curves, temperature dependence of yield stress values) and validated by gas chromatographic measurements using the most polar and apolar stationary phases. Dedicated to the memory of late Dr. Gábor Alexander, who was the inventor of this film stabilization method, and took active part in the early experiments.     

Gas Chromatographic Analysis of Cholesterol Oxidation Products on a Thermostable Medium Polarity Capillary Column

The performance of a fused silica column coated with 50% phenyl-/50% dimethyl-polysiloxane, characterized by a high thermal stability, was evaluated for the gas chromatographic determination of cholesterol oxidation products. A silylated mixture of eighteen oxysterol standards (0.1 mg/ml of each compound) was injected into the gas chromatographic system. The temperature was programmed from 230 to 260°C at 2.5°/min and then to 290°C at 1°/min; the injector and detector temperatures were set at 325°C, and the gas linear velocity was 22.8 cm/s. The column gave a fast (15 min) and satisfactory resolution of the main cholesterol oxides. Good separation of the hydroxy from the epoxy derivatives was achieved.The suitability of the method for the determination of oxysterols in food matrices was successfully tested on a saponified lipid extract from egg yolk powder, previously enriched and purified by NH₂ solid phase extraction.     

Analysis of light hydrocarbons C1–C5 with Porous Layer Open Tubular fused silica columns of aluminum oxide. Part 1: The column

A method is described for the preparation of a Porous Layer Open Tubular (PLOT) fused silica column coated with submicron particles of aluminum oxide for the analysis of light hydrocarbons. The column is thermally stable and provides reproducible analytical data over a long period of time. The column can be operated at temperatures easily controlled by commercially available gas chromatographic apparatus. 1,3-Butadiene is retarded much more than its principal impurities: thus the polarity of aluminum oxide is extremely useful for butadiene analysis because none of the contaminants is obscured by the butadiene peak. The analysis of the 16 most common C₁–C₄ hydrocarbons is achieved within 5 min at 60°C with helium as the carrier gas. Conditioning of the carrier gas with water vapor from CuSO₄.5H₂O to decrease the activity of the aluminum oxide is described. Some applications of a 30 m × 0.32 mm aluminum oxide PLOT column are given.     

Solid-Phase Extraction and Capillary Gas Chromatographic Determination of Triazine Herbicides in Water

Abstract

A facile and efficient method is described for the determination of trace quantities of triazine herbicides, terbutryn, prometryn and ametryn in water. The procedure involved preconcentration of water samples by sorption on chromatographic grade silica gel particles with chemically modified surface, being covalently bonded with a nonofunctional C₈H₁₇ group. This was followed by solvent desorption with 2-propanol. The determinative step was achieved by capillary gas chromatography on Supelcowax-10 fused silica column using a nitrogen-phosphorus detector. The limit of detection was 0.1 μg-10 μgL^?1.     

The Analysis of volatile compounds by purge and trap with whole column cryotrapping (WCC) on a fused silica capillary column

The purge and trap (P&T) method of analysis has been interfaced with fused silica capillary column gas chromatography. This interfacing has been accomplished without splitting the P&T trap desorption carrier gas. Thus, 100% of the purged compounds are transferred to the column. The analytes are cryofocussed on the column using whole column cryotrapping (WCC) at ?80°C. The resulting P&T/WCC procedure is extremely well-suited to the analysis of trace purgeable aqueous organic compounds. Samples and standards containing a variety of aromatic standard compounds were analyzed. The standards included benzene, toluene, ethylbenzene, xylenes, C₃-C₄-benzenes, and naphthalene, as well as three P&T internal standard compounds. Chromatographic peak widths were uniformly less than 6 s at the base and excellent precision was obtained in the relative retention time data for all compounds. The chromatogram of a groundwater sample contaminated with aromatic gasoline compounds is also presented. Since P&T/WCC works well with fused silica capillary columns, the full sensitivity and chromatographic efficiency of capillary gas chromatography is made available to P&T analyses.