Characterization of complex hydrocarbon mixtures using on-line coupling of size-exclusion chromatography and normal-phase liquid chromatography to high-resolution gas chromatography

An on-line coupling of size-exclusion Chromatography (SEC), normal-phase liquid Chromatography (NPLC), and gas Chromatography (GC) for the characterization of complex hydrocarbon mixtures is described. The hyphenated system separates according to size, polarity, and boiling point. The use of size exclusion as the first separation step allows for the direct injection of complex (“dirty”) samples withont prior clean-up. SEC-NPLC coupling was realized using an on-line solvent evaporator based on fully concurrent solvent evaporation (FCSE) using a modified loop-type interface, vapor exit and co-solvent trapping. Complete reconcentration of the analytes was realized by the introduction of a cryogenic cold trap. For the subsequent hydrocarbon group-type separation an ammo-silica column with n-heptane as eluent was used. The NPLC-GC coupling was based on an on-column interface using partially concurrent solvent evaporation (PCSE) and an early vapor exit. Initial results obtained on the analysis of a residue from the atmospheric crude-oil distillation (a so-called long residue) are presented as an example of the enormous separation power of the SEC-NPLC-GC system. The application of the system for quantitative analysis has not yet been studied.     

Rapid determination of ethanol in fermentation liquor by full evaporation headspace gas chromatography

This paper reports a full evaporation (FE) headspace gas chromatographic (GC) method for rapid determination of ethanol in fermentation liquor. The data show that ethanol in the fermentation liquor was transferred to the vapor phase (headspace) almost completely within 3 min at a temperature of 105 °C when a very small volume (<50 μL) of sample was directly added to a sealed headspace sample vial (20 mL). The ethanol in the vapor phase was then measured by headspace GC using a flame ionization detector. The results show that the present method has an excellent measurement precision (RSD = 1.62%) and accuracy (recovery = 98.1 (±1.76%)) for the ethanol quantification in fermentation liquors. The method requires no sample pretreatment and is very simple and rapid.     

Rapid determination of furfural in biomass hydrolysate by full evaporation headspace gas chromatography

This paper reports a full evaporation (FE) headspace gas chromatographic (HS-GC) method for rapid determination of furfural in the biomass hydrolysate. The data show that a near-complete mass transfer of furfural in the sample from biomass hydrolysate to the vapor phase (headspace) was achieved within 3 min at 105°C when a very small (<40 μL) sample was added to a 20 mL headspace sample vial. The acid-catalyzed furfural decomposition under these conditions was negligible. The furfural in the vapor phase was then determined by HS-GC using a flame ionization detector. The results showed that the method has an excellent measurement precision (RSD<0.5%) and accuracy (recovery=100.2±1.7%) for furfural quantification in carbohydrate hydrolysate samples. The method requires no sample pretreatment, so it is simple, rapid and accurate, and suitable for applications in lignocellulosic biomass conversion to fuel ethanol or other high value-added products.     

Analysis of volatile fatty acids by gas chromatography separation of benzyl esters

Volatile fatty acids in aqueous media were esterfied in situ with phenyldiazomethane (PDM). Complete esterification was achieved in 3 h at 40°C under continuous stirring of an ether/water system. The process involved immediate transfer of benzyl esters into the organic phase. The separation of benzyl esters mixtures was carried out in glass capillary GC columns. The retention data and FID molar responses were determined for C1 to C6 acid benzyl esters, including 2-methylpropionic, 3-methylbutyric, 2-methylvaleric, and 2-ethylbutyric acid. An unusual relationship was observed between benzyl ester relative molar responses and carbon atom number.     

Analysis of anesthetic gas mixtures of halothane,nitrous oxide and oxygen by gas chromatography

Summary A simple dual-column system with a thermal conductivity detector is described, that can be used for the quantitative analysis of anesthetic gas mixtures of halothane (2-bromo-2-chloro-1,1,1-trifluoroethane), nitrous oxide and oxygen. The separation was performed on a Carbopack (SP 1000) column and a Porapak Q column arranged in series across the detector.     

On-line analysis of complex hydrocarbon mixtures using comprehensive two-dimensional gas chromatography

This paper discusses the first setup for on-line qualitative and quantitative comprehensive two-dimensional gas chromatography (GC × GC) of complex hydrocarbon mixtures. A built-in 4-port 2-way valve allows switching between flame ionization detection (FID) and time-of-flight mass spectrometry (TOF-MS) between runs, without the need to cool down and vent the MS. Proper selection of GC carrier gas flow rates enables maximal agreement between the obtained chromatograms in both configurations. For on-line analysis of reactor effluents, a dedicated sampling system allows automatic sampling of the hot reactor effluent gases and immediate injection of the sample on the GC × GC. To determine a complete effluent composition in a single run of the GC × GC, a subzero oven starting temperature was employed. Modulation is started when the oven temperature reaches 40 °C, thus dividing the chromatogram in a conventional 1D and a comprehensive 2D part. This work illustrates the mature and robust character of GC × GC, extending its capabilities from mere laboratory use to on-line routine analysis for industrial processes in the (petro-)chemical industry.     

Obtimization of separation conditions in reversed phase liquid chromatography using complex solvent mixtures

Summary Four different methods of calculation of retention in ternary mobile phases were compared and it was found that the simple calculation based only on two values of the capacity factors (one for each binary system that composes the ternary mobile phase) provides the accuracy of prediction that is, at least, comparable to the other methods of calculation that require a large number of preliminary experiments. The deviations from ideal behaviour in ternary solvent mixtures are discussed; some sources of errors can be avoided, at least partially, using binary systems of adequate compositions for preparation of ternary mobile phases. Several examples show the comparison of calculated and experimental selectivities in ternary solvent systems. A simple calculation can be used for rapid selection of an adequate ternary (or more complex) mobile phase, if it is necessary to achieve the separation of a given sample mixture.Presented at the 14th International Symposium on Chromatography London, September, 1982     

Measurement of the composition of gas desorbed from coal by gas chromatography

Summary Direct methods for the determination of the gas content of a coal seam are based upon extracting a coal sample, enclosing it in a sealed container and measuring the volume of the gas evolved. In our work we measured evolved gas as a function of time, type and quantity of low rank coal (lignite) at normal (atmospheric pressure and temperature) conditions. The evolved gas was, collected in gas sampling bags and analyzed by GC for its main components (carbon dioxide, methane and dimethyl sulfide). From the parameters obtained (gas volume, CH₄:CO₂ ratio, rate of gas desorption, time concentration profile and different lithotypes of lignite) a more detailed identification of hazardous areas in underground coal extraction could be ensured. Presented at: Balaton Symposium on High-Performance Separation Methods, Siófok, Hungary, September 3–5, 1997.     

毛细管柱气相色谱法测定土壤中的有机氯农药

研究了使用毛细管柱气相色谱法测定土壤中有机氯农药的分离条件、萃取方法、净化方法以及用替代品进行全程质量控制的方法。有机氯农药检出限在 1 .1～ 4.0 μg L之间 ,各化合物保留时间的RSD <0 .1 % ,所测定化合物的质量浓度在 0 .0 0 6～ 0 .2 0mg L范围内 ,各物质校正曲线 (浓度与峰面积 )的相关系数在 0 .992 6～ 0 .9971之间。用正己烷 丙酮 ( 1 1 ) 1 0 0mL超声波萃取 ,有机氯农药的萃取回收率在 96.3%～ 1 1 4% ,RSD为 0～ 1 1 %。用国产硅镁吸附剂净化 ,有机氯农药的回收率在 1 0 0 %～ 1 40 %之间 ,弗罗里硅土的回收率在 1 0 4 %～ 1 33%之间 ,硅镁吸附剂可以替代弗罗里硅土用于样品的净化。     

潜指纹残留物中油脂的气相色谱分析

建立一种适于分析潜指纹残留物中油脂组成的简便快速、灵敏可靠的GC/FID分析方法。以V(正己烷)∶V(CH2Cl2)=1∶10为提取剂,HP-5毛细管色谱柱和氢火焰离子检测器进行分析。潜指纹残留物中油脂组成复杂,不同个体捺印所得样品组成之间既有共同之处,又有各自典型特征;暗处保存及自然光照条件下,油脂组成发生变化,油脂含量总体呈下降趋势,但部分物质含量呈波动性变化;两种老化方式下的变化趋势相似,但自然光照条件下油脂衰减速度较快,光照10天后的潜指纹残留物中仍可见含量丰富的油脂。方法灵敏度能够达到单枚指纹残留物检测要求。     

Analysis of volatile fatty acids in biological specimens by capillary gas chromatography

A method was developed to analyze and quantitate volatile fatty acids such as acetic, propionic, butyric, iso-butyric, valeric, and iso-valeric acid from samples of biological origin. A capillary column system including an automatic on-column injection device as well as a precolumn of larger internal diameter than the analytical column was elaborated for this purpose. In order to obtain well resolved and correctly quantifiable chromatographic peaks it turned out to be essential to work under acidic/aqueous conditions. To achieve a better sample transfer into the chromatographic system an organic solvent had to be used together with the aqueous milieu, thus improving wetting properties of the liquid sample plug introduced into the column. Cold on-column injection was applied in order to avoid discrimination of the various acids due to sample splitting and the automatic technique was chosen in view of the large number of samples from biological extractions which had to be analyzed.     

Experimental study of gas mixtures in strong non-uniform electric fields

Argon-based gas mixtures of various concentration ratios at low pressures were studied in a gas proportional counter. Over-exponential increase of gas gain in mixtures with low partial pressure of any admixture was observed. The best energy resolution was measured at a gas gain of several hundreds for lower admixture concentrations, but at high gas gains R degraded very fast. The first Townsend ionization coefficient /P in low-pressure gases depended also on the gas pressure. The single-electron spectra had a peaked shape in mixtures with relatively high content of the molecular gas. In mixtures with lower molecular gas amount they changed the shape toward the over-exponential distribution. A partial pressure of 10 kPa was determined as a requirement for good quenching property of the mixture.     

四元共聚物的热裂解色谱-质谱分析

报道了2－丁烯、甲基丙烯酸甲酯、丙烯酸丁酯、丙烯酸辛酯四元共聚物在不同裂解温度下的热裂解行为。用热裂解色谱－质谱分析方法，研究了裂解温度对裂解产物的影响，并讨论了四元共聚物的热裂解规律。     

Fast determination of evaporation enthalpies of solvents and binary mixtures using a microsilicon chip device with integrated thin film transducers

A silicon chip device with two types of integrated platinum thin film resistors was applied for microcaloric measurements. It was shown that the device is capable of fast characterization of liquid evaporation behaviour and allows the determination of evaporation enthalpies for pure liquids and mixtures. The applicability was demonstrated for a wide range of solvents from nonpolar aliphatic solvents over polar organics to protic solvents (e.g. iso-octane, toluene, acetone, ethanol, methanol and water). The sample volumes were in the range of about 2-5 μL. The determination of transient times, in case of constant power mode, or the power integral over time was used for the fast estimation of binary liquid mixtures. Thermo-resistive measurements of 5 μL droplets of solvent mixtures like methanol/iso-propanol, ethanol/water, iso-octane/iso-propanol and iso-octane/1,4-dioxane showed significant changes in temperature characteristics and evaporation enthalpies in dependence on composition. The applied heating power was about 1 W, which corresponds to measurement times between a few seconds and a minute.     

Gas chromatography and gas chromatography/mass spectrometry for the characterization of complex mixtures of large oligosaccharides

High temperature gas chromatography and gas chromatography/mass spectrometry are used in the characterization of complex natural mixtures of permethylated oligosaccharides released from proteins or lipids. The high resolution allows separation of isomeric compounds and the mass range extends to oligosac-charides around molecular mass 2000 daltons or 10 sugar residues for isomalto-oligosaccharides. The mass spectra of permethylated oligosaccharide alditols from mucin glycopeptides are very informative and the approach allows a simple and rapid characterization of these complex components.     

Automatic system for rapid analysis of volatile compounds by purge-and-cold-trapping/capillary gas chromatography

A system for automatic analysis of volatile compounds by purge-and-cold-trapping/capillary gas chromatography is described. It is suitable for analysis of volatile compounds in a wide variety of samples, such as water, food products and environmental samples. Possibilities and limitations of the system are evaluated in relation to several parameters. The efficiency of different types of cryogenic trap (open tubular, coated, packed) is also investigated; it depends on purge-flow rate, temperature of trapping, and total purge volume. Examples of the analysis of volatile compounds in foods and water are given.     

土壤中多种有机氯及拟除虫菊酯类农药的GC-ECD测定

气相色谱法同时测定土壤中多种有机氯及拟除虫菊酯类农药。对土壤的分析结果：有机氯农药的检出限0．001～0、003μg／mL，拟除虫菊酯类农药检出限0.008～0．02μg／mL，线性相关系数0．9978～0．9999。用y（石油醚）：V（丙酮）=3：1超声波提取，有机氯农药回收率94．2％～124．0％，相对标准偏差为3．3％～8．8％（n=5）；拟除虫菊酯类农药回收率95．2％～118．3％，相对标准偏差为5．7％～7．1％（n=5）；方法适用于土壤样品中农药残留测定。     

Revisiting the problem of correcting retention parameters for pressure and temperature in gas chromatography

Summary It has been shown [1, 2] that the compressibility correction factor equals the ratio of gas pressure at the column outlet to the average pressure in the column,j=p _o /p _c , and, therefore, by multiplying by this factor, all experimentally measured retention volumes and flow rates are converted from ambient pressure to the average pressure in the column. This makes retention volumes corrected in this way independent of pressure. In contrast, correcting retention times for gas compressibility has no physical meaning and terms such as “corrected retention time” and “net retention time” should not be used. Similarly, recalculating corrected retention volumes to a standard temperature of 273 K appears to provide a thermodynamically sound basis for comparison of data obtained at different temperatures. In reality, it distorts actual relationships and should not be used. Presented at: Balaton Symposium on High-Performance Separation Methods, Siófok, Hungary, September 3–5, 1997.