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101.
通过吸附丝富集样品中的游离烃,热解析后直接进行色谱-质谱分析,该法适用于土、岩石、水及油气样品,操作简便,灵敏度高,可检测至C16的烃类,是油敢化探中行之有效的一种新方法。 相似文献
102.
Volkova L. K. Rudakov E. S. Nikolaenko A. V. 《Theoretical and Experimental Chemistry》2003,39(1):30-35
It was shown that at 70 °C sulfuric acid ([H2SO4] > 85 wt.%) solutions of 1-hydroxyadamantane and the solutions obtained in the reaction of adamantane with concentrated sulfuric acid oxidize saturated hydrocarbons (RH). Data on the kinetics, selectivity, kinetic isotope effect, and the effect of the acidity of the medium on the oxidation rate of RH indicate cleavage of the C—H bond in the substrate at the rate-determining stage and the direct participation of adamantyl carbocations. 相似文献
103.
Michael C. Bhm Joachim Schulte Rafael Ramírez 《International journal of quantum chemistry》2002,86(3):280-296
The absolute magnetic shieldings of benzene and ethylene have been theoretically studied under the conditions of thermal equilibrium, i.e., under explicit consideration of the nuclear degrees of freedom. For this purpose we have combined the Feynman path integral quantum Monte Carlo (PIMC) formalism with the gauge‐including atomic orbital (GIAO) approach in the Hartree–Fock (HF) approximation. The HF operator has been employed to derive the NMR parameters of the two hydrocarbons via an ensemble averaging over large sets of molecular configurations that are populated in thermal equilibrium. The nuclear fluctuations are responsible for a deshielding of the nuclei relative to the shieldings at the vibrationless minimum of the potential energy surface (PES). The influence of the nuclear degrees of freedom is largest for the isotropic part of the 13C shielding tensor. The theoretical results can be explained on the basis of simple geometrical considerations. The bond lengths in thermal equilibrium are larger than the bond lengths at the minimum of the PES. This length enhancement is the prerequisite for a deshielding of the nuclei in thermal equilibrium. The vibrational corrections of the nuclear magnetic resonance (NMR) parameters of benzene and ethylene are quantum driven; classical thermal degrees of freedom of the nuclei are of minor importance. Conceptual problems of theoretical studies of NMR parameters on the basis of a single molecular geometry are emphasized. The influence of the spatial uncertainty of the nuclei becomes decisive in molecules with light atoms. It is pointed out that the combination of the PIMC formalism with electronic Hamiltonians of state‐of‐the‐art quality renders possible accurate determinations of NMR parameters. © 2002 John Wiley & Sons, Inc. Int J Quantum Chem 86: 280–296, 2002 相似文献
104.
A rapid and simple fractionation procedure using solid-phase extraction (SPE) cartridges was developed for an accurate determination of aliphatic and polycyclic aromatic hydrocarbons in petroleum residues and further application in chemical fingerprinting of oil spills by gas chromatography-mass spectrometry (GC-MS). Among the adsorbents evaluated, SiO2/C3-CN exhibited the best selectivity, providing, by elution with n-hexane (4 ml) and n-hexane-CH2Cl2 (1:1) (5 ml), two well-resolved aliphatic and aromatic hydrocarbon fractions, with recoveries of 97 +/- 7.2 and 99.7 +/- 13.9%, respectively. The SPE fractionation procedure was compared with the conventional silica-alumina adsorption chromatography showing similar results but practical advantages in terms of reproducibility, analysis time, solvent reduction and cost. Moreover, is particularly suitable for routine analysis with a high sample throughput. The developed methodology was tested in the characterization of fuel-oil samples collected along the Spanish north-west coast, after the Prestige oil spill accident. 相似文献
105.
Magdalena Kurdziel Elżbieta Szczepaniec-Cieciak Monika Watorczyk Barbara Dabrowska 《Journal of solution chemistry》2004,33(5):453-464
The solubility of solid 2-methyl-1,3-butadiene (isoprene) in liquid argon at a temperature of 87.3 K and in liquid nitrogen at 77.4 K has been measured by the filtration method. The hydrocarbon contents in solutions were determined using gas chromatography. GC–MS was used to identify impurities in the solute. The experimental value of the mole fraction solubility of solid isoprene in liquid argon at 87.3 K is (1.41 ± 0.27) × 10–6 and (1.56 ± 0.36) × 10–7 in liquid nitrogen at 77.4 K. The Preston–Prausnitz method was used for calculation of the solubilities of solid hydrocarbon in liquid argon in the temperature range 84.0–110.0 K and in liquid nitrogen from 64.0 to 90.0 K. The solvent–solute interaction parameters l
12 were also calculated. At 90.0 K liquid argon is a better solvent for isoprene than is liquid nitrogen. The experimental values of the solubilities of isoprene in liquid argon and nitrogen were compared with results obtained for selected unsaturated and aromatic hydrocarbons. 相似文献
106.
Magdalena Kurdziel Elżbieta Szczepaniec-Cięciak Barbara Dąbrowska Wojciech Nitek Katarzyna Paliś Edyta Ślusarska 《Journal of solution chemistry》2003,32(7):601-615
The solubilities of solid 2,3-dimethylbutane and cyclopentene in liquid argon at a temperature of 87.3 K and in liquid nitrogen at 77.4 K have been measured by the filtration method. The hydrocarbon contents in solutions were determined using gas chromatography. GC–MS was used to identify impurities in solutes. The experimental value of the mole fraction solubility of solid 2,3-dimethyl-butane in liquid argon at 87.3 K is (8.26 ± 1.60) × 10–6 and (2.77 ± 0.94) × 10–8 in liquid nitrogen at 77.4 K. The experimental value of the mole fraction solubility of solid cyclopentene in liquid argon at 87.3 K is (5.11 ± 0.44) × 10–6 and (4.60 ± 0.76) × 10–8 in liquid nitrogen at 77.4 K. The Preston–Prausnitz method was used for calculation of the solubilities of solid hydrocarbons in liquid argon in the temperature range 84.0–110.0 K and in liquid nitrogen from 64.0 to 90.0 K. The solvent–solute interaction parameters l
12 were also calculated. At 90.0 K liquid argon is a better solvent for investigated solid hydrocarbons than is liquid nitrogen. 相似文献
107.
The excess molar enthalpies H
m
E
for the binary mixtures of furfural with the aromatic hydrocarbons namely benzene, toluene, ethylbenzene and o-, m-, and p-xylenes were determined at 35°C. The values for all the mixtures studied are positive over the entire range of composition and follow the order: o-xylene>m-xylene>ethylbenzene>p-xylene>benzene>toluene. The results are discussed in terms of the unlike specific interactions present in the binary mixtures. 相似文献
108.
J.F. Fernández-Sánchez C. Cruces-Blanco A. Fernández-Gutiérrez 《Analytica chimica acta》2004,506(1):1-7
We describe here a method for detecting and quantifying the highly carcinogenic polycyclic aromatic hydrocarbon (PAH) benzo[a]pyrene (BaP) in water, based on a flow-trough optical sensor. The technique is fast (response time of 40 s) and simple and at the same time meets the standards of sensitivity and selectivity required by the European Guidelines on Water for Human Consumption. The optosensor is based on the on-line immobilization of BaP on a non-ionic resin (Amberlite XAD-4) solid support in a continuous-flow system. BaP was analyzed in a 15 mM H2PO4−/HPO42− buffer solution with 25% (v/v) 1,4-dioxane at pH 7. Fluorescence intensity was measured at λex/em=392/406 nm. The experimental conditions (reagent phase, pH, type and concentration of buffer solution and organic solvent) and flow-injection values (flow rate and injection volume) were carefully controlled. Under these conditions the optosensor was sensitive to a linear concentration range of between 3.0 and 250.0 ng l−1 with a detection limit of 3.0 ng l−1 and a standard deviation of 1.5% at 150 ng l−1. The optosensor was applied to the quantification of BaP in drinking and waste water samples (95-105% recovery) in presence of the other 15 EPA PAHs at 1000 ng l−1 concentration level. The influence of other fluorescent polycyclic aromatic hydrocarbons and potential interference from ions usually present in water was also evaluated. 相似文献
109.
110.
J. Nassar J. Goldbach 《International journal of environmental analytical chemistry》2013,93(2):145-159
Abstract The problem of determining the concentration changes of reactive hydrocarbon immissions as a function of time was solved by means of an automatic gas chromatograph which, without enrichment, could record ethylene and acetylene in ppb concentrations. At the same time various other pollutants were covered, so that by a mutual allocation of the individual components it was possible to identify certain emitter groups. The results clearly show that ethylene and acetylene primarily originate from the combustion processes of the automobiles, while the handling and storage of petroleum products and their processing do not exert any influence on the immission of the two components. By way of time series measurements during a summer week in 1976 with very intensive solar radiation it was possible to show indirect secondary photochemical reactions. 相似文献