基于基团贡献法的HFC＋HC混合物气液相平衡性质预测

基于基团贡献法的思想,本文采用改进的SRK状态方程和修正的MHV1混合规则,将UNIFAC基团贡献法扩展用于HFC HC二元混合物气液相平衡性质的描述,给出了基团划分表和基团间的相互作用参数,使用该方法可以较好地再现HFC HC二元混合物的气液相平衡性质,并且具有良好的预测效果.     

Solid–liquid equilibria based on an equation of state for chain fluids

Solid–liquid equilibria were studied using an equation of state previously developed for fluids containing chain-like molecules. The method was used to correlate solubilities of normal alkanes and aromatic compounds with high molecular mass in hydrocarbon solvents. With one temperature independent parameter for the interaction energy, good agreement can be obtained between calculated results and experimental data for selected systems.     

Quantification of Polycyclic Aromatic Hydrocarbons in Avian Dried Blood Spots by Ultra-performance Liquid Chromatography with Simple Liquid Extraction and Phospholipid Solid-phase Extraction Preparation

Here, a simple, reliable method for the quantification of the 16 EPA priority polycyclic aromatic hydrocarbons in dried blood spots is outlined using liquid extraction and phospholipid solid-phase sample cleanup coupled with analysis by ultra-performance liquid chromatography with ultraviolet–visible detection. Whole blood spotted on Whatman FTA cards was efficiently quantified by extraction into acidified methanol and passed through a phospholipid solid-phase extraction well plate before injection into a liquid chromatography under reverse-phase conditions. The analyte recoveries in quality control samples ranged from 63.4 to 104.1%, with relative standard deviations from 0.48 to 2.04%. These figures of merit are comparable with measurements in whole blood or serum using similar techniques. The method detection limits were from 45.0?ng·g^?1 for benzo[g,h,i]perylene to 118.7?ng·g^?1 for chrysene, with matrix spike recoveries from 64.3 to 99.4%, demonstrating acceptable sensitivity and low matrix interference. With a simple liquid extraction approach and short 16-min liquid chromatography, the dried blood spots were effectively and rapidly analyzed.     

PDMS-Au复合基底上多环芳烃分子的表面增强拉曼光谱

利用聚二甲基硅氧烷(PDMS)对有机物的富集功能,通过在金纳米粒子单层膜(Au MLF)表面旋涂薄层PDMS膜制备PDMS-Au MLF复合表面增强拉曼光谱(SERS)基底.研究了SERS增强性能与旋涂液浓度及稀释溶剂间的关系,考察了复合基底增强活性的均匀性.研究发现,采用叔丁醇为稀释溶剂,浓度为2%(质量分数)的旋涂液时所得复合基底表面多环芳烃(PAHs)的SERS信号强度最高,且此基底SERS信号强度偏差小于10%.分别以PDMS-Au MLF复合材料和Au MLF作为基底,对比研究了对萘、蒽、菲和芘4种多环芳烃的SERS检测能力.结果表明,PDMS-Au MLF复合基底对以上4种有机物的检出限分别为10~(-6),10~(-7),10~(-8)及10~(-7)mol/L,相比于单一Au MLF基底,其检测限至少降低了1个数量级,这主要源自于PDMS对PAHs的富集作用,且此类复合基底可用于多种多环芳烃混合物的特征识别.     

Supercritical fluid chromatography hyphenated with twin comprehensive two-dimensional gas chromatography for ultimate analysis of middle distillates

This paper reports the conditions of online hyphenation of supercritical fluid chromatography (SFC) with twin comprehensive two-dimensional gas chromatography (twin-GC × GC) for detailed characterization of middle distillates; this is essential for a better understanding of reactions involved in refining processes. In this configuration, saturated and unsaturated compounds that have been fractionated by SFC are transferred on two different GC × GC columns sets (twin-GC × GC) placed in the same GC oven. Cryogenic focusing is used for transfer of fractions into the first dimension columns before simultaneous GC × GC analysis of both saturated and unsaturated fractions. The benefits of SFC–twin-GC × GC are demonstrated for the extended alkane, iso-alkane, alkene, naphthenes and aromatics analysis (so-called PIONA analysis) of diesel samples which can be achieved in one single injection. For that purpose, saturated and unsaturated compounds have been separated by SFC using a silver loaded silica column prior to GC × GC analysis. Alkenes and naphthenes are quantitatively recovered in the unsaturated and saturated fractions, respectively, allowing their identification in various diesel samples. Thus, resolution between each class of compounds is significantly improved compared to a single GC × GC run, and for the first time, an extended PIONA analysis of diesel samples is presented.     

有机化合物的氧化溴化研究进展

综述了几类在氧化剂存在下的羰基α位、芳环、烯烃双键、烷基苯苄位及烷烃上的氧化溴化反应。氧化溴化体系主要有Br-/H2O2和Br-/BrO3-体系。总结了不同反应条件对反应收率的影响,并展望了该领域的研究前景。     

Densities, speeds of sound and viscosities of binary liquid mixtures of octan-2-ol with benzene and halobenzenes at 298.15 and 303.15 K

Densities ρ, speeds of sound u, viscosities η and refractive indices n_D of binary mixtures of octan-2-ol with benzene, chlorobenzene and bromobenzene have been measured over the entire range of composition at 298.15 and 303.15 K and atmospheric pressure. From the experimental data, excess molar volumes V^E, isentropic compressibilities κ_S, excess isentropic compressibilities κ_S^E, and deviations of speeds of sound u^D, have been calculated at 298.15 and 303.15 K. These excess functions have been fitted to the Redlich-Kister polynomial equation. The viscosity data have been correlated using Kendall-Monroe, Grunberg-Nissan, Tamura-Kurata, Hind-Mclaughlin Ubbelohde and Katti-Chaudhary viscosity models, and McAllister's three-body interaction model at different temperatures.     

Correlation between hydrocarbon distribution and water-hydrocarbon ratio in Fischer-Tropsch synthesis

In order to shorten the evaluation cycle of cobalt catalyst before the optimized catalyst is fixed on, a mathematical method is proposed to calculate weight percentage of C5+ hydrocarbons. Based on the carbide polymerization mechanism and the main hydrocarbons being linear alkanes and α-olefins, the correlation between hydrocarbon distribution and the molecular mass ratio of water to hydrocarbons is discussed. The result shows the ratio was within the range of 1.125-1.286 and the lower the ratio, the more gaseous hydrocarbons were obtained. Moreover, a linear equation between the weight percentage of C5+ hydrocarbons and the weight ratio of C5+ hydrocarbons to the total water is established. These results are validated by corresponding experiments. The weight percentage of C5+ hydrocarbons could be immediately calculated by this linear equation without detailed gas chromatography (GC) analysis of them.     

Interplay between bulk viscoelasticity and surface energy in autohesive tack of rubber‐tackifier blends

The effects of change in surface energy and bulk viscoelastic properties on the autohesive tack strength of brominated isobutylene‐co‐p‐methylstyrene (BIMS) rubber have been investigated by the addition of hydrocarbon resin (HCR) tackifier and maleated hydrocarbon resin (MA‐g‐HCR) tackifier. The addition of compatible HCR tackifier results in a reasonable increment in the tack strength of BIMS rubber by modifying only the bulk viscoelastic properties (compliance, entanglement molecular weight, relaxation time, self‐diffusion, and monomer friction coefficient values) of BIMS rubber to perform better during the course of bonding and debonding steps of the peel test. Incorporation of MA‐g‐HCR tackifier (containing 5–20 wt % of grafted maleic anhydride) steadily increases the tack strength of BIMS rubber further by precisely modifying both the surface energy and bulk viscoelastic properties to perform much better in the bonding and debonding steps. However, beyond 20 wt % of grafted maleic anhydride in the HCR tackifier, the tack strength starts decreasing due to the incompatibility between the blend components, and hence, the bulk viscoelastic properties required for bond formation are severely retarded by the interrelated reinforcing effect and the phase separation effect of the brittle MA‐g‐HCR tackifier in the BIMS rubber. Hence, the polar groups in a tackifier will contribute to significant enhancement of autohesive tack strength only if the bulk viscoelastic property of the rubber‐tackifier blend is favorable for bond formation and bond separation. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 972–982, 2010