Supercritical fluid chromatography of industrial paraffins and waxes

Summary The application of capillary SFC for SIMDIST investigations of paraffins and waxes is reported. Pressure, density and temperature of the mobile phase are optimized to obtain high chromatographic resolution of complex mixtures of industrial products. Isothermal linear pressure programming and asymptotic pressure and density programming are used in the range from 15 to 35 MPa in the isothermic mode above 100°C. SFC chromatograms of natural and synthetic paraffins, microcrystalline wax and candle wax are compared. The retention behaviour of paraffin mixtures and waxes has been investigated on methyl/phenyl and biphenyl capillary columns. The polarity of the stationary phases influences the absolute retention time more than it influences the chromatographic resolution.     

Structural and magnetic investigations of the mixed-valence Fe(II,III) two-dimensional layer complex, [Fe2(II) Fe2(III)(HCOO)10(C6H7N)6]n.

The structure of the complex, [Fe2(II)Fe2(III)(HCOO)10(C6H7N6)n, (1) exhibits a neutral two-dimensional layer network of alternating iron(II) and iron(III) ions, bridged equatorially by formate groups. All iron atoms are octahedrally coordinated, with iron(III) coordinating axially to one gamma-picoline and one formate group, while the iron(II) centers interact axially with two gamma-picoline groups, above and below the layer plane. The complex crystallizes in the triclinic space group P1 at all studied temperatures [at 120 K, the cell dimensions are: a = 10.228(1), b = 12.071(1), c = 12.072(1) A, alpha = 89.801(2), beta = 71.149(2), gamma = 73.371(2) degrees]. An intralayer antiferromagnetic exchange interaction of J = -2.8 cm(-1) between iron(II) and iron(III) was observed in the magnetic studies. Decreasing the temperature to close to 20 K causes a magnetic-ordering phenomenon to occur and a low-temperature phase with a long-range antiferromagnetic spin orientation appears. The magnetic phase transition was confirmed by M?ssbauer spectroscopic studies at temperatures above and below the critical temperature. Structural information of 1 from synchrotron X-ray diffraction data collected at room temperature and 16 K suggests that the antiferromagnetic ordering is caused by an enhanced pi-pi interaction between chi-picoline groups from adjacent layers.     

催化裂化USY／ZnO／Al2O3脱硫添加剂的高温水热失活

 对USY／ZnO／Al2O3汽油催化裂化脱硫添加剂经高温水热老化处理前后的脱硫性能进行了考察，发现老化后添加剂的脱硫性能大幅度下降．采用XRD和IR等技术对USY／ZnO／Al2O3添加剂在高温和高温水热条件下失活的原因进行了研究．结果表明，在高温下，ZnO可与USY沸石中的铝发生固相反应生成ZnAl2O4尖晶石，从而造成USY晶体结构崩塌，转变成无定形状态．在ZnO含量较高的条件下，ZnO可继续与USY晶体结构崩塌后生成的无定形的硅和铝的氧化物反应，生成Zn2SiO4硅锌矿和ZnAl2O4尖晶石结构．这一方面使添加剂失去了可形成硫化物吸附中心的ZnO，另一方面破坏了硫化物的裂化活性组分USY，从而造成添加剂脱硫性能下降甚至失去脱硫活性．ZnO对USY的破坏作用主要与温度有关．在USY／ZnO／Al2O3体系中，ZnO被ZnO与Al2O3之间形成的锌铝尖晶石膜固定并与USY隔离，单纯的高温条件对添加剂的破坏不显著，而水蒸气可以促进ZnO的移动，有利于ZnO与USY的接触，因此在高温和有水蒸气存 在的条件下添加剂的结构易遭到破坏．     

Construction of solid-liquid phase diagrams in ternary systems by titration calorimetry

Titration calorimetry was used to construct the solid-liquid equilibrium line in ternary systems containing the solute and an aqueous mixed solvent by measuring the heat of dissolution of the solid solute during successive additions of the liquid solvent. The plot of cumulated heats versus the mole ratio, n_solvent/n_solute, yields two (almost) linear increases of different slopes. These two lines represent successively the enthalpy of dissolution then the enthalpy of dilution of the medium; their intersection gives the solubility and the enthalpy of dissolution of the solute. Phase diagrams have been established over the whole concentration range for o-anisaldehyde, 1,3,5-trimethoxybenzene and vanillin, in water + methanol, +ethanol, or +n-propanol at 303, 313 and 318 K.     

铜基催化剂的结构、物性及其对混合碳四选择加氢反应的催化性能

 用XRD，XPS，SEM和H2－TPR等手段研究了铜基负载型催化剂的结\r\n构和物性及其对混合碳四加氢脱炔的催化性能．结果表明，在负载铜催\r\n化剂中加入一定量的Co可提高催化剂的加氢脱炔活性，而Co含量较少时\r\n加入少量的Ce也能提高催化剂的活性和选择性．Cu和Co之间存在着相互\r\n协同作用，使得活性组分在催化剂表面偏析，CuO在催化剂表面呈非晶\r\n相分散状态，催化剂颗粒粒径变小，催化剂更容易被还原，从而改善了\r\n催化剂的催化性能．     

{[Gd(DMF)_3(DMSO)(H_2O)_3](μ-CN)[Fe(CN)_5]}·2H_2O的合成,结构表征和磁性(英文)

0IntroductionThefirstmolecule鄄basedmagnetswerereportedin1986[1].Duringthelasttwodecades,moreandmoreattentionhasbeenpaidtothesynthesisofmolecule鄄basedmagnets,especiallytoPrussianBlueanalogu鄄es[2].TheoldPrussianBlueanalogueshavebeenbroughtuptodateduetoth…     

Dealkylation ofpara-nitrophenyldimethyl thiophosphate in micellar and liquid-crystalline media of then-decylammonium chloride-n-decylamine-water system

The kinetics of decomposition of p-nitrophenyldimethyl thiophosphate (1) were investigated spectrophotometrically in the n-decylammonium chloride-n-decylamine-water system (DAC-DA-H₂O), in which micellar or lamellar liquid-crystalline phases are formed as a function of the concentration of components. It was shown that1 is dealkylated in both phases. An increase in the surface charge density of associates decreases the rate of dealkylation. The activation energy in the lamellar phase is significantly higher than in the micellar phase.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan' Scientific Center, Russian Academy of Sciences, 420083 Kazan'. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 5, pp. 1042–1048, May, 1992.     

Headspace single-drop microextration for the detection of organotin compounds

The performance of single-drop microextraction (SDME), coupled with gas chromatography/mass spectrometry, was assessed for the determination of tributyltin compounds in water and solid samples. Experimental parameters impacting the performance of SDME, such as microextraction solvent and sampling and stirring time, were investigated. Analytical results obtained by SDME were compared with those generated by conventional solid phase microextraction (SPME) and liquid-liquid extraction (LLE) for the determination of TBT in PACS-2 sediment certified reference material (CRM).     

Selective Oxidation of Isobutene over CsFeCoBiMnMoOx Mixed Oxide Catalyst

Mixed oxide catalyst Cs0.1Fe2Co6BiMnMo12Ox was prepared by the coprecipitation method.Selective oxidation of isobutene was carried out in a fixed-bed reactor over Cs0.1Fe2Co6BiMnMo12Ox.The results showed that the catalyst had high catalytic activity. Under the optimum reaction conditions(n(i-C4):n(O2)=1:2-1:4, space velocity=180 h^-1, T=360℃), the yields of methacrolein and methacrylic acid can reach 80% and 8%, respectively. The total yield of liquid products (methacrolein, methacrylic acid and acetic acid) can reach about 90%.