Excess molar enthalpies of binary mixtures of 1-hexene with some cyclic and aromatic hydrocarbons at 298.15 K

Microcalorimetric measurements of excess molar enthalpies, at 298.15 K, are reported for the four binary systems formed by mixing 1-hexene with the cycloalkanes: cyclohexane and methylcyclohexane, and with the aromatic hydrocarcons: benzene and toluene. Smooth Redlich-Kister representations of the results are presented. It was found that the Liebermann-Fried model also provided good representations of the results.     

Refractive index of standard oils as a function of wavelength and temperature

The refractive indices (n) of eight standard oils from Physikalisch Technische Bundesanstalt, Germany were determined with an accuracy of ±1×10⁻⁴ by using Abbe Refractometer. The measurements were performed at temperature 20°C in the spectral range 0.4–0.7 μm. The experimental data were fitted to the simple Cauchy dispersion formula and the results were found to be consistent within the limits of experimental error. In all cases, the refractive index decreased monotonically with increasing wavelength. The refractive indices (n) of these oils have been measured as a function of the temperature t (20°C up to 50°C) at λ=0.589 μm and were found to have linear temperature dependencies. The refractive indices of the studied oils and the uncertainty in their values are calculated at λ=0.589. The Lorentz–Lorenz (L–L) formula has been tested and it was found to be valid with a maximum deviation of 0.4% and was used to calculate the molecular polarizability θ.     

Characterization of Metallo Bis(terpyridine) Diblock Polymers by Nonaqueous Capillary Zone Electrophoresis

A method of nonaqueous capillary zone electrophoresis (CZE) has been developed to characterize block (co)polymers of poly(ethylene oxide) and poly(styrene) containing metallo bis(terpyridine) complexes as bridging units. Specific CZE separation conditions had to be applied, with barium perchlorate dissolved in N-methylformamide (NMF) as background electrolyte and OV-1701-OH deactivated capillaries. For detection UV absorption was measured at a wavelength of 316 nm. Metallo diblock polymers with molecular weights up to 30,000 Da could be analyzed by the proposed nonaqueous CZE method. Experiments performed with polymeric compounds containing Fe, Ni or Ru as central metal ions showed that their electrophoretic mobilities were independent of the type of metal ion. Therefore, the data on the size of the polymeric compounds could be obtained using just one set of calibration standards. Polydispersities of the samples calculated from the experimental results were in correlation with the polydispersities of the polymers used in the synthesis of the metallo diblock polymers. Several polymeric samples contained metallo mono(terpyridine) complexes as impurities. These by-products could be separated from the main product. With symmetrical diblock polymers only one by-product was detected, while with an asymmetric diblock polymer two types of mono-complexes were found. The amount of the mono-complexes present as impurities was dependent on the type of central metal ion (Ni > Fe >> Ru).     

Excess enthalpies of some 2-alkanone + 1-chloroalkane binary mixtures at 25 and 35°C

Excess molar enthalpies h^E at 25 and 35° C and atmospheric pressure, are reported for the binary mixtures formed by a 2-butanone and 2-pentanone with 1-chlorobutane, 1-chloropentane, 1-chlorohexane, or 1-chlorooctane. The h^E values for all the mixtures are positive, increasing as the 1-chloroalkane length increases and as the ketone length decreases. Excess molar enthalpies depend slightly on the temperature. The experimental values together with those from the literature were used to calculate the interaction parameters for the Dang-Tassios version of the UNIFAC model.Communicated at the Festsymposium celebrating Dr. Henry V. Kehiaian's 60^th birthday, Clermont-Ferrand, France, 17–18 May 1990.     

Studies on pre-hump and main fractions of cellulose-2,5-acetate in acetone

Technical cellulose-2.5-acetates (CA 2.5) were characterized regarding their carbohydrate composition in comparison to the raw material. The association of the CA 2.5 samples in acetone was studied by size exclusion chromatography (SEC) using various acetone grades and styrene divinylbenzene copolymer columns. In HPLC grade acetone with and without addition of 1% water up to three different pre-humps eluted in front of the main fraction of the polymer. The evaluation of the main peak by light scattering measurements resulted in high molar masses indicating that for these technical CA 2.5 samples even the main fraction is not dissolved without association. No pre-humps or association phenomena were observed after addition of 1 ppm LiBr to HPLC grade acetone or with p.a. grade acetone. In addition pre-hump enriched and pre-hump free fractions were isolated by fractionated precipitation. The carbohydrate composition of these fractions was determined and correlated with their association pattern in SEC investigations.     

Calculation of cyclodextrin-mediated enantiomer ratio shifting of racem norgestrel in aqueous solutions

Enantioselective solubility of rac-norgestrel was found in the presence of γ-cyclodextrin or hydroxypropyl-γ-cyclodextrin. In both cases the efficacious enantiomer was dissolved in greater extent. Calculating the molar absorptivity and molar ellipticity spectra of the γ- and hydroxypropyl-γ-cyclodextrin aqueous complexes, a simple and rapid direct circular dichroism (CD) spectrometric method was obtained for the determination of the enantiomer ratio in aqueous solutions.     

Molar extinction coefficients of solutions of some organic compounds

Molar extinction coefficients of aqueous solutions of some organic compounds, viz. formamide (CH₃NO),N-methylformamide (C₂H₅NO),NN-dimethylformamide (C₃H₇NO),NN-dimethylacetamide (C₄H₉NO), 1,4-dioxane (C₄H₈O₂₄), succinimide (C₄H₅NO₂) and solutions of acetamide (C₂H₅NO) and benzoic acid (C₇H₆O₂) in 1,4-dioxane (C₄H₈O₂) have been determined by narrow beam γ-ray transmission method at 81, 356, 511, 662, 1173 and 1332 keV. The experimental values of mass attenuation coefficients of these compounds have been used to calculate effective atomic numbers and electron densities. The additivity rule earlier used for aqueous solution has been extended to non-aqueous (1,4-dioxane) solutions.     

Excess enthalpies of mixing tetrahydrofuran and tetrahydropyran with some chloroalkanes at 26.9°C

Excess enthalpies of mixing H _m ^E of tetrahydrofuran and tetrahydropyran with trichloromethane, tetrachloromethane, 1,2-dichloroethane, 1,1,2-trichloroethane and 1,1,2,2-tetrachloroethane have been determined at 26.9°C and are found to be negative over the entire composition range for both sets of the ether mixtures. H _m ^E decreases in the sequence; dichloroethane > tetrachloromethane > trichloroethane > trichloromethane > tetrachloroethane. The results are explained on the basis of strong O...H-C and weak Cl...O specific interactions. Flory's theory has been used to correlate the experimental data with good agreement found between the theoretical and experimental values of H _m ^E .     

反相液体色谱中饱和醇保留行为的研究 Ⅰ.低碳醇保留行为与溶质分子结构的关系

本文从吸附-疏溶剂理论出发,根据热力学平衡观点,导出了一定固定相和流动相时,描述溶质保留行为与其分子结构关系的理论模型,并用之预测了饱和醇的保留值,获满意结果。从而表明本模型不但能用于同系物,而且亦可用于同分异构体及立体异构体保留行为的预测。